US20170165929A1 - Emulsion coagulant and tire puncture repair kit - Google Patents

Emulsion coagulant and tire puncture repair kit Download PDF

Info

Publication number
US20170165929A1
US20170165929A1 US15/116,921 US201515116921A US2017165929A1 US 20170165929 A1 US20170165929 A1 US 20170165929A1 US 201515116921 A US201515116921 A US 201515116921A US 2017165929 A1 US2017165929 A1 US 2017165929A1
Authority
US
United States
Prior art keywords
emulsion
anionic
coagulant
puncture repair
tire puncture
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.)
Granted
Application number
US15/116,921
Other versions
US9694549B1 (en
Inventor
Takahiro Okamatsu
Masahiro Naruse
Hideyuki Takahara
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.)
Yokohama Rubber Co Ltd
Original Assignee
Yokohama Rubber Co 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
Application filed by Yokohama Rubber Co Ltd filed Critical Yokohama Rubber Co Ltd
Assigned to THE YOKOHAMA RUBBER CO., LTD. reassignment THE YOKOHAMA RUBBER CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: NARUSE, MASAHIRO, OKAMATSU, TAKAHIRO, TAKAHARA, HIDEYUKI
Publication of US20170165929A1 publication Critical patent/US20170165929A1/en
Application granted granted Critical
Publication of US9694549B1 publication Critical patent/US9694549B1/en
Assigned to THE YOKOHAMA RUBBER CO., LTD. reassignment THE YOKOHAMA RUBBER CO., LTD. CHANGE OF ADDRESS FOR ASSIGNEE Assignors: THE YOKOHAMA RUBBER CO., LTD.
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C73/00—Repairing of articles made from plastics or substances in a plastic state, e.g. of articles shaped or produced by using techniques covered by this subclass or subclass B29D
    • B29C73/16—Auto-repairing or self-sealing arrangements or agents
    • B29C73/163—Sealing compositions or agents, e.g. combined with propellant agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C1/00—Treatment of rubber latex
    • C08C1/14—Coagulation
    • C08C1/15—Coagulation characterised by the coagulants used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/02—Starch; Degradation products thereof, e.g. dextrin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/24—Homopolymers or copolymers of amides or imides
    • C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber
    • C08L7/02—Latex
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/16—Amines or polyamines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2003/00—Use of starch or derivatives as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2030/00—Pneumatic or solid tyres or parts thereof

