KR20170058089A - Oral composition for tooth whitening - Google Patents

Abstract

The present invention relates to an oral composition for whitening teeth, comprising: a first agent including peroxide; and a second agent including at least one peroxide activator selected from the group consisting of an exothermic agent, an alkali agent and metal salt, wherein one of the first agent and the second agent is a paste agent and the other one is a dry film agent.

Description

ORAL COMPOSITION FOR TOOTH WHITENING BACKGROUND OF THE INVENTION [0001]

The present invention relates to an oral composition for tooth whitening.

The teeth are located in the oral cavity and provide many functions, such as a function of mastication as a primary function of digestion, and a function of assisting in pronunciation as a structure that can distinguish detailed sounds in pronunciation. The teeth are composed of apatite crystals, that is, dentin composed of apatite and enamel surrounding enamel, that is enamel, while enamel is translucent, while dentin is basically yellowish, teeth usually yellow, When dark colored beverages and smokes cause tooth discoloration, the teeth may be discolored from dark yellow to black.

However, there is a wide demand for teeth whitening that changes the color of the teeth to whitish as the white tooth is set as a standard of beauty, but the tooth is exposed to the food, drink and smoking depending on the person continuously through the oral cavity , It is difficult to overcome the inherent dentin color and acquired tooth coloration by simply brushing or scaling and changing it to a white tooth.

Products that bleach the coloring material by penetrating the bleaching material into the teeth by applying a product containing the bleaching material such as hydrogen peroxide for tooth whitening are used, but the product containing the bleaching material such as hydrogen peroxide is used as the bleaching material Due to instability, attempts have been made to stabilize the formulation.

The following patent document 1 discloses a composition in which a peroxide and a peroxide activator are separated into two parts of a paste / paste, and although such a composition shows improved whitening effect over a composition of a single formulation, However, bleaching reaction occurred in the entire oral cavity, and the whitening target tooth area did not show a significant whitening improvement effect.

The following Patent Documents 2 and 3 disclose compositions separated by a peroxide activator which is a dry film agent and a peroxide activator having a plurality of layers. Such a composition can cause an effective bleaching reaction within a whitened target tooth area range, Due to the interlayer transfer structure, the bleaching reaction takes time to take place, and the amount of peroxide is limited, so that a significant whitening improvement effect has not been exhibited.

Therefore, there is a tooth whitening agent that can achieve a significant whitening improvement effect while intensively bleaching reaction occurs in a desired whitening target tooth area range because there is only a tooth whitening agent that focuses on formulation stabilization of unstable peroxides I did.

Korean Patent Registration No. 877981 (Jan. 12, 2009) Korean Unexamined Patent Publication No. 2004-0095898 (November 16, 2004) Korean Registered Patent No. 553433 (Feb. 20, 2006)

The present invention provides an oral composition for teeth whitening which is superior in formulation stability, contains peroxide as a whitening ingredient, has a whitening reaction intensively in a desired whitening target tooth area range, and simultaneously achieves a significant whitening improvement effect I want to.

The present invention relates to a first agent comprising a peroxide; And a second agent comprising at least one member selected from the group consisting of an exothermic agent, an alkali agent and a metal salt, wherein one of the first agent and the second agent is a paste agent, One is a dry film adhesive composition for tooth whitening.

The oral care composition for teeth whitening according to the present invention is a tooth whitening ingredient which is separated into a paste form and a dry form form different from each other as a paste whitening ingredient, The bleaching reaction can be induced, and the paste agent can contain one of the peroxide and peroxide activator components sufficiently to cause an excellent bleaching reaction, and bleaching reaction takes place in a short time, and after the bleaching reaction is completed, Is decomposed after the whitening reaction and rinses the mouth with water, so that it can be easily removed together with the paste agent.

As used herein, the term " tooth " refers to bone tissue exposed to the outside of the oral epithelium of an animal, and is specifically described on the basis of human teeth, but is also to be interpreted to include animal teeth.

As used herein, " whitening " means increasing the brightness of the color of the teeth.

Hereinafter, the oral care composition for teeth whitening according to the present invention will be described in detail.

The first agent

The oral care composition for teeth whitening according to the present invention comprises a first agent, wherein the first agent comprises a peroxide.

