JP2000026561A - Reemulsifiable polymer and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a (co)polymer having a reemulsification function in water at pH>=5 by constituting particles of a core/shell structure in which at least one part of a specific core surface is coated with a prescribed shell. SOLUTION: This (co)polymer is composed of particles having a core/shell structure in which at least a part of core of (B) a (co)polymer having (b) >=0 wt.% and <40 wt.% repeating unit selected from (i) a repeating unit containing a pendant group of formula I (R1 and R2 are each H, a 1-12C alkyl or the like) and (ii) a repeating unit containing a pendant group of formula II (R3 is a 1-30 alkylene or the like) as a repeating unit is coated with a shell of (A) a (co)polymer having (a) >=20 wt.% and <100 wt.% reaping unit selected from the component (i) and the component (ii) as a repeating unit. The amount of the component A is 15-85 wt.% and that of the component B is 85-15 wt.% based on the total of the components A and B. The content of the component (a) is higher than that of the component (b).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a (co) polymer particle having a function of substantially re-emulsifying in water having a pH of 5 or more, and a method for producing the same.

[0002]

2. Description of the Related Art Since an aqueous emulsion obtained by an emulsion polymerization method generally contains 30 to 90% by weight of water as a dispersion medium, a large amount of water is carried during distribution and transportation. There were problems, both in terms of cost and cost.

[0003] On the other hand, the re-emulsifiable polymer is in a solid or paste form containing no or almost no water, as opposed to a normal aqueous emulsion, so that it can be easily distributed, transported and stored. It is characteristic in that it can be returned to an emulsion similar to a normal aqueous emulsion by adding it to water when necessary.

[0004] The re-emulsifiable polymer or its powder can be premixed with other powders such as cement, gypsum, pigment and the like in a desired formulation and provided as a one-packaged product. A product obtained by premixing a re-emulsifiable polymer or its powder into one package has been widely applied in the field of cement modifiers. Such a product obtained by premixing a re-emulsifiable polymer or a powder thereof into a single package is a compact and lightweight powder in the course of distribution, transportation and storage, and is used together with the powder at a construction site during use. By mixing the water, the desired concrete can be prepared in one step and used immediately. When the polymer is mixed, a complicated procedure such as a measuring operation can be largely omitted, so that there is a great merit in that the workability is extremely improved. Gallon cans and drums, which are necessary in the case of ordinary aqueous emulsions, are no longer required, so packing costs can be reduced at the time of shipment, and the amount of packing materials such as gallon cans and drums to be disposed of after use is greatly reduced. This is advantageous in that it can be reduced. In the case of a premixed one-package product, since it is accurately measured in advance to a desired prescription, the quality control of concrete at the time of construction is facilitated, and the reliability of the construction is further improved.

[0005] Therefore, the re-emulsifiable polymer or its powder according to the present invention is advantageous at least in the following points as compared with ordinary aqueous emulsions. Costs and energy required for distribution, transportation, and storage can be reduced. Since a large liquid container is not required, the packaging cost can be reduced. Since a large liquid container is not required, industrial waste can be reduced. In the case of a premixed one package product,
Since almost no weighing operation is required at the construction site,
Significant labor savings can be realized. In the case of a premixed one package product,
By mixing the powder and water, the desired concrete can be prepared in one step, so that significant labor savings can be realized. In the case of a premixed one package product,
Since the desired formulation is accurately measured in advance, the quality control of the concrete at the time of construction is facilitated.

[0006] However, the re-emulsifiable polymer produced by the conventional technique is disadvantageous in at least the following points since it employs a conventional spray drying method (conventional spray drying method). The particles are thermally fused together by heating in the conventional spray drying method, so that the re-emulsifiability is not sufficient. The conventional spray drying method requires a large-scale apparatus, and
Since a large amount of energy is consumed, it is disadvantageous in terms of cost.

A. Conventional Techniques Related to Polymer Particles Conventional techniques related to polymer particles are shown below, but none of them show re-emulsifiability or re-emulsifiability was not always satisfactory. In addition, any of the prior arts relating to polymer particles exhibiting re-emulsifiability shown below adopt a conventional spray drying method, and the re-emulsifiability is not sufficient because of the inevitable method. .

[Japanese Patent Laid-Open No. 59-193903]
No. 9-193903 (Applicant; Tosoh Corporation) discloses an unsaturated monomer in the presence of a special water-soluble copolymer which acts as a stabilizer or a powdering agent at a specific pH value. A technique for easily obtaining a powder composition having no lumps by polymerizing the compounds is disclosed. Specifically, the method comprises polymerizing a stable emulsion in the presence of a water-soluble copolymer of methacrylamide and an unsaturated carboxylic acid, followed by p
This is a production method in which the polymer is separated, dehydrated and dried at H4 or lower. However, to the extent disclosed, it is understood that the configuration of the invention is as follows.

In the invention disclosed in JP-A-59-193903, the water-soluble copolymer functions as a stabilizer for stably performing the emulsion polymerization, and for obtaining a powder without lumps. Function as a powdering agent,
It has two functions. According to this technique, emulsion polymerization is performed in the presence of a water-soluble copolymer having a function as a stabilizer to obtain a powder having no aggregate. That is, (A) a radical-polymerizable unsaturated bond-containing monomer (eg, styrene or the like) is converted into an aqueous solution of (B) methacrylamide and an unsaturated carboxylic acid (preferably, methacrylic acid or itaconic acid). First, in the presence of a water-soluble copolymer, polymerization is performed in an aqueous medium at a pH of 5 or more to obtain a stable emulsion by the action of the component B as a stabilizer, and then the pH is lowered to 4 or less. The polymer is separated from the emulsion by the action of the component B as a powdering agent, and the polymer is further dehydrated.
Dry to obtain a powder composition.

The weight ratio of the radically polymerizable monomer having an unsaturated bond (A) to the water-soluble copolymer (B) is (A) 1
(B) 1 to 10 parts by weight based on 00 parts by weight,
It is described that if (B) is less than 1 part by weight, the effect of pulverization of the emulsion is reduced, and if the amount exceeds 10 parts by weight, it becomes expensive and is unnecessary. In fact, in Examples 7 to 9, 2 parts by weight of (B) was used for 100 parts by weight of (A).

In preparing a water-soluble copolymer, when methacrylic acid or itaconic acid is used as a monomer as an unsaturated carboxylic acid, the composition ratio of methacrylic acid and itaconic acid to methacrylamide is 9/1. It is disclosed that the water-soluble copolymer has a function as a powdering agent in the range of up to 1/9. As a mode for lowering the pH, a method of adding hydrochloric acid or the like while stirring is disclosed.

The problem to be solved by this technique is only powdering of the polymer, and no re-emulsification of the powdered polymer is planned at all. Also, redispersibility is not inherent in the disclosed powdered polymers.

[Japanese Patent Publication No. 3-54973] Japanese Patent Publication No. 3-5
No. 4973 (Applicant; Wakka Himmie GMBH)
Is prepared by emulsion polymerization of an ethylenically unsaturated compound in the presence of a specific protective colloid and a free radical-forming initiator, followed by drying to obtain a dispersed powder having excellent fluidity and good redispersibility. A manufacturing technique is disclosed. That is, a protective colloid selected from a water-soluble starch having an amylose content of 30% by weight or less, a water-swellable starch, a dispersed starch, a cyanalkylated, hydroxyalkylated and / or carboxylated starch, and a water-soluble protein. Emulsion (co) polymerization of one or more copolymerizable ethylenically unsaturated compounds in an aqueous medium containing 5% by weight or more and a free radical-forming initiator (eg, isopropyl hydroperoxide) To obtain an aqueous dispersion having a solid content of 10 to 75% by weight. Next, if necessary, 0 to 40% by weight of an anti-tackiness agent (eg, PVA) and / or an atomization aid (eg, dextrin) is added to the aqueous dispersion, followed by spray drying.

[JP-A-3-210336]
No. 210336 (Applicant; Nippon Paint Co., Ltd.)
In a method of obtaining crosslinked resin particles by a predetermined post-emulsion method from a resin having a glass transition temperature of 0 ° C. or less, inter-particle fusion is performed by adding a plurality of specific substances to the resin and subjecting the resin to a post-emulsification method. There is disclosed a technique for obtaining crosslinked resin particles having no resiliency and excellent storage stability.

That is, a step of dispersing a resin component in water from a resin having a glass transition temperature (Tg) of 0 ° C. or less such as an elastomer such as acrylic rubber, polybutadiene, polyisoprene, chloroprene, polyε-caprolactone, and polytetramethylene glycol. In a method of obtaining crosslinked resin particles by a post-emulsification method comprising a step of three-dimensionalizing the inside of the dispersed particles and a step of removing the aqueous medium, a resin having a Tg higher than that of the resin by 20 ° C. or more in a polymerized state is given. Monomer (eg, styrene) or Tg 2
After blending a resin (eg, PS) higher than 0 ° C. or higher and a polyfunctional vinyl compound (eg, neopentyl glycol methacrylate) with the resin component, the mixture is subjected to the above-mentioned post-emulsification method.

[Japanese Patent Publication No. 4-59324] Japanese Patent Publication No. 4-5
No. 9324 (Applicant; BASF AG)
Non-adhesive, non-adhesive, which can be stored at room temperature by spray drying an aqueous dispersion containing a water-soluble alkali (earth) metal salt of a vinylpyrrolidone-vinyl acetate copolymer or a naphthalenesulfonic acid-formaldehyde condensation product. A method for producing a polymer powder that is soluble and redispersible in water is disclosed. That is, as a water-soluble polymer substance, (A) 20 to 70% by weight of vinylpyrrolidone and 30 to 30% by weight of vinyl acetate
From 80% by weight of the copolymer and / or (B) the water-soluble alkali metal salt and / or alkaline earth metal salt of the naphthalenesulfonic acid-formaldehyde condensation product, from 2 to 40% by weight, based on the polymer of the dispersion After addition in%, the aqueous polymer dispersion is spray-dried. The redispersible polymer powders thus obtained are particularly suitable as additives to hydraulic binders such as gypsum, cement, mortar and magnesia cement.

[Japanese Patent Application Laid-Open No. 5-194681]
194681 (Applicant; Rohm and Haas C
O) discloses a technique relating to a method for producing a novel redispersible core-shell polymer powder effective as a mortar modifier. That is, by spray-drying a core / shell polymer produced by polymerizing the core in the presence of an alkali-soluble shell, wherein the core and shell are chemically grafted through the use of a polyfunctional compound. The resulting redispersible polymer powder is disclosed. More specifically, it has a shell of an alkali-soluble emulsion polymer and a core of a water-insoluble emulsion polymer, and the core polymer and the shell polymer are chemically grafted by using a polyfunctional compound. A redispersible polymer powder made from a core-shell polymer that has been bound. This core-shell polymer is produced by a two-stage sequential emulsion polymerization method in which an alkali-insoluble emulsion polymer core is polymerized in the presence of an alkali-solubilized emulsion polymer. When this core-shell polymer powder of the present invention is used as a cement modifier, improvements in the physical properties of the powder and the properties of the cement mortar are noted.

[Tokuhei Hei 5-501575] Tokuhyo Hei Hei 5-
No. 501575 (Applicant; Henkel KG Auf Actien) discloses that the pH of an aqueous solution of a stabilizer comprising a starting amphoteric polymer is adjusted to an isoelectric point with an acid or the like, and the starting amphoteric polymer is precipitated from the aqueous solution. The value is adjusted and redissolved, a catalyst and the like are added, emulsion polymerization is carried out, and shear stability and water resistance are excellent. A method for making a polymer dispersion is disclosed. That is, the pH of an aqueous solution of a stabilizer comprising a starting amphoteric polymer made of a compound having a specific chemical structure and a monomer such as styrene is adjusted to the isoelectric point with a non-volatile acid or base to start. The amphoteric polymer is precipitated from the aqueous solution and, using a volatile acid or base, adjusted to the desired pH value for the emulsion polymerization and redissolved, after which the unsaturated monomer of the vinyl structure is non-volatile neutralized. The mixture is neutralized with an agent, added together with a catalyst and, if necessary, an auxiliary, and emulsion-polymerized to obtain a desired dispersion.

B. 2. Related Art of Protective Colloid Polymerization The protective colloid polymerization method is a known and publicly used polymerization method. The concept of the words "protective colloid polymerization" and "protective colloid"
And the concept and principle of the protective colloid polymerization method is, for example,
"Introduction to Emulsion (Tsuntaka Matsumoto) Industrial Materials, Volume 24
No. 3, pages 10 to 15 ". Above all, in the review, "FIG. 2 Emulsion Polymerization of Hydrophilic Monomer" (page 12) and its description ("Emulsion Polymerization of Hydrophilic Monomer" on page 12), and further, "FIG. Stabilization ”(page 13) and its description (12
項 Page 13 “Stabilization of emulsion particles”), there is an easy-to-understand explanation.

In the present specification, unless otherwise specified,
Clarifying the cited documents and cited ranges is part of the disclosure of the present specification, and by referring to the specified cited ranges, those skilled in the art can directly and Matters that can be uniquely derived are also disclosed in the specification of the present application.

Specific examples of known techniques of the protective colloid polymerization method include, for example, the techniques disclosed in the following JP-A-2-173003 and JP-A-4-185607.

[JP-A-4-185607] JP-A-4-185607
No. 185607 (applicant; Hoechst Gosei Co., Ltd.) is an invention relating to a protective colloid-based redispersible acrylic resin emulsion powder and a method for producing the same. In other words, by using a water-soluble protective colloid, an acrylic monomer is emulsified (co) polymerized in the presence of a specific amount of a chain transfer agent, and the resulting emulsion is spray-dried, thereby being excellent in redispersibility and film properties. To obtain the title powder. Using an acrylic monomer (eg, polyvinyl alcohol) in the presence of a chain transfer agent (eg, trichloroethylene) in an amount of 0.1 to 50% by weight based on the acrylic monomer, Methyl methacrylate) is emulsion-polymerized with 30% by weight or less of a copolymerizable monomer (eg, styrene), if desired. Then, the obtained acrylic resin emulsion is spray-dried to obtain a protective colloid-based redispersible acrylic resin emulsion powder. The obtained resin emulsion powder is suitably used as an adhesive, a paint binder, a cement additive and the like.

[JP-A-2-173003] JP-A-2-173003
No. 173003 (applicant; Mitsui Toatsu Chemicals, Inc.)
An oil phase containing a polymerizable monomer and a diluent is dispersed in an aqueous medium containing a dispersant, and then polymerized under specific conditions. Techniques for efficiently obtaining particles have been disclosed. That is, (a) an aqueous medium (b) containing 0.1 to 10% by weight of a dispersant which is a partially saponified PVA having a saponification degree of 50 to 95%, and (c) a vinyl insoluble or hardly soluble in the component b. A polymerizable monomer that is a monomer having a group,
(D) a diluent that is soluble in the component c, insoluble or hardly soluble in the component b, and has no polymerizability;
The oil phase (e) having a volume ratio of 10 to 1: 1 with the component
After being dispersed in a spherical shape of about 50 μm, the dispersed particles are aggregated to a diameter of 0.1 to 3 mm while being polymerized while the component c is being polymerized to obtain a polymer particle aggregate. Next, the aggregate is washed to remove the component a and the component d is extracted, and then the aggregate is redispersed to a size of 1 to 5 μm.

C. Technical background on re-emulsifiability and film-forming properties [Re-emulsifiability and film-forming properties] Some re-emulsifiable polymers or their powders do not form films at room temperature,
For use in a wide range of applications, a re-emulsifiable polymer or a powder thereof which is dried at room temperature to form a film is preferred. When an aqueous emulsion that forms a film at room temperature is dried, there is a serious problem that the dispersed particles are coagulated and fused to lose re-emulsifiability because the polymer is soft.

[Anti-Binder] In order to prevent agglomeration and fusion of powder particles, a method of adding an inorganic fine powder or an organic fine powder having no binder ability as an anti-binder is known. However, in such a case, when the re-emulsified liquid is dried to form a film, there is a problem in that various properties such as transparency are unfavorably affected. As for the use of the re-emulsifiable polymer or its powder, even with a cement admixture expected to have little problem even if the inorganic fine powder is mixed, an increase in the flow value is observed due to the large water absorption of the inorganic fine powder. And the water / cement ratio had to be increased. Furthermore, the water absorption of the obtained cement product increases,
There was also a problem that the fine powder was liable to float and non-uniformity was likely to be caused. From such a problem, a re-emulsifiable polymer which does not require an anti-binder has been desired. [Core-Shell Polymer Having Alkali-Soluble Shell] In the prior art relating to re-emulsifiable polymer powder, in the method utilizing a core-shell polymer having an alkali-soluble shell, the density of the shell is low due to its solubility. Therefore, fusion of the particles during drying could not be completely prevented, and there was a problem in re-emulsifiability. Further, there is a problem that fusion of particles cannot be prevented unless an anti-binder is used.

[Spray drying technique] The re-emulsifiable polymer powder
Most are produced by spray-drying techniques, which evaporate the water while preventing agglomeration and obtain a powder directly. In the conventional spray-drying technology, since it is usually dried at a high temperature of 100 ° C. or more, fusion of particles cannot be completely prevented,
There was a problem in re-emulsifiability. In addition, during spray drying, deposits may be formed on the inner wall of the drying tower, and the yield may be significantly reduced. In addition, the production of large scales and batches is very problematic in that it requires enormous amounts of time and energy.

[0027] The present inventors have considered that there is a problem with respect to the prior art for producing the re-emulsifiable polymer or its powder as described above in that it requires an enormous amount of time and energy.

D. Technical background on cement admixtures [Proceedings of the 50th Cement Technology Conference (1996)
324-325] In the case of a polymer cement mortar mixed with a re-emulsifying type powder resin, technical problems such as redispersibility remain, and it is described that compressive strength and flexural strength are sometimes reduced. [Proceedings of the 50th Cement Technology Conference (1996)
322-323] In the case of a polymer cement mortar mixed with a re-emulsifying type powder resin, air is easily entrained in the cement, so that the compressive strength and flexural strength are reduced, which may adversely affect various physical properties. In view of this teaching content, if a re-emulsifying powder resin with excellent re-emulsifying properties is developed, water, cement, sand, etc. can be mixed in a short time,
It is believed that it is expected that the amount of air entrained in the cement can be reduced and physical properties can be improved.

[0029]

SUMMARY OF THE INVENTION In view of the above problems of the prior art, the present inventors have utilized conventional re-emulsifiable polymer production techniques (for example, spray drying techniques, etc.) which require an enormous amount of time and energy. Technology that is completely different from that used in energy-saving, labor-saving, space-saving, and process-saving efficient manufacturing methods to provide high-quality re-emulsifiable polymer products with reduced distribution costs, reduced transportation costs, reduced waste, and reduced waste. Is a very significant task.

That is, the problems to be solved by the present invention are as follows. Polymer powdering: A solution to the problem of removing (co) polymer particles of a polymer emulsion by agglomeration. Re-emulsification of powdered polymer: The problem to be solved is to provide the (co) polymer particles agglomerated in the above with a function of substantially re-emulsifying in water having a pH of 5 or more. Such a unique recognition of the present inventors has heretofore been hardly recognized by those skilled in the art. Therefore, it is needless to say that the invention according to the present application has novelty and inventive step. However, the “problem to be solved by the invention” that forms the basis of the completion of the invention according to the present application is also novel. And it has inventive step.

The present inventors have made intensive studies and as a result, an aqueous emulsion obtained by polymerizing a specific ethylenically unsaturated monomer under specific conditions can be converted into an aggregate by adding an acid or a metal salt. And, surprisingly,
This agglomerate was found to have a function of substantially re-emulsifying in water having a pH of 5 or more, and the present invention was completed. An object of the present invention is to provide the following (co) polymer, a method for producing the (co) polymer, and a composition.

[0032]

(A) A core / shell structure in which at least a part of the core surface is covered by a shell, wherein the core is represented by a general formula (1)
At least one type of repeating unit selected from the group consisting of a repeating unit having a pendant group represented by 3) and the group consisting of a repeating unit having a pendant group represented by the general formula (2) Is a (co) polymer (α2) having at least 0% by weight and less than 40% by weight of

[0033]

Embedded image (In the general formula (1), R ¹ and R ² are the same or different and are each hydrogen, an alkyl group having 1 to 12 carbon atoms or an alkyl group having an —OH group having 1 to 12 carbon atoms. In the general formula (2), R ³ has 1 to 1 carbon atoms.
30 alkylene groups, or -R ³ OH is-(R
²² -O-) _n -H. (However, R ²² has 2 carbon atoms.
5 to 5 identical or different alkylene groups, and n is 2 to 3
0)) The shell has a repeating unit represented by the general formula (1)
At least one type of repeating unit selected from the group consisting of a repeating unit having a pendant group represented by 3) and the group consisting of a repeating unit having a pendant group represented by the general formula (2) 20% by weight or more
A (co) polymer (α1) having 0% by weight or less, and (α) based on the total weight of (α1) and (α2)
1) is 15 to 85% by weight, and (α2) is 85 to 15% by weight.
At least 1 having a pendant group represented by the general formula (1) and / or (2) in (α1).
Having a function of substantially re-emulsifying in water having a pH of 5 or more, comprising particles characterized in that the content of the kind of repeating unit is higher than the content of the at least one kind of repeating unit in (α2). (Co) polymers.

(A) A mixture comprising the particles (A) and a protective colloid, wherein the particles (A) have the general formula (1)
At least one member selected from the group consisting of a repeating unit having a pendant group represented by the general formula (2) and the group consisting of a repeating unit having a pendant group represented by the general formula (2) A (co) polymer (α2) having a repeating unit of 0% by weight or more and less than 40% by weight,

[0035]

Embedded image (In the general formula (1), R ¹ and R ² are the same or different and are each hydrogen, an alkyl group having 1 to 12 carbon atoms or an alkyl group having an —OH group having 1 to 12 carbon atoms. In the general formula (2), R ³ has 1 to 1 carbon atoms.
30 alkylene groups, or -R ³ OH is-(R
²² -O-) _n -H. (However, R ²² has 2 carbon atoms.
5 to 5 identical or different alkylene groups, and n is 2 to 3
0)) The protective colloid has a repeating unit represented by the general formula (1)
At least one member selected from the group consisting of a repeating unit having a pendant group represented by the general formula (2) and the group consisting of a repeating unit having a pendant group represented by the general formula (2) A (co) polymer (α1) having a repeating unit in an amount of 20% by weight or more and 100% by weight or less, and based on the total weight of (α1) and (α2),
(Α1) is 15 to 85% by weight, and (α2) is 85 to 85% by weight.
The content of at least one repeating unit having a pendant group represented by the general formula (1) and / or (2) in (α1) is 15% by weight, (Co) polymer having a function of substantially re-emulsifying in water having a pH of 5 or more, comprising particles characterized by having a content of a repeating unit higher than the above.

(C) Of the repeating units constituting (α1) and (α2), other than at least one type of repeating unit having a pendant group represented by the general formula (1) and / or (2) The repeating unit has the general formula (v), (w),
The (co) polymer according to any one of (a) to (a), which is constituted by at least one of (x), (y) and (z) (Formula 15).

[0037]

Embedded image (In the general formulas (v) to (z), R ¹¹ is hydrogen or a methyl group, R ¹² is hydrogen or an alkyl group having 1 to 12 carbon atoms, R ¹³ is hydrogen, an alkyl group having 1 to 20 carbon atoms,
An alkene or phenyl group having 1 to 20 carbon atoms, R
¹⁴ is the same or different hydrogen, or an alkyl group having 1 to 12 carbon atoms, a sulfonic acid group or a metal sulfonate,
R ¹⁵ is an unsaturated hydrocarbon having or not having a side chain having 1 to 6 carbon atoms.

(D) (α1) is represented by the general formula (2)
(A) to (C), wherein at least one kind of repeating unit selected from the group consisting of repeating units having a pendant group represented by 6) is contained in an amount of 20% by weight or more and 100% by weight or less. Described,

[0039]

Embedded image (In the general formula (2), R ₃ is an alkylene group having 1 to 30 carbon atoms, or —R ³ OH is — (R ²² —O
−) _N −H. (Wherein, R ²² are the same or different alkylene group having 2 to 5 carbon atoms, n represents a is 2 to 30) (co) having the function of substantially redispersible relative) pH 5 or more water United.

(E) The at least one repeating unit having a pendant group represented by the general formula (2) (Formula 17) is derived from 2-hydroxyethyl methacrylate ( D) The (co) polymer as described above.

[0041]

Embedded image As a specific method for producing the above (co) polymer, (f) as step 1 (aqueous emulsion production step), an ethylenically unsaturated monomer having a pendant group represented by the general formula (1) 20% by weight or more and 100% by weight or less of at least one member selected from the group consisting of a body and a group consisting of an ethylenically unsaturated monomer having a pendant group represented by the general formula (2). A protective colloid (a1) obtained by radical (co) polymerization of an ethylenically unsaturated monomer containing the same, and an ethylenically unsaturated monomer having a pendant group represented by the general formula (1) At least one selected from the group consisting of a compound consisting of a compound and a group consisting of an ethylenically unsaturated monomer having a pendant group represented by the general formula (2) Copolymer containing The ethylenically unsaturated monomer constituting (a2)

[0042]

Embedded image (In the general formula (1), R ¹ and R ² are the same or different and are each hydrogen, an alkyl group having 1 to 12 carbon atoms or an alkyl group having an —OH group having 1 to 12 carbon atoms. In the general formula (2), R ³ has 1 to 1 carbon atoms.
30 alkylene groups, or -R ³ OH is-(R
²² -O-) _n -H. (However, R ²² has 2 carbon atoms.
5 to 5 identical or different alkylene groups, and n is 2 to 3
0)), and (a1) is 15 to 85% by weight based on the total weight of (a1) and (a2);
(A2) is 85 to 15% by weight, and the content of at least one monomer having a pendant group represented by the general formula (1) and / or (2) in (a1) is in (a2). (2) a step of producing an aqueous emulsion comprising a dispersed phase of (co) polymer particles (A) and a continuous phase of water by radical (co) polymerization so as to be higher than the content of the monomer; As a (aggregate production step), a mineral acid and / or an organic acid is added to the aqueous emulsion produced in the step 1,
Aggregating the (co) polymer particles (A) by making H4 or less to produce an aggregate (A ′) of (co) polymers, Has a function of substantially re-emulsifying in water having a pH of 5 or more (co)
A method for producing a polymer.

(G) In the step 1 (core particle polymerization step), a group consisting of a pendant group-containing ethylenically unsaturated monomer represented by the general formula (1) ) Ethylene constituting a copolymer (a2) containing at least one selected from the group consisting of ethylenically unsaturated monomers having a pendant group represented by (Chemical Formula 19) in an amount of 0 to 40% by weight. Emulsion (co) polymerization of the unsaturated monomer,

[0044]

Embedded image (In the general formula (1), R ¹ and R ² are the same or different and are each hydrogen, an alkyl group having 1 to 12 carbon atoms or an alkyl group having an —OH group having 1 to 12 carbon atoms. In the general formula (2), R ³ has 1 to 1 carbon atoms.
30 alkylene groups, or -R ³ OH is-(R
²² -O-) _n -H. (However, R ²² has 2 carbon atoms.
5 to 5 identical or different alkylene groups, and n is 2 to 3
0)) a dispersed phase of (co) polymer core particles (A ⁰ );
And a step of producing an aqueous emulsion comprising a continuous phase of water, and as a step 2 (shell polymerization step), the (co) polymer core particles (A) in the aqueous emulsion produced in the step 1
⁰ ) and a group consisting of an ethylenically unsaturated monomer having a pendant group represented by the general formula (1) (Formula 19);
20% by weight or more and 100% by weight or less of a copolymer (a1) comprising at least one selected from the group consisting of ethylenically unsaturated monomers having a pendant group represented by the general formula (2) And comprising an ethylenically unsaturated monomer constituting (a) and (a1) and (a2),
(A1) is 15 to 85% by weight, and (a2) is 85 to 85% by weight.
(A1) having at least one pendant group represented by the general formula (1) and / or (2).
In a reaction system in which the content of the species monomer is higher than the content of the monomer in (a2), the shell (S) comprising a protective colloid is obtained by radical (co) polymerization.
Is formed on at least a part of the particle surface of the (co) polymer core particles (A ⁰ ) in the aqueous emulsion produced in the step 1, and a core / shell structure in which at least a part of the core surface is covered with a shell Core / shell type (with)
As a step of producing an aqueous emulsion, comprising a dispersed phase of the polymer particles (A) and a continuous phase of water, as a step 3 (aggregate production step), the aqueous emulsion produced in the step 2 is treated with a mineral acid and / or Adding an organic acid to adjust the pH to 4 or less to aggregate the core / shell type (co) polymer particles (A) to produce an aggregate (A ′) of the (co) polymer. PH5 characterized by comprising
A method for producing a (co) polymer having a function of substantially re-emulsifying in water as described above.

