WO2009084316A1 - 射出成形品の製造方法及びそれに用いるマスターバッチ - Google Patents
射出成形品の製造方法及びそれに用いるマスターバッチ Download PDFInfo
- Publication number
- WO2009084316A1 WO2009084316A1 PCT/JP2008/069342 JP2008069342W WO2009084316A1 WO 2009084316 A1 WO2009084316 A1 WO 2009084316A1 JP 2008069342 W JP2008069342 W JP 2008069342W WO 2009084316 A1 WO2009084316 A1 WO 2009084316A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- cyclic olefin
- olefin resin
- molecular weight
- resin
- mass
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
-
- 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
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2345/00—Characterised by the use of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2445/00—Characterised by the use of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Definitions
- the present invention relates to a method for producing an injection-molded article using a low molecular weight cyclic olefin resin and a master batch containing the low molecular weight cyclic olefin resin used therefor.
- Cyclic olefin-based resins are excellent in transparency, chemical resistance, moisture resistance, mechanical properties, etc., and are therefore used as materials for optical applications, pharmaceutical or medical equipment applications, and the like.
- the cyclic olefin-based resin is excellent in melt processability and fluidity, and is also used for film-shaped or sheet-shaped molded products and packaging materials.
- cyclic olefin resin is excellent also in heat shrinkability and printing characteristics.
- the cyclic olefin resin is used in various fields.
- the cyclic olefin-based resin also has a surface in which a gel-like material is generated when melt molding is performed, the molding surface is roughened and appearance characteristics are deteriorated. This deterioration in appearance characteristics has a great influence particularly when a cyclic olefin-based resin is used as a transparent material, optical application, or packaging material.
- Patent Document 1 discloses a technique in which the surface of a molded product becomes smooth even by melt molding by combining a high molecular weight cyclic olefin resin and a low molecular weight cyclic olefin resin. Is disclosed. International Publication WO 2007/132641 Pamphlet
- an injection molding method is often used which is complicated, sophisticated and highly accurate in one process and completes a molded product in a short time.
- the injection molding method it is possible to process various materials such as daily necessities, parts of electric products, and parts for automobiles.
- the mold structure has become complicated, sophisticated, parts are consolidated, and parts are being integrated, and there are many parts that can only be injection molded.
- Patent Document 1 when a low molecular weight cyclic olefin resin and a cyclic olefin resin are used as molding materials and injection molding is performed, the bite property of the resin is deteriorated and the measurement time is increased. For this reason, in the method of Patent Document 1, it takes time to supply the molding material for each molding shot, and the productivity is lowered. In addition, when the low molecular weight cyclic olefin resin and the cyclic olefin resin are melted, the quality of the molded product obtained is unstable due to variations in the supply amount and measurement time for each molding shot. Therefore, there is a need for a technique that enables easy injection molding while taking advantage of the characteristics of the low molecular weight cyclic olefin resin.
- the present invention has been made to solve the above-described problems, and an object of the present invention is to provide a technique that enables easy injection molding while taking advantage of the characteristics of a low-molecular-weight cyclic olefin resin. .
- the inventors of the present invention have made extensive studies to solve the above problems. As a result, the inventors perform injection molding after the step of dry blending a master batch containing a cyclic olefin resin and a low molecular weight cyclic olefin resin having a number average molecular weight of 10,000 or less, and the cyclic olefin resin. Thus, it was found that injection molding can be easily performed, and the present invention has been completed. More specifically, the present invention provides the following.
- a high-quality injection molded product can be easily obtained. If a low molecular weight cyclic olefin resin is used without making a masterbatch as in the past, the glass transition point is low, the pellets are very brittle due to the low molecular weight, and are easily crushed by compression and friction during plasticization. It becomes powder and adheres to the pellet surface of the base. Due to the influence of this powder, the friction with the cylinder becomes small during transportation of the solid in the first half of plasticization, and the bite property becomes worse. In addition, the low molecular weight cyclic olefin resin rapidly melts into a low viscosity liquid state.
- the resin becomes difficult to move forward, and when the coefficient of friction between the resin and the screw exceeds the coefficient of friction between the resin and the cylinder, the resin Will not be transferred forward. Accordingly, when the low molecular weight cyclic olefin resin is used without making a masterbatch, there is a problem in the biting property of the resin into the screw.
- the glass transition point of the master batch becomes lower than the glass transition point of the low molecular weight cyclic olefin resin, and the toughness of the pellet is increased, and the plasticity is increased. Even if there is compression or friction at the time of conversion, it is difficult to become a powder, so that rapid melting can be suppressed and the biting property of the resin can be improved.
- the master batch is a master batch in which the content of the cyclic olefin resin is 20% by mass to 95% by mass, and the content of the low molecular weight cyclic olefin resin is 5% by mass to 80% by mass
- the step of dry blending is a method for producing an injection-molded product according to (1), wherein the master batch is a blend of 5 parts by mass to 100 parts by mass with respect to 100 parts by mass of the cyclic olefin resin.
- the master batch pellet is It has sufficient toughness and has the effect that the amount of generated powder is small and it is difficult to cause measurement problems.
- a masterbatch used in the method for producing an injection-molded product according to any one of (1) and (2), wherein the cyclic olefin resin content is from 20% by mass to 95% by mass, and the low molecular weight cyclic product The masterbatch whose content of olefin resin is 5 mass% to 80 mass%.
- the content of the low-molecular-weight cyclic olefin-based resin is in the above range, so that the biting property of the molding material is improved and the gel generation is sufficiently suppressed. it can. Therefore, an even higher quality injection molded product can be manufactured with high productivity.
