JP2016060888A - Liquid detergent composition for spray, and detergent packed in spray container using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid detergent composition for spray, having high safety and good dispersion stability, capable of being atomized by spraying, and being free from liquid sagging after spraying, and to provide a detergent packed in a spray container using the same.SOLUTION: The liquid detergent composition for spray comprises a component (A), a component (B), and a component (C). (A) Cellulose fiber having a number average fiber diameter of 2 nm or more and 500 nm or less, in which hydroxyl groups in the cellulose molecules are substituted with a degree of substitution of 0.01 or more and 0.5 or less, and the fiber has a crystal structure of type I or type II and an aspect ratio of 50 or more; (B) a surfactant; and (C) water.SELECTED DRAWING: None

Description

  The present invention relates to a liquid detergent composition for spray and a detergent contained in a spray container using a sole.

  Liquid detergent compositions are widely used in industrial and household applications. In particular, when used as a cleaning agent for kitchen sinks, bathtubs, bathrooms, screen doors, etc. at home, the cleaning agent is allowed to adhere to the object to be cleaned without touching the liquid cleaning agent from the viewpoint of user convenience. After adhering, it is required that the cleaning operation can be performed without rubbing or the like and without touching the cleaning agent. By uniformly adhering and retaining the cleaning composition on the object to be cleaned, the cleaning workability and cleaning efficiency increase, so cleaning of kitchen sinks, glass doors, screen doors, houses, bathtubs, bathroom walls, etc. A cleaning agent is applied by spraying.

  Then, after evenly adhering, if it stays attached to the object to be cleaned for a certain period of time without sagging, it can be washed without rubbing, that is, without touching the cleaning agent directly. Since the work can be performed, the convenience of the worker is good. In order to prevent liquid sag, it is preferable that the viscosity of the cleaning composition is high, so that a thickener is blended. In addition to the purpose of improving the above convenience in use, various thickeners are blended in the liquid detergent composition for the purpose of improving the stability of the liquid detergent composition.

  Conventionally, fatty acid alkanolamides are most often used as thickeners in liquid detergent compositions. However, since fatty acid alkanolamides contain nitrogen atoms in the molecular structure, there is a problem that coloring with time occurs depending on the blending conditions. The fatty acid alkanolamides contain N-nitrosodiethanolamine as an impurity, which has been pointed out by the US Food and Drug Administration as being carcinogenic, and has a problem with safety.

  Under such a background, as a conventional liquid detergent composition, for example, a liquid detergent composition (Patent Document 1) containing propylene glycol monofatty acid ester as a thickener or an alkyl having a specific structure A liquid detergent composition (Patent Document 2) containing polyglyceryl ethers as a thickener has been proposed.

JP-A-62-84196 JP 2006-348073 A

  However, the thickener used in the liquid detergent composition described in Patent Documents 1 and 2 cannot satisfy both the thickening effect and the spray characteristics. In other words, increasing the blending amount of the thickener increases the viscosity of the cleaning composition, so that dripping can be prevented, but since the viscosity increases, spraying by spray becomes impossible, and a cleaning agent is added to the object to be cleaned. The problem that it becomes impossible to adhere uniformly occurs. Conversely, if the blending amount of the thickener is decreased, the viscosity of the cleaning composition decreases, so spraying by spraying becomes possible, but liquid sag occurs after the cleaning agent is sprayed on the cleaning target, and the cleaning target There was a problem that the cleaning agent could not stay in the product. As described above, the liquid detergent composition using the conventional thickener cannot achieve both the thickening effect and the spray characteristics.

  The present invention has been made in view of such circumstances, and is a liquid detergent composition for spraying that has high safety, good dispersion stability, can be sprayed by spraying, and does not generate liquid dripping after spraying. It is an object of the present invention to provide a product and a cleaning agent containing a spray container using the product.

  The inventors of the present invention have intensively studied to solve the above problems, and as a result, have found that the above problems can be solved by using specific cellulose fibers, surfactants, and water. It came to complete.

That is, the present invention relates to the invention described below.
(1) A liquid detergent composition for spraying containing (A) component, (B) component, and (C) component.
(A) Cellulose fibers having a number average fiber diameter of 2 nm or more and 500 nm or less, wherein a substituent is introduced into the hydroxyl group in the cellulose molecule, the degree of substitution is 0.01 or more and 0.5 or less, type I and Cellulose fibers having an / II type crystal structure and an aspect ratio of 50 or more.
(B) Surfactant.
(C) Water.
(2) The liquid detergent composition for spraying according to claim 1, wherein the content (solid content mass) of component (A) is in the range of 0.2 to 5.0 mass% of the whole liquid detergent composition for spraying. object.
(3) A spray container-containing cleaning agent, which is filled with the spray liquid cleaning composition according to (1) or (2).

  According to the present invention, a liquid detergent composition for spraying and cleaning in a spray container using the same, which has high safety, good dispersion stability, can be sprayed by spraying, and does not cause dripping after spraying. An agent can be provided.

