Patent Application
20160289501
The present invention relates to an adhesive composition comprising latex of a highly saturated nitrile rubber.
A composite of rubber and fiber is used in various fields such as belt, rubber hose, diaphragm, tire, etc. In the field of belt, there are a timing belt for automobile, polyribbed belt, wrapped belt, V belt, etc.; and they are normally made by a composite of a base cloth of woven fabric and a rubber. For instance, a canvas protects around belt of V belt and a covering cloth is layered on teeth of toothed belt.
Conventionally, oil resistant rubbers such as chloroprene rubber and acrylonitrile-butadiene copolymer rubber were mainly used for the rubber. In recent years, however, a high-level heat resistance is demanding in order to cope with automobile exhaust gas restriction countermeasure, downsizing of engine compartment for light weighting of automobile, sealing of engine compartment for noise countermeasure, etc. Therefore, a highly saturated nitrile rubber resistant to both oil and heat is becoming used.
Taking an example of a timing belt, in which teeth are covered with a base cloth of nylon, the base cloth is generally treated with a solvent-based rubber paste. This is to improve an adhesive strength between the rubber and the base cloth and to inhibit abrasion by an engagement of belt and a toothed wheel. Recently, however, treatment techniques using water based adhesives instead of techniques using solvent based rubber pastes are demanding in order to prevent an environmental pollution by organic solvents.
As an example of the treatment techniques using water based adhesives, patent article 1 discloses an adhesive composition including a carboxyl group containing highly saturated nitrile rubber latex and a resorcinol-formaldehyde resin. However, requests to materials are becoming more severe along with improved performances of automobile engine compartments. Thus, there was a further demand for an adhesive composition which is able to form an adhesive layer superior in abrasion resistance after heat aging.
Patent document 1: Japanese Patent Application Laid-Open No. H6-286015
The object of the present invention is to provide an adhesive composition which enables to form an adhesive layer superior in abrasion resistance after heat aging.
By keen examination for solving said problem, the inventors have found that an object of the present invention can be achieved by an adhesive composition including: latex of a highly saturated nitrile rubber comprising a specific amount of a specific monomer unit; and a specific crosslinking aid. The present invention was attained based on such knowledge.
According to the present invention, an adhesive composition including a latex of a highly saturated nitrile rubber (A), comprising 10 to 55 wt % of α,β-ethylenically unsaturated nitrile monomer unit, 25 to 89 wt % of conjugated diene monomer unit and 1 to 20 wt % of α,β-ethylenically unsaturated dicarboxylic acid monoester monomer unit and having a iodine value of 120 or less; and a crosslinking aid (B) comprising 2 or more ethylenically unsaturated groups in a molecule is provided.
α,β-ethylenically unsaturated dicarboxylic acid monoester monomer unit above is preferably α,β-ethylenically unsaturated dicarboxylic acid monoalkylester monomer unit, and more preferably, mono n-butyl maleate unit.
In addition, the crosslinking aid (B) comprising 2 or more ethylenically unsaturated groups in a molecule is preferably maleimides comprising 2 or more ethylenically unsaturated groups in a molecule.
Further, in the invention, the composite of a fiber base material and a highly saturated nitrile rubber, obtained by bonding the fiber base material and the highly saturated nitrile rubber with the above adhesive composition, is provided. The composite is preferably belt, hose, diaphragm, or tire.
According to the present invention, an adhesive composition, which can form an adhesive layer superior in an abrasion resistance property after heat aging, can be provided.
The adhesive composition according to the present invention is an adhesive composition including latex of a highly saturated nitrile rubber (A), comprising 10 to 55 wt % of α,β-ethylenically unsaturated nitrile monomer unit, 25 to 89 wt % of conjugated diene monomer unit and 1 to 20 wt % of α,β-ethylenically unsaturated dicarboxylic acid monoester monomer unit and having a iodine value of 120 or less; and a crosslinking aid (B) comprising 2 or more ethylenically unsaturated groups in a molecule.
A highly saturated nitrile rubber (A) of the invention is a rubber obtained via a copolymerization process of α,β-ethylenically unsaturated nitrile monomer, a conjugated diene monomer, α,β-ethylenically unsaturated dicarboxylic acid monoester monomer, and other monomers added as needed which can copolymerize with each of said monomers. The rubber shows an iodine value of 120 or less.
α,β-ethylenically unsaturated nitrile monomer is not particularly limited with the proviso that it is α,β-ethylenically unsaturated compound comprising nitrile group; and there may be mentioned acrylonitrile; α-halogenoacrylonitrile such as α-chloroacrylonitrile, α-bromoacrylonitrile; α-alkylacrylonitrile such as methacrylonitrile; etc. Among these, acrylonitrile and methacrylonitrile are preferable, and acrylonitrile is the most preferable. α,β-ethylenically unsaturated nitrile monomer may be used alone or in combination.
A content of α,β-ethylenically unsaturated nitrile monomer unit with respect to all monomer units constituting highly saturated nitrile rubber (A) is 10 to 55 wt %, preferably 20 to 53 wt % and more preferably 25 to 50 wt %. In case when a content of α,β-ethylenically unsaturated nitrile monomer unit is too small, oil resistance of the obtained hardened adhesive layer (an adhesive composition hardened layer, formed after bonding using the adhesion composition of the invention) may decrease, while too large, low-temperature resistance thereof may decrease.
The conjugated diene monomer is not particularly limited, however, conjugated diene monomers of carbon numbers 4 to 6 such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, etc. are preferable, 1,3-butadiene and isoprene are more preferable, and 1,3-butadiene is the most preferable. Said conjugated diene monomers may be used alone or in combination.
A content of the conjugated diene monomer unit with respect to all monomer units constituting highly saturated nitrile rubber (A) is 25 to 89 wt %, preferably 32 to 78 wt % and more preferably 40 to 73 wt %. In case when the content of the conjugated diene monomer unit is too small, flexibility of the obtained hardened adhesive layer may decrease, while too large, heat resistance and chemical stability thereof may deteriorate. The content amount of the conjugated diene monomer unit includes hydrogenated parts, in case when copolymer is hydrogenated as described below.
