KR101687866B1 - Carboxylic acid modified-nitrile based copolymer latex composition and latex composition for dip-forming comprising thereof - Google Patents

Abstract

The present invention relates to a carboxylic acid-modified nitrile-based copolymer latex composition comprising a reactive carbodiimide compound having excellent crosslinking performance without addition of sulfur and a vulcanization accelerator in the production of a dip product using a latex composition, a dip molding composition containing the same And a composition for dip molding comprising a carboxylic acid-modified nitrile-based copolymer latex composition and a reactive carbodiimide-based compound. The composition for dip molding according to the present invention does not require sulfur and a vulcanization accelerator. Therefore, when a latex composition for dip molding is manufactured, a long stirring aging step is not required, so that productivity can be increased and problems such as allergy reaction by sulfur and vulcanization accelerator There is an advantage not to cause.

Description

[0001] The present invention relates to a carboxylic acid-modified nitrile-based copolymer latex composition and a latex composition for dip-

The present invention relates to a carboxylic acid-modified nitrile-based copolymer latex composition comprising a reactive carbodiimide compound having excellent crosslinking performance without addition of sulfur and a vulcanization accelerator in the production of a dip product using a latex composition, a dip molding composition containing the same And a composition for dip molding comprising a carboxylic acid-modified nitrile-based copolymer latex composition and a reactive carbodiimide-based compound.

Rubber gloves, which are widely used in everyday life such as housework, food industry, electronics industry, and medical field, are made by dip molding of natural rubber or carboxylic acid modified nitrile copolymer latex. In recent years, carbonic acid denatured nitrile gloves have been attracting attention in the disposable glove market due to allergies and unstable supply and demand due to the natural protein of natural rubber.

The carboxylic acid-modified nitrile glove is prepared by preparing a latex composition by blending sulfur and a vulcanization accelerator with a carboxylic acid-modified nitrile-based copolymer latex and then subjecting the latex composition to dip molding.

However, as described above, the process of preparing rubber gloves by mixing sulfur and a vulcanization accelerator has a disadvantage in that productivity is lowered because a long stirring aging process is usually performed after blending the sulfur and the vulcanization accelerator into the latex have. In addition, rubber gloves containing sulfur and a vulcanization accelerator as essential components may cause a substance which causes an unpleasant odor due to the chemical reaction between the sulfur and the vulcanization accelerator and the functional groups in the carboxylic acid-modified nitrile-based copolymer latex, The product value is lowered, and some users are caused allergic reaction to cause stinging.

Accordingly, there is a need for a latex composition having high oil resistance and mechanical strength and soft touch without addition of sulfur and a vulcanization accelerator which causes an unpleasant odor and an allergic reaction, and a dip molded article using the latex composition.

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made keeping in mind the above problems occurring in the prior art, and an object of the present invention is to provide a process for producing a carbodiimide- It is an object of the present invention to provide a carboxylic acid-modified nitrile-based copolymer latex composition having a high and soft touch.

Another object of the present invention is to provide a composition for dip molding comprising a carboxylic acid-modified nitrile-based copolymer latex composition containing the above-mentioned reactive carbodiimide compound.

It is still another object of the present invention to provide a latex composition for carboxylic acid-modified nitrile-based copolymer latex composition containing no reactive carbodiimide compound and a latex composition for deep molding comprising a reactive carbodiimide-based compound.

In order to solve the above-mentioned problems, the present invention provides a process for producing a copolymer, which comprises 0.1 to 10 parts by weight of a reactive carbodiimide compound based on 100 parts by weight of a monomer mixture, wherein the monomer mixture comprises a) 40 to 90% weight%; b) from 9% to 50% by weight of an ethylenically unsaturated nitrile-based monomer; And c) 0.1% by weight to 10% by weight of an ethylenic unsaturated acid monomer. The present invention also provides a carboxylic acid-modified nitrile-based copolymer latex composition.

