JP2737457B2 - Dishwashing method and anti-adhesive and rinse aid - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dishwashing method for making it difficult for foods such as leftovers to adhere to the surface of washed dishes, an antiadhesive agent and a rinse aid used in this method.

[0002]

2. Description of the Related Art Conventionally, as shown in FIG. 21, for example, a dishwasher used for business use in a restaurant or the like is known. In this commercial dishwashing apparatus, tableware B is inserted between a pair of rotating washing arms 23 and 24 and rinsing arms 25 and 26 which are arranged vertically opposite a washing chamber 22 provided in a casing 21 and which are turned. Rack 2
7 is stored and the detergent liquid C stored at the bottom of the cleaning chamber 22 is supplied to a cleaning pipe 30 by a cleaning pump 29 having a filter 28.
After washing the dishes by squirting from the washing arms 23 and 24 through the above, the tap water passing through the solenoid valve 31 is warmed by the electric water heater 32, and the warmed warm water W is rinsed through the rinsing pipe 33 and the rinse arms 25 and 26. And the tableware B is rinsed out. The strainer pan 3 at the bottom of the cleaning chamber 22
Detergent liquid and water overflowing beyond 4 are discharged from the drain plug 35 to the outside via the drain pipe 36. Washed with detergent solution,
The tableware B rinsed with warm water is naturally dried without a dishwasher since the temperature of the warm water is as high as about 80 ° C., and is taken out of the washing room 22 after drying.

[0003] As a dishwasher used for home use, for example, there is one as shown in FIG.
In this household dishwashing apparatus, a rack 73 containing tableware B is accommodated in a washing chamber 72 provided in a casing 71, and a washing liquid C stored in a tank 74 at the bottom of the washing chamber is filtered by a filter 7.
After the tableware B is washed by squirting from the arm 78 to the upper rack 73 via the pipe 77 by the circulation pump 76 having 5, the washing liquid C in the tank 74 is discharged by the drainage pump 79. Next, the solenoid valve 80 is opened, fresh water is supplied to the tank 74 through the water supply pipe 81, and the fresh water is ejected from the arm 78 again by the circulation pump 76, and the tableware B
The rinsing is performed at least once. The tableware B washed with the detergent solution and rinsed with fresh water is taken out of the washing room 72 and wiped. In this way, the tableware B, which has been washed and dried by the commercial and household dishwashing apparatus, is provided with food such as cooked rice and side dishes, and is provided to a restaurant visitor or a family at home.

On the other hand, in the rinsing step of any of the above-mentioned dishwashing apparatuses, a rinsing auxiliary mainly composed of a surfactant is added to warm water W or fresh water. This rinse aid promotes the wetting of the tableware surface, causes a thin film of water to flow on the tableware surface, thereby washing away the detergent liquid used in the cleaning process remaining on the tableware surface, It is heated at the temperature of the washing liquid during washing and the temperature of the rinsing liquid during rinsing.The surplus heat evaporates the surface water in the form of a film, and insoluble substances such as minerals contained in the water concentrate on the tableware surface. This is to prevent remaining (water spot).

[0005]

When cooked rice provided to a visitor at a restaurant is left over and left on the surface of the tableware, the cooked rice is dried over time, and the cooked rice is more firmly placed on the tableware. Since it sticks, there is a problem that it does not easily peel off only by washing with a commercial dishwasher. In particular, this problem is serious and serious in a commercial dishwasher that collectively cleans a large number of dishes that have been used for a long time, unlike a home dishwasher. Thus, in order to solve this problem, in restaurants and the like, countermeasures have been taken in restaurants and the like, in which tableware with sticks of residual rice after use is immersed in a water bath before washing to make it easy to peel off the cooked rice. However, this countermeasure requires a considerable amount of labor and time for immersion, and thus has the drawback that the dishwashing apparatus hinders the original purpose of saving and speeding up dishwashing.

Also, at home, the whole family often cannot eat together, so that the dishes of the person who first eats are washed together with the dishes of the person who last eats. In such a case, the cooked rice may be washed together with the tableware of the meal, and in such a case, there is a disadvantage that the cooked rice sticks firmly to the tableware at the time of washing, and the rice will not be peeled off unless washed for a long time with a household dishwasher.

On the other hand, the rinsing aid used in the rinsing step includes esters of polyhydric alcohols such as sorbitan and sucrose with fatty acids such as capric acid and stearic acid,
Or a partial ester thereof or a pluronic surfactant. However, these rinse aids have the disadvantage that the surfactant itself remains on the dish surface as spots or spots (water spots) and loses the gloss of the dish surface. Further, these rinsing assistants can be used only in a narrow concentration range of 100 to 50 ppm, so that there is a disadvantage that concentration adjustment is difficult.

Accordingly, an object of the present invention is to provide an original idea that foods such as cooked rice sticking to tableware with drying during use after use are easily peeled from the tableware from the beginning.
In addition to providing an anti-adhesion agent, the anti-adhesion agent provides a dishwashing method capable of saving labor and speeding up dishwashing by omitting a conventional hot water bath immersion in a restaurant or washing for a long time at home. It is in. Another object of the present invention is to provide an excellent luster without leaving spots and spots on the surface of the tableware after rinsing, having both a function of preventing adhesion that facilitates peeling of food and a function of assisting rinsing,
Further, it is an object of the present invention to provide a rinse aid having a wide usable concentration range and to provide a dishwashing method capable of saving labor and speeding up dishwashing and achieving a good rinse finish by using the rinse aid.

[0009]

In order to achieve the above object, the present invention provides a method of applying an anti-adhesion agent to the surface of tableware made of porcelain, porcelain, glass or metal in order to easily peel off food. There, such an anti-adhesion agent is a compound having a fluoroalkyl group, a perfluoroalkyl group-containing phosphate, a homopolymer of an acrylate or methacrylate having a fluoroalkyl group and a hydrophilic group, and ( a) a structural unit derived from an acrylate or methacrylate having a fluoroalkyl group and (b) acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, an acrylate and methacrylate having a hydrophilic group, acrylamide and A few selected from the group consisting of methacrylamide Characterized in that both at least one compound selected from the group consisting of a copolymer consisting of derived constituent unit of one. Further, the copolymer, ethylene, vinyl chloride, vinylidene halide, styrene, acrylic acid and its alkyl ester, methacrylic acid and its alkyl ester, benzyl methacrylate, vinyl alkyl ketone, vinyl alkyl ether, butadiene, isoprene, chloroprene and It is preferred to have at least one other structural unit derived from a polymerizable compound not containing at least one fluoroalkyl group selected from the group consisting of maleic anhydride. On the other hand, the dishwashing method of the present invention is characterized in that the above-mentioned anti-adhesion agent for preventing food from adhering is applied to the surface of tableware made of pottery, porcelain, glass or metal. Also,
The anti-adhesion agent may be applied to the tableware by adding it to the rinse water during the rinsing step or spraying it after the rinsing step.

[0010] In order to achieve the above another object,
The present invention is a rinsing aid having both the function of preventing adhesion and the function of assisting rinsing, which facilitates peeling of food, pottery, porcelain,
It is to be applied to the surface of tableware made of glass or metal, and such a rinse aid has a homopolymer of an acrylate or methacrylate having a fluoroalkyl group and a hydrophilic group and (a) having a fluoroalkyl group Structural units derived from acrylate or methacrylate and (b) selected from the group consisting of acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, acrylate and methacrylate having a hydrophilic group, acrylamide and methacrylamide Characterized in that it contains at least one polymer selected from the group consisting of copolymers composed of constituent units derived from at least one of the above as an active ingredient. Further, the copolymer, ethylene, vinyl chloride,
Vinylidene halide, styrene, acrylic acid and its alkyl ester, methacrylic acid and its alkyl ester, benzyl methacrylate, vinyl alkyl ketone,
It preferably has at least one other structural unit derived from a polymerizable compound not containing at least one fluoroalkyl group selected from the group consisting of vinyl alkyl ether, butadiene, isoprene, chloroprene and maleic anhydride. . On the other hand, the dishwashing method of the present invention comprises applying the above-mentioned rinse aid, which has both a function of preventing adhesion that facilitates peeling of food and a function of assisting rinsing, to the surface of tableware made of pottery, porcelain, glass or metal. Features. The rinsing aid may be added to the rinsing water during the rinsing step, or may be applied to the tableware by spraying the tableware after the rinsing step.

[0011]

The anti-adhesion agent of the present invention is adsorbed on the surface of ceramic, porcelain, glass, or metal tableware by a hydrogen bond through a hydrophilic group, and is almost non-polar to food such as cooked rice left on the tableware by a hydrophobic group. It is considered that the food is in contact only with the dispersing force acting between the sex molecules, and the bond between the food and the hydrophobic group of the anti-adhesion agent is weak because it is a dispersing force. Therefore, the dried cooked rice is easily peeled from the tableware by washing. Further, the anti-adhesion agent is a compound having a fluoroalkyl group and is a specific chemical substance such as a perfluoroalkyl group-containing phosphoric acid ester, so that the effect of removing food by washing is improved. The dishwashing method of the present invention is applied to the surface of a ceramic, porcelain, glass, or metal tableware with the above-mentioned anti-adhesive agent that facilitates the peeling of food, so that the cooked rice left over on the washed tableware is peeled off. Even if this cooked rice is dried, it can be easily peeled off from the tableware in the later washing. In addition, when the anti-adhesion agent is sprayed after the rinsing step, the anti-adhesion agent can be applied evenly to a clean tableware surface, and when added to the rinsing water during the rinsing step, the residual heat drying with high-temperature rinsing water As a result, the anti-adhesion agent adheres to the dishes without waste.

