JP2009167567A - Protective glove, security protective glove, and method for detecting damage on security glove - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a protective glove worn inside a security glove during work to operate harmful substance such as strong acid or strong alkali, and detecting damage on the security glove to urge to stop using the damaged security glove or replace it for another one in view of change in color of the part of the protective glove with which penetrated harmful substance gets into touch when the surface of the security glove is damaged and the harmful substance penetrates into the inside of the security glove, so that a wearer is prevented from suffering from medicinal wound on her (his) fingers due to contact with the harmful substance. <P>SOLUTION: The protective glove is made of resin or rubber and is provided with a color-presentation layer showing color reaction against the substance harmful to the human body, and a medicine-resistant layer comprising olefin-based block copolymer on the inside of the color-presentation layer. The security glove having the medicine-resistant layer blocking the harmful substance is worn outside, and the protective glove is worn inside to detect the damage of the security glove from the color presentation of the protective glove. <P>COPYRIGHT: (C)2009,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. Protective gloves that detect damage and encourage the discontinuation or replacement of damaged protective gloves and, as a result, prevent hand burns from contact with harmful substances, and protection using the protective gloves together with outer protective gloves The present invention relates to protective gloves and a method for detecting damage to protective gloves.

  Metal processing plants such as metal plating, precision machinery manufacturing factories, machining factories, etc. are working on substances that are harmful to human bodies, such as strong acid and strong alkaline chemicals, and chemical injury caused by these harmful substances In order to prevent this, work is performed while wearing protective gloves made of water-resistant or chemical-resistant resin or rubber. However, if there is a hole in this protective glove, even if this hole is as small as a pinhole, harmful substances will enter the protective glove through this hole and come into contact with your fingers to cause chemical injury. cause. 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). These inspections detect damages formed in the manufacturing and processing steps, and prevent chemical injury.

However, even when working with protective gloves that have been confirmed to have no damage such as pinholes by the above inspection, wear of protective gloves due to use, fatigue, etc. In many cases, the protective gloves are damaged and damaged during handling of substances harmful to the human body due to contact or collision. 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.
To avoid such a situation, it is necessary to detect damage as soon as possible after breaking the glove, stop using it, and replace it with a new glove. Since it is impossible to detect the damage, it is the actual situation to know that the damage was caused by the skin sensation of the worker, that is, the pain caused by the chemical injury, and the work is enthusiastic. Dealing with so much delay may cause severe burns.
Examples of the chemical resistant gloves include chlorosulfonated polyethylene resin and chloroprene rubber (Patent Document 5). However, these materials are not always sufficiently resistant to chemicals and may remain uneasy.
Japanese Patent Laid-Open No. 5-10843 JP-A-7-128179 JP 7-151635 A JP-A-7-218377 JP-A-5-230702

In order to solve the above-mentioned problems of the prior art, the present inventor has developed a protective glove made of resin or rubber, which contains or contains a substance harmful to the human body and a substance exhibiting a color reaction (PCT / JP2007). / 589).
This protective glove has a clear discoloration at the part where it comes into contact with the hazardous substance, so that the harmful substance can enter from the protective glove worn on the outside, that is, damage such as pin holes that allow the protective glove to enter the hazardous substance. It has been shown that the chemical resistance is not always sufficient, although it shows an excellent effect of preventing chemical burns and the like of the fingers.

In view of such circumstances, the present invention can detect the occurrence of damage and the location of damage as soon as possible in order to eliminate the above-mentioned problems and prevent chemical injury due to the invasion of harmful substances. It is an object of the present invention to provide a protective glove provided with a resin layer having excellent chemical resistance, a protective protective glove using the protective glove together with an outer protective glove, and a method of detecting damage to the protective glove.
As a result of diligent research to solve the above problems, the inventor has attached or contained a substance that exhibits a color reaction and a substance harmful to the human body, and a specific arrangement disposed inside the color layer. By wearing a protective glove consisting of a chemical-resistant layer made of the above-mentioned resin on the inside of a normal protective glove, it is possible to quickly detect whether or not the outer protective glove is damaged and the location of the damage, It has been found that the superior chemical resistance of a specific resin can prevent the protective gloves from being deteriorated by the infiltrated chemicals, thereby preventing chemical injury, and the present invention has been completed.