The peroxide according to the present invention means a compound having peroxide group (-OO-) or peroxide carboxyl group (-C (= O) -OO-) or capable of generating hydrogen peroxide ion (O ₂ ^2- ) The peroxide is an oxidizing / reducing action that bleaches the surface of the tooth.

In one embodiment of the present invention, the peroxide is at least one selected from the group consisting of hydrogen peroxide, carbamide peroxide, calcium peroxide, sodium pyrophosphate, and sodium percarbonate.

In one embodiment of the present invention, the content of the peroxide is 0.1 wt% to 20 wt% with respect to the total weight of the first agent. If the content of the peroxide is less than 0.1% by weight, an effective whitening effect can not be obtained. If the content of the peroxide is more than 20% by weight, peroxide may stimulate the nervous system to cause symptoms of acylation or irritation and irritation to the gums .

Second article

The oral composition for tooth whitening according to the present invention comprises a second agent, wherein the second agent comprises at least one peroxide activator selected from the group consisting of a heat-generating agent, an alkali agent and a metal salt.

The peroxide activator according to the present invention means promoting a reaction for generating free radicals from the peroxide or a reaction for generating hydrogen peroxide ions (O ₂ ^2- ).

The exothermic agent in the peroxide activator according to the present invention means to accelerate the reaction by increasing the temperature of the peroxide.

In one embodiment of the present invention, the exothermic agent is zeolite, calcium chloride, or a mixture thereof.

In one embodiment of the invention, the zeolite as long as generating heat by reaction with water is not particularly limited, for example, zeolite A, zeolite X, zeolite Y, the general formula xM _{2 / n} O · Al such as zeolite L ₂ O ₃ · YSiO ₂ ZH ₂ O wherein x, y and z represent an arbitrary number, M represents an alkali metal or an alkaline earth metal metal, and n represents the valence thereof.

In one embodiment of the present invention, the content of the exothermic agent is 5 wt% to 50 wt% with respect to the total weight of the second agent. When the amount of the exothermic agent is less than 5 mass%, the effect of exothermic effect can hardly be felt at the time of brushing. When the amount of the exothermic agent is more than 50 mass%, pain is felt during tooth brushing due to excessive heat generation.

The alkali agent in the peroxide activator according to the present invention means that the pH of the peroxide is adjusted to be 8 to 11 to promote the reaction.

In one embodiment of the present invention, the alkali agent is at least one selected from the group consisting of sodium hydroxide, sodium bicarbonate, and sodium percarbonate.

In one embodiment of the present invention, the content of the alkali agent is 0.01 wt% to 5 wt% with respect to the total weight of the second agent. If the content of the alkaline agent is less than 0.01% by weight, the effect of the activator is insufficient. If the content of the alkaline agent is more than 5% by weight, it may be activated too quickly or may irritate the teeth or gums.

The metal salt in the peroxide activator according to the present invention means to accelerate the reaction by releasing metal ions which promote the decomposition of hydrogen peroxide. The metal ions promoting the decomposition of the hydrogen peroxide may be, for example, Fe ^{3 +} , Cu ^{2 +} , Al ^{3 +} , Mn ^{2 +} .

In one embodiment of the present invention, the metal salt is selected from the group consisting of iron chloride, iron sulfate, iron nitrate, copper sulfate, copper nitrate, aluminum sulfate, aluminum sulfate, manganese sulfate, manganese gluconate, manganese citrate and manganese dioxide It is more than one.

In one embodiment of the present invention, the content of the metal salt is 0.001 wt% to 1 wt% with respect to the total weight of the second agent. If the content of the metal salt is less than 0.001% by weight, the effect of the activator is insufficient. If the content of the metal salt is more than 1% by weight, it may be activated too quickly or irritation and bad taste may be given to teeth or gums.

Paste

In the oral care composition for teeth whitening according to the present invention, either the first agent or the second agent is a paste.

The paste composition according to the present invention basically means a composition which is liquid at room temperature but may be a solid phase in which all or a part of the composition is continuously deformed due to shear stress at room temperature and is viscous. But may be in the form of a solid or a gas dispersed in a liquid or a liquid and specifically includes a solution formulation, a gas / liquid foam formulation, a liquid / liquid emulsion formulation, a solid / liquid / RTI > suspension formulation, a liquid / solid suspension formulation, or a liquid / solid gel formulation.

