TWI458767B - Vulcanization accelerator-and sulfur-free elastomer rubber glove for clean rooms - Google Patents

Description

Elastomeric rubber gloves for clean room without vulcanization accelerator and sulfur

The present invention relates to the first step of adding an unsaturated carboxylic acid to acrylonitrile butadiene with or without an unsaturated carboxylic acid to add an unsaturated carboxylic acid to acrylonitrile butadiene. The cross-linking of the stage and the composition obtained after the cross-linking of the second stage are attached to the surface of a mold or a mold in the form of a film, and form a film glove which is crosslinked and hardened, since Containing sulfur as a crosslinking agent and a sulfur compound as a vulcanization accelerator, so users of gloves do not cause type IV allergies, and can be used in a good hygienic state, even if they do not contain sulfur as a crosslinking agent. The sulfur compound as a vulcanization accelerator can be used in a state of strength or tensile strength, and it is less dusty, and does not generate metals or chlorine contained in gloves such as sodium or calcium. The invention relates to an elastomer rubber glove for a clean room in which the product is defective.

Operations such as the manufacture of products in the field of electronic equipment or precision processing are carried out in a clean room where the dust or dust is extremely reduced. A rubber glove used by an operator who operates in a clean room is formed by the presence of sulfur or zinc oxide as a crosslinking agent and a sulfur compound as a crosslinking accelerator. There are also cases where a sulfur-adding accelerator containing a sulfur compound is used at the same time. When a worker uses a glove containing a sulfur-containing agent and a vulcanization accelerator as a rubber glove, the skin of the worker is in contact with the rubber glove, and sometimes causes symptoms of type IV allergy, and there is a problem of health damage. It is a pity that it is still difficult to achieve the use of unused crosslinkers and sulfurization. Gloves formed by the rubber of the sulfur and sulfur compounds.

When using such gloves, the user suffers from the injury caused by type IV allergy. In the field of precision work led by semiconductors, dust or impurities may contact and accumulate in the product, which may adversely affect the performance of the product, which is not preferable. Gloves for clean room also require physical properties such as easy extension and not easy to break. The gloves after use must be recycled, so the gloves must be formed from materials that are easy to recycle.

U.S. Patent No. 5,014,362 (Patent Document 1) is a crosslinking method using a carboxylated nitrile rubber of zinc oxide and sulfur. A typical carboxylated nitrile rubber is formed by a segment of acrylonitrile, butadiene, and an organic acid formed in various ratios. Crosslinking composed of covalent bonds can be formed in the sub-segment of butadiene by using sulfur and a vulcanization accelerator. Further, in the carboxylated acrylonitrile (organic acid), an ionic bond can be generated by using a metal oxide such as zinc oxide or another metal salt. Ion crosslinking is carried out by zinc ions, and crosslinking by sulfur is employed. Further, a method of producing a glove of NBR using zinc oxide or the like as a crosslinking agent is disclosed in the specification of US Pat. No. 6,673,871 (Patent Document 1) regarding an elastomer product such as a glove, which does not use a sulfur-containing crosslinking agent or The sulfur promoter is a metal oxide composed of zinc oxide or the like as a crosslinking agent. However, it is still insufficient when only zinc oxide is used.

In the specification of US Pat. No. 7,005,478 (Patent Document 2), it is stated that when a product composed of an elastomer is to be obtained, it contains: (a) a carboxylic acid or a derivative, and (b) contains a divalent or trivalent metal. a compound and (c) an amine or an amine compound, (d) a state in which at least a part of the carboxylic acid group in the base polymer is neutralized and neutralized to have a carboxyl group The content of the body reaction. At this time, Thiram and Carbamate were used as vulcanization accelerators. The polymer to be used as the matrix is, for example, a natural latex rubber, a synthetic latex polymer (acrylonitrile or the like), a butadiene rubber such as a synthetic butadiene rubber or a carboxylated butadiene rubber, but does not contain MMA or the like. Further, carboxylated acrylonitrile was not used. In this method, the above (c) amine or amine compound is an essential component. The amine or amine group is reacted with a carboxylic acid derivative to form a mismatch with a divalent or trivalent metal. From the point of view of the formation of a reaction by misalignment, it is difficult to achieve stabilization, and as a result, it is difficult to obtain a stable product.

In Non-Patent Document 1 (Andrew Kells and Bob Grobes "Cross-linking in carboxylated nitrile rubber dipped films" LATEX24-25, January 2006, Frankfurt, Germany), it is shown that a trace amount of sulfur is used, and as a sulfur-containing addition. Sulfur accelerator (TMTD), 2,2'-dithio-bis(benzothiazole) (MBTS), N-cyclohexylbenzothiazole sulfinamide (CBS) and diethyl thioamine The addition of zinc carbamic acid (ZDEC) and the necessary zinc oxide gives the content of the latex with improved tensile strength. On the contrary, it is difficult to obtain a carboxylated nitrile latex glove having durability when sulfur and a sulfur-based vulcanization accelerator are not used.

There is no technical description in the literature regarding the effect of attempting to manufacture gloves from self-crosslinking materials and the self-crosslinking properties necessary to produce the desired gloves. It is known that the technical description of self-crosslinking latex has not yet yielded sufficient results.

Non-Patent Document 2 (Dr. SorenBuzs "Tailored synthetic dipping latices: New approach for thin soft and strong Gloves and for accelerator-free dipping"LATEX23-24, January 2008, Madrid, Spain) are two methods: replacing the previous sulfur cross-linking with a functional reactive group (R) to directly crosslink the NBR latex. The method and the method of forming a crosslink between the carboxyl groups of the NBR latex by an ionic bond formed by zinc oxide are established. This method shows a promising approach as a future technical direction. Unfortunately, the functional basis for the action in the covalent bond has not been specifically described. Attempts to clarify this specific formation method have not been successful.

Further, for this problem, the applicant filed an application on the same day as the present application.

The inventors of the present invention have completed the following inventions as an elastomer rubber and an elastomer rubber product which do not use a vulcanization accelerator and sulfur (the application is "an elastomer rubber and an elastomer rubber product which do not use a vulcanization accelerator and sulfur").

"An elastomer composition characterized by being 25 to 30% by weight of acrylonitrile, 62 to 71% by weight of butadiene, and 4 to 8% by weight (100% by weight of total) of unsaturated carboxylic acid, and Crosslinking is formed by bonding formed by a substituent having at least a part of the unsaturated carboxylic acid, and the unsaturated substituent has at least a part of the substituent of the substituent, and the remaining substituent is in a free state, and the crosslinking is formed. The Mooney viscosity (ML ₍₁₊₄₎ (100 ° C)) is 100 to 220, and the film has a weight swelling ratio of 200 to 400%".

And completed "an elastomer composition characterized by being 25 to 30% by weight of acrylonitrile, 62 to 71% by weight of butadiene, and 4 to 8% by weight (100% by weight of total) of unsaturated carboxylic acid, And forming a covalent bond by bonding formed by a substituent of at least a part of the unsaturated carboxylic acid, and the remaining substituent of the substituent having at least a part of the unsaturated carboxylic acid is formed via a divalent metal ion An emulsion formed by crosslinking an ion bond to form a crosslinked product having a weight swelling ratio of 200 to 400%, and using the elastomer composition to complete the following invention: "A glove composed of an elastomer, the system It is composed of an elastomer comprising 25 to 30% by weight of acrylonitrile, 62 to 71% by weight of butadiene, and 4 to 8% by weight (100% by weight of total) of the unsaturated carboxylic acid, and the aforementioned unsaturated carboxylic acid a bond formed by a bond formed by at least a portion of the substituent, and the remaining substituent of the substituent having at least a portion of the unsaturated carboxylic acid is crosslinked by a divalent metal, wherein, as a crosslinking agent, Sulfur and sulfuration as a vulcanization accelerator And it consists of at least a portion having the aforementioned substituents of the group formed by bonding an unsaturated carboxylic acid and cross-linking of the elastomeric Munich viscosity _{(ML (1 + 4) (} 100 ℃)) 100 to 220 on the glove The glove having a thinner elastomer film is a sulfur-free compound as a crosslinking agent and a sulfur compound as a vulcanization accelerator, and has a thickness of 0.05 to 0.15 mm, and a glove swelling ratio of 240 to 320 when the glove is formed. The tensile stress is 22 to 35 MPa, the elongation at break is 480 to 620%, and the tensile stress at 500% elongation is 15 to 35 MPa.

In the glove, even if it is a trace amount, it does not contain sulfur and sulfur compounds as a means of crosslinking, and the result successfully completes the crosslinking means which does not cause the type IV allergy which was previously a problem. At the same time, it can be achieved: "The thickness is 0.05 to 0.15mm, the glove swelling ratio of the glove is 240 to 320, the tensile stress is 22 to 35MPa, the elongation at break is 480 to 620%, and the elongation is 500%. The tensile stress is 15 to 35 MPa.

This result completes the glove with sufficient performance for general work. Correct In this new glove, it is necessary to develop a glove that does not move metal ions or the like contained in the glove to a precision part or a precision member when working in a clean room.

As a result, even if the worker wears the glove, the hand must be in the same state as the state in which the glove is not worn, and the hand can be operated without difficulty without excessive force. Further, in such an operation, when the glove is adhesive when the hand is inserted into the glove, the hand may not easily slide and it is difficult to insert the hand. When the fingers or hands are bent and stretched, sometimes the gloves are close to the hands and difficult to separate. Therefore, it is required to strongly avoid the characteristics of this situation.

When entering the clean room, it must be in a state where it will not be exposed to dust or dust. In the operation in the clean room, it is necessary to strictly manage the sweat, oil, and the like generated by the human body from adhering to the manufactured product. In the operation in the clean room, it is required to pay careful attention to prevent dust or dust from adhering to the introduced raw product.

Gloves used in clean rooms used by workers in clean rooms may be in direct contact with items. It is believed that even if the glove contains a small amount of impurities, the impurities sometimes move to the product through the glove, resulting in the effect of the moving impurities directly affecting the product. When contacting a product via a glove, it is necessary to make an impurity metal or an anion (Na, K, Ca, Al, Mg, Fe, P, Cl ^- , SO ₄ ^2- , Zn, Pb, Cr, Cd, etc.) which is a problem in semiconductor manufacturing. ) does not move from the glove to the product. In order to achieve this, it is necessary to take measures such as reducing the amount contained in the glove and preventing the metal contained therein from moving. In actual measurement, the amount of elution of the metal to water is measured to measure the movement state of the metal, and the amount of elution is required to be extremely small, and the glove after washing also requires less contaminating particles and low dusting property.

By briefly reviewing the development trajectory of the glove for the clean room, the problem of the glove for the clean room is clarified.

In order to prevent the movement of dust or metal, it is known that (1) a film or the like is provided on the glove to prevent movement of dust or metal, and (2) a means for washing the glove with water is used. In the case of changes in dust or metal types and an increase in the amount, a new method must be adopted.

(1) The method of setting the anti-moving film of dust or metal is as follows.

The selection of materials and the prevention of dust generation are as follows. A method of forming a glove using a non-porous, moisture-permeable urethane foam (Japanese Patent Laid-Open Publication No. Hei 5-195303) and a porous stretched polytetrafluoroethylene resin film are used. In the glove layer, a glove composed of a heat-sealable film layer in a dust-free state is produced by a protective film layer, and the protective film is peeled off to obtain a glove. (Patent Document 5: JP-A-H09-137310). These are made of cutting-edge materials, which are time-consuming and labor-intensive to manufacture, and depending on the situation, metals such as sodium ions are sometimes penetrated by a small amount due to the presence of pores. For rubber materials with good characteristics, it cannot compete. The vinyl chloride resin is used as a working glove for a clean room to satisfy the conditions for preventing the movement of heavy metals (Japanese Patent Laid-Open Publication No. Hei 11-12823, Japanese Patent Application Laid-Open No. Hei No. Hei 6-79737). However, when a vinyl chloride resin is used, there is a problem of chlorine generation when it is recovered, and it is difficult to actively use vinyl chloride from this point of view.

(2) There are inventions in which the glove is washed with water or the like. Only join New impurity metals or metal ions, or in the case of increased amounts, can only be treated with water, and must be cleaned with water. In order to prevent the metal contained in the rubber material from moving to the object to be contacted, it is treated with water, and the metal content is reduced as much as possible to reduce the amount of metal released during use. The details are as follows.

There is an invention in which the amount of movement of the object to be contacted between the rubber glove and the rubber glove is reduced to 200 ppb or less (Patent Document No. Hei 11-302911). Specifically, a rubber latex having a small sodium content is polymerized by a polymerization method generally known using the above-mentioned raw materials. Specifically, the reaction tank and the stirring blade used in the polymerization are washed with ion-exchanged water or the like before the polymerization. A rubber latex having a small sodium content is obtained by superfiltration of a rubber latex composed of a raw material containing no sodium in a chemical formula. It is used for post-ion removal treatment, and is generally immersed in flowing warm water of about 40 ° C for about 72 hours. Further, there is an invention in which vibration is generated in ultrapure water to ultrasonically clean the glove disposed in pure water. An invention of removing ions from a rubber glove in a very short time compared to the case of immersion only (Patent Document 9 Japanese Patent Laid-Open Publication No. Hei No. Hei 10-25607). But the whole system is too complicated to reach industrialization.

In the manufacture of precision electronic parts or the manufacture of semiconductor parts, the particles attached to the surface of the rubber glove or the metal ions contained in the rubber gloves may cause adverse effects on the semi-products or products, so pre-purified water or ultrapure water is used. Rubber gloves after washing. Therefore, there is a type of soaked molded article which has a low surface resistivity and a lower surface resistivity than that of the prior art after being washed with ultrapure water, and is used by: A surfactant composition is prepared by blending an acrylonitrile-butadiene rubber latex obtained by copolymerizing a monomer having a carboxyl group, whereby the rubber is not solidified and stably dispersed (Patent Document 10) Bulletin 2004-300386).

Washing with water is an effective means for removing metal ions and the like contained in the obtained rubber glove. However, depending on the material to be used, the content of metal ions may be large, and when it is washed only by water, the movement of the metal by metal ions cannot be excluded.

Gloves for clean room are required to have good physical properties such as elongation and fracture. It can be fully extended during hand operation, allowing the operator to fully perform the desired work. In this type of work, there are more cases where the hand and the glove are dense and difficult to separate. There are the following methods that can be easily worn and worn. (1) Dispersing powder such as talc on the inner surface of the glove, (2) providing other layers on the inside of the glove to prevent adhesion between the hand and the glove, and (3) providing irregularities on the inner surface of the glove by chlorine treatment. (4) Choose a soft material.

