JP2006002081A - Drying and finishing agent composition for automatic washer, sorbitan fatty acid ester therefor and method for rinsing dish, etc., using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a drying and finishing agent composition for an automatic washer for dishes, etc., having excellent dilution stability, storage stability, finishing property and low foaming tendency. <P>SOLUTION: The drying and finishing agent composition for an automatic washer contains (a) a polyglycerol fatty acid ester produced by esterifying an 8-12C fatty acid with a polyglycerol having a specific average degree of polymerization n (n=6 to 10) and containing a ring structure in an amount of ≤25 mass% in the composition, (b) a sorbitan fatty acid ester containing a sorbitan fatty acid ester as the main component and free sorbide and free sorbitol as unreacted components wherein the amount of the free sorbide is ≥0.5 pt.wt. based on 1 pt.wt. of the free sorbitol, (c) at least one kind of water-soluble solvent selected from propylene glycol, glycerol, polyethylene glycol and ethyl alcohol and (d) water. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a dry finish composition for an automatic washing machine, sorbitan fatty acid esters used therein, and a method for rinsing tableware and the like using the same.

  2. Description of the Related Art Conventionally, automatic dishwashers have been widely used in hotels, restaurants, schools, hospitals, restaurants, catering companies, company cafeterias, and the like in order to efficiently wash used dishes and utensils. Examples of the material for tableware and cooking utensils include glass, ceramics, porcelain, metal and plastic. In addition to tableware and cooking utensils, automatic washing machines are used in various manufacturing factories, processing factories, etc. to wash food processing machinery and equipment, parts, containers, plastic containers used for distribution, etc. Yes.

  And in the said automatic dishwasher, the rinse process by the rinse water containing a dry finish agent is normally performed following the washing | cleaning process by a cleaning agent. In the case of a mechanism in which rinsing is repeated a plurality of times, rinsing is performed with rinsing water containing a dry finish at the time of final rinsing.

  The drying finish is used to promote the drying of the tableware after rinsing, prevent the formation of water marks (spots) on the tableware, etc., and is used to obtain a good finish. Food additives such as sucrose fatty acid esters, sorbitan fatty acid esters, glycerin fatty acid esters, etc. that are excellent in emulsifying power, dispersing power, etc., remain in tableware, etc., and are safe even if they enter the mouth are used as the main components.

  In recent years, dry finishes based on polyglycerin fatty acid esters have been widely used. For example, (A) HLB 3-13 polyglycerin fatty acid ester is an essential component, and (B) a nonionic surfactant such as sorbitan fatty acid ester and (C) a solubilizing agent such as ethanol are added as necessary. A rinsing aid is disclosed (see Patent Document 1). In addition, as the polyglycerin component of component A, polyglycerin having a polymerization degree of 2-12 such as diglycerin and triglycerin is preferable, and as the fatty acid component, C6-22 unsaturated / saturated such as caproic acid and lauric acid. Fatty acids are preferred.

  In addition, the following technical ideas are disclosed as a drying finish for a dishwasher using a polyglycerin fatty acid ester and a sorbitan fatty acid ester and a method for solubilizing a sorbitan fatty acid ester that is hardly soluble in water.

  First, C6-10 fatty acid and sorbitan or glycerin partially esterified with a water-insoluble fatty acid ester (for example, sorbitan or glycerin caproic acid, caprylic acid, capric acid ester) and water to C6 A partial ester of 10 to 10 fatty acids and hexaglycerin or decaglycerin, specifically, caproic acid, caprylic acid, capric acid ester (especially monoester thereof) of hexaglycerin or decaglycerin within a specific region A method for solubilizing a water-insoluble fatty acid ester, which is added in the amount shown, is disclosed (see Patent Document 2).

  Moreover, with respect to the composition which consists of C6-10 fatty acid, a partial ester of sorbitan or glycerin and water, C6-10 fatty acid and glycerin have an average degree of polymerization of 2-5 polyglycerin, particularly tetra Solubilized products obtained by adding monoesters of glycerin caproic acid, caprylic acid, capric acid within the range indicated in the specific area are free from risks such as safety and flammability, and costly It is disclosed that it is useful when used in foods, cosmetics, detergents, etc., and is useful for applications requiring low foaming properties such as rinsing aids for dishwashers (patents). (Ref. 3).

