TW201313833A - Elastomer ribber without using vulcanization promoting agent and sulfur, and elastomer rubber products - Google Patents

Abstract

It is a glove formed by an elastomer containing 25 to 30 wt% acrylonitrile, 62 to 71 wt% butadiene and 4 to 8 wt% unsaturated carboxylic acid (total: 100 wt%), wherein the elastomer is cross-linked by a bond of at least a part of the substituent having the unsaturated carboxylic acid, and the at least a part of the substituent having the unsaturated carboxylic acid has a residual substituent which is cross-linked by a di-valent metal. The elastomer does not contain sulfur as a cross-linking agent, nor does it contain a sulfur compound as a vulcanization promoting agent. The elastomer cross-linked by the bond of at least a part of the substituent having the unsaturated carboxylic acid has a Mooney viscosity (ML(1+4)(100 DEG C)) of 100 to 220, the glove is characterized in having a thin film of elastomer which does not use sulfur as a cross-linking agent, nor a sulfur compound as a vulcanization promoting agent, the thin film having a thickness of 0.05 to 0.15mm, a glove expansion rate at the time of glove-forming of 240 to 320%, a tensile stress of 22 to 35MPa, an elongation at breakage of 480 to 620%, and a tensile stress of 15 to 35MPa at the 500% elongation.

Description

Elastomeric rubber and elastic rubber products without sulfur vulcanization accelerator and sulfur

The present invention relates to the formation of an unsaturated carboxylic acid end by adding an unsaturated carboxylic acid to an acrylonitrile butadiene unsaturated carboxylic acid with or without an unsaturated carboxylic acid added to an acrylonitrile butadiene unsaturated carboxylic acid. Crosslinking of the base and the unsaturated carboxylic acid with zinc oxide, and attaching the composition containing the same to the surface of a mold or a mold, and forming a thin film which is crosslinked and hardened Rubber gloves.

In the manufacture of latex products after immersion such as rubber medical gloves, natural rubber latex has been used as a raw material for many years. The medical glove made of the natural rubber latex produced as described above is known to have excellent stretchability and is a barrier against the movement of pathogens contained in the blood.

In the method for producing a natural rubber glove, sulfur is conventionally added as a crosslinking agent and a crosslinking accelerator. Specifically, a mold or a molding die having a shape of a hand is immersed in a natural rubber latex mixture to which a crosslinking agent and a crosslinking accelerator are added one or several times to form a desired surface on a mold or a molding die. The layer of thickness. The rubber glove of the desired thickness is dried and crosslinked under heating conditions.

Crosslinking is a basic step for imparting a high degree of stretchability to a natural rubber film. The natural rubber glove thus manufactured has excellent barrier properties, mechanical properties and physical properties.

The natural rubber latex contains 5% or less of a non-rubber component composed of a protein, a lipid, and a trace component. Due to the non-rubber component, along with The increase in the use of natural rubber latex gloves in hospitals has led to an increase in the incidence of type I allergies in this user. Type I allergies caused by direct contact with natural rubber latex gloves are known to be caused by extractable latex proteins remaining in natural rubber. Symptoms that cause immediate symptoms are caused within 2 hours of contact with the gloves. The causative substance is produced by IgE (antibody in circulating blood), thereby causing an allergic reaction. At this time, on the surface of the skin, a state of hives which is in a state of being mixed with the point of contact with the latex is exhibited.

Allergic symptoms caused by the whole body, such as itching of the eyes, swelling of the lips and tongue, shortness of breath, dizziness, abdominal pain, nausea, extreme tension and occasional shock caused by allergies.

For those who develop symptoms of allergies caused by natural rubber latex proteins, it is recommended to avoid further contact with natural rubber latex and articles made from natural rubber latex.

The synthetic latex obtained by synthesizing the nitrile rubber, the carboxylated nitrile latex, the polychloroprene latex or the polybutadiene latex does not cause the aforementioned allergy because it does not contain the aforementioned protein. For those who are allergic to proteins, it is recommended to use gloves made of synthetic latex such as nitrile rubber, carboxylated nitrile latex, polychloroprene latex or polybutadiene latex.

The glove produced by the synthetic rubber latex is not as good as the viewpoint of the physical properties from the viewpoint of physical properties, although it is equally or well evaluated.

The method of manufacturing medical gloves from synthetic rubber is the same as the method of manufacturing gloves by natural rubber.

Following the same procedure as the method of manufacturing a glove by natural rubber, the elastomer latex composition of the synthetic rubber is attached to the surface of a mold or a molding die formed into a shape of a hand, and then dried, crosslinked, and hardened. A glove of a film of desired thickness. The thus obtained glove obtained by synthesizing the formed elastomer can obtain a glove having desired mechanical and physical properties. Gloves formed from a large number of synthetic rubber elastomers have been developed and are currently on the market. As a result, the carboxylated nitrile rubber is widely used as a starting material for producing a synthetic rubber glove.

In the method of producing a glove from a synthetic rubber latex, sulfur is used as a crosslinking agent, and a sulfur-containing compound is used as a crosslinking accelerator. Specific examples of the sulfur-containing compound include dithiocarbamate, thiolan (TMTD), and mercaptobenzothiazole (MBT). These sulfur-containing compounds promote the rate of sulfurization. When a vulcanization accelerator is not used, only sulfur is used for the sulfur addition reaction. At this time, the treatment was carried out for several hours at a high temperature of 140 ° C, and the reaction was allowed to proceed slowly.

The result of actively using a vulcanization accelerator when manufacturing rubber gloves causes health problems. Specifically, these vulcanization accelerators cause symptoms of delayed type IV allergy of contact dermatitis as an allergic symptom. Delayed type IV allergies can be caused after 24 to 72 hours after contact. Symptoms are usually found on the surface of the hands or wrists and usually produce punctate rashes, red skin, sometimes skin cracking or blisters.

When the use of the natural rubber latex glove was stopped and the nitrile rubber latex glove was inspected, it was found that an excessive amount of the vulcanization accelerator remained as a residue in the nitrile rubber latex. Due to the cessation of the use of natural rubber latex gloves, although type I allergies can be avoided, the result is delayed by the nitrile rubber latex. Symptoms of type IV allergy.

Therefore, it has become a matter of urgency to develop a method for eliminating the use of sulfur as a crosslinking agent or a vulcanization accelerator to manufacture synthetic rubber gloves. When sulfur is not used as a crosslinking agent and a sulfur-containing compound is used as a vulcanization accelerator to form a crosslinked carboxylated nitrile rubber latex, it is necessary to carry out crosslinking by using a crosslinking agent which does not employ sulfur. In the case of this method, a method of forming a crosslink in accordance with an ionic bond using a divalent or trivalent metallic zinc is discussed. Compared with the case of sulfur, this method can be regarded as the same in terms of bonding, but from the viewpoint of physical properties such as strength and elongation of sulfur products, it is impossible to obtain desired results and still exist. problem. In the present invention, a divalent metal salt such as zinc oxide is used as a main structure.

U.S. Patent No. 5,014,362 (Patent Document 1) is a method of forming a crosslinked coal carboxylated nitrile rubber using zinc oxide and sulfur. A typical carboxylated nitrile rubber is formed from a segment composed of acrylonitrile, butadiene, and an organic acid formed in various ratios. Crosslinking can be formed by covalent bonds in the sub segment of butadiene by using sulfur and a vulcanization accelerator. Further, for the carboxylated acrylonitrile (organic acid) portion, an ionic bond can be produced by using a metal oxide such as zinc oxide or another metal salt or the like. It is ionic crosslinked by zinc ions and crosslinked by sulfur. Although the physical properties such as tension, breaking force, and abrasion resistance can be improved compared with the film formed by ionic crosslinking by zinc ions, the problem is that the disadvantages caused by the use of sulfur remain.

As described above, when the mechanism of crosslinking is based only on ionic bonds, it has to be used as a quality reliable because of its resistance to oil and chemicals. A rubber product with a lower degree of properties.

In general common sense, a carboxylated nitrile rubber product such as a glove, by using a combination of a covalent bond formed by a sulfur and a vulcanization accelerator, and an ion formed by a metal oxide such as zinc oxide or a metal salt Sexual cross-linking treatment, and effective cross-linking.

The use of such a sulfur-adding accelerator as a cross-linking method raises new health problems for delayed type IV allergy.

Regarding the strength of the rubber, in order to promote the polymerization reaction by using an organic oxide, it is known to add zinc organic zinc dimethacrylate and/or zinc methacrylate to the rubber to increase the strength.

Specifically, it is as follows. Polybutadiene and methacrylic acid can be mixed, and then zinc oxide is mixed to obtain a composition having excellent abrasion resistance. (Patent Document 2, JP-A-53-125139, and Patent Document 3, JP-A-52-121653 It is possible to obtain a synthetic polymer having a tensile property superior to that of a natural latex by adding a non-polymerizable carboxylic acid to a mixture of a diene rubber and methacrylic acid, zinc oxide, or an organic peroxide. (Patent Document 4, JP-A-53-85842). By using methacrylic acid, zinc oxide, and peroxide, crosslinking of NBR can be performed even if no ionic bond is present.

In the case of 100 parts by weight of (a) the ethylenically unsaturated nitrile-conjugated diene copolymer rubber, (b) coarse particles of 20 μm or more are blended as 5 in the patent document 5 (Japanese Patent Publication No. 8-19264). 10 to 60 parts by weight of the zinc compound or less, (c) 20 to 60 parts by weight of methacrylic acid, and (d) 0.2 to 10 parts by weight of the sulfur-containing rubber composition of the organic peroxide.

A rubber-sulphurized material having a good strength characteristic and a sulfur-added rubber composition are useful for the manufacture of hoses, rolls, anti-vibration rubbers, etc., but are not made of a thin sheet of gloves. .

A rubber composition having high rigidity obtained by crosslinking in the presence of a sulfur hardening accelerator or zinc oxide-free (divalent zinc-free), has tension and chemical resistance, and is soft compared with the prior art. A soft nitrile rubber product (Patent Document 6 Japanese Patent No. 3517246, Japanese Patent Publication No. 2000-512684). The vulcanization accelerator is a thiolanium in combination with mercaptobenzothiazole (MBT). The soft nitrile rubber of the reaction product still contains sulfur.

As a carboxylated nitrile rubber of a copolymer of acrylonitrile and butadiene and an unsaturated carboxylic acid, an ionic bond can be formed by allowing zinc and a carboxyl group to exist. However, it is difficult to form a covalent bond by a compound containing zinc, and thus it is important to use a less added amount of sulfur and compensate for the disadvantage by crosslinking of zinc. In particular, JP-A-2002-527632 (Patent Document 7) describes a method for using acrylonitrile with butadiene and an unsaturated carboxylic acid by using 1 to 3 phr of sulfur and 0.5 phr of a polyvalent metal oxide. The carboxylated nitrile rubber of the copolymer forms a crosslinked glove.

In the specification of U.S. Patent No. 6,673,871 (Patent Document 8), an elastomer product such as a glove is used, and a sulfur-containing crosslinking agent or a vulcanization accelerator is not used, and a metal oxide such as zinc oxide is used as a crosslinking agent. In Japanese Laid-Open Patent Publication No. 2004-526063 (Patent Document 8), the synthetic polymer is crosslinked without using a promoter, and is essentially composed of a metal oxide and is subjected to sulfur substitution. In the case of the crosslinking agent, the aforementioned synthetic polymer is crosslinked and hardened at a temperature of 85 ° C or lower. specific For example, a copolymer solution sold under the trade name of BARRIERPRO BP2000 and sold by Reichhold Chemicals, Inc. was crosslinked in the presence of a specific concentration of water and zinc oxide as a crosslinking agent. However, it is not clear how the copolymer acts in cross-linking, and the content of the cross-linking is also unknown. Regarding the crosslinking formed by the sulfur-substituted crosslinking agent, the synthetic polymer is hardened by crosslinking at a temperature of 85 ° C or lower, but when the temperature is too low, it is not always possible to obtain good crosslinking. The product. And the content of the cross-linking is not clearly stated, and it is considered that the specific response is still accompanied by difficulties.

JP-A-2008-534754 (Patent Document 9) relates to a rubber dispersion, a rubber dispersion for producing a latex foam, a method for producing a latex foam, and a rubber dispersion from the invention An invention of the obtained latex foam comprising a) 51 to 90% by weight of matrix latex polymer particles; and b) 10 to 49% by weight of an aromatic vinyl monomer and a conjugated diene monomer The reinforced polymer polymer particles of the structural unit, and the reinforced polymer polymer particles have a water reinforced rubber dispersion of a single glass transition temperature (Tg) of -25 ° C to 28 ° C measured by differential scanning calorimetry (DSC) The weight % is based on the total weight of the polymer particles in the rubber dispersion, and the matrix latex polymer particles have a Tg lower than the Tg of the strengthened latex particles measured according to DSC. This is not for latex foam.

This is to avoid the loss of the latex foam with respect to the viscoelastic property, that is, the elastic force and the recovery speed of the foam after compression, and is not intended to be a material of a thin glove as in the present invention.

Japanese Laid-Open Patent Publication No. 2008-545814 (Patent Document 10), which comprises the following steps and producing an elastomer article, that is, (a) producing zinc oxide containing 0.25 to 1.5 parts per 100 parts of dry rubber, and including A carboxylated nitrile is prepared by using a base, a stabilizer, a promoter selected from the group consisting of hydrazine and a dithiocarbamate and a thiazole compound as desired, with a pH of about 8.5 or more. a step of impregnating the rubber composition of the olefin; (b) a step of immersing the forming mold in the rubber composition prepared with the carboxylated nitrile butadiene; and (c) preparing the rubber composition having the carboxylated nitrile butadiene as described above The step of hardening to form the aforementioned elastomeric article.

Zinc oxide is used for crosslinking. In order to maintain the desired degree of chemical resistance of the article, a combination of vulcanization accelerators is included. The vulcanization accelerator uses dithiocarbamate. In order to increase the barrier property against chemical substances, a mixture of a dithiocarbamate vulcanization accelerator, a biphenyl hydrazine and a mercaptobenzothiazole zinc is used, whereby a higher degree of effect can be obtained. However, the cross-linking of rubber uses sulfur and a vulcanization accelerator, and the gloves thus produced still cause problems of type IV allergy.

