JP2004300596A - Aramid-made work glove - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aramid-made work glove which can prevent the strike-through of a rubber latex, is flexible, and has high adhesion strength. <P>SOLUTION: This aramid-made work glove is characterized by coating with a rubber latex on a knitted glove substrate consisting mainly of aramid-made spun yarns having on the surfaces coating films comprising the condensation product of one or more hydrolysable substituent-having organic metal compounds comprising titanium, zirconium, aluminum and/or tin, and then integrally molding the coated knitted glove substrate. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【００２１】
【表２】

【００２２】
比較例１のアラミド繊維（スパン糸）編み原手と凝固加工法によるＮＢＲゴムとの最大密着強度は１．９４ｋｇｆである。ここでの最大密着強度とは、ＮＢＲコンパウンドが原手裏面まで浸透していない状態でもっとも高い値のこととしている。これに比べ、実施例１の加水分解可能な置換基を持つ有機金属化合物のイソプロパノール溶液で処理すると２．８１ｋｇｆとなり、約４５％密着強度が向上している。比較例３のメチルトリエトキシシランのようなアルコキシシラン化合物で処理をした場合、密着強度の向上は見られないが、実施例２のように加水分解可能な置換基を持つ有機金属化合物を添加することによって３９％〜４７％向上する。また、アルコキシシラン化合物中にフェニル基を２重量％〜７２重量％含有していると実施例３、実施例４、実施例５のように５１％〜６５％向上する。有機金属化合物を添加すればさらに７１％まで効果が上がる。フェニル基が２重量％を下回れば比較例４のように効果は見られない。比較例２よりアラミド製フィラメント糸は表面処理効果が全く出なかった。
【００２３】
比較例１の処理していないアラミド製スパン糸を材料とする編み手袋と感熱加工法によるＮＲゴムとの最大密着強度は２．０６ｋｇｆである。これに比べ、実施例１の加水分解可能な置換基を持つ有機金属化合物のイソプロパノール溶液で処理すると３．４０ｋｇｆとなり、約６５％密着強度が向上する。比較例３のメチルトリエトキシシランのようなアルコキシシラン化合物で処理をした場合、密着強度の向上は見られないが、実施例２のように加水分解可能な置換基を持つ有機金属化合物を添加することによって３８％〜４８％向上する。また、アルコキシシラン化合物中にフェニル基を２重量％〜７２重量％含むと実施例３、実施例４、実施例５のように５０％〜６６％向上する。有機金属化合物を添加すればさらに７４％まで効果が上がる。フェニル基が２重量％を下回れば比較例４のように効果は見られない。比較例２よりアラミド製フィラメント糸は表面処理効果が全く出なかった。
【００２４】
【発明の効果】
以上のように本発明によれば、有機金属化合物の添加もしくはアルコキシシラン化合物からなる縮合体を表面被覆させたアラミド製スパン糸の編み手袋を用いることによってゴムラテックスの裏抜けを防止し、柔軟で且つ密着強度の強いアラミド製作業用手袋を提供することができる。[0001]
TECHNICAL FIELD OF THE INVENTION
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aramid work glove for protecting a hand from being damaged in a meat dismantling operation, a glass handling operation, an engine assembling operation of a car or an airplane, and the like.
[0002]
[Prior art]
Conventionally known aramid fibers have an inactive surface and have poor adhesion to rubber compared to other fiber materials, so that rubber latex penetrates deeply into the aramid fiber base material to achieve a physical anchor effect. Gloves processed by a method of holding and improving adhesion are used. In order to make the adhesion strength between the rubber and the aramid fiber practically usable, there are means such as infiltrating the rubber latex to the back side of the aramid fiber base material, or increasing the thickness of the aramid fiber base material, Glove texture and flexibility are impaired, resulting in gloves with poor workability. Therefore, the rubbery latex is not penetrated to the back surface of the aramid fiber base material, but the thickness is reduced, and the adhesion strength with the rubber is increased, so that a flexible and handy product can be obtained. In order to improve the adhesion between the aramid fiber base material and the rubber, for example, a method of physically etching the surface of the aramid fiber to form irregularities as disclosed in Patent Document 1, a chemical treatment method using sulfuric acid, Although a method of performing surface modification by plasma discharge is adopted, there is a problem that the adhesion strength between the aramid fiber base material and the rubber does not increase.
