KR20180021989A - Multi-function ceramic ware and Manufacturing Method thereof - Google Patents

Abstract

The present invention relates to: a basis material composition and a glaze composition having functionalities; a method for manufacturing ceramics having a function of emitting far infrared rays and anion using the compositions; and multi-functional oxygen ceramics manufactured by the method. In the present invention, white clay and sericite are added at a predetermined ratio to the basis material composition and the glaze composition for ceramics to obtain a deodorizing effect as well as the function of emitting far infrared rays and anion, and in particular, by adding Pinus densiflora materials, Quercus dentata materials, and Pteridium aquilinum var. latiusculum materials as well as the white clay and sericite to the glaze composition, the function of emitting far infrared rays and anion can be maximized. Accordingly, the basis material composition and the glaze composition for ceramics of the present invention can create a comfortable indoor living environment through various beneficial functions native to the far infrared rays as well as the deodorizing effect, thereby being expected to be used and applied to related fields.

Description

TECHNICAL FIELD [0001] The present invention relates to a multi-functional oxygen porcelain and a manufacturing method thereof,

The present invention relates to a substrate composition and a glaze composition having functionalities, a method for manufacturing ceramics having far infrared rays and anion emission function using the same, and a multifunctional oxygen ceramics manufactured thereby.

Pottery is a term that includes pottery and porcelain. Ceramics are mainly made of materials such as clay, feldspar, silica, pyrophyllite, and stonite. Ceramics are products obtained by mixing and molding these materials at a certain ratio, followed by firing and curing.

These ceramics are a part of ceramics, and they cover a wide range from porcelain vases and tiles used for assembling or decorating buildings to ceramics, to tableware for everyday life.

The term "glaze" refers to a coating applied to give gloss to the surface of a pot or pottery in the field of ceramics technology. In the past, the glaze is mainly composed of feldspar, silica, limestone, limestone, talc, bone meal, CMC, However, it has been found that the above-described light used as a melting agent can be obtained by heating lead or lead oxide, which leads to the elution of lead oxide, which is a heavy metal, and its use has been banned. In recent years, Glazes, limestone, clay, kaolin, manganese, titanium, CMC and the like, as the metal materials of the present invention are developed.

Conventional jars or ceramics are used for decorative purposes, but they are generally used as dishware or containers. However, since the materials are not easily purchased, the manufacturing process is complicated, and the mass productivity is low, Or stainless steel utensils or containers are used.

However, in modern people who live in a busy environment in a polluted environment, as the consciousness and concern about health gradually increase, especially in health, in the diet, the advantages Are emerging. Therefore, in the production of dishware or containers made of ceramics, it has been developed as a tendency to promote the health of the human body, and the glaze has also been developed to meet the above object.

The inventors of the present invention have found that by adding white clay and sericite to a composition of a ceramic composition and a glaze composition at a predetermined ratio to produce ceramics having various functions, they have a deodorizing effect and a far-infrared emission and anion emission effect. In order to maximize the emission effect of far infrared ray and anion, synergy effect was examined by adding pine wood, oak wood and bracken as far infrared rays and anion emitting materials to the glaze composition containing the clay and sericite. As a result, it was confirmed that the glaze composition added with pine wood, oak wood and bracken relative to the known material (zeolite, elvan or loess) with far-infrared emission effect was excellent in far-infrared ray and anion emission effect Thus completing the present invention.

Korean Patent Publication No. 10-1991-0005051 Korean Patent No. 10-1105159

Accordingly, an object of the present invention is to provide a functional glaze composition having an excellent deodorizing effect and a far infrared ray and anion emission effect.

Another object of the present invention is to provide a method for manufacturing ceramics having excellent deodorizing property and a far infrared ray and anion emission effect.

Another object of the present invention is to provide a multi-functional ceramics having a far-infrared ray and anion radiation function together with the deodorization produced by the above method.

In order to achieve the above-mentioned object of the present invention,

The present invention relates to a method for producing a fermented soybean milk comprising 20 to 30% by weight of white clay, 20 to 50% by weight of sericite, 10 to 15% by weight of frit, 10 to 15% by weight of titanium oxide, 1 to 10% To 10% by weight of the glaze composition.

In one embodiment of the present invention, the composition may further include at least one member selected from the group consisting of pine wood, oak wood, bracken, zeolite, and elvan.