In the specification of U.S. Patent No. 7,005,478 (Patent Document 11), it is described that when a product composed of an elastomer is produced, it contains: (a) a carboxylic acid or a derivative, and (b) contains a divalent or trivalent. The metal compound and (c) the amine or amine compound, and (d) at least a portion of the carboxylic acid group in the matrix polymer neutralize the neutralizing agent to react the elastomer having a carboxyl group. The vulcanization accelerator, thiocyanate, and carbamate are not used at this time. Examples of the polymer to be used as the matrix include natural latex rubber, synthetic latex polymer (acrylonitrile, etc.), butadiene rubber such as synthetic butadiene rubber and carboxylated butadiene rubber. But does not contain MMA and so on. In addition, the carboxylated acrylonitrile is not used. In the method, the above (c) amine or amine compound is used as an essential component. (c) An amine group or an amine group is reacted with a carboxylic acid derivative and formed in a misalignment with a divalent or trivalent metal. However, it is difficult to achieve stability in terms of applying a mismatch formation reaction, and it has been pointed out that it is difficult to obtain a stable product.

Japanese Laid-Open Patent Publication No. 2008-512526 (Patent Document 12) describes a polymer latex which is a soft phase portion and which independently contains a source selected from the group consisting of: a conjugated diene; an ethylenically unsaturated monocarboxylic acid; Ethylene-type unsaturated dicarboxylic acid, the anhydride, monoester and monodecylamine; (meth)acrylonitrile; styrene; substituted styrene; α-methylstyrene; (meth)acrylic acid C1 to C10 An ester of (meth)acrylic acid; a polymer latex of a structural unit of a monomer comprising a group consisting of an N-hydroxymethylguanamine group and an ethylenically unsaturated compound of the ester and an ether derivative, In any of the foregoing polymer latexes, the hard phase portion, independently of each other, is derived from: an ethylenically unsaturated monocarboxylic acid; an unsaturated dicarboxylic acid, the anhydride, a monoester, and a monodecylamine; - hydroxymethyl guanamine, and ethylenically unsaturated compounds of the esters and ether derivatives; and mixtures thereof; (meth)acrylonitrile; styrene; substituted styrene; alpha-methyl styrene; a C1 to C8 ester of methyl)acrylic acid; a decylamine of (meth)acrylic acid; and a group of such mixtures The structural unit of the monomer. And the crosslinking formed by the N-hydroxymethyl guanamine group is explained.

Japanese Laid-Open Patent Publication No. 2010-144163 (Patent Document 13) describes the crosslinking formed by a vinyl group or an epoxy group.

Japanese Patent Publication No. 2002-532164 (Patent Document 14) describes a combination of a crosslinking bond accepting functional group and a crosslinking agent.

Japanese Patent Publication No. 2009-525411 (Patent Document 15) describes self-crosslinking of polyvinyl alcohol.

Japanese Patent Publication No. 2005-049725 (Patent Document 16) uses an organic peroxide under specific conditions.

U.S. Patent No. 2006/0057320 (Patent Document 17) uses alkoxyalkyl melamine and zinc oxide for crosslinking.

U.S. Patent No. 2004/0132886 (Patent Document 18) uses a combination of zinc oxide and a peroxide as a crosslinking agent.

U.S. Patent No. 2003/0017286 (Patent Document 19) uses zinc oxide and a carboxylic acid, an amine or an amine compound as a crosslinking agent.

In Non-Patent Document 1 (Andrew Kells and Bob Grobes "Cross-linking in carboxylated nitrile rubber dipped films" LATEX24-25, January 2006, Frankfurt, Germany), it is shown that a trace amount of sulfur is used, and as a sulfur-containing addition. Sulfur accelerator (TMTD), 2,2'-dithio-bis(benzothiazole) (MBTS), N-cyclohexylbenzothiazole sulfinamide (CBS) and diethylthioamino group Addition of zinc formate (ZDEC) and the necessary zinc oxide to obtain the content of the latex having improved tensile strength. On the contrary, it is difficult to obtain a carboxylated nitrile latex glove having durability when sulfur and a sulfur-based vulcanization accelerator are not used.

There is no technical description in the literature regarding the effect of attempting to manufacture gloves from self-crosslinking materials and the self-crosslinking properties necessary to produce the desired gloves. Knowing the technical description of self-crosslinking latex has not yet yielded sufficient results.

Non-Patent Document 2 (Dr. Soren Buzs "Tailored synthetic dipping latices: New approach for thin soft and strong gloves and for accelerator-free dipping" LATEX 23-24, January 2008, Madrid, Spain) is used by: replacing the previous sulfur Crosslinking is carried out by using a functional reactive group (R) to directly form a crosslink of the NBR latex, and a method of using the ionic bond formed by zinc oxide to form a crosslink between the carboxyl groups of the NBR latex. This method shows a promising approach as a future technical direction. Unfortunately, the functional basis for the action in the covalent bond has not been specifically described. Attempts to clarify this specific formation method have not been successful.

In NICHIAS Technical Information (No. 5, 2000, No. 321) (Non-Patent Document 3), epoxidized natural rubber and carboxylated NBR are used in combination as self-crosslinking.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] US Patent No. 5014362

[Patent Document 2] JP-A-53-125139

[Patent Document 3] JP-A-52-121653

[Patent Document 4] JP-A-53-85842

[Patent Document 5] Japanese Patent Publication No. 8-19264

[Patent Document 6] Japanese Patent No. 3517246, Japanese Patent Publication No. 2000-503292

[Patent Document 7] Japanese Patent Publication No. 2002-527632

[Patent Document 8] US Patent No. 6,673,871, Japanese Patent Laid-Open Publication No. 2004-526063

[Patent Document 9] Japanese Patent Publication No. 2008-534754

[Patent Document 10] Japanese Patent Laid-Open Publication No. 2008-545814

[Patent Document 11] US Patent No. 7005478

[Patent Document 12] Japanese Patent Publication No. 2008-512526

[Citation 13] Japanese Patent Laid-Open Publication No. 2010-144163

[Citation 14] Japanese Special Publication No. 2002-532164

[Citation 15] Japanese Special Publication 2009-525411

[Citation 16] Japanese International Publication No. 2005-049725

[cited document 17] US Patent 2006/0057320

[Citation 18] US Patent 2004/0132886

[cited document 19] US Patent 2003/0017286

[Non-patent literature]

[Non-Patent Document 1] Andrew Kells and Bob Grobes "CROSS LINKING IN KARBOXYLATED NITRILE RUBBER DIPED FILMS" LATEX24-25, JANUARY 2006, Frankfurt, Germany

[Non-Patent Document 2] Dr. SorenBuzs "TAILORED SYNTHETIC DIPPING LATICES: NEW APPROACH FOR THIN SOFT AND STORNG GLOVES AND FOR ACCELERATOR FREEDIPPING" LATEX23-24, JANUARY 2008, Madrid, Spain

[Non-Patent Document 3] NICHIAS Technical Information (No. 5, 2000)

When a latex of butadiene, acrylonitrile and an unsaturated carboxylic acid elastomer is used, For sulfur and sulfur-containing vulcanization accelerators (also known as sulfur-containing cross-linking accelerators), when a part of the above sulfur is substituted with zinc oxide and zinc oxide and sulfur and sulfur-containing vulcanization accelerator are used, When using zinc oxide, there is no problem in terms of strength and the like. The medical gloves obtained by cross-linking contain a sulfur-containing vulcanization accelerator even in a small amount. This medical glove does not use natural rubber. Although it is possible to prevent type I allergies caused by natural rubber which has been a problem in the past, there is no sufficient countermeasure against type IV allergies caused by a delayed sulfur-containing vulcanization accelerator. Therefore, it is required to respond to this situation.

As described above, in order to carry out crosslinking without using sulfur as a crosslinking agent, a metal oxide mainly composed of zinc oxide has been studied. However, since zinc oxide, a butadiene, and an unsaturated carboxylic acid elastomer which are crosslinked by using zinc oxide as a crosslinking agent, sufficient characteristics cannot be obtained in terms of strength.

As described above, when zinc oxide is used as the crosslinking agent, it is insufficient in terms of strength and the like, and therefore it must be used in combination with other crosslinking agents and crosslinking accelerators. When used in combination with a cross-linking agent composed of sulfur and a cross-linking accelerator containing sulfur, even a small amount may cause delayed type IV allergy. Therefore, a crosslinking agent composed of sulfur and a sulfur-containing crosslinking accelerator cannot be used. Therefore, a cross-linking means for type IV allergy that does not cause delayed type is required.

The first problem to be solved by the present invention is to provide a terminal group of an unsaturated carboxylic acid of acrylonitrile, butadiene and an unsaturated carboxylic acid elastomer, and other acrylonitrile, butadiene and unsaturated carboxylic acid. The terminal groups of the bulk unsaturated carboxylic acid are bonded to form a crosslinked elastomer composition having strength.

The second problem to be solved by the present invention is to provide a class with the above The terminal group of the unsaturated carboxylic acid of acrylonitrile, butadiene and unsaturated carboxylic acid elastomer obtained from the problem, and the terminal group of the unsaturated carboxylic acid of other acrylonitrile, butadiene and unsaturated carboxylic acid elastomers Bonding to form a crosslink having strength, but additionally forming an acrylonitrile, butadiene, and unsaturated in a free state without using sulfur as a crosslinking agent and a sulfur compound as a vulcanization accelerator. The terminal group of the unsaturated carboxylic acid of the carboxylic acid elastomer forms an ionic bond with the terminal group of the unsaturated carboxylic acid of the other acrylonitrile, butadiene, and unsaturated carboxylic acid elastomer in a free state via the divalent metal ion. Crosslinking is formed, and by this two kinds of crosslinking means, an elastomer composition having good dynamic viscoelastic properties is formed.

The third problem to be solved by the present invention is to use the cross-linking obtained in the first stage and the cross-linking in the second stage obtained in the second problem, without using sulfur as a crosslinking agent and as a vulcanization accelerator. An elastomer composition having a good dynamic viscoelastic property produced by a sulfur compound, and the resulting elastomer composition is used to manufacture a glove, and as a result, a thinned glove can be provided under the type IV allergy which does not cause delayed type of hair. Gloves with tensile stress and strength at break, elongation, and sufficient tensile stress at break.

The present inventors have found the following new solutions and have completed the present invention.

a terminal group of an unsaturated carboxylic acid added to an acrylonitrile butadiene unsaturated carboxylic acid obtained by adding an unsaturated carboxylic acid to acrylonitrile butadiene or an acrylonitrile butadiene unsaturated carboxylic acid; Acrylonitrile butadiene obtained by adding carboxylic acid to acrylonitrile butadiene or acrylonitrile butadiene unsaturated carboxylic acid The terminal group of the unsaturated carboxylic acid added to the saturated carboxylic acid is reacted to thereby bond the terminal groups of the unsaturated carboxylic acid, so that the first-stage crosslinking (crosslinking in the first stage) can be carried out. Although the crosslinking can be carried out only by the bond, the crosslinking method cannot be completely solved. Therefore, the terminal group of the unsaturated carboxylic acid added to the acrylonitrile butadiene unsaturated carboxylic acid can be obtained by an unsaturated carboxylic acid which is not added to other acrylonitrile butadiene unsaturated carboxylic acid. The terminal group is bonded to the remaining acrylonitrile butadiene unsaturated carboxylic acid to be in a free state, and an ionic bond (crosslinking of the second stage) is formed by the metal salt via the terminal group in the free state.

In the crosslinking of the first stage, the terminal group of the unsaturated carboxylic acid may be a reaction product selected from the group consisting of a carboxyl group, a hydroxymethyl guanamine group, a carboxyl group and a diamine, and a reaction product of a carboxyl group and an alkylenediamine. And a bond of a reaction product of a carboxyl group and an alkyl alcohol.

(1) The elastomer composition obtained by crosslinking in the first stage is as follows.

The elastomer composition is composed of 25 to 30% by weight of acrylonitrile, 62 to 71% by weight of butadiene, and 4 to 8% by weight (100% by weight of total) of the unsaturated carboxylic acid, and is the aforementioned unsaturated carboxylic acid. a bond having at least a part of a substituent formed to form a crosslink, and the remaining substituent of the substituent having at least a part of the unsaturated carboxylic acid is in a free state, and the Mooney viscosity of the crosslinked product ( ML ₍₁₊₄₎ (100 ° C)) is 100 to 220, and the film has a weight swelling ratio of 200 to 400%.

Crosslinking is as follows.

Adding carboxylic acid to acrylonitrile butadiene or acrylonitrile butadiene carboxylic acid The terminal group of the unsaturated carboxylic acid added to the acrylonitrile butadiene carboxylic acid, and the propylene obtained by adding the carboxylic acid to the acrylonitrile butadiene or the acrylonitrile butadiene carboxylic acid The characteristics of the product in which the terminal group of the unsaturated carboxylic acid added to the nitrile carboxylic acid is reacted to form a bonding group and thereby cross-linking in the first stage are as follows.

The characteristics are as follows. In the acrylonitrile butadiene carboxylic acid of the present invention, the Mooney viscosity (ML ₍₁₊₄₎ (100 ° C)) is from 100 to 220, which is a relatively high molecular weight state, and is excellent in processing properties as a glove, and further, obtained Gloves are sufficiently thick and have material barrier properties and have sufficient strength or tensile strength. Further, the film weight swelling ratio (heat treatment at 40 ° C and measurement as a uniform film) was 200 to 400%. Judged as a good glove material. Since sulfur as a crosslinking agent and a sulfur compound as a vulcanization accelerator are not used, it does not cause delayed type IV allergy. When an anionic surfactant is used as a dispersing agent, sulfur as a crosslinking agent and a vulcanization accelerator are not used, so that delayed type IV allergy is not caused.

(2) The elastomer composition obtained by crosslinking in the second stage is as follows.

An elastomer composition composed of 25 to 30% by weight of acrylonitrile, 62 to 71% by weight of butadiene, and 4 to 8% by weight (100% by weight of total) of unsaturated carboxylic acid, and a bond formed by at least a part of the substituent of the saturated carboxylic acid to form a covalent bond, and the remaining substituent of the substituent of at least a part of the unsaturated carboxylic acid is formed by forming an ionic bond via the divalent metal ion The crosslinked, crosslinked product has a film weight swelling ratio of 200 to 400%.

In the second-stage cross-linking, for the cross-linked elastomer composition of the first stage described above, the uncrosslinked portion is crosslinked according to the ionic bond by the divalent metal ion compound.