- the master batch since the glass transition point of the master batch is 100 ° C. or less, the master batch is melted prior to the cyclic olefin resin during the melt molding, and the shear force applied to the cyclic olefin resin is further increased. Can be small. For this reason, generation
- a masterbatch containing a cyclic olefin resin and a low molecular weight cyclic olefin resin having a number average molecular weight of 10,000 or less, and a cyclic olefin resin to injection molding after the step of dry blending, A high-quality injection-molded product can be easily obtained while taking advantage of the characteristics of the low molecular weight cyclic olefin resin.
- the present invention provides an injection molded product that is injection-molded after a step of dry blending a cyclic olefin resin with a master batch containing a cyclic olefin resin and a low molecular weight cyclic olefin resin having a number average molecular weight of 10,000 or less. It is a masterbatch used for the method and its manufacturing method.
- the present invention is characterized by using a masterbatch containing a cyclic olefin resin and a low molecular weight cyclic olefin resin having a number average molecular weight of 10,000 or less.
- the masterbatch used in the present invention contains a cyclic olefin resin and a low molecular weight cyclic olefin resin having a number average molecular weight of 10,000 or less.
- the cyclic olefin resin used in the present invention contains a cyclic olefin component as a copolymerization component, and is not particularly limited as long as it is a polyolefin resin containing a cyclic olefin component in the main chain.
- (A4) A resin obtained by grafting and / or copolymerizing an unsaturated compound having a polar group on the resins (a1) to (a3).
- Examples of the polar group include a carboxyl group, an acid anhydride group, an epoxy group, an amide group, an ester group, and a hydroxyl group.
- Examples of the unsaturated compound having a polar group include (meth) acrylic acid and maleic acid. Acid, maleic anhydride, itaconic anhydride, glycidyl (meth) acrylate, alkyl (meth) acrylate (carbon number 1-10) ester, alkyl maleate (carbon number 1-10) ester, (meth) acrylamide, (meta And 2-hydroxyethyl acrylate.
- the cyclic olefin resins (a1) to (a4) containing the above cyclic olefin component as a copolymerization component may be used singly or in combination of two or more.
- cyclic olefin resin containing the cyclic olefin component used in the present invention as a copolymerization component a commercially available resin can also be used.
- commercially available cyclic olefin resins include TOPAS (registered trademark) (TOPAS ADVANCED POLYMER), Apel (registered trademark) (Mitsui Chemicals), Zeonex (registered trademark) (manufactured by Nippon Zeon), Examples include ZEONOR (registered trademark) (manufactured by ZEON Corporation), ARTON (registered trademark) (manufactured by JSR Corporation), and the like.
- the (a2) cyclic olefin / ⁇ -olefin addition copolymer preferably used in the composition of the present invention is not particularly limited. Particularly preferred examples include a copolymer comprising [1] an ⁇ -olefin component having 2 to 20 carbon atoms and [2] a cyclic olefin component represented by the following general formula (I).
- R 1 to R 12 may be the same or different and are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group, and R 9 and R 10 , R 11 and R 12 may be integrated to form a divalent hydrocarbon group, and R 9 or R 10 and R 11 or R 12 may form a ring with each other, and n is Represents 0 or a positive integer, and when n is 2 or more, R 5 to R 8 may be the same or different in each repeating unit.
- ⁇ -olefin component having 2 to 20 carbon atoms which is a copolymer component of an addition polymer of a cyclic olefin component preferably used in the present invention and another copolymer component such as ethylene, is not particularly limited.
- ethylene propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-octene Examples include decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicocene. These ⁇ -olefin components may be used alone or in combination of two or more. Of these, ethylene is most preferably used alone.
- R 1 to R 12 in the general formula (I) may be the same or different and are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group.
- R 1 to R 8 include, for example, a hydrogen atom; a halogen atom such as fluorine, chlorine and bromine; a lower alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group. May be different from each other, may be partially different, or all may be the same.
- R 9 to R 12 include, for example, hydrogen atom; halogen atom such as fluorine, chlorine, bromine; methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, hexyl group, stearyl.
- Alkyl group such as cyclohexyl group; cycloalkyl group such as cyclohexyl group; substituted or unsubstituted aromatic hydrocarbon group such as phenyl group, tolyl group, ethylphenyl group, isopropylphenyl group, naphthyl group, anthryl group; benzyl group, phenethyl And an aralkyl group in which an aryl group is substituted with an alkyl group, and the like. These may be different from each other, may be partially different, or all may be the same.
- R 9 and R 10 or R 11 and R 12 are integrated to form a divalent hydrocarbon group
- alkylidene groups such as an ethylidene group, a propylidene group, and an isopropylidene group. Can be mentioned.
- the formed ring may be monocyclic or polycyclic, or may be a polycyclic ring having a bridge.
- a ring having a double bond, or a ring composed of a combination of these rings may be used.
- these rings may have a substituent such as a methyl group.