On the other hand, it is considered that the rinse aid of the present invention exerts its effects by the following mechanism. That is, when applied to tableware made of pottery, porcelain, glass, or metal, it is adsorbed on the surface of the tableware by a hydrophilic group surrounding the hydrophobic group, and the surface of the tableware is made hydrophilic during rinsing to improve water penetration. Therefore, the detergent solution remaining on the tableware surface in the washing step and the insoluble matter in the rinse water are sufficiently washed away. When the dishes are dried after rinsing, the hydrophilic groups continue to be adsorbed on the surface of the ceramic, porcelain, glass, or metal tableware by hydrogen bonding, while the hydrophobic groups previously surrounded by the hydrophilic groups appear on the atmosphere side.
These hydrophobic groups then come into contact with food such as cooked rice left on the tableware with only a weak dispersing force acting between substantially nonpolar molecules. In other words, the leftover food is weakened in adhesion to the tableware by the rinse aid, so that it is easily separated from the tableware by washing even after drying. As described above, the rinsing aid has both functions of preventing adhesion and assisting rinsing, so that the tableware that is rinsed only in the rinsing step can be provided with an adhesion preventing effect, and the cleaning operation and the cleaning device can be simplified. . Further, the rinsing aid is a homopolymer of an acrylate or methacrylate having a fluoroalkyl group and a hydrophilic group, or (a) is derived from an acrylate or methacrylate having a fluoroalkyl group. Structural unit and (b) a structural unit derived from at least one selected from the group consisting of acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, acrylate and methacrylate having a hydrophilic group, acrylamide and methacrylamide Since it is a copolymer consisting of, in addition to the above-described effects, an effect is obtained in which, as a rinsing aid, no stains or spots are left on the surface of tableware after rinsing, excellent gloss is given, and the usable concentration range is widened. .

In another dishwashing method of the present invention, a rinse aid having both functions of preventing adhesion and assisting rinsing is applied to the surface of ceramic, porcelain, glass, or metal dishware.
The cooked rice left over after being washed on the tableware is easily peeled off, and even if the cooked rice is dried, it can be easily peeled off from the tableware in the subsequent washing. Further, the rinsing aid is a homopolymer of an acrylate or methacrylate having a fluoroalkyl group and a hydrophilic group,
Or (a) a structural unit derived from an acrylate or methacrylate having a fluoroalkyl group and (b) acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, an acrylate and a methacrylate having a hydrophilic group, Because it is a copolymer consisting of constituent units derived from at least one selected from the group consisting of acrylamide and methacrylamide, it does not leave stains or spots on the surface of tableware after rinsing, gives excellent gloss, and has a wide It can be used in a concentration range. Furthermore, if the rinsing aid is added to the rinsing water during the rinsing step, the rinsing aid adheres to the tableware without waste by preheating drying with a high-temperature rinsing water, and the tableware can be given an adhesion preventing effect in the rinsing step, The cleaning operation and the cleaning device can be simplified. Further, if spraying is performed after the rinsing step, the rinsing aid can be applied evenly to a clean tableware surface.

[0014]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to the illustrated embodiments. The anti-adhesion agent of the present invention is applied to the surface of tableware in order to make food less likely to adhere, and is composed of a compound that is adsorbed on the surface of tableware with a hydrophilic group and is adsorbed on the surface of food with a hydrophobic group. In many cases, the hydrophilic group and the hydrophobic group are bonded by a divalent organic group.

Embedded image M is a hydrogen atom, an alkali metal atom, an alkaline earth metal atom ammonium group, a substituted ammonium group A is a hydrogen atom, a lower alkyl group X is a halogen atom m is an integer of 1 to 20

As the hydrophobic group,

Embedded image n is an integer of 1 to 8 As the divalent organic group, for example,

Embedded image [Where Z is H, CH ₃ , C ₂ H ₅ , Cl, OR ′ (R ′ is H, C
H ₃ , C ₂ H ₅ , COCH ₃ , COC ₂ H ₅ ), and R has 1 to 4 carbon atoms.
I is an integer of 0 to 4, j is an integer of 1 to 4, k is 1
Or an integer of 3 or a combination of two or more of these.

Generally, tableware is made of pottery, porcelain, glass, metal or plastic, and food such as leftover rice cooked on the surface of tableware is made of starch or protein. Food adheres to the surface of tableware due to the van der Waals force acting between the molecules constituting the tableware and the molecules constituting the food, and the van der Waals force includes non-polar intermolecular molecules. It is thought that there is a dispersing force acting on the surface, a dipole force acting between molecules having an electric dipole, and a hydrogen bonding force when an atom having a high electronegativity in the molecule forms a hydrogen bond with a hydrogen atom. I have. Although the dispersing force is smaller than the dipole force and the hydrogen bonding force, tableware and food are each composed of a unique molecule.
It has all the powers of the species. And since it is impossible to change the material of the tableware and the food, in order to make it difficult for the food to adhere to the surface of the tableware, it is necessary to apply an anti-adhesion agent that sticks to the food only with the weak dispersing force. It is effective.
Therefore, a compound which strongly adsorbs on the surface of tableware excluding plastics by a hydrophilic group through a hydrogen bond due to a hydrophilic group and which is weakly adsorbed on a food surface mainly by a hydrophobic group with a hydrophobic group is used as an anti-adhesion agent.

The above compound has a fluoroalkyl group, and is preferably a perfluoroalkyl group-containing phosphoric acid ester. When an aqueous solution of a perfluoroalkyl group-containing phosphate ammonium salt is applied to, for example, a ceramic surface, the perfluoroal group-containing phosphate is converted into its OH group, as shown in FIG.
(Hydrophilic group) makes a hydrogen bond with the OH group in the upper cavity of the pottery surface, while the fluorocarbon chain (hydrophobic group) is oriented in the normal direction of the surface. The fluorocarbon chains prevent food such as cooked rice made of starch from adhering to the upper surface of the pottery surface. Further, since the oxide film and the adsorbed water also exist on the surface of the metal tableware, the perfluoroalkyl group-containing phosphate ester acts in the same manner as described above. The effect of preventing the adhesion of starch and the like is large when the perfluoroalkyl group-containing phosphate ester adsorbed on the ceramic surface is a monomolecular film, and when a polymolecular film of a certain degree or more is formed, the above-mentioned orientation is lost, and the effect of the starch and the starch is reduced. It is considered that a dipole force acts between them, and conversely, it becomes smaller. For this purpose, for example, the appropriate concentration of an aqueous solution of a perfluoroalkyl group-containing phosphate ammonium salt or the like exhibiting the above-mentioned inhibitory effect is set at 0.1% by weight in consideration of economy. It is desirable to set it from several% to 0.00 several%.

The following are examples of the present invention.

Embedded image

Embedded image The main component of Example 19 is a perfluoroalkyl group-containing phosphate compound, and the main component of Example 20 is a polymer containing a perfluoroalkyl group.

After a predetermined amount of each anti-adhesive agent was added to hot water of 83 ± 2 ° C. and stirred (see the concentration column in Tables 1 and 2), a cleaned ceramic dish was immersed in each hot water for 10 seconds. Then, it was dried by remaining heat. After the cooked rice liquor prepared by the cooked rice liquor preparation method was applied to the dried dish, it was dried at 20 ° C. for 20 hours to obtain a sample. At this point, the state of adhesion of the cooked rice to the dish was visually observed. The result was evaluated as I. Next, the dish after the visual observation was washed with the dishwasher described in FIG. 22, and the state of the cooked rice remaining after spraying an iodine solution on the dish surface after washing was observed. And this observation result was set to evaluation II. The results of each test are as shown in Table 1. In the figure, ◎, ○, △, × indicate evaluation I and II, in which order of the amount of rice cooked was extremely small, little, little, slightly little, no. It represents the same level as the processing dish.

[Table 1]

[Table 2]

As is clear from Tables 1 and 2, the composition comprising a fluoroalkyl compound has the effect of preventing the adhesion of cooked rice, and the composition of Example 19 comprising a fluoroalkyl group compound having a perfluoroalkyl group at the terminal. It can be seen that the higher the concentration, the higher the adhesion prevention effect. That is,
The fluorocarbon chains, which are the hydrophobic groups of the above-mentioned anti-adhesion agents, which have been hydrogen-bonded to the surface of the ceramic dish by OH groups, prevent adhesion of the cooked rice liquor itself to the dish and peel off the adhered cooked rice liquor from the dish. Is easy. All of the above adhesion preventive agents are applied to the surface of tableware on which food is to be served, and may adhere to food and be partially eaten. Therefore, an acute oral toxicity test using mice for the following four types of phosphate compounds having four kinds of perfluoroalkyl groups having the same structure as that of the most prominent anti-adhesion agent (1) to (4) was performed as follows. Performed as follows.

