WO2016080425A1 - 変性エチレン系重合体、接着性樹脂組成物、積層体、その用途 - Google Patents
変性エチレン系重合体、接着性樹脂組成物、積層体、その用途 Download PDFInfo
- Publication number
- WO2016080425A1 WO2016080425A1 PCT/JP2015/082357 JP2015082357W WO2016080425A1 WO 2016080425 A1 WO2016080425 A1 WO 2016080425A1 JP 2015082357 W JP2015082357 W JP 2015082357W WO 2016080425 A1 WO2016080425 A1 WO 2016080425A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- ethylene polymer
- laminate
- modified ethylene
- modified
- adhesive
- Prior art date
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Images
Classifications
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
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- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J7/00—Adhesives in the form of films or foils
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- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
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- 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
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- B32B2597/00—Tubular articles, e.g. hoses, pipes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/354—Applications of adhesives in processes or use of adhesives in the form of films or foils for automotive applications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2423/00—Presence of polyolefin
- C09J2423/04—Presence of homo or copolymers of ethene
- C09J2423/046—Presence of homo or copolymers of ethene in the substrate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2429/00—Presence of polyvinyl alcohol
- C09J2429/006—Presence of polyvinyl alcohol in the substrate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2451/00—Presence of graft polymer
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2477/00—Presence of polyamide
- C09J2477/006—Presence of polyamide in the substrate
Definitions
- the present invention relates to a modified ethylene polymer and its use. Specifically, the present invention relates to a modified ethylene polymer that can provide an adhesive resin composition having high fuel barrier properties and excellent adhesiveness and mechanical strength, and a laminate using the polymer.
- Polyethylene resin has recently been widely used as a fuel tank for automobiles. Since the polyethylene resin has high fuel permeability, there is a method of laminating a resin having a gas barrier property superior to that of the polyethylene resin, such as a saponified ethylene / vinyl acetate copolymer (hereinafter referred to as “EVOH”), on the polyethylene resin. . At this time, since the adhesion between polyethylene and EVOH was extremely low, a multilayer fuel tank was obtained by bonding using an adhesive resin such as a modified product obtained by graft-modifying polyethylene with carboxylic acids (Patent Document 1).
- EVOH saponified ethylene / vinyl acetate copolymer
- a laminate composed of a gas barrier resin and a modified ethylene polymer is used, and by heating and remelting (welding) the modified ethylene polymer part, The tank peripheral member was fused to the polyethylene gasoline tank through the modified ethylene polymer portion.
- the demand for fuel permeation suppression for plastic fuel tanks becomes more severe, it is becoming difficult for the conventional technology to satisfy the demand.
- an object of the present invention is to provide a modified ethylene polymer having excellent adhesion to polyethylene such as a gasoline tank, mechanical strength, and good fuel barrier properties, and lamination using the same. Is to provide a body.
- an adhesive resin composition using a modified ethylene polymer having specific physical properties and a laminate obtained from the adhesive resin composition are excellent in solving the above problems.
- the inventors have found that the present invention has an effect and completed the present invention.
- the configuration of the present invention is as follows.
- [3] The modified ethylene polymer according to [1] or [2], wherein at least a part of the ethylene polymer is obtained by polymerization in the presence of a metallocene catalyst.
- An adhesive resin composition comprising the modified ethylene polymer according to any one of [1] to [3].
- [5] A laminate comprising an adhesive layer made of the adhesive resin composition according to [4], and a resin layer provided on at least one surface of the adhesive layer.
- the resin layer is made of at least one selected from polyamide and ethylene-vinyl alcohol copolymer.
- the laminate according to [5] or [6] produced by a coextrusion molding method.
- the laminate according to [5] or [6] which is produced by an injection molding method.
- the modified ethylene polymer of the present invention is subjected to a predetermined graft modification, and the elution amount by CFC (cross fractionation chromatography) which is one of the scales of crystallinity evaluation is adjusted to be within a predetermined range. Therefore, it exhibits excellent adhesiveness and mechanical strength, and exhibits good fuel barrier properties. Therefore, when such a modified ethylene polymer is used in an adhesive resin composition to form an adhesive layer of a laminate, the laminate has high adhesive strength with polyethylene, etc., and excellent long-term durability and impact resistance. Is obtained.
