JP2023146755A - Oil stain detergent for hard surface and cleaning method - Google Patents

Abstract

To provide an oil stain detergent for a hard surface which is excellent in oil stain re-attachment prevention (antifouling property) to an inorganic hard surface such as a glass, is also excellent in oil stain detergency and re-attachment prevention on an organic hard surface such as a resin, and is especially suitably used as a detergent for a dishwasher, and a method for cleaning oil stain on a hard surface using the same.SOLUTION: An oil stain detergent for a hard surface contains an amphoteric polymer compound containing a cationic constitutional unit (1) having at least one group selected from a primary amino group, a secondary amino group and a tertiary amino group in the structure, and an anionic constitutional unit (2).SELECTED DRAWING: None

Description

The present invention relates to an oil stain cleaning agent for hard surfaces and a method for cleaning oil stains on hard surfaces, and more specifically, to a method for preventing oil stains from re-adhering to inorganic hard surfaces such as glass (antifouling properties). The present invention relates to an oil stain cleaning agent for hard surfaces that has excellent oil stain cleaning power and re-adhesion prevention properties on organic hard surfaces such as resins, and a method for cleaning oil stains on hard surfaces using the same.

Various cleaning agents have been developed to remove stains from hard surfaces such as tableware, and efforts have been made to improve their cleaning power. On the other hand, cleaning agents are also required to have antifouling properties, from the perspective of reducing the effort required to remove dirt, such as by reducing the number of times of washing, and from the perspective of preventing dirt from re-adhering once removed during washing. There is. In this way, as an antifouling cleaning agent for hard surfaces with detergency and antifouling properties, a structural unit having one or more groups selected from amino groups and quaternary ammonium salts and a structural unit derived from sulfur dioxide are used. A cleaning agent containing a polymer containing a certain proportion has been proposed (see, for example, Patent Document 1).

Dishwashers are rapidly becoming popular both for commercial use in restaurants and hotels, and for general household use, and a special cleaning agent for dishwashers is used in the dishwashers. Traditionally, before washing dishes in a dishwasher, a pre-wash was performed to remove some of the food and dirt that had adhered to the dishes, but recently, with the spread of dishwashers, there is a tendency to not perform this pre-wash. , detergents for dishwashers are required to further improve their cleaning power. If you wash dishes that have a large amount of dirt on them without pre-washing, the oil stains may remain or become slimy after washing, or they may contaminate other dishes, especially because the oil stain cleaning properties are insufficient. I had something to do. In addition, detergents for dishwashers are required to have foam-inhibiting properties, since foaming can lead to malfunction of the dishwasher.
In the conventional technology, for the purpose of improving the ability to prevent stains from re-deposition on tableware, a polymer compound containing a monomer constitutional unit having a cationic group derived from a quaternary ammonium salt and a monomer constitutional unit having an anionic group is used. A cleaning agent for dishwashers containing the following has been proposed (see, for example, Patent Document 2).

However, the detergents according to the above-mentioned conventional techniques do not necessarily have sufficient cleaning power or re-deposition prevention properties for oil stains, and in particular, when used on organic hard surfaces such as resins, for example, in the case of detergents for dishwashers, PP, PE, etc. The detergency of resin dishes, containers, etc. is insufficient, and oil stains and slimy residues may remain after washing, and a solution to this problem has been desired.

Japanese Patent Application Publication No. 2003-313600 JP2012-214538A

In view of the limitations of the prior art described above, the present invention has excellent oil stain re-adhesion prevention properties (antifouling properties) on inorganic hard surfaces such as glass, and oil stain cleaning ability on organic hard surfaces such as resin. It is an object of the present invention to provide an oil stain cleaning agent for hard surfaces that has excellent anti-redeposition properties and is particularly suitable for use as a cleaning agent for dishwashers, and a method for cleaning oil stains on hard surfaces using the same. purpose.

As a result of intensive studies to solve the above problems, the present inventors found that a cationic compound having at least one group selected from a primary amino group, a secondary amino group, and a tertiary amino group in its structure. An oil stain cleaning agent for hard surfaces containing an amphoteric polymer compound containing a structural unit and an anionic structural unit has excellent properties for preventing oil stains from re-deposition (antifouling properties) on inorganic hard surfaces such as glass. In addition, the present inventors have discovered that the present invention has excellent oil stain cleaning power and re-adhesion prevention properties on organic hard surfaces such as resins, and have completed the present invention.
That is, the present invention
[1]
A cationic structural unit (1) having at least one group selected from a primary amino group, a secondary amino group, and a tertiary amino group in its structure, and an anionic structural unit (2). This is an oil stain cleaning agent for hard surfaces, which contains an amphoteric polymer compound containing.

Below, [2] to [12] are respectively preferred aspects and embodiments of the present invention [2]
The oil stain for hard surfaces according to [1], wherein the molar ratio of the cationic structural unit (1) to the anionic structural unit (2) in the amphoteric polymer compound is from 0.4 to 25.0. Washing soap.
[3]
The oil stain cleaning agent for hard surfaces according to [1] or [2], wherein the cationic structural unit (1) has a primary amino group.
[4]
The oil stain cleaning agent for hard surfaces according to any one of [1] to [3], wherein the cationic structural unit (1) has a structure derived from a monoallylamine monomer.
[5]
The oil stain cleaning agent for hard surfaces according to any one of [1] to [4], wherein the anionic structural unit (2) has a structure derived from an unsaturated carboxylic acid and/or a sulfonic acid.
[6]
The hard surface oil stain cleaning agent according to any one of [1] to [5], further comprising a surfactant.
[7]
The oil stain cleaning agent for hard surfaces according to [6], wherein the surfactant contains a cationic surfactant and an anionic surfactant.
[8]
The hard surface oil stain cleaning agent according to any one of [1] to [7], further containing at least one selected from the group consisting of a chelating agent, a polyol, an alkali metal compound, and a thickener. .
[9]
The oil stain cleaning agent for hard surfaces according to any one of [1] to [8], wherein the content of the amphoteric polymer compound is 0.01 to 50% by mass.
[10]
A method for cleaning oil stains on a hard surface using the oil stain cleaning agent for hard surfaces according to any one of [1] to [9].
[11]
The method for cleaning oil stains on a hard surface according to [10], wherein the hard surface is a surface of tableware, sanitary ware, or tiles.
[12]
The method for cleaning oil stains on a hard surface according to [10] or [11], which uses a dishwasher.

According to the present invention, it not only has excellent oil stain re-deposition prevention properties (antifouling properties) on inorganic hard surfaces such as glass, but also has excellent oil stain cleaning power and re-deposition prevention properties on organic hard surfaces such as resin. Provided are an oil stain cleaning agent for hard surfaces and a method for cleaning oil stains on hard surfaces, which have high practical technical value.
The oil stain cleaning agent for hard surfaces and the method for cleaning oil stains on hard surfaces of the present invention are particularly suitable for cleaning oil stains on hard surfaces using a dishwasher, such as glass dishes, containers, and ceramics. It achieves technical effects that have particularly high practical value, such as excellent ability to prevent stains from re-adhering to dishes and containers.

It is a schematic diagram showing the structure of a PP plate used for evaluation of oil stain cleaning performance and oil stain redeposition prevention property (organic hard surface) in Examples/Comparative Examples of the present application, (a) is the surface, (b) is The back side is shown, and (c) is a perspective view.

The present invention provides a cationic structural unit (1) having at least one group selected from a primary amino group, a secondary amino group, and a tertiary amino group in its structure, and an anionic structural unit. (2) An oil stain cleaning agent for hard surfaces, which contains an amphoteric polymer compound containing the following.
That is, the oil stain cleaning agent for hard surfaces of the present invention has a cationic structural unit having at least one group selected from a primary amino group, a secondary amino group, and a tertiary amino group in its structure. (1) and an anionic structural unit (2) (hereinafter also referred to as "specific amphoteric polymer compound").
The oil stain cleaning agent for hard surfaces of the present invention may be composed only of the specific amphoteric polymer compound, or may be composed of the specific amphoteric polymer compound and other components. From the perspective of achieving high cleaning performance, other ingredients such as surfactants (hereinafter also referred to as "cleaning ingredients") that are commonly used as cleaning agents in this technical field are included. It is preferable.
There is no particular restriction on the content of the specific amphoteric polymer compound in the oil stain cleaning agent for hard surfaces of the present invention, but it is preferably 0.01 to 50% by mass, and preferably 0.015 to 30% by mass. is more preferable, and particularly preferably 0.02 to 10% by mass.

Specific amphoteric polymer compound As mentioned above, the specific amphoteric polymer compound used in the oil stain cleaning agent for hard surfaces of the present invention has a primary amino group, a secondary amino group, and a tertiary amino group in its structure. It is an amphoteric polymer compound containing a cationic structural unit (1) having at least one group selected from amino groups and an anionic structural unit (2).
The specific amphoteric polymer compound may be composed only of a cationic structural unit (1) and an anionic structural unit (2), or a cationic structural unit (1) and an anionic structural unit (2). ), it may contain other structural units, such as nonionic structural units and cationic structural units other than the cationic structural unit (1).

