WO2014142425A1 - Composition de latex pour moulage par immersion et produit moulé produit à partir de celle-ci - Google Patents

Composition de latex pour moulage par immersion et produit moulé produit à partir de celle-ci Download PDF

Info

Publication number
WO2014142425A1
WO2014142425A1 PCT/KR2013/011836 KR2013011836W WO2014142425A1 WO 2014142425 A1 WO2014142425 A1 WO 2014142425A1 KR 2013011836 W KR2013011836 W KR 2013011836W WO 2014142425 A1 WO2014142425 A1 WO 2014142425A1
Authority
WO
WIPO (PCT)
Prior art keywords
dip molding
latex
starch
dip
weight
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/KR2013/011836
Other languages
English (en)
Korean (ko)
Inventor
양승훈
김병윤
김정은
여승욱
한정수
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 KR1020130149342A external-priority patent/KR101577501B1/ko
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to MYPI2014002395A priority Critical patent/MY185224A/en
Priority to US14/371,372 priority patent/US9771471B2/en
Priority to CN201380007858.4A priority patent/CN104169354B/zh
Publication of WO2014142425A1 publication Critical patent/WO2014142425A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/003Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor characterised by the choice of material
    • AHUMAN NECESSITIES
    • A41WEARING APPAREL
    • A41DOUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D19/00Gloves
    • A41D19/0055Plastic or rubber gloves
    • A41D19/0058Three-dimensional gloves
    • AHUMAN NECESSITIES
    • A41WEARING APPAREL
    • A41DOUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D19/00Gloves
    • A41D19/0055Plastic or rubber gloves
    • A41D19/0058Three-dimensional gloves
    • A41D19/0062Three-dimensional gloves made of one layer of material
    • AHUMAN NECESSITIES
    • A41WEARING APPAREL
    • A41DOUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D19/00Gloves
    • A41D19/04Appliances for making gloves; Measuring devices for glove-making
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/02Shaping 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
    • B29C41/14Dipping a core
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L13/00Compositions of rubbers containing carboxyl groups
    • C08L13/02Latex
    • AHUMAN NECESSITIES
    • A41WEARING APPAREL
    • A41DOUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D2500/00Materials for garments
    • A41D2500/50Synthetic resins or rubbers
    • A41D2500/54Synthetic resins or rubbers in coated form
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/02Starch; Degradation products thereof, e.g. dextrin