[0021]

Embedded image

Each of the above-mentioned compounds suspended in a 1.5% aqueous solution of carboxymethylcellulose was added to a group of five female and male mice (about 20 g in weight) at the age of 5 weeks at a time using a metallic stomach zolde. Gavage was administered and the general symptoms were observed for 7 days after administration. As a result, no symptoms were observed in any of the mice. From this result, the acute oral toxicity median lethal dose LD ₅₀ for each compound was observed with 1 g / kg or more. Based on this value, it can be concluded that there is little risk of acute oral toxicity if the above-mentioned compound is ingested by humans via food from the surface of dishes.

The rinsing aid of the present invention is applied to the surface of tableware having both a function of preventing adhesion that facilitates peeling of food and a function of assisting rinsing, and has a hydrophilic group and a hydrophobic group. It is composed of a polymer that is sometimes adsorbed on the surface of tableware by a hydrophilic group surrounding a hydrophobic group, and is adsorbed on the surface of food by a hydrophobic group that appears on the surface after drying. For example, as the hydrophobic group, there is a polyfluoroalkyl group Rf, and as the hydrophilic group, there is methoxypolyoxyethylene PEG,
It is considered that both are copolymerized into a compound having a molecular structure as shown in FIG. Note that Rf: CF ₃
CF ₂ (CF ₂ CF ₂ ) n-; n = 2 to 8 (mainly 3)

Embedded image

The above compound, as shown in FIG.
When diluted with water, hydrophilic PEG appears on the outside of the hydrophobic thread-like polymer Rf and adapts to water. Then, when the compound aqueous solution is applied or sprayed on the tableware surface, FIG. 19 (C)
As shown in (1), it is considered that hydrophilic PEG is adsorbed on the surface of the tableware, and the surface of the tableware is made hydrophilic to improve water penetration. Further, when the moisture on the tableware surface dries, FIG.
As shown in (D), PEG remains adsorbed on the dish surface,
It is considered that hydrophobic Rf comes out to the atmosphere side, prevents food such as cooked rice left behind after being put on tableware, and promotes peeling of food during washing. Since the state of FIG. 19D is considered to be the same as the mechanism already described in FIG. 14 for the anti-adhesion agent, the explanation of the anti-adhesion function and effect of the above-mentioned compound as a rinse aid will be omitted. The appropriate concentration of the polymer aqueous solution of the present invention is desirably in the range of several percent to 0.000 several percent by weight in consideration of economy.

The above polymer may be a homopolymer of an acrylate or methacrylate having a fluoroalkyl group and a hydrophilic group, or (a) a derivative derived from an acrylate or methacrylate having a fluoroalkyl group. And a structural unit derived from at least one selected from the group consisting of (b) acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, acrylate and methacrylate having a hydrophilic group, acrylamide and methacrylamide Preferred acrylates or methacrylates having a fluoroalkyl group and a hydrophilic group consisting of a copolymer consisting of units are represented by the general formula: CH ₂ = C (R ² ) COOCH (CH ₂ Rf) CH ₂ O ( R ¹⁰ O) n ₃ R ^{11 _{or, CH 2 = C (R 2}} ) COO ( in ^{_{R 10 O) n 3 R 1}} Rf [ wherein, R ¹ is A linear or branched alkylene group having 10 carbon ^{_{atoms, -SO 2 N (R 3)}} R 4 - group, -C
H ₂ CH (OR ⁵ ) CH ₂ — group (where R ³ is an alkyl group having 1 to 10 carbon atoms, R ⁴ is a linear or branched alkylene group having 1 to 10 carbon atoms) , R ⁵ is a hydrogen atom or an acyl group having 1 to 10 carbon _{atoms), -. CH 2 CH (} oR 5) CH 2 (oR 10) n 3 - group, -
A CH ₂ OCH ₂ CH (OR ₅ ) CH ₂ — group or

Embedded image R ² is a hydrogen atom or a methyl group, R ¹⁰ is an alkylene group having 2 to 6 carbon atoms, R ¹¹ is a hydrogen atom or a methyl group, Rf
Represents a linear or branched polyfluoroalkyl group having 3 to 20 carbon atoms, and n ₃ represents 1 to 50. ] It is a compound represented by these.

Examples of such compounds include the following.

Embedded image

A preferred monomer for forming the structural unit (a) has the general formula: RfR ¹ OCOC (R ² ) = CH ₂ [wherein Rf, R ¹ and R ² are as defined above. ] It is a compound represented by these. Examples of such monomers include the following. CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₁₀ OCOCH = CH ₂ CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₁₀ OCOC (CH ₃ ) = CH ₂ CF ₃ (CF ₂ ) ₆ CH ₂ OCOCH = CH ₂ CF ₃ (CF ₂ ) ₆ CH ₂ OCOC (CH ₃ ) = CH ₂ (CF ₃ ) ₂ CF (CF ₂ ) ₆ (CH ₂ ) ₂ OCOCH = CH ₂ (CF ₃ ) ₂ CF (CF ₂ ) ₈ (CH ₂ ) ₂ OCOCH = CH ₂ (CF ₃ ) ₂ CF (CF ₂ ) ₁₀ (CH ₂ ) ₂ OCOCH = CH ₂ (CF ₃ ) ₂ CF (CF ₂ ) ₆ (CH ₂ ) ₂ OCOC (CH ₃ ) = CH ₂ (CF ₃ ) ₂ CF (CF ₂ ) ₈ (CH ₂ ) ₂ OCOC (CH ₃ ) = CH ₂ (CF ₃ ) ₂ CF (CF ₂ ) ₁₀ (CH ₂ ) ₂ OCOC (CH ₃ ) = CH ₂ CF ₃ CF ₂ (CF ₂ ) ₆ (CH ₂ ) ₂ OCOCH = CH ₂ CF ₃ CF ₂ (CF ₂ ) ₈ (CH ₂ ) ₂ OCOCH = CH ₂ CF ₃ CF ₂ (CF ₂ ) ₁₀ (CH ₂ ) ₂ OCOCH = CH ₂ CF ₃ CF ₂ (CF ₂ ) ₆ (CH ₂ ) ₂ OCOC (CH ₃ ) = CH ₂ CF ₃ CF ₂ (CF ₂ ) ₈ (CH ₂ ) ₂ OCOC (CH ₃ ) = CH ₂ CF ₃ CF ₂ (CF ₂ ) ₁₀ (CH ₂ ) ₂ OCOC (CH ₃ ) = CH ₂ H (CF ₂ ) ₈ CH ₂ OCOC (CH ₃ ) = CH ₂ H (CF ₂ ) ₈ CH ₂ OCOCH = CH ₂ CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) (CH ₂ ) ₂ OCOCH = CH ₂ CF ₃ (CF ₂ ) ₇ SO ₂ N (C ₂ H ₅ ) (CH ₂ ) ₂ OCOC (CH ₃ ) = CH ₂ (CF ₃ ) ₂ CF (CF ₂ ) ₈ CH ₂ CH (OCOCH ₃ ) CH ₂ OCOC (CH ₃ ) = CH ₂ (CF ₃ ) ₂ CF (CF ₂ ) ₈ CH ₂ CH (OH) CH ₂ OCOCH = CH ₂ CF ₃ CF ₂ (CF ₂ ) ₆ CH ₂ CH (OH) CH ₂ (OCH ₂ CH ₂ ) ₄ OCOCH = CH ₂ CF ₃ CF ₂ (CF ₂ ) ₆ CH ₂ CH (OH) CH ₂ (OCH ₂ CH ₂ ) ₈ OCOC (CH ₃ ) = CH ₂ (CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH (OCOCH ₃ ) CH ₂ (OCH ₂ CH ₂ ) ₁₂ OCOC (CH ₃ ) = CH ₂

Embedded image

The hydrophilic groups include -OH, -COOM, -OS
O ₃ M, -SO ₃ M,

Embedded image [Wherein, M is a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium group, a substituted ammonium group, A is a hydrogen atom, a lower alkyl group X is a halogen atom m is an integer of 1 to 20 R ⁹ is an alkylene group having 1 to 5 carbon atoms. ].

The acrylic acid ester and methacrylic acid ester having a hydrophilic group include a general formula: CH ₂ = CR ⁶ COO (R ⁷ O) n ₁ (R ⁸ O) n ₂ R ⁹ wherein R ⁶ is hydrogen Atom or methyl group, R ⁷ has 3 carbon atoms
To 6 alkylene groups, R ⁸ represents —CH ₂ CH ₂ —, R ⁹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and n ₁ +
n ₂ ≧ 1, n ₁ represents an integer of 0 to 50, and n ₂ represents an integer of 0 to 50. There is a compound represented by the formula: Usually as _{^{R 7, -CH (CH 3)}} CH 2 - , but are suitable, -CH (C ₂
H ₅ ) CH ₂ — or the like. Of course, the type of R ^7, n
Any one or two or more of ₁ and n ₂ may be used in the form of a mixture of two or more different types.