Definitions

  • the present invention relates to an emulsion coagulant and a tire puncture repair kit.
  • a coagulant is used to coagulate an emulsion such as a tire puncture repair liquid (tire puncture sealing material) after repairing a punctured tire.
  • Patent Document 1 the inventors of the present invention suggest “an emulsion coagulant for coagulating a tire puncture sealing material containing emulsion particles, in which the emulsion coagulant contains a mineral that induces aggregation of the emulsion particles as a result of weakening a surface charge of the emulsion particles and/or as a result of hydrogen bonding with the emulsion particles, and a gelling agent” (claim 1).
  • Patent Document 2 the present inventors suggests “a liquid coagulant that coagulates an emulsion containing natural rubber latex, in which the liquid coagulant has a pH of 2.0 to 4.0, and contains a urethane resin and/or an acrylic resin having a cationic functional group” (claim 1).
  • Patent Document 1 Japanese Unexamined Patent Application Publication No. 2009-041006A
  • Patent Document 2 Japanese Unexamined Patent Application Publication No. 2011-246610A
  • An object of the present invention is to provide an emulsion coagulant having excellent coagulation performance (ability to rapidly coagulate an emulsion) in the same manner as Patent Documents 1 and 2, and a tire puncture repair kit that uses the emulsion coagulant.
  • An emulsion coagulant comprising an ⁇ -starch and an anionic polyacrylamide
  • a molecular weight of the anionic polyacrylamide being from 500,000 to 2,000,000;
  • a mass ratio (W A :W B ) of a content (W A ) of the ⁇ -starch to a content (W B ) of the anionic polyacrylamide being from 5:95 to 80:20.
  • a ratio of repeating units having the carboxylate group to all repeating units in the anionic polyacrylamide is from 20 to 70 mol %.
  • the content of aluminum sulfate is not less than 1.0 parts by mass per total of 10 parts by mass of the ⁇ -starch and the anionic polyacrylamide.
  • emulsion coagulant according to any one of (1) to (3) above, wherein the emulsion coagulant is an emulsion coagulant for coagulating a tire puncture repair liquid containing a natural rubber latex, a synthetic resin emulsion, and an antifreezing agent.
  • a tire puncture repair kit comprising the emulsion coagulant described in any one of (1) to (5) above and a tire puncture repair liquid.
  • FIG. 1 is a schematic cross-sectional view illustrating an example of a method for recovering a tire puncture repair liquid that uses the emulsion coagulant of the present invention.
  • a numerical range represented using “from . . . to . . . ” refers to a range including the numerical values stated before and after the “from . . . to . . . ” as an upper limit value and a lower limit value.
  • the emulsion coagulant of the present invention (also called the “coagulant of the present invention” hereafter) contains an ⁇ -starch and an anionic polyacrylamide.
  • the molecular weight of the anionic polyacrylamide is from 500,000 to 2,000,000.
  • the mass ratio (W A :W B ) of the content (W A ) of the ⁇ -starch to the content (W B ) of the anionic polyacrylamide is from 5:95 to 80:20.
  • the coagulant of the present invention is thought to exhibit excellent coagulation performance as a result of employing such a structure.
  • the coagulant of the present invention contains an ⁇ -starch and an anionic polyacrylamide. Therefore, when the coagulant of the present invention is compounded into an emulsion, emulsion particles in the emulsion are incorporated into a mesh structure formed by the three-dimensional entanglement of the ⁇ -starch and the anionic polyacrylamide, and the emulsion is thus coagulated.
  • the polyacrylamide contained in the coagulant of the present invention has an anionic functional group, the charge repulsion between emulsion particles is weak due to the interaction with the emulsion particles, which is thought to efficiently promote the coagulation of the emulsion.
  • the ⁇ -starch contained in the coagulant of the present invention is not particularly limited.
  • the term ⁇ -starch refers to a starch in a state in which the hydrogen bonds between saccharide chains in the starch have been broken down and the saccharide chains are free, and more specifically, refers to processed starch in which non-gelatinized starch (hereinafter, also referred to as “raw material starch”) that has been gelatinized by adding water to, heated, and dried rapidly.
  • raw material starch examples include non-gelatinized starch separated from potatoes, wheat, rice, corn, sweet potato, cassava, arrowroot, dogtooth violet, broad bean, mung beans, red beans, and the like.
  • the ⁇ -starch may be a starch in which processing treatment such as esterification, etherification, or cross-linking have been further carried out on ⁇ -starch.
  • the content of the ⁇ -starch is not particularly limited as long as the mass ratio (W A :W B ) described below is from 5:95 to 80:20, but the content is preferably from 5 to 80 mass %, more preferably from 10 to 70 mass %, and even more preferably from 10 to 50 mass % with respect to the total amount of the emulsion coagulant.
  • anionic polyacrylamide contained in the coagulant of the present invention (also called an “anionic PA” hereinafter) is not particularly limited as long as it is a polyacrylamide having an anionic functional group.
  • a polyacrylamide refers to a homopolymer of an acrylamide or a copolymer of an acrylamide and another monomer.
  • the other monomer is not particularly limited but is preferably a monomer having a double bond and is more preferably a vinyl monomer (monomer having a vinyl group (CH 2 ⁇ CH—)).
  • the anionic functional group of the anionic polyacrylamide is not particularly limited, but specific examples include carboxylate groups, sulfonate groups, and phosphonate groups.
  • a carboxylate group refers to a group formed by an ionic bond between —COO ⁇ and a cation (for example, a metal cation; preferably an alkali metal cation).
  • a sulfonate group refers to a group formed by an ionic bond between —SO 3 ⁇ and a cation (for example, a metal cation; preferably an alkali metal cation).
  • a phosphonate group refers to a group formed by an ionic bond between —PO 3 2 ⁇ or —PO 3 H ⁇ and a cation (for example, a metal cation; preferably an alkali metal cation).
  • the anionic functional group of the anionic polyacrylamide is preferably a carboxylate group.
  • Anionic functional groups are ordinarily ionized in an emulsion coagulant and are present as anions (for example, —COO ⁇ ).
  • the ratio of repeating units having a carboxylate group to all repeating units in the anionic polyacrylamide is not particularly limited but is preferably from 15 to 80 mol %, more preferably from 20 to 70 mol %, and even more preferably from 22 to 50 mol %.
  • the anionic polyacrylamide is a compound comprising only 70 repeating units represented by Formula (a1) described below and 30 repeating units represented by Formula (a2) described below (repeating units having a carboxylate group)
  • An example of a preferred mode of the anionic polyacrylamide is compound A having repeating units represented by Formula (a1) below and repeating units represented by Formula (a2) below.
  • the substance is preferably a compound comprising only repeating units represented by Formula (a1) below and repeating units represented by Formula (a2) below.
  • X represents a monovalent cation.
  • the monovalent cation is not particularly limited but is preferably a monovalent cation of an alkali metal (preferably sodium).
  • the ratio of repeating units having a carboxylate group to all repeating units in compound A is not particularly limited but is preferably from 15 to 80 mol %, more preferably from 20 to 70 mol %, and even more preferably from 22 to 50 mol %.
  • the molecular weight of the anionic polyacrylamide is from 500,000 to 2,000,000. Of these, the molecular weight is preferably from 600,000 to 1,800,000 and more preferably from 1,000,000 to 1,500,000. When the molecular weight of the anionic polyacrylamide is outside the range of from 500,000 to 2,000,000, it becomes difficult to incorporate the emulsion particles, and the coagulation performance is diminished.
  • the molecular weight refers to the weight average molecular weight (Mw) (expressed in terms of polyethylene glycol) measured using gel permeation chromatography (GPC) under the following conditions.
  • the method for producing the anionic polyacrylamide is not particularly limited, and a publicly known method may be used.
  • the anionic polyacrylamide may be produced by copolymerizing an acrylamide and an anionic vinyl monomer.
  • an anionic vinyl monomer is a vinyl monomer having an anionic functional group.
  • the definition, specific examples, and preferred aspects of the anionic functional group are as described above.
  • the content of the anionic polyacrylamide is not particularly limited as long as the mass ratio (W A :W B ) described below is from 5:95 to 80:20, but the content is preferably from 20 to 95 mass %, more preferably from 30 to 90 mass %, and even more preferably from 50 to 90 mass % with respect to the entire amount of the emulsion coagulant.
  • the mass ratio (W A :W B ) of the content (W A ) of the ⁇ -starch to the content (W B ) of the anionic polyacrylamide is from 5:95 to 80:20. Of these, the mass ratio is preferably from 10:90 to 70:30 and more preferably from 10:90 to 50:50.
  • the coagulant of the present invention may also contain other components (optional components) in addition to the components described above as necessary.
  • optional components include fillers, antiaging agents, antioxidants, pigments (dyes), plasticizers, thixotropic agents, UV absorbents, flame retardants, surfactants, dispersants, dewatering agents, and antistatic agents.
  • the coagulant of the present invention preferably further contains aluminum sulfate in that the resulting coagulant exhibits even better coagulation performance.
  • Aluminum sulfate is ordinarily present as a positively charged ion in water, so aluminum sulfate functions as a negatively charged fine particle adsorbent.
  • the content of the aluminum sulfate is not particularly limited but is preferably not less than 0.1 parts by mass and more preferably not less than 1.0 parts by mass per total of 10 parts by mass of the ⁇ -starch and the anionic polyacrylamide.
  • the upper limit is not particularly limited but is preferably not more than 10 parts by mass and more preferably not more than 5 parts by mass per total of 10 parts by mass of the ⁇ -starch and the anionic polyacrylamide.
  • the content of the aluminum sulfate is preferably from 1 to 50 mass % and more preferably from 7 to 30 mass % with respect to the total amount of the emulsion coagulant.
  • the method for producing the coagulant of the present invention is not particularly limited, and an example thereof is a method of mixing each of the components described above using an agitator.
  • the coagulant of the present invention is particularly useful as an emulsion coagulant for coagulating a tire puncture repair liquid (tire puncture repair liquid after repairing a punctured tire).
  • a tire puncture repair liquid that is coagulated by the coagulant of the present invention is not particularly limited.
  • the tire puncture repair liquid examples include a repair liquid that contains a natural rubber latex and/or a synthetic resin emulsion, a repair liquid that contains an antifreezing agent in addition to these, or the like.
  • a repair liquid containing a natural rubber latex, a synthetic resin emulsion, and an antifreezing agent is preferable.
  • the phase of the synthetic resin which is a dispersoid, may be a liquid phase or a solid phase.
  • emulsion a system in which a liquid phase dispersoid is dispersed in a liquid phase dispersion medium
  • a system in which a solid phase dispersoid is dispersed in a liquid phase dispersion medium is called a “suspension”; however, in the present specification, the term “emulsion” includes “suspension”.
  • the natural rubber latex described above is not particularly limited, and a conventionally known natural rubber latex can be used.
  • natural rubber latex examples include material sampled from Hevea brasiliensis by tapping, and so-called “deproteinized natural rubber latex”, which is protein-free natural rubber latex.
  • the synthetic resin emulsion is not particularly limited, and conventionally known synthetic resin emulsions can be used.
  • examples of the synthetic resin emulsion include a urethane emulsion, an acrylic emulsion, a polyolefin emulsion, an ethylene vinyl acetate copolymer emulsion, a polyvinyl acetate emulsion, an ethylene-vinyl acetate-vinyl versatate copolymer emulsion, a polyvinyl chloride emulsion, and the like, and a single type thereof may be used independently, or two or more types may be used in combination.
  • the antifreezing agent is not particularly limited, and it is possible to use a conventionally-known antifreezing agent.
  • examples of the antifreezing agent include ethylene glycol, propylene glycol, diethylene glycol, glycerin, methanol, ethanol, isopropyl alcohol and the like, and a single type thereof may be used independently, or two or more types may be used in combination.
  • the antifreezing agent is preferably at least one type of a compound selected from the group consisting of ethylene glycol, propylene glycol, and diethylene glycol.
  • the tire puncture repair liquid that is coagulated by the coagulant of the present invention can include various additives such as a filler, an anti-aging agent, an antioxidant, a pigment (dye), a plasticizer, a thixotropic agent, a UV absorbent, a flame retardant, a surfactant (including a leveling agent), a dispersant, a dehydrating agent, or an antistatic agent as necessary.
  • the amount of the emulsion coagulant used per 100 parts by mass of the tire puncture repair liquid is not particularly limited but is preferably from 1 to 100 parts by mass, more preferably from 3 to 50 parts by mass, and even more preferably from 5 to 10 parts by mass.
  • Examples of the form (for example, the usage form or marketing form) of the coagulant of the present invention include individual use of the emulsion coagulant, and a set including the coagulant and a tire puncture repair liquid (a tire puncture repair kit).
  • a method for recovering tire puncture repair liquid that uses the coagulant of the present invention (hereinafter, also referred to as a “method of using the coagulant of the present invention”) will be described below using FIGS. 1A to 1C . Additionally, the method of using the coagulant of the present invention is not particularly limited to the aspect that is illustrated in FIGS. 1A to 1C .
  • FIGS. 1A to 1C are schematic cross-sectional views illustrating an example of a method for recovering a tire puncture repair liquid that uses the coagulant of the present invention.
  • a valve core (not illustrated in the drawing) is detached from a tire valve 3 of a wheel 2 in which a tire puncture repair liquid 4 is injected inside a pneumatic tire 1 .
  • a tube 5 is inserted inside the pneumatic tire 1 via the tire valve 3 .
  • the tire puncture repair kit of the present invention includes the coagulant of the present invention and a tire puncture repair liquid.
  • the tire puncture repair liquid in the tire puncture repair kit of the present invention is the same as the above-mentioned tire puncture repair liquid that is described as the target for coagulation by the coagulant of the present invention.
  • a tire puncture repair liquid was prepared by mixing the components shown in Table 1 below at the ratios (parts by mass) shown in the table using an agitator.
  • Emulsion coagulants (each emulsion coagulant of the working examples and the comparative examples) were produced by mixing the components shown in Table 2 below at the ratios (parts by mass) shown in the table using an agitator.
  • an emulsion coagulant was produced by mixing 0.5 parts by mass of an ⁇ -starch ( ⁇ -tapioca for industrial use) and 9.5 parts by mass of anionic PA1 (acrylamide-sodium acrylate copolymer) using an agitator.
  • Each of the emulsion coagulants of the working examples and the comparative examples was compounded in 100 parts by mass of the prepared tire puncture repair liquid in the “amount of emulsion coagulant used (parts by mass) per 100 parts by mass of the tire puncture repair liquid” respectively shown in Table 2 and stirred.
  • the coagulation performance was then evaluated using the following criteria.
  • the results are shown in Table 2.
  • the result is preferably from AA to C, more preferably from AA to B, and even more preferably AA or A.
  • the anionic PA1 to PA15 are anionic polyacrylamides having carboxylate groups as anionic functional groups.
  • a cationic PA is a polyacrylamide (cationic polyacrylamide) which does not have an anionic functional group and has a cationic functional group (quaternary ammonium).
  • Working Examples 27 to 29 and 31 which further contained aluminum sulfate and in which the content of the aluminum sulfate was not less than 1.0 parts by mass per total of 10 parts by mass of the ⁇ -starch and the anionic polyacrylamide, exhibited superior coagulation performance.
  • Working Examples 27 to 29 and 31 having a carboxylate group unit ratio of from 20 to 70 mol % exhibited even better coagulation performance.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Sealing Material Composition (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Tires In General (AREA)