Cationic structural unit (1)
The cationic structural unit (1) constituting the specific amphoteric polymer compound used in the present invention has at least one group selected from a primary amino group, a secondary amino group, and a tertiary amino group in its structure. It is a cationic structural unit having a species group.
The cationic structural unit (1) has at least one group selected from a primary amino group, a secondary amino group, and a tertiary amino group as a cationic functional group in its structure. There are no restrictions other than that it is a structural unit, and therefore it is a structural unit that has at least one group selected from a primary amino group, a secondary amino group, and a tertiary amino group in its structure. As long as the following conditions are satisfied, structural units with various structures can be employed as the cationic structural unit (1). From the viewpoints of low foaming properties, re-deposition prevention properties on inorganic surfaces such as glass, etc., it is preferable that the cationic structural unit (1) has a primary amino group.
Examples of the cationic structural unit (1) include allylamine structural units and diallylamine structural units having at least one group selected from a primary amino group, a secondary amino group, and a tertiary amino group. , aminated (meth)acrylamide-based structural units such as aminoalkyl (meth)acrylamide-based structural units, polyethyleneimine-based structural units, aminated (meth)acrylic acid-based structural units such as aminoethylated (meth)acrylic acid, etc. can be mentioned. Among these, allylamine-based structural units, diallylamine-based structural units, aminated acrylamide-based structural units such as aminopropylacrylamide are preferred, and allylamine-based structural units are particularly preferred.

Allylamine-based structural unit As the cationic structural unit (1), allylamine-based structural units are particularly preferred.
The allylamine-based structural unit is a structural unit having a structure represented by the following general formula (I-a) or a structure that is an acid addition salt thereof.

In the formula, R ¹ and R ² are each independently a hydrogen atom or a monovalent hydrocarbon group, and the monovalent hydrocarbon group is an alkyl group having 1 to 12 carbon atoms which may have a hydroxyl group. , an aralkyl group having 7 to 12 carbon atoms, or a cycloalkyl group having 5 to 6 carbon atoms.
The alkyl group or aralkyl group having 1 to 12 carbon atoms, which is preferable as the monovalent hydrocarbon group, may be either linear or branched. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, decyl, dodecyl. , benzyl group, etc. Furthermore, examples of the cycloalkyl group having 5 to 6 carbon atoms which are preferable as the monovalent hydrocarbon group include, but are not limited to, a cyclopentyl group and a cyclohexyl group.
R ¹ and R ² are preferably each independently a hydrogen atom, a methyl group, an ethyl group, or a benzyl group, and particularly preferably a hydrogen atom or a methyl group.
When R ¹ and R ² are hydrogen atoms at the same time, the allylamine-based structural unit becomes a cationic structural unit (1) having a primary amino group, resulting in low foaming properties and prevention of redeposition to inorganic surfaces such as glass. Particularly preferred from the viewpoint of performance and the like.

When the allylamine-based structural unit is an acid addition salt having a structure represented by general formula (I-a), there are no particular restrictions on the type of addition salt, but from the viewpoint of availability and ease of reaction control, etc. , such as hydrochloride, sulfate, phosphate, nitrate, sulfite, phosphite, nitrite, hydrobromide, acetate, amidosulfate, methanesulfonate, trifluoroacetate, p- Toluenesulfonate and the like can be used.
Among these, hydrochlorides, sulfates, phosphates, and amidosulfates are preferred, and hydrochlorides, sulfates, phosphates, and amidosulfates having a structure derived from monoallylamine are particularly preferred.

Diallylamine-based structural unit The diallylamine-based structural unit is a structural unit having a structure represented by the following general formula (I-b) or an acid addition salt thereof, or a structure represented by the following general formula (I-c).

In the formula, R ³ is a hydrogen atom or a monovalent hydrocarbon group, and examples of the monovalent hydrocarbon group include an alkyl group having 1 to 10 carbon atoms which may have a hydroxyl group, and an alkyl group having 5 to 10 carbon atoms, which may have a hydroxyl group. A cycloalkyl group or an aralkyl group having 7 to 10 carbon atoms is preferred. R ³ is preferably a hydrogen atom, a methyl group, an ethyl group, or a benzyl group, and particularly preferably a hydrogen atom or a methyl group.

It may have a structure that is a diallylamine-based structural unit, an inorganic acid salt having a structure represented by the above structural formula (1-b), an organic acid salt, or the like, that is, a structure that is an acid addition salt.
When the specific amphoteric polymer compound has a diallylamine-based structural unit, it is preferable to use a diallylamine monomer having an addition salt in the production of the specific amphoteric polymer compound from the viewpoint of production costs and the like. The process of removing addition salts such as HCl from polymers is complicated and increases costs. This is a preferred embodiment from the viewpoint of cost and the like.
From the viewpoint of ease of availability and controllability of the reaction, the inorganic acid salt or organic acid salt in the diallylamine-based structural unit of this embodiment is a hydrochloride, a carboxylate, a sulfonate, or an alkyl sulfate salt. is preferred, and hydrochloride is particularly preferred.

In the formula, R ⁴ and R ⁵ are each independently a hydrogen atom or a monovalent hydrocarbon group, provided that at least one of R ⁴ and R ⁵ is a hydrogen atom. The monovalent hydrocarbon group is preferably an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms, which may have a hydroxyl group. . X ^a- represents a counter ion, and a represents the valence of the counter ion.
As long as at least one of R ⁴ and R ⁵ is a hydrogen atom, each independently is preferably a hydrogen atom, a methyl group, an ethyl group, or a benzyl group, and a hydrogen atom or a methyl group is particularly preferred. preferable.

The counter ion X ^a- is not particularly limited, but from the viewpoint of ease of availability and controllability of the reaction, it is preferably a chloride ion, a carboxylate ion, a sulfonate ion, or an alkyl sulfate ion; or ethyl sulfate ion is particularly preferred.
In producing the specific amphoteric polymer compound, it is preferable to use a diallylamine monomer having a counter ion from the viewpoint of production costs and the like. Since the process of removing counter ions from polymers is complicated and causes increased costs, we have developed a specific amphoteric product containing a counter ion type diallylamine structural unit that can be produced without the need for such a process. Using a polymer compound is a preferred embodiment from the viewpoint of cost and the like.

Aminoalkyl (meth)acrylamide-based structural unit An aminoalkyl (meth)acrylamide-based structural unit can also be preferably used as the cationic structural unit (1).
The aminoalkyl (meth)acrylamide-based structural unit is a structural unit having a structure represented by the following general formula (I-d) or a structure that is an acid addition salt thereof.

In the formula, R ⁶ represents a hydrogen atom or a methyl group, R ⁷ and R ⁸ each independently represent a hydrogen atom or a monovalent hydrocarbon group, and n is an integer of 2 to 4.
R ⁶ is preferably a methyl group, and n is preferably 2 to 3.
R ⁷ and R ⁸ are each independently preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom or a methyl group. When R ⁷ and R ⁸ are hydrogen atoms at the same time, the aminoalkyl (meth)acrylamide-based structural unit becomes a cationic structural unit (1) having a primary amino group. It is particularly preferred from the viewpoint of preventing re-adhesion to the surface.
When the aminoalkyl (meth)acrylamide-based structural unit is an acid addition salt having a structure represented by the general formula (I-d), there is no particular restriction on the type of addition salt, but the type of addition salt is not particularly limited; From the viewpoint of the Acetate, p-toluenesulfonate, etc. can be used.
Among these, hydrochlorides, sulfates, phosphates, and amidosulfates are preferred, and hydrochlorides, sulfates, phosphates, and amidosulfates having a structure derived from aminopropyl (meth)acrylamide are particularly preferred.

The specific amphoteric polymer compound may contain only one type of cationic structural unit (1), or may contain two or more types of cationic structural unit (1).
The proportion of the cationic structural unit (1) in the total structural units of the specific amphoteric polymer compound is usually 10 to 90 mol%, preferably 30 to 70 mol%, particularly preferably 40 to 60 mol%. It is. The above ratio when two or more types of cationic structural units (1) are included is defined based on the total amount of the two or more types of cationic structural units (1).

Anionic structural unit (2)
The anionic structural unit (2) constituting the specific amphoteric polymer compound used in the present invention is a structural unit having an anionic functional group in its structure.
The anionic structural unit (2) is not subject to any restrictions other than that it is a structural unit that contains an anionic functional group in its structure; therefore, it is a structural unit that contains an anionic functional group in its structure. As long as the following conditions are satisfied, structural units with various structures can be employed as the anionic structural unit (2). Among these, structural units derived from unsaturated carboxylic acids and structural units derived from sulfonic acids can be preferably used.
Particularly preferable structural units as the anionic structural unit (2) include the following structural units (2-1), structural units (2-2), structural units (2-3), and structural units (2-4). be able to. Among these, preferred are structural unit (2-1), structural unit (2-2), and structural unit (2-3), that is, structural units having a structure derived from an unsaturated dicarboxylic acid.
Furthermore, structural units having a structure derived from an unsaturated monocarboxylic acid, such as the structural unit (2-4), and structural units having a structure derived from a sulfonic acid are also preferably used as the anionic structural unit (2). be able to.

