JP2001081615A - Gloves and their production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain gloves of acrylic resin having tensile properties equal to or higher than those of gloves made of natural rubber or a vinyl chloride resin and excellent tear strength by forming an acrylic resin emulsion containing an acrylic staple into a film. SOLUTION: Molds of gloves are immersed in an acrylic resin emulsion containing at least an acrylic staple and coating films composed of the resin emulsion are formed on the surfaces of the molds to give the objective gloves. The gloves can be obtained by a simple method by a conventional immersion process. Since a vinyl chloride resin is not contained in the coating films of the gloves, the gloves have no fear of evolution of dioxin and contaminate an environment in scrapping and incineration. A crosslinking agent such as zinc flower, melamine resin, epoxy resin, etc., useful for processing a polymer may be cited as the crosslinking agent. The amount of the crosslinking agent compounded is preferably 1-10 pts.wt., especially 1-5 pts.wt. based on 100 pts.wt. of resin solid of the acrylic resin emulsion.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to gloves made of acrylic resin, and more particularly, to gloves made of acrylic resin having excellent mechanical strength such as tear strength and a method for producing the glove.

[0002]

2. Description of the Related Art Gloves generally used for home use, work, inspection, surgery and the like are roughly classified into rubber gloves and vinyl chloride resin gloves. Of these, the gloves made of a vinyl chloride resin having a higher modulus are more excellent in terms of wearability and detachability. However, the vinyl chloride resin has a problem that it causes dioxin to be generated during disposal and incineration. For this reason, in recent years, in particular, the use of the glove has been suppressed while the interest in environmental issues has been increasing, and it has been demanded to obtain gloves having excellent properties such as wearability and detachability without using a vinyl chloride resin. I have.

Japanese Patent Application Laid-Open No. 8-283522 discloses a resin glove which does not use a vinyl chloride resin, which is disclosed in, for example, a latex of a copolymer of an unsaturated nitrile having a carboxyl group in a molecule and a conjugated diene, and a polyurethane resin emulsion. A glove formed using a composition comprising: However, such gloves are intended to improve oil resistance and solvent resistance, and their wearability and desorption properties are insufficient compared to gloves made of vinyl chloride resin.

Further, in order to impart lubricity to the inner surface of a glove, a glove base made of NBR latex is provided with an acrylic resin layer on part or all of the inner surface.
BR gloves (JP-A-8-337910) and gloves in which the inner surface of a glove is coated with a coating made of ionic polyurethane and a blend of the polyurethane and another polymer (JP-A-2677850) are disclosed. However, the glove disclosed in the above publication requires a lamination and coating process, and has a problem that the manufacturing process is complicated and the manufacturing cost is high. Further, the problem that the wearability and the detachability are low as compared with a glove made of a vinyl chloride resin cannot be solved.

[0005]

As a material for gloves instead of the vinyl chloride resin, an acrylic resin may be used in addition to the materials disclosed in the above-mentioned publication. However, gloves formed from an acrylic resin emulsion have a problem that their tear strength is lower than that of rubber gloves or vinyl chloride resin gloves. Therefore, an object of the present invention is to provide an acrylic resin glove having tensile properties equal to or higher than that of natural rubber or vinyl chloride resin gloves, and also having excellent tear strength, and a method for producing the same. .

[0006]

Means for Solving the Problems and Effects of the Invention The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, when acrylic short fibers are blended in an acrylic resin emulsion, an acrylic resin In order to improve the tear strength, which was a weak point of such a glove, without impairing the tensile properties of the glove formed from the resin emulsion, the inventors have found a new fact that the glove can be excellent, and completed the present invention. Reached.

That is, the glove according to the present invention is formed by using an acrylic resin emulsion containing at least short acrylic fibers. Further, the method for producing a glove of the present invention is characterized in that a glove mold is immersed in an acrylic resin emulsion containing at least an acrylic short fiber to form a film made of the resin emulsion on the surface of the mold. . The glove according to the present invention is based on an acrylic resin emulsion, and is formed by adding an acrylic short fiber to the film to form a film. The glove made of an acrylic resin has sufficient tensile properties and excellent wearing properties. Further, while maintaining the desorption property, the reinforcing effect by the addition of the acrylic short fiber, that is, the tear strength can be improved.

Further, the glove according to the present invention can be obtained by a simple method using a conventional immersion method,
Since vinyl chloride resin is not contained in the glove film, there is no danger of generating dioxin during disposal or incineration and polluting the environment.

[0009]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a glove according to the present invention will be described in detail. (Acrylic resin emulsion) As the acrylic resin emulsion used in the present invention, (1) acrylic acid, acrylic acid ester, methacrylic acid,
Or an emulsion of a homopolymer of a methacrylate (2) an emulsion of a copolymer obtained by combining at least two of the four monomers disclosed in the above (1); (3) an emulsion of the above (1) and (2) )) And an emulsion of a copolymer of any of the polymers disclosed in the above and vinyl acetate, styrene or acrylonitrile. (4) In the polymer disclosed in the above (1) to (3), a hydroxyl group, a carboxyl group, an N-methylol group, -Various grades from hard to soft, such as emulsions of polymers obtained by copolymerizing monomers having a crosslinkable group such as a methylol ether group. 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 described later.

