Latex composition for dip molding, molded article molded therefrom, and method for producing same

Abstract

A dip-molded article includes an external molded layer and internal molded layer. The external molded layer includes a content of an ethylenically unsaturated nitrile-based monomer-derived repeating unit is 35 wt% to 60 wt%, and the internal molded layer in which a content of an ethylenically unsaturated nitrile-based monomer-derived repeating unit is 10 wt% to 28 wt%.

Description

Latex composition for deep molding, molded article molded therefrom, and method for manufacturing the same

[0001] Cross-citation with related applications

[0002] This application claims the benefit of priority from Korean Patent Application No. 10-2019-0123605, filed October 7, 2019, the entire contents of which are incorporated herein by reference.

[0003] Technology field

[0004] The present invention relates to a dip-molded product, and more particularly, to the dip-molded product, a latex composition for dip-molding for producing the dip-molded product, and a method for producing the dip-molded product.

[0005] The use of nitrile rubber gloves is rapidly expanding across various industries, including medical, food, chemical, electronics, and industrial, as well as in everyday life. Glove manufacturers are striving to develop gloves with diverse qualities for diverse applications, keeping pace with customer and market changes.

[0006] Natural rubber gloves offer excellent comfort due to their low modulus and high elasticity. Based on these advantages, natural rubber gloves have long been used for medical and surgical applications. However, they suffer from very poor chemical resistance, including oil resistance. Furthermore, proteins contained within natural rubber can trigger certain allergies and skin rashes, limiting their intended use.

[0007] Nitrile rubber gloves offer excellent chemical and oil resistance, offering the advantage of protecting skin in a variety of work environments. However, their high modulus makes them stiff when donned, and can easily lead to hand fatigue when worn for extended periods. Furthermore, their low elasticity prevents the gloves from forming a tight seal, making them unsuitable for delicate tasks.

[0008] Although rubber gloves require excellent wearing comfort and chemical resistance, it is very difficult to develop and manufacture gloves that satisfy these properties simultaneously.

[0009] The problem to be solved by the present invention is to simultaneously improve the wearability and chemical resistance of a deep-molded product in order to solve the problems mentioned in the background technology of the above invention.

[0010] That is, the purpose of the present invention is to provide a dip-molded product and a manufacturing method thereof that simultaneously improves wearability and chemical resistance by forming a plurality of layers using latex compositions for dip-molding each having a different content of ethylenically unsaturated nitrile monomer when manufacturing a dip-molded product.

[0011] According to one embodiment of the present invention for solving the above problem, the present invention provides a dip-molded product including an outer molding layer having a content of 35 wt% to 60 wt% of repeating units derived from an ethylenically unsaturated nitrile monomer; and an inner molding layer having a content of 10 wt% to 28 wt% of repeating units derived from an ethylenically unsaturated nitrile monomer.

[0012] In addition, the present invention comprises a step (S10) of attaching a coagulant to a dip mold; a step (S20) of immersing the dip mold with the coagulant attached thereto in a first dip molding latex composition to form a first dip molding latex composition-derived layer; a step (S30) of immersing the dip mold with the first dip molding latex composition-derived layer formed thereon in a second dip molding latex composition to form a second dip molding latex composition-derived layer; And a step (S40) of heating the first molding latex composition-derived layer and the second dip molding latex composition-derived layer to crosslink the first dip molding latex composition and the second dip molding latex composition, wherein the first dip molding latex composition includes a carboxylic acid-modified nitrile-based copolymer latex having a content of 35 wt% to 60 wt% of an ethylenically unsaturated nitrile-based monomer-derived repeating unit, and the second dip molding latex composition includes a carboxylic acid-modified nitrile-based copolymer latex having a content of 10 wt% to 28 wt% of an ethylenically unsaturated nitrile-based monomer-derived repeating unit. A method for manufacturing a dip molded product is provided.

[0013] The deep-molded product according to the present invention can simultaneously realize excellent wearing comfort and chemical resistance by including an outer molding layer having a high content of repeating units derived from ethylenically unsaturated nitrile monomers and an inner molding layer having a low content of repeating units derived from ethylenically unsaturated nitrile monomers.

[0014] The terms or words used in the description and claims of the present invention should not be interpreted as limited to their usual or dictionary meanings, but should be interpreted as meanings and concepts that conform to the technical idea of ​​the present invention, based on the principle that the inventor can appropriately define the concept of the term to explain his or her own invention in the best possible manner.

[0015]

[0016] Hereinafter, the present invention will be described in more detail to help understand the present invention.

[0017] In the present invention, the term 'monomer-derived repeating unit' may indicate a component, structure, or substance itself derived from a monomer, and may mean a repeating unit formed within a polymer by a monomer introduced during polymerization of the polymer and participating in the polymerization reaction.

[0018] In the present invention, the term 'latex' may mean a polymer or copolymer polymerized by polymerization that exists in a form dispersed in water, and as a specific example, it may mean a polymer or copolymer of rubber polymerized by emulsion polymerization that exists in a form dispersed in water in a colloidal state.

[0019] In the present invention, the term 'derived layer' may refer to a layer formed from a polymer or copolymer, and as a specific example, may refer to a layer formed from a polymer or copolymer by attaching, fixing, and / or polymerizing the polymer or copolymer on a dip mold during the manufacture of a dip molded product.

[0020]

[0021] According to the present invention, a dip-molded product is provided. The dip-molded product may include an outer molding layer having a content of repeating units derived from an ethylenically unsaturated nitrile monomer of 35 wt% to 60 wt%; and an inner molding layer having a content of repeating units derived from an ethylenically unsaturated nitrile monomer of 10 wt% to 28 wt%.

[0022] According to one embodiment of the present invention, in the dip-molded product, the outer molding layer may refer to a layer that directly contacts the external environment and external substances. The outer molding layer that directly contacts the external environment and external substances requires not only stress (modulus) and tensile properties related to wearability, but also excellent chemical resistance. If a dip-molded product that does not have such excellent chemical resistance is handled with an organic solvent for a long time, there is a problem that the molded product becomes soft and tears. In response to this, the present invention manufactures the outer molding layer to include 35 wt% to 60 wt% of an ethylenically unsaturated nitrile-based monomer-derived repeating unit, i.e., to include a high content of an ethylenically unsaturated nitrile-based monomer-derived repeating unit, thereby simultaneously realizing excellent tensile properties and chemical resistance.