- cyclic olefin component represented by the general formula (I) include bicyclo [2.2.1] hept-2-ene (common name: norbornene), 5-methyl-bicyclo [2.2.1] hepta. -2-ene, 5,5-dimethyl-bicyclo [2.2.1] hept-2-ene, 5-ethyl-bicyclo [2.2.1] hept-2-ene, 5-butyl-bicyclo [2 2.1] hept-2-ene, 5-ethylidene-bicyclo [2.2.1] hept-2-ene, 5-hexyl-bicyclo [2.2.1] hept-2-ene, 5-octyl -Bicyclo [2.2.1] hept-2-ene, 5-octadecyl-bicyclo [2.2.1] hept-2-ene, 5-methylidene-bicyclo [2.2.1] hept-2-ene 5-vinyl-bicyclo [2.2.1]
- Tricyclo [4.3.0.1 2,5 ] deca-3,7-diene (common name: dicyclopentadiene), tricyclo [4.3.0.1 2,5 ] dec-3-ene; tricyclo [ 4.4.0.1 2,5 ] undeca-3,7-diene or tricyclo [4.4.0.1 2,5 ] undeca-3,8-diene or a partially hydrogenated product thereof (or cyclopentadiene) Tricyclo [4.4.0.1 2,5 ] undec-3-ene; 5-cyclopentyl-bicyclo [2.2.1] hept-2-ene, 5-cyclohexyl-bicyclo [2.2.1] hept-2-ene, 5-cyclohexenylbicyclo [2.2.1] hept-2-ene, 5-phenyl-bicyclo [2.2.1] hept-2-ene A cyclic olefin of the ring;
- Tetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene also simply referred to as tetracyclododecene
- 8-methyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene 8-ethyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene
- 8-methylidenetetracyclo 4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene
- cyclic olefin components may be used singly or in combination of two or more.
- a method for polymerizing an ⁇ -olefin component having 2 to 20 carbon atoms and a [2] cyclic olefin component represented by formula (I) and a method for hydrogenating the obtained polymer are particularly limited. Instead, it can be carried out according to known methods. It may be random copolymerization or block copolymerization.
- the polymerization catalyst used is not particularly limited and can be obtained by a known method using a conventionally known catalyst such as a Ziegler-Natta, metathesis, or metallocene catalyst.
- a conventionally known catalyst such as a Ziegler-Natta, metathesis, or metallocene catalyst.
- the addition copolymer of cyclic olefin and ⁇ -olefin or a hydrogenated product thereof preferably used in the present invention is preferably produced using a metallocene catalyst or a Ziegler-Natta catalyst.
- metathesis catalyst examples include molybdenum or tungsten-based metathesis catalysts known as cycloolefin ring-opening polymerization catalysts (for example, described in JP-A Nos. 58-127728 and 58-129003).
- the polymer obtained by the metathesis catalyst uses an inorganic carrier-supported transition metal catalyst, etc., and 90% or more of the double bonds in the main chain and 98% or more of the carbon-carbon double bonds in the side chain aromatic ring are hydrogenated. It is preferable to add.
- the (a2) addition copolymer of cyclic olefin and ⁇ -olefin particularly preferably used in the composition of the present invention comprises [1] the ⁇ -olefin component having 2 to 20 carbon atoms and [2] the general formula (I
- other copolymerizable unsaturated monomer components may be contained as necessary within the range not impairing the object of the present invention.
- the unsaturated monomer that may be optionally copolymerized is not particularly limited, and examples thereof include hydrocarbon monomers containing two or more carbon-carbon double bonds in one molecule. Can be mentioned. Specific examples of hydrocarbon monomers containing two or more carbon-carbon double bonds in one molecule include 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 4 Chain non-conjugated dienes such as methyl-1,5-hexadiene, 5-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene; cyclohexadiene, di Cyclopentadiene, methyltetrahydroindene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-is
- 1,4-hexadiene, 1,6-octadiene, and cyclic nonconjugated dienes especially dicyclopentadiene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-methylene-2 -Norbornene, 1,4-hexadiene, 1,6-octadiene are preferred.
- the glass transition point of the cyclic olefin-based resin may be 80 ° C. or higher, for example, 80 ° C. to 180 ° C., preferably 100 ° C. to 170 ° C., more preferably 110 ° C. to 160 ° C.
- the glass transition point can be controlled by adjusting the proportion of the copolymer component, the molecular weight, and the like.
- Tg glass transition point of the cyclic olefin resin used in the present invention, a value measured by a method described in JIS K7121 at a temperature rising rate of 10 ° C./min is adopted.
- the cyclic olefin resin is preferably a high molecular weight cyclic olefin resin having a number average molecular weight exceeding 10,000. More specifically, the number average molecular weight of the cyclic olefin resin is preferably 15,000 to 200,000, more preferably 20,000 to 100,000, and still more preferably 30,000 to 80,000.
- cyclic olefin resin examples include the cyclic olefin resins exemplified in the section of the cyclic olefin resin.
- these cyclic olefin resins it is preferable to use the same or the same type of resin as the cyclic olefin resin from the viewpoint of compatibility.
- the proportion of copolymerizable monomers is selected from the range of about 0 to 99 mol% in the total monomers. However, it may be, for example, about 50 to 99 mol%, preferably about 55 to 95 mol% from the viewpoint of appearance characteristics and the like.
- the proportion of ethylene may be, for example, about 60 to 90 mol%, preferably about 70 to 85 mol% from the viewpoint of appearance characteristics and the like.
- the glass transition point of the low molecular weight cyclic olefin resin is preferably 70 ° C. or less, more preferably 40 ° C. to 70 ° C. If the glass transition point is 70 ° C. or lower, the low-molecular-weight cyclic olefin-based resin dissolves before the normal cyclic olefin-based resin, so that the shearing force applied to the cyclic olefin-based resin by the screw is eased during melt molding. be able to.
- the glass transition point of the low molecular weight cyclic olefin resin is preferably lower than the glass transition point of the cyclic olefin resin.
- the difference is preferably 10 ° C. to 100 ° C., more preferably 20 ° C. to 100 ° C.
- the number average molecular weight of the low molecular weight cyclic olefin resin is 10,000 or less.
- the number average molecular weight is preferably 500 to 8000, more preferably 1000 to 7000, and still more preferably 1500 to 6000.
