JP2021172715A - Antifouling cleaning agent, cleaning product and antifouling cleaning method - Google Patents

Abstract

To provide an antifouling detergent, a water-decomposable cleaning product, and an antifouling cleaning method that make it possible to maintain the antifouling property of cleaning targets for a long period of time.SOLUTION: An antifouling cleaning agent comprising a) 0.01 to 30 wt.% of ternary amphoteric polymers composed of 15 to 40% (molar ratio) of quaternary ammonium salt monomers of diallyldimethylammonium salt or methacrylamidopropyltrimethylammonium salt, 30 to 60% (molar ratio) of acrylamide monomers, and 10 to 45% (molar ratio) of anionic monomers of acrylic acid or its salt or methacrylic acid or its salt, and b) a surfactant; a cleaning product in which the antifouling cleaning agent is held in an infiltrated state in water-soluble paper; and a hard surface antifouling cleaning method that treats a hard surface with the antifouling cleaning agent.SELECTED DRAWING: None

Description

The present invention relates to an antifouling detergent, a cleaning product, and an antifouling cleaning method capable of removing stains and suppressing stains.

Dirt occurs in various places in the house. Various cleaning agents are provided to remove those stains.

Toilet spaces and toilet bowls are frequently used and are the most dirty places in the house. Therefore, the frequency of cleaning is high, and it is a time-consuming place to maintain cleanliness. Against this background, many products have been proposed to make it easier to clean the toilet.

It is installed under the faucet of the hand-washing tank of the toilet, and when water is flushed, a small amount of detergent is supplied to clean the inside of the toilet bowl and make it difficult to get dirty. Detergents have been proposed. Alternatively, a cleaning agent that is sprayed directly inside and outside the toilet bowl or around the toilet bowl to remove stains and prevent them from getting dirty is also provided.

Many so-called antifouling technologies have been found so far that make it difficult for such stains to adhere. For example, Japanese Patent Application Laid-Open No. 2002-60786 describes a polymer having a molecular weight of 1000 to 6000000 and a ratio of monomer units having a quaternary ammonium group of 10 to 100 mol% with respect to all monomers, and 4 having a molecular weight of 1000 or less. A sterilizing and cleaning agent for hard surfaces containing a sterilizing agent having a quaternary ammonium group is described. Japanese Unexamined Patent Publication No. 2002-146395 contains one or more surfactants selected from nonionic surfactants and amphoteric surfactants, and polymers containing monomer units having a quaternary ammonium group or a tertiary amino group. A cleaning agent for hard surfaces to be used is described. JP-A-2003-313600 discloses, a monomer having a group selected from amino groups and quaternary ammonium groups in the molecule one or more, -SO 2 _- in the antifouling cleaning hard surfaces comprising the monomer represented The agent is listed. Japanese Patent Application Laid-Open No. 2008-523184 discloses a surface protectant and a cleaning composition containing a polymer having a cationic monomer containing a diallyldimethylammonium group as a part of a constituent unit.

Further, a gel-like detergent has been proposed which adheres to the surface of a toilet bowl portion or the like and continuously releases an active ingredient by running water to perform cleaning, aroma, and deodorization. For example, Japanese Patent Application Laid-Open No. 2011-57780 describes a gel-like cleaning composition for toilets containing polyoxyethylene alkyl ether. Japanese Unexamined Patent Publication No. 2015-199936 describes a gel-like detergent composition containing a polyoxyalkylene block polymer and water. Japanese Unexamined Patent Publication No. 2017-12508 discloses a gel-like detergent composition containing a tetraalkylammonium salt, a polyoxyalkylene block polymer, a polyoxyalkylene alkyl ether, and / or a water-soluble inorganic chloride.

On the other hand, as a sheet-shaped cleaning article impregnated with a cleaning agent, a product has been proposed that can be washed and disposed of in the toilet after removing dirt inside and outside the floor, wall, tank, and toilet bowl of the toilet by wiping. For example, Japanese Patent Application Laid-Open No. 2-149237 provides an article in which a water-dissolved paper containing a water-soluble binder having a carboxyl group is impregnated with an aqueous cleaning agent containing metal ions and an organic solvent as essential components. Japanese Patent No. 4652884 proposes a toilet cleaning sheet impregnated with a cleaning liquid containing an amphoteric polymer compound having an antifouling function.

As described above, various technologies and products have been proposed for toilets, but no product has been proposed that maintains antifouling properties for a long period of time by one-time cleaning and cleaning.

JP-A-2002-60786 JP-A-2002-146395 Japanese Unexamined Patent Publication No. 2003-313600 Japanese Patent Application Laid-Open No. 2008-523184 Japanese Unexamined Patent Publication No. 2011-57780 Japanese Unexamined Patent Publication No. 2015-199936 Japanese Unexamined Patent Publication No. 2017-125088 Japanese Unexamined Patent Publication No. 2-149237 Japanese Patent No. 4652884

An object of the present invention is to provide an antifouling detergent, a water-decomposable cleaning product, and an antifouling cleaning method capable of maintaining the antifouling property of the object to be cleaned or cleaned for a long period of time.

The present invention a) quaternary ammonium salt monomers of diallyldimethylammonium salt or methacrylamidepropyltrimethylammonium salt 15 to 40% (molar ratio), acrylamide monomer 30 to 60% (molar ratio) and acrylic acid or a salt thereof or methacryl. An antifouling cleaning agent containing 0.01 to 30% by weight of a ternary amphoteric polymer composed of 10 to 45% (molar ratio) of anionic monomers of an acid or a salt thereof and b) a surfactant.
A water-decomposable cleaning product having a specific configuration in which the water-detergent is impregnated with the antifouling detergent, and a hard surface antifouling cleaning method for treating a hard surface with the antifouling detergent.

