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WO2016105112A1 - Composition de latex pour moulage par immersion et article moulé par immersion obtenu à l'aide de la composition - Google Patents

Composition de latex pour moulage par immersion et article moulé par immersion obtenu à l'aide de la composition Download PDF

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Publication number
WO2016105112A1
WO2016105112A1 PCT/KR2015/014158 KR2015014158W WO2016105112A1 WO 2016105112 A1 WO2016105112 A1 WO 2016105112A1 KR 2015014158 W KR2015014158 W KR 2015014158W WO 2016105112 A1 WO2016105112 A1 WO 2016105112A1
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WO
WIPO (PCT)
Prior art keywords
latex
weight
latex composition
dip molding
dip
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2015/014158
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English (en)
Korean (ko)
Inventor
조원태
김현우
여승욱
양승훈
김지현
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LG Chem Ltd
Original Assignee
LG Chem Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020150183167A external-priority patent/KR101775798B1/ko
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to CN201580056644.5A priority Critical patent/CN107075141B/zh
Priority to US15/516,727 priority patent/US10100179B2/en
Priority to JP2017516740A priority patent/JP6458139B2/ja
Publication of WO2016105112A1 publication Critical patent/WO2016105112A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B29C41/14—Dipping a core
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/02—Direct processing of dispersions, e.g. latex, to articles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02—Copolymers with acrylonitrile
    • C08L9/04—Latex

Definitions

  • the present invention relates to a latex composition for dip molding comprising a nitrile-based hybrid latex, and a dip molded article having high tensile strength and elongation at the same time, with improved fit and reduced modulus.
  • natural rubber has been mainly used as a raw material for products requiring elasticity such as industrial, medical, food gloves and balloons.
  • natural rubber is rapidly being replaced by nitrile rubber, causing side effects such as severe protein allergies in some users.
  • nitrile rubber has high oil resistance, so it is widely used in work gloves, medical, and food gloves that handle organic solvents, and it is not easily penetrated by needles, etc., compared to natural products, so it is used for medical workers who handle scalpels or needles. This is suitable.
  • glove manufacturers are aiming to produce thin, hard-to-tear gloves to increase the productivity of glove production. From the beginning of nitrile glove production, glove manufacturers can produce gloves with high tensile strength and durability. There is a constant demand for latex for dip molding.
  • a dip molded product To provide a dip molded product.
  • 100 parts by weight of a nitrile-based hybrid latex comprising a first latex and a second latex having different glass transition temperatures; And 2 to 8 parts by weight of the ion conductive polymer having a weight average molecular weight of 400 to 1000 is provided.
  • the first latex may have a glass transition temperature of -50 to -25 ° C
  • the second latex may have a glass transition temperature of -25 to -15 ° C.
  • the first latex may have an average particle diameter of 90 to 200 nm
  • the second latex may have an average particle diameter of 100 to 200 nm.
  • the hybrid latex may include 30 to 80 wt% of the first latex and 20 to 70 wt% of the second latex.
  • the ion conductive polymer may have a weight average molecular weight of 550 to 650.
  • the ion conductive polymer may be one or more selected from the group consisting of polyethylene glycol, polyethylene oxide, polypropylene glycol, and polyethylene glycol methacrylate.
  • the ion conductive polymer may be polyethylene glycol, polyethylene oxide or a mixture thereof.
  • the ion conductive polymer may be diluted to 5-20% in an aqueous solvent.
  • the ion conductive polymer may include a glass transition temperature of -45 to -35 °C.
  • the dip molding latex composition may include a pH of 8 to 12.
  • the dip molding latex composition may have a concentration of solids of 10 to 40% by weight.
  • the step of manufacturing the first and second latex, respectively, the glass transition temperature is different; Preparing a first latex composition and a second latex composition by mixing an ion conductive polymer having a weight average molecular weight of 400 to 1000 with the first latex and the second latex, respectively; And blending the first latex composition and the second latex composition to produce a nitrile-based hybrid latex composition, wherein the nitrile-based hybrid latex is 100 parts by weight and the weight average molecular weight is 400 to 1000 1 to 8 parts by weight of the ion conductive polymer.
  • a method for producing a latex composition for dip molding comprising the step of: blending as possible.
  • the nitrile-based hybrid latex includes 30 to 80 wt% of the first latex having a glass transition temperature of -50 to -25 ° C and 20 to 70 wt% of the second latex having a glass transition temperature of -25 to -15 ° C. Can be.
  • the ion conductive polymer may be polyethylene glycol, polyethylene oxide or a mixture thereof.
  • the preparing of the first latex and the second latex may include 40 to 89 wt% of the conjugated diene monomer, 10 to 50 wt% of the ethylenically unsaturated nitrile monomer, and 0.1 to 15 wt% of the ethylenically unsaturated acid monomer. It may be to include the step of preparing a monomer mixture.