  According to a first aspect of the present invention for achieving the above object, a color layer formed by adhering or containing a substance that exhibits a color reaction and a substance harmful to the human body is disposed on the surface of the glove, and an inner surface of the color layer. A protective glove made of resin or rubber characterized in that a chemical-resistant layer made of an olefin block copolymer is disposed on the surface.

  A second aspect of the present invention includes the protective glove according to the first aspect, wherein the olefin-based block copolymer is a block copolymer of styrene and olefin.

  A third aspect of the present invention includes the protective glove according to the first aspect, wherein the olefin block copolymer is a styrene-isobutylene block copolymer.

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

  A fifth aspect of the present invention includes the protective glove according to any one of the first to fourth aspects, wherein the substance exhibiting a color reaction is a fluorescent dye having a coumarin skeleton.

  A sixth aspect of the present invention includes the protective glove according to the fifth aspect, wherein the fluorescent dye having a coumarin skeleton is an oxazolyl coumarin dye or a thiazolyl coumarin dye.

  Claim 7 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 protection according to any one of claims 1 to 6, wherein the protective glove is used on the inside of the protective glove. Includes multiple protective gloves characterized by consisting of gloves.

  Claim 8 of the present invention provides a protective glove having a chemical resistant layer that prevents a substance harmful to the human body from passing outside when handling a substance harmful to the human body. The protective glove damage detection method is characterized in that the protective glove described above is worn inside and the damage of the protective glove is detected by coloration of the protective glove.

  Since the protective glove of the present invention adheres to or contains a substance that exhibits a color reaction with a substance harmful to the human body and has an excellent chemical resistant layer, when worn inside the protective glove having chemical resistance, When a protective glove worn on the outside is damaged and a substance harmful to the human body enters inside, the substance that shows a color reaction that is attached to or contained in the protective glove is harmful to this human body. The protective glove changes color by reacting with the substance and coloring, thereby easily detecting whether or not the protective glove worn on the outside is damaged and where it is damaged. As a result, the use or replacement of the protective gloves is promoted, and chemical injury can be prevented in advance.

  The chemical-resistant layer is composed of an olefin block copolymer, and the olefin block copolymer is preferably a block copolymer of styrene and olefin, particularly when it is a styrene-isobutylene block copolymer. Even if the glove is unsupported or supported, it has excellent chemical resistance, so even if a substance harmful to the human body reaches the protective glove of the present invention, it touches the operator's finger through the glove. Since it takes a long time to complete, it can be protected for a long time, which is preferable.

  When the material of the colored layer is polyurethane resin or acrylic resin, it is moisture permeable regardless of whether the protective gloves are unsupported type or support type. Harmful substances permeate inside the colored layer and cause the colored substance contained inside the colored layer to also color, so the color reaction becomes more vivid and the protective gloves are vividly colored and protected at a glance. This is preferable because breakage of gloves can be detected.

Examples of substances harmful to the human body include acids and alkalis (for example, hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, aqueous sodium hydroxide, aqueous potassium hydroxide, etc.), and substances exhibiting a color reaction include dyes, pigments, An indicator etc. can be illustrated.
When a substance harmful to the human body is an acid, if a fluorescent dye having a coumarin skeleton is used as a dye, not only the resin or rubber is easily dyed and colored, but also the fluorescent dye having a yellow fluorescent coumarin skeleton is converted to an acid. Since it reacts to turn red, it is easy to check the coloration and to easily detect damage to the protective gloves. 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.
Protective gloves can be composed of a chemical-resistant layer (inner side) that prevents the entry of substances harmful to the human body and a colored layer (outer surface side) that contains substances harmful to the human body and substances that exhibit a color reaction. . In this case, the chemical resistant layer and the colored layer may be the same substance.

