JP2011127012A - Lustering agent material for floor and lustering agent for floor utilizing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a lustering agent material for floor and a lustering agent for floor utilizing the same that simultaneously improve gloss retention and stain resistance without diminishing resistance to black heel marks and releasability. <P>SOLUTION: The polyrotaxane 10 comprises cyclic molecules 12, a linear molecule 11 which penetrates through the rings of the cyclic molecules 12 to form a clathrate with the cyclic molecules 12, and blocking groups 13 disposed at the both ends of the linear molecule 11 so as to prevent the cyclic molecules 12 from separating from the linear molecule 11. The lustering agent material for floor comprises a modified polyrotaxane 10 obtained by providing hydrophobic groups 14 and hydrophilic groups 15 to the cyclic molecules 12 of the polyrotaxane 10. The lustering agent for floor contains the lustering agent material for floor and an aqueous crosslinking agent. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a floor polish material and a floor polish using the same.

  Among the polishes, the floor polish is classified according to Standard-00 of the Japan Floor Polish Industry Association (JFPA). Of the floor polishes defined in this standard, aqueous polymer types dominate as floor polishes. This water-based polymer type floor polishing agent is, for example, an acrylic copolymer resin emulsion component, a wax emulsion component, an alkali-soluble resin, as described in Patent Documents 1 and 2 and Non-Patent Document 1 below. , plasticizer, which consists of other, this type is the current mainstream. However, the above-mentioned floor polish described in Patent Documents 1 and 2 and Non-Patent Document 1 below has a drawback that it is difficult to obtain slip resistance.

  For this reason, for example, the following Patent Document 3 proposes a floor polish containing an aqueous polyurethane resin emulsion for the purpose of improving the slip resistance. However, the floor polish described in the following Patent Document 3 also has an insufficient performance point. For example, in the following Patent Document 4 etc., the black heel resistance which is regarded as a weak point Made from aliphatic or alicyclic isocyanates and aliphatic polyesters or aliphatic polyethers for the purpose of improving markability, scuff resistance, and abrasion resistance, and improving gloss, leveling properties, etc. A floor polish comprising an aqueous dispersion or emulsion of urethane resin is proposed.

  In such a floor polish, in addition to the above, for example, an acrylic copolymer resin emulsion component that is a main component of a floor polish and affects its properties, and a black heel mark Various researches and developments such as the composition of wax emulsion components and the synthesis thereof for improving the properties have been conducted.

Japanese Patent Publication No. 44-24407 Japanese Patent Publication No.49-1458 Japanese Patent Publication No.53-22548 Japanese Patent Publication No. 6-6694 Japanese Examined Patent Publication No. 44-24409 Japanese Patent Publication No. 49-1548 International Publication No. 2005/052026 Pamphlet International Publication No. 2005/080469 Pamphlet

Cosmetic Chemical Specialities, 61 (9), 86, (1985) Macromolecules 1993, 26, 5698-5703 Manufacturing Chemist and Aerosol News June, 31, (1969)

  By the way, in the floor polish as described above, each component may affect the performance of each component independently, but each component affects each other and affects the performance in many cases. For example, when it was going to improve the gloss maintenance property of the formed film, the stain resistance of the film was lowered.

  For this reason, the present invention is for floors that can simultaneously improve gloss retention and stain resistance without degrading other properties such as black heel mark resistance and peelability of the formed film. An object of the present invention is to provide a polish material and a floor polish using the same.

  In order to solve the above-described problems, the floor polish agent material according to the present invention includes a cyclic molecule and a straight chain that is included in the cyclic molecule through the inside of the ring of the cyclic molecule. A hydrophobic group and a hydrophilic group on the cyclic molecule of the polyrotaxane comprising a molecule and a blocking group disposed at both ends of the linear molecule to prevent the cyclic molecule from detaching from the linear molecule It consists of the modified | denatured polyrotaxane which provided the group.

  Moreover, floor polishes material according to the present invention, in the above-mentioned floor polish material, wherein the cyclic molecule is cyclodextrin, the hydrophobic group and the at least a portion of the hydroxyl groups in the cyclodextrin The hydrophilic group is modified.

  The floor polish material according to the present invention is characterized in that in the floor polish material described above, at least a part of the hydrophilic group is modified with the hydrophobic group.

  The floor polish material according to the present invention is characterized in that in the floor polish material described above, at least a part of the hydrophobic group is modified with the hydrophilic group.

  Moreover, floor polishes material according to the present invention is a floor polish material described above, the hydrophobic group is characterized by a resulting modified groups by ring-opening polymerization from the lactone monomer .

  Further, the floor polish agent material according to the present invention is the floor polish agent material described above, wherein the hydrophilic group is an alkyl alcohol group, a polyalkyl oxide group, a carboxylic acid group, a salt of a carboxylic acid group, a sulfone. It consists of a modifying group having at least one of an acid group and a salt of a sulfonic acid group.

  Further, the floor polish agent material according to the present invention is the above-described floor polish agent material, wherein the maximum number of the hydroxyl groups of the cyclodextrin that can be modified is 1, and The modification degree is 0.02 or more.

  Further, the floor polish agent material according to the present invention is the floor polish agent material described above, wherein the hydrophilic group is 0.01 to 0.9 in a ratio to the total hydroxyl groups of the cyclodextrin. The cyclodextrin is provided directly or indirectly.

  Further, the floor polish agent material according to the present invention is the above-described floor polish agent material, wherein the hydrophobic property is such that the amount of the lactone monomer is 2 to 9 equivalents relative to the total hydroxyl amount of the cyclodextrin. A group is provided directly or indirectly with respect to the cyclodextrin.

  The floor polish material according to the present invention is the floor polish material described above, wherein the cyclodextrin is at least one of α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin. It is characterized by being.

