WO2020138030A1 - Latex, composition de latex, corps moulé et caoutchouc mousse - Google Patents

Latex, composition de latex, corps moulé et caoutchouc mousse Download PDF

Info

Publication number
WO2020138030A1
WO2020138030A1 PCT/JP2019/050504 JP2019050504W WO2020138030A1 WO 2020138030 A1 WO2020138030 A1 WO 2020138030A1 JP 2019050504 W JP2019050504 W JP 2019050504W WO 2020138030 A1 WO2020138030 A1 WO 2020138030A1
Authority
WO
WIPO (PCT)
Prior art keywords
latex
weight
conjugated diene
butyl rubber
rubber
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/JP2019/050504
Other languages
English (en)
Japanese (ja)
Inventor
友哉 谷山
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.)
Zeon Corp
Original Assignee
Zeon Corp
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
Application filed by Zeon Corp filed Critical Zeon Corp
Priority to JP2020563283A priority Critical patent/JP7543912B2/ja
Publication of WO2020138030A1 publication Critical patent/WO2020138030A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/30—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by mixing gases into liquid compositions or plastisols, e.g. frothing with air
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C08L23/22—Copolymers of isobutene; Butyl rubber; Homopolymers or copolymers of other iso-olefins
    • 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 capable of giving a molded product having a short gelling time and excellent oil resistance, and a latex composition, a molded product, and a foam rubber using the latex.
  • Foam rubber manufactured using polymer rubber latex is used for various purposes such as mattresses, cosmetic sponges (puffs), rolls, and shock absorbers.
  • foam rubber a sponge that has good oil resistance to cosmetics, is easy to take in cosmetics, and has good adhesiveness (adhesion) to the skin, especially for puffs. It has been demanded.
  • acrylonitrile-butadiene copolymer rubber (NBR) latex has been conventionally used as a polymer latex for obtaining such a rubber foam (for example, Patent Document 1). reference).
  • NBR acrylonitrile-butadiene copolymer rubber
  • the rubber foam obtained by using the acrylonitrile-butadiene copolymer rubber latex has oil resistance depending on the type of ingredients used as cosmetics. It may not be sufficient, more specifically, the oil resistance to ultraviolet absorbers such as octyl paramethoxycinnamate is not sufficient, therefore, a polymer latex showing oil resistance to such components is Was wanted.
  • the present invention has been made in view of such actual circumstances, a time required for gelation is short, and a latex capable of giving a molded article excellent in oil resistance, and a latex composition using the same It is intended to provide articles, molded articles, and foam rubber.
  • the present inventors include butyl rubber, a nitrile group-containing conjugated diene copolymer, and water, and a weight ratio of the butyl rubber and the nitrile group-containing conjugated diene copolymer is appropriately adjusted.
  • the present inventors have completed the present invention by finding that it is possible to provide a molded product having a short gelation time and excellent oil resistance.
  • butyl rubber, a nitrile group-containing conjugated diene copolymer, and water are contained, and the weight ratio of the butyl rubber and the nitrile group-containing conjugated diene copolymer is 85:15 to 10:90.
  • a latex is provided.
  • the latex of the present invention preferably further contains an anionic emulsifier.
  • the content ratio of the isobutylene unit in the butyl rubber is preferably 95 mol% or more.
  • the butyl rubber preferably has a Mooney viscosity (ML1+8, 125° C.) of 20 to 70.
  • the content ratio of the ethylenically unsaturated nitrile monomer unit in the nitrile group-containing conjugated diene copolymer is preferably 5 to 80% by weight.
  • a latex composition containing the above latex and a crosslinking agent.
  • the latex composition of the present invention preferably further contains a crosslinking accelerator.
  • the latex composition of the present invention preferably further contains a cell stabilizer.
  • a molded article obtained by using the above latex or the above latex composition.
  • a foam rubber obtained by using the above latex or the above latex composition.
  • a latex capable of giving a molded product having a short gelling time and excellent oil resistance, and a latex composition, a molded product, and a foam rubber using the latex. be able to.
  • the latex of the present invention contains butyl rubber, a nitrile group-containing conjugated diene-based copolymer, and water.
  • the butyl rubber used in the present invention is a rubber made of a polymer having a repeating unit derived from isobutylene (isobutene), and more specifically, a rubber made of a copolymer of isobutylene and a small amount of isoprene (isobutylene-isoprene rubber). ). Further, the butyl rubber may be a halogenated butyl rubber obtained by halogenating a part of a copolymer of isobutylene and a small amount of isoprene.
  • the content ratio of the isobutylene unit in the butyl rubber is not particularly limited, but is preferably 95 mol% or more and less than 100 mol %, more preferably 97 to 99.9 mol %.
  • the content ratio (unsaturation) of the isoprene unit in the butyl rubber is not particularly limited, but is preferably more than 0 mol% and 5 mol% or less, more preferably 0.1 to 3 mol%.
  • the butyl rubber preferably has a Mooney viscosity (ML1+8, 125° C.) in the range of 20 to 70, more preferably 20 to 65, and further preferably 25 to 60.
  • Mooney viscosity ML1+8, 125° C.
  • the volume cumulative particle diameter d50 of rubber particles made of butyl rubber in the latex of the present invention is preferably 100 to 5,000 nm, more preferably 150 to The thickness is 4,000 nm, more preferably 250 to 3,000 nm, and particularly preferably 500 to 2,000 nm.
  • the volume cumulative particle diameter d50 of the rubber particles made of butyl rubber can be controlled by, for example, the type and amount of anionic emulsifier used in the production of a latex of butyl rubber described below, the emulsification conditions during emulsification, and the like.
  • the nitrile group-containing conjugated diene-based copolymer used in the present invention is a copolymer obtained by copolymerizing a conjugated diene monomer and an ethylenically unsaturated nitrile monomer, and in addition to these, necessary It may be a copolymer obtained by copolymerizing another ethylenically unsaturated monomer copolymerizable therewith, which is used according to the above.
  • the ethylenically unsaturated nitrile monomer is not particularly limited as long as it is an ethylenically unsaturated monomer containing a nitrile group, and examples thereof include acrylonitrile, methacrylonitrile, fumaronitrile, ⁇ -chloroacrylonitrile, ⁇ -cyanoethylacrylonitrile. And so on. Of these, acrylonitrile and methacrylonitrile are preferable, and acrylonitrile is more preferable. These ethylenically unsaturated nitrile monomers may be used alone or in combination of two or more.
