Composition for latex polymerization having excellent durability, latex for dip molding, and dip molded article produced therefrom

Abstract

One embodiment of the present specification provides a composition for latex polymerization, which includes a conjugated diene monomer, an ethylenically unsaturated nitrile monomer, an ethylenically unsaturated acid monomer, an ionic organic compound, and an ionic inorganic compound, and in which the weight ratio of the ionic inorganic compound to the ionic organic compound is 4.7 or more.

Description

TECHNICAL FIELD

[0001] The present specification relates to a latex polymerization composition having excellent durability, a dip-molding latex, and a dip-molding product manufactured therefrom. BACKGROUND

[0002] In the past, the main raw material for gloves for medical, livestock processing, and industrial uses has been natural rubber latex. However, when using gloves made of natural rubber latex, there are often problems in that the glove users suffer from contact dermatitis due to the proteins contained in the natural rubber latex. Therefore, attempts have been made to manufacture gloves by applying synthetic rubber latexes, such as nitrile-based copolymer latexes, which do not contain proteins. Nitrile-based copolymer latex gloves have excellent mechanical strength compared to natural rubber latex gloves, and thus there is a tendency for the demand to increase in the medical or food fields where frequent contact with sharp objects occurs.

[0003] As the amount of use of nitrile-based copolymer latexes increases, the demand for improvement in the quality of dip-molding products also increases, and thus attempts have been made to improve the durability, such as tensile strength and elongation, of dip-molding products manufactured from dip-molding latexes. However, despite these attempts to improve mechanical properties, there have been continuous occurrences of accidents in which human lives are lost or desired purposes cannot be achieved due to damage to dip-molding products.

[0004] This is because, when the products are actually used, the physical properties of the products deteriorate due to contact with weakly acidic human skin or body fluids such as sweat, and the tensile strength and elongation, which are the existing mechanical properties, are measured in air at room temperature, and if these properties are excellent, the pre-use durability of the dip-molding products can be ensured, but the durability under actual use conditions is poor. Therefore, there is a need to develop a technology for manufacturing dip-molding products having excellent durability under actual use conditions.

[0005] In addition, there is an increasing demand for dip-molding latexes having a high solid content, which exhibit excellent quality even in small amounts, but when the solid content is increased by concentrating existing dip-molding latexes, the particle stability decreases, and thus there is a problem in that the viscosity rapidly increases when the content exceeds a certain level. In addition, dip-molding latexes generally contain particulate polymers having an average particle diameter of about 800 A, and when they are concentrated or increased by chemical treatment or the like in order to improve the quality of the latexes, there is a problem in that the stability of the latexes rapidly deteriorates.

[0006] Therefore, there is a need to develop a dip-molding latex and a dip-molding product that satisfy a high solid content, a large particle diameter, and low viscosity, which are in a trade-off relationship, and have excellent durability under actual use. SUMMARY

[0007] Technical Problem to be Solved The present specification is intended to solve the problems of the prior art described above, and one object of the present specification is to provide a latex for dip molding having excellent stability, a large particle size, a high solid content, and low viscosity characteristics, and a polymerization composition for preparing the same.

[0008] Another object of the present specification is to provide a dip molded product having excellent durability in actual use.

[0009] Technical solution to solve the technical problem According to one aspect, a latex polymerization composition is provided, which includes a conjugated diene-based monomer, an olefinically unsaturated nitrile monomer, an olefinically unsaturated acid monomer, an ionic organic compound, and an ionic inorganic compound, the weight ratio of the ionic inorganic compound to the ionic organic compound being 4.7 or more.

[0010] In one embodiment, the conjugated diene-based monomer can be one selected from the group consisting of 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 2-phenyl-1,3-butadiene, 3-methyl-1,3-pentadiene, 2-chloro-1,3-butadiene, 3-butyl-1,3-octadiene, octadiene, and combinations of two or more thereof.

[0011] In one embodiment, the olefinically unsaturated nitrile monomer can be one selected from the group consisting of acrylonitrile, methacrylonitrile, fumaronitrile, α-chloronitrile, α-cyanoethyl acrylonitrile, and combinations of two or more thereof.

[0012] In one embodiment, the olefinically unsaturated acid monomer can be one selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, maleic anhydride, citraconic anhydride, styrene sulfonic acid, monobutyl fumarate, monobutyl maleate, mono-2-hydroxypropyl maleate, and combinations of two or more thereof.

[0013] In one embodiment, the ionic organic compound can be one selected from the group consisting of ethylenediaminetetraacetic acid (EDTA) or a sodium salt thereof, ethylene glycol tetraacetic acid (EGTA) or a sodium salt thereof, nitrilotriacetic acid (NTA) or a sodium salt thereof, iminodiacetic acid (IDA) or a sodium salt thereof, quinolinic acid (QNA) or a sodium salt thereof, and combinations of two or more thereof.

[0014] In one embodiment, the ionic inorganic compound can be one selected from the group consisting of potassium sulfate (K2SO4), sodium carbonate (Na2CO3), sodium chloride (NaCl), potassium chloride (KCl), calcium chloride (CaCl2), magnesium chloride (MgCl2), sodium nitrate (NaNO3), potassium nitrate (KNO3), calcium nitrate (Ca(NO3)2), magnesium nitrate (Mg(NO3)2), sodium sulfate (Na2SO4), calcium sulfate (CaSO4), magnesium sulfate (MgSO4), sodium hydroxide (NaOH), potassium hydroxide (KOH), calcium hydroxide (Ca(OH)2), magnesium hydroxide (Mg(OH)2), sodium bicarbonate (NaHCO3), potassium bicarbonate (KHCO3), potassium carbonate (K2CO3), sodium bisulfite (NaHSO4), potassium bisulfite (KHSO4), sodium pyrophosphate (Na4P2O7), potassium pyrophosphate (K4P2O7), trisodium phosphate (Na3PO4), tripotassium phosphate (K3PO4), monosodium phosphate (Na2HPO4), monopotassium phosphate (K2HPO4), and a combination of two or more thereof.

