JPWO2013084519A1 - Polishing agent composition and method for producing the same - Google Patents

Abstract

  Provided is a technique relating to a polish that is excellent in performance to suppress the occurrence of shoe marks and scratches, durability, and gloss retention, and that does not easily cause luster even when overcoated. When the core-shell structure particle 100 having an average particle diameter of 40 to 200 nm having a core part 150 and a shell part 200 covering the core part 150 is included, and the core part 150 is dissolved in tetrahydrofuran at a glass transition point of −70 to 0 ° C. The insoluble content of 0 to 20 mass% of the copolymer (A) is included, the shell part 200 includes the copolymer (B) having a glass transition point of 20 to 70 ° C., and the core-shell structured particle 100 has a weight average molecular weight. Is a composition for a polishing agent, having an insoluble content of 80 to 80% by mass when dissolved in tetrahydrofuran.

Description

  The present invention relates to a composition for a polish and a method for producing the same.

  A polishing agent is sometimes used to protect the flooring and the like and to maintain a beautiful appearance of the flooring. When the polishing agent is applied to the flooring material, a coating of the polishing agent is formed on the surface of the flooring material, and as a result, the flooring material can be given gloss. At the same time, the surface of the flooring material is covered with the polishing agent film, so that the generation of scratches on the surface of the flooring material can be suppressed.

  Also, the flooring is usually stepped on frequently with shoes or the like. For this reason, the polishing agent film formed on the surface of the flooring material is required to have durability (for example, difficulty in peeling off from the flooring material) and resistance to occurrence of shoe marks.

  Therefore, a polishing agent containing an acrylic resin emulsion has been proposed as a technique aimed at improving glossiness and durability and suppressing generation of shoe prints (for example, Patent Documents 1 and 2).

JP 2004-91713 A JP 2005-350543 A

  However, in the above-described technique, when a polishing agent is applied to a flooring and a long period of time passes, there is a possibility that a film formed from the polishing agent is deteriorated. In the above-described technology, when a floor material coated with a polishing agent film is strongly stepped on with a shoe or the like, there is a possibility that a large number of shoe marks or scratches may still be generated on the floor material or the film. Furthermore, in the above-described technique, glossing may occur when recoating.

  In view of the above problems, the present invention is excellent in performance, durability, and gloss retention that suppress the occurrence of shoe marks, scratches, etc., and is also a glossy product that is less likely to be glossy even when overcoated. It aims at providing the technique regarding an agent.

  The present invention is the following composition for a polish and a method for producing the same.

[1] A core-shell structure particle having an average particle diameter of 40 to 200 nm having a core part and a shell part covering the core part, wherein the core part is dissolved in tetrahydrofuran at a glass transition point of −70 to 0 ° C. The insoluble content includes a copolymer (A) of 0 to 20% by mass, the shell portion includes a copolymer (B) having a glass transition point of 20 to 70 ° C., and the core-shell structure particles have a weight average molecular weight. A composition for a polishing agent, which has 80,000 to 800,000 and an insoluble content of 0 to 30% by mass when dissolved in tetrahydrofuran.

[2] In the shell part, the copolymer (B) is obtained by copolymerizing an αβ unsaturated carboxylic acid monomer and a monomer other than the αβ unsaturated carboxylic acid monomer. The composition for a polishing agent according to the above [1].

[3] In the shell part, the copolymer (B) has a carboxyl group and contains a polyvalent metal of less than 1 chemical equivalent to the carboxyl group. The composition for the glossing agent described.

[4] Copolymer (A) having a glass transition point of −70 to 0 ° C., an average particle diameter of 20 to 110 nm, and an insoluble content of 0 to 20% by mass when dissolved in tetrahydrofuran is 1 to 10 parts by mass. Under the reaction system, αβ unsaturated carboxylic acid monomer (b1) 5 to 30 parts by mass and monomer (b2) copolymerizable with the αβ unsaturated carboxylic acid monomer 60 to 94 parts by mass [ However, the manufacturing method of the composition for polishes which obtains a copolymer (B) by emulsion-polymerizing (A) + (b1) + (b2) = 100 mass parts].

  According to the composition for a polishing agent of the present invention, it is excellent in performance to suppress the occurrence of shoe marks and scratches, durability, and gloss retention, and further, it is difficult to cause glossing even when it is overcoated. . According to the method for producing a composition for a polishing agent of the present invention, it is excellent in performance for suppressing the occurrence of shoe marks and scratches, durability, and gloss retention, and even when it is overcoated. It is possible to obtain a composition for a polishing agent that is less prone to cause the occurrence of rust.

It is sectional drawing of the core-shell structure particle | grains contained in one Embodiment of the composition for glazing agents of this invention. It is explanatory drawing of the usage condition of one Embodiment of the composition for polish agents of this invention.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. The present invention is not limited to the following embodiments, and changes, modifications, and improvements can be added without departing from the scope of the present invention.

1. Polishing composition:
The composition for a polishing agent of the present invention includes core-shell structured particles having an average particle diameter of 40 to 200 nm having a core part and a shell part covering the core part. In the composition for a polishing agent of the present invention, the core portion has a glass transition point of −70 to 0 ° C. and an insoluble content (hereinafter referred to as “THF insoluble content”) of 0 to 20 mass% when dissolved in tetrahydrofuran. A polymer (A) is included. Moreover, in the composition for polish agents of this invention, a shell part contains the copolymer (B) whose glass transition point is 20-70 degreeC. Furthermore, in the composition for a polishing agent of the present invention, the core-shell structured particles have a weight average molecular weight of 80,000 to 800,000 and a THF insoluble content of 0 to 30% by mass.

