JP2010133032A - Protection glove, guard protection glove utilizing the same, and method for detecting damage of guard glove - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a protection glove which is worn inside a guard glove in operations for handling toxic substance such as strong acid and/or strong alkali, and detects the damage of the guard glove by following up a color change in the region of the protection glove brought into contact with the toxic substance penetrated when the guard glove at its surface is damaged and thus the toxic substance penetrates inside the guard glove, and accordingly recommends stop of use or replacement of the damaged guard glove, so as to prevent the occurrence of medicinal injury on the fingers of a wearer due to contact with the toxic substance. <P>SOLUTION: The resin- or rubber-made protection glove is produced by adhesion or inclusion of substance showing color reaction with toxic substance. The guard glove provided with a chemical-resistant layer prohibiting the penetration of the toxic substance is worn outside, and the protection glove is worn inside. Damage on the guard glove is detected while following up color expression on the protection glove. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a protective glove, a protective glove, and a method for detecting damage to the protective glove, which are used in the handling of substances that are harmful to the human body, such as strong acids and strong alkalis. When handling a hazardous substance while worn on the protective glove, if the surface of the protective glove is damaged and the harmful substance penetrates into the inside of the protective glove, the protective glove will discolor due to discoloration of the part of the protective glove that has come into contact with the harmful glove. The present invention relates to a protective glove, a protective glove, and a protective glove damage detecting method capable of detecting damage and encouraging the discontinuation or replacement of damaged protective gloves and, as a result, preventing chemical burns of fingers due to contact with harmful substances. .

  Metal plating factories, precision machinery manufacturing, processing factories, etc. are working on substances that are harmful to the human body, such as strong acid and strong alkaline chemicals, and in order to prevent chemical injury caused by these harmful substances, Work is carried out by wearing protective gloves made of chemical-resistant resin or rubber. However, if there is a hole in the protective glove, even if the hole is as small as a pinhole, harmful substances will flow into the protective glove from this hole and come into contact with the fingers, causing chemical injury. . Therefore, in order to prevent such an accident, the presence or absence of a pinhole is inspected before shipment or use of the product.

  Conventionally, such inspection is performed by injecting compressed air into the glove after manufacture or before use, and ejecting the air from the pinhole to make the ejected air foamy in water (Patent Document 1). This is performed by observing a temperature change caused by the air (Patent Document 2) or observing an ultrasonic wave generated during ejection (Patent Document 3 and Patent Document 4). By these inspections, damages formed in the manufacturing and processing steps are detected, thereby preventing chemical injury.

However, even when working with protective gloves that have been confirmed to be free of damage such as pinholes by the above inspections, wear or fatigue due to use, contact with sharp members, Collisions often cause damage and damage to protective gloves during work with substances harmful to the human body. If damage occurs during the work, harmful substances can enter the gloves from this damage, causing chemical injury to the fingers. In such cases, it is often the case that attention is paid to work and it is delayed to notice damage to fingers, and chemical burns may become serious inside the gloves.
In order to avoid such a situation, it is necessary to detect damage as soon as possible after the breakage of the glove and stop using the glove or replace it with a new glove. Since it is impossible to detect the damage that occurs, it is the actual situation to know that the damage has been caused by the operator's skin sensation, that is, the pain caused by drug injury, and the work is enthusiastic. However, the treatment is delayed so much that chemical burns may become serious.
Japanese Patent Laid-Open No. 5-10843 JP-A-7-128179 JP 7-151635 A JP-A-7-218377

In view of such circumstances, the present invention eliminates the problems of the prior art as described above, and protects gloves that can detect the occurrence of damage and the location of damage as soon as possible in order to prevent chemical injury due to the invasion of harmful substances. The object is to provide a method for detecting damage to gloves and protective gloves.
As a result of diligent research to solve the above problems, the present inventors use protective gloves made of resin or rubber that are attached to or contain a substance that exhibits a color reaction and a substance harmful to the human body. It has been found that by wearing a glove inside a normal protective glove, it is possible to quickly detect the damage of the outer protective glove and the location of the damage, thereby preventing chemical injury in advance. It came to complete.

  Claim 1 of the present invention for achieving the above object comprises a protective glove made of resin or rubber, characterized in that it adheres or contains a substance harmful to the human body and a substance exhibiting a color reaction. To do.

  A second aspect of the present invention includes the protective glove according to the first aspect, wherein the substance harmful to the human body is an acid.

  A third aspect of the present invention includes the protective glove according to the second aspect, wherein the substance exhibiting a color reaction is a coumarin fluorescent dye.

