Oil stain remover and cleaning method for hard surfaces

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

[Technical Field]

[0001] The present invention relates to an oil stain remover for hard surfaces and a method for removing oil stains from hard surfaces. More specifically, it relates to an oil stain remover for hard surfaces that exhibits excellent resistance to preventing re-adhesion of oil stains (anti-fouling properties) to inorganic hard surfaces such as glass, and also exhibits excellent oil stain removal power and re-adhesion prevention properties to organic hard surfaces such as resins, and to a method for removing oil stains from hard surfaces using the same. [Background technology]

[0002] Various cleaning agents have been developed to remove dirt from hard surfaces such as tableware, and efforts have been made to enhance 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 reducing the number of washes, and from the perspective of preventing the re-adhesion of dirt that has been removed during washing. As an antifouling cleaning agent for hard surfaces that possesses both cleaning power and antifouling properties, a cleaning agent has been proposed that contains a polymer containing a predetermined ratio of constituent units having one or more groups selected from amino groups and quaternary ammonium salts and constituent units derived from sulfur dioxide (see, for example, Patent Document 1).

[0003] Dishwashers are rapidly becoming popular both in commercial settings such as restaurants and hotels, and in private homes, and require special dishwasher detergents. Traditionally, dishes were pre-washed to remove some of the food residue and dirt before being placed in a dishwasher. However, with the recent proliferation of dishwashers, this pre-washing is becoming less common, and dishwasher detergents need to be even more effective. When heavily soiled dishes are washed without pre-washing, the detergents often fail to adequately remove grease, resulting in residual grease, a slimy feeling, or contamination of other dishes after washing. Furthermore, dishwasher detergents need to be anti-foaming, as excessive foaming can lead to dishwasher malfunctions. In the prior art, dishwasher detergents have been proposed that contain polymer compounds containing monomer units having cationic groups and monomer units having anionic groups derived from quaternary ammonium salts, with the aim of improving the ability to prevent dirt from re-adhering to tableware (see, for example, Patent Document 2).

[0004] However, conventional cleaning agents described above do not always have sufficient cleaning power for oil stains or for preventing re-adhesion. In particular, they lack sufficient cleaning power for hard organic surfaces such as resins, for example, in the case of dishwasher cleaning agents, they are insufficient for resin plates and containers made of PP or PE, and oil stains or sliminess may remain after cleaning, so a solution to this problem was desired. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2003-313600 [Patent Document 2] Japanese Patent Publication No. 2012-214538 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] In view of the limitations of the above-mentioned conventional technology, the present invention provides for the prevention of re-adhesion of oil stains to inorganic hard surfaces such as glass (fouling resistance). In the same way as conventional technology The objective is to provide a hard surface oil stain remover that is excellent in terms of its ability to remove oil stains from hard organic surfaces such as resins and its ability to prevent re-adhesion, and which is particularly suitable for use as a dishwasher detergent, and a method for cleaning oil stains from hard surfaces using the same. [Means for solving the problem]

[0007] As a result of diligent research to solve the above problems, the present inventors have found that a hard surface oil stain cleaner containing an amphoteric polymer compound having a cationic constituent unit having at least one group selected from primary, secondary, and tertiary amino groups in its structure, and an anionic constituent unit, not only exhibits excellent resistance to preventing re-adhesion of oil stains (anti-fouling properties) on inorganic hard surfaces such as glass, but also exhibits excellent oil stain cleaning power and re-adhesion prevention properties on organic hard surfaces such as resins, thus completing the present invention. In other words, the present invention is [1] This is a cleaning agent for hard surfaces that removes oil stains, containing an amphoteric polymer compound comprising a cationic structural unit (1) having at least one group selected from primary, secondary, and tertiary amino groups in its structure, and an anionic structural unit (2).

[0008] Hereinafter, [2] to

[12] are preferred embodiments or models of the present invention. [2] The hard surface oil stain cleaner according to [1], wherein the molar ratio of cationic constituent units (1) to anionic constituent units (2) in the amphoteric polymer compound is 0.4 to 25.0. [3] The oil stain cleaner for hard surfaces according to [1] or [2], wherein the cationic constituent unit (1) has a primary amino group. [4] The oil stain cleaner for hard surfaces according to any one of [1] to [3], wherein the cationic constituent unit (1) has a structure derived from a monoallylamine monomer. [5] The hard surface oil stain cleaner according to any one of [1] to [4], wherein the anionic constituent unit (2) has a structure derived from an unsaturated carboxylic acid and / or a sulfonic acid. [6] A hard surface oil stain cleaner according to any one of items [1] to [5], further containing a surfactant. [7] The hard surface oil stain cleaner according to [6], wherein the surfactant comprises a cationic surfactant and an anionic surfactant. [8] Furthermore, the cleaning agent for oil stains on hard surfaces according to any one of [1] to [7] contains at least one selected from the group consisting of chelating agents, polyols, alkali metal compounds, and thickeners. [9] A cleaning agent for hard surfaces containing oil stains, 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 an oil stain cleaner for hard surfaces described in any one of items [1] to [9].

[11] The method for cleaning oil stains on a hard surface according to

[10] , wherein the hard surface is the surface of tableware, sanitary ware, or tiles.

[12] A method for cleaning oily stains on hard surfaces, as described in

[10] or

[11] , using a dishwasher. [Effects of the Invention]

[0009] The present invention provides an oil stain cleaner for hard surfaces and a method for cleaning oil stains on hard surfaces, which have high practical technical value, as they not only have excellent properties for preventing oil stains from re-adhering to inorganic hard surfaces such as glass (anti-fouling properties), but also excellent oil stain cleaning power and re-adhesion prevention properties for organic hard surfaces such as resins. The present invention provides an oil stain remover for hard surfaces and a method for removing oil stains from hard surfaces, which are particularly suitable for use in cleaning oil stains from hard surfaces using a dishwasher. They achieve technical effects that have particularly high practical value, such as excellent resistance to re-adhesion of dirt to glass plates, containers, ceramic plates, and containers. [Brief explanation of the drawing]

[0010] [Figure 1]This is a schematic diagram showing the structure of the PP dish used to evaluate the oil stain cleaning ability and oil stain re-adhesion prevention ability (organic hard surface) in the examples / comparative examples of this application, where (a) shows the front surface, (b) shows the back surface, and (c) is a perspective view. [Modes for carrying out the invention]

[0011] The present invention is an oil stain remover for hard surfaces, containing an amphoteric polymer compound comprising a cationic structural unit (1) having at least one group selected from primary, secondary, and tertiary amino groups in its structure, and an anionic structural unit (2). In other words, the oil stain cleaning agent for hard surfaces of the present invention contains an amphoteric polymer compound (hereinafter also referred to as "specific amphoteric polymer compound") comprising a cationic structural unit (1) having at least one group selected from primary amino groups, secondary amino groups, and tertiary amino groups in its structure, and an anionic structural unit (2). The hard surface oil stain cleaner of the present invention may consist solely of a specific amphoteric polymer compound, or it may consist of a specific amphoteric polymer compound and other components. From the viewpoint of achieving high cleaning performance, it is preferable to include components commonly used as cleaning agents in this art, such as surfactants (hereinafter also referred to as "cleaning components"), as the other components. There are no particular restrictions on the content of the specific amphoteric polymer compound in the hard surface oil stain cleaner of the present invention, but it is preferably 0.01 to 50% by mass, more preferably 0.015 to 30% by mass, and particularly preferably 0.02 to 10% by mass.

[0012] Specific amphoteric polymer compounds As described above, the specific amphoteric polymer compound used in the hard surface oil stain cleaning agent of the present invention is an amphoteric polymer compound comprising a cationic structural unit (1) having at least one group selected from primary amino groups, secondary amino groups, and tertiary amino groups in its structure, and an anionic structural unit (2). The specific amphoteric polymer compound may consist only of a cationic structural unit (1) and an anionic structural unit (2), or it may have other structural units in addition to the cationic structural unit (1) and anionic structural unit (2), such as nonionic structural units or cationic structural units other than cationic structural unit (1).