  As in the polishing composition of the present invention, a core portion containing a copolymer (A) having a glass transition point of −70 to 0 ° C. and a THF insoluble content of 0 to 20% by mass, and a glass transition point of 20 to 70 ° C. When the core-shell structure particles having a shell part containing the copolymer (B) are contained, and the core-shell structure particles have a weight average molecular weight of 80,000 to 800,000 and a THF insoluble content of 0 to 30% by mass, It is excellent in performance to suppress the occurrence of shoe marks and scratches, durability, and gloss retention, and it is difficult for gloss to be lost even when it is overcoated.

  In the polishing agent composition of the present invention, from the viewpoint of further improving durability and gloss retention, the core portion has a glass transition point of −70 to 0 ° C. and a THF insoluble content of 0 to 20 mass%. It is preferable that it consists of a coalescence (A) and a shell part consists of a copolymer (B) whose glass transition point is 20-70 degreeC.

  Further, the polish composition of the present invention is excellent in durability expression, and when the film formed from the polish composition is subjected to an impact, the effect of buffering the impact is further enhanced. The solidified product obtained by drying the copolymer (A) contained in the core part of the core-shell structured particles at room temperature is preferably in the form of a paste. “Paste-like” as used herein means that when the copolymer (A) is dried at room temperature, it does not form a film that recovers from deformation and becomes a semi-solid state.

  FIG. 1 is a cross-sectional view of a core-shell structured particle 100 included in an embodiment of a polishing agent composition of the present invention. As shown in the figure, the core-shell structure particle 100 included in the composition for a polishing agent of the present embodiment has a core portion 150 at the center. Furthermore, the periphery of the core part 150 is covered with the shell part 200.

  Drawing 2 is an explanatory view about one use mode of the constituent for polish of this embodiment. When using the polishing agent composition of the present embodiment, it is applied to the floor 500 or the like to form the film 300 containing the polishing agent composition.

  As shown in the figure, in the coating 300 formed from the polishing agent composition of the present embodiment, a large number of core-shell structured particles 100 are scattered throughout the coating 300. When the surface of the floor 500 is covered with such a coating 300, the surface of the floor 500 can be polished by the action of the core-shell structured particles 100 included in the coating 300.

  The core part 150 of the core-shell structured particle 100 included in the polishing agent composition of the present embodiment has a glass transition point (−70 to 0 ° C.) lower than room temperature (20 ° C.) and a THF insoluble content of 0 to 20 Since the copolymer (A) is contained in an amount of mass%, it is soft in an environment at room temperature (20 ° C.), and as a result, it can exhibit a buffering action against impact. Therefore, when the coating 300 is formed on the surface of the floor 500 using the polishing agent composition of the present embodiment, a strong impact is applied to the floor 500 or the coating 300 under a normal environment. In addition, the occurrence of scratches on the floor 500 and the coating 300 can be suppressed by the buffering action of the core portion 150 of the core-shell structured particle 100.

  Generally, when the glass transition point is less than room temperature (20 ° C.) as in the copolymer (A) [glass transition point: −70 to 0 ° C.] contained in the polishing composition of the present embodiment, It causes stickiness in an environment of room temperature (20 ° C.). In the composition for a polishing agent of this embodiment, the core part 150 containing the copolymer (A) is wrapped by the shell part 200. Therefore, it is suppressed that the core part 150 containing a copolymer (A) is exposed to the surface 350 of the membrane | film | coat 300 formed from the composition for polish agents of this embodiment. Moreover, since the copolymer (B) contained in the shell part 200 has a glass transition point (20 to 70 ° C.) at room temperature (20 ° C.) or higher, it is difficult to cause stickiness. As a result, the surface 350 of the film 300 formed from the polishing agent composition of the present embodiment is suppressed from stickiness. When the stickiness of the surface 350 of the film 300 is suppressed in this way, dust and the like are less likely to adhere to the surface 350 of the film 300, so that dirt adheres to the surface of the floor 500 and the film 300, and shoes caused by the adhesion of dirt. It is possible to suppress the occurrence of traces.

  In particular, in the film 300 formed from the composition for the polishing agent of the present embodiment, since there is a buffering action by the core part 150 described above, the floor 500 and the film 300 are strongly stepped on by the shoe sole, or a heavy desk or chair is used. Even when placed, the pressure from the shoe sole and the legs of the desk or chair can be relieved. Therefore, if the floor 500 is covered with the coating 300 of the composition for the polish of the present embodiment, even if the shoe sole or the leg of the desk or chair is contaminated, the stain is removed from the floor 500 and the coating. As a result, the pressure applied to the surface of the shoe 300 is weakened, and as a result, dirt attached to the legs such as the shoe sole and the desk is less likely to adhere to the floor 500 and the film 300. That is, if the floor 500 is covered with the coating 300 of the composition for a polishing agent of the present embodiment, it is possible to suppress the occurrence of shoe marks and the like on the surfaces of the floor 500 and the coating 300.

  In the composition for a polishing agent of this embodiment, the average particle diameter of the core-shell structured particles 100 is 40 to 200 nm. When the average particle diameter of the core-shell structured particles 100 is 40 to 200 nm as in the polishing agent composition of the present embodiment, when forming the coating 300 of the polishing agent composition, Even when the composition is overcoated on the floor 500, the infinite number of core-shell structured particles 100 are likely to be evenly scattered throughout the coating 300, and as a result, the occurrence of luster can be suppressed.

  In the polishing agent composition of the present invention, from the viewpoint of suppressing the occurrence of scratches on the surface of the film formed with the polishing agent composition and the surface of the floor coated with the coating, The glass transition point of the polymer (A) is preferably −60 to −10 ° C., and more preferably −50 to −20 ° C.

  In the polishing agent composition of the present invention, the average particle size of the copolymer (A) is 20 to 110 nm in the core part because the overcoatability can be improved more reliably. Is more preferable, more preferably 30 to 90 nm, and most preferably 30 to 60 nm. In this specification, “overcoatability” means that a coating film is formed by recoating the composition for a polishing agent, and this coating film is dried to form a film. It refers to the ability to suppress the occurrence of In the case where the overcoatability is improved, the occurrence of luster is significantly suppressed even if the polishing agent composition is repeatedly applied.