Definitions

  • the present invention relates to a latex composition for dip molding and a molded article prepared therefrom, and more particularly, by using a mixture of carboxylic acid-modified nitrile copolymer latex and starch in a dip molding operation, excellent workability, non-sticky and tensile It relates to a latex composition for dip molding capable of producing a molded article having excellent strength and a molded article prepared therefrom.
  • an object of the present invention is a carboxylic acid-modified nitrile system that can produce a product with excellent synergy and less sticky than the existing dip molding, excellent tensile strength It is to provide a copolymer latex composition.
  • Another object of the present invention is to provide a molded article prepared from the carboxylic acid-modified nitrile copolymer latex composition.
  • the present invention provides a latex composition for dip molding comprising a carboxylic acid-modified nitrile copolymer latex and starch.
  • the present invention has a viscosity of 300 cPs or less when 85 to 98% by weight of a carboxylic acid-modified nitrile copolymer latex having a glass transition temperature of -50 ° C to -15 ° C and an average particle diameter of 50 nm or more and a temperature of 50 ° C and a concentration of 30% by weight.
  • the carboxylic acid-modified nitrile copolymer latex composition for dip molding of the present invention is characterized by comprising a carboxylic acid-modified nitrile copolymer latex and starch.
  • the glass transition temperature of the carboxylic acid-modified nitrile copolymer latex is -50 ° C to -15 ° C.
  • the glass transition temperature of the carboxylic acid-modified nitrile copolymer latex may be -45 °C to -20 °C, when in this range, excellent tensile strength, and does not cause cracks in the dip molded product.
  • the average particle diameter of the carboxylic acid-modified nitrile copolymer latex may be 50 nm or more.
  • the average particle diameter of the carboxylic acid-modified nitrile copolymer latex may be 50nm to 500nm, 50nm to 300nm or 60 to 200nm, the viscosity of the latex does not increase within this range to produce a latex at a high concentration And also the tensile strength does not decrease after glove manufacture.
  • the glass transition temperature and the average particle diameter of the latex are the glass transition temperature and the average particle diameter of the polymer included in the latex.
  • the average particle diameter is a weight average particle diameter.
  • the starch may have a viscosity of 300 cPs or less when the temperature is 50 ° C. and the aqueous solution concentration is 30 wt%.
  • the latex composition for dip molding according to the present invention may include, for example, 70:30 to 99.9: 0.1, 75:25 to 99: 1, 81:19 to 99: 1, or 98: of the carboxylic acid-modified nitrile copolymer latex. It may be included in a weight ratio of 2 to 85:15.
  • the width is large, the stickiness of the dip molded product is less, and the tensile strength is also excellent.
  • the latex composition for dip molding comprising a carboxylic acid-modified nitrile copolymer latex according to the present invention is a vulcanizing agent, ionic crosslinking agent, pigment, vulcanization catalyst, filler, thickener and pH It may comprise one or more additives selected from the group consisting of regulators.
  • the dip molded article according to the present invention is also obtained by dip molding the latex composition for dip molding.
  • the dip molded article of the present invention is a latex is prepared by adding an emulsifier, a polymerization initiator, and a molecular weight regulator to each monomer constituting the latex, and the temperature is 70 to 90 °C, or 75 through a separate route
  • the latex and starch are mixed at a temperature of 40 to 60 ° C, or 45 to 55 ° C
  • the composition is prepared and then dip molded to produce the final product.
  • Latex according to the present invention is prepared by emulsion polymerization by adding an emulsifier, a polymerization initiator, a molecular weight regulator, and other additives to each monomer constituting the carboxylic acid-modified nitrile copolymer.
  • Monomers constituting the carboxylic acid-modified nitrile copolymer are, for example, conjugated diene monomers, ethylenically unsaturated nitrile monomers, and ethylenically unsaturated acid monomers.
  • the carboxylic acid-modified nitrile copolymer may further include, for example, an unsaturated ethylenic monomer copolymerizable with the monomers.
  • conjugated diene monomer constituting the carboxylic acid-modified nitrile copolymer according to the present invention include 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3- Butadiene, 1,3-pentadiene and isoprene selected from the group consisting of 1,3-butadiene and isoprene, and among these, 1,3-butadiene is most preferably used.
  • the conjugated diene monomer is included in 40 to 89% by weight, 45 to 80% by weight, or 50 to 78% by weight of the total monomers constituting the carboxylic acid-modified nitrile copolymer, for example.
  • the dip molded product is flexible and comfortable to wear, and the dip molded article is excellent in oil resistance and tensile strength.
  • the ethylenically unsaturated nitrile monomer is acrylonitrile, methacrylonitrile, fumaronitrile, ⁇ -chloronitrile and ⁇ -cyano ethyl acryl At least one selected from the group consisting of ronitrile, of which acrylonitrile and methacrylonitrile are preferred, and acrylonitrile is most preferably used.
  • the ethylenically unsaturated nitrile monomer is included in 10 to 50% by weight, 15 to 45% by weight, or 20 to 40% by weight of the total monomers constituting the carboxylic acid-modified nitrile copolymer, for example.
