WO2011102231A1 - トリアジン誘導体およびその応用 - Google Patents
トリアジン誘導体およびその応用 Download PDFInfo
- Publication number
- WO2011102231A1 WO2011102231A1 PCT/JP2011/052249 JP2011052249W WO2011102231A1 WO 2011102231 A1 WO2011102231 A1 WO 2011102231A1 JP 2011052249 W JP2011052249 W JP 2011052249W WO 2011102231 A1 WO2011102231 A1 WO 2011102231A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- crosslinkable
- group
- polymer
- triazine derivative
- triazine
- Prior art date
Links
- 0 BN(C(N(C)C(N1*)=O)=O)C1=O Chemical compound BN(C(N(C)C(N1*)=O)=O)C1=O 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/42—One nitrogen atom
- C07D251/46—One nitrogen atom with oxygen or sulfur atoms attached to the two other ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/48—Two nitrogen atoms
- C07D251/52—Two nitrogen atoms with an oxygen or sulfur atom attached to the third ring carbon atom
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L15/00—Compositions of rubber derivatives
- C08L15/02—Rubber derivatives containing halogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/30—Only oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/54—Three nitrogen atoms
- C07D251/70—Other substituted melamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/22—Incorporating nitrogen atoms into the molecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/28—Reaction with compounds containing carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2810/00—Chemical modification of a polymer
- C08F2810/20—Chemical modification of a polymer leading to a crosslinking, either explicitly or inherently
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
Definitions
- the present invention relates to a triazine derivative and its application, and more particularly to a triazine derivative having a novel structure and its application.
- the crosslinkable polymer refers to both a crosslinkable elastomer and a crosslinkable thermoplastic resin.
- Isocyanurate derivatives particularly triallyl isocyanurate (hereinafter referred to as TAIC) are known as useful crosslinking agents for curing a crosslinkable polymer to obtain a molded product.
- TAIC triallyl isocyanurate
- a polymer molded body using TAIC is excellent in chemical resistance and compression set, but has insufficient heat resistance. Further, when TAIC is used for a substituted polyolefin, particularly an ethylene vinyl acetate copolymer, there is a disadvantage that the crosslinking process takes a long time because the crosslinking speed is slow.
- triazine derivatives such as tris (diallylamino) -s-triazine are used as a crosslinking agent (Patent Document 1), and such triazine derivatives are excellent in heat resistance as compared with TAIC.
- An object of the present invention is to provide a novel triazine derivative which is excellent in heat resistance and has a high crosslinking rate as compared with TAIC and can be suitably used as a crosslinking agent.
- the first gist of the present invention resides in the triazine derivative represented by the general formula (I).
- X and Y each independently represent a diallylamino group, a monoallylamino group, an allyloxy group or a metaallyloxy group, and Z represents an allyloxy group or a metaallyloxy group.
- the second gist of the present invention resides in a crosslinking agent characterized by comprising a triazine derivative represented by the general formula (I) or a prepolymer thereof.
- the third gist of the present invention is that the crosslinkable polymer is blended with at least the triazine derivative represented by the general formula (I) or a prepolymer thereof, and the triazine derivative or the prepolymer thereof is added to 100 parts by weight of the crosslinkable polymer.
- the crosslinkable polymer composition is characterized in that the ratio of the polymer is 0.05 to 15 parts by weight.
- the fourth gist of the present invention is that the triazine derivative represented by the above general formula (I) or a prepolymer thereof is used as a crosslinking agent in a method for producing a polymer molded body for curing a crosslinkable polymer. It exists in the manufacturing method of the polymer molded object to make.
- the fifth aspect of the present invention is a polymer molded body cured by the action of a cross-linking agent, and uses the triazine derivative represented by the general formula (I) or a prepolymer thereof as the cross-linking agent. It exists in the polymer molded object characterized by this.
- a novel triazine derivative which is excellent in heat resistance and has a high crosslinking rate as compared with TAIC and can be suitably used as a crosslinking agent.
- the triazine derivative of the present invention is represented by the general formula (I).
- X and Y each independently represent a diallylamino group, a monoallylamino group, an allyloxy group or a metaallyloxy group, and Z represents an allyloxy group or a metaallyloxy group.
- triazine derivative represented by the general formula (I) examples include 4,6-bis (diallylamino) -2-allyloxy-1,3,5-triazine, 4,6-bis (allylamino) -2- Allyloxy-1,3,5-triazine, 4,6-bis (allyl-methylamino) -2-allyloxy-1,3,5-triazine, 4,6-bis (diallylamino) -2-metaallyloxy-1, 3,5-triazine, 4,6-bis (allylamino) -2-methallyloxy-1,3,5-triazine, 4,6-bis (allyl-methylamino) -2-methallyloxy-1,3,5-triazine 4,6-bis (allyloxy) -2-diallylamino-1,3,5-triazine, 4,6-bis (allyloxy) -2-allylamino-1,3,5-triazine, 4,6-bis ( Liloxy) -2- (allyl)
- the triazine derivative represented by the general formula (I) can be easily obtained by, for example, reacting cyanuric chloride with diallylamine or monoallylamine in the presence of a base and further reacting the resulting reaction product with allyl alcohol or the like. I can do it.
