KR101791643B1 - Manufacture method of substrate layer and tape - Google Patents

Abstract

The present invention relates to a method of producing a tape comprising a substrate layer. The tape comprising the substrate layer produced according to the method of the present invention has improved properties such as cold resistance, heat resistance, durability, impact absorbability, water resistance and resistance to repulsion, The gap adhesion between the substrate and the substrate is excellent.

Description

Technical Field [0001] The present invention relates to a substrate layer manufacturing method and a tape manufacturing method,

The present invention relates to a substrate layer production method and a tape manufacturing method.

BACKGROUND ART An acrylic foam tape having a substrate layer is used in portable electronic devices such as mobile phones and portable game machines and electronic devices such as televisions and displays for personal computers. For example, in Korean Patent Laid-Open Publication No. 2008-0060544, an acrylic pressure-sensitive adhesive layer formed on one side of an acrylic foam layer having a predetermined thickness, a base layer formed on one side of both sides of the acrylic foam layer, a pressure- The present invention also provides a double-faced acrylic foam tape having a substrate layer, which is constituted by a releasing paper to be formed.

However, in the case of the base layer based on the conventional acrylic foam layer including the above-mentioned prior art documents, it has not been able to meet the requirements of the related art in terms of shock absorbing property, anti-rebound property, and gap adhesion with the adherend. In addition, when the tape including the conventional base layer is placed at a low temperature or a high temperature, the physical properties of the tape may be lowered, and the tape can not cope with the diversified conditions. As a result, there has been a need for improvement of cold resistance, heat resistance, waterproofness, impact absorbability and durability, and studies have been actively carried out to improve these properties.

Korea Patent Publication No. 2008-0060544

Disclosure of Invention Technical Problem [8] The present invention has been made to solve the above-mentioned problems and it is an object of the present invention to provide a base layer production method in which physical properties such as cold resistance, heat resistance, durability, impact absorbability, water resistance and resistance to repulsion are improved and gap- It is an object of the present invention to provide a tape manufacturing method.

The object of the present invention described above is achieved by a method for producing a substrate layer comprising mixing a binder resin and a thermally expandable microsphere to prepare a composition for producing a base layer and heating the composition for preparing a base layer to foam the thermally expandable microspheres Can be achieved.

According to another preferred feature of the present invention, it is possible to further include a step of laminating the composition for preparing a substrate layer on one side or both sides of the substrate before foaming the thermally expandable microspheres.

According to another preferred aspect of the present invention, the step of foaming the thermally expandable microspheres may heat the composition for preparing a substrate layer such that the thermally expandable microspheres have a temperature of 100 to 170 ° C.

According to another preferred feature of the present invention, the thermally expandable microspheres are composed of an outer shell made of a thermoplastic resin and a blowing agent contained in the outer shell and having a boiling point lower than the softening point of the thermoplastic resin, wherein the blowing agent is a hydrocarbon having 1 to 12 carbon atoms , Halides of hydrocarbons having 1 to 12 carbon atoms, and compounds capable of pyrolyzing by heating to produce a gas.

According to another preferred feature of the present invention, the step of preparing the base layer composition may include adding at least one of a crosslinking agent and a coloring agent to the binder resin and the thermally expandable microspheres.

According to another preferred aspect of the present invention, the average particle diameter of the thermally expandable microspheres may be 5 to 50 탆.

According to another preferred feature of the present invention, the expansion ratio of the thermally expandable microspheres may be 2 to 20 times the magnetic volume.

According to another preferred feature of the present invention, the thermally expandable microspheres can be reduced in density by heating.

It is another object of the present invention to provide a method for manufacturing a pressure-sensitive adhesive tape, which comprises the steps of forming a pressure-sensitive adhesive layer on one side of a release film, and laminating a release film having the pressure-sensitive adhesive layer on one side or both sides of the base layer produced by the manufacturing method according to the present invention The present invention provides a method of manufacturing a tape.