  • the dip molded article is excellent in oil resistance and tensile strength, and the dip molded article is flexible and comfortable to wear.
  • the ethylenically unsaturated acid monomer is an ethylenically unsaturated monomer containing at least one acidic group selected from the group consisting of carboxyl group, sulfonic acid group and acid anhydride group
  • carboxylic acid monomers such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid
  • Polycarboxylic acid anhydrides such as maleic anhydride and citraconic anhydride
  • Ethylenically unsaturated sulfonic acid monomers such as styrene sulfonic acid
  • ethylenically unsaturated polycarboxylic acid partial ester monomers such as monobutyl fumarate, monobutyl maleate, and mono-2-hydroxypropyl maleate.
  • methacrylic acid is particularly preferable
  • the ethylenic unsaturated acid monomer is included in 0.1 to 10% by weight, 0.5 to 9% by weight, or 1 to 8% by weight of the total monomers constituting the carboxylic acid-modified nitrile copolymer, for example.
  • the dip molded article is excellent in tensile strength, and the dip molded article is flexible and comfortable to wear.
  • the carboxylic acid-modified nitrile copolymer according to the present invention may further include other ethylenically unsaturated monomers that can be optionally copolymerized with the above monomers, for example, vinyl aromatic monomers 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, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, dibutyl maleate, Dibutyl fuma
  • the amount of the copolymerizable other ethylenically unsaturated monomer may be used, for example, in 20% by weight, or 0.01 to 20% by weight of the total monomers constituting the carboxylic acid-modified nitrile copolymer. Within this range there is a balance between a soft fit and tensile strength.
  • the carboxylic acid-modified nitrile copolymer latex of the present invention may be prepared by emulsion polymerization by adding an emulsifier, a polymerization initiator, an activator, a molecular weight modifier, and the like to the monomer constituting the carboxylic acid-modified nitrile copolymer.
  • an emulsifier emulsifier, a polymerization initiator, an activator, a molecular weight modifier, and the like
  • anionic surfactant a nonionic surfactant, cationic surfactant, an amphoteric surfactant, etc.
  • anionic surfactants selected from the group consisting of alkylbenzene sulfonates, aliphatic sulfonates, sulfuric acid ester salts of higher alcohols, ⁇ -olefin sulfonate salts, and alkyl ether sulfuric acid ester salts can be particularly preferably used.
  • the usage-amount of an emulsifier is 0.3-10 weight part, 0.8-8 weight part, or 1.5-6 weight part with respect to 100 weight part of monomers which comprise the said carboxylic acid modified nitrile copolymer, for example.
  • the amount of the emulsifier is less than 0.3 parts by weight, the stability during the polymerization is lowered, if it exceeds 10 parts by weight, there is a problem that the production of dip molded article is difficult to increase the foaming.
  • a radical initiator can be used.
  • inorganic peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate, 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; At least one selected from the group consisting of azobis isobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexane carbonitrile, and
  • the usage-amount of a polymerization initiator is 0.01-2 weight part, 0.02-1.5 weight part, or 0.05-1.0 weight part with respect to 100 weight part of all monomers which comprise the said carboxylic acid modified nitrile copolymer, for example. Within this range, the rate of polymerization can be controlled to easily produce the final product and the polymerization stability is also excellent.
  • the activator may be at least one selected from the group consisting of sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrroline and sodium sulfite.
  • molecular weight modifier such as (alpha) -methylstyrene dimer, t-dodecyl mercaptan, n-dodecyl mercaptan, 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.
  • molecular weight modifiers may be used alone or in combination of two or more thereof.
  • mercaptans are preferable, and t-dodecyl mercaptan can be used more preferably.
  • the usage-amount of a molecular weight modifier is 0.1-2.0 weight part, 0.2-1.5 weight part, or 0.3-1.0 weight part with respect to 100 weight part of all monomers which comprise the said carboxylic acid modified nitrile copolymer, for example. Within this range, there is an effect that the physical properties and polymerization stability of the dip molded article are remarkably improved.
  • additional materials such as chelating agent, dispersing agent, pH adjusting agent, deoxygenating agent, particle size adjusting agent, anti-aging agent, oxygen scavenger and the like can be added.
  • the method of adding the monomer mixture constituting the carboxylic acid-modified nitrile copolymer may be, for example, a method of introducing the monomer mixture into the polymerization reactor at once, a method of continuously adding the monomer mixture into the polymerization reactor, or a portion of the monomer mixture into the polymerization reactor. And the remaining monomers are continuously supplied to the polymerization reactor.
  • the polymerization temperature at the time of the said emulsion polymerization is not specifically limited, For example, they are 10-90 degreeC, 20-80 degreeC, or 25-75 degreeC.
  • the conversion rate at the time of stopping a polymerization reaction is 90% or more, 90%-99.9%, or 93%-99%, for example.