  A fourth aspect of the present invention includes the protective glove according to the third aspect, wherein the coumarin fluorescent dye is an oxazolyl coumarin dye or a thiazolyl coumarin dye.

  A fifth aspect of the present invention includes the protective glove according to any one of the first to fourth aspects, wherein the resin is a polyurethane resin.

  A sixth aspect of the present invention includes the protective glove according to any one of the first to fourth aspects, wherein the rubber is chloroprene rubber or chlorosulfonated polyethylene rubber.

  Claim 7 of the present invention is a support-type protection characterized in that the surface of the fiber hand is covered with a resin or rubber containing or containing a substance useful for the human body and a substance exhibiting a color reaction. Contains gloves.

  Claim 8 of the present invention is a protective glove having a chemical-resistant layer that does not allow the passage of substances harmful to the human body, and the protective glove according to any one of claims 1 to 7 that is used by being superimposed on the inside of the protective glove. Protective and protective gloves characterized by comprising

  Claim 9 of the present invention includes the protective glove according to claim 8, wherein the protective glove is transparent or translucent.

  According to a tenth aspect of the present invention, the protective glove having a chemical-resistant layer that does not allow the passage of a harmful substance to the human body when carrying out a work for handling a harmful substance to the human body is provided on the outer side. A protective glove damage detection method comprising: wearing a protective glove inside; and detecting damage to the protective glove by coloring the protective glove.

  Since the protective glove of the present invention adheres or contains a substance that exhibits a color reaction and a substance harmful to the human body, the protective glove worn on the outside can be worn by wearing it inside the protective glove having chemical resistance. If a substance harmful to the human body enters inside due to damage, the protective glove discolors due to the color reaction of the substance that is attached to or contained in the protective glove and reacts with the harmful substance. Damage to the protective gloves worn on the outside and the location of damage are easily detected. As a result, the use or replacement of the protective gloves is promoted, and chemical injury can be prevented in advance.

  When coumarins fluorescent dyes are used as substances that exhibit a color reaction when the harmful substance to the human body is an acid, not only is it easy to dye and color resins and rubbers, but also yellow fluorescent coumarins fluorescent dyes Since it reacts with acid and turns red, coloration is easy to check and damage to protective gloves is easy to detect. As the coumarins, oxazolyl coumarin dyes or thiazolyl coumarin dyes are preferable. In this case, the change in color tone becomes remarkable, and damage to protective gloves is easily detected.

  If the resin is a polyurethane resin and the rubber is chloroprene rubber or chlorosulfonated polyethylene rubber, it is a substance that is harmful to the human body because it has excellent chemical resistance regardless of whether it is unsupported or supported. Even when it reaches the protective glove of the present invention, since it takes a long time to touch the operator's finger through the glove, it can be protected for that long time.

  As described above, the protective glove of the present invention is used by being layered on the inner side of the protective glove having a chemical-resistant layer that does not pass a harmful substance to the human body. As a result, even if the protective gloves worn on the outside are damaged and harmful substances enter the human body, the protective gloves not only protect the fingers, but also protect the fingers. Because the glove is colored, it is possible to detect damage to the protective glove, so that the use or replacement of the damaged protective glove is prompted. The protective glove of the present invention can not only detect damage to the protective glove, but also detect the location of damage to the protective glove. For example, the damaged part can be repaired if necessary. . If the outer protective glove is transparent or translucent, the color of the inner protective glove can be observed without taking off the protective glove, so that it can be detected easily and quickly even during work. be able to.

The protective glove of the present invention is worn inside the protective glove when working with a substance harmful to the human body to prevent chemical burns of fingers due to the damage of the protective glove. It adheres or contains the substance which shows a color reaction.
The substances harmful to the human body here refer to all substances that adversely affect the human body when touched directly, such as acidic solutions, alkaline solutions, poisons, powerful drugs, heavy metals.
The color reaction here refers to all reactions in which a change in color tone can be visually confirmed, and includes not only reactions that develop or change color, but also reactions in which the dye changes to colorless or transparent.

  Substances that are harmful to the human body (hereinafter simply referred to as hazardous substances) and substances that exhibit a color reaction (hereinafter simply referred to as color substances) are not particularly limited as long as a change in color tone can be visually confirmed by reaction with the harmful substances. Examples include pH indicators such as methyl orange, methyl red, phenolphthalein and litmus, metal indicators such as Eriochrome Black T, and fluorescent dyes. Fluorescent dyes are preferred because of their high reactivity and rapid color change and clarity. The fluorescent dye referred to here is a dye that emits excitation light fluorescence in the ultraviolet and visible regions.