  Further, the floor polish agent material according to the present invention is the above-described floor polish agent material when the maximum inclusion amount at which the linear molecule can include the cyclic molecule is 1 in the floor polish agent material described above. The inclusion amount of the cyclic molecule with respect to the chain molecule is 0.001 to 0.6.

  Further, the floor polish agent material according to the present invention is characterized in that in the above-described floor polish agent material, the molecular weight of the linear molecule is 10,000 or more.

  And the floor polish which concerns on this invention for solving the subject mentioned above contains the floor polish agent material mentioned above and the water-system crosslinking agent, It is characterized by the above-mentioned.

  The floor polish according to the present invention is characterized in that, in the above-described floor polish, the content ratio of the material for floor polish is 5 to 70% by mass with respect to the film forming component. .

  Further, the floor polish according to the present invention is the floor polish described above, wherein the aqueous crosslinking agent is an aziridine crosslinking agent, a carbodiimide crosslinking agent, an oxazoline crosslinking agent, an epoxy crosslinking agent, or a silane cup. It consists of at least 1 type of a ring agent and the metal crosslinking agent of a polyvalent metal compound, It is characterized by the above-mentioned.

  Furthermore, the floor polishing film according to the present invention is characterized by comprising the above-described floor polishing agent solidified.

  According to the floor polish material and the floor polish using the same according to the present invention, the formed film has excellent stretchability, viscoelasticity and stress due to the sliding movement action (pulley effect) of the modified polyrotaxane. Since the dispersibility and the like are developed, it is possible to simultaneously improve the gloss maintenance property and the stain resistance without deteriorating other properties such as black heel mark resistance and peelability of the formed film.

It is explanatory drawing of the structure of the polyrotaxane which comprises the polish agent material for floors concerning this invention.

  Embodiments of a floor polish material according to the present invention and a floor polish using the same will be described below with reference to the drawings. However, the present invention is limited only to the following embodiments described with reference to the drawings. Is not to be done.

[Flatening material for floor]
As shown in FIG. 1, the floor polish material according to the present embodiment includes a cyclic molecule 12 and a linear shape that is included in the cyclic molecule 12 through the inside of the ring of the cyclic molecule 12 in a skewered manner. Hydrophobic group in the cyclic molecule 12 of the polyrotaxane 10 comprising a molecule 11 and a blocking group 13 disposed at both ends of the linear molecule 11 to prevent the elimination of the cyclic molecule 12 from the linear molecule 11 14 and a modified polyrotaxane 10 provided with a hydrophilic group 15.

<Linear molecule 11>
The linear molecule 11 is a molecule extending linearly and is not particularly limited. For example, polyvinyl alcohol, polyvinyl pyrrolidone, poly (meth) acrylic acid, cellulose resin (carboxymethyl cellulose, Hydroxyethyl cellulose, hydroxypropyl cellulose, etc.), polyacrylamide, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyvinyl acetal resin, polyvinyl methyl ether, polyamine, polyethyleneimine, casein, gelatin, starch, etc. and / or copolymers thereof, Polyolefin resins such as polyethylene, polypropylene, and other copolymer resins with olefin monomers, polyester resins, polyvinyl chloride resins, polystyrene and acrylonites Polystyrene resins such as ru-styrene copolymer resins, acrylic resins such as polymethyl methacrylate and (meth) acrylate copolymers, acrylonitrile-methyl acrylate copolymer resins, polycarbonate resins, polyurethane resins, vinyl chloride-vinyl acetate Copolymer resins, polyvinyl butyral resins, etc .; and derivatives or modified products thereof, polyisobutylene, polytetrahydrofuran, polyaniline, acrylonitrile-butadiene-styrene copolymer (ABS resin), polyamides such as nylon, polyimides, polyisoprene, Polydienes such as polybutadiene, polysiloxanes such as polydimethylsiloxane, polysulfonic acids, polyimines, polyacetic anhydrides, polyureas, polysulfides, polyphosphazenes, polyketo S, polyphenylenes, polyhaloolefins, as well as derivatives thereof.

  However, the linear molecule 11 is preferably polyethylene glycol, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, or polypropylene, and in particular, polyethylene glycol, polypropylene glycol, Polytetrahydrofuran, polydimethylsiloxane, polyethylene, or polypropylene is more preferable, and polyethylene glycol is most preferable.

  The linear molecule 11 preferably has a molecular weight of 10,000 or more (particularly 20,000 or more, more preferably 30,000 or more).

<Cyclic molecule 12>
The cyclic molecule 12 is a molecule having a cyclic structure and is not particularly limited. However, the cyclic molecule 12 is preferably an optionally substituted cyclodextrin, and more preferably any of α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, and derivatives thereof. .

<Blocking group 13>
The blocking group 13 is provided at both ends of the linear molecule 11 so as not to desorb the cyclic molecule 12 from the linear molecule 11, and is particularly limited as long as it can cause such an action. Is not to be done.

  However, examples of the blocking group 13 include dinitrophenyl groups, cyclodextrins, adamantane groups, trityl groups, fluoresceins, pyrenes, substituted benzenes, optionally substituted polynuclear aromatics, and steroids. preferable to be any one of, in particular, dinitrophenyl groups, cyclodextrins, adamantane groups, trityl groups, fluoresceins, and more preferable to be one of pyrenes, further adamantane group such or trityl group such Is most preferable.

  In addition, the substituents of the substituted benzenes and optionally substituted polynuclear aromatics are not particularly limited. For example, alkyl, alkyloxy, hydroxy, halogen, cyano, sulfonyl, carboxyl, amino And phenyl. Here, the substituent is not limited to one, and a plurality of substituents may be present.

  In addition, the blocking group 13 is not necessarily the same as that provided at one end of the linear molecule 11 and that provided at the other end, and can be different.

