JPH08325891A - Woven and nonwoven fabric for packaging metal - Google Patents

Abstract

PURPOSE: To obtain a woven or a nonwoven fabric packaging material excellent in rust preventing effects and physical properties in order to package various metallic products requiring rust prevention. CONSTITUTION: This woven or nonwoven fabric for packaging a metallic product comprises synthetic fibers containing a water-soluble glass powder and a suitable well-known vaporizable rust preventing agent. Split yarns of a synthetic resin film or sheet containing the water-soluble glass powder and the suitable well- known vaporizable rust preventing agent may be used as the synthetic fibers. Furthermore, a coating layer containing the water-soluble glass powder and suitable well-known vaporizable rust preventing agent may be formed on the surface of a woven or a nonwoven fabric made of the synthetic or natural fibers.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a woven fabric or a non-woven fabric for metal packaging for packaging various metal products requiring rust prevention. Woven or non-woven fabric for metal packaging of the present invention,
Particularly, it is useful as a packaging material for packaging and protecting heavy objects and sharp metals.

[0002]

2. Description of the Related Art Conventionally, when packaging metal products, woven or non-woven fabrics made of synthetic fibers are often used in consideration of packaging strength. However, these woven fabrics or non-woven fabrics do not have anti-corrosion properties against metal, and at the contact part between the fiber and the metal, dew condensation easily occurs on the metal surface with good thermal conductivity due to changes in temperature and humidity during storage, resulting in rust. Tended to occur. In particular, a gas difference cell is formed by the action of dissolved oxygen in dew condensation water at the contact portion, and the surface inside the gap where the supply of dissolved oxygen is small serves as an anode to the free surface where supply is large, and rust progresses. Since this rust is a major defect on the product, it has been proposed to store the product in an environment where dew does not occur, but enormous capital investment is required and economical rust preventive packaging material for metal products. Was required. It was also considered that various rust preventives were kneaded into a thermoplastic resin such as a polyolefin resin to form a film, and a woven fabric and a non-woven fabric were heat-welded to each other. It is not always effective against both metals, and the rust preventive agent vaporizes and disappears due to heat during heat welding with woven or non-woven fabric, and if the sealing temperature is high, the rust preventive agent contained in the film is thermally decomposed. It was not preferable because a pinhole was generated in the film due to the generation of decomposition gas. For this reason, the mechanical strength of the woven fabric and the non-woven fabric is lost, and the appearance of the packaged product tends to be impaired due to fading due to thermal decomposition. Further, in order to avoid these problems, bonding with an adhesive was proposed instead of heat welding of these materials, but the bonding process was complicated and the cost was high, which was not economical.

[0003]

DISCLOSURE OF THE INVENTION The present invention has solved the problems which could not be solved by the conventional techniques.
It has an excellent rust prevention effect on most metals, and
An object of the present invention is to provide a woven or non-woven fabric for metal packaging, which maintains a rust preventive effect for a long period of time.

[0004]

DISCLOSURE OF THE INVENTION The present invention relates to a woven fabric in which synthetic fibers containing water-soluble glass powder are used as warp and / or weft, or short fibers or long fibers of synthetic fibers containing water-soluble glass powder. By using non-woven fabric as the packaging material, it was possible to exert a remarkable anti-corrosion effect. Further, it is also possible to prepare a coating solution consisting of a solution or dispersion of a solvent containing water-soluble glass powder, apply the coating solution to a woven or non-woven fabric as a base, and dry it to form a coating layer. The same effect was able to be exhibited. Furthermore, the present inventor has found that the rust preventive effect can be further improved by additionally adding at least one volatile anticorrosive agent together with the water-soluble glass powder.

The water-soluble glass powder used in the present invention has a composition and a particle size in consideration of the physical and chemical characteristics of the glass so as to have a controlled solubility, for example, a solubility of 1% by weight or more in water. It is a prepared water-soluble glass powder, and a B ₂ O ₃ —SiO ₂ —Na ₂ O system is used as a typical component composition. Further, the particle diameter of the glass powder is preferably 100 μm or less, more preferably 60 μm or less.

