TWI573849B - Composition for gloss agent and fabricating method thereof - Google Patents

Description

Composition for gloss agent and method for producing same

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

A gloss agent is sometimes used in order to protect a floor panel or the like or to maintain a beautiful appearance of a floor material or the like. When the gloss agent is applied to the floor material, a film of the gloss agent is formed on the surface of the floor board, and as a result, the floor board can be provided with gloss. At the same time, the surface of the floor panel is covered by the film of the gloss agent, thereby also preventing damage to the surface of the floor panel.

In addition, floor panels are often stepped on by shoes and the like. Therefore, the film of the gloss agent formed on the surface of the flooring material is required to have durability (for example, it is difficult to peel off from the floor material), or it is difficult to produce a shoe print or the like.

Therefore, as a technique for improving the glossiness and durability and further suppressing the generation of shoe prints and the like, a gloss agent containing an acrylic resin emulsion has been proposed (for example, Patent Document 1 and Patent Document 2).

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-91713

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2005-350543

However, in the above technique, if the gloss agent is applied to the flooring material and it takes a long time, the film formed of the gloss agent may be deteriorated. Further, in the above technique, when a floor material covered with a film of a gloss agent is severely struck by a shoe or the like, a plurality of shoe prints or damages may occur on the floor plate or the film. Further, in the above technique, in the case of overlapping coating, Sometimes there is a drop in gloss.

In view of the above problems, an object of the present invention is to provide a technique relating to a gloss agent which is excellent in performance, durability, and gloss retention for suppressing occurrence of shoe prints, damage, and the like, and even in the case of overlapping coating. It is also not easy to produce a drop in gloss.

The present invention is a composition for a gloss agent shown below and a method for producing the same.

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

[2] The composition for a gloss agent according to the above [1], wherein the copolymer (B) is other than the αβ unsaturated carboxylic acid monomer and the αβ unsaturated carboxylic acid monomer in the shell portion. The monomer is obtained by copolymerization.

[3] The composition for a gloss agent according to the above [1] or [2] wherein, in the shell portion, the copolymer (B) has a carboxyl group and contains less than 1 chemical equivalent relative to the carboxyl group. Price metal.

[4] A method for producing a composition for a glossing agent, wherein the αβ unsaturated carboxylic acid monomer (b1) is 5 parts by mass to 30% by mass in a reaction system containing 1 part by mass to 10 parts by mass of the copolymer (A). And can be compared with the above αβ 60 parts by mass to 94 parts by mass of the monomer (b2) copolymerized with the saturated carboxylic acid monomer [wherein (A) + (b1) + (b2) = 100 parts by mass] is subjected to emulsion polymerization, whereby a copolymer (B) is obtained. The copolymer (A) has a glass transition point of -70 ° C to 0 ° C, an average particle diameter of 20 nm to 110 nm, and an insoluble content when dissolved in tetrahydrofuran is 0% by mass to 20% by mass.

According to the composition for a gloss agent of the present invention, it is excellent in performance, durability, and gloss retention which suppress the occurrence of shoe prints, damage, and the like, and further, it is less likely to cause a decrease in gloss even in the case of overlap coating. According to the method for producing a composition for a brightener of the present invention, the following composition for a glossing agent can be obtained, which is excellent in performance, durability, and gloss retention for suppressing generation of shoe prints, damage, and the like, and even in the case of overlapping coating. It is also not easy to produce a drop in gloss.

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 modifications, corrections, and improvements can be made without departing from the scope of the invention.

1. Composition for glossing agent:

The composition for a gloss agent of the present invention contains core-shell structured particles having a core portion and a shell portion covering the core portion, and having an average particle diameter of 40 nm to 200 nm. In the composition for a gloss agent of the present invention, the core portion contains the copolymer (A), and the glass transition point of the copolymer (A) is -70 ° C to 0 ° C, and the insoluble component when dissolved in tetrahydrofuran (hereinafter referred to as The "THF insoluble component" is 0% by mass to 20% by mass. Further, in the composition for a gloss agent of the present invention, the shell portion contains a copolymer having a glass transition point of from 20 ° C to 70 ° C (B). Furthermore, in the composition for a gloss agent of the present invention, the weight average molecular weight of the core-shell structured particles is from 80,000 to 800,000, and the THF-insoluble component is from 0% by mass to 30% by mass.

When the weight average molecular weight of the core-shell structured particles is from 80,000 to 800,000 and the THF-insoluble content is from 0% by mass to 30% by mass, the core-shell structured particles are contained as in the composition for a gloss agent of the present invention. It is excellent in performance, durability, and gloss retention which suppress the occurrence of shoe prints, damage, and the like, and further causes a decrease in gloss even in the case of overlap coating; the core-shell structure particles have a core portion and a shell portion, and the core portion contains The glass transition point is -70 ° C to 0 ° C and the THF insoluble component is 0% by mass to 20% by mass of the copolymer (A), and the shell portion contains the copolymer (B) having a glass transition point of 20 ° C to 70 ° C.

Further, from the viewpoint of further improving durability and gloss retention, the composition for a gloss agent of the present invention preferably has a core portion containing a glass transition point of -70 ° C to 0 ° C and a THF insoluble content of 0% by mass. 20% by mass of the copolymer (A), and the shell portion contains the copolymer (B) having a glass transition point of 20 ° C to 70 ° C.

Further, in the composition for a gloss agent of the present invention, the cured product obtained by drying the copolymer (A) contained in the core portion of the core-shell structured particles at room temperature is preferably a paste, because the durability is exhibited. It is excellent, and when the film formed from the composition for a gloss agent is subjected to an impact, the effect of buffering the impact can be further enhanced. The "paste" as used in the present specification means that when the copolymer (A) is dried at room temperature, the film which is restored with respect to deformation is not formed, and the film is in a semi-solid state.