Abstract

An object of the present invention is to provide an emulsion coagulant having excellent coagulation performance and a tire puncture repair kit that uses the emulsion coagulant. The emulsion coagulant of the present invention is an emulsion coagulant containing an α-starch and an anionic polyacrylamide; a molecular weight of the anionic polyacrylamide being from 500,000 to 2,000,000; and a mass ratio (WA:WB) of a content (WA) of the α-starch to a content (WB) of the anionic polyacrylamide being from 5:95 to 80:20.

Description

    TECHNICAL FIELD
  • The present invention relates to an emulsion coagulant and a tire puncture repair kit.
    • BACKGROUND ART
  • Conventionally, a coagulant is used to coagulate an emulsion such as a tire puncture repair liquid (tire puncture sealing material) after repairing a punctured tire.
  • For example, in Patent Document 1, the inventors of the present invention suggest “an emulsion coagulant for coagulating a tire puncture sealing material containing emulsion particles, in which the emulsion coagulant contains a mineral that induces aggregation of the emulsion particles as a result of weakening a surface charge of the emulsion particles and/or as a result of hydrogen bonding with the emulsion particles, and a gelling agent” (claim 1).
  • In addition, in Patent Document 2, the present inventors suggests “a liquid coagulant that coagulates an emulsion containing natural rubber latex, in which the liquid coagulant has a pH of 2.0 to 4.0, and contains a urethane resin and/or an acrylic resin having a cationic functional group” (claim 1).
    • CITATION LIST Patent Literature
  • Patent Document 1: Japanese Unexamined Patent Application Publication No. 2009-041006A
  • Patent Document 2: Japanese Unexamined Patent Application Publication No. 2011-246610A
    • SUMMARY OF INVENTION Technical Problem
  • An object of the present invention is to provide an emulsion coagulant having excellent coagulation performance (ability to rapidly coagulate an emulsion) in the same manner as Patent Documents 1 and 2, and a tire puncture repair kit that uses the emulsion coagulant.
    • Solution to Problem
  • As a result of conducting dedicated research on the object described above, the present inventors discovered that using an α-starch and an anionic polyacrylamide with a specific molecular weight in combination at a specific mass ratio yields excellent coagulation performance.
  • Specifically, the inventors discovered that the object described above can be achieved by the following features.
  • (1) An emulsion coagulant comprising an α-starch and an anionic polyacrylamide;
  • a molecular weight of the anionic polyacrylamide being from 500,000 to 2,000,000; and
  • a mass ratio (WA:WB) of a content (WA) of the α-starch to a content (WB) of the anionic polyacrylamide being from 5:95 to 80:20.
  • (2) The emulsion coagulant according to (1) above, wherein an anionic functional group of the anionic polyacrylamide is a carboxylate group; and
  • a ratio of repeating units having the carboxylate group to all repeating units in the anionic polyacrylamide is from 20 to 70 mol %.
  • (3) The emulsion coagulant according to (1) or (2) above further comprising aluminum sulfate;
  • wherein the content of aluminum sulfate is not less than 1.0 parts by mass per total of 10 parts by mass of the α-starch and the anionic polyacrylamide.
  • (4) The emulsion coagulant according to any one of (1) to (3) above, wherein the emulsion coagulant is an emulsion coagulant for coagulating a tire puncture repair liquid containing a natural rubber latex, a synthetic resin emulsion, and an antifreezing agent.
  • (5) The emulsion coagulant according to (4) above, wherein the antifreezing agent is at least one type of compound selected from the group consisting of ethylene glycol, propylene glycol, and diethylene glycol.
  • (6) A tire puncture repair kit comprising the emulsion coagulant described in any one of (1) to (5) above and a tire puncture repair liquid.
    • Advantageous Effects of Invention
  • As illustrated below, according to the present invention, it is possible to provide an emulsion coagulant having excellent coagulation performance, and a tire puncture repair kit that uses the emulsion coagulant.
    • BRIEF DESCRIPTION OF DRAWINGS
  • FIG. 1 is a schematic cross-sectional view illustrating an example of a method for recovering a tire puncture repair liquid that uses the emulsion coagulant of the present invention.
    •  DESCRIPTION OF EMBODIMENTS
  • The emulsion coagulant and the like of the present invention will be described hereinafter.
  • In this specification, a numerical range represented using “from . . . to . . . ” refers to a range including the numerical values stated before and after the “from . . . to . . . ” as an upper limit value and a lower limit value.
    • Emulsion Coagulant
  • The emulsion coagulant of the present invention (also called the “coagulant of the present invention” hereafter) contains an α-starch and an anionic polyacrylamide. Here, the molecular weight of the anionic polyacrylamide is from 500,000 to 2,000,000. The mass ratio (WA:WB) of the content (WA) of the α-starch to the content (WB) of the anionic polyacrylamide is from 5:95 to 80:20.
  • The coagulant of the present invention is thought to exhibit excellent coagulation performance as a result of employing such a structure.
  • Although the reason is not clear, it is assumed to be as follows.
  • As described above, the coagulant of the present invention contains an α-starch and an anionic polyacrylamide. Therefore, when the coagulant of the present invention is compounded into an emulsion, emulsion particles in the emulsion are incorporated into a mesh structure formed by the three-dimensional entanglement of the α-starch and the anionic polyacrylamide, and the emulsion is thus coagulated. Here, since the polyacrylamide contained in the coagulant of the present invention has an anionic functional group, the charge repulsion between emulsion particles is weak due to the interaction with the emulsion particles, which is thought to efficiently promote the coagulation of the emulsion. As illustrated in the working examples and comparative examples described below, this is also predicted from the fact that the coagulation performance is better when an α-starch and an anionic polyacrylamide are used in combination (working examples of this application) than when only an α-starch is used without using an α-starch and an anionic polyacrylamide in combination (Comparative Example 5), when only an anionic polyacrylamide is used (Comparative Example 1), and when an α-starch and a polyacrylamide are used in combination but the polyacrylamide does not have an anionic functional group (Comparative Example 10).
  • Each component contained in the coagulant of the present invention will be described hereinafter.
    • α-Starch
  • The α-starch contained in the coagulant of the present invention is not particularly limited. Here, the term α-starch refers to a starch in a state in which the hydrogen bonds between saccharide chains in the starch have been broken down and the saccharide chains are free, and more specifically, refers to processed starch in which non-gelatinized starch (hereinafter, also referred to as “raw material starch”) that has been gelatinized by adding water to, heated, and dried rapidly.
  • Examples of the above-mentioned raw material starch include non-gelatinized starch separated from potatoes, wheat, rice, corn, sweet potato, cassava, arrowroot, dogtooth violet, broad bean, mung beans, red beans, and the like.
  • Additionally, the α-starch may be a starch in which processing treatment such as esterification, etherification, or cross-linking have been further carried out on α-starch.