- the base include alkali metal carbonates such as potassium carbonate and sodium carbonate, and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide.
- a tertiary amine such as triethylamine or an amine which is a reaction component may be used as the base.
- reaction solvent tetrahydrofuran (THF), dioxane, toluene, N, N-dimethylformamide, N, N-dimethylacetamide and the like are used.
- the reaction temperature varies depending on the type of reaction components and the like, but is generally about 20 to 200 ° C. Identification analysis of the obtained compound can be performed by NMR spectrum measurement, GC-MS analysis, HPLC analysis, melting point measurement and the like.
- the crosslinking agent of the present invention comprises a triazine derivative represented by the above general formula (I) or a prepolymer thereof.
- the prepolymer of the above triazine derivative can be obtained by radical polymerization of a monomer using an organic peroxide or the like as an initiator, and its number average molecular weight is usually 1000 to 20000, preferably 2000 to 7000.
- the crosslinkable polymer composition of the present invention comprises at least a triazine derivative represented by the general formula (I) or a prepolymer thereof blended in a crosslinkable polymer, and the triazine derivative or 100 parts by weight of the crosslinkable polymer The proportion of the prepolymer is 0.05 to 15 parts by weight.
- the crosslinkable polymer used in the present invention is a crosslinkable elastomer and a crosslinkable thermoplastic resin.
- the crosslinkable elastomer refers to an elastomer having an active site that can be cross-linked by radical generation.
- the type of the crosslinkable elastomer is not particularly limited.
- natural rubber, isoprene rubber, butadiene rubber, ethylene propylene rubber, styrene rubber, nitrile rubber, hydrogenated nitrile rubber, chloroprene rubber, chlorosulfonated polyethylene, acrylic rubber, ethylene Acrylic rubber, silicone rubber, fluorine rubber, hydrin rubber and the like can be mentioned.
- the substituted polyolefin which is a copolymer of olefins, such as ethylene and propylene, and vinyl alcohol, acrylic acid, methacrylic acid, ethyl acrylate, glycidyl methacrylate, vinyl acetate, etc. is mentioned. Further, a blend rubber composed of two or more of these may be used. Preferred is fluororubber.
- the kind of fluororubber is not particularly limited, and examples thereof include FKM, FFKM, FEPM, and TFE.
- substituted polyolefin such as ethylene vinyl acetate copolymer or fluororubber is preferable.
- the vinyl acetate content of the ethylene vinyl acetate copolymer is usually 10 to 40% by weight, preferably 20 to 35% by weight.
- the crosslinkable thermoplastic resin refers to a thermoplastic resin having an active point that can be cross-linked by radical generation.
- the type of the crosslinkable thermoplastic resin is not particularly limited, and examples thereof include vinyl chloride resin, polyolefin resin, acrylic resin, polystyrene resin, polycarbonate resin, polyester resin, polyamide resin, polyphenylene ether resin, polyacetal resin, and fluorine resin. These two or more kinds of blend resins may be used. Polyamide resins and polyester resins are preferable, and polyamide 6, polyamide 66, and polybutylene terephthalate are more preferable.
- the blending ratio of the triazine derivative or its prepolymer to the crosslinkable polymer is preferably 0.05 to 15% by weight.
- crosslinking agent may be used in combination with the above crosslinking agent.
- the other crosslinking agent is not particularly limited, but isocyanurate derivatives represented by the following general formula (II) are preferable.
- At least two of A, B and C each independently represent an optionally substituted allyl group, and the rest represent a hydrogen atom or an optionally substituted hydrocarbon group. Show.
- hydrocarbon group examples include an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.
- the aliphatic hydrocarbon group may have a branched structure, and these may have a substituent.
- Specific examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkoxy group, a thioalkyl group, an alkoxycarbonyl group, a cyclohexyl group, a phenyl group, and a benzyl group.
- A, B, and C may be the same or different.
- the isocyanurate derivatives represented by the general formula (II) are already known, and specific examples thereof include triallyl isocyanurate (TAIC), diallylmethallyl isocyanurate, diallylbenzyl isocyanurate, diallyl-4-trifluoro Examples thereof include methyl benzyl isocyanurate, trimethallyl isocyanurate, ethoxycarbonylmethyl diallyl isocyanate and the like.
- the total amount is generally 0.05 to 15 parts by weight, preferably 0.5 to 100 parts by weight of the crosslinkable polymer. ⁇ 5 parts by weight.
- the proportion of the isocyanurate derivative is usually 5 to 95% by weight as a proportion of the total crosslinking agent.
- polyfunctional (meth) acrylates may be used in combination.