The present invention also provides a latex composition for deep molding comprising 80% by weight to 99% by weight of a carboxylic acid-modified nitrile-based copolymer latex composition comprising the above-mentioned reactive carbodiimide compound.

In addition, the present invention relates to a process for preparing a rubber composition comprising a carboxylic acid-modified nitrile latex composition and a reactive carbodiimide compound; Wherein the carboxylic acid-modified nitrile latex composition comprises: a) from 40% to 90% by weight of a conjugated diene monomer; b) from 9% to 50% by weight of an ethylenically unsaturated nitrile-based monomer; And c) 0.1% by weight to 10% by weight of an ethylenically unsaturated acid monomer, based on the total weight of the latex composition.

The latex composition for dip molding according to the present invention comprises a mixture of a carboxylic acid-modified nitrile-based copolymer latex composition containing a reactive carbodiimide compound or a carboxylic acid modified nitrile-based copolymer latex composition and a reactive carbodiimide compound It is possible to produce a dip molded article having excellent cross-linking properties without addition of sulfur and a vulcanization accelerator and having excellent oil resistance and mechanical strength and having a soft touch.

In addition, since sulfur and a vulcanization accelerator are not required, a long stirring aging step is not needed when producing a latex composition for dip molding, which can increase the productivity and does not cause problems such as an allergic reaction caused by sulfur and a vulcanization accelerator .

Hereinafter, the present invention will be described in detail in order to facilitate understanding of the present invention.

The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention It should be construed as meaning and concept consistent with the technical idea of the present invention.

The present invention provides a carboxylic acid-modified nitrile-based copolymer latex composition comprising a reactive carbodiimide compound for crosslinking in place of sulfur and a vulcanization accelerator.

The carboxylic acid-modified nitrile-based copolymer latex composition according to an embodiment of the present invention comprises 0.1 to 10 parts by weight of a reactive carbodiimide compound based on 100 parts by weight of a monomer mixture, 40% to 90% by weight of a conjugated diene monomer; b) from 9% to 50% by weight of an ethylenically unsaturated nitrile-based monomer; And c) 0.1 to 10% by weight of an ethylenically unsaturated acid monomer.

The carboxylic acid-modified nitrile-based copolymer latex composition according to an embodiment of the present invention may contain 0.1 to 10 parts by weight of a reactive carbodiimide compound per 100 parts by weight of the monomer mixture. Preferably 0.5 to 7 parts by weight. If the reactive carbodiimide compound is contained in an amount of less than 0.1 part by weight, the tensile strength of the dip-molded article may be lowered. If the reactive carbodiimide compound is contained in an amount exceeding 10 parts by weight, the feeling of wearing and elongation of the dip-

The reactive carbodiimide compound is a reactive compound having a carbodiimide group (N═C═N), and is preferably a compound represented by the formula: 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide (EDC) or dicyclohexylcarbodi (DCC), and there are E-02, E-03A, V-02 and V-04 of Japan Nissinbo which are useful in the market.

The reactive carbodiimide compound may be used alone, or two or more compounds may be used in combination.

Preferably, the reactive carbodiimide compound may be 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide.

The reactive carbodiimide compound according to the present invention is less toxic than a conventional crosslinking agent, has no volatile organic compound (VOC), has a long usable time and is excellent in crosslinking performance, and thus contains the reactive carbodiimide compound The additional sulfur and vulcanization accelerator is not required when the carboxylic acid-modified nitrile-based copolymer latex composition is used as a composition for dip molding. Thus, it is possible to omit the long stirring aging step in the production of the composition for dip molding, which not only increases the productivity but also does not cause the allergic reaction by the sulfur and the vulcanization accelerator.

