JP2020037635A - Glove dip composition, method for manufacturing glove, and glove - Google Patents

Abstract

To provide a glove dip composition that can produce a glove having a high tensile strength, by producing a glove without reducing the film-forming property even if thinner-wall and lighter-weight are aimed.SOLUTION: The problem is solved by a glove dip composition containing an elastomer and a silicon-containing organic coagulant for coagulating the glove dip composition.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a glove dip composition, a method for producing a glove, and a glove.

General rubber gloves widely used in various industrial fields such as the food industry, electronic component manufacturing industry, pharmaceutical industry and the like, work in ordinary households, and the like are manufactured by dip molding of latex containing an elastomer.
In recent years, gloves have been made thinner and lighter in order to reduce the cost of gloves. However, in general, when the thickness and weight of the glove are reduced, there is a problem that the tensile strength of the glove is reduced.

In the field of gloves, development for improving mechanical properties such as tensile strength has been conventionally promoted. For example, Patent Literature 1 uses a carboxylated acrylonitrile butadiene containing an unsaturated carboxylic acid as an elastomer. Further, a rubber glove having improved mechanical properties by using two-step crosslinking consisting of self-crosslinking with an unsaturated carboxylic acid and metal crosslinking with an inorganic coagulant is disclosed.
Further, Patent Literature 2 discloses a rubber glove using the same elastomer as that of Patent Literature 1 and improving mechanical properties by using multipoint crosslinking with polycarbodiimide.

WO2012 / 043893A International Publication No. WO2018 / 117109

  The inventions disclosed in Patent Literatures 1 and 2 described above improve the tensile strength by using an elastomer having a specific structure and improving the strength of a bond related to crosslinking in the structure. In these inventions, when trying to reduce the thickness and weight, it is necessary to reduce the concentration of the elastomer, the coagulant and the like in the latex. However, there is a problem that the film forming property is reduced due to the reduction of these raw materials, and as a result, the tensile strength is reduced.

  Therefore, the present invention provides a glove dip composition that can produce gloves without reducing film-forming properties even when the thickness and weight are reduced, and that can produce gloves having high tensile strength. That is the task.

  The present inventor has conducted intensive studies to solve the above problems, and as a result, by adding a small amount of a silicon-containing organic coagulant for coagulating the glove dip composition to the glove dip composition containing the elastomer, the tensile strength was increased. The present inventors have found that a rubber glove having high strength and excellent film forming properties can be manufactured, and the present invention has been achieved.

（式（１）において、０．１ｍｏｌ％≦ｘ≦１．０ｍｏｌ％、０．５ｍｏｌ％≦ｙ≦１．２ｍｏｌ％、４５ｍｏｌ％≦ｍ≦５６ｍｏｌ％、及び４２ｍｏｌ％≦ｎ≦５５ｍｏｌ％である。）
［６］ ［１］〜［５］の何れかに記載の手袋用ディップ組成物を撹拌しながら放置する撹拌工程、及び
手袋成形型を、前記手袋用ディップ組成物に浸漬するディッピング工程、
を含む、手袋の製造方法。
［７］ 前記ディッピング工程の前に、手袋成形型を、カルシウムイオン含有無機凝固剤を含む凝固剤液中に浸して、該凝固剤を手袋成形型に付着させる無機凝固剤付着工程、を含む、［６］に記載の手袋の製造方法。
［８］ エラストマーを含み、かつ、ケイ素含有量が０．０００５〜０．３重量％である手袋。 That is, the present invention provides the following specific embodiments [1] to [8].
[1] A glove dip composition comprising an elastomer and a silicon-containing organic coagulant for coagulating the glove dip composition.
[2] The glove dip composition according to [1], wherein the content of the silicon-containing organic coagulant is 0.1 to 3.0% by weight based on the total solid content of the glove dip composition. .
[3] The glove dip composition according to [1] or [2], wherein the silicon-containing organic coagulant is a silicone oil.
[4] The glove dip composition according to [3], wherein the silicone oil is a polyether-modified silicone oil.
[5] The glove dip composition according to [4], wherein the polyether-modified silicone oil is represented by the following formula (1).

(In the formula (1), 0.1 mol% ≦ x ≦ 1.0 mol%, 0.5 mol% ≦ y ≦ 1.2 mol%, 45 mol% ≦ m ≦ 56 mol%, and 42 mol% ≦ n ≦ 55 mol%. )
[6] a stirring step of leaving the glove dip composition according to any one of [1] to [5] with stirring, and a dipping step of dipping a glove mold into the glove dip composition;
A method for producing gloves.
[7] Before the dipping step, an inorganic coagulant adhering step of immersing the glove mold in a coagulant liquid containing a calcium ion-containing inorganic coagulant to adhere the coagulant to the glove mold is included. The method for producing a glove according to [6].
[8] A glove containing an elastomer and having a silicon content of 0.0005 to 0.3% by weight.

ADVANTAGE OF THE INVENTION According to this invention, the glove dip composition which can manufacture gloves with large tensile strength can be provided by manufacturing gloves without reducing film-forming properties even if the thickness and weight are reduced. .
Furthermore, in the case of ordinary rubber gloves, the elongation rate in a tensile test tends to decrease with a decrease in the thickness of the glove, but according to the present invention, the elongation rate is hard to decrease even when the glove thickness is reduced. A glove dip composition from which gloves can be manufactured can be provided.

It is sectional drawing which showed typically an example of the fatigue durability test apparatus. It is a figure which shows the relationship between film thickness and FAB in the cured film produced using polycarbodiimide as a crosslinking agent. It is a figure which shows the relationship between film thickness and FAB in the cured film produced using the epoxy group containing compound as a crosslinking agent. It is a figure which shows the relationship between film thickness and fatigue durability in the cured film produced using polycarbodiimide as a crosslinking agent. It is a figure which shows the relationship between film thickness and fatigue durability in the cured film produced using the epoxy group containing compound as a crosslinking agent. It is a figure which shows the relationship between a film thickness and a tensile elongation in the cured film produced using polycarbodiimide as a crosslinking agent.

Hereinafter, embodiments of the present invention will be described in detail. The following embodiments are examples (representative examples) of the embodiments of the present invention, and the present invention is not limited to these. In addition, the present invention can be arbitrarily modified and implemented without departing from the gist thereof.
In the present invention, “(meth) acryl” means acryl and / or methacryl.

<1. Glove dip composition>
The glove according to the embodiment of the present invention is formed by a manufacturing method described below using a glove dip composition having the following composition (hereinafter, also simply referred to as “glove dip composition” or “dip composition”). It is obtained by doing.
Dip composition: comprises an elastomer and a silicon-containing organic coagulant for coagulating the glove dip composition.

<1-1. Silicon-containing organic coagulant>
The silicon-containing organic coagulant is a substance that coagulates (eg, gels) under specific conditions. For example, a thermosensitive coagulant is a substance that coagulates at a specific temperature or higher. By dispersing the coagulant in the dip composition and coagulating the coagulant, it is possible to obtain a glove having a higher tensile strength than when coagulating without containing the coagulant.
As the coagulant, there is an inorganic coagulant such as calcium nitrate. However, the inorganic coagulant tends to form an aggregate and hardly disperse uniformly. On the other hand, since the organic coagulant has a higher affinity for the elastomer than the inorganic coagulant, it is easily dispersed uniformly in the dip composition. Therefore, since the solidified resin is coagulated in a state of being uniformly dispersed in the latex, not only the tensile strength of the obtained glove becomes uniform, but also the film forming property of the finally obtained cured film is improved.
In addition, a metal salt containing an element such as calcium, which is an inorganic coagulant generally used in the production of rubber gloves, forms a crosslink by ionic bonding with a polar group such as a carboxyl group in the elastomer. It improves the mechanical properties such as the tensile strength of the glove to be obtained. That is, the effect as a coagulant differs depending on the type of the crosslinking reaction. On the other hand, the silicon-containing organic coagulant improves mechanical properties such as tensile strength by gelling and coagulating the coagulant itself. Therefore, the effect as a coagulant can be stably exhibited irrespective of the type of the elastomer, the crosslinking agent, and the like. However, since the silicon-containing organic coagulant may affect the cross-linking reaction depending on the type of the cross-linking agent, the degree of influence on the tensile strength changes depending on the type of the elastomer, the cross-linking agent, and the like.

The type of the silicon-containing organic coagulant is not particularly limited, and for example, a silicone oil which is a heat-sensitive coagulant can be used.
When silicone oil is used, its type is not limited, and polyether-modified silicone oil, alkyl-modified silicone oil, aralkyl-modified silicone oil, ester-modified silicone oil, amide-modified silicone oil, phenyl-modified silicone oil, amine-modified silicone oil, epoxy Modified silicone oil, mercapto-modified silicone oil, carboxyl-modified silicone oil, carbinol-modified silicone oil, hydrogen-modified silicone oil, or the like can be used. Among them, non-reactive silicone oils such as polyether-modified silicone oil, alkyl-modified silicone oil, aralkyl-modified silicone oil, ester-modified silicone oil, and amide-modified silicone are preferable from the viewpoint of stably exerting the effect as a coagulant. Oil and phenyl-modified silicone oil are preferred, and polyether-modified silicone oil is particularly preferred from the viewpoints of releasability and completion.

As the polyether-modified silicone oil, for example, those having a structure represented by the following formula (1) can be used.

The above structure can be analyzed by performing a nuclear magnetic resonance spectrum analysis under the following conditions.
Measurement model: AL400 type (manufactured by JEOL Ltd.)
Measurement nuclei: ¹ H and ²⁹ Si
Measurement solvent: D ₂ O
Pretreatment: The sample was dried overnight at room temperature under N ₂ gas flow, and then dissolved in D ₂ O. Pulse delay time: 2 seconds Measurement temperature: 25 ° C

  In the above formula (1), from the viewpoint of improving the tensile strength, x is preferably 0.1 mol% ≦ x ≦ 1.0 mol%, and preferably 0.2 mol% ≦ x ≦ 0.6 mol%. More preferably, y is preferably 0.5 mol% ≦ y ≦ 1.2 mol%, more preferably 0.6 mol% ≦ y ≦ 1.0 mol%, and m is 45 mol% ≦ m ≦ 56 mol. %, More preferably 50 mol% ≦ m ≦ 56 mol%, and n is preferably 42 mol% ≦ n ≦ 55 mol%, and more preferably 43 mol% ≦ n ≦ 50 mol%. More preferred.

