CN101443511A - Slipperiness improving agent granulate for washing - Google Patents
Slipperiness improving agent granulate for washing Download PDFInfo
- Publication number
- CN101443511A CN101443511A CNA2007800177565A CN200780017756A CN101443511A CN 101443511 A CN101443511 A CN 101443511A CN A2007800177565 A CNA2007800177565 A CN A2007800177565A CN 200780017756 A CN200780017756 A CN 200780017756A CN 101443511 A CN101443511 A CN 101443511A
- Authority
- CN
- China
- Prior art keywords
- washing
- improving agent
- potassium
- potassium metaphosphate
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/06—Phosphates, including polyphosphates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
A granulated slipperiness improver for washing which contains potassium metaphosphate exhibiting a viscosity of 200mPa s or above in the form of an aqueous solution as determined by adding 2g of potassium metaphosphate to 50mL of water, stirring the obtained mixture for one minute, adding a solution of 4g of sodium tripolyphosphate (manufactured by Shimonoseki Mitsui Kagaku Kabushiki Kaisha) in 50mL of water to the resulting mixture, stirring the thus obtained mixture for three hours, and then determining the viscosity of the thus obtained solution at 25 DEG C with a Brookfield type viscometer. The slipperiness improver can be suitably used in washing clothes by hand, particularly in washing them by hand through long-time soaking.
Description
Technical field
The present invention relates to Slipperiness improving agent granulate for washing.In detail, additive when the present invention relates to the washing based on following brand-new imagination: when hand washing is washed, by improving the slickness between washings, can be with the washing of light power and improve the speed (speed of washing by rubbing with the hands of unit interval) of washing washings by rubbing with the hands etc. easily, thereby can improve the hand washing performance, and suppress because the cut wound of the damage of the washings that the friction between washings causes and the hand that causes owing to the friction of washings and hand, scratch etc.In addition, also relate to the composition of detergent that contains aforementioned Slipperiness improving agent granulate for washing.
Background technology
As washing methods, be broadly divided into hand washing and wash and washing machine washing two big classes.In recent years, because the tendency of the universal washing machine washing of washing machine increases to some extent, still, from the viewpoint of soil release characteristics and economy, the demand of washing for hand washing is still a lot.
Therefore, hand-washing the exploitation that has the washing agent of preferred rerum natura when washing at present.For example, cited at patent documentation 1, disclose with special ratios and cooperated anion surfactant, cationic surfactant, non-ionic surface active agent, thus when improving hand washing and washing for irritating method of skin.In addition, relate to the adjusting foam, general known have: the LAS and the contour foaming characteristic surfactant of AS that use when increasing foam, the non-ionic surface active agents such as polyoxyethylene alkyl ether that use when suppressing foam use soap etc. for improving defoaming during rinsing.Specifically, in patent documentation 2, disclose with special ratios and contained the anion surfactant enumerated, specific non-ionic surface active agent and fatty acid soaps, the composition of detergent of dissolubility, foaming characteristic and rinsing excellence.
Patent documentation 1: the flat 10-504056 communique of special table
Patent documentation 2: special fair 8-13987 communique
Summary of the invention
The present invention relates to:
(1) a kind of Slipperiness improving agent granulate for washing, it is the above potassium metaphosphate of 200mPas that this Slipperiness improving agent granulate for washing contains the viscosity in aqueous solution of measuring under the following conditions, described condition is: the 2g potassium metaphosphate is added in the 50ml water, stirred 1 minute, to wherein adding 4g sodium phosphate trimer (ShiShimonoseki Mitsui Chemicals system) is dissolved in the 50ml water and the solution that obtains, stirred 3 hours, and be determined at viscosity under 25 ℃ with Brookfield viscometer;
(2) a kind of composition of detergent, this composition of detergent contain aforementioned (1) described Slipperiness improving agent granulate for washing; And
(3) a kind of hand washing method of washing, this method is with aforementioned (2) described composition of detergent water-soluble, makes the concentration of the potassium metaphosphate in the water more than 15mg/L.
The specific embodiment
Following technology is arranged: be conceived to hand-wash the easiness (slickness when washing washings by rubbing with the hands) of washing, by in composition of detergent, cooperating specific potassium metaphosphate, frictional force between washings is reduced, improve slickness, thereby keeping the washing performance that improves hand washing under the constant prerequisite of washing force.
But, hand-washing when washing, in most cases be, composition of detergent is dissolved in soak in the liquid that forms in the water and leave standstill washings a few minutes to several hours after, begin again to hand-wash to wash.At this moment, by the effect of the raising slickness that dissolving showed of specific potassium metaphosphate, can As time goes on and constantly descend.In addition, can prolong the duration of slickness, but exist the dissolving of potassium metaphosphate residual and for the problem of adhering to of clothing by the particle diameter that increases this potassium metaphosphate powder.
Therefore, the washing methods that the present invention relates to Slipperiness improving agent granulate for washing, contains the composition of detergent of this Slipperiness improving agent granulate for washing and use this Slipperiness improving agent granulate for washing.Wherein, described Slipperiness improving agent granulate for washing can not cause residual and adhering to for clothing of the dissolving of potassium metaphosphate, do not soak placement or soaking the good slickness that to keep when placing between the washings, can be with the washing of light power, increase the speed of washing washings by rubbing with the hands (unit interval wash by rubbing with the hands number of times) etc., wash thereby hand-wash easily.
Present inventors consider, hand-washing when washing, it is more to begin to hand-wash the situation of washing again after carrying out the washing by soaking of a few minutes about by several hours, slickness when therefore being conceived to wash by rubbing with the hands between the washings is furtherd investigate, it found that: by using specific potassium metaphosphate is carried out the particle that granulation forms separately, perhaps specific potassium metaphosphate and adhesive and/or other composition are carried out the particle that granulation forms, not only after interpolation, directly hand-wash when washing, and in washing through the hand washing of a few minutes to about several hours the washing by soaking, all can be and can improve the speed of washing washings by rubbing with the hands (unit interval wash by rubbing with the hands number of times) etc. with the washing of light power, thereby the sense of touch in the time of can improving hand washing, and finished the present invention.
The Slipperiness improving agent granulate for washing of the application of the invention, can realize following effect: residual and the adhering to of dissolving that can not cause potassium metaphosphate for clothing, under the situation of not soaking placement and under the situation of placing through long-time immersion, can keep the good slickness between the washings, can wash and improve the speed of washing washings by rubbing with the hands (unit interval wash by rubbing with the hands number of times) etc. with light power, thus the sense of touch when improving hand washing.In addition, when washing machine washs, destroy, by improving the slickness between the fiber, thereby can avoid the damage of cloth at the external form that the fibre damage that is produced by mechanical forces such as stirrings brings.
＜Slipperiness improving agent granulate for washing 〉
The principal character of Slipperiness improving agent granulate for washing of the present invention is: contain the potassium metaphosphate with particular viscosity, and it is shaped as graininess.Slipperiness improving agent granulate for washing of the present invention with this feature, has following effect: residual and the adhering to of dissolving that can not cause potassium metaphosphate for clothing, though be under the situation of not soaking placement, or soaking under the situation of placing through long-time, all can keep the good slickness between the washings, can be with light power washing, and the speed of washings etc. is washed in increase by rubbing with the hands easily, washs thereby hand-wash easily.
In the present invention, so-called " particle " expression is carried out the particle that granulation forms separately with potassium metaphosphate, or potassium metaphosphate and adhesive and/or other composition are carried out the particle that granulation forms, and as its shape, can enumerate graininess, capsule shape etc.