<Hydrophobic group 14 and hydrophilic group 15>
The hydrophobic group 14 is provided directly or indirectly as a modifying group with respect to the cyclic molecule 12 to improve compatibility with other compositions of a floor polish and to provide flexibility as a coating. It is to improve.

  Such a hydrophobic group 14 is not particularly limited. For example, ring opening of a lactone monomer such as ε-caprolactone, γ-butyrolactone, α-methyl-γ-butyrolactone, δ-valerolactone, and the like. A modifying group obtained by polymerization is preferable, and a modifying group obtained by ring-opening polymerization of ε-caprolactone is more preferable.

  The hydrophilic group 15 is provided directly or indirectly as a modifying group with respect to the cyclic molecule 12, and improves the solubility and dispersibility of the polyrotaxane 10 in water or an aqueous solvent, thereby improving the floor polish. As a material for the floor, it is present in a stable state in a floor polish and, as will be described later, the polyrotaxanes 10 or the hydrophilic groups (for example, hydroxyl groups, —COOH groups, etc.) of the polyrotaxanes 10 and other resin emulsion components. ).

Such a hydrophilic group 15 is not particularly limited. For example, —CH ₂ CH (OH) CH ₃ , —CH ₂ CH (OH) CH ₂ OH, —CH ₂ CH (NH ₂ ) Modification group having a hydroxyl group or amino group such as CH ₃ ; alkylene oxide such as — (OCH ₂ CH ₂ ) _m OH, — (OCH (CH ₃ ) CH ₂ ) _m OH, — (NHCH ₂ CH ₂ ) _m NH ₂ Or a modifying group having a group derived from alkyleneimine; -COOH formed by reaction of succinic anhydride, glutaric anhydride, diglycolic anhydride, phthalic anhydride, trimeric anhydride, and derivatives thereof and these A modified group having a salt of: -COOH formed by oxidation reaction of alkyl alcohol and its derivatives and a modified group having these salts; by reaction of propane sultone and its derivatives Examples thereof include -SO ₃ H formed and modifying groups having these salts.

  A method of introducing the hydrophobic group 14 and the hydrophilic group 15 into the polyrotaxane 10, that is, a method of modifying the cyclic molecule 12 is not particularly limited. By applying dextrin and utilizing the hydroxyl group, the modifying groups 14 and 15 can be directly or indirectly modified with respect to the dextrin.

  Further, the procedure for introducing the hydrophobic group 14 and the hydrophilic group 15 into the polyrotaxane 10, that is, the procedure for modifying the cyclic molecule 12 is not particularly limited. when applying α- cyclodextrin, for the hydroxyl group, after modifying the compound to be a hydrophilic group 15 by chemical reaction, or be modified subsequently by chemically reacting a compound serving as a hydrophobic group 14, a hydrophobic the compound as a sex group 14 after modified by chemical reaction, and to continue to modified by chemical reaction of the compound of the hydrophilic group 15 is divided and a hydrophilic group 15 and a hydrophobic group 14 into a plurality of times alternately And introducing a plurality of types of hydrophilic groups 15 and hydrophobic groups 14 alternately for each type.

  At this time, the hydrophobic group 14 and the hydrophilic group 15 are not only provided by directly modifying the hydroxyl group of the cyclodextrin, but, for example, at least modified directly to the hydroxyl group of the cyclodextrin Modifying the hydrophobic group 14 with respect to some of the hydrophilic groups 15 and indirectly introducing it into the cyclodextrin, or modifying at least a part of the hydrophobic group directly modified with the hydroxyl group of the cyclodextrin Modifying the hydrophilic group 15 with respect to the group 14 to introduce it indirectly into the cyclodextrin, or modifying the hydrophilic group 15 with respect to the hydrophobic group 14 introduced indirectly. Further introduction into the cyclodextrin, or modification of the hydrophobic group 14 with respect to the hydrophilic group 15 introduced indirectly to the cyclodextrin. It is possible such as to introduce into.

  Specifically, for example, after introducing a hydroxyalkyl group that becomes the hydrophilic group 15 to the hydroxyl group of α-cyclodextrin, a modification group of a polymer that is made of a lactone monomer that becomes the hydrophobic group 14 is changed to α- Examples thereof include introduction into a hydroxyl group and a hydroxyalkyl group of cyclodextrin, and further modification of the hydrophilic group 15 having a —COOH group or a salt thereof to the lactone polymer.

  Here, when the maximum number of functional groups of the cyclic molecule 12, that is, for example, the hydroxyl group of the cyclodextrin can be modified is 1, the modification degree of the hydroxyl group of the cyclodextrin is preferably 0.02 or more. In particular, it is more preferably 0.1 or more, and most preferably 0.3 or more.

  The hydrophilic group 15 is preferably provided directly or indirectly with respect to the cyclodextrin so that the ratio to the total hydroxyl groups of the cyclodextrin is 0.01 to 0.9. 0.05 to 0.8 is more preferable, and 0.1 to 0.6 is most preferable.

  Further, when the hydrophobic group 14 is a modified group obtained by from ring-opening polymerization of lactones monomer, such that 2-9 equivalents in an amount of the lactone monomer to total amount of hydroxyl groups of the cyclodextrin, the hydrophobic group 14 Is preferably provided directly or indirectly with respect to the cyclodextrin, more preferably 2.5 to 8.5 equivalents, and most preferably 3.5 to 6 equivalents. .

<Polyrotaxane 10>
The polyrotaxane 10 has a maximum inclusion amount of the cyclic molecule 12 that can penetrate the cyclic molecule 12 in a skewered manner with respect to the linear molecule 11, that is, the linear molecule 11 is the cyclic molecule 12. The amount of inclusion of the cyclic molecule 12 with respect to the linear molecule 11 is preferably 0.001 to 0.6, particularly 0.01 to More preferably, it is 0.5, and most preferably it is 0.05 to 0.4.