The liquid detergent composition for spray of this invention contains (A) component, (B) component, and (C) component.
(A) Cellulose fibers having a number average fiber diameter of 2 nm or more and 500 nm or less, wherein a substituent is introduced into the hydroxyl group in the cellulose molecule, the degree of substitution is 0.01 or more and 0.5 or less, type I and Cellulose fibers having an / II type crystal structure and an aspect ratio of 50 or more.
(B) Surfactant.
(C) Water.

  The cellulose fiber (A) of the present invention is a cellulose fiber having a number average fiber diameter of 2 nm or more and 500 nm or less, wherein a substituent is introduced into a hydroxyl group in the cellulose molecule, and the degree of substitution is 0.01 or more and 0.5. It has a crystal structure of type I and / or type II and an aspect ratio of 50 or more.

  The number average fiber diameter of the (A) cellulose fiber of the present invention is 2 nm to 500 nm, preferably 2 nm to 150 nm. If it is these ranges, it is preferable from the liquid detergent composition for sprays becoming uniform, without a cellulose fiber settling.

  In the present invention, the analysis of the number average fiber diameter can be performed, for example, as follows. Specifically, an aqueous dispersion of cellulose fibers having a solid content of 0.05 to 0.1% by mass was prepared, and the dispersion was cast on a carbon film-coated grid that had been subjected to a hydrophilic treatment, and a transmission electron microscope. (TEM) observation sample. In addition, when the fiber of the big fiber diameter outside this invention is included, you may observe the scanning electron microscope (SEM) image of the surface cast on glass. Then, observation with an electron microscope image is performed at a magnification of 5000 times, 10000 times, or 50000 times depending on the size of the constituent fibers. At that time, an axis having an arbitrary vertical and horizontal image width is assumed in the obtained image, and the sample and observation conditions (magnification, etc.) are adjusted so that 20 or more fibers intersect the axis. Then, after obtaining an observation image that satisfies this condition, two random axes, vertical and horizontal, per image are drawn on this image, and the fiber diameter of the fiber that intersects the axis is visually read. In this way, images of at least three non-overlapping surface portions are taken with an electron microscope, and the fiber diameter values of the fibers intersecting with each of the two axes are read (thus, at least 20 × 2 × 3 = 120). Information on the fiber diameter of the book is obtained). The number average fiber diameter is calculated from the fiber diameter data thus obtained.

  The substituent introduced into the hydroxyl group in the cellulose molecule in the cellulose fiber (A) of the present invention is not particularly limited as long as it is a substituent that generates an ether bond with the hydroxyl group in the cellulose molecule. Examples thereof include carboxymethyl group, methyl group, ethyl group, cyanoethyl group, hydroxyethyl group, hydroxypropyl group, ethylhydroxyethyl group, hydroxypropylmethyl group and the like. Of these, a carboxymethyl group is preferred.

  The degree of substitution in the (A) cellulose fiber of the present invention refers to the average value of the number of moles of substituents per mole of anhydroglucose unit. The degree of substitution is 0.01 or more and 0.5 or less, preferably 0.01 or more and 0.25 or less. Within these ranges, the cellulose fibers are preferably defibrated, have good thickening and dispersion stability, and do not have spinnability or stickiness.

The (A) cellulose fiber of the present invention has a crystal structure of type I and / or type II. Having a crystal structure is, for example, an X-ray diffraction pattern typical of cellulose type I or type II (type I: diffraction angle 2θ = 12.1 °, 19 in a diffraction profile obtained by wide-angle X-ray diffraction image measurement. .8 °, 22.0 °, type II: diffraction angle 2θ = 12.1 °, 19.8 °, 22.0 °).

  The (A) cellulose fiber of the present invention has an aspect ratio of 50 or more. More preferably, it is 100 or more. When the aspect ratio is 50 or more, the gel property of the gel composition is well maintained.

The aspect ratio of the cellulose can be measured by the following method, that is, a TEM image (magnification: 10000) negatively stained with 2% uranyl acetate after the cellulose is cast on a carbon film-coated grid that has been hydrophilized. The number average width of the short width and the number average width of the long width were observed. That is, according to each method described above, the number average width of the shorter width and the number average width of the longer width were calculated, and the aspect ratio was calculated according to the following formula using these values.
Aspect ratio = Number average width (nm) for longer width / number average width (nm) for shorter width

  In order to obtain the cellulose fiber (A) of the present invention, the cellulose exemplified below needs to be anion-modified using a known method. The following manufacturing method can be mention | raise | lifted as the example. Cellulose is used as a raw material, and the solvent is 3 to 20 times lower alcohol, specifically methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, etc. alone, or Use a mixture of two or more mixtures and water. In addition, the mixing ratio of a lower alcohol is 60-95 mass%. As the mercerizing agent, 0.5 to 20 times moles of alkali metal hydroxide, specifically sodium hydroxide or potassium hydroxide is used per glucose residue of cellulose. Cellulose is formed by mixing cellulose, a solvent, and a mercerizing agent. The reaction temperature at this time is 0 to 70 ° C., preferably 10 to 60 ° C., and the reaction time is 15 minutes to 8 hours, preferably 30 minutes to 7 hours. Thereafter, the etherification reaction is carried out by adding 0.05 to 10-fold mol of carboxymethylating agent per glucose residue. The reaction temperature at this time is 30 to 90 ° C., preferably 40 to 80 ° C., and the reaction time is 30 minutes to 10 hours, preferably 1 to 4 hours.