[0013] Cationic constituent unit (1) The cationic constituent unit (1) constituting the specific amphoteric polymer compound used in the present invention is a cationic constituent unit having at least one group selected from primary amino groups, secondary amino groups, and tertiary amino groups in its structure. The cationic structural unit (1) is not subject to any restrictions other than having at least one group selected from primary, secondary, and tertiary amino groups as a cationic functional group in its structure. Therefore, as long as it satisfies the condition that it has at least one group selected from primary, secondary, and tertiary amino groups in its structure, structural units of various structures can be adopted as cationic structural unit (1). From the viewpoint of low foaming and resistance to re-adhesion to inorganic surfaces such as glass, it is preferable that the cationic structural unit (1) has a primary amino group. Examples of cationic constituent units (1) include allylamine constituent units, diallylamine constituent units, aminoalkyl(meth)acrylamide constituent units such as aminoalkyl(meth)acrylamide constituent units, polyethyleneimine constituent units, and aminoethylated(meth)acrylic acid constituent units such as aminoethylated(meth)acrylic acid, all of which have at least one group selected from primary, secondary, and tertiary amino groups. Among these, allylamine constituent units, diallylamine constituent units, and aminopropylacrylamide constituent units such as aminopropylacrylamide are preferred, and allylamine constituent units are particularly preferred.

[0014] Allylamine system constituent units As the cationic constituent unit (1), allylamine-based constituent units are particularly preferred. Allylamine-based structural units are structural units having a structure represented by the following general formula (Ia), or a structure that is an acid addition salt thereof. [ka] In the formula, R 1 and R 2 Each of these is independently a hydrogen atom or a monovalent hydrocarbon group, and as the monovalent hydrocarbon group, a C1-C12 alkyl group which may have a hydroxyl group, a C7-C12 aralkyl group, or a C5-C6 cycloalkyl group is preferred. The preferred C1-C12 alkyl or aralkyl group as the monovalent hydrocarbon group may be linear or branched. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, decyl, dodecyl, and benzyl groups. Furthermore, while cyclopentyl and cyclohexyl groups are preferred C5-C6 cycloalkyl groups as the monovalent hydrocarbon group, the invention is not limited to these. R 1 and R 2 Each of these is preferably independently a hydrogen atom, a methyl group, an ethyl group, or a benzyl group, and is particularly preferably a hydrogen atom or a methyl group. R 1 and R 2 When both atoms are hydrogen atoms, the allylamine-based constituent unit becomes a cationic constituent unit (1) having a primary amino group, which is particularly preferable from the viewpoint of low foaming and resistance to re-adhesion to inorganic surfaces such as glass.

[0015] While there are no particular restrictions on the type of addition salt when the allylamine system unit is an acid addition salt of the structure represented by general formula (Ia), from the viewpoint of availability and ease of reaction control, for example, hydrochloride, sulfate, phosphate, nitrate, sulfite, phosphate, nitrite, hydrobromide, acetate, amide sulfate, methanesulfonate, trifluoroacetate, p-toluenesulfonate, etc. can be used. Among these, hydrochloride salts, sulfate salts, phosphate salts, and amide sulfate salts are preferred, and hydrochloride salts, sulfate salts, phosphate salts, and amide sulfate salts with structures derived from monoallylamine are particularly preferred.

[0016] diallylamine system constituent units Diallylamine-based structural units are structural units having a structure represented by the following general formula (Ib) or its acid addition salt, or a structure represented by the following general formula (Ic). [ka] In the formula, R 3 R is a hydrogen atom or a monovalent hydrocarbon group, and as the monovalent hydrocarbon group, a C1-C10 alkyl group which may have a hydroxyl group, a C5-C10 cycloalkyl group, or a C7-C10 aralkyl group is preferred. 3 It is preferably a hydrogen atom, a methyl group, an ethyl group, or a benzyl group, and is particularly preferably a hydrogen atom or a methyl group.

[0017] The structure may have a diallylamine system component, an inorganic salt or organic salt of the structure shown in the above structural formula (1-b), i.e., a structure that is an acid addition salt. When a specific amphoteric polymer compound has a diallylamine-based structural unit, in the production of the specific amphoteric polymer compound, from the perspective of production cost and the like, it is preferable to use a diallylamine monomer having an addition salt. The process of removing an addition salt such as HCl from the polymer is complicated and also causes an increase in cost. Therefore, using an addition salt type diallylamine-based structural unit that can be produced without such a process is a preferred embodiment from the perspective of cost and the like. From the perspective of ease of availability and reaction controllability, etc., the inorganic acid salt or organic acid salt in the diallylamine-based structural unit of this embodiment is preferably a hydrochloride, carboxylate, sulfonate, or alkyl sulfate salt, and particularly preferably a hydrochloride.

[0018]

Chemical formula

[0019] The counter ion X a- is not particularly limited, but from the perspective of ease of availability and reaction controllability, etc., it is preferably a chloride ion, a carboxylate ion, a sulfonate ion, or an alkyl sulfate ion, and particularly preferably a chloride ion or an ethyl sulfate ion. In the production of specific amphoteric polymer compounds, it is preferable to use diallylamine monomers having counterions from the viewpoint of production costs, etc. The process of removing counterions from polymers is complicated and can lead to increased costs, so using specific amphoteric polymer compounds having counterionic diallylamine-based constituent units that can be produced without such a process is a preferred embodiment from the viewpoint of costs, etc.

[0020] aminoalkyl(meth)acrylamide system building units As the cationic constituent unit (1), aminoalkyl(meth)acrylamide-based constituent units can also be preferably used. The aminoalkyl(meth)acrylamide system is a structural unit having a structure represented by the following general formula (Id), or a structure that is an acid addition salt thereof. [ka] R in the formula 6 R represents a hydrogen atom or a methyl group. 7 and R 8 Each of these independently represents a hydrogen atom or a monovalent hydrocarbon group, and n is an integer between 2 and 4. R 6 It is preferably a methyl group, and n is preferably 2 to 3. R 7 and R 8 Each of these is preferably an independent hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom or a methyl group. 7 and R 8 When both atoms are hydrogen atoms, the aminoalkyl(meth)acrylamide system constituent unit becomes a cationic constituent unit (1) having a primary amino group, which is particularly preferable from the viewpoint of low foaming and resistance to re-adhesion to inorganic surfaces such as glass. There are no particular restrictions on the type of addition salt when the aminoalkyl(meth)acrylamide system constituent unit is an acid addition salt with a structure represented by general formula (Id). However, from the viewpoint of availability and ease of reaction control, for example, hydrochloride, sulfate, phosphate, nitrate, sulfite, phosphate, nitrite, hydrobromide, acetate, amide sulfate, methanesulfonate, trifluoroacetate, p-toluenesulfonate, etc. can be used. Among these, hydrochloride salts, sulfates, phosphates, and amide sulfates are preferred, and hydrochloride salts, sulfates, phosphates, and amide sulfates with structures derived from aminopropyl(meth)acrylamide are particularly preferred.

[0021] The specific amphoteric polymer compound may contain only one type of cationic structural unit (1), or it may contain two or more types of cationic structural units (1). The proportion of cationic constituent units (1) to the total constituent units of a specific amphoteric polymer compound is usually 10 to 90 mol%, preferably 30 to 70 mol%, and particularly preferably 40 to 60 mol%. When two or more types of cationic constituent units (1) are included, the above proportion is defined based on the total amount of those two or more types of cationic constituent units (1).

[0022] Anionic constituent 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. There are no restrictions on the anionic structural unit (2) other than that it contains an anionic functional group in its structure. Therefore, as long as it satisfies the condition of containing an anionic functional group in its structure, various structural units can be adopted as 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 preferred as anionic structural units (2) are structural units (2-1), (2-2), (2-3), and (2-4) listed below. Among these, structural units (2-1), (2-2), and (2-3), i.e., structural units having a structure derived from an unsaturated dicarboxylic acid, are preferred. Furthermore, structural units having structures derived from unsaturated monocarboxylic acids, including structural units (2-4), and structural units having structures derived from sulfonic acids can also be preferably used as anionic structural unit (2).