  By the way, the maximum inclusion amount can be obtained from the length of the linear molecule 11 and the thickness of the cyclic molecule 12. For example, in Non-Patent Document 2 and the like, the maximum inclusion amount of the polyrotaxane 10 when the linear molecule 11 is polyethylene glycol and the cyclic molecule 12 is α-cyclodextrin is experimentally obtained. The maximum inclusion amount of the polyrotaxane 10 can be determined by means described in Non-Patent Document 2 and the like.

  As the polyrotaxane 10, it is most preferable that the linear molecule 11 is polyethylene glycol and the cyclic molecule 12 is α-cyclodextrin which may be substituted.

[Glossing agent for floor]
Further, the floor polish according to this embodiment contains the above-described floor polish material, that is, the above-described modified polyrotaxane 10 and an aqueous crosslinking agent. More specifically, together with the polyrotaxane 10, an acrylic copolymer resin emulsion component (resin solid content), a wax emulsion component (resin solid content), an alkali-soluble resin (leveling) used in an existing floor polish. Agent: Resin solids), plasticizers, and other components (for example, film forming agents, wettability improvers, urethane resin emulsion components (resin solids), antifoaming agents, preservatives, emulsion modifiers, perfumes In combination with the hydrophilic group 15 of the polyrotaxane 10 or an aqueous crosslinking agent that crosslinks the hydrophilic group 15 of the polyrotaxane 10 and the hydrophilic group of the resin emulsion component. And mixed with water or an aqueous solvent.

  Here, it is preferable that the polyrotaxane 10 is blended in a state of being previously dissolved in water or an aqueous solvent, or in a state of being emulsified using an emulsifier. Such a solution or emulsion of the polyrotaxane 10 can be prepared when a floor polish is manufactured, or can be prepared prior to manufacturing a floor polish.

  In such a floor polish, the content ratio of the polyrotaxane 10 to the film-forming component (resin solid content) is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, Furthermore, it is most preferable in it being 20-50 mass%. This is because, if the ratio is less than 5 mass%, the polyrotaxane 10 becomes difficult to sufficiently exhibit the effect by, it becomes difficult to sufficiently increase the stress distribution of the formed film, scratch resistance is sufficiently there is one where there is a risk that not be obtained, if the proportion exceeds 70 wt%, the flexibility of the formed film becomes too high, it becomes impossible to sufficiently withstand scratches by walking fear Because.

<Acrylic copolymer resin emulsion component>
Examples of the acrylic copolymer resin emulsion component include styrene, methylstyrene, acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, 2-ethyl-hexyl acrylate, and methacrylic acid. Of acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethyl-hexyl methacrylate, vinyl acetate, acrylonitrile, itaconic acid, maleic acid, and copolymers of these types These may be used singly or as a mixture (see, for example, Patent Document 5). Moreover, it is also possible to apply the metal bridge | crosslinking type thing to which the polyvalent metal chelating agent was added (refer the said patent document 6 and the said nonpatent literature 3, etc.).

<Wax emulsion component>
Examples of the wax emulsion component include natural wax and synthetic wax. Specifically, for example, carnauba wax, candelilla wax, montan wax, montan derived wax, ceresin wax, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, amide wax, polyethylene wax and its carboxyl-modified wax, oxidized polyethylene wax, Examples thereof include carboxyl-modified wax, polypropylene wax and its carboxy-modified wax, oxidized polypropylene wax and its carboxy-modified wax, glycol-modified oxide polyethylene wax, glycol-modified oxide polypropylene wax, and ethylene-acrylic acid copolymer wax. Polyethylene wax and polypropylene wax are preferable.

<Alkali-soluble resin>
Examples of the alkali-soluble resin include rosin-modified maleic acid, styrene-maleic anhydride copolymer, diisobutylene-maleic anhydride copolymer, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene. -Α-methylstyrene-acrylic acid copolymer, styrene-α-methylstyrene-methacrylic acid copolymer, styrene-acrylic acid ester-acrylic acid copolymer, styrene-methacrylic acid ester-acrylic acid copolymer, styrene -Methacrylic acid ester-Methacrylic acid copolymer, Styrene-α-methylstyrene-Acrylic acid ester-Acrylic acid copolymer, Styrene-α-Methylstyrene-Methacrylic acid ester-Acrylic acid copolymer, Styrene-α-Methyl Styrene-methacrylic acid ester-methacrylic acid copolymer , Acrylic acid ester-acrylic acid copolymer, methacrylic acid ester-acrylic acid copolymer, methacrylic acid ester-methacrylic acid copolymer, and shellac. These may be used alone or in combination of two or more. be able to.

<Plasticizer>
Examples of the plasticizer include phosphate esters such as tributoxyethyl phosphate (TBEP), tributyl phosphate, and triphenyl phosphate, phthalate esters such as dibutyl phthalate, citrate esters, and adipic acid esters. be able to.

<Film forming agent>
Examples of the film forming agent component include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, and dipropylene. Examples include glycol ethers such as glycol monomethyl ether and tripropylene glycol monomethyl ether, and alcohols such as ethanol and isopropyl alcohol.

<Wettability improver>
Examples of the wettability improver include a fluorine-based surfactant.

<Water-based crosslinking agent>
The water-based cross-linking agent cross-links between the hydrophilic groups 15 of the polyrotaxane 10 or between the hydrophilic groups 15 of the polyrotaxane 10 and the hydrophilic groups of the acrylic resin emulsion component and the urethane resin emulsion component. It is.

  Preferred as such an aqueous crosslinking agent, for example, aziridine, carbodiimide, oxazoline, existing aqueous crosslinking agent such as epoxy based, silane coupling agent, mention may be made of metal crosslinking agent of the polyvalent metal compound In particular, a carbodiimide type is more preferable, and these can be used alone or in combination of two or more.