  As described above, the protective glove of the present invention is used by being superimposed on the inner side of the protective glove having a chemical-resistant layer that does not allow a harmful substance to pass through 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, not only can the fingers be protected by the protective gloves worn on the inside, but also chemical damage can be prevented. Because of the color of the protective gloves, it is possible to detect damage to the outer protective gloves, so that the use or replacement of damaged protective gloves is encouraged. 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 gloves are transparent or translucent, the color of the inner protective gloves can be observed without taking off the outer protective gloves, so that the protective gloves can be easily and quickly damaged even during work. Can be detected.

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 damage of the protective glove. It is characterized in that a colored layer formed by adhering or containing a harmful substance and a substance exhibiting a color reaction is disposed, and a chemical resistant layer made of an olefinic block copolymer is disposed on the inner surface thereof.
Here, the protective gloves refer to gloves conventionally used for the purpose of preventing chemical damage.
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, and heavy metals.
In addition, the color reaction here refers to all reactions in which a change in color 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. However, dyes, pigments and indicators can be exemplified, and a plurality of coloring substances can be mixed and used.

In the present invention, the method for forming the color layer by adhering or containing the color substance to the protective gloves is not particularly limited, and a known method can be adopted according to the properties of the color substance. For example, when the coloring material is a dye, the dye is attached to the surface of the rubber or resin that is the material of the coloring layer (dyeing or coloring) by immersing gloves in a heated dye solution dispersed in water. And a method of attaching the dye-attached cloth to the surface of the color layer rubber or resin, and in the case of a pigment or indicator, it is directly blended into the color layer material rubber or resin. (Kneading) and then forming it into a glove mold, or mixing it with organosol, resin solution, latex, etc., which is the material of the color layer, to coat it with a glove And a method of coating a glove with a coating material in which a coloring substance is attached to or contained in a cloth or film. Of course, dyes can also be used in the same manner as pigments and indicators.
The material forming the colored layer is not particularly limited as long as the colored substance can be confirmed when it reacts with a harmful substance. For example, as described above, rubber or a material that forms a glove is used. Resins, organosols that form coating materials, resin solutions, latexes, and cloths and films. In particular, in the case of a polyurethane resin or polyacrylic resin that has good compatibility with water, harmful substances permeate into the colored layer, and the colored substance contained in the colored layer can also be colored. The color reaction becomes more vivid, the protective gloves are vividly colored, and the breakage of the protective gloves can be detected at a glance.

As the coloring substance in the present invention, a dye is suitable because it is easy to color the resin or rubber that is the material of the coloring layer, has high reactivity with various chemicals, has a fast color change, and is clear.
The dye that can be used as the coloring substance in the present invention is not particularly limited as long as it exhibits a color reaction with a substance harmful to the human body. Condensation, azo, anthraquinone, pyrimidine, indigo, thioindigo, quinophthalone System, triphenylmethane system, and the like.
The method for attaching the dye is not particularly limited, and any known adhesion (dyeing, coloring) method such as dispersion, direct, cation, acidity, reaction, and vat dyeing can be suitably used. Moreover, you may color by making dye contain in resin or rubber | gum. From the viewpoint of shortening the process and preventing discoloration, it is preferable to contain a dye in the resin or rubber.

  The amount of dye used can be appropriately determined depending on the type of dye, the degree of coloration, etc. The amount of dye used when adhering (dyeing or coloring) is 0.00001 per 1 part by weight of the glove. -0.05 weight part is preferable. If the amount is less than 0.00001 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. When the dye is contained in the resin or rubber, the amount of the dye used is about 0.001 to 5 parts by weight with respect to 100 parts by weight of the resin or rubber solid content. 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 5 parts by weight, the color change is constant and uneconomical.

  Among the dyes, fluorescent dyes are particularly preferable in terms of vivid color reaction. Fluorescein skeleton, eosin skeleton, oxazine skeleton, thiazine skeleton, dioxazine skeleton, azo, azomethine or methine-type polycationic fluorescent colorant alone or a mixture thereof.

  Among fluorescent dyes, fluorescent dyes with cationic or non-cationic coumarin skeletons are not only easy to color resin and rubber, which are the materials of gloves, but also react with harmful substances to show sensitive color changes. It can be particularly preferably used. 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.