The present invention also provides a method for preparing a ceramic composition, comprising the steps of: a) preparing a substrate composition for ceramics comprising 20 to 30 wt% of clay, 50 to 60 wt% of sericite, 10 to 15 wt% of stones, and 5 to 15 wt% of bentonite; b) from 20 to 30% by weight of clay, from 20 to 50% by weight of sericite, from 10 to 15% by weight of frit, from 10 to 15% by weight of titanium oxide, from 1 to 10% by weight of ore and from 1 to 10% ≪ / RTI > c) shaping and drying the base composition for a ceramic article; d) cooling the dried molded product after the first calcination by the step c); And e) applying the glaze composition to the molding subjected to the first firing and then firing secondarily.

In one embodiment of the present invention, the glaze composition in the step b) may further include at least one member selected from the group consisting of pine wood, oak wood, bracken, zeolite, and elvan.

In one embodiment of the present invention, drying in step c) may be performed at 110 ° C for 1 to 3 hours.

In one embodiment of the present invention, the first firing in step d) may be performed at a temperature of 50 to 800 ° C. for 15 to 20 hours.

In one embodiment of the present invention, the secondary firing in step e) may be performed at 1250 to 1280 캜 for 22 to 26 hours.

In addition, the present invention provides a pottery having a far-infrared ray and anion radiating function manufactured by the above method.

The present invention can provide a deodorizing effect and a far infrared ray emission effect and an anion emission effect by adding white clay and sericite to a constitution of a basecoat composition and a glaze composition at a predetermined ratio; In particular, by adding pine wood, sericite, pine wood, oak wood, and bracken to the glaze composition, far infrared rays and anion emission effects can be maximized. Therefore, the present composition and the glaze composition for pottery of the present invention have the effect of creating a pleasant indoor living environment through various beneficial functions inherent to far-infrared rays, as well as a deodorizing function, and their use and application in related fields are expected.

The present invention provides a substrate composition comprising 20 to 30% by weight of clay, 50 to 60% by weight of sericite, 10 to 15% by weight of stones and 5 to 15% by weight of bentonite.

In the present invention, the term "body" refers to a ceramic body. The composition of a general substrate is composed of three components such as aggregates, plasticizers, and fluxes. Depending on the composition of each raw material and the firing temperature, Porcelain vagina, and porcelain vagina.

Generally, the raw materials for ceramics are composed of quartzite, quartzite, feldspar, or feldspar, and feldspar, which is a plastic material. Especially, for a dishwasher mainly for spinning, it is required to have proper plasticity . This plasticity is mainly obtained from clay minerals such as clay, kaolin, sericite, stonite, bentonite, and pyrophyllite.

All raw materials of ceramics are first crushed and used, but they must be crushed because they must be taken from natural to powdery state and taken in bulk form.

Generally, a raw material that is calculated in the form of powder is referred to as a " plastic raw material ", and a raw material that must be pulverized is called an " non-plastic raw material ". When making ceramics, various materials are mixed homogeneously. The mixing ratio at this time is determined according to the combination ratio. Finally, the combination, ie clay, must be able to form.

The base composition of the present invention is prepared by mixing 20 to 30% by weight of clay having micropores and 50 to 60% by weight of sericite and adding 10 to 15% by weight of stones and 5 to 15% by weight of bentonite, Followed by aging for 10 to 20 days.

The 'white soil' is also called 'white soil' and 'white water'. As a raw material for white ceramics, it refers to white clay or kaolin. It is a pure white color and a little gray, but it becomes white when baked at high temperature. The white clay is calculated in Hwanghae Island Bongsan, Pyeongando Island, Gangwon-do Yanggu, Gyeonggi-do Gwangju, Hadong, Seosan, Jinyang, Gyeongju.

The term 'sericite' is a kind of plastic clay, which is a fine muscovite minerals and has a luster similar to that of the surface. The characteristic of the sericite as a raw material for ceramics is that it has a high plasticity, a high dry strength, a role of feldspar, and fine particles of iron, especially iron sulfide, not included.

The 'Bentonite' is a clay material consisting of volcanic ash or montmorillonite Al ₂ O ₃ .4SiO ₂ .2H ₂ O which is transformed into tuff as a main mineral, .