Fig. 1 is a cross-sectional view showing a core-shell structured particle 100 contained in an embodiment of a composition for a gloss agent of the present invention. As shown in the figure, in the core-shell structured particle 100 contained in the composition for a glossing agent of the present embodiment, the core portion 150 is present at the center portion. Further, the periphery of the core portion 150 is covered by the shell portion 200.

Fig. 2 is an explanatory view showing a use aspect of the composition for a glossing agent of the embodiment. When the composition for a glossing agent of the present embodiment is used, it is applied to the floor panel 500 or the like to form a film 300 containing a composition for a glossing agent.

As shown in the figure, in the film 300 formed of the composition for a gloss agent of the present embodiment, a plurality of core-shell structure particles 100 are dispersed throughout the film 300. When the surface of the floor panel 500 is covered with such a film 300, the surface of the floor panel 500 can be lighted by the action of the core-shell structure particles 100 contained in the film 300.

The core portion 150 of the core-shell structured particle 100 contained in the composition for a gloss agent of the present embodiment contains a copolymer (A) having a glass transition point (-70) lower than room temperature (20 ° C). °C~0°C) and the THF-insoluble component is 0% by mass to 20% by mass, so it is soft at room temperature (20°C), and as a result, it can exert a buffering effect on impact. Therefore, when the film composition 300 is formed on the surface of the floor panel 500 in advance using the composition for a gloss agent of the present embodiment, even if the floor surface 500 or the film 300 is strongly impacted in a normal environment, it can be used by the core. The buffering action of the core portion 150 of the shell structure particles 100 suppresses damage to the floor panel 500 or the film 300.

In general, the glass transition point of the copolymer (A) [glass transition point: -70 ° C to 0 ° C] contained in the composition for a gloss agent of the present embodiment is lower than room temperature. In the case of (20 ° C), it will become sticky at room temperature (20 ° C). In the composition for a gloss agent of the present embodiment, the core portion 150 containing the copolymer (A) is coated by the shell portion 200. Therefore, it is possible to prevent the core portion 150 containing the copolymer (A) from being exposed on the surface 350 of the film 300 formed of the composition for a gloss agent of the present embodiment. Further, since the copolymer (B) contained in the shell portion 200 has a glass transition point (20 ° C to 70 ° C) at room temperature (20 ° C) or higher, it is not easily tacky. As a result, the surface 350 of the film 300 formed of the composition for a gloss agent of the present embodiment is sticky. When the adhesion of the surface 350 of the film 300 is suppressed, dust or the like is less likely to adhere to the surface 350 of the film 300. Therefore, it is possible to suppress the adhesion of dirt on the surface of the floor panel 500 and the film 300, or the shoe print due to adhesion of dirt. produce.

In particular, since the film 300 formed of the composition for a gloss agent of the present embodiment has the cushioning action of the core portion 150, even if the floor panel 500 or the film 300 is severely stepped on the sole, or a heavy table or chair is placed In this case, the pressure from the soles of the soles and the table or chair can be alleviated. Therefore, if the floor panel 500 is covered with the film 300 of the composition for a gloss agent of the present embodiment in advance, even if dirt is present on the sole or the foot of the table or the chair, the dirt can be pressed against the floor 500. The pressure on the surface of the film 300 is weakened, and as a result, the dirt adhering to the soles of the sole or the table is less likely to adhere to the floor panel 500 and the film 300. In other words, when the floor panel 500 is covered with the film 300 of the composition for a brightener of the present embodiment, it is possible to suppress the occurrence of shoe prints and the like on the surfaces of the floor panel 500 and the film 300.

In the composition for a gloss agent of the present embodiment, the core-shell structure particles The average particle diameter of 100 is 40 nm to 200 nm. When the average particle diameter of the core-shell structure particles 100 is 40 nm to 200 nm as in the composition for a gloss agent of the present embodiment, even when the film 300 of the composition for a gloss agent is formed, the composition for a gloss agent is overcoated. On the floor panel 500, it is also easy to uniformly disperse the core-shell structure particles 100 throughout the entire film 300, and as a result, the occurrence of gloss reduction can be suppressed.

In the composition for a gloss agent of the present invention, it is preferred to use a copolymer in the core portion from the viewpoint of suppressing damage to the surface of the film formed of the composition for a gloss agent or the surface of the floor material covered by the film. The glass transition point of A) is -60 ° C ~ -10 ° C, and more preferably -50 ° C ~ -20 ° C.

In the composition for a gloss agent of the present invention, the average particle diameter of the copolymer (A) in the core portion is preferably from 20 nm to 110 nm, more preferably from 30 nm to 90 nm, and most preferably from 30 nm to 60 nm. It is that the overlap coating property can be improved more reliably. In addition, the term "overlap coating property" as used in the present specification refers to a case where a coating film is formed by superimposing a composition for a gloss agent to form a coating film, and the coating film is dried to form a film. The performance of suppressing the decrease in gloss is suppressed. In the case where the overlap coating property is improved, even if the gloss agent composition is superposed and coated in multiple layers, the occurrence of gloss reduction can be intentionally suppressed.

In the composition for a gloss agent of the present invention, the copolymer (A) contained in the core portion is preferably a (meth)acrylic copolymer because the copolymerization property is good and the adjustment of the glass transition point is easy. . In addition, the term "copolymerization" as used herein means a property of easily copolymerizing two or more kinds of monomers [a specific example of the (meth)acrylic copolymer will be described later].