When x and y that specify the structure of the main chain of the polyether-modified silicone oil are within the above range, the low surface tension specific to silicone oil is sufficiently exhibited, and high water repellency, high mold release, and high defoaming properties are obtained. Is expressed.
On the other hand, when the m of the polyethylene glycol (PEG) portion and the n of the polypropylene glycol (PPG) portion, which specify the structure of the water-soluble copolymerized side chain, are within the above ranges, the side chain structure itself becomes cloudy. The point tends to be 40-70 ° C. This side chain structure dissolves in water when the temperature is lower than 40 to 80 ° C., but in this temperature range, a dehydration reaction occurs and separation / precipitation due to gelation easily occurs, and the solidification function is excellent.
In addition, the present inventors have found that when the molecular weight of the polyether-modified silicone oil is large and the PEG / PPG ratio is small (rich in PPG), the tensile strength of the finally obtained molded article can be significantly increased. I found what I could do. On the other hand, when the molecular weight of the polyether-modified silicone oil is small and the PEG / PPG ratio is large (PEG rich), it is possible to increase the breaking time of the finally obtained molded article in artificial sweat liquid. I found it.

The content of silicon in the silicon-containing organic coagulant is preferably 0.5% by weight or more, more preferably 0.7% by weight or more, and still more preferably 1.0% by weight or more. The content is preferably 10% by weight or less, more preferably 5% by weight or less, and particularly preferably 3% by weight or less.
If it exceeds the upper limit of the above range, the glove finally obtained will be too hard and excessive, and if it is below the lower limit of the above range, the required film forming property and tensile strength will be lower.
The silicon content in the silicon-containing organic coagulant can be measured by ICP emission spectroscopy. For example, using an ICPE-9820 type (manufactured by Shimadzu Corporation) as an analysis model, put a sample and an acid in a decomposition container as an analysis sample, seal the sample, irradiate with microwaves, heat decompose, and then make a volume with ultrapure water. It can be measured using a solution prepared as a test solution.

The content of the silicon-containing organic coagulant is preferably 0.1% by weight or more, more preferably 0.2% by weight or more, and more preferably 0.3% by weight based on the total solid content of the dip composition. %, More preferably 0.4% by weight or more, particularly preferably 5% by weight or less, more preferably 4% by weight or less, and still more preferably 3% by weight or less. It is particularly preferred that there is.
If it exceeds the upper limit of the above range, the glove finally obtained will be too hard and excessive, and if it is below the lower limit of the above range, the required film forming property and tensile strength will be lower.

<1-2. Elastomer>
As described above, the effect of improving the tensile strength of the silicon-containing organic coagulant is manifested irrespective of the type of the elastomer, although the degree of the effect may vary. Therefore, the type of the elastomer is not particularly limited as long as it can be generally used as a raw material for rubber gloves. As a structural unit constituting the elastomer, for example, butadiene rubber, acrylonitrile-butadiene rubber, styrene-butadiene rubber, ethylene-propylene-diene rubber, isoprene rubber, butyl rubber, halogenated butyl rubber, chloroprene rubber, isobutylene-isoprene rubber, silicone rubber, acrylic Structural units derived from rubber, synthetic rubber such as epoxidized natural rubber, acrylate butadiene rubber and the like, and those in which the molecular chain terminals of these synthetic rubbers or natural rubbers have been modified can be selected. Or two or more of them may be used in any combination and in any ratio.
The ratio of the structural units in the elastomer can be simply determined from the weight ratio (solid content ratio) of the raw materials used for producing the elastomer used in the embodiment of the present invention.

When an elastomer having a butadiene-derived structural unit is used, the type of the structural unit is not particularly limited, but is preferably a 1,3-butadiene-derived structural unit. Structural units derived from butadiene may be used to impart flexibility to rubber gloves.
The ratio of butadiene-derived structural units, that is, the ratio of butadiene residues, is usually at least 50% by weight, preferably at least 53% by weight, particularly preferably at least 53% by weight, based on 100% by weight of the elastomer, from the viewpoint of improving tensile strength and flexibility. Is 55% by weight or more, and usually 80% by weight or less, preferably 75% by weight or less, particularly preferably 70% by weight or less.

  Further, it may include a structural unit derived from (meth) acrylonitrile, which is an element that mainly gives strength to the rubber glove. The structural unit derived from (meth) acrylonitrile is excellent in tensile strength and chemical resistance, but is too hard if the content is too large. The ratio of the structural unit derived from (meth) acrylonitrile, that is, the ratio of the (meth) acrylonitrile residue is based on 100% by weight of the elastomer, from the viewpoint of improving tensile strength and chemical resistance and preventing the resin from becoming too hard. It is usually at least 20% by weight, preferably at least 25% by weight, particularly preferably at least 30% by weight, and usually at most 50% by weight, preferably at most 45% by weight, particularly preferably at most 40% by weight. is there.

Furthermore, from the viewpoint of improving the tensile strength, a structural unit derived from an unsaturated carboxylic acid having a carboxyl group that can be a crosslinking point may be included. The unsaturated carboxylic acid forming a structural unit derived from an unsaturated carboxylic acid is not particularly limited, and may be a monocarboxylic acid having one carbonyl group in the molecule or a polycarboxylic acid having two or more carbonyl groups in the molecule. . More specifically, examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, crotonic acid, maleic acid, and fumaric acid. Among them, acrylic acid and / or methacrylic acid are preferably used, and more preferably methacrylic acid.
The elastomer may contain structural units derived from a plurality of types of unsaturated carboxylic acids in any combination. As the unsaturated carboxylic acid, by using part or all of the unsaturated dicarboxylic acid, a large amount of carboxyl groups can be introduced with respect to the weight ratio of the unsaturated carboxylic acid.
It is easy to adjust the crosslink density of the elastomer.
The ratio of the structural unit derived from the unsaturated carboxylic acid, that is, the ratio of the unsaturated carboxylic acid residue is usually 2% by weight or more, preferably 3% by weight or more based on 100% by weight of the elastomer from the viewpoint of improving the tensile strength. It is particularly preferably at least 4% by weight, usually at most 10% by weight, preferably at most 9% by weight.

When the elastomer has a structural unit derived from butadiene, a structural unit derived from (meth) acrylonitrile, or a structural unit derived from an unsaturated carboxylic acid, the elastomer further includes a structural unit derived from another polymerizable monomer. Other polymerizable monomers include aromatic vinyl monomers such as styrene, α-methylstyrene and dimethylstyrene; and ethylenic monomers such as (meth) acrylamide, N, N-dimethylacrylamide and N-methylolacrylamide. Unsaturated carboxylic acid amides; unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid and fumaric acid; and vinyl acetate. Any of these may be used alone or in combination of two or more.
The content of the structural units derived from other polymerizable monomers in the elastomer is preferably 30% by weight or less, more preferably 20% by weight or less, and even more preferably 15% by weight or less.

As described above, the elastomer may be, for example, a copolymer elastomer of acrylonitrile-butadiene or butadiene-unsaturated carboxylic acid, or a terpolymer elastomer of acrylonitrile-butadiene-unsaturated carboxylic acid ester, or may be another polymerized elastomer. A quaternary copolymer elastomer containing a hydrophilic compound can also be used.
When an acrylonitrile-butadiene-unsaturated carboxylic acid ester terpolymer elastomer is used, it can be used, for example, in the form of an elastomer disclosed in WO2018 / 117109.

  The content of the elastomer is preferably 0.1% by weight or more, and more preferably 0.2% by weight or more, based on the total solid content of the glove dip composition, in order to secure the tensile strength required for the gloves. Is more preferably 0.3% by weight or more, still more preferably 0.4% by weight or more, further preferably 5% by weight or less, and preferably 4% by weight or less. More preferably, it is more preferably 3% by weight or less.

<1-3. Crosslinking Agent, Crosslinking Accelerator>
The dip composition may include a crosslinking agent and / or a crosslinking accelerator. In this case, as described above, the effect of improving the tensile strength of the silicon-containing organic coagulant is manifested irrespective of the type of the cross-linking agent and the like, although the degree of the effect may vary. Therefore, the type of the crosslinking agent that can be included in the dip composition is not particularly limited as long as it can be generally used as a raw material for a rubber glove.

<1-3-1. Crosslinking with structural units derived from diene rubber>
When an elastomer having a structural unit derived from a diene rubber such as butadiene rubber is used as the elastomer, a sulfur-based crosslinking agent can be used as the crosslinking agent. In addition, in this application, when performing bridge | crosslinking with a sulfur element, bridge | crosslinking may be expressed as "vulcanization." Examples of the sulfur-based crosslinking agent include sulfur such as powdered sulfur, oil-treated powdered sulfur, precipitated sulfur, colloidal sulfur, and dispersible sulfur, and organic sulfur-containing compounds such as tetramethylthiuram disulfide and N, N-dithiobismorpholine. One or more of these can be used.
When sulfur is used as a cross-linking agent, a cross-linking accelerator can be added. For example, di-o-tolyl guanidine, 1,3-diphenyl guanidine, 1-o-tolyl biguanide, dicatechol borate Guanidine-based accelerators such as di-o-tolyl guanidine salt; thiazole-based accelerators such as 2-mercaptobenzothiazole and di-2-benzothiazyl disulfide; sulfones such as N-cyclohexyl-2-benzothiazylsulfenamide Phenamide-based accelerators; thiuram-based accelerators such as tetrameterthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, dipentamethylenethiuram tetrasulfide; zinc dithiocarbamate, zinc diethyldithiocarbamate, tellurium diethyldithiocarbamate, and the like May be used alone or two or more of such thiourea accelerator; dithio acid salt-based.
However, sulfur-based crosslinking accelerators may cause delayed type IV hypersensitivity, which is contact dermatitis, which is an allergic symptom. Therefore, from this viewpoint, it is not preferable to use a sulfur-based crosslinking agent as the crosslinking agent.