  Further, (A) water containing a partial ester of C6-18 fatty acid and polyglycerol, or component (A) and (B) a partial ester of C6-18 fatty acid and sorbitol, sorbitan, sorbide, glycerin or diglycerin (C) by allowing the carboxylate or dehydroacetate salt represented by the predetermined formula to coexist in the water containing the component (A) or the component (A) and the component (C) in the temperature range of −5 to 50 ° C. However, it is disclosed that a transparent liquid which is soluble and stabilized in an aqueous composition can be obtained (see Patent Document 4).

Further, as essential components, a fatty acid ester of a polyhydric alcohol selected from the group of sorbitan, sorbitol, sorbide, and glycerin or a mixture of two or more of these, 10 to 70% by weight, sucrose fatty acid ester 1 to 30% by weight, A rinse agent composition obtained by dissolving 10 to 85% by weight of a hydric or polyhydric alcohol or a mixture thereof in water and adjusting to weakly acidic to weakly alkaline with a pH adjuster has performance required as a rinse aid. In addition, it is disclosed that stable solubilization and transparency are maintained even when diluted with water (see Patent Document 5).
JP 60-053599 A JP-A-2-67247 JP-A-4-208248 JP-A-4-244045 JP 2000-239697 A

  As described above, several methods have been disclosed for solubilizing sorbitan fatty acid esters that are sparingly soluble in water, but all are sufficient for use in dry finish compositions for automatic washing machines such as dishwashers. It was not something. Moreover, what mix | blended the sucrose fatty acid ester is generally excellent in storage stability and dilution stability, but tends to be inferior in terms of low foamability. Furthermore, when the polyglycerin fatty acid ester is blended in a large amount, the solubilization performance is enhanced, while the low foaming property is inferior, and particularly when it flows into a washing liquid containing a large amount of protein dirt, the foaming power is increased. In some cases, the cleaning water pressure is reduced by pumping air into the pump, leading to a reduction in cleaning power.

  For example, in Patent Document 2, as a method for solubilizing a fatty acid having 6 to 10 carbon atoms and a partial ester of sorbitan or glycerin, a polyglycerol fatty acid ester of a partial ester of a fatty acid having 6 to 10 carbon atoms and hexaglycerin or decaglycerin. However, the stability evaluation is limited to the stability at 25 ° C. In addition, it is clear that when the amount of sorbitan fatty acid ester exceeds the amount of polyglycerin fatty acid ester, a solubilized aqueous solution cannot be obtained stably, and a drying finish composition for dishwashers There is no suggestion about the effects and practicality when used for things. Moreover, in the said technical thought, the quantity exceeding the compounding quantity of expensive polyglycerol fatty acid ester of sorbitan fatty acid ester is mix | blended actively.

  Patent Document 3 discloses a solubilization method using a polyglycerol fatty acid ester of a polyglycerol having a polymerization degree of 2 to 5 and a fatty acid having 6 to 10 carbon atoms, and a rinsing aid for an automatic dishwasher using the same. Although an agent (dry finish) is disclosed, as an example in which good low foam performance cannot be obtained, Comparative Example 11 includes a combination of sorbitan monocaprylate and hexaglycerin fatty acid ester, and Comparative Example 12 Shows a combination of sorbitan monocaprylate and decaglycerin monocaprylate.

  And in patent document 4, the combination (sample No. 24) with sorbitan monocaprylate, sorbitan monolaurate, and decaglycerin monocaprylate is somewhat inferior in stability (-5 degreeC, 10 days), and stable. It shows that the property (45 ° C., 10 days) is extremely inferior. Furthermore, it is clearly shown that the stability (45 ° C., 10 days) is not improved even in a combination (sample No. 33) in which propylene glycol is added to the same combination.

  As a result of intensive studies to solve these problems, the present inventors used special sorbitan fatty acid esters, and could not be obtained conventionally by combining with specific polyglycerin fatty acid esters. The present inventors have found that it is possible to provide a dry finish composition for an automatic washing machine such as tableware having excellent dilution stability, storage stability, finish, and low foamability, and have reached the present invention.

