KR102586517B1 - Dip article and method of preparing the same - Google Patents

Abstract

The present invention relates to dip molded products. More specifically, at least one copolymer selected from the group consisting of nitrile-based copolymers and carboxylic acid-modified nitrile-based copolymers; Phenolic emulsifier; and a dip molded product containing an antistatic polymer and a method for manufacturing the same.

Description

Dip molded product and method of manufacturing the same {DIP ARTICLE AND METHOD OF PREPARING THE SAME}

The present invention relates to dip molded products, and more particularly, to dip molded products and methods for manufacturing the same.

Conventionally, natural rubber has been mainly used as a raw material for products that require elasticity, such as industrial, medical, and food gloves, balloons, and condoms. However, in recent years, natural rubber has been replaced by nitrile-based rubber due to the side effect of causing serious protein allergies in some users. Nitrile-based rubber has high oil resistance, and is especially widely used in work gloves used by users who handle organic solvents, as well as medical and food gloves. In addition, products made from nitrile rubber have the advantage of being less easily pierced by needles, etc., compared to products made from natural rubber, making them suitable for use by medical professionals who handle sharp scalpels or needles.

In addition, recently, due to the unstable supply and demand of natural rubber, many glove manufacturing companies are converting their natural rubber glove production lines to nitrile-based rubber glove production lines, and as awareness of safety increases, disposable gloves made from nitrile-based rubber are being replaced. Usage is continuously increasing.

However, when using non-conductive natural rubber or carboxylic acid-modified nitrile-based gloves, large and small static electricity is inevitably generated, and the static electricity generated at this time causes fine foreign substances such as surrounding dust to stick to the gloves, contaminating the gloves. There is a problem that is causing this.

KR 2018-0087588 A KR 2017-0006686 A

The problem to be solved by the present invention is to prevent electrostatic and physical adsorption of fine contaminants in the dip molded product when manufacturing dip molded products such as gloves in order to solve the problems mentioned in the background technology of the above invention. The purpose is to provide a dip molded product and a method for manufacturing the same.

According to one embodiment of the present invention for solving the above problems, the present invention includes at least one copolymer selected from the group consisting of nitrile-based copolymers and carboxylic acid-modified nitrile-based copolymers; Phenolic emulsifier; and a dip molded article containing an antistatic polymer.

In addition, the present invention includes the step of attaching a coagulant to the dip mold (S10); And the dip molding mold to which the coagulant is attached is filled with at least one copolymer selected from the group consisting of a nitrile-based copolymer and a carboxylic acid-modified nitrile-based copolymer; Phenolic emulsifier; and forming a layer derived from the first latex composition for dip molding by immersing the first dip molding latex composition containing an antistatic polymer (S20).

In addition, the present invention includes the step of attaching a coagulant to the dip mold (S100); The dip molding mold to which the coagulant is attached is filled with at least one copolymer selected from the group consisting of nitrile-based copolymers and carboxylic acid-modified nitrile-based copolymers; and a phenol-based emulsifier; forming a layer derived from the second latex composition for dip molding by immersing in the second latex composition for dip molding (S200); and immersing the dip mold on which the second layer derived from the latex composition for dip molding is formed in a solution containing an antistatic polymer to form an antistatic polymer derived layer (S300). .

When manufacturing a dip molded product according to the present invention, an antistatic effect can be expected due to the antistatic polymer contained in the dip molded product, which has the effect of preventing electrostatic and physical adsorption of fine contaminants in the dip molded product. There is.

1 is a schematic diagram of a method of manufacturing a dip molded product according to the present invention, (a) is a schematic diagram of a method of manufacturing a molded product manufactured according to Example 1, and (b) is a schematic diagram of a manufacturing method of a molded product manufactured according to Example 2. This is a schematic diagram of the manufacturing method.
Figure 2 is a dip molded product according to the present invention, (a) is a photograph of the molded product manufactured according to Example 1, (b) is a photograph of the molded product manufactured according to Example 2, and (c) is a photograph of the molded product manufactured according to Example 3. This is a photo of a molded product manufactured according to .
Figure 3 is a dip molded product according to the present invention, (a) is a photograph of the molded product manufactured according to Comparative Example 1, and (b) is a photograph of the molded product manufactured according to Comparative Example 2.

Terms or words used in the description and claims of the present invention should not be construed as limited to their ordinary or dictionary meanings, and the inventor should appropriately use the concept of the term to explain his or her invention in the best way. Based on the principle of definability, it must be interpreted with meaning and concept consistent with the technical idea of the present invention.

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

In the present invention, the term 'monomer-derived repeating unit' may refer to a component, structure, or the substance itself derived from a monomer. As a specific example, during polymerization of a polymer, the input monomer participates in the polymerization reaction and repeats within the polymer. It may mean a unit.

In the present invention, the term 'latex' may mean that a polymer or copolymer polymerized by polymerization exists in a dispersed form in water, and as a specific example, a polymer or copolymer polymerized by emulsion polymerization. This may mean that the fine particles exist in a colloidal state dispersed in water.

In the present invention, the term 'derived layer' may refer to a layer formed from a polymer or copolymer, and as a specific example, when manufacturing a dip molded product, the polymer or copolymer is attached, fixed, and/or polymerized on the dip mold to form a polymer or It may mean a layer formed from a copolymer.

In the present invention, the term 'compound-derived cross-linking portion' may refer to a component, structure, or the substance itself derived from a compound, and serves as a cross-linking within or between polymers formed by the action and reaction of the cross-linking agent composition. It may mean a cross linking part.

In the present invention, the term 'alkyl' refers to a linear or branched saturated monovalent hydrocarbon of carbon atoms, such as methyl, ethyl, propyl, 2-propyl, n-butyl, iso-butyl, tert-butyl, pentyl, hexyl, dodecyl, etc. It may mean that it includes not only unsubstituted ones but also those substituted by substituents.

In the present invention, the term 'cycloalkyl' refers to cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, cyclooctyl, decahydronaphthalenyl, adamantanyl, norbornyl (i.e. Bicyclo [2,2,1] hept-5-enyl), etc., at least one hydrogen atom of the alkyl group defined above is a saturated or unsaturated cyclic hydrocarbon, monovalent monocyclic, bicyclic or It may mean substituted with a tricyclic hydrocarbon, and may mean not only unsubstituted but also substituted with a substituent.

In the present invention, the term 'aryl' may mean that one or more hydrogen atoms of the above-defined alkyl group are substituted with an aryl group, such as phenyl, naphthalenyl, fluorenyl, etc., and may be unsubstituted as well as substituted. It may mean that it also includes those substituted by .

In the present invention, the term 'alkenyl' refers to a linear or alkenyl group of carbon atoms, such as ethenyl, 1-propenyl, 2-propenyl, 2-butenyl, 3-butenyl, pentenyl, 5-hexenyl, dodecenyl, etc. Alkenyl may refer to a branched monovalent hydrocarbon, and alkenyl may be bonded through a carbon atom containing a carbon-carbon double bond or through a saturated carbon atom, and may be unsubstituted as well as substituted by a substituent. It can mean including.