  • the carboxylic acid-modified nitrile copolymer latex can be obtained by removing the unreacted monomer and adjusting the solid content concentration and pH.
  • the glass transition temperature can be adjusted according to the content of the conjugated diene monomer, and the average particle size and particle size distribution can be adjusted according to the type or content of the emulsifier.
  • the latex glass transition temperature was measured by differential scanning calorimetry, and the average particle diameter was measured by a laser scattering analyzer (Nicomp).
  • the carboxylic acid-modified nitrile copolymer latex may have a solid content (concentration) of 20 to 70 wt%, 30 to 60 wt%, or 40 to 50 wt%.
  • Starch according to the present invention can be used for all commercially available products, for example, when the temperature is 50 °C and the aqueous solution concentration is 30% by weight may be a viscosity of 300 cPs or less.
  • the viscosity may be a Brookfield viscometer.
  • the starch is, for example, a mixture of amylose and amylopectin, and in another example, a mixture including 0 to 40% by weight of amylose and 60 to 100% by weight of amylopectin, or 10 to 30% by weight of amylose and 70 to amylotectin. It may be a mixture consisting of 90% by weight.
  • the viscosity of the starch may be 10 cPs to 300 cPs when the temperature is 50 ° C. and the concentration is 30 wt%.
  • the viscosity of the starch is 300 cPs or less, the viscosity does not increase even after mixing with the latex, making it easy to manufacture a dip molded article.
  • the starch may be, for example, a starch solution or a starch suspension.
  • the starch solution may be, for example, an aqueous starch solution.
  • the starch suspension may be, for example, a suspension of starch dispersed in water.
  • the starch solution or starch suspension may, for example, have a concentration of 0.1 to 60% by weight, 1 to 55% by weight, 10 to 45% by weight, or 20 to 40% by weight, within which the synergy is gentle and sticky. Less blurring and excellent tensile strength.
  • the starch may be, for example, starch extracted from various grains such as rice, barley, corn, potato, sweet potato, and tapioca.
  • a vulcanizing agent for example, in a mixture of latex and starch obtained by the above method, a vulcanizing agent, an ionic crosslinking agent, a pigment such as titanium oxide, a vulcanizing catalyst, a filler such as silica, a thickener and a pH adjusting agent such as ammonia or alkali hydroxide
  • a vulcanizing agent for example, a vulcanizing agent, an ionic crosslinking agent, a pigment such as titanium oxide, a vulcanizing catalyst, a filler such as silica, a thickener and a pH adjusting agent such as ammonia or alkali hydroxide
  • a filler such as silica
  • a thickener such as silica
  • a pH adjusting agent such as ammonia or alkali hydroxide
  • the carboxylic acid-modified nitrile copolymer latex in the composition is one of the glove physical properties of the dip molded article of the present invention, for example, contained in the composition 80-99% by weight, 85-98% by weight, or 88-97% by weight Preferred at
  • Solid content concentration of the latex composition for dip molding of this invention is 5-40 weight%, 8-35 weight%, or 10-33 weight% as an example.
  • PH of the latex composition for dip molding of this invention is 8.0-12, 9-11, or 9.3-10.5 as an example.
  • a conventional method can be used, and examples thereof include a direct dipping method, an anode adhesion dipping method, and a Teague adhesion dipping method.
  • an anode adhesion dipping method is preferable because of the advantage that a dip molded article having a uniform thickness can be easily obtained.
  • the dip molded article may be a surgical glove, an inspection glove, a condom, a catheter, an industrial glove, a household glove or a health care product.
  • coagulants include metal halides such as barium chloride, calcium chloride, magnesium chloride, zinc chloride and aluminum chloride; Nitrates such as barium nitrate, calcium nitrate and zinc nitrate; Acetates such as barium acetate, calcium acetate and zinc acetate; Sulfates such as calcium sulfate, magnesium sulfate and aluminum sulfate. Of these, calcium chloride and calcium nitrate are preferred.
  • the coagulant solution is a solution in which such coagulant is dissolved in water, alcohol or a mixture thereof. The concentration of coagulant in the coagulant solution is usually 5 to 75% by weight, or 8 to 55% by weight.
  • the dip molding mold to which the coagulant is attached is immersed in the latex composition for dip molding of the present invention, and then the dip molding mold is taken out to form a dip molding layer.
  • the syneresis time in the heat treatment can be measured by measuring, for example, the time that the water component falls from the dip mold. Dropping the water droplets within 1 minute may cause contamination of the dip molding composition in the field process, so it is preferable that the water droplets do not fall within 1 minute.
  • the water component evaporates first and curing through crosslinking is performed. Subsequently, the crosslinked dip molding layer is peeled off from the dip mold to obtain a dip molded article.
  • stickiness can be expressed by the ten-point method as a hand feel. Ten points are the least sticky and easily peeled off the dip mold, and one point means a lot of stickiness cannot be peeled off from the dip mold.
  • a dumbbell-shaped test piece can be produced from the obtained dip molded product in accordance with ASTM D-412. The specimen can then be pulled at a stretching rate of 500 mm / min using a universal testing machine (UTM) and the tensile strength at break can be measured.
  • UPM universal testing machine