- the difference in the number average molecular weight between the cyclic olefin-based resin and the low molecular weight cyclic olefin-based resin is not particularly limited, but is preferably 1,000 to 200,000, more preferably 10,000 to 150,000, still more preferably 20,000 to 100,000, and most preferably. Is 30000-80000. If the difference in number average molecular weight between the cyclic olefin-based resin and the low molecular weight cyclic olefin-based resin is 1000 or more, it is preferable because the effect of suppressing the generation of gel-like substances becomes remarkable. Is within the allowable range and is preferable because it does not adversely affect the workability during molding.
- the present invention is characterized in that a low molecular weight cyclic olefin resin is used as a master batch with a cyclic olefin resin.
- a low molecular weight cyclic olefin resin is used as a master batch with a cyclic olefin resin.
- the cyclic olefin resin in the master batch is preferably 10% by mass to 95% by mass. More preferably, it is 20% by mass to 90% by mass. If the content of the cyclic olefin resin in the master batch is in the above range, the master batch pellet has sufficient toughness if the amount of the low molecular weight cyclic olefin resin is equal to or less than the amount of the cyclic olefin resin, This is preferable because the amount of generated powder is small and it is difficult to cause measurement problems.
- the low molecular weight cyclic olefin-based resin is preferably 5% by mass to 90% by mass. More preferably, it is 10% by mass to 80% by mass. If it is 5% by mass or more, it is preferable because of the gel reduction effect, and if it is 90% by mass or less, the master batch pellet is sufficient if the amount of the low molecular weight cyclic olefin resin is equal to or less than the amount of the cyclic olefin resin. It is preferable because it has toughness, and the amount of generated powder is small and hardly causes a measurement problem.
- Preparation of the master batch is preferably carried out by introducing a cyclic olefin resin and a low molecular weight cyclic olefin resin into an extruder and extruding.
- the kind of extruder is not specifically limited. Due to the rapid melting of low molecular weight cyclic olefin resins, it is difficult to produce a masterbatch by injection molding.
- the cylinder temperature is preferably 180 ° C. to 340 ° C. because the low molecular weight cyclic olefin resin rapidly melts. More preferably, it is 200 ° C to 320 ° C.
- the rotational speed of the screw is preferably 50 rpm to 300 rpm, more preferably 100 rpm to 250 rpm.
- the extrusion rate is preferably 5 kg / hr to 200 kg / hr. More preferably, it is 10 kg / hr to 100 kg / hr.
- the glass transition point of the obtained master batch is preferably 100 ° C. or lower. More preferably, it is 50 ° C to 100 ° C. If the glass transition point is within the above range, the low-molecular-weight cyclic olefin resin necessary for preventing rapid melting of the masterbatch and facilitating injection molding can be transferred more smoothly during injection molding. Therefore, it is preferable.
- Cyclic olefin resin examples of the cyclic olefin resin to be dry blended with the master batch include the same as those exemplified in the description of the cyclic olefin resin contained in the master batch.
- the cyclic olefin resin to be dry blended with the master batch may be a resin different from the cyclic olefin resin contained in the master batch, but it is preferable to use the same resin from the viewpoint of compatibility and the like.
- injection molding The feature of the present invention is injection molding. Therefore, the reason why it is preferable to use the master batch by dividing the injection molding into several steps will be described below.
- Injection molding can be divided into a material charging process, a plasticizing process, and an injection / holding / cooling process.
- the injection molding in the present invention is characterized by dry blending. If it is not dry blend, since there are few low molecular weight cyclic olefin-type resins which appear on the surface, generation
- Injection molding is facilitated even if cyclic olefin resin pellets with a high content of low molecular weight cyclic olefin resin are used as the molding material.
- an increase in the content of the low molecular weight cyclic olefin resin in the injection molded product is not preferable because mechanical strength such as tensile elongation at break decreases. Therefore, dry blending is necessary to effectively suppress the generation of gel-like material and to obtain a high-quality injection-molded product.
- the shape of the cyclic olefin resin to be dry-blended with the master batch is not particularly limited, and may be a powder, but is preferably a pellet.
- ⁇ Plasticization process In the plasticizing process, a cyclic olefin resin, a masterbatch and the like (molding material) supplied from the hopper are transferred and melted to make a homogeneous melt.
- Molding materials such as cyclic olefin resin and master batch charged from the hopper are transferred from the hopper side to the nozzle direction side by the rotation of the screw.
- a screw consists of a feed zone (supply part), a compression zone (compression part), and a metering zone (metering part) from the hopper side.
- the supply unit generally serves to transfer the resin pellets from the hopper side to the nozzle direction side at a temperature setting that does not melt the resin pellets. Although it is performed at a low temperature, preheating by an external heater is performed as a preparation stage for melting. Further, since the resin pellet is sandwiched between the rotating screw and the cylinder, a frictional force is applied to the resin pellet, and frictional heat is generated. Low molecular weight cyclic olefin resins having a low glass transition point generally have a low melting point. When pellets containing a large amount of such low molecular weight cyclic olefin resins are used as molding materials, they are melted by the above preheating or frictional heat. There is a case.
- the molding material melts at this stage, it will rotate around with the screw and the molding material will not be transferred successfully. Moreover, even if the pellet containing a large amount of the low-molecular-weight cyclic olefin resin does not melt, it may become a large lump together with the cyclic olefin-based resin pellet. If the screw groove is shallow compared to the size of the lump, the molding material cannot be transferred successfully. If the transfer becomes unsuccessful, the measurement time becomes longer, and the productivity of the injection molded product decreases. Further, since the transfer does not proceed smoothly, the difference in measurement time for each shot becomes large. It affects the quality of the injection-molded product obtained by variation of the measuring time.
