WO2010113734A1

WO2010113734A1 - Cleaning agent composition and cleaning method

Info

Publication number: WO2010113734A1
Application number: PCT/JP2010/055157
Authority: WO
Inventors: 英実寺; 裕幸土手; 芳弘勘藤
Original assignee: 松本油脂製薬株式会社
Priority date: 2009-04-03
Filing date: 2010-03-25
Publication date: 2010-10-07
Also published as: JP2011246722A; JPWO2010113734A1; JP4830057B2; CN102378810B; CN102378810A; JP5651081B2

Abstract

Disclosed is a cleaning agent composition which contains at least one enzyme selected from among amylases, cellulases and pectinases, and an anionic surfactant that does not inhibit the activity of the enzyme, while having excellent permeability and wettability. The cleaning agent composition has excellent working environment properties, permeability, wettability and cleaning properties. Also disclosed is a cleaning method. The cleaning agent composition contains (A) at least one enzyme selected from among amylases, cellulases and pectinases, and (B) an anionic surfactant which is obtained by anionizing an alkylene oxide addition product of an aliphatic amine having 8-18 carbon atoms.

Description

Cleaning composition and cleaning method

The present invention relates to a cleaning composition and a cleaning method containing at least one enzyme selected from amylase, cellulase, and pectinase and a specific anionic surfactant that does not inhibit the activity of the enzyme.

In order to remove dirt from objects to be washed such as clothing and tableware, detergent components such as surfactants, bleaches and enzymes are blended in the detergent composition. Examples of such enzymes include amylase, cellulase, protease, lipase and the like.

In particular, amylase is blended in detergents for clothes and dishes to improve the removal of starch-based stains on objects to be cleaned such as clothes and dishes. In addition, it has been used in the textile industry for a long time because of its excellent ability to remove starch-based dirt.

For fiber washing, especially cellulose fibers, there are fiber-derived resins and waxes among natural fibers. For woven fabrics, pastes such as acrylate resins, polyvinyl alcohols, starches, and waxes are used. The agent component is present as a contaminant. Therefore, a scouring process (including a desizing process, a fiber-derived resin, and a process for removing impurities such as wax) is performed to remove them. Cellulosic fiber scouring treatment includes enzyme scouring treatment using α-amylase, which is excellent in removing starch-based paste components, or oxidative scouring treatment using an alkali.

In the oxidation scouring treatment, an alkali is used in combination, which is not preferable from the viewpoint of the working environment, and also requires neutralization of the waste water. In addition, in the oxidative scouring treatment, there is a concern that some of the cellulose fibers may be changed to oxidized cellulose by the oxidant, which may cause embrittlement of the fibers and dyeing spots. Therefore, from the viewpoint of maintaining the working environment and workability, and the quality of the fiber, the enzyme scouring treatment is preferable to the oxidative scouring treatment using alkali.
However, although α-amylase conventionally used for enzyme scouring treatment can remove starch-based paste components, other components such as fiber-derived wax and wax components cannot be sufficiently scoured. Further, in order to promote the action of the enzyme scouring treatment agent, it is necessary to use a surfactant having excellent penetrability and wettability, but as disclosed in Patent Document 1, an anion having excellent penetrability and wettability. Since the surfactant inhibits the enzyme activity, it is recommended to use a nonionic surfactant in combination because it does not inhibit the enzyme activity. As described above, a scouring agent excellent in scouring properties (paste-freeness, detergency) including an enzyme such as amylase and an anionic surfactant that has excellent permeability and wettability and does not inhibit the activity of the enzyme. Never before.

These are the same problems not only with the scouring agent for scouring and washing the fibers, but also with the cleaning agent for washing the object to be washed. That is, in order to promote the action of a detergent containing an enzyme, it is necessary to use a surfactant having excellent penetrability and wettability, but it has excellent penetrability and wettability with an enzyme such as amylase, and There has never been a detergent composition excellent in detergency, comprising an anionic surfactant that does not inhibit the activity of an enzyme.

JP 2004-218180 A

An object of the present invention includes at least one enzyme selected from amylase, cellulase, and pectinase, and an anionic surfactant that is excellent in permeability and wettability and does not inhibit the activity of the enzyme. It is to provide a cleaning composition and a cleaning method excellent in wettability and cleanability.

As a result of intensive investigations to solve the above problems, the present inventors have found that a specific anionic surfactant is excellent in permeability and wettability and does not inhibit the activity of the enzyme, from amylase, cellulase and pectinase. It has been found that a cleaning composition comprising at least one selected enzyme and this anionic surfactant in combination has excellent working environment and cleaning properties.

That is, the present invention relates to an anionic surfactant obtained by anionizing at least one enzyme (A) selected from amylase, cellulase and pectinase and a (poly) alkylene oxide adduct of an aliphatic amine having 8 to 18 carbon atoms ( B) and a cleaning composition.

The anionic surfactant (B) is preferably a compound represented by the following general formula (1).
_{_{_{RN [(AO) m (CH}}} 2) p COOM] [(AO) n X] (1)
(In the formula, R represents an aliphatic hydrocarbon group having 8 to 18 carbon atoms. AO represents at least one alkylene oxide group selected from an ethylene oxide group (EO) and a propylene oxide group (PO). May constitute a block adduct, an alternating adduct, or a random adduct, X represents a (CH ₂ ) _p COOM group or a hydrogen atom, M represents a hydrogen atom or an alkaline group, and m and n represents an integer of 1 to 50, and p represents an integer of 1 to 3.)

In the general formula (1) of the anionic surfactant (B), R is an aliphatic hydrocarbon group having 10 to 16 carbon atoms, AO is an ethylene oxide group (EO), and m and n are 2 to 10 It is preferable that

The weight ratio (A / B) between the enzyme (A) and the anionic surfactant (B) is 5/95 to 99/1, and the enzyme (A) and the anion occupy the entire nonvolatile content of the cleaning composition. The total weight ratio of the surfactant (B) is preferably 10 to 100% by weight.

The cleaning composition of the present invention further includes a nonionic surfactant (C), and the weight ratio of the nonionic surfactant (C) to the entire nonvolatile content of the cleaning composition is 1 to 90 wt%. The total weight ratio of the enzyme (A) and the anionic surfactant (B) is preferably 10 to 99% by weight.
The cleaning composition of the present invention is preferably for fiber scouring.