In the present invention, the term '(meth)acrylate' may mean that both acrylate and methacrylate are possible.

The dip molded article according to the present invention includes at least one copolymer selected from the group consisting of nitrile-based copolymers and carboxylic acid nitrile-based copolymers; Phenolic emulsifier; And it may include an antistatic polymer.

According to one embodiment of the present invention, the antistatic polymer is polyethylenedioxythiophene:polystyrenesulfonate (PEDOT:PSS), polyacetylene, polypyrrole, polythiophene, polyparaphenylene, polyphenylene. It may include one or more selected from the group consisting of sulfide, polyparaphenylene vinylene, and polyaniline.

According to one embodiment of the present invention, the antistatic polymer is 0.005 parts by weight to 2 parts by weight based on 100 parts by weight of at least one copolymer selected from the group consisting of the nitrile-based copolymer and carboxylic acid-modified nitrile-based copolymer, It may be 0.01 part by weight to 1 part by weight, or 0.1 part by weight to 1.5 part by weight, and within this range, the dip molded product is molded from the latex composition for dip molding containing the nitrile-based copolymer or the carboxylic acid-modified nitrile-based copolymer. It is flexible, has excellent touch and fit, and has excellent oil resistance and tensile strength.

According to one embodiment of the present invention, the nitrile-based copolymer may include a repeating unit derived from an ethylenically unsaturated nitrile-based monomer and a repeating unit derived from a conjugated diene-based monomer. In addition, according to one embodiment of the present invention, the carboxylic acid-modified nitrile-based copolymer may include a repeating unit derived from an ethylenically unsaturated nitrile-based monomer, a repeating unit derived from a conjugated diene-based monomer, and a repeating unit derived from an ethylenically unsaturated acid monomer. there is.

According to one embodiment of the present invention, the ethylenically unsaturated nitrile-based monomer forming the repeating unit derived from the ethylenically unsaturated nitrile-based monomer of the nitrile-based copolymer and the carboxylic acid-modified nitrile-based copolymer is acrylonitrile and methacrylonitrile. , may be one or more selected from the group consisting of fumaronitrile, α-chloronitrile, and α-cyano ethyl acrylonitrile, and specific examples may include acrylonitrile and methacrylonitrile. More specific examples include acrylonitrile, It may be nitrile.

The content of the repeating unit derived from the ethylenically unsaturated nitrile monomer of the nitrile-based copolymer and the carboxylic acid-modified nitrile-based copolymer is each independently 10 wt. It may be % to 50% by weight, 15% to 45% by weight, or 20% to 40% by weight, and within this range, the latex for dip molding containing the nitrile-based copolymer or carboxylic acid-modified nitrile-based copolymer Dip molded products made from the composition are flexible, have excellent touch and fit, and have excellent oil resistance and tensile strength.

According to one embodiment of the present invention, the conjugated diene monomer forming the repeating unit derived from the conjugated diene monomer of the nitrile-based copolymer and the carboxylic acid-modified nitrile-based copolymer is 1,3-butadiene, 2,3-dimethyl- It may be one or more selected from the group consisting of 1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene, and isoprene, and specific examples include 1,3-butadiene or isoprene. As a specific example, it may be 1,3-butadiene.

The content of the repeating unit derived from the conjugated diene monomer included in the nitrile-based copolymer is 50% by weight to 90% by weight, 55% by weight to 85% by weight, or 60% by weight to 80% by weight based on the total content of the nitrile-based copolymer. It may be, the content of the repeating unit derived from the conjugated diene monomer included in the carboxylic acid-modified nitrile-based copolymer is 40% by weight to 89% by weight, 40% by weight to 80% by weight based on the total content of the carboxylic acid-modified nitrile-based copolymer. It may be % by weight, or 50% by weight to 78% by weight, and within this range, the dip molded article molded from the latex composition for dip molding containing the nitrile-based copolymer or the carboxylic acid-modified nitrile-based copolymer is flexible, It has excellent touch and fit, as well as excellent oil resistance and tensile strength.

In addition, according to one embodiment of the present invention, the ethylenically unsaturated acid monomer forming the repeating unit derived from the ethylenically unsaturated acid monomer of the carboxylic acid-modified nitrile-based copolymer contains an acidic group such as a carboxyl group, a sulfonic acid group, and an acid anhydride group. It may be an ethylenically unsaturated monomer, and specific examples include ethylenically unsaturated acid monomers such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid; polycarboxylic anhydrides such as maleic anhydride and citraconic anhydride; ethylenically unsaturated sulfonic acid monomers such as styrene sulfonic acid; It may be one or more selected from the group consisting of ethylenically unsaturated polycarboxylic acid partial ester monomers such as monobutyl fumarate, monobutyl maleate, and mono-2-hydroxypropyl maleate, and more specific examples include acrylic acid and methacrylic acid. , itaconic acid, maleic acid, and fumaric acid. A more specific example may be methacrylic acid. During polymerization, the ethylenically unsaturated acid monomer may be used in the form of a salt such as an alkali metal salt or ammonium salt.

The content of repeating units derived from ethylenically unsaturated acid monomers contained in the carboxylic acid-modified nitrile-based copolymer is 0.1% by weight to 15% by weight, 0.5% by weight to 9% by weight, or It may be 1% by weight to 8% by weight, and within this range, a dip molded product molded from the latex composition for dip molding containing the carboxylic acid-modified nitrile-based copolymer is flexible and has excellent wearing comfort, as well as resistance and tensile strength. It has excellent strength effects.

According to one embodiment of the present invention, the nitrile-based copolymer and the carboxylic acid-modified nitrile-based copolymer include a repeating unit derived from a conjugated diene monomer, a repeating unit derived from an ethylenically unsaturated nitrile monomer, and a repeating unit derived from an ethylenically unsaturated acid monomer. In addition, it may optionally further include a repeating unit derived from an ethylenically unsaturated monomer.

The ethylenically unsaturated monomer forming the repeating unit derived from the ethylenically unsaturated monomer may include a vinyl aromatic monomer selected from the group consisting of styrene, aryl styrene, and vinyl naphthalene; Fluoroalkyl vinyl ethers such as fluoro ethyl vinyl ether; (meth)acrylamide, N-methylol (meth)acrylamide, N,N-dimethylol(meth)acrylamide, N-methoxy methyl(meth)acrylamide, and N-propoxy methyl(meth)acrylamide An ethylenically unsaturated amide monomer selected from the group consisting of; Non-conjugated diene monomers such as vinyl pyridine, vinyl norbornene, dicyclopentadiene, and 1,4-hexadiene; Methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, trifluoroethyl (meth)acrylate, tetrafluoropropyl (meth)acrylate, dibutyl maleate, Dibutyl fumarate, diethyl maleate, methoxymethyl (meth)acrylate, ethoxyethyl (meth)acrylate, methoxyethoxyethyl (meth)acrylate, cyanomethyl (meth)acrylate, 2-cyano (meth)acrylate. Ethyl, 1-cyanopropyl (meth)acrylic acid, 2-ethyl-6-cyanohexyl (meth)acrylic acid, 3-cyanopropyl (meth)acrylic acid, hydroxyethyl (meth)acrylic acid, hydroxy (meth)acrylic acid It may be one or more types selected from the group consisting of ethylenically unsaturated carboxylic acid ester monomers selected from the group consisting of propyl, glycidyl (meth)acrylate, and dimethylamino ethyl (meth)acrylate.

