JP2015203037A - Rubber composition, crosslinked product formed from rubber composition, and production method of said crosslinked product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a crosslinked rubber having the characteristics of polyrotaxane, in particular the desired tensile strength and/or the desired tensile elongation percentage and/or the desired compression set, a rubber composition forming said crosslinked rubber, and a method for producing crosslinked rubber having said characteristics.SOLUTION: The problem is solved by a rubber composition containing: A) polyrotaxane in which stopper groups are placed at both ends of a pseudopolyrotaxane, which is formed of a ring-shape molecule whose opening is clathrated by a straight chain-shape molecule in a skewer state, so as the ring-shape molecule not to leave; B) non-diene-based rubber; and C) crosslinking agent for the crosslinking between said A) polyrotaxane and the B) non-diene-based rubber, as well as by a crosslinked product formed and comprising the rubber composition.

Description

  The present invention relates to a rubber composition having a polyrotaxane and a non-diene rubber, a crosslinked product formed from the rubber composition, and a method for producing the crosslinked product.

  Polyrotaxane has properties such as viscoelasticity and low compression set due to the cross-linked products of polyrotaxanes, cross-linked products of polymers other than polyrotaxanes and polyrotaxanes, etc., because the cyclic molecules constituting the polyrotaxane move on linear molecules Arise. Since such characteristics can be imparted, the polyrotaxane is expected to have various applications, and its research and development is actively performed.

Research has also been conducted on blending this polyrotaxane into a rubber composition.
For example, Patent Document 1 discloses a rubber composition in which a polyrotaxane or a crosslinked polyrotaxane is blended with a liquid styrene-butadiene copolymer for the purpose of achieving both steering stability and durability of the tire. However, in Patent Document 1, the polyrotaxane or the crosslinked polyrotaxane is dispersed in the styrene-butadiene rubber composition, but does not describe that the rubber composition and the polyrotaxane are crosslinked by vulcanization.

  Patent Document 2 discloses a composition in which a polyrotaxane or a crosslinked polyrotaxane is blended with a resin having a tackifying property with a softening point of 80 to 200 ° C. for the purpose of achieving both steering stability and durability of the tire. Disclose. However, Patent Document 2 does not describe the crosslinking between the rubber composition and the polyrotaxane as well as Patent Document 1. Therefore, “durability”, which is one of the purposes, has not been improved even in the system disclosed in Patent Document 2, and is comparable to the system in which no polyrotaxane is blended.

JP2009-062485A. JP2009-062484A.

Then, the objective of this invention is providing the rubber composition which forms the crosslinked body which the polyrotaxane and the rubber component bridge | crosslinked, and this crosslinked body.
Another object of the present invention is to form a crosslinked product having the properties of polyrotaxane, in particular, a desired tensile strength and / or a desired tensile elongation and / or a desired compression set, in addition to the above-mentioned purpose. It is to provide a rubber composition.
Furthermore, the objective of this invention provides the manufacturing method of a crosslinked body which has the characteristic of a polyrotaxane, especially the desired tensile strength and / or the desired tensile elongation rate, and / or the desired compression set in addition to the said objective. There is.

The inventors have found the following invention.
<1> A. A polyrotaxane in which a blocking group is arranged so that the cyclic molecule is not detached at both ends of a pseudopolyrotaxane in which the opening of the cyclic molecule is skewered by a linear molecule;
B. Non-diene rubber; and C.I. A. Polyrotaxane and B.I. A rubber composition comprising: a crosslinking agent for crosslinking with a non-diene rubber.

<2> In the above item <1>, A. It is preferable that the cyclic molecule of the polyrotaxane has at least one selected from the group consisting of a group having an unsaturated double bond and a functional group capable of causing a hydrogen abstraction reaction.
<3> In the above item <2>, the group having an unsaturated double bond has at least one selected from the group consisting of an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, a styryl group, and a cinnamoyl group. Good.
<4> In the above <2> or <3>, the functional group capable of causing hydrogen abstraction reaction is alkyloxy group, polyether group, alkyl ester group, polyester group, alkyl ketone group, polycarbonate group, t-butyl group, thiol. It is preferable to have at least one selected from the group consisting of a group and a phenol group.

<5> In any one of the above items <1> to <4>, The non-diene rubber may be at least one selected from the group consisting of ethylene / propylene rubber, ethylene / propylene / diene rubber, isobutylene / isoprene rubber, and silicone rubber.
<6> In any one of the above items <1> to <5>, C.I. The crosslinking agent may be a sulfur crosslinking agent and / or an organic peroxide crosslinking agent.
<7> In any one of the above items <1> to <6>, C.I. The crosslinking agent may be an organic peroxide crosslinking agent.

<8> In any one of the above items <1> to <7>, C.I. The cross-linking agent is A. of the rubber composition. Polyrotaxane and B.I. The total amount with the non-diene rubber is 100 parts by weight, but it is 1 to 10 parts by weight, preferably 2 to 6 parts by weight, more preferably 2 to 5 parts by weight.
<9> In any one of the above items <1> to <8>, The polyrotaxane is a rubber composition A.I. Polyrotaxane and B.I. When the total amount with the non-diene rubber is 100 parts by weight, 1 to 40 parts by weight, preferably 5 to 30 parts by weight, and more preferably 10 to 25 parts by weight in the 100 parts by weight.