[0023] The characteristic amphoteric polymer compound may contain only one type of anionic constituent unit (2), or it may contain two or more types of anionic constituent units (2). When it contains two or more types of anionic constituent units (2), the two or more types of anionic constituent units (2) may be a combination of constituent units that are both classified as constituent unit (2-1), a combination of constituent units that are both classified as constituent unit (2-2), a combination of constituent units that are both classified as constituent unit (2-3), or a combination of constituent units that are both classified as constituent unit (2-4), or a combination of constituent units that are classified as different from constituent units (2-1) to (2-4). It is also possible to use a combination of anionic constituent units that do not fall under any of constituent units (2-1) to (2-4).

[0024] Constituent units (2-1) The constituent unit (2-1) is a constituent unit having a structure represented by the following general formula (II-a). [ka] R in the formula 9 is either hydrogen or a methyl group, and Y independently represents hydrogen, Na, K, NH4, 1 / 2Ca, 1 / 2Mg, 1 / 2Fe, 1 / 3Al, or 1 / 3Fe for each bonded carboxyl group. R 9It is preferably hydrogen, and Y is preferably hydrogen or Na. The constituent unit (2-1) is particularly preferably derived from maleic acid.

[0025] Constituent units (2-2) The constituent unit (2-2) is a constituent unit having a structure represented by the following general formula (II-b). [ka] In the formula, Y independently represents hydrogen, Na, K, NH4, 1 / 2Ca, 1 / 2Mg, 1 / 2Fe, 1 / 3Al, or 1 / 3Fe for each bonded carboxyl group. Y is preferably hydrogen or sodium.

[0026] Constituent units (2-3) The constituent unit (2-3) is a constituent unit having a structure represented by the following general formula (II-c). [ka] In the formula, Y is independently hydrogen, Na, K, NH4, 1 / 2Ca, 1 / 2Mg, 1 / 2Fe, 1 / 3Al, or 1 / 3Fe for each bonded carboxyl group. Y is preferably hydrogen or sodium.

[0027] Constituent units (2-4) The constituent unit (2-4) is a constituent unit having a structure represented by the following general formula (II-d). [ka] R in the formula 10 R is either a hydrogen or methyl group, and Y is independently hydrogen, Na, K, NH4, 1 / 2Ca, 1 / 2Mg, 1 / 2Fe, 1 / 3Al, or 1 / 3Fe for each bonded carboxyl group. 10 It is preferable that is hydrogen, and Y is preferably hydrogen or Na. The constituent units (2-4) are preferably derived from (meth)acrylic acid, and are particularly preferably derived from acrylic acid.

[0028] From the viewpoint of oil stain removal properties and re-adhesion prevention properties on organic surfaces such as polypropylene, a structural unit having a structure derived from sulfonic acid can preferably be used as the anionic structural unit (2). Examples of structural units derived from sulfonic acid include structural units derived from acrylamide 2-methylpropanesulfonic acid, structural units derived from sodium allylsulfonate, vinylsulfonic acid, and structural units derived from sodium vinylsulfonate, among which structural units derived from acrylamide 2-methylpropanesulfonic acid are particularly preferred.

[0029] The specific amphoteric polymer compound used in the present invention contains the above-mentioned cationic structural unit (1) and anionic structural unit (2), and is therefore an amphoteric polymer compound having both cationic and anionic properties. The mechanism by which the present invention achieves remarkable technical effects—that the oil stain cleaner for hard surfaces of the present invention not only exhibits excellent resistance to preventing re-adhesion of oil stains on inorganic hard surfaces (anti-fouling properties) but also excellent oil stain cleaning power and re-adhesion prevention properties on organic hard surfaces—by using a specific amphoteric polymer compound having the above-described cationic structural unit (1) and an anionic structural unit (2), is not entirely clear, but it is presumed that this is related to the fact that the specific amphoteric polymer compound interacts with components such as surfactants contained in the cleaning agent, thereby assisting the oil stain dispersion effect of the surfactant.

[0030] As described above, in a specific amphoteric polymer compound, it is preferable that the cationic structural unit is an allylamine-based structural unit, and that the anionic structural unit (2) is a structural unit derived from an unsaturated dicarboxylic acid. Therefore, 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) can be used particularly favorably from the viewpoint of oil stain cleaning power, re-adhesion prevention, foam suppression, etc.

[0031] There are no particular restrictions on the proportion of the total number of cationic constituent units (1) and anionic constituent units (2) to the total number of constituent units of the specific amphoteric polymer compound, but it is usually 50 mol% or more, preferably 65 to 100 mol%, more preferably 80 to 100 mol%, and particularly preferably 90 to 100 mol%. There are no particular restrictions on the ratio of cationic constituent units (1) to anionic constituent units (2), but typically the molar ratio of cationic constituent units (1) to anionic constituent units (2) is in the range of 0.4 to 25.0, preferably in the range of 0.5 to 10.0, and more preferably in the range of 0.7 to 5.0. By having the molar ratio of cationic constituent units (1) to anionic constituent units (2) within the above range, advantageous effects such as obtaining polymers in high yield and maintaining sufficient water solubility when used as a detergent can be realized. When the anionic component (2) is derived from an unsaturated dicarboxylic acid, the molar ratio of the cationic component (1) to the anionic component (2) is preferably 0.5 to 2.0, and particularly preferably 1.0 to 2.0.

[0032] The molar ratio of cationic constituent units (1) to anionic constituent units (2) in a specific amphoteric copolymer can be measured by conventionally known methods, such as elemental analysis. 1 H-NMR, 13 It can be measured by NMR methods such as 13C-NMR. In addition, depending on the type of constituent units in a specific amphoteric copolymer, the proportion (molar ratio) of constituent units derived from each monomer often closely matches the initial composition (molar ratio) of each monomer during copolymerization. In such cases, the monomer blending ratio may be conveniently treated as the proportion (molar ratio) of constituent units. The molar ratio of cationic constituent unit (1) to anionic constituent unit (2) in a specific amphoteric copolymer can be appropriately adjusted by selecting and adjusting the type and amount of each monomer supplied in the production (copolymerization) of the specific amphoteric copolymer, particularly the monomer that leads to cationic constituent unit (1) and the monomer that leads to anionic constituent unit (2), as well as the production (copolymerization) conditions, such as the type and amount of catalyst, copolymerization temperature and time, etc.

[0033] Other constituent units (3) The specific amphoteric polymer compound may have other constituent units in addition to the cationic constituent unit (1) and anionic constituent unit (2) described above. Other constituent units include the nonionic constituent units (3-1) described later, and cationic constituent units (3-2) that have structures that do not fall under the cationic constituent units (1), i.e., those that do not have any primary, secondary, or tertiary amino groups. Specific amphoteric polymer compounds Other constituent units (3) are not essential constituent units of the specific amphoteric polymer compound, but can be introduced into the specific amphoteric polymer compound for purposes such as improving polymerizability, water solubility, and compatibility with detergent components.

[0034] Nonionic constituent units (3-1) In this embodiment, the nonionic constituent unit (3-1) may be any constituent unit derived from a nonionic monomer copolymerizable with the cationic constituent unit (1) and the anionic constituent unit (2), and there are no other particular restrictions. However, constituent units derived from methacrylate ester monomers, acrylic acid ester monomers, methacrylamide monomers, acrylamide monomers, sulfur dioxide, etc., can be preferably used. More specific examples include constituent units derived from 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-t-butylcyclohexyl acrylate, or sulfur dioxide. It is particularly preferable to use structural units derived from acrylamide, methacrylamide, or hydroxyethylacrylamide. Nonionic constituent units (3-1) can usually be introduced into specific amphoteric polymer compounds by using nonionic monomers as monomers.

[0035] When a specific amphoteric polymer compound has nonionic constituent units (3-1), there are no particular restrictions on the content of these nonionic constituent units (3-1), and the preferred amount varies depending on the type of nonionic constituent unit (3-1). However, it is preferable to contain 1 to 50 mol%, and more preferably 1 to 20 mol%, of 100 mol% of the total constituent units. When the nonionic constituent unit (3-1) is derived from a methacrylate monomer, an acrylic acid monomer, a methacrylamide monomer, or an acrylamide monomer, the above content is preferably 1 to 50 mol%, and more preferably 1 to 20 mol%. When the nonionic constituent unit (3-1) is derived from sulfur dioxide, the above content is preferably 1 to 50 mol%, and more preferably 20 to 50 mol%.