  The fluorescent dye that can be used in the present invention is not particularly limited. Examples include eosines, oxazines, thiazines, dioxazines, azo, azomethine or methine type polycationic fluorescent colorants alone or in a mixture.

  Among these, cationic or non-cationic coumarin fluorescent dyes are compounds having a coumarin skeleton, which not only easily colors the resin and rubber used as the material of gloves, but also reacts with harmful substances and is sensitive. In particular, it can be suitably used to exhibit a color change. Furthermore, oxazolyl coumarin dyes or thiazolyl coumarin dyes are particularly preferred because they have good colorability for resins and rubbers, good hue, and clear discoloration against harmful substances.

Incidentally, coumarins such as oxazolyl coumarin dyes or thiazolyl coumarin dyes are described in detail in Japanese Patent Publication Nos. 51-6266 and 56-59872.
Examples of the dye containing such a substance include Dianix (registered trademark) Luminous Yellow 10G: manufactured by Dyster, Kayalon (registered trademark) Polyester Flavin FG-S: Nippon Kayaku Kayanol (registered trademark) Bryl Flavin (Nippon Kayaku Co., Ltd., Nirosan (registered trademark) B flavin E8GZ125: Clariant, etc. are commercially available.

  Examples of the carrier that increases the diffusion rate of the dye into the fiber and increases the dyeability include trichlorobenzene, o-phenylphenol, p-phenylphenol, methylnaphthalene, and the like. These may be used alone or as necessary. Used in combination of more than one species.

  The method for adhering or containing the color developing substance to the protective gloves is not particularly limited, and a known method can be adopted according to the properties of the color developing substance. For example, when the coloring substance is a dye, a method of coloring the surface of rubber or resin by immersing gloves in heated dye dispersed in water, or a cloth colored with this dye on the surface of rubber or resin For example, in the case of a pigment, a method of directly blending with a rubber or resin and then molding it into a glove mold, or a method of coating a glove after mixing it with an organosol, resin solution, latex, etc. Can be illustrated. Of course, dyes can also be used in the same manner as pigments.

  The amount of the coloring substance used can be appropriately determined depending on the type of coloring substance, the degree of coloring, etc., but the amount added when the coloring substance is adhered is 0.001 with respect to 1 part by weight of the glove. ~ 0.05 parts by weight. If the amount is less than 0.001 part by weight, the color change is small, so that the detection of damage is not easy. On the other hand, if the amount exceeds 0.05 part by weight, the color change is constant and uneconomical. Moreover, content in the case of containing a coloring substance is 0.01-5 weight part with respect to 100 weight part of resin or rubber solid content. If the amount is less than 0.01 parts by weight, the color change is small, so that the detection of damage is not easy. On the other hand, if the amount exceeds 5 parts by weight, the color change is constant and is uneconomical.

The resin or rubber that can be used as a material for the protective gloves of the present invention is not particularly limited as long as it can protect the fingers of workers from harmful substances that have entered the protective gloves, and the resin is a soft polyvinyl chloride resin, A polyacrylic ester resin, a polyvinyl acetate resin, a polyurethane resin, etc. can be illustrated, and it is used individually or in combination of 2 or more types as needed. Examples of the rubber include natural rubber, nitrile butadiene rubber, styrene butadiene rubber, chloroprene rubber, chlorosulfonated polyethylene rubber, isoprene rubber, fluorine rubber, butyl rubber, silicone rubber, etc., alone or in combination of two or more as necessary. Can be used.
Among these, polyvinyl chloride resin, polyurethane resin, natural rubber, nitrile butadiene rubber, chloroprene rubber, and chlorosulfonated polyethylene rubber have good affinity with dyes and can be colored beautifully by a simple method, but also protected The dye adhering to the surface of the glove causes a color reaction efficiently, so that the discoloration is easy to observe, and this makes it easy to detect damage to the protective glove.
In addition, polyurethane resin, chloroprene rubber, and chlorosulfonated polyethylene rubber are excellent in chemical resistance, so even if harmful substances reach the protective gloves, the protective gloves are not violated for a long time. Can be protected over a long period of time.

