JP2007076013A - Laminated film material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminated film material that has no humidity independency, is free from a problem such as the stickiness of a surface, does not cause deterioration in performance in terms of a time lapse, is reduced in color difference between colors of surfaces of the film materials, and superior in both a design property and a charge preventive function, by forming an extremely thin conductive inorganic oxide film on the surface of a well-known film material such as a material for tarpaulin, canvas, a tent, a flexible container, a partition, a mesh sheet and truck hood cloth, and so on. <P>SOLUTION: The laminated film material is constituted such that: a thermoplastic resin layer is formed on at least the single side of cloth; a contamination-proof thermoplastic resin mixed with inorganic oxide particles having conductivity is coated on the surface of the thermoplastic resin layer; and the coating layer has a surface resistance value not larger than 1.0×10<SP>11</SP>Ω/m<SP>2</SP>. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a laminated film material used for tarpaulins, canvases, tents, flexible containers, partitions, mesh sheets, truck hoods, and the like.

  In general, a synthetic resin material such as a sheet made of a thermoplastic resin is very easily charged.For example, when it is used for a construction sheet or various partitions, it is easily charged and dust adheres to the human body. There was a problem due to static electricity.

As countermeasures, a method of kneading an antistatic agent in a thermoplastic resin, a method of coating carbon black on the surface of a thermoplastic resin sheet, and the like have been adopted.
As an antistatic agent kneaded in a thermoplastic resin, a surfactant anionic antistatic agent such as a long-chain alkyl compound having a low molecular weight sulfonate group (see Patent Document 1) is known. Polymeric antistatic agents include polymers having an ionized nitrogen element in the main chain (see Patent Document 2 and Patent Document 3), sulfonate-modified polystyrene (see Patent Document 4), and the like. Are known. These antistatic agents exhibit the effect by obtaining moisture in the air by shifting to the surface of the thermoplastic resin over time. Also known are methods of obtaining an antistatic effect by coating a coating containing carbon black on the surface of a thermoplastic resin sheet or kneading carbon black into a thermoplastic resin. Since there is a problem in that transparency is inhibited by carbon black, a method of coating a paint containing carbon black as a continuous pattern is employed as a method for preventing transparency from being disturbed so much.
JP-A-4-28729 JP-A-3-255139 JP-A-4-288127 JP-A-5-320390

  As described above, when a low molecular weight antistatic agent is used, the surfactant moves to the surface of the thermoplastic resin as the antistatic agent migrates to the surface, and the antistatic effect is caused by moisture depending on the humidity in the air. Although the effect can be maintained, there is a problem that adhesion or contamination to an article that comes into contact with the surface of the thermoplastic resin due to sticking to the surface occurs, and a problem that the antistatic effect decreases with time. Further, when a polymer type antistatic agent is used, a large amount of the antistatic agent needs to be blended, which is not economical. The use of a polymer antistatic agent reduces the problem of migration compared to the case of using a low molecular antistatic agent, but this polymer antistatic agent also has humidity in the air. There is a problem that the dependence on is high, and there is a problem that the antistatic effect is low in a dry state where dust is flying, and sufficient performance cannot be obtained. Furthermore, the surface color is black even when coating as a continuous pattern so that the transparency of the coating method containing carbon black on the surface of the thermoplastic resin sheet is not so hindered. There is a problem that it can only be used in a field where black coloring is not regarded as a problem.

  The object of the present invention is to solve such problems, and a very thin conductive inorganic oxide film on the surface of a known film material such as tarpaulin, canvas, tent, flexible container, partition, mesh sheet, truck hood, etc. The film does not depend on humidity, does not cause problems such as stickiness of the surface, does not deteriorate in performance over time, has a small color difference in the surface color of the film material, and is superior in both design and antistatic functions. An object of the present invention is to provide a laminated film material having a property.

The laminated film material according to claim 1 of the present invention is a stain-resistant heat in which a thermoplastic resin layer is provided on one surface of a fabric, and conductive inorganic oxide fine particles are mixed on the surface of the thermoplastic resin layer. A plastic resin is coated, and this coating layer is configured to have a surface resistance value of 1.0 × 10 ¹¹ Ω / m ² or less.

