JPH10183197A - Bottled nonionic detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a bottled nonionic detergent composition that can prevent the strength deterioration of the bottle in which the amount of plastic material used is reduced, and can store the nonionic detergent composition for a long period of time, as the detergency of the nonionic detergent composition is effectively prevented from reducing. SOLUTION: A bottle is filled with a nonionic detergent composition. The bottle is constituted with paper laminated with at least one kind of resin selected from the group consisting of nylon, polypropylene and polyethylene and the jointing parts are coated with a resin. This nonionic surfactant comprises a polyoxyalkylene alkyl (or alkenyl) ether or a fatty acid alkylalkoxylate prepared by adding an alkylene oxide to a fatty acid alkyl ether having a melting point of <=40 deg.C and a HLB of 9-16.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a nonionic detergent composition in a container, and more particularly, to a container in which the amount of plastic material used is reduced, it is possible to prevent the strength of the container from deteriorating and effectively reduce the detergency of the detergent. The present invention relates to a nonionic detergent composition in a container, which can prevent the nonionic detergent composition from being stored for a long period of time.

[0002]

2. Description of the Related Art Nonionic surfactants generally have a low foaming property, their detergency is hardly affected by the hardness of water, and they are particularly excellent in mud dirt and dispersibility at low temperatures. Furthermore, it is an excellent surfactant having good biodegradability, low environmental load, low toxicity and no problem in safety. Therefore, a detergent containing a nonionic surfactant, such as a granular nonionic detergent composition or a paste-like composition, which makes use of characteristics of the nonionic surfactant, has been proposed. However, nonionic surfactants are generally liquid at room temperature, and in the case of a granular nonionic detergent composition, they are easy to exude from the detergent, and when nonionic surfactant exudes from a nonionic granular detergent product to a detergent container, it occurs. This degrades the appearance of the product, lowers the detergency due to the decrease in the nonionic surfactant at the container contact portion, and further adversely affects the fluidity of the detergent particles and the caking resistance. Of course, when the nonionic detergent composition is stored in a container integrally manufactured from a plastic that is resistant to nonionic surfactant, there is no effect on the appearance of the container, but the flowability of the detergent particles and This is the same in that adverse effects are exerted on the caking resistance.

In recent years, from the viewpoint of saving plastic resources and protecting the environment, it has been demanded to reduce the amount of plastic materials used as much as possible. In such a case,
It is conceivable to form the container using plastic-laminated paper. However, when trying to form a container using such a material, it is difficult to integrally manufacture the container,
There will be a joint. Usually, when joining plastic containers, vinyl acetate-based adhesives are widely used, but when a nonionic detergent composition is stored in a container made of a laminated material joined with such an adhesive,
It has been found that nonionic surfactant exuding from granular nonionic detergent or nonionic surfactant from pasty nonionic detergent attacks vinyl acetate-based adhesives and weakens the strength of the container. Also, in such containers, the nonionic surfactant, after attacking the adhesive, soaks into the paper under the plastic, further reducing the concentration of nonionic surfactant in the detergent that contacts the container, and This causes a reduction in force and a problem of deteriorating the appearance of the container.

[0004]

SUMMARY OF THE INVENTION Accordingly, the present invention provides a container in which the amount of plastic material used is reduced, while preventing deterioration of the strength of the container and effectively preventing a decrease in the cleaning power of the detergent for a long period of time. An object of the present invention is to provide a nonionic detergent composition in a container that can be stored.

[0005]

The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a polyoxyalkylene alkyl (or alkenyl) ether having a melting point of 40 ° C. or less and an HLB of 9 to 16 or When filling a nonionic detergent composition comprising a specific nonionic surfactant comprising a fatty acid alkyl ester alkoxylate obtained by adding an alkylene oxide to a fatty acid alkyl ester, the container is selected from the group consisting of nylon, polypropylene and polyethylene. The present invention has been found to be able to effectively achieve the above-mentioned object by being made of paper laminated with at least one kind of resin and covering the joining portion with the resin, thereby achieving the present invention.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The nonionic surfactant used in the present invention is a fatty acid alkyl ester alkoxylate obtained by adding an alkylene oxide to a polyoxyalkylene alkyl (or alkenyl) ether or fatty acid alkyl ester having a melting point of 40 ° C. or less and an HLB of 9 to 16. It is. In places where nonionic detergents are stored, the temperature may exceed 40 ° C., especially in summer. Therefore, it is very important to be able to effectively store nonionic detergents using such nonionic surfactants having a low melting point. The melting point of the nonionic surfactant that can be preferably used in the present invention is preferably 30 ° C. or lower, particularly preferably 25 ° C. or lower. For example, the lower limit is usually 5 ° C. The HLB of the nonionic surfactant is preferably 10%.
To 15, particularly preferably 11 to 14.

