阅读说明：本技术 叠层体及充气轮胎的制造方法 (The manufacturing method of laminated body and pneumatic tire ) 是由 柴田宽和 丹野笃 于 2018-04-11 设计创作，主要内容包括：提供一种叠层体,是包含聚酰亚胺树脂的层和未硫化橡胶组合物的层的叠层体,橡胶组合物包含：橡胶成分(A)；聚酰胺聚醚弹性体(B),其量相对于橡胶成分(A)100质量份为20～100质量份；缩合物(C),上述缩合物为下述式(1)所示的化合物与甲醛的缩合物(式中,R<Sup>1</Sup>、R<Sup>2</Sup>、R<Sup>3</Sup>、R<Sup>4</Sup>和R<Sup>5</Sup>独立地选自氢原子、羟基、碳原子数1～8的烷基、碳原子数1～8的羟基烷基、和碳原子数1～8的烷氧基)；亚甲基供体(D)；以及硫化剂(E)。本发明的叠层体在聚酰亚胺树脂的层与橡胶组合物的层之间显示提高了的粘接强度。<Image he="459" wi="700" file="DDA0002232444020000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(A kind of laminated body is provided, is the laminated body comprising the layer of polyimide resin and the layer of unvulcanized rubber composition, rubber composition includes: rubber constituent (A)；Polyamide polyether elastomer (B), amount are 20~100 mass parts relative to 100 mass parts of rubber constituent (A)；Condensation product (C), above-mentioned condensation product be following formula (1) compound represented and formaldehyde condensation product (in formula, R 1 、R 2 、R 3 、R 4 And R 5 Independently selected from hydrogen atom, hydroxyl, the alkyl of carbon atom number 1~8, the hydroxy alkyl of carbon atom number 1~8 and carbon atom number 1~8 alkoxy)；Methylene donor (D)；And vulcanizing agent (E).Laminated body of the invention shows the adhesive strength improved between the layer of polyimide resin and the layer of rubber composition.)

1. a kind of laminated body, it includes the layer of the layer of polyimide resin and unvulcanized rubber composition, the half finished rubber Composition includes:

Rubber constituent (A)；

Polyamide polyether elastomer (B), amount are 20~100 mass parts relative to 100 mass parts of rubber constituent (A)；

Condensation product (C), the condensation product are the condensation of phenol system compound and formaldehyde substituted or unsubstituted shown in following formula (1) Object；

In formula, R¹、R²、R³、R⁴And R⁵Independently selected from hydrogen atom, hydroxyl, the alkyl of carbon atom number 1~8, carbon atom number 1~8 The alkoxy of hydroxy alkyl and carbon atom number 1~8；

Methylene donor (D)；And

Vulcanizing agent (E).

2. laminated body according to claim 1, the amount of condensation product (C) is 0.5 relative to 100 mass parts of rubber constituent (A) ~10 mass parts, the amount of methylene donor (D) are 0.25~50 mass parts, methylene relative to 100 mass parts of rubber constituent (A) The mass ratio of donor (D) and condensation product (C) are 0.5:1~5:1.

3. laminated body according to claim 1 or 2, methylene donor (D) be selected from modified etherfied methylol melamine, It is at least one kind of in paraformaldehyde, hexa, pentamethylene tetramine and hexamethoxymethyl melamine.

4. laminated body described in any one of claim 1 to 3, polyamide polyether elastomer (B) is containing including polyamides The copolymer of the hard segment of amine and the soft chain segment comprising polyethers.

5. laminated body according to any one of claims 1 to 4, condensation product (C) is indicated by formula (2) or formula (3),

In formula, n be 1~20 integer；

In formula, m be 1~20 integer.

6. laminated body according to any one of claims 1 to 5, rubber constituent (A) is diene series rubber.

7. a kind of manufacturing method of pneumatic tire, it includes following processes:

The process for forming the green tire comprising laminated body according to any one of claims 1 to 6；And

The process that the green tire is vulcanized.

Technical field

The present invention relates to the laminated bodies and use of the layer comprising polyimide resin and the layer of unvulcanized rubber composition The manufacturing method of the pneumatic tire of the laminated body.

