Classifications

• • 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
  • C08L23/10—Homopolymers or copolymers of propene
  • C08L23/14—Copolymers of propene
  • C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
• • 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 polypropylene resin composition. More specifically, the present invention relates to a polypropylene resin composition containing a xylene-soluble component having a specific composition distribution. More specifically, the present invention relates to a polypyrene resin composition having excellent transparency and excellent impact resistance, heat resistance and rigidity at low temperatures. Background art
• Molded articles made of polypropylene are economical and are used in a wide variety of fields.
• a molded article using a propylene homopolymer has high rigidity, but has a drawback that it has poor impact resistance, particularly low-temperature impact resistance.
• a propylene block copolymer obtained by first producing a propylene homopolymer and then producing an ethylene-propylene copolymer elastomer. Molded articles using this propylene-based block copolymer are widely used in various industrial fields such as automobiles and home appliances because of their excellent impact resistance.
• this propylene block copolymer is excellent in low-temperature impact resistance and rigidity, but has poor transparency, and is not applicable to applications requiring transparency, and thus has a drawback that the application is restricted.
• Japanese Unexamined Patent Publication No. Hei 6-93061 Japanese Unexamined Patent Publication No. Hei 6-310408, Japanese Unexamined Patent Publication No. Hei 7-280620 and Japanese Unexamined Patent Publication No. Hei 8-27238
• the publication discloses a propylene block copolymer in which the viscosities of the crystalline polypropylene and the propylene copolymer elastomer, the viscosity ratio and the content thereof are controlled.
• the present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a polypropylene resin composition which is excellent in balance between low-temperature impact resistance and rigidity and transparency, and which is excellent in heat seal strength when formed into a film. It is intended for. Disclosure of the invention
• the present inventors have focused on the composition distribution of xylene-soluble components that solves the above-mentioned problems of the prior art, and as a result, have found that a propylene block copolymer having a xylene-soluble component having a specific composition distribution is:
• the inventors have found that not only the balance between impact resistance and rigidity at low temperatures and the transparency but also the heat seal strength when formed into a film are excellent, and the present invention has been completed.
• the polypropylene resin composition of the present invention comprises (A) 50 to 80% by mass of a polypropylene component, and (B) 50 to 80% by mass of a copolymer elastomer of propylene and ethylene and / or ⁇ -olefin having 4 to 12 carbon atoms. 20% by mass,
• the unit derived from propylene in the component (B) of the copolymer elastomer is 50 to 85% by mass. /. , And,
• the xylene-soluble component Xs satisfies the following requirements (I) to (V).
• a propylene content F p is 50 to 80 mass 0/0.
• the propylene content (P p ) of the high propylene content component defined by the two-site model is 60 mass 0 /. Or more and less than 95 wt%, propylene emissions content of the low propylene content component (P 'p) is less than 20 wt% to 60 wt%.
• a molded article using the same has excellent balance of impact resistance and rigidity at low temperatures and transparency, and also has excellent heat sealing strength when formed into a film. Therefore, it can be used for a wider range of applications, including the automotive and home appliance fields.
• propylene content F p of the xylene-soluble portion X s is preferably more than 60 mass 0/0.
• the refractive index of the xylene-insoluble component Xi is 1.490. It is preferable that the refractive index of the xylene-soluble component Xs be in the range of 1.470 to 1.490.
• FIG. 1 is an example of a 13 C-NMR spectrum of a propylene-ethylene copolymer elastomer.
• FIG. 2 is a diagram showing names of carbons derived from a linkage distribution. BEST MODE FOR CARRYING OUT THE INVENTION