According to the method for producing a base layer and the method for producing a tape according to the present invention, since the base layer and the tape comprise the base layer composition, the physical properties such as cold resistance, heat resistance, durability, impact absorbability, water resistance and anti- Can be kept excellent.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. It is to be understood, however, that the embodiments described below are only for explanation of the embodiments of the present invention so that those skilled in the art can easily carry out the invention, It does not mean anything.

The present invention relates to a substrate layer production method and a tape manufacturing method. First, the method for manufacturing a base layer will be described in detail and then the tape manufacturing method will be described.

Hereinafter, a method for producing a substrate layer according to the present invention will be described in detail.

The method for producing a base layer according to the present invention comprises the steps of forming a composition for preparing a base layer by mixing a binder resin and a thermally expandable microspheres, and heating the composition for base layer formation to foam the thermally expandable microspheres. ≪ / RTI >

The binder resin is a copolymer resin polymerized with an acrylic monomer and at least one selected from the group consisting of methyl (meth) acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and lauryl acrylate is polymerized . ≪ / RTI >

And may be obtained by polymerizing at least one monomer selected from a monomer having a hydroxyl group, a monomer having an amide group, a monomer having a tertiary amine group, and a monomer having a carboxyl group. At this time, the monomer may be mixed so as to include 0.1 to 50 wt%, preferably 1 to 20 wt%, based on the total composition.

Examples of the monomer having a hydroxy group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-deoxybutyl (meth) acrylate, 4-hydroxybutyl Acrylate, 2-hydroxypropyleneglycol (meth) acrylate, hydroxyalkylene glycol (meth) acrylate having 2 to 4 carbon atoms in the alkylene group, (Meth) acrylate, 4-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, 7-hydroxyheptyl vinyl ether, 8-hydroxyoctyl vinyl ether, Nonyl vinyl ether, 10-hydroxydecyl vinyl ether, and the like.

Examples of the monomer having an amide group include (meth) acrylamide, N-isopropyl acrylamide, N-tertiary butyl acrylamide, 3-hydroxypropyl (meth) acrylamide, 4-hydroxybutyl (Meth) acrylamide, 8-hydroxyoctyl (meth) acrylamide and 2-hydroxyethylhexyl (meth) acrylamide. Of these, (meth) acrylamide is preferable.

Examples of the monomer having a tertiary amine group include N, N- (dimethylamino) ethyl (meth) acrylate, N, N- (diethylamino) ethyl (meth) ) Acrylate, and the like.

As the monomer having a carboxyl group, acrylic acid, methacrylic acid, itaconic acid, maleic anhydride and the like are preferable.

The method for producing the copolymer is not particularly limited and can be produced by methods such as bulk polymerization, solution polymerization, emulsion polymerization or suspension polymerization, which are commonly used in the art, and solution polymerization is preferable. In addition, a solvent, a polymerization initiator, a chain transfer agent for molecular weight control and the like which are usually used in polymerization can be used.

In the present invention, the thermally expandable microspheres have a structure in which the thermoplastic resin is outer shell and the foaming agent is enclosed therein. Specifically, the thermally expandable microspheres have a closed-cell shape.

The thermoplastic resin includes at least one selected from a nitrile monomer, a carboxyl group-containing monomer, vinylidene chloride, vinyl acetate, a (meth) acrylic acid ester monomer, a styrene monomer, an acrylamide monomer and a maleimide monomer , And preferably one obtained by polymerization from a nitrile-based monomer.

The foaming agent is contained in the outer shell and has a boiling point of not higher than the softening point of the thermoplastic resin and is characterized by being able to improve impact resistance, anti-repulsion property, adhesion agent and gap adhesion property of the base layer composition as it is foamed upon heating.

The foaming agent may include one selected from the group consisting of hydrocarbons having 1 to 12 carbon atoms, halides of hydrocarbons having 1 to 12 carbon atoms, and compounds capable of pyrolyzing by heating to produce a gas.

Specifically, the hydrocarbon having 1 to 12 carbon atoms is preferably selected from the group consisting of propane, cyclopropane, propylene, normal butane, isobutane, cyclobutane, normal pentane, cyclopentane, isopentane, neopentane, normal hexane, isohexane, cyclohexane, Cycloheptane, octane, isooctane, cyclooctane, 2-methylpentane, 2,2-dimethylbutane, petroleum ether and the like.

