WO2023218848A1 - Resin composition for forming polypropylene film, polypropylene film, and multilayer body - Google Patents

Resin composition for forming polypropylene film, polypropylene film, and multilayer body Download PDF

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Publication number
WO2023218848A1
WO2023218848A1 PCT/JP2023/014906 JP2023014906W WO2023218848A1 WO 2023218848 A1 WO2023218848 A1 WO 2023218848A1 JP 2023014906 W JP2023014906 W JP 2023014906W WO 2023218848 A1 WO2023218848 A1 WO 2023218848A1
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film
antioxidant
resin composition
light stabilizer
polypropylene
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PCT/JP2023/014906
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French (fr)
Japanese (ja)
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浩介 高柳
雄太 桶屋
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凸版印刷株式会社
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Publication of WO2023218848A1 publication Critical patent/WO2023218848A1/en

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    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/32—Compounds containing nitrogen bound to oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3435—Piperidines
    • 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
    • C08L23/12—Polypropene

Definitions

  • the present invention relates to a resin composition for forming a polypropylene film, a polypropylene film, and a laminate.
  • Films made from polypropylene resin have excellent transparency, gloss, heat resistance, etc., and are therefore used in various fields such as packaging and industry.
  • films made of polyethylene, polyethylene terephthalate, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, etc., aluminum foil, etc. are added to polypropylene film.
  • Various laminated bodies are also known.
  • antioxidants reduce the molecular weight of polypropylene due to the effects of heat from the extruder during film formation, shear force from the extruder screw, or catalyst residue contained in the polypropylene resin. It is added to prevent the progress of oxidative deterioration.
  • primary antioxidants such as hindered phenol antioxidants, which have a primary antioxidant function that captures peroxy radicals (ROO ⁇ ), and phosphorus-based antioxidants, etc. It is common to add it to polypropylene resin in combination with a secondary antioxidant that has a secondary antioxidant function that decomposes hydroperoxide (ROOH), such as antioxidants and sulfur-based antioxidants. It is.
  • ROOH hydroperoxide
  • Phosphorous antioxidants which are secondary antioxidants, undergo a hydrolysis reaction to produce phosphorous acid when stored alone before film formation and during the storage process after film formation. It has been known. When phosphorous acid is produced, the antioxidant performance is reduced and at the same time, it causes damage such as staining to equipment such as extruders and take-off machines.
  • Irgafos168 main component: tris(2,4-di-t-butylphenyl) phosphite
  • BASF Japan Co., Ltd. shown in formula (1)
  • Patent Document 1 discloses the use of the above-mentioned phosphite antioxidant in combination with a phenolic antioxidant, a lactone antioxidant, or the like.
  • the above-mentioned phosphite-based antioxidants can prevent the progress of the hydrolysis reaction, but at the same time, the affinity for oxygen atoms and the performance as an antioxidant may decrease, so it is difficult to obtain sufficient antioxidant effects. It is necessary to increase its content.
  • the antioxidant and its decomposition products are deposited on the film surface during film formation, during post-processes such as lamination after film formation, or during storage after film formation. There is a risk that the product may bleed out, staining equipment such as extruders and take-off machines, and causing trouble during post-processing.
  • the present invention was made in view of the above circumstances, and provides a resin composition for forming a polypropylene film that can exhibit processing stability during film formation and long-term thermal stability after film formation while suppressing the amount of additives used.
  • the purpose is to Another object of the present invention is to provide a polypropylene film obtained using the resin composition, and a laminate including the polypropylene film.
  • a polypropylene film-forming resin composition according to one aspect of the present invention includes a polypropylene resin, a hindered amine light stabilizer having a function of capturing carbon radicals, and a hydroxylamine having a primary antioxidant function and a secondary antioxidant function.
  • a system antioxidant includes a hindered amine light stabilizer having a function of capturing carbon radicals, and a hydroxylamine having a primary antioxidant function and a secondary antioxidant function.
  • the above resin composition contains a hindered amine light stabilizer that has the function of capturing carbon radicals (R.) and a hydroperoxide that has the function of capturing peroxy radicals (ROO.) during the oxidative deterioration cycle of polypropylene resin. It also contains a hydroxylamine-based antioxidant that also has the function of decomposing (ROOH).
