JP2020133082A - Glove - Google Patents

Abstract

To provide a glove having high chemical resistance and excellent durability allowing the performance to be retained even when it is repeatedly used.SOLUTION: A glove is such that: a substrate of the glove is formed of a cured product of an active energy ray curable composition containing a thermoplastic resin and an ethylenic unsaturated group-containing cross-linking agent; the thermoplastic resin is a polyvinyl chloride-based resin; 0.5-20 pts.mass of the ethylenic unsaturated group-containing cross-linking agent is contained based on 100 pts.mass of the thermoplastic resin in the active energy ray curable composition; the ethylenic unsaturated group-containing cross-linking agent is trimethylolpropane triacrylate; and the active energy ray is an electron ray.SELECTED DRAWING: None

Description

The present invention relates to a thermoplastic resin glove with improved chemical resistance.

Gloves are used for various types of work to protect hands from dirt and chemicals, but gloves made of thermoplastic resin such as polyvinyl chloride have the advantage of not developing rubber allergies. However, there is a drawback that the permeation resistance to some chemicals is insufficient as compared with gloves made of coagulated rubber latex such as natural rubber and nitrile rubber.
Therefore, in order to improve the chemical resistance performance, gloves (Patent Document 1) in which a thin film layer of an ultraviolet curing agent is formed on the surface of gloves and irradiated with ultraviolet rays, or acrylic having a glass transition temperature of about -30 ° C to about 30 ° C. Gloves containing a barrier layer containing a polymer (Patent Document 2) are known.

Japanese Unexamined Patent Publication No. 56-121729 Japanese Patent Application Laid-Open No. 2007-503532

However, as in Patent Documents 1 and 2, gloves in which a thin film layer or a barrier layer and a substrate are formed in a layered state are deteriorated in chemical resistance due to cracks or peeling of the thin film layer or the barrier layer due to repeated use. There was a possibility that the chemical resistance could not be exhibited reliably when handling chemicals. Therefore, there has been a demand for gloves having high chemical resistance and excellent durability that can maintain their performance even after repeated use.

The glove of the present invention that solves this problem is characterized in that the substrate thereof is composed of a cured product of an active energy ray-curable composition containing a thermoplastic resin and an ethylenically unsaturated group-containing cross-linking agent.

Further, in the present invention, the following steps (1a) to (3a);
(1a) A step of immersing the hand mold in an active energy ray-curable composition containing a thermoplastic resin and an ethylenically unsaturated group-containing cross-linking agent, then pulling up the hand mold and drying it to form a substrate.
(2a) A step of immersing the hand mold on which the substrate is formed in a thermoplastic resin composition, pulling up the hand mold, and drying to form a back treatment layer on the surface of the substrate.
(3a) The present invention provides a method for manufacturing a glove, which includes a step of inverting and peeling a substrate provided with a back treatment layer from a hand mold and then irradiating the substrate with active energy rays to form a glove.

Further, the present invention describes the following steps (1b) to (3b);
(1b) A step of immersing the hand mold in an active energy ray-curable composition containing a thermoplastic resin and an ethylenically unsaturated group-containing cross-linking agent, then pulling up the hand mold and drying to form a substrate.
(2b) A step of immersing the hand mold on which the substrate is formed in an adhesive layer, pulling up the hand mold, and flocking hair on the adhesive layer.
(3b) A step of forming gloves by irradiating the substrate with active energy rays after inverting and peeling the flocked substrate from the hand mold.
It provides a method of manufacturing a glove including.

Further, the present invention describes the following steps (1c) and (3c);
(1c) The hand mold is covered with fibrous gloves, immersed in an active energy ray-curable composition containing a thermoplastic resin and an ethylenically unsaturated group-containing cross-linking agent, and then the hand mold is pulled up and dried to form a substrate. Process to do,
(3c) A step of forming gloves by irradiating the substrate with active energy rays after peeling the substrate from the hand mold.
It provides a method of manufacturing a glove including.

Since the glove of the present invention is obtained by imparting chemical resistance to the base body of the glove without separately providing a layer having chemical resistance, the layer may crack or peel off even after repeated use. It is possible to maintain and exert chemical resistance for a long period of time without deterioration of chemical resistance due to the above.