  In the case of a fluorescent dye, since a larger amount of dye tends to be required than a normal dye, the addition amount is preferably 0.001 to 0.05 parts by weight with respect to 1 part by weight of the glove. 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 of a colored layer. 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.

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 material include Dianix (Luminous Yellow) 10G: manufactured by Dystar Texilcarben GmbH & Co., Kayalon (registered trademark) Polyester Flavin (Kayalon Polyflavin -S: Nippon Kayaku Co., Ltd., Kayanol (registered trademark) Brill Flavin FL: Nippon Kayaku Co., Ltd., Nirosan (registered trademark) B flavin E8GZ125: Clariant Japan Co., Ltd. The product etc. are marketed.

  The pigment that can be used as the coloring substance in the present invention is not particularly limited as long as it exhibits a color reaction with a substance harmful to the human body, and both organic pigments and inorganic pigments can be used. Is preferable because an inorganic complex easily reacts to show a structural change and a color reaction is easily distinguished. Specific examples include ultramarine blue and malachite.

In general, the pigment is added to the glove by mixing it directly into a resin or rubber.
Although the usage-amount of a pigment can be suitably determined with the kind of pigment, the degree of coloring, etc., 0.01-20 weight part is preferable with respect to 100 weight part of resin or rubber solid content of a colored layer. 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 20 parts by weight, the color change is constant and uneconomical.

  The indicator that can be used as the coloring substance in the present invention is not particularly limited as long as it exhibits a color reaction with a substance harmful to the human body, but pH indicators such as methyl orange, methyl red, phenolphthalein, thymol blue, litmus, Examples thereof include redox indicators such as methylene blue, barrier amine B, diphenylamine, and ferroin, and metal indicators such as eriochrome black T.

The indicator can be attached to or contained in the glove, but is preferably contained in the resin or rubber because of its low affinity with the resin or rubber.
Although the usage-amount of an indicator can be suitably determined by the kind of indicator, the degree of coloring, etc., 0.001-1 weight part is preferable with respect to 100 weight part of resin or rubber solid content of a colored layer. 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 1 part by weight, the color change is constant and uneconomical.

  There are no particular limitations on the carrier that increases the diffusion rate of the colored substance into the resin or rubber and increases the dyeing property, and any known carrier can be used, for example, trichlorobenzene, o-phenylphenol, p-phenylphenol, methylnaphthalene. These may be used alone or in combination of two or more as required.

  In the present invention, the material that can be used as the chemical-resistant layer is one that can protect the fingers of workers from harmful substances that have entered inside from the outer protective gloves, and an olefin-based block copolymer is used as a main component. Examples of the olefin block monomer of the olefin block copolymer include ethylene, propylene, 1-butene, 2-butene, isobutylene, 1-pentene, 3-methyl-1-butene, 2-methyl-2-butene and 1-hexene. 2,3-dimethyl-2-butene, 1-pentene, 1-octene, 1-nonene, 1-decene and other ethylene-based hydrocarbons. Further, diene hydrocarbons and acetylene hydrocarbons can also be mentioned. When these are used as monomers, it is preferable from the viewpoint of chemical resistance that they are hydrogenated and saturated in a later step. These may be used alone or in combination. Among them, it is preferable to use isobutylene as a monomer for the olefin block from the viewpoint of rubber elasticity and chemical resistance. The block other than olefin is a vinyl block, and examples thereof include styrene, methylstyrene, butylstyrene, vinyltoluene, vinyl chloride, acrylic acid, methacrylic acid, acrylonitrile and the like. Among them, it is preferable to use styrene as a monomer for the vinyl block from the viewpoints of easy polymerization, easy control of the glass transition temperature, and physical properties. In particular, as the olefin block copolymer, it is preferable to use a styrene-isobutylene block copolymer or a styrene-ethylenebutylene block copolymer. Among them, it is preferable to use a styrene-isobutylene block copolymer in view of chemical resistance, ease of blending, and ease of processing. The chemical resistance is that the styrene component is 10 to 40% by weight and the isobutylene component is 90 to 60% by weight. From the balance of physical properties and flexibility. The number average molecular weight is preferably 40,000 to 500,000. When the number average molecular weight is less than 40,000, physical properties such as chemical resistance deteriorate, and when it exceeds 500,000, moldability tends to deteriorate. An example of the styrene-isobutylene block copolymer is SIBSTAR (registered trademark) 102T (manufactured by Kaneka Corporation). Here, the main component means a case where the solid content of the chemical-resistant layer is 80% or more, and known additives such as softeners and stabilizers can be added. Is preferably 95% or more, more preferably 99% or more.