In the present invention, granulating also has following advantage: can improve the operability when being added in the composition of detergent in manufacture process, and can suppress to lump under the situation of not adding simultaneously with composition of detergent in when washing.
Slipperiness improving agent granulate for washing of the present invention (below, abbreviate " slickness improver " as) can mix mutually as the washing agent that contains the slickness improver with washing agent and use, also can when washing, directly add use and not add use simultaneously with composition of detergent, but simplicity, deliquescent viewpoint during from use preferably contain the slickness improver in composition of detergent.And aforementioned smooth property improvement agent is not subjected to the qualification of composition, form, manufacture method of employed composition of detergent etc., all can bring into play its effect in all composition of detergent that contain aftermentioned solubilizer etc.
In addition, Slipperiness improving agent granulate for washing of the present invention also has following effect: improve the slickness between the washings when hand washing is washed, make hand washing carry out easily, and further improve the sense of touch when hand-washing, also have the effect of handguard, protection clothing.Therefore, Slipperiness improving agent granulate for washing of the present invention also be used for the hand washing wash.
Below, employed each composition among the present invention is described.And, be called for short sometimes below the Slipperiness improving agent granulate for washing of the present invention " particle ".In addition, so-called " cleaning solution " is meant the liquid that is used to wash, and dissolves, is suspended with aforementioned Slipperiness improving agent granulate for washing and composition of detergent in this liquid.
1. potassium metaphosphate
Among the present invention employed potassium metaphosphate be the viscosity in aqueous solution of measuring according to viscosimetry described later be more than the 200mPas, be preferably more than the 250mPas, the potassium metaphosphate more than the 300mPas more preferably.In addition, the viewpoint of being easy to get property is set out calmly, is preferably below the 800mPas, more preferably below the 600mPas.Potassium metaphosphate with this class particular viscosity, its advantage is, significantly improve slickness, have useful performance with washing agent as hand washing, so add in the washing agent combination by the Slipperiness improving agent granulate for washing that will contain this class potassium metaphosphate, also have the advantage of the amount that can reduce the slickness improver.
In the present invention, the potassium metaphosphate viscosity in aqueous solution is measured by the following method: the 2g potassium metaphosphate is added in the 50ml water, stirred 1 minute, add then 4g sodium phosphate trimer (ShiShimonoseki Mitsui Chemicals system) is dissolved in the 50ml water and the solution that obtains, stirred 3 hours, use Type B viscosity agent is determined at the viscosity under 25 ℃.
Employed potassium metaphosphate is usually with the method for making manufacturing shown in following among the present invention.
nKH
2PO
4→(KPO
3)
n+nH
2O
That is, by heated phosphoric potassium dihydrogen (KH
2PO
4) make intermolecular dehydration, generate potassium metaphosphate, but different because of factors such as heating-up temperature and times, can obtain the goods of the various degree of polymerization, high polymerization degree is high more more to carry out the temperature of dehydration.This degree of polymerization and slickness have dependency relation, and from improving the viewpoint of hand washing property, the molecular weight of potassium metaphosphate is preferably more than 10,000, more preferably more than 100,000, further is preferably more than 200,000, further is preferably more than 500,000.Moreover the viewpoint of being easy to get property is set out calmly, is preferably below 5,000 ten thousand, more preferably below 2,000 ten thousand.In addition, so-called in the present invention molecular weight index average molecular weight.
Potassium metaphosphate general formula (KPO
3)
nExpression, but it is constructed as follows shown in the formula.
PO
4Total oxygen and in conjunction with (polymerization) between the tetrahedron forms the anionic network of polyphosphoric acid, in and the anionic charge balance of polyphosphoric acid, present structure with the potassium ion coordination.Shown in above-mentioned structure, the element that will form the anionic network of polyphosphoric acid usually as phosphorus is called " network forming element ", with the network forming element of phosphorus homotype displacement (isomorphous replacement), total oxygen and combination forms anionic network.In addition, the element that will bear the task of the electric charge of adjusting polyphosphoric acid anion network as potassium is called " network modification element ".
Employed potassium metaphosphate can contain and the network forming element of phosphorus homotype displacement (isomorphous replacement) and the network modification element except that potassium with specified quantitative among the present invention.With the network forming element of phosphorus homotype displacement and the network modification element except that potassium, promptly can in the raw material of potassium metaphosphate, contain, also can in manufacture process, contain.
Known potassium metaphosphate uses as the synergist of washing agent, in this purposes, about replacing the network forming element of (isomorphous replacement) and the network modification element except that potassium with the phosphorus homotype as described above, without any restriction, contain the performance that can not damage greatly as synergist with any ratio.On the other hand, be used in the potassium metaphosphate of purposes of the present invention, have only when its content is limited to particular range, could show to be suitable for performance of the present invention.
As the raw material of potassium metaphosphate,, can enumerate the so-called rock phosphate in powder of the natural product that contains a large amount of calcium phosphate etc. as industrial available phosphate cpd, furtherly as the phosphorus source.These rocks phosphate in powder of natural recovery become the phosphate cpd of phosphoric acid (salt) etc. through industrial processes through yellow phosphorus, phosphorous oxide etc.Under the situation that does not comprise refining step or fully do not make with extra care, the phosphate cpd class that originates from natural rock phosphate in powder contains a large amount of arsenic etc. and the network forming element displacement of phosphorus homotype, and these elements just are contained in wherein when being exploited as rock phosphate in powder.The phosphate cpd class that is used for the cheap industrial level of washing agent purposes lattice of equal value is not carried out highly purified, such phosphate cpd class to it usually and is contained the network forming element a large amount of and displacement of phosphorus homotype.According to difference of the manufacturing procedure of the grown place of rock phosphate in powder, rock phosphate in powder etc., content with the network forming element displacement of phosphorus homotype that contained changes to some extent, but in general, the phosphate cpd class of commercially available industrial level contains about tens～100 ppm by weight and network forming element phosphorus homotype displacement.
On the other hand, as the raw material of potassium metaphosphate,, can enumerate potassium hydroxide that obtains by electrolytic chlorination potassium etc. as industrial available potassium source.Potassium chloride is to utilize the industrialness crystallization to make with extra care impure mixtures such as carnallite, kainite (kainite), sylvite (sylvine), haraz-salz to obtain, the potassium chloride of this class industrial level contains a large amount of with inexpungible other composition of crystallization, promptly contains a large amount of sodium chloride or magnesium chloride etc.The composition of this class except that potassium chloride is carried in the potassium hydroxide that obtains after the electrolysis, so the potassium hydroxide of industrial level contains a large amount of network modification elements except that potassium.
Moreover, carry out a series of phosphorus manufacturing procedure or the producer of its a part of operation, phosphoric acid-potassium compound class product in addition of also producing the raw material that can become potassium metaphosphate without exception substantially from rock phosphate in powder to the phosphate cpd class.Like this, the phosphorus processer is for effective utilization of process equipment, for example in process equipments such as shared retort, drying machine, firing furnace, implement the processing of the phosphoric acid-sodium compound class of deriving by source of phosphoric acid and sodium source, the production of phosphoric acid-potassium compound class that can become the raw material of potassium metaphosphate or the production of potassium metaphosphate self usually.When changing the production kind, equipment such as cleaning, process management at kind order or process equipment do not have under the abundant ready-made situation, even be ready to be suitable for all various raw materials of potassium metaphosphate of the present invention, in manufacturing procedure, also can increase not preferred composition in the purposes of the present invention.