The monomer mixture according to an embodiment of the present invention may contain 40% by weight to 90% by weight, preferably 45% by weight to 80% by weight, of the conjugated diene monomer. When the conjugated diene monomer is contained in an amount of less than 40% by weight, the amount of the conjugated diene monomer may be too small, resulting in a molded article using the latex composition, which may result in hardness and poor wearing feeling. The amount of the conjugated dienic monomer is too large, so that the oil resistance of the molded article using the latex composition is deteriorated, and the tensile strength is lowered.

The conjugated diene monomer may be 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene, isoprene or a combination thereof.

Preferably 1,3-butadiene or isoprene, and most preferably 1,3-butadiene.

The monomer mixture according to an embodiment of the present invention may contain 9 to 50% by weight, preferably 15 to 45% by weight, of the ethylenically unsaturated nitrile-based monomer. If the amount of the ethylenically unsaturated nitrile monomer is less than 9% by weight, the amount of the ethylenically unsaturated nitrile monomer is too small. If the amount of the ethylenically unsaturated nitrile monomer is less than 50% by weight, The amount of the latex composition may become too high, resulting in a problem that the resulting molded article is hardened and the wearing feeling is deteriorated.

The ethylenically unsaturated nitrile-based monomer may be acrylonitrile, methacrylonitrile, fumaronitrile, a-chloronitrile, a-cyanoethyl acrylonitrile or a combination thereof.

The monomer mixture according to an embodiment of the present invention may comprise from 0.1% to 10% by weight, preferably from 0.5% to 9% by weight, of the ethylenically unsaturated acid monomer, and most preferably from 1% % To 8% by weight. If the ethylenic unsaturated acid monomer is contained in an amount of less than 0.1% by weight, the tensile strength of the resulting molded article is lowered. If the ethylenic unsaturated acid monomer is contained in an amount exceeding 10% by weight, the resulting molded article may become hard and the feeling of wearing may be deteriorated .

The ethylenic unsaturated acid monomer may be an ethylenically unsaturated monomer containing an acidic group such as a carboxyl group, a sulfonic acid group or an acid anhydride group, and may be an ethylenically unsaturated carboxylic acid monomer such as acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid, An ethylenically unsaturated polycarboxylic acid moiety such as maleic anhydride and citraconic anhydride, an ethylenically unsaturated sulfonic acid monomer such as styrenesulfonic acid, an ethylenically unsaturated polycarboxylic acid partial ester such as monobutyl fumarate, monobutyl maleate, and mono-2-hydroxypropyl maleate (partial ester) monomer.

Preferably acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid, and most preferably methacrylic acid.

In the present invention, the ethylenic unsaturated acid monomer may be used in the form of an alkali metal salt or an ammonium salt, and the respective components may be used singly or in combination of two or more.

The carboxylic acid-modified nitrile-based copolymer latex composition according to an embodiment of the present invention may have -COOH group by including an ethylenic unsaturated acid monomer as one monomer. Accordingly, it is possible to more easily lead to the rubberization of the latex composition when a dip molded article is produced using the latex composition for deep molding comprising the same.

The monomer mixture according to an embodiment of the present invention may further include 0.1 to 20 parts by weight of an ethylenically unsaturated monomer per 100 parts by weight of the monomer mixture. If the ethylenically unsaturated monomer is out of the above range, the balance between the soft feeling and the tensile strength does not match well, resulting in a poor wearing feeling and a deteriorated tensile strength.

The ethylenically unsaturated monomer is a substance copolymerizable with the ethylenically unsaturated nitrile monomer and the ethylenically unsaturated acid monomer contained in the monomer mixture, and includes styrene, alkylstyrene, vinylnaphthalene, fluoroethyl vinyl ether, (meth) acrylamide, N (Meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-propoxymethyl (meth) acrylamide, vinylpyridine, vinylnorbornene, (Meth) acrylate, dibutyl (meth) acrylate, dicyclopentadiene, 1,4-hexadiene, methyl (meth) acrylate, ethyl (Meth) acrylic acid esters such as tetrafluoropropyl acrylate, dibutyl maleate, dibutyl fumarate, diethyl maleate, methoxymethyl (meth) acrylate, ethoxyethyl Ethyl (meth) acrylate, cyanomethyl (meth) acrylate, 2-cyanoethyl (meth) acrylate, 1-cyanopropyl (Meth) acrylate, hydroxypropyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate or combinations thereof.

