WO2013141152A1 - ゴム組成物および当該ゴム組成物を用いたロール成型品 - Google Patents
ゴム組成物および当該ゴム組成物を用いたロール成型品 Download PDFInfo
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- WO2013141152A1 WO2013141152A1 PCT/JP2013/057370 JP2013057370W WO2013141152A1 WO 2013141152 A1 WO2013141152 A1 WO 2013141152A1 JP 2013057370 W JP2013057370 W JP 2013057370W WO 2013141152 A1 WO2013141152 A1 WO 2013141152A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/023—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets using multilayered plates or sheets
- B29C55/026—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets using multilayered plates or sheets of preformed plates or sheets coated with a solution, a dispersion or a melt of thermoplastic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
- B29C55/06—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique parallel with the direction of feed
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- 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
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3445—Five-membered rings
- C08K5/3447—Five-membered rings condensed with carbocyclic rings
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/16—EPM, i.e. ethylene-propylene copolymers; EPDM, i.e. ethylene-propylene-diene copolymers; EPT, i.e. ethylene-propylene terpolymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
- B29K2995/0034—Polarising
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- 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
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- 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 rubber composition containing ethylene-propylene-diene copolymer rubber as a main component and a roll molded product using the rubber composition.
- a polarizing film in which a dichroic dye is adsorbed and oriented on a polyvinyl alcohol film has been used. That is, an iodine polarizing film using iodine as a dichroic dye, a dye polarizing film using a dichroic dye as a dichroic dye, and the like are known. These polarizing films are usually used as polarizing plates by attaching a protective film such as triacetyl cellulose to one or both sides of the polarizing film via an adhesive made of an aqueous solution of a polyvinyl alcohol resin.
- a nip roll and a guide roll are used as a method for producing a polarizing film.
- a polyvinyl alcohol film is immersed in water to swell, then dyed with a dichroic dye, stretched, and then fixed with iodine to the film. Therefore, a method is known in which a polyvinyl alcohol film is treated with boric acid, washed with water and then dried. At this time, the film is stretched by giving a peripheral speed difference to the nip rolls before and after the treatment bath, the film transport direction is changed by the guide roll, and the film is introduced into and taken out of the treatment liquid (for example, Japanese Patent Laid-Open No. 10-170721 (see Patent Document 1).
- Patent Document 2 discloses a nip roll for manufacturing a polarizing film having excellent durability.
- a nip roll is composed of a rubber layer whose main component is EPDM (ethylene-propylene-diene rubber) containing at least a surface of carbon black and vulcanized with a peroxide.
- EPDM ethylene-propylene-diene rubber
- the surface layer made of the rubber composition of the nip roll is worn out if it is used for a long time.
- the present invention is a rubber composition mainly composed of EPDM, which is excellent in chemical resistance to chemicals used in the production process of a polarizing film, and further has excellent wear resistance and can form a roll molded product having a long life, and
- An object of the present invention is to provide a roll molded product using the roll molded product and a method for producing a polarizing film using the roll molded product.
- the present invention relates to a rubber composition
- a rubber composition comprising an ethylene-propylene-diene copolymer rubber blended with a vulcanizing agent, carbon black, and an antioxidant, and the ethylene-propylene-diene copolymer rubber has a Mooney viscosity of 80 or more.
- a rubber composition in which the arithmetic average particle diameter of carbon black is 25 nm or less and the anti-aging agent is a benzimidazole compound.
- the present invention also relates to a rubber composition obtained by blending an ethylene-propylene-diene copolymer rubber with a vulcanizing agent, carbon black, and an antioxidant, and the ethylene-propylene-diene copolymer rubber has a Mooney viscosity of 80.
- a rubber composition in which the average particle size of carbon black is 25 nm or less and the anti-aging agent is a reactive anti-aging agent.
- the present invention is a roll-molded product used in the manufacturing process of a polarizing film having a rubber layer formed from the rubber composition on the surface.
- the present invention is a production method for producing a polarizing film by subjecting a polyvinyl alcohol film to swelling treatment, dyeing treatment, boric acid treatment and washing treatment in this order, and producing a polarizing film, wherein at least one of these treatments
- a uniaxial stretching process is performed using the difference in peripheral speed between the two nip rolls, and at least one of the roll molded products constituting the nip roll is the roll molding of the present invention. It is a product.
- the rubber composition of the present invention is excellent in chemical resistance to chemicals used in the manufacturing process of a polarizing film, and further excellent in wear resistance, and is useful for the surface layer of a roll molded product used for manufacturing a polarizing film. It is.
- the present invention is a rubber composition obtained by blending an ethylene-propylene-diene copolymer rubber with a vulcanizing agent, carbon black, and an antioxidant.
- ethylene-propylene-diene copolymer rubber EPDM
- EPM ethylene-propylene rubber
- the third component include ethylidene norbornene (ENB), 1,4-hexadiene (1,4-HD), dicyclopentadiene (DCP), and the like.
- EPDM having a Mooney viscosity of 80 or more is used. When the Mooney viscosity of EPDM is 80 or more, the wear resistance is improved.
- the iodine value of EPDM is preferably 5 to 24.
- the rubber composition in the present invention may contain EPDM as a main component and other rubber components.
- EPDM as a main component
- other rubber components include, but are not limited to, EPM, butyl rubber, styrene-butadiene rubber, chloroprene rubber, and the like.