Be used to modulate the various raw materials of potassium metaphosphate of the present invention, also will carry out detailed inspection, according to circumstances preferably take the refining means that wait the composition beyond dephosphorization or the potassium.For example, be example in preferable range with content with the network forming element of phosphorus homotype displacement, in order to modulate potassium metaphosphate of the present invention, preferred use as highly refined food additives be supplied to, phosphoric acid-potassium compound such as potassium dihydrogen phosphate.
With the network forming element of phosphorus homotype displacement and the network modification element except that potassium, as long as its content is suitable, just may be mixed in in the potassium metaphosphate, the proterties that performance and phosphorus or potassium are same, give full play to the desired performance of potassium metaphosphate of the present invention, that is, significantly improve slickness, give full play to as the useful performance of hand washing with washing agent by having particular viscosity.As with the network forming element of phosphorus homotype displacement, be not particularly limited, but illustration B, As, Si, Ge, Sb, Ti, Sn, Al, Zr etc.With respect to the 1kg potassium metaphosphate, the content of the network forming element (NWF) of these and phosphorus homotype displacement is preferably 0～0.7mmol, more preferably 0.0001～0.4mmol, 0.0002～0.1mmol more preferably.
Moreover the network modification element as except that potassium is not particularly limited, but illustration Fe, Mg, Ni, Zn, Co, Ca, Sr, Ba, Li, Na, Rb, Cs etc.With respect to the 1kg potassium metaphosphate, the content of these network modification elements (NWM) except that potassium is preferably 0～100mmol, more preferably 0.0001～75mmol, 0.0002～25mmol more preferably.
In addition, the content of above-mentioned network forming element or network modification element is according to method described later, uses atomic absorption spectrum analysing arrangement or ICP apparatus for analyzing luminosity to measure.
In addition, in the present invention, the mol ratio of potassium in the potassium metaphosphate compound and phosphorus (hereinafter referred to as " K/P than ") is not particularly limited, but is preferably less than 1, more preferably 0.999～0.94, more preferably 0.99～0.98.When K/P than less than 1 the time, its advantage is that the polyphosphoric acid anion in the potassium metaphosphate is a following formula:
Shown crosslinked configuration becomes the two-dimensional layer macromolecule from the one-dimensional chain macromolecule, and the degree of polymerization uprises, the slickness that easier performance is high.In addition, the mol ratio of K/P can utilize the assay method described in the embodiment described later to measure.
The manufacture method of potassium metaphosphate then, is described.As above-mentioned, potassium metaphosphate obtains by dehydrating condensation potassium dihydrogen phosphate at high temperature, but in the present invention, in order to adjust the K/P ratio, and mixed phosphate potassium dihydrogen and phosphoric acid, and obtain by at high temperature making it dehydrating condensation.
The mixing of potassium dihydrogen phosphate and phosphoric acid is preferably even mixing.Potassium metaphosphate forms liquation in fusion more than 800 ℃.Therefore, when the synthesis temperature of potassium metaphosphate is to become the liquation state more than 800 ℃ the time, but the uniformly mixing raw material just of the diffusion by liquid.But, when below 800 ℃ when synthetic, because for being solid phase reaction, so, be preferably in advance and burn till behind the uniformly mixing raw material from the viewpoint of slickness.As the mixing example of concrete raw material, because potassium dihydrogen phosphate and phosphoric acid are water-soluble substances, so be preferably them as uniform aqueous solution and carry out spray-dired method.Mix example as this type of, mix the method for the aqueous solution in potassium sources such as phosphorus sources such as containing phosphoric acid and potassium hydroxide in fact also the method with above-mentioned is the same with adequate rate, can obtain effect of the present invention.Moreover, pulverous potassium dihydrogen phosphate can be put in the mixer, mixer is rotated at a high speed, utilize the method that makes aqueous phosphoric acid spraying or drip to mix.Be preferably solid blender as mixer, but for example illustration horizontal circle cartridge type mixer, V-Mixer, double-deck pyramid type mixer, banding pattern mixer, pyramid type helical form mixer, high velocity stream ejector half mixer, rotational circle dish-type mixer, air-flow agitating type mixer, free-falling type mixer, agitating type mixer etc.Wherein, being preferably can more mixed uniformly high velocity stream ejector half mixer by high-speed mixing.Moreover, potassium dihydrogen phosphate is dissolved in the water, after phosphoric acid mixes, utilize spray-dired gimmick, can obtain the mixed-powder that potassium dihydrogen phosphate and phosphoric acid mix more equably.
In addition, viewpoint from the slickness of resulting potassium metaphosphate, also preferably in the aqueous solution that mixes above-mentioned potassium dihydrogen phosphate and phosphoric acid, for example also can contain and the network forming element of phosphorus homotype displacement and/or the network modification element except that potassium, it is evenly mixed the back spray drying, thus the method for modulation potassium metaphosphate.
From flooding the viewpoint of back slickness, the firing temperature when carrying out condensation reaction is preferably more than 400 ℃, more preferably more than 500 ℃, more preferably more than 600 ℃; Moreover, from the viewpoint of energy expenditure, be preferably below 1500 ℃, more preferably below 1300 ℃, more preferably below 1200 ℃, further be preferably below 800 ℃.
In the granulation chemical industry preface of the potassium metaphosphate that is fired into after being supplied to, residual or be attached to viewpoint on the clothing, preferred small particle diameterization from suppressing dissolving.
From the viewpoint of operability, the average grain diameter of potassium metaphosphate is preferably more than the 0.5 μ m, more preferably more than the 1 μ m, more preferably more than the 5 μ m, more preferably more than the 10 μ m, further is preferably more than the 30 μ m.On the other hand, the viewpoint from granulation and dissolubility (suppress dissolving residual/attached on the clothing) is preferably below the 300 μ m, more preferably below the 200 μ m, more preferably below the 100 μ m.
Be adjusted at method in the above-mentioned scope as average grain diameter with potassium metaphosphate, can enumerate and utilize Fuji Paudal (strain) society system Atomizer, Hosokawa Micron Corporation system Pin Mill, Turbo Kogyo Co., known pulverizers such as Ltd system Turbo Mill carry out the method for pulverization process.
From the viewpoint of conformability, the content of the potassium metaphosphate in the Slipperiness improving agent granulate for washing of the present invention is preferably more than 10 weight %, more preferably more than 30 weight %, further preferably more than 50 weight %.On the other hand, from deliquescent viewpoint, its content is preferably below 95 weight %, more preferably below 90 weight %, further preferably below 80 weight %.
In the present invention, aforementioned potassium metaphosphate can carry out granulation separately, also can with carry out granulation after adhesive, solubilizer and other composition mix.
2. adhesive
As adhesive, as long as have the composition ability of combination each other that constitutes Slipperiness improving agent granulate for washing that makes, just be not particularly limited, but, deliquescent viewpoint from this particle, the preferred water soluble adhesive from the viewpoint of storage stability, more preferably has the thermoplasticity water-soluble binder that has associativity solidifying below 40 ℃.As water-soluble binder, can enumerate mean molecule quantity is 2000～30000, is preferably 5000～15000 polyethylene glycol, and carbon number is 8～18 a saturated or unrighted acid etc., still, and wherein preferred polyethylene glycol.It can be used alone, but also also mix together.With respect to potassium metaphosphate, the amount of adhesive is preferably 0.05 times more than the amount by weight, and more preferably 0.07 times more than the amount, in addition, be preferably 10 times below the amount, more preferably 4 times below the amount, more preferably 3 times below the amount.