The above-mentioned 'Pottrey stone' is a raw material of ceramics made of quartz, ceriseite (mica clay minerals) and kaolinite as main constituent minerals. It is made of monolithic ceramics It means the raw material that can be made, that is, it means a combination stone made by nature. The stone crushing material is plastic in a short time and has a property of magnetizing at a relatively low temperature when it is calcined. The greater the number of sericite, the greater the plasticity and the greater the dry strength. Also, the degree of refinement of the silica greatly affects the properties of the product. The chemical composition of stover is 65 to 80% of SiO ₂ , 13 to 20% of Al ₂ O ₃ , 0.04 to 1% of Fe ₂ O ₃ , 0.03 to 0.8% of CaO, 0.4% or less of MgO, 0.06 to 7% of K ₂ O, 0.1 to 3%, and H ₂ O 1.5 to 5%. Chemically, the content of alumina and alkali is high and it becomes a raw material of ceramics. In Korea, it is calculated in large quantities in Hadong, Yangsan, Gyeongbuk Cheongsong, Gyeonggi Siheung, and Kangwon Yanggu in Korea.

The clay, sericite, dolomite and bentonite which are constituents of the base composition of the present invention can be purchased from the market, or mined from a nationwide mountain in the country.

The present invention also relates to a method for producing a fermented beverage comprising 20 to 30% by weight of white clay, 20 to 50% by weight of sericite, 10 to 15% by weight of frit, 10 to 15% by weight of titanium oxide, 1 to 10% 1 to 10% by weight of a powder.

The glaze composition of the present invention is prepared by mixing 20 to 30% by weight of white clay, 20 to 50% by weight of sericite and 10 to 15% by weight of frit, pulverizing the mixture into 250 to 350 mesh, adding 10 to 15% 10% by weight and torumarin 1 to 10% by weight, and natural aging for 40 to 50 days.

In the present invention, the term 'glaze' refers to a glassy lye applied to thinly cover and adhere to a baked ground when a pottery is manufactured.

The term 'frit' generally refers to a glassy powder, which is used as a glaze blend component of ceramics or as a glaze main component of enamel.

The 'bone ash' is an important raw material of bone china and is made by calcining bones. Bones of various animals have been used as raw material bones, but bones (beef bone) are used because they can be burned to white with less iron oxide. Thorns are mostly used as raw materials of thorns, but they act as fluxes and increase whiteness and translucency of the base.

The term "Tourmaline" is a borosilicate having hexagonal columnar crystals and is a natural mineral belonging to the hexagonal system. The tourmaline crystal itself has the characteristic of generating electricity and has the nickname "tourmaline".

In an embodiment of the present invention, the glaze composition may further include pine wood, oak, and other materials in addition to clay, sericite, frit, titanium oxide, bone ash and torumarin powder, And may further include at least one member selected from the group consisting of wood, bracken, zeolite and elvan.

Surplus clay, sericite, frit, titanium oxide, molybdenum, and torumarin, which are components of the glaze composition of the present invention, can be purchased commercially and used. On the other hand, pine wood, oak wood and bracken materials can be directly manufactured and used. In brief, materials obtained by burning each of pine, oak, and bracken can be used. For example, it can be carried out through a process of burning pine, oak, and bracken, respectively, so that the obtained ash is successively seated.

The present invention also provides a method for preparing a ceramic composition, comprising the steps of: a) preparing a substrate composition for ceramics comprising 20 to 30 wt% of clay, 50 to 60 wt% of sericite, 10 to 15 wt% of stones, and 5 to 15 wt% of bentonite; b) from 20 to 30% by weight of clay, from 20 to 50% by weight of sericite, from 10 to 15% by weight of frit, from 10 to 15% by weight of titanium oxide, from 1 to 10% by weight of ore and from 1 to 10% ≪ / RTI > c) shaping and drying the base composition for a ceramic article; d) cooling the dried molded product after the first calcination by the step c); And e) applying the glaze composition to the molding subjected to the first firing and then firing secondarily.

The step a) of the present invention is a step of preparing a basecoat composition for ceramic, more specifically 20 to 30% by weight of clay having fine pores in natural raw materials, 50 to 60% by weight of sericite, % And bentonite in an amount of 5 to 15% by weight, pulverizing the mixture into 300 to 350 mesh, and aging the mixture for 10 to 20 days to prepare a basecoat composition for a pottery.