<10> A crosslinked product formed by including the rubber composition according to any one of the above items <1> to <9>. In particular, a crosslinked product formed by having the rubber composition according to any one of <1> to <9> above, Polyrotaxane and B.I. It is preferable to include a crosslinked structure with a non-diene rubber.
In <11> above <10>, constitutes a tensile strength _{S M} of the crosslinked M of the <10>, the crosslinked body M A. Polyrotaxane was added to B.I. The ratio S _M / S _N to the tensile strength S _N of the crosslinked product N formed by having a rubber composition obtained by substituting with a non-diene rubber is 1.10 or more, preferably 1.20 or more, more Preferably it is 1.30 or more.
<12> In the above item <10> or <11>, constitutes a tensile elongation ratio _{R M} of the crosslinked M of the <10> or <11>, the crosslinked body M A. Polyrotaxane was added to B.I. The ratio R _{M /} R _N with tensile elongation ratio R _N of the crosslinked N formed with a rubber composition obtained by replacing the non-diene-based rubber is 1.10 or more, preferably 1.30 or more, More preferably, it is 1.50 or more.

In any one of <13> above <10> - <12>, constituting a compression set _{X M} of either a crosslinked form M of the <10> - <12>, the crosslinked body M A. Polyrotaxane was added to B.I. The ratio X _M / X _N to the compression set X _N of the crosslinked product N formed by having a rubber composition obtained by replacing with a non-diene rubber is 1.0 or less, preferably 0.9 or less, More preferably, it is 0.8 or less.
<14> A molded article having the crosslinked product of any one of <10> to <13>.

<15> A. A polyrotaxane in which a blocking group is arranged so that the cyclic molecule is not detached at both ends of a pseudopolyrotaxane in which the opening of the cyclic molecule is skewered by a linear molecule;
B. Non-diene rubber; and C.I. A. Polyrotaxane and B.I. A method for producing a crosslinked product from a rubber composition comprising a crosslinking agent for crosslinking with a non-diene rubber,
I. A. B. polyrotaxane; Non-diene rubber; and C.I. A. Polyrotaxane and B.I. Preparing a rubber composition containing a crosslinking agent for crosslinking with a non-diene rubber;
II. Kneading the rubber composition; and III. Forming the kneaded material obtained;
The method as described above, wherein a crosslinked product is obtained by having

<16> In the above item <15>, A. The cyclic molecule of polyrotaxane preferably has at least one selected from the group consisting of a group having an unsaturated double bond and a functional group capable of causing a hydrogen abstraction reaction.
<17> In the above <16>, the group having an unsaturated double bond has at least one selected from the group consisting of an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, a styryl group, and a cinnamoyl group. Good.
<18> In the above <16> or <17>, the functional group capable of causing a hydrogen abstraction reaction is an alkyloxy group, a polyether group, an alkyl ester group, a polyester group, an alkyl ketone group, a polycarbonate group, a t-butyl group, or a thiol. It is preferable to have at least one selected from the group consisting of a group and a phenol group.

<19> In any one of the above items <15> to <18>, The non-diene rubber may be at least one selected from the group consisting of ethylene / propylene rubber, ethylene / propylene / diene rubber, isobutylene / isoprene rubber, and silicone rubber.
<20> In any one of the above items <15> to <19>, C.I. The crosslinking agent may be a sulfur crosslinking agent and / or an organic peroxide crosslinking agent.
<21> In any one of the above items <15> to <20>, C.I. The crosslinking agent may be an organic peroxide crosslinking agent.

<22> In any one of the above items <15> to <21>, C.I. The cross-linking agent is A. of the rubber composition. Polyrotaxane and B.I. The total amount with the non-diene rubber is 100 parts by weight, but it is 1 to 10 parts by weight, preferably 2 to 6 parts by weight, more preferably 2 to 5 parts by weight.
<23> In any one of the above items <15> to <22>, The polyrotaxane is a rubber composition A.I. Polyrotaxane and B.I. When the total amount with the non-diene rubber is 100 parts by weight, 1 to 40 parts by weight, preferably 5 to 30 parts by weight, and more preferably 10 to 25 parts by weight in the 100 parts by weight.

In any one of <24> above <15> - <23>, constituting the <15> and a tensile strength _{S M} of either a crosslinked form M to <23>, the crosslinked body M A. Polyrotaxane was added to B.I. The ratio S _M / S _N to the tensile strength S _N of the crosslinked product N formed by having a rubber composition obtained by substituting with a non-diene rubber is 1.10 or more, preferably 1.20 or more, more Preferably it is 1.30 or more.
In any one of <25> above <15> - <24>, constituting the <15> and a tensile elongation ratio _{R M} of the crosslinked M to <24>, the crosslinked body M A. Polyrotaxane was added to B.I. The ratio R _{M /} R _N with tensile elongation ratio R _N of the crosslinked N formed with a rubber composition obtained by replacing the non-diene-based rubber is 1.10 or more, preferably 1.30 or more, More preferably, it is 1.50 or more.

In any one of <26> above <15> - <25>, constituting the <15> and compression set _{X M} of either a crosslinked form M to <25>, the crosslinked body M A. Polyrotaxane was added to B.I. The ratio X _M / X _N to the compression set X _N of the crosslinked product N formed by having a rubber composition obtained by replacing with a non-diene rubber is 1.0 or less, preferably 0.9 or less, More preferably, it is 0.8 or less.

According to the present invention, it is possible to provide a crosslinked product obtained by crosslinking a polyrotaxane and a rubber component, and a rubber composition that forms the crosslinked product.
Further, according to the present invention, in addition to the above-described effects, a crosslinked product having the characteristics of polyrotaxane, particularly a desired tensile strength and / or a desired tensile elongation and / or a desired compression set, and a rubber forming the crosslinked product A composition can be provided.
Furthermore, the present invention provides a method for producing a crosslinked product having the characteristics of polyrotaxane, in particular, a desired tensile strength and / or a desired tensile elongation and / or a desired compression set, in addition to the above effects. is there.

Hereinafter, the invention described in the present application will be described in detail.
The present application discloses a rubber composition, a crosslinked product formed with the rubber composition, and a molded article having the crosslinked product. Hereinafter, it demonstrates in order.