The laminated film material according to claim 2, wherein a thermoplastic resin layer is provided on both surfaces of the fabric, and the surface of at least one of the thermoplastic resin layers is mixed with inorganic oxide fine particles having conductivity. A thermoplastic resin is coated, and this coating layer is characterized by having a surface resistance value of 1.0 × 10 ¹¹ Ω / m ² or less.

  In the laminated film material according to claim 3, the conductive inorganic oxide fine particles include oxides such as titanium, zinc, antimony, tin, cerium, indium, and phosphorus, and have a particle diameter of 100 nm or less. It is characterized in that inorganic oxide fine particles having a property are mixed in a stain-resistant thermoplastic resin which is an acrylic compound, a fluorine compound, a mixture thereof, or a copolymer thereof.

  The laminated film material according to claim 4, wherein the surface of the thermoplastic resin layer is formed by using a stain-resistant thermoplastic resin mixed with conductive inorganic oxide fine particles as a continuous linear pattern such as a mesh or lattice. It is characterized by being coated.

  The laminated film material according to claim 5 is obtained by mixing metal fine particles made of aluminum, stainless steel, copper, or the like with a small piece of metal foil into a contamination-resistant thermoplastic resin into which conductive inorganic oxide fine particles are mixed. It is characterized by that.

  As described above, the laminated film material of the present invention is a mechanism for achieving an antistatic effect by causing electricity to flow by moving between fine particles in contact with each other by free electrons generated in a crystal such as an inorganic oxide, The performance dependency of humidity is low.

  The stain-resistant thermoplastic resin used in the present invention is excellent in weather resistance, light resistance, scratch resistance, transparency, and excellent heat-fusibility. For example, an acrylic compound, a fluorine-based compound, or these compounds There is a mixture or a copolymer thereof.

  Such a stain-resistant thermoplastic resin is a soft vinyl chloride or ethylene vinyl acetate copolymer as a resin provided on the surface of known membrane materials such as tarpaulins, canvas, tents, flexible containers, partitions, meshes, truck hoods, etc. It is used in consideration of the fact that thermoplastic resins such as can be heat-sealed. By using this stain-resistant thermoplastic resin, the heat-sealing property of the thermoplastic resin provided on the surface of the film material is inhibited. And the effect of excellent surface contamination resistance is obtained. In addition, this stain-resistant thermoplastic resin is excellent in stain resistance and has the effect of delaying or preventing the migration of the plasticizer component from the soft vinyl chloride.

  The same effect can be obtained by coating the surface of the thermoplastic resin layer with a stain-resistant thermoplastic resin mixed with conductive inorganic oxide fine particles as a continuous linear pattern such as a mesh or lattice. Obviously, the amount of the stain-resistant thermoplastic resin and inorganic oxide fine particles to be used is small when a continuous linear pattern such as a mesh or lattice is used.

  The particle size of the inorganic oxide fine particles is desirably 100 nm or less, preferably 30 nm or less. When the particle size of the inorganic oxide is 100 nm or more, coloring becomes strong and transparency is lowered. In addition, when the particle size is extremely small, there are a problem of dispersibility and a problem of cost.

  In addition, the contamination resistance thermoplastic resin is mixed with inorganic oxide fine particles as well as metal fine particles made of aluminum, stainless steel, copper, etc. or a small piece of metal foil, so that a larger energization than when only inorganic oxide fine particles are used. Therefore, even if the amount of inorganic oxide fine particles added is reduced, a high static elimination effect can be achieved. The maximum particle diameter of the metal fine particles is several hundreds μm or less, and the maximum width of the metal foil piece is several thousand μm or less.

  Film materials that have undergone antistatic processing with inorganic oxide fine particles have a very thin layer thickness, making it difficult to distinguish between the processed and non-processed surfaces. By mixing a small piece of foil, a metallic luster is developed, and it becomes easy to distinguish between a processed surface and a non-processed surface.

  This also has a foolproof effect that prevents the antistatic treatment surface from being mistakenly used because the antistatic treatment surface can be discriminated in the case where these treatments are performed on one side of the fabric.

  Even when the surface of the thermoplastic resin layer is coated with a stain-resistant thermoplastic resin mixed with conductive inorganic oxide fine particles as a continuous linear pattern such as mesh or lattice, together with inorganic oxide fine particles Metal fine particles or small pieces of metal foil may be mixed in, thereby obtaining the same effect.