  • the content ratio of the ethylenically unsaturated nitrile monomer unit formed by the ethylenically unsaturated nitrile monomer in the nitrile group-containing conjugated diene copolymer is preferably 5 to 80% by weight, more preferably Is 15 to 70% by weight, more preferably 20 to 60% by weight, and particularly preferably 31 to 60% by weight.
  • conjugated diene monomer examples include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene and chloroprene. To be Of these, 1,3-butadiene and isoprene are preferable. These conjugated diene monomers can be used alone or in combination of two or more.
  • the content ratio of the conjugated diene monomer unit formed by the conjugated diene monomer in the nitrile group-containing conjugated diene copolymer is preferably 20 to 95% by weight, more preferably 30 to 85% by weight. %, more preferably 40 to 80% by weight, particularly preferably 40 to 69% by weight.
  • the ratio of the 1,3-butadiene unit and the isoprene unit in the nitrile group-containing conjugated diene-based copolymer is 5/in the ratio of 1,3-butadiene unit/isoprene unit. It is preferably in the range of 5 to 9/1.
  • ethylenically unsaturated monomers copolymerizable with the conjugated diene monomer and the ethylenically unsaturated nitrile monomer include, for example, (meth)acrylic acid, (anhydrous) maleic acid, fumaric acid, itaconic acid.
  • Ethylenically unsaturated carboxylic acid such as; methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, maleic acid mono- or dimethyl, fumaric acid mono Or mono- or di-alkyl ester of ethylenically unsaturated carboxylic acid such as diethyl, mono- or di-n-butyl fumarate, mono- or di-n-butyl itaconic acid; ethylenic such as methoxy acrylate, ethoxy acrylate, methoxy ethoxy ethyl acrylate Alkoxyalkyl ester of unsaturated carboxylic acid; (meth)acrylate having hydroxyalkyl group such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)
  • the content ratio of the other monomer unit formed by the other ethylenically unsaturated monomer in the nitrile group-containing conjugated diene copolymer is preferably 40% by weight or less, more preferably 30% by weight. % Or less, more preferably 20% by weight or less.
  • the volume cumulative particle diameter d50 of the rubber particles made of the nitrile group-containing conjugated diene-based copolymer in the latex of the present invention is preferably 420 to 1500 nm. , More preferably 460 to 1250 nm, further preferably 500 to 1000 nm.
  • the content ratio of the butyl rubber and the nitrile group-containing conjugated diene copolymer in the latex of the present invention is 85:15 to 10:90 by the weight ratio of (butyl rubber:nitrile group-containing conjugated diene copolymer). It is preferably 85:15 to 20:80, more preferably 80:20 to 30:70. If there is too much butyl rubber, it will take a long time for gelation. In addition, when a molded article such as foam rubber is manufactured using latex, it is greatly shrunk during molding. On the other hand, if the amount of the nitrile group-containing conjugated diene-based copolymer is too large, the oil resistance of the obtained molded product is insufficient.
  • the total content ratio (solid content concentration) of the butyl rubber and the nitrile group-containing conjugated diene-based copolymer in the latex of the present invention is preferably 50% by weight or more, more preferably 55 to 70% by weight, further It is preferably 60 to 70% by weight.
  • the latex of the present invention preferably contains an anionic emulsifier.
  • the anionic emulsifier is not particularly limited, but fatty acid salts such as sodium laurate, potassium myristate, sodium palmitate, potassium oleate, and sodium linolenate; sodium dodecylbenzenesulfonate, potassium dodecylbenzenesulfonate, decylbenzenesulfone.
  • Alkylbenzenesulfonates such as sodium acidate, potassium decylbenzenesulfonate, sodium cetylbenzenesulfonate, potassium cetylbenzenesulfonate, etc.; sodium di(2-ethylhexyl)sulfosuccinate, potassium di(2-ethylhexyl)sulfosuccinate, dioctylsulfosuccinic acid
  • Alkyl sulfosuccinates such as sodium; alkyl sulphate salts such as sodium lauryl sulphate and potassium lauryl sulphate; polyoxyethylene alkyl ether sulphate salts such as sodium polyoxyethylene lauryl ether sulphate and potassium polyoxyethylene lauryl ether sulphate; lauryl phosphorus Monoalkyl phosphates such as sodium acidate and potassium lauryl phosphate; rosin acid salts such as sodium rosinate and potassium rosinate;
  • a fatty acid salt having 6 to 30 carbon atoms (that is, a carboxylic acid salt of a chain hydrocarbon having no ring structure) is preferable because the storage stability of the obtained latex can be further increased
  • a fatty acid salt having 10 to 24 carbon atoms is preferable
  • a fatty acid salt having 13 to 21 carbon atoms is more preferable
  • potassium oleate is particularly preferable.
  • the anionic emulsifier, in the latex of the present invention in addition to the effect of emulsifying and dispersing the butyl rubber and the nitrile group-containing conjugated diene-based copolymer, when producing a molded article such as foam rubber, as a foaming agent Also works.
  • the latex of the present invention can further shorten the time required for gelation of the latex by containing the anionic emulsifier. Further, when a molded article such as foam rubber is manufactured using latex, shrinkage during molding can be suppressed.
  • an emulsifier other than the anionic emulsifier for example, a cationic emulsifier or a nonionic emulsifier may be used together.
  • the time required for gelation of the obtained latex can be further shortened, and further, when producing a molded article such as foam rubber using the latex, it is possible to suppress shrinkage during molding,
  • the content ratio of the anionic emulsifier in the emulsifier used is preferably 5% by weight or more, more preferably 7% by weight or more, particularly preferably 10% by weight or more, and as an emulsifier, It is preferable to use an anionic emulsifier only.
  • the content of the anionic emulsifier in the latex of the present invention is preferably 2 to 10 parts by weight based on 100 parts by weight of the butyl rubber and the nitrile group-containing conjugated diene copolymer in total.
  • the latex of the present invention can be produced, for example, by blending a latex of butyl rubber and a latex of a nitrile group-containing conjugated diene copolymer.
  • the method for producing butyl rubber is not particularly limited, and examples thereof include a method of slurry polymerization of isobutylene and isoprene at -100 to -90°C in methylene chloride using aluminum chloride as a catalyst.
  • the butyl rubber is a halogenated butyl rubber, it is obtained by slurry polymerization in hexane at 4 to 60° C. using bromine (Br 2 ) or chlorine (Cl 2 ) as a halogenating agent. It can be produced by a method of halogenating butyl rubber.