The property-specific amphoteric polymer compound may contain only one type of anionic structural unit (2), or may contain two or more types of anionic structural unit (2). In the case where two or more types of anionic structural units (2) are included, the two or more types of anionic structural units (2) are a combination of structural units that are both classified as structural units (2-1), or a combination of structural units that are both classified as structural units (2-1). A combination of constituent units classified as unit (2-2), a combination of constituent units both classified as constituent unit (2-3), or a combination of constituent units both classified as constituent unit (2-4). It may be a combination of structural units that are classified as different from each other among structural units (2-1) to (2-4). Anionic structural units that do not fall under any of the structural units (2-1) to (2-4) may be used in combination.

Constituent unit (2-1)
The structural unit (2-1) is a structural unit having a structure represented by the following general formula (II-a).

In the formula, R ⁹ is hydrogen or a methyl group, and Y is hydrogen, Na, K, NH ₄ , 1/2Ca, 1/2Mg, 1/2Fe, 1/3Al, or 1/2 for each bonded carboxy group. Represents 3Fe.
R ⁹ is preferably hydrogen, and Y is preferably hydrogen or Na. It is particularly preferable that the structural unit (2-1) is derived from maleic acid.

Constituent unit (2-2)
The structural unit (2-2) is a structural unit having a structure represented by the following general formula (II-b).

In the formula, Y each independently represents hydrogen, Na, K, NH ₄ , 1/2Ca, 1/2Mg, 1/2Fe, 1/3Al, or 1/3Fe for each bonded carboxy group.
Preferably, Y is hydrogen or Na.

Constituent unit (2-3)
The structural unit (2-3) is a structural unit having a structure represented by the following general formula (II-c).

In the formula, Y is hydrogen, Na, K, NH ₄ , 1/2Ca, 1/2Mg, 1/2Fe, 1/3Al, or 1/3Fe for each bonded carboxy group.
Preferably, Y is hydrogen or Na.

Constituent unit (2-4)
The structural unit (2-4) is a structural unit having a structure represented by the following general formula (II-d).

In the formula, R ¹⁰ is hydrogen or a methyl group, and Y is hydrogen, Na, K, NH ₄ , 1/2Ca, 1/2Mg, 1/2Fe, 1/3Al, or 1/2 for each bonded carboxy group. It is 3Fe. R ¹⁰ is preferably hydrogen, and Y is preferably hydrogen or Na.
The structural unit (2-4) is preferably derived from (meth)acrylic acid, particularly preferably derived from acrylic acid.

From the viewpoint of cleaning properties of oil stains on organic surfaces such as polypropylene, prevention of redeposition, etc., a structural unit having a structure derived from sulfonic acid can be preferably used as the anionic structural unit (2).
Examples of structural units having a structure derived from sulfonic acid include a structural unit derived from acrylamide 2-methylpropanesulfonic acid, a structural unit derived from sodium allylsulfonate, a structural unit derived from vinylsulfonic acid, and a structural unit derived from sodium vinylsulfonate. Among them, a structural unit derived from acrylamide 2-methylpropanesulfonic acid is particularly preferred.

The specific amphoteric polymer compound used in the present invention contains the above-mentioned cationic structural unit (1) and anionic structural unit (2), and therefore becomes an amphoteric polymer compound having cationic and anionic properties.
By using the specific amphoteric polymer compound having the cationic structural unit (1) having the above-mentioned specific structure and the anionic structural unit (2), the hard surface oil stain cleaning agent of the present invention can be used to clean inorganic hard surfaces. The mechanism by which the remarkable technical effects of not only excellent oil stain re-deposition prevention properties (antifouling properties) on surfaces but also excellent oil stain cleaning ability and re-deposition prevention properties on organic hard surfaces are realized is not necessarily clear. Although it is not clear, there may be some relationship between the fact that specific amphoteric polymer compounds can assist the oil stain dispersion effect of surfactants by interacting with components such as surfactants contained in cleaning agent components. Presumed.

As mentioned above, in the specific amphoteric polymer compound, the cationic structural unit is preferably an allylamine structural unit, and the anionic structural unit (2) is preferably a structural unit derived from an unsaturated dicarboxylic acid. Since it is preferable, a specific amphoteric polymer compound having an allylamine-based structural unit as the cationic structural unit (1) and a structural unit derived from an unsaturated dicarboxylic acid as the anionic structural unit (2) is used for cleaning oil stains. It can be used particularly preferably from the viewpoints of strength, anti-redeposition properties, anti-foaming properties, etc.

There is no particular restriction on the ratio of the total of the cationic structural unit (1) and anionic structural unit (2) to the total structural units of the specific amphoteric polymer compound, but it is usually 50 mol% or more, and is preferably is 65 to 100 mol%, more preferably 80 to 100 mol%, particularly preferably 90 to 100 mol%.
There is no particular restriction on the ratio of cationic structural unit (1) to anionic structural unit (2), but usually the molar ratio of cationic structural unit (1)/anionic structural unit (2) is within the range of 0.4 to 25.0, preferably within the range of 0.5 to 10.0, and more preferably within the range of 0.7 to 5.0. When the molar ratio of cationic structural unit (1)/anionic structural unit (2) is within the above range, a polymer can be obtained in high yield, and when used as a cleaning agent, it has sufficient water solubility. It is possible to achieve advantageous effects such as preservation.
When the anionic structural unit (2) is derived from an unsaturated dicarboxylic acid, the molar ratio of the cationic structural unit (1)/anionic structural unit (2) is 0.5 to 2.0. It is preferably 1.0 to 2.0, particularly preferably 1.0 to 2.0.

The molar ratio between the cationic structural unit (1) and the anionic structural unit (2) in the specific amphoteric copolymer can be measured by conventionally known methods, such as elemental analysis or ¹ H- It can be measured by NMR methods such as NMR and ¹³ C-NMR.
Depending on the type of each structural unit in the specific amphoteric copolymer, the ratio (molar ratio) of the structural units derived from each monomer may be different from the charging composition (molar ratio) of each monomer during copolymerization. In many cases, they almost match, and in such cases, the blending ratio of the monomers may be treated as the ratio (molar ratio) of the structural units for convenience.
The molar ratio of cationic structural unit (1)/anionic structural unit (2) in the specific amphoteric copolymer is determined based on each monomer supplied in the production (copolymerization) of the specific amphoteric copolymer, especially the cationic structural unit (2). The type and amount of the monomer that leads to the ionic structural unit (1) and the monomer that leads to the anionic structural unit (2), conditions for production (copolymerization), such as the type and amount of the catalyst, and the copolymerization temperature. It can be adjusted as appropriate by selecting and adjusting the time, time, etc.

Other constituent units (3)
In addition to the above-mentioned cationic structural unit (1) and anionic structural unit (2), the specific amphoteric polymer compound may have other structural units.
Other structural units include nonionic structural units (3-1) described below and structures that do not fall under cationic structural units (1), i.e., primary amino groups, secondary amino groups. , and a cationic structural unit (3-2) having neither a tertiary amino group nor a tertiary amino group.
Specified amphoteric polymer compound Other structural units (3) are not essential structural units of the specified amphoteric polymer compound, but for the purpose of improving polymerization, water solubility, and compatibility with cleaning agent components, etc. It can be introduced into specific amphoteric polymer compounds.

Nonionic structural unit (3-1)
The nonionic structural unit (3-1) in this embodiment is a structural unit derived from a nonionic monomer copolymerizable with the cationic structural unit (1) and the anionic structural unit (2). There are no particular limitations other than this, but a structure derived from methacrylic acid ester monomers, acrylic acid ester monomers, methacrylamide monomers, acrylamide monomers, sulfur dioxide, etc. Units etc. can be preferably used. More specific examples include methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, methacrylamide, N-methylmethacrylamide, dimethylmethacrylamide, N-(3- (dimethylaminopropyl) methacrylamide, acrylamide, dimethylacrylamide, hydroxyethylacrylamide, dimethylaminopropylacrylamide, dimethylaminopropylacrylamide methyl chloride quaternary salt, acryloylmorpholine, isopropylacrylamide, 4-tert-butylcyclohexyl acrylate, or sulfur dioxide The structural units that can be derived can be listed. Particular preference is given to using building blocks derived from acrylamide, methacrylamide or hydroxyethylacrylamide.
The nonionic structural unit (3-1) can usually be introduced into the specific amphoteric polymer compound by using a nonionic monomer as the monomer.

When the specific amphoteric polymer compound has a nonionic structural unit (3-1), there is no particular restriction on the content of the nonionic structural unit (3-1). Although the preferable amount varies depending on the type of (), it is preferably contained in an amount of 1 to 50 mol%, more preferably 1 to 20 mol%, based on 100 mol% of all structural units.
When the nonionic structural unit (3-1) is derived from a methacrylic ester monomer, an acrylic ester monomer, a methacrylamide monomer, or an acrylamide monomer, the above content ratio is preferably 1 to 50 mol%, more preferably 1 to 20 mol%.
When the nonionic structural unit (3-1) is derived from sulfur dioxide, the content is preferably 1 to 50 mol%, more preferably 20 to 50 mol%.