According to the present invention, it is possible to provide a cleaning agent, a water-decomposable cleaning product, and an antifouling cleaning method capable of maintaining the antifouling property of the object to be cleaned or cleaned for a long period of time.

The antifouling detergent of the present invention contains a) a ternary amphoteric polymer and b) a surfactant. The cleaning product of the present invention holds the antifouling cleaning agent of the present invention in a water-melted paper in a soaked state, and the hard surface antifouling cleaning method of the present invention uses the antifouling cleaning agent of the present invention to clean a hard surface. It is to be processed.

(1) Three-way amphoteric polymer

(1-1) In the present invention, the antifouling function is exhibited a) 15 to 40% (molar ratio) of a quaternary ammonium salt monomer of diallyldimethylammonium salt or a quaternary ammonium salt monomer of methacrylicamidopropyltrimethylammonium salt. , 30 to 60% (molar ratio) of acrylamide monomer and anionic monomer of acrylic acid or its salt or 10 to 45% (molar ratio) of anionic monomer of methacrylic acid or its salt. It is a former amphoteric polymer.

It is composed of the above-mentioned cation monomer, nonion monomer, and anion monomer, and when the copolymerization ratio thereof is in the above range, it is possible to exhibit a highly durable antifouling function.

In addition to the antifouling function, a cleaning function is indispensable for keeping a hard surface such as a toilet clean and tidy. For that purpose, a cleaning agent containing both a surfactant and an antifouling agent and its cleaning Sheet-shaped cleaning products impregnated with an agent are useful. The above-mentioned polymer in the present invention is an amphoteric polymer having both cationic and anionic properties, but even if this ternary amphoteric polymer and most of the surfactants are mixed together, a uniform solution state can be obtained. It can be maintained and the blended mixture can exhibit detergency and antifouling properties at the same time.

(1-2) The ternary amphoteric polymer in the present invention is represented by the following general formula [1] or [2].

．．．．［１］

.. .. .. .. [1]

．．．．［２］

.. .. .. .. [2]

In the general formulas [1] and [2], R represents a hydrogen atom or a methyl group, and n, m and z represent the molar ratio of each monomer unit. n + m + z = 100, m is 15 to 40, z is 30 to 60, and n is 10 to 45. When n, m and z are within this range, a uniform cleaning liquid can be obtained even when used in combination with most surfactants, and continuous antifouling property can be exhibited.

The copolymerization ratio (molar ratio) of each monomer in this ternary amphoteric polymer can be measured by, for example, the following method.

The amount (weight) of the cation monomer in the polymer is calculated by quantifying chlorine (Cl), which is the counterion of the cation monomer, by the combustion ion chromatography method. Next, the total amount of nitrogen (N) present in the present polymer is quantified by total nitrogen analysis (Total Nitrogen Analysis) or CHN analysis. Since the amount of cation monomer has been calculated, the amount of acrylamide monomer (weight) is calculated by calculating the amount of N corresponding to the amount of cation monomer and subtracting it from the total amount of N in the polymer. Further, the weight of acrylic acid can be calculated by subtracting the weight of the cation monomer and the weight of the acrylamide monomer from the weight (solid content) of the entire polymer. Since the solid content of the polymer contains a small amount of water, it is preferable to measure the water content by a heat vaporization method or the like to calculate the weight ratio of each monomer to the polymer solid content after water subtraction. By dividing (dividing) the weight ratio of each obtained monomer by the molecular weight of each monomer, it is possible to convert it into the molar ratio of each monomer in the polymer.

Further, by measuring the 1H-NMR spectrum and the 13C-NMR spectrum using an NMR measuring instrument, it is possible to assign a signal peculiar to each monomer and quantify the copolymerization ratio.

(1-3) The ternary amphoteric polymer of the present invention is blended in an antifouling detergent in an amount of 0.01 to 30% by weight. If it is 0.01% by weight or less, it is difficult to develop sustainable antifouling performance, and if it exceeds 30% by weight, the viscosity of the antifouling detergent becomes high, and it becomes difficult to apply it to various product forms.

The ternary amphoteric polymer supplied to the surface to be cleaned exhibits antifouling properties from a low concentration of 0.01% by weight, and the concentration in the product is preferably adjusted appropriately depending on the product form.

For example, when the antifouling detergent is directly discharged to the target surface with a spray bottle or a squeeze bottle, it is preferably blended in an amount of 0.01 to 2% by weight. Further, it is more preferably 0.05 to 0.5% by weight from the viewpoint of antifouling performance and economy.

In addition, an antifouling detergent that is installed under the faucet of the hand-washing tank of the toilet and is supplied into the tank while being diluted with a part of the detergent mixed with the water supplied from the faucet when washed with water. In the case where a gel-like antifouling detergent is fixed to the bowl of the toilet bowl and gradually dissolved in water during washing and supplied to the target surface, the concentration should be set in consideration of the dilution ratio. preferable. In such products, it is preferably blended in an amount of 0.5 to 30% by weight. Further, it is preferably 1 to 10% by weight from the viewpoint of antifouling performance and manufacturing suitability.

In addition, in products such as paper and non-woven sheets that are pre-impregnated with a liquid antifouling detergent and held in an infiltrated state, compared to the antifouling detergent used for spray bottles and squeeze bottles, Since the amount of the antifouling detergent adhering to the target surface is reduced, it is preferable to set the concentration according to the product characteristics. In such products, 0.25 to 10% by weight is preferably blended in the antifouling detergent.

(1-4) The weight average molecular weight of the ternary amphoteric polymer in the present invention is preferably 5000 to 3000000. Further, it is preferably 50,000 to 2000000, and particularly preferably 100,000 to 1800000. When the weight average molecular weight is in the range of 5000 to 3000000, a uniform solution can be easily obtained even when used in combination with most surfactants, and excellent antifouling properties can be easily exhibited.