  • the butyl rubber latex used for the production of the latex was obtained by, for example, a step of obtaining an emulsion by mixing a butyl rubber solution in which butyl rubber is dissolved in a solvent with water in the presence of an anionic emulsifier. It can be manufactured through a step of removing the solvent from the emulsion.
  • a polymerization solution obtained by slurry polymerization may be used as it is, or a solid butyl rubber is taken out from the polymerization solution obtained by slurry polymerization, and then obtained by dissolving it in a solvent again. You may use the thing.
  • the solvent used in this case is not particularly limited, but preferably includes hexane, isohexane, pentane, cyclohexane, heptane, isooctane, xylene, toluene, benzene, and carbon dioxide in a supercritical state. Cyclohexane is preferable from the viewpoint that the latex of can be obtained more appropriately.
  • Butyl rubber solution, in the presence of an anionic emulsifier, by emulsifying by mixing with water, as a method of obtaining an emulsion is not particularly limited, butyl rubber solution, a method of mixing an aqueous solution containing an anionic emulsifier and , A butyl rubber solution containing an anionic emulsifier and mixing it with water, a method of mixing a butyl rubber solution containing an anionic emulsifier with an aqueous solution containing an anionic emulsifier, and the like.
  • an emulsifying device can be used, and as the emulsifying device, a commercially available emulsifying device or disperser can be used without limitation.
  • the emulsifying device examples include a batch type emulsifier such as a trade name "homogenizer” (manufactured by IKA), a trade name “Polytron” (manufactured by Kinematica), and a trade name “TK Auto Homo Mixer” (manufactured by Tokushu Kika Kogyo).
  • a batch type emulsifier such as a trade name "homogenizer” (manufactured by IKA), a trade name “Polytron” (manufactured by Kinematica), and a trade name “TK Auto Homo Mixer” (manufactured by Tokushu Kika Kogyo).
  • Membrane emulsifiers such as trade name "Membrane emulsifier” (made by Refrigeration Industry Co., Ltd.); Vibratory emulsifiers such as trade name “Vibro Mixer” (made by Refuse Industry Co., Ltd.); Trade name “Ultrasonic homogenizer” (Branson Ultrasonic wave emulsifying machine; manufactured by the same company; and the like.
  • the conditions of the emulsification operation are not particularly limited, and the treatment temperature, the treatment time and the like may be appropriately selected so as to obtain a desired dispersion state.
  • anionic emulsifier used to obtain the emulsion from the butyl rubber solution those mentioned above as the anionic emulsifier that can be contained in the latex can be used.
  • a butyl rubber latex can be obtained by performing a solvent removal operation on the obtained emulsion.
  • the method for removing the solvent from the emulsion is not particularly limited as long as the content of the solvent in the latex of the obtained butyl rubber can be 500 ppm by weight or less, for example, vacuum distillation, Methods such as atmospheric distillation, steam distillation, and centrifugal separation can be adopted.
  • the vacuum distillation can be carried out by heating the emulsion, preferably under a reduced pressure of 500 to 900 hPa.
  • the temperature in vacuum distillation may be appropriately selected according to the type of solvent used, but is preferably 50 to 90°C.
  • Centrifugation is performed, for example, using a centrifugal separator such as a continuous centrifuge, and the centrifugal force is preferably within the range of 100 to 10,000 G, more preferably within the range of 2,000 to 8,000 G.
  • the flow rate fed into the centrifuge is preferably 500 to 1700 Kg/hr, and the back pressure (gauge pressure) of the centrifuge is preferably 0.03 to 1.6 MPa. It is preferable to carry out under the conditions.
  • a butyl rubber latex can be obtained as a light liquid after centrifugation.
  • the butyl rubber latex obtained by removing the solvent may be subjected to a concentration treatment, if necessary, to adjust the solid content concentration.
  • concentration treatment include a method of partially evaporating water by reducing pressure, a method of centrifugation, and the like.
  • the content ratio of butyl rubber (solid content concentration) in the latex of butyl rubber used for producing latex is preferably 50% by weight or more, more preferably 55 to 70% by weight, further preferably 60 to 70% by weight. Is.
  • the content of the anionic emulsifier in the latex of butyl rubber is preferably 2 to 10 parts by weight with respect to 100 parts by weight of butyl rubber.
  • the latex of the nitrile group-containing conjugated diene-based copolymer used for the production of the latex for example, a step of copolymerizing a mixture of monomers constituting the nitrile group-containing conjugated diene-based copolymer by an emulsion polymerization method. Can be manufactured.
  • auxiliary polymerization materials such as an emulsifier (surfactant), a polymerization initiator, a chelating agent, an oxygen scavenger, and a molecular weight modifier can be used. ..
  • the method of adding these polymerization auxiliary materials is not particularly limited, and any method such as an initial batch addition method, a divided addition method, or a continuous addition method may be used.
  • the emulsifier is not particularly limited, and examples thereof include anionic emulsifiers and nonionic emulsifiers, with anionic emulsifiers being preferred.
  • anionic emulsifier those described above as the anionic emulsifier that can be contained in the latex can be used.
  • the amount of the emulsifier used is preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the monomer mixture.
  • the polymerization initiator is not particularly limited, and examples thereof include inorganic peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate, and hydrogen peroxide; diisopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, di-t-butylperoxide, di- ⁇ - Organic peroxides such as cumyl peroxide, acetyl peroxide, isobutyryl peroxide, benzoyl peroxide, octanoyl peroxide, 3,5,5-trimethylhexanoyl peroxide; azobisisobutyronitrile, azobis-2 , 4-dimethylvaleronitrile, azo compounds such as methyl azobisisobuty
  • polymerization initiators can be used alone or in combination of two or more kinds.
  • the amount of the polymerization initiator used is preferably 0.01 to 10 parts by weight, more preferably 0.01 to 2 parts by weight, based on 100 parts by weight of the monomer mixture.
  • the peroxide initiator can be used as a redox polymerization initiator in combination with a reducing agent.
  • the reducing agent is not particularly limited, but a compound containing a metal ion in a reduced state such as ferrous sulfate and cuprous naphthenate; a sulfonic acid compound such as sodium methanesulfonate; an amine compound such as dimethylaniline ; And the like.
  • These reducing agents can be used alone or in combination of two or more.
  • the amount of the reducing agent used is preferably 3 to 1000 parts by weight with respect to 100 parts by weight of the peroxide.