(G) Step 1 (aqueous emulsion production step) includes a group consisting of an ethylenically unsaturated monomer having a pendant group represented by the following general formula (1) and the general formula (2) ) Emulsifying an ethylenically unsaturated monomer containing at least one selected from the group consisting of ethylenically unsaturated monomers having a pendant group represented by the following chemical formula (0 to 40% by weight); (Co) polymer (a2)

[0046]

Embedded image (In the general formula (1), R ¹ and R ² are the same or different and are each hydrogen, an alkyl group having 1 to 12 carbon atoms or an alkyl group having an —OH group having 1 to 12 carbon atoms. In the general formula (2), R ³ has 1 to 1 carbon atoms.
30 alkylene groups, or -R ³ OH is-(R
²² -O-) _n -H. (However, R ²² has 2 carbon atoms.
5 to 5 identical or different alkylene groups, and n is 2 to 3
0)) a dispersed phase of (co) polymer core particles (A ⁰ );
And a step of producing an aqueous emulsion comprising a continuous phase of water, step 2 (protective colloid production step), wherein an ethylenically unsaturated monomer having a pendant group represented by the general formula (1) And the general formula (2)
An ethylenically unsaturated monomer containing at least one selected from the group consisting of ethylenically unsaturated monomers having a pendant group represented by the formula A) the step of producing the protective colloid (a1) by polymerization; the step 3 (mixing step); the aqueous emulsion produced in the step 1; and the step 2
(A1) is 15 to 85% by weight based on the total weight of (a1) and (a2),
(A2) is 85 to 15% by weight, and the content of at least one monomer having a pendant group represented by the general formula (1) and / or (2) in (a1) is in (a2). Mixing so as to be contained higher than the content of the monomer,
In step 4 (aggregate production step), a mineral acid and / or an organic acid is added to a mixture of the aqueous emulsion mixed in step 3 and the protective colloid produced in step 2 to adjust the pH to 4 or less (co). Aggregating the polymer particles (A) and the protective colloid to produce a (co) polymer aggregate (A ′).
A method for producing a (co) polymer having a function of substantially re-emulsifying in water having a pH of 5 or more.

(G) Step 1 (a step of producing an aqueous emulsion) includes a group consisting of an ethylenically unsaturated monomer having a pendant group represented by the following general formula (1) and the general formula (2) A) a radical of an ethylenically unsaturated monomer containing 20% by weight or more and 100% by weight or less of at least one selected from the group consisting of ethylenically unsaturated monomers having a pendant group represented by A group consisting of a protective colloid (a1) obtained by (co) polymerization, an ethylenically unsaturated monomer having a pendant group represented by the general formula (1) (formula 21), and a general formula (2)
Ethylenic constituting the copolymer (a2) containing at least one member selected from the group consisting of ethylenically unsaturated monomers having a pendant group represented by the following formula (0) and less than 40% by weight: Unsaturated monomers,

[0048]

Embedded image (In the general formula (1), R ¹ and R ² are the same or different and are each hydrogen, an alkyl group having 1 to 12 carbon atoms or an alkyl group having an —OH group having 1 to 12 carbon atoms. In the general formula (2), R ³ has 1 to 1 carbon atoms.
30 alkylene groups, or -R ³ OH is-(R
²² -O-) _n -H. (However, R ²² has 2 carbon atoms.
5 to 5 identical or different alkylene groups, and n is 2 to 3
0)), and (a1) is 15 to 85% by weight based on the total weight of (a1) and (a2);
(A2) is 85 to 15% by weight, and the content of at least one monomer having a pendant group represented by the general formula (1) and / or (2) in (a1) is in (a2). Radical (co) so as to be contained higher than the content of the monomer
By polymerizing, as a step of producing an aqueous emulsion comprising a dispersed phase of (co) polymer particles (A) and a continuous phase of water, step 2 (aggregate production step), the aqueous emulsion produced in step 1 Adding a metal salt and salting out the (co) polymer particles (A) to produce an aggregate (A ′) of the (co) polymer. A method for producing a (co) polymer having a function of substantially re-emulsifying in water having a pH of 5 or more.

(K) Step 1 (core particle polymerization step) includes a group consisting of an ethylenically unsaturated monomer having a pendant group represented by the general formula (1) ) Ethylene constituting a copolymer (a2) containing at least one selected from the group consisting of ethylenically unsaturated monomers having a pendant group represented by the following chemical formula (0) and less than 40% by weight: (Co) polymerization of unsaturated monomer

[0050]

Embedded image (In the general formula (1), R ¹ and R ² are the same or different and are each hydrogen, an alkyl group having 1 to 12 carbon atoms or an alkyl group having an —OH group having 1 to 12 carbon atoms. In the general formula (2), R ³ has 1 to 1 carbon atoms.
30 alkylene groups, or -R ³ OH is-(R
²² -O-) _n -H. (However, R ²² has 2 carbon atoms.
5 to 5 identical or different alkylene groups, and n is 2 to 3
0)) a dispersed phase of (co) polymer core particles (A ⁰ );
And a step of producing an aqueous emulsion comprising a continuous phase of water, and as a step 2 (shell polymerization step), the (co) polymer core particles (A) in the aqueous emulsion produced in the step 1
⁰ ) and a group consisting of an ethylenically unsaturated monomer having a pendant group represented by the general formula (1) (Formula 22);
A copolymer (a1) containing at least one member selected from the group consisting of ethylenically unsaturated monomers having a pendant group represented by the general formula (2) and 20% by weight to 100% by weight. And comprising an ethylenically unsaturated monomer constituting (a) and (a1) and (a2),
(A1) is 15 to 85% by weight, and (a2) is 85 to 85% by weight.
(A1) having at least one pendant group represented by the general formula (1) and / or (2).
A shell (S) made of a protective colloid is produced in step 1 by radical (co) polymerization so that the content of the species monomer is higher than the content of the monomer in (a2). (Co) polymer core particles (A) in the prepared aqueous emulsion
^The core / shell type (co) polymer particles (A), which are particles having a core / shell structure in which at least a part of the core surface is covered with a shell by being formed on at least a part of the particle surface of ⁰ ) In a step of producing an aqueous emulsion comprising a dispersed phase and a continuous phase of water, as a step 3 (aggregate production step), a metal salt is added to the aqueous emulsion produced in the step 2, and a core / shell type ( Salting out the (co) polymer particles (A) to produce the (co) polymer aggregates (A ′). For producing a (co) polymer having the function of substantially re-emulsifying by

(1) Step 1 (a process for producing an aqueous emulsion) includes a group consisting of an ethylenically unsaturated monomer having a pendant group represented by the following general formula (1) and the general formula (2). ) Emulsifying an ethylenically unsaturated monomer containing at least one selected from the group consisting of ethylenically unsaturated monomers having a pendant group represented by (Chemical Formula 23) from 0% by weight to less than 40% by weight ( (Co) polymerize to form a (co) polymer (a2),

[0052]

Embedded image (In the general formula (1), R ¹ and R ² are the same or different and are each hydrogen, an alkyl group having 1 to 12 carbon atoms or an alkyl group having an —OH group having 1 to 12 carbon atoms. In the general formula (2), R ³ has 1 to 1 carbon atoms.
30 alkylene groups, or -R ³ OH is-(R
²² -O-) _n -H. (However, R ²² has 2 carbon atoms.
5 to 5 identical or different alkylene groups, and n is 2 to 3
0)) a dispersed phase of (co) polymer core particles (A ⁰ );
And a step of producing an aqueous emulsion composed of a continuous phase of water, as step 2 (a step of producing a protective colloid), an ethylenically unsaturated monomer having a pendant group represented by W general formula (1) 20% by weight or more and 100% by weight or less of at least one selected from the group consisting of a group consisting of a body and a group consisting of an ethylenically unsaturated monomer having a pendant group represented by the general formula (2) A process of producing a protective colloid (a1) by radical (co) polymerization of an ethylenically unsaturated monomer containing the same, as a step 3 (mixing step), an aqueous emulsion produced in the step 1 and a production in the step 2 (A1) is 15 to 85% by weight, (a2) is 85 to 15% by weight, and the (a1) is 85 to 15% by weight based on the total weight of (a1) and (a2).
The content of at least one monomer having a pendant group represented by the general formula (1) and / or (2) in 1) is higher than the content of the monomer in (a2). As a step of mixing (Step 4 (aggregate production step)), a metal salt is added to the mixture of the aqueous emulsion and the protective colloid mixed in Step 3, and the (co) polymer particles (A) and the protective colloid are added. Producing a (co) polymer aggregate (A ′) by salting out, wherein substantially re-emulsifying with respect to water having a pH of 5 or more. A method for producing a (co) polymer having

(A) (a1) is represented by the general formula (2)
(4) The composition according to any one of (1) to (3), wherein the composition is obtained by using at least one selected from the group consisting of ethylenically unsaturated monomers having a pendant group represented by 4). Manufacturing method.

[0054]

Embedded image (In the general formula (2), R ³ is an alkylene group having 1 to 30 carbon atoms, or —R ³ OH is — (R ²² —O
−) _N −H. (Wherein, R ²² are the same or different alkylene group having 2 to 5 carbon atoms, n represents a is 2 to 30) (co) having the function of substantially redispersible relative) pH 5 or more water A method of manufacturing coalescence.

(S) The at least one monomer is 2
-The production method according to (1), which is hydroxyethyl methacrylate.

(C) A (co) polymer having a function of substantially re-emulsifying in water having a pH of 5 or more, which is obtained by the production method according to any one of (F) to (G).

(G) Particles having a core / shell structure in which at least a part of the core surface is covered with a shell, wherein the core is a (co) polymer insoluble in water, and the shell is A water-soluble (co) polymer having a pH of 5 or more, and a substantially re-emulsifiable (co) polymer having a pH of 5 or more.

(T) Particles having a core / shell structure in which at least a part of the core surface is covered by a shell, wherein the core is a water-insoluble (co) polymer, and the shell is a water-soluble (co) polymer at a pH of 5 or more and wherein the shell has a weight of 15
A (co) polymer which is substantially re-emulsifiable at a pH of 5 or more, which is at least by weight

(H) The core has a core / shell structure in which at least a part of the core surface is covered with a shell. The core has a glass transition temperature of -40 to 30 ° C., and the glass transition temperature of the shell is Particles having a function of aggregating at a pH of 4 or less at least 10 ° C. or higher than the glass transition temperature of the core and 15% by weight or more based on the total weight of the particles, and having substantially no blocking property between particles.

(T) When converted to a dry state, the (co) polymer described in any one of (A) to (E) and (SE) to (H) is added to the hydraulic cement in an amount of 0. A hydraulic cement composition comprising 5 to 60% by weight.

(T) Any one of (A) to (E) and (S) to (H) corresponding to 0.5 to 60% by weight of the hydraulic cement in terms of the dry state. (Co)
A method in which a cement composition obtained by mixing a water-curable cement composition to which a polymer has been added with water is cast to form a hardened cement body.

[0062]

BEST MODE FOR CARRYING OUT THE INVENTION The aggregate of the present invention can be easily separated into solid and liquid by a simple operation such as filtration, centrifugation and decantation, so that it is not always necessary to perform spray drying. Such aggregates are characteristic in that contaminating free protective colloids, free acids and other free water-soluble substances can be removed by washing during and / or after solid-liquid separation. Such an aggregate is characteristic in that it has excellent anti-caking properties without using an anti-caking agent (inorganic fine powder, organic fine powder, etc.) as an essential component.

The re-emulsifiable polymer according to the invention, when used as a cement modifier, has a tensile strength of cement,
It is intended to improve bending strength, compressive strength, adhesive strength, abrasion resistance and the like.

The present invention is characterized in that an anti-binder (for example, an inorganic fine powder, an organic fine powder having no film-forming property) is not necessarily required. For example, civil engineering building materials, paper processing agents, paints,
It can be applied to a wide range of fields where ordinary aqueous emulsions are used, such as adhesives and fiber treatment agents. In addition,
The aspect, morphology and morphology of the “(co) polymer having a function of substantially re-emulsifying in water having a pH of 5 or more” according to the present invention is such that the “(co) polymer” has a There is no particular limitation as long as it has the function of substantially re-emulsifying the powder, but usually, embodiments such as powders, granules, pastes, wet cakes after filtration, or granules thereof are preferred.

Hereinafter, the present invention will be described in detail.

A. Basic Concept The glass transition point (Tg) of the (co) polymer described in the present invention can be measured by a usual method, for example, DSC or the like. [Calculated glass transition point to glass transition point of copolymer (T
Evaluation of g)] The glass transition point (Tg) of the copolymer and the methodology of its evaluation are as follows. The glass transition point (Tg) of a copolymer having a specific monomer composition can be obtained by calculation using the Fox equation. Here, the Fox equation means that for each monomer forming a copolymer, the Tg of a homopolymer of the monomer is obtained.
Is used to calculate the Tg of the copolymer based on the following formula: Bulletin of the American Physical Society, Series 2 (Bulleti
n of the American Physica
l Society, Series 2) Volume 1, Issue 3
P. 123 (1956). The term "calculated glass transition point" used in the specification of the present application also includes a glass transition point calculated by the Fox equation. The Tg of a homopolymer of various monomers serving as a basis for calculating the Tg of the copolymer by the Fox equation is described in, for example, Polymer Data Handbook Basic Edition (edited by the Society of Polymer Science), pp. 525-546. Numerical values or actual values measured by a usual method can be adopted.

[Concept of the word "emulsion (co) polymerization"] The term "emulsion (co) polymerization" used in the aqueous emulsion production step in the production method according to the present invention includes not only ordinary emulsion (co) polymerization method but also ordinary emulsion (co) polymerization method. And special emulsion (co) polymerization, protective colloid (co) polymerization, miniemulsion (co) polymerization, microemulsion (co) polymerization, and the like. In addition, the method of emulsifying or forcibly emulsifying a polymer by mixing a solvent and an emulsifier is also included in the concept of emulsification of the present invention.

[Protective Colloid Polymerization Method] The concept of the words “protective colloid polymerization” and “protective colloid”, and the concept and principle of the protective colloid polymerization method are described in, for example, “Emulsion Overview (Matsumoto Tsunetaka) Industrial Materials No. 24 Vol. 3, No. 10
15 ". In particular, the review of "Fig. 2 Emulsion polymerization of hydrophilic monomer" (12
Page) and its description ("Emulsion Polymerization of Hydrophilic Monomer" on page 12) and "Figure 3 Stabilization of Water Emulsion" (page 13) and its description ("Page 12-13"). In the section “Stabilization of emulsion particles”, there is an easy-to-understand explanation. As a well-known typical example of the protective colloid polymerization method, there is a technique disclosed in the above-mentioned JP-A-2-173003.

[Concept of "(co) polymer"] The concept of the term "(co) polymer" used in the specification of the present application is as follows.
Includes homopolymers and copolymers. There is no particular restriction on the type of arrangement in the copolymer (copolymer), and the copolymer may be any of a random copolymer, an alternating copolymer, a block copolymer, a graft copolymer and the like. The “(co) polymer” used in the specification of the present application is at least partially a linear, cyclic, macrocyclic, branched, star, three-dimensional network, IPN (inter penetrated network). , PIC (polyion complex) or the like.

The concept of “substantially re-emulsifying with respect to water having a pH of 5 or more”
The concept of "substantially re-emulsifying in 5 or more waters" means that a re-emulsification rate that cannot be achieved by the conventional spray drying method can be exhibited. For example, “Re-emulsification rate (%)” defined in [Evaluation Example 1-2] described below.
Is 40 to 100%, preferably 60
To 100%, more preferably 80 to 100%. Furthermore, in [Evaluation Example 7-5], 20 to 1
00%, preferably 40 to 100%.

[Properties of aggregate (A ') of (co) polymer]
In the present invention, the properties of the (co) polymer aggregate (A ′) are usually in a paste state containing a small amount of water in many cases. Not only in this state, but also tablets, granules,
Any other properties such as a film shape may be used.

["(Co) polymer having a function of substantially re-emulsifying in water having a pH of 5 or more"]
The (co) polymer having a function of substantially re-emulsifying in water of H5 or more "has an aspect, form and morphology of:
The "(co) polymer" is not particularly limited as long as it has a function of substantially re-emulsifying in water having a pH of 5 or more, and usually, embodiments such as powder, granules, and paste are preferable.

[Concept of the word "particle"] The concept of the term "particle" used in the specification of the present application completely encompasses the concept that these words generally have in polymer chemistry, but is not necessarily equivalent. Not something. Regarding aspects of scanning electron microscopic morphology of "particles" as used in this application,
For example, an embodiment having many projections in the form of raspberry or gold rice sugar (kontoito, confetti in Portuguese), an erythroid flat aspect, a rugby ball-like spheroid-like aspect, an Escherichia coli-like spindle-like, or hollow Embodiments in which particles are further present in the particles and hollow particles are also included.

The term “particles” used in the specification of the present application includes, for example, polymer emulsions, latex, and microspheres constituting a polymer suspension. Is a general embodiment. As described above, the term “particle” used in the present application is not necessarily equivalent to the concept that these words generally have in polymer chemistry, but the essence of the heteropolymer system according to the present invention. For convenience, the term “aspect” is frequently used when referring to it.

[Particles Having a Core / Shell Structure] The terms “core”, “shell” and “core / shell” used in the specification of the present application refer to the concept these terms generally have in polymer chemistry. Includes but is not necessarily equivalent. For example, the “core / shell” particles according to the present invention include embodiments in which the “core” is at least partially surrounded by the “shell”. Thus, the terms “core”, “shell” and “core / shell” as used in the claims and specification of the present application are:
Although these terms are not necessarily equivalent to the general concept of polymer chemistry, they are used for convenience in describing the essential "aspects" of the heteropolymer systems of the present invention frequently. I do.

In polymer chemistry, generally,
The term “core” is “core, center, n
ucleus) "," core (center) "
And "seed" are used equivalently, and the term "shell" is used as the term "shell, s
kin, husk), "sheath" and "robe". Accordingly, the term “core” as used in the specification of the present application refers to “core, center, nuc”.
leus), "core, center" and "seed". Similarly, for the word "shell", "shell (sh
ell, skin, husk) "," sheath (seat)
h) "and" robe ".

[Structure of Particle] The primary structure of the (co) polymer particle (A) may be in the form of a particle having an ethylenically unsaturated monomer (a2) present in the particle.
A structure usually called a core / shell type in which the surface of the (co) polymer particles is covered with a protective colloid (a1), and an ethylenically unsaturated monomer (a2) present in the particles.
A structure in which the protective colloid (a1) partially deposits on the (co) polymer particles of (a) and is not completely covered, protection in the (co) polymer particles of the ethylenically unsaturated monomer (a2) A so-called salami structure containing the colloid (a1) is exemplified. The morphology is not particularly limited, including particles having a special shape such as hollow particles and a structure in which particles further exist in the hollow particles. However, if the protective colloid (a1) is present outside the (co) polymer particles of the ethylenically unsaturated monomer (a2) in such a manner as to be rich enough to exhibit re-emulsifiability, these embodiments However, the present invention is not limited to this structure.

[Higher-Order Particles] In the present invention, when the (co) polymer particles (A) are primary particles, the (co) polymer aggregates (A ′) may be secondary particles, There are no particular restrictions on the tertiary particles to which a plurality of secondary particles adhere, or even higher-order particles, as long as they are suitable. In the present invention, the (co) polymer agglomerate (A ′) is usually obtained by attaching a plurality of (co) polymer particles (A) as primary particles to form secondary particles. Generally, the particles become secondary to higher-order particles. When they are added to water or alkaline water, they are easily emulsified and return to the form of primary particles or almost similar thereto. In the present invention, the (co) polymer aggregate (A ′)
May usually be a secondary particle obtained by adhering a plurality of (co) polymer particles (A) as primary particles, but also easily emulsified in water or alkaline water to form primary particles. Alternatively, it returns to a form close to it.

[Concept of the term "salting out"] The concept of the term "salting out" used in the specification of the present application completely includes the concept that the term generally has in polymer chemistry.
They are not necessarily equivalent. For example, "Chemical Dictionary 1
(Aiue) (Kyoritsu Shuppan, 1960) ”, 1108 pages
From the left column to the right column, there is a commentary on the word "salting out",
There is a description that "salting out" means "adding other substances (mainly inorganic salts) to an aqueous solution to agglomerate previously dissolved substances." The concept of the term "salting out" as used in the specification of the present application fully encompasses concepts generally recognized in chemistry, such as those described in the Dictionary of Chemistry, The term fully encompasses the concepts that the term generally has in colloid chemistry and polymer chemistry, as described below.

That is, "Chemistry of Polymer Latex (Souichi Muroi, Polymer Publishing Association, 1980)", 187-20
As described on page 0, by adding an electrolyte to particles (for example, a polymer emulsion, a latex, or a microsphere constituting a polymer suspension) which maintains a uniform dispersion state, a dispersion breaking action (salting out) is obtained. It also includes the phenomenon of causing salting out) and coagulating particles. Thus, the term "salting out" as used in the claims and specification of the present application is not necessarily equivalent to the concept that these terms are recognized in general chemistry. For frequent reference to the essential "aspects" of the invention, they will be used for convenience.

The (co) polymer of the present invention has a core / shell structure in which at least a part of the core surface is covered with a shell, and the core is represented by the following general formula (1) A group consisting of a repeating unit having a pendant group represented by formula (2):
A (co) polymer (α2) having 0% by weight or more and less than 40% by weight of at least one kind of repeating unit selected from the group consisting of repeating units having a pendant group represented by (Chemical Formula 25),

[0082]

Embedded image (In the general formula (1), R ¹ and R ² are the same or different and are each hydrogen, an alkyl group having 1 to 12 carbon atoms or an alkyl group having an —OH group having 1 to 12 carbon atoms. In the general formula (2), R ³ has 1 to 1 carbon atoms.
30 alkylene groups, or -R ³ OH is-(R
²² -O-) _n -H. (However, R ²² has 2 carbon atoms.
5 to 5 identical or different alkylene groups, and n is 2 to 3
0)) The shell is represented by a group consisting of a repeating unit having a pendant group represented by the general formula (1) (Chemical formula 25) in the repeating unit, and a general formula (2) (Chemical formula 25) (Α1) polymer having at least one kind of repeating unit selected from the group consisting of repeating units having a pendant group in an amount of 20% by weight or more and 100% by weight or less.
And (α1) is 15 to 85% by weight and (α2) is 8% by weight based on the total weight of (α1) and (α2).
5 to 15% by weight and the general formula (1) in (α1)
And / or particles characterized in that the content of at least one type of repeating unit having a pendant group represented by (2) is higher than the content of the at least one type of repeating unit in (α2). A (co) polymer having a function of substantially re-emulsifying in water having a pH of 5 or more.

A mixture comprising particles (A) and a protective colloid, wherein the particles (A) have the general formula (1)
At least one selected from the group consisting of a repeating unit having a pendant group represented by (Chemical Formula 26) and the group consisting of a repeating unit having a pendant group represented by Formula (2) (Chemical Formula 26) A (co) polymer (α2) having a repeating unit of 0% by weight or more and less than 40% by weight,

[0084]

Embedded image (In the general formula (1), R ¹ and R ² are the same or different and are each hydrogen, an alkyl group having 1 to 12 carbon atoms or an alkyl group having an —OH group having 1 to 12 carbon atoms. In the general formula (2), R ³ has 1 to 1 carbon atoms.
30 alkylene groups, or -R ³ OH is-(R
²² -O-) _n -H. (However, R ²² has 2 carbon atoms.
5 to 5 identical or different alkylene groups, and n is 2 to 3
0)) The protective colloid includes, as a repeating unit, a group consisting of a repeating unit having a pendant group represented by the general formula (1) (formula 26), and a general formula (2) (formula 2)
(A) a (co) polymer having at least one repeating unit selected from the group consisting of repeating units having a pendant group represented by 6) in an amount of 20% by weight or more and 100% by weight or less, and (α1) ) And (α2), (α1) is 15 to 85% by weight, and (α1)
2) is 85 to 15% by weight, and the content of at least one type of repeating unit having a pendant group represented by formula (1) and / or (2) in (α1) is (α2)
A (co) polymer having a function of substantially re-emulsifying in water having a pH of 5 or more, comprising particles characterized by having a content of at least one type of repeating unit therein. The present invention provides the following (co) polymers.
(In the present specification, a composition containing two or more kinds of (co) polymers is also included in the concept of (co) polymer.) The present invention specifies a repeating unit essential in the present invention such as α1 in a specific amount. The effect of the present invention is exhibited if the (co) polymer containing the above and the (co) polymer α2 containing no or less than a specific amount of the essential repeating unit of α1 are essential components.

For example, the invention of the present application is a (co) polymer containing a specific repeating unit of the general formula (1) and / or (2) described above and above, which can exhibit the effects of the present invention. The repeating unit other than (1) and / or (2) does not need to be particularly defined, but is preferably, for example, a (co) polymer.

Among the repeating units constituting (α1) and (α2), other repeating units other than at least one type of repeating unit having a pendant group represented by the general formula (1) and / or (2) General formulas (v), (w),
A (co) polymer comprising at least one of (x), (y) and (z) (Formula 27).

[0087]

Embedded image (In the general formulas (v) to (z), R ¹¹ is hydrogen or a methyl group, R ¹² is hydrogen or an alkyl group having 1 to 12 carbon atoms, R ¹³ is hydrogen, an alkyl group having 1 to 20 carbon atoms,
An alkene or phenyl group having 1 to 20 carbon atoms, R
¹⁴ is the same or different hydrogen, or an alkyl group having 1 to 12 carbon atoms, a sulfonic acid group or a metal sulfonate,
R ¹⁵ is an unsaturated hydrocarbon having or not having a side chain having 1 to 6 carbon atoms. Further, the present invention is a particle having a core / shell structure in which at least a part of a core surface is covered by a shell, wherein the core is a water-insoluble (co) polymer, and the shell is
It is a water-soluble (co) polymer having a pH of 5 or more.
The (co) polymer which can be substantially re-emulsified above.

A particle having a core / shell structure in which at least a part of the core surface is covered with a shell, wherein the core is a (co) polymer insoluble in water, and the shell has a pH of 5 or more. A water-soluble (co) polymer and the shell is 15% by weight of the total core / shell
A (co) polymer which is substantially re-emulsifiable at a pH of 5 or more, which is at least by weight

A core / shell structure in which at least a part of the core surface is covered by a shell, wherein the core comprises:
The glass transition temperature is -40 to 30 ° C., the glass transition temperature of the shell is at least 10 ° C. or higher than the glass transition temperature of the core, and 15% by weight based on the total weight of the particles.
Particles having the function of coagulating at pH 4 or less and having substantially no blocking property between particles.

The (co) polymer of the present invention is a particle having a core / shell structure in which at least a part of the core surface is covered with a shell, wherein the shell and the core have a pH of 5 or more specified as described above. It is intended to provide a substantially re-emulsifiable (co) polymer. A more specific configuration of the (co) polymer of the present invention is, for example, the following (co) polymer.