[0003]
[Patent Document 1]
JP-A-11-335972
[Problems to be solved by the invention]
An object of the present invention is to solve such a problem, and an object of the present invention is to provide a work glove made of aramid, which is flexible and has high adhesion strength by preventing strike-through of rubber latex.
[0005]
[Means for Solving the Problems]
In order to solve this problem, the present invention mainly comprises aramid spun yarn having on its surface a coating made of a condensate of one or more organometallic compounds consisting of titanium, zirconium, aluminum and tin having a hydrolyzable substituent. A rubber latex is coated on a base material of a knitted glove to be formed, and is integrally formed by heating. Further, the present invention is mainly based on an aramid spun yarn having an alkoxysilane condensate cured and solidified by one or more organometallic compounds comprising titanium, zirconium, aluminum and tin having a hydrolyzable substituent on a surface coating. The gist of the present invention is that a rubber latex is coated on a knitted glove base material and is integrally formed by heating. The gist of the present invention is that a rubber latex is coated on a knitted glove base material mainly composed of an aramid spun yarn having a phenyl group-containing alkoxysilane condensate as a surface coating, and integrally molded by heating. Is what you do. Further, the present invention provides an alkoxysilane condensate containing 2% to 72% by weight of a phenyl group cured and solidified by one or more organometallic compounds including titanium, zirconium, aluminum and tin having a hydrolyzable substituent. The gist of the present invention is that a rubber latex is coated on a knitted glove base material mainly composed of aramid spun yarn having a surface coating and is integrally formed by heating.
[0006]
The condensate consisting of one or more organometallic compounds of titanium, zirconium, aluminum, and tin having a hydrolyzable substituent according to the present invention is tetrapropoxy titanate, tetrabutoxy titanate, tetrapropoxy zirconate, tetrabutoxy zirconate. A single condensate or a mixed condensate of tripropoxyaluminate, aluminum acetylacetate, dibutyltin diacetate or dibutyltin dilaurate. When added at least 0.1% by weight or more based on the weight of alkoxysilane, water repellency is imparted to aramid spun yarn. Appear, and the adhesion strength can be increased without penetrating the rubber latex to the back surface of the knitting original material substrate. The alkoxysilane condensate is a monomer or dimer of a trifunctional alkoxysilane having three hydrolyzable substituents in one molecule and a bifunctional alkoxysilane having two hydrolyzable substituents in one molecule. Is a single condensate or a mixed condensate such as an oligomer of isomer to 15-mer, and in one molecule, an epoxy group, a vinyl group, an amino group, a mercapto group, a sulfide group, an isocyanate group, a methacryloxy group, an acryloxy group, a ureide group, It may contain a chloropropyl group or a phenyl group. In particular, when the phenyl group is contained in an amount of 2% by weight to 72% by weight based on the weight of the alkoxysilane condensate, the adhesion strength to the rubber is improved without adding the above-mentioned organometallic compound. A synergistic effect appears. Alkoxysilanes, solvents of organometallic compounds, glycols such as ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, ethanol, methanol, etc. to facilitate chemical reaction with the aramid spun yarn surface Isopropanol, butanol, hexane, toluene, chlorobenzene and the like may be used alone or in combination of two or more. The surface of the aramid spun yarn is treated by dipping the aramid spun yarn in a solution containing an alkoxysilane or an organometallic compound, or dipping a knitted glove mainly composed of the aramid spun yarn, and pulling up the fiber with respect to the weight of the fiber. The squeezing rate is adjusted so as to adhere to a weight% to 8 weight%, and the fiber surface is coated by drying at about 150 ° C. for about 10 minutes. Aramid fibers include spun yarn (spun yarn) and filament yarn. Aramid spun yarn can be used alone, but it is also possible to use a composite yarn with acrylic yarn, polyethylene yarn, PVC, nylon yarn, polyester yarn, cotton yarn, etc. mainly consisting of spun