[0036] The content ratio of nonionic structural units (3-1) in specific amphoteric copolymers can also be measured by conventionally known methods, such as elemental analysis. 1 H-NMR, 13 It can be measured by NMR methods such as 13C-NMR. In addition, depending on the type of constituent unit in a specific amphoteric copolymer, the proportion (molar ratio) of constituent units derived from each monomer often closely matches the initial composition (molar ratio) of each monomer during copolymerization. In such cases, for convenience, the blending ratio (moles) of the monomers that derive nonionic constituent units (3-1) from the total amount (moles) of monomers can be treated as the content ratio of nonionic constituent units (3-1). The content ratio of nonionic structural units (3-1) in a specific amphoteric copolymer can be appropriately adjusted by selecting and adjusting the type and amount of each monomer supplied in the production (copolymerization) of the specific amphoteric copolymer, particularly the monomer that leads to the nonionic structural units (3-1), as well as the production (copolymerization) conditions, such as the type and amount of catalyst, copolymerization temperature and time, etc.

[0037] Cationic constituent units that do not have primary, secondary, or tertiary amino groups (3-2) There are no particular restrictions on the type of cationic constituent unit (3-2) that does not have a primary amino group, a secondary amino group, or a tertiary amino group. A monomer copolymerizable with the monomer that leads to the cationic constituent unit (1) and the monomer that leads to the anionic constituent unit (2) can be appropriately introduced, and constituent units derived from a cationic monomer that does not have a primary amino group, a secondary amino group, or a tertiary amino group can be appropriately introduced. Cationic monomers that do not have primary, secondary, or tertiary amino groups include, but are not limited to, diallylamine monomers having a quaternary amino group.

[0038] When a specific amphoteric polymer compound has a cationic constituent unit (3-2) that does not have any primary, secondary, or tertiary amino groups, there are no particular restrictions on the content of the cationic constituent unit (3-2) that does not have any primary, secondary, or tertiary amino groups. Furthermore, the preferred amount varies depending on the type of cationic constituent unit (3-2) that does not have any secondary or tertiary amino groups, but it is preferable to contain 1 to 35 mol%, and more preferably 1 to 10 mol%, based on 100 mol% of the total constituent units. The method for measuring and preparing the content of cationic constituent units (3-2) that do not have either secondary or tertiary amino groups in a specific amphoteric copolymer is the same as that described above in relation to the content of nonionic constituent units (3-1).

[0039] Physical properties of specific amphoteric polymer compounds There are no particular restrictions on the molecular weight of the specific amphoteric polymer compound. Depending on the usage form of the hard surface oil stain cleaner and its relationship with other components, a specific amphoteric polymer compound with a suitable molecular weight can be obtained or polymerized as appropriate. However, from the viewpoint of handling and solubility, a weight-average molecular weight (Mw) of 500 to 200,000 is usually used. From the viewpoint of achieving excellent solubility, the weight-average molecular weight (Mw) of the specific amphoteric polymer compound is preferably 500 to 150,000, and more preferably 500 to 100,000. From the viewpoint of carrying out polymerization 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, and more preferably 50,000 or less. The weight-average molecular weight (Mw) of a specific amphoteric polymer compound can be measured, for example, by gel permeation chromatography (GPC) using a liquid chromatograph. More specifically, it can be measured by the method described in the examples of this application. The molecular weight of a specific amphoteric polymer compound can be appropriately adjusted by adjusting the type and composition of the monomers used as raw materials, the temperature, time, and pressure in the polymerization process, and the type and amount of radical initiator used in the polymerization process.

[0040] There are no particular restrictions on the rotational viscosity [η] of the specific amphoteric polymer compound, and it can be set appropriately depending on the usage form of the hard surface oil stain cleaner and its relationship with other components, but it is preferably 5 to 2,000 mPa·s (25℃), and particularly preferably 10 to 1,000 mPa·s (25℃). The rotational viscosity [η] can be measured by methods commonly used in this industry, for example, by an AMETEK Brookfield DV-3T digital type B viscometer. Measurement is typically performed using a ULA adapter, with 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 the monomers used as raw materials, the temperature, time, and pressure in the polymerization process, and the type and amount of radical initiator used in the polymerization process.

[0041] Method for producing specific amphoteric polymer compounds There are no particular restrictions on the method for producing specific amphoteric polymer compounds, and they can be produced by methods conventionally known in the art. For example, they can be produced by copolymerizing a cationic monomer having a structure corresponding to a cationic structural unit (1), an anionic monomer having a structure corresponding to an anionic structural unit (2), and other monomers such as a nonionic monomer having a structure corresponding to a nonionic structural unit (3) if desired.

[0042] The solvent used when copolymerizing a cationic monomer with a structure corresponding to a cationic structural unit (1), an anionic monomer with a structure corresponding to an anionic structural unit (2), etc., is not particularly limited and may be an aqueous solvent or an organic solvent such as an alcohol, ether, sulfoxide, or amide, but an aqueous solvent is preferred. When copolymerizing a cationic monomer with a structure corresponding to a cationic structural unit (1), an anionic monomer with a structure corresponding to an anionic structural unit (2), etc., the monomer concentration varies depending on the type of monomer and the type of solvent used for copolymerization, but 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, but preferred examples include peroxides such as t-butyl hydroperoxide, persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate, and water-soluble azo compounds such as azobis and diazo compounds.

[0043] The amount of radical polymerization catalyst added is generally 0.1 to 20 mol%, preferably 1.0 to 10 mol%, relative to the total monomer. 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. Polymerization can be carried out in the atmosphere of air without causing significant problems, but it can also be carried out in an atmosphere of an inert gas such as nitrogen.

[0044] Cleansing ingredients In addition to the specific amphoteric polymer compounds described above, the present invention may contain other components, such as surfactants and other components commonly used as cleaning agents in this art (hereinafter also referred to as "cleaning components"), from the viewpoint of achieving high cleaning performance and improving the dispersibility of dirt components. There are no particular restrictions on the type of cleaning component in this embodiment, but it is especially preferable to include various surfactants, including cationic surfactants and anionic surfactants. The cleaning agent may further contain one or more components selected from chelating agents, polyols, alkali metal compounds, thickeners, enzymes, and bleaching agents.

[0045] surfactants In this embodiment, the hard surface oil stain cleaner preferably contains a surfactant as a cleaning component for purposes such as enhancing the anti-fouling cleaning effect and providing foaming properties to improve the feeling of cleaning effectiveness and adhesion during use. The surfactant preferably consists of one or more selected from anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants.

[0046] Examples of anionic surfactants include alkylbenzene sulfonates, alkanesulfonates, α-olefin sulfonates, alkyl sulfates, polyoxyethylene (average number of added moles 1 to 10) alkyl ether sulfates, and polyoxyethylene (average number of added moles 1 to 10) alkyl ether acetates. Among these, alkylbenzene sulfonates with 10 to 15 alkyl groups, alkyl sulfates with 8 to 14 alkyl groups, and polyoxyethylene (average number of added moles 1 to 5) alkyl ether sulfates with 10 to 14 alkyl groups are preferred. Sodium or potassium salts are preferred as the salts.

[0047] As nonionic surfactants, compounds of general formula (3) and / or general formula (4) below are preferred from the viewpoint of anti-fouling and cleaning effect. R 11 -T-[(R 12 O) a -R 13 ] b -(3) [In the formula, R 11 R is an alkyl or alkenyl group having 8 to 20 carbon atoms, preferably 10 to 18 carbon atoms. 12 R is an alkylene group having 2 or 3 carbon atoms, preferably an ethylene group. 13 b is an alkyl group having 1 to 3 carbon atoms, or a hydrogen atom. a represents a number from 1 to 100, preferably 3 to 80, more preferably 5 to 40, and particularly preferably 5 to 20. T is -O-, -COO-, -CON-, or -N-, and if T is -O- or -COO-, b is 1, and if T is -CON- or -N-, b is 1 or 2.