  • the ability to suppress oxidative deterioration of polypropylene resin due to the heat of the extruder during film formation (processing stability), and the ability to suppress oxidative deterioration of polypropylene resin during storage after film formation (long-term thermal stability) are obtained. be able to.
  • the hydroxylamine-based antioxidant may be dialkylhydroxylamine.
  • the hydroxylamine-based antioxidant may be bis-octadecylhydroxylamine.
  • the weight average molecular weight of the hindered amine light stabilizer may be less than 2,000.
  • the hindered amine light stabilizer may be bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate.
  • the content of the light stabilizer may be 150 mass ppm or more, and the content of the antioxidant is 150 mass ppm, based on the total amount of the polypropylene resin, the light stabilizer, and the antioxidant. or more, and the total content of the light stabilizer and antioxidant may be 2500 mass ppm or less.
  • a polypropylene film according to one aspect of the present invention is formed from the above resin composition.
  • the melt flow rate (according to JIS K6921-2, temperature 230° C., load 2.16 kg) may be 20.0 g/10 min or less.
  • a laminate according to one aspect of the present invention includes the above film.
  • the present invention it is possible to provide a resin composition for forming a polypropylene film that can exhibit processing stability during film formation and long-term thermal stability after film formation while suppressing the amount of additives used. Further, according to the present invention, it is possible to provide a polypropylene film obtained using the resin composition and a laminate including the polypropylene film.
  • the polypropylene film-forming resin composition includes a polypropylene resin, a hindered amine light stabilizer that has a function of capturing carbon radicals, and a hydroxylamine-based antioxidant that has a primary antioxidant function and a secondary antioxidant function.
  • the resin composition for forming a polypropylene film may be simply referred to as a resin composition.
  • Polypropylene resins include homopolymer (propylene homopolymer), which is a polymer of only propylene, random copolymer (propylene/ethylene random copolymer), which is a copolymer of propylene and ethylene, and ethylene-propylene in homopolymer. Examples include block copolymers (propylene/ethylene block copolymers) having a structure in which polymers are interspersed, and any of the polymers can enjoy the effects of the light stabilizer and antioxidant. Further, the stereoregularity of the polypropylene resin may be any of isotactic, syndiotactic, and atactic. When polymerizing the polypropylene resin, any known catalyst such as a Ziegler-Natta catalyst or metallocene catalyst may be selected, and any known production method may be used.
  • any known catalyst such as a Ziegler-Natta catalyst or metallocene catalyst may be selected, and any known production method may be used.
  • a hindered amine light stabilizer As the light stabilizer, a hindered amine light stabilizer is used which has a function of capturing carbon radicals (R.) during the oxidative deterioration cycle of polypropylene resin. Hindered amine light stabilizers are known to exhibit the function of capturing carbon radicals in a low temperature range (approximately 150° C. or lower), and are likely to exhibit long-term thermal stability after film formation.
  • the light stabilizer preferably includes a hindered amine light stabilizer having a weight average molecular weight of less than 2000.
  • the light stabilizer In a film formed using a resin composition containing such a light stabilizer, the light stabilizer easily migrates inside the film. Therefore, when the light stabilizer near the film surface layer is consumed, new light stabilizer is easily replenished, making it easier to exhibit long-term thermal stability.
  • the weight average molecular weight can be 1500 or less, may be 1000 or less, or may be 500 or less.
  • the light stabilizer may further include a hindered amine light stabilizer having a weight average molecular weight of 2000 or more.
  • a hindered amine light stabilizer having a weight average molecular weight of 2000 or more This makes it difficult for the light stabilizer to bleed out onto the film surface, making it easier to prevent staining of equipment such as an extruder and take-off machine and troubles during post-processes.
  • the amount of hindered amine light stabilizer with a weight average molecular weight of less than 2000 contained in the light stabilizer should be 20% by mass or more, 50% by mass or more, or 80% by mass. % or more, and may be 100% by mass.
  • the lower limit of the weight average molecular weight can be set to 500 or more from the viewpoint of easily developing long-term thermal stability.
  • hindered amine light stabilizers with a weight average molecular weight of less than 2000 include bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (molecular weight: 480.72) and bis(1,2 malonate). ,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butyl (molecular weight: 685), N,N'-bis (2,2,6,6-tetramethyl-4-piperidyl)-N,N'-diformylhexamethylene diamine (molecular weight: 451) and the like.