[0015] In one embodiment, the composition can include 30 parts by weight to 98 parts by weight of the conjugated diene-based monomer, 1 part by weight to 55 parts by weight of the ethylenically unsaturated nitrile monomer, and 0.001 part by weight to 20 parts by weight of the ethylenically unsaturated acid monomer.

[0016] In one embodiment, the composition can further include water, an emulsifier, a polymerization initiator, and a molecular weight regulator.

[0017] According to another aspect, there is provided a dip-molding latex including a copolymer derived from the latex polymerization composition described above.

[0018] According to still another aspect, there is provided a dip-molding product manufactured from the dip-molding latex described above.

[0019] In one embodiment, the dip-molding product can be a surgical glove, a medical glove, a livestock processing glove, an industrial glove, a condom, a cosmetic material, a catheter, or a health care molding product.

[0020] Effects of the Invention The latex polymerization composition according to one aspect of the present specification has high ionic conductivity, and thus can improve the stability of a polymer during latex polymerization, and thus the dip-molding latex according to another aspect of the present specification can satisfy high solid content, large particle size, and low viscosity, which are in a trade-off relationship, at the same time.

[0021] In addition, the dipped molded article according to another aspect of the present specification is excellent in practical use durability, and thus can be applied to various fields such as surgical gloves, medical gloves, gloves for livestock product processing, industrial gloves, condoms, materials for cosmetics, catheters, health care molded articles, and the like.

[0022] Effects of one aspect of the present specification are not limited to the above-mentioned effects, and it is understood that all effects included in the structure of the application described in the detailed description of the present specification or the attached claims are inferred. DETAILED DESCRIPTION

[0023] Hereinafter, one aspect of the present specification will be described with reference to specific examples. However, the contents described in the present specification can be implemented in various different forms, and are not limited to the examples described in the present specification.

[0024] Throughout the specification, when a component is described as "connected to" another component, it not only includes the case where the component is "directly connected to" the other component, but also includes the case where the component is "connected to" the other component with another component interposed therebetween. In addition, when a part is referred to as "including" a component, unless otherwise specified, it can mean that the part can further include another component, instead of excluding any other component, unless otherwise specified.

[0025] In the present specification, when a range of numerical values is described, unless otherwise specified, the values have the precision of significant figures provided according to the standard rules in chemistry for significant figures. For example, 10 includes a range of 5.0 to 14.9, and the number 10.0 includes a range of 9.50 to 10.49.

[0026] Emulsion polymerization composition The latex polymerization composition according to one aspect of the present specification includes a conjugated diene-based monomer, an olefinically unsaturated nitrile monomer, an olefinically unsaturated acid monomer, an ionic organic compound, and an ionic inorganic compound.

[0027] The ionic organic compound and the ionic inorganic compound described above can improve the stability of a latex by increasing the ionic conductivity of the composition described above, and can form a copolymer having a large particle size of 1,000 A or more. In addition, a latex containing a copolymer derived from the composition described above maintains low viscosity even at a high solid content of 50% by weight or more, and thus can satisfy high solid content, large particle size, and low viscosity, which are in a trade-off relationship, at the same time.

[0028] The weight ratio of the above-mentioned ionic inorganic compound to the above-mentioned ionic organic compound can be 4.7 or more. For example, the above-mentioned weight ratio can be 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, a range between two of the values or more than one of the values. If the weight ratio of the ionic inorganic compound to the ionic organic compound is less than the above-mentioned range, the polymerization rate can decrease, resulting in a decrease in the final conversion rate, and, as the amount of the remaining unreacted monomer increases, the mechanical properties and the practical use durability of the dip-molded product manufactured therefrom can sharply decrease. On the other hand, in the present application, the greater the weight ratio of the above-mentioned ionic inorganic compound to the above-mentioned ionic organic compound, the more favorable it is for the mechanical properties and the practical use durability of the dip-molded product, and thus there is no particular limitation on the upper limit thereof, but, in consideration of the possibility of spoilage upon long-term storage of the latex, it can be limited to 5.9 or less.

[0029] The above-mentioned conjugated diene monomer can be one selected from the group consisting of 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 2-phenyl-1,3-butadiene, 3-methyl-1,3-pentadiene, 2-chloro-1,3-butadiene, 3-butyl-1,3-octadiene, octadiene, and combinations of two or more thereof, but is not limited thereto. In the latex copolymer for dip-molding, the structure derived from the above-mentioned conjugated diene monomer can impart softness to the dip-molded product.

[0030] The above-mentioned ethylenically unsaturated nitrile monomer can be one selected from the group consisting of acrylonitrile, methacrylonitrile, fumaronitrile, α-chloronitrile, α-cyanoethyl acrylonitrile, and combinations of two or more thereof, but is not limited thereto. In the latex copolymer for dip-molding, the structure derived from the above-mentioned ethylenically unsaturated nitrile monomer can improve the strength and chemical resistance of the dip-molded product.

[0031] The above-mentioned ethylenically unsaturated acid monomer can be one selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, maleic anhydride, citraconic anhydride, styrene sulfonic acid, monobutyl fumarate, monobutyl maleate, mono-2-hydroxypropyl maleate, and combinations of two or more thereof, but is not limited thereto. In the latex copolymer for dip-molding, the structure derived from the above-mentioned ethylenically unsaturated acid monomer can form a crosslinking structure to improve the mechanical properties of the dip-molded product.

[0032] The above-mentioned ionic organic compound and the above-mentioned ionic inorganic compound can improve the stability of the copolymer that is reacted upon polymerization of the above-mentioned latex polymerization composition, and can inhibit the coagulation of the latex even after polymerization.

[0033] The ionic organic compound can be one selected from the group consisting of ethylenediaminetetraacetic acid (EDTA) or a sodium salt thereof, ethylene glycol tetraacetic acid (EGTA) or a sodium salt thereof, nitrilotriacetic acid (NTA) or a sodium salt thereof, iminodiacetic acid (IDA) or a sodium salt thereof, quinolinic acid (QNA) or a sodium salt thereof, and a combination of two or more thereof, for example, can be ethylenediaminetetraacetic acid (EDTA), but is not limited thereto.

