JPH11269708A - Glove - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a glove easy to put on/off, with feeling when worn not running unfavorable even in case the inside of the glove gets wet, by laminating the inner surface of rubber or resin base layer(s) with a collagen-contg. rubber or resin lubricating layer. SOLUTION: This glove is obtained by laminating the inner surface of a glove provided with at least one rubber or resin base layer with a collagen- contg. rubber or resin lubricating layer; wherein the content of the collagen is pref. 30 pts.wt. based on 100 pts.wt. of the rubber or resin; when inorganic or resinous fine particles are also to be incorporated in the lubricating layer the content of the fine particles is <=130 pts.wt. based on 100 pts.wt. of the rubber or resin and the total content of the collagen and fine particles is set at <=200 pts.wt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to rubber or resin gloves.

[0002]

2. Description of the Related Art Conventionally, so-called rubber gloves (rubber or soft resin gloves) widely used in homes and the like include an unsupported rubber glove made of at least one rubber or resin base layer. There are known gloves of the support type and gloves of the support type in which the base layer is reinforced with a thin cloth glove body.

In addition, these conventional gloves are formed in a fixed shape and size without considering the size and shape of the user's hand in consideration of versatility, and are not suitable for fine work. As an alternative glove suitable for particularly fine work, a glove in which a base layer is formed of an extensible film so as to fit snugly in a user's hand has been proposed (JP-A-5-247704, etc.). ).

[0004] However, the above-mentioned stretchable gloves, in particular, enhance the fit to the wearer's hand, but are difficult to put on and take off, and sweat on the hand while wearing the glove or water that is handled with gloves. However, there is a problem that if the glove is accidentally put into the glove and the inside of the glove gets wet, the feeling of wearing is deteriorated. Such a problem has also occurred with conventional gloves such as the unsupported type.

[0005]

Therefore, in order to improve the lubricity of the glove to the hand and make it easy to put on and take off, a glove provided with a layer (lubricating layer) having a high lubricity to the hand on its inner surface has been proposed. Was done. For example, Japanese Patent Application Laid-Open No. 5-1161 discloses that as the lubricating layer, a copolymer of 2-hydroxyethyl methacrylate (HEMA) and methacrylic acid (MMA) or 2-ethylhexyl acrylate (EHA) or the above-mentioned HEMA A layer of a terpolymer of MMA and EHA has been proposed, and it is disclosed that such a lubricating layer be formed on the inner surface of a glove, such as for surgical use.

However, all of the conventional lubricating layers including the above-mentioned ones only take lubricating properties into consideration, and the feeling of wearing when the inside of the glove is wet is still poor.
The problem of such a feeling of wearing could not be solved. In addition, if the inner surface of the glove or the hand is wet, the lubricating effect of the lubricating layer is greatly reduced, and there is a problem that the glove is difficult to detach.

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel glove which can be easily attached and detached irrespective of whether the inner surface of the glove or the hand is wet or not and the feeling of wearing does not deteriorate even when the glove is wet. is there.

[0008]

Means for Solving the Problems In order to solve the above problems, the present inventors have studied variously the configuration of the lubricating layer formed on the inner surface of the glove. As a result, when collagen is contained in the lubricating layer of rubber or resin, the lubricating layer has high lubricity and excellent moisture absorption and water absorption due to the action of the collagen, and also quickly releases moisture after absorbing and absorbing water. Because it also has excellent moisture release properties, it has been found that gloves that can be easily attached and detached regardless of whether the inner surface of the glove or the hand is wet or not and that the wearing feeling does not deteriorate even if the inside of the glove gets wet, The present invention has been completed.

That is, the glove of the present invention is provided with at least one rubber or resin base layer, and is characterized in that a rubber or resin lubricating layer containing collagen is laminated on the inner surface thereof. And Further, in the present invention, in order to further enhance the lubricity of the lubricating layer, it is preferable that the lubricating layer also contains at least one type of inorganic or resinous fine particles.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below. As described above, the glove of the present invention is formed by laminating a rubber or resin lubricating layer containing collagen or containing collagen and fine particles on its inner surface. Such a lubricating layer can be formed on the inner surface of the glove by various methods.