• the polypropylene resin composition of the present invention is a composition containing (A) a polypropylene component and (B) one copolymer elastomer component.
• the (A) polypropylene component in the present invention is a propylene homopolymer, or a copolymer with ethylene and Z or ⁇ -olefin having 4 to 12 carbon atoms. Body, and mixtures thereof.
• ⁇ -olefins having 4 to 12 carbon atoms include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 4-methyl-1-pentene, and the like. Things are available. These polymers may be used alone or in combination of two or more.
• the (II) polypropylene component in the present invention means a component having 95% by mass or more of units derived from propylene, and the content of these copolymer components is 5.0% by mass or less. More preferably, the copolymer component is 0.1 to 3.5% by mass. If the content of ethylene and / or ⁇ -olefin having 4 to 12 carbon atoms is more than 5% by mass, the rigidity and heat resistance of the molded article are remarkably reduced, which is not preferable.
• These polymers are produced, for example, by a known polymerization method using a known Ziegler-Natta catalyst or a metallocene catalyst.
• the polypropylene component is preferably a propylene homopolymer when rigidity and heat resistance are particularly required, and propylene and ethylene when impact resistance and transparency are particularly required. It is preferably a ct-olefin copolymer.
• the polypropylene component desirably has an intrinsic viscosity [77] force S of 2.0 to 4.8 dL / g. More preferably, it is in the range of 2.5 to 4.5 dLZg, and even more preferably in the range of 2.8 to 4.0 dL / g. If the intrinsic viscosity [7] exceeds 4.8 d LZg, poor extrusion may occur during molding and the transparency of the molded product may decrease. When the intrinsic viscosity [rj] is less than 2.0 dLZg, the extrusion rigidity and the decrease in transparency during molding are less likely to occur, but the rigidity and impact resistance of the product may be reduced.
• the (B) copolymer elastomer component of the present invention is a copolymer elastomer component of propylene and ethylene and Z or ⁇ -olefin having 4 to 12 carbon atoms.
• the ⁇ -olefin having 4 to 12 carbon atoms constituting one component of the copolymer elastomer any one can be used. Specifically, 1-butene, 1_pentene, 1-hexene, 1_heptene, 1-octene, Examples are 1-decene, 4-methyl-1--1-pentene, etc.
• (B) a copolymer elastomer single-component, the units derived from propylene refers to 50 to 85 weight 0/0. Preferably 55 to 85 weight 0/0, more favorable Mashiku is 55-80 wt%. If it exceeds 85% by mass, the impact resistance at low temperatures becomes insufficient, and if it is less than 50% by mass, the transparency or the heat seal strength may decrease.
• the polypropylene resin composition of the present invention contains (A) 50 to 80% by mass of a polypropylene component and (B) 50 to 20% by mass of one component of a copolymer elastomer.
• the content of one component (B) of the copolymer elastomer in the composition of the present invention is less than 20% by mass, the impact resistance is poor, and when it exceeds 50% by mass, the rigidity and heat resistance are poor.
• the content of one component of the copolymer elastomer is preferably in the range of 45 to 20% by mass, and more preferably in the range of 40 to 23% by mass.
• the polypropylene resin composition of the present invention has a melt flow rate (hereinafter sometimes referred to as MFR).
• MFR melt flow rate
• the range is preferably 0.5 to: 10.0 g / 10 min, and more preferably 0.7 to 7.0 gZlO. If the MFR is less than 0.1 gZlO, the components may be poorly dispersed or ejected during kneading or molding by an extruder, resulting in impact resistance, rigidity or transparency of the molded product May be reduced. If the MFR exceeds 15.0 g / 10 minutes, impact resistance and transparency may be reduced.
• the MFR is a value measured at 230 ° C and a load of 2.16 kg according to JIS K7210.
• the polypropylene resin composition of the present invention contains 20 to 50% by mass of xylene-soluble component Xs.
• the xylene-soluble content Xs is preferably in the range of 20 to 45% by mass, more preferably 23 to 40% by mass. / 0 range.