<1-3-2. Crosslinking with a structural unit derived from an unsaturated carboxylic acid>
When an elastomer having a structural unit derived from an unsaturated carboxylic acid is used as the elastomer, the crosslinking agent may be a polycarbodiimide crosslinking agent, an epoxy crosslinking agent (also referred to as an “epoxy group-containing frame compound” in the present application), or a polyoxazoline crosslinking agent. Agents, polyisocyanate crosslinking agent, blocked isocyanate crosslinking agent, polysiloxane crosslinking agent, aziridine crosslinking agent, urea resin-based crosslinking agent such as alkylated melamine, hydrazide-based crosslinking agent, etc., when wet with sweat during use. It is preferable to use a polycarbodiimide cross-linking agent or an epoxy cross-linking agent from the viewpoint of excellent durability (fatigue durability, measurement method will be described later). Hereinafter, specific examples of the case where a polycarbodiimide crosslinking agent or an epoxy crosslinking agent is used as the crosslinking agent will be described.
When a functional group capable of reacting with a carboxyl group such as an amide group or an amine group is present in the elastomer, the functional group is bonded to the carboxyl group of the unsaturated carboxylic acid to form a crosslink (hereinafter, referred to as “ Self-crosslinking "). That is, if self-crosslinking is used, crosslinking can be caused between molecular chains of the elastomer without using a crosslinking agent. Specific embodiments of self-crosslinking include, for example, embodiments such as the first-stage crosslinking disclosed in WO2012 / 043893.

<1-3-2-1. Polycarbodiimide crosslinking agent>
As the polycarbodiimide, those composed of a central portion that undergoes a cross-linking reaction with a carboxyl group in a structural unit derived from an unsaturated carboxylic acid and a hydrophilic segment added to the end can be used. Further, some of the ends may be sealed with a sealant.
Hereinafter, specific embodiments of the polycarbodiimide are shown, but the present invention is not limited to these embodiments. For example, the polycarbodiimide may be used in the embodiments disclosed in International Publication No. WO2017 / 217542 and International Publication No. WO2018 / 117109.

(Central part of polycarbodiimide)
The chemical formula of the central part of polycarbodiimide is shown below.
^{NCO- (R 1 - (N =} C = N) -) m-R 1 OCN (2)
-N = C = N- in the above formula (2) is a carbodiimide group and reacts with a carboxyl group.
R ¹ is a lower alkyl group, and R ² is an alkylene, polyalkylene or oxyalkylene group having 1 to 10 carbon atoms. The lower alkyl group preferably has 6 or less carbon atoms, and more preferably 4 or less from the viewpoint of availability. The quaternary ammonium salt of dialkylamino alcohol represented by the above (1) can be used, and a quaternary salt of 2-dimethylaminoethanol is particularly preferable. In this case, the ionicity of the polycarbodiimide is of the cation type.
m is an integer of 4 to 20 and indicates the degree of polymerization.
By setting m to 4 or more, multipoint cross-linking between the carboxyl groups of the elastomer can be performed, so that the elastomer can be largely grouped, so that very good fatigue durability can be obtained as compared with a conventional two-point cross-linking cross-linking agent. Is considered to be a factor that can be obtained.
The central portion of the polycarbodiimide is usually formed by decarboxylation of diisocyanate, and has isocyanate residues at both ends. In the above formula (2), both ends are shown as isocyanate groups. Examples of the diisocyanate include an aromatic diisocyanate, an aliphatic diisocyanate, an alicyclic diisocyanate, and a mixture thereof. Specifically, 1,5-naphthylene diisocyanate, 4,4-diphenylmethane diisocyanate, 4,4-diphenyldimethylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, hexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4 , 4'-diisocyanate, methylcyclohexane diisocyanate, tetramethylxylylene diisocyanate, and the like. From the viewpoint of weather resistance, it is preferable to blend a polycarbodiimide formed by a condensation reaction of an aliphatic or alicyclic diisocyanate with decarbonation. A representative type of diisocyanate is dicyclohexylmethane-4,4'-diisocyanate.

(Hydrophilic segment)
Since the carbodiimide group easily reacts with water, a part of the polycarbodiimide has a hydrophilic segment at the terminal (isocyanate group) in the dip composition for gloves in order to protect it from water so as not to lose the reaction force with the elastomer. ) Are required.
The structure of the hydrophilic segment is shown in the following formula (3).
_{^{R 5 -O- (CH 2 -CHR 6}} -O-) m -H (3)
In the above formula (3), R ⁵ is an alkyl group having 1 to 4 carbon atoms, R ⁶ is a hydrogen atom or a methyl group, and m is an integer of 5 to 30.
The hydrophilic segment has a function of protecting the carbodiimide group by surrounding the central portion of the polycarbodiimide that easily reacts with water in the glove dip composition (dip liquid) (in water) (shell / core structure).
On the other hand, when dried, the hydrophilic segment is opened, and the carbodiimide group appears and becomes ready for reaction. Therefore, in the production of gloves by dip molding, unlike paint, it is important to avoid drying in a complicated process until the final heat crosslinking (curing) process to avoid a reaction with water. For this purpose, it is also effective to add a humectant described below to the glove dip composition.
In addition, the hydrophilic segment may be provided at both ends of the central portion, or may be provided at one side. Further, a mixture of those having a hydrophilic segment and those having no hydrophilic segment may be used.
The end to which no hydrophilic segment is added is sealed with a sealant.

The formula of the sealant is represented by the following formula (4).
_{^{(R 1) 2 -N-R}} 2 -OH (4)
In the above formula (4), R ¹ is an alkyl group having 6 or less carbon atoms, and is preferably an alkyl group having 4 or less carbon atoms from the viewpoint of availability. R ² is an alkylene, polyalkylene or oxyalkylene group having 1 to 10 carbon atoms.

(Degree of polymerization, molecular weight, equivalent)
The average degree of polymerization of polycarbodiimide (number average molecular weight / carbodiimide equivalent) is 3.8 or more, preferably 4 or more, and more preferably 9 or more. This is necessary in order to properly form a multipoint cross-linking structure, which is a feature of the glove according to the embodiment of the present invention, and to impart high fatigue durability to the glove.
The molecular weight of the polycarbodiimide is preferably from 500 to 5,000 in number average molecular weight, more preferably from 1,000 to 4,000.
The number average molecular weight can be measured by the GPC method (calculated in terms of polystyrene) as follows.
RI detector: RID-6A (manufactured by Shimadzu Corporation)
Column: KF-806, KF-804L, KF-804L (manufactured by Showa Denko KK)
Developing solvent: THF 1 ml / min.
Regarding the carbodiimide equivalent, when the addition amount of the polycarbodiimide is 3% by weight, the fatigue durability exceeds 1500 minutes in the range of the equivalent of 260 to 600. However, in the case of adding 1% by weight, if the equivalent weight exceeds 440, the fatigue durability becomes extremely low at 100 minutes or less. For this reason, the carbodiimide equivalent is preferably in the range of 260 to 440. Note that the lower limit is a range where the product exists.
The carbodiimide equivalent is a value calculated by the following equation (5) from the carbodiimide group concentration determined by a reverse titration method using oxalic acid.
Carbodiimide equivalent = formula number of carbodiimide group (40) × 100 / carbodiimide group concentration (%) (5)
The amount of the polycarbodiimide added in the glove dip composition may be 0.1 to 4.0% by weight based on the solid content in the glove dip composition, and may be 0.1 to 2.5% by weight. %, More preferably 0.3 to 2.0% by weight. Regarding the range of the content, when the content exceeds 7.0 parts by weight, the fatigue durability is reduced. On the other hand, a relatively small addition amount of 0.5 part by weight has high fatigue durability exceeding other sulfur-based gloves. We verify that we can let you.

<1-3-2-2. Epoxy crosslinking agent>
Epoxy crosslinker (epoxy group-containing compound) should be used as a crosslinker for unsaturated carboxylic acid because the epoxy group in the molecule is hydrolyzed to form a ring during crosslinking and the resulting hydroxyl group reacts with the carboxyl group. Can be.
The epoxy group-containing compound is not particularly limited as long as it has two or more epoxy groups in one molecule.
Hereinafter, specific embodiments of the epoxy group-containing compound will be described, but the present invention is not limited to these embodiments.

As an epoxy group-containing compound used for producing a dip molded product, specifically, a polyglycidyl ether having an epoxy group in one molecule via an ether bond, and a polyglycidylamine, a polyglycidyl ester, or an epoxy compound And alicyclic or aliphatic epoxides such as epoxidized polybutadiene and epoxidized soybean oil.
Further, one kind of the epoxy group-containing compound may be used alone, or a plurality of kinds may be used in combination.

  Specific examples of polyglycidyl ether include glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, sorbitan polyglycidyl ether, xylitol polyglycidyl ether, erythritol polyglycidyl ether, and trimethylolpropane poly. Aliphatic polyglycidyl ethers such as glycidyl ether, trimethylolethane polyglycidyl ether and pentaerythritol polyglycidyl ether; aromatic polyglycidyl ethers such as cresol novolak polyglycidyl ether and trishydroxyphenylmethane polyglycidyl ether;

Specific examples of polyglycerol polyglycidyl ether include triglycerol hexaglycidyl ether, triglycerol pentaglycidyl ether, triglycerol tetraglycidyl ether, triglycerol triglycidyl ether, triglycerol diglycidyl ether, tetraglycerol octaglycidyl ether, and tetraglycerol heptaglycidyl. Examples thereof include ether, tetraglycerol hexaglycidyl ether, tetraglycerol pentaglycidyl ether, tetraglycerol tetraglycidyl ether, and tetraglycerol triglycidyl ether.
A specific example of glycerol polyglycidyl ether includes glycerol triglycidyl ether.
Specific examples of sorbitol polyglycidyl ether include sorbitol triglycidyl ether, sorbitol tetraglycidyl ether, sorbitol pentaglycidyl ether, and sorbitol hexaglycidyl ether.
Specific examples of trimethylolpropane polyglycidyl ether include trimethylolpropane triglycidyl ether.
Specific examples of diglycerol polyglycidyl ether include diglycerol tetraglycidyl ether, diglycerol triglycidyl ether, and diglycerol diglycidyl ether.