Containing 100 phr of the crosslinked elastomer composition in the first stage, and 0.5 to 4.0 phr of the crosslinking agent composed of divalent metal ions, and 0.1 to 2.0 by pH adjuster for adjusting the pH to 9 to 10. The phr and the dispersing agent are composed of 0.5 to 2.0 phr and water, and the amount of water is treated in such a manner that the concentration of the total solid phase material (TSC) generated when the mixture is mixed is 18 to 30% by weight.

By this treatment, the terminal group which is added to the terminal group of the unsaturated carboxylic acid of the acrylonitrile butadiene unsaturated carboxylic acid and is in a free state is similarly added to the unsaturated carboxylic acid of acrylonitrile butadiene. The terminal group of the acid unsaturated carboxylic acid and the terminal group in a free state, and the crosslinking formed by the divalent metal ion via the divalent metal ion, specifically, the second stage of crosslinking via the zinc metal ion.

The characteristics of the crosslinked product obtained by the second stage of crosslinking are as follows.

Sulfur and sulfur-containing substances were not used as crosslinking agents and sulfurization promoters in the first stage. At least a portion of the terminal group of the unsaturated carboxylic acid added to the acrylonitrile butadiene unsaturated carboxylic acid and other propylene in a state which does not contain sulfur and sulfur-containing substances as observed in the previous crosslinked product The terminal group of a part of the unsaturated carboxylic acid added to the nitrile butadiene unsaturated carboxylic acid is bonded to form a crosslink. At least a portion of the terminal group of the remaining unsaturated carboxylic acid other than the addition to the acrylonitrile butadiene carboxylic acid is not in contact with other acrylonitrile butadiene The terminal group of a part of the unsaturated carboxylic acid added to the saturated carboxylic acid is bonded to form a cross-linking, but a terminal group remaining as a free state remains. The terminal group in a free state is bonded to a terminal group of a partially unsaturated carboxylic acid added to another acrylonitrile butadiene carboxylic acid in a free state via a divalent metal ion when treated under the aforementioned conditions. Form crosslinks.

In the formation of the cross-linking, in order to carry out the emulsified state, it is carried out using a dispersing agent. In order to form a good dispersion state, it is indispensable to use a surfactant such as an alkylbenzenesulfonate as an anionic surfactant. The alkylbenzene sulfonic acid is not a crosslinking agent and a vulcanization accelerator, but a dispersing agent. The vulcanization accelerator formed by the presence of the sulfur compound does not cause allergic symptoms of contact dermatitis. Hair style type IV allergy.

The dynamic viscoelastic motion was investigated as the characteristic, and as a result, the following contents were confirmed. The Tg temperature of the crosslinked acrylonitrile butadiene unsaturated carboxylic acid in the second stage was -10.1 °C. On the other hand, as another raw material, 6322 was 12.2 ° C and Nipol 550 was -11.8 ° C. It is known that the cross-linked acrylonitrile butadiene unsaturated carboxylic acid of the second stage is higher than the above. This can be considered for the entanglement of this, and the self-crosslinking crosslink density is in a higher state. Further, the length of the flat portion of the rubber-like region is extremely short in the Nipol 550 which is considered to be not self-crosslinking, and this is not the case in the present invention.

When comparing the dynamic viscoelasticity results of the acrylonitrile butadiene unsaturated carboxylic acid after crosslinking of the second stage of the present invention with the acrylonitrile butadiene unsaturated carboxylic acid which is usually crosslinked by sulfur, zinc is formed. The crosslink density of acrylonitrile butadiene unsaturated carboxylic acid after crosslinking in the second stage is increased, and the elastic modulus is higher. The crosslinks formed by sulfur are larger. This is considered to be the result of the zinc of the divalent metal salt according to the present invention.

The second stage cross-linked acrylonitrile butadiene unsaturated carboxylic acid (Tg: -11.0 to 1.5 ° C) of the present invention is higher than the crosslinked rubber (-14.5 ° C to -15.9 ° C) formed by sulfur. This is due to the increase in the crosslink density caused by the zinc cross-linking, and thus the decrease in the elastic modulus is also shifted to the high temperature side, and the amplitude of the transfer temperature region is broadened, and the storage elastic modulus is slowly lowered. The elastic modulus of the flat portion is increased.

From the results of the dynamic viscoelastic properties described below, it was found that the products of the present invention obtained the following characteristics under the results of crosslinking formed by the first-stage cross-linking and the second-stage cross-linking.

(a) The temperature at which the maximum value of the loss tangent (ratio of storage elastic modulus/loss elastic modulus) indicated by tan δ is shown, which corresponds to the glass transition in the transition temperature region where the rubber starts from the low temperature frozen state. Temperature (Tg), glass transition temperature, the higher the basic molecular motion is inhibited (difficult to move), such as the harder molecular chain or the higher the crosslink density, the higher.

In the acrylonitrile butadiene unsaturated carboxylic acid (denoted as SXL) of the present invention, -10.1 ° C was measured. In the previous product of 6322, the glass transition temperature was -12.2 ° C, and in Nipol 550, -11.6 ° C was measured.

The acrylonitrile butadiene unsaturated carboxylic acid of the present invention (expressed as SXL) gives higher results than in other cases. This speculation may be the highest crosslink density formed by the self-crosslinking of the entanglement. In addition, the Nipol 550 was observed to be extremely short.

(b) Flat rubbery shape in the high temperature region after the glass transition temperature The storage elastic modulus of the region tends to increase as the crosslinking density formed by the entanglement is higher and the molecular weight (Mc) between the crosslinked chains is lower. As is well known, the flat portion length (temperature region) of the rubber-like region shows correlation with the interlaced data per molecule.

According to Fig. 9, the increase in the modulus of elasticity in the flat portion of the rubber-like region of the acrylonitrile butadiene unsaturated carboxylic acid glove brought by the addition of zinc and sulfur is larger than that of the sulfur-based vulcanized product, and zinc is added. The increase in the elastic modulus is large, which reflects the increase in the crosslink density brought about by the addition of zinc.

According to Figure 7, the Tg temperature (-11.0 to 1.5 ° C) of the acrylonitrile butadiene unsaturated carboxylic acid glove is higher than that of the sulfur-based vulcanized rubber (-14.5 to -15.9 ° C). The increase in crosslink density causes the glass transition temperature to shift to the high temperature side, and thus the decrease in the modulus of elasticity is also shifted to the high temperature side, and the amplitude of the transition temperature region is broadened, and the storage elastic modulus is slowly lowered. The elastic modulus of the flat portion is increased.

The acrylonitrile butadiene unsaturated carboxylic acid elastomer emulsified composition after crosslinking in the first stage and the second stage is characterized in that the sulfur is not contained as a crosslinking agent and the sulfur compound as a vulcanization accelerator is obtained. The result of the acrylonitrile butadiene unsaturated carboxylic acid, and it can be confirmed from the foregoing that the property is good. From the acrylonitrile butadiene unsaturated carboxylic acid elastomer emulsified composition after the crosslinking in the first stage and the second stage, a glove having the following characteristics can be produced.

(3) attaching the elastomer composition obtained by crosslinking in the first stage and cross-linking in the second stage to the surface of a mold or a molding die of a general glove forming means, and hardening by crosslinking This completion has the following characteristics Gloves.

A glove composed of an elastomer which is composed of an elastomer containing 25 to 30% by weight of acrylonitrile, 62 to 71% by weight of butadiene and 4 to 8% by weight of unsaturated carboxylic acid can be obtained. 100% by weight of the whole, and a bond formed by a bond formed by at least a part of the substituent of the unsaturated carboxylic acid, and the remaining substituent of the substituent having at least a part of the unsaturated carboxylic acid is 2 The valence metal is crosslinked, the glove does not contain sulfur as a crosslinking agent and a sulfur compound as a vulcanization accelerator, and forms a crosslink by a bond formed by a substituent of at least a part of the aforementioned unsaturated carboxylic acid. The elastomer's Mui viscosity (ML ₍₁₊₄₎ (100 ° C)) is 100 to 220. Regarding the characteristics of the glove, the elastomer thinner film of the glove does not contain sulfur as a crosslinking agent and as a vulcanizing agent. The sulfur compound of the accelerator has a thickness of 0.05 to 0.15 mm, a glove swelling ratio of 240 to 320 when the glove is formed, a tensile stress of 22 to 35 MPa, an elongation at break of 480 to 620%, and an elongation of 500%. The tensile stress is 15 to 35 MPa.

(4) The description of the steps of the glove for producing the characteristics obtained in the above (3) is as follows.

The elastomer composition obtained in the step of (3) is cross-linked and hardened to obtain a glove.

The manufacturing steps are as follows.

(a) a step of washing a mold or a mold with a washing liquid and drying, (b) a step of immersing a mold or a molding die in a coagulant solution, and (c) a mold to which a coagulant is attached or a step of drying the molding die, (d) a mold or a molding die to which the coagulant is attached and dried, at 30 a step of immersing in the elastomer composition of the above (3) at a temperature of ° C for 1 to 20 seconds, and (e) drying the mold or molding die obtained in the above step (d) at 80 to 120 ° C a step, and (f) adding acrylonitrile to the surface of the mold or the molding die obtained in the above step (e) at 120 to 150 ° C as described in the above (3) An elastomer made of an olefin elastomer, which is subjected to a treatment for 20 to 30 minutes for crosslinking hardening.

In the present invention, the following effects can be achieved.

(1) The elastomer composition after the first stage of crosslinking is 25 to 30% by weight of acrylonitrile, 62 to 71% by weight of butadiene, and 4 to 8% by weight of unsaturated carboxylic acid (100% by weight of total) In the case where the Mooney viscosity (ML ₍₁₊₄₎ (100 ° C)) is 100 to 220, and the film is formed into a film, the film has a weight swelling ratio of 200 to 400%.

The production step is a terminal group of an unsaturated carboxylic acid added to an acrylonitrile butadiene carboxylic acid obtained by adding a carboxylic acid to acrylonitrile butadiene or acrylonitrile butadiene carboxylic acid, and the like. The terminal group of the unsaturated carboxylic acid added to the acrylonitrile butadiene carboxylic acid obtained by adding a carboxylic acid to acrylonitrile butadiene carboxylic acid or acrylonitrile butadiene carboxylic acid is reacted to form a bond, Perform the first stage of cross-linking.

(2) The elastomer composition after the second stage of crosslinking is 25 to 30% by weight of acrylonitrile, 62 to 71% by weight of butadiene, and 4 to 8% by weight of unsaturated carboxylic acid (100% by weight of the whole) And a covalent bond formed by a bond formed by a substituent of at least a part of the unsaturated carboxylic acid, and the remaining substituent of the substituent of at least a part of the unsaturated carboxylic acid is via The divalent metal ion forms an ionic bond to form a cross-linking, and the cross-linked product has a Mui viscosity (ML ₍₁₊₄₎ (100 ° C)) of 100 to 220, and the film has a weight swelling ratio of 200 to 400%. Elastomer composition. When the terminal group of the unsaturated carboxylic acid added to the acrylonitrile butadiene carboxylic acid obtained by adding the carboxylic acid to the acrylonitrile butadiene carboxylic acid is not present, the bond is not formed, and the terminal group is formed. In a free state.

The specific processing conditions are as follows. 100 to phr of the above-mentioned elastomer composition and 0.5 to 4.0 phr of a crosslinking agent composed of a divalent metal ion, and 0.1 to 2.0 phr of a pH adjusting agent for adjusting the pH to 9 to 10, and a dispersing agent 0.5 to 2.0 phr and water are formed, and the amount of water is treated under conditions of a concentration of 18 to 30% by weight of the total solid phase material (TSC) generated when mixing, by using zinc ions as divalent metal ions. Ion crosslinking is formed (the above is the second stage of crosslinking).

The novel crosslinked product of the present invention can be obtained by combining the crosslinking of the first stage and the second stage. When investigating the storage modulus, it was found that due to the crosslinking, in the case of the present invention, the Tg is increased, the crosslinking density is increased, and when crosslinking is formed by zinc, the zinc crosslink density is increased, and the glass is increased. The transfer temperature is increased.

(3) The characteristics of the glove are as follows.

A glove formed of an elastomer, which is formed of an elastomer containing 25 to 30% by weight of acrylonitrile, 62 to 71% by weight of butadiene, and 4 to 8% by weight of unsaturated carboxylic acid (all 100) % by weight, and crosslinked with a bond formed by at least a part of the substituents of the aforementioned unsaturated carboxylic acid, and the remaining substituent of at least a part of the substituent of the unsaturated carboxylic acid is composed of a divalent metal Cross-linking, the glove containing no sulfur as a crosslinking agent and a sulfur compound as a vulcanization accelerator, and an elastomer crosslinked by a bond formed by a substituent of at least a part of the aforementioned unsaturated carboxylic acid Muni's viscosity (ML ₍₁₊₄₎ (100 °C)) is 100 to 220. Regarding the characteristics of the glove, the glove with a thinner elastomer film does not contain sulfur as a crosslinking agent and sulfur as a vulcanization accelerator. The compound has a thickness of 0.05 to 0.15 mm, a glove swelling ratio of 240 to 320 when the glove is formed, a tensile stress of 22 to 35 MPa, an elongation at break of 480 to 620%, and a tensile stress at an elongation of 500%. 15 to 35 MPa.

In the present invention, an acrylonitrile butadiene unsaturated carboxylic acid obtained by adding an unsaturated carboxylic acid to acrylonitrile butadiene or an acrylonitrile butadiene unsaturated carboxylic acid is prepared: (1) forming the first The elastomer composition of the emulsion of the acrylonitrile butadiene unsaturated carboxylic acid after one stage of crosslinking, (2) after the first stage of crosslinking, the second stage of the crosslinked acrylonitrile An elastomer composition of an emulsion of an ethylenically unsaturated carboxylic acid. (3) A glove having a novel property is obtained by using the obtained elastomer composition of the emulsion of the acrylonitrile butadiene unsaturated carboxylic acid after the crosslinking of the second stage of the above (2). The product obtained in the above (1) to (3) has unique characteristics.

(1) The elastomer composition of the emulsion of the acrylonitrile butadiene unsaturated carboxylic acid after the first stage of crosslinking is formed as follows.