In one embodiment of the present invention, the viscosity of the paste is 20,000 cps to 1,600,000 cps. When the viscosity of the paste is less than 20,000 cps, the viscosity is too low to lower the stability of the formulation. When the paste viscosity is more than 1,600,000 cps, the viscosity is too high.

In the present specification, the viscosity value refers to a viscosity value measured at 25 ° C and 1 atm using a viscometer LVT-RV (trade name, manufactured by Brookfield Engineering Laboratories, Inc.).

In one embodiment of the present invention, as the wetting agent component, glycerin, sorbitol solution, polyethylene glycol, propylene glycol or the like may be used alone or in admixture of two or more in an amount of 20% by weight to 60% by weight relative to the total weight of the paste And further added to the paste agent.

 In one embodiment of the present invention, in order to prevent the activity of the cationic fungicide from being lowered, the foam stabilizer may be selected from polyoxyethylene sorbitan fatty acid esters, polyoxyethylene (hardened) castor oil, glycerin fatty acid esters, sorbitan fatty acid esters, A nonionic surfactant such as sucrose fatty acid ester, alkylolamide or alkyl glucoside, or a cationic surfactant such as N-alkyldiaminoethylglycine, alone or in admixture of two or more, in an amount of 0.5 wt% To 10% by weight, preferably 0.5% by weight to 8% by weight.

In one embodiment of the present invention, the binder may be selected from the group consisting of hydroxyethyl cellulose, hydroxypropyl cellulose, xanthan gum, carrageenan, sodium alginate, etc. in an amount of 0.1 wt% to 5 wt% By weight, preferably 0.1% by weight to 2% by weight, based on the total weight of the paste.

In one embodiment of the present invention, saccharine, sodium saccharin, aspartame, stevioside, xylitol, licorice acid and the like are used alone or in admixture of two or more as sweeteners, and 0.05 to 5 wt% Is further added to the paste agent.

In one embodiment of the present invention, citric acid, tartaric acid, phosphoric acid, and the like may be used alone or as a mixture of two or more thereof as the acidic pH regulator, and as the preservative there may be used methyl paraoxybenzoate, propyl pamooxybenzoate, sodium benzoate, And further added to the paste preparation.

In one embodiment of the present invention, the active ingredient includes sodium fluoride, sodium fluorophosphate, tin fluoride, chlorohexidine, allantoin chlorohydroxy aluminate, aminocaproic acid, triclosan chloride, cetylpyridinium chloride, zinc chloride, Pyridoxine hydrochloride, tocopherol acetate or the like are used alone or in combination of two or more. As the fragrance, an appropriate amount of peppermint oil, spearmint oil, menthol, anethole and the like are mixed and used. The brightener is titanium dioxide, The coloring matter is used as a solvent, and purified water and ethanol are used according to a conventional method for producing toothpaste.

Dry film

The oral care composition for tooth whitening according to the present invention is characterized in that the second agent is a dry film agent if the first agent is the paste agent and the first agent is a dry film agent if the second agent is the paste agent.

The dry film preparation according to the present invention refers to a solid form preparation in the form of a sheet having a long width and a thickness by drying a composition having the composition of the first or second agent, The width does not limit the extent to which more than one tooth can be covered.

The dry film preparation according to the present invention comprises the steps of: forming a film containing the composition of the first agent or a composition containing the constituents of the second agent; Drying the composition containing the component of the first agent or the composition containing the constituent of the second agent; Or a combination of these processes.

The film forming process may include the blown film process, the cast film process, the thermoforming process, the vacuum forming process or the extrusion coating process , But is not limited thereto, so long as it is capable of producing a solid form of sheet-like form having a width and a thickness of a length by drying.

In the present specification, when the first agent or the second agent is a dry film agent, the content of the composition means the composition in a state of mixture before the first agent or the second agent is subjected to the film forming step or the drying step .

The tooth whitening composition according to the present invention may be in the form of a liquid, specifically a paste having a viscosity, and may further include a toothpaste component commonly used in the related art. Preferably, May be a dry film formulation.

In one embodiment of the present invention, the average thickness of the dry film is 0.05 mm to 0.5 mm. When the thickness of the dry film is less than 0.05 mm, the film is too thin to achieve an effective whitening effect. When the thickness is more than 0.5 mm, the film is too thick to have a strong bonding force to the surface of the tooth, There is a problem.