[0023] The ethylenically unsaturated nitrile monomer forming the above ethylenically unsaturated nitrile monomer-derived repeating unit may include at least one selected from the group consisting of acrylonitrile, methacrylonitrile, fumaronitrile, α-chloronitrile, and α-cyano ethyl acrylonitrile, and as a specific example, may be acrylonitrile and methacrylonitrile, and as a more specific example, may be acrylonitrile.

[0024] According to one embodiment of the present invention, the content of the repeating unit derived from the ethylenically unsaturated nitrile monomer with respect to the total content of the outer molding layer may be 35 wt% to 55 wt%, 35 wt% to 50 wt%, or 35 wt% to 45 wt%. By including the repeating unit derived from the ethylenically unsaturated nitrile monomer within the above range, the outer molding layer can realize excellent wearing comfort and improve chemical resistance at the same time.

[0025] According to one embodiment of the present invention, the outer molding layer may further include, in addition to the repeating unit derived from an ethylenically unsaturated nitrile monomer, a repeating unit derived from a conjugated diene monomer and a repeating unit derived from an ethylenically unsaturated acid monomer.

[0026] The conjugated diene monomer forming the above conjugated diene monomer-derived repeating unit may include at least one selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene and isoprene, and as a specific example, it may be 1,3-butadiene or isoprene, and as a more specific example, it may be 1,3-butadiene.

[0027] The content of the repeating unit derived from the above conjugated diene monomer may be 30 wt% to 65 wt%, 35 wt% to 65 wt%, or 40 wt% to 60 wt% based on the total content of the outer molding layer, and within this range, the dip-molded product is flexible and has excellent touch and wearability, as well as excellent oil resistance and tensile strength.

[0028] 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 may be an ethylenically unsaturated monomer containing an acidic group such as a carboxyl group, a sulfonic acid group, or an acid anhydride group, and specific examples thereof 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 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-hydroxypropyl maleate, and more specifically, it may be at least one selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid, and a more specific example may be 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.

[0029] The content of the repeating unit derived from the ethylenically unsaturated acid monomer may be 0.1 wt% to 10 wt%, 0.5 wt% to 9 wt%, or 2 wt% to 8 wt% based on the total content of the outer molding layer, and within this range, the dip-molded product is flexible and has excellent wearability, and at the same time has excellent polymerization stability and tensile strength.

[0030] According to one embodiment of the present invention, the outer molding layer may further include an ethylenically unsaturated monomer-derived repeating unit formed from another ethylenically unsaturated monomer copolymerizable with the ethylenically unsaturated nitrile monomer and the ethylenically unsaturated acid monomer.

[0031] 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; a fluoroalkyl vinyl ether such as fluoroethyl vinyl ether; an ethylenically unsaturated amide monomer selected from the group consisting of (meth)acrylamide, N-methylol (meth)acrylamide, N,N-dimethylol (meth)acrylamide, N-methoxy methyl (meth)acrylamide, and N-propoxy methyl (meth)acrylamide; a non-conjugated diene monomer 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-cyanoethyl (meth)acrylate, 1-cyanopropyl (meth)acrylate, 2-ethyl-6-cyanohexyl (meth)acrylate, 3-cyanopropyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, It may be at least one selected from the group consisting of ethylenically unsaturated carboxylic acid ester monomers selected from the group consisting of glycidyl (meth)acrylate, and dimethylamino ethyl (meth)acrylate.

[0032] The content of the repeating unit derived from the above ethylenically unsaturated monomer may be within 20 wt%, 0.01 wt% to 20 wt%, or 0.01 wt% to 15 wt%, based on the total content of the outer molding layer, and within this range, the dip-molded product has excellent touch and wearability, and at the same time, excellent tensile strength.

[0033] According to one embodiment of the present invention, in the dip-molded product, the inner molding layer may refer to a layer that comes into contact with a part of the human body of a user wearing the dip-molded product. As such, the inner molding layer that comes into contact with a part of the human body of the user requires excellent wearing comfort. In this regard, the present invention manufactures the inner molding layer to include 10 wt% to 28 wt% of an ethylenically unsaturated nitrile-based monomer-derived repeating unit, that is, to include a low content of an ethylenically unsaturated nitrile-based monomer-derived repeating unit and to increase the content of a conjugated diene-based monomer-derived repeating unit that improves wearing comfort, thereby providing a dip-molded product that is flexible, has excellent touch and wearing comfort, and has excellent oil resistance and tensile strength.

[0034] A specific description of the ethylenically unsaturated nitrile monomer forming the repeating unit derived from the ethylenically unsaturated nitrile monomer included in the inner molding layer may be the same as the description of the ethylenically unsaturated nitrile monomer forming the repeating unit derived from the ethylenically unsaturated nitrile monomer included in the outer molding layer described above. In this case, the ethylenically unsaturated nitrile monomers forming the repeating unit derived from the ethylenically unsaturated nitrile monomer of the outer molding layer and the inner molding layer may be the same or different. As a specific example, the ethylenically unsaturated nitrile monomer included in the inner molding layer may be acrylonitrile.

[0035] According to one embodiment of the present invention, the content of the repeating unit derived from the ethylenically unsaturated nitrile monomer with respect to the total content of the inner molding layer may be 13 wt% to 28 wt%, 15 wt% to 28 wt%, or 20 wt% to 28 wt%. The inner molding layer can realize excellent wearing comfort while maintaining chemical resistance by including the repeating unit derived from the ethylenically unsaturated nitrile monomer within the above range.

[0036] According to one embodiment of the present invention, the inner molding layer may further include, in addition to the repeating unit derived from an ethylenically unsaturated nitrile monomer, a repeating unit derived from a conjugated diene monomer and a repeating unit derived from an ethylenically unsaturated acid monomer.