- the rubber composition in the present invention preferably contains EPDM in a proportion of 70 to 100% by weight. When the blending amount of EPDM is less than 70% by weight, the wear resistance and chemical resistance are improved. May decrease.
- the rubber composition of the present invention contains a vulcanizing agent for vulcanizing (crosslinking) EPDM.
- a vulcanizing agent for vulcanizing (crosslinking) EPDM examples include benzoyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 1,1′-di-t-butylperoxy-3,3, Peroxides such as 5-trimethylenecyclohexane and 1,3-di- (t-butylperoxy) -diisopropylbenzene are preferred.
- the addition amount of the vulcanizing agent is preferably 1 to 10 parts by weight, and more preferably 5 to 10 parts by weight with respect to 100 parts by weight of EPDM.
- the rubber composition of the present invention contains carbon black having an arithmetic average particle size of 25 nm or less as a reinforcing agent.
- the arithmetic average particle diameter of carbon black exceeds 25 nm, the wear resistance decreases.
- An example of carbon black used in the present invention is Seest 3 manufactured by Tokai Carbon Co., Ltd.
- the amount of carbon black added is preferably 30 to 90 parts by weight and more preferably 40 to 70 parts by weight with respect to 100 parts by weight of EPDM. When the added amount of carbon black is less than 30 parts by weight, the wear resistance is not improved and the moldability is also inferior, and when the added amount of carbon black exceeds 90 parts by weight, it becomes difficult to mold, which is not preferable.
- the rubber composition of the present invention contains an anti-aging agent.
- a benzimidazole compound and / or a reactive antiaging agent is used as an antiaging agent.
- the benzimidazole compound include 2-mercaptomethylbenzimidazole and 2-mercaptobenzimidazole.
- the reactive anti-aging agent include N-phenyl-N ′-(3-methacryloyloxy-2-hydroxypropyl) -p-phenylenediamine and N- (4-anilinophenyl) methacrylamide.
- the addition amount of the anti-aging agent is preferably 0.5 to 3.0 parts by weight, more preferably 0.8 to 2.0 parts by weight with respect to 100 parts by weight of EPDM.
- additives can be blended in addition to the vulcanizing agent, carbon black, and antiaging agent described above.
- additives include reinforcing agents other than carbon black, fillers, paraffinic, naphthenic and aromatic process oils, and vulcanization accelerators such as stearic acid and zinc white.
- the reinforcing agent and filler include acid-resistant additives such as silica and clay.
- the rubber composition of the present invention can be used for production of various molded products such as roll molded products. Since the rubber composition of the present invention is excellent in chemical resistance and abrasion resistance to chemicals used in the production of a polarizing film, a roll molded product in which a surface layer is formed using the rubber composition of the present invention is a polarizing film. It is suitable as a roll used for production.
- the obtained roll molded product is suitable for a nip roll used in the manufacturing process of a polarizing film.
- the hardness of the rubber layer surface (JIS Type A) is preferably 60 to 85 by a rubber hardness meter. When the rubber hardness of the surface is less than 60, the life and wear resistance of the roll are deteriorated. On the other hand, when the rubber hardness of the surface exceeds 85, the cushioning property is deteriorated, which may adversely affect the film to be processed.
- the rubber hardness (JIS Type A) on the surface is more preferably 65-80.
- the method for producing a polarizing film of the present invention is a method for producing a polarizing film by subjecting a polyvinyl alcohol film to swelling treatment, dyeing treatment, boric acid treatment and washing treatment in this order. Furthermore, a uniaxial stretching process is performed in parallel with at least one of the processes described above or separately from these processes. When performing uniaxial stretching separately from the above-mentioned process, the process of the wet extending process for performing uniaxial stretching is added between the above-mentioned processes. The uniaxial stretching process may be performed in one step, but may be performed in a plurality of steps. Moreover, you may uniaxially stretch a polyvinyl alcohol-type film in gas, such as air or an inert gas, before a swelling process. The final cumulative draw ratio is 4.5 to 7.0 times, preferably 5.0 to 6.5 times.
- At least one step of the uniaxial stretching process is a step of performing uniaxial stretching by utilizing a peripheral speed difference between the nip roll disposed on the upstream side and the nip roll disposed on the downstream side.
- at least 1 of the roll molded product which comprises the nip roll used for an upstream side and a downstream is the rubber layer of the surface formed with the rubber composition of this invention, More preferably, it comprises a nip roll. All of the roll molded products have the rubber layer formed on the surface thereof by the rubber composition of the present invention. The details of the roll molded product having the rubber layer formed on the surface thereof by the rubber composition of the present invention are as described above.
- the roll molded product in which the rubber layer on the surface is formed by the rubber composition of the present invention is excellent in chemical resistance and abrasion resistance, and is an environment where chemicals for boron treatment or chemicals for dyeing adhere. Even if it is used for a long time below, there is little deterioration and the polarizing film can be clamped satisfactorily.
- the polyvinyl alcohol resin forming the polyvinyl alcohol film in the present invention is typically exemplified by a saponified polyvinyl acetate resin.
- the degree of saponification is usually 85 mol% or more, preferably 90 mol% or more, more preferably 99 mol% to 100 mol%.