Having a core / shell structure, wherein the core comprises:
The repeating unit includes a group consisting of a repeating unit having a pendant group represented by the general formula (1) (Formula 28) and a repeating unit having a pendant group represented by the formula (2) (Formula 28). A (co) polymer (a) of an ethylenically unsaturated monomer having at least one but not less than 40% by weight of at least one ethylenically unsaturated monomer selected from the group
2)

[0092]

Embedded image (In the general formula (1), R ₁ and R ₂ are the same or different and are each hydrogen, an alkyl group having 1 to 12 carbon atoms or an alkyl group having an —OH group having 1 to 12 carbon atoms. In the general formula (2), R ₃ has 1 to 1 carbon atoms.
30 alkylene groups, or -R ³ OH is-(R
²² -O-) _n -H. (However, R ²² has 2 carbon atoms.
5 to 5 identical or different alkylene groups, and n is 2 to 3
0)) The shell is a (co) polymer, and the shell is a group consisting of a repeating unit having a pendant group represented by the general formula (1) (Formula 28) in the repeating unit; An ethylenically unsaturated monomer having at least one kind of ethylenically unsaturated monomer selected from the group consisting of repeating units having a pendant group represented by the general formula (2) (A) a saturated monomer (co) polymer, and (a1) and (a)
(A1) is 15 to 85% by weight based on the total weight of 2)
(A2) is 85 to 15% by weight, and (α
The content of at least one type of repeating unit having a pendant group represented by the general formula (1) and / or (2) in 1) is higher than the content of the at least one type of repeating unit in (α2). Having a function of substantially re-emulsifying in water having a pH of 5 or more, comprising particles characterized by having
Polymer.

A mixture comprising the particles (A) and a protective colloid, wherein the particles (A) are a (co) polymer and have a pendant group represented by the general formula (1) 0% by weight of at least one ethylenically unsaturated monomer selected from the group consisting of a repeating unit having a pendant group represented by formula (2) and the pendant group represented by the general formula (2). A (co) polymer (a2) of an ethylenically unsaturated monomer having at least 40% by weight,

[0094]

Embedded image (In the general formula (1), R ¹ and R ² are the same or different and are each hydrogen, an alkyl group having 1 to 12 carbon atoms or an alkyl group having an —OH group having 1 to 12 carbon atoms. In the general formula (2), R ³ has 1 to 1 carbon atoms.
30 alkylene groups, or -R ³ OH is-(R
²² -O-) _n -H. (However, R ²² has 2 carbon atoms.
5 to 5 identical or different alkylene groups, and n is 2 to 3
0)) The protective colloid is a (co) polymer, and the protective colloid is a group consisting of a repeating unit having a pendant group represented by the general formula (1) (Formula 29) in the repeating unit; And at least one ethylenically unsaturated monomer selected from the group consisting of repeating units having a pendant group represented by the general formula (2) (formula 29) in an amount of 20% by weight or more and 100% by weight or less. (A) a (co) polymer of an ethylenically unsaturated monomer, and (a1) and (a)
(A1) is 15 to 85% by weight based on the total weight of 2)
(A2) is 85 to 15% by weight, and (α
The content of at least one type of repeating unit having a pendant group represented by the general formula (1) and / or (2) in 1) is higher than the content of the at least one type of repeating unit in (α2). A (co) polymer having a function of substantially re-emulsifying in water having a pH of 5 or more.

[Ethylenically unsaturated monomer having a pendant group represented by the general formula (1)]
0) an ethylenically unsaturated monomer having a pendant group represented by

[0096]

Embedded image (In the general formula (1), R ¹ and R ² are the same or different and are each hydrogen, an alkyl group having 1 to 12 carbon atoms or an alkyl group having an —OH group having 1 to 12 carbon atoms. )), For example, general formulas (3) to
(6) (Formula 31).

[0097]

Embedded image (In the general formula (4), R ¹ and R ² are the same or different and are each hydrogen or an alkyl group having 1 to 12 carbon atoms or an alkyl group having an —OH group having 1 to 12 carbon atoms. In the general formula (5), R ⁵ is an alkylene group having 1 to 12 carbon atoms or —O having 1 to 12 carbon atoms.
It is an alkylene group having an H group. General formula (3)-
In (6), R ⁴ is hydrogen or a group having 1 to 12 carbon atoms.
Is an alkyl group. In the general formula (6), n is 1
Is an integer of up to 20. [Ethylenically unsaturated monomer having a pendant group represented by general formula (2)] As an embodiment of the ethylenically unsaturated monomer having a pendant group represented by general formula (2), for example, General formulas (7) to (9) (Formula 32) are exemplified.

[0098]

Embedded image (In the general formulas (7) to (9), R ⁴ is hydrogen or an alkyl group having 1 to 12 carbon atoms. In the general formula (9), m and n are respectively m = 1 to 16, n = 0
It is an integer of ~ 14. As an example of R ^{6 in} the general formula (9) (Formula 32),
For example, general formulas (10) and (11) (Formula 33) can be mentioned.

[0099]

Embedded image Examples of R ^{7 in} the general formula (9) (Formula 32) include:
For example, general formulas (12) to (14) (Formula 34) can be mentioned.

[0100]

Embedded image In the present invention, the content of at least one monomer having a pendant group represented by the above general formula (1) and / or general formula (2) is 0 in (a2) with respect to all monomers.
-40% by weight, preferably 0-30% by weight, more preferably 0-20% by weight, and in (a1) 20-10% by weight.
0% by weight, preferably 30 to 100% by weight, more preferably 40 to 100% by weight.

Further, at least one pendant group represented by the general formula (1) and / or (2) in (a1)
It is necessary that the content of the species is higher than the content of the at least one species in (a2).
It is 95% by weight, more preferably 20-90% by weight, more preferably 40-80% by weight.

[Repeating Unit Having Pendant Group Represented by General Formula (1)] A repeating unit having a pendant group represented by General Formula (1)

[0103]

Embedded image (In the general formula (1), each of R ₁ and R ₂ is the same or different and is hydrogen or an alkyl group having 1 to 12 carbon atoms or an alkyl group having an —OH group having 1 to 12 carbon atoms. In the general formula (2), R ₃ has 1 carbon atom.
A 30 alkylene group, or -R ³ OH is -
(R ²² -O-) _n -H. (However, R ²² is the same or different alkylene group having 2 to 5 carbon atoms, and n is 2
To 30)), for example, the general formula (1
5) to (18) (Formula 36).

[0104]

Embedded image (In the general formula (16), R ₁ and R ₂ each represent
The same or different, hydrogen, or an alkyl group having 1 to 12 carbon atoms or an alkyl group having an -OH group having 1 to 12 carbon atoms. In the general formula (17), R ⁵ is an alkylene group having 1 to 12 carbon atoms or 1 to 12 carbon atoms.
Is an alkyl group having an —OH group. General formula (15)
In (18), R ⁴ is hydrogen or a compound having 1 to 1 carbon atoms.
12 alkyl groups. In the general formula (18), n
Is an integer of 1 to 20. [Repeating Unit Having Pendant Group Represented by General Formula (2)] As an embodiment of the repeating unit having a pendant group represented by General Formula (2), for example, the general formula (19)
To (21) (Formula 37).

[0105]

Embedded image (In the general formulas (19) to (21), R ⁴ is hydrogen or an alkyl group having 1 to 12 carbon atoms. The general formula (2)
In 1), m and n are respectively m = 1 to 16,
n is an integer of 0 to 14. Examples of the mode of R ^{6 in} the general formula (21) (Formula 37) include the general formulas (10) and (11) (Formula 38).

[0106]

Embedded image Examples of R ^{7 in} the general formulas (21) and (37) include the general formulas (12) to (14) (chemical formula 39).

[0107]

Embedded image In the present invention, the content of the repeating unit represented by the general formula (1) and / or the general formula (2) is 0 to 40% by weight, preferably 0 to 30% by weight in (α2) relative to all the repeating units. , More preferably 0 to 20% by weight, and in (α1), 20 to 100% by weight, preferably 3% by weight.
0-100% by weight, more preferably 40-100% by weight
It is.

Further, at least one compound having a pendant group represented by the general formula (1) and / or (2) in (α1)
It is necessary that the content of the kind of repeating unit is higher than the content of the at least one kind of repeating unit in (α2), and the difference is 5 to 95% by weight, more preferably 20 to 90% by weight, more preferably Is 40 to 80% by weight.

[Blocking] The term "blocking" used in the present application is described, for example, in the section "Blocking" on page 403 on the right column of Polymer Dictionary (edited by The Society of Polymer Science, Asakura Shoten, Tokyo, 1988). As has been
"Crimping (blocking)" means, specifically,
This means a sticking phenomenon in which polymer particles dispersed in a solvent come into contact with each other, the contact surfaces adhere to each other, and cannot be easily separated. In principle, the expression of re-emulsifiability means that when added to water, the polymer particles are individually dispersed in water, so that the adhesion of polymer particles called blocking is performed firmly. If you do
It will be in the state which cannot be easily peeled off, and re-emulsifiability will fall.

Therefore, in order to exhibit excellent re-emulsifiability, it is necessary to suppress the blocking as much as possible so that the film can be easily peeled off. In the present invention, by causing the protective colloid or the shell to participate in the polymer particles under specific conditions, blocking between the polymer particles was suppressed, and the polymer particles were able to exhibit excellent re-emulsifiability. That is, as the function of the protective colloid or shell in the present invention, the function as an anti-blocking agent between polymer particles is most important. Therefore, in the present invention, the protective colloid does not necessarily have to function as an emulsion polymerization stabilizer, and when the protective colloid does not function as an emulsion polymerization stabilizer, a surfactant is used. Then, a stable polymerization reaction may be realized. That is, the degree of re-emulsifiability in the present invention is closely correlated with the anti-blocking function of the protective colloid or shell.

Therefore, (a1) is set to 85 to 15 with respect to the total amount of the (co) polymer (a2) of the ethylenically unsaturated monomer and the protective colloid (a1) or the shell (S).
It is important to make the weight% and (a2) 15 to 85 weight%. Here, the latter is preferably at least 15% by weight, more preferably at least 25% by weight, still more preferably at least 35% by weight, particularly preferably at least 45% by weight, and the upper limit is preferably at most 85% by weight, preferably at most 70% by weight. Or less, more preferably 60% by weight or less.

The glass transition point of the protective colloid (a1) or the shell (S) is preferably at least 20 ° C., more preferably at least 30 ° C., further preferably at least 40 ° C., particularly preferably at least 50 ° C.

As a preferred embodiment of the material of the protective colloid or the shell, a repeating unit having a pendant group represented by the general formula (1) (Formula 35), which is an essential component,
And / or a copolymer having a repeating unit having a carboxyl group in addition to the repeating unit having a pendant group represented by the general formula (2) (Formula 35). Here, the weight% of the repeating unit having a carboxyl group
Is preferably 0.5 to 30% by weight, more preferably 0.5 to 10% by weight, based on the copolymer in the case of the repeating unit of the general formula (1).
% By weight, more preferably 1 to 3% by weight, and in the case of the repeating unit of the general formula (2), preferably 0.5 to 60% by weight based on the copolymer (a1),
0.5 to 40% by weight is more preferable, and 0.5 to 20% by weight is further preferable.

The copolymer having a repeating unit having a carboxyl group is characterized in that it has particularly good solubility in water and is easily aggregated in the aggregation step.

[Anti-blocking property] As a general cause of blocking, the glass transition point (T
Since g) is low, the polymer particles soften in a high-temperature environment and exhibit adhesiveness. The term "anti-blocking"
Even if the polymer particles come into contact with each other, the property that the pressure-bonding property and the sticking property are not exhibited is included.

B. Mechanism [Mechanism of Aggregation by Addition of Acid in Aggregate Production Step] In the aggregate production step, a (co) polymer particle (A) is aggregated by adding a mineral acid and / or an organic acid to adjust the pH to 4 or less. Thus, an aggregate (A ′) of the (co) polymer is produced. The scientific mechanism of the phenomenon that the (co) polymer particles (A) according to the present invention coagulate with an acid is not always clear. However, in the present invention, since the protective colloid or the shell (which has the property of insolubilizing and coagulating under acidity alone) is present in a specific amount, the mineral acid and / or the organic acid can be removed. By the addition, the (co) polymer particles (A) aggregate,
It is considered to be an aggregate (A ′) of the (co) polymer. That is, the intervening protective colloid or shell is p
It is presumed that the (co) polymer particles (A) are agglomerated by making them hydrophobic at H4 or less and acting as an aggregating agent.

As the flocculant, a polymer having a flocculating effect, which is called a polymer flocculant, is also generally known.
It is believed that the particles settle or reduce the zeta potential on the surface of the suspended particles, thereby causing the suspended particles to aggregate.

In the present invention, it is considered that the protective colloid or the shell induces aggregation of the (co) polymer particles (A) by a similar mechanism under acidic conditions. The details of the aggregation mechanism of the above-mentioned polymer flocculant are described on pages 1 to 90 of the polymer flocculant (Eizo Omori, Polymer Publishing Association, 1975).

[Mechanism of Aggregation by Addition of Metal Salt in Aggregate Production Step] In the aggregate production step, a metal salt is added to aggregate the (co) polymer particles (A),
An aggregate (A ′) of the (co) polymer is produced. The scientific mechanism of the phenomenon that the (co) polymer particles (A) according to the present invention aggregate with a metal salt is not always clear.
A method for separating a solid polymer by utilizing a salting out phenomenon of forming an aggregate by adding a metal salt to a (co) polymer particle dispersion produced by emulsion (co) polymerization is known. From a polymer physicochemical perspective, van der Waals attraction (intermolecular force), electrostatic repulsion, and steric repulsion on the particle surface act between (co) polymer particles in an aqueous emulsion. Is believed to be. It is believed that the balance (equilibrium) of these attractive forces and repulsive forces (repulsive forces) determines the dispersibility and cohesiveness of the (co) polymer particles. In such a system, the metal salt mainly has an action of reducing electrostatic repulsion. Therefore, the dispersed phase ((co)
When a metal salt is added to an aqueous emulsion in which the (polymer particles) are uniformly dispersed, the repulsion between the (co) polymer particles is suppressed, and the (co) polymer particles aggregate from the dispersed state. It is considered to make a transition to the state. (Co)
For more information on polymer physicochemical considerations of polymer particle aggregation mechanisms, see Polymer Latex Chemistry (Souichi Muroi,
Polymer Publishing Association, 1980), pp. 187-200. It is presumed that at least a part of the mechanism of aggregation due to the addition of the metal salt in the aggregate production step is due to the above mechanism.

[Mechanism of exhibiting a function of substantially re-emulsifying in water having a pH of 5 or more] Usually, when an aqueous emulsion produced in an aqueous emulsion production step is dried by spray drying, it is rapidly dried at a high temperature. , Fusion of the (co) polymer particles (A) becomes remarkable,
The re-emulsifiability is remarkably reduced, and furthermore, a large amount of deposits are generated on the wall surface of the drying tower, and the workability and productivity are reduced. However, by the aggregate production step of the production method according to the present invention,
By forming the (co) polymer aggregate (A ′), it has a function of substantially re-emulsifying in water by itself or by further drying it and further pulverizing after drying. (Co) polymer having the same can be obtained. Further, by performing sufficient washing during and / or after the solid-liquid separation, the aggregate (A ′) of the (co) polymer is recovered, and contaminating free protective colloid, free acid, and other free aqueous solutions are collected. By removing the aggressive substance, it is possible to remove a substance that adversely affects the performance of the aggregate (A ′) of the (co) polymer.

Obtained by the production method according to the present invention,
A general mode of the (co) polymer particles (A) as primary particles is a composite particle in which a protective colloid (a1) is attached to a (co) polymer of an ethylenically unsaturated monomer (a2). Includes what is forming. The general mode as the primary particles of the (co) polymer particles (A) obtained by the production method according to the present invention is as follows: And the protective colloid (a1) richly present and forming composite particles.

The (co) polymer particles (A) obtained in the aqueous emulsion production step have a function of substantially re-emulsifying with water by being aggregated in the aggregate production step of the production method according to the present invention. (A ′) (co) polymer aggregate.

The (co) polymer aggregate (A ′) thus formed is present in the (co) polymer particles (A) due to the buffering action of the protective colloid (a1) present in the particles. To reduce the interaction between particles of the (co) polymer (a2) of the ethylenically unsaturated monomer, control the adhesion strength of the particles, and form an aggregate (A ′) of the (co) polymer. It is thought that it will exhibit the function of substantially re-emulsifying with water.

[Problems of Spray Drying] The spray drying method is a method of drying by spraying (co) polymer particles dispersed in water into a high-temperature gas from a nozzle. In the case of the spray drying method,
When the dispersion of the (co) polymer particles is sprayed from a nozzle into a high-temperature gas for drying, the capillary water between the (co) polymer particles evaporates rapidly, and the capillary between the (co) polymer particles evaporates. Since the pressure due to the pressure and the heat of the system are applied to the particles, there is a problem that the fusion force between the particles is increased and the particles are irreversibly fused. The theory of capillary pressure when the (co) polymer particles are fused together is described in "Chemistry of Polymer Latex (Souichi Muroi, Polymer Publishing Association)", pages 242 to 248 (1980).
Year).

In the case of the present invention, it is important to point out that unnecessary capillary pressure and high heat, which are inevitable in the case of spray drying, are not applied in order to form aggregates without heating the particles. It is.

In the case of the present invention, if there is no fusion between the particles, it is possible to reversibly easily substantially destroy the fused state and induce a dispersed state, if any. In the case of the present invention, the reversible inter-particle fusion state between particles (once, Even in the fused state, substantially, reversibly, again
Since it is possible to control the state of being able to be in a dispersed state, it is inevitable in the case of spray drying. , Which cannot be reversibly induced again into a dispersed state) can be substantially avoided.

[Polymerization of protective colloid or shell] In the present invention, the protective colloid or shell is water-soluble or hydrophilic by itself, and has a property of insolubilizing and coagulating under acidic conditions or in the presence of a metal salt. And has anti-blocking properties. That is, the degree of re-emulsifiability in the present invention is closely correlated with the anti-blocking function of the protective colloid or shell.

Therefore, in the radical (co) polymerization of the protective colloid (a1) or the shell (S), the general formula (1)
A group consisting of an ethylenically unsaturated monomer having a pendant group represented by the general formula (2);
It is important to use at least one monomer selected from the group consisting of ethylenically unsaturated monomers having a pendant group represented by 0).

[0129]

Embedded image (In the general formula (1), R ₁ and R ₂ are the same or different and each represents hydrogen, methyl group, ethyl group, an alkyl group having 3 to 12 carbon atoms, or —O having 1 to 12 carbon atoms.
It is an alkyl group having an H group. In the general formula (2), R ₃ is a methylene group, an ethylene group or a group having 3 carbon atoms.
A 30 alkylene group, or -R ³ OH is -
(R ²² -O-) _n -H. (However, R ²² is the same or different alkylene group having 2 to 5 carbon atoms, and n is 2
To 30)) Furthermore, based on the total weight of the ethylenically unsaturated monomer (a2) and the protective colloid (a1) or the shell (S), the former is 85 to 15% by weight, and the latter is 15 to 85
It is important to make the weight%. Here, the latter is preferably at least 15% by weight,
% By weight or more, more preferably 35% by weight or more, and particularly preferably 45% by weight or more.

The calculated value of the glass transition point of the protective colloid (a1) or the shell (S) is preferably at least 20 ° C., more preferably at least 30 ° C., further preferably at least 40 ° C., particularly preferably at least 50 ° C. The upper limit is not particularly limited, but a temperature of about 300 ° C. can be preferably used.

Preferred examples of the material of the protective colloid or the shell include a repeating unit having a pendant group represented by the following general formula (1), which is an essential component:
And / or a copolymer having a repeating unit having a carboxyl group in addition to the repeating unit having a pendant group represented by the general formula (2) (Formula 40). Here, the weight% of the repeating unit having a carboxyl group
Is preferably 0.5 to 30% by weight, more preferably 0.5 to 10% by weight, based on the copolymer in the case of the repeating unit of the general formula (1).
% By weight, more preferably 1 to 3% by weight, and in the case of the repeating unit of the general formula (2), preferably 0.5 to 60% by weight based on the copolymer (a1),
0.5 to 40% by weight is more preferable, and 0.5 to 20% by weight is further preferable.

The copolymer having a repeating unit having a carboxyl group is characterized in that it has particularly good solubility in water and is easily aggregated in an aggregation step.

[Ethylenically unsaturated monomer having a pendant group represented by the general formula (1)]
As an embodiment of the ethylenically unsaturated monomer having a pendant group represented by 0), for example, general formulas (3) to (6)
(Formula 41).

[0134]

Embedded image (In the general formula (4), R ¹ and R ² are the same or different and are each hydrogen or an alkyl group having 1 to 12 carbon atoms or an alkyl group having an —OH group having 1 to 12 carbon atoms. In the general formula (5), R ⁵ is an alkylene group having 1 to 12 carbon atoms or -O having 1 to 12 carbon atoms.
It is an alkyl group having an H group. General formulas (3) to (6)
In the formula, R ⁴ is hydrogen or an alkyl group having 1 to 12 carbon atoms. In the general formula (6), n is 1 to 20
Is an integer. When frequently referring to the ethylenically unsaturated monomer having a pendant group represented by the general formula (1) (Formula 40) in the present specification, it is referred to as “ethylenically unsaturated monomer having an amide group” for convenience. The term "mer" may be used. Specific examples of the ethylenically unsaturated monomer having an amide group include, for example, acrylamide, methacrylamide, N-
Methylol methacrylamide, N-methylolacrylamide, N-acryloylpyridine, N, N-dimethylacrylamide, N-isopropylacrylamide, N
-Hexylacrylamide, N-octylacrylamide, N-dodecylacrylamide, N, N-diethylacrylamide, N-acryloylpyrrolidine, diacetoneacrylamide, maleic amide, and the like,
Methacrylamide, N, N-dimethylacrylamide,
N-isopropylacrylamide, N-hexylacrylamide, N-octylacrylamide, N, N-diethylacrylamide, N-acryloylpyrrolidine and the like are particularly preferable, and these are used alone or in combination of two or more. Particularly, methacrylamide is preferred.

[Concept of the term "amide group"] The concept of the term "amide group" used in the specification of the present application completely encompasses the concept that the term generally has in polymer chemistry, but not necessarily. It is not equivalent. For example, "Chemical Dictionary 1 (Aiue) (Kyoritsu Publishing, 1960)" 24
On the left column on page 4, there is a commentary on the word "amide",
The term “amide” refers to “[1] a group in which an amino group —NH ₂ is bonded to an acid group (acyl group) to form an RCONH— form, for example, CH ₃ CONH— is referred to as acetamide. 2] (1) Hydrogen of ammonia is converted to an acid group (acyl group)
Replaced by RCONH ₂ . Same as acid amide. There is a description. The concept of the term "amide group" as used in the specification of the present application completely encompasses the concept generally recognized in chemistry, as described in the Dictionary of Chemistry, General formula (1)
The concept based on the pendant group represented by 0) is completely included. Thus, the term "amide group" as used in the claims and specification of the present application is not necessarily equivalent to the concept recognized in general chemistry. Essential "aspect" of the invention
Are frequently used for convenience.

[Ethylenically unsaturated monomer having a pendant group represented by the general formula (2)]
As an embodiment of the ethylenically unsaturated monomer having a pendant group represented by 0), for example, general formulas (7) to (9)
(Formula 42).

[0137]

Embedded image (In the general formulas (7) to (9), R ₄ is hydrogen or an alkyl group having 1 to 12 carbon atoms. In the general formula (9), m and n are respectively m = 1 to 16, n = 0
It is an integer of ~ 14. As an embodiment of R _{6 in} the general formula (9) (Formula 42),
For example, general formulas (10) and (11) (Formula 43) can be mentioned.

[0138]

Embedded image Examples of R ^{7 in} the general formula (9) (Formula 42) include:
For example, general formulas (12) to (14) (Formula 44) can be mentioned.

[0139]

Embedded image When frequently referring to the ethylenically unsaturated monomer having a pendant group represented by the general formula (2) (Formula 40) in the present specification, it is referred to as "an ethylenically unsaturated monomer having a hydroxyl group" for convenience. May be used. This "ethylenically unsaturated monomer having a hydroxyl group" was used (co)
Polymers are preferred because they provide good stability when used for cement. Specific examples of the ethylenically unsaturated monomer having a hydroxyl group include, for example, hydroxymethyl-, 2-hydroxyethyl-, hydroxypropyl-, hydroxybutyl-, hydroxypentyl-,
Preferred are acrylates or methacrylates such as polyethylene glycol mono-, polypropylene glycol mono-, polyethylene glycol polypropylene glycol mono-, polyethylene glycol polytetramethylene glycol mono-, and polypropylene glycol polytetramethylene glycol-, and these are used alone or in combination with 2 or more.
A mixture of more than one species is used.

Particularly preferred is 2-hydroxyethyl methacrylate.

[Ethylenic unsaturated monomer having a carboxyl group] Particularly preferred specific examples of the ethylenically unsaturated monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and the like. Examples include unsaturated carboxylic acid compounds such as acrylic acid anhydride, methacrylic anhydride, maleic anhydride, itaconic anhydride, and fumaric anhydride.

[Other Ethylenically Unsaturated Monomers] (a
The ethylenically unsaturated monomer having a pendant group represented by the general formula (1) and the pendant group represented by the general formula (2) which constitutes 1) Saturated monomers, and other than the ethylenically unsaturated monomer having a carboxyl group, as particularly preferred specific examples of other ethylenically unsaturated monomers, the following ~
And an ethylenically unsaturated monomer that can be copolymerized with an unsaturated monomer.

Alkyl acrylates having 1 to 12 carbon atoms, ie methyl-, ethyl-, isopropyl-, n-butyl-, isobutyl-, n-amyl-, isoamyl-, n-hexyl-, 2-ethylhexyl-, Acrylates to which octyl, decyl, dodecyl, octadecyl, cyclohexyl, phenyl, benzyl and the like are added.

Alkyl methacrylates having 1 to 12 carbon atoms, ie, methyl-, ethyl-, isopropyl-, n-butyl-, isobutyl-, n-amyl-, isoamyl-, n-hexyl-, 2-ethylhexyl-,
Octyl-, decyl-, dodecyl-, octadecyl-,
Methacrylate to which cyclohexyl-, phenyl-, benzyl- and the like are added.

Others Glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, isopropenyl-α,
α-dimethylbenzyl isocyanate, styrene, acrylonitrile, methacrylonitrile, sodium styrenesulfonate, acrylamido-2-methylpropanesulfonic acid and soda salts thereof.

[Initiator] In the present invention, the initiator used in the protective colloid production step or the shell polymerization step is not particularly limited, and examples thereof include persulfates such as hydrogen peroxide, ammonium persulfate and potassium persulfate; Sodium azobiscyanovalerate; or a metal ion such as iron ion and a redox initiator or the like in combination with a reducing agent such as sodium sulfoxylate, formaldehyde, sodium pyrosulfite, sodium hydrogen sulfite, L-ascorbic acid, etc. No. These polymerization initiators are generally used in an amount of 0.01 to 25 parts by weight based on 100 parts by weight of all monomers charged when polymerizing the protective colloid (a1) and the shell (S). .

[Molecular weight regulator] In the present invention, in the protective colloid production step and the shell polymerization step, if necessary, mercaptans such as t-dodecylmercaptan and n-dodecylmercaptan, allylsulfonic acid, methallylsulfonic acid and Allyl compounds such as soda salts and the like can also be used as molecular weight regulators.

[Properties of Protective Colloid or Shell] In the present invention, the material of the protective colloid (a1) or the shell (S), if used alone, is a substantially water-soluble or hydrophilic (co) polymer. There is no particular limitation as long as it has a property of insolubilizing and coagulating under acidic conditions or in the presence of a metal salt. The weight average molecular weight of the protective colloid (a1) is generally 1,000 to 500,000, preferably 1,000 to 350,000,
More preferably, it is about 1,000 to 200,000. In order to make the re-emulsifiability of the (co) polymer aggregate (A ′) substantially complete, the calculated glass transition temperature of the protective colloid (a1) or the shell (S) is 20 C. or higher, more preferably 30.degree. C. or higher, still more preferably 40.degree. C. or higher, and particularly preferably 50.degree. C. or higher.

[Ethylenically unsaturated monomer constituting (a2)] The ethylenically unsaturated monomer constituting (a2) used in the present invention is substantially polymerized to a desired (co) There is no particular limitation as long as it produces polymer particles. Specific examples of the ethylenically unsaturated monomer include:
For example, monomers used in the production of aqueous emulsions used for civil engineering building materials, paper processing agents, paints, adhesives, fiber processing agents and the like can be mentioned.