Preferred nonionic surfactants include, for example, the following. (1) An aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms and an alkylene oxide having 2 to 4 carbon atoms on average 3
Polyoxyalkylene alkyl (or alkenyl) ether added to ３０30 mol, preferably 7-20 mol. Among them, polyoxyethylene alkyl (or alkenyl) ether and polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether are preferable. (2) Polyoxyalkylene (eg, ethylene) alkyl (or alkenyl) phenyl ether. (3) A fatty acid alkyl ester alkoxylate represented by the following formula in which an alkylene oxide is added between ester bonds of a long-chain fatty acid alkyl ester.

R ¹ CO (OA) _n OR ² (R ¹ CO represents a fatty acid residue having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms. OA represents 2 to 4 carbon atoms such as ethylene oxide and propylene oxide. Represents an addition unit of alkylene oxide, preferably 2 to 3. n represents an average number of added moles of alkylene oxide, and generally represents 3 to 3
0, preferably a number from 7 to 20. R ² has 1 carbon atom
Represents a lower alkyl group which may have 1 to 3 substituents. (4) Polyoxyethylene sorbitan fatty acid esters. (5) Polyoxyethylene sorbite fatty acid ester. (6) Polyoxyethylene fatty acid esters. (7) Polyoxyethylene hydrogenated castor oil. (8) Glycerin fatty acid ester.

The nonionic surfactant is contained in the nonionic detergent composition at preferably 15 to 40% by weight, more preferably 18 to 35% by weight, and particularly preferably 20 to 30% by weight. When the amount is less than 15% by weight, the concentration of nonionic surfactant in the obtained detergent particles becomes low, and a good cleaning effect cannot be obtained. On the other hand, if it exceeds 40% by weight,
In particular, in the case of a granular nonionic detergent, the solidification property deteriorates at high temperatures. On the other hand, in the case of the paste-like nonionic detergent, the nonionic surfactant is at least 10% by weight, preferably at least 15% by weight, based on the weight of the paste-like nonionic detergent. The upper limit is preferably 60% by weight, more preferably 5% by weight.
0% by weight. 10% by weight of nonionic surfactant
If the amount is smaller than the above range, the detergency deteriorates, which is not preferable. Water can be added as needed. In particular, a paste-like nonionic detergent may be required. The nonionic detergent paste can be used in a gelling region or a non-gelling region of the nonionic surfactant. For example, gelation tends to occur when the amount of the nonionic surfactant is in the range of 40 to 80% by weight based on the total amount of the nonionic surfactant and water. In the nonionic detergent composition used in the present invention, a clay mineral, an oil-absorbing carrier, and a nonionic gelling agent can be added, if necessary, in addition to the nonionic surfactant.

As the clay mineral optionally used in the present invention, in particular, those belonging to the smectite group and having a crystal structure of a three-layered dioctahedral or three-layered trioctahedral structure are preferably used. it can. Such a clay mineral has a cleavage property and has a layered structure. This clay mineral has a smaller oil absorption than the oil-absorbing carrier described below. In addition, when the clay mineral is used particularly in a granular nonionic detergent composition, the clay mineral has a property of forming a chemical adsorption by a hydrogen bond between crystal layers and retaining the nonionic surfactant inside the clay mineral. Therefore,
In the granular nonionic detergent composition, the clay mineral has an effect of preventing exudation of the nonionic surfactant. On the other hand, it was found that the clay mineral has a function as a viscosity modifier that stably holds the paste-like nonionic detergent composition in the container in the non-gelling region of the nonionic surfactant.