  Among the above, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, diglycerol triglycidyl ether, sorbitol triglycidyl ether and using an epoxy group-containing compound containing at least one selected from sorbitol tetraglycidyl ether. It is preferable to use an epoxy group-containing compound containing at least one of glycerol triglycidyl ether and trimethylolpropane triglycidyl ether.

The number of epoxy groups present in one molecule of the epoxy group-containing compound is preferably three or more, rather than two, from the following viewpoints.
Compounds in which two epoxy groups present in one molecule are present only at both ends of the molecule as disclosed in WO 2017/126660 are attacked by hydroxy ions present in the dip molding composition. And one epoxy group is easily deactivated. When such an epoxy group-containing compound is used as a crosslinking agent, when one epoxy group of the epoxy group-containing compound is deactivated, only another undeactivated epoxy group is present in the elastomer. Bonds with carboxyl groups derived from unsaturated carboxylic acids. In that case, the crosslinking in the elastomer child is not sufficiently formed.
On the other hand, when an epoxy crosslinking agent containing a compound having three or more epoxy groups in one molecule is used, even if one epoxy group of the epoxy group-containing compound is deactivated, the remaining 2 It is possible to maintain a state where more than one epoxy group can bond with a carboxyl group derived from unsaturated carboxylic acid present in the elastomer. Of course, if none of the epoxy groups is deactivated, many crosslinking points in the molecule of the elastomer will be formed, and the tensile strength will be good. In addition, the upper limit of the number of epoxy groups is not particularly limited.

Along with the number of epoxy groups in one molecule, the number of epoxy groups contained in the epoxy group-containing crosslinking agent can be represented by “epoxy equivalent”. The epoxy equivalent is preferably 50 g / eq or more and 300 g / eq or less, and 80 g / eq or more and 250 g / eq or less from the viewpoint of performing multipoint crosslinking of the elastomer and obtaining good fatigue durability of the dip molded product. Is more preferable, and it is particularly preferable that it is 100 g / eq or more and 200 g / eq or less.
The epoxy equivalent is a value obtained by dividing the molecular weight of the epoxy group-containing compound by the number of functional groups.

  Further, the number of epoxy groups contained in the epoxy group-containing compound can be expressed, for example, as the average number of epoxy groups of the epoxy group-containing compound. The epoxy group-containing compound preferably has an average number of epoxy groups contained therein of more than 2, more preferably has an average number of epoxy groups of 2.20 or more, still more preferably 2.25 or more. . The average number of epoxy groups is obtained by multiplying the number of epoxy groups in one molecule of each compound contained in the epoxy group-containing compound by the number of moles of the compound, and calculating the number of epoxy groups for each epoxy group-containing compound. The value is obtained by dividing the value by the total number of moles of all the epoxy group-containing compounds contained in the epoxy group-containing compound.

<2. Other ingredients>
The dip composition may contain other components other than the above components as long as the effects of the present invention are not impaired. Other components are not particularly limited and include, for example, an emulsifier, a polymerization initiator, a molecular weight adjuster, a pH adjuster, a humectant, a filler, a dispersant, an antioxidant, a colorant, an antistatic agent, a slip agent, Examples include a thickener, an antifoaming agent, and a plasticizer. Hereinafter, specific embodiments of some of these components will be described.

(emulsifier)
Examples of the emulsifier include anionic surfactants such as dodecylbenzene sulfonate and aliphatic sulfonate; cationic surfactants such as polyethylene glycol alkyl ether and polyethylene glycol alkyl ester; and amphoteric surfactant. Preferably, an anionic surfactant is used.

(Polymerization initiator)
The polymerization initiator is not particularly limited as long as it is a radical initiator. Inorganic peroxides such as ammonium persulfate and potassium perphosphate; t-butyl peroxide, cumene hydroperoxide, p-menthane hydroperoxide, di-peroxide Organic peroxides such as -t-butyl peroxide, t-butyl cumyl peroxide, dibenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, t-butyl peroxyisobutyrate; Examples thereof include azo compounds such as lonitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, and methyl azobisisobutyrate.

(Molecular weight regulator)
Examples of the molecular weight modifier include mercaptans such as t-dodecyl mercaptan and n-dodecyl mercaptan, and halogenated hydrocarbons such as carbon tetrachloride, methylene chloride and methylene bromide, and t-dodecyl mercaptan; n-dodecyl mercaptan and the like. Are preferred.

(PH adjuster)
When an acid-base reaction is used as the crosslinking reaction, for example, in a crosslinking reaction by a carboxyl group of an unsaturated carboxylic acid, the pH of the dip composition affects the crosslinking reaction. . A general pH adjuster can be used, and the type thereof is not particularly limited.
For example, in the reaction of the unsaturated carboxylic acid with a carboxyl group, it is preferable to adjust the pH of the dip composition to 9 to 11.5. As the pH adjuster, ammonia, an ammonium compound such as ammonium hydroxide, an amine compound, Alternatively, it is preferable to use potassium hydroxide.
The amount of the pH adjuster used is usually about 0.1 to 5.0% by weight based on the total solid content of the glove dip composition in the glove dip composition.

(Moisturizer)
When the humectant is contained in the glove dip composition, the hydrophilic segment of the polycarbodiimide may be excessively dried at a stage prior to a drying step (for example, a precure step described later) in the glove production by dip molding. Can be prevented from opening.
Examples of the humectant include polyols, and among them, a divalent or trivalent compound is preferably used. Specifically, bivalent ones include ethylene glycol, propylene glycol, tetramethylene glycol, diethylene glycol, dipropylene glycol, polyethylene glycol and the like. Glycerin can be mentioned as a trivalent one. Among these, it is preferable to include glycerin as a humectant.
The amount of the humectant may be about 1.0 to 5.0 parts by weight, and preferably 1.5 to 3.0 parts by weight, based on 100 parts by weight of the elastomer in the glove dip composition. Is more preferable.

<3. Glove manufacturing method>
A method for manufacturing a glove according to another embodiment of the present invention includes a stirring step of leaving the above-described glove dip composition while stirring, and a dipping step of immersing the glove mold in the glove dip composition. Glove manufacturing method.
The method for producing gloves may include various steps other than the above steps as long as the effects of the present invention are not impaired. For example, gloves are produced by the method described in WO2018 / 117109. be able to.
Hereinafter, a method for manufacturing a glove will be described by way of example, but the present invention is not limited to the method.

Gloves can be manufactured by the following manufacturing method.
(1) a stirring step in which the above-described glove dip composition is left while being stirred,
(2) a dipping step of dipping a glove mold into the glove dip composition;
(3) a gelling step of leaving the glove mold to which the dip molding attachment remains attached, and forming a cured film precursor on the glove mold;
(4) a leaching step of removing impurities from the effect film precursor,
(5) After the leaching step, a beading step of forming a winding around the cuff portion of the glove;
(6) a pre-curing step of heating and drying the cured film precursor after the beading step,
(7) a curing step of heating the cured film precursor to obtain a cured film;
And a method for producing gloves, wherein the steps (1) to (7) are performed in the above order.
Hereinafter, in the case of using a compound capable of reacting with an unsaturated carboxylic acid such as a polycarboxyl or an epoxy group-containing compound as a cross-linking agent, the method for producing the above glove is particularly suitable when an epoxy group-containing compound is used. Will be described in more detail. When a crosslinking agent other than the above compounds is used, treatment such as pH adjustment is not required.
In the present specification, the cured film precursor is a state in which the carboxyl group of the elastomer is not exposed, and the carboxyl group of the elastomer and the epoxy group of the epoxy group-containing compound are not crosslinked.

(1) Stirring Step The above-mentioned glove dip composition is adjusted with a pH adjuster so that the pH becomes about 10 to 10.5.
When obtaining a mixed liquid in which a dispersant for dispersing a cross-linking agent or the like is dispersed, it is preferable to separately prepare a mixed liquid of the cross-linking agent or the like and a dispersant.
The dip molding composition to which the mixture of the crosslinking agent and the dispersant of the crosslinking agent is added is stirred. The weight ratio of each of the cross-linking agent and the cross-linking agent dispersant in the mixture is preferably from 4: 1 to 1: 1.
The dip molding composition to which the mixture of the crosslinking agent and the dispersant of the crosslinking agent is added is stirred.
This step is also called an aging step. By performing this aging, the composition for dip molding can be prevented from becoming non-uniform, which contributes to the uniform finish of the glove obtained.
In addition, the aging may be performed for 5 hours or more, and is preferably performed within 150 hours.
(2) Dipping Step This is a step of immersing the glove mold in the composition for dip molding, for example, at a temperature of 25 to 60 ° C. for 1 to 60 seconds. The dip molding composition is adhered, and this is a dipping step. In the dipping step, the elastomer in the dip molding composition is formed into a film on the surface of the glove mold.
Before the dipping step, the method may include an inorganic coagulant adhering step of immersing the glove mold in a coagulant solution containing a calcium ion-containing inorganic coagulant and adhering the coagulant to the glove mold. By this step, in the dipping step, the elastomer in the composition for dip molding can be aggregated on the surface of the glove mold by calcium ions contained in the coagulant to facilitate the formation of a film.
As described above, the pH of the dip molding composition is adjusted to 9 or more by a pH adjuster such as potassium hydroxide. When a non-volatile base such as potassium hydroxide is used as the pH adjuster instead of ammonia or the like, the reactivity of the carboxylate and the epoxy group-containing compound does not decrease because the base does not volatilize.

(Calcium ion-containing inorganic coagulant)
The type of the calcium ion-containing inorganic coagulant is not particularly limited, and calcium nitrate and calcium chloride can be used. From the viewpoint of versatility, calcium nitrate is preferable. Calcium ions (Ca ²⁺ ) contained in the coagulant form an ionic bond with a polar group such as a carboxyl group in the elastomer, so that the tensile strength of the glove can be improved.