  • a hydroxylamine-based antioxidant As the antioxidant that has (also has) a primary antioxidant function and a secondary antioxidant function, a hydroxylamine-based antioxidant is used. Hydroxylamine-based antioxidants have both the function of capturing peroxy radicals (ROO.) and the function of decomposing hydroperoxides (ROOH) in the cycle of oxidative deterioration of polypropylene resin.
  • ROO. peroxy radicals
  • ROOH hydroperoxides
  • dialkylhydroxylamine which has two hydrocarbon groups added to the nitrogen atom of hydroxylamine.
  • Dialkylhydroxylamine has good compatibility with polypropylene resin and is easily dispersed uniformly within the polypropylene resin, so that it can more effectively exhibit the antioxidant function of the polypropylene resin.
  • the hydrocarbon group is preferably a saturated linear hydrocarbon group, and the number of carbon atoms contained in the hydrocarbon group is preferably 12 or more. .
  • hydrocarbon group examples include dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, and the like.
  • dialkylhydroxylamine it is particularly preferable to use bis-octadecylhydroxylamine.
  • bis-octadecylhydroxylamine in addition to the function of preventing oxidative deterioration of polypropylene resin, it also prevents discoloration of the film and decomposition of polypropylene resin when the formed film is irradiated with radiation such as gamma rays or electron beams. A function to prevent this can be added.
  • the antioxidant may further contain another antioxidant having a primary antioxidant function or a secondary antioxidant function.
  • Other antioxidants include antioxidants that have a primary antioxidant function that captures peroxy radicals (ROO), such as hindered phenol antioxidants, phosphorus antioxidants, and sulfur antioxidants.
  • ROO peroxy radicals
  • examples include secondary antioxidants having a secondary antioxidant function of decomposing hydroperoxide (ROOH) such as ROOH.
  • ROOH hydroperoxide
  • the amount of hydroxylamine-based antioxidant contained in the antioxidant should be 50% by mass or more or 80% by mass or more. is preferable, and may be 100% by mass.
  • hindered phenol antioxidants examples include 2,6-di-tert-butyl-4-methylphenol, stearyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and tetrakis[ Examples include pentaerythritol (3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid).
  • the content of the light stabilizer is preferably 150 mass ppm or more, and the antioxidant content is preferably 150 mass ppm or more, based on the total amount of the polypropylene resin, light stabilizer, and antioxidant. Thereby, it is easy to obtain the effect of preventing oxidative deterioration of the polypropylene resin.
  • the content of the light stabilizer is more preferably 250 mass ppm or more or 500 mass ppm or more, and the antioxidant content is more preferably 250 mass ppm or more or 500 mass ppm or more.
  • the total content of the light stabilizer and antioxidant is preferably 2500 mass ppm or less based on the total amount of the polypropylene resin, light stabilizer, and antioxidant.
  • the total content of the light stabilizer and antioxidant is more preferably 2000 mass ppm or less, or 1500 mass ppm or less.
  • the content of the light stabilizer can be 1250 mass ppm or less, and the antioxidant content can be 1250 mass ppm or less.
  • the mass ratio of the light stabilizer content to the antioxidant content is preferably 0.1 to 2, and preferably 0.2 to 1. It is more preferable that there be. Thereby, it is easy to obtain the effect of preventing oxidative deterioration of the polypropylene resin.
  • the resin composition contains, as other components, a neutralizing agent to neutralize catalyst residue, a nucleating agent to act as a core during crystallization of polypropylene, a lubricant to reduce the coefficient of friction on the film surface, and a film to be wound.
  • a neutralizing agent to neutralize catalyst residue
  • a nucleating agent to act as a core during crystallization of polypropylene
  • a lubricant to reduce the coefficient of friction on the film surface
  • a film to be wound a film to be wound.
  • Ingredients such as anti-blocking agents to prevent blocking when stored in the removed state, anti-static agents to prevent foreign matter from adhering to the film surface and the film from being charged and adhering to processing machines and other films (other additives) may be included as appropriate depending on the actual use.
  • a polypropylene film is formed from the above resin composition for forming a polypropylene film.
  • various methods such as hot pressing, extrusion molding, casting molding, and calender molding can be appropriately selected.