[0034] The ionic inorganic compound can be one selected from the group consisting of potassium sulfate (K2SO4), sodium carbonate (Na2CO3), sodium chloride (NaCl), potassium chloride (KCl), calcium chloride (CaCl2), magnesium chloride (MgCl2), sodium nitrate (NaNO3), potassium nitrate (KNO3), calcium nitrate (Ca(NO3)2), magnesium nitrate (Mg(NO3)2), sodium sulfate (Na2SO4), calcium sulfate (CaSO4), magnesium sulfate (MgSO4), sodium hydroxide (NaOH), potassium hydroxide (KOH), calcium hydroxide (Ca(OH)2), magnesium hydroxide (Mg(OH)2), sodium bicarbonate (NaHCO3), potassium bicarbonate (KHCO3), potassium carbonate (K2CO3), sodium bisulfite (NaHSO4), potassium bisulfite (KHSO4), sodium pyrophosphate (Na4P2O7), potassium pyrophosphate (K4P2O7), trisodium phosphate (Na3PO4), tripotassium phosphate (K3PO4), monosodium phosphate (Na2HPO4), monopotassium phosphate (K2HPO4), and a combination of two or more thereof, for example, can be a combination of potassium sulfate and sodium carbonate, but is not limited thereto.

[0035] The composition can include 30 to 98 parts by weight of the conjugated diene-based monomer, 1 to 55 parts by weight of the ethylenically unsaturated nitrile monomer, and 0.001 to 20 parts by weight of the ethylenically unsaturated acid monomer, but is not limited thereto.

[0036] For example, the conjugated diene-based monomer content of the above composition can be 30 parts by weight, 32 parts by weight, 34 parts by weight, 36 parts by weight, 38 parts by weight, 40 parts by weight, 42 parts by weight, 44 parts by weight, 46 parts by weight, 48 parts by weight, 50 parts by weight, 52 parts by weight, 54 parts by weight, 56 parts by weight, 58 parts by weight, 60 parts by weight, 62 parts by weight, 64 parts by weight, 66 parts by weight, 68 parts by weight, 70 parts by weight, 72 parts by weight, 74 parts by weight, 76 parts by weight, 78 parts by weight, 80 parts by weight, 82 parts by weight, 84 parts by weight, 86 parts by weight, 88 parts by weight, 90 parts by weight, 92 parts by weight, 94 parts by weight, 96 parts by weight, 98 parts by weight, or a range between any two of the above values. If the content of the conjugated diene-based monomer is less than the above range, the dip-molded product can be excessively cured, thus poor in wearing comfort, and if the content of the conjugated diene-based monomer exceeds the above range, the durability or chemical resistance of the dip-molded product can be lowered.

[0037] The content of the ethylenically unsaturated nitrile monomer in the above composition can be 1 part by weight, 2.5 parts by weight, 5 parts by weight, 7.5 parts by weight, 10 parts by weight, 12.5 parts by weight, 15 parts by weight, 17.5 parts by weight, 20 parts by weight, 22.5 parts by weight, 25 parts by weight, 27.5 parts by weight, 30 parts by weight, 32.5 parts by weight, 35 parts by weight, 37.5 parts by weight, 40 parts by weight, 42.5 parts by weight, 45 parts by weight, 47.5 parts by weight, 50 parts by weight, 52.5 parts by weight, 55 parts by weight, or a range between any two of the above values. If the content of the ethylenically unsaturated nitrile monomer is less than the above range, the chemical resistance or mechanical strength of the dip-molded product can be lowered, and if the content of the ethylenically unsaturated nitrile monomer exceeds the above range, the elongation of the dip-molded product can be lowered, resulting in a decrease in usability.

[0038] For example, the content of the ethylenically unsaturated acid monomer in the above composition can be 0.001 parts by weight, 0.5 parts by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, 5 parts by weight, 5.5 parts by weight, 6 parts by weight, 6.5 parts by weight, 7 parts by weight, 7.5 parts by weight, 8 parts by weight, 8.5 parts by weight, 9 parts by weight, 9.5 parts by weight, 10 parts by weight, 10.5 parts by weight, 11 parts by weight, 11.5 parts by weight, 12 parts by weight, 12.5 parts by weight, 13 parts by weight, 13.5 parts by weight, 14 parts by weight, 14.5 parts by weight, 15 parts by weight, 15.5 parts by weight, 16 parts by weight, 16.5 parts by weight, 17 parts by weight, 17.5 parts by weight, 18 parts by weight, 18.5 parts by weight, 19 parts by weight, 19.5 parts by weight, 20 parts by weight, or a range between two of the values. If the content of the ethylenically unsaturated acid monomer is less than the above range, the tensile strength of the dip-molded product can decrease, and if the content of the ethylenically unsaturated acid monomer exceeds the above range, the dip-molded product can be over-cured, and thus the wearing comfort can be poor.

[0039] The above conjugated diene-based monomer can include isoprene. For example, the above conjugated diene-based monomer can include isoprene and one or more conjugated diene-based monomers other than isoprene.

[0040] The above conjugated diene-based monomer can include 29 parts by weight to 97 parts by weight of isoprene and 1 part by weight to 50 parts by weight of a conjugated diene-based monomer other than isoprene, but is not limited thereto. For example, the content of the above isoprene can be 29 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight, 80 parts by weight, 85 parts by weight, 90 parts by weight, 95 parts by weight, 97 parts by weight, or a range between two of the values, and if the content of the isoprene is less than the above range, the durability of the dip-molded product manufactured from the above composition can decrease.

[0041] The weight ratio of the above isoprene to the above ethylenically unsaturated nitrile monomer can be 1.0 to 3.5. If the weight ratio of the isoprene to the ethylenically unsaturated nitrile monomer exceeds the above range, the durability of the dip-molded product manufactured from the above composition can decrease.

[0042] The weight ratio of the above ethylenically unsaturated acid monomer to the above ethylenically unsaturated nitrile monomer can be 0.1 to 0.4. If the weight ratio of the ethylenically unsaturated acid monomer to the ethylenically unsaturated nitrile monomer exceeds the above range, the durability of the dip-molded product manufactured from the above composition can decrease.