[0037] A specific description of the conjugated diene monomer forming the repeating unit derived from the conjugated diene monomer included in the inner molding layer may be the same as the description of the conjugated diene monomer forming the repeating unit derived from the conjugated diene monomer included in the outer molding layer described above. In this case, the conjugated diene monomer forming the repeating unit derived from the conjugated diene monomer of the outer molding layer and the inner molding layer may be the same or different. As a specific example, the conjugated diene monomer included in the inner molding layer may be 1,3-butadiene.

[0038] The content of the repeating unit derived from the above conjugated diene monomer may be 62 wt% to 90 wt%, 65 wt% to 85 wt%, or 67 wt% to 80 wt% based on the total content of the inner molding layer, and within this range, the dip-molded product is flexible and has excellent touch and wearability, as well as excellent chemical resistance and tensile strength.

[0039] According to one embodiment of the present invention, a specific description of the ethylenically unsaturated acid monomer forming the ethylenically unsaturated acid monomer-derived repeating unit included in the inner molding layer may be the same as the description of the ethylenically unsaturated acid monomer forming the ethylenically unsaturated acid monomer-derived repeating unit included in the outer molding layer described above. In this case, the ethylenically unsaturated acid monomers forming the ethylenically unsaturated acid monomer-derived repeating unit of the outer molding layer and the inner molding layer may be the same or different. As a specific example, the ethylenically unsaturated acid monomer included in the inner molding layer may be methacrylic acid.

[0040] The content of the repeating unit derived from the ethylenically unsaturated acid monomer may be 0.1 wt% to 10 wt%, 0.5 wt% to 9 wt%, or 2 wt% to 8 wt% based on the total content of the inner molding layer, and within this range, the dip-molded product is flexible and has excellent wearability, and at the same time has excellent polymerization stability and tensile strength.

[0041] According to one embodiment of the present invention, the inner molding layer may further include an ethylenically unsaturated monomer-derived repeating unit formed from another ethylenically unsaturated monomer copolymerizable with the ethylenically unsaturated nitrile monomer and the ethylenically unsaturated acid monomer.

[0042] The description of the ethylenically unsaturated monomer forming the ethylenically unsaturated monomer-derived repeating unit included in the inner molding layer may be the same as the description of the ethylenically unsaturated monomer forming the ethylenically unsaturated monomer-derived repeating unit included in the outer molding layer described above. In this case, the ethylenically unsaturated monomers forming the ethylenically unsaturated monomer-derived repeating unit of the outer molding layer and the inner molding layer may be the same or different.

[0043] The content of the repeating unit derived from the ethylenically unsaturated monomer may be within 20 wt%, 0.01 wt% to 20 wt%, or 0.01 wt% to 15 wt%, based on the total content of the inner molding layer, and within this range, the dip-molded product has excellent touch and wearability, and excellent tensile strength.

[0044] According to one embodiment of the present invention, the thickness ratio of the outer molding layer and the inner molding layer may be 1:9 to 9:1. For example, the thickness ratio of the outer molding layer and the inner molding layer may be 1:4 to 4:1, 1.5:1 to 2.5:1. By adjusting the thickness of the outer molding layer and the inner molding layer within the above range, the wearability and chemical resistance of the deep molded product composed of the outer molding layer and the inner molding layer can be improved at the same time.

[0045]

[0046] In addition, according to the present invention, a method for manufacturing a dip-molded product is provided. The method for manufacturing a dip-molded product includes a step of attaching a coagulant to a dip-molding mold (S10); a step of immersing the dip-molding mold with the coagulant attached thereto in a first dip-molding latex composition to form a first dip-molding latex composition-derived layer (S20); a step of immersing the dip-molding mold with the first dip-molding latex composition-derived layer formed thereon in a second dip-molding latex composition to form a second dip-molding latex composition-derived layer (S30); And a step (S40) of heating the first molding latex composition-derived layer and the second dip molding latex composition-derived layer to crosslink the first dip molding latex composition and the second dip molding latex composition, wherein the first dip molding latex composition may include a carboxylic acid-modified nitrile-based copolymer latex having a content of 35 wt% to 60 wt% of an ethylenically unsaturated nitrile-based monomer-derived repeating unit, and the second dip molding latex composition may include a carboxylic acid-modified nitrile-based copolymer latex having a content of 10 wt% to 28 wt% of an ethylenically unsaturated nitrile-based monomer-derived repeating unit.

[0047] The method for manufacturing a molded product for molding the above molded product may include a step of immersing the latex composition for dip molding by a direct immersion method, an anodic adhesion immersion method, a Teague adhesion immersion method, etc., and as a specific example, it may be performed by an anodic adhesion immersion method, and in this case, there is an advantage in that a dip molded product of uniform thickness can be obtained.

[0048] The above step (S10) is a step of immersing the dip mold in a coagulant solution to attach the coagulant to the surface of the dip mold in order 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 may be 5 wt% to 75 wt%, 7 wt% to 60 wt%, or 15 wt% to 55 wt% based on the total content of the coagulant solution.

[0049] The coagulant may be at least one selected from the group consisting of 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; acetates such as barium acetate, calcium acetate, and zinc acetate; and sulfates such as calcium sulfate, magnesium sulfate, and aluminum sulfate, and a specific example thereof may be calcium chloride or calcium nitrate.

[0050] According to one embodiment of the present invention, the step (S20) may be a step of immersing a dip mold having a coagulant attached thereto to form an outer molding layer in a first dip molding latex composition, and taking it out to form a first dip molding latex composition-derived layer, i.e., an outer molding layer, in the dip mold.

[0051] In the step (S20), the first latex composition for dip molding may include a first carboxylic acid-modified nitrile copolymer latex including a repeating unit derived from an ethylenically unsaturated nitrile monomer, a repeating unit derived from a conjugated diene monomer, and a repeating unit derived from an ethylenically unsaturated acid monomer. In this case, a detailed description of the repeating unit derived from the ethylenically unsaturated nitrile monomer, the repeating unit derived from the conjugated diene monomer, and the repeating unit derived from the ethylenically unsaturated acid monomer may be the same as the description of the repeating unit derived from the ethylenically unsaturated nitrile monomer, the repeating unit derived from the conjugated diene monomer, and the repeating unit derived from the ethylenically unsaturated acid monomer included in the outer molding layer of the dip molded product described above.