  • the polypropylene film may be subjected to various stretching processes such as uniaxial stretching, sequential biaxial stretching, simultaneous biaxial stretching, and multistage stretching.
  • the melt flow rate (according to JIS K6921-2, temperature 230° C., load 2.16 kg) of the polypropylene film is preferably 20.0 g/10 min or less. This indicates that the light stabilizer and antioxidant function sufficiently and that oxidative deterioration of the polypropylene resin tends to be difficult to progress due to the heat of the extruder during film formation.
  • the melt flow rate is more preferably 13.0 g/10 min or less. When the melt flow rate exceeds 20.0 g/10 min, the melt viscosity of the polypropylene resin is low and the discharge amount from the T-die is difficult to stabilize, so the thickness of the film formed tends to fluctuate easily. Furthermore, the impact resistance of the formed film tends to decrease.
  • the lower limit of the melt flow rate is not particularly limited, but when using the above-mentioned polypropylene resin, it can be set to 3.0 g/10 min or more.
  • the type and amount of the light stabilizer and antioxidant in the polypropylene film can be determined, for example, by an elution test (a method in which the film is immersed in a solvent to extract additives such as the antioxidant).
  • the stability (degree of decomposition) of the additive in the polypropylene film can be evaluated, for example, as follows. When the peak area value ratio ((BB')/(AA')) shown below is 1.0 or more and less than 1.6, the decomposition of the additive is difficult to proceed and the additive is stable. It can be said that it is a polypropylene film that exists.
  • the peak area value ratio is preferably 1.5 or less, more preferably 1.4 or less.
  • ⁇ Peak area value ratio calculation method> A polypropylene film is cut into A4 size (width direction 210 mm x flow direction 291 mm) and stored in a constant temperature machine at a set temperature of 150° C. for 60 days. This performs a deterioration treatment on the polypropylene film. The films before and after the deterioration treatment are each cut into 10 cm square pieces, cut into strips, placed in a vial, and 10 ml of ethanol is added and sealed. The area of the film in contact with ethanol (liquid contact area) is adjusted to be 0.05 ml/cm 2 or less.
  • the obtained ethanol extract is collected and subjected to GC/MS analysis.
  • the obtained total ion chromatogram is analyzed by GC/MS analysis. From the total ion chromatogram of the film extract before deterioration treatment, the baseline was subtracted from the peaks at retention times of 6 to 40 minutes to determine the total peak area value (A). ) is calculated by subtracting the peak area value (A') of (AA').
  • the hydrocarbon peaks are compared with the peaks detected in the polypropylene film without additives, and the peaks with the same retention time and mass spectrum are targeted.
  • the peak area value (B) of hydrocarbons is subtracted to calculate (BB'). From these results, the peak area value ratio ((BB')/(AA')) is calculated.
  • the thickness of the polypropylene film is not particularly limited, but can be 10 to 300 ⁇ m. If the thickness is 10 ⁇ m or more, troubles such as breakage or tearing during the process after film formation or during film handling will be less likely to occur, and if the thickness is 300 ⁇ m or less, the film will not be easily damaged during winding after film formation. Troubles such as curling or loose winding due to insufficient tension are less likely to occur.
  • the laminate includes the polypropylene film described above.
  • a polypropylene film may be produced as a single layer film, but it can be made into two or more layers by using multiple extruders and coextruding the same or different types of polypropylene resin by a feed block method or a multi-manifold method. It may also be formed as a multilayer film. That is, the laminate can include a plurality of polypropylene films of the same or different types.
  • the laminate can include various layers known as packaging materials on one or both sides of a single-layer or multi-layer polypropylene film.
  • layers include a sealant layer, a metal foil layer, a vapor deposition layer (aluminum vapor deposition layer, alumina vapor deposition layer, silica vapor deposition layer, etc.), a printing layer, an adhesive layer, a surface protection layer, and the like.
  • These layers can be laminated by known methods such as dry lamination, thermal adhesion, printing on the film surface, coating, vapor deposition, and the like. Note that by providing a vapor deposited layer on a polypropylene film, it can be suitably used as a film having barrier stability while suppressing the antioxidant content.
