KR19980042330A - Alkaline liquid cleaner for metals, preparation and use of the same - Google Patents

Abstract

Providing an alkaline cleaning agent for metals by emulsifying or dispersing or dissolving a surfactant containing a highly chelating agent or an alkali builder, and also an antifoaming agent, for use in electrolytic cleaning.

(A) 35-70 weight% of alkali chemicals, (E) molecular weight is 1,000-3,000,000 ethylenically unsaturated organic acid monomers alone or copolymer, or its salt, (B) cleaning surfactant, (C) antifoamer, and (D) A one-component alkaline liquid detergent for dry baths on suspension, containing two or more selected from chelating agents, a two-component detergent for dry baths divided into two, and some of these A one-component or two-component detergent for replenishment lacking, these dilutions, and a method for producing the same and an electrolytic cleaning method using the same. In order to enhance the emulsion dispersibility of the surfactant, it may also contain (F) smectite-based clay minerals.

Description

Alkaline liquid cleaner for metals, preparation and use of the same

The present invention is excellent in cleanability and liquid stability after a lapse of time, and even if it contains a high concentration of alkali components, it contains a high concentration of the detergent active ingredient having a solubility or higher in a uniform emulsion dispersion state, and can be reduced in cost. An alkaline liquid detergent for metals, and a method for producing and using the same. Cleaning of metal by the alkaline liquid detergent for metals of this invention is generally performed by electrolytic cleaning.

In general, industrial metal surfaces have dirt substances such as oil and fat, grease, mineral oil, rolled oil, cutting oil, press oil, and freshener, and the like, and metal powder or the like is attached to the dirt. It may be mixed. These contaminants need to be removed at a later stage, e.g. annealing, plating, pre-painting, or painting, and are generally alkaline cleaners for metals containing alkali and surfactants and chelating agents. Remove the material.

Examples of the alkali agent used in the alkaline cleaning agent for metals include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal salts of silicic acid such as ortho sodium silicate and sodium metasilicate, sodium phosphate or sodium carbonate, and the like. It is used for various uses, such as saponification reaction of the same fats and oils.

Next, as surfactant, it can divide roughly into surfactant for washing | cleaning and surfactant for defoaming. Most of the cleaning surfactants are used alone or in combination with nonionic surfactants and anionic surfactants. The surfactants can be used as a penetrating, emulsifying, and dispersing agent for the above substances. Remove dirt. As the antifoaming surfactant, a nonionic surfactant having a relatively low HLB type or an alcohol is generally used. The antifoaming effect on foaming caused by the cleaning surfactant is generally saponified. It is one which has the effect of suppressing foaming by dolbi which is saponified and produced by the component.

The chelating agent mainly removes metals such as iron generated from rolling, cutting and pressing processes, and hard water components such as calcium and magnesium contained in industrial water when anionic surfactants are used. It has an action of forming an insoluble dye with a surfactant to prevent the surfactant from lowering, so-called blocking of a hard water component.

The alkaline detergent for metals generally used exhibits the outstanding washing | cleaning power by the combined effect | action of each said component.

These conventional industrial alkaline cleaners are generally supplied in a concentrated state and diluted when used, and are used for salt precipitation of surfactants by strong alkali builders (mainly alkali metal hydroxides) or low solubility builders (mainly alkali metal silicates). Liquid crystals in a concentrated state due to precipitation of crystals of alkali metal phosphates or polyphosphates), etc., so that the supply of chemicals is mixed with a surfactant or a chelating agent with respect to the powder or flake strong alkali builders. It was carried out in the form of a powder or in a two-packed form of an aqueous solution of an alkali builder and a chelating agent and an aqueous solution of a surfactant. However, it is necessary to use the powder cleaner after dissolving it to a certain concentration of aqueous solution to users, and also workability such as adhesion of mist or dissolved solution to the skin, and poor working environment. This pointed out. In addition, in the case of the two-component detergent, the alkali builder aqueous solution and the surfactant aqueous solution are replenished, respectively, and there is a problem of liquid management that it is difficult to secure the component balance, and it also contains a sufficient amount of the chelating agent or the low solubility builder and is concentrated. It was difficult to store the aqueous alkaline builder solution at room temperature due to crystallization phenomenon or the like. Accordingly, users using these cleaning solutions have longed for the development of concentrated alkaline liquid cleaners that contain a sufficient amount of detergent components as needed.

So far, according to the above requirements, (1) to (3) have been reported in which a dissolution aid such as a solubilizer is blended in an alkali builder and the production of a uniform and transparent one-component alkaline cleaner is reported, the summary is shown below.

(1) Japanese Unexamined Patent Publication No. 64-4226

(a) 3 to 50% by weight strong alkali

(b) 0.01-30% by weight of a nonionic surfactant of HLB 3-18, and

(c) 0.01-30% by weight of solubilizer represented by general formula: RCOOM

(Wherein R represents a straight chain aliphatic hydrocarbon group having 4 to 14 carbon atoms or a branched aliphatic hydrocarbon group having 4 to 18 carbon atoms, and M represents hydrogen, an alkali metal, an aliphatic amine having 1 to 4 carbon atoms, ammonia or an alkanol amine) ), And a strongly alkaline aqueous solution of a nonionic surfactant, characterized in that the pH is 10 or more.

(2) Japanese Patent Publication No. Hei 3-46038

(a) 3 to 50% by weight strong alkali

(b) 0.01-30% by weight of a nonionic surfactant of HLB 3-18, and

(c) 0.01-30% by weight of solubilizer represented by general formula: RX- (CH ₂ ) mCOOM

(Wherein X represents = NH, = N (CH ₂ ) _n COOM or = CHCOOM, and R represents a saturated or unsaturated aliphatic hydrocarbon group or an aryl group having 4 to 18 carbon atoms. And M represents an alkali metal, an aliphatic amine having 1 to 4 carbon atoms, ammonia or an alkanol amine, and m or n represent an integer of 1 to 3, respectively.)

And a strong alkaline detergent composition characterized by having a pH of 10 or more.

(3) Japanese Unexamined Patent Application Publication No. Hei 5-230498

(a) 25 to 40% by weight strong alkali

(b) 0.1 to 7% by weight of nonionic surfactant of HLB 3-18

(c) 0.2 to 10% by weight of one or more chelating agents selected from amino polycarboxylic acid chelating agents and oxycarboxylic acid chelating agents, and

(d) A high concentration strongly alkaline aqueous solution composition containing 0.5 to 15% by weight of at least one compound selected from 2-methylbutyric acid, 3-methylbutyric acid, and alkali metal salts or lower amine salts thereof is disclosed.

However, in the case of the soluble one-component alkaline cleaner using the solubilizer disclosed in the invention of (1) to (3), the degreasing property is good, but due to the high cost ratio of the solubilizer to the raw material cost of the one-component alkaline cleaner. The increase in drug cost, and furthermore, the limit of the concentration of strong alkaline agent is not high enough up to about 20-30%. Therefore, the high cost caused by the increase of drug transportation cost due to the large number of times of payment of practical supply drugs there is a problem. In order to improve this, when the one-component alkaline cleaner is further concentrated, the solubilizer itself is precipitated with salt, and the effect as a dissolving aid is lost, and when the alkali builder or the chelating agent is concentrated at a temperature higher than the solubility at room temperature, Precipitation or separation occurs due to the precipitation of crystals, which is a great restriction in sufficiently high concentration of the one-component detergent at room temperature. In addition, when solubilizing a nonionic surfactant having a high HLB to obtain a better cleaning agent, it is necessary to increase the amount of the solubilizer added, but the increase is limited as described above, and also a low anti-foaming HLB low In the case of solubilizing a warm surfactant, it is not possible to freely select a compound to be dissolved and to solubilize the salt by separating and solubilizing it. This is the current situation. In addition, when performing one-liquidization, the load on waste water treatment property which causes high COD by the solubilizer used in large quantities becomes a problem.

Therefore, since the invention of the following (4) and (5) is filed for solving these problems, the outline | summary is introduced below.

(4) Japanese Unexamined Patent Application Publication No. Hei 7-41974;

A high concentration one-component alkaline cleaner composition comprising 10 to 35 wt% of an alkali agent (based on Na ₂ O) and 0.1 to 20 wt% of an aromatic compound having 2 to 50 polar groups in one molecule, and a detergent obtained by diluting it. A composition, and a method for producing the high concentration one-pack alkaline detergent composition are disclosed.

Since the high concentration one-component alkaline detergent composition as in the present invention contains an excellent slurry stabilizer, it is possible to mix alcohol, surfactant, aliphatic, chelating agent, etc. which are generally poorly soluble at high alkali concentrations, Satisfying all aspects of low COD and low cost can provide a more stable product to the user.

