JPH083878A - Production of air permeable vinyl chloride leather and film - Google Patents

Abstract

PURPOSE:To provide a vinyl-coated leather having air permeability by heat- bonding a polyvinyl chloride film to a fiber base with a resin adhesive containing a foaming agent. CONSTITUTION:This method for producing a vinyl-coated leather and film having air permeability is to coat an interface between a fiber base (or a releasable sheet) and a polyvinyl chloride film with an aqueous emulsion (or a solvent type resin) containing a foamable inorganic salt capable of easily generating a gas (e.g. ammonium bicarbonate, ammonium chloride or sodium carbonate), scatter a hot-melt adhesive polymer selected from a polyamide, a polyester, a polyacetal and a polyolefin and having high crystallinity and a melting point with little difference from that of the polyvinyl chloride and press and bond the fiber base and the polyvinyl chloride film (at 140-100 deg.C for 10-40sec.).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a breathable vinyl chloride leather or film from a vinyl chloride film.

 Since vinyl chloride is flexible, has high tensile strength, strong tearing power, is highly waterproof, and is inexpensive, it has many uses such as raincoats and cashier wear. However, in the field of breathable articles, its manufacturing method has not been solved yet. Conventionally, only how to make holes in a film has been studied, but it has not been put to practical use because it causes deterioration of water resistance, tensile strength and flexibility and loses the properties peculiar to vinyl chloride.

 Conventional methods for providing air permeability to coatings are: 1, mechanical perforation, 2, ultrasonic or electron beam method, 3, blowing agent, and 4, extraction of special components from polymer mixture. The following methods are known: 5, a method for coagulating in an aqueous solution, 6, a method for stretching, and the like. Most sports and waterproof products currently on the market are manufactured by water-repellent treatment on the surface of fiber cloth or by coating with a synthetic resin solution containing a foaming agent. Vinyl duck is mainly used for agricultural work duck and raincoat for commuting work which requires water proofing. However, it has a stuffy defect, and a breathable solution is a desperate hope of many workers. It is still not possible to directly give air permeability to a film of vinyl chloride, nylon, polyester, polyacetal, or polyolefin. It is unresolved. Therefore, it is an object of the present invention to provide breathability to a vinyl chloride film without losing its properties. According to the present invention, when the fiber substrate and the vinyl chloride film are adhered, two kinds of adhesives are applied to the intermediate surface thereof. One is a polymer powder having a high crystallinity and a melting point not much different from that of polyvinyl chloride among polyamides, polyesters, polyacetals, and polyolefins as hot-melt adhesive powders, and one is ammonium hydrogen carbonate, chloride. Aqueous emulsion or solvent type adhesive containing at least one gas generating inorganic salt such as ammonium or sodium carbonate is applied individually or as a mixed dispersion liquid, and the temperature is not lower than the melting point of the molten polymer. The present invention relates to a method for producing a breathable vinyl chloride sol by heating and melting the mixture at a temperature of 100 to 100 ° C. for 10 to 40 seconds and adhering the both.

 It is conceivable that the water vapor or the generated gas of the aqueous emulsion penetrates the melted film and becomes porous, but when the film is cooled and taken out, it sticks or shrinks, and the porosity is not maintained. The point is to maintain the porosity.

Japanese Patent Publication No. 38-26872 and Japanese Patent Publication No. 51-18991 describe that a highly crystalline polymer is stretched at a temperature 10 ° C. to 40 ° C. higher than the melting point and heat-set to obtain a porous film. ing. By stretching a highly polymerized polymer at high temperature, the mechanical arrangement of the crystal of the film begins to be disturbed, it is subject to large strain and is easily broken, but a polymer with a high crystal weight is slightly aerated by such a method. It is known to get sex. Assuming now, if a vinyl chloride film is entirely coated with a highly inert resin, it may become porous only by stretching, but the pliability, feel and strength peculiar to vinyl chloride film will be lost. Not only economical. By subjecting the polymer having high crystallinity such as polyamide, polyester, polyacetal, and polyolefins in the present invention to spot fusion bonding, in the state of being melted to a temperature higher than the melting point, the porous body is formed by the breakthrough of water vapor or gas. Not only does it prevent adhesion shrinkage of the film and does not impair the flexibility of the vinyl chloride film, but the adhesive strength between the vinyl chloride film and the substrate is generally higher than that of a water-soluble or solvent-type adhesive. It is strengthened by using together. Polymer powders of polyamide, polyolefin, polyester, and polyacetals with high crystallinity are heat-welded to vinyl chloride film to immobilize the flexible film and prevent it from shrinking when cooled, and it is opened in the film and polymer. It seems to prevent the blockage of the ventilation holes.