In the composition for a gloss agent of the present invention, preferably, in the shell portion, 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 reason for this is that it is possible to improve the durability or more reliably suppress the generation of shoe prints and the like (a specific example of the monomer other than the αβ unsaturated carboxylic acid monomer and the αβ unsaturated carboxylic acid monomer will be described later).

In the composition for a gloss agent of the present invention, it is preferred that the copolymer (B) has a carboxyl group in the shell portion and contains a polyvalent metal of less than 1 chemical equivalent with respect to the carboxyl group, because the durability can be improved. Sexually or more reliably suppresses the generation of shoe prints and the like, and the stability of the composition for a gloss agent can be improved (a specific example of a polyvalent metal will be described later).

In the composition for a gloss agent of the present invention, it is preferred that the glass transition point of the copolymer (B) in the shell portion is 30 ° C to 70 ° C, and more preferably 40 ° C to 60 ° C. It is more reliably suppressed that a shoe print or the like is generated on the surface of the film formed of the composition for a gloss agent.

In the composition for a gloss agent of the present invention, it is preferable that the core-shell structure particles have a core portion of from 1 part by mass to 10 parts by mass, and the shell portion is set to 100 parts by mass. The reason is 90 parts by mass to 99 parts by mass, because the durability is favorably exhibited, and the polymerization stability is favorably imparted when the core-shell structured particles are produced.

In the composition for a gloss agent of the present invention, the THF-insoluble component of the core-shell structured particles is preferably 0% by mass to 20% by mass, because the overlap coating property can be improved.

The composition for a gloss agent of the present invention described so far can be obtained, for example, by the following production method.

2. Method for producing a composition for a gloss agent:

In the method for producing a composition for a brightener of the present invention, the αβ unsaturated carboxylic acid monomer (b1) is 5 parts by mass to 30 parts by mass in a reaction system containing 1 part by mass to 10 parts by mass of the copolymer (A). And 60 parts by mass to 94 parts by mass of the monomer (b2) copolymerizable with the above αβ unsaturated carboxylic acid monomer, wherein (A)+(b1)+(b2)=100 parts by mass, emulsion polymerization is carried out. This obtained the copolymer (B) in which the glass transition point of the copolymer (A) was -70 ° C to 0 ° C, the average particle diameter was 20 nm to 110 nm, and the THF insoluble content was 0% by mass to 20% by mass.

In the method for producing a composition for a brightener of the present invention, core-shell structured particles obtained by covering a periphery of a core portion containing the copolymer (A) with a shell portion containing the copolymer (B) can be obtained. form.

The copolymer (A) which can be used in the method for producing a composition for a brightener of the present invention is, for example, a (meth)acrylic copolymer. Further, the (meth)acrylic copolymer usable as the copolymer (A) in the present invention can be obtained, for example, by mixing the following monomer mixture with an emulsifier, whereby the monomer is previously dispersed in the monomer In the emulsifier, a polymerization initiator such as a persulfate is added to carry out emulsion polymerization; and the monomer mixture is one or more monomers corresponding to alkyl (meth)acrylate, and further one or more equivalent to αβ unsaturated carboxylic acid A monomer of any one of an acid monomer, an aromatic vinyl monomer, and a polyfunctional monomer is mixed [at least a (meth)acrylic acid alkyl ester, and further contains an αβ unsaturated carboxylic acid monomer, aroma a monomer mixture of at least one of a group of vinyl monomers and a polyfunctional monomer].

The above (meth)acrylic copolymer which can be used as the copolymer (A) In the "alkyl (meth) acrylate" of the raw material, alkyl acrylate may, for example, be methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate or tributyl acrylate. , n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate and lauryl acrylate. Further, in the "alkyl (meth)acrylate" which is a raw material of the (meth)acrylic copolymer, examples of the alkyl methacrylate include methyl methacrylate, ethyl methacrylate, and methacrylic acid. Isopropyl ester, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, Lauryl methacrylate and trimethyl decyl methacrylate. Among the monomers exemplified herein, at least one of n-butyl acrylate, 2-ethylhexyl acrylate, and methyl methacrylate is preferably used as the (meth) copolymer (A). The reason why the raw material of the acrylic copolymer is used in the present invention is that it is a versatile raw material and has good copolymerizability, and suppresses the occurrence of damage or suppresses the surface of the film formed of the composition for a gloss agent. The performance of the shoe prints and the like is improved.

Examples of the "αβ unsaturated carboxylic acid monomer" which is a raw material of the (meth)acrylic copolymer which can be used as the copolymer (A) include acrylic acid, methacrylic acid, crotonic acid, vinyl acetic acid, and itacon. Acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid, and the like. Among the monomers enumerated herein, it is preferred to use at least acrylic acid and methacrylic acid as raw materials of the (meth)acrylic copolymer which can be used as the copolymer (A) in the present invention because It is a raw material which is versatile and has good copolymerization property, and adjustment of an acid value is easy.

The above (meth)acrylic copolymer which can be used as the copolymer (A) Examples of the "aromatic vinyl monomer" of the raw material include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, o-ethylstyrene, p-ethylstyrene, and α. -chlorostyrene, p-chlorostyrene, p-methoxystyrene, p-aminostyrene, p-ethoxylated styrene, sodium styrene sulfonate, α-vinylnaphthalene, 1-vinylnaphthalene-4 Sodium sulfonate, 2-vinyl fluorene, 2-vinyl pyridine, 4-vinyl pyridine, and the like. Among the monomers enumerated herein, from the viewpoint of being a versatile raw material and imparting gloss, it is preferred that at least styrene is used as the (meth)acrylic copolymer which can be used as the copolymer (A). The raw materials are used in the present invention.