Hereinafter, embodiments of the present invention will be specifically described based on examples and comparative examples.
Example 1
Polyvinyl chloride resin composition in which 100 parts by mass of polyvinyl chloride resin, 63 parts by mass of dioctyl phthalate (hereinafter referred to as DOP) as plasticizer, 4 parts by mass of stabilizer, and 40 parts by mass of calcium carbonate as filler are mixed. Was melt-mixed with two rolls set at 160 ° C. to obtain a film having a thickness of 0.2 mm. A film having a thickness of 0.2 mm was bonded to one side as a fabric with a fabric weight of 190 g / m ² using a polyester spun yarn in a hot press set at 155 ° C. to obtain a laminated sheet of 450 g / m ² .

ELCOM (registered trademark) P-3030 manufactured by Catalytic Chemical Industry Co., Ltd., which is a sol in which tin oxide and antimony trioxide are combined as inorganic oxide fine particles having conductivity, solid content of 30.0% and solid content of 12% The contamination-resistant thermoplastic resin mixed at a mixing ratio of acrylic compound at 25:75 is coated on one side of the laminated sheet obtained above, and subjected to heat treatment at 120 ° C. for 30 seconds to fix it. Thus, a laminated film material having an adhesion amount of 5 g / m ² was obtained. When the surface resistance value of this laminated film material was measured, a surface resistance value of 1.3 × 10 ¹⁰ Ω / m ² was obtained.

Example 2
100 parts by mass of polyvinyl chloride resin, D.I. O. A polyvinyl chloride resin composition obtained by mixing 63 parts by mass of P, 4 parts by mass of a stabilizer, and 40 parts by mass of calcium carbonate was melted and mixed with a test roll set at 160 ° C. to obtain a molten film having a thickness of 0.15 mm. At set a film having a thickness of 0.15mm to 155 ° C. hot press, the fabric weight 190 g / ^{m 2} using polyester spun yarn bonded to both surfaces as cloth, to obtain a laminated sheet of 570 g / ^{m 2.}

A contamination-resistant thermoplastic resin prepared by mixing the conductive inorganic oxide fine particle sol and the acrylic compound having a solid content of 12% in the same manner as in Example 1 at a mixing ratio of 25:75 was obtained as described above. Coating was performed on one side of the laminated sheet, heat treatment was performed at 120 ° C. for 30 seconds, and this was fixed to obtain a laminated film material having an adhesion amount of 5 g / m ² . When the surface resistance value of this laminated film material was measured, a surface resistance value of 1.2 × 10 ¹⁰ Ω / m ² was obtained.

Example 3
A contamination-resistant thermoplastic resin prepared by mixing the conductive inorganic oxide fine particle sol and the fluorine-containing compound having a solid content of 12% in the same manner as in Example 1 at a mixing ratio of 25:75 is the same as in Example 2. Coating was performed on one side of the laminated sheet prepared in (1) above, heat treatment was performed at 120 ° C. for 30 seconds, and this was fixed to obtain a laminated film material having an adhesion amount of 5 g / m ² . When the surface resistance value of this laminated film material was measured, a surface resistance value of 3.7 × 10 ¹⁰ Ω / m ² was obtained.

Example 4
With respect to 100 parts by mass of the contamination-resistant thermoplastic resin prepared by mixing the inorganic oxide fine particle sol having conductivity and the acrylic compound having a solid content of 12%, which is made in the same manner as in Example 1, with metal fine particles. A certain aluminum powder One side of a laminated sheet made in the same manner as in Example 2 was added with 0.5 part by weight of 900 (manufactured by Daiwa Metal Industry Co., Ltd.), and subjected to a heat treatment at 120 ° C. for 30 seconds. A laminated film material having an adhesion amount of 5 g / m ² was obtained by immobilization. When the surface resistance value of this laminated film material was measured, a surface resistance value of 1.6 × 10 ⁹ Ω / m ² was obtained.

  According to this Example 4, the result that the surface resistance value was improved as compared with the Example in which the metal fine particles were not added was obtained. This is because the energized portion is increased by adding metal fine particles. Further, since the surface to which the metal fine particles are added can be discriminated, it is possible to prevent erroneous use of the surface having the antistatic effect.