  • Agitator, thermometer, cooler, nitrogen inlet and 10L high pressure reactor equipped with a monomer, emulsifier, and polymerization initiator are continuously replaced with nitrogen, and acrylonitrile 25% by weight, 1,3-butadiene 2.5 weight part of sodium alkyl benzene sulfonates, 0.5 weight part of t-dodecyl mercaptans, and 140 weight part of ion-exchange water were added with respect to 100 weight part of monomer mixtures of 70 weight% and 5 weight% of methacrylic acid, and it heated up to 40 degreeC.
  • the glass transition temperature is -40 °C
  • the average particle diameter is shown to 130nm
  • the latex prepared by the above is called 'latex-A'.
  • starch (gencoat of Samyang Genex), which is widely used for paper coating on the market, was prepared at a temperature of 80 ° C. at a concentration of 30% by weight, and a viscosity of 252 cPs at a temperature of 50 ° C.
  • the starch is called 'starch-A'.
  • a mixture was prepared by mixing Latex-A and Starch-A in 9: 1.
  • a 3% potassium hydroxide solution and an appropriate amount of secondary distilled water were added to the mixture to obtain a dip molding composition having a solid concentration of 15% and a pH of 10.0.
  • a coagulant solution was prepared by mixing 12 parts by weight calcium nitrate, 87.5 parts by weight distilled water, and 0.5 parts by weight wetting agent (Teric 320 produced by Huntsman Corporation, Australia). The hand-shaped ceramic mold was immersed in this solution for 1 minute, taken out, and dried at 80 ° C. for 3 minutes to attach a coagulant to the hand-shaped mold.
  • the mold to which the coagulant was applied was immersed in the dip molding composition for 1 minute, pulled up, dried at 120 ° C. for 4 minutes, and then soaked in water or hot water for 3 minutes. It was confirmed by the synergy time by checking the time of dropping water drops at 120 °C drying for 4 minutes.
  • the mold was dried at 120 ° C. for 3 minutes and crosslinked at 130 ° C. for 20 minutes. Sticking was measured while peeling off the cross-linked dip molding layer from the hand-shaped mold to obtain a dip molded article in the form of a glove.
  • the syneresis time, stickiness, and tensile strength are shown in Table 1 below.
  • Agitator, thermometer, cooler, nitrogen gas inlet and 10L high pressure reactor equipped with a monomer, emulsifier, and polymerization initiator can be continuously added with nitrogen, and then acrylonitrile 35% by weight, 1,4-butadiene 60 3 parts by weight of sodium alkyl benzene sulfonate, 0.5 parts by weight of t-dodecyl mercaptan and 140 parts by weight of ion-exchanged water were added to 100 parts by weight of the monomer mixture of 5% by weight and methacrylic acid, and the temperature was raised to 40 ° C.
  • the glass transition temperature is -23 °C
  • the average particle diameter is shown to 130nm, and from now on the latex produced by the above is called 'latex-B'.
  • starch (Ecosynthetics Ecosphere) having low viscosity at high concentration was prepared at a concentration of 30% by weight, and the viscosity was 35 cPs at 50 ° C.
  • the starch is called 'starch-B'.
  • a mixture was prepared by mixing latex-B and starch-B in a weight ratio of 9: 1.
  • Dip molded article was prepared in the same manner as in Example 1 and the physical properties are shown in Table 1 below.
  • Example 1 Except for mixing the latex-A and starch-A in Example 1 in a weight ratio of 98: 2 was prepared in the same manner as in Example 1, a dip molded article in the form of a glove, the physical properties are shown in Table 1 below.
  • Example 1 Except for mixing the latex-A and starch-A in Example 1 in a weight ratio of 85:15 to prepare a dip molded article in the form of a glove in the same manner as in Example 1, the physical properties are shown in Table 1 below.
  • Example 1 Except for mixing the latex-A and starch-B in Example 1 in a weight ratio 9: 1 was prepared in the same manner as in Example 1, a dip molded article in the form of a glove, the physical properties are shown in Table 1 below.
  • Example 1 Except for mixing the latex-B and starch-A in Example 1 in a weight ratio 9: 1 was prepared in the same manner as in Example 1, a dip molded article in the form of a glove, the physical properties are shown in Table 1 below.
  • Example 1 Except for mixing the latex-A and starch-A in Example 1 in a weight ratio of 8: 2, a dip molded article was prepared in the same manner as in Example 1, the physical properties are shown in Table 1 below.
  • Example 1 Except for mixing the latex-B and starch-B in Example 1 in a weight ratio of 8: 2 was prepared in the same manner as in Example 1 glove-shaped dip molded article, the physical properties are shown in Table 1 below.
  • Example 1 Except that the latex-A alone in Example 1 was prepared in the same manner as in Example 1 glove-shaped dip molded article, the physical properties are shown in Table 1 below.
  • Example 1 Except that the latex-B alone in Example 1 was prepared in the same manner as in Example 1 glove-shaped dip molded article, the physical properties are shown in Table 1 below.
  • Example 1 Syneresis (Sec.) Stickiness (10 points method) Tensile strength (MPa) Example 1 183 8 27.1 Example 2 128 9 33.1 Example 3 95 7 24.7 Example 4 > 240 10 25.0 Example 5 154 9 28.4 Example 6 121 9 33.9 Example 7 > 240 10 19.5 Example 8 > 240 10 21.3 Comparative Example 1 41 3 25.3 Comparative Example 2 55 2 32.2
  • a dip molded article made of a carboxylic acid-modified nitrile-based latex mixed with carboxylic acid-modified nitrile-based latex and starch according to the present disclosure was prepared in Comparative Examples 1 to 2 Compared to the dip molded products, the syneresis was gentle, the stickiness was low, and the tensile strength was excellent.