However, the base layer of the rubber or resin, which is the main body of the glove, is mainly composed of a pre-vulcanized rubber latex or a resin emulsion, which is the basis of the base layer, and then dipped and dried. It is formed by a so-called immersion method that is solidified and further post-vulcanized in the case of rubber, so in consideration of the manufacturing process and equipment, the lubricating layer is also formed by the immersion method in the same manner as the base layer. preferable.

That is, a glove having a single-layer or multi-layer structure including a base layer is formed on the surface of the above-mentioned glove mold. Unvulcanized or pre-vulcanized rubber latex in which is dispersed, or immersed in a resin emulsion, pulled up, dried and solidified, and in the case of rubber, further heated and vulcanized together with the mold, its outermost surface, That is, a lubricating layer containing collagen or containing collagen and fine particles is laminated and formed on the inner surface of the actual glove.

On the contrary, first, on the surface of the glove mold,
After forming a lubricating layer containing collagen or containing collagen and fine particles by an immersion method, a single-layer or multi-layer glove including a base layer may be laminated and formed thereon. As the rubber latex for the lubricating layer used in the above-mentioned immersion method, any of various rubber-based rubber latexes can be used, but in consideration of the lubricity of the lubricating layer, butadiene rubber latex, acrylonitrile −
Synthetic rubber latex such as butadiene copolymer rubber latex, styrene-butadiene copolymer rubber latex, and isoprene rubber latex, or butadiene rubber latex modified with methyl methacrylate and the like are preferably used.

In consideration of the lubricity of the lubricating layer to the hands, among resin emulsions commonly used for gloves, resin emulsions such as urethane and acrylic resin emulsions are used. It is preferably used. As collagen added to the rubber latex or resin emulsion and contained in the lubricating layer formed on the inner surface of the glove, any of conventionally known various forms can be used. In consideration of the dispersibility in the resin emulsion and the dispersibility in the formed lubricating layer, powdered collagen having an average particle size of about 5 to 15 μm is preferably used. Specific examples of such powdered collagen include, but are not limited to, powdered collagen of the trade name “TORIAZET” series manufactured by Showa Denko KK, and the like.

The fine particles which may be contained in the lubricating layer together with the collagen include, for example, inorganic fine particles such as silica and mica, and resin fine particles such as acrylic, urethane, olefin and vinyl chloride. Is raised. Further, among these, resin fine particles, for example, in order to impart heat resistance that can withstand the heat during the vulcanization of rubber,
It may be crosslinked.

Such fine particles are not limited to these,
It is preferable that the average particle size is about 3 to 30 μm. If the average particle size of the fine particles is less than the above range, the effect of further improving the lubricity of the lubricating layer due to the inclusion of the fine particles may be insufficient, and conversely, when the average particle size exceeds the above range. In this case, the surface of the lubricating layer, that is, the inner surface of the glove may be rough, which may make the wearing feeling worse.

The content of the above-mentioned collagen and fine particles in the lubricating layer is not particularly limited. Among them, collagen is a rubber or resin constituting the lubricating layer.
It is preferable that the content is 30 parts by weight or more based on parts by weight. If the content of collagen is less than this range,
The effect of imparting lubricity, moisture absorption, water absorption, moisture release, etc. to the lubricating layer due to the inclusion of collagen in the lubricating layer may be insufficient.

Since the fine particles are components that need not be contained in the lubricating layer as described above, the lower limit of the content is, of course, 0 parts by weight. However, considering the above-described effect of improving the lubricity of the lubricating layer due to the inclusion of the fine particles, the fine particles account for at least 30 parts by weight based on 100 parts by weight of the rubber or resin constituting the lubricating layer. It is preferable to contain them.

In addition, the collagen and the fine particles are considered to have a characteristic that the lubricating layer does not come off from the base (adhesion at the time of elongation), especially when the glove is elongated, so that the lubricating layer is sufficiently elongated following the glove. It is preferable that the lubricating layer contains 200 parts by weight or less in total with respect to 100 parts by weight of the rubber or resin constituting the lubricating layer. From the same viewpoint, it is preferable that the fine particles are contained in a proportion of 130 parts by weight or less based on 100 parts by weight of the rubber or resin constituting the lubricating layer.