Specific examples of the above ethylenically unsaturated monomers include, for example, acrylic esters; methyl-, ethyl-, isopropyl-, n-butyl-, isobutyl-,
n-amyl-, isoamyl-, n-hexyl-, 2-ethylhexyl-, octyl-, decyl-, dodecyl-,
Octadecyl-, cyclohexyl-, phenyl-, benzyl-, 2-hydroxyethyl-, hydroxypropyl-acrylate, methacrylates; methyl-,
Ethyl-, isopropyl-, n-butyl-, isobutyl-, n-amyl-, isoamyl-, n-hexyl-, 2
-Ethylhexyl-, octyl-, decyl-, dodecyl-, octadecyl-, cyclohexyl-, phenyl-,
Other alkyl acrylates having 3 to 12 carbon atoms such as benzyl-, 2-hydroxyethyl-, hydroxypropyl-methacrylate, and other alkyl methacrylates having 3 to 12 carbon atoms, 2-methoxyethyl acrylate, 2-ethoxyethyl Acrylate, acrylonitrile, methacrylonitrile, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, unsaturated carboxylic acids; acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, acrylic anhydride, methacrylic anhydride, maleic anhydride , Amino-containing monomers such as itaconic anhydride and fumaric anhydride; N
Aromatic vinyls such as -methylaminoethyl acrylate, N-methylaminoethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate; styrene, 2-methylstyrene, t-butylstyrene, chlorostyrene, vinylanisole, vinylnaphthalene And vinyl esters such as divinylbenzene; vinyl acetate, vinyl propionate, and vinyl esters of fatty acids (eg, VeoVa from Shell Chemical Co., Ltd.);
Vinyl halides; vinyl chloride, vinylidene halides; olefins such as vinylidene chloride and vinylidene fluoride; ethylene, propylene, dienes; isoprene;
Butadiene, chloroprene, and others; vinylpyrrolidone, acrylonitrile, methacrylonitrile, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,3-butylene Glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polyethylene glycol diacrylate, 1,6
-Hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, tetramethylol methane triacrylate, tetramethylol methane tetraacrylate, allyl methacrylate , Dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, isopropenyl-α, α-dimethylbenzyl isocyanate, allyl mercaptan, amides; acrylamide, methacrylamide, N-methylol methacrylamide, N-methylol acrylamide;
Examples thereof include diacetone acrylamide and maleic amide, which can be used alone or in combination of two or more.

Of these, preferred are aromatic vinyl compounds, dienes, olefins, (meth) acrylates, and vinyl esters.
Butyl acrylate, 2-ethyl-hexyl acrylate, butadiene, methyl methacrylate, vinyl acetate,
Vinyl esters of fatty acids (for example, V
eoVa), ethylene and the like. When used for cement, an alkali-resistant monomer is preferred.

[Polymerization Method] In the present invention, an aqueous emulsion production step, a core particle production step, and an aqueous emulsion consisting essentially of a dispersed phase of (co) polymer particles (A) and a continuous phase of water can be produced. The method is not particularly limited as long as it is a method, but usually, an emulsion polymerization method is preferably employed. In the emulsion polymerization method, a surfactant, p
Even if an H adjuster or the like is used, no problem may occur.

In the present invention, specific examples of the polymerization method employed in the aqueous emulsion production step and the core particle production step include, for example, a method in which a polymerization is carried out by adding a polymerization initiator in the presence of an ethylenically unsaturated monomer, When the polymerization heat is large, it is preferable to add a polymerization initiator and carry out polymerization while dropping the ethylenically unsaturated monomer.Dissolving the polymerization initiator in the ethylenically unsaturated monomer, A method in which the polymerization is carried out while dropping the solution, a method in which the polymerization initiator is dissolved in an appropriate solvent, and the ethylenically unsaturated monomers are separately dropped simultaneously and polymerized.

In the present invention, specific examples of the polymerization method employed in the step of producing the protective colloid include, for example, mixing the monomers constituting the protective colloid, heating the mixture to a desired polymerization temperature, and then polymerizing. A method in which an initiator is added to perform polymerization; a method in which a polymerization initiator is preferably added, and a method in which a polymerization initiator is added and polymerization is performed while dropping monomers constituting the protective colloid; A method of dissolving in a constituent monomer and polymerizing while dripping the same, A method of dissolving a polymerization initiator in an appropriate solvent and simultaneously dropping a monomer constituting the protective colloid separately and polymerizing the same. And the like.

In the process of producing an aqueous emulsion according to the present invention, a protective colloid polymerization method can be employed. Therefore, by polymerizing in the presence of a protective colloid, the polymerization stability is improved and the amount of surfactant used Has the characteristic that it can be reduced.

In the shell polymerization step of the present invention, a hydrophilic ethylenically unsaturated monomer having a pendant group represented by the general formula (1) or (2) is used. Therefore, there is a feature that the polymerization stability is improved and the amount of the surfactant used can be reduced. Since the amount of the surfactant used can be reduced, there is an advantage that when a re-emulsifiable liquid of the re-emulsifiable polymer is formed into a film, the water resistance of the film is improved. In the production method according to the present invention, the polymerization of the ethylenically unsaturated monomer (a1) is carried out in the presence of the protective colloid (a1) described below. ) Can be carried out according to a usual emulsion polymerization method carried out in the absence of the protective colloid (a1).

[Surfactant] The surfactant which can be used in the emulsion polymerization method used in the present invention is not particularly limited as long as it can be formed substantially continuously, uniformly and stably in an aqueous continuous phase. Not done. As the surfactant, known surfactants used for ordinary emulsion polymerization can be suitably used alone or in combination. Hereinafter, specific examples of the nonionic surfactant, the anionic surfactant, and the cationic surfactant are listed, and these can be suitably used alone or in combination.

Nonionic surfactant Specific examples of the nonionic surfactant used in step 1 (aqueous emulsion production step) of the production method according to the present invention include polyoxyethylene lauryl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene octyl phenyl ether and polyoxyethylene lauryl ether. Oxyethylene oleyl ether, polyoxyethylene nonyl phenyl ether, oxyethylene / oxypropylene block copolymer and the like can be mentioned, and these can be used alone or in combination.

Anionic surfactants Specific examples of the anionic surfactant used in step 1 (aqueous emulsion production step) of the production method according to the present invention include sodium dodecylbenzenesulfonate, sodium lauryl sulfate, and alkyldiphenyl ether disulfone. Sodium acid, sodium alkylnaphthalenesulfonate, sodium dialkylsulfosuccinate, potassium stearate, potassium oleate, sodium dioctyl sulfosuccinate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate, sodium stearate, sodium olein And the like, and these can be used alone or as a mixture.

Cationic Surfactant Specific examples of the cationic surfactant used in Step 1 (aqueous emulsion production step) of the production method according to the present invention include lauryl trimethyl ammonium chloride,
Stearyl trimethyl ammonium chloride and the like can be mentioned, and these can be used alone or in combination.

[Amount of Surfactant] The amount of surfactant used is such that the micelles are substantially formed in the reaction system or the dispersed phase containing the monomer in the aqueous continuous phase is substantially maintained. The amount is not particularly limited as long as it is a stable and uniform amount. Generally, the type and concentration of the surfactant are determined while taking into account the CMC (critical micelle formation concentration) value and the HLB (hydrophilic-hydrophobic balance) value specific to the surfactant.
Conditions for substantially realizing desired particle characteristics (layer structure, morphology, particle size, particle size distribution, etc.) are appropriately selected. Generally, the surfactant can be used in an amount of 0.1 to 10% by weight based on the total weight of all the monomers supplied to the reaction system.

[Polymerization Initiator] The polymerization initiator that can be used in the emulsion polymerization method used in the present invention is not particularly limited as long as it can substantially exhibit the function of initiating polymerization. Specific examples of the polymerization initiator include, for example, hydrogen peroxide; persulfates such as ammonium persulfate and potassium persulfate; organic peroxides such as cumene hydroperoxide and tert-butyl hydroperoxide; azobisisobutyro Azo compounds such as nitriles; or metal ions such as iron ions and sodium sulfoxylate, formaldehyde, sodium pyrosulfite, sodium bisulfite, L
-Redox initiators and the like in combination with reducing agents such as ascorbic acid. These polymerization initiators are generally used with respect to 100 parts by weight of the ethylenically unsaturated monomer.
0.01 to 15 parts by weight are used.

[Molecular weight regulator] In the emulsion polymerization method employed in the present invention, if necessary, mercaptans such as t-dodecyl mercaptan and n-dodecyl mercaptan, allylsulfonic acid, methallylsulfonic acid and the like. It is also possible to use an allyl compound such as a soda salt as a molecular weight regulator.

[Characteristics of (Co) polymer Particle (A)] In the present invention, the weight average molecular weight of the (co) polymer particle (A) is usually preferably from 50,000 to 90,000,000.

[Particle size of (co) polymer particles (A)]
As for the particle diameter of the (co) polymer particles (A), the average particle diameter measured by a laser light scattering method in a wet state is preferably 50 to 5000 nanometers, and 70 to 3 nm.
000 nanometers is more preferable, and
Nanometers are more preferred. Usually, the particle size is
As it is reduced to less than 50 nanometers,
The viscosity of the re-emulsified liquid obtained by re-emulsifying the (co) aggregate (A ') of the (co) polymer suddenly increases, and the workability during use tends to decrease, and the specific surface area of the particles also increases. As a result, the stability of the re-emulsified liquid itself of the aggregate (A ′) of the (co) polymer tends to decrease. On the other hand, usually, as the particle diameter is increased to 5000 nanometers or more, the film-forming ability of the re-emulsified liquid is reduced, and the water resistance and strength of the composition obtained by adding the particles of the present invention are reduced. Tend to do so.

[Characteristics of Aqueous Emulsion Produced in Core Particle Polymerization Step] In the present invention, the aqueous emulsion produced in the core particle polymerization step generally includes a re-emulsion liquid which forms a film by drying at room temperature. Re-emulsifiable polymers that can be formed are useful. In the production of such a re-emulsifiable polymer, it is effective to use an aqueous emulsion which forms a film by drying at room temperature. In particular, in order to form a film by drying at room temperature, Tg determined by the Fox equation is preferably about -40 ° C to about + 30 ° C, more preferably about −30 ° C.
30 ° C to about + 20 ° C. In the polymer of the present invention, the core needs to have a lower Tg than the shell, and the temperature difference is preferably at least 10 ° C, more preferably at least 40 ° C. In the present invention, the polymerization method employed in the core particle polymerization step is most preferably an emulsion polymerization method in which a particle having a small particle diameter can be easily obtained, the particle diameter can be easily controlled, and the stability is excellent.

[Mineral acid and / or organic acid used in aggregate production step] Mineral acid and / or organic acid used in aggregate production step
Or the organic acid substantially converts the (co) polymer particles (A) into
There is no particular limitation as long as it has a function of insolubilizing as an aggregate (A ′) of a (co) polymer. Specific examples of the mineral acid and the organic acid include, for example, sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, acetic acid, and the like, and these can be used alone or in combination of two or more. In addition, sulfuric acid which can reduce the amount of addition and does not contain chlorine is particularly preferable.

[Embodiment of Method of Adding Mineral Acid and / or Organic Acid in Aggregate Production Process] In addition, when forming an aggregate, an alcohol or an electrolyte is added, and coagulation or salting out phenomenon is used together to prevent aggregation. Making it easy to wake up is also effective. As the electrolyte, those having an aluminum ion exhibiting an effect with a small amount are preferable, and examples thereof include aluminum sulfate (sulfate band). The temperature of the emulsion system when adding a mineral acid and / or an organic acid is not particularly limited as long as the aqueous emulsion or a mixture of the aqueous emulsion and the protective colloid can maintain a liquid phase. The temperature of the emulsion system when adding the acid is
Usually, it is 0 to 100 ° C. Usually, the higher the temperature, the stronger and larger the agglomerates and the easier the solid-liquid separation becomes. However, in the case of agglomeration, the fusion of the particles becomes stronger and the re-emulsifiability may decrease. Generally, it is preferably from 10 ° C to 80 ° C, and more preferably from 20 ° C to 60 ° C. After the acid is added, the system can be heated to cause aggregation.

[Amount of Mineral Acid and / or Organic Acid Added in Aggregate Production Process] The amount of the mineral acid and / or organic acid is usually adjusted so that the pH of the aqueous emulsion or the mixture of the aqueous emulsion and the protective colloid is 4 or less. Is more preferable, and more preferably, the pH is 3 or less. In general,
When the addition amount of the acid is small, the aggregation is incomplete and solid-liquid separation becomes difficult, and when the addition amount of the acid is large, the original properties of the (co) polymer particles (A) may not be exhibited, It may be difficult to remove the acid by washing during and / or after solid-liquid separation.

[Method of Adding Mineral Acid and / or Organic Acid in Aggregate Production Process] The method of adding the mineral acid and / or organic acid is not particularly limited. Usually, in order to mix the acid more uniformly and from the viewpoint of safety, the acid is preferably an aqueous solution, but is not necessarily limited to an aqueous solution. Usually, it is preferable to add it as an aqueous solution of 50% or less.

[Metal Salt Used in Aggregate Production Step] The metal salt used in the aggregate production step is substantially
There is no particular limitation as long as it has a function of insolubilizing the (co) polymer particles (A) as an aggregate (A ′) of the (co) polymer. Specific examples of metal salts include, for example, aluminum sulfate, aluminum chloride, ammonium alum, potassium alum, polyaluminum chloride, polyaluminum sulfate, and ferrous sulfate, ferric sulfate, and ferric chloride as iron salts. , Poly (ferric chloride), poly (ferric sulfate), zinc chloride, zinc sulfate as zinc salt, magnesium oxide, magnesium carbonate, magnesium sulfate as magnesium salt, aluminum hydroxide, iron hydroxide, calcium chloride, sodium chloride, etc. Calcium thiosulfate, calcium nitrite, calcium formate, potassium sulfate, potassium nitrate and the like,
These can be used alone or in combination of two or more. Generally, it is preferable to use a polyvalent metal salt such as an aluminum salt or an iron salt, because the higher the valence of the metal ion, the stronger the cohesion and the smaller the amount of the metal ion. Further, from the viewpoint of safety such as drainage, aluminum salts and iron salts are preferable.

[PH at Addition of Metal Salt in Aggregate Production Process] The pH at the time of adding the metal salt is generally
It is preferably from 6 to 2, more preferably from 5 to 3. This is because the more acidic the acid, the more the amount of the metal salt used can be reduced, and an aggregate which is easily separated into solid and liquid is generated, thereby improving the yield. At this time, mineral acids and / or organic acids can be used as the pH adjuster.
Specific examples of the pH adjuster include, for example, hydrochloric acid, sulfuric acid, phosphoric acid, and acetic acid. Usually, sulfuric acid which does not contain chlorine is preferable because the amount of the pH adjuster can be reduced. When the temperature of the emulsion system when adding the metal salt is within a temperature range in which the aqueous emulsion obtained in Step 2 (aqueous emulsion production step) can maintain a liquid phase,
There is no particular limitation. The temperature of the emulsion system when adding the metal salt is usually 0 to 100 ° C. However, since the agglomerate becomes stronger and larger as the agglomeration at a higher temperature becomes easier and the solid-liquid separation becomes easier, generally, The temperature is preferably from 10 ° C to 80 ° C, and more preferably from 20 ° C to 60 ° C.

[Amount of Metal Salt Added in Aggregate Production Process] The amount of the metal salt added is usually (co) polymer particle (A)
Preferably from 0.01 to 70% by weight, more preferably from 1 to 50% by weight, even more preferably from 5 to 30% by weight, based on solids. In general, when the amount of the metal salt added is small, coagulation is incomplete and solid-liquid separation becomes difficult,
When the addition amount of the metal salt is large, it is difficult to remove the metal salt by washing during and / or after the solid-liquid separation, because the (co) polymer particles (A) do not exhibit their original properties. Problem.

[Method of Adding Metal Salt in Aggregate Production Step] The method of adding the metal salt is not particularly limited. Usually, in order to mix the metal salt more uniformly, it is preferable to add it as a solution. Further, from the viewpoint of safety, the metal salt solution is preferably an aqueous solution, but is not necessarily limited to an aqueous solution. Examples of the method of adding the metal salt include, for example, a method in which the metal salt is added to the aqueous emulsion in a solid state, a method in which the metal salt is dissolved in a solvent capable of dissolving a certain amount or more, and a method in which the solution is added to the aqueous emulsion. And the like.

[Method of Separating / Drying / Pulverizing Aggregate (A ') of (Co) polymer] The solid-liquid separation method in the method of the present invention is not particularly limited as long as it is a commonly used method. However, commonly used separation techniques such as filtration, centrifugation, decantation, etc. can be used. Further, the separated aggregate can be dried and used. There is no particular limitation on the drying method. For example, drying can be performed by hot air drying, vacuum drying, or the like. Aggregates may be further aggregated by drying. In general, a re-emulsifiable polymer obtained by completely drying a solid-liquid separated aggregate at a temperature of from room temperature to 100 ° C. is hard and has no tackiness, and can be ground. The method of pulverizing the dried re-emulsifiable polymer is not particularly limited, and an ordinary device, for example, a hammer mill, a jet mill, a pin mill or the like can be used. In this pulverization, it is not necessary to pulverize to primary particles, but it is sufficient to make the powder into a workable size. Further, in order to increase the re-emulsifiability rate, it is desirable to pulverize to an average particle size (diameter) of preferably 1 mm or less, more preferably 500 μm or less, and still more preferably 300 μm or less.

[Uses and Applications-Hydraulic Cement Composition]
The re-emulsifiable polymer according to the present invention is preferably used as a modifier for hydraulic cement, and for hydraulic cement,
By mixing 0.5 to 60% by weight, preferably 1 to 40% by weight, more preferably 2 to 20% by weight of the re-emulsifiable polymer, the hydraulic cement composition can be modified.

[Uses and Applications-Method of Casting Hydraulic Cement] 0.5 to 60% by weight, preferably 1 to 40% by weight, more preferably 2 to 20% by weight, based on the hydraulic cement.
By mixing the re-emulsifiable polymer according to the present invention with water together with water and casting the mixture, an excellent hardened cement structure can be obtained. When the re-emulsifiable polymer of the present invention is used as a cement admixture, the following remarkable effects are exhibited. 1. 1. Improvement of bending strength 2. Improvement of tensile strength 3. Improved adhesive strength (increased adhesive strength to hardened mortar, concrete, plywood, metal, tile, etc.) 4. Maintain adhesive strength after water immersion. 5. Maintenance of adhesive strength over a long period Since the fluidity at the time of mixing the water-hardening cement is improved, it is effective as a water reducing agent, and the amount of water used can be reduced, and the strength is improved by further reducing the amount of water. 7. Due to its excellent re-emulsifiability, mixing can be performed in a short time, and entrainment of air into the mixed cement can be prevented. 8. 8. Improvement of water resistance Improved wear resistance

[0178]

EXAMPLES The present invention will be described more specifically with reference to examples and comparative examples. In the specification of the present application, examples, production examples, and aspects are provided to assist understanding of the contents of the invention according to the present application, and the description does not limit the present invention in any way. . “%” Used in the following description means “% by weight” unless otherwise specified.

The abbreviations of the various raw materials used in the tables describing the following Examples and Comparative Examples are shown below. MAm: methacrylamide, AAm: acrylamide HEA: 2-hydroxyethyl acrylate, HEMA:
2-hydroxyethyl methacrylate, MAc: methacrylic acid ST: styrene, BA: n-butyl acrylate, n-
DM: n-dodecyl mercaptan, MMA: methyl methacrylate, t-DM: t-dodecyl mercaptan, B
D: butadiene, AN: acrylonitrile, AA: acrylic acid, Al sulfate: aluminum sulfate, Cacl ₂ : calcium chloride, Fe: ferric sulfate Example in which an aqueous emulsion produced by a protective colloid polymerization method is coagulated with an acid (system using an ethylenically unsaturated monomer having an amide group).

[Example 1-1] Step 1 (aqueous emulsion production step) <Preparation of protective colloid (a1)> A reaction vessel equipped with a stirrer, a reflux condenser and a thermometer was charged with 785.0 pure water.
g, 150.0 g of methacrylamide, and stirred.
The temperature was raised to 75 ° C. in a nitrogen atmosphere, and this temperature was maintained. After the methacrylamide was completely dissolved, 45.0 g of a 5% aqueous ammonium persulfate solution was added, and the mixture was added at 75 hours for 75 hours.
It was kept at ° C. Add ammonia water and pure water to this,
A protective colloid (B-1) having a resin content of 15% and a pH of 9 was obtained. This protective colloid (B-1) is converted into p
When H was lowered to 3, the polymer aggregated.

<Protective Colloid Polymerization> A reaction vessel equipped with a stirrer, a reflux condenser and a thermometer was charged with 666.7 g of the protective colloid (B-1), and stirred at 80 ° C. in a nitrogen atmosphere at a temperature of 80 ° C. to remove potassium persulfate. 0.5 g was added.
On the other hand, an emulsion having the following composition was prepared, and this emulsion was added dropwise to the above protective colloid at 80 ° C. for 3 hours and stirred at 80 ° C. for 3 hours. Pure water 40.0 g Sodium dodecylbenzenesulfonate 0.1 g Styrene 40.0 g N-butyl acrylate 50.0 g 2-Hydroxyethyl methacrylate 5.0 g Methacrylic acid 3.0 g Acrylamide 2.0 g 0.1 g of n-dodecyl mercaptan Aqueous emulsion (C-1) having a resin content of 10% and a pH of 9 was prepared by adding aqueous ammonia and pure water to the obtained polymer.

Step 2 (Aggregate Production Step) When a 5% aqueous sulfuric acid solution was added to 1,000 g of (C-1) at room temperature until the pH became 2.5, an aggregate was formed. This solid was separated into solid and liquid by filtration, and then dried at 80 ° C. until the residual water content became 2% or less (the residual water content was JIS).
It was measured by the method of measuring loss on heating of K5407.5.
Hereinafter, all the residual moisture amounts described in the present specification are values measured by this method). The re-emulsifiable polymer powder was obtained by pulverizing the dried aggregate.

Example 1-2 With the composition shown in Table 1-1,
(B-2) was prepared in the same manner as in Example 1-1. (This protective colloid (B-2)
When H was lowered to 3, the polymer aggregated. ) Subsequently, protective colloid polymerization was performed to prepare an aqueous emulsion (C-2) having a resin content of 10% and a pH of 9 and a re-emulsifiable polymer powder was obtained by the same operation.

[Example 1-3] With the composition shown in Table 1-1,
(B-3) was prepared in the same manner as in Example 1-1. (This protective colloid (B-3)
When H was lowered to 3, the polymer aggregated. ) Subsequently, protective colloid polymerization was performed to prepare an aqueous emulsion (C-3) having a resin content of 10% and a pH of 9 and a re-emulsifiable polymer powder was obtained by the same operation.

[Example 1-4] With the composition shown in Table 1-1,
(B-4) was prepared in the same manner as in Example 1-1, and (this protective colloid (B-4)
When H was lowered to 3, the polymer aggregated. ) Subsequently, protective colloid polymerization was carried out to prepare an aqueous emulsion (C-4) having a resin content of 10% and a pH of 9 and a re-emulsifiable polymer powder was obtained by the same operation.

Example 1-5 The composition shown in Table 1-1 was used.
(B-5) was prepared in the same manner as in Example 1-1. (This protective colloid (B-5)
When H was lowered to 3, the polymer aggregated. ) Subsequently, protective colloid polymerization was carried out to prepare an aqueous emulsion (C-5) having a resin content of 10% and a pH of 9 and a re-emulsifiable polymer powder was obtained by the same operation.

[Example 1-6] With the composition shown in Table 1-1,
(B-6) was prepared in the same manner as in Example 1-1, and (this protective colloid (B-6) was converted to p
When H was lowered to 3, the polymer aggregated. ) Subsequently, protective colloid polymerization was carried out to prepare an aqueous emulsion (C-6) having a resin content of 10% and a pH of 9 and a re-emulsifiable polymer powder was obtained by the same operation.

[Example 1-7] With the composition shown in Table 1-1,
(B-7) was prepared by the same operation as in Example 1-1, and (this protective colloid (B-7) was converted to p
When H was lowered to 3, the polymer aggregated. ) Subsequently, protective colloid polymerization was carried out to prepare an aqueous emulsion (C-7) having a resin content of 10% and a pH of 9 and a re-emulsifiable polymer powder was obtained by the same operation.

[Example 1-8] The composition shown in Table 1-1 was used.
(B-8) was prepared by the same operation as in Example 1-1, and (this protective colloid (B-8) was converted to p
When H was lowered to 3, the polymer aggregated. ) Subsequently, protective colloid polymerization was carried out to prepare an aqueous emulsion (C-8) having a resin content of 10% and a pH of 9 and a re-emulsifiable polymer powder was obtained by the same operation.

[Example 1-9] With the composition shown in Table 1-1,
(B-1) was prepared in the same manner as in Example 1-1, followed by protective colloid polymerization under the following conditions, and an aqueous emulsion (C-9) having a resin content of 10% and a pH of 9
Was prepared, and a re-emulsifiable polymer powder was obtained by the same operation. <Protective Colloid Polymerization> A protective colloid (B-1) 40 was placed in a reaction vessel equipped with a stirrer, a reflux condenser and a thermometer.
0.0 g and 210 g of pure water were charged, and 0.7 g of potassium persulfate was added at a temperature of 80 ° C. with stirring in a nitrogen atmosphere. On the other hand, an emulsion monomer having the following composition was prepared, dropped into the above aqueous solution in 3 hours, and aged for 3 hours. Pure water 56.0 g Sodium dodecylbenzenesulfonate 0.14 g Styrene 56.0 g n-butyl acrylate 70.0 g 2-hydroxyethyl methacrylate 7.0 g Methacrylic acid 4.2 g Acrylamide 2.8 g n- 0.14 g of dodecyl mercaptan [Example 1-10] Same as Example 1-4 except that a 5% aqueous solution of hydrochloric acid was added instead of the 5% aqueous solution of sulfuric acid used to obtain the aggregates in Example 1-4 Thus, a re-emulsifiable polymer powder was obtained.

[Example 1-11] Re-emulsification was carried out in the same manner as in Example 1-4 except that a 5% acetic acid aqueous solution was added instead of the 5% sulfuric acid aqueous solution used for obtaining the aggregates in Example 4. A polymer powder was obtained. Example 1-12 Example 1 was repeated except that washing with sufficient pure water was repeated when filtering and separating the aggregates in Example 1-4.
-4, a re-emulsifiable polymer powder was obtained. This and the re-emulsifiable polymer powder of Example 1-4 were each added to a 1% aqueous sodium hydroxide solution to obtain a re-emulsified solution, and these were applied to a glass plate and dried at room temperature for 3 days to obtain a film. When immersed in day water and measured for water absorption, Example 1-12 had a lower water absorption and was superior in water resistance.

[Example 1-13] The composition of the aqueous emulsion (C) was changed by changing the composition of the emulsion used in Example 1-1 to those shown in Table 1-4, and otherwise using the same operation as in Example 1-1. −
10) to obtain a re-emulsifiable polymer powder. Pure water 40.0 g Sodium dodecylbenzenesulfonate 0.1 g Methyl methacrylate 50.0 g Butyl acrylate 40.0 g 2-Hydroxyethyl methacrylate 5.0 g Methacrylic acid 3.0 g Acrylamide 2.0 g n-dodecyl mercaptan 0.1 g [ Example 1-14] An aqueous emulsion (C-11) was obtained in the same manner as in Example 1-13, except that the protective colloid (B-1) was changed to the protective colloid (B-4). A polymer powder was obtained.

Example 1-15 666.7 g of the protective colloid (B-1) was charged into an autoclave equipped with a stirrer, and 1.0 g of potassium persulfate was added at 70 ° C. in a nitrogen atmosphere with stirring. On the other hand, an emulsion having the following composition was prepared, and the protective colloid was dropped at 70 ° C. over 6 hours, followed by stirring at the same temperature. Pure water 40.0 g Sodium lauryl sulfate 0.3 g Styrene 28.0 g Butadiene 70.0 g Acrylic acid 2.0 g T-dodecyl mercaptan 0.3 g Ammonia water and pure water were added to the obtained polymer, and the solid content was 10%, pH = 9 aqueous emulsion (C-12)
Was prepared. (C-12) When a 5% aqueous sulfuric acid solution was added to 1000 g at room temperature until the pH became 2.5, aggregates were formed. This solid is separated into solid and liquid by filtration.
It was dried at 0 ° C. until the residual water content became 2% or less. The re-emulsifiable polymer powder was obtained by pulverizing the dried aggregate.

