JP2001131813A - Method for producing working glove with meshy cleat - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a working glove with a polyvinyl chloride coating having meshy anti-slip structure. SOLUTION: This method for producing working glove with meshy anti-slip structure comprises such processes that a foaming agent-containing polyvinyl chloride paste is applied on a basic fabric glove followed by foaming the resin coating film through heat melting and then depressurization while keeping the molten state to expand the foamed layer and deaerate the gas inside the bubbles of the foamed layer without breaking the bubbles; thereafter, a mesh-, crater-, and pleat-shaped structure is formed on the resin layer by crushing the resultant cavities through the atmospheric pressure. By this method, a glove rich in air permeability can be produced; besides, if a non-foamed polyvinyl chloride glove is laminatedly coated with a foamable sol, a glove having a combination of excellent anti-slip effect owing to meshy structure with liquid- shielding ability can be produced.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing coated gloves made of vinyl chloride resin for the purpose of protecting workers' hands.
Provided is a method for processing gloves covered with a vinyl chloride resin film having a network structure having high flexibility and breathability.

[0002]

2. Description of the Related Art Conventionally, natural rubber,
Cloth gloves that are entirely or partially covered with a resin such as vinyl chloride have been produced as work gloves. Since the surface of such work gloves (coated gloves) is smooth and slippery, anti-slip processing is often performed. As such non-slip processing, a method of attaching coarse particles to the surface of gloves, that is, a method of performing top coating using a vinyl chloride resin organosol or the like in which coarse particles are dispersed as a coating liquid. Is common, but
Many other processing methods have been proposed. Among them,
A method using a resin foaming technique can provide gloves with a high coefficient of friction, an excellent anti-slip effect, and air permeability for alleviating stuffiness of hands. Such an example is disclosed in JP-B-63-5822 (JP-A-58-9180).
1, filed by Towa Globe Co., Ltd.)
68 (filed by Towa Globe Co., Ltd.), JP-A-5-518
04 (our company application) is known.

[0003] The conventional anti-slip processing has a shallow unevenness, and a sufficient anti-slip effect may not be obtained depending on the work. For this reason, anti-slip processing which has deeper and sharp irregularities has been required. For example, the "protrusions" described in JP-B-63-5822 and the "infinite number of irregular mesh-like recesses"
Has an excellent anti-slip effect on light dirt containing oil and moisture, which has deep irregularities. This patent is also excellent in that it provides gloves that are breathable through holes. However, on the other hand, the through-hole is too easy for liquid to pass through. Therefore, when used for normal oil work or water work, the liquid permeates and does not work. Also, when used for handling fine powders such as fumed silica, a considerable amount of powder passes through the gloves, so that there is a problem in the protective action as working gloves, for example, the hand may be roughened by degreasing.

According to Japanese Patent Publication No. Sho 63-5822, there are cases where a through hole is opened and a case where it is not opened, but it is actually difficult to adjust the number and diameter of the through holes. . JP-B-63-5822 [Claim 1] describes that "in the sol state, it is formed by the rupture of countless air bubbles in the resin solution ..." The bubbles are ruptured one after another in a sol state.
After the coating solution is foamed in a sol state as described in "..", the foam is broken, so that the breaking occurs in a chain, and at the time of the foam breaking, rapid aggregation occurs. Also, Japanese Patent Application Laid-Open No. 2-2
As described in 42968, agglomeration tends to occur along the stitches of the base fabric, and therefore, through holes are likely to occur in the stitches between the yarns.

[0005] In addition, when the method of Japanese Patent Publication No. 63-5822 is followed, even if foaming treatment such as decompression and air blowing is not performed, foaming spontaneously occurs at the start of heating and cohesion on the base fabric yarn. Is likely to occur, and it is difficult to reduce the number of through holes or reduce the diameter of the holes. If the conditions for reducing the through-holes are adjusted, the apparent foam breakage may be reduced, but the pear-skin pattern will not be generated, the surface will be smooth, and the original anti-slip effect will not be obtained . Moreover, only the outermost layer does not break, and the state of the internal through-holes (open cells) hardly changes.

[0006] In contrast to Japanese Patent Publication No. Sho 63-5822, the resin layer of a glove is an open-cell body, whereas Japanese Patent Application Laid-Open No. 5-51804 proposes a foamed glove comprising closed cells. Although both methods have their advantages and disadvantages, they are comparable in terms of anti-slip performance. Although the gloves of JP-A-5-51804 are slightly inferior in terms of air permeability, the size of the foam, the expansion ratio, the blending amount (softness) of the plasticizer, and the like are relatively controlled by adjusting the amount of the foaming agent and the foaming conditions. Can be adjusted freely. However, it is difficult to obtain open cells with through holes up to the lining.For example, even if the amount of the foaming agent is extremely increased or the firing temperature is adjusted to a higher value, the foam film alone can be used to form bubbles on the glove surface. Drilling holes is extremely difficult. If it is intended to obtain a breathable glove by this method, after cooling and solidifying, it is necessary to make a hole in the skin layer by a method such as rubbing the surface of the foam layer coating with a bundle. It is not practical for processing gloves with complicated shapes. Also, this glove is not suitable for handling liquids. The reason for this is that the closed cell layer constituting the coating is divided by a thin coating, and there is a high risk that the coating will be easily broken during use and the liquid will permeate.

[0007] Working gloves having such a non-slip property by the foamed resin and having a shielding property against liquids have been studied, but have not been successful with vinyl chloride gloves.
An ordinary non-foamed vinyl chloride glove is prepared in advance, and this is used as a base glove. A vinyl chloride paste containing a foaming agent described in JP-A-5-51804 is applied to the base glove in place of the conventional anti-slip working liquid. We considered coating, heating, melting and foaming. However, (as is well known to those skilled in the art) the decomposition gas accumulates between the initial coating layer and the foam layer, causing delamination or a bubble-like cavity having a diameter exceeding 1 cm. No work gloves could withstand practical use because of the occurrence of cracks and the fact that the foamed layer was easily torn and rubbed off.