Halides of hydrocarbons having 1 to 12 carbon atoms include methyl chloride, methylene chloride, chloroform, carbon tetrachloride, and the like.

Examples of the compound which pyrolyzes by heating to generate a gas include azodicarbonamide, N, N'-dinitrosopentamethylenetetramine, 4,4'-oxybis (benzenesulfonylhydride) and the like.

When the composition for making the base layer is heated, the thermally expandable microspheres can be foamed. That is, the thermally expandable microspheres can be foamed by heating. The thermally expandable microspheres can be foamed at the foaming temperature. The foaming temperature of the thermally expandable microspheres may be 100-170 캜, preferably 100-150 캜. Therefore, for the foaming of the thermally expandable microspheres, the composition for preparing the base layer may be heated to 100 to 170 占 폚, preferably 100 to 150 占 폚.

The present invention improves the physical properties such as the adhesive strength of the substrate layer as the thermally expandable microspheres are foamed by heating the composition for preparing the base layer containing the thermally expandable microspheres and the binder resin to a specific temperature before foaming. That is, in order to improve the physical properties of the base layer, the base layer composition may be heated to the above-mentioned range of temperatures.

The density of the thermally expandable microspheres can be reduced by heating, and the density of the heat-expandable microspheres after heating can be reduced by about 0.01 to 0.5 g / cm ³ compared to before heating.

The expansion ratio of the thermally expanding microspheres may be from 2 to 50, preferably from 2 to 20, based on the magnetic volume.

The particle size of the thermally expandable microspheres may be 1 to 100 탆, preferably 5 to 50 탆.

The thermally expandable microspheres may be mixed in an amount of 1 to 15 parts by weight, preferably 2 to 7 parts by weight, based on 100 parts by weight of the binder resin. When the thermally expandable microspheres are mixed according to the above-mentioned criteria and are included in the composition for preparing a base layer, they exert more excellent effects in terms of adhesion, heat resistance and cold resistance.

The step of preparing the composition for making the base layer may include adding a crosslinking agent to the binder resin and the thermally expandable microspheres. And mixing the binder resin and the thermally expandable microspheres with the colorant. Most preferably, the step of preparing the composition for making a base layer may include the step of adding a crosslinking agent and a coloring agent to the binder resin and the thermally expansible microspheres.

The crosslinking agent is a component for imparting durability by reinforcing the cohesive strength or the adhesive strength of the composition for the base layer formation by chemical bonding. The crosslinking agent may include an isocyanate compound, an epoxy compound, and the like, and these may be used alone or in combination of two or more. An isocyanate-based compound, and the like, the heat resistance can be improved.

Examples of the isocyanate compound include tolylene diisocyanate, xylene diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethyl xylene diisocyanate , Diisocyanate compounds such as naphthalene diisocyanate, adducts obtained by reacting 1 mole of a polyhydric alcohol compound such as trimethylolpropane with 3 moles of a diisocyanate compound, isocyanurate compounds in which 3 moles of a diisocyanate compound is self-condensed, diisocyanate Polyfunctional isocyanate compounds containing three functional groups such as burette, triphenylmethane triisocyanate and methylene bistriisocyanate, in which the remaining one mole of diisocyanate is condensed with diisocyanate urea obtained from 2 moles of 3 moles of the compound have.

Examples of the epoxy compound include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol Hexanediol diglycidyl ether, polytetramethylene glycol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, glycerol diglycidyl ether, glycerol diglycidyl ether, Diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, resorcinol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, trimethylol propane triglycidyl ether, pentaerythritol Polyglycidyl ether, sorbitol polyglycidyl ether, adipic acid diglycidyl ester, phthalic acid diglycidyl ester, tris (glycidyl) isocyanurate N, N ', N'-tetraglycidyl-m-glycidoxyethyl isocyanurate, 1,3-bis (N, N-glycidylaminomethyl) cyclohexane, Xylylenediamine, and the like.