Landscapes

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

Abstract

La présente invention concerne une composition de latex pour un moulage par immersion comprenant un latex de copolymère à base de nitrile modifié par acide carboxylique et de l'amidon, et un produit moulé produit ainsi, et fournit un produit moulé par immersion ayant une synérèse lente, une faible adhésivité et une excellente résistance à la traction par mélange et utilisation d'un latex de copolymère à base de nitrile modifié par acide carboxylique et de l'amidon.
PCT/KR2013/011836 2013-03-15 2013-12-18 Composition de latex pour moulage par immersion et produit moulé produit à partir de celle-ci Ceased WO2014142425A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
MYPI2014002395A MY185224A (en) 2013-03-15 2013-12-18 Latex composition for dip molding and dip-molded article produced therefrom
US14/371,372 US9771471B2 (en) 2013-03-15 2013-12-18 Latex composition for dip molding and dip-molded article produced therefrom
CN201380007858.4A CN104169354B (zh) 2013-03-15 2013-12-18 用于浸渍模塑的胶乳组合物以及由其制备的浸渍模塑制品

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20130027635 2013-03-15
KR10-2013-0027635 2013-03-15
KR10-2013-0149342 2013-12-03
KR1020130149342A KR101577501B1 (ko) 2013-03-15 2013-12-03 딥 성형용 라텍스 조성물 및 이로부터 제조된 성형품

Publications (1)

Publication Number Publication Date
WO2014142425A1 true WO2014142425A1 (fr) 2014-09-18

