JP6387199B1 - Hard surface treatment agent - Google Patents

Abstract

A hard surface treatment agent having excellent antifouling durability is provided.
A hard surface treating agent according to this embodiment includes a copolymer (A) of diallyldialkylammonium halide (a1) and (meth) acrylate (a2), and a repeating unit having a sulfonate. The polymer (B) containing is included. The mass ratio of the copolymer (A) and the polymer (B) is preferably (A) / (B) = 0.05-10. The hard surface treatment agent may further contain a surfactant (B).
[Selection figure] None

Description

  The present invention relates to a hard surface treatment agent.

  Conventionally, a treatment liquid containing a hydrophilic polymer has been used as a hard surface treatment agent for imparting antifouling properties to hard surfaces such as ceramics, porcelain and glass. For example, Patent Document 1 proposes a surface treatment agent containing a copolymer containing a specific structural unit having a betaine group and a specific structural unit having a cationic group.

  However, in general, the hydrophilic polymer tends to flow down with water, so that the antifouling property tends to be lowered, that is, the antifouling durability is poor.

JP 2017-190381 A

  An object of the embodiment of the present invention is to provide a hard surface treatment agent having excellent antifouling durability.

The hard surface treating agent according to the embodiment of the present invention includes a copolymer (A) of diallyldialkylammonium halide (a1) and (meth) acrylate (a2), and a repeating unit having a sulfonate. polymer (B), only contains those wherein the polymer (B) is at least one selected from the group consisting of styrene sulfonic acid salt-based polymer and (meth) acrylamide alkyl sulfonate polymer It is.

  When it is the hard surface treatment agent, it easily adheres to the hard surface, and the antifouling property can be imparted to the hard surface by the formed coating film. In addition, the coating film hardly flows off even when rinsed with water, and therefore has excellent antifouling durability.

  The hard surface treating agent according to this embodiment includes a copolymer (A) of diallyldialkylammonium halide (a1) and (meth) acrylate (a2), and a polymer containing a repeating unit having a sulfonate. (B), and is used to impart antifouling properties to the hard surface. The copolymer (A) can easily adhere to the hard surface of inorganic materials such as ceramics, porcelain and glass due to the cationic group of (a1), and can improve the durability of the coating film formed on the hard surface. it is conceivable that. Moreover, it is thought that a hydrophilic coating film is formed by the anionic group which (a2) has, and it can exhibit the antifouling property with respect to oil dirt, and is excellent in antifouling durability. Moreover, antifouling durability can be further improved by using together the polymer (B) which has a sulfonate.

[Copolymer (A)]
In the copolymer (A), the diallyldialkylammonium halide (a1) may be diallyldimethylammonium halide or diallyldialkylammonium chloride. Specifically, diallyldimethylammonium chloride is preferred.

  (Meth) acrylate (a2) means acrylate and / or methacrylate, and includes alkali metal salts, ammonium salts, and alkanolamine salts of acrylic acid and / or methacrylic acid. An alkali metal acrylate such as sodium acrylate is preferable.

  In one embodiment, the copolymer (A) includes a repeating unit (a10) represented by the following formula (1) and a repeating unit (a20) represented by the following formula (2). (A10) is a repeating unit corresponding to the monomer (a1), and (a20) is a repeating unit corresponding to the monomer (a2).

In formula (1), R ¹ and R ² each independently represents an alkyl group having 1 to 5 carbon atoms, preferably a methyl group. X ⁻ represents a halide ion, preferably Cl ⁻ . In formula (2), R ³ represents a hydrogen atom or a methyl group. Y ⁺ represents an alkali metal ion, an ammonium ion, or an onium ion of an alkanolamine, and is preferably an alkali metal ion such as Na ⁺ or K ⁺ .

  In the copolymer (A), the content ratios of (a1) and (a2) are not particularly limited. For example, 30% by mass of diallyldialkylammonium halide (a1) is contained in all monomers constituting the copolymer (A). The content is preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more. By increasing the content of (a1), the effect of improving antifouling durability can be enhanced. The upper limit of the content of (a1) may be, for example, 98% by mass or less, 95% by mass or less, or 93% by mass or less.

  The content of the (meth) acrylate (a2) in all monomers constituting the copolymer (A) is preferably 2% by mass or more, may be 5% by mass or more, and may be 7% by mass or more. Good. Moreover, the upper limit may be 70 mass% or less, for example, 50 mass% or less, 30 mass% or less, or 20 mass% or less.