In addition, an isocyanate compound, an epoxy compound, and a melamine compound may be used alone or in admixture of two or more. Examples of the melamine-based compound include hexamethylol melamine, hexamethoxymethyl melamine, and hexabutoxymethyl melamine.

The crosslinking agent may be contained in an amount of 0.1 to 10 wt%, preferably 0.3 to 3 wt%, based on the total composition.

The colorant is a component to be added for the shading effect and is not particularly limited to the color of the colorant, but may preferably be a black colorant.

As the black colorant, a black pigment or a black dye can be used. As the black pigment, organic pigments or inorganic pigments generally used in the art can be used. As the pigment, various pigments used for printing ink, ink-jet ink and the like can be used, and examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts. The black dye can be used without limitation as long as it has solubility in an organic solvent.

In addition to the above-described components, the step of preparing the composition for preparing a substrate layer may further include additives such as fillers, antistatic agents, antioxidants, and silane coupling agents in order to control the adhesion, cohesion, viscosity, Lt; / RTI >

The step of preparing the composition for forming a base layer may further include a step of drying to adjust the viscosity according to the purpose. The drying conditions are not particularly limited, and drying can be carried out according to methods known in the art.

The step of heating the composition for preparing a base layer to foam the thermally expandable microspheres may heat the composition for preparing a base layer such that the thermally expandable microspheres have a temperature of 100 to 170 ° C, preferably 100 to 150 ° C.

When the composition for the base layer is heated to the foaming temperature, the thermally expandable microspheres are foamed to improve physical properties such as cold resistance, heat resistance, durability, impact absorbability, and resilience of the substrate layer and maintain excellent gap adhesion with the adherend .

In addition, the present invention may further include a step of laminating a composition for forming a base layer on one surface or both surfaces of the substrate. A composition for making a base layer may be laminated on one side of the base material, or a composition for producing a base layer may be laminated on both sides of the base material.

The step of laminating the composition for making a base layer on one side or both sides of the substrate may be carried out before foaming the thermally expandable microspheres. That is, it is possible to foam the thermally expandable microspheres by heating the composition for the base layer formation after laminating the composition for the base layer on one side or both sides of the base.

The substrate is not particularly limited and includes all types of substrates known in the art such as paper, fabric, thin metal, PET, glass, and the like. The substrate may be a commonly used transparent plastic resin substrate. For example, the substrate may be made of a material selected from the group consisting of polyesters such as polyethylene terephthalate (PET), polyethylene such as ethylene vinyl acetate (EVA), cyclic olefin polymer (COP) But are not limited to, cyclic olefin copolymers (COC), polyacrylate (PAC), polycarbonate (PC), polyethylene (PE), polymethylmethacrylate (PMMA) (PEEK), polyimide (PI), triacetylcellulose (TAC), methyl methacrylate (MMA), or fluorine-based polymers such as polyetheretherketone (PEEK), polyethylene naphthalate (PEN), polyetherimide Resin or the like. The substrate may be a single layer or a multilayer structure including two or more substrates made of the same or different materials, and is not particularly limited.

Further, the present invention can also produce a base layer without laminating the base layer composition on the base material. A tape manufactured using such a base layer is referred to as an inorganic material type tape. In this case, the thermally expandable microspheres can be foamed by laminating the prepared composition for the base layer production on one side of the release film and heating the composition for the base layer lamination laminated on the release film.

The release film is for preventing the substrate layer from being contaminated. Thus, the release film can be removed from the substrate layer during tape manufacturing. The release film may be removed from the substrate layer when the substrate layer and the adhesive layer are laminated.

The release film may be a silicone release film or a release paper of a silicone release treated paper. The release film is not limited anymore.

Hereinafter, a tape manufacturing method according to the present invention will be described in detail.

The present invention relates to a process for producing a base film, which comprises the steps of forming an adhesive layer on one side of a release film and joining a release film having an adhesive layer on one or both sides of the base layer produced by the base layer production method according to the present invention Lt; / RTI >

The manufacturing method of the base layer will not be described in the overlapping portions of the base layer manufacturing method described above.