  Although the cellulose raw material of the present invention is not particularly limited, for example, natural cellulose such as cellulose produced by microorganisms such as bleached or unbleached wood pulp, refined linter, acetic acid bacteria, cellulose as a copper ammonia solution, morpholine derivative, etc. Regenerated cellulose dissolved in some solvent and re-spun, and fine cellulose that has been depolymerized by hydrolysis, alkali hydrolysis, enzymatic degradation, explosion treatment, vibration ball milling, etc. Cellulose is exemplified.

  Although the cellulose fiber of this invention is not specifically limited, For example, it can obtain by carrying out the fibrillation process of the anion-modified cellulose with a high pressure homogenizer etc. A high-pressure homogenizer is a device that pressurizes a fluid with a pump and ejects it from a very delicate gap provided in a flow path. It is possible to emulsify, disperse, defibrate, grind, and make ultrafine particles by using total energy such as collision between particles and shear force due to pressure difference.

  The treatment conditions with the homogenizer of the present invention are not particularly limited, but the pressure conditions are 30 MPa or more, preferably 100 MPa or more, more preferably 140 MPa or more. In addition, prior to defibration / dispersion treatment with a high-pressure homogenizer, if necessary, pretreatment of anion-modified cellulose is performed using a known mixing, stirring, emulsifying, and dispersing device such as a high-speed shear mixer. Is also possible.

  Content (solid content mass) of the said specific cellulose fiber (A component) in the liquid cleaning composition of this invention is 0.05-5.0 mass% of the whole liquid cleaning composition as a cellulose fiber solid content. The range is preferably 0.1 to 3.0% by mass. Within these ranges, dripping, economy and manufacturability are good.

  Although it does not specifically limit as surfactant (B component) of this invention, For example, anionic surfactant, nonionic surfactant, cationic surfactant, amphoteric surfactant etc. are mention | raise | lifted. These can be used alone or in combination of two or more. These surfactants (component B) are detergency, emulsifying properties, penetrating power, acid stability, alkali stability, heat resistance, foaming properties, biodegradability depending on the purpose and application of the liquid detergent composition. Selection can be made in consideration of sex and the like.

<Anionic surfactant>
Examples of the anionic surfactant include alkyl (carbon number 10 to 15) benzenesulfonate, alkyl (carbon number 6 to 18) sulfate ester, polyoxyalkylene (addition mole number 1 mol to 30 mol) alkyl ( C6-C18) ether sulfate ester salt, fatty acid (C6-C18) salt, alkane (C6-C18) sulfonate, olefin (C8-C18) sulfonate, naphthalene sulfonate condensation , Alkyl (carbon number 6-18) sulfosuccinic acid ester salt, polyoxyalkylene (addition mole number 1 mol-30 mol) alkyl (carbon number 6-18) ether sulfosuccinate, alkyl (carbon number 6-18) phosphorus Acid ester salt, polyoxyalkylene (addition mole number 1 mol-30 mol) alkyl (carbon number 6-18) ether phosphate ester Salt, polyoxyalkylene (addition mole number 1 mole to 30 mole) alkyl (carbon number 6-18) ether acetate and the like. Examples of the salt include alkali metals such as sodium and potassium, alkaline earth metals such as calcium and magnesium, and amines such as ammonia and alkanolamine. These can be used alone or in combination of two or more.

<Nonionic surfactant>
Examples of the nonionic surfactant include polyoxyalkylene (addition mole number 1 to 50 mol) alkyl (carbon number 6 to 18) ether, polyoxyalkylene (addition mole number 1 to 50 mol) acyl (carbon). Formula 6-18) ester, alkyl (C6-18) diethanolamide, polyoxyalkylene (addition mole number 1 mol-100 mol) triglyceride (fatty acid carbon number 6-18) ether, sorbitan fatty acid (C6-18) ) Ester, sucrose fatty acid (carbon number 6-18) ester, polyoxyalkylene (addition mole number 1 mol-50 mol) sorbitan fatty acid (carbon number 6-18) ester, alkyl (carbon number 6-18) polyglycoside, Examples include polyoxyethylene polyoxypropylene block polymers. These can be used alone or in combination of two or more.

<Cationic surfactant>
Examples of the cationic surfactant include monoalkyl (carbon number 6 to 18) amine salt, dialkyl (carbon number 6 to 18) amine salt, trialkyl (carbon number 6 to 18) amine salt, alkyl (carbon number 6). -18) Trimethylammonium salt, dialkyl (C6-18) dimethylammonium salt, alkyldimethylbenzylammonium salt, alkyl (C6-18) dimethylaminopropylamide and the like. 1 type (s) or 2 or more types can be used. Examples of the salt include halogens such as chlorine and bromine.