Background technique

The excellents such as obdurability, heat resistance, gas blocking and the chemical stability of known polyimide resin.Cause This, if it is possible to it engages polyimide resin molded product with not same material, then can obtain and have polyimide resin The complex of excellent characteristics can expand the purposes of polyimide resin.For example, in order to make polyimide resin as inflated wheel The reinforcing material of tire works, and needs to keep polyimide resin Nian Jie with the rubber component of tire is constituted.It is public in patent document 1 A kind of resin combination has been opened, has been the resin combination being bonded to the polyimides molded product for forming the forms such as film, packet 80~100 weight % of elastomer containing polyamide polyether.

Summary of the invention

Problems to be solved by the invention

However, not proposed the layer and building rubber compound of polyimide resin without using bonding agent so far The technology of the layer engagement of object.In addition, being as 80~100 weight % about resin combination disclosed in patent document 1 It at high proportion include the resin combination of polyamide polyether elastomer, according to the type for the rubber constituent for being glued object without showing Cementability.

Therefore, the purpose of the present invention is to provide what can be engaged in the case where not using bonding agent includes polyimides The manufacturing method of the laminated body of the layer of the layer and unvulcanized rubber composition of resin and the pneumatic tire using the laminated body.

The method used for solving the problem

The inventors discovered that comprising rubber constituent, relative to the rubber constituent be specific quantity polyamide polyether elastomer, Specific phenol system compound and the condensation product of formaldehyde and the rubber composition of methylene donor show polyimide resin excellent Different cementability, so as to complete the present invention.

It is layer and unvulcanized rubber composition comprising polyimide resin that is, according to the present invention, providing a kind of laminated body Layer laminated body, rubber composition includes:

Rubber constituent (A)；

Polyamide polyether elastomer (B), amount are 20~100 mass parts relative to 100 mass parts of rubber constituent；

Condensation product (C), above-mentioned condensation product are the contracting of phenol system compound and formaldehyde substituted or unsubstituted shown in following formula (1) Close object；

(in formula, R¹、R²、R³、R⁴And R⁵Independently selected from hydrogen atom, hydroxyl, the alkyl of carbon atom number 1~8, carbon atom number 1 ~8 hydroxy alkyl and the alkoxy of carbon atom number 1~8)

Methylene donor (D)；And

Vulcanizing agent (E).

According to the present invention, it is further provided a kind of manufacturing method of pneumatic tire, it includes following processes: being formed comprising upper The process for stating the green tire of laminated body；And the process for vulcanizing the green tire.

The present invention, specifically, including following proposal 1~8.

[scheme 1]

A kind of laminated body is the laminated body comprising the layer of polyimide resin and the layer of unvulcanized rubber composition, non-sulphur Changing rubber composition includes:

Rubber constituent (A)；

Polyamide polyether elastomer (B), amount are 20~100 mass parts relative to 100 mass parts of rubber constituent (A)；

Condensation product (C), above-mentioned condensation product are the contracting of phenol system compound and formaldehyde substituted or unsubstituted shown in following formula (1) Close object；

(in formula, R¹、R²、R³、R⁴And R⁵Independently selected from hydrogen atom, hydroxyl, the alkyl of carbon atom number 1~8, carbon atom number 1 ~8 hydroxy alkyl and the alkoxy of carbon atom number 1~8)

Methylene donor (D)；And

Vulcanizing agent (E).

[scheme 2]

According to laminated body described in above scheme 1, the amount of condensation product (C) is relative to 100 mass parts of rubber constituent (A) 0.5~10 mass parts, the amount of methylene donor (D) is 0.25~50 mass parts relative to 100 mass parts of rubber constituent (A), sub- The mass ratio of methyl donor (D) and above-mentioned condensation product (C) are 0.5:1~5:1.

[scheme 3]

The laminated body according to above scheme 1 or 2, methylene donor (D) are selected from modified etherfied methylol melamine It is at least one kind of in amine, paraformaldehyde, hexa, pentamethylene tetramine and hexamethoxymethyl melamine.

[scheme 4]

The laminated body according to any one of above scheme 1~3, polyamide polyether elastomer (B) are containing including rouge The copolymer of the hard segment of fat polyamide and the soft chain segment comprising aliphatic polyether.

[scheme 5]

The laminated body according to any one of above scheme 1~4, condensation product (C) are indicated by formula (2) or formula (3).