[Glossy coating for floor]
In addition, the floor polishing film according to this embodiment is applied to the floor surface in the same manner as the conventional floor polishing agent described above, and then dried at room temperature or dried by heating. Then, by evaporating the water and solidifying, it can be formed on the floor surface with the same work efficiency as the conventional floor polish.

  The thickness of the floor polish film is not particularly limited. For example, the floor polish is applied to the floor surface so that the formed thickness is 10 to 100 μm. It is preferable.

  In such the floor polish film, made from the floor (in particular, wood flooring such as wood, plastic-based flooring material made of synthetic resin of a vinyl such as, concrete, marble, etc. inorganic-based flooring materials such When formed on the floor surface, the polyrotaxane 10 exhibits excellent stretchability, viscoelasticity and stress dispersibility due to the slide movement action (pulley effect), etc. Thus, it is possible to simultaneously improve gloss maintenance and stain resistance without deteriorating other properties such as the above. This will be described in detail below.

  In the glossy coating for floors, in order to improve the gloss maintenance, usually the flexibility is improved. As a material that can form a film having such flexibility, conventionally, an acrylic copolymer resin having a low glass transition point (Tg) or a polyethylene wax having a slightly lower melting point is used. In many cases, a urethane resin having toughness is used in combination.

  However, the film made of urethane resin and acrylic copolymer resin is not in a state in which urethane resin and acrylic copolymer resin are chemically bonded to each other like crosslinking, but acrylic copolymer resin. Since the urethane resin is dispersed and present in the inside (a state where urethane resin islands are scattered in the sea of acrylic copolymer resin), a load is applied locally. If this occurs, a part of the molecular structure may be destroyed (generally an acrylic copolymer resin part), and gloss maintenance may not be sufficiently exhibited. There was a problem that dirt such as earth and sand easily enters and stays in the recess, and the dirt resistance is likely to be lowered.

  Therefore, the present inventors do not destroy the molecular structure even when a load is applied locally, and make it easy to restore the original state, i.e., toughness or expansion / contraction that does not destroy the molecular structure. As a result of earnest research, it is possible to improve gloss maintenance and stain resistance at the same time, and as a result of using the slide movement action (pulley effect) of polyrotaxane, the above problems can be solved. They found that it could be solved.

  As described above, the polyrotaxane is composed of the cyclic molecule 12, the linear molecule 11 penetrating the inside of the ring of the cyclic molecule 12 and being included in the cyclic molecule 12, and the linear molecule 11. And a blocking group 13 disposed at both ends to prevent the detachment of the cyclic molecule 12 from the linear molecule 11, and the cyclic molecule 12 has a circumferential direction and an axis relative to the linear molecule 11. It has a structure that can move freely in the direction.

  To introduce a hydrophobic group 14 to such a polyrotaxane so as to have an affinity with a resin component, while at the same time achieving an affinity with water or an aqueous solvent and enabling crosslinking with a resin component or the like. In the floor polish film formed by incorporating the hydrophilic group 15 into the floor polish agent as the modified polyrotaxane 10 together with the water-based crosslinking agent, the cyclic molecule 12 is a resin. Since it is cross-linked with the components and the like, when a load is locally applied, the cross-linking point of the cyclic molecule 12 slides, that is, the coating itself becomes greatly depressed. The impact applied to the cross-linking points can be greatly buffered, and the destruction of the molecular structure of the coating can be greatly suppressed. As a result, the cross-linking point of the cyclic molecule 12 slides to restore the original position, that is, the depression of the coating itself is restored (self-healing). It becomes difficult to stay inside.

  As a result, the above-described glazing coating for floors exhibits excellent stretchability, viscoelasticity, stress dispersibility, and the like, and maintains glossiness without reducing other properties such as black heel mark resistance and peelability. The stain resistance can be improved at the same time.

  In order to confirm the effect of the floor polish agent material according to the present invention and the floor polish agent using the same, examples carried out based on the above-described embodiment will be described below. It is not limited only to the embodiment described in the above.

[Preparation of floor polish material]
<Test Material A: Modified Polyrotaxane Introduced Hydrophobic Group Derived from ε-Caprolactone Polymer and Hydrophilic Group of Hydroxypropyl Group and —COOH Group Derived from Succinic Acid>

(1) Preparation of polyrotaxane Polyethylene glycol (PEG) (weight average molecular weight: 35,000) is a linear molecule, α-cyclodextrin (α-CD) is a cyclic molecule, and a group derived from adamantamine is a blocking group. The prepared polyrotaxane was prepared based on the method described in Patent Document 7. The polyrotaxane thus obtained was analyzed by ¹ H-NMR at 400 MHz (“JNM-AL400 (model number)” manufactured by JEOL Ltd.). As a result, the inclusion amount of α-CD was 0.25, As a result of measurement by GPC, the average weight molecular weight Mw was 140,000. The measurement conditions for GPC are as follows.

-GPC device: “HCL-8220GPC (trade name)” manufactured by Tosoh Corporation
-Column used: "TSK guard column super AW-H (trade name)" manufactured by Tosoh Corporation and "TSK gel super AWM-H (trade name)" connected.-Eluent: dimethyl sulfoxide / 0.01M LiBr
-Column oven: 50 ° C
・ Flow rate: 0.5 ml / min ・ Sample concentration: about 0.2 wt / vol%
・ Injection volume: 20 microliters ・ Standard molecular weight: PEO conditions

(2) Hydroxypropyl group introduction Next, based on the method described in Patent Document 8, the polyrotaxane obtained in (1) was hydroxypropylated to produce a hydroxypropylated polyrotaxane. The hydroxypropylated polyrotaxane thus obtained was analyzed by ¹ H-NMR at 400 MHz (“JNM-AL400 (trade name)” manufactured by JEOL Ltd.). As a result, the hydroxypropyl group with respect to the hydroxyl group of α-CD The degree of modification was 0.48, and as a result of measurement by GPC, the average weight molecular weight Mw was 150,000. The GPC measurement conditions are the same as described above.

