JP3449817B2 - Pneumatic tire and method of manufacturing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a pneumatic tire having an air permeation preventive layer excellent in adhesiveness with a rubber layer as well as to reduce the weight of the tire without impairing air pressure retention in the tire. It relates to a manufacturing method.

[0002]

2. Description of the Related Art Reducing the fuel consumption rate is one of the major technical problems in automobiles, and as part of this measure, there is an increasing demand for weight reduction of pneumatic tires.

By the way, an inner liner layer made of rubber having low gas permeability such as butyl rubber is provided on the inner surface of the pneumatic tire in order to keep the tire air pressure constant. However, since halogenated butyl rubber has a large hysteresis loss, after vulcanization of the tire,
In the gap between the carcass cords, when the inner surface rubber of the carcass layer and the inner liner layer are corrugated, the inner liner rubber layer is deformed along with the deformation of the carcass layer, which causes a problem of increased rolling resistance. Therefore, in general, the inner liner layer (halogenated butyl rubber) and the inner surface rubber of the carcass layer are joined together via a rubber sheet called tie rubber having a small hysteresis loss. Therefore, in addition to the thickness of the inner liner layer of halogenated butyl rubber, the thickness of tie rubber is added, resulting in a layer thickness of more than 1 mm (1000 μm), resulting in an increase in the weight of the product tire. It was one.

Techniques have been proposed in which various materials are used in place of low gas permeability rubber such as butyl rubber for the air permeation preventive layer of pneumatic tires. For example, Japanese Patent Publication No. 47-3
No. 1761 discloses that an inner surface of a vulcanized tire has an air permeability coefficient [cm ³ (standard state) / cm · sec · mmHg] of 1.0 at 30 ° C.
× 10 ^-12 or less, of 5.0 × 10 ^-12 or less at 70 ° C., polyvinylidene chloride, saturated polyester resin, a solution or dispersion of a synthetic resin such as polyamide resin be applied in 0.1mm or less is disclosed ing.

However, the technique disclosed in this publication is
It is stated that a synthetic resin coating layer having a specific air permeability coefficient is provided on the inner peripheral surface of the carcass of the vulcanized tire or on the inner peripheral surface of the inner liner so that the thickness of the synthetic resin coating layer is 0.1 mm or less. However, the pneumatic tire described in this publication has a problem in adhesiveness between rubber and synthetic resin. It should be noted that this publication does not describe the use of alkoxyalkylated polyamide.

JP-A-5-330307 discloses that the inner surface of a tire is subjected to a halogenation treatment (using a conventionally known chlorination treatment liquid, a bromine solution and an iodine solution), and a methoxymethylated nylon, Polymer film of polymerized nylon, blend of polyurethane and polyvinylidene chloride, blend of polyurethane and polyvinylidene fluoride (film thickness 1
However, the adhesiveness is still insufficient, and there is still a problem.

Further, in Japanese Patent Laid-Open No. 5-318618,
A pneumatic tire using a methoxymethylated nylon thin film as an inner liner is disclosed. According to this technique, a methoxymethylated nylon solution or emulsion is sprayed or applied on the inner surface of a green tire, and then the tire is vulcanized. Alternatively, a pneumatic tire is manufactured by spraying or applying a solution or emulsion of methoxymethylated nylon onto the inner surface of the tire after vulcanization. However, since the tire inner surface rubber and the methoxymethylated nylon are not adhered in the technology disclosed in this publication, the methoxymethylated nylon film peels from the tire inner surface rubber when the tire is used under high load. However, there is still a problem that the inner liner layer is inferior in moisture resistance (or water resistance) and heat resistance due to the fact that methoxymethylated nylon is not crosslinked or cured. More broadly, there is no disclosure of the use of alkoxyalkylated nylons and the corresponding crosslinking or curing methods.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to use an air permeation preventive layer which can reduce the weight of a tire without impairing the air pressure retention of the tire and which has excellent adhesiveness with a rubber layer. The present invention provides a pneumatic tire and a manufacturing method thereof.

[0009]

According to the present invention, a thin film of at least one aliphatic polyamide resin in which at least a part of amide groups is modified with an alkoxyalkyl group is empty.
As an air permeation preventive layer, the rubber and voids of the carcass layer are
Phenolic resin type adhesive that reacts with the resin of the air permeation preventive layer
Adhesive, chlorinated rubber adhesive or isocyanate adhesive
A pneumatic tire formed by laminating via an adhesive is provided.

According to the present invention, the carcass layer of the green tire made of unvulcanized rubber or the surface of the rubber layer provided on the surface of the carcass layer of the green tire is treated with a carcass layer of the unvulcanized rubber during vulcanization.
Phenol that reacts with the rubber and resin of the air permeation preventive layer
Resin adhesive, chlorinated rubber adhesive or isocyanate
After spraying or applying a system adhesive , a liquid composition containing at least one aliphatic polyamide resin in which at least a part of amide groups is modified with an alkoxyalkyl group is sprayed or applied on the adhesive surface, and then, A method for manufacturing a pneumatic tire, which comprises vulcanizing the green tire is provided.