In one embodiment of the present invention, the dry film agent further contains a water-insoluble polymer or a semi-water-soluble polymer. The water-insoluble polymer or semi-water-soluble polymer is not limited as long as it can maintain a solid state at room temperature and can not be completely dissolved upon contact with saliva. For example, there may be mentioned cellulose acetate phthalate, polyvinyl acetate, ethyl cellulose, polymethyl methacrylate, methacryloyl ethyl betaine / methacrylate copolymer (Yukaformer: Mitsubishi, methacryloylethyl betain / methacrylate copolymer) (Methacrylic acid copolymer (Eudragit L 100, Eudragit L 12,5, Eudragit L 100-55, Eudragit L 30D-55), aminoalkyl methacrylate copolymer (Eudragit E 100, Eudragit E 12 , 5, Eudragit RL 100, Eudragit RL 30D.

In one embodiment of the present invention, the content of the water-insoluble polymer or semi-water-soluble polymer is 20% by weight to 60% by weight based on the total weight of the first agent or the second agent. When the content of the polymer is less than 20% by weight, the film is not uniformly formed to a thickness of more than a certain thickness. When the polymer content is more than 60% by weight, the solubility is lowered.

In one embodiment of the present invention, the first agent is the paste agent and the second agent is the dry film agent.

In one embodiment of the present invention, the second agent is the paste agent, and the first agent is the dry film agent.

Chelating agent

In one embodiment of the present invention, the first agent or the second agent is selected from the group consisting of tetrasodium pyrophosphate, sodium acid pyrophosphate, sodium tripolyphosphate, sodium hexametaphosphate, and acidic polyphosphate And further comprises at least one chelating agent.

In one embodiment of the present invention, the chelating agent content is 0.01 wt% to 5 wt% with respect to the total weight of the first agent or the second agent.

Hereinafter, the present invention will be described in more detail by way of examples. However, these embodiments are intended to illustrate the present invention only, and the scope of the present invention is not limited by these embodiments.

< Reference example  1> Paste  Preparation of composition

The compositions of pastes 1 and 2 were respectively prepared by the composition shown in the following Table 1 (unit: wt% based on the total weight of the pasted paste), and the detailed procedure is as follows. First, polyethylene glycol and glycerin, which are polyols, were put into a container, and then sodium saccharin, sodium fluorophosphate and polyvinylpyrrolidone were dissolved or dispersed at a temperature of 70 to 80 ° C. In the vacuum state, hydrated silicic acid, anhydrous zeolite (used only in the case of paste No. 2) and sodium lauryl sulfate were added and stirred well for 20 minutes. After cooling to 40 캜, a flavor and hydrogen peroxide solution (used only for paste No. 1) were put into a container and dissolved for 20 minutes to prepare a paste composition.

ingredient Paste first Paste second Polyethylene glycol ^{1 )} 37.94 29.94 Glycerin ^{2 )} 35.00 25.00 Fragrance ^{3 )} 1.00 1.00 Sodium lauryl sulfate ^{4 )} 2.00 2.00 Sodium saccharin ^{5 )} 0.30 0.30 Sodium fluoride phosphate ^{6 )} 0.76 0.76 Polyvinylpyrrolidone ^{7 )} 1.00 1.00 Functional silicic acid ^{8 )} 20.00 20.00 Anhydrous zeolite ^{9 )} - 20.00 Hydrogen peroxide water (concentration 35%) ¹⁰⁾ 2.00 -

1) Dow Chemical / CARBOWAX SENTREY POLYETHYLENE GLYCOL 400 NF

2) LG Household & Health Care / ELOGLYN R995

3) Takasako / Fureaver

4) KAO / Emal 10PT

5) KAIFENG XINGHUA FINE CHEMICAL / SODIUM SACCHARIN

6) HUBEI XINGFA CHEMICALS GROUP CO./Sodium Monofluorophosphate

7) Basf / Luviskol K30

8) Rhodia / TIXOSIL 43K

9) Jisim Tech / JST-Calolite (LP)

10) Hansol Chemical / HP 35M, the content of the first hydrogen peroxide in the paste was 0.7 wt%

The viscosity of the paste composition was measured using a viscometer LVT-RV manufactured by Brookfield Engineering Laboratories, Inc. under a temperature of 25 ° C and a pressure of 1 atm. The viscosity of the paste composition was 400,000 cps. As a result, The viscosity of 2 was 440,000 cps.