The substrate of the glove of the present invention is composed of a cured product of an active energy ray-curable composition containing a thermoplastic resin and an ethylenically unsaturated group-containing cross-linking agent.

The above-mentioned thermoplastic resin is not particularly limited, and for example, ethylene-vinyl acetate copolymer, polyurethane, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinyl acetate, chlorinated polyethylene, chlorinated polypropylene, vinyl chloride. Examples include system resins, polystyrene, acrylic resins and the like.

Among these, vinyl chloride resin is preferable from the viewpoint of excellent compatibility with the plasticizer and good texture. The vinyl chloride resin includes not only polyvinyl chloride (vinyl chloride homopolymer) but also a copolymer containing vinyl chloride as a main component. Examples of the monomer copolymerizable with vinyl chloride include vinylidene chloride, ethylene, propylene, acrylic acid, methacrylic acid, vinyl acetate, acrylonitrile and the like. Of these, polyvinyl chloride is particularly preferable. The method for producing the vinyl chloride resin is not particularly limited, and those obtained by conventionally known production methods such as an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, and a bulk polymerization method can be used. The average degree of polymerization of the vinyl chloride resin is not particularly limited, but is preferably 700 to 2000, more preferably 900 to 1500, from the viewpoint of softening the film and improving the texture of the gloves.

The ethylenically unsaturated group-containing cross-linking agent is a compound having an ethylenically unsaturated group in the molecule. Examples of the ethylenically unsaturated group include a vinyl group, a (meth) acryloyl group, a vinyl ether group, an allyl group, an isopropenyl group, and the like. Among these, (meth) acryloyl from the viewpoint of high reactivity with active energy rays. Groups are preferred. The ethylenically unsaturated group-containing cross-linking agent may be a monofunctional type, a bifunctional type, a polyfunctional type, or a polymer type. Specific examples of the monofunctional type include tetrahydrofurfuryl acrylate (THFA), phenoxyethyl acrylate (PEA), lauryl acrylate (LA), 2-ethylhexyl carbitol acrylate (EHCA), isobornyl acrylate (IBOA), 2-. Hydroxy-3-phenoxypropyl acrylate, acryloyl morpholine (ACMO), N-vinylpyrrolidone (NVP), N-vinylcaprolactam (NVC), glycidyl methacrylate (GMA), 2-acryloyloxyethyl isocyanate (AOI), (3-ethyl) Examples thereof include oxetan-3-yl) methyl acrylate and 2- (2-vinyloxyethoxy) ethyl acrylate (VEEA). Specific examples of the bifunctional type include 1,6-hexanediol diacrylate (HDDA), neopentyl glycol diacrylate (NPGDA), tetraethylene glycol diacrylate (TEGDA), tripropylene glycol diacrylate (TPGDA), and tricyclo. Examples thereof include decanedimethanol diacrylate (TCDDA) and bisphenol A / EO4 molar modified diacrylate. Specific examples of the polyfunctional type include trimethylolpropane triacrylate (TMPTA), dipentaerythritol hexaacrylate (DPHA), dimethylolpropanetetraacrylate (DTMPTA), pentaerythritol triacrylate (PETA), and isocyanuric acid EO-modified triacrylate. (THEIC-TA), glycerin triacrylate (MT-3547) and the like. Specific examples of the polymer type include polyester acrylate consisting of hexanediol and phthalic acid, polyester acrylate consisting of trimethylolpropane and adipic acid, polytetramethylene glycol (PTMG), tolylene diisocyanate (TDI) and hydroxyethyl acrylate (HEA). ), Urethane acrylate composed of polyethylene glycol adipate, isophorone diisocyanate (IPDI) and hydroxyethyl acrylate (HEA), bisphenol A type epoxy acrylate, phenol novolac type epoxy acrylate and the like. Of the above, the trifunctional compound is preferable because it has high reactivity with active energy rays, and trimethylolpropane triacrylate (TMPTA) is more preferable.

The blending amount of the ethylenically unsaturated group-containing cross-linking agent in the active energy ray-curable composition is not particularly limited, but is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the thermoplastic resin. 10 parts by mass is more preferable. If the amount of the vinyl group-containing cross-linking agent is less than 0.5 parts by mass, sufficient chemical resistance cannot be obtained, and if it is more than 20 parts by mass, the flexibility of the glove may be impaired.

