JP2011032590A - Method for producing rubber glove, and rubber glove - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a rubber glove comprising using environmentally-friendly latex made of chlorosulfonated polyethylene (CSM) excellent in chemical resistance to produce a rubber glove having even thickness as much as possible: and to provide a rubber glove having even thickness produced by the method. <P>SOLUTION: The method comprises a process for making the CSM latex thermosensitive, soaking a heated hand mold corresponding to the three-dimensional shape of the rubber glove in the latex, and pulling up the hand mold from the latex followed by drying the hand mold, so as to form the CSM coating film on the surface of the hand mold. The rubber glove is produced by the method, and is favorably used for protecting the hand of a worker from chemical substance treated particularly in chemical factories and the like where the chemical substance is treated because the rubber glove has no fear of reduction in workability due to enlargement of the thickness of its finger tips, and/or reduction in chemical resistance due to reduction in the thickness of its palm part and/or its back part. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a rubber glove manufacturing method and a rubber glove manufactured by the manufacturing method.

The so-called non-support type rubber gloves consisting entirely of thin rubber or resin film, or the so-called support type rubber gloves where the rubber film is reinforced with fiber knitted gloves It is widely used not only in the medical field but also in various industries.
For example, in chemical factories that handle chemical substances, rubber gloves are used to protect workers' hands from the chemical substances they handle. The rubber gloves used for the above-described applications are required to have high chemical resistance that is not eroded by a high concentration of strong acid, strong alkali, or organic solvent. In order to satisfy this requirement, for example, the entire rubber glove may be formed of rubber or resin having excellent chemical resistance, or at least the outermost layer of the rubber glove may be formed of the rubber or resin.

In Patent Document 1, the outermost layer of the rubber glove is made of chlorosulfonated polyethylene (CSM) which has excellent chemical resistance, weather resistance, ozone resistance, heat resistance, etc. because it does not contain a double bond in the main chain. In other words, it describes that a rubber glove formed by a so-called dipping method and having a laminated structure of the outermost layer and a base layer underneath is excellent in chemical resistance.
However, in the invention described in Patent Document 1, a solution in which the CSM is dissolved in a large amount of an organic solvent is used as the liquid composition containing the CSM. For example, in Example 1 of Patent Document 1, 350 parts by mass of an organic solvent per 100 parts by mass of CSM is added to prepare the solution.

Therefore, the manufacturing method described in Patent Document 1 has a problem that the load on the environment is large.
That is, the organic solvent is removed by vaporization in the drying step after lifting the hand mold from the solution as described above, but if the removed organic solvent is directly diffused into the atmosphere, air pollution, Causes environmental pollution.

  Further, even if the organic solvent is burned and decomposed, carbon dioxide, which is a greenhouse gas, or air pollutants may be generated. Even if the adsorbent is adsorbed, environmental pollution may occur when the adsorbent is discarded.

JP-A-5-230702

  An object of the present invention is a method of manufacturing a rubber glove excellent in chemical resistance, weather resistance, ozone resistance, heat resistance, etc., and having a low environmental load, and the manufacturing method described above. An object of the present invention is to provide a rubber glove having a uniform thickness and excellent chemical resistance, weather resistance, ozone resistance, heat resistance and the like.

The inventor examined the use of CSM latex in which the CSM was colloidally dispersed in water by the action of an emulsifier as the liquid composition for the dipping method.
However, a normal film cannot be formed even if rubber gloves are formed by a dipping method using CSM latex.
This may be because the CSM latex adhered to the surface of the hand mold by the dipping method flows until it is dried.

Even if a coagulant such as calcium nitrate is applied to the surface of the hand mold before dipping in latex, the flow cannot be suppressed, and it is still difficult to form a normal film.
Therefore, as a result of further study, the inventor found that a pre-heated hand mold was immersed in a heat-sensitive CSM latex and then pulled up, and then the CSM in the latex was adhered to the surface of the hand mold in a solidified state to form a normal film. The present invention has been completed.

  That is, the present invention is a manufacturing method for producing a rubber glove by forming at least a CSM film on a surface of a hand mold corresponding to the three-dimensional shape of the rubber glove, and then removing the mold to heat-sensitize the latex of the CSM. A method of manufacturing a rubber glove comprising the step of forming the CSM film on the surface of the hand mold by immersing the heated hand mold in latex, pulling it up and drying it.