[Comparative Example 1-1] The protective colloid (B-1) used in Example 1-1 was replaced with 650.0 g of pure water, except that the protective colloid (B-1) was operated in the same manner as in Example 1-1. An aqueous emulsion polymer (C-13) containing no (B-1) was obtained, and a 5% aqueous sulfuric acid solution was added until the pH became 2.5 in the same manner as in Example 1-1. Did not generate.

[Comparative Example 1-2] The protective colloid (B-1) used in Example 1-13 was replaced with 650.0 g of pure water, and the other operations were the same as in Example 1-13. An aqueous emulsion polymer (C-14) containing no (B-1) was obtained, and a 5% aqueous sulfuric acid solution was added until the pH reached 2.5 in the same manner as in Example 1-13. Did not generate.

[Comparative Example 1-3] The protective colloid (B-1) used in Example 15 was replaced with 650.0 g of pure water.
Otherwise by the same operation as in Example 1-15, an aqueous emulsion polymer containing no protective colloid (B-1) (C
-14) was obtained, and a 5% aqueous sulfuric acid solution was added until the pH reached 2.5 in the same manner as in Example 1-15, but none of the aggregates was formed.

[Comparative Example 1-4] Aqueous emulsion (C-
Regarding 1) to (C-12), each was not coagulated by acid, but the inlet air temperature was 120 ° C and the outlet air temperature was 60 ° C.
To obtain a re-emulsifiable polymer powder. All of the mixtures produced a large amount of deposits on the inner wall of the drying tower, the yield was 30% or less, and the re-emulsifiability was extremely poor.

[Evaluation Example 1-1] The solid weight of the aqueous emulsion was defined as (M1), and the weight (M2) of the aggregate dried after filtration at 80 ° C. and the residual water content (A (%))
The yield was calculated by the following equation. Yield (%) = {(M2−M2 × A / 100) / M1} × 1
The yield was rated as follows. ◎: yield is 95% or more ○: yield is 90% or more to less than 95% Δ: yield is 30 to 90% ×: yield is 30% or less [Evaluation Example 1-2] Re-emulsifiable polymer powder Is ground to a particle size of 1 mm or less, and the solid content is 10.00%.
3% by adding to 1% aqueous sodium hydroxide solution
The mixture was sufficiently stirred for 0 minutes, and then allowed to stand for 24 hours. The supernatant was collected, and the solution was filtered through a 300-mesh (50 μm) filter cloth to remove insoluble components, thereby preparing a re-emulsified liquid. . In addition, since the re-emulsifiable polymer obtained by spray drying in Comparative Examples 1-4 is already obtained in the form of powder,
These are sifted through a 16 mesh (1 mm) sieve to 1 mm
A re-emulsion was prepared in the same manner as described above for powders having the following particle sizes. The appearance, re-emulsifiability, and room temperature film-forming properties of these re-emulsified liquids were evaluated as follows.

Re-emulsifiability: The solid content of the re-emulsified liquid was determined according to JIS.
K5407.4. (Measurement method of heating residue), and the re-emulsification ratio was measured from the following calculation formula. Re-emulsification rate (%) = (solid content of re-emulsion liquid (%) / 10.0
0) × 100 The re-emulsification rate was rated as follows: ◎: Re-emulsification rate is 100% to 80% or more. : Re-emulsification rate is less than 80% to 40% or more. Δ: Re-emulsification rate is less than 40% to 10% or more. X: Re-emulsification rate is less than 10% to 0%. Appearance: The appearance of the re-emulsified liquid was visually evaluated. Room Temperature Film Formability: The re-emulsified liquid was applied to a glass plate and dried at room temperature for one day. The appearance of the film was visually evaluated and rated as follows. ：: A film is formed. Δ: Cracks are formed in the coating. ×: No film is formed.

[Evaluation Example 1-3] The re-emulsifiable polymer powder was
Pulverization was performed until the residue on an 80-mesh (200 μm) sieve became 5% or less, and this was mixed with cement in the following ratio, and the kneading time, workability, flexural strength, and compressive strength were tested. However, since the re-emulsifiable polymer obtained by spray drying in Comparative Examples 1-4 was already obtained in the form of powder, the residue on an 80 mesh (200 μm) sieve was reduced to 5%.
% Of the powder was tested in the same manner as described above. Portland cement 1000 g Toyoura standard sand 2000 g Solid defoamer 5 g Re-emulsifiable polymer powder 100 g Water was mixed with the above dry mix so that the flow value became 170 ± 10 mm. Curing is moist air (20 ℃, 80%
After 2 days, the reaction was performed at 20 ° C. and 65% RH. The test method is shown below. Kneading time: The time required from mixing water in the dry mix to kneading to a uniform wet state was measured. Iron workability: The workability when performing surface leveling with an iron was rated as follows. ◎: Excellent ○: Good △: Normal ×: Poor Flexural strength: JIS for material age 7 and 28 days
Tested according to A1172. Compressive strength: JIS for material age 7 and 28 days
Tested according to A1172. In addition, a test using no re-emulsifiable polymer powder as a blank was also performed.

The compositions of the protective colloids used in the above Examples and Comparative Examples are shown in Table 11-, the compositions of the aqueous emulsions are shown in Tables 1-2 to 1-4, and the composition and evaluation of the re-emulsifiable polymer powder. The results are shown in Tables 1-5 to 1-15.

[0202]

[Table 1]

[0203]

[Table 2]

[0204]

[Table 3]

[0205]

[Table 4]

[0206]

[Table 5]

[0207]

[Table 6]

[0208]

[Table 7]

[0209]

[Table 8]

[0210]

[Table 9]

[0211]

[Table 10]

[0212]

[Table 11]

[0213]

[Table 12]

[0214]

[Table 13]

[0215]

[Table 14]

[0216]

[Table 15] Table 1-15. Composition and evaluation result of re-emulsifiable polymer powder (6)

[0219]

[Table 16] Table 1-16. Composition and evaluation result of re-emulsifiable polymer powder (6) (continued) 2. Example of Aggregating Aqueous Emulsion Produced by Core / Shell Polymerization Method with Acid (System Using Ethylenically Unsaturated Monomer Having Amide Group) [Example 2-1] Aqueous Solution of Step 1 (Core Particle Polymerization Step) Preparation of emulsion An aqueous emulsion (A-1) was prepared by the following operation. An aqueous solution consisting of 785 g of pure water and 3 g of sodium dodecylbenzenesulfonate (abbreviated as DBS) was charged into a reaction vessel equipped with a stirrer, a reflux condenser, and a thermometer. Was added. On the other hand, prepare an emulsion having the following composition,
This emulsion is added dropwise to the above aqueous solution at 80 ° C. in 3 hours,
Thereafter, the temperature was maintained at 80 ° C. for 3 hours. Pure water 400 g DBS 1 g Styrene 400 g n-butyl acrylate 500 g 2-hydroxyethyl methacrylate 50 g methacrylic acid 30 g acrylamide 20 g n-dodecyl mercaptan 1 g To the obtained aqueous emulsion, ammonia water and pure water were added. The resin content was adjusted to 45%. This aqueous emulsion is designated as (A-1).

Step 2 (Shell Polymerization Step) In a reaction vessel equipped with a stirrer, a reflux condenser, and a thermometer, 222.2 g of the aqueous emulsion (A-1) and pure water 6
47.8 g of methacrylamide and 100.0 g of methacrylamide were charged, and the temperature was raised to 75 ° C. in a nitrogen atmosphere with stirring, and this temperature was maintained. 5% after methacrylamide is completely dissolved
An aqueous ammonium persulfate solution (30.0 g) was added, and the mixture was kept at 75 ° C. for 7 hours. Thereby, resin content = 20%, p
An aqueous emulsion of H = 9 was obtained. This aqueous emulsion is designated as (C-1).

Step 3 (Aggregate Production Step) The aqueous emulsion (C-1) was diluted with pure water so as to have a solid content of 10%, and 1000 g of the diluted product was adjusted to pH 2.5 with a 5% aqueous sulfuric acid solution at room temperature. Aggregates were formed when the addition was continued. After this aggregate is separated into solid and liquid by filtration,
Drying was carried out at a temperature of 2 ° C. until the residual water content became 2% or less. The re-emulsifiable polymer powder was obtained by pulverizing the dried aggregate.

[Examples 2-2 to 9] Preparation of aqueous emulsion in step 1 (core particle polymerization step) An aqueous emulsion (A-1) was obtained in the same manner as in Example 2-1. Step 2 (Shell polymerization step) Aqueous emulsion (C-2 to 9) having the composition shown in Table 2-2
Was prepared. Step 3 (Aggregate Production Step) From the aqueous emulsion (C-2 to 9), a re-emulsifiable polymer powder was obtained by the same operation as in Example 2-1.

Example 2-10 Preparation of Aqueous Emulsion in Step 1 (Core Particle Polymerization Step) The aqueous emulsion (A) was prepared using the monomer composition shown in Table 2-1.
In the same manner as in -1), an aqueous emulsion (A-2) having a pH of 9 and a solid content of 45% was obtained. Step 2 (Shell polymerization step) An aqueous emulsion (C-10) having the composition shown in Table 2-3 was prepared. Step 3 (Aggregate Production Step) From the aqueous emulsion (C-10), a re-emulsifiable polymer powder was obtained by the same operation as in Example 2-1.

Example 2-11 Preparation of Aqueous Emulsion of Step 1 (Core Particle Polymerization Step) An aqueous emulsion (A-2) was prepared in the same manner as in Example 2-10.
I got Step 2 (Shell polymerization step) An aqueous emulsion (C-11) having the composition shown in Table 2-3 was prepared. Step 3 (Aggregate Production Step) From the aqueous emulsion (C-11), a re-emulsifiable polymer powder was obtained by the same operation as in Example 2-1.

Example 2-12 Preparation of Aqueous Emulsion in Step 1 (Core Particle Polymerization Step) An aqueous emulsion (A-3) was prepared by the following operation. An autoclave equipped with a stirrer was charged with 790 g of pure water, 2 g of sodium lauryl sulfate and 1 g of sodium bicarbonate, and 10 g of potassium persulfate was added at 70 ° C. under a nitrogen atmosphere with stirring. On the other hand, an emulsion having the following composition was prepared and added dropwise to the aqueous solution at 70 ° C. over 6 hours.
It was kept at the same temperature. Pure water 400 g Sodium lauryl sulfate 3 g Styrene 280 g Butadiene 700 g Acrylic acid 20 g T-dodecyl mercaptan 3 g To the obtained SBR latex, aqueous ammonia (A) having a pH of 9 and a solid content of 45% was added by adding ammonia water and pure water. -3) was prepared. Step 2 (Shell polymerization step) An aqueous emulsion (C-12) having the composition shown in Table 2-3 was prepared. Step 3 (Aggregate Production Step) From the aqueous emulsion (C-12), a re-emulsifiable polymer powder was obtained by the same operation as in Example 2-1.

[Example 2-13] Instead of the 5% sulfuric acid aqueous solution used for obtaining the aggregate in Example 2-4, 5%
A re-emulsifiable polymer powder was obtained in the same manner as in Example 2-4 except that an aqueous hydrochloric acid solution was added.

[Example 2-14] Instead of the 5% sulfuric acid aqueous solution used for obtaining the aggregate in Example 2-4, 5%
A re-emulsifiable polymer powder was obtained in the same manner as in Example 2-4, except that an aqueous acetic acid solution was added.

[Example 2-15] A re-emulsifiable polymer was prepared in the same manner as in Example 2-4, except that the aggregates were separated by filtration in Example 2-4, except that washing with sufficient pure water was repeated. A powder was obtained. This and the re-emulsifiable polymer powder of Example 2-4 were each added to a 1% aqueous sodium hydroxide solution to obtain a re-emulsified solution. These were applied to a glass plate and dried at room temperature for 3 days to obtain a film. When the film was immersed in day water and the water absorption of the film was measured, Example 2-15 was lower and excellent in water resistance.

[Comparative Examples 2-1 to 2-3] Each of the aqueous emulsions (A-1) to (A-3) was diluted with pure water to a solid content of 10%, and then diluted with 1000 g of the diluted product at room temperature by 5%. An aqueous sulfuric acid solution was added until the pH reached 2.5, but none of the aggregates formed.

[Comparative Example 2-4] Aqueous emulsion (C-
1) to (C-12), each having an inlet air temperature of 120
By spray-drying at 60 ° C. and an outlet air temperature of 60 ° C., a re-emulsifiable polymer powder was obtained. Each of the aqueous emulsions produced a large amount of deposits on the inner wall of the drying tower, the yield was 30% or less, and the re-emulsifiability was extremely poor.

[Evaluation Example 2-1] The yield was calculated and graded in the same manner as in Evaluation Example 1-1.

[Evaluation Examples 2-2 to 3] Re-emulsifiable liquids were prepared in the same manner as in Evaluation Examples 1-2 to 3 and the re-emulsifiable polymer powder.
In addition, since the re-emulsifiable polymer obtained by spray drying in Comparative Example 2-4 is already obtained in the form of powder, these are sieved through a 16 mesh (1 mm) sieve, and the same applies to powder having a particle size of 1 mm or less. A re-emulsion was prepared by the method described above.

The appearance, re-emulsifiability, and room-temperature film-forming properties of these re-emulsified liquids were evaluated by preparing a cement mixture according to the method described in Evaluation Example 1-2 and the method described in Evaluation Example 1-3.

However, since the re-emulsifiable polymer obtained by spray drying in Comparative Example 2-4 was already obtained in powder form,
These powders, which were classified so that the residue on an 80 mesh (200 μm) sieve was 5% or less, were tested in the same manner as described above.

Step 1 used in the above Examples and Comparative Examples
Table 2-1 shows the composition of the aqueous emulsion produced in Table 2, and Table 2-2 shows the composition of the aqueous emulsion produced in Step 2.
Table 2-3 shows the composition and evaluation results of the re-emulsifiable polymer powder in Tables 2-4 to 2-13.

[0234]

[Table 17] Table 2-1. Composition of aqueous emulsion obtained in step 1

[0235]

[Table 18]

[0236]

[Table 19]

[0237]

[Table 20]

[0238]

[Table 21]

[0239]

[Table 22]

[0240]

[Table 23]

[0241]

[Table 24]

[0242]

[Table 25]

[0243]

[Table 26]

[0244]

[Table 27]

[0245]

[Table 28] Table 2-12. Composition and evaluation result of re-emulsifiable polymer powder (6)

[0246]

[Table 29] Table 2-13. Composition and evaluation result of re-emulsifiable polymer powder (6) (continued) 3. Example of Aggregating Aqueous Emulsion / Protective Colloid Mixture with Acid (System Using Ethylenically Unsaturated Monomer Having Amide Group) [Example 3-1] Aqueous Emulsion Production Step An aqueous emulsion (A- 1) was prepared. An aqueous solution consisting of 785 g of pure water and 3 g of sodium dodecylbenzenesulfonate (abbreviated as DBS) was charged into a reaction vessel equipped with a stirrer, a reflux condenser and a thermometer. Was added. On the other hand, prepare an emulsion having the following composition,
The rollers were added dropwise to the above aqueous solution at a temperature of 80 ° C. over 3 hours and kept at the same temperature for 3 hours. Pure water 400 g DBS 1 g Styrene 400 g n-butyl acrylate 500 g 2-hydroxyethyl methacrylate 50 g methacrylic acid 30 g acrylamide 20 g n-dodecyl mercaptan 1 g To the obtained aqueous emulsion, ammonia water and pure water were added, and pH = 9. The resin content was adjusted to 45%. This aqueous emulsion is designated as (A-1).

Protective Colloid Production Step A protective colloid (a1) was prepared by the following operation.
850 g of pure water and 100.0 g of methacrylamide were charged into a reaction vessel equipped with a stirrer, a reflux condenser and a thermometer, and the temperature was raised to 75 ° C. in a nitrogen atmosphere with stirring, and this temperature was maintained. After the methacrylamide was completely dissolved, 30.0 g of a 5% aqueous solution of ammonium persulfate was added, and the mixture was kept at 75 ° C. for 7 hours. Aqueous ammonia and pure water were added thereto to obtain a protective colloid (B-1) having a resin content of 10% and a pH of 9.

Mixing Step Aqueous emulsion (A-1) and protective colloid (B-1)
Were mixed and stirred so that the solid ratio became 50/50.

Aggregate Production Step The mixture of the aqueous emulsion (A-1) and the protective colloid (B-1) produced in the mixing step is diluted with pure water so as to have a resin content of 10%. Aggregates formed when 5% sulfuric acid was added to 1000 g at room temperature until the pH reached 2.5. After the aggregate was separated into solid and liquid by filtration, it was dried at 80 ° C. until the residual water content became 2% or less. The re-emulsifiable polymer powder was obtained by pulverizing the dried aggregate.

[Examples 3-2 to 9] Aqueous emulsion production process In the same manner as in Example 3-1, aqueous emulsions (A-1 to 3) having the compositions shown in Table 3-1 were prepared. Protective colloid production process Protective colloids (B-2 to 8) having the compositions shown in Table 3-2 were prepared in the same manner as in Example 3-1. Mixing step Aqueous emulsion (A-1-3) and protective colloid (B-
2 to 8) were mixed and stirred so that the solid ratio became 50/50 or 70/30. Aggregate Production Step A re-emulsifiable polymer powder was obtained in the same manner as in Example 3-1.

[Example 3-10] Instead of the 5% sulfuric acid aqueous solution used for obtaining the aggregate in Example 3-4, 5%
A re-emulsifiable polymer powder was obtained in the same manner as in Example 3-4 except that an aqueous hydrochloric acid solution was added.

[Example 3-11] Instead of the 5% sulfuric acid aqueous solution used for obtaining the aggregate in Example 3-4, 5%
A re-emulsifiable polymer powder was obtained in the same manner as in Example 4 except that an acetic acid aqueous solution was added.

[Example 3-12] A re-emulsifiable polymer was prepared in the same manner as in Example 3-4, except that the aggregates were separated by filtration in Example 3-4, except that washing with sufficient pure water was repeated. A powder was obtained. This and the re-emulsifiable polymer powder of Example 3-4 were each added to a 1% aqueous sodium hydroxide solution to obtain a re-emulsified solution, which was applied to a glass plate and dried at room temperature for 3 days. As a result, Example 3-12 was more excellent in water resistance.

[Example 3-13] Aqueous emulsion (A
-2) The protective colloid (B-1) was added at a solid ratio of 50 /
After mixing and stirring to 50, a re-emulsifiable polymer powder was obtained by the same operation as in Example 3-1.

[Example 3-14] Aqueous emulsion (A
-2) The protective colloid (B-4) was added at a solid ratio of 50 /
After mixing and stirring to 50, a re-emulsifiable polymer powder was obtained by the same operation as in Example 3-1.

Example 3-15 Aqueous emulsion production process An aqueous emulsion (A-3) was prepared by the following operation. In an autoclave equipped with a stirrer, 790 g of pure water, 2 g of sodium lauryl sulfate and 1 g of sodium bicarbonate were charged, and 10 g of potassium persulfate was added at a temperature of 70 ° C. with stirring in a nitrogen atmosphere. On the other hand, an emulsified monomer having the following composition was prepared and dropped into the above aqueous solution over 6 hours, followed by aging. Pure water 400 g Sodium lauryl sulfate 3 g Styrene 280 g Butadiene 700 g Acrylic acid 20 g T-dodecyl mercaptan 3 g To the obtained SBR latex, aqueous ammonia (pH = 9, solid content = 45%) was added by adding ammonia water and pure water. -3) was prepared. Protective Colloid Production Step A protective colloid (B-1) having the composition shown in Table 3-2 was prepared in the same manner as in Example 3-1. Mixing step Aqueous emulsion (A-3) and protective colloid (B-1)
Were mixed and stirred so that the solid ratio became 50/50. Aggregate Production Step A re-emulsifiable polymer powder was obtained in the same manner as in Example 3-4, except that, when the aggregate was separated by filtration in Example 3-4, washing with sufficient pure water was repeated.

[Comparative Examples 3-1 to 3-3] Each of the aqueous emulsions (A-1) to (A-3) was diluted with pure water to a solid content of 10%, and then diluted with 1000 g of the diluted product at room temperature by 5%. An aqueous sulfuric acid solution was added until the pH reached 2.5, but none of the aggregates formed.

[Comparative Example 3-4] Each of the mixtures of the aqueous emulsions and protective colloids prepared in Examples 3-1 to 3-9 and Examples 3-13 to 3-15 was treated with an inlet air temperature of 1
By spray drying at 20 ° C. and an outlet air temperature of 60 ° C., a re-emulsifiable polymer powder was obtained. All of the mixtures produced a large amount of deposits on the inner wall of the drying tower, the yield was 30% or less, and the re-emulsifiability was extremely poor.

[Evaluation Example 3-1] The yield was calculated and graded in the same manner as in Evaluation Example 1-1.

[Evaluation Examples 3-2 to 3] Re-emulsifiable liquids were prepared from the re-emulsifiable polymer powder in the same manner as in Evaluation Examples 1-2 to 3. The re-emulsifiable polymer obtained by spray drying in Comparative Example 2-4 was already obtained in powder form.
A re-emulsion was prepared in the same manner as described above for powder having a particle size of 1 mm or less through a 6-mesh (1 mm) sieve.

The appearance, re-emulsifiability, and room-temperature film-forming properties of these re-emulsified liquids were evaluated by preparing a cement composition according to the method described in Evaluation Example 1-2 and the method described in Evaluation Example 1-3.

However, since the re-emulsifiable polymer obtained by spray drying in Comparative Example 3-4 was already obtained in powder form,
These are sifted through a 16 mesh (1 mm) sieve to 1 mm
A re-emulsion was prepared in the same manner as described above for powders having the following particle sizes.

Table 1 shows the compositions of the aqueous emulsions used in the above Examples and Comparative Examples, and Table 3 shows the compositions of the protective colloids.
Table 2 shows the composition of the re-emulsifiable polymer powder and the evaluation results.
-3 to Table 3-14.

[0264]

[Table 30]

[0265]

[Table 31]

[0266]

[Table 32]

[0267]

[Table 33]

[0268]

[Table 34]

[0269]

[Table 35]

[0270]

[Table 36]

[0271]

[Table 37]

[0272]

[Table 38]

[0273]

[Table 39]

[0274]

[Table 40]

[0275]

[Table 41]

[0276]

[Table 42] Table 3-13. Composition and evaluation result of re-emulsifiable polymer powder (6)

[0277]

Table 3-14. Composition and evaluation result of re-emulsifiable polymer powder (6) (continued) 4. Example of Aggregating an Aqueous Emulsion Produced by Protective Colloid Polymerization Method with Polyvalent Metal Salt (System Using Ethylenically Unsaturated Monomer Having Amide Group) [Example 4-1] Step 1 (Aqueous emulsion production step) <Preparation of protective colloid (a1)> A reaction vessel equipped with a stirrer, a reflux condenser and a thermometer was charged with 785.0 pure water.
g, 150.0 g of methacrylamide, and stirred.
The temperature was raised to 75 ° C. in a nitrogen atmosphere, and this temperature was maintained. After the methacrylamide was completely dissolved, 45.0 g of a 5% aqueous ammonium persulfate solution was added, and the mixture was added at 75 hours for 75 hours.
The solution was kept at ℃ to obtain an aqueous solution. Aqueous ammonia and pure water were added thereto to obtain a protective colloid (B-1) having a resin content of 15% and a pH of 9. <Polymerization of protective colloid> In a reaction vessel equipped with a stirrer, a reflux condenser and a thermometer, a protective colloid (B-1) 66 was added.
6.7 g was charged, and the temperature was 80 ° C. in a nitrogen atmosphere with stirring.
Then, 0.5 g of potassium persulfate was added. On the other hand, an emulsion having the following composition was prepared, added dropwise to the above aqueous solution at 80 ° C. over 3 hours, and kept for 3 hours. Pure water 40.0 g Sodium dodecylbenzenesulfonate 0.1 g Styrene 40.0 g N-butyl acrylate 50.0 g 2-Hydroxyethyl methacrylate 5.0 g Methacrylic acid 3.0 g Acrylamide 2.0 g 0.1 g of n-dodecyl mercaptan Aqueous emulsion (C-1) having a resin content of 10% and a pH of 9 was prepared by adding aqueous ammonia and pure water to the obtained polymer. Step 2 (Aggregate Production Step) When 50 g of a 45% aqueous solution of aluminum sulfate was added to 1000 g of (C-1) at room temperature, an aggregate was formed. After the aggregate was separated into solid and liquid by filtration, it was dried at 80 ° C. until the residual water content became 2% or less. Hereinafter, all the residual moisture amounts are values measured by this method). The re-emulsifiable polymer powder was obtained by pulverizing the dried aggregate.

[Examples 4-2 to 8] Step 1 (aqueous emulsion production step) <Preparation of protective colloid (a1)> The same operation as in Example 4-1 was carried out to obtain a protective colloid (a1) having the composition shown in Table 4-1. Colloid (B
-2) to (B-8) were prepared. <Protective colloid polymerization> By the same operation as in Example 4-1, the protective colloid (B-1) was replaced with the protective colloids (B-2) to (B-8) instead of the protective colloid (B-1). And aqueous emulsions (C-2) to (C-8)
I got Step 2 (Agglomerate Production Step) By the same operation as in Example 4-1, instead of the aqueous emulsion (C-1) of Example 4-1, the aqueous emulsions (C-2) to (C-8) were obtained. Substituting for each gave a re-emulsifiable polymer powder.

Example 4-9 Step 1 (Aqueous Emulsion Production Step) <Preparation of Protective Colloid (a1)> A protective colloid (B-1) was prepared in the same manner as in Example 4-1. <Protective Colloid Polymerization> A protective colloid (B-1) 40 was placed in a reaction vessel equipped with a stirrer, a reflux condenser and a thermometer.
0.0 g and 210 g of pure water were charged, and 0.7 g of potassium persulfate was added at a temperature of 80 ° C. with stirring in a nitrogen atmosphere. On the other hand, an emulsion having the following composition was prepared, dropped into the above aqueous solution in 3 hours, and aged for 3 hours. Pure water 56.0 g Sodium dodecylbenzenesulfonate 0.14 g Styrene 56.0 g n-butyl acrylate 70.0 g 2-hydroxyethyl methacrylate 7.0 g Methacrylic acid 4.2 g Acrylamide 2.8 g n- Dodecyl mercaptan 0.14 g Aqueous emulsion (C-9) having a resin content of 10% and a pH of 9 was prepared by adding aqueous ammonia and pure water to the obtained polymer. Step 2 (Aggregate Production Step) When 50 g of a 45% aluminum sulfate aqueous solution was added to 1000 g of (C-9) at room temperature, an aggregate was formed. After the aggregate was separated into solid and liquid by filtration, it was dried at 80 ° C. until the residual water content became 2% or less. The re-emulsifiable polymer powder was obtained by pulverizing the dried aggregate.

Example 4-10 Example 4-10 was repeated, except that 225 g of a 10% ferric sulfate aqueous solution was added instead of the 45% aluminum sulfate aqueous solution used for obtaining the aggregate in Example 4-4. -4, a re-emulsifiable polymer powder was obtained.

Example 4-11 A re-emulsifiable polymer powder was obtained in the same manner as in Example 4-4, except that the temperature of the aqueous emulsion was changed to 70 ° C. and then 45% of aluminum sulfate was added. Agglomerates were larger than in Example 4-4, so that the solid-liquid separation time by filtration was reduced to 1/10, and workability was improved.

Example 4-12 Example 4-4 was repeated, except that 225 g of a 10% aqueous solution of calcium chloride was added instead of the 45% aqueous solution of aluminum sulfate used to obtain the aggregates in Example 4-4. A re-emulsifiable polymer powder was obtained in the same manner as described above.

Example 4-13 The pH of an aqueous emulsion was adjusted with sulfuric acid before adding a polyvalent metal salt in Example 4-12.
Was adjusted to 4 and then 225 g of a 10% aqueous solution of calcium chloride was added as a polyvalent metal salt.
By the same operation as in Example 12, a re-emulsifiable polymer powder was obtained. Agglomerates were larger than those in Example 4-12, and the solid-liquid separation time by filtration was shortened to 1/3, and workability was improved.

[Example 4-14] A re-emulsifiable polymer powder was obtained in the same manner as in Example 4-4, except that the amount of 45% aluminum sulfate added in Example 4-4 was changed to 6.5 g. Was.