The step b) of the present invention is a step of preparing a glaze composition. More specifically, 20 to 30% by weight of white clay, 20 to 50% by weight of sericite and 10 to 15% by weight of frit are mixed, Pulverized, and then the glaze composition is prepared by adding 10-15% by weight of titanium oxide, 1-10% by weight of bone meal and 1-10% by weight of torumarin and naturally aging the mixture for 40 to 50 days.

In one embodiment of the present invention, in the step b), the glaze composition may be added in addition to clay, sericite, frit, titanium oxide, bone ash and torumarin powder to enhance the far- Pine wood, oak wood, bracken, zeolite, and elvan stone.

The step (c) of the present invention is a step of molding and then drying the basecoat composition for ceramic. More specifically, the basecoat prepared through step (a) is kept warm and moistened to form a desired shape, Drying at 100 to 120 ° C for 1 to 3 hours.

In the step (d) of the present invention, the first molding step may be performed after the first molding step and the first molding step may be performed at a temperature of 750 to 800 ° C for 15 to 20 hours, The cooling process can be carried out by natural cooling at room temperature (20 to 30 ° C).

The step (e) of the present invention is a step of applying a glaze composition prepared through the step b) to a molded product subjected to a first firing process, followed by a second firing process, wherein the second firing process is performed at a temperature of 1250 to 1280 캜, Time.

The molded product subjected to the second firing process can be naturally cooled at room temperature (20 to 30 ° C) to finally obtain a multifunctional ceramics of the present invention having a deodorizing function and a far-infrared ray and anion radiating function.

The present invention also provides a multi-functional ceramics produced by the above method.

The multifunctional oxygen porcelain according to the present invention manufactured in the above-described manner can provide a comfortable environment by radiating far-infrared rays and negative ions, which are beneficial to the indoor living space, in addition to the existing simple functional and decorative effects. In addition, when used as a tableware, the smell of food can be effectively deodorized, and oxygen, far-infrared rays, and anions are released, thereby having an advantage that hygienic foods can be stored for a long time.

Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are for further illustrating the present invention, and the scope of the present invention is not limited to these examples.

< Example  1>

The Versatile  Ceramics manufacturing

&Lt; 1-1 > Preparation of substrate composition for ceramics

20 to 30% by weight of clay and 50 to 60% by weight of sericite were mixed, 10 to 15% by weight of stonite and 5 to 15% by weight of bentonite were added thereto and pulverized to 300 to 350 mesh to be aged for 10 to 20 days. Whereby the inventive ceramic composition (retort) for ceramics was produced. Each of the clay, sericite, stones and bentonite used in the production of the ceramics was purchased and used in the market.

<1-2> Production of glaze composition

20 to 30% by weight of white clay, 20 to 50% by weight of sericite, and 10 to 15% by weight of frit are mixed and pulverized to 250 to 350 mesh. 10 to 15% by weight of titanium oxide, bone ash 1 And 10% by weight of torumarin powder were added thereto, followed by natural aging for 40 to 50 days to prepare a glaze composition of the present invention. Surplus clay, sericite, frit, titanium oxide, boron, and torumarin used in the production of the glaze were generally purchased from commercial sources.

&Lt; 1-3 > Production of ceramics of the present invention

The molded article prepared by the method of Example <1-1> was moistened and molded into a desired shape, dried at 110 ° C. for 1 to 3 hours to have a constant weight (ie, no weight change), and then dried at 750 ° C. to 800 ° C. Lt; 0 &gt; C for 15 to 20 hours. Then, the glaze prepared in the above Example <1-2> was applied to the above-mentioned primary firing product, and the firing was performed at 1250 to 1280 ° C for 22 to 26 hours, followed by natural cooling at room temperature for 45 to 50 hours The multifunctional doser of the invention was prepared.

The combination ratio (% by weight) of the constituent components in the glaze composition Composition of glaze composition Example 1 Example 2 Example 3 Clay 20 25 30 Sericite 30 40 45 Frit 15 10 10 Titanium oxide 15 10 10 Gullet 10 5 4 Torumarin 10 10 One Gross weight 100 100 100

< Experimental Example  1>

Measuring deodorization effect of ceramics of the present invention

As a functional evaluation of the ceramics manufactured in Example 1, the ammonia water deodorizing ability test was conducted using a gas detection tube method in order to evaluate the ability to remove various odors by installing it in a residential space.