According to the present invention, the CSM in the latex can be adhered in a coagulated state to the surface of the hand mold by immersing the pre-heated hand mold in the heat-sensitive CSM latex as described above and then pulling it up. it can. Therefore, after the pulling up, it is possible to manufacture a rubber glove having a uniform thickness as much as possible by suppressing the flow of latex before drying.
In addition, according to the production method of the present invention, since the latex in which CSM is colloidally dispersed in water is used, the burden on the environment can be reduced.

  The rubber glove manufactured according to the present invention may have only the CSM film, or may have a laminated structure in which the CSM film and another rubber or resin film are laminated. . In order to manufacture the latter rubber gloves having a laminated structure by the manufacturing method of the present invention, at least one time before and after forming the CSM film on the surface of the hand mold, rubber or resin other than the CSM The film and the CSM film may be laminated by forming the film.

  Further, the rubber glove produced according to the present invention may be a non-support type consisting only of a rubber or resin film including the CSM film, or a support type in which the film is reinforced with a fiber knitted glove. Also good. In order to manufacture the latter type of support type rubber gloves by the manufacturing method of the present invention, a film including at least the CSM film is formed on the surface of the hand mold in a state in which a fiber knitted glove is previously attached. By doing so, the film and the knitted glove may be integrated.

  In order to heat-sensitize the latex of CSM, at least one selected from the group consisting of polyvinyl methyl ether, polyalkylene glycol, polyether polyol, and sensitive polysiloxane is added to the latex as a heat-sensitive agent. preferable. The polyvinyl methyl ether is particularly excellent in the function of heat-sensing CSM latex, and by using the polyvinyl methyl ether as a heat-sensitive agent, the thickness of rubber gloves can be made even more uniform.

  Since the rubber glove of the present invention is manufactured by the manufacturing method of the present invention, it is provided with a film having a uniform thickness made of CSM. Therefore, the rubber glove of the present invention is excellent in chemical resistance, weather resistance, ozone resistance, heat resistance and the like.

  According to the present invention, a rubber glove manufacturing method having excellent chemical resistance, weather resistance, ozone resistance, heat resistance, etc., and a method for manufacturing a rubber glove having a small environmental load, and the manufacturing method described above, A rubber glove having a uniform thickness and excellent chemical resistance, weather resistance, ozone resistance, heat resistance and the like can be provided.

<Method of manufacturing rubber gloves>
The method for producing a rubber glove of the present invention includes the step of forming a CSM film on the surface of the hand mold by heat-sensitizing the latex of CSM, dipping the heated hand mold, and then drying it. It is characterized by.
The CSM (Chlorosulfonated Polyethylene) is made by introducing 25% or more and 45% or less chlorine and about 1% sulfur into polyethylene, and has both the properties as an elastomer and the vulcanization properties, and the main chain. It is a generic name for polymers that have excellent chemical resistance, weather resistance, ozone resistance, heat resistance, etc. because they do not contain double bonds (according to the classification of ASTM D1418 of the American Society for Testing Materials).

The CSM latex is a latex in which the CSM is colloidally dispersed in water by the action of an emulsifier. The solid content concentration of the latex, that is, the content ratio of CSM is preferably 30% by mass or more and 60% by mass or less.
If the solid content concentration is less than the above range, the thickness of the film formed on the surface of the hand mold is too small by immersing the hand mold once in latex and then drying it to form a film with the required thickness. For this reason, the steps of dipping, pulling up and drying must be repeated twice or more, which may reduce the productivity of rubber gloves. Further, as the above process is repeated, there is a possibility that non-uniform thickness due to latex flow tends to occur.

Moreover, when solid content concentration exceeds the said range, there exists a possibility that latex cannot be maintained stably.
As the latex of CSM, for example, CSM-450 manufactured by Sumitomo Seika Co., Ltd. [white aqueous liquid, solid content concentration: 40% by mass, pH: 2.5, specific gravity: 1.03, viscosity: 15 mPa · s, average Particle size 1.2 μm, emulsifier: anionic interfacial lubricant], and CSM-200 [white aqueous liquid, solid content concentration: 40 mass%, pH: 2.5, specific gravity: 1.05, viscosity: 70 mPa · s , Average particle diameter of 2.5 μm, emulsifier: anionic interfacial lubricant].