According to the present invention, when dew condensation occurs on the surface of a metal inside when a metal product is packed due to a change in temperature and humidity of the outside air,
The water-soluble glass deposited on the surface of the woven or non-woven fabric is dissolved in dew condensation water, and the glassy component is selectively adsorbed on the metal surface to form an extremely thin glass film. Therefore, the elution of metal ions such as iron is prevented, and the rust preventive effect is exhibited as an anode agent. When the saturated concentration is reached, the water-soluble glass remains without being melted, and the rust preventive effect is maintained for a long period of time. At this time, the dissolution rate and the saturation concentration can be appropriately adjusted by changing the composition ratio of the glass components. At this time, if the solubility in water is high, it will be agglomerated due to moisture absorption, which makes handling difficult, and if the solubility in water is very small, the anticorrosive effect will be poor and it will be unsuitable for use. Therefore, in the present invention, the solubility
It is necessary to adjust it to about 0.1 to 10% by weight.

In order to obtain a sufficient rust preventive effect, if the content of the water-soluble glass powder is less than 0.1% by weight based on the synthetic fiber raw material resin, the rust preventive effect is not exhibited. On the contrary, when the glass powder is added in an amount more than necessary, for example, 20% by weight or more, to the resin raw material, the monofilament breaks or becomes brittle during drawing during fiber production, which is a serious problem in production. Also when forming a coating layer of water-soluble glass powder applied to the surface of the woven or non-woven fabric, the desired rust-preventive effect can be obtained if the water-soluble glass concentration in the woven or non-woven fabric is 1.0 mg / m ² or less. Absent. As a method for containing the water-soluble glass powder in the synthetic fiber raw material resin, pellets of the synthetic fiber raw material resin, the powder and the like are mixed using an appropriate kneading means, and a Banbury mixer, a mixing roll kneader, a twin-screw kneading extruder, etc. It is obtained by compounding with a device. Furthermore, in order to improve the rust-preventing effect, it has been found that the rust-preventing effect can be further enhanced by coexisting with a known vaporizable rust-preventive agent described later in addition to the water-soluble glass powder. Compounds of crushed vaporizable rust preventives are also obtained by the same method, blended with raw resin,
Perform molding.

The raw material resin of the synthetic fiber constituting the woven or non-woven fabric is preferably a resin having excellent drawing performance from the viewpoint of fiber strength, but polyolefin resins, particularly high density polyethylene and polypropylene are preferable in terms of performance and economy. Appropriate. Other examples include polyvinyl chloride resins, polyvinyl alcohol resins, polyacrylic resins, polyvinylidene chloride resins, polyamide resins, polyester resins and modified or copolymerized polymers belonging to these series. A film or sheet is uniaxially stretched several times or more in the longitudinal direction so as to be easy to tear in a direction perpendicular to the stretching direction, and is made into a fiber,
So-called "split yarn" etc. can also be used.

The woven or non-woven fabric for metal packaging, which comprises the synthetic fiber containing the water-soluble glass powder of the present invention as a constituent material, can be produced by a known production method. Specifically, a synthetic resin containing a predetermined water-soluble glass powder is used as a raw material and a fiber having an appropriate fineness is spun by a melt spinning method. That is, it is produced by spinning by a regular spinning method, a composite spinning method, a spun bond method, a melt blow method or the like, and imparting stretching, crimping or the like as necessary. The degree of weaving of this fiber is about 1 to 100 denier for staple and multifilament,
In the case of a monofilament, it can be about 5 to 5000 denier, and these fibers are used to produce a woven or non-woven fabric by a known method. In addition, as a method for producing fibers,
There is a method of melt-extruding a film or sheet, stretching and splitting.

Further, as the vaporizable rust preventive added to the water-soluble glass powder in the present invention, dicyclohexylammonium nitrite, dicyclohexylammonium caprylate, cyclohexylamine carbamate, cyclohexylamine laurate, diisopropylammonium are used.・ Nitrite, nitronaphthalene ammonium nitrite, ammonium benzoate, cyclohexylamine benzoate, dicyclohexylamine phosphate, benzotriazole, 3-methyl-5-hydroxypyrazole, sodium nitrite, etc.
Or there is a compound.