The content ratio of the nonionic structural unit (3-1) in the specific amphoteric copolymer can also be measured by conventionally known methods, such as elemental analysis, ¹ H-NMR, ¹³ C-NMR, etc. It can be measured by NMR method.
Depending on the type of each structural unit in the specific amphoteric copolymer, the ratio (molar ratio) of the structural units derived from each monomer may be different from the charging composition (molar ratio) of each monomer during copolymerization. In many cases, they almost match, so in such cases, it is convenient to calculate the blending ratio (mol) of the monomer that leads to the nonionic structural unit (3-1) relative to the total monomer supply amount (mol). may be treated as the content ratio of the nonionic structural unit (3-1).
The content ratio of the nonionic structural unit (3-1) in the specific amphoteric copolymer also depends on each monomer supplied in the production (copolymerization) of the specific amphoteric copolymer, especially the nonionic structural unit (3-1). It can be adjusted as appropriate by selecting and adjusting the type and amount of the monomer that leads to 1), the conditions for production (copolymerization), such as the type and amount of catalyst, copolymerization temperature and time, etc.

Cationic structural unit (3-2) having no primary amino group, secondary amino group, or tertiary amino group
There is no particular restriction on the type of the cationic structural unit (3-2) that does not have any of a primary amino group, a secondary amino group, and a tertiary amino group, and the cationic structural unit ( A monomer copolymerizable with the monomer leading to (1) and the monomer leading to the anionic structural unit (2), which comprises a primary amino group, a secondary amino group, and a tertiary amino group. A structural unit derived from a cationic monomer having no groups can be introduced as appropriate.
Examples of cationic monomers that do not have a primary amino group, a secondary amino group, or a tertiary amino group include diallylamine monomers that have a quaternary amino group. but are not limited to these.

Primary amino group when the specified amphoteric polymer compound has a cationic constitutional unit (3-2) that does not have any of a primary amino group, a secondary amino group, and a tertiary amino group There is no particular restriction on the content of the cationic structural unit (3-2) having neither a secondary amino group nor a tertiary amino group. The preferred amount varies depending on the type of cationic structural unit (3-2) that does not have any tertiary amino group, but it is contained in an amount of 1 to 35 mol% based on 100 mol% of all structural units. The content is preferably 1 to 10 mol%, and more preferably 1 to 10 mol%.
The method for measuring and adjusting the content ratio of the cationic structural unit (3-2) that does not have either a secondary amino group or a tertiary amino group in the specified amphoteric copolymer is based on the nonionic This is the same as that explained above in relation to the content ratio of the structural unit (3-1).

Physical properties of the specified amphoteric polymer compound There is no particular restriction on the molecular weight of the specified amphoteric polymer compound, and the specified amphoteric polymer has a suitable molecular weight depending on the usage form of the oil stain cleaning agent for hard surfaces and other components. The compound may be obtained or polymerized, but from the viewpoint of handling properties, solubility, etc., those having a weight average molecular weight (Mw) of 500 or more and 200,000 or less are usually used.
From the viewpoint of achieving excellent solubility, the weight average molecular weight (Mw) of the specific amphoteric polymer compound is preferably 500 or more and 150,000 or less, more preferably 500 or more and 100,000 or less.
From the viewpoint of polymerizing in a practically acceptable time and cost, the weight average molecular weight (Mw) of the specific amphoteric polymer compound is preferably 80,000 or less, more preferably 50,000 or less. .
The weight average molecular weight (Mw) of the specific amphoteric polymer compound can be measured, for example, by gel permeation chromatography (GPC method) using a liquid chromatograph. More specifically, it can be measured, for example, by the method described in the Examples of the present application.
The molecular weight of the specific amphoteric polymer compound can be adjusted as appropriate by adjusting the type and composition of the monomers used as raw materials, the temperature, time and pressure in the polymerization process, the type and amount of the radical initiator used in the polymerization process, etc. be able to.

There is no particular limit to the rotational viscosity [η] of the specific amphoteric polymer compound, and it can be set appropriately depending on the usage form of the oil stain cleaning agent for hard surfaces and other components, etc., but it is 5 to 2,000 mPa.・s (25°C) is preferable, and 10 to 1,000 mPa·s (25°C) is particularly preferable.
The rotational viscosity [η] can be measured by a method commonly used in the art, for example, using a digital B-type viscometer DV-3T manufactured by AMETEK Brookfield. In the measurement, a ULA adapter is used, and the measurement can typically be performed at a liquid volume of 16 mL and a liquid temperature of 25°C.
The rotational viscosity [η] can also be adjusted as appropriate by adjusting the dilution concentration, the type and composition of monomers used as raw materials, the temperature, time and pressure in the polymerization process, the type and amount of the radical initiator used in the polymerization process, etc. can do.

Method for producing specific amphoteric polymer compound There is no particular restriction on the method for producing the specific amphoteric polymer compound, and it can be produced by a method conventionally known in the technical field. and an anionic monomer with a structure corresponding to the anionic structural unit (2), and optionally a nonionic monomer with a structure corresponding to the nonionic structural unit (3). It can be produced by copolymerizing other monomers such as monomers.

When copolymerizing a cationic monomer with a structure corresponding to the cationic structural unit (1), an anionic monomer with a structure corresponding to the anionic structural unit (2), etc., the solvent is particularly limited. The solvent may be an aqueous solvent or an organic solvent such as alcohol, ether, sulfoxide, or amide, but an aqueous solvent is preferable.
Monomer concentration when copolymerizing a cationic monomer with a structure corresponding to the cationic structural unit (1), an anionic monomer with a structure corresponding to the anionic structural unit (2), etc. Although it varies depending on the type of monomer and the type of solvent used for copolymerization, it is usually 10 to 75% by mass in the case of an aqueous solvent. This copolymerization reaction is usually a radical polymerization reaction, and is carried out in the presence of a radical polymerization catalyst. The type of radical polymerization catalyst is not particularly limited, and preferred examples thereof include peroxides such as t-butyl hydroperoxide, persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate, azobis-based catalysts, Examples include water-soluble azo compounds such as diazo compounds.

The amount of the radical polymerization catalyst added is generally 0.1 to 20 mol%, preferably 1.0 to 10 mol%, based on the total monomers. The polymerization temperature is generally 0 to 100°C, preferably 5 to 80°C, and the polymerization time is generally 1 to 150 hours, preferably 5 to 100 hours. The polymerization may be carried out in an atmosphere of an inert gas such as nitrogen, although there is no major problem in polymerization even in the air.

Cleaning Components The hard surface oil stain cleaning agent of the present invention contains, in addition to the specific amphoteric polymer compound described above, other components from the viewpoint of achieving high cleaning performance and improving the dispersibility of stain components. Components that are commonly used as cleaning agents in this technical field, such as surfactants (hereinafter also referred to as "cleaning components"), can be included.
Although there is no particular restriction on the type of cleaning component in this embodiment, it is particularly preferable to include various surfactants such as cationic surfactants and anionic surfactants.
The cleaning component may further contain one or more components selected from chelating agents, polyols, alkali metal compounds, thickeners, enzymes, and bleaching agents.

Surfactant The hard surface oil stain cleaning agent of this embodiment has the following objectives: to enhance the antifouling cleaning effect, and to add foaming properties to increase the feeling of cleaning effect and adhesion during use. It is preferable to include a surfactant as a cleaning component. The surfactant is preferably one or more selected from anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants.

Examples of anionic surfactants include alkylbenzene sulfonates with alkyl groups having 8 to 18 carbon atoms, alkanesulfonates, α-olefin sulfonates, alkyl sulfate ester salts, polyoxyethylene (average number of moles added is 1 to 18), 10) Examples include alkyl ether sulfate salts, polyoxyethylene (average number of added moles of 1 to 10) alkyl ether acetates, among others, alkylbenzene sulfonates having an alkyl group of 10 to 15 carbon atoms, Preferred are alkyl sulfate ester salts having 8 to 14 carbon atoms and polyoxyethylene sulfates having an alkyl group of 10 to 14 carbon atoms (average number of added moles of 1 to 5). Moreover, as the salt, sodium salt or potassium salt is preferable.

As the nonionic surfactant, a compound represented by the following general formula (3) and/or a compound represented by the general formula (4) is preferable from the viewpoint of antifouling and cleaning effects.
R ¹¹ -T-[(R ¹² O) _a -R ¹³ ] _b -(3)
[In the formula, R ¹¹ is an alkyl group or alkenyl group having 8 to 20 carbon atoms, preferably 10 to 18 carbon atoms, and R ¹² is an alkylene group having 2 or 3 carbon atoms, preferably an ethylene group. R ¹³ is an alkyl group having 1 to 3 carbon atoms or a hydrogen atom. a represents a number of 1 to 100, preferably 3 to 80, more preferably 5 to 40, particularly preferably 5 to 20. T is -O-, -COO-, -CON- or -N-; if T is -O- or -COO-, b is 1; if T is -CON- or -N-, b is 1 or 2].