  • In the coagulant of the present invention, the content of the α-starch is not particularly limited as long as the mass ratio (WA:WB) described below is from 5:95 to 80:20, but the content is preferably from 5 to 80 mass %, more preferably from 10 to 70 mass %, and even more preferably from 10 to 50 mass % with respect to the total amount of the emulsion coagulant.
    • Anionic Polyacrylamide
  • The anionic polyacrylamide contained in the coagulant of the present invention (also called an “anionic PA” hereinafter) is not particularly limited as long as it is a polyacrylamide having an anionic functional group.
  • Here, a polyacrylamide refers to a homopolymer of an acrylamide or a copolymer of an acrylamide and another monomer. The other monomer is not particularly limited but is preferably a monomer having a double bond and is more preferably a vinyl monomer (monomer having a vinyl group (CH2═CH—)).
  • The anionic functional group of the anionic polyacrylamide is not particularly limited, but specific examples include carboxylate groups, sulfonate groups, and phosphonate groups. Here, a carboxylate group refers to a group formed by an ionic bond between —COO− and a cation (for example, a metal cation; preferably an alkali metal cation). Similarly, a sulfonate group refers to a group formed by an ionic bond between —SO3 − and a cation (for example, a metal cation; preferably an alkali metal cation). A phosphonate group refers to a group formed by an ionic bond between —PO3 2− or —PO3H− and a cation (for example, a metal cation; preferably an alkali metal cation). The anionic functional group of the anionic polyacrylamide is preferably a carboxylate group.
  • Anionic functional groups are ordinarily ionized in an emulsion coagulant and are present as anions (for example, —COO−).
  • The ratio of repeating units having a carboxylate group to all repeating units in the anionic polyacrylamide (also called the “carboxylic acid unit ratio” hereafter) is not particularly limited but is preferably from 15 to 80 mol %, more preferably from 20 to 70 mol %, and even more preferably from 22 to 50 mol %.
  • For example, when the anionic polyacrylamide is a compound comprising only 70 repeating units represented by Formula (a1) described below and 30 repeating units represented by Formula (a2) described below (repeating units having a carboxylate group), the carboxylic acid unit ratio is 30 mol % (=30/(70+30)).
  • An example of a preferred mode of the anionic polyacrylamide is compound A having repeating units represented by Formula (a1) below and repeating units represented by Formula (a2) below. Of these, the substance is preferably a compound comprising only repeating units represented by Formula (a1) below and repeating units represented by Formula (a2) below.
  • Figure US20170165929A1-20170615-C00001
  • In Formula (a2) above, X represents a monovalent cation. The monovalent cation is not particularly limited but is preferably a monovalent cation of an alkali metal (preferably sodium).
  • The ratio of repeating units having a carboxylate group to all repeating units in compound A is not particularly limited but is preferably from 15 to 80 mol %, more preferably from 20 to 70 mol %, and even more preferably from 22 to 50 mol %.
  • The molecular weight of the anionic polyacrylamide is from 500,000 to 2,000,000. Of these, the molecular weight is preferably from 600,000 to 1,800,000 and more preferably from 1,000,000 to 1,500,000. When the molecular weight of the anionic polyacrylamide is outside the range of from 500,000 to 2,000,000, it becomes difficult to incorporate the emulsion particles, and the coagulation performance is diminished. In this specification, the molecular weight refers to the weight average molecular weight (Mw) (expressed in terms of polyethylene glycol) measured using gel permeation chromatography (GPC) under the following conditions.
      • Solvent: dimethylformamide
      • Measurement temperature: 40° C.
  • The method for producing the anionic polyacrylamide is not particularly limited, and a publicly known method may be used. For example, the anionic polyacrylamide may be produced by copolymerizing an acrylamide and an anionic vinyl monomer. Here, an anionic vinyl monomer is a vinyl monomer having an anionic functional group. The definition, specific examples, and preferred aspects of the anionic functional group are as described above.
  • In the coagulant of the present invention, the content of the anionic polyacrylamide is not particularly limited as long as the mass ratio (WA:WB) described below is from 5:95 to 80:20, but the content is preferably from 20 to 95 mass %, more preferably from 30 to 90 mass %, and even more preferably from 50 to 90 mass % with respect to the entire amount of the emulsion coagulant.
  • Mass Ratio (WA:WB)
  • The mass ratio (WA:WB) of the content (WA) of the α-starch to the content (WB) of the anionic polyacrylamide is from 5:95 to 80:20. Of these, the mass ratio is preferably from 10:90 to 70:30 and more preferably from 10:90 to 50:50.
  • When the mass ratio (WA:WB) is outside the range of from 5:95 to 80:20, it becomes difficult to incorporate the emulsion particles, and the coagulation performance is diminished.
    • Optional Components
  • The coagulant of the present invention may also contain other components (optional components) in addition to the components described above as necessary. Examples of such optional components include fillers, antiaging agents, antioxidants, pigments (dyes), plasticizers, thixotropic agents, UV absorbents, flame retardants, surfactants, dispersants, dewatering agents, and antistatic agents.
    • Aluminum Sulfate
  • The coagulant of the present invention preferably further contains aluminum sulfate in that the resulting coagulant exhibits even better coagulation performance. Aluminum sulfate is ordinarily present as a positively charged ion in water, so aluminum sulfate functions as a negatively charged fine particle adsorbent.
  • The content of the aluminum sulfate is not particularly limited but is preferably not less than 0.1 parts by mass and more preferably not less than 1.0 parts by mass per total of 10 parts by mass of the α-starch and the anionic polyacrylamide. The upper limit is not particularly limited but is preferably not more than 10 parts by mass and more preferably not more than 5 parts by mass per total of 10 parts by mass of the α-starch and the anionic polyacrylamide.
  • The content of the aluminum sulfate is preferably from 1 to 50 mass % and more preferably from 7 to 30 mass % with respect to the total amount of the emulsion coagulant.
    • Production Method of the Emulsion Coagulant
  • The method for producing the coagulant of the present invention is not particularly limited, and an example thereof is a method of mixing each of the components described above using an agitator.
    • Application
  • The coagulant of the present invention is particularly useful as an emulsion coagulant for coagulating a tire puncture repair liquid (tire puncture repair liquid after repairing a punctured tire).
    • Tire Puncture Repair Liquid
  • A tire puncture repair liquid that is coagulated by the coagulant of the present invention is not particularly limited.
  • Examples of the tire puncture repair liquid include a repair liquid that contains a natural rubber latex and/or a synthetic resin emulsion, a repair liquid that contains an antifreezing agent in addition to these, or the like. Of these, a repair liquid containing a natural rubber latex, a synthetic resin emulsion, and an antifreezing agent is preferable.
  • Additionally, in a synthetic resin emulsion, the phase of the synthetic resin, which is a dispersoid, may be a liquid phase or a solid phase.