In addition, the carboxylic acid-modified nitrile-based copolymer latex composition according to an embodiment of the present invention may further include a polymerization initiator, a molecular weight modifier, and an emulsifier.

When the carboxylic acid-modified nitrile-based copolymer latex composition contains an emulsifier, the emulsifier may be contained in an amount of 0.3 to 10 parts by weight, preferably 0.8 to 8 parts by weight, per 100 parts by weight of the monomer mixture, . The emulsifier is not particularly limited, but may be, for example, an anionic surfactant, a nonionic surfactant, a cationic surfactant, or a positive surfactant. Preferably, it may be an anionic surfactant of an alkylbenzenesulfonic acid salt, an aliphatic sulfonic acid salt, a higher alcohol sulfuric acid ester salt, an a-olefin sulfonic acid salt, and an alkyl ether sulfuric acid ester salt.

When the carboxylic acid-modified nitrile-based copolymer latex composition contains a polymerization initiator, the polymerization initiator may be included in an amount of 0.01 to 2 parts by weight based on 100 parts by weight of the monomer mixture.

The polymerization initiator is not particularly limited, but may be, for example, a radical initiator. The radical initiator may be selected from the group consisting of inorganic peroxides such as sodium persulfate, potassium persulfate, potassium antacid ammonium, potassium perphosphate, hydrogen peroxide, t-butyl peroxide, cumene hydroperoxide, p- menthol hydroperoxide, di- , organic peroxides such as t-butylcumyl peroxide, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, dibenzoyl peroxide, 3,5,5-trimethylhexanol peroxide and t-butyl peroxyisobutylate A nitrogen compound such as azobisisobutyronitrile, peroxides, azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, and azobisisobutyric acid (butyl acid) methyl. The above-mentioned polymerization initiator may be used alone or in combination of two or more.

When the carboxylic acid-modified nitrile-based copolymer latex composition includes a molecular weight modifier, the molecular weight modifier may be included in an amount of 0.1 part by weight to 0.9 part by weight with respect to 100 parts by weight of the monomer mixture.

Examples of the molecular weight modifier include, but are not limited to, mercaptans such as a-methylstyrene dimer, t-dodecyl mercaptan, n-dodecyl mercaptan and octyl mercaptan, halogenated hydrocarbons such as methylene chloride, methylene bromide, Containing compounds such as tetraethylthiuram disulfide, dipentamethylenethiuramdisulfide, diisopropylkantogen disulfide, and the like. Preferably t-dodecylmercaptan.

The present invention also provides a process for producing a carboxylic acid-modified nitrile-based copolymer latex composition comprising a conjugated diene monomer, an ethylenically unsaturated nitrile monomer, an ethylenically unsaturated acid monomer and a reactive carbodiimide compound.

The above-mentioned monomers, the reactive carbodiimide compound and the additives such as the polymerization initiator, the molecular weight modifier, and the emulsifier which may be further added are as mentioned above.

The method for preparing the carboxylic acid-modified nitrile-based copolymer latex composition according to an embodiment of the present invention is not particularly limited and may be produced through emulsion polymerization commonly used in the art, A method of simultaneously adding the respective components such as a conjugated diene monomer, an ethylenically unsaturated nitrile monomer, an ethylenically unsaturated acid monomer and a reactive carbodiimide compound to a polymerization reactor at the same time, a method of continuously adding each component to a polymerization reactor Or by firstly adding each monomer constituting the latex composition to a polymerization reactor and adding the reactive carbodiimide compound to the polymerization reactor after the polymerization is initiated.