As a result, as shown in Table 2, the deodorization rate of the ceramics according to the elapsed time was increased. In particular, in Example 3, the deodorization rate was 76% at the time point of one hour, and it was confirmed that the deodorizing effect was excellent in a very short time compared with the other examples.

Changes in gas concentration and deodorization rate of the ceramics according to the elapsed time Example Measurement item / measurement time Early 30 minutes 60 minutes 90 minutes 120 minutes Example 1 Reference concentration (PPM) 500 480 460 450 440 Sample concentration (PPM) 500 200 150 130 120 Deodorization rate (%) - 58 67 71 73 Example 2 Reference concentration (PPM) 500 480 460 450 440 Sample concentration (PPM) 500 210 150 140 130 Deodorization rate (%) - 56 67 69 70 Example 3 Reference concentration (PPM) 500 480 460 450 440 Sample concentration (PPM) 500 150 110 95 80 Deodorization rate (%) - 69 76 79 82

< Experimental Example  2>

The far infrared ray emissivity of the ceramics of the present invention

The far infrared ray emissivity of the ceramics prepared in Example 1 was measured. The emissivity measurement was expressed as the estimated result of BLACK BODY using FT-IR Spectrometer (model: FTS 40, black body: WS 143, detector: MCT, resolution: 2 cm, USA). Specimens of 30x30x2 mm were prepared for the ceramics of the present invention.

As a result, as shown in Table 3, the far infrared ray emissivity of the ceramics of the present invention was found to reach 0.90 to 0.92. As a result, it was confirmed that the ceramics of the present invention exhibited a high far-infrared ray emissivity.

The emissivity of nuclear ceramics of the present invention Example Emissivity (3 to 20 탆) Radiant energy (W / ㎡ μm) Example 1 0.92 3.70 x 10 ^-2 Example 2 0.90 3.44 x 10 ^-2 Example 3 0.90 3.44 x 10 ^-2

< Experimental Example  3>

Anion release experiment of ceramics of the present invention

The degree of anion release from the ceramics prepared in Example 1 was measured. The measurement was carried out using a KICM-FIR-1012 test method using a charge particle measuring device. The test was performed under conditions of room temperature of 22 ° C, humidity of 41%, and anion number of 15 cc in the atmosphere. Anions emitted from the specimens were measured and expressed as ION per unit volume. Specimens of 30x30x2 mm were prepared for the ceramics of the present invention.

As a result, as shown in the following Table 4, the emission of anions of the inventive ceramics reached 20 ~ 21. Thus, it was confirmed that the ceramics of the present invention had a high anion emission effect.

Anion release of ceramics according to the invention Example Anion (ION / cc) Example 1 20 Example 2 20.5 Example 3 21.0

< Example  2>

Manufacture of pottery with maximized far-infrared radiation effect

As a result of the above experiment, it was confirmed that when the ceramics were manufactured using the glaze composition (20-30 wt% of white clay and 20-50 wt% of sericite) mixed with clay and sericite, the deodorization rate, far infrared ray and anion emission effect were excellent. In the experiment, we tried to manufacture ceramics with maximized far - infrared radiation effect by adding specific materials to these glaze compositions. Thus, glaze compositions were prepared by adding pine wood, oak wood, bracken, zeolite, loess, and quartz in the following proportions, respectively. The glaze composition was used in the same manner as in Example <1-3> Ceramics were produced. Zeolite, loess, and elvan are generally purchased from the market, and pine wood, oak wood, and bracken are directly manufactured by burning pine, oak and bracken as raw materials, Respectively.

Glaze composition (weight%) per far-infrared ray emitting material Composition of glaze composition Example 4 Example 5 Example 6 Example 7 Clay 30 30 30 30 Sericite 20 20 20 20 Frit 10 10 10 10 Titanium oxide 10 10 10 10 Gullet 5 5 5 5 Torumarin 10 10 10 10 Zeolite 15 - - - Elven stone - 15 - - ocher - - 15 - Pine tree - - - 5 Oak wood - - - 5 Bracken - - - 5 Gross weight 100 100 100 100

< Experimental Example  4>

Influence of Addition of Far Infrared Emissive Materials on Far Infrared Emissivity of Ceramics

The far infrared ray emissivity of the ceramics of the present invention prepared in Example 2 was measured in the same manner as in Experiment 2.