R ¹⁴ - (OR ¹⁵ ) _c G _d - (4)
[In the formula, R ¹⁴ is a linear alkyl group having 8 to 16 carbon atoms, preferably 10 to 16 carbon atoms, particularly preferably 10 to 14 carbon atoms, and R ¹⁵ is an alkylene group having 2 to 4 carbon atoms, preferably an ethylene group or propylene group. group, in particular an ethylene group, G is a residue derived from a reducing sugar, c is a number with an average value of 0 to 6, d is a number with an average value of 1 to 10, preferably 1 to 5, particularly preferably 1 to 2 shows. ].

The following compounds can be mentioned as specific examples of the compound of general formula (3).
R ¹¹ -O-(C ₂ H ₄ O) _e -H
[In the formula, R ¹¹ has the above meaning. e is a number from 1 to 100, preferably from 5 to 20. ]
R ¹¹ -O-(C ₂ H ₄ O) _f -(C ₃ H ₆ O) _g -H
[In the formula, R ¹¹ has the above meaning. f and g are each independently a number from 1 to 20, preferably from 1 to 10, and EO and propylene oxide may be a random or block adduct. ]

[In the formula, R ¹¹ has the above meaning. h and i are each independently a number from 0 to 40, preferably from 0 to 20, and h+i is a number from 1 to 20, preferably from 1 to 15. R ¹⁶ and R ¹⁷ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ]

In the compound of general formula (4), G is a residue derived from a reducing sugar, and the reducing sugar as a raw material may be either an aldose or a ketose, or a triose having 3 to 6 carbon atoms. , tetrose, pentose, and hexose. Specific examples of aldoses include apiose, arabinose, galactose, glucose, lyxose, mannose, aldose, idose, talose, and xylose, and examples of ketoses include fructose. In this embodiment, among these, aldopentoses or aldohexoses having 5 or 6 carbon atoms are particularly preferred, and glucose is most preferred.

As the cationic surfactant, (alkyl)amidoamine compounds of the following general formula (5) and compounds of the following general formulas (6) to (8) are preferred from the viewpoint of antifouling effect.

In the general formula (5), R ¹⁸ is a linear or branched alkyl group having 11 to 21 carbon atoms or a linear or branched alkenyl group having 11 to 21 carbon atoms.
The number of carbon atoms in the alkyl group and the alkenyl group in R ¹⁸ is 11 to 21, respectively, and the number of carbon atoms is preferably 13 to 21, more preferably, since the foam suppressing effect of suppressing foaming and the detergency against oil stains are further enhanced. has 15 to 21 carbon atoms, particularly preferably 15 to 19 carbon atoms.
R ¹⁸ is preferably a linear or branched alkyl group having 13 to 21 carbon atoms.

R ¹⁹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group having 1 to 4 carbon atoms.
The number of hydroxy groups in the hydroxyalkyl group in R ¹⁹ may be one or two or more.
R ¹⁹ is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

R ²⁰ is an alkylene group having 1 to 4 carbon atoms.
The alkylene group in R ²⁰ has 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms, more preferably 2 or 3 carbon atoms, and particularly preferably 3 carbon atoms.

R ²¹ and R ²² are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
The alkyl group in R ²¹ and R ²² each has 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms, more preferably 1 or 2 carbon atoms, and particularly preferably 1 or 2 carbon atoms. be.
R ²¹ and R ²² are each preferably an alkyl group having 1 to 4 carbon atoms, and preferably the same.

Examples of the (alkyl)amidoamine compounds of general formula (5) include dimethylaminoethylamide laurate, diethylaminoethylamide laurate, dipropylaminoethylamide laurate, dimethylaminopropyl laurate, and diethylaminopropyl laurate. Amide, lauric acid dipropylaminopropylamide, myristic acid dimethylaminoethylamide, myristic acid diethylaminoethylamide, myristic acid dipropylaminoethylamide, myristic acid dimethylaminopropylamide, myristic acid diethylaminopropylamide, myristic acid dipropylaminopropyl Amide, palmitic acid dimethylaminoethylamide, palmitic acid diethylaminoethylamide, palmitic acid dipropylaminoethylamide, palmitic acid dimethylaminopropylamide, palmitic acid diethylaminopropylamide, palmitic acid dipropylaminopropylamide, stearic acid dimethylaminoethylamide , stearic acid diethylaminoethylamide, stearic acid dipropylaminoethylamide, stearic acid dimethylaminopropylamide, stearic acid diethylaminopropylamide, stearic acid dipropylaminopropylamide, behenic acid dimethylaminoethylamide, behenic acid diethylaminoethylamide, behen Acid dipropylaminoethylamide, behenic acid dimethylaminopropylamide, behenic acid diethylaminopropylamide, behenic acid dipropylaminopropylamide, lauric acid dimethylaminoethylmethylamide, myristic acid dimethylaminoethylmethylamide, palmitic acid dimethylaminoethylmethylamide amide, stearic acid dimethylaminoethylmethylamide, behenic acid dimethylaminoethylmethylamide, lauric acid dimethylaminopropylmethylamide, myristate dimethylaminopropylmethylamide, palmitic acid dimethylaminopropylmethylamide, stearic acid dimethylaminopropylmethylamide, Examples include behenic acid dimethylaminopropylmethylamide.
Among these, myristic acid dimethylaminopropylamide, palmitic acid dimethylaminopropylamide, stearic acid dimethylaminopropylamide, and behenic acid dimethylaminopropylamide are preferable because they are more likely to provide a foam suppressing effect.
The (alkyl)amidoamine compounds of general formula (5) may be used alone or in combination of two or more.

[In the formula, R ²³ is an alkyl group having 5 to 18, preferably 6 to 14, particularly preferably 8 to 12, or an alkenyl group, preferably an alkyl group, and R ²⁵ and R ²⁶ are an alkyl group having 1 to 3 carbon atoms. It is an alkyl group or a hydroxyalkyl group. U is -COO-, OCO-, -CONH-, -NHCO-,

It is. j is a number of 0 or 1. R ²⁴ is an alkylene group having 1 to 6 carbon atoms or -(O-R ³³ ) _k -. Here, R ³³ is an ethylene group or a propylene group, preferably an ethylene group, and k is a number from 1 to 10, preferably from 1 to 5. R ²⁷ is an alkylene group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms. R ²⁸ is an alkyl group having 8 to 16 carbon atoms. Furthermore, two or more (preferably two) of R ²⁹ , R ³⁰ , R ³¹ , and R ³² are alkyl groups having 8 to 18 carbon atoms, preferably 8 to 12 carbon atoms, and the rest are alkyl groups having 1 to 12 carbon atoms. 3 is an alkyl group or a hydroxyalkyl group. Furthermore, Z ⁻ is an anionic group, preferably a halogen ion or an alkyl sulfate ion having 1 to 3 carbon atoms. ]

Among the cationic surfactants represented by formulas (6) to (8), particularly preferred are the following.

As the amphoteric surfactant, a compound represented by the following general formula (9) and a compound represented by the general formula (10) are preferred.

[In the formula, R ³⁴ is a straight-chain alkyl group or alkenyl group having 8 to 16 carbon atoms, preferably 10 to 16 carbon atoms, particularly preferably 10 to 14 carbon atoms, and R ³⁶ and R ³⁷ are alkyl groups having 1 to 3 carbon atoms. or a hydroxyalkyl group. R ³⁵ is an alkylene group having 1 to 5 carbon atoms, preferably 2 or 3 carbon atoms. A is a group selected from -COO-, -CONH-, -OCO-, -NHCO-, and -O-, and a is a number of 0 or 1, preferably 1. ]

[In the formula, R ³⁸ is an alkyl group or alkenyl group having 9 to 23 carbon atoms, preferably 9 to 17 carbon atoms, particularly preferably 10 to 16 carbon atoms, and R ³⁹ is an alkyl group or alkenyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, particularly Preferably it is 2 or 3 alkylene groups. B is a group selected from -COO-, -CONH-, -OCO-, -NHCO-, and -O-, and b is 0 or 1, preferably 0. R ⁴⁰ and R ⁴¹ are each independently an alkyl group or hydroxyalkyl group having 1 to 3 carbon atoms, preferably a methyl group, ethyl group or hydroxyethyl group, and R ⁴² may be substituted with a hydroxy group. It is an alkylene group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms. D is a group selected from -COO ^- , -SO ₃ ^- , and -OSO ₃ ^-, and -COO ^- is particularly good in terms of foaming properties because -SO ₃ ^- adjusts the viscosity to the desired level. . ]

In this embodiment, a cationic surfactant or an anionic surfactant is preferred from the viewpoint of antifouling effect, and it is particularly preferred to use a combination of a cationic surfactant and an anionic surfactant. As the cationic surfactant, an (alkyl)amidoamine compound of general formula (5) is preferable, and as the anionic surfactant, an alkylbenzene sulfonate having an alkyl group of 8 to 18 carbon atoms is preferable, and a combination of the two is preferable. Particularly preferred is the use of

The surfactant is preferably contained in the hard surface oil stain cleaning agent of the present embodiment in an amount of 0.001 to 50% by mass, particularly preferably 0.005 to 30% by mass, and even more preferably 0.01 to 25% by mass. When cleaning a hard surface by spraying with a spray device such as a trigger or aerosol, or by coating, the concentration of the surfactant should be 0.001 to 0.001. 10% by mass, more preferably 0.005 to 5% by mass, and even more preferably 0.01 to 3% by mass; on the other hand, in a cleaning method using water in the toilet tank, the amount of water in the tank or any water supply route is When used in a toilet auto-cleaner that can administer an appropriate amount of cleaning liquid to the water in the tank by providing a device, it is 0.1 to 50% by mass, more preferably 1 to 30% by mass, and even more preferably 5 to 50% by mass. Contains 25% by mass. The concentration of the surfactant in the tank is preferably 0.01 to 20 ppm, particularly preferably 0.1 to 10 ppm.