< Reference example  2> Preparation of dry film

Each of the dried films 1 to 3 was prepared by the composition (unit: wt% based on the total weight of the composition) shown in the following Table 2, and the detailed procedure is as follows.

First, purified water and ethanol are put into a container, and polyethylene glycol and polyvinylpyrrolidone are slowly added thereto at a temperature of 50 to 60 ° C, and they are dissolved with stirring using an agitator for 20 minutes. Thereafter, the mixture was cooled to 25 DEG C, and the remaining components were put into a container at once and dissolved and dispersed for 20 minutes to prepare a mixed composition.

100 g of the mixed composition was allowed to stand for 30 minutes, degassed, cast on a silicone-treated polyester film, and then dried in a hot air drier at 50 DEG C for 20 minutes to prepare a dry film.

The average thickness of the dried films 1 to 3 was measured and found to be 0.25 mm.

Ingredients Dry film 1st Dry Film Second Dry Film Third Eudragit ^{1 )} 20.00 20.00 20.00 Polyvinylpyrrolidone ^{2 )} 10.00 10.00 10.00 Sodium lauryl sulfate ³⁾ 8.00 8.00 8.00 Zeolite ⁴⁾ 10.00 - - Calcium carbonate ⁵⁾ - 10.00 10.00 Saccharin ⁶⁾ 0.60 0.60 0.60 Polyethylene glycol ^{7 )} 5.00 5.00 5.00 Fragrance ⁸⁾ 2.00 2.00 2.00 Hydrogen peroxide water (concentration 35%) ^{9 )} - - 2.00 Ethanol ^{11 )} 44.40 44.40 42.40

1) EVONIK / EUDRAGIT E PO

2) Basf / Luviskol K30

3) KAO / Emal 10PT

4) Jisim Tech / JST-Calolite (LP)

5) Baekwang Industry / BKEIFG-1000

6) KAIFENG XINGHUA FINE CHEMICAL / SODIUM SACCHARIN

7) Dow Chemical / CARBOWAX SENTERY POLYETHYLENE GLYCOL 400 NF

8) Takasako / Fureaver

9) Hansol Chemical / HP 35M, the content of the third hydrogen peroxide in the dried film is 0.7 wt%

10) Samseon / Ethyl Alcohol, concentration 95.0%

< Reference example  3> 2 Formulation  Preparation of oral compositions for whitening

Using the pastes and dry film preparations prepared in Referential Examples 1 and 2, a 2-form whitening oral composition was prepared by the combination of Example 1 and Comparative Examples 1 to 3 as shown in Table 3 below.

The first agent Second article Example 1 Paste first Dry film 1st Example 2 Dry Film Third Paste second Comparative Example 1 Paste first Dry Film Second Comparative Example 2 Paste first Paste second Comparative Example 3 Dry film 1st Dry Film Third

< Test Example  1) Tooth whitening effect test Vivo )

In order to measure tooth whitening effect of tooth whitening toothpaste according to the present invention, 100 healthy male and female workers were selected as a sample, and tooth brightness before and after use was measured.

The test group was divided into five groups to which Examples 1 and 2 and Comparative Examples 1 to 3 were respectively applied. The subject's original tooth tone was measured using SHADEEYE-EX (SHOFU Co.LTD., Japan) .

The SHADEEYE-EX tip was irradiated with a beam perpendicular to the maxillary left central incisor, 2mm above the cervical spine, in the middle of the myocardium, and the baseline (primary reference value) data were measured and collected. The rats were allowed to brush three times a day as follows.

Test group of Example 1: The second agent was applied to the tooth, the toothbrush was immersed in the first agent,

Test group of Example 2: After the first agent was applied to the tooth, the toothbrush was immersed in the second agent,

Test group of Comparative Example 1: After the second agent was applied to the teeth, tooth furrowing for 3 minutes with the first agent,

Test group of Comparative Example 2: The first and second agents were put on a toothbrush together,

Test group of Comparative Example 3: The first agent is applied to the teeth, the second agent is applied on the teeth, and the teeth are cleaned.

During the test period, food was ingested according to his usual eating habits, but coffee, cola and cigarettes were prohibited before measuring the color of the day when the color was measured. After one month of use, the chromaticity was measured (secondary measurement).

