JP2009280690A - Adhesive composition for tire label - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive composition for tire labels, which is excellent in adhesiveness and environmental protection, ensures flexibility, improves dynamic durability, and is suitable for adhering to the surfaces of tire sidewall portions. <P>SOLUTION: Provided is the room temperature-curable adhesive composition characterized by containing a urethane prepolymer having a plurality of isocyanate group terminals in the molecule as a main component, containing an aromatic polyamine compound and/or an oxazolidine compound, blending an aminic compound containing no ketimine in an amount of 0.8 to 1.4 equivalents per equivalent of the isocyanate group, blending a polyisocyanate oligomer in an amount of 0 to 40 pts.wt. per 100 pts.wt. of the urethane prepolymer, and having a stress on 1 to 50% tensile deformation of the adhesive composition, after cured, in a quantity of ≤1.5 times a stress, when the tensile deformation of the surface rubber of the sidewall portion is identical. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to an adhesive composition for tire labels, and more specifically, it is excellent in adhesion and environmental conservation, secures flexibility and improves dynamic durability, thereby providing tires on the surface of sidewall portions of tires. The present invention relates to an adhesive composition for a tire label suitable for attaching a label.

  There is a tire label that displays a logo or the like that is affixed to the surface of a sidewall portion of a pneumatic tire for decoration or the like (see, for example, Patent Document 1). As a method of attaching such a tire label to the sidewall portion surface, there are a method by vulcanization adhesion and a method using an adhesive. Since the method using an adhesive is simpler than vulcanization bonding, there is an advantage that a user can easily attach a tire label that suits his / her preference to a purchased pneumatic tire.

However, since the surface of the sidewall portion of the pneumatic tire is composed of vulcanized rubber, conventional urethane, epoxy and silicone adhesives are excluded except chloroprene rubber adhesives and cyanoacrylate adhesives. Then, sufficient adhesive strength could not be obtained. Moreover, since the chloroprene rubber adhesive contains a large amount of toluene as a solvent, it should not be used for environmental protection. In addition, the chloroprene rubber adhesive has sufficient peel strength statically, but because it peels when subjected to repeated expansion and contraction and centrifugal force during tire running, like the sidewall surface of a pneumatic tire, It could not be used for bonding with tires. Although the cyanoacrylate adhesive has a sufficient peel strength statically, it does not have flexibility after curing, so it peels off during running of the tire and is insufficient in dynamic durability and cannot be used.
Japanese Patent Laid-Open No. 10-187044

  An object of the present invention is a tire label suitable for adhering a tire label to the surface of a sidewall portion of a tire by ensuring flexibility and improving environmental durability while being excellent in adhesiveness and environmental conservation. It is to provide an adhesive composition.

  The tire label adhesive composition of the present invention that achieves the above object is a room temperature curable tire label adhesive composition for sticking a tire label to the surface of a sidewall portion of a tire, and the adhesive composition thereof. The main component is a urethane prepolymer having a plurality of isocyanate group terminals in the molecule, and an amine compound is blended in an amount of 0.8 to 1.4 equivalents with respect to the isocyanate group, and a polyisocyanate oligomer is mixed with the urethane prepolymer. 0 to 40 parts by weight per 100 parts by weight, and the amine compound comprises an aromatic polyamine compound and / or an oxazolidine compound and does not contain ketimine, and 1% to 1% of the adhesive composition after curing The stress at the time of 50% tensile deformation is the stress when the amount of tensile deformation of rubber on the sidewall surface is the same. Characterized in that at .5 times or less.

  This adhesive composition for tire labels can be suitably used when a tire label is stuck on a sidewall portion of a pneumatic tire.