Examples of the α,β-ethylenically unsaturated dicarboxylic acid monoester monomer may include α,β-ethylenically unsaturated dicarboxylic acid monoalkylester monomer such as monomethyl maleate, monoethyl maleate, monopropyl maleate, mono-n-butyl maleate, monomethyl fumarate, monoethyl fumarate, monopropyl fumarate, mono-n-butyl fumarate, monomethyl itaconate, monoethyl itaconate, monopropyl itaconate, mono-n-butyl itaconate, monomethyl citraconate, monoethyl citraconate, monopropyl citraconate and mono-n-butyl citraconate; α,β-ethylenically unsaturated dicarboxylic acid monocycloalkylester monomer such as monocyclopentyl maleate, monocyclohexyl maleate, monocycloheptyl maleate, monocyclopentyl fumarate, monocyclohexyl fumarate, monocycloheptyl fumarate, monocyclopentyl itaconate, monocyclohexyl itaconate, monocycloheptyl itaconate, monocyclopentyl citraconate, monocyclohexyl citraconate and monocycloheptyl citraconate; α,β-ethylenically unsaturated dicarboxylic acid monoalkylcycloalkylester monomer such as monomethylcyclopentyl maleate, monoethylcyclohexyl maleate, monomethylcyclopentyl fumarate, monoethylcyclohexyl fumarate, monomethylcyclopentyl itaconate, monoethylcyclohexyl itaconate, monomethylcyclopentyl citraconate and monoethylcyclohexyl citraconate; α,β-ethylenically unsaturated dicarboxylic acid monohydroxyalkylester monomer such as mono-2-hydroxyethyl maleate, mono-3-hydroxypropyl maleate, mono-2-hydroxyethyl fumarate, mono-2-hydroxypropyl fumarate, mono-2-hydroxyethyl itaconate, mono-3-hydroxypropyl itaconate and mono-2-hydroxyethyl citraconate; α,β-ethylenically unsaturated dicarboxylic acid monoester monomer including alicyclic structure such as monocyclohexenyl maleate and monocyclohexenyl fumarate; etc. Among all, α,β-ethylenically unsaturated dicarboxylic acid monoalkylester monomer is preferable, monoalkylester maleate is more preferable, and mono-n-butyl maleate is the most preferable to make effects of the invention remarkable. Carbon number in alkyl group of the above alkylester is preferably 2 to 8.
A content of α,β-ethylenically unsaturated dicarboxylic acid monoester monomer unit with respect to all monomer units constituting highly saturated nitrile rubber (A) is 1 to 20 wt %, preferably 2 to 15 wt % and more preferably 2 to 10 wt %. In case when a content of α,β-ethylenically unsaturated dicarboxylic acid monoester monomer unit is within the above range, an adhesive composition which enables to form an adhesive layer superior in abrasion resistance after heat aging can be easily obtained.
Highly saturated nitrile rubber (A) of the invention may be a copolymerization of α,β-ethylenically unsaturated nitrile monomer, conjugated diene monomer, α,β-ethylenically unsaturated dicarboxylic acid monoester monomer and the other monomers copolymerizable with each of said monomers, in such a range as not to deteriorate the effects of the invention.
Examples of the other monomers may include ethylene, α-olefin monomer, aromatic vinyl monomer, a carboxyl group containing monomer besides α,β-ethylenically unsaturated dicarboxylic acid monoester monomer (including polycarboxylic acid anhydride), α,β-ethylenically unsaturated carboxylic acid ester monomer (which does not include unsubstituted (free) carboxyl group which is not esterified), fluorine containing vinyl monomer, copolymerizable anti-aging agent, etc.
Carbon number of said a-olefin monomer is preferably 3 to 12; and there may be exemplified propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, etc.
As the aromatic vinyl monomer, styrene, a-methylstyrene, vinylpyridine, etc., may be exemplified.
Examples of carboxyl group containing monomer besides α,β-ethylenically unsaturated dicarboxylic acid monoester monomer (including polycarboxylic acid anhydride) may include α,β-ethylenically unsaturated monocarboxylic acid monomer such as acrylic acid, methylacrylic acid, ethylacrylic acid, crotonic acid and cinnamic acid; α,β-ethylenically unsaturated polycarboxylic acid such as fumaric acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, allyl malonic acid and teraconic acid; α,β-unsaturated polycarboxylic acid anhydride such as maleic acid anhydride, itaconic acid anhydride and citraconic acid anhydride, etc.
Examples of α,β-ethylenically unsaturated carboxylic acid ester monomer (which does not include unsubstituted (free) carboxyl group which is not esterified) may include (meth)acrylic ester (abbr. for methacrylate ester and acrylate ester hereinafter) including an acrylic group with carbon number of 1 to 18 such as methyl acrylate, ethyl acrylate, n-butyl acrylate, n-dodecyl acrylate, methyl methacrylate and ethyl methacrylate; (meth)acrylic ester including an alkoxyalkyl group with carbon number of 2 to 12 such as methoxymethyl acrylate, 2-methoxyethyl acrylate and 2-methoxyethyl methacrylate; (meth)acrylic ester including a cyanoalkyl group with carbon number of 2 to 12 such as a-cyanoethyl acrylate, α-cyanoethyl methacrylate and a-cyanobutyl methacrylate; (meth)acrylic ester including a hydroxyalkyl group with carbon number of 1 to 12 such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate and 2-hydroxyethyl methacrylate; (meth)acrylic ester including a fluoroalkyl group with carbon number of 1 to 12 such as trifluoroethyl acrylate and tetrafluoropropyl methacrylate; α,β-ethylenically unsaturated dicarboxylic acid diallyl ester such as dimethyl maleate, dimethyl fumarate, dimethyl itaconate and diethyl itaconate; a dialkylamino group containing α,β-ethylenically unsaturated carboxylic acid ester such as dimethylaminomethyl acrylate and diethylaminoethyl acrylate; etc.
Examples of the fluorine containing vinyl monomer may include fluoroethylvinyl ether, fluoropropylvinyl ether, o-trifluoromethylstyrene, pentafluoro vinylbenzoate, difluoroethylene, tetrafluoroethylene, etc.
Examples of the copolymerizable anti-aging agent may include N-(4-anilinophenyl)acrylamide, N-(4-anilinophenyl)methacrylamide, N-(4-anilinophenyl)cinnamamide, N-(4-anilinophenyl)crotonamide, N-phenyl-4-(3-vinylbenzyloxy)aniline, N-phenyl-4-(4-vinylbenzyloxy)aniline, etc.