The content of the calcium ion-containing inorganic coagulant is preferably 0.4% by weight or more, and more preferably 0.5% by weight or more, based on the total solid content in the calcium-containing inorganic coagulant-containing coagulating liquid. More preferably, the content is 0.6% by weight or more, further preferably 1.5% by weight or less, more preferably 1.4% by weight or less, and more preferably 1.3% by weight or less. More preferably, it is particularly preferably at most 1.2% by weight.
Further, it may include a zinc content that forms a zinc metal ion crosslink that affects the strength properties of the film, and the content of the zinc-containing inorganic coagulant is based on the total solid content of the glove dip composition. It is preferably at least 0.4% by weight, more preferably at least 0.5% by weight, even more preferably at least 0.6% by weight, and preferably at most 1.5% by weight. Preferably, it is 1.2% by weight or less, more preferably 1.0% by weight or less.
If it exceeds the upper limit of the above range, the glove finally obtained will be too hard and excessive, and if it is below the lower limit of the above range, the required film forming property and tensile strength will be lower.

(3) Gelling Step The glove mold to which the composition for dip molding has adhered in the dipping step is allowed to stand under the conditions exemplified below to prevent the elastomer from being eluted in the subsequent leaching step. is there. When the inorganic coagulant is used, by performing this gelling step, in the elastomer contained in the dip molding composition that was only gathered on the surface of the glove mold, calcium ions contained in the inorganic coagulant Is infiltrated into the elastomer to form a crosslinked structure, so that the elastomer does not elute in the subsequent leaching step.
The conditions of the gelling step in the embodiment of the present invention include the following aspects.

Examples of the conditions of the gelling step include an embodiment in which the gel is left at room temperature (15 to 25 ° C., more specifically, 23 ° C.) for 20 seconds to 20 minutes, and an embodiment in which the gel is left for 30 seconds to 10 minutes. it can.
On the other hand, the gelling step can be performed at a temperature equal to or higher than room temperature (a temperature exceeding 25 ° C.). In this case, the standing time may be, for example, about 20 seconds to about 20 minutes. In addition, even when the temperature of the gelling step is 50 to 90 ° C., an embodiment in which the gel is left for 20 seconds or more and less than 7 minutes can be mentioned, and an embodiment in which the gel is left for 30 seconds to 5 minutes can also be mentioned.
Here, in the gelling step, `` leave '' means that the glove mold to which the dip molding composition has adhered does not perform an operation such as adding any substance or the like, and is allowed to stand still. In addition to the state in which the glove mold is moving, the glove mold is moving on the production line without standing still in a normal factory.
Regarding any of the above conditions, it is basically preferable to leave the gloves at the ambient temperature (room temperature) at the time of manufacturing, that is, to perform the gloves under the condition that heating is not performed. Regarding the production of gloves, the ambient temperature (room temperature) may be around 23 ° C., or about 50 ° C., about 90 ° C., or even 110 ° C. in the case of a higher temperature, depending on the location of the factory. The above-mentioned temperature range takes into consideration such a location condition of the factory. For example, even if the temperature is left at around 50 ° C., it is basically required to heat to that temperature and raise the temperature. Is not assumed.
In addition, there can be mentioned an embodiment in which the gelling step is performed under the condition of 40 to 60% RH.

(4) Leaching Step After the gelling step, the mold or former to which the elastomer has adhered is washed with water to remove the chemical, and this is the leaching step. Here, the partially dried elastomer-coated glove mold is washed (reached) in hot water or hot water (30 to 70 ° C.) for 60 seconds to 10 minutes, preferably for about 60 seconds to 6 minutes. I do.
By performing this leaching, components caused by the pH adjuster and components caused by the coagulant such as calcium ions and nitrate ions are removed. Thus, excessive gelling can be suppressed.

(5) Beading Step After the leaching step is completed, beading (sleeve winding) is performed on the cuff portion of the glove. This is the beading step.

(6) Precuring step After the beading step, the glove mold is dried in an oven at 60 to 80 ° C, more preferably 65 to 75 ° C, for 30 seconds to 5 minutes. This is a precuring step. The presence of the pre-curing step can prevent partial expansion of the glove, which may be caused by a sudden decrease in moisture in the subsequent curing step.

(7) Curing Step The curing step in which the glove mold after drying in the pre-curing step is heated at a temperature and for a time sufficient for the carboxyl group of the elastomer to react with the group of the crosslinking agent is the curing step.
More specifically, for example, this is a step of heating the elastomer for 20 to 30 minutes so that the surface temperature becomes 110 to 130 ° C. to crosslink and cure the elastomer. In addition, when polycarbodiimide is used as a cross-linking agent, under the above conditions, for example, conditions of 70 to 110 ° C. and 10 to 30 minutes can be applied.
In the curing step, the elastomer is cross-linked, thereby forming a molecular chain, and can impart various preferable properties to the glove.

<4. Dip molding (gloves)>
A glove, which is a dip-formed product according to another embodiment of the present invention, is a glove that contains an elastomer and has a silicon content of 0.0005 to 0.3% by weight, and is manufactured by the above manufacturing method. Can be.
The silicon content in the glove is 0.0005 to 0.3% by weight, preferably 0.0008 to 0.1% by weight, more preferably 0.001 to 0.05% by weight, Preferably it is 0.0011-0.049 weight%.
If it exceeds the upper limit of the above range, the glove finally obtained will be too hard and excessive, and if it is below the lower limit of the above range, the required film forming property and tensile strength will be lower.

  The silicon content in the glove can be calculated from the amount of Si in the silicon-containing organic coagulant determined by the ICP-AES analyzer and the addition amount of the silicon-containing organic coagulant used at the time of film production.

(FAB)
In the present invention, Force at Break (FAB) is used as an index indicating the tensile strength.
In the tensile test of the film forming the glove, the FAB (EN standard) having a film thickness of 0.045 mm is preferably 6 N or more, more preferably 6.5 N or more, and the upper limit is not particularly limited.
Particularly, in a conventional rubber glove, the FAB under the condition of a thickness of 0.045 mm is at most about 4.8 to 5.0 N, and it has been difficult to manufacture a rubber glove of 6.0 N or more. Therefore, in the present embodiment, if the thickness is 6.0 N or more under the condition of a thickness of 0.045 mm, this indicates that the glove is much more excellent in strength than the conventional glove.
FAB can be measured, for example, using a tester STA-1225 (manufactured by A & D) at a test speed of 500 mm / min and a chuck-to-chuck distance of 75 mm according to the method of EN455-2: 2009 standard.

(Fatigue durability)
In the fatigue test of the film forming the glove by the Palm method, the fatigue durability is preferably 150 minutes or more, more preferably 200 minutes or more, and the upper limit is not particularly limited.
In particular, in the case of rubber gloves, it is desirable that the fatigue durability under the condition of a thickness of 0.045 mm exceed 234 minutes (corresponding to 90 minutes by the Crotch method).
If the fatigue durability is 350 minutes or more, it is preferable because it can be worn almost all day, indicating that the glove is much more durable than conventional products.

Here, the fatigue durability is determined by the following procedure.
A JIS K6251 No. 1 dumbbell test piece having a length of 120 mm and a predetermined thickness (in the case of thin gloves, for example, 0.04 to 0.07 mm) is prepared from a cured film, and the lower portion thereof is fixed to an artificial length of 60 mm. Pulling the upper part of the test piece in the state of being immersed in sweat, repeatedly elongating and relaxing between the maximum length of 195 mm and the minimum length of 147 mm in the length direction, the time until the test piece breaks is the fatigue durability. . Elongation (195 mm) and relaxation (147 mm) are performed by repeating a cycle (12.5 seconds per cycle) of holding the relaxation state for 11 seconds, and then extending to 195 mm in 1.5 seconds and returning to 147 mm. Can be.
The fatigue durability improves as the thickness of the cured film increases, but in the case of the gloves according to the embodiment of the present invention, the gloves are particularly thin (having a thickness of 0.04 to 0.07 mm). Also have good fatigue durability as described below.

More specifically, a fatigue durability test can be performed using a dumbbell-shaped test piece and an apparatus as shown in FIG. 1 as in the case of performing a tensile test or the like of a rubber product. As shown in FIG. 1A, the lower end of the test piece is fixed with a clamp, and up to 60 mm is immersed in artificial sweat. The upper end of the test piece is sandwiched, and is vertically expanded and contracted by using a pneumatic piston so as to be in the relaxed state of FIG. 1 (b) → the extended state of FIG. 1 (c) → the relaxed state of FIG. 1 (b). 1 (b) → FIG. 1 (c) → FIG. 1 (b) is defined as one cycle, and the evaluation is made by measuring the number of cycles and time until breakage. When the test piece breaks, the photoelectric sensor reacts and the device stops.

  As an artificial sweat liquid, an aqueous solution containing 20 g of sodium chloride, 17.5 g of ammonium chloride, 17.05 g of lactic acid, and 5.01 g of acetic acid in 1 liter and adjusted to pH 4.7 with an aqueous sodium hydroxide solution can be used. .

(Tensile elongation)
In the tensile test of the film forming the glove, the tensile elongation at a film thickness of 0.045 mm is preferably from 450% to 750%, more preferably from 500% to 700%.
The FAB can be measured, for example, using a tester STA-1225 (manufactured by A & D) at a test speed of 500 mm / min and a chuck-to-chuck distance of 65 mm in accordance with the standard of EN455-2: 2009 + A2: 2013.
The tensile elongation is measured, for example, by using a tensile tester STA-1225 (manufactured by A & D) at a test speed of 500 mm / min and a chuck-to-chuck distance of 75 mm using a method of Japanese Industrial Standards (JIS K6251). : 1993 vulcanized rubber tensile test method) and the following formula (6).
Tensile elongation (%) = 100 × (distance between marked lines at break in tensile test−distance between marked lines) / distance between marked lines (6)

上記式（８）において、ｎ：膨潤前試料の架橋密度、Ｖｇｏｍ：試料中のゴム容積分率、Ｖ：溶媒の分子容、Ｖｒ：膨潤ゲル中のゴム容積分率、μ：コム溶媒相互作用定数（＝０．３５０） (Crosslink density)
The crosslink density of the glove is not particularly limited, but is usually 1.0 × 10 ^{−4 to} 2.0 × 10 ⁻³ mol / cm ³ , and 2.0 × 10 ^{−4 to} 1.0 × 10 ⁻³ mol. / Cm ³ is preferable. If the upper limit of the above range is exceeded, the glove finally obtained will be too hard and excessive, and if it is below the lower limit of the above range, the required tensile strength will be lower. The crosslinking density can be adjusted by controlling the number of crosslinking points in the elastomer, the crosslinking temperature, and the crosslinking time.
The crosslink density can be calculated, for example, by measuring the weight of the test piece when the test piece is immersed in toluene at room temperature for 72 hours according to the Flory-Rehner formula (7).