Examples of the "polyfunctional monomer" which is a raw material of the (meth)acrylic copolymer which can be used as the copolymer (A) include allyl methacrylate, diallyl phthalate, and trimerization. Triallyl cyanate, triallyl cyanurate, divinylbenzene, ethylene glycol dimethacrylate, butanediol diacrylate, hexamethylene glycol dimethacrylate, etc. . Among the monomers enumerated herein, at least one of allyl methacrylate, divinylbenzene, and ethylene glycol dimethacrylate is preferably used as the copolymer (A). The reason for using the raw material of the acryl-based copolymer in the present invention is that the copolymerization property is good, and it is easy to adjust the THF-insoluble component which is important in terms of improving durability and gloss retention.

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

In addition, the αβ unsaturated carboxylic acid monomer (b1) which can be used in the method for producing a composition for a brightener of the present invention is exemplified by acrylic acid and methacryl. Semi-esters such as acid, itaconic acid, maleic acid, fumaric acid, and mono[2-(methyl)propenyloxyethyl] phthalate, succinic acid mono [2-(methyl) Acryloxyethyl]ester, carboxyethyl acrylate, and the like. The αβ unsaturated carboxylic acid monomer (b1) exemplified herein may be used in the present invention in a single type or in combination of two or more. In particular, in the αβ unsaturated carboxylic acid monomer (b1) exemplified above, it is preferred that the stability at the time of polymerization is improved and the durability of the obtained composition for a gloss agent is improved. At least any one of acrylic acid and methacrylic acid is used in the present invention.

Further, examples of the monomer (b2) which can be used in the method for producing a composition for a brightener of the present invention include acrylate monomers (specific examples are n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, acrylic acid - 2-ethylhexyl ester, n-octyl acrylate, isodecyl acrylate, lauryl acrylate, and the like. Among the monomers exemplified herein, the film formed of the composition for a gloss agent suppresses the occurrence of damage to the flooring material or the like, or suppresses the occurrence of shoe print on the surface of the film formed of the composition for the gloss agent. In other words, at least one of n-butyl acrylate and isobutyl acrylate is preferably used as the monomer (b2) in the present invention.

Further, examples of the monomer (b2) which can be used in the method for producing a composition for a brightener of the present invention include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, and isopropyl acrylate. An alkyl-based unsaturated monomer such as an alkyl acrylate or an alkyl methacrylate having an alkyl group having 3 or less carbon atoms such as isopropyl methacrylate; or a (meth)acrylic acid ring such as cyclohexyl (meth)acrylate; Alkyl ester; aromatic (meth) acrylate such as phenoxyalkyl (meth) acrylate or benzyl (meth) acrylate; hydroxyalkyl acrylate Ester, hydroxyalkyl methacrylate, polyoxyethylene (meth) acrylate, methoxyethyl acrylate, ethoxymethyl acrylate, glycidyl acrylate, glycidyl methacrylate, etc. (methyl) Acrylate; (meth) propylene such as acrylamide, methacrylamide, N-methylol acrylamide, N-methoxymethyl acrylamide, N-methoxybutyl acrylamide Indoleamine; vinyl methyl ketone, vinyl ethyl ketone, vinyl n-propyl ketone, vinyl isopropyl ketone, vinyl n-butyl ketone, vinyl isobutyl ketone, vinyl tert-butyl ketone a radical polymerizable monomer containing an aldehyde group and/or a ketone group such as a vinyl phenyl ketone, a vinyl benzyl ketone, a divinyl ketone or a diacetone acrylamide; (meth)acrylonitrile, butenenitrile a nitrile group-containing unsaturated compound such as 2-cyanoethyl (meth)acrylate, 2-cyanopropyl (meth)acrylate or 3-cyanopropyl (meth)acrylate; Polyfunctional monomers such as benzene, (poly)ethylene glycol di(meth)acrylate, allyl methacrylate; styrene, o-vinyl benzene, m-vinyl benzene, pair B Monovinyl aromatic compounds such as alkenylbenzene, p-ethylvinylstyrene, α-methylstyrene, α-fluorostyrene; halogenated vinyls such as vinyl chloride and vinylidene chloride; and ethylene such as vinyl propionate Esters and the like. Among the monomers exemplified herein, the film formed of the composition for a gloss agent suppresses the occurrence of damage to the flooring material or the like, or suppresses the occurrence of shoe print on the surface of the film formed of the composition for the gloss agent. In other words, at least one of methyl methacrylate and cyclohexyl (meth)acrylate is preferably used as the monomer (b2) in the present invention.

Further, in the method for producing a composition for a brightener of the present invention, an aromatic vinyl monomer (for example, styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, or the like) may be used. O-ethyl styrene, p-ethyl benzene Ethylene, α-chlorostyrene, p-chlorostyrene, p-methoxystyrene, p-aminostyrene, p-ethoxylated styrene, sodium styrene sulfonate, α-vinylnaphthalene, 1-vinyl Sodium naphthalene-4-sulfonate, 2-vinyl anthracene, 2-vinylpyridine, 4-vinylpyridine or the like) is used as the monomer (b2). In particular, among the monomers exemplified herein, it is preferable to use a styrene-based single article as a raw material of another resin composition, which is excellent in versatility, and can suppress the production cost, and can improve gloss. The body is used as the monomer (b2) in the present invention.

In the method for producing a composition for a brightener of the present invention, the αβ unsaturated carboxylic acid monomer (b1), the monomer (b2), and the molecular weight may be adjusted in the presence of the copolymer (A) during emulsion polymerization. The pre-emulsion is prepared in advance by mixing an agent, water, or the like, and emulsification by adding an emulsifier thereto. Further, by using the pre-emulsion, the polymerization reaction is usually carried out in an inert atmosphere. As a result, a copolymer dispersion containing core-shell structured particles having a core portion containing a copolymer (A) and a shell portion [containing a copolymer (B) which contains α? A monomer mixture of the unsaturated carboxylic acid monomer (b1) and the monomer (b2) is formed].