When the nitrile-based copolymer or the carboxylic acid-modified nitrile-based copolymer includes a repeating unit derived from the ethylenically unsaturated monomer, the content of the repeating unit derived from the ethylenically unsaturated monomer is the nitrile-based copolymer or the carboxylic acid-modified nitrile-based copolymer. It may be 25% by weight or less, 0.01 to 25% by weight, or 0.01 to 20% by weight based on the total content of the polymer, and within this range, the nitrile-based copolymer or the carboxylic acid-modified nitrile-based copolymer for dip molding. The dip molded product made from the latex composition has excellent feel and fit, and has excellent tensile strength.

According to one embodiment of the present invention, the phenol-based emulsifier may be represented by the following formula (1).

[Formula 1]

In Formula 1, R ₁ , R ₂ and R ₃ are each independently hydrogen; or substituted or unsubstituted linear or branched alkyl having 1 to 30 carbon atoms, 1 to 20 carbon atoms, or 1 to 10 carbon atoms, where at least one of R ₁ to R ₃ is substituted or unsubstituted. linear or branched alkyl having 1 to 30 carbon atoms, and R is hydrogen; Polymerizable functional group; an alkoxy group having 1 to 30 carbon atoms, 1 to 20 carbon atoms, or 1 to 10 carbon atoms; inorganic or organic salts; non-ionic group; or halogen, m is an integer of 1 to 20, 1 to 10, or 1 to 5, and n is an integer of 1 to 100, 4 to 80, or 8 to 25.

Substituents that may be substituted for the linear or branched alkyl include linear or branched alkyl having 1 to 30 carbon atoms, 1 to 20 carbon atoms, or 1 to 10 carbon atoms; cycloalkyl having 3 to 30 carbon atoms, 3 to 20 carbon atoms, or 6 to 10 carbon atoms; aryl having 6 to 30 carbon atoms, 6 to 20 carbon atoms, 6 to 10 carbon atoms; And it may be one or more types selected from the group consisting of halogen.

The alkyl may be methyl, ethyl, propyl, 2-propyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, dodecyl, etc.

The cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, cyclooctyl, decahydronaphthalenyl, adamantanyl, norbornyl (i.e., bicyclo [2, 2,1] hept-5-enyl), etc.

The aryl may be phenyl, naphthalenyl, fluorenyl, etc.

The polymerizable functional group is (meth)acrylate; Alkyl (meth)acrylate having 1 to 30 carbon atoms, 1 to 20 carbon atoms, or 1 to 10 carbon atoms; and alkenyl (meth)acrylates having 2 to 30 carbon atoms, 2 to 20 carbon atoms, and 2 to 10 carbon atoms.

The alkoxy group may be methoxy, ethoxy, protoxy, isobutylmethoxy, butoxy, etc.

The inorganic or organic salts include phosphonate (-PO ₃ -M ⁺ ), phosphate (PO ₄ -M ⁺ ), sulfate (SO ₄ -M ⁺ ), sulfonate (SO ₃ -M ⁺ ), carboxylate ( It may be COO-M ⁺ ), etc. At this time, M ⁺ may be H ⁺ , Na ⁺ , NH ₄ ⁺ , K ⁺ , Li ⁺ , etc.

The nonionic group may be a hydroxyl group (-OH), cyanide (-CN), carboxylic acid group (-COOH), amide group (-CONH ₂ ), etc.

The halogen may be F, Cl, Br, I, etc.

As a specific example, R ₁ , R ₂ and R ₃ are each independently hydrogen, butyl, tert-butyl, isobutyl, It may be, etc.

According to one embodiment of the present invention, the phenol-based emulsifier may be represented by the following formula (2).

[Formula 2]

In Formula 2, R is hydrogen; Polymerizable functional group; an alkoxy group having 1 to 10 carbon atoms; inorganic or organic salts; non-ionic group; or halogen, and n is an integer of 1 to 100, 4 to 80, or 8 to 25.

The polymerizable functional group is (meth)acrylate; Alkyl (meth)acrylate having 1 to 30 carbon atoms, 1 to 20 carbon atoms, or 1 to 10 carbon atoms; and alkenyl (meth)acrylates having 2 to 30 carbon atoms, 2 to 20 carbon atoms, and 2 to 10 carbon atoms.

The alkyl (meth)acrylate includes methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, It may be heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, etc.

The alkenyl (meth)acrylate may be vinyl (meth)acrylate, allyl (meth)acrylate, 1,1-dimethylpropenyl (meth)acrylate, 3,3-dimethylbutenyl (meth)acrylate, etc. .

As another example, the polymerizable functional groups include acrylo, methacrylo, acrylamido, methacrylamido, diallylamino, allyl ether, vinyl ether, α-alkenyl, maleinido, styrenyl, and α- It may be one or more types selected from the group consisting of alkyl styrenyl groups.

The content of the phenol-based emulsifier may be 0.06 parts by weight to 7 parts by weight, 0.1 parts by weight to 5.5 parts by weight, or 0.1 parts by weight to 4 parts by weight, based on 100 parts by weight of the carboxylic acid-modified nitrile-based copolymer, based on solid content. Within this range, the syneresis time with the latex composition for dip molding containing the phenol-based emulsifier increases, improving stability, and the modulus is reduced, improving the wearing comfort of the molded product manufactured using the latex composition for dip molding. It has excellent effects.

The number average molecular weight of the phenol-based emulsifier may be 250 g/mol to 30,000 g/mol or 300 g/mol to 20,000 g/mol, and within this range, it has excellent dispersion in the solvent, making it suitable for use in nitrile-based copolymer latex or carboxylic acid. When manufacturing acid-modified nitrile-based copolymer latex, the stability of nitrile-based copolymer latex or carboxylic acid-modified nitrile-based latex is improved, and the syneresis time of the latex composition for dip molding is increased, which not only improves stability but also reduces modulus. This results in excellent wearing comfort for molded products manufactured using the latex composition for dip molding.

According to one embodiment of the present invention, the phenol-based emulsifier contains a hydrophilic group, so it is easily soluble in water and can be easily mixed and dispersed, and is fixed to the surface of the nitrile-based copolymer or carboxylic acid-modified nitrile-based copolymer particles. This has the effect of improving the stability of latex.