The protective glove according to the present invention may be a so-called unsupport type formed by molding a resin or rubber into a glove shape, or a so-called support type formed by coating the surface of a fiber hand with the resin or rubber. Also good.
The manufacturing method of the protective gloves of the present invention is not particularly limited, and all known methods can be used. For example, in the case of an unsupported glove, a method of immersing the hand mold in a resin or rubber raw material liquid, or the surface of the hand mold The method of spraying a raw material liquid can be mentioned. In the case of support-type gloves, after covering the hand mold with a fiber hand, a method of immersing the hand mold with the fiber hand in a resin or rubber raw material liquid, or a hand-type fiber hand Examples thereof include a method of spraying the raw material liquid on the surface. In addition, a flat film may be cut into a glove shape, and two edges may be bonded together to form a glove shape, or a film laminated on a cloth may be cut into a glove shape and bonded to the edge. Commercially available waterproof and chemical resistant unsupports or support gloves can also be used.

In addition, when making the protective glove of this invention into an unsupport type, the slip-on process and the flocking process may be given to the inner surface of this protective glove.
In addition, when the protective glove of the present invention is a support type, it can be appropriately determined according to the use as the material of the fiber hand, for example, polyester fiber, polyamide fiber, polyaramid fiber, vinylon fiber, polyolefin fiber, Examples include polyurethane fiber, polyacrylonitrile fiber, polyacrylate fiber, polyethylene fiber, acetate fiber, rayon fiber, polynosic fiber, and cotton. These may be used alone or in combination of two or more. Among these, polyester fiber, polyacrylate fiber, polyamide fiber, and cotton are preferable from the viewpoint of good texture and versatility.

  Although the thickness of a protective glove can be suitably determined according to a use, the thickness of the film or coating has preferable about 0.02 mm-0.5 mm. If it is less than 0.02 mm, pinholes may be generated during the creation of the glove, and if it exceeds 0.5 mm, it may be stiff when worn inside the protective glove. Further, the film or coating may be a single layer or multiple layers.

  The protective glove of the present invention can be worn alone and used to detect whether a substance handled by coloration (discoloration) is harmful to the human body, but preferably a substance harmful to the human body is used. Used on top of protective gloves with a chemical resistant layer that does not pass through. In this way, when the outer protective gloves are damaged during work and harmful substances enter from there, the colored substances attached to or contained in the protective gloves react with the harmful substances to cause coloration. By observing this, the damage and location of the outer protective gloves can be detected, and the use or replacement of the damaged protective gloves is promoted. As a result, since harmful substances are blocked by the inner protective gloves and do not reach the inside, the fingers are protected and chemical injury can be prevented.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further in detail, this invention is not restrict | limited at all by these. In the following Examples and Comparative Examples, “%” and “part” represent “% by weight” and “part by weight” unless otherwise specified.

Example 1
A colored tank consisting of 1 part aqueous solution of 1% aqueous solution of coumarin-based disperse dye Dianix (registered trademark) Luminous Yellow 10G (manufactured by Dystar) and 20 parts of water is prepared, and a colorless translucent polyurethane unsupported glove (Dairobe H3 (registered) (Trademark), Dia Rubber Co., Ltd.) 1 part was colored in the coloring bath at 130 ° C. with stirring for 60 minutes, washed with water and dried to prepare colored polyurethane unsupported gloves. The surface of the glove was yellow fluorescent color.
Cover the obtained yellow fluorescent glove on a hand mold, and further cover a used water-resistant chlorosulfonated polyethylene glove with a sleeve (Dairobe A95, manufactured by Dia Rubber Co., Ltd.). After immersing the wrist part of 15 cm for 5 minutes, the surface of the glove was lightly washed and the outer chlorosulfonated polyethylene glove was removed from the hand mold. A red spot having a diameter of about 5 mm was observed at the bending / extending part of the index finger on the surface of the inner colored polyurethane gloves. When the hole was confirmed by pressurizing with air from the inside of the used chlorosulfonated polyethylene glove in water, it was found that bubbles were generated from the bending / extending part of the index finger and a small hole was formed.