Adding unsaturated carboxylic acid to acrylonitrile butadiene or acrylonitrile a terminal group of an unsaturated carboxylic acid added to an acrylonitrile butadiene unsaturated carboxylic acid obtained by an ethylenically unsaturated carboxylic acid, and other carboxylic acid added to acrylonitrile butadiene or acrylonitrile The terminal group of the unsaturated carboxylic acid added to the acrylonitrile butadiene unsaturated carboxylic acid obtained by reacting an ethylenically unsaturated carboxylic acid is thereby bonded, whereby the crosslinking after the formation of the first stage is obtained An emulsion composed of an acrylonitrile butadiene unsaturated carboxylic acid elastomer obtained by adding an unsaturated carboxylic acid to acrylonitrile butadiene or an acrylonitrile butadiene unsaturated carboxylic acid.

The acrylonitrile butadiene unsaturated carboxylic acid of the product is composed of 25 to 30% by weight of acrylonitrile, 62 to 71% by weight of butadiene, and 4 to 8% by weight (100% by weight of total) of the unsaturated carboxylic acid, and It is specified by the amount ratio of each component. The portion considered to form crosslinks is formed from a larger amount of butadiene from 62 to 71% by weight. The unsaturated carboxylic acid used for crosslinking is the least of the three components.

An acrylonitrile butadiene unsaturated carboxylic acid elastomer obtained by adding a saturated carboxylic acid to an acrylonitrile butadiene or an acrylonitrile butadiene unsaturated carboxylic acid after crosslinking in the first stage The characteristics of the constituted emulsion are as follows.

An elastomer composition characterized by 25 to 30% by weight of acrylonitrile, 62 to 71% by weight of butadiene, and 4 to 8% by weight (100% by weight of total) of unsaturated carboxylic acid, and The bond formed by the substituent of at least a part of the unsaturated carboxylic acid to form a crosslink, and the remaining substituent of the substituent having at least a part of the unsaturated carboxylic acid is in a free state, and the cross-linking is formed. The Mooney viscosity (ML ₍₁₊₄₎ (100 ° C)) is 100 to 220, and the film has a weight swelling ratio of 200 to 400%.

A raw material composition composed of 25 to 30% by weight of acrylonitrile, 62 to 71% by weight of butadiene, and 4 to 8% by weight (100% by weight of total) of the unsaturated carboxylic acid is used to make the composition in the presence of a dispersing agent. Mixed raw material composition.

The unsaturated methacrylic acid was added to a mixture of acrylonitrile butadiene, and the following mixture was used for use.

A carboxylated acrylonitrile polybutadiene latex (SXL-XNRR manufactured by Synthomer Co., Ltd., 746SXL manufactured by Synthomer Co., Ltd.) can be used. In addition, it can be used under the Pure Protect 560 from Polymer Latex or the Polyac 560 from Shin Foong Company.

Adding unsaturated methacrylic acid to an unsaturated carboxylic acid of acrylonitrile butadiene, although forming a terminal group, other unsaturated methacrylic acid is added to the unsaturated carboxylic acid of acrylonitrile butadiene, It can be considered that no bond is formed between the terminal groups.

The terminal group of the unsaturated carboxylic acid to be used for crosslinking can be suitably used as long as it can form a bond with a terminal group of another unsaturated carboxylic acid. The terminal group of the unsaturated carboxylic acid used for the bond may be a reaction product selected from the group consisting of a carboxyl group, a hydroxymethylguanamine group, a carboxyl group and a diamine, and a reaction product of a carboxyl group and an alkylenediamine, and a carboxyl group and an alkyl group. The bond of the alcohol reaction product. These terminal groups may be directly introduced into the unsaturated carboxylic acid or may be appropriately introduced by means of substitution or the like.

Crosslinking is carried out by heating at about 40 °C. It is carried out in the presence of water or in the presence of a surfactant.

The formation reaction of crosslinking is as follows.

Adding unsaturated carboxylic acid to acrylonitrile butadiene or acrylonitrile a terminal group of an unsaturated carboxylic acid added to an acrylonitrile butadiene unsaturated carboxylic acid obtained by an ethylenically unsaturated carboxylic acid, and other carboxylic acid added to acrylonitrile butadiene or acrylonitrile The terminal group of the unsaturated carboxylic acid added to the acrylonitrile butadiene unsaturated carboxylic acid obtained by reacting an ethylenically unsaturated carboxylic acid is thereby bonded, whereby the first stage of crosslinking can be obtained. An acrylonitrile butadiene unsaturated carboxylic acid elastomer obtained by adding an unsaturated carboxylic acid to acrylonitrile butadiene or an acrylonitrile butadiene unsaturated carboxylic acid. This line is synonymous with the following reaction methods.

This is an unsaturated carboxylic acid (or methacrylic acid) formed by adding an unsaturated carboxylic acid (or methacrylic acid) to an acrylonitrile butadiene with or without an unsaturated carboxylic acid (or methacrylic acid). After the acrylonitrile butadiene elastomer, the unsaturated carboxylic acid (or methacrylic acid) is added to the acrylonitrile butadiene polymer to add the unsaturated carboxylic acid (or methacrylic acid) to the acrylonitrile Between the acrylonitrile butadiene portion of the olefin, or the addition of acrylonitrile butadiene or acrylonitrile butadiene unsaturated carboxylic acid (or methacrylic acid) to the unsaturated carboxylic acid (or methacrylic acid) An elastomer obtained by adding a polymer to an unsaturated carboxylic acid (or methacrylic acid) between acrylonitrile butadiene.

In the above form, acrylonitrile and butadiene are emulsion-polymerized to prepare acrylonitrile and a butadiene polymer. A copolymer of an unsaturated carboxylic acid (or methacrylic acid) and acrylonitrile butadiene was prepared by initially adding an unsaturated carboxylic acid (or methacrylic acid) (Case 1). In other cases, acrylonitrile and the butadiene polymer itself were used when the unsaturated carboxylic acid (or methacrylic acid) was not initially added (Case 2).

The above means that the unsaturated carboxylic acid (or methyl group) is initially or not added. Acrylonitrile butadiene of acrylic acid). The amount of unsaturated carboxylic acid (or methacrylic acid) in the case of case 1 means that a very small amount is added.

Adding an unsaturated carboxylic acid (or methacrylic acid) to obtain a polymer of an unsaturated carboxylic acid, methacrylic acid and acrylonitrile butadiene, and further adding an unsaturated carboxylic acid (or methacrylic acid) to obtain A polymer of an unsaturated carboxylic acid (or methacrylic acid) present in the butadiene portion of the same or different polymer as described above and a polymer of acrylonitrile butadiene (Case 3) ).

Adding an unsaturated carboxylic acid (or methacrylic acid) to an acrylonitrile and butadiene polymer to which an unsaturated carboxylic acid (or methacrylic acid) is not initially added, thereby obtaining an unsaturated carboxylic acid (or methacrylic acid) A polymer of an unsaturated carboxylic acid (or methacrylic acid) and an acrylonitrile butadiene between the butadiene portions of the same or different polymers as described above (Case 4).

The reaction caused in Case 3 and Case 4 is as follows.

The butadiene portion of acrylonitrile butadiene is active. The unsaturated carboxylic acid (or methacrylic acid) is added to the acrylonitrile butadiene in such a portion to form a branch or to carry out graft polymerization to prolong.

Depending on the case, the butadiene portion of the other unsaturated carboxylic acid (or methacrylic acid) and the adjacent one is added to form a branch or a graft polymerization state with the active portion. presence.

As described above, a part of the terminal group is bonded to a terminal group of another acrylonitrile butadiene elastomer unsaturated carboxylic acid, and at least a part of the remaining part remains as an elastomer composition in an unbonded state, which is the first Cross-linking of the stage.

The following conditions were confirmed by actual measurement by the characteristics of the acrylonitrile butadiene unsaturated carboxylic acid elastomer obtained by crosslinking in the first stage.

The Mooney viscosity (ML ₍₁₊₄₎ (100 °C)) ranges from 100 to less than 220.

When it exceeds 220, the molecular weight is high and the processability is poor. When it is less than 100, although the strength is maintained, it becomes difficult to form the film itself. When comparing the Mooney viscosity with similar products, Synthomer's 746SXL is about 128, the previous product is 6322 is 122, and the Nipol 550 is about 94. In addition, in general, NBR has a Mooney viscosity of 30 to 130.

In this stage of crosslinking, by using the Mooney viscosity, it is known that the molecular weight is high molecular weight (weight average) compared to the previous product.

When an emulsified composition produced by cross-linking is produced, even if a small amount of sulfur is not contained, and a vulcanization accelerator is not used, there is no delayed type IV allergy caused by the addition of the vulcanization accelerator. doubt.

The emulsified composition obtained by crosslinking in the first stage can be processed into a film shape at a temperature of about 40 ° C, and the film weight swelling ratio can be measured. From the results, it was found that the film weight swelling ratio showed a characteristic of 200 to 400%.

The film weight swelling ratio is defined as follows.

Film weight swelling ratio (%) = weight after swelling (g) × 100 / weight before swelling (g) - 100

The film has a weight swelling ratio of 200 to 400%, and it has been found that a film having a certain degree of crosslinking even without crosslinking treatment can be obtained under a drying treatment at 40 °C. Since this is the result of cross-linking of the first stage, it can be considered that in the present invention, a glove having sufficient physical properties (tensile strength, breaking strength, etc.) can be obtained without performing sulfur crosslinking.

Further, the characteristic that the film has a weight swelling ratio of 200 to 400% shows that the property is soft.

As a result of the emulsified composition obtained by crosslinking in the first stage, the range of the specific range of the Mooney viscosity and the range of the film weight swelling ratio of the combination is the characteristic at the end of the crosslinking stage of the first stage. From the results, it was found that even if the molecular weight is relatively high, it exhibits good properties of flexibility.

As a result of the measurement, as will be described later, the results of the Mooney viscosity 151, the film weight swelling ratio of 287%, the Mooney viscosity of 180, and the film weight swelling ratio of 336% were obtained.

(2) The emulsion elastomer composition after the crosslinking in the first stage and the second stage is formed as follows.

An elastomer composition comprising 25 to 30% by weight of acrylonitrile, 62 to 71% by weight of butadiene, and 4 to 8% by weight (100% by weight of total) of unsaturated carboxylic acid, and the aforementioned unsaturated carboxylic acid a bond formed by at least a part of the substituent of the acid to form a covalent bond, and the remaining substituent of the substituent having at least a part of the unsaturated carboxylic acid forms an ionic bond via the divalent metal ion to form a crosslink The film has a weight swelling ratio of 200 to 400%. Since the cross-linking is formed based on the divalent metal ions, the Mooney viscosity cannot be measured.

When the second-stage cross-linking is carried out, the cross-linking of the elastomer composition after the cross-linking of the first stage is formed by ionic bonds formed by metal ions.

Containing 100 phr of the elastomer composition, and 0.5 to 4.0 phr of a crosslinking agent composed of a divalent metal oxide, and 0.1 to 2.0 phr of a pH adjusting agent for adjusting the pH to 9 to 10, and a dispersing agent of 0.5 to 2.0 Phra and water In the configuration, the amount of water is added so that the concentration of the total solid phase substance (TSC) generated when the mixture is mixed is 18 to 30% by weight to produce an emulsified composition.

The aforementioned elastomer composition is an emulsified elastomer formed in the first stage. Specifically, it is an emulsified elastomer composition which is composed of 25 to 30% by weight of acrylonitrile, 62 to 71% by weight of butadiene, and 4 to 8% by weight (100% by weight of total) of unsaturated carboxylic acid, and Is a bond formed by a bond formed by a substituent of at least a part of the unsaturated carboxylic acid, and the remaining substituent of the substituent having at least a part of the unsaturated carboxylic acid is in a free state, and the emulsion is obtained. The Mooney viscosity (ML ₍₁₊₄₎ (100 ° C)) of the resultant product is from 100 to 220, and the film has a weight swelling ratio of 200 to 400%.

25 to 30% by weight of the aforementioned acrylonitrile, 62 to 71% by weight of butadiene, and 4 to 8% by weight (100% by weight of the total) of the unsaturated carboxylic acid, such that the unsaturated carboxylic acid is added with or without an unsaturated carboxylic acid Acetic acid acrylonitrile butadiene derived.

The terminal group of the unsaturated carboxylic acid used for the bond formed by the substituent of at least a part of the unsaturated carboxylic acid is a reaction product selected from the group consisting of a carboxyl group, a hydroxymethylguanamine group, a carboxyl group and a diamine. And a reaction product of a carboxyl group and an alkylenediamine, and a bond of a reaction product of a carboxyl group and an alkyl alcohol, and a terminal group of the acrylonitrile butadiene elastomer unsaturated carboxylic acid via a terminal group of the one or more A knot, and at least some other portion of the elastomer composition in an unbonded state.

By this treatment, the terminal group added to the terminal group of the unsaturated carboxylic acid of the acrylonitrile butadiene carboxylic acid and in a free state is also unsaturated for the addition of the acrylonitrile butadiene unsaturated carboxylic acid. End group of carboxylic acid and at In the terminal state of the free state, crosslinking by the divalent metal ion is carried out by forming a ionic bond by a divalent metal ion, specifically by a zinc metal ion.

a portion which is carboxylated by a reaction according to an unsaturated carboxylic acid (or methacrylic acid) after forming a branch by a reaction for forming a terminal group or performing graft polymerization, and one of the two The olefin moiety or further reacts in the same manner as the other butadiene moiety to bond the unsaturated carboxylic acid monomer (or methacrylic acid) via a divalent metal ion, as shown in the lower left diagram of FIG. 1 and the right side of FIG. Figure.

After the branching is formed by the above reaction or the graft polymerization is carried out, it is sometimes stopped at the stage in this stage. For this portion, a divalent metal ion is sometimes bonded to form an ionic bond.

The above crosslinking treatment can be regarded as causing the following reaction to the carboxylated acrylonitrile butadiene. The cross-linking reaction considered is as follows.

(A) A double bond carbon of a butadiene moiety in a carboxylated acrylonitrile butadiene graft polymerized by a methacrylic acid monomer. The carboxyl group of methacrylic acid forms an ionic bond via a carboxyl group and a zinc ion of the carboxylated acrylonitrile butadiene to form a crosslink.

(B) a methacrylic acid polymer having a dimer or more, graft-polymerized to a double bond carbon of a butadiene portion in the carboxylated acrylonitrile butadiene. The carboxyl group of methacrylic acid forms an ionic bond via a carboxyl group and a zinc ion of the carboxylated acrylonitrile butadiene to form a crosslink.