According to the present invention, the rubber of the carcass layer and the air permeation preventive layer during vulcanization are further provided on the surface of the carcass layer of the tire after vulcanization or on the surface of the rubber layer provided on the surface of the carcass layer.
Phenolic resin adhesives and salts that undergo an adhesive reaction with the resin of the stop layer
A liquid composition containing at least one aliphatic polyamide resin in which at least a part of amide groups is modified with an alkoxyalkyl group on the adhesive surface after spraying or applying a synthetic rubber adhesive or an isocyanate adhesive . A method for manufacturing a pneumatic tire is provided, which comprises spraying or applying.

According to the present invention, furthermore, a fat obtained by crosslinking at least one aliphatic polyamide resin in which at least a part of amide groups is modified with an alkoxyalkyl group by heat treatment in the presence of an acid catalyst. A thin film of group-polyamide resin is applied to the
Phenolic resin type adhesive that reacts with the resin of the air permeation preventive layer
Provided is a pneumatic tire which is laminated as an air permeation preventive layer through a binder, a chlorinated rubber adhesive or an isocyanate adhesive .

According to the present invention, the carcass layer on the surface of the carcass layer of the green tire made of unvulcanized rubber or the surface of the rubber layer provided on the surface of the carcass layer is further carcassed during vulcanization.
The rubber that is adhesively reacted with the rubber of the layer and the resin of the air permeation preventive layer.
Knoll resin adhesive, chlorinated rubber adhesive or isocyanate
After spraying or applying a salt adhesive, an acid catalyst is added to the liquid composition containing at least one aliphatic polyamide resin in which at least a part of the amide groups is modified with an alkoxyalkyl group on the surface of the adhesive. There is provided a method for producing a pneumatic tire, which comprises spraying or applying the prepared liquid and then vulcanizing the green tire.

According to the present invention, furthermore, the rubber and air permeability of the carcass layer are vulcanized during vulcanization on the surface of the carcass layer of the tire after vulcanization or on the surface of the rubber layer provided on the surface of the carcass layer.
Phenolic resin-based adhesive that reacts with the resin of the overcoat layer
Agent, a chlorinated rubber-based adhesive or an isocyanate-based adhesive is sprayed or applied, and then a liquid containing at least one aliphatic polyamide-based resin in which at least a part of amide groups is modified with an alkoxyalkyl group on the adhesive surface. There is provided a method for producing a pneumatic tire, which comprises spraying or applying a solution to which an acid catalyst has been added to the composition, and then heating.

According to the present invention, further, (i) at least one amide group is modified with an alkoxyalkyl group and / or a group having a curable unsaturated bond, and at least one aliphatic polyamide resin and ( ii) The surface of the carcass layer of the pneumatic tire or the surface of the rubber layer provided on the surface of the carcass layer of the polymer composition containing at least one cross-linking agent and / or the curable resin is carcassed during vulcanization.
Fabric that reacts adhesively with the rubber of the rubber layer and the resin of the air permeation preventive layer.
Enol resin adhesive, chlorinated rubber adhesive or isocyanate
There is provided a pneumatic tire having an air permeation preventive layer which is formed by applying a nate-based adhesive to the surface on which the adhesive has been applied and crosslinking the same.

According to the present invention, the carcass layer on the surface of the carcass layer of the green tire made of unvulcanized rubber or the surface of the rubber layer provided on the surface of the carcass layer is carcassed during vulcanization.
The rubber that is adhesively reacted with the rubber of the layer and the resin of the air permeation preventive layer.
Knoll resin adhesive, chlorinated rubber adhesive or isocyanate
After spraying or applying over preparative based adhesive, the adhesive surface, (i) at least one fat which at least part of the amide groups have been modified with alkoxyalkyl groups and / or groups having curable unsaturated bonds A method for producing a pneumatic tire comprising spraying or applying a polymer composition containing a group polyamide resin and (ii) at least one cross-linking agent and / or a curing resin, and then vulcanizing the green tire. Provided.

According to the present invention, furthermore, the rubber and air permeability of the carcass layer are vulcanized during vulcanization on the surface of the carcass layer of the tire after vulcanization or on the surface of the rubber layer provided on the surface of the carcass layer.
Phenolic resin-based adhesive that reacts with the resin of the overcoat layer
Agent or a chlorinated rubber adhesive or an isocyanate adhesive is sprayed or applied, and then (i) at least a part of the amide group is a group having an alkoxyalkyl group and / or a curable unsaturated bond on the adhesive surface. Process for producing a pneumatic tire, which comprises spraying or applying a polymer composition containing at least one modified aliphatic polyamide resin and (ii) at least one cross-linking agent and / or a curing resin and heating the polymer composition. Will be provided.