- the glass transition point and melting point of the masterbatch are increased, so that it melts in the supply section. None will happen. Therefore, if a low molecular weight cyclic olefin resin is masterbatched with a cyclic olefin resin, the low molecular weight cyclic olefin resin can be smoothly transferred.
- the master batch contains 50% by mass to 95% by mass of the cyclic olefin-based resin, more preferably 20% by mass to 95% by mass.
- the content of the low molecular weight cyclic olefin resin should be small, and it is preferable to contain 5% by mass to 80% by mass of the low molecular weight cyclic olefin resin. More preferably, it is 10% by mass to 60% by mass.
- the glass transition point of the master batch is preferably 100 ° C. or lower. If a glass transition point is 100 degrees C or less, it can prevent that a masterbatch melt
- the depth of the screw groove gradually becomes shallower. For this reason, pressure is applied to the resin pellets in the compression section. Therefore, in the compression unit, the resin pellets are transferred further forward (in the direction from the hopper to the nozzle) while melting.
- the generation of the gel is due to the shearing force applied during melting.
- the shearing force applied to the cyclic olefin resin can be reduced.
- a master batch containing a cyclic olefin-based resin and a low-molecular-weight cyclic olefin-based resin is used in order to make the transfer in the supply unit smooth.
- This master batch is less soluble than a pellet made of only a low-molecular-weight cyclic olefin resin, but needs to be a master batch that dissolves before the cyclic olefin resin pellet and relieves the shearing force applied to the cyclic olefin resin.
- the master batch of the present invention may contain 5% by mass to 80% by mass of the low molecular weight cyclic olefin resin so that the master batch containing the low molecular weight cyclic olefin resin is dissolved before the cyclic olefin resin.
- 5% by mass to 80% by mass of the low molecular weight cyclic olefin resin so that the master batch containing the low molecular weight cyclic olefin resin is dissolved before the cyclic olefin resin.
- it is 10% by mass to 60% by mass.
- the reason why the masterbatch is dissolved first is that a certain low molecular weight cyclic olefin resin is present on the surface of the masterbatch.
- the content of the low molecular weight cyclic olefin resin is within the above range, the shear force applied to the cyclic olefin resin by the previously dissolved low molecular weight cyclic olefin resin can be reduced.
- the low molecular weight cyclic olefin resin is also a cyclic olefin resin, if there is too much low molecular weight cyclic olefin resin, there is a risk that a gel-like material is generated due to the shearing force applied at this time. Therefore, the content of the low molecular weight cyclic olefin tree contained in the master batch is preferably within the above range.
- the resin pellets preferably have a width of 4 mm to 1 mm, a length of 5 mm to 1 mm, and a thickness of 4 mm to 1 mm. If the size of the pellet is within the above range, even if a small amount of low molecular weight cyclic olefin resin is used, the probability that a low molecular weight cyclic olefin resin will appear on the pellet surface is preferable.
- the master batch In order to alleviate the shearing force applied to the cyclic olefin resin, it is preferable to use 5 to 100 parts by mass of the master batch with respect to 100 parts by mass of the cyclic olefin resin to be dry blended with the master batch. More preferably, it is 10 to 100 parts by mass.
- the metering unit functions to melt the molding material completely, to make the plasticization uniform, and to send it further forward.
- uniformity of plasticization is essential.
- One cause of non-uniform plasticization is the difference in the temperature at which the molding material begins to melt.
- injection molding is performed using a low molecular weight cyclic olefin-based resin master batch that intentionally begins to melt first. Therefore, it is necessary to select a molding material so that uniform plasticization can be realized.
- the masterbatch used in the present invention has a cyclic olefin resin content of 20% to 95% by mass, and a low molecular weight cyclic olefin resin content of 5% to 80% by mass. It is preferable that The master batch is preferably used in an amount of 5 to 50 parts by mass with respect to 100 parts by mass of the cyclic olefin resin to be dry blended with the master batch. More preferably, it is 10 to 100 parts by mass.
- the difference in glass transition temperature between the master batch containing the low molecular weight cyclic olefin resin and the cyclic olefin resin to be dry blended with the master batch is preferably 5 ° C. to 250 ° C. . More preferably, it is 10 ° C to 200 ° C.
- the compression ratio is preferably in the range of 2 to 4 and the L / D is preferably in the range of 15 to 25 for uniform plasticization and productivity improvement.
- the “compression ratio” is the ratio of the volume of the supply unit 1 pitch to the volume of the measurement unit 1 pitch.
- the “screw” length is the length from the bottom of the hopper to the tip of the screw part.
- the injection process is a process of extruding molten resin from a cylinder into a mold.
- the injection speed and injection pressure are injected at a preferable injection speed depending on the molding material used.
- the pressure holding step is a step of continuously applying pressure to the molten resin in the cavity from the cylinder side of the injection molding apparatus through the gate part of the mold after injection of the molten molding material.
- the resin in the cavity shrinks with cooling, but the molten resin can be replenished into the cavity by holding pressure. For this reason, excessive volume shrinkage in the cavity can be suppressed.
- a certain quality can be maintained by maintaining the pressure for the gate sealing time or longer.
- Cyclic olefin resin (resin A) to be dry blended with the masterbatch Topas Advanced Polymers GmbH, trade name “TOPAS5013”, number average molecular weight 40000, glass transition point 140 ° C.
- Cyclic olefin-based resin (B1) contained in the master batch manufactured by Topas Advanced Polymers GmbH, trade name “TOPAS5010”, number average molecular weight 30000, glass transition point 110 ° C.