  In the composition for a polishing agent of the present invention, the copolymer (A) contained in the core part is (meth) acrylic because the copolymerizability is good and the glass transition point can be easily adjusted. It is preferable that it is a copolymer. The term “copolymerizable” as used herein refers to the ability to easily copolymerize two or more monomers (specific examples of (meth) acrylic copolymers will be described later).

  In the polishing agent composition of the present invention, in the shell part, the copolymer (B) is used because it is possible to more reliably suppress the improvement of durability and the occurrence of shoe marks. It is preferably obtained by copolymerizing an αβ unsaturated carboxylic acid monomer and a monomer other than the αβ unsaturated carboxylic acid monomer (αβ unsaturated carboxylic acid monomer and αβ unsaturated carboxylic acid monomer). Specific examples of monomers other than the acid monomer will be described later).

  In the composition for a polishing agent of the present invention, it is possible to more reliably suppress the improvement of durability and the occurrence of shoe marks, and the stability of the composition for a polishing agent can be improved. In the shell portion, the copolymer (B) preferably has a carboxyl group and contains a polyvalent metal of less than 1 chemical equivalent to the carboxyl group (specific examples of the polyvalent metal will be described later). ).

  In the polishing agent composition of the present invention, in the shell portion, the copolymer (B) is used because the generation of shoe marks and the like on the surface of the film formed from the polishing agent composition can be more reliably suppressed. The glass transition point of is preferably 30 to 70 ° C, and more preferably 40 to 60 ° C.

  Further, in the composition for a polishing agent according to the present invention, the core-shell structure is used because of the excellent development of durability and the good imparting of polymerization stability when producing core-shell structured particles. When the total of the core part and the shell part is 100 parts by mass, the particle is preferably 1 to 10 parts by mass of the core part and 90 to 99 parts by mass of the shell part.

  In the polishing agent composition of the present invention, the core-shell structure particles preferably have a THF-insoluble content of 0 to 20% by mass because the overcoatability can be improved.

  About the composition for polish agents of this invention described so far, it is possible to obtain by the following manufacturing methods, for example.

2. Method for producing a composition for a polishing agent:
The method for producing a composition for a polishing agent of the present invention comprises a copolymer (A) having a glass transition point of -70 to 0 ° C., an average particle size of 20 to 110 nm, and a THF insoluble content of 0 to 20% by mass. Under a reaction system including 10 parts by mass, 5 to 30 parts by mass of the αβ unsaturated carboxylic acid monomer (b1), and a monomer (b2) 60 copolymerizable with the αβ unsaturated carboxylic acid monomer. ~ 94 parts by mass [however (A) + (b1) + (b2) = 100 parts by mass] is subjected to emulsion polymerization to obtain a copolymer (B).

  In the method for producing a polishing agent composition of the present invention, it is possible to obtain core-shell structured particles having a form in which the periphery of the core portion containing the copolymer (A) is covered by the shell portion containing the copolymer (B). become.

  As a copolymer (A) which can be used for the manufacturing method of the composition for polish agents of this invention, a (meth) acrylic-type copolymer can be mentioned, for example. In addition, the (meth) acrylic copolymer that can be used as the copolymer (A) in the present invention is, for example, one or more monomers corresponding to alkyl (meth) acrylate, and an αβ unsaturated carboxylic acid monomer. Monomer mixture in which one or more monomers corresponding to any of a monomer, an aromatic vinyl monomer, and a polyfunctional monomer are mixed [including at least an alkyl (meth) acrylate Furthermore, by mixing an αβ unsaturated carboxylic acid monomer, an aromatic vinyl monomer, and a monomer mixture containing at least one of polyfunctional monomers] and an emulsifier, It can be obtained by dispersing a monomer in an emulsifier in advance and adding a polymerization initiator such as persulfate to carry out emulsion polymerization.

  Among the “alkyl (meth) acrylates” that can be used as the raw material of the (meth) acrylic copolymer that can be used as the copolymer (A), methyl acrylate, ethyl acrylate, isopropyl acrylate, and n-butyl are used as the alkyl acrylate. Examples thereof include acrylate, isobutyl acrylate, tert-butyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, and lauryl acrylate. Among the “alkyl (meth) acrylates” used as the raw material for the (meth) acrylic copolymer, the alkyl methacrylate includes methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert- Examples thereof include butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, and trimethylsilyl methacrylate. Among those listed here, it is a highly versatile raw material and good copolymerization, and it suppresses the generation of scratches and the scars on the surface of the film formed from the composition for the polish. For the reason that the performance is improved, at least one of n-butyl acrylate, 2-ethylhexyl acrylate, and methyl methacrylate can be used as the copolymer (A) of the (meth) acrylic copolymer. It is preferable to use it as a raw material in the present invention.

  Examples of the “αβ unsaturated carboxylic acid monomer” used as a raw material for the (meth) acrylic copolymer that can be used as the copolymer (A) include acrylic acid, methacrylic acid, crotonic acid, vinyl acetic acid, and itaconic acid. , Maleic acid, maleic anhydride, fumaric acid, citraconic acid and the like. Among the materials listed here, at least acrylic acid and methacrylic acid are used as a copolymer because it is a versatile raw material, has good copolymerizability, and easily adjusts the acid value. It is preferably used in the present invention as a raw material for a (meth) acrylic copolymer that can be used as (A).