  • the molecular weight modifier examples include alkyl mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, t-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-stearyl mercaptan; dimethylxanthogen disulfide, diisopropylxanthogendi Xanthogen compounds such as sulfides; thiuram-based compounds such as tetramethylthiuram disulfide, tetraethylthiuram disulfide and tetramethylthiuram monosulfide; phenolic compounds such as 2,6-di-t-butyl-4-methylphenol and styrenated phenol; Allyl compounds such as allyl alcohol; halogenated hydrocarbon compounds such as dichloromethane, dibromomethane, carbon
  • molecular weight modifiers can be used alone or in combination of two or more kinds.
  • the amount of the molecular weight modifier used is preferably 0.1 to 3 parts by weight, more preferably 0.2 to 2 parts by weight, particularly preferably 0.3 to 1.5 parts by weight, based on 100 parts by weight of the monomer mixture. It is a department.
  • the amount of water used for emulsion polymerization is preferably 80 to 600 parts by weight, and particularly preferably 100 to 300 parts by weight, based on 100 parts by weight of all the monomers used.
  • the emulsion polymerization reaction may be either continuous type or batch type, and the polymerization time is not particularly limited.
  • the method of adding the monomer include, for example, a method of adding the monomers used in the reaction vessel all at once, a method of continuously or intermittently adding as the polymerization proceeds, or a part of the monomer being added. And a reaction is carried out to a specific conversion rate, and then the remaining monomer is continuously or intermittently added to carry out polymerization, and any method may be adopted.
  • the composition of the mixture may be constant or may be changed. Further, each monomer may be added to the reaction vessel after mixing various monomers to be used in advance, or may be added to the reaction vessel separately.
  • the proportion of the conjugated diene monomer added after the polymerization reaction is started is preferably 20 to 60% by weight based on the total amount of the conjugated diene monomer used for the polymerization.
  • a polymerization auxiliary material such as a chelating agent, a dispersant, a pH adjusting agent, an oxygen scavenger, and a particle diameter adjusting agent can be used. It is not particularly limited.
  • the polymerization conversion rate at the time of stopping the polymerization is not particularly limited, but is preferably 90% by weight or more. If this polymerization conversion rate is too low, the productivity tends to decrease.
  • the polymerization temperature is not particularly limited, but is preferably 0 to 50°C, more preferably 2 to 35°C.
  • the polymerization terminator is not particularly limited, and examples thereof include hydroxylamine, hydroxyamine sulfate, diethylhydroxylamine, hydroxyamine sulfonic acid and alkali metal salts thereof, sodium dimethyldithiocarbamate, hydroquinone derivative, catechol derivative, and hydroxydimethyl.
  • examples thereof include aromatic hydroxydithiocarboxylic acids such as benzenethiocarboxylic acid, hydroxydiethylbenzenedithiocarboxylic acid and hydroxydibutylbenzenedithiocarboxylic acid, and alkali metal salts thereof.
  • the amount of the polymerization terminator used is preferably 0.05 to 2 parts by weight with respect to 100 parts by weight of the monomer mixture.
  • the polymerization reaction can be performed as described above to obtain an emulsion. After the polymerization reaction is stopped to obtain the emulsion, the unreacted monomer may be removed from the emulsion as needed.
  • the volume cumulative particle diameter d50 is set within the above range. It is adjustable.
  • a method for adjusting the volume cumulative particle diameter (i) a method of enlarging particles in the emulsion by coalescing them, a method of performing a particle size enlargement treatment, and (ii) particles contained in the emulsion After coagulating to obtain a coagulated product, the coagulated product is dissolved in an organic solvent to obtain a solution, and then the obtained solution is emulsified in water in the presence of an emulsifier, and the organic solvent is removed if necessary. (Iii) a method of mixing two or more emulsions having different volume cumulative particle diameters, and the like.
  • the method of particle size enlargement treatment is not particularly limited, but for example, (1) after completion of the polymerization, a conjugated diene compound such as 1,3-butadiene or toluene is added to the emulsion. Is added as a solvent, and the mixture is vigorously stirred, and (2) a particle size increasing agent such as a carboxyl group-containing polymer latex is added to the emulsion, and the mixture is vigorously stirred.
  • a conjugated diene compound such as 1,3-butadiene or toluene is added to the emulsion.
  • a particle size increasing agent such as a carboxyl group-containing polymer latex
  • the amount of the solvent added is preferably 30 to 300 parts by weight with respect to 100 parts by weight of the nitrile group-containing conjugated diene copolymer in the emulsion. It is a department.
  • the stirring conditions are not particularly limited, but for example, using a stirring device such as a paddle type stirring blade, the rotation speed is preferably Is 50 to 2,500 rpm, and the stirring time is preferably 0.5 to 12.0 hours.
  • a method of coagulating particles contained in the emulsion for example, a method of mixing the emulsion and a water-soluble organic solvent, a method of mixing the emulsion and an acid, an emulsion and a salt And a method of mixing with.
  • water-soluble organic solvent it is more preferable to select a solvent that does not dissolve the polymer in the latex.
  • organic solvents include methanol, ethanol, isopropyl alcohol, ethylene glycol and the like.
  • the acid include acetic acid, formic acid, phosphoric acid, hydrochloric acid and the like.
  • salt include calcium chloride, sodium chloride, aluminum sulfate, potassium chloride and the like.
  • organic solvent used in the method (ii) examples include aromatic hydrocarbon solvents such as benzene, toluene and xylene; alicyclic hydrocarbon solvents such as cyclopentane, cyclopentene, cyclohexane and cyclohexene; pentane, hexane and heptane.
  • aromatic hydrocarbon solvents such as benzene, toluene and xylene
  • alicyclic hydrocarbon solvents such as cyclopentane, cyclopentene, cyclohexane and cyclohexene
  • pentane hexane and heptane.
  • Aliphatic hydrocarbon solvent such as ethylene dichloride; acetone, methyl ethyl ketone, diethyl ketone, diisopropyl ketone, methyl isobutyl ketone, methylhexyl ketone, diisobutyl ketone, butyraldehyde, propyl acetate, Ketone solvents such as butyl acetate and amyl acetate; ester solvents such as ethyl propionate, ethyl isobutyrate and butyl butyrate; ether solvents such as dimethyl ether, dihexyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether; etc. Can be mentioned.