3. solubilizer
The potassium metaphosphate utmost point is insoluble in water, but presents water-soluble in the presence of solubilizer.Here said " solubilizer " is meant the source of sodium ions that contains the potassium in the replaceable potassium metaphosphate and/or the compound of lithium ion source and/or ammonium ion source.Therefore, by in containing the cleaning solution of potassium metaphosphate, cooperating the compound of the supply source that can be used as sodium ion and/or lithium ion and/or ammonium ion, make the potassium metaphosphate dissolving, washings become the viscous solution of washing agent shape, consequently, have the slickness that improves between washings, the advantage that improves hand washing property.
As above-mentioned solubilizer, can enumerate the potassium of displacement in the potassium metaphosphate, all comprise the solubilizer of sodium source and/or lithium ion source and/or ammonium ion source.And, the usefully inorganic salts of sodium, lithium and ammonium and organic salt, carboxylic acid sodium such as sodium carbonate, sodium chloride, sodium sulphate, sodium sulfite, natrium citricum for example, sodium phosphate, sodium metasilicate, polycarboxylic acid polymer sodium salt, poly-sulfonic acid polymer sodium salt, lithium halide and lithium sulfate.Wherein, the more preferably inorganic salts of sodium or organic salt.Moreover the salt form of surfactant or aliphatic acid, metal ion sealer etc. also can be used as solubilizer.
Above-mentioned potassium metaphosphate is presented water-soluble by sodium ion and/or lithium ion and/or ammonium ion displacement by the potassium ion in the potassium metaphosphate, therefore, in order to obtain good hand washing performance, require to use with soluble state with potassium metaphosphate.As long as the part of the potassium in the replaceable potassium metaphosphate, but with regard to display effect, but from the viewpoint of economy, the amount of solubilizer is preferably sodium ion and/or the lithium ion and/or the ammonium ion of the amount that can supply with the potassium ion in the potassium metaphosphate that is contained in the complete displacement washing liquid of energy.Amount as such solubilizer, when will supply with potassium metaphosphate in potassium ion when being one times of equivalent with the sodium ion of amount and/or the amount of lithium ion and/or ammonium ion, preferred its use amount is 0.5 times more than the equivalent, more preferably 1 times more than the equivalent, more preferably 2 times more than the equivalent, further be preferably 3 times more than the equivalent.On the other hand, with respect to potassium ion, in the presence of the sodium ion of surplus and/or lithium ion and/or ammonium ion, the hand washing performance to improve effect little.From this viewpoint, the amount of solubilizer is preferably 400 times below the equivalent, and more preferably 200 times below the equivalent, more preferably 100 times below the equivalent.Moreover, improve the viewpoint of effect from further keeping slickness, above-mentioned amount is preferably 30 times below the equivalent, more preferably 20 times below the equivalent.
In addition, when the sodium ion that cooperates necessary amount in the composition of detergent for other purpose and/or lithium ion and/or ammonium ion, need not to add in addition solubilizer.
As other composition in the particle, so long as do not hinder moving and, just can using this material of potassium metaphosphate, can suitably use metal enclosed dose, silicate, phosphate etc. as the material that composition of detergent is used usually.
In addition, the kind or the amount of the granulation aid by suitable selection particle can further continue washing performance.According to the kind or the amount of granulation aid, can cooperate potassium metaphosphate with low use level, thereby improve the free degree that activating agent cooperates.In this case, the ratio of the potassium metaphosphate in the particle is preferably below the 80 weight %, more preferably below the 60 weight %.Therefore, particle of the present invention is characterised in that and contains potassium metaphosphate, and the free degree of the use level of potassium metaphosphate is subjected to the restriction of the compositions such as adhesive in the particle, and this potassium metaphosphate improves washing performance by improving slickness keeping under the constant situation of washing force.In addition, as the granulation aid except that solubilizer, can enumerate normally used excipient.Specifically, starch derivatives and analytes thereof such as TOKUSIL, starch, Pine Flow.
4. the manufacture method of particle
Particle of the present invention, particularly when the use level of potassium metaphosphate is hanged down, when carrying out granulation in order evenly to mix with solubilizer etc. under the situation that uneven distribution does not take place, do not carry out the situation of the common potassium metaphosphate of granulation to compare with use, the former can bring into play effect.Particle of the present invention is not particularly limited, can be with for example stirring manufacturings such as rotating comminution granulation, extruding pelletization method, spray cooling.Rotate comminution granulation as stirring, for example have: mix other composition of potassium metaphosphate and adhesive and solubilizer (sodium source and/or lithium source) etc., heating up makes the adhesive dissolving, carries out the method for cooling off after the granulation; The limit mixes other composition of potassium metaphosphate and solubilizer (sodium source and/or lithium source) etc., and the limit is added the adhesive limit of fusion and carried out process for granulating; The limit mixes other composition of potassium metaphosphate and solubilizer (sodium source and/or lithium source) etc., after limit interpolation binder aqueous solution carries out granulation, implements dry method etc.As the extruding pelletization method, for example have: other composition of melting mixing potassium metaphosphate and adhesive and solubilizer (sodium source and/or lithium source) etc., carry out process for granulating by extruding granulator; Other composition of melting mixing potassium metaphosphate, binder aqueous solution and solubilizer (sodium source and/or lithium source) etc., carry out granulation by extruding granulator after, implement dry method etc.As spray cooling, for example have: other composition of melting mixing potassium metaphosphate, adhesive and solubilizer (sodium source and/or lithium source) etc., spray to low temperature space from nozzle, obtain the method for particle etc.
In addition, when using solubilizer, because potassium metaphosphate can be dissolved by moisture in the presence of solubilizer, tackify, therefore, the moisture when granulation is carried out in preferred inhibition.At this moment, as binder substance, preferably use to have fusible thermoplastic water-soluble binder solidifying below 40 ℃.As such water-soluble binder, as previously mentioned, can enumerate mean molecule quantity 2000～30000, the saturated or unrighted acid of preferred 5000～15000 polyethylene glycol, carbon number 8～18 etc., wherein, more preferably polyethylene glycol.In addition, when making water and binder aqueous solution, preferably in the operation of back, implement dry fully as adhesive.
The device that uses when carrying out granulation; the high speed disintegrator of for example dark river industry (strain) production, the colter mixer (Ploughshare Mixer) that Pacific Ocean machine worker (strain) produces etc. are arranged in stirring the rotation comminution granulation; as extruding granulator for example Fuji Paudal Co. is arranged, the wet type extruding granulator (twin dome gran) that the biaxial granulation machine (Pelleter Double) that Ltd. produces, DALTON company make etc.
Particle so that such method obtains after carrying out granulation, for the purpose that improves outward appearance and yield etc., can carry out the whole grain of fragmentation, spheroidization etc. as required.Can enumerate crush type comminutor (Power Mill), the FujiPaudal Co. that Dalton company produces as the device of fragmentation usefulness; the high speed disintegrator (Speed mill) that the Comil pulverizer that the Fitz pulverizer that the quick pulverizer (Flash Mill) that Ltd produces, Fitzpatrick company (U.S.) produce, Comil company (Canada) produce, field, ridge Seiko (strain) are produced etc.; can enumerate Fuji Paudal Co. as the spheroidization device, the Marumerizer that Ltd produces etc.When using above-mentioned thermoplastic water-soluble binder, supply with the temperature of giving disintegrating machine and preferably be cooled near the temperature of normal temperature, for example, pellet supply is vibrated cooler, to be cooled broken to design temperature enforcement afterwards, have this moment and suppress the advantage that broken thing adheres in disintegrating machine.
