JPH10259344A - Ink-form protective film forming agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ink-form protective film forming agent which is lowly viscous and can form a uniform coat excellent in film stability under high- temperature high-humidity conditions without using any ultraviolet irradiator or ultraviolet-curing ink by mixing a polyamide resin soluble in an alcohol solvent with nitrocellulose, a colorant and an organometallic coordination compound. SOLUTION: An aliphatic monocarboxylic acid mixture comprising 10-50 equivalent % 4C or lower aliphatic monocarboxylic acid and 30-90 equivalent % 12-22C aliphatic monocarboxylic acid, a polymer fatty acid, an alkylenepolyamine and 10-50 equivalent % aromatic polyamine are condensed with each other at 150-250 deg.C in an inert gas atmosphere to obtain a polyamide being soluble in an alcoholic solvent and having a total amine value(ToAmV) of 1-6 KOHmg/g, an acid value (AV) of [ToAmV+(1.0-5.0)] and a viscosity of 500 cP or below. 100 pts.wt. obtained resin is mixed with 5-40 pts.wt. nitrocellulose, 1-70 pts.wt. colorant and 0.05-5 pts.wt., per 100 pts.wt., in total, resin and nitrocellulose, organometallic coordination compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink-based protective film agent for protecting a reflective film provided on a signal recording surface of a disk substrate.

[0002]

2. Description of the Related Art An optical disk is provided with a reflective film formed by depositing gold, aluminum or the like on a resin molded substrate of polycarbonate or the like, and a film for preventing oxidation of the reflective film is required on the reflective film. Generally, an ultraviolet curable resin is used for this film, and an ultraviolet irradiation device for curing is required, so that the process is correspondingly complicated. In a method of applying a resin solution that does not require the use of an ultraviolet irradiation device, it is necessary to use a solvent that does not dissolve the disk substrate, for example, a resin that is soluble in an alcohol-based solvent, but it has not yet been put to practical use.

Conventionally, as resins soluble in alcohol solvents, polyamide resins using a dibasic acid containing a spiroacetal ring described in JP-B-44-32485 and hydroxyl groups described in JP-B-41-19997 are disclosed. Polyamide resin using a monobasic acid, or JP-A-55-965
Polyamide resins using a polyol having a hydroxyl group described in JP-A No. 1 have been proposed. However, since these polyamide resins have a small molecular weight, they are sufficient as a protective film agent for disks in terms of film stability at high temperature and high humidity. Not.

Further, conventionally, when printing a label on a disk, printing is performed with an ultraviolet-curable ink on a protective film of an ultraviolet-curable resin. Attempts have been made to form a protective film with an ultraviolet-curable ink to simplify this process, but the ultraviolet-curable ink has a high viscosity and cannot be uniformly coated, and has not been put to practical use.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a high-temperature, high-temperature high-temperature resin-based polyamide resin that does not affect the disk substrate without using an ultraviolet irradiation device or an ultraviolet-curable ink. An object of the present invention is to provide an ink-based protective film agent which is excellent in film stability under moisture and has a low viscosity, and can be uniformly coated by a method such as spin coating.

[0006]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that aliphatic monocarboxylic acids having 4 or less carbon atoms and aliphatic monocarboxylic acids having 12 to 22 carbon atoms can be obtained. A polyamide resin obtained by performing a condensation reaction by combining an aliphatic monocarboxylic acid that is a mixture with a carboxylic acid, a polymerized fatty acid, an alkylene polyamine, and an aromatic polyamine in a specific range, the performance of a conventional polyamide resin. Is found to be dramatically soluble in alcohol-based solvents or hydrocarbon-based solvents while maintaining
Furthermore, since the ink composition in which a coloring agent is blended with the polyamide resin or the like has a low viscosity and can be uniformly coated by a method such as spin coating, a protective film is formed on the disk as a protective film agent for the inked disk. The present invention was found to be able to be used when printing a label, and the present invention was completed.