[0008] JP-B-63-5822 and JP-A-2-242
When the foamed sol of 968 is top-coated on the base glove in the same manner as in the above method, the foamed sol is coated on the glove by the diluent or foaming agent incorporated in the foamed sol because the first coating layer is smooth. It does not stay and slides down, making it impossible to coat in the first place. This is also because the foamed sol has poor fluidity and is very thickly attached. In addition, as for the film after gelation, the diluent or the foaming agent exerts a peeling effect with the first coating layer, so that the adhesion is poor. Although there is no particular provision in the patent, it is essential that a large amount of diluent or foaming agent be blended in order to foam the foamed sol as in the examples, and these components are used from a practical point of view. It is difficult to eliminate. Further, the surface of the first coating layer is a smooth surface different from the surface of the cloth, and the foamed sol cannot sufficiently expect an anchor effect due to permeation or coagulation with the base cloth glove. Therefore, the sol flows uprooted due to aggregation at the time of foam breakage, and uniform projections cannot be obtained on the entire surface.

[0009]

[Problems to be Solved by the Invention] In the method for producing coated gloves made of vinyl chloride, a mesh-like, crater-like, fold-like, non-slip structure having complicated and sharp irregularities such as Japanese Patent Publication No. 63-5822 has been proposed. An object of the present invention is to provide a method for producing non-slip work gloves having finer irregularities than 63-5822 and having a flexible property which cannot be achieved by conventional vinyl chloride coated gloves.

In the production of the above gloves, a chemical foaming method as disclosed in Japanese Patent Application Laid-Open No. 5-51804 is used. Provided is a method for manufacturing a glove, which does not require a foaming tank and has relatively few restrictions on the formulation of a coating liquid, such as not requiring a diluent or the like for easily foaming a sol liquid. thing.

In the method of producing coated vinyl chloride gloves having air permeability, despite the use of a foaming method using a pyrolysis gas as disclosed in JP-A-5-51804, the gloves have through holes and have sufficient air permeability. To provide a vinyl chloride coating. The through hole can be freely adjusted within a range that can be adjusted in the above foaming method. This means
In particular, compared with the method of JP-B-63-5822, it is possible to open a very small through-hole. To provide a good glove recipe.

A knitted, crater-shaped, or fold-shaped non-slip with deep, sharp irregularities (hereinafter referred to as "mesh-shaped non-slip" or "mesh-like structure") is a normal non-foamed material. An object of the present invention is to provide a working glove which is formed on top of a vinyl chloride base glove by top coating, does not slip easily even when handling a liquid such as water or oil, and has a sufficient shielding property against the liquid. In addition, the present invention provides a method for producing gloves having a non-slip structure in which the mesh-shaped non-slip is sufficiently melted and adhered by the residual heat of the resin.

[Means for Solving the Problems]

The glove made according to the present invention has an appearance similar to that of Japanese Patent Publication No. 63-5822 among conventional non-slip gloves. However, when viewed in detail, it clearly differs in its shape and configuration, in particular, in its characteristics such as flexibility and ventilation and shielding. The present invention has also found an application method of an original foaming technique which is not limited to work gloves and is not known in other processing fields from the viewpoint of a manufacturing method.

In the present invention, Japanese Patent Publication No. 63-5822
Rather than breaking the foamed sol in the sol state as in the above, the sol containing the foaming agent is heated and melted in a melting furnace to form a foamed resin layer containing closed cells. Transfer to a vacuum vessel while in the molten gel state, expand the closed cells formed by the molten gel without breaking bubbles,
It is characterized in that the gas inside the bubbles is degassed without accompanied by bubble breaking.

[0015] The expansion of the foam layer without foam breakage is as follows.
This is considered to be because the bubble film permeates the air very similar, the inside of the bubble is degassed, and the expansion stops. In this process, the bubble film is a gel in a molten state, and the film becomes thinner and thinner due to expansion, and the gas becomes more and more easily permeated. Now, after sufficient degassing, when the reduced pressure is released and the pressure is rapidly returned to normal pressure, the closed cells that have not been broken shrink inward due to the atmospheric pressure. At this time, the closed cells also overlap in the thickness direction, so that the coating layer is crushed in a complicated manner to form a film having a mesh-like non-slip structure.

At this time, it is considered that a part of each closed cell is crushed intricately and broken small to form a through hole. In addition, the decompression container has almost no air,
Insulated. If the decompression time is appropriate, the temperature of the molten gel is maintained at a high temperature, so that the films crushed and overlapped in the molten state cause fusion between the films or between the film and the base layer, Strengthen the network structure.

The present invention has been found by studying the improvement of the method of Japanese Patent Application Laid-Open No. 5-51804 to produce working gloves having excellent anti-slip performance. It has also been found by focusing on the characteristics of the molten state of soft vinyl chloride, which is an intermediate state that usually waits for cooling and solidification. As described above, the method of forming a mesh-shaped non-slip according to the present invention has been outlined. However, there are many parts that require more detailed explanation, and therefore, the present invention will be described in detail below.

The cloth gloves described in the first aspect include sewing gloves made of cotton knitted cloth, work gloves knitted by a glove knitting machine, 10-gauge gloves, and 13-gauge gloves.
Materials include synthetic fibers such as cotton, wool, nylon and polyester, high cut resistance fibers such as Vectran (manufactured by Kuraray Co., Ltd.) and Kevlar (manufactured by DuPont), and knitted gloves made of elastic wooly nylon yarn. Also includes gloves woven with rubber threads. Hereinafter, these are referred to as base cloth gloves.

In the present invention, when the base cloth glove is lifted from the mold at a fingertip or a constricted part of a wrist, abnormal heating, that is, excessive foaming occurs due to overheating. Among these hyperfoams, those having a large area cause an abnormality in the appearance of the final product also in the present invention. The abnormality referred to here is that a flat foamed layer which does not exhibit a network structure even when partially released under reduced pressure is partially generated. Therefore, as the base cloth gloves, knitted gloves such as 10-gauge gloves and 13-gauge gloves that fit a mold are preferable. However, the use of knitted sewing gloves, which are tougher than knitted gloves, has the characteristic that a glove having flexibility and fit in a low-stretch region, which has not been seen in the past, can be produced, as described later.