These other copolymerizable monomers above may be used in combination. A content of the other monomer unit with respect to all monomer units constituting highly saturated nitrile rubber (A) is preferably 40 wt % or less, more preferably 30 wt % or less, and the most preferably 30 wt % or less.
Iodine value of highly saturated nitrile rubber (A) is 120 or less, preferably 60 or less, and the most preferably 30 or less. In case when iodine value of highly saturated nitrile rubber (A) is too high, it is likely to lower heat resistance and ozone resistance of the obtained hardened adhesive layer.
Polymer mooney viscosity [ML1+4 (100° C.)] of highly saturated nitrile rubber (A) is preferably 15 to 250, more preferably 20 to 200 and the most preferably 30 to 150. In case when polymer mooney viscosity of highly saturated nitrile rubber (A) is too low, mechanical properties of the obtained hardened adhesive layer may be reduced; while when too high, adhesion thereof may be reduced.
Latex of highly saturated nitrile rubber (A) used as the adhesive composition of the invention is obtained by copolymerizing the above monomer, hydrogenating carbon-carbon double bond in the obtained copolymer (X) (hereinafter, sometimes simply referred to as “nitrile rubber”) with a conventionally known method when necessary, and emulsifying thereof when necessary as well. Though polymerization method is not particularly limited and any known polymerization method can be used, emulsion polymerization is preferable in view of an industrial productivity.
As concrete methods of the hydrogenation, there may be mentioned (i) a hydrogenating method wherein copolymer (X) in latex state is hydrogenated using gaseous hydrogen, (ii) a method wherein hydrogen atom is added to copolymer (X) in latex state by using a reducing agent such as hydrazine, (iii) a method wherein copolymer (X) in latex state is coagulated, dried and separated, solving thereof to an organic solvent, hydrogenating the solved copolymer (X), and then making thereof to a latex state by phase inversion emulsification method, etc. In view of productivity improvement, the above method (i) is preferable.
Conventionally known methods can be used for the emulsion polymerization. Emulsifier used in the polymerization is generally anionic surfactant, cationic surfactant, nonionic surfactant, the amphoteric surfactant, etc. Among all, anionic surfactant is preferable; and although the amount used thereof is not particularly limited, in view of adhesive force of the adhesive composition obtained from this latex, it is 1 to 10 wt % and preferably 2 to 6 wt % with respect to 100 wt % of all monomers. Polymerization initiator conventionally in use can be used.
Polymerization method is not particularly limited; and it may be batch method, semibatch method or continuous method. Polymerization temperature and polymerization pressure are also not particularly limited.
Note, in case when an amount of the carbon-carbon double bond (derived from conjugated diene monomer unit) in copolymer (X) is small, which causes iodine value of the obtained nitrile rubber by emulsifying polymerization to be desired value or less, hydrogenation is not necessarily required
In the above method (i), it is preferable that latex of copolymer (X) adjusted by emulsifying polymerization is diluted by water when required, and then hydrogen is supplied in the presence of a hydrogenation catalyst performing hydrogenation reaction.
The hydrogenation catalyst is not particularly limited if it is a compound hardly decomposed by water.
Concrete examples thereof include, as palladium catalyst, palladium salts of carboxylic acid such as formic acid, propionic acid, lauric acid, succinic acid, oleic acid and phthalic acid; palladium chlorinated compounds such as palladium chloride, dichloro(cyclooctadiene)palladium, dichloro(norbornadiene)palladium and hexachloropalladium acid (IV) ammonium; iodide compounds such as iodide palladium; palladium sulfide dihydrate, etc.
Among all, the palladium salt of carboxylic acid, dichloro(norbornadiene)palladium and hexachloropalladium acid (IV) ammonium are the most preferable.
Although the amount of the hydrogenation catalyst used is suitably determined, it is preferably 5 to 6,000 wt·ppm and more preferably 10 to 4,000 wt·ppm.
The reaction temperature of hydrogenation reaction is preferably 0 to 300° C., more preferably 20 to 150° C., and the most preferably 30 to 100° C.
In case when the reaction temperature is too low, the reaction rate will be at the risk of being lowered, while when too high, a side reaction such as a hydrogenation of nitrile group may be induced.
A hydrogen pressure is preferably 0.1 to 30 MPa and more preferably 0.5 to 20 MPa. In addition, a reaction time is preferably 0.5 to 15 hours, more preferably 1 to 15 hours, and the most preferably 1 to 10 hours.
An average particle diameter of latex of thus obtained highly saturated nitrile rubber (A) is preferably 0.01 to 0.5 μm. Solid concentration of said latex, in order to prevent coagulation, is preferably 60 wt % or less, more preferably 5 to 60 wt %, and the most preferably 5 to 50 wt %.
The adhesive composition of the present invention includes latex of highly saturated nitrile rubber (A).
Content of highly saturated nitrile rubber (A) in the adhesive composition of the present invention is preferably 5 to 60 wt %, and more preferably 10 to 50 wt %.
Cross Linking Aid (B)
Adhesive composition of the present invention comprises a cross linking aid (B) having 2 or more ethylenically unsaturated groups in a molecule. The ethylenically unsaturated group included in the molecule of cross linking aid (B) is preferably 5 or less.
Note that the ethylenically unsaturated group in the invention defines a functional group including a carbon-carbon double bond wherein said carbon-carbon double bond is not an aromatic carbon-carbon double bond.
Examples of the ethylenically unsaturated group may include vinyl group, allyl group, maleimide group, butenyl group, (meth)acrylic group, (meth)acryloyl group, etc. Among all, vinyl group, allyl group and maleimide group are preferable, and maleimide group is the most preferable to make effects of the invention remarkable.