- ⁇ Preparation of master batch> A blend of a cyclic olefin resin (A or B1) and a low molecular weight cyclic olefin resin (B2) having the composition shown in Tables 1 and 2 is charged into an extruder (TEX30C manufactured by Nippon Steel Works), and a cylinder temperature of 190 Master batches of Examples 1 to 10 and Comparative Examples 1 and 2 having a length of 2.5 mm, a width of 2.5 mm, and a thickness of 2.5 mm at a temperature of ° C., an extrusion rate of 10 kg / hr, and a screw rotation speed of 150 rpm were prepared. In Example 1, it was possible to extrude the master batch, but the strands were easily broken, and half of them became long pellets.
- the resin pellets of the cyclic olefin resin (A) and the resin pellets of the master batches of the examples or comparative examples are molded as resin raw materials with the formulations shown in Tables 1 and 2.
- Machine SE75D manufactured by Sumitomo Heavy Industries, Ltd.
- Molding conditions were a 70 mm square 2 mmt flat plate (film gate) as a mold, cylinder temperature 270 ° C., mold temperature 110 ° C., injection speed 150 mm / s, holding pressure 30 MPa ⁇ 30 s, cooling 40 s, weighing 50 mm, screw rotation speed 200 rpm.
- the back pressure was 15 MPa, and the VP switching position was 11 mm.
- the obtained injection molded product had a length of 70 mm, a width of 70 mm, and a thickness of 2 mm.
- the weighing time of Comparative Example 1 exceeded 60 seconds on average, and the difference between the longest weighing time and the shortest weighing time could not be measured.
- the weighing times of Examples 1 to 10 were all within 60 seconds, and the difference between the longest weighing time and the shortest weighing time was 28.6 seconds at the longest. Therefore, the productivity of the injection-molded product is improved by using the low molecular weight cyclic olefin resin as a master batch with the cyclic olefin resin.
- the average weighing time is very short, and the difference between the longest weighing time and the shortest weighing time is also very short. The effect of quality stability is also obtained.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
Description
以下、本発明により製造される射出成形品及び本発明のマスターバッチの必須成分となる環状オレフィン系樹脂について説明する。本発明に用いられる環状オレフィン系樹脂は、環状オレフィン成分を共重合成分として含むものであり、環状オレフィン成分を主鎖に含むポリオレフィン系樹脂であれば、特に限定されるものではない。例えば、
(a1)環状オレフィンの付加重合体又はその水素添加物、
(a2)環状オレフィンとα-オレフィンの付加共重合体又はその水素添加物、
(a3)環状オレフィンの開環(共)重合体又はその水素添加物、を挙げることができる。
(a4)上記(a1)~(a3)の樹脂に、極性基を有する不飽和化合物をグラフト及び/又は共重合したもの。
本発明に好ましく用いられる環状オレフィン成分とエチレン等の他の共重合成分との付加重合体の共重合成分となる炭素数2~20のα-オレフィンは、特に限定されるものではない。例えば、エチレン、プロピレン、1-ブテン、1-ペンテン、1-ヘキセン、3-メチル-1-ブテン、3-メチル-1-ペンテン、3-エチル-1-ペンテン、4-メチル-1-ペンテン、4-メチル-1-ヘキセン、4,4-ジメチル-1-ヘキセン、4,4-ジメチル-1-ペンテン、4-エチル-1-ヘキセン、3-エチル-1-ヘキセン、1-オクテン、1-デセン、1-ドデセン、1-テトラデセン、1-ヘキサデセン、1-オクタデセン、1-エイコセン等を挙げることができる。また、これらのα-オレフィン成分は、1種単独でも2種以上を同時に使用してもよい。これらの中では、エチレンの単独使用が最も好ましい。
本発明に好ましく用いられる環状オレフィン成分とエチレン等の他の共重合成分との付加重合体において、共重合成分となる一般式(I)で示される環状オレフィン成分について説明する。
本発明の組成物に特に好ましく用いられる(a2)環状オレフィンとα-オレフィンの付加共重合体は、上記の〔1〕炭素数2~20のα-オレフィン成分と、〔2〕一般式(I)で示される環状オレフィン成分以外に、本発明の目的を損なわない範囲で、必要に応じて他の共重合可能な不飽和単量体成分を含有していてもよい。
低分子量環状オレフィン系樹脂としては、前記環状オレフィン系樹脂の項で例示された環状オレフィン系樹脂が例示できる。これらの環状オレフィン系樹脂のうち、相溶性等の観点から、環状オレフィン系樹脂と同系統又は同種の樹脂を用いることが好ましい。
本発明は、低分子量環状オレフィン系樹脂を環状オレフィン系樹脂とマスターバッチ化して用いることが特徴である。マスターバッチ化することで射出成形の際に低分子量環状オレフィン系樹脂の急速な溶融を防ぐことができる。このため、樹脂の食い込み性が向上し、成形材料がスムーズに移動する。その結果、射出成形の際にショット毎の計量時間が短くなり、射出成形品の生産性が向上する。