(in formula, n be 1~20 integer)；

(in formula, m be 1~20 integer)

[scheme 6]

The laminated body according to any one of above scheme 1~5, rubber constituent (A) are diene series rubber.

[scheme 7]

A kind of manufacturing method of pneumatic tire, it includes following processes:

The process for forming the green tire comprising laminated body described in any one of above scheme 1~6；And

The process that green tire is vulcanized.

The effect of invention

Although laminated body of the invention is uncoated between the layer of polyimide resin and the layer of unvulcanized rubber composition Bonding agent, but by being heated under following predetermined temperatures, it can be in the layer of polyimide resin and the layer of rubber composition Between show high-adhesive-strength.Laminated body of the invention can be removed needed for coating adhesive due to not including bonding agent The equipment wanted, operation, can simply manufacture compared with the prior art for using bonding agent.Further, laminated body of the invention It does not need to improve cementability to be surface-treated the layer of polyimide resin in advance.Since polyimide resin is tough The excellents such as property, heat resistance, gas blocking and chemical stability, therefore by using laminated body of the invention, it can make Make the excellent spy such as the obdurability for imparting the layer from polyimide resin, heat resistance, gas blocking and chemical stability The pneumatic tire of property.Further, in the layer that will constitute the unvulcanized rubber composition of laminated body of the invention and with piece or film Other half finished rubber molded products of the arbitrary shapes such as shape lamination or it is adjacent in the state of vulcanization in the case where, by non-sulphur Change rubber composition layer and half finished rubber molded product between vulcanization reaction also occurs and in the layer of rubber composition and non-sulphur Change and also shows firm bonding between molded rubber article.Therefore, according to the present invention it is possible to by polyimide resin layer via rubber Composition layer and with other molded rubber articles, such as constitute pneumatic tire other rubber components be bonded securely, as a result, can Simply to obtain the complex of the excellents such as obdurability, heat resistance, gas blocking and chemical stability.

Specific embodiment

Hereinafter, explaining the present invention in detail.

[polyimide resin]

About the layer of the polyimide resin in laminated body of the invention, polyimide resin be make by tetracarboxylic dianhydride with Polyimide precursor hot-imide or chemical imidization that diamines obtains and the producing high-molecular with imide bond that obtains Object is closed, can be well known compound in this technical field.

As the example of tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride, ester ring type four can be enumerated Carboxylic acid dianhydride etc..As the concrete example of tetracarboxylic dianhydride's ingredient, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydrides, equal benzene tetramethyl can be enumerated Acid dianhydride, 3,3 ', 4,4 '-oxygen, two O-phthalic acid dianhydride, diphenyl sulfone -3,4,3 ', 4 '-tetracarboxylic acid dianhydrides, bis- (3,4- dicarboxyls Base phenyl) thioether dianhydride, bis- (3,4- the dicarboxyphenyi) -1,1,1,3,3,3- hexafluoropropane dianhydrides of 2,2- etc..Tetracarboxylic dianhydride It may be used singly or in combination of two or more.

As the example of diamines, aromatic diamine, aliphatic diamine, ester ring type diamines etc. can be enumerated.Tool as diamines Body example can enumerate p-phenylenediamine, 4,4 '-diamino-diphenyl ethers, 3,4 '-diamino-diphenyl ethers, tolidine, distich first Aniline, 5- amino -2- (p-aminophenyl) benzoAzoles, 4,4 '-diamino-benzanilide (4,4'- Diaminobenzanilide), bis- (4- amino-benzene oxygen) benzene of 1,3-, bis- (3- amino-benzene oxygen) benzene of 1,4-, bis- (the 4- ammonia of 1,4- Phenoxyl) benzene, 3,3 '-bis- (3- amino-benzene oxygen) biphenyl, 3,3 '-bis- (4- amino-benzene oxygen) biphenyl, 4,4 '-bis- (3- ammonia Phenoxyl) biphenyl, 4,4 '-bis- (4- amino-benzene oxygen) biphenyl, bis- (3- (3- amino-benzene oxygen) phenyl) ethers, bis- (3- (4- ammonia Phenoxyl) phenyl) ether, bis- (4- (3- amino-benzene oxygen) phenyl) ethers, bis- (4- (4- amino-benzene oxygen) phenyl) ethers, 2,2- be bis- (3- (3- amino-benzene oxygen) phenyl propane, 2,2- bis- (3- (4- amino-benzene oxygen) phenyl propanes, bis- (4- (the 3- amino of 2,2- Phenoxy group) phenyl propane, bis- (4- (4- amino-benzene oxygen) phenyl propanes etc. of 2,2-.Diamines can be used alone, can also group It closes and uses two or more.