(1) A powder such as talc is scattered on the inner surface of the glove as follows.

In the glove obtained by the method of dispersing the powder, the powder is detached from the glove during the dressing or wearing period. Therefore, when used as a medical glove (surgical glove), the powder that has fallen off may have a problem. It is not appropriate to look at this point.

(2) Other layers are provided on the inside of the glove to prevent adhesion between the hand and the glove. Specifically, there are the following methods.

"A rubber glove having an inner coating layer formed of a coating agent containing a resin particle and a latex, and a unit surface of the surface of the inner coating layer In the resin particles observed by the product, the maximum particle diameter is 2 to 20 μm, and the ratio of the total projected area to the unit area (projected area ratio) is 5 to 50%." Patent Document 11 Japanese Patent Application Publication No. 2002- Bulletin 88541)

"A powder-free medical glove having a first surface of a powder-free coagulant which is obtained by embedding a layer of salt-like discrete particles in a previously formed liquid layer to colloid or harden the layer; A second surface for modifying a vinyl acetate polymer to be modified by a coating for facilitating the wearing" (Patent Document 12, JP-A-2007-525336)

"A glove is a glove with a textured surface or a textured foamed coating that is produced by texturing or dissolving discrete particles by processing the foamed surface with residual texture" (Patent Document 13 Japanese Special Table 2007) -524772 bulletin)

"A glove comprising a support body and a coated elastic article present on an inner side surface of the support body, the support system comprising a layer made of an elastic material and partitioning the inner side surface and the outer side surface, the covering area separating the article a hydrogel network structure in which the user and the contacted surface have cross-linking to form an active agent capable of imparting convenience to the user, and the mesh can be obtained from the mesh when the coating is in contact with the aqueous environment. The active drug is released in the structure" (Patent Document 14: JP-A-2007-515565).

In the specification of US Pat. No. 6,709,225 (Patent Document 15), "In order to provide a non-adhesive glove having good sliding characteristics, a thin layer of a synthetic polymer having a low coefficient of friction of 7 μm or less is usually used to laminate the hand. Set of surfaces. The latex barrier layer of the glove is a skin irritant such as calcium lauryl sulfate which is a general-purpose surfactant or a calcium sulphate which is a commonly used coagulant, or a vulcanization promotion. In the case of allergens such as agents and latex proteins, and other rubber-handling chemicals that cause skin irritation or allergic reactions, it is stated that the sodium and calcium are not contained, and the elastomer layer is laminated so that these do not leak out."

(3) The surface which is easy to slide is completed on the inner surface of the glove by chlorine treatment, and a slight unevenness is provided for use. The formed glove can be chlorine treated. Chlorine treatment typically involves the step of contacting the formed article with a chlorine-containing solution or a chlorine-containing gas. The outer surface of the formed article reacts with chlorine during this step in the process. Specifically, the chlorine treatment is used to reduce the adhesion of the glove (Patent Document 16 Japanese Patent Publication No. 2004-526063).

The method of specifying a site to be subjected to chlorine treatment has the following invention.

In the NBR work glove which can be suitably used as a clean room or medical use, the inner surface of the NBR work glove which exhibits the excellent characteristics of both grip and wearability is described, and the inner surface is smoothed by chlorine treatment. machining. Thereby, the gripping property is exerted on the outer side of the glove body (the side on which the user holds the article or the like while wearing the glove body), and is on the inner surface side of the glove body (close to the user's hand or wrist) One of the sides is a glove that exhibits a predetermined slidability (Patent Document No. JP-A-2004-131885).

Japanese Patent Publication No. 2010-520927 (Patent Document 18) describes a chlorination system for removing powder from an elastomer article, improving the inner surface to improve wearability, and weakening the grip strength of the outer surface.

(4) A means for eliminating the viscous (adhesiveness) of the material forming the rubber glove and imparting flexibility.

NBR gloves, compared with natural rubber or PVC gloves, have better oil resistance, wear resistance, etc., and have low dust generation and low static electricity generation. Compared with the NR, it is pointed out that the rebound property is extremely poor and lacks flexibility, and the disadvantage that the surface of the glove easily slides when the article is grasped may become a problem in terms of work safety. When an alkyl acrylate-acrylonitrile-acrylic acid or methacrylic acid copolymerized latex is blended into the NBR latex, the skin mold is soft and hardly slips when leaking, and in addition, when the rosin-based resin latex and the terpene are used When one or both of the resin emulsions are added in an amount of 1 to 10 parts by weight based on the NBR emulsion solid content, the relaxation strength is lowered, and the tensile strength of 200 kg/cm ² or more based on practicality can be maintained (Patent Document 19 Japan) JP-A-2000-290816).

The glove body is formed into a very thin film having a thickness of 0.05 to 0.15 mm by hand-coating an NBR latex material having a composition of at least 1 to 2 wt% of sulfur and 0.5 to 1 wt% of a vulcanization accelerator in 94 to 96 wt% of NBR latex. The portion 1 is formed to cover the user's hand in close contact with each other, and the wrist covering portion 2 is formed to be almost the same size as the wrist or the edge of the wrist, and the inner surface of the glove body is subjected to sliding processing. (Patent Document 20: JP-A-2004-131885). This is a problem that complicates the manufacturing process steps. It is also indicated that the inner surface of the glove body is preferably treated with chlorine.

In the above materials for use in gloves, it is necessary to use a material which is not problematic in health without causing symptoms of type IV allergies which are delayed by contact with the skin. It must also be easily recycled. The characteristics of the glove material must be such that the physical properties such as elongation and breakage are good when working in a clean room, so that the user does not break when the hand is operated as expected, and can be sufficiently elongated to allow The operator can completely carry out the work to be performed. In this work, it is sometimes difficult to put the hand in the glove or cause viscous, so it is necessary to avoid the adhesion between the hand and the glove and the separation. Gloves for comfortable work, in addition, the quality of clean room gloves must not have a direct impact on the product. For example, impurities and metals (Na, K, Ca, Al, Mg, Fe, P, Cl ^- , SO ₄ ^2- , Zn, Pb, Cr, Cd, etc.) that are a problem in semiconductor manufacturing do not move from gloves. The material that is in contact with the glove, or when the inside of the glove is treated with the inner surface treatment agent, does not have dusting properties. When the mobility is measured by the amount of elution of the above metal in water, the amount of elution is required to be extremely small, and the glove after washing is required to have a small number of contaminated particles and low dusting property.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] US Patent No. 6,673,871, Japanese Patent Laid-Open Publication No. 2004-526063

[Patent Document 2] US Patent No. 7005478

[Patent Document 3] Japanese Patent Laid-Open No. Hei 5-195303

[Patent Document 4] Japanese Patent Laid-Open No. Hei 7-216610

[Patent Document 5] Japanese Patent Laid-Open Publication No. Hei 9-137310

[Patent Document 6] Japanese Patent Laid-Open No. 11-12823

[Patent Document 7] Japanese Patent Laid-Open No. Hei 6-79737

[Patent Document 8] Japanese Patent Laid-Open No. Hei 11-302911

[Patent Document 9] Japanese Patent Laid-Open No. 10-25607

[Patent Document 10] Japanese Patent Laid-Open Publication No. 2004-300386

[Patent Document 11] Japanese Patent Laid-Open Publication No. 2002-88541

[Patent Document 12] Japanese Patent Publication No. 2007-525336

[Patent Document 13] Japanese Patent Publication No. 2007-524772

[Patent Document 14] Japanese Patent Publication No. 2007-515565

[Patent Document 15] US Patent No. 6709725

[Patent Document 16] Japanese Patent Publication No. 2004-526063

[Patent Document 17] Japanese Laid-Open Patent Publication No. 2004-131885

[Patent Document 18] Japanese Patent Publication No. 2010-520927

[Patent Document 19] Japanese Patent Laid-Open Publication No. 2000-290816

[Patent Document 20] Japanese Patent Laid-Open Publication No. 2004-131885

[Non-patent literature]

[Non-Patent Document 1] Andrew Kells and Bob Grobes "Cross-linking in carboxylated nitrile rubber dipped films" LATEX24-25, January 2006, Frankfurt, Germany

[Non-Patent Document 2] Dr. Soren Buzs "Tailored synthetic dipping latices: New approach for thin soft and strong gloves and for accelerator-free dipping" LATEX 23-24, January 2008, Madrid, Spain

SUMMARY OF THE INVENTION The first object of the present invention is to provide a material which is formed of a material which does not cause symptoms of type IV allergies which are delayed in appearance by contact with the skin, and which is formed of a material which is easily recovered. New elastomer gloves. Specifically, the object of the present invention is to provide a combination of a metal oxide such as sulfur, sulfur, and zinc, or a metal oxide such as zinc as a crosslinking agent, and a sulfur-containing compound as a sulfurization accelerator. Instead of using such a new cross-linking agent to crosslink the elastomer having a novel structure, the glove is formed by cross-linking the elastomer.

A second object is to provide a glove which has physical properties such as being easy to stretch and which is not easily broken, and can be operated without difficulty in the same state as in a state in which no gloves are worn.

The third problem is to provide a method in which even if the hand is inserted into the glove, the hand is easily slipped into the glove, the hand is easily inserted into the glove, and the glove or the hand is not bent when the finger or the hand is bent straight. Gloves that are intimately characteristic, and it is expected that the amount of impurities and metals contained in the elastomer will change due to the use of a new crosslinking agent, so that the amount is increased, so as much as possible A glove used in a clean room in which the impurity metal and the anion are reduced to the extent that the impurity metal and the anion are not moved to the article in the work.

The present inventors have studied the above-mentioned problems and found the following contents, and invented a rubber glove that solves the problem.

(1) "An elastomer composition characterized by comprising 25 to 30% by weight of acrylonitrile, 62 to 71% by weight of butadiene, and 4 to 8% by weight of unsaturated carboxylic acid (100% by weight of total), and An emulsion formed by bonding formed by a substituent of at least a part of the unsaturated carboxylic acid, and the remaining substituent of the substituent having at least a part of the unsaturated carboxylic acid is in a free state. The Mooney viscosity (ML ₍₁₊₄₎ (100 ° C)) of the combined product is 100 to 220, and the film has a weight swelling ratio of 200 to 400%".

And completed "an elastomer composition characterized by comprising 25 to 30% by weight of acrylonitrile, 62 to 71% by weight of butadiene and 4 to 8% by weight of unsaturated carboxylic acid (100% by weight of total), and a bond formed by a substituent of at least a part of the unsaturated carboxylic acid to form a covalent bond, and a residual substituent of at least a part of the substituent of the unsaturated carboxylic acid, forming an ion via a divalent metal ion The bond forms a cross-linking, and the film of the cross-linked product has a weight swelling ratio of 200 to 400%. Using the elastomer composition, the following invention is completed: "A glove composed of an elastomer, the elastic system Containing 25 to 30% by weight of acrylonitrile, 62 to 71% by weight of butadiene, and 4 to 8% by weight (100% by weight of total) of the unsaturated carboxylic acid, and having at least a part of the substituent of the aforementioned unsaturated carboxylic acid The formed bond is crosslinked, and the remaining substituent of at least a portion of the substituent of the unsaturated carboxylic acid is crosslinked by a divalent metal, wherein: sulfur as a crosslinking agent is not contained and as a vulcanization accelerator Sulfur compound, and by the aforementioned And a carboxylic acid formed by the bonding of at least a portion having a substituent and Munich viscosity of the crosslinked elastomer _{(ML (1 + 4) (} 100 ℃)) of 100 to 220, about the characteristics of the glove, the elastomer The thinner film glove contains no sulfur as a crosslinking agent and a sulfur compound as a vulcanization accelerator, and has a thickness of 0.05 to 0.15 mm, a glove swelling ratio of 240 to 320 when the glove is formed, and a tensile stress of 22 To 35 MPa, the elongation at break is 480 to 620%, and the tensile stress at 500% elongation is 15 to 35 MPa.

As a result, the inventors have completed the following inventions and solved the first problem, that is, "a glove composed of an elastomer comprising 25 to 30% by weight of acrylonitrile and 62 to 71% by weight of butadiene and 4 to 8 wt% of the unsaturated carboxylic acid (100 wt% in total), and crosslinked by a bond formed by at least a part of the substituents of the aforementioned unsaturated carboxylic acid, and at least a part of the unsaturated carboxylic acid The remaining substituent of the substituent is crosslinked by a divalent metal, wherein: sulfur is not contained as a crosslinking agent and a sulfur compound as a sulfurization promoter, and is composed of at least a part of the aforementioned unsaturated carboxylic acid. The bond between the substituents and the crosslinked elastomer has a Mui viscosity (ML ₍₁₊₄₎ (100 ° C)) of 100 to 220. Regarding the characteristics of the glove, the thinner film of the elastomer is not Sulfur as a crosslinking agent and a sulfur compound as a vulcanization accelerator have a thickness of 0.05 to 0.15 mm, a glove swelling ratio of 240 to 320 when the glove is formed, a tensile stress of 22 to 35 MPa, and an elongation at break. 480 to 620%, tensile stress at 500% elongation is 15 to 35MP a".

(2) After obtaining a glove for solving the first problem by using a new crosslinking agent, it was found that a part of the step can be newly provided to solve the second problem.

The steps for the new setup are as follows.

(c) Step: drying the mold or the mold to which the coagulant is attached at 50 to 70 ° C, and drying the surface or a part thereof

(h) Step: a step of treating at a temperature of 120 to 150 ° C for 20 to 30 minutes to form a cross-linking and hardening in a state in which a composition for producing an elastomer is attached to a surface of a mold or a molding die

(3) After obtaining the glove for solving the second problem, it was found that a part of the step can be newly set to solve the problem.

The steps for the new setup are as follows.

(j) performing chlorine treatment on the surface of the film of the elastomer subjected to the drying step after the post-leaching step (i), removing the viscosity (adhesion) of the surface of the elastomer film, and then performing neutralization. Processing steps

(k) a step of washing and drying the film of the elastomer obtained by subjecting the surface obtained in the above (j) to a chlorine-treated mold or a molding die

(l) a step of peeling off the film of the elastomer after the chlorine treatment on the mold or the molding die and turning it to the inside

(m) Chlorine treatment of the inverted glove (off-line chlorine treatment)

(n) washing the glove after chlorinating the outside of the glove in the above step (m) with pure water and drying it

(4) The entire steps of the steps of manufacturing the glove are as follows.