In the acrylamide and methacrylamide having a hydrophilic group, a compound represented by the general formula CH ₂ 2CR ⁶ CONR ¹² R ¹³ [wherein R ⁶ is as defined above, and R ¹² is hydrogen or —CH ₂
OH, R ¹³ represents hydrogen or -CH ₂ OH. There is a compound represented by the formula:

Examples of the monomer forming the structural unit (b) include the following.

Embedded image

The copolymer according to the present invention comprises the above structural unit
In addition to (a) and (b), ethylene, vinyl chloride, vinylidene halide, styrene, acrylic acid and its alkyl ester, methacrylic acid and its alkyl ester,
It may have other structural units derived from a polymerizable compound not containing a fluoroalkyl group such as benzyl methacrylate, vinyl alkyl ketone, vinyl alkyl ether, butadiene, isoprene, chloroprene, and maleic anhydride. This can result in a copolymer that is advantageous in terms of durability and cost, or has solubility,
Various other properties can be appropriately improved. However, the amount of such other constituent units is preferably 10% by weight or less based on the copolymer.

Further, the compound was subjected to various anti-adhesion effects tests and rinsing tests described below. As a result, unlike the conventional rinsing aid, it gave excellent gloss without leaving stains or spots on the surface of tableware. It was confirmed that the concentration range was widened. The following are examples of the compounds used in the adhesion prevention effect test and the rinsing test. Example 1 CF ₃ CF ₂ (CF ₂ CF ₂ ) nCH ₂ CH ₂ OCOCH = CH
70 g of a compound represented by the formula: ₂ (a mixture of n = 3, 4, 5 in a weight ratio of 5: 3: 1), CH ₂ 2C (CH ₃ ) COO (CH ₂
30 g of CH ₂ O) ₈ CH ₃ and 400 g of isopropanol were placed in a glass four-necked flask (volume: 1 liter) equipped with a mercury thermometer and a polytetrafluoroethylene crescent blade stirrer, and stirred under a nitrogen stream. To sufficiently disperse. After nitrogen blowing for about 1 hour, 1.0 g of azobisisobutyronitrile was added, and the mixture was further stirred at 70 ° C. for 10 hours under a nitrogen stream to carry out a copolymerization reaction.
According to gas chromatography, the conversion of the copolymerization reaction was 9
It was shown to be greater than 9%. From this conversion, it was found that the ratio of each structural unit in the obtained copolymer was almost the same as the ratio of the charged monomers. The resulting dispersion contained 20% copolymer solids.

This copolymer dispersion was diluted with water so that the copolymer solid had a predetermined concentration (see the concentration column in Tables 3 to 6). This was used as an anti-adhesion agent.

The anti-adhesion agent was heated to 83 ± 2 ° C., and a cleaned ceramic dish (230 mmφ) and a transparent glass cup (65 mmφ × 122 mmH) were immersed for 10 seconds. It was taken out and dried by heat.

The cup after drying was visually observed, and the presence or absence of spots on the surface and the gloss of the surface were evaluated. Tables 3 and 4 show the results as evaluations III and IV, respectively.

In a dish, 20 ml of cooked rice liquor prepared by the method of preparing cooked rice liquor was put with a pipette and dried at 20 ° C. for 20 hours. After drying, the state of adhesion of the cooked rice to the plate was visually observed, and the observation result was shown as evaluation I. The cup was coated with a fixed amount of lipstick (Shiseido Elekseal), which had been applied to the thumb and forefinger in advance, by pinching the two fingers together.

Next, the dish and the cup were washed with a dishwasher, and an iodine solution was sprayed on the dish surface after washing to observe the state of the cooked rice remaining. And evaluate this observation II
As shown. Further, the state of adhesion of the lipstick on the cup after washing was visually observed, and the result was shown as evaluation V. Table 5 shows the evaluations I, II and V.

Preparation method of cooked rice liquid Cook cooked rice by a conventional method, and after making it fuzzy for 15 minutes, cook rice 7
500 ml of distilled water is added to 5 g, and the mixture is stirred for 30 minutes with a homogenizer. This was kept at 30 ° C. while stirring with a magnetic stirrer in a constant temperature water bath at 30 ° C. This was cooked rice liquid.

Examples 2 to 14 Polymerization was carried out in the same manner as in Example 1 with the following composition, and then diluted with water so that the copolymer solid in the copolymer dispersion had a predetermined concentration. The same evaluation was performed. The results are shown in Tables 1 and 3.

% By weight Example 1 (a) C ₂ F ₅ (CF ₂ CF ₂ ) nCH ₂ CH ₂ OCOCH = CH ₂ 70 (n = 3,4,5 Compounds in a Weight Ratio of 5: 3: 1 ) (b) CH ₃ (OCH ₂ CH ₂ ) ₈ OCOC (CH ₃ ) = CH ₂ 30

Example 2 (a) Same as (a) in Example 1 45 (b) H (OCH ₂ CH ₂ ) ₉ {OCH (CH ₃ ) CH ₂ } ₇ OCOC (CH ₃ ) = CH ₂ 35 HOCH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ 20

Example 3 (a) Same as (a) of Example 1 (b) H (OCH ₂ CH ₂ ) ₈ OCOC (CH ₃ ) = CH ₂ 35 CH ₂ = C (CH ₃ ) CO (OCH ₂ CH ₂ ) ₉ OCOC (CH ₃ ) = CH ₂ 5

Example 4 (a) CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ 65 (b) NCCH = CH ₂ 8 CH ₃ (OCH ₂ CH _{2) 23 OCOCH = CH 2 18} CH 3 (OCH 2 CH 2) 9 OCOC (CH 3) = CH 2 7 C 4 H 9 OCH 2 NHCOCH = CH 2 2

Example 5 (a) (CF ₃ ) ₂ CF (CF ₂ CF ₂ ) nCH ₂ CH (OH) CH ₂ OCOCH = CH ₂ 60 (n = 3,4,5 weight ratio of compound: 5: 3 (B) NCC (CH ₃ ) = CH ₂ 12 H (OCH ₂ CH ₂ ) ₉ OCOC (CH ₃ ) = CH ₂ 25 HOCH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ 3

Example 6 (a) CF ₃ CF ₂ (CF ₂ CF ₂ ) ₃ CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ 45 (b) H (OCH ₂ CH ₂ ) ₉ OCOC (CH ₃ ) = CH ₂ 25 HOCH ₂ CH ₂ OCOCH = CH ₂ 20 (c) H {OCH (CH ₃ ) CH ₂ } OCOC (CH ₃ ) = CH ₂ 10

Example 7 (a) Same as (a) of Example 1 60 (b) CH ₃ (OCH ₂ CH ₂ ) ₈ OCOC (CH ₃ ) = CH ₂ 33 (c) CH ₂ CHCH ₂ OCOC (CH ₃ ) = CH ₂ 2 ＼ / OC ₄ H ₉ CH (C ₂ H ₅ ) CH ₂ OCOC (CH ₃ ) = CH ₂ 5

Example 8 (a) H (CF ₂ CF ₂ ) ₄ CH ₂ OCOCH = CH ₂ 60 (b) H (OCH ₂ CH ₂ ) ₉ OCOC (CH ₃ ) = CH ₂ 30 (c) C ₄ H ₉ CH (C ₂ H ₅ ) CH ₂ OCOC (CH ₃ ) = CH ₂ 10

Example 9 (a) CF ₃ CF ₂ (CF ₂ CF ₂ ) ₃ CH ₂ 100 | CH ₃ (OCH ₂ CH ₂ ) ₄ OCH ₂ CHOCCH = CH ₂ ‖O

Example 10 (a) (CF ₃ ) ₂ CF (CF ₂ CF ₂ ) ₃ CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ 60 (b) NCC (CH ₃ ) = CH ₂ 30 HOCH ₂ NHCOCH = CH ₂ 10

Example 11 (a) CF ₃ CF ₂ (CF ₂ CF ₂ ) ₃ CH ₂ CH (OCOCH ₃ ) CH ₂ OCOCH = CH ₂ 70 (b) HOCOC (CH ₃ ) = CH ₂ 10 H (OCH ₂ CH ₂ ) ₉ OCOCH = CH ₂ 20

Example 12 (a) CF ₃ CF ₂ (CF ₂ CF ₂ ) ₃ CH ₂ CH (OH) CH ₂ (OCH ₂ CH ₂ ) ₁₂ OCOCH = CH ₂ 30 CF ₃ CF ₂ (CF ₂ CF ₂ ) ₃ CH ₂ CH (OCOCH ₃ ) CH ₂ OCOC (CH ₃ ) = CH ₂ 30 (b) HOCOCH = CH ₂ 10 H (OCH ₂ CH ₂ ) ₈ OCOCH = CH ₂ 20

Example 13 (a) Same as (a) of Example 1 53 (b) CH ₃ (OCH ₂ CH ₂ ) ₉ OCOC (CH ₃ ) = CH ₂ 21 H {OC (CH ₃ ) CH ₂ } ₁₂ OCOC (CH ₃ ) 13 CH ₂ CHCH ₂ OCOC (CH ₃ ) = CH ₂ 13 ＼ / O

Example 14 (a) CF ₃ CF ₂ (CF ₂ CF ₂ ) ₃ SO ₂ N (C ₂ H ₅ ) CH ₂ CH ₂ OCOCH = CH ₂ 40 CF ₃ CF ₂ (CF ₂ CF ₂ ) ₃ CH ₂ | CH ₃ (OCH ₂ CH ₂ ) ₄ OCH ₂ CHOCOC (CH ₃ ) = CH ₂ 20 (b) CH ₃ (OCH ₂ CH ₂ ) ₃ OCOCH = CH ₂ 30 (HOCH ₂ ) ₂ NCOCH = CH ₂ 10

Comparative Example 1 Evaluations I, II, III, IV and V were carried out in the same manner as in Example 1 except that the copolymer of Example 1 was replaced with sorbitan monocaprylate.
The results are shown in Tables 4, 5, and 6.