Moreover, the cleaning method of the present invention includes a step of cleaning an object to be cleaned using the cleaning composition. Moreover, it is preferable that the said to-be-washed | cleaned material is a fiber, and the said process is a process of scouring a fiber using the cleaning composition for fiber scouring.
Moreover, the fiber refined by the cleaning method of the present invention is also included in the present invention.

Further, the cleaning method of the present invention comprises an anionic surface activity obtained by anionizing at least one enzyme (A) selected from amylase, cellulase and pectinase and a (poly) alkylene oxide adduct of an aliphatic amine having 8 to 18 carbon atoms. It also includes a step of cleaning the object to be cleaned using the agent (B). That is, the object to be cleaned may be cleaned using the enzyme (A) and the anionic surfactant (B) simultaneously, or the object to be cleaned may be cleaned separately.
The anionic surfactant (B) used is preferably a compound represented by the above general formula (1). Moreover, it is preferable that the said to-be-cleaned object is a fiber, and the said process is a process of refine | purifying a fiber using the said enzyme (A) and the said anionic surfactant (B).
Further, the fiber scoured by this washing method is also included in the present invention.

Since it is a detergent composition in which at least one enzyme (A) selected from amylase, cellulase and pectinase is used in combination with an anionic surfactant (B) which is excellent in permeability and wettability and does not inhibit the activity of the enzyme, Excellent work environment, permeability, wettability and cleanability.

The present invention relates to an anionic surfactant (B) obtained by anionizing at least one enzyme (A) selected from amylase, cellulase and pectinase and a (poly) alkylene oxide adduct of an aliphatic amine having 8 to 18 carbon atoms. A cleaning composition comprising: This will be described in detail below.

(enzyme)
The detergent composition of the present invention essentially contains at least one enzyme (A) selected from amylase, cellulase and pectinase. Therefore, one type of enzyme may be used, or two or more types of enzymes may be used in combination. Amylase improves the removability of starch-based stains or starch-based paste components of articles to be cleaned such as clothing and tableware. Cellulase improves the removability of dirt between clothes containing cellulose or dirt on cellulosic fibers. Pectinase improves the removal of stains such as stains on fruit juice or stains on cellulosic fibers on objects to be washed such as clothing and tableware. By including these enzymes (A), the removability of each soil component is improved, and the soil component and / or the starch-based paste component can be more efficiently removed by using two or more kinds of enzymes in combination. In the case of a cleaning composition for scouring fibers, it is preferable to essentially contain amylase in order to remove the starch-based paste component.
The concentration of the enzyme (A) in the cleaning composition is not particularly limited as long as it can be suitably cleaned and scoured according to the type and state of the laundry, tableware or fiber to be treated. For example, the concentration of the enzyme (A) in the cleaning composition is preferably 1 to 2000 units / ml, more preferably 10 to 1000 units / ml, and even more preferably 20 to 500 units / ml.

As the amylase, any conventionally known enzyme may be used, and examples thereof include α-amylase, β-amylase, γ-amylase and the like. Any of them is preferably used, but it is particularly preferable to use α-amylase.
When amylase is used, the concentration of amylase in the detergent composition is not particularly limited as long as it can be suitably washed and scoured according to the type and state of the laundry, tableware or fiber to be treated. For example, when scouring a fabric, the concentration of amylase in the scouring agent is preferably 1 to 2000 units / ml, more preferably 10 to 1000 units / ml, and even more preferably 20 to 500 units / ml.

When cellulase is used, the concentration of cellulase in the detergent composition is not particularly limited as long as it can be suitably scoured according to the type and state of the laundry, tableware, or fiber to be treated. For example, when scouring cotton fabric, the concentration of cellulase in the scouring agent is preferably 1 to 2000 units / ml, more preferably 10 to 1000 units / ml, and even more preferably 20 to 500 units / ml. .

As the pectinase, any conventionally known enzyme may be used, and examples thereof include pectin methylesterase, pectin depolymerase, and protopectinase. Any of them is preferably used, but protopectinase is particularly preferably used.
When pectinase is used, the concentration of pectinase in the cleaning composition is not particularly limited as long as it can be suitably scoured according to the type and state of the laundry, tableware, or fiber to be treated. For example, when scouring a cotton fabric using protopectinase as pectinase, the concentration of protopectinase in the scouring agent is preferably 1 to 2000 units / ml, more preferably 10 to 1000 units / ml. 20 to 500 units / ml are more preferable.

(Anionic surfactant)
The detergent composition of the present invention essentially contains an anionic surfactant (B) obtained by anionizing a (poly) alkylene oxide adduct of an aliphatic amine having 8 to 18 carbon atoms in addition to the enzyme (A) described above. To do. Such an anionic surfactant (B) has excellent penetrability and wettability and does not inhibit the activity of the enzyme. The cleaning composition of the present invention has an anionic surfactant (B) as an enzyme (A). Since it is used in combination, it is excellent in work environment, permeability, wettability and cleanability. Further, such an anionic surfactant (B) does not deactivate or inhibit the enzyme activity even when mixed with the enzyme for a long period of time, and is excellent in stability over time of the detergent composition.
In the anionic surfactant (B), when the aliphatic amine has less than 8 carbon atoms, sufficient oil agent removability and anti-redeposition effect cannot be obtained. On the other hand, when the aliphatic amine has more than 18 carbon atoms, sufficient permeability cannot be obtained, so that a sufficient cleaning effect cannot be obtained.

The (poly) alkylene oxide adduct of an aliphatic amine having 8 to 18 carbon atoms herein refers to an ethylene oxide group (EO) or propylene oxide group (PO) to a primary amine or secondary amine having 8 to 18 carbon atoms. ) And at least one (poly) alkylene oxide group selected from butylene oxide (BO). These may constitute any of a block adduct, an alternating adduct, or a random adduct.
The anionization here refers to introducing an anionic group such as a carboxyl group, a phosphoric acid group, a sulfonic acid group, or a sulfuric ester group into the molecule by a chemical reaction such as an addition reaction, a substitution reaction, or a condensation reaction. . Among these, an amino ether carboxylic acid type anionic surfactant having a carboxyl group introduced into the molecule of the (poly) alkylene oxide adduct or a phosphate group introduced into the molecule of the (poly) alkylene oxide adduct. Amino ether phosphate type anionic surfactants are preferred, and amino ether carboxylic acid type anionic surfactants are particularly preferred.

