JP3382879B2 - NBR gloves - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glove made of NBR suitable for home use or work, and more particularly, to a glove having sufficient film strength as a glove, being flexible and flexible. The present invention relates to a glove made of NBR, which is rich in properties and has significantly improved slippage on the surface of the glove during wearing work. [0002] Gloves made of NBR (acrylonitrile butadiene rubber) are more oil-resistant than gloves made of NR (natural rubber) or PVC (polyvinylchloride). It has excellent properties such as resistance, thrust resistance and abrasion resistance. On the other hand, gloves made of NBR have the drawback that they have extremely poor rebound resilience and lack flexibility compared to NR, and they are slippery on the glove surface when grasping an object. Was often viewed as a problem. In order to remedy this drawback, attempts have conventionally been made to soften the composition by adjusting the blending of a vulcanizing agent or by adding a softener. In the preparation of vulcanizing agents, various kinds of chemicals are provided as vulcanizing agents for NBR. However, sulfur (S) and zinc oxide (ZnO) are mainly used. Is generally used, and the strength and flexibility of the NBR film formed by vulcanization are greatly influenced by the number of parts of sulfur (S) and zinc oxide (ZnO). NB for home and work
In the vulcanization system blended in R gloves, the total blended amount of sulfur (S) and zinc oxide (ZnO) is often used in the range of usually 2 to 5 parts by weight, and the tensile strength of the film is strong. Yes, but generally low flexibility, especially in low temperature range (around 0 ° C)
Then it is hard. [0004] Therefore, the inventors of the present invention have repeatedly studied and found that both the flexibility and the slipperiness of the glove surface are related to the physical properties of the glove film, and the slipperiness is determined by the glove surface film when the object is gripped. It has been demonstrated that the contact area between the glove and the object surface becomes larger, that is, the softness of the glove surface film is greatly related. Among them, the total blending amount of sulfur (S) and zinc oxide (ZnO) is used in the range of 1 to 2 parts by weight, and the 100% modulus value is set to 20 kg / cm ² or less to improve the slip prevention effect. However, this method alone has a disadvantage that it is difficult to obtain sufficient strength as a glove film. As the softener, adipate-based plasticizers, mineral oils, vegetable oils, and the like are often used. These additives greatly contribute to softening when added in small amounts, but gradually migrate to the glove surface. Then, there was a problem that it became very slippery when working in a water leak situation. An object of the present invention is to solve such a problem, and an object of the present invention is to provide an NBR glove having a soft formed film, low slipperiness on the film surface, and a film strength enough to withstand practical use. SUMMARY OF THE INVENTION [0006] We have found that
The intense research has been conducted on the development of a technique which has both film strength and flexibility enough to be practically used as a working NBR glove, and simultaneously prevents the glove surface from slipping when gripped. Then, as a result of selecting the type and ratio of the monomer in the acrylate-based copolymer latex and proceeding with the development, an alkyl acrylate-acrylonitrile-
Acrylic acid or methacrylic acid copolymer latex
When blended with R latex, the film is rich in flexibility and hardly slips when water leaks, and one or both of a rosin-based resin latex and a terpene-based resin latex is 1 to 10 times the solid content of NBR latex.