Example 2
Using a solution in which a polyurethane resin (raw material: Crisbon (registered trademark) 8166, manufactured by Dainippon Ink & Chemicals, Inc.) is adjusted to a solid content of 10% with DMF (N, N-dimethylformamide) on the surface of the polyester fiber hand. A foamed resin film is prepared by a wet method, and a polyurethane resin (raw material: Crisbon 7166SL, manufactured by Dainippon Ink & Chemicals, Inc.) and a coumarin-based disperse dye Kayaron (registered trademark) polyester flavin FG-S (Nippon Kayaku) A waterproof resin coating is prepared by a dry method using a solution prepared by DMF (N, N-dimethylformamide) and MEK (methyl ethyl ketone) (DMF / MEK = 3/2, solid content 10%) A support-type glove with a colored polyurethane surface was obtained. The surface of the obtained glove was yellow fluorescent color.
The obtained yellow fluorescent glove is put on the hand mold again, and a water-resistant NBR glove with a sleeve (Yellowb, manufactured by Showa Glove Co., Ltd.) is further put on the glove, and a 40% sulfuric acid aqueous solution is applied to the wrist part about 15 cm from the fingertip. After being soaked for 5 minutes, the surface of the glove was pulled up and washed gently with water to remove the NBR glove from the hand mold. As a result, there was no change in color or other changes in the inner colored glove.
Next, a hole is made with a sewing needle in the fingertip portion of the index finger of the NBR glove, and the NBR glove is put on a hand mold that is similarly covered with a yellow fluorescent glove, and about 15 cm from the fingertip to 40% sulfuric acid aqueous solution. After soaking up to the wrist for 5 minutes, pulling it up, gently washing the surface with water, and removing the NBR gloves from the handprint, a red spot with a diameter of about 2 mm is seen on the index fingertip on the inner colored polyurethane gloves surface. It was.

Example 3
Coumarin acid dye Nirosan (registered trademark) B Flavin E8GZ125 (manufactured by Clariant) 1% aqueous solution, water 35 parts, acetic acid 0.005 parts coloring tank, prepared on the surface of the polyester fiber hand A foamed resin film is prepared by a wet method using a solution prepared by using DMF of a resin (raw material: Crisbon 8166, manufactured by Dainippon Ink Chemical Co., Ltd.), and a polyurethane resin (raw material: Crisbon 7166SL, Dainippon Ink, Ltd.) is further formed thereon. A waterproof resin coating was prepared by a dry method using a solution (DMF / MEK = 3/2, solid content: 10%) prepared by adjusting DMF and MEK from Chemical Industry Co., Ltd. 1 part of this support-type glove and the above-mentioned coloring tank are heated at a rate of 1 ° C./min from 35 ° C. to 90 ° C. with stirring, colored at 90 ° C. for 60 minutes, washed with water and dried to support the colored polyurethane surface. Made gloves. The surface of the obtained glove was yellow fluorescent color.
The obtained yellow fluorescent color glove is put on the hand mold again, and a water-resistant chlorosulfonated polyethylene glove with a sleeve (Dairobe A95, manufactured by Dia Rubber Co., Ltd.) is further put on the glove. After soaking up to the wrist for 5 minutes, the surface of the glove was pulled up, washed gently with water, and the glove made of chlorosulfonated polyethylene was removed from the hand mold.
Next, a hole is made with a sewing needle in the fingertip portion of the index finger of the chlorosulfonated polyethylene glove, and the chlorosulfonated polyethylene glove is put on a hand mold that is similarly covered with a yellow fluorescent glove, and 40% nitric acid is added. After immersing from the fingertip to the wrist part of about 15 cm in aqueous solution for 5 minutes, pulling it up and gently washing the surface with water, the chlorosulfonated polyethylene glove was removed from the handprint. A red spot having a diameter of about 2 mm was observed.

Example 4
Coumarin-based acid dye Kayanol (registered trademark) Brilliant Flavin Conch (manufactured by Nippon Kayaku Co., Ltd.) provides a 1% aqueous solution, 35 parts of water, and 0.005 parts of acetic acid. Using 1 part of support gloves (Dairobe H3 (registered trademark), manufactured by Dia Rubber Co., Ltd.) and the coloring tank, the temperature was raised from 35 ° C. to 90 ° C. at 1 ° C./min and colored at 90 ° C. for 60 minutes. Unsupported gloves made of colored polyurethane were made by washing with water and drying. The surface of the glove was yellow fluorescent color.
The obtained yellow fluorescent glove is covered again with a hand mold, and further covered with a water-resistant chlorosulfonated polyethylene glove with a sleeve (Dairobe A95, manufactured by Dia Rubber Co., Ltd.). After soaking up to the wrist for 5 minutes, the surface of the glove was pulled up, washed gently with water, and the glove made of chlorosulfonated polyethylene was removed from the hand mold.
Next, a hole is made with a sewing needle in the fingertip portion of the index finger of the chlorosulfonated polyethylene glove, and the chlorosulfonated polyethylene glove is put on a hand mold covered with a yellow fluorescent color glove, and 30% hydrochloric acid is added. After immersing from the fingertip to the wrist part of about 15 cm in aqueous solution for 5 minutes, pulling it up and gently washing the surface with water, the chlorosulfonated polyethylene glove was removed from the handprint, and the fingertip part of the index finger on the inner colored polyurethane glove surface was removed. A red spot having a diameter of about 2 mm was observed.