- the polyfunctional (meth) acrylate has 2 or more, preferably 3 or more (meth) acryloyl groups in one molecule.
- the added amount of these polyfunctional (meth) acrylates is 0.05 to 15 parts by weight with respect to 100 parts by weight of the crosslinkable polymer.
- organic peroxide can be blended in the crosslinkable polymer composition.
- the organic peroxide is usually an essential component for heat crosslinking, and is not particularly limited as long as it is a known organic peroxide that generates a peroxy radical under vulcanization conditions.
- the compounding amount of the organic peroxide varies depending on the crosslinkable polymer to be used, but is usually 0.1 to 10% by weight, preferably 0.5 to 5% by weight, based on 100 parts by weight of the crosslinkable polymer. . In the case of radiation crosslinking, an organic peroxide is not always necessary.
- polymerization inhibitors for example, known polymerization inhibitors, fillers, pigments, stabilizers, lubricants, mold release agents, plasticizers, anti-aging agents, silane coupling agents, ultraviolet absorbers, flame retardants, acid acceptors, etc. Can be used.
- anti-aging agents include di-t-butyl-P-cresol, pentaerythrityl-tetraxy [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2′methylenebis (2-methyl-6-t-butylphenyl), bis (2,2,6,6-tetramethyl-4-piperazyl) sebacate, N, N′-hexane-1,6-diylbis [3- (3 5-di-tert-butyl-4-hydroxyphenyl) propionamide], bis (2,2,6,6-tetramethyl-4-piperazyl) sebacate, hydroquinone monomethyl ether, methyl hydroquinone and the like.
- silane coupling agents ⁇ -chloropropyltrimethoxysilane, vinyltriethoxysilane, vinyl-tris- ( ⁇ -methoxyethoxy) silane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ - (3,4- Ethoxycyclohexyl) ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -aminopropyltrimethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropyltrimethoxysilane Etc.
- ultraviolet absorbers examples include 2-hydroxy-4-n-octyloxybenzophenone, 2,2-hydroxy-4,4-dimethoxybenzophenone, 2- (2′-hydroxy-5-methylphenyl) benzotriazole, pt -Butylphenyl salsylate and the like.
- the ratio of the above additives is usually 10 parts by weight or less, preferably 5 parts by weight or less, with respect to 100 parts by weight of the crosslinkable polymer.
- the above-mentioned components are mixed by a conventional kneader such as a Banbury mixer, a kneader, or an open roll to obtain a crosslinkable polymer composition.
- a conventional kneader such as a Banbury mixer, a kneader, or an open roll to obtain a crosslinkable polymer composition.
- the production method of the present invention is a method for producing a polymer molded body for curing a crosslinkable polymer.
- the triazine derivative represented by the said general formula (I) or its prepolymer is used as a crosslinking agent. Either heat crosslinking or radiation crosslinking may be used, but heat crosslinking is preferred.
- the heat crosslinking is performed by filling a mold having a desired shape with a predetermined amount of a crosslinkable polymer composition, performing a primary crosslinking by a heating process, and then performing a secondary crosslinking in an oven as necessary.
- the shape of the mold of the molding machine can be arbitrarily selected according to the use of the polymer molded body to be obtained, such as a sheet shape, a rod shape, a ring shape, and various complicated block shapes.
- the primary crosslinking is usually performed by heating at 120 ° C. to 200 ° C. for 2 to 30 minutes using, for example, an injection molding machine or a pressure molding machine.
- Secondary crosslinking is performed under conditions of 120 ° C. to 300 ° C. and 1 to 72 hours. In particular, when secondary crosslinking is carried out by heating at 200 ° C. to 300 ° C. for 1 to 72 hours, a polymer molded article having good mechanical strength can be obtained.
- an accelerated electron beam X-ray, ⁇ -ray, ⁇ -ray, ⁇ -ray, etc.
- the irradiation dose is usually 0.1 to 500 kGy, although it varies depending on the crosslinkable elastomer used.
- the polymer molded body of the present invention is a polymer molded body cured by the action of a crosslinking agent, and is formed using a triazine derivative represented by the above general formula (I) or a prepolymer thereof as a crosslinking agent.
- the manufacturing method is as described above.
- the polymer molded body of the present invention is sufficiently suppressed in deterioration of mechanical properties due to heat.
- the tensile strength (measured in accordance with ASTM D 638 before and after the thermal deterioration test under the conditions described below) (MPa) change rate (difference between post-test tensile strength and pre-test tensile strength and pre-test tensile strength) is ⁇ 55% to 0%.
- gear oven for example, “Gear Heat Aging Tester” (ACR-60A type) manufactured by Toyo Seiki Seisakusho Co., Ltd., which is commercially available as an accelerated heat aging tester for polymer materials such as rubber and plastic, is suitable. Can be used.
- the filtrate was distilled under reduced pressure to recover the solvent.