(C) a methacrylic acid monomer which crosslinks the double bond carbon of the butadiene portion of the carboxylated acrylonitrile butadiene. Carboxylic acid of methacrylic acid The carboxyl group and the zinc ion of the acrylonitrile butadiene after carboxylation form an ionic bond.

The (meth) methacrylic acid polymer of the dimer or more crosslinks the double bond carbon of the butadiene moiety in the carboxylated acrylonitrile butadiene. The carboxyl group of methacrylic acid forms an ionic bond via a carboxyl group and a zinc ion of the carboxylated acrylonitrile butadiene.

When comparing the previously used sulfurization reaction by sulfur and ion crosslinking formed by metal ions (left side of Fig. 2), it is crosslinked with the reactive vinyl compound of the present invention and formed by the metal. When the formed ionic crosslinks (on the right side of Fig. 2) are observed, the former is such that the alkyl group exists between the butadiene portions of different polymers via sulfur, and the crosslinks are formed by a simple structure, whereas the latter is via Forming branches or performing graft polymerization, or not through such states, but by internal crosslinking formed by unsaturated carboxylic acid (or methacrylic acid) and formation of ionic bonds by carboxyl groups via zinc oxide Crosslinking, thereby taking advantage of more complex and diverse cross-linking reactions. In the latter case, it is possible to create a state in which it is easy to crosslink when it is crosslinked.

In the latter case, in the case where an unsaturated carboxylic acid (or methacrylic acid) is added to the above polymer of acrylonitrile butadiene, it is understood that an unsaturated carboxylic acid (or methacrylic acid) remains as a residue. The case of unreacted materials.

In the actual measurement using GCMAS (Fig. 3), the latter (in the case of the present invention, the lower diagram of Fig. 3), the peak 1 of the unsaturated carboxylic acid (or methacrylic acid) monomer was observed. In the upper graph shown in Fig. 3, which uses a sulfur and sulfur compound to form a crosslinked elastomer, no peak 1 of the unsaturated carboxylic acid monomer was observed.

In the formation of cross-linking, in order to carry out in an emulsified state, a dispersing agent is used. Come on. In order to form a good dispersion state, it is indispensable to use a surfactant such as an alkylbenzenesulfonate as an anionic surfactant. The alkylbenzenesulfonic acid is not a crosslinking agent and a vulcanization accelerator, but a dispersant. The emulsion of the cross-linking which is completed in the second stage is in a state of containing an alkylbenzenesulfonate as an anionic surfactant as a dispersing agent. Sulfur can be determined by containing the substance. There is no sulfur or sulfide as a crosslinking agent. The vulcanization accelerator formed by the presence of the sulfur compound does not cause allergy symptoms and is a delayed type IV allergy of contact dermatitis.

Potassium hydroxide is used as a pH adjuster. This is used to adjust the pH to 9 to 10 as a crosslinking condition, which is 0.1 to 2.0 phr relative to 100 phr of the mixture. When it is less than 0.1 and more than 2.0 phr, the aforementioned pH cannot be sufficiently maintained.

An anionic surfactant is used as a dispersant. Specifically, a sodium salt of a naphthalenesulfonic acid polycondensate, an alkylbenzenesulfonate or the like can be used as a dispersing agent. Although these are sulfur compounds, they are used as dispersants and are detected during analysis. This is not used as a cross-linking agent or a vulcanization accelerator, and it does not cause allergies.

Commercial products can be purchased for use. For example, Tamol NN9104 or the like can be used. This amount is from 0.5 to 2.0 phr. This dispersant is beneficial for interfacial polymerization. Further, it can be sufficiently discharged by performing treatment under temperature conditions.

Titanium oxide is added as a whitening agent or a coloring agent. Colorants can be added to the mixture if necessary. An organic dye can be used for the color material.

As the antioxidant, specifically, a non-contaminating type of a polymer hindered phenol can be used, and for example, Wingstay L can be used.

When the composition for producing the above elastomer is used, the concentration of the total solid phase material (TSC) generated when the components are mixed is 18 to 30% by weight, and the amount is adjusted by the amount of water.

The dynamic viscoelasticity action was investigated for the characteristics of the acrylonitrile butadiene unsaturated carboxylic acid which was crosslinked by the first stage and subjected to the second stage of crosslinking, and the results confirmed the following.

In the invention of the present application, sulfur and a sulfur-containing substance are not used as a crosslinking agent and a vulcanization accelerator in the first stage. In the state of not containing sulfur and sulfur-containing substances as observed in the previous cross-linked product, the present invention can form cross-linking which does not cause delayed type IV allergy (when an anionic surfactant is used as a dispersing agent, the amount is Less and will not cause delayed type IV allergy).

From the results of the dynamic viscoelastic properties described below, it was found that the product of the present invention can enhance the effect of crosslinking by crosslinking formed by the first-stage crosslinking and the second-stage crosslinking. In particular, the effect of using zinc is as follows.

(1) The temperature at which the maximum value of the loss tangent (the ratio of the storage elastic modulus/loss elastic modulus) indicated by Tan δ is shown, which corresponds to the glass transition temperature in the transition temperature region where the rubber starts from the low-temperature freezing state and the micro-Brown motion (Tg), the glass transition temperature, the more the basic molecular motion is inhibited (difficult to move), such as the harder molecular chain or the higher the crosslink density, the higher (Fig. 7).

In the acrylonitrile butadiene unsaturated carboxylic acid (denoted as SXL) of the present invention, -10.1 ° C was measured. In the previous product of 6322, the glass transition temperature was -12.2 ° C, and in Nipol 550, -11.6 ° C was measured.

The acrylonitrile butadiene unsaturated carboxylic acid of the present invention (expressed as SXL), In other cases, higher results are obtained. This speculation may be that the crosslink density formed by self-crosslinking of the entanglement is high. In addition, the Nipol 550 was observed to be extremely short.

(2) The storage elastic modulus of the flat rubber-like region in the high temperature region after the glass transition temperature, the higher the crosslinking density formed by the entanglement, and the lower the molecular weight (Mc) between the crosslinked chains, the elastic modulus There is a tendency to increase. As is well known, the flat portion length (temperature region) of the rubber-like region shows a correlation with the number of interlaces per molecule.

According to Fig. 7, the increase in the modulus of elasticity in the flat portion of the rubber-like region of the acrylonitrile butadiene unsaturated carboxylic acid glove brought by the addition of zinc and sulfur is larger than that of the sulfur-based vulcanized product, and zinc is added. The increase in the elastic modulus is large, which reflects the increase in the crosslink density brought about by the addition of zinc.

According to Fig. 8, the Tg temperature (-11.0 to 1.5 ° C) of the acrylonitrile butadiene unsaturated carboxylic acid glove is higher than that of the sulfur-based vulcanized rubber (-14.5 to -15.9 ° C), which is due to the addition of zinc. The increase in crosslink density causes the glass transition temperature to shift to the high temperature side, and thus the decrease in the modulus of elasticity is also shifted to the high temperature side, and the amplitude of the transition temperature region is broadened, and the storage elastic modulus is slowly lowered. The elastic modulus of the flat portion is increased.

In the case of the present invention, the effect of addition can be confirmed from the discussion of Figs. 7 and 8.

The formulation of the second-stage cross-linking treatment after the first-stage cross-linking treatment is as shown in Table 1.

A glove composed of a thin film of an elastomer formed through a step comprising the following steps.

A glove composed of an elastomer formed of an elastomer having 25 to 30% by weight of acrylonitrile, 62 to 71% by weight of butadiene, and 4 to 8% by weight of unsaturated carboxylic acid (total 100 weight%) %), and is crosslinked by a bond formed by a substituent of at least a part of the aforementioned unsaturated carboxylic acid, and the remaining substituent of at least a part of the substituent of the unsaturated carboxylic acid is a divalent metal Crosslinked, the glove containing no sulfur as a crosslinking agent and a sulfur compound as a vulcanization accelerator, and an elastomer crosslinked by a bond formed by a substituent of at least a part of the aforementioned unsaturated carboxylic acid Muni's viscosity (ML ₍₁₊₄₎ (100 °C)) is 100 to 220. Regarding the characteristics of the glove, the thinner film of the elastomer is free of sulfur as a crosslinking agent and as a vulcanization accelerator. A sulfur compound having a thickness of 0.05 to 0.15 mm, a glove swelling ratio of 240 to 320 when the glove is formed, a tensile stress of 22 to 35 MPa, an elongation at break of 480 to 620%, and a tensile stress at an elongation of 500%. 15 to 35 MPa, characterized by being formed via a step comprising the following steps (a) a step of washing a mold or a mold with a washing liquid and drying, (b) a step of immersing a mold or a molding die in a coagulant solution, and (c) a mold to which a coagulant is attached or a step of drying the molding die, (d) immersing the mold or the molding die to which the coagulant is attached and dried, at a temperature of 30 ° C, in an elastomer composition as in claim 4 or 5 a step of up to 20 seconds, (e) a step of drying the mold or molding die obtained in the aforementioned step (d) at 80 to 120 ° C, (f) molding or molding obtained in the aforementioned step (e) On the surface of the mold, an unsaturated carboxylic acid is added to the elastomer crosslinked composition of the acrylonitrile butadiene elastomer as disclosed in claim 4 of the patent application.

In the present invention, a glove composed of a thin film of an elastomer is formed through the following steps.

(a) Washing the mold or molding die with a cleaning solution to remove dirt, and washing and drying with cold water

(b) a step of immersing a mold or a molding die in a coagulant solution containing 8 to 17% by weight of Ca ²⁺ ions

The coagulant is prepared by adding calcium nitrate to water to contain an aqueous solution of 8 to 17% by weight of calcium, preferably 8.0 to 17.0% by weight of Ca ²⁺ ions. A mold or a molding die is immersed in the aqueous solution. As a result, the coagulant is attached to the surface of the mold or molding die. The time can be decided appropriately. Usually 10 to 20 seconds. Wetting agents and anti-adhesives can also be added. Specifically, it is zinc stearate and calcium stearate.

(c) a step of drying a mold or a mold to which a coagulant is attached at 50 to 70 ° C to dry all or a part of the surface

The mold or mold to which the coagulant is attached is dried at 50 to 70 ° C to dry the surface or a portion.

(d) immersing the mold or mold having the coagulant obtained in the above step (c) at a temperature of 30 ° C for 1 to 20 seconds in the composition for producing the elastomer of the present invention. step

The composition for producing the elastomer is attached by immersing the mold or the molding die to which the coagulant is attached at a temperature of 25 to 35 ° C for 1 to 20 seconds in the composition for producing the elastomer. The impregnation step is carried out several times. Usually, it is performed twice or more times.

(e) a step of washing the mold or molding die obtained in the aforementioned step (d) to remove the agent (dipping)

A partially formed mold is formed by partially drying the latex, and leaching is performed in a immersion tank in hot water (30 to 70 ° C) for 90 to 140 seconds.

(f) a step of subjecting the molding or molding die obtained in the above step (e) to a round edge (curl processing)

After the leaching step is completed, the round edge (curl edge processing) is performed.

(g) a step of drying the mold or molding die obtained in the above step (f) in a furnace

The glove molding die is dried at 80 to 120 ° C for 250 to 300 seconds.

(h) a step of crosslinking the molding or molding die obtained in the above step (g)

The glove molding mold in which the dried latex is formed into a coating film is crosslinked at 120 to 150 ° C for 20 to 30 minutes.

(i) a step of drying after the cross-linked elastomer on the surface of the mold or the mold obtained in the above step (h) is subjected to post-leaching (washing to remove the contained agent)

The post leaching system is carried out at 30 to 80 ° C for 60 seconds to 80 seconds.

Through the above series of steps, a glove composed of a thin film of elastomer can be produced.

The following steps can also be added.

(j) after the leaching of the step (i), the surface of the film of the elastomer subjected to the drying step is subjected to chlorine treatment to remove the viscous (adhesiveness) of the surface of the elastomer film, followed by neutralization treatment and washing with water. step

The chlorine treatment is a method of forming a crosslinked elastomer film in a dry state on a mold or a molding die, and immersing it in a chlorine solution in a treatment tank. As a result, the formation of the elastomer can be reacted on the surface of the film in the form of a glove, so that the thickness of the surface is only slightly reduced.

(k) A film of the elastomer obtained by subjecting the surface obtained in the above step (j) to a chlorine-treated mold or a molding die to water washing and drying. The surface viscous (adhesion) is removed at this stage.

(l) a step of peeling and turning the film of the elastomer after the chlorine treatment on the mold or the molding die

The main steps in the foregoing steps are as follows.

(a) a step of immersing a mold or a molding die in a coagulant solution containing 8 to 17% by weight of Ca ²⁺ ions, and (b) a molding or molding die to which a coagulant is attached at 50 to 70 ° C a step of drying to dry all or a part of the surface, (c) immersing the mold or mold having the coagulant obtained in the above step (b) at a temperature of 30 ° C for immersing the invention a step of 1 to 20 seconds in the composition of the elastomer, (d) a step of drying the mold or molding die obtained in the above step (c) at 80 to 120 ° C, (e) the aforementioned (d) The molded body obtained in the step or the elastomer on the surface of the molding die is treated at 120 to 150 ° C for 20 to 30 minutes to form a step of crosslinking and hardening.

The properties of the glove obtained in the present invention are as follows.

The gloves of the present application, which do not contain sulfur and sulfur-containing cross-linking materials and sulfur-containing vulcanization accelerators, are as shown in the examples.

The composition of the test piece of the rubber glove was analyzed (11 components: C, H, N, O, S, Zn, Ca, Cl, Na, K, and Ti). As a result of quantitative analysis using an ICP luminescence analyzer, sulfur was detected to be 0.31% by weight. The sulfur can be considered to be a sulfonic acid group derived from an anionic surfactant used as a dispersing agent. The overall results are shown in the fifth table of the fourth embodiment and the sixth table of the fifth embodiment.

Regarding the characteristics of the present invention, the relationship between the Mooney viscosity, the glove swelling ratio, Zn, the elongation at break, and the tensile stress at an elongation of 500% is shown in Table 2.

Compared with other gloves, it is shown in Table 3.

In Example 7, the skin sensitivity test results (Table 12) were shown. In the product of the present invention, it was found that there was no symptom of the type IV allergy, and there was no problem of health damage.