That is, the gist of the present invention is to provide a reflective film on a disk substrate characterized by comprising [1] a polyamide resin, a nitrified cotton, a coloring agent and an organometallic coordination compound which are soluble in an alcohol-based solvent. Ink protective film agent to be protected, [2] polyamide resin comprising at least aliphatic monocarboxylic acid (A), polymerized fatty acid (B), alkylene polyamine (C), and aromatic polyamine (D) The protective film agent according to the above [1], which is a polyamide resin obtained by subjecting the components to a condensation reaction.
[3] A polyamide resin obtained by subjecting a polyamide resin to a condensation reaction with at least a component comprising an aliphatic monocarboxylic acid (A), a polymerized fatty acid (B), an alkylene polyamine (C), and an aromatic polyamine (D). Wherein the ratio of (A) is 10 to 50 equivalent% of the total carboxylic acid component, and (A) is an aliphatic monocarboxylic acid (E) having 4 or less carbon atoms and an aliphatic monocarboxylic acid having 12 to 22 carbon atoms. A mixture with carboxylic acid (F), wherein the ratio of (E) is 30
(2) wherein the ratio of (D) is 10 to 50 equivalent% of the total amine component.
[4] Aromatic polyamine (D)
Is a xylylenediamine or a metaxylylenediamine, the protective film agent according to the above [2] or [3], [5] the total amine value of the polyamide resin (ToAm
V) is 1 to 6 KOHmg / g, and the acid value (AV) is (ToAmV + (1.0 to 5.0)). The protective film according to any one of the above [1] to [4], Agent.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The ink-formed protective film agent of the present invention is characterized by containing a polyamide resin, nitrified cotton, a coloring agent and an organic metal coordination compound which are soluble in an alcohol-based solvent. The polyamide resin used in the present invention is a polyamide obtained by subjecting at least a component composed of an aliphatic monocarboxylic acid (A), a polymerized fatty acid (B), an alkylene polyamine (C), and an aromatic polyamine (D) to a condensation reaction. A resin comprising ethanol, isopropanol, n
-Resin soluble in alcohol solvents such as propanol and n-butanol.

1. About aliphatic monocarboxylic acid (A) Aliphatic monocarboxylic acid (A) is a mixture of aliphatic monocarboxylic acid (E) having 4 or less carbon atoms and aliphatic monocarboxylic acid (F) having 12 to 22 carbon atoms. It is. Examples of the aliphatic monocarboxylic acid having 4 or less carbon atoms (E) used in the present invention include acetic acid, propionic acid, and butyric acid, and these can be used alone or in combination at an arbitrary ratio.

As the aliphatic monocarboxylic acid (F) having 12 to 22 carbon atoms used in the present invention, a saturated or unsaturated aliphatic monocarboxylic acid can be used. Examples of the saturated aliphatic monocarboxylic acid include lauric acid, palmitic acid, stearic acid, argidic acid, behenic acid and the like. Examples of unsaturated aliphatic monocarboxylic acids include oleic acid, linoleic acid, linolenic acid, eicosenoic acid, and erucic acid, and mixed fatty acids obtained from natural fats and oils (tall oil fatty acid, rice bran fatty acid, soybean oil fatty acid, beef tallow) Fatty acids, etc.) can be used effectively. When the number of carbon atoms is less than 12, the low-temperature stability of the alcohol solution of the obtained polyamide resin tends to decrease, and a problem that the solution solidifies in winter may occur. When the number of carbon atoms exceeds 22, the softening point of the obtained polyamide resin tends to decrease, and the film stability under high temperature and high humidity deteriorates.

In the present invention, as the carboxylic acid component,
A dicarboxylic acid or the like is used in addition to the above aliphatic monocarboxylic acid. The ratio of the aliphatic monocarboxylic acid (A) in the present invention is 10 to 50 equivalent% of the total carboxylic acid component.
It is preferred that More preferably, it is 15 to 40 equivalent%. In addition, the total carboxylic acid component here also includes the polymerized fatty acid (B) described below. If the ratio of the aliphatic monocarboxylic acid (A) is less than 10 equivalent% in the total carboxylic acid component, the ratio of the dicarboxylic acid becomes high in the total carboxylic acid component, the molecular weight of the polyamide resin becomes too large, and the alcohol solubility is reduced. I do. On the other hand, if it exceeds 50 equivalent%, the molecular weight of the polyamide becomes small, and the film stability under high temperature and high humidity decreases.