(2) Surfactant

The antifouling detergent of the present invention may contain one or more surfactants.

(2-1) At least one of the surfactants contained in the antifouling detergent of the present invention is preferably a cationic surfactant selected from quaternary ammonium salts. This cationic surfactant has a high sterilizing power and is effective in suppressing the generation and accumulation of stains due to the growth of bacteria and the generation of malodor due to metabolism. Specific examples thereof include those of the following chemical formulas [3] and [4], but the present invention is not limited to these, and for example, a double-chain type quaternary ammonium salt having two C8 or higher alkyl groups. It may be a type, and the counter ion may be other than chloride ion.

．．．．［３］

.. .. .. .. [3]

．．．．［４］

.. .. .. .. [4]

In formulas [3] and [4], R represents an alkyl group of C8 to C16.

The antifouling detergent of the present invention preferably contains 0.01 to 20% by weight of a cationic surfactant selected from such quaternary ammonium salts. It is more preferably 0.01 to 10% by weight, and most preferably 0.01 to 5% by weight. Even if the cationic surfactant is used as the surfactant, the antifouling property of the ternary amphoteric polymer in the antifouling detergent of the present invention is not impaired, and the antifouling property having excellent durability can be exhibited.

(2-2) At least one of the surfactants contained in the antifouling detergent of the present invention is preferably an alkyl glucoside or an alkyl amine oxide. Both the alkyl glucoside and the alkyl amine oxide have excellent compatibility with the ternary amphoteric polymer in the antifouling detergent of the present invention. Further, both the alkyl glucoside and the alkyl amine oxide have excellent compatibility with the ternary amphoteric polymer when used in combination with a cationic surfactant such as a quaternary ammonium salt, and are excellent in compatibility with the cationic surfactant. It does not impair sterilization performance.

The antifouling detergent of the present invention using an alkyl glucoside or an alkylamine oxide as at least one of the surfactants has good wettability and permeability to fixed stains and is also excellent in detergency. In addition, the antifouling property of the ternary amphoteric polymer is not impaired. Even when an anionic surfactant is used in combination, it is easy to obtain a uniform and stable cleaning solution.

Examples of the alkyl glucoside include those having the following chemical formula [5].
R ¹ − (OR ² ) nGm. .. .. .. [5]

In the formula [5], R ¹ is an alkyl group of C8 to C18, R ² is an alkylene group of C2 to C4, G is a group derived from a reducing sugar, and n is an average number of moles (0 to 5). , M represent the average degree of condensation (1 to 3), respectively.

The reducing sugar may be either aldose or ketose, but glucose is preferable.

More specific examples of alkyl glucosides include octyl polyglucoside, 2-ethylhexyl poly glucoside, decyl poly glucoside, lauryl poly glucoside, myristyl poly glucoside, palmityl poly glucoside, stearyl lauryl poly glucoside, oleyl poly glucoside and the like. .. Among these, an alkyl glucoside having an alkyl group having 16 or less carbon atoms is preferable.

Examples of alkylamine oxides include those of the following chemical formula [6].

．．．．［６］

.. .. .. .. [6]

In formula [6], R ¹ represents an alkyl group or an alkenyl group of C8 to C18, and R ² and R ³ represent an alkyl group of C1 to C4 independently of each other.

More specific examples of alkylamine oxides include lauryldimethylamine oxide, myristyldimethylamine oxide, coconut alkyldimethylamine oxide, lauryl-bis (2-hydroxyethyl) amine oxide, and myristyl-bis (2-hydroxyethyl) amine. Examples thereof include oxides and coconut alkyl-bis (2-hydroxyethyl) amine oxides. These can be used alone or in admixture of two or more. Preferred are lauryldimethylamine oxide and coconut alkyldimethylamine oxide.

The antifouling detergent of the present invention preferably contains 0.1 to 20% by weight of an alkyl glucoside or an alkyl amine oxide. It is more preferably 0.2 to 10% by weight, and most preferably 0.2 to 5% by weight. Even if the alkyl glucoside or alkyl amine oxide type surfactant is used as the surfactant, the antifouling function of the ternary amphoteric polymer in the antifouling detergent of the present invention is not impaired, and the antifouling property is excellent in durability. It can be dirty.

(2-3) The antifouling cleaning agent of the present invention includes various surfactants other than cationic surfactants, alkyl glucosides or alkyl amine oxides, for example, commonly used anionic surfactants and nonionic surfactants. , Amphoteric surfactant, etc. can be used.

The anionic surfactant may form an insoluble matter by forming a complex with the ternary amphoteric polymer in the antifouling detergent of the present invention, and the above-mentioned alkylaminooxide type surfactant or sodium citrate may be produced. By using the above in combination, it is possible to prepare a uniform cleaning solution without precipitates.

(3) Other ingredients of antifouling detergent

(3-1) The antifouling detergent of the present invention preferably contains 1 to 10% by weight of sulfamic acid (amide sulfate) when dissolving and removing adhered urinary stone stains. If it is less than 1% by weight, the detergency of urinary stone stains is not sufficient, and if it exceeds 10% by weight, there is not much difference in detergency and it is not efficient. The content of sulfamic acid is more preferably 3 to 8% by weight, most preferably 4 to 7 to%. Even if sulfamic acid is used in combination, the antifouling function of the ternary amphoteric polymer in the antifouling detergent of the present invention is not impaired, and the antifouling property having excellent durability can be exhibited.

(3-2) The antifouling detergent of the present invention may contain 2 to 10% by weight of hypochlorite when removing organic stains and urinary stone stains adhering to the toilet bowl. preferable. If it is less than 2% by weight, the detergency of organic stains and urinary stone stains is not sufficient, and if it exceeds 10% by weight, there is not much difference in detergency, which is not efficient. Even if hypochlorite is used in combination, the antifouling function of the ternary amphoteric polymer in the antifouling detergent of the present invention is not impaired, and the antifouling property having excellent durability can be exhibited. In addition, in the cleaning agent containing hypochlorite, the above sulfamic acid is not used in combination.