  • In general, a system in which a liquid phase dispersoid is dispersed in a liquid phase dispersion medium is called an “emulsion”, and a system in which a solid phase dispersoid is dispersed in a liquid phase dispersion medium is called a “suspension”; however, in the present specification, the term “emulsion” includes “suspension”.
    • Natural Rubber Latex
  • The natural rubber latex described above is not particularly limited, and a conventionally known natural rubber latex can be used.
  • Specific examples of the natural rubber latex include material sampled from Hevea brasiliensis by tapping, and so-called “deproteinized natural rubber latex”, which is protein-free natural rubber latex.
    • Synthetic Resin Emulsion
  • The synthetic resin emulsion is not particularly limited, and conventionally known synthetic resin emulsions can be used.
  • More specifically, examples of the synthetic resin emulsion include a urethane emulsion, an acrylic emulsion, a polyolefin emulsion, an ethylene vinyl acetate copolymer emulsion, a polyvinyl acetate emulsion, an ethylene-vinyl acetate-vinyl versatate copolymer emulsion, a polyvinyl chloride emulsion, and the like, and a single type thereof may be used independently, or two or more types may be used in combination.
    • Antifreezing Agent
  • The antifreezing agent is not particularly limited, and it is possible to use a conventionally-known antifreezing agent.
  • More specifically, examples of the antifreezing agent include ethylene glycol, propylene glycol, diethylene glycol, glycerin, methanol, ethanol, isopropyl alcohol and the like, and a single type thereof may be used independently, or two or more types may be used in combination. Of these, the antifreezing agent is preferably at least one type of a compound selected from the group consisting of ethylene glycol, propylene glycol, and diethylene glycol.
    • Additives
  • In addition to each of the above-mentioned components, the tire puncture repair liquid that is coagulated by the coagulant of the present invention can include various additives such as a filler, an anti-aging agent, an antioxidant, a pigment (dye), a plasticizer, a thixotropic agent, a UV absorbent, a flame retardant, a surfactant (including a leveling agent), a dispersant, a dehydrating agent, or an antistatic agent as necessary.
  • When the coagulant of the present invention is used as an emulsion coagulant of a tire puncture repair liquid, the amount of the emulsion coagulant used per 100 parts by mass of the tire puncture repair liquid is not particularly limited but is preferably from 1 to 100 parts by mass, more preferably from 3 to 50 parts by mass, and even more preferably from 5 to 10 parts by mass.
  • Examples of the form (for example, the usage form or marketing form) of the coagulant of the present invention include individual use of the emulsion coagulant, and a set including the coagulant and a tire puncture repair liquid (a tire puncture repair kit).
    • Recovery Method
  • A method for recovering tire puncture repair liquid that uses the coagulant of the present invention (hereinafter, also referred to as a “method of using the coagulant of the present invention”) will be described below using FIGS. 1A to 1C. Additionally, the method of using the coagulant of the present invention is not particularly limited to the aspect that is illustrated in FIGS. 1A to 1C.
  • FIGS. 1A to 1C are schematic cross-sectional views illustrating an example of a method for recovering a tire puncture repair liquid that uses the coagulant of the present invention.
  • Firstly, as illustrated in FIG. 1A, a valve core (not illustrated in the drawing) is detached from a tire valve 3 of a wheel 2 in which a tire puncture repair liquid 4 is injected inside a pneumatic tire 1.
  • Next, as illustrated in FIG. 1B, a tube 5 is inserted inside the pneumatic tire 1 via the tire valve 3.
  • Subsequently, as illustrated in FIG. 1C, when the tip end of the tube 5, which is inserted, reaches the liquid surface of the tire puncture repair liquid 4, the tire puncture repair liquid 4 flows backward from inside the pressurized pneumatic tire 1 through the tube 5, and it is possible to recover the tire puncture repair liquid in a recovery pouch 7 into which the emulsion coagulant 6 is inserted in advance.
    • Tire Puncture Repair Kit
  • The tire puncture repair kit of the present invention includes the coagulant of the present invention and a tire puncture repair liquid. In this instance, the tire puncture repair liquid in the tire puncture repair kit of the present invention is the same as the above-mentioned tire puncture repair liquid that is described as the target for coagulation by the coagulant of the present invention.
    • EXAMPLES
  • Hereinafter, the present invention will be further described in detail using working examples; however, the present invention is not limited thereto.
    • Preparation of Tire Puncture Repair Liquid
  • A tire puncture repair liquid was prepared by mixing the components shown in Table 1 below at the ratios (parts by mass) shown in the table using an agitator.
  • TABLE 1
    Tire puncture repair liquid
    Natural rubber latex 30
    Synthetic resin emulsion 30
    Antifreezing agent 40
  • The details of each component shown in Table 1 are as follows.
      • Natural rubber latex: natural rubber latex (HA Latex, solid content: 60 mass %, produced by Golden Hope Co., Ltd.)
      • Synthetic resin emulsion: ethylene-vinyl acetate copolymer emulsion (solid content: 51 mass %, Sumika Flex S-408HQE, produced by Sumika Chemtex Co., Ltd.)
      • Antifreezing agent: polypropylene glycol (solid content: 100 mass %, produced by Wako Pure Chemical Industries Co., Ltd.)
    Production of Emulsion Coagulant
  • Emulsion coagulants (each emulsion coagulant of the working examples and the comparative examples) were produced by mixing the components shown in Table 2 below at the ratios (parts by mass) shown in the table using an agitator. For example, in Working Example 1, an emulsion coagulant was produced by mixing 0.5 parts by mass of an α-starch (α-tapioca for industrial use) and 9.5 parts by mass of anionic PA1 (acrylamide-sodium acrylate copolymer) using an agitator.
    • Evaluation: Coagulation Performance
  • Each of the emulsion coagulants of the working examples and the comparative examples was compounded in 100 parts by mass of the prepared tire puncture repair liquid in the “amount of emulsion coagulant used (parts by mass) per 100 parts by mass of the tire puncture repair liquid” respectively shown in Table 2 and stirred.
  • After stirring, the mixtures were left to stand at −40° C., and the time (coagulation time) until fluidity is lost without the liquid content oozing out from the mixture of the tire puncture repair liquid and the emulsion coagulant was measured.
  • The coagulation performance was then evaluated using the following criteria. The results are shown in Table 2. The result is preferably from AA to C, more preferably from AA to B, and even more preferably AA or A.
      • “AA”: coagulation time not more than 5 minutes
      • “A”: coagulation time more than 5 minutes and not more than 15 minutes
      • “B”: coagulation time more than 15 minutes and not more than 30 minutes
      • “C”: coagulation time more than 30 minutes and not more than 1 hour
      • “D”: coagulation time more than 1 hour
  • TABLE 2
    Carboxylate Comparative Comparative
    Mw group unit Examples Working Examples Examples
    (×10,000) ratio (mol %) 1 2 1 2 3 4 5 6 7 8 9 3 4 5 10
    α-starch 0 0.3 0.5 1 2 3 4 5 6 7 8 8.5 9 10 3
    Anionic PA1 140 35 10 9.7 9.5 9 8 7 6 5 4 3 2 1.5 1 0
    Cationic PA 7
    Amount of emulsion coagulant used 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10