In order to give the latex a function of heat-sensitizing, that is, coagulating CSM dispersed in the latex when heated to a certain temperature or higher, a heat-sensitive agent is blended.
Examples of the heat-sensitive agent include polyvinyl methyl ether, zinc ammonium complex salt, polyalkylene glycol, polyether polyol, and sensitive polysiloxane. Among these, polyvinyl methyl ether, polyalkylene glycol, polyether polyol, and sensitive At least one selected from the group consisting of polysiloxanes is preferred.

Among them, polyvinyl methyl ether is particularly excellent in the function of heat-sensitizing CSM latex, and the use of the polyvinyl methyl ether can make the thickness of rubber gloves even more uniform.
Examples of the heat-sensitive agent containing polyvinyl methyl ether include Lutnar (registered trademark) M40 (concentration of polyvinyl methyl ether as an active ingredient of 10% by mass) manufactured by BASF.

The blending ratio of the heat-sensitive agent is preferably 0.1 parts by mass or more and 5 parts by mass or less, particularly 0.5 parts by mass or more and 3 parts by mass or less per 100 parts by mass of the solid in the latex.
If the blending ratio is less than the above range, the effect of blending the heat-sensitive agent may not be sufficiently obtained. That is, the CSM in the latex cannot be adhered to the surface of the hand mold in a sufficiently solidified state, and the latex easily flows after being pulled out of the latex and then dried. The thickness may not be sufficiently uniform. In addition, the thickness of the film formed on the surface of the hand mold is too small by immersing the hand mold once in latex and then drying it, so that the film is formed with the necessary thickness. The process of drying and drying must be repeated twice or more, and the productivity of rubber gloves may be reduced.

Moreover, even if the blending ratio exceeds the above range, not only the effect is not obtained, but also the viscosity of the latex rises and it becomes difficult to control the film thickness of the film, and it is difficult to prevent the mixing of bubbles. There is a fear.
The blending ratio of the heat-sensitive agent is the blending ratio of the active ingredient in the heat-sensitive agent. For example, in the case of Lutonal M40, the total blending amount is set so that the blending ratio of polyvinyl methyl ether as an active ingredient per 100 parts by mass of CSM is within the above range.

The CSM latex may further contain stabilizers and other additives as necessary.
The hand mold may be the same as the conventional one. That is, as the hand mold, a hand mold corresponding to the three-dimensional shape of the rubber glove to be manufactured, which is integrally formed of ceramic, ceramic, or metal (aluminum or the like) can be used.

The surface of the hand mold can be formed with irregularities so as to provide an irregular pattern for preventing slippage on the surface and the back surface of the rubber glove to be manufactured, or can be finished on a satin surface to finish the surface and the back surface with a matte finish. The ceramic hand mold may be an unglazed hand mold or a glazed hand mold.
(Manufacturing method of single layer non-support type rubber gloves)
When producing a non-support type rubber glove having a single-layer CSM film by the production method of the present invention, the hand mold is first heated to a predetermined temperature. The heating temperature is preferably 40 ° C. or higher and 80 ° C. or lower, particularly 50 ° C. or higher and 70 ° C. or lower when expressed by the surface temperature of the hand mold.

If the heating temperature is less than the above range, the CSM latex cannot be sufficiently coagulated, and the film may not be obtained normally.
Moreover, when the temperature of heating exceeds the said range, it is easy to produce defects, such as a coagulum, in latex.
Next, the heated hand mold is immersed in the heat-sensitive CSM latex as described above at a constant speed as much as possible, and maintained for a certain period of time (standing), then pulled up at a constant speed as much as possible. Dry and vulcanize the CSM.

Drying is preferably performed under heating. Thereby, the latex adhered to the surface of the hand mold is solidified in a short time to prevent the flow, and a rubber glove having a more uniform thickness can be manufactured.
The heating conditions differ depending on the film thickness of the rubber glove to be formed, but the heating temperature is shorter than that of a rubber glove that is uniform in thickness and sufficiently vulcanized with CSM and excellent in strength and chemical resistance. Considering efficient production in time, it is preferably 100 ° C. or higher and 120 ° C. or lower. For the same reason, the heating time is preferably 20 minutes or longer and 60 minutes or shorter.

