JP2009051893A - Tire puncture sealer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a tire puncture sealer having excellent storage stability and sealability after heat cycle. <P>SOLUTION: The tire puncture sealer comprises a synthetic resin emulsion, a tackifier and an antifreezing agent and has the coefficient of volumetric expansion of a synthetic resin emulsion film of 0-30% obtained when the synthetic resin emulsion film of volume V<SB>1</SB>obtained by drying the synthetic resin emulsion at 20°C for 12 hours and then at 50°C for 10 hours is immersed in a mixed solution containing 100 parts by mass of propylene glycol and 100 parts by mass of water at 80°C for 7 days, the volume expansion test of the synthetic resin emulsion is carried out, the volume V<SB>2</SB>of the synthetic resin emulsion after the volume expansion test is measured and the volume V<SB>1</SB>and the volume V<SB>2</SB>are applied to a numerical expression (1): the coefficient (%) of volumetric expansion of the synthetic resin emulsion film=(V<SB>2</SB>-V<SB>1</SB>)/(V<SB>1</SB>×100). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a tire puncture seal material.

Conventionally, as a tire puncture sealant for repairing a punctured tire, a natural rubber latex blended with a tackifying resin emulsion and an antifreezing agent has been frequently used (for example, see Patent Document 1).
This tire puncture sealant is a latex in which natural rubber particles and tackifying resin particles are repelled by ionic repulsion in an aqueous solution of an antifreeze and dispersed.

  A tire puncture seal material using synthetic rubber latex such as acrylonitrile-butadiene rubber (NBR) latex or styrene-butadiene rubber (SBR) latex has also been proposed (see Patent Document 2).

  Further, it contains natural rubber latex and antifreeze, further contains a resin emulsion, the resin emulsion uses a nonionic surfactant as an emulsifier, a modified phenol resin, a petroleum resin and a resin component. A puncture sealing agent characterized in that at least one selected from the group consisting of carboxylic acid-modified terpene resins is used (see Patent Document 3).

  The tire puncture seal material as described above is normally injected into the tire from the air filling portion of the tire, filled with air up to a predetermined air pressure, and then traveled to reach the puncture hole. And the aggregate of rubber particles is formed by the compressive force and shearing force received when the tire is in contact with the rotation, and the puncture hole is sealed.

  The tire puncture frequency that has been used recently is usually said to be once every few years, and the frequency with which the sealant is actually used is very low. For this reason, the tire puncture sealant has not only excellent sealing performance but also performance that can withstand long-term storage in the vehicle.

JP 2004-035867 A JP 2005-170973 A JP 2006-111726 A

  However, the natural rubber latex tire puncture sealant described in Patent Document 1 has low storage stability, for example, a life of about one year when left in an automobile trunk. If it is too much, it solidifies or gels, and the fluidity is remarkably lowered, which makes it impossible to inject into a punctured tire.

  In addition, the inventors of the present application have found that a tire puncture sealant containing an ethylene-vinyl acetate resin emulsion as a synthetic resin emulsion is subjected to a heat cycle deterioration test between -40 ° C and 80 ° C assuming long-term storage. We found that there is room for improvement in sealability.

  Therefore, an object of the present invention is to provide a tire puncture sealant that is excellent in storage stability and sealability after heat cycle.

As a result of intensive studies on the above problems, the inventors of the present application contain a synthetic resin emulsion, a tackifier, and an antifreezing agent, and the synthetic resin emulsion is dried at 20 ° C. for 12 hours and further at 50 ° C. A synthetic resin emulsion obtained by immersing a synthetic resin emulsion film having a volume of V ₁ obtained by drying for 10 hours in a mixed solution containing 100 parts by mass of propylene glycol and 100 parts by mass of water at 80 ° C. for 7 days. A volume swelling test of the film was performed to measure the volume V ₂ of the synthetic resin emulsion film after the volume swelling test, and the volume V ₁ and the volume V ₂ were expressed by the following formula (1).
Volume swelling ratio of synthetic resin emulsion film (%) = (V ₂ −V ₁ ) / V ₁ × 100 (1) (where V ₁ is the volume of the synthetic resin emulsion film before the volume swelling test, and V ₂ is the volume of the synthetic resin emulsion film after the volume swelling test.) The composition in which the volume swelling ratio of the synthetic resin emulsion film is 0 to 30%, which is obtained by applying to the above, is storage stability, heat The inventors of the present invention have found that the tire puncture sealant is excellent in sealing performance after the cycle, and the present inventors have completed the present invention based on this finding.

That is, the present invention provides the following (1) to (8).
(1) Contains a synthetic resin emulsion, a tackifier, and an antifreezing agent,
A synthetic liquid emulsion having a volume of V ₁ obtained by drying the synthetic resin emulsion at 20 ° C. for 12 hours and further drying at 50 ° C. for 10 hours, a mixed solution containing 100 parts by mass of propylene glycol and 100 parts by mass of water. The volume swelling test of the synthetic resin emulsion film, which is immersed for 7 days under the condition of 80 ° C., is performed, and the volume V ₂ of the synthetic resin emulsion film after the volume swelling test is measured, and the volume V ₁ and the volume are measured. A tire puncture sealant in which the volume swelling ratio of the synthetic resin emulsion film is 0 to 30%, which is obtained by applying V ₂ to the following formula (1).
Volume swelling ratio (%) of synthetic resin emulsion film = (V ₂ −V ₁ ) / V ₁ × 100 (1)
(In the formula, V ₁ is the volume of the synthetic resin emulsion film before the volume swelling test, and V ₂ is the volume of the synthetic resin emulsion film after the volume swelling test.)
(2) The tire puncture sealant according to (1), wherein the synthetic resin emulsion is an ethylene-vinyl acetate resin emulsion.
(3) The tire puncture according to (2), wherein a mass ratio (ethylene / vinyl acetate) of ethylene and vinyl acetate as a monomer constituting the ethylene-vinyl acetate resin emulsion is 20/80 to 50/50. Seal material.
(4) The tire puncture sealant according to (2) or (3) above, wherein the surfactant used in the ethylene-vinyl acetate resin emulsion is polyvinyl alcohol.
(5) The tire puncture sealant according to (4) above, wherein the saponification degree of the polyvinyl alcohol is 65 to 95 mol%.
(6) The tire puncture seal according to any one of (1) to (5), wherein the solid content of the tackifier is 20 to 200 parts by mass with respect to 100 parts by mass of the solid content of the synthetic resin emulsion. Wood.
(7) The tire puncture sealing material according to any one of (1) to (6), wherein the amount of the antifreezing agent is 100 to 500 parts by mass with respect to 100 parts by mass of the solid content of the synthetic resin emulsion. .
(8) The tire puncture sealant according to any one of (1) to (7), wherein the hydrogen ion index is 5.5 to 7.0.

  The tire puncture sealant of the present invention is excellent in storage stability and sealability after heat cycle.

Hereinafter, the present invention will be described in more detail.
The tire puncture seal material of the present invention is
Contains a synthetic resin emulsion, a tackifier, and an antifreeze agent,
A synthetic liquid emulsion having a volume of V ₁ obtained by drying the synthetic resin emulsion at 20 ° C. for 12 hours and further drying at 50 ° C. for 10 hours, a mixed solution containing 100 parts by mass of propylene glycol and 100 parts by mass of water. The volume swelling test of the synthetic resin emulsion film, which is immersed for 7 days under the condition of 80 ° C., is performed, and the volume V ₂ of the synthetic resin emulsion film after the volume swelling test is measured, and the volume V ₁ and the volume are measured. The volume swelling ratio of the synthetic resin emulsion film, which is obtained by applying V ₂ to the following formula (1), is 0 to 30%.
Volume swelling ratio (%) of synthetic resin emulsion film = (V ₂ −V ₁ ) / V ₁ × 100 (1)
(In the formula, V ₁ is the volume of the synthetic resin emulsion film before the volume swelling test, and V ₂ is the volume of the synthetic resin emulsion film after the volume swelling test.)