マスターバッチとドライブレンドする環状オレフィン系樹脂としては、マスターバッチに含まれる上記環状オレフィン系樹脂の説明で例示したものと同様のものを例示することができる。
本発明の特徴は射出成形をすることである。そこで、以下、射出成形をいくつかの工程に分けて、上記マスターバッチを用いることが好ましい理由を説明する。
本発明における射出成形は、ドライブレンドすることが特徴である。ドライブレンドでなければ、表面に現れる低分子量環状オレフィン系樹脂が少ないため、ゲル状物発生を効果的に抑制することができない。
可塑化工程では、ホッパから供給された環状オレフィン系樹脂、マスターバッチ等(成形材料)を移送・溶融して、均質な溶融体を作る。
射出工程は、溶融した樹脂をシリンダーから金型内へ押出す工程である。射出速度や射出圧力は、用いる成形材料によって好ましい射出速度で射出する。
マスターバッチとドライブレンドする環状オレフィン系樹脂(樹脂A):Topas Advanced Polymers GmbH社製、商品名「TOPAS5013」、数平均分子量40000、ガラス転移点140℃。
マスターバッチに含まれる環状オレフィン系樹脂(B1):Topas Advanced Polymers GmbH社製、商品名「TOPAS5010」、数平均分子量30000、ガラス転移点110℃。
低分子量環状オレフィン系樹脂(B2):Topas Advanced Polymers GmbH社製、商品名「TOPAS TM」、数平均分子量4400、ガラス転移点67℃。
上記成形材料の数平均分子量は、以下の条件で測定した。
(測定条件)
装置:Shodex SYSTEM-21(RI)
溶媒:トルエン(ナカライHPLCグレード)
カラム:Polymer Laboratories社製、MIXED-C(1本)
流速:0.8ml/分
温度:40℃
試料濃度:0.2w/v%(予め0.2μmのメンブレンフィルタで濾過)
注入量:100μl
標準試料:分子量1090000、706000、427000、190000、96400、37900、18100、10200、5970、2630、1050、500のPS(0.1w/v%濃度のポリスチレン)
解析:PS換算の分子量を評価
繰り返した測定回数:2回
表1、2に示す配合で環状オレフィン系樹脂(A又はB1)と低分子量環状オレフィン系樹脂(B2)とのブレンド物を押出機(株式会社日本製鋼所製TEX30C)に投入し、シリンダー温度190℃、押出し量10kg/hr、スクリュ回転数150rpmで、長さ2.5mm、幅2.5mm、厚さ2.5mmの実施例1~10及び比較例1、2のマスターバッチを作製した。実施例1ではマスターバッチの押出しは可能であったが、ストランドが折れやすく、半分がロングペレットになり押出し良好とはいえない。
表1、2に示す配合で樹脂原料として環状オレフィン系樹脂(A)の樹脂ペレットと実施例又は比較例のマスターバッチの樹脂ペレットと(比較例3は環状オレフィン系樹脂(A)のみ)を成形機(住友重機械工業株式会社製SE75D)に投入し射出成形品を作製した。成形条件は金型として70mm角2mmt平板(フィルムゲート)を用い、シリンダー温度270℃、金型温度110℃、射出速度150mm/s、保圧30MPa×30s、冷却40s、計量50mm、スクリュ回転数200rpm、背圧15MPa、VP切替位置11mmとした。得られた射出成形品は長さ70mm、幅70mm、厚さ2mmであった。
上記実施例及び比較例の射出成形品の成形の際に計量時間を測定した。測定回数は30回とした。計量時間の平均(AVG)と、最長の計量時間と最短の計量時間の差とを計算し、結果を表1に示した。
実施例、比較例の射出成形品1gを20gのシクロヘキサンに入れ、マグネティックスターラーで500rpmにて2時間攪拌し射出成形品を溶解した。その後、溶液内の不溶物量を目視で評価した。評価は不溶物無しの場合が5、不溶物が少ない場合が4、不溶物がやや少ない場合が3、不溶物がやや多い場合が2、不溶物が多い場合が1とした。これらの評価結果を表1に示した。
射出速度を40mm/sに変更した以外は上記実施例、比較例と同様に射出成形品を得た。射出成形品を目視で評価し、その評価はスプレーマーク無しを◎、スプレーマークが少ない場合を○、スプレーマークが多い場合を×とした。評価結果を表1に示した。
Claims (5)
- 環状オレフィン系樹脂と、数平均分子量が10000以下である低分子量環状オレフィン系樹脂と、を用いた射出成形品の製造方法であって、
前記環状オレフィン系樹脂と前記低分子量環状オレフィン系樹脂とを含むマスターバッチと、
前記環状オレフィン系樹脂と、をドライブレンドする工程後に射出成形する射出成形品の製造方法。 - 前記マスターバッチは、前記環状オレフィン系樹脂の含有量が20質量%から95質量%、前記低分子量環状オレフィン系樹脂の含有量が5質量%から80質量%であるマスターバッチであって、
前記ドライブレンドする工程は、前記環状オレフィン系樹脂100質量部に対して、前記マスターバッチを5質量部から100質量部のブレンドである請求項1に記載の射出成形品の製造方法。 - 請求項1又は2に記載の射出成形品の製造方法に用いるマスターバッチであって、
環状オレフィン系樹脂の含有量が20質量%から95質量%、
前記低分子量環状オレフィン系樹脂の含有量が5質量%から80質量%であるマスターバッチ。 - 前記低分子量環状オレフィン系樹脂の含有量が10質量%から70質量%である請求項3に記載のマスターバッチ。
- ガラス転移点が100℃以下である請求項3又は4に記載のマスターバッチ。
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2008801224002A CN101910296B (zh) | 2007-12-27 | 2008-10-24 | 注射成型品的制造方法及其所用的母料 |
KR1020107014412A KR101205542B1 (ko) | 2007-12-27 | 2008-10-24 | 사출성형품의 제조 방법 및 그것에 이용하는 마스터배치 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2007336204A JP5341347B2 (ja) | 2007-12-27 | 2007-12-27 | 射出成形品の製造方法及びそれに用いるマスターバッチ |
JP2007-336204 | 2007-12-27 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2009084316A1 true WO2009084316A1 (ja) | 2009-07-09 |
Family
ID=40824039
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2008/069342 WO2009084316A1 (ja) | 2007-12-27 | 2008-10-24 | 射出成形品の製造方法及びそれに用いるマスターバッチ |
Country Status (5)
Country | Link |
---|---|
JP (1) | JP5341347B2 (ja) |
KR (1) | KR101205542B1 (ja) |
CN (1) | CN101910296B (ja) |
TW (1) | TWI448373B (ja) |
WO (1) | WO2009084316A1 (ja) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5043709B2 (ja) * | 2008-02-14 | 2012-10-10 | ポリプラスチックス株式会社 | Dnaチップ |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH1180492A (ja) * | 1997-08-29 | 1999-03-26 | Kishimoto Akira | 耐熱性及び耐衝撃性の改善された透明環状オレフィン系共重合体組成物 |