The present invention provides the active energy ray-curable composition with a plasticizer, a metal oxide, a vulcanizing agent, a vulcanization accelerator, a filler, an antioxidant, a thickener, a pigment, etc., depending on the application and required characteristics. Can be added within a range that does not impair the effect of.

The production of the glove of the present invention is not particularly limited, but for example, it is produced by molding a glove substrate by a dip molding method and then irradiating the substrate with active energy rays. In the dip molding method, the hand mold is immersed in a dip molding composition composed of a sol of a thermoplastic resin, the hand mold is pulled up, and the dip molding composition adhering to the surface of the hand mold is solidified to form a film. This is a method of manufacturing gloves by peeling them from the hand mold. The manufacturing conditions in the dip molding method are not particularly limited, and the hand mold temperature and immersion time when the hand mold is immersed in the dip molding composition, the heating time, the thickness of the glove, the laminating of the back treatment layer or the flocking layer. And the manufacturing conditions such as the thickness thereof can be appropriately adjusted. Further, by covering the hand mold with the fiber gloves in advance and then applying the dip molding method in the same manner as described above, the substrate can be formed on the outer surface of the fiber gloves.

After molding the substrate by the dip molding method, it is irradiated with active energy rays and cured. Examples of active energy rays include ultraviolet rays, infrared rays, microwaves, electron beams, alpha rays, beta rays, neutron rays, gamma rays, X-rays, etc. Among these, electron beams easily adjust the penetrating power to the irradiated object. It is preferable in that. When an electron beam is used as the active energy ray, the irradiation intensity of the electron beam is preferably 10 to 200 kGy, more preferably 30 to 120 kGy. If the irradiation intensity of the electron beam is less than 10 kGy, sufficient chemical resistance may not be obtained, and if it exceeds 200 kGy, discoloration of the thermoplastic resin may occur.

The timing of irradiating the active energy rays is from the hand mold as long as it is after the substrate is formed by solidifying the dip molding composition and forming a film, even before the substrate is peeled from the hand mold. It may be after peeling. When an electron beam is used as the activation energy ray, the electron beam can pass through a packaging material made of resin or paper, so that the substrate may be packed in a resin film or in a cardboard box. By adjusting the irradiation intensity of the electron beam, it is possible to impart sufficient chemical resistance to the gloves.

As a preferred embodiment of the glove manufacturing method of the present invention, the following steps (1a) to (3a);
(1a) A step of immersing the hand mold in an active energy ray-curable composition containing a thermoplastic resin and an ethylenically unsaturated group-containing cross-linking agent, then pulling up the hand mold and drying it to form a substrate.
(2a) A step of immersing the hand mold on which the substrate is formed in a thermoplastic resin composition, pulling up the hand mold, and drying to form a back treatment layer on the surface of the substrate.
(3a) An example is a method including a step of forming gloves by irradiating the substrate with active energy rays after inverting and peeling the substrate provided with the back treatment layer from the hand mold.

In the above step (1a), for example, a ceramic hand mold is immersed in an active energy ray-curable composition (dip molding composition) containing a thermoplastic resin and an ethylenically unsaturated group-containing cross-linking agent. The hand mold is preferably preheated to about 40 to 80 ° C. before immersion. The immersion time may be about 2 to 10 minutes. After the immersion, the hand mold is pulled up from the active energy ray-curable composition, and then the active energy ray-curable composition adhering to the surface of the hand mold is dried and solidified / formed to form a substrate. Drying may be carried out at 150 to 250 ° C. for 1 to 20 minutes, for example. After drying, if necessary, the substrate surface is cooled to about 10 to 80 ° C.

In the above step (2a), a back treatment layer is formed on the surface of the substrate formed in the step (1a). First, the hand mold obtained in the step (1a) having a substrate formed on the surface is immersed in the thermoplastic resin composition. The thermoplastic resin is not particularly limited, and is, for example, ethylene-vinyl acetate copolymer, polyurethane, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinyl acetate, chlorinated polyethylene, chlorinated polypropylene, vinyl chloride-based. Examples thereof include resin, polystyrene, and acrylic resin.