(3) Introduction of Hydrophobic Group Derived from ε-Caprolactone Polymer The dried hydroxypropylated polyrotaxane (1.0 g) obtained in (2) above was placed in a three-necked flask, and ε-caprolactone ( 4.5 g: 3.9 equivalents based on the total hydroxyl amount of the hydroxypropylated polyrotaxane), uniformly stirred with a mechanical stirrer (80 ° C. × 30 minutes), heated (100 ° C.), After adding tin 2-ethylhexanoate (0.16 g) as a toluene solution (50 wt%) and allowing it to react (4 hours), the reaction solvent (toluene) was removed, and ε-caprolactone was subjected to ring-opening polymerization. A polyrotaxane into which a hydrophobic group composed of the grafted chain was introduced was prepared. This hydrophobized polyrotaxane had a total hydroxyl amount (total amount of α-CD hydroxyl groups remaining without modification with the modifying group and hydroxyl groups in the modifying group) of 1.8 mmol / g.

(4) Introduction of hydrophilic group derived from succinic acid The hydrophobized polyrotaxane (5.5 g) obtained in (3) above was placed in a flask and dissolved by adding dehydrated acetone (30 ml), and then succinic anhydride. (0.80 g: 80 mol% with respect to the total amount of hydroxyl groups of the hydrophobized polyrotaxane) and triethylamine (1.1 ml) are added and stirred (40 ° C. × 24 hours). The mixture was allowed to cool to room temperature, diethylene glycol monoethyl ether (6.3 g) was added and stirred, and then the reaction solvent (acetone) was removed by an evaporator, whereby a hydrophilic group consisting of -COOH groups was removed by succinic anhydride. An introduced polyrotaxane was obtained.

  The modified polyrotaxane thus obtained (Test Material A), that is, derived from a hydroxypropyl group that is a hydrophilic group, a polycaprolactone graft chain that is a hydrophobic group, and a succinic anhydride that is a hydrophilic group. results polyrotaxane introduced a -COOH group, the amount of -COOH groups is 1.25 mmol / g (degree of modification is 0.8 -COOH groups relative to the total amount of hydroxyl groups in the hydrophobic polyrotaxane), as measured by GPC The average weight molecular weight Mw was 586,800, and the molecular weight distribution Mw / Mn was 1.7.

<Test Material B: Modified Polyrotaxane Introduced Hydrophobic Group Derived from ε-Caprolactone Polymer and Hydrophilic Group of Hydroxypropyl Group and -COOH Group Derived from Trimellitic Acid>

(1) Production of polyrotaxane A polyrotaxane was produced in the same manner as in the test material A.

(2) Hydroxypropyl group introduction In the same manner as in the test material A, a hydroxypropyl group was introduced.

(3) Introduction of Hydrophobic Group Derived from ε-Caprolactone Polymer In the same manner as in Test Material A, a hydrophobic group derived from ε-caprolactone polymer was introduced.

(4) Introduction of hydrophilic group derived from trimellitic acid The hydrophobized polyrotaxane (5.5 g) obtained in (3) above was placed in a flask and dissolved by adding dehydrated acetone (30 ml), and then trimellitic acid. Anhydrous anhydride (0.8 g: 40 mol% with respect to the total hydroxyl amount of the hydrophobized polyrotaxane) and triethylamine (0.6 ml) are added and stirred (40 ° C. × 24 hours). After allowing to cool to room temperature, diethylene glycol monoethyl ether (6.3 g) was added and stirred, and then the reaction solvent (acetone) was removed with an evaporator, whereby a hydrophilic group consisting of —COOH groups was obtained with trimellitic anhydride. To obtain a polyrotaxane.

  The modified polyrotaxane thus obtained (test material B), that is, derived from a hydroxypropyl group which is a hydrophilic group, a polycaprolactone graft chain which is a hydrophobic group, and trimellitic anhydride which is a hydrophilic group the polyrotaxane introduced a -COOH group, the amount of -COOH groups is 1.25 mmol / g (degree of modification of the -COOH groups to the total amount of hydroxyl groups in the hydrophobic polyrotaxane is 0.4), were measured by GPC As a result, the average weight molecular weight Mw was 751,000, and the molecular weight distribution Mw / Mn was 1.3. The GPC measurement conditions are the same as described above.

<Comparative Material A: Modified Polyrotaxane Introducing Only Hydrophilic Group of Hydroxypropyl Group and Succinic Acid-Derived -COOH Group>

(1) Production of polyrotaxane A polyrotaxane was produced in the same manner as in the test materials A and B.

(2) Hydroxypropyl group introduction Hydroxypropyl groups were introduced in the same manner as the test materials A and B.

(3) Introduction of hydrophilic group derived from succinic acid The dried hydroxypropylated polyrotaxane (5.0 g) obtained in (2) above was dissolved in DMF (15 ml) and succinic acid dissolved in DMF (5 ml). Anhydrous anhydride (0.78 g: 16 mol% based on the total hydroxyl amount of hydroxypropylated polyrotaxane) and pyridine (1.8 ml) were added and reacted with stirring (6 hours), and then in a large amount of isopropyl alcohol. After dropping, the precipitated product was collected, washed with isopropyl alcohol, and dried to obtain a polyrotaxane having a hydrophilic group composed of -COOH group introduced by succinic anhydride.

  The thus obtained modified polyrotaxane (Comparative material A), i.e., a polyrotaxane which is introduced to -COOH groups derived from hydroxypropyl groups and succinic anhydride is a hydrophilic group, the amount of -COOH groups 1.34mmol / g a (degree of modification of the -COOH groups to the total hydroxyl group amount of the hydroxypropylated polyrotaxane is 0.16), the results of measurement by GPC, and the average weight molecular weight Mw of 120,000, molecular weight distribution Mw / Mn 1.2. The GPC measurement conditions are the same as described above.