  The tire label adhesive composition of the present invention comprises a urethane prepolymer having a plurality of isocyanate group terminals in the molecule as a main component, an aromatic polyamine compound and / or an oxazolidine compound as a curing agent, and an amine not containing ketimine. In addition to blending the amount of the compound to 0.8 to 1.4 equivalents with respect to the isocyanate group, the polyisocyanate oligomer is blended in an amount of 0 to 40 parts by weight with respect to 100 parts by weight of the urethane prepolymer. As a result, the environmental conservation is excellent, and the adhesive force between the tire label and the tire sidewall portion surface can be increased. In addition, the stress at the time of 1% to 50% tensile deformation of the cured adhesive composition was set to be 1.5 times or less of the stress when the amount of tensile deformation of the rubber on the sidewall portion surface was made the same. Therefore, the flexibility of the adhesive composition after curing is maintained even on the surface of the sidewall portion where the deformation during running of the tire is large, and the dynamic durability can be improved.

  1A and 1B show an example of a tire label, where FIG. 1A is a plan view, FIG. 1B is a side view seen from the k direction of FIG. It is a side view which shows an example of a entering tire, 1 is a tire label and T is a pneumatic tire.

  1A and 1B, a tire label 1 is composed of a base material layer 2 and a cover layer 3, and a logo, a mark or the like is printed on the surface 2a of the base material layer 2 on the cover layer 3 side by silk printing or offset printing. Design is given. The surface 2b on the opposite side of the base material layer 2 is attached to the surface of the sidewall portion of the pneumatic tire T via an adhesive. The base material layer 2 is made of an elastic material mainly composed of a rubber component such as natural rubber or synthetic rubber, and gives flexibility to the tire label 1 formed by being laminated with the cover layer 3. As the elastic material constituting the base material layer 2, styrene butadiene rubber, acrylonitrile butadiene rubber, and chloroprene rubber are preferable. The cover layer 3 is made of a flexible and transparent resin, and examples thereof include a polyester resin, a polyolefin resin, a polyurethane resin, and the like. Among these, a polyurethane resin is preferable.

  As shown in FIG. 2, the tire label 1 is attached to the surface Ta of the sidewall portion T1 of the pneumatic tire T with an adhesive. The surface Ta of the sidewall portion T1 of the pneumatic tire T is formed, for example, by vulcanizing a natural rubber, isoprene rubber, butadiene rubber, styrene butadiene rubber, acrylonitrile butadiene rubber, butyl rubber or the like or a rubber composition blended with these. ing. Therefore, sufficient adhesive strength could not be obtained even if the tire label was attached using a conventional urethane, epoxy, or silicone adhesive. Further, as described above, although the chloroprene rubber adhesive has a large adhesive strength, it should not be used for environmental protection because it contains a large amount of toluene as a solvent. In addition, since the cyanoacrylate adhesive has no flexibility after curing, there is a problem inherent to a pneumatic tire that the tire label is peeled off during running of the tire and the dynamic durability is insufficient.

  Even if the adhesive composition for tire labels of the present invention is used on the surface of a tire sidewall portion that repeatedly undergoes large deformation during tire running, the cured adhesive composition maintains flexibility, so tire running Sometimes the label does not peel off, and the dynamic durability is excellent.

  In the present invention, the relationship between the flexibility of the cured adhesive composition and the rubber constituting the sidewall surface of the tire is such that the stress during tensile deformation of the adhesive composition is 1% to 50%. The amount of tensile deformation of the rubber on the surface is made to be 1.5 times or less, preferably 1.0 times or less of the stress when made the same. If the stress of the adhesive composition after curing is higher than 1.5 times the stress of rubber, the flexibility will be insufficient and it will not be possible to follow changes in the surface of the sidewall during tire running, and peeling will occur easily. Dynamic durability deteriorates. Further, the lower limit of the stress of the adhesive composition is not particularly limited, but is preferably about 0.2 times the stress of rubber in order to ensure adhesion.

  In the present invention, the cured adhesive composition and the stress of the rubber constituting the surface of the sidewall portion of the tire are subjected to a tensile test in accordance with JIS K6251 at a tensile speed of 500 mm / min. Each stress is in the range of 1% to 50%.