<Rubber composition>
The present application relates to A.I. A polyrotaxane in which a blocking group is arranged so that the cyclic molecule is not detached at both ends of a pseudopolyrotaxane in which the opening of the cyclic molecule is skewered by a linear molecule;
B. Non-diene rubber; and C.I. A. Polyrotaxane and B.I. A crosslinking agent for crosslinking with non-diene rubber;
A rubber composition containing is disclosed.

<< A. Polyrotaxane >>
A. The polyrotaxane is formed by arranging blocking groups so that the cyclic molecule is not detached at both ends of the pseudopolyrotaxane in which the opening of the cyclic molecule is skewered by the linear molecule.
<< A-1. Cyclic molecule >>
A. The cyclic molecule of polyrotaxane is not particularly limited as long as it is cyclic, has an opening, and is included in a skewered manner by linear molecules.
The cyclic molecule is an A.I. Components other than polyrotaxane, specifically, B.I. In order to promote crosslinking with the non-diene rubber, it is preferable to have a group having an unsaturated double bond and / or a functional group capable of causing a hydrogen abstraction reaction.
Examples of the group having an unsaturated double bond include, but are not limited to, an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, a styryl group, and a cinnamoyl group.

Examples of functional groups capable of causing hydrogen abstraction include alkyloxy groups, polyether groups, alkyl ester groups, polyester groups, alkyl ketone groups, polycarbonate groups, t-butyl groups, thiol groups, and phenol groups. However, it is not limited to these.
In addition to the above, B.I. Examples of the group for promoting crosslinking with the non-diene rubber include an amine, a carboxylic acid group, and an oxime group, but are not limited thereto.
Of these, it preferably has an acryloyl group, an allyl group, an alkyl ester group, or a polyester group.

In addition to the above-mentioned groups, the cyclic molecule has a group having the following hydrophobic group in consideration of compatibility with other components in the rubber composition, a molding process from the rubber composition to a crosslinked body, and the like. It may be.
For example, as a group having a hydrophobic group, acetyl group, butyl ester group, hexyl ester group, octadecyl ester group, polycaprolactone group, polyalkylene carbonate group, polypropylene glycol group, polytetramethylene glycol group, polyacrylic acid methyl group, Examples thereof include, but are not limited to, a group having a hydrophobic group such as a polyethyl acrylate hexyl group. Of these, a polycaprolactone group and a polyalkylene carbonate group are preferable.

  For example, the cyclic molecule may be selected from the group consisting of α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin. The group having the hydrophobic group or the group other than the group having the hydrophobic group is preferably contained by substituting a part of the —OH group such as α-cyclodextrin. For example, a group having the hydrophobic group or a group other than the group having the hydrophobic group may be bonded to the cyclic molecule through a spacer. In order to bind the spacer, the cyclic molecule used as a raw material preferably has a hydroxyl group.

<< A-2. Linear molecule >>
A. The linear molecule of polyrotaxane is not particularly limited as long as it can be included in a skewered manner in the opening of the cyclic molecule to be used.
For example, as linear molecules, polyvinyl alcohol, polyvinyl pyrrolidone, poly (meth) acrylic acid, cellulosic resins (carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, etc.), polyacrylamide, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyvinyl Polyolefin resins such as acetal resins, polyvinyl methyl ether, polyamines, polyethyleneimine, casein, gelatin, starch, and / or copolymers thereof, polyethylene, polypropylene, and copolymers of other olefin monomers; Polyester resins, polyvinyl chloride resins, polystyrene resins such as polystyrene and acrylonitrile-styrene copolymer resins, polymethyl Acrylic resins such as tacrylate, (meth) acrylic acid ester copolymer, acrylonitrile-methyl acrylate copolymer resin, polycarbonate resin, polyurethane resin, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, etc .; and their derivatives or Modified products, polyisobutylene, polytetrahydrofuran, polyaniline, acrylonitrile-butadiene-styrene copolymer (ABS resin), polyamides such as nylon, polyimides, polydienes such as polyisoprene and polybutadiene, polysiloxanes such as polydimethylsiloxane , Polysulfones, polyimines, polyacetic anhydrides, polyureas, polysulfides, polyphosphazenes, polyketones, polyphenylenes, polyhaloolefins, and It may be selected from the group consisting of these derivatives. For example, it may be selected from the group consisting of polyethylene glycol, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, polypropylene, polyvinyl alcohol and polyvinyl methyl ether. Particularly preferred is polyethylene glycol.

The linear molecule should have a weight average molecular weight of 1,000 or more, preferably 3,000 to 100,000, more preferably 6,000 to 50,000.
A. In the polyrotaxane, the combination of (cyclic molecule, linear molecule) may be (derived from α-cyclodextrin, derived from polyethylene glycol).

<< A-3. Blocking group >>
A. The blocking group of the polyrotaxane is not particularly limited as long as it is a group that is arranged at both ends of the pseudopolyrotaxane and acts so that the cyclic molecule to be used does not leave.
For example, as a blocking group, dinitrophenyl groups, cyclodextrins, adamantane groups, trityl groups, fluoresceins, silsesquioxanes, pyrenes, substituted benzenes (substituents are alkyl, alkyloxy, hydroxy, Examples include, but are not limited to, halogen, cyano, sulfonyl, carboxyl, amino, phenyl, etc. One or more substituents may be present), optionally substituted polynuclear aromatics (substituted) Examples of the group include, but are not limited to, the same as described above, and one or more substituents may be present.) And a group consisting of steroids. It is preferably selected from the group consisting of dinitrophenyl groups, cyclodextrins, adamantane groups, trityl groups, fluoresceins, silsesquioxanes, and pyrenes, more preferably adamantane groups or cyclodextrins. It should be similar.