The addition of parts by weight alleviates the decrease in strength, and has found that a tensile strength of 200 kg / cm ² or more, which is the standard of practicality, can be maintained, and the present invention has been completed. [0007] That NBR gloves of the present invention, NBR
For latex, a copolymer consisting of alkyl acrylate, acrylonitrile and acrylic or methacrylic acid
And polymerized latex, is characterized in that formed by molding using the NBR latex blend is mixed with at least one of latex rosin resin and terpene resin material. Here, the rosin-based resin latex and the terpene-based resin latex are excellent compatibilizers in different types of latex blends, and are auxiliary reinforcing agents that enhance the tensile strength without increasing the modulus by 100%, that is, without curing the NBR film. As an important function. The NBR latex used in the present invention comprises:
A so-called low to high acrylonitrile NBR containing 20 to 45 mol% of acrylonitrile,
% Or less of a carboxyl-modified group, and those having a molecular weight in a range generally used as a glove material can be used. Rosin resin is a resin acid obtained by modifying rosin acid, which is a monocarboxylic acid containing abietic acid as a main component, with maleic acid or fumaric acid, or after stabilizing them by disproportionation or hydrogenation, What is esterified by reacting with various polyalcohols and emulsified in the presence of an emulsifier is used. The terpene resins include terpene resins and terpene phenol resins. The terpene resins are mainly terpenes of α-pinene, β-pinene and dipentene (limonene), either alone or copolymerized. Further, α-pinene phenol resin, dipentene phenol resin, terpene bisphenol resin, etc. obtained by polymerizing various phenols on terpene resin can be used. As the alkyl acrylate component, ethyl acrylate, n-butyl acrylate, iso-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate and the like are effective. The composition ratio of the monomer of the copolymer of alkyl acrylate-acrylonitrile-acrylic acid or methacrylic acid is as follows: alkyl acrylate; 94 to 75 mol (%), acrylonitrile; 5 to 20 mol (%), acrylic acid or methacrylic acid; 5 mol (%) is preferred and the NB to be blended
An alkyl acrylate copolymer polymerized in an appropriate ratio according to the properties of the R latex is provided. There is no particular limitation on the molecular weight of the copolymer. In the production of gloves made of NBR, a dipping process or a coating process is performed using NBR latex containing the above-mentioned components as a material. DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described based on embodiments, but the present invention is not limited to these. Embodiment 1 A ceramic glove mold was immersed in a 30% calcium nitrate methanol solution, then immersed in an NBR latex compound having the following composition (1) for 30 seconds, pulled up, and pulled up to 80 ° C. × 20.
After drying for min, heat treatment was performed at 130 ° C. × 1 hr, and the mold was inverted and released from a hand mold to produce a prototype NBR glove. A test piece (63.5 mm x 63.5 m) was taken from the palm of this glove.
m), measure the dynamic friction coefficient under wet conditions,
Calculated. The tensile strength and 100% modulus of this glove were measured and calculated using a test piece cut from the glove hem. Table 1 shows the result data. However, the NBR latex in the compounding raw material is Nippol LX550 (manufactured by Nippon Zeon Co., Ltd .; the same applies hereinafter), and the nBA-AN-AA copolymer latex is n-butyl acrylate; 88 mol%
Acrylonitrile; 10 mol% -acrylic acid; 2 mol% copolymer latex having a molecular weight of about 200,000, both of which are indicated by solids weight. Formulation (1) NBR latex 70 parts by weight nBA-AN-AA copolymer latex 30 parts by weight Zinc oxide 2 parts by weight Sulfur 1 part by weight Vulcanization accelerator 0.5 part by weight Antioxidant 1 part by weight Pigment appropriate amount modification Rosinate 5 parts by weight Embodiment 2 A glove mold made of ceramics is immersed in a 30% calcium nitrate methanol solution, then immersed in an NBR latex compound of the following formulation (2) for 30 seconds, pulled up, and pulled up to 80 ° C. × 20.
After drying for min, heat treatment was performed at 130 ° C. × 1 hr, and the mold was inverted and released from a hand mold to produce a prototype NBR glove. A test piece (63.5 mm x 63.5 m) was taken from the palm of this glove.
m), measure the dynamic friction coefficient under wet conditions,
Calculated. The tensile strength and 100% modulus of this glove were measured and calculated using a test piece cut from the glove hem. Table 1 shows the result data. Formulation (2) NBR latex 70 parts by weight nBA-AN-AA copolymer latex 30 parts by weight Zinc oxide 2 parts by weight Sulfur 1 part by weight Vulcanization accelerator 0.5 part by weight Antioxidant 1 part by weight Pigment appropriate amount Terpene Phenol 5 parts by weight Embodiment 3 A ceramic glove mold was immersed in a 30% calcium nitrate methanol solution, then immersed in an NBR latex compound having the following composition (3) for 30 seconds, pulled up, and pulled up to 80 ° C. × 20.
After drying for min, heat treatment was performed at 130 ° C. × 1 hr, and the mold was inverted and released from a hand mold to produce a prototype NBR glove. A test piece (63.5 mm x 63.5 m) was taken from the palm of this glove.
m), measure the dynamic friction coefficient under wet conditions,
Calculated. Also, the glove's tensile strength and 100 g
% Modulus measured on a test piece cut from the glove hem,
Calculated. Table 1 shows the result data. However, the 2EHA-AN-AA copolymer latex in the compounding raw material is a copolymer latex of 2-ethylhexyl acrylate; 88 mol% -acrylonitrile; 10 mol% -acrylic acid; 2 mol%, and has a molecular weight of about 200,000. is there. Formulation (3) NBR latex 70 parts by weight 2EHA-AN-AA copolymer latex 30 parts by weight Zinc oxide 2 parts by weight Sulfur 1 part by weight Vulcanization accelerator 0.5 part by weight Antioxidant 1 part by weight Pigment appropriate amount modification Rosinate 5 parts by weight Embodiment 4 A ceramic glove mold is immersed in a 30% calcium nitrate methanol solution, then immersed in an NBR latex compound having the following composition (4) for 30 seconds, and pulled up to 80 ° C. × 20.