- the adhesive resin composition of the present invention is used in a laminate for tank peripheral members, it has high adhesiveness to gasoline tank members and maintains sufficient adhesive strength even when contacted with high-temperature gasoline or light oil. Excellent long-term durability.
- the laminated body which concerns on this invention can be used suitably for tank peripheral members, such as a valve
- modified ethylene polymer The modified ethylene polymer of the present invention is obtained by graft-modifying a part or all of an ethylene polymer with an unsaturated carboxylic acid or a derivative thereof.
- unsaturated carboxylic acid or its derivative examples include acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acid (endocis-bicyclo [2,2,1] Unsaturated carboxylic acids such as hept-5-ene-2,3-dicarboxylic acid; or derivatives thereof such as acid halides, amides, imides, anhydrides, esters and the like.
- Such derivatives include, for example, maleyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate and the like.
- unsaturated carboxylic acids or acid anhydrides thereof are suitable, and maleic acid, nadic acid or acid anhydrides thereof are particularly preferably used.
- the modified ethylene polymer according to the present invention can be obtained by various known methods. As a specific method, an ethylene polymer is dissolved in an organic solvent, and then an unsaturated carboxylic acid or a derivative thereof and a radical initiator such as an organic peroxide as necessary are added to the obtained solution.
- a radical initiator such as an unsaturated carboxylic acid or a derivative thereof and, if necessary, an organic peroxide is added to the mixture, and usually at a temperature not lower than the melting point of the ethylene polymer, preferably at a temperature of 120 to 350 ° C.
- the method of making it react for minutes is mentioned.
- the unmodified ethylene polymer that is the basis of the modified ethylene polymer according to the present invention is an ethylene homopolymer or a copolymer of ethylene and an ⁇ -olefin.
- the ⁇ -olefin to be copolymerized with ethylene is an ⁇ -olefin having 3 or more carbon atoms, preferably 3 to 10, specifically, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, Examples include 1-decene, 4-methyl-1-pentene, and combinations of two or more thereof.
- the copolymerization amount of ⁇ -olefin is not particularly limited, but is usually 10 mol% or less.
- the ethylene-based polymer before modification is not particularly limited as long as the density of the resulting modified ethylene-based polymer is within the range described below, but the density is in the range of 930 to 980 kg / m 3 , and the MFR is It is desirable to be in the range of 0.1 to 50 g / 10 minutes.
- the ethylene-based polymer before modification can be produced by a known method using a known Philips type catalyst (chromium-based), Ziegler-type catalyst (titanium-based), or metallocene-based catalyst.
- Philips type catalyst chromium-based
- Ziegler-type catalyst titanium-based
- metallocene-based catalyst those obtained by polymerization in the presence of a metallocene catalyst are suitable for satisfying the predetermined elution amount of the present invention.
- the modified ethylene polymer has a density in the range of 920 to 960 kg / m 3 and a melt flow rate (MFR) measured by ASTM D1238 (190 ° C., 2160 g load) of 0.1 to 10 g / 10 min, preferably Is in the range of 0.1 to 1.0 g / 10 min.
- MFR melt flow rate
- melt flow rate, density, and I 10 / I 2 are in the above ranges, it has sufficient mechanical strength as an adhesive resin composition for multilayer molded parts around gasoline tanks, and crack resistance against long-term low stress Excellent in injection moldability and blow moldability.
- the weight of the graft monomer with respect to the ethylene polymer before modification is preferably in the range of 0.15 to 0.40% by weight, preferably in the range of 0.15 to 0.30% by weight. More preferably, it is in the range of 0.15 to 0.25% by weight, and part or all is graft-modified with an unsaturated carboxylic acid or derivative thereof.
- the adhesive resin composition for a multilayer molded member around the gasoline tank has sufficient adhesive strength to the gas barrier resin, and adheres to long-term gasoline immersion. Excellent at holding power.