The release film on which the adhesive layer is formed prevents the surface of the adhesive layer from being contaminated. The release film can be removed when a tape by the tape manufacturing method according to the present invention is used.

The release film may be a silicone release film or a release paper of a silicone release treated paper. However, the adhesive release film is not limited any more.

The adhesive layer may be formed of an acrylic pressure sensitive adhesive (PSA, Pressure Sensitive Adhesive).

The adhesive layer may comprise an acrylic monomer. The acrylic monomer may include at least one member selected from the group consisting of methyl (meth) acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and lauryl acrylate.

The adhesive layer may comprise a monomer having a functional group. The monomer having a functional group may be selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, maleic anhydride, 2-hydroxyethyl (meth) acrylate acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hydroxyethyl acrylate hydroxyethylacrylate, hydroxybutylacrylate and hydroxybutylacrylate.

The adhesive layer may include a tackifier. The tackifier may comprise at least one of a rosin-based resin, a terpene-based resin and a phenolic resin.

The adhesive layer may include a crosslinking agent for improving heat resistance. The crosslinking agent for improving heat resistance may include at least one of an isocyanate crosslinking agent, an epoxy crosslinking agent and a melamine crosslinking agent.

When the base layer is of an inorganic type, the release film of the base layer may be removed and a release film having an adhesive layer formed on one side or both sides of the base layer may be laminated.

Hereinafter, the present invention will be described in more detail with reference to Examples, Comparative Examples and Experimental Examples. However, the following examples, comparative examples and experimental examples are for illustrating the present invention, and the present invention is not limited by the following examples, comparative examples and experimental examples, and can be variously modified and changed.

Manufacturing example  1. Synthesis of binder resin

45 parts by weight of n-butyl acrylate (BA), 45 parts by weight of 2-ethylhexyl acrylate, and 10 parts by weight of acrylic acid were added to a 1 L reactor equipped with a cooling device for regulating the temperature of the nitrogen gas, 100 parts by weight of ethyl acetate was added as a solvent. Nitrogen gas was then purged for 1 hour to remove oxygen and then maintained at 80 ° C. After the mixture was homogenized, 0.07 part by weight of azobisisobutyronitrile (AIBN) was added as a reaction initiator and reacted for 6 hours to prepare an acrylic binder resin.

Manufacturing example  2. Preparation of black colorant

12 parts by weight of C.I. Pigment Black 1 and 4.0 parts by weight of BYK-2001 as a pigment dispersant were mixed in an organic solvent and the pigment was sufficiently dispersed using a bead mill to prepare a black colorant.

Example  One

(1) Composition for producing a base layer

On the basis of the solid content, 100 parts by weight of the acrylic copolymer of Production Example 1, 5 parts by weight of F-50D (average particle diameter: 15 mu m) as thermally expandable microspheres and 10 parts by weight of other additives were mixed, And then diluted with an organic solvent to prepare a composition for preparing a base layer.

(2)

The base layer composition prepared in the above step (1) was allowed to stand at room temperature for about 30 minutes to remove bubbles, and was then applied onto a PET film (50um, corresponding to the substrate) and dried under the conditions shown in Table 1 The thermally expandable microspheres were foamed) to form a base layer. And another layer of a release film was laminated thereon.

In Table 1, the foaming rate was calculated according to the following equation (1).

&Quot; (1) "

(15 占 퐉) of the thermally expandable microspheres (15 占 퐉) of the thermally expandable microspheres;

Drying temperature (캜) Application amount (탆) Foaming ratio (F-50D) 80 30 1.0 times (unfired) 90 30 1.0 times (unfired) 100 35 ± 3 1.13 ~ 1.5 times 110 42 ± 3 1.6 to 2 times 120 53 ± 3 2.3 to 2.9 times 130 65 ± 5 3 to 3.7 times 140 80 ± 5 4 to 4.7 times 150 78 ± 5 3.9 to 4.5 times 160 65 ± 5 3 to 3.7 times 170 50 ± 5 2 to 2.7 times

As shown in Table 1, the thermally expandable microspheres (F-50D) started foaming at about 100 ° C. and reached maximum foaming at about 145 ° C., and from about 150 ° C. or higher, the foaming rate Respectively.