In the present invention, the aliphatic monocarboxylic acid is
As described above, a mixture of the aliphatic monocarboxylic acid (E) having 4 or less carbon atoms and the aliphatic monocarboxylic acid (F) having 12 to 22 carbon atoms, and the aliphatic monocarboxylic acid (E) having 4 or less carbon atoms ) Is preferably 30 to 90 equivalent% of (A). More preferably 45 to 75 equivalent%
It is. When the proportion of the aliphatic monocarboxylic acid (E) having 4 or less carbon atoms is less than 30 equivalent%, the film stability under high temperature and high humidity is poor. On the other hand, if it exceeds 90 equivalent%, the softening point becomes too high and the alcohol solubility is lowered.

2. Regarding the polymerized fatty acid (B) The polymerized fatty acid (B) used in the present invention is obtained by polymerization of a dry or semi-dry fat or oil fatty acid or an ester thereof. That is, the polymerized fatty acid is a monobasic fatty acid containing a polyunsaturated fatty acid or an ester thereof in the range of 8 to 24.
Is a polymer obtained by polymerizing a compound having the following carbon number, and contains, as its components, a monobasic fatty acid, a dimerized polymerized fatty acid, a trimerized polymerized fatty acid, and the like. At present, many commercially available fatty acids are based on unsaturated fatty acids having 18 carbon atoms, and among them, those having the following composition are preferable. Monobasic acid having 18 carbon atoms 0 to 10% by weight Dibasic acid having 36 carbon atoms 60 to 99% by weight Tribasic acid having 54 or more carbon atoms or more 30% by weight or less. In addition, the above-mentioned polymerized fatty acids may be used alone, or a polymerized fatty acid having a tribasic acid content of 40% by weight or more in all the acids may be used in an optional ratio. In the present invention, the ratio of these polymerized fatty acids is preferably 50 to 90 equivalent% of the total carboxylic acid component. More preferably, 60 to 8
5 equivalent%. If the ratio of the polymerized fatty acid is less than 50 equivalent% of the total carboxylic acid components, the molecular weight of the polyamide resin becomes small, and the film stability is undesirably reduced. Also, 9
If it exceeds 0 equivalent%, the molecular weight of the polyamide resin becomes too large, and the alcohol solubility decreases.

3. Alkylene polyamine (C) Examples of the alkylene polyamine (C) used in the present invention include aliphatic amines such as ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine. Can be used alone or in any combination. In addition, a monoamine having 4 or less carbon atoms can be used without affecting the performance.
Examples of the monoamine having 4 or less carbon atoms include ethylamine, propylamine, and butylamine, and these can be used alone or in combination at an arbitrary ratio. In the present invention, the ratio of the alkylene polyamine (C) is 50 to 90 equivalent% of the total amine component. Preferably, 6
0 to 80 equivalent%. The ratio of the alkylene polyamine (C) is 50 equivalent% from the viewpoint of film stability under high temperature and high humidity.
The above is preferable, and 90 equivalent% or less is preferable from the viewpoint of solubility in an alcohol solvent.

4. Aromatic Polyamine (D) Examples of the aromatic polyamine (D) used in the present invention include xylylenediamine such as meta-xylylenediamine and para-xylylenediamine, and aromatic amine such as diaminophenylmethane. These can be used alone or in any combination. In particular, xylylenediamine is preferred from the viewpoint of solubility in alcohol solvents, and metaxylylenediamine is more preferred. The ratio of the aromatic polyamine (D) in the present invention is 10 to 50% by weight of the total amine component. Preferably 20-4
0 equivalent%. The ratio of the aromatic polyamine (D) is
It is preferably at least 10 equivalent% from the viewpoint of solubility in alcoholic solvents, and from the viewpoint of film stability under high temperature and high humidity.
The equivalent% or less is preferable.

The polyamide resin of the present invention can be easily produced by using at least the components (A) to (D) and by a method similar to a general method for synthesizing a polyamide resin. The reaction temperature is 150-250 ° C., preferably 160
At ~ 230 ° C, the reaction is desirably performed in an inert gas, and the reaction may be performed under reduced pressure. Further, the carboxyl equivalent and the amine equivalent do not differ so much, that is, the equivalent ratio (carboxyl equivalent / amine equivalent) is 10 / 9-10.
It is preferably about / 10 in terms of physical properties of the resin. That is,
If the carboxyl equivalent is too large relative to the amine equivalent, a polyamide resin preferable in terms of molecular weight cannot be produced.