<Amphoteric surfactant>
Examples of the amphoteric surfactant include alkyl (carbon number 6-18) betaine, fatty acid (carbon number 6-18) amidopropyl betaine, 2-alkyl (carbon number 6-18) -N-carboxylmethyl-N-. Examples thereof include hydroxyethyl-imidazolinium betaine, alkyl (carbon number 6-18) diethylenetriaminoacetic acid, dialkyl (carbon number 6-18) diethylenetriaminoacetic acid, alkyl (carbon number 6-18) amine oxide, and the like. 1 type (s) or 2 or more types can be used.

  The content of the surfactant (component B) is preferably in the range of 0.1 to 80.0% by mass, more preferably in the range of 0.2 to 50.0% by mass of the entire liquid detergent composition. . If it is these ranges, a cleaning effect and handling property will become favorable.

  The liquid detergent composition for spray of the present invention contains water (component C). In the liquid detergent composition of the present invention, the remaining amount excluding the contents of the A component and the B component and the following optional components is the content of water (C component).

  In the liquid detergent composition of the present invention, an optional component (D component) can be used within a range that does not impair the effects of the liquid detergent composition of the present invention.

  Although it does not specifically limit as said arbitrary component (D component), For example, a natural extract, a builder component, a powder component, fats and oils, solvents, antifoaming agents, water-soluble polymer, antiseptic | preservative, disinfectant, antioxidant Agents, vitamins, sugars / glycols, fragrances, bleaches, acids, alkalis, enzymes, colorants and the like. These can be used alone or in combination of two or more.

<Natural extract>
The natural extract is not particularly limited. Etc. These can be used alone or in combination of two or more.

<Builder component>
The builder component is not particularly limited. For example, sodium tripolyphosphate, sodium pyrophosphate, silicate, carbonate, borate, sulfate, zeolite, nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, oxalic acid , Tartaric acid, citric acid, gluconic acid, polyacrylic acid, maleic anhydride polymer, alginic acid, carboxymethylcellulose, carboxymethyl starch and the like. These can be used alone or in combination of two or more.

<Powder component>
The powder component is not particularly limited. For example, talc, kaolin, mica, sericite, magnesium carbonate, zirconium silicate, aluminum silicate, barium silicate, calcium silicate, zinc silicate, magnesium silicate, strontium silicate, tungstate, Silica, zeolite, barium sulfate, calcined gypsum, calcium phosphate, fluorine apatite, hydroxyapatite, ceramic powder, activated carbon, metal soaps, boron nitride, polyamide powder, polyethylene powder, acrylic resin powder, polystyrene powder, benzoguanamine resin powder, melamine resin powder , Polytetrafluoroethylene powder, cellulose powder and the like. These can be used alone or in combination of two or more.

<Oils and fats>
The fats and oils are not particularly limited, for example, salad oil, rapeseed oil, cottonseed oil, avocado oil, camellia oil, grape seed oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, sunflower oil, egg yolk oil, Sesame oil, Persic oil, Wheat germ oil, Sasanka oil, Castor oil, Linseed oil, Saflower oil, Eno oil, Soybean oil, Peanut oil, Tea seed oil, Kaya oil, Rice bran oil, Sinagiri oil, Kiri oil, Jojoba oil, Germ oil, trioctanoic acid glyceride, triisopalmitic acid glyceride, cocoa butter, coconut oil, horse tallow, hydrogenated coconut oil, palm oil, beef tallow, sheep fat, hardened beef tallow, palm kernel oil, pork tallow, molasses, beeswax, carnauba wax, Montan wax, nukarou, lanolin, kapok wax, lanolin acetate, liquid lanolin, sugarcane wax, lanolin fatty acid isop Pill, hexyl laurate, reduced lanolin, jojoba wax, hard lanolin, shellac wax, liquid paraffin, ozokerite, squalene, pristane, paraffin, squalane, petrolatum, microcrystalline wax, lauric acid, myristic acid, palmitic acid, behenic acid, oleic acid, 12-hydroxystearic acid, undecylenic acid, tall oil fatty acid, coconut oil fatty acid, palm fatty acid, palm kernel fatty acid, isostearic acid, linoleic acid, linolenic acid, eicosapentaenoic acid, docosahexaenoic acid, saturated and unsaturated with 6 to 20 carbon atoms Examples thereof include alcohols, saturated and unsaturated esters having 2 to 20 carbon atoms, and the like. These can be used alone or in combination of two or more.

<Solvents>
Although it does not specifically limit as said solvents, For example, C1-C8 alcohols, such as methanol and ethanol, ester, ketones, hydrocarbons, ethers, glycols, etc. are mention | raise | lifted. These can be used alone or in combination of two or more.