The synthetic resin emulsion used for the tire puncture seal material of the present invention is not particularly limited, and examples thereof include conventionally known ones.
Preferable examples of the synthetic resin emulsion include ethylene-vinyl acetate resin emulsion, acrylic emulsion, urethane emulsion, polyolefin emulsion, vinyl acetate emulsion, and polyvinyl chloride emulsion.
The synthetic resin emulsion has relatively good stability at pH 5.5 to 7.0.
The synthetic resin emulsions can be used alone or in combination of two or more.
Among these, an ethylene-vinyl acetate resin emulsion, a urethane emulsion, and an acrylic emulsion are preferable, and an ethylene-vinyl acetate resin emulsion is more preferable from the viewpoint of excellent storage stability and sealing properties after heat cycle.

<Ethylene-vinyl acetate resin emulsion>
The ethylene-vinyl acetate resin emulsion (hereinafter sometimes referred to as “EVA emulsion”) is not particularly limited as long as ethylene and vinyl acetate are used as monomers constituting the ethylene-vinyl acetate resin emulsion. For example, a conventionally well-known thing is mentioned.

  The mass ratio (ethylene / vinyl acetate) of ethylene and vinyl acetate as a monomer constituting the ethylene-vinyl acetate resin emulsion is 20/80 to 20% from the viewpoint that the volume swelling ratio is low and the sealing performance after heat cycle is excellent. 50/50 is preferable, and 40/60 to 50/50 is more preferable.

Moreover, the ethylene-vinyl acetate resin emulsion can use another monomer as needed other than ethylene and vinyl acetate as a monomer used when manufacturing an ethylene-vinyl acetate resin emulsion.
Examples of monomers other than ethylene and vinyl acetate that can be used in producing an ethylene-vinyl acetate resin emulsion include acrylic acid esters such as 2-ethylhexyl acrylate, butyl acrylate, and ethyl acrylate; methyl methacrylate , Methacrylate esters such as butyl methacrylate; vinyl esters such as vinyl chloride and vinyl versatate; monomers containing carboxyl groups such as acrylic acid and methacrylic acid; sulfonic acid groups, hydroxy groups, epoxy groups, methylol groups, amino acids And various monomers containing functional groups such as amide groups.

  The ethylene-vinyl acetate resin emulsion is not particularly limited for its production. For example, there may be mentioned a method in which ethylene, vinyl acetate and other monomers as required are used as monomers and copolymerized (emulsion polymerization) using an emulsifying dispersant.

The emulsifying dispersant used in the production of the ethylene-vinyl acetate resin emulsion is not particularly limited, and examples thereof include nonionic surfactants; anionic surfactants; cationic surfactants; zwitterionic surfactants; A reactive surfactant having a reactive double bond in the surfactant molecule; water-soluble polymers such as polyvinyl alcohol and starch.
Among these, a water-soluble polymer that can be used as a protective colloid is preferable, polyvinyl alcohol and carboxymethyl cellulose are more preferable, and only polyvinyl alcohol is more preferable, from the viewpoint of excellent sealing properties after heat cycle.

The polyvinyl alcohol as the emulsifying dispersant used in the production of the ethylene-vinyl acetate resin emulsion is not particularly limited as long as it is a polymer having a repeating unit represented by —CH ₂ —CH (—OH) —. For example, a conventionally well-known thing is mentioned.
The weight average molecular weight of polyvinyl alcohol is not particularly limited. For example, the thing of 100,000-500,000 is mentioned.
Polyvinyl alcohol is not particularly limited for its production. For example, a conventionally well-known thing is mentioned.
Especially, it is preferable that it is 65-95 mol% from a viewpoint that the saponification degree of polyvinyl alcohol is excellent by the sealing performance after a heat cycle, and it is more preferable that it is 65-88 mol%.

  Nonionic surfactants include, for example, fatty acid sorbitan esters, polyoxyethylene fatty acid sorbitans, polyoxyethylene higher alcohol ethers, polyoxyethylene-propylene higher alcohol ethers, polyoxyethylene fatty acid esters, polyoxyethylene alkylphenols, polyoxyethylenes. Examples include alkylamines and polyoxyethylene-polyoxypropylene block polymers.

  Examples of the anionic surfactant include fatty acid alkali metal salts, alkyl sulfates, alkyl ether sulfates, alkylbenzene sulfonates, N-acyl-N-methyl taurates, dialkyl sulfosuccinates, N-alkyl- N, N-dimethyl oxide and the like can be mentioned.

  Examples of the cationic surfactant include quaternary ammonium salts such as alkylamine acetate and alkyltrimethylammonium chloride.

Examples of the zwitterionic surfactant include dimethylalkyl betaine and alkylamide betaine.
The emulsifying dispersants can be used alone or in combination of two or more.

The weight average molecular weight of the EVA emulsion is preferably 10,000 to 500,000, and more preferably 50,000 to 200,000, from the viewpoint of excellent sealing properties.
The EVA emulsion preferably has a solid content of 40 to 70 mass%, more preferably 50 to 65 mass%, from the viewpoint of excellent sealing properties.

  In the present invention, a commercially available product can be used as the EVA emulsion. Specific examples thereof include ethylene vinyl acetate emulsion (Sumikaflex 408HQE, 401HQ, 400HQ, 950HQ) manufactured by Sumika Chemtex.

<Acrylic emulsion>
An acrylic emulsion is not specifically limited, A conventionally well-known acrylic emulsion can be used.
Examples of the acrylic emulsion include methacrylic acid esters, acrylic acid esters, aromatic vinyl monomers, unsaturated nitriles, conjugated diolefins, polyfunctional vinyl monomers, amide monomers, and hydroxyl group-containing monomers. Body, caprolactone addition monomer, amino group-containing monomer, glycidyl group-containing monomer, acid monomer, vinyl monomer, etc., are obtained by polymerization (emulsion polymerization) using an emulsifying dispersant. A water-based emulsion etc. are mentioned suitably.

Specific examples of the methacrylic acid ester include methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, nonyl methacrylate, and lauryl methacrylate.
Specific examples of the acrylic ester include butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, and the like.

Specific examples of the aromatic vinyl monomer include paramethyl styrene, α-methyl styrene, parachloroethylene, chloromethylene styrene, vinyl toluene, and the like.
Specific examples of the unsaturated nitrile include acrylonitrile and methacrylonitrile.
Specific examples of the conjugated diolefin include butadiene, isoprene, chloroprene and the like.
Specific examples of the polyfunctional vinyl monomer include divinylbenzene, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene diglycol dimethacrylate, allyl methacrylate, diallyl phthalate, and trimethylol. Examples include propane triacrylate, glyceryl diallyl ether, polyethylene glycol dimethacrylate, and polyethylene glycol diacrylate.

Specific examples of the amide monomer include acrylamide, methacrylamide, n-methylol methacrylamide, and the like.
Specific examples of the hydroxy group-containing monomer include β-hydroxyethyl acrylate and β-hydroxy methacrylate.
Specific examples of the caprolactone addition monomer include, for example, β-hydroxyethyl acrylate, β-hydroxy methacrylate such as FA-1, FA-2, FA-3, and FM-1 manufactured by Daicel Chemical. It is done.
Specific examples of the amino group-containing monomer include dimethylaminoethyl acrylate and diethylaminoethyl acrylate.
Specific examples of the glycidyl group-containing monomer include glycidyl acrylate and diglycidyl methacrylate.
Specific examples of the acid monomer include acrylic acid, methacrylic acid, itaconic acid, paravinyl benzoic acid, and the like.
Specific examples of the vinyl monomer include vinyl acetate, vinyl chloride, and vinylidene chloride.