The method of applying a vinyl chloride paste can be roughly divided into two methods. The first is to put a base cloth glove on a flat plate, or to attach it to a mold obtained by cutting a flat plate into a hand shape, and to perform screen printing. In this method, a suitable amount of vinyl chloride paste is applied in the form of a spot or a line by a method such as that described above, and then gelled and melted in a melting furnace as it is.
The second method is to attach a base cloth glove to a three-dimensional aluminum casting glove mold in the shape of a human hand, and then apply vinyl chloride paste (sol-free paste vinyl chloride resin) on top of it. Is coated by a dip coating method or a pressureless coating method using a flow coating such as a shower coat or a curtain coat. In the second method, usually, after coating, excessively adhered vinyl chloride paste is dropped and flowed off, and when a uniform film is formed, gelation, temporary shaping, and complete melting in a melting furnace are performed.
The scope of claim 1 includes both the first method and the second method. In addition, in the description of the present application, since there are many overlapping portions, the description has been made mainly on the non-pressure coating using the shower coat in the second method.

As a coating glove method other than that described above, a ceramic glove mold is directly immersed and applied to a polyvinyl chloride paste without using a base cloth glove to produce gloves without a lining, so-called cooking gloves. The present invention can be applied to a method of manufacturing gloves and disposable gloves. However, at this time, it is difficult to adjust the thinness of the coating and the thickness (hardness).
Since practical application is considered difficult, in the present invention, the scope of the present invention was limited to that coated on a base cloth glove as described in claims 1 and 2.

The blowing agent used in claims 1 and 2 is a compound such as azodicarbonamide (ADCA), and mainly generates nitrogen gas by a thermal decomposition reaction when the resin is melted at the maximum temperature of the melting furnace. It is a compound that is generated. Also, low boiling hydrocarbons such as gasoline and kerosene may be used. The foaming agent used in the present invention may be any as long as most of the gas generated during the melting and foaming of the resin passes through the resin coating in some form and diffuses out of the system. By the way, in an example using azodicarbonamide as a foaming agent as shown in Examples described later, good results are obtained in a compounding range of 1.0 to 4.0 PHR. However, the present invention is not limited to the present invention, and since such a foaming phenomenon is affected by temperature, time, and the like, the quality of foaming cannot be uniquely determined only by the amount of the foaming agent.

The above foaming agent is gasified in the molten resin,
Although bubbles forming the foam layer are generated by movement, aggregation, coalescence, etc., the volume of the foam layer formed is much smaller than the amount of gas generated. This is because most of the generated gas is diffused to the outside during foaming, and it is also known that the gas in the bubbles is replaced with external air during and after foaming. In addition, azodicarbonamide (ADC)
In the chemical foaming according to A) and the like, utilizing the fact that the thermal decomposition of the foaming agent is affected by the heating time, the foaming agent is not completely decomposed in order to adjust the foaming state. In many cases, foaming is stopped at the stage of decomposition. For this reason, a part of the foaming agent remains in the resin without being decomposed, and when it is rapidly taken out of the molten state as in the present invention, it is conceivable that a slight amount of gas is continuously generated due to residual heat for a while.

Incidentally, azodicarbonamide (ADC)
In the case of chemical foaming by A), etc., it is easy to adjust the state of the foam layer such as the density and size of the bubbles by selecting the type of foaming agent, the particle size, the stabilizer, the kicker, the cell regulator and the melt viscosity of the resin.

On the other hand, in the method of JP-B-63-5822, since the pressure is reduced while maintaining the sol state, it is difficult to create a stable foamed shape due to a chain of foaming and rapid aggregation of the sol solution. . In other words, according to the method of Japanese Patent Publication No. Sho 63-5822, the shape of the final irregularities is not directly reflected at the beginning, but the shape of the irregularities is determined at the time of foam breaking. There is a strong tendency that the irregularities after foam breakage become coarser than the foam density.

The composition of the vinyl chloride paste used in the present invention is not particularly limited. In the case of general vinyl chloride paste processing, the resin film usually reaches the molten state, and if it is placed in a reduced pressure state as in the present invention, it is easily affected by the melt viscosity and the like, but easily expands under reduced pressure and degassed. In principle, the invention can be implemented. However, the network structure may not be partially generated due to non-uniform foaming. In carrying out the present invention, it is more desirable to take into consideration such as described in Examples 3 and 4 described later. Also, only when directly coating the base fabric, it is necessary to use a non-penetrable paste resin such as ZEST HM in Examples as conventionally known.

The time and temperature for setting in the melting furnace for heat melting and heat foaming vary depending on the composition and the performance of the melting furnace, and are not particularly limited. In various experiments when the examples described below were examined for reference, in the case where 0.5 to 4.0 parts by weight of azodicarbonamide (ADCA) was used as the blowing agent, 1
When placed in a melting furnace at 90 ° C. to 200 ° C. for 9 to 11 minutes, relatively good results were obtained.

Claim 1 states, "... Generates closed cells in the molten coating and transfers it to a decompression container while the coating is in a molten state or does not solidify by cooling." In the experiments when examining the example of the above, it was taken out of the melting furnace by hand, and transferred to a vacuum container to reduce the pressure.
It took about 1 minute and 30 seconds to reach Hg. During this time, the resin layer is left at room temperature, and the resin layer is gradually cooled from the surface. Therefore, the state of the resin surface at this time is not appropriate to be described as a molten state, and is expressed as "or during the time when it is not cooled and solidified". However, in practice, it is preferable to be able to perform the next expansion under reduced pressure in a state close to the molten state as much as possible. By the way, when left to cool at room temperature during the transfer, if it is left for about 4 minutes, there is almost no effect on the vacuum expansion. Tends to be difficult to perform well, and this is likely to occur in the network structure.

When observing the practice of the present invention, it is observed that some of the bubbles in the outermost skin layer break at the time of pressure reduction. However, in many cases, foaming of the skin layer is not even observed, and even if it occurs, it is very slight and has no effect on the large number. ... ”is used. By the way, the presence or absence of bubble breakage can be observed from the state in which expansion occurs in the entire foamed layer, and can also be determined based on whether or not contraction upon opening under reduced pressure is normal. In the present invention, the foamed layer that has been expanded at the time of opening under reduced pressure is tightened by being pressed down, and a knitted structure having sufficient strength as a non-slip is completed, and sufficient strength without this shrinkage is obtained. No unevenness is obtained. Ultimately, it is important whether this shrinkage forms a mesh-like non-slip structure, and it does not matter whether partial foaming has occurred in the intermediate process. Of course, if a large amount of foam is generated, no shrinkage occurs when the vacuum is released, and a normal network structure does not occur. It is often preferable not to generate such a large amount of foam breakage of the skin layer.