Comparative Example 2 The same evaluations III and IV as in Example 1 were performed on untreated cups. Table 4 shows the results.

Comparative Example 3 Evaluations I, II and V in the same manner as in Example 1 using an untreated plate and a glass
Was done. The results are shown in Tables 5 and 6.

[0058]

[Table 3]

[Table 4]

[Table 5]

[Table 6] Evaluation I ◎ Most of the cooked rice rises from the plate ○ 半 Half 〃 △ 〃 Partially 〃 × 〃 All adhere to the plate Evaluation II, V ◎ Extremely small amount of adhesion ○ 少 な い Low △ △ Somewhat Less × 同 じ Same level as no processing

1 to 6 are longitudinal sectional views showing a dishwashing apparatus used in a dishwashing method in which the antiadhesive agent of the present invention is added to rinse water during a rinsing step and applied to dishes. Among these devices, those shown in FIGS. 1, 3, and 5 each include a hydraulically driven diaphragm pump, an electric diaphragm pump, and an ejector, and a built-in electric water heater, which can be accommodated under a sink. It is a counter type. On the other hand, those shown in FIGS. 2, 4, and 6 each include a hydraulically driven diaphragm pump, an electric diaphragm pump, and an ejector, and an external gas water heater so that a large amount of dishes can be washed at once. It is a high door type.

The dishwasher shown in FIG. 1 is different from the conventional apparatus shown in FIG. 21 in that a tank 1 storing an anti-adhesion agent A and a passage for introducing the anti-adhesion agent A in the tank 1 to an electric water heater 32. 2
In addition, a diaphragm pump 3 driven by the discharge pressure of the washing pump 29 is provided in this passage 2 via check valves 4 and 5, and the same members as those in the apparatus of FIG. ing. The diaphragm pump 3 sucks a certain amount of the anti-adhesion agent A through the check valve 4 by the push-back operation of the diaphragm 7 by the back spring 6 when the cleaning pump 29 is stopped, and the detergent discharged from the cleaning pump 29 during operation. When the diaphragm 7 is pushed out by the liquid pressure of the liquid (see the dashed line in the figure), the anti-adhesion agent A is discharged into the electric water heater 32 through the check valve 5.

FIG. 3 shows a modification of the apparatus shown in FIG. 1. In this modification, an electric diaphragm pump 8 is provided in place of the diaphragm pump 3 shown in FIG. 1, and the electric diaphragm pump 8, the washing pump 29, and the electric hot water are used. A controller 9 is provided for controlling the sequence of the heater of the boiler 32 and the electromagnetic valve 31 for water supply in accordance with the cleaning process. The controller 9 controls the cleaning pump 29 based on the control program.
Is turned on for a predetermined time to execute the cleaning process, and the electromagnetic valve 31
Is opened for a predetermined time to execute the rinsing step, and controls the pause time between the two steps, and also controls the timing of the suction and discharge operations of the electric diaphragm pump 8. FIG. 5 is a simplified version of the device of FIG.
In this modification, the diaphragm pump 3 of FIG. 1 is omitted, the passage 2 for leading the anti-adhesion agent A is joined to the rinsing pipe 33, and a check valve 11 is provided at the end of the passage 2.
, And the ejector 10 is disposed in the rinsing pipe 33. When the rinsing water W is fed into the rinsing pipe 33 by opening the water supply electromagnetic valve 31, the anti-adhesion agent A is sucked into the rinsing water W by the ejector 10.

On the other hand, the door-type dishwasher shown in FIGS. 2, 4 and 6 is basically different from the under-counter type dishwasher shown in FIGS. The configuration is the same. That is, in this apparatus, the upper part of the casing 21 is directly used as the washing chamber 22, and the washing chamber 22 is moved up and down to allow the rack 27 containing the tableware B to be taken in and out from three directions. A cleaning tank 13 for storing liquid C, and a water supply ball tap 15
An external gas water heater 14 having a rinsing pump 16 is used to boil and supply the rinsing water W. Other components such as an anti-adhesion agent tank 1, a diaphragm pump 3, an electric diaphragm pump 8, and an ejector 10 are the same. FIG. 2 is FIG. 1, FIG. 4 is FIG. 3, and FIG. 5, respectively. In addition, instead of the anti-adhesion agent A in the tank 1, if a rinsing aid described later is stored,
Add this rinse aid to the rinse water during the rinsing process,
Can be applied to tableware.

A method of adding an anti-adhesion agent to the rinsing water during the rinsing step and applying the anti-adhesion agent to the dishes by the dishwashing apparatus having the above configuration will be described with reference to FIG. 1 as an example. In FIG. 1, the diaphragm pump 3 sucks a certain amount of the anti-adhesion agent A from the tank 1 through the check valve 4 in the passage 2 by the operation of pushing back the diaphragm 7 by the back spring 6 when the cleaning pump 29 stops. When the cleaning pump 29 is started at the same time as the operation starts, the diaphragm 7 is pushed out by the pressure of the detergent liquid C discharged from the pump 29, and the anti-adhesive agent A is passed through the check valve 5 of the passage 2 to the electric water heater 3.
2 and the anti-adhesion agent A is added to the rinse water W. Further, the cleaning pump 29 sends the detergent solution C at the bottom of the cleaning chamber 22 to the upper and lower cleaning arms 23 and 24 in the cleaning chamber 22 via the cleaning pipe 30 and from there to the tableware B in the rack 27. By spouting, the tableware B is washed.

When the cleaning pump 29 is stopped after a certain period of operation and a certain period of time has elapsed, the solenoid valve 31 is opened to supply water to the electric water heater 32, and the water heater 32 supplies water to the electric water heater 32.
The water containing the anti-adhesion agent A, which has been warmed to
3, and is ejected toward the tableware B from the upper and lower rinse arms 25 and 26. Thereby, the detergent liquid C remaining on the surface of the tableware B is washed away, and the anti-adhesion agent A in the rinse water is strongly adsorbed to the surface of the tableware B by hydrogen bonding (FIG. 1).
4) and adheres without waste by drying with residual heat with high-temperature rinse water. When the cooked rice is put on the washed tableware B and left over and dried, the cooked rice having many hydroxyl groups is repelled by the hydrophobic group of the anti-adhesive agent A on the surface of the tableware B, and the tableware is dried. A basic effect is obtained that it can be easily peeled off from the tableware B only by washing with the dishwashing apparatus without performing the conventional pretreatment of hardly adhering to the dish B and immersing in the hot water tank for a long time. Therefore, by omitting the pre-treatment of immersion in a hot water bath, labor saving and speeding up of dishwashing as a business especially in a restaurant or the like can be realized. In the embodiment of FIG. 1, the diaphragm pump 3
Is driven by the discharge liquid pressure of the cleaning pump 29, so that there is no need to provide a separate driving means, and there is an advantage that the apparatus can be reduced in cost and size.

In the modification shown in FIG. 3, the electric diaphragm pump 8 is used, and the pump 8, the washing pump 29, the heater 17 of the electric water heater 32 and the solenoid valve 31 are sequence-controlled by the controller 9, so that In addition to the basic effects described in the above embodiment, there is an advantage that the cleaning time, the pause time, the rinsing time, the rinsing water temperature, and the timing of adding the anti-adhesive agent can be arbitrarily and easily set by a program. In the modification of FIG. 5, the diaphragm pump 3
Is omitted, and the ejector 10 is provided in the rinsing pipe 33. In addition to the basic effects described in the above embodiment, during the rinsing step of opening the solenoid valve 31, the anti-adhesion agent A is continuously connected to the rinsing water W. There is an advantage that it can be added, and the apparatus can be further reduced in cost and size. Further, the embodiments and modified examples of FIGS. 2, 4 and 6 differ from those of FIGS.
Since the structure is the same as that of the third or fifth embodiment, the same operation and effect can be obtained.