(3-3) The antifouling cleaning agent of the present invention contains sodium carbonate and / or sodium hydrogen carbonate when removing sebum stains and denatured stubborn oil stains, and the pH is adjusted to 9 to 11. Is preferable. Weakly alkaline carbonate is a cleaning base that is excellent in safety, has no sliminess, and has excellent rinsing properties. It can be used in combination with a surfactant, or can exert a certain detergency without using a surfactant in combination. Further, even when sodium carbonate and / or sodium hydrogen carbonate is used in combination, the antifouling function of the ternary amphoteric polymer in the antifouling cleaning agent of the present invention is not impaired, and the antifouling property having excellent durability is exhibited. can.

(3-4) The antifouling detergent of the present invention may contain components other than the above as long as the action and effect of the present invention are not impaired.

(4) Hydrolyzable cleaning supplies

(4-1) The antifouling cleaning agent of the present invention can be kept in an infiltrated state by impregnating water-decomposable paper or the like to provide a water-decomposable cleaning product.

That is, it is a cleaning product in which a liquid antifouling detergent is held in an infiltrated state in a water-dissolved paper containing a water-soluble binder having a carboxyl group, and contains calcium ions and / or zinc ions. The liquid antifouling cleaning agent is a water-decomposable cleaning product which is the above-mentioned antifouling cleaning agent containing 10 to 40% by weight of a water-soluble solvent.

For example, Japanese Patent Application Laid-Open No. 2-149237 discloses an article in which a water-dissolved paper containing a water-soluble binder having a carboxyl group is impregnated with an aqueous cleaning agent containing metal ions and an organic solvent as essential components. By impregnating such a water-decomposable cleaning article with the cleaning agent having the antifouling function of the present invention, the antifouling effect can be exhibited after cleaning the back edge of the toilet bowl, the bowl portion and the like. In hydrolyzed paper containing a water-soluble binder having a carboxyl group, the hydrolyzed paper is impregnated with a cleaning agent containing divalent metal ions such as calcium and zinc and a water-soluble organic solvent to maintain the strength at the time of cleaning. It has both water wash disposal performance (water decomposability).

On the other hand, even if a required amount of the ternary amphoteric polymer of the antifouling cleaning agent of the present invention is added to the cleaning agent having such a composition, a uniformly dissolved antifouling cleaning liquid can be obtained, so that antifouling can be performed by a simple process. It is possible to manufacture a water-decomposable cleaning product having a function. Further, even if the antifouling cleaning agent of the present invention is cleaned with a water-decomposable sheet held in an infiltrated state, the antifouling function of the polymer of the present invention is not impaired, and the antifouling property having excellent durability can be exhibited. ..

Calcium ions and / or zinc ions as metal ions that contribute to the temporary water resistance of the water-soluble binder having a carboxyl group are blended in an antifouling cleaning agent and infiltrated into the water-dissolved paper containing the water-soluble binder. It can be contained in the cleaning product by holding it in a state, but it is not limited to this. It can also be contained in.

(4-2) The amount of the antifouling cleaning agent of the present invention to be retained in the water-dissolved paper in an infiltrated state is preferably 150 to 400% by weight with respect to the water-dissolved paper. When the target surface is treated by wiping with a water-melting paper that holds the antifouling cleaning agent in an infiltrated state, if it is less than 150% by weight, the amount of the cleaning agent and thus the antifouling component adhering to the target surface becomes insufficient. If it exceeds 400% by weight, the residual amount of the cleaning agent on the target surface such as the toilet seat increases and stickiness tends to occur. More preferably, it is 200 to 300% by weight based on the water-dissolved paper.

(4-3) When the target surface is treated by wiping with a cleaning product that holds the antifouling detergent of the present invention in a water-melted paper in an infiltrated state, the antifouling detergent is applied to the target surface by spraying or squeezing. The amount of antifouling cleaning agent adhering to the target surface tends to be smaller than when it is applied directly. Therefore, in the case of an antifouling detergent that is infiltrated into water-melted paper, the concentration of the above-mentioned ternary amphoteric polymer that exerts an antifouling function should be higher than when it is directly applied by spraying or squeeze. Is preferable. In that case, the preferable concentration of the ternary amphoteric polymer is 0.25 to 10% by weight, more preferably 0.5 to 5% by weight.

(4-4) In order to uniformly dissolve divalent metal ions such as calcium and zinc in the antifouling cleaning agent of the present invention, the weight average molecular weight of the above ternary amphoteric polymer must be 500,000 or less. preferable. If the weight average molecular weight exceeds 500,000, there may be a disadvantage that a complex with a divalent metal ion is formed and insolubilized.

(4-5) The water-decomposable cleaning product of the present invention contains a water-soluble binder, a surfactant, a divalent metal salt, a water-soluble solvent, a fragrance, etc. as disclosed in Japanese Patent Application Laid-Open No. 2-149237. As the water-soluble binder, carboxymethyl cellulose (CMC), as the divalent metal salt, a water-soluble salt of calcium or zinc, and as the water-soluble solvent, those having a slower volatilization rate than water are preferable.

(5) Hard surface antifouling cleaning method

The specific form of the hard surface antifouling cleaning method for treating a hard surface using the antifouling cleaning agent of the present invention is not particularly limited, but for example, an antifouling cleaning agent can be used by using a sprayer such as a trigger or aerosol. A method of spraying directly on the object, a method of discharging the antifouling cleaning agent directly onto the object while squeezing using a squeeze bottle, a sponge or a sponge together with the antifouling cleaning agent applied directly to the object by spraying or squeezing. Clean the target surface by a method such as rubbing the target surface with a cleaning tool such as a brush, or by impregnating a sheet-like base material such as paper or non-woven fabric with an antifouling detergent to keep it in a soaked state. Examples include a wiping method and a method of supplying an antifouling cleaning agent to the toilet bowl together with water at the time of flushing, such as a water washing auto cleaner.