As polyimide resin, well known polyimide resin can be used.As particularly suitable as to rubber group The commercially available product for closing the polyimide resin of the adherend of nitride layer can enumerate space portion emerging production (strain) ユ ー ピ レ ッ Network ス processed (note Volume trade mark) S series and R series, カ プ ト Application (registered trademark) series of east レ デ ュ Port Application (strain) system etc..ユーピレック ス S is using 3,3 ', the 4,4 '-bibenzene tetracarboxylic dianhydrides as tetracarboxylic dianhydride's ingredient and the p-phenylenediamine as diamine component Polyimide resin as principal component.ユ ー ピ レ ッ Network ス R is using 3,3 ', the 4,4 '-biphenyl as tetracarboxylic dianhydride's ingredient Tetracarboxylic acid dianhydride, the polyimide resin with the 4,4 '-diamino-diphenyl ethers as diamine component as principal component.カプト Application H be using as tetracarboxylic dianhydride's ingredient pyromellitic acid anhydride, with as diamine component 4,4 '-diamino-diphenyl ethers Polyimide resin as principal component.

[unvulcanized rubber composition]

Rubber constituent (A)

About the layer of the unvulcanized rubber composition in laminated body of the invention, rubber that unvulcanized rubber composition is included Glue ingredient (A) is preferably diene series rubber.As the concrete example of diene series rubber, natural rubber (NR), isoprene can be enumerated Rubber (IR), epoxy natural rubber, butadiene-styrene rubber (SBR), butadiene rubber (BR) (high-cis BR and low cis BR), propylene Nitrile butadiene rubber (NBR) etc..Diene series rubber be selected from natural rubber (NR), butadiene-styrene rubber (SBR), butadiene rubber (BR), With their combination of more than two kinds, this is in terms of the layer of processability and the unvulcanized rubber composition is to the cementability of sheet rubber Consideration is preferred.

Polyamide polyether elastomer (B)

In the present invention, the polyamide polyether elastomer (B) that unvulcanized rubber composition is included is containing comprising polyamides The copolymer of the hard segment of amine and the soft chain segment comprising polyethers.Polyamide polyether elastomer (B) is preferably comprising being used as hard segment Polyamide-block and the polyether block as soft chain segment block copolymer.Polyamide polyether elastomer (B) more preferably wraps Block copolymer containing the fatty polyamide block as hard segment and the aliphatic polyether block as soft chain segment.

In a preferred scheme, polyamide polyether elastomer (B) is indicated by the following general formula (I).

-[A_k-X-B_m]_n- (I)

(in formula, A_kIndicate polyamide-block, B_mIndicate that polyether block, X are indicated polyamide-block in conjunction with polyether block Combination base, n indicate 1 or more integer.)

In repetitive unit [A_k-X-B_m] between, polyamide-block A_kIt can be the same or different.Respectively combine base X preferably independent Ground is the group in-CO-NH- and-CO-O-.Polyamide polyether elastomer (B) preferably has 1.0 × 10⁴~2.0 × 10⁵ Matter average molecular weight.