[0043] In the present specification, the "total sum of monomers" refers to the total sum of the above-mentioned conjugated diene-based monomer, the above-mentioned ethylenically unsaturated nitrile monomer, and the above-mentioned ethylenically unsaturated acid monomer, however, the above-mentioned latex polymerization composition can further include a polymerizable monomer other than the above-mentioned conjugated diene-based monomer, ethylenically unsaturated nitrile monomer, and ethylenically unsaturated acid monomer, in which case, the "total sum of monomers" further includes the above-mentioned polymerizable monomer.

[0044] The total content of the above-mentioned ionic organic compound and the above-mentioned ionic inorganic compound can vary depending on the monomer composition ratio and the type of ionic compound. The total content of the above-mentioned ionic organic compound and the above-mentioned ionic inorganic compound can be 0.1 parts by weight to 0.6 parts by weight, based on 100 parts by weight of the total sum of monomers. For example, the total content can be 0.1 parts by weight, 0.11 parts by weight, 0.12 parts by weight, 0.13 parts by weight, 0.14 parts by weight, 0.15 parts by weight, 0.16 parts by weight, 0.17 parts by weight, 0.18 parts by weight, 0.19 parts by weight, 0.2 parts by weight, 0.21 parts by weight, 0.22 parts by weight, 0.23 parts by weight, 0.24 parts by weight, 0.25 parts by weight, 0.26 parts by weight, 0.27 parts by weight, 0.28 parts by weight, 0.29 parts by weight, 0.3 parts by weight, 0.31 parts by weight, 0.32 parts by weight, 0.33 parts by weight, 0.34 parts by weight, 0.35 parts by weight, 0.36 parts by weight, 0.37 parts by weight, 0.38 parts by weight, 0.39 parts by weight, 0.4 parts by weight, 0.41 parts by weight, 0.42 parts by weight, 0.43 parts by weight, 0.44 parts by weight, 0.45 parts by weight, 0.46 parts by weight, 0.47 parts by weight, 0.48 parts by weight, 0.49 parts by weight, 0.5 parts by weight, 0.51 parts by weight, 0.52 parts by weight, 0.53 parts by weight, 0.54 parts by weight, 0.55 parts by weight, 0.56 parts by weight, 0.57 parts by weight, 0.58 parts by weight, 0.59 parts by weight, 0.6 parts by weight, or a range between two of the values. If the total content of the ionic organic compound and the ionic inorganic compound is less than the above range, the ionic conductivity of the composition can decrease, or the stability of the latex can decrease, and due to the decrease in the particle size of the latex and the increase in the viscosity due to the high polymerization reaction speed, difficulties in product storage and reaction heat control can occur. If the total content of the ionic organic compound and the ionic inorganic compound exceeds the above range, the polymerization reaction speed can decrease, resulting in a decrease in the final conversion rate, and the mechanical properties and practical use durability of the dip-molded product manufactured therefrom can decrease.

[0045] The ionic conductivity of the above composition can be 250 μs / cm or more. For example, the ionic conductivity can be 250 μs / cm, 255 μs / cm, 260 μs / cm, 265 μs / cm, 270 μs / cm, 275 μs / cm, 280 μs / cm, 285 μs / cm, 290 μs / cm, 295 μs / cm, 300 μs / cm, 305 μs / cm, 310 μs / cm, 315 μs / cm, 320 μs / cm, 325 μs / cm, 330 μs / cm, 335 μs / cm, 340 μs / cm, 345 μs / cm, 350 μs / cm, 355 μs / cm, 360 μs / cm, 365 μs / cm, 370 μs / cm, 375 μs / cm, 380 μs / cm, 385 μs / cm, 390 μs / cm, 395 μs / cm, 400 μs / cm, a range between two of the values, or one of the values or more. If the ionic conductivity of the composition is lower than the above range, the stability of the polymerized latex can decrease, and the viscosity can rapidly increase when the solid matter is concentrated.

[0046] The ionic conductivity of the above composition can be 10 ms / cm or less, 5 ms / cm or less, or 1 ms / cm or less, but is not limited thereto. If the ionic conductivity of the above composition is too high, the components not required in polymerization increase, and thus the stability of the latex deteriorates.

[0047] The above composition can further include water, an emulsifier, a polymerization initiator, and a molecular weight regulator.

[0048] The content of the water described above can be 75 parts by weight to 150 parts by weight, for example, 75 parts by weight, 77.5 parts by weight, 80 parts by weight, 82.5 parts by weight, 85 parts by weight, 87.5 parts by weight, 90 parts by weight, 92.5 parts by weight, 95 parts by weight, 97.5 parts by weight, 100 parts by weight, 102.5 parts by weight, 105 parts by weight, 107.5 parts by weight, 110 parts by weight, 112.5 parts by weight, 115 parts by weight, 117.5 parts by weight, 120 parts by weight, 122.5 parts by weight, 125 parts by weight, 127.5 parts by weight, 130 parts by weight, 132.5 parts by weight, 135 parts by weight, 137.5 parts by weight, 140 parts by weight, 142.5 parts by weight, 145 parts by weight, 147.5 parts by weight, 150 parts by weight, or a range between two of these values, based on 100 parts by weight of the total of the monomers described above. If the content of the water is less than the range described above, the viscosity at the time of polymerization can excessively increase and it can be difficult to produce a molded product, and if the content of the water exceeds the range described above, the content of the solid matter can excessively decrease. The ionic conductivity of the water described above can be 5 μs / cm or less, 2.5 μs / cm or less, or 1 μs / cm or less. For example, the water described above can be ion-exchanged water, ultrapure water, or purified water. When water having a high ionic conductivity is used, impurities that adversely affect the stability of polymerization or the stability of the latex can be contained.

[0049] The emulsifier described above can be an anionic surfactant, a nonionic surfactant, a cationic surfactant, or an amphoteric surfactant. For example, as the anionic surfactant, one or more selected from the group consisting of alkylbenzenesulfonate, fatty sulfonate, sulfate ester of higher alcohol, a-olefin sulfonate, and alkyl ether sulfate can be used, but the present application is not limited thereto. The content of the emulsifier described above can be 0.8 parts by weight to 8 parts by weight, based on 100 parts by weight of the total of the monomers described above.