In the above formula (8), n: crosslink density of the sample before swelling, Vgom: rubber volume fraction in the sample, V: molecular volume of solvent, Vr: rubber volume fraction in the swollen gel, μ: comb solvent interaction Constant (= 0.350)

(Molecular weight between crosslinking points)
Molecular weight N between crosslinking points of the glove is not particularly limited, from the viewpoint of maintaining the tensile strength and flexibility required in the glove is usually 500~10000g / cm ^3, to be 1000~5000g / cm ³ preferable. The molecular weight between crosslinking points can be adjusted by controlling the molecular weight of the crosslinking agent.
By substituting the crosslinking density n into the following equation (8), the molecular weight N between crosslinking points can be calculated.
N = 1 / n (8)

The gloves preferably contain neither a sulfur as a cross-linking agent nor a sulfur compound as a vulcanization accelerator to reduce the risk of allergy, and the content of sulfur element detected by neutralization titration of combustion gas Is preferably 1% by weight or less of the weight of the glove.

The glove according to the present embodiment has sufficient tensile strength (strength and rigidity) even as a thin glove. Therefore, the thickness of the glove is not particularly limited, but is preferably 0.04 to 0.35 mm, and more preferably 0.04 to 0.3 mm.
The glove according to the present embodiment preferably has a thickness of 0.04 to 0.15 mm when the glove is thin, and 0.04 to 0.07 mm when the glove is thin. It is preferable that the thickness be greater than .15 mm to 0.4 mm.

  Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to only these Examples. Unless otherwise specified, “%” is “% by weight” and “parts” are “parts by weight”.

[Experiment I]
<Manufacture of dip composition>
(Preparation of elastomer)
As the elastomer solution, a carboxylated acrylonitrile-butadiene copolymer (XNBR) having a trade name of NL128 (manufactured by LG Chem) was used. This elastomer has the following properties:
Mooney viscosity (ML (1 + 4) 100 ° C): 102
MEK insoluble content: 1.8% by weight
MMA (COOH) amount: 5.2% by weight
AN amount: 31% by weight
Solid content: 45%

上記式（１）において、ｍｏｌ比で、ｘ＝０．２、ｙ＝０．８、ｍ＝５５．７、及びｎ＝４３．３
Ｓｉ含有量：０．４ｗｔ％（固形分量基準：１．６重量％） (Preparation of silicon-containing organic coagulant)
As the silicon-containing organic coagulant 1, a silicone oil having a trade name of INDUSIL 139 (manufactured by Momentive Performance Materials Inc., solid content: 35.4% by weight) was used. This silicone oil has the following properties. The structure of the silicon-containing organic coagulant was analyzed by the nuclear magnetic resonance spectrum described above.
Specific gravity (20 ° C): 1.03 g / ml
Viscosity (25 ° C): 45 cSt
Cloud point: 36 ° C
pH: 8.0
Construction:

In the above formula (1), x = 0.2, y = 0.8, m = 55.7, and n = 43.3 by mol ratio.
Si content: 0.4 wt% (based on solid content: 1.6 wt%)

上記式（１）において、ｍｏｌ比で、ｘ＝０．５、ｙ＝１．０、ｍ＝５０．２、及びｎ＝４８．３
Ｓｉ含有量：０．５７ｗｔ％（固形分量基準：１．２重量％） As a silicon-containing organic coagulant 2, trade name TPA4380 (Momentive Per)
performance Materials Inc. Silicone oil having a solid content of 34.5% by weight). This silicone oil has the following properties.
Specific gravity (25 ° C): 1.04 g / ml
Viscosity (25 ° C): 100 cSt
Cloud point: 38 ° C
pH: 7.0
Construction:

In the above formula (1), x = 0.5, y = 1.0, m = 50.2, and n = 48.3 in mol ratio.
Si content: 0.57 wt% (based on solid content: 1.2 wt%)

(Preparation of crosslinking agent)
As the cross-linking agent 1, polycarbodiimide having a trade name of Carbodilite V-02-L2 (manufactured by Nisshinbo Co., Ltd.) was used. Information on Carbodilite V-02-L2 is shown below.
Structure of hydrophilic segment: polyethylene glycol monomethyl ether (PEGME)
Structure of polycarbodiimide (type of organic diisocyanate): dicyclohexylmethane diisocyanate (DCHM)
Number average molecular weight (measured value): 3600
Average degree of polymerization = number average molecular weight / equivalent (calculated value): 9.4
Equivalent = molecular weight / degree of polymerization (catalog of Nisshinbo Chemical): 385

As the cross-linking agent 2, an epoxy group-containing compound having a trade name of EX-321 (manufactured by Nagase ChemteX Corporation) was used. The information of EX-321 is shown below.
Water solubility: 27%
Epoxy equivalent: 140 g / eq.
Average number of epoxy groups: 2.65
Active ingredient: trimethylolpropane triglycidyl ether, trimethylolpropane diglycidyl ether

(Production of dip composition)
[Dip composition 1]
170 g of the XNBR solution (solid content: 45%) of the above elastomer was placed in a 1 L beaker (manufactured by AS ONE Corporation, body diameter: 105 mm × height: 150 mm), diluted with 100 g of ion-exchanged water, and stirred. The pH was adjusted to 10 using ammonia. Further, based on the latex solid content, 0.5 phr of the above-mentioned crosslinking agent, 1.0 phr of zinc oxide (trade name “CHEMPERSEC ZnO-50”, manufactured by Farben Technique (M) Sdn Bhd), and 1.0 phr of titanium oxide (trade name “trade name”) FARSPERSE WHITE PW601 ”, manufactured by Farben Technology (M) Sdn Bhd) 1.0 phr, and an antioxidant (trade name“ CHEMPERSE CVOX-50 ”, manufactured by Farben Technique (M) Sdn Bhd) and weighed 0.2 The mixture was diluted with 150 g of ion-exchanged water, and added to the latex while washing with ion-exchanged water (step X). Thereafter, 80 g of ion-exchanged water was further added so that the total solid content (TSC) became 16%, and the mixture was stirred overnight, to obtain a dip composition 1.

[Dip composition 2]
In step X, dip composition 2 was obtained under the same manufacturing conditions as dip composition 1, except that 0.5 phr of the silicon-containing organic coagulant 1 was further added.

[Dip composition 3]
In Step X above, Dip Composition 3 was obtained under the same manufacturing conditions as Dip Composition 1, except that 0.5 phr of the above-mentioned silicon-containing organic coagulant 2 was further added.

[Dip composition 4]
190 g of the XNBR solution (solid content: 45%) of the above elastomer was placed in a 1 L beaker (manufactured by AS ONE Corporation, body diameter: 105 mm × height: 150 mm), diluted with 100 g of ion-exchanged water, and stirred. The pH was adjusted to 9.2 using a 5% KOH solution. Further, based on the latex solid content, 0.7 phr of the above crosslinking agent, 1.0 phr of zinc oxide (trade name "CHEMPERSE CZnO-50", manufactured by Farben Technique (M) Sdn Bhd), and 1.0 phr of titanium oxide (trade name "trade name") 1.5 phr of FARSPERSE WHITE PW601, manufactured by Farben Technology (M) Sdn Bhd), and an antioxidant (trade name: “CHEMPERSE CVOX-50”, manufactured by Farben Technique (M) Sdn Bhr), and weighed by 0.2 The mixture was diluted with 150 g of ion-exchanged water, and added to the latex while washing with ion-exchanged water (step X). At this time, the crosslinking agent was added to the latex while washing with diethylene glycol (DEG, trade name "diethylene glycol", manufactured by Kanto Chemical Co., Ltd.). Thereafter, the pH was adjusted to pH 10.0 with a 5% KOH solution, 27 g of ion-exchanged water was further added so that the total solid content (TSC) became 18%, and the mixture was stirred overnight. Obtained.

[Dip composition 5]
In Step X above, Dip Composition 5 was obtained under the same manufacturing conditions as Dip Composition 4, except that 10.5 phr of the above-mentioned silicon-containing organic coagulant was further added.

[Dip composition 6]
In Step X above, Dip Composition 6 was obtained under the same production conditions as Dip Composition 4, except that 0.5 phr of the above-mentioned silicon-containing organic coagulant was further added.

<Manufacture of coagulation liquid>
Huntsman Corporation's surfactant "Teric 320" (trade name) 0.56 g dissolved in 42.0 g of water was dissolved in a solution of 42.0 g of water, and "S-9" (trade name of CRESAGE INDUSTRY) was used as a release agent. 19.6 g (solids concentration 25.46%) was slowly added after diluting about 2-fold with a portion of 30 g of water measured in advance. The whole amount was added while washing the remaining S-9 with the remaining water, and the mixture was stirred for 3 to 4 hours. Separately, the calcium nitrate tetrahydrate concentration (referred to as “Ca (NO ₃ ) ₂ concentration” in the present specification) of the finally obtained coagulation liquid is 5%, 7%, 9%, and 11%. Each calcium nitrate tetrahydrate was prepared, and the above calcium nitrate tetrahydrate was placed in a 1 L beaker (manufactured by AS ONE Corporation, body diameter 105 mm × height 150 mm) containing 196.2 g of water. Four solutions were obtained. While stirring these four types of solutions, the previously prepared S-9 dispersion was added to the aqueous calcium nitrate solution. The pH was adjusted to 8.5 to 9.5 with 5% aqueous ammonia, and water was added so that S-9 had a solid concentration of 1.0% to obtain 500 g of four types of coagulating liquids. The obtained coagulation liquid was continuously stirred in a 1 L beaker until use.
Hereinafter, the finally obtained coagulation liquids having Ca (NO ₃ ) ₂ concentrations of 5%, 7%, 9%, and 11% were respectively changed to coagulation liquid 5%, coagulation liquid 7%, coagulation liquid 9%, and coagulation liquid. Called 11%. By using coagulating liquids having different Ca (NO ₃ ) ₂ concentrations, finally, cured films having different thicknesses can be obtained.