Example 5
The metal fine particles used in Example 4 with respect to 100 parts by mass of the contamination-resistant thermoplastic resin produced by mixing the inorganic oxide fine particle sol having conductivity and the fluorine-based compound produced in the same manner as in Example 3. A laminated film material similar to that of Example 3 was obtained except that 0.5 part by mass of was added. When the surface resistance value of this laminated film material was measured, a surface resistance value of 1.4 × 10 ⁹ Ω / m ² was obtained.

  Also in this Example 5, the result that the value of the surface resistance value was improved as compared with the Example in which the metal fine particles were not added was obtained. This is because the energized portion is increased by adding metal fine particles. Further, since the surface to which the metal fine particles are added can be discriminated, it is possible to prevent erroneous use of the surface having the antistatic effect.

Example 6
A stain-resistant thermoplastic resin made by mixing an inorganic compound fine particle sol having conductivity and an acrylic compound made in the same manner as in Example 1 into a grid-like gravure roll having a grid width of 15 mm and a line width of 3 mm. Then, one surface of the polyvinyl chloride sheet obtained in Example 2 was coated, subjected to heat treatment at 120 ° C. for 30 seconds, and fixed to obtain a laminated film material having an adhesion amount of 2 g / m ² . When the surface resistance value of this laminated film material was measured, a surface resistance value of 2.9 × 10 ¹⁰ Ω / m ² was obtained.

Example 7
A contamination-resistant thermoplastic resin made by mixing a conductive inorganic oxide fine particle sol made in the same manner as in Example 3 and a fluorine-based compound is applied to one side of the polyvinyl chloride sheet obtained in Example 2. In the same manner as in Example 6, coating was performed with a grid-like gravure roll, heat treatment was performed at 120 ° C. for 30 seconds, and this was fixed to obtain a laminated film material having an adhesion amount of 2 g / m ² . When the surface resistance value of this laminated film material was measured, a surface resistance value of 5.8 × 10 ¹⁰ Ω / m ² was obtained.

Example 8
Polyvinyl chloride obtained in Example 2 was prepared by using the same conductive inorganic oxide fine particle sol, metal fine particles, and acrylic compound made in the same manner as in Example 4 in a stain-resistant thermoplastic resin. One side of the sheet was coated with a lattice gravure roll in the same manner as in Example 6, heat-treated at 120 ° C. for 30 seconds, and fixed to obtain a laminated film material having an adhesion amount of 2 g / m ² . When the surface resistance value of this laminated film material was measured, a surface resistance value of 8.7 × 10 ⁹ Ω / m ² was obtained.

Comparative Example 1
100 parts by mass of polyvinyl chloride resin, D.I. O. Surfactant type antistatic agent TB-160 (manufactured by Matsumoto Yushi Seiyaku Co., Ltd.) 5 parts by mass with respect to polyvinyl chloride resin composition in which 83 parts by mass of P, 4 parts by mass of stabilizer, and 50 parts by mass of calcium carbonate are mixed. Was added with a test roll set at 160 ° C. to obtain a film having a thickness of 0.15 mm. At a film having a thickness of 0.15 mm 155 ° C. set to thermal pressing machine, the fabric weight 190 g / ^{m 2} using polyester spun yarn adhered to one side as the fabric, to obtain a sheet of 570 g / ^{m 2.} When the surface resistance value of this sheet was measured, it was 1.2 × 10 ⁹ Ω / m ² .

Comparative Example 2
One side of the laminated sheet obtained in Example 2 was coated with a conductive carbon ink of 19% solid content of VSKH conductive black (C) manufactured by Dainichi Seika Kogyo Co., Ltd., and subjected to a heat treatment at 120 ° C. for 30 seconds. A film material having an adhesion amount of 5.7 g / m ² was obtained. When the surface resistance value of this film material was measured, it was 1.6 × 10 ⁶ Ω / m ² .

  Table 1 shows the results of comparison of the surface resistance values, the difference between the front and back surfaces during visual discrimination, the stain resistance, the color difference, and the surface stickiness of the samples of Examples 1 to 8 and Comparative Examples 1 and 2 described above.