  Of these, acrylic acid esters and methacrylic acid esters are preferable from various viewpoints such as cost, handleability, and physical properties.

  Examples of the emulsifying dispersant include nonionic surfactants, anionic surfactants, cationic surfactants, and zwitterionic surfactants. Among these, nonionic surfactants are preferable because they are neutral and have a low odor.

  Specific examples of the nonionic surfactant include, for example, fatty acid sorbitan esters, polyoxyethylene fatty acid sorbitans, polyoxyethylene higher alcohol ethers, polyoxyethylene-propylene higher alcohol ethers, polyoxyethylene fatty acid esters, polyoxyethylene. Examples thereof include alkylphenol, polyoxyethylene alkylamine, and polyoxyethylene-polyoxypropylene block polymer.

  Specific examples of anionic surfactants include fatty acid alkali metal salts, alkyl sulfates, alkyl ether sulfates, alkylbenzene sulfonates, N-acyl-N-methyl taurates, and dialkyl sulfosuccinates. N-alkyl-N, N-dimethyl oxide and the like.

  Specific examples of the cationic surfactant include quaternary ammonium salts such as alkylamine acetate and alkyltrimethylammonium chloride.

  Specific examples of the zwitterionic surfactant include dimethylalkyl betaine and alkylamide betaine.

Further, as the emulsifying dispersant, a reactive surfactant having a reactive double bond in the surfactant molecule; a water-soluble polymer such as polyvinyl alcohol and starch can be used.
The above emulsifying dispersants may be used alone or in combination of two or more.

The acrylic emulsion preferably has a weight average molecular weight of 10,000 to 500,000, more preferably 50,000 to 200,000.
Moreover, it is preferable that solid content is 30-60 mass%, and it is more preferable that the said acrylic emulsion is 40-55 mass%.

  In the present invention, commercially available products may be used as the acrylic emulsion, and specific examples thereof include A6001 manufactured by Regex Corporation, Lx823 manufactured by Nippon Zeon Co., Ltd., and the like.

<Urethane emulsion>
The urethane emulsion is obtained by dispersing polyurethane particles in water. Preferable examples of the urethane emulsion include those obtained by reacting a urethane prepolymer having an ionic group with a neutralizing agent or a quaternizing agent in water.

  Specific examples of the urethane prepolymer include, for example, a polyisocyanate compound (A) having two or more isocyanate groups, a compound (B) having two or more active hydrogens, and a group having reactivity with an isocyanate group. Preferred examples include urethane prepolymers obtained by copolymerizing a compound (C) having an ionic group with an ionic group.

As said polyisocyanate compound (A), the various thing used for manufacture of a normal polyurethane resin can be used. Specifically, for example, TDI such as 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate; MDI such as diphenylmethane-4,4′-diisocyanate; tetramethylxylylene diisocyanate (TMXDI), trimethylhexamethylene Diisocyanate (TMHMDI), 1,5-naphthalene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), xylylene diisocyanate (XDI), triphenylmethane triisocyanate, norbornane skeleton And modified products such as diisocyanates (NBDI) having these and isocyanurate forms thereof.
These may be used alone or in combination of two or more.

  Among these isocyanate group-containing compounds, TDI and MDI are preferable. Since these polyisocyanates are general-purpose, they are inexpensive and easily available.

The compound (B) is not particularly limited as long as it is a compound having two or more active hydrogens. Specific examples include a polyol compound, an amine compound, and an alkanolamine. These may be used alone or in combination of two or more.
Among these, a polyol compound is preferable.

Specific examples of the polyol compound include polyether polyols such as polytetramethylene glycol, polyethylene glycol, polypropylene glycol, polyoxypropylene glycol, and polyoxybutylene glycol; polycaprolactone polyols; polycarbonate polyols; Polyolefin polyols such as isoprene polyols; Adipate polyols; Polyester polyols such as castor oil. These may be used alone or in combination of two or more.
Among these, polyether polyol, polycaprolactone polyol, polycarbonate polyol, and polyester polyol are preferable, and polyether polyol and polyester polyol are more preferable because of superior storage stability.

  The polyol compound preferably has a number average molecular weight of about 500 to 10000, more preferably about 2000 to 6000.

  Specific examples of the amine compound include ethylenediamine and hexamethylenediamine.

  Specific examples of the alkanolamine include ethanolamine and propanolamine.

The compound (C) is a compound having an isocyanate group-reactive group and an ionic group.
Specific examples of the group having reactivity with the isocyanate group include a hydroxy group, an amino group (—NH ₂ ), an imino group (—NH—), and a mercapto group.

Here, the ionic group means a group that can be positively or negatively charged by neutralization. Specifically, it means an anionic group or a cationic group.
An anionic group refers to a group that can be negatively charged by neutralization with a base. Specifically, for example, a carboxy group, a sulfo group, a phosphoric acid group and the like are preferable. The cationic group refers to a group that can be positively charged by neutralizing with acid or reacting with a quaternizing agent. Specifically, for example, a tertiary amino group is preferably exemplified.

  When the ionic group is an anionic group, it is usually not necessary to adjust the pH of the tire puncture sealant, and the tire puncture sealant obtained is preferable because it has no irritating odor and hardly corrodes the steel cord. .

  Specific examples of compounds having an isocyanate group-reactive group and an anionic group (hereinafter referred to as “compound (C1)”) include fatty acids such as hydroxyacetic acid, hydroxypropionic acid, and hydroxybutyric acid. Aromatic monohydroxycarboxylic acids such as hydroxybenzoic acid, hydroxyethylbenzoic acid and hydroxycinnamic acid; dihydroxycarboxylic acids such as dimethylolpropionic acid, dimethylolbutanoic acid and dimethylolacetic acid; mercaptoacetic acid and mercapto Mercaptocarboxylic acids such as propionic acid and mercaptobenzoic acid; aminocarboxylic acids such as aminoadipic acid and aminobenzoic acid; hydroxysulfonic acids such as hydroxybenzenesulfonic acid; mercaptosulfonic acids such as 3N-mercaptoethanesulfonic acid; And amino sulfonic acids such as benzenesulfonic acid. These may be used alone or in combination of two or more.

Examples of the compound having a reactive group with an isocyanate group and a cationic group (hereinafter referred to as “compound (C2)”) include a group having reactivity with an isocyanate group and a tertiary amino group. Preferred examples include compounds having the same.
Suitable examples of such compounds include compounds represented by the following formula (1).

In the above formula (1), R represents an alkyl group or hydroxyalkyl group having 1 to 4 carbon atoms, R ¹ and R ² may be the same or different and each an alkylene group having 1 to 4 carbon atoms Represents.
The compound represented by the above formula (1) includes a diol compound having a tertiary amino group and a triol compound having a tertiary amino group.

  Specific examples of such a compound (C2) include N-methyl-N, N-diethanolamine, N-ethyl-N, N-diethanolamine, N-isobutyl-N, N-diethanolamine, and diisopropanolamine. And alkanolamines such as triethanolamine. These may be used alone or in combination of two or more.

Although the manufacturing method of the said urethane prepolymer is not specifically limited, For example, the method of superposing | polymerizing a polyisocyanate compound (A), a compound (B), and a compound (C) by stirring simultaneously etc. is mentioned.
In the production of the urethane prepolymer, the order in which the compound (B) and the compound (C) are added is not particularly limited, and may be added simultaneously, or one of them may be added first. For example, in accordance with a normal method for producing a urethane prepolymer, a method in which a polyisocyanate compound (A) and a compound (B) are reacted to produce a urethane prepolymer, and then a compound (C) is added and added is used. it can.