• the propylene content Fp of the xylene-soluble component is 50 to 80 mass 0 /. And preferably from 60 to 80% by weight. In particular, it is more than 60% by mass. Further more preferred details, 65-80 mass%, further, the range of 70 to 80 wt%, even more favorable Mashiku 70-78 weight 0 /. It is. If the propylene content of the xylene-soluble component is less than 50% by mass, the transparency is reduced, and the heat sealing strength when formed into a film may be reduced. Also, when the propylene content Fp exceeds 80% by mass, Impact resistance at temperature decreases.
• the intrinsic viscosity [77] XS of the xylene-soluble component in the polypropylene resin composition of the present invention is in the range of 1.4 to 5.0 dLZg, preferably in the range of 2.0 to 4.5 dL / g, and more preferably in the range of 2.5 to 4.0 d. It is in the range of LZg.
• the intrinsic viscosity [77] Xs exceeds 5.0 dL / g, the impact resistance is improved but the transparency is reduced. Further, when the intrinsic viscosity [77] Xs is less than 1.4 dLZg, the impact resistance is lowered, which is not preferable.
• the ratio of the intrinsic viscosity of the xylene-soluble component [] Xs to the intrinsic viscosity of the xylene-insoluble component [77] Xi of the polypropylene resin composition Is in the range of 0.7 to 1.5. It is preferably in the range of 0.7 to: 1.3, and more preferably in the range of 0.8 to 1.2.
• the ratio is less than 0.7, the transparency is improved, but the impact resistance at low temperatures is reduced.
• the ratio exceeds 1.5 the transparency is reduced.
• the refractive index of the xylene-soluble component is expected to be 1.470 to 1.490.
• Masure It is preferably from 1.470 to: 1.485, more preferably from 1.473 to: 1.485. If the refractive index of the xylene-soluble component is greater than 1.490, the transparency may be improved, but the impact resistance may be reduced. If it is less than 1.470, the impact resistance is improved, but the transparency is apt to be reduced.
• the refractive index of the xylene-insoluble component is desirably 1.490 to 1.510.
• the range is from 1.493 to: L.505, more preferably from 1.495 to: 1.503.
• the refractive index of the xylene-insoluble component is less than 1.490, transparency and impact resistance are improved, but rigidity and heat resistance may be reduced.
• it is larger than 1.510 the rigidity and heat resistance are improved, but the impact resistance is reduced.
• the propylene content P p of the high propylene content component defined by the two-site model in the xylene-soluble component Xs is defined as P p
• the propylene content P ′ p of the low propylene content component, the proportion P fl of the high propylene content component in the F p, and the proportion (1—P fl ) of the low propylene content component in the F p are represented by the formula (1) and (2) is satisfied.
• P P ZP 'P is 1. is less than 90, or P fl Z - in the case (1 P fl) is 2.00 or less, because the interface strength between the xylene-soluble portion and the xylene-insoluble portion decreases, This results in a decrease in heat seal strength.
• P fl Z (1-P fl ) is 6.00 or more, the interface strength is improved, but the rigidity and impact resistance are reduced.
• These formulas are indices indicating the composition distribution of the xylene-soluble component.
• the formula (1) is a measure of the composition difference between components generated from the two active points
• the formula (2) is a measure of the two activities. It is a measure for the amount of components generated from points.
• the propylene content (P p ) of the high propylene content component is 60% by mass or more and less than 95% by mass. Preferably it is 65 to 90% by mass, more preferably 70 to 90% by mass. /. It is. Propylene content of low propylene content component (P'p) is less than 60 mass% 20 mass 0/0 above. Preferably 25 to 55 mass. /. And more preferably 30 to 50% by mass.
• P p and P ′ p preferably satisfy the following expression (4), more preferably the following expression (5).
• P fl / (1 P fl ) preferably satisfies the following expression (6), and more preferably the following expression (7). 2.50 ⁇ P fl / (1-P fl ) ⁇ 5.50... (6)
• P p , P ' p , F p and P fl can be obtained by statistical analysis of 13 C_NMR spectrum.
• component (B) is a propylene-ethylene copolymer elastomer.
• Figure 1 shows a 13 C-NMR spectrum of a typical propylene-ethylene copolymer elastomer, which gives ten different peaks due to differences in the chain distribution (the order of ethylene and propylene).
• the name of this chain is described in Macromolecules, Vol. 10, p536-544 (1977), and is named as shown in FIG.