The present invention will be described in more detail below. The air permeation preventive layer of the pneumatic tire according to the present invention is at any position inside the tire, that is, inside or outside the carcass layer, or inside or outside the rubber layer provided adjacent to the carcass layer, or at any other position. Can be placed at. In short, if the air pressure inside the tire can be maintained for a long period of time by preventing the permeation and release of air from the inside of the tire, the arrangement is not a problem.

FIG. 1 is a half sectional view in the meridian direction illustrating a typical example of the arrangement of the air permeation preventive layer of a pneumatic tire. In FIG. 1, a carcass layer 2 is mounted between a pair of left and right bead cores 1, 1 and an inner liner layer 3 is provided on the inner surface of the tire inside the carcass layer 2. In the present invention, the inner liner layer 3 is composed of a cured body or a crosslinked body of the first or second composition. In FIG. 1, 4 indicates a sidewall.

According to the invention, as the aliphatic polyamide resin, a modified fat in which at least one amide group is modified with (i) an alkoxyalkyl group and / or (ii) a group having a curable unsaturated bond Group polyamide-based resins are used.

As described above, in the modified aliphatic polyamide resin used in the present invention, first, at least a part of the amide group is an alkoxyalkyl group --R ¹ --O--R ² (wherein R ¹ has ¹ carbon atoms). ~ 4 alkylene groups such as methylene, ethylene, propylene, butylene groups, R ² is an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, propyl, butyl groups) and / or as described below. It is modified with a group having a curable unsaturated bond.

Examples of the group having a curable unsaturated bond include N-methylolacrylamide group, acryloyl group, methacryloyl group, vinyl group and allyl group. For example, reaction of unsaturated acid chloride with> NH group of amide group or N- having an unsaturated bond.
It can be introduced by reaction with a methylol compound. The alkoxyalkyl group can be introduced into, for example, a> NH group of polyamide by a method of reacting methanol and paraformaldehyde under an alkaline catalyst.

Further, it is also possible to have an alkoxyalkyl group and an unsaturated bond at the same time. For example, a> NH group of polyamides is reacted with an unsaturated acid chloride to form a relatively stable> N-CO- bond. And then remain> NH
Method for alkoxyalkylating a group, or N-methylol compound or N- having a> NH group of polyamides and an unsaturated bond having good reactivity with the polyamides
It can be obtained by a method of dehydration or dealcoholization reaction with an alkoxyalkylated product, that is, a condensation reaction to introduce an unsaturated bond into the side chain of polyamides, and further alkoxyalkylation of the remaining> NH group.

Examples of polyamides include 6 nylon, 66 nylon, 11 nylon, 610 nylon, 6
A linear polyamide usually called nylon such as 12 nylon, 10 nylon, and 6.66 nylon and a polymer having a —NH ₂ group in the side chain can also be used as extremely useful ones. Examples of unsaturated acid chlorides include acrylic acid chloride, methacrylic acid chloride, crotonic acid chloride, and cinnamoyl chloride. Further, as the N-methylol compound having an unsaturated bond,
Examples thereof include N-methylol acrylamide and N-methylol methacrylamide, and examples of N-alkoxyalkylated compounds having an unsaturated bond include, for example, N-
Examples include methoxymethyl acrylamide and N-butoxymethyl acrylamide.

Further, when the residual> NH group or the --NH ₂ group is alkoxyalkylated, the residual group is treated with an aldehyde such as formaldehyde or acetaldehyde.
And alcohols such as methanol and ethanol. In the crosslinkable elastic polyamide used in the present invention produced by these methods, the amount of the unsaturated bond introduced is an amount that does not impair the flexibility of the crosslinked molded article, that is, 50% or less, and further 3%. It is preferable to be 20%. Further, the softening by N-alkoxyalkylation needs to keep the physical properties within a practically preferable range, and it is preferable to use one having an N-substitution rate of 30 to 50%.

The group having an unsaturated bond is, for example, as described in JP-A-51-24677, page 2, lower left column to lower right column, a polyamide resin such as 6-nylon and N-methylol acrylamide, chloride. Immersion in an aqueous solution of ammonium and hydroquinone (or copper chloride), heat treatment for drying, washing with water and drying. This reaction product can be introduced into a polyamide resin by dissolving it in formic acid containing phenol, adding it to a formalin solution containing methanol, KOH, paraformaldehyde, and oxalic acid for reaction.

The modified aliphatic polyamide resin according to the present invention is used by being dissolved in a solvent at the time of coating, and such a solvent is not particularly limited as long as it is a solvent capable of dissolving the modified aliphatic polyamide resin. However, examples thereof include aliphatic alcohols such as methanol and ethanol and aromatic alcohols such as phenol and cresol. Further, water, ethyl acetate, toluene, methyl ethyl ketone, benzene, chloroform and the like can be added to these alcohol solvents. The concentration of the total amount of the modified aliphatic polyamide resin and the crosslinking agent, the curing resin, and the curing agent of the curing resin is not particularly limited, but preferably 5 to
It is 30% by weight.