Among the above, the anionic surfactant (B) used in the present invention is preferably a compound represented by the above general formula (1). In the general formula (1), R represents an aliphatic hydrocarbon group having 8 to 18 carbon atoms. The aliphatic hydrocarbon group may be saturated or unsaturated, and may be linear or branched. In terms of excellent penetrability and biodegradability, the aliphatic hydrocarbon group preferably has a branched structure. The number of carbon atoms of the aliphatic hydrocarbon group is preferably 8 to 16, more preferably 10 to 16, and further preferably 10 to 14.

Examples of the aliphatic hydrocarbon group include n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, isodecyl, n-undecyl, n-dodecyl, isododecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, Octadecyl and the like can be mentioned, and among these, a branched structure is preferable in terms of excellent penetrability and biodegradability, and isodecyl and isotridecyl are more preferable.

In the general formula (1), AO represents at least one alkylene oxide group selected from an ethylene oxide group (EO) and a propylene oxide group (PO). AO may be composed of EO or PO alone, and may be composed of a block adduct, an alternating adduct, or a random adduct of EO and PO. Among these, AO is preferably an ethylene oxide group (EO).

In the general formula (1), X represents a (CH ₂ ) _p COOM group or a hydrogen atom. X is preferably a (CH ₂ ) _p COOM group in terms of excellent permeability.
M represented by the general formula (1) and X represents a hydrogen atom or an alkaline group. Examples of the alkaline group include alkali metals such as Li, Na, and K, alkaline earth metals such as Ca and Mg, ammonium salts, amine salts, and quaternary ammonium salts. Examples of the quaternary ammonium salt include alkyltrimethylammonium chloride salt and dialkyldimethylammonium chloride salt. Further included are mixtures of any of the above materials. Among these, M is preferably an alkali metal, more preferably Na or K.

In general formula (1), m and n each independently represents an integer of 1 to 50. Among them, m and n are preferably 1 to 20, more preferably 2 to 10, and further preferably 3 to 7.
In the general formula (1), p represents an integer of 1 to 3, and 2 is preferable.

The weight ratio (A / B) of the enzyme (A) and the anionic surfactant (B) used in the present invention is preferably 5/95 to 99/1. When the weight ratio (A / B) is less than 5/95, the removal of soil by the enzyme may not be sufficiently exhibited, and when it exceeds 99/1, the permeability may not be sufficient. The weight ratio (A / B) is more preferably 20/80 to 90/10, further preferably 30/70 to 80/20, and particularly preferably 40/60 to 70/30.

As the method for producing the anionic surfactant (B) used in the present invention, a known method can be employed. For example, an addition reaction between an ethylene oxide adduct of an aliphatic amine having 8 to 18 carbon atoms, which is a nonionic surfactant, and an acrylate, or ether carboxy (salt) formation by a reaction with monochloroacetic acid.

(Nonionic surfactant)
The cleaning composition of the present invention preferably further contains a nonionic surfactant (C) from the viewpoint of preventing re-deposition of the removed soil component, particularly the oil component.
The nonionic surfactant (C) may be a known nonionic surfactant used in detergents for clothes, dishwashing detergents, scouring agents, etc., for example, polyoxyethylene hexyl ether, polyoxyethylene octyl ether, poly Polyoxyalkylene linear alkyl ethers such as oxyethylene decyl ether, polyoxyethylene lauryl ether, polyoxyethylene polyoxypropylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene polyoxypropylene oleyl ether; Polyoxyalkylene branched primary alkyl ethers such as polyoxyethylene 2-ethylhexyl ether, polyoxyethylene isocetyl ether, polyoxyethylene isostearyl ether; Polyoxyalkylene branches such as polyethylene 1-hexyl hexyl ether, polyoxyethylene 1-octyl hexyl ether, polyoxyethylene 1-hexyl octyl ether, polyoxyethylene 1-pentyl heptyl ether, polyoxyethylene 1-heptyl pentyl ether Secondary alkyl ethers; polyoxyalkylene alkenyl ethers such as polyoxyethylene oleyl ether; polyoxyalkylene alkyl aryl ethers such as polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether; polyoxy Alkylene aryl ethers; polyoxyalkylene alkyl amines, aliphatic alkanolamides, polyoxyalkylene fats Amides; polyhydric alcohol fatty acid esters (glycerin fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester, etc.), polyoxyalkylene glycol, fatty acid polyethylene glycol, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxy Fatty acid polyoxyalkylene sorbitans such as ethylene sorbitan laurate and polyoxyethylene sorbitan octylate; polyoxyalkylene castor oil ethers such as polyoxyethylene castor oil ether; polyoxyalkylene cured castor oil ethers such as polyoxyethylene hydrogenated castor oil ether Oxyethylene-oxypropylene block or random copolymer; oxyethylene-oxypropylene block or run Examples include terminal alkyl etherified products of dam copolymers; terminal sucrose etherified products of oxyethylene-oxypropylene blocks or random copolymers. The nonionic surfactant (C) may be used alone or in combination of two or more.
Among these nonionic surfactants, polyoxyalkylene alkyl ethers, fatty acid polyalkylene glycols, fatty acid alkanolamides and the like are preferable because they improve the permeability and wettability to the object to be cleaned and prevent reattachment of the removed oil agent.

The nonionic surfactant (C) is preferably a nonionic surfactant having an HLB of 8 to 18 by the Griffin method in order to prevent the redeposition of the soil components, and since a cleaning effect is also obtained, the HLB is 12 to 15 More preferred are nonionic surfactants.

(Other ingredients)
The cleaning composition of the present invention may contain other components within a range that does not inhibit the effects of the present invention, particularly within a range that does not inhibit the enzyme activity. Other components include general desizing agents, scouring agents, pH buffering agents used in cleaning agents; chelating agents; polyoxyalkylene ethers, silicone oils, mineral oils, natural fatty acid salts (coconut oil fatty acid potassium salt) Etc.); an enzyme stabilizer, an enzyme activator and the like.