When the dried film is removed from the hand mold, a non-support type rubber glove having a single-layer film of CSM is obtained.
The thickness of the CSM film forming the single-layer non-support type rubber gloves is preferably 0.1 mm or more and 2.0 mm or less, particularly 0.3 mm or more and 1.0 mm or less.
If the thickness of the film is less than the above range, the chemical resistance of the rubber gloves may be insufficient. Moreover, when exceeding the said range, there exists a possibility that the workability | operativity of the operation | work which mounted | wore the rubber glove may fall. In addition, the production cost of rubber gloves may be high.

(Manufacturing method of non-support type rubber gloves having laminated structure)
In order to manufacture a non-support type rubber glove having a laminated structure of a CSM film and a rubber or resin film other than the CSM by the manufacturing method of the present invention, the CSM film described above is formed. The other film may be formed on the surface of the hand mold at at least one time point before and after the process.

For example, on the surface of the hand mold, first, the other film is formed by various conventionally known forming methods, and then the heated hand mold is immersed in a heat-sensitive CSM latex and allowed to stand for a certain period of time, then pulled up, By drying and laminating the CSM film on the other film and then removing the film, a non-support type rubber glove having the laminated structure can be manufactured.
On the other hand, the heated hand mold is immersed in a heat-sensitive CSM latex, allowed to stand for a certain period of time, pulled up and dried to form a CSM film, and then another film is formed by various conventionally known forming methods. A non-support type rubber glove having the above-mentioned laminated structure can be manufactured even if it is laminated after being laminated on the CSM film.

Further, by repeating the above-described lamination step, a non-support type rubber glove having, for example, a laminated structure of three or more layers and at least one of which is a CSM film can be manufactured.
In order to impart chemical resistance to the coated rubber glove, it is preferable to place a CSM film on at least the outermost layer of the rubber glove. For that purpose, the order of formation of each film may be set so that the CSM film is positioned on the outermost layer of the rubber glove, or demolding and subsequent processing may be set.

  For example, in the case of a non-support type rubber glove in which the two-layered film (CSM film and other film) described above is laminated, the one in which the CSM film is laminated on the outside is, for example, air between the hand mold. The CSM film can be located on the outermost layer by removing the mold while maintaining the laminated state by blowing or the like. Further, the CSM film can be positioned on the outermost surface layer even if the front and back surfaces are reversed again after demolding while reversing the front and back surfaces.

  In addition, among the two-layer structure non-support type rubber gloves, the CSM film laminated on the inner side can be placed on the outermost layer by removing the mold while inverting the front and back. it can. Further, the CSM film can be positioned on the outermost layer even if the front and back surfaces are reversed after releasing the mold while maintaining the laminated state by blowing air or the like between it and the hand mold.

The same applies to a rubber glove having a multilayer structure of three or more layers. The CSM film can be positioned on the outermost layer by combining the order of forming each film and the processes such as demolding and reversal.
The conditions for forming the CSM film by the dipping method are the same as those for the single-layer non-support type rubber gloves.
Examples of other rubbers or resins forming other films laminated with the CSM film include natural rubber, deproteinized natural rubber, acrylonitrile butadiene rubber (NBR), and chloroprene rubber (CR).

The other film can be formed by an arbitrary forming method, but it is preferable to form the other film by an immersion method using latexes of various rubbers, particularly in consideration of reducing the load on the environment. In the latex used in the dipping method, any additive such as a stabilizer, a vulcanizing agent, a vulcanization accelerator, a filler, a pigment, and the like can be blended depending on the type of rubber or resin.
The conditions of the dipping method can be arbitrarily set. The thickness of the other film can also be set arbitrarily.

The thickness of the CSM film may be about the same as that of the single-layer rubber gloves.
However, since the thickness of the rubber glove can be ensured by laminating the other film, the thickness of the CSM film is within the above range, or depending on the level of chemical resistance required for the rubber glove. It may be smaller than the range. In particular, the total thickness of the other films and the CSM film is preferably set to be approximately equal to the thickness of the previous single-layer film. In that case, the productivity of rubber gloves can be improved and the cost can be reduced by selecting a general-purpose rubber or resin for forming another film.