After the elastic body is formed into a thin film shape by using a mold or a molding die, a series of steps of a glove composed of a thin film of an elastomer is produced.

(a) Washing the mold or molding die with a cleaning solution to remove dirt, and washing and drying with cold water

By either a direct immersion method or a coagulant immersion method This step is carried out by a dry mold or molding die. The distinction between these uses is determined by the product. The direct immersion method directly soaks the dried mold or molding die of the article in the mixture prepared by the formulation of the present invention.

(b) a step of immersing a mold or a molding die in a coagulant solution containing 8 to 17% by weight of Ca ²⁺ ions

The coagulant is prepared by adding calcium nitrate to water to contain an aqueous solution of 8 to 17% by weight of calcium, preferably 8.0 to 17.0% by weight of Ca ²⁺ ions. A mold or a molding die is immersed in the aqueous solution. As a result, the coagulant is attached to the surface of the mold or molding die. The time can be decided appropriately. Usually 10 to 20 seconds. Wetting agents and anti-adhesives can also be added. Specifically, it is zinc stearate and calcium stearate.

(c) a step of drying a mold or a mold to which a coagulant is attached at 50 to 70 ° C to dry the surface or a part thereof

The mold or mold to which the coagulant is attached is dried at 50 to 70 ° C to dry the surface or a portion.

(d) a step of immersing the mold or mold having the coagulant obtained in the above step (c) at a temperature of 25 to 25 ° C for 1 to 20 seconds in the composition for producing the elastomer

The composition for producing the elastomer is attached by immersing the mold or the molding die to which the coagulant is attached at a temperature of 25 to 35 ° C for 1 to 20 seconds in the composition for producing the elastomer. The impregnation step is carried out several times. Usually, it is performed twice or more times.

(e) the step of washing with water to remove the drug (leaching)

Forming a mold or molding die with a partially dried latex, in heat In water (30 to 70 ° C), leaching is carried out in a dipping tank for 90 to 140 seconds.

(f) beading (curling edge) step

After the leaching step is completed, the round edge (curl edge processing) is performed.

(g) In-furnace drying step

The glove molding die is dried at 80 to 120 ° C for 250 to 300 seconds.

(h) a step of treating at 120 to 150 ° C for 20 to 30 minutes to form a cross-linking and hardening in a state where the composition for producing an elastomer is attached to the surface of a mold or a molding die

(i) post-leaching (washing to remove the contained drug) on the surface of the film of the elastomer containing the divalent metal as a crosslinking agent on the surface of the mold or the molding die obtained in the above step (h) After drying step

The post leaching system is carried out at 30 to 80 ° C for 60 seconds to 80 seconds.

(j) a step of performing a neutralization treatment after subjecting the surface of the film of the elastomer subjected to the drying step after the leaching of the above step (i) to chlorine treatment to remove the viscosity (adhesion) of the surface of the elastomer film

The chlorine treatment is to form a crosslinked elastomer film in a state of being dried on a mold or a molding die, and is immersed in an aqueous solution having a chlorine concentration of 50 ppm to 200 ppm in the treatment tank. As a result, the formation of the elastomer forms a reaction on the surface of the film in the form of a glove, so that the thickness of the surface is only slightly reduced.

(k) A film of the elastomer obtained by subjecting the surface obtained in the above step (j) to a chlorine-treated mold or a molding die to water washing and drying. The surface viscous (adhesion) is removed at this stage.

(l) a step of peeling off the film of the elastomer after the chlorine treatment on the mold or the molding die and turning it to the inside

The film of the elastomer after the chlorine treatment on the mold or the molding die is peeled off from the mold or the molding die, and the surface after the treatment is turned into an inner surface. At this stage, it is an on-line step. A glove is obtained in which the portion in contact with the hand is smoothed and the hand is easily slid in the glove.

(m) Put the inverted glove into a chlorine treatment device, add chlorine water and immerse the glove therein for the chlorine treatment step (offline chlorine treatment).

The glove was placed in a chlorine treatment device, chlorine water was added thereto, and the glove was immersed therein, and the chlorine treatment was performed while stirring. The chlorine treatment conditions are as follows.

The glove was placed in a chlorine treatment unit, chlorine water was added and the glove was immersed therein for off-line chlorine treatment. The chlorine treatment apparatus is provided with a horizontal cylindrical cage, and the glove is placed in a cage and rotated to perform processing while stirring. The chlorine treatment conditions are as follows.

Wash before: 7 to 13 minutes

Chlorine concentration: 50 to 70 ppm

Chlorine water temperature: 25 to 30 ° C

Chlorine treatment time: 7 to 13 minutes

Neutralization processing time: 5 to 10 minutes

Cleaning 1:10 minutes

Cleaning 2:10 minutes

Cleaning 3:10 minutes

Pre-drying: 13 to 18 minutes at room temperature

Drying temperature: 70 °C ± 15 °C

Drying time: 160 to 200 minutes (using a tumble dryer)

Cooling time: 20 to 40 minutes

(n) washing the glove after chlorinating the outside of the glove in the above step (m) with pure water and drying it

Then wash with pure water.

Quantity: 5000 gloves (30Kg)

Water volume: 500 to 600L (1st, 2nd)

Pure water conditions: resistivity 18M Ω. Ion exchange water above cm

Water temperature: 20 to 30 ° C

Washing time: 10 to 20 minutes (the first and second times are the same)

Washing sequence: steps after washing (first time), draining, washing, washing, centrifuging, dehydrating, and drying

[There is no dehydration step between the first and second washes]

Drying temperature: 65 °C ± 15 °C

Drying time: 1 hour

(a) to (l) can be performed by online processing. Then, from (m) to (o), offline processing is possible.

According to the present invention, since the sulfur as a crosslinking agent and the sulfur compound as a vulcanization accelerator are not used, the symptoms of type IV allergy can be suppressed, which is hygienic; the one is easy to stretch and is not easily broken. Features, easy to use without excessive restraint during work; even when the hand is inserted into the glove, the hand can easily slide into the glove and easily insert the hand into the glove for easy operation; When the hand is bent and stretched, the glove and the hand are not tight; due to the impurity metal contained in the elastomer And the anion also changes and may increase the amount of such an amount, so that the impurity metal and the anion are removed as much as possible, and the amount of the impurity metal and the anion does not move to the working article, thereby preventing the operation in the clean room. When a large amount of metal or the like is moved to the product, a good precision machine can be manufactured.

In the present invention, an acrylonitrile butadiene unsaturated carboxylic acid obtained by adding an unsaturated carboxylic acid to acrylonitrile butadiene or an acrylonitrile butadiene unsaturated carboxylic acid is prepared: (1) forming the first The elastomer composition of the emulsion of the acrylonitrile butadiene unsaturated carboxylic acid after one stage of crosslinking, (2) after the first stage of crosslinking, the second stage of the crosslinked acrylonitrile An elastomer composition of an emulsion of an ethylenically unsaturated carboxylic acid. (3) A glove having a novel property is obtained by using the obtained elastomer composition of the emulsion of the acrylonitrile butadiene unsaturated carboxylic acid after the crosslinking of the second stage of the above (2). The products obtained in the above (1) to (3) have unique characteristics.

(1) An elastomer composition for forming an emulsion of an acrylonitrile butadiene unsaturated carboxylic acid after crosslinking in the first stage is as follows.

a terminal group of an unsaturated carboxylic acid added to an acrylonitrile butadiene unsaturated carboxylic acid obtained by adding an unsaturated carboxylic acid to acrylonitrile butadiene or an acrylonitrile butadiene unsaturated carboxylic acid; Carrying out terminal groups of an unsaturated carboxylic acid added to an acrylonitrile butadiene unsaturated carboxylic acid obtained by adding a carboxylic acid to acrylonitrile butadiene or an acrylonitrile butadiene unsaturated carboxylic acid The reaction is thereby bonded, thereby obtaining an unsaturated carboxylic acid which is added to the acrylonitrile butadiene or the acrylonitrile butadiene unsaturated carboxylic acid after the crosslinking in the first stage is formed. An emulsion of an acrylonitrile butadiene unsaturated carboxylic acid elastomer.

The product of the acrylonitrile butadiene unsaturated carboxylic acid is composed of 25 to 30% by weight of acrylonitrile, 62 to 71% by weight of butadiene, and 4 to 8% by weight (100% by weight of total) of the unsaturated carboxylic acid. And it is specified by the amount ratio of each component. The portion considered to form crosslinks is formed from a larger amount of butadiene from 62 to 71% by weight. The unsaturated carboxylic acid used for crosslinking is the least of the three components.

An acrylonitrile butadiene unsaturated carboxylic acid elastomer obtained by adding a saturated carboxylic acid to an acrylonitrile butadiene or an acrylonitrile butadiene unsaturated carboxylic acid after crosslinking in the first stage The characteristics of the constituted emulsion are as follows.

An elastomer composition characterized by 25 to 30% by weight of acrylonitrile, 62 to 71% by weight of butadiene, and 4 to 8% by weight (100% by weight of total) of unsaturated carboxylic acid, and a bond formed by at least a part of the substituents of the unsaturated carboxylic acid to form a cross-linking, and the remaining substituent of the substituent having at least a part of the unsaturated carboxylic acid is in a free state, the cross-linking The resultant Mooney viscosity (ML ₍₁₊₄₎ (100 ° C)) is 100 to 220, and the film has a weight swelling ratio of 200 to 400%.

a raw material composition composed of 25 to 30% by weight of acrylonitrile, 62 to 71% by weight of butadiene, and 4 to 8% by weight (100% by weight of total) of the unsaturated carboxylic acid, in the presence of a dispersant Mixed raw material composition.

The unsaturated methacrylic acid was added to a mixture of acrylonitrile butadiene, and the following mixture was used for use.

Carboxylated acrylonitrile polybutadiene latex (Synthomer) SXL-XNRR, 746SXL manufactured by Synthomer Corporation). In addition, it can be used under the Pure Protect 560 from Polymer Latex or the Polyac 560 from Shin Foong Company.

Adding unsaturated methacrylic acid to an unsaturated carboxylic acid of acrylonitrile butadiene, although forming a terminal group, other unsaturated methacrylic acid is added to the unsaturated carboxylic acid of acrylonitrile butadiene, It can be considered that no bond is formed between the terminal groups.

The terminal group of the unsaturated carboxylic acid to be used for crosslinking can be suitably used as long as it can form a bond with a terminal group of another unsaturated carboxylic acid. The terminal group of the unsaturated carboxylic acid used for the bonding may be a reaction product selected from the group consisting of a carboxyl group, a hydroxymethylguanamine group, a carboxyl group and a diamine, and a reaction product of a carboxyl group and an alkylenediamine, and a carboxyl group and an alkane. The bond of the reaction product of the base alcohol. These terminal groups may be directly introduced into the unsaturated carboxylic acid or may be appropriately introduced by means of substitution or the like.

Crosslinking is carried out by heating at about 40 °C. It is carried out in the presence of water or in the presence of a surfactant.

The formation reaction of crosslinking is as follows.

a terminal group of an unsaturated carboxylic acid added to an acrylonitrile butadiene unsaturated carboxylic acid obtained by adding an unsaturated carboxylic acid to acrylonitrile butadiene or an acrylonitrile butadiene unsaturated carboxylic acid; Carrying out terminal groups of an unsaturated carboxylic acid added to an acrylonitrile butadiene unsaturated carboxylic acid obtained by adding a carboxylic acid to acrylonitrile butadiene or an acrylonitrile butadiene unsaturated carboxylic acid The reaction is thereby bonded, thereby obtaining an unsaturated carboxylic acid which is added to the acrylonitrile butadiene or the acrylonitrile butadiene unsaturated carboxylic acid after the crosslinking in the first stage is formed. An acrylonitrile butadiene unsaturated carboxylic acid elastomer. This line is synonymous with the following reaction methods.

This is an unsaturated carboxylic acid (or methacrylic acid) formed by adding an unsaturated carboxylic acid (or methacrylic acid) to an acrylonitrile butadiene with or without an unsaturated carboxylic acid (or methacrylic acid). After the acrylonitrile butadiene elastomer, the unsaturated carboxylic acid (or methacrylic acid) is added to the acrylonitrile butadiene polymer to add the unsaturated carboxylic acid (or methacrylic acid) to the acrylonitrile Between the acrylonitrile butadiene portion of the olefin, or the addition of acrylonitrile butadiene or acrylonitrile butadiene unsaturated carboxylic acid (or methacrylic acid) to the unsaturated carboxylic acid (or methacrylic acid) An elastomer obtained by adding a polymer to an unsaturated carboxylic acid (or methacrylic acid) between acrylonitrile butadiene.

In the above form, acrylonitrile and butadiene are emulsion-polymerized to prepare acrylonitrile and a butadiene polymer. A copolymer of an unsaturated carboxylic acid (or methacrylic acid) and acrylonitrile butadiene was prepared by initially adding an unsaturated carboxylic acid (or methacrylic acid) (Case 1). In other cases, when the unsaturated carboxylic acid (or methacrylic acid) is not initially added, acrylonitrile and the butadiene polymer itself (case 2) are used.

The above means acrylonitrile butadiene with or without the addition of an unsaturated carboxylic acid (or methacrylic acid). The amount of unsaturated carboxylic acid (or methacrylic acid) in the case of case 1 means that a very small amount is added.

Adding an unsaturated carboxylic acid (or methacrylic acid) to obtain a polymer of an unsaturated carboxylic acid, methacrylic acid and acrylonitrile butadiene, and further adding an unsaturated carboxylic acid (or methacrylic acid) to obtain a butyl group in which an unsaturated carboxylic acid (or methacrylic acid) is present in the same or different polymer as described above A polymer of an unsaturated carboxylic acid (or methacrylic acid) and an acrylonitrile butadiene between the diene moieties (Case 3).

Adding an unsaturated carboxylic acid (or methacrylic acid) to an acrylonitrile and butadiene polymer to which an unsaturated carboxylic acid (or methacrylic acid) is not initially added, thereby obtaining an unsaturated carboxylic acid (or methacrylic acid) A polymer of an unsaturated carboxylic acid (or methacrylic acid) and an acrylonitrile butadiene between the butadiene portions of the same or different polymers as described above (Case 4).

The reaction caused in Case 3 and Case 4 is as follows.

The butadiene portion of acrylonitrile butadiene is active. The unsaturated carboxylic acid (or methacrylic acid) is added to the acrylonitrile butadiene in these portions to form a branch or to carry out graft polymerization to prolong.