In order to reduce micro mist and/or meal, can adjust to the granularity of expectation by classification to the particle that whole grain is crossed.Adjust granularity by classification, can improve the outward appearance when using.Particulate that is produced by classification and/or meal are for example implemented to pulverize and be used as granulating raw material to it, or implement to be used as raw material after the fusion again, thereby can improve yield.
5. the quality of particle
From keeping the viewpoint of hand washing property improvement effect, as particle grain size of the present invention, more than the preferred 100 μ m of average grain diameter, more preferably more than the 150 μ m, further more than the preferred 200 μ m.In addition,,, be more preferably less than 1500 μ m, further preferably less than 1000 μ m preferably less than 2000 μ m from outward appearance and deliquescent viewpoint.In the present invention, so-called average grain diameter refers to the particle diameter of weight 50%.
From the viewpoint of outward appearance and graded properties, coating of particles is most preferably spherical, under the situation of extruding particle of not carrying out spheroidization, preferably extrudes diameter and length ratio near 1 particle.In addition, from the viewpoint of outward appearance, size distribution preferably is consistent as far as possible.On the other hand, from the viewpoint of storage stability, the moisture value in the particle is preferably in end article below the 10 weight %, more preferably below the 5 weight %, more preferably below the 1 weight %.
＜composition of detergent 〉
The notable feature of composition of detergent of the present invention is, contains above-mentioned Slipperiness improving agent granulate for washing or aforementioned Slipperiness improving agent granulate for washing and solubilizer and/or other composition.Because have above-mentioned feature; when washing; the cleaning solution that is dissolved with composition of detergent becomes the viscous solution of washing agent shape; when hand washing is washed; can improve hand washing property with light power washing by improving the slickness of being cleaned between the thing, and; dried skin softness after hand washing is washed, smooth presents handguard effect and the effect of protecting clothing.
Composition of detergent can be the arbitrary formulation in powder, particle, liquid or the paste, perhaps, also can be configured as agglomerate, tablet etc. by secondary operations, but in order to present the slickness to clothing rapidly and equably, preferred powder or particle shape.Wherein, preferably use with powder detergent as washing.
The content of the aforementioned Slipperiness improving agent granulate for washing in the composition of detergent is preferably 0.1～30 weight %, 0.5～20 weight % more preferably.
In order to improve the slickness between the washings, the content of the potassium metaphosphate in composition of detergent is preferably more than the 0.5 weight %, more preferably more than the 1 weight %, more preferably more than the 3 weight %, more preferably more than the 5 weight %, more preferably more than the 7 weight %, further be preferably more than the 10 weight %.In addition, though that slickness is improved effect is high owing to the usability that can reduce the washings after the washing, therefore, its content is preferably below the 30 weight %, more preferably below the 20 weight %.
In addition, from obtaining the viewpoint of good hand washing, concentration is preferably more than the 15mg/L in the potassium metaphosphate water during dissolving detergent composition modulation cleaning solution, more preferably more than the 30mg/L, further is preferably more than the 60mg/L.Moreover the viewpoint of usability of the washings after the washing is preferably below the 3000mg/L, more preferably below the 1500mg/L, further is preferably below the 1000mg/L.And, (ratio of the weight of water and clothing: the increase of the increase of reduction water weight/clothes weight), cleaning solution hardness, the non-ionic surface active agent in the composition of detergent, with respect to the rising of the weight rate of the non-ionic surface active agent composition of composition of detergent preferably increases concentration in the water of above-mentioned potassium metaphosphate according to bath raio.
As solubilizer, as long as identical with the solubilizer that can be used for aforementioned particles.In addition, as the amount of the solubilizer in the composition of detergent, preferred 0.5 times more than the equivalent with respect to the potassium ion in the potassium metaphosphate, more preferably 1 times more than the equivalent, further preferred 2 times more than the equivalent, further preferred 3 times more than the equivalent.In addition, improve the viewpoint of effect from keeping slickness, preferred 30 times below the equivalent, more preferably 20 times below the equivalent.In addition, as long as in Slipperiness improving agent granulate for washing, contain solubilizer, with regard to the unnecessary solubilizer that in composition of detergent, also contains.
Can further contain surfactant and/or synergist in the composition of detergent of the present invention.
As surfactant, can use normally used surfactant.For example can enumerate anion surfactant, non-ionic surface active agent.With regard to its example, can enumerate the anion surfactant of alkylbenzenesulfonate, alkyl ether or alkene ether sulfate, alkyl or alkenyl sulfuric acid, alpha-olefin sulfonate, alkane sulfonate, N-acyl amino acid type surfactant, alkyl ether or alkene ether carboxylate, amino acid type surfactant, alkyl or alkenyl phosphate or its salt etc.; Non-ionic surface active agents such as polyoxyalkylene alkyl (thiazolinyl) ether, polyoxyethylene alkyl phenyl ether, higher fatty acids alkanolamide or its alkylene oxide addition product, sucrose fatty ester, alkyl glycoside, fatty mono glyceride.
Wherein, from improving the viewpoint of slickness effect, be preferably alkylbenzenesulfonate, alkyl ether sulfate, alkyl sulfate salt, more preferably sodium alkyl benzene sulfonate.
Viewpoint from scourability, the content of the surfactant in the composition of detergent be preferably 5 weight % above, more preferably more than the 10 weight %, more preferably 12 weight % above, further be preferably 15 weight % above, further be preferably more than the 17 weight %.In addition, from the viewpoint of powder physical property, its content is preferably below the 40 weight %, more preferably below the 35 weight %, more preferably below the 30 weight %, further is preferably below the 26 weight %.
The surfactant that can also suitably cooperate betaine type amphoteric surfac-tant, phosphoric acid ester surfactant, soap, cationic surfactant etc. in the composition of detergent of the present invention.
As synergist, can enumerate metal ion sealer, alkaline agent, contamination preventing agent etc. again.
Owing to become the rising of deal along with the hardness in the washings, can reduce slickness and improve effect, so, the metal ion sealer is coupled in the composition of detergent as synergist, catch the hardness composition in the washings, can present the performance of potassium metaphosphate very effectively.And calcium ion capturing ability is 100mgCaCO
3Metal ion sealer more than the/g is more effective.As this type of metal ion sealer, can enumerate water soluble organic substance matter such as chelating agent such as zeolite, crystallized silicon hydrochlorate plasma permutoid, polyacrylate, acrylic acid-maleic acid polymer such as (salt), sodium phosphate trimer, edetate, methylglycine diacetin, citrate.
In addition, in the metal ion sealer, do not contain potassium metaphosphate, sodium carbonate, noncrystalline silicic acid sodium.
Can enumerate carbonate or silicate as alkaline agent.From improving the viewpoint of slickness effect, be preferably noncrystalline silicic acid sodium.
As contamination preventing agent again, can enumerate carboxymethyl cellulose, polyethylene glycol etc.
From improving the viewpoint of hand washing property, in composition of detergent, the use level of synergist is preferably more than the 5 weight %, more preferably more than the 10 weight %, more preferably more than the 15 weight %, further is preferably more than the 20 weight %; In addition, from the viewpoint of the balance that cooperates, its use level is preferably below the 60 weight %, more preferably below the 40 weight %, more preferably below the 30 weight %.