<Antifoaming agent>
Although it does not specifically limit as said antifoamer, For example, a silicone type compound, polyoxyalkylene ether, etc. are mention | raise | lifted. These can be used alone or in combination of two or more.

<Water-soluble polymer>
The water-soluble polymer is not particularly limited. For example, carboxymethylcellulose, methylcellulose, hydroxypropylmethylcellulose, hydroxyethylcellulose, guar gum, xanthan gum, alginic acid, pectin, polyvinyl alcohol, polyacrylic acid, polyvinylpyrrolidone, hyaluronic acid, carboxyvinyl. Examples include polymers, carrageenan, gum arabic, polyethylene oxide, polyethylene glycol and the like. These can be used alone or in combination of two or more. These water-soluble polymers are preferably blended at a low concentration as long as the sprayability of the liquid detergent composition is not impaired.

<Preservatives and bactericides>
The antiseptic / bactericidal agent is not particularly limited, and examples thereof include benzoic acid, dehydroacetic acid, sorbic acid, p-hydroxybenzoic acid esters, butylhydroxyanisole, butylhydroxytoluene, and ethanol. These can be used alone or in combination of two or more.

<Antioxidant>
The antioxidant is not particularly limited, and examples thereof include vitamin E, dibutylhydroxytoluene, butylhydroxyanisole, gallic acid ester, ascorbic acid, phytic acid, and the like. These can be used alone or in combination of two or more.

<Vitamins>
Examples of the vitamins include, but are not limited to, vitamin A, vitamin B1, vitamin B2, vitamin B6, vitamin B12, pantothenic acid, biotin, vitamin C, vitamin D, vitamin E, and derivatives thereof. These can be used alone or in combination of two or more.

<Sugars and glycols>
The sugars / glycols are not particularly limited, and examples thereof include glucose, fructose, lactose, sucrose, maltose, water-soluble dextrin, cyclodextrin, starch, ethylene glycol, propylene glycol, butanediol, pentaerythritol, sorbitol, and xylitol. Etc. These can be used alone or in combination of two or more.

<Fragrance>
The fragrance is not particularly limited, and examples thereof include synthetic fragrance compounds and natural essential oils, and blended fragrances prepared by blending them, such as jasmine, floral, bouquet, rose, mugue, aldehydic, green, citrus Fragrances such as woody, animal, fruity and spices. These can be used alone or in combination of two or more.

<Bleaching agent>
The bleaching agent is not particularly limited. For example, chlorine bleaching agents such as sodium hypochlorite, bleaching powder, dichloroisocyanuric acid, oxygen bleaching agents such as sodium perborate and sodium percarbonate, hydrosal Fight, thiourea dioxide and the like. These can be used alone or in combination of two or more.

<Acid>
The acid is not particularly limited, and examples thereof include inorganic acids such as sulfuric acid, hydrochloric acid, and phosphoric acid, and organic acids such as oxalic acid, tartaric acid, citric acid, and gluconic acid. These can be used alone or in combination of two or more.

<Alkali>
The alkali is not particularly limited, and examples thereof include inorganic alkalis such as sodium hydroxide, potassium hydroxide and sodium carbonate, and organic alkalis such as ammonia and alkanolamine. These can be used alone or in combination of two or more.

<Enzyme>
The enzyme is not particularly limited, and examples thereof include animal and plant-derived or microorganism-derived proteolytic enzymes (proteases), lipolytic enzymes (lipases), starch-degrading enzymes (amylases), and fibrinolytic enzymes (cellulases). It is done. These can be used alone or in combination of two or more.

<Colorant>
Although it does not specifically limit as said coloring agent, For example, red No. 2, red No. 3, red No. 102, red No. 104, red No. 106, yellow No. 4, yellow No. 5, green No. 3, blue No. 1, blue No. 2, pigments such as Industren Blue RS, Wool Green BS, Quinoline Yellow, Patent Blue V, Chlorine Titanium Oxide Pigment, Oil Furnace Black, Yellow Lead, Yellow Iron Oxide, Kaolin Clay, Cadmium Yellow, Cadmium Red, Fluorescent Pigment, black iron oxide, ultra-fine calcium carbonate, cobalt blue, cobalt green, cobalt purple, pepper powder, bitumen, thermal black, chromium oxide, titanium oxide (Atanus), titanium oxide (rutile), disazo yellow, red iron oxide, brown Iron oxide, carbon black, iron black, copper phthalocyanine blue, copper phthalocyanine green, dolomite Powder, permanent red, fine titanium oxide particles, fine particles of barium sulfate, Fast Yellow 10G, red iron oxide, pigments such as molybdenum red and the like. These can be used alone or in combination of two or more.

  In the liquid detergent composition of the present invention, a surfactant (component B), water (component C), and other optional components are added to the aqueous dispersion of cellulose fibers (component A) obtained as described above. Can be appropriately mixed and dispersed.

  The mixing / dispersing treatment is not particularly limited. A homogenizer or the like can be used. In addition, by selecting the type and operating conditions of the mixing / dispersing apparatus, it is possible to prepare a liquid detergent composition having desired properties according to the physicochemical properties of any additive.