  Examples of the “aromatic vinyl monomer” used as a raw material for the (meth) acrylic copolymer that can be used as the copolymer (A) include styrene, α-methylstyrene, o-methylstyrene, and p-methyl. Styrene, o-ethylstyrene, p-ethylstyrene, α-chlorostyrene, p-chlorostyrene, p-methoxystyrene, p-aminostyrene, p-acetoxystyrene, sodium styrenesulfonate, α-vinylnaphthalene, 1-vinyl Examples thereof include sodium naphthalene-4-sulfonate, 2-vinylfluorene, 2-vinylpyridine, 4-vinylpyridine and the like. Among those listed here, from the viewpoint of being a versatile raw material and imparting gloss, at least styrene can be used as a raw material for a (meth) acrylic copolymer that can be used as a copolymer (A). It is preferable to use it.

  Examples of the “polyfunctional monomer” used as a raw material for the (meth) acrylic copolymer that can be used as the copolymer (A) include allyl methacrylate, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, and divinyl. Examples thereof include benzene, ethylene glycol dimethacrylate, butylene glycol diacrylate, hexamethylene glycol dimethacrylate and the like. Among those listed here, at least allyl methacrylate, divinylbenzene, and the like, because of good copolymerizability and easy adjustment of THF-insoluble matter important for enhancing durability and gloss retention. Any one or more of ethylene glycol dimethacrylate is preferably used in the present invention as a raw material for a (meth) acrylic copolymer that can be used as the copolymer (A).

  In the method for producing a polishing agent composition of the present invention, when the average particle size of the copolymer (A) is 20 to 110 nm, the average particle size of the obtained core-shell structured particles tends to be 40 to 200 nm. .

  Examples of the αβ-unsaturated carboxylic acid monomer (b1) that can be used in the method for producing a polishing agent composition of the present invention include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and monophthalic acid. A half ester such as [2- (meth) acryloyloxyethyl], succinic acid mono [2- (meth) acryloyloxyethyl], carboxyethyl acrylate, and the like can be given. The αβ unsaturated carboxylic acid monomer (b1) listed here can be used in the present invention alone or in combination of two or more. In particular, in the αβ unsaturated carboxylic acid monomer (b1) listed here, from the viewpoint of improving the stability during polymerization, and from the viewpoint of enhancing the durability of the resulting polish composition, It is preferable to use at least one of acrylic acid and methacrylic acid in the present invention.

  Moreover, as a monomer (b2) which can be used for the manufacturing method of the composition for polish agents of this invention, acrylic acid ester monomer (For example, n-butyl acrylate, i-butyl acrylate, t- Butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isononyl acrylate, lauryl acrylate) and the like. Among those listed here, the film formed from the composition for the polishing agent is used to suppress the occurrence of scratches on the flooring material, and the occurrence of shoe marks on the surface of the film formed from the composition for the polishing agent. From the viewpoint of suppressing the above, it is preferable to use at least one of n-butyl acrylate and i-butyl acrylate as the monomer (b2) in the present invention.

  In addition, the monomer (b2) that can be used in the method for producing the composition for a polishing agent of the present invention includes carbon atoms of alkyl groups such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isopropyl acrylate, and isopropyl methacrylate. Is an ethylenically unsaturated monomer such as an acrylic acid alkyl ester or methacrylic acid alkyl ester of 3 or less; (meth) acrylic acid cyclic alkyl ester such as cyclohexyl (meth) acrylate; phenoxyalkyl (meth) acrylate, benzyl (meth) Aromatic (meth) acrylic acid esters such as acrylate; hydroxyalkyl acrylate, hydroxyalkyl methacrylate, polyoxyethylene (meth) acrylate, methoxyethyl acrylate, ethoxy (Meth) acrylic acid esters such as acrylate, glycidyl acrylate and glycidyl methacrylate; (meth) acrylic acid amides such as acrylamide, methacrylamide, N-methylolacrylamide, N-methoxymethylacrylamide and N-methoxybutylacrylamide; vinyl methyl ketone , Vinyl ethyl ketone, vinyl-n-propyl ketone, vinyl-i-propyl ketone, vinyl-n-butyl ketone, vinyl-i-butyl ketone, vinyl-t-butyl ketone, vinyl phenyl ketone, vinyl benzyl ketone, divinyl ketone, diacetone Aldo group and / or keto group-containing radical polymerizable monomers such as acrylamide; (meth) acrylonitrile, crotonnitrile, 2-cyanoethyl (meth) acrylate, 2 Nitrile group-containing unsaturated compounds such as cyanopropyl (meth) acrylate and 3-cyanopropyl (meth) acrylate; polyfunctional monomers such as divinylbenzene, (poly) ethylene glycol di (meth) acrylate and allyl methacrylate; styrene Monovinyl aromatic compounds such as o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-ethylvinylstyrene, α-methylstyrene, α-fluorostyrene; vinyl halides such as vinyl chloride and vinylidene chloride; And vinyl esters such as vinyl propionate. Among those listed here, the film formed from the composition for the polishing agent is used to suppress the occurrence of scratches on the flooring material, and the occurrence of shoe marks on the surface of the film formed from the composition for the polishing agent. From the viewpoint of suppressing the above, it is preferable to use at least one of methyl methacrylate and cyclohexyl (meth) acrylate as the monomer (b2) in the present invention.

  In the method for producing a composition for a polishing agent of the present invention, an aromatic vinyl monomer (for example, styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, o-ethylstyrene, p-ethylstyrene, α-chlorostyrene, p-chlorostyrene, p-methoxystyrene, p-aminostyrene, p-acetoxystyrene, sodium styrenesulfonate, α-vinylnaphthalene, 1-vinylnaphthalene- 4-sulfonic acid sodium, 2-vinylfluorene, 2-vinylpyridine, 4-vinylpyridine, etc.) may be used. In particular, among those listed here, styrenic monomers are excellent in versatility that they can be used as raw materials for other resin compositions, which can reduce manufacturing costs and improve gloss. From the viewpoint of being, it is preferable to use it as the monomer (b2) in the present invention.