  • the latex composition for dip molding according to the present invention includes an ion conductive polymer in a nitrile-based hybrid latex, thereby improving compatibility when blending, and thus greatly improving low temperature stability of the composition, such as tensile strength and elongation of the manufactured dip molded product.
  • the mechanical properties can be improved, and the fit can be greatly improved due to the reduction of modulus.
  • mechanical properties and modulus can be controlled, which is advantageous for the production of a target product suitable for the purpose, and a dip molded product manufactured using the same is required. It can be easily applied to industries such as rubber gloves industry.
  • a latex composition for deep molding in which a predetermined amount of a nitrile-based hybrid latex and an ion conductive polymer having a specific weight average molecular weight are mixed in order to achieve the effects of improving the wearing comfort, improving the tensile strength and improving the elongation rate of the dip molded product.
  • Dip molding latex composition 100 parts by weight of a nitrile-based hybrid latex comprising a first latex and a second latex having different glass transition temperatures; And 2 to 8 parts by weight of the ion conductive polymer having a weight average molecular weight of 400 to 1000.
  • the dip molding latex composition may include a carboxylic acid-modified nitrile latex.
  • the latex may include, for example, a latex having a glass transition temperature of -50 to -15 ° C, or -45 to -25 ° C.
  • the glass transition temperature of the carboxylic acid-modified nitrile-based latex satisfies the above range, the dip molded product produced by this may have excellent tensile strength and elongation.
  • the glass transition temperature is higher than -15 ° C, cracks may easily occur in the manufacturing of the dip molded product.
  • the glass transition temperature is lower than -50 ° C, the tensile strength of the product may be significantly lowered when the dip molding is manufactured.
  • the carboxylic acid-modified nitrile-based latex may include an average particle diameter of 90 to 200 nm.
  • the average particle diameter of the carboxylic acid-modified nitrile latex is less than 90 nm, the viscosity of the latex itself may be increased, and a quality problem may occur in which the dip molded product is made transparent.
  • the average particle diameter exceeds 200 nm, excessive time is required during latex production, which may lead to a decrease in productivity, and the tensile strength of the manufactured article may be lowered.
  • the carboxylic acid-modified nitrile-based latex may be a hybrid latex including two kinds of latex having different glass transition temperatures. That is, a hybrid latex obtained by mixing two kinds of latexes having different glass transition temperatures in a predetermined ratio may be applied to the latex composition for dip molding.
  • a hybrid latex obtained by mixing two kinds of latexes having different glass transition temperatures in a predetermined ratio may be applied to the latex composition for dip molding.
  • the first latex may have a glass transition temperature of -50 to -25 ° C
  • the second latex may have a glass transition temperature of -25 to -15 ° C.
  • two kinds of latexes having different glass transition temperatures may be selected, prepared, and used.
  • the first latex When the carboxylic acid-modified nitrile-based latex is a mixed latex, the first latex may have an average particle diameter of 90 to 200 nm, and the second latex may have an average particle diameter of 100 to 200 nm.
  • latexes of different sizes When selecting two latexes, latexes of different sizes may be selected and used as the first and second latexes, or latexes of the same size may be selected, and a mixture of these latexes may be applied as a hybrid latex.
  • the average particle diameter of the second latex exceeds 200 nm, it may be mixed with the first latex so that a uniform film may not be formed when the dip molded article is manufactured, and thus tensile strength may be lowered.
  • the mixing ratio of the two latexes may be 30 to 80 wt% of the first latex and 20 to 70 wt% of the second latex. That is, the first latex and the second latex may be mixed at a weight ratio of 3: 7 to 8: 2, and if the first latex is included less than the ratio of 3: 7, the elongation may be sharply lowered and durability may be deteriorated. In addition, when the first latex is included more than the ratio of 8: 2, the degree of improvement in tensile strength may be insignificant.
  • the latex composition for dip molding may include an ion conductive polymer, and may include 2 to 8 parts by weight of an ion conductive polymer relative to 100 parts by weight of the nitrile-based mixed latex mixed together in the composition.
  • the ion conductive polymer can lower the modulus of the dip molded product manufactured by acting as a plasticizer on the nitrile-based hybrid latex, thereby greatly improving the wearing comfort and greatly improving the low temperature stability of the composition itself.
  • the syneresis time may be shortened when preparing the latex composition for dip molding, and the stability of the latex composition for dip molding may be reduced, and the dip molded article may be too sticky. It may give a feeling or decrease the physical properties.
  • the ion conductive polymer is included in the range of 1 to 8 parts by weight, the low temperature stability effect of the latex composition for dip molding may be excellent, and the mixing property with the carboxylic acid-modified nitrile latex is excellent to achieve uniform mixing. Can be.