  In order to achieve the above object, the present invention provides (a) a fatty acid having 8 to 12 carbon atoms and a polyglycerol having a specific average polymerization degree n (n = 6 to 10), and a cyclic structure in the composition. Polyglycerin fatty acid ester obtained by esterifying a product set to 25% by mass or less, (b) Along with sorbitan fatty acid ester as the main component, free sorbide and free sorbitol as unreacted components, The amount of sorbide is 1 with the amount of free sorbitol, and sorbitan fatty acid esters of 0.5 or more on a weight basis; (c) at least one water-soluble solvent selected from propylene glycol, glycerin, polyethylene glycol and ethyl alcohol; And (d) A first finish is a dry finish composition for automatic washing machines containing water.

  In addition, the present invention has, in particular, a dry finish composition for an automatic washing machine in which the HLB of the polyglycerin fatty acid ester as the component (a) is 10 or more, and the above (b) In the sorbitan fatty acid ester which is a component, the third summary is a dry finish composition for an automatic washing machine in which the fatty acid constituting the same has 6 to 12 carbon atoms.

  Furthermore, in the present invention, among them, in particular, the sorbitan fatty acid ester as the component (b) contains a monoester and a diester, and the weight ratio of the monoester to the diester is 5: 2 to 2. A dry finish composition for an automatic washing machine that is in the range of 1: 1 is the fourth gist, and the weight ratio of the component (a) to the component (b) is in the range of 1: 1 to 2: 5. A dry finish composition for an automatic washing machine is a fifth aspect.

  And among these, especially, this invention contains the monoglycerin fatty acid ester formed by esterifying the fatty acid of 8-12 carbon atoms and glycerin together with said (a)-(d) component. The dry finish composition for automatic washing machines is a sixth aspect, and in particular, the weight ratio of the component (a) to the component (b component + e component) is 1: 1 to 2: 5. A seventh aspect of the present invention is a dry finish composition for an automatic washing machine that falls within the range of

  In addition, among the above, the present invention provides, in particular, a dry finish composition for an automatic washing machine in which the total amount of the surfactant is set in the range of 7 to 50% by mass in the whole composition. And

  Furthermore, the present invention is a sorbitan fatty acid ester used in the dry finish composition for automatic washing machines according to the first or second aspect, and is free as an unreacted component together with a sorbitan fatty acid ester as a main component. The ninth gist is sorbitan fatty acid esters containing sorbide and free sorbitol, wherein the amount of free sorbide is 0.5 or more on a weight basis, with the amount of free sorbitol being 1.

  And especially this invention makes the 10th summary the sorbitan fatty acid ester whose carbon number of the fatty acid which comprises this is 6-12 in the said sorbitan fatty acid ester, The said sorbitan fatty acid ester is A sorbitan fatty acid ester containing a monoester and a diester and having a weight ratio of the monoester to the diester in the range of 5: 2 to 1: 1 is an eleventh aspect.

  Further, the present invention provides a dry finish obtained by diluting the dry finish composition for an automatic washing machine according to any one of the first to eighth items by 1000 to 40000 times in a rinsing step by an automatic washing machine. A rinsing method for rinsing tableware and the like using an aqueous agent solution is a twelfth aspect.

  That is, the dry finish for an automatic washing machine of the present invention is a combination of a specific polyglycerin fatty acid ester, a specific sorbitan fatty acid ester, a water-soluble solvent, and water. As a result of the synergistic action of sorbitan fatty acid ester and sorbitan fatty acid ester, it has excellent dryness, finish, and safety, low foaming properties, and stable solubilization and dilution stability even when diluted in water. It is also excellent in storage stability at various temperatures.

  In particular, it has good solubilization performance without containing a large amount of expensive polyglycerin fatty acid ester, and has relatively good storage stability not only at low temperature but also at high temperature of 40 ° C. Even a washing liquid containing protein stains in the washing tank has good low-foaming properties, and is excellent in dilution stability when diluted to an arbitrary magnification.

  Next, the best mode for carrying out the present invention will be described in detail.