Incidentally, the clay mineral has a property of swelling as the nonionic surfactant is retained inside. The clay mineral which can be preferably used in the present invention preferably has an oil absorption of less than 80 ml / 100 g, more preferably 30 to 70 ml / 1.
On the other hand, the bulk density is preferably at least 0.1 g / cc, particularly preferably 0.2 to 1.5 g / cc. Specific examples of such clay minerals include, for example, montmorillonite (oil absorption:
50 ml / 100 g, bulk density: 0.3 g / cc), nontronite (oil absorption: 40 ml / 100 g, bulk density: 0.5 g / cc), beiderite (oil absorption: 62 ml / 100 g, bulk density: 0.55 g) / c
c), pyrophyllite (oil absorption: 70 ml / 100 g, bulk density: 0.63 g / cc), and on the other hand, as a clay mineral having a trioctahedral type three-layer structure, saponite (oil absorption: 73 ml) / 100 g, bulk density: 0.15 g / cc), hectorite (oil absorption: 72 ml / 100 g, bulk density: 0.7 g / c)
c), Stephensite (oil absorption: 30 ml / 100 g, bulk density: 1.2 g / cc), talc (oil absorption: 70 ml / 100 g, bulk density: 0.1 g / cc). These clay minerals generally include those naturally produced and those artificially hydrothermally synthesized, but are not particularly limited. Such clay minerals may be those in which a peak derived from the spread of the clay layer detected at 10 to 20 ° in X-ray analysis and a peak derived from the three-layer structure of the clay detected at 4 to 5 ° are developed. It can be used without any particular restrictions. In addition, clay minerals may contain a large amount of impurities such as quartz, cristobalite, calcite and opal feldspar, particularly in the case of natural products, and those having a large amount of these impurities are not suitable for the present invention and have a purity of at least 60%. And more preferably 70% or more, and most preferably 100%. Particularly preferably used clay minerals include Na-type montmorillonite, Ca-type montmorillonite, activated bentonite (Na / Ca-type montmorillonite), Na-type hectorite, and Ca-type hectorite.

The clay mineral is contained in the nonionic detergent composition preferably at 0.1 to 30% by weight, more preferably at 1 to 20% by weight, particularly preferably at 3 to 10% by weight. In the granular nonionic detergent composition, within this range, the fluidity of the detergent particles under high temperature and high humidity is improved. On the other hand, in the case of the paste-like nonionic detergent, the liquid dripping prevention property is improved within this range. The oil-absorbing carrier arbitrarily used in the present invention, particularly when used in a granular nonionic detergent composition, suppresses nonion exudation and solidification of detergent particles under high temperature and high humidity, while the detergent is used. Is added to improve the solubility of the detergent. The oil-absorbing carrier is
A porous fine powder sufficient to adsorb and retain nonionic surfactants, physically adsorb nonionic surfactants,
On the other hand, it does not swell. The oil absorption of the oil-absorbing carrier used in the present invention is larger than that of the clay mineral. Preferred oil-absorbing carriers include JIS-K6
The oil absorption expressed by the 220 test method is 80 ml / 100 g or more,
It is preferably 150-600 ml / 100 g oil-absorbent and has a bulk density of less than 0.1 g / cc, preferably 0.001-0.08.
A substance having a g / cc is preferably used. As such an oil-absorbing carrier, for example, amorphous silicic acid (oil absorption: 250 ml)
/ 100 g, bulk density: 0.06 g / cc) (Toxor made by Tokso, Aerosil made by Nippon Aerosil, Nip seal made by Nippon silica), amorphous calcium silicate (oil absorption: 450 ml / 1)
00g, bulk density: 0.03g / cc) (Tokusso Florite, Cofuran Chemical Thixolex), amorphous aluminosilicate (oil absorption: 150ml / 100g, bulk density: 0.08)
g / cc), magnesium silicate (oil absorption: 180 ml / 100 g,
Bulk density: 0.08 g / cc), magnesium carbonate (oil absorption: 1)
50 ml / 100 g, bulk density: 0.08 g / cc), calcium carbonate (oil absorption: 110 ml / 100 g, bulk density: 0.09 g / cc), spinel (oil absorption: 600 ml / 100 g, bulk density: 0.008 g / cc)
cc), cordierite (oil absorption: 600 ml / 100 g, bulk density: 0.008 g / cc), mullite (oil absorption: 560 ml / 1)
00g, bulk density: 0.009g / cc), starch degradation product (oil absorption:
200 ml / 100 g, bulk density: 0.06 g / cc) (Pine Flow, manufactured by Matsutani Chemical). These oil-absorbing carriers may be used as a mixture.