- Polyvinyl acetate resins include polyvinyl acetate, which is a homopolymer of vinyl acetate, and copolymers of vinyl acetate and other monomers copolymerizable therewith, such as ethylene-vinyl acetate copolymer. Examples include coalescence.
- Examples of other copolymerizable monomers include unsaturated carboxylic acids, olefins, vinyl ethers, and unsaturated sulfonic acids.
- the degree of polymerization of the polyvinyl alcohol-based resin is usually about 1000 to 10,000, preferably about 1500 to 5,000.
- polyvinyl alcohol resins may be modified.
- polyvinyl formal modified with aldehydes polyvinyl acetal, polyvinyl butyral, and the like may be used.
- an unstretched film of a polyvinyl alcohol film having a thickness of 20 to 100 ⁇ m, preferably 30 to 80 ⁇ m is used as a starting material for producing a polarizing film.
- the width of the film is practically 1500 mm to 6000 mm.
- the unstretched film is processed in the order of swelling treatment, dyeing treatment, boric acid treatment (crosslinking treatment), washing treatment, and finally dried to obtain a polyvinyl alcohol polarizing film having a thickness of, for example, about 5 to 50 ⁇ m. .
- the swelling treatment is performed for the purpose of removing foreign matter on the film surface, removing the plasticizer in the film, imparting easy dyeability in the next step, and plasticizing the film.
- the treatment conditions are determined within a range in which these objects can be achieved and within a range in which problems such as extreme dissolution and devitrification of the base film do not occur.
- the film In order to swell an unstretched raw film from the beginning, the film is immersed in an aqueous solution of, for example, 10 ° C. to 50 ° C., preferably 20 ° C. to 40 ° C.
- the immersion time of the film is preferably about 30 seconds to 300 seconds, more preferably about 60 seconds to 240 seconds.
- Uniaxial stretching may be performed in parallel with the swelling treatment, and the stretching ratio in that case is usually 1.2 to 3.0 times, preferably 1.3 to 2.5 times.
- the speed of the transport roll before and after the processing tank is set to eliminate sagging of the film in the transport direction. It is preferable to take measures such as control.
- the swelling treatment bath used in the range of 0.01 to 10% by weight was added to the swelling treatment bath used in the range of 0.01 to 10% by weight. It is also possible to use an aqueous solution.
- the dyeing step with the dichroic dye is performed for the purpose of adsorbing and orienting the dichroic dye on the film.
- the treatment conditions are determined within a range in which these objects can be achieved and within a range in which problems such as extreme dissolution and devitrification of the base film do not occur.
- the immersion treatment is performed at a concentration of ⁇ 10 / 100 for 30 seconds to 600 seconds, preferably 60 seconds to 300 seconds.
- potassium iodide instead of potassium iodide, other iodides such as zinc iodide may be used. Other iodides may be used in combination with potassium iodide. In addition, compounds other than iodide, such as boric acid, zinc chloride, and cobalt chloride, may coexist.
- boric acid When boric acid is added, it is distinguished from the following boric acid treatment in that it contains iodine. Any dye containing 0.003 parts by weight or more of iodine with respect to 100 parts by weight of water can be regarded as a dyeing tank.
- An immersion treatment is performed at a concentration of 1/100 for 30 seconds to 600 seconds, preferably 60 seconds to 300 seconds.
- the aqueous solution of the dichroic dye to be used may have a dyeing assistant or the like, and may contain, for example, an inorganic salt such as sodium sulfate, a surfactant or the like.
- the dichroic dye may be used alone, or two or more dichroic dyes may be used at the same time.
- the cumulative draw ratio up to the dyeing treatment (if there is no draw treatment before the treatment, the draw ratio in the treatment) is usually 1.6 to 4.5 times, preferably 1.8 to 4.0 times. .
- the draw ratio of integration up to the dyeing process is less than 1.6 times, the frequency of film breakage increases, and the yield tends to deteriorate.
- the boric acid treatment is performed by immersing a polyvinyl alcohol film dyed with a dichroic dye in an aqueous solution containing, for example, 1 to 10 parts by weight of boric acid with respect to 100 parts by weight of water.
- the dichroic dye is iodine
- iodide include potassium iodide and zinc iodide.
- compounds other than iodide such as zinc chloride, cobalt chloride, zirconium chloride, sodium thiosulfate, potassium sulfite, sodium sulfate, etc. may coexist.
- This boric acid treatment is carried out for water resistance and hue adjustment (to prevent bluishness, etc.) by crosslinking.
- a cross-linking agent such as glyoxal or glutaraldehyde can be used in addition to or together with boric acid, if necessary.
- the boric acid treatment for water resistance may be referred to by names such as water resistance treatment, crosslinking treatment, and immobilization treatment.
- boric acid treatment for hue adjustment may be referred to by a name such as complementary color treatment or re-dyeing treatment.
- This boric acid treatment is performed by appropriately changing the concentration of boric acid and iodide and the temperature of the treatment bath according to the purpose.
- the boric acid treatment for water resistance and the boric acid treatment for hue adjustment are not particularly distinguished, but are carried out under the following conditions.
- boric acid is added in an amount of 3 to 10 parts by weight and iodide in 100 parts by weight of water.
- a boric acid treatment bath containing 1 to 20 parts by weight is used, and it is usually carried out at a temperature of 50 ° C. to 70 ° C., preferably 53 ° C. to 65 ° C.