(5) Japanese Laid-Open Patent Publication No. 7-41975 is a related application of Japanese Laid-Open Patent Publication No. 7-41974;

A high-concentration one-component alkaline cleaner composition comprising 10 to 35 wt% of an alkali agent (based on Na ₂ O) and 0.1 to 20 wt% of an aliphatic compound having 2 to 6 polar groups in one molecule, and a detergent obtained by diluting it. A composition, and a method for producing the high concentration one-pack alkaline detergent composition are disclosed.

Since the high concentration one-component alkaline detergent composition shown in this invention contains an excellent slurry stabilizer, it can mix | blend alcohol, surfactant, aliphatic, a chelating agent etc. which are generally hardly soluble at high alkali concentration, and require high washing | cleaning, Satisfying all aspects of low COD and low cost can provide a more stable product to the user.

The inventions shown in (4) and (5) have been considerably improved to meet the demands for high cleanliness, low cost, and low COD that are currently required, but they contain a low solubility builder such as orthosilicate silicate that can be stored at room temperature. The development of a medicament, further improved cost reduction by higher concentration of alkali builder aqueous solution, further improved low COD, and the like, and at present, have not obtained a liquid detergent composition that can satisfy these requirements.

The present invention is to solve the problems of the prior art, the interface of the alkali builders such as sodium hydroxide to 35% by weight or more, and contains an antifoaming agent that can not be contained in the stable by the supersaturation precipitation originally Uniform emulsification and dispersing of active agents, high concentration detergent active ingredients containing chelating agents, low solubility alkali builder aqueous solutions, etc. enables uniform liquid at room temperature, low COD for better wastewater treatment and emulsion dispersion stability over time. It aims at providing the alkaline liquid detergent for metals of the one-part suspension state at normal temperature more than favorable and also the washability.

The present invention also provides an alkaline liquid detergent for two-component metals comprising an aqueous alkaline builder composition obtained by uniformly emulsifying and dispersing a high concentration of a chelating agent or a low solubility alkali builder and an aqueous surfactant composition containing a surfactant containing an antifoaming agent. It aims to provide.

Another object of the present invention is to provide a method for producing the alkaline liquid detergent for one-component metal and a method for using the alkaline liquid detergent for metal.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining about the means for solving the problem which the said prior art has, as a result, it contains 35-70 weight% of high concentration alkali chemicals, a cleaning surfactant, an antifoamer, and a chelating agent, or the said alkali chemicals and a chelate Cleaning and defoaming surfactants, precipitated chelating agents, and optionally alkaline agents precipitated by supersaturation in an alkaline aqueous solution containing the agent as a substance capable of stably dispersing even after elapse of time. The inventors have found that the above problems can be solved by blending a single or copolymer of an ethylenically unsaturated organic acid monomer having a molecular weight of 1,000 to 3,000,000, or a salt thereof, and have completed the present invention.

That is, the present invention, in a broader range, includes (A) an alkali agent and (E) a single or copolymer of an ethylenically unsaturated organic acid monomer having a molecular weight of 1,000 to 3,000,000 (including a copolymer of other ethylenic monomers. Homologous) or its salt, and water, The present invention relates to an alkaline liquid detergent for metals in a suspended state. The present invention has a broad range of the following: (A) 35 to 70% by weight of alkali chemicals (values based on the total weight of the detergent, the same as described below in the claims), and (E) ethylenic having a molecular weight of 1,000 to 3,000,000. Suspension characterized in that it contains only one or a copolymer of an unsaturated organic acid monomer, or a salt thereof, (B) a cleaning surfactant, (C) an antifoaming agent, and (D) a chelating agent, and water. It relates to an alkaline liquid detergent for metal in a state.

More specifically, the present invention comprises (A) 35 to 70% by weight of alkali chemicals, (B) 0.1 to 20% by weight of cleaning surfactant, (C) 0.01 to 10% by weight of antifoaming agent, and (D) 0.1 to 20% by weight of chelating agent. (E) Alkaline liquid detergent (composition) for one-component metal for dry baths in suspension, characterized in that it contains a single or copolymer of an ethylenically unsaturated organic acid monomer having a molecular weight of 1,000 to 3,000,000, or a salt thereof and water. It is about.

The present invention also provides 35 to 70% by weight of the alkaline liquid detergent for metal (A), which is the one-component alkaline liquid detergent, 0.1 to 20% by weight of the (D) chelating agent, and (E) molecular weight of 1,000 to 3,000,000. 0.1-15% by weight of a single or copolymer of a phosphorus ethylenically unsaturated organic acid monomer or a salt thereof, and water, and a composition in a suspended state (hereinafter referred to as an alkali builder composition), in combination with this Concentration of component (B) as it is a composition containing (B) cleaning surfactant and (C) antifoaming agent for use, or containing component (B), component (C) and water, as it is or when diluted with water. Is 0.1 to 20% by weight, the concentration of component (C) relates to an alkaline liquid detergent for two-component metals for dry bath, which is composed of a composition (hereinafter referred to as a surfactant).

Moreover, although the component which acts as a washing | cleaning surfactant may generate | occur | produce during a washing | cleaning process, a washing | cleaning surfactant is not necessary as a replenishment agent in this case. Therefore, the present invention further provides (A) 35 to 70% by weight of alkaline agent, (C) 0.01 to 25% by weight of antifoaming agent, (D) 0.1 to 20% by weight of chelating agent, and (E) molecular weight of 1,000 to 3,000,000. Alkali liquid detergent (composition) for single-component metals for replenishment in suspension, characterized in that it contains 0.1 to 15% by weight of a monounsaturated organic acid monomer alone or a copolymer or salt thereof, and water, and (A) 0.1 to 15% by weight of an alkali or 35 to 70% by weight of (D) a chelating agent, 0.1 to 20% by weight of (E) an ethylenically unsaturated organic acid monomer having a molecular weight of 1,000 to 3,000,000, or a salt thereof, (C) Defoamer for use in combination with a suspension state (henceforth alkali-builder composition) containing water, and a composition containing an antifoamer and water (henceforth it consists of a defoaming agent alone. And for convenience, referred to as a surfactant composition) The present invention also relates to an alkaline liquid detergent for two-component metals that is made for replenishment.

The cleaning agent of the one-pack type present invention for replenishment preferably contains from 0 to 25% by weight or less of the component (B) as a cleaning surfactant, and the two-pack type of the present invention for replenishment. The surfactant composition in the cleaning agent is a composition further containing component (B), and the concentration of component (C) when the concentration of component (B) is as large as -20 wt% from 0 when diluted as it is or with water. It is generally preferable that the composition is 0.01 to 25% by weight.

In order to enhance the emulsion dispersion stability by adsorb | sucking the detergent surfactant and antifoamer which precipitate-separates salt in the high concentration aqueous alkali solution, it is preferable to contain smectite type clay mineral as an arbitrary component in this one-component cleaning agent of this invention.

In the alkaline liquid detergent for the metal, the alkali agent is preferably at least one selected from sodium hydroxide, ortho sodium silicate, and sodium phosphate (or sodium hydrogen phosphate), and is also used alone or in air of the ethylenically unsaturated organic monomer. The copolymer or salt thereof is at least one selected from polyacrylic acid, polymaleic acid, copolymers with acrylic acid, copolymers containing 70 mol% or more of acrylic acid units and / or maleic acid units, and salts of these alone or copolymers. desirable.

This invention relates to the alkaline liquid detergent for metals which diluted with the alkali agent concentration at the time of using the detergent of each said aspect again.

The present invention also provides an aqueous solution in which component (D) (chelating agent) is dissolved, or a component or copolymer of component (D) (whole quantity) and component (E) (molecular weight of 1,000 to 3,000,000 monomers, or a copolymer thereof). In the aqueous solution in which a part of the salt) is dissolved, component (A) (alkali agent) is stirred and mixed so that the concentration of the alkali agent is 40% by weight or more, and all or part of the chelating agent, or all or part of the chelating agent and part of the alkaline agent. After the suspension (1) is prepared as a suspension component, the component (B) (the cleaning surfactant), the component (C) (the antifoaming agent), the component (E) (the whole amount or the remainder used in the ①) and water are stirred and mixed. A liquid or a component (C), a component (E) (whole amount or the remainder used in ①) and water, and a liquid (2), which are agitated and mixed, are added and mixed in small amounts while stirring (1) and (2). Alkaline liquid for one-component metals It relates to a process for the preparation of the tablet. By this manufacturing method, an alkaline liquid detergent for one-component metal can be efficiently produced. In the case of containing the smectite clay mineral of component (F), the liquid preparation of (2) above is carried out in components (B), (C) and (E) (whole quantity or ①) in a dispersion in which component (F) is dispersed in water. It is preferable to add by adding the remainder used, or by adding the component (C) and the component (E) (the whole amount or the remainder used in ①) and stirring and mixing.