As a result, as shown in Table 6, the far infrared ray emissivity of the ceramics to which the glaze composition of Example 7 including the pine wood material, the oak wood material and the bracken material was added as the far-infrared ray emitting material was 0.98, .

The far infrared ray emissivity of the present invention ceramics Example Emissivity (3 to 20 탆) Radiant energy (W / ㎡ μm) Example 4 0.92 3.70 x 10 ^-2 Example 5 0.92 3.70 x 10 ^-2 Example 6 0.90 3.44 x 10 ^-2 Example 7 0.99 3.88 × 10 ^-2

As a result, the far infrared ray emitting materials added to the glaze composition (20-30 wt% of white clay and 20-50 wt% of sericite) mixed with white clay and sericite of the present invention as zeolite, On the other hand, a mixture of pine wood, oak wood and brackish material exhibits a remarkable synergistic effect of releasing foreign acid when applied to the above materials, and thus the material is most suitable as a far-infrared ray emitting material to be added together with clay and sericite I could confirm the fact.

< Experimental Example  5>

Influence of Addition of Far Infrared Emission Materials on Anion Emission from Ceramics

The degree of anion release to the ceramics of the present invention prepared in Example 2 was measured in the same manner as in Experiment 3.

As a result, as shown in Table 7, a mixture of pine wood, oak wood and bracken as a far-infrared ray emitting material The ceramics to which the glaze composition of Example 7 was added exhibited the highest anion release of 23, and the anion emission was also excellent in the ceramics to which the glaze composition of Example 5 containing the elvan was added.

Anion release of ceramics according to the invention Example Anion (ION / cc) Example 4 20 Example 5 21 Example 6 20.5 Example 7 23

As a result, it has been found that when a ceramic is manufactured using a glaze composition mixed with clay and sericite (20-30 weight% of clay and 20-50 weight% of sericite), the deodorization ratio, far infrared ray and anion emission In order to maximize the far-infrared emission effect, it has been found that the addition of pine wood, oakwood and bracken to the glaze composition including white clay and sericite is the most preferable combination.

The present invention has been described with reference to the preferred embodiments. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. Therefore, the disclosed embodiments should be considered in an illustrative rather than a restrictive sense. The scope of the present invention is defined by the appended claims rather than by the foregoing description, and all differences within the scope of equivalents thereof should be construed as being included in the present invention.

Claims (8)

20 to 30% by weight of clay, 20 to 50% by weight of sericite, 10 to 15% by weight of frit, 10 to 15% by weight of titanium oxide, 1 to 10% by weight of bone ash and 1 to 10% % &Lt; / RTI &gt; The method according to claim 1,
Wherein the composition further comprises at least one member selected from the group consisting of pine wood, oak wood, bracken, zeolite and elvan. a) preparing a substrate composition for ceramics comprising 20 to 30% by weight of clay, 50 to 60% by weight of sericite, 10 to 15% by weight of stones and 5 to 15% by weight of bentonite;
b) from 20 to 30% by weight of clay, from 20 to 50% by weight of sericite, from 10 to 15% by weight of frit, from 10 to 15% by weight of titanium oxide, from 1 to 10% by weight of ore and from 1 to 10% &Lt; / RTI &gt;
c) shaping and drying the base composition for a ceramic article;
d) cooling the dried molded product after the first calcination by the step c);
and e) applying the glaze composition to the molded product subjected to the first firing and then firing secondarily. The method of claim 3,
Wherein the glaze composition further comprises at least one selected from the group consisting of pine wood, oak wood, bracken, zeolite, and elvan. The method of claim 3,
Wherein the drying in step c) is performed at 110 ° C for 1 to 3 hours. The method of claim 3,
Wherein the first firing is performed at a temperature of 50 to 800 ° C. for 15 to 20 hours in the step d). The method of claim 3,
Wherein the second firing in step e) is performed at 1250 to 1280 캜 for 22 to 26 hours. A ceramics having a far-infrared ray and anion radiating function, produced by the method according to any one of claims 3 to 7.