- the immersion time is usually about 10 to 600 seconds, preferably 20 to 300 seconds, and more preferably 20 to 200 seconds.
- the temperature of the boric acid treatment bath is usually 50 ° C. to 85 ° C., preferably 55 ° C. to 80 ° C.
- boric acid treatment for hue adjustment may be performed.
- the dichroic dye is iodine
- a boric acid treatment bath containing 1 to 5 parts by weight of boric acid and 3 to 30 parts by weight of iodide for 100 parts by weight of water is used for this purpose.
- it is carried out at a temperature of 10 ° C to 45 ° C.
- the immersion time is usually about 1 to 300 seconds, preferably 2 to 100 seconds.
- boric acid treatments may be performed a plurality of times and are usually performed 2 to 5 times in many cases.
- the aqueous solution composition and temperature of each boric acid treatment tank to be used may be the same or different within the above range.
- the boric acid treatment for water resistance and the boric acid treatment for hue adjustment may be performed in a plurality of steps, respectively.
- the washing treatment is performed, for example, by immersing a polyvinyl alcohol film treated with boric acid for water resistance and / or color tone adjustment in water, spraying water as a shower, or using both immersion and spraying.
- the temperature of water in the cleaning treatment is usually about 2 to 40 ° C., and the immersion time is preferably about 2 to 120 seconds.
- the polyvinyl alcohol film is dried in a drying furnace at a temperature of about 40 to 100 ° C. for about 60 to 600 seconds to obtain a polarizing film.
- the final integrated draw ratio of the polarizing film in the present invention is usually 4.5 to 7 times, preferably 5 to 6.5 times.
- FIG. 1 is an explanatory diagram showing an embodiment of a uniaxial stretching treatment method in which a uniaxial stretching treatment is performed in parallel with a swelling treatment, a dyeing treatment, or a boric acid treatment.
- nip rolls 2 and 2 ′ are provided on the upstream side and the downstream side of the treatment tank 10, respectively, and the peripheral speed of the nip roll 2 ′ on the downstream side is controlled to be higher than the peripheral speed of the nip roll 2 on the upstream side.
- the polyvinyl alcohol film 1 is uniaxially stretched.
- the treatment tank 10 is one of a treatment tank for swelling treatment, a treatment tank for dyeing treatment, and a treatment tank for boric acid treatment, and the treatment tank 10 is filled with a treatment solution 4 for immersion.
- a treatment solution 4 for immersion it is preferable that all of the roll molded products constituting the nip rolls 2 and 2 'have a rubber layer formed on the surface thereof by the rubber composition of the present invention. Since the rubber composition according to the present invention is excellent in chemical resistance and abrasion resistance, the dye solution and the boric acid treatment solution adhere to the nip rolls 2 and 2 'made of a roll molded product formed using the rubber composition. It can withstand long-term use even if used continuously in an environment.
- the polyvinyl alcohol film 1 is guided into the treatment solution 4 by a plurality of guide rolls 5.
- the guide roll 5 may also have a rubber layer formed on the surface thereof made of the rubber composition according to the present invention. Since the rubber composition according to the present invention is excellent in chemical resistance and wear resistance, the guide roll 5 formed using the rubber composition may be used by being immersed in the treatment solution 4, for example. It can withstand long-term use.
- FIG. 1 shows an embodiment in which both the upstream and downstream nip rolls 2 and 2 ′ are installed in the gas, one or both of these nip rolls 2 and 2 ′ are installed in the processing solution 4. Also good.
- a polarizing plate is obtained by pasting a protective film with an adhesive on at least one side of the polarizing film thus produced.
- protective films include films made of acetyl cellulose resins such as triacetyl cellulose and diacetyl cellulose, films made of polyester resins such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate, and films made of polycarbonate resins.
- a film made of a cycloolefin resin examples of commercially available thermoplastic cycloolefin-based resins include “Topas” (registered trademark) sold by Ticona of Germany and “Arton” (trademark) sold by JSR Co., Ltd.
- a film formed from such a cycloolefin-based resin is used as a protective film.
- a known method such as a solvent casting method or a melt extrusion method is appropriately used.
- the formed cycloolefin resin film is also commercially available, for example, “Essina” and “SCA40” sold by Sekisui Chemical Co., Ltd.
- the protective film has a function as a retardation film, a function as a brightness enhancement film, a function as a reflection film, a function as a transflective film, a function as a diffusion film, a function as an optical compensation film, etc. It can also have an optical function. In this case, for example, by laminating an optical functional film such as a retardation film, a brightness enhancement film, a reflection film, a transflective film, a diffusion film, an optical compensation film on the surface of the protective film, it has such a function.
- the protective film itself can be provided with such a function.
- the protective film itself may have a plurality of functions such as a diffusion film having the function of a brightness enhancement film.
- EPDM ethylene-propylene-diene copolymer rubber
- 3090EM manufactured by Mitsui Chemicals (diene species: ethylidene norbornene, Mooney viscosity: 87) and carbon black “Seast 6” (arithmetic average) particle size: 22 nm, DBP absorption amount: 114 cm 3/100 g), a benzimidazole compound as an anti-aging agent LANXESS Corp.