Example 2. Impact resistance test

The composition prepared in Example 1 (1) was allowed to stand at room temperature for about 30 minutes to remove air bubbles and then applied on a PET film (50um), and dried under the conditions shown in Table 1 (heat- The microspheres were foamed) to form a base layer. At this time, the thickness of the base layer including the PET film was 120 mu m.

An acrylic pressure-sensitive adhesive was coated on both sides of the base layer to form a pressure-sensitive adhesive layer, and then left at 60 DEG C for 2 days. The laminate was cut into a size of 15.5 mm X 15.5 mm and adhered to PC and glass adhered to both sides with a force of 5 kg / 5 sec. The sample was left standing at room temperature for 72 hours.

The weight of the specimen was dropped from 50 mm to 500 mm at an interval of 50 mm while the weight was dropped. The weights were measured while increasing the weight from 50 g to 10 g or 50 g, and the average value was calculated by repeating this experiment three times. The results are shown in Table 2 below.

As a control, a pressure-sensitive adhesive layer was formed on both sides of a (PE foam, 120 μm thickness) acrylic adhesive, and the same test was conducted after standing at 60 ° C. for 2 days.

Specimen (including thermally expandable microspheres) Control group Vertical test 392 mJ 196 mJ Shear test 4737 mJ 2548 mJ

As shown in Table 2 above, it was shown that the specimen including the substrate layer including the thermally expandable microspheres was able to withstand a stronger impact than the control. This indicates that the thermoexpandable microspheres contained in the composition play a role in relieving the impact.

Example  3. Thermal expansion Microchip  Impact resistance test according to content

As shown in the following Table 3, the composition for preparing the base layer was prepared by varying the content (unit: parts by weight) of thermally expandable microspheres, and the impact resistance test was carried out in the same manner as in Example 2.

Thermally expandable microsphere content Vertical test Shear test 0 147 mJ 1960 mJ 0.5 196 mJ 2450 mJ One 245 mJ 3267 mJ 2 294 mJ 3756 mJ 5 392 mJ 4737 mJ 10 392 mJ 4573 mJ 15 343 mJ 3822 mJ 20 180 mJ 2450 mJ

As shown in Table 3, when the thermally expandable microspheres were contained in an amount of 1 to 15 parts by weight based on 100 parts by weight of the acrylic copolymer, excellent impact resistance was exhibited.

Claims (9)

A binder resin and a thermally expansible microspheres to prepare a composition for producing a base layer;
Laminating the composition for making a base layer on one side or both sides of the base; And
And laminating the composition for forming a base layer on the base material and then heating the composition for base layer formation to foam the thermally expandable microspheres. delete The method according to claim 1,
Wherein the step of foaming the thermally expandable microspheres comprises heating the composition for preparing a substrate layer such that the thermally expandable microspheres have a temperature of 100 to 170 占 폚. The method according to claim 1,
Wherein the thermally expandable microspheres comprise an outer periphery made of a thermoplastic resin and a foaming agent contained in the outer periphery and having a boiling point lower than the softening point of the thermoplastic resin,
Wherein the foaming agent comprises one selected from the group consisting of hydrocarbons having 1 to 12 carbon atoms, halides of hydrocarbons having 1 to 12 carbon atoms, and compounds decomposing by heating to produce a gas. The method according to claim 1,
Wherein the step of preparing the base layer composition comprises adding at least one of a crosslinking agent and a coloring agent to the binder resin and the thermally expansible microspheres. The method according to claim 1,
Wherein the thermally expandable microspheres have an average particle diameter of 5 to 50 占 퐉. The method according to claim 1,
Wherein the expansion ratio of the thermally expandable microspheres is 2 to 20 relative to the magnetic volume. The method according to claim 1,
Wherein the thermally expandable microspheres have a reduced density by heating. Forming an adhesive layer on one surface of the release film; And
A method for producing a tape, comprising the step of laminating a release film having the adhesive layer formed on one side or both sides of a base layer produced by the manufacturing method according to any one of claims 1 and 3 to 8.