By in composition of detergent of the present invention, further cooperating silicate and/or phosphate, can further improve slickness and improve effect.
As silicate, known have noncrystalline, crystalline silicate, can use any silicate.Here, SiO
2/ M
2O mol ratio (M is an alkali metal) is preferably more than 1, more preferably more than 1.5, more preferably more than 2; In addition, this ratio is preferably below 4, more preferably below 3.Here, more preferably noncrystalline silicic acid sodium can suitably use No. 2 sodium metasilicate of JIS1 sodium metasilicate or JIS.From the viewpoint of hand washing performance, its use level in composition of detergent is preferably more than the 3 weight %, more preferably more than the 5 weight %, more preferably more than the 7 weight %.Moreover, the viewpoint of the dissolving residual volume when suppressing washing when improving effect from keeping high slickness, above-mentioned use level is preferably below the 30 weight %, more preferably below the 20 weight %.
As phosphate (except potassium metaphosphate), can enumerate sodium phosphate trimer, sodium pyrophosphate, sodium dihydrogen phosphate, sodium hydrogen phosphate, tertiary sodium phosphate etc., be preferably sodium phosphate trimer, viewpoint from hand washing property, its use level in composition of detergent is preferably more than the 5 weight %, more preferably more than the 10 weight %, more preferably more than the 15 weight %.Moreover, improve the viewpoint of effect and washing force from taking into account slickness, its use level is preferably below the 40 weight %, more preferably below the 30 weight %.
In the present invention, cooperate metal ion sealer, silicate, phosphate in the above-mentioned composition, its advantage to be, also can keep good hand washing performance even reduce the use level of potassium metaphosphate with above-mentioned amount.
Also can suitably add enzyme, spices, fluorescent dye, pigment etc. in the composition of detergent of the present invention.
Composition of detergent of the present invention with above-mentioned formation can be made by above-mentioned each composition of suitable mixing with known method.As the example of this class composition of detergent, for example can enumerate the composition of detergent that obtains with composition of being put down in writing in special permission Room communique 10 (1998)-25 (7159) the known conventional techniques collection (dress material powder detergent) and manufacture method etc.
In addition, the potassium metaphosphate that is contained in the composition of detergent of the present invention, as mentioned above, in water, in the presence of solubilizer, present water-soluble, so preferably reduce manufacturing process or the moisture when preserving.For example, when with spray drying manufactured composition of detergent, in the granulating working procedure after the spray drying operation, surface modification operation and the back mixed processes etc., preferably add slickness improver particle.
In addition, when hand washing is washed, also can add composition of detergent and the slickness improver particle made by the composition except that slickness improver particle respectively, thus the modulation cleaning solution.To lump in order suppressing to dissolve, preferably to use slickness improver particle.
The composition of detergent of the present invention that has above-mentioned formation by use, under the residual situation of adhering to for clothing in the dissolving that does not cause potassium metaphosphate, do not soak when placing or soak when placing, all can bring into play following effect: keep the slickness cleaned between the thing, do not hinder cleaning, hand washing wash easily, can also handguard.
Embodiment
Below, by embodiment the present invention is specifically described, still, the invention is not restricted to these embodiment.
＜viscosity measurement 〉
The 2g potassium metaphosphate is added in the 50ml water, stirred 1 minute, 4g sodium phosphate trimer (ShiShimonoseki Mitsui Chemicals, Inc system) is dissolved in the 50ml water and the solution that obtains stirred 3 hours, use Brookfield viscometer, be determined at the viscosity under 25 ℃ to wherein adding.
The mensuration of＜sodium content 〉
The 0.1g sample dissolution in water, is added the HCl aqueous solution (1:1 (Capacity Ratio)) of 4ml, and making full dose is 50ml.Use this solution, with atomic absorption spectrum analysing arrangement (VARIAN corporate system atom extinction device, SpectraAA220) sodium (Na) content in the mensuration sample.
＜arsenic Determination on content 〉
The 5g sample dissolution in water, is added the HCl aqueous solution (1:1 (Capacity Ratio)) of 4ml, and making full dose is 50ml.Use this solution, with ICP apparatus for analyzing luminosity (HORIBA/JOBINYVON corporate system, JY238ULTRAACE) arsenic (As) content in the mensuration sample.
The assay method of＜K/P mol ratio 〉
Get the 0.1g sample and place in the platinum crucible, add the Li of 5g again
2B
4O
7And 0.5g remover (Li
2CO
3: LiBr:LiNO
3=5:1:1 (weight ratio)), (Tokyo science (strain) system NT-2100), 1230 ℃ of following fusions, is made bead to utilize Bead-Sampler.
((strain) Rigaku system ZSX100e), is measured K and P (XRF intensity) in the bead under following condition to utilize the fluorescent X-ray device.
X-ray source: Rh manages ball
Electric current and voltage: 50kV, 50mA
Beam split crystallization detector angle
K:LiF SC (scintillation counter) 136.68deg
P:Ge PC (proportional counter) 141.19deg
The computational methods of K/P mol ratio are as follows: similarly measure KH with sample
2PO
4(Sigma-Aldrich Japan Co., Ltd. system, reagent superfine) as the benchmark of K/P mol ratio 1.00, calculates the K/P mol ratio of sample by following calculating.
The assay method of the average grain diameter of＜potassium metaphosphate 〉
(the hole field makes made with laser light scattering size distribution meter, LA-920), be 1.2 in refractive index, ultrasonic intensity is 7, the ultrasonic irradiation time is that 1 minute, mixing speed are under 4 the condition, measure sample (potassium metaphosphate) with 25 ℃ of ion exchange waters as dispersant, try to achieve the average grain diameter (μ m) of volume reference.In the present invention, so-called average grain diameter refers to median particle diameter.
The assay method of the average grain diameter of＜particle 〉
Average grain diameter (Dp) refers to the particle diameter of weight 50%, measures and calculates by following method.Promptly, use is by the metal system mesh screen (mesh: 2000 μ m of JIS Z8801-1,1410 μ m, 1000 μ m, 710 μ m, 500 μ m, 355 μ m, 250 μ m, 180 μ m, 125 μ m) and the grading plant that constitutes of pallet and Ro-Tap type oscillator, after with 3 minutes the 100g particle that becomes sample being carried out progressive operation, the cumulative weight frequency successively from particulate to coarse grain, the weight frequency of accumulative total is counted a μ m at the mesh of the initial sieve more than 50%, and, in the time of will counting b μ m than the mesh of the sieve of the big one-level of a μ m, at the cumulative amount of the weight frequency of sieve that will be from pallet to a μ m as c%, under the situation of weight frequency more than the sieve of a μ m as d%, can be according to following (formula) in the hope of average grain diameter (Dp).
Dp=10
A(formula)
Wherein, A=[50-(c-d/ (logb-loga) * logb)]/[d/ (logb-loga)]
In addition, according to the granularity of object sample, be necessary to increase and measure with the sieve of the corresponding mesh of this granularity.
The modulation example 1 of potassium metaphosphate
Each KH that 2880g is contained Na, the As of the amount of Table 1
2PO
4Being dissolved in 36 lifts away from the sub-exchanged water.Then, add H
3PO
4(Wako Pure Chemical Industries, Ltd., reagent superfine, purity 85%) is adjusted into the value shown in the table 1 with the K/P mol ratio, and further stirs.With spray-drying installation (Tokyo Physico-chemical Apparatus Co., Ltd.'s system, spray dryer SD-1000 type) this solution of spray drying, obtain powder.Resulting powder dislocation in the aluminum crucible, was burnt till under 700 ℃ 3 hours, obtain the potassium metaphosphate of the 1-1～1-5 shown in the table 1.