[Fabrication of floor polish]
The floor polish using the test materials A and B is prepared and prepared at the blending ratios shown in Table 1 below (test agents 1 to 4), and the floor polish using the comparative material A is prepared. The agents were prepared and prepared at the blending ratios shown in Table 2 below (Comparative agents 1 and 2). For comparison, floor polishes not containing a polyrotaxane were also prepared and prepared at the blending ratios shown in Table 3 below (Comparative agents 3 to 6).

  In Tables 1 to 3 below, the acrylic copolymer resin emulsion used is “Primal E-2409 (trade name)” manufactured by Rohm and Haas, USA, and the styrene-acrylic copolymer resin emulsion is US Rohm. use & Haas Co. to "Dura plus-2 (trade name)", water-based cross-linking agent (carbodiimide-based) uses made of Nisshinbo Chemical Co., Ltd. "Carbodilite V-02-L2 (trade name)", polyethylene wax Emulsion uses “Hi-Tech E-6020 (trade name)” manufactured by Toho Chemical Industry Co., Ltd., and alkali-soluble resin uses “SMA-17352P (trade name)” manufactured by Sartomer, USA, a fluorine-based surfactant. Used “Surflon S-111 (trade name)” manufactured by AGC Seimi Chemical Co., Ltd.

[contents of the test]
Each test of the following item is performed by the method shown below with respect to the polishing film for floors formed by apply | coating the said test agents 1-4 and the said comparative agents 1-6 to a flooring material, and making it dry and solidify, respectively. It was.

(1) Gloss test A gloss value was measured according to a polymer type defined in Japanese Industrial Standard “JIS-K3920” (three times coating).

(2) Gloss maintenance test <Preparation of sample>
The test agents 1 to 4 and the comparison agents 1 to 6 were applied to a black homogeneous vinyl floor tile (15 cm × 10 cm: “MS plane 5608 (trade name)” manufactured by Toli Co., Ltd.) (10 ml per 1 m ² ). Each is dried in a thermostatic bath (20 ° C. × 45 minutes). Next, the test agents 1 to 4 and the comparative agents 1 to 6 are applied again in the same manner as described above and applied again to form a second layer and dried in the same manner as described above. 1 to 4 and the comparative agents 1 to 6 are further overcoated to form a third layer, which is then left to stand in a thermostatic bath for final drying (20 ° C. × 48 hours). Samples each having a film formed of 1-4 and the comparative agents 1-6 are prepared.

<Test method>
Then, after measuring the gloss value of the sample in the same manner as the gloss test (initial value), each sample was laid in a pedestrian passage, and after a predetermined period (2 months), the gloss test and Similarly, the gloss value of the sample was measured again (elapsed value), and the gloss maintenance property was obtained based on the difference (elapsed value) between the initial value and the elapsed value.

(3) Dirt resistance test <Preparation of sample>
The test agents 1 to 4 and the comparison agents 1 to 6 were applied to a white homogeneous vinyl floor tile (15 cm × 10 cm: “MS Plane 5601 (trade name)” manufactured by Toli Co., Ltd.) (10 ml per 1 m ² ). Each is dried in a thermostatic bath (20 ° C. × 45 minutes). Next, the test agents 1 to 4 and the comparative agents 1 to 6 are applied again in the same manner as described above and applied again to form a second layer and dried in the same manner as described above. 1 to 4 and the comparative agents 1 to 6 are further overcoated to form a third layer, which is then left to stand in a thermostatic bath for final drying (20 ° C. × 48 hours). Samples each having a film formed of 1-4 and the comparative agents 1-6 are prepared.

<Test method>
After measuring the L * value of the sample with a color difference meter (initial value), each sample is laid in a pedestrian passage, and after a predetermined period (two months), the sample with the color difference meter The L * value was measured again (elapsed value), and the stain resistance was determined based on the difference (elapsed value) between the initial value and the elapsed value.

(4) Black heel mark resistance test A confirmation test was conducted in accordance with the rules of Japanese Industrial Standard "JIS-K3920".

(5) Peelability test <Preparation of sample>
The test agent 1 to 4 and the comparison agent 1 to 6 are applied to a black composition vinyl floor tile (15 cm × 10 cm: “P tile P-60 (trade name)” manufactured by Tajima Co., Ltd.) (per 1 m ²⁾ . 10 ml) After drying (room temperature × 45 minutes) four times, the test agent 1 to 4 and the comparison agent 1 to 6 are applied in the same manner as described above to form the fifth layer and dry. By carrying out (room temperature × 1 hour), samples each having a film formed of the test agents 1 to 4 and the comparison agents 1 to 6 are prepared.

<Test method>
Then, each of the samples is transferred to a thermostatic bath and allowed to stand overnight (50 ° C.). The next day, the sample is taken out from the thermostatic bath and allowed to cool to room temperature. Next, immerse in a water tank filled with tap water (1 hour), dry well with a blower, transfer again to a thermostatic bath and leave overnight (50 ° C.), then remove from the thermostatic bath the next day to room temperature Allow to cool. Thereafter, this procedure (water immersion → air drying → constant temperature standing → cooling) is further repeated twice, and then the sample is cut to prepare a sample piece (2 cm × 4.5 cm).

  Next, after immersing the sample piece in a release agent and elapses for a predetermined time (5 minutes), the sample piece is pulled up from the release agent, rubbed with a soft sponge while being applied to running water (20 times), and then dried. The state of the coating was visually confirmed. As a release agent, a diluted solution (5 times) of an alkaline release agent “Clear Z (trade name)” manufactured by Linley Co., Ltd. and a diluted solution of a neutral release agent “ECO-500 (trade name)” manufactured by Linley Co., Ltd. Two types with different types (5 times) were prepared, and the difference due to each release agent was also confirmed.