In order to facilitate the polymerization, additives such as a chelating agent, a dispersing agent, a pH adjuster, an oxygen scavenger, a particle size regulator, an anti-aging agent and an oxygen scavenger may be additionally used, Deg.] C to 90 [deg.] C, but may preferably be in a temperature range of 25 [deg.] C to 75 [deg.] C.

In addition, the present invention relates to a latex composition (A) for dip molding comprising a carboxylic acid-modified nitrile-based copolymer latex composition containing the above-mentioned reactive carbodiimide compound, or a carboxylic acid- There is provided a latex composition (B) for dip molding comprising a modified copolymer latex composition and a reactive carbodiimide compound.

Specifically, the latex composition (A) for dip molding according to one embodiment of the present invention is characterized by comprising a carboxylic acid-modified nitrile-based copolymer latex composition comprising the reactive carbodiimide-based compound.

As described above, the carboxylic acid-modified nitrile-based copolymer latex composition comprising the reactive carbodiimide compound contained in the late molding latex composition (A) for dip molding is prepared by mixing the respective components constituting the carboxylic acid modified nitrile-based copolymer latex composition Or may be prepared by polymerizing a monomer and a reactive carbodiimide compound together.

The latex composition (A) for dip molding is prepared by mixing an ionic bond cross-linking agent such as zinc oxide, a pigment such as titanium oxide, a filler such as silica, a dispersing agent , a pH adjusting agent, and the like may be added and mixed.

The latex composition (B) for dip molding according to another embodiment of the present invention comprises a carboxylic acid-modified nitrile-based copolymer latex composition not containing a reactive carbodiimide-based compound and a reactive carbodiimide-based compound; Wherein the carboxylic acid-modified nitrile latex composition comprises: a) from 40% to 90% by weight of a conjugated diene monomer; b) from 9% to 50% by weight of an ethylenically unsaturated nitrile-based monomer; And c) 0.1% to 10% by weight of an ethylenically unsaturated acid monomer.

The monomer mixture may further comprise 0.1 to 20 parts by weight of an ethylenically unsaturated monomer per 100 parts by weight of the mixture.

The specific contents and kinds of the reactive carbodiimide compound, the conjugated diene monomer, the ethylenically unsaturated nitrile monomer, the ethylenic unsaturated acid monomer and the ethylenic unsaturated monomer are as mentioned above.

The carboxylic acid-modified nitrile-based copolymer latex composition contained in the late molding latex composition (B) is prepared by mixing the respective monomers constituting the carboxylic acid-modified nitrile-based copolymer latex composition with only the additives using the above- ≪ / RTI >

The latex composition (B) for dip molding may be prepared by adding a reactive carbodiimide compound and an additive to a carboxylic acid-modified nitrile-based copolymer latex composition containing no reactive carbodiimide compound. At this time, the additive is the same as mentioned above.

The latex composition (A or B) for dip molding of the present invention may be prepared by mixing a carboxylic acid modified nitrile-based copolymer latex composition containing a reactive carbodiimide compound or a carboxylic acid modified nitrile based latex composition containing no reactive carbodiimide- May comprise from 80% by weight to 99% by weight, preferably from 85% by weight to 98% by weight, and more preferably from 88% by weight to 97% by weight of the coalescent latex composition.

The late forming latex compositions A and B may have a solids concentration of 10 wt% to 40 wt%, but preferably have a solids concentration of 15 wt% to 35 wt%. More preferably 18% by weight to 33% by weight.

The pH of the latex composition for deep molding (A and B) may be 8.0 to 1.2, preferably 9 to 11, and more preferably 9,3 to 10.5.

In addition, the latex composition for deep-forming of the present invention can be easily used for producing a dip-molded article.

The method of manufacturing the dip-molded article according to an embodiment of the present invention is not particularly limited and a conventionally known method can be used in the art. For example, a direct dipping method, an anode adhesion dipping method, Dipping method and the like. Preferably, anodic adhesion dipping may be used. There is an advantage that a dip-shaped article having a uniform thickness can be obtained when a dip-molded article is produced using the positive-electrode deposition-dipping method.