The total amine value (T) of the polyamide resin of the present invention
oAmV) is desirably 1 to 6 KOHmg / g from the viewpoint of reactivity with the organometallic coordination compound when a protective film agent is prepared by mixing nitrified cotton and the organometallic coordination compound. For the same reason, the acid value (AV) of the polyamide resin is slightly higher than the total amine value, specifically, (ToAmV + (1.0 to 5.0)) KOHmg / g.
It is desirable that Total amine value is 1 KOHmg / g
If it is lower, the reactivity between the nitrified cotton and the organometallic coordination compound when the organometallic coordination compound is blended is low, and as a result, the film stability under high temperature and high humidity is undesirably reduced. If the total amine value exceeds 6 KOH mg / g, the solution tends to gel when nitrified cotton and an organometallic coordination compound are blended to form a solution, which is not preferable.

The acid value is (ToAmV + (1.0))
If the KOH is lower than mg / g, the total amine value of the resin is 6 KO.
The tendency tends to be the same as the case of higher than Hmg / g, and when nitrifying cotton and an organometallic coordination compound are mixed to form a solution, the solution tends to gel, which is not preferable. In addition, the acid value is (To
If (AmV + (5.0)) KOH mg / g is exceeded, the tendency is the same as when the total amine value of the resin is lower than 1 KOH mg / g, and the film stability under high temperature and high humidity is undesirably reduced.

The viscosity of the polyamide resin of the present invention is cyclohexane / isopropyl alcohol / ethyl acetate = 4 /
Using a 4/2 (weight ratio) solvent, 25% of a 35% resin solution was used.
The viscosity at ° C is measured using a B-type viscometer (model BM, rotor N
o. 2, 500 rpm when measured at 60 rpm)
It is preferably p or less. Such a polyamide resin of the present invention is a resin that is soluble in alcohol solvents such as ethanol, isopropanol, n-propanol, and n-butanol. It is also soluble in hydrocarbon solvents such as hexane, cyclohexane and cyclohexanone.

The protective film agent formed into an ink of the present invention is obtained by blending nitrified cotton, a colorant and an organometallic coordination compound with the above polyamide resin. Nitrified cotton is obtained by substituting a part or most of the three hydroxyl groups of the glucose unit of cellulose with a nitric acid group. The nitrogen content is 10.0 to 12.5% by weight, preferably 10. 5-
12.2% by weight, more preferably 10.7-11.5% by weight is used. If the nitrogen content of the nitrified cotton is less than 10.0% by weight, the affinity with the polyamide resin is insufficient, which is not preferable. If the nitrogen content of the nitrified cotton exceeds 12.5% by weight, it is difficult to dissolve in an alcohol-based solvent, and a safety problem occurs. The amount of the nitrified cotton is preferably 5 to 40 parts by weight, more preferably 10 to 30 parts by weight, based on 100 parts by weight of the polyamide resin. From the viewpoint of forming a strong protective film, the amount is preferably 5 parts by weight or more. In addition, from the viewpoint of adhesion, 40 parts by weight or less is preferable.

As the colorant used in the present invention, a general dye or pigment can be used. As the compounding amount of the coloring agent, with respect to 100 parts by weight of the polyamide resin,
The amount is preferably 1 to 70 parts by weight, more preferably 10 to 60 parts by weight. From the viewpoint of concealability, 1 part by weight or more is preferable.
Also, from the viewpoint of the viscosity of the ink and the strength of the coating film, the amount is preferably 70 parts by weight or less.

Examples of the organometallic coordination compound used in the present invention include alkyl titanate compounds and aluminum compounds. Alkyl titanate compounds are preferable, such as tetraisopropyl titanate and tetra n-butyl titanate. Can be mentioned. The amount of the organometallic coordination compound was determined based on 100 parts by weight of the polyamide resin and the nitrified cotton.
0.05 to 5 parts by weight, more preferably 0.1 to 3 parts by weight is preferred. From the viewpoint of forming a strong protective film, 0.0
5 parts by weight or more is preferable. Also, from the viewpoint of solvent stability of the compound, the amount is preferably 5 parts by weight or less.