Example 5
NBR latex formulation (NBR latex (Nipol (R) Latex Lx-550) 100 parts in solids, 0.5 parts potassium hydroxide, 1 part sulfur, 1 part zinc oxide, 0.2 parts zinc dibutyldithiocarbamate, 1 part of titanium oxide and 1 part of sodium dodecylbenzene sulfonate adjusted to 35% solids with water and stirred well) are dipped in a hand mold coated with 40% calcium nitrate methanol solution, dried and vulcanized before leaving the mold The NBR rubber unsupported gloves were obtained by reversal release. Next, 1 part aqueous solution of coumarin-based disperse dye Kayaron (registered trademark) polyester flavin FG-S (manufactured by Nippon Kayaku Co., Ltd.) and 20 parts water, ETC-56 (phenylphenol compound, manufactured by Senka Co., Ltd.) as a carrier ) Prepare a coloring tank consisting of 0.02 parts, put 1 part of the above NBR rubber unsupported gloves into the coloring tank, color under stirring at 97 ° C. for 40 minutes, wash with water and dry to color NBR rubber Made unsupported gloves. The surface of the obtained glove was yellow fluorescent color.
The obtained yellow fluorescent color gloves are put on the hand mold again, and further covered with a water-resistant chlorosulfonated polyethylene glove with a sleeve (Dairobe A95, manufactured by Dia Rubber Co., Ltd.), and about 15 cm from a fingertip to a 40% nitric acid aqueous solution. After immersing up to the wrist portion for 5 minutes, the surface of the glove was pulled up, washed gently with water, and the glove made of chlorosulfonated polyethylene was removed from the hand mold. As a result, the inner colored glove had no color or other changes.
Next, a hole is made with a sewing needle in the fingertip portion of the index finger of the chlorosulfonated polyethylene glove, and the chlorosulfonated polyethylene glove is put on a hand mold that is similarly covered with a yellow fluorescent glove, and 40% nitric acid is added. After immersing from the fingertip to the wrist part of about 15 cm for 5 minutes in the aqueous solution, pulling it up and gently washing the surface with water, and removing the chlorosulfonated polyethylene glove from the handprint, the fingertip part of the index finger on the surface of the inner colored NBR rubber glove A red spot having a diameter of about 2 mm was observed.

Example 6
Coumarin-based disperse dyes Dianics (registered trademark) Luminous Yellow 10G (manufactured by Dystar) 1 part of 1% aqueous solution and water 20 parts, as carrier ETC-56 (phenylphenol compound, manufactured by Senka Co., Ltd.) 0.02 parts A coloring tank is prepared, and 1 part of colorless and translucent polyvinyl chloride unsupport gloves (Nice Hand Easy, Showa Glove Co., Ltd.) is colored with stirring in a coloring tank at 97 ° C. for 40 minutes, washed with water, An unsupported glove made of colored polyvinyl chloride was made by drying. The surface was yellow fluorescent color.
The obtained yellow fluorescent glove is covered again with a hand mold, and further covered with a water-resistant chlorosulfonated polyethylene glove with a sleeve (Dairobe A95, manufactured by Dia Rubber Co., Ltd.). After soaking up to the wrist for 5 minutes, the surface of the glove was pulled up, washed gently with water, and the glove made of chlorosulfonated polyethylene was removed from the hand mold.
Next, a hole is made with a sewing needle in the fingertip portion of the index finger of the chlorosulfonated polyethylene glove, and this chlorosulfonated polyethylene glove is covered on a hand mold covered with a yellow fluorescent color glove. After immersing from the fingertip to the wrist part of about 15 cm in aqueous solution for 5 minutes, the surface of the index finger on the inner surface of the colored polyvinyl chloride glove is removed by pulling it up and gently washing the surface with water to remove the chlorosulfonated polyethylene glove from the handprint. A red spot having a diameter of about 2 mm was observed in the part.