- Phosphoric acid as a vulcanization accelerator an inorganic filler zinc oxide manufactured by Hakusui Tech Co., was used Sanshin Chemical Co., Ltd. of "Sun ester TMP" (trimethylolpropane trimethacrylate) as a crosslinking agent.
- EPDM 100 parts by weight Carbon black 50 parts by weight Anti-aging agent 1 part by weight Vulcanizing agent 7 parts by weight Plasticizer (paraffin oil) 10 parts by weight Vulcanization accelerator (stearic acid) 1 part by weight Inorganic filler (zinc oxide) 5 parts by weight Part Crosslinking aid (trimethylolpropane trimethacrylate)
- Plasticizer paraffin oil
- Vulcanization accelerator stearic acid
- Inorganic filler zinc oxide
- Crosslinking aid trimethylolpropane trimethacrylate
- the rubber composition to which each of the above components was added was sufficiently kneaded with a rubber kneader and then applied to a calender machine to prepare and prepare an unvulcanized rubber sheet having a thickness of 1.5 mm.
- the rubber sheet was laminated several times on a metal core which had been previously blasted and coated with an adhesive to cover the rubber.
- a rubber roll having a rubber layer with a thickness of 35 mm on the surface was molded.
- vulcanization was performed at a pressure of 0.5 MPa and a temperature of 160 ° C. for 480 minutes, and after cooling, polishing was performed to obtain a rubber roll of Example 1 having a rubber layer with a thickness of 25 mm on the roll surface.
- Example 2 The same material as in Example 1 was used except that “APMA” (N- (4-anilinophenyl) methacrylamide) manufactured by Seiko Chemical Co., Ltd., which is a reactive anti-aging agent, was used as the anti-aging agent.
- APMA N- (4-anilinophenyl) methacrylamide
- EPDM 100 parts by weight Carbon black 50 parts by weight Anti-aging agent 2 parts by weight Vulcanizing agent 7 parts by weight Plasticizer (paraffin oil) 10 parts by weight Vulcanization accelerator (stearic acid) 1 part by weight Inorganic filler (zinc oxide) 5 parts by weight Part Crosslinking aid (trimethylolpropane trimethacrylate)
- Plasticizer paraffin oil
- Vulcanization accelerator stearic acid
- Inorganic filler zinc oxide
- Crosslinking aid trimethylolpropane trimethacrylate
- a rubber roll of Example 2 was obtained in the same manner as Example 1 using the rubber composition to which the above components were added.
- EPDM ethylene-propylene-diene copolymer rubber
- EP65 die species: ethylidene norbornene, Mooney viscosity: 74
- Seast 3 arithmetic average particle
- TMDQ Ouchi Shinko chemical Co., Ltd. as an anti-aging agent (2,2,4-trimethyl-1,2-dihydroquinoline polymer
- a rubber roll of Comparative Example 1 was obtained in the same manner as in Example 1 using the rubber composition to which the above components were added.
- a rubber roll of Comparative Example 2 was obtained in the same manner as in Example 1 using the rubber composition to which the above components were added.
- Example 3 The same material as in Example 1 was used except that “EP65” (diene species: ethylidene norbornene, Mooney viscosity: 74) manufactured by JSR Corporation was used as EPDM (ethylene-propylene-diene copolymer rubber).
- EPDM 100 parts by weight Carbon black 50 parts by weight Anti-aging agent 1 part by weight Vulcanizing agent 7 parts by weight Plasticizer (paraffin oil) 10 parts by weight Vulcanization accelerator (stearic acid) 1 part by weight Inorganic filler (zinc oxide) 5 parts by weight Part Crosslinking aid (trimethylolpropane trimethacrylate)
- Plasticizer paraffin oil
- Vulcanization accelerator stearic acid
- Inorganic filler zinc oxide
- Crosslinking aid trimethylolpropane trimethacrylate
- a rubber roll of Comparative Example 3 was obtained in the same manner as in Example 1 by using the rubber composition to which the above components were added.
- a rubber roll of Comparative Example 4 was obtained in the same manner as in Example 1 by using the rubber composition to which the above components were added.
- EPDM 100 parts by weight Carbon black 50 parts by weight Anti-aging agent 1 part by weight Vulcanizing agent 7 parts by weight Plasticizer (paraffin oil) 10 parts by weight Vulcanization accelerator (stearic acid) 1 part by weight Inorganic filler (zinc oxide) 5 parts by weight Part Crosslinking aid (trimethylolpropane trimethacrylate)
- Plasticizer paraffin oil
- Vulcanization accelerator stearic acid
- Inorganic filler zinc oxide
- Crosslinking aid trimethylolpropane trimethacrylate
- a rubber roll of Comparative Example 5 was obtained in the same manner as in Example 1 using the rubber composition to which the above components were added.
- EPDM 100 parts by weight Carbon black 55 parts by weight Anti-aging agent 1 part by weight Vulcanizing agent 7 parts by weight Plasticizer (paraffin oil) 10 parts by weight Vulcanization accelerator (stearic acid) 1 part by weight Inorganic filler (zinc oxide) 5 parts by weight Part Crosslinking aid (trimethylolpropane trimethacrylate)
- Plasticizer paraffin oil
- Vulcanization accelerator stearic acid
- Inorganic filler zinc oxide
- Crosslinking aid trimethylolpropane trimethacrylate
- a rubber roll of Comparative Example 6 was obtained in the same manner as in Example 1 using the rubber composition to which each of the above components was added.