The present invention further relates to a method of performing electrolytic cleaning of the metal material with the diluted alkaline liquid detergent for metal.

In addition, the above-mentioned alkaline detergent for one-component metal for dry bath, alkaline detergent for two-component metal for dry bath, alkaline detergent for one-component metal for replenishment, and alkaline detergent for two-component metal for replenishment In view of the fact that the alkaline liquid cleaner is the same in the industrial field of application, the concentration of the alkaline builder is increased, and even if the concentration of the chelating agent is further increased, the alkaline liquid detergent for metals having a good emulsion dispersibility after elapse of time is provided. Since the problem to be solved is common, it can be understood that it satisfies the requirements of Article 37 (1) of the Patent Act.

In addition, the four types of alkaline cleaning agents for metals may contain a single or copolymer of an ethylenically unsaturated organic acid monomer which is a component (E) of a system containing at least an alkali agent, a chelating agent and water, thereby providing a stable dispersion system. It is common in that it is produced. Therefore, these can be understood as satisfying even the requirements of Article 37 (2) of the Patent Act, since the principal parts are also the same invention.

In addition, it can be understood that the method for producing and using the alkaline cleaning agent for metal of the present invention satisfies the requirements of Article 37 (3) of the Patent Act.

That is, this patent application can be interpreted as satisfying the so-called singleness requirement of the application.

Hereinafter, the present invention will be described in detail.

First, referring to the general principle in the description, when a group or a class of substances is described and included as being suitable or desirable for the purpose given to the invention, a mixture of two or more of the group or class members is likewise. Suitable or preferred; In addition, the component description in a chemical term relates to the said component at the time of addition to make it into any combination specified in the specification, and does not necessarily exclude the chemical interaction between the components of the mixture once mixed. ; In addition, a desiccant means the detergent which ensures the washing | cleaning property when using as a washing | cleaning bath newly (at the time of a bath), or from a dry bath to a steady state, and a replenishment agent is in the middle or normal It means the detergent used for replenishment in a state.

As the component (A) alkali agent used in the alkaline liquid detergent for metals of the present invention, any water-soluble alkali agent can be used. Specific examples include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal silicates such as ortho silicate, sodium metasilicate, potassium orthosilicate and potassium metasilicate, sodium phosphate and sodium hydrogen phosphate (NaH ₂ PO ₄ , Na Alkali metal polyphosphates, such as alkali metal phosphates such as ₂ HPO ₄ ), potassium phosphate, potassium hydrogen phosphate (KH ₂ PO ₄ , K ₂ HPO ₄ ) or hydrogen phosphate, potassium tripolyphosphate, sodium tripolyphosphate, sodium carbonate, carbonate Alkali metal carbonates, such as potassium, etc. are mentioned. These can be used individually or in combination of 2 or more types, respectively.

Component (A) may not necessarily contain alkali metal hydroxides as constituents, but generally alkali metal hydroxides, in particular at least 1 mol% of sodium hydroxide and, if not 100 mol%, other alkali agents, preferably alkali metals. It is preferable that it is comprised by at least 1 sort (s) of alkali builders, especially ortho sodium silicate, and at least 1 sort (s) of sodium phosphate or sodium hydrogen phosphate, such as a silicate, alkali metal phosphate or alkali metal hydrogen phosphate, and alkali metal polyphosphate.

In addition, when using alkali metal phosphate, alkali metal phosphate, or alkali metal polyphosphate, it is generally preferable to use alkali metal hydroxide (generally more than twice mole).

In the cleaning agent of the present invention, that is, in the one-component main detergent for dry bath, in the one-component main detergent for replenishment, in the alkali builder composition in the two-component main detergent for dry bath, and in the two-component main cleaner for replenishment It is necessary that the compounding quantity of the alkali agent of the component (A) in the alkali builder composition of 35-70 weight% is preferable, It is preferable that it is 35-65 weight%, It is more preferable that it is 35-60 weight%, 35-55 weight It is more preferable than%, and it is still more preferable that it is 38-50 weight%. When the blending amount is less than 35% by weight, it is difficult to prepare a suspension in which the supersaturated precipitation component of the chelating agent or the low solubility alkali builder is stably dispersed, so that the stability of the liquid is not secured, and the sufficient high concentration region for the purpose of the present invention. It is not said that it becomes meaningless. Moreover, when it is more than 70 weight%, the extreme viscosity increase or solidification of the alkali builder composition in a one-component main detergent or a two-component main detergent is easy to occur.

In more detail about the compounding quantity of component (A), when component (A) consists of alkali metal hydroxide, especially sodium hydroxide alone, the compounding quantity of component (A) is preferable 35-60 weight%, and 35-55 Weight% is more preferable, and 37-50 weight% is still more preferable. When component (A) consists of alkali metal silicates, especially sodium ortho silicate alone, 35-45 weight% is preferable and, as for the compounding quantity of component (A), 35-40 weight% is more preferable. When component (A) consists of alkali metal hydroxides, especially sodium hydroxide and alkali metal silicates, especially sodium ortho silicate, the blending amount of component (A) is preferably 35 to 50% by weight, more preferably 35 to 45% by weight. 37-43 weight% is more preferable. When component (A) consists of alkali metal hydroxides, especially sodium hydroxide and the alkali metal phosphate or phosphate, especially sodium phosphate or sodium hydrogen phosphate, the compounding quantity of component (A) is preferable 35-65 weight%, 45 60 weight% is more preferable.

Since the solubility is relatively high with respect to the alkali metal hydroxide in the said alkali chemicals component in the cleaning agent of this invention, it can be considered to exist as a suspension component in the state exceeding a solubility component or solubility, but about other low solubility alkali builders, It can be considered that most of them exist as precipitated suspension components. The effective mechanism is not definite, but the solubility of single or copolymer of ethylenically unsaturated crude organic acid monomer or its salt, ie, component (E), in the molecule to be described later, dissolved or finely dispersed in the composition of the present invention. It penetrates between particles of the alkali builder component that precipitates in excess of the particles, thereby impairing the access between the particles, the crystal growth inhibitory effect and the steric stabilization effect on the polymer adsorption to the particle surface, and the adsorption of the water-soluble polymer having a group capable of ionization. It can be considered that it is stably dispersed by the dispersion action by the electrostatic effect stabilized by the electrostatic repulsive force caused by them, their synergistic effects, and the like.

As surfactant for washing of the component (B) used by this invention, the nonionic surfactant whose HLB is 8 or more and 18 or less is mentioned first. The said nonionic surfactant is very useful as a washability improvement agent, and has a permeability | permeability, emulsification property, dispersibility, and foamability. In addition, anionic surfactants may also be used as detergency enhancing agents, but insoluble salts may be formed by relatively high foaming properties, calcium ions and magnesium ions, which are hardness components in water, and are removed during water washing after washing. Since it is difficult to do so, it is preferable to use a nonionic surfactant alone or to use a nonionic surfactant and an anionic surfactant together rather than using anionic surfactant alone. That is, when using together, it is preferable that at least 80 weight% of the whole is a nonionic surfactant. Moreover, as a component (B), a cationic surfactant or an amphoteric surfactant can also be used individually or in combination with the said surfactant as needed, respectively.

Examples of the nonionic surfactant that can be used as the detergent in the present invention are shown in (a) below, examples of the anionic surfactant below (b), and examples of cationic surfactant below (c). Although the example of surfactant is shown to following (d), in this invention, it is not specifically limited to this.

(a) As nonionic surfactant, polyoxyethylene alkyl ether (alkyl is generally C6-C16), polyoxyethylene polyoxy propylene alkyl ether (alkyl is generally C6-C16), polyoxyethylene alkyl aryl ether (Alkyl generally is C6 to C16, aryl is generally phenyl), polyoxyethylene polyoxypropylene alkylaryyl ether (alkyl is generally C6 to C16, aryl is generally phenyl), polyoxyethylene alkylamino ether (alkyl Is usually C6 to C16), polyoxyethylene sorbitan fatty acid esters (usually monoesters) (higher fatty acids are typically saturated or unsaturated monovalent fatty acids of C12 to C18), polyoxyethylene higher fatty acid esters (mono or di Esters (higher fatty acids are generally C12 to C18 saturated or unsaturated monovalent fatty acids), ethylene oxide-propylene oxide copolymers, and the like. Can be. Particularly effective examples of cleaning agents include polyoxyethylene hetotosyl ether, polyoxyethylene octyl ether, polyoxyethylene decyl ether, polyoxyethylene lauryl ether, polyoxyethylene octylphenyl ether, and polyoxyethylene nonylphenyl ether. , Polyoxyethylene decylphenyl ether, ethylene oxide propylene oxide copolymer, polyoxyethylene polyoxy propylene ether, and the like. The said nonionic surfactant can be used individually or in combination of 2 or more types.