[0052] The above first carboxylic acid modified nitrile copolymer latex may further include a repeating unit derived from an ethylenically unsaturated monomer, and in this case, a detailed description of the ethylenically unsaturated monomer forming the repeating unit derived from the ethylenically unsaturated monomer may be the same as the description of the ethylenically unsaturated monomer included in the outer molding layer of the dip-molded product described above.

[0053] The above first carboxylic acid-modified nitrile copolymer latex can be manufactured by adding an emulsifier, a polymerization initiator, an activator, a molecular weight regulator, a polymerization terminator, etc. to the monomer mixture constituting the first carboxylic acid-modified nitrile copolymer and performing emulsion polymerization. At this time, in the polymerization, the type and content of the monomer mixture can be input as the type and content of the monomers included in the outer molding layer of the dip-molded product, and the input method can be selected from a batch input method, a continuous input method, or a divided input method.

[0054] In producing the above first carboxylic acid-modified nitrile copolymer latex, an emulsifier is added to provide stability to the latex during and after the polymerization reaction, and various types of anionic emulsifiers and nonionic emulsifiers can be used. For example, anionic emulsifiers include alkyl benzene sulfonates such as sodium alkyl benzene sulfonate, alcohol sulfates, alcohol ether sulfonates, alkyl phenol ether sulfonates, alpha olefin sulfonates, paraffin sulfonates, ester sulfosuccinates, phosphate esters, etc., and nonionic emulsifiers can include alkyl phenol ethoxylates, phenoxyamine ethoxylates, fatty acid ethoxylates, alkanoamides, etc. These emulsifiers can be used alone or in combination of two or more. In addition, 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 6 parts by weight based on 100 parts by weight of the total monomer mixture content, and within this range, the polymerization stability is excellent, and the amount of foaming is small, making it easy to manufacture a molded product.

[0055] In addition, in producing the first carboxylic acid-modified nitrile copolymer latex, the polymerization initiator may be a radical initiator. For example, the radical initiator may be an inorganic peroxide such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate, hydrogen peroxide, etc.; an organic peroxide such as t-butyl peroxide, cumene hydroperoxide, p-menthane hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, dibenzoyl peroxide, 3,5,5-trimethylhexanol peroxide, t-butyl peroxy isobutyrate, etc.; It may include nitrogen compounds such as azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, and azobisisobutyrate methyl. The polymerization initiator may be used alone or in combination of two or more. As a specific example, the radical initiator may be an inorganic peroxide, and as a more specific example, the radical initiator may be a persulfate. The polymerization initiator may be added in an amount of 0.01 to 2 parts by weight or 0.02 to 1.5 parts by weight based on 100 parts by weight of the total monomer mixture, and within this range, there is an effect of maintaining the polymerization rate at an appropriate level.

[0056] In addition, in producing the first carboxylic acid-modified nitrile copolymer latex, the activator may be at least one selected from the group consisting of sodium formaldehyde, sulfoxylate, sodium ethylenediamine tert-butyl acetate, ferrous sulfate, dextrose, sodium pyrophosphate, and sodium sulfite. In addition, the activator may be added in an amount of 0.01 to 2.0 parts by weight, 0.02 to 1.5 parts by weight, or 0.05 to 1.0 parts by weight based on 100 parts by weight of the total monomer mixture, and within this range, there is an effect of maintaining the polymerization rate at an appropriate level.

[0057] In addition, in producing the first carboxylic acid-modified nitrile copolymer latex, the molecular weight modifier may include, for example, mercaptans such as α-methylstyrene dimer, t-dodecyl mercaptan, n-dodecyl mercaptan, and octyl mercaptan; halogenated hydrocarbons such as carbon tetrachloride, methylene chloride, and methylene bromide; and sulfur-containing compounds such as tetraethylthiuram disulfide, dipentamethylenethiuram disulfide, and diisopropylxanthogen disulfide. These molecular weight modifiers may be used alone or in combination of two or more. As a specific example, the molecular weight modifier may be mercaptans, and as a more specific example, the molecular weight modifier may be t-dodecyl mercaptan. The above molecular weight regulator can 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 part by weight based on 100 parts by weight of the total monomer mixture content, and within this range, the polymerization stability is excellent, and when manufacturing a molded product after polymerization, the physical properties of the molded product are excellent.

[0058] In addition, according to one embodiment of the present invention, in the method for producing the first carboxylic acid-modified nitrile copolymer latex, polymerization may be performed in water as a medium, specifically, deionized water, and, in order to secure ease of polymerization, additives such as a chelating agent, a dispersing agent, a pH regulator, a deoxidizing agent, a particle size regulator, an anti-aging agent, and an oxygen scavenger may be further included as needed.

[0059] According to one embodiment of the present invention, the emulsifier, polymerization initiator, molecular weight regulator, additive, etc. may be introduced into the polymerization reactor in batches or in portions together with the monomer mixture, and may be introduced continuously at each injection.

[0060] According to one embodiment of the present invention, when polymerizing the first carboxylic acid-modified nitrile copolymer latex, auxiliary materials such as a chelating agent, a dispersing agent, a pH regulator, a deoxidizing agent, a particle size regulator, an anti-aging agent, and an oxygen scavenger may be added as needed.

[0061] The polymerization temperature during the above emulsion polymerization can be, for example, carried out at a polymerization temperature of 10°C to 90°C, 20°C to 80°C, or 25°C to 75°C, and excellent latex stability is achieved within this range.