  • the ion conductive polymer is a polymer containing at least one hydroxyl group at a terminal, and may be used without particular limitation as long as it has the characteristics of primary alcohol, but if possible, polyethylene glycol, polyethylene oxide, polypropylene glycol, polyethylene glycol methacrylate or Mixtures of these may be used, and polyethylene glycol and polyethylene oxide may be preferably used.
  • the weight average molecular weight of the ion conductive polymer that can be applied may be about 400 to 1000.
  • the ion conductive polymer has a low molecular weight, it is greatly influenced by the reactivity of the terminal functional group, and when the molecular weight is high, the ratio of the terminal group is lowered. Since hydrogen bonds to oxygen atoms can have an important effect, it may be important to control the weight average molecular weight in an appropriate range.
  • the weight average molecular weight is 400 to 1000
  • the physical properties of the latex composition for deep molding and a dip molded product using the same may be improved, and when the weight average molecular weight is less than 400, it may be difficult to impart plasticity to the hybrid latex. If 1000 is exceeded, there is a fear that it will interfere with the compatibility.
  • the weight average molecular weight is in the range of 400 to 1000
  • the hygroscopicity according to the relative humidity of the ion conductive polymer may be appropriate, and thus the workability (synergy) may be excellent, but within the above range, the relative humidity of the surrounding environment may be Therefore, it is necessary to adjust the weight average molecular weight appropriately.
  • the present invention is not limited thereto, and the weight average molecular weight may be preferably 550 to 650.
  • the ion conductive polymer may be applied to the aqueous solvent diluted to a concentration of 5 to 20%.
  • the ion conductive polymer may be mostly a polymer having an alcohol group, and since the alcohol group may decompose the latex particles mixed together in the latex composition for dip molding, which may cause aggregation between the particles. It is preferable to dilute and use in a solvent.
  • aqueous solvent for example, deionized water, distilled water or the like may be used, and any solvent that is water-soluble among organic solvents may be applied without limitation, but it may be preferable to use an aqueous solvent such as water.
  • concentration when diluting the ion conductive polymer, the concentration may be adjusted to about 5 to 20%, preferably 8 to 12%.
  • the ion conductive polymer may include one having a glass transition temperature of -45 to -35 ° C., but in selecting an ion conductive polymer included in a dip molding latex composition according to the present disclosure, the glass transition temperature of the ion conductive polymer Is not greatly limited. That is, when the glass transition temperature of the ion conductive polymer is in the above range, when the composition is formed by mixing with a carboxylic acid-modified nitrile latex, the glass transition temperature of the composition is lowered to -15 ° C or lower, and the average particle diameter is adjusted to 90 nm or more. It can play a role. This may be because the ion conductive polymer is generally excellent in hygroscopicity and has excellent mixing properties when forming a composition (compound) with latex.
  • the dip molding latex composition may have a pH of 8 to 12. When the pH is outside the range of 8 to 12, there is a fear that the stability of the latex composition for dip molding may be lowered, preferably 9 to 11, more preferably 9.1 to 10.8.
  • the latex composition for dip molding may have a concentration of 10 to 40% by weight of solids.
  • concentration of the solid content is less than 10% by weight, the transport efficiency of the latex composition for dip molding may be lowered and the productivity may be lowered.
  • concentration of the solid content exceeds 40% by weight, the viscosity of the composition may be increased to cause solidification or aggregation. May cause problems with storage stability.
  • the concentration of the solid content is preferably 10 to 40% by weight, may be 15 to 35% by weight, and may be 18 to 33% by weight.
  • the latex composition for dip molding may further include an additive, and may further control the physical properties such as viscosity, pH, and the like of the dip molding latex composition by further administering the additive. Can be configured.
  • a vulcanizing agent for example, a vulcanizing agent, a vulcanization accelerator, an ionic crosslinking agent, a pigment, a filler, a thickener, a pH adjuster or a mixture thereof may be applied.
  • the vulcanizing agent may be used without particular limitation as long as it can be generally included in a dip molding latex composition, for example, powdered sulfur, precipitated sulfur, colloidal sulfur, surface-treated sulfur, insoluble sulfur, or a mixture thereof may be applied. And, based on 100 parts by weight of the solid content contained in the dip molding latex composition, it may be included in about 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight.