Compared with the previous products, it has the result of low Zn, Ca, Na, and K.

The measurement result of the thickness of the glove of the thin film of the elastic body of the present invention varies depending on the site, but is 0.05 to 0.15 m. The tensile stress (strength) of the glove of the thinner film of the elastomer of the present invention is 22 to 35 MPa, and the elongation at break is 480 to 620%.

The glove of the thinner film of the elastomer of the present invention has a modulus coefficient of 500% between 10 and 15 MPa. These are shown in Example 6. The results are shown in Table 7. This information is in no way inferior to previous products using sulfur and sulfur-containing materials (Table 8).

[Example 1]

Further, methacrylic acid was added to the above-mentioned acrylonitrile butadiene in which methacrylic acid was initially added or not, and methacrylic acid was added to acrylonitrile butadiene (Synthomer Co., Ltd. product name Synthomer 746- SXL) is a composition which is mixed with potassium hydroxide, zinc oxide, titanium oxide, a dispersant, an antioxidant, a colorant, and water to form a concentration shown in Table 2.

This composition was used to produce a thin film of an elastomer which does not contain sulfur as a crosslinking agent and a vulcanization accelerator.

[Embodiment 2]

Using the composition consisting of the mixture obtained according to the fourth table, a glove composed of a thin film of an elastomer was produced by the immersion method shown below.

(a) Washing the mold or molding die with a cleaning solution to remove dirt, and washing and drying with cold water

This step is carried out on the dried mold or molding die by any of the direct immersion method or the coagulant immersion method. The distinction between these uses is determined by the product. The direct immersion method directly soaks the dried mold or molding die of the article in the mixture prepared by the formulation of the present invention.

(b) a step of immersing a mold or a molding die in a coagulant solution containing 8 to 17% by weight of Ca ²⁺ ions

The coagulant is prepared by adding calcium nitrate to water to contain an aqueous solution of 10% by weight of Ca ²⁺ ions. A mold or a molding die is immersed in the aqueous solution. As a result, the coagulant is attached to the surface of the mold or molding die. The time is 10 to 20 seconds. Wetting agents and anti-adhesives can also be added. Specifically, it is zinc stearate and calcium stearate.

(c) a step of drying a mold or a mold to which a coagulant is attached at 60 ° C to dry the surface or a portion

(d) immersing the dry mold or molding die to which the coagulant is attached, obtained in the above step (c), at a temperature of 30 ° C for 1 to 20 seconds in the composition for producing the elastomer of the present invention Step

The composition for producing the elastomer was attached by immersing a mold or a molding die to which the coagulant adhered at a temperature of 30 ° C for 15 seconds in the composition for producing the elastomer. The impregnation step is carried out several times. Usually, it is performed twice or more times.

(e) a step of treating the mold or molding die obtained in the above step (d) with water and separating the medicament (dipping)

A partially formed latex is formed into a coating film of a coating film, and leached in a immersion tank for 90 to 140 seconds in hot water (30 to 70 ° C).

(f) a step of subjecting the mold or the mold obtained in the above step (e) to a round edge (curl edge processing)

After the leaching step is completed, the round edge (curl edge processing) is performed.

(g) a step of drying the mold or molding die obtained in the above step (f)

The glove molding die is dried at 80 to 120 ° C for 250 to 300 seconds.

(h) a step of crosslinking the molding or molding die obtained in the above step (g)

The glove molding mold in which the dried latex is formed with the coating film is subjected to crosslinking at 120 to 150 ° C for 20 to 30 minutes.

(i) drying the surface of the film of the elastomer after cross-linking on the surface of the mold or the molding die obtained in the above step (h), followed by leaching (washing to remove the contained agent), followed by drying Step

The post leaching system is carried out at 30 to 80 ° C for 60 seconds to 80 seconds. It is divided into 2 times.

(j) Chlorination of the glove surface as a desired step.

Through the series of steps described above, a glove composed of a thin film of elastomer can be produced.

[Example 3]

Also shown together with the comparative example.

A mixture of methacrylic acid added to acrylonitrile butadiene with or without methacrylic acid added to acrylonitrile butadiene (Synthomer's product name Synthomer) SCL-XNBR746SXL), according to the formula of the second table to manufacture gloves.

In the comparative example, a glove containing ZnO (1.5% by weight) and sulfur (1.0% by weight) in a carboxylated acrylonitrile butadiene latex (product name, Synthomer 6322 manufactured by Synthomer Co., Ltd.) generally used was used to manufacture gloves, and compared. Both gloves. The zinc oxide, the dispersant, the pH adjuster, the antioxidant, and the contents thereof are the same as those shown in the examples. Solid phase weight It is 30% by weight. A gloved article (product name VERTE 710N) was produced from the above composition in accordance with the procedure shown in Example 2.

[Example 4]

The fifth table shows the result of the comparison of the component analysis of the article of the present invention and the article of the comparative example (VERTE 710N).

Component analysis of test pieces of rubber gloves using CHNO analyzer (EA1110 from CE Instruments) and ICP-AES system (11 components: C, H, N, O, S, Zn, Ca, Cl, Na, K and Ti).

The quantitative method of elemental sulfur is as follows.

Quantitative analysis of Zn and Ca, after weighing about 0.1 g of each evaporation residue sample, placed in a platinum crucible to mix the flux (Na ₂ CO ₃ :Na ₂ B ₄ O ₇ =2:1) 2 g The mixture was melted, extracted with 30 ml of hydrochloric acid (HCl: H ₂ O = 1:1), diluted to 100 ml, and quantitatively analyzed using an absorption analyzer. C1, after weighing about 1 g of each evaporation residue sample, placed in a platinum crucible, melted with an Eschka mixture, and then subjected to an aqueous solution extracted with 100 ml of pure water using an absorption analyzer. Quantitative analysis. On the other hand, the same aqueous solution was quantitatively analyzed by sulfur using an ICP emission spectrometer.

Sulfur content

According to the invention, the sulfur content is 0.31% by weight.

In VERTE 710N, it was 1.10% by weight.

Zinc content

According to the invention, the zinc content is 0.76% by weight of a small amount. In the previous product, it was 1.15 wt%. In the product of the invention, the content of zinc is earlier than that of the prior art Less products.

[Example 5]

Comparison of acetone soluble components

The amount of light components (unreacted rate, unsulfurized NBR) in rubber glove products: Soxhlet extraction was performed in acetone solvent for 24 hours according to the quantitative method of JIS K 6299 rubber solvent extract. . Qualitative analysis of the acetone extract was carried out using an infrared absorption (FT-IR) spectroscopic analyzer.

For the measurement device of the FT-IR, the IRP Prestage-21/FTIR-8400S model manufactured by Shimadzu Corporation was used. The measurement method was a penetration method (using a diamond unit), and the number of integrations was 40 times.

The swelling test of the sample obtained from the rubber glove was immersed in a toluene solvent, and the weight increase of the rubber sample after 72 hours at normal temperature was measured (generally as a method for easily evaluating the state of vulcanization, when immersed in sulfurization) In the good solvent of rubber, the cross-linked polymer such as sulfurized rubber is inhibited by the elastic force of the mesh to achieve the swelling balance, so that the sulfurized density of the vulcanized rubber is good. The equilibrium swelling ratio in the solvent has an inverse relationship. The weight swelling ratio of each sample (the weight of the sample after swelling × 100 / the weight of the sample before swelling, unit: %) is calculated as a sulfurized rubber. Crosslink density.

The acetone-soluble component of the present invention was 11.3% by weight, 12.0% by weight, and 10.5 to 15% by weight, and the acetone-soluble component of VERTE 710N of the prior product was 7.7% by weight. The weight swelling ratio of the present invention was 340%, and the weight swelling ratio of the prior product VERTE 710N (KLT-C) was 377% (Table 6).

As a result of infrared analysis of the acetone-soluble component, unreacted nitrile butadiene was observed. In the present invention, the absorption peak of the carboxylic acid group is present in the vicinity of 1700 cm ^-1 .

The fourth table together describes the metal element analysis values of the surface and the inner surface of the ring finger of the glove.

[Embodiment 6]

A latex glove of the present invention further comprising adding methacrylic acid to a mixture of acrylonitrile butadiene initially added or not added with methacrylic acid to add methacrylic acid to acrylonitrile butadiene, and The product was subjected to a tensile test and measured by a test method of ASTM-6319-00 using a carboxylated nitrile latex of a glove manufactured by a conventional crosslinking method using sulfur and a promoter.

Hardened at 150 ° C, respectively. Next, the glove to be a sample was aged under the conditions of a humidity of 50% and a temperature of 23 ° C for 24 hours. The glove was aged at 70 ° C for 7 days.

Regarding the glove of the present invention, the seventh table shows the results of physical tests of the cured glove and the aged glove. Also for the gloves of the previous products, they were hardened at 150 ° C, respectively. Next, the glove to be a sample was aged under the conditions of a humidity of 50% and a temperature of 23 ° C for 24 hours. Regarding the glove, it was aged for 7 days under the condition of 70 ° C, and the eighth table showed the result of the physical test of the glove.

The tension of the glove produced by the present invention is comparable to the strain of the prior art using a cross-linking method of ZnO (1.5% by weight) and sulfur (1.0% by weight). The elongation of the glove produced by the present invention is higher than that of the glove of the prior art.

In general, the gloves produced by the present invention have good properties after aging as compared with the gloves produced by the prior methods.

Next, the composition of the latex will be explained again.

A latex composition in which a methacrylic acid is further added to the above-mentioned acrylonitrile butadiene in which methacrylic acid is initially added or methacrylic acid is added to acrylonitrile butadiene, and the pH is adjusted to 9 to 10, and adjusted by water so that the content of the solid phase becomes 18% by weight to 30% by weight.

The glove produced by using the formulation of the composition of the first table and following the above steps is considered to be good in the following respects.

Advantage 1: The point of defense against type I allergies

The product manufactured according to the present invention is not used because it causes latex The point of natural rubber caused by the presence of protein in type I allergy.

Advantage 2: The point of prevention of type IV allergies caused by late delay

Type IV allergy is caused by the use of a sulfur-promoting agent containing thiocyanate, dithiocarbamate and mercaptobenzotriazole in the manufacture of gloves. In the present invention, a vulcanization accelerator which causes type IV allergy caused by lateness after use is not used.

Advantage 3: Good physical and chemical properties

A system of latex having good film properties is supplied in accordance with the formulation of the latex of Table 1. This results in an extremely thin film and excellent barrier properties. The dimensions of the gloves are as follows. It was found that the manufactured gloves were thinner than the previous gloves (Table 9).

The physical characteristics are shown in Table 10 below. The tension and elongation at break of the glove of the present invention are the same as or higher than the tension and elongation of the prior glove.

[Embodiment 7]

In Example 1, sulfur and an accelerator were not used as the crosslinking agent, but the evaluation of the potential ability of the article of the present invention to cause immunoreactivity to delayed type IV allergy upon contact with the skin was carried out. Epidermal sensitivity test. Delayed type IV allergies are mainly caused by chemicals such as accelerators used in previous cross-linking methods. The method used in this test is based on 50, 56 and 312 of Chapter 21 of the US Federal Regulations (CFR).

The purpose of this test is to repeat the test and determine the change and/or sensitivity to the glove from the state of the patch test caused by the human skin. This is based on the results of a total of 220 people based on 35 males and 185 females.

The test was carried out in two stages. In the test stage at the time of introduction, a glove film having a length of one side of approximately four inches was placed on the surface of a sealing medical tape manufactured by 3M Company. Place the patch on the back between the shoulder and the waist. The trial was conducted on 9 Mondays, Wednesdays and Fridays. Test. After the test, the patch was removed after 24 hours. A 24-hour break is available on Tuesdays and Thursdays, and a 48-hour break after Saturdays. Before the next patch test, the trained and testee will record the equipment and the items returned to the site.

At the end of the test at the time of import, the items used in the test are removed and the test is not carried out within 2 weeks thereafter. The re-challenge test was conducted after the break. Re-challenge the test system on the new test site. After the removal test, the parts were recorded separately after 24 hours and 72 hours after application. In the phase of the end of the final reading of the re-challenge test, for all the late on the skin, it is indicated that all items are reported.

The state of the skin is recorded according to the following recording criteria (Table 11).

Table 12 is a summary of the results of the trials derived from subjects of 220 people.

In any project, it does not mean getting sick. Regarding several projects (a total of six), it does not last until the end of the trial. According to the glove manufactured in the first embodiment, there is no evidence showing a medically problematic skin disease or an allergic disease caused by contact with a human. These are the results consistent with the FDA's considerations for the display of mild skin disorders.

[Embodiment 8]

Implementation of the skin sensitivity test (Maximization test)

The test is based on the basic considerations of the biosafety test required for the manufacture of medical devices (input) (February 13, 2015, Pharmaceutical Review No. 0213001) and "Basic with Biosafety Tests" "Reference-related reference materials" (March 19, 2015, Medical Equipment Review, Medical Equipment Review No. 36) was conducted by the Japan Food and Drug Safety Center (Qinye City, Kanagawa Prefecture, Japan).

Test substance

VERTE CheMax 7th Sense as a test substance (abbreviation: 7th Sense, material: nitrile rubber, lot number: PB30061114103022), blue The color of the glove is provided by Midori Security Co., Ltd., and is kept away from direct sunlight or high temperature before use.

2. Compare control substances

VERTE 710N (abbreviation: 710N, material: nitrile rubber, lot number: 0104170) as a comparative control substance, in the shape of a blue glove, provided by Midori Security Co., Ltd., avoiding direct sunlight or high temperature before use, at 10 Store indoors at °C to 40 °C.

3. Content of the experiment

The VERTE CheMax 7th Sense methanol extract was used to evaluate the biosafety of the gloves of the present invention, and the VERTE CheMax 7th Sense methanol extract was used to perform the skin of the woodchuck for the purpose of comparison with VERTE 710N. Sensitivity test.