  In the method for producing a polishing agent composition of the present invention, when emulsion polymerization is performed, an αβ unsaturated carboxylic acid monomer (b1), a monomer (b2), a molecular weight in the presence of the copolymer (A). A pre-emulsion may be prepared in advance by mixing a regulator, water, and the like, adding an emulsifier thereto, and emulsifying the mixture. Further, this pre-emulsion is usually used for a polymerization reaction under an inert atmosphere. As a result, a core part containing a copolymer (A) and a shell part [a copolymer formed from a monomer mixture containing an αβ unsaturated carboxylic acid monomer (b1) and a monomer (b2) A copolymer dispersion containing core-shell structured particles having (including (B)] can be obtained.

  Moreover, in the manufacturing method of the composition for polishes of this invention, an emulsion polymerization reaction can be performed, supplying a pre-emulsion and a polymerization initiator to a reaction system continuously or intermittently.

  Examples of the polymerization initiator that can be used in the method for producing the composition for a polishing agent of the present invention include persulfates and redox polymerization initiators. In the method for producing a polishing agent composition of the present invention, only a persulfate may be used as a polymerization initiator, or a persulfate and a redox polymerization initiator may be used in combination. The redox polymerization initiator here is a polymerization initiator in which an oxidizing agent and a reducing agent are combined.

  In the method for producing a polishing agent composition of the present invention, examples of the oxidizing agent used for the redox polymerization initiator include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate; hydrogen peroxide, t- Butyl hydroperoxide, t-butyl peroxymaleic acid, succinic acid peroxide, benzoyl peroxide, cumene hydroperoxide, diisopropyl peroxydicarbonate, cumyl peroxyneodecanoate, cumyl peroxyoctoate, diisopropylbenzene hydro And peroxides such as peroxide, p-menthane hydroperoxide, and 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane.

  On the other hand, in the method for producing a polishing agent composition of the present invention, examples of the reducing agent used for the redox polymerization initiator include acidic sodium sulfite, sodium dithionite, sodium thiosulfate, Rongalite, ascorbic acid, fructose. And iron salts such as ferrous sulfate and ferric sulfate. Further, in the method for producing a polishing agent composition of the present invention, when the above reducing agent is used as a redox polymerization initiator, a chelating agent such as sodium ethylenediaminetetraacetate may be used in combination. .

  In the method for producing a polishing agent composition of the present invention, when a redox polymerization initiator is used, the oxidation agent used for the redox polymerization initiator is only one kind [for example, oxidation of potassium persulfate and the like listed above. One of the agents] or a mixture of a plurality of [for example, two or more of the oxidizing agents such as potassium persulfate listed above] may be used. In this case, the reducing agent used for the redox polymerization initiator may be only one type [for example, one type of reducing agents such as sodium sulfite listed above] or a plurality of types [for example, listed above. 2 or more of reducing agents such as acidic sodium sulfite] may be mixed.

In the method for producing a polishing agent composition of the present invention, when a redox polymerization initiator is used for the polymerization reaction, the preferred combination of the oxidizing agent, the reducing agent and the chelating agent mentioned above includes, for example, the following 2 A combination of combinations (combination A, combination B) can be given.
(Combination A) Persulfate, acidic sodium sulfite, ferrous sulfate (Combination B) t-butyl hydroperoxide, acidic sodium sulfite, ferrous sulfate

  In the method for producing a polishing agent composition of the present invention, when a redox polymerization initiator is used, durability of the resulting polishing agent composition (or a film formed from the polishing agent composition) is imparted. From the reason that it is possible to improve the stability over time, the proportion of the redox polymerization initiator used is the copolymer (A) and the αβ unsaturated carboxylic acid monomer ( The total amount of b1) and the monomer (b2) is preferably 0.01 to 5.0 parts by weight, more preferably 0.01 to 3.0 parts by weight, based on 100 parts by weight. Particularly preferred is 0.1 to 2.0 parts by mass. In addition, in the manufacturing method of the composition for polish agents of this invention, when the oxidizing agent used for a redox-type polymerization initiator is only a persulfate, a copolymer (A) and an alpha beta unsaturated carboxylic acid monomer ( It is preferable that the usage-amount of a redox type polymerization initiator is 0.1-1.0 mass part with respect to 100 mass parts of total amounts of b1) and a monomer (b2).

  In the method for producing a polishing agent composition of the present invention, as an emulsifier that can be used in the polymerization reaction, polyoxyethylene alkyl ether, polyoxyethylene alkyl sulfate salt, polyoxyethylene polycyclic phenyl ether sulfate salt, polyoxyethylene Surfactants such as sodium ethylene alkyl succinate, sodium lauryl sulfate, and sodium dodecylbenzene sulfonate can be listed.

  In the method for producing a polishing agent composition of the present invention, from the viewpoint of improving the polymerization stability, and from the viewpoint of easily controlling the particle diameter of the obtained core-shell structure particles to a desired size, the use ratio of the emulsifier is The total amount of the copolymer (A), the αβ unsaturated carboxylic acid monomer (b1) and the monomer (b2) is preferably 0.2 to 7.0 parts by mass. Further, it is more preferably 0.3 to 5.0 parts by mass, and most preferably 0.5 to 3.0 parts by mass.

  In the method for producing a polishing agent composition of the present invention, examples of the molecular weight regulator that can be used in the polymerization reaction include butyl mercaptan, dodecyl mercaptan, octyl thioglycolate, isopropyl alcohol, methanol, and carbon tetrachloride. .