[0048] R 14 -(OR 15 ) c G d -(4) [In the formula, R 14 R is a linear alkyl group having 8 to 16 carbon atoms, preferably 10 to 16, and particularly preferably 10 to 14 carbon atoms. 15 is an alkylene group having 2 to 4 carbon atoms, preferably an ethylene group or a propylene group, particularly an ethylene group; G is a residue derived from a reducing sugar; c is a number with an average value of 0 to 6; and d is a number with an average value of 1 to 10, preferably 1 to 5, particularly preferably 1 to 2.

[0049] The following compounds can be given as specific examples of compounds of general formula (3). R 11 -O-(C2H4O) e -H [In the formula, R 11 The above indicates the meaning. e is a number between 1 and 100, preferably between 5 and 20. R 11 -O-(C2H4O) f -(C3H6O) g -H [In the formula, R 11 The above meaning is indicated. f and g are each independently a number from 1 to 20, preferably from 1 to 10, and EO and propylene oxide may be random or block adducts.

[0050] [ka] [In the formula, R 11 The above indicates the meaning. h and i are each independently numbers from 0 to 40, preferably from 0 to 20, and h+i is a number from 1 to 20, preferably from 1 to 15. 16 , R 17 Each of these is independently either a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

[0051] In the compound of general formula (4), G is a residue derived from a reducing sugar, and the starting reducing sugar may be either an aldose or a ketose, or it may be a triose, tetrose, pentose, or hexose having 3 to 6 carbon atoms. Specifically, examples of aldoses include apiose, arabinose, galactose, glucose, lyxose, mannose, aldose, idose, talose, and xylose, and an example of a ketose is fructose. In this embodiment, among these, aldopentoses or aldhexoses having 5 or 6 carbon atoms are particularly preferred, and glucose is the most preferred among them.

[0052] As cationic surfactants, compounds of the (alkyl)amideamine system of general formula (5) and compounds of general formulas (6) to (8) below are preferred from the viewpoint of antifouling effect. [ka] In general formula (5), R 18 This 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. R 18 The alkyl and alkenyl groups in the compound each have 11 to 21 carbon atoms, and the anti-foaming effect and cleaning power against oily stains are enhanced, so preferably the number of carbon atoms is 13 to 21, more preferably 15 to 21, and particularly preferably 15 to 19. R 18 Preferably, the alkyl group is a linear or branched alkyl group having 13 to 21 carbon atoms.

[0053] R 19 These are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group having 1 to 4 carbon atoms. R 19 The number of hydroxyl groups in the hydroxyalkyl group may be one or two or more. R 19Preferably, the members are 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.

[0054] R 20 This is an alkylene group having 1 to 4 carbon atoms. R 20 The alkylene group in the compound 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.

[0055] R 21 and R 22 Each of these is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R 21 and R 22 The number of carbon atoms in each alkyl group is 1 to 4, preferably 1 to 3, more preferably 1 or 2, and particularly preferably 1. R 21 and R 22 Preferably, each of these is an alkyl group having 1 to 4 carbon atoms, and it is preferable that they are the same.

[0056] Examples of (alkyl)amideamine compounds of general formula (5) include dimethylaminoethyl laurate, diethylaminoethyl laurate, dipropylaminoethyl laurate, dimethylaminopropyl laurate, diethylaminopropyl laurate, dipropylaminopropyl laurate, dimethylaminoethyl myristate, diethylaminoethyl myristate, dipropylaminoethyl myristate, dimethylaminopropyl myristate, diethylaminopropyl myristate, dipropylaminopropyl myristate, dimethylaminoethyl palmitate, diethylaminoethyl palmitate, dipropylaminoethyl palmitate, dimethylaminopropyl palmitate, diethylaminopropyl palmitate, dipropylaminopropyl palmitate, dimethylaminoethyl stearate, diethylaminoethyl stearate Examples include amides, dipropylaminoethyl stearate, dimethylaminopropyl stearate, diethylaminopropyl stearate, dipropylaminopropyl stearate, dimethylaminoethyl behenate, diethylaminoethyl behenate, dipropylaminoethyl behenate, dimethylaminopropyl behenate, diethylaminopropyl behenate, dipropylaminopropyl behenate, dimethylaminoethyl methyl laurate, dimethylaminoethyl methyl myristate, dimethylaminoethyl methyl palmitate, dimethylaminoethyl methyl stearate, dimethylaminoethyl methyl behenate, dimethylaminopropyl methyl laurate, dimethylaminopropyl methyl myristate, dimethylaminopropyl methyl palmitate, dimethylaminopropyl methyl stearate, and dimethylaminopropyl methyl behenate. Among these, dimethylaminopropyl myristate, dimethylaminopropyl palmitate, dimethylaminopropyl stearate, and dimethylaminopropyl behenate are preferred because they provide a more effective anti-foaming effect. The (alkyl)amideamine compounds of general formula (5) may be used individually or in combination of two or more.

[0057] [ka] [In the formula, R 23 R is an alkyl group or alkenyl group of 5 to 18, preferably 6 to 14, particularly preferably 8 to 12, and R is an alkyl group. 25 , R 26 is an alkyl group or hydroxyalkyl group having 1 to 3 carbon atoms. U is -COO-, OCO-, -CONH-, -NHCO-, [ka] j is a number that is either 0 or 1. 24 This is an alkylene group having 1 to 6 carbon atoms, or -(OR 33 ) k - is the case here R 33 R 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. 27 R is an alkylene group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms. 28 R is an alkyl group having 8 to 16 carbon atoms. 29 , R 30 , R 31 , R 32 Of these, two or more (preferably two) are alkyl groups having 8 to 18 carbon atoms, preferably 8 to 12 carbon atoms, and the remainder are alkyl groups or hydroxyalkyl groups having 1 to 3 carbon atoms. Furthermore, Z - This is an anionic group, preferably a halogen ion or an alkyl sulfate ion having 1 to 3 carbon atoms.

[0058] Among the cationic surfactants of General Formulas (6) to (8), the following are particularly preferred.

Chem.

[0059] As the amphoteric surfactant, the compound of the following General Formula (9) and the compound of General Formula (10) are preferred.

Chem.

[0060]

Chem.

[0061] In this embodiment, a cationic surfactant or an anionic surfactant is preferable from the viewpoint of antifouling effect, and it is particularly preferable to use them in combination. As the cationic surfactant, a (alkyl)amidoamine-based compound of the general formula (5) is preferable, and as the anionic surfactant, an alkylbenzenesulfonate having 8 to 18 carbon atoms in the alkyl group is preferable, and it is particularly preferable to use them in combination.

[0062] The surfactant is preferably contained in the hard surface oil stain cleaner of this embodiment at 0.001 to 50% by mass, particularly preferably 0.005 to 30% by mass, and more preferably 0.01 to 25% by mass. When cleaning the target hard surface by spraying with a spraying device such as a trigger or an aerosol, or by a method such as coating, the concentration of the surfactant is 0.001 to 10% by mass, more preferably 0.005 to 5% by mass, and still more preferably 0.01 to 3% by mass. On the other hand, in the cleaning method using the water in the toilet tank, when used in an automatic cleaner for toilets 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 path, it contains 0.1 to 50% by mass, more preferably 1 to 30% by mass, and still more preferably 5 to 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.

[0063] In this embodiment, when an anionic surfactant is used as the surfactant, the antifouling effect may be reduced. Therefore, from the viewpoint of antifouling effect, it is preferable that the content of the anionic surfactant be 70% by mass or less, preferably 50% by mass or less, relative to the total amount of surfactant. In particular, when a cationic surfactant represented by general formulas (5) to (7) and an anionic surfactant are used in combination, it is preferable that the ratio of the anionic surfactant to the mass of the cationic surfactant is less than 1.4 by mass, and especially less than 1.0.

[0064] polyol In this embodiment, for the purpose of improving cleaning power against organic stains and ensuring stability during storage, it is preferable to include a water-soluble solvent as a cleaning component, preferably a monohydric alcohol having 1 to 5 carbon atoms, and more preferably a polyol having 4 to 12 carbon atoms, with the addition of a polyol being preferable.

[0065] Common examples of monohydric alcohols include ethanol, propyl alcohol, and isopropyl alcohol. By incorporating these lower alcohols, the stability of the system at low temperatures can be further improved.

