JP2001020112A - Treating agent for inner face of acrylic resin glove and glove produced by using the agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a treating agent for the inner face of an acrylic resin glove to enable easy wearing and removal of the glove and provide a glove made of an acrylic resin and having excellent wearing and removing performance. SOLUTION: This inner face treating agent contains an acrylic resin emulsion and at least one kind of organic filler selected from (meth)acrylic resin particles, polyolefin resin fine powder and cellulose beads and having an average particle diameter of 3-10 μm. The content of the organic filler is 2-8 wt.% based on the whole agent. The acrylic resin glove is produced by applying the above treating agent to the inner surface of an acrylic resin glove.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a treatment agent for improving the lubricity of the inner surface of an acrylic resin glove, and to an acrylic resin glove which can be smoothly attached and detached.

[0002]

2. Description of the Related Art Conventionally, gloves for home use, work use, inspection use, surgery use, etc. are made of natural rubber (NR).
Various materials such as those made of synthetic rubber such as acrylonitrile-butadiene rubber (NBR) and styrene-butadiene rubber (SBR) and those made of synthetic resin such as vinyl chloride resin and polyurethane resin are known.

[0003] These gloves generally have high adhesion to hands and have a sticky feeling, so that they cannot be worn and removed smoothly. Therefore, conventionally, the inner surface of a glove is subjected to a powdering treatment for adhering a release agent such as talc powder, mica powder, starch, or the like, or a chlorine treatment or flocking is applied to the surface, so that the friction coefficient of the surface (that is, adhesiveness) is reduced. Attempts have been made to reduce the gloves' gloves and increase the slipperiness of the glove's inner surface.

However, the release agent and the implanted hair attached to the inner surface of the glove are easily separated from the glove body by repeatedly using or washing the glove, and the effect of improving the lubrication over a long period of time. Cannot be maintained. In addition, since the release agent may adhere to hands after gloves are detached or stain the surroundings, the production of electronic components, etc.
It cannot be used for work that requires extreme avoidance of dust. Furthermore, depending on the type of the release agent, direct contact with hand skin may cause allergic symptoms.

[0005] On the other hand, when chlorination is performed, even if only the inner surface of the glove is processed, even the outer surface is liable to slip, which causes a problem that the workability when wearing the glove is reduced. However, there is a problem that discoloration occurs in gloves. Furthermore, in the recent efforts to address the dioxin problem, which has been particularly attracting attention, there is a tendency to avoid products containing chlorine, and for this reason chlorine treatment is being avoided.

[0006]

Therefore, in recent years, by providing a layer containing fine particles on the inner surface of the glove, the operability at the time of wearing the glove has been maintained, and the inner surface has been improved in slipperiness to achieve good wearing. -Attempts have been made to obtain desorption properties, and various internal surface treatment agents and methods for forming the inner surface for forming the layer, and various gloves subjected to internal surface treatment have been proposed.

Japanese Patent Application Laid-Open No. 8-337910 discloses an NBR glove having an acrylic resin layer containing inorganic fine particles such as silica powder on the inner surface of a glove base composed of acrylonitrile-butadiene rubber (NBR) latex. Japanese Patent Application Laid-Open No. 4-119102 discloses a glove made of a vinyl chloride resin in which a layer made of a synthetic resin emulsion containing an organic filler is provided to improve the inner surface of the glove.

[0008] However, the glove thus obtained also has
The feeling of wearing and removing is still insufficient. Furthermore, N
Since BR gloves and gloves made of vinyl chloride resin have not so good adhesion to the acrylic resin layer, there is also a problem that the acrylic resin layer peels off after long-term use.

Japanese Patent Application Laid-Open No. 8-337910 discloses an organic fine particle such as a vinyl chloride resin instead of an inorganic fine particle as a fine powder added to improve the lubricity of an acrylic resin layer. There is a description that can be used. However, when a vinyl chloride resin is used, dioxin may be generated at the time of disposal as described above. The invention described in Japanese Patent Application Laid-Open No. 4-119102 relates to gloves made of vinyl chloride resin. Such gloves have a problem in that the gloves themselves have poor oil resistance and mechanical strength, and also have a problem in disposal. Dioxin may be generated.