Examples of cross linking aid (B) having 2 or more ethylenically unsaturated groups in a molecule may include a polyfunctional vinyl compound such as divinylbenzene and divinylnaphthalen; isocyanurates having 2 or more ethylenically unsaturated groups in a molecule such as triallylisocyanurate and trimethallyl isocyanurate; cyanurates having 2 or more ethylenically unsaturated groups in a molecule such as triallyl cyanurate; maleimides having 2 or more ethylenically unsaturated groups in a molecule such as N,N-m-phenylenedimaleimide, 4,4′-diphenylmethane bismaleimide, bisphenol A diphenylether bismaleimide, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide, N,N-(4-methyl-1,3-phenylene)bis(maleimide); polyfunctional allyl ester such as diallyl phthalate, diallyl isophthalate, diallyl maleate, diallyl fumarate, diallyl sebacate, and triaryl phosphate; diethylene glycol bisallyl carbonate; allyl ethers having 2 or more ethylenically unsaturated groups in a molecule may include ethylene glycol diallyl ether, triallylether of trimethylol propan, partial allyl ether of pentaerythritol; allyl-modified resin such as allyl novolak and allyl resole resin; methacrylate compounds or acrylate compounds having 3 to 5 functional groups such as trimethylolpropane trimethacrylate and trimethylolpropane triacrylate, etc. Among all, maleimides having 2 or more ethylenically unsaturated groups in a molecule is preferable, and 4,4′-diphenylmethane bismaleimide and N,N-m-phenylenedimaleimide are the most preferable to make effects of the invention remarkable. Note, for instance, carbon-carbon double bond at both terminals of 4,4′-diphenylmethane bismaleimide of the following formula (1) is the “ethylenically unsaturated groups”.
The above cross linking aid (B) having 2 or more ethylenically unsaturated groups in a molecule may be used alone or two or more may be used in combination.
Cross linking aid (B) is preferably 1 to 100 pts·wt. and more preferably 5 to 60 pts·wt. with respect to 100 pts·wt. of highly saturated nitrile rubber (A). In case when said amount used is too high, flexibility of the obtained hardened adhesive layer may be reduced; while when too low, an abrasion resistance property after heating of the obtained hardened adhesive layer tends to deteriorate.
Cross linking aid (B) in water dispersed state (aqueous dispersion) is preferably added to latex of highly saturated nitrile rubber (A).
Adhesive composition of the invention may include crosslinking agent, and an organic peroxide crosslinking agent is preferable for the crosslinking agent.
Examples of the organic peroxidecrosslinking agent may include 1,3-bis(t-butylperoxyisopropyl)benzene, cumene hydroperoxide, p-menthane hydroperoxide, di-t-butyl peroxide, t-butyl cumyl peroxide, acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, dibenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, t-butyl peroxyisobutyrate, etc. Among all, 1,3-bis(t-butylperoxyisopropyl)benzene is preferable. Note that the above organic peroxidecrosslinking agent may be used alone or two or more may be used in combination.
Content amount of the cross linking aid in the adhesive composition of the invention, when included, is preferably 0.1 to 10 pts·wt., and more preferably 0.5 to 5 pts·wt., with respect to 100 pts·wt. of highly saturated nitrile rubber (A).
The adhesive composition of the invention is preferable to include reinforcing agent such as carbon black, silica, etc., and more preferable to include carbon black, in view of improving an abrasion resistance property. As carbon black, furnace black, acetylene black, thermal black, channel black, etc. may be used.
Content of reinforcing agent in adhesive composition of the invention is preferably 1 to 100 pts·wt., more preferably 1 to 50pts·wt., and the most preferably 2 to 20 pts·wt., with respect to 100 pts·wt. of highly saturated nitrile rubber (A) in said adhesive composition.
The adhesive composition of the invention may include resins such as resorcinol-formaldehyde resin, melamine resin, epoxy resin and isocyanate resin; fillers such as calcium carbonate, aluminum silicate, magnesium silicate, calcium silicate, talc and clay; metallic oxide, plasticizer and anti-aging agent.
An example of the composite, obtained by bonding the adhesive composition of the invention, is a composite of a fiber base material and a highly saturated nitrile rubber made from the fiber base material and the highly saturated nitrile rubber.
Physical form of the composite of a fiber base material and a highly saturated nitrile rubber is not particularly limited; however, sticking the fiber base material and the highly saturated nitrile rubber and burying whole of or a part of the fiber base material to the highly saturated nitrile rubber, etc. may be exemplified.
A kind of fiber constituting the fiber base material is not particularly limited; concrete examples thereof may include polyester fibers, nylon fibers, vinylon fibers, polyamide fibers such as aramid (aromatic polyamide) fibers, glass fibers, cotton, rayon fibers, etc.
A shape of the fiber base material is not particularly limited; and concrete examples thereof include a filament, a staple, a code shape, a rope shape and a woven fabric such as canvas. It is suitably determined according to the use of the composite of a fiber base material and a highly saturated nitrile rubber. Examples may include a core-wire contained highly saturated nitrile rubber made toothed belt by using the code shape as fiber base material, and a base cloth covered highly saturated nitrile rubber made toothed belt using a fiber base material in a state of base cloth such as canvas, etc.
A highly saturated nitrile rubber (hereinafter, it is defined as “highly saturated nitrile rubber (C)” to distinguish from highly saturated nitrile rubber (A) used in the adhesive composition. Highly saturated nitrile rubber (C) and highly saturated nitrile rubber (A) may be the same or may be different; however, it is preferable that they are different.) used in the composite of a fiber base material and a highly saturated nitrile rubber is a copolymer obtained by copolymerizing essential monomers of conjugated diene and α,β-ethylenically unsaturated nitrile and, when necessary, monomers copolymerizable with the essential monomers and hydrogenating thereof. Examples of the other copolymerizable monomers may include the same monomers used to synthesize highly saturated nitrile rubber (A).
Concrete examples of highly saturated nitrile rubber (C) may include a highly saturated butadiene-acrylonitrile copolymer rubber, a carboxyl group included highly saturated butadiene-acrylonitrile copolymer rubber, a highly saturated isoprene-butadiene-acrylonitrile copolymer rubber, a highly saturated isoprene-acrylonitrile copolymer rubber, a highly saturated butadiene-methyl acrylate acrylonitrile copolymer rubber, a highly saturated butadiene-acrylic acid-acrylonitrile copolymer rubber, a highly saturated butadiene-ethylene-acrylonitrile copolymer rubber, etc.
Among all, as the highly saturated nitrile rubber (C) for the composite of a fiber base material and a highly saturated nitrile rubber used for an automobile in particular, a highly saturated butadiene-acrylonitrile copolymer rubber is preferable in view of oil resistance and heat resistance.
Hydrogenation rate of highly saturated nitrile rubber (C), in terms of an iodine value, it is preferably 120 or less, more preferably 100 or less and the most preferably 50 or less. In case when the iodine value is too high, heat resistance of the obtained composite of a fiber base material and a highly saturated nitrile rubber is likely to lower.