<Production of cured film>
[Comparative Examples I-1 to I-4, Examples I-1 to I-8]
5% of the obtained coagulating liquid was heated to 50 ° C. while stirring, filtered through a 200-mesh nylon filter, placed in an immersion container, washed and then heated to 60 ° C. on a ceramic plate (200 × 80 × 3 mm, hereinafter referred to as “ceramic plate”). Specifically, after the tip of the porcelain plate came into contact with the liquid surface of the coagulating liquid, the plate was immersed for 4 seconds from the tip of the porcelain plate to a position of 18 cm, held for 4 seconds while immersed, and extracted for 3 seconds. . The coagulating liquid adhering to the surface of the ceramic plate was immediately shaken off, and the surface of the ceramic plate was dried. The dried ceramic plate was again warmed to 60 ° C. in preparation for dipping of the dip composition 1.
The dip composition 1 was filtered at room temperature through a 200-mesh nylon filter, and then placed in an immersion container, and a porcelain plate at 60 ° C. to which the above-described coagulating liquid was adhered was immersed. Specifically, the ceramic plate was dipped for 6 seconds, held for 4 seconds, and extracted for 3 seconds. After the dip composition did not drip, it was held in the air for 30 seconds, and the latex droplet attached to the tip was lightly shaken off.
Thereafter, each porcelain plate immersed in the dip composition 1 was left at room temperature (23 ° C.) for 1 minute (gelling), and leached with ion exchanged water at 50 ° C. for 3 minutes. Thereafter, it was dried at 70 ° C. for 5 minutes (precuring), and thermally cured at 130 ° C. for 30 minutes (curing).
The obtained cured film was peeled cleanly from the ceramic plate, sandwiched between thin papers, and stored in an environment at a temperature of 23 ° C. ± 2 ° C. and a humidity of 50% ± 10% until subjected to a physical property test to obtain a cured film of Comparative Example I-1. Was.
5% of the above-mentioned coagulation liquid was changed to 7%, 9%, and 11% of the coagulation liquid, and otherwise, cured films were produced in the same manner as in Comparative Example I-1. -4 was obtained.
Furthermore, the above-mentioned dip composition 1 was changed to dip compositions 2 and 3, and otherwise, a cured film was produced in the same manner as in the above-mentioned comparative examples I-1 to I-4. To I-4 and I-5 to I-8 were obtained.

[Comparative Examples I-5 to I-8, Examples I-9 to I-16]
5% of the coagulation liquid obtained above was heated to 50 ° C. while stirring, filtered through a 200-mesh nylon filter, placed in an immersion container, washed and then heated to 60 ° C. on a ceramic plate (200 × 80). × 3 mm, hereinafter referred to as “ceramic plate”). Specifically, after the tip of the porcelain plate came into contact with the liquid surface of the coagulating liquid, the plate was immersed for 4 seconds from the tip of the porcelain plate to a position of 18 cm, held for 4 seconds while immersed, and extracted for 3 seconds. . The coagulating liquid adhering to the surface of the ceramic plate was immediately shaken off, and the surface of the ceramic plate was dried. The dried ceramic plate was again heated to 60 ° C. in preparation for dipping of the dip composition 4.
The dip composition 4 was filtered at room temperature through a 200-mesh nylon filter, and then placed in an immersion container, and a 60 ° C. porcelain plate to which the above-described coagulation liquid was adhered was immersed. Specifically, the ceramic plate was dipped for 6 seconds, held for 4 seconds, and extracted for 3 seconds. After the dip composition did not drip, it was dried at 70 ° C. for 2 minutes.
Thereafter, each porcelain plate immersed in the dip composition 4 was left at room temperature (23 ° C.) for 1 minute (gelling), and leached with ion exchanged water at 50 ° C. for 2 minutes. Thereafter, it was dried at 90 ° C. for 5 minutes (precuring), and thermally cured at 130 ° C. for 30 minutes (curing).
The obtained cured film was peeled cleanly from the porcelain plate, sandwiched between thin paper sheets, and stored in an environment of 23 ° C. ± 2 ° C. and 50% ± 10% humidity until subjected to a physical property test, to obtain a cured film of Comparative Example I-5. .
5% of the above-mentioned coagulation liquid was changed to 7%, 9%, and 11% of the coagulation liquid, and otherwise, a cured film was produced in the same manner as in Comparative Example I-5, and Comparative Examples I-6 to I -8 cured film was obtained.
Further, the above-mentioned dip composition 4 was changed to dip compositions 5 and 6, and otherwise, a cured film was produced in the same manner as in the above-mentioned comparative examples I-5 to I-8, and a cured film was obtained. To I-12 and I-13 to I-16 were obtained.

<Evaluation of cured film>
(appearance)
When the surface of the obtained cured film was visually observed, Examples I-1 to I-16 had smaller surface irregularities than Comparative Examples I-1 to I-8, and a uniform film was obtained. Was done.
It is considered that this is because the addition of the silicon-containing organic coagulant facilitated the dispersion of calcium nitrate in the inorganic coagulation liquid that could form an aggregate.

(FAB)
From the cured film that had passed 7 days or more after production, a test piece was punched out using a die in accordance with the EN standard as a test piece, and was overnight (16 ° C.) in an environment of a temperature of 23 ° C. ± 2 ° C. and a humidity of 50% ± 5%. For more than an hour). Thereafter, a mark of 25 mm was placed at the center, the thickness of three points between the marks was measured, and the average thickness of the test piece was calculated. The FAB was measured using a tensile tester STA-1225 (manufactured by A & D) at a test speed of 500 mm / min and a distance between chucks of 75 mm according to the method of EN455-2: 2009 standard.
The results of FAB measurement using Comparative Examples I-1 to I-4 and Examples I-1 to I-8 are shown in Table 1 below, and were also shown in Comparative Examples I-5 to I-8 and Example I. The results of FAB measurement using -9 to I-16 are shown in Table 2 below. Further, FIG. 1 shows a plot of the measurement results in Table 1 with the film thickness on the horizontal axis and FAB on the vertical axis, and FIG. 2 shows a plot of the measurement results in Table 2.

上記式（７）において、n：膨潤前試料の架橋密度、Ｖｇｏｍ：試料中のゴム容積分率、
Ｖ：溶媒の分子容、Ｖｒ：膨潤ゲル中のゴム容積分率、μ：コム溶媒相互作用定数（＝０．３５０） (Crosslink density)
The crosslink density of the glove was calculated by measuring the weight of the test piece when the test piece was immersed in toluene at room temperature for 72 hours according to the following Flory-Rehner formula (7).

In the above formula (7), n: crosslink density of the sample before swelling, Vgom: rubber volume fraction in the sample,
V: molecular volume of solvent, Vr: rubber volume fraction in swollen gel, μ: comb solvent interaction constant (= 0.350)

(Molecular weight between crosslinking points)
The molecular weight N between crosslinking points was calculated by substituting the crosslinking density n into the following equation (8).
N = 1 / n (8)

From Tables 1 and 2 and FIGS. 2 and 3, it can be seen that the cured film produced using the dip composition according to the embodiment of the present invention has a larger FAB than the film not belonging to. This is considered to be because the silicon-containing organic coagulant was cured in a state of being uniformly dispersed in the dip composition, and the film-forming property was improved. In addition, it is considered that the coagulant itself formed a film in the cured film and improved the strength.
Further, when the crosslinking agent 1 was used, the effect of increasing the FAB due to the addition of the silicon-containing organic coagulant was larger than when the crosslinking agent 2 was used. That is, it is understood that the crosslinking with the polycarbodiimide is more susceptible to the addition of the silicon-containing organic coagulant than the crosslinking with the epoxy group-containing compound.

(Fatigue durability)
A JIS K6251 No. 1 dumbbell test piece was cut out from the cured film, and the cut piece was used as an artificial sweat (containing 20 g of sodium chloride, 17.5 g of ammonium chloride, 17.05 g of lactic acid, and 5.01 g of acetic acid in 1 liter, and an aqueous sodium hydroxide solution). (Adjusted to pH 4.7), and the fatigue durability was evaluated using the durability test apparatus described above.

  That is, a 15 mm portion from each of two ends of a dumbbell test piece having a length of 120 mm was sandwiched between a fixed chuck and a movable chuck, and up to 60 mm from below the test piece on the fixed chuck side was immersed in artificial sweat liquid. After moving the movable chuck to the minimum position (relaxed state) of 147 mm (123%) and holding it for 11 seconds, the maximum position (extended state) where the length of the test piece becomes 195 mm (163%) and the minimum again It was moved to the position (relaxed state) over 1.5 seconds, and this was taken as one cycle to perform a cycle test. The time for one cycle was 12.5 seconds, and the number of cycles until the test piece was broken was multiplied to obtain the fatigue durability time (minute).

  The results of the measurement of fatigue durability using Comparative Examples I-1 to I-8, Examples I-1 to I-4, and I-9 to I-12 are shown in Table 3 below. Further, plotting the measurement results of Table 3 with the horizontal axis representing the film thickness and the vertical axis representing the fatigue durability is shown in FIG. 4 for Comparative Examples I-1 to I-4 and Examples I-1 to I-4. FIG. 5 shows Comparative Examples I-5 to I-8 and Examples I-9 to I-12. Dotted lines in the graphs of FIGS. 4 and 5 indicate that the fatigue durability is 234 minutes.