Depending on the case, the butadiene moiety to which the unsaturated carboxylic acid (or methacrylic acid) is attached and adjacent to the other is formed by branching or grafting polymerization with the active moiety. presence.

As described above, a part of the terminal group is bonded to a terminal group of another acrylonitrile butadiene elastomer unsaturated carboxylic acid, and at least some of the remaining part is in a residual state as an elastomer composition in an unbonded state. The first stage of cross-linking.

The following conditions were confirmed by actual measurement by the characteristics of the acrylonitrile butadiene unsaturated carboxylic acid elastomer obtained by crosslinking in the first stage.

The Mooney viscosity (ML ₍₁₊₄₎ (100 °C)) ranges from 100 to less than 220.

When it exceeds 220, the molecular weight increases, resulting in poor workability. When it is less than 100, although the strength is maintained, it becomes difficult to form the film itself. Synthomer's 746SXL is about 128 when comparing similar properties with Mooney viscosity. Left and right, the previous product of 6322 is 122, and Nipol is about 94. In addition, in general, NBR has a Mooney viscosity of 30 to 130.

In this stage of crosslinking, by using the Mooney viscosity, it is known that the molecular weight is high molecular weight (weight average) compared to the previous product.

When an emulsified composition produced by cross-linking is produced, even if a small amount of sulfur is not contained, and a vulcanization accelerator is not used, there is no delayed type IV allergy caused by the addition of the vulcanization accelerator. doubt.

The emulsified composition obtained by crosslinking in the first stage can be processed into a film shape at a temperature of about 40 ° C, and the film weight swelling ratio can be measured. From the results, it was found that the film weight swelling ratio showed a characteristic of 200 to 400%.

The film weight swelling ratio is defined as follows.

Film weight swelling ratio (%) = weight after swelling (g) × 100 / weight before swelling (g) - 100

The film has a weight swelling ratio of 200 to 400%, and it has been found that a film which is crosslinked at a certain degree even without forming a crosslinking treatment can be obtained only under a drying treatment at 40 °C. Since this is a cross-linked product obtained in the first stage, it is considered that in the present invention, a glove having sufficient physical properties (tensile strength, breaking strength, etc.) can be obtained without performing sulfur crosslinking.

Further, the film has a weight swelling ratio of 200 to 400%, and this property shows flexibility.

The emulsified composition obtained by the first-stage cross-linking, as a result of the range of the aforementioned specific Munney viscosity and the range of the film weight swelling ratio, shows the characteristics in the stage of crosslinking at the end of the first stage. It is known from the results that even if the molecular weight is relatively high, it exhibits good flexibility. characteristic.

As a result of the measurement, as will be described later, the results of the Mooney viscosity 151, the film weight swelling ratio of 287%, the Mooney viscosity of 180, and the film weight swelling ratio of 336% were obtained.

(2) The emulsion elastomer composition after crosslinking in the first stage and the second stage is as follows.

An elastomer composition characterized by comprising 25 to 30% by weight of acrylonitrile, 62 to 71% by weight of butadiene, and 4 to 8% by weight (100% by weight of total) of unsaturated carboxylic acid, and is composed of a covalent bond is formed by a bond formed by a substituent of at least a part of the unsaturated carboxylic acid, and a residual substituent of at least a part of the substituent of the unsaturated carboxylic acid is formed via a divalent metal ion The ionic bond forms a cross-linking, and the film has a weight swelling ratio of 200 to 400%. Since the crosslinks are formed by divalent metal ions, the Mooney viscosity cannot be measured.

When the second-stage crosslinking is carried out, the cross-linked elastomer composition formed by the first stage is formed by crosslinking with an ionic bond formed by a metal ion.

Containing 100 phr of the elastomer composition, and 0.5 to 4.0 phr of a crosslinking agent composed of a divalent metal oxide, and 0.1 to 2.0 phr of a pH adjusting agent for adjusting the pH to 9 to 10, and a dispersing agent of 0.5 to 2.0 The composition of the phr and the water is added so that the concentration of the total solid phase material (TSC) generated when the mixture is mixed is 18 to 30% by weight to produce an emulsified composition.

The aforementioned elastomer composition is an emulsified elastomer formed in the first stage. Specifically, it is an emulsified elastomer composition composed of 25 to 30% by weight of acrylonitrile, 62 to 71% by weight of butadiene, and 4 to 8% by weight (100% by weight of total) of unsaturated carboxylic acid, and is composed of An emulsion formed by bonding formed by a substituent of at least a part of the unsaturated carboxylic acid, and the remaining substituent of the substituent having at least a part of the unsaturated carboxylic acid is in a free state. The Mooney viscosity (ML ₍₁₊₄₎ (100 ° C)) of the resultant product is from 100 to 220, and the film has a weight swelling ratio of 200 to 400%.

25 to 30% by weight of the aforementioned acrylonitrile, 62 to 71% by weight of butadiene, and 4 to 8% by weight (100% by weight of the total) of the unsaturated carboxylic acid, such that the unsaturated carboxylic acid is added with or without an unsaturated carboxylic acid Acetic acid acrylonitrile butadiene derived.

The terminal group of the unsaturated carboxylic acid used for the bonding formed by the substituent of at least a part of the unsaturated carboxylic acid is formed by reacting a carboxyl group, a hydroxymethyl guanamine group, a carboxyl group and a diamine. a bond between a product and a reaction product of a carboxyl group and an alkylenediamine, and a bond of a reaction product of a carboxyl group and an alkyl alcohol, and a terminal group of the other acrylonitrile butadiene elastomer unsaturated carboxylic acid via the terminal group of the portion A knot, and at least some other portion of the elastomer composition in an unbonded state.

By this treatment, the terminal group which is added to the terminal group of the unsaturated carboxylic acid of the acrylonitrile butadiene carboxylic acid and is in a free state is similarly added to the acrylonitrile butadiene unsaturated carboxylic acid. Crosslinking via a divalent metal ion is carried out by forming a terminal group of a saturated carboxylic acid and a terminal group in a free state, and a divalent metal ion, specifically, an ionic bond by a zinc metal ion.

After forming a branch by a reaction for forming a terminal group or performing graft polymerization, a part of the butadiene is carboxylated in a reaction by an unsaturated carboxylic acid (or methacrylic acid). Part or further with other The butadiene portion is reacted in the same manner to bond with the unsaturated carboxylic acid monomer (or methacrylic acid) via a divalent metal ion, as shown in the lower left diagram of FIG. 1 and the right side of FIG. .

After the branching is formed by the above reaction or the graft polymerization is carried out, it is sometimes stopped at the stage in this stage. The divalent metal ions are sometimes bonded to form an ionic bond with respect to the portion.

The above crosslinking treatment is considered to cause the following reaction with respect to the carboxylated acrylonitrile butadiene. The cross-linking process considered is as follows.

(A) A double bond carbon of a butadiene moiety in a carboxylated acrylonitrile butadiene graft polymerized by a methacrylic acid monomer. The carboxyl group of methacrylic acid forms an ionic bond via a carboxyl group and a zinc ion of the carboxylated acrylonitrile butadiene to form a crosslink.

(B) a methacrylic acid polymer having a dimer or more, graft-polymerized to a double bond carbon of a butadiene portion in the carboxylated acrylonitrile butadiene. The carboxyl group of methacrylic acid forms an ionic bond via a carboxyl group and a zinc ion of the carboxylated acrylonitrile butadiene to form a crosslink.

(C) a methacrylic acid monomer which crosslinks the double bond carbon of the butadiene portion of the carboxylated acrylonitrile butadiene. The carboxyl group of methacrylic acid forms an ionic bond via a carboxyl group and a zinc ion of the carboxylated acrylonitrile butadiene.

The (meth) methacrylic acid polymer of the dimer or more crosslinks the double bond carbon of the butadiene moiety in the carboxylated acrylonitrile butadiene. The carboxyl group of methacrylic acid forms an ionic bond via a carboxyl group and a zinc ion of the carboxylated acrylonitrile butadiene.

When comparing previous sulfurization reactions by sulfur and by metal separation When the ion formed by the sub-crosslinking (on the left side of FIG. 2), it is observed with the pre-crosslinking formed by the reactive vinyl compound of the present invention and the ion crosslinking formed by the metal (the right side of FIG. 2). In the former, the alkyl group is present between the butadiene portions of different polymers via sulfur, and the cross-linking is formed by a simple structure, whereas the latter is in a state of forming a branch or performing graft polymerization, or Without such a state, cross-linking is formed by internal cross-linking formed by an unsaturated carboxylic acid (or methacrylic acid) and ionic bond formation of a carboxyl group via zinc oxide, thereby utilizing a more complicated and diverse cross-linking reaction. . In the latter case, it is possible to create a state in which it is easy to crosslink when it is crosslinked.

In the latter case, in the case where an unsaturated carboxylic acid (or methacrylic acid) is added to the above polymer of acrylonitrile butadiene, it is understood that an unsaturated carboxylic acid (or methacrylic acid) remains as a residue. The case of unreacted materials.

In the actual measurement using GCMAS (Fig. 3), the latter (in the present invention, the lower diagram of Fig. 3), the peak 1 of the unsaturated carboxylic acid (or methacrylic acid) monomer was observed. In the upper graph shown in Fig. 3, which uses a sulfur and sulfur compound to form a crosslinked elastomer, no peak 1 of the unsaturated carboxylic acid monomer was observed.

In the formation of cross-linking, in order to carry out in an emulsified state, it is carried out using a dispersing agent. In order to form a good dispersion state, it is indispensable to use a surfactant such as an alkylbenzenesulfonate of an anionic surfactant. The alkylbenzenesulfonic acid is not a crosslinking agent and a vulcanization accelerator, but a dispersant. The emulsion which is crosslinked in the second stage is in a state of containing an alkylbenzenesulfonate as an anionic surfactant as a dispersing agent. Sulfur can be determined by containing the substance. There is no sulfur or sulfide as a crosslinking agent. by The vulcanization accelerator formed by the presence of the sulfur compound does not cause delayed allergic type IV allergy of contact dermatitis with allergic symptoms.

The pH adjuster uses potassium hydroxide. This is used to adjust the pH to 9 to 10 as a crosslinking condition for the user, which is 0.1 to 2.0 phr relative to 100 phr of the mixture. When it is less than 0.1 and more than 2.0 phr, it is not enough to maintain the aforementioned pH.

The dispersant uses an anionic surfactant. Specifically, a sodium salt of a naphthalenesulfonic acid polycondensate, an alkylbenzenesulfonate or the like can be used as a dispersing agent. Although these are sulfur compounds, they are used as dispersants and are detected during analysis. This is not used as a cross-linking agent or a vulcanization accelerator, and it does not cause allergies.

Commercial products can be purchased for use. For example, Tamol NN9104 or the like can be used. This amount is from 0.5 to 2.0 phr. This dispersant is beneficial for interfacial polymerization. Further, it can be sufficiently discharged by performing treatment under temperature conditions.

Titanium oxide is added as a whitening agent or a coloring agent. Colorants can be added to the mixture if necessary. An organic dye can be used for the color material.

As the antioxidant, specifically, a non-contaminating type of a polymer hindered phenol can be used, and for example, Wingstay L can be used.

When the composition for producing the above-mentioned elastomer is used, it is adjusted by the amount of water so that the concentration of the total solid phase substance (TSC) generated when the components are mixed is 18 to 30% by weight.

The dynamic viscoelastic action was investigated for the characteristics of the acrylonitrile butadiene unsaturated carboxylic acid after the second stage of crosslinking by the first stage crosslinking. The result confirms the following.

In the invention of the present application, sulfur and sulfur are not used in the first stage. The substance acts as a crosslinking agent and a vulcanization accelerator. In the state of not containing sulfur and sulfur-containing substances as observed in the previous cross-linked product, the present invention can form cross-linking which does not cause delayed type IV allergy (when an anionic surfactant is used as a dispersing agent, The amount is small and does not cause delayed type IV allergy).

From the results of the dynamic viscoelastic properties described below, it was found that the product of the present invention can enhance the effect of crosslinking by crosslinking formed by the first-stage crosslinking and the second-stage crosslinking. In particular, the effect of using zinc is as follows.

(1) The temperature at which the maximum value of the loss tangent (the ratio of the storage elastic modulus/loss elastic modulus) indicated by Tan δ is shown, which corresponds to the glass transition temperature in the transition temperature region where the rubber starts from the low-temperature freezing state and the micro-Brown motion (Tg), the glass transition temperature, the more the basic molecular motion is inhibited (difficult to move), such as the harder molecular chain or the higher the crosslink density, the higher (Fig. 7).

In the acrylonitrile butadiene unsaturated carboxylic acid (denoted as SXL) of the present invention, -10.1 ° C was measured. In the previous product of 6322, the glass transition temperature was -12.2 ° C, and in Nipol 550, -11.6 ° C was measured.

The acrylonitrile butadiene unsaturated carboxylic acid of the present invention (expressed as SXL) gives higher results than in other cases. This speculation may be that the crosslink density formed by the self-crosslinking of the entanglement is high. In addition, the Nipol 550 was observed to be extremely short.

(2) The storage elastic modulus of the flat rubber-like region in the high temperature region after the glass transition temperature, the higher the crosslinking density formed by the entanglement, and the lower the molecular weight (Mc) between the crosslinked chains, the elastic modulus There is a tendency to increase. It is known that the length of the flat portion (temperature region) of the rubber-like region is shown There is a correlation with the number of interlaces per molecule.

According to Fig. 7, the increase in the modulus of elasticity in the flat portion of the rubber-like region of the acrylonitrile butadiene unsaturated carboxylic acid glove brought by the addition of zinc and sulfur is greater than that of the sulfur-based vulcanized product. The increase in the modulus of elasticity brought about by zinc is large, which reflects the increase in the crosslink density brought about by the addition of zinc.

According to Fig. 8, the Tg temperature (-11.0 to 1.5 ° C) of the acrylonitrile butadiene unsaturated carboxylic acid glove is higher than that of the sulfur-based vulcanized rubber (-14.5 to -15.9 ° C), which is due to the addition of zinc. The increase in crosslink density causes the glass transition temperature to shift to the high temperature side, and thus the decrease in the modulus of elasticity is also shifted to the high temperature side, and the amplitude of the transition temperature region is broadened, and the storage elastic modulus is slowly lowered. The elastic modulus of the flat portion is increased.

In the case of the present invention, the effect of addition can be confirmed from the discussion of Figs. 7 and 8.

The formulation of the second-stage cross-linking treatment after the first-stage cross-linking treatment is as shown in Table 1.