[0050] The polymerization initiator described above can be a free radical initiator. For example, the free radical initiator described above can be at least one selected from the group consisting of inorganic peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium peroxodisulfate, and hydrogen peroxide; organic peroxides such as tertiary butyl peroxide, cumene hydroperoxide, p-menthane hydroperoxide, di-tertiary butyl peroxide, tertiary butyl cumyl peroxide, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, dibenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, and tertiary butyl isobutyrate peroxide; and azo initiators such as azobis isobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanenitrile, and methyl azobis isobutyrate, but the present application is not limited thereto. The content of the polymerization initiator described above can be 0.01 parts by weight to 1.5 parts by weight, based on 100 parts by weight of the total of the monomers described above.

[0051] The molecular weight regulator can be a mercaptan such as α-methylstyrene dimer, tertiary dodecyl mercaptan, n-dodecyl mercaptan, and octyl mercaptan; a halogenated hydrocarbon such as carbon tetrachloride, dichloromethane, and dibromomethane; and a sulfur-containing compound such as tetraethylthiuram disulfide, dipentamethylene thiuram disulfide, and diisopropyl xanthogen disulfide, but is not limited thereto. The content of the molecular weight regulator can be 0.1 to 1 parts by weight based on 100 parts by weight of the total of the monomers. For example, the content of the molecular weight regulator can be 0.1 parts by weight, 0.15 parts by weight, 0.2 parts by weight, 0.25 parts by weight, 0.3 parts by weight, 0.35 parts by weight, 0.4 parts by weight, 0.45 parts by weight, 0.5 parts by weight, 0.55 parts by weight, 0.6 parts by weight, 0.65 parts by weight, 0.7 parts by weight, 0.75 parts by weight, 0.8 parts by weight, 0.85 parts by weight, 0.9 parts by weight, 0.95 parts by weight, 1 parts by weight, or a range between two of the values. If the content of the molecular weight regulator is less than the above range, a gel is formed, resulting in a decrease in stability of the latex, and if the content of the molecular weight regulator is greater than the above range, in addition to a poor tensile strength or a decrease in stress retention rate, actual use durability is also decreased.

[0052] Emulsion for dip molding The dip-molding latex according to another aspect of the present specification can include a copolymer derived from the latex polymerization composition described above.

[0053] The average particle diameter of the copolymer described above can be 1,000 to 3,000 Å. For example, the average particle diameter described above can be 1,000 Å, 1,050 Å, 1,100 Å, 1,150 Å, 1,200 Å, 1,250 Å, 1,300 Å, 1,350 Å, 1,400 Å, 1,450 Å, 1,500 Å, 1,550 Å, 1,600 Å, 1,650 Å, 1,700 Å, 1,750 Å, 1,800 Å, 1,850 Å, 1,900 Å, 1,950 Å, 2,000 Å, 2,050 Å, 2,100 Å, 2,150 Å, 2,200 Å, 2,250 Å, 2,300 Å, 2,350 Å, 2,400 Å, 2,450 Å, 2,500 Å, 2,550 Å, 2,600 Å, 2,650 Å, 2,700 Å, 2,750 Å, 2,800 Å, 2,850 Å, 2,900 Å, 2,950 Å, 3,000 Å, or a range between two of the values. The dip-molding latex is prepared by polymerizing a composition containing an ionic organic compound and an ionic inorganic compound, thereby minimizing a decrease in stability and increasing the particle diameter of the copolymer. In addition, the latex described above has a low oligomer content, and thus can have more excellent stability.

[0054] The zeta potential of the above-mentioned latex for dip molding can be 60 mV or more, 62.5 mV or more, 65 mV or more, 67.5 mV or more, or 70 mV or more in absolute value. The latex satisfying these conditions has excellent stability, and can suppress the increase in viscosity even when concentrated to a high solid content of 50% by weight or more.

[0055] The viscosity of the above-mentioned latex for dip molding at 25°C can be 50 cps to 2,500 cps, for example, 50 cps, 75 cps, 100 cps, 125 cps, 150 cps, 175 cps, 200 cps, 225 cps, 250 cps, 275 cps, 300 cps, 325 cps, 350 cps, 375 cps, 400 cps, 425 cps, 450 cps, 475 cps, 500 cps, 525 cps, 550 cps, 575 cps, 600 cps, 625 cps, 650 cps, 675 cps, 700 cps, 725 cps, 750 cps, 775 cps, 800 cps, 825 cps, 850 cps, 875 cps, 900 cps, 925 cps, 950 cps, 975 cps, 1,000 cps, 1,100 cps, 1,200 cps, 1,300 cps, 1,400 cps, 1,500 cps, 1,600 cps, 1,700 cps, 1,800 cps, 1,900 cps, 2,000 cps, 2,100 cps, 2,200 cps, 2,300 cps, 2,400 cps, 2,500 cps, or a range between any two of these values. The latex having a viscosity outside the above-mentioned range can be substantially impossible to manufacture, or can be difficult to dip mold.

[0056] The solid content of the above-mentioned latex for dip molding can be 50% to 65% by weight, for example, 50% by weight, 52.5% by weight, 55% by weight, 57.5% by weight, 60% by weight, 62.5% by weight, 65% by weight, or a range between any two of these values. If the solid content exceeds the above-mentioned range, the effect produced by the above-mentioned stability improvement can not be needed, or coagulation of the latex can occur.

[0057] The impregnation molding latex can satisfy the average particle diameter, the solid content, and the viscosity at the same time in the above pH range. Although the solid content and the average particle diameter can vary when the pH of the latex is adjusted by an additive, the impregnation molding latex can satisfy the average particle diameter, the solid content, and the viscosity at the same time in the above pH range.

[0058] The impregnation molding latex can further include one or more additives selected from the group consisting of a chelating agent, a dispersant, a pH adjuster, an oxygen absorber, a particle diameter adjuster, an antioxidant, and an oxygen scavenger. As the additives, a configuration known in the art can be used, and the additives can be added before or after polymerization of the copolymer.

[0059] The impregnation molding latex satisfies low viscosity, high solid content, and large particle diameter at the same time, so that the stability of the latex itself can be good. Thus, even in the case of application of external impact or long-term storage, the quality deterioration of the impregnation molded product can be prevented.