Family

ID=51537037

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2013/011836 Ceased WO2014142425A1 (fr) 2013-03-15 2013-12-18 Composition de latex pour moulage par immersion et produit moulé produit à partir de celle-ci

Country Status (2)

Country Link
MY (1) MY185224A (fr)
WO (1) WO2014142425A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018048122A1 (fr) * 2016-09-09 2018-03-15 주식회사 엘지화학 Composition de latex pour moulage par immersion et article moulé fabriqué à partir de la composition
US20180201767A1 (en) * 2015-11-24 2018-07-19 Lg Chem, Ltd. Carboxylic acid-modified nitrile-based copolymer latex, method for preparing same, latex composition for dip molding containing same, and dip-molded article
GB2609537A (en) * 2021-05-27 2023-02-08 Korea Kumho Petrochemical Co Ltd A method for preparing latex composition for dip-forming

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1161527A (ja) * 1997-08-25 1999-03-05 Honny Chem Ind Co Ltd 着脱性に優れたゴム製手袋及びその製造方法
WO2005095508A1 (fr) * 2004-03-31 2005-10-13 Zeon Corporation Composition pour le formage par immersion et moulage obtenu par formage par immersion
KR20110053980A (ko) * 2008-08-27 2011-05-24 킴벌리-클라크 월드와이드, 인크. 얇은, 매끄러운 니트릴 고무 장갑
KR20120069222A (ko) * 2010-12-20 2012-06-28 주식회사 엘지화학 딥 성형용 라텍스 조성물 및 이를 사용하여 제조된 니트릴 고무 제품
KR20120086927A (ko) * 2011-01-27 2012-08-06 주식회사 엘지화학 딥 성형용 카르본산 변성 니트릴계 공중합체 라텍스, 이를 포함하는 딥 성형용 라텍스 조성물 및 이로부터 제조된 성형품

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1161527A (ja) * 1997-08-25 1999-03-05 Honny Chem Ind Co Ltd 着脱性に優れたゴム製手袋及びその製造方法
WO2005095508A1 (fr) * 2004-03-31 2005-10-13 Zeon Corporation Composition pour le formage par immersion et moulage obtenu par formage par immersion
KR20110053980A (ko) * 2008-08-27 2011-05-24 킴벌리-클라크 월드와이드, 인크. 얇은, 매끄러운 니트릴 고무 장갑
KR20120069222A (ko) * 2010-12-20 2012-06-28 주식회사 엘지화학 딥 성형용 라텍스 조성물 및 이를 사용하여 제조된 니트릴 고무 제품
KR20120086927A (ko) * 2011-01-27 2012-08-06 주식회사 엘지화학 딥 성형용 카르본산 변성 니트릴계 공중합체 라텍스, 이를 포함하는 딥 성형용 라텍스 조성물 및 이로부터 제조된 성형품

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180201767A1 (en) * 2015-11-24 2018-07-19 Lg Chem, Ltd. Carboxylic acid-modified nitrile-based copolymer latex, method for preparing same, latex composition for dip molding containing same, and dip-molded article
US10703884B2 (en) * 2015-11-24 2020-07-07 Lg Chem, Ltd. Carboxylic acid-modified nitrile-based copolymer latex, method for preparing same, latex composition for dip molding containing same, and dip-molded article
WO2018048122A1 (fr) * 2016-09-09 2018-03-15 주식회사 엘지화학 Composition de latex pour moulage par immersion et article moulé fabriqué à partir de la composition
US10858469B2 (en) 2016-09-09 2020-12-08 Lg Chem, Ltd. Latex composition for dip molding, and molded product manufactured therefrom
GB2609537A (en) * 2021-05-27 2023-02-08 Korea Kumho Petrochemical Co Ltd A method for preparing latex composition for dip-forming
GB2609537B (en) * 2021-05-27 2025-03-26 Korea Kumho Petrochemical Co Ltd Method for preparing latex composition for dip-forming