As described above, the essence of the present invention is clearly different from Japanese Patent Publication No. Sho 63-5822 and Japanese Patent Application Laid-Open No. Hei 2-242968, which aim at forming projections or irregularities by breaking bubbles.

In the method of the present invention, it is also possible in principle to break a large number of closed cells at reduced pressure. Instead of taking out the melted and foamed gloves outside the melting furnace, it is sufficient to take out the gloves from the furnace while keeping them completely warm, start decompression, and deaerate very quickly. Unfortunately, such a technique has not been established, and the state of bubble breakage is extremely non-uniform with the current technique, and is not at a practical stage. In order to make this practical, more precise foam control, heating method,
At the present time, practical application is difficult. In addition, such a large amount of foam breaks becomes a crater-like depression or a sponge-like porous body, and hardly occurs when the vacuum is released. In JP-B-63-5822 and JP-A-2-242968, the foamed sol rapidly agglomerates when foaming to form a protruding shape. However, in the present invention, since foaming occurs in a molten gel state, Due to the network structure at the molecular level, rapid aggregation and chain breakage are inhibited, and it is difficult to generate protrusions. In any case, in practicing the present invention, foam breakage of the skin layer usually occurs very partially or does not occur within a range that can be visually observed.

The pressure-reducing container used in the embodiment of the present invention is obtained by cutting the upper part of the pressure-resistant tank having a diameter of about 50 cm horizontally, laying a circular rubber packing on the edge thereof, and forming a transparent lid of 20 mm in thickness as a lid from above. A plate made of acrylic resin is placed. Therefore, the state of the glove during decompression can be observed very well.

Although it is difficult to measure the expansion of the foam layer at the time of decompression, it is difficult to measure the expansion of the glove fork.
It is about 10 times to 10 times. However, it is conceivable that the film may further expand due to the influence of the thickness of the original film, the amount of the resin adhered, the degree of foaming, and the hardness of the resin.

According to the present invention, a glove is coated with a vinyl chloride paste containing a foaming agent, and then placed in a melting furnace to form a foamed resin layer containing completely independent cells in the vinyl chloride resin layer. When the foamed glove in the molten state is transferred into a decompression container and decompression is started, first, the foam layer starts to expand. As the decompression progresses, most of the bubbles in the foamed resin layer are
It expands as a closed cell and stops expansion when expanded to some extent, or stops expansion when contracted slightly. Unlike the case of JP-B-63-5822, bubbles are hardly broken even under a reduced pressure of not more than 400 mmHg or 10 mmHg. In addition, the air inside the bubbles is degassed and almost completely degassed in about 4 minutes. In this state, when the pressure is released and the pressure is quickly returned to normal pressure, the individual closed cells that have not broken are crushed and the foam layer shrinks, causing complex irregularities such as craters, meshes, and folds. To form a structure.

By the way, the cause of stopping the expansion of the foamed layer which has begun to expand at the beginning of the decompression and the cause of degassing the inside of the non-bubble air bubbles have not been clearly confirmed. In general, polymer compounds have a coarser molecular structure than metals and ceramics, and are said to be easy to pass through air.However, there are no reports such as research reports on gas permeability in the molten state related to the present invention. No confirmation has been made. However, no breakage of the coating is observed with the naked eye when the coating is expanded during decompression, and a point where the coating is crushed to form a stitch pattern when released under reduced pressure. It is evident that it is clear that the interior of the bubble is almost completely degassed. The possible causes are introduced below.

For example, a rubber balloon of a toy will wither if it is fully inflated and left for several days. The thin film of the polymer compound usually easily permeates the gas, which is in a molten state as described in claim 1 of the present invention.
It is easy to imagine that a gaseous film made of a molten gel at a temperature close to ° C. is more permeable to gas. 20
At a high temperature close to 0 ° C., the molecules in the molten gel move violently irrespective of the PVC or plasticizer, and should be more permeable to gas molecules than at room temperature.

The pressure difference between the inside of the bubble and the inside of the depressurized container due to the reduced pressure, and the fact that the film of the bubble is gradually and extremely thinly stretched due to the expansion of the bubble, the gas is more permeable. It is considered as a factor that makes it easier. Incidentally, at this time, the film of the bubble can be stretched very thin because of the viscosity caused by the network structure of the molecules of the molten gel. It is thought that the membrane was maintained. If this is a solid-liquid dispersion system such as a sol, it will be at an earlier stage, ie, Japanese Patent Publication No. 63-5822 or
It is considered that bubbles were broken at around 400 mmHg described in 2968.

When diazocarbonamide is used as a foaming agent as described in Example 1 below, the decomposition gas generated inside the bubbles is nitrogen gas or carbon monoxide gas. It is considered that the solubility in the gel and the dipole moment of the molecules in the system also affect the gel. However, even considering these factors, the gas permeation rate of the bubble membrane at the time of decompression according to the present invention is extremely high. Therefore, the following factors are considered to be acting in parallel.

The foaming mechanism of the chemical foaming used in the present invention has been studied for a long time, and generation and movement of decomposition gas, generation of small bubbles, growth of bubbles due to coalescence, formation of cells and skin layers. Mechanisms such as formation are known. The outermost layer of the foam layer is called a skin layer, and the film tends to be thicker than other portions of the bubbles. As mentioned earlier, even in ordinary foaming processing, most of the decomposition gas generated by the chemical reaction escapes to the outside world, and the gas passes through the outermost skin layer and escapes to the outside world. There is no doubt that a relatively thick coating such as a skin layer will pass gas relatively easily. Of course, this is during the foaming agent being decomposed in all parts of the resin and generating gas, but if the decompression is started immediately after foaming as in the present invention, the gas in the coating There is a high possibility that a fine structure that passes through remains.