    (parts by mass) per 100 parts by
    mass of the tire puncture repair
    liquid
    Coagulation performance D D C A A A A A B B C D D D D
    Carboxylate Comparative
    Mw group unit Examples Working Examples
    (×10,000) ratio (mol %) 6 7 8 9 10 11 12 13 14 15 16 32
    α-starch 1 5 1 5 3 5 3 5 3 3 1.5 7.5
    Anionic PA2 45 35 9 5
    Anionic PA3 50 35 7 5
    Anionic PA4 70 35 7
    Anionic PA5 110 35 1.5
    Anionic PA1 140 35 7.5
    Anionic PA6 160 35 7
    Anionic PA7 190 35 7 5
    Anionic PA8 220 35 9 5
    Amount of emulsion coagulant used 10 10 10 10 10 10 10 10 10 10 3 15
    (parts by mass) per 100 parts by
    mass of the tire puncture repair
    liquid
    Coagulation performance D D D D C C C C B B C A
    Carboxylate Working
    Mw group unit Examples
    (×10,000) ratio (mol %) 17 18 19 20 21 22 23 24
    α-starch 5 5 5 5 5 5 7 7
    Anionic PA9 110 15 5 3
    Anionic PA10 110 17.5 5
    Anionic PA11 110 22 5
    Anionic PA5 110 35 5
    Anionic PA12 110 55 5
    Anionic PA13 110 80 5 3
    Amount of emulsion coagulant used 10 10 10 10 10 10 10 10
    (parts by mass) per 100 parts by
    mass of the tire puncture repair
    liquid
    Coagulation performance C C A A B C C C
    Carboxylate
    group unit
    Mw ratio Working Examples
    (×10,000) (mol %) 25 26 27 28 29 30 31
    α-starch 3 3 3 3 3 5 5
    Anionic 190 22 7 7 7 7 7
    PA14
    Anionic 190 80 5 5
    PA15
    Aluminum sulfate 0.5 1 2 3 0.5 1
    Amount of emulsion coagulant used 10 10.5 11 12 13 10.5 11
    (parts by mass) per 100 parts by
    mass of the tire puncture repair
    liquid
    Coagulation performance B B AA AA AA B A
  • The details of each component shown in Table 2 above are as follows. The anionic PA1 to PA15 are anionic polyacrylamides having carboxylate groups as anionic functional groups. A cationic PA is a polyacrylamide (cationic polyacrylamide) which does not have an anionic functional group and has a cationic functional group (quaternary ammonium).
      • α-starch: α-tapioca for industrial use (amylopectin content: 75 mass %, produced by Sanwa Starch Co. Ltd.)
      • Anionic PA1: acrylamide-sodium acrylate copolymer (reagent, produced by Wako Pure Chemical Industries, Ltd., Mw: 1,400,000, carboxylate unit ratio: 35 mol %)
      • Anionic PA2: acrylamide-sodium acrylate copolymer (reagent, produced by Wako Pure Chemical Industries, Ltd., Mw: 450,000, carboxylate unit ratio: 35 mol %)
      • Anionic PA3: acrylamide-sodium acrylate copolymer (reagent, produced by Wako Pure Chemical Industries, Ltd., Mw: 500,000, carboxylate unit ratio: 35 mol %)
      • Anionic PA4: acrylamide-sodium acrylate copolymer (reagent, produced by Wako Pure Chemical Industries, Ltd., Mw: 700,000, carboxylate unit ratio: 35 mol %)
      • Anionic PA5: acrylamide-sodium acrylate copolymer (reagent, produced by Wako Pure Chemical Industries, Ltd., Mw: 1,100,000, carboxylate unit ratio: 35 mol %)
      • Anionic PA6: acrylamide-sodium acrylate copolymer (reagent, produced by Wako Pure Chemical Industries, Ltd., Mw: 1,600,000, carboxylate unit ratio: 35 mol %)
      • Anionic PA7: acrylamide-sodium acrylate copolymer (reagent, produced by Wako Pure Chemical Industries, Ltd., Mw: 1,900,000, carboxylate unit ratio: 35 mol %)
      • Anionic PA8: acrylamide-sodium acrylate copolymer (reagent, produced by Wako Pure Chemical Industries, Ltd., Mw: 2,200,000, carboxylate unit ratio: 35 mol %)
      • Anionic PA9: acrylamide-sodium acrylate copolymer (reagent, produced by Wako Pure Chemical Industries, Ltd., Mw: 1,100,000, carboxylate unit ratio: 15 mol %)
      • Anionic PA10: acrylamide-sodium acrylate copolymer (reagent, produced by Wako Pure Chemical Industries, Ltd., Mw: 1,100,000, carboxylate unit ratio: 17.5 mol %)
      • Anionic PA11: acrylamide-sodium acrylate copolymer (reagent, produced by Wako Pure Chemical Industries, Ltd., Mw: 1,100,000, carboxylate unit ratio: 22 mol %)
      • Anionic PA12: acrylamide-sodium acrylate copolymer (reagent, produced by Wako Pure Chemical Industries, Ltd., Mw: 1,100,000, carboxylate unit ratio: 55 mol %)
      • Anionic PA13: acrylamide-sodium acrylate copolymer (reagent, produced by Wako Pure Chemical Industries, Ltd., Mw: 1,100,000, carboxylate unit ratio: 80 mol %)
      • Anionic PA14: acrylamide-sodium acrylate copolymer (reagent, produced by Wako Pure Chemical Industries, Ltd., Mw: 1,900,000, carboxylate unit ratio: 22 mol %)
      • Anionic PA15: acrylamide-sodium acrylate copolymer (reagent, produced by Wako Pure Chemical Industries, Ltd., Mw: 1,900,000, carboxylate unit ratio: 80 mol %)
      • Aluminum sulfate: aluminum sulfate (reagent, produced by Wako Pure Chemical Industries, Ltd.)
      • Cationic PA: acrylamide-quaternary ammonium salt monomer copolymer (reagent, produced by Wako Pure Chemical Industries, Ltd.)
  • As is clear from Table 2, the working examples of the present application, which have an α-starch and an anionic polyacrylamide and in which the Mw of the anionic polyacrylamide is from 500,000 to 2,000,000 and the mass ratio (WA:WB) of the content (WA) of the α-starch to the content (WB) of the anionic polyacrylamide is from 5:95 to 80:20, all exhibited excellent coagulation performance in comparison to Comparative Example 1, which does not contain an α-starch, Comparative Example 5, which does not contain an anionic polyacrylamide, Comparative Example 10, which contains a cationic polyacrylamide instead of an anionic polyacrylamide, Comparative Examples 2 to 4 which contain an α-starch and an anionic polyacrylamide but have a mass ratio (WA:WB) outside the range of from 5:95 to 80:20, and Comparative Examples 6 to 9 which contain an α-starch and an anionic polyacrylamide and have a mass ratio (WA:WB) of from 5:95 to 80:20 but have an anionic polyacrylamide molecular weight outside the range of from 500,000 to 2,000,000.
  • In a comparison of Working Examples 1 to 9, Working Examples 2 to 8 having a mass ratio (WA:WB) of from 10:90 to 70:30 exhibited superior coagulation performance. Of these, Working Examples 2 to 6 having a mass ratio (WA:WB) of from 10:90 to 50:50 exhibited even better coagulation performance.
  • In a comparison of Working Examples 4, 6, and 10 to 15, Working Examples 4, 6, 14, and 15, in which the Mw of the anionic polyacrylamide was from 600,000 to 1,800,000, exhibited superior coagulation performance. Of these, Working Examples 4 and 6 having an anionic polyacrylamide Mw of from 1,000,000 to 1,500,000 exhibited even better coagulation performance.
  • In a comparison of Working Examples 16 and 20, Working Example 20, in which the amount of the emulsion coagulant used per 100 parts by mass of the tire puncture repair liquid was not less than 5 parts by mass, exhibited superior coagulation performance.
  • In a comparison of Working Examples 17 to 24, Working Examples 19 to 21 having a carboxylate group unit ratio of from 20 to 70 mol % exhibited superior coagulation performance. Of these, Working Example 19 and 20 having a carboxylate group unit ratio of from 22 to 50 mol % exhibited even better coagulation performance.
  • In a comparison of Working Examples 25 to 31, Working Examples 27 to 29 and 31, which further contained aluminum sulfate and in which the content of the aluminum sulfate was not less than 1.0 parts by mass per total of 10 parts by mass of the α-starch and the anionic polyacrylamide, exhibited superior coagulation performance. In particular, of Working Examples 27 to 29 and 31, Working Examples 27 to 29 having a carboxylate group unit ratio of from 20 to 70 mol % exhibited even better coagulation performance.
    • REFERENCE SIGNS LIST
    • 1 Pneumatic tire
    • 2 Wheel
    • 3 Tire valve
    • 4 Tire puncture repair liquid
    • 5 Tube
    • 6 Emulsion coagulant
    • 7 Recovery pouch