- the modified ethylene polymer has an elution amount at 80 ° C. or lower, preferably an elution amount to o-dichlorobenzene at 80 ° C. or lower in CFC measurement of 10% by weight or less.
- Those that satisfy these elution amounts have little change in crystallinity due to environmental changes, little swelling to gasoline, etc., high mechanical strength, high adhesive strength at high temperatures, and long-term stable gas barrier properties. is doing.
- ethylene polymers are not composed of uniform crystallinity, have a crystalline distribution, and those with a large amount of elution have thick and thin crystals mixed together. It is considered that as the temperature rises, the crystallinity is lost from the thin crystal and the crystal component responsible for the fuel barrier property is reduced, so that the barrier property is lowered.
- the elution amount at 80 ° C. or lower in CFC measurement can be adjusted as appropriate by those skilled in the art, but can be adjusted by adjusting, for example, the density, composition distribution (MFR), and graft amount.
- the elution amount can be adjusted to 10% by weight or less by using, for example, an ethylene polymer having a narrow composition distribution produced in the presence of a metallocene catalyst.
- the modified ethylene polymer has a time until breakage of not less than 100 hr in the all-around notch creep test in 5.5 MPa / 80 ° C. warm water based on JIS K6774.
- the time until the rupture by the creep test is in the above range, the crack in the modified polyolefin caused by long-term low stress acting on the tank peripheral member accompanying deformation of the polyethylene gasoline tank has high crack resistance.
- the modified ethylene polymer is used as a constituent material of a gas barrier resin peripheral member joined to a polyethylene gasoline tank. More specifically, after molding a tank peripheral member consisting of a gas barrier resin and a modified ethylene polymer by injection molding, tube extrusion molding, blow molding, etc., the modified ethylene polymer part is heated and remelted to modify The tank peripheral member is fused and joined to a polyethylene gasoline tank through the ethylene polymer portion.
- the adhesive resin composition of the present invention contains the modified ethylene polymer.
- the elution amount of the adhesive resin composition of the present invention is desirably about the same as the elution amount of the modified ethylene polymer of the present invention.
- the adhesive resin composition of the present invention may contain an unmodified ethylene polymer having a density of 930 to 980 kg / m 3 .
- the amount of the unmodified ethylene polymer is preferably 30% by weight or less with respect to 100% by weight of the total amount of the modified ethylene polymer and the unmodified ethylene polymer.
- an unmodified ethylene polymer polymerized in the presence of a metallocene catalyst may be used for the purpose of adjusting the elution amount of the adhesive resin composition of the present invention to a desired range. preferable.
- the above-described adjustment method can be applied in the same manner.
- an antioxidant in the adhesive resin composition of the present invention, an antioxidant, a weather stabilizer, an antistatic agent, an antifogging agent, an antiblocking agent, a lubricant, a nucleating agent, and a pigment that are usually used within the range not impairing the object of the present invention.
- Etc. or other polymers, rubber and the like can be blended as required.
- the adhesive resin composition of the present invention preferably, Izod impact strength was measured at -40 °C atmosphere according to ASTM D 256 is 10 kJ / m 2 or more, preferably 12 kJ / m 2 or more.
- Izod impact strength in the ⁇ 40 ° C. atmosphere is in this range, the low temperature drop impact strength is high when used in a multilayer structure.
- the adhesive resin composition of the present invention can be obtained by various known methods, for example, a method of dry blending the modified ethylene polymer within the above range using a Henschel mixer, a tumbler blender, a V-blender, etc. It can be prepared by a melt kneading method using a screw extruder, a multi-screw extruder, a Banbury mixer or the like, or by stirring and mixing in the presence of a solvent.
- the laminate of the present invention has an adhesive layer (A) formed from the adhesive resin composition and a resin layer (B) formed on at least one side of the adhesive layer (A). Moreover, the same or different resin layer (C) as the resin layer (B) may be formed on the other surface of the adhesive layer (A).