As is well known, this skin layer
It may be thick and strong depending on the conditions. However, in the present invention, such a phenomenon slows down the deaeration speed,
It may cause cavitation due to breakage inside the foamed layer, which may cause defects, and it is preferable to take some measures. For example, as in Example 3, a plasticizer is soaked into the skin layer later by spraying or dipping, and the surface layer is softened before foaming. Another example is simply to increase the amount of plasticizer in the sol formulation. That is, when the present invention is carried out, the blending amount of the plasticizer in the sol containing a foaming agent is from 180 to 220 parts by weight.
In such a case, it has been observed that degassing can be performed relatively stably irrespective of other conditions, and a network-like structure is also uniformly generated.

It is considered that the foaming agent such as diazocarbonamide has been decomposed in a minute amount for a while after being taken out of the melting furnace. This degradation is insignificant,
Although gas pressure is not generated enough to generate new bubbles, gas permeability may be sufficiently affected. Further, in the case of diazocarbonamide, a sublimate is easily generated when the pressure is reduced, and the generation of a sublimation gas having a large molecular weight in the resin film may also affect the gas permeability.

Very rarely, some of the bubbles that have been degassed after decompression and expansion have been sufficiently degassed, but only a pinhole is opened in the film of the bubbles and do not even burst. Such bubbles often maintain their size, although the bubbles slightly shrink. By the way, the existence of a pinhole that is too small to be observed with the naked eye has not been confirmed,
There is no way to confirm the state of closed cells inside the foamed layer, and there remains a question as to how the existence of such fine pores is involved in the subsequent shrinkage upon opening under reduced pressure. However, it has definitely been observed that most of the bubbles are completely shrunk by the rapid decompression and release, thereby forming a network-like structure. Even if it is, it cannot be called bubble breakage in a general sense, and it is considered that there is no particular effect on the establishment of the present invention.

Next, a network structure generated by releasing the vacuum will be described. JP-B-63-5822 and JP-A-2-
According to 242968, a chain breakage occurs, and a large-diameter through-hole is easily formed. In addition, the chained foam breaks not only the through holes but also the irregularities themselves. According to the method of the present invention, chain breakage hardly occurs, and irregularities are formed with the size of the initially generated closed cells, so that extremely fine crater-like irregularities can be obtained. Basically, the network generated at this time extends completely to the inside of the coating.

The resin coating of Example 1 has few large through-holes that can be observed with the naked eye, but some fine holes are formed, and when the inside of the completed glove is filled with water, water droplets slowly grow. Oozing out. This phenomenon can be more clearly confirmed when the water in the glove is pressurized. However, the diameter of the hole is clearly smaller and the number is smaller than that of a glove prototype manufactured according to Japanese Patent Publication No. 63-5822 or a glove commercially available based on the patent. Even when used for actual work, when used for handling objects with dirt such as water or oil, the present invention

The method of claim 3 showed much less water and oil seepage. This can easily be inferred from the difference in the manufacturing method, and the reason will be described below.

In the present invention, the mechanism by which through holes are generated has not been elucidated yet, but one of the possibilities will be described below. Although bubbles and pinholes may be observed at a very small portion when the details are observed as described above, according to the present invention, the bubbles do not basically occur. Further, even at the time of rapid decompression release, no bubble breakage can be confirmed by visual observation. The bubble breakage at the time of decompression is only a very small part of the entire bubble, and to this extent, such a large number of through-holes for seeping out tap water as described above cannot be generated. More than anything,
If a large amount of foam breakage occurs in the process before the depressurization, the atmospheric pressure can not crush the air bubbles at the time of decompression release, a foam layer having a smooth surface remains, and it can be easily confirmed. Although most of the foamed layer remains partially, most of the other coating resin layers form a network structure.

Therefore, it is considered that the through holes are generated when the pressure reduction is released in the last step. Since the closed cells also overlap in the thickness direction of the film, the film of the gas bubbles is crushed into a complicated and unnatural shape, and is considered to be torn at this time. The closed cells should be thinned by expansion under reduced pressure, and the coating should be somewhat hardened by cooling by adiabatic expansion. . At this time, it is sufficiently conceivable that the film of air bubbles is simply broken by the force of decompression release.

The anti-slip according to the present invention is characterized mainly by an excellent anti-slipping effect and air permeability, but also increases the flexibility of the coating. In general, as described in JP-A-5-51804, a foamed resin is much more flexible than a non-foamed film. However, the coating according to the present invention provides a softer glove than such a foamed glove. This glove has a specific low rebound at low elongation. This is a feature that has not been considered in conventional coated gloves and clothing, and it is easy for humans to feel particularly soft when worn. The reason will be described below.

According to the present invention, the glove is decompressed in the decompression container after the coated resin is fired. At this time, the foam expands to a thickness of about 2 to 10 times. This is virtually the same state as when foaming was performed at a higher magnification. In addition, if the resin expands at this time, if the solidification of the resin surface by cooling is small, the polyvinyl chloride in the molten state has almost no rebound resilience, so it is not irreversible deformation like rubber but irreversible deformation. Get offended. for that reason,
The foamed resin layer becomes foamed at this high magnification, and expands so as to be pulled to the basic cloth in some cases as described later. The skeleton portion of the structure formed at this time is almost maintained even after the opening under reduced pressure. In other words, after sufficient degassing, when the decompression is rapidly released, the cavities of individual bubbles are crushed and shrunk by atmospheric pressure, but this skeleton does not shrink, but instead folds in a wrinkle-like manner due to the shrinkage of the cavities. It is depressed so that it only shrinks, apparently shrinking. The softness in the tensile direction of the resin film formed in this manner is described in
It is much softer than a conventional foam coating as seen in -51804. In particular, in a low elongation region where the entire foamed layer expands at the time of decompression, the tensile resistance involving the base fabric is extremely small, and the properties when the fiber woven fabric is pulled slightly approach. For this reason, when the present invention is used, depending on the conditions, even though knitted sewing gloves are used for the base cloth, 1
It is possible to obtain a feeling close to that obtained when using 3-gauge knitted gloves for the base cloth.