  The tire label adhesive composition of the present invention is mainly composed of a urethane prepolymer having a plurality of isocyanate group terminals in the molecule. The urethane prepolymer is preferably liquid at room temperature from the viewpoint of handling. A urethane prepolymer is a reaction product obtained by reacting a polyol compound and a polyisocyanate compound, and is a polymer containing a plurality of isocyanate groups at the molecular ends. This isocyanate group may be bonded to either an aromatic hydrocarbon or an aliphatic hydrocarbon.

  Examples of the polyisocyanate compound include 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), 4,4′-diphenylmethane diisocyanate (MDI), 2 , 4'-diphenylmethane diisocyanate (2,4'-MDI), 1,4-phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, tolidine diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI), hexamethylene diisocyanate (HDI) Xylylene diisocyanate (XDI), isophorone diisocyanate (IPDI), tetramethylxylylene diisocyanate (TMXDI), and the like. A polyisocyanate compound can be used individually or in combination of 2 types or more, respectively.

  It does not specifically limit as a polyol compound, For example, any of polyether polyol, polyester polyol, acrylic polyol, polycarbonate polyol, and another polyol may be sufficient. These polyols may be used alone or in combination. Specifically, polyethylene glycol, polypropylene glycol, polyoxyethylene glycol, polyoxypropylene glycol, polyoxypropylene triol, polytetramethylene ether glycol, polymer polyol, poly (ethylene adipate), poly (diethylene adipate), poly (propylene) Adipate), poly (tetramethylene adipate), poly (hexamethylene adipate), poly (neopentylene adipate), poly-ε-caprolactone, poly (hexamethylene carbonate), silicone polyol and the like are preferable. A natural polyol compound such as castor oil may be used.

  Moreover, since the polyol compound has excellent physical properties after curing, a polyether polyol having a number average molecular weight of 1500 to 15000 is preferable, and a polyether polyol having 2000 to 10,000 is more preferable.

  The combination of the polyol compound and the polyisocyanate compound is not particularly limited, and each of the polyol compound and each of the polyisocyanate compound can be arbitrarily combined. Specifically, for example, it is obtained from at least one selected from the group consisting of polyoxyethylene glycol, polyoxypropylene glycol and polyoxypropylene triol and at least one selected from the group consisting of TDI, MDI and XDI. Urethane prepolymers are preferred from the viewpoints of physical property adjustment, cost, and availability.

  The mixing ratio of the polyol compound and the polyisocyanate compound is preferably such that the molar ratio (NCO / OH) of the isocyanate group in the polyisocyanate compound to the hydroxy group in the polyol compound is 1.3 to 2.5. More preferably, it is 5 to 2.3. In such a range, the viscosity of the urethane prepolymer is moderate and the elongation of the cured product is excellent.

  The reaction between the polyol compound and the polyisocyanate compound is not particularly limited, and examples thereof include a method in which the polyol compound and the polyisocyanate compound having the above-mentioned quantitative ratio are heated and stirred at 50 to 100 ° C. It is done. If necessary, a urethanization catalyst such as an organic tin compound, an organic bismuth, or a tertiary amine can be used.

  The amine compound blended as a curing agent in the tire label adhesive composition of the present invention contains an aromatic polyamine compound and / or an oxazolidine compound and does not contain ketimine. The ketimine is composed of a compound having a> C═N bond (ketimine bond) derived from a carbonyl compound and an amine, and includes an aldimine having a —HC═N bond.

  By using an amine compound composed of an aromatic polyamine compound and / or an oxazolidine compound as a curing agent, it can be cured at room temperature and can be used for a long period of time, which is suitable as an adhesive for tire labels. The pot life is preferably 10 minutes or longer, more preferably 10 to 50 minutes.

  The aromatic polyamine compound is an aromatic compound having at least two amino groups in the molecule and is not particularly limited as long as it is usually used as a curing agent. Examples of the aromatic polyamine compound include 4,4′-methylenebis (3-chloro-2,6-diethylaniline), 4,4′-methylenebis (2-chloroaniline) (MOCA), and 4,4′-diamino. Diphenylmethane, 2,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,4-diaminophenol, 2 , 5-diaminophenol, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,3-tolylenediamine, 2,4-tolylenediamine, 2,5-tolylenediamine, 2,6-tolylenediamine Range amine, 3,4-tolylenediamine, diethyltoluenediamine (DETDA), vinyl (Methylthio) include toluene diamine and the like. Of these, MOCA and DETDA are preferable.

