KR20200090050A - Dip article and method of preparing the same - Google Patents

Abstract

The present invention relates to a dip molded article. More particularly, the present invention provides a dip molded article comprising: at least one copolymer selected from the group consisting of a nitrile-based copolymer and a carboxylic acid-modified nitrile-based copolymer; a phenolic emulsifier; and an antistatic polymer, and a manufacturing method thereof. The present invention can expect an antistatic effect due to the antistatic polymer included in the dip molded article.

Description

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

The present invention relates to a dip molded article, and more particularly, to a dip molded article and a manufacturing method thereof.

Conventionally, natural rubber has been mainly used as a raw material for products requiring elasticity, such as gloves for industrial use, medical use, and food, and balloons and condoms. However, recently, natural rubber is being replaced with nitrile rubber instead of natural rubber due to side effects that cause serious protein allergy to some users. Nitrile-based rubber has a high oil resistance, and is especially used in work gloves used by users dealing with organic solvents, or in medical and food gloves. In addition, products made from nitrile-based rubber have characteristics that are not easily pierced by injection needles, etc., compared to products made from natural rubber, and thus have an advantage that is suitable for medical personnel handling sharp scalpels or injection needles.

In addition, in recent years, due to the unstable supply and demand of natural rubber, many glove manufacturing companies are converting the natural rubber glove production line to a nitrile rubber glove production line, and as safety awareness increases, disposable gloves made from nitrile rubber Usage is steadily increasing.

However, when using non-conductive natural rubber and carboxylic acid-modified nitrile-based gloves, large and small static electricity inevitably occurs, and static electricity generated at this time causes fine foreign matter such as dust to stick to the gloves to contaminate the gloves. There are problems causing.

KR 2018-0087588 A KR 2017-0006686 A

The problem to be solved in the present invention, in order to solve the problems mentioned in the technology that is the background of the invention, when manufacturing a dip molded article, such as gloves, prevents electrostatic and physical adsorption of fine contaminants of the dip molded article An object of the present invention is to provide a dip-molded product for manufacturing and a method for manufacturing the same.

According to an embodiment of the present invention for solving the above problems, the present invention is at least one copolymer selected from the group consisting of a nitrile-based copolymer and a carboxylic acid-modified nitrile-based copolymer; Phenolic emulsifiers; And an antistatic polymer.

In addition, the present invention is a step of attaching a coagulant to the dip molding mold (S10); And one or more copolymers selected from the group consisting of a nitrile-based copolymer and a carboxylic acid-modified nitrile-based copolymer for the dip molding frame to which the coagulant is attached; Phenolic emulsifiers; And immersing in a first dip molding latex composition comprising an antistatic polymer to form a layer derived from the first dip molding latex composition (S20).

In addition, the present invention is a step of attaching a coagulant to the dip molding mold (S100); One or more copolymers selected from the group consisting of a nitrile-based copolymer and a carboxylic acid-modified nitrile-based copolymer for the dip molding mold to which the coagulant is attached; And a phenol-based emulsifier; immersing in a second dip molding latex composition to form a second dip molding latex composition derived layer (S200); And immersing the dip molding mold in which the second latex composition for dip molding derived layer is formed in a solution containing an antistatic polymer to form an antistatic polymer derived layer (S300). .

In the case of manufacturing the dip molded article according to the present invention, an antistatic effect can be expected due to the antistatic polymer contained in the dip molded article, and thereby, the effect of preventing electrostatic and physical adsorption to the micropollutants of the dip molded article There is.

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

Terms or words used in the description and claims of the present invention should not be construed as being limited to ordinary or lexical meanings, and the inventor appropriately explains the concept of terms in order to best explain his or her invention in the best way. Based on the principle that it can be defined, it should be interpreted as meanings and concepts consistent with the technical spirit of the present invention.

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

In the present invention, the term'monomer-derived repeating unit' may refer to a component, a structure derived from a monomer, or a substance itself, and in a specific example, upon polymerization of a polymer, a monomer to be introduced participates in a polymerization reaction and is repeated in 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 for example, a polymer on rubber or a copolymer on rubber polymerized by emulsion polymerization. It may mean that the fine particles are present 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 in a specific example, when manufacturing a dip molded article, the polymer or copolymer is attached, fixed, and/or polymerized on a dip mold to form a polymer or It may mean a layer formed from a copolymer.

In the present invention, the term'cross-linked portion derived from a compound' may refer to a component, a structure, or a substance itself derived from a compound, and a cross-linking agent composition functions and reacts to perform cross-linking in a polymer or a polymer formed by reaction. It may mean a cross-linking part (cross linking part).

The term'alkyl' in the present invention is 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, and may include that which is substituted by a substituent as well as unsubstituted.

The term'cycloalkyl' in the present invention is cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, cyclooctyl, decahydronaphthalenyl, adamantanyl, norbornyl (ie, Bicyclo [2,2,1] hept-5-enyl) and the like, wherein at least one hydrogen atom of the alkyl group as defined above is saturated or unsaturated non-aromatic monovalent monocyclic, bicyclic or cyclic hydrocarbon. It may mean that it is substituted with a tricyclic hydrocarbon, and it may mean that it includes not only unsubstituted but also substituted by a substituent.