The present inventors have previously filed a patent application for an invention relating to acrylic resin gloves (Japanese Patent Application No. 11-107066). This acrylic resin glove has the advantage of having a large modulus, and also has the advantage of not causing environmental pollution at the time of disposal, unlike vinyl chloride. However, the conventionally known inner surface treatment agent for gloves is mainly for rubber gloves and is based on latex, and has low adhesion to acrylic resin gloves, which is not practical.

[0011] Also, Japanese Patent Application Laid-Open No. 8-3379
In the case where only the acrylic resin layer disclosed in Japanese Patent Publication No. 10 is formed, sufficient lubricity cannot be obtained, and conversely, the addition of the fine powder causes a feeling of roughness. on the other hand,
When a layer made of a synthetic resin emulsion disclosed in Japanese Patent Application Laid-Open No. 4-119102 is provided on the inner surface of an acrylic resin glove, there is a problem that the layer is easily peeled off due to low adhesion between the two.

[0012] Accordingly, a practical inner surface treating agent capable of improving the inner surface lubricity of the acrylic resin glove has not yet been known. Therefore, an object of the present invention is to provide an inner surface treatment agent for improving the wearability and detachability of an acrylic resin glove, and an acrylic resin glove excellent in wearability and detachability.

[0013]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, the acrylic resin emulsion contained fine particles of a predetermined organic filler and contained the same. When the amount is set in the predetermined range, the wearability and the detachability are excellent, and the wearability and the detachability do not decrease even after long-term use,
Furthermore, they have found a completely new fact that acrylic resin gloves having little effect on the environment during disposal can be obtained, and have completed the present invention.

That is, the inner surface treating agent for acrylic resin gloves according to the present invention comprises an acrylic resin emulsion and (meth) acrylic resin fine particles, polyolefin resin fine particles and cellulose beads having an average particle diameter of 3 to 10 μm. And at least one organic filler selected from the group consisting of: and a content of the organic filler is 2 to 8% by weight of the whole.

According to this internal surface treatment agent, since the resin emulsion serving as the base of the internal surface treatment agent is a resin similar to the acrylic resin constituting the main body of the acrylic resin glove, the internal surface treatment provided on the glove body by the internal surface treatment It has good adhesion between the agent layer and the glove body, and does not peel off even after long-term use. Further, while the inner surface treatment agent contains fine particles of the predetermined organic filler,
Since the content is set in the predetermined range, excellent lubricity can be imparted to the inner surface of the acrylic resin glove.

The above-mentioned inner surface treatment agent of the present invention is preferably an acrylic resin emulsion containing a crosslinking agent. In this case, the main body of the acrylic resin glove and the layer of the inner surface treatment agent provided on the inner surface thereof can be simultaneously crosslinked, and the adhesion between the layer of the inner surface treatment agent and the main body of the acrylic resin glove is further improved. Can be something.

An acrylic resin glove according to the present invention is characterized in that the inner surface treating agent according to the present invention is formed on the inner surface of an acrylic resin glove body. The acrylic resin glove according to the present invention has a very good feeling of wearing and demounting,
It is possible to make the gloves made of acrylic resin excellent in the wearing feeling and the detaching feeling without damaging the large modulus inherent in the gloves.

[0018]

(Inner surface treatment agent)

(Acrylic resin emulsion) The acrylic resin emulsion that can be used for the inner surface treatment agent according to the present invention includes:
For example, (1) an emulsion of a homopolymer of acrylic acid, acrylic acid ester, methacrylic acid or methacrylic acid ester; (2) a copolymer obtained by combining at least two of the four monomers disclosed in the above (1) (3) an emulsion of a polymer obtained by copolymerizing any one of the polymers disclosed in the above (1) and (2) with vinyl acetate, styrene or acrylonitrile; and (4) an emulsion of the above (1) to ( Various grades from hard to soft, such as emulsions of polymers obtained by copolymerizing the polymer disclosed in 3) with a monomer having a crosslinkable group such as a hydroxyl group, a carboxyl group, an N-methylol group, or an N-methylol ether group. One. In particular, when an acrylic resin emulsion having self-crosslinking properties as described in (3) and (4) above is used, gloves with high modulus can be obtained without blending a crosslinking agent.