Content of α,β-ethylenically unsaturated nitrile monomer unit in highly saturated nitrile rubber (C) with respect to all monomer units constituting highly saturated nitrile rubber (C) is preferably 10 to 60 wt %, more preferably 15 to 50 wt %, and the most preferably 20 to 50 wt %. In case when said content of α,β-ethylenically unsaturated nitrile monomer unit is too small, oil resistance of the composite of a fiber base material and a highly saturated nitrile rubber may deteriorate, while too large, low-temperature resistance thereof may decrease.
Mooney viscosity [ML1+4 (100° C.)] of highly saturated nitrile rubber (C) is preferably 10 to 300, more preferably 20 to 250 and the most preferably 30 to 200. In case when mooney viscosity of highly saturated nitrile rubber (C) is too low, mechanical and formability properties may be deteriorated; while when too high, formability property thereof may be deteriorated.
The highly saturated nitrile rubber (C) may include, in addition to crosslinking agents such as sulfer, an organic peroxide crosslinking agent, and a polyamine crosslinking agent, compounding agents generally blended when rubber processing, such as reinforcing agents of carbon black, silica, short fiber, etc.; an anti-aging agent; a plasticizer; a pigment; a tackifier; a processing aid; an antiscorcing agent; and silane coupling agent when required. Among all, it is preferable to add the crosslinking agent, and it is the most preferable to add the organic peroxide crosslinking agent.
Examples of the organic peroxide crosslinking agent may include a, α′-bis(t-butylperoxyisopropyl)benzene, cumene hydroperoxide, p-menthane hydroperoxide, di-t-butyl peroxide, t-butyl cumyl peroxide, acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, dibenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, t-butyl peroxyisobutyrate, etc. Among all, α,α′-bis(t-butylperoxyisopropyl)benzene is preferable. The above organic peroxide crosslinking agents may be used alone or in combination of two or more.
Compounding amount, when compounding crosslinking agents to highly saturated nitrile rubber (C), is preferably 0.1 to 20 pts·wt. and more preferably 1 to 10 pts·wt. with respect to 100 pts·wt. of highly saturated nitrile rubber (C).
Method to obtain composite of a fiber base material and a highly saturated nitrile rubber is not particularly limited; however, it may be performed by placing a fiber base material, on which adhesive composition of the invention is bonded by dip treatment and the like, on highly saturated nitrile rubber (C), and then heating and pressing thereof.
The pressing may be performed by using a press molding machine, a metal roll, an injection molding machine, etc.
Pressure of the pressing is preferably 0.5 to 20 MPa and more preferably 2 to 10 MPa; heat temperature is preferably 130 to 300° C. and more preferably 150 to 250° C.; and the operation time is preferably 1 to 180 mins, and more preferably 5 to 120 mins.
According to the above method, vulcanizing and molding of highly saturated nitrile rubber (C) and bonding between the fiber base material and highly saturated nitrile rubber (C) can be done simultaneously.
In order to attain a desired surface shape of highly saturated nitrile rubber (C) in the objective composite of a fiber base material and a highly saturated nitrile rubber, a mold on inner face of compressor mold or on roll surface may be formed.
An embodiment of the composite of a fiber base material and a highly saturated nitrile rubber may include a composite of a fiber base material and a highly saturated nitrile rubber and a fiber base material.
The composite of a fiber base material and a highly saturated nitrile rubber and a fiber base material is, for instance, a combination of a fiber base material (it may be a combination of two or more fiber base materials) and a composite of a fiber base material and a highly saturated nitrile rubber.
In concrete, a core-wire of the fiber base material, highly saturated nitrile rubber (C) and a base cloth of the fiber base material are laminated (the adhesive composition of the invention is suitably bonded to the core-wire and the base cloth at this time), and then pressured while heated thereof.
The composite of a fiber base material and a highly saturated nitrile rubber obtained by bonding adhesive composition of the invention is superior in a mechanical strength, an abrasion resistance property and a water resistance property.
Therefore, it is preferable for belts such as flat belt, V belt, V ribbed belt, round belt, square belt, toothed belt, etc; it is the most preferable for in-oil belt.
Further, the composite of a fiber base material and a highly saturated nitrile rubber obtained by bonding the adhesive composition of the invention is preferably used for hose, tube, diaphragm, tire, etc.
The hose exemplifies single pipe rubber hose, multilayer rubber hose, braiding reinforced hose, winding reinforced hose, etc. The diaphragm exemplifies flat diaphragm, rolling diaphragm, etc.
The composite of a fiber base material and a highly saturated nitrile rubber obtained by bonding the adhesive composition of the invention may be used for industrial products such as seal, rubber roll, etc., in addition to the above use. The seal exemplifies moving part seals, such as for rotating, rocking, reciprocating, etc., and fixing part seals. The moving part seals exemplify oil seal, piston seal, mechanical seal, boots, dust cover, diaphragm, accumulator, etc. The fixing part seals exemplify O-ring, various gaskets, etc.
Examples of the rubber roll may include rolls which are parts of office automation equipments such as a printing equipment, a copying equipment, etc.; fiber processing rolls such as stretching rolls for spinning and draft rolls for spinning, etc.; iron making rolls such as bridle roll, snubber roll, steering roll, etc.
Hereinafter, the present invention will be described based on the examples. Note that, “parts” in the present examples are based on the weight unless mentioned otherwise.
In the examples and the comparative examples, various properties are evaluated as follows.
Composition Analysis of Rubber included in Highly Saturated Nitrile Rubber Latex
Content ratio of each monomer unit in highly saturated nitrile rubber included in highly saturated nitrile rubber latex was measured with the following methods.
At first, an excess amount of methanol was added to highly saturated nitrile rubber latex, deposited rubber was removed, and then stirred and washed thereof with methanol for several times. Subsequently, it was dried for 24 hrs. under a reduced pressure at 60° C., and then highly saturated nitrile rubber was obtained. Content ratio of each monomer unit constituting thus obtained highly saturated nitrile rubber was measured with the following methods.