In the present invention, the term'aryl' may mean that one or more hydrogen atoms of the alkyl group as defined above are substituted with an aryl group, such as phenyl, naphthalenyl, fluorenyl, and the like, as well as unsubstituted substituents. It may mean to include those substituted by.

In the present invention, the term'alkenyl' refers to a linear or linear carbon atom, such as ethenyl, 1-propenyl, 2-propenyl, 2-butenyl, 3-butenyl, pentenyl, 5-hexenyl, dodecenyl, etc. It may mean 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 unsubstituted as well as substituted by a substituent. It can mean to include.

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 a nitrile-based copolymer and a nitric acid-based copolymer; Phenolic emulsifiers; And antistatic polymers.

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

According to an 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, A dip molded article formed from a latex composition for dip molding, which may be 0.01 parts by weight to 1 part by weight, or 0.1 parts by weight to 1.5 parts by weight, and includes the nitrile-based copolymer or carboxylic acid-modified nitrile-based copolymer within this range It has the effect of being flexible, excellent in touch and wearing, and excellent in oil resistance and tensile strength.

According to an 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. Further, according to an 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. have.

According to an embodiment of the present invention, the ethylenically unsaturated nitrile-based monomer forming a 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 or methacrylonitrile. , Fumaronitrile, α-chloronitrile, and α-cyano ethyl acrylonitrile, and may be one or more selected from the group consisting of, for example, acrylonitrile and methacrylonitrile, and more specifically, acrylonitrile. Nitrile.

The content of the repeating units derived from the ethylenically unsaturated nitrile-based monomers of the nitrile-based copolymer and the carboxylic acid-modified nitrile-based copolymer, respectively, is 10 weights based on the total content of the nitrile-based copolymer or the carboxylic acid-modified nitrile-based copolymer, respectively. % To 50% by weight, 15% to 45% by weight, or 20% to 40% by weight, and within this range, the dip latex for dip molding comprising the nitrile-based copolymer or the carboxylic acid-modified nitrile-based copolymer The dip molded article molded from the composition is flexible, has excellent feel and fit, and has excellent oil resistance and tensile strength.

According to an embodiment of the present invention, the conjugated diene-based monomer forming the repeating unit derived from the conjugated diene-based 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 thereof may be 1,3-butadiene or isoprene, and more As a specific example, it may be 1,3-butadiene.

The content of the repeating unit derived from the conjugated diene-based monomer contained in the nitrile-based copolymer is 50% to 90% by weight, 55% to 85% by weight, or 60% to 80% by weight relative to the total content of the nitrile-based copolymer. The content of the repeating unit derived from the conjugated diene-based monomer contained in the carboxylic acid-modified nitrile-based copolymer may be 40 wt% to 89 wt%, 40 wt% to 80 based on the total content of the carboxylic acid-modified nitrile-based copolymer It may be 50% by weight, or 50% by weight to 78% by weight, and within this range, a dip molded article formed from a latex composition for dip molding comprising the nitrile-based copolymer or the carboxylic acid-modified nitrile-based copolymer is flexible, At the same time, it has an excellent effect on touch and wearing, and has an excellent oil resistance and tensile strength.

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

The content of the repeating unit derived from the ethylenically unsaturated acid monomer contained in the carboxylic acid-modified nitrile-based copolymer is 0.1% to 15% by weight, 0.5% to 9% by weight, or It may be 1% by weight to 8% by weight, and within this range, the dip-molded article molded from the latex composition for dip molding containing the carboxylic acid-modified nitrile-based copolymer is flexible, has excellent fit, and at the same time is resistant and tensile It has an excellent strength effect.

According to an embodiment of the present invention, the nitrile-based copolymer and the carboxylic acid-modified nitrile-based copolymer are repeat units derived from conjugated diene monomers, repeat units derived from ethylenically unsaturated nitrile monomers, and repeat units derived from ethylenically unsaturated acid monomers. 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 is 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 Ethylenically unsaturated amide monomer selected from the group consisting of; Non-conjugated diene monomers such as vinyl pyridine, vinyl norbornene, dicyclo pentadiene 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, (meth)acrylic acid 1-cyanopropyl, (meth)acrylic acid 2-ethyl-6-cyanohexyl, (meth)acrylic acid 3-cyanopropyl, (meth)acrylic acid hydroxyethyl, (meth)acrylic acid hydroxy It may be one or more 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 the 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 relative to the total content of the coalescence, and for dip molding including the nitrile-based copolymer or the carboxylic acid-modified nitrile-based copolymer within this range The dip molded article molded from the latex composition is excellent in touch and fit, and has excellent tensile strength.