The thickness of the chemical resistant layer can be appropriately determined according to the use, but when the chemical resistant layer is a glove material itself, it is the thickness of the glove, and the film or coating layer to be coated on the surface of the glove. In the case of (coating), the thickness is preferably about 0.02 mm to 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.
The chemical resistant layer is disposed on the inner side of the above-described colored layer. The chemical resistant layer is not necessarily in contact with the inner surface of the colored layer, and a rubber or resin layer (for example, a resin or rubber layer of a glove) may be interposed therebetween.

The resin or rubber that can be used as the material for the protective gloves of the present invention is not particularly limited as long as it can protect the operator's fingers from harmful substances that have entered inside from the outer protective gloves. Examples of the resin include acrylic resins such as polyacrylic ester resins, soft polyvinyl chloride resins, polyvinyl acetate resins, polyurethane resins, and the like, and can be used alone or in combination of two or more as required. Moreover, the chemical-resistant layer which consists of an olefin type block copolymer can also be made into the raw material of a protective glove simultaneously.
Among these, polyvinyl chloride resin and polyurethane resin have good affinity with dyes, and not only can they be colored neatly by a simple method, but also dyes attached to the surface of protective gloves cause a color reaction efficiently. The discoloration is easy to observe, which makes it easy to detect damage to the protective gloves.

  As rubber, natural rubber (NR), nitrile butadiene rubber (NBR), styrene butadiene rubber (SBR), chloroprene rubber (CR), chlorosulfonated polyethylene rubber (CSM), isoprene rubber (IR), fluoro rubber, butyl rubber, silicone A rubber etc. can be illustrated and can be used individually or in combination of 2 or more types as needed.

The protective glove of the present invention may be a so-called unsupport type formed by molding a resin or rubber into a glove shape, or may be a so-called support type formed by coating the surface of a fiber glove with the resin or rubber. 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 putting a fiber glove on the hand mold, a method of immersing the hand mold covered with the fiber glove in a resin or rubber raw material liquid, or a raw material on the surface of the hand-type fiber glove Examples include a method of spraying the liquid. 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 the edges may be bonded together. 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, the material of the fiber glove can be appropriately determined according to the use. For example, polyester fiber, polyamide fiber, polyaramid fiber, vinylon fiber, polyolefin fiber, polyurethane Examples thereof include 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.