Examples of the substituent constituting the ester moiety in the acrylate and methacrylate include those having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, i-propyl, n-butyl and t-butyl. And the like. Specific examples of the acrylic resin emulsion include trade names “LX851” (Tg = 15 ° C.) and “LX852” (T
g = −6 ° C., soft), “LX854” (Tg = −10)
C.), "LX857" (Tg = 43 ° C., hard) and the like (the trade name is followed by the glass transition temperature Tg and whether the material belongs to the hard or soft grade).

In the present invention, in order to ensure sufficient adhesion between the layer formed by the inner surface treating agent and the acrylic resin glove, and to improve the strength of the acrylic resin glove, a base emulsion of the inner surface treating agent is used. It is preferable to add a crosslinking agent to a certain acrylic resin emulsion.
When the emulsion of the above (3) and (4) having self-crosslinking property is used as the acrylic resin emulsion,
Although the film can be formed without a cross-linking agent, the strength of the acrylic resin glove can be further improved by adding the cross-linking agent.

Examples of the crosslinking agent include various known crosslinking agents used for processing polymers, such as zinc white, melamine resin and epoxy resin. The amount of the crosslinking agent is not particularly limited, but is preferably 1 to 10 parts by weight based on 100 parts by weight of the resin solid content of the acrylic resin emulsion.
In particular, it is preferably 1 to 5 parts by weight.

To the acrylic resin emulsion, besides the crosslinking agent and the organic filler described later, various conventionally known additives such as an antioxidant, a filler and a dispersant are added as required. be able to. In general, non-staining phenols are preferably used as the antioxidant, but amines may be used. The amount of the antioxidant added is 10% of the resin solid content of the acrylic resin emulsion.
It is preferably about 0.5 to 3 parts by weight with respect to 0 parts by weight. Examples of the filler include kaolin clay, hard clay, calcium carbonate and the like. The amount of the filler added is preferably 10 parts by weight or less based on 100 parts by weight of the resin solid content. The dispersant is added to improve the dispersibility of various compounding agents in the acrylic resin emulsion, and includes, for example, an anionic surfactant. The amount of the dispersant added is preferably about 0.3 to 1.0% by weight based on the weight of the component to be dispersed.

(Organic filler) In the inner surface treating agent according to the present invention, the acrylic resin emulsion contains (meth) acrylic resin fine particles such as methyl methacrylate (PMMA); polyolefin resin fine particles such as polyethylene and polypropylene. Or an organic filler of cellulose beads is added.

The average particle size of the organic filler is 3 to 10 μm.
Is set in the range. If the average particle size is below the above range, sufficient lubricity cannot be imparted to the inner surface of the acrylic resin glove. Therefore, there is a possibility that the acrylic resin glove may not be able to provide a good feeling of wearing and a feeling of detachment. Conversely, if the average particle size exceeds the above range, the inner surface of the acrylic resin glove will have a rough feeling. Therefore, there is a possibility that the feeling of wearing and removing gloves may be impaired. The average particle size of the organic filler is
It is particularly preferable to be 3 to 6 μm in the above range.

The amount of the organic filler to be added is set to 2 to 8% by weight based on the whole inner surface treatment agent. If the amount is less than the above range, sufficient lubricity cannot be imparted to the inner surface of the acrylic resin glove. Therefore, there is a possibility that the acrylic resin glove may not be able to provide a good feeling of wearing and a feeling of detachment. Conversely, if the addition amount exceeds the above range, it may be difficult to form a layer of the inner surface treating agent, or a rough feeling may occur on the inner surface of the acrylic resin glove, which may impair the feeling of wearing and removing the glove. Occurs. The addition amount of the organic filler is particularly preferably 2 to 6% by weight in the above range.