That is, when the total content of collagen and fine particles exceeds 200 parts by weight or the content of fine particles exceeds 130 parts by weight with respect to 100 parts by weight of the rubber or resin constituting the lubricating layer. When the glove is stretched, the lubricating layer may not be sufficiently stretched to follow the glove, and may be separated from the base. In addition, in a system in which only the collagen is contained without containing the fine particles in the lubricating layer, also taking into consideration the adhesion at the time of elongation of the lubricating layer,
Collagen is replaced with rubber or resin 100 constituting a lubricating layer.
It is preferable that the content is 200 parts by weight or less based on parts by weight. In addition, in such a single system, considering the balance of the respective characteristics described above, collagen is used in an amount of 50 to 1 with respect to 100 parts by weight of rubber or resin constituting the lubricating layer.
More preferably, the content is 50 parts by weight.

In the combination system of collagen and fine particles,
Again considering the balance of each characteristic explained above,
It is preferable that collagen is contained in a range of 50 to 100 parts by weight, fine particles are contained in about 50 parts by weight, and both are contained in a proportion of 150 parts by weight or less based on 100 parts by weight of rubber or resin constituting the lubricating layer. More preferred. In order to adjust the content of collagen and fine particles within the above range, for example, when the lubricating layer is formed by the immersion method as described above, the solid content (rubber content, rubber content, (Resin content) The amount of both components added to 100 parts by weight of the resin may be adjusted.

The rubber latex or the resin emulsion which forms the above-mentioned lubricating layer may be appropriately added with various conventionally known additives which are added to these compositions in the dipping method, if necessary. Good. That is, examples of additives that may be added to the rubber latex include vulcanization accelerators, vulcanization acceleration aids, antioxidants, fillers, and dispersants, in addition to vulcanizing agents for vulcanizing rubber. Additives that may be added to the resin emulsion include an antioxidant, a filler,
And dispersants.

The lubricating layer may be formed by a dipping method using a rubber melt or a resin emulsion, a melt obtained by heating and melting a resin, or a solution obtained by dissolving a resin in an appropriate organic solvent. The rubber latex, resin emulsion, melt, solution, or the like may be sprayed onto a part or all of the inner surface of the glove formed in advance to form the glove. Also, collagen in rubber and resin,
Alternatively, a lubricating layer may be formed by attaching a sheet in which collagen and fine particles are dispersed to part or all of the inner surface of the glove.

Although the thickness of the lubricating layer is not particularly limited, the thickness of the lubricating layer formed by the dipping method or the spray coating method is preferably about 1 to 5 μm. If the thickness of the lubricating layer is less than the above range, the lubricating layer may be worn away relatively quickly when gloves are used, and may disappear. However, when the glove is stretched, the lubricating layer may not be sufficiently stretched to follow the glove, and the glove may be peeled off from the substrate. In any of these cases, there is a possibility that the effect of the present invention by the lubricating layer is not maintained until the service life of the glove and is lost before that.

The thickness of the lubricating layer should be within the above range, especially 2-3 μm, in consideration of the balance between the above-mentioned properties.
It is preferably about 3 μm, and more preferably about 3 μm. As the glove on which the lubricating layer is formed, various conventionally known rubber or resin glove configurations are employed.

That is, (1) an unsupported type glove formed of only at least one rubber or resin base layer, or (2) a thin cloth glove body formed of the rubber or resin base layer. The above-mentioned lubricating layer is formed on the inner surface of a support type glove reinforced with the above, to constitute the glove of the present invention.

Specific examples of the unsupported gloves of the above (1) include (1-1) one having only one rubber base layer, and (1-2) two or more rubber base layers. (1-3) One having only one resin base layer, (1-4) Two or more resin base layers laminated, (1-5) Rubber One or more layers of the base layer and the resin base layer are laminated one by one. Examples of the support type glove (2) include the above-mentioned structures (1-1) to (1-5). For example, a thin cloth glove body may be inserted at an arbitrary position. Also, the palm of the outer surface of the glove,
A portion such as the belly of the finger may be provided with a projection or the like for preventing slippage. Furthermore, in order to impart lubricity to the surface of the glove, the manufactured glove may be chlorinated by dipping in about 100 to 500 ppm of chlorine water for about 5 to 10 minutes.