Hereinafter, a method of manufacturing a dip molded article according to an embodiment of the present invention will be described in detail.

The method of manufacturing the deep-formed article includes the steps of: (1) attaching a coagulant to the surface of the dope molding die; (Step 2) of immersing the latex composition for dip molding in a dip forming mold to which the coagulant is adhered to form a dip molding layer; And heating the dip molding layer to crosslink the latex composition.

Step 1 is a step of immersing a dip forming mold in a coagulant solution to form a coagulant on the surface of a dip forming mold in order to form a coagulant in a dip forming mold.

The coagulant solution is a solution in which the coagulant is dissolved in water, an alcohol or a mixture thereof. The coagulant in the coagulant solution may typically be contained in an amount of 5 to 75 wt%, preferably 15 to 55 wt% . Examples of the coagulant include, but are not limited to, metal halides such as barium chloride, calcium chloride, magnesium chloride, zinc chlorate, and aluminum chlorite; Nitrates such as barium nitrate, calcium nitrate and zinc nitrate; Potassium sulfate, magnesium sulfate, and sulfate such as aluminum sulfate, such as calcium acetate, barium acetate, calcium acetate and zinc acetate. Preferably calcium chloride or calcium nitrate.

Step 2 is a step of immersing a dip forming mold having a coagulant attached thereto to form a dip forming layer in the latex composition (A or B) for dip molding according to the present invention, and removing the dip forming mold to form a dip forming layer in a dip forming mold .

Step 3 is a step of heating the dip molding layer formed in the dip forming mold to obtain a dip molded product to evaporate the liquid component and crosslink the latex composition to proceed the curing.

The dip-molded product is not particularly limited, but may be household gloves, industrial gloves, condoms, catheters or health care products.

Hereinafter, the present invention will be described in more detail with reference to the following examples and experimental examples. However, the following examples and experimental examples are provided for illustrating the present invention, and the scope of the present invention is not limited thereto.

Example  One

(1) Production of Carboxylic Acid Modified Nitrile Copolymer Latex Composition for Deep Molding

To the reaction vessel was added a monomer mixture composed of 21 wt% of acrylonitrile, 74 wt% of 1.4-butadiene and 5 wt% of methacrylic acid and 0.5 wt part of tert-dodecyl mercaptan to 100 wt parts of the monomer mixture, 2.3 parts by weight of benzenesulfonate, 140 parts by weight of water and 1 part by weight of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide (EDC) were charged and the temperature was raised to 40 DEG C to initiate emulsion polymerization. When the conversion reached 65%, the temperature was elevated to 70 ° C to proceed the polymerization. When the conversion reached 94%, 0.2 part by weight of sodium dimethyldithiocarbamate was added to terminate the polymerization. Unreacted monomers were removed through a deodorization process, and ammonia water, an antioxidant and a defoaming agent were added to obtain a carboxylic acid-modified nitrile-based copolymer latex composition having a solid concentration of 44.5% and pH 8.0.

To the carboxylic acid-modified nitrile-based copolymer latex composition was added zinc oxide, titanium oxide, a 5% potassium hydroxide solution and an appropriate amount of secondary distilled water to prepare a carboxylic acid-modified nitrile-based copolymer latex for dip molding with a solid concentration of 30% A composition was obtained.

(2) Production of deep-formed products

A coagulant solution was prepared by mixing 22 wt% calcium nitrate, 69.5 wt% methanol, 8 wt% calcium carbonate, and 0.5 wt% humectant (Teric 320, Huntsman Corporation, Australia). A hand-shaped ceramic mold was immersed in this solution for 1 minute, pulled out, and dried at 70 ° C for 3 minutes to apply a coagulant to the hand mold. Thereafter, the mold coated with the coagulant was immersed in the carboxylate-modified nitrile-based copolymer latex composition for dip molding prepared in Example 1- (1) for 1 minute, pulled out, dried at 70 ° C for 1 minute, Min and leaching was performed. The mold was again dried at 70 DEG C for 3 minutes and then crosslinked at 125 DEG C for 20 minutes. The crosslinked deep linear layer was stripped from the hand mold to obtain a glove-shaped dip-molded article.