<< B. Non-diene rubber >>
Non-diene rubbers are rubbers characterized in that they do not have a double bond in the polymer main chain or have very few even if they have. In addition, “very slightly present” means that the degree of unsaturation representing the amount of double bonds is 2.5 mol% or less.
Non-diene rubbers are resistant to oxidation and have excellent weather resistance, aging resistance, and ozone resistance.

Non-diene rubbers include, but are not limited to, ethylene / propylene rubber (EPM), ethylene / propylene / diene rubber (EPDM), isobutylene / isoprene rubber (IIR), silicone rubber, urethane rubber, fluorine rubber, and the like. Not. In particular, ethylene / propylene rubber (EPM), ethylene / propylene / diene rubber (EPDM) and silicone rubber are preferable, and ethylene / propylene / diene rubber (EPDM) is more preferable.
IIR has isoprene double bonds “very slightly” in the main chain. The ethylene / propylene / diene rubber (EPDM) has an ethylene component, a propylene component, and a third component other than the ethylene component and the propylene component, and has a double bond in the side chain of the third component. . It is considered that IIR or EPDM has these double bonds, and thus is important for crosslinking between polyrotaxane and IIR or EPDM.

<< C. Cross-linking agent >>
The cross-linking agent is Polyrotaxane and B.I. There is no particular limitation as long as it has a function of crosslinking with non-diene rubber. The cross-linking agent is B.B in the rubber composition. You may have the effect | action which bridge | crosslinks rubber components, such as non-diene rubber.
Sulfur, sulfur compounds, organic peroxides, selenium, magnesium oxide, lead monoxide and zinc oxides, polyamines, P-quinone dioxime and P, P'-dibenzoylquinone dioxime oximes as crosslinking agents, Examples include, but are not limited to, nitroso compounds of P-dinitrosobenzidine, alkylphenol-formaldehyde resins, melamine-formaldehyde condensate resins, ammonium benzoate ammonium salts, and the like.
Sulfur and organic peroxides are preferable, and organic peroxides are more preferable.

The organic peroxide is preferably selected in consideration of the temperature of the rubber kneading process and the temperature of the molding process.
1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl as organic peroxide -2,5-di (t-butylperoxy) hexane, 1,3-bis (t-butylperoxy-isopropyl) -benzene, di-t-hexyl peroxide, t-butyl peroxide benzoate, etc. Although it can, it is not limited to these.

  In order to promote the function of the crosslinking agent, a crosslinking aid can be used in combination. For example, sulfur or sulfur compounds such as dipentamethylene thiuram tetrasulfide and 2-mercaptobenzothiazole, ethylene di (meth) acrylate, polyethylene di (meth) acrylate, divinylbenzene, diallyl phthalate, triallyl cyanurate, phenylene dimaleimide, toluy Examples thereof include polyfunctional monomers such as range maleimide, oxime compounds such as p-quinone oxime and p, p′-benzoylquinone oxime, and stearic acid.

<< Ingredient ratio, etc. >>
A. The polyrotaxane is an A.I. Polyrotaxane and B.I. When the total with the non-diene rubber is 100 parts by weight, the amount is 1 to 35 parts by weight, preferably 3 to 15 parts by weight, and more preferably 5 to 10 parts by weight.
C. The cross-linking agent is A. of the rubber composition. Polyrotaxane and B.I. The total amount with the non-diene rubber is 100 parts by weight, but it is 1 to 10 parts by weight, preferably 2 to 6 parts by weight, more preferably 2 to 5 parts by weight.
Here, “to 100 parts by weight” means “to” with respect to, for example, C.I. If the amount of cross-linking agent is 3 parts by weight, Polyrotaxane, B.I. Non-diene rubber, and C.I. It means that the total amount with the crosslinking agent is 103 parts by weight.

<< Other components of rubber composition >>
The rubber composition of the present invention may contain a filler in addition to the components A to C in order to impart reinforcement, increase in weight, and special functions.
Examples of the filler include, but are not limited to, carbon black, silica, clay, calcium carbonate, talc, styrene, reinforcing short fibers, and the like.
The rubber composition of the present invention may contain other components in addition to the components A to C and the filler. Examples of other components include, but are not limited to, an anti-aging agent, an anti-scotch agent, a peptizer, a plasticizer, a coupling agent, and a colorant.

  Amine antioxidants such as N-phenyl-N′-1,3-dimethylbutyl-p-phenylenediamine, 2,2,4-trimethyl-1,2 dihydroquinoline polymer, 2,2 ′ Polyphenolic antioxidants such as methylenebis (4-methyl-6-tert-butylphenol, 4,4'-thiobis (3-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole, tris (nonylated phenyl) Secondary anti-aging agents such as phosphite, and combinations thereof can be mentioned, but are not limited thereto.

Examples of the scotch inhibitor include, but are not limited to, phthalic anhydride and N-cyclohexylthiophthalimide.
Examples of the peptizer include, but are not limited to, o, o′-dibenzamide diphenyl sulfide, zinc salt of 2-benzamidothiophenol, and the like.

  As plasticizers (softeners), oil softeners such as paraffinic, naphthenic, aromatic and coal tar, plant-derived softeners such as cottonseed oil, stearic acid and rosin, dioctyl phthalate, dioctyl sebacate phenol resin, etc. Examples include, but are not limited to, synthetic softeners.

  Examples of the coupling agent include vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, and bis (3- (triethoxysilyl) propyl) tetrasulfide. It is not limited.