From Table 3 and FIGS. 4 and 5, it can be seen that the fatigue durability is improved by adding the silicon-containing organic coagulant regardless of the type of the crosslinking agent.
This is probably because due to plasticizing effect of -CH 2 _-CH 2 _-O- chain is a soft segment in the silicon-containing organic coagulants.

(Tensile elongation)
A test piece was punched out from a cured film that had passed 7 days or more after production using a JIS K6251 No. 5 dumbbell test piece as a test piece, and was subjected to a temperature of 23 ° C. ± 2 ° C. and a humidity of 50% ± 10%. Stored overnight. Thereafter, a mark of 25 mm was placed at the center, the thickness of three points between the marks was measured, and the average thickness of the test piece was calculated. The tensile elongation was measured using a tensile tester STA-1225 (manufactured by A & D), at a test speed of 500 mm / min and a chuck-to-chuck distance of 75 mm, according to the method of Japanese Industrial Standards (JIS K 6251: 1993. Test method).
The results of measurement of the tensile elongation using Comparative Examples I-1 to I-4 and Examples I-1 to I-8 are shown in Table 4 below. Further, FIG. 6 shows a plot of the measurement results of Table 4 with the horizontal axis representing the film thickness and the vertical axis representing the tensile elongation.
The tensile elongation was determined based on the following equation (7).
Tensile elongation (%) = 100 × (distance between marked lines at break in tensile test−distance between marked lines) / distance between marked lines (7)

From the above Table 4 and FIG. 6, it can be seen that in Comparative Examples I-1 to I-3 which do not belong to the embodiment of the present invention, the tensile elongation decreases as the film thickness decreases. This is the behavior of a general elastomer. On the other hand, in Examples I-1 to I-4 and I-5 to I-8 belonging to the embodiment of the present invention, the behavior as in the above comparative example was not observed, and even if the film thickness was reduced, the tensile strength was not increased. Elongation did not decrease.
Therefore, by using the dip composition according to the embodiment of the present invention, gloves having excellent tensile elongation can be manufactured even when the thickness and the weight are reduced.

[Experiment II]
<Preparation of crosslinking agent>
As the cross-linking agent 3, polycarbodiimide (trade name: Carbodilite V-04, manufactured by Nisshinbo Co., Ltd.) was used. The information of Carbodilite V-04 is shown below.
Structure of hydrophilic segment: polyethylene glycol monomethyl ether (PEGME)
Structure of polycarbodiimide (type of organic diisocyanate): m-tetramethylxylylene dithiocyanate (TMX)
Number average molecular weight (measured value): 1900
Average polymerization degree = number average molecular weight / equivalent (calculated value): 5.7
Equivalent = molecular weight / degree of polymerization (catalog of Nisshinbo Chemical): 335

<Manufacture of dip composition>
[Dip composition 7]
170 g of the XNBR solution (solid content: 45%) of the above elastomer was placed in a 1 L beaker (manufactured by AS ONE Corporation, body diameter: 105 mm × height: 150 mm), diluted with 100 g of ion-exchanged water, and stirred. The pH was adjusted to 10 using ammonia. Further, based on the latex solid content, 0.7 phr of the above-mentioned crosslinking agent, 1.0 phr of zinc oxide (trade name “CHEMPERSEC ZnO-50”, manufactured by Farben Technique (M) Sdn Bhd), and 1.0 phr of titanium oxide (trade name “trade name”) 1.5 phr of FARSPERSE WHITE PW601, manufactured by Farben Technology (M) Sdn Bhd), and an antioxidant (trade name: “CHEMPERSE CVOX-50”, manufactured by Farben Technique (M) Sdn Bhr), and weighed by 0.2 The mixture was diluted with 150 g of ion-exchanged water, and added to the latex while washing with ion-exchanged water (step X). Thereafter, 80 g of ion-exchanged water was further added so that the total solid content (TSC) became 18%, and the mixture was stirred overnight to obtain Dip Composition 1.

[Dip composition 8]
In Step X above, Dip Composition 8 was obtained under the same manufacturing conditions as Dip Composition 7, except that 0.46% by weight of the above-mentioned silicon-containing organic coagulant was further added.

[Dip composition 9]
In Step X above, Dip Composition 9 was obtained under the same production conditions as Dip Composition 7, except that 0.93% by weight of the above-mentioned silicon-containing organic coagulant was further added.

[Dip composition 10]
In Step X above, Dip Composition 10 was obtained under the same manufacturing conditions as Dip Composition 7, except that 1.38% by weight of the silicon-containing organic coagulant 2 was further added.

<Production of coagulation liquid A>
Huntsman Corporation's surfactant “Teric 320” (trade name) 0.56 g dissolved in 42.0 g of water was dissolved in a solution of 42.0 g of water, and “S-9” (trade name of CRESAGE INDUSTRY) as a release agent was used. 19.6 g (solids concentration 25.46%) was slowly added after diluting about 2-fold with a portion of 30 g of water measured in advance. The whole amount was added while washing the remaining S-9 with the remaining water, and the mixture was stirred for 3 to 4 hours. Separately, calcium nitrate tetrahydrate having a calcium nitrate tetrahydrate concentration (hereinafter referred to as “Ca (NO ₃ ) ₂ concentration”) of a finally obtained coagulation solution of 7% is used, respectively. Each of the calcium nitrate tetrahydrates described above was placed in a 1 L beaker (manufactured by AS ONE Corporation, body diameter 105 mm × height 150 mm) containing 196.2 g of water to obtain four types of solutions. While stirring these four types of solutions, the previously prepared S-9 dispersion was added to the aqueous calcium nitrate solution. The pH was adjusted to 8.5 to 9.5 with 5% aqueous ammonia, and water was added so that S-9 had a solid concentration of 1.0% to obtain 500 g of four types of coagulating liquids. The obtained coagulation liquid A was continuously stirred in a 1 L beaker until use.

<Production of cured film>
[Comparative Example II-1, Examples II-1 to II-3]
The obtained coagulation liquid A was heated to 50 ° C. with stirring, filtered through a 200-mesh nylon filter, placed in an immersion container, washed and then heated to 60 ° C. on a ceramic plate (200 × 80 × 3 mm). , Hereinafter referred to as “ceramic plate”). Specifically, after the tip of the porcelain plate came into contact with the liquid surface of the coagulating liquid, the plate was immersed for 4 seconds from the tip of the porcelain plate to a position of 18 cm, held for 4 seconds while immersed, and extracted for 3 seconds. . The coagulating liquid adhering to the surface of the ceramic plate was immediately shaken off, and the surface of the ceramic plate was dried. The dried ceramic plate was again heated to 60 ° C. in preparation for dipping of the dip composition 7.
After the dip composition 7 was filtered at room temperature through a 200 mesh nylon filter, it was placed in an immersion container, and a 60 ° C. porcelain plate to which the above-mentioned coagulating liquid was adhered was immersed. Specifically, the ceramic plate was dipped for 6 seconds, held for 4 seconds, and extracted for 3 seconds. After the dip composition did not drip, it was held in the air for 30 seconds, and the latex droplet attached to the tip was lightly shaken off.
Thereafter, each porcelain plate immersed in the dip composition 7 was left at room temperature (23 ° C.) for 1 minute (gelling), and leached with 50 ° C. ion-exchanged water for 3 minutes. Thereafter, it was dried at 70 ° C. for 5 minutes (precuring), and thermally cured at 130 ° C. for 30 minutes (curing).
The obtained cured film was peeled cleanly from the ceramic plate, sandwiched between thin papers, and stored in an environment at a temperature of 23 ° C. ± 2 ° C. and a humidity of 50% ± 10% until subjected to a physical property test to obtain a cured film of Comparative Example II-1. Was.
The above-described dip composition 7 was changed to dip compositions 8, 9, and 10, except for that, cured films were produced in the same manner as in Comparative Example II-1, and Examples II-1 to II-3 were prepared. A cured film was obtained.
The film thicknesses of Comparative Example II-1 and Examples II-1 to II-3 were all 0.041 to 0.050.

<FAB>
FAB was measured under the same conditions as in Experiment I.
The results of FAB measurement using Comparative Example II-1 and Examples II-1 to II-3 are shown in Table 5 below.

  From Table 5 above, it can be seen that FAB increases with the addition of the silicon-containing organic coagulant, and that the FAB increasing effect is maintained even when the amount of the silicon-containing organic coagulant is changed.

  According to an embodiment of the present invention, comprising an elastomer, and a silicon-containing organic coagulant for coagulating the glove dip composition, when preparing a glove dip composition, even when thinning and weight reduction, film forming It is possible to provide a glove dip composition capable of producing gloves without reducing the properties and producing gloves having high tensile strength.

Claims (8)

  A glove dip composition comprising an elastomer and a silicon-containing organic coagulant for coagulating the glove dip composition.   2. The glove dip composition according to claim 1, wherein the content of the silicon-containing organic coagulant is 0.1 to 3.0% by weight based on the total solid content of the glove dip composition.   The dip composition for gloves according to claim 1 or 2, wherein the silicon-containing organic coagulant is a silicone oil.   The glove dip composition according to claim 3, wherein the silicone oil is a polyether-modified silicone oil. The glove dip composition according to claim 4, wherein the polyether-modified silicone oil is represented by the following formula (1).

(In the formula (1), 0.1 mol% ≦ x ≦ 1.0 mol%, 0.5 mol% ≦ y ≦ 1.2 mol%, 45 mol% ≦ m ≦ 56 mol%, and 42 mol% ≦ n ≦ 55 mol%. ) A stirring step of leaving the glove dip composition according to any one of claims 1 to 5 with stirring, and a dipping step of immersing a glove mold in the glove dip composition.
A method for producing gloves.   7. An inorganic coagulant adhering step of immersing the glove mold in a coagulant solution containing a calcium ion-containing inorganic coagulant and adhering the coagulant to the glove mold before the dipping step. The method for producing a glove according to the above.   A glove comprising an elastomer and having a silicon content of 0.0005 to 0.3% by weight.

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