When another film is first formed on the surface of the hand mold by a dipping method, and then a CSM film is laminated thereon, a coagulant is attached to the surface of the hand mold before forming the other film. May be.
Examples of the coagulant include metal salts such as calcium nitrate, aluminum chloride, zinc chloride, calcium chloride, and zinc acetate, and organic acids such as formic acid and acetic acid. The hand mold can be attached to the surface of the hand mold by immersing the hand mold in a coagulation liquid obtained by dissolving the coagulant in a solvent such as water or alcohol, allowing the mold to stand for a certain period of time, and lifting and drying.

Moreover, the latex which becomes the basis of another film may be heat-sensitized, and the heated hand mold may be immersed.
(Manufacturing method of support type rubber gloves)
In order to manufacture a support-type rubber glove in which a knitted glove and a film including at least the CSM film are integrated by the manufacturing method of the present invention, first, a fiber knitted fabric is first formed on the surface of the hand mold. Wear gloves.

And, when the film is a single layer of only the CSM film, the heated hand mold is immersed in the heat-sensitive CSM latex as in the case of the single-layer non-support type rubber gloves. The support-type rubber glove can be manufactured by leaving it for a certain period of time, pulling it up, drying it, integrating the CSM film with the knitted glove and then removing the mold.
If the film is a laminated structure of CSM film and other film, the support type rubber is formed by sequentially laminating the film on the surface of the hand mold and integrating it with the knitted glove. Gloves can be manufactured.

However, for support type rubber gloves, the knitted glove needs to be located in the innermost layer, and the rubber glove manufactured through the above process cannot reverse the front and back. A CSM film must be formed.
For example, when the film has a two-layer structure consisting of another film and a CSM film, the other film is first formed on the surface of the hand mold on which the knitted glove is worn, and then the film and the knitted glove are integrated. The heated hand mold is immersed in a heat-sensitive CSM latex, allowed to stand for a certain period of time, lifted and dried, and then the CSM film is laminated on the other film, and then demolded. Rubber gloves can be manufactured.

The conditions for forming the CSM film by the dipping method and the conditions for forming other films are the same as those for the non-support type rubber gloves.
When the film to be integrated with the knitted glove is a single layer made of only a CSM film, the thickness of the film may be the same as that of a single layer non-support type rubber glove.
Moreover, when the said film | membrane is the laminated structure of another film | membrane and the film | membrane of CSM, the thickness of each film | membrane can be set similarly to the case of the non-support type rubber glove which has a laminated structure.

As the knitted gloves, seamless knitted gloves and knitted knitted gloves obtained by knitting fibers such as cotton, nylon, and polyester are preferable.
<Rubber gloves>
Since the rubber glove of the present invention manufactured by the manufacturing method includes at least a CSM film having a uniform thickness, particularly in a chemical factory that handles chemical substances, the operator's hands are protected from the chemical substances handled. Can be suitably used.

The rubber gloves of the following examples and comparative examples were produced in an environment of a temperature of 23 ± 1 ° C. and a relative humidity of 55%. Therefore, the temperature of the hand mold and the like other than those specially specified was 23 ± 1 ° C.
<Example 1>
(Preparation of heat-sensitive CSM latex)
Latex of CSM [CSM-200 manufactured by Sumitomo Seika Co., Ltd., white aqueous liquid, solid content concentration: 40% by mass, pH: 2.5, specific gravity: 1.05, viscosity: 70 mPa · s, average A heat-sensitive agent (Lutneral M40 manufactured by BASF, Inc., concentration of polyvinyl methyl ether as an active ingredient of 10% by mass) was added to a particle size of 2.5 μm and an emulsifier: an anionic interfacial slipping agent to make it heat sensitive. . The blending ratio of the heat-sensitive agent was set so that the blending ratio of the two components was 1 part by mass of polyvinyl methyl ether in Lutnar M40 per 100 parts by mass of CSM in the latex.