• Such a chain can be expressed as a product of the reaction probabilities, assuming a copolymerization reaction mechanism. Therefore, when the overall peak intensity is set to 1, the relative intensities of the peaks of (1) to (10) are calculated by Bernoulli statistics using the reaction probability and the abundance ratio of each site as parameters. It can be expressed as a probability equation.
• the method for producing the polypropylene resin composition of the present invention is not particularly limited, and a known method can be employed.
• the components (A) and (B) are mixed using a ribbon blender, tumbler, Henschel mixer, or the like, and then kneaded at a temperature of 170 to 280 ° C, preferably 190 to 260 ° C. It can be obtained by melt-kneading using a mixing roll, a Banbury mixer, a single-screw or twin-screw extruder, etc.
• the polypropylene resin composition of the present invention is obtained by mixing the component (A) and the component (B) in multiple stages.
• composition may further contain the component (A) and / or the component (B).
• the polypropylene component (A) and the copolymer elastomer component (B) can be produced by a known method. Specifically, it can be produced by polymerizing propylene or copolymerizing propylene and other olefins using a Ziegler catalyst or a meta-mouth catalyst.
• a Ziegler catalyst include a titanium trichloride-based catalyst and a magnesium-supported titanium catalyst.
• magnesium-supported catalyst system As a magnesium-supported catalyst system,
• a catalyst system comprising (a) a solid catalyst component containing titanium, magnesium, and halogen as essential components, (b) an organoaluminum compound, and (c) an electron-donating compound.
• a solid catalyst component containing titanium, magnesium, and halogen as essential components
• an organoaluminum compound containing titanium, magnesium, and halogen as essential components
• an organoaluminum compound containing titanium, magnesium, and halogen as essential components
• a method of manufacturing under polymerization conditions where the composition distribution, stereoregularity distribution, or molecular weight distribution is relatively wide ie, (a) by changing the polymerization conditions such as the temperature of each stage and the monomer composition ratio by multistage polymerization.
• B) The method for producing the component (Mouth) Since the composition distribution varies depending on the composition of the generally obtained polymer, the composition of the copolymer elastomer is adjusted so that the desired composition distribution is obtained.
• a polypropylene resin composition in which the composition distribution of the xylene-soluble component is controlled can be easily obtained.
• Polymerization methods such as slurry polymerization, bulk polymerization, or solution polymerization or gas phase polymerization conducted in the presence of inert hydrocarbons such as heptane, kerosene, or liquefied ⁇ -olefin solvent such as propylene are adopted.
• the reaction is carried out in a temperature range of 200 ° C., preferably 30 ° to 150 ° C., and a pressure range of 0.2 to 5.50 MPa.
• the reactor in the polymerization step those usually used in the technical field can be appropriately used.
• a continuous system, a semi-batch system, a batch system using a stirred bed reactor, a fluidized bed reactor, and a circulation reactor can be used. Any of these methods may be used.
• the molecular weight of the obtained polymer can be adjusted by adding hydrogen or the like.
• other resin additives and the like can be blended within a range that does not impair the purpose of the present invention. Examples of these other additives include antioxidants, weathering stabilizers, antistatic agents, lubricants, antiblocking agents, antifoggants, dyes, pigments, oils, waxes and the like.
• the resin composition of the present invention can be formed into a film, a sheet, a tube, a bottle, and the like by a known forming method. In addition, it can be used alone, or can be used by laminating with other materials.
• a method for producing a film and a sheet known methods are possible, and examples thereof include a water-cooled or air-cooled extrusion inflation method and a T-die method. In the case of laminating with other materials, the co-extrusion method, dry lamination method, and extrusion lamination method of the above-mentioned method can be used.