According to one embodiment of the 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 a substituted or unsubstituted linear or branched alkyl having 1 to 30 carbon atoms, 1 to 20 carbon atoms, or 1 to 10 carbon atoms, wherein at least one of R ₁ to R ₃ is substituted or unsubstituted carbon atoms 1 to 30 carbon atoms linear or branched alkyl, R is hydrogen; Polymerizable functional groups; An alkoxy group having 1 to 30 carbon atoms, 1 to 20 carbon atoms, or 1 to 10 carbon atoms; Inorganic or organic salts; Nonionic group; Or halogen, m is an integer from 1 to 20, 1 to 10, or 1 to 5, and n is an integer from 1 to 100, 4 to 80, or 8 to 25.

Substituents which 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, and 6 to 10 carbon atoms; And it may be one or more selected from the group consisting of halogen.

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

Said cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, cyclooctyl, decahydronaphthalenyl, adamantanyl, norbornyl (ie bicyclo [2, 2,1] hept-5-enyl) and the like.

The aryl may be phenyl, naphthalenyl, fluorenyl, and the like.

The polymerizable functional group is (meth)acrylate; Alkyl (meth)acrylates having 1 to 30 carbon atoms, 1 to 20 carbon atoms, or 1 to 10 carbon atoms; And it may be one or more selected from the group consisting of alkenyl (meth) acrylate having 2 to 30 carbon atoms, 2 to 20 carbon atoms, 2 to 10 carbon atoms.

The alkoxy group may be methoxy, ethoxy, protoxy, isobutylmethoxy, butoxy, and the like.

The inorganic or organic salt is phosphonate (-PO ₃ -M ⁺ ), phosphate (PO ₄ -M ⁺ ), sulfate (SO ₄ -M ⁺ ), sulfonate (SO ₃ -M ⁺ ), carboxylate ( COO-M ⁺ ). In this case, M ⁺ may be H ⁺ , Na ⁺ , NH ₄ ⁺ , K ⁺ , Li ^+, or the like.

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

The halogen may be F, Cl, Br, I, and the like.

등 일 수 있다. As a specific example, R ₁ , R ₂ and R ₃ are each independently hydrogen, butyl, tert-butyl, isobutyl,

Etc.

According to an embodiment of the present invention, the phenolic emulsifier may be represented by the following Chemical Formula 2.

[Formula 2]

In Formula 2, R is hydrogen; Polymerizable functional groups; An alkoxy group having 1 to 10 carbon atoms; Inorganic or organic salts; Nonionic group; Or halogen, n is an integer from 1 to 100, 4 to 80, or 8 to 25.

The polymerizable functional group is (meth)acrylate; Alkyl (meth)acrylates having 1 to 30 carbon atoms, 1 to 20 carbon atoms, or 1 to 10 carbon atoms; And it may be one or more selected from the group consisting of alkenyl (meth) acrylate having 2 to 30 carbon atoms, 2 to 20 carbon atoms, 2 to 10 carbon atoms.

The alkyl (meth)acrylate is methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, Heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and the like.

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

In another example, the polymerizable functional groups are acryl, methacryl, acrylamido, methacrylamido, diallylamino, allyl ether, vinyl ether, α-alkenyl, maleinido, styrenyl, and α- It may be one or more selected from the group consisting of alkyl styrenyl groups.

The content of the phenolic 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, In this range, not only the syneresis time to the latex composition for dip molding containing the phenolic emulsifier is increased to improve stability, but also the modulus is reduced, so that the molded product manufactured using the latex composition for dip molding is worn. It has an excellent effect.

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 the dispersion in the solvent is excellent within this range, so that the nitrile-based copolymer latex or car When manufacturing the present acid-modified nitrile-based copolymer latex, the stability of the nitrile-based copolymer latex or the carboxylic acid-modified nitrile-based latex is improved, and the syneresis time of the latex composition for dip molding is increased to improve stability and reduce modulus. There is an excellent effect of wearing a molded article manufactured using a latex composition for dip molding.

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

On the other hand, when the phenol-based emulsifier includes a bulky benzene ring as well as a hydrophilic group, such as the phenol-based emulsifier represented by Formula 2, when preparing a molded article with a composition for dip molding containing the same, it serves to slow the film formation. It has the effect of increasing the syneresis time.

The dip molded article according to the present invention may include an antistatic polymer, thereby preventing electrostatic and physical adsorption to micro contaminants due to the antistatic effect in the manufacture of the dip molded article. The antistatic polymer is a water-soluble polymer material exhibiting conductivity, and serves to impart conductivity to a dip molded article including the same. That is, when manufacturing a dip molded product, static electricity may be generated due to the continuous accumulation of electrons in a non-conductive dip molded product. When an antistatic polymer is included, the accumulation of electrons can be prevented, thereby preventing static electricity. have.

On the other hand, the dip molded article according to the present invention includes both an antistatic polymer and a phenolic emulsifier when manufacturing the dip molded article, thereby further increasing the conductivity, and thus has an excellent antistatic effect.