Polyamide-block A_kIt can be the polyamides such as the salt formed by lactams, amino carboxylic acid, diamines and dicarboxylic acids The one kind or two or more polymerization of amine formative monomer and derivative polyamide-block.As the example of lactams, ε-can be enumerated The carbon atom numbers 5~20 such as caprolactam, ω-oenantholcatam, ω-spicy inner formyl amine, ω-ten lactams, omega-lauric lactam Aliphatic lactams can preferably enumerate the aliphatic lactams of carbon atom number 5~12.As the example of amino carboxylic acid, can enumerate Omega-amino caproic acid, omega-amino enanthic acid, omega-amino octanoic acid, omega-amino n-nonanoic acid (ア ミ ノ ペ Le U Application acid), omega-amino capric acid, The carbon atom numbers 5 such as 6-aminocaprolc acid, 7- aminoheptylic acid, 9 aminononanoic acid, 11- amino undecanoic acid, 12 amino dodecanoic acid~ It 20, is preferably the amino carboxylic acid of carbon atom number 5~11.The example of the diamines in salt formed as diamines and dicarboxylic acids, can lift Ethylenediamine, triethylenediamine, entprol, 1,5- pentanediamine, 1,6- hexamethylene diamine, 1,7- diaminoheptane, 1,8- diamino are pungent out The diamines of the carbon atom numbers 2~20 such as alkane, 1,9- diamino nonane, 1,10- diamino decane, phenylenediamine, m-xylene diamine.As The example of dicarboxylic acids in the salt of diamines and dicarboxylic acids can enumerate oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, the last of the ten Heavenly stems two Acid, terephthalic acid (TPA), M-phthalic acid, suberic acid, azelaic acid, nonane dicarboxylic acid, decane dicarboxylic, tetradecane dioctyl phthalate, ten Eight alkane dioctyl phthalate, fumaric acid, phthalic acid, phenylenedimethylidyne dioctyl phthalate, dimeric dibasic acid (by using linoleic acid, oleic acid as it is main at Point unsaturated fatty acid synthesis carbon atom number 36 unsaturated dicarboxylic) etc. carbon atom numbers 2~36 dicarboxylic acids.Diamines with The salt that dicarboxylic acids is formed is preferably the salt that foregoing illustrative diamines and dicarboxylic acids are formed, and is more preferably selected from ethylenediamine, three second two 1 kind in amine, entprol and 1,6- hexamethylene diamine with selected from oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, decanedioic acid, The salt of a kind of formation in terephthalic acid (TPA) and M-phthalic acid.

As the example for the polyamide units for constituting polyamide-block, polycaprolactam (nylon 6), acyl in poly- heptan can be enumerated Amine (nylon 7), poly capryllactam (nylon 8), poly- nonyl lactams (nylon 9), poly- 11 lactams (nylon 11), in polyoxyethylene lauryl base The ring-opening polymerization polymer of the lactams such as amide (nylon 12)；Caprolactam/lauryl lactam copolymer (nylon 6/12), in oneself The ring-opening copolymer of the lactams such as amide/nonyl lactams copolymer (nylon 6/9)；Poly hexamethylene adipamide ethylenediamine (nylon 26) gathers Adipyl butanediamine (nylon 46), polyhexamethylene adipamide (nylon66 fiber), polyhexamethylene sebacamide (nylon 610), poly- dodecane Two acyl hexamethylene diamines (nylon 612), polyoctamethylene adipamide (nylon 8 6), polydecamethylene adipamide (nylon 106), the poly- decanedioyl last of the ten Heavenly stems The polycondensation of the diamines and dicarboxylic acids such as diamines (nylon 108), adipyl ethylenediamine/hexamethylene adipamide copolymer (nylon 26/66) Object；Caprolactam/hexamethylene adipamide copolymer (nylon 6/66), lauryl lactam/hexamethylene adipamide copolymer (nylon 12/66), the own diammonium copolymer (nylon66 fiber/610) of caprolactam/hexamethylene adipamide/decanedioic acid, adipic acid second diammonium/oneself two Lactams/diamines/dicarboxylic acids copolymers such as the own diammonium copolymer (nylon 6/66/610) of acyl hexamethylene diamine/decanedioic acid.Wherein, The preferably ring-opening polymerization polymer and copolymer of lactams, particularly preferably polylauryllactam (nylon 12).

Polyether block B_mCan for by polyethylene glycol, polypropylene glycol, polytetramethylene ether diol, by following formula (II) tables The one kind or two or more polymerizations of the polyethers such as the ABA type triblock polyether, the polyether diamine that show and derivative polyether block.

In above-mentioned formula (II), the integer that x is 1~20, preferably 2~6 integer, the integer that y is 4~50, preferably 6 ~12 integer, the integer that z is 1~20, preferably 1~5 integer.

The number-average molecular weight of hard segment is preferably 300~15000, and more preferably 300~600.The equal molecule of the number of soft chain segment Amount preferably 200~6000, more preferably 650~2000.Above-mentioned hard segment and above-mentioned soft chain segment mass ratio (i.e. hard segment: Soft chain segment) it is preferably 20:80~95:5, more preferably 30:70~80:20.