  • the vulcanization accelerator may be used without particular limitation as long as it can be generally used in a latex composition for dip molding, for example, 2-mercaptobenzothiazole, 2,2-dithiobisbenzothiazole-2 -Sulfenamide (2,2-dithiobisbenzothiozole-2-sulfenamide), N-cyclohexylbenzothiazole-2-sulfenamide, 2-orpolyolinobenzothiazole ), Tetramethylthiuram monosulfide, tetramethylthiuram desulfide, zinc diethyldithiocarbamate, zinc di-n-butyl-dithiocarbamate (zinc di- n-buthyl-dithiocarbamate), diphenylguanidine, di-o-tolyguanidine, or a mixture thereof may be applied, and the weight of the solid contained in the latex composition for dip molding is 100 wt%. To wealth And, it is from about 0.1 to 10
  • ionic crosslinking agents, pigments, fillers, thickeners and the like can also be selectively added as needed, as long as they can be generally added in the manufacture of latex compositions for dip molding in the art, and the pH adjuster is an aqueous potassium hydroxide solution or ammonia Aqueous solution and the like can be applied.
  • the concentration of the pH adjuster may be about 1 to 5%, and through this, the pH of the composition can be adjusted to achieve stability of the composition itself.
  • the steps of preparing the first and second latex, respectively, the glass transition temperature is different; Preparing a first latex composition and a second latex composition by mixing an ion conductive polymer having a weight average molecular weight of 400 to 1000 with the first latex and the second latex, respectively; And blending the first latex composition and the second latex composition to produce a nitrile-based hybrid latex composition, wherein the nitrile-based hybrid latex is 100 parts by weight and the weight average molecular weight is 400 to 1000 1 to 8 parts by weight of the ion conductive polymer.
  • a method for producing a latex composition for dip molding comprising the step of: blending as possible.
  • the preparing of the nitrile-based latex may be a step of mixing the monomers of the first latex and the second latex, administering additives to the mixture of monomers, and then performing a polymerization reaction.
  • the preparing of the first latex and the second latex may include 40 to 89 wt% of the conjugated diene monomer, 10 to 50 wt% of the ethylenically unsaturated nitrile monomer, and 0.1 to 15 wt% of the ethylenically unsaturated acid monomer. It may comprise the step of preparing a monomer mixture.
  • the glass transition temperature or average particle diameter of the latex produced by controlling the content of the respective components of the monomer mixture can be controlled.
  • 1,3-butadiene 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene, isoprene , Or a mixture thereof, and the like, and preferably 1,3-butadiene or isoprene may be applied, and 1,3-butadiene may be mainly used, but is not limited thereto.
  • the conjugated diene monomer may include 40 to 89% by weight relative to the total weight of the monomer mixture.
  • the content of the conjugated diene-based monomer is less than 40% by weight, the hardness of the manufactured dip molded product may be increased, and the wearing comfort may be greatly reduced.
  • the content of the conjugated diene monomer exceeds 89% by weight, the oil resistance and tensile strength of the manufactured dip molded product may be reduced. It is preferable to use 40 to 89% by weight to improve physical properties such as oil resistance and tensile strength of the dip molded article, and to improve the fit of the dip molded article.
  • the conjugated diene-based monomer may be preferably included in 45 to 80% by weight, 50 to 75% by weight, by controlling the content of the conjugated diene-based monomer, to control the glass transition temperature of each latex included in the nitrile-based hybrid latex As may be the case, it may be important to adjust the appropriate amount.
  • Compounds that can be applied to the ethylenically unsaturated nitrile monomer may be, for example, acrylonitrile, methacrylonitrile, fumaronitrile,? -Chloronitrile,? -Cyano ethyl acrylonitrile, or a mixture thereof, and the like.
  • acrylonitrile or methacrylonitrile may be applied, but is not limited thereto.
  • the ethylenically unsaturated nitrile monomer may include 10 to 50% by weight relative to the total weight of the monomer mixture, if the content is less than 10% by weight may lower the oil resistance and tensile strength of the manufactured dip molded product, more than 50% by weight Since the hardness of the dip molded product to be manufactured may increase due to the hardness of the dip molded product, the use of 10 to 50% by weight may improve the physical properties such as oil resistance and tensile strength of the dip molded product and improve the fit of the dip molded product.
  • the ethylenically unsaturated nitrile monomer may be included in an amount of 15 to 45 wt%, or 20 to 40 wt%.
  • the ethylenically unsaturated acid monomers include, for example, ethylenically unsaturated carboxylic acid monomers such as acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid; Polycarboxylic anhydrides such as maleic anhydride or citraconic anhydride; Ethylenically unsaturated sulfonic acid monomers such as styrene sulfonic acid; Ethylenically unsaturated polycarboxylic acid partial ester monomers such as monobutyl fumarate, monobutyl maleate or mono-2-hydroxy propyl maleate; Or a mixture thereof may be applied.
  • methacrylic acid may be preferably used, but is not limited thereto.