[0013] The oil-absorbing carrier is, for example, preferably 0.1 to 20% by weight, more preferably 0.5 to 15% by weight, particularly preferably 1 to 10% by weight in the granular nonionic detergent composition.
It is contained in. By being used within this range,
Solidification and dusting of detergent particles under high temperature and high humidity (dust generation)
Is improved. On the other hand, in the paste-like nonionic detergent, the oil-absorbing carrier does not need to be particularly blended. The nonionic gelling agent optionally used in the present invention, for example, when used in a granular nonionic detergent composition, acts to gel nonionic surfactant and solidify and retain the nonionic surfactant in the granular detergent. Having. By using this nonionic gelling agent, the prevention of exudation of the nonionic surfactant, the fluidity of the detergent particles and the anti-caking properties are significantly improved under high temperature and high humidity. Therefore, various nonionic gelling agents can be used as long as the nonionic gelling agent has such a function. As the nonionic gelling agent used in the present invention, those similar to those conventionally used as oil gelling agents can be used. Among such nonionic gelling agents, when a specific nonionic surfactant is gelled by the nonionic gelling agent, 40%
It is preferable to use one having a maximum compressive stress of 30 g / cm ² or more at ° C. The maximum compressive stress is determined by measuring the weight ratio of the alcohol ethoxylate type nonionic surfactant (carbon chain length 12, average number of moles of ethylene oxide added 9, melting point 20 ° C.) of a general detergent to the nonionic gelling agent to be measured. After mixing at 70 ° C. at 5/1, cooling to 20 ° C., and then allowing to stand at 20 ° C. for 3 hours, 5 cm × 5 cm
× After preparing a rectangular parallelepiped test piece having a height of 1 cm, the maximum compressive stress when a cylindrical jig having a cross-sectional diameter of 1.5 cm was pressed at 40 ° C and a compression speed of 20 mm / min was applied to the test piece. Measure.

[0014] In the present invention, the nonionic gelling agent
The maximum compressive stress under the above conditions is 30 g / cm^TwoLess than
Tendency of the detergent particles to be insufficiently fluid at high temperatures
There is. Further preferred maximum compressive stress is 50 to 2000
g / cm^Two The particularly preferred maximum compressive stress is 100 to 150.
0g / cm^Two It is. Preferred nonions that can be used in the present invention
Examples of the gelling agent include 12-hydroxystearyl
Acid (Maximum compressive stress 520g / cm^Two ) (KF Trading
Hydroxystearin (trade name), dibenzylide
Sorbitol (maximum compressive stress 30g / cm^Two ) (New Japan Science
Gel All D (trade name)), lithium stearate
(Maximum compressive stress 50g / cm^Two ) (L made by KF Trading
i-ST (trade name)), aluminum palmitate (most
Large compressive stress 50g / cm^Two ) (KF Trading Al-
PL (trade name)), lithium 2-ethylhexanoate (most
Large compressive stress 66g / cm ^Two ) (KF Trading Li-
2EH (trade name)), 12-hydroxystearic acid
Lumilium (Maximum compressive stress 126g / cm^Two ) (KF tray
Al-OHST (trade name), Lauroirg
Dibutyl glutamic acid (maximum compressive stress 200g / cm
^Two ) (Ajinomoto Coagulant GP-1 (trade name))
Uroylglutamic acid stearylamide (maximum compressive stress
53g / cm^Two ) (Made by Ajinomoto), dicaproyl lysine lauri
Luamide (maximum compressive stress 183g / cm^Two ) (Made by Ajinomoto),
Dicaproyl lysine lauramide (maximum compressive stress 91
g / cm^Two ) (Made by Ajinomoto), dicaproyl lysine laurylue
Stell (maximum compressive stress 45g / cm^Two ) (Made of Ajinomoto), lau
Roylphenylalanine lauramide (maximum compressive stress
37g / cm^Two ) (Made by Ajinomoto), polystyrene polybutadier
Block copolymer (molecular weight: 200,000, composition: police)
Tylene / polybutadiene = 40/60) (maximum compressive stress)
60g / cm^Two ) (KF Trading KF21 (Product
Name)), polyacrylamide (molecular weight: 100,000) -iso
Paraffin mixture (maximum compressive stress 83g / cm^Two ) (Fuso Ko
Soragam SD401 (trade name), polystyrene
Block copolymer of block and polybutadiene block
-(Molecular weight: 100,000, composition: polystyrene / polybutadi
EN = 30/70) (Maximum compressive stress 48g / cm)^Two ) (KF
Trading), dextrin palmitate
(Maximum compressive stress 80g / cm^Two ) (Chiba Milling Leopard)
KL (trade name)) or a mixture thereof
Can be. Mix these nonionic gelling agents.
And can provide the desired maximum compressive stress
You. In the present invention, the nonionic gelling agent is, for example,
In the granular nonionic detergent composition, preferably 0.1 to 30 weight
%, More preferably 0.5 to 20% by weight, particularly preferably
Is contained at 1 to 10% by weight. This amount is less than 0.1% by weight
At full, the resulting detergent particles have high fluidity under high temperature and high humidity.
It tends to worsen, which is not preferable. On the other hand, 30
If the amount exceeds%, the solubility of the obtained detergent particles tends to deteriorate.
Not preferred. On the other hand, in the paste nonionic detergent
Is the melting point of the nonionic surfactant within this range.
It has the function of raising and suppressing the deterioration of the container.