  The protective glove of the present invention can be worn alone, for example, to detect whether a substance handled by coloration (discoloration) is harmful to the human body, but is preferably used normally. Used on the inside of protective gloves with a chemical resistant layer that does not allow the passage of harmful substances. When used in such a manner, when the outer protective gloves are damaged during work and harmful substances enter the protective gloves and reach the protective gloves, the colored substances attached to or contained in the protective gloves react with the harmful substances. By observing this, the protective glove is discolored, and by observing this, the presence or absence and damage location of the outer protective glove can be detected, and the use or replacement of the damaged protective glove 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 wet process using a solution prepared by adjusting a polyurethane (PU) resin solution (raw material: Crisbon 8166, manufactured by Dainippon Ink & Chemicals, Inc.) to a solid content of 10% with DMF on the surface of a nylon fiber glove covered with a hand mold. A foamed resin coating is prepared, and a styrene-isobutylene block copolymer (SIBS) resin (raw material: SIBSTAR102T, Kaneka Co., Ltd.) xylene solution (solid content 25%) is dip-coated on the top, dried and chemically resistant. Next, 100 parts of PU resin solution (raw material: UST-125HV, manufactured by Dainippon Ink & Chemicals, Inc., solid content of about 25%) and pH indicator thymol blue (Kanto Chemical Co., Ltd.) A colored layer is prepared by a dry method using a solution (solid content: 12%) prepared by diluting 0.1 part of xylene and MEK with 0.1 part, and then released from the hand mold and colored PU surface To obtain a support-type gloves. The surface of the obtained glove was yellow.
The obtained colored glove is put on the hand mold again, and a water-resistant chlorosulfonated polyethylene (CSM) glove with a sleeve (Dairobe (registered trademark) A95, manufactured by Dia Rubber Co., Ltd.) is further put on the hand. After immersing the wrist part of about 15 cm to about 15 cm for 60 minutes, the surface of the glove was gently washed with water to remove the CSM glove from the hand mold. As a result, the inner colored glove had no color or other changes.
Next, a hole is formed with a sewing needle in the fingertip portion of the index finger of the CSM glove, and the CSM glove is put on a hand mold that is similarly covered with a colored glove, and the wrist about 15 cm from the fingertip is covered with 98% sulfuric acid aqueous solution. After soaking for 60 minutes, the surface was pulled up and washed lightly with water, and when the CSM glove was removed from the hand mold, a red spot with a diameter of about 10 mm was seen on the fingertip of the index finger on the inner glove surface. It was confirmed that the occurrence of damage in the CSM gloves was detected. Moreover, no corrosion of the chemical resistant layer was confirmed, and it was confirmed that the fingers were protected and safe even if concentrated sulfuric acid entered from the damage of the outer CSM gloves.

Example 2
The hand mold is immersed in a xylene solution (solid content: 25%) of a styrene-isobutylene block copolymer (SIBS) resin (raw material: SIBSTAR102T, manufactured by Kaneka Corporation) and dried to create a chemical resistant layer. On this chemical-resistant layer, 100 parts of a PU resin solution (raw material: UST-125HV, manufactured by Dainippon Ink & Chemicals, Inc., solid content of about 25%) and Dian Luminous Yellow 10G (manufactured by Dystar Textileben GmbH & Co.) 3 Create a colored layer by a dry method using a solution prepared with a 1: 1 dilution of xylene and MEK (solid content 12%), release from the hand mold, and unsupported gloves on the colored PU surface Got. The surface of the obtained glove was yellow.
The obtained colored glove was subjected to the color development and chemical resistance tests in the same manner as in Example 1. As a result, a red spot having a diameter of about 10 mm was observed on the fingertip portion of the index finger on the inner glove surface. It was confirmed that the occurrence of damage in the CSM gloves was detected. Moreover, no corrosion of the chemical resistant layer was confirmed, and it was confirmed that the fingers were protected and safe even if concentrated sulfuric acid entered from the damage of the outer CSM gloves.

Example 3
NBR latex compound (NBR latex (Nipol (registered trademark) Latex Lx-550, manufactured by Nippon Zeon Co., Ltd.)) 100 parts, 0.5 parts of potassium hydroxide, 1 part of sulfur, 1 part of zinc oxide, Immerse a hand mold with 40% calcium nitrate methanol solution in 0.2 parts of zinc dibutyldithiocarbamate, 1 part of titanium oxide, and 1 part of sodium dodecylbenzenesulfonate adjusted to 35% solids with water and stirred well) After drying and vulcanization, the chemical-resistant layer is formed by dipping in a xylene solution (solid content 25%) of a styrene-isobutylene block copolymer (SIBS) resin (raw material: SIBSTAR 102T, manufactured by Kaneka Corporation) 100 parts of PU resin solution (raw material: UST-125HV, manufactured by Dainippon Ink & Chemicals, Inc., solid content of about 25%) and Dianix Lum A colored layer was prepared by a dry method using a solution (solid content 12%) prepared by mixing 3 parts of nous Yellow 10G (manufactured by DYSTAR Texilfarben GmbH & Co.) with a 1: 1 dilution of xylene and MEK. Release from the hand mold to obtain an unsupported glove with colored PU surface. The surface of the obtained glove was yellow.
The obtained colored glove was subjected to the color development and chemical resistance tests in the same manner as in Example 1. As a result, a red spot having a diameter of about 10 mm was observed on the fingertip portion of the index finger on the inner glove surface. It was confirmed that the occurrence of damage in the CSM gloves was detected. Moreover, no corrosion of the chemical resistant layer was confirmed, and it was confirmed that the fingers were protected and safe even if concentrated sulfuric acid entered from the damage of the outer CSM gloves.