[Acrylic Resin Glove] The acrylic resin glove according to the present invention is manufactured through the following steps (a) to (d). (a) A heat-sensitive agent and an anode coagulant are added to a predetermined acrylic resin emulsion, and a crosslinking agent is further added if necessary.

(B) Next, a heated glove mold is dipped in the resin emulsion to gel the resin emulsion to form a film. (c) Further, the mold of the glove on which the film is formed is immersed in the preliminarily heated inner surface treating agent according to the present invention to form a layer of the inner surface treating agent on the surface of the film. (d) After heating the film and the layer of the inner surface treatment agent to simultaneously crosslink both, the laminate of the film and the layer of the inner surface treatment agent is inverted and released from the glove mold.

Examples of the thermal sensitizer used in the above step (a) include inorganic or organic ammonium salts such as ammonium nitrate, ammonium acetate and zinc ammonium complex, or polyvinyl methyl ether, for example.
The cloud point of polyalkylene glycol, polyether polyformal, functional polysiloxane, etc.
A water-soluble polymer having a temperature of 0 ° C. or lower can be used.

Examples of the anode adhesive include divalent or higher-valent metal salts such as calcium nitrate and calcium chloride, and organic alkylamine salts such as tetramethylammonium hydrochloride. The amount of the heat sensitizer or the anode coagulant may be set according to a conventional method.
To 5 parts by weight, particularly 0.5 to 2.0 parts by weight.

The type and amount of the cross-linking agent are the same as the cross-linking agent added to the inner surface treatment agent and the amount thereof.
In the step (b), the heating temperature of the glove mold is appropriately set in accordance with the type of the acrylic resin emulsion to be used.
It is set to be about 00 ° C. As the glove mold, conventionally known ones such as, for example, ceramics and ceramics can be used.

The crosslinking treatment in the above step (d) is not particularly limited.
Then, it may be performed for about 20 to 60 minutes. In the present invention,
From the viewpoint of further improving various properties such as modulus, flexibility and elongation of gloves, JIS K6
251 (Tensile test method for vulcanized rubber) has a tensile stress M ₃₀₀ at 300% elongation (that is, modulus) of 7.0.
It is preferably set to be not less than MPa, especially in the range of 7.0 to 8.0 MPa. Tensile stress M ₃₀₀ of the glove, the type of the acrylic resin emulsion to be used, especially other soft or hard, can be appropriately adjusted by the mixing ratio or the like. The tensile stress M
_{If 300} is less than 7.0 MPa, there is a possibility that it is not possible to obtain the same or more wearability and desorption property as or more than gloves made of vinyl chloride resin.

[0032]

Next, the present invention will be described with reference to examples and comparative examples. Example 1 (Manufacture of inner surface treatment agent) As a base emulsion of the inner surface treatment agent, an acrylic resin emulsion “LX85” was used.
2 "(trade name, manufactured by Zeon Corporation, Tg = -6 ° C, soft) and" LX857 "(trade name, manufactured by the company, Tg = 43)
C., hard) at a ratio of 80:20.

Zinc white (crosslinking agent) is added to 100 parts by weight of the dry polymer (resin solid content) of the base emulsion.
After adding 3 parts by weight, the concentration of the dry polymer is reduced to 0.
It was diluted with distilled water to 4% by weight. Next, particles of polymethyl methacrylate (PMMA) as an organic filler [trade name “Julima MB-S” manufactured by Nippon Pure Chemical Co., Ltd.,
μm] at a ratio of 2% by weight to obtain an inner surface treating agent for an acrylic resin emulsion.

(Preparation of glove body) As an acrylic resin emulsion, the above-mentioned "LX852" and "LX857"
And the weight ratio of the dry polymer (resin solids) is 80: 2.
What was mixed so that it might be set to 0 was used. Total amount of dry polymer in the acrylic resin emulsion 100
5 parts by weight of zinc white (crosslinking agent), 0.5 parts by weight of polyvinyl methyl ether (thermal sensitizer) and 1.5 parts by weight of calcium nitrate (anode coagulant) were added to the parts by weight,
Heat sensitivity was imparted to the acrylic resin emulsion.