 The manufacturing process will be described with reference to FIG. Before the fiber substrate 1 passes through the upper side of the Tyco roll 2 and enters the heat-resistant rubber endless belt 7, the aqueous emulsion is first coated with the aqueous emulsion coating machine 3, and then the heat-melting is performed by the electrostatic roll. The powder is sprayed on the entire surface by the polymer powder spraying machine 4. On the other hand, the vinyl chloride film 6 passes through the tyrocolor 5 and enters the infinite belt 7 while being bonded to the above-mentioned fiber substrate. After passing through an infinite belt heated to 140 ° C to 100 ° C by far infrared rays or electric heat 7 for 10 seconds to 40 seconds, the vinyl chloride film 6 and the substrate 1 are bonded and integrated, and then the press roll 11 is formed. Then, it is pressure-bonded, slightly stretched and solidified by a water-cooling roll 12, and wound by a winding roll 13.

In the meantime, the integrated film and substrate run along the infinite belt 7, and there is a space 10 between the infinite belt 7 and the upper part, and water vapor and gas evaporated from the aqueous emulsion break through the molten film and escape. It is possible to produce a porous film without exception.

 With this heating machine, the temperature, speed, amount of adhesive, and amount of spraying can be adjusted appropriately.

 Figure 2 is a plan view of the breathable vinyl chloride film as seen through a microscope, taken at the Gifu Prefectural Textile Industry Laboratory. The hot-melt powder 14 scattered in the film 16 and innumerable vent holes 15 are shown. Under the electron microscope 45 times, only the hot melt powder 14 can be seen, but at 1000 times magnification, numerous vent holes 15 are seen between the hot melt powder 14.

At a magnification of 8000 times, there is a slight bulge around the ventilation holes, and it is possible to find finer holes in the back.

 The present invention will be specifically described below with reference to examples.

Example 1, Mitsubishi Kasei vinyl product sunplane Thickness 0.08 m / m Width 92 cm Tensile strength 165 kg / cm ² Elongation 350% Right angle tearing force 25 kg / cm ² 100% Modulus 55 kg / cm ² Base cloth 30 × 20 Nylon half Kiryu tricot Adhesive made vinyl acetate, ethylene, methylol acrylate copolymer emulsion 50% liquid 1000 g Adhesive hot melt powder Polyamide No. 12 30 g Both adhesives are sprayed as dispersion in water and heat treated at 130 ° C for 15 seconds.

Air permeability 0.21 cm ³ / cm ² / sec JIS. L1096.6.27.1A method Water resistance 1000 cm or more JIS. L102.5.1.1 A method Abrasion strength 331 times JIS. L1096.6.17.1A method Penetration 150 g / m ² / 24h JIS. Z0208 Example 2 An aqueous emulsion containing 1% by weight of ammonium hydrogen carbonate was processed for adhesion of the same film and substrate. It was sprayed with (1000 g of 50% emulsion, 10 g of ammonium bicarbonate and 200 g of water).

Air permeability 0.58 cm ³ / cm ² / sec JIS. L1096.6.27A method The air permeability was increased by about 3 times as compared with Example 1.

Example 3 In Example 1, both adhesives were sprayed as the same dispersion liquid, but since the amount of the hot-melt polymer is limited, first the water-soluble emulsion is sprayed and then the hot-melt polymer is added at 30 g / m ² It was sprinkled and heated at 130 ° C. for 15 seconds in the same manner.

The air permeability was 0.42, and the good result was obtained from Example 1.

Example 4 An experiment was conducted in the same manner as in Example 3 except that the hot-melt polymer was an acid-biethylene copolymer.

The air permeability was 0.39 and there was no great difference.

Example 5 The air permeability was 0 when a large amount of 30 g / m ^{2 was} sprayed with only the hot-melt polymer and polyamide 12.

Example 6 In order to increase the amount of gas generated, the above aqueous emulsion liquid was spray-bonded and heated with ammonium bicarbonate 50 g, water 400 g, emulsion 50% liquid 500 g.