  The mass ratio (a1) / (a2) of (a1) to (a2) in the copolymer (A) is not particularly limited, but is preferably 0.5 or more, for example, 1 or more, or 2 or more. Three or more may be sufficient. By increasing the mass ratio (a1) / (a2), the effect of improving antifouling durability can be enhanced. The mass ratio (a1) / (a2) is also preferably 50 or less, 30 or less, 20 or less, 15 or less, or 10 or less.

  Monomers constituting the copolymer (A) are basically only (a1) and (a2), but monomers other than (a1) and (a2) may be used as long as the effects of the present embodiment are not impaired. You may contain.

  The molecular weight of the copolymer (A) is not particularly limited. For example, the weight average molecular weight (Mw) may be 10,000 to 1,000,000, or 100,000 to 500,000. The weight average molecular weight can be measured by GPC method.

  The copolymer (A) is preferably a random copolymer.

  The method for synthesizing the copolymer (A) is not particularly limited, and can be synthesized by a known polymerization method, for example, by radical polymerization. In addition, about (meth) acrylate (a2), you may neutralize (meth) acrylic acid in any step before superposition | polymerization before superposition | polymerization.

  Content of a copolymer (A) is not specifically limited, 0.01 mass% or more may be sufficient with respect to the whole quantity of a hard surface treating agent, 0.03 mass% or more may be sufficient, 0.05 mass% or more But you can. Moreover, 3 mass% or less may be sufficient, 1 mass% or less may be sufficient, 0.7 mass% or less may be sufficient, and 0.5 mass% or less may be sufficient.

[Polymer (B)]
The polymer (B) is a hydrophilic anionic polymer having a sulfonate in a repeating unit (hereinafter, the polymer (B) may be referred to as a sulfonate polymer). The polymer (B) may be a polymer composed only of a repeating unit having a sulfonate, or may be a copolymer including other repeating units together with the repeating unit. The sulfonate is a group represented by —SO ₃ ⁻ M ⁺ (wherein M ⁺ represents an alkali metal ion, an ammonium ion, or an onium ion of an alkanolamine), and is a sulfonic acid sodium salt or sulfonic acid. A sulfonic acid alkali metal salt such as a potassium salt is preferred.

  Specific examples of the sulfonate polymer (B) include polystyrene sulfonate and styrene sulfonate polymers such as copolymers of styrene sulfonate and other vinyl monomers; poly (meth) acrylamide (Meth) acrylamide alkyl sulfonate-based polymers such as alkyl sulfonates and copolymers of (meth) acrylamide alkyl sulfonates with other vinyl monomers; and polyvinyl sulfonates and vinyl sulfonates And vinyl sulfonate-based polymers such as copolymers with other vinyl monomers. Any one of these may be used, or two or more of these may be used in combination. Examples of the other vinyl monomers include (meth) acrylic monomers such as (meth) acrylamide, (meth) acrylic acid, and (meth) acrylic acid esters. Here, “(meth) acryl” means “acryl” and / or “methacryl”. When the sulfonate polymer (B) is a copolymer, the polymer (B) preferably contains 50% by mass or more of repeating units having a sulfonate, more preferably 70% by mass or more. .

  The molecular weight of the sulfonate polymer (B) is not particularly limited. For example, the weight average molecular weight (Mw) may be 5,000 to 1,000,000, or 10,000 to 700,000. The weight average molecular weight can be measured by GPC method.

  The content of the sulfonate polymer (B) is not particularly limited, and may be 0.01% by mass or more, 0.03% by mass or more, and 0.05% with respect to the total amount of the hard surface treatment agent. It may be greater than or equal to mass%. Moreover, 3 mass% or less may be sufficient, 1 mass% or less may be sufficient, 0.7 mass% or less may be sufficient, and 0.5 mass% or less may be sufficient.

  The mass ratio of the copolymer (A) to the sulfonate polymer (B) in the hard surface treatment agent is preferably (A) / (B) = 0.05 to 10 and has antifouling durability. The improvement effect can be enhanced. The lower limit of the mass ratio (A) / (B) is more preferably 0.1 or more, still more preferably 0.15 or more, and the upper limit is more preferably 8 or less, still more preferably 6 or less. It is.

[Surfactant (C)]
The hard surface treating agent according to the present embodiment preferably contains a surfactant (C) together with the copolymer (A) and the sulfonate polymer (B). Examples of the surfactant (C) include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants, and these can be used alone or in combination of two or more.