A glove characterized by a film of a thinner elastomer formed through the steps of the following steps.

A glove composed of an elastomer composed of 25 to 30% by weight of acrylonitrile, 62 to 71% by weight of butadiene, and 4 to 8% by weight (100% by weight of total) of unsaturated carboxylic acid, and is Crosslinking with a bond formed by at least a part of the substituents of the aforementioned unsaturated carboxylic acid, and the remaining substituent of at least a part of the substituent of the unsaturated carboxylic acid is an elastic bond crosslinked by a divalent metal And an elastomer which is crosslinked by a bond formed by a bond formed by a substituent having at least a part of the unsaturated carboxylic acid as a sulfur compound as a crosslinking agent and a sulfur compound as a vulcanization accelerator Muni's viscosity (ML ₍₁₊₄₎ (100 °C)) is 100 to 220. Regarding the characteristics of the glove, the elastomer thinner film of the glove does not contain sulfur as a crosslinking agent and as a vulcanization accelerator. A sulfur compound having a thickness of 0.05 to 0.15 mm, a glove swelling ratio of 240 to 320 when the glove is formed, a tensile stress of 22 to 35 MPa, an elongation at break of 480 to 620%, and a tensile stress at an elongation of 500%. A glove of 15 to 35 MPa characterized by the steps comprising the following steps Form:

(a) Washing the mold or molding die with a cleaning solution to remove dirt, and washing and drying with cold water

This step is carried out on the dried mold or molding die by any of the direct immersion method or the coagulant immersion method. The distinction between these uses is determined by the product. The direct immersion method directly soaks the dried mold or molding die of the article in the mixture prepared by the formulation of the present invention.

(b) a step of immersing a mold or a molding die in a coagulant solution containing 8 to 17% by weight of Ca ²⁺ ions

The coagulant is prepared by adding calcium nitrate to water to contain an aqueous solution of 8 to 17% by weight of calcium, preferably 8.0 to 17.0% by weight of Ca ²⁺ ions. A mold or a molding die is immersed in the aqueous solution. As a result, the coagulant is attached to the surface of the mold or molding die. The time can be decided appropriately. Usually 10 to 20 seconds. Wetting agents and anti-adhesives can also be added. Specifically, it is zinc stearate and calcium stearate.

(c) a step of drying a mold or a mold to which a coagulant is attached at 50 to 70 ° C to dry the surface or a part thereof

The mold or mold to which the coagulant is attached is dried at 50 to 70 ° C to dry the surface or a portion.

(d) a step of immersing the mold or mold having the coagulant obtained in the above step (c) at a temperature of 25 to 35 ° C for 1 to 20 seconds in the composition for producing the elastomer

The composition for producing the elastomer is attached by immersing the mold or the molding die to which the coagulant is attached at a temperature of 25 to 35 ° C for 1 to 20 seconds in the composition for producing the elastomer. The impregnation step is carried out several times. Usually, it is performed twice or more times.

(e) the step of washing with water to remove the drug (leaching)

A mold or a mold for forming a film is formed by partially drying the latex, and leaching is performed in a immersion tank for 90 to 140 seconds in hot water (30 to 70 ° C).

(f) Round edge (curl edge processing) step

After the leaching step is completed, the round edge (curl edge processing) is performed.

(g) Drying in the furnace

The glove molding die is dried at 80 to 120 ° C for 250 to 300 seconds.

(h) a step of subjecting the molding or molding die obtained in the above step (g) to treatment at 120 to 150 ° C for 20 to 30 minutes to form a cross-linking and hardening step

The composition for producing the elastomer is attached to the surface of the mold or the molding die, and treated at 120 to 150 ° C for 20 to 30 minutes to form a crosslink and harden.

(i) post-leaching (washing to remove the contained drug) on the surface of the film of the elastomer containing the divalent metal as a crosslinking agent on the surface of the mold or the molding die obtained in the above step (h) After drying step

The post leaching system is carried out at 30 to 80 ° C for 60 seconds to 80 seconds.

(j) a step of performing neutralization treatment after performing on-line chlorine treatment on the surface of the film of the elastomer subjected to the drying step after the leaching of the above step (i) to remove the viscosity (adhesion) of the surface of the elastomer film

The chlorine treatment is to form a crosslinked elastomer film in a state of being dried on a mold or a molding die, and is immersed in an aqueous solution having a chlorine concentration of 50 ppm to 200 ppm in the treatment tank. As a result, the formation of the elastomer forms a reaction on the surface of the film in the form of a glove, so that the thickness of the surface is only slightly reduced.

(k) A film of the elastomer obtained by subjecting the surface obtained in the above step (j) to a chlorine-treated mold or a molding die to water washing and drying. The surface viscous (adhesion) is removed at this stage.

The glove is taken out from the mold or the molding die while being turned over, and one side after the chlorine treatment becomes the inner side when worn, and the inner side of the glove can be one side without sticking.

(l) stripping the film of the elastomer after chlorine treatment on a mold or a molding die Step off and flip to the inside

The film of the elastomer after the chlorine treatment on the mold or the molding die is peeled off from the mold or the molding die, and the surface after the treatment is turned into an inner surface. At this stage, it is an online step. A glove is obtained in which the portion in contact with the hand is smoothed and the hand is easily slid in the glove.

(m) Steps of placing the glove in the chlorine treatment unit and chlorine treatment on the outside of the glove

The glove was placed in a chlorine treatment unit, chlorine water was added and the glove was immersed therein for off-line chlorine treatment. The chlorine treatment apparatus is provided with a horizontal cylindrical cage, and the glove is placed in a cage and rotated to perform processing while stirring. The chlorine treatment conditions are as follows.

Wash before: 7 to 13 minutes

Chlorine concentration: 50 to 70 ppm

Chlorine water temperature: 25 to 30 ° C

Chlorine treatment time: 7 to 13 minutes

Neutralization processing time: 5 to 10 minutes

Cleaning 1:10 minutes

Cleaning 2:10 minutes

Cleaning 3:10 minutes

Pre-drying: 13 to 18 minutes at room temperature

Drying temperature: 70 °C ± 15 °C

Drying time: 160 to 200 minutes (using a tumble dryer)

Cooling time: 20 to 40 minutes

(n) Washing the outer side of the glove in the above step (m) by washing with pure water Steps of the glove

Then wash with pure water.

Quantity: 5000 gloves (30Kg)

Water volume: 500 to 600L (1st, 2nd)

Pure water conditions: resistivity 18M Ω. Ion exchange water above cm

Water temperature: 20 to 30 ° C

Washing time: 10 to 20 minutes (the first and second times are the same)

Washing sequence: steps after washing (first time), draining, washing, washing, centrifuging, dehydrating, and drying

[There is no dehydration step between the first and second washes]

Drying temperature: 65 °C ± 15 °C

Drying time: 1 hour

About chlorine treatment

The chlorine treatment as a step of removing surface viscous (adhesiveness) is a mold or a molding die in which a surface of a film which has a dry state and a vulcanized elastomer is formed into a glove form, and chlorine immersed in the treatment tank Solution.

As a result, the formation of the elastomer forms a reaction on the surface of the film in the form of a glove, and the thickness of the surface is reduced. After the end of the operation, it was washed with water and dried. This state is an operation for the inside of the glove, and after the operation is completed, it is taken out from the mold or the molding die and turned over, and the inner surface up to the present is turned over to the surface. The glove or the inverted mold is then immersed in an aqueous solution having a chlorine concentration of 30 ppm to 180 ppm, preferably 50 to 100 ppm, for 5 minutes to 25 minutes. As a result, the impurity metal contained in the surface of the elastomer becomes a chloride, and the solubility is increased, and it is easily removed by washing with pure water. When the chlorine concentration is too low In this case, the effect is small, and the amount of eluted metal is increased. When the chlorine concentration is too high, the double bond of butadiene is added to harden the glove, and the surface is easily damaged.

The film glove of the elastomer obtained by removing the metal ions obtained in the foregoing step is washed with water and dried. After the treatment, the elastic film glove was taken out.

The result is a reaction on the surface of the glove that reduces the adhesion of the glove. Since the glove is used for flipping during use, it is easy to slide the hand into use when in use.

The main steps in the foregoing steps are as follows.

(a) a step of immersing a mold or a molding die in a coagulant solution containing 8 to 17% by weight of Ca ²⁺ ions, and (b) a molding or molding die to which a coagulant is attached at 50 to 70 ° C a step of drying to dry the whole or a part of the surface, (c) immersing the mold or mold having the coagulant obtained in the above step (b) at a temperature of 30 ° C, and immersing it in the present invention a step of producing a composition of the elastomer for 1 to 20 seconds, (d) a step of drying the mold or molding die obtained in the above step (c) at 80 to 120 ° C, (e) the aforementioned (d) The molded body obtained in the step or the elastomer on the surface of the molding die is treated at 120 to 150 ° C for 20 to 30 minutes to form a step of crosslinking and hardening, and (f) the elastomer on the molding die is subjected to chlorine treatment, And drying (washing step after washing), (g) turning the glove out of the molding die and taking it out for chlorine treatment (off-line washing step), (h) washing with pure water and chlorinating off-line The step of the treated glove.

The properties of the glove obtained in the present invention are as follows.

The gloves of the present application are free of sulfur and sulfur-containing cross-linking materials as well as sulfur-containing vulcanization accelerators, as shown in the examples.

The composition of the test piece of the rubber glove was analyzed (11 components: C, H, N, O, S, Zn, Ca, Cl, Na, K, and Ti). As a result of quantitative analysis using an ICP luminescence analyzer, sulfur was detected to be 0.31% by weight. This sulfur is considered to be a sulfonic acid group derived from an anionic surfactant used as a dispersing agent. The overall results are shown in the fifth table of the fourth embodiment and the sixth table of the fifth embodiment.

Regarding the characteristics of the present invention, the relationship between the Mooney viscosity, the glove swelling ratio, Zn, the elongation at break, and the tensile stress at an elongation of 500% is shown in Table 2.

Compared with other gloves, it is shown in Table 3.

In Example 7, the skin sensitivity test results (Table 12) were shown. It was found that the product of the present invention did not cause symptoms of type IV allergy, and there was no problem of health damage.

Compared with the previous products, it has the result of low Zn, Ca and Na.

The measurement result of the thickness of the glove of the thin film of the elastic body of the present invention varies depending on the site, but is 0.05 to 0.15 mm. The tensile stress (strength) of the glove of the thinner film of the elastic body of the present invention is 22 to 35 MPa, and the elongation at break is 480 to 620%.

The glove of the thinner film of the elastomer of the present invention has a modulus coefficient of 500% between 10 and 15 MPa. These are shown in Example 6. The results are shown in Table 7. This information is in no way inferior to previous products using sulfur and sulfur-containing materials (Table 8).

[Example 1]

Further, methacrylic acid was added to the above-mentioned acrylonitrile butadiene in which methacrylic acid was initially added or not, and methacrylic acid was added to acrylonitrile butadiene (Synthomer Co., Ltd. product name Synthomer 746- SXL) is a composition which is mixed with potassium hydroxide, zinc oxide, titanium oxide, a dispersant, an antioxidant, a colorant, and water to form a concentration shown in Table 4.

This composition was used to produce a thin film of an elastomer which does not contain sulfur as a crosslinking agent and a vulcanization accelerator.

[Embodiment 2]

Using the composition consisting of the mixture obtained according to the fourth table, a glove composed of a thin film of an elastomer was produced by the immersion method shown below.

(a) Washing the mold or molding die with a cleaning solution to remove dirt, and washing and drying with cold water

This step is carried out on the dried mold or molding die by any of the direct immersion method or the coagulant immersion method. The distinction between these uses is determined by the product. The direct immersion method directly soaks the dried mold or molding die of the article in the mixture prepared by the formulation of the present invention.

(b) a step of immersing a mold or a molding die in a coagulant solution containing 8 to 17% by weight of Ca ²⁺ ions

The coagulant is prepared by adding calcium nitrate to water to contain an aqueous solution of 10% by weight of Ca ²⁺ ions. A mold or a molding die is immersed in the aqueous solution. As a result, the coagulant is attached to the surface of the mold or molding die. The time is 10 to 20 seconds. Wetting agents and anti-adhesives can also be added. Specifically, it is zinc stearate and calcium stearate.

(c) a step of drying a mold or a mold to which a coagulant is attached at 60 ° C to dry the surface or a portion

(d) immersing the dry mold or molding die to which the coagulant is attached, obtained in the above step (c), at a temperature of 30 ° C for 1 to 20 seconds in the composition for producing an elastomer of the present invention. Step

The composition for producing the elastomer was attached by immersing the dry mold or molding die to which the coagulant adhered at a temperature of 30 ° C for 15 seconds in the composition for producing an elastomer of the present invention. The impregnation step is carried out several times. Usually, it is performed twice or more times.

(e) a step of treating the mold or molding die obtained in the above step (d) with water and separating the medicament (dipping)

A partially formed latex is formed into a coating film of a coating film, and leached in a immersion tank for 90 to 140 seconds in hot water (30 to 70 ° C).

(f) a step of subjecting the mold or the mold obtained in the above step (e) to a round edge (curl edge processing)

After the leaching step is completed, the round edge (curl edge processing) is performed.

(g) a step of drying the mold or molding die obtained in the above step (f)

The glove molding die is dried at 80 to 120 ° C for 250 to 300 seconds.

(h) a step of crosslinking the molding or molding die obtained in the above step (g)

Forming a gloved mold with a coated latex in a dry latex, at 120 to Crosslinking was carried out under the conditions of treatment at 150 ° C for 20 to 30 minutes.

(i) drying the surface of the film of the elastomer after cross-linking on the surface of the mold or the molding die obtained in the above step (h), followed by leaching (washing to remove the contained agent), followed by drying Step

The post leaching system is carried out at 30 to 80 ° C for 60 seconds to 80 seconds. It is divided into 2 times.

(j) Chlorination of the glove surface as a desired step.

Through the series of steps described above, a glove composed of a thin film of elastomer can be produced.

[Example 3]

The comparison example is also shown.

A mixture of methacrylic acid added to acrylonitrile butadiene with or without methacrylic acid added to acrylonitrile butadiene (Synthomer's product name Synthomer) SCL-XNBR746SXL), according to the formula of Table 4 to make gloves.