  • Examples of the laminate include the following. A laminate having a layer structure of polypropylene (20 ⁇ m)/polyethylene (60 ⁇ m), which is obtained by coextruding the above polypropylene resin and polyethylene resin. A laminate having a layer structure of polypropylene (20 ⁇ m)/ethylene-vinyl alcohol copolymer (15 ⁇ m)/polyethylene (60 ⁇ m), which is obtained by coextruding the above polypropylene resin, ethylene-vinyl alcohol copolymer resin, and polyethylene resin.
  • Example 1 PX600N (propylene homopolymer) manufactured by Sun Allomer Co., Ltd. was used as a raw material for the polypropylene resin.
  • Chiguard 770 main component: bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate
  • Chitec Technology Co., Ltd. which is a hindered amine light stabilizer
  • bis-octadecylhydroxylamine which is a hydroxylamine-based antioxidant having a primary antioxidant function and a secondary antioxidant function, was used.
  • Example 2-4 Comparative Examples 1-4
  • a film was formed in the same manner as in Example 1, except that the amounts of Chiguard 770 and bis-octadecylhydroxylamine were changed as shown in Table 1.
  • Irganox 1010 (mainly manufactured by BASF Japan Co., Ltd.), which is a hindered phenol antioxidant that has a primary antioxidant function (has only the function of a primary antioxidant), is used.
  • Comparative example 6 A film was formed in the same manner as in Comparative Example 5, except that the amounts of Irganox 1010 and Irgafos 168 were changed as shown in Table 1.
  • melt flow rate (MFR) of each film in accordance with JIS K6921-2 was measured using a melt indexer (FF-01) manufactured by Toyo Seiki Seisakusho Co., Ltd.
  • the set temperature of the melt indexer was 230°C.
  • the film of each example was cut into a size of about 5 mm square to prepare a sample.
  • the weight of the sample was approximately 5 g (approximately 5 ⁇ 1 g). This sample was placed in a melt indexer, and the mass of resin discharged in 30 seconds was measured with a load of 2.16 kg applied. This measured value was multiplied by 20 to calculate the MFR value.
  • Table 1 The results are shown in Table 1.
  • the film of the example was formed by adding Chiguard 770, a light stabilizer that has the function of capturing carbon radicals, and bis-octadecylhydroxylamine, which has both primary and secondary antioxidant functions.
  • the melt flow rate value was kept low compared to the film of Comparative Example 1, which was formed without adding any antioxidant, and the films of Comparative Example 2 and Comparative Example 3, which were formed by adding only Chiguard 770. It was getting worse.
  • the examples show that the oxidative deterioration of the polypropylene resin due to the heat of the extruder is relatively difficult to progress, and the processing stability is good.
  • the film of each example was cut into an A4 size (210 mm in the width direction x 291 mm in the machine direction) and stored in a constant temperature machine (HT310) manufactured by ESPEC Co., Ltd. at a set temperature of 150° C. for 60 days. This subjected the film to deterioration treatment.
  • the films of each example before and after the deterioration treatment were cut into 10 cm square pieces, cut into strips, placed in a vial, and 10 ml of ethanol (manufactured by Kanto Kagaku, special reagent grade, 99.5% purity) was added and sealed.
  • the area of the film in contact with ethanol was adjusted to be 0.05 ml/cm 2 or less.
  • the vial was stored in a dry oven (DO-450A manufactured by As One) set at 60° C. for 10 days. Thereafter, the obtained ethanol extract was collected and subjected to GC/MS analysis.
  • GC/MS analysis conditions are shown below.
  • Device model number GC6890/5973MSD (manufactured by Agilent Technologies) ⁇ GC conditions>
  • Runtime 44.00min.
  • Carrier gas He (constant flow mode: 1.0ml/min.)
  • Pulse pressure 20psi Pulse time: 1.5min.
  • the film extract of each example was analyzed by GC/MS under the above analysis conditions, and the resulting total ion chromatogram was analyzed using MSD ChemStation (E.02.02.1431). From the total ion chromatogram of the film extract before deterioration treatment, the baseline was subtracted from the peaks at retention times of 6 to 40 minutes to determine the total peak area value (A). ) was calculated by subtracting the peak area value (A') of (AA'). At this time, a peak detected in a polypropylene film without additives (Comparative Example 1) was compared, and a peak with the same retention time and mass spectrum was determined to be a hydrocarbon peak.