yarn. This aramid spun yarn has particularly improved adhesion strength with rubber as compared with filament yarn. Further, the rubber latex used in the present invention may be a natural rubber, isoprene, chloroprene, acrylate ester, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, urethane, butyl rubber, polybutadiene rubber, silicone rubber, or other such homopolymer. Coated latex or copolymer latex is a copolymer latex having 10% by weight or less of a carboxyl-modified group. These are blended to form a known crosslinking agent, vulcanization accelerator, antioxidant, thickener, Organic or inorganic fillers, plasticizers and the like are added. The term natural rubber includes not only natural rubber alone but also natural rubber-methyl methacrylate copolymer and epoxidized modified natural rubber copolymer (latex). The term acrylic ester rubber is n-butyl acrylate, n-butyl methacrylate, iso-butyl acrylate, iso-butyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, iso-propyl acrylate, iso A homopolymer such as -propyl methacrylate or a copolymer, including a copolymer containing acrylonitrile, methyl methacrylate, allyl methacrylate, N-methylolacrylamide, acrylic acid, methacrylic acid, and the like. The method for producing rubber gloves is as follows. A knitted glove made of aramid fiber is put on a hand mold, rubber latex is coated by a heat-sensitive agent method or a coagulant method, and solidified by heating at 120 to 130 ° C. for about 1 hour. Reaching of the glove may be performed before or after heating the glove. The heat-sensitive agent method is a processing method in which the rubber latex has a gel point at which it gels when it reaches a certain temperature, and the rubber and the base material adhere to each other while suppressing the penetration by adjusting the liquid temperature of the rubber latex and the mold temperature. The coagulant method is a processing method of coagulating a salt with a water or methanol solution of a divalent metal salt such as calcium nitrate, calcium chloride or zinc chloride. When the knitted glove made of aramid coated with the alkoxysilane condensate of the present invention is used, a glove having strong adhesion strength without rubber strikethrough can be obtained.
[0007]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described based on examples. However, these examples do not limit the invention.
[0008]
Example 1
A knitted glove made of aramid spun yarn is immersed in an isopropyl alcohol solution of dibutyltin diacetate (solid content: 1%), and the drawing ratio is adjusted so that the attached solid content is 2% by weight based on the fiber weight. Dry at 10 ° C. for 10 minutes. After covering the surface-treated knitted gloves with a hand mold, the gloves are immersed in a coagulant solution, dried for 1 minute, and then immersed in a compound having the following composition (1), and then at 130 ° C. for 40 minutes. Was cured. A test piece was cut from the palm of the released glove, and a peel strength test was performed. The coagulant used was calcium nitrate (parts by weight) / zinc chloride (parts by weight) = 0.4 / 0.2, 0.6 / 0.3, 0.8 / 0. A trial production was performed with the ratio changed to 4, 1.0 / 0.5, and the adhesion strength was a relative comparison of the maximum adhesion strength in a state where the rubber latex did not penetrate. Table 1 shows the test results. A knitted glove mainly made of spun yarn made of aramid, which has been surface-treated in the same manner, is put on a hand mold, and then dipped in a compound having the following composition (2), which is kept at a constant liquid temperature of 23 ° C., and pulled up. Curing was performed at 40 ° C. for 40 minutes. Prototypes were manufactured by changing the hand mold temperature (° C.) to 65 ° C., 70 ° C., 80 ° C., and 90 ° C., and an adhesion strength test was performed. Table 2 shows the test results.
[0009]
Example 2
Gloves made of aramid spun yarn are immersed in an isopropyl alcohol solution of methyltrimethoxysilane (solid content 6%) and dibutyltin diacetate (solid content 0.4%), and the solid content adhered to the fiber weight is 2 weight. %, And dried at 150 ° C. for 10 minutes. The methyltrimethoxysilane used was (A) a monomer, (B) a pentamer, and (C) a 15-mer. The gloves were prototyped in the same manner as in Example 1, and the results of peel strength are shown in Tables 1 and 2.