After drying for min, heat treatment was performed at 130 ° C. × 1 hr, and the mold was inverted and released from a hand mold to produce a prototype NBR glove. A test piece (63.5 mm x 63.5 m) was taken from the palm of this glove.
m), measure the dynamic friction coefficient under wet conditions,
Calculated. In addition, the tensile strength of gloves made of NBR and 100
% Modulus measured on a test piece cut from the glove hem,
Calculated. Table 1 shows the result data. However, nBA-AN-MA copolymer latex of the compounding raw material is n
Butyl acrylate; 88 mol% acrylonitrile; 10 mol% methacrylic acid; 2 mol% copolymer latex having a molecular weight of about 200,000. Formulation (4) NBR latex 70 parts by weight nBA-AN-MA copolymer latex 30 parts by weight Zinc oxide 2 parts by weight Sulfur 1 part by weight Vulcanization accelerator 0.5 part by weight Antioxidant 1 part by weight Pigment appropriate amount modification Rosin acid ester 5 parts by weight Comparative Example 1 As in Embodiment 1, a ceramic glove mold was immersed in a 30% calcium nitrate methanol solution, then immersed in an NBR latex compound having the following composition (5) for 30 seconds, and pulled up. After drying at 80 ° C x 20 min, 1
A heat treatment was performed at 30 ° C. × 1 hr, and the mold was inverted and released from the hand mold to produce a prototype NBR glove. A test piece (63.5 mm × 63.5 mm) was cut out from the palm of this glove, and the dynamic friction coefficient under wet conditions was measured and calculated. Further, the tensile strength and the 100% modulus of the NBR glove were measured and calculated using a test piece cut from the glove hem. Table 1 shows the result data. Formulation (5) NBR latex 70 parts by weight nBA-AN-AA copolymer latex 30 parts by weight Zinc oxide 2 parts by weight Sulfur 1 part by weight Vulcanization accelerator 0.5 part by weight Antioxidant 1 part by weight Pigment appropriate amount comparison Example 2 As in Embodiment 1, a ceramic glove mold was immersed in a 30% calcium nitrate methanol solution, then immersed in an NBR latex compound having the following composition (6) for 30 seconds, pulled up and dried at 80 ° C. × 20 min. After one
A heat treatment was performed at 30 ° C. × 1 hr, and the mold was inverted and released from the hand mold to produce a prototype NBR glove. A test piece (63.5 mm × 63.5 mm) was cut out from the palm of this glove, and the dynamic friction coefficient under wet conditions was measured and calculated. Further, the tensile strength and the 100% modulus of the NBR glove were measured and calculated using a test piece cut from the glove hem. Table 1 shows the result data. Formulation (6) NBR latex 100 parts by weight Zinc oxide 2 parts by weight Sulfur 1 part by weight Vulcanization accelerator 0.5 part by weight Antioxidant 1 part by weight Pigment suitable amount Comparative Example 3 As in the first embodiment, porcelain After the glove mold was dipped in a 30% calcium nitrate methanol solution, it was dipped in an NBR latex compound having the following composition (7) for 30 seconds, pulled up and dried at 80 ° C. for 20 minutes.
A heat treatment was performed at 30 ° C. × 1 hr, and the mold was inverted and released from the hand mold to produce a prototype NBR glove. A test piece (63.5 mm × 63.5 mm) was cut out from the palm of this glove, and the dynamic friction coefficient under wet conditions was measured and calculated. Further, the tensile strength and the 100% modulus of the NBR glove were measured and calculated using a test piece cut from the glove hem. Table 1 shows the result data. Formulation (7) NBR latex 100 parts by weight Adipate ester plasticizer 10 parts by weight Zinc oxide 2 parts by weight Sulfur 1 part by weight Vulcanization accelerator 0.5 parts by weight Antioxidant 1 part by weight Pigment appropriate amount Measurements, calculations, and evaluations based on the forms 1-4 and Comparative Examples 1-3 were performed as follows. Measurement and Calculation of Dynamic Friction Coefficient Based on ASTM D 1894, an NBR film test piece cut from a glove palm was attached to a moving weight based on ASTM D 1894, and one piece of water was placed on a stainless steel plate with a fixed amount of water.