Further, in the case of forming a coating layer containing a water-soluble glass powder on the surface of a woven fabric or a non-woven fabric in the present invention, the water-soluble glass powder or a suitable vaporizable rust preventive agent is previously added to vinyl chloride / vinyl acetate. The copolymer is dispersed in a solution of a solvent such as ethyl acetate or dispersed in an aqueous solution containing a pressure-sensitive adhesive such as an acrylic ester polymer, to fabricate a base of synthetic or natural fiber. A coating layer is formed by coating and drying a cloth or a non-woven fabric by means of coating, spraying, dipping, or the like. As another method, a water-soluble glass powder is mixed and dispersed in a hot-melt type adhesive, the fibers constituting a woven or non-woven fabric are fixed by heat welding, and a coating layer containing the water-soluble glass powder is formed. There is also a method of forming. Further, the water-soluble glass powder does not undergo thermal change at least at 400 ° C. or less, and therefore does not undergo performance deterioration due to foaming or the like.

These woven and non-woven fabrics may be processed into a bag shape or a belt shape, or may be attached to a container such as kraft paper, cardboard, recycled paper, metal, thermosetting resin or thermoplastic resin, or a container. It is possible.

The preferred embodiments of the present invention will be described below.

Example 1 A water-soluble glass powder having a glass composition of B ₂ O ₃ 60 (mol%) / SiO ₂ 25 (same) / Na ₂ O 15 (same) pulverized to a maximum particle size of 30 μm or less was applied to high-density polyethylene (Mitsui For Petrochemical Co., Ltd. Hi-Zex 5000S, MI = 0.80, density = 0.954)
After adding 20% by weight and kneading with a twin-screw extruder at a temperature of 200 ° C., master batch pellets were prepared through a pelletizer. 100 parts by weight of the masterbatch and 100 parts by weight of the resin used therein were well blended to form a flattened tubular film at a forming temperature of 195 ° C. by an inflation method. One end of the tube was cut into a flat film, and a 0.07 mm-thick film that was uniaxially stretched 2.2 times at 145 ° C was cut into 2 mm parallel to the stretching direction.
We made fine cracks and slitted them into fibers. This fibrous material was used as 0.04 mm low density polyethylene (Sumitomo Chemical Co., Ltd.).
F218-1 MI = 1.0 (density 0.919) made by F218-1 and placed vertically and horizontally on the film and heat-welded at 150 ° C to a thickness of 0.10 mm.
A laminate of a non-woven fabric containing 10% by weight of water-soluble glass and a film was prepared. The low-density polyethylene film used here was formed by another inflation molding machine at a molding temperature of 140 ° C. The non-woven fabric side for metal packaging was wrapped so as to be in contact with the test piece and subjected to a rust prevention test. The results of the bankcher impact strength test are also shown in Table 2.

[0014]

Example 2 A water-soluble glass powder having a glass composition of B ₂ O ₃ 60 (mol%) / SiO ₂ 20 (same) / Na ₂ O 20 (same) pulverized to a maximum particle size of 20 μm or less was converted into polypropylene (Nippon Petrochemical). Made by J65
20% by weight was added to 0M density = 0.905, MI = 8.0), the mixture was kneaded with a twin-screw extruder, cooled by air cooling, and then passed through a pelletizer to prepare masterbatch pellets. 15 parts by weight of this water-soluble glass masterbatch was blended with 100 parts by weight of the above-mentioned resin polypropylene to obtain raw material pellets. The pellets were melt-spun at a discharge rate of 200 g / min and a temperature of 230 ° C. using a spinneret having a hole diameter of 1.5 mm and a number of holes of 60 to obtain an undrawn yarn. This undrawn yarn was drawn at a draw ratio of 3.0 times at a temperature of 80 ° C, and the fiber length was cut to 50 mm.
A staple having a single yarn fineness of 20 denier was obtained. This staple was carded using a card machine to form a web, and a nonwoven fabric having a basis weight of 300 g / m ² was obtained by the needle punching method. This non-woven fabric contains 2.6% by weight of water-soluble glass. Table 2 shows the results of the anticorrosion test and the bankcher impact strength test of this non-woven fabric for metal packaging.