[0062] Meanwhile, according to one embodiment of the present invention, the method for producing the first latex composition for dip molding can be produced by including at least one additive selected from the group consisting of a curing agent, an ionic crosslinking agent, a pigment, a filler, a thickener, and a pH regulator in the first carboxylic acid-modified nitrile copolymer latex described above. At this time, the curing agent, the ionic crosslinking agent, the pigment, the filler, the thickener, and the pH regulator can be those commonly used in producing a latex composition for dip molding, and are not particularly limited.

[0063] The content of the first carboxylic acid-modified nitrile copolymer latex included in the first dip-molding latex composition may be 80 wt% to 99 wt%, 85 wt% to 98 wt%, or 88 wt% to 97 wt%. By forming a first dip-molding latex composition-derived layer using the first dip-molding latex composition including the first carboxylic acid-modified nitrile copolymer latex in the above range, the physical properties of the dip-molded product can be improved.

[0064] According to one embodiment of the present invention, the solid content (concentration) of the first latex composition for dip molding may be 10 wt% to 20 wt%, 12 wt% to 20 wt%, or 15 wt% to 20 wt%. Within this range, the efficiency of latex transportation is excellent, and an increase in latex viscosity is prevented, resulting in excellent storage stability.

[0065] According to one embodiment of the present invention, 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, excellent processability and productivity are achieved when manufacturing a dip molded product. The pH of the latex composition for dip molding may be adjusted by adding the pH adjusting agent described above. The pH adjusting agent may be, for example, an aqueous potassium hydroxide solution having a concentration of 1 wt% to 5 wt%, or an aqueous ammonia solution having a concentration of 1 wt% to 5 wt%.

[0066] According to one embodiment of the present invention, the immersion time in the step (S20) may be 5 to 20 seconds, 5 to 15 seconds, or 6 to 12 seconds. By controlling the immersion time in the step (S20) within the above range, the thickness of the first dip molding latex composition-derived layer can be adjusted.

[0067] According to one embodiment of the present invention, after the step (S20), a step of evaporating the water component by heating at a temperature higher than a certain temperature may be further included.

[0068] According to one embodiment of the present invention, the step (S30) may be a step of immersing a dip mold having a first dip molding latex composition-derived layer formed thereon in a second dip molding latex composition to form an inner molding layer, and taking it out to form a second dip molding latex composition-derived layer, i.e., an inner molding layer.

[0069] In the above step (S30), the second dip-molding latex composition may include a second carboxylic acid-modified nitrile-based copolymer latex including 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. In this case, a detailed description of the repeating unit derived from the ethylenically unsaturated nitrile-based monomer, the repeating unit derived from the conjugated diene-based monomer, and the repeating unit derived from the ethylenically unsaturated acid monomer may be the same as the description of the repeating unit derived from the ethylenically unsaturated nitrile-based monomer, the repeating unit derived from the conjugated diene-based monomer, and the repeating unit derived from the ethylenically unsaturated acid monomer included in the inner molding layer of the dip-molded product described above.

[0070] The above second carboxylic acid modified nitrile copolymer latex may further include a repeating unit derived from an ethylenically unsaturated monomer, and in this case, a detailed description of the ethylenically unsaturated monomer forming the repeating unit derived from the ethylenically unsaturated monomer may be the same as the description of the ethylenically unsaturated monomer included in the inner molding layer of the dip-molded product described above.

[0071] The above second carboxylic acid-modified nitrile copolymer latex can be produced by adding an emulsifier, a polymerization initiator, an activator, a molecular weight regulator, a polymerization terminator, etc. to the monomer mixture constituting the first carboxylic acid-modified nitrile copolymer and performing emulsion polymerization. At this time, when performing emulsion polymerization of the second carboxylic acid-modified nitrile copolymer latex, detailed descriptions of polymerization conditions and additives, etc. may be the same as the descriptions of polymerization conditions and additives, etc. of the first carboxylic acid-modified nitrile copolymer latex described above.

[0072] According to one embodiment of the present invention, the method for producing the second latex composition for dip molding can be produced by including at least one additive selected from the group consisting of a curing agent, an ionic crosslinking agent, a pigment, a filler, a thickener, and a pH regulator in the second carboxylic acid-modified nitrile copolymer latex described above. In this case, the curing agent, the ionic crosslinking agent, the pigment, the filler, the thickener, and the pH regulator can be those commonly used in producing a latex composition for dip molding, and are not particularly limited.

[0073] The content of the second carboxylic acid-modified nitrile copolymer latex included in the second dip-molding latex composition may be 80 wt% to 99 wt%, 85 wt% to 98 wt%, or 88 wt% to 97 wt%. By forming a second dip-molding latex composition-derived layer using the second dip-molding latex composition including the second carboxylic acid-modified nitrile copolymer latex in the above range, the physical properties of the dip-molded product can be improved.

[0074] According to one embodiment of the present invention, the solid content (concentration) of the second latex composition for dip molding may be 21 wt% to 35 wt%, 21 wt% to 32 wt%, or 21 wt% to 30 wt%. Within this range, the latex transport efficiency is excellent, and an increase in latex viscosity is prevented, resulting in excellent storage stability.

[0075] According to one embodiment of the present invention, 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, excellent processability and productivity are achieved when manufacturing a dip molded product. The pH of the latex composition for dip molding may be adjusted by adding the pH adjusting agent described above. The pH adjusting agent may be, for example, an aqueous potassium hydroxide solution having a concentration of 1 wt% to 5 wt%, or an aqueous ammonia solution having a concentration of 1 wt% to 5 wt%.

[0076] According to one embodiment of the present invention, the immersion time in the step (S30) may be 5 to 20 seconds, 5 to 18 seconds, or 6 to 14 seconds. By controlling the immersion time in the step (S30) within the above range, the thickness of the latex composition-derived layer for the first dip molding can be adjusted.

[0077] According to one embodiment of the present invention, after the step (S30), a step of evaporating the water component by heating at a temperature higher than a certain temperature may be further included.

[0078] According to one embodiment of the present invention, the step (S40) may be a step of heating the first molding latex composition-derived layer and the second molding latex composition-derived layer formed in the mold to first evaporate the water component, and crosslinking the first molding latex composition and the second molding latex composition to proceed with hardening in order to obtain a molded product.