Examples of the colorant include, but are not limited to, titanium oxide, zinc oxide, carbon black, azo pigments, and phthalocyanine pigments.
A small amount of diene rubber is added to non-diene rubber by an existing method, specifically, A. of rubber composition. Polyrotaxane and B.I. When the total with the non-diene rubber is 100 parts by weight, 10 parts by weight or less may be added to 100 parts by weight. In this case, the crosslinked body obtained from the composition can be obtained as follows. That is, the diene rubber is preferably vulcanized with a non-diene rubber by an existing vulcanization method, and the polyrotaxane is vulcanized with a non-diene rubber. More specific examples include, but are not limited to, a system in which styrene-butadiene rubber is vulcanized in EPDM with a peroxide and the EPDM is also vulcanized with polyrotaxane.

<The manufacturing method of the crosslinked body formed having a rubber composition>
The present application relates to A.I. B. polyrotaxane; Non-diene rubber; and C.I. A method for producing a crosslinked product from a rubber composition containing a crosslinking agent,
I. A. B. polyrotaxane; Non-diene rubber; and C.I. Preparing a rubber composition containing a crosslinking agent;
II. Kneading the rubber composition; and III. Forming the kneaded material obtained;
The method of obtaining a crosslinked body by having is provided.
“A. Polyrotaxane”, “B. Non-diene rubber”, “C. Crosslinking agent” and “Rubber composition” are as described above.

<< Step I >>
Step I comprises A. B. polyrotaxane; Non-diene rubber; and C.I. A rubber composition containing a crosslinking agent.
<< Step IA >>
A. The polyrotaxane can be prepared by a conventionally known method. For example, it can prepare with reference to Unexamined-Japanese-Patent No. 2005-154675 and Unexamined-Japanese-Patent No. 2007-91938.

When the cyclic molecule has a group having an unsaturated double bond, and / or has a functional group capable of causing a hydrogen abstraction reaction, and / or has a group other than the above, these groups are as follows: Can be introduced. That is, the cyclic molecule of polyrotaxane preferably has a hydroxyl group, and these groups can be introduced using a reaction with the hydroxyl group, for example, the reaction shown below.
When the cyclic molecule has, for example, a group having an unsaturated double bond, the introduction of the group is carried out by introducing a methacrylic acid ester group, an acrylic acid ester group, or a cinnamic acid ester group by an esterification reaction; Examples thereof include, but are not limited to, introduction of acryloyloxyethylcarbamoyl group, methacryloyloxyethylcarbamoyl group, and allylcarbamoyl group; and vinyl group and alkylstyryl group by etherification reaction.

In addition, when the cyclic molecule has a functional group capable of causing a hydrogen abstraction reaction, for example, the hexyloxy group, octadecyloxy group, alkylphenol group, alkylene ketone group by etherification reaction; Examples include, but are not limited to, a caprolactone group, a polycarbonate group, a polypropylene group, a polytetramethyloxy group, a polyalkylene amide group, and a polyacryl ester group.
Furthermore, for example, when the cyclic molecule has an amine, a carboxylic acid group, etc., the hexylamide group, amino acid residue, ethylthiol group, alkylamine group by an amidation reaction; Examples thereof include, but are not limited to, ester groups; alkylurea groups obtained by urea reaction;

  In addition, when the cyclic molecule has a group having a hydrophobic group, for example, to introduce the group, introduction of acetyl group, butyl ester group, hexyl ester group, benzyl ester group, etc. by esterification reaction; urethanization reaction Incorporation of butylcarbamoyl group, ethylhexylcarbamoyl group, and the like by, but not limited to.

<< Step IB >>
B. The non-diene rubber can be prepared by purchasing a commercially available rubber or by producing it independently.
<< Step IC >>
C. The cross-linking agent can be prepared by purchasing a commercially available product or by producing it independently.
The rubber composition can be obtained by mixing the components A to C and, if necessary, other components.

<< Step II >>
Step II is a step of kneading the rubber composition obtained in Step I.
The kneading step is a step of not only mixing the above-described rubber composition but also mixing other additive components and uniformly dispersing them by applying mechanical shear stress. This step can be performed by a conventionally known method, for example, by using a two-roll kneader, a closed biaxial mixer, or the like, but is not limited thereto.

<< Step III >>
Step III is a step of molding the kneaded product obtained in Step II.
The molding step depends on the rubber composition to be used, the obtained kneaded product, the shape of the crosslinked product to be obtained, etc., but can be performed by a conventionally known method, for example, by press molding or a screw type extruder. Although it can carry out using extrusion processing, calendar processing, injection molding, paste processing by a knife coater or a roll coater, it is not limited to these.
Crosslinking of the polyrotaxane and the non-diene rubber can be performed in Step II and / or Step III. In these steps, crosslinking between polyrotaxanes and crosslinking between non-diene rubbers may be performed.

A method of crosslinking using heat generated in the kneading in Step II, and a method of crosslinking by further applying heat in Step II and / or Step III can be used.
In Step III, crosslinking can be performed with heat applied during molding.
Depending on the rubber composition to be used, the shape of the molded product, and the type of the crosslinking agent, in Step II and / or Step III, for example, the crosslinking may be performed by heating at 100 to 200 ° C. for 3 to 20 minutes. However, the crosslinking is not limited to this.
After the molding in Step III, the molded product may be further heated to provide a step of secondary crosslinking (which may be vulcanized).

<Crosslinked product>
The crosslinked body of the present application is a crosslinked body formed with the rubber composition described above. The cross-linked product is obtained from A.I. Polyrotaxane and B.I. Includes a crosslinked structure with non-diene rubber.
The crosslinked product of the present application may have the following characteristics. Hereinafter, the crosslinked body of the present invention is referred to as “crosslinked body M”. In addition, among the “crosslinked bodies M”, A. All of the polyrotaxane A crosslinked product as a comparative control formed by using a rubber composition obtained by substituting with a non-diene rubber is referred to as “crosslinked product N”.