[0015] The nonionic detergent composition of the present invention further comprises:
If necessary, the following components usually blended in detergent materials can be blended. (1) As inorganic washing builders, sodium carbonate, potassium carbonate, sodium silicate, potassium silicate, crystalline zeolite, sodium tripolyphosphate, sodium pyrophosphate and the like. (2) As organic washing builders, citrate, succinate, polyacrylate, polyacrylic acid-maleic acid copolymer, EDTA and the like. (3) Bis (triazinylamino) stilbene disulfonic acid derivatives, bis (sulfostyryl) biphenyl salts [Tinopearl CBS], etc. as fluorescent agents. (4) As enzymes, lipase, protease, cellulase, amylase and the like. (5) Percarbonates, perborates and the like as bleaching agents. (6) Cationic surfactants such as dialkyl-type quaternary ammonium salts as antistatic agents. (7) As surface modifiers, fine calcium carbonate, fine zeolite, polyethylene glycol and the like. (8) As anionic surfactants, α-sulfofatty acid methyl ester salt, linear alkyl benzene sulfonate,
α-olefin sulfonate, alkyl sulfate, fatty acid soap and the like. (9) Cellulose derivatives such as carboxymethylcellulose as the anti-redeposition agent. (10) As a bulking agent, sodium sulfate, potassium sulfate, sodium chloride and the like. (11) As a reducing agent, sodium sulfite, potassium sulfite and the like. Various methods can be applied to the compounding method of these components,
For example, when manufacturing a granular nonionic detergent composition,
These components can be produced by stirring granulation or extrusion granulation followed by crushing granulation. On the other hand, the paste-like nonionic detergent can be easily produced by mixing a nonionic surfactant, water, and other components, for example, in a vertical kneader.
These manufacturing methods are obvious to those skilled in the art.

For example, in the case of producing a granular nonionic detergent composition, a nonionic surfactant, a clay mineral used as required, a nonionic gelling agent, an oil-absorbing carrier, and other optional components are mixed together with stirring. Into the granulator,
It can be obtained by stirring granulation. Preferably, before the stirring granulation treatment, the nonionic surfactant and the nonionic gelling agent are mixed in advance. Thus, the reason why these components are previously mixed is that the nonionic surfactant and the nonionic gelling agent can be more uniformly mixed and the exudation of the nonionic surfactant can be suppressed. Also,
Mixing is, for example, 60 ° C. or more, preferably 60 to 90
C., particularly preferably at a temperature of 70 to 80.degree. By mixing these components at a temperature of 60 ° C. or higher, uniform mixing can be achieved. In addition, stirring granulation is usually performed at 20 to 60 ° C, preferably 30 to 50 ° C,
It is particularly preferably performed at 35 to 50 ° C. Temperature is 20 ° C
If it is lower than the above range, granulation becomes difficult to proceed, which is not preferable. On the other hand, if the temperature exceeds 60 ° C., on the other hand, the adhesion in the granulator increases and the load tends to be excessive, which is not preferable. The processing time in the stirring granulator is usually 1 to 10 minutes, preferably 2 to 8 minutes.

The granular nonionic detergent composition obtained in this manner usually has a bulk density of 0.3 to 1.2 g / cc, preferably 0.3 g / cc.
Obtained as a 5 to 1 g / cc compact. In addition, the granular nonionic detergent composition generally has an average particle size of 300 to 3000.
μm, preferably 350 to 2000 μm, particularly preferably 400 to 1000 μm. As a stirring granulator that can be used, a stirring blade is provided inside a granulator such as a high-speed mixer, a Sugi mixer, and a Loedige mixer, and 30 g of the stirring granulator is interposed between the stirring blade and the inner wall of the granulator.
Internal stirring type granulator with clearance of less than mm
It is suitably used for obtaining high bulk density detergent particles. Also,
Enzymes, fragrances, and silicone particles obtained by adsorbing silicone to a neutral inert powder such as silicic anhydride may be added later to the detergent particles subjected to the stirring granulation treatment.

In the present invention, the container filled with the nonionic detergent composition is made of paper laminated with at least one resin selected from the group consisting of nylon, polypropylene and polyethylene. These plastics are chemically resistant to nonionic surfactants. In addition, since it is laminated on paper, it is possible to produce a high-strength plastic even if the amount of plastic used is small, as compared with the case where the plastic is used alone. As nylon, polypropylene and polyethylene, various known materials can be used without limitation. As the nylon, for example, 6-nylon or 66-nylon can be used. The molecular weight of nylon is preferably 30,000 to 200,000, and more preferably 50,000 to 150,000. As the polypropylene, for example, the molecular weight is 30,000-
200,000, preferably 50,000 to 150,0
00 or the like can be used. Furthermore, as polyethylene, for example, the molecular weight is 30,000-20.
0000, preferably 50,000 to 150,000
Low-density or high-density polyethylene. Further, a mixture of these plastics, or these plastics may be laminated on paper in a plurality of layers. It is preferable that a metal film such as an aluminum foil is further laminated.