Examples of the acid catalyst which can be used for crosslinking the modified aliphatic polyamide resin in the present invention include citric acid, tartaric acid, glutaric acid, lactic acid, itaconic acid, azelaic acid, succinic acid and glycolic acid. , Crotonic acid, hypophosphorous acid, lauric acid, chloroacetic acid, boric acid, maleic acid, oxalic acid, adipic acid, malonic acid and the like. Aromatic sulfonic acids can also be preferably used. Examples of such aromatic sulfonic acids include paratoluenesulfonic acid, orthotoluenesulfonic acid, metatoluenesulfonic acid, benzenesulfonic acid, paracresolsulfonic acid,
One or more selected from ortho-cresol sulfonic acid, meta-cresol sulfonic acid, naphthalene sulfonic acid, dodecylbenzene sulfonic acid and the like can be mentioned. The amount of the acid catalyst used can be conventional and is preferably 3 per 100 parts by weight of the modified aliphatic polyamide.
~ 5 parts by weight.

In the present invention, as the cross-linking agent other than the acid catalyst which can be used for cross-linking the modified aliphatic polyamide resin, for example, a sulfur simple substance, a sulfur-releasing compound (for example, tetramethylthiuram disulfide, monophorine disulfide) is used. sulfide, tetraethyl thiuram disulfide, tetrabutyl thiuram disulfide, dipentamethylenethiuram disulfide, dimethyl diphenyl disulfide), rubber vulcanization accelerator (e.g., 2-mercaptobenzothiazole, dibenzothiazyl disulfide, 2-mercapto Zinc salts of benzothiazole, thiazoles such as cyclohexyl, benzothiazyl, sulfenamide, tetramethylthiuram disulfide, tetramethylthiuram monosulfide, tetraethylthiazole Ram disulfide, thiurams such as dipentamethylenethiuram-tetrasulfide,
Dithioates such as zinc dimethyldithiocarbamate,
Examples thereof include guanidines such as diphenylguanidine and thioureas such as 1,3-diphenylthiourea). The thiurams may be used in combination with a vulcanization accelerator. The amount of these cross-linking agents used is conventional and not particularly limited, but preferably 0.1 to 10 per 100 parts by weight of the polymer, although it depends on the type of cross-linking agent used.
Parts by weight, more preferably 0.1 to 5 parts by weight. In addition to these, peroxides such as dicumyl peroxide (DCP) can also be used.

The cross-linking agent may be an organic halogen donor (eg, chlorosulfonated polyethylene, chloroprene) or an inorganic halide (eg, tin chloride, calcium chloride, iron chloride, aluminum chloride) in order to further improve the cross-linking reaction. Zinc chloride, calcium fluoride (zinc bromide) and the like can be used together as catalysts, for example, 0.1 to 5 parts by weight per 100 parts by weight of the polymer.

Examples of the curing resin that can be used to cure the modified aliphatic polyamide resin in the present invention include epoxide compounds and the like. Glycidyl ether type, epoxy urethane resin type, glycidyl ether / ester type, glycidyl type. It can be freely selected from amine-based linear aliphatic epoxy resins and aliphatic epoxy resins. As the curing agent for the curing resin, various curing agent systems such as aromatic amines, acid anhydrides, polyamide systems, aliphatic amines and latent curing agents can be used, but metaphenylene diamine, diaminodiphenylmethane as a general system, In addition to maleic anhydride, pyromellitic dianhydride, phthalic anhydride such as hexahydrophthalic anhydride, hexamethylenediamine, etc., sebacic acid dihydrazide, dicyandiamide, biperazine-sebacate, etc. may be mentioned. The curing resin varies depending on the combination with the curing agent, but is preferably 60 parts by weight or less with respect to 100 parts by weight of the crosslinkable elastic polyamide.

In the present invention, in order to crosslink the modified aliphatic polyamide resin, further, for example, JP-A-51-
It is also possible to use an alkylphenol formalin resin or an alkylresorcinol formalin resin as described in JP-A 18756, page 3, upper left column to page 4, upper right column.

The first method for manufacturing a pneumatic tire according to the present invention will be described with reference to FIG. 1, in which the inner liner layer 3 is arranged inside the carcass layer 2. The green layer is made of unvulcanized rubber. After applying an adhesive to the inner surface of the carcass layer of the tire, at least a part of the amide group is sprayed or applied with at least one aliphatic polyamide-based resin modified with an alkoxyalkyl group, and then this green A desired lightweight pneumatic tire can be manufactured by vulcanizing the tire according to a conventional method. When the inner liner layer is provided on the outer peripheral surface of the carcass layer, this can be done in accordance with this.

On the other hand, when the air permeation preventive layer is arranged on the surface (that is, the inner peripheral surface) of the carcass layer of the tire after vulcanization, in the case of the vulcanized carcass layer vulcanized by a conventional method, After applying an adhesive to the surface, at least a part of the amide groups is sprayed or applied with at least one aliphatic polyamide-based resin modified with an alkoxyalkyl group, and the desired weight-saving air is obtained by heating. A filled tire can be manufactured.