As the rubber constituting the base layer of the glove, when the base layer is formed by the dipping method described above,
Natural rubber latex is suitably used, and synthetic rubber latex such as acrylonitrile-butadiene copolymer rubber and chloroprene rubber, and composite rubber latex of natural rubber latex and synthetic rubber latex can also be used.

The rubber latex contains a vulcanizing agent for vulcanizing the rubber, a vulcanization accelerator,
Various additives such as a vulcanization accelerator, an antioxidant, a filler, and a dispersant are appropriately added as needed. When the base layer is formed by the above-described immersion method, a soft resin-based emulsion such as vinyl chloride or urethane is preferably used as the resin constituting the base layer.

As in the case of the lubricating layer, various additives such as an antioxidant, a filler and a dispersant are appropriately added to the resin emulsion as needed. The rubber or resin base layer constituting the glove is formed by a dipping method using a rubber latex or a resin emulsion as described above, or a melt obtained by heating and melting a resin, or a resin in an appropriate organic solvent. It may be formed by a dipping method using a dissolved solution, or may be formed by another molding method.

The base layer has an elongation of 700 to 700 determined by a measurement method specified in JIS K6251 so that the glove can be easily attached / detached and has elasticity necessary for exhibiting good fit. It may have an elasticity of about 1000%, preferably about 800 to 900%.
As the vulcanizing agent among the additives added to the lubricating layer constituting the glove of the present invention and the rubber latex for the base layer, for example, sulfur and organic sulfur-containing compounds may be mentioned. It is preferably about 0.5 to 3 parts by weight based on 100 parts by weight of the solid content (rubber content) in the rubber latex.

As the vulcanization accelerator, for example, PX (N-
Zinc ethyl-N-phenyldithiocarbamate), PZ
(Zinc dimethyldithiocarbamate), EZ (Zinc diethyldithiocarbamate), BZ (Zinc dibutyldithiocarbamate), MZ (Zinc salt of 2-mercaptobenzothiazole), TT (Tetramethylthiuram disulfide) and the like. These can be used alone or in combination of two or more. The compounding amount is preferably about 0.5 to 3 parts by weight based on 100 parts by weight of the rubber component.

Examples of the vulcanization accelerator include zinc white and stearic acid. The compounding amount is preferably 0.5 to 3 parts by weight based on 100 parts by weight of the rubber component. In general, non-staining phenols are preferably used as the antioxidant, but amines may be used. The amount of the antioxidant is preferably about 0.5 to 3 parts by weight based on 100 parts by weight of the rubber component. Further, each component below the antioxidant may be added to the resin emulsion, and the compounding amount thereof is also 0.5% based on 100 parts by weight of the solid content (resin content) in the resin emulsion.
It is preferably about 3 parts by weight.

Examples of the filler include kaolin clay, hard clay, calcium carbonate and the like.
The compounding amount is preferably 10 parts by weight or less based on 100 parts by weight of the rubber or resin component. The dispersing agent is compounded for improving the dispersion of the above-mentioned additives in the rubber latex or the resin emulsion. Examples of the dispersing agent include various anionic surfactants. The compounding amount of the dispersant is preferably about 0.3 to 1.0% by weight of the total amount of the components to be dispersed.