FIGS. 7, 8 and 11 are longitudinal sectional views showing a dishwashing apparatus used in a dishwashing method in which the antiadhesive agent is sprayed and applied to the dish after the rinsing step. Each of these devices is of the undercounter type, and its basic structure is the same as that provided with the controller 9 described in FIG. If a rinsing aid described below is stored in the tank 1 of these devices instead of the anti-adhesion agent A,
After the rinsing step, the rinse aid can be sprayed and applied to tableware. That is, instead of the anti-adhesion agent supply system shown in FIG. 3, the dishwashing apparatus shown in FIGS. And a diaphragm pump for supplying the anti-adhesion agent A therein to the spray nozzle 18 via the spray pipe 19, and the diaphragm pump 3 in FIG.
The electric diaphragm pump 8 of FIG. 8 is driven by the discharge pressure 9 and is controlled by the controller 9. The controller 9 shown in FIG.
Is also controlled.

On the other hand, in the dishwashing apparatus of FIG. 11, instead of the adhesion preventing agent supply system of FIG. 3, a spray nozzle 42 for spraying water toward the tableware B is provided at the tip and an electromagnetic on-off valve 43 is provided at the base. A water pipe 41 having the same, an anti-adhesion agent pipe 44 connected to the tank 1, and an ejector 10 provided at the end of the pipe 44 via the check valve so as to be located in the water pipe 41. The electromagnetic opening / closing valve 43 is controlled by the controller 9. The apparatus shown in FIGS. 9 and 10 is a modification of the dishwashing apparatus of FIG.
A water tank 45 is provided at the position of the ejector 10 in place of the ejector 10, and the water tank 45 is provided to the water tank 45 by the hydraulically driven diaphragm pump 3 (see FIG. 9) or the electric diaphragm pump 8 interposed in the anti-adhesion agent pipe 44. The anti-adhesion agent A is supplied.

Next, a method of applying the antiadhesive agent by the dishwashing apparatus having the above-described configuration will be described. In FIG.
After the rinsing step is completed based on the program (see P in FIG. 12A), the controller 9 closes the electromagnetic on-off valve 20 and starts the cleaning pump 29 (S1 in FIG. 12B).
reference). Then, the detergent liquid C discharged from the cleaning pump 29 drives the diaphragm pump 3 without being sent to the cleaning nozzles 23 and 24, whereby a certain amount of the adhesion preventing agent A previously sucked into the diaphragm pump 3.
Is sprayed from the spray nozzle 18 toward the tableware B via the check valve 5. Then, after a certain time has elapsed, the controller 9 stops the cleaning pump 29 and opens the electromagnetic on-off valve 20 (see S2 and S3 in FIG. 12B).

Thus, the clean tableware B which has been completely cleaned is obtained.
The anti-adhesion agent A can be applied evenly to the surface of the substrate. Therefore,
The above-described basic effect that the leftovers dried and adhered to the surface of the tableware can be easily peeled off only by washing with the tableware washing apparatus is obtained, and the labor and speed of the tableware washing are realized. In addition,
In the embodiment shown in FIG. 7, since the diaphragm pump 3 driven by the hydraulic pressure is used, there is an advantage that the apparatus can be made inexpensive and compact. In the modification shown in FIG. 8, the electric diaphragm pump 8 controlled by the controller 9 is used.
There is an advantage that the spray timing of the anti-adhesion agent A can be arbitrarily and easily set even without the above.

In the dishwashing apparatus having the above configuration (see FIG. 11), after the rinsing step is completed (see FIG. 12).
(Refer to P in (a)), the electromagnetic on-off valve 43 is opened. Then, the anti-adhesion agent A is sucked into the water pressure-fed to the water pipe 41 via the electromagnetic on-off valve 43 via the pipe 44 by the ejector 10, and the anti-adhesion agent diluted with water is supplied from the spray nozzle 18 to the tableware B. Sprayed towards. Thus, in the same manner as described with reference to FIG. 7, the basic effect of easily removing the debris that has dried and adhered to the surface of the dish after the washing has been completed is obtained only by washing with the dishwashing apparatus. Speed is achieved. In the embodiment of FIG. 11, the diaphragm pump 3 of FIG.
Since 0 is provided, there is an advantage that the anti-adhesion agent A can be continuously added to water during the water supply period, and the apparatus can be further reduced in cost and size.

In the modification shown in FIG. 9, a water tank 45 is provided instead of the ejector 10, and the anti-adhesion agent A is provided by the diaphragm pump 3 driven by the discharge pressure of the cleaning pump 29.
Is provided, and in addition to the basic effects of the above-described embodiment, there is an advantage that the apparatus can be reduced in cost and size by omitting the pump drive source. Further, in the modified example of FIG. 10, the electric diaphragm pump 8 controlled by the controller 9 is provided instead of the diaphragm pump 3 of FIG. 9, so that the addition of the anti-adhesion agent A is added to the basic effect of the above embodiment. There is an advantage that the timing can be set arbitrarily and easily.

FIG. 12 (a) is a flowchart generally showing the operation sequence of the under counter dishwasher (see FIGS. 1, 3, 5, 7, 8 to 11). Each of the above devices
When the operation switch is turned on in step S1, the cleaning pump 29 is turned on in step S2, and the detergent C is ejected from the cleaning arms 23 and 24 to the tableware B, and the cleaning process starts. Then, in the apparatus of FIGS. 1 and 9, the discharge pressure of the cleaning pump 29 causes the diaphragm pump 3 to transfer the anti-adhesion agent A previously sucked into the rinsing water W of the electric water heater 32 or the water W ′ of the water tank 45. Discharge. Next, step S3
After the predetermined cleaning time has elapsed, the cleaning pump 29 is turned off in step S4, and the cleaning is completed. At this time,
The diaphragm pump 3 newly sucks the anti-adhesion agent A from the tank 1 by the back spring 6.

Next, at step S5, a predetermined pause time is counted, and the apparatus enters a pause state. Then, step S
6, the rinsing solenoid valve 31 is opened, and the rinsing water W passing through the electric water heater 32 is jetted from the rinsing arms 25 and 26 to the tableware B, and the rinsing process starts. Then, in the apparatus of FIG. 1, the anti-adhesion agent A has already been added to the rinse water in step S <b> 2, and in the apparatus of FIG. 5, the anti-adhesion agent A is added to the rinse water W flowing through the rinse pipe 33 by the ejector 10. Inhaled. Next, when a predetermined rinsing time elapses in step S7, the rinsing solenoid valve 31 is closed in step S8, and the rinsing is completed. Thus, in the apparatus shown in FIGS. 1 and 5, the anti-adhesion agent A is added to the rinsing water W during the rinsing step and applied to the tableware B. In the apparatus of FIG. 3, the controller 9 operates the electric diaphragm pump 8 at an arbitrary time in the cycle of FIG.
Although the anti-adhesion agent A can be added to the rinsing water W, the application to the tableware B is performed during the rinsing step in which the electromagnetic valve 31 is opened as described above.

Further, at the time point P after the end of the rinsing step in step S8, the apparatus shown in FIGS.
12 enters the subroutine shown in FIG. 12 (b), the controller 9 of FIG. 8 causes the electric diaphragm pump 8 to perform the discharging operation, and the controller 9 of FIGS.
Opens the electromagnetic on-off valve 41. Then, in the apparatus of FIG. 7, based on the above subroutine (S1 to S3 of FIG. 12B), the anti-adhesion agent A of the tank 1 is sprayed from the spray nozzle 18 to the tableware B by the hydraulically driven diaphragm pump 3. 8 and 9, the anti-adhesion agent A is sprayed onto the tableware B from the spray nozzle 18 or 42 directly or diluted with water. Thus, in these apparatuses, the anti-adhesion agent A is sprayed and applied to the tableware B after the rinsing step. In the apparatus shown in FIG. 10, the controller 9 can operate the electric diaphragm pump 8 at any time in the cycle shown in FIG. 12A to add the anti-adhesion agent A to the water W ′. As described above, this is after the rinsing step in which the electromagnetic on-off valve 43 opens.

On the other hand, FIG. 13 is a flowchart generally showing the operation sequence of the door-type dishwashing apparatus (see FIGS. 2, 4, and 6). In each of the above apparatuses, when the operation switch is turned on in step S1, the cleaning pump 29 is turned on in step S2, and the detergent liquid C is ejected from the cleaning arms 23 and 24 to the tableware B to start the cleaning process. At this time, in the apparatus shown in FIG. 2, the diaphragm pump 3 uses the discharge pressure of the cleaning pump 29 so that the anti-adhesion agent A, which has been sucked in advance, is supplied to the gas water heater 1.
4 is discharged to the rinse water W. Next, when a predetermined cleaning time has elapsed in step S3, the cleaning pump 29 is turned off in step S4, and the cleaning ends.