For example, when dip molded products are used, polyethylene dioxythiophene: polystyrene sulfonate (PEDOT: PSS) is used as an antistatic polymer in combination with a phenolic emulsifier, and polystyrene sulfonate material, which is a non-conductor of polyethylene dioxythiophene: polystyrene sulfonate, is extracted. At this time, the polyethylene dioxythiophene: polystyrene sulfonate is changed to a polyethylene dioxythiophene: phenolic emulsifier, and the conductivity is increased due to excellent contact between particles made of polyethylene dioxythiophene, thereby preventing antistatic effect. There is.

In addition, the present invention provides a dip molded article manufacturing method for manufacturing the dip molded article. The dip molded product manufacturing method may include a step of dipping the latex composition for dip molding by a direct immersion method, an anode adhesion immersion method, a teag adhesion immersion method, and the like, specifically, by an anode adhesion immersion method. It can be carried out, in this case there is an advantage that can obtain a dip molded article of a uniform thickness.

As a specific example, the method for manufacturing a dip molded article may be manufactured as a dip molded article as shown in FIG. 1(a), and in a more specific example, attaching a coagulant to the dip mold (S10); And one or more copolymers selected from the group consisting of a nitrile-based copolymer and a carboxylic acid-modified nitrile-based copolymer for the dip molding frame to which the coagulant is attached; Phenolic emulsifiers; And immersing in a first dip molding latex composition containing an antistatic polymer to form a layer derived from the first dip molding latex composition (S20).

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

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

The coagulant is a metal halide such as barium chloride, calcium chloride, magnesium chloride, zinc chloride and aluminum chloride; Nitrates such as barium nitrate, calcium nitrate and zinc nitrate; Acetates such as barium acetate, calcium acetate and zinc acetate; And it may be one or more selected from the group consisting of sulfates such as calcium sulfate, magnesium sulfate and aluminum sulfate, and specifically, it may be calcium chloride or calcium nitrate.

In addition, according to an embodiment of the present invention, the step (S10) is, for attaching the coagulant to the dip molding mold, the dip molding mold to the coagulant solution for at least 1 minute, 1 minute to 10 minutes, or 1 minute to 5 minutes After soaking, after taking out may further include a step of drying at 70 ℃ to 150 ℃, 70 ℃ to 130 ℃, or 70 ℃ to 100 ℃.

According to an embodiment of the present invention, in the step (S20), a dip molding frame to which a coagulant is attached is immersed in a first dip molding latex composition to form a dip molding layer, and taken out to take a first dip molding into a dip molding frame. It may be a step of forming a layer derived from the latex composition. As a specific example, the step (S20) may be carried out by repeating two or more times, two to twelve times, or two to ten times as necessary, in this case, by further solidifying the first layer of the latex composition for dip molding It has excellent mechanical properties such as tensile properties and durability of dip molded products.

In addition, according to an embodiment of the present invention, in the step (S20), to form a dip molding layer on a dip molding frame, a dip molding frame with a coagulant attached to the first dip molding latex composition for at least 1 minute, 1 It may further include a step of dipping for 10 minutes, or 1 minute to 5 minutes, and then drying at 70 °C to 150 °C, 70 °C to 130 °C, or 70 °C to 100 °C after removal.

On the other hand, according to an embodiment of the present invention, the first dip molding latex composition of step (S20) polymerizes a nitrile-based copolymer or a carboxylic acid-modified nitrile-based copolymer by polymerizing a nitrile-based copolymer latex, Or preparing a carboxylic acid-modified nitrile-based copolymer latex (S21); And (S21) in the nitrile-based copolymer latex prepared in step, or a carboxylic acid-modified nitrile-based copolymer latex, a phenol-based emulsifier, a crosslinking agent composition and an antistatic polymer is introduced and mixed (S22) Can.

According to an embodiment of the present invention, the polymerization of the nitrile-based copolymer or the carboxylic acid-modified nitrile-based copolymer of step (S21) may be carried out by emulsion polymerization. The polymerization may be carried out by polymerization of the monomer mixture, and each monomer included in the monomer mixture may be introduced in the type and content of the aforementioned monomers, and may be introduced in batches or continuously.

On the other hand, during the polymerization of the step (S21), the monomer mixture may be introduced into the polymerization reactor at the same time prior to polymerization, and a part of the monomer mixture is first introduced into the polymerization reactor, and the residual monomer mixture is introduced after polymerization is started. Can be practiced. As described above, when the monomer mixture is divided into inputs, when a repeat unit derived from a monomer derived from each monomer is formed in a nitrile-based copolymer or a carboxylic acid-modified nitrile-based copolymer, the monomers due to the reaction rate difference for each monomer are The distribution can be made uniform, and accordingly, there is an effect of improving the balance between the physical properties of a dip molded product prepared by including a nitrile-based copolymer or a carboxylic acid-modified nitrile-based copolymer. In addition, in the polymerization of the step (S21), the polymerization may be carried out by injecting the glycidyl ether-based compound together with the monomer mixture, in this case, a nitrile system prepared by the polymerization of the step (S21) A crosslinked portion derived from a glycidyl ether-based compound may be formed in the copolymer or the carboxylic acid-modified nitrile-based copolymer.