The copolymerization is preferably performed so that the isocyanate group content (NCO%) of the resulting urethane prepolymer is 0.3 to 3%.
Moreover, 1-50 mass% of polyisocyanate compound (A), 30-90 mass% of compound (B) with respect to the total mass of polyisocyanate compound (A), compound (B), and compound (C), compound It is preferable to contain 0.1 to 20% by mass of (C) and stir these under an inert gas atmosphere at 60 to 90 ° C. for about 2 to 8 hours. Here, NCO% represents mass% of NCO groups with respect to the total mass of the urethane prepolymer.

Moreover, the said copolymerization can be performed in presence of urethanization catalysts, such as an organotin compound, an organic bismuth, and an amine as needed, and it is preferable to carry out in presence of an organotin compound.
Specific examples of the organic tin compound include stannous acetate such as stannous acetate, stannous octoate, stannous laurate, and stannous oleate; dibutyltin acetate, dibutyltin dilaurate, and dibutyltin. Dialkyltin salts of carboxylic acids such as maleate, dibutyltin di-2-ethylhexoate, dilauryltin diacetate, dioctyltin diacetate; hydroxylations such as trimethyltin hydroxide, tributyltin hydroxide, trioctyltin hydroxide Trialkyltin: Dialkyltin oxides such as dibutyltin oxide, dioctyltin oxide and dilauryltin oxide; dialkyltin chlorides such as dibutyltin dichloride and dioctyltin dichloride, and the like. These may be used alone or in combination of two or more.
Of these, dibutyltin dilaurate, dibutyltin acetate, and dibutyltin maleate are preferred because they are relatively inexpensive and easy to handle.

  The weight average molecular weight of the urethane prepolymer obtained by such copolymerization is preferably 1500 to 30000, and more preferably 3000 to 20000.

  The urethane prepolymer is emulsified by reacting with a neutralizing agent in water to form a stabilized urethane emulsion. When a urethane prepolymer having a cationic group is used, a quaternizing agent may be used instead of the neutralizing agent.

As the neutralizing agent, when a urethane prepolymer having an anionic group is used, a base can be used, and it is not particularly limited as long as it is a Lewis base. Specifically, for example, sodium hydroxide, hydroxide Examples include potassium and tertiary amines. These may be used alone or in combination of two or more. Of these bases, triethylamine is preferred.
Further, when a urethane prepolymer having a cationic group is used, an acid can be used as a neutralizing agent, and it is not particularly limited as long as it is a Lewis acid. Specifically, for example, hydrochloric acid, sulfuric acid, nitric acid, phosphorus Examples thereof include inorganic acids such as acids and phosphorous acid, and organic acids such as acetic acid, propionic acid, formic acid, butyric acid, lactic acid, malic acid, and citric acid. These may be used alone or in combination of two or more. Of these acids, hydrochloric acid and acetic acid are preferred.

  The quaternizing agent is a compound capable of quaternizing the tertiary amino group of the urethane prepolymer. Specifically, for example, ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, etc. Epoxy compounds; dialkyl sulfates such as dimethyl sulfate and diethyl sulfate; alkyl sulfonates such as methyl paratoluenesulfonate; alkyl halides such as methyl chloride, ethyl chloride, benzyl chloride, methyl bromide, and ethyl bromide .

  The urethane prepolymer can be dispersed in water by adding a viscosity modifier and a chain extender, if necessary, in addition to the neutralizing agent or quaternizing agent.

  Examples of the viscosity modifier include organic solvents that are compatible with water, and specific examples thereof include ethyl acetate, acetone, and methyl ethyl ketone.

  Specific examples of the chain extender include aliphatic diamines such as ethylenediamine, propylenediamine, hexamethylenediamine, and triethylenetetramine; alicyclic diamines such as isophoronediamine and piperazine; aromatic diamines such as diphenyldiamine; A triamine etc. are mentioned.

  The method for producing the urethane emulsion is not particularly limited. For example, the urethane prepolymer and the neutralizing agent or the quaternizing agent, and if necessary, the viscosity modifier, the chain extender, etc. are added to water. Thus, a method of mixing with stirring may be mentioned.

<Polyolefin emulsion>
The polyolefin emulsion is not particularly limited, and a conventionally known polyolefin emulsion can be used.
Examples of the polyolefin-based emulsion include those in which a polyolefin having a hydrophilic group introduced is dispersed in water. Examples of the hydrophilic group include a carboxy group, a sulfonic acid group, a phosphoric acid group, a hydroxy group, and an amino group.
Specific examples of the polyolefin emulsion include polyethylene emulsion, polypropylene emulsion, ethylene-propylene copolymer emulsion, and polybutene emulsion.
These may be used alone or in combination of two or more.

The polyethylene emulsion is not particularly limited, and a conventionally known polyethylene emulsion can be used.
Examples of the polyethylene emulsion include those in which a polyethylene having a hydrophilic group introduced is dispersed in water. Examples of the hydrophilic group include a carboxy group, a sulfonic acid group, a phosphoric acid group, a hydroxy group, and an amino group.

  The emulsifying dispersant is the same as that used for the acrylic emulsion described above.

As said polyethylene, the thing whose melting | fusing point is 90-150 degreeC is preferable, and the thing whose weight average molecular weight is 1,000-1,000,000 is preferable.
In the present specification, the melting point refers to a value measured by a softening point test method (ring ball method) defined in JIS K2207.

  In the present invention, commercially available products may be used as the polyethylene emulsion. Specific examples thereof include Johnson Polymer JW-150, Clariant Wax Dispersion W867, and San Nopco Nopcoat. PEM-17, PE401 manufactured by Naruse Chemical Co., etc., can be mentioned.

The said polypropylene emulsion is not specifically limited, A conventionally well-known polypropylene emulsion can be used.
Examples of the polypropylene emulsion include those in which a polypropylene having a hydrophilic group introduced is dispersed in water. Examples of the hydrophilic group include a carboxy group, a sulfonic acid group, a phosphoric acid group, a hydroxy group, and an amino group.

Moreover, what the polypropylene was disperse | distributed in water with the emulsification dispersing agent can also be used as said polypropylene emulsion.
The emulsifying dispersant is the same as that used for the acrylic emulsion described above.

  As said polypropylene, the thing whose melting | fusing point is 90-150 degreeC is preferable, and the thing whose weight average molecular weight is 1,000-1,000,000 is preferable.

  In the present invention, commercially available products may be used as the polypropylene emulsion, and specific examples thereof include PP emulsion manufactured by Maruyoshi Kasei Co., Ltd.

The ethylene-propylene copolymer emulsion is not particularly limited, and a conventionally known ethylene-propylene copolymer emulsion can be used.
Examples of the ethylene-propylene copolymer emulsion include those in which an ethylene-propylene copolymer having a hydrophilic group introduced is dispersed in water. Examples of the hydrophilic group include a carboxy group, a sulfonic acid group, a phosphoric acid group, a hydroxy group, and an amino group.

Moreover, what the ethylene-propylene copolymer was disperse | distributed in water with the emulsification dispersing agent can also be used as said ethylene-propylene copolymer emulsion.
The emulsifying dispersant is the same as that used for the acrylic emulsion described above.

  As the ethylene-propylene copolymer, those having a melting point of 90 to 150 ° C. are preferable, and those having a weight average molecular weight of 1,000 to 1,000,000 are preferable.

  In the present invention, a commercially available product may be used as the ethylene-propylene copolymer emulsion, and specific examples thereof include HS manufactured by Regitex.