[0066] Preferably, polyols having 4 to 12 carbon atoms include isoprene glycol, 2,2,4-trimethyl-1,3-pentanediol, 1,4-butanediol, 1,5-pentanediol, 1,8-octanediol, 1,9-nonanediol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, and monoalkylglyceryl ethers with 3 to 8 carbon atoms in the alkyl group.

[0067] The above-mentioned polyols may be contained in the hard surface oil stain cleaner of this embodiment in an amount of 0.1 to 50% by mass, more preferably 0.5 to 30% by mass. When cleaning a hard surface by spraying with a spraying device such as a trigger or aerosol, or by applying the solution, the concentration of polyols is usually 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, and particularly preferably 0.5 to 7% by mass. On the other hand, when used in an automatic toilet cleaner that uses water in a toilet tank and can dispense an appropriate amount of cleaning solution into the water in the tank by installing a device in the tank or any water supply path, the concentration is usually 1 to 50% by mass, more preferably 3 to 40% by mass, and even more preferably 5 to 30% by mass. The concentration of polyols in the toilet tank is preferably 0.01 to 20 ppm, and more preferably 0.1 to 10 ppm.

[0068] Chelating agents In this embodiment, it is preferable to further incorporate a chelating agent for the purpose of dissolving inorganic stains, improving cleaning power, and further enhancing the anti-fouling effect. Suitable chelating agents include (1) tripolyphosphate, pyrophosphate, orthophosphate, hexametaphosphate and their alkali metal salts, (2) ethylenediaminetetraacetic acid, hydroxyiminodiacetic acid, dihydroxyethylglycine, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid and their alkali metal salts or alkaline earth metal salts, (3) aminotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, aminotrimethylenephosphonic acid, and their alkali metal salts. (4) Monopolymers or copolymers of monomers selected from acrylic acid and methacrylic acid, acrylic acid-maleic acid copolymers, poly-α-hydroxyryl acid and alkali metal salts thereof, (5) One or more polycarboxylic acids selected from citric acid, succinic acid, malic acid, fumaric acid, tartaric acid, malonic acid, maleic acid and alkali metal salts thereof, (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 salts thereof are preferred, and compounds (2), (3), and (5) above are particularly preferred.

[0069] The chelating agent is preferably contained in the hard surface oil stain cleaner of this embodiment at a concentration of 0.1 to 30% by mass. When cleaning a hard surface by spraying with a spraying device such as a trigger or aerosol, or by applying the cleaner, the concentration of the chelating agent is preferably 0.1 to 20% by mass, more preferably 0.3 to 10% by mass. On the other hand, when used in an automatic toilet cleaner that utilizes water in a toilet tank and allows an appropriate amount of cleaning solution to be dispensed into the water in the tank by installing a device in the tank or any water supply path, the concentration is preferably 0.1 to 20% by mass, more preferably 0.1 to 10% by mass. The concentration of the chelating agent in the toilet tank is preferably 0.01 to 20 ppm.

[0070] Alkali metal compounds The anti-fouling cleaning agent for hard surfaces of the present invention is preferably made of an alkali metal compound, especially when used in a dishwasher-based cleaning method, from the viewpoint of preventing re-adhesion and reducing odor after cleaning. The alkali metal compound is preferably an alkali metal carbonate and / or alkali metal hydroxide, more preferably sodium carbonate, potassium carbonate, sodium hydroxide, or potassium hydroxide, and particularly preferably sodium hydroxide or potassium hydroxide.

[0071] The alkali metal compound content in the antifouling cleaning agent for hard surfaces of this embodiment is preferably 5 to 30% by mass, and more preferably 7 to 25% by mass, from the viewpoint of preventing re-adhesion of dirt and reducing odor after cleaning.

[0072] Thickening agent In this invention, a thickening agent such as a water-soluble polymer may be added to improve ease of use by providing adhesion during use. The type of thickening agent is not particularly limited, but for example, (i) Natural polymers of plant origin such as guar gum, locust bean gum, carrageenan, alginic acid, gum arabic, and pectin. (ii) Microbial-derived natural polymers such as xanthan gum, (iii) Cellulose, starch, and starch derivatives and cellulose derivatives obtained by processing cellulose starch with oxidation, methylation, carboxymethylation, hydroxyethylation, hydroxypropylation, cationization, etc. (iv) Polyacrylic acid derivatives which are polyacrylic acid homopolymers or copolymers of monomers copolymerizable with acrylic acid, and crosslinked polyacrylic acid homopolymers or polyacrylic acid derivatives. (v) Natural polymers of animal origin 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 by oxidation, methylation, carboxymethylation, hydroxyethylation, hydroxypropylation, cationization, etc. (vii) Alginic acid derivatives such as ammonium alginate and propylene glycol alginate, (viii) Complete or incomplete saponified vinyl acetate homopolymers or copolymers of vinyl acetate and other monomers, or polyvinyl alcohol or polyvinyl alcohol derivatives obtained by crosslinking these with, for example, an aldehyde. (ix) Polyalkylene glycols such as polyethylene oxide, polypropylene oxide, copolymers of ethylene oxide and propylene oxide, (x) Polydimethylaminoethyl methacrylate and its quaternary derivatives or copolymers of dimethylaminoethyl methacrylate and monomers copolymerizable with dimethylaminoethyl methacrylate and their quaternary derivatives, ring-closed polymers of dimethyldiallylammonium chloride, and synthetic cationic polymers such as poly(N-vinyl-2,3-dimethylimidazolinium chloride) can be preferably used. The content of the thickener in the anti-fouling cleaning agent for hard surfaces of this embodiment is preferably 0.05 to 2.0% by mass, and more preferably 0.1 to 0.5% by mass, from the viewpoint of handling properties, uniform solubility, etc.

[0073] In addition to the above-mentioned components, the antifouling cleaning agent for hard surfaces of the present invention may contain additives commonly found in cleaning agents, such as fragrances, antibacterial agents, viscosity modifiers, pigments, dyes, suspending agents, hydrotropes, antioxidants, pH adjusters, etc., to the extent that they do not impair the effects of the present invention.

[0074] When using the antifouling cleaning agent for hard surfaces of the present invention, the specific amphoteric polymer compound may be dissolved or dispersed in a solvent as a single agent, or any number of agents may be used in combination with the cleaning components. Furthermore, by combining the 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 that have sustained-release properties. In addition, one of the specific amphoteric polymer compound and the cleaning component may be used in liquid form and the other in solid form such as powder.

[0075] Oil stain remover for hard surfaces, and method for removing oil stains from hard surfaces. The present invention preferably provides a liquid cleaning agent for hard surfaces containing a specific amphoteric polymer compound and a cleaning component, with the remainder being water. There are no particular restrictions on the water content, but it is usually 10 to 99.99% by mass, preferably 20 to 98% by mass, and more preferably 50 to 90% by mass.

[0076] The form in which the antifouling cleaning agent for hard surfaces of the present invention is used is not particularly limited, but it is preferably used in cleaning methods that use dishwashers such as automatic dishwashers. It is also preferably used for cleaning walls, floors, fixtures, and equipment throughout a dwelling, especially in kitchens, bathrooms, toilets, and washbasins. In the latter case, preferred methods include spraying the agent directly onto the object using a sprayer such as a trigger or aerosol, impregnating the object with the antifouling cleaning agent using a water-absorbing flexible material and rubbing the object, and immersing the object in a solution in which the antifouling cleaning agent is dissolved. Based on the above, in the method for cleaning oil stains on hard surfaces using the hard surface oil stain cleaner of the present invention, the hard surfaces preferably targeted for cleaning are tableware (which have inorganic hard surfaces such as glass, ceramics, and metal, or organic hard surfaces such as resin), sanitary ware, tiles, etc. [Examples]

[0077] The present invention will be described in more detail below with reference to the examples. However, the scope of the present invention is not limited in any way by these examples.