[0079] In this way, by forming a first latex composition-derived layer for dip molding and a second latex composition-derived layer for dip molding, each having a different content of repeating units derived from an ethylenically unsaturated nitrile monomer, and manufacturing a dip molded product through crosslinking, it is possible to simultaneously improve wearability and chemical resistance.

[0080] According to one embodiment of the present invention, after step (S40), the first dip-molding latex composition-derived layer and the second dip-molding latex composition-derived layer crosslinked by heat treatment in step (S40) are peeled off from the dip-molding mold to obtain a dip-molded product.

[0081] According to one embodiment of the present invention, the molded product may be a glove, such as a surgical glove, an examination glove, an industrial glove, or a household glove, a condom, a catheter, or a health care product.

[0082]

[0083] Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are intended to illustrate the present invention, and it will be apparent to those skilled in the art that various changes and modifications are possible within the scope and technical spirit of the present invention, and the scope of the present invention is not limited to these examples alone.

[0084]

[0085] Manufacturing example

[0086] Manufacturing Example 1

[0087] <Manufacture of the first carboxylic acid-modified nitrile copolymer latex>

[0088] After a 10L high-pressure reactor equipped with a stirrer, a thermometer, a cooler, a nitrogen gas inlet, and a device for continuously introducing monomers, emulsifiers, and polymerization initiators was replaced with nitrogen, 2.4 parts by weight of sodium alkylbenzene sulfonate, 0.6 parts by weight of t-dodecyl mercaptan, and 140 parts by weight of ion-exchanged water were introduced into 100 parts by weight of a monomer mixture of 39 wt% of acrylonitrile, 57 wt% of 1,3-butadiene, and 4 wt% of methacrylic acid, and the temperature was raised to 40°C.

[0089] After heating, 0.3 parts by weight of potassium persulfate, a polymerization initiator, was added, and when the conversion rate reached 95%, 0.1 parts by weight of sodium dimethyl dithiocarbamate was added to stop the polymerization. Unreacted monomers were removed through a deodorization process, and ammonia water, an antioxidant, an antifoaming agent, etc. were added to obtain a first deep carboxylic acid-modified nitrile copolymer latex (Latex-A) with a solid content of 45% and a pH of 8.5.

[0090]

[0091] <Preparation of latex composition for first deep molding>

[0092] 1 wt% of sulfur, 1 wt% of zinc dibutyldithiocarbamate (ZDBC), 1.3 wt% of zinc oxide, 1.0 wt% of titanium oxide, 1.6 wt% of potassium hydroxide solution, and double-distilled water were added to 100 wt% (based on solid content) of the above-mentioned manufactured latex-A to obtain a first dip molding latex composition (composition-A) having a pH of 10 and a solid content concentration of 18 wt% and 25 wt%, respectively.

[0093]

[0094] Manufacturing Example 2

[0095] <Manufacture of a second carboxylic acid-modified nitrile copolymer latex>

[0096] After a 10L high-pressure reactor equipped with a stirrer, a thermometer, a cooler, a nitrogen gas inlet, and a device for continuously introducing monomers, emulsifiers, and polymerization initiators was replaced with nitrogen, 3 parts by weight of sodium alkylbenzene sulfonate, 0.7 parts by weight of t-dodecyl mercaptan, and 140 parts by weight of ion-exchanged water were introduced into 100 parts by weight of a monomer mixture of 24 wt% of acrylonitrile, 72 wt% of 1,3-butadiene, and 4 wt% of methacrylic acid, and the temperature was raised to 40°C.

[0097] After heating, 0.3 parts by weight of potassium persulfate, a polymerization initiator, was added, and when the conversion rate reached 95%, 0.1 parts by weight of sodium dimethyl dithiocarbamate was added to stop the polymerization. Unreacted monomers were removed through a deodorizing process, and ammonia water, an antioxidant, an antifoaming agent, etc. were added to obtain a second deep carboxylic acid-modified nitrile copolymer latex (Latex-B) with a solid content of 45% and a pH of 8.5.

[0098]

[0099] <Manufacturing of latex composition for second deep molding>

[0100] 1 wt% of sulfur, 1 wt% of zinc dibutyldithiocarbamate (ZDBC), 1.3 wt% of zinc oxide, 1.0 wt% of titanium oxide, 1.6 wt% of potassium hydroxide solution, and double-distilled water were added to 100 wt% (based on solid content) of the above-mentioned manufactured latex-B to obtain a second dip molding latex composition (composition-B) having a pH of 10 and solid content concentrations of 18 wt% and 25 wt%.

[0101]

[0102] Manufacturing Example 3

[0103] <Manufacture of tertiary carboxylic acid-modified nitrile copolymer latex>

[0104] After replacing a 10L high-pressure reactor equipped with a stirrer, a thermometer, a cooler, a nitrogen gas inlet, and a nitrogen gas inlet to allow continuous input of monomers, emulsifiers, and polymerization initiators with nitrogen, 3 parts by weight of sodium alkylbenzene sulfonate, 0.7 parts by weight of t-dodecyl mercaptan, and 140 parts by weight of ion-exchanged water were added to 100 parts by weight of a monomer mixture of 31 wt% of acrylonitrile, 63 wt% of 1,3-butadiene, and 6 wt% of methacrylic acid, and the temperature was raised to 40°C.

[0105] After heating, 0.3 parts by weight of potassium persulfate, a polymerization initiator, was added, and when the conversion rate reached 95%, 0.1 parts by weight of sodium dimethyl dithiocarbamate was added to stop the polymerization. Unreacted monomers were removed through a deodorizing process, and ammonia water, an antioxidant, an antifoaming agent, etc. were added to obtain a third deep carboxylic acid-modified nitrile copolymer latex (Latex-C) with a solid content of 45% and a pH of 8.5.

[0106]

[0107] <Manufacturing of latex composition for second deep molding>

[0108] 1 wt% of sulfur, 1 wt% of zinc dibutyldithiocarbamate (ZDBC), 1.3 wt% of zinc oxide, 1.0 wt% of titanium oxide, 1.6 wt% of potassium hydroxide solution, and double-distilled water were added to 100 wt% (based on solid content) of the above-mentioned manufactured latex-C to obtain a second dip molding latex composition (composition-C) having a pH of 10 and solid content concentrations of 18 wt% and 25 wt%.