  The oxazolidine compound does not function as a curing agent until the amine is regenerated by hydrolysis with water, and is a latent cure that regenerates the amine by hydrolysis with water in the air or water contained in the composition. It is an agent. The oxazolidine compound can be used as a curing agent for a two-component adhesive or a one-component moisture-curable adhesive composition.

  An oxazolidine compound is a compound having a saturated 5-membered heterocyclic ring containing oxygen and nitrogen, and having an oxazolidine ring that opens in the presence of moisture (water) and reacts with an isocyanate group to cure. Specifically, N-hydroxyalkyl oxazolidine and its polyisocyanate adduct, oxazolidine silyl ether, carbonate oxazolidine, ester oxazolidine and the like can be mentioned.

  The oxazolidine compound is preferably a primary hydroxyl group-containing oxazolidine compound among the above oxazolidine compounds or a polyfunctional oxazolidine compound containing two or more oxazolidine rings in the compound.

  Specific examples of the primary hydroxyl group-containing oxazolidine compound include N-hydroxyalkyloxazolidine, for example, 2-isopropyl-3- (2-hydroxyethyl) oxazolidine, 2- (1-methylbutyl) -3- (2- Hydroxyethyl) oxazolidine, 2-phenyl-3- (2-hydroxyethyl) oxazolidine, 2- (p-methoxyphenyl) -3- (2-hydroxyethyl) oxazolidine, 2- (2-methylbutyl) -3- (2 -Hydroxyethyl) -5-methyloxazolidine. Such an N-hydroxyalkyloxazolidine may be prepared by a dehydration condensation reaction between an alkanolamine and a ketone or aldehyde.

The compounding quantity of an amine compound is 0.8-1.4 equivalent by the equivalent with respect to the isocyanate group in a urethane prepolymer, Preferably it is good to set it as 0.9-1.1 equivalent. Here, the equivalent refers to the molar ratio (NH ₂ / NCO) of the amino group (NH ₂ ) in the amine compound to the isocyanate group (NCO) in the urethane prepolymer. When the compounding amount of the amine compound is less than 0.8 equivalent or exceeds 1.4 equivalent, curing of the urethane prepolymer becomes incomplete and the adhesive strength is insufficient.

  The tire label adhesive composition of the present invention is a two-part adhesive or one-part adhesive composed of the urethane prepolymer and amine compound described above, and cures at room temperature and has a workability for label sticking. Fast curing speed while maintaining good pot life. Further, since it does not contain volatile organic compounds such as toluene and xylene, it is preferable from the viewpoint of environmental protection, and it is suitable for the user to stick the tire label on the surface of the sidewall part.

  In this invention, a polyisocyanate oligomer can be mix | blended as an arbitrary component. By mix | blending a polyisocyanate oligomer, the adhesive strength of a tire label and a tire sidewall part surface can be made high. The polyisocyanate oligomer is a dimer or trimer of a polyisocyanate monomer, and may be a trimer.

  Although it does not restrict | limit especially as a polyisocyanate monomer, Hexamethylene diisocyanate (HDI), TDI, IPDI etc. can be illustrated.

  The polyisocyanate monomer trimer is preferably in the form of a biuret or isocyanurate. The polyisocyanate oligomer is preferably an HDI biuret, HDI, TDI, IPDI, or TMXDI isocyanurate. Among them, the chain biuret body tends to have a lower modulus than the cyclic isocyanurate body, and the HDI biuret body is preferred.

  The compounding quantity of a polyisocyanate oligomer is 0-40 weight part with respect to 100 weight part of urethane prepolymers. If the blending amount of the polyisocyanate oligomer exceeds 40 parts by weight, the cured adhesive composition becomes too hard, so that it is difficult to follow the deformation of the sidewall part during running of the tire, and peeling easily occurs. Durability deteriorates. Moreover, when mix | blending a polyisocyanate oligomer, it is good to mix | blend preferably 10 weight part or more, and can make adhesive strength still higher.