  • the ethylenically unsaturated acid monomer may include 0.1 to 15% by weight relative to the total weight of the monomer mixture, when the content is less than 0.1% by weight may lower the oil resistance and tensile strength of the manufactured dip molded product, if it exceeds 15% by weight Since the hardness of the manufactured dip molded product may be increased, the wearing comfort may be greatly reduced. Therefore, the use of 0.1 to 15% by weight is preferable for improving the physical properties such as oil resistance and tensile strength of the dip molded product and improving the fit of the dip molded product.
  • the ethylenically unsaturated acid monomer may be included in an amount of 0.5 to 9.0% by weight, or 1.0 to 8.0% by weight.
  • the first latex and the second latex may optionally further copolymerize with the ethylenically unsaturated nitrile monomer and the ethylenically unsaturated acid monomer, but may further include ethylenically unsaturated monomers different from each other.
  • a vinyl aromatic monomer selected from the group consisting of styrene, alkyl styrene, and vinyl naphthalene; Fluoroalkyl vinyl ethers such as fluoro ethyl vinyl ether; (Meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethylol (meth) acrylamide, N-methoxy methyl (meth) acrylamide, and N-propoxy methyl (meth) acrylamide Ethylenically unsaturated amide monomers selected from the group consisting of; Non-conjugated diene monomers such as vinyl pyridine, vinyl norbornene, dicyclopentadiene and 1,4-hexadiene; Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, trifluoro
  • the ethylenically unsaturated monomer that can be optionally used in the copolymerization can be used in an amount of up to 20% by weight of the total weight of the monomer mixture, if exceeded, there is a mismatch between the tensile strength and the soft fit of the dip molded article The quality may be poor.
  • the method of adding the monomers constituting each of the first and second latexes is not particularly limited, and a method of simultaneously introducing the monomer mixture into the polymerization reactor, a method of continuously introducing the monomer mixture into the polymerization reactor, or a part of the monomer mixture May be applied to the polymerization reactor and any of the methods for continuously supplying the remaining monomers to the polymerization reactor.
  • each of the first and second latexes may further include adding an emulsifier to the monomer mixture.
  • anionic surfactant nonionic surfactant, cationic surfactant, amphoteric surfactant, etc.
  • anionic surfactants such as alkylbenzene sulfonates, aliphatic sulfonates, sulfuric acid ester salts of higher alcohols, ⁇ -olefin sulfonates, alkyl ether sulfate ester salts, or mixtures thereof, but is not limited thereto. It doesn't happen.
  • the emulsifier is not particularly limited in amount, but may be added in an amount of about 0.3 to 10 parts by weight, preferably 0.8 to 8 parts by weight, or 1.5 to 6 parts by weight, relative to 100 parts by weight of the monomer mixture.
  • the emulsifier is added in an amount of less than 0.3 parts by weight, the stability of the polymerization reaction may be lowered, and when it is added in an amount greater than 10 parts by weight, a large amount of bubbles may be generated on the composition, which may cause problems in manufacturing a dip molded product.
  • the type and content of the emulsifier are important factors for controlling the average particle diameter of each of the latexes included in the nitrile-based hybrid latex, and it is important to select the type and the amount of the emulsifier to prepare the latex of the required physical properties. can do.
  • the preparing of the first latex and the second latex may further include adding a polymerization initiator to the monomer mixture.
  • a radical initiator may be used, and examples of the radical initiator include inorganic peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate and hydrogen peroxide; t-butyl peroxide, cumene hydroperoxide, p-mentanehydro peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, dibenzoyl peroxide Organic peroxides such as oxides, 3,5,5-trimethylhexanol peroxide and t-butyl peroxy isobutylate; Azobis isobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexane carbonitrile, azobis isobutyric acid (butyl acid)
  • the polymerization initiator is not particularly limited, but may be added in an amount of about 0.01 to 2 parts by weight, preferably 0.02 to 1.5 parts by weight, relative to 100 parts by weight of the monomer mixture.
  • the polymerization initiator is added in an amount of less than 0.01 part by weight, it may be difficult to complete the reaction because the rate of polymerization is excessively slow, and when it is added in excess of 2 parts by weight, the polymerization rate is excessively fast to control the polymerization reaction. Can be difficult.
  • the preparing of the first latex and the second latex may further include adding a molecular weight modifier to the monomer mixture.
  • the molecular weight modifiers include mercaptans such as ⁇ -methylstyrene dimer, t-dodecyl mercaptan, n-dodecyl mercaptan and octyl mercaptan; Halogenated hydrocarbons such as carbon tetrachloride, methylene chloride and methylene bromide; And sulfur compounds such as tetraethyl thiuram disulfide, dipentamethylene thiuram disulfide, and diisopropylquixanthogen disulfide.
  • the molecular weight modifiers may be used alone or in combination of two or more, mercaptans may be preferred among them, and t-dodecyl mercaptan may be more preferably used, but is not limited thereto.