  • an emulsifying device can be used to emulsify the obtained solution in water in the presence of an emulsifier.
  • the method of adding the emulsifier is not particularly limited, and may be added to the solution in advance, or may be added to the solution during the emulsification operation, or may be added all at once or in divided portions. Good.
  • the emulsifying device for example, the one described above as the emulsifying device used for emulsifying the butyl rubber solution can be similarly used.
  • Examples of the emulsifier used in the method (ii) include anionic emulsifiers and nonionic emulsifiers, with anionic emulsifiers being preferred.
  • anionic emulsifier those described above as the anionic emulsifier that can be contained in the latex can be used.
  • the amount of the emulsifier used is preferably 0.5 to 50 parts by weight, more preferably 0.5 to 30 parts by weight, and further preferably 5 to 25 parts by weight, based on 100 parts by weight of the particles. By appropriately adjusting the amount of the emulsifier used, the volume cumulative particle diameter can be adjusted within a desired range.
  • examples of methods for removing the organic solvent include methods such as vacuum distillation, atmospheric distillation, steam distillation, and centrifugation.
  • two or more emulsions may be mixed so that the desired volume cumulative particle diameter is obtained, and the mixing method is not particularly limited.
  • the combination of the emulsions is not limited, and for example, two emulsions having different volume cumulative particle diameters obtained by the method (i) may be mixed, or the volume accumulated particles obtained by the method (ii) may be mixed. You may mix two emulsions with different diameters. Further, the emulsion obtained by polymerization and the emulsion obtained by the method (i) and/or (ii) may be mixed by a known method, or obtained by the method (i). You may mix an emulsion and the emulsion obtained by the method of (ii).
  • the content ratio (solid content) of the nitrile group-containing conjugated diene copolymer in the latex of the nitrile group-containing conjugated diene copolymer used for producing the latex is preferably 50% by weight or more, It is preferably 55 to 70% by weight, more preferably 60 to 70% by weight.
  • the content of the anionic emulsifier in the latex of the nitrile group-containing conjugated diene copolymer is preferably 2 to 10 parts by weight with respect to 100 parts by weight of the nitrile group-containing conjugated diene copolymer.
  • the latex obtained by blending the latex of butyl rubber and the latex of the nitrile group-containing conjugated diene copolymer may be subjected to concentration treatment, if necessary, to adjust the solid content concentration.
  • concentration treatment include a method of partially evaporating water by reducing pressure, a method of centrifugation, and the like.
  • the latex of the present invention Since the latex of the present invention has a short gelling time, it can be molded in a short time, whereby a desired molded product can be obtained in a short time. Furthermore, since the latex of the present invention has a short gelling time, it is possible to gel at a high expansion ratio, and when the latex of the present invention is used to produce a foam rubber, it has flexibility. It is possible to obtain excellent foam rubber with high productivity. Therefore, the latex of the present invention is suitable for use as a foam rubber.
  • the latex composition of the present invention contains the above-mentioned latex of the present invention and a crosslinking agent.
  • cross-linking agent examples include powdered sulfur, sulfur flower, precipitated sulfur, colloidal sulfur, surface-treated sulfur, sulfur such as insoluble sulfur; sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, N,N′-dithio.
  • sulfur-containing compounds such as -bis(hexahydro-2H-azepinone-2), phosphorus-containing polysulfide, polymer polysulfide, and 2-(4'-morpholino dithio)benzothiazole.
  • sulfur can be preferably used.
  • the crosslinking agent may be used alone or in combination of two or more.
  • the content of the cross-linking agent is not particularly limited, but is preferably 0.1 to 15 parts by weight, more preferably 0.2 to 8 parts by weight based on 100 parts by weight of the total of the butyl rubber and the nitrile group-containing conjugated diene copolymer. Parts by weight.
  • the latex composition of the present invention preferably contains a crosslinking accelerator.
  • a crosslinking accelerator those usually used in the production of a molded article obtained by using a latex composition such as foam rubber can be used, and examples thereof include diethyldithiocarbamic acid, dibutyldithiocarbamic acid, di-2-ethylhexyldithiocarbamic acid, Dithiocarbamic acids such as dicyclohexyldithiocarbamic acid, diphenyldithiocarbamic acid and dibenzyldithiocarbamic acid, and dithiocarbamic acid crosslinking accelerators such as zinc salts thereof; 2-mercaptobenzothiazole, 2-mercaptobenzothiazole zinc, 2-mercaptothiazoline, dibenzothia Dil disulfide, 2-(2,4-dinitrophenylthio)benzothiazole, 2-(N,N-diethylthiocarbaylthi
  • the content of the crosslinking accelerator is preferably 0.1 to 15 parts by weight, more preferably 0.2 to 10 parts by weight, based on 100 parts by weight of the total amount of the butyl rubber and the nitrile group-containing conjugated diene copolymer. Is. By setting the content of the crosslinking accelerator within the above range, the strength of the obtained molded article such as foam rubber can be further increased.
  • the latex composition of the present invention preferably contains a crosslinking aid.
  • a crosslinking aid those commonly used in the production of molded articles obtained by using a latex composition such as foam rubber can be used, and examples thereof include zinc oxide, stearic acid and zinc salts thereof.
  • the content of the crosslinking aid is preferably 0.5 to 10 parts by weight, more preferably 0.5 to 8 parts by weight, based on 100 parts by weight of the total of the butyl rubber and the nitrile group-containing conjugated diene copolymer. ..
  • the content of the crosslinking aid is preferably 0.5 to 10 parts by weight, more preferably 0.5 to 8 parts by weight, based on 100 parts by weight of the total of the butyl rubber and the nitrile group-containing conjugated diene copolymer. ..
  • the latex composition of the present invention preferably further contains a cell stabilizer.
  • a cell stabilizer By using the foam stabilizer, when the latex of the present invention is used for foam rubber, it is possible to make the bubbles contained in the obtained foam rubber fine and uniform, which results in flexibility and The strength can be improved.
  • the bubble stabilizer includes, for example, an alkyl chloride/formaldehyde/ammonia reaction product obtained by reacting an alkyl chloride such as ethyl chloride with formaldehyde and ammonia.