The ratio S _M / S _N of the tensile strength S _M of the crosslinked body _M and the tensile strength S _N of the crosslinked body _N is 1.10 or more, preferably 1.10 to 2.50, more preferably 1.20 to 2 .50, most preferably 1.30 to 2.50.
A tensile elongation rate _{R M} of the crosslinked M, the ratio _R M / _{R N} with tensile elongation ratio _{R N} of the crosslinked N 1.10 or more, preferably from 1.10 to 3.50, more preferably 1.30 ~ 3.50, most preferably 1.50 to 3.50.
The ratio X _M / X _N between the compression set X _M of the crosslinked product _M and the compression set X _N of the crosslinked product _N is 1.0 or less, preferably 0.1 to 1.0, more preferably 0.1. It is good that it is -0.9, Most preferably, it is 0.1-0.8.

<< Tensile strength >>
In the present application, the tensile strength is measured as follows.
It is measured by a tensile test according to JIS K 6251: 2010. The test piece is pulled, and the stress when it breaks is defined as the tensile strength.

<< Tensile elongation >>
In the present application, the tensile elongation is measured as follows.
It is measured by a tensile test according to JIS K 6251: 2010. The test piece (length L ₀ before the test) is pulled, the length of the test piece when it is broken is Lt, and the tensile elongation is obtained by the following equation.
Tensile elongation (%) = (Lt−L ₀ ) / L ₀ × 100.

<< compression set >>
In the present application, compression set is measured as follows.
Measured according to JIS K 6262: 2006. The measurement conditions are as follows. That is, using a test piece having a radius of 29 mm and a thickness of 12.5 mm, measurement is performed under the conditions of i) 70 ° C. ± 1 ° C. for 24 hours, or ii) 100 ° C. ± 1 ° C. for 22 hours, and a compressibility of 25%. In addition, although i) "or" ii) is described, in the present application, "crosslinked body M" and "crosslinked body N" are the same conditions, that is, both "crosslinked body M" and "crosslinked body N" are i. ) Or ii), the compression set ratio X _M / X _N obtained by measurement may be obtained.

The crosslinked body of the present application is A. Polyrotaxane and B.I. By cross-linking with the non-diene rubber, a part of the three-dimensional structure formed only from the rubber component is replaced with a polyrotaxane structure.
In general, polyrotaxane has a pulley effect in which a cyclic molecule is movable on a linear molecule of polyrotaxane. For this reason, when an external stress is applied to the cross-linked body, the stress is not concentrated on a part of the cross-linked body but dispersed throughout the cross-linked body due to the pulley effect. Therefore, it is considered that the tensile strength and tensile elongation of the crosslinked product of the present application are improved by the pulley effect.
In a preferred embodiment of the crosslinked product of the present application, since the polyrotaxane has a group having an unsaturated double bond and / or a functional group capable of causing a hydrogen abstraction reaction, the polyrotaxane and the non-diene rubber can be crosslinked at many sites. In addition, it is considered that deformation recovery due to external stress is due to entropy elasticity (general rubber elasticity) of polymer chains and entropy elasticity due to deviation of cyclic molecules. Therefore, it is considered that a crosslinked body having flexibility and reduced compression set can be provided while increasing the crosslinking density.

Since the crosslinked product of the present invention has the above properties, it can be applied to various rubber-related fields. Examples include, but are not limited to, automotive rubber parts, industrial rubber, mechanical rubber, and architectural rubber. Specific products include automotive parts such as wiper blades, glassons, weatherstrips, wire / cable coatings, hoses, bumpers, interior materials, films, etc .; industries such as OA rolls, heat-resistant rubber sheets, polymer insulators, and conveyor belts. Rubber products for machinery; Rubber parts for machinery such as switchboard packing, insulation tubes; Rubber parts for construction such as window frame rubber, door seals, drainage materials, roofing, sealing, etc., but are not limited thereto.
EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to a present Example.

<Preparation of polyrotaxane>
Polyrotaxane was prepared by the method described in WO2005 / 080469 or WO2010 / 024431.
In addition, ¹ H-NMR analysis of the polyrotaxane synthesized below was performed with 400 MHz JEOL JNM-AL400 (manufactured by JEOL Ltd.).
The molecular weight and molecular weight distribution of the polyrotaxane were measured with a TOSOH HLC-8220 GPC apparatus. Column: TSK guard column Super AW-H and TSKgel Super AWM-H (two linked), eluent: dimethyl sulfoxide (DMSO) /0.01 M LiBr, column oven: 50 ° C., flow rate: 0.5 ml / min, sample The concentration was measured under the conditions of about 0.2 wt / vol%, injection amount: 20 μl, pretreatment: filtration through a 0.2 μm filter, and standard molecular weight: PEO. Further, infrared spectroscopic analysis (IR) was measured with Nicolet 4700 (manufactured by Thermo Fisher Scientific Co., Ltd.).

(Synthesis Example 1: Preparation of polyrotaxane (PR-1) having a caprolactone group)
A polyrotaxane (HAPR) modified with a hydroxypropyl group disclosed in Example 3 of WO2005 / 080469 was prepared.
In order to obtain compatibility with the non-diene rubber, a polyrotaxane having a caprolactone group was produced by the following method. 10 g of HAPR was placed in a three-necked flask, and 45 g of ε-caprolactone was introduced while slowly flowing nitrogen. After stirring uniformly with a mechanical stirrer at 100 ° C. for 30 minutes, the reaction temperature was raised to 130 ° C., and 1.6 g of tin 2-ethylhexanoate (50 wt% solution) previously diluted with toluene was added and allowed to react for 5 hours. The solvent was removed to obtain 55 g of a polyrotaxane (PR-1) having a caprolactone group. Moreover, weight average molecular weight Mw: 580,000 and molecular weight distribution Mw / Mn: 1.5 were confirmed by GPC.