The polybutene emulsion is not particularly limited, and a conventionally known polybutene emulsion can be used.
Examples of the polybutene emulsion include those in which a polybutene having a hydrophilic group introduced is dispersed in water. Examples of the hydrophilic group include a carboxy group, a sulfonic acid group, a phosphoric acid group, a hydroxy group, and an amino group.

Moreover, what the polybutene was disperse | distributed in water with the emulsification dispersing agent can also be used as said polybutene emulsion.
The emulsifying dispersant is the same as that used for the acrylic emulsion described above.

  Specifically, as the polybutene emulsion, for example, a polymer having a structural unit based on a phosphorylcholine-like group-containing methacrylic acid ester represented by the following formula (2) (hereinafter referred to as polymer (D)). Preferable examples include an emulsion of polybutene and water.

In the formula (2), R ³ is, - (CH _{2) m} - or _{- (CH 2 CH 2 O)} n -CH 2 CH 2 - and is, m, n are each is an integer from 1 to 10 .

Specific examples of the monomer represented by the above formula (2) include 2-methacryloyloxyethyl-2 ′-(trimethylammonio) ethyl phosphate, 3-methacryloyloxypropyl-2 ′-(trimethylammonio). ) Ethyl phosphate, 4-methacryloyloxybutyl-2 '-(trimethylammonio) ethyl phosphate, 2-methacryloyloxyethoxyethyl-2'-(trimethylammonio) ethyl phosphate, 2-methacryloyloxydiethoxyethyl-2'- (Trimethylammonio) ethyl phosphate and the like. These may be used alone or in combination of two or more.
Among these, 2-methacryloyloxyethyl-2 ′-(trimethylammonio) ethyl phosphate is preferable.

The polymer (D) is a homopolymer obtained by polymerizing the monomer represented by the formula (2) alone or a copolymer obtained by copolymerizing another copolymerizable vinyl monomer.
Examples of other copolymerizable vinyl monomers include styrene monomers such as styrene, methylstyrene, and chlorostyrene; vinyl ether monomers such as vinyl acetate and vinyl propionate; methyl (meth) acrylate, ethyl (meth) acrylate, Alkyl (meth) acrylate monomers such as n-butyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2-ethylhexyl (meth) acrylate; (meth) acrylic acid; 2-hydroxyethyl (meth) Functional group-containing (meth) acrylates such as acrylate and glycerol (meth) acrylate; polyalkylene glycol (meth) acrylates such as polyethylene glycol (meth) acrylate and polypropylene glycol (meth) acrylate DOO; (meth) acrylic acid amide, N- vinylpyrrolidone, and nitrogen-containing monomers such as acrylonitrile and the like. These may be used alone or in combination of two or more.
Among these, a (meth) acrylate monomer is preferable from the viewpoint of controlling the balance between the hydrophilicity and hydrophobicity of the polymer (D) and copolymerization during the reaction. From the viewpoint of the stability of the polybutene emulsion, a (meth) acrylate monomer having an alkyl chain having 1 to 24 carbon atoms is preferred.

  When the monomer represented by the formula (2) is copolymerized with another monomer, the content of the monomer represented by the formula (2) is preferably 1 to 90% by mass, and more preferably 5 to 80% by mass. . If it is this range, the characteristic of the monomer represented by Formula (2) and another monomer can fully express.

  The polymer (D) has an effect as a dispersant or an emulsifier of polybutene in water, and also has an effect as a stabilizer for fillers, drugs, and the like added as necessary. On the other hand, it is inert and less irritating and can be used safely.

The polymer (D) is, for example, bulk polymerization, suspension polymerization, emulsion polymerization, solution of each monomer component described above in the presence of a radical polymerization initiator in an inert gas atmosphere such as nitrogen, carbon dioxide, and helium. It can be obtained by polymerization by a known method such as polymerization.
The polymerization initiator is not particularly limited. For example, benzoyl peroxide, lauroyl peroxide, diisopropyl peroxydicarbonate, t-butylperoxy-2-ethylhexanoate, t-butylperoxypivalate, t-butylperoxy Examples thereof include diisobutyrate, azobisisobutyronitrile, azoisobisdimethylvaleronitrile, persulfate, and persulfate-bisulfite system.
As for the preparation amount of the said polymerization initiator, 0.0001-10 mass parts is preferable with respect to 100 mass parts of monomer components, and 0.01-5 mass parts is more preferable.
The polymerization temperature is preferably 20 to 100 ° C., and the polymerization time is preferably 0.5 to 72 hours.

  The weight average molecular weight of the polymer (D) is preferably 1,000 to 5,000,000, and preferably 10,000 to 1,000,000 from the viewpoint of miscibility with polybutene and water and the viscosity of the blend. More preferred.

The polybutene includes isobutylene homopolymer, copolymer of isobutylene and its isomer, copolymer of isobutylene and other olefin, copolymer of isobutylene, its isomer and other olefin, and hydride thereof. It is. These may be used alone or in combination of two or more. Among these, hydrogenated polybutene, which is a hydride, is preferable because it is less susceptible to oxidative degradation due to heat and light.
Examples of the isomer include 1-butene, cis-2-butene, and trans-2-butene.

The polybutene is produced, for example, by polymerizing a gas mixture containing isobutylene or the like using an acid catalyst such as aluminum chloride, and adding hydrogen as necessary.
When producing polybutene, a high-viscosity polybutene can be produced from a low-viscosity light polybutene by adjusting the amount of catalyst added and the reaction temperature.
Polybutene is a highly safe material, is an oily polymer that is inert to biological components, and can impart sealing properties.

The polybutene is preferably liquid or viscous, and liquid polybutene is particularly preferable for preparing an emulsion.
The number average molecular weight of the polybutene is preferably from 150 to 4000 from the viewpoint of being liquid or viscous.

1-50 mass% is preferable and, as for content of a polymer (D), 2-40 mass% is more preferable. Within this range, the stability of the emulsion is excellent and the viscosity does not become too high.
10-90 mass% is preferable, and, as for content of polybutene, 20-80 mass% is more preferable.
The water content is preferably 9 to 89% by mass.

The emulsion preferably further contains a surfactant. The stability of the emulsion can be improved by adding a surfactant.
Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, and zwitterionic surfactants. These may be used alone or in combination of two or more.
In the above surfactant, the preferred carbon chain length of the fatty acid and alkyl group is 8 to 18 carbon atoms.

  Specific examples of the nonionic surfactant include, for example, fatty acid sorbitan esters, polyoxyethylene fatty acid sorbitans, polyoxyethylene higher alcohol ethers, polyoxyethylene-propylene higher alcohol ethers, polyoxyethylene fatty acid esters, polyoxyethylene. Examples thereof include alkylphenol, polyoxyethylene alkylamine, and polyoxyethylene-polyoxypropylene block polymer.

  Specific examples of the anionic surfactant include, for example, fatty acid alkali metal salts, alkyl sulfates, alkyl ether sulfates, alkylbenzene sulfonates, N-acyl-N-methyl taurates, and dialkyl sulfosuccinates. N-alkyl-N, N-dimethyl oxide and the like.

Specific examples of the cationic surfactant include quaternary ammonium salts such as alkylamine acetate and alkyltrimethylammonium chloride.
Specific examples of the zwitterionic surfactant include dimethylalkyl betaine and alkylamide betaine.

  0.01-10 mass% is preferable and, as for the addition amount of the said surfactant, 0.1-2 mass% is more preferable. Within this range, the effect of adding a surfactant can be sufficiently obtained, and the safety such as less irritation to the skin is also excellent.