[0035]

The present invention will be described below based on examples and comparative examples. Example 1 <Preparation of rubber latex composition for lubricating layer> 50 parts by weight of powder in a methyl methacrylate-modified polybutadiene rubber latex [methyl methacrylate content of 35% by weight] with respect to 100 parts by weight of a rubber component in the rubber latex. Collagen (trade name: Triazet CX285-1, manufactured by Showa Denko KK, average particle size: 6 μm, bulk specific gravity: 0.1)
5 g / ml, oil absorption 1.1 ml / g] to prepare a rubber latex composition for a lubricating layer for an immersion method. <Manufacture of rubber gloves> A rubber glove consisting of a single layer of a natural rubber base layer (thickness: about 0.2 mm) formed on the surface of a glove mold by a dipping method in accordance with a conventional method is coated with nitric acid as a coagulating liquid. After being immersed in an ethanol solution of calcium (concentration 15% by weight), pulled up and air-dried for 1 minute at room temperature, immersed in the rubber latex composition for a lubricating layer prepared above for 20 seconds, and slowly pulled up to room temperature. After drying for several minutes, the mold was heated and vulcanized at 100 ° C. for 30 minutes in an oven to form a lubricating layer.

Then, the rubber glove was removed from the mold while turning over, and a rubber glove having a 3 μm-thick lubricating layer laminated on its inner surface was manufactured. Examples 2 to 4 In the rubber latex composition for the lubricating layer, the compounding amount of the powdered collagen was 100 parts by weight (Example 2), 150 parts by weight (Example 3), and 200 parts by weight (Example 4). Except for this, in the same manner as in Example 1, the inner surface has a thickness of 3
A rubber glove having a μm lubricating layer laminated thereon was manufactured.

Comparative Example 1 A rubber glove having a 3 μm-thick lubricating layer laminated on its inner surface in the same manner as in Example 1 except that powdered collagen was not added to the rubber latex composition for the lubricating layer. Was manufactured. Moisture Absorption, Water Absorption and Moisture Release Test of Lubricating Layer The same portion of each rubber glove produced in Examples 1 to 4 and Comparative Example 1 was cut out to have a certain size, and the temperature was set to 20.
The sample was left standing for 3 hours under the conditions of a temperature of 40 ° C. and a humidity of 40% RH to prepare a sample.

Next, after weighing the above sample, 60
The substrate was immersed in water for 2 seconds to absorb water, then the surface water was wiped off and weighed again, and the amount of water absorption [g / m ² ] per unit area of the lubricating layer was determined from the increase in weight. Then, the sample in the water-absorbing state is left again for 3 hours under the condition of a temperature of 20 ° C. and a humidity of 40% RH, and is weighed. The amount of moisture released per unit [g / m ² ] was determined.

Table 1 shows the results.

[0040]

[Table 1]

As can be seen from the table, all the gloves of Examples 1 to 4 in which the lubricating layer contained collagen had high water absorption unlike the glove of Comparative Example 1 in which the lubricating layer did not contain collagen. It was found that the higher the content of, the higher the water absorption. In addition, it was also found that all the gloves of each example, when left to dry, release the same amount of water as the amount of water absorbed, and quickly return to the original state.

From these facts, it was confirmed that all of the gloves of the respective examples were excellent in moisture absorption and water absorption, and also excellent in moisture release. Examples 5 and 6 Crosslinked polymethyl methacrylate beads [average particle size 3 μm] were further added to the rubber latex composition for a lubricating layer.
A rubber glove having a 3 μm-thick lubricating layer laminated on the inner surface thereof was produced in the same manner as in Examples 1 and 2 except that 0 part by weight was blended.

Dynamic Friction Coefficient Test The rubbery gloves produced in Examples 1 to 3, Examples 5 and 6 and Comparative Example 1 had a flat portion as close to the cuff as possible.
A coefficient of dynamic friction of the lubricating layer in a state where the sample was cut and dried at a temperature of 20 ° C. and a humidity of 40% RH for 3 hours (Dry) was cut out into a rectangular shape of cm × 10 cm. (ΜK) was measured under the following measurement conditions using a surface property measuring instrument [HEIDON-4S / Shinto Scientific Instruments Co., Ltd.]
D-type]. Then, the dynamic friction coefficient (μK) of the lubricating layer was measured again with the same surface property measuring device under the following measurement conditions in a state where the above-mentioned sample was wet with water (Wet). (Measurement conditions) Indenter used: 30 mm x 30 mm metal flat plate indenter Load: 100 g Moving distance: 100 mm Moving speed: 50 mm / min Detachability test Each rubber produced in Examples 1 to 3, Examples 5 and 6, and Comparative Example 1 The gloves were allowed to dry for 3 hours under the conditions of a temperature of 20 ° C. and a humidity of 40% RH. The gloves were attached and detached by ten subjects whose hands were sufficiently dried. Dry) was evaluated for removability.