- Mooney Viscosity of EPDM is 1 minute preheating, measuring temperature 100 ° C., measuring time 4 minutes using Mooney Viscometer “SMV-300” manufactured by Shimadzu Corporation. It is a measured value.
- Example 1 and Comparative Examples 1 to 6 were sufficiently kneaded with a rubber kneader and then applied to a calender machine to produce a 2.2 mm thick unvulcanized rubber sheet.
- vulcanization was carried out at a vulcanization temperature of 170 ° C. to obtain a rubber sheet having a thickness of 2 mm.
- JIS K 6264 the rubber sheet is polished for 6 minutes using a polishing cloth AA-240 with a pressing load of 3.62 kg, the mass before and after polishing is measured, the polishing mass is divided by the rubber density, and wear The volume was determined.
- Test pieces of 20 mm ⁇ 50 mm and dumbbell shape No. 3 were prepared from the rubber sheets comprising the compositions of Examples 1 and 2 and Comparative Examples 2 to 6. Next, the test piece was immersed in a 95 ⁇ 1 ° C. aqueous solution containing 4 parts by weight of boric acid and 12 parts by weight of potassium iodide for 28 days, and the wear volume was measured using a test tube type aging tester manufactured by Toyo Seiki Seisakusho. Asked.
- each test piece shall be the same Examples 1 and 2 and Comparative Examples 1 to 6 as the corresponding rubber roll.
- Table 1 shows the compositions and test results of the rubber compositions of Examples 1 and 2 and Comparative Examples 1 to 6.
- Example 3 Manufacture of polarizing film
- a 75 ⁇ m-thick polyvinyl alcohol film (Kurarevinilon VF-PS # 7500, polymerization degree 2,400, saponification degree 99.9 mol% or more) is kept in pure water at 30 ° C. so that the film does not loosen.
- the film was immersed for about 130 seconds to fully swell the film.
- the film was immersed in an aqueous solution of iodine / potassium iodide / water in a weight ratio of 0.02 / 1.5 / 100 and dyed to perform uniaxial stretching.
- the film was immersed in a boric acid crosslinking treatment solution having a composition of 4.0 parts by weight of boric acid, 12 parts by weight of potassium iodide, and 100 parts by weight of water at a temperature of 54 ° C.
- Uniaxial stretching was performed until the cumulative stretching ratio from the original fabric reached 5.9 times.
- the nip roll comprised with the rubber roll obtained in Example 1 was each installed before and after the boric-acid bridge
- a washing treatment was performed in pure water at 15 ° C. for 9 seconds. Next, it was dried at a temperature of 60 ° C. for 2 minutes to obtain a polarizing film.
- the rubber composition of the present invention is useful for forming a rubber roll used for producing a polarizing film.
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- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