In the comparative example, a glove containing Zn0 (1.5% by weight) and sulfur (1.0% by weight) in a carboxylated acrylonitrile butadiene latex (product name, Synthomer 6322 manufactured by Synthomer Co., Ltd.) generally used was used to manufacture gloves, and compared. Both gloves. The zinc oxide, the dispersant, the pH adjuster, the antioxidant, and the contents thereof are the same as those shown in the examples. The weight of the solid phase was 30% by weight. A gloved article (product name Verte 710N) was produced from the above composition in accordance with the procedure shown in Example 2.

[Example 4]

Table 5 shows the results of the comparison of the component analysis of the product of the present invention and the product of Comparative Example (Verte 710N).

Component analysis of test pieces of rubber gloves using CHNO analyzer (EA1110 from CE Instruments) and ICP-AES system (11 components: C, H, N, O, S, Zn, Ca, Cl, Na, K and Ti).

The quantitative method of elemental sulfur is as follows.

Quantitative analysis of Zn and Ca, after weighing about 0.1 g of each evaporation residue sample, placed in a platinum crucible to mix the flux (Na ₂ CO ₃ :Na ₂ B ₄ O ₇ =2:1) 2 g The mixture was melted, extracted with 30 ml of hydrochloric acid (HCl: H ₂ O = 1:1), diluted to 100 ml, and quantitatively analyzed using an absorption analyzer. Cl, after weighing about 1 g of each evaporation residue sample, placed in a platinum crucible, melted with an Eschka mixture, and then extracted into 100 ml of pure water to form an aqueous solution, using an absorption analysis device. Quantitative analysis of the aqueous solution. On the other hand, the same aqueous solution was quantitatively analyzed by sulfur using an ICP emission spectrometer.

Sulfur content

According to the invention, the sulfur content is 0.31% by weight.

In Verte 710N, it was 1.10% by weight.

Zinc content

According to the invention, the zinc content is 0.76% by weight of a small amount. In the previous product, it was 1.15 wt%. The amount of zinc in the articles of the invention is less than in previous articles.

[Example 5]

Comparison of acetone soluble components

The amount of light components (unreacted, unsulfurized NBR) in rubber glove products: Soxhlet extraction in acetone solvent for 24 hours according to the quantitative method of JIS K 6299 rubber solvent extract Calculated. Qualitative analysis of the acetone extract was carried out using an infrared absorption (FT-IR) spectroscopic analyzer.

The FT-IR measurement apparatus was an IRP Prestage-21/FTIR-8400S type manufactured by Shimadzu Corporation. The measurement method was a penetration method (using a diamond unit), and the number of integrations was 40 times.

The swelling test of the sample obtained from the rubber glove was immersed in a toluene solvent, and the weight increase of the rubber sample after 72 hours at normal temperature was measured (generally as a method for easily evaluating the state of vulcanization, when immersed in sulfurization) In a good solvent for rubber, the cross-linked polymer such as sulfurized rubber is inhibited by the elastic force of the mesh to achieve a swelling balance, which makes the vulcanization density of the vulcanized rubber inversely proportional to the equilibrium swelling ratio in the good solvent. , calculate each of the above trials The weight swelling ratio (weight of the sample after swelling × 100 / weight of the sample before swelling, unit: %), and the crosslinking density of the vulcanized rubber.

The acetone-soluble component of the present invention was 11.3% by weight, 12.0% by weight, and 10.5 to 15% by weight, and the acetone-soluble component of VERTE 710N of the prior product was 7.7% by weight. The weight swelling ratio of the present invention was 340%, and the weight swelling ratio of the prior product VERTE 710N (KLT-C) was 377% (Table 6).

As a result of infrared analysis of the acetone-soluble component, unreacted nitrile butadiene was observed. In the present invention, the absorption peak of the carboxylic acid group is present in the vicinity of 1700 cm ^-1 .

The fourth table together describes the metal element analysis values of the surface and the inner surface of the ring finger of the glove.

[Embodiment 6]

A latex glove of the present invention further comprising adding methacrylic acid to a mixture of acrylonitrile butadiene initially added or not added with methacrylic acid to add methacrylic acid to acrylonitrile butadiene, and A carboxylated nitrile latex of a product manufactured by a prior art method using a cross-linking method of sulfur and a promoter, which is pulled by the ASTM-6319-00 test method. Stretch test and measure.

Hardened at 150 ° C, respectively. Next, the glove to be a sample was aged under the conditions of a humidity of 50% and a temperature of 23 ° C for 24 hours. The glove was aged at 70 ° C for 7 days.

Regarding the glove of the present invention, the seventh table shows the results of physical tests of the cured glove and the aged glove. Also for the gloves of the previous products, they were hardened at 150 ° C, respectively. Next, the glove to be a sample was aged under the conditions of a humidity of 50% and a temperature of 23 ° C for 24 hours. The glove was aged for 7 days under the conditions of 70 ° C, and the eighth table shows the results of the physical test of the glove.

Gloves made by the method of the present invention using a cross-linking method of ZnO (1.5% by weight) and sulfur (1.0% by weight) The tension is comparable. The elongation of the glove produced by the present invention is higher than that of the glove of the prior art.

In general, the gloves produced by the present invention have good properties after aging as compared with the gloves produced by the prior methods.

Next, the composition of the latex will be explained again.

The pH of the latex composition was further adjusted by adding methacrylic acid to a latex composition in which methacrylic acid was added to acrylonitrile butadiene with or without methacrylic acid and methacrylic acid butadiene. Up to 10, and adjusted by water so that the content of the solid phase becomes 18% by weight to 30% by weight.

The glove produced by using the formulation of the composition of the first table and following the above steps is considered to be good in the following respects.

Advantage 1: The point of defense against type I allergies

According to the product produced by the present invention, the point of natural rubber which causes type I allergy caused by the presence of protein in the latex is not used.

Advantage 2: The point of prevention of type IV allergies caused by late delay

Type IV allergy is caused by the use of a sulfur-promoting agent containing thiocyanate, dithiocarbamate and mercaptobenzothiazole in the manufacture of gloves. In the present invention, a vulcanization accelerator which causes type IV allergy caused by lateness after use is not used.

Advantage 3: Good physical and chemical properties

A system of latex having good film properties is supplied in accordance with the formulation of the latex of Table 1. This results in an extremely thin film and excellent barrier properties. The dimensions of the gloves are as follows. Know the gloves that were made, and the previous ones The gloves are thinner (Table 9).

The physical characteristics are shown in Table 10 below. The tension and elongation at break of the glove of the present invention are the same as or higher than the tension and elongation of the prior glove.

[Embodiment 7]

In Example 1, sulfur was not used as a crosslinking agent and an accelerator, but the article of the present invention was evaluated here, and the potential for immunoreactivity to delayed type IV allergy was not caused when it was in contact with the skin. Perform a skin susceptibility test. Delayed type IV allergies are mainly caused by chemicals such as accelerators used in previous cross-linking methods. The method used in this test is based on 50, 56 and 312 of Article 21 of the CFR.

The purpose of the test is to repeat the test and introduce it from the human skin. The state of the patch test is used to determine the change and/or sensitivity to the glove. This is based on the results of a total of 220 people based on 35 males and 185 females.

The test was carried out in two stages. In the test stage at the time of introduction, a glove film having substantially one side of four sides was placed on the surface of a sealing medical tape manufactured by 3M Company. Place the patch inward between the shoulder and the waist. The trial was conducted on nine projects on Monday, Wednesday and Friday. After the test, the patch was removed after 24 hours. A 24-hour break is available on Tuesdays and Thursdays, and a 48-hour break after Saturdays. Before the next patch test, the trained and testee will record the equipment and the items returned to the site.

At the end of the test at the time of import, the items used in the test are removed and the test is not carried out within 2 weeks thereafter. The re-challenge test was conducted after the break. Re-challenge the test system on the new test site. After the removal test, the parts were recorded separately after 24 hours and 72 hours after application. For those who are in the stage of the end of the final reading of the re-challenge test, for those who are late on the skin, it is indicated that all items are reported.

The state of the skin was recorded according to the following recording criteria (Table 12).

Table 12 is a summary of the results of the trials derived from subjects of 220 people.

In any project, it does not mean getting sick. Regarding several projects (a total of six), it does not last until the end of the trial. According to the glove manufactured in Example 1, there is no evidence showing a medically problematic skin disease or an allergic disease caused by contact with a human. These are the results consistent with the FDA's considerations for the display of mild skin disorders.

[Embodiment 8]

Implementation of the skin sensitivity test (Maximization test)

The test is based on the basic considerations of the biosafety test required for the manufacture of medical devices (input) (February 13, 2015, Pharmaceutical Review No. 0213001) and "Basic with Biosafety Tests" "Reference-related reference materials" (March 19, 2015, Medical Device Review No. 36) was conducted by the Japan Food and Drug Safety Center (Qinye City, Kanagawa Prefecture, Japan).

Test substance

VERTE CheMax 7th Sense as a test substance (abbreviation: 7th Sense, material: nitrile rubber, lot number: PB30061114103022), in the shape of a blue glove, provided by Midori Security Co., Ltd., avoid direct sunlight or high temperature before use, and store at room temperature.

2. Compare control substances

VERTE 710N (abbreviation: 710N, material: nitrile rubber, lot number: 0104170) as a comparative control substance, in the shape of a blue glove, provided by Midori Security Co., Ltd., avoiding direct sunlight or high temperature before use, at 10 Store indoors at °C to 40 °C.

3. Content of the experiment

The VERTE CheMax 7th Sense methanol extract was used to evaluate the biosafety of the gloves of the present invention, and the VERTE CheMax 7th Sense methanol extract was used to perform the marmot (marmot) for comparison with VERTE 710N. ) Skin sensitivity test (Maximization test).

For the preparation of the drug sample, a methanol extract of VERTE CheMax 7th Sense (hereinafter referred to as 7th Sense-M) or a methanol extract of VERTE 710N (hereinafter referred to as 710N-M) is used for the extraction from the extraction. The extract obtained in 1 g of the test substance was a ratio of 1 mL and suspended in ethanol to form a 100 v/v% 7th Sense-M ethanol suspension or a 100 v/v% 710 N-M ethanol suspension. Further, a liquid obtained by dissolving only the negative control (BLANK) obtained from methanol in the same amount as that of 7th Sense-M or 710N-M was formed to be equivalent to 100 v/v%. The BLANK ethanol solution constitutes a negative control. In a sensitive test, 10v/v% 7th Sense-M ethanol suspension or 10v/v% 710N-M ethanol suspension was taken Use an equal amount of olive oil to prepare a 10v/v% 7th Sense-M olive oil suspension or a 10v/v% 710N-M olive oil suspension. In the secondary sensitivity test, 100v/v% 7th Sense-M ethanol suspension or 100v/v% 710N-M ethanol suspension was replaced with the same amount of olive oil to prepare 100v/v% 7th Sense-M olive oil. Use as a suspension or 100v/v% 710N-M olive oil suspension. In the induction test, 100v/v% 7th Sense-M ethanol suspension or 100v/v% 710N-M ethanol suspension was gradually diluted with ethanol to prepare. Further, a BLANK ethanol solution equivalent to 100 v/v% was used as it was.

In a sensitive test (Day 1 of treatment), 10v/v% 7th Sense-M olive oil suspension or 10v/v% 710N-M olive oil suspension and 'Freund's complete adjuvant were administered to the upper part of the scapula of the groundhog. Pinet. On the 7th day of treatment, 10 w/w% sodium lauryl sulfate was applied in advance to the area containing the intradermal administration site, and the next day (disposal day 8), 100 v/v% 7th Sense-M olive The oil suspension or 100v/v% 710N-M olive oil suspension was affixed to the same site for 48 hours as a secondary sensitivity test. In the induction test (treatment day 22), a 100, 20, 4, 0.8, 0.16 v/v% ethanol suspension of 7th Sense-M or 710N-M and a BLANK equivalent to 100 v/v% were attached closed. Ethanol solution for 24 hours.

Experimental conclusion

The judgement was carried out 24 hours and 48 hours after the attachment was removed according to the criteria of the Draize method. As a result, a positive reaction (erythema) was observed in 100 and 20 v/v% of the 7th Sense-M administration group and 100, 20, 4 and 0.8 v/v% concentrations of the 710N-M administration group.

From the above results, it was found that 7th Sense-M and 710N-M showed a positive reaction, so under the test conditions, VERTE CheMax 7th Sense and VERTE 710N showed skin sensitivity to the woodchuck, and the lowest induced concentration was extracted. The VERTE CheMax 7th Sense is 20 v/v% and the VERTE 710N is 0.8 v/v%.

In the glove of the present invention, VERTE CheMax 7th Sense, when it is a high concentration of 20 v/v%, causes a positive reaction, and VERTE 710N has a result of 0.8 v/v%. Information on biosafety assessments and comparisons with VERTE 710N were performed using a methanol extract of VERTE CheMax 7th Sense to perform a Maximization test on woodchucks.

The results are shown in the table.

Individual weight result

Group result

Results after removal of the attachment

Benchmark

Positive rate: (number of positive animals in the group / number of animals in the group) × 100

Average assessment point: total of group assessment points / number of animals in the group

Individual assessment after removal of attachments

Individual assessment after removal of attachments (2)

Individual assessment after removal of attachments (3)

[Embodiment 9]

Using the viscoelastic property measurement test apparatus, the storage modulus of the dynamic viscoelastic property is stored in the tensile mode by the sample of the glove of the present invention and the sample of the prior product of VERTE 710, and the loss modulus is measured. E" and loss tangent tan δ, the results are shown in Table 11. From this result, the main curve showing dynamic viscoelasticity (Fig. 5, Fig. 6) is shown.

The present invention achieves good results in comparison with prior art data.

Using the viscoelastic property measurement test apparatus, the storage modulus of the dynamic viscoelastic property is stored in the tensile mode by the sample of the glove of the present invention and the sample of the prior product of VERTE 710, and the loss modulus is measured. E", and the loss tangent tan δ, and the dynamic viscoelasticity is obtained from the result The main curve is displayed (Figure 5). The results of the samples of the gloves of the present invention are shown. Figure 6 shows the results of VERTE 710 of the previous product. In the present invention, the results of measuring the storage modulus storage elastic modulus E', the loss modulus E", and the loss tangent tan δ as dynamic viscoelastic properties in the tensile mode are good.

[Embodiment 10]

Analysis results of raw material emulsion

The analysis result of the raw material emulsion of the 746SXL of the present invention, the 6322 of the prior product, and the Nipol 550 of the prior product was heat-dried at 80 ° C for 8 hours under reduced pressure, and the resinous residue was finely weighed and calculated in the latex. Solid amount.