As the combination of above-mentioned hard segment and above-mentioned soft chain segment, each of the above-mentioned hard segment enumerated and soft chain segment can be enumerated A combination.Wherein, the preferably combination of the open loop condensation polymer and polyethylene glycol of lauryl lactam, the open loop of lauryl lactam The combination of condensation polymer and polypropylene glycol, the open loop condensation polymer of lauryl lactam and polytetramethylene ether diol combination, laurel The combination of the open loop condensation polymer of base lactams and the ABA type triblock polyether of above-mentioned logical formula (II), particularly preferably in lauryl The combination of the open loop condensation polymer of amide and the ABA type triblock polyether of above-mentioned logical formula (II).As including lauryl lactam The example of the combined polyamide polyether elastomer of open loop condensation polymer and the ABA type triblock polyether of above-mentioned logical formula (II), can lift UBESTA XPA (registered trademark) P9040X1 out.

The fusing point of polyamide polyether elastomer (B) is not particularly limited, in order in the curing temperature of half finished rubber Under be hot-melted polyamide polyether elastomer to the layer of polyimide resin, it is more excellent preferably with 90~180 DEG C of fusing point Select the fusing point with 90~130 DEG C.

Polyamide polyether elastomer as described above is commercially available, and as the example of commercially available product, can enumerate the emerging production strain formula in space portion Each series etc. of the UBESTA XPA (registered trademark) of commercial firm.Wherein can particularly preferably use UBESTA XPA 9040X1, UBESTA XPA 9040F1、UBESTA XPA9048X1、UBESTA XPA 9048F1、UBESTA XPA 9055X1、UBESTA XPA9055F1、UBESTA XPA 9063X1、UBESTA XPA 9063F1、UBESTA XPA9068X1、UBESTA XPA 9068F1、UBESTA XPA 9040X2、UBESTA XPA9048X2、UBESTA XPA 9040F2、UBESTA XPA The polyetheramide elastomerics body such as 9048F2, UBESTA XPA9035X.

The amount of polyamide polyether elastomer (B) is 20~100 mass parts preferably with respect to 100 mass parts of rubber constituent (A), Preferably 40~80 mass parts.Polyamide polyether elastomer (B) amount relative to 100 mass parts of rubber constituent (A) be less than It, cannot be and laminated body of the invention be heated under following predetermined temperatures in polyamides Asia in the case where 20 mass parts The raising of sufficient adhesive strength is brought between amine resin layer and unvulcanized rubber composition layer, if it exceeds 100 mass parts, then It is difficult to make the unvulcanized rubber composition for constituting laminated body of the invention after by laminated body of the invention and other sheet rubber laminations The layer of object and other sheet rubber bonding by Vulcanization.

The condensation product (C) of phenol system compound and formaldehyde substituted or unsubstituted

1 preference of phenol system compound substituted or unsubstituted shown in formula (1) is R¹、R²、R³、R⁴And R⁵Among at least 1 group is the alkyl that carbon atom number is 1~8, and the alkyl that remaining group is hydrogen atom or carbon atom number is 1~8 Compound.Another 1 preference of formula (1) compound represented is R¹、R²、R³、R⁴And R⁵Among at least one group be hydroxyl, The compound for the alkyl that remaining group is hydrogen atom or carbon atom number is 1~8.Phenol system compound substituted or unsubstituted is more preferable For cresols, resorcinol, p-Octylphenol.As the example of phenol system compound substituted or unsubstituted and the condensation product (C) of formaldehyde, Cresol/formaldehyde condensation product, resorcinol-formaldehyde condensation product etc. can be enumerated.In addition, these condensation products can not damage the present invention Effect in the range of be modified.For example, the modification resorcinol-formaldehyde condensation product for being at least partially epoxidized polymer modified can also make For the present invention.These condensation products are commercially available, in the present invention it is possible to use commercially available product.Condensation product (C) is preferably by following The cresol/formaldehyde condensation product that formula (2) indicates or the resorcinol-formaldehyde condensation product indicated by formula (3).

In formula, the integer that n is 1~20, preferably 1~10 integer, more preferably 1~5 integer.

In formula, the integer that m is 1~20, preferably 1~10 integer, more preferably 1~3 integer.