- the obtained residue was diluted with ethyl acetate, washed with a 5% by weight aqueous hydrochloric acid solution, further washed with water, dried over anhydrous magnesium sulfate and filtered.
- Ethyl acetate in the obtained filtrate was recovered by distillation under reduced pressure, and the residue was further distilled (distillation temperature: 155 ° C., vacuum: 0.5 Torr) to give 4,6-bis (diallylamino) as a 27.4 g liquid.
- -2-Allyloxy-1,3,5-triazine was obtained (LC purity 99%, yield 80%).
- the structure of the synthesized triazine derivative was identified by NMR and GC-MS.
- the measurement conditions of NMR and GC-MS are as shown in Tables 1 and 2 below.
- LC purity is measured by liquid chromatography using an “INERTSIL ODS-3” column (25 cm) loaded on “LC-10ADVP” manufactured by Shimadzu Corporation and using a mixed solvent of acetonitrile and water. It was calculated as an area percentage.
- the filtrate was distilled under reduced pressure to recover the solvent.
- the obtained residue was diluted with ethyl acetate, washed with a 5% by weight aqueous hydrochloric acid solution, further washed with water, dried over anhydrous magnesium sulfate and filtered.
- Ethyl acetate in the obtained filtrate was recovered by distillation under reduced pressure, and the residue was further distilled (distillation temperature: 155 ° C., vacuum: 0.5 Torr) to obtain 4,6- liquid as 11.6 g (0.04 mol) of liquid.
- Bis (allyloxy) -2-diallylamino-1,3,5-triazine was obtained (LC purity 99%, yield 40%).
- the identification of the compound and the “LC purity” measurement were carried out in the same manner as in Synthesis Example 1.
- ⁇ Evaluation method> (1) Physical properties of tensile strength (MPa), 100% tensile stress (MPa), and elongation (%) were performed according to ASTM D638. The hardness (Shore A) was measured according to JIS K 6253.
- the thermal deterioration test was performed by using a test piece punched into a dumbbell shape No. 3 defined in JIS K6251 and treating it at 250 ° C. for 70 hours in a gear oven.
- the gear oven used was “Gear Thermal Aging Tester” (ACR-60A type) manufactured by Toyo Seiki Seisakusho.
- Examples 4 to 5 and Comparative Example 2 Each component shown in Table 5 was kneaded into an ethylene vinyl acetate copolymer (EVA) by an open roll at a ratio shown in the same table. The obtained composition was subjected to hot press crosslinking (primary crosslinking) at 150 ° C. to obtain a sheet having a thickness of 1 mm.
- EVA ethylene vinyl acetate copolymer
- the torque of the composition (150 ° C.) was measured by reading the value over 15 minutes with a curast meter.
- the intermediate value between the minimum torque value and the maximum torque value was defined as “50% cross-linking torque”, and the time taken to reach it was defined as “50% cross-linking time”.
- a value of 30% of the difference between the minimum torque value and the maximum torque value was set as “30% cross-linking torque”, and the time to reach it was set as “30% cross-linking time”.
- the evaluation results are shown in Table 6.
- the test piece was formed into a dumbbell shape (JIS K 6251 tensile No. 3 type) to prepare a tensile test piece.
- a tensile test of a test piece prepared using an autograph AGS-10kNG type manufactured by Shimadzu Corporation was performed, and the stress (MPa) when the elongation between marked lines increased 100% at the start of the test was measured. Measured to 100% modulus.
- the tensile speed was 200 mm / min.
- test piece was cut into small pieces (width 10 mm, length 20 mm) to obtain a test piece for measuring the degree of swelling.
- the prepared test piece for measuring the degree of swelling was immersed in 30 mL of tetrahydrofuran at 25 ° C. for 24 hours, and the degree of swelling of the test piece was determined from the weight change before and after the swelling test using the following formula.
- the molded product of the crosslinkable elastomer composition of the present invention using an ethylene vinyl acetate copolymer as a substituted polyolefin is composed of various packaging materials such as foods, pharmaceuticals, industrial chemicals, agricultural chemicals, various adhesive films, and sealing films for solar cells. In addition, it is useful in the fields of hemodialysis, plasma component separation, protein solution desalting, fractionation, concentration, fruit juice concentration, and wastewater treatment.