  The dry finish composition for an automatic washing machine of the present invention comprises (a) a specific polyglycerin fatty acid ester, (b) a specific sorbitan fatty acid ester, (c) a specific water-soluble solvent, and (d) water. It contains.

  The polyglycerol fatty acid ester of the component (a) can be obtained by reacting polyglycerol with a fatty acid.

  The currently commercially available polyglycerin is obtained by polymerizing glycerin-related substances such as glycerin, glycidol, and epichlorohydrin. Moreover, as a manufacturing method of polyglycerol currently used industrially, the glycidol method, the glycerol polymerization method, the epichlorohydrin method, the diglycerol crosslinking method etc. are mention | raise | lifted. And most of the polyglycerin obtained by these methods contains 25 to 40% by mass of a cyclic structure, and in particular, the polyglycerin polymerized using the glycidol method produces a cyclic structure. Can be kept low.

  Therefore, in the dry finish composition for an automatic washing machine of the present invention, in particular, a polyglycerin fatty acid ester synthesized using polyglycerin in which the amount of cyclic structure in the polyglycerin is suppressed to 25% by mass or less is used. Yes. This is the first feature of the present invention. That is, in the polyglycerin fatty acid ester obtained by using polyglycerin containing more than 25% by mass of the cyclic structure, the number of hydroxyl groups that are hydrophilic groups is reduced and the hydrophilicity is inferior. This is because the excellent effects of the present invention such as storage stability and dilution stability cannot be obtained even when combined with the specific sorbitan fatty acid ester described later, which is a component (b).

  The amount of the cyclic structure in the polyglycerol can be easily determined by analysis by LC / MS measurement, and the average degree of polymerization of the polyglycerol can be determined by the hydroxyl value.

  And polyglycerol fatty acid ester can be obtained by making the said polyglycerol and a fatty acid react, removing reaction leaving water under a 200-280 degreeC, nitrogen stream, and a catalyst.

  The polyglycerin fatty acid ester used in the present invention must be the above polyglycerin having an average degree of polymerization of 6 to 10 and a fatty acid having 8 to 12 carbon atoms esterified. That is, when the average degree of polymerization of polyglycerin is less than 6, the storage stability of the dry finish composition decreases from the balance with other components, and when it exceeds 10, the spot prevention performance decreases. Further, when the number of carbon atoms of the fatty acid is less than 8, the spot preventing performance is lowered and the odor is hardened, and when it exceeds 12, the low foamability of the dry finish composition is lowered.

  Examples of such polyglycerin fatty acid esters include hexaglycerin caprylic acid ester, hexaglycerin capric acid ester, hexaglycerin lauric acid ester, decaglycerin caprylic acid ester, decaglycerin capric acid ester, decaglycerin lauric acid ester and the like. These 1 type may be used independently or may be used in combination of 2 or more type.

  And it is preferable to set the average esterification rate of the said polyglyceryl fatty acid ester to 5 to 20%, More preferably, it is 12 to 20%. This is because if the average esterification rate is out of the range of 5 to 20%, the spot prevention performance is deteriorated.

  In addition, as ester of polyglyceryl fatty acid ester, what contains 40-95 mass% of monoester, diester, and triester is preferable, and what contains 15-50 mass% of monoester is especially preferable.

  The polyglycerin fatty acid ester preferably has an HLB of 10 or more. This is because if the HLB is less than 10, storage stability, solubilization performance and dilution stability may be impaired.

  The blending amount of the polyglycerin fatty acid ester as the component (a) is preferably set in the range of 2.5 to 25% by mass (hereinafter abbreviated as “%”) with respect to the entire composition. . That is, if the blending amount is less than 2.5%, the desired storage stability, solubilization performance and dilution stability may be poor, and if it exceeds 25%, the balance as a whole becomes worse and the storage stability is reduced. This is because there is a possibility that the low foaming performance may become insufficient while the properties are lowered.

  On the other hand, the sorbitan fatty acid esters which are the component (b) of the present invention contain sorbitan fatty acid esters as the main components and free sorbide and free sorbitol as unreacted components.