(1) The NBR rubber solid content in each latex sample when moisture was removed under reduced pressure at 80 ° C was about 45 to 46%.

(2) The elemental analysis values (C, H) of the solid content in each latex sample were almost the same (C78 to 79%, H9.8 to 10.0% by weight). The nitrogen content of Nipol 550 (from acrylonitrile) is about 3% lower than that of other samples on the basis of acrylonitrile. Both are located in the range of nitriles (25 to 30% of AN). On the other hand, the amount of S derived from the surfactant is from 0.3 to 0.5% by weight.

(3) The amount of volatile unreacted MMA monomer of 6322 was 13 ppm (the upper graph of Figure 3 is a graph showing the amount of volatile unreacted MMA monomer of the previous product).

The amount of volatile unreacted MMA monomer of the 746SXL of the present invention is 370 ppm (the lower graph of Figure 3 is a graph showing the amount of volatile unreacted MMA monomer of the present invention).

[Example 11]

Mui's viscosity measurement

Further adding methacrylic acid to the aforementioned acrylonitrile butadiene with or without methacrylic acid added to add methacrylic acid to acrylonitrile butadiene and ending the first stage of the emulsion's Mooney viscosity (ML) ₍₁₊₄₎ (100 ° C)) is 100 to 220.

The measurement of the Mooney viscosity is specified in JIS K 6300 and ASTM D1646.

In order to determine the viscosity of the unsulfurized rubber measured by the Munni plasticizer (viscometer), the scale of the instrument is printed in the unit of Muney and directly shows the viscosity of the Mooney. In general, a large rotor was used at 100 ° C, and after the preheating for 1 minute, the rotor was started to operate, and the value at 4 minutes was read and expressed as ML ₍₁₊₄₎ (100 ° C).

(a) In the measurement of the Mooney viscosity, methacrylic acid was added to acrylonitrile butadiene with respect to 200 ml of a mixed saturated aqueous solution of calcium nitrate and calcium carbonate. The unsaturated carboxylic acid (or methacrylic acid) is reacted with the butadiene portion of acrylonitrile butadiene and other butadiene portions of acrylonitrile butadiene. Adding an unsaturated carboxylic acid (or methacrylic acid) to a butadiene portion in a state of a large number of branches, or a part of an unsaturated carboxylic acid (or methacrylic acid) in a graft polymerization form The latex in the state of the addition was dropped by a pipette and stirred for 10 minutes (23 ° C, stirring speed: 900 rpm), and the precipitation of the solid rubber was confirmed after the dropwise addition.

The obtained solid rubber was taken out, washed with about 1000 ml of ion-exchanged water (temperature: 23 ° C, stirring speed: 500 rpm), and this operation was repeated 10 times.

The washed solid rubber was dried and dehydrated, and then vacuum dried at 60 ° C for 72 hours.

In this state, the glove molding mold described later is immersed in a coagulant, coated and dried or partially dried at a temperature ranging from 50 to 70 ° C, and immersed in the latex mixed by the formulation of the present invention. The glove molding die is a state in which it is immersed at a specific time and is surely applied to a glove molding die and dried, and is used to measure the Mooney viscosity in a state where it is not crosslinked.

The thickness of the glove molding die is not made too thick. The immersion time of the glove forming mold in the latex is determined by the total solid phase material (TSC) content of the latex after mixing and the desired coating thickness. This time is from 1 to 20 seconds, preferably from 12 to 17 seconds.

This is a polymer composed of a mixture of methacrylic acid and acrylonitrile butadiene added by further adding methacrylic acid to acrylonitrile butadiene with or without methacrylic acid under the above conditions. And the viscosity of the Muss measured without cross-linking.

(b) According to JIS K6300-1:2001 (un-vulcanized rubber - physical properties - Part 1: viscosity and scorch time measured according to the Mui viscometer), will be recovered from each latex The solid solid rubber portion was dried and passed through an 8-inch roll having a roll gap of 1.00 mm 10 times, and then provided for the test.

(c) The 746SXL of the present invention has a Mooney viscosity (ML ₍₁₊₄₎ (100 ° C)) of 151, and the previous product of 6322 has a Mooney viscosity of 122. In the previous measurements, they were 180 and 128, respectively.

In general, NBR (acrylonitrile butadiene) latex is a polymer polymerization obtained by copolymerizing a part of an unsaturated carboxylic acid such as methacrylic acid. Things.

The degree of polymerization can be determined by various methods, and the Mooney viscosity is an effective index when it is insoluble in an organic solvent. The NBR (acrylonitrile butadiene) latex used in the present invention can form a covalent bond with two double bonds of butadiene by sulfur, so NBR (acrylonitrile butadiene) latex becomes high-order Crosslinked rubber elastomer. Further, since zinc is used as a divalent metal ion to form a crosslink of two unsaturated carboxylic acids, the crosslinked structure is made stronger. However, in the present invention, since there is no crosslinked structure formed of sulfur, the molecular weight (degree of polymerization) of the NBR latex is increased, and the strength of the rubber elastic body is assisted by the intertwining or mutual intrusion of the NBR latex. Therefore, the NBR latex of the present invention is from 100 to 220 with respect to the previous NBR latex having a Mui viscosity of about 30 to 80, which is more polymer (high degree of polymerization) than the prior art.

Therefore, if the more polymer NBR latex is intertwined or invaded each other, it is extremely advantageous for the improvement of strength. Further, if a part of the copolymerized unsaturated carboxylic acid is crosslinked by zinc of a divalent metal ion between the entangled or mutually invaded NBR latex, the strength is stronger.

In NBR latex with a viscosity of less than 100, the effect of the intertwining or mutual intrusion is small due to the small molecular chain. In addition, when the Mooney viscosity is above 220, the NBR latex itself will be intertwined, and the interlacing with other NBR latex becomes smaller, so that the mutual intrusion of the NBR latexes becomes smaller.

In addition, the crosslinking formed by zinc is increased by the unsaturated carboxylic acid in the same NBR latex polymer, and the phenomenon of cross-linking a plurality of NBR latexes by zinc is extremely small, thereby lowering the strength. Easy to break.

In the various experiments of the inventors, the optimum value is a range of 100 to 220. Inside.

[Embodiment 12]

Latex particle size distribution assay

Each emulsion liquid was diluted to about 0.002% with ion-exchanged water, and ultrasonic dispersion was performed for about 1 minute, and then the particle size distribution measurement was performed by the following submicron particle diameter measuring apparatus.

(particle size measurement conditions)

Measuring equipment: COULTER N4 PLUS

Liquid viscosity: 0.9333cp

Temperature: 23 ° C

Automatic SDP: 10nm to 1000m

Angle selection: 90°

The latex particle size of the 746SXL of the present invention measured last time, the average particle diameter = 168 nm, and the standard deviation was 28.9 nm (Fig. 4).

The latex particle size of the 746SXL of the present invention measured this time, the average particle diameter = 170 nm, and the standard deviation was 16 nm.

The latex particle size of the previous product of 6322, the average particle diameter of 6322 = 178 nm, and the standard deviation was 30.0 nm (Fig. 4, lower panel). The latex particle size of the 6322 of the previous product measured this time, the average particle diameter = 184 nm, and the standard deviation was 53 nm.

The particle size distribution of the Nipol of the previous product measured this time was 141 nm and the standard deviation was 24 nm.

[Example 13]

Evaluation of reactivity of latex raw materials

(a) Test method for ZnO addition system

The zinc oxide (ZnO) slurry was added to the solid content of each latex in an amount of 1.2 parts by weight in terms of the oxidized solid content, and then stirred in a sealed container at room temperature for 24 hours, and then transferred to a glass container having a flat bottom surface. (Liquid height: 2 mm), after drying and thinning at 40 ° C, heat treatment was performed at a predetermined temperature (150 ° C) for 1 hour.

(b) Test method for ZnO unadded lines

Each latex was directly transferred to a glass container having a flat bottom surface (liquid surface height: 2 mm), dried at 40 ° C, and then heat-treated at a predetermined temperature (150 ° C) for 1 hour.

(c) Quantification method of carboxylic acid

The emulsion solid content (resin film) after drying at each temperature was measured by infrared spectroscopy to determine the peak intensity ratio of the carboxylic acid group derived from MMA and the acrylonitrile group (the peak intensity of the COOH group of 1699 cm ^-1 ) The peak intensity of the CN group of /2235 cm ^-1 ), using a calibration curve (a calibration curve made of a resin film obtained by adding polyacrylic acid (PAA) of 1 to 3 wt% on a solid basis to 746SXL latex) ), the PAA conversion value of the amount of unreacted carboxylic acid in the solid fraction was calculated.

(d) Analysis of light components (unreacted NBR)

The amount of light components (unreacted rate, unsulfurized NBR amount) in the latex raw material film: Soxhlet extraction in acetone solvent for 24 hours according to JIS K 6299 (quantification method of rubber-solvent extract) (Soxhlet) Extraction).

(e) Method for measuring weight swelling ratio

The swelling test of the latex raw material film is carried out by immersing the film in a toluene solvent, and measuring the weight increase after 27 hours at normal temperature (generally, as a method for easily evaluating the vulcanization state of the vulcanized rubber, it is added When the sulfur rubber is immersed in a good solvent, the good solvent will diffuse by dissolving the polymer chain, but in a crosslinked polymer such as a sulfurized rubber, it is inhibited by the elastic force of the mesh to achieve a swelling balance, and the sulfurization density is The equilibrium swelling ratio in the good solvent has an inverse relationship. The weight swelling ratio of each latex raw material film data is calculated and set as the standard for the crosslinking state of the vulcanized rubber.

In the crosslinked polymer of the product of the present invention, the swelling is inhibited by the elastic force of the mesh to achieve a swelling balance, so the crosslink density is inversely proportional to the equilibrium swelling ratio in the good solvent.

The 19th table shows the results of the above analysis of the dried product at 40 ° C, and the 20th table shows the results of the above analysis of the heat-treated product at 150 ° C for 1 hour.

The 746SXL of the present invention and the 6322 of the prior art substantially did not observe a decrease in the amount of the carboxylic acid group by heat drying in the absence of ZnO. In Nipol 550, a decrease in the amount of carboxylic acid groups of about 1 to 20% was observed.

Next, when ZnO was added to both of 746SXL of the present invention and 6322 of the prior art, a case where the amount of the carboxylic acid was significantly reduced by heat treatment at 150 ° C was observed, and the tendency to decrease (increased reaction rate) was in 746 SXL. More significant. It is judged to be formed by the promotion of cross-linking.

The amount of acetone-soluble component (unreacted NBR rubber) of 746SXL was 33.7 wt% and 27.4 wt% in two batches of ZnO unadded system, and 150 ° C for 1 hour in batch 1. The heat treatment was reduced to 26.9%. On the other hand, in the ZnO addition system, the heat treatment at 150 ° C for 1 hour was remarkably reduced from 32.4% to 14.2%, and zinc was observed. Bring the cross-linking effect.

The weight swelling ratio of the 40°C dried product of 746SXL in which ZnO was not added was 287% and 336% in the measurement of the two batches, and the crosslinking density was relatively high. The ZnO additives are also almost identical.

The amount of acetone soluble component and weight swelling ratio of 6322 is the same as that of 746SXL.

On the other hand, in the case of Nipol 550, unlike the above-mentioned sample, the weight swelling ratio in the 40 ° C dried product was 501% in the ZnO unadded system, and the added value was 529%, and the temperature was 150 ° C. In the 1 hour treatment, the addition of ZnO will increase. This shows that the crosslinking treatment is not carried out in Nipol 550, and a film having a high crosslinking density cannot be obtained. Even if ZnO is added, the crosslinking density cannot be increased. This can be considered as the MISS viscosity of 746SXL (ML ₍₁₊₄₎ (100 °C)) is larger 151 and 180 in the two batches of measurement, compared to the smaller 94 in Nipol 550. Therefore, in Nipol 550, the effect of entanglement or mutual intrusion becomes small due to the small molecular chain.

[Embodiment 14]

The electrical properties of the gloves of the present invention were determined.

(a) Surface resistivity

The measurement method is as follows. The measuring device is shown in Fig. 12.

According to IEC specification 61340-2-1 A.5.4

Measurement environment: 20 ° C, 40% RH

Test equipment: Surface resistance meter MODEL 152 (manufactured by TREK)

Applied voltage: 100V

The measurement result was 2.65 × 10 ¹² Ω/sq.

(b) Resistance value when the glove is worn

The measurement method is as follows. The measuring device is shown in Fig. 13.

According to IEC specification 61340-2-1 A.5.4

Measurement environment: 20 ° C, 40% RH

Equipment used: Surface resistance meter MODEL 152 (manufactured by TREK)

Applied voltage: 100V

Specification value: 7.5×10 ⁵ ≦Rg≦1×10 ¹²

The measurement result was 1.22 × 10 ⁸ Ω.

(c) Charge decay measurement

The measurement method is as follows. The measuring device is shown in Fig. 14.

According to IEC specification 61340-2-1 A A2.2

Measurement environment: 20 ° C, 40% RH

Equipment used: charged flat panel monitor MODEL 158 Charge (TREK company)

Specification value: less than 2 seconds

A gloved hand of a subject equipped with a wrist strap was placed on a plate with an electric charge of ±1000 V, and the time during which the plate was attenuated to ±100 V was measured.

The measurement results are as follows. The time required to attenuate from 1000 V to 100 V is 0.48 seconds when the polarity is - and 0.35 seconds when the polarity is +.

As described above, the glove of the present invention exhibits good electrical characteristics.

[Example 15]

The results of SEM/EDX analysis of the outer surface of each rubber glove are as follows.

Granular attachment of the outer side surface of the ring finger of each rubber glove sample Morphological analysis of the material was carried out using an electron microscope (ES-SEM, 30 to 5000 times), and the component analysis was carried out using an energy dispersive characteristic X-ray (EDX) analyzer attached to the electron microscope.

FE-SEM/EDX measurement conditions

Device: Model S-4100 manufactured by Hitachi Ltd.

Measurement conditions: accelerating voltage 15KV, Pt to Pd evaporation treatment for 30 seconds

EDX measurement conditions: Quantum detector manufactured by KEVEX Co., Ltd. (determination element B to U, decomposition energy 143 eV)

Fig. 15 is a view showing the outer surface of the ring finger of the present invention and the presence of elements of the outer surface of the ring finger of the glove of the present invention. Figure 15B is a diagram showing the outer surface of the ring finger of the prior art and the presence of elements of the outer surface of the ring finger of the glove of the prior art.