When using an anionic surfactant as a surfactant in this embodiment, the antifouling effect may be reduced, so the content of the anionic surfactant is set to 70% by mass or less based on the total amount of surfactant. The content is preferably 50% by mass or less from the viewpoint of antifouling effect. In particular, when using a cationic surfactant represented by general formulas (5) to (7) together with an anionic surfactant, the ratio of the anionic surfactant to the mass of the cationic surfactant is It is preferred that the ratio is less than 1.4, particularly less than 1.0.

Polyol In this embodiment, a water-soluble solvent is preferably blended as a cleaning component for the purpose of improving cleaning power against organic stains and for stability during storage, and preferably a monohydric alcohol having 1 to 5 carbon atoms. It is preferable to add a polyol, preferably having 4 to 12 carbon atoms, and it is preferable to add a polyol.

Monohydric alcohols generally include ethanol, propyl alcohol, and isopropyl alcohol. By blending these lower alcohols, the stability of the system at low temperatures can be further improved.

Preferably, polyols having 4 to 12 carbon atoms include isoprene glycol, 2,2,4-trimethyl-1,3-pentanediol, 1,4-butanediol, 1,5-pentanediol, and 1,8-octane. In addition to diol, 1,9-nonanediol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, monoalkyl glyceryl ethers in which the alkyl group has 3 to 8 carbon atoms can be mentioned.

The above-mentioned polyol and the like may be contained in the hard surface oil stain cleaning agent of the present embodiment in an amount of 0.1 to 50% by mass, more preferably 0.5 to 30% by mass. When cleaning hard surfaces by spraying with a spray device such as a trigger or aerosol, or by coating, when using polyol, the concentration is usually 0.1 to 20% by mass. %, more preferably 0.5 to 10% by mass, particularly preferably 0.5 to 7% by mass. On the other hand, in the cleaning method using water in the toilet tank, the device is not installed in the tank or in any water supply route. When used in a toilet auto-cleaner that can administer an appropriate amount of cleaning liquid to the water in the tank, it is usually 1 to 50% by mass, more preferably 3 to 40% by mass, and even more preferably 5 to 30% by mass. Contains. The concentration of polyol, etc. in the toilet tank is preferably 0.01 to 20 ppm, more preferably 0.1 to 10 ppm.

Chelating Agent In this embodiment, it is preferable to further incorporate a chelating agent for the purpose of dissolving inorganic stains and improving detergency and further improving the antifouling effect. Chelating agents include (1) tripolyphosphoric acid, pyrophosphoric acid, orthophosphoric acid, hexametaphosphoric acid, and alkali metal salts thereof, (2) ethylenediaminetetraacetic acid, hydroxyiminodiacetic acid, dihydroxyethylglycine, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, Diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid and their alkali metal or alkaline earth metal salts, (3) aminotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriamine Pentamethylenephosphonic acid, aminotrimethylenephosphonic acid, and alkali metal salts or alkaline earth metal salts thereof; (4) homopolymers or copolymers of monomers selected from acrylic acid and methacrylic acid; acrylic acid-maleic acid; Copolymer, polyα-hydroxyacrylic acid and alkali metal salt thereof, (5) polyhydric carboxylic acid selected from citric acid, succinic acid, malic acid, fumaric acid, tartaric acid, malonic acid, maleic acid and their alkalis One or more selected from metal salts, (6) alkylglycine-N,N-diacetic acid, aspartic acid-N,N-diacetic acid, serine-N,N-diacetic acid, glutamic acid diacetic acid, ethylenediamine disuccinic acid, or These salts are preferred, and the compounds (2), (3), and (5) above are particularly preferred.

The chelating agent is preferably contained in the hard surface oil stain cleaning agent of this embodiment in an amount of 0.1 to 30% by mass, and can be applied to the target by spraying with a spray device such as a trigger or aerosol, or by coating. When cleaning hard surfaces, the concentration of the chelating agent is preferably 0.1 to 20% by mass, more preferably 0.3 to 10% by mass, while cleaning methods using water in the toilet tank When used in a toilet auto-cleaner that can administer an appropriate amount of cleaning liquid to the water in the tank by providing a device in the tank or any water supply route, it is preferably 0.1 to 20% by mass, more preferably is contained in an amount of 0.1 to 10% by mass. The concentration of the chelating agent in the toilet tank is preferably 0.01 to 20 ppm.

Alkali metal compound The antifouling cleaning agent for hard surfaces of the present invention contains an alkali metal compound, especially when used in a cleaning method using a dishwasher, from the viewpoint of preventing redeposition and reducing odor after cleaning. It is preferable to do so.
The alkali metal compound is preferably an alkali metal carbonate and/or an alkali metal hydroxide, more preferably sodium carbonate, potassium carbonate, sodium hydroxide, or potassium hydroxide, and particularly preferably sodium hydroxide or potassium hydroxide.

The content of the alkali metal compound in the antifouling cleaning agent for hard surfaces of the present embodiment is preferably 5 to 30% by mass, and 7 to 25% by mass, from the viewpoint of preventing soil redeposition and reducing odor after cleaning. Mass% is more preferred.

Thickener In the present invention, a thickener such as a water-soluble polymer can be added for the purpose of providing adhesive properties during use and improving ease of use. The type of thickener is not particularly limited, but for example,
(i) Plant-derived natural polymers such as guar gum, locust bean gum, carrageenan, alginic acid, gum arabic, and pectin;
(ii) Natural polymers derived from microorganisms such as xanthan gum,
(iii) starch derivatives and cellulose derivatives obtained by processing cellulose, starch, and cellulose starch through treatments such as oxidation, methylation, carboxymethylation, hydroxyethylation, hydroxypropylation, and cationization;
(iv) a polyacrylic acid derivative which is a polyacrylic acid homopolymer or a copolymer of a monomer copolymerizable with acrylic acid, and a crosslinked product of the polyacrylic acid homopolymer or the polyacrylic acid derivative;
(v) animal-derived natural polymers such as gelatin, casein, albumin and shellac;
(vi) Guar gum derivatives and locust bean gum derivatives obtained by processing guar gum and locust bean gum through treatments such as oxidation, methylation, carboxymethylation, hydroxyethylation, hydroxypropylation, and cationization;
(vii) alginic acid derivatives such as ammonium alginate and alginate propylene glycol ester;
(viii) completely or incompletely saponified products of vinyl acetate homopolymers or copolymers of vinyl acetate and other monomers, or polyvinyl alcohols or polyvinyl alcohol derivatives obtained by crosslinking these with, for example, aldehydes;
(ix) polyalkylene glycols such as polyethylene oxide, polypropylene oxide, copolymers of ethylene oxide and propylene oxide,
(x) Polydimethylaminoethyl methacrylate and its quaternized product, or a copolymer of dimethylaminoethyl methacrylate and a copolymerizable monomer and its quaternized product, a ring-closing polymer of dimethyldiallylammonium chloride, and poly(N-vinyl-2 , 3-dimethylimidazolinium chloride), etc. can be preferably used.
The content of the thickener in the antifouling cleaning agent for hard surfaces of the present embodiment is preferably 0.05 to 2.0% by mass, and 0.1 to 0.0% by mass from the viewpoint of handling properties, uniform solubility, etc. 5% by mass is more preferred.

In addition to the above-mentioned components, the antifouling cleaning agent for hard surfaces of the present invention includes additives that are included in ordinary cleaning agents to the extent that they do not impair the effects of the present invention, such as fragrances, antibacterial agents, viscosity modifiers, Pigments, dyes, suspending agents, hydrotropes, antioxidants, pH adjusters, etc. can be added.

When using the antifouling cleaning agent for hard surfaces of the present invention, the specific amphoteric polymer compound may be dissolved or dispersed as a single agent in a solvent, or an arbitrary number of agents may be used in combination with cleaning components. Good too. Furthermore, by combining cleaning components, it may be used in the form of one or more powders or tablets that dissolve immediately in a solvent such as water or have sustained release properties. Furthermore, it is also possible to use one of the specific amphoteric polymer compound and the cleaning component in a liquid state and the other in a solid state such as a powder.

Oil stain cleaning agent for hard surfaces and method for cleaning oil stains on hard surfaces The oil stain cleaning agent for hard surfaces of the present invention is a liquid cleaning agent containing a specific amphoteric polymer compound and a cleaning component, and the balance being water. It is preferable.
The water content is not particularly limited, but is usually 10 to 99.99% by weight, preferably 20 to 98% by weight, and more preferably 50 to 90% by weight.