[0078] In the following examples and comparative examples, the various characteristics were evaluated using the following methods. • Solid content in the cleansing ingredients To determine the solid content of the cleaning agent, take approximately 2.0g 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 after drying (B). The solid content concentration is calculated according to the following formula. Furthermore, the amount of solid content contained in one dose (6g) of the cleaning agent is calculated according to the following formula. Solid content concentration [%] = (Weight after drying (B) / Sample weight (A)) × 100 Solid content [g] = (solid content concentration [%] / 100) x 6

[0079] • Foaming 30 mL of a 1 wt% aqueous solution of washing agent was placed in a 100 mL sample tube (manufactured by Maruemu Co., Ltd., No. 8, 40 mm x 120 mm), shaken vertically 20 times, and then allowed to stand for 10 seconds. The height of the bubbles (mm) was then measured.

[0080] • Oil stain removal and oil stain re-adhesion prevention properties (organic hard surface) Two 23cm diameter PP (polypropylene) plates were each dripped with 1g of melted beef tallow and allowed to solidify at room temperature for at least 30 minutes. Four plates in total—two with beef tallow and two without—were placed alternately in the large plate compartment of an automatic dishwasher (Panasonic electric dishwasher / dryer, model number: NP-TZ200-W). 6g of the cleaning component with the composition described below, along with an amphoteric polymer compound added in equal amounts to the cleaning component and solid content, were placed in the detergent dispenser. After washing and drying at washing level 3, the oil-stained surfaces of the PP plates were examined. The oil-stained surfaces were divided into five sections on the front of the PP plate (Figure 1(a)) and four sections on the back (Figure 1(b), the bottom (center) section of the back was excluded from evaluation because its surface condition differed from the other sections). The number of oil-stained sections was then counted. The oil stain removal performance was evaluated by the number of oily surfaces on plates with beef tallow attached, and the oil stain re-adhesion prevention performance was evaluated by the number of oily surfaces on plates without beef tallow attached.

[0081] • Prevents oil stains from re-adhering (inorganic hard surface) Three microscope slides were placed in the glass holder of an automatic dishwasher. 3g of beef tallow was added to the dishwasher, and 6g of cleaning components with the composition described below, along with an amphoteric polymer compound, were added to the detergent dispenser in an amount equal to the cleaning components in solid content. After washing and drying at washing level 1, the contact angle of the microscope slide surface was measured. Ten contact angle measurements were taken for each microscope slide, and the average value was used.

[0082] (Example 1) Using an allylamine-maleic acid copolymer (copolymerization ratio 1.2:1) synthesized by the following method as an amphoteric polymer, cleaning agents were constructed by combining them with cleaning components of the compositions shown in Table 1, from 1 to 11. The oil stain cleaning performance and oil stain re-adhesion prevention performance (organic hard surfaces), as well as the oil stain re-adhesion prevention performance (inorganic hard surfaces), were evaluated. The results are shown in Tables 3 and 4. Furthermore, Table 2 shows the results of evaluating the foaming properties when combined with the cleansing ingredients shown in Table 1, Item 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, stirrer, and condenser. Then, 342.60 g (6.00 mol) of allylamine was added dropwise while cooling, and the temperature was raised to 65°C. Polymerization was initiated by adding 28.5% by mass aqueous solution of ammonium persulfate so that the ammonium persulfate content reached 1 mol% of the total monomer content after 3 hours, and so on, after 24 and 28 hours, so that the ammonium persulfate content reached 2 mol% of the total monomer content after 24 and 28 hours, and the reaction was continued overnight. [Table 1]

[0083] (Comparative Example 1) The detergent was constructed and evaluated in the same manner as in Example 1, except that a diallyldimethylammonium chloride / maleic acid copolymer (copolymerization ratio 2:1) synthesized by the method described below was used as the amphoteric polymer compound, instead of the allylamine-maleic acid copolymer. The results are shown in Tables 3 and 4. Furthermore, Table 2 shows the results of evaluating the foaming properties when combined with the cleansing ingredients shown in Table 1, Item 1. [Synthesis method] A 500 mL four-necked flask equipped with a thermometer, stirrer, and condenser was charged with 174.12 g (0.70 mol) of 65% by mass diallyldimethylammonium chloride, 34.32 g (0.35 mol) of maleic anhydride, and 99.16 g of distilled water, and the internal temperature was raised to 60°C. Polymerization was initiated by adding 2 mol% (0.021 mol) of 28.5% by mass aqueous solution of ammonium persulfate relative to the monomer. After 2, 4, and 24 hours, 2 mol% of 28.5% by mass aqueous solution of ammonium persulfate was added each time, and the reaction was allowed to continue overnight.

[0084] (Example 2) The detergent was constructed and evaluated in the same manner as in Example 1, except that a diallylamine hydrochloride / maleic acid copolymer (copolymerization ratio 1:1) synthesized by the method described below was used as the amphoteric polymer compound, instead of the allylamine-maleic acid copolymer. The results are shown in Tables 3 and 4. Furthermore, Table 2 shows the results of evaluating the foaming properties when combined with the cleansing ingredients shown in Table 1, Item 1. [Synthesis method] A 500 mL four-necked flask equipped with a thermometer, stirrer, and condenser was charged with 144.53 g (0.75 mol) of 69.34% by mass diallylamine hydrochloride, 73.55 g (0.75 mol) of maleic anhydride, and 31.62 g of distilled water, and the internal temperature was raised to 50°C. Polymerization was started by adding a 28.5% by mass aqueous solution of ammonium persulfate in such an amount that the amount of ammonium persulfate in the aqueous solution was 0.5% by mass of the total amount of monomer. After 4 hours, an amount of the ammonium persulfate aqueous solution was added that resulted in 0.5% by mass of ammonium persulfate relative to the total amount of monomer. After 20 and 26 hours, an amount of the ammonium persulfate aqueous solution was added that resulted in 1.0% by mass of ammonium persulfate relative to the total amount of monomer. After 45 and 51 hours, an amount of the ammonium persulfate aqueous solution was added that resulted in 1.5% by mass of ammonium persulfate relative to the total amount of monomer. The reaction was allowed to proceed for 68 hours.

[0085] (Example 3) The detergent was constructed and evaluated in the same manner as in Example 1, except that a diallylmethylamine / maleic acid copolymer (copolymerization ratio 1:1) synthesized by the method described below was used as the amphoteric polymer compound instead of the allylamine-maleic acid copolymer. The results are shown in Tables 3 and 4. Furthermore, Table 2 shows the results of evaluating the foaming properties when combined with the cleansing ingredients shown in Table 1, Item 1. [Synthesis method] 1.86 kg (19.0 mol) of maleic anhydride and 0.34 kg of distilled water were charged into a 20 L four-necked flask equipped with a thermometer, stirrer, and condenser, and 2.11 kg (19.0 mol) of diallylmethylamine was added dropwise under cooling. The internal temperature was then raised to 50°C. Polymerization was initiated by adding a 28.5% by mass aqueous solution of ammonium persulfate in an amount equal to 0.5% by mass of the total amount of monomer. After 3, 21, and 25 hours, the same aqueous solution of ammonium persulfate was added in an amount equal to 1.0% by mass of the total amount of monomer, and the reaction was allowed to continue overnight.

[0086] (Comparative Example 2) The detergent was constructed and evaluated in the same manner as in Example 1, except that allylamine hydrochloride polymer (manufactured by Nitto Boseki Medical Co., Ltd., brand name: PAA-HCl-3L) was used as the polymer compound instead of allylamine-maleic acid copolymer, and foaming properties were not evaluated. The results are shown in Tables 3 and 4.

[0087] (Example 4) The detergent was constructed and evaluated in the same manner as in Example 1, except that an allylamine-itaconic acid copolymer (copolymerization ratio 2:1) synthesized by the method described below was used as the amphoteric polymer compound instead of the allylamine-maleic acid copolymer, and foaming properties were not evaluated. The results are shown in Tables 3 and 4. [Synthesis method] 52.04 g (0.4 mol) of itaconic acid and 59.59 g of distilled water were charged into a 300 mL four-necked flask equipped with a thermometer, stirrer, and condenser, and 45.68 g (0.8 mol) of monoallylamine was added dropwise under cooling. The internal temperature was then raised to 60°C. Polymerization was initiated by adding 2 mol% (0.024 mol) of 28.5% by mass aqueous solution of ammonium persulfate relative to the monomer. After 2 and 4 hours, 2 mol% of 28.5% by mass aqueous solution of ammonium persulfate was added, and the reaction was allowed to proceed overnight.