Namely, content ratios of mono n-butyl maleate unit and methacrylate unit were calculated as following. 0.2 g of highly saturated nitrile rubber in square with a side 2 mm long was dissolved by adding 100 ml of 2-butanon and stirred thereof for 16 hrs. And then 20 ml of ethanol and 10 ml of water were added, stirred thereof, and a mole number of carboxyl groups per 100 g of the highly saturated nitrile rubber was obtained by titration using 0.02N ethanol solution of potassium hydroxide with thymolphtalein as the indicator at room temperature. Thus obtained mole number was converted to mono n-butyl maleate unit and methacrylate unit.
Content ratio of acrylonitrile unit was calculated by measuring nitrogen content in highly saturated nitrile rubber by Kjeldahl method in accordance with JIS K6384.
Content ratio of 1,3-butadiene unit (including a hydrogenated part) was measured in the same way as above: an excess amount of methanol was added to nitrile rubber latex before hydrogenation reaction, and then washed and dried the deposited rubber. And nitrile rubber before hydrogenation reaction was obtained; and it was calculated by measuring an iodine value (in accordance with JIS K 6235) thereof.
Iodine value was measured in accordance with JIS K6235 by using highly saturated nitrile rubber obtained by the same method with the above rubber composition analysis.
A composite of a nylon base cloth of 15 cm long and 15 cm wide as a fiber base material and a highly saturated nitrile rubber was held in gear oven at 150° C. for 168 hrs. And then, an abrasion resistance property of the composite was evaluated by using Taber's abrasion tester (tradename “Taber Abraser 5150”, made by TALEDYNE TABER) and rubbing with disc of nylon base cloth side. Test conditions were load of 1.0 kg, surface temperature of the abrasion at 120° C. (an infrared light lamp irradiation) and number of disc revolution for 15,000 times (rotational speed 60 rpm).
Abrasion resistance properties after heat aging were evaluated with abrasion loss amount on nylon base cloth side by 7 grades according to the following standard.
To a reaction vessel, 180 parts of ion-exchange water, 25 parts of sodium dodecylbenzenesulfonate solution in a concentration of 10 wt %, 37 parts of acrylonitrile, 4 parts of mono-n-butyl maleate and 0.65 part of t-dodecyl mercaptan (a molecular weight modifier) were added in sequence, and after replacing the internal gas with nitrogen for 3 times, 57 parts of 1,3-butadiene were added. The reaction vessel was kept at 5° C., and added with 0.1 part of cumene hydroperoxide (a polymerization initiator) to continue polymerization reaction with stirring the reaction vessel. And when polymerization conversion was 40% and 60%, 1 part of mono-n-butyl maleate were respectively added. Next, when polymerization conversion reached 85%, 0.1 part of hydroquinone aqueous solution (polymerization terminator) in a concentration of 10 wt % was added to terminate the polymerization, and the remaining monomers were removed under a reduced pressure with a water-temperature of 60° C. to obtain a latex of an nitrile rubber (X1) (a solid content concentration of about 30 wt %).
So as to have a palladium content of 1,000 wt·ppm with respect to dry weight of the rubber included in the above obtained latex of nitrile rubber (X1), latex of nitrile rubber (X1) and palladium catalyst (a mixed solution of equivalent weights of 1 wt % palladium acetate-acetone solution and ion-exchange water) were added into an autoclave, and hydrogenation reaction was performed at a hydrogen pressure of 3 MPa and a temperature at 50° C. for 6 hours to obtain latex (L1-1) of a highly-saturated nitrile rubber (A1-1) (a solid content concentration of 30 wt %) by adjusting solid content concentration.
Content ratio of each monomer unit in highly-saturated nitrile rubber (A1-1) was 35.7 wt % of acrylonitrile unit, 5.7 wt % of mono-n-butyl maleate unit and 58.6 wt % of 1,3-butadiene unit (including hydrogenated parts). Iodine value was 9.
Except for changing additional amount of palladium catalyst so as to have a palladium content of 700 wt·ppm with respect to dry weight of the rubber included in latex of nitrile rubber (X1) in Synthesis Example 1, the same procedures as in the Synthesis Example 1 were conducted to prepare latex (L1-2) (a solid content concentration of 30 wt %) of a highly-saturated nitrile rubber (A1-2).
Content ratio of each monomer unit in highly-saturated nitrile rubber (A1-2) was 35.7 wt % of acrylonitrile unit, 5.7 wt % of mono-n-butyl maleate unit and 58.6 wt % of 1,3-butadiene unit (including hydrogenated parts). Iodine value was 30.
To a reaction vessel, 180 parts of ion-exchange water, 25 parts of sodium dodecylbenzenesulfonate solution in a concentration of 10 wt %, 50 parts of acrylonitrile, 6 parts of mono-n-butyl maleate and 0.65 part of t-dodecyl mercaptan (a molecular weight modifier) were added in sequence, and after replacing the internal gas with nitrogen for 3 times, 44 parts of 1,3-butadiene were added. The reaction vessel was kept at 5° C., and added with 0.1 part of cumene hydroperoxide (a polymerization initiator) to continue polymerization reaction with stirring the reaction vessel. Next, when polymerization conversion reached 85%, 0.1 part of hydroquinone aqueous solution (a polymerization terminator) in a concentration of 10 wt % was added to terminate the polymerization, and the remaining monomers were removed under a reduced pressure with a water-temperature of 60° C. to obtain a latex of an nitrile rubber (X2) (a solid content concentration of about 30 wt %).
So as to have a palladium content of 1,000 wt·ppm with respect to dry weight of the rubber included in the above obtained latex of nitrile rubber (X2), latex of nitrile rubber (X2) and palladium catalyst (a mixed solution of equivalent weights of 1 wt % palladium acetate-acetone solution and ion-exchange water) were added into an autoclave, and hydrogenation reaction was performed at a hydrogen pressure of 3 MPa and a temperature at 50° C. for 6 hours to obtain latex (L2) (a solid content concentration of 30 wt %) of highly-saturated nitrile rubber (A2) by adjusting solid content concentration.
Content ratio of each monomer unit in highly-saturated nitrile rubber (A2) was 44.5 wt % of acrylonitrile unit, 5.0 wt % of mono-n-butyl maleate unit and 50.5 wt % of 1,3-butadiene unit (including hydrogenated parts). Iodine value was 11.