  • the alkyl chloride/formaldehyde/ammonia reaction product is preferably one having an alkyl carbon number of 4 or less, and a specific example thereof is an ethyl chloride/formaldehyde/ammonia reaction product.
  • an alkyl quaternary ammonium chloride preferably an alkyl quaternary ammonium chloride having an alkyl carbon number of 4 or less
  • an alkyl aryl sulfonate preferably an alkyl aryl sulfonate having an alkyl carbon number of 4 or less
  • higher fatty acid ammonium preferably higher fatty acid ammonium in which alkyl has 4 or less carbon atoms; hexafluorosilicate, etc., can be used as the bubble stabilizer.
  • the alkyl chloride-formaldehyde-ammonia reaction product is preferable, the alkyl chloride-formaldehyde-ammonia reaction product having an alkyl carbon number of 4 or less is more preferable, and the ethyl chloride.
  • Formaldehyde-ammonia reaction products are particularly preferred.
  • a commercial product such as a trade name “Trimen Base” (manufactured by Crompton Corp.) can be used.
  • the content of the cell stabilizer is preferably 0.4 to 10 parts by weight, more preferably 0.4 to 6 parts by weight, based on 100 parts by weight of the total amount of the butyl rubber and the nitrile group-containing conjugated diene copolymer. ..
  • the content of the cell stabilizer is preferably 0.4 to 10 parts by weight, more preferably 0.4 to 6 parts by weight, based on 100 parts by weight of the total amount of the butyl rubber and the nitrile group-containing conjugated diene copolymer. ..
  • the latex composition of the present invention further comprises a dispersant (for example, NASF (formalin naphthalene sulfonate) for stably dispersing antioxidants, colorants and the like, or the above-mentioned various compounding agents in the latex.
  • a dispersant for example, NASF (formalin naphthalene sulfonate) for stably dispersing antioxidants, colorants and the like, or the above-mentioned various compounding agents in the latex.
  • a thickener for example, polyacrylic acid and its sodium salt, sodium alginate, polyvinyl alcohol, etc.
  • a surfactant as a foaming agent for example, an aliphatic alkali such as potassium oleate. Soap, sulfates of higher alcohols such as sodium dodecylsulfate, etc.
  • the method for preparing the latex composition of the present invention is not particularly limited, but for example, after the latex is obtained as described above, the latex may be prepared, if necessary, using a dispersing machine such as a ball mill, a kneader or a disper.
  • a dispersing machine such as a ball mill, a kneader or a disper.
  • a method of mixing various compounding agents to be compounded a method of preparing an aqueous dispersion of compounding ingredients other than latex by using the above-mentioned disperser, and then mixing the aqueous dispersion with latex. ..
  • the molded article of the present invention is obtained by using the above-mentioned latex or latex composition.
  • the molded product of the present invention is not particularly limited, but a film-shaped molded product obtained by molding a latex (latex composition) on a substrate by a method such as a method, or a latex (latex composition)
  • a method such as a method, or a latex (latex composition)
  • examples include dip-molded articles obtained by dip-molding, or various molded articles obtained by coagulating latex (latex composition) and molding the obtained coagulated rubber into a desired shape.
  • foam rubber is preferable.
  • the case where the molded product of the present invention is foam rubber will be described as an example, but the molded product of the present invention is not particularly limited to foam rubber.
  • the molded product of the present invention is obtained by using the above-mentioned latex or latex composition.
  • the foam rubber of the present invention can be obtained by foaming and coagulating the above-mentioned latex or latex composition at a desired expansion ratio.
  • Air is usually used for foaming, but carbonates such as ammonium carbonate and sodium bicarbonate; azo compounds such as azodicarboxylic acid amide and azobisisobutyronitrile; gas generating substances such as benzenesulfonyl hydrazide can also be used.
  • the latex latex composition
  • the latex can be agitated and bubbled by incorporating air.
  • a stand mixer, an Oaks foaming machine, an ultrasonic foaming machine or the like can be used.
  • the expanded latex (latex composition) is solidified in order to fix the foamed state.
  • Any coagulation method can be used as long as it can gelate and solidify the latex, and conventionally known methods can be used.
  • sodium hexafluorosilicate sodium silicofluoride
  • potassium hexafluorosilicate sica
  • Dunlop method cold coagulation method in which a room temperature coagulating agent such as a potassium fluoride) or a silicon fluoride compound such as titanium silicofluoride is added to the foamed latex (latex composition); organopolysiloxane, polyvinyl methyl ether
  • a heat-sensitive coagulation method in which a heat-sensitive coagulant such as a zinc ammonium sulfate complex salt is added to a foamed latex (latex composition); a freeze coagulation method or the like is used.
  • the amount of the coagulant such as the room temperature coagulant and the heat-sensitive coagulant is not particularly limited, but preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the butyl rubber and the nitrile group-containing conjugated diene copolymer. , And more preferably 0.5 to 8.
  • foam rubber can be obtained by adding a coagulant to the foamed latex (latex composition), transferring it to a mold of a desired shape, and coagulating it. Further, after coagulation, heating may be performed in order to crosslink the latex (latex composition).
  • the conditions for the cross-linking may be a temperature of 100 to 160° C., preferably a heat treatment of 15 to 120 minutes.
  • the washing method is not particularly limited, and examples thereof include a method of washing by using a washing machine or the like with water at about 20 to 70° C. for about 5 to 15 minutes with stirring. After washing, it is preferable to drain water and dry at a temperature of about 30 to 90° C. so as not to impair the texture of the foam rubber.
  • the foam rubber thus obtained can be used as a puff (cosmetic sponge), for example, by slicing it into a predetermined thickness, cutting it into a predetermined shape, and polishing the side surface with a rotary grindstone or the like. it can.
  • the foam rubber obtained by using the latex (latex composition) of the present invention can be suitably used for various applications such as mattresses, puffs (cosmetic sponges), rolls and shock absorbers.
  • the foam rubber obtained by using the latex (latex composition) of the present invention has oil resistance to a plurality of components used as cosmetics, particularly paraffin and an ultraviolet absorber (eg, used as components of cosmetics). Since it has excellent oil resistance to octyl paramethoxycinnamate (2-ethylhexyl 4-methoxycinnamate, etc.), it can be suitably used as a puff (cosmetic sponge) impregnated with liquid cosmetics.