  The liquid detergent composition of the present invention preferably has a viscosity of 500 mPa · s or more, more preferably 1000 mPa · s or more. The viscosity mentioned above refers to a viscosity measured after 180 seconds at 25 ° C. using a BH viscometer at rotor number 5 and 2.5 rpm.

  Since the liquid cleaning composition of the present invention can be used by spraying the object to be cleaned, it is excellent in convenience and cleaning effect.

  The spraying method is not particularly limited. For example, a dispenser type spray equipped with a sprayable pump type nozzle, a trigger type spray, an aerosol type spray, a human power sprayer, a power sprayer, a boom sprayer, a punkle sprayer, a sprinkler, a mist Machine, speed sprayer, room temperature fume mister, spur sputter sprayer, etc.

  When the liquid detergent composition of the present invention is used for a household detergent, etc., the convenience for the user can be further enhanced by using a spray container-containing detergent previously filled in a spray container.

  The spray container used for the detergent contained in the spray container of the present invention can be easily filled with the liquid detergent composition of the present invention, and preferably functions as a spray, considering the versatility and high spray accuracy, A dispenser type spray container equipped with a sprayable pump type nozzle, a trigger type spray container, and an aerosol type spray container are more preferable.

<Dispenser type spray container equipped with a sprayable pump type nozzle>
The spray container can be sprayed at atmospheric pressure, does not require pressurized gas and the like, and has a relatively simple container structure. Therefore, the spray container is highly safe and suitable for portable use. The structure is composed of an extrusion pump type nozzle equipped with a suction type tube and a screw type container which is fixed and filled with contents. In order to enhance the spray function, conditions such as the hole diameter of the pump type nozzle and the pumping volume per pump can be selected and adjusted according to the object to be cleaned and the purpose of cleaning.

<Trigger type spray container>
The above-mentioned trigger type spray container has a pistol type trigger type spray device attached to the mouth of the container body filled with the contents, and can operate the spray at atmospheric pressure, and is highly versatile as a spray container. is there. The trigger spray container includes all modified trigger spray containers in order to enhance the spray function.

<Aerosol spray container>
The aerosol-type spray container enables continuous spraying that cannot be realized by the two spray devices by filling the container with a propellant. The aerosol spray container includes all improvements in the spray device portion of the aerosol container. In general, the spray using this spray container enables finer mist compared to the above two sprays carried out under atmospheric pressure. The propellant used in the aerosol spray container is not particularly limited, and examples thereof include dimethyl ether, liquefied petroleum gas, carbon dioxide gas, nitrogen gas, argon gas, air, oxygen gas, and chlorofluorocarbon gas. Two or more types can be used.

  The liquid detergent composition and the detergent contained in the spray container of the present invention are not particularly limited. For example, the liquid detergent composition and the detergent contained in a spray container are used for detergents for industrial use, household use, and the like. , Oven cleaner, grill cleaner, ventilation fan cleaner, range cleaner, sink cleaner, pipe cleaner, floor cleaner, floor cleaner, glass cleaner, window glass cleaner, screen door cleaner, concrete cleaner, toilet cleaner, magnetic / tile cleaner, Graffiti remover, paint remover, ink remover, water pipe cleaner, car cleaner, car shampoo, tire cleaner, radiator cleaner, engine cleaner, metal cleaner, leather cleaner, plastic cleaner, glasses cleaner, bath Cleaner, wall cleaner, bathtub cleaner, kitchen sink cleaner, furniture cleaner, home appliance cleaner, building exterior cleaner, concrete cleaner, insulator cleaner, medical instrument cleaner, semiconductor cleaner, electronic component cleaner, ship cleaner, Aircraft cleaner, boiler cleaner, precision equipment cleaner, lens cleaner, bottle container cleaner, air cleaner cleaner, tree cleaner, facial cleaner, body shampoo, shaving agent, shampoo, hand soap, pet shampoo, liquid It can be used for toothpaste, laundry detergent and the like.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example and a comparative example, of course this invention is not limited to these. The concentration is mass% unless otherwise specified.

[Production Example 1]
To the stirrer, 200 g of pulp (LBKP, Nippon Paper Industries Co., Ltd.) in dry mass and 18 g of sodium hydroxide in dry mass were added, and water was added so that the pulp solid content concentration was 15%. Then, after stirring for 30 minutes at 30 ° C., the temperature was raised to 70 ° C., and 23 g (in terms of active ingredient) of sodium monochloroacetate was added. After reacting for 1 hour, the reaction product was taken out, neutralized and washed to obtain anion-modified cellulose having a substitution degree of 0.01 per glucose unit. Thereafter, water was added to the anion-modified pulp to a solid content concentration of 5%, and it was treated 5 times with a high-pressure homogenizer at 20 ° C. and a pressure of 140 MPa, and the number-average fiber diameter was 74 nm, the aspect ratio was 67, and the cellulose having a crystal structure A dispersion of fiber 1 was obtained.