  Examples of the nonionic surfactant include polyoxyalkylene alkyl phenyl ether, polyoxyalkylene alkyl ether, polyoxyalkylene fatty acid ester, polyhydric alcohol fatty acid ester alkylene oxide adduct, alkylamine alkylene oxide adduct, fatty acid amide alkylene oxide. Examples include adducts, alkyl glycosides, and sucrose fatty acid esters. Any of these may be used alone or in combination of two or more.

  As an anionic surfactant, for example, alkyl sulfate ester salt, polyoxyalkylene alkyl ether sulfate ester salt, alkylbenzene sulfonate, alkyl naphthalene sulfonate, alkyl phosphate ester salt, polyoxyalkylene alkyl ether phosphate ester salt, Examples include polyoxyalkylene alkyl ether carboxylate salts, polycarboxylic acid salts, alkyl diphenyl ether sulfonate salts, and the like. Any of these may be used alone or in combination of two or more.

  Examples of cationic surfactants include alkylamine salts, fatty acid triethanolamine monoester salts, acylaminoethyl diethylamine salts, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, alkylpyridinium salts, and acylaminoalkyls. Examples thereof include pyridinium salts and diacyloxyethylammonium salts. Any of these may be used alone or in combination of two or more.

  Examples of amphoteric surfactants include fatty acid amidopropyl betaine, fatty acid amidopropyldimethylaminoacetic acid betaine, lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, laurylhydroxysulfobetaine. Betaine-type amphoteric surfactants such as sodium lauroylamidoethylhydroxyethylcarboxymethylbetaine hydroxypropyl sodium phosphate; amino acid-type amphoteric surfactants such as sodium β-laurylaminopropionate; amine-oxide-type amphoteric interfaces such as lauryldimethylamine oxide An active agent etc. are mentioned. Any of these may be used alone or in combination of two or more.

  Among these surfactants, use of at least one selected from the group consisting of a nonionic surfactant (C1) and an amphoteric surfactant (C2) can enhance the effect of improving antifouling durability. It is possible to use an amphoteric surfactant (C2). In addition, you may use together about an anionic surfactant from a viewpoint which provides a hard surface treatment agent with washability. The cationic surfactant may be used in combination from the viewpoint of imparting antibacterial properties to the hard surface treatment agent.

  Content of surfactant (C) is not specifically limited, 0.1 mass% or more may be sufficient with respect to the whole quantity of a hard surface treating agent, 0.3 mass% or more may be sufficient, 0.5 mass% or more But you can. Moreover, 15 mass% or less may be sufficient, 10 mass% or less may be sufficient, and 8 mass% or less may be sufficient.

  The content ratio of the surfactant (C) to the copolymer (A) is not particularly limited. For example, when the mass ratio (C) / (A) = 0.01 to 70, wettability and antifouling are achieved. The durability can be further improved, which is preferable. The mass ratio (C) / (A) may be 0.1 or more, 0.5 or more, 1 or more, or 2 or more. Further, the mass ratio (C) / (A) may be 50 or less, 40 or less, or 30 or less.

[Hard surface treatment agent]
The hard surface treatment agent according to this embodiment preferably contains water together with the copolymer (A), the sulfonate polymer (B), and the surfactant (C) which is an optional component. That is, the hard surface treatment agent according to the present embodiment may be solid, but the hard surface treatment agent according to a preferred embodiment is a sulfonate salt together with the copolymer (A) that is a water-soluble polymer. This is an aqueous solution containing the polymer (B), and can therefore be referred to as a hard surface treatment liquid.

  The water content is preferably 80% by mass or more, more preferably 90% by mass or more, based on the total amount of the hard surface treatment agent. The upper limit of the water content is not particularly limited, and may be, for example, 99.98% by mass or less, 99.88% by mass or less, or 99% by mass or less. When the water content is 80% by mass or more, it is possible to suppress the viscosity of the hard surface treatment agent and improve the handleability when processing the hard surface by spraying or the like.

  In the hard surface treating agent according to the present embodiment, in addition to the above components, various additives blended in the normal hard surface treating agent within a range not impairing the effects of the present embodiment, for example, chelating agents, organic You may mix | blend a solvent, an antibacterial agent, a fragrance | flavor, etc.

  The hard surface treatment agent according to the present embodiment includes a copolymer (A), a sulfonate polymer (B), and optionally a surfactant (C), water, and other components, It can be prepared by stirring and mixing by a known method.