(b) Anionic surfactants as detergent enhancers include higher fatty acid salts (higher fatty acids are usually saturated or unsaturated monovalent fatty acids having from C12-18), alkylsulphate ester salts (alkyl generally being alkyl with C12-18), alkyl Benzene sulfonate (alkyl is usually C11-C15 alkyl), alkylnaphthalene sulfonate (alkyl is generally C4 alkyl), dialkylsulfosuccinic ester salt (typically 10-20 carbon atoms in total) , Alkylphosphoric acid ester salts (alkyl is generally C12-18 alkyl), formalin condensed naphthalene sulfonates, polyoxyethylene alkylsulfuric acid ester salts (alkyl is generally C8 or C9 alkyl), polyoxyethylene alkylphenylsulphate ester salts (Alkyl is generally C8 or C9 alkyl). Salts of the anionic surfactants are generally alkali metal salts, of which sodium salt is preferably used. The said anionic surfactant can be used individually or in combination of 2 or more types.

(c) As cationic surfactant mix | blended as needed as a washability improvement agent, an alkylamine acetate, an alkylamine hydrochloride, a quaternary ammonium salt, etc. are mentioned. Moreover, as (d) amphoteric surfactant, alkyldimethylamine oxide, alkylcarboxy methylhydroxy ethyl imidazolium betaine, alkylamino carboxylate, etc. are mentioned. The said cationic surfactant and the amphoteric surfactant can be used individually or in combination of 2 or more types.

The compounding quantity of the washing | cleaning surfactant of the component (B) in the one-component type washing | cleaning agent for dry baths is 0.1-20 weight%, Preferably it is 0.5-15 weight%, More preferably, it is 2-10 weight%. . When this compounding quantity is less than 0.1 weight%, the effect as a washability improvement agent is not exhibited, and when it is more than 20 weight%, the effect becomes saturated, and it is uneconomical.

Most of the cleaning surfactants are not dissolved because they have a salt precipitation effect in a high concentration of strongly alkaline aqueous solution, but are stably dispersed as a part of the suspending component in the one-part type cleaning agent in a dry bath. have. Although the mechanism of the effect is not constant, the single or copolymer of an ethylenically unsaturated organic acid monomer which will be described later, which is dissolved or finely dispersed in the composition of the present invention, or a salt thereof, that is, component (E) is dissolved in a strongly alkaline aqueous solution. As a result of impingement between the particles of the cleaning surfactant that cannot be deposited and impede the access between the particles, or the steric stabilization effect in the polymer adsorption to the particle surface, the electrostatic effect that is stabilization by the electrostatic repulsive force, the dispersing action by such synergistic effects, etc. It can be thought of as being stably dispersed.

As for the compounding quantity of (B) in the washing | cleaning agent of 1-part type this invention for replenishment, it may be good also when it is 0, as described in the section [Means for solving a problem]. That is, in the degreasing process of the continuous annealing line of a cold rolled steel sheet (rolled lubricant containing a tallow etc.), for example, the reduction (soap) of the produced rolling lubricant oil contributes greatly to steel plate washability, In the case of a replenishment, no cleaning surfactant is required.

However, when the cleaning agent of the present invention is used, it is preferable to blend component (B), which is a cleaning surfactant, among other replenishing agents in many other cleaning processes, and the amount of component (B) in that case is from 25 to 25. It is 0.1 weight% or less, Preferably it is 0.1-20 weight%, More preferably, it is 0.5-15 weight%, More preferably, it is 2-10 weight%. When this compounding quantity is less than 0.1 weight%, the effect as a washing | cleaning improvement agent is not exhibited except the case where the cleaning surfactant component which replaces component (B) is produced at the time of dry-bath operation, and when it is more than 25 weight%, the effect Is uneconomical as is saturated.

Moreover, the upper limit of the said compounding quantity is set higher than the upper limit of the compounding quantity of the component (B) in the 1-component type washing | cleaning agent for dry baths. The reason for this is that in the line for cleaning and removing insensitive fats and oils such as mineral oil, the required amount of the antifoaming agent (C) is reduced by the defoaming effect of the mineral oil, but on the contrary, the consumption of the surfactant or the oil concentration in the oil / water separator is reduced. This is because the weight of the cleaning surfactant is required due to the decrease in the emulsion performance caused by the increase.

Since the use ratio of the alkali builder composition and surfactant composition in the two-component type | system | group cleaning agent for dry bath can be selected when using a washing | cleaning agent, in a washing | cleaning agent, for example, surfactant for washing of a component (B) and It is not necessary to consider the mutual ratio with the alkali agent of component (A), and only the mutual ratio of component (B) and component (C) (defoamer) in surfactant composition should be considered about the compounding quantity of component (B). The ratio of the two components is 0.1-20 wt%, preferably 0.5-15 wt%, more preferably 2-10 wt%, when the surfactant composition is diluted as it is or with water. In this case, the concentration of the component (C) is defined as 0.01 to 10% by weight, preferably 0.1 to 8% by weight, more preferably 0.5 to 5% by weight.

In addition, when component (B) and component (C) can ensure liquid supply property as its own liquid, water is not necessarily required in surfactant composition.

The compounding amount of the component (B) in the surfactant composition in the two-pack detergent of the present invention for replenishment is the same as the compounding amount of the component (B) in the detergent of the present invention of one-pack type of the refilling agent for 0 days. Although it is good also at this time, except for this, generally, it is preferable to mix | blend a component (B). The ratio of component (B) and component (C) (antifoaming agent) in such a case is such that the concentration of component (B) when the surfactant composition is diluted as it is or with water is large from 0 to 25% by weight, preferably 0.2 to 20% by weight, more preferably 0.5 to 15% by weight, even more preferably 2 to 10% by weight, the concentration of component (C) is 0.01 to 25% by weight, preferably 0.05 to 15% by weight, It is prescribed | regulated to the composition more preferably 0.1 to 10 weight%, still more preferably 0.5 to 5 weight%.

Next, the antifoamer of component (C) used by this invention is effective in suppressing foaming in a washing process. As the antifoaming agent, an antifoaming surfactant generally used as an antifoaming agent is used, for example, sorbitan higher fatty acid monoester (higher fatty acid is generally C12-18 saturated or unsaturated monovalent fatty acid), sorbitan higher fatty acid triester ( The higher fatty acids are generally C12-18 saturated or unsaturated monovalent fatty acids), ethylene oxide low mole adducts of nonylphenol, ethylene oxide propylene oxide copolymers having low ethylene oxide addition amount, ethylene as polyoxyethylene polyoxypropylene polyhydric alcohol ether. The addition amount of oxide is low, the polyoxyethylene polyoxypropylene polyhydric alcohol ether has a low addition amount of ethylene oxide, the water solubility is low, and the turbid dispersion or separation in water is mentioned. The said nonionic surfactant can be used individually or in combination of 2 or more types.

The compounding quantity of the antifoamer of component (C) in the one-component type washing | cleaning agent for dry baths is 0.01-10 weight%, Preferably it is 0.1-8 weight%, More preferably, it is 0.5-5 weight%. When this compounding quantity is less than 0.1 weight%, the effect as an antifoamer is not exhibited, and when it is more than 10 weight%, the effect becomes saturated, and it is uneconomical. In this detergent, a defoaming agent is also disperse | distributed stably as a part of suspension component, and the mechanism of the effect can be considered to be the same as the dispersion mechanism of the said surfactant for cleaning.

The compounding amount of the component (C) in the one-pack detergent of the present invention for replenishment is 0.01 to 25% by weight, preferably 0.05 to 15% by weight, more preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight. When this compounding quantity is less than 0.01 weight%, the effect as an antifoamer is not expressed, but when it is more than 25 weight%, the effect will be saturated, and it is uneconomical.

In addition, the upper limit of the said compounding quantity is set higher than the upper limit of the compounding quantity of the component (C) in the 1-component type washing | cleaning agent for dry baths. The reason for this is that the amount of soap generated after elapse of time increases and the cleaning performance is enhanced in the line which removes by washing of the susceptible fat and oil, while the deterioration of foaming resistance becomes remarkable.

The defoaming agent compounding quantity of component (C) in the surfactant composition in the two-component type washing | cleaning agent for dry baths is the same as when the compounding quantity of component (B) was demonstrated.

Regarding the surfactant composition in the two-pack detergent of the present invention for replenishment, when the compounding amount of component (B) is 0, the surfactant composition may be composed only of component (C) (antifoaming agent), and C) and water. When the component (C) consists of water and the concentration of the component (C), the concentration of the component (C) is 0.01 to 25% by weight, preferably 0.05 to 15% by weight, when the surfactant composition is as it is or when it is diluted with water. The concentration is more preferably 0.1 to 10% by weight, even more preferably 0.5 to 5% by weight. In addition, when a component (B) is mix | blended, the mutual ratio of a component (B) and a component (C) is the same as when the compounding quantity of the component (B) was demonstrated.