Example  2

1 part by weight of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide (EDC) was not added at the same time as the monomer mixture at the time of emulsion polymerization, but after the production of the carboxylic acid-modified nitrile- A dip-shaped article was obtained in the same manner as in Example 1 above.

Example  3

Except that 2.2 parts by weight of dicyclohexylcarbodiimide was used instead of 1 part by weight of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide (EDC). .

Example  4

Except that 1 part by weight of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide (EDC) was used instead of 1.5 parts by weight of E-02 available from Nisshinbo of Japan. .

Comparative Example  One

A dip-molded article was prepared in the same manner as in Example 1, except that 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide (EDC) was not used. That is, the dip-shaped article of Comparative Example 1 was prepared using a carboxylic acid-modified nitrile-based copolymer latex composition containing no reactive carbodiimide compound.

Experimental Example

In order to compare the physical properties of each of the dip-molded articles prepared in Examples 1 to 4 and Comparative Example 1, the following several characteristics were analyzed, and the results are shown in Table 1.

1) Measurement of stress, tensile strength and elongation at 300% elongation

Dumbbell-shaped specimens were prepared from each of the dip-molded articles prepared in the above Examples and Comparative Examples in accordance with ASTM D-412. Then, each test piece was pulled at a stretching speed of 500 mm / min, and the stress at the elongation percentage of 300%, the tensile strength at breakage, and the elongation at breakage were measured.

A circular specimen having a diameter of 2.5 cm was prepared from each of the dip-molded articles prepared in the above-mentioned Examples and Comparative Examples. After immersing the specimen in cyclohexanone polar solvent for 30 minutes, the length of the increased diameter was compared with the initial diameter to obtain a swelling ratio,%) were measured. The swelling was calculated by the following formula.

2) Chemical resistance measurement

A circular specimen having a diameter of 2.5 cm was prepared from each of the dip-molded articles prepared in the above-mentioned Examples and Comparative Examples. After immersing the specimen in cyclohexanone polar solvent for 30 minutes, the length of the increased diameter was compared with the initial diameter to obtain a swelling ratio,%) were measured. The swelling was calculated by the following formula.

3) Evaluation of molded article condition

The state of each molded article (glove) prepared in the above Examples and Comparative Examples was evaluated in consideration of basic physical properties, pinhole formation, stickiness, and the like.

division Tensile Strength (MPa) Elongation (%) Stress at 300% elongation (MPa) Swelling rate (%) Deep molding (glove) condition Example 1 24 547 6.0 248 Good Example 2 28 581 5.2 244 Good Example 3 25 550 5.8 252 Good Example 4 27 563 5.5 232 Good Comparative Example 1 16 516 3.5 340 usually

As shown in Table 1, the dip molded articles (Example 1 and Example 4) prepared using the composition for dip molding containing the carboxylic acid-modified nitrile-based copolymer latex composition containing the reactive carbodiimide compound and A dip molded article prepared using a composition for dip molding prepared by adding a reactive carbodiimide compound to a carboxylic acid-modified nitrile-based copolymer latex composition containing no reactive carbodiimide compound (Example 2 and Example 3 ) Exhibited remarkably excellent activity in all physical properties measured as compared with the dip-molded article (Comparative Example 1) produced using the composition for dip molding not containing the reactive carbodiimide compound.

This means that the dip-molded article of Comparative Example 1, to which the reactive carbodiimide compound was not added, was not sufficiently crosslinked.