On the other hand, when the phenol-based emulsifier contains not only a hydrophilic group but also a bulky benzene ring, such as the phenol-based emulsifier represented by Formula 2, it plays a role in slowing down film formation when manufacturing a molded article with a composition for dip molding containing it. This has the effect of increasing syneresis time.

By containing an antistatic polymer, the dip molded product according to the present invention can prevent electrostatic and physical adsorption of fine contaminants due to the antistatic effect during the manufacture of the dip molded product. The antistatic polymer is a water-soluble polymer material that exhibits conductivity, and serves to provide conductivity to dip molded products containing it. In other words, when manufacturing a dip molded product, static electricity may be generated as electrons continuously accumulate in the non-conductive dip molded product. When an antistatic polymer is included, the accumulation of electrons can be prevented, which has the effect of preventing static electricity. there is.

Meanwhile, the dip molded product according to the present invention further increases conductivity by including both an antistatic polymer and a phenol-based emulsifier when manufacturing the dip molded product, thereby providing an excellent antistatic effect.

For example, when polyethylenedioxythiophene:polystyrenesulfonate (PEDOT:PSS) is used together with a phenol-based emulsifier as an antistatic polymer when manufacturing dip molded products, polystyrenesulfonate material, which is a nonconductor of polyethylenedioxythiophene:polystyrenesulfonate, is extracted. At this time, the bond between polyethylenedioxythiophene:polystyrenesulfonate is changed to polyethylenedioxythiophene:phenolic emulsifier, and conductivity increases due to excellent contact between particles made of polyethylenedioxythiophene, resulting in excellent antistatic effect. There is.

In addition, the present invention provides a dip molded product manufacturing method for manufacturing the dip molded product. The method for producing a dip molded product may include the step of immersing the latex composition for dip molding by a direct immersion method, an anode adhesion immersion method, a Teague adhesion immersion method, etc., and as a specific example, an anode adhesion immersion method. This can be done, and in this case, there is an advantage in obtaining dip molded products of uniform thickness.

As a specific example, the method for manufacturing a dip molded product can manufacture a dip molded product as shown in FIG. 1(a), and as a more specific example, the step of attaching a coagulant to the dip mold (S10); And the dip molding mold to which the coagulant is attached is filled with at least one copolymer selected from the group consisting of a nitrile-based copolymer and a carboxylic acid-modified nitrile-based copolymer; Phenolic emulsifier; and forming a layer derived from the first latex composition for dip molding by immersing the first dip molding latex composition containing an antistatic polymer (S20).

According to one embodiment of the present invention, the step (S10) may be a step of attaching the coagulant to the surface of the dip mold by immersing the dip mold in a coagulant solution to form a coagulant in the dip mold.

The coagulant solution is a solution in which a coagulant is dissolved in water, alcohol, or a mixture thereof, and the content of the coagulant in the coagulant solution is 5% by weight to 50% by weight, 7% to 45% by weight, or 10% by weight based on the total content of the coagulant solution. It may be from % to 40% by weight.

The coagulants include metal halides such as barium chloride, calcium chloride, magnesium chloride, zinc chloride, and aluminum chloride; nitrates such as barium nitrate, calcium nitrate and zinc nitrate; Acetate salts such as barium acetate, calcium acetate and zinc acetate; and sulfate such as calcium sulfate, magnesium sulfate, and aluminum sulfate. Specific examples may include calcium chloride or calcium nitrate.

In addition, according to one embodiment of the present invention, in the step (S10), in order to attach the coagulant to the dip molding mold, the dip molding mold is placed in the coagulant solution for at least 1 minute, 1 minute to 10 minutes, or 1 minute to 5 minutes. It may further include soaking for a while, taking it out, and then drying it at 70°C to 150°C, 70°C to 130°C, or 70°C to 100°C.

According to one embodiment of the present invention, in the step (S20), a dip mold to which a coagulant is attached to form a dip molding layer is immersed in the first dip molding latex composition, taken out, and first dip molded in the dip mold. This may be a step of forming a layer derived from the latex composition. As a specific example, the step (S20) may be repeated 2 or more times, 2 to 12 times, or 2 to 10 times as necessary, and in this case, the layer derived from the first dip molding latex composition is further strengthened. It has excellent mechanical properties such as tensile properties and durability of dip molded products.

In addition, according to one embodiment of the present invention, in the step (S20), in order to form a dip molding layer in the dip molding mold, the dip molding mold with the coagulant attached is dipped in the first dip molding latex composition for 1 minute or more. It may further include soaking for 1 minute to 10 minutes, or 1 minute to 5 minutes, taking it out, and drying it at 70°C to 150°C, 70°C to 130°C, or 70°C to 100°C.

Meanwhile, according to one embodiment of the present invention, the first dip molding latex composition in the step (S20) is produced by polymerizing a nitrile-based copolymer or carboxylic acid-modified nitrile-based copolymer to form a nitrile-based copolymer latex, or preparing a carboxylic acid-modified nitrile-based copolymer latex (S21); And a step (S22) of adding and mixing a phenol-based emulsifier, a cross-linking agent composition, and an antistatic polymer to the nitrile-based copolymer latex or carboxylic acid-modified nitrile-based copolymer latex prepared in step (S21). You can.

According to one embodiment of the present invention, the polymerization of the nitrile-based copolymer or carboxylic acid-modified nitrile-based copolymer in step (S21) may be performed by emulsion polymerization. The polymerization may be carried out by polymerizing the monomer mixture, and each monomer included in the monomer mixture may be added in the type and amount of the monomer mentioned above, and may be added all at once or continuously.

Meanwhile, during the polymerization in step (S21), the monomer mixture may be simultaneously introduced into the polymerization reactor prior to polymerization, or a portion of the monomer mixture may be first introduced into the polymerization reactor, and the remaining monomer mixture may be added after the start of polymerization. It can be implemented. As described above, when the monomer mixture is divided and added, when repeating units derived from each monomer in the nitrile-based copolymer or carboxylic acid-modified nitrile-based copolymer are formed, the monomer The distribution can be made uniform, and thus, there is an effect of improving the balance between the physical properties of dip molded products manufactured including a nitrile-based copolymer or a carboxylic acid-modified nitrile-based copolymer. In addition, during the polymerization in the (S21) step, the polymerization may be performed by adding a glycidyl ether-based compound together with the monomer mixture. In this case, the nitrile-based compound prepared by the polymerization in the (S21) step A cross-linked portion derived from a glycidyl ether-based compound may be formed in the copolymer or carboxylic acid-modified nitrile-based copolymer.

Additionally, according to one embodiment of the present invention, polymerization of the nitrile-based copolymer or carboxylic acid-modified nitrile-based copolymer may be carried out in the presence of an emulsifier, a polymerization initiator, an activator, and a molecular weight regulator.