Next, when the counting of the predetermined pause time is finished in step S5, the rinsing pump 16 is turned on in step S6, and the rinsing water W passing through the gas water heater 14 is ejected from the rinsing arms 25 and 26 to the tableware B. Then, the rinsing process starts. At this time, in the apparatus of FIG. 2, the anti-adhesion agent A has already been added to the rinse water W in step S2, and in the apparatus of FIG. A is sucked. Next, when a predetermined rinsing time has elapsed in step S7, the rinsing pump 16 stops in step S8, and the rinsing ends. Thus, in the apparatus of FIGS. 2 and 6, the anti-adhesion agent A is added to the rinsing water W during the rinsing step and applied to the tableware B. In the apparatus shown in FIG. 4, the controller 9 can operate the electric diaphragm pump 8 at any time in the cycle shown in FIG. 13 to add the anti-adhesion agent A to the rinsing water W. Similarly, the rinsing pump 16 operates during the rinsing process.

As described above, when the anti-adhesion agent A of the present invention is used in any of the dishwashing apparatuses shown in FIGS. 1 to 11, any of the dishwashing methods of the present invention can be executed, and the washing is completed. Even if the rice left over on tableware B dries,
The basic effect is that the cooked rice can be easily peeled off from the tableware only by washing with the dishwasher, without the pretreatment of immersion in a hot water bath, which requires the time and effort as in the past, and the labor saving and speeding up of tableware washing are realized. it can.

FIG. 15 shows a dishwashing apparatus used in a dishwashing method in which the rinse aid of the present invention is added to rinsing water during the rinsing step and applied to dishes. FIGS. 16 to 18 show the above rinse aid. It is a longitudinal cross-sectional view which shows the dishwashing apparatus used for the dishwashing method of spraying and apply | coating an agent to tableware after completion of a rinsing process. These devices have the same basic structure as the conventional household device described with reference to FIG. 22, but are provided with a tank 51 storing a rinsing aid D and a means for supplying the rinsing aid. Therefore, the same members as those in the apparatus of FIG. 22 are denoted by the same reference numerals.

The dishwashing apparatus shown in FIG. 15 differs from the conventional apparatus shown in FIG. 22 in that a tank 51 storing a rinse aid D and a rinse aid D in the tank 51 are supplied to a tank 74 at the bottom of a cleaning chamber 72. And a rinsing aid D controlled by a controller 54 in the passage 52.
Diaphragm pump 53 for feeding the pressure.
The controller 54 controls the sequence of the electric diaphragm pump 53, the circulation pump 76, the drain pump 79, and the solenoid valve 80 according to the cleaning process based on the control program.

That is, the controller 54 opens the solenoid valve 80 to supply water to the tank 74 containing the detergent liquid in advance until it is full, and then drives the circulation pump 76 for a predetermined time to execute the cleaning process. By driving 79, the tank 74 is drained. Next, the solenoid valve 80 is opened and the tank 7 is opened.
4 and supply fresh water W until it is full.
Is driven for a predetermined time to perform rinsing, and then the drainage pump 7
Run a series of rinsing steps several times to drive and drain 9
Repeat (eg 4 times). Then, before, during, after or during the last rinse step, the electric diaphragm pump 53 is driven to supply a predetermined amount of the rinse aid D to the water in the tank 74 via the passage 52 (FIG. 20). Note that if the aforementioned anti-adhesion agent A is stored in the tank 51 in place of the rinsing aid D and the electric diaphragm pump 53 is driven by the controller 54 during the cleaning process or the rinsing process, it will be described with reference to FIGS. The anti-adhesive agent can be applied to the dishes as in the case of the apparatus.

On the other hand, the dishwashing apparatus shown in FIG. 16 is provided with a spray nozzle 55 for spraying the rinse aid D up and down in the washing chamber 72 and a rinse aid in the tank 51 as supply means for the rinse aid D. D through the spray pipe 56 and the spray nozzle 5
5 is provided. The diaphragm pump 53 is driven after a series of rinsing steps by the controller 54 similar to the above, and the rinse aid D is evenly applied to the cleaned surface of the tableware B.
Spray. Further, the dishwashing apparatus of FIG. 17 has a spray nozzle 57 for spraying water from above and below toward the dish B as a supply means of the rinse aid D, and a water pipe 59 having a solenoid valve 58 at the base end. And an ejector 61 provided in a water pipe 59 at the end of the pipe 60 via a check valve, and the electromagnetic valve 58 is controlled by the controller 54. Open control is performed after a series of rinsing steps are completed.

Further, the dishwashing apparatus of FIG.
Instead of this, a water tank 62 is provided at the position of the ejector 61 of the dishwasher, and the rinse aid D is supplied to the water tank 62 by an electric diaphragm pump 53 interposed in the agent pipe 60. , Electric diaphragm 53
And the electromagnetic valve 58 are similarly controlled by the controller 54. In addition, the aforementioned anti-adhesion agent A is stored in the tank 51 of the dishwashing apparatus of FIGS. 6 to 8 instead of the rinsing aid D, and the controller 54 controls the supply unit between the washing step and the rinsing step or between the rinsing step and the rinsing step. If operated after the end, the anti-adhesion agent can be applied to the tableware as in the apparatus described in FIGS.

A method of adding a rinse aid to the rinse water during the rinsing step and applying the rinse aid to the tableware with the above-structured tableware cleaning apparatus of FIG. 15 will be described with reference to the flowchart of FIG. When the operation switch is turned on, the dishwashing device opens the solenoid valve 80 as a water supply valve until the tank 74 filled with the detergent liquid is filled in advance in step S1 until it is full. (Steps S2 and S3
reference). Next, in step S4, the number of rinses n is set to 3, and in step S5, the circulating pump 76 is driven for a predetermined time t, and the cleaning liquid is ejected from the arm 78 toward the tableware B to execute the cleaning process (step S6). , S7). When the cleaning step is completed, the drainage pump 79 as a drainage unit is driven until the tank 74 becomes empty, and the drainage step is executed (see steps S8, S9, S10).

Further, a series of rinsing steps from step S11 to S20 is repeated four times. That is, the solenoid valve 80 is opened until the tank 74 is full, and fresh water is supplied to the tank 74 (see S8 to S13). The fresh water may be tap water or hot water heated by a heater or the like. Next, in step S14, the circulation pump 76
Is driven for a predetermined time t ′, and fresh water is spouted from the arm 78 toward the tableware B to execute a rinsing step (S14 to S14).
See S16). At the end of the repeated series of rinsing steps, ie, the fourth step,
The electric diaphragm pump 53 is driven to supply the rinse aid D stored in the tank 51 to the passage 5 (immediately before S11), water supply (S11), after filling (S13) or during rinsing (S14).
2 to supply fresh water in the tank 74.

As a result, the rinsing aid D contained in the fresh water is applied to the surface of the tableware B having no detergent solution, and the rinse aid D is put on the washed tableware B and left over from the cooked rice. Has an anti-adhesion effect that makes it difficult to adhere to the tableware surface, and imparts excellent gloss without leaving stains or spots on the tableware surface after rinsing. In addition, in this dishwashing device, a rinsing aid that also has an anti-adhesion function is added to the rinsing water in the rinsing step, so there is no need for a tank or pipe for separately adding the anti-adhesion agent, and a separate application step can be omitted. Further, it is possible to simplify the cleaning operation and the cleaning device. In each series of rinsing steps, the drain pump 79 is connected to the tank 7.
Draining process (S1) driven until the rinsing water in 4 is empty
7 to S19), and the number of repetitions of the rinsing process in step 20 is determined. That is, if the number of repetitions is 3
If not (n ≧ 1), n is decremented by 1 in step S22, and the process returns to the start step S11 of the rinsing process. On the other hand, if the number of times reaches 4 (n = 0), the process exits the repetition loop and passes through the drying process (see S21). End the operation.

On the other hand, the method of spraying and applying the rinse aid to the dishes after the rinsing step is completed by the dishwashing apparatus of FIGS. The operation of each device is as described above, except for the That is, the controller 5
4 immediately before step S21 in the flowchart (FIG. 20), the electric diaphragm pump 53 (see FIG. 16) and / or the solenoid valve 58 (see FIG. 17) or both (FIG. 18).
) Is driven to spray the rinse aid D stored in the tank 51 from the spray nozzle 55 via the spray pipe 56 or from the spray nozzle 57 via the water pipe 59 toward the tableware B. Therefore, the rinse aid D can be applied evenly to the clean tableware surface after rinsing, and the applied rinse aid exhibits the same adhesion-preventing effect, spotting prevention, and gloss-imparting effect as described above. Needless to say, the anti-adhesive agent, rinsing aid and dishwashing method and apparatus of the present invention are not limited to the illustrated embodiment.