[Example 4-15] The re-emulsifiable polymer was prepared in the same manner as in Example 4-4, except that washing with sufficient pure water was repeated when the aggregates were separated by filtration in Example 4-4. A powder was obtained. This and the re-emulsifiable polymer powder of Example 4-4 were each added to a 1% aqueous sodium hydroxide solution to obtain a re-emulsified solution. These were applied to a glass plate and dried at room temperature for 3 days to obtain a film. When the film was immersed in day water and the water absorption of the film was measured, the water absorption of Example 4-15 was lower and the water resistance was better.

[Example 4-16] Step 1 (aqueous emulsion production step) <Preparation of protective colloid (a1)> A protective colloid (B-1) was prepared in the same manner as in Example 4-1. <Protective Colloid Polymerization> The emulsion used in Example 4-1 was changed as follows, and an aqueous emulsion (C-10) was obtained by the same operation as in Example 4-1. A powder was obtained. Pure water 40.0 g Sodium dodecylbenzenesulfonate 0.1 g Methyl methacrylate 50.0 g Butyl acrylate 40.0 g 2-Hydroxyethyl methacrylate 5.0 g Methacrylic acid 3.0 g Acrylamide 2.0 g n-Dodecyl mercaptan 0.1 g 2 (Aggregate production process) In the same manner as in Example 4-1, a re-emulsifiable polymer powder was obtained.

[Example 4-17] Protective colloid (B-
Example 4-1 was changed from 1) to protective colloid (B-4).
Aqueous emulsion (C-11) was obtained in the same manner as in 6,
Further, a re-emulsifiable polymer powder was obtained from this.

Example 4-18 Step 1 (Aqueous Emulsion Production Step) <Preparation of Protective Colloid (a1)> A protective colloid (B-1) was prepared in the same manner as in Example 4-1. <Protective Colloid Polymerization> In an autoclave equipped with a stirrer, 666.7 g of the protective colloid (B-1) was charged, and 1.0 g of potassium persulfate was added at 70 ° C. under stirring in a nitrogen atmosphere. On the other hand, an emulsion having the following composition was prepared and dropped into the above aqueous solution over 6 hours to ripen. Pure water 40.0 g Sodium lauryl sulfate 0.3 g Styrene 28.0 g Butadiene 70.0 g Acrylic acid 2.0 g T-dodecyl mercaptan 0.3 g To the obtained polymer, ammonia water and pure water were added, and a resin component was obtained. 10%, pH = 9 aqueous emulsion (C-12)
Was prepared. Step 2 (Aggregate Production Step) When 50 g of a 45% aqueous solution of aluminum sulfate was added to 1000 g of (C-12) at room temperature, an aggregate was formed. After the aggregate was separated into solid and liquid by filtration, it was dried at 80 ° C. until the residual water content became 2% or less. The re-emulsifiable polymer powder was obtained by pulverizing the dried aggregate.

[Comparative Example 4-1] The protective colloid (B-1) used in Example 4-1 was replaced with 650.0 g of pure water, and the other operations were the same as in Example 4-1. An aqueous emulsion polymer (C-13) containing no (B-1) was obtained, and an attempt was made to obtain a re-emulsifiable polymer powder therefrom. However, since the aggregate after drying was soft, pulverization was impossible. The re-emulsifiability was evaluated without grinding.

[Comparative Example 4-2] The protective colloid (B-1) used in Example 4-16 was replaced with 650.0 g of pure water, and the other operations were the same as in Example 4-16. An aqueous emulsion polymer (C-14) containing no (B-1) was obtained, and an attempt was made to obtain a re-emulsifiable polymer powder therefrom. However, since the aggregate after drying was soft, pulverization was impossible. The re-emulsifiability was evaluated without grinding.

[Comparative Example 4-3] The protective colloid (B-1) used in Example 4-18 was replaced with 650.0 g of pure water, except that the protective colloid was used in the same manner as in Example 4-18. An aqueous emulsion polymer (C-15) containing no (B-1) was obtained, and an attempt was made to obtain a re-emulsifiable polymer powder therefrom. However, since the aggregate after drying was soft, pulverization was impossible. The re-emulsifiability was evaluated without grinding.

[Comparative Example 4-4] Aqueous emulsion (C-
Regarding 1) to (C-12), re-emulsifiable polymer powders were obtained by spray drying at 120 ° C. inlet air temperature and 60 ° C. outlet air temperature instead of coagulation with polyvalent metal salts. All of the mixtures produced a large amount of deposits on the inner wall of the drying tower, the yield was 30% or less, and the re-emulsifiability was extremely poor.

[Comparative Example 4-5] A re-emulsifiable polymer powder was obtained in the same manner as in Example 4-4 except that the amount of 45% aluminum sulfate added in Example 4-4 was changed to 0.01 g. However, no aggregate was formed.

[Evaluation Example 4-1] The yield was calculated and graded in the same manner as in Evaluation Example 1-1.

[Evaluation Example 4-2] A re-emulsifiable polymer powder was prepared and evaluated in the same manner as in Evaluation Example 1-2.
However, since the re-emulsifiable polymers of Comparative Examples 4-1 to 3 were all soft and could not be pulverized, they were not pulverized. In addition, since the re-emulsifiable polymer obtained by spray drying in Comparative Example 4-4 was already obtained in a powder form, these were reconstituted in 16 mesh (1
mm), a re-emulsion liquid was prepared in the same manner as described above for powder having a particle size of 1 mm or less.

[Evaluation Example 4-3] Evaluation was performed in the same manner as in Evaluation Example 1-3. However, since the re-emulsifiable polymer obtained by spray drying in Comparative Example 4-4 was already obtained in the form of a powder, the residue on a sieve of 80 mesh (200 μm) was reduced to 5%.
% Of the powder was tested in the same manner as described above.

Table 4-1 shows the composition of the protective colloid used in the above Examples and Comparative Examples, and Tables 4-2 to 4-4 show the compositions of the aqueous emulsions. The evaluation results are shown in Tables 4-5 to 4-13.

[0298]

[Table 44]

[0299]

[Table 45]

[0300]

[Table 46]

[0301]

[Table 47]

[0302]

[Table 48]

[0303]

[Table 49]

[0304]

[Table 50]

[0305]

[Table 51]

[0306]

[Table 52]

[0307]

[Table 53]

[0308]

[0309]

[Table 55]

[0310]

[Table 56]

[0311]

[Table 57]

[0312]

[Table 58] Table 4-15. Composition and evaluation result of re-emulsifiable polymer powder (3) (continued)

[0313]

[Table 59] Table 4-16. Composition and evaluation result of re-emulsifiable polymer powder (3) (continued) 5. Example of Aggregating Aqueous Emulsion Produced by Core / Shell Polymerization Method with Polyvalent Metal Salt (System Using Ethylenically Unsaturated Monomer Having Amide Group) [Example 5-1] Step 1 (Core Particle Polymerization Step) Preparation of Aqueous Emulsion A) An aqueous emulsion (A-1) was prepared by the following operation. 785 g of pure water and 3 g of sodium dodecylbenzenesulfonate (abbreviated as DBS) are charged into a reaction vessel equipped with a stirrer, a reflux condenser and a thermometer, and 5 g of potassium persulfate is added at 80 ° C. with stirring in a nitrogen atmosphere. The prepared aqueous solution was prepared. On the other hand, an emulsion having the following composition was prepared and added dropwise to the above aqueous solution at 80 ° C. in 3 hours.
It was kept at the same temperature for a time. Pure water 400 g DBS 1 g Styrene 400 g n-butyl acrylate 500 g 2-hydroxyethyl methacrylate 50 g methacrylic acid 30 g acrylamide 20 g n-dodecyl mercaptan 1 g To the obtained aqueous emulsion, ammonia water and pure water were added. The resin content was adjusted to 45%. This aqueous emulsion is designated as (A-1). Step 2 (Shell polymerization step) In a reaction vessel equipped with a stirrer, a reflux condenser and a thermometer, 222.2 g of the aqueous emulsion (A-1), 647.8 g of pure water, and 100.0 g of methacrylamide were charged.
Under stirring, the temperature was raised to 75 ° C. in a nitrogen atmosphere, and this temperature was maintained. After methacrylamide is completely dissolved, 5
30.0 g of a 10% aqueous solution of ammonium persulfate was added, and the mixture was kept at 75 ° C. for 7 hours. Thereby, resin content = 20%, p
An aqueous emulsion of H = 9 was obtained. This aqueous emulsion is designated as (C-1). Step 3 (Aggregate Production Step) The aqueous emulsion (C-1) was diluted with pure water to a resin content of 10%, and 50 g of a 45% aluminum sulfate aqueous solution was added to 1000 g of the diluted product at room temperature to form an aggregate. This solid was separated into solid and liquid by filtration, and then dried at 80 ° C. until the residual water content became 2% or less (the residual water content was JI
It was measured by the method of measuring loss on heating of SK5407.5. Hereinafter, all the residual moisture amounts are values measured by this method). The re-emulsifiable polymer powder was obtained by pulverizing the dried aggregate.

[Examples 5-2 to 12] Preparation of aqueous emulsion of step 1 (core particle polymerization step) i) Preparation of aqueous emulsion (A-1) The aqueous emulsion (A-1) was prepared in the same manner as in Example 5-1. A-1) was prepared.

Ii) Preparation of Aqueous Emulsion (A-2) The monomer composition shown in Table 5-1 was used to prepare the aqueous emulsion (A-1) in the same manner as in the preparation method of the aqueous emulsion (A-1) shown in Example 5-1. 9. An aqueous emulsion (A-2) having a resin content of 45% was obtained. iii) Preparation of aqueous emulsion (A-3) In an autoclave equipped with a stirrer, 790 g of pure water, 2 g of sodium lauryl sulfate, and 1 g of sodium bicarbonate were charged, and 10 g of potassium persulfate at 70 ° C under stirring in a nitrogen atmosphere.
Was added. On the other hand, an emulsion having the following composition was prepared and dropped into the above aqueous solution over 6 hours to ripen. Pure water 400 g Sodium lauryl sulfate 3 g Styrene 280 g Butadiene 700 g Acrylic acid 20 g T-dodecylmercaptan 3 g To the obtained SBR latex, aqueous ammonia (pH = 9, resin content = 45%) was added by adding ammonia water and pure water. -3) was prepared. Step 2 (Shell polymerization step) Table 5-2 and Table 5-3 were obtained by the same operation as in Example 5-1.
Aqueous emulsions (C-2) to (C-1)
2) was prepared. Step 3 (Aggregate Production Step) By the same operation as in Example 5-1, a re-emulsifiable polymer powder was obtained from each of the aqueous emulsions (C-2) to (C-12).

Example 5-13 Example 5-13 was repeated, except that 225 g of a 10% aqueous ferric sulfate solution was added in place of the 45% aluminum sulfate aqueous solution used to obtain the aggregates in Example 5-4. In the same manner as in Example 4, a re-emulsifiable polymer powder was obtained.

Example 5-14 The procedure of Example 5-4 was repeated, except that the temperature of the aqueous emulsion was changed to 70 ° C., and then 45% aluminum sulfate was added. A combined powder was obtained. Agglomerates were larger than in Example 5-4, and the solid-liquid separation time by filtration was reduced to 1/10, and workability was improved.

Example 5-15 Example 5-4 was repeated, except that 225 g of a 10% calcium chloride aqueous solution was added instead of the 45% aluminum sulfate aqueous solution used for obtaining the aggregates in Example 5-4. A re-emulsifiable polymer powder was obtained in the same manner as described above.

[Example 5-16] In Example 5-15, the pH of the aqueous emulsion was adjusted with sulfuric acid before adding the polyvalent metal salt.
Was adjusted to 4 and then 225 g of a 10% aqueous calcium chloride solution was added as a polyvalent metal salt.
By the same operation as in Example 15, a re-emulsifiable polymer powder was obtained. Agglomerates were larger than those in Example 5-15, and the solid-liquid separation time by filtration was shortened to 1/3, and workability was improved.

Example 5-17 A re-emulsifiable polymer powder was obtained in the same manner as in Example 5-4, except that the amount of 45% aluminum sulfate added in Example 5-4 was changed to 6.5 g. Was.

[Example 5-18] The re-emulsifiable polymer was prepared in the same manner as in Example 5-4, except that washing with sufficient pure water was repeated when the aggregates were separated by filtration in Example 5-4. A powder was obtained. This and the re-emulsifiable polymer powder of Example 5-4 were each added to a 1% aqueous sodium hydroxide solution to obtain a re-emulsified solution, and these were applied to a glass plate and dried at room temperature for 3 days. When the film was immersed in day water and the water absorption of the film was measured, the water absorption of Example 5-18 was lower and the water resistance was better.

[Comparative Examples 5-1 to 3] Each of the aqueous emulsions (A-1) to (A-3) was diluted with pure water to a resin content of 10%, and then diluted with 1000 g of 45% aluminum sulfate at room temperature. When 50 g of the aqueous solution was added, aggregates were formed. After the aggregate was separated into solid and liquid by filtration, it was dried at 80 ° C. until the residual water content became 2% or less. However, all the dried aggregates were soft and could not be ground. The re-emulsifiability was evaluated without grinding.
[Comparative Example 5-4] Aqueous emulsions (C-1) to (C-)
12) Each was spray-dried at an inlet air temperature of 120 ° C and an outlet air temperature of 60 ° C to obtain a re-emulsifiable polymer powder. Each of the aqueous emulsions produced a large amount of deposits on the inner wall of the drying tower, the yield was 30% or less, and the re-emulsifiability was extremely poor.

Comparative Example 5-5 A re-emulsifiable polymer powder was obtained in the same manner as in Example 5-4, except that the amount of 45% aluminum sulfate added in Example 5-4 was changed to 0.01 g. However, no aggregate was formed.

[Evaluation Example 5-1] The yield was calculated and graded in the same manner as in Evaluation Example 1-1.

[Evaluation Example 5-2] A re-emulsified liquid was prepared from the re-emulsifiable polymer powder in the same manner as in Evaluation Example 1-2. However, since the re-emulsifiable polymers of Comparative Examples 5-1 to 3 were all soft and could not be pulverized, the re-emulsifiable liquid was prepared in the same manner as described above without pulverization. Comparative Example 5
-4, the re-emulsifiable polymer obtained by spray-drying is already obtained in powder form.
m) The powder having a particle size of 1 mm or less was sieved to prepare a re-emulsion liquid in the same manner as described above.
-2.

[Evaluation Example 5-3] The re-emulsifiable polymer powder was tested in the same manner as in Evaluation Example 1-3. However, since the re-emulsifiable polymer obtained by spray-drying in Comparative Example 5-4 was already obtained in the form of a powder, these were 80 mesh (200 μm).
The powder classified so that the residue on the sieve was 5% or less was tested in the same manner as described above.

Step 1 used in the above Examples and Comparative Examples
Table 5-1 shows the composition of the aqueous emulsion produced in Table 5, and Table 5-2 shows the composition of the aqueous emulsion produced in Step 2.
Table 5-3 shows the composition of the re-emulsifiable polymer powder and the evaluation results thereof.

[0328]

Table 5-1. Composition of aqueous emulsion obtained in step 1

[0329]

[Table 61]

[0330]

[Table 62]

[0331]

[Table 63]

[0332]

[Table 64]

[0333]

[Table 65]

[0334]

[Table 66]

[0335]

[Table 67]

[0336]

[Table 68]

[0337]

[Table 69]

[0338]

[Table 70]

[0339]

[Table 71]

[0340]

[Table 72]

[0341]

[Table 73] Table 5-14. Composition and evaluation result of re-emulsifiable polymer powder (6)

[0342]

[Table 74] Table 5-15. Composition and evaluation result of re-emulsifiable polymer powder (6) (continued) 6. Example of Aggregating Aqueous Emulsion / Protective Colloid Mixture with Polyvalent Metal Salt System Using Ethylenically Unsaturated Monomer Having Amide Group [Example 6-1] Aqueous emulsion production process A-1) was prepared. 785 g of pure water and 3 g of sodium dodecylbenzenesulfonate (abbreviated as DBS) are charged into a reaction vessel equipped with a stirrer, a reflux condenser and a thermometer, and 5 g of potassium persulfate is added at 80 ° C. with stirring in a nitrogen atmosphere. Thus, an aqueous solution was prepared. On the other hand, an emulsion having the following composition was prepared and added dropwise to the above aqueous solution at 80 ° C. in 3 hours.
It was kept at the same temperature for 3 hours. Pure water 400 g DBS 1 g Styrene 400 g n-butyl acrylate 500 g 2-hydroxyethyl methacrylate 50 g methacrylic acid 30 g acrylamide 20 g n-dodecyl mercaptan 1 g To the obtained aqueous emulsion, ammonia water and pure water were added. The resin content was adjusted to 45%. This aqueous emulsion is designated as (A-1). Protective colloid production process A protective colloid (a1) was prepared by the following operation.
A reaction vessel equipped with a stirrer, a reflux condenser and a thermometer was charged with 850 g of pure water and 100.0 g of methacrylamide, and heated to 75 ° C. in a nitrogen atmosphere under stirring.
This temperature was maintained. After the methacrylamide was completely dissolved, 30.0 g of a 5% aqueous solution of ammonium persulfate was added, and the mixture was kept at 75 ° C. for 7 hours. Aqueous ammonia and pure water were added thereto to obtain a protective colloid (B-1) having a resin content of 10% and a pH of 9. Mixing step Aqueous emulsion (A-1) and protective colloid (B-1)
Were mixed and stirred so that the solid ratio became 50/50. Aggregate Production Step The mixture of the aqueous emulsion (A-1) and the protective colloid (B-1) produced in the mixing step is diluted with pure water so as to have a resin content of 10%, and further diluted with 1000 g of the diluted product at room temperature. When 50 g of 45% aluminum sulfate was added, aggregates were formed. After the aggregate was separated into solid and liquid by filtration, it was dried at 80 ° C. until the residual water content became 2% or less. The re-emulsifiable polymer powder was obtained by pulverizing the dried aggregate.

Examples 6-1 to 8-8 Aqueous Emulsion Production Step i) Preparation of Aqueous Emulsion (A-1) An aqueous emulsion (A-1) was prepared in the same manner as in Example 6-1.

Ii) Preparation of Aqueous Emulsion (A-2) In the same manner as in the preparation method of aqueous emulsion (A-1) shown in Example 6-1, the monomer composition shown in Table 6-1 was used and the pH was adjusted.
= 9, resin content = 45% aqueous emulsion (A-2) was obtained. iii) Preparation of aqueous emulsion (A-3) In an autoclave equipped with a stirrer, 790 g of pure water, 2 g of sodium lauryl sulfate, and 1 g of sodium bicarbonate were charged, and potassium persulfate 10 was stirred at 70 ° C in a nitrogen atmosphere.
g was added. On the other hand, an emulsion having the following composition was prepared and dropped into the above aqueous solution over 6 hours to ripen. Pure water 400 g Sodium lauryl sulfate 3 g Styrene 280 g Butadiene 700 g Acrylic acid 20 g T-dodecylmercaptan 3 g To the obtained SBR latex, aqueous ammonia (pH = 9, resin content = 45%) was added by adding ammonia water and pure water. -3) was prepared. Protective colloid production process Protective colloid (B-2) was prepared in the same manner as in Example 6-1.
~ (B-8) was prepared. Mixing Step The aqueous emulsion (A-1) is mixed with the protective colloid (B-
Each of 2) to (B-8) was 50/5 in terms of solids ratio.
It was mixed and stirred so as to be 0. Aggregate Production Step A re-emulsifiable polymer powder was obtained in the same manner as in Example 6-1.

[Example 6-9] Aqueous emulsion (A-
1) and protective colloid (B-1) in a solid ratio of 70/3
After mixing and stirring to obtain 0, a re-emulsifiable polymer powder was obtained in the same manner as in Example 6-1.

Example 6-10 Example 6-6 was repeated except that 225 g of a 10% ferric sulfate aqueous solution was added instead of the 45% aluminum sulfate aqueous solution used for obtaining the aggregate in Example 6-4. In the same manner as in Example 4, a re-emulsifiable polymer powder was obtained.

Example 6-11 The same operation as in Example 6-4 was carried out except that the temperature of the mixture of the aqueous emulsion and the protective colloid was changed to 70 ° C., and then 45% of aluminum sulfate was added. Thus, a re-emulsifiable polymer powder was obtained. Agglomerates were larger than in Example 6-4, and the solid-liquid separation time by filtration was reduced to 1/10, and workability was improved.

Example 6-12 Example 6-4 was repeated, except that 225 g of a 10% aqueous solution of calcium chloride was added instead of the 45% aqueous solution of aluminum sulfate used to obtain the aggregates in Example 6-4. A re-emulsifiable polymer powder was obtained in the same manner as described above.

[Example 6-13] In Example 6-12, before adding the polyvalent metal salt, the pH of the mixture of the aqueous emulsion and the protective colloid was adjusted to 4 with sulfuric acid. A re-emulsifiable polymer powder was obtained in the same manner as in Example 6-12, except that 225 g of a 10% aqueous calcium chloride solution was added. Agglomerates were larger than in Example 6-12, so that the solid-liquid separation time by filtration was reduced to 1/3, and workability was improved.

[Example 6-14] A re-emulsifiable polymer powder was obtained in the same manner as in Example 6-4, except that the amount of 45% aluminum sulfate added in Example 6-4 was changed to 6.5 g. Was.

Example 6-15 A re-emulsifiable polymer was prepared in the same manner as in Example 6-4, except that washing with sufficient pure water was repeated when the aggregates were separated by filtration in Example 6-4. A powder was obtained. This and the re-emulsifiable polymer powder of Example 6-4 were each added to a 1% aqueous sodium hydroxide solution to obtain a re-emulsified solution, and these were applied to a glass plate and dried at room temperature for 3 days. When the film was immersed in day water and the water absorption of the film was measured, the water absorption of Example 6-15 was lower and the water resistance was better.

Example 6-16 Aqueous emulsion (A
-2) The protective colloid (B-1) was added at a solid ratio of 50 /
After mixing and stirring to 50, a re-emulsifiable polymer powder was obtained by the same operation as in Example 6-1.

[Example 6-17] Aqueous emulsion (A
-2) The protective colloid (B-4) was added at a solid ratio of 50 /
After mixing and stirring to 50, a re-emulsifiable polymer powder was obtained by the same operation as in Example 6-1.

Example 6-18 Aqueous emulsion (A
-3), the protective colloid (B-1) was added at a solid ratio of 50 /
After mixing and stirring to 50, a re-emulsifiable polymer powder was obtained by the same operation as in Example 6-1.

[Comparative Examples 6-1 to 3] Each of the aqueous emulsions (A-1) to (A-3) was diluted with pure water to a resin content of 10%, and then diluted with 1000 g of the diluted product at room temperature by 45% aluminum sulfate. When 50 g of the aqueous solution was added, aggregates were formed. After solid-liquid separation of this aggregate by filtration,
It was dried at 80 ° C. until the residual water content became 2% or less. However, all the dried aggregates were soft and could not be ground. The re-emulsifiability was evaluated without grinding.

[Comparative Example 6-4] Each of the mixtures of the aqueous emulsions and the protective colloids prepared in Examples 6-1 to 9 and 6-16 to 18 was treated with an inlet air temperature of 120.
By spray-drying at 60 ° C. and an outlet air temperature of 60 ° C., a re-emulsifiable polymer powder was obtained. All of the mixtures produced a large amount of deposits on the inner wall of the drying tower, the yield was 30% or less, and the re-emulsifiability was extremely poor.

Comparative Example 6-5 A re-emulsifiable polymer powder was obtained in the same manner as in Example 6-4, except that the amount of 45% aluminum sulfate added in Example 6-4 was changed to 0.01 g. However, no aggregate was formed.

[Evaluation Example 6-1] The yield was calculated and graded in the same manner as in Evaluation Example 1-1.

[Evaluation Example 6-2] A re-emulsion was prepared and evaluated in the same manner as in Evaluation Example 1-2. However, Comparative Example 6-1
Since the re-emulsifiable polymers of Nos. 3 to 3 were all too soft to be pulverized, they were not pulverized, and the re-emulsifiable liquid was prepared in the same manner as described above except for the above. In addition, since the re-emulsifiable polymer obtained by spray drying in Comparative Example 6-4 was already obtained in the form of powder, these were sieved through a 16-mesh (1 mm) sieve to obtain particles of 1 mm or less [Evaluation Example 6-3]. The emulsifiable polymer powder was blended with cement in the same manner as in Evaluation Examples 1-3, and tested. However, Comparative Example 6
-4, the re-emulsifiable polymer obtained by spray-drying is already obtained in powder form.
The powder classified so that the residue on the sieve (μm) was 5% or less was tested in the same manner as described above.

Table 6-1 shows the composition of the aqueous emulsion used in the above Examples and Comparative Examples, Table 6-2 shows the composition of the protective colloid, and Table 6 shows the composition and evaluation results of the re-emulsifiable polymer powder. -3 to Table 6-14.

[0361]

Table 6-1. Composition of aqueous emulsion

[0362]

[Table 76]

[0363]

[Table 77]

[0364]

[Table 78]

[0365]

[Table 79]

[0366]

[Table 80]

[0367]

[Table 81]

[0368]

[Table 82]

[0369]

[Table 83]

[0370]

[Table 84]

[0371]

[Table 85]

[0372]

[Table 86]

[0373]

Table 6-13. Composition and evaluation result of re-emulsifiable polymer powder (6)

[0374]

[Table 88] Table 6-14. Composition and evaluation result of re-emulsifiable polymer powder (6) (continued) 7. Example of Aggregating Aqueous Emulsion Produced by Protective Colloid Polymerization Method with Metal Salt (System Using Ethylenically Unsaturated Monomer Having Hydroxyl Group) [Example 7-1] Step 1 (Process of Producing Aqueous Emulsion) <Protective Colloid> Preparation of (a1)> A reaction vessel equipped with a stirrer, a reflux condenser and a thermometer was charged with 700.0 g of a 1.5% aqueous sodium hydroxide solution, 90.0 g of 2-hydroxyethyl methacrylate, and 10.0 g of methacrylic acid, and stirred. The temperature was raised to 40 ° C. in a nitrogen atmosphere.
When this temperature was maintained, potassium persulfate was used.
0 g was added, and after this was dissolved, 15% was used as a reducing agent.
25.6 g of aqueous sodium bisulfite solution was further added,
An aqueous solution was prepared by holding at 40 ° C. for 6 hours. 1.5% aqueous sodium hydroxide 700.0 g 2-hydroxyethyl methacrylate 90.0 g methacrylic acid 10.0 g potassium persulfate 10.0 g 15% aqueous sodium bisulfite 25.6 g Resin content = 15%, pH = 9 Protection A colloid (B-1) was obtained. <Polymerization of protective colloid> In a reaction vessel equipped with a stirrer, a reflux condenser and a thermometer, a protective colloid (B-1) 66 was added.
6.7 g was charged, and the temperature was 80 ° C. in a nitrogen atmosphere with stirring.
Then, 0.5 g of potassium persulfate was added. On the other hand, an emulsion having the following composition was prepared, which was added dropwise to the above aqueous solution at 80 ° C. for 3 hours, and further kept at the same temperature for 3 hours. Pure water 40.0 g Sodium dodecylbenzenesulfonate 0.1 g Styrene 50.0 g n-butyl acrylate 40.0 g 2-hydroxyethyl methacrylate 5.0 g Methacrylic acid 3.0 g Acrylamide 2.0 g 0.1 g of n-dodecyl mercaptan Aqueous emulsion (C-1) having a resin content of 10% and a pH of 9 was prepared by adding aqueous ammonia and pure water to the obtained polymer. The particle size of this aqueous emulsion (C-1) was 0.18 μm. Step 2 (Aggregate Production Step) When 50 g of a 45% aqueous solution of aluminum sulfate was added to 1000 g of (C-1) at room temperature, an aggregate was formed. This solid was separated into solid and liquid by filtration, and then dried at 80 ° C. until the residual water content became 2% or less (the residual water content was JIS).
It was measured by the method of measuring loss on heating of K5407.5. Hereinafter, all the residual moisture amounts are values measured by this method). The dried agglomerates were crushed and crushed to 50 mesh (300
μm) to obtain a powder of 300 μm or less. This bulk density was 670 g / liter.