When the polymerization of the nitrile-based copolymer or the carboxylic acid-modified nitrile-based copolymer is carried out including an emulsifier, the emulsifier is, for example, a group consisting of an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant. It may be one or more types selected from, and specific examples may be one or more anionic surfactants selected from the group consisting of alkylbenzene sulfonates, aliphatic sulfonates, higher alcohol sulfuric acid ester salts, α-olefin sulfonates, and alkyl ether sulfuric acid ester salts. there is.

The emulsifier may be added in an amount of 0.3 to 10 parts by weight, 0.8 to 8 parts by weight, or 1.5 to 8 parts by weight based on 100 parts by weight of the total monomer mixture, and within this range, polymerization stability is excellent. , the amount of foam generated is small, which makes it easy to manufacture molded products.

In addition, when the polymerization of the nitrile-based copolymer or the carboxylic acid-modified nitrile-based copolymer is carried out including a polymerization initiator, the polymerization initiator may be an inorganic peroxide such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate, and hydrogen peroxide. ; t-butyl peroxide, cumene hydroperoxide, p-menthane hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, dibenzoyl peroxide oxide, organic peroxides such as 3,5,5-trimethylhexanol peroxide and t-butyl peroxy isobutyrate; It may be one or more selected from the group consisting of nitrogen compounds such as azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, and methyl azobisisobutyric acid (butyric acid), A specific example may be an inorganic peroxide, and a more specific example may be persulfate.

The polymerization initiator may be added in an amount of 0.01 parts by weight to 2 parts by weight, 0.02 parts by weight to 1.5 parts by weight, or 0.05 parts by weight to 1 part by weight based on 100 parts by weight of the total content of the monomer mixture, and within this range, the polymerization rate It has an effect that is easy to control.

In addition, when the polymerization of the nitrile-based copolymer or carboxylic acid-modified nitrile-based copolymer is carried out including a molecular weight regulator, the molecular weight regulator is, for example, α-methylstyrene dimer; mercaptans such as t-dodecyl mercaptan, n-dodecyl mercaptan, and octyl mercaptan; halogenated hydrocarbons such as carbon tetrachloride, methylene chloride, and methylene bromide; It may be one or two or more types selected from the group consisting of sulfur-containing compounds such as tetraethyl thiuram disulfide, dipentamethylene thiuram disulfide, and diisopropylxanthogen disulfide, and specific examples include mercaptans. A specific example may be t-dodecyl mercaptan. The molecular weight regulator may be added in an amount of 0.1 to 2 parts by weight, 0.2 to 1.5 parts by weight, or 0.3 to 1.0 parts by weight based on 100 parts by weight of the total monomer mixture, and within this range, polymerization stability is excellent. And when manufacturing molded products after polymerization, the physical properties of the molded products are excellent.

In addition, when the polymerization of the nitrile-based copolymer or carboxylic acid-modified nitrile-based copolymer is carried out including an activator, the activator may be sodium formaldehyde, sulfoxylate, sodium ethylenediamine teraacetate, or ferrous sulfate. , it may be one or more selected from the group consisting of dextrose, sodium pyrrolate, and sodium sulfite.

The activator may be added in an amount of 0.01 parts by weight to 5.0 parts by weight, 0.01 parts by weight to 3 parts by weight, or 0.01 parts by weight to 2.0 parts by weight based on 100 parts by weight of the total content of the monomer mixture, and the polymerization rate is optimized within this range. It has the effect of maintaining the level.

In addition, according to an embodiment of the present invention, the polymerization of the nitrile-based copolymer or the carboxylic acid-modified nitrile-based copolymer may be carried out in water as a medium, for example, deionized water, and to ensure ease of polymerization, as necessary. It may be carried out by further including additives such as chelating agents, dispersants, pH adjusters, deoxidizers, particle size adjusters, anti-aging agents, and oxygen scavengers.

According to one embodiment of the present invention, the emulsifier, polymerization initiator, molecular weight regulator, additives, etc. may be added to the polymerization reactor as a bulk or divided portion, like the monomer mixture, or may be added continuously at each injection.

In addition, according to one embodiment of the present invention, the polymerization of the nitrile-based copolymer or the carboxylic acid-modified nitrile-based copolymer is carried out at a polymerization temperature of 10 ℃ to 90 ℃, 20 ℃ to 80 ℃, or 25 ℃ to 75 ℃. It can be, and within this range, latex stability is excellent.

Meanwhile, according to one embodiment of the present invention, the step (S21) may include terminating the polymerization reaction to obtain nitrile-based copolymer latex or carboxylic acid-modified nitrile-based copolymer latex. Termination of the polymerization reaction of the nitrile-based copolymer or carboxylic acid-modified nitrile-based copolymer may be carried out when the polymerization conversion rate is 90% or more, 90% to 99.9%, or 93% to 99%, and a polymerization terminator, This can be done by adding pH adjusters and antioxidants. In addition, the step (S21) may further include a step of removing unreacted monomers by a deodorizing concentration process after completion of the reaction.

In addition, according to one embodiment of the present invention, a step (S22) of adding and mixing a phenol-based emulsifier, a cross-linking agent composition, and an antistatic polymer to the prepared nitrile-based copolymer latex or carboxylic acid-modified nitrile-based copolymer latex It can be implemented. The step (S22) may be a step for producing a first latex composition for dip molding from nitrile-based copolymer latex or carboxylic acid-modified nitrile-based copolymer latex. At this time, the type and content of the phenolic emulsifier and antistatic polymer may be the same as described above. Additionally, the phenol-based emulsifier may be different from the emulsifier added during polymerization described above.

In addition, according to one embodiment of the present invention, the antistatic polymer is mixed with the prepared nitrile-based copolymer or carboxylic acid-modified nitrile-based copolymer latex to remove fine contaminants when manufacturing the first dip molding latex composition containing the same. It has the effect of preventing electrostatic and physical adsorption.

Meanwhile, the crosslinkable composition added in step (S22) may include one or more crosslinking agents selected from the group consisting of a vulcanizing agent, a vulcanization accelerator, and zinc oxide.

According to one embodiment of the present invention, the vulcanizing agent is used to vulcanize the latex composition for first dip molding, and may be sulfur such as powdered sulfur, precipitated sulfur, colloidal sulfur, surface-treated sulfur, and insoluble sulfur. When forming a crosslinking portion including sulfur, the amount of sulfur is 0.1 to 10 parts by weight based on 100 parts by weight (based on solid content) of the nitrile-based copolymer or carboxylic acid-modified nitrile-based copolymer in the first dip molding latex composition. parts, or 1 to 5 parts by weight, and within this range, excellent crosslinking ability is achieved.