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Abstract
Description
本発明は、エチレン-プロピレン-ジエン共重合ゴムに加硫剤、カーボンブラック、老化防止剤が配合されてなるゴム組成物である。エチレン-プロピレン-ジエン共重合ゴム(EPDM)は、よく知られているように、エチレンとプロピレンとの共重合体であるエチレン-プロピレンゴム(EPM)に、少量の第3成分(ジエン成分)を導入し、主鎖中に二重結合をもたせたものである。第3成分としては、たとえばエチリデンノルボルネン(ENB)、1,4-ヘキサジエン(1,4-HD)、ジシクロペンタジエン(DCP)などが挙げられる。EPDMは、ムーニー粘度が80以上であるものを用いる。EPDMのムーニー粘度が80以上であることにより、耐摩耗性が向上する。EPDMのヨウ素価は5~24であるのが好ましい。
本発明のロール成型品の製造方法の一例を説明する。上述の本発明のゴム組成物を混合し充分に混練した後、所定の押出し成形などによりロールの芯金の外周面上にゴム層を被覆し、ついで加圧下で加硫し、研磨することによりロール成型品が得られる。加硫温度は、使用する加硫剤の分解温度以上である。芯金とゴム層との間には接着層を介在させてもよい。この接着層の硬度は、特に限定されないが、表面ゴム層のゴム硬度以上であるのが、ロール使用時の耐圧性や薬品による接着層の剥離防止のうえで好ましい。接着層は、エポキシ化ゴム等の、芯金との接着性に優れたゴム種が挙げられるが、特に限定されるものではない。
本発明の偏光フィルムの製造方法は、ポリビニルアルコール系フィルムに、膨潤処理、染色処理、ホウ酸処理および洗浄処理をこの順に行ない、偏光フィルムを製造する製造方法である。さらに、上述の少なくともいずれか一つの処理と並行して、またはこれらの処理とは別に、一軸延伸処理を行なう。上述の処理とは別に一軸延伸を行なう場合、上述の処理の間に一軸延伸を行なうための湿式延伸処理の工程を加える。一軸延伸処理は、1つの工程で行なってもよいが、複数の工程で行なってもよい。また、膨潤処理の前に予めポリビニルアルコール系フィルムを空気あるいは不活性ガスなどの気体中で一軸延伸処理を行なってもよい。最終的な積算延伸倍率は、4.5~7.0倍、好ましくは5.0~6.5倍である。
EPDM(エチレン-プロピレン-ジエン共重合ゴム)として三井化学株式会社製の「3090EM」(ジエン種:エチリデンノルボルネン、ムーニー粘度:87)、カーボンブラックとして東海カーボン株式会社製の「シースト6」(算術平均粒子径:22nm、DBP吸収量:114cm3/100g)、老化防止剤としてベンズイミダゾール系化合物であるLANXESS社製の「Vulkanox MB2」(2-メルカプトメチルベンズイミダゾール)、加硫剤として有機過酸化物である日本油脂株式会社製の「パーヘキサ25B40」(2,5-ジメチル-2,5-ジ(t-ブチルパーオキシ)ヘキサン)を使用し、さらに出光興産株式会社製の「PW380」(パラフィンオイル)を可塑剤として、日本精化株式会社製のステアリン酸を加硫促進剤として、ハクスイテック株式会社製の酸化亜鉛を無機充填剤として、三新化学株式会社製の「サンエステルTMP」(トリメチロールプロパントリメタクリレート)を架橋助剤として使用した。
EPDM 100重量部
カーボンブラック 50重量部
老化防止剤 1重量部
加硫剤 7重量部
可塑剤(パラフィンオイル) 10重量部
加硫促進剤(ステアリン酸) 1重量部
無機充填剤(酸化亜鉛) 5重量部
架橋助剤(トリメチロールプロパントリメタクリレート) 3.4重量部
で実施例1のゴム組成物を配合した。
老化防止剤として反応性の老化防止剤である精工化学社製「APMA」(N-(4-アニリノフェニル)メタクリルアミド)を用いた点以外は実施例1と同様の材料を使用した。
EPDM 100重量部
カーボンブラック 50重量部
老化防止剤 2重量部
加硫剤 7重量部
可塑剤(パラフィンオイル) 10重量部
加硫促進剤(ステアリン酸) 1重量部
無機充填剤(酸化亜鉛) 5重量部
架橋助剤(トリメチロールプロパントリメタクリレート) 3.4重量部
で実施例2のゴム組成物を配合した。
EPDM(エチレン-プロピレン-ジエン共重合ゴム)としてJSR株式会社製の「EP65」(ジエン種:エチリデンノルボルネン、ムーニー粘度:74)、カーボンブラックとして東海カーボン株式会社製の「シースト3」(算術平均粒子径:28nm、DBP吸収量:101cm3/100g)、老化防止剤として大内振興化学株式会社製の「TMDQ」(2,2,4-トリメチル-1,2-ジヒドロキノリン重合物)を用いた点以外は、実施例1と同様の材料を使用した。
EPDM 100重量部
カーボンブラック 55重量部
老化防止剤 1重量部
加硫剤 7重量部
可塑剤(パラフィンオイル) 10重量部
加硫促進剤(ステアリン酸) 1重量部
無機充填剤(酸化亜鉛) 5重量部
架橋助剤(トリメチロールプロパントリメタクリレート) 3.4重量部
で比較例1のゴム組成物を配合した。
カーボンブラックとして東海カーボン株式会社製の「シースト3」(算術平均粒子径:28nm、DBP吸収量:101cm3/100g)、老化防止剤として大内振興化学株式会社製の「TMDQ」(2,2,4-トリメチル-1,2-ジヒドロキノリン重合物)を用いた点以外は、実施例1と同様の材料を使用した。
EPDM 100重量部
カーボンブラック 55重量部
老化防止剤 1重量部
加硫剤 7重量部
可塑剤(パラフィンオイル) 10重量部
加硫促進剤(ステアリン酸) 1重量部
無機充填剤(酸化亜鉛) 5重量部
架橋助剤(トリメチロールプロパントリメタクリレート) 3.4重量部
で比較例2のゴム組成物を配合した。
EPDM(エチレン-プロピレン-ジエン共重合ゴム)としてJSR株式会社製の「EP65」(ジエン種:エチリデンノルボルネン、ムーニー粘度:74)を用いた点以外は実施例1と同様の材料を使用した。
EPDM 100重量部
カーボンブラック 50重量部
老化防止剤 1重量部
加硫剤 7重量部
可塑剤(パラフィンオイル) 10重量部
加硫促進剤(ステアリン酸) 1重量部
無機充填剤(酸化亜鉛) 5重量部
架橋助剤(トリメチロールプロパントリメタクリレート) 3.4重量部