- the resin layer (B) is composed of a gas barrier resin.
- the gas barrier resin refers to a resin having gasoline permeability lower than that of polyolefin. Specific examples include polyamide resins and ethylene / vinyl alcohol copolymers.
- nylon 6, nylon 66, nylon 610, nylon 11, nylon 12, MXD nylon, amorphous nylon, terephthalic acid / adipic acid / hexamethylenediamine copolymer and the like are preferably used as the polyamide resin.
- ethylene / vinyl alcohol copolymer a copolymer having an ethylene content of 20 to 50 mol% is preferably used.
- a polyethylene resin or the like can be used, for example, an ethylene homopolymer or a random copolymer of ethylene and ⁇ -olefin.
- the copolymerization amount of the ⁇ -olefin is not particularly limited as long as the density of the polyethylene resin is within the following range, but is usually preferably 10 mol% or less, more preferably 5 mol% or less.
- the ⁇ -olefin is preferably an ⁇ -olefin having 3 to 10 carbon atoms, and specifically, for example, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene and the like. Can be mentioned.
- the melt flow rate (MFR) [ASTM D 1238 (temperature: 190 ° C., load: 2160 g load)] of the polyethylene resin is preferably 0.01 to 3.0 g / 10 minutes, more preferably 0.05 to 1.5 g.
- the density is preferably in the range of 0.940 to 0.980 g / cm 3 , more preferably in the range of 0.950 to 0.970 g / cm 3 .
- a filler in the layers (A), (B), and (C) constituting the laminate of the present invention, a filler, a stabilizer, a lubricant, an antistatic agent, a flame retardant, and foam are within the range not impairing the object of the present invention.
- Additives known per se, such as an agent, can be blended.
- the production method of the laminate of the present invention can employ a known method without particular limitation, and is performed by, for example, a co-extrusion method.
- the coextrusion molding method is not particularly limited, and examples thereof include known coextrusion molding methods such as a coextrusion multilayer die method and a feed block method in which melt extrusion is performed using a plurality of extruders.
- the conditions at the time of coextrusion molding are also not particularly limited, and the resin constituting the layer (A) and the layer (B) is heated to a melting temperature or higher and melt-extruded using the above-mentioned extruder so as to reach a predetermined temperature. Just cool it down.
- the adhesion between the layer (A) and the layer (B) is strengthened by producing the laminate by coextrusion molding. Furthermore, since the laminated body manufactured by coextrusion molding can be manufactured in one process, it is excellent in productivity.
- the laminating method uses a so-called extrusion laminating method in which a film is extruded by an extruder equipped with a die such as a coat hanger die, T die, or I die, or a pre-formed adhesive film (A), A method of thermocompression bonding with a nip roll on a resin film (B) heated to a temperature higher than the softening temperature of the film (A), an adhesive film (A) or a resin film (B) placed on a mold, and then the resin layer (B Or injection molding to obtain a laminate through heating and cooling steps by introducing a resin constituting the adhesive layer (A).
- a die such as a coat hanger die, T die, or I die
- A A method of thermocompression bonding with a nip roll on a resin film (B) heated to a temperature higher than the softening temperature of the film (A)
- an adhesive film (A) or a resin film (B) placed on a mold and then the resin layer (B
- the modified ethylene polymer constituting the laminate of the present invention has a predetermined graft modification, and the amount of elution at 80 ° C. or lower in CFC measurement is adjusted to a predetermined range or lower, so that adhesion and mechanical strength are reduced.
- the adhesive force is considered to be derived not only from the intermolecular interaction between the adhesive and the adherend but also from the mechanical strength of the base resin. As the modification rate increases, the intermolecular interaction becomes stronger, but it is presumed that the mechanical structure of the base resin has a large change in crystal structure and the mechanical strength of the adhesive layer may be lowered.
- the mechanical strength of the base resin structure contributes more to the adhesive strength than the modified rate. Is estimated to be high. Therefore, when such a modified ethylene polymer is used in an adhesive resin composition to form an adhesive layer of a laminate, the adhesive strength and the adhesive strength after contact with gasoline or light oil are high, and long-term durability and impact resistance. A laminate having excellent properties can be obtained.