The ink-formed protective film agent of the present invention can be applied to a disc substrate of a polyamide resin by mixing and combining a specific polyamide resin, a nitrifying cotton, a colorant, and an organic metal coordination compound such as an alkyl titanate. It has the characteristics of both good adhesion and the strength of the protective film of nitrified cotton, and the terminal functional groups (amino group, carboxyl group) of polyamide resin by the organometallic coordination compound.
And a functional group (nitro group) of nitrified cotton, whereby more excellent film stability is improved. Further, since the protective film agent of the present invention is made into an ink with a colorant and has a low viscosity, uniform coating can be performed by a method such as spin coating. Therefore, it can be used as a protective film agent for a disk and as an ink when printing a label on the disk. That is, in the present invention, the term "inking" refers to a composition obtained by dispersing a colorant in a solution of a polyamide resin and then adding an organometallic coordination compound and nitrified cotton.

The protective film agent formed into an ink of the present invention is usually an alcohol such as ethanol and isopropanol,
The polyamide resin is dissolved in hydrocarbons such as hexane, cyclohexane and cyclohexanone, esters such as ethyl acetate, or a mixture thereof (for example, cyclohexane / isopropyl alcohol / ethyl acetate = 4/4/2 (weight ratio)). Thereafter, an organometallic coordination compound such as nitrified cotton and alkyl titanate is mixed to be used as an ink and as a protective film agent. The amount of the solvent used is 65 to 90 parts by weight based on 100 parts by weight of the protective film agent. In the preparation of the protective film agent, a compounding agent such as a plasticizer may be further appropriately mixed and used.

The present invention provides a method for forming a protective film for a disk, which comprises applying the ink protective film agent of the present invention onto a reflective film provided on a signal recording surface of a disk substrate. The application of the protective film agent is performed by a spin coater or a screen printing machine. Further, the present invention provides a disk having a protective film formed in this way.

[0026]

EXAMPLES Next, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples. still,
“Parts” and “%” indicate “parts by weight” and “% by weight”, respectively, unless otherwise specified.

Polyamide Resin Production Examples 1 to 7 and Comparative Production Examples 1 to 7 The raw materials (equivalents) described in Tables 1 and 2 were mixed with a thermometer, a stirring system,
The mixture was placed in a four-necked round-bottomed flask equipped with a dehydrating tube and a nitrogen blowing tube, and the mixture was stirred and a slight amount of nitrogen was flowed in order to prevent coloring of the contents. Then, a polyamide resin was obtained. Table 2 also shows the properties of the resin thus obtained.

Among the resin properties shown in Table 2, the softening point was measured by a ring and ball method, and the solution viscosity was 35% resin solution using a solvent of cyclohexane / isopropyl alcohol / ethyl acetate = 4/4/2 (weight ratio). Was measured at 25 ° C using a B-type viscometer (model BM, rotor No. 2, rotation speed 60 rpm).
m). The polymerized fatty acid used was Haridimer 250 (2.9% monobasic acid, manufactured by Harima Chemicals, Inc.).
Dibasic acid 78.8%, tribasic acid 18.3%).

[0029]

[Table 1]

[0030]

[Table 2]

[0031]

[Table 3]

Examples 1 to 7 and Comparative Examples 1 to 7 The polyamide resins of Production Examples 1 to 7 and Comparative Production Examples 1 to 7 were prepared by adding cyclohexane / isopropyl alcohol / ethyl acetate =
The resultant was dissolved in a 4/4/2 (weight ratio) solution to prepare a solution () having a resin concentration of 35%. Dissolve nitrified cotton (FQRS1 / 2, manufactured by Daicel Chemical Industries, Ltd.) in ethyl acetate and add
() Was prepared with 5% non-volatile content. These (), (), TiO ₂ as a coloring agent, and a solvent were mixed in the following composition. The obtained mixture was dispersed together with 100 parts of glass beads using a paint shaker for 2 hours to obtain a white ink. Further, to 100 parts of this white ink, 1.5 parts of an organometallic coordination compound (4 parts of tetraisopropyl titanate dissolved in 6 parts of acetylacetone) was added, and mixed for 15 minutes with a paint shaker to form a white ink. A protective film solution was prepared. Resin solution () 33.0 parts Nitrified cotton solution () 15.4 parts TiO ₂ 25.0 parts Solvent (cyclohexane / IPA / ethyl acetate = 4/4/2) 25.1 parts (IPA; isopropyl alcohol)