  Such sorbitan fatty acid esters can be obtained by reacting sorbitol with a fatty acid to produce a sorbitan fatty acid ester. That is, when a sorbitan fatty acid ester is produced by reacting sorbitol with a fatty acid, it is difficult to purify the sorbitan fatty acid ester from the reaction mixture. Therefore, the produced product generally has various amounts of sorbitol fatty acid esters and sorbide fatty acid esters. Along with the esters, unreacted components such as free sorbitan, free sorbitol, free sorbide, and fatty acids are included. Therefore, conventional sorbitan fatty acid esters (usually marketed as “sorbitan fatty acid esters”) contain free sorbitan, free sorbide, and free sorbitol, and the content (total amount) of sorbitan fatty acid esters is It is 5-40 mass% with respect to the whole kind.

  On the other hand, the sorbitan fatty acid esters of the present invention are prepared by intentionally adjusting the amount of free sorbide and the amount of free sorbitol contained as the unreacted components, and the amount of free sorbide is less than the amount of free sorbitol. Then, the weight is set to be 0.5 or more. This is the second feature of the present invention. That is, if the amount of free sorbide is less than 0.5 relative to the amount of free sorbitol 1, the low foam performance is poor. In particular, the amount of free sorbide is preferably set to 0.6 to 23.0 on a weight basis with respect to the amount of free sorbitol.

  And in the sorbitan fatty acid ester of this invention, although the fatty acid which comprises ester may be a saturated fatty acid or an unsaturated fatty acid, it is preferable that the carbon number is 6-12. That is, when the number of carbon atoms of the fatty acid is less than 6, the spot prevention performance and the solubilization performance are inferior. When the number of carbon atoms exceeds 12, the low-foaming property of the dry finish is lowered.

  The ester contained in the sorbitan fatty acid esters may be a monoester or a diester, but the weight ratio of the monoester to the diester (monoester: diester) is 5: 2-1: Those in the range of 1 are preferred. That is, when there are more monoesters than the above range, low foaming and drying properties are poor, and conversely, when there are few monoesters, storage stability and spot prevention performance at high temperatures (40 ° C) are poor. Because it becomes.

  In addition, the weight ratio of free sorbide and free sorbitol and the weight ratio of monoester and diester in sorbitan fatty acid esters can be easily determined by analysis using a gas chromatograph. Incidentally, in the present invention, GC-12A manufactured by Shimadzu Corporation, filler silicon OV-17 glass column was used, trimethylsilylation was performed as a pretreatment, and then analysis was performed at a temperature rising condition of 10 ° C./min from 60 to 330 ° C. Went. And the quantity of free sorbide and free sorbitol was computed in the peak area of the gas chromatograph analysis chart. The weight ratio of monoester to diester is the total amount of monoester of sorbitol, sorbitan sorbide and fatty acid and the total amount of diester of sorbitol, sorbitan sorbide and fatty acid, based on the peak area of the gas chromatographic analysis chart. Calculated.

  The blending amount of the sorbitan fatty acid esters as the component (b) is preferably set within a range of 4 to 35% with respect to the entire composition. That is, when the blending amount is less than 4%, there is a possibility that the desired low foam performance and storage stability due to balance with other components may be poor, and when it exceeds 35%, the balance as a whole becomes poor and solubilized. This is because the performance and dilution stability are lowered, and the spot prevention performance may be insufficient.

  In addition, it is suitable to mix | blend the said (a) component and the said (b) component so that it may become the range of 1: 1-2: 5 by weight ratio. That is, the polyglycerin fatty acid ester that has been conventionally blended in a large amount as the main component is expensive, but according to the composition of the present invention, the proportion of the component (a) is set relatively low as described above. In addition, the sorbitan fatty acid ester is sufficiently solubilized, and it is possible to realize dilution stability in water as a drying finish for dishwashers and storage stability in a wide range of temperatures. Therefore, the material cost can be kept low.

  And as a water-soluble solvent which is the said (c) component, propylene glycol, polyethyleneglycol, glycerol, ethyl alcohol, etc. are mention | raise | lifted. These may be used alone or in combination of two or more. Of these, propylene glycol, glycerin, and ethyl alcohol are preferable from the viewpoint of storage stability, odor, safety, and the like, and particularly preferably, propylene glycol and glycerin are used from the viewpoint of balance with other components and dilution stability.