  • the molecular weight modifier is not particularly limited, but may be added in an amount of about 0.1 to 2.0 parts by weight, preferably 0.2 to 1.5 parts by weight, or 0.3 to 1.0 parts by weight, relative to 100 parts by weight of the monomer mixture.
  • the molecular weight modifier is added in an amount of less than 0.1 part by weight, the physical properties of the dip molded article may be significantly lowered, and when added in excess of 2.0 parts by weight, the stability of the polymerization reaction may be reduced.
  • the preparing of the first latex and the second latex may further include injecting an additive into the monomer mixture.
  • the additive include, for example, an activator, a chelating agent, a dispersant, and an oxygen scavenger. , Particle size adjusting agents, anti-aging agents, oxygen trapping agents or mixtures thereof may be additionally added.
  • sodium formaldehyde sulfoxylate sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrrolate, sodium sulfite, or a mixture thereof may be applied, but is not limited thereto. .
  • the preparing of the first latex and the second latex may further include polymerizing the monomer mixture by adding an emulsifier, a molecular weight modifier, a polymerization initiator, and other additives.
  • an emulsifier such as the emulsifier, the molecular weight regulator, the polymerization initiator, the subadditives, and the monomer mixture
  • the order of adding the materials such as the emulsifier, the molecular weight regulator, the polymerization initiator, the subadditives, and the monomer mixture may start the polymerization reaction after administering the monomer mixture, and the additives may be administered in the middle of the reaction in a specific order. Certain additives may be administered prior to the reaction, so there is no particular limitation on this order of administration.
  • the polymerization reaction may be carried out at a temperature of 10 to 90 °C, preferably 20 to 80 °C, or may be carried out at 25 to 75 °C, the conversion rate when stopping the polymerization reaction is specifically 90% or more More specifically 93% or more.
  • the unreacted monomer can be removed, and the carboxylic acid-modified nitrile latex can be obtained by adjusting the solid content concentration and pH.
  • concentration of the solids may be adjusted using water such as distilled water or deionized water, and as described above, the concentration of the solids needs to be adjusted to be 10 to 40% by weight.
  • the pH needs to be adjusted to 8 to 12, as described above, which may be adjusted using 1 to 5% aqueous potassium hydroxide solution or ammonia water.
  • the hybrid latex composition may be prepared by mixing and blending the first and second latexes with an ion conductive polymer.
  • a first latex having a glass transition temperature of -50 to -25 ° C and an average particle diameter of 90 to 200 nm is prepared, and a glass transition temperature of -25 to -15 ° C and an average particle diameter of 100 to 200 nm.
  • 2 latex may be prepared, and hybrid latex may be prepared by mixing 30 to 80 wt% of the first latex and 20 to 70 wt% of the second latex.
  • the type and content of the emulsifier and the content of the conjugated diene monomer are appropriately adjusted to control the glass transition temperature and the average particle diameter in accordance with the first and second latexes.
  • the preparing of the hybrid latex composition may be performed by first mixing each of the first and second latexes prepared by the above-described method with an ion conductive polymer and blending the first and second latex compositions. Can be.
  • the ion conductive polymer included in the hybrid latex composition may be 2 to 8 parts by weight based on 100 parts by weight of the hybrid latex.
  • the preparing of the composition may further include administering an additive to the composition, and the additive may be applied with a vulcanizing agent, a vulcanization accelerator, an ionic crosslinking agent, a pigment, a filler, a thickener, or a mixture thereof. Since the detailed description thereof is the same as that described above, the description thereof is omitted.
  • the method for producing a dip molded article may include, in particular, (a) dipping the dip mold into a coagulant solution to attach a coagulant to the surface of the dip mold; (b) immersing the dip molding mold to which the coagulant is attached to the latex composition for dip molding to form a dip molding layer; And (c) cross-linking the latex resin by heating the dip molding layer formed on the dip mold.
  • the step (a) may be a step of immersing the dip mold in a coagulant solution to attach the coagulant to the surface of the dip mold.
  • Such coagulants include metal halides such as barium chloride, calcium chloride, magnesium chloride, zinc chloride, aluminum chloride and the like; Nitrates such as barium nitrate, calcium nitrate and zinc nitrate; Acetates such as barium acetate, calcium acetate and zinc acetate; Sulfates such as calcium sulfate, magnesium sulfate and aluminum sulfate; and the like. Of these, calcium chloride and calcium nitrate may be preferred, but are not limited thereto.
  • the coagulant solution may be a solution in which the coagulant is dissolved in water, alcohol or a mixture thereof.
  • the concentration of coagulant in the coagulant solution may generally be 5 to 75% by weight, specifically 15 to 55% by weight, or 18 to 40% by weight.