In addition, according to one embodiment of the present invention, the vulcanization accelerator among the crosslinking agents is 2-mercaptobenzothiazole (MBT, 2-mercaptobenzothiazole), 2,2-dithiobisbenzothiazole-2-sulfenamide (MBTS, 2 ,2-dithiobisbenzothiazole-2-sulfenamide), N-cyclohexylbenzothiazole-2-sulfenamide (CBS, N-cyclohexylbenzothiasole-2-sulfenamide), 2-morpholinothiobenzothiazole (MBS, 2-morpholinothiobenzothiazole) , tetramethylthiuram monosulfide (TMTM), tetramethylthiuram disulfide (TMTD), zinc diethyldithiocarbamate (ZDEC), di-n-butyldithiocarba It may be one or more types selected from the group consisting of zinc mate (ZDBC, zinc di-n-butyldithiocarbamate), diphenylguanidine (DPG, diphenylguanidine), and di-o-tolylguanidine (di-o-tolylguanidine).

When forming a crosslinking portion including the vulcanization accelerator, the vulcanization accelerator is 0.1 part by weight based on 100 parts by weight (based on solid content) of the nitrile-based copolymer or carboxylic acid-modified nitrile-based copolymer in the first dip molding latex composition. It may be from 10 parts by weight, or from 0.5 parts by weight to 5 parts by weight, and within this range, the crosslinking ability is excellent.

In addition, according to one embodiment of the present invention, zinc oxide among the crosslinking agents may be present in a mixed form as a zinc oxide solution in the first dip molding latex composition, and the zinc oxide solution may include zinc oxide, ammonium carbonate, and aqueous ammonia. and water, and the content of zinc oxide in the zinc oxide solution may be 1% by weight to 20% by weight, or 1% by weight to 15% by weight, and within this range, crosslinking ability is excellent and latex stability is excellent. It is excellent and has excellent tensile strength and flexibility of the manufactured dip molded product.

According to one embodiment of the present invention, the nitrile-based copolymer latex or carboxylic acid-modified nitrile-based copolymer latex has a glass transition temperature of -50 ℃ to -15 ℃, -47 ℃ to -15 ℃, or -45 ℃ to - It may be 20°C, and within this range, deterioration of tensile properties, such as tensile strength, and occurrence of cracks in molded products dip-molded from the latex composition for dip molding containing the nitrile-based copolymer latex or carboxylic acid-modified nitrile-based copolymer latex. It has a low stickiness effect and provides excellent wearing comfort. The glass transition temperature may be measured using differential scanning calorimetry.

In addition, according to one embodiment of the present invention, the average particle diameter of the nitrile-based copolymer in the nitrile-based copolymer latex or the carboxylic acid-modified nitrile-based copolymer particles in the carboxylic acid-modified nitrile-based copolymer latex is 100 nm to 500 nm, It may be 100 nm to 200 nm, or 120 nm to 150 nm, and within this range, the viscosity of the nitrile-based copolymer latex or the carboxylic acid-modified nitrile-based copolymer latex does not increase, so that the nitrile-based copolymer latex or the carboxylic acid-modified nitrile-based copolymer latex does not increase. Nitrile-based copolymer latex can be produced at a high concentration, and the tensile properties such as tensile strength of molded products dip molded from the first latex composition for dip molding containing it are excellent. In addition, within the above range, the film formation speed is excellent, resulting in excellent synergy characteristics. The average particle diameter may be measured using a laser scattering analyzer (Nicomp).

In addition, according to one embodiment of the present invention, the first latex composition for dip molding has a solid content (concentration) of 10% by weight to 40% by weight, 15% by weight to 35% by weight, or 18% by weight to 33% by weight. It may be % by weight, and within this range, the efficiency of latex transportation is excellent and the storage stability is excellent by preventing an increase in latex viscosity.

As another example, the first latex composition for dip molding may have a pH of 8 to 12, 9 to 11, or 9.3 to 10.5, and within this range, it has excellent processability and productivity when manufacturing dip molded products. The pH of the latex composition for dip molding can be adjusted by adding the pH adjuster described above. For example, the pH adjuster may be an aqueous solution of potassium hydroxide at a concentration of 1% to 5% by weight, or aqueous ammonia at a concentration of 1% to 5% by weight.

Meanwhile, according to one embodiment of the present invention, in order to maximize the antistatic effect of the dip molded product, an antistatic polymer is added when manufacturing the latex composition for dip molding to produce a first latex composition for dip molding containing the antistatic polymer. Rather than forming a derived layer, that is, a dip molding layer, a second dip molding latex composition derived layer that does not contain an antistatic polymer is formed in a dip molding mold to which a coagulant is attached, and then the antistatic polymer derived layer is formed. In this case, the dip molding layer may include a layer derived from a latex composition for dip molding and a layer derived from an antistatic polymer.

As a specific example, the method of manufacturing a dip molded product when the dip molding layer includes a layer derived from a second latex composition for dip molding and a layer derived from an antistatic polymer can produce a dip molded product as shown in FIG. 1(b). As a more specific example, attaching a coagulant to a dip mold (S100); The dip molding mold to which the coagulant is attached is filled with at least one copolymer selected from the group consisting of nitrile-based copolymers and carboxylic acid-modified nitrile-based copolymers; and a phenol-based emulsifier; forming a layer derived from the second latex composition for dip molding by immersing in the second latex composition for dip molding (S200); And it may include a step (S300) of forming an antistatic polymer-derived layer by immersing the dip molding mold on which the second dip molding latex composition-derived layer is formed in a solution containing an antistatic polymer.

The step (S100) may be a step of attaching the coagulant to the surface of the dip mold by immersing the dip mold in a coagulant solution to form a coagulant in the dip mold, and is carried out in the same manner as the previously mentioned step (S10). It can be.

The step (S200) is a step of immersing a dip mold to which a coagulant is attached in order to form a dip molding layer into the second dip molding latex composition, taking it out, and forming a layer derived from the second dip molding latex composition in the dip molding mold. It may be performed in the same manner as the step (S20) mentioned above.

Meanwhile, according to one embodiment of the present invention, the second latex composition for dip molding in the step (S200) is produced by polymerizing a nitrile-based copolymer or polymerizing a carboxylic acid-modified nitrile-based copolymer to form a nitrile-based copolymer latex, Or preparing a carboxylic acid-modified nitrile-based copolymer latex (S201); and a step (S202) of adding and mixing a phenol-based emulsifier and a cross-linking agent composition to the nitrile-based copolymer latex or the carboxylic acid-modified nitrile-based copolymer latex prepared in the step (S201). The step (S201) may be performed in the same manner as the step (S21) mentioned above, and the step (S202) may be performed in the same manner as the step (S22) mentioned above.

According to one embodiment of the present invention, in the step (S300), in order to form a dip molding layer, the dip molding mold on which the layer derived from the second dip molding latex composition is formed is immersed in an antistatic polymer solution, taken out, and placed in the dip molding mold. This may be a step of forming an antistatic polymer-derived layer.

In order to form a dip molding layer in the (S300) dip molding mold, the dip molding mold on which the second dip molding latex composition-derived layer is formed is placed in the antistatic polymer solution for less than 1 minute, 1 second to 30 seconds, or 1 second. It may further include dipping for 10 to 10 seconds, taking it out, and drying it at 30°C to 70°C, 30°C to 60°C, or 35°C to 55°C.