  The tire label adhesive composition may contain other compounding agents as long as the object of the present invention is not impaired. Examples of the compounding agent include a curing catalyst, a filler, a plasticizer, an antioxidant, an anti-aging agent, an inorganic pigment, an organic pigment, an adhesion imparting agent, a flame retardant, a dehydrating agent, a solvent, a silane coupling agent, and a thixotropy imparting agent. And antistatic agents. The amount of the compounding agent is not particularly limited, and an amount that can be generally used in the urethane-based adhesive composition can be blended. The plasticizer may be added to dissolve the solid amine compound.

  Examples of the filler include organic or inorganic materials of various shapes, such as carbon black, calcium carbonate, silica (white carbon), clay talc, iron oxide, zinc oxide, titanium oxide, barium oxide, magnesium oxide, quick lime, Carbonates (eg, magnesium carbonate, zinc carbonate, flour), alumina hydrate (eg, hydrous aluminum hydroxide), diatomaceous earth, barium sulfate (eg, precipitated barium sulfate), mica, alumina sulfate, lithopone, graphite, Examples include molybdenum disulfide, pumice powder, glass powder, silica sand, zeolite, and surface treated products such as these fatty acids, resin acids, fatty acid esters, and higher alcohol-added isocyanate compounds, glass balloons, and resin balloons.

  Examples of calcium carbonate include heavy calcium carbonate, precipitated calcium carbonate (light calcium carbonate), colloidal calcium carbonate, and the like. Moreover, the surface treatment calcium carbonate surface-treated with a fatty acid, a resin acid, a fatty acid ester, a higher alcohol addition isocyanate compound, etc. can also be used. Specifically, as calcium carbonate surface-treated with fatty acids, Calfine 200 (manufactured by Maruo Calcium Co., Ltd.), Viscolite MBP (manufactured by Shiraishi Calcium Co., Ltd.), Whiteon 305 (heavy calcium carbonate, manufactured by Shiraishi Calcium Co., Ltd.), As calcium carbonate surface-treated with a fatty acid ester, Sealet 200 (manufactured by Maruo Calcium Co., Ltd.) or the like is preferably used. Among these, those surface-treated with fatty acids, fatty acid esters, higher alcohol addition isocyanate compounds, and the like are particularly preferable. The surface-treated calcium carbonate contributes to shape retention and workability because the viscosity is increased, and contributes to storage stability because the surface is hydrophobic.

  Examples of the silica include fumed silica, calcined silica, precipitated silica, pulverized silica, fused silica, anhydrous fine powder silicic acid, hydrous fine powder silicic acid, hydrous aluminum silicate, hydrous calcium silicate, and the like.

  The blending amount of the filler is preferably 10 to 200 parts by weight and more preferably 20 to 80 parts by weight with respect to 100 parts by weight of the urethane prepolymer. When the blending amount of the filler is within this range, the obtained adhesive composition of the present invention has good workability and excellent reinforcing effect.

  The adhesive composition for tire labels of the present invention can be suitably used when the tire label is attached to the surface of the sidewall portion. In this way, pneumatic tires with tire labels attached to the tire sidewalls not only have high static adhesion to the tire labels, but also have a dynamic durability that is difficult to peel off even when subjected to repeated large deformations during tire running. High nature. The type of pneumatic tire is not particularly limited, but passenger tires, truck / bus tires, and racing tires are suitable.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, the scope of the present invention is not limited to these Examples.

  A main agent composed of the compositions shown in Tables 1 and 2 was prepared by the following method, curing agents A to D composed of the compositions shown in Table 3 were prepared, and the main component and the curing agent were combined as a two-part adhesive. Each of the curing agents was blended into the main agent so as to have the equivalents shown in Tables 1 and 2, and 13 types of mixed adhesive compositions (Examples 1 to 9 and Comparative Examples 1 to 4) were prepared. The usable time, peel strength, flexibility, stress at 20% elongation, and tensile elongation at break of the obtained 13 types of adhesive compositions were evaluated by the following methods. In addition, since the adhesive composition of Comparative Example 4 had a very short pot life and was difficult to apply, a predetermined test piece for evaluation could not be prepared.