In the production of the pneumatic tire according to the present invention, the surface of the carcass layer or the rubber layer on the carcass layer can be halogenated by a conventional method. For such halogenation treatment, for example, a general rubber halogenation treatment chlorine solution, bromine solution, iodine solution or the like can be used. As such a solution, a dilute aqueous solution of 12N hydrochloric acid can be used in addition to an aqueous solution containing chlorine, bromine or iodine, and further, a -N (X) C (O)-group (in the formula, X represents halogen). It is preferable to use a dilute solution of the compound containing an organic solvent. Specific examples of such a compound include trichloro-, dichloro-, or monochloro-isocyanuric acid, and the trichloroisocyanuric acid of 2 to
Most preferred is the use of a 20 wt% organic solvent solution (eg a ketone organic solvent solution such as methyl ethyl ketone or an ester organic solvent solution such as ethyl acetate).

The adhesive applied to the surface of the carcass layer in the method for producing a pneumatic tire according to the present invention is a resin for forming the rubber of the carcass layer and the resin of the air permeation preventive layer during vulcanization due to the heat during heating. Adhesive reaction and self-curing reaction. Phenolic resin adhesive, chlorinated rubber adhesive, isocyanate
Anate adhesives can be used.

As a preferable example of such an adhesive,
Phenolic resin type (for example, Chemlock 23 manufactured by Lord Co.)
4B), a chlorinated rubber type (for example, Chemlock 2 manufactured by Lord Co.)
05), an isocyanate type (for example, Chemloc 402 manufactured by Lord Co., Ltd.) and the like can be used.

The material of the rubber layer on which the inner liner layer according to the present invention is laminated is not particularly limited, and any rubber material conventionally used as a rubber material for tires can be used. Examples of such rubbers include diene rubbers such as NR, IR, BR, SBR, halogenated butyl rubbers, ethylene-propylene copolymer rubbers, styrene elastomers, etc., and carbon black, process oils, vulcanizing agents, etc. A rubber composition to which an agent is added can be prepared.

The inner liner layer according to the present invention is air permeable.
Excess coefficient is above 80 ℃, preferably above 100 ℃
25 x 10^-12cc / cm / cm²・ Sec ・ cmHg or less, preferred
Kuha 5 × 10^-12cc / cm / cm²・ Sec ・ cmHg or less
It Air permeability coefficient 25 × 10 ^-12cc / cm / cm²・ Sec
・ The thickness of the inner liner layer can be adjusted to below cmHg.
The thickness of the conventional inner liner layer to 1/2 or less.
You can

On the other hand, the Young's modulus is 1 to 500 MPa, preferably 10 to 300 MPa, and the thickness is 0.01 to 1.0 mm, preferably 0.02 to 0.5 mm. Young's modulus is 1 MPa
When it is less than 500 MPa, it is not preferable because handling becomes difficult due to wrinkles during tire molding. On the contrary, when it exceeds 500 MPa, it is not preferable because the tire deformation during running cannot be followed.

[0041]

EXAMPLES Examples 1 to 24 and Comparative Examples 1 to 3 Hereinafter, the present invention will be described more specifically according to Examples, but it goes without saying that the present invention is not limited to the following Examples. Examples 1 to 11 are examples in which an alkoxyalkylated aliphatic polyamide resin was applied before tire vulcanization. An adhesive was sprayed onto the inner surface of a green tire made of unvulcanized rubber molded by a conventional method. , At room temperature, 30
After drying for a minute, a solution prepared by dissolving 20% by weight of alkoxyalkylated aliphatic polyamide resin in a mixed solvent of 70% by weight of methanol and 30% by weight of methyl ethyl ketone is applied by spraying, and hot air at 80 ° C. is applied. After applying it for 2 minutes to dry it, use a tire vulcanizer at 185 ° C for 15 minutes,
Vulcanization molding was performed under a pressure of 2.3 MPa. In addition, Example 1
2 to 24 and Comparative Example 3 were similar to the above in which the inner surface of a tire vulcanized by the conventional method under the same vulcanization conditions was applied with an adhesive, and then the solution prepared in the same manner as above was applied by spraying, Crosslinking and curing were performed according to the crosslinking and curing treatment conditions shown in Table II. In Comparative Examples 1 and 2, the adhesive was not applied, but the unvulcanized green tire or the inner surface of the tire after vulcanization was halogenated (a 3.3% ethyl acetate solution of trichloroisocyanuric acid was applied with a brush). Dried for 2 hours). The vulcanization conditions are the same as above. Further, in the tire of the standard example, the butyl rubber composition having the following formulation table was used as the inner liner layer. Butyl rubber compound (unit: parts by weight) ────────────────────── Br-IIR 100 Carbon black (GPF) 60 Stearic acid 1 Petroleum hydrocarbon resin ^{* 1} 10 Paraffin-based process oil No. 103 ZnO 3 DM 1 Sulfur 0.6 ───────────────────── * 1: Esso Chemicals Escoletz 1102 Used in the following examples The evaluation method was as follows.