Among these, vinyl chloride resin is preferable from the viewpoint of excellent compatibility with the plasticizer and good texture. The vinyl chloride resin includes not only polyvinyl chloride (vinyl chloride homopolymer) but also a copolymer containing vinyl chloride as a main component. Examples of the monomer copolymerizable with vinyl chloride include vinylidene chloride, ethylene, propylene, acrylic acid, methacrylic acid, vinyl acetate, acrylonitrile and the like. Of these, polyvinyl chloride is particularly preferable. The method for producing the vinyl chloride resin is not particularly limited, and those obtained by conventionally known production methods such as an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, and a bulk polymerization method can be used. The average degree of polymerization of the vinyl chloride resin is not particularly limited, but is preferably 700 to 2000, more preferably 900 to 1500, from the viewpoint of softening the film and improving the texture of the gloves.

In the thermoplastic resin composition, in addition to the above-mentioned thermoplastic resin, water, a surfactant, a stabilizer, a pigment and the like can be used as needed within a range that does not impair the effects of the present invention.

The immersion time in the thermoplastic resin composition may be about 10 seconds to 2 minutes. After the immersion, the hand mold is pulled up from the thermoplastic resin composition, and then the thermoplastic resin composition adhering to the surface of the substrate is dried to be solidified and formed into a film to form a back treatment layer. Drying may be carried out at 150 to 250 ° C. for 1 to 20 minutes, for example. After drying, if necessary, the surface is cooled to about 10 to 80 ° C. By forming the back treatment layer in this way, there is an advantage that the slip when putting a hand on the glove is improved. The back treatment layer forming step of the step (2a) can be omitted, and after forming the substrate by the step (1a), the substrate may be cured by the step (3a) described later.

Next, in step (3a), after the substrate having the back treatment layer is inverted and peeled from the hand mold, the substrate is irradiated with active energy rays and cured to form gloves composed of the cured product. .. When an electron beam is used as the active energy ray, the irradiation intensity of the electron beam is preferably 10 to 200 kGy, more preferably 30 to 120 kGy. If the irradiation intensity of the electron beam is less than 10 kGy, sufficient chemical resistance may not be obtained, and if it exceeds 200 kGy, discoloration of the thermoplastic resin may occur.

Further, as a preferred embodiment of the glove manufacturing method of the present invention, the following steps (1b) to (3b);
(1b) A step of immersing the hand mold in an active energy ray-curable composition containing a thermoplastic resin and an ethylenically unsaturated group-containing cross-linking agent, then pulling up the hand mold and drying to form a substrate.
(2b) A step of immersing the hand mold on which the substrate is formed in an adhesive layer, pulling up the hand mold, and flocking hair on the adhesive layer.
(3b) A step of forming gloves by irradiating the substrate with active energy rays after inverting and peeling the flocked substrate from the hand mold.
A method including the above is exemplified.

In the above step (1b), for example, a ceramic hand mold is immersed in an active energy ray-curable composition (dip molding composition) containing a thermoplastic resin and an ethylenically unsaturated group-containing cross-linking agent. The hand mold is preferably preheated to about 40 to 80 ° C. before immersion. The immersion time may be about 2 to 10 minutes. After the immersion, the hand mold is pulled up from the active energy ray-curable composition, and then the active energy ray-curable composition adhering to the surface of the hand mold is dried and solidified / formed to form a substrate. Drying may be carried out at 150 to 250 ° C. for 1 to 20 minutes, for example. After drying, if necessary, the substrate surface is cooled to about 10 to 80 ° C.

In the above step (2b), a flocking layer is formed on the surface of the substrate formed in the step (1b). First, the hand mold with the substrate formed on the surface obtained in the step (1b) is immersed in the adhesive layer. The adhesive in the adhesive layer is not particularly limited, and for example, ethylene-vinyl acetate copolymer, polyurethane, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinyl acetate, chlorinated polyethylene, chlorinated polypropylene, chloride. Examples include vinyl-based resin, polystyrene, acrylic resin and the like.

Among these, the acrylic resin is preferable from the viewpoint that the flocking can be uniformly flocked with high adhesive strength and high flocking density.