  • the step (b) may be a step of forming a dip molding layer by immersing a dip molding mold having a coagulant attached to the surface in the above-described dip molding latex composition. That is, after the dip molding mold to which the coagulant is adhered is immersed in the latex composition for dip molding, the dip molding mold may be taken out to form a dip molding layer in the dip molding mold.
  • the step (c) may be a step of crosslinking the latex resin by heating the dip molding layer formed in the dip mold.
  • the water component may be evaporated first, and curing through crosslinking may be performed, and the dip molded layer crosslinked by the heat treatment may be peeled off from the dip mold to obtain a dip molded product as a final product.
  • Dip molded article according to another embodiment of the present specification is manufactured through the method as described above, for example, surgical gloves, examination gloves, condoms, catheters (catheter), industrial gloves, household gloves, health care products, etc. It can be applied to gloves that can be used in a variety of fields, if the resin product needs a soft fit of a thin material may be applicable without particular limitations.
  • a monomer mixture was prepared by mixing 67.5 wt% and 5.5 wt% methacrylic acid. To 100 parts by weight of the monomer mixture, 3.0 parts by weight of sodium alkyl benzene sulfonate as an emulsifier, 0.6 parts by weight of t-dodecyl mercaptan as a molecular weight modifier and 140 parts by weight of ion-exchanged water were heated up to 40 ° C.
  • the glass transition temperature of the first latex was measured according to a conventional method using differential scanning calotimetry, and the average particle diameter was measured according to a conventional method using a laser scattering analyzer (Nicomp). It was. As a result, the glass transition temperature was -33 ° C and the average particle diameter was 120 nm.
  • a monomer mixture was prepared by mixing 29% by weight of acrylonitrile, 64.5% by weight of 1,4-butadiene and 6.5% by weight of methacrylic acid. With respect to 100 parts by weight of the monomer mixture, 1.5 parts by weight of sodium alkyl benzene sulfonate as an emulsifier, 0.65 parts by weight of t-dodecyl mercaptan and 140 parts by weight of ion-exchanged water were added as a molecular weight modifier. In the same manner, a second latex having a glass transition temperature of ⁇ 25 ° C. and an average particle diameter of 120 nm was prepared.
  • Ion conductive polymer polyethylene glycol having a weight average molecular weight of 600 diluted by 10% based on 100 parts by weight based on the mixed latex mixed with the two latexes in each of the first and second latexes prepared in 1) above 1 parts by weight of each to prepare a latex composition, blending the two compositions to prepare a nitrile-based hybrid latex composition (total 2 parts by weight of PEG added), a 3% potassium hydroxide solution and an appropriate amount of secondary Distilled water was added to obtain a latex composition for dip molding having a solid content concentration of 25% and a pH of 10.0.
  • PEG polyethylene glycol
  • the ceramic mold to which the coagulant was applied was immersed in the latex composition for dip molding prepared in 2) for 1 minute, dried at 80 ° C for 1 minute, and soaked in warm water for 3 minutes. The mold was dried at 80 ° C. for 3 minutes and crosslinked at 120 ° C. for 20 minutes. The crosslinked dip molding layer was peeled off from the ceramic mold to obtain a dip molded article.
  • the first and second latexes were prepared in the same manner as in Example 1, except that each composition was prepared by mixing 2 parts by weight of polyethylene glycol (PEG) (4 parts by weight of PEG added).
  • PEG polyethylene glycol
  • a latex composition for dip molding was prepared in the same manner as in Example 1.
  • the first and second latexes were prepared in the same manner as in Example 1, except that 3 parts by weight of polyethylene glycol (PEG) were mixed to prepare respective compositions (total amount of PEG was added in a total of 6 parts by weight).
  • a latex composition for dip molding was prepared in the same manner as in Example 1.
  • the first and second latexes were prepared in the same manner as in Example 1, except that 4 parts by weight of polyethylene glycol (PEG) were mixed to prepare the respective compositions (total amount of PEG was added in a total of 8 parts by weight).
  • a latex composition for dip molding was prepared in the same manner as in Example 1.
  • a dip molded article was manufactured in the same manner as in Example 1, except that the first latex and the second latex prepared in Example 1 were blended without adding PEG.
  • a dip molded article was manufactured in the same manner as in Example 1, except that the first latex prepared in Example 1 was used alone without adding PEG.
  • a dip molded article was manufactured in the same manner as in Example 1, except that the second latex prepared in Example 1 was used alone without adding PEG.
  • Each dip molded product was manufactured in a dumbbell-shaped specimen according to ASTM D-412, and cross head speed was measured using a universal testing machine (UTM) device (Model: 4466, Instron) according to ASTM D638. After pulling at 500 mm / min, the points at which each of the specimens were cut were measured. Tensile strength was calculated by the following equation (1). In addition, the elongation (%) was calculated by the following equation (2), the stress at 300% (MPa) is the tensile strength when the specimen is stretched three times the initial length, the stress (MPa) at 500% is Tensile strength at the time of elongation 5 times the initial length was measured.