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 the presence of an emulsifier, polymerization initiator, activator and molecular weight modifier.

When the polymerization of the nitrile-based copolymer or the carboxylic acid-modified nitrile-based copolymer is performed including an emulsifier, the emulsifier is, for example, a group consisting of anionic surfactant, nonionic surfactant, cationic surfactant, and amphoteric surfactant. It may be at least one selected from the group, and specific examples may be at least one anionic surfactant selected from the group consisting of alkylbenzenesulfonates, aliphatic sulfonates, higher alcohol sulfate ester salts, α-olefin sulfonate salts and alkyl ether sulfate ester salts. have.

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

In addition, when polymerization of the nitrile-based copolymer or carboxylic acid-modified nitrile-based copolymer is carried out including a polymerization initiator, the polymerization initiator is an inorganic peroxide such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate and hydrogen peroxide. ; t-butyl peroxide, cumene hydro peroxide, p-mentanhydro peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, dibenzoyl peroxide Organic peroxides such as oxide, 3,5,5-trimethylhexanol peroxide and t-butyl peroxy isobutylate; It may be at least one selected from the group consisting of nitrogen compounds such as azobis isobutyronitrile, azobis-2,4-dimethylvalero nitrile, azobiscyclohexanecarbonitrile, and azobis isobutyrate (butyl acid) methyl, and the like. A specific example may be an inorganic peroxide, and a more specific example may be a 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 amount of the monomer mixture, and within this range The effect is easy to adjust.

In addition, when the polymerization of the nitrile-based copolymer or the carboxylic acid-modified nitrile-based copolymer is carried out including a molecular weight modifier, the molecular weight modifier 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 selected from the group consisting of sulfur-containing compounds such as tetraethyl thiuram disulfide, dipentamethylene thiuram disulfide, and diisopropylxanthogen disulfide, and more specifically mercaptans. As a specific example, it may be t-dodecyl mercaptan. The molecular weight modifier may be added in 0.1 parts by weight to 2 parts by weight, 0.2 parts by weight to 1.5 parts by weight, or 0.3 parts by weight to 1.0 parts by weight based on 100 parts by weight of the total amount of the monomer mixture, and has excellent polymerization stability within this range. And, when manufacturing a molded article after polymerization, there is an effect of excellent physical properties of the molded article.

In addition, when the polymerization of the nitrile-based copolymer or the carboxylic acid-modified nitrile-based copolymer is performed including an activator, the activator is sodium formaldehyde, sulfoxylate, sodium ethylenediamine teraacetate, ferrous sulfate , 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 amount of the monomer mixture, and the polymerization rate is titrated within this range. There is an effect that can be maintained at a level.

Further, 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, specifically, deionized water, as a medium, and in order to secure polymerization ease, if necessary It may be carried out by further including additives such as chelating agent, dispersing agent, pH adjusting agent, deoxidizing agent, particle size adjusting agent, anti-aging agent and oxygen scavenger.

According to an embodiment of the present invention, the emulsifier, polymerization initiator, molecular weight modifier, additives, etc. may be introduced into the polymerization reactor in a batch or divided manner, such as the monomer mixture, or may be continuously introduced at each input.

Further, according to an 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 °C to 90 °C, 20 °C to 80 °C, or 25 °C to 75 °C. It can be, and within this range, there is an effect of excellent latex stability.

On the other hand, according to an embodiment of the present invention, the step (S21) may include the step of obtaining a nitrile-based copolymer latex or carboxylic acid-modified nitrile-based copolymer latex by terminating the polymerization reaction. The termination of the polymerization reaction of the nitrile-based copolymer or the carboxylic acid-modified nitrile-based copolymer may be carried out at a time when the polymerization conversion rate is 90% or more, 90% to 99.9%, or 93% to 99%, a polymerization terminator, It can be carried out by adding a pH adjusting agent and an antioxidant. In addition, the (S21) step, after the completion of the reaction, may further include a step of removing unreacted monomers by a deodorization concentration process.

In addition, according to an embodiment of the present invention, the step of introducing and mixing a phenol-based emulsifier, a crosslinking agent composition and an antistatic polymer in the prepared nitrile-based copolymer latex or carboxylic acid-modified nitrile-based copolymer latex (S22) Can be practiced. The (S22) step may be a step for preparing a first dip molding latex composition for dip molding from a nitrile-based copolymer latex or a 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. In addition, the phenolic emulsifier may be different from the emulsifier introduced during polymerization described above.

In addition, according to an embodiment of the present invention, the antistatic polymer is mixed with the prepared nitrile-based copolymer or carboxylic acid-modified nitrile-based copolymer latex, and the micro-polluting material in the preparation of the first dip molding latex composition comprising the same It has the effect of preventing electrostatic and physical adsorption on.