- the molded article of the crosslinkable elastomer composition of the present invention using fluororubber is useful in the fields of automobile oil seals, O-rings, packings, hoses, electric wires, semiconductors and the like.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明のトリアジン誘導体は一般式(I)で表される。
本発明の橋剤は前記の一般式(I)で表されるトリアジン誘導体またはそのプレポリマーから成る。
本発明の架橋性高分子組成物は、架橋性高分子に少なくとも前記一般式(I)で表されるトリアジン誘導体またはそのプレポリマーを配合して成り、架橋性高分子100重量部に対するトリアジン誘導体またはそのプレポリマーの割合が0.05~15重量部である。
本発明の製造方法は架橋性高分子を硬化する高分子成形体の製造方法である。そして、架橋剤として前記一般式(I)で表されるトリアジン誘導体またはそのプレポリマーを使用する。加熱架橋と放射線架橋の何れでもよいが、加熱架橋が好ましい。
本発明の高分子成形体は、架橋剤の作用によって硬化された高分子成形体であり、架橋剤として前記一般式(I)で表されるトリアジン誘導体またはそのプレポリマーを使用して成る。その製造方法は前記の通りである。
JIS K6251に規定されたダンベル状3号形に打ち抜かれた試験片を使用し、ギヤオーブン内で250℃70時間処理する。
1,4-ジオキサン140gに炭酸ナトリウム21.2g(0.20mol)と塩化シアヌール20.0g(0.10mol)を添加して溶解した後、ジアリルアミン19.8g(0.20mol)を徐々に添加し、更に、苛性ソーダ8.4g(0.20mol)を添加した。反応熱により反応液の温度は約60℃となりその温度で2時間反応させた。その後、冷却し、反応混合物を濾過して副生した塩化ナトリウムを除去し、この濾液を減圧蒸留して溶媒を回収し、4,6-ビス(ジアリルアミノ)-2-クロロ-1,3,5-トリアジン34g(0.09mol)を得た。
1,4-ジオキサン140gに炭酸ナトリウム10.6g(0.10mol)と塩化シアヌール20.0g(0.10mol)を添加して溶解した後、ジアリルアミン9.9g(0.10mol)を徐々に添加し、更に、苛性ソーダ4.2g(0.10mol)を添加した。反応熱により反応液の温度は約60℃となりその温度で3時間反応させた。その後、冷却し、反応混合物を濾過して副生した塩化ナトリウムを除去し、この濾液を減圧蒸留して溶媒を回収し、4,6-ジクロロ-2-ジアリルアミノ-1,3,5-トリアジン18.3g(0.05mol)を得た。
オープンロールにより、90℃で表3に示す各成分を同表に示す割合でフッ素ゴムへ混練りした。得られた組成物を原料とし、表3に示す条件でプレス架橋(一次架橋)を行い、次いで表4に示す条件で二次架橋を行なった。そして、各架橋物の機械的特性を評価した。その結果を表4に示す。なお、以下の諸例で使用した評価方法は以下の通りである。
(2)Carbons Inc.製「サーマックスMT N990」
(3)2,5-ジメチル-2,5-(t-ブチルパーオキシ)ヘキサン(日本油脂(株)製)
(4)合成例1で得た4,6-ビス(ジアリルアミノ)-2-アリロキシ-1,3,5-トリアジン
(5)合成例2で得た4,6-ビス(アリロキシ)-2-ジアリルアミノ-1,3,5-トリアジン
(6)トリアリルイソシアヌレート(日本化成(株)製)
(1)引張り強度(MPa)、100%引張り応力(MPa)、伸び(%)の各物性は、ASTM D 638に準拠して行った。硬さ(ショアA)はJIS K 6253に準拠して行った。
オープンロールにより、表5に示す各成分を同表に示す割合でエチレン酢酸ビニル共重合物(EVA)へ混練りした。得られた組成物を得られた組成物を150℃で熱プレス架橋(一次架橋)して厚さ1mmのシートを得た。
(2)2,5-ジメチル-2,5-(t-ブチルパーオキシ)ヘキサン(日本油脂(株)製)
(3)合成例1で得た4,6-ビス(ジアリルアミノ)-2-アリロキシ-1,3,5-トリアジン
(4)トリアリルイソシアヌレート(日本化成(株)製)
(5)γ-メタクリロキシプロピルトリメトキシシラン
(6)2-ヒドロキシ-4-n-オクトキシベンゾフェノン
表7に示す各成分を同表に示す割合で混練し、150℃で20分間熱プレスしてシート状のエチレン酢酸ビニル共重合体成形体を得た。なお、表7中の比較例2の組成物は表5中の比較例2と同一組成物であり、表7中の各成分は「架橋剤-2」を除き表5におけるものと同じである。
試験片をダンベル状(JIS K 6251 引張3号形)に成形し、引張試験片を作成した。次に、オートグラフ(島津製作所製 AGS-10kNG型)を用いて作製した試験片の引張試験を行い、標線間の伸びが試験開始時の100%増になった時の応力(MPa)を測定し、100%モジュラスとした。なお、引張速度は200mm/minで行った。
試験片を小片状(幅10mm、長さ20mm)に切出し、膨潤度測定用試験片とした。次に、作成した膨潤度測定用試験片を25℃のテトラヒドロフラン30mLに24時間浸漬し、膨潤試験前後の重量変化から以下の式を用い、試験片の膨潤度を求めた。
膨潤度(-)=(膨潤試験後の試験片重量(g)-膨潤試験前の試験片重量(g))/膨潤試験前の試験片重量(g)
試験片をヘイズメーター(日本電色工業製 NDH-2000型)を用い、試験片の全光線透過率を3箇所測定し、その平均値を算出した。
Claims (15)
- 一般式(I)で表されるトリアジン誘導体またはそのプレポリマーから成ることを特徴とする架橋剤。
- 架橋性高分子に少なくとも前記一般式(I)で表されるトリアジン誘導体またはそのプレポリマーを配合して成り、架橋性高分子100重量部にに対するトリアジン誘導体またはそのプレポリマーの割合が0.05~15重量部であることを特徴とする架橋性高分子組成物。
- 架橋性高分子が架橋性エラストマーである請求項3に記載の架橋性高分子組成物。
- 架橋性エラストマーがフッ素ゴム又は置換ポリオレフィンである請求項4に記載の架橋性高分子組成物。
- 置換ポリオレフィンがエチレン酢酸ビニル共重合体である請求項5に記載の架橋性高分子組成物。
- 架橋性高分子を硬化する高分子成形体の製造方法において、架橋剤として前記一般式(I)で表されるトリアジン誘導体またはそのプレポリマーを使用することを特徴とする高分子成形体の製造方法。
- 架橋性高分子が架橋性エラストマーである請求項7に記載の製造方法。
- 架橋性エラストマーがフッ素ゴム又は置換ポリオレフィンである請求項8に記載の製造方法。