[0015]

Example 3 A water-soluble glass powder having a glass composition of B ₂ O ₃ 60 (mol%) / SiO ₂ 20 (same) / Na ₂ O 20 (same) pulverized to a maximum particle size of 40 μm or less is stirred and dispersed in MEK. Then, it was mixed and dissolved with a butyl acrylate adhesive (manufactured by Sanyo Kasei Co., Ltd.). Further, to 100 parts by weight of the adhesive, 6 parts by weight of a melamine resin-based crosslinking agent (Hitachi Chemical Co., Ltd.) and 0.06 parts by weight of a phosphoric acid monobutyl ester crosslinking accelerator (manufactured by Johoku Chemical Co., Ltd.) were added to obtain a coating solution. Was prepared. The polypropylene resin (J650M density = 0.905, MI = 8.0, manufactured by Nippon Petrochemical Co., Ltd.) used in Example 2 was melt-spun by the spunbond method to form a 1.0 mm-thick non-woven fabric. Spray the previously prepared coating solution onto the surface of the non-woven fabric that comes in contact with the metal using the spray method,
The coating layer containing 5.2 g / m ² of water-soluble glass was formed by drying with hot air at ℃. Table 2 shows the results of the rust prevention test and the bankcher impact strength test of this non-woven fabric for metal packaging.

[0016]

Example 4 A powder of water-soluble glass having a glass composition of B ₂ O ₃ 60 / SiO ₂ 22 / Na ₂ O 18 (mol%) crushed to an average particle size of 60 μm and dicyclohexylammonium nitrite as a vaporizable rust preventive agent. The powder was stirred and dispersed in MEK, and mixed and dissolved with a butyl acrylate adhesive (manufactured by Sanyo Kasei Co., Ltd.). Further, 6 parts by weight of a melamine resin-based crosslinking agent (Hitachi Chemical Co., Ltd.) and 0.06 parts by weight of a phosphoric acid monobutyl ester crosslinking accelerator (manufactured by Johoku Chemical Co., Ltd.) were added to 100 parts by weight of the adhesive to prepare a coating solution. did. The non-woven fabric is polypropylene (FL6S manufactured by Mitsubishi Yuka Co., Ltd. density = 0.
90, MI = 2.3) was made from thermoplastic resin fibers by the spunbond method. This non-woven fabric is immersed in a coating solution containing the above-mentioned water-soluble glass, an adhesive, and a rust preventive by a dipping method,
The excess adhesive was squeezed with a squeezing roll and then dried with hot air at 80 ° C. to obtain a nonwoven fabric. A 1.6 mm-thick non-woven fabric was formed to form a coating layer containing a water-soluble glass concentration of 1.5% by weight and a volatile rust preventive agent of 1.2% by weight with respect to the base nonwoven fabric.
Table 2 shows the results of the rust prevention test and the bankcher impact strength test of this non-woven fabric for metal packaging.

[0017]

[Comparative Example 1] High-density polyethylene (HIZEX 5000S manufactured by Mitsui Petrochemical Co., Ltd., MI = 0.80, density = 0.40) was produced by the same production method as in Example 1 except that the water-soluble glass powder was not contained.
954) was formed into a flattened tubular film by the inflation method at a molding temperature of 195 ° C. One end of the tube was cut into a flat film, and a 0.07 mm-thick film that was uniaxially stretched at 145 ° C. by a factor of 2.2 was made into a fibrous slit with 2 mm fine cracks parallel to the stretching direction. This fibrous material is laminated vertically and horizontally at 150 ° C.
0.04 mm low density polyethylene (F218- manufactured by Sumitomo Chemical Co., Ltd.)
1 MI = 1.0 Density 0.919) Heat-welded together with a film to a thickness of 0.10 mm to prepare a laminate of a non-woven fabric and a film. The low-density polyethylene film used here was produced by another inflation molding machine at a molding temperature of 140 ° C.
What was formed into a film was used. Table 2 shows the results of the rust prevention test and the bankcher impact strength measurement of this nonwoven fabric.