Next, a glove mold heated to about 100 ° C. was immersed in the acrylic resin emulsion for about 5 seconds, and then the glove mold was pulled up. (Manufacture of Acrylic Resin Glove Treated with Inner Surface) The film of the acrylic resin emulsion formed on the mold surface of the glove by the above “Preparation of Glove Body” is treated with the “emulsion of the inner treatment agent” while the resin emulsion remains in a gel state. The glove mold was immersed in the inner surface treatment agent obtained by "manufacturing" for about 20 seconds, thereby forming a layer of the inner surface treatment agent on the surface of the film.

In forming the layer of the inner surface treatment agent, the inner surface treatment agent was used at room temperature, and the film of the acrylic resin emulsion was immersed in the inner surface treatment agent for about 20 seconds. After pulling up the glove mold from the inner surface treating agent, it was heated at 100 to 130 ° C. for 20 to 60 minutes to crosslink the film (glove body) formed on the mold surface and the layer of the inner surface treating agent. Next, the formed layer of the resin emulsion and the inner surface treating agent was inverted and removed from the mold of the glove to obtain an acrylic resin glove having a lubricated inner surface.

Examples 2 and 4 An acrylic resin having an inner surface subjected to a lubrication treatment in the same manner as in Example 1 except that the addition amount of the organic filler in the inner surface treatment agent was set to the value shown in Table 1. I got gloves. Example 3
The same procedure as in Example 1 was repeated except that an organic filler having the particle size shown in Table 1 was used as the organic filler in the inner surface treatment agent, and the amount of addition was set to the value shown in Table 1. Acrylic resin gloves subjected to a sexual treatment were obtained.

Comparative Examples 1 and 2 The same procedure as in Example 1 was carried out except that the amount of the organic filler added in the inner surface treating agent was set to the value shown in Table 2, and the acrylic resin having the inner surface subjected to lubrication treatment was used. I got gloves. Comparative Examples 3 and 4 The same procedure as in Example 1 was carried out except that an organic filler having the particle size shown in Table 2 was used as the organic filler in the inner surface treatment agent and the amount of addition was set to the value shown in Table 2. Thus, an acrylic resin glove having a lubricated inner surface was obtained.

Comparative Example 5 1 part by weight of sulfur (vulcanizing agent), 1 part by weight of zinc white (crosslinking agent), 100 parts by weight of rubber solids in natural rubber (NR) latex as a base latex, dibutyl carbamic acid One part by weight of zinc (vulcanization accelerator, BZ) was added, and the mixture was diluted so that the concentration of the rubber solids became 0.4% by weight to obtain a base NR latex.

As the inner surface treating agent, the above NR latex was used in place of the acrylic resin emulsion.
In the same manner as in Example 1, an acrylic resin glove having an inner surface subjected to a lubrication treatment was obtained. Comparative Example 6 Rubber solid content of 100 in acrylonitrile-butadiene rubber (NBR) latex as base latex
1 part by weight of sulfur (vulcanizing agent), 1 part by weight of zinc white (crosslinking agent), and 1 part by weight of zinc dibutylcarbamate (vulcanization accelerator, BZ) are added to parts by weight, and the concentration of rubber solids Is 0.
It was diluted to 4% by weight to obtain a base NBR latex.

An acrylic resin glove having an inner surface subjected to a lubrication treatment was obtained in the same manner as in Example 1 except that the above NBR latex was used in place of the acrylic resin emulsion as the inner surface treating agent. [Evaluation of physical properties] (Measurement of friction coefficient) Haydon 10 type (trade name "Tribogear" manufactured by Shinto Kagaku Co., Ltd., TYPE: H)
EIDON-10DR] was used to determine the coefficient of static friction of the inner surface (the surface having the inner surface treatment agent layer with higher lubricity) of the gloves obtained in the above Examples and Comparative Examples before cleaning (before use) ) And after washing. It should be noted that plain paper was used as an object when measuring the friction coefficient, and the measurement was performed under the condition of a load of 50 g.