[0010]
Example 3
A knitted glove made of aramid spun yarn is immersed in an isopropyl alcohol solution of diphenyldiethoxysilane (solid content: 6%), and the drawing ratio is adjusted so that the attached solid content is 2% by weight based on the fiber weight. Dry at 150 ° C. for 10 minutes. This diphenyldiethoxysilane used a monomer. The gloves were prototyped in the same manner as in Example 1, and the results of peel strength are shown in Tables 1 and 2.
[0011]
Example 4
Immerse knitted gloves made of aramid spun yarn in isopropyl alcohol solution of methyltrimethoxysilane (solid content 6%, about dimer) and phenyltriethoxysilane (solid content 6%, monomer) The squeezing rate was adjusted so that the attached solid content was 2% by weight with respect to the weight, and dried at 150 ° C. for 10 minutes. The ratios of methyltrimethoxysilane (wt%) and phenyltriethoxysilane (wt%) were 90/10, 50/50, 0/100, and dibutyltin diacetate (solid content of 0. 4%) was used. The gloves were prototyped in the same manner as in Example 1, and the results of peel strength are shown in Tables 1 and 2.
[0012]
Example 5
A knitted glove made of aramid spun yarn is immersed in an isopropyl alcohol solution of N-phenyl-γ-aminopropyltrimethoxysilane (solid content: 6%, monomer) to obtain a solid content of 2% based on the fiber weight. The squeezing rate was adjusted so as to be% by weight, and dried at 150 ° C. for 10 minutes. The gloves were prototyped in the same manner as in Example 1, and the results of peel strength are shown in Tables 1 and 2.
[0013]
Comparative Example 1
Gloves were prototyped in the same manner as in Example 1 using knitted gloves made of spun yarn made of aramid without surface treatment. The results of peel strength are shown in Tables 1 and 2.
[0014]
Comparative Example 2
Example 1 Using a knitted glove made of an aramid filament yarn without surface treatment and a knitted glove made of an aramid filament yarn treated with an isopropanol solution of dibutyltin diacetate (1% solids) of Example 1 A glove prototype was produced in the same manner as described above, and the results of the peel strength are shown in Tables 1 and 2.
[0015]
Comparative Example 3
A knitted glove made of aramid spun yarn is immersed in an isopropyl alcohol solution of methyltrimethoxysilane (solid content: 6%), and the drawing ratio is adjusted so that the attached solid content is 2% by weight based on the fiber weight. And dried at 150 ° C. for 10 minutes. The methyltrimethoxysilane used was (A) a monomer, (B) a pentamer, and (C) a 15-mer. The gloves were prototyped in the same manner as in Example 1, and the results of peel strength are shown in Tables 1 and 2.
[0016]
Comparative Example 4
Immerse knitted gloves made of aramid spun yarn in isopropyl alcohol solution of methyltrimethoxysilane (solid content 6%, about dimer) and phenyltriethoxysilane (solid content 6%, monomer) The squeezing rate was adjusted so as to be 2% by weight based on the weight, and dried at 150 ° C. for 10 minutes. The ratio of this methyltrimethoxysilane (% by weight) to phenyltriethoxysilane (% by weight) was 100/0 and 95/5. The gloves were prototyped in the same manner as in Example 1, and the results of peel strength are shown in Tables 1 and 2.
[0017]
-Adhesion strength test Two test pieces of 25 mm x 10 cm were cut from the palms of the prototype glove, and both ends having been peeled off by 20 mm were gripped by grips of a testing machine, and peeled off by 50 mm at a pulling speed of 50 mm / min. The peel strength is a median value measured according to JIS K6256. The unit was kgf.
[0018]
Evaluation of adhesion strength The peel strength was relatively compared at a level at which rubber latex did not penetrate into the back side of the knitted glove made of aramid fiber, and the larger the value, the stronger the adhesion strength.