In addition to the acrylic resin described above, water, a surfactant, a stabilizer, a pigment, or the like can be used as necessary for the adhesive layer as long as the effects of the present invention are not impaired.

The immersion time in the adhesive layer may be about 10 seconds to 2 minutes. After the immersion, the hand mold is pulled up from the adhesive layer, and then a flocked body such as a pile is naturally dropped onto the surface of the substrate or the hair is transplanted by electrostatic induction on the adhesive adhering to the surface of the substrate to form a flocked layer. After flocking, if necessary, cool until the surface reaches about 10 to 80 ° C. Forming the flocked layer in this way has the advantage of improving slippage when putting a hand on the glove.

Next, in the step (3b), after the substrate having the flocked layer is inverted and peeled from the hand mold, the substrate is irradiated with active energy rays and cured to form gloves composed of the cured product. When an electron beam is used as the active energy ray, the irradiation intensity of the electron beam is preferably 10 to 200 kGy, more preferably 30 to 120 kGy. If the irradiation intensity of the electron beam is less than 10 kGy, sufficient chemical resistance may not be obtained, and if it exceeds 200 kGy, discoloration of the thermoplastic resin may occur.

Further, as a preferred embodiment of the method for producing a glove of the present invention, the following steps (1c) and (3c);
(1c) The hand mold is covered with fibrous gloves, immersed in an active energy ray-curable composition containing a thermoplastic resin and an ethylenically unsaturated group-containing cross-linking agent, and then the hand mold is pulled up and dried to form a substrate. Process to do,
(3c) A step of forming gloves by irradiating the substrate with active energy rays after peeling the substrate from the hand mold.
A method including the above is exemplified.

In the above step (1c), for example, an active energy ray-curable composition (dip molding composition) containing a thermoplastic resin and an ethylenically unsaturated group-containing cross-linking agent by covering a metal hand mold with fibrous gloves. Immerse in. The immersion time may be about 2 to 10 minutes. After immersion, the hand mold is pulled up from the active energy ray-curable composition, and then the active energy ray-curable composition adhering to the surface of the fiber glove is dried and solidified / formed to form a substrate on the surface of the fiber glove. To form. Drying may be carried out at 150 to 250 ° C. for 1 to 20 minutes, for example. After drying, if necessary, the substrate surface is cooled to about 10 to 80 ° C.

The active energy ray-curable composition (dip molding composition) containing the thermoplastic resin and the ethylenically unsaturated group-containing cross-linking agent is an active energy ray containing the above-mentioned thermoplastic resin and the ethylenically unsaturated group-containing cross-linking agent. In addition to the curable composition, water, a surfactant, a stabilizer, a pigment and the like can be used, if necessary, as long as the effects of the present invention are not impaired.

Next, in the step (3c), after peeling the substrate from the hand mold, the substrate is irradiated with active energy rays and cured to form gloves composed of the cured product. When peeling the substrate from the hand mold, the active energy ray-curable composition is dried, solidified, and formed into a film without inversion, and the substrate is peeled off with the outer surface as the outer surface. When an electron beam is used as the active energy ray, the irradiation intensity of the electron beam is preferably 10 to 200 kGy, more preferably 30 to 120 kGy. If the irradiation intensity of the electron beam is less than 10 kGy, sufficient chemical resistance may not be obtained, and if it exceeds 200 kGy, discoloration of the thermoplastic resin may occur.

In any of the embodiments, the timing of irradiating the active energy rays is after the substrate is formed by solidifying the thermoplastic resin composition and forming a film, before the substrate is peeled off from the hand mold. It may be present or after it has been peeled off from the hand mold. When an electron beam is used as the activation energy ray, the electron beam can pass through a packaging material made of resin or paper, so that the substrate may be packed in a resin film or in a cardboard box. By adjusting the irradiation intensity of the electron beam, it is possible to impart sufficient chemical resistance to the gloves.

The glove of the present invention obtained as described above is excellent in chemical resistance, and the insoluble fraction in tetrahydrofuran after manufacturing the glove is preferably 30% or more, and more preferably 40% or more. In particular, it is preferably 50% or more. Tetrahydrofuran is a good solvent for many thermoplastic resins such as polyvinyl chloride, and the insoluble fraction in tetrahydrofuran is an index of the chemical resistance of gloves. The insoluble fraction in tetrahydrofuran after deterioration is preferably 20% or more, more preferably 30% or more, and particularly preferably 40% or more. The insoluble fraction in tetrahydrofuran after preparation and deterioration is measured by the method described in Examples.