Further, in the method for producing a composition for a brightener of the present invention, the emulsion polymerization reaction can be carried out while continuously or intermittently supplying the pre-emulsion and the polymerization initiator to the reaction system.

The polymerization initiator which can be used in the method for producing a composition for a brightener of the present invention may, for example, be a persulfate or a redox polymerization initiator. In the method for producing a composition for a brightener of the present invention, as the polymerization initiator, only persulfate may be used, or a persulfate and a redox polymerization initiator may be used in combination. The redox polymerization initiator described herein means that it will be oxidized. A polymerization initiator which is a combination of a reducing agent and a reducing agent.

In the method for producing a composition for a brightener of the present invention, examples of the oxidizing agent used in the redox polymerization initiator include persulfate such as potassium persulfate, sodium persulfate or ammonium persulfate; and hydrogen peroxide; Tert-butyl hydroperoxide, tert-butylperoxymaleic acid, peroxysuccinic acid, benzammonium peroxide, cumene hydroperoxide, diisopropyl peroxydicarbonate, Peroxyphenyl neodecanoate, cumene peroxyoctanoate, dicumyl hydroperoxide, hydroperoxide, menthane, 2,2-bis(4,4-di-t-butyl A peroxide such as cyclohexyl)propane is oxidized.

On the other hand, in the method for producing a composition for a brightener of the present invention, examples of the reducing agent used in the redox polymerization initiator include acidic sodium sulfite, sodium dithionite, sodium thiosulfate, and white powder ( Rongalite), ascorbic acid, reducing sugars such as fructose, iron salts such as ferrous sulfate and ferric sulfate. Further, in the method for producing a composition for a glossing agent of the present invention, when the reducing agent is used in a redox polymerization initiator, a chelating agent such as sodium edetate may be used in combination as needed.

In the method for producing a composition for a brightener of the present invention, in the case of using a redox polymerization initiator, the oxidizing agent used in the redox polymerization initiator may be only one kind [for example, as enumerated above). One of the oxidizing agents such as potassium sulfate may be mixed with a plurality of [for example, two or more kinds of oxidizing agents such as potassium persulfate listed above]. Further, in this case, the reducing agent used in the redox polymerization initiator may be only one kind [such as one of the reducing agents such as the above-exemplified acidic sodium sulfite], or may be mixed in a plurality [for example, Two of the reducing agents such as acidic sodium sulfite listed the above].

In the method for producing a composition for a brightener of the present invention, when a redox polymerization initiator is used in the polymerization reaction, a preferred combination of the above-exemplified oxidizing agent, reducing agent, and chelating agent is exemplified. The combination of the following two groups (combination A, combination B).

(combination A) persulfate, acid sodium sulfite, ferrous sulfate

(combination B) tributyl peroxide, acid sodium sulfite, ferrous sulfate

In the method for producing a composition for a brightener of the present invention, in the case of using a redox polymerization initiator, the copolymer (A), the αβ unsaturated carboxylic acid monomer (b1), and the monomer (b2) are used. 100 parts by mass of the total amount of the redox polymerization initiator is preferably from 0.01 part by mass to 5.0 parts by mass, more preferably from 0.01 part by mass to 3.0 parts by mass, particularly preferably from 0.1 part by mass to 2.0. The reason for the mass portion is that durability can be imparted to the obtained composition for a glossing agent (or a film formed of a composition for a glossing agent), or stability with time can be improved. Further, in the method for producing a composition for a brightener of the present invention, in the case where the oxidizing agent used in the redox polymerization initiator is only a persulfate, it is preferably relative to the copolymer (A), αβ. 100 parts by mass of the total of the unsaturated carboxylic acid monomer (b1) and the monomer (b2), and the use ratio of the redox polymerization initiator are 0.1 parts by mass to 1.0 part by mass.

In the method for producing a composition for a brightener of the present invention, examples of the emulsifier which can be used in the polymerization reaction include polyoxyethylene alkyl ether, polyoxyethylene alkyl sulfate, and polyoxyethylene polycyclic phenyl ether sulfate. Ester salt, polyoxyethylene oxide A surfactant such as sodium succinate, sodium lauryl sulfate or sodium dodecylbenzenesulfonate.

In the method for producing a composition for a brightener of the present invention, the copolymer (A) is improved from the viewpoint of improving the polymerization stability and the particle size of the obtained core-shell structured particles to be controlled to a desired size. The total amount of the αβ unsaturated carboxylic acid monomer (b1) and the monomer (b2) is 100 parts by mass, and the use ratio of the emulsifier is preferably 0.2 parts by mass to 7.0 parts by mass, and more preferably 0.3 parts by mass to 5.0. The parts by mass are particularly preferably from 0.5 part by mass to 3.0 parts by mass.

In the method for producing a composition for a brightener of the present invention, examples of the molecular weight modifier which can be used in the polymerization reaction include butyl mercaptan, dodecyl mercaptan, octyl mercaptoacetate, isopropanol, methanol, and tetra. Carbon chloride and the like.

In the method for producing a composition for a brightener of the present invention, when a molecular weight modifier is used, the composition for a gloss agent (or a film formed of a composition for a gloss agent) can be improved by adjusting the molecular weight. From the viewpoint of durability, the molecular weight modifier is preferably used in an amount of 0.001 by mass based on 100 parts by mass of the total of the copolymer (A), the αβ unsaturated carboxylic acid monomer (b1), and the monomer (b2). The amount is preferably 0.80 parts by mass, more preferably 0.005 parts by mass to 0.60 parts by mass, and particularly preferably 0.01 parts by mass to 0.40 parts by mass.