[Test results]
The results of each test conducted as described above are shown in Table 4 below. The evaluation criteria for each test are as follows.

(1) Gloss test x: Gloss value is less than 60.
(Triangle | delta): A gloss value is 61-70.
○: Gloss value is 71-80.
A: The gloss value is 81 or more.

(2) Gloss maintenance test x: Warp value is 46 or more.
(Triangle | delta): A time-varying value is 36-45.
A: The time-varying value is 26 to 35.
(Double-circle): A time-varying value is 0-25.

(3) Stain resistance test x: The warp value is 3.6 or more.
(Triangle | delta): A time-varying value is 2.6-3.5.
A: The time-varying value is 1.6 to 2.5.
A: The transformation value is 0 to 1.5.

(4) Black heel mark resistance test x: Many heel marks adhere.
Δ: Slightly attached heel mark.
○: Slightly attached heel mark.
A: Almost no heel mark adheres

(5) Peelability test x: Both the alkaline release agent and the neutral release agent could not be peeled off.
Δ: Almost all of the alkaline release agent was peeled off, but the neutral release agent was not peeled off.
○: The alkaline release agent was able to be completely peeled off, and the neutral release agent was able to be peeled off mostly.
A: Both the alkaline release agent and the neutral release agent were completely peeled off.

  As can be seen from Table 4 above, in Comparative Examples 1 and 2 (Comparator 1 (Polyrotaxane modified with only hydrophilic group)), the film-forming property of the formed film is high. As a result, the glossiness was very low, and a polished coating for floors capable of exhibiting sufficient performance could not be obtained. On the other hand, in the test agents 1 to 4 (floor polish using the floor polish material according to the present invention), the glossiness is not particularly reduced without degrading the black heel mark resistance and the peelability. It was confirmed that a polished floor coating capable of exhibiting excellent performance in terms of maintainability and stain resistance can be formed. Therefore, it can be said that the glazing agent for floors according to the present invention can maintain high aesthetics even when applied to a floor surface having a large amount of walking.

  Floor polishes utilizing glazing material and this floor according to the present invention, since the performance of the coating, such as gloss retention properties and stain resistance of the formed film can be improved at the same time, industrial Can be used very beneficially.

10 Modified polyrotaxane (flooring material for flooring)
11 linear molecule 12 cyclic molecule 13 blocking group 14 hydrophobic group 15 hydrophilic group

Claims (16)

A cyclic molecule,
A linear molecule penetrating the inside of the ring of the cyclic molecule in a skewered manner and being included in the cyclic molecule;
A hydrophobic group and a hydrophilic group are provided on the cyclic molecule of the polyrotaxane, which is disposed at both ends of the linear molecule and has a blocking group for preventing the elimination of the cyclic molecule from the linear molecule. A floor polish material characterized by comprising a modified polyrotaxane. In the floor polish agent material according to claim 1,
The floor polish material, wherein the cyclic molecule is cyclodextrin and at least a part of the hydroxyl groups of the cyclodextrin is modified with the hydrophobic group and the hydrophilic group. In the floor polish agent material according to claim 2,
A floor polish agent material, wherein at least a part of the hydrophilic group is modified with the hydrophobic group. In the floor polish agent material according to claim 2 or claim 3,
A floor polish material, wherein at least a part of the hydrophobic group is modified with the hydrophilic group. In the floor polish agent material as described in any one of Claims 2-4,
The hydrophilic group comprises a modifying group having at least one of an alkyl alcohol group, a polyalkyl oxide group, a carboxylic acid group, a salt of a carboxylic acid group, a sulfonic acid group, and a salt of a sulfonic acid group. Flooring glaze material. In the floor polish agent material as described in any one of Claims 2-5,
The floor polish agent material, wherein the hydrophobic group is a modifying group obtained by ring-opening polymerization of a lactone monomer. In the floor polish agent material as described in any one of Claims 2-6,
A floor polish agent material characterized in that when the maximum number of the hydroxyl groups of the cyclodextrin that can be modified is 1, the modification degree of the hydroxyl groups of the cyclodextrin is 0.02 or more. In the floor polish agent material as described in any one of Claims 2-6,
The floor gloss is characterized in that the hydrophilic group is provided directly or indirectly to the cyclodextrin so that the ratio of the hydrophilic group to the total hydroxyl group of the cyclodextrin is 0.01 to 0.9. Dispensing material. The floor polish material according to claim 6,
The floor is characterized in that the hydrophobic group is provided directly or indirectly with respect to the cyclodextrin so that the amount of the lactone monomer is 2 to 9 equivalents relative to the total amount of hydroxyl groups of the cyclodextrin. Polishing material. In the floor polish agent material according to any one of claims 2 to 9,
The above-mentioned cyclodextrin is at least one of α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin. In the floor polish agent material according to any one of claims 1 to 10,
When the maximum inclusion amount that the linear molecule can include the cyclic molecule is 1, the inclusion amount of the cyclic molecule with respect to the linear molecule is 0.001 to 0.6. Floor polish material characterized by. In the floor polish agent material as described in any one of Claims 1-11,
A floor polish material, wherein the linear molecule has a molecular weight of 10,000 or more. A floor polish material according to any one of claims 1 to 12,
A floor polishing agent characterized by comprising an aqueous crosslinking agent. In the floor polish according to claim 13,
The floor polish is characterized in that the content of the material for floor polish with respect to the film-forming component is 5 to 70% by mass. In the floor polish according to claim 13 or 14,
The aqueous crosslinking agent is composed of at least one of an aziridine crosslinking agent, a carbodiimide crosslinking agent, an oxazoline crosslinking agent, an epoxy crosslinking agent, a silane coupling agent, and a metal crosslinking agent of a polyvalent metal compound. A floor polish. A floor polishing film comprising the solidified floor polishing agent according to any one of claims 13 to 15.

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