(Manufacture of rubber gloves)
As a hand mold, a ceramic product was used. After heating the hand mold in an oven at 100 ° C. for 15 minutes, the heated hand mold immediately after taking out from the oven was kept at a liquid temperature of 20 ° C. It is immersed in the heat-sensitive CSM latex at a constant speed, left to stand for 1 minute, then pulled up at a constant speed, and then heated in an oven at 100 ° C. for 60 minutes to dry the latex and vulcanize the CSM. Thereafter, the mold was removed to produce a single-layer non-support type rubber glove made of a CSM film.

<Example 2>
(Preparation of natural rubber latex for immersion method)
Commercially available natural rubber latex, 0.5 parts by mass of oleic acid as a stabilizer, 0.5 parts by mass of potassium hydroxide and 1 mass of sulfur as a vulcanizing agent per 100 parts by mass of the solid content in the natural rubber latex 1 part by weight, vulcanization accelerator [Nouchira (registered trademark) BZ made by Ouchi Shinsei Chemical Co., Ltd.], anti-aging agent (Nocrack (registered trademark) PBK made by Ouchi Shinsei Chemical Industries) 1 A latex for the dipping method was prepared by blending 2 parts by mass of titanium oxide as a filler with a mass part.

(Manufacture of rubber gloves)
The same ceramic hand mold used in Example 1 was first dipped in a 45% calcium nitrate aqueous solution, pulled up and dried to attach calcium nitrate as a coagulant to the surface of the hand mold.
Next, the unheated hand mold is dipped in the natural rubber latex for dipping method at a constant temperature of 20 ° C. and left to stand for 15 seconds, then pulled up at a constant rate, and then 100 ° C. In the oven for 15 minutes to dry the latex and vulcanize the natural rubber.

  Next, the heated hand mold immediately after taking out from the oven is immersed in the heat-sensitive CSM latex kept at a liquid temperature of 20 ° C. at a constant speed and allowed to stand for 30 seconds, and then pulled up at a constant speed. Next, it is heated in an oven at 100 ° C. for 60 minutes to dry the latex and vulcanize the CSM, and then demold, to form a non-support type having a laminated structure of a natural rubber film and a CSM film. Rubber gloves were manufactured.

<Example 3>
A natural rubber film is formed by the dipping method and integrated with the knitted glove under the same conditions as in Example 2 except that a cotton knitted glove is attached to the same ceramic hand mold used in Example 1. Further, a support type rubber glove was manufactured by laminating a CSM film on the natural rubber film.

<Comparative example 1>
The same ceramic hand mold used in Example 1 was first dipped in a 45% calcium nitrate aqueous solution, pulled up and dried to attach calcium nitrate as a coagulant to the surface of the hand mold.
Next, the unheated hand mold was kept constant in a CSM latex (CSM-200 manufactured by Sumitomo Seika Co., Ltd.) with a liquid temperature maintained at 20 ° C. and not containing a heat-sensitive agent. When it was immersed at a speed and allowed to stand for 30 seconds and then pulled up at a constant speed, the latex flowed and a normal film could not be formed on the surface of the hand mold. Therefore, we gave up the production of rubber gloves.

<Comparative example 2>
The same ceramic hand mold used in Example 1 was first dipped in a 30% calcium nitrate aqueous solution, pulled up and dried to attach calcium nitrate as a coagulant to the surface of the hand mold.
Next, the hand mold that was not heated was immersed in a natural rubber latex for the same dipping method as used in Example 2 at a liquid temperature of 20 ° C. and allowed to stand for 15 seconds. Pull up at a constant speed, then heat in an oven at 100 ° C. for 60 minutes to dry the latex, vulcanize the natural rubber, and then demold to make a single layer non-support type rubber made of natural rubber film Gloves were manufactured.

<Comparative Example 3>
(Preparation of NBR latex for immersion method)
Commercially available NBR latex [LX552 manufactured by Nippon Zeon Co., Ltd.] per 100 parts by mass of the solid content in the NBR latex, 0.5 parts by mass of surfactant, 1 part by mass of sulfur as a vulcanizing agent, vulcanization Accelerator [Noxeller (registered trademark) BZ manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.] 1 part by weight, 1 part by weight of zinc oxide, and 2 parts by weight of titanium oxide as a filler are mixed to form a latex for dipping method. Prepared.