According to one embodiment of the present invention, the step (S20) or step (S300) may further include drying and heating to completely form the dip molding layer attached to the dip molding mold after immersion, During drying and heating, liquid components such as water first evaporate, and then through a crosslinking reaction between the nitrile-based copolymer or carboxylic acid-modified nitrile-based copolymer in the first or second dip molding latex composition and the crosslinking agent. Curing may be effected.

Thereafter, the dip molded layer crosslinked by heat treatment can be peeled off from the dip mold to obtain a dip molded product.

According to one embodiment of the present invention, the molded article may be a glove such as surgical gloves, examination gloves, industrial gloves, and household gloves, condoms, catheters, or health care products.

Hereinafter, the present invention will be described in more detail through examples. However, the following examples are intended to illustrate the present invention, and it is obvious to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention, and the scope of the present invention is not limited to these alone.

Example

Example 1

<Manufacture of latex composition for dip molding>

A 10L high-pressure reactor equipped with a stirrer, thermometer, cooler, nitrogen gas inlet, and an inlet for continuously introducing monomers, emulsifiers, and polymerization initiators was replaced with nitrogen, and then 25% by weight of acrylonitrile, 1,3% by weight, was added to the reactor. -A monomer mixture consisting of 70% by weight of butadiene and 5% by weight of methacrylic acid, and 2.5 parts by weight of sodium dodecyl benzene sulfonate, 0.5 parts by weight of t-dodecyl mercaptan, and 140 parts by weight of water were added to 100 parts by weight of the monomer mixture. And the temperature was raised to 40°C. After the temperature of the reactor reached 40°C, polymerization was performed by adding 0.25 parts by weight of potassium persulfate, a polymerization initiator, and when the polymerization conversion rate was 95%, 0.1 parts by weight of sodium dimethyl dithiocarbamate was added to stop the polymerization. I ordered it. Subsequently, unreacted monomers were removed through a deodorization process, and ammonia water, antioxidants, and antifoaming agents were added to obtain carboxylic acid-modified nitrile-based copolymer latex with a solid content of 45% by weight and pH of 8.5. At this time, the glass transition temperature of the prepared carboxylic acid-modified nitrile-based copolymer latex was -30°C, and the average particle diameter of the carboxylic acid-modified nitrile-based copolymer in the latex was 120 nm.

Next, to 100 parts by weight (based on solid content) of the carboxylic acid-modified nitrile-based copolymer latex obtained above, 2 parts by weight of a potassium hydroxide solution with a concentration of 1.25% by weight, 0.5 parts by weight of a phenol-based emulsifier (TSP-16, steppan), and sulfur powder 1.2 parts by weight, 0.7 parts by weight of zinc di-n-butyldithiocarbamate, 0.1 parts by weight of PEDOT:PSS, and double distilled water were added to obtain a latex composition for dip molding with a solid content concentration of 18% by weight and a pH of 10.0.

<Manufacture of deep molded products>

A coagulant solution was prepared by mixing 18 parts by weight of calcium nitrate, 81.5 parts by weight of water, and 0.5 parts by weight of a wetting agent (Teric 320, Huntsman Corporation, Australia). The hand-shaped ceramic mold was immersed in the prepared coagulant solution for 3 minutes, taken out, dried at 80°C for 4 minutes, and the coagulant was applied to the hand-shaped mold.

Thereafter, the mold to which the coagulant was applied was immersed in the obtained latex composition for dip molding for 3 minutes, taken out, and dried at 80° C. for 2 minutes. Next, the hand-shaped mold was immersed in the monomer solution for 3 minutes, taken out and dried at 40° C. for 10 minutes, and the dip molded product was peeled off from the hand-shaped mold to obtain a glove-shaped dip molded product.

Example 2

<Manufacture of latex composition for dip molding>

A 10L high-pressure reactor equipped with a stirrer, thermometer, cooler, nitrogen gas inlet, and an inlet for continuously introducing monomers, emulsifiers, and polymerization initiators was replaced with nitrogen, and then 25% by weight of acrylonitrile, 1,3% by weight, was added to the reactor. -A monomer mixture consisting of 70% by weight of butadiene and 5% by weight of methacrylic acid, and 2.5 parts by weight of sodium dodecyl benzene sulfonate, 0.5 parts by weight of t-dodecyl mercaptan, and 140 parts by weight of water were added to 100 parts by weight of the monomer mixture. And the temperature was raised to 40°C. After the temperature of the reactor reached 40°C, polymerization was performed by adding 0.25 parts by weight of potassium persulfate, a polymerization initiator, and when the polymerization conversion rate was 95%, 0.1 parts by weight of sodium dimethyl dithiocarbamate was added to stop the polymerization. I ordered it. Subsequently, unreacted monomers were removed through a deodorization process, and ammonia water, antioxidants, and antifoaming agents were added to obtain carboxylic acid-modified nitrile-based copolymer latex with a solid content of 45% by weight and pH of 8.5. At this time, the glass transition temperature of the prepared carboxylic acid-modified nitrile-based copolymer latex was -30°C, and the average particle diameter of the carboxylic acid-modified nitrile-based copolymer in the latex was 120 nm.

Next, to 100 parts by weight (based on solid content) of the carboxylic acid-modified nitrile-based copolymer latex obtained above, 2 parts by weight of a potassium hydroxide solution with a concentration of 1.25% by weight, 0.5 parts by weight of a phenol-based emulsifier (TSP-16, steppan), and sulfur powder 1.2 parts by weight, 0.7 parts by weight of zinc di-n-butyldithiocarbamate, and double distilled water were added to obtain a latex composition for dip molding with a solids concentration of 18% by weight and a pH of 10.0.

<Manufacture of deep molded products>

A coagulant solution was prepared by mixing 18 parts by weight of calcium nitrate, 81.5 parts by weight of water, and 0.5 parts by weight of a wetting agent (Teric 320, Huntsman Corporation, Australia). The hand-shaped ceramic mold was immersed in the prepared coagulant solution for 3 minutes, taken out, dried at 80°C for 4 minutes, and the coagulant was applied to the hand-shaped mold.

Thereafter, the mold to which the coagulant was applied was immersed in the obtained latex composition for dip molding for 3 minutes, taken out, and dried at 80° C. for 2 minutes. Then, the hand-shaped mold was dipped into the monomer solution for 3 minutes, taken out and dried at 40°C for 10 minutes, dipped into a PEDOT:PSS 1% aqueous solution for 3 seconds, taken out and dried at 45°C for 10 minutes, and the dip molded product was hand dried. A glove-shaped dip molded product was obtained by peeling it from the shaped mold.

Example 3

In Example 1, when preparing a latex composition for dip molding, 0.5 parts by weight of a phenolic emulsifier (TSP-2850, Steppan) was used instead of 0.5 parts by weight of a phenolic emulsifier (TSP-16, Steppan). The same as Example 1. It was carried out using this method.