[Examples 7-2 to 7] Step 1 (aqueous emulsion production step) <Preparation of protective colloid (a1)> Protective colloid having the composition shown in Table 7-1 was prepared in the same manner as in Example 7-1. (B-
2) to (B-7) were prepared. <Protective Colloid Polymerization> By the same operation as in Example 7-1, the protective colloid (B-1) of Example 7-1 was replaced with protective colloids (B-2) to (B-7). And aqueous emulsions (C-2) to (C-7)
I got Step 2 (Aggregate Production Step) By the same operation as in Example 7-1, instead of the aqueous emulsion (C-1) of Example 7-1, the aqueous emulsions (C-2) to (C-7) were obtained. Substituting for each gave a re-emulsifiable polymer powder.

[Example 7-8] In a reaction vessel equipped with a stirrer, a reflux condenser and a thermometer, a protective colloid (B-
2) 400.0 g and 210 g of pure water were charged, and 0.7 g of potassium persulfate was added at a temperature of 80 ° C. with stirring in a nitrogen atmosphere. On the other hand, an emulsion having the following composition was prepared, dropped into the above aqueous solution in 3 hours, and aged for 3 hours. Pure water 56.0 g Sodium dodecylbenzenesulfonate 0.14 g Styrene 70.0 g n-butyl acrylate 56.0 g 2-hydroxyethyl methacrylate 7.0 g Methacrylic acid 4.2 g Acrylamide 2.8 g n- Dodecyl mercaptan 0.14 g Aqueous emulsion (C-8) having a resin content of 10% and a pH of 9 was prepared by adding aqueous ammonia and pure water to the obtained polymer. (C-8) When 50 g of a 45% aqueous solution of aluminum sulfate was added to 1000 g at room temperature, an aggregate was formed. This solid is separated into solid and liquid by filtration,
And dried until the residual water content became 2% or less. The re-emulsifiable polymer powder was obtained by pulverizing the dried aggregate.

Example 7-9 Example 7-9 was repeated, except that 225 g of a 10% ferric sulfate aqueous solution was added instead of the 45% aluminum sulfate aqueous solution used for obtaining the aggregates in Example 7-2. In the same manner as in Example 2, a re-emulsifiable polymer powder was obtained.

Example 7-10 Re-emulsifiability was carried out in the same manner as in Example 7-2, except that the temperature of the aqueous emulsion was changed to 70 ° C. and then 45% aluminum sulfate was added. A polymer powder was obtained. Agglomerates were larger than in Example 7-2, and the solid-liquid separation time by filtration was reduced to 1/10, and workability was improved.

Example 7-11 Example 7-2 was repeated except that 225 g of a 10% calcium chloride aqueous solution was added instead of the 45% aluminum sulfate aqueous solution used for obtaining the aggregate in Example 7-2. A re-emulsifiable polymer powder was obtained in the same manner as described above.

Example 7-12 In Example 7-11, the pH of the aqueous emulsion was adjusted with sulfuric acid before adding the polyvalent metal salt.
Was adjusted to 4 and then 225 g of a 10% calcium chloride aqueous solution was added as a polyvalent metal salt.
By the same operation as in Example 11, a re-emulsifiable polymer powder was obtained. Agglomerates were larger than in Examples 7-11, and the solid-liquid separation time by filtration was reduced to 1/3, and workability was improved.

Example 7-13 A re-emulsifiable polymer powder was obtained in the same manner as in Example 7-2, except that the amount of 45% aluminum sulfate added in Example 7-2 was changed to 6.5 g. Was.

[Example 7-14] A re-emulsifiable polymer was prepared in the same manner as in Example 7-2, except that in the case of separating the aggregates by filtration in Example 7-2, washing was repeated with sufficient pure water. A powder was obtained. This and the re-emulsifiable polymer powder of Example 7-2 were each added to a 1% aqueous sodium hydroxide solution to obtain a re-emulsified solution. These were applied to a glass plate and dried at room temperature for 3 days. When the film was immersed in water, the water absorption of the film was measured.
-14 was lower in water absorption and more excellent in water resistance.

[Example 7-15] The emulsion used in Example 7-1 was changed as follows, and an aqueous emulsion (C-9) was obtained in the same manner as in Example 7-1. A re-emulsifiable polymer powder was obtained. Pure water 40.0 g Sodium dodecylbenzenesulfonate 0.1 g Methyl methacrylate 30.0 g Butyl acrylate 60.0 g 2-Hydroxyethyl methacrylate 5.0 g Methacrylic acid 3.0 g Acrylamide 2.0 g n-dodecyl mercaptan 0.1 g [ Example 7-16] An aqueous emulsion (C-10) was obtained in the same manner as in Example 7-15, except that the protective colloid (B-1) was changed to the protective colloid (B-2). A polymer powder was obtained.

Example 7-17 In an autoclave equipped with a stirrer, 666.7 g of the protective colloid (B-2) was charged, and 1.0 g of potassium persulfate was added at 70 ° C. in a nitrogen atmosphere with stirring. On the other hand, an emulsion having the following composition was prepared and dropped into the above aqueous solution over 6 hours to ripen. Pure water 40.0 g Sodium lauryl sulfate 0.3 g Styrene 28.0 g Butadiene 70.0 g Acrylic acid 2.0 g T-dodecyl mercaptan 0.3 g To the obtained polymer, ammonia water and pure water were added, and a resin component was obtained. 10%, pH = 9 aqueous emulsion (C-11)
Was prepared. (C-11) When 50 g of a 45% aqueous solution of aluminum sulfate was added to 1000 g at room temperature, an aggregate was formed. This solid is separated into solid and liquid by filtration.
It was dried at 0 ° C. until the residual water content became 2% or less. The re-emulsifiable polymer powder was obtained by pulverizing the dried aggregate.

[Comparative Example 7-1] The protective colloid (B-2) used in Example 7-2 was replaced with 650.0 g of pure water, and otherwise the same operation as in Example 7-2 was carried out. An aqueous emulsion polymer (C-12) containing no (B-2) was obtained, and an attempt was made to obtain a re-emulsifiable polymer powder therefrom. However, since the aggregate after drying was soft, pulverization was impossible. The re-emulsifiability was evaluated without grinding.

[Comparative Example 7-2] The protective colloid (B-2) used in Example 7-13 was replaced with 650.0 g of pure water, and otherwise the same operation as in Example 7-2 was carried out. An aqueous emulsion polymer (C-13) containing no (B-2) was obtained, and an attempt was made to obtain a re-emulsifiable polymer powder therefrom. However, since the aggregate after drying was soft, pulverization was impossible. The re-emulsifiability was evaluated without grinding.

[Comparative Example 7-3] The protective colloid (B-2) used in Example 7-14 was replaced with 650.0 g of pure water, and otherwise the same operation as in Example 7-16 was carried out. An aqueous emulsion polymer (C-14) containing no (B-2) was obtained, and an attempt was made to obtain a re-emulsifiable polymer powder therefrom. However, since the aggregate after drying was soft, pulverization was impossible. The re-emulsifiability was evaluated without grinding.

[Comparative Example 7-4] Aqueous emulsion (C-
Regarding 1) to (C-11), re-emulsifiable polymer powders were obtained by spray drying at 120 ° C inlet air temperature and 60 ° C outlet air temperature instead of coagulation with polyvalent metal salts. All of the mixtures produced a large amount of deposits on the inner wall of the drying tower, the yield was 30% or less, and the re-emulsifiability was extremely poor.

[Comparative Example 7-5] A re-emulsifiable polymer powder was obtained in the same manner as in Example 7-2 except that the amount of 45% aluminum sulfate added in Example 7-2 was changed to 0.01 g. However, no aggregate was formed.

[Evaluation Example 7-1] Measurement was performed in the same manner as in Evaluation Example 1-1.

[Evaluation Example 7-2] A re-emulsifiable polymer powder was prepared and evaluated in the same manner as in Evaluation Example 1-2.
However, since the re-emulsifiable polymers of Comparative Examples 7-1 to 3 were all soft and could not be pulverized, the re-emulsifiable liquid was prepared in the same manner as described above except that the re-emulsifiable polymer was not pulverized. In addition, since the re-emulsifiable polymer obtained by spray drying in Comparative Example 7-4 was already obtained in the form of powder, these were reconstituted in 16 mesh (1 mesh).
mm), a re-emulsion liquid was prepared in the same manner as described above for powder having a particle size of 1 mm or less.

[Evaluation Example 7-3] The re-emulsifiable polymer powder was mixed with cement in the same manner as in Evaluation Examples 1-3, and tested. However, since the re-emulsifiable polymer obtained by spray drying in Comparative Example 7-4 was already obtained in powder form, these were classified so that the residue on an 80 mesh (200 μm) sieve was 5% or less. The powder thus obtained was tested in the same manner as described above.

[Evaluation Example 7-4] Example 7-4 of this specification
The following blending was performed on the polymer powder obtained in
° C, 80% R.C. H. (Relative humidity) and evaluated for odor and hardening. <Blending> Portland cement 1000 g Re-emulsifiable polymer powder 100 g Water 500 g <Evaluation> Odor: After one day, the presence or absence of ammonia odor was evaluated. Curing: The termination after one-day curing was measured by a setting test according to JIS R5201. <Results> Odor: None. Curing: finished.

[Evaluation Example 7-5] Evaluation of re-emulsifiability assuming emulsification in cement The re-emulsifiability was evaluated by the following method. 1. 100 g of cement and 500 g of water were mixed for 1 minute, and a filter paper (qualitative filter paper No. manufactured by Advantech Toyo Co., Ltd.) was used.
Filtration was performed in 1) to obtain a filtrate. 2. 94 g of the above filtrate was collected in a 100 ml Erlenmeyer flask, and 3 g of calcium hydroxide (powder) was mixed therein. 3. This was further ground and sieved, and 3 g of a resin powder having a size of 300 μm or less was added, and the mixture was shaken well for 3 minutes. Immediately after 4.3 minutes, the solution was filtered through a filter paper (qualitative filter paper No. 1 manufactured by Advantech Toyo Co., Ltd.) to obtain a filtrate, and the nonvolatile content of the filtrate was measured according to JIS K5407.4. wt%). 5.2. 3. Mixture prepared in 4. Filtration was performed in the same manner as described above, and the non-volatile content was measured to be N2 (%). 6. The re-emulsification rate was calculated by the following equation. Re-emulsification rate assuming emulsification in cement = ｛(N1-N
2) / 3 @ X100 The re-emulsification ratio of the polymer powder obtained in Example 7-2 was 4
0% or more, which was good. On the other hand, when the polymer of Example 7-2 was dried by spray drying, the re-emulsification rate was not good at 15% or less.

The compositions of the protective colloids used in the above Examples and Comparative Examples are shown in Table 7-1, the compositions of the aqueous emulsions are shown in Tables 7-2 and 7-3, and the compositions of the re-emulsifiable polymer powder and The evaluation results are shown in Tables 7-4 and 7-5.

[0396]

[Table 89]

[0397]

[Table 90]

[0398]

[Table 91]

[0399]

[Table 92]

[0400]

[Table 93]

[0401]

[Table 94]

[0402]

[Table 95]

[0403]

[Table 96]

[0404]

[Table 97]

[0405]

[Table 98]

[0406]

[Table 99]

[0407]

[Table 100]

[0408]

[Table 101]

[0409]

[Table 102]

[0410]

[Table 103] Table 7-6. Composition and evaluation result of re-emulsifiable polymer powder (3) (continued)

[0411]

[Table 104] Table 7-6. Composition and evaluation result of re-emulsifiable polymer powder (3) (continued) 8. Example of Aggregating Aqueous Emulsion Produced by Core / Shell Polymerization Method with Metal Salt (System Using Ethylenically Unsaturated Monomer Having Hydroxyl Group) [Example 8-1] Aqueous Solution of Step 1 (Core Particle Polymerization Step) Preparation of emulsion An aqueous emulsion (A-1) was prepared by the following operation. 785 g of pure water and 3 g of sodium dodecylbenzenesulfonate (abbreviated as DBS) are charged into a reaction vessel equipped with a stirrer, a reflux condenser and a thermometer, and 5 g of potassium persulfate is added at 80 ° C. with stirring in a nitrogen atmosphere. Thus, an aqueous solution was prepared. On the other hand, an emulsion having the following composition was prepared, added dropwise to the above aqueous solution at 80 ° C. for 3 hours, and kept at the same temperature for 3 hours. Pure water 400 g DBS 1 g Styrene 500 g n-butyl acrylate 400 g 2-hydroxyethyl methacrylate 50 g methacrylic acid 30 g acrylamide 20 g n-dodecyl mercaptan 1 g To the obtained aqueous emulsion, ammonia water and pure water were added, and the pH = 9, Min = 45%. This aqueous emulsion is designated as (A-1). The particle size of the aqueous emulsion (A-1) was 0.11 μm.

Step 2 (Shell Polymerization Step) In a reaction vessel equipped with a stirrer, a reflux condenser and a thermometer, 222.2 g of the aqueous emulsion (A-1), 725.0 g of pure water, and 2-hydroxyethyl methacrylate 9
0.0 g and methacrylic acid 10.0 g were charged and stirred.
Adjust to pH 9.5 with sodium hydroxide. Under stirring,
The temperature was raised to 40 ° C. in a nitrogen atmosphere, and this temperature was maintained. After completion of the heating, 10.0 g of potassium persulfate was added,
After dissolution, an additional 10% aqueous sodium bisulfite solution
4 g was added and kept at 40 ° C. for 6 hours. Aqueous emulsion polymer (A-1) 222.2 g Pure water 725.0 g 2-hydroxyethyl methacrylate 90.0 g Methacrylic acid 10.0 g Sodium hydroxide 6.6 g Potassium persulfate 10.0 g 10% sodium bisulfite 38.4 g As a result, an aqueous emulsion having a resin content of 20% and a pH of 8 was obtained. This aqueous emulsion is designated as (C-1). The particle size of this aqueous emulsion (C-1) is 0.1
It was 3 μm.

Step 3 (Aggregate Production Step) The aqueous emulsion (C-1) was diluted to a purity of 10% with a resin content, and 50 g of a 45% aqueous solution of aluminum sulfate was added to 1000 g of the diluted product at room temperature to form aggregates. Generated. After this aggregate is separated into solid and liquid by filtration,
Drying was carried out at a temperature of 2 ° C. until the residual water content became 2% or less. The re-emulsifiable polymer powder was obtained by pulverizing the dried aggregate.
50μm (300μm) sieve 300μ
m or less was obtained. This bulk density is 640
g / liter.

[Examples 8-2 to 11 ] Preparation of aqueous emulsion of step 1 (core particle polymerization step) i) Preparation of aqueous emulsion (A-1) Aqueous emulsion was prepared in the same manner as in Example 5-1. (A-1) was prepared.

Ii) Preparation of Aqueous Emulsion (A-2) The monomer composition shown in Table 8-1 was used to prepare the aqueous emulsion (A-1) in the same manner as in the preparation method of the aqueous emulsion (A-1) shown in Example 8-1. 9. An aqueous emulsion (A-2) having a resin content of 45% was obtained. iii) Preparation of aqueous emulsion (A-3) In an autoclave equipped with a stirrer, 790 g of pure water, 2 g of sodium lauryl sulfate, and 1 g of sodium bicarbonate were charged, and 10 g of potassium persulfate at 70 ° C under stirring in a nitrogen atmosphere.
Was added to prepare an aqueous solution. On the other hand, an emulsion having the following composition was prepared, added dropwise to the above aqueous solution at 70 ° C. over 6 hours, and kept at the same temperature for 6 hours. Pure water 400 g Sodium lauryl sulfate 3 g Styrene 280 g Butadiene 700 g Acrylic acid 20 g T-dodecylmercaptan 3 g To the obtained SBR latex, aqueous ammonia (pH = 9, resin content = 45%) was added by adding ammonia water and pure water. -3) was prepared. Step 2 (Shell polymerization step) By the same operation as in Example 8-1, Table 8-2 and Table 8-3
Aqueous emulsions (C-2) to (C-1)
1) was prepared. Step 3 (Aggregate Production Step) By the same operation as in Example 8-1, a re-emulsifiable polymer powder was obtained from each of the aqueous emulsions (C-2) to (C-12).

Example 8-12 Example 8-2 was repeated except that 225 g of a 10% ferric sulfate aqueous solution was added instead of the 45% aluminum sulfate aqueous solution used for obtaining the aggregate in Example 8-2. In the same manner as in Example 2, a re-emulsifiable polymer powder was obtained.

Example 8-13 The re-emulsifiable polymer was prepared in the same manner as in Example 8-2, except that the temperature of the aqueous emulsion was changed to 70 ° C. and then 45% aluminum sulfate was added. A combined powder was obtained. Agglomerates were larger than in Example 8-2, and the solid-liquid separation time by filtration was reduced to 1/10, and workability was improved.

Example 8-14 Example 8-2 was repeated, except that 225 g of a 10% calcium chloride aqueous solution was added instead of the 45% aluminum sulfate aqueous solution used for obtaining the aggregate in Example 8-2. A re-emulsifiable polymer powder was obtained in the same manner as described above.

[Examples 8-15] In Examples 8-14, the pH of the aqueous emulsion was adjusted with sulfuric acid before adding the polyvalent metal salt.
Was adjusted to 4 and then 225 g of a 10% aqueous calcium chloride solution was added as a polyvalent metal salt.
By the same operation as in 14, a re-emulsifiable polymer powder was obtained. Agglomerates were larger than in Examples 8-17, and the solid-liquid separation time by filtration was reduced to 1/3, and workability was improved.

[Example 8-16] A re-emulsifiable polymer powder was obtained in the same manner as in Example 8-2 except that the amount of 45% aluminum sulfate added in Example 8-2 was changed to 6.5 g. Was.

[Example 8-17] The re-emulsifiable polymer was prepared in the same manner as in Example 8-2, except that washing with sufficient pure water was repeated when the aggregates were separated by filtration in Example 8-2. A powder was obtained. This and the re-emulsifiable polymer powder of Example 8-2 were each added to a 1% aqueous sodium hydroxide solution to obtain a re-emulsified liquid, and these were applied to a glass plate and dried at room temperature for 3 days to obtain a film. When immersed in sun water and the water absorption of the membrane was measured,
In Examples 8-17, the water absorption was lower and the water resistance was better.

[Comparative Examples 8-1 to 3] Each of the aqueous emulsions (A-1) to (A-3) was diluted with pure water to a resin content of 10%, and then diluted with 1000 g of 45% aluminum sulfate at room temperature. When 50 g of the aqueous solution was added, aggregates were formed. After the aggregate was separated into solid and liquid by filtration, it was dried at 80 ° C. until the residual water content became 2% or less. However, all the dried aggregates were soft and could not be ground. The re-emulsifiability was evaluated without grinding. [Comparative Example 8-4] Aqueous emulsions (C-1) to (C-
11) Each was spray-dried at an inlet air temperature of 120 ° C and an outlet air temperature of 60 ° C to obtain a re-emulsifiable polymer powder. Each of the aqueous emulsions produced a large amount of deposits on the inner wall of the drying tower, the yield was 30% or less, and the re-emulsifiability was extremely poor.

Comparative Example 8-5 A re-emulsifiable polymer powder was obtained in the same manner as in Example 8-2 except that the amount of 45% aluminum sulfate added in Example 8-2 was changed to 0.01 g. However, no aggregate was formed.

[Evaluation Example 8-1] Measurement and evaluation were performed in the same manner as in Evaluation Example 1-1.

[Evaluation Example 8-2] A re-emulsifiable polymer powder was prepared and evaluated in the same manner as in Evaluation Example 1-2.
However, all of the re-emulsifiable polymers of Comparative Examples 8-1 to 3 were not pulverized because they were all soft and could not be pulverized. In addition, since the re-emulsifiable polymer obtained by spray drying in Comparative Example 8-4 was already obtained in the form of powder, these were reconstituted in 16 mesh (1 mesh).
mm), a re-emulsion liquid was prepared in the same manner as described above for powder having a particle size of 1 mm or less.

[Evaluation Example 8-3] The re-emulsifiable polymer powder was mixed with cement in the same manner as in Evaluation Example 1-3, and tested. However, since the re-emulsifiable polymer obtained by spray drying in Comparative Example 8-4 was already obtained in the form of powder, these were classified so that the residue on an 80 mesh (200 μm) sieve was 5% or less. The powder thus obtained was tested in the same manner as described above.

[Evaluation Example 8-4] Example 8-4 of this specification
The odor and curing were evaluated for the polymer powder obtained in the same manner as in Evaluation Example 7-4. <Results> Odor: None. Curing: finished.

[Evaluation Example 8-5] Evaluation of re-emulsifiability assuming emulsification in cement The re-emulsifiability was evaluated by the method of Evaluation Example 7-5.

The re-emulsification rate of the polymer powder obtained in Example 8-2 was 40% or more, which was good. On the other hand, when the polymer of Example 8-2 was dried by spray drying, the re-emulsification rate was not good at 15% or less.

Step 1 used in the above Examples and Comparative Examples
Table 8-1 shows the composition of the aqueous emulsion produced in Table 8, and Table 8-2 shows the composition of the aqueous emulsion produced in Step 2.
Table 8-3 shows the composition and evaluation results of the re-emulsifiable polymer powders in Tables 8-4 to 8-15.

[0431]

[Table 105] Table 8-1. Composition of aqueous emulsion obtained in step 1

[0432]

[Table 106]

[0433]

[Table 107]

[0434]

Table 108-3. Composition of aqueous emulsion obtained in step 2 (continued)

[0435]

[Table 109]

[0436]

[Table 110]

[0437]

[Table 111]

[0438]

[Table 112]

[0439]

[Table 113]

[0440]

[Table 114]

[0441]

[Table 115]

[0442]

[Table 116]

[0443]

[Table 117]

[0444]

[Table 118]

[0445]

[Table 119] Table 8-14. Composition and evaluation result of re-emulsifiable polymer powder (6)

[0446]

[Table 120] Table 8-15. Composition and evaluation result of re-emulsifiable polymer powder (6) (continued) 9. Example of Aggregating Aqueous Emulsion / Protective Colloid Mixture with Metal Salt (System Using Ethylenically Unsaturated Monomer Having Hydroxyl Group) [Example 9-1] Aqueous Emulsion Production Step An aqueous emulsion (A- 1) was prepared. 785 g of pure water and 3 g of sodium dodecylbenzenesulfonate (abbreviated as DBS) are charged into a reaction vessel equipped with a stirrer, a reflux condenser and a thermometer, and 5 g of potassium persulfate is added at 80 ° C. with stirring in a nitrogen atmosphere. An aqueous solution was prepared. On the other hand, an emulsion having the following composition was prepared and added dropwise to the above aqueous solution at 80 ° C. over 3 hours, and kept at the same temperature for 3 hours. Pure water 400 g DBS 1 g Styrene 500 g n-butyl acrylate 400 g 2-hydroxyethyl methacrylate 50 g methacrylic acid 30 g acrylamide 20 g n-dodecyl mercaptan 1 g To the obtained aqueous emulsion, ammonia water and pure water were added, and the pH = 9, Min = 45%. This aqueous emulsion is designated as (A-1). The particle size of the aqueous emulsion (A-1) was 0.11 μm.

Protective Colloid Production Step A protective colloid (a1) was prepared by the following operation.
In a reaction vessel equipped with a stirrer, a reflux condenser and a thermometer, 700.0 g of a 1.5% aqueous sodium hydroxide solution was added.
90.0 g of 2-hydroxyethyl methacrylate and 10.0 g of methacrylic acid were charged, and under a nitrogen atmosphere under stirring.
The temperature was raised to 40 ° C. When this temperature was maintained, 10.0 g of potassium persulfate was added and, after this was dissolved, 15% sodium bisulfite as a reducing agent.
An additional 6 g was added and kept at 40 ° C. for 6 hours. 1.5% aqueous sodium hydroxide 700.0 g 2-hydroxyethyl methacrylate 90.0 g methacrylic acid 10.0 g potassium persulfate 10.0 g 15% sodium bisulfite 25.6 g A protective colloid (B-1) having a pH of 5 and 10% was obtained.

Mixing Step Aqueous emulsion (A-1) and protective colloid (B-1)
Were mixed and stirred so that the solid ratio became 50/50.

Aggregate Production Step The mixture of the aqueous emulsion (A-1) and the protective colloid (B-1) produced in the mixing step is diluted with pure water so as to have a resin content of 10%. When 50 g of 45% aluminum sulfate was added to 1000 g at room temperature, an aggregate was formed. After the aggregate was separated into solid and liquid by filtration, it was dried at 80 ° C. until the residual water content became 2% or less. The re-emulsifiable polymer powder was obtained by pulverizing the dried aggregate. This was sieved through a 50 mesh (300 μm) sieve to obtain a powder having a size of 300 μm or less. This bulk density was 605 g / liter.

[Examples 9-2 to 7] Production process of aqueous emulsion i) Preparation of aqueous emulsion (A-1) An aqueous emulsion (A-1) was prepared in the same manner as in Example 9-1.

Ii) Preparation of aqueous emulsion (A-2) In the same manner as in the preparation method of aqueous emulsion (A-1) shown in Example 9-1, the monomer composition shown in Table 6-1 was used,
= 9, resin content = 45% aqueous emulsion (A-2) was obtained. iii) Preparation of aqueous emulsion (A-3) In an autoclave equipped with a stirrer, 790 g of pure water, 2 g of sodium lauryl sulfate, and 1 g of sodium bicarbonate were charged, and potassium persulfate 10 was stirred at 70 ° C in a nitrogen atmosphere.
g was added. On the other hand, an emulsion having the following composition was prepared, dropped into the above aqueous solution over 6 hours, and kept at the same temperature for 6 hours. Pure water 400 g Sodium lauryl sulfate 3 g Styrene 280 g Butadiene 700 g Acrylic acid 20 g T-dodecylmercaptan 3 g To the obtained SBR latex, aqueous ammonia (pH = 9, resin content = 45%) was added by adding ammonia water and pure water. -3) was prepared. Protective colloid production process Protective colloid (B-2) was prepared in the same manner as in Example 9-1.
~ (B-7) was prepared. Mixing Step The aqueous emulsion (A-1) is mixed with the protective colloid (B-
Each of 2) to (B-7) was 50/5 in solid ratio.
It was mixed and stirred so as to be 0. Aggregate Production Step A re-emulsifiable polymer powder was obtained in the same manner as in Example 9-1.

[Example 9-8] Aqueous emulsion (A-
1) and protective colloid (B-2) in a solid ratio of 70/3
After mixing and stirring so as to be 0, a re-emulsifiable polymer powder was obtained by the same operation as in Example 9-2.

Example 9-9 Example 9-9 was repeated except that 225 g of a 10% ferric sulfate aqueous solution was added instead of the 45% aluminum sulfate aqueous solution used for obtaining the aggregate in Example 9-2. In the same manner as in Example 2, a re-emulsifiable polymer powder was obtained.

Example 9-10 The same operation as in Example 9-2 was carried out except that the temperature of the mixture of the aqueous emulsion and the protective colloid was changed to 70 ° C., and then 45% aluminum sulfate was added. Thus, a re-emulsifiable polymer powder was obtained. Agglomerates were larger than in Example 9-2, and the solid-liquid separation time by filtration was reduced to 1/10, and workability was improved.

Example 9-11 Example 9-2 was repeated, except that 225 g of a 10% calcium chloride aqueous solution was added instead of the 45% aluminum sulfate aqueous solution used for obtaining the aggregate in Example 9-2. A re-emulsifiable polymer powder was obtained in the same manner as described above.

[Example 9-12] In Example 9-11, before adding the polyvalent metal salt, the pH of the mixture of the aqueous emulsion and the protective colloid was adjusted to 4 with sulfuric acid. A re-emulsifiable polymer powder was obtained in the same manner as in Example 9-11, except that 225 g of a 10% calcium chloride aqueous solution was added. Agglomerates were larger than in Examples 9-11, and the solid-liquid separation time by filtration was reduced to 1/3, and workability was improved.

[Example 9-13] A re-emulsifiable polymer powder was obtained in the same manner as in Example 9-2, except that the amount of 45% aluminum sulfate added in Example 9-2 was changed to 6.5 g. Was.