  • the total peak area value (B) was determined in the same manner as above, and then the peak area value (B') of hydrocarbons was subtracted to calculate (BB'). From these results, the peak area value ratio ((BB')/(AA')) was calculated. As an example, in Example 1, (AA') was 55,220,614, (BB') was 65,986,934, and the value of (BB')/(AA') was approximately 1.2. .
  • the peak area value ratios of all examples are shown in Table 2.
  • the resin composition for forming a polypropylene film in the present disclosure can suppress oxidative deterioration of the polypropylene resin during film formation and over a long period of time after film formation.
  • the polypropylene film produced from the resin composition can be expected to be used in various fields such as flexible packaging materials, electronics packaging materials, medical/pharmaceutical packaging materials, toiletry products, liquid composite paper containers, and chilled/frozen food packaging materials. .

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Abstract

The present invention provides a resin composition for forming a polypropylene film, the resin composition containing: a polypropylene resin; a hindered amine light stabilizer that has a function of trapping carbon radicals; and a hydroxylamine-based antioxidant that has a primary antioxidant function and a secondary antioxidant function.

Description

ポリプロピレンフィルム形成用樹脂組成物、ポリプロピレンフィルム、及び積層体Resin composition for forming polypropylene film, polypropylene film, and laminate
　本発明は、ポリプロピレンフィルム形成用樹脂組成物、ポリプロピレンフィルム、及び積層体に関する。 The present invention relates to a resin composition for forming a polypropylene film, a polypropylene film, and a laminate.
　ポリプロピレン樹脂を原料として製膜されたフィルムは、透明性、光沢性、耐熱性等に優れることから、包装用や産業用等の様々な分野に用いられている。また、防湿性や酸素遮断性等を高めることを目的として、ポリプロピレンフィルムに、ポリエチレン、ポリエチレンテレフタラート、エチレン－酢酸ビニル共重合体、エチレン－ビニルアルコール共重合体等からなるフィルム、アルミニウム箔などを積層させた積層体も、種々知られている。 Films made from polypropylene resin have excellent transparency, gloss, heat resistance, etc., and are therefore used in various fields such as packaging and industry. In addition, for the purpose of increasing moisture resistance and oxygen barrier properties, films made of polyethylene, polyethylene terephthalate, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, etc., aluminum foil, etc. are added to polypropylene film. Various laminated bodies are also known.
　一般的に、ポリプロピレン樹脂を原料としてフィルムを製膜する場合には、酸化防止剤、滑剤、アンチブロッキング剤、帯電防止剤等の種々の添加剤が用いられる。 Generally, when forming a film using polypropylene resin as a raw material, various additives such as antioxidants, lubricants, antiblocking agents, and antistatic agents are used.
　上記の添加剤のうち酸化防止剤は、フィルムを製膜する場合の押出機の熱、押出機のスクリューによる剪断力、あるいはポリプロピレン樹脂に含まれる触媒残渣等の影響で、ポリプロピレンの分子量が低下したり、酸化劣化が進行したりすることを防ぐ目的で添加されている。 Among the above additives, antioxidants reduce the molecular weight of polypropylene due to the effects of heat from the extruder during film formation, shear force from the extruder screw, or catalyst residue contained in the polypropylene resin. It is added to prevent the progress of oxidative deterioration.
　一般的に、ポリプロピレン樹脂の酸化劣化は、以下のようなサイクルによって進行することが知られている。
（１）高分子（ＲＨ）が、熱や光などの作用によって炭素ラジカル（Ｒ・）を発生。
（２）Ｒ・が酸素と反応して、パーオキシラジカル（ＲＯＯ・）を発生。
（３）ＲＯＯ・が周辺のＲＨからＨ・を引き抜きハイドロパーオキサイド（ＲＯＯＨ）となり、同時にＲ・を再生。 It is generally known that oxidative deterioration of polypropylene resin progresses through the following cycles.
(1) Polymer (RH) generates carbon radicals (R.) by the action of heat, light, etc.
(2) R. reacts with oxygen to generate peroxy radical (ROO.).
(3) ROO• extracts H• from the surrounding RH and becomes hydroperoxide (ROOH), and at the same time regenerates R•.