  • volume-based particle size distribution The volume-based particle size distribution of the latex was measured using a light scattering diffraction particle size measuring device (model “LS-13320”, manufactured by Beckman Coulter, Inc.). The volume cumulative particle size d50 was determined based on the obtained volume-based particle size distribution.
  • the latex composition for foam rubber was foamed by stirring with a stand mixer (manufactured by Electrolux, ESM945), and the time until the volume reached 5.0 times the volume before stirring was determined.
  • ⁇ Swelling rate with respect to ultraviolet absorber> The foam rubber is immersed in an ultraviolet absorbent (2-ethylhexyl 4-methoxycinnamate, manufactured by Tokyo Kasei Kogyo Co., Ltd.) at 23° C. for 24 hours, and the volume of the foam rubber after immersion is relative to the volume of the foam rubber before immersion.
  • the ratio (swelling ratio (%) (volume of foam rubber after immersion)/(volume of foam rubber before immersion) ⁇ 100) was calculated. It can be judged that the lower the swelling ratio, the better the oil resistance to the ultraviolet absorber.
  • ⁇ Preparation Example 1 (Preparation of butyl rubber latex)> 100 parts of butyl rubber (product name “JSR BUTYL365”, manufactured by JSR, Mooney viscosity (ML1+8, 125° C.): 33, degree of unsaturation 2.3 mol %) are mixed with 550 parts of cyclohexane, and the temperature is 60 with stirring. The butyl rubber was dissolved by raising the temperature to °C to obtain a butyl rubber solution. Separately, potassium oleate and water were mixed to obtain a 15 wt% potassium oleate aqueous solution.
  • the butyl rubber solution obtained above and the potassium oleate aqueous solution prepared above were mixed with a multi-line mixer (product name “multi-line mixer MS26-MMR-5.5L”, manufactured by Satake Chemical Machinery Co., Ltd. ), followed by mixing and emulsifying at 15,000 rpm using an emulsifying device (product name “Milder MDN310”, manufactured by Taihei Kiki Co., Ltd.) to obtain an emulsion.
  • a multi-line mixer product name “multi-line mixer MS26-MMR-5.5L”, manufactured by Satake Chemical Machinery Co., Ltd.
  • an emulsifying device product name “Milder MDN310”, manufactured by Taihei Kiki Co., Ltd.
  • the obtained emulsion is heated to 75° C. under reduced pressure of 700 to 800 hPa to distill off cyclohexane, and then centrifuged at 4,000 to 6,000 G using a centrifuge.
  • a concentration operation By performing a concentration operation, a latex of butyl rubber having a solid content concentration of 62% by weight and a volume cumulative particle size d50: 1.72 ⁇ m was obtained as a light liquid.
  • ⁇ Preparation Example 2 (Preparation of latex of nitrile group-containing conjugated diene copolymer)>
  • 0.05 part of cumene hydroperoxide was added as a polymerization initiator, and emulsion polymerization was started at a reaction temperature of 5°C.
  • a polymerization stopper solution consisting of 0.25 parts of diethylhydroxylamine and 5 parts of water was added to stop the polymerization reaction to obtain an emulsion.
  • the content of the ethylenically unsaturated nitrile monomer unit in the nitrile group-containing conjugated diene copolymer of the obtained latex was measured according to the above method, and it was 36% by weight.
  • the solid content concentration of the obtained latex was 66% by weight, and the volume cumulative particle size d50 was 0.80 ⁇ m.
  • Example 1 The butyl rubber latex obtained in Preparation Example 1 and the latex of the nitrile group-containing conjugated diene copolymer obtained in Preparation Example 2 were used as solid weight of "butyl rubber: nitrile group-containing conjugated diene copolymer". The mixture was mixed so that the ratio was 67:33 to obtain a latex for foam rubber. The solid content concentration of the obtained latex for foam rubber was measured according to the above method. The results are shown in Table 1.
  • the foaming time of the obtained latex composition for foam rubber was measured according to the method described above.
  • the latex composition for foam rubber was stirred and foamed using a stand mixer (model “ESM945”, manufactured by Electrolux) to obtain a foamed product.
  • ESM945 manufactured by Electrolux
  • the weight, specific volume, gelation time and shrinkage of 82 ml of the foam were measured according to the method described above. The results are shown in Table 1.
  • an aqueous sodium silicofluoride dispersion (solid content concentration: 20% by weight) was added in an amount of 1.5 parts of sodium silicofluoride with respect to 100 parts of the polymer in the obtained foam. And added for 1 minute, and then poured into a mold for molding (15 cm in length ⁇ 25 cm in width ⁇ 1 cm in height), solidified, and then crosslinked by heating at 110°C for the time shown in Table 1. Then, it was taken out of the mold, washed with water at 40° C. for 10 minutes, dried in an oven at 60° C. for 4 hours, and punched into a circle having a diameter of 3 cm to obtain a disk-shaped foam rubber. Then, with respect to the obtained foam rubber, the swelling ratio with respect to the ultraviolet absorber and the swelling ratio with respect to the liquid paraffin were evaluated according to the above method. The results are shown in Table 1.
  • a latex composition and foam rubber were obtained and evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 3 The butyl rubber latex obtained in Preparation Example 1 and the latex of the nitrile group-containing conjugated diene copolymer obtained in Preparation Example 2 were used as solid weight of "butyl rubber: nitrile group-containing conjugated diene copolymer".
  • a latex for foam rubber, a latex composition for foam rubber and a foam rubber were obtained in the same manner as in Example 2 except that mixing was performed so that the ratio was 50:50, and the same evaluation as in Example 1 was performed. The results are shown in Table 1.
  • Example 1 A latex composition for foam rubber and a foam rubber were obtained in the same manner as in Example 1 except that the latex of the nitrile group-containing conjugated diene copolymer obtained in Preparation Example 2 was used as the latex for foam rubber. The evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.
  • the latex composition for foam rubber containing the above and a cross-linking agent had a short gelation time. Further, the obtained foam rubber had a low swelling rate with respect to liquid paraffin and a low swelling rate with respect to an ultraviolet absorber, and was excellent in oil resistance (Examples 1 to 3).
  • the foam rubber obtained by using the foam rubber latex containing no butyl rubber had a high swelling ratio with respect to the ultraviolet absorber and was poor in oil resistance (Comparative Example 1).
  • a latex for foam rubber having an excessively small amount of nitrile group-containing conjugated diene copolymer was used, the time required for gelation was long, and the obtained foam rubber had poor oil resistance (Comparative Example 2).