Example 7
Coumarin disperse dye Kayalon (registered trademark) Polyester Flavin 1 part of 1% aqueous solution of FG-S (manufactured by Nippon Kayaku Co., Ltd.) and 20 parts of water, ETC-56 (phenylphenol compound, manufactured by Senka Corporation) as carrier 0 .02 parts of a coloring tank is prepared, and 1 part of a pale yellow natural rubber unsupport glove (supple and thin, manufactured by Showa Glove Co., Ltd.) is placed in the coloring tank and colored under stirring at 97 ° C. for 40 minutes. Unwashed gloves made of colored natural rubber were prepared by washing with water and drying. The surface was yellow fluorescent color.
The obtained yellow fluorescent glove is covered again with a hand mold, and further covered with a water-resistant chlorosulfonated polyethylene glove with a sleeve (Dairobe A95, manufactured by Dia Rubber Co., Ltd.). After soaking up to the wrist for 5 minutes, the surface of the glove was pulled up, washed gently with water, and the glove made of chlorosulfonated polyethylene was removed from the hand mold.
Next, a hole is made with a sewing needle in the fingertip portion of the index finger of the chlorosulfonated polyethylene glove, and the chlorosulfonated polyethylene glove is put on a hand mold covered with a yellow fluorescent color glove, and 30% hydrochloric acid is added. After immersing from the fingertip to the wrist part of about 15 cm in aqueous solution for 5 minutes, pulling it up, gently washing the surface with water, and removing the chlorosulfonated polyethylene glove from the bill, the fingertip part of the index finger on the surface of the colored natural rubber glove inside A red spot having a diameter of about 2 mm was observed.

Example 8
Chloroprene latex blend (100 parts by weight of chloroprene latex (raw material: Skyprene (registered trademark), Latex LA-502, manufactured by Tosoh Corporation)), 1 part of sulfur, 3 parts of zinc oxide, 1 part of zinc dibutyldithiocarbamate, oxidized 1 part of titanium and 1 part of sodium dodecylbenzenesulfonate adjusted to 45% solids with water and stirred well) are dipped in a hand mold coated with 40% calcium nitrate methanol solution, dried and vulcanized and then reversed from the mold The mold was released to obtain an unsupported glove made of chloroprene rubber. Next, a coloring tank consisting of 1 part of a 1% aqueous solution of coumarin disperse dye Dianix (registered trademark) Luminous Yellow 10G (manufactured by Dystar) and 20 parts of water is prepared, and 130 parts of the above chloroprene unsupported gloves are prepared. After coloring with stirring for 60 minutes in the coloring bath at 0 ° C., washing with water and drying were performed to prepare colored chloroprene unsupported gloves. The surface was yellow fluorescent color.
The obtained yellow fluorescent glove is covered again with a hand mold, and further covered with a water-resistant chlorosulfonated polyethylene glove with a sleeve (Dairobe A95, manufactured by Dia Rubber Co., Ltd.). After soaking up to the wrist for 5 minutes, the surface of the glove was pulled up, washed gently with water, and the glove made of chlorosulfonated polyethylene was removed from the hand mold.
Next, a hole is made with a sewing needle in the fingertip portion of the index finger of the chlorosulfonated polyethylene glove, and this chlorosulfonated polyethylene glove is covered on a hand mold covered with a yellow fluorescent color glove. After immersing from the fingertip to the wrist part of about 15 cm in aqueous solution for 5 minutes, pulling it up and gently washing the surface with water to remove the chlorosulfonated polyethylene glove from the handprint, the fingertip of the index finger on the surface of the colored chloroprene glove inside A red spot having a diameter of about 2 mm was observed.

Example 9
A foamed resin film is formed by a wet method using a solution in which a polyurethane resin (raw material: Crisbon (registered trademark) 8166, manufactured by Dainippon Ink & Chemicals, Inc.) is adjusted with DMF on the surface of a polyester fiber raw hand. A support type glove made of chlorosulfonated polyethylene rubber with a surface coated with chlorosulfonated polyethylene (raw material: TOSO-CSM TS-340, manufactured by Tosoh Corporation) and 4 times its volume of toluene and dried. Obtained. Next, 1 part of 1% aqueous solution of Coumarin disperse dye Dianix (registered trademark) Luminous Yellow 10G (manufactured by Dystar) and 20 parts of water, ETC-56 (phenylphenol compound, manufactured by Senka Corporation) as carrier 0.02 A support tank is made of chlorosulfonated polyethylene rubber, which is prepared by coloring 1 part of the previous support type gloves with stirring at 97 ° C. for 40 minutes, washing with water and drying. It was created. The obtained glove surface was yellow fluorescent color.
The obtained yellow fluorescent color glove is put on the hand mold again, and a water-resistant chlorosulfonated polyethylene glove with a sleeve (Dairobe A95, manufactured by Dia Rubber Co., Ltd.) is further put on the glove. After soaking up to the wrist for 5 minutes, the surface of the glove was pulled up, washed gently with water, and the glove made of chlorosulfonated polyethylene was removed from the hand mold.
Next, this chlorosulfonated polyethylene glove (Dairobe A95, manufactured by Diamond Rubber Co., Ltd.) is drilled with a sewing needle in the fingertip portion of the index finger, and this chlorosulfonated polyethylene is placed on a hand mold covered with a yellow fluorescent color glove. Put on gloves and immerse the fingertip part of about 15 cm from the fingertips in a 40% nitric acid solution for 5 minutes, pull it up, gently wash the surface and remove the chlorosulfonated polyethylene gloves from the handprint. A red spot having a diameter of about 2 mm was observed on the index finger part of the surface of the polyethylene glove.