[0060] Process for preparing emulsion for dip molding The method of preparing an impregnation molding latex according to another aspect of the present specification can include a step (a) of preparing a monomer mixture including a conjugated diene-based monomer, an ethylenically unsaturated nitrile monomer, and an ethylenically unsaturated acid monomer; a step (b) of adding an ionic organic compound, an ionic inorganic compound, an emulsifier, and water to the monomer mixture; and a step (c) of preparing the impregnation molding latex by adding a polymerization initiator.

[0061] The weight ratio of the ionic inorganic compound to the ionic organic compound added in the above step (b) can be 4.7 or more.

[0062] The above step (a) is a step of preparing a monomer mixture including a conjugated diene-based monomer, an ethylenically unsaturated nitrile monomer, and an ethylenically unsaturated acid monomer as monomers constituting a carboxylic acid-modified nitrile-based copolymer, and can be performed under a nitrogen atmosphere.

[0063] The above step (b) is a step of adding an ionic compound to prepare the latex polymerization composition. In the above step (b), an additional molecular weight adjuster can be added.

[0064] The polymerization of the above step (c) can be performed at 10°C to 90°C, for example, at 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, or a temperature between two of the temperatures, but is not limited thereto, and the polymerization temperature can be adjusted according to the target conversion rate.

[0065] The polymerization in the above step (c) can be performed for 2 hours to 24 hours, for example, for 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours, 24 hours, or for a time between two of the times, but is not limited thereto.

[0066] The above step (c) can further include a step of stopping the polymerization by adding a polymerization termination agent.

[0067] The above polymerization termination agent can be one selected from the group consisting of hydroxylamine, hydroxylamine sulfate, diethylhydroxylamine, hydroxylamine sulfonate and alkali metal ions thereof, sodium dimethyl dithiocarbamate, a hydroxy diethyl benzene dithiocarboxylic acid, a hydroxy dibutyl benzene dithiocarboxylic acid, and aromatic hydroxy dithiocarboxylic acids such as a hydroxy diethyl benzene dithiocarboxylic acid, and a combination of two or more thereof. The content of the above polymerization termination agent can be 0.02 parts by weight to 1.5 parts by weight with respect to 100 parts by weight of the above monomer mixture.

[0068] In the above step (c), the final conversion rate of the polymerization reaction can be 92% or more. For example, the above final conversion rate can be 92% or more, 93% or more, 94% or more, 95% or more, 96% or more, 97% or more, 98% or more, but is not limited thereto. If the conversion rate is less than the above range, the mechanical properties and actual use durability of the dip-molded product manufactured therefrom can be reduced as the amount of remaining unreacted monomers increases.

[0069] In addition, other raw materials, contents, and the like used in the above preparation method are as previously described.

[0070] Dip molded article The dip-molded product according to another aspect of the present specification can be manufactured from the above dip-molding latex.

[0071] The above dip-molded product can be manufactured by adding 1 parts by weight to 2 parts by weight of sulfur, 0.1 parts by weight to 1 part by weight of zinc oxide, and 0.3 parts by weight to 1.5 parts by weight of a vulcanization accelerator to the above dip-molding latex based on 100 parts by weight of the above dip-molding latex, and then performing dip-molding, but is not limited thereto.

[0072] The above-mentioned sulfur can form a crosslinked structure by reacting with a structure derived from the above-mentioned conjugated diene-based monomer. When the ionic organic compound and the ionic inorganic compound within the above-mentioned weight ratio range are put in, shrinkage of the molded product due to syneresis during vulcanization can be suppressed. For example, the content of the above-mentioned sulfur can be 1 part by weight, 1.1 parts by weight, 1.2 parts by weight, 1.3 parts by weight, 1.4 parts by weight, 1.5 parts by weight, 1.6 parts by weight, 1.7 parts by weight, 1.8 parts by weight, 1.9 parts by weight, 2 parts by weight, or a range between two of these values. If the content of sulfur is less than the above-mentioned range, the mechanical properties such as tensile strength and the actual use durability can be reduced, and if the content of the above-mentioned sulfur exceeds the above-mentioned range, an allergic reaction of the user can be caused.

[0073] The above-mentioned zinc oxide can form a crosslinked structure by forming an ionic bond with a structure derived from the above-mentioned ethylenically unsaturated acid. Furthermore, when the ionic organic compound and the ionic inorganic compound within the above-mentioned weight ratio range are put in, the above-mentioned ionic bond strength can be improved to improve the durability. For example, the content of the above-mentioned zinc oxide can be 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.4 parts by weight, 0.5 parts by weight, 0.6 parts by weight, 0.7 parts by weight, 0.8 parts by weight, 0.9 parts by weight, 1 part by weight, or a range between two of these values. If the content of zinc oxide is less than the above-mentioned range, the actual use durability can be reduced, and if the content of zinc oxide exceeds the above-mentioned range, the tensile strength can be reduced.

[0074] The above-mentioned dip-molded product can be dip-molded after adjusting the solid content by adding an aqueous potassium hydroxide solution to the above-mentioned dip-molding latex, but is not limited thereto.

[0075] The tensile strength of the above-mentioned dip-molded product can be 3 MPa or more, 5 MPa or more, 7 MPa or more, 9 MPa or more, 11 MPa or more, 13 MPa or more, 15 MPa or more, 20 MPa or more, 25 MPa or more, 30 MPa or more, or 35 MPa or more, but is not limited thereto. The higher the tensile strength, the higher the durability during storage, but other mechanical properties such as elongation can be reduced.

[0076] The elongation of the above-mentioned dip-molded product can be 600% or more, 650% or more, 700% or more, 750% or more, 800% or more, 850% or more, or 900% or more, but is not limited thereto. The higher the elongation, the better the wearing feeling, etc., but there can be a trade-off relationship with other mechanical properties.

[0077] The durability test result of the above-mentioned impregnated molded product according to the following durability test method is 60 minutes or more, which indicates that the practical use durability is excellent and the quality is high. For example, the durability test result of the above-mentioned impregnated molded product can be 60 minutes or more, 90 minutes or more, 120 minutes or more, 150 minutes or more, 180 minutes or more, 210 minutes or more, or 240 minutes or more.