Alkoxyalkylated fat for use in tires
Method for preparing aliphatic polyamide resin solution In a mixed solvent of 30% by weight of methyl ethyl ketone and 70% by weight of methanol, a polymer concentration of 30% by weight is obtained by adding the polymer, the cross-linking agent and other additives shown in Formulations 1 to 8 below. Dissolved in.

The formulations used were as shown in formulations 1 to 8 below. ─────────────────────────────────── Formula 1 Formula 2 Formula 3 Formula 8 Formula ──────── ──────────────────────────── Polymer A ^{* 1} 100 100 100 − Polymer B ^{* 2} − − − 100 Sulfur 1.5 − − 1.5 Peroxide (Dicumi-1.0 --- Rulperoxide) Sulfur-releasing compound (Tet --- 1.5-Lamethylthylium Disulfide) DM 3.0-3.0M 2.0 --- 2.0 MZ 2.0 − − 2.0 SnCl ₂ 1.0 − − 1.0 ───────────────────────────── ───────

* 1 Polymer A: Polymer A is disclosed in JP-A-51.
No. 24657, page 3, lower right, synthesis was carried out as follows according to the method described in Production Example (2) (parts represent parts by weight). 500 parts of 6-nylon and 2 in a reactor equipped with a reflux device
Add 000 parts of formic acid and stir well to form a uniform solution.
While maintaining the temperature at 70 ° C, add 3 parts of phenol and 1
Add 0 parts N-methylol acrylamide and continue stirring for 30 minutes. In this process, N-methylolacrylamide and the> NH group contained in the 6-nylon molecule undergo a dehydration condensation reaction.

Separately, methanol 300 kept at 60 ° C.
After adding 10 parts of KOH to 0 parts to make a uniform solution, 2500 parts of paraformaldehyde was added and completely dissolved, and gradually added to the above 6-nylon-formic acid solution to carry out N-methoxymethylation reaction. To end. At this time,
The temperature of the reaction system is 60 to 64 ° C. Also, the time until the addition of the methanol-paraformaldehyde solution is completed is 10
The reaction is completed within 60 minutes from the start of addition. The target solution is collected by pouring the obtained reaction completed liquid into water. What was thoroughly washed and dried was a flexible substance having good elasticity. * 2 Polymer B: Polymer B was synthesized as follows (all parts are parts by weight). Into a reactor equipped with a reflux device , 500 parts of 66-nylon and 2000 parts of formic acid are put and sufficiently stirred to form a uniform solution. While maintaining the temperature at 70 ° C., 3 parts of phenol and 10 parts of N-methylol acrylamide were added to 30
Continue stirring for minutes. In this process, N-methylolacrylamide and the> NH group contained in the 66-nylon molecule undergo a dehydration condensation reaction.

――――――――――――――――――――――――――― Recipe 4 Recipe 5 ―――――――――――――――― ――――――――――― Lactamide 5003 ^{* 1} 100 100 Epicoat # 828 ^{* 2} 15 30 (epoxy compound ) dihydrazide sebacate 3.5 7.5 (hardener) ――――――――― ―――――――――――――――――― * 1: Laccamide 5003: Dainippon Ink and Chemicals, Inc. 8 Nylon: 6 Nylon based methoxymethylated aliphatic polyamide resin (amide substitution rate 28% or more) * 2: Epicoat # 828: Bisphenol A diglycidyl ether (manufactured by Shell Chemical)

──────────────────────────── Blend 6 Blend 7 ───────────────── ─────────── Raccamide 5003 100 100 Hitanol 1502 ^{* 1} 12-Takkyroll 250-1 ^* 2-20 Zinc white 33 boric acid 1- ────────────── ────────────── * 1: Hitanol 1502: Resole-type phenol resin with a molecular weight of about 800 (manufactured by Nititsu Kasei Co., Ltd.) * 2: Takkyrol 250-1: Brominated alkylphenol formaldehyde resin (Manufactured by Taoka Chemical Co., Ltd.)

Preparation of film sample A solution of the alkoxyalkylated aliphatic polyamide resin in the proportions of each Example and Comparative Example dissolved in a mixed solvent of 70% by weight of methanol and 30% by weight of methyl ethyl ketone in a proportion of 20% by weight was dissolved. A film was prepared by a casting method (a polymer solution was uniformly cast on an endless belt, continuously dried by applying hot air of 60 to 90 ° C., and peeled to form a film). After drying, it was left in a heater at 130 ° C. for 15 minutes for crosslinking and curing treatment. (Film: thickness about 100 μm)

Melting point measuring method Using a differential scanning calorimeter (DSC), the temperature was raised at 10 ° C./min and the peak temperature of the endotherm due to the melting point was read, or if this peak was unclear, a thermomechanical test was conducted. Machine (TM
In A), a compression test was performed with a load of 5 g, and the temperature was read from the inflection point temperature.