で比較例3のゴム組成物を配合した。
カーボンブラックとして東海カーボン株式会社製の「シースト3」(算術平均粒子径:28nm、DBP吸収量:101cm3/100g)を用いた点以外は実施例1と同様の材料を使用した。
EPDM 100重量部
カーボンブラック 55重量部
老化防止剤 1重量部
加硫剤 7重量部
可塑剤(パラフィンオイル) 10重量部
加硫促進剤(ステアリン酸) 1重量部
無機充填剤(酸化亜鉛) 5重量部
架橋助剤(トリメチロールプロパントリメタクリレート) 3.4重量部
で比較例4のゴム組成物を配合した。
EPDM(エチレン-プロピレン-ジエン共重合ゴム)としてJSR株式会社製の「E
P65」(ジエン種:エチリデンノルボルネン、ムーニー粘度:74)、老化防止剤として大内振興化学株式会社製の「TMDQ」(2,2,4-トリメチル-1,2-ジヒドロキノリン重合物)を用いた点以外は実施例1と同様の材料を使用した。
EPDM 100重量部
カーボンブラック 50重量部
老化防止剤 1重量部
加硫剤 7重量部
可塑剤(パラフィンオイル) 10重量部
加硫促進剤(ステアリン酸) 1重量部
無機充填剤(酸化亜鉛) 5重量部
架橋助剤(トリメチロールプロパントリメタクリレート) 3.4重量部
で比較例6のゴム組成物を配合した。
ールを得た。
EPDM(エチレン-プロピレン-ジエン共重合ゴム)としてJSR株式会社製の「E
P65」(ジエン種:エチリデンノルボルネン、ムーニー粘度:74)、カーボンブラッ
クとして東海カーボン株式会社製の「シースト3」(算術平均粒子径:28nm、DBP
吸収量:101cm3/100g)を用いた点以外は実施例1と同様の材料を使用した。
EPDM 100重量部
カーボンブラック 55重量部
老化防止剤 1重量部
加硫剤 7重量部
可塑剤(パラフィンオイル) 10重量部
加硫促進剤(ステアリン酸) 1重量部
無機充填剤(酸化亜鉛) 5重量部
架橋助剤(トリメチロールプロパントリメタクリレート) 3.4重量部
で比較例7のゴム組成物を配合した。
ールを得た。
EPDMのムーニー粘度は、JIS K 6300に準拠して、島津製作所株式会社製のムーニービスコメータ「SMV-300」のLロータを使用して、予熱1分、測定温度100℃、測定時間4分で測定した値である。
上記実施例1、比較例1~6のゴム組成物をゴム練り機にて充分に混練りした後、カレンダー機に掛け、2.2mmの厚さの未加硫のゴムシートを作製し、JIS K 6299「ゴム―試験用試料の作製方法」に準じて、加硫温度170℃で加硫し、2mm厚のゴムシートを得た。該ゴムシートについて、JIS K 6264に準拠して、研磨布AA-240を用い、押し付け荷重3.62kgで6分間研磨し、研磨前後の質量を測定し、研磨質量をゴムの密度で割り、摩耗容積を求めた。
上記実施例1、2、比較例2~6の組成物からなるゴムシートから20mm×50mm及びダンベル状3号形の試験片を作製した。ついで、ホウ酸4重量部、ヨウ化カリウム12重量部を含む95±1℃の水溶液に試験片を28日間浸漬して、東洋精機製作所株式会社製のテストチューブ式老化試験機を用いて摩耗容積を求めた。
(偏光フィルムの製造)
厚さ75μmのポリビニルアルコールフィルム(クラレビニロンVF-PS#7500、重合度2,400、ケン化度99.9モル%以上)を30℃の純水に、フィルムが弛まないように緊張状態を保ったまま約130秒間浸漬しフィルムを十分に膨潤させた。次にヨウ素/ヨウ化カリウム/水が重量比で0.02/1.5/100の水溶液に浸漬して染色処理をしつつ一軸延伸を行った。
Claims (5)
- エチレン-プロピレン-ジエン共重合ゴムに加硫剤、カーボンブラック、老化防止剤が配合されてなるゴム組成物であって、
前記エチレン-プロピレン-ジエン共重合ゴムのムーニー粘度が80以上であり、
前記カーボンブラックの算術平均粒子径が25nm以下であり、
前記老化防止剤がベンズイミダゾール系化合物である、ゴム組成物。 - エチレン-プロピレン-ジエン共重合ゴムに加硫剤、カーボンブラック、老化防止剤が配合されてなるゴム組成物であって、
前記エチレン-プロピレン-ジエン共重合ゴムのムーニー粘度が80以上であり、
前記カーボンブラックの平均粒子径が25nm以下であり、
前記老化防止剤が反応性老化防止剤である、ゴム組成物。 - 前記エチレン-プロピレン-ジエン共重合ゴム100重量部に対して、前記加硫剤を1~10重量部、前記カーボンブラックを30~90重量部、前記老化防止剤を0.5~3.0重量部含む、請求項1または2に記載のゴム組成物。
- 請求項1~3のいずれかに記載のゴム組成物から形成されたゴム層を表面に有する、偏光フィルムの製造工程で用いられるロール成型品。
- ポリビニルアルコール系フィルムに、膨潤処理、染色処理、ホウ酸処理および洗浄処理をこの順に行ない、偏光フィルムを製造する製造方法であって、
これらの処理のうち少なくともいずれか一つの処理と並行して、またはこれらの処理とは別に、二つのニップロールの周速差を利用して一軸延伸処理を行ない、
前記ニップロールを構成するロール成型品の少なくとも一つは、請求項4に記載のロール成型品である、偏光フィルムの製造方法。
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JP2018013780A (ja) * | 2016-07-12 | 2018-01-25 | 住友化学株式会社 | 貼合ロール、光学フィルム積層体の製造装置及び製造方法 |
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CN104204075A (zh) | 2014-12-10 |
KR20140134650A (ko) | 2014-11-24 |
KR101839650B1 (ko) | 2018-03-16 |
JPWO2013141152A1 (ja) | 2015-08-03 |
TWI551641B (zh) | 2016-10-01 |
TW201348320A (zh) | 2013-12-01 |
JP6100239B2 (ja) | 2017-03-22 |
CN104204075B (zh) | 2016-08-24 |
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