JP2007016102A (ja) * | 2005-07-06 | 2007-01-25 | Nippon Zeon Co Ltd | 環状オレフィン系重合体組成物および成形材料 |
JP2008195890A (ja) * | 2007-02-15 | 2008-08-28 | Nippon Zeon Co Ltd | 樹脂組成物及びフィルム |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11195890A (ja) | 1998-01-05 | 1999-07-21 | Nippon Paint Co Ltd | 特定範囲の周波数の電磁波を反射する新規な導電性双極性素子パターン及びこれを有する周波数選択性電磁波シールド材 |
JP5079221B2 (ja) * | 2004-11-26 | 2012-11-21 | 出光興産株式会社 | マスターバッチ組成物、それを含有するポリオレフィン系樹脂組成物およびその成形体 |
JPWO2007132641A1 (ja) | 2006-05-12 | 2009-09-24 | ダイセル化学工業株式会社 | 環状オレフィン系樹脂組成物 |
-
2007
- 2007-12-27 JP JP2007336204A patent/JP5341347B2/ja not_active Expired - Fee Related
-
2008
- 2008-10-24 WO PCT/JP2008/069342 patent/WO2009084316A1/ja active Application Filing
- 2008-10-24 KR KR1020107014412A patent/KR101205542B1/ko not_active IP Right Cessation
- 2008-10-24 CN CN2008801224002A patent/CN101910296B/zh not_active Expired - Fee Related
- 2008-11-19 TW TW097144649A patent/TWI448373B/zh not_active IP Right Cessation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH1180492A (ja) * | 1997-08-29 | 1999-03-26 | Kishimoto Akira | 耐熱性及び耐衝撃性の改善された透明環状オレフィン系共重合体組成物 |
JP2007016102A (ja) * | 2005-07-06 | 2007-01-25 | Nippon Zeon Co Ltd | 環状オレフィン系重合体組成物および成形材料 |
JP2008195890A (ja) * | 2007-02-15 | 2008-08-28 | Nippon Zeon Co Ltd | 樹脂組成物及びフィルム |
Also Published As
Publication number | Publication date |
---|---|
CN101910296B (zh) | 2012-04-04 |
JP2009155507A (ja) | 2009-07-16 |
JP5341347B2 (ja) | 2013-11-13 |
KR20100108541A (ko) | 2010-10-07 |
TW200932476A (en) | 2009-08-01 |
TWI448373B (zh) | 2014-08-11 |
CN101910296A (zh) | 2010-12-08 |
KR101205542B1 (ko) | 2012-11-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Hassan et al. | Mechanical and morphological properties of PP/NR/LLDPE ternary blend—effect of HVA-2 | |
WO2018107969A1 (zh) | 一种pc/abs组合物及其制备方法和应用 | |
EP2208757B1 (en) | Cyclic olefin resin composition | |
JP5341347B2 (ja) | 射出成形品の製造方法及びそれに用いるマスターバッチ | |
WO2009110296A1 (ja) | 透明樹脂組成物 | |
JP5043709B2 (ja) | Dnaチップ | |
US8088865B2 (en) | Method for producing resin composition | |
JP6256353B2 (ja) | 光学用重合体及びそれを成形してなる光学素子 | |
JP5155703B2 (ja) | 環状オレフィン系樹脂ペレットの製造方法 | |
JP4786065B2 (ja) | 切削フィルム用超高分子量ポリエチレン樹脂組成物、切削フィルム用厚肉成形体、超高分子量ポリエチレン切削フィルムの製造方法および切削フィルム | |
WO2011162098A1 (ja) | 成形体の製造方法 | |
KR20100090190A (ko) | 펠릿 혼합물, 성형체, 및 성형체의 제조 방법 | |
JP2009040949A (ja) | 熱可塑性樹脂組成物および成形品 | |
JP2007230016A (ja) | 射出成形体の製造方法 | |
WO2023189303A1 (ja) | 樹脂組成物、成形体及び光学部材 | |
JP4136996B2 (ja) | 熱可塑性ノルボルネン系樹脂からなる物品の成形方法 | |
WO2023027020A1 (ja) | 半導体封止プロセス用熱可塑性離型フィルム、及びこれを用いた電子部品の製造方法 | |
JP2011140595A (ja) | 熱可塑性樹脂組成物およびその成形品 | |
JP2024027021A (ja) | ゲル化物抑制剤、ペレット混合物、押出成形体、及び押出成形体の製造方法 | |
JP2001031844A (ja) | 成形体 | |
JP2001310952A (ja) | 熱収縮フィルム | |
WO2012043046A1 (ja) | 環状オレフィン系樹脂ペレットの製造方法及び環状オレフィン系樹脂ペレット | |
JP2024519118A (ja) | ペレット型ポリプロピレン樹脂の製造方法、ペレット型ポリプロピレン樹脂及びそれを含む成形品 | |
JP2003311813A (ja) | 環状オレフィン系樹脂の成形方法および成形体 | |
JP2001038773A (ja) | 光学部品用成形体の成形方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200880122400.2 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 08867498 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20107014412 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: PI 2010002788 Country of ref document: MY |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 08867498 Country of ref document: EP Kind code of ref document: A1 |