When used as a liquid, the detergent composition of the present invention comprises an enzyme (A) and an anionic surfactant (B), and if necessary, a nonionic surfactant (C) as a solvent such as water, alcohols or polyethylene glycol. It is dissolved in In consideration of safety, cost, and environmental impact, it is preferable to use water as the main solvent. The water used in the present invention may be any of pure water, distilled water, purified water, soft water, ion exchange water, tap water and the like. The polyethylene glycol used here preferably has a molecular weight of 600 or less, which is liquid at room temperature, from the viewpoint of workability, and the molecular weight is more preferably 200 to 600, and even more preferably 200 to 400.

The detergent composition of the present invention comprises an enzyme (A), an anionic surfactant (B), and if necessary, a nonionic surfactant (C) mixed with polyethylene glycol having a molecular weight of more than 600 in a powder form. It is good. In this case, the molecular weight of polyethylene glycol is preferably 1000 to 20000, more preferably 1000 to 10000, still more preferably 2000 to 8000, and particularly preferably 4000 to 6000.

In the cleaning composition of the present invention, it is preferable not to use caustic soda used in the oxidation scouring treatment in order to denature the enzyme. Specifically, the weight ratio of caustic soda in the entire nonvolatile content of the cleaning composition is preferably 1% by weight or less, more preferably 0.1% by weight or less, and still more preferably 0.01% by weight or less.

Moreover, the detergent composition of the present invention preferably contains substantially no anionic surfactant, heavy metal (ion) and other enzyme inhibitors that inhibit enzyme activity. Specifically, it is preferably 1% by weight or less, more preferably 0.1% by weight or less, and still more preferably 0.01% by weight or less with respect to the enzyme (A).
Anionic surfactants that inhibit enzyme activity include aliphatic monocarboxylate polyoxyalkylene decyl ether acetate, alkane sulfonate, alkylbenzene sulfonate, alkyl sulfate polyoxyalkylene alkyl ether sulfate, oil and fat Examples thereof include a sulfate ester salt, an alkyl phosphate, a polyoxyalkylene alkyl ether phosphate, and a polyoxyalkylene alkyl phenyl ether phosphate. Examples of heavy metal ions that inhibit enzyme activity include Hg ²⁺ , Cu ²⁺ , Fe ²⁺ , and Al ³⁺ . Examples of enzyme inhibitors that inhibit enzyme activity include vanillin and tannic acid.

(Cleaning composition)
In the cleaning composition of the present invention, the enzyme (A) and the anionic surfactant (B) are preferably contained in the weight ratio (A / B) described above. The total weight ratio of the enzyme (A) and the anionic surfactant (B) in the entire nonvolatile content of the cleaning composition is preferably 10 to 100% by weight, more preferably 10 to 99% by weight, and 25 to 99% by weight. % Is more preferable, 50 to 95% by weight is particularly preferable, and 75 to 90% by weight is most preferable. Here, the non-volatile content (also referred to as solid content) means that a certain amount of the sample is spread flat on an aluminum sheet and dried at 110 ° C. under irradiation with an infrared lamp, and the fluctuation range of volatile content for 150 seconds is 0.15% by weight. This is the remainder when the end point of the measurement is taken.

When the cleaning composition of the present invention further contains a nonionic surfactant (C), the weight ratio of the nonionic surfactant (C) to the whole nonvolatile content of the cleaning composition is 1 to 90% by weight. It is preferably 1 to 85% by weight, more preferably 1 to 75% by weight, particularly preferably 5 to 50% by weight, and most preferably 10 to 25% by weight.

Further, the non-volatile content of the cleaning composition of the present invention is preferably 0.1 to 20 g / L, more preferably 0.5 to 15 g / L, and further preferably 1 to 10 g / L.

The cleaning composition of the present invention includes a cleaning composition for washing clothes including household use and industrial use; a cleaning composition for cleaning including household use and industrial use; a cleaning composition for dishware; Examples thereof include a fiber scouring detergent (also referred to as a scouring agent) composition, which includes a treatment, a fiber-derived resin, and a process for removing impurities such as wax.
Among these, a detergent composition for scouring fibers is particularly suitable. For fiber scouring, it is particularly preferred to be used for fiber desizing.

The method for preparing the cleaning composition of the present invention is not particularly limited, and the mixing order of the enzyme (A), the anionic surfactant (B), the nonionic surfactant (C), water, and the solvent is as long as it can be mixed uniformly. As the addition method, a known method can be adopted.

(Cleaning method)
The cleaning method of the present invention includes a step of cleaning an object to be cleaned using the above-described cleaning composition. Moreover, the case where the washing | cleaning method of this invention includes the process of wash | cleaning to-be-washed | cleaned material using the above-mentioned enzyme (A) and the above-mentioned anionic surfactant (B) may be sufficient. That is, as in the above-described cleaning composition, the object to be cleaned may be cleaned using the enzyme (A) and the anionic surfactant (B) simultaneously. The enzyme (A) and the anionic surfactant (B) Even if it wash | cleans a to-be-washed object separately using an enzyme (A) and an anionic surfactant (B) so that it may wash | clean with the process liquid containing any one of these, and then it wash | cleans with the process liquid containing the other. Good. As the cleaning method of the present invention, it is preferable to clean the article to be cleaned using the enzyme (A) and the anionic surfactant (B) simultaneously.

Examples of the objects to be cleaned include clothes, tableware, and fibers used in the manufacturing process of textile products, which are objects to be washed and cleaned.
In general, natural fibers such as cotton, hemp, and wool are adhered to impurities such as fiber-derived resin and wax. Adhesive components such as sizing oil and glue used during weaving are attached to compound fibers such as polyester, nylon, rayon, and triacetate, blended and woven fibers of these, and blended and woven fibers of these and natural fibers. is doing. If impurities and / or paste components adhering to the fibers are not sufficiently removed in the scouring step, troubles will occur in the subsequent processing steps such as bleaching, dyeing and softening. The fiber used in the textile manufacturing process refers to a woven fabric to which the contaminant and / or the paste component is attached, which is used in the scouring process to remove the contaminant and / or the paste component. . In the cleaning method of the present invention, fabrics to which the paste component is adhered, cotton, hemp, cotton, or a mixed spun fiber of hemp and other fibers in which fiber-derived resin or wax is present are particularly suitable.