Next, in the washing | cleaning agent of this invention, the chelating agent of a component (D) is mix | blended in order to improve the washing | cleaning effect. Such chelating agents include, for example, aminecarboxylic acids such as triacetic acid, ethylenediamine tetraacetic acid, ethylenediamine diacetic acid, triethylenetetramic acid hexaacetic acid, or alkali metal salts thereof (for example, sodium salts and potassium salts), or the like. Salts such as ammonium salts or lower amine salts (e.g. triethylamine salts), oxycarboxylic acids such as malic acid, citric acid, gluconic acid, heptogluconic acid or alkali metal salts thereof (e.g. sodium salts, potassium salts) or ammonium salts Or salts, such as a lower amine salt (for example, triethylamine salt), etc. are mentioned. Among these, it is preferable to use oxycarboxylic acid or its salt, especially the alkali metal salt of oxycarboxylic acid. The said chelating agent can be used individually or in combination of 2 or more types.

In the present cleaner, all or part of these chelate builders are precipitated at a concentration exceeding solubility in a high concentration strong alkaline aqueous solution, and a single or copolymer of an ethylenically unsaturated organic acid monomer which will be described later, or a salt thereof, that is, a component (E It is dispersed stably as a part of the suspending component by the dispersing and coagulation suppressing action. Moreover, since this chelating agent precipitate has the effect of further improving the stable dispersion, such as the supersaturation precipitate of the said low solubility alkali builder, the washing | cleaning surfactant, an antifoamer, etc. in this composition, it is estimated that it also expresses the effect as a dispersion adjuvant.

In the cleaning agent of the present invention, that is, in the one-component liquid cleaner for dry bath, in the one-component liquid cleaner for replenishment, in the alkaline builder composition in the two-component liquid cleaner for dry bath, and in the two-component bone for replenishment The compounding quantity of the chelating agent of (D) in the alkali builder composition in a washing | cleaning agent is 0.1-20 weight%, Preferably it is 1-10 weight%. When this compounding quantity is less than 0.1 weight%, the improvement of a washing | cleaning effect is inadequate, and when it is more than 20 weight%, this composition becomes extremely thick, or the effect is saturated and it is uneconomical.

Next, the sole or copolymer of the ethylenically unsaturated organic acid monomer of component (E) used in the present invention, or a salt thereof, is a cleaning surfactant or component for component (B) that precipitates and separates the salt in a highly concentrated aqueous solution of alkali. It is essential to stably emulsify and disperse the antifoaming agent (C), the chelating agent of the supersaturated precipitate (D), or the low solubility alkali builder in the component (A) in a high concentration strong alkaline aqueous solution. Moreover, depending on the structure of component (E), it can understand that it acts also as a chelating agent for the purpose of improving the washing | cleaning effect. In addition, it can be considered that component (E) is melt | dissolved or disperse | distributed finely in the alkaline liquid detergent for metals of this invention.

As a single or copolymer of the said ethylenically unsaturated organic acid monomer, At least 1 sort (s) of the homopolymer or 2 or more types of ethylenic unsaturated organic acid monomer, or ethylenically unsaturated organic acid monomer, and at least 1 sort (s) of another ethylenic monomer, The copolymer of is mentioned. Among these, other copolymers of ethylenic monomers are preferable because copolymers containing 70 mol% or more and 90 mol% or more of the units of the ethylenically unsaturated organic acid monomers have the above stable dispersion effect.

More detailed examples of the ethylenically unsaturated organic acid monomer alone or as copolymers include homopolymers of the ethylenically unsaturated organic acid monomers as shown in the following (1) or copolymers composed of two or more thereof or those shown in the following (1). And at least one copolymer of at least one of the ethylenically unsaturated organic acid monomers and monomers of the following (2) to (6). As a copolymer of the monomer of following (1) and the monomer of following (2)-(6), the copolymer containing 70 mol% or more and 90 mol% or more of units of the monomer of following (1) is said stable It is preferable because it brings a dispersing effect.

Examples of the ethylenically unsaturated organic acid monomers include ethylenically unsaturated carboxylic acid monomers and ethylenically unsaturated sulfonic acid monomers as in the following (1), but ethylenically unsaturated carboxylic acid monomers are more preferred.

Thus, the homopolymer of these ethylenically unsaturated organic acid monomers or its salt is preferable, The homopolymer of the ethylenically unsaturated carboxylic acid monomer of the following (1), or the copolymer which consists of two or more thereof, or (1) A copolymer of at least one of the ethylenically unsaturated carboxylic acid monomers of the monomer and at least one of the monomers of the following (2) to (6), wherein the monomer unit is contained at least 70 mol%, more preferably at least 90 mol% Copolymers or alkali metal salts thereof, more preferably homopolymerization of acrylic acid or maleic acid, or copolymers in any ratio of both, or at least one of acrylic acid and maleic acid and at least one monomer of the following (2) to (6): As the copolymer with the species, a copolymer containing 70 mol% or more, more preferably 90 mol% or more of the unit of the carboxylic acid monomer, or an alkali metal salt thereof .

As a salt of an ethylenically unsaturated organic acid monomer alone or a copolymer, the alkali metal salt (for example, sodium salt, potassium salt), ammonium salt, or lower amine salt (for example triethylamine salt) of the said single or copolymer is used Can be mentioned. In addition, all or part of the organic acid monomer units in the polymer may be salts.

It is also possible, of course, to use a commercially available single or copolymer of the ethylenically unsaturated organic acid monomer or a salt thereof, and can generally be obtained as an aqueous solution.

The sole or copolymer of the ethylenically unsaturated organic acid monomer used in the present invention is a surfactant for cleaning the component (B) or an antifoaming agent of (C), a chelating agent of the component (D) and a low solubility alkali in the component (A). The molecular weight (= average molecular weight), as measured by gel permeation chromatography using an acrylic ester resin as a standard, should be 1,000 to 3,000,000, and preferably 1,000 to 1,000,000, as it brings about a stable dispersion of the builder. It is more preferable if it is 1,000-300,000, It is still more preferable if it is 2,000-150,000, It is still more preferable that it is 3,000-20,000. When the molecular weight is less than 1000, the dispersion stability is poor, and when the molecular weight exceeds 3,000,000, the single or copolymer of the ethylenically unsaturated organic acid monomer of component (E) becomes extremely high in viscosity and the concentration of the aqueous solution cannot be increased. The handleability becomes very bad, making it difficult to blend the required amount as the dispersant of the present invention.

(1) ethylenically unsaturated carboxylic acid monomers such as half esters of dibasic acids, such as acrylic acid, maleic acid, methacrylic acid, crotonic acid, itaconic acid and fumar, vinylsulfonic acid, metharylsulfonic acid, styrenesulfonic acid, 2- Ethylenic unsaturated sulfonic acid monomers such as acrylamide-2-methylpropanesulfonic acid

(2) (meth) having N-unsubstituted or lower alkyl-substituted methylol groups such as N-methylol acrylamide, N-methylol methacrylamide, N-butoxymethylacrylamide, N-butoxymethyl methacrylamide, etc. ) Acrylamide; (Meth) acrylamide); N-alkyl, such as N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, Nn-propyl (meth) acrylamide, Nt-butyl (meth) acrylamide, and Nt-octyl (meth) acrylamide (C = 1-8, especially C = 1-4) (meth) acrylamide; N, N- dimethyl (meth) acrylamide N, N- lower alkyl (meth) acrylamide, such as N, N- dimethyl (meth) acrylamide; N-benzyl (meth) acrylamide; (Meth) acrylamide type monomers, such as N-cyclohetotosyl (meth) acrylamide

(3) phosphonyloxy, such as phosphonyloxymethyl acrylate, phosphonyloxyethyl acrylate, phosphonyloxypropyl acrylate, phosphonyloxymethyl acrylate, phosphonyloxyethyl methacrylate, and phosphonyloxypropyl acrylate Lower alkyl (meth) acrylate

(4) methoxymethyl acrylate, methoxyethyl acrylate, ethoxymethyl acrylate, ethoxyethyl acrylate, methoxymethyl acrylate, methoxyethyl methacrylate, ethoxymethyl methacrylate, ethoxyethyl Lower alkoxy lower alkyl (meth) acrylates such as methacrylate and ethoxybutyl acrylate; Hydroxy lower alkyl (meth) acrylates, such as hydroxy, such as 2-hydroxyethyl (meth) acrylate and 3-hydroxypropyl (meth) acrylate

(5) Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, t-butyl acrylate, 2-ethylheto Alkyl (C = 1-8) (meth) acrylates, such as tosyl methacrylate and octyl acrylate,

(6) Other ethylenic monomers, such as styrene, methyl styrene, vinyl acetate, acrylonitrile, the vinyl ester of saturated carboxylic acid branched on (alpha), vinyl chloride, vinyltoluene, ethylene.