For the preparation of the drug sample, the methanol extract of VERTE CheMax 7th Sense (described below as 7th Sense-M) or the methanol extract of VERTE 710N (described below as 710N-M) is used in relation to the extraction used in the extraction. The extract obtained in the test substance 1 g was a ratio of 1 mL and suspended in ethanol to form a 100 v/v% 7th Sense-M ethanol suspension or a 100 v/v% 710 N-M ethanol suspension. Further, a negative control (BLANK) obtained only from methanol was dissolved in a liquid equivalent to the amount of ethanol suspended in 7th Sense-M or 710N-M to form a BLANK ethanol equivalent to 100 v/v%. The solution formed a negative control. In a sensitive test, replace 10v/v% 7th Sense-M ethanol suspension or 10v/v% 710N-M ethanol suspension with equal amount of olive oil to prepare 10v/v% 7th Sense-M olive oil suspension. Or 10v/v% Use 710N-M olive oil suspension. In a secondary sensitivity test, 100v/v% 7th Sense-M ethanol suspension or 100v/v% 710N-M ethanol suspension was substituted for the same amount of olive oil to prepare 100v/v% 7th Sense-M olive oil suspension. Use liquid or 100v/v% 710N-M olive oil suspension. In the induction test, a 100 v/v% 7th Sense-M ethanol suspension or a 100 v/v% 710 N-M ethanol suspension was diluted with ethanol to prepare a stage. Further, a BLANK ethanol solution equivalent to 100 v/v% was used as it was.

In a sensitive test (treatment day 1), 10v/v% 7th Sense-M olive oil suspension or 10v/v% 710N-M olive oil suspension and Freund's complete adjuvant were administered to the soil. The inner part of the scapula of the rat's shoulder. On the 7th day of treatment, 10 w/w% sodium lauryl sulfate was applied in advance to the area containing the intradermal administration site, and the next day (disposal day 8), 100 v/v% 7th Sense-M olive The oil suspension or 100v/v% 710N-M olive oil suspension was affixed to the same site for 48 hours as a secondary sensitivity test. In the induction test (disposal day 22), 100, 20, 4, 0.8, 0.16 v/v% ethanol suspension of 7th Sense-M or 710N-M and a 100 v/v% equivalent of BLANK ethanol solution were attached closed. 24 hours.

Experimental conclusion

The judgement was carried out 24 hours and 48 hours after the attachment was removed according to the criteria of the Draize method. As a result, a positive reaction (erythema) was observed in 100 and 20 v/v% of the 7th Sense-M administration group and 100, 20, 4 and 0.8 v/v% concentrations of the 710N-M administration group.

From the above results, it was found that 7th Sense-M and 710N-M showed a positive reaction, so under the test conditions, VERTE CheMax 7th Sense and VERTE 710N showed skin sensitivity to groundhog, the lowest induced concentration, VERTE CheMax 7th Sense was 20v/v%, and VERTE 710N was 0.8v/v%.

In the glove of the present invention, VERTE CheMax 7th Sense, when it is a high concentration of 20 v/v%, causes a positive reaction, and VERTE 710N has a result of 0.8 v/v%. Information on biosafety assessments and the use of VERTE CheMax 7th Sense methanol extracts for the purpose of comparison with VERTE 710N were performed on the woodchuck's Maximization test.

The results are shown in the table.

Individual weight result

Group result

Results after removal of the attachment

Separation of solids after removal of the attachment

Evaluation of solids after removal of attachments (2)

Evaluation of solids after removal of attachments (3)

[Embodiment 9]

Using the viscoelastic property measurement test apparatus, the storage modulus of the dynamic viscoelastic property, E?, loss modulus, was measured in a tensile mode by the sample of the glove of the present invention and the sample of VERTE 710 of the prior product. E" and the loss tangent tan δ, the results are shown in Table 11. From the results, the main curve of the dynamic viscoelasticity was obtained and displayed (Fig. 5, Fig. 6).

The present invention achieves good results in comparison with prior art data.

Using the viscoelastic property measurement test apparatus, the storage modulus of the dynamic viscoelastic property is stored in the tensile mode by the sample of the glove of the present invention and the sample of the prior product of VERTE 710, and the loss modulus is measured. E", and the loss tangent tan δ, and the main curve of the dynamic viscoelasticity is obtained from the result to be displayed (Fig. 5). The result of the sample of the glove of the present invention is shown. Fig. 6 shows the previous product. The result of VERTE 710. In the present invention, the storage modulus as the dynamic viscoelastic property, the storage modulus E', the loss modulus E", and the loss tangent tan δ were measured in a tensile mode.

[Embodiment 10]

Analysis results of raw material emulsion

For the analysis results of the raw material emulsion of the 746SXL of the present invention, the 6322 of the prior product, and the Nipol 550 of the prior product, the mixture was heated and dried under reduced pressure at 80 ° C for 8 hours, and the dendritic residue was weighed out and the solid content of the latex was calculated. .

(1) The NBR rubber solid content in each latex sample when moisture was removed under reduced pressure at 80 ° C was about 45 to 46%.

(2) The elemental analysis values (C, H) of the solid content in each latex sample were almost the same (C78 to 79%, H9.8 to 10.0% by weight). The nitrogen content of Nipol 550 (from acrylonitrile) is about 3% lower than that of other samples on the basis of acrylonitrile. Both are located in the range of nitriles (25 to 30% of AN). The other side The amount of S from the surfactant is from 0.3 to 0.5% by weight.

(3) The amount of volatile unreacted MMA monomer of 6322 was 13 ppm (the upper graph of Figure 3 is a graph showing the amount of volatile unreacted MMA monomer of the previous product).

The amount of volatile unreacted MMA monomer of the 746SXL of the present invention is 370 ppm (the lower graph of Figure 3 is a graph showing the amount of volatile unreacted MMA monomer of the present invention).

[Example 11]

Mui's viscosity measurement

Adding further methacrylic acid to the aforementioned acrylonitrile butadiene with or without methacrylic acid added to add methacrylic acid to acrylonitrile butadiene and ending the first stage of the emulsion's Mooney viscosity (ML) ₍₁₊₄₎ (100 ° C)), from 100 to 220.

The measurement of the Mooney viscosity is specified in JIS K 6300 and ASTM D1646.

In order to determine the viscosity of the unsulfurized rubber measured by the Munni plasticizer (viscometer), the scale of the instrument is printed in the unit of Muney and directly shows the viscosity of the Mooney. In general, a large rotor was used at 100 ° C, and after the rotor was started to warm up for 1 minute, the value of 4 minutes was read and expressed as ML ₍₁₊₄₎ (100 ° C).

(a) In the measurement of the Mooney viscosity, methacrylic acid was added to acrylonitrile butadiene with respect to 200 ml of a mixed saturated aqueous solution of calcium nitrate and calcium carbonate. The unsaturated carboxylic acid (or methacrylic acid) is reacted with the butadiene portion of acrylonitrile butadiene with other butadiene portions of acrylonitrile butadiene. Adding an unsaturated carboxylic acid (or methacrylic acid) to the butadiene portion in a state with a large number of branches a state in which the fraction of the unsaturated carboxylic acid (or methacrylic acid) is added in the form of graft polymerization, which is dropped by a pipette and stirred for 10 minutes (23 ° C, stirring speed) At 900 rpm), precipitation of the solid rubber was confirmed after the dropwise addition.

The obtained solid rubber was taken out, washed with about 1000 ml of ion-exchanged water (temperature: 23 ° C, stirring speed: 500 rpm), and this operation was repeated 10 times.

The washed solid rubber was dried and dehydrated, and then vacuum dried at 60 ° C for 72 hours.

In this state, the glove molding mold described later is immersed in a coagulant, coated and dried or partially dried at a temperature ranging from 50 to 70 ° C, and immersed in the latex mixed by the formulation of the present invention. The glove molding die is immersed in a glove molding die and dried in a state of being immersed for a specific period of time, and is used for measuring the Mooney viscosity in a state in which it is not crosslinked.

The thickness of the glove molding die is not made too thick. The immersion time of the glove forming mold in the latex is determined by the total solid phase material (TSC) content of the blended latex and the desired coating thickness. This time is from 1 to 20 seconds, preferably from 12 to 17 seconds.

This is a polymer composed of a mixture of methacrylic acid and acrylonitrile butadiene added by further adding methacrylic acid to acrylonitrile butadiene with or without methacrylic acid under the above conditions. And the viscosity of the Muss measured without cross-linking.

(b) According to JIS K6300-1:2001 (un-vulcanized rubber - physical properties - Part 1: Viscosity and scorch time measured according to the Muny viscometer) Method) The dried solid rubber fraction recovered from each latex was passed through an 8-inch roll having a roll gap of 1.00 mm 10 times and then provided for the test.

(c) The 746SXL of the present invention has a Mooney viscosity (ML ₍₁₊₄₎ (100 ° C)) of 151, and the previous product of 6322 has a Mooney viscosity of 122. In the previous measurements, they were 180 and 128, respectively.

In general, NBR (acrylonitrile butadiene) latex is a high molecular polymer obtained by copolymerizing a part of an unsaturated carboxylic acid such as methacrylic acid.

The degree of polymerization can be determined by various methods, and the Mooney viscosity is an effective index when it is insoluble in an organic solvent. The NBR (acrylonitrile butadiene) latex used in the present invention can form a covalent bond with two double bonds of butadiene by sulfur, so that NBR (acrylonitrile butadiene) latex is highly advanced. Crosslinked rubber elastomer. Further, since zinc is used as a divalent metal ion to form a crosslink of two unsaturated carboxylic acids, the crosslinked structure is made stronger. In the present invention, since the crosslinked structure formed of sulfur is not provided, the molecular weight (degree of polymerization) of the NBR latex is increased, and the strength of the rubber elastic body is assisted by the intertwining or mutual intrusion of the NBR latex. Therefore, the NBR latex of the present invention is from 100 to 220 with respect to the previous NBR latex having a Mui viscosity of about 30 to 80, which is more polymer (high degree of polymerization) than the prior art.

Therefore, if the more polymer NBR latex is intertwined or invaded each other, it is extremely advantageous for the improvement of strength. Further, if a part of the copolymerized unsaturated carboxylic acid is crosslinked by zinc of a divalent metal ion between the entangled or mutually invaded NBR latex, the strength is stronger.

In NBR latex with a viscosity of less than 100, the molecular chain is small, Therefore, the effect of the entanglement or mutual intrusion is small. In addition, when the Mooney viscosity is above 220, the NBR latex itself will be intertwined, and the interlacing with other NBR latex becomes smaller, so that the mutual intrusion of the NBR latexes becomes smaller. Further, the crosslinking formed by zinc increases the probability of being caused in the unsaturated carboxylic acid in the same NBR latex polymer, and the phenomenon of crosslinking the plurality of NBR latexes by zinc becomes extremely small, thereby lowering the strength. Easy to break.

In various experiments by the inventors, the optimum value is in the range of 100 to 220.

[Embodiment 12]

Latex particle size distribution assay

Each emulsion liquid was diluted to about 0.002% with ion-exchanged water, and ultrasonic dispersion was performed for about 1 minute, and then the particle size distribution measurement was performed by the following submicron particle diameter measuring apparatus.

(particle size measurement conditions)

Measuring equipment: COULTER N4 PLUS

Liquid viscosity: 0.9333cp

Temperature: 23 ° C

Automatic SDP: 10nm to 1000m

Angle selection: 90°

The latex particle size of the 746SXL of the present invention measured last time, the average particle diameter = 168 nm, and the standard deviation was 28.9 nm (Fig. 4).

The latex particle size of the 746SXL of the present invention measured this time, the average particle diameter = 170 nm, and the standard deviation was 16 nm.

The latex particle size of the previous product of 6322, the balance of 6322 The average particle diameter = 178 nm, and the standard deviation was 30.0 nm (Fig. 4, lower panel). The latex particle size of the 6322 of the previous product measured this time, the average particle diameter = 184 nm, and the standard deviation was 53 nm.

The particle size distribution of Nipol 550 of the previous product measured this time was 141 nm and the standard deviation was 24 nm.

[Example 13]

Evaluation of reactivity of latex raw materials

(a) Test method for ZnO addition system

The zinc oxide (ZnO) slurry was added to the solid content of each latex in an amount of 1.2 parts by weight based on the oxidized solid content, and then stirred in a sealed container at room temperature for 24 hours, and then transferred to a glass having a flat bottom surface. The container (liquid surface height: 2 mm) was dried at 40 ° C to form a film, and then heat-treated at a predetermined temperature (150 ° C) for 1 hour.

(b) Test method for ZnO unadded lines

Each latex was directly transferred to a glass container having a flat bottom surface (liquid surface height: 2 mm), dried at 40 ° C, and then heat-treated at a predetermined temperature (150 ° C) for 1 hour.

(c) Quantification method of carboxylic acid

The emulsion solid content (resin film) after drying at each temperature was measured by infrared spectroscopy to determine the absorption peak intensity ratio of the carboxylic acid group derived from MMA and the acrylonitrile group (the peak intensity of the COOH group of 1699 cm ^-1 / The peak intensity of the CN group of 2235 cm ^-1 ), using a calibration curve (a calibration curve made of a resin film obtained by adding polyacrylic acid (PAA) of 1 to 3 wt% on a solid basis to 746SXL latex) To calculate the PAA conversion value of the amount of unreacted carboxylic acid in the solid portion.

(d) Analysis of light components (unreacted NBR)

Amount of light components (unreacted, unsulfurized NBR) in the latex raw material film: Soxhlet extraction (Soxhlet Extraction) in acetone solvent for 24 hours according to JIS K 6229 (quantification method of rubber-solvent extract) ) and seek.

(e) Method for measuring weight swelling ratio

The swelling test of the latex raw material film is performed by immersing the film in a toluene solvent, and measuring the weight increase after 27 hours at normal temperature (generally as a method for easily evaluating the vulcanization state of the vulcanized rubber, when the vulcanized rubber is to be used) When immersed in a good solvent, the good solvent is intended to dissolve and diffuse the polymer chain. However, in a crosslinked polymer such as a sulfurized rubber, it is suppressed by the elastic force of the mesh to achieve a swelling balance, and the sulfur density is good. The equilibrium swelling ratio in the solvent has an inverse relationship. The weight swelling ratio of each latex raw material film data is calculated and set as the standard for the crosslinking state of the vulcanized rubber.

In the crosslinked polymer of the product of the present invention, the swelling is inhibited by the elastic force of the mesh to achieve a swelling balance, so the crosslink density is inversely proportional to the equilibrium swelling ratio in the good solvent.

The 19th table shows the results of the above analysis of the dried product at 40 ° C, and the 20th table shows the results of the above analysis of the heat-treated product at 150 ° C for 1 hour.

The 746SXL of the present invention and the 6322 of the prior art substantially did not observe a decrease in the amount of the carboxylic acid group by heat drying in the absence of ZnO. In Nipol 550, a decrease in the amount of carboxylic acid groups of about 1 to 20% was observed.