The present invention will be described in detail with reference to Examples below, but the present invention is not limited to these Examples.

Example 1
(Preparation of active energy ray-curable composition)
100 parts by mass of polyvinyl chloride (trade name "PSM-30", manufactured by Toso Co., Ltd.), 100 parts by mass of plasticizer alkyl sulfonate phenyl ether (trade name "Messamol", manufactured by LANXESS), large epoxidation Soybean oil (trade name "ADEKA Sizer O-130P", manufactured by ADEKA Corporation), 5 parts by mass, ethylenically unsaturated group-containing cross-linking agent trimethylolpropantriacrylate (TMPTA) (trade name "Viscoat # 295", Osaka Organic Chemicals) Mix and stir 3 parts by mass of Kogyo Co., Ltd., 5 parts by mass of viscosity modifier (trade name "Leoseal QS-102", manufactured by Tokuyama Co., Ltd.), and 3 parts by mass of titanium dioxide (manufactured by Ishihara Sangyo Co., Ltd.). To prepare a sol-like active energy ray-curable composition.

(Preparation of thermoplastic resin composition)
100 parts by mass of polyvinyl chloride (trade name "C-38", manufactured by Tosoh Co., Ltd.), 400 parts by mass of ion-exchanged water, 4 mass of surfactant (trade name "GWIS-120", manufactured by Nippon Emulsion Co., Ltd.) A thermoplastic resin composition was prepared as a back treatment liquid by mixing and stirring 8 parts by mass of a part and a stabilizer (trade name "ADEKA STUB SC-35", manufactured by ADEKA Corporation).

(Making thermoplastic resin gloves)
The entire ceramic hand mold preheated to a surface temperature of 60 ° C. is immersed in an active energy ray-curable composition, heated at 200 ° C. for 3 minutes, and then allowed to cool until the surface temperature reaches 60 ° C. did. Further, the gloves were immersed in a thermoplastic resin composition, heated at 200 ° C. for 5 minutes, allowed to cool, and then the film was peeled off while being inverted from the hand mold and irradiated with an electron beam of 50 kGy to obtain thermoplastic resin gloves. ..

(Chemical resistance test: after production)
Two test pieces of 2 cm in length and 2 cm in width are cut out from the palm of the obtained glove, immersed in 50 g of tetrafdrofuran at 25 ° C for 24 hours in a glass container with a lid, and then opened 200 mesh. The wire mesh was filtered through a stainless steel wire mesh, and the wire mesh was dried at 25 ° C. for 48 hours, and the dry mass of the test piece remaining on the wire mesh was measured. The insoluble fraction was calculated and measured by dividing the mass of the undissolved test piece by the mass before immersion in tetrahydrofuran. Table 1 shows the measurement results.

(Chemical resistance test: after deterioration)
Two test pieces having a length of 2 cm and a width of 2 cm were cut out from the palm of the glove and heated in a gear oven at 72 ° C. for 72 hours. The heated test piece is immersed in 50 g of tetrafdrofuran at 25 ° C. for 24 hours in a glass container with a lid, filtered through a stainless steel wire mesh with a 200 mesh opening, and the wire mesh is filtered at 25 ° C. for 48 hours. The dry mass of the test piece that had been dried and remained on the wire mesh was measured. The insoluble fraction was calculated and measured by dividing the mass of the undissolved test piece by the mass before immersion in tetrahydrofuran. Table 1 shows the measurement results.

Example 2
The same operation as in Example 1 was performed except that the amount of trimethylolpropane triacrylate (TMPTA) (trade name "Viscoat # 295", manufactured by Osaka Organic Chemical Industry Co., Ltd.) was changed to 5 parts by mass. Plastic resin gloves were produced and their chemical resistance was evaluated after production and after deterioration. Table 1 shows the evaluation results.

Example 3
The same operation as in Example 1 was carried out except that the irradiation intensity of the electron beam was changed to 100 kGy, and a thermoplastic resin glove was produced, and the chemical resistance was evaluated after the production and after deterioration. Table 1 shows the evaluation results.