It was found that the glove of the present invention reduced the element by chlorine treatment.

The measurement results of the product are as follows.

The sixth table in the above-mentioned Example 5 shows the results of analyzing the outer side and the inner side by the EDX on the powder of the ring finger surface of the present invention; and analyzing the outer side and the inner side by the EDX on the ring finger surface of the present invention The results; the powders relating to the EDX results of the ring finger surface of the present invention and the prior art are the results of analyzing the outside and inside of the glove; the EDX results for the ring finger surface of the prior art are the results of analyzing the outside and inside of the glove. Together, it shows the amount of acetone soluble components and the weight swelling rate.

[Example 16]

The measurement results of the product are as follows. The chlorination on the outside of the glove is carried out at a chlorine concentration of 50 to 150 ppm. Knowing the average particle size of the article of the invention The value is also small, and the tensile strength and the amount of dissolved metal and chlorine are also small. Can be a good product. The rubber glove obtained by chlorine treatment to remove metal ions was allowed to stand in water for 1 hour, and the main contaminated components (Na, K, Ca, Zn, Cl) of the rubber glove were extracted (5 cm from the cuff) ).

The extract was taken out in a clean room and analyzed by ICP-MS and ion chromatography (IC) apparatus installed in a clean room (Table 12).

The number of particle diameters of 0.3 μm or more is two in the average in the present invention. The other is more than three. The results are shown in Table 21.

[Example 17]

The surface of the glove of the present invention was compared with the previous sulfur/zinc crosslinked NBR glove by an electron microscope and compared. The result is shown in Figure 16. The surface of the glove of the present invention is relatively smooth compared to prior articles, which can be considered as a factor that is easily removed from the glove by contaminating particles or metal ions.

[Industry use possibility]

According to the present invention, it is possible to provide a type IV allergy which does not cause delayed type Elasticity of the disease. This can be utilized in a variety of products. Further, the crosslinking method shown in the present invention can also be considered.

Fig. 1 is a view showing a state in which the raw material composition of the present invention is crosslinked.

Fig. 2 is a view showing the state in which the crosslinked state of the present invention is formed and the state in which the crosslink is formed.

Figure 3 is a graph showing the amount of volatile unreacted MMA monomer contained in the present invention and prior articles. The lower panel of Figure 3 (in the context of the present invention) shows the amount of volatile unreacted MMA monomer of 746 SXL. The top panel of Figure 3 (in the case of previous articles) shows the amount of volatile unreacted MMA monomer.

The upper graph of Fig. 4 is a measurement result of the particle size of the latex of the 746SXL of the present invention. The lower graph of Fig. 4 shows the measurement results of the latex particle size of the previous product of 6322.

Fig. 5 is a view showing a sample of the glove of the present invention (an emulsion film obtained by casting a film of an aqueous solution of an emulsion and drying under reduced pressure at 40 ° C for 72 hours), as measured by a tensile mode as a dynamic viscoelastic property. In the results of storing the modulus storage elastic modulus E', the loss modulus E", and the loss tangent tan δ, the results of the main curve of the dynamic viscoelasticity are calculated.

Fig. 6 is a view showing a storage modulus E', a loss modulus E", which is measured as a dynamic viscoelastic property as a storage modulus of a dynamic viscoelastic property by a sample of VERTE 710 of the prior art (the same as Fig. 5). And the result of the loss tangent tan δ, the result of the main curve of the dynamic viscoelasticity is calculated.

Figure 7 is for SXL (the product of the invention, glass transfer temperature -10.1 °C), 6322 (glass transition temperature -12.2 °C), Nipol 550 compare the loss tangent tan δ.

Fig. 8 is a graph comparing the loss tangent tan δ of the CHM-based raw material emulsion (the raw material emulsion of the present invention) and the product glove.

Figure 9 is a graph comparing the loss tangent tan δ of a sulfur-added sulfur-containing raw material emulsion and a product glove.

Fig. 10 is a graph showing the loss tangent tan δ for a CHM-based raw material emulsion (the raw material emulsion of the present invention) and a sulfur-sulphurized raw material emulsion.

Figure 11 is a graph showing the relationship between the amount of unsulfurized rubber and the weight swelling ratio for glove products.

Fig. 12 is a view showing a measuring device for the surface resistivity of the glove.

Fig. 13 is a view showing a measuring device for measuring the resistance value when wearing gloves.

Fig. 14 is a view showing a measuring device for charge attenuation of a glove.

Fig. 15 is a view showing the outer surface of the ring finger of the present invention and the presence of elements of the outer surface of the ring finger of the glove of the present invention. Figure 15B is a diagram showing the outer surface of the ring finger of the prior art and the presence of elements of the outer surface of the ring finger of the glove of the prior art.

Figure 16 is an electron micrograph showing the surface of the glove of the present invention and the prior sulfur/zinc crosslinked glove.

Claims (12)

A glove formed from an elastomer composition comprising an elastomer comprising 25 to 30% by weight of acrylonitrile, 62 to 71% by weight of butadiene and 4 to 8% by weight of unsaturated carboxylic acid (all 100) % by weight, and crosslinked by a bond formed by a substituent of at least a part of the aforementioned unsaturated carboxylic acid, and the remaining substituent of at least a part of the substituent of the unsaturated carboxylic acid is a divalent metal Crosslinked, wherein the glove does not contain sulfur as a crosslinking agent and a sulfur compound as a vulcanization accelerator, and is crosslinked by a bond formed by a substituent of at least a part of the aforementioned unsaturated carboxylic acid. The elastomer has a Mui viscosity (ML ₍₁₊₄₎ (100 ° C)) of 100 to 220, a thickness of 0.05 to 0.15 mm, a glove swelling ratio of 240 to 320% when the glove is formed, and a tensile stress of 22 to 35 MPa. The elongation at break is 480 to 620%, and the tensile stress at 500% elongation is 15 to 35 MPa. Both sides of the inner surface and the outer surface are treated with chlorine, and the surface contact with the glove user's hand does not have Adhesive state, on the other hand, the surface in contact with the material during operation is flat , As a metal or metal salt by dissolution process of impurities contained, stand for 1 hour so that the dissolution of the total amount of Na and K is less 3.9μg in water, the content of the metal contained in the metal salt or anionic reduced. The glove according to claim 1, wherein the metal or metal salt contained as the impurity is Na, K, Ca or Zn. The glove of claim 1, wherein the anion is Chloride. A glove formed from an elastomer composition comprising an elastomer comprising 25 to 30% by weight of acrylonitrile, 62 to 71% by weight of butadiene and 4 to 8% by weight of unsaturated carboxylic acid (all 100) % by weight, and crosslinked by a bond formed by a substituent of at least a part of the aforementioned unsaturated carboxylic acid, and the remaining substituent of at least a part of the substituent of the unsaturated carboxylic acid is a divalent metal Crosslinked, wherein the glove does not contain sulfur as a crosslinking agent and a sulfur compound as a vulcanization accelerator, and is crosslinked by a bond formed by a substituent of at least a part of the aforementioned unsaturated carboxylic acid The elastomer has a Mui viscosity (ML ₍₁₊₄₎ (100 ° C)) of 100 to 220, a thickness of 0.05 to 0.15 mm, a glove swelling ratio of 240 to 320 when the glove is formed, and a tensile stress of 22 to 35 MPa. The elongation at break is 480 to 620%, and the tensile stress at 500% elongation is 15 to 35 MPa, and the surface in contact with the glove user's hand is chlorinated to be non-adhesive. The surface in contact with the substance during the operation is treated with chlorine in a chlorination vessel to form The smooth surface, the metal or the metal salt contained as an impurity is subjected to a dissolution treatment, and the total amount of Na and K eluted in the water for one hour is 3.9 μg or less, and the content of the contained metal, metal salt or anion is reduced; The glove is formed by the steps comprising the steps of: (a) washing the mold or molding die and drying, and (b) immersing the mold or molding die with 8 to 17% by weight of Ca ²⁺ ions. a step in the coagulant solution, (c) a step of drying the mold or mold to which the coagulant is attached at 50 to 70 ° C, (d) the above step (c) at a temperature of 25 to 35 ° C a mold or mold having a coagulant attached thereto, a step of immersing in the elastomer composition for 1 to 20 seconds, and (e) a mold having an elastomer composition adhered to the surface of the step (d) a step of washing a mold or a mold to remove a chemical (leaching), (f) a round edge (curl processing) step, and (g) an elastic body attached to a surface of a mold or a molding die at 80 to 120 ° C The composition is dried for 250 to 300 seconds, (h) the aforementioned dried elastomer composition is at 120 to 150 ° C a step of hardening for crosslinking for 20 to 30 minutes, (i) a step of drying after the film of the elastomer composition obtained in the above step (h) is subjected to post-leaching, (j) After the chlorine treatment of the surface of the film after the step (i), the step of neutralizing, (k) the step of washing and drying the film obtained in the above step (j), (1) the film a step of peeling off from a mold or a molding die, and inverting, (m) a step of chlorine-treating the inverted glove, and (n) washing the above-mentioned (m) step with pure water, and chlorinating the outside Gloves and drying steps. A glove formed from an elastomer composition comprising an elastomer comprising 25 to 30% by weight of acrylonitrile, 62 to 71% by weight of butadiene, and 4 to 8% by weight of unsaturated carboxylic acid (all 100) % by weight), and contains crosslinks formed by reactive vinyl compounds and crosslinks formed by divalent metal ions, free of sulfur as a crosslinking agent and sulfur compounds as a vulcanization accelerator, and reacted by The cross-linked Mooney viscosity (ML ₍₁₊₄₎ (100 ° C)) formed by the vinyl compound is 100 to 220; wherein both sides of the inner surface and the outer surface are treated with chlorine to allow to stand in water The total amount of Na and K eluted in one hour was 3.9 μg or less. A glove formed from an elastomer composition comprising an elastomer comprising 25 to 30% by weight of acrylonitrile, 62 to 71% by weight of butadiene, and 4 to 8% by weight of unsaturated carboxylic acid (all 100) And % by weight, and comprises cross-linking formed by a reactive vinyl compound and cross-linking formed by a divalent metal ion, containing no sulfur as a crosslinking agent and a sulfur compound as a vulcanization accelerator, and The crosslinked Mooney viscosity (ML ₍₁₊₄₎ (100 ° C)) formed by the reactive vinyl compound is 100 to 220; wherein both sides of the inner surface and the outer surface are treated with chlorine, so that The total amount of Na and K dissolved in water for 1 hour is 3.9 μg or less, and the glove is formed through a step comprising the steps of: (a) washing the mold or molding die and drying, (b) a step of immersing a mold or a molding die in a coagulant solution containing 8 to 17% by weight of Ca ²⁺ ions, (c) a step of drying a mold or a mold to which a coagulant is attached at 50 to 70 ° C, (d) molding or molding the coagulant obtained in the above step (c) at a temperature of 25 to 35 ° C a step of immersing in the above-mentioned elastomer composition for 1 to 20 seconds, (e) a mold or a molding die to which an elastomer composition is adhered on the surface of the above step (d), followed by water washing to remove the drug (leaching) Step, (f) a round edge (curl edge processing) step, (g) drying the aforementioned elastomer composition attached to the surface of the mold or the molding die at 80 to 120 ° C for 250 to 300 seconds, (h) The above-mentioned dried elastomer composition is subjected to a step of curing at 120 to 150 ° C for 20 to 30 minutes for crosslinking, and (i) consisting of the elastomer composition obtained in the above step (h). After the film is subjected to post-leaching, the step of drying is carried out, (j) the step of neutralizing the surface of the film after the step (i) is subjected to a chlorine treatment, and (k) the step obtained in the above step (j) a step of washing and drying the film, (1) a step of peeling the film from the mold or the molding die, and a step of inverting, (m) a step of chlorine-treating the inverted glove, and (n) a pure water The step of the chlorination of the outer side obtained in the above step (m) and drying is carried out. The glove according to claim 1 or 5, wherein the chlorine treatment on the outer surface is carried out by immersing in an aqueous solution having a chlorine concentration of 30 ppm to 180 ppm. The glove according to claim 4, wherein the chlorine treatment in the step (m) is carried out by immersing in an aqueous solution having a chlorine concentration of 30 ppm to 180 ppm. The glove according to the first, fourth, fifth or sixth aspect of the invention, wherein the amount of Cl dissolved in water for one hour is 6.3 μg or less. The glove according to any one of the above-mentioned claims, wherein the total amount of Na, K, Ca, Zn and Cl dissolved in water for one hour is 40.5 μg or less. A glove as claimed in claim 1, 4, 5 or 6 is attached to a clean room user. A method of making a glove formed from an elastomer composition comprising an elastomer comprising 25 to 30% by weight of acrylonitrile, 62 to 71% by weight of butadiene, and 4 to 8 parts by weight of unsaturated carboxylic acid. % (100% by weight in total), and crosslinked by a bond formed by a substituent of at least a part of the aforementioned unsaturated carboxylic acid, and the remaining substituent of at least a part of the substituent of the unsaturated carboxylic acid is Crosslinked by a divalent metal, and the glove does not contain sulfur as a crosslinking agent and a sulfur compound as a vulcanization accelerator, and the glove is produced by the following steps: (a) washing the mold or molding die and a step of drying, (b) a step of immersing a mold or a molding die in a coagulant solution containing 8 to 17% by weight of Ca ²⁺ ions, and (c) attaching a coagulant at 50 to 70 ° C a step of drying a mold or a mold, (d) immersing the mold or mold having the coagulant obtained in the above step (c) at a temperature of 25 to 35 ° C, in the above elastomer composition a step of 1 to 20 seconds, (e) an elastomer group attached to the surface of the aforementioned step (d) a step of washing a plastic mold or a mold to remove a chemical (leaching), (f) a round edge (curl processing) step, and (g) attaching the foregoing to a mold or a molding die at 80 to 120 ° C The step of drying the surface elastomer composition for 250 to 300 seconds, (h) treating the dried elastomer composition after the treatment at 120 to 150 ° C for 20 to 30 minutes for crosslinking and hardening, (i) After the film composed of the elastomer composition obtained in the above step (h) is subjected to post-leaching, the step of drying is carried out, (j) after the surface of the film after the step (i) is subjected to chlorine treatment, a step of performing a neutralization treatment, (k) a step of washing and drying the film obtained in the above step (j), (1) a step of peeling off the film from a mold or a molding die, and inverting, (m) The step of subjecting the inverted glove to chlorine treatment, and (n) washing the step obtained in the above (m) step with pure water, and then chlorinating the glove on the outside and drying.