  In the method for producing a polishing agent composition of the present invention, when a molecular weight regulator is used, the durability of the resulting polishing agent composition (or a film formed from the polishing agent composition) is adjusted by adjusting the molecular weight. From the viewpoint that the molecular weight regulator can be increased, the total amount of the copolymer (A), the αβ unsaturated carboxylic acid monomer (b1), and the monomer (b2) is 100 parts by mass. Is preferably 0.001 to 0.80 parts by mass, more preferably 0.005 to 0.60 parts by mass, and particularly preferably 0.01 to 0.40 parts by mass. Most preferred.

  In the method for producing a polishing agent composition of the present invention, the core shell contained in the copolymer dispersion (the polishing agent composition) obtained by appropriately selecting the type and use ratio of the molecular weight regulator. It becomes possible to make the structured particles have a desired weight average molecular weight (Mw) and a desired THF-insoluble amount.

  In the method for producing a composition for a polishing agent of the present invention, the resulting composition for a polishing agent (or a film formed from the composition for a polishing agent) has high durability and stability, and generation of shoe marks and the like. From the reason that it is possible to obtain a composition for a polishing agent that can more effectively suppress the rust, a copolymer dispersion in which core-shell structure particles are dispersed, and a polyvalent metal compound in a slurry state or a chelate solution It is preferable to add.

In the method for producing a polishing agent composition of the present invention, zinc oxide, calcium oxide, calcium hydroxide, aluminum hydroxide can be used as the polyvalent metal compound that can be added after preparation of the copolymer dispersion containing core-shell structured particles. , Zinc carbonate ammonia, calcium carbonate, Mg (OH) ₂ , MgO, MgCO ₃ , and Mg (OH) ₂ .3H ₂ O, zinc ammonium acetate, zinc acrylate ammonium, zinc malate ammonia, alanine calcium ammonia, etc. be able to.

  When a polyvalent metal compound is used in the method for producing a polishing agent composition of the present invention, from the viewpoint of improving viscosity adjustment and addition / mixing stability of the polishing agent composition, The total amount of the copolymer (A), the αβ unsaturated carboxylic acid monomer (b1), and the monomer (b2) is preferably 0.5 to 7.0 parts by mass. Furthermore, it is more preferable that it is 1.0-5.0 mass parts, and it is especially preferable that it is 1.5-4.0 mass parts.

  In the method for producing a composition for a polishing agent of the present invention, the coating film of the composition for a polishing agent is dried when the composition for a polishing agent is used by appropriately selecting the type and use ratio of the polyvalent metal. In the process, the copolymer (B) contained in the shell part of the core-shell structured particle and the polyvalent metal are metal-crosslinked, and as a result, various performances such as improved durability, water resistance and peelability are improved. It becomes possible to raise it more reliably.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these Examples.

(1) Preparation of polishing agent composition:
(Examples 1-5, Comparative Examples 2-8, 10, 11)
For Examples 1 to 5 and Comparative Examples 2 to 8, 10, and 11, each monomer (a) was mixed in the formulation shown in Table 1, and emulsion polymerization was performed, thereby copolymer ( A) was obtained. In Table 1, the numerical value shown in the column of each monomer (a) represents the amount of the monomer (a) in “parts by mass”. In Table 1, “-” instead of a numerical value in each monomer (a) column means that the monomer (a) is not used.

  Specifically, first, in the reaction vessel, a non-reactive emulsifier [Emar 2FG or Latem E-118B (both manufactured by Kao Corporation)] or a reactive emulsifier [KH-1025 (Daiichi Kogyo Seiyaku Co., Ltd.) ], Water, and monomer (a) were charged, and the temperature of the liquid was raised to 65 ° C. while stirring in a nitrogen stream. Thereafter, an aqueous catalyst solution (0.5% aqueous ammonium persulfate solution) was added and reacted for 0.75 hour to obtain a copolymer (A) of the core part.

  Furthermore, the copolymer (B) of the shell part was synthesized by emulsion polymerization of the monomer (b) with the formulation shown in Table 1 in the presence of the copolymer (A) of the core part. A copolymer dispersion (a composition for a polishing agent) containing core-shell structured particles was obtained. In Table 1, the numerical value shown in the column of each monomer (b) represents the amount of the monomer (b) in “parts by mass”. In Table 1, “-” shown in the column of each monomer (b) instead of a numerical value means that the monomer (b) is not used.

  Specifically, a pre-emulsion is prepared by mixing and stirring a mixed solution of the monomer (b), 24 parts by weight of water, and 0.9 part by weight of a reactive or non-reactive emulsifier, and pre-emulsifying. Got. Next, a pre-emulsion and a catalyst aqueous solution (0.25% ammonium persulfate aqueous solution) are dropped in parallel at 75 ° C. over about 3 hours toward the dispersion containing the core copolymer (A). After finishing the above, the mixture was kept at 85 ° C. for about 2 hours to obtain a copolymer dispersion containing core-shell structured particles.

Subsequently, for Examples 1 to 3 and Comparative Examples 2 to 8, 10, and 11, less than one chemical equivalent of Zn with respect to the carboxyl group of the copolymer (B) contained in the shell portion of the core-shell structured particle Thus, a chelate solution containing Zn or a ZnO slurry was added to the copolymer dispersion containing the core-shell structured particles at 80 ° C. Further, for Example 5, the co-polymer containing the core-shell structured particles so that less than one chemical equivalent of Mg is contained with respect to the carboxyl group of the copolymer (B) contained in the shell portion of the core-shell structured particles. Mg (OH) ₂ was added to the combined dispersion at 80 ° C.

  Further, for Example 4, the pH of the copolymer dispersion containing core-shell structured particles was adjusted to 7.0 using potassium carbonate and stirred for 2 hours.

(Comparative Examples 1 and 9)
For Comparative Examples 1 and 9, the monomer (b) was emulsion polymerized with the formulation shown in Table 1 to obtain a copolymer dispersion (a composition for a polishing agent) containing a copolymer. .