Regarding the softness, see Japanese Unexamined Patent Publication No.
42968 and JP-A-2-242968,
Because the sol melts and solidifies in the form of aggregation toward the base fabric,
In addition, the gloves are hardened because the stitches of the base cloth are fixed due to the penetration during the aggregation. To obtain a glove with softness as seen in the present invention,
It is sufficient to blow off the foamed sol as shown in the method of JP-A-2-242968, but the amount of resin adhered is reduced too much, and the through-hole becomes too large, so that the shielding performance for protecting hands as a coated glove is not sufficient. Not enough. On the other hand, according to the present invention, a relatively soft glove can be obtained to some extent even if the coating is thick and the amount of the applied resin is large.

Incidentally, this characteristic is clearly exhibited by the following measures. In the practice of the present invention, after attaching the base cloth glove to the mold, a vinyl adhesive tape having a width of 5 cm is wound around the cuff of the base cloth glove, and the base cloth glove is attached to the mold. Next, the sol is applied so as to hang the vinyl adhesive tape when coating the sol, and the air between the mold and the glove is completely sealed. If the pressure is reduced in this state, the gloves bulge like balloons in parallel with the expansion of the foam layer itself, and the base cloth gloves are greatly stretched. However, since the air between the glove and the mold is also rapidly degassed, the expansion stops at a certain stage. Often the base gloves are a few millimeters from the mold
It is in a state of rising about 2 cm, and this is crushed by opening under reduced pressure. When wearing and using gloves made in this way, if the size expanded during decompression,
It can be pulled and stretched with very weak force compared to ordinary coated gloves. The reason is that the size of the film and the basic cloth at the time of expansion under reduced pressure is basically reflected in the final product. Even if the shrinkage at the time of decompression release is macroscopic shrinkage, if attention is paid to individual bubbles, it is a phenomenon that the shrunk individual bubbles overlap so as to be folded, and such a network-like coating It is considered that the basic cloth shrinks under the influence of the folding deformation of the resin film in the fine structure when forming the stitch-like structure, more than the fact that is soft and rich in elasticity. Such a discovery that the base fabric and the substrate itself can be stretched and shrunk during the coating process is considered to be an original method that is not used in any processing field regardless of rubber or plastic.

There is another important point in establishing the present invention. It is heat fusion by residual heat. As is well known to those skilled in the art, when the gloves are rapidly removed from the melting furnace as in the present invention, the gloves and the mold are not immediately cooled. Therefore, even in the present invention, the film cooled during the depressurization is sufficiently warm for about several minutes even if the adiabatic expansion of air bubbles is taken into consideration. Thermal fusion occurs in a state of unevenness. Due to the difference in heat capacity and cooling time due to the original amount of adhesion (thickness) of the resin, although there is some difference, sufficient fusion occurs to maintain the tip shape. This is considered to be a proof that the closed cells are not broken and the pressing by the atmospheric pressure is functioning sufficiently.

Regarding this heat fusion, the degassing rate inside the bubbles is faster than generally conceivable, compared with the cooling rate due to the adiabatic expansion inside the bubbles at the start of decompression, and the heat capacity and thermal conductivity of the molten gel; Many factors such as the heat retention effect in a decompression container of 10 mmHg or less and the residual heat from the mold with the base cloth interposed therebetween are not clearly understood. However, as a result, it has been observed that sufficient fusion has occurred for the present invention.

In the second aspect of the present invention, this thermal fusion phenomenon has a further important meaning. In addition to the vinyl chloride resin processing, it is generally difficult to apply the foamed resin repeatedly, particularly in the case of paste coating with vinyl chloride. Although there are examples such as beach sandals made of foamed ethylene vinyl acetate, which are practically used under pressure, there are few examples of processing such as gloves which are complicated and cannot be pressed uniformly.

Also in the present invention, the situation until foaming occurs in the melting furnace is the same as in the conventional processing method, and peeling due to the accumulation of decomposition gas is likely to occur as in the above-described example. However, in the present invention, there are steps of releasing under reduced pressure and shrinking and fusing. Ultimately, the presence of this gas pool does not cause peeling, so that it is unlikely to cause a serious problem. In other words, this gas reservoir is also a closed cell, and the interior of the reservoir is also degassed when depressurized, and contracts, adheres, and thermally fuses when decompression is released, so that it does not cause separation. Such a gas reservoir part expands more greatly when depressurized than a bubble, and eventually generates fold-like irregularities. By the way, if this fold is small, it does not cause any problem, but if it is large, it can be picked with a finger and easily cut. For this reason, better results can be obtained by preparing conditions under which gas accumulation is less likely to occur during foaming. However, in the present invention, the target unevenness and the thermal fusion can be generally obtained irrespective of the presence or absence of such an intermediate gas pool.

Incidentally, when the present invention is actually practiced, a partially smooth foam layer may remain in the mesh-like irregularities. This occurs when over-foaming occurs during foaming in the melting furnace when the degassing is incomplete, and the closed cells inside are broken or the coating of the closed cells becomes thinner than necessary. This phenomenon is a serious problem in practicing the present invention because the appearance is impaired. Therefore, it is necessary to sufficiently examine the amount of the foaming agent, the temperature at the time of melting, the melting, and the adjustment of the kicker of zinc oxide and carbon black. Further, even if the basic method as described in Examples 1 and 2 described below is followed, a smooth foamed layer is generated even in the case of gloves at 30% or less of the total surface area of the resin portion. At least 70% exhibit complicated mesh-like or fold-like irregularities as described in the claims. Even in such a state, there is no problem in practical use, and it is considered that there is a sufficient anti-slip effect. Therefore, no limitation relating to this problem is described in the claims of the present invention.

The present invention is limited to the production of working gloves using a vinyl chloride paste. This is because confirmation work as in the embodiment is not performed. Processing by foaming, degassing under reduced pressure, and opening under reduced pressure of the molten resin as in the present invention is an unprecedented original processing method. You can do it. For example, processing a thermoplastic resin that can form a foam with closed cells, extruding vinyl chloride containing a foaming agent, powder slush molding of vinyl chloride or ethylene acetate, unvulcanized natural rubber, thermoplastic synthetic elastomer The present invention can be applied to processing of an elastomer. That is, a foam containing closed cells can be molded, and when it is placed at a high temperature, it can be heated and melted or sufficiently softened. It is considered that the foam of the plastic polymer compound can deaerate the inside of the cell without breaking the bubble. Those that require a short time for degassing are less susceptible to the effects of cooling due to adiabatic expansion, and if expansion stops, the inside of the decompression vessel is hard to cool because there is no air, and it has complex irregularities due to opening of decompression Form a structure.