  The blending amount of the water-soluble solvent is preferably set within a range of 5 to 40% with respect to the entire composition. That is, if it is less than 5%, the desired storage stability and solubilization performance may not be improved, and if it exceeds 40%, the balance as a whole becomes worse and the storage stability decreases. This is because there is a possibility that a synergistic effect with other components cannot be obtained any more.

  And as the water which is said (d) component, tap water, soft water, ion-exchange water, pure water, purified water etc. are mention | raise | lifted, Preferably tap water and soft water are used. The above-mentioned “water” is the sum of water contained in the form of crystal water or aqueous solution derived from each component constituting the composition of the present invention and water added from the outside, and is a dry finish for automatic washing machines. It mix | blends so that the whole composition may be 100%.

  In addition, a monoglycerin fatty acid ester can be used as the component (e) in addition to the components (a) to (d) which are essential components in the dry finish composition for an automatic washing machine of the present invention. As the monoglycerin fatty acid ester, a monoglycerin fatty acid ester in which a saturated or unsaturated fatty acid having 8 to 12 carbon atoms and glycerin are ester-bonded is used. That is, if the number of carbon atoms of the fatty acid is less than 8, the spot preventing ability is lowered and the odor is hardened, and if it exceeds 12, the storage stability and low foaming property of the dry finish are lowered.

  Examples of such fatty acids include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, erucic acid, 2-ethylhexylic acid, and isostearic acid. These fatty acids may be used alone or as a mixture of two or more. Of these, saturated fatty acids are preferable, and caprylic acid, capric acid, lauric acid, and the like are preferable.

  The blending amount of the monoglycerin fatty acid ester is preferably set within a range of 0.1 to 3% with respect to the entire composition. That is, if it is less than 0.1%, the desired storage stability and low foam performance may be poorly improved. If it exceeds 3%, the low foam performance becomes saturated and synergistic with other components. This is because no further effect can be obtained. In view of cost, it is particularly preferable to set the content in the range of 0.5 to 2%.

  In addition, when mix | blending the monoglycerin fatty acid ester which is the said (e) component, the total amount (b + e) of (a) component and the said (b) component and (e) component is 1: 1-2 by weight ratio. : It is suitable to mix | blend so that it may become the range of 5. As described above, even if the proportion of the expensive component (a) is set low, the sorbitan fatty acid ester and monoglycerin fatty acid ester are sufficiently solubilized, and water as a drying finish for dishwashers is used. This is because the material cost can be kept low because it is possible to realize the dilution stability and the storage stability in a wide range of temperatures.

  The dry finish composition for automatic washing machines of the present invention includes, as optional components, a pH adjuster, an organic acid and its salt, a dye, a fragrance, a metal corrosion inhibitor, a bactericide, a deodorant, and an antistatic agent. Etc. can be used.

  The dry finish composition for an automatic washing machine of the present invention, which contains the above-mentioned essential components and optional components as appropriate, is diluted 1000 to 40000 times to form a dry finish aqueous solution as glass, ceramic, porcelain, metal, plastic. It can be used in the rinsing process of an automatic dishwashing machine that efficiently cleans tableware, cooking utensils, and the like made of such materials. The above dry finishing aqueous solution is excellent in drying property, finishing property, safety, low foaming property, very stable solubilization and dilution stability, and excellent storage stability in a wide range of temperatures. It has become.

  In particular, it has good solubilization performance even without containing a large amount of expensive polyglycerin fatty acid ester, has good storage stability not only at low temperature but also at high temperature of 40 ° C., in a washing tank of a dishwasher Even if it becomes a washing | cleaning liquid containing a protein stain | pollution | contamination, it has favorable low-foaming property.

  In addition to tableware and cooking utensils, in various manufacturing factories, processing factories, etc., in the rinsing process of automatic washing machines intended for washing food processing machine tools and their parts, containers, plastic containers used for distribution, etc. Can also be suitably used.

  Next, examples will be described together with comparative examples. The present invention is not limited to these.

  First, in order to prepare a composition, each component was prepared as follows.