- the surfaces to be joined are usually brought into contact with each other and pressed together.
- the dissimilar members are usually poorly joined or not joined.
- the specific modified ethylene polymer constitutes the adhesive layer of the laminate, so that good bonding can be obtained.
- These joints are not only strong, but also have low leakage (liquid and gas) and can be sealed well, using these methods to create systems that handle liquids and / or gases, especially under pressure and / or vacuum Can do.
- the automobile fuel tank body is often made of polyethylene due to low cost and physical strength, but according to the present invention, it can be firmly joined to polyethylene. Therefore, the laminated body of the present invention can be used for peripheral members of fuel tanks such as fuel valves, fuel system fixtures, fuel pipes (rigid and flexible), fuel gauge members, fuel injectors, fuel pumps, and components of these products. It can be suitably used, and is particularly suitable as a fuel valve.
- MFR (g / 10 min) The temperature was measured at 190 ° C. and a load of 2160 g in accordance with ASTM D 1238.
- the proportion (wt%) of o-dichlorobenzene soluble component at 80 ° C. or lower was determined by CFC measurement under the following conditions.
- Apparatus Cross fractionation chromatograph CFC2 (Polymer ChAR), Detector (built-in): Infrared spectrophotometer IR4 (Polymer ChAR), Detection wavelength: 3.42 ⁇ m (2,920 cm ⁇ 1); fixed, Sample concentration: 120 mg / 30 mL, injection volume: 0.5 mL, Temperature drop time: 1.0 ° C./min, Elution category: 4.0 ° C intervals (-20 ° C to 140 ° C), GPC column: Shodex HT-806M ⁇ 3 (Showa Denko), GPC column temperature: 140 ° C., GPC column calibration: monodisperse polystyrene (Tosoh Corporation), Molecular weight calibration method: General-purpose calibration method (polystyrene conversion), Mobile phase: o-dichlorobenzene (with BHT added), flow rate: 1.0 mL / min.
- the full circumference notch creep test was measured in accordance with ISO16770. Specifically, it was cut out from a 6 mm thick press-molded sheet, and the length of the test piece was 40 mm. Thereafter, using a predetermined jig, an incision having a depth of 1 mm was made in the entire periphery of the center of the test piece. The atmosphere was warm water of 80 ° C., a constant load of 5.0 MPa was applied to the test piece, and the time until breakage was measured.
- samples for evaluation of adhesive strength were prepared by an injection molding machine. Specifically, the modified ethylene polymers of Examples and Comparative Examples were injection molded at 200 ° C. to obtain strip-shaped resin pieces having a width of 12 mm, a length of 130 mm, and a thickness of 3 mm. Thereafter, the strip made of the modified ethylene polymer was inserted into a mold different from the mold used above, and a polyamide resin (PA6) was injected onto the modified ethylene polymer at 280 ° C.
- PA6 polyamide resin
- Fuel Permeability Coefficient A 2 mm thick sheet-shaped test in which 18 mL of Fuel-C, which is a simulated fuel, is placed in a SUS container (open area: 1.26 ⁇ 10 ⁇ 3 m 2 ) having a volume of 20 mL and press-molded. A test piece was prepared by setting the piece in the container opening and sealing it. The test specimen was placed in a thermostatic device (65 ° C.), the weight of the test specimen was measured, and when the weight loss per unit time became constant, the fuel permeability coefficient was determined by the following formula.