(Synthesis Example 2: Preparation of polyrotaxane (PR-2) having an allyl group)
50 g of PR-1 obtained in Synthesis Example 1 above, 50 g of xylene, and 5 mg of tin dibutyldilaurate (manufactured by Tokyo Chemical Industry Co., Ltd.) were placed in a three-necked flask, and while slowly flowing nitrogen and stirring at room temperature, 5.3 g of allyl isocyanate ( Aldrich) was slowly added dropwise and stirred overnight. Infrared spectroscopic analysis (IR) confirmed that the isocyanate group-derived peak (2260 cm ⁻¹ ) had disappeared, removed the solvent, and obtained an allyl group-containing polyrotaxane (PR-2). A signal (5.1, 5.8 ppm) derived from a vinyl group was confirmed from ¹ H-NMR (DMSO-d ⁶ ) of the obtained compound (PR-2).

<Preparation of rubber composition>
Unvulcanized rubber compositions A-1 to A-11 and B-1 to B-4 were prepared with the compositions shown in Table 1 below. The numbers in Table 1 are parts by weight. The components in Table 1 below are shown below.
"Rubber 1" and "Rubber 2" were ethylene-propylene-diene rubber EPT3045 (Mitsui Chemicals) and EPT4045 (Mitsui Chemicals), respectively. In addition, the diene component of EPT3045 and EPT4045 is 5-ethylidene-2-norbornene, and the content rate of a diene component is 4.7 wt% and 8.1%, respectively.
The “peroxide” was 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (Perhexa ™ 25B (manufactured by NOF Corporation)).
In Table 1, “CB” means carbon black, and Seast So (manufactured by Tokai Carbon Co., Ltd.) was used.
Zinc oxide was manufactured by Hakusui Tech.
As stearic acid, a product manufactured by Nippon Oil & Fats was used.
As the paraffin oil, PW-380 (manufactured by Idemitsu Kosan) was used.
“Sulfur” was manufactured by Kawagoe Chemical.
"Vulcanization accelerator 1" is 2-mercaptobenzothiazole (Noxeller MP (manufactured by Ouchi Shinsei Chemical Co., Ltd.)), and "Vulcanization accelerator 2" is tetramethyltyrium disulfide ( Noxeller TT-P (Ouchi Shinsei Chemical Co., Ltd.)).

<Preparation of crosslinked body>
Each of the compositions A-1 to A-11 and B-1 to B-4 in Table 1 was kneaded with an 8-inch water-cooled roll HF-2R (manufactured by Daihan Co., Ltd.) and then press-molded at 170 ° C ( Electric heat press No.61-034, manufactured by Otake Machinery Co., Ltd., and a cross-linked specimen were prepared. When the test piece was a sheet having a thickness of 2 mm (150 mm × 150 mm × thickness 2 mm), the pressing time was 15 minutes, and in the case of a cylindrical shape (radius 29 mm, thickness 12.5 mm), it was 20 minutes.

<Degree of vulcanization of crosslinked product>
The degree of vulcanization of each crosslinked product was measured according to JIS K 6300-2 (2001). A vulcanization degree tester (Flat Die Rheometer FDR, manufactured by Ueshima Seisakusho) was used under the conditions of 170 ° C., amplitude ± 1 °, 1.67 Hz. Based on the results of the vulcanization degree test, the vulcanization time of each composition was determined.

(Examples 1-11 and Comparative Examples 1-4)
<Evaluation of physical properties of cross-linked specimen>
The following physical properties were evaluated using each cross-linked specimen. The results are shown in Table 2 below.
<< Density measurement >>
The density was measured according to JIS K 6268: 1998.
Using a test piece of 20 mm × 20 mm × thickness 2.0 mm, it was measured by an automatic densimeter Densimeter-H (manufactured by Toyo Seiki Seisakusho) under the condition of temperature 23 ° C. ± 2 ° C. by the method A described in JIS.

<< Hardness measurement >>
Hardness was measured according to JIS K 6253: 2006.
Three sheet-shaped vulcanized crosslinked bodies having a thickness of 2.0 mm were laminated and measured with an Asuka rubber hardness meter (durometer) A type (manufactured by Kobunshi Keiki Co., Ltd.) at a temperature of 23 ° C. ± 2 ° C.
<< Tensile test-Measurement of tensile strength and tensile elongation->>
As described above, a tensile test was performed according to JIS K 6251: 2010, and the tensile strength and the tensile elongation were measured.
Cut out a 2.0mm thick sheet-like vulcanized cross-section into a dumbbell-shaped No. 3 test piece, precision universal testing machine Autograph AG-10kNXplus (manufactured by Shimadzu Corporation) at a temperature of 23 ° C ± 2 ° C and a tensile speed of 500mm / min. Was used to measure tensile strength and tensile elongation.

<< Compression set test >>
As described above, in accordance with JIS K 6262: 2006, compression set was measured by a gear type aging tester AG-1110 (manufactured by Ueshima Seisakusho).
<< Rebound resilience test >>
The impact resilience was measured according to JIS K 6255: 1996.
Using a test piece having a radius of 29 mm and a thickness of 12.5 mm, measurement was performed with a Ruppke-type rebound resilience tester (manufactured by Kobunshi Keiki Co., Ltd.) under the conditions of 29-39N holding force and temperature of 23 ° C. ± 2 ° C.