[0078] Durability test method An impregnated molded product having a width of 30 mm, a length of 135 mm, and a thickness of 0.06 mm to 0.08 mm is stretched by 20% in the length direction, and immersed in a solution of 35°C, pH 4.0 to 4.3, and the process of stretching the above-mentioned molded product by 50% in the length direction for 10 seconds, fixing for 2 seconds, and then relaxing by 20% in the length direction for 10 seconds is repeatedly performed, thereby measuring the time at which the above-mentioned molded product is damaged.

[0079] The above-mentioned durability test method is to confirm whether the sample is damaged by repeatedly elongating and relaxing in a solution of 35°C, pH 4.0 to 4.3, which is a condition similar to the skin and body fluid having a high possibility of contact when the impregnated molded product is actually used. For example, if the above-mentioned molded product is a glove, the durability of the impregnated molded product under actual use conditions can be measured by simulating the case in which the molded product is repeatedly elongated and relaxed according to the movement of the fingers.

[0080] The above-mentioned impregnated molded product can be a surgical glove, a medical glove, a livestock processing glove, an industrial glove, a condom, a cosmetic material, a catheter, or a health care molded product, but is not limited thereto. For example, the above-mentioned impregnated molded product can be a surgical glove or other medical glove, an industrial glove such as a chemical handling glove, or a cosmetic material such as a puff.

[0081] Hereinafter, the embodiments of the present specification will be described in more detail. However, the following experimental results are only representative experimental results in the above-mentioned embodiments, and the embodiments and the like should not be understood as limiting or restricting the scope and content of the present specification. The effects of the various embodiments of the present specification not explicitly presented hereinafter are specifically described in the corresponding parts.

[0082] Examples and comparative examples A 1L high-pressure reactor equipped with a stirrer, a thermometer, a cooler, and a nitrogen inlet / outlet, and allowing continuous addition of each component such as monomers, an emulsifier, a polymerization initiator, etc. was prepared. As ion exchange water, water having a conductivity of 1 μs / cm or less was prepared. After the above reactor was replaced with nitrogen, a monomer mixture of 40 wt% isoprene (IP), 25 wt% 1,3-butadiene (BD), 30 wt% acrylonitrile (AN), and 5 wt% methacrylic acid (MAA) based on the total weight of the monomer mixture was added. Then, with respect to 100 parts by weight of the above monomer mixture, ethylenediaminetetraacetic acid (EDTA) as an ionic organic compound, potassium sulfate (K2SO4) and sodium carbonate (Na2CO3) as ionic inorganic compounds, 0.5 parts by weight of t-dodecyl mercaptan (TDDM) as a molecular weight regulator, 2 parts by weight of sodium alkylbenzenesulfonate as an emulsifier, and 120 parts by weight of ion exchange water were added to the above reactor, thereby preparing a composition for latex polymerization. After the temperature of the above reactor was raised to about 40°C, 0.3 parts by weight of potassium persulfate as a polymerization initiator was added. After 12 hours of polymerization, 0.9 parts by weight of sodium hydroxide was added to terminate the polymerization reaction. Thereafter, unreacted monomers, etc. were removed through a deodorization process, and ammonia water, an antioxidant, and a defoaming agent, etc. were added to obtain a carboxylic acid-modified nitrile-based copolymer latex having a pH of 8.5.

[0083] The content of the ionic compound used in each of the examples and the comparative example and the weight ratio thereof are shown in Table 1 below.

[0084] Table 1

[0085] Experimental example 1 The final conversion rate, the initial conversion rate (after 2 hours of polymerization), the average particle diameter, the ionic conductivity, the solid content, the viscosity at 25°C, and the zeta potential of the carboxylic acid-modified nitrile-based copolymer latex obtained in the above examples and comparative example were measured, and the results are shown in Table 2 below.

[0086] - Average particle diameter (Å): measured by dynamic laser light scattering using Nanorac 150.

[0087] - Ionic conductivity (μs / cm): The ionic conductivity was determined by Nyquist representation after measuring the resistance by electrochemical impedance spectroscopy (EIS) using a two-electrode method. The resistance was measured at a frequency of 60 Hz to 1 kHz, a current of 10.0 mV, and a voltage range of ±10 V. The ionic conductivity was measured after calibration using a standard solution within the expected range. A graphite electrode was used as the electrode. The ionic conductivity is a value corrected at 25°C.

[0088] - 25°C viscosity (cps): The Brookfield viscometer was used to measure the viscosity at 62 and 100 rpm.

[0089] - Zeta potential (mV): The zeta potential at 25°C was measured using a Malvern Zetasizer instrument.

[0090] Table 2

[0091] Referring to Table 2 above, Examples 1 to 3 all exhibited high conversion rates, had higher ionic conductivities compared to the latex of Comparative Example 3 in which no ionic compound was added, and the zeta potential size indicating the electrical stability of the latex particles was measured to be relatively large. In addition, the latexes of Examples 1 to 3 achieved a large particle size of 1,000 A or more and a high solid content of 50% by weight or more, while exhibiting low viscosity.

[0092] In the case of Comparative Examples 1 and 2, the ionic conductivity was higher compared to the latex of Comparative Example 3 in which no ionic compound was added, the zeta potential size was measured to be larger, a large particle size of 1,000 A or more and a high solid content of 50% by weight or more were achieved, while exhibiting low viscosity, and in this regard, they showed similar physical properties to the above-described Examples 1 to 3. However, the reaction speed was slow, so the initial conversion rate was lower than in the examples, and the final conversion rate was also low, and thus it can be confirmed that a relatively large amount of unreacted monomer still remained even after the polymerization was completed.

[0093] The zeta potential size measured from the latex of Comparative Example 3 in which no ionic compound was added was small, and it was difficult to simultaneously achieve a large particle size, a high solid content, and low viscosity due to low stability. In addition, the reaction speed was fast, the particle size was small, and the viscosity was high, and there were difficulties in product storage and reaction heat control. In particular, the latex of Comparative Example 3 in which the particle size was small had a problem in that the viscosity sharply increased when the solid content was increased by concentration.