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- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Laminated Bodies (AREA)
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Abstract
Description
[1]グラフト変性量が0.15重量%~0.40重量%の範囲であり、かつ、クロス分別クロマトグラフィー測定における80℃以下での溶出量が10重量%以下である、エチレン系重合体の少なくとも一部が不飽和カルボン酸またはその誘導体でグラフト変性された変性エチレン系重合体。
[2] 前記溶出量が、80℃以下でのo-ジクロロベンゼンへの溶出量である、[1]に記載の変性エチレン系重合体。
[3]前記エチレン系重合体の少なくとも一部が、メタロセン触媒の存在下で重合して得られたものである、[1]または[2]に記載の変性エチレン系重合体。
[4]前記[1] ~[3]に記載の変性エチレン系重合体を含む接着性樹脂組成物。
[5]前記[4]に記載の接着性樹脂組成物からなる接着層、および該接着層の少なくとも片面に設けられた樹脂層を備える積層体。
[6]前記樹脂層が、ポリアミドおよびエチレン-ビニルアルコール共重合体から選ばれる少なくとも1種からなるものである[5]に記載の積層体。
[7]共押出成形法により製造された[5]または[6]に記載の積層体。
[8]射出成形法により製造された[5]または[6]に記載の積層体。
[9]前記[5]~[8]に記載の積層体を用いたプラスチック燃料タンク用の燃料バルブ。
本発明の変性エチレン系重合体は、エチレン系重合体が、その一部もしくは全部が不飽和カルボン酸もしくはその誘導体でグラフト変性されたものである。
本発明の接着性樹脂組成物は、前記変性エチレン系重合体を含む。本発明の接着性樹脂組成物の溶出量は、本発明の変性エチレン系重合体の溶出量と同程度であることが望ましい。
本発明の積層体は、前記接着性樹脂組成物から形成される接着層(A)と、当該接着層(A)の少なくとも片面に形成された樹脂層(B)とを有する。また、接着層(A)の他方の面に樹脂層(B)と同一または異なる樹脂層(C)が形成されていてもよい。
ASTM D 1238に準拠し、温度:190℃、2160g荷重で測定した。
ASTM D 1505に準拠して測定した。
クロス分別クロマトグラフィー(CFC)にて測定した。
検出器(内蔵):赤外分光光度計 IR4(Polymer ChAR)、
検出波長:3.42μm(2,920cm-1);固定、
試料濃度:120mg/30mL、注入量:0.5mL、
降温時間: 1.0℃/min、
溶出区分: 4.0℃間隔(-20℃~140℃)、
GPCカラム:Shodex HT-806M×3本(昭和電工社)、
GPCカラム温度:140℃、GPCカラム較正:単分散ポリスチレン(東ソー社)、
分子量較正法:汎用較正法(ポリスチレン換算)、
移動相:o-ジクロロベンゼン(BHT添加)、流量:1.0mL/min。
全周フルノッチクリープ試験は、ISO16770に従って測定した。具体的には、厚さ6mmのプレス成形シートから切出し、試験片の長さを40mmとした。その後、所定の治具を用いて、試験片中央部全周に、深さ1mmの切り込みを入れた。雰囲気は80℃の温水とし、5.0MPaの定荷重を試験片に与え、破断までの時間を測定した。
燃料浸漬後の接着強度は、積層体の側面から10mm幅でサンプルを切り出し、65℃のFuel-C(イソオクタン/トルエン重量比=50/50)中に200時間浸漬した後、接着層(A)と樹脂層(B)との間の接着強度を室温(23℃)の恒温槽内で測定した。
20mLの容積を有するSUS製容器(開放部面積1.26×10-3m2)に模擬燃料であるFuel-Cを18mL入れて、プレス成形した2mm厚のシート状試験片を容器開放部にセットして密閉することで、試験体とした。該試験体を恒温装置(65℃)に入れ、試験体の重量を測定し、単位時間あたりの重量減少が一定となったところで下記の式により燃料透過係数を求めた。
メタロセン系触媒の存在下で製造された密度=951kg/m3、MFR=0.27g/10分の高密度ポリエチレンを一部用い、無水マレイン酸0.22g/100gを押出機内で溶融グラフト変性した変性エチレン系重合体(MFR=0.27g/10分:密度=951kg/cm3)を用意し、前述の方法により、上記(1)~(6)を評価した。
メタロセン系触媒の存在下で製造された密度=951kg/m3、MFR=0.27g/10分の高密度ポリエチレンを用い、無水マレイン酸0.15g/100gを押出機内で溶融グラフト変性した変性エチレン系重合体(MFR=0.26g/10分:密度=951kg/cm3)を用意し、実施例1と同様に評価した。