Claims (9)

1. An emulsion coagulant comprising an α-starch and an anionic polyacrylamide;
a molecular weight of the anionic polyacrylamide being from 500,000 to 2,000,000; and
a mass ratio (WA:WB) of a content (WA) of the α-starch to a content (WB) of the anionic polyacrylamide being from 5:95 to 80:20.
2. The emulsion coagulant according to claim 1, wherein an anionic functional group of the anionic polyacrylamide is a carboxylate group; and
a ratio of repeating units having the carboxylate group to all repeating units in the anionic polyacrylamide is from 20 to 70 mol %.
3. The emulsion coagulant according to claim 1 further comprising aluminum sulfate;
wherein the content of aluminum sulfate is not less than 1.0 parts by mass per total of 10 parts by mass of the α-starch and the anionic polyacrylamide.
4. The emulsion coagulant according to claim 1, wherein the emulsion coagulant is an emulsion coagulant for coagulating a tire puncture repair liquid containing a natural rubber latex, a synthetic resin emulsion, and an antifreezing agent.
5. The emulsion coagulant according to claim 4, wherein the antifreezing agent is at least one type of compound selected from the group consisting of ethylene glycol, propylene glycol, and diethylene glycol.
6. A tire puncture repair kit comprising the emulsion coagulant described in claim 1 and a tire puncture repair liquid.
7. The emulsion coagulant according to claim 2 further comprising aluminum sulfate;
wherein the content of aluminum sulfate is not less than 1.0 parts by mass per total of 10 parts by mass of the α-starch and the anionic polyacrylamide.
8. A tire puncture repair kit comprising the emulsion coagulant described in claim 2 and a tire puncture repair liquid.
9. A tire puncture repair kit comprising the emulsion coagulant described in claim 7 and a tire puncture repair liquid.
US15/116,921 2014-02-13 2015-02-13 Emulsion coagulant and tire puncture repair kit Active US9694549B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2014-025350 2014-02-13
JP2014025350 2014-02-13
PCT/JP2015/053996 WO2015122497A1 (en) 2014-02-13 2015-02-13 Emulsion coagulant and punctured tire repairing kit