  The hard surface treating agent according to this embodiment is used for treating a hard surface. Examples of the hard surface include inorganic solid surfaces such as ceramics, porcelain, glass, glazing, tiles, ceramics, aluminum, and stainless steel. As a preferred embodiment, it may be used as a surface treatment agent for imparting antifouling properties to the toilet bowl surface. For example, the toilet bowl surface is washed and a hydrophilic film is formed on the toilet bowl surface to form a hydrophilic surface. It may be used as a surface treatment agent for imparting antifouling properties by making it.

  It does not specifically limit as a processing method of a hard surface, What is necessary is just to make the hard surface treating agent which concerns on this embodiment contact a hard surface. For example, the method of spraying or apply | coating a hard surface treating agent to a hard surface is mentioned. Moreover, the method of immersing a hard surface in a hard surface treating agent is mentioned.

  In the method of spraying or applying the hard surface treatment agent to the hard surface, it may be dried after being sprayed or applied. If necessary, after spraying, it may be rinsed with water, or after spraying, it may be spread thinly using a sponge or the like.

The amount of the hard surface treatment agent sprayed or applied to the hard surface is not particularly limited, but may be 1 to 100 mg per 10 cm ^{2 of} the hard surface, for example. The temperature of the hard surface treatment agent when treating the hard surface may be, for example, 5 ° C. or higher, 10 ° C. or higher, and 15 ° C. or higher. Further, it may be 50 ° C. or lower, 40 ° C. or lower, or 30 ° C. or lower.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.

  A hard surface treating agent was obtained by mixing each raw material according to the formulation (parts by mass) shown in Table 1 below. The composition in Table 1 is a ratio as a solid content for components other than water, and the amount of water is the total amount of the hard surface treatment agent including the amount of water contained in the components other than water. is there.

The details of each component in Table 1 are as follows.
(A-1) Copolymer 1: Copolymer obtained in Synthesis Example 1 below (A-2) Copolymer 2: Copolymer obtained in Synthesis Example 2 below (B-1) Sulfonate-based polymer 1: Sodium polystyrene sulfonate (trade name: Polynus PS-5, manufactured by Tosoh Organic Chemical Co., Ltd., weight average molecular weight = 50,000)
(B-2) sulfonate polymer 2: sodium polyacrylamide alkyl sulfonate (trade name: Aron A-6012, manufactured by Toagosei Co., Ltd., weight average molecular weight = 10,000)
(C-1) Nonionic surfactant: polyoxyethylene alkyl ether (trade name: DKSNL-80, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
(C-2) Anionic surfactant: sodium alkyl sulfate (trade name: Monogen Y-500, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
(C-3) Amphoteric surfactant: Fatty acid amidopropyl betaine (trade name: Amogen CB-H, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
(A-1) Sodium polyacrylate (trade name: Charol AN-103P, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
(A-2) Polydiallyldimethylammonium chloride (trade name: Charol DC-902P, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
(A-3) Polydimethylaminoethyl methacrylate quaternized product (trade name: UNISENS FPV-1000L, manufactured by Senka Corporation).

[Synthesis Example 1]
81 g of diallyldimethylammonium chloride, 6.9 g of acrylic acid, and 50 g of water were mixed and adjusted to pH 4 using an aqueous sodium hydroxide solution (concentration: 48% by mass) to obtain a dropped aqueous solution. Further, 0.02 g of ammonium persulfate and 20 g of deionized water were mixed to obtain an aqueous solution of ammonium persulfate.

  In a 1 liter reaction vessel purged with nitrogen, 9 g of diallyldimethylammonium chloride, 0.8 g of acrylic acid, 0.15 g of ethylenediaminetetraacetic acid tetrasodium and 275 g of deionized water were added to obtain a homogeneous solution, and hydrochloric acid (concentration: 5% by mass) Was adjusted to pH 4 and heated to 100 ° C. To this aqueous solution, the dropping aqueous solution and the ammonium persulfate aqueous solution were simultaneously dropped. In addition, the dropping aqueous solution was dripped over 60 minutes, and the ammonium persulfate aqueous solution was dripped at the speed | rate of 0.1 mL / min. After completion of all the additions, the reaction was further performed at 100 ° C. for 30 minutes, and then 2.6 mL of sodium metabisulfite (concentration: 1% by mass) was added dropwise at 0.3 mL / min, and the reaction was further performed at 100 ° C. for 30 minutes. After cooling to 25 ° C. and adding deionized water to a solid concentration of 20% by mass, an aqueous solution of diallyldimethylammonium chloride / sodium acrylate copolymer (concentration: 20% by mass, in all monomers) A ratio of (a1): 90% by mass, (a1) / (a2) = 9 (weight ratio)) was obtained.