• Examples of the method for producing the tube include a usual extrusion hollow molding method. The tube is formed to an appropriate thickness and diameter depending on the field of use. Example
• MFR Melt flow rate
• JNM-GS X400 manufactured by JEOL Measured by JNM-GS X400 manufactured by JEOL (measurement mode: proton decoupling method, pulse width: 8.0 // s, pulse repetition time: 3.0 s, number of integrations: 10,000 times, measurement temperature: 120 ° C, Internal standard: hexamethyldisiloxane, solvent: 1,2,4-trichlorobenzene benzene / benzene-d6 (volume ratio 3Z1), sample concentration: 0.1 g gZm l). p, was determined the P'p and P f t.
• a film having a thickness of 50 to 80 jum is press-formed (preheating at 230 ° C for 5 minutes, degassing for 30 seconds, pressurizing at 6MPa for 1 minute, and 30. C for 3 minutes in a press). After conditioning the obtained film at room temperature for 24 hours, it was measured with an Abbe refractometer manufactured by Patago Co. using ethyl salicylate as an intermediate liquid.
• the component (A) is produced in the first stage of the multistage polymerization according to the following, and then in the second stage ( B)
• One component of the copolymer elastomer was prepared. Tables 2 and 3 show the physical properties of these components.
• the obtained white solid was thoroughly washed with anhydrous heptane, dried in a vacuum at room temperature, and partially deethanolated under a nitrogen stream.
• the resulting Mg C 1 2 ⁇ 1.2C 2 H 5 OH spherical solid 30 g was suspended in anhydrous heptane 20 Om 1. While stirring at 0 ° C, 500 ml of titanium tetrachloride was added dropwise over 1 hour. Next, when the temperature reached 40 ° C after the start of heating, 4.96 g of diisoptinophthalate was added, and the temperature was raised to 100 ° C in about 1 hour. After reacting at 100 ° C. for 2 hours, a solid portion was collected by filtration under heating.
• n-heptane 50 Om1 6.0 g of triethylaluminum, 0.99 g of cyclohexylmethyldimethoxysilane and 10 g of the polymerization catalyst obtained above were charged, and 0 to 5 ° C. The mixture was stirred for 5 minutes in the temperature range described above.
• propylene was supplied into the autoclave so that 10 g of propylene was polymerized per 1 g of the polymerization catalyst, and prepolymerization was performed for 1 hour in a temperature range of 0 to 5 ° C.
• the resulting prepolymerized catalyst was washed three times with n-heptane (50 Om1) and used for the following polymerization. 2) Main polymerization
• Second stage (B) Polymerization was carried out in the same manner as in the production of PP-1, except that hydrogen was used in the production of propylene-ethylene copolymer elastomer at 50,00 Omo 1 ppm. Was. As a result, 6.3 kg of a polymer was obtained.
• Second stage (B) Polymerization was carried out in the same manner as PP-1 except that hydrogen was used in the production of propylene-ethylene copolymer elastomer at 20,00 Omo 1 ppm. Was. As a result, 5.8 kg of a polymer was obtained.
• Second stage (B) Production of propylene-ethylene copolymer elastomer Hydrogen was supplied to 40,00 Omo 1 ppm, and polymerization was carried out in the same manner as PP_1 except that polymerization was carried out for 40 minutes. went. As a result, 5.7 kg of a polymer was obtained.
• Polymerization was carried out in the same manner as in the production of PP-1, except that the mass ratio of the ethylene / propylene mixed gas was changed to 50/50.
• Polymerization was carried out in the same manner as in the production of PP-1, except that the mass ratio of the ethylene / propylene mixed gas was 38/62.
• the polypropylene resin compositions of Comparative Examples 3 and 4 shown in Table 3 were produced using a solid catalyst in which titanium tetrachloride was supported on magnesium chloride, a catalyst comprising an organoaluminum compound and an electron-donating compound.
• PP- solid catalyst 20 g obtained in the first production method was suspended in toluene 300 meters 1, the temperature 25, the resulting T i C 1 4 [C 6 H, (COO i C 4 H 9) 2 ] was added and the mixture was stirred for 1 hour, and a solid portion was collected by hot filtration. Thereafter, the reaction product was washed three times with 50 Om1 of toluene at 90 ° C. and three times with 5 mL of hexane at room temperature. The titanium content in the obtained solid catalyst component was 1.78% by mass.