Therefore, the reactive carbodiimide compound according to the present invention is excellent in crosslinking performance, so that when the composition for dip molding containing the reactive carbodiimide compound is used, the long stirring aging process can be omitted, But it does not require any additional sulfur and vulcanization accelerators and does not cause an allergic reaction caused by sulfur and vulcanization accelerators.

Claims (14)

0.1 to 10 parts by weight of a reactive carbodiimide compound per 100 parts by weight of the monomer mixture,
Wherein the monomer mixture comprises
a) from 40% to 90% by weight of a conjugated diene monomer;
b) from 9% to 50% by weight of an ethylenically unsaturated nitrile-based monomer; And
c) 0.1% to 10% by weight of an ethylenically unsaturated acid monomer.
The method according to claim 1,
Wherein the reactive carbodiimide compound is at least one compound selected from the group consisting of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide (EDC), dicyclohexylcarbodiimide (DCC) Copolymer latex composition.
3. The method of claim 2,
Wherein the reactive carbodiimide compound is 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide.
The method according to claim 1,
Wherein the conjugated diene monomer is 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene, isoprene, Carboxylic acid-modified nitrile-based copolymer latex composition.
The method according to claim 1,
Wherein the ethylenically unsaturated nitrile monomer is at least one selected from the group consisting of acrylonitrile, methacrylonitrile, fumaronitrile, a-chloronitrile, a-cyanoethyl acrylonitrile, Composition.
The method according to claim 1,
The ethylenic unsaturated acid monomer is selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, maleic anhydride, citraconic anhydride, styrenesulfonic acid, monobutyl fumarate, monobutyl maleate, mono-2- Wherein the carboxylic acid-modified nitrile-based copolymer latex composition is a combination thereof.
The method according to claim 1,
Wherein the monomer mixture further comprises 0.1 to 20 parts by weight of an ethylenically unsaturated monomer relative to 100 parts by weight of the mixture.
8. The method of claim 7,
(Meth) acrylamide, N, N-dimethylol (meth) acrylamide, N-methylol (Meth) acrylates such as methoxymethyl (meth) acrylamide, N-propoxymethyl (meth) acrylamide, vinylpyridine, vinylnorbornene, dicyclopentadiene, 1,4- (Meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, trifluoroethyl (meth) acrylate, tetrafluoropropyl (Meth) acrylate, methoxymethyl (meth) acrylate, ethoxyethyl (meth) acrylate, methoxyethoxyethyl (meth) acrylate, cyanomethyl Methacrylic acid 2-ethyl-6- (Meth) acrylate, dimethylaminoethyl (meth) acrylate, and the like, or a mixture of these compounds. Wherein the carboxylic acid-modified nitrile-based copolymer latex composition is a combination thereof.
The method of claim 1,
Wherein the latex composition further comprises 0.1 to 0.9 parts by weight of a molecular weight modifier relative to 100 parts by weight of the monomer mixture.
A latex composition for deep molding comprising 80% by weight to 99% by weight of a carboxylic acid-modified nitrile-based copolymer latex composition of any one of claims 1 to 9.
A carboxylic acid-modified nitrile-based latex composition and a reactive carbodiimide-based compound;
Wherein the carboxylic acid-modified nitrile latex composition comprises:
a) from 40% to 90% by weight of a conjugated diene monomer;
b) from 9% to 50% by weight of an ethylenically unsaturated nitrile-based monomer; And
c) 0.1% to 10% by weight of an ethylenically unsaturated acid monomer, based on the total weight of the latex composition.
12. The method of claim 11,
Wherein the reactive carbodiimide compound is included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the monomer mixture.
12. The method of claim 11,
Wherein the reactive carbodiimide compound is 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide (EDC), dicyclohexylcarbodiimide (DCC) .
12. The method of claim 11,
Wherein the monomer mixture further comprises 0.1 to 20 parts by weight of an ethylenically unsaturated monomer relative to 100 parts by weight of the mixture.