[Synthesis Example 2]
72 g of diallyldimethylammonium chloride, 13.8 g of acrylic acid and 50 g of water were mixed and adjusted to pH 4 using an aqueous sodium hydroxide solution (concentration: 48% by mass) to obtain a dropped aqueous solution. Further, 0.02 g of ammonium persulfate and 20 g of deionized water were mixed to obtain an aqueous solution of ammonium persulfate.

  In a 1-liter reaction vessel purged with nitrogen, 8 g of diallyldimethylammonium chloride, 1.5 g of acrylic acid, 0.15 g of ethylenediaminetetraacetic acid tetrasodium and 275 g of deionized water were added to obtain a homogeneous solution, and hydrochloric acid (concentration: 5% by mass) Was adjusted to pH 4 and heated to 100 ° C. To this aqueous solution, the dropping aqueous solution and the ammonium persulfate aqueous solution were simultaneously dropped. In addition, the dropping aqueous solution was dripped over 60 minutes, and the ammonium persulfate aqueous solution was dripped at the speed | rate of 0.1 mL / min. After completion of all the additions, the reaction was further performed at 100 ° C. for 30 minutes, and then 2.6 mL of sodium metabisulfite (concentration: 1% by mass) was added dropwise at 0.3 mL / min, and the reaction was further performed at 100 ° C. for 30 minutes. After cooling to 25 ° C. and adding deionized water to a solid concentration of 20% by mass, an aqueous solution of diallyldimethylammonium chloride / sodium acrylate copolymer (concentration: 20% by mass, in all monomers) A ratio of (a1): 80% by mass, (a1) / (a2) = 4 (mass ratio)) was obtained.

  The antifouling durability of each of the hard surface treatment agents of Examples 1 to 10 and Comparative Examples 1 to 6 obtained was evaluated by the following method.

20 mg of a hard surface treatment agent was applied in a range of 4 cm × 2.5 cm on the surface of the glass plate and allowed to stand at 20 ° C. for 5 minutes. This was rinsed with running water (20 ° C., 3 L / min) for 10 seconds, stood at 90 ° and allowed to stand at 20 ° C. for 1 hour to form a coating film on the surface of the glass plate. Next, 20 mg of olive oil was dropped on the surface of the glass plate on which the coating film was formed, and then rinsed with running water (20 ° C., 3 L / min) for 3 seconds. And the surface of the glass plate was confirmed visually and evaluated on the following reference | standard. When the evaluation was A, the glass plate was rinsed for a long time before being allowed to stand for 1 hour after application of the hard surface treatment agent, and the same measurement was performed until the evaluation was B. The rinsing time was 30 seconds, 50 seconds, 100 seconds, 150 seconds, 200 seconds, 300 seconds, and 400 seconds.
A: Olive oil does not remain on the surface of the glass plate.
B: Olive oil remains on the surface of the glass plate.

  A result is as showing in Table 1, and it is antifouling property with respect to Comparative Examples 1-4 as it is Examples 1-10 which mix | blended the copolymer (A) and the sulfonate-type polymer (B). It was excellent and its sustainability was also excellent. In addition, Examples 1 to 10 were superior to Comparative Example 5 in antifouling durability. From the comparison between Example 1 and Examples 3 and 5 to 10, by using a nonionic surfactant or an amphoteric surfactant together with the copolymer (A) and the sulfonate polymer (B), The soil durability could be further improved.

  As mentioned above, although some embodiment of this invention was described, these embodiment is shown as an example and is not intending limiting the range of invention. These embodiments can be implemented in various other forms, and various omissions, replacements, and changes can be made without departing from the spirit of the invention. These embodiments and their omissions, replacements, changes, and the like are included in the inventions described in the claims and their equivalents as well as included in the scope and gist of the invention.

Claims (3)

Copolymers of diallyl dialkyl ammonium halide and (a1) and (meth) acrylate (a2) (A), and, seen containing a polymer (B), containing a repeating unit having a sulfonic acid salt, said polymer A hard surface treating agent , wherein (B) is at least one selected from the group consisting of a styrene sulfonate-based polymer and a (meth) acrylamide alkyl sulfonate-based polymer .   The hard surface treating agent according to claim 1, wherein a mass ratio of the copolymer (A) to the polymer (B) is (A) / (B) = 0.05-10.   The hard surface treating agent according to claim 1 or 2, further comprising a surfactant (C).