The contents of the abbreviations relating to the monomer (a) and the monomer (b) shown in Table 1 are as follows.
BA: Butyl acrylate [Wako Pure Chemical Industries, Ltd.]
2EHA: 2-ethylhexyl acrylate [manufactured by Toagosei Co., Ltd.]
ST: Styrene [Mitsubishi Chemical Corporation]
MAA: Methacrylic acid [Kuraray Co., Ltd.]
AMA: Allyl methacrylate [Mitsubishi Gas Chemical Co., Ltd.]
EDMA: ethylene glycol dimethacrylate [manufactured by Shin-Nakamura Chemical Co., Ltd.]
MMA: Methyl methacrylate [Mitsubishi Rayon Co., Ltd.]
CHMA: Cyclohexyl methacrylate [Mitsubishi Rayon Co., Ltd.]
AA: Acrylic acid [Toagosei Co., Ltd.]
NASS: Sodium p-styrenesulfonate [manufactured by Tosoh Organic Chemical Co., Ltd.]
DVB: DVB-570 [manufactured by Nippon Steel Chemical Co., Ltd.]

(2) Measurement of average particle size:
The average particle diameter is determined by the Stokes-Einstein equation [the following equation (I)] from the diffusion coefficient D (m ² / s) detected by FPAR-1000 [manufactured by Otsuka Electronics Co., Ltd.] using the dynamic light scattering method. The obtained Stokes diameter was measured.
Formula (I): d = kT / 3πη ₀ D
[In the formula (I), d is the average particle diameter (m), k is Boltzmann's constant (= 1.3804868 × 10 ⁻²³ J / K), T is the absolute temperature (K), η ₀ is the viscosity of the solvent (Pa・ S)]

  Average particle diameter (nm) of the copolymer (A) of the core part obtained in Examples 1 to 5 and Comparative Examples 2 to 8, 10, and 11, Examples 1 to 5, Comparative Examples 2 to 8, 10 Table 1 shows the average particle size (nm) of the core-shell structure particles obtained in Nos. 11 and 11 and the average particle size (nm) of the copolymer obtained in Comparative Examples 1 and 9.

(3) Measurement of glass transition point:
In measuring the glass transition point, first, 1 to 10 g of the copolymer was thinly stretched on a glass plate and dried at 25 ° C. for 3 days to obtain a dry film. Then, using the differential scanning calorimeter (TA Instruments make, MDSC Q200 type | mold), the temperature increase rate is 20 degree-C / min and a temperature range is -90 to 100 degreeC for the obtained dry film. Measurement was performed under a nitrogen atmosphere. The amount of the sample was measured under the condition of 5 to 10 mg. The glass transition point (Tg) (° C.) was defined as the temperature between the inflection point and the end point of the differential curve of differential scanning calorimetry obtained by the measurement [glass transition point (Tg) measured by the above method] (° C.) is referred to as “glass transition point (° C.)” in this specification. In addition, about the copolymer extended thinly to the glass plate as a sample, the product of the polymerization reaction of each step performed in each above-mentioned Example and each comparative example was used as it was. In Examples 1 to 5 and Comparative Examples 2 to 8, 10, and 11, the glass transition point for the core copolymer (A) obtained in Examples 1 to 5 and Comparative Examples 2 to 8, 10, and 11 Table 1 shows the glass transition point of the obtained copolymer (B) of the shell part and the glass transition point (° C.) of the copolymer obtained in Comparative Examples 1 and 9.

(4) Measurement of tetrahydrofuran insoluble matter (THF insoluble matter):
In the method for measuring the insoluble content (THF insoluble content) when dissolved in tetrahydrofuran, first, the copolymer containing the copolymer (A) of the core portion of Examples 1 to 5 and Comparative Examples 2 to 8, 10, and 11 is used. Copolymer dispersion (reaction product obtained by copolymerization of monomer (a)), copolymer dispersion containing core-shell structured particles of Examples 1 to 5 and Comparative Examples 2 to 8, 10, and 11 (glazing agent) Composition) and a copolymer dispersion (a composition for a polish) containing the copolymer of Comparative Examples 1 and 9 were applied to a plastic tray (Disposer DT-1 manufactured by ASONE Corporation). A film was prepared by drying at room temperature. Subsequently, 0.15 g of the film was added to 50 mL of tetrahydrofuran and dissolved by stirring for 16 hours. The obtained solution was filtered using filter paper corresponding to two types of JISP3801, and 10 mL of the filtrate was collected and dried. The insoluble matter (gel fraction) was calculated from the dried mass. Copolymer (A) of core parts of Examples 1 to 5 and Comparative Examples 2 to 8, 10, and 11, Core-shell structured particles of Examples 1 to 5 and Comparative Examples 2 to 8, 10, and 11, and Comparative Example 1 Table 1 shows the THF-insoluble content (mass%) of the copolymer of No. 9 and No. 9.

(5) Measurement of weight average molecular weight:
Copolymer dispersion containing the core-shell structured particles of Examples 1 to 5 and Comparative Examples 2 to 8, 10, and 11 (a composition for a polishing agent), and a copolymer containing the copolymers of Comparative Examples 1 and 9 Regarding the weight average molecular weight of the dispersion (a composition for a polishing agent), after immersing the composition in tetrahydrofuran at room temperature for 24 hours, the weight average molecular weight of the tetrahydrofuran-soluble matter was measured by gel permeation chromatography [GPC]. And evaluated. The results are shown in Table 1.