[Production Example 2]
A dispersion of cellulose fiber 2 was obtained in the same manner as in Production Example 1 except that 176 g of sodium hydroxide and 234 g of sodium monochloroacetate (active ingredient conversion) were changed. In addition, the substitution degree per glucose unit of the obtained cellulose fiber was 0.10, the number average fiber diameter was 10 nm, the aspect ratio was 140, and it had a crystal structure.

[Production Example 3]
A dispersion of cellulose fiber 3 was obtained in the same manner as in Production Example 1, except that sodium hydroxide was changed to 308 g and sodium monochloroacetate was changed to 410 g (in terms of active ingredient). In addition, the substitution degree per glucose unit of the obtained cellulose fiber was 0.25, the number average fiber diameter was 6 nm, the aspect ratio was 160, and it had a crystal structure.

[Production Example 4]
A dispersion of cellulose fiber 4 was obtained in the same manner as in Production Example 1, except that the sodium hydroxide was changed to 9 g and the sodium monochloroacetate was changed to 12 g (converted to the active ingredient). In addition, the substitution degree per glucose unit of the obtained cellulose fiber was 0.005, the number average fiber diameter was 620 nm, the aspect ratio was 18, and it had a crystal structure.

[Production Example 5]
A dispersion of cellulose fiber 5 was obtained in the same manner as in Production Example 1, except that sodium hydroxide was changed to 476 g and sodium monochloroacetate was changed to 632 g (in terms of active ingredient). In addition, the substitution degree per glucose unit of the obtained cellulose was 0.6, the number average fiber diameter could not be measured, and no crystal structure was observed.

[Production Example 6] A dispersion of cellulose fiber 6 was obtained in the same manner as in Production Example 1 except that 308 g of sodium hydroxide, 410 g of sodium monochloroacetate (active ingredient conversion), and the treatment with the high-pressure homogenizer was changed to 20 times. . In addition, the substitution degree per glucose unit of the obtained cellulose fiber was 0.25, the number average fiber diameter could not be measured, and no crystal structure was observed.

[Production Example 7] 200 g dry pulp (LBKP, Nippon Paper Industries Co., Ltd.) and 308 g sodium hydroxide dry mass are added to a stirrer, and water is added so that the pulp solids concentration is 15%. It was. Then, after stirring for 9 hours at 70 ° C., 410 g of sodium monochloroacetate (in terms of active ingredient) was added. After reacting for 1 hour, the reaction product was taken out, neutralized and washed to obtain anion-modified cellulose having a substitution degree of 0.28 per glucose unit. Thereafter, water was added to the anion-modified pulp to a solid content concentration of 5%, and it was treated 5 times with a high-pressure homogenizer at 20 ° C. and a pressure of 140 MPa to obtain a dispersion of cellulose fibers 7. The number average fiber diameter could not be measured, and no crystal structure was observed.

<Measurement method of substitution degree per glucose unit>
Cellulose fiber is prepared in a slurry of 0.6% by mass, 0.1M hydrochloric acid aqueous solution is added to adjust the pH to 2.4, and 0.05N sodium hydroxide aqueous solution is added dropwise until the pH reaches 11. The amount of carboxyl groups was measured from the amount of sodium hydroxide consumed in the neutralization step of a weak acid with a gradual change in electrical conductivity, and calculated using the following formula. The degree of substitution referred to here represents the average value of the number of moles of substituents per mole of anhydroglucose unit.
Carboxymethyl substitution degree = (162 × C) / (1-58 × C)
C: Amount of carboxyl group (mol / g)

<Measurement method of number average fiber diameter>
Water was added to the cellulose fiber to make a slurry of 2 mass%, and a finer treatment was performed for 10 minutes at a rotation speed of 8,000 rpm using a disper type mixer. The maximum fiber diameter and the number average fiber diameter of each cellulose fiber were observed using a transmission electron microscope (TEM) (JEM-1400, manufactured by JEOL Ltd.). That is, after each cellulose fiber was cast on a hydrophilized carbon film-coated grid and negatively stained with 2% uranyl acetate, the number average fiber diameter was determined according to the method described above. Was calculated.

<Confirmation method of crystal structure>
A wide-angle X-ray diffraction image was measured using an X-ray diffractometer (RINT-Utima 3 manufactured by Rigaku Corporation), and the X-ray diffraction pattern typical for cellulose type I or type II (type I: (Diffraction angle 2θ = 12.1 °, 19.8 °, 22.0 °, type II: diffraction angle 2θ = 12.1 °, 19.8 °, 22.0 °) has a crystal structure. I decided.