- 置換ポリオレフィンがエチレン酢酸ビニル共重合体である請求項9に記載の製造方法。
- 架橋剤の作用によって硬化された高分子成形体であり、架橋剤として前記一般式(I)で表されるトリアジン誘導体またはそのプレポリマーを使用して成ることを特徴とする高分子成形体。
- 架橋性高分子が架橋性エラストマーである請求項11に記載の高分子成形体。
- 架橋性エラストマーがフッ素ゴム又は置換ポリオレフィンである請求項12に記載の高分子成形体。
- 置換ポリオレフィンがエチレン酢酸ビニル共重合体である請求項13に記載の高分子成形体。
- 以下に記載する条件下の熱劣化試験の前後におけるASTM D 638に準拠して測定した引張り強度(MPa)の変化率(試験後引張り強度と試験前引張り強度の差と試験前引張り強度の比率)が-55%~0%である請求項9~11の何れかに記載の高分子成形体。
[熱劣化試験の条件]
JIS K6251に規定されたダンベル状3号形に打ち抜かれた試験片を使用し、ギヤオーブン内で250℃70時間処理する。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020127017761A KR101706582B1 (ko) | 2010-02-17 | 2011-02-03 | 트리아진 유도체 및 그의 응용 |
CN201180008353.0A CN102741235B (zh) | 2010-02-17 | 2011-02-03 | 三嗪衍生物及其应用 |
US13/579,376 US8987383B2 (en) | 2010-02-17 | 2011-02-03 | Triazine derivatives and application thereof |
EP11744519.7A EP2537833A4 (en) | 2010-02-17 | 2011-02-03 | TRIAZINE DERIVATIVE AND APPLICATION THEREOF |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010032467 | 2010-02-17 | ||
JP2010-032467 | 2010-02-17 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011102231A1 true WO2011102231A1 (ja) | 2011-08-25 |
Family
ID=44482822
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2011/052249 WO2011102231A1 (ja) | 2010-02-17 | 2011-02-03 | トリアジン誘導体およびその応用 |
Country Status (7)
Country | Link |
---|---|
US (1) | US8987383B2 (ja) |
EP (1) | EP2537833A4 (ja) |
JP (1) | JP5857408B2 (ja) |
KR (1) | KR101706582B1 (ja) |
CN (1) | CN102741235B (ja) |
TW (1) | TWI508953B (ja) |
WO (1) | WO2011102231A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015149222A1 (en) * | 2014-03-31 | 2015-10-08 | Dow Global Technologies Llc | Crosslinkable polymeric compositions with diallyl isocyanurate crosslinking coagents, methods for making the same, and articles made therefrom |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014119693A1 (ja) * | 2013-01-31 | 2014-08-07 | 大日本印刷株式会社 | 電子線硬化性樹脂組成物、リフレクター用樹脂フレーム、リフレクター、半導体発光装置、及び成形体の製造方法 |
WO2014119692A1 (ja) * | 2013-01-31 | 2014-08-07 | 大日本印刷株式会社 | 電子線硬化性樹脂組成物、リフレクター用樹脂フレーム、リフレクター、半導体発光装置、及び成形体の製造方法 |
CN103819420A (zh) * | 2013-07-01 | 2014-05-28 | 江阴摩尔化工新材料有限公司 | 紫外光固化低聚物、其合成方法及含有该低聚物的紫外光固化涂料 |
WO2015149221A1 (en) | 2014-03-31 | 2015-10-08 | Dow Global Technologies Llc | Crosslinkable polymeric compositions with n,n,n',n',n",n"-hexaallyl-1,3,5-triazine-2,4,6-triamine crosslinking coagent, methods for making the same, and articles made therefrom |
KR102003345B1 (ko) * | 2017-04-28 | 2019-07-24 | 삼성에스디아이 주식회사 | 레지스트 하층막용 조성물 및 이를 이용한 패턴형성방법 |
CN107151272A (zh) * | 2017-05-15 | 2017-09-12 | 江南大学 | 一种三嗪衍生物改性纤维素纳米晶体的制备方法 |
CN107978769B (zh) * | 2017-11-19 | 2020-05-15 | 湖南辰砾新材料有限公司 | 一种钒电池用基于三嗪衍生物隔膜及其制备方法 |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2308560A1 (de) * | 1973-02-21 | 1974-09-05 | Siemens Ag | Verfahren zur herstellung von 2,4dienoxy-6-aminoalkyl(-en)-s-triazinen |
DE2506105A1 (de) * | 1975-02-13 | 1976-08-26 | Siemens Ag | Radikalisch vernetzbare polymersysteme |
JPS5438342A (en) * | 1977-09-02 | 1979-03-22 | Furukawa Electric Co Ltd:The | Polyolefin composition |