The substituent constituting the ester moiety in the acrylate and methacrylate esters is, for example, one 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).

[Acrylic short fibers] The acrylic short fibers used in the present invention are not particularly limited, and various conventionally known acrylic short fibers can be used. Also,
Either straight fibers or crimped fibers can be used. The fiber length of the acrylic short fiber is not particularly limited, but is 0.4 to 0.8 mm, preferably 0.4 to 0, from the viewpoint of the reinforcing effect of the glove and the dispersibility in the acrylic resin emulsion. .6m
It is preferable to use m.

Although the content of the acrylic short fiber in the glove of the present invention is not particularly limited, it is usually one to one in a film formed using an acrylic resin emulsion.
It is preferable to adjust the content to be within the range of 8% by weight. When the content ratio of the acrylic short fiber falls below the above range,
The effect of improving the tear strength of gloves can no longer be obtained,
The tear strength may be insufficient for practical use. Conversely, if the blended amount of the acrylic short fibers exceeds the above range, the tear strength may be increased, but the tensile properties may be reduced and may be insufficient for practical use.

The content ratio of the acrylic short fiber is preferably 2 to 6% by weight, more preferably 2 to 4% by weight in the above range. In order to set the content ratio of the acrylic short fiber in the above range, the content of the acrylic short fiber in the acrylic resin emulsion at the time of forming the film is set to be 0.1 to 100 parts by weight of the resin solid content in the resin emulsion. It is preferable to set the amount to be 1 to 4 parts by weight.

The blending amount of the acrylic short fiber in the acrylic resin emulsion is particularly preferably 2 to 4 parts by weight, more preferably about 4 parts by weight in the above range. In the present invention, since the resin emulsion constituting the film of the glove is an acrylic resin emulsion, the fibers to be incorporated in order to improve the tear strength of the glove also include the same acrylic resin as the emulsion. It is preferable to use acrylic short fibers.

As described above, when acrylic short fibers made of the same resin as the emulsion are used, the compatibility between the acrylic short fibers and the emulsion is good, and the acrylic short fibers are uniformly and stably dispersed in the emulsion. Can be dispersed. On the other hand, when fibers having low compatibility with the acrylic resin emulsion, such as cotton fibers, are added, the fibers may be clumped or easily separated, making it impossible to manufacture gloves.

[Crosslinking Agent] In the present invention, the acrylic resin emulsion preferably contains a crosslinking agent in order to make the acrylic resin sufficiently crosslinkable and to improve the strength of the glove. When the emulsion of the above (3) and (4), that is, an emulsion having self-crosslinking property, is used as the acrylic resin emulsion,
Although the film can be formed without the cross-linking agent, the strength of the 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, particularly preferably 1 to 5 parts by weight, based on 100 parts by weight of the resin solid content of the acrylic resin emulsion. [Other Additives] The glove of the present invention may contain various conventionally known additives such as an antioxidant, a filler and a dispersant, in addition to the crosslinking agent.

In general, non-staining phenols are preferably used as the antioxidant, but amines may be used. The compounding amount of the antioxidant is 0.5 to 0.5 parts by weight of the resin solid content of the acrylic 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 1% of the above resin solid content.
It is preferably 10 parts by weight or less with respect to 00 parts by weight. Further, a dispersant may be blended in order to improve the dispersion of the additives in the acrylic resin emulsion. Examples of such a dispersant include various anionic surfactants. The compounding amount of the dispersant is preferably about 0.3 to 1.0% by weight of the weight of the component to be dispersed.

[Tear properties of gloves] In the gloves of the present invention, in order to prevent the film from being torn when using the gloves, JIS K 6252 (Tear test method for vulcanized rubber) is used.
Is preferably 15 N / mm or more, more preferably 20 N / mm or more, and especially 2 N / mm or more.
It is preferably at least 5 N / mm. [Tensile properties of gloves] In the gloves of the present invention, JIS K6251 is used from the viewpoint of further improving various properties such as modulus, flexibility, and elongation of the gloves.
The tensile stress M ₃₀₀ at 300% elongation (that is, modulus) specified in (Tensile test method for vulcanized rubber) is 2.5 MPa.
Or more, more preferably 3.0 MPa
Above, especially 3.5 MPa or more is preferable.