A description will be given of the point that the target of pressure reduction is set to 10 mmHg or less in claims 1 and 2. The purpose of decompression in the present invention is to degas inside the bubbles,
If the degassing is insufficient, shrinkage does not completely occur when the vacuum is released, and heat fusion also becomes insufficient. Therefore, a stitch-like structure is not formed or a through hole is not opened. In Example 1 and the like to be described later, 10 mm 1 minute and 30 seconds after the start of decompression.
Hg is reached, but it is better to continue degassing for about 4 minutes thereafter. During this time, the minimum pressure may be below 1 mmHg to keep the vacuum pump running, but 10 mmHg
If it is below, generally good results can be obtained. 1mmHg
In the vicinity, since the boiling point of the main plasticizer approaches 200 ° C., it is necessary to pay close attention to the minimum pressure and the selection of the plasticizer.

A method of blending a luminous pigment in a resin is known as a safety measure for nighttime work among vinyl chloride coated work gloves. By the way, when the luminous pigment is blended in the vinyl chloride paste used in claims 1 and 2 of the present invention, the thick and thin portions of the coating are divided into bright and dark portions along the stitch pattern during light emission, Phosphorescent gloves exhibiting the following contrast: These gloves are easier to see than gloves of comparable brightness without contrast. Further, the reason why the glove is easy to recognize may be related to the fact that the effective surface area of the glove is extremely large due to the network-like unevenness.

[0059]

EXAMPLES In the following examples, the sol applied to a base cloth glove to form an impervious vinyl chloride resin film is referred to as an impervious sol. Some gloves may penetrate unless oil-repellent is applied. In recent years, in the art, a base cloth glove is often subjected to an oil-repellent treatment using an emulsion of a fluorine-based compound, and thus a sol having such a composition that easily causes penetration may be used. Here, the sol having such a composition is also referred to as an impervious sol according to the current situation. In addition, the number of parts in the following blending is the number of parts by weight (PHR: percent per resin) when the total amount of the vinyl chloride resin in the blending is 100. In addition, the adjustment of the vinyl chloride paste based on the blending was performed by kneading with a grinder and then defoaming under reduced pressure according to a conventional method. In the following formulation, the kneaded viscosity is approximately 500
-10,000 CPS.

[0060]

Embodiment 1

[Table 1]

First, a sewing glove made of cotton knit, which is a base cloth glove, is attached to an aluminum alloy glove mold, and the base cloth glove is subjected to an oil-repellent treatment according to a conventional method. After drying, wait for the mold to cool, apply a vinyl chloride paste on the base cloth glove, then drop it for 6 minutes, place it in a melting furnace at 200 ° C for 10 minutes, heat and melt, melt and foam . After that, the gloves and the mold were quickly transferred into a decompression container, and the pressure was reduced by a vacuum pump.
After the pressure has become equal to or less than mmHg, the pressure is further reduced for 4 minutes to completely degas the gas inside the bubbles. Thereafter, the valve was quickly opened, the pressure was released under reduced pressure, and after cooling, the gloves were removed from the mold.

This glove is very flexible and highly elastic,
Deep mesh-like irregularities were formed on the surface of the glove, and the structure was finer than that of JP-B-63-5822, and no through-hole could be confirmed with the naked eye.

Now, in order to confirm the air permeability of this glove,
The amount of through holes was measured. First, add 50 tap water to the beaker.
Weigh 0 g. An empty plastic bucket is placed on the electronic device, and the glove produced in Example 1 is hung on the empty bucket, and 500 g of tap water is poured into the glove. At this time,
Make sure that all the tap water flowing out of the through hole is received by the bucket, and after 3 minutes from the end of pouring, the glove is removed from the bucket and the amount of the effluent is measured. For comparison, a glove manufactured in accordance with Japanese Patent Publication No. 63-5822, Vinister Sunday (manufactured by Towa Glove Co., Ltd., size L) and a glove of Example 1 were prototyped, and an operation of transporting 500 cases of about 10 kg was performed. The same experiment was performed on the used gloves used and the gloves of the fully foamed gloves prototyped according to JP-A-5-51804. The results are described below.

[Table 2]

In the case of Vinister Sunday gloves, almost no water was accumulated in the gloves, and water flowed out. In the glove of Example 1, although the amount of outflow was small, it was observed that water droplets permeated from several tens of places of the glove during the experiment. Although the used glove of Example 1 flows out vigorously at first, the amount of outflow decreases after about 2 minutes. In addition, as in the case of the unused gloves of Example 1, a large number of water droplets were observed in portions where water flow was small, and the existence of through holes was confirmed. In this experiment, it was considered that there was sufficient air permeability because a large number of through holes were observed. In particular, it is important that there is a through-hole enough to allow unpressurized water to seep out, and that the air has sufficient air permeability considering that the viscosity of air is much smaller than the viscosity of water. Because I thought it could be considered. The fact that there are many through-holes to the extent that water droplets seep out and that the amount of outflow is small suggests that there are through-holes having a small diameter as originally intended.

[0065]

Embodiment 2

[Table 3]

[0066]

[Table 4]

According to the method of the second aspect of the present invention, a trial production of a water work glove having a stitched anti-slip structure and having sufficient shielding properties against liquid was attempted. In addition, in Example 2, it was considered to produce a flexible light work glove. That is, a thin film is formed on the first layer using the non-penetrable sol of the vinyl chloride paste of Formulation 2, and then the vinyl chloride paste of Formulation 3 is used on the first layer. This is an attempt to perform a coating process as seen again to provide a non-slip structure having stitch-like irregularities on the first layer.

First, a base cloth glove was mounted on a glove mold according to a conventional method, subjected to an oil-repellent treatment, and dried. Next, the PVC paste of Formulation 2 is applied to the base cloth gloves, dropped for 6 minutes, and then the mold is raised over the shbank to gel or semi-gel the paste sol to form the first layer, and the base glove is formed. Preliminary shaping was performed. After allowing to cool for 2 minutes, the base glove was dipped from a fingertip to a wrist in a polypropylene bucket filled with a PVC paste of Formulation 3, immediately pulled up, and dropped again for 6 minutes. Thereafter, after performing heat melting, melt foaming, degassing under reduced pressure, and opening under reduced pressure in exactly the same manner as in Example 1, the gloves were extracted from the mold after cooling.