Table 1
In addition, after the potassium metaphosphate usefulness hammer coarse crushing that obtains, with sprayer (Fuji Paudal (strain) system), hammer winding number when pulverizing by making, the delivery rate (feeding speed) of raw material, the percent opening of sieve, the perforate of sieve directly change, be ground into the particle diameter of expection, and measure average grain diameter separately.In addition, for the potassium metaphosphate of 1-1, the modulation average grain diameter different 2 in crushed material.
The modulation example 1 of basis composition of detergent
No. 2 aqueous silicate solutions, 100kg sodium carbonate, 147.5kg sodium sulphate, 5kg polyethylene glycol, the CBS type fluorescent dye of 2.5kg, the 125kg zeolite of the dodecylphenyl sodium sulfonate aqueous solution of the 50 weight % of mixing 370kg water, 200kg, the 40 weight % of 50kg, after being modulated into uniform slurry, the spray drying slurry obtains basic composition of detergent.
Embodiment 1～3 and comparative example 1～2
With the 0.4kg potassium metaphosphate crushed material shown in the table 2 and 0.086kg lauryl sodium sulfate (Kao Corp's system, the EMAL10 powder) is fed into 80 ℃ (Mitsui three ponds (strain) system that is adjusted into, capacity is 2L, sheath is housed) in the super mixer, be that to be stirred to mixture temperature under the 3600r/min condition be 70 ℃ in spindle revolutions.Subsequently, (Kao Corp's system KPEG6000), further continues to stir 3 minutes to add the polyethylene glycol that 0.086kg is adjusted into 70 ℃.Subsequently, the mixture that obtains is packed in the extruding granulator ((strain) Dalton system, dome granDG-L1 type), directly be in perforate
0.5mm condition under extrude, densificationization.After the extrudate cooling that obtains, further use pelletizing machine ((strain) Dalton system, Power Mill, sieve
1.0mm) separate broken, classification, be adjusted at average grain diameter below the 700 μ m and more than the 355 μ m.
With resulting particle and the aforementioned basic composition of detergent extruded, evenly mix according to the ratio of respectively do for oneself 4.3 weight %, 95.7 weight %, obtain composition of detergent.
Comparative example 3～4
When mixing mutually with basic composition of detergent, pulverizing product with potassium metaphosphate replace extruding particle, to pulverize product and aforementioned basic composition of detergent, ratio according to respectively do for oneself 3.0 weight %, 97.0 weight % is evenly mixed, in addition identical with embodiment 1, thus composition of detergent obtained.
Embodiment 4～5
When particle modulator, append sodium palmitate shown in the table 3 (powder product) and Pine Flow KH (loose paddy chemical industry (strain) system) as raw material, in addition identical with embodiment 1, thus obtain extruding particle.The particle of extruding that obtains is evenly mixed according to the ratio of respectively do for oneself 6 weight %, 94 weight % with aforementioned basic composition of detergent, obtain composition of detergent.
In the present invention, wash, improve effect thereby estimate preferred slickness by under wash conditions, hand-washing based on the washing evaluation method of hand washing as follows.
The test evaluation that example 1＜hand washing is washed 〉
In the polypropylene system wash basin (YAZAKI system) of diameter 30cm, degree of depth 13cm, capacity 8.2L, fill and adjust to 25 ℃ the 89.3mgCaCO that is equivalent to
3/ liter 2 liters of hard water (the Ca/Mg mol ratio is 7/3), after Xiang Shuizhong drops into the resulting composition of detergent of 8.48g, do not continue to stir with hand from the degree that wash basin disperses with water.Stir beginning after 30 seconds,, pure continuous T-shirt (Gunze system, white, L size) is immersed in the clean water in the wash basin in all abundant moistening mode of T-shirt.Begin to flood after 1 minute and after 15 minutes, carry out following washing step (1)～(3), estimate slickness based on following evaluation criterion.In addition, flood after 15 minutes, then continue to repeat washing step below 15 minutes (1) and (2), the easiness of washing by rubbing with the hands of this moment is similarly estimated.For each composition of detergent, calculate 6 personnel evaluation results' of panel mean value.The result is illustrated in table 2 and 3.In addition, the evaluation criterion of called torulopsis is a grade 1, is expressed as follows state: when only carrying out this evaluation with above-mentioned adjustment hard water, the fold of T-shirt hinders slickness, and because of not steeping on the part of washing by rubbing with the hands mutually, so be very difficult to wash by rubbing with the hands, slickness is poor.In addition, only to aforementioned basic composition of detergent and when only the commercially available washing agent that does not cooperate potassium metaphosphate being carried out same evaluation in Japan, the slickness grade is 1.
[washing step]
(1) from the back part of T-shirt, with two chests that hold T-shirt, leaving under the state of cleaning water, wash the chest of T-shirt mutually by rubbing with the hands,
(2) part that just will wash by rubbing with the hands mutually for (1) three to five times of every repetition is immersed in and cleans in the water,
(3) continuously (1) and (2) repetition five times, the easiness of washing by rubbing with the hands when washing by rubbing with the hands is mutually estimated its slickness.
[evaluation criterion of slickness]
Grade 1: slickness is very low, harsh feeling is arranged, that hand washing is washed is very difficult.
Grade 2: slickness is low, harsh feeling is arranged, difficulty is washed in hand washing.
Grade 3: slickness is moderate, do not have harsh feeling, can hand-wash and wash.
Class 4: the slickness height, do not have harsh feeling, hand washing to wash easily.
Class 5: slickness is very high, do not have harsh feeling, hand washing is washed very easy.
Test example 2 (dissolving residual evaluation)
Carry out the washing machine washing under the following conditions.
Washing machine: the NA-F42Y5 of Matsushita Electric Industries
Washing clothes: 20 blocks of black cloths [blending (polyester/cotton=65/35 (weight ratio))]
Washing agent: 40g
Washing process: middle water level (water flowmeter is shown 40 liters)
Wash 9 minutes → float 2 times → dehydration 3 minutes → dry (under 20 ℃, 40%RH, placing 24 hours)
Behind the cloth drying, in 20 blocks of black cloths, select 10 arbitrarily.Based on adhering to/residual of the following evaluation criterion evaluation water-insoluble of this moment on black cloth.The result is illustrated in table 2 and 3.
The evaluation of residual [adhere to /]
Zero: no problem (not having attachment)
△: some adhering to arranged
*: attachment is arranged
* *: has adheres to residue in a large number
Table 2
Table 3
From above result as can be known: viscosity is the composition of detergent of the embodiment that contains the potassium metaphosphate particle 1～3 more than the 200mPas, is keeping good slickness, does not also have the problem of residual/tack.On the other hand, as can be known: viscosity is less than the composition of detergent of the comparative example that contains the potassium metaphosphate particle 1～2 of 200mPas, although there is not the problem of residual/tack, in dipping slickness variation after 1 minute; In addition, use the product of pulverizing to replace the composition of detergent of the comparative example 3～4 of potassium metaphosphate particle, although the slickness of flooding after 1 minute is good, prolonging slickness in time can variation.Further, as can be known: because the composition of detergent of the embodiment 4～5 that the use level of potassium metaphosphate reduces can be kept good slickness, the problem that does not also have residual/tack, therefore, as long as suitably select auxiliary agent, can with viscosity the composition of detergent of the use level minimizing of the potassium metaphosphate particle modulation potassium metaphosphate more than the 200mPas just.