  Moreover, 12 types of adhesive compositions (Examples 1-9, Comparative Examples 1-3) except the comparative example 4 were used, and the tire label of FIG. 1 was made into tire size 185 / 60R14 like FIG. A pneumatic tire adhered to two locations on the surface of the sidewall portion of the tire was obtained. The base material layer of the tire label was composed of chloroprene rubber, and the rubber on the sidewall surface was composed of a rubber composition having the composition shown in Table 4. A drum running test of a pneumatic tire with a tire label attached was performed by the following method.

Preparation of main agent As shown in Tables 1 and 2, a TDI prepolymer prepared by the following method was used as a urethane prepolymer, and HDI biuret, silane coupling agent, calcium carbonate and silica were mixed in predetermined amounts to prepare a main agent. .

TDI prepolymer Polyol compound consisting of 20 g of polypropylene ether triol (G-3000, number average molecular weight Mn3000, manufactured by Asahi Glass Co., Ltd.) and 80 g of polypropylene ether diol (D-2000, number average molecular weight Mn2000, manufactured by Asahi Glass Co., Ltd.) is treated with tolylene diisocyanate (TDI). The NCO / OH molar ratio with Cosmonate T-80 manufactured by Mitsui Chemicals Polyurethane Co., Ltd. was adjusted to 2.0 and reacted in a nitrogen stream at 80 ° C. with stirring for 8 hours to obtain a TDI prepolymer. It was.

Evaluation of tire label adhesive composition Pot life The obtained main agent and curing agent were mixed, the time [min] from the start of mixing until the surface was covered was measured, and the results obtained are shown in Tables 1 and 2.

2. Peel strength A chloroprene rubber sheet having a length of 200 mm, a width of 150 mm, and a thickness of 2 mm and a natural rubber sheet having the same size were prepared as adherends. Each adhesive composition was applied to a sheet of chloroprene rubber so as to be 0.2 kg / m ^2, and a natural rubber sheet was bonded thereto to obtain an adhesive. The obtained adhesive was cured by curing for 7 days under conditions of 23 ° C. and 55% RH. Next, based on the T-type peel test method of JIS K6854-3, the peeled force (unit: N / 25 mm) under the condition of a tensile speed of 100 mm / min is measured and the average value is obtained for the cured adhesive body. This value was taken as the peel strength, and the results are shown in Tables 1 and 2.

3. Stress at 20% elongation, elongation at break at break, and flexibility The adhesive composition obtained by mixing the obtained main agent and curing agent was applied on a Teflon (registered trademark) sheet and cured at 20 ° C. and 55% RH for 7 days. did. Thereafter, a dumbbell-shaped No. 3 test piece having a thickness of 2 mm was cut out from the cured product. Using each dumbbell-shaped No. 3 test piece, a tensile test (tensile speed: 500 mm / min) was conducted according to JIS K6251, and the stress at 20% elongation [N / mm ² ] and tensile elongation at break [%] Was measured. The obtained results are shown in Tables 1 and 2, respectively.

A rubber composition having a composition shown in Table 4 was used to prepare a vulcanized sheet having a thickness of 2 mm, and a dumbbell-shaped No. 3 specimen was cut out. Using this test piece, a tensile test (tensile speed: 500 mm / min) was performed according to JIS K6251 to measure a stress [N / mm ² ] at 20% elongation. The stress at 20% elongation of the rubber constituting the surface of the sidewall portion was 0.40 N / mm ² .