<Aspect ratio measurement method>
From the TEM image (magnification: 10000 times) that was negatively stained with 2% uranyl acetate after the cellulose was cast on a hydrophilic membrane-coated carbon film grid, the number average width and the long width of the short width of cellulose The number average width of was observed. That is, according to each method described above, the number average width of the shorter width and the number average width of the longer width were calculated, and the aspect ratio was calculated according to the following formula using these values.
Aspect ratio = Number average width (nm) for longer width / number average width (nm) for shorter width

[Example 1-6, Comparative Example 1-11]
Next, each component shown in Table 1 and Table 2 was blended in the ratio shown in the same table using the aqueous dispersion of cellulose fiber obtained above. The cellulose fiber is the amount of cellulose fiber in the aqueous dispersion of cellulose fiber, and the amount of water in the cellulose aqueous dispersion was taken into account when adding the remaining water. Next, this compound was treated at 12000 rpm for 15 minutes using a vacuum emulsifier to obtain a cleaning composition.

Tables 1 and 2 show the dispersion stability of the resulting cleaning composition.
<Dispersion stability>
The dispersion stability after standing for 1 week at 25 ° C. was evaluated visually according to the following criteria.
×: Separation is observed ○: Uniform

250 ml of a 500 ml capacity trigger spray container was filled with the detergent composition. A glass plate was stood at an angle of 45 degrees, sprayed from a position 20 cm away, and spray (spraying) characteristics (spraying state and dripping) were evaluated according to the following criteria. The evaluation results are shown in Tables 1 and 2.
<Spray state>
X: Not sprayed in a mist state or clogging occurs and cannot be sprayed.
(Triangle | delta): The thing injected in mist form and the thing which does not become mist form coexist.
○: Sprayed in a mist form.
<Drainage>
X: The liquid dripping within 1 minute after spraying.
○: No dripping from spray over 1 minute.

Using the above spray, the cleaning power was evaluated by the following method. The evaluation results are shown in Tables 1 and 2.
<Detergency A>
Heat-denatured tempura oil was colored with a red oil paint. 3 g of this was applied to a glass plate and allowed to dry naturally. The glass plate was erected vertically, and the spray was applied once and allowed to stand for 30 minutes. After rinsing with water, a glass plate was placed over a high-intensity lamp, and the area of the residual oil portion was visually determined.
×: Over 50%, Δ: 25-50%, ○: less than 25% <Detergency B>
Mineral oil was colored with carbon black. 3 g of this was applied to a glass plate and allowed to dry naturally. The glass plate was erected vertically, and the spray was applied once and allowed to stand for 30 minutes. After rinsing with water, a glass plate was placed over a high-intensity lamp, and the area of the residual oil portion was visually determined.
×: Over 50%, Δ: 25-50%, ○: Less than 25%

＊いずれも、水酸化ナトリウムを添加しｐＨ４に調整した。

* In each case, the pH was adjusted to 4 by adding sodium hydroxide.

As is clear from the results in Tables 1 and 2 above, Examples 1-6 using the liquid detergent composition for spray of the present invention and the detergent contained in the spray container using the same are dispersion stability, spray state, It can be seen that both the dripping and the detergency are good. On the other hand, the degree of substitution or aspect ratio is outside the scope of the present invention, and Comparative Example 1-11 using no cellulose fiber cannot achieve both of these characteristics.

  The liquid cleaning composition and the cleaning agent in a spray container of the present invention are used for cleaning agents for industrial use, household use, etc., specifically, mat cleaning agents, carpet shampoos, kitchen detergents, oven cleaners, grills. Cleaner, ventilation fan cleaner, range cleaner, sink cleaner, pipe cleaner, floor cleaner, floor cleaner, glass cleaner, window glass cleaner, screen cleaner, concrete cleaner, toilet cleaner, magnetic / tile cleaner, graffiti remover, paint Remover, ink remover, water pipe cleaner, car cleaner, car shampoo, tire cleaner, radiator cleaner, engine cleaner, metal cleaner, leather cleaner, plastic cleaner, glasses cleaner, bathroom cleaner, wall cleaner Cleaner, bathtub cleaner, kitchen sink cleaner, furniture cleaner, home appliance cleaner, building exterior cleaner, concrete cleaner, insulator cleaner, medical instrument cleaner, semiconductor cleaner, electronic component cleaner, ship cleaner, aircraft cleaner , Boiler cleaner, precision equipment cleaner, lens cleaner, bottle container cleaner, air cleaner cleaner, tree cleaner, facial cleanser, body shampoo, shaving agent, shampoo, hand soap, pet shampoo, liquid toothpaste, laundry It can be used for detergents.

Claims (3)

A liquid detergent composition for spraying containing the component (A), the component (B), and the component (C).
(A) Cellulose fibers having a number average fiber diameter of 2 nm or more and 500 nm or less, wherein a substituent is introduced into the hydroxyl group in the cellulose molecule, the degree of substitution is 0.01 or more and 0.5 or less, type I and Cellulose fibers having an / II type crystal structure and an aspect ratio of 50 or more. (B) Surfactant.
(C) Water.   2. The liquid detergent composition for spraying according to claim 1, wherein the content (solid mass) of the component (A) is in the range of 0.05 to 5.0 mass% of the whole liquid detergent composition for spraying.   A spray container-containing cleaning agent, comprising the spray liquid cleaning composition according to claim 1 or 2.