To a reaction vessel, 180 parts of ion-exchange water, 25 parts of sodium dodecylbenzenesulfonate solution in a concentration of 10 wt %, 35 parts of acrylonitrile, 4 parts of methacrylate and 0.5 part of t-dodecyl mercaptan (a molecular weight modifier) were added in sequence, and after replacing the internal gas with nitrogen for 3 times, 61 parts of 1,3-butadiene were added. The reaction vessel was kept at 5° C., and added with 0.1 part of cumene hydroperoxide (a polymerization initiator) to continue polymerization reaction with stirring the reaction vessel. Next, when polymerization conversion reached 85%, 0.1 part of hydroquinone (polymerization terminator) aqueous solution in a concentration of 10 wt % was added to terminate the polymerization, and the remaining monomers were removed under a reduced pressure with a water-temperature of 60° C. to obtain a latex of an nitrile rubber (X3) (a solid content concentration of about 30 wt %).
So as to have a palladium content of 700 wt·ppm with respect to dry weight of the rubber included in the above obtained latex of nitrile rubber (X3), latex of nitrile rubber (X3) and palladium catalyst (a mixed solution of equivalent weights of 1 wt % palladium acetate-acetone solution and ion-exchange water) were added into an autoclave, and hydrogenation reaction was performed at a hydrogen pressure of 3 MPa and a temperature of 50° C. for 6 hours to obtain latex (L3) (a solid content concentration of 30 wt %) of highly-saturated nitrile rubber (A3) by adjusting solid content concentration.
Content ratio of each monomer unit in highly-saturated nitrile rubber (A3) was 33.5 wt % of acrylonitrile unit, 3.5 wt % of methacrylate unit and 63.0 wt % of 1,3-butadiene unit (including hydrogenated parts). Iodine value was 32.
To a reaction vessel, 180 parts of ion-exchange water, 25 parts of sodium dodecylbenzenesulfonate solution in a concentration of 10 wt %, 37 parts of acrylonitrile and 0.5 part of t-dodecyl mercaptan (a molecular weight modifier) were added in sequence, and after replacing the internal gas with nitrogen for 3 times, 63 parts of 1,3-butadiene were added. The reaction vessel was kept at 5° C., and added with 0.1 part of cumene hydroperoxide (a polymerization initiator) to continue polymerization reaction with stirring the reaction vessel. Next, when polymerization conversion reached 85%, 0.1 part of hydroquinone aqueous solution (polymerization terminator) in a concentration of 10 wt % was added to terminate the polymerization, and the remaining monomers were removed under a reduced pressure with a water-temperature of 60° C. to obtain a latex of an nitrile rubber (X4) (a solid content concentration of about 30 wt %).
So as to have a palladium content of 700 wt·ppm with respect to dry weight of the rubber included in the above obtained latex of nitrile rubber (X4), latex of nitrile rubber (X4) and palladium catalyst (a mixed solution of equivalent weights of 1 wt % palladium acetate-acetone solution and ion-exchange water) were added into an autoclave, and hydrogenation reaction was performed at a hydrogen pressure of 3 MPa and a temperature at 50° C. for 6 hours to obtain latex (L4) (a solid content concentration of 30 wt %) of highly-saturated nitrile rubber (A4) by adjusting solid content concentration.
Content ratio of each monomer unit in highly-saturated nitrile rubber (A4) was 36.2 wt % of acrylonitrile unit and 63.8 wt % of 1,3-butadiene unit (including hydrogenated parts). Iodine value was 35.
11 parts of resorcin, 8.1 parts of formalin (a concentration of 37 wt %) and 3 parts of sodium hydroxide (a concentration of 10 wt %) were dissolved in 194 parts of distilled water, stirred for 20 hours at room temperature, and then resorcinol-formaldehyde resin liquid (RF1) (a concentration of 6.6 wt %) was obtained.
Latex (L1-1) (a content amount of highly saturated nitrile rubber (A1-1) was 100 parts), 4,4′-diphenylmethane bismaleimide (content amount of 4,4′-diphenylmethane bismaleimide is 25 parts) which is an aqueous dispersion having a concentration of 50 wt % and N330 carbon black (content amount of N330 carbon black is 10 parts) which is an aqueous dispersion having a concentration of 25 wt % were mixed, and then an adhesive composition (p1) was obtained. A base cloth (woven fabric) made by nylon 66 as fiber base material was dipped in the adhesive composition (p1), taken out, and was coated with the adhesive composition (p1). At this time, 20 parts of the adhesive composition (p1) was made to bond with respect to 100 parts of nylon 66 made base cloth. Subsequently, adhesive composition (p1) coated base cloth was heated for 3 minutes at 150° C. by an air circulating oven, and a pretreated base cloth was obtained.
In addition, the compositions described in Table 1 were kneaded with a roll, and then a crosslinking highly saturated nitrile rubber composition sheet having a thickness of about 2.5 mm was manufactured.
Next, the crosslinking highly saturated nitrile rubber composition sheet was laminated on the above pretreated base cloth (a planar of 15 cm length and 15 cm width), and then crosslinked by holding for 30 minutes at 170° C. while applying pressure of 5 MPa by a pressing machine. Then, a composite of nylon 66 made base cloth as a fiber base material and a highly saturated nitrile rubber (a composite of a fiber base material and a highly saturated nitrile rubber) was obtained. “An abrasion resistance property test on the composite of a fiber base material and a highly saturated nitrile rubber after heat aging” was performed to thus obtained composite. Results are shown in Table 2.
Except for further adding 1,3-bis(t-butylperoxyisopropyl)benzene (an organic peroxide) (content amount of 1,3-bis(t-butylperoxyisopropyl)benzene is 1.5 parts) which is an aqueous dispersion having a concentration of 50 wt %, the same procedures as in Example 1 were conducted to obtain an adhesive composition (p2). Except for using adhesive composition (p2) instead of adhesive composition (p1), a composite of nylon 66 made base cloth as a fiber base material and a highly saturated nitrile rubber (a composite of a fiber base material and a highly saturated nitrile rubber) was obtained in the same manner as Example 1. “An abrasion resistance property test on the composite of a fiber base material and a highly saturated nitrile rubber after heat aging” was performed to thus obtained composite. Results are shown in Table 2.