Paste components adhering to the above fibers include polyvinyl alcohol, starch (such as corn starch and wheat starch), processed starch, carboxymethyl cellulose and its derivatives, acrylate resins, wax components (paraffin, hydrogenated oil, carnauba) Wax, etc.). Examples of the resin derived from the fibers adhering to the fibers include pectin and the like, and examples of the wax include cotton wax.

When washing or cleaning clothes and the like using the cleaning composition of the present invention, examples of the cleaning method include the following.
Regardless of hand washing or machine use, an object to be cleaned such as clothing is immersed or impregnated in an aqueous solution (cleaning liquid) containing a cleaning composition according to the degree of dirt. It may be soaked, or it may be physically promoted to remove dirt effectively, such as rubbing and tapping. The cleaning temperature may be room temperature, but in cleaning, a high temperature is preferable for efficiently removing dirt, and 40 ° C. or higher is more preferable. In view of not inhibiting the enzyme activity, the pH of the washing solution is preferably 4 to 10, more preferably 5 to 9. After washing, wash with water or hot water to remove the cleaning solution along with dirt.
The non-volatile content concentration in the cleaning liquid may be suitably selected depending on the type and state of the fiber to be processed, and is not particularly limited. For example, when the underwear is washed, the concentration of nonvolatile components in the washing liquid is preferably 0.1 to 20 g / L, more preferably 0.5 to 15 g / L, and further preferably 1 to 10 g / L.

When washing tableware etc. using the detergent composition of the present invention, examples of the washing method include the following.
As a cleaning method for cleaning tableware or the like using an automatic dishwasher, a normal method can be employed using an aqueous solution (cleaning solution) containing the cleaning composition of the present invention. It may be pickled in advance. In order to efficiently remove dirt, a high temperature is preferable, 40 ° C or higher is more preferable, and 60 ° C or higher is particularly preferable. In view of not inhibiting the enzyme activity, the pH of the washing solution is preferably 4 to 10, and more preferably 5 to 9. The non-volatile content concentration in the cleaning liquid may be suitably selected depending on the type and state of the tableware to be processed, and is not particularly limited. For example, the concentration of the nonvolatile content in the cleaning agent is preferably from 0.1 to 20 g / L, more preferably from 0.5 to 15 g / L, and even more preferably from 1 to 10 g / L.
As a dishwashing method for hand-washing, for example, an object to be cleaned such as tableware is impregnated directly or moderately diluted with an aqueous solution (cleaning solution) containing a cleaning composition on a sponge, brush, cloth, etc., and adhered to the tableware. What is necessary is just to remove the dirt. It may be pickled in advance. The concentration of the nonvolatile content in the cleaning liquid is preferably 0.1 to 20 g / L, more preferably 0.5 to 15 g / L, and further preferably 1 to 10 g / L.

When the fiber used in the fiber product production process is washed using the cleaning composition of the present invention (sometimes referred to as a scouring process), examples of the cleaning method including the scouring process include the following. The scouring process includes a desizing process and / or a process for removing impurities such as fiber-derived resin and wax.
The scouring process may be performed by using a scouring machine, and may be either a normal batch system or a continuous system. In a batch type scouring processing machine, a scouring agent (scouring agent) is applied to a woven fabric in which a paste component and / or a fiber-derived resin, a wax or other contaminants (hereinafter referred to as a paste component, etc.) adheres to the treatment bath. Agent) It is immersed in an aqueous solution (cleaning liquid) containing the composition, and after cleaning, the paste component and the like are sufficiently removed together with the cleaning liquid by washing with hot water and / or water. The continuous scouring machine mainly comprises a processing tank (a processing tank called mainly a saturator in the continuous system), a steamer box having squeezing rollers and multistage rolls, a hot water wash and / or a water wash tank. For example, the continuous scouring treatment is performed by filling a saturator tank with a cleaning solution, immersing a woven fabric having a paste component or the like attached thereto, and sequentially passing through a roller and a steamer box. Thereby, the paste component and the like are removed together with the cleaning liquid. Thereafter, the paste component and the like are sufficiently removed together with the washing liquid by washing with hot water and / or washing with water.

The temperature of the scouring treatment is 20 to 140 ° C. depending on the type of fiber. In order to efficiently remove dirt, a high temperature is preferable, and 50 to 110 ° C. is preferable. In the batch method, 80 ° C. or higher is preferable. In a continuous steamer box, 90 ° C. or higher is preferable, and 95 ° C. or higher is more preferable.
The time for the scouring treatment depends on the kind of the glue component and the like attached and the amount of the scouring treatment, but is preferably 5 minutes or more, more preferably 10 minutes or more, and further preferably 20 minutes or more in a batch type scouring treatment machine. If it exceeds 120 minutes, it cannot be said that the workability is good, and it is preferable to perform hot water washing and / or water washing at the stage where the paste components and the like are removed. In a continuous scouring machine, the steaming time is preferably 1 minute or longer, more preferably 3 minutes or longer, and even more preferably 10 minutes or longer. If it exceeds 60 minutes, it cannot be said that workability is good, and it is preferable to perform hot water washing and / or water washing at the stage where the paste component and the like are removed.
Further, the concentration of the nonvolatile content in the cleaning liquid is preferably 0.1 to 20 g / L, more preferably 0.5 to 15 g / L, and further preferably 1 to 10 g / L. In view of not inhibiting the enzyme activity, the pH of the washing solution is preferably 4 to 10, and more preferably 5 to 9.

The scoured fiber is then subjected to normal processing such as bleaching, dyeing, and softening treatment as necessary to obtain a fiber product.