　上記のような酸化劣化のサイクルの進行を防ぐため、ヒンダードフェノール系酸化防止剤等のように、パーオキシラジカル（ＲＯＯ・）を捕捉する一次酸化防止機能を有する一次酸化防止剤と、リン系酸化防止剤、イオウ系酸化防止剤等のように、ハイドロパーオキサイド（ＲＯＯＨ）を分解する二次酸化防止機能を有する二次酸化防止剤とを併用して、ポリプロピレン樹脂に添加することが一般的である。 In order to prevent the progression of the oxidative deterioration cycle described above, primary antioxidants such as hindered phenol antioxidants, which have a primary antioxidant function that captures peroxy radicals (ROO・), and phosphorus-based antioxidants, etc. It is common to add it to polypropylene resin in combination with a secondary antioxidant that has a secondary antioxidant function that decomposes hydroperoxide (ROOH), such as antioxidants and sulfur-based antioxidants. It is.
　二次酸化防止剤であるリン系の酸化防止剤は、フィルム製膜前に単体で保管する際、及びフィルム製膜後の保管工程において、加水分解反応が進行して亜リン酸を生成することが知られている。亜リン酸が生成すると、酸化防止性能が低下すると同時に、押出機や引取機等の設備に汚損等の損害を与える原因となる。 Phosphorous antioxidants, which are secondary antioxidants, undergo a hydrolysis reaction to produce phosphorous acid when stored alone before film formation and during the storage process after film formation. It has been known. When phosphorous acid is produced, the antioxidant performance is reduced and at the same time, it causes damage such as staining to equipment such as extruders and take-off machines.
　このため、加水分解を起こしにくい種々のリン系酸化防止剤が考案されている。例えば式（１）に示したＢＡＳＦジャパン株式会社製のＩｒｇａｆｏｓ１６８（主成分：トリス（２，４－ジ－ｔ－ブチルフェニル）ホスファイト）は、３つのオルト位がｔ－ブチル基で置換されたフェノールであり、フェノールのオルト位にある置換基のスペース障害を強化することで、リン原子が水分子と接触し難くなり、加水分解反応の進行を防止する。 For this reason, various phosphorus-based antioxidants that are less susceptible to hydrolysis have been devised. For example, Irgafos168 (main component: tris(2,4-di-t-butylphenyl) phosphite), manufactured by BASF Japan Co., Ltd., shown in formula (1), has three ortho positions substituted with t-butyl groups. It is a phenol, and by strengthening the space hindrance of the substituent at the ortho position of the phenol, the phosphorus atom becomes difficult to come into contact with water molecules, thereby preventing the progress of the hydrolysis reaction.
　例えば特許文献１には、上記のホスファイト系酸化防止剤をフェノール系酸化防止剤やラクトン系酸化防止剤等と組み合わせて用いることが開示されている。 For example, Patent Document 1 discloses the use of the above-mentioned phosphite antioxidant in combination with a phenolic antioxidant, a lactone antioxidant, or the like.
特開２００７－１２６６４４号公報Japanese Patent Application Publication No. 2007-126644
　ところで、上記のホスファイト系酸化防止剤は、加水分解反応の進行は防止できるが、同時に酸素原子に対する親和性及び酸化防止剤としての性能の低下が生じる場合があり、十分な酸化防止効果を得るにはその含有量を増量する必要がある。 By the way, the above-mentioned phosphite-based antioxidants can prevent the progress of the hydrolysis reaction, but at the same time, the affinity for oxygen atoms and the performance as an antioxidant may decrease, so it is difficult to obtain sufficient antioxidant effects. It is necessary to increase its content.
　しかしながら、酸化防止剤の含有量を増量すると、フィルム製膜時、製膜後のラミネートなどの後工程の際、あるいは製膜後の保管時等において、フィルム表面に酸化防止剤及びその分解物等がブリードアウトし、押出機や引取機等の設備の汚損、後工程の際のトラブル等が生じる虞がある。 However, when the content of antioxidant is increased, the antioxidant and its decomposition products are deposited on the film surface during film formation, during post-processes such as lamination after film formation, or during storage after film formation. There is a risk that the product may bleed out, staining equipment such as extruders and take-off machines, and causing trouble during post-processing.