The air permeability was 0. It was found that breathability does not appear with a single adhesive.

Example 7 The same film as in Example 1 was used, and release paper was used instead of the base fabric. After passing through the heating chamber and cooling, the release paper was peeled off to prepare a film.

To the hot-melt polymer, 50 g of ammonium carbonate, 400 g of water, and 1000 g of 50% emulsion were applied as an aqueous emulsion of 30 g / m ² of ethylene acid bipolymer.

Air permeability 0.61 cm ³ / cm ² / sec JIS. L1096 Water resistance 400 cm or more Penetration 800 g / m ² / h JIS. Z0208 The method for producing a breathable vinyl chloride leather or film according to the present invention is a method in which a hot-melting polymer powder having a high crystallinity and a gas generating solution are simultaneously used as an adhesive agent, and after cooling, a vent hole is formed in the film and the polymer. Although some examples have been shown that there is no adhesion or contraction, those skilled in the art can use modifications or equivalents such as solid powder type, gas generating inorganic substance type, film type etc. Changes in the principles of the invention are intended to be within the scope of the following claims because it is obvious to do so.

[Brief description of drawings]

 FIG. 1 is a schematic diagram of an apparatus used in the method of the present invention. FIG. 2 is a plan view of the breathable vinyl chloride film as seen with an electron microscope. A is 1000 magnification B is 8000 magnification Taken by Gifu Textile Industry Laboratory

[Procedure amendment]