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

According to an embodiment of the present invention, the vulcanizing agent is for vulcanizing the first dip molding latex composition, and may be sulfur, such as powdered sulfur, sedimented sulfur, colloidal sulfur, surface-treated sulfur, and insoluble sulfur. When forming a cross-linking portion including the sulfur, the sulfur is 0.1 parts by weight 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 Part, or may be 1 to 5 parts by weight, there is an excellent effect of crosslinking ability within this range.

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

When forming a cross-linking part including the vulcanization accelerator, the vulcanization accelerator is 0.1 parts by weight based on 100 parts by weight (based on solid content) of the nitrile-based copolymer or the 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, there is an excellent effect of crosslinking ability.

In addition, according to an embodiment of the present invention, zinc oxide in the crosslinking agent may be present in the form of a zinc oxide solution mixed in the first dip molding latex composition, the zinc oxide solution is zinc oxide, ammonium carbonate, ammonia water And may include water, 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, excellent crosslinking ability in this range, and latex stability Excellent, it has the effect of excellent tensile strength and flexibility of the manufactured dip molded product.

According to an 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 °C to -15 °C, -47 °C to -15 °C, or -45 °C to- It may be 20 ℃, within this range of the nitrile-based copolymer latex or a carboxylic acid-modified nitrile-based copolymer latex for dip molding from a latex composition for dip molding, such as the tensile strength of the molded product such as tensile strength degradation and crack generation While preventing, it is less sticky and has an excellent wearing effect. The glass transition temperature may be measured using a differential scanning calorimetry.

In addition, according to an 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 latex 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 carboxylic acid-modified nitrile-based copolymer latex is not increased so that the nitrile-based copolymer latex or carboxylic acid is modified. Nitrile-based copolymer latex can be prepared at a high concentration, and has excellent effect in tensile properties such as tensile strength of a molded product dip-formed from a first dip-molding latex composition containing the same. In addition, the film forming speed within the above range is excellent, there is an effect of excellent syneresis characteristics. The average particle diameter may be measured using a laser scattering analyzer (Nicomp).

In addition, according to an embodiment of the present invention, the first dip molding latex composition has, for example, 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 It may be a weight percent, and within this range, the efficiency of transporting latex is excellent, and an increase in latex viscosity is prevented to have an excellent storage stability.

As another example, the first dip molding latex composition may have a pH of 8 to 12, 9 to 11, or 9.3 to 10.5, and within this range, there is an effect of excellent workability and productivity when manufacturing a dip molded product. The pH of the latex composition for dip molding may be adjusted by the introduction of the pH adjusting agent described above. The pH adjusting agent may be, for example, 1% to 5% by weight of potassium hydroxide aqueous solution, or 1% to 5% by weight of ammonia water.

Meanwhile, according to an embodiment of the present invention, in order to maximize an antistatic effect of a dip molded product, a first dip molded latex composition containing the antistatic polymer is introduced by introducing an antistatic polymer when preparing the latex composition for dip molding Instead of forming a derived layer, i.e., a dip molding layer, after forming a second layer of a latex composition for dip molding that does not contain an antistatic polymer in a dip molding frame to which a coagulant is attached, an antistatic polymer derived layer is formed. In this case, the dip molding layer in this case may include a layer derived from a latex composition for dip molding and a layer derived from an antistatic polymer.

As a specific example, a dip molded article manufacturing method when the dip molded layer includes a layer derived from a second latex composition for dip molding and an antistatic polymer-derived layer can be produced as shown in FIG. 1(b), and more As a more specific example, attaching a coagulant to the dip molding mold (S100); One or more copolymers selected from the group consisting of a nitrile-based copolymer and a carboxylic acid-modified nitrile-based copolymer for the dip molding frame to which the coagulant is attached; And a phenol-based emulsifier; immersing in a second dip molding latex composition to form a second dip molding latex composition derived layer (S200); And immersing the dip molding frame in which the second latex composition for dip molding derived layer is formed in a solution containing an antistatic polymer to form an antistatic polymer derived layer (S300).

The (S100) step may be a step of attaching a coagulant to the surface of the dip molding frame by dipping the dip molding frame in a coagulant solution in order to form a coagulant in the dip molding frame, and is carried out in the same manner as the aforementioned (S10) step Can be.

In the step (S200), a dip molding frame to which a coagulant is attached is immersed in a second dip molding latex composition to form a dip molding layer, and taken out to form a layer derived from the second dip molding latex composition in a dip molding frame. It may be, it may be carried out in the same way as the above-mentioned (S20) step.

On the other hand, according to an embodiment of the present invention, the second dip molding latex composition of step (S200) polymerizes a nitrile-based copolymer, or a carboxylic acid-modified nitrile-based copolymer by polymerizing a nitrile-based copolymer latex, Or preparing a carboxylic acid-modified nitrile-based copolymer latex (S201); And in the nitrile-based copolymer latex prepared in step (S201), or a carboxylic acid-modified nitrile-based copolymer latex, a phenol-based emulsifier and a crosslinking agent composition may be added and mixed (S202). The step (S201) may be carried out in the same manner as the step (S21) mentioned above, and the step (S202) mentioned above (S22).