[0109]

[0110] Example

[0111] Example 1

[0112] <Manufacturing of deep molded products>

[0113] A coagulant solution was prepared by mixing 15 parts by weight of calcium nitrate, 84.5 parts by weight of distilled water, and 0.5 parts by weight of a wetting agent (Teric 320 produced by Huntsman Corporation, Australia). A hand-shaped ceramic dip mold was immersed in this solution for 8 seconds, taken out, and dried at 120°C for 2 minutes and 30 seconds to apply the coagulant to the hand-shaped mold (S10).

[0114] Then, the dip-molding mold to which the coagulant was applied was immersed in the composition-A having a solid content concentration of 18 wt% prepared above for 8 seconds, pulled up, and dried at 120°C for 30 seconds (S20). Then, it was immersed in the composition-B having a solid content concentration of 25 wt% prepared above for 12 seconds, pulled up, dried at 80°C for 30 seconds, and then immersed in water or hot water for 30 seconds (S30). Thereafter, it was crosslinked at 120°C for 20 minutes (S40). The crosslinked dip-molding layer was peeled off from the hand-shaped mold to obtain a glove-shaped dip-molded product.

[0115]

[0116] Example 2

[0117] In the above Example 1, a dip-molded product in the shape of a glove was obtained in the same manner as in Example 1, except that in step (S20), the product was immersed in composition-A having a solid concentration of 18 wt% for 10 seconds instead of 8 seconds, and in step (S30), the product was immersed in composition-B having a solid concentration of 25 wt% for 8 seconds instead of 12 seconds.

[0118]

[0119] Comparative example

[0120] Comparative Example 1

[0121] In the above Example 1, a dip-molded product in the shape of a glove was obtained in the same manner as Example 1, except that in step (S30), the product was immersed in Composition-A having a solid concentration of 25 wt% instead of Composition-B having a solid concentration of 25 wt%.

[0122]

[0123] Comparative Example 2

[0124] In the above Example 1, a dip-molded product in the shape of a glove was obtained in the same manner as Example 1, except that in step (S20), the product was immersed in Composition-B having a solid content concentration of 18 wt% instead of Composition-A having a solid content concentration of 18 wt%.

[0125]

[0126] Comparative Example 3

[0127] In the above Example 2, a dip-molded product in the shape of a glove was obtained in the same manner as Example 2, except that in step (S30), the product was immersed in Composition-A having a solid content concentration of 25 wt% instead of Composition-B having a solid content concentration of 25 wt%.

[0128]

[0129] Comparative Example 4

[0130] In the above Example 2, a dip-molded product in the shape of a glove was obtained in the same manner as Example 2, except that in step (S20), the product was immersed in Composition-B having a solid content concentration of 18 wt% instead of Composition-A having a solid content concentration of 18 wt%.

[0131]

[0132] Comparative Example 5

[0133] In the above Example 1, a dip-molded product in the shape of a glove was obtained in the same manner as in Example 1, except that in step (S20), the composition-B having a solid content concentration of 18 wt% was immersed instead of the composition-A having a solid content concentration of 18 wt%, and in step (S30), the composition-A having a solid content concentration of 25 wt% was immersed instead of the composition-B having a solid content concentration of 25 wt%.

[0134]

[0135] Comparative Example 6

[0136] In the above Example 2, a dip-molded product in the shape of a glove was obtained in the same manner as in Example 2, except that in step (S20), the composition-B having a solid content concentration of 18 wt% was immersed instead of the composition-A having a solid content concentration of 18 wt%, and in step (S30), the composition-A having a solid content concentration of 25 wt% was immersed instead of the composition-B having a solid content concentration of 25 wt%.

[0137]

[0138] Comparative Example 7

[0139] In the above Example 1, a dip-molded product in the shape of a glove was obtained in the same manner as in Example 1, except that in step (S20), the composition-C having a solid content concentration of 18 wt% was immersed instead of the composition-A having a solid content concentration of 18 wt%, and in step (S30), the composition-C having a solid content concentration of 25 wt% was immersed instead of the composition-B having a solid content concentration of 25 wt%.

[0140]

[0141] Experimental example

[0142] Experimental Example 1

[0143] In the dip-molded products manufactured in Examples 1 to 2 and Comparative Examples 1 to 7, the type of composition used in Step (S20) and Step (S30), the solid content concentration, the thickness of the molded layer, the stress (modulus) at an elongation of 300% of the dip-molded product, the stress retention rate, the chemical resistance, and the durability were measured under the following conditions and are shown in Table 1 below.

[0144] * Stress at 300% elongation (300% Modulus, MPa): For the dip-molded products obtained in each example and comparative example, dumbbell-shaped test pieces were produced in accordance with EN 455-2. Subsequently, these test pieces were pulled at an elongation rate of 500 mm / min using a UTM (Universal Testing Machine), and the tensile strength and elongation at break were measured, and the feel was measured using the stress at 300% elongation. The higher the tensile strength and elongation, the better the quality of the dip-molded product. The lower the stress value at 300% elongation, the better the wearing comfort of the dip-molded product, indicating superior quality.

[0145] * Stress retention rate (%): For the deep-molded products obtained in each example and comparative example, dumbbell-shaped test pieces were manufactured in accordance with EN 455-2, and both ends of the specimen were stretched 100% from a standard section of 20 mm to 40 mm at a speed of 500 mm / min. At that point, the stretching was stopped and the stress M100(0) at this time was measured, and the stress M100(5) was measured after 5 minutes had elapsed. The value of M100(5) with respect to M100(0) was calculated as a percentage, and this value was defined as the stress retention rate. At this time, the larger the value, the better the wearing comfort is determined to be.