In addition, in said (1)-(6), "lower" in lower alkyl and lower alkoxy shows C1-C4, especially 1-2.

In the cleaning agent of the present invention, that is, in the one-component type cleaning agent for dry bath, in the one-component type cleaning agent for replenishing, in the alkali builder composition in the two-component type cleaning agent for dry bath, and in the two-component type for replenishing In the alkali builder composition in the cleaning agent, the compounding amount of the ethylenically unsaturated organic acid monomer as the component (E) or the copolymer or its salt needs to be 0.1 to 15% by weight, and preferably 0.5 to 10% by weight, and 0.5 When it is-7 weight%, it is more preferable. Dispersion stability is inadequate when this compounding quantity is less than 0.1 weight%, and when it mixes more than 15 weight%, this detergent is extremely thickened or the effect becomes saturated, and it is uneconomical.

In addition, since the viscosity increases when the molecular weight of the component (E) alone or the copolymer increases, the blending amount is preferably 1% by weight or less and 100,000 to 100,000% by weight of 5% or less when the molecular weight is greater than 100,000.

Subsequently, the smectite low earth mineral of component (F) used by this invention adsorb | sucks the surfactant for washing | cleaning which precipitates and isolates a salt in high aqueous alkali solution, and an antifoamer, emulsifies these surfactant components in the washing | cleaning agent of this invention. In order to strengthen dispersion stability, it is contained in this detergent as an arbitrary component. For this reason, it is not necessary to mix | blend the component (F) with the two-component type washing | cleaning agent of this invention, and component (F) is contained arbitrarily only in the washing | cleaning agent of this invention which is a one-component type for dry bath or replenishment.

The smectite clay mineral of component (F) used by this invention is a following general formula,

[Si ₈ (Mg _a Li _b ) O ₂₀ (OH) _c F _4-c ] ^-x Me ^{+ x} (0a≤6, 0b≤6, 4a + b8, 0≤c≤4, x = 12-2a- b, Me: Na, K, Li and at least one of NH ₄ ). This clay mineral is produced naturally but can also be obtained as a synthetic product.

Specific examples of the smectite-based clay mineral used in the present invention include montmorillonite, soconite, biderite, hectorite and the like, and hectorite is preferable in view of small particle diameter. Hectorite includes natural hectorite and synthetic hectorite, and any of them can be used in the present invention, but synthetic hectorite having a smaller particle size is generally more preferable.

The smectite clay mineral has a layered structure, and each layer of the crystal structure in the layered structure is composed of a two-dimensional platelet having a thickness of about 1 mμ. Some of the magnesium and aluminum atoms present in the platelet unit are homogenously substituted with the low atom cationic atoms, and as a result, the platen unit is negatively charged. In the dry state, these negative charges balance each other with a displaceable cation outside the lattice structure of the plate surface, and in solid phase these particles are bound together by van der Waals forces and form a flat plate bundle. do.

When the smectite clay mineral is dispersed in an aqueous phase, a substitutable cation is hydrated to cause swelling of the particles, and a stable sol can be obtained by dispersing using a general disperser such as a high-speed dissolver. In this state of separation in the aqueous phase, the platelet becomes a negative charge on the surface, and electrostatic repulsion occurs to form a sol subdivided into platelet-shaped primary particles. The aqueous dispersion of the smectite-based clay mineral is a two-dimensional platelet having a thickness of about 1 mμ, that is, a square or disc-shaped plate, and one side or diameter of the plate surface can be viewed as 20 to 500 mμ. Synthetic hectorite, which is a disk-shaped particle having a shape of the primary particles having a thickness of about 1 μm and having a diameter of 20 to 40 μm, is commercially available.

The compounding quantity of the smectite clay mineral of the component (F) in the one-component type | mold for a dry bath and replenishment is 0.01 to 0.5 weight%, Preferably it is 0.05 to 0.3 weight%. When this compounding quantity is less than 0.01 weight%, sufficient effect cannot be acquired, and when it exceeds 0.5 weight%, thickening or solidification at the time of low temperature storage will become easy to occur, and it is disadvantageous also in terms of cost.

The method for producing a one-component alkaline liquid detergent for metals in the dry bath of the present invention may also take a commercial method of finally adding an alkali agent while mixing and mixing a component other than the alkali agent in water in advance. In order to raise the liquid stability of the washing | cleaning agent of this invention, the stirring equipment which has a strong shearing force is used, and stirring for a long time is required.

However, if the following manufacturing method is taken, productivity improvement can be expected. In other words, the alkali agent is dissolved in an aqueous solution in which component (D) (chelating agent) is dissolved or in an aqueous solution in which component (D) (forward) and (E) (the sole or copolymer of ethylenically unsaturated organic acid monomer or a salt thereof) are dissolved. The component (A) (alkali agent) is stirred and mixed to have a concentration of 40% by weight or more, preferably 40 to 75% by weight, more preferably 45 to 65% by weight, and the whole or part of the chelating agent, or After preparing a suspension ① in which all or part of the chelating agent and a part of the alkaline agent are precipitated as a suspending component, component (B) (surfactant for cleaning), component (C) (defoamer) and component (E) (whole quantity or ① It is preferable to use a production method in which the mixed liquid ② obtained by stirring and mixing the water) and water is added to the ① by a small amount of stirring by various stirring methods and mixed in small portions.

In case of using component (F) (smectite clay mineral), component (B), component (C) and component (E) (whole quantity or It is preferable to manufacture by adding, stirring and mixing the remainder used in (1).

Specifically, the temperature of ① when adding ② to ① is preferably 50 ° C. or higher, and further 60 ° C. or higher, and the stirring equipment uses a homomixer, a line mixer, a gear pump or the like having a high shear force. It is preferable.

In addition, the alkaline liquid detergent for metal which is integrated in the replenishment is carried out in the same manner as described above using the same liquid except that the component (B) is not contained in the above (2). Can be prepared.

In addition, when using the alkaline liquid detergent for metals which are a two-component type | mold for a dry bath or replenishment, when producing an alkali builder composition, the liquid which consists of water of component (E) (the whole quantity or the remainder used by ①) is used as said (2). Can be. In addition, although the surfactant composition in the two-component alkaline liquid detergent for metals for dry baths or replenishment can be used as it is only from component (C), in other cases, component (B) and component (C) or It can manufacture by mixing component (B), component (C), and water, or mixing component (C) and water.

The alkaline liquid detergent for one-component metals for dry bath or replenishment of the present invention is generally diluted with water in an amount of 2 to 5% by weight in terms of alkylating agent (e.g. sodium hydroxide) concentration, followed by various metal materials (cold rolled steel, electric Plated steel, aluminum materials, etc.), in particular dirt and metals such as animal and vegetable oils, greases, mineral oils, rolled oils, cutting oils, press oils, and oil-based substances, such as cold rolled steels. It can be applied to washing of powder.

This washing can be performed at a processing liquid temperature of about 50 to 80 ° C. by immersion cleaning, spray cleaning, electrolytic cleaning, or the like. Especially, electrolytic cleaning is preferable that the cleaning effect is more excellent.

In addition, when using the two-component alkaline liquid detergent for metals for drying or replenishing, the alkali builder composition, the surfactant composition, and water may be mixed and used in the same manner as above, and the alkali builder composition and the surfactant composition may be used. May be diluted separately with water and sprayed under the same spray conditions, for example, in separate nozzles. Regardless of the method used, the ratio of use of the alkali builder composition and the surfactant composition at the time of use is not changeable, and a mixture of the alkali builder composition, the surfactant composition, and the water at the time of use for the metal may be prepared. In the case, the concentration ratio of each component therein is in the range of the above-mentioned concentration ratio in the one-component cleaning composition for dry baths or the one-component cleaning composition for replenishment, depending on whether the concentration ratio of each component is for drying or replenishment. It needs to be heard.

EXAMPLE

Hereinafter, the present invention will be specifically described according to the following examples and comparative examples. However, the present invention is not limited to these embodiments.