According to an embodiment of the present invention, in the step (S300), to form a dip molding layer, a dip molding mold having a layer derived from the second latex composition for dip molding is immersed in an antistatic polymer solution, and then taken out and dip molded It may be a step of forming a layer derived from an antistatic polymer.

In order to form a dip molding layer on the (S300) dip molding mold, a dip molding mold having a layer derived from a second dip molding latex composition is formed in the antistatic polymer solution within 1 minute, 1 second to 30 seconds, or 1 second. After soaking for 10 seconds, after taking out may further include a step of drying at 30 ℃ to 70 ℃, 30 ℃ to 60 ℃, or 35 ℃ to 55 ℃.

According to an embodiment of the present invention, the step (S20) or the step (S300) may further include a step of drying and heating to completely form a dip molding layer attached to the dip molding frame after immersion. During drying and heating, a liquid component such as water first evaporates, and a crosslinking reaction between a nitrile-based copolymer or a carboxylic acid-modified nitrile-based copolymer in a first dip molding latex composition or a second dip molding latex composition and a crosslinking agent Curing can be carried out.

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

According to an embodiment of the present invention, the molded article may be a surgical glove, an examination glove, an industrial glove, a glove such as a household glove, a condom, a catheter, or a health care product.

Hereinafter, the present invention will be described in more detail by examples. However, the following examples are intended to illustrate the present invention, and it is apparent to those skilled in the art that various changes and modifications can be made within the scope and technical scope of the present invention, and the scope of the present invention is not limited thereto.

Example

Example 1

<Production of latex composition for dip molding>

Agitator, thermometer, cooler, nitrogen gas inlet and monomer, emulsifier and polymerization initiator are replaced with nitrogen to replace the 10L high-pressure reactor equipped with an inlet so that nitrogen can be continuously introduced into the reactor, followed by acrylonitrile 25 wt%, 1,3 -A monomer mixture composed 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 with respect to 100 parts by weight of the monomer mixture And heated up 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 as a polymerization initiator, and when polymerization conversion was 95%, 0.1 part by weight of sodium dimethyl dithio carbamate was added to stop polymerization. Ordered. Subsequently, unreacted monomers were removed through a deodorization process, and ammonia water, an antioxidant, and an antifoaming agent were added to obtain a carboxylic acid-modified nitrile copolymer latex having a solid content concentration of 45% by weight and a 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 latex was 120 nm.

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

<Deep molded product manufacturing>

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). A hand-shaped ceramic mold was immersed in the prepared coagulant solution for 3 minutes, then taken out and dried at 80° C. for 4 minutes to apply the coagulant to the hand-shaped mold.

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

Example 2

<Production of latex composition for dip molding>

Agitator, thermometer, cooler, nitrogen gas inlet and monomer, emulsifier and polymerization initiator are replaced with nitrogen to replace the 10L high-pressure reactor equipped with an inlet so that nitrogen can be continuously introduced into the reactor, followed by acrylonitrile 25 wt%, 1,3 -A monomer mixture composed 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 with respect to 100 parts by weight of the monomer mixture And heated up 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 as a polymerization initiator, and when polymerization conversion was 95%, 0.1 part by weight of sodium dimethyl dithio carbamate was added to stop polymerization. Ordered. Subsequently, the unreacted monomer was removed through a deodorization process, and ammonia water, an antioxidant, and an antifoaming agent were added to obtain a carboxylic acid-modified nitrile copolymer latex having a solid content concentration of 45% by weight and a 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 latex was 120 nm.

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

<Deep molded product manufacturing>

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). A hand-shaped ceramic mold was immersed in the prepared coagulant solution for 3 minutes, then taken out and dried at 80° C. for 4 minutes to apply the coagulant to the hand-shaped mold.

Thereafter, the mold coated with the coagulant was immersed in the obtained latex composition for dip molding for 3 minutes, then taken out and dried at 80° C. for 2 minutes. Subsequently, the hand-shaped mold was immersed in the monomer solution for 3 minutes, taken out, dried at 40°C for 10 minutes, immersed in a PEDOT:PSS 1% aqueous solution for 3 seconds, then taken out and dried at 45°C for 10 minutes, and the dip molded product was hand operated. It was peeled from the shaped mold to obtain a glove-shaped dip molded article.

Example 3

In Example 1, when preparing the latex composition for dip molding, the same as in Example 1, except that 0.5 parts by weight of phenolic emulsifier (TSP-2850, steppan) was used instead of 0.5 parts by weight of phenolic emulsifier (TSP-16, steppan). It was carried out by the method.

Example 4

In Example 2, when producing the latex composition for dip molding, the same as in Example 1, except that 0.5 parts by weight of phenolic emulsifier (TSP-2850, steppan) was used instead of 0.5 parts by weight of phenolic emulsifier (TSP-16, steppan) It was carried out by the method.