Except for using Latex (L1-2) (content amount of highly saturated nitrile rubber (A1-2) was 100 parts) instead of Latex (L1-1) (content amount of highly saturated nitrile rubber (A1-1) was 100 parts), the same procedures as in Example 1 were conducted to obtain an adhesive composition (p3). Except for using adhesive composition (p3) instead of adhesive composition (p1), a composite of nylon 66 made base cloth as a fiber base material and a highly saturated nitrile rubber (a composite of a fiber base material and a highly saturated nitrile rubber) was obtained in the same manner as Example 1. “An abrasion resistance property test on the composite of a fiber base material and a highly saturated nitrile rubber after heat aging” was performed to thus obtained composite. Results are shown in Table 2.
Except for using N,N-m-phenylenedimaleimide (content amount of N,N-m-phenylenedimaleimide is 25 parts) which is an aqueous dispersion having a concentration of 50 wt % instead of 4,4′-diphenylmethane bismaleimide (content amount of 4,4′-diphenylmethane bismaleimide is 25 parts) which is an aqueous dispersion having a concentration of 50 wt %, the same procedures as in Example 3 were conducted to obtain an adhesive composition (p4). Except for using adhesive composition (p4) instead of adhesive composition (p1), a composite of nylon 66 made base cloth as a fiber base material and a highly saturated nitrile rubber (a composite of a fiber base material and a highly saturated nitrile rubber) was obtained in the same manner as Example 1. “An abrasion resistance property test on the composite of a fiber base material and a highly saturated nitrile rubber after heat aging” was performed to thus obtained composite. Results are shown in Table 2.
Except for using Latex (L2) (content amount of highly saturated nitrile rubber (A2) was 100 parts) instead of Latex (L1-1) (content amount of highly saturated nitrile rubber (A1-1) was 100 parts), the same procedures as in Example 1 were conducted to obtain an adhesive composition (p5). Except for using adhesive composition (p5) instead of adhesive composition (p1), a composite of nylon 66 made base cloth as a fiber base material and a highly saturated nitrile rubber (a composite of a fiber base material and a highly saturated nitrile rubber) was obtained in the same manner as Example 1. “An abrasion resistance property test on the composite of a fiber base material and a highly saturated nitrile rubber after heat aging” was performed to thus obtained composite. Results are shown in Table 2.
Resorcinol-formaldehyde resin liquid (RF1) (solid amount of resorcinol-formaldehyde resin is 10 parts) and 65.2 parts of distilled water were added to latex (L1-1) (content amount of highly saturated nitrile rubber (A1-1) was 100 parts), and stirred thereof. Subsequently left for 20 hours at 25° C., and then, N330 carbon black (content amount of carbon black was 100 parts) which is an aqueous dispersion having a concentration of 25 wt % was mixed to obtain adhesive composition (pc1). Except for using adhesive composition (pc1) instead of adhesive composition (p1), a composite of nylon 66 made base cloth as a fiber base material and a highly saturated nitrile rubber (a composite of a fiber base material and a highly saturated nitrile rubber) was obtained in the same manner as Example 1. “An abrasion resistance property test on the composite of a fiber base material and a highly saturated nitrile rubber after heat aging” was performed to thus obtained composite. Results are shown in Table 2.
Except for changing latex (L1-2) (content amount of highly saturated nitrile rubber (A1-2) was 100 parts) to latex (L3) (content amount of highly saturated nitrile rubber (A3) was 100 parts) when obtaining an adhesive composition, adhesive composition (pc2) was obtained in the same manner as Example 4. Except for using adhesive composition (pc2) instead of adhesive composition (p1), a composite of nylon 66 made base cloth as a fiber base material and a highly saturated nitrile rubber (a composite of a fiber base material and a highly saturated nitrile rubber) was obtained in the same manner as Example 1. “An abrasion resistance property test on the composite of a fiber base material and a highly saturated nitrile rubber after heat aging” was performed to thus obtained composite. Results are shown in Table 2.
Except for changing latex (L1-1) (content amount of highly saturated nitrile rubber (A1-1) was 100 parts) to latex (L4) (content amount of highly saturated nitrile rubber (A4) was 100 parts) when obtaining an adhesive composition, adhesive composition (pc3) was obtained in the same manner as Example 1. Except for using adhesive composition (pc3) instead of adhesive composition (p1), a composite of nylon 66 made base cloth as a fiber base material and a highly saturated nitrile rubber (a composite of a fiber base material and a highly saturated nitrile rubber) was obtained in the same manner as Example 1. “An abrasion resistance property test on the composite of a fiber base material and a highly saturated nitrile rubber after heat aging” was performed to thus obtained composite. Results are shown in Table 2.
Table 2 shows that in case when the adhesive composition of the invention comprising: latex of a highly saturated nitrile rubber, which comprises the α,β-ethylenically unsaturated nitrile monomer unit, the conjugated diene monomer unit and the α,β-ethylenically unsaturated dicarboxylic acid monoester monomer unit and has an iodine value of 120 or less; and a crosslinking aid (which has 2 or more ethylenically unsaturated groups in a molecule) which has two maleimide groups in a molecule was used, the composite of nylon 66 made base cloth and a highly saturated nitrile rubber (the composite of a fiber base material and a highly saturated nitrile rubber) was superior in an abrasion resistance property after heat aging (Ex. 1 to 5).
To the contrary, when an adhesive composition, including latex of highly saturated nitrile rubber and resorcinol-formaldehyde resin while not including a crosslinking aid which has 2 or more ethylenically unsaturated groups in a molecule, and which do not satisfy the requirements of the invention, was used, the composite of nylon 66 made base cloth and a highly saturated nitrile rubber (the composite of a fiber base material and a highly saturated nitrile rubber) was inferior in an abrasion resistance property after heat aging (Comp. Ex. 1)
Further, even when an adhesive composition includes a crosslinking aid which has two maleimide groups in a molecule (a crosslinking aid which has two or more ethylenically unsaturated groups in a molecule), said adhesive composition may not satisfy the requirements of the invention by including latex of a highly saturated nitrile rubber which do not include α,β-ethylenically unsaturated dicarboxylic acid monoester monomer unit; and when said adhesive composition was used, the composite of nylon 66 made base cloth and a highly saturated nitrile rubber (the composite of a fiber base material and a highly saturated nitrile rubber) was inferior in an abrasion resistance property after heat aging (Comp. Ex. 2 and Comp. Ex. 3).
| Number | Date | Country | Kind |
|---|---|---|---|
| 2013-059382 | Mar 2013 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2014/056625 | 3/13/2014 | WO | 00 |