The amount of plastic in the laminate is
The thickness (as a single layer) of the plastic coated on the paper is preferably 5 to 50 μm, preferably 10 to 50 μm.
It is preferably set to μm. Within this range, plastic resources can be significantly reduced while maintaining container strength. The joint in the container needs to be joined with the above resin material. Thereby, it is possible to suppress the nonionic surfactant from deteriorating the joint portion of the container and further the paper, and to suppress the decrease in the detergency due to the decrease in the concentration of the nonionic surfactant. It is necessary that the container is made of paper laminated with the above resin, and that the joint is covered with the resin. As long as it has such a configuration, the shape of the container is not important, and containers having various shapes can be used. For example, a container such as a box-shaped container or a cylindrical container can be used. Typically, from a material obtained by laminating the above resin, a developed sheet material for forming a box body is formed, assembled, and the resulting joint is bonded to the above resin by using the above resin as an adhesive. A box can be manufactured by joining by means such as ultrasonic fusion.

[0020]

The present invention will be described below in more detail with reference to Examples and Comparative Examples. However, in Examples and Comparative Examples, the obtained nonionic detergent compositions were evaluated by the following test methods. The container used in the test was made of paper laminated with polypropylene (thickness of polypropylene: 20 μm, paper thickness: 500 μm), assembled into a box, and used polypropylene as an adhesive, and ultrasonically fused the container. This is a box-shaped container formed by fusing the joints.

The storage conditions of the detergent prior to the following test are as follows. [Preservation test of detergent] 1 kg of detergent was put into the above-mentioned container, and 50
It was stored for 60 days in a thermo-hygrostat at 85 ° C. and 85% RH. [Detergency test] Clean cotton cloth (cotton cloth No. 60 designated by the Japan Oil Chemical Society, 5 × 5 cm) in a dirt bath having the following artificial dirt composition:
After immersion, the water was squeezed with two rubber rolls to make the amount of adhered dirt uniform. After drying this soiled cloth at 105 ° C. for 30 minutes, the surface of the cloth was rubbed left and right 25 times. Of these, those with a reflectance of 42 ± 2% were used as dirty cloth. 60 pieces of the soiled cloth and 12 g of the sample detergent were put into a two-tub washing machine (CW-225 type, manufactured by Mitsubishi Electric Corporation), and the temperature was set at 15 ° C. and 30 ° C.
After washing with 10 liters of water (3 ° DH) for 10 minutes,
Dehydrated for 1 minute. Then, rinsing for 3 minutes with 30 liters of water at 15 ° C. and dehydration for 1 minute were repeated twice.
Then, after the cloth to be washed was air-dried indoors for 48 hours, the reflectance of this cloth to be washed was measured, and the cleaning rate was calculated by the following equation. Cleaning rate (%) = (K / S of dirty cloth−K / S of cleaning cloth) /
(K / S of soiled cloth-K / S of unsoiled cloth) × 100 K / S = (1−R / 100) ² / (2R / 100) (Formula of Kubelka-Munk) Soil composition (% ) Ratio (%) Oleic acid 28.3 Triolein 15.6 Cholesterol oleate 12.2 Liquid paraffin 2.5 Squalene 2.5 Cholesterol 2.5 Gelatin 7.0 Inorganic dirt 29.85 Carbon black (Nippon Oil Chemical Association) 0.5 [Solubility test] Tap water cooled to 5 ° C is gently stirred with a stirrer, 5 g of detergent is added thereto, and the mixture is stirred for 8 minutes. After drying the particles left over at 105 ° C. for 2 hours,
The weight of the undissolved particles was weighed, and the dissolution residue was calculated by the following equation. Dissolved residue (%) = ｛weight of undissolved particles (g) / 5
(G) Δ × 100 [Fluidity test] Based on JIS Z2502, 45
The measurement was performed on the detergent particles after storage at 85 ° C. and 85% RH for 3 days. Furthermore, the detergent particles after storage at room temperature for 90 days were measured in the same manner. [Dusting test] 2-tub washing machine (Mitsubishi Electric Corporation, CW
225), a spoonful (approximately 25 g) of detergent was dropped from a height of about 70 cm into an empty washing machine, and the state of dust generation was visually evaluated according to the following criteria. ◎: No dust generation is observed. ○: Slight dust generation is observed. Δ: Dust generation is slightly observed. X: Dust generation is observed. [Exudation test] 1 kg of detergent is filled in a container, and this is stored as described above. After storage under the conditions, the entire amount of the detergent was taken out, and the state of seepage of the nonionic surfactant into the container was observed. ：: Exudation is not observed. Δ: Exudation is slightly observed. ×: Exudation is observed much.