• Second stage Production of propylene-ethylene copolymer elastomer
• a film was formed under the conditions of a screw rotation speed of 80 rpm, a take-up speed of 12 m / sec, and a chill roll temperature of 50 ° C. to form a finolem having a thickness of about 70 ⁇ m.
• a resin composition and a film were produced in the same manner as in Example 1, except that those shown in Tables 2 and 3 were used instead of PP-1.
• a PET film having a thickness of 60 ⁇ m with an adhesive resin laminated thereon and a film made of the above-mentioned polypropylene resin composition are overlapped in two sets so that the polypropylene resin composition film is on the inside, and a tester manufactured by Tester Sangyo Co., Ltd. Heat-sealed using a sealing machine (heat seal bar width 5 mm, seal temperature 160 ° C and 170 ° C, pressurized at 0.21 ⁇ 3 for 1 second, perpendicular to the resin flow direction (MD) during molding) Direction).
• a sealing machine heat seal bar width 5 mm, seal temperature 160 ° C and 170 ° C, pressurized at 0.21 ⁇ 3 for 1 second, perpendicular to the resin flow direction (MD) during molding
• heat-sealed film After conditioning at room temperature for 48 hours, heat-sealed film is sampled to a width of 15 mm, and heat-sealed in a direction to open the heat-sealed part 180 ° at a chucking distance of 50 mm and a pulling speed of 300 mm / min. The tensile load was applied until the part broke, and the average strength during that period was determined. The average value of the seven points of the average strength was defined as the heat seal strength.
• the film was sampled to a size of 10 cm X lm and left in a constant temperature room at 15 ° C for 2 hours. After that, a 1Z2-inch radius tip was attached to a film impact tester manufactured by Toyo Seiki Seisakusho in this constant temperature room, and a single sample was tested 10 times to measure the impact energy. Divide these impact energy values by the thickness of the film and use the average value of the 10 points as the film impact to measure the impact resistance. Degree.
• the flow direction (MD) of the resin during molding was measured under the conditions of a sample width of 20 mm, a chuck distance of 250 mm, and a pulling speed of 5 mm / min.
• Comparative Example 1 where the unit derived from propylene in the component (B) of the copolymer elastomer is small, the transparency is low. Further, in Comparative Example 2 not satisfying the lower limit of the expression (2) and Comparative Example 3 not satisfying the expression (1), the heat seal strength is low. Furthermore, in Comparative Example 4 in which the propylene content Fp of Xs is large and does not satisfy the upper limit of the expression (2), the heat seal strength and the impact resistance are low. (2) The lower limit of the formula is not satisfied. In Comparative Example 5, the heat seal strength was low. Industrial applicability
• a molded article using the same is excellent in balance between impact resistance and rigidity at low temperatures and transparency, and furthermore, heat seal strength when formed into a film. Excellent.
• the xylene-soluble component Xs can be used for a wider range of applications, including the automotive and consumer electronics fields.
• the propylene content Fp of the xylene-soluble component Xs to more than 60% by mass, transparency and heat
• the sealing strength can be further increased.
• the refractive index of the xylene-insoluble component Xi and the refractive index of the xylene-soluble component Xs within a specific range, the transparency, impact resistance, rigidity, and heat resistance are balanced at a higher level. be able to.

Landscapes

• Chemical & Material Sciences (AREA)
• Crystallography & Structural Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Manufacture Of Macromolecular Shaped Articles (AREA)

Priority Applications (1)

Applications Claiming Priority (2)

Publications (1)

Family

ID=29416758

Family Applications (1)

Country Status (3)

Families Citing this family (6)

Citations (3)

Family Cites Families (2)

• 2003
  • 2003-05-09 AU AU2003235918A patent/AU2003235918A1/en not_active Abandoned
  • 2003-05-09 CN CNB038103583A patent/CN1314744C/zh not_active Expired - Fee Related
  • 2003-05-09 WO PCT/JP2003/005836 patent/WO2003095551A1/ja active Application Filing

Patent Citations (3)

Also Published As

Similar Documents

Legal Events