The amount of condensation product (C) is preferably 0.5~10 mass parts relative to 100 mass parts of rubber constituent (A), more preferably 1.5~6.0 mass parts.The case where it is less than 0.5 mass parts that the amount of condensation product (C) is relative to 100 mass parts of rubber constituent (A) Under, cannot be brought and being heated laminated body of the invention under following predetermined temperatures polyimide resin layer with The raising of sufficient adhesive strength between unvulcanized rubber composition layer, condensation product (C) amount relative to rubber constituent (A) 100 mass parts be more than 10 mass parts in the case where, resulting rubber composition does not have sufficient elongation characteristics after curing, It is easy to be broken.

Methylene donor (D)

In the present specification, so-called " methylene donor " refers to and produces formaldehydogenic alkali cpd by heating etc., as The example of methylene donor can enumerate hexa, pentamethylene tetramine, 1,6- hexamethylene diamine, melamine methylol, ether Change melamine methylol, modified etherfied methylol melamine, esterification melamine methylol, hexamethoxy methyl melamine Amine, hexamethylolmelamine, six (ethoxyl methyl) melamines, six (methoxy) melamines, N, N ', N "-three Methyl-N, N ', N "-trimethylol melamine, N, N ', N "-trimethylol melamine, N- melamine methylol, N, N '- Bis- (methoxy) melamines, N, N ', N "-tributyl-N, N ', N "-trimethylol melamine, paraformaldehyde etc..It is excellent Selecting methylene donor (D) is selected from modified etherfied methylol melamine, paraformaldehyde, hexa, pentamethylene four It is at least one kind of in amine and hexamethoxymethyl melamine.Wherein, from the viewpoint of the release temperature of formaldehyde, preferably change Property etherfied methylol melamine.

The amount of methylene donor (D) is preferably 0.25~50 mass parts relative to 100 mass parts of rubber constituent (A), more excellent It is selected as 0.75~18 mass parts.Methylene donor amount relative to 100 mass parts of rubber constituent (A) be less than 0.25 mass parts In the case where, the reaction of condensation product (C) is not in the case where heated laminated body of the invention under following predetermined temperatures It sufficiently carries out, as a result, being difficult to improve adhesive strength.It, may be to rubber composition if the amount of methylene donor is excessive Curing system brings adverse effect.

The mass ratio of methylene donor (D) and condensation product (C) are preferably 0.5:1~5:1, more preferably 1:1~3:1.Such as Fruit methylene donor (D) is too small relative to the ratio of condensation product (C), then by laminated body of the invention under following predetermined temperatures The reaction of condensation product (C) does not carry out sufficiently in the case where heating, it is difficult to improve adhesive strength.If methylene donor (D) is opposite It is excessively high in the ratio of condensation product (C), then adverse effect may be brought to the curing system of rubber composition.

Vulcanizing agent (E)

As the example of vulcanizing agent, inorganic system's vulcanizing agent and organic system vulcanizing agent can be enumerated.As inorganic system's vulcanizing agent Example can enumerate sulphur, sulfur monochloride, selenium, tellurium, zinc oxide, magnesia, lead monoxide etc., as the example of organic system vulcanizing agent, Organic compounds containing sulfur, dithiocar-bamate, oximes, four chloro- 1,4-benzoquinone, dinitroso aromatic compounds, modified phenol can be enumerated Resin, polyamines, organic peroxide etc..Wherein, preferably sulphur, 1,3- it is bis--(t-butylperoxyisopropyl)-benzene as have Modified phenolic resin, zinc oxide, organic compounds containing sulfur as machine peroxide, bromo alkyl phenol-formaldehyde condensate.

The amount of vulcanizing agent is relative to 100 mass parts of rubber constituent (A), preferably 0.2~5.0 mass parts, more preferably 1.0 ~4.0 mass parts.In the case where the amount of vulcanizing agent is very few, laminated body of the invention is heated under following predetermined temperatures In the case of the vulcanization reaction of rubber constituent (A) do not carry out sufficiently, it may occur however that removed as caused by material damage, if vulcanizing agent Amount it is excessive, then prevulcanization (incipient scorch) may occur before defined vulcanization process.

Within the scope of the effect of the invention, rubber composition may include the reinforcing agents such as carbon black, silica (filler), vulcanizing agent, vulcanization accelerator, vulcanization accelerator additive, softening agent, processing aid, anti-aging agent etc. are generally used in rubber The various additives of composition.