[Solidification test] The resin container was filled with 1 kg of the detergent, and after storing the resin under the above-mentioned storage conditions and after storing the resin under a load of 20 kg, the upper part of the container was opened and JIS standard 4 was applied. After carefully moving the sieve on the mesh sieve and gently vibrating the sieve, the weight on the sieve and the total weight were measured, and the solidification was calculated from the following equation. Solidification (%) = {weight on screen (g) / total weight (g)} × 100 [Bulk density test] The bulk density was measured according to JIS Z2504. [Production Example of Granular Nonionic Detergent Composition] In the table, zeolite, sulfite, soda ash and a fluorescent agent were dissolved or dispersed in water to prepare a slurry, and this slurry was spray-dried to obtain dried particles. Next, together with the dried particles, a nonionic surfactant, an oil-absorbing carrier, a nonionic gelling agent, and a clay mineral were mixed with a Ledige mixer (Matsubo Co., Ltd., M-
20 type), and stirred and granulated until the average particle diameter became 450 to 550 μm (main shaft 200 rpm, chopper 6000 rpm, granulation time 3 minutes). Finally, zeolite was added in a tumbling drum to coat the obtained detergent particles, and an enzyme and a fragrance were added to obtain a granular nonionic detergent composition (average particle diameter: 450 to 550 μm). [Raw Materials] The nonionic surfactant, nonionic gelling agent, clay mineral, and oil-absorbing carrier used in Examples and Comparative Examples are as follows. Nonionic surfactant (A) (1) A- 1 C 12-13 H 25-27 O (CH 2 CH 2 O) 7 H ( Shin Nippon Rika Co., Ltd. Konoru 20P (primary alcohols, carbon atoms 1
2, branching degree 0%) and Diadoll 13 manufactured by Mitsubishi Chemical Corporation
(Primary alcohol, 13 carbon atoms, degree of branching 50%) and an alcohol mixed at a weight ratio of 1: 4, polyoxyethylene alkyl ether obtained by adding 7 mol of ethylene oxide on average, manufactured by Lion Chemical Co., Ltd., trade name : NALG-8
3, melting point, 17 ° C, HLB: 12) (2) A-2 polyoxyethylene sorbitan monooleate (polyoxyethylene sorbitan fatty acid ester obtained by adding an average of 20 moles of ethylene oxide to sorbitan monooleate, manufactured by Nikko Chemicals Corporation, TO -10, melting point, 5 ° C, HL
B: 15) Oil-absorbing carrier (1) B-1 amorphous sodium aluminosilicate (manufactured by Mizusawa Chemical Co., Ltd., oil absorption 170 ml / 100 g) (2) B-2 amorphous water-containing amorphous silicic acid (Co., Ltd.) Tokusyl N manufactured by Tokuyama, oil absorption 280 ml / 100 g) Nonionic gelling agent C-1 12-hydroxystearic acid (manufactured by Kawaken Fine Chemical Co., Ltd.) Clay mineral D-1 Ca montmorillonite (manufactured by Meiwa Sangyo KK, BPW00)
9) [Container] (1) E-1 The box-shaped container described above (product of the present invention) (2) E-2 (control) A commercially available wax-coated paper is assembled in a box shape, and the joint is formed of vinyl acetate. (3) E-3 (Control) Carton container with commercial paperboard laminated with polyethylene on the surface of processed paper, assembled into a box, and joints bonded with vinyl acetate adhesive

[0023]

Table 1 Example composition (% by weight) 1 2 3 4 5 6 7 Type of container used A A A A A A A Nonionic surfactant (A) A-1 24 24 15 18 30 35 24 A -2 11 1 1 1 2 3 1 Optional component oil-absorbing carrier B-1 4 10 2 4 B-2 4 0.8 1.5 8 10 Nonionic gelling agent C-1 4 25 0.8 Clay mineral D-1 7 15 0.2 Zeolite 30 30 23 30 18 19 30 Sulfite 1 1 3 2 1 1 1 Soda ash 25 23 20 22 20 20 20 Fluorescent agent 0.2 0.3 0.5 0.4 0.2 0.2 0.2 Enzyme 1 1 3 2 1 1 1 Fragrance 0.2 0.2 0.2 0.2 0.3 0.5 0.2 Other small amount Component Bla * Bla Bla Bla Bla Bla Bla Evaluation result Fluidity (45 ° C) 35 35 35 35 40 45 90 Fluidity (room temperature) 35 35 35 35 35 40 40 45 Dust generation ◎ ◎ ◎ ◎ ○ ◎ ◎ Bulk density (g / l) 0.9 0.9 0.83 0.87 0.9 0.9 0.9 Exudability ○ ○ ○ ○ ○ ○ ○ Solidification (%) High temperature 0 0 1 0 1 3 5 Under load 0 0 5 3 0 15 Detergency (%) Immediately after production 85 85 82 84 88 88 85 after storage 85 85 82 84 88 88 85 residue dissolved ( ) 0 0 3 1 0 0 0 Note) Bla * means the remaining amount.