[Component a]

[Component b]

[Component c]
・ Propylene glycol ・ Ethyl alcohol ・ Glycerin

[D component]
·Tap water

[E component]
・ Monoglycerin fatty acid ester 1: carbon number 8, monoester ・ Monoglycerin fatty acid ester 2: carbon number 8, mixture of monoester and diester

[Examples 1 to 45, Comparative Examples 1 to 13]
Next, using each of the above components, dry finish compositions for automatic washing machines having the compositions shown in Tables 3 to 14 below are prepared, storage stability, drying property, finish (spot prevention), low foam Evaluation was made on six items of property 1, low-foam property 2, and dilution stability. The evaluation results are shown in Tables 3 to 14 below. The numerical values in the table are shown as they are. Moreover, the test method and evaluation method of each said item are as showing below. However, those with poor storage stability (25 ° C.) results (not satisfying practicality) were not evaluated for other evaluation items. In addition, the above results include those separated and precipitated immediately after compounding.

(1) [Storage stability test]
Test method: The test dry finish composition is placed for one month at three storage conditions: room temperature (about 25 ° C.), low temperature (−5 ° C. to 5 ° C .; 24-hour cycle), and high temperature (40 ° C.). did. And it evaluated on the following references | standards.
・ Evaluation criteria ◎: No separation, precipitation, or discoloration ○: Separation or precipitation is not observed, but slight cloudiness is observed (no problem in practical use)
Δ: No separation or precipitation is observed, but slight cloudiness and discoloration are observed (no problem in practical use)
X: Separation, precipitation or discoloration is observed (there is a problem in practical use)

(2) [Dryability test]
Test method A plate-shaped glass test piece (50 mm × 100 mm × thickness 2 mm) is placed in 200 ml of a dry finish aqueous solution (concentration 0.005%, temperature 80 ° C.) diluted with warm water for 30 seconds. After soaking, it was slowly pulled up and allowed to stand at room temperature, and the time required for water droplets and water film to disappear was measured. And it evaluated on the following references | standards.
・ Evaluation criteria ◎: 1 minute or less ○: Over 1 minute and within 2 minutes △: Over 2 minutes and within 3 minutes ×: Over 3 minutes

(3) [Finishability test (spot prevention test)]
・ Test method Using a door type washer (DW-DR61, Sanyo Electric Co., Ltd.), set 170 glass tempered glass cups (HS tumbler, Sasaki Glass Co., Ltd.) in the center of the rack, and wash, rinse and dry. went. Washing was carried out by spraying a standard working concentration (0.18%) solution of a detergent for automatic dishwashers (Deterfine LK, manufactured by Teapol Diversity) at 60 ° C. for 43 seconds. The rinsing was performed by rinsing a test dry finish composition (concentration 0.005%) solution at 80 ° C. for 15 seconds. Note that there is a rest of 3 seconds between washing and rinsing. After rinsing, the glass was naturally dried at room temperature for 10 minutes, and then held over a fluorescent lamp to observe the surface state. The evaluation criteria are as follows.
・ Evaluation criteria ◎: No spot, excellent transparency and uniform finish ○: There are several drops of spot, but there is a sense of transparency △: Spot is partially (more than half of the surface), it is cloudy white X: Spots on the entire surface are clouded white

(4) [Low Foam Test 1]
Test Method 50 ml of a sample adjusted to a concentration of 0.1% and 60 ° C. was placed in a 200 ml stoppered graduated cylinder, shaken upside down 20 times, allowed to stand, and the amount of foam generated was measured. And it evaluated on the following references | standards.
・ Evaluation criteria ◎: Almost inferior ○: 10 ml or less Δ: Over 10 ml and 50 ml or less x: Over 50 ml

(5) [Low Foam Test 2]
Test Method Using a conveyor type washer (JWF-365, manufactured by Ishikawajima-Harima Heavy Industries Co., Ltd.), the amount of foaming in the washing tank during operation for 10 minutes was evaluated according to the following criteria.
<Operating conditions>
Washing temperature: 60 ° C
Detergent: Deterfine LK (manufactured by Teapole Diversity)
Detergent concentration: 0.18%
Washing tank capacity: 110 liters Rinsing water temperature: 80 ° C
Test dry finish concentration: 0.01%
Rinsing water amount: 12 liters / minute Dirty (dried egg white): 0.005% (relative to washing tank capacity)
Evaluation criteria A: Foam less than 5 cm from the cleaning liquid surface (draft) ○: Foam from 5 to less than 8 cm from the cleaning liquid surface (draft) Δ: Foam from 8 to less than 12 cm from the cleaning liquid surface (draft) ×: More than 12 cm Foaming (overflow from washing tank / lack of practicality)