Hereinafter, examples of the present invention will be shown and the present invention will be described in more detail. However, the present invention is not limited to these examples. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

[Preparation of anionic surfactant (B1)]
In a reaction vessel having a capacity of 1 liter equipped with a thermometer, a reflux condenser and a stirrer, in the following general formula (2), amino ether polyoxyethylene (7 mol) isodecyl ether (wherein R is an isodecyl group and m + n is 7) b1) 500 g, ethyl acrylate 155 g, and sodium methylate (24 wt%) 10 g were charged. The mixture was heated with stirring and reacted at 60 ° C. for 2 hours. After adding 40 g of sodium hydroxide and 250 g of soft water, the mixture was further reacted at 90 ° C. for 2 hours, neutralized with hydrochloric acid, desalted, and light yellow transparent amino An anionic surfactant (B1) which is an ether carboxylic acid type anionic surfactant was obtained.
_{RN [(AO) m H]} [(AO) n H] (2)

[Preparation of anionic surfactants (B2 to B10)]
In the preparation of the anionic surfactant (B1), the same procedure was followed except that the amino ether polyoxyethylene (7 mol) isodecyl ether (b1) was changed to the following (b2) to (b10) respectively. Anionic surfactants (B2 to B10) which are carboxylic acid type anionic surfactants were obtained.
Amino ether polyoxyethylene (2 mol) isodecyl ether (b2)
Amino ether polyoxyethylene (10 mol) isodecyl ether (b3)
Amino ether polyoxyethylene (20 mol) isodecyl ether (b4)
Amino ether polyoxyethylene (50 mol) isodecyl ether (b5)
Amino ether polyoxyethylene (7 mol) 2-ethylhexyl (b6)
Amino ether polyoxyethylene (7 mol) n-decyl (b7)
Amino ether polyoxyethylene (7 mol) isotridecyl ether (b8)
Amino ether polyoxyethylene (7 mol) tetradecyl (b9)
Amino ether polyoxyethylene (7 mol) octadecyl (b10)

[Preparation of anionic surfactant (B11)]
In a reaction vessel having a capacity of 1 liter equipped with a thermometer, a reflux condenser, and a stirrer, 500 g of amino ether polyoxyethylene (7 mol) isodecyl ether (b1) was heated with stirring, and 100 g of phosphoric anhydride was gradually added. Prepared. After reacting at 90 ° C. for 2 hours, 40 g of sodium hydroxide and 300 g of soft water were added, followed by further reaction at 90 ° C. for 2 hours, neutralization with hydrochloric acid, desalting, and a pale yellow transparent amino ether phosphate type anionic surface activity An anionic surfactant (B11) as an agent was obtained.

Example 1
A cleaning composition comprising an aqueous solution containing 0.1% by weight of α-amylase (A1) (Wako Pure Chemical Industries) and 0.1% by weight of an anionic surfactant (B1) was prepared. % Starch aqueous solution was mixed at a ratio of 1: 1 to obtain a mixed solution containing 0.05% by weight of α-amylase (A1) and anionic surfactant (B1) and 1% by weight of starch, respectively. When 0.02 N iodine solution was immediately added to this mixed solution so that it might become 0.02 weight%, it confirmed that it exhibited blue. Next, a mixture solution containing 0.05% by weight of α-amylase (A1) and anionic surfactant (B1) prepared in the same manner and 1% by weight of starch was allowed to stand at 40 ° C. for 10 minutes. When the normal iodine solution was added to 0.02% by weight, yellowish brown color was exhibited by the iodo starch reaction, so that it was confirmed that starch was decomposed. The results are shown in Table 1.
[Enzyme activity of detergent composition (after time)]
The enzyme activity of the cleaning composition after aging was confirmed in the same manner as in the above evaluation except that the cleaning composition was changed to the next cleaning composition (after aging). The results are shown in Table 1 as “enzyme activity (after time)”.
Cleaning composition (after time): An aqueous solution containing 25% by weight of α-amylase (A1) and 25% by weight of an anionic surfactant (B1) was allowed to stand at 30 ° C. for 30 days, and then diluted 250 times with soft water. liquid

(Examples 2 to 12, Comparative Examples 1 to 6, Reference Example 1)
In the cleaning composition of Example 1, the same treatment as in Example 1 was performed except that the anionic surfactant (B1) was changed to the surfactants shown in Table 1 and their weight percentages, respectively, and Examples 2 to 12 Comparative Examples 1 to 6 and Reference Example 1 (no anionic surfactant) were used. The results are shown in Table 1. It should be noted that the enzyme activities of the detergent compositions (over time) of Comparative Examples 1 to 6 were not evaluated. The nonionic surfactant (C1) in Tables 1 to 3 represents polyoxyethylene (15 mol) stearyl ether.

As shown in Table 1, it can be seen that the anionic surfactants (B1 to B11) of the examples do not inhibit the enzyme activity of α-amylase. It can also be seen that the anionic surfactants (B1 to B11) of the examples do not inactivate or inhibit the enzyme activity of α-amylase even when mixed with α-amylase for a long time.
Further, the pH (20 ° C.) of the cleaning compositions of Examples 1 to 12 was measured and found to be in the range of 6.0 to 6.5. This shows that the cleaning composition of the present invention is excellent in work environment.

(Example 13)
A cleaning composition comprising an aqueous solution containing 0.1% by weight of cellulase (A2) (Wako Pure Chemical Industries) and 0.1% by weight of an anionic surfactant (B1) was prepared. The methylcellulose solution was mixed at a ratio of 1: 1 to obtain a mixed solution containing 0.05% by weight of cellulase (A2) and anionic surfactant (B1) and 1% by weight of carboxymethylcellulose, respectively. When the viscosity immediately after mixing was immediately measured with a B-type viscometer (20 ° C.), it was 400 mPa · s. The liquid mixture containing this detergent composition was allowed to stand at 40 ° C. for 10 minutes, and when the viscosity was measured immediately, it decreased to 30 mPa · s, and thus the enzyme activity was confirmed. The results are shown in Table 2.
[Enzyme activity of detergent composition (after time)]
The enzyme activity of the cleaning composition after aging was confirmed in the same manner as in the above evaluation except that the cleaning composition was changed to the next cleaning composition (after aging). The results are shown in Table 1 as “viscosity (after time)”.
Detergent composition (after time): A solution obtained by allowing an aqueous solution containing 25% by weight of cellulase (A2) and 25% by weight of anionic surfactant (B1) to stand at 30 ° C. for 30 days, and then diluted 250 times with soft water

(Examples 14 to 24, Comparative Examples 7 to 12, Reference Example 2)
In the cleaning composition of Example 13, the same treatment as in Example 13 was performed except that the anionic surfactant (B1) was changed to the surfactants shown in Table 2 and their weight percentages, respectively, and Examples 14 to 24 Comparative Examples 7 to 12 and Reference Example 2 (no anionic surfactant) were used. The results are shown in Table 2. It should be noted that the enzyme activity of the detergent compositions (time course) of Comparative Examples 7 to 12 was not evaluated.