Comparative Example 1
Using a polyurethane (PU) resin solution (raw material: Crisbon (registered trademark) 8166, manufactured by Dainippon Ink & Chemicals, Inc.) adjusted to a solid content of 10% with DMF on the surface of a nylon fiber glove covered with a hand mold A foamed resin film is prepared by a wet method, and a solution composed of chlorosulfonated polyethylene (CSM) (raw material: TOSO-CSM TS-340, manufactured by Tosoh Corporation) and four times the amount of toluene is applied thereon. Dry and create a chemical-resistant layer, then, on this chemical-resistant layer, 100 parts of PU resin solution (raw material: UST-125HV, manufactured by Dainippon Ink & Chemicals, Inc., solid content about 25%) and pH indicator thymol blue (Manufactured by Kanto Chemical Co., Inc.) Using a solution (solid content 12%) in which 0.1 part was adjusted with a 1: 1 dilution of xylene and MEK, a colored layer was created by a dry method and separated from the hand mold Molded and colored PU surface To obtain a support-type gloves. The surface of the obtained glove was yellow.
The obtained colored glove was subjected to the color development and chemical resistance tests in the same manner as in Example 1. As a result, a red spot having a diameter of about 10 mm was observed on the fingertip portion of the index finger on the inner glove surface. It was confirmed that the occurrence of damage in the CSM gloves was detected. However, corrosion of about 10 mm in diameter was confirmed in the chemical resistant layer, and there was a problem in safety.

Comparative Example 2
Chloroprene (CR) latex compounded into hand mold (solid content CR latex (raw material: Skyprene (registered trademark) Latex LA-502, manufactured by Tosoh Corporation)) 100 parts, sulfur 1 part, zinc oxide 3 parts, dibutyldithiocarbamic acid 1 part of zinc, 1 part of titanium oxide and 1 part of sodium dodecylbenzenesulfonate are adjusted to a solid content of 45% with water and stirred well), and a hand mold coated with 40% calcium nitrate / methanol solution is dipped, dried and heated After vulcanization, 100 parts of PU resin solution (raw material: UST-125HV, manufactured by Dainippon Ink and Chemicals, solid content of about 25%) and 0.1 part of pH indicator thymol blue (manufactured by Kanto Chemical Co., Ltd.) are mixed with xylene and MEK. Using a solution prepared with a 1: 1 dilution (solid content 12%), create a colored layer by the dry method, and release it from the hand mold. When the color and chemical resistance tests were performed in the same manner as in No. 1, red spots with a diameter of about 10 mm were observed on the fingertips of the index finger on the surface of the inner glove, and damage occurred on the outer CSM glove. Was confirmed to be detected. However, corrosion of about 10 mm in diameter was confirmed in the chemical resistant layer, and there was a problem in safety.