[Date of submission] Flat 3.8.13 (Attachment 1, page 5, inserted between lines 19 and 20) The hot-melt powder in the present invention is 400 in 1 inch square.
Spread in the range of 4900 pieces. The spread amount is an approximate formula, 2
Calculated according to 5.4-ax = bx '. x is the number of powders per inch, a is the powder diameter, and b is the required vent hole diameter. In the above formula, 25.4-ax is the total amount of space in the powder scattered within 1 inch, b
x'of x'is the number of spaces and is imitated as x = x '. Example 50
In the case of requesting a ventilation hole of μ, if the diameter of the powder is 0.5 mm, 25.4-0.5x = 0.05x is obtained from the above equation, so that x = 46 squared per 46 inches. 25.4
= X (2a + 0.05), for example, 38 x 38 x 1444 per 1 inch of powder that is generally used in the market today, the contact point with b = 0 is 0.67 mm.
When fusing 0.67 mm powder, it is necessary to form a 0.05 mm hole. If it becomes 0.67-0.05 = 0.62, and if the powder height becomes 0.1 mm due to pressure and heating, The bottom area of the powder is about double, so
62 ÷ 2 = 0.31, which is 0.
You will need a powder diameter of 31mm. In this way the diameter of the powder can be calculated. If the amount and diameter of the powder used is an existing product, for example, if 1 inch 38 co-powder has a diameter of 0.25, the ventilation hole b =
Calculated from the formula of 25.4-2ax, b = 0.17. Since the 170 U hole is water resistant, it is not suitable as a vinyl chloride film, so there is a problem how to make a hole of 10 μm or less. This point will be described below. In the calculated powder amount and diameter, there is no relation to the heating temperature and time, and it is easy to form the ventilation holes above the film break line described later. Also, you can always get a certain amount of ventilation holes with peace of mind. The part of the powder fused to the film is thicker than the thickness of the film,
The film portion is rapidly melted by heating, and countless holes are generated to shrink due to the effect of surface tension. Even if the accurately calculated b, that is, the space is completely melted at a high temperature, the number of ventilation holes does not exceed 10 U, so that the achievement of the object is constant and easy. It is possible to make the film porous by ignoring the water resistance of the film within the line of damage of the film by heating and pressure, but since the favorite of vinyl chloride is the water resistance, it is difficult to see how water can pass through. The problem is how to make a film that is not breathable. The breaking point varies depending on the softening point of the film, the type, particularly the amount and thickness of the solvent, the type of the fiber substrate, especially the mesh body, the pressing pressure, the type of the adhesive, the amount of the gas generating inorganic salt, etc. It's another. An example is for a film with certain conditions. 170 ° C for 10 seconds, 160 ° C for 18 seconds, 150 ° C for 25 seconds, 140 ° C for 40 seconds, 130
The film was broken at 55 ° C., at 120 ° C. for 75 seconds, at 110 ° C. for 100 seconds, and the points are connected to each other, and the broken line of the film is obtained. On the left side of the line, the film does not break, and on the inside, a 10U hole forming line and a 5U forming line can be selected by experiments. However, the selection of the broken line is almost impossible with general machines. An accurate thermostat of heating temperature and time, ON. Overshoot when off,
A general laminating machine, which is difficult unless it is a device that incorporates recent electronics and mechatronics where the unstable element of temperature due to undershoot is taken out,
Coaching machine is not suitable. If the initial PVC film containing water and the substrate that entered the release belt are dried and the heating temperature changes, certain data cannot be obtained. It requires constant data anytime, anywhere. If the film damage line can be selected, select the 5μ forming line, and whether the high temperature and low time are good, or the low temperature and long time are good,
The selection of this line and point is important at the processing stage, because appropriate points should be selected and various results will be obtained under various conditions. According to the result of the experiment, when the powder amount and diameter are as calculated, low temperature and long time are preferable, but generally, high temperature and short time processing can prevent shrinkage after heating, that is, after hole formation. When the size of the hole becomes 250μ, how to make it less than 10μ is to reduce the pressing pressure first. It should be tested to replace the base cloth with a smooth one, and most importantly, several experiments should be conducted by decreasing the temperature and time to determine the desired ventilation hole. Tato 25
Even if the pore size is 0 μ, the space fixed by the powder can form innumerable vent holes inside the breaking point at a certain temperature and time. Next, a brief description will be given of the case where the hot-melt powder is not used. When the base cloth is a flat paper, it is almost impossible to form air holes having a diameter of 10 μm or less, and it is also difficult to use general fiber cloth, non-woven cloth and the like.
However, it is possible to form ventilation holes on the fiber substrate or embossing roll when the powder is 1 inch square 400 to 4900 indentations with a diameter of 0.6 mm to 0.15 mm. Generally, however, pores tend to be large because the adhesive strength of the convex part is weaker than that of powder, the film tends to shrink, and it is difficult to form small holes because the pores are blocked, so it is necessary to treat at high temperature. It depends. However, since it is possible to form a hole of 50 μ in an uneven roll of 25.4 = x (a + b) and b = 0.05, it is essentially the same as the present invention, and therefore, it is not included in the examples. An example was given. A general film sheet in which a vinyl chloride film or another thermosetting film and a substrate are adhered can be pressed by the embossing roll to produce a breathable film. For a film with too large a hole diameter, a urethane foam resin solution is coated on the film surface, or a vinyl chloride resin solution is sprayed or coated as a thin liquid that does not block the air holes. It is also possible to manufacture When processing a vinyl chloride sheet which is particularly required to have washing resistance, it is necessary to mix an adhesive with a gas generating agent such as ammonium carbonate, since an adhesive of m square 50 g or more is required. Attachment 2 Inserted between page 17, lines 17 and 18 The following examples 8 to 16 are tabulated for comparison. The vinyl chloride film is trade name Achilles, thickness 80 micron, 50% softener, base nylon half 30 denier, solid powder polyamide diameter 0.3 mm inch square 6
444, adhesive 50% acrylic acid vinyl acrylate copolymer aqueous solution, gas generating agent ammonium hydrogen carbonate 2% weight

Claims (2)

[Claims] 1. A method for providing breathability in a bonding process with a fiber substrate, not a method of directly making holes in the film for producing breathable vinyl chloride leather and film, the method comprising: Or, apply two kinds of adhesives on the intermediate surface of vinyl chloride film. One kind has a high crystallinity in hot-melt adhesive powder, polyamide, polyester, polyacetal, and polyolefins, and is very different from polyvinyl chloride. Polymer powders with no melting point, one with water-based emulsion containing at least one inorganic salt that easily generates gas such as ammonium hydrogen carbonate, ammonium chloride, and sodium carbonate, or solvent-type adhesive, separately. Alternatively, it is applied as a mixed dispersion liquid, and the temperature is not lower than the melting point of the molten polymer 140 ° C. to 100 ° C. for 10 seconds to 40 seconds. A method of manufacturing the Rureza. 2. A method for producing a breathable film by using a releasable sheet instead of a fibrous substrate and cooling the sheet to release the sheet.