メタロセン系触媒の存在下で製造された密度=951kg/m3、MFR=0.27g/10分の高密度ポリエチレンを用い、無水マレイン酸0.30g/100gを押出機内で溶融グラフト変性した変性エチレン系重合体(MFR=0.30g/10分:密度=951kg/cm3)を用意し、実施例1と同様に評価した。
チーグラー系触媒の存在下で製造された密度=951kg/m3、MFR=0.11g/10分の高密度ポリエチレンを用い、無水マレイン酸0.22g/100gを押出機内で溶融グラフト変性した変性エチレン系重合体(MFR=0.12g/10分:密度=951kg/cm3)を用意し、実施例1と同様に評価した。
メタロセン系触媒の存在下で製造された密度=951kg/m3、MFR=0.27g/10分の高密度ポリエチレンを一部用い、無水マレイン酸0.11g/100gを押出機内で溶融グラフト変性した変性エチレン系重合体(MFR=0.25g/10分:密度=951kg/cm3)を用意し、実施例1と同様に評価した。
メタロセン系触媒の存在下で製造された密度=951kg/m3、MFR=0.27g/10分の高密度ポリエチレンを一部用い、無水マレイン酸0.44g/100gを押出機内で溶融グラフト変性した変性エチレン系重合体(MFR=0.32g/10分:密度=951kg/cm3)を用意し、実施例1と同様に評価した。
2 ポリアミド
3 ローラー
Claims (9)
- グラフト変性量が0.15重量%~0.40重量%の範囲であり、かつ、クロス分別クロマトグラフィー測定における80℃以下での溶出量が10重量%以下である、エチレン系重合体の少なくとも一部が不飽和カルボン酸またはその誘導体でグラフト変性された変性エチレン系重合体。
- 前記溶出量が、80℃以下でのo-ジクロロベンゼンへの溶出量である、請求項1に記載の変性エチレン系重合体。
- 前記エチレン系重合体の少なくとも一部が、メタロセン触媒の存在下で重合して得られたものである、請求項1または2に記載の変性エチレン系重合体。
- 請求項1~3のいずれか1項に記載の変性エチレン系重合体を含む接着性樹脂組成物。
- 請求項4に記載の接着性樹脂組成物からなる接着層、および該接着層の少なくとも片面に設けられた樹脂層を備える積層体。
- 前記樹脂層が、ポリアミドおよびエチレン-ビニルアルコール共重合体から選ばれる少なくとも1種からなるものである請求項5に記載の積層体。
- 共押出成形法により製造された請求項5または6に記載の積層体。
- 射出成形法により製造された請求項4または5に記載の積層体。
- 請求項5~8のいずれか1項に記載の積層体を用いたプラスチック燃料タンク用の燃料バルブ。
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EP15861386.9A EP3222638B1 (en) | 2014-11-18 | 2015-11-18 | Modified ethylenic polymer, adhesive resin composition, laminate, and use of same |
JP2016560255A JP6644704B2 (ja) | 2014-11-18 | 2015-11-18 | 変性エチレン系重合体、接着性樹脂組成物、積層体、その用途 |
ES15861386T ES2821825T3 (es) | 2014-11-18 | 2015-11-18 | Polímero etilénico modificado, composición de resina adhesiva, laminado, y uso de los mismos |
US15/523,520 US20170321092A1 (en) | 2014-11-18 | 2015-11-18 | Modified ethylene polymer, adhesive resin composition, laminate, and use thereof |
CN201580062369.8A CN107108784B (zh) | 2014-11-18 | 2015-11-18 | 改性乙烯系聚合物、粘接性树脂组合物、叠层体及其用途 |
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CN107108784B (zh) | 2021-01-15 |
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EP3222638B1 (en) | 2020-09-02 |
JP6644704B2 (ja) | 2020-02-12 |
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US20170321092A1 (en) | 2017-11-09 |
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