The method for measuring the air permeation coefficient of the air permeation preventive layer was conformed to JIS K7126 "Method for testing gas permeation rate of plastic films and sheets (method A)". Test: The film sample prepared above was used. Test gas: Air (N ₂ : O ₂ = 8: 2) Test temperature: 30 ° C

The method for measuring the Young's modulus of the air permeation preventive layer was based on JIS K6251 "Tensile test method for vulcanized rubber". Test piece: The film sample prepared above was placed parallel to the flow direction of the solution (the flow direction of the endless belt),
I punched it out with JIS No. 3 dumbbells. A tangent line was drawn on the curve of the initial strain region of the obtained stress-strain curve, and Young's modulus was obtained from the slope of the tangent line.

Measurement of peel strength of air permeation preventive layer / carcass layer
According to the constant test JIS K6258 "Adhesion test method for vulcanized rubber". Test piece: Disassemble the finished tire and punch it into a strip shape with a width of 25 mm in the carcass cord arrangement direction. Test temperature: 20 ° C. test: The inner liner layer and the carcass layer of the sample are peeled off in advance. Grasp each layer of the sample on the chuck of the tensile tester and peel at the following pull rates. 50.0 ± 5.0 mm / min

Long-term durability test method 165SR13 Steel radial tire (rim 13
× 41 / 2-J), 1500cc at air pressure of 200kPa
In a passenger car in a class, a load equivalent to that of four passengers (65 kg
/ Person) and drive 20,000 km on the actual road. After running, the tire is removed from the rim, and the liner layer on the inner surface of the tire is visually observed. If the liner layer has cracks, visible wrinkles, or peeling / lifting of the liner layer, it is rejected. The purpose of this test is to comprehensively evaluate the strength deterioration and adhesion deterioration of the liner layer in an actual vehicle.

Long-term water resistance / moisture absorption resistance test method 165SR13 Steel radial tire (rim 13
× 4 1/2 -J), air pressure 200 kPa, load 5.
5kN and room temperature 38 ℃, speed 80 on φ1707mm drum
Drive at km / h. After running 10,000 km, the inner surface of the tire is visually inspected, and cracks in the inner liner layer, visible wrinkles, and peeling / lifting of the liner layer are rejected. Immediately before the test run, the tire is left for 10 days at a relative humidity of 98% and a room temperature of 70 ° C.

Tire Air Leakage Performance Test Method 165SR13 Steel Radial Tire (Rim 13
The pressure was measured at an interval of 4 days with an initial pressure of 200 kPa and no load at room temperature of 21 ° C. for 3 months. As the measured pressure Pt, the initial pressure Po, and the elapsed days t, the α value is obtained by regressing the function: Pt / Po = exp (−αt). Using the obtained α, t = 30
Is substituted into the following formula to obtain β = [1−exp (−αt)] × 100 β value. This β value is the rate of pressure drop per month (% /
Month).

Rubber compound for tire carcass ────────────────────── Product name Weight part ───────────────── ────── Natural rubber 80.0 SBR1502 20.0 FEF carbon black 50.0 Stearic acid 2.0 Zinc white 3.0 Sulfur yellow 3.0 Vulcanization accelerator (NS) 1.0 Aroma oil 2. 0 ──────────────────────

The evaluation results are shown in Tables I and II.

[0058]

[Table 1]

[0059]

[Table 2]

[0060]

[Table 3]

[0061]

[Table 4]

* 1 Polymer C: Nylon to be reacted was synthesized as 6/66/610/12 nylon in the same manner as in Polymer B.

[0063]

As described above, according to the present invention,
It is possible to obtain a pneumatic tire having an air permeation preventive layer that is excellent in adhesiveness with a rubber layer, while reducing the weight of the tire while maintaining good air pressure retention in the tire.

[Brief description of drawings]

FIG. 1 is a meridional direction half sectional view showing a structure of a pneumatic tire of the present invention.

[Explanation of symbols]

1 ... bead core 2 ... Carcass layer 3 ... Inner liner layer 4 ... Sidewall

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazuo Suga 2-1, Oiwake, Hiratsuka City, Kanagawa Yokohama Rubber Co., Ltd. Hiratsuka Factory (56) References JP-A-5-318618 (JP, A) JP-A 5-330307 (JP, A) JP-A-7-40702 (JP, A) JP-A-51-18756 (JP, A) JP-A-51-24677 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B60C 5 / 12,5 / 14 C08J 5/12

Claims (9)