Example 4
Except for changing the amount of trimethylolpropane triacrylate (TMPTA) (trade name "Viscoat # 295", manufactured by Osaka Organic Chemical Industry Co., Ltd.) to 5 parts by mass and changing the electron beam irradiation intensity to 100 kGy. All the same operations as in Example 1 were carried out to prepare thermoplastic resin gloves, and the chemical resistance was evaluated after the preparation and after deterioration. Table 1 shows the evaluation results.

Comparative Example 1
The same operation as in Example 1 was performed except that trimethylolpropane triacrylate (TMPTA) (trade name "Viscoat # 295", manufactured by Osaka Organic Chemical Industry Co., Ltd.) was not added to prepare thermoplastic resin gloves. The chemical resistance was evaluated after production and after deterioration. Table 1 shows the evaluation results.

Comparative Example 2
Except for the fact that trimethylolpropane triacrylate (TMPTA) (trade name "Viscoat # 295", manufactured by Osaka Organic Chemical Industry Co., Ltd.) was not added and the electron beam irradiation intensity was changed to 100 kGy, all of them were the same as Example 1. The same operation was carried out to prepare thermoplastic resin gloves, and the chemical resistance was evaluated after the preparation and after deterioration. Table 1 shows the evaluation results.

From Table 1, it was shown that the gloves obtained in each example had a higher insoluble fraction in tetrahydrofuran and were excellent in chemical resistance as compared with the gloves of the comparative example. Further, it was found that the gloves obtained in each example had a higher insoluble fraction in tetrahydrofuran even after deterioration as compared with the gloves of the comparative example, indicating that the chemical resistance could be maintained for a long period of time.

Since the gloves of the present invention have high chemical resistance and excellent durability of the effect, they can be advantageously used as gloves for work and the like.

Claims (8)

A glove having a glove substrate composed of a cured product of an active energy ray-curable composition containing a thermoplastic resin and an ethylenically unsaturated group-containing cross-linking agent. The glove according to claim 1, wherein the thermoplastic resin is a polyvinyl chloride resin. The glove according to claim 1 or 2, wherein the active energy ray-curable composition contains 0.5 to 20 parts by mass of an ethylenically unsaturated group-containing cross-linking agent with respect to 100 parts by mass of a thermoplastic resin. The glove according to any one of claims 1 to 3, wherein the ethylenically unsaturated group-containing cross-linking agent is trimethylolpropane triacrylate. The glove according to any one of claims 1 to 4, wherein the active energy ray is an electron beam. Next steps (1a) to (3a);
(1a) A step of immersing the hand mold in an active energy ray-curable composition containing a thermoplastic resin and an ethylenically unsaturated group-containing cross-linking agent, then pulling up the hand mold and drying it to form a substrate.
(2a) A step of immersing the hand mold on which the substrate is formed in a thermoplastic resin composition, pulling up the hand mold, and drying to form a back treatment layer on the surface of the substrate.
(3a) A method for manufacturing a glove, which comprises a step of inverting and peeling a substrate having a back treatment layer from a hand mold and then irradiating the substrate with active energy rays to form a glove. Next steps (1b) to (3b);
(1b) A step of immersing the hand mold in an active energy ray-curable composition containing a thermoplastic resin and an ethylenically unsaturated group-containing cross-linking agent, then pulling up the hand mold and drying to form a substrate.
(2b) A step of immersing the hand mold on which the substrate is formed in an adhesive layer, pulling up the hand mold, and flocking hair on the adhesive layer.
(3b) A method for manufacturing a glove, which comprises a step of inverting and peeling a flocked substrate from a hand mold and then irradiating the substrate with active energy rays to form a glove. Next steps (1c) and (3c);
(1c) The hand mold is covered with fibrous gloves, immersed in an active energy ray-curable composition containing a thermoplastic resin and an ethylenically unsaturated group-containing cross-linking agent, and then the hand mold is pulled up and dried to form a substrate. Process to do,
(3c) A method for manufacturing a glove, which comprises a step of forming a glove by irradiating the substrate with active energy rays after peeling the substrate from the hand mold.