Also Published As

Publication number Publication date
MY185224A (en) 2021-04-30

Similar Documents

Publication Publication Date Title
WO2013077585A1 (fr) Latex de copolymère de nitrile modifié par de l'acide carbonique pour le moulage par immersion, composition de latex destinée au moulage par immersion l'incluant et pièce moulée fabriquée à partir de cette composition
WO2010143912A2 (fr) Latex pour moulage par immersion, composition pour moulage par immersion, procédé de préparation de produit moulé par immersion et produit moulé par immersion ainsi préparé
WO2019172539A1 (fr) Composition de latex d'un copolymère à base de nitrile modifié par l'acide carbonique, procédé de production associé, composition de latex le contenant pour moulage par immersion, et produit moulé, moulé à partir de cette dernière
WO2018043984A1 (fr) Composition de latex pour moulage par immersion, et article moulé préparé à partir de celle-ci
WO2010035955A2 (fr) Composition de résine à base de latex pour gants en caoutchouc, ne contenant ni soufre, ni accélérateur de vulcanisation, et procédé de production d'un moule de moulage par immersion reposant sur l'utilisation de ladite composition
KR101577501B1 (ko) 딥 성형용 라텍스 조성물 및 이로부터 제조된 성형품
WO2018048122A1 (fr) Composition de latex pour moulage par immersion et article moulé fabriqué à partir de la composition
WO2017069433A1 (fr) Composition de latex pour moulage par immersion et article moulé fabriqué à partir de la composition
WO2015030533A1 (fr) Composition de latex copolymère à base de nitrile modifié par un acide carboxylique et produit moulé par immersion comprenant ladite composition
WO2018048121A1 (fr) Composition de latex pour le moulage par immersion, et produit moulé fabriqué à partir de cette dernière
WO2019112312A1 (fr) Latex de copolymère à base de nitrile modifié avec de l'acide carbonique, procédé de préparation associé, composition de latex pour moulage par trempage comprenant celui-ci et produit moulé qui est moulé à partir de celui-ci
WO2013109033A1 (fr) Composition de latex pour le formage par immersion
WO2017090882A1 (fr) Latex copolymère à base de nitrile modifié par un acide carboxylique, procédé de préparation associé, composition de latex pour moulage par immersion le contenant et article moulé par immersion
WO2014142424A1 (fr) Composition de copolymère à base de nitrile modifié par acide carboxylique et article moulé par immersion fabriqué à partir de celle-ci
WO2020116793A1 (fr) Composition de latex pour moulage par immersion, son procédé de fabrication et article moulé à partir de cette dernière
WO2016105112A1 (fr) Composition de latex pour moulage par immersion et article moulé par immersion obtenu à l'aide de la composition
KR20120083031A (ko) 딥 성형용 카르본산 변성 니트릴계 공중합체 라텍스, 이를 포함하는 딥 성형용 라텍스 조성물 및 이로부터 제조된 성형품
KR101338539B1 (ko) 딥 성형용 카르본산 변성 니트릴계 공중합체 라텍스, 이를 포함하는 딥 성형용 라텍스 조성물 및 이로부터 제조된 성형품
WO2014142425A1 (fr) Composition de latex pour moulage par immersion et produit moulé produit à partir de celle-ci
KR101192276B1 (ko) 카르본산 변성 니트릴계 공중합체 라텍스와 이를 포함하는 딥 성형용 라텍스 조성물
WO2020130330A1 (fr) Composition de latex de copolymère à base de nitrile modifié par l'acide carbonique, composition de latex comprenant celle-ci pour moulage par immersion, et produit moulé à partir de celle-ci
WO2021071086A1 (fr) Composition de latex pour moulage par immersion, son procédé de production, et produit moulé par immersion produit à l'aide de celle-ci
WO2021071078A1 (fr) Procédé de préparation de latex de copolymère à base de nitrile modifié par un acide carboxylique
KR20120069222A (ko) 딥 성형용 라텍스 조성물 및 이를 사용하여 제조된 니트릴 고무 제품
KR102068791B1 (ko) 딥 성형용 라텍스, 딥 성형용 조성물, 딥 성형물 제조방법 및 그 방법에 의해 제조된 딥 성형물

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201380007858.4

Country of ref document: CN

WWE Wipo information: entry into national phase

Ref document number: 14371372

Country of ref document: US

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13877973

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13877973

Country of ref document: EP

Kind code of ref document: A1