(57) [Claims] 1. A thin film of at least one aliphatic polyamide resin in which at least a part of amide groups is modified with an alkoxyalkyl group is used as an air permeation-preventing layer to prevent vulcanization during vulcanization.
Adhesive reaction with the rubber of the carcass layer and the resin of the air permeation preventive layer
Phenolic resin adhesive, chlorinated rubber adhesive or iso
A pneumatic tire formed by laminating a cyanate-based adhesive agent . 2. A rubber and air permeation preventive for a carcass layer during vulcanization on a surface of a carcass layer of a green tire made of unvulcanized rubber or on a surface of a rubber layer provided on the surface of the carcass layer.
Chlorinated phenolic resin adhesive that reacts with the resin in the layer
After spraying or applying a rubber-based adhesive or an isocyanate-based adhesive , a liquid composition containing at least one aliphatic polyamide-based resin in which at least a part of amide groups is modified with an alkoxyalkyl group is applied to the adhesive surface. A method for producing a pneumatic tire, which comprises spraying or coating, and then vulcanizing the green tire to form an air permeation preventive layer. 3. The surface of a carcass layer of a tire after vulcanization or the surface of a rubber layer provided on the surface of the carcass layer , during vulcanization.
Adhesion reaction with rubber of carcass layer and resin of air permeation preventive layer
Phenolic resin adhesive, chlorinated rubber adhesive or
After spraying or applying a isocyanate-based adhesive, the adhesive surface is sprayed or applied with a liquid composition containing at least one aliphatic polyamide resin in which at least a part of the amide groups is modified with an alkoxyalkyl group. A method for producing a pneumatic tire, which comprises an air permeation preventive layer. 4. A thin film of an aliphatic polyamide-based resin obtained by crosslinking at least one aliphatic polyamide-based resin in which at least a part of amide groups is modified with an alkoxyalkyl group, by heat treatment in the presence of an acid catalyst. , Vulcanization
Adhesive with rubber of carcass layer and resin of air permeation prevention layer
Reactive phenol resin adhesive, chlorinated rubber adhesive or
Is a pneumatic tire laminated as an air permeation preventive layer through an isocyanate adhesive . 5. A rubber and air permeation preventive for a carcass layer during vulcanization on a surface of a carcass layer of a green tire made of unvulcanized rubber or a surface of a rubber layer provided on the surface of the carcass layer.
Chlorinated phenolic resin adhesive that reacts with the resin in the layer
After spraying or applying a rubber-based adhesive or an isocyanate-based adhesive , a liquid composition containing at least one aliphatic polyamide-based resin in which at least a part of amide groups is modified with an alkoxyalkyl group is applied to the adhesive surface. A method for producing a pneumatic tire, comprising spraying or applying a liquid to which an acid catalyst is added, and then vulcanizing the green tire to form an air permeation preventive layer. 6. The surface of a carcass layer of a tire after vulcanization or the surface of a rubber layer provided on the surface of the carcass layer , during vulcanization.
Adhesion reaction with rubber of carcass layer and resin of air permeation preventive layer
Phenolic resin adhesive, chlorinated rubber adhesive or
After spraying or applying a socyanate adhesive, an acid catalyst was added to the liquid composition containing at least one aliphatic polyamide resin in which at least some amide groups were modified with alkoxyalkyl groups on the adhesive surface. A method for producing a pneumatic tire, which comprises spraying or applying a liquid and then heating it to form an air permeation preventive layer. 7. (i) At least one amide group modified with an alkoxyalkyl group and / or a group having a curable unsaturated bond, and at least one aliphatic polyamide resin, and (ii) at least one crosslinking agent. And / or a curable resin-containing polymer composition on the surface of the carcass layer of a pneumatic tire or on the surface of a rubber layer provided on the surface of the carcass layer.
Phenolic resin adhesives and salts that undergo an adhesive reaction with the resin of the stop layer
A pneumatic tire which serves as an air permeation preventive layer by being applied to a surface coated with a synthetic rubber adhesive or an isocyanate adhesive and then being crosslinked or cured to form an air permeation preventive layer. 8. A rubber and air permeation preventive for a carcass layer during vulcanization on a surface of a carcass layer of a green tire made of unvulcanized rubber or a surface of a rubber layer provided on the surface of the carcass layer.
Chlorinated phenolic resin adhesive that reacts with the resin in the layer
After spraying or applying a rubber adhesive or an isocyanate adhesive , (i) at least a part of amide groups was modified with an alkoxyalkyl group and / or a group having a curable unsaturated bond on the surface of the adhesive. A polymer composition containing at least one aliphatic polyamide resin and (ii) at least one crosslinking agent and / or a curing resin is sprayed or applied, and then the green tire is vulcanized to form an air permeation preventive layer. A method for manufacturing a pneumatic tire characterized by the above. 9. The surface of a carcass layer of a tire after vulcanization or the surface of a rubber layer provided on the surface of the carcass layer , during vulcanization.
Adhesion reaction with rubber of carcass layer and resin of air permeation preventive layer
Phenolic resin adhesive, chlorinated rubber adhesive or
After spraying or applying a cyanate-based adhesive, at least one aliphatic group in which (i) at least a part of the amide group is modified with an alkoxyalkyl group and / or a group having a curable unsaturated bond on the surface of the adhesive. Manufacture of a pneumatic tire characterized in that a polymer composition containing a polyamide resin and (ii) at least one crosslinking agent and / or a curing resin is sprayed or applied and heated to form an air permeation preventive layer. Law.