Example 5

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

Example 6

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

Comparative Example 1

In Example 1, when preparing the latex composition for dip molding, it was carried out in the same manner as in Example 1 without using a phenolic emulsifier (TSP-16, steppan) and PEDOT:PSS.

Comparative Example 2

In Example 1, when preparing the latex composition for dip molding, it was carried out in the same manner as in Example 1 without using a phenolic emulsifier (TSP-16, steppan).

Comparative Example 3

In Example 1, when preparing the latex composition for dip molding, it was carried out in the same manner as in Example 1 without using PEDOT:PSS.

Experimental Example

To compare the physical properties of each of the dip molded products prepared 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 shown in Table 1 below. .

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

* Tensile strength (MPa), elongation, stress at 300% elongation (MPa) and stress at 500% elongation (MPa): Dumbbell-shaped specimens were prepared according to EN 455-2. Subsequently, the specimen was pulled at an elongation rate of 500 mm/min, and the tensile strength at break and the tensile strength at breaks of 300% and 500%, respectively, were measured.

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 ∞ The 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, when the dip molded article is prepared, an embodiment including both a phenolic emulsifier and an antistatic polymer is equivalent to or higher than a comparative example that does not include any of the phenolic emulsifier and an antistatic polymer. It was confirmed that the tensile properties of.

On the other hand, in the case of Examples 1 to 6 manufactured according to the present invention, it was confirmed that the production of the dip molded product includes both a phenolic emulsifier and an antistatic polymer to reduce the electrical resistance of the dip molded product surface to prevent static electricity generation.

On the other hand, in the case of Comparative Examples 1 and 3, which did not include the antistatic polymer, it can be confirmed that the dip molded article produced as the electrical resistance of the surface of the dip molded product is infinite, exhibits nonconductivity, and includes an antistatic polymer, but contains a phenolic emulsifier. In the case of Comparative Example 2, which did not include, it was confirmed that the anti-static effect was insignificant because the electrical resistance of the surface was greater than that of the example including both the phenolic emulsifier and the antistatic polymer.

Claims (10)

At least one copolymer selected from the group consisting of nitrile-based copolymers and carboxylic acid-modified nitrile-based copolymers; Phenolic emulsifiers; And an antistatic polymer. According to claim 1,
The antistatic polymer is in the group consisting of polyethylene dioxythiophene: polystyrene sulfonate (PEDOT: PSS), polyacetylene, polypyrrole, polythiophene, polyparaphenylene, polyphenylene sulfide, polyparaphenylene vinylene, polyaniline. Dip molded product comprising at least one selected. According to claim 1,
The antistatic polymer is a dip molded article that is included in 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. According to claim 1,
The phenolic emulsifier is a dip molded article 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 carbons, at least one of R ₁ to R ₃ is substituted or unsubstituted linear or branched alkyl having 1 to 30 carbons, R Silver hydrogen; Polymerizable functional groups; An alkoxy group having 1 to 30 carbon atoms; Inorganic or organic salts; Nonionic group; Or halogen, m is an integer from 1 to 20, and n is an integer from 1 to 100. According to claim 1,
The phenolic emulsifier is a dip molded article represented by the following formula (2):
[Formula 2]

In Formula 2, R is hydrogen; Polymerizable functional groups; An alkoxy group having 1 to 10 carbon atoms; Inorganic or organic salts; Nonionic group; Or halogen, n is an integer from 1 to 100. According to claim 1,
The phenolic emulsifier is a dip molded article that is included in 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. According to claim 1,
The molded article may include at least one copolymer selected from the group consisting of a nitrile-based copolymer and a carboxylic acid-modified nitrile-based copolymer; Phenolic emulsifiers; And a first layer of a latex composition for dip molding comprising an antistatic polymer. According to claim 1,
The molded article may include at least one copolymer selected from the group consisting of a nitrile-based copolymer and a carboxylic acid-modified nitrile-based copolymer; And a second layer derived from a latex composition for dip molding comprising a phenolic emulsifier, and an antistatic polymer derived layer comprising an antistatic polymer. Attaching a coagulant to the dip molding mold (S10); And
One or more copolymers selected from the group consisting of a nitrile-based copolymer and a carboxylic acid-modified nitrile-based copolymer for the dip molding mold to which the coagulant is attached; Phenolic emulsifiers; And immersing in a first dip molding latex composition containing an antistatic polymer to form a layer derived from the first dip molding latex composition (S20). Attaching a coagulant to the dip molding mold (S100);
One or more copolymers selected from the group consisting of a nitrile-based copolymer and a carboxylic acid-modified nitrile-based copolymer for the dip molding mold to which the coagulant is attached; And a phenol-based emulsifier; immersing in a second dip molding latex composition to form a second dip molding latex composition derived layer (S200); And
A method of manufacturing a dip molded article comprising; immersing a dip molding mold in which the second latex composition for dip molding derived layer is formed in a solution containing an antistatic polymer to form an antistatic polymer derived layer (S300).

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