  • step (c) it is to grasp when the water drops from the dip molded article facing downward during the heat treatment of step (c). Since a change in solid content of the resin may affect workability, a lower syneresis value may mean that workability may be degraded.
  • the dip molded articles of Examples 1 to 4 prepared by blending after adding PEG to each of the two carboxylic acid-modified nitrile-based latexes have improved tensile strength as compared to the dip molded articles of Comparative Examples 1-3. It can be seen that the modulus (modulus) and the elongation (elelongation) through the increase in the elongation and stress improves the fit is excellent. In addition, it can be seen that the effect is significant in improving workability (synergy) and low temperature stability. Through this, it was confirmed that the hybrid latex can be enhanced compatibility by the addition of PEG, to maximize the physical properties of the blended hybrid latex.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Moulding By Coating Moulds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition de latex pour moulage par immersion, comprenant : 100 parties en poids d'un latex hybride à base de nitrile comprenant un premier latex et un second latex qui présentent différentes températures de transition vitreuse ; et de 2 à 8 parties en poids d'un polymère conducteur d'ions qui présente une masse moléculaire moyenne en poids de 400 à 1000. La composition de latex pour moulage par immersion pésente une excellente stabilité à basse température, et un article moulé par immersion obtenu à l'aide de la composition présente une excellente résistance à la traction, un allongement satisfaisant et une meilleure résistance à l'usure due à un module d'élasticité réduite, et peut donc être facilement utilisée dans des industries requérant cette dernière.
PCT/KR2015/014158 2014-12-23 2015-12-23 Composition de latex pour moulage par immersion et article moulé par immersion obtenu à l'aide de la composition Ceased WO2016105112A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201580056644.5A CN107075141B (zh) 2014-12-23 2015-12-23 用于浸渍成型的胶乳组合物及由其制得的浸渍成型制品
US15/516,727 US10100179B2 (en) 2014-12-23 2015-12-23 Latex composition for dip forming and dip-formed article prepared therefrom
JP2017516740A JP6458139B2 (ja) 2014-12-23 2015-12-23 ディップ成形用ラテックス組成物及びこれから製造されたディップ成形品

Applications Claiming Priority (4)

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KR10-2014-0186881 2014-12-23
KR20140186881 2014-12-23
KR1020150183167A KR101775798B1 (ko) 2014-12-23 2015-12-21 딥 성형용 라텍스 조성물 및 이로부터 제조된 딥 성형품
KR10-2015-0183167 2015-12-21

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WO2019039523A1 (fr) * 2017-08-25 2019-02-28 日本ゼオン株式会社 Composition de latex
JP2019510854A (ja) * 2016-09-07 2019-04-18 エルジー・ケム・リミテッド ディップ成形用ラテックス組成物及びこれより製造された成形品
JP2019515974A (ja) * 2016-09-01 2019-06-13 エルジー・ケム・リミテッド ディップ成形用ラテックス組成物及びこれより製造された成形品
JPWO2018155243A1 (ja) * 2017-02-22 2019-12-19 日本ゼオン株式会社 ラテックス組成物
CN113265095A (zh) * 2020-02-17 2021-08-17 锦湖石油化学株式会社 浸渍成型用胶乳组合物及包括其的浸渍成型品

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US6391409B1 (en) * 1999-02-12 2002-05-21 Allegiance Corporation Powder-free nitrile-coated gloves with an intermediate rubber-nitrile layer between the glove and the coating and method of making same
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JP2019515974A (ja) * 2016-09-01 2019-06-13 エルジー・ケム・リミテッド ディップ成形用ラテックス組成物及びこれより製造された成形品
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JP2019510854A (ja) * 2016-09-07 2019-04-18 エルジー・ケム・リミテッド ディップ成形用ラテックス組成物及びこれより製造された成形品
JPWO2018155243A1 (ja) * 2017-02-22 2019-12-19 日本ゼオン株式会社 ラテックス組成物
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JP7127649B2 (ja) 2017-08-25 2022-08-30 日本ゼオン株式会社 ラテックス組成物
US11884761B2 (en) 2017-08-25 2024-01-30 Zeon Corporation Latex composition
CN113265095A (zh) * 2020-02-17 2021-08-17 锦湖石油化学株式会社 浸渍成型用胶乳组合物及包括其的浸渍成型品
CN113265095B (zh) * 2020-02-17 2023-05-02 锦湖石油化学株式会社 浸渍成型用胶乳组合物及包括其的浸渍成型品

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