A: Eight or more subjects judged that the detachability was good. Very good detachability. ：: 5 to 7 subjects judged that the detachability was good. Good detachability. Δ: Three to four subjects judged that the detachability was good. Slight decrease in detachability. However, no problem in practical use. X: Only two or less subjects judged that the detachability was good. Poor detachability.

Next, the rubber gloves of the respective examples and comparative examples were soaked in water, and they were detached by the same number of subjects who had their hands wet with water. Was evaluated for detachability. Wearing feeling test In the above-mentioned detachability test, each subject during the test of the detachability in a wet state was confirmed whether the feeling of wearing gloves was good or bad. Then, the feeling of wearing in a wet state was evaluated according to the following criteria.

A: Eight or more subjects judged that the wearing feeling was good. Very good fit. ：: 5 to 7 subjects judged that the wearing feeling was good. Good wearing feeling. Δ: Three to four subjects judged that the wearing feeling was good. A feeling of wearing is slightly reduced. However, no problem in practical use. X: Only two or less subjects judged that the wearing feeling was good. Poor wearing feeling.

Adhesion test during elongation Each of the rubber gloves produced in Examples 1 to 3, Examples 5 and 6 and Comparative Example 1 was turned over so that the lubricating layer was on the outside and 300%
In a stretched state, the lubricating layer was rubbed with a finger, and the state was observed. Then, the adhesion at the time of elongation of the lubricating layer was evaluated according to the following criteria.

：: No change in the lubricating layer. Good adhesion. ×: The lubricating layer peeled off. Poor adhesion. Table 2 shows the above results.

[0049]

[Table 2]

From the table, it can be seen that the gloves of Examples 1 to 3, 5 and 6 in which the lubricating layer contained collagen all had an inner surface of the glove as compared with the glove of Comparative Example 1 in which the lubricating layer did not contain collagen. It was found that it was always easy to put on and take off, regardless of whether the hands were wet or not, and that even if the gloves got wet, the wearing feeling did not deteriorate. Also, comparing the gloves of the examples, it is found that the greater the amount of collagen contained in the lubricating layer, the more the detachability and the feeling of wearing are improved, and that the fine particles contained in the lubricating layer further improve the detachability. Was.

[0051]

As described in detail above, according to the present invention,
It has the unique effect of being able to provide a novel glove, which can be easily attached and detached regardless of whether the inner surface of the glove or the hand is wet or not, and the wearing feeling does not deteriorate even when the glove is wet.

Continued on the front page (72) Inventor Toshimichi Shimizu 41-1, Shimizu, Uozumi-cho, Akashi-shi, Hyogo Sumitomo Rubber Fish House (72) Inventor Tadao Nishimatsu 244-1, Kobayashi, Bessho-cho, Miki-shi, Hyogo Hirono Kagaku Kogyo Co., Ltd. (72) Inventor Taro Nakura 3-33 Hiyoshicho, Nagata-ku, Kobe City, Hyogo Prefecture Inside Honey Chemical Co., Ltd.

Claims (5)

[Claims] 1. A glove comprising at least one rubber or resin base layer, wherein a lubrication layer of a rubber or resin containing collagen is laminated on the inner surface thereof. 2. The glove according to claim 1, wherein the lubricating layer contains collagen in an amount of 30 parts by weight or more based on 100 parts by weight of rubber or resin constituting the lubricating layer. 3. The glove according to claim 1, wherein the lubricating layer also contains at least one kind of fine particles made of an inorganic material or a resin. 4. A lubricating layer comprising the fine particles in a proportion of not more than 130 parts by weight and the fine particles and collagen in a total amount of 100 parts by weight of rubber or resin constituting the lubricating layer.
The glove according to claim 3, wherein the glove is contained in a proportion of not more than 00 parts by weight. 5. The glove according to claim 1, wherein the lubricating layer is formed by a dipping method from a rubber latex or a resin emulsion in which at least collagen is dispersed.