In the method for producing a composition for a brightener of the present invention, the core-shell structured particles contained in the obtained copolymer dispersion (the composition for a gloss agent) can be set by appropriately selecting the type or the use ratio of the molecular weight modifier. The desired weight average molecular weight (Mw), the amount of THF insoluble component required.

In the method for producing a composition for a brightener of the present invention, it is preferred to further add a polyvalent metal compound in the form of a slurry or a chelating liquid to the copolymer dispersion in which the core-shell structured particles are dispersed. The following composition for a glossing agent can be obtained: the obtained composition for a glossing agent (or a film formed of a composition for a glossing agent) has high durability and stability, and can suppress the generation of shoe prints and the like more effectively.

In the method for producing a composition for a brightener of the present invention, a polyvalent metal compound which can be added after preparing a copolymer dispersion containing core-shell structured particles is exemplified by zinc oxide, calcium oxide, calcium hydroxide, and aluminum hydroxide. Zinc carbonate, calcium carbonate, Mg(OH) ₂ , MgO, MgCO ₃ and Mg(OH) ₂ . 3H ₂ O, zinc ammonium acetate, zinc amide ammonia, zinc malate ammonia, calcium alanine ammonia, and the like.

In the case where a polyvalent metal compound is used in the method for producing a composition for a glossing agent of the present invention, the copolymer is adjusted with respect to the viscosity of the composition for a glossing agent and the improvement of the addition/mixing stability. A), the total amount of the αβ unsaturated carboxylic acid monomer (b1) and the monomer (b2) is 100 parts by mass, and the use ratio of the polyvalent metal compound is preferably 0.5 parts by mass to 7.0 parts by mass, and more preferably 1.0 mass%. It is preferably 5.0 parts by mass, and particularly preferably 1.5 parts by mass to 4.0 parts by mass.

In the method for producing a composition for a glossing agent of the present invention, the type of the polyvalent metal or the ratio of use is appropriately selected, and when the composition for a glossing agent is used, in the process of drying the coating film of the composition for a glossing agent, The copolymer (B) contained in the shell portion of the core-shell structured particles is crosslinked with the polyvalent metal, and as a result, various properties such as durability, water resistance, and peelability can be more reliably improved.

[Example]

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to the examples.

(1) Preparation of a composition for a glossing agent:

(Example 1 to Example 5, Comparative Example 2 to Comparative Example 8, Comparative Example 10, and Comparative Example 11)

With respect to Examples 1 to 5, Comparative Example 2 to Comparative Example 8, Comparative Example 10, and Comparative Example 11, each monomer (a) was mixed in the formulation shown in Table 1, and emulsion polymerization was carried out to obtain a core portion. Copolymer (A). In Table 1, the numerical values shown in the column of each monomer (a) are the amounts of the monomer (a) in terms of "parts by mass". Further, in Table 1, in the column of each monomer (a), the case where "-" is shown instead of a numerical value means that the monomer (a) is not used.

Specifically, first, a non-reactive emulsifier [Emal 2FG or Latemul E-118B (all manufactured by Kao Co., Ltd.)] or a reactive emulsifier [KH-1025 (First Industrial Pharmaceuticals) is added to the reaction vessel. Ltd.), water and monomer (a), while stirring under a nitrogen stream, the temperature of the liquid is raised to 65 °C. Thereafter, an aqueous catalyst solution (0.5% aqueous ammonium persulfate solution) was added and reacted for 0.75 hours, whereby a copolymer (A) of a core portion was obtained.

Further, in the presence of the copolymer (A) in the core portion, the monomer (b) was subjected to emulsion polymerization in the formulation shown in Table 1, thereby synthesizing the copolymer (B) in the shell portion to obtain a core-shell structured particle. Copolymer dispersion (composition for gloss). In Table 1, the numerical values shown in the column of each monomer (b) are the amounts of the monomer (b) in terms of "parts by mass". In addition, in Table 1, in the column of each monomer (b), when "-" is shown, it is not a numerical value. It means that the monomer (b) is not used.

Specifically, a mixed solution of the monomer (b), 24 parts by mass of water, and 0.9 parts by mass of a reactive or non-reactive emulsifier are mixed and stirred to carry out pre-emulsification, thereby obtaining a pre-emulsion. Then, the pre-emulsion and the aqueous catalyst solution (0.25% aqueous ammonium persulfate solution) were simultaneously added dropwise to the dispersion of the copolymer (A) containing the core portion at about 3 hours at 75 ° C, and the addition was continued after the completion of the dropwise addition. The copolymer dispersion containing the core-shell structured particles was obtained by holding at 85 ° C for about 2 hours.

Then, in Examples 1 to 3 and Comparative Examples 2 to 8, 8 and Comparative Example 11, the carboxyl group of the copolymer (B) contained in the shell portion of the core-shell structure particles was less than 1 chemical. In a manner equivalent to Zn, a Zn-containing chelating solution or ZnO slurry was added at 80 ° C in a copolymer dispersion containing core-shell structured particles. Further, in Example 5, the copolymer dispersion containing the core-shell structured particles was contained in a manner of containing less than 1 chemical equivalent of Mg 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 at 80 °C.

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

(Comparative Example 1 and Comparative Example 9)

In Comparative Example 1 and Comparative Example 9, the monomer (b) having the formulation shown in Table 1 was subjected to emulsion polymerization to obtain a copolymer dispersion (a composition for a gloss agent) containing a copolymer.

The contents of the abbreviations related to the monomer (a) and the monomer (b) shown in Table 1 are as follows.

BA: butyl acrylate [manufactured by Wako Pure Chemical Industries Co., Ltd.]