[0019]
・ Formulation (1)
NBR latex (Lx550 manufactured by Zeon Corporation) 100 parts by weight G-15 (anionic emulsifier manufactured by Kao Corporation) 0.2 parts by weight Colloidal sulfur 1.5 parts by weight Zinc oxide 1.5 parts by weight Vulcanization accelerator (Dithiocarbamate type) 0.5 parts by weight Antioxidant (bisphenol type) 0.5 parts by weight Pigment suitable amount thickener (polyacrylate type) suitable amount / mixing (2)
NR latex 100 parts by weight G-15 (anionic emulsifier manufactured by Kao Corporation) 0.2 parts by weight Colloidal sulfur 1.0 part by weight Zinc oxide 0.8 parts by weight Vulcanization accelerator (dithiocarbamate type) 0.3 part by weight Part antiaging agent (bisphenol-based) 0.5 parts by weight pigment proper amount thickener (sodium alginate) proper amount [0020]
[Table 1]

[0021]
[Table 2]

[0022]
The maximum adhesion strength between the aramid fiber (spun yarn) knitted fabric of Comparative Example 1 and the NBR rubber by the coagulation method is 1.94 kgf. Here, the maximum adhesion strength is the highest value in a state where the NBR compound has not penetrated to the back side of the original hand. On the other hand, when treated with the isopropanol solution of the organometallic compound having a hydrolyzable substituent of Example 1, the weight becomes 2.81 kgf, and the adhesion strength is improved by about 45%. When treated with an alkoxysilane compound such as methyltriethoxysilane of Comparative Example 3, no improvement in adhesion strength is observed, but an organometallic compound having a hydrolyzable substituent as in Example 2 is added. This improves 39% to 47%. In addition, when the alkoxysilane compound contains 2% by weight to 72% by weight of a phenyl group, the content is improved by 51% to 65% as in Examples 3, 4, and 5. The effect is further increased to 71% by adding an organometallic compound. If the phenyl group content is less than 2% by weight, no effect is observed as in Comparative Example 4. From Comparative Example 2, the aramid filament yarn had no surface treatment effect.
[0023]
The maximum adhesion strength between the knitted glove made of the untreated aramid spun yarn of Comparative Example 1 and the NR rubber by the heat-sensitive processing method is 2.06 kgf. On the other hand, when treated with the isopropanol solution of the organometallic compound having a hydrolyzable substituent of Example 1, the weight becomes 3.40 kgf, and the adhesion strength is improved by about 65%. When treated with an alkoxysilane compound such as methyltriethoxysilane of Comparative Example 3, no improvement in adhesion strength is observed, but an organometallic compound having a hydrolyzable substituent as in Example 2 is added. This improves 38% to 48%. Further, when the alkoxysilane compound contains 2% by weight to 72% by weight of a phenyl group, the content is improved by 50% to 66% as in Examples 3, 4, and 5. The effect increases up to 74% if an organometallic compound is added. If the phenyl group content is less than 2% by weight, no effect is observed as in Comparative Example 4. From Comparative Example 2, the aramid filament yarn had no surface treatment effect.
[0024]
【The invention's effect】
As described above, according to the present invention, the addition of an organometallic compound or the use of an aramid spun yarn knitted glove whose surface is coated with a condensate formed of an alkoxysilane compound prevents the rubber latex from slipping through, and is flexible and flexible. In addition, it is possible to provide an aramid work glove having strong adhesion strength.

Claims (4)

Rubber latex on a knitted glove base material mainly composed of spun yarn made of aramid with a coating consisting of a condensate of one or more organometallic compounds consisting of titanium, zirconium, aluminum and tin having hydrolyzable substituents An aramid working glove, which is coated and integrally formed by heating. On a knitted glove base material mainly composed of aramid spun yarn having an alkoxysilane condensate cured and solidified with one or more organometallic compounds consisting of titanium, zirconium, aluminum, and tin having a hydrolyzable substituent on its surface coating Aramid work gloves, characterized by being coated with rubber latex and integrally molded by heating. Aramid work, characterized in that a rubber latex is coated on a knitted glove base material mainly composed of aramid spun yarn having a phenyl group-containing alkoxysilane condensate on the surface coating and integrally molded by heating. gloves. Aramid having, on its surface coating, an alkoxysilane condensate containing 2% to 72% by weight of a phenyl group cured and solidified by one or more organometallic compounds of titanium, zirconium, aluminum, and tin having a hydrolyzable substituent Aramid working gloves, characterized in that a rubber latex is coated on a knitted glove base mainly composed of spun yarn, and is integrally formed by heating.