(6) According to the above-described embodiment of the present invention, it is possible to effectively remove stains, suppress stain adhesion, and easily remove stains (of stains attached after applying an antifouling cleaning agent). By cleaning, cleaning, etc. (for example, one-time cleaning, cleaning, etc.), the antifouling property of the object to be cleaned or cleaned can be continued for a long period of time.

For example, it is excellent by applying it to the whole house, especially the walls, floors and fixtures of kitchens, bathrooms, toilets, wash basins, etc., especially the inside and outside of toilet bowls, wash basins, sinks and other water areas, especially hard surfaces. It can be effective.

Example 1

(1) Polymer 1 [Mercoat 3331 (weight average molecular weight 1600000), which is a ternary amphoteric polymer (diallyldimethylammonium chloride / acrylamide / acrylic acid): manufactured by Nippon Lubrizol Co., Ltd., Merquat is a trademark of the same company] Prevents 0.25% by weight of solid content and 0.3% by weight of lauryl glucoside (Mydor 12: manufactured by Kao Co., Ltd., Mydor is a trademark of the same company), which is a nonionic surfactant, at a solid content of 0.3% by weight. A fouling cleaning solution was prepared.

(2) Except that polymer 1 was replaced with polymer 1'[Marcoat 3940 (weight average molecular weight 150,000): manufactured by Nippon Lubrizol Co., Ltd.], which is a ternary amphoteric polymer (diallyldimethylammonium chloride / acrylamide / acrylic acid). An antifouling cleaning solution was prepared in the same manner as in (1).

(3) Except that polymer 1 was replaced with polymer 2 [Mercoat 2003PR (weight average molecular weight 12000000): manufactured by Nippon Lubrizol Co., Ltd.], which is a ternary amphoteric polymer (methacrylamide propyltrimethylammonium chloride / acrylamide / acrylic acid). Prepared an antifouling cleaning solution in the same manner as in (1).

The compositions of the obtained antifouling cleaning agents are shown in Table 1, respectively.

Comparative Example 1

(4) Polymer 1 was replaced with polymer 3 [ternary amphoteric polymer (methacrylamide propyltrimethylammonium chloride / acrylic acid / methyl acrylate Marcourt 2001 (weight average molecular weight 12000000): manufactured by Nippon Lubrizol Co., Ltd.]. An antifouling cleaning solution was prepared in the same manner as in Example 1 (1) except for the above.

(5) Example 1 except that polymer 1 was replaced with polymer 4 [Marcoat 280 (weight average molecular weight 450,000): manufactured by Nippon Lubrizol Co., Ltd.] which is a binary amphoteric polymer (diallyldimethylammonium chloride / acrylic acid). An antifouling cleaning solution was prepared in the same manner as in (1).

(6) Example 1 except that polymer 1 was replaced with polymer 5 [Marcoat 550 (weight average molecular weight 1600000), which is a binary cationic polymer (diallyldimethylammonium chloride / acrylamide): manufactured by Nippon Lubrizol Co., Ltd.]. An antifouling cleaning solution was prepared in the same manner as in (1).

(7) (7) of Example 1 except that polymer 1 was replaced with polymer 6 [Marcoat 100 (weight average molecular weight 150,000) which is a single cationic polymer (diallyldimethylammonium chloride): manufactured by Nippon Lubrizol Co., Ltd.]. An antifouling cleaning solution was prepared in the same manner as in 1).

(8) An antifouling cleaning solution was prepared so that the nonionic surfactant lauryl glucoside (Mydor 12: manufactured by Kao Corporation) had a solid content concentration of 0.3% by weight.

The compositions of the obtained comparative antifouling detergents are shown in Table 1, respectively.

<Anti-fouling property evaluation>

2 ml of the prepared antifouling detergent was dropped onto the top surface (white mosaic tile) of a 45 mm × 45 mm × 7 mm white pottery tile so as to cover the top surface of the tile. After leaving for 3 minutes (180 seconds), the tile surface was tilted vertically to wash away the antifouling detergent, and at the same time, the tile surface was rinsed with 20 ml of ion-exchanged water, and then air-dried at room temperature.

After drying, the tiles were rinsed by sprinkling tap water at a flow rate of 25 ml / sec for 8 seconds (200 ml in total) toward the center of the top surface of the tile, and then dried in a constant temperature dryer maintained at 50 ° C. for 30 minutes.

Rinsing with running water using tap water and drying with a constant temperature dryer were repeated 6 times (200 ml x 6 times = rinse equivalent to 1200 ml).

The tile that has been repeatedly rinsed and dried after the antifouling agent treatment has been performed once is placed in the center of the bottom surface of a transparent glass beaker having a capacity of 600 ml with the top surface facing up, and the center of the top surface of the tile. 0.5 g of model stain (a mixture of 50 g of oleic acid and 50 g of rapeseed oil, to which 0.015 g of methyl red was added and dissolved by heating) was added dropwise thereto.

In that state, if you slowly fill the tap water along the wall of the beaker, it will get wet from around the tile, and as it progresses, the rolling up of model dirt will be promoted, and finally the model Most of the dirt now floats on the surface of the water away from the tile surface.

After collecting the model dirt floating on the water surface with a dropper, the state of the dirt remaining on the tile top surface was photographed from above, and the state of the dirt remaining on the tile was photographed from the horizontal direction.