The test piece was run at a moving distance of 130 mm at a speed of 50 mm / min, a load changed by friction between the test piece and the stainless steel plate was measured, and a running resistance (dynamic friction coefficient) was calculated. Contact Area of Moving Weight 63.5 mm × 63.5 mm Formula μK (Coefficient of Dynamic Friction) = C / D C = Average Load Value (g) after Uniform Running D = Weight of Moving Weight Measurement of 200 g tensile strength, 100% modulus Test piece (63.5 mm × 6
3.5mm), cut out 4 pieces, tensile strength and 100%
The modulus was measured according to JIS K6301. Evaluation of anti-slip It was determined that the larger the value of the dynamic friction coefficient, the more effective the anti-slip effect. Evaluation of Softness The lower the 100% modulus, the more flexible. [Table 1] Comparative Example 2 shows the physical properties of a conventional NBR glove generally used as a household or work glove, and the tensile strength was 42%.
Although it is as tough as 0 kg / cm ² , it has a 100% modulus as hard as 28.0 kg / cm ² . In Comparative Example 1, nBA-AN-AA (nBA / AN / AA = 88) was added to the NBR latex.
(Mol% / 10 mol% / 2 mol%) The gloves blended with the copolymerized latex have the physical properties, but when the 100% modulus becomes 20 kg / cm ² or less, the tensile strength becomes 170.
200k as the standard for practical strength, down to kg / cm ²
g / cm ² . On the other hand, in the first embodiment, the modified rosin acid ester was added in an amount of 5 parts by weight as compared with the comparative example 1.
The tensile strength is 222 kg / cm ² and about 30% while maintaining the flexibility at 100% modulus of 18.0 kg / cm ^2.
Has also been enhanced. In the second embodiment, terpene phenol is added in an amount of 5 parts by weight instead of the modified rosin acid ester in the compounding raw material of the first embodiment, but the 100% modulus is as flexible as 18.3 kg / cm ² , The tensile strength is 235 kg / cm ² , about 40% as compared with Comparative Example 1.
Has also been enhanced. In the third embodiment, the n-butyl acrylate-acrylonitrile-acrylic acid copolymer in the compounding raw material of the first embodiment is replaced with a 2-ethylhexyl acrylate-acrylonitrile-acrylic acid copolymer. In the embodiment 4, n- in the compounding raw material of the embodiment 1
Butyl acrylate-acrylonitrile-acrylic acid copolymer was converted to n-butyl acrylate-acrylonitrile-
In place of the methacrylic acid copolymer, both are flexible with a 100% modulus of 20 kg / cm ² or less, and have a reinforced tensile strength of 200 kg / cm ² or more. In terms of the anti-slip effect associated with flexibility,
In Embodiments 1 to 4 and Comparative Examples 1 and 2, it can be seen that the lower the modulus, the more effective it is in preventing slippage. In Comparative Example 3 in which a plasticizer was added, the dynamic friction coefficient μK was 0.17
Which indicates that the anti-slip effect is remarkably inferior. As described above, according to the present invention, NBR latex and alkyl acrylate-acrylonitrile-
By blending an appropriate amount of a copolymerized latex of acrylic acid or methacrylic acid with a rosin acid-based resin or terpene-based resin, an NBR glove can have a sufficiently durable film strength for home use or work use. It is possible to work comfortably without slipping on the surface of the glove even when gripping an object.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification code FI C08L 33/20 C08L 33/20 93/00 93/00 93/04 93/04 // B29K 9:00 B29K 9:00 33: 00 33:00 86:00 86:00 B29L 31:48 B29L 31:48 (56) References JP-A-11-81014 (JP, A) WO 99/6481 (WO, A1) WO 98/3584 ( (WO, A1) (58) Field surveyed (Int. Cl. ⁷ , DB name) A41D 19/00

Claims (1)

(57) [Claim 1] A copolymer latex comprising an alkyl acrylate, acrylonitrile, acrylic acid or methacrylic acid, and a rosin-based resin with respect to NBR latex.
Mixing at least one latex terpene resin and
If the NBR latex blend is molded using the material name Ru NBR gloves.