[0018]

Comparative Example 2 Polypropylene (J650M density = 0.905, MI = 8.0, manufactured by Nippon Petrochemical Co., Ltd.) prepared in the same manner as in Example 2 except that it does not contain water-soluble glass powder 2
Melt spinning was performed at 30 ° C., and the fiber length was cut to 50 mm to obtain a staple having a single yarn fineness of 20 denier. This staple was carded using a card machine to form a web, and a nonwoven fabric having a basis weight of 300 g / m ² was obtained by the needle punching method. Table 2 shows the results of the rust prevention test and the bankcher impact strength test of this nonwoven fabric.

[0019]

[Comparative Example 3] A powder of dicyclohexyl ammonium nitrite as a vaporizable rust preventive was stirred and dispersed in MEK by the same manufacturing method as in Example 4 except that the water-soluble glass powder was not contained. (Sanyo Chemical
(Manufactured by K.K.) and dissolved. Furthermore, 6 parts by weight of a melamine resin-based crosslinking agent (Hitachi Chemical Co., Ltd.) per 100 parts by weight of the adhesive,
Monobutyl phosphate cross-linking accelerator (Johoku Chemical Co., Ltd.)
0.06 part by weight was added to prepare a coating solution. The non-woven fabric is
Polypropylene molded at a molding temperature of 190 ° C (Mitsubishi Yuka
FL6S Density = 0.90, MI = 2.3) manufactured by Co., Ltd. was prepared from thermoplastic resin fibers by the spunbond method. This non-woven fabric,
The above adhesive by the dipping method, soaked in a coating solution containing a rust preventive agent, after squeezing the excess adhesive with a squeezing roll,
A layer that is dried with hot air at 80 ° C to form a coating layer containing 1.2% by weight of a volatile rust inhibitor on the base nonwoven fabric.
A 0 mm non-woven fabric was prepared. Table 2 shows the results of the rust prevention test and the bankcher impact strength test of this nonwoven fabric.

Anticorrosion test Each non-woven fabric was cut into a size of 150 x 150 mm, ultrasonically washed with solvent naphtha, and air dried to give a test piece (Table 1).
Wrapped with the prepared non-woven fabric for metal packaging and non-woven fabric, and allowed to stand in the environment (50 ° C, 95% RH) for 40 days. Then, the rust occurrence rate on the surface of the test piece was evaluated according to the evaluation criteria (a).
Shown in the table.

[0021]

[Table 1] (B) Evaluation criteria ◎: No rust, no discoloration ○: Spot rust, slight discoloration occurred △: Less than 10% relative to the area of the test piece Rust or discolored ×: 10 to less than 50% relative to the area of the test piece Rust or discoloration XX: 50% or more of the area of the test piece Rust or discoloration Bankchar impact strength test According to JIS P 8134. Test with triangular weight

[0022]

[Table 2]

[0023]

Industrial Applicability As described above, a thermoplastic resin which has a strength suitable for packaging heavy objects and sharp-edged metals and maintains a rust preventive effect on most metals for a long period of time. It becomes possible to provide a woven cloth and a nonwoven cloth for metal packaging.

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Claims (5)

[Claims] 1. A woven or non-woven fabric for metal packaging, which is made of synthetic fiber containing water-soluble glass powder. 2. A woven or non-woven fabric for metal packaging, which comprises a coating layer containing a water-soluble glass powder on the surface of a fibrous material. 3. The woven or non-woven fabric for metal packaging according to claim 2, wherein a woven or non-woven fabric of natural fiber is used. 4. The woven fabric or non-woven fabric for metal packaging according to claim 1, wherein, in addition to the water-soluble glass powder, at least one volatile anticorrosive agent coexists. 5. The woven fabric or non-woven fabric for metal packaging according to claim 2, wherein at least one or more vaporizable rust preventives are allowed to coexist in addition to the water-soluble glass powder.