The form in which the antifouling cleaning agent for hard surfaces of the present invention is used is not particularly limited, but it can be preferably used in a cleaning method using a dishwasher such as an automatic dishwasher. It can also be preferably used for cleaning walls, floors, appliances, equipment, etc. in the house in general, especially in the kitchen, bathroom, toilet, washstand, etc. The latter methods include spraying directly onto the object using a sprayer such as a trigger or aerosol, soaking the antifouling cleaning agent into a water-absorbing flexible material and rubbing it against the object, and dissolving the antifouling cleaning agent. A method in which the object is immersed in a solution is suitable.
From the above, in the method for cleaning oil stains on hard surfaces using the oil stain cleaning agent for hard surfaces of the present invention, the hard surface can be used to clean tableware (inorganic hard surfaces such as glass, ceramics, metal, etc., organic hard surfaces such as resin). ), sanitary ware, tiles, etc. are the preferred cleaning targets.

Hereinafter, the present invention will be described in further detail with reference to Examples. Note that the scope of the present invention is not limited in any way by these Examples.

In the Examples/Comparative Examples below, various characteristics were evaluated by the following methods.
- Amount of solid content in the cleaning component To determine the solid content in the cleaning component, take approximately 2.0 g of the cleaning agent and measure the sample weight (A). Dry in a hot air dryer at 120°C for 2 hours. Measure the weight (B) after drying. The solid content concentration is calculated according to the formula below. Furthermore, the amount of solids contained in one serving (6 g) of the cleaning agent is calculated according to the following formula.

Solid content concentration [%] = (weight after drying (B) / sample weight (A)) x 100

Solid content [g] = (solid content concentration [%] / 100) x 6

・Foaming property: Put 30 mL of cleaning agent adjusted to 1 wt% aqueous solution into a 100 mL sample tube (manufactured by Maruem Co., Ltd., No. 8, 40 mm x 120 mm), shake it vertically 20 times, and let it stand for 10 seconds to determine the foam height. The length (mm) was measured.

・Oil stain cleaning property and oil stain re-deposition prevention property (organic hard surface)
1 g of melted beef tallow was dropped into two 23 cm diameter PP (polypropylene) plates and allowed to solidify at room temperature for 30 minutes or more. A total of 4 plates, 2 plates with beef tallow attached and 2 plates without beef tallow attached, were placed alternately in the large plate holder of an automatic dishwasher (Electric dishwasher/dryer manufactured by Panasonic, product number: NP-TZ200-W). 6g of the cleaning ingredient with the composition described below and an amphoteric polymer compound added to the same amount of solid content as the cleaning ingredient were placed in a detergent container, and after cleaning and drying at cleaning level 3, the oil stains on the surface of the PP plate were removed. The adhesion surface was confirmed. The surface with oil stains was evaluated by dividing the front surface of the PP plate into 5 parts (Fig. 1 (a)) and the back surface into 4 parts (Fig. 1 (b)). (excluded from the target) and counted the number of surfaces with oil stains.
The ability to clean oil stains is evaluated by the number of surfaces with oil stains on a plate with beef tallow, and the ability to prevent oil stains from re-deposition is evaluated by the number of surfaces with oil stains on a plate without beef tallow. was evaluated.

・Prevents oil stains from re-deposition (inorganic hard surface)
Set 3 glass slides in the glass holder of an automatic dishwasher, put 3g of beef tallow into the chamber, and add 6g of the cleaning ingredient with the composition described below and an amphoteric polymer compound so that the solid content is the same as the cleaning ingredient. After washing and drying at cleaning level 1, the contact angle on the surface of the glass slide was measured. The contact angle was measured at 10 points on one glass slide, and the average value was used.

(Example 1)
An allylamine/maleic acid copolymer (copolymerization ratio 1.2:1) synthesized by the following method is used as an amphoteric polymer compound, and is combined with the cleaning components of each composition shown in Table 1 from 1 to 11 to create a cleaning agent. was constructed and evaluated for oil stain cleaning performance, oil stain re-deposition prevention property (organic hard surface), and oil stain re-deposition prevention property (inorganic hard surface). The results are shown in Tables 3 and 4.
Further, Table 2 shows the results of evaluating the foaming properties when combined with the cleaning components shown in 1 of Table 1.
[Synthesis method]
842.93 g of distilled water and 488.34 g (4.98 mol) of maleic anhydride were charged into a 3 L four-necked flask equipped with a thermometer, a stirrer, and a condenser. Thereafter, 342.60 g (6.00 mol) of allylamine was added dropwise while cooling, and the temperature was raised to 65°C. A 28.5% by mass ammonium persulfate aqueous solution was added in an amount such that ammonium persulfate was 1 mol% based on the total amount of monomers to initiate polymerization. After 3 hours, the ammonium persulfate aqueous solution was added in an amount such that ammonium persulfate was 1 mol % based on the total amount of monomers, and after 24 and 28 hours, the amount of ammonium persulfate was 2 mol % based on the total amount of monomers, and the reaction was continued overnight.

(Comparative example 1)
Example 1 except that diallyldimethylammonium chloride/maleic acid copolymer (copolymerization ratio 2:1) synthesized by the following method was used as the amphoteric polymer compound instead of allylamine/maleic acid copolymer. A cleaning agent was prepared and evaluated in the same manner as above. The results are shown in Tables 3 and 4.
Further, Table 2 shows the results of evaluating the foaming properties when combined with the cleaning components shown in 1 of Table 1.
[Synthesis method]
In a 500 mL four-necked flask equipped with a thermometer, stirrer, and condenser, 174.12 g (0.70 mol) of 65% by mass diallyldimethylammonium chloride, 34.32 g (0.35 mol) of maleic anhydride, and distilled 99.16 g of water was charged, and the internal temperature was raised to 60°C. A 28.5% by mass ammonium persulfate aqueous solution was added in an amount of 2 mol % (0.021 mol) based on the monomer to initiate polymerization. After 2, 4, and 24 hours, 2 mol % of a 28.5 mass % ammonium persulfate aqueous solution was added, and the reaction was continued overnight.

(Example 2)
Example 1 except that diallylamine hydrochloride/maleic acid copolymer (copolymerization ratio 1:1) synthesized by the following method was used as the amphoteric polymer compound instead of allylamine/maleic acid copolymer. A cleaning agent was constructed and evaluated in the same manner. The results are shown in Tables 3 and 4.
Further, Table 2 shows the results of evaluating the foaming properties when combined with the cleaning components shown in 1 of Table 1.
[Synthesis method]
In a 500 mL four-necked flask equipped with a thermometer, stirrer, and condenser, add 69.34% by mass diallylamine hydrochloride 144.53 g (0.75 mol), maleic anhydride 73.55 g (0.75 mol), distilled. 31.62 g of water was charged, and the internal temperature was raised to 50°C. Polymerization was started by adding a 28.5% by mass ammonium persulfate aqueous solution in an amount such that the amount of ammonium persulfate in the aqueous solution was 0.5% by mass based on the total amount of monomers. After 4 hours, the amount of ammonium persulfate becomes 0.5% by mass based on the total amount of monomers, after 20 and 26 hours, the amount of ammonium persulfate becomes 1.0% by mass based on the total amount of monomers, and after 45 and 51 hours, the amount of ammonium persulfate becomes 1.0% by mass based on the total amount of monomers. The above ammonium persulfate aqueous solution was added in an amount such that ammonium persulfate was 1.5% by mass, and the mixture was reacted for 68 hours.

(Example 3)
Example 1 except that diallylmethylamine/maleic acid copolymer (copolymerization ratio 1:1) synthesized by the following method was used as the amphoteric polymer compound instead of allylamine/maleic acid copolymer. A cleaning agent was constructed and evaluated in the same manner. The results are shown in Tables 3 and 4.
Further, Table 2 shows the results of evaluating the foaming properties when combined with the cleaning components shown in 1 of Table 1.
[Synthesis method]
1.86 kg (19.0 mol) of maleic anhydride and 0.34 kg of distilled water were placed in a 20 L four-necked flask equipped with a thermometer, stirrer, and condenser, and 2.11 kg (19.0 mol) of diallylmethylamine was added. ) was added dropwise under cooling. Thereafter, the internal temperature was raised to 50°C. A 28.5% by mass ammonium persulfate aqueous solution was added in an amount such that ammonium persulfate was 0.5% by mass based on the total amount of monomers to initiate polymerization. After 3, 21, and 25 hours, the ammonium persulfate aqueous solution was added in an amount such that ammonium persulfate was 1.0% by mass based on the total amount of monomers, and the reaction was continued overnight.

(Comparative example 2)
As a polymer compound, allylamine hydrochloride polymer (manufactured by Nitto Bo Medical Co., Ltd., brand name: PAA-HCl-3L) was used instead of allylamine-maleic acid copolymer, and foaming property was not evaluated. A cleaning agent was prepared and evaluated in the same manner as in Example 1 except for the following. The results are shown in Tables 3 and 4.