As shown in Table 2, it can be seen that the anionic surfactants (B1 to B11) of the examples do not inhibit the enzyme activity of cellulase. It can also be seen that the anionic surfactants (B1 to B11) of the examples do not deactivate or inhibit the enzyme activity of cellulase even when mixed with cellulase for a long time.
Further, when the pH (20 ° C.) of the cleaning compositions of Examples 13 to 24 was measured, it was in the range of 6.0 to 6.5. This shows that the cleaning composition of the present invention is excellent in work environment.

(Example 25)
100 g of a detergent composition, which is an aqueous solution containing 0.1% by weight of pectinase (A3) (Wako Pure Chemical Industries) and 0.1% by weight of an anionic surfactant (B1), was prepared, and the detergent composition, warp and weft 100 g of an aqueous solution containing 10 g of cotton cloth using 20 counts of cotton yarn was mixed to obtain 200 g of a mixed solution containing 0.05% by weight of pectinase (A3) and anionic surfactant (B1) and 10 g of cotton cloth, respectively. The mixture was allowed to stand at 40 ° C. for 10 minutes, and then the cotton cloth was taken out, washed thoroughly with water, and dried at 90 ° C. for 60 minutes to obtain a scoured cloth.
The enzyme activity was evaluated by the pectin removal rate and measured as follows. The untreated cotton cloth and the resulting scoured treated cloth were immersed in a solution containing 0.5% by weight caustic soda and 0.1% by weight of polyoxyethylene (15 mol) stearyl ether so as to have a bath ratio of 1:20 and boiled. The pectin remaining on the fiber was decomposed into galacturonic acid by the above, and the extracted galacturonic acid was quantified by absorbance at 235 nm. The results are shown in Table 3.
Pectin removal rate (%) = (galacturonic acid of untreated cotton cloth−galacturonic acid of scoured cloth) ÷ galacturonic acid of untreated cotton cloth × 100
[Enzyme activity of detergent composition (after time)]
The enzyme activity of the cleaning composition after aging was confirmed in the same manner as in the above evaluation except that the cleaning composition was changed to the next cleaning composition (after aging). The results are shown in Table 1 as “pectin removal rate (after time)”.
Detergent composition (after time): Liquid containing 25% by weight of pectinase (A3) and 25% by weight of anionic surfactant (B1), left at 30 ° C. for 30 days, and then diluted 250 times with soft water

(Examples 26 to 36, Comparative Examples 13 to 18, Reference Example 3)
In the cleaning composition of Example 25, the same treatment as in Example 25 was performed except that the anionic surfactant (B1) was changed to the surfactants shown in Table 3 and their weight percentages, respectively, and Examples 26 to 36 were performed. Comparative Examples 13 to 18 and Reference Example 3 (no anionic surfactant) were used. The results are shown in Table 3. It should be noted that the enzyme activities of the detergent compositions (timed) of Comparative Examples 13 to 18 were not evaluated.

As shown in Table 3, it can be seen that the anionic surfactants (B1 to B11) of Examples do not inhibit the enzyme activity of pectinase. It can also be seen that the anionic surfactants (B1 to B11) of the examples do not inactivate or inhibit the enzyme activity of pectinase even when mixed with pectinase for a long time.
Further, when the pH (20 ° C.) of the cleaning compositions of Examples 25 to 36 was measured, it was in the range of 6.0 to 6.5. This shows that the cleaning composition of the present invention is excellent in work environment.

(Example 37)
A plain weave of cotton / polyester blended yarn (65/35% by weight) (70 warps / cotton / polyester blended yarn, 70 weft yarn / 55 cotton / polyester blended yarn / inch) was used as a test fabric. This test cloth had an oil component adhesion rate of 1.06% by weight composed of a wax component and cotton wax, and an adhesion rate of a paste component composed of polyvinyl alcohol, starch, and an acrylate ester resin was 11.50% by weight.
The cleaning method (scouring method) was performed as follows. 150 g of a cleaning agent (scouring agent) composition which is an aqueous solution containing 0.5% by weight of α-amylase (A1) and 0.5% by weight of an anionic surfactant (B1) is prepared and attached to the following scouring apparatus. Placed in staining pot. Next, 10 g of the test cloth was put in a dyeing pot and subjected to scouring treatment at 80 ° C. for 5 minutes under the following scouring treatment conditions. The scoured fabric was sufficiently washed with water and dried in a dryer at 90 ° C. for 60 minutes. The re-wetability, residual fat ratio and residual paste ratio of the scoured treated cloth after drying were measured. The results are shown in Table 4.

<Scouring conditions>
Testing machine: A rotating pot dyeing tester (12EL type) manufactured by Tecsum Giken Co., Ltd. was used.
Fabric amount: 10g
Treatment concentration: detergent composition containing 0.5% by weight of α-amylase (A1) and 0.5% by weight of anionic surfactant (B1) Treatment bath: 99% by weight of tap water as a solvent Scouring temperature × scouring time : 80 ° C x 5 minutes bath Ratio: 1:15
Washing with water: 60 seconds Drying: 90 ° C x 60 minutes Number of rotations of dyeing pot: 50 rpm

The Examples and Comparative Examples were evaluated by the following methods.
<Residual fat percentage>
The scoured cloth was extracted with a Soxhlet extractor using hexane, and the residual fat ratio was measured. Under these conditions, the residual fat ratio is desirably 0.25% or less.
<Residual paste ratio>
After measuring the residual fat ratio, the scoured cloth is washed with boiling water for 1 hour in a solution containing 1.5% by weight of sodium hydroxide, 0.1% by weight of polyethylene ethylene (10 mol) lauryl ether and 0.1% by weight of sodium dodecyl sulfate. Thereafter, the residual paste ratio was measured from the change in weight. Under this condition, it is desirable that the residual paste rate is 3% or less.
<Penetration>
Cotton twill high-density production machine (warp 30/2 cotton 99 / inch, weft 10 cotton 88 / inch) Float 1.5cm square on the liquid surface of each cleaning composition at 30 ° C and contact The time until settling was measured for 5 sheets. Under this condition, the permeability is desirably 140 seconds or less.
<Rewetability>
Based on the judgment criteria that 0.1 ml of a direct dye (Sumlight Supra Turquoise Blue G conc.) Solution (5 g / L) is dropped on the scoured cloth, and the spread is sufficiently large and the weft is not uneven. Appearance was judged.
A: Good (the dyeing solution dripped with the background is sufficiently large and round)
○: Middle (stained dripping solution greatly spreads but the shape is distorted)
Δ: bad (stained dripping solution spreads, but small and distorted in shape),
×: Not wet