The emulsion may contain various additives as long as the object of the present invention is not impaired.
Specific examples of the additives include oily materials such as vegetable oils, animal fats, waxes, waxes, paraffins other than polybutene, petrolatum, fatty acid esters, higher fatty acids, higher alcohols, titanium oxide, zinc oxide, talc. , Inorganic compounds such as silica, kaolin, sodium carbonate, borax, organic solvents such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerin, polyethylene glycol, polypropylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone, carboxymethyl cellulose, ethylene oxide and propylene Other water-soluble polymers such as a block copolymer of oxide and a copolymer of maleic anhydride and methyl vinyl ether are included.

  The manufacturing method of the said emulsion is not specifically limited, It can carry out by a well-known method. For example, polybutene, polymer (D), water and optionally surfactants and various additives are emulsified in a temperature range of room temperature to 90 ° C. using an emulsifier or kneader such as a homogenizer or a homomixer. Can be manufactured.

  In the present invention, commercially available products may be used as the polybutene emulsion, and specific examples thereof include Emmawet 10E, Emmawet 30E (both manufactured by NOF Corporation) and the like.

<Vinyl acetate emulsion>
The vinyl acetate emulsion is not particularly limited, and a conventionally known vinyl acetate emulsion can be used.
Suitable examples of the vinyl acetate emulsion include an aqueous emulsion obtained by polymerizing vinyl acetate using an emulsifying dispersant (emulsion polymerization).

  Moreover, in this invention, you may copolymerize another monomer as needed in the said superposition | polymerization. Specific examples of the other monomer include ethylenic compounds such as ethylene and propylene; acrylic acid esters such as 2-ethylhexyl acrylate, butyl acrylate, and ethyl acrylate; methyl methacrylate, butyl methacrylate, and the like. Methacrylic acid esters; vinyl esters such as vinyl chloride and vinyl versatic acid; In addition to monomers containing carboxyl groups such as acrylic acid and methacrylic acid, other monomers containing functional groups such as sulfonic acid groups, hydroxy groups, epoxy groups, methylol groups, amino groups, amide groups, etc. Monomers can also be used.

  As the emulsifying dispersant, those similar to the emulsifying dispersant used in the EVA emulsion can be used.

The weight average molecular weight of the vinyl acetate emulsion is preferably 10,000 to 500,000, and more preferably 50,000 to 200,000.
The vinyl acetate emulsion preferably has a solid content of 40 to 70% by mass, and more preferably 50 to 65% by mass.

  In the present invention, commercially available products may be used as the above-mentioned vinyl acetate emulsion, and specific examples thereof include Pegar manufactured by High Pressure Gas Industry Co., Ltd.

<Polyvinyl chloride emulsion>
The polyvinyl chloride emulsion is not particularly limited, and a conventionally known polyvinyl chloride emulsion can be used.
Preferable examples of the polyvinyl chloride emulsion include an aqueous emulsion obtained by polymerizing (emulsion polymerization) vinyl chloride using an emulsifying dispersant.

  Moreover, in this invention, you may copolymerize another monomer as needed in the said superposition | polymerization. Specific examples of the other monomer include, for example, ethylenic compounds such as ethylene and propylene; acrylic acid esters such as 2-ethylhexyl acrylate, butyl acrylate, and ethyl acrylate; methyl methacrylate, butyl methacrylate, and the like. And methacrylic acid esters. In addition to monomers containing carboxyl groups such as acrylic acid and methacrylic acid, various monomers containing functional groups such as sulfonic acid groups, hydroxy groups, epoxy groups, methylol groups, amino groups, amide groups, etc. Monomers can also be used.

  As the emulsifying dispersant, those similar to the emulsifying dispersant used in the EVA emulsion can be used.

The polyvinyl chloride emulsion preferably has a weight average molecular weight of 10,000 to 500,000, and more preferably 50,000 to 200,000.
The polyvinyl chloride emulsion preferably has a solid content of 40 to 70 mass%, more preferably 50 to 65 mass%.

  In the present invention, commercially available products may be used as the polyvinyl chloride emulsion, and specific examples thereof include SE-1010 manufactured by Sumika Chemtex Co., Ltd.

The tackifier will be described below.
The tackifier contained in the tire puncture seal material of the present invention is not particularly limited as long as it is a compound having adhesiveness that can be used for the tire puncture seal material. For example, a conventionally well-known thing is mentioned.
Specifically, for example, rosin resins such as rosin esters, polymerized rosin esters, and modified rosins; terpene resins such as terpene phenols and aromatic terpenes; hydrogenated terpene resins obtained by hydrogenating terpene resins; phenol resins; Examples include xylene resins.
In addition, an emulsion obtained by emulsifying these resins is mentioned as one of preferred embodiments from the viewpoint of excellent compatibility with the synthetic resin emulsion.

Especially, it is at least one selected from the group consisting of a rosin resin, a terpene resin and a hydrogenated terpene resin from the viewpoint of excellent sealing properties, storage stability, and excellent sealing properties after heat cycle. Is preferred.
A tackifier can be used individually or in combination of 2 types or more, respectively.

The solid content of the tackifier is 20 to 200 parts by mass with respect to 100 parts by mass of the solid content of the synthetic resin emulsion from the viewpoint of excellent sealing properties, storage stability, and excellent sealing properties after heat cycle. Is preferable, 20-150 mass parts is more preferable, and 20-100 mass parts is still more preferable.
Here, the solid content of the synthetic resin emulsion means the total amount of the synthetic resin emulsion excluding water and the solvent.
The solid content of the tackifier means the total amount of the tackifier excluding water and the solvent.

The antifreezing agent will be described below.
The antifreezing agent contained in the tire puncture seal material of the present invention is not particularly limited as long as it is a compound that can prevent water from freezing.
Specific examples include ethylene glycol and propylene glycol.
Among these, propylene glycol is preferable from the viewpoint that it is not a chemical substance targeted in PRTR (Pollutant Release and Transfer Register).
Antifreeze agents can be used alone or in combination of two or more.

  The amount of the antifreezing agent is preferably 100 to 500 parts by mass, and 100 to 200 parts by mass with respect to 100 parts by mass of the solid content of the synthetic resin emulsion, from the viewpoint of excellent performance for preventing the tire puncture sealant from freezing. Part is more preferable, and 100 to 150 parts by mass is still more preferable.

  The tire puncture seal material of the present invention may contain, for example, a filler, an anti-aging agent, an antioxidant, a pigment (dye), a plasticizer, if necessary, in addition to the synthetic resin emulsion, tackifier and anti-freezing agent. , Thixotropic agents, ultraviolet absorbers, flame retardants, surfactants (including leveling agents), dispersants, dehydrating agents, antistatic agents, and the like.

  Examples of the filler include organic or inorganic fillers having various shapes. Specifically, for example, fumed silica, calcined silica, precipitated silica, ground silica, fused silica; diatomaceous earth; iron oxide, zinc oxide, titanium oxide, barium oxide, magnesium oxide; calcium carbonate, magnesium carbonate, zinc carbonate; Waxite clay, kaolin clay, calcined clay; carbon black; these fatty acid treated products, resin acid treated products, urethane compound treated products, fatty acid ester treated products, and the like.

Specific examples of the anti-aging agent include hindered phenol compounds.
Specific examples of the antioxidant include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA).

  Specific examples of the pigment include inorganic pigments such as titanium oxide, zinc oxide, ultramarine, bengara, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride, sulfate, etc .; azo pigment, phthalocyanine pigment, quinacridone Pigment, quinacridone quinone pigment, dioxazine pigment, anthrapyrimidine pigment, anthanthrone pigment, indanthrone pigment, flavanthrone pigment, perylene pigment, perinone pigment, diketopyrrolopyrrole pigment, quinonaphthalone pigment, anthraquinone pigment, thioindigo pigment, benzimidazolone Examples thereof include organic pigments such as pigments, isoindoline pigments, and carbon black.