Next, when ZnO was added to both of 746SXL of the present invention and 6322 of the prior art, a case where the amount of the carboxylic acid was significantly reduced by heat treatment at 150 ° C was observed, and the tendency to decrease (increased reaction rate) was in 746 SXL. More significant. It is judged to be formed by the promotion of cross-linking.

746SXL acetone soluble component (unreacted NBR rubber) in ZnO In the unadded system, the measurement results of the two batches were 33.7 wt% and 27.4 wt%, and in the batch 1, the heat treatment at 150 ° C for one hour was reduced to 26.9%. On the other hand, in the ZnO addition system, the heat treatment at 150 ° C for 1 hour was remarkably reduced from 32.4% to 14.2%, and the crosslinking effect by zinc was observed.

The weight swelling ratio of the 40°C dried product of 746SXL in which ZnO was not added was 287% and 336% in the measurement of the two batches, and the crosslinking density was relatively high. The ZnO additives are also almost identical.

The amount of acetone soluble component and weight swelling ratio of 6322 is the same as that of 746SXL.

On the other hand, in the case of Nipol 550, unlike the above-mentioned sample, the weight swelling ratio in the 40 ° C dried product was 501% in the ZnO unadded system, and the added value was 529%, and the temperature was 150 ° C. In the 1 hour treatment, the addition of ZnO will increase. This shows that the crosslinking treatment is not carried out in Nipol 550, and a film having a high crosslinking density cannot be obtained. Even if ZnO is added, the crosslinking density cannot be increased. This can be considered as the MISS viscosity of 746SXL (ML ₍₁₊₄₎ (100 °C)) is larger 151 and 180 in the two batches of measurement, compared to the smaller 94 in Nipol 550. Therefore, in Nipol 550, the effect of entanglement or mutual intrusion becomes small due to the small molecular chain.

[Embodiment 14]

The electrical properties of the gloves of the present invention were determined.

(a) Surface resistivity

The measurement method is as follows. The measuring device is shown in Fig. 12.

According to IEC specification 61340-2-1 A.5.4

Measurement environment: 20 ° C, 40% RH

Test equipment: Surface resistance meter MODEL 152 (manufactured by TREK)

Applied voltage: 100V

The measurement result was 2.65 × 10 ¹² Ω/sq.

(b) Resistance value when the glove is worn

The measurement method is as follows. The measuring device is shown in Fig. 13.

According to IEC specification 61340-2-1 A.5.4

Measurement environment: 20 ° C, 40% RH

Equipment used: Surface resistance meter MODEL 152 (manufactured by TREK)

Applied voltage: 100V

Specification value: 7.5×10 ⁵ ≦Rg≦1×10 ¹²

The measurement result was 1.22 × 10 ⁸ Ω.

(c) Charge decay measurement

The measurement method is as follows. The measuring device is shown in Fig. 14.

According to IEC specification 61340-2-1 A A2.2

Measurement environment: 20 ° C, 40% RH

Equipment used: charged flat panel monitor MODEL 158 Charge (TREK company)

Specification value: less than 2 seconds

A gloved hand of a subject equipped with a wrist strap was placed on a plate with an electric charge of ±1000 V, and the time during which the plate was attenuated to ±100 V was measured.

The measurement results are as follows. The time required to attenuate from 1000 V to 100 V is 0.48 seconds when the polarity is - and 0.35 seconds when the polarity is +.

As described above, the glove of the present invention exhibits good electrical characteristics.

[Industry use possibility]

According to the present invention, an elastomer which does not cause delayed type IV allergy can be provided. This can be utilized in a variety of products. Further, the crosslinking method shown in the present invention can also be considered.

Fig. 1 is a view showing a state in which the raw material composition of the present invention is crosslinked.

Fig. 2 is a view showing the state in which the crosslinked state of the present invention is formed and the state in which the crosslink is formed.

Figure 3 is a graph showing the amount of volatile unreacted MMA monomer contained in the present invention and prior articles. The lower panel of Figure 3 (in the context of the present invention) shows the amount of volatile unreacted MMA monomer of 746 SXL. The top panel of Figure 3 (in the case of previous articles) shows the amount of volatile unreacted MMA monomer.

The upper graph of Fig. 4 is a measurement result of the particle size of the latex of the 746SXL of the present invention. The lower graph of Fig. 4 shows the measurement results of the latex particle size of the previous product of 6322.

Fig. 5 is a view showing a sample of the glove of the present invention (an emulsified film obtained by forming an emulsified aqueous solution into a cast film and drying under reduced pressure at 40 ° C for 72 hours), as measured by a tensile mode as a dynamic viscoelastic property. In the results of storing the modulus storage elastic modulus E', the loss modulus E", and the loss tangent tan δ, the results of the main curve of the dynamic viscoelasticity are calculated.

Figure 6 shows a sample of VERTE 710 from the previous product (same as Figure 5), measured from the tensile mode as a storage of dynamic viscoelastic properties. In the results of the storage modulus storage elastic modulus E', the loss modulus E", and the loss tangent tan δ, the results of the main curve of the dynamic viscoelasticity are calculated.

Fig. 7 is a graph comparing the loss tangent tan δ for SXL (product of the invention, glass transition temperature -10.1 °C), 6322 (glass transition temperature - 12.2 °C), and Nipol 550.

Fig. 8 is a graph comparing the loss tangent tan δ of the CHM-based raw material emulsion (the raw material emulsion of the present invention) and the product glove.

Figure 9 is a graph comparing the loss tangent tan δ of a sulfur-added sulfur-containing raw material emulsion and a product glove.

Fig. 10 is a graph showing the loss tangent tan δ for a CHM-based raw material emulsion (the raw material emulsion of the present invention) and a sulfur-sulphurized raw material emulsion.

Figure 11 is a graph showing the relationship between the amount of unsulfurized rubber and the weight swelling ratio for glove products.

Fig. 12 is a view showing a measuring device for the surface resistivity of the glove.

Fig. 13 is a view showing a measuring device for the resistance value when the glove is worn.

Fig. 14 is a view showing a measuring device for charge attenuation of a glove.

Since Figures 1, 2, and 12 to 14 of the present case are schematic views; Figures 3 to 11 are experimental data, which are not representative of the case. Therefore, there is no designated representative map in this case.

Claims (16)

An elastomer composition comprising an emulsion comprising 25 to 30% by weight of acrylonitrile, 62 to 71% by weight of butadiene, and 4 to 8% by weight (100% by weight of total) of unsaturated carboxylic acid, and Crosslinking is formed by a bond formed by a substituent of at least a part of the unsaturated carboxylic acid, and the remaining substituent of at least a part of the substituent of the unsaturated carboxylic acid is in a free state, and the crosslinked product is The Mooney viscosity (ML ₍₁₊₄₎ (100 ° C)) is 100 to 220, and the film has a weight swelling ratio of 200 to 400%. The elastomer composition according to claim 1, wherein the acrylonitrile is 25 to 30% by weight, the butadiene is 62 to 71% by weight, and the unsaturated carboxylic acid is 4 to 8% by weight (100% by weight in total). An unsaturated carboxylic acid is added to acrylonitrile butadiene with or without an unsaturated carboxylic acid. The elastomer composition according to claim 1, wherein the terminal group of the unsaturated carboxylic acid used in the bond formed by the substituent of at least a part of the unsaturated carboxylic acid is formed to be selected from a carboxyl group. a reaction product of a hydroxymethyl decylamino group, a reaction product of a carboxyl group and a diamine, a reaction product of a carboxyl group and an alkylenediamine, and a bond of a reaction product of a carboxyl group and an alkyl alcohol, and a terminal group and other The terminal group of the acrylonitrile butadiene elastomer unsaturated carboxylic acid is bonded, and at least the other part remaining is in an unbonded state. An elastomer composition comprising an emulsion comprising 25 to 30% by weight of acrylonitrile, 62 to 71% by weight of butadiene, and 4 to 8% by weight (100% by weight of total) of unsaturated carboxylic acid, and The aforementioned unsaturated carboxylic acid a bond formed by at least a part of the substituent to form a covalent bond, and the remaining substituent of the substituent of at least a part of the unsaturated carboxylic acid forms an ionic bond via the divalent metal ion to form a crosslink, The film of the crosslinked product has a weight swelling ratio of 200 to 400%. The elastomer composition according to claim 4, wherein the divalent metal ion is a divalent metal ion selected from the group consisting of zinc ions, magnesium ions and barium ions or a mixture thereof. The elastomer composition according to claim 4, wherein the divalent metal ion is a zinc ion. The elastomer composition according to claim 4, wherein the elastomer composition of the above-mentioned application scope 4 is 25 to 30% by weight of acrylonitrile, 62 to 71% by weight of butadiene, and unsaturated carboxylic acid. 4 to 8% by weight of the acid (100% by weight in total) is obtained by adding an unsaturated carboxylic acid to acrylonitrile butadiene having or without an unsaturated carboxylic acid. The elastomer composition according to claim 4, wherein the terminal group of the unsaturated carboxylic acid used in the bond formed by the substituent of at least a part of the unsaturated carboxylic acid is formed to be selected from a carboxyl group. a reaction product of a hydroxymethyl decylamino group, a reaction product of a carboxyl group and a diamine, a reaction product of a carboxyl group and an alkylenediamine, and a bond of a reaction product of a carboxyl group and an alkyl alcohol, and a terminal group and other The terminal group of the acrylonitrile butadiene elastomer unsaturated carboxylic acid is bonded, and at least the other part is in an unbonded state. An elastomer composition comprising: 25 to 30% by weight of acrylonitrile, 62 to 71% by weight of butadiene, and 4 to 8% by weight of unsaturated carboxylic acid (100% by weight of total) And forming a crosslink by a bond formed by a substituent of at least a part of the unsaturated carboxylic acid, and the remaining substituent of the substituent having at least a part of the unsaturated carboxylic acid is in a free state emulsion, The crosslinked product has a Mui viscosity (ML ₍₁₊₄₎ (100 ° C)) of 100 to 220, an emulsion elastomer composition having a film weight swelling ratio of 200 to 400%; and a divalent metal oxide; a crosslinking agent of 0.5 to 4.0 phr; a pH adjusting agent for adjusting the pH to 9 to 10, 0.1 to 2.0 phr, a dispersing agent of 0.5 to 2.0 phr, and water, the amount of water being such that the total solid phase produced when mixing The concentration of the substance (TSC) is added in an amount of 18 to 30% by weight; and the emulsion contains 25 to 30% by weight of acrylonitrile, 62 to 71% by weight of butadiene, and 4 to 8% by weight of unsaturated carboxylic acid (all 100% by weight), forming a covalent bond with a bond formed by a substituent of at least a part of the aforementioned unsaturated carboxylic acid, Further, the remaining substituent of the substituent of at least a part of the unsaturated carboxylic acid forms an ionic bond via a divalent metal ion to form a crosslink, and the film has a weight swelling ratio of 200 to 400%. The elastomer composition according to claim 9, wherein the pH adjusting agent is potassium hydroxide. The elastomer composition of claim 9, which contains titanium oxide as a colorant. The elastomer composition according to claim 9, wherein a hindered phenolic polymer is added as an antioxidant. The elastomer composition of claim 9, wherein the aforementioned The dispersant is an anionic surfactant. The elastomer composition of claim 13, wherein the anionic surfactant is sodium alkylbenzene sulfonate. An elastomer-containing glove formed of an elastomer containing 25 to 30% by weight of acrylonitrile, 62 to 71% by weight of butadiene, and 4 to 8% by weight of unsaturated carboxylic acid (100% by weight of the whole) And forming a crosslink by a bond formed by a substituent of at least a part of the aforementioned unsaturated carboxylic acid, and the remaining substituent of the substituent having at least a part of the unsaturated carboxylic acid is a divalent metal In combination, the glove does not contain sulfur as a crosslinking agent and a sulfur compound as a vulcanization accelerator, and a bond formed by a substituent of at least a part of the unsaturated carboxylic acid to form a crosslinked elastomer Negative viscosity (ML ₍₁₊₄₎ (100 °C)) is 100 to 220. Regarding the characteristics of gloves, gloves with thinner elastomer films, no sulfur as a crosslinking agent and sulfur compounds as a vulcanization accelerator. The thickness is 0.05 to 0.15 mm, the glove swelling ratio of the glove is 240 to 320, the tensile stress is 22 to 35 MPa, the elongation at break is 480 to 620%, and the tensile stress at the elongation of 500% is 15 To 35MPa. An elastomer-containing glove formed of an elastomer containing 25 to 30% by weight of acrylonitrile, 62 to 71% by weight of butadiene, and 4 to 8% by weight of unsaturated carboxylic acid (100% by weight of the whole) And crosslinking with a bond formed by at least a part of the substituent of the aforementioned unsaturated carboxylic acid, and the remaining substituent of the substituent having at least a part of the unsaturated carboxylic acid is crosslinked by a divalent metal The glove does not contain sulfur as a crosslinking agent and a sulfur compound as a vulcanization accelerator, and the Mooney viscosity of the elastomer crosslinked by a bond formed by at least a part of the substituent of the unsaturated carboxylic acid (ML ₍₁₊₄₎ (100 °C)) is a glove with a thinner film of the characteristics of the glove, which does not contain sulfur as a crosslinking agent and a sulfur compound as a vulcanization accelerator. 0.05 to 0.15 mm, the glove swelling ratio when the glove is formed is 240 to 320, the tensile stress is 22 to 35 MPa, the elongation at break is 480 to 620%, and the tensile stress at the elongation of 500% is 15 to 35 MPa. , the glove is formed by the steps comprising the following steps: (a) washing a step of washing a mold or a mold and drying it, (b) a step of immersing the mold or the mold in the coagulant solution, and (c) a step of drying the mold or the mold to which the coagulant is attached, ( d) a step of immersing a mold or a mold after drying with a coagulant and drying it in an elastomer composition as in claim 4 or 9 (e) at 80 to 120 ° C (d) a step of drying the mold or the mold obtained in the step, and (f) adding the unsaturated carboxylic acid to the surface of the mold or the mold obtained in the above step (e) at 120 to 150 ° C The elastomer obtained by applying the acrylonitrile butadiene elastomer of the fourth aspect of the patent is subjected to a treatment for 20 to 30 minutes for crosslinking hardening.