(Example 4)
As an amphoteric polymer compound, allylamine-itaconic acid copolymer (copolymerization ratio 2:1) synthesized by the following method was used instead of allylamine-maleic acid copolymer, and the foaming property was evaluated. A cleaning agent was prepared and evaluated in the same manner as in Example 1, except that there was no problem. The results are shown in Tables 3 and 4.
[Synthesis method]
A 300 mL four-necked flask equipped with a thermometer, stirrer, and condenser was charged with 52.04 g (0.4 mol) of itaconic acid and 59.59 g of distilled water, and 45.68 g (0.8 mol) of monoallylamine was added. It was added dropwise under cooling. Thereafter, the internal temperature was raised to 60°C. A 28.5% by mass ammonium persulfate aqueous solution was added in an amount of 2 mol% (0.024 mol) based on the monomer to initiate polymerization. After 2.4 hours, 28.5% by mass ammonium persulfate aqueous solution was added in 2% by mole portions and allowed to react overnight.

(Example 5)
As an amphoteric polymer compound, allylamine/itaconic acid copolymer (copolymerization ratio 1.2:1) synthesized by the following method was used instead of allylamine/maleic acid copolymer, and evaluation of foaming property A cleaning agent was prepared and evaluated in the same manner as in Example 1, except that the above was not carried out. The results are shown in Tables 3 and 4.
[Synthesis method]
A 300 mL four-necked flask equipped with a thermometer, stirrer, and condenser was charged with 39.03 g (0.3 mol) of itaconic acid and 59.59 g of distilled water, and 20.56 g (0.36 mol) of monoallylamine was added. It was added dropwise under cooling. Thereafter, the internal temperature was raised to 60°C. A 28.5% by mass ammonium persulfate aqueous solution was added in an amount of 2 mol % (0.0132 mol) based on the monomer to initiate polymerization. After 2.4 hours, 28.5% by mass ammonium persulfate aqueous solution was added in 2% by mole portions and allowed to react overnight.

(Example 6)
As an amphoteric polymer compound, allylamine/acrylamide 2-methylpropanesulfonic acid copolymer (copolymerization ratio 1:2) synthesized by the following method was used instead of allylamine/maleic acid copolymer, and foaming A cleaning agent was prepared and evaluated in the same manner as in Example 1, except that the properties were not evaluated. The results are shown in Tables 3 and 4.
[Synthesis method]
32.07 g (0.2 mol) of 58.35% by mass allylamine hydrochloride and 95.16 g of distilled water were placed in a 500 mL four-necked flask equipped with a thermometer, stirrer, and cooling tube, and the internal temperature was adjusted to 60°C. The temperature rose to . A mixed solution of 84.59 g of 98% by mass sodium acrylamide-2-methylpropanesulfonate and 126.89 g of distilled water was started to be added dropwise over 6 hours, and at the same time, initiator V-50 (2,2'-azobis(2- Methylpropionamidine dihydrochloride) was added in an amount such that V-50 was 1 mol % (0.006 mol) based on the total amount of monomers to initiate polymerization. After 2, 4, and 6 hours, 1 mol % (0.006 mol) of V-50 was added and reacted overnight. Thereafter, 100.80 g (0.63 mol) of sodium hydroxide having a concentration of 25% by mass was added under cooling to 30° C. or lower. Thereafter, demonomerization was performed using an evaporator (50° C., 2 hours). After removing the monomer, the concentration was adjusted to 15%, and desalination was performed by electrodialysis (approximately 3 hours, completed 1 hour after the electrical conductivity had completely decreased).

(Example 7)
As an amphoteric polymer compound, allylamine/citraconic acid copolymer (copolymerization ratio 2:1) synthesized by the following method was used instead of allylamine/maleic acid copolymer, and the foaming property was evaluated. A cleaning agent was prepared and evaluated in the same manner as in Example 1, except that there was no problem. The results are shown in Tables 3 and 4.
[Synthesis method]
A 300 mL four-necked flask equipped with a thermometer, stirrer, and condenser was charged with 73.02 g (0.55 mol) of 98% by mass citraconic acid and 32.12 g of distilled water, and 62.81 g (1. 1 mol) was added dropwise under cooling. Thereafter, the internal temperature was raised to 60°C. A 28.5% by mass ammonium persulfate aqueous solution was added in an amount of 2 mol % (0.033 mol) based on the monomer to initiate polymerization. After 4, 22, 25, and 28 hours, 2 mol % of a 28.5 mass % ammonium persulfate aqueous solution was added, and the reaction was continued overnight.

(Example 8)
As an amphoteric polymer compound, allylamine/acrylic acid copolymer synthesized by the following method (copolymerization ratio 1:1) was used instead of allylamine/maleic acid copolymer, and the foaming property was evaluated. A cleaning agent was prepared and evaluated in the same manner as in Example 1, except that there was no problem. The results are shown in Tables 3 and 4.
[Synthesis method] 80.17 g (0.5 mol) of allylamine hydrochloride of 58.35% by mass and 36.33 g of distilled water were placed in a 500 mL four-necked flask equipped with a thermometer, stirrer, and cooling tube. The temperature was raised to 60°C. A mixed solution of 36.03 g (0.5 mol) of acrylic acid and 84.07 g of distilled water was started to be added dropwise over 6 hours, and at the same time, initiator V-50 (2,2'-azobis(2-methylpropionamidine) di Hydrochloride) was added in an amount such that V-50 was 0.5 mol % (0.005 mol) based on the total amount of monomers to initiate polymerization. After 2 or 4 hours, 0.5 mol % (0.005 mol) of V-50 was added, and after 6 hours, 1.0 mol % (0.010 mol) of V-50 was added, and the mixture was allowed to react overnight. Thereafter, 168.00 g (1.05 mol) of sodium hydroxide having a concentration of 25% by mass was added under cooling to 30° C. or lower. Thereafter, demonomerization was performed using an evaporator (50° C., 2 hours). After removing the monomer, the concentration was adjusted to 15%, and desalination was performed by electrodialysis (approximately 4 hours, completed 1 hour after the electrical conductivity had completely decreased).

According to the present invention, a cationic structural unit (1) having at least one group selected from a primary amino group, a secondary amino group, and a tertiary amino group in its structure, and an anionic structural unit ( 2) In each example using an amphoteric polymer compound (specific amphoteric polymer compound) containing We were able to achieve excellent performance in anti-adhesion properties.
In Comparative Example 1, which used an amphoteric polymer compound that does not fall under the specified amphoteric polymer compound, the ability to prevent oil stains from re-adhering to inorganic hard surfaces was good, but the ability to clean oil stains from organic hard surfaces was poor. And the re-deposition prevention property was not necessarily good. In Comparative Example 2 using a cationic polymer compound that is not an amphoteric polymer compound, neither the oil stain re-deposition prevention property on inorganic hard surfaces nor the oil stain cleaning power and redeposition prevention property on organic hard surfaces , it wasn't necessarily good.

The oil stain cleaning agent for hard surfaces and the method for cleaning oil stains on hard surfaces of the present invention not only have excellent oil stain re-adhesion prevention properties (antifouling properties) on inorganic hard surfaces, but also It has excellent oil stain cleaning power and re-adhesion prevention properties, so it is particularly suitable for cleaning oil stains on hard surfaces using a dishwasher, and is suitable for cleaning personal items, daily necessities, household goods, barber/hygiene, cleaning, buildings, etc. It has high potential for use in various industries such as maintenance, food and beverage industry, accommodation facilities, leisure and sports facilities, and healthcare, medical care, health care, and nursing care.

Claims (12)

A cationic structural unit (1) having at least one group selected from a primary amino group, a secondary amino group, and a tertiary amino group in its structure, and an anionic structural unit (2). An oil stain cleaning agent for hard surfaces containing an amphoteric polymer compound. The oil stain for hard surfaces according to claim 1, wherein the molar ratio of the cationic structural unit (1) to the anionic structural unit (2) in the amphoteric polymer compound is from 0.4 to 25.0. Washing soap. The oil stain cleaning agent for hard surfaces according to claim 1 or 2, wherein the cationic structural unit (1) has a primary amino group. The oil stain cleaning agent for hard surfaces according to any one of claims 1 to 3, wherein the cationic structural unit (1) has a structure derived from a monoallylamine monomer. The oil stain cleaning agent for hard surfaces according to any one of claims 1 to 4, wherein the anionic structural unit (2) has a structure derived from an unsaturated carboxylic acid and/or a sulfonic acid. The oil stain cleaning agent for hard surfaces according to any one of claims 1 to 5, further comprising a surfactant. The oil stain cleaning agent for hard surfaces according to claim 6, wherein the surfactant contains a cationic surfactant and an anionic surfactant. The hard surface oil stain cleaning agent according to any one of claims 1 to 7, further comprising at least one selected from the group consisting of a chelating agent, a polyol, an alkali metal compound, and a thickener. The oil stain cleaning agent for hard surfaces according to any one of claims 1 to 8, wherein the content of the amphoteric polymer compound is 0.01 to 50% by mass. A method for cleaning oil stains on a hard surface using the hard surface oil stain cleaning agent according to any one of claims 1 to 9. The method for cleaning oil stains on a hard surface according to claim 10, wherein the hard surface is a surface of tableware, sanitary ware, or tiles. The method for cleaning oil stains on hard surfaces according to claim 10 or 11, using a dishwasher.