(6) [Dilution stability test]
Test method An aqueous solution obtained by diluting the test dry finish composition 5 times and 10 times with ion-exchanged water is placed at room temperature (25 ° C.), and the state after 24 hours is observed. evaluated.
Evaluation criteria ○: Almost transparent to transparent, no precipitation or separation is observed Δ: Slightly cloudy but no precipitation or separation is observed ×: Precipitation or separation is recognized

  From the evaluation results in Tables 3 to 14, Examples 1 to 45 are almost good in any of the items of storage stability, drying property, finishing property (spot prevention property), low-foam property test, and dilution stability. It can be seen that a good result is obtained. On the other hand, it can be seen that Comparative Examples 1 to 13 have practical problems in at least some items.

Claims (12)

  (A) a fatty acid having 8 to 12 carbon atoms and a polyglycerin having a specific average polymerization degree n (n = 6 to 10), wherein the cyclic structure in the composition is set to 25% by mass or less A polyglycerin fatty acid ester obtained by esterification of (b), sorbitan fatty acid ester as a main component, and free sorbide and free sorbitol as unreacted components, and the amount of the free sorbide is defined as 1. Sorbitan fatty acid esters of 0.5 or more on a weight basis, (c) at least one water-soluble solvent selected from propylene glycol, glycerin, polyethylene glycol and ethyl alcohol, and (d) water. Dry finish composition for automatic washing machines.   The dry finish composition for an automatic washing machine according to claim 1, wherein the polyglycerin fatty acid ester as the component (a) has an HLB of 10 or more.   In the sorbitan fatty acid ester which is said (b) component, carbon number of the fatty acid which comprises this is 6-12, The dry-finishing agent composition for automatic washing machines of Claim 1 or 2.   The sorbitan fatty acid ester as the component (b) contains a monoester and a diester, and the weight ratio of the monoester and the diester is in the range of 5: 2 to 1: 1. The dry-finishing agent composition for automatic washing machines as described in any one.   The dry finish composition for an automatic washing machine according to any one of claims 1 to 4, wherein a weight ratio of the component (a) to the component (b) is in the range of 1: 1 to 2: 5. .   The monoglycerin fatty acid ester formed by esterifying (e) a fatty acid having 8 to 12 carbon atoms and glycerin together with the components (a) to (d) described above. The dry finish composition for an automatic washing machine as described.   The dry finish composition for an automatic washing machine according to claim 6, wherein the weight ratio of the component (a) to the component (b component + component e) is in the range of 1: 1 to 2: 5.   The dry finish composition for an automatic washing machine according to any one of claims 1 to 7, wherein the total amount of the surfactant is set in a range of 7 to 50% by mass in the whole composition.   A sorbitan fatty acid ester used in the dry finish composition for an automatic washing machine according to claim 1 or 2, comprising sorbitan fatty acid ester as a main component, and free sorbide and free sorbitol as unreacted components. A sorbitan fatty acid ester characterized in that the amount of free sorbide is 0.5 or more on a weight basis, with the amount of free sorbitol being 1.   The sorbitan fatty acid esters according to claim 9, wherein the fatty acid constituting the sorbitan fatty acid esters has 6 to 12 carbon atoms.   The sorbitan fatty acid ester according to claim 9 or 10, wherein the sorbitan fatty acid ester contains a monoester and a diester, and the weight ratio of the monoester to the diester is in the range of 5: 2 to 1: 1. .   In the rinsing process by an automatic washing machine, the tableware is prepared by using a dry finishing aqueous solution obtained by diluting the dry finishing composition for automatic washing machine according to any one of claims 1 to 8 to 1000 to 40000 times. A method of rinsing dishes, etc., characterized by rinsing etc.