[manufacture of laminated body]

Laminated body of the invention can manufacture as follows: by the layer laminate to above-mentioned polyimide resin include it is above-mentioned at Divide the layer of the unvulcanized rubber composition of (A)~(E) and forms layer and unvulcanized rubber composition comprising polyimide resin The laminated body (hereinafter referred to as " unvulcanized laminated body ") of the layer of object, then, by resulting unvulcanized laminated body at 120 DEG C It is heated under~200 DEG C of predetermined temperature to vulcanize, the layer of polyimide resin is engaged with the layer of rubber composition, i.e., one Body.More specifically the manufacture of unvulcanized laminated body can be implemented, but be not limited to following methods by following methods. Firstly, unvulcanized rubber composition is shaped to stratiform with molding machines such as T-shaped mould extruders, the layer of rubber composition is made, Next, manufacturing unvulcanized laminated body by the layer laminate of polyimide resin on the layer of unvulcanized rubber composition.Pass through The integration that the vulcanization of unvulcanized laminated body carries out can be implemented with such as 50 seconds~320 minutes vulcanization times.

In the present specification, so-called " unvulcanized laminated body ", although refer to the layer of above-mentioned polyimide resin with it is upper The layer laminate for the rubber composition stated, but do not carry out the heating under above-mentioned predetermined temperature of unvulcanized rubber composition Laminated body.Here, about " layer of polyimide resin " and " layer of rubber composition ", term as " layer " refers to polyamides Asia Polyimide resin and rubber composition have the form of piece or film, and so-called " lamination " refers to the layer and rubber composition of polyimide resin Layer be at least partly directly overlapped along their thickness direction.

The thickness of the layer of the thickness and unvulcanized rubber composition of the layer of polyimide resin is not particularly limited.In this hair Bright laminated body as pneumatic tire reinforcing material and in the case where use, the layer and half finished rubber group of polyimide resin As long as the layer for closing object has the effect of that the thickness as reinforcing material can be played.In laminated body of the invention as inflation The reinforcing material of such as sidewall of tire and in the case where use, the thickness of the layer of polyimide resin is preferably 0.1~ 0.3mm, the thickness of the layer of unvulcanized rubber composition are preferably 0.15~2mm.

Laminated body of the invention is the layer comprising 1 polyimide resin and 1 unvulcanized rubber in one embodiment The laminated body of the layer of glue composition.In addition, laminated body of the invention can be to include alternately lamination in another embodiment 1 or 2 or more polyimide resin layer and 1 or 2 or more the layer of unvulcanized rubber composition 3 layers or more of lamination Body.That is, laminated body of the invention further includes the layer of at least one polyimide resin, at least one unvulcanized rubber composition Layer or at least one polyimide resin layer and at least one unvulcanized rubber composition layer, can be following laminations Body:

(a) layer of n-layer (integer that n is 1 or more) polyimide resin and the layer of (n+1) layer unvulcanized rubber composition are handed over Alternately lamination, two outermost layers are the layer of unvulcanized rubber composition, or

(b) layer of the layer of (n+1) strata imide resin and n-layer unvulcanized rubber composition alternately lamination, two is outermost Layer is the layer of polyimide resin, or

(c) layer of m layers (integer that m is 2 or more) polyimide resin replaces folded with the layer of m layers of unvulcanized rubber composition The laminated body of layer.According to the present invention, by the way that the cementability to polyimide resin layer is low but to high its of the cementability of rubber Its material is Chong Die with the layer of outermost unvulcanized rubber composition of laminated body of the invention, together with the other materials of overlapping Laminated body of the invention is heated under above-mentioned predetermined temperature, so as to manufacture polyimide resin layer via building rubber compound Nitride layer and complex with other materials Composite.In the case where laminated body of the invention is 3 layers or more of laminated body, respectively Polyimide resin layer and each unvulcanized rubber composition layer can also be respectively provided with the thickness in above range.

Laminated body of the invention can be used, manufacture pneumatic tire by conventional method.For example, on tire building drum The unvulcanized rubber member for successively folding the Tire productions such as patch liner layer, carcass, belt, tyre surface, is formed and forms life When tire, as 1 or more among these unvulcanized rubber members, using the laminated body of the invention with desired shape, Green tire is vulcanized, so as to use laminated body of the invention to manufacture pneumatic tire.