US4460748A (en) * | 1982-07-06 | 1984-07-17 | Luperox Gmbh | Process for crosslinking and, if desired, foaming natural or synthetic homo- and/or copolymers |
JPH06206955A (ja) * | 1993-01-07 | 1994-07-26 | Asahi Chem Ind Co Ltd | 新規なるポリフェニレンエーテル系樹脂組成物 |
JP2003238761A (ja) * | 2002-02-21 | 2003-08-27 | Nof Corp | 架橋性樹脂組成物、架橋性成形品および架橋成形品 |
JP2006273995A (ja) * | 2005-03-29 | 2006-10-12 | Toray Ind Inc | ポリ乳酸架橋発泡体の製造法 |
JP2009057501A (ja) * | 2007-08-31 | 2009-03-19 | Sankyo Kasei Kk | 分子接着剤、架橋反応性固体表面及び該架橋反応性固体表面の製造方法 |
WO2009139141A1 (ja) * | 2008-05-12 | 2009-11-19 | 日本化成株式会社 | 架橋剤、架橋性高分子組成物、及びその成形体 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2537816A (en) * | 1951-01-09 | Method-of preparing tjnsaturated | ||
DE1064071B (de) * | 1957-09-12 | 1959-08-27 | Akad Wissenschaften Ddr | Verfahren zur Herstellung von Triallyl- bzw. Trimethallylcyanurat |
NL244981A (ja) * | 1958-11-05 | |||
US4116914A (en) * | 1977-02-14 | 1978-09-26 | Monsanto Company | Elastoplastic compositions of ethylene-vinyl acetate rubber and polyolefin resin |
US5672703A (en) * | 1995-03-21 | 1997-09-30 | Cytec Technology Corp. | 1,3,5-triazine compounds substituted with acetal and/or cyclized acetal-based groups |
JP4423626B2 (ja) * | 1999-07-29 | 2010-03-03 | 日本農薬株式会社 | 除草剤組成物 |
JP4753336B2 (ja) * | 2001-09-04 | 2011-08-24 | 日本化薬株式会社 | 新規アリル化合物及びその製法 |
-
2011
- 2011-02-03 KR KR1020127017761A patent/KR101706582B1/ko active IP Right Grant
- 2011-02-03 CN CN201180008353.0A patent/CN102741235B/zh not_active Expired - Fee Related
- 2011-02-03 WO PCT/JP2011/052249 patent/WO2011102231A1/ja active Application Filing
- 2011-02-03 US US13/579,376 patent/US8987383B2/en active Active
- 2011-02-03 EP EP11744519.7A patent/EP2537833A4/en not_active Withdrawn
- 2011-02-03 JP JP2011021469A patent/JP5857408B2/ja active Active
- 2011-02-16 TW TW100105078A patent/TWI508953B/zh active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2308560A1 (de) * | 1973-02-21 | 1974-09-05 | Siemens Ag | Verfahren zur herstellung von 2,4dienoxy-6-aminoalkyl(-en)-s-triazinen |
DE2506105A1 (de) * | 1975-02-13 | 1976-08-26 | Siemens Ag | Radikalisch vernetzbare polymersysteme |
JPS5438342A (en) * | 1977-09-02 | 1979-03-22 | Furukawa Electric Co Ltd:The | Polyolefin composition |
US4460748A (en) * | 1982-07-06 | 1984-07-17 | Luperox Gmbh | Process for crosslinking and, if desired, foaming natural or synthetic homo- and/or copolymers |
JPH06206955A (ja) * | 1993-01-07 | 1994-07-26 | Asahi Chem Ind Co Ltd | 新規なるポリフェニレンエーテル系樹脂組成物 |
JP2003238761A (ja) * | 2002-02-21 | 2003-08-27 | Nof Corp | 架橋性樹脂組成物、架橋性成形品および架橋成形品 |
JP2006273995A (ja) * | 2005-03-29 | 2006-10-12 | Toray Ind Inc | ポリ乳酸架橋発泡体の製造法 |
JP2009057501A (ja) * | 2007-08-31 | 2009-03-19 | Sankyo Kasei Kk | 分子接着剤、架橋反応性固体表面及び該架橋反応性固体表面の製造方法 |
WO2009139141A1 (ja) * | 2008-05-12 | 2009-11-19 | 日本化成株式会社 | 架橋剤、架橋性高分子組成物、及びその成形体 |
Non-Patent Citations (6)
Title |
---|