[Examples 1-51 and Comparative Examples 1-35]

1. Preparation of Pharmaceuticals and Detergent Compositions

(1) Pharmaceutical

(A) Alkaline:

(A-1) sodium hydroxide (96%, reagent express)

(A-2) Sodium Silicate (from Nippon Kagaku Kogyo Co., Ltd., Granular, Purity 90% or more)

(A-3) Sodium dihydrogen phosphate anhydride (more than 99% of Kantogagaku Co., Ltd. purity)

(B) Cleaning surfactant:

(B-1) Nonylphenol ethylene oxide 9 mol adduct HLB = 12

(B-2) Nonylphenol ethylene oxide 20 mol adduct HLB = 16

(B-3) lauryl alcohol sodium sulfate ester

(B-4) Nonylphenol ethylene oxide 94 mole adduct HLB = 19

(C) defoamer:

(C-1) polyhydric alcohol ethylene oxide 10 mol propylene oxide 20 adduct

(C-2) nonylphenol ethylene oxide 2 mole adduct

(D) Chelating Agents:

(D-1) Sodium Gluconate

(D-2) Ethylenediaminetetraacetic acid tetrasodium salt

(E) homo or copolymer of ethylenically unsaturated organic acid monomers or salts thereof or other polymers:

(E-1) polyacrylic acid (molecular weight: 3,000)

(E-2) polyacrylic acid (molecular weight 10,000)

(E-3) polyacrylic acid (molecular weight 70,000)

(E-4) polyacrylic acid (molecular weight 150,000)

(E-5) Polyacrylic Acid (Molecular Weight 1,600,000)

(E-6) Polymaleic Acid (Molecular Weight 20,000)

(E-7) copolymer of acrylic acid and maleic acid (molar ratio: acrylic acid / maleic acid = 70 mol% / 30 mol%) (molecular weight 10,000)

(E-8) copolymer of acrylic acid and styrene (molar ratio: acrylic acid / styrene = 80 mol% / 20 mol%) (molecular weight 10,000)

(E-9) Sodium polystyrene sulfonate (molecular weight 10,000)

(E-10) copolymer of acrylic acid and styrene (molar ratio: acrylic acid / styrene = 50 mol% / 50 mol%) (molecular weight 10,000, comparative product)

(E-11) polyacrylic acid (molecular weight 500, comparative product)

(E-12) Sodium polyacrylate (molecular weight 4,300,000, comparative product)

(E-13) polyvinyl alcohol (molecular weight 1,500, 88 mol%, degree of comparative product)

(E-11) polyethylene glycol (molecular weight 20,000, comparative product)

(F) Smectite clay minerals:

(F-1) Commercially available synthetic hectorite [Si ₈ (Mg _5.34 Li _0.66 ) O ₂₀ (OH + F) ₄ ] Na _0.66 (primary particle shape: thickness 1mμ, diameter 20-40mμ in the form of a disc

(G) solubilizer:

(G-1) 2-methylbutyric acid (used in JP-A-5-230498)

(G-2) 2-octenyl succinic acid (used in Japanese Patent Publication No. 3-46038)

(2) Preparation of Cleaning Composition

Each detergent composition used in the Example and the comparative example was prepared as follows using each said component.

(1) Alkali concentration of the ethylenically unsaturated organic acid monomer of (E) alone or in copolymers or salts or other polymers in an aqueous solution in which 1 to 20% of the total amount of the compound and the chelating agent of (D) are dissolved in water The alkali agent of (A) is mixed so that it may become 40 weight% or more, and the suspension or aqueous solution containing a part of (E) and (A) and (D) is obtained.

(2) alone or copolymers or salts or other polymers of the cleaning surfactant of (B), the antifoaming agent of (C), and the remaining ethylenically unsaturated organic acid monomer of (E) Accordingly, an aqueous solution or emulsion obtained by further mixing the smectite clay mineral of (F) or (G) solubilizer in water at a predetermined ratio is obtained.

However, in the case of the two-component alkaline liquid detergent for dry bath and replenishment, the cleaning surfactant of (B) and the antifoaming agent of (C) are excluded.

(3) While stirring the suspension or aqueous solution prepared in (1) at 6000 rpm with a high speed mixer, the aqueous solution or emulsion prepared in (2) was gradually added, followed by stirring for 1 hour to obtain an alkaline liquid detergent (composition) or an alkali builder composition for a one-component metal.

2. Test method

2.1 Liquid stability test

Each prepared one-part alkaline liquid detergent or alkali builder composition is left standing or continuously stirred at room temperature (15 ° C or 30 ° C), and the presence or absence of separation, thickening and solidification is visually observed and evaluated by the following liquid stability evaluation criteria. It was.

In addition, in consideration of storage during transportation of the product or in the storage tank from a practical point of view, a minimum of product stability (Δ or more) of at least 1 day in a stationary state and at least 3 days in a stirring state is required.

Liquid stability criteria:

◎; 1 week or more in stationary state and 2 weeks or more in agitation state, stable and free from segregation or extreme thickening (including solidification)

○; 3 days or more in stationary state and 1 week or more in agitation state, stable or free from segregation or extreme thickening (including solidification)

△; At least 1 day in stationary state and at least 3 days in agitation state, stable and free from segregation or extreme thickening (including solidification)

×; In stationary conditions of less than 1 day and in agitation conditions of less than 3 days, when separated or extremely thickened (including solidification)

Stirring conditions: 200 g of each test solution was put in a glass beaker, it sealed, and it stirred at the rotation speed of 300 rpm using the magnet star.

2.2 Cleanliness Test

Each dry one-component alkaline liquid detergent prepared above was diluted with water so as to have an alkali concentration of 2% by weight to obtain a washing liquid. Each washing solution was heated to 80 ° C. and used to electrolytically clean the steel sheet to which the synthetic ester rolling oil was attached, and immediately afterwards, washed with water and left for 15 seconds to visually evaluate the leaked area. Electrolytic cleaning conditions are current density: 4A / dm ² , processing time: 1 second at the cathode and 1 second at the anode.

Evaluation standard:

○: 100% or more leakage area 100%

(Triangle | delta): Leakage area is 70% or more and less than 95%

X: Leakage area is less than 70%

2.3 Foam Test

Each of the dry liquid one-part alkaline liquid detergents prepared above was diluted with water so as to have an alkali concentration of 2% by weight to obtain a washing liquid. Each washing | cleaning liquid was heated to 50 degreeC, and 50 ml of 100 ml of oily measuring cylinders are extract | collected. Immediately after the harvesting, the genetic measuring cylinder was shaken 30 times at a rate of 1 time during 1 second, and the height of the foam after shaking was measured by the scale of the measuring measuring cylinder.

Evaluation standard:

○: less than 5 ml in height of the foam

△: more than 5 ml of the height of the bubble less than 10 ml

X: More than 10 ml of the height of the bubble

2.4 Cost

When each one-component type alkaline liquid detergent for dry bath prepared above was diluted with water so as to have an alkalinizer concentration of 2%, the relative raw material cost of the conventional product was 100. As a conventional product, the comparative example 14 of Table 2 mentioned later was used.

Evaluation standard:

○: less than 50

△: 50 or more and less than 80

×: 80 or more

In Table 1, Examples 1-28 of the 1-component alkaline liquid detergent for dry baths, and Table 2 are Comparative Examples 1-20 of the 1-component alkaline liquid detergent for dry baths, and Table 3 Examples 29-40 of the 1-component alkaline liquid detergent for replenishment. In Comparative Examples 21 to 28 and Table 4, the tests were carried out according to the compositions of the respective alkaline liquid detergents of Examples 41 to 51 and Comparative Examples 29 to 35 of the two-component alkaline liquid detergent for dry bath and replenishment, and the test method and evaluation results. One result is shown. In addition, only the liquid stability evaluation result was shown about the 1-component alkaline liquid detergent for replenishment of Table 3, and only the liquid stability evaluation result of the alkaline builder composition was shown for the 2-component alkaline liquid detergent for dry baths and replenishment of Table 4.

Examples 1 to 28 as in Table 1 are generally balanced in terms of liquid stability, detergency, foamability and cost, and Examples 29 to 40 as in Table 3 and Examples 41 to 51 as in Table 4 Also, liquid stability was excellent and it was practically satisfying the objective of this invention.

On the other hand, in Comparative Examples 1 to 20 shown in Table 2, any one evaluation item of liquid stability, detergency, foamability, and cost was bad, and in Comparative Examples 21 to 28 and Table 4 shown in Table 4, Liquid stability was inferior.

That is, it does not contain a single or copolymer of ethylenically unsaturated organic acid monomer or its salt (E), the molecular weight is out of standard, the copolymerization ratio of ethylenically unsaturated organic acid monomer is less than 70 mol%, or different polymers In the used comparative examples 1-7, 21-25, and 29-33, liquid stability is inferior. Detergency was inferior in the comparative example 8 which does not contain the washing | cleaning surfactant (B), or the comparative example 9 which used surfactant out of the range of HLB. In Comparative Example 10 in which the antifoaming agent was not contained, foamability was high. In Comparative Example 11 in which the chelating agent (D) was not contained, detergency was poor. Further, in Comparative Examples 14, 15 and 17 using the solubilizing agents described in Japanese Patent Application Laid-open No. Hei 3-46038 or Japanese Patent Application Laid-open No. Hei 5-230498, the cleaning property and the liquid stability are good but the cost is high. The comparative example 13, 28, 34, and 35 which tested the high concentration using the comparatively high lipophilic property, and the liquid stability was inferior in the comparative example 16 which used the high performance antifoamer (C-1). In addition, in the comparative examples 12, 18-20, 26, and 27 in which compounding quantity of an alkali agent (A), a chelating agent (D), an ethylenically unsaturated organic acid monomer, or a copolymer, its salt (E), etc. is outside the range of this invention, Liquid stability was inferior.