Landscapes

  • 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)
  • Materials Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un latex contenant : du butylcaoutchouc ; un copolymère de diène conjugué contenant un groupe nitrile ; et de l'eau, le rapport en poids entre le butylcaoutchouc et le copolymère de diène conjugué contenant un groupe nitrile étant compris entre 85:15 et 10:90. La présente invention permet d'obtenir un latex qui a un temps de gélification court, et au moyen duquel un corps moulé ayant une excellente résistance à l'huile peut être obtenu.
PCT/JP2019/050504 2018-12-26 2019-12-24 Latex, composition de latex, corps moulé et caoutchouc mousse Ceased WO2020138030A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2020563283A JP7543912B2 (ja) 2018-12-26 2019-12-24 ラテックス、ラテックス組成物、成形体、およびフォームラバー

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018-242964 2018-12-26
JP2018242964 2018-12-26

Publications (1)

Publication Number Publication Date
WO2020138030A1 true WO2020138030A1 (fr) 2020-07-02

Family

ID=71127018

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/050504 Ceased WO2020138030A1 (fr) 2018-12-26 2019-12-24 Latex, composition de latex, corps moulé et caoutchouc mousse

Country Status (2)

Country Link
JP (1) JP7543912B2 (fr)
WO (1) WO2020138030A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102372220B1 (ko) * 2021-10-01 2022-03-11 전명지 방수기능을 가진 직물 소재 제조 장치 및 그 방법

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0673220A (ja) * 1992-08-26 1994-03-15 Nippon Zeon Co Ltd フォームラバー用ラテックス及びフォームラバー
JP2000308519A (ja) * 1999-04-27 2000-11-07 Erubu:Kk 化粧用パフおよびその製造法
JP2004524407A (ja) * 2001-02-23 2004-08-12 ファット クッション リミテッド ライアビリティ カンパニー フォームクッションならびにその製造方法および使用方法
JP2005257727A (ja) * 2004-03-09 2005-09-22 Toray Ind Inc 感光性樹脂組成物、それを用いた感光性フレキソ印刷版原版およびフレキソ印刷版
JP2006137859A (ja) * 2004-11-12 2006-06-01 Sumitomo Seika Chem Co Ltd ポリマーラテックスの製造方法
JP2006206677A (ja) * 2005-01-26 2006-08-10 Sumitomo Seika Chem Co Ltd ブチルゴム系熱可塑性エラストマーのアニオン性水性分散体およびその製造方法
WO2009145009A1 (fr) * 2008-05-30 2009-12-03 日本ゼオン株式会社 Composition de latex copolymère pour caoutchouc cellulaire, composition de latex copolymère pour caoutchouc cellulaire vulcanisable et caoutchouc cellulaire
CN105440354A (zh) * 2015-12-16 2016-03-30 宁国天运橡塑制品有限公司 一种缓冲垫用回弹性好强度高的橡胶材料

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0673220A (ja) * 1992-08-26 1994-03-15 Nippon Zeon Co Ltd フォームラバー用ラテックス及びフォームラバー
JP2000308519A (ja) * 1999-04-27 2000-11-07 Erubu:Kk 化粧用パフおよびその製造法
JP2004524407A (ja) * 2001-02-23 2004-08-12 ファット クッション リミテッド ライアビリティ カンパニー フォームクッションならびにその製造方法および使用方法
JP2005257727A (ja) * 2004-03-09 2005-09-22 Toray Ind Inc 感光性樹脂組成物、それを用いた感光性フレキソ印刷版原版およびフレキソ印刷版
JP2006137859A (ja) * 2004-11-12 2006-06-01 Sumitomo Seika Chem Co Ltd ポリマーラテックスの製造方法
JP2006206677A (ja) * 2005-01-26 2006-08-10 Sumitomo Seika Chem Co Ltd ブチルゴム系熱可塑性エラストマーのアニオン性水性分散体およびその製造方法
WO2009145009A1 (fr) * 2008-05-30 2009-12-03 日本ゼオン株式会社 Composition de latex copolymère pour caoutchouc cellulaire, composition de latex copolymère pour caoutchouc cellulaire vulcanisable et caoutchouc cellulaire
CN105440354A (zh) * 2015-12-16 2016-03-30 宁国天运橡塑制品有限公司 一种缓冲垫用回弹性好强度高的橡胶材料

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Example of Blend Rubber Compound Design", vol. 87, no. 11, 2014, pages 460 - 464, Retrieved from the Internet <URL:https://doi.org/10.2324/gomu.87.460> *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102372220B1 (ko) * 2021-10-01 2022-03-11 전명지 방수기능을 가진 직물 소재 제조 장치 및 그 방법

Also Published As

Publication number Publication date
JPWO2020138030A1 (ja) 2021-11-18
JP7543912B2 (ja) 2024-09-03

Similar Documents

Publication Publication Date Title
JP7283400B2 (ja) フォームラバー用ラテックス
JPWO2009145009A1 (ja) フォームラバー用共重合体ラテックス組成物、加硫性フォームラバー用共重合体ラテックス組成物およびフォームラバー
US11926724B2 (en) Method for manufacturing foam rubber
JP7543912B2 (ja) ラテックス、ラテックス組成物、成形体、およびフォームラバー
JP5186992B2 (ja) フォームラバー用共重合体ラテックス、フォームラバー用共重合体ラテックス組成物およびファームラバー
JP4133152B2 (ja) ゴム発泡体用共重合体ラテックスの製造方法
CN110914348B (zh) 泡沫橡胶的制造方法
JP7428097B2 (ja) フォームラバー用ラテックスの製造方法およびフォームラバーの製造方法
JP5859693B1 (ja) フォームラバー用水系組成物及びフォームラバー
JP7615612B2 (ja) ラテックス組成物、発泡体およびパフ
JP4741837B2 (ja) 化粧パフ用共重合体ラテックス
JP4634002B2 (ja) 化粧パフ用共重合体ラテックス組成物
JP7604995B2 (ja) ラテックス組成物、フォームラバー、およびパフ、ならびにラテックス組成物の製造方法
JP7676876B2 (ja) ラテックス組成物、フォームラバー、およびパフ
JP2024072730A (ja) ラテックス組成物および発泡体
JP7351303B2 (ja) ラテックス組成物、成形体およびフォームラバー
JP7383983B2 (ja) ラテックス組成物、成形体およびフォームラバー
JP2019183119A (ja) 発泡成型用共重合体ラテックス
JP7604942B2 (ja) ラテックス組成物およびディップ成形体
CN116888159A (zh) 改性共轭二烯系聚合物胶乳的制造方法
JP2014177536A (ja) フォームラバー用高分子水分散体
JP2004262998A (ja) 化粧パフ用共重合体ラテックス組成物

Legal Events

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

Ref document number: 19906122

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2020563283

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19906122

Country of ref document: EP

Kind code of ref document: A1