In addition, about the surface resistance value, it measured using the surface resistance value measuring device of SM10E type (setting voltage 500V) by Toa Denpa Kogyo Co., Ltd. As a surface resistance value measurement test of the samples shown in Table 1, those having a surface resistance value of 1.0 × 10 ¹¹ Ω / m ² or less were regarded as passing the antistatic effect.

  The difference between the front and back of the laminated film material obtained by visual inspection was determined by visual observation. Examples 4, 5, and 8 in which metal fine particles are mixed can be prevented from being used by mistake due to the metallic luster.

  As for stain resistance, each sample was put into an antifouling compound, shaken for 1 hour, and then the surface dirtiness was confirmed. In order to check the soiling, the change in the color difference of the surface was measured using a color difference meter (CR-200) manufactured by Minolta Camera Co., Ltd., and used as a judgment standard. In the stain resistance, ◎ indicates that the stain resistance is very excellent, ○ indicates that the stain resistance is excellent, xx indicates that the stain resistance is very poor, and × indicates that the stain resistance is poor. The antifouling compound comprises 38 parts by mass of field soil, 17 parts by mass of kaolin, 17 parts by mass of cement, 1 part by mass of white carbon, 1.75 parts by mass of carbon black, 0.5 part by mass of ferric oxide, mechanic oil. 8.75 parts by mass was crushed with a mortar and applied to a 150 mesh sieve.

  Moreover, the samples of Examples 1 to 8 and Comparative Examples 1 and 2 were cured for 1 week in a 90% wet heat oven at 80 ° C. and dried in a 20 ° C. oven for 24 hours. When the surface state of each sample was observed after this drying, the samples of Examples 1 to 8 and Comparative Example 2 were not changed, but the sample to which the surfactant type antistatic agent of Comparative Example 1 was added was not changed. Stickiness occurred. In the surface stickiness state of Table 1, ◎ indicates that there is no stickiness, ○ indicates that there is a little stickiness, and xx indicates that there is very stickiness.

以上のように、布帛の表面に設けた熱可塑性樹脂層の表面に、導電性を有する無機酸化物微粒子を混入させた耐汚染性熱可塑性樹脂をコーティングし、このコーティング層は１．０×１０^１１Ω／ｍ^２以下の表面抵抗値を持つように構成したことにより、耐汚染性に優れ、表面のべたつきも発生することがなく、着色することにより任意の色相の積層膜材料を得ることができる。

As described above, the surface of the thermoplastic resin layer provided on the surface of the fabric is coated with a stain-resistant thermoplastic resin mixed with conductive inorganic oxide fine particles, and this coating layer has a thickness of 1.0 × 10. By being configured so as to have a surface resistance value of ¹¹ Ω / m ² or less, it is possible to obtain a laminated film material having an arbitrary hue by coloring, without being excellent in stain resistance and without causing surface stickiness. it can.

Claims (5)

A thermoplastic resin layer is provided on one side of the fabric, and the surface of the thermoplastic resin layer is coated with a stain-resistant thermoplastic resin mixed with conductive inorganic oxide fine particles. A laminated film material having a surface resistance value of 10 ¹¹ Ω / m ² or less. A thermoplastic resin layer is provided on both sides of the fabric, and the surface of at least one of the thermoplastic resin layers is coated with a stain-resistant thermoplastic resin mixed with conductive inorganic oxide fine particles. A laminated film material having a surface resistance value of 1.0 × 10 ¹¹ Ω / m ² or less. The conductive inorganic oxide fine particles include oxides such as titanium, zinc, antimony, tin, cerium, indium, and phosphorus, and the conductive inorganic oxide fine particles have a particle diameter of 100 nm or less. 3. The laminated film material according to claim 1, wherein the laminated film material is mixed with a contamination-resistant thermoplastic resin which is a fluorine-based compound, a mixture thereof or a copolymer thereof. 2. The surface of the thermoplastic resin layer is coated with a stain-resistant thermoplastic resin mixed with conductive inorganic oxide fine particles as a continuous linear pattern such as a mesh or lattice. The laminated film material according to any one of claims 1 to 3. The metal fine particles made of aluminum, stainless steel, copper or the like or small pieces of metal foil are mixed into a contamination-resistant thermoplastic resin into which inorganic oxide fine particles having conductivity are mixed. 5. The laminated film material according to any one of 4 to 4.