Slipperiness improving agent granulate for washing of the present invention is applicable to that the hand washing of clothing for example etc. washs, and wherein, is particularly useful for soaking the hand washing of placing and washing for a long time.
Claims (13)
1. a Slipperiness improving agent granulate for washing is characterized in that,
It is the above potassium metaphosphate of 200mPas that described Slipperiness improving agent granulate for washing contains the viscosity in aqueous solution of measuring under the following conditions,
The 2g potassium metaphosphate is added in the 50ml water, stirred 1 minute, 4g sodium phosphate trimer (ShiShimonoseki Mitsui Chemicals system) is dissolved in the 50ml water and the solution that obtains stirred 3 hours, be determined at viscosity under 25 ℃ with Brookfield viscometer to wherein adding.
2. Slipperiness improving agent granulate for washing according to claim 1 is characterized in that,
With respect to the 1kg potassium metaphosphate, with the content of the network forming element of phosphorus homotype displacement be 0～0.7mmol, the content of the network modification element except that potassium is 0～100mmol.
3. Slipperiness improving agent granulate for washing according to claim 1 and 2 is characterized in that,
The aqueous solution by spray drying potassium dihydrogen phosphate and phosphoric acid or contain potassium dihydrogen phosphate, phosphoric acid, with the network forming element of phosphorus homotype displacement and/or the aqueous solution of the network modification element except that potassium, and enforcement is burnt till and is obtained described potassium metaphosphate.
4. according to each the described Slipperiness improving agent granulate for washing in the claim 1～3, it is characterized in that,
The average grain diameter of described potassium metaphosphate is more than the 0.5 μ m and below the 200 μ m.
5. according to each the described Slipperiness improving agent granulate for washing in the claim 1～4, it is characterized in that,
Also contain adhesive.
6. Slipperiness improving agent granulate for washing according to claim 5 is characterized in that,
Described adhesive is a polyethylene glycol.
7. according to each the described Slipperiness improving agent granulate for washing in the claim 1～6, it is characterized in that,
Also contain solubilizer.
8. according to each the described Slipperiness improving agent granulate for washing in the claim 1～7, it is characterized in that,
This Slipperiness improving agent granulate for washing is that the Slipperiness improving agent granulate for washing of usefulness is washed in hand washing.
9. according to each the described Slipperiness improving agent granulate for washing in the claim 1～8, it is characterized in that,
The average grain diameter of this Slipperiness improving agent granulate for washing is more than 100 μ m and less than 2000 μ m.
10. a composition of detergent is characterized in that,
Contain each the described Slipperiness improving agent granulate for washing in the claim 1～9.
11. a composition of detergent is characterized in that,
Contain each described Slipperiness improving agent granulate for washing and solubilizer in the claim 1～9.
12. according to claim 10 or 11 described composition of detergent, it is characterized in that,
Also contain surfactant and/or synergist.
13. the method that hand washing is washed is characterized in that,
With each the described composition of detergent water-soluble in the claim 10～12, make the concentration of potassium metaphosphate more than 15mg/L.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006138304A JP2007308826A (en) | 2006-05-17 | 2006-05-17 | Slipperiness improving agent granulate for washing |
| JP138304/2006 | 2006-05-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101443511A true CN101443511A (en) | 2009-05-27 |
Family
ID=38693887
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007800177565A Pending CN101443511A (en) | 2006-05-17 | 2007-05-14 | Slipperiness improving agent granulate for washing |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2007308826A (en) |
| CN (1) | CN101443511A (en) |
| WO (1) | WO2007132796A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103663402A (en) * | 2012-11-14 | 2014-03-26 | 云南莱德福科技有限公司 | Preparation method for high-viscosity potassium metaphosphate |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5557627B2 (en) * | 2009-07-28 | 2014-07-23 | ライオン株式会社 | Detergent composition, method for producing the same, and washing method |
| CN102897740B (en) * | 2012-11-14 | 2015-01-14 | 云南莱德福科技有限公司 | Production method and production equipment of potassium polymetaphosphate |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4824649A (en) * | 1987-08-31 | 1989-04-25 | Stauffer Chemical Company | High viscosity potassium metaphosphate |
| JPH0825731B2 (en) * | 1990-09-20 | 1996-03-13 | 信越化学工業株式会社 | Method for producing rare earth phosphate |
| JPH09175812A (en) * | 1995-12-26 | 1997-07-08 | Kao Corp | Production of crystalline silicic acid compound |
| JP2003077707A (en) * | 2001-09-03 | 2003-03-14 | Otowa Denki Kogyo Kk | Method for manufacturing non linear resistor |
| CN1774496B (en) * | 2003-05-15 | 2011-04-06 | 花王株式会社 | Slipping property-improving agent granulate for washing |
| JP2005104818A (en) * | 2003-07-01 | 2005-04-21 | Mitsui Chemicals Inc | Aluminum nitride sintered powder, method of manufacturing the same, amd its application |
-
2006
- 2006-05-17 JP JP2006138304A patent/JP2007308826A/en active Pending
-
2007
- 2007-05-14 CN CNA2007800177565A patent/CN101443511A/en active Pending
- 2007-05-14 WO PCT/JP2007/059825 patent/WO2007132796A1/en active Application Filing
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103663402A (en) * | 2012-11-14 | 2014-03-26 | 云南莱德福科技有限公司 | Preparation method for high-viscosity potassium metaphosphate |
| CN103663402B (en) * | 2012-11-14 | 2015-08-26 | 云南莱德福科技有限公司 | The preparation method of high-viscosity potassium metaphosphate |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2007132796A1 (en) | 2007-11-22 |
| JP2007308826A (en) | 2007-11-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1217301A (en) | Granular bleaching activator | |
| US7446085B2 (en) | Process for preparing detergent particles | |
| CN101443511A (en) | Slipperiness improving agent granulate for washing | |
| JPH07509268A (en) | detergent composition | |
| CN102858945A (en) | Granulated detergent composition | |
| JP2012107165A (en) | Method for manufacturing detergent particle group | |
| JP4176595B2 (en) | Cleaning composition | |
| CN1774496B (en) | Slipping property-improving agent granulate for washing | |
| KR20010085390A (en) | Granules for carrying surfactant and method for producing the same | |
| JP2672814B2 (en) | High density granular detergent composition | |
| EP1550712B1 (en) | Process for producing a granular anionic surfactant | |
| JP4393862B2 (en) | Manufacturing method of detergent particles | |
| CN100545254C (en) | Granular detergent composition and production method thereof | |
| JP4237532B2 (en) | Surfactant-supporting granules | |
| KR100841514B1 (en) | Nonionic surfactant-containing particle and method for producing same | |
| JP4667730B2 (en) | Method for treating crystalline alkali metal silicate | |
| JP2001003082A (en) | Surface modifier and group of detergent particle | |
| JP2006161031A (en) | Slipping property-improving agent for washing | |
| JP5612808B2 (en) | Detergent particles | |
| JP2022026081A (en) | Granular detergent composition for clothing and producing method of granular detergent composition for clothing | |
| JP4173836B2 (en) | Slippery improver granule for washing | |
| JP2004115791A (en) | Detergent particle group | |
| JPS63265999A (en) | High-density, particulate and concentrated detergent composition | |
| JP4188222B2 (en) | Bleach cleaning composition | |
| JP4447400B2 (en) | Surfactant-supporting granules |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20090527 |