This prototype had a good appearance and no smooth foam layer was observed. This is considered to be because the second layer was not applied directly to the base fabric but was applied on the smooth first layer, so that it could be applied thinly and uniformly. Also, when foaming in a melting furnace, decomposition gas is accumulated between the first layer which is a non-foamed layer and the second layer of the foamed layer,
Although there was concern about the problem of peeling, it is considered that there is no major problem. Such delamination due to accumulation of gas was observed during decompression in some of the prototypes, but the diameter of the delaminated portion was large in rice grains. The inside of the circle was sufficiently adhered by heat fusion.

By the way, with respect to this prototype, tap water was poured into the inside of the glove in the same manner as in Example 1 and the presence or absence of a through hole was confirmed. As a result, no through hole was found.

[0071]

Example 3 A basic cloth glove was applied to a mold, and a vinyl chloride paste of Formulation 1 was applied and dripped in the same manner as in Example 1. After dripping for 6 minutes, the sol is gelled or semi-gelled by holding the mold over the shbank, and the glove is temporarily shaped. The polypropylene-made bucket is filled with DOP or ATBC, and the glove which has been temporarily shaped is immersed in this bucket, immediately pulled up, and dropped again for 6 minutes. To stop drip, heat it again by holding it over the shbank,
After a part of the BC was absorbed, heating, melt foaming, degassing under reduced pressure, and opening under reduced pressure were carried out in exactly the same manner as in Example 1. After cooling, the gloves were removed from the mold.

According to this method, the melt foaming and the expansion under reduced pressure were performed without any abnormality, and the generation of a smooth foamed layer was suppressed.

The method of Example 3 utilizes the property that the fine structure remains in the PVC resin at the time of the semi-gel and easily absorbs the plasticizer. This is a method that we have studied in the past for the purpose. However,
This time, instead of such a purpose, we aimed to generate more uniform closed cells in the outermost layer, by making only the outermost layer near the skin layer soft and easy to swell, and by thinning the bubble film. Degassing could be performed smoothly.

The cause of the generation of a smooth foam layer is the breakage of closed cells before degassing. This tear is due to overfoaming and is affected by excessive growth of the skin layer. This can be easily understood by focusing on one of the closed cells near the skin layer. If a skin layer that is thicker than necessary is generated, the expansion will concentrate on the relatively thin inner film of the closed-cell film during overheating foaming or decompression expansion, causing expansion and foam breakage inside the foam layer. It is believed that there is.

[0075]

Embodiment 4

[Table 5]

Using the vinyl chloride paste of Formulation 4, gloves were produced in exactly the same manner as in Example 1.

The generation of a smooth foamed layer similar to that in Example 3 could be suppressed. The difference between Example 1 and Example 4 is the difference in parts by weight during compounding. All are 145 parts by weight and the latter are 190 parts by weight. As a result of examination, when the weight part exceeds 180 parts by weight, relatively good results tend to be easily obtained.

[0078]

[Embodiment 5] According to the present invention, a mesh-like anti-slip having a large unevenness can be obtained. In order to solve this problem, the strength of the coating may be increased, and a method of increasing the molecular weight of the vinyl chloride resin, that is, a method of increasing the strength by a crosslinking reaction may be considered. In the following Example 5, a blending example utilizing a crosslinking reaction between vinyl chloride resins utilizing a dechlorination reaction with a triazine-based crosslinking agent was examined.

[0079]

[Table 6]

According to the method of Example 2 described above,
A glove was prepared using Formulation 5 in place of the above.

Although discoloration was observed to some extent, it was slightly harder than the glove of Example 2 and a slip resistant non-slip glove was obtained. In the taper abrasion test, the gloves according to the present embodiment suffered severe wear of the non-slip at about 4000 rotations,
It became almost the same at 0 rotation. In addition, the foamed PVC glove according to Japanese Patent Application Laid-Open No. 5-51804, which is marketed by the Company, wears out to almost the same degree at 3000 rotations. From this result, it can be seen that the present example has some advantages, and from the results of the above-mentioned gloves on the market, it was determined that the present invention itself did not hinder actual use in terms of wear.

[0082]

[Embodiment 6] According to the present invention, it is possible to obtain a mesh-like anti-slip with deep irregularities, but the anti-slip effect is most expected in this anti-slip effect. In Example 6 below, a method for producing an oil-resistant glove using the present invention will be described.

[0083]

[Table 7]

According to Example 2 above, gloves were made using Formulation Example 2 for the first layer coating and Formulation Example 6 for the second layer coating.

The finished glove, as originally intended, was not slippery even when used for oil work, and exhibited flexibility not found in conventional oil-resistant gloves. It is considered that such oil-resistant gloves can be further enhanced with an anti-slip effect by blending coarse vinyl chloride powder or the like as disclosed in JP-B-63-5822.

Claims (2)

[Claims] 1. A method for producing coated gloves, in which a vinyl chloride paste containing a foaming agent is applied from above a cloth glove, heated and melted in a melting furnace, and heated to generate closed cells in a molten film. Reduce the pressure to 10 mmHg or less while the coating is not molten or solidified by cooling,
By continuing decompression for several minutes, the closed cells are expanded without breaking, and the inside of the bubbles is evacuated. Then, by rapidly returning the pressure to normal pressure and shrinking the foam layer, it is possible to form a film having a complex structure having a flexible and non-slip effect, such as a mesh-like, crater-like, or fold-like structure. Production method of work gloves with a stop. 2. A glove made of a cloth coated with a vinyl chloride resin is coated with a vinyl chloride paste containing a foaming agent on the surface of the glove, and is heated and melted in a melting furnace to form foam. Non-slip coating gloves that produce a foam layer that is 10 mmHg while the foam layer is in a molten state or not solidified by cooling
The pressure is reduced below, and the closed cells are expanded without breaking by the reduced pressure, and the inside of the bubbles is degassed. Thereafter, the pressure is rapidly returned to normal pressure, and the foamed layer is shrunk to form a non-slip layer having a mesh-like complex unevenness on the surface of the base glove.