(Examples 38 to 58, Comparative Examples 19 to 25)
Examples 38 to 58 and Comparative Examples 19 to 25 were evaluated in the same manner as in Example 37, except that the cleaning composition of Example 37 was changed to the cleaning compositions shown in Tables 4 to 6. The results are shown in Tables 4-6. The nonionic surfactants (C1 to C4) in Tables 4 to 6 are as follows.
Nonionic surfactant (C1): Polyoxyethylene (15 mol) stearyl ether Nonionic surfactant (C2): Polyoxyethylene (10 mol) stearyl ether Nonionic surfactant (C3): Polyoxyethylene (15 Mol) oleyl ether nonionic surfactant (C4): polyoxyethylene (10 mol) lauryl ether

As shown in Tables 4 to 6, the cleaning composition of the present invention exhibits excellent oil-removability, desizing, penetrability, and wettability, and a scouring-treated cloth excellent in rewetting is obtained by scouring. I understand that
Further, the pH (20 ° C.) of the cleaning compositions of Examples 38 to 58 was measured and found to be in the range of 6.0 to 6.5. This shows that the cleaning composition of the present invention is excellent in work environment.

(Example 59)
20 g of cooked rice was placed on a petri dish in a circle with a diameter of 4 cm, and 20 mL of 20% by weight of kaleau was hung from it and allowed to stand for 2 hours to prepare a sample for evaluating food stains. The washing method was as follows.
1 kg of a detergent composition, which is an aqueous solution containing 0.1% by weight of α-amylase (A1) and 0.1% by weight of an anionic surfactant (B1), was prepared in a vat, and a sample for food dirt evaluation was gently immersed. . After leaving still at 40 ° C. for 20 minutes, the sample was taken out and placed at an angle of 45 ° C., and 100 mL of 40 ° C. water was applied from the top of the soil, and the remaining soil was visually judged based on the following criteria. The results are shown in Table 7.
○: Good (no dirt remains)
Δ: Intermediate (slightly dirty)
×: Defect (dirt remains)

(Examples 60 to 70, Comparative Examples 26 to 31 and Reference Example 4)
The cleaning composition of Example 59 was treated in the same manner as in Example 59 except that the anionic surfactant (B1) was changed to the surfactants shown in Table 7 and their weight percentages, respectively. Examples 60 to 70 Comparative Examples 26 to 31 and Reference Example 4 (no anionic surfactant) were used. The results are shown in Table 7.
As shown in Table 7, it can be seen that the cleaning composition of the present invention is excellent in soil removability.

The cleaning composition of the present invention contains an enzyme and a specific anionic surfactant that does not inhibit the enzyme activity. The detergent composition of the present invention is particularly suitable for the case where a detergent using an enzyme further imparts excellent work environment properties, permeability, wettability, and washability.

Claims

At least one enzyme (A) selected from amylase, cellulase, and pectinase, and an anionic surfactant (B) obtained by anionizing a (poly) alkylene oxide adduct of an aliphatic amine having 8 to 18 carbon atoms, Cleaning composition.
The cleaning composition of Claim 1 whose said anionic surfactant (B) is a compound shown by following General formula (1).
RN [(AO) m (CH 2) p COOM] [(AO) n X] (1)
(In the formula, R represents an aliphatic hydrocarbon group having 8 to 18 carbon atoms. AO represents at least one alkylene oxide group selected from an ethylene oxide group (EO) and a propylene oxide group (PO). May constitute a block adduct, an alternating adduct, or a random adduct, X represents a (CH 2 ) p COOM group or a hydrogen atom, M represents a hydrogen atom or an alkaline group, and m and n represents an integer of 1 to 50, and p represents an integer of 1 to 3.)
In the general formula (1) of the anionic surfactant (B), R is an aliphatic hydrocarbon group having 10 to 16 carbon atoms, AO is an ethylene oxide group (EO), and m and n are 2 to 10 The cleaning composition according to claim 2, wherein
The weight ratio (A / B) of the enzyme (A) to the anionic surfactant (B) is 5/95 to 99/1, and the enzyme (A) and the anion occupy the entire nonvolatile content of the cleaning composition. The cleaning composition according to any one of claims 1 to 3, wherein the total weight ratio of the surfactant (B) is 10 to 100% by weight.
The nonionic surfactant (C) is further included, and the nonionic surfactant (C) has a weight ratio of 1 to 90% by weight based on the whole nonvolatile content of the cleaning composition. The enzyme (A) and the enzyme The cleaning composition according to any one of claims 1 to 4, wherein the total weight ratio of the anionic surfactant (B) is 10 to 99% by weight.
The cleaning composition according to any one of claims 1 to 5, wherein the cleaning composition is used for scouring fibers.
A cleaning method comprising a step of cleaning an object to be cleaned using the cleaning composition according to any one of claims 1 to 6.
The cleaning method according to claim 7, wherein the object to be cleaned is a fiber, and the step is a step of scouring the fiber using a fiber scouring detergent composition.
A fiber scoured by the method according to claim 8.
Washing with at least one enzyme selected from amylase, cellulase and pectinase (A) and an anionic surfactant (B) obtained by anionizing a (poly) alkylene oxide adduct of an aliphatic amine having 8 to 18 carbon atoms A cleaning method comprising a step of cleaning an object.
The washing | cleaning method of Claim 10 whose said anionic surfactant (B) is a compound shown by following General formula (1).
RN [(AO) m (CH 2) p COOM] [(AO) n X] (1)
(In the formula, R represents an aliphatic hydrocarbon group having 8 to 18 carbon atoms. AO represents at least one alkylene oxide group selected from an ethylene oxide group (EO) and a propylene oxide group (PO). May constitute a block adduct, an alternating adduct, or a random adduct, X represents a (CH 2 ) p COOM group or a hydrogen atom, M represents a hydrogen atom or an alkaline group, and m and n represents an integer of 1 to 50, and p represents an integer of 1 to 3.)
The cleaning method according to claim 10 or 11, wherein the object to be cleaned is a fiber, and the step is a step of scouring the fiber using the enzyme (A) and the anionic surfactant (B).
A fiber scoured by the method according to claim 12.