[0087]

As apparent from the above description, the anti-adhesion agent of the present invention is a compound containing a fluoroalkyl group, and is composed of a perfluoroalkyl group-containing phosphoric acid ester, a fluoroalkyl group and a hydrophilic group. Acrylate or methacrylate homopolymer having (a)
A structural unit derived from an acrylate or methacrylate having a fluoroalkyl group; and
(b) acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, acrylic acid ester having a hydrophilic group and methacrylic acid ester, acrylamide, and methacrylamide, which are structural units derived from at least one selected from the group consisting of Being at least one compound selected from the group consisting of polymers,
Food hardly adheres to the surface of the tableware, and the adhered food can be easily separated from the tableware by washing. On the other hand, the rinse aid of the present invention is derived from a homopolymer of an acrylate or methacrylate having a fluoroalkyl group and a hydrophilic group, and (a) an acrylate or methacrylate having a fluoroalkyl group. Structural unit and (b) a structural unit derived from at least one selected from the group consisting of acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, acrylate and methacrylate having a hydrophilic group, acrylamide and methacrylamide Since it contains at least one polymer selected from the group consisting of copolymers consisting of as an active ingredient, when applied to the surface of tableware, in addition to the function of assisting rinsing, the food left over is peeled off. It can exhibit the adhesion prevention function that makes it easier. Also,
In the dishwashing method of the present invention, the anti-adhesion agent is added to the rinsing water during the rinsing step and applied to the tableware, or sprayed after the rinsing step and applied to the tableware. The remaining food such as cooked rice is less likely to adhere, and the adhered food can be easily peeled off from the tableware only by washing without the pretreatment of immersion in a water bath. realizable. On the other hand, another dishwashing method of the present invention is to add the above-mentioned rinsing aid to rinse water or the like during the rinsing step and apply it to the dish, or spray it after the rinsing step and apply it to the dish,
The effect of preventing water spots and the effect of imparting gloss together with the above-described effect of preventing adhesion can be achieved, and the cleaning operation can be simplified.

[Brief description of the drawings]

FIG. 1 is a longitudinal sectional view showing various embodiments of a dishwashing apparatus according to the present invention.

FIG. 2 is a longitudinal sectional view showing various embodiments of the dishwashing apparatus of the present invention.

FIG. 3 is a longitudinal sectional view showing various embodiments of the dishwashing apparatus of the present invention.

FIG. 4 is a longitudinal sectional view showing various embodiments of the dishwashing apparatus of the present invention.

FIG. 5 is a longitudinal sectional view showing various embodiments of the dishwashing apparatus of the present invention.

FIG. 6 is a longitudinal sectional view showing various embodiments of the dishwashing apparatus of the present invention.

FIG. 7 is a longitudinal sectional view showing various embodiments of the dishwashing apparatus of the present invention.

FIG. 8 is a longitudinal sectional view showing various embodiments of the dishwashing apparatus of the present invention.

FIG. 9 is a longitudinal sectional view showing various embodiments of the dishwashing apparatus of the present invention.

FIG. 10 is a longitudinal sectional view showing various embodiments of the dishwashing apparatus of the present invention.

FIG. 11 is a longitudinal sectional view showing various embodiments of the dishwashing apparatus of the present invention.

FIG. 12 is a flowchart showing the operation of the under counter type of the embodiment.

FIG. 13 is a flowchart showing an operation of the door type embodiment.

FIG. 14 is a view showing the operation of an example of the adhesion preventing agent of the present invention.

FIG. 15 is a longitudinal sectional view showing various embodiments of another dishwashing apparatus of the present invention.

FIG. 16 is a longitudinal sectional view showing various embodiments of another dishwashing apparatus of the present invention.

FIG. 17 is a longitudinal sectional view showing various embodiments of another dishwashing apparatus of the present invention.

FIG. 18 is a longitudinal sectional view showing various embodiments of another dishwashing apparatus of the present invention.

FIG. 19 is a view showing the action of an example of the rinse aid of the present invention.

FIG. 20 is a flowchart showing the operation of another embodiment.

FIG. 21 is a longitudinal sectional view showing a conventional commercial dishwashing apparatus.

FIG. 22 is a longitudinal sectional view showing a conventional household dishwashing apparatus.

[Explanation of symbols]

1 ... tank, 2 ... passage, 3, 8 ... diaphragm pump,
Reference numeral 22: cleaning chamber, 23, 24: cleaning arm, 25, 26: rinsing arm, 27: rack, 29: cleaning pump, 30 ...
Cleaning pipe, 32 ... Electric water heater, 33 ... Rinse pipe, 51
... tank, 52 ... passage, 53 ... electric diaphragm pump, 55, 57 ... spray nozzle, 56 ... spray pipe, 59 ...
Piping for water, 60 ... Piping for agent, 61 ... Ejector, 62 ...
Water tank, A: anti-adhesion agent, B: tableware, C: detergent liquid, D
... Rinse aid, W ... Rinse hot water or fresh water, W '... Water.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yoshio Amimoto 1-1, Nishiichitsuya, Settsu-shi, Osaka Daikin Industries, Ltd. Yodogawa Works (72) Ryutaro Ohashi 1304, Kanaokacho, Sakai-shi, Osaka Daikinko (56) References JP-A-54-103808 (JP, A) JP-A-62-263298 (JP, A) JP-A-56-106634 (JP, A) JP JP-A-262831 (JP, A) JP-A-61-266487 (JP, A) JP-A-58-41996 (JP, A) JP-A-60-40254 (JP, A) ) Japanese Utility Model Showa 57-147655 (JP, U) Japanese Utility Model Hei 2-45182 (JP, U)

Claims (10)

(57) [Claims] 1. A dishwashing method comprising a step of applying an antiadhesive agent for facilitating food peeling to the surface of tableware made of pottery, porcelain, glass or metal, wherein the antiadhesive agent contains a fluoroalkyl group. A perfluoroalkyl group-containing phosphate, a homopolymer of an acrylate or methacrylate having a fluoroalkyl group and a hydrophilic group, and (a) an acrylate or methacryl having a fluoroalkyl group A structural unit derived from an acid ester and (b) at least one selected from the group consisting of acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, acrylic acid esters and methacrylic esters having a hydrophilic group, acrylamide and methacrylamide Units derived from Dishwashing wherein the at least one compound selected from the group consisting of Ranaru copolymer. 2. The copolymer further comprises ethylene, vinyl chloride, vinylidene halide, styrene, acrylic acid and its alkyl ester, methacrylic acid and its alkyl ester, benzyl methacrylate, vinyl alkyl ketone, vinyl alkyl ether, butadiene, 2. The dishwashing method according to claim 1, further comprising at least one other structural unit derived from a polymerizable compound not containing at least one fluoroalkyl group selected from the group consisting of isoprene, chloroprene and maleic anhydride. 3. The dishwashing method according to claim 1, wherein the anti-adhesion agent is added to the rinsing water during the rinsing step and applied to the tableware. 4. The dishwashing method according to claim 1, wherein the anti-adhesion agent is applied by spraying to the dish after the rinsing step. 5. A rinsing aid which has a function of preventing adhesion that facilitates peeling of food and a function of assisting rinsing,
In a dishwashing method having a treatment step of applying to the surface of tableware made of porcelain, glass or metal, the rinsing aid includes a homopolymer of an acrylate or methacrylate having a fluoroalkyl group and a hydrophilic group, and ( a) a structural unit derived from an acrylate or methacrylate having a fluoroalkyl group and (b) acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, an acrylate and methacrylate having a hydrophilic group, acrylamide, and A dishwashing method comprising, as an active ingredient, at least one polymer selected from the group consisting of copolymers composed of at least one constituent unit selected from the group consisting of methacrylamide. 6. The dishwashing method according to claim 5, wherein the rinse aid is added to the rinse water during the rinsing step and applied to the tableware. 7. The dishwashing method according to claim 5, wherein the rinse aid is applied by spraying to the dish after the rinsing step is completed. 8. An adhesion inhibitor for dishwashing applied to the surface of tableware made of pottery, porcelain, glass or metal in order to easily peel off food, wherein the adhesion inhibitor is a compound containing a fluoroalkyl group. A perfluoroalkyl group-containing phosphates, homopolymers of acrylates or methacrylates having a fluoroalkyl group and a hydrophilic group, and (a) acrylates or methacrylates having a fluoroalkyl group Derived from the structural unit and (b) at least one selected from the group consisting of acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, acrylate and methacrylate having a hydrophilic group, acrylamide and methacrylamide Copolymer consisting of different structural units Preventive agent for dishwashing, characterized in that at least one compound selected from the group consisting of. 9. The copolymer further comprises ethylene, vinyl chloride, vinylidene halide, styrene, acrylic acid and its alkyl ester, methacrylic acid and its alkyl ester, benzyl methacrylate, vinyl alkyl ketone, vinyl alkyl ether, butadiene, 9. The antifouling agent for dishwashing according to claim 8, having at least one other structural unit derived from a polymerizable compound not containing at least one fluoroalkyl group selected from the group consisting of isoprene, chloroprene and maleic anhydride. 10. A rinsing aid for dishwashing applied to the surface of tableware made of ceramics, porcelain, glass or metal, having both a function of preventing adhesion that facilitates peeling of food and a function of assisting rinsing, Rinsing aid is a homopolymer of an acrylate or methacrylate having a fluoroalkyl group and a hydrophilic group, and (a) a structural unit derived from an acrylate or methacrylate having a fluoroalkyl group and (b) ) Acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, copolymer having a structural unit derived from at least one selected from the group consisting of acrylates and methacrylates having a hydrophilic group, acrylamide and methacrylamide At least one selected from the group consisting of Auxiliaries rinse for dishwashing, characterized in that it contains a polymer as an active ingredient.