(6) Evaluation of black heel mark (BHM) resistance:
The operation of applying the copolymer dispersions (compositions for polishing agents) of Examples 1 to 5 and Comparative Examples 1 to 11 on a homogeneous style at a coating amount of 10 g / m ² and drying is repeated three times. This produced a sample for evaluation. This sample for evaluation was installed as a flooring in a place with a lot of traffic (traffic volume = 50 to 100 people / day) for 10 days, and the degree of adhesion of the black heel mark (BHM) was visually observed. Further, the black heel mark (BHM) was evaluated according to the following criteria. The BHM resistance evaluated by such a method is an index for evaluating the gloss maintenance rate and the durability of the film. The results are shown in Table 1. In addition, in the following evaluation criteria, the case of 4 or more was determined to be acceptable, and the case of less than 4 was determined to be unacceptable. The results are shown in Table 1.
5: Adhesion of BHM is not recognized. (10 or less BHM)
4.5: Almost no BHM adhesion is observed (11 to 20 BHM)
4: There is little adhesion of BHM. (21 to 40 BHM)
3: Adhesion of BHM is slightly higher. (41-60 BHM)
2: There is much adhesion of BHM. (61-80 BHM)
1: There is very much adhesion of BHM. (BHM is 81 or more)

(7) Gloss retention:
An evaluation sample was prepared by the same operation as in the evaluation of “black heel mark (BHM) resistance”. For this evaluation sample, the 60 ° reflectance immediately after production (initial gloss) and the 60 ° reflectance after standing for 2 weeks (gloss after standing) were measured, and the gloss maintenance rate (%) was calculated using the following formula. Calculated. The 60 ° reflectance was measured using a micro-TRI-gloss manufactured by Big Gardner. The gloss retention rate (%) is shown in Table 1. The gloss maintenance rate was determined to be 91% or more as acceptable, and less than 91% as unacceptable. The results are shown in Table 1.
Gloss maintenance rate (%) = (Gloss after standing × 100) / (Initial gloss)

(8) Overcoatability:
The operations of applying the copolymer dispersions (the compositions for the polishing agent) of Examples 1 to 5 and Comparative Examples 1 to 11 on a homogeneous style at a coating amount of 10 g / m ² and drying are repeated 5 times. This produced a sample for evaluation. The glossy state on the surface of this evaluation sample was visually observed. The glossy state was evaluated according to the following criteria. The results are shown in Table 1.
Good: No gloss finish Bad: With gloss finish

  INDUSTRIAL APPLICABILITY The present invention can be used as a polishing agent composition used for polishing floor materials and the like and a method for producing the same.

100: Core-shell structure particles, 150: Core part, 200: Shell part, 300: Film, 350: Surface (of film), 500: Floor.

[1] A core-shell structure particle having an average particle diameter of 40 to 200 nm having a core part and a shell part covering the core part, wherein the core part is dissolved in tetrahydrofuran at a glass transition point of −70 to 0 ° C. The insoluble content includes a copolymer (A) of 0 to 20% by mass, the shell portion includes a copolymer (B) having a glass transition point of 20 to 70 ° C., and the core-shell structure particles have a weight average molecular weight. 80000-800000 and Ri insolubles 0-30 wt% der when dissolved in tetrahydrofuran, the core-shell structured particle, when the total of 100 parts by mass of the said core portion and the shell portion, 1 to 10 parts by mass of the copolymer (A), 90 to 99 parts by mass of the copolymer (B), and the copolymer (B) is derived from an αβ unsaturated carboxylic acid monomer. 5 to 30 parts by mass of structural unit It polishes for composition.

In [2] the shell portion, the copolymer (B) is obtained and a monomer of the αβ-unsaturated carboxylic acid monomers than the αβ unsaturated carboxylic acid monomers by copolymerizing The composition for a polishing agent according to the above [1].

[4] Copolymer (A) having a glass transition point of −70 to 0 ° C., an average particle diameter of 20 to 110 nm, and an insoluble content of 0 to 20% by mass when dissolved in tetrahydrofuran is 1 to 10 parts by mass. Under the reaction system, αβ unsaturated carboxylic acid monomer (b1) 5 to 30 parts by mass and monomer (b2) copolymerizable with the αβ unsaturated carboxylic acid monomer 60 to 94 parts by mass [ However, the copolymer (B) is synthesized by emulsion polymerization of (A) + (b1) + (b2) = 100 parts by mass], the core part containing the copolymer (A), and the copolymer production method of the polymer and a shell portion comprising (B), polishes composition insolubles derives its shell structure particles is 0-30% by mass when dissolved in tetrahydrofuran.

Claims (4)

Including core-shell structured particles having an average particle diameter of 40 to 200 nm having a core part and a shell part covering the core part,
The core portion includes a copolymer (A) having a glass transition point of −70 to 0 ° C. and an insoluble content of 0 to 20% by mass when dissolved in tetrahydrofuran,
The shell part includes a copolymer (B) having a glass transition point of 20 to 70 ° C.,
The core-shell structured particle is a composition for a polishing agent having a weight average molecular weight of 80,000 to 800,000 and an insoluble content of 0 to 30% by mass when dissolved in tetrahydrofuran.   In the shell part, the copolymer (B) is obtained by copolymerizing an αβ unsaturated carboxylic acid monomer and a monomer other than the αβ unsaturated carboxylic acid monomer. Item 2. A composition for a polishing agent according to Item 1.   In the said shell part, the said copolymer (B) has a carboxyl group, and contains the polyvalent metal of less than 1 chemical equivalent with respect to this carboxyl group for the polish agent of Claim 1 or 2 Composition.   Reaction system containing 1 to 10 parts by mass of a copolymer (A) having a glass transition point of -70 to 0 ° C., an average particle diameter of 20 to 110 nm, and an insoluble content of 0 to 20% by mass when dissolved in tetrahydrofuran. The αβ unsaturated carboxylic acid monomer (b1) 5 to 30 parts by mass and the αβ unsaturated carboxylic acid monomer copolymerizable with the αβ unsaturated carboxylic acid monomer (b2) 60 to 94 parts by mass [provided that ( A) + (b1) + (b2) = 100 parts by mass]. A method for producing a composition for a polishing agent to obtain a copolymer (B) by emulsion polymerization.

Images