[0024]

[Table 2]

The following were used as optional components. Zeolite: crystalline sodium aluminosilicate (manufactured by Mizusawa Chemical Co., Ltd.) Sulfite: sodium sulfite (manufactured by Shinshu Chemical Co., Ltd., anhydrous sulfite) Soda ash: heavy sodium carbonate (manufactured by Asahi Glass Co., Ltd., grain ash) Fluorescent agent: 2: 4,4'-bis (2-sulfostyryl) biphenyl disodium (Ciba Geigy, Tinopearl C
BS-X) Enzyme: A mixture of alkali protease granules and alkali lipase granules in a ratio of 7/2 (weight ratio) (manufactured by Novo Nordisk, a mixture of Savinase 12T / Lipolase EX = 7/2) The fragrance has the following composition. ing.

Perfume composition parts by weight 3,7-dimethyl-1,6-octadien-3-ol 80 3,7-dimethyl-1,6-octadien-3-yl-acetate 60 3,7-dimethyl-6-octene -1-ol 40 β-phenylethyl alcohol 50 p-tert-butyl-α-methylhydrocinnamic aldehyde 70 α-methyl-p-isopropylphenylpropionaldehyde 60 α-n-amylcinnamic aldehyde 20 α-n-hexylsine Namic aldehyde 60 7-acetyl-1,1,3,4,4,6-80 hexamethyltetrahydronaphthalene 3- (5,5,6-trimethyl-norbarnan-20 2-yl) cyclohexane-1-ol Beltfix 30 2-ethyl-4- (2,2,3-trimethyl-3- 10 cyclopent-1-yl) -2-butan-1-ol 10% α, α-dimethyl-p-ethylhydrocinnamic aldehyde 40 2,4-dimethyl-3-cyclohexene-1- 10 carboxaldehyde cis-3- Hexenol 10 2-trans-3,7-dimethyl-2,6-30 octadien-1-ol n-decylaldehyde 5 10-undecene-1-al 5 methylnonylacetaldehyde 5 4- (4-hydroxy-4-methylpentyl) ) -3-30 Cyclohexene-1-carboxaldehyde naphthalene-2-acetyl-1,2,3,4,6,7,830-octahydro2,3,8,8-tetramethyl 5- (2-methylene- 6,6-dimethyl-cyclohexyl) 50-4-penten-3-one 2-methoxy 4-propenylphenol 20 allylcyclohexanepropionate 10 6,7-dihydro-1,1,2,3,3-pentamethyl-5 4 (5H) -indanone p-propenylphenyl methyl ether 5 methyl-2-aminobenzoate 5 Lemon oil 30 Orange oil 20 Lavandin oil 20 Patchouli oil 10 3,7-Dimethyl-2,6-octadienal 30 Methyldihydrojasmonate 50 Perfume components having a boiling point of 230 degrees Celsius (1 atm) account for 66 in all perfumes Ratio (wt%)

[0027]

According to the present invention, in a container in which the amount of plastic material used is reduced, the strength of the container can be prevented from deteriorating, and the nonionic detergent composition can be lengthened while effectively preventing the detergent from deteriorating. A nonionic detergent composition in a container which can be stored for a long period of time is obtained.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Seiji Abe 1-3-7 Honjo, Sumida-ku, Tokyo Inside Lion Corporation

Claims (2)

[Claims] 1. A nonionic detergent composition containing a nonionic surfactant filled in a container, wherein the container is laminated with at least one resin selected from the group consisting of nylon, polypropylene and polyethylene. Wherein the nonionic surfactant is a polyoxyalkylene alkyl (or alkenyl) ether or fatty acid alkyl ester having a melting point of 40 ° C. or less and an HLB of 9 to 16. A detergent composition in a container, comprising a fatty acid alkyl alkoxylate obtained by adding an alkylene oxide to a container. 2. The detergent composition in a container according to claim 1, wherein the nonionic detergent composition is a granular nonionic detergent composition.