The tensile strength T _B (JIS K 6251) is preferably not less than 4.5 MPa, more preferably about 5.0 MPa. In addition, the elongation at cutting E _B (J
IS K6251) is preferably at least 350%, more preferably at least 400%, particularly preferably at least 450%. The tensile stress M ₃₀₀ is 2.5M
Or below Pa, or less than the tensile strength T _B is 4.5 MPa, the elongation at break E _B is or below 350%, equivalent to the rubber glove and made of vinyl chloride resin glove or more wearability and desorption There is a possibility that the property cannot be obtained.

[Manufacturing method of gloves] As described above, the gloves of the present invention contain a heat-sensitive agent, an anode coagulant, a cross-linking agent, and the like, if necessary, in an acrylic resin emulsion containing at least short acrylic fibers. Then, if necessary, a preheated glove mold is immersed, the resin emulsion is gelled on the surface of the mold, and further dried.

The heating temperature of the glove mold is appropriately set according to the type of the acrylic resin emulsion to be used, and is usually set so that the mold surface temperature is about 70 to 100 ° C. . As the glove mold, conventionally known ones such as, for example, ceramics and ceramics can be used. Examples of the thermal sensitizer include ammonium nitrate,
Inorganic or organic ammonium salts such as ammonium acetate and zinc ammonium complex salts, or water-soluble resins having a cloud point of normal temperature or higher and 100 ° C or lower such as polyvinyl methyl ether, polyalkylene glycol, polyether polyformal, and functional polysiloxane. Molecules.

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 compounding amount of the above-mentioned heat sensitizer or anode coagulant may be set according to a conventional method, and is usually 0.5 to 5 parts by weight, particularly 0.5 to 2 parts by weight, per 100 parts by weight of the resin solids in the resin emulsion. It is set in the range of 0.0 parts by weight.

[0024]

[Manufacture of gloves]

Example 1 As an acrylic resin emulsion, ZEON Corporation
Product name “LX852” and its product name “LX8
51 "when the weight ratio of dry polymer (resin solids) is 8
After mixing at 0:20, 3 parts by weight of zinc white (crosslinking agent), 0.5 parts by weight of polyvinyl methyl ether (thermal sensitizer), and nitric acid were added to 100 parts by weight of the total amount of the two dry polymers. 1.5 parts by weight of calcium (anode adhesive) and 2 parts by weight of acrylic short fibers (fiber length 0.4 mm) were added.

Next, a glove mold previously heated to about 100 ° C. is immersed in this resin emulsion for about 10 seconds, and then the glove mold is pulled up and dried at room temperature. Gloves were obtained by leaving them in an oven at 100 ° C. for 30 minutes and drying them completely. Examples 2 to 4 With respect to the acrylic short fiber added to the acrylic resin emulsion, the fiber length (mm) and the amount added (parts by weight) to the acrylic resin emulsion were set to the values shown in Table 1, except that A glove was obtained in the same manner as in Example 1.

Comparative Example 1 A glove was obtained in the same manner as in Example 1 except that no acrylic short fiber was added to the acrylic resin emulsion. Comparative Example 2 Example 1 was repeated except that 2 parts by weight of a cotton fiber (fiber length 0.3 mm) was blended in an acrylic resin emulsion instead of 2 parts by weight of an acrylic short fiber (fiber length 0.4 mm).
A glove was obtained in the same manner as described above.

[Tear Test] The gloves obtained in the above Examples and Comparative Examples were punched out, and a test piece of “(b) Angle type with cut” described in JIS K 6252 (Tear test method for vulcanized rubber) was used. Produced. Then, for each test piece, according to the test method described in JIS K6252,
The tear strength TR (N / mm) was determined. Table 1 shows the results.

[Tensile test] The gloves obtained in the above Examples and Comparative Examples were punched out to prepare "dumbbell-shaped No. 4" test pieces described in JIS K6251 (Tensile test method for vulcanized rubber). . Then, for each test piece,
According to the test method described in US Pat.
% Stress M ₃₀₀ Tensile during elongation (MPa), tensile strength T _B (MPa) and elongation at break T _B (%) was measured. Table 1 shows the results.

[Evaluation of Blend State] With respect to the acrylic resin emulsion used for manufacturing the gloves of the above Examples and Comparative Examples, the suspension state, particularly the suspension state of acrylic short fibers and cotton fibers, was observed. (Blend) The state which was uniform and stable was extremely good, and the state of suspension was inadequate for practical use. Those which became clumpy or easily separated were evaluated as x. Table 1 shows the results.

[0030]

[Table 1]

As apparent from Table 1, a comparison between Examples 1 to 4 and Comparative Example 1 revealed that the addition of short acrylic fibers increased the tear strength. Comparative Example 2
The results indicated that the cotton fiber had low compatibility with the acrylic resin emulsion and could not be used for glove production.

Claims (2)

[Claims] 1. A glove formed using an acrylic resin emulsion containing at least an acrylic short fiber. 2. A method for producing gloves, wherein a glove mold is dipped in an acrylic resin emulsion containing at least acrylic short fibers to form a film made of the resin emulsion on the surface of the mold.