DATABASE CAPLUS AHNE, H. ET AL.: "Partial aminolysis of 2,4,6- triallyloxy-s-triazine. I. Preparation of 2-alkyl(-en)amino-4,6-diallyloxy-s-triazines", Database accession no. 82:156228 * |
DATABASE CAPLUS KAZUKO SETA ET AL.: "Kobunshi Hashikakezai to shite no Fuhowa Cyanurate-gata Novolac", Database accession no. 68:50432 * |
DATABASE CAPLUS VOROTYNTSEVA, V.D. ET AL.: "Infrared spectra and Raman spectra of s-triazine derivatives with amino, alkoxy, and alkylamino type substituents", Database accession no. 77:145872 * |
SYNTHESIS, no. 3, 1975, pages 182 - 184 * |
THE JOURNAL OF CHEMICAL INDUSTRY, vol. 70, no. 5, 1968, pages 784 - 788 * |
ZHURNAL PRIKLADNOI SPEKTROSKOPII, vol. 17, no. 2, 1972, pages 286 - 289 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015149222A1 (en) * | 2014-03-31 | 2015-10-08 | Dow Global Technologies Llc | Crosslinkable polymeric compositions with diallyl isocyanurate crosslinking coagents, methods for making the same, and articles made therefrom |
Also Published As
Publication number | Publication date |
---|---|
US8987383B2 (en) | 2015-03-24 |
JP2011190431A (ja) | 2011-09-29 |
TW201141843A (en) | 2011-12-01 |
KR20130000371A (ko) | 2013-01-02 |
CN102741235A (zh) | 2012-10-17 |
CN102741235B (zh) | 2015-09-09 |
JP5857408B2 (ja) | 2016-02-10 |
KR101706582B1 (ko) | 2017-02-27 |
EP2537833A1 (en) | 2012-12-26 |
EP2537833A4 (en) | 2013-06-19 |
TWI508953B (zh) | 2015-11-21 |
US20130023629A1 (en) | 2013-01-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5857408B2 (ja) | トリアジン誘導体およびその応用 | |
WO2011096477A1 (ja) | 架橋性エラストマー用架橋剤およびその応用 | |
JP6767390B2 (ja) | 加硫可能な混合物および加硫物を製造するための、改良された低温特性および良好な耐オイル性を有するアクリレートゴムの使用 | |
EP3322752B1 (en) | Fluorinated thermosetting plastic with iodine endgroups | |
JP4984743B2 (ja) | 架橋剤、架橋性エラストマー組成物およびその成形体、架橋性熱可塑性樹脂組成物およびその成形体 | |
WO2011102230A1 (ja) | 架橋性エラストマー用架橋剤およびその応用 | |
EP2837657B1 (en) | Acrylic rubber composition, and crosslinked product thereof | |
JP5453909B2 (ja) | 架橋剤、架橋性高分子組成物、及びその成形体 | |
JP2011162634A (ja) | 高分子成形体およびその製造方法 | |
US20200040157A1 (en) | Nanosubstance-containing composition | |
JP5998588B2 (ja) | 含フッ素エラストマーブレンド物およびその組成物 | |
WO2021166664A1 (ja) | 含フッ素共重合体組成物及びその架橋体、並びに化合物 | |
CN113544160A (zh) | 交联橡胶 | |
CN113544159A (zh) | 组合物、交联橡胶及其制造方法 | |
US20050124773A1 (en) | Extrudable fluoroelastomer composition | |
JP2010084000A (ja) | 新規架橋助剤、架橋性フッ素ゴム組成物および架橋ゴム物品 | |
JP2011225692A (ja) | 架橋用高分子組成物および高分子成形体 | |
EP3936534A1 (en) | Fluorine-containing copolymer composition, crosslinked rubber and method for producing same | |
JP4479515B2 (ja) | 含フッ素エラストマー組成物 | |
WO2020116394A1 (ja) | エラストマー組成物及びシール材 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201180008353.0 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11744519 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20127017761 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 7220/DELNP/2012 Country of ref document: IN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2011744519 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13579376 Country of ref document: US |