In this experiment, SHADEEYE-EX, which is used for optical colorimetry, is a chromatic system dedicated to measuring the color of natural teeth. After irradiating a certain amount of rays to the tooth, the amount of reflected light is measured by three filters of red, yellow, A3 = 9, D4 = 8, C2 = 7, A3.5 = 12, B3 = 11, D3 = 10, A3 = 9, And the corresponding brightness value is outputted by comparing and analyzing the color of the image with the color of C1 = 6, A2 = 5, D2 = 4, B2 = 3, A1 = 2, B1 = And averages for the second measurement a month later are averaged for each group, and are shown in Table 4 below.

Primary measurement
(baseline mean) Secondary measurement
(Average after one month) Example 1 7.9 6.14 Example 2 7.92 6.25 Comparative Example 1 7.89 7.32 Comparative Example 2 7.87 6.94 Comparative Example 3 7.91 6.84

If the tooth brightness value of the secondary measurement is lower than the tooth brightness value of the primary measurement, it means "improvement." If the tooth brightness value of the secondary measurement is equal to the tooth brightness value of the primary measurement, The results are shown in Table 5 below. Table 5 shows the number of persons according to the judgment result and the reference ratios of the persons in each group.

Improving No change worse Example 1 15 (75%) 5 (25%) 0 (0%) Example 2 14 (70%) 6 (30%) 0 (0%) Comparative Example 1 4 (20%) 16 (80%) 0 (0%) Comparative Example 2 7 (35%) 13 (65%) 0 (0%) Comparative Example 3 7 (45%) 11 (55%) 0 (0%)

The result of SHADEEYE-EX is not dependent on the non-color environment condition, but it is possible to minimize the tip diameter of the measuring instrument, reduce the direction of light, absorbency, You can get a specific figure of tooth brightness. The tooth brightness value is a total of 16 steps. The lower the value, the brighter the tooth.

In Table 4, Comparative Examples 1 to 3 showed a decrease in the average value of tooth brightness values for one month, but were lower than those of Examples 1 and 2. In Table 5, Examples 1 and 2 were more than two-thirds of the corresponding group, whereas Comparative Examples 1 to 3 had no improvement in tooth brightness to 50%, or as much as 80%, of the corresponding group.

Thus, it can be seen that Examples 1 and 2 according to the present invention are comparative examples 1 and 2 of a peroxide-containing paste agent and a peroxide-active agent-free dry film-containing second agent, a peroxide- It was confirmed that Comparative Example 2, which is a dry film preparation containing peroxide, and Comparative Example 3, which is a dry film-containing dry film preparation containing peroxide active agent, were more excellent in tooth brightness improvement, that is, tooth whitening improvement effect.

Claims (9)

A first agent comprising a peroxide; And
And a second agent comprising at least one peroxide activator selected from the group consisting of an antioxidant, an exothermic agent, an alkali agent and a metal salt,
Wherein one of the first agent and the second agent is a paste,
And the other one is a dry film adhesive for whitening teeth. The method according to claim 1,
Wherein the first agent is the paste agent,
And the second agent is the dry film agent. The method according to claim 1,
Wherein the peroxide is at least one selected from the group consisting of hydrogen peroxide, carbamide peroxide, calcium peroxide, sodium pyrophosphate, and sodium percarbonate. The method according to claim 1,
Wherein the exothermic agent is zeolite, calcium chloride, or a mixture thereof. The method according to claim 1,
Wherein the alkaline agent is at least one selected from the group consisting of sodium hydroxide, sodium bicarbonate, and sodium percarbonate. The method according to claim 1,
Wherein the metal salt is at least one selected from the group consisting of iron chloride, iron sulfate, iron nitrate, copper sulfate, aluminum nitrate, aluminum sulfate, aluminum potassium sulfate, manganese sulfate, manganese gluconate, manganese citrate and manganese dioxide. The method according to claim 1,
Wherein the first agent or the second agent further comprises at least one chelating agent selected from the group consisting of tetrasodium pyrophosphate, sodium acid pyrophosphate, sodium tripolyphosphate, sodium hexametaphosphate, and acidic polyphosphate &Lt; / RTI &gt; The method according to claim 1,
Wherein the paste has a viscosity of 20,000 cps to 1,600,000 cps. The method according to claim 1,
Wherein the dry film has an average thickness of 0.05 mm to 0.5 mm.