2EHA: 2-ethylhexyl acrylate [manufactured by East Asia Synthetic Co., Ltd.]

ST: styrene [Mitsubishi Chemical Co., Ltd.]

MAA: Methacrylic acid [Manufactured by Kuraray Co., Ltd.]

AMA: allyl methacrylate [Mitsubishi Gas Chemical Co., Ltd.]

EDMA: ethylene glycol dimethacrylate [manufactured by Shin-Nakamura Chemical Industry Co., Ltd.]

MMA: Methyl methacrylate [Mitsubishi Riyang (stock) manufacturing]

CHMA: cyclohexyl methacrylate [Mitsubishi Laiyang Co., Ltd.]

AA: Acrylic [East Asian Synthetic (Stock) Manufacturing]

NASS: sodium p-styrene sulfonate [Tosoh Organic Chemicals Co., Ltd.]

DVB: DVB-570 [Nippon Steel Chemical Co., Ltd.]

(2) Determination of average particle size:

The average particle diameter is obtained by measuring a Stokes diameter which is a diffusion coefficient D detected by a dynamic light scattering method by FPAR-1000 [manufactured by Otsuka Electronics Co., Ltd.]. (m ² /s) was obtained by the Stokes-Einstein type (the following formula (I)).

Formula (I): d=kT/3πη ₀ D

[In the formula (I), d is an average particle diameter (m), k is a Boltzmann constant (=1.3806488×10 ^-23 J/K), T is an absolute temperature (K), and η ₀ is a viscosity of a solvent ( Pa.s)]

The average particle diameter (nm) of the copolymer (A) of the core portion obtained in Examples 1 to 5, Comparative Example 2 to Comparative Example 8, Comparative Example 10, and Comparative Example 11, Examples 1 to 5, and Comparative Example 2 The average particle diameter (nm) of the core-shell structured particles obtained in Comparative Example 8, Comparative Example 10, and Comparative Example 11 and the average particle diameter (nm) of the copolymer obtained in Comparative Example 1 and Comparative Example 9 are shown in Table 1. in.

(3) Determination of glass transfer point:

In the measurement of the glass transition point, first, 1 g to 10 g of the copolymer was thinly stretched on a glass plate, and dried at 25 ° C for 3 days, thereby obtaining a dried film. Then, the obtained dried film was subjected to a differential scanning calorimeter (TA Instruments (manufactured by TA Instruments, MDSC Q200 type)) under a nitrogen atmosphere at a temperature rising rate of 20 ° C / min and a temperature range of -90 ° C to 100 ° C. The measurement was carried out. Tested under the condition that the amount of the sample is 5 mg to 10 mg. set. The intermediate temperature of the inflection start point and the end point of the differential curve of the differential scanning calorimetry obtained by the measurement is taken as the glass transition point (Tg) (° C.) [The glass transition point (Tg) (° C.) measured by the above method is taken as "Glass transfer point (°C)" as described in this manual]. Further, as for the copolymer which is thinly extended on the glass plate as a sample, the products of the polymerization reaction in each stage of each of the above examples and the respective comparative examples were used as they were. The glass transition points of the copolymer (A) of the core portion obtained in Examples 1 to 5, Comparative Example 2 to Comparative Example 8, Comparative Example 10, and Comparative Example 11, Examples 1 to 5, and Comparative Examples 2 to Comparative Examples 8. The glass transition point of the copolymer (B) of the shell portion obtained in Comparative Example 10 and Comparative Example 11 and the glass transition point (°C) of the copolymer obtained in Comparative Example 1 and Comparative Example 9 are shown in Table 1.

(4) Determination of tetrahydrofuran insoluble components (THF insoluble components):

In the method for measuring an insoluble component (THF-insoluble component) when dissolved in tetrahydrofuran, the core-containing copolymers of Examples 1 to 5 and Comparative Examples 2 to 8, 8 and Comparative Example 11 were first placed ( Copolymer dispersion of A) [Reaction product obtained by copolymerization of monomer (a)], core-shell structure of Examples 1 to 5 and Comparative Example 2 to Comparative Example 8, Comparative Example 10, and Comparative Example 11 The copolymer dispersion of the particles (the composition for the gloss agent) and the copolymer dispersion (the composition for the gloss agent) of Comparative Example 1 and Comparative Example 9 were respectively applied to a plastic tray (AS-1 (share)) Manufactured on Dispotray DT-1), dried at room temperature to produce a film. Then, 0.15 g of the film was added to 50 mL of tetrahydrofuran, and the mixture was stirred for 16 hours to be dissolved. The obtained solution was filtered using two kinds of filter papers corresponding to JISP 3801, and then 10 mL of the filtrate was dried. Then, the insoluble component (gel fraction) was calculated from the weight after drying. The copolymer (A) of the core portion of Examples 1 to 5 and Comparative Example 2 to Comparative Example 8, Comparative Example 10, and Comparative Example 11, Examples 1 to 5, Comparative Example 2 to Comparative Example 8, and Comparative Example 10, The THF-insoluble components (wt%) of the core-shell structured particles of Comparative Example 11 and the copolymers of Comparative Example 1 and Comparative Example 9 are shown in Table 1.

(5) Determination of weight average molecular weight:

The core-shell structured particle-containing copolymer dispersion (the composition for a gloss agent) of Examples 1 to 5 and Comparative Example 2 to Comparative Example 8, Comparative Example 10, and Comparative Example 11 and the contents of Comparative Example 1 and Comparative Example 9 The weight average molecular weight of the copolymer dispersion of the copolymer (the composition for the gloss agent), and the composition was immersed in tetrahydrofuran at room temperature for 24 hours, and then measured by a gel permeation chromatograph [Gel Permeation Chromatography, GPC]. The weight average molecular weight of the tetrahydrofuran-dissolved component was evaluated. The results are shown in Table 1.