To evaluate the stain removal, the residual area ratio with respect to the tile top surface is approximately obtained from a plan photograph taken from above, and the contact angle of the dirt remaining on the tile surface underwater is determined by a cross-sectional photograph (horizontal photograph). I asked. The contact angle was estimated by the formula ^{θ = tan-} 12a / b from the length (b) in which the dirt (oil droplets) is in contact with the tile surface and the height (a) of the dirt in the cross-sectional photograph of the model dirt. ..

The level of antifouling property was ranked based on the following indicators.
AAA: No dirt residue.
AA: Residual area ratio (S) ≤ 0.75% and dirt contact angle (θ) ≥ 40 °
A: Residual area ratio (S) ≤ 1.05% and dirt contact angle (θ) ≥ 34 °
BBB: Residual area ratio (S) ≤ 1.25% and dirt contact angle (θ) ≥ 34 °
BB: Residual area ratio (S) ≤ 1.50% and dirt contact angle (θ) ≥ 34 °
B: Residual area ratio (S) ≤ 1.85% and dirt contact angle (θ) ≥ 30 °
CCC: Residual area ratio (S) ≤ 2.50% and dirt contact angle (θ) ≥ 18 °
CC: Residual area ratio (S) ≤ 4.0% and dirt contact angle (θ) ≥ 18 °
C: Residual area ratio (S) ≤ 10% and dirt contact angle (θ) ≥ 5 °
D: Residual area ratio (S) ≤ 100% and dirt contact angle (θ) ≥ 0 ° (those that do not fall into any of the above levels)

The results are shown in Table 1.

Those using Polymer 1, Polymer 1'and Polymer 3 showed excellent antifouling performance as compared with those using other polymers.

Example 2

The copolymerization ratios of the polymer 1 in (1) and the polymer 1'in (2) of Example 1 were analyzed.

Chlorine (Cl), which is the counter ion of the cation monomer, was quantified by the combustion ion chromatography method to calculate the amount (weight) of the cation monomer in the polymer. Next, the total amount of nitrogen (N) present in the polymer was quantified by CHN analysis. Since the amount of cation monomer has been calculated, the amount of acrylamide monomer (weight) was calculated by calculating the amount of N corresponding to the amount of cation monomer and subtracting it from the total amount of N in the polymer. Further, the weight of acrylic acid was calculated by subtracting the weight of the cation monomer and the weight of the acrylamide monomer from the weight (solid content) of the entire polymer. Since the solid content of the polymer contains a small amount of water, the water content was measured by the heat vaporization method, and the weight ratio of each monomer was calculated with respect to the solid content of the polymer after the water content was subtracted.

Table 2 shows the results converted into the molar ratio of each monomer in the polymer by dividing (dividing) the weight ratio of each obtained monomer by the molecular weight of each monomer.

Example 3

An antifouling detergent containing sulfamic acid (amide sulfate) as the main base for dissolving and removing urinary stone stains was prepared.

5% by weight of sulfamic acid (reagent manufactured by Wako Pure Chemical Industries, Ltd.) from the viewpoint of dissolution and removal of urinary stone stains, and lauryldimethylamine oxide (manufactured by Anhitor 20N Kao Co., Ltd.) from the viewpoint of improving wettability and permeability to urinary stone stains. Xanthan gum (KELZAN AP-AS: CP Kelco A Huber Company, KELZAN is manufactured by KELZAN AP-AS: CP Kelco A Huber Company, KELZAN is manufactured by KELZAN AP-AS) (Trademark of) was blended in an amount of 0.5% by weight. Further, in order to exhibit the antifouling function, the antifouling polymer 1 of Example 1 (1) was blended in an amount of 0.25% by weight. All the blending amounts were prepared as the solid content concentration. The composition of the obtained sulfamic acid-based antifouling detergent is shown in Table 3.

Comparative Example 2

A sulfamic acid-based antifouling detergent was prepared in the same manner as in Example 3 except that the antifouling polymer 1 was not blended. The composition of the obtained cleaning agent is shown in Table 3.

<Storing stability of cleaning agent>

The uniform stability of the cleaning agents obtained in Example 3 and Comparative Example 2 was observed after being stored for 14 days under the conditions of −5 ° C., room temperature (5 ° C. to 20 ° C.), and 50 ° C., and discoloration and precipitation were observed. , The case where the initial state was maintained without separation and precipitation of insoluble matter was evaluated as 〇.

<Evaluation of detergency of complex urinary stone stains>

An evaluation test was conducted using the model stains prepared as follows.

(1) Preparation of urinary stone complex stains

Add 30 g of ion-exchanged water to 14 g of calcium phosphate (manufactured by Wako Pure Chemical Industries, Ltd., tricalcium phosphate), 2 g of urea (manufactured by Wako Pure Chemical Industries, Ltd.) and 4 g of casein (manufactured by Wako Pure Chemical Industries, Ltd.), and further add 0.2 g of blue dye No. 1. In addition, a paste-like model stain was prepared by kneading.

Using a spatula on the center of the top surface of a white pottery tile (108 mm x 60 mm x 8 mm) whose weight (T) was measured in advance with a last three-digit balance, use a spatula so that the model stain is about 0.5 to 0.55 g. It was applied evenly. This was dried in a constant temperature dryer at 50 ° C. for 30 minutes, and then the room temperature was adjusted for a certain period of time, and then the weight (D ₀ ) of the tile with model stains was measured with the same balance.

(2) Detergency evaluation method

The tile with the stains is placed on a horizontal surface, and 1.5 ml of the cleaning agent of Example 3 is applied to the tiles so as to spread over the entire stains, and 10 minutes later, 2 liters of tap water is applied. The tiles were shaken and rinsed while grasping the edges of the tiles by hand in the contained plastic container for 30 seconds. Then, after further rinsing with running water at a flow rate of 40 ml / sec for 20 seconds, it is dried in a constant temperature dryer at 50 ° C. for 30 minutes, and then room temperature humidity control is performed for a certain period of time, and then the weight of the washed tile (D). ₁ ) was measured with the same balance.