Publications (2)

Publication Number Publication Date
US20170165929A1 true US20170165929A1 (en) 2017-06-15
US9694549B1 US9694549B1 (en) 2017-07-04

Family

ID=53800237

Family Applications (1)

Application Number Title Priority Date Filing Date
US15/116,921 Active US9694549B1 (en) 2014-02-13 2015-02-13 Emulsion coagulant and tire puncture repair kit

Country Status (7)

Country Link
US (1) US9694549B1 (en)
JP (1) JP6264381B2 (en)
KR (1) KR101850358B1 (en)
CN (1) CN105899637B (en)
DE (1) DE112015000813B4 (en)
RU (1) RU2653373C2 (en)
WO (1) WO2015122497A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3524415A1 (en) 2018-02-07 2019-08-14 Sumitomo Rubber Industries, Ltd. Puncture sealing agent and puncture repair system
US11472986B2 (en) 2018-08-22 2022-10-18 Sumitomo Rubber Industries, Ltd. Puncture sealing agent and puncture repair system

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113121727B (en) * 2021-04-13 2023-03-14 长春工业大学 Method for flocculating and demulsifying ABS (acrylonitrile butadiene styrene) graft copolymer

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5342188A (en) * 1976-09-29 1978-04-17 Sanyo Chem Ind Ltd Novel thickener
CN1037516C (en) * 1995-07-03 1998-02-25 潘金海 Additive for metallurgy
JP4691709B2 (en) * 2005-06-06 2011-06-01 独立行政法人産業技術総合研究所 Waste liquid treatment method
US7745511B2 (en) 2007-07-17 2010-06-29 The Yokohama Rubber Co., Ltd. Emulsion coagulant
RU2501819C2 (en) * 2008-06-27 2013-12-20 Акцо Нобель Н.В. Redispersible polymer powder
JP4784694B1 (en) * 2010-05-27 2011-10-05 横浜ゴム株式会社 Liquid coagulant and tire puncture sealant set
US20130072594A1 (en) 2010-05-27 2013-03-21 The Yokohama Rubber Co., Ltd. Liquid coagulant and tire puncture sealing material set
RU2615424C1 (en) 2013-08-01 2017-04-04 Дзе Йокогама Раббер Ко., Лтд. Coagulants and kit for sealing punctures in tire

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3524415A1 (en) 2018-02-07 2019-08-14 Sumitomo Rubber Industries, Ltd. Puncture sealing agent and puncture repair system
US10836126B2 (en) 2018-02-07 2020-11-17 Sumitomo Rubber Industries, Ltd. Puncture sealing agent and puncture repair system
US11472986B2 (en) 2018-08-22 2022-10-18 Sumitomo Rubber Industries, Ltd. Puncture sealing agent and puncture repair system

Also Published As

Publication number Publication date
CN105899637A (en) 2016-08-24
DE112015000813T5 (en) 2016-11-03
CN105899637B (en) 2018-02-02
RU2016133284A3 (en) 2018-03-16
RU2653373C2 (en) 2018-05-08
DE112015000813B4 (en) 2019-10-02
JP6264381B2 (en) 2018-01-24
RU2016133284A (en) 2018-03-16
KR101850358B1 (en) 2018-04-19
US9694549B1 (en) 2017-07-04
KR20160093669A (en) 2016-08-08
JPWO2015122497A1 (en) 2017-03-30
WO2015122497A1 (en) 2015-08-20

Similar Documents

Publication Publication Date Title
US10245795B2 (en) Coagulant and tire puncture repair kit
US9694549B1 (en) Emulsion coagulant and tire puncture repair kit
DE102011080788B4 (en) Tire puncture sealant
DE102009046938B4 (en) A sealant composition for repairing a punctured tire
US9527985B2 (en) Tire puncture sealant, and tire puncture repair kit using same
US9067369B2 (en) Tire puncture sealant
CN104045868A (en) Preparation method of nano cerium oxide/natural rubber composite material
JP2013006949A (en) Flat tire-sealing material
US9217076B2 (en) Emulsion coagulant
CN104072907B (en) A kind of PVC profile for wear-resisting indoor floor and production method thereof
US9657164B2 (en) Emulsion coagulant and tire puncture repair kit using same
CN104341691A (en) Directly extruded rigid PVC tube stock dedicated material and preparation method thereof
CN107118462A (en) A kind of automotive sealant of high-performance easy processing MPR/PVC rubber hot melt materials
MX2016005983A (en) Sealant composition and preparation method therefor.
CN104150810A (en) Water-based sealant for bentonite waterproof blanket and preparation method thereof
Leiva Campusano et al. Block Copolymers in the Synthesis of Gold Nanoparticles. Two New Approaches: Copolymer Aggregates as Reductants and Stabilizers and Simultaneous Formation of Copolymer Aggregates and Gold Nanoparticles
CN104693649A (en) Monocyclic carboxylate nucleating agent modified polytrifluorochloroethylene
CN104744997A (en) Thin film printing ink auxiliary

Legal Events

Date Code Title Description
AS Assignment

Owner name: THE YOKOHAMA RUBBER CO., LTD., JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:OKAMATSU, TAKAHIRO;NARUSE, MASAHIRO;TAKAHARA, HIDEYUKI;REEL/FRAME:039353/0450

Effective date: 20160801

STCF Information on status: patent grant

Free format text: PATENTED CASE

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 4TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1551); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Year of fee payment: 4

AS Assignment

Owner name: THE YOKOHAMA RUBBER CO., LTD., JAPAN

Free format text: CHANGE OF ADDRESS FOR ASSIGNEE;ASSIGNOR:THE YOKOHAMA RUBBER CO., LTD.;REEL/FRAME:065626/0740

Effective date: 20231025