(6) Black Heel Mark (BHM) evaluation:

The copolymer dispersions of the examples 1 to 5 and the comparative examples 1 to 11 (the composition for a gloss agent) were applied onto a homogeneous tile at a coating amount of 10 g/m ² and dried. This operation was repeated 3 times to prepare a sample for evaluation. The sample for evaluation was set as a flooring material at a place where the flow rate of humans was large (passage amount = 50 persons/day to 100 persons/day) for 10 days, and the degree of adhesion of black shoe print (BHM) was visually observed. Further, the black shoe print (BHM) was evaluated on the basis of the following criteria. The BHM resistance evaluated by this method is an index for evaluating the gloss retention rate or the durability of the film. The results are shown in Table 1. In addition, the case of 4 or more of the following evaluation criteria was judged as pass, and the case of less than 4 was judged to be unacceptable. The results are shown in Table 1.

5: Adhesion of BHM was not confirmed. (BHM is 10 or less)

4.5: Almost no adhesion to BHM was confirmed (BHM was 11 to 20)

4: BHM has less adhesion. (BHM is 21~40)

3: BHM has a little more adhesion. (BHM is 41 to 60)

2: BHM has a lot of adhesion. (BHM is 61 to 80)

1: BHM has a lot of adhesion. (BHM is 81 or more)

(7) Gloss retention:

A sample for evaluation was produced by the same operation as the case of the evaluation of "BHM resistance". The evaluation sample was measured for the 60° reflectance (initial gloss) immediately after the preparation and the 60° reflectance (gloss after placement) after leaving for 2 weeks, and the gloss retention ratio (%) was calculated using the following calculation formula. Further, the 60° reflectance was measured using a micro-TRI-gloss manufactured by BYK Gardner. The gloss maintenance ratio (%) is shown in Table 1. Further, regarding the gloss retention ratio, 91% or more was judged as pass, and less than 91% was judged as unacceptable. The results are shown in Table 1.

Gloss retention rate (%) = (gloss after placement × 100) / (initial gloss)

(8) Overlap coating properties:

The copolymer dispersions of the examples 1 to 5 and the comparative examples 1 to 11 (the composition for a gloss agent) were applied onto a homogeneous ceramic tile at a coating amount of 10 g/m ² and dried, and this operation was repeated 5. Then, a sample for evaluation was prepared. The gloss-reduced state of the surface of the sample for evaluation was visually observed. The gloss reduction state was evaluated on the basis of the following criteria. The results are shown in Table 1.

Good: no gloss drop

Bad: shiny drop

[Industrial availability]

The present invention can be used as a composition for a glossing agent for glazing of a flooring material or the like and a method for producing the same.

100‧‧‧ core-shell structured particles

150‧‧‧Nuclear Department

200‧‧‧Shell Department

300‧‧ ‧ film

350‧‧‧ (film) surface

500‧‧‧floor

Fig. 1 is an explanatory view of core-shell structured particles contained in an embodiment of a composition for a gloss agent of the present invention.

Fig. 2 is an explanatory view showing a use aspect of an embodiment of a composition for a gloss agent of the present invention.

100‧‧‧ core-shell structured particles

150‧‧‧Nuclear Department

200‧‧‧Shell Department

Claims (3)

A composition for a gloss agent, comprising core-shell structured particles having a core portion and a shell portion covering the core portion, and having an average particle diameter of 40 nm to 200 nm, wherein the core portion contains a glass transition point of -70 a copolymer (A) having an insoluble content of 0% by mass to 20% by mass when dissolved in tetrahydrofuran at °C to 0° C., and a copolymer (B) having a glass transition point of 20° C. to 70° C., the core The weight average molecular weight of the shell structure particles is 80,000 to 800,000, and the insoluble content when dissolved in tetrahydrofuran is 0% by mass to 30% by mass, and when the total amount of the core portion and the shell portion is 100 parts by mass, The copolymer (A) is 1 to 10 parts by mass, the copolymer (B) is 90 to 99 parts by mass, and the copolymer (B) contains 5 to 30 parts by mass of a composition derived from an αβ unsaturated carboxylic acid monomer. In the above shell portion, the copolymer (B) has a carboxyl group and contains a polyvalent metal of less than 1 chemical equivalent with respect to the carboxyl group. The composition for a gloss agent according to claim 1, wherein in the shell portion, the copolymer (B) is other than the αβ unsaturated carboxylic acid monomer and the αβ unsaturated carboxylic acid monomer. The monomer is obtained by copolymerization. A method for producing a composition for a brightener, comprising 5 parts by mass to 30 parts by mass of the αβ unsaturated carboxylic acid monomer (b1) in a reaction system containing 1 part by mass to 10 parts by mass of the copolymer (A), and 60 parts by mass to 94 parts by mass of the monomer (b2) copolymerizable with the above α? unsaturated carboxylic acid monomer [wherein (A) + (b1) + (b2) = 100 parts by mass], emulsion polymerization is carried out, whereby the copolymer (B) is obtained, wherein the copolymer (A) has a glass transition point of -70 ° C to 0 ° C, The average particle diameter is 20 nm to 110 nm, and the insoluble component when dissolved in tetrahydrofuran is 0% by mass to 20% by mass, wherein the obtained composition for a gloss agent has a core portion containing the above copolymer (A) and contains the above copolymer In the shell portion of (B), the insoluble component when dissolved in tetrahydrofuran is 0% by mass to 30% by mass; in the shell portion, the copolymer (B) has a carboxyl group and contains less than 1 chemical equivalent with respect to the carboxyl group. Multivalent metal.