Further, another tile to which the stain was attached was treated in the same manner with 1.5 ml of the cleaning agent of Comparative Example 2, and the weight (D ₁ ) of the tile after cleaning was measured with the same balance.

The cleaning rate of urinary stone complex stains was calculated from the following formula.
Cleaning rate (%) = {[Stain-attached tile weight before cleaning (D ₀ ) -Tile weight after cleaning (D ₁ )] (Amount of dirt removed) / [D ₀ -Tile weight (T)] ( Amount of dirt applied)} x 100

Table 3 shows the evaluation results of the cleaning rate and antifouling performance of the urinary stone composite stains for the cleaning agents of Example 3 and Comparative Example 2. The antifouling performance was evaluated by the same method as in Example 1.

The cleaning agent containing the antifouling polymer in the present invention (the antifouling cleaning agent of the present invention) maintained good cleaning agent stability and exhibited excellent detergency for urinary stone composite stains. In addition, the antifouling polymer showed excellent antifouling performance with excellent durability without impairing the function of other blended components.

Example 4

An antifouling detergent containing sodium hypochlorite as the main base was prepared, which strongly acts on organic stains as well as urinary stone stains to decompose and remove stains in the toilet bowl.

Sodium hypochlorite is 5% by weight from the viewpoint of decomposing and removing organic stains, and sodium hydroxide is 1% by weight from the viewpoint of stabilizing sodium hypochlorite. Wetting and permeability of stains and peeling Lauryl dimethylamine oxide (manufactured by Anhitor 20N Kao Co., Ltd.) 1% by weight and sodium lauryl sulfate (non-sal LN-) 1 day Oil Co., Ltd., non-sal is a trademark of the company) 0.87% by weight was blended respectively. Further, in order to exhibit the antifouling function, the antifouling polymer 1 of Example 1 (1) was blended in an amount of 0.25% by weight. All the blending amounts were prepared as the solid content concentration. The composition of the obtained hypochlorous acid-based antifouling detergent is shown in Table 4.

Comparative Example 3

A hypochlorous acid-based antifouling detergent was prepared in the same manner as in Example 4 except that the antifouling polymer 1 was not blended. The composition of the obtained cleaning agent is shown in Table 4.

Table 4 shows the results of evaluating the storage stability, the detergency of the urinary stone composite stain, and the antifouling performance of the cleaning agents of Example 4 and Comparative Example 3 in the same manner as in Example 3.

The cleaning agent containing the antifouling polymer in the present invention maintained good cleaning agent stability and exhibited excellent cleaning power for urinary stone composite stains. In addition, the antifouling polymer showed excellent antifouling performance with excellent durability without impairing the function of other blended components.

Example 5

An antifouling detergent containing an inorganic salt as a main base was prepared, which is excellent in detergency of oil stains and sebum stains due to alkalinity, has appropriate polishing power, and has good rinsing properties.

Sodium hydrogen carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) 1% by weight and sodium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) 1% by weight as inorganic salts, benzalkonium chloride (manufactured by Wako Pure Chemical Industries, Ltd.) 0.02% by weight as disinfectant , 1'0.25% by weight of the antifouling polymer of Example 1 (2) was blended in order to exhibit the antifouling function. All the blending amounts were prepared as the solid content concentration. The composition of the obtained inorganic antifouling detergent is shown in Table 5.

Comparative Example 4

An inorganic antifouling detergent was prepared in the same manner as in Example 5 except that the antifouling polymer 1'was not blended. The composition of the obtained cleaning agent is shown in Table 5.

Table 5 shows the results of evaluating the storage stability and antifouling performance of the cleaning agents of Example 5 and Comparative Example 4 in the same manner as in Example 3.

The cleaning agent containing the antifouling polymer in the present invention maintained good cleaning agent stability. In addition, the antifouling polymer showed excellent antifouling performance with excellent durability without impairing the function of other blended components.

Example 6

From the raw material of softwood bleached kraft pulp, a toilet paper-like water-decomposable sheet having a ^{grain size of 24 g / m 2 was prepared using a general papermaking device.} A sodium salt of carboxymethyl cellulose (CMC-FL100: manufactured by Taka Special Engineering Co., Ltd.) dissolved in water on the front and back of a three-layered sheet obtained by slitting the water-decomposable sheet to a predetermined width is placed in a dry state. The CMC content was added by a coating roll so as to be 6% by weight with respect to the three-layered sheet, and the mixture was dried.

The three-layered sheet containing CMC dried in this way is embossed by passing it between a metal roll having regular protrusions and a smooth metal roll, and then cut to a certain length in the vertical and horizontal directions. A CMC-containing sheet (hereinafter referred to as "water-dissolved paper") having a size of 160 mm × 250 mm and having a regular protrusion structure and a grain size of 69 g / m ^{2 was obtained.}

On the other hand, an antifouling cleaning agent having the composition shown in Table 6 [cleaning agent containing the antifouling polymer 1'of Example 1 (2)] was prepared.

Wet tension is used as a physical property of the water-decomposable cleaning product obtained by uniformly impregnating the above-mentioned water-melting paper with this antifouling cleaning agent so as to have a weight of 2.5 times (250%). The strength, water solubility, detergency, and antifouling property were evaluated by the following methods. The results are shown in Table 6.

Comparative Example 5

A water-decomposable cleaning product was prepared in the same manner as in Example 6 except that the antifouling polymer 1'was not added to the cleaning agent. The composition of the obtained cleaning agent is shown in Table 6.

Reference example

The antifouling property was evaluated by the same method as in Example 1 only for the antifouling detergent used in the water-decomposable cleaning product of Example 6.

<Storing stability of cleaning agent>

The stability of the cleaning agent before impregnation was evaluated by the same method as in Example 3.