Example 10
NBR latex formulation (NBR latex (Nipol (R) Latex Lx-550) 100 parts in solids, 0.5 parts potassium hydroxide, 1 part sulfur, 1 part zinc oxide, 0.2 parts zinc dibutyldithiocarbamate, 40 parts to 1 part of titanium oxide, 1 part of sodium dodecylbenzenesulfonate, 1 part of coumarin disperse dye DIANIX (registered trademark) Luminous Yellow 10G (manufactured by Dystar) adjusted to 35% solids with water and stirred well) A hand mold coated with a% calcium nitrate methanol solution was immersed, and after drying and vulcanization, the mold was inverted and released from the mold to obtain a colored NBR rubber unsupported glove. The surface of the obtained glove was yellow fluorescent color.
The obtained yellow fluorescent color gloves are put on the hand mold again, and further covered with a water-resistant chlorosulfonated polyethylene glove with a sleeve (Dairobe A95, manufactured by Dia Rubber Co., Ltd.), and about 15 cm from a fingertip to a 40% nitric acid aqueous solution. After immersing up to the wrist portion for 5 minutes, the surface of the glove was pulled up, washed gently with water, and the glove made of chlorosulfonated polyethylene was removed from the hand mold. As a result, the inner colored glove had no color or other changes.
Next, a hole is made with a sewing needle in the fingertip portion of the index finger of the chlorosulfonated polyethylene glove, and the chlorosulfonated polyethylene glove is put on a hand mold that is similarly covered with a yellow fluorescent glove, and 40% nitric acid is added. After immersing from the fingertip to the wrist part of about 15 cm for 5 minutes in the aqueous solution, pulling it up and gently washing the surface with water, and removing the chlorosulfonated polyethylene glove from the handprint, the fingertip part of the index finger on the surface of the inner colored NBR rubber glove A red spot having a diameter of about 4 mm was observed.

  As mentioned above, since the protective glove of the present invention adheres or contains a substance that shows a color reaction with a substance harmful to the human body, it can be worn on the inside of the protective glove that protects fingers from harmful substances. Even if the protective gloves are damaged and harmful substances enter the inside, not only will the fingers be protected by the inner protective gloves to prevent chemical injury, but the protective gloves will change color and inform you of the damage and the location of the protective gloves. It allows the use of damaged protective gloves to be stopped, repaired and promptly replaced, and protects fingers from chemical injury. Therefore, the protective glove of the present invention is useful as a protective glove worn inside the protective glove, for example, when working with a hazardous substance in a metal plating factory, precision machine manufacturing, processing factory, or the like.

Claims (10)

  A protective glove made of resin or rubber comprising a substance harmful to the human body and a substance exhibiting a color reaction.   The protective glove according to claim 1, wherein the substance harmful to the human body is an acid.   The protective glove according to claim 2, wherein the substance exhibiting a color reaction is a fluorescent dye of coumarins.   The protective glove according to claim 3, wherein the coumarin fluorescent dye is an oxazolyl coumarin dye or a thiazolyl coumarin dye.   The protective glove according to any one of claims 1 to 4, wherein the resin is a polyurethane resin.   The protective glove according to any one of claims 1 to 4, wherein the rubber is chloroprene rubber or chlorosulfonated polyethylene rubber.   A support-type protective glove characterized in that the surface of a fiber hand is covered with a resin or rubber containing or containing a substance useful for the human body and a substance exhibiting a color reaction.   A protective glove comprising a protective glove having a chemical-resistant layer that does not allow a harmful substance to pass through to the human body, and the protective glove according to any one of claims 1 to 7, wherein the protective glove is used by being superimposed inside the protective glove. Protective gloves.   The protective glove according to claim 8, wherein the protective glove is transparent or translucent.   When working to handle substances harmful to the human body, wear protective gloves having a chemical resistant layer that does not allow the passage of harmful substances to the human body on the outside, wear the protective gloves according to any one of claims 1 to 7, A method for detecting damage to a protective glove, wherein damage to the protective glove is detected by coloration of the protective glove.