  Specific examples of the plasticizer include diisononyl phthalate (DINP); dioctyl adipate, isodecyl succinate; diethylene glycol dibenzoate, pentaerythritol ester; butyl oleate, methyl acetylricinoleate; tricresyl phosphate, trioctyl phosphate An adipate propylene glycol polyester, an adipate butylene glycol polyester, and the like.

  Specific examples of the thixotropic agent include aerosil (manufactured by Nippon Aerosil Co., Ltd.), disparon (manufactured by Enomoto Kasei Co., Ltd.) and the like.

Specific examples of the flame retardant include chloroalkyl phosphate, dimethyl / methyl phosphonate, bromine / phosphorus compound, ammonium polyphosphate, neopentyl bromide-polyether, brominated polyether, and the like.
Specific examples of the antistatic agent include quaternary ammonium salts; hydrophilic compounds such as polyglycols and ethylene oxide derivatives.

  The production of the tire puncture seal material of the present invention is not particularly limited. For example, a synthetic resin emulsion, a tackifier, an antifreezing agent, and an additive that can be used as needed are put in a reaction vessel to form a mixture, and the mixture is stirred using a stirrer such as a mixing mixer under reduced pressure. The method of mixing thoroughly is mentioned.

The hydrogen ion index (pH) of the tire puncture sealant of the present invention is 5.5 to 7.0 from the viewpoint that it is difficult to corrode the steel cord, has a little irritating odor, and is excellent in stability during handling. Preferably, it is 6.5 to 7.0.
In addition, the tire puncture seal material of the present invention can maintain a relatively stable state as a synthetic resin emulsion when the hydrogen ion index (pH) of the tire puncture seal material is 5.5 to 7.0. By containing a substance, the amount of ammonia or the like can be suppressed, or it is not necessary to add ammonia or the like, and the pungent odor is small.

Moreover, an acid or a base can be further added to the tire puncture sealant of the present invention to adjust the pH within the above range.
The acid is not particularly limited. Specific examples include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and phosphorous acid, and organic acids such as acetic acid, propionic acid, formic acid, butyric acid, lactic acid, malic acid, and citric acid. These may be used alone or in combination of two or more.
The base is not particularly limited and preferably has no irritating odor, and specific examples thereof include sodium hydroxide, potassium hydroxide, and tertiary amine. These may be used alone or in combination of two or more. Among these, triethylamine is preferable from the viewpoints of safety and water resistance after sealing.

The volume swelling test of the synthetic resin emulsion film will be described below.
The volume swelling test of the synthetic resin emulsion film carried out in the present invention is carried out by subjecting a synthetic resin emulsion film of volume V ₁ obtained by drying the synthetic resin emulsion at 20 ° C. for 12 hours and further drying at 50 ° C. for 10 hours. It is immersed for 7 days at 80 ° C. in a mixed liquid containing 100 parts by mass of propylene glycol and 100 parts by mass of water.

The synthetic resin emulsion film used for the volume swelling test is obtained by drying the synthetic resin emulsion contained in the tire puncture sealant of the present invention at 20 ° C. for 12 hours and further at 50 ° C. for 10 hours.
The size of the resulting synthetic resin emulsion film is 1 cm long, 2 cm wide, and 0.4 to 0.6 mm thick.
The volume of the synthetic resin emulsion should be calculated by the product of the vertical, horizontal and thickness of the resulting synthetic resin emulsion film (the length of the synthetic resin emulsion film x the width of the synthetic resin emulsion film x the thickness of the synthetic resin emulsion film). Can do. Let V ₁ be the volume of the resulting synthetic resin emulsion film.

The mixed solution in which the obtained synthetic resin emulsion film is immersed contains 100 parts by mass of propylene glycol and 100 parts by mass of water. Use a mixture that is well mixed and uniform.
When the synthetic resin emulsion film is immersed in the mixed solution, the entire synthetic resin emulsion film is immersed in the mixed solution.
The synthetic resin emulsion film immersed in the mixed solution is placed under a condition of 80 ° C. for 7 days. A container containing a mixed solution in which a synthetic resin emulsion film is immersed can be placed in a heating device such as an oven.

After the volume swelling test, the synthetic resin emulsion film is taken out from the mixed solution, and the volume of the synthetic resin emulsion film can be calculated by the product of the vertical, horizontal and thickness of the synthetic resin emulsion film taken out from the mixed solution. Let V ₂ be the volume of the synthetic resin emulsion film obtained after the volume swelling test.

The volume swelling rate of the synthetic resin emulsion film is obtained by applying the obtained volume V ₁ and volume V ₂ to the following mathematical formula (1).
Volume swelling ratio (%) of synthetic resin emulsion film = (V ₂ −V ₁ ) / V ₁ × 100 (1)
(In the formula, V ₁ is the volume of the synthetic resin emulsion film before the volume swelling test, and V ₂ is the volume of the synthetic resin emulsion film after the volume swelling test.)

In the present invention, the volume swelling ratio of the synthetic resin emulsion film is 0 to 30% from the viewpoint of excellent storage stability and sealability after heat cycle.
In addition, the volume swelling ratio of the synthetic resin emulsion film is preferably 0 to 30%, more preferably 0 to 10%, from the viewpoint of excellent storage stability and sealing properties after heat cycle.

Hereinafter, the usage method of the tire puncture sealing material of this invention is demonstrated. However, the method of using the tire puncture seal material of the present invention is not limited to the following method.
First, the tire puncture seal material of the present invention is injected into the tire from the air filling portion of the tire. The method for injecting the tire puncture sealant of the present invention into the tire is not particularly limited, and a conventionally known method can be used, and examples thereof include a method using a syringe, a spray can and the like. The amount of the tire puncture sealant injected into the tire is not particularly limited, and is appropriately selected according to the size of the puncture hole.
Next, air is filled up to a predetermined air pressure.
Then, drive the car. Aggregates such as synthetic resin particles can be formed by the compressive force and shear force received when the tire is in contact with the rotating ground, and the puncture holes can be sealed.

So far, the inventors of the present application have been researching a tire puncture seal material containing an ethylene-vinyl acetate resin emulsion as a synthetic resin emulsion.
Among them, tire puncture seal material after heat cycle assuming long-term storage (more specifically, tire puncture seal material after deterioration by heat cycle between -40 ° C. and 80 ° C.) sealability Found that there was room for improvement.
Such a decrease in sealability after heat cycle is caused by the fact that the antifreezing agent contained in the tire puncture sealant swells the synthetic resin emulsion and seals the tire puncture hole by swelling of the synthetic resin emulsion. The inventors of the present application speculate that an emulsion cannot be formed or is difficult to form.
In addition, said mechanism is a presumption of this inventor to the last, and even if it is a case where it differs from the said mechanism, it is in the range of this invention.

  Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.

1. Synthetic Resin Emulsion Film (1) Production of Synthetic Resin Emulsion Film Using the synthetic resin emulsion shown in Table 1, the synthetic resin emulsion is dried at 20 ° C. for 12 hours and further dried at 50 ° C. for 10 hours. A film having a thickness of 0.4 to 0.6 mm was obtained.

(2) Volume swelling test of synthetic resin emulsion film The volume of the synthetic resin emulsion film was calculated by the product of the length, width and thickness of the obtained synthetic resin emulsion film. Let V ₁ be the volume of the resulting synthetic resin emulsion film.
Next, the synthetic resin emulsion film is dipped in a mixed solution containing 100 parts by mass of propylene glycol and 100 parts by mass of water, placed at 80 ° C. for 7 days, pulled up from the mixed solution, and this is a synthetic resin after volume swelling test. An emulsion film was obtained.
Using the synthetic resin emulsion film after the volume swelling test, the volume of the synthetic resin emulsion film after the volume swelling test was calculated in the same manner as the volume of the synthetic resin emulsion film. The volume of the synthetic resin emulsion film after the obtained volume swell test and V _2.