<Measurement of wet strength>

A wet water-decomposable cleaning product was cut into strips having a width of 30 mm and a length of 150 mm to prepare test pieces.

Five test pieces are stacked, and the upper and lower ends with the length direction in the vertical direction are inserted and fixed by 50 mm in each of the upper and lower clamps, and the Tencilon tensile tester RTC-1350A (trade name: Orientec Co., Ltd.) ) With a distance between chucks of 50 mm. The five-ply test piece was pulled at a speed of 20 mm / min, the strength at break was measured, and the value was taken as the wet strength. The measurement was performed in both MD (Machine Direction at the time of papermaking) and CD (Cross Machine Direction at the time of papermaking). Wet tensile strength (N / m) was calculated from the obtained measured values.

<Measurement of water solubility>

This was done according to JIS P 4501-1993. Water was placed in a beaker having a capacity of 300 ml, and a stirrer (Star head 35 mmφ × 12 mm manufactured by NALGENE) was rotated at a rotation speed of 600 ± 10 rpm to stir the water.

With respect to the water being stirred, a test piece cut into 114 mm × 114 mm was put into the water by peeling off the outer one of the three layers of water-decomposable cleaning articles. At the time of putting in, the time measurement was started.

The rotation speed of the stirrer decreased to 500 rpm or less due to the injection of the test piece, but began to increase with the hydrolysis of the test piece. The time until the rotation speed of the stirrer reached 540 rpm was measured and used as the value of easiness of loosening (water solubility).

<Measurement of urine stain cleaning power>

1 ml of human urine was applied to a white tile having a top surface of 108 mm × 60 mm and dried at 50 ° C. for 1 hour.

The dried and solidified human urine stain was folded in eight with a 160 mm × 250 mm water-decomposable cleaning product, and wiped once from the front to the back to evaluate the degree of removal of the human urine stain. The evaluation criteria are as follows.
〇: The dirt is almost removed.
Δ: About 10 to 20% of the area is left unwiped.
X: An area of more than 20% of the wiping residue is observed.

<Measurement of antifouling property>

The antifouling property was evaluated by a method according to Example 1.

The top surface (white mosaic tile) of a 45 mm × 45 mm × 7 mm white pottery tile was wiped once from the front to the back with the cleaning product folded in eight. At that time, the amount of liquid adhering to the tile was measured by weighing before and immediately after wiping.

Then, the tile surface was rinsed with 20 ml of ion-exchanged water and air-dried at room temperature.

After drying, the tiles were rinsed by sprinkling tap water at a flow rate of 25 ml / sec for 8 seconds (200 ml in total) toward the center of the top surface of the tile, and then dried in a constant temperature dryer maintained at 50 ° C. for 30 minutes.

Rinsing with running water using tap water and drying with a constant temperature dryer were repeated 6 times (200 ml x 6 times = rinse equivalent to 1200 ml).

The antifouling property of the tiles that had been repeatedly rinsed and dried after being treated with the antifouling agent once was evaluated in the same manner as in Example 1.

Table 6 shows the evaluation results of the water-decomposable cleaning products of Example 6 and Comparative Example 5, the cleaning agents used, and the reference examples.

Detergents containing antifouling polymers maintained good cleaning stability. The sheet-shaped cleaning product that holds the antifouling cleaning agent in an infiltrated state has the same wet strength, water solubility, and urine stain cleaning power as the sheet-shaped cleaning product that holds the cleaning agent that does not contain an antifouling polymer in an infiltrated state. Demonstrated.

The amount of cleaning liquid adsorbed on the target surface when wiped with a sheet-shaped cleaning product was very small, 1/10 of the amount of cleaning liquid adsorbed in the case of the reference example, but the antifouling polymer was added to other components. The antifouling function was not impaired, and the antifouling performance was excellent in durability without being adsorbed on pulp or binder (CMC) in the water-melting paper.

Claims (10)

a) Teruary ammonium salt monomer 15-40% (molar ratio) of diallyldimethylammonium salt or methacrylamidepropyltrimethylammonium salt, acrylamide monomer 30-60% (molar ratio) and acrylic acid or its salt or methacrylic acid or its salt. 0.01 to 30% by weight of a ternary amphoteric polymer composed of 10 to 45% (molar ratio) of anionic monomers.
And b) Antifouling cleaning agent containing a surfactant. The antifouling detergent according to claim 1, wherein the weight average molecular weight of the ternary amphoteric polymer is 5000 to 3000000. The antifouling detergent according to claim 1 or 2, which contains a cationic surfactant selected from a quaternary ammonium salt as at least one component of the surfactant. The antifouling detergent according to any one of claims 1 to 3, which contains an alkyl glucoside or an alkyl amine oxide as at least one component of the surfactant. The antifouling cleaning agent according to any one of claims 1 to 4, which is an acidic system containing 1 to 10% by weight of sulfamic acid. The antifouling cleaning agent according to any one of claims 1 to 5, which is a hypochlorous acid-based substance containing 2 to 10% by weight of hypochlorite in terms of effective chlorine concentration. The antifouling detergent according to any one of claims 1 to 3, which contains sodium carbonate and / or sodium hydrogen carbonate and whose pH is adjusted to 9 to 11. A cleaning product in which a liquid antifouling detergent is infiltrated into water-dissolved paper containing a water-soluble binder having a carboxyl group.
Contains calcium and / or zinc ions
The water-decomposable cleaning product according to any one of claims 1 to 7, wherein the liquid antifouling cleaning agent contains 10 to 40% by weight of a water-soluble solvent. An antifouling cleaning method for a hard surface, wherein the hard surface is treated with the antifouling cleaning agent according to any one of claims 1 to 7. The method according to claim 9, wherein the hard surface is an inner surface of a toilet bowl or a pottery tile.