Example 4
By wet method using a solution of polyurethane (PU) resin solution (raw material: Crisbon 8166, manufactured by Dainippon Ink & Chemicals, Inc.) adjusted to 10% solid content with DMF on the surface of nylon fiber glove put on hand mold A foamed resin coating is prepared, and a styrene-isobutylene block copolymer (SIBS) resin (raw material: SIBSTAR102T, Kaneka Co., Ltd.) xylene solution (solid content 25%) is dip-coated on the top, dried and chemically resistant. Next, 100 parts of PU resin solution (raw material: UST-125HV, manufactured by Dainippon Ink & Chemicals, Inc., solid content of about 25%) and pH indicator thymol blue (Kanto Chemical Co., Ltd.) A colored layer is prepared by a dry method using a solution (solid content: 12%) prepared by diluting 0.1 part of xylene and MEK with 0.1 part, and then released from the hand mold and colored PU surface To obtain a support-type gloves. The surface of the obtained glove was yellow.
Put the obtained colored glove on the hand mold again, and insert a PH test paper inserted between the colored glove and the hand mold in 36% hydrochloric acid from the fingertip to the wrist part of about 15 cm for 60 minutes, and then pull it up. When the surface of the glove was lightly washed and removed from the hand mold, the colored layer of the colored glove turned red and corrosion was observed, but corrosion of the chemical resistant layer was not confirmed. Therefore, since a colored glove is colored (colored) by a harmful substance even by itself, it can be used as a protective glove for detecting whether or not a handled substance is harmful and protecting a finger.

Comparative Example 3
Using a polyurethane (PU) resin solution (raw material: Crisbon (registered trademark) 8166, manufactured by Dainippon Ink & Chemicals, Inc.) adjusted to a solid content of 10% with DMF on the surface of a nylon fiber glove covered with a hand mold A foamed resin film is prepared by a wet method, and a solution composed of chlorosulfonated polyethylene (CSM) (raw material: TOSO-CSM TS-340, manufactured by Tosoh Corporation) and four times the amount of toluene is applied thereon. Dry and create a chemical-resistant layer, then, on this chemical-resistant layer, 100 parts of PU resin solution (raw material: UST-125HV, manufactured by Dainippon Ink & Chemicals, Inc., solid content about 25%) and pH indicator thymol blue (Manufactured by Kanto Chemical Co., Inc.) Using a solution (solid content 12%) in which 0.1 part was adjusted with a 1: 1 dilution of xylene and MEK, a colored layer was created by a dry method and separated from the hand mold Molded and colored PU surface To obtain a support-type gloves. The surface of the obtained glove was yellow.
The obtained colored gloves were tested for coloration and chemical resistance in the same manner as in Example 4. As a result, the colored gloves turned red, but both the colored layer and the chemical resistant layer corroded and permeated hydrochloric acid. Was seen, there was a problem with safety, and it could not be used as protective gloves.

As described above, the protective glove of the present invention is formed from an olefin block copolymer having excellent chemical resistance on the inner surface of a colored layer formed by adhering or containing a substance harmful to the human body and a substance exhibiting a color reaction. The chemical-resistant layer is placed on the inside of the protective gloves that protect the fingers from harmful substances, so that even if the outer protective gloves are damaged and harmful substances enter the inside, Not only is the protective glove protected against chemical burns, but the protective glove is discolored to notify the presence or absence of damage to the protective glove, so that the use of the damaged protective glove can be stopped, repaired and promptly replaced. , Can protect your 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 (8)

  A colored layer formed by adhering or containing a substance harmful to the human body and a substance exhibiting a color reaction is disposed on the surface of the glove, and a chemical-resistant layer made of an olefin block copolymer is disposed inside the colored layer. Protective gloves made of resin or rubber.   The protective glove according to claim 1, wherein the olefin-based block copolymer is a block copolymer of styrene and olefin.   2. The protective glove according to claim 1, wherein the olefin block copolymer is a styrene-isobutylene block copolymer.   The protective glove according to any one of claims 1 to 3, wherein the colored layer is a polyurethane resin.   The protective glove according to any one of claims 1 to 4, wherein the substance exhibiting a color reaction is a fluorescent dye having a coumarin skeleton.   The protective glove according to claim 5, wherein the fluorescent dye having a coumarin skeleton is an oxazolyl coumarin dye or a thiazolyl coumarin dye.   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 6, wherein the protective glove is used by being superimposed inside the protective glove. Multiple protective protective gloves to do.   7. When carrying out work to handle substances harmful to the human body, wear protective gloves with a chemical-resistant layer that does not allow the passage of substances harmful to the human body on the outside, and wear the protective gloves according to any one of claims 1 to 6 on the inside And detecting damage to the protective glove based on coloration of the protective glove.