TABLE 1

Example of 1-component alkaline liquid detergent for dry bath

TABLE 2

Comparative example of one-component alkaline liquid detergent for dry bath

TABLE 3

1-component alkaline liquid cleaner

TABLE 4

2 component alkaline liquid cleaner for dry bath

The composition of the present invention does not have to add a large amount of solubilizer in a high concentration of strong alkali agent as in the prior art, and avoids precipitation separation of salts. It is equal to or more than the product and also a low cost product, which greatly contributes to the improvement of the work efficiency or the low cost. In addition, since the solubilizer, which is an organic substance other than the cleaning essential ingredient, which has been blended in a large amount due to the high concentration according to the prior art, is not used, the BOD or COD can be reduced, and thus the wastewater treatment property is better than the conventional products. Furthermore, since it is not a dissolution type but an emulsion dispersion type suspension, it is possible to increase the concentration of the alkali builder component having a relatively low solubility, to expand the selectivity of the cleaning surfactant and the antifoaming component, and to expand the degree of freedom of the mixing balance of the cleaning surfactant and the antifoaming component. As a result, it is possible to design a cleaning agent suitable for the use situation, and the practical effect can be said to be quite large.

Claims (18)

(A) Alkali agent, (E) Single or copolymer of ethylenically unsaturated organic acid monomer whose molecular weight is 1,000-3,000,000 (The copolymer of other ethylenic monomer is also included. It is the same as follows in description of a claim.), Or its A salt and water, The alkaline liquid detergent for metals of suspension state characterized by the above-mentioned. (A) 35 to 70% of alkali chemicals (values based on the total weight of the detergent, the same as described below in the claims), (E) single or copolymer of ethylenically unsaturated organic acid monomer having a molecular weight of 1,000 to 3,000,000 or At least 1 sort (s) chosen from a salt, (B) washing | cleaning surfactant, (C) antifoamer, and (D) chelating agent, and water, The alkaline liquid detergent for metals of suspension state characterized by the above-mentioned. (A) 35-70 weight% of alkali chemicals, (B) 0.1-20 weight% of cleaning surfactants, (C) 0.01-10 weight% of antifoamers, (D) 0.1-20 weight% of chelating agents, (E) molecular weight 1,000 An alkaline liquid detergent for one-part type metal liquid for drying in a suspended state, comprising from 0.1 to 15% by weight of a single or copolymer of an ethylenically unsaturated organic acid monomer of 3,000,000 or a salt thereof and water. The alkaline liquid detergent for one-component metal for dry bath according to claim 3, wherein the alkali agent (component (A)) is at least one selected from sodium hydroxide, sodium ortho silicate, and sodium phosphate or sodium hydrogen phosphate. The alkaline liquid detergent for one-component metal for dry bath according to claim 3, wherein the alkali agent (component (B)) is at least one selected from a nonionic surfactant and an anionic surfactant having an HLB of 8 or more and 18 or less. The method according to claim 3, wherein the single or copolymer of the ethylenically unsaturated organic acid monomer or a salt thereof (component (E)) is a polyacrylic acid, a polymaleic acid, a copolymer of acrylic acid and maleic acid, an acrylic acid unit and / or a maleic acid unit. The alkaline liquid detergent for 1-component metals for dry baths which is at least 1 sort (s) chosen from the copolymer containing mol% or more, and the salt of such a unit or a copolymer. The alkaline liquid detergent for 1-component metal for dry baths of Claim 3 which further contains 0.01-0.5 weight% of (F) smectite-type clay minerals. The alkaline liquid detergent for one-component metal for dry baths according to any one of claims 3 to 7, wherein the dilution with water is such that the alkali agent concentration when used is used. (A) 35-70 weight% of alkaline agents, (C) antifoaming agent 0.01-25 weight%, (D) chelating agent 0.1-20 weight%, and (E) molecular weight of 1,000-3,000,000 ethylenically unsaturated organic acid monomers alone Or 0.1-15 weight% of copolymers or its salt, and water are contained, The alkaline liquid detergent for one-component metals for replenishment in suspension state characterized by the above-mentioned. 10. The alkylliquid liquid cleaner for a one-pack type metal according to claim 9, further comprising (B) a cleaning surfactant 0 to 25% by weight or less. (F) Alkaline liquid detergent for metals as described in Claims 9-10 which further contain 0.01-0.5 weight% of smectite-type clay minerals. 0.1-20 weight% of (A) alkali chemicals, 0.1-20 weight% of (D) chelating agents, and (E) 0.1-weight, the sole or copolymer of ethylenically unsaturated organic acid monomer of 1,000-3,000,000, or its salt (B) A nonionic surfactant having an HLB of 8 or more and 18 or less for use in combination with a composition in a suspended state (hereinafter referred to as an alkali builder composition) containing 15% by weight, and anionic surfactant A composition containing component (B), component (C) and water containing at least one cleaning surfactant selected from (C) and an antifoaming agent, and the concentration of component (B) as it is or when diluted with water The alkaline liquid detergent for two-component metals for dry baths which consists of a composition (henceforth a surfactant composition) whose density | concentration of component (C) becomes 0.01 to 10 weight% when it is 0.1 to 20%. (A) 35 to 70% by weight of an alkali agent, (D) 0.1 to 20% by weight of a chelating agent, and (E) a single or copolymer of an ethylenically unsaturated organic acid monomer having a molecular weight of 1,000 to 3,000,000, or a salt thereof, of 0.1 to 15 (C) (defoamer) or a composition containing an antifoaming agent and water (hereinafter referred to as an antifoaming agent) for use in combination with a weight%, a composition in suspension containing water (hereinafter referred to as an alkali builder composition) The alkaline liquid detergent for replenishment two-component metal which consists of a surfactant composition for convenience), also including the case where it consists of. The component (C) according to claim 13, wherein the surfactant composition is a composition further containing (B) a cleaning surfactant, when the concentration of (B) is from 25 to 25% by weight as it is or when diluted with water. The alkaline liquid detergent for replenishment two-component metal which is a composition whose density | concentration of () is 0.01 to 25 weight%. Ethylene unsaturated in any one of Claims 3-6 in the aqueous solution which melt | dissolved component (D) (chelating agent), or component (D) (whole quantity) and component (E) (molecular weight 1,000-3,000,000). Component (A) (alkali agent) is stirred and mixed in an aqueous solution in which an organic acid monomer alone or a part of a copolymer or a salt thereof) is dissolved so that the concentration of the alkali agent is 40% by weight or more, and the whole or part of the chelating agent, or After preparing a suspension (1) in which all or part of the chelating agent and part of the alkaline agent are precipitated as a suspending component, component (B) (cleaning surfactant), component (C) (antifoaming agent) and component (E) (whole quantity or ①) A method of producing a one-component alkaline liquid detergent for metal, characterized in that the solution (2) obtained by stirring and mixing the remaining water) and water is added in small portions while stirring (1) to (1). The component (B), component (C) and component (E) (whole quantity or the like) according to claim 7, wherein the suspension (1) according to claim 15 is dispersed in water in which component (F) (smectite clay mineral) is dispersed in water. A method of producing an alkaline liquid detergent for one-component metal for dry bath, wherein the remaining liquid used in (1) is added and the mixed solution (2) is added in small amounts while stirring (1). 11. The singly of the ethylenically unsaturated organic acid monomer of Claim 9 or 10 in which the component (D) (chelating agent) melt | dissolved, or component (D) (whole quantity) and component (E) (molecular weight are 1,000-3,000,000). Or component (A) (alkali agent) is stirred and mixed in an aqueous solution in which a part of the copolymer or a salt thereof) is dissolved so that the concentration of the alkali agent is 40% by weight or more, and the whole or part of the chelating agent or the whole amount of the chelating agent. Alternatively, after preparing a suspension (1) in which a part and a part of the alkali agent are precipitated as a suspension component, a solution (2) or a solution (2) obtained by stirring and mixing component (C) (antifoam), component (E) (whole amount or the remainder used in ①) and water A method of producing a one-component metal alkaline liquid detergent for replenishment, characterized in that a small amount is added to and mixed with and mixed with ①. The washing | cleaning method of the metal material which performs washing | cleaning of the metal material by the alkaline liquid detergent for one-component metals for dry baths of Claim 8.