(3) Volume swelling rate of synthetic resin emulsion film after volume swelling test The volume V ₁ of the synthetic resin emulsion film and the volume V ₂ of the synthetic resin emulsion film after the volume swelling test are applied to the following formula (1) to synthesize The volume swelling ratio of the resin emulsion film was calculated. The results are shown in Table 1.
Volume swelling ratio (%) of synthetic resin emulsion film = (V ₂ −V ₁ ) / V ₁ × 100 (1)
(In the formula, V ₁ is the volume of the synthetic resin emulsion film, and V ₂ is the volume of the synthetic resin emulsion film after the volume swelling test.)

The details of the synthetic resin emulsions 1 to 7 shown in Table 1 are as follows.
・ Synthetic resin emulsion 1: Sumikaflex 408HQE, manufactured by Sumika Chemtex ・ Synthetic resin emulsion 2: Sumikaflex 401HQ, manufactured by Sumika Chemtex ・ Synthetic resin emulsion 3: Sumikaflex 400HQ, manufactured by Sumika Chemtex ・ Synthetic resin emulsion 4 : Sumikaflex 305HQ, manufactured by Sumika Chemtex ・ Synthetic resin emulsion 5: Sumikaflex 7400HQ, manufactured by Sumika Chemtex ・ Synthetic resin emulsion 6: Sumikaflex 470HQ, manufactured by Sumika Chemtex ・ Synthetic resin emulsion 7: Sumikaflex 510HQ, Made by Sumika Chemtex

2. Manufacture of tire puncture sealant The components shown in Table 2 below were mixed using a stirrer with the composition (parts by mass) shown in Table 2 to obtain tire puncture sealants shown in Table 2.
N-ethyldiethanolamine was added to each obtained tire puncture sealant to adjust the pH to 5.5 to 7.0. A pH meter (manufactured by Hitachi High-Technologies Corporation) was used for measurement of pH (hydrogen ion index). The pH of the tire puncture sealant after pH adjustment is shown in Table 2.

2. Evaluation of tire puncture sealant Each tire puncture sealant was evaluated for sealability, thermal cycle stability, sealability after a thermal cycle test, and storage stability by the following methods. The results are shown in Table 2.

(1) Sealing property A puncture hole having a diameter of 2 mm was drilled in a tread groove portion of the tire, and the tire having the hole was attached to a drum testing machine.
On the other hand, each tire puncture sealant is packed in a separate plastic container, the polycontainer containing the tire puncture sealant is connected to the valve opening of the tire, and the plastic container is squeezed by hand to put the tire puncture sealant into the valve opening. Was injected into the tire.
Next, the tire was filled with air so that the internal pressure of the tire was 250 kPa, and then the obtained tire was run for 8 minutes under the conditions of a load of 350 kg and a speed of 30 km per hour.
After running, the presence or absence of air leakage was observed visually and soap water was sprayed on the tire puncture hole and the vicinity of the puncture hole.
The evaluation criteria for sealability were “◯” when there was no leakage and “x” when there was leakage.

(2) Cooling cycle stability Each tire puncture sealant was placed in a container and purged with nitrogen, and then sealed. The container was cooled at −40 ° C. for 2 hours and then heated at 80 ° C. for 2 hours. This cycle was repeated 200 times. Thereafter, the dispersion state of the tire puncture sealant was visually observed.
The evaluation criteria for the thermal cycle stability are “○” when the tire puncture sealant has no precipitate and the tire puncture sealant is uniformly dispersed, and “when the appearance (color) of the tire puncture sealant changes” “△”, and “x” when the tire puncture sealant formed an aggregate or film.

(3) Sealability after the thermal cycle test (2) Using the tire puncture seal material after the evaluation of the thermal cycle stability, a test similar to the evaluation of (1) sealability was performed.
The evaluation criteria for sealability after the thermal cycle test are the same as (1) evaluation criteria for sealability.

(4) Storage stability A tire puncture sealant was placed in a container, purged with nitrogen, and then sealed, and the container was placed at 80 ° C. for 30 days. Thereafter, the state of the tire puncture sealant was observed, and the dispersion state was visually observed.
The evaluation criteria for storage stability are “○” when the tire puncture sealant has no precipitate and the tire puncture sealant is uniformly dispersed, and “△” when the appearance (color) of the tire puncture sealant is changed. The case where the tire puncture sealant formed an aggregate or a film was indicated as “x”.

Details of the components shown in Table 2 are as follows.
Synthetic resin emulsions 1 to 7: Synthetic resin emulsions shown in Table 1. Tackifier: Harrier Star SK508H, manufactured by Harima Chemicals, solid content 55 mass%, pH 6.5
-Antifreeze agent: propylene glycol, manufactured by Wako Pure Chemical Industries, Ltd., solid content: 100% by mass
In addition, the amount of the synthetic resin emulsions 1 to 7 and the tackifier described in Table 2 is an amount as an emulsion.

As is apparent from the results shown in Table 2, Comparative Examples 1 to 8 containing a synthetic resin emulsion having a volume swelling ratio exceeding 30% were inferior in sealability after the heat cycle.
On the other hand, Examples 1-18 were excellent in the storage stability and the sealing performance after a heat cycle.

Claims (8)

Contains a synthetic resin emulsion, a tackifier, and an antifreeze agent,
A synthetic liquid emulsion having a volume of V ₁ obtained by drying the synthetic resin emulsion at 20 ° C. for 12 hours and further drying at 50 ° C. for 10 hours, a mixed solution containing 100 parts by mass of propylene glycol and 100 parts by mass of water. The volume swelling test of the synthetic resin emulsion film, which is immersed for 7 days under the condition of 80 ° C., is performed, and the volume V ₂ of the synthetic resin emulsion film after the volume swelling test is measured, and the volume V ₁ and the volume are measured. A tire puncture sealant in which the volume swelling ratio of the synthetic resin emulsion film is 0 to 30%, which is obtained by applying V ₂ to the following formula (1).
Volume swelling ratio (%) of synthetic resin emulsion film = (V ₂ −V ₁ ) / V ₁ × 100 (1)
(In the formula, V ₁ is the volume of the synthetic resin emulsion film before the volume swelling test, and V ₂ is the volume of the synthetic resin emulsion film after the volume swelling test.)   The tire puncture sealant according to claim 1, wherein the synthetic resin emulsion is an ethylene-vinyl acetate resin emulsion.   The tire puncture sealing material according to claim 2, wherein a mass ratio (ethylene / vinyl acetate) of ethylene and vinyl acetate as a monomer constituting the ethylene-vinyl acetate resin emulsion is 20/80 to 50/50.   The tire puncture sealant according to claim 2 or 3, wherein the surfactant used in the ethylene-vinyl acetate resin emulsion is polyvinyl alcohol.   The tire puncture sealing material according to claim 4, wherein the saponification degree of the polyvinyl alcohol is 65 to 95 mol%.   The tire puncture sealing material according to any one of claims 1 to 5, wherein a solid content of the tackifier is 20 to 200 parts by mass with respect to 100 parts by mass of the solid content of the synthetic resin emulsion.   The tire puncture sealant according to any one of claims 1 to 6, wherein the amount of the antifreezing agent is 100 to 500 parts by mass with respect to 100 parts by mass of the solid content of the synthetic resin emulsion.   The tire puncture sealant according to any one of claims 1 to 7, which has a hydrogen ion index of 5.5 to 7.0.