(Manufacture of rubber gloves)
The same ceramic hand mold used in Example 1 was first dipped in a 45% calcium nitrate aqueous solution, pulled up and dried to attach calcium nitrate as a coagulant to the surface of the hand mold.
Next, the unheated hand mold is immersed in the NBR latex for dipping method at a constant temperature, kept at a liquid temperature of 20 ° C., allowed to stand for 30 seconds, then pulled up at a constant rate, and then 100 ° C. In the oven, the latex was dried for 60 minutes, and NBR was vulcanized and then demolded to produce a single-layer non-support type rubber glove composed of an NBR film.

<Comparative example 4>
(Preparation of CR latex for immersion method)
To a commercially available CR latex (Neoprene (registered trademark) 671A manufactured by DuPont) per 100 parts by mass of the solid content in the NBR latex, 0.5 parts by mass of a surfactant, 1 part by mass of sulfur as a vulcanizing agent, Vulcanization accelerator (Nouchira (registered trademark) BZ manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.) 1 part by mass, 1 part by mass of zinc oxide, and 2 parts by mass of titanium oxide as a filler are used for the dipping method. A latex was prepared.

(Manufacture of rubber gloves)
The same ceramic hand mold used in Example 1 was first immersed in a 35% calcium nitrate aqueous solution, pulled up, and dried to allow calcium nitrate as a coagulant to adhere to the surface of the hand mold.
Next, the unheated hand mold is immersed in the CR latex for immersion method at a constant temperature, kept at a liquid temperature of 20 ° C., allowed to stand for 30 seconds, then pulled up at a constant rate, and then 100 ° C. The latex was dried in an oven for 60 minutes to dry the latex, and the CR was vulcanized and then demolded to produce a single-layer non-support type rubber glove composed of a CR film.

<Chemical resistance evaluation>
For the rubber gloves produced in the examples and comparative examples, the time (minutes) until the target chemical substance is detected at 8 ppm or more is obtained by chemical permeation evaluation according to the European standard EN374. The longer the is, the better the chemical resistance against the corresponding chemical substance. Moreover, the test was performed over 480 minutes, and what was not detected more than 8 ppm of the target chemical substance after 480 minutes is described as “> 480” in the table.

As target chemical substances, 35% hydrochloric acid, 96% sulfuric acid, 99% acetic acid, 50% aqueous sodium hydroxide and 34% hydrogen peroxide were used.
The results are shown in Table 1.

From Table 1, in Comparative Example 1 in which the CSM film was formed by the conventional method using a coagulant, the latex flowed as described above, and a normal film was formed on the surface of the hand mold. Gloves could not be manufactured. Therefore, chemical resistance evaluation was not performed.
It was also found that the rubber gloves of Comparative Examples 2 to 4 using natural rubber, NBR, and CR instead of CSM have insufficient chemical resistance.

  On the other hand, it was confirmed that the rubber gloves of Examples 1 to 3 manufactured by the manufacturing method of the present invention are all excellent in chemical resistance.

Claims (5)

  A manufacturing method for producing a rubber glove by forming at least a chlorosulfonated polyethylene film on a hand-shaped surface corresponding to a three-dimensional shape of a rubber glove, and then removing the mold to heat-sensitize the latex of the chlorosulfonated polyethylene. A method for producing a rubber glove comprising the step of forming a film of the chlorosulfonated polyethylene on the surface of the hand mold by immersing and lifting the hand mold heated in the latex and then drying it .   By forming a film of rubber or resin other than the chlorosulfonated polyethylene on at least one time before and after forming the chlorosulfonated polyethylene film on the surface of the hand mold, the film and the chlorosulfonated The manufacturing method of the rubber glove of Claim 1 which laminates | stacks with the membrane | film | coat of polyethylene.   2. The film and the knitted glove are integrated by forming a film containing at least the chlorosulfonated polyethylene film on the surface of the hand mold with a fiber knitted glove attached in advance. Or the manufacturing method of the rubber glove of 2.   The method for producing a rubber glove according to any one of claims 1 to 3, wherein the latex of the chlorosulfonated polyethylene is heat-sensitized by adding polyvinyl methyl ether as a heat-sensitive agent.   A rubber glove manufactured by the manufacturing method according to any one of claims 1 to 4.