<< Williams abrasion test >>
According to JIS K 6264-2: 2005, a Williams wear test was performed, and a wear mass (mg) and a wear volume per work (cm ³ / MJ) were measured.
Using a test piece of 20 mm × 20 mm × 2.0 mm in thickness, under the conditions of a temperature of 23 ° C. ± 2 ° C., an additional force of 35.5 N on the test piece, abrasive paper A-P240, and a running time of 6 minutes It measured with the abrasion tester (made by Ueshima Seisakusho).
<< T-R (low temperature elastic recovery) test >>
In accordance with JIS K 6261: 2006, a TR (low temperature elastic recovery) test was performed, and the temperature at each recovery rate (10 to 70%) was measured.
Fully automatic TR tester TM-3531 using I-shaped test piece (parallel part between grips 2.0mm x 50m x thickness 2.0mm) under conditions of temperature 23 ° C ± 2 ° C and elongation 50% It was measured by.

< _SM / _SN , _RM / _RN, and _XM / _XN >
Tensile strength ratio S _M / S _N , tensile elongation ratio R _M / R _N , and compression set ratio X _M between the crosslinked body of Example (crosslinked body M) and the crosslinked body of Comparative Example (crosslinked body N) / a X _N, each tensile strength was determined from the tensile elongation percentage and the value of the compression set. Each ratio is also shown in Table 2.
The tensile strength ratio S _M / S _N , the tensile elongation ratio R _M / R _N , and the compression set ratio X _M / X _N of Example 1 are the ratios between the values of Example 1 and Comparative Example 1. I asked for it. Moreover, each ratio of Examples 2-6 was calculated | required from ratio of the value of each Example, and the value of Comparative Example 2. Further, each ratio of Example 7 was obtained from the ratio of the value of Example 7 and the value of Comparative Example 3. Moreover, each ratio of Examples 8-11 was calculated | required from the ratio of the value of each Example, and the value of the comparative example 4. FIG.

Table 2 shows the following.
In general, it is difficult to achieve all three properties of tensile strength, tensile elongation, and compression set, or two of the three to a desired value. However, see each of S _M / S _N (tensile strength ratio), R _M / R _N (tensile elongation ratio), and X _M / X _N (compression set) of Examples 1-11 in Table 2. When the polyrotaxane is blended and the polyrotaxane and the non-diene rubber are cross-linked, it can be seen that the tensile strength, tensile elongation, and compression set are improved. In particular, it can be seen that at least two of the three properties of tensile strength, tensile elongation, and compression set can be improved simultaneously.

It can also be seen that there is an effect of reducing the wear volume per work amount.
Looking at Examples 2 to 5 (components A-2 to A-5) and Examples 8 to 11 (components A-8 to A-11), increasing the blending amount can increase the tensile elongation. I understood.

Claims (13)

A. A polyrotaxane in which a blocking group is arranged so that the cyclic molecule is not detached at both ends of a pseudopolyrotaxane in which the opening of the cyclic molecule is skewered by a linear molecule;
B. Non-diene rubber; and C.I. A. Polyrotaxane and B. A crosslinking agent for crosslinking with non-diene rubber;
Containing a rubber composition.   A. The rubber composition according to claim 1, wherein the cyclic molecule of the polyrotaxane has at least one selected from the group consisting of a group having an unsaturated double bond and a functional group capable of causing a hydrogen abstraction reaction.   B. above. The rubber composition according to claim 1 or 2, wherein the non-diene rubber is at least one selected from the group consisting of ethylene / propylene rubber, ethylene / propylene / diene rubber, isobutylene / isoprene rubber, and silicone rubber.   C. above. The rubber composition according to any one of claims 1 to 3, wherein the crosslinking agent is a sulfur crosslinking agent and / or an organic peroxide crosslinking agent.   C. above. The rubber composition according to any one of claims 1 to 4, wherein the crosslinking agent is an organic peroxide crosslinking agent.   C. above. The crosslinking agent is the A. of the rubber composition. Polyrotaxane and B. The rubber composition according to any one of claims 1 to 5, wherein the total amount with respect to the non-diene rubber is 100 parts by weight relative to 1 to 10 parts by weight.   A. Polyrotaxane is the A. of the rubber composition. Polyrotaxane and B. The rubber composition according to any one of claims 1 to 6, wherein the total amount with the non-diene rubber is 1 to 40 parts by weight based on 100 parts by weight.   The crosslinked body formed by having the rubber composition of any one of Claims 1-7. The A. constituting the tensile strength S _M of the crosslinked M according to claim 8, the crosslinked M Polyrotaxane is converted into the B. The cross-linked product according to claim 8, wherein the ratio S _M / S _N to the tensile strength S _N of the cross-linked product N having a rubber composition obtained by replacing with a non-diene rubber is 1.10 or more. . Tensile and elongation rate R _M of the crosslinked M according to claim 8 or 9, constituting the crosslinked product M wherein A. Polyrotaxane is converted into the B. Claim 8 or 9, wherein the ratio R _{M /} R _N with tensile elongation ratio R _N of the crosslinked N formed with a rubber composition obtained by replacing the non-diene-based rubber is 1.10 or more Cross-linked product. A compression set X _M of the crosslinked body M of any one of claims 8 to 10, wherein forming the crosslinked M A. Polyrotaxane is converted into the B. The ratio X _M / X _N to the compression set X _N of the crosslinked body N formed by having a rubber composition obtained by substituting with a non-diene rubber is 1.0 or less. The crosslinked body of any one of Claims 1.   A molded article having the crosslinked body according to any one of claims 8 to 110. A. A polyrotaxane in which a blocking group is arranged so that the cyclic molecule is not detached at both ends of a pseudopolyrotaxane in which the opening of the cyclic molecule is skewered by a linear molecule;
B. Non-diene rubber; and C.I. A. Polyrotaxane and B. A method for producing a crosslinked product from a rubber composition comprising a crosslinking agent for crosslinking with a non-diene rubber,
I. A. A polyrotaxane; A non-diene rubber; Preparing a rubber composition containing a crosslinking agent;
II. Kneading the rubber composition; and III. Forming the kneaded material obtained;
The said method of obtaining the said crosslinked body by having.