Also, the stress in the 1-50% elongation region during the tensile test was compared between the adhesive composition and the rubber constituting the sidewall surface, and the flexibility was evaluated according to the following criteria. The results obtained are shown in Table 1. , 2.
○: The stress of the adhesive composition is not more than 1.5 times the stress of the rubber of the sidewall portion in the entire region of 1 to 50% elongation. Is more than 1.5 times the stress of rubber in the sidewall

4). Drum running test Fifteen types of tires with tire labels attached are mounted on a rim (5.5 JJ x R14), air pressure is 200 kPa, an indoor drum tester (drum diameter 1707 mm) compliant with JIS D4230, and JISMA specified load Then, a drum running test of 3000 km was performed under the condition of a speed of 80 km / h, and the running distance until the tire label peeled was measured. When the tire label did not peel off after traveling for 3000 km, it was set as “over 3000 km” and the results are shown in Tables 1 and 2.

The types of raw materials used in Tables 1 and 2 are shown below.
HDI biuret: HDI biuret body, Death Module N3200 manufactured by Sumika Bayer
Silane coupling agent: γ-glycidoxypropyltrimethoxysilane, Shin-Etsu Chemical KBM403
Octyl acid: Wako Pure Chemical Industries calcium carbonate: Fatty acid-treated calcium carbonate, Maruo Calcium Calfine 200
Silica: Nippon Aerosil Co., Ltd. R972

In Table 3, the types of raw materials used are shown below.
MOCA: 4,4′-methylenebis (2-chloroaniline), Iharacamine-MT manufactured by Ihara Chemical Industry Co., Ltd.
DETDA: diethyltoluenediamine, Ethacure 100 manufactured by Ethyl Corporation
Oxazolidine A: 2- (1-methylbutyl) -3- (2-hydroxyethyl) oxazolidine NBDA: norbornanediamine, DOP manufactured by Mitsui Chemicals, Inc .: Bis (2-ethylhexyl) phthalate, Sunsizer DOP manufactured by Shin Nippon Rika Co., Ltd.
Carbon black: Shin Nikka Carbon # 20Y
The same calcium carbonate and silica as in Tables 1 and 2 were used.

In addition, the kind of raw material used in Table 4 is shown below.
NR: natural rubber, RSS # 1
BR: butadiene rubber, Nipol BR1220 manufactured by Nippon Zeon
Carbon black: HTC 100 manufactured by Chubu Carbon Co.
Zinc Oxide: Toho Zinc Co., Ltd., Silver Zinc Hana, Stearic Acid: Industrial Stearic Acid, Kao Soap Co., Ltd. Lunac YA
Anti-aging agent 1: Nocrack 6C manufactured by Ouchi Shinsei Chemical Co., Ltd.
Antiaging agent 2: Nocrack 224 manufactured by Ouchi Shinsei Chemical Co., Ltd.
Wax: Microcrystalline wax, Sannok oil manufactured by Ouchi Shinsei Chemical Co., Ltd .: Aromatic process oil, KOMOlex 300 manufactured by Nippon Oil Corporation
Vulcanization accelerator: NOCELLER DM manufactured by Ouchi Shinsei Chemical
Sulfur: Powder sulfur produced by Karuizawa Refinery

(A) (B) is an example of the tire label stuck using the adhesive composition of this invention, (A) is a plain view, (B) is a side view. 1 is a side view of a tire in which a tire label is attached to a surface of a sidewall portion of a pneumatic tire.

Explanation of symbols

1 Tire label T Pneumatic tire T1 Side wall part Ta Side wall part surface

Claims (2)

  A room temperature curable adhesive composition for tire labels, in which a tire label is attached to the surface of a sidewall portion of a tire, the adhesive composition comprising a urethane prepolymer having a plurality of isocyanate group ends in a molecule. Main component, 0.8 to 1.4 equivalents of amine compound in terms of equivalent to isocyanate group, 0 to 40 parts by weight of polyisocyanate oligomer with respect to 100 parts by weight of urethane prepolymer, and amine compound Comprises an aromatic polyamine compound and / or an oxazolidine compound and no ketimine, and the adhesive composition after curing has a stress at the time of tensile deformation of 1% to 50% of the rubber on the sidewall surface. An adhesive composition for a tire label that is 1.5 times or less of the stress when the amount of tensile deformation is the same.   A pneumatic tire in which a tire label is attached to a sidewall portion of the tire using the tire label adhesive composition according to claim 1.

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