[0094] Preparation example To 100 parts by weight of each of the carboxylic acid-modified nitrile-based copolymer latex prepared according to the above examples and comparative examples, 1.8 parts by weight of sulfur (S), 0.7 parts by weight of zinc oxide (ZnO), and 1.2 parts by weight of zinc dibutyl dithiocarbamate (ZDBC) as a vulcanization accelerator were added. Then, 4% of an aqueous potassium hydroxide solution and distilled water were added to prepare a latex composition for dip molding having a solid content of 20% and a pH of 10.0.

[0095] Experimental example 2 From each of the latex compositions for dip molding prepared according to the above preparation examples, rectangular samples having a width of 30 mm, a length of 135 mm, and a thickness of 0.072 to 0.074 mm were manufactured, and the durability of the samples was evaluated. The results are shown in Table 3 below.

[0096] - Durability: A solution having a pH of 4 was prepared using citric acid and maintained at 35°C. The rectangular sample was added to the above solution in a state of being elongated by 20% along the length. After repeating the work of stretching the above sample by 50% for 10 seconds, fixing for 2 seconds, and then relaxing by 20% for 10 seconds, the time until the sample was broken was measured.

[0097] Table 3

[0098] Referring to Table 3 above, the samples manufactured using the latexes of Examples 1 to 3 exhibited excellent actual use durability compared to the samples manufactured using the latexes of Comparative Examples 1 to 3. In particular, the samples manufactured using the latexes of Comparative Examples 1 or 2 were broken within 1 hour, confirming that the actual use durability was insufficient.

[0099] The above description of the present specification is merely illustrative, and as long as a person having ordinary skill in the art to which the present specification belongs can understand that it can be easily modified into other specific forms without changing the technical idea or essential characteristics of the present specification. Therefore, it should be understood that the above-described examples are merely illustrative in all aspects, but are not limited thereto. For example, each of the structural components described as a single type can be implemented in a dispersed manner, and similarly, each of the structural components described in a dispersed manner can be implemented in a combined manner.

[0100] The scope of the present specification is represented by the appended claims, not by the above detailed description, and all modifications or variations derived from the meaning, range, and equivalent concept of the appended claims should be interpreted as being included in the scope of the present specification.

Claims

1. A composition for emulsion polymerization, comprising a conjugated diene-based monomer, an ethylenically unsaturated nitrile monomer, an ethylenically unsaturated acid monomer, an ionic organic compound, and an ionic inorganic compound, wherein, The weight ratio of the ionic inorganic compound to the ionic organic compound is 4.7 or more.

2. The latex polymerization composition of claim 1, wherein, The conjugated diene monomer is one selected from the group consisting of 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 2-phenyl-1,3-butadiene, 3-methyl-1,3-pentadiene, 2-chloro-1,3-butadiene, 3-butyl-1,3-octadiene, octadiene, and combinations of two or more thereof.

3. The latex polymerization composition of claim 1, wherein, The ethylenically unsaturated nitrile monomer is one selected from the group consisting of acrylonitrile, methacrylonitrile, fumaronitrile, α-chloronitrile, α-cyanoethyl acrylonitrile, and combinations of two or more thereof.

4. The latex polymerization composition of claim 1, wherein, The ethylenically unsaturated acid monomer is one selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, maleic anhydride, citraconic anhydride, styrene sulfonic acid, monobutyl fumarate, monobutyl maleate, mono-2-hydroxypropyl maleate, and combinations of two or more thereof.

5. The latex polymerization composition of claim 1, wherein, The ionic organic compound is one selected from the group consisting of ethylenediaminetetraacetic acid (EDTA) or a sodium salt thereof, ethylene glycol tetraacetic acid (EGTA) or a sodium salt thereof, nitrilotriacetic acid (NTA) or a sodium salt thereof, iminodiacetic acid (IDA) or a sodium salt thereof, quinolinic acid (QNA) or a sodium salt thereof, and combinations of two or more thereof.

6. The latex polymerization composition of claim 1, wherein, The ionic inorganic compound is one selected from the group consisting of potassium sulfate (K2SO4), sodium carbonate (Na2CO3), sodium chloride (NaCl), potassium chloride (KCl), calcium chloride (CaCl2), magnesium chloride (MgCl2), sodium nitrate (NaNO3), potassium nitrate (KNO3), calcium nitrate (Ca(NO3)2), magnesium nitrate (Mg(NO3)2), sodium sulfate (Na2SO4), calcium sulfate (CaSO4), magnesium sulfate (MgSO4), sodium hydroxide (NaOH), potassium hydroxide (KOH), calcium hydroxide (Ca(OH)2), magnesium hydroxide (Mg(OH)2), sodium bicarbonate (NaHCO3), potassium bicarbonate (KHCO3), potassium carbonate (K2CO3), sodium bisulfite (NaHSO4), potassium bisulfite (KHSO4), sodium pyrophosphate (Na4P2O7), potassium pyrophosphate (K4P2O7), trisodium phosphate (Na3PO4), tripotassium phosphate (K3PO4), monosodium phosphate (Na2HPO4), monopotassium phosphate (K2HPO4), and combinations of two or more thereof.

7. The latex polymerization composition of claim 1, wherein, The composition includes 30 to 98 parts by weight of the conjugated diene monomer, 1 to 55 parts by weight of the ethylenically unsaturated nitrile monomer, and 0.001 to 20 parts by weight of the ethylenically unsaturated acid monomer.

8. The latex polymerization composition of claim 1, wherein, The composition further includes water, an emulsifier, a polymerization initiator, and a molecular weight regulator.

9. A latex for dip molding, comprising a copolymer derived from the latex polymerization composition according to claim 1.

10. A dip-molded article produced from the latex for dip molding according to claim 9.

11. The dip-molded article of claim 10, wherein, The dip-molded product is a surgical glove, a medical glove, a livestock processing glove, an industrial glove, a condom, a cosmetic material, a catheter, or a health care molded product. The dip-molded product is a surgical glove, a medical glove, a livestock processing glove, an industrial glove, a condom, a cosmetic material, a catheter, or a health care molded product.

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