[0088] (Example 5) The detergent was constructed and evaluated in the same manner as in Example 1, except that an allylamine-itaconic acid copolymer (copolymerization ratio 1.2:1) synthesized by the method described below was used as the amphoteric polymer compound instead of the allylamine-maleic acid copolymer, and foaming properties were not evaluated. The results are shown in Tables 3 and 4. [Synthesis method] 39.03 g (0.3 mol) of itaconic acid and 59.59 g of distilled water were charged into a 300 mL four-necked flask equipped with a thermometer, stirrer, and condenser, and 20.56 g (0.36 mol) of monoallylamine was added dropwise under cooling. The internal temperature was then raised to 60°C. Polymerization was initiated by adding 2 mol% (0.0132 mol) of a 28.5% by mass ammonium persulfate aqueous solution relative to the monomer. After 2 and 4 hours, 2 mol% of the 28.5% by mass ammonium persulfate aqueous solution was added, and the reaction was allowed to proceed overnight.

[0089] (Example 6) The detergent was constructed and evaluated in the same manner as in Example 1, except that an allylamine-acrylamide 2-methylpropanesulfonic acid copolymer (copolymerization ratio 1:2), synthesized by the method described below, was used as the amphoteric polymer compound instead of the allylamine-maleic acid copolymer, and foaming properties were not evaluated. The results are shown in Tables 3 and 4. [Synthesis method] A 500 mL four-necked flask equipped with a thermometer, stirrer, and condenser was charged with 32.07 g (0.2 mol) of 58.35% by mass allylamine hydrochloride and 95.16 g of distilled water, and the internal temperature was raised to 60°C. A mixed solution of 84.59 g (98% by mass) acrylamide-2-methylpropanesulfonate sodium and 126.89 g of distilled water was added dropwise over 6 hours, and at the same time, the initiator V-50 (2,2′-azobis(2-methylpropionamidine) dihydrochloride) was added in an amount equal to 1 mol% (0.006 mol) of V-50 relative to the total amount of monomer to initiate polymerization. After 2, 4, and 6 hours, 1 mol% (0.006 mol) of V-50 was added each time, and the reaction was allowed to proceed overnight. Subsequently, 100.80 g (0.63 mol) of 25% by mass sodium hydroxide was added under cooling conditions below 30°C. Subsequently, demonomerization was performed using an evaporator (50°C, 2 hours). After demonomerization, the concentration was adjusted to 15%, and desalting was performed by electrodialysis (approximately 3 hours, ending 1 hour after the conductivity had completely decreased).

[0090] (Example 7) The detergent was constructed and evaluated in the same manner as in Example 1, except that an allylamine-citraconic acid copolymer (copolymerization ratio 2:1) synthesized by the method described below was used as the amphoteric polymer compound instead of the allylamine-maleic acid copolymer, and foaming properties were not evaluated. The results are shown in Tables 3 and 4. [Synthesis method] 73.02 g (0.55 mol) of 98% by mass citraconic acid and 32.12 g of distilled water were charged into a 300 mL four-necked flask equipped with a thermometer, stirrer, and condenser. 62.81 g (1.1 mol) of monoallylamine was added dropwise under cooling. The internal temperature was then raised to 60°C. Polymerization was initiated by adding 2 mol% (0.033 mol) of 28.5% by mass aqueous ammonium persulfate to the monomer. After 4, 22, 25, and 28 hours, 2 mol% of 28.5% by mass aqueous ammonium persulfate was added each time, and the reaction was continued overnight.

[0091] (Example 8) The detergent was constructed and evaluated in the same manner as in Example 1, except that an allylamine-acrylic acid copolymer (copolymerization ratio 1:1) synthesized by the method described below was used as the amphoteric polymer compound instead of the allylamine-maleic acid copolymer, and foaming properties were not evaluated. The results are shown in Tables 3 and 4. [Synthesis Method] 80.17 g (0.5 mol) of 58.35% by mass allylamine hydrochloride and 36.33 g of distilled water were charged into a 500 mL four-necked flask equipped with a thermometer, stirrer, and condenser, and the internal 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 added dropwise over 6 hours, and at the same time, the initiator V-50 (2,2′-azobis(2-methylpropionamidine) dihydrochloride) was added in an amount equal to 0.5 mol% (0.005 mol) of V-50 relative to the total amount of monomer to start polymerization. After 2 and 4 hours, 0.5 mol% (0.005 mol) of V-50 was added each time, and after 6 hours, 1.0 mol% (0.010 mol) of V-50 was added, and the reaction was allowed to proceed overnight. Subsequently, 168.00 g (1.05 mol) of 25% by mass sodium hydroxide was added under cooling conditions below 30°C. Then, demonomerization was performed using an evaporator (50°C, 2 hours). After demonomerization, the concentration was adjusted to 15%, and desalting was performed by electrodialysis (approximately 4 hours, ending 1 hour after the conductivity had completely decreased).

[0092] [Table 2]

[0093] [Table 3]

[0094] [Table 4]

[0095] In each example using an amphoteric polymer compound (specific amphoteric polymer compound) containing a cationic structural unit (1) having at least one group selected from primary, secondary, and tertiary amino groups in its structure, and an anionic structural unit (2), according to the present invention, excellent performance was achieved in preventing the re-adhesion of oil stains to inorganic hard surfaces, and in cleaning power and re-adhesion prevention of oil stains to organic hard surfaces. In Comparative Example 1, which used an amphoteric polymer compound that does not fall under the category of specific amphoteric polymer compounds, the ability to prevent re-adhesion of oil stains to inorganic hard surfaces was good, but the oil stain cleaning power and re-adhesion prevention ability to organic hard surfaces were not necessarily good. In Comparative Example 2, which used a cationic polymer compound that is not an amphoteric polymer compound, neither the ability to prevent re-adhesion of oil stains to inorganic hard surfaces nor the oil stain cleaning power and re-adhesion prevention ability to organic hard surfaces were necessarily good. [Industrial applicability]

[0096] The present invention provides an oil stain remover for hard surfaces and a method for removing oil stains from hard surfaces. This method not only exhibits excellent resistance to preventing re-adhesion of oil stains to inorganic hard surfaces (anti-fouling properties), but also excels in oil stain removal power and re-adhesion prevention on organic hard surfaces. Therefore, it is particularly suitable for use in cleaning oil stains from hard surfaces using dishwashers and has high applicability in various industrial fields such as personal belongings, household goods, barber shops and hygiene, cleaning, building maintenance, food service, accommodation facilities, leisure and sports facilities, and healthcare, medical care, and nursing care.

Claims

1. A dishwasher oil stain remover for hard surfaces, comprising an amphoteric polymer compound comprising a cationic structural unit (1) having a structure derived from a monoallylamine monomer and / or a diallylamine monomer and 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 structural unit (2) having a structure derived from an unsaturated carboxylic acid and / or a sulfonic acid, wherein the sum of the cationic structural unit (1) and the anionic structural unit (2) accounts for 65 to 100 mol% of the total structural units of the amphoteric polymer compound.

2. The hard surface oil stain cleaner according to claim 1, wherein the molar ratio of cationic constituent units (1) to anionic constituent units (2) in the amphoteric polymer compound is 0.4 to 25.

0.

3. The oil stain cleaner for hard surfaces according to claim 1 or 2, wherein the cationic constituent unit (1) has a primary amino group.

4. A cleaning agent for oil stains on hard surfaces according to any one of claims 1 to 3, further comprising a surfactant.

5. The hard surface oil stain cleaner according to claim 4, wherein the surfactant contains a cationic surfactant and an anionic surfactant.

6. Furthermore, the hard surface oil stain cleaner according to any one of claims 1 to 5, further comprising at least one selected from the group consisting of chelating agents, polyols, alkali metal compounds, and thickeners.

7. The hard surface oil stain cleaner according to any one of claims 1 to 6, wherein the content of the amphoteric polymer compound is 0.01 to 50% by mass.

8. A method for cleaning oil stains on a hard surface using a dishwasher and a hard surface oil stain cleaner according to any one of claims 1 to 7.

9. The method for cleaning oil stains on a hard surface according to claim 8, wherein the hard surface is the surface of a dish.

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