[0146] * Chemical resistance (min): For the deep-molded products obtained in each example and comparative example, test specimens were prepared according to EN374-3:2003. Subsequently, the test specimens were permeated with isopropyl alcohol in a GC-FID, and the isopropyl alcohol was applied to the test specimens at a concentration of 1 ㎍ / cm. 2 The time taken for penetration at a rate of / min was measured in minutes (min). A longer time indicates better chemical resistance.

[0147] * Durability (times): A solution for measuring the durability of dip-molded products at 25°C was prepared, consisting of 16 parts by weight of sodium chloride, 16 parts by weight of lactic acid, 3.2 parts by weight of urea, and 64.8 parts by weight of water. Then, the dip-molded product specimens obtained in each example and comparative example were placed in a durability measuring device, and the number of times the specimens were stretched to twice their initial length (up to 2.6 times when stretched, and at least 1 time when shortened) was measured until they broke. A higher number of times is considered to indicate better durability.

[0148] (S20)(S30)300%Modulus(MPa)Stress retention(%)Chemical resistance(min.)Durability(times)CompositionSolid concentration(wt%)Thickness(㎛)CompositionSolid concentration(wt%)Thickness(㎛)Example 1A1864B25354.5547.229.3609Example 2A1866B25284.5943.622.3710Comparative Example 1A1864A25325.9843.061.1668Comparative Example 2B1863B25352.9354.60.0622Comparative Example 3A18 66A25265.4840.340.2853Comparative Example 4B1868B25262.9756.70.0654Comparative Example 5B1863A25314.8144.83.0612Comparative Example 6B1865A25264.6745.01.5620Comparative Example 7C1867C25315.5136.07.0550

[0149]

[0150] Referring to Table 1 above, in the case of Examples 1 and 2, which were manufactured by sequentially immersing Composition-A having a high content of repeating units derived from ethylenically unsaturated nitrile monomers and Composition-B having a low content, it was confirmed that the 300% Modulus and stress retention rate were superior to those of Comparative Examples 1 and 3, which were manufactured by immersing only Composition-A having a high content of ethylenically unsaturated nitrile monomers, thereby exhibiting high wearing comfort.

[0151] In addition, in the case of Comparative Examples 2 and 4, which were manufactured by immersing only with Composition-B having a low content of ethylenically unsaturated nitrile monomer, it was confirmed that the chemical resistance was lowered compared to Examples 1 and 2.

[0152] In addition, in the case of Comparative Examples 5 and 6, which were manufactured by sequentially immersing Composition-B having a low content of repeating units derived from ethylenically unsaturated nitrile monomers and Composition-A having a high content, it was confirmed that the chemical resistance was significantly reduced compared to Examples 1 and 2. This was confirmed to be because the outer molding layer, which accounts for about 2 / 3 of the total thickness of the molded product, was manufactured with Composition-B having a low content of repeating units derived from ethylenically unsaturated nitrile monomers.

[0153] In addition, in the case of Comparative Example 7, which was prepared by immersing only Composition-C, in which the content of repeating units derived from ethylenically unsaturated nitrile monomers is between Composition-A and Composition-B, it was confirmed that the Modulus, stress retention, and chemical resistance were all reduced by 300% compared to Examples 1 and 2.

Claims

1. An outer molding layer having a content of 35 to 60 wt% of repeating units derived from ethylenically unsaturated nitrile monomers; and A deep-molded product comprising an inner molding layer having a content of 10 to 28 wt% of repeating units derived from an ethylenically unsaturated nitrile monomer.

2. In paragraph 1, A deep-molded product wherein the outer molding layer and the inner molding layer further comprise a repeating unit derived from a conjugated diene monomer and a repeating unit derived from an ethylenically unsaturated acid monomer.

3. In paragraph 2, A deep-molded product in which the content of repeating units derived from conjugated diene monomers included in the outer molding layer is 30 to 65 wt%, and the content of repeating units derived from ethylenically unsaturated acid monomers is 0.1 to 10 wt%.

4. In paragraph 2, A deep-molded product in which the content of repeating units derived from conjugated diene monomers contained in the inner molding layer is 60 to 90 wt%, and the content of repeating units derived from ethylenically unsaturated acid monomers is 0.1 to 10 wt%.

5. In paragraph 1, A deep-molded product having a thickness ratio of the outer molding layer and the inner molding layer of 1:9 to 9:

1.

6. In paragraph 1, A deep-molded product having a thickness ratio of the outer molding layer and the inner molding layer of 1.5:1 to 2.5:

1.

7. Step of attaching a coagulant to a deep mold (S10); A step (S20) of immersing the dip mold to which the above coagulant is attached into a first dip molding latex composition to form a first dip molding latex composition-derived layer; Step (S30) of forming a second dip molding latex composition-derived layer by immersing the dip mold having the first dip molding latex composition-derived layer formed thereon into a second dip molding latex composition; and It includes a step (S40) of heating the first molding latex composition-derived layer and the second dip molding latex composition-derived layer to crosslink the first dip molding latex composition and the second dip molding latex composition, The first latex composition for deep molding comprises a carboxylic acid-modified nitrile copolymer latex having a content of 35 to 60 wt% of repeating units derived from ethylenically unsaturated nitrile monomers, A method for manufacturing a dip-molded product, wherein the second dip-molding latex composition comprises a carboxylic acid-modified nitrile copolymer latex having a content of 10 to 28 wt% of repeating units derived from ethylenically unsaturated nitrile monomers.

8. In paragraph 7, A method for manufacturing a deep-molded product, wherein the immersion time in the above steps (S20) and (S30) is 5 to 20 seconds.

9. In paragraph 7, The solid content concentration of the first latex composition for deep molding is 10 wt% to 20 wt%, A method for manufacturing a dip-molded product, wherein the solid content concentration of the second dip-molding latex composition is 21 wt% to 35 wt%.

10. In paragraph 7, A method for manufacturing a dip-molded product, wherein each of the carboxylic acid-modified nitrile copolymer latexes included in the first dip-molding latex composition and the second dip-molding latex composition further comprises a repeating unit derived from a conjugated diene monomer and a repeating unit derived from an ethylenically unsaturated acid monomer.