The acrylic resin glove obtained in Reference Example was used as a control without being treated with an inner surface treating agent. For this control, the friction coefficient was measured in the same manner as described above. [Glove Wearability / Removability] Ten test subjects actually wore the gloves of the above Examples, Comparative Examples and Controls, and the feeling of wearing gloves (easiness of work while wearing rubber gloves) The degree of burden on the hands and the degree of tightness of the hands, so-called fit, and the feeling of putting on and taking off (handling when attaching or detaching rubber gloves) were evaluated.

The wearability and the detachability were evaluated according to the following criteria, and expressed as an average of the evaluations of each subject. (Wearability) ：: The feeling of wearing was extremely soft, the fingers could be bent and stretched naturally, and it felt as if they were not wearing gloves. 〇: The feeling of wearing was soft, and the fingers could be bent and stretched naturally. Δ: The glove was felt somewhat hard, but there was no practical problem. X: The feeling of wearing was extremely poor, and fatigue was generated in the hands after wearing for a long time.

(Removability) A: Very easy to wear (easy to wear) and easy to take off. ：: easy to wear and take off. Δ: Hard to wear and hard to remove. X: Extremely difficult to wear and take off.

The above results are shown in Tables 1 and 2.

[0046]

[Table 1]

[0047]

[Table 2]

As is clear from Tables 1 and 2, in Examples 1 to 4 in which the inner surface treatment agent layer according to the present invention was provided on the inner surface of the acrylic resin glove, the inner surface had a low coefficient of static friction and was excellent in lubricity. I knew it was. In addition, the feeling of wearing and the feeling of attaching and detaching were good, and the lubricity could be sufficiently improved as compared with acrylic resin gloves not subjected to the inner surface treatment. Furthermore, since the feeling of wearing and the feeling of desorption were good both before and after washing, it was found that the effect of forming the layer of the inner surface treatment agent could be maintained for a long period of time.

On the other hand, in Comparative Example 1 in which the amount of the organic filler in the inner surface treatment agent was small and Comparative Example 3 in which the particle size of the organic filler was small, the lubricity could not be sufficiently improved. The feeling of wearing and the feeling of demounting could not be improved. In Comparative Example 2 in which the amount of the organic filler added in the inner surface treatment agent was too large, and in Comparative Example 4 in which the particle size was too large, although the coefficient of friction was low, roughening occurred, and the feeling of attachment and detachment was insufficient. there were.

On the other hand, NR or NBR to which a vulcanizing agent is added
In Comparative Examples 5 and 6 using a latex-based inner surface treatment agent such as those described above, the adhesiveness between the layer of the inner surface treatment agent and the main body of the acrylic resin glove was insufficient, so that it was already attached at the stage before cleaning. The feeling and the desorption feeling were poor. Further, from this, it was found that it is preferable to use, as the inner surface treatment layer of the acrylic resin glove, a resin emulsion of the same type as the resin constituting the glove body.

[0051]

As described above in detail, according to the inner surface treating agent of the present invention, the inner surface can be improved in lubricity without deteriorating the physical properties of the acrylic resin glove, and the state can be maintained for a long time. Can be maintained. Therefore, according to the acrylic resin glove according to the present invention which has been treated using the above-mentioned inner surface treating agent, it is possible to smoothly carry out attachment and detachment over a long period of time.

Claims (3)

[Claims] 1. An acrylic resin emulsion and at least one organic filler selected from the group consisting of (meth) acrylic resin fine particles, polyolefin resin fine particles and cellulose beads having an average particle diameter of 3 to 10 μm. An inner surface treating agent for acrylic resin gloves, wherein the content of the organic filler is 2 to 8% by weight of the whole. 2. The inner surface treating agent for acrylic resin gloves according to claim 1, further comprising a crosslinking agent. 3. An acrylic resin glove, wherein the inner surface treating agent according to claim 1 or 2 is formed on the inner surface of the acrylic resin glove body.