[Example 9-14] A re-emulsifiable polymer was prepared in the same manner as in Example 9-2, except that washing with sufficient pure water was repeated when filtering and separating the aggregates in Example 9-2. A powder was obtained. This and the re-emulsifiable polymer powder of Example 9-2 were each added to a 1% aqueous sodium hydroxide solution to obtain a re-emulsified solution, and these were applied to a glass plate and dried at room temperature for 3 days. When immersed in water, Examples 9-14 were more excellent in water resistance.

Example 9-15 Aqueous emulsion (A
-2) The protective colloid (B-1) was added at a solid ratio of 50 /
After mixing and stirring to 50, a re-emulsifiable polymer powder was obtained by the same operation as in Example 9-1.

[Examples 9-16] Aqueous emulsions (A
-2), the protective colloid (B-2) was added at a solid ratio of 50 /
After mixing and stirring to 50, a re-emulsifiable polymer powder was obtained by the same operation as in Example 9-2.

[Examples 9-17] Aqueous emulsion (A
-3) with a protective colloid (B-2) of 50 /
After mixing and stirring to 50, a re-emulsifiable polymer powder was obtained by the same operation as in Example 9-1.

[Comparative Examples 9-1 to 3] Each of the aqueous emulsions (A-1) to (A-3) was diluted with pure water to a resin content of 10%, and then diluted with 1000 g of the diluted product at room temperature by 45% aluminum sulfate. When 50 g of the aqueous solution was added, aggregates were formed. After solid-liquid separation of this aggregate by filtration,
It was dried at 80 ° C. until the residual water content became 2% or less. However, all the dried aggregates were soft and could not be ground. The re-emulsifiability was evaluated without grinding.

[Comparative Example 9-4] Each of the mixtures of the aqueous emulsions and protective colloids prepared in Examples 9-1 to 8 to 9 and 17 to 17 was charged with an inlet air temperature of 120.
By spray-drying at 60 ° C. and an outlet air temperature of 60 ° C., a re-emulsifiable polymer powder was obtained. All of the mixtures produced a large amount of deposits on the inner wall of the drying tower, the yield was 30% or less, and the re-emulsifiability was extremely poor.

[Comparative Example 9-5] A re-emulsifiable polymer powder was obtained in the same manner as in Example 9-2, except that the amount of 45% aluminum sulfate added in Example 9-2 was changed to 0.01 g. However, no aggregate was formed.

[Evaluation Example 9-1] The yield was calculated and graded in the same manner as in Evaluation Example 1-1.

[Evaluation Example 9-2] From the re-emulsifiable polymer powder, a re-emulsion liquid was prepared and evaluated in the same manner as in Evaluation Example 1-2. However, since the re-emulsifiable polymers of Comparative Examples 9-1 to 3 were all soft and could not be pulverized, they were not pulverized. In addition, since the re-emulsifiable polymer obtained by spray drying in Comparative Example 9-4 was already obtained in the form of a powder, these were reconstituted in 16 mesh (1 m
The powder having a particle size of 1 mm or less was sieved through m) to prepare a re-emulsion liquid in the same manner as described above.

[Evaluation Example 9-3] The re-emulsifiable polymer powder was mixed with cement in the same manner as in Evaluation Example 1-3, and the kneading time and
Workability, bending strength and compression strength were tested. However, since the re-emulsifiable polymer obtained by spray drying in Comparative Example 9-4 was already obtained in the form of a powder, these were recombined with 80 mesh (2
The powder classified so that the residue on the (00 μm) sieve was 5% or less was tested in the same manner as described above.

[Evaluation Example 9-4] Example 9-2 in this specification
Was evaluated for odor and curing in the same manner as in Evaluation Example 7-4. <Results> Odor: None. Curing: finished.

[Evaluation Example 9-5] Evaluation of re-emulsifiability assuming emulsification in cement The re-emulsifiability was evaluated by the method of Evaluation Example 7-5.

The re-emulsification rate of the polymer powder obtained in Example 9-2 was 40% or more, which was good. On the other hand, when the polymer of Example 9-2 was dried by spray drying, the re-emulsification ratio was 15% or less, which was poor.

Table 9-1 shows the composition of the aqueous emulsion used in the above Examples and Comparative Examples, Table 9-2 shows the composition of the protective colloid, and Table 9 shows the composition and evaluation results of the re-emulsifiable polymer powder. -3 to Table 9-14.

[0472]

[Table 121]

[0473]

[Table 122]

[0474]

[Table 123]

[0475]

[Table 124]

[0476]

[Table 125]

[0477]

[Table 126]

[0478]

[Table 127]

[0479]

[Table 128]

[0480]

[Table 129]

[0481]

[Table 130]

[0482]

[Table 131]

[0483]

[Table 132]

[0484]

[Table 133] Table 9-13. Composition and evaluation result of re-emulsifiable polymer powder (6)

[0485]

[Table 134] Table 9-14. Composition and evaluation result of re-emulsifiable polymer powder (6) (continued)

[0486]

According to the present invention, a (co) polymer or polymer powder having a function of substantially re-emulsifying in water having a pH of 5 or more can be obtained. When these are used as hydraulic cement modifiers, they show good iron workability,
A cured cement material having excellent flexural strength and compressive strength can be obtained. The re-emulsifiable polymer according to the present invention is characterized in that it does not require an anti-binder. Therefore, since it is not necessary to add the inorganic fine powder, it is inevitable when adding the inorganic fine powder, water absorption due to the inorganic fine powder, an increase in the flow value, uneven floating of the fine powder, etc. are caused. And the water / cement ratio can be reduced. Furthermore, since there is no need to add inorganic fine powder,
There is no increase in the water absorption of the obtained cement product. The re-emulsifiable polymer according to the present invention is advantageous at least in the following points as compared with a normal aqueous emulsion. Costs and energy required for distribution, transportation, and storage can be reduced. Since a large liquid container is not required, the packaging cost can be reduced. Since a large liquid container is not required, industrial waste can be reduced. In the case of a premixed one package product,
Since almost no weighing operation is required at the construction site,
Significant labor savings can be realized. In the case of a premixed one package product,
By mixing powder and water, the desired mortar or concrete can be prepared in one step, so that significant labor savings can be realized. In the case of a premixed one package product,
Since the desired formulation is accurately measured in advance, the quality control of the mortar and concrete during construction becomes easy.

The re-emulsifiable polymer produced by the prior art employing the conventional spray drying method was disadvantageous in at least the following points. The particles are easily thermally fused to each other, and the re-emulsifiability is not always satisfactory. The conventional spray-drying method (conventional spray-drying method) is disadvantageous in cost because the equipment is large-scale and consumes a large amount of energy. However, the present invention has solved such a problem. According to the present invention, when used as a cement modifier, tensile strength, bending strength, compressive strength, adhesive strength, wear resistance, and the like can be imparted. The present invention is characterized in that it does not necessarily require an anti-binder (for example, an inorganic fine powder, an organic fine powder having no film-forming property),
As applications other than the cement modifier, for example, it can be applied to a wide range of fields in which ordinary aqueous emulsions are used, such as civil engineering building materials, paper processing agents, paints, adhesives, and fiber treatment agents.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 51/00 C08L 51/00 (31) Priority claim number Japanese Patent Application No. 7-325743 (32) Priority date Heisei December 14, 1995 (December 14, 1995) (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 7-339041 (32) Priority date December 26, 1995 ( (December 26, 1995) (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 7-339042 (32) Priority date December 26, 1995 (December 26, 1995) ( 33) Priority claim country Japan (JP) (31) Priority claim number Japanese Patent Application No. 8-27653 (32) Priority date February 15, 1996 (Feb. 15, 1996) (33) Priority claim country Japan (JP) (31) Priority claim number Japanese Patent Application No. 8-27654 (32) Priority date February 15, 1996 (Feb. 15, 1996) (33) Priority claim country Japan (JP) (31) ) Priority claim number Japanese Patent Application No. 8-27655 (32) Priority date February 15, 1996 (Feb. 15, 1996) (33) Priority claim country Japan (JP) (31) Priority claim number Hei 8-35067 (32) Priority date February 22, 1996 (Feb. 22, 1996) (33) Priority claim country Japan (JP) (31) Priority claim number Japanese Patent Application Hei 8-35068 (32) Priority date February 22, 1996 (22 February 1996) (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 8-35069 (32) Priority date February 1996 22nd (1996.2.22) (33) Priority Country Japan (JP) (72) Futoshi Hoshino 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside Mitsui Chemicals Co., Ltd. (72) Yoshio Kikuta Kanagawa Prefecture 1190 Kasama-cho, Sakae-ku, Yokohama Mitsui Chemicals, Inc.

Claims (19)

[Claims] 1. A core / shell structure in which at least a part of a core surface is covered by a shell, and the core has a pendant group represented by the general formula (1) (Chemical Formula 1) in a repeating unit. 0% by weight or more and less than 40% by weight of at least one kind of repeating unit selected from the group consisting of repeating units and the group consisting of repeating units having a pendant group represented by the general formula (2) (Co) polymer (α2), (In the general formula (1), R ¹ and R ² are the same or different and are each hydrogen, an alkyl group having 1 to 12 carbon atoms or an alkyl group having an —OH group having 1 to 12 carbon atoms. In the general formula (2), R ³ has 1 to 1 carbon atoms.
30 alkylene groups, or -R ³ OH is-(R
²² -O-) _n -H. (However, R ²² has 2 carbon atoms.
5 to 5 identical or different alkylene groups, and n is 2 to 3
0)) The shell is represented by the general formula (1)
And at least one type of repeating unit selected from the group consisting of a repeating unit having a pendant group represented by the formula and a group consisting of a repeating unit having a pendant group represented by the general formula (2) A (co) polymer (α1) having at least 100% by weight and not more than 100% by weight, and (α1) is 15 to 85% by weight based on the total weight of (α1) and (α2); Is 85 to 15% by weight
And the content of at least one repeating unit having a pendant group represented by formula (1) and / or (2) in (α1) is at least 1 in (α2).
A (co) polymer having a function of substantially re-emulsifying in water having a pH of 5 or more, comprising particles characterized by having a content higher than the kind of the repeating unit. 2. A mixture comprising particles (A) and a protective colloid, wherein the particles (A) are a group consisting of a repeating unit having a pendant group represented by the general formula (1) (formula 2). And having at least one kind of repeating unit selected from the group consisting of repeating units having a pendant group represented by the general formula (2) (formula 2) in an amount of 0% by weight or more and less than 40% by weight (co)
A polymer (α2), (In the general formula (1), R ¹ and R ² are the same or different and are each hydrogen, an alkyl group having 1 to 12 carbon atoms or an alkyl group having an —OH group having 1 to 12 carbon atoms. In the general formula (2), R ³ has 1 to 1 carbon atoms.
30 alkylene groups, or -R ³ OH is-(R
²² -O-) _n -H. (However, R ²² has 2 carbon atoms.
5 to 5 identical or different alkylene groups, and n is 2 to 3
0)) The protective colloid has a repeating unit represented by the general formula (1)
At least one member selected from the group consisting of a repeating unit having a pendant group represented by (Chemical Formula 2) and the group consisting of a repeating unit having a pendant group represented by General Formula (2) (Formula 2) 20% by weight or more of repeating unit 1
(Α1) is 15 to 85% by weight and (α2) is 85 to 85% by weight based on the total weight of (α1) and (α2). 15% by weight
And the content of at least one repeating unit having a pendant group represented by formula (1) and / or (2) in (α1) is at least 1 in (α2).
A (co) polymer having a function of substantially re-emulsifying in water having a pH of 5 or more, comprising particles characterized by having a content higher than the kind of the repeating unit. 3. A repeating unit other than at least one repeating unit having a pendant group represented by the general formula (1) and / or (2) among the repeating units constituting (α1) and (α2). The unit is the general formula (v), (w),
The (co) polymer according to any one of claims 1 to 2, comprising at least one of (x), (y) and (z) (formula 3). Embedded image (In the general formulas (v) to (z), R ¹¹ is hydrogen or a methyl group, R ¹² is hydrogen or an alkyl group having 1 to 12 carbon atoms, R ¹³ is hydrogen, an alkyl group having 1 to 20 carbon atoms,
An alkene or phenyl group having 1 to 20 carbon atoms, R
¹⁴ is the same or different hydrogen, or an alkyl group having 1 to 12 carbon atoms, a sulfonic acid group or a metal sulfonate,
R ¹⁵ is an unsaturated hydrocarbon having or not having a side chain having 1 to 6 carbon atoms. ) 4. The method according to claim 1, wherein (α1) comprises at least one repeating unit selected from the group consisting of repeating units having a pendant group represented by the general formula (2) and (Chem. 4) in an amount of from 20% by weight to 100% by weight. 4. The method according to claim 1, wherein: (In the general formula (2), R ₃ is an alkylene group having 1 to 30 carbon atoms, or —R ³ OH is — (R ²² —O
−) _N −H. (Wherein, R ²² are the same or different alkylene group having 2 to 5 carbon atoms, n represents a is 2 to 30) (co) having the function of substantially redispersible relative) pH 5 or more water United. 5. The at least one repeating unit having a pendant group represented by the general formula (2):
The (co) polymer according to 4, characterized in that it is derived from 2-hydroxyethyl methacrylate. (In the general formula (2), R ₃ is an alkylene group having 1 to 30 carbon atoms, or —R ³ OH is — (R ²² —O
−) _N −H. (Wherein, R ²² are the same or different alkylene group having 2 to 5 carbon atoms, n represents 2 to 30)) 6. The step 1 (aqueous emulsion production step) includes a group consisting of a pendant group-containing ethylenically unsaturated monomer represented by the general formula (1) and the general formula (2). An ethylenically unsaturated monomer containing 20% by weight or more and 100% by weight or less of at least one selected from the group consisting of ethylenically unsaturated monomers having a pendant group represented by the following formula ) A protective colloid (a1) obtained by polymerization, and a general formula (1)
Selected from the group consisting of ethylenically unsaturated monomers having a pendant group represented by the formula: and the group consisting of ethylenically unsaturated monomers having a pendant group represented by the general formula (2). The ethylenically unsaturated monomer constituting the copolymer (a2) containing 0% by weight or more and less than 40% by weight of the at least one kind is represented by the following formula: (In the general formula (1), R ¹ and R ² are the same or different and are each hydrogen, an alkyl group having 1 to 12 carbon atoms or an alkyl group having an —OH group having 1 to 12 carbon atoms. In the general formula (2), R ³ has 1 to 1 carbon atoms.
30 alkylene groups, or -R ³ OH is-(R
²² -O-) _n -H. (However, R ²² has 2 carbon atoms.
5 to 5 identical or different alkylene groups, and n is 2 to 3
0)), and (a1) is 15 to 85% by weight and (a2) is 85 to 15% by weight based on the total weight of (a1) and (a2).
And the content of at least one monomer having a pendant group represented by the general formula (1) and / or (2) in (a1) is higher than the content of the monomer in (a2). A step of producing an aqueous emulsion composed of a dispersed phase of (co) polymer particles (A) and a continuous phase of water by radical (co) polymerization to a high degree; Step 2 (aggregate production step) Adding a mineral acid and / or an organic acid to the aqueous emulsion produced in 1;
aggregating the (co) polymer particles (A) by adjusting the pH to 4 or less to produce a (co) polymer aggregate (A '). pH 5
A method for producing a (co) polymer having a function of substantially re-emulsifying in water as described above. 7. Step 1 (core particle polymerization step) includes a group consisting of an ethylenically unsaturated monomer having a pendant group represented by the general formula (1) and the general formula (2).
Ethylenic constituting a copolymer (a2) containing at least one selected from the group consisting of ethylenically unsaturated monomers having a pendant group represented by the following formula (0) and not more than 40% by weight: Emulsion (co) polymerization of the unsaturated monomer, (In the general formula (1), R ¹ and R ² are the same or different and are each hydrogen, an alkyl group having 1 to 12 carbon atoms or an alkyl group having an —OH group having 1 to 12 carbon atoms. In the general formula (2), R ³ has 1 to 1 carbon atoms.
30 alkylene groups, or -R ³ OH is-(R
²² -O-) _n -H. (However, R ²² has 2 carbon atoms.
5 to 5 identical or different alkylene groups, and n is 2 to 3
0)) a dispersed phase of (co) polymer core particles (A ⁰ );
And a step of producing an aqueous emulsion composed of a continuous phase of water, and as step 2 (shell polymerization step), (co) polymer core particles (A ⁰ ) in the aqueous emulsion produced in step 1,
A group consisting of an ethylenically unsaturated monomer having a pendant group represented by the general formula (1) (formula 7), and an ethylenically unsaturated monomer having a pendant group represented by the general formula (2) (formula 7) 20% by weight or more and 100% by weight or less of a copolymer (a)
(A1) is 15 to 85% by weight, and (a2) is 85 to 15% by weight, based on the total weight of (a1) and (a2). weight%
And the content of at least one monomer having a pendant group represented by the general formula (1) and / or (2) in (a1) is higher than the content of the monomer in (a2). By radical (co) polymerization, the shell (S) composed of the protective colloid is formed at least partially on the particle surface of the (co) polymer core particles (A ⁰ ) in the aqueous emulsion produced in step 1 And a dispersed phase of core / shell type (co) polymer particles (A) having a core / shell structure in which at least a part of the core surface is covered by a shell, and a continuous phase of water. A step of producing an aqueous emulsion; Step 3 (aggregate production step): adding a mineral acid and / or an organic acid to the aqueous emulsion produced in Step 2;
aggregating the core / shell type (co) polymer particles (A) by adjusting the pH to 4 or less to produce a (co) polymer aggregate (A ′). A method for producing a (co) polymer having a function of substantially re-emulsifying in water having a pH of 5 or more. 8. A process 1 (aqueous emulsion production process) comprising a group consisting of a pendant group-containing ethylenically unsaturated monomer represented by the general formula (1) and the general formula (2) Emulsifying an ethylenically unsaturated monomer containing at least one selected from the group consisting of ethylenically unsaturated monomers having a pendant group represented by the following formula (0 to 40% by weight) ) The polymer (a2) is (In the general formula (1), R ¹ and R ² are the same or different and are each hydrogen, an alkyl group having 1 to 12 carbon atoms or an alkyl group having an —OH group having 1 to 12 carbon atoms. In the general formula (2), R ³ has 1 to 1 carbon atoms.
30 alkylene groups, or -R ³ OH is-(R
²² -O-) _n -H. (However, R ²² has 2 carbon atoms.
5 to 5 identical or different alkylene groups, and n is 2 to 3
0)) a dispersed phase of (co) polymer core particles (A ⁰ );
And a step of producing an aqueous emulsion composed of a continuous phase of water. Step 2 (a step of producing a protective colloid) is represented by the general formula (1)
From the group consisting of an ethylenically unsaturated monomer having a pendant group represented by (Chemical Formula 8), and a group consisting of an ethylenically unsaturated monomer having a pendant group represented by Formula (2) 20% by weight of at least one selected from the group consisting of
Radical (co) polymerization of an ethylenically unsaturated monomer containing not less than 100% by weight and protective colloid (a1)
In step 3 (mixing step), the aqueous emulsion produced in step 1 and the protective colloid produced in step 2 are mixed with (a1) based on the total weight of (a1) and (a2). 15 to 85% by weight, and (a2) is 85 to 15% by weight.
And the content of at least one monomer having a pendant group represented by the general formula (1) and / or (2) in (a1) is higher than the content of the monomer in (a2). Step 4 of mixing so as to be contained at a high level, Step 4 (aggregate production step): adding a mineral acid and / or an organic acid to the mixture of the aqueous emulsion mixed in Step 3 and the protective colloid produced in Step 2 a step of aggregating the (co) polymer particles (A) and the protective colloid by adjusting the pH to 4 or less to produce an aggregate (A ′) of the (co) polymer. A method for producing a (co) polymer having a function of substantially re-emulsifying in water having a pH of 5 or more. 9. Step 1 (aqueous emulsion production step) includes a group consisting of a pendant group-containing ethylenically unsaturated monomer represented by the general formula (1) and the chemical formula (2). An ethylenically unsaturated monomer containing at least one selected from the group consisting of ethylenically unsaturated monomers having a pendant group represented by the following formula (Chem. ) A protective colloid (a1) obtained by polymerization, and a general formula (1)
Selected from the group consisting of ethylenically unsaturated monomers having a pendant group represented by the formula: and the group consisting of ethylenically unsaturated monomers having a pendant group represented by the general formula (2). An ethylenically unsaturated monomer constituting a copolymer (a2) containing at least one of the above at least 0% by weight and less than 40% by weight, (In the general formula (1), R ¹ and R ² are the same or different and are each hydrogen, an alkyl group having 1 to 12 carbon atoms or an alkyl group having an —OH group having 1 to 12 carbon atoms. In the general formula (2), R ³ has 1 to 1 carbon atoms.
30 alkylene groups, or -R ³ OH is-(R
²² -O-) _n -H. (However, R ²² has 2 carbon atoms.
5 to 5 identical or different alkylene groups, and n is 2 to 3
0)), and (a1) is 15 to 85% by weight and (a2) is 85 to 15% by weight based on the total weight of (a1) and (a2).
And the content of at least one monomer having a pendant group represented by the general formula (1) and / or (2) in (a1) is higher than the content of the monomer in (a2). Radical (co) polymerization so that it is highly contained, (co)
A step of producing an aqueous emulsion, comprising a dispersed phase of the polymer particles (A) and a continuous phase of water; Step 2 (aggregate production step): adding a metal salt to the aqueous emulsion produced in Step 1; The (co) polymer particles (A) are subjected to salting out to form an aggregate (A ′) of the (co) polymer.
And a step of producing a (co) polymer having a function of substantially re-emulsifying in water having a pH of 5 or more. 10. Step 1 (core particle polymerization step)
A group consisting of an ethylenically unsaturated monomer having a pendant group represented by the general formula (1) (formula 10) and an ethylenic unsaturated monomer having a pendant group represented by the general formula (2) (formula 10) A copolymer containing at least one member selected from the group consisting of saturated monomers in an amount of 0% by weight or more and less than 40% by weight (a
Emulsion (co) polymerization of the ethylenically unsaturated monomer constituting 2) is carried out. (In the general formula (1), R ¹ and R ² are the same or different and are each hydrogen, an alkyl group having 1 to 12 carbon atoms or an alkyl group having an —OH group having 1 to 12 carbon atoms. In the general formula (2), R ³ has 1 to 1 carbon atoms.
30 alkylene groups, or -R ³ OH is-(R
²² -O-) _n -H. (However, R ²² has 2 carbon atoms.
5 to 5 identical or different alkylene groups, and n is 2 to 3
0)) a dispersed phase of (co) polymer core particles (A ⁰ );
And a step of producing an aqueous emulsion composed of a continuous phase of water, and as step 2 (shell polymerization step), (co) polymer core particles (A ⁰ ) in the aqueous emulsion produced in step 1,
A group consisting of an ethylenically unsaturated monomer having a pendant group represented by the general formula (1) (formula 10) and an ethylenic unsaturated monomer having a pendant group represented by the general formula (2) (formula 10) (A1) containing an ethylenically unsaturated monomer constituting a copolymer (a1) containing at least one member selected from the group consisting of saturated monomers in an amount of 20% by weight or more and 100% by weight or less; (a1) is 15 to 85% by weight and (a2) is 85 to 15% by weight based on the total weight of a2).
And the content of at least one monomer having a pendant group represented by the general formula (1) and / or (2) in (a1) is higher than the content of the monomer in (a2). The radical (co) polymerization is carried out so that the shell (S) composed of the protective colloid is contained at a high level so that at least one of the particle surfaces of the (co) polymer core particles (A ⁰ ) in the aqueous emulsion produced in the step 1 is formed. And a dispersion phase of core / shell type (co) polymer particles (A), which are particles having a core / shell structure in which at least a part of the core surface is covered by a shell, and water Step of producing an aqueous emulsion comprising a phase; Step 3 (aggregate production step): adding a metal salt to the aqueous emulsion produced in Step 2 to obtain core / shell type (co) polymer particles (A) Is salted out and (co) polymerized Producing a (co) polymer having a function of substantially re-emulsifying with respect to water having a pH of 5 or more, comprising a step of producing an aggregate (A ′) of a body. Method. 11. Step 1 (aqueous emulsion production step)
A group consisting of an ethylenically unsaturated monomer having a pendant group represented by the general formula (1) (formula 11);
Ethylenically unsaturated monomer containing at least one selected from the group consisting of ethylenically unsaturated monomers having a pendant group represented by the general formula (2) (0 to 40% by weight) The product is emulsified (co) polymerized into a (co) polymer (a2), (In the general formula (1), R ¹ and R ² are the same or different and are each hydrogen, an alkyl group having 1 to 12 carbon atoms or an alkyl group having an —OH group having 1 to 12 carbon atoms. In the general formula (2), R ³ has 1 to 1 carbon atoms.
30 alkylene groups, or -R ³ OH is-(R
²² -O-) _n -H. (However, R ²² has 2 carbon atoms.
5 to 5 identical or different alkylene groups, and n is 2 to 3
0)) a dispersed phase of (co) polymer core particles (A ⁰ );
And a step of producing an aqueous emulsion composed of a continuous phase of water. Step 2 (a step of producing a protective colloid) is represented by the general formula (1)
A group consisting of an ethylenically unsaturated monomer having a pendant group represented by the general formula (2);
20) at least one selected from the group consisting of ethylenically unsaturated monomers having a pendant group represented by 1)
A step of producing a protective colloid (a1) by radically (co) polymerizing an ethylenically unsaturated monomer containing at least 100% by weight and not more than 100% by weight; Step 3 (mixing step); And the protective colloid produced in the step 2, wherein (a1) is 15 to 85% by weight and (a2) is 85 to 15% by weight based on the total weight of (a1) and (a2).
And the content of at least one monomer having a pendant group represented by the general formula (1) and / or (2) in (a1) is higher than the content of the monomer in (a2). Step 4 (aggregate production step) of mixing so as to be contained in a high amount. A metal salt is added to the mixture of the aqueous emulsion and the protective colloid mixed in Step 3, and the (co) polymer particles (A)
And salting out the protective colloid to produce a (co) polymer aggregate (A ′). A method for producing a (co) polymer having a function of emulsifying. 12. (a1) is represented by the general formula (2)
12. The method according to claim 6, wherein the compound is obtained by using at least one selected from the group consisting of ethylenically unsaturated monomers having a pendant group represented by the formula: Method. Embedded image (In the general formula (2), R ³ is an alkylene group having 1 to 30 carbon atoms, or —R ³ OH is — (R ²² —O
−) _N −H. (Wherein, R ²² are the same or different alkylene group having 2 to 5 carbon atoms, n represents a is 2 to 30) (co) having the function of substantially redispersible relative) pH 5 or more water A method of manufacturing coalescence. 13. The method according to claim 13, wherein the at least one monomer is 2-
13. The production method according to claim 12, wherein the production method is hydroxyethyl methacrylate. 14. A (co) polymer obtained by the production method according to claim 6 and having a function of substantially re-emulsifying in water having a pH of 5 or more. 15. A particle having a core / shell structure in which at least a part of a core surface is covered with a shell, wherein the core is a water-insoluble (co) polymer, and the shell has a pH of 5 or more. A (co) polymer which is a water-soluble (co) polymer as described above and which can be substantially re-emulsified at a pH of 5 or more. 16. A particle having a core / shell structure in which at least a part of a core surface is covered by a shell, wherein the core is a water-insoluble (co) polymer, and the shell has a pH of 5 or more. The above is a water-soluble (co) polymer, and the shell is 15% based on the total weight of the core / shell.
A (co) polymer which is substantially re-emulsifiable at a pH of 5 or more, which is at least by weight 17. A core / shell structure in which at least a part of a core surface is covered by a shell, wherein the core comprises:
The glass transition temperature is -40 to 30 ° C., the glass transition temperature of the shell is at least 10 ° C. or higher than the glass transition temperature of the core, and 15% by weight based on the total weight of the particles.
Particles having the function of coagulating at pH 4 or less and having substantially no blocking property between particles. 18. The hydraulic cement as claimed in claim 1 to 5 and 14 to 1 in terms of a dry state.
7. A hydraulic cement composition comprising the (co) polymer according to any one of 7 to 0.5 to 60% by weight. 19. The method according to claim 1, wherein the equivalent to 0.5 to 60% by weight of the hydraulic cement is converted into a dry state. A method of mixing a water-curable cement composition to which a (co) polymer has been added with water and casting the resulting cement composition to form a hardened cement body.