Next, a reflective film is formed on a substrate formed of a polycarbonate resin by vapor deposition of aluminum, and the above-mentioned protective film agent solution made into white ink is applied on the reflective film to a film thickness of about 10 μm by a spin coater. After drying, the film stability of the disk under high temperature and high humidity and the printing performance of the ink were examined.

The test method and criteria are as follows. 1) Film stability under high temperature and high humidity: A disk was inserted into a bag made of nonwoven fabric and polypropylene film so that the polypropylene film surface and the protective film surface were in contact with each other, and a 1.5 kg load was applied to the disk surface. 85 ° C, 80%
It is left in a constant temperature and humidity chamber of RH for 24 hours to check the state of the protective film surface. ：: No change in the protective film surface. ×: The protective film surface is deformed or peeled.

2) Alcohol solubility: Polyamide resin is dissolved in (cyclohexane / IPA / ethyl acetate = 4/4/2)
(Weight ratio) The temperature at which the solution dissolved in the mixed solvent to a concentration of 35% solidified was examined. ：: 5 ° C or less △: 5 to 10 ° C ×: 10 ° C or more

3) Printing Performance of Ink When the condition of the printing surface was visually checked, Comparative Production Example 7 was obtained.
Had unevenness in the film thickness. Others had a uniform surface state.

As a result of the test, when the resins obtained in Production Examples 1 to 7 were used, all of the film stability under high temperature and high humidity, the solubility in alcohol, and the printing performance of the ink were excellent. When the resins obtained in Production Examples 1 to 7 were used, satisfactory results were not obtained.

[0038]

According to the present invention, there is provided an ink-based protective film agent comprising a polyamide resin, nitrified cotton, a colorant and an organometallic coordination compound which is soluble in an alcohol-based solvent. Has a sufficient performance as a protective film, and can simplify the manufacturing process as compared with the case where a conventional ultraviolet curable resin is used. Further, since the protective film agent of the present invention has a low viscosity, it can be uniformly coated by a method such as spin coating, and can be used as an ink when printing a label on a disk.

 ──────────────────────────────────────────────────続 き Continued on front page (72) Inventor Shingo Tanaka 1334 Minato, Wakayama

Claims (5)

[Claims] 1. An ink-based protective film agent for protecting a reflective film on a disk substrate, comprising a polyamide resin soluble in an alcohol-based solvent, nitrified cotton, a colorant, and an organometallic coordination compound. . 2. A polyamide resin obtained by subjecting at least a component comprising an aliphatic monocarboxylic acid (A), a polymerized fatty acid (B), an alkylene polyamine (C), and an aromatic polyamine (D) to a condensation reaction. The protective film agent according to claim 1, which is a polyamide resin. 3. A polyamide resin obtained by subjecting at least a component comprising an aliphatic monocarboxylic acid (A), a polymerized fatty acid (B), an alkylene polyamine (C), and an aromatic polyamine (D) to a condensation reaction. A polyamide resin, wherein the ratio of (A) is 10 to 50 of the total carboxylic acid component.
(A) is a mixture of an aliphatic monocarboxylic acid (E) having 4 or less carbon atoms and an aliphatic monocarboxylic acid (F) having 12 to 22 carbon atoms, and the ratio of (E) is ( A) -3
3. The composition of claim 2, wherein the amount of (D) is 10 to 50 equivalent% of the total amine component.
The protective film agent according to the above. 4. The protective film agent according to claim 2, wherein the aromatic polyamine (D) is xylylenediamine or metaxylylenediamine. 5. The total amine value (ToAm) of a polyamide resin.
V) is 1-6 KOHmg / g, and acid value (AV) is (ToAmV + (1.0-5.0)), The protective film agent in any one of Claims 1-4 characterized by the above-mentioned.