Example 4

In Example 2, when preparing a latex composition for dip molding, 0.5 parts by weight of a phenolic emulsifier (TSP-2850, Steppan) was used instead of 0.5 parts by weight of a phenolic emulsifier (TSP-16, Steppan). The same as Example 1. It was carried out using this method.

Example 5

In Example 1, the latex composition for dip molding was prepared in the same manner as Example 1, except that 1 part by weight of PEDOT:PSS was used instead of 0.1 part by weight.

Example 6

In Example 1, the latex composition for dip molding was prepared in the same manner as Example 1, except that 1.5 parts by weight of PEDOT:PSS was used instead of 0.1 parts by weight.

Comparative Example 1

In Example 1, the latex composition for dip molding was prepared in the same manner as Example 1 without using a phenol-based emulsifier (TSP-16, steppan) and PEDOT:PSS.

Comparative Example 2

In Example 1, the latex composition for dip molding was prepared in the same manner as Example 1 without using a phenol-based emulsifier (TSP-16, steppan).

Comparative Example 3

In Example 1, the latex composition for dip molding was prepared in the same manner as Example 1 without using PEDOT:PSS.

Experiment example

To compare the physical properties of each dip molded product manufactured in Examples 1 to 6 and Comparative Examples 1 to 3, surface resistance, tensile strength, elongation, and stress at 300% and 500% were measured and are shown in Table 1 below. .

*Surface resistance [MΩ/sq]: Measured using PROSTAT's PRS-801 measuring device at room temperature.

* Tensile strength (MPa), elongation, stress at 300% elongation (MPa), and stress at 500% elongation (MPa): A dumbbell-shaped specimen was produced in accordance with EN 455-2. This specimen was then pulled at an elongation rate of 500 mm/min, and the stress and tensile strength at break were measured when the elongation rates were 300% and 500%, respectively.

division Example Comparative example One 2 3 4 5 6 One 2 3 surface resistance
(MΩ/sq) 11.2 0.53 13.0 0.61 3.3 3.1 ∞ 20 ∞ tensile strength
(MPa) 33.251 36.517 33.005 36.282 30.494 31.051 34.477 31.623 35.311 300% modulus
(MPa) 5.230 6.251 5.196 6.040 4.887 4.799 5.587 5.922 5.462 500% modulus
(MPa) 12.041 14.724 12.324 14.622 11.274 11.812 13.297 14.054 12.871

As shown in Table 1, the Examples including both the phenol-based emulsifier and the antistatic polymer when manufacturing dip molded products were at an equivalent or higher level when compared to the Comparative Examples that did not include either the phenolic emulsifier or the antistatic polymer. It was confirmed that the tensile properties of

Meanwhile, in the case of Examples 1 to 6 manufactured according to the present invention, it was confirmed that the inclusion of both a phenol-based emulsifier and an antistatic polymer reduced the electrical resistance of the surface of the dip molded product and prevented the generation of static electricity.

On the other hand, in the case of Comparative Examples 1 and 3, which do not contain an antistatic polymer, the electrical resistance of the surface of the dip molded product is infinite, confirming that the manufactured dip molded product exhibits non-conductivity, and includes an antistatic polymer but does not contain a phenol-based emulsifier. In the case of Comparative Example 2, which did not include a phenol-based emulsifier and an antistatic polymer, the electrical resistance of the surface was greater than that of the example prepared including both an antistatic polymer, and it was confirmed that the antistatic effect was minimal.

Claims (10)

At least one copolymer selected from the group consisting of nitrile-based copolymers and carboxylic acid-modified nitrile-based copolymers; Phenolic emulsifier; and an antistatic polymer,
The phenol-based emulsifier is a dip molded product represented by the following formula (1):
[Formula 1]

In Formula 1, R ₁ , R ₂ and R ₃ are each independently hydrogen; or substituted or unsubstituted linear or branched alkyl having 1 to 30 carbon atoms, where at least one of R ₁ to R ₃ is substituted or unsubstituted linear or branched alkyl having 1 to 30 carbon atoms, and R silver hydrogen; Polymerizable functional group; An alkoxy group having 1 to 30 carbon atoms; inorganic or organic salts; non-ionic group; or halogen, m is an integer from 1 to 20, and n is an integer from 1 to 100. According to paragraph 1,
The antistatic polymer is from the group consisting of polyethylenedioxythiophene:polystyrenesulfonate (PEDOT:PSS), polyacetylene, polypyrrole, polythiophene, polyparaphenylene, polyphenylene sulfide, polyparaphenylene vinylene, and polyaniline. A dip molded product containing one or more selected species. According to paragraph 1,
The antistatic polymer is a dip molded product in an amount of 0.005 parts by weight to 2 parts by weight based on 100 parts by weight of at least one copolymer selected from the group consisting of the nitrile-based copolymer and the carboxylic acid-modified nitrile-based copolymer. delete According to paragraph 1,
The phenol-based emulsifier is a dip molded product represented by the following formula (2):
[Formula 2]

In Formula 2, R is hydrogen; Polymerizable functional group; an alkoxy group having 1 to 10 carbon atoms; inorganic or organic salts; non-ionic group; or halogen, and n is an integer from 1 to 100. According to paragraph 1,
A dip molded product in which the phenol-based emulsifier is contained in an amount of 0.1 to 4 parts by weight based on 100 parts by weight of the carboxylic acid-modified nitrile-based copolymer based on solid content. According to paragraph 1,
The molded article includes at least one copolymer selected from the group consisting of nitrile-based copolymers and carboxylic acid-modified nitrile-based copolymers; Phenolic emulsifier; and a first dip molding latex composition-derived layer containing an antistatic polymer. According to paragraph 1,
The molded article includes at least one copolymer selected from the group consisting of nitrile-based copolymers and carboxylic acid-modified nitrile-based copolymers; and a second dip molding latex composition-derived layer containing a phenol-based emulsifier, and an antistatic polymer-derived layer containing an antistatic polymer. Attaching a coagulant to the dip mold (S10); and
The dip molding mold to which the coagulant is attached is filled with at least one copolymer selected from the group consisting of nitrile-based copolymers and carboxylic acid-modified nitrile-based copolymers; Phenolic emulsifier; and forming a layer derived from the first latex composition for dip molding by immersing in the first latex composition for dip molding containing an antistatic polymer (S20). Attaching a coagulant to the dip mold (S100);
The dip molding mold to which the coagulant is attached is filled with at least one copolymer selected from the group consisting of nitrile-based copolymers and carboxylic acid-modified nitrile-based copolymers; and a phenol-based emulsifier; forming a layer derived from the second latex composition for dip molding by immersing in the second latex composition for dip molding (S200); and
A method for producing a dip molded product comprising a step (S300) of forming an antistatic polymer derived layer by immersing the dip mold on which the second dip molding latex composition-derived layer is formed in a solution containing an antistatic polymer.