　本発明は上記事情に鑑みなされたものであり、添加剤使用量を抑えつつ、製膜時の加工安定性及び製膜後の長期熱安定性を発現できる、ポリプロピレンフィルム形成用樹脂組成物を提供することを目的とする。また本発明は、当該樹脂組成物を用いて得られるポリプロピレンフィルム、及び当該ポリプロピレンフィルムを備える積層体を提供することを目的とする。 The present invention was made in view of the above circumstances, and provides a resin composition for forming a polypropylene film that can exhibit processing stability during film formation and long-term thermal stability after film formation while suppressing the amount of additives used. The purpose is to Another object of the present invention is to provide a polypropylene film obtained using the resin composition, and a laminate including the polypropylene film.
　本発明の一側面に係るポリプロピレンフィルム形成用樹脂組成物は、ポリプロピレン樹脂と、炭素ラジカルを捕捉する機能を有するヒンダードアミン系の光安定剤と、一次酸化防止機能及び二次酸化防止機能を有するヒドロキシルアミン系の酸化防止剤と、を含む。 A polypropylene film-forming resin composition according to one aspect of the present invention includes a polypropylene resin, a hindered amine light stabilizer having a function of capturing carbon radicals, and a hydroxylamine having a primary antioxidant function and a secondary antioxidant function. A system antioxidant.
　上記樹脂組成物は、ポリプロピレン樹脂の酸化劣化のサイクルにおいて、炭素ラジカル（Ｒ・）を捕捉する機能を有するヒンダードアミン系の光安定剤と、パーオキシラジカル（ＲＯＯ・）を捕捉する機能及びハイドロパーオキサイド（ＲＯＯＨ）を分解する機能を併せ持つヒドロキシルアミン系の酸化防止剤とを共に含むものである。これらの光安定剤及び酸化防止剤を併用することで、従来と比較して添加剤の使用量を低く抑えながらポリプロピレン樹脂の酸化劣化を防ぐことが可能である。すなわち、フィルム製膜時の押出機の熱によるポリプロピレン樹脂の酸化劣化抑制性（加工安定性）、及びフィルム製膜後の保管の際におけるポリプロピレン樹脂の酸化劣化抑制性（長期熱安定性）を得ることができる。 The above resin composition contains a hindered amine light stabilizer that has the function of capturing carbon radicals (R.) and a hydroperoxide that has the function of capturing peroxy radicals (ROO.) during the oxidative deterioration cycle of polypropylene resin. It also contains a hydroxylamine-based antioxidant that also has the function of decomposing (ROOH). By using these light stabilizers and antioxidants in combination, it is possible to prevent oxidative deterioration of polypropylene resin while keeping the amount of additives used lower than in the past. That is, the ability to suppress oxidative deterioration of polypropylene resin due to the heat of the extruder during film formation (processing stability), and the ability to suppress oxidative deterioration of polypropylene resin during storage after film formation (long-term thermal stability) are obtained. be able to.
　樹脂組成物の一態様において、ヒドロキシルアミン系の酸化防止剤は、ジアルキルヒドロキシルアミンであってよい。 In one embodiment of the resin composition, the hydroxylamine-based antioxidant may be dialkylhydroxylamine.
　樹脂組成物の一態様において、ヒドロキシルアミン系の酸化防止剤は、ビス－オクタデシルヒドロキシルアミンであってよい。 In one embodiment of the resin composition, the hydroxylamine-based antioxidant may be bis-octadecylhydroxylamine.
　樹脂組成物の一態様において、ヒンダードアミン系の光安定剤の重量平均分子量は２０００未満であってよい。 In one embodiment of the resin composition, the weight average molecular weight of the hindered amine light stabilizer may be less than 2,000.
　樹脂組成物の一態様において、ヒンダードアミン系の光安定剤は、セバシン酸ビス（２，２，６，６－テトラメチル－４－ピペリジル）であってよい。 In one embodiment of the resin composition, the hindered amine light stabilizer may be bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate.
　樹脂組成物の一態様において、ポリプロピレン樹脂、光安定剤及び酸化防止剤の全量を基準として、光安定剤の含有量は１５０質量ｐｐｍ以上であってよく、酸化防止剤の含有量は１５０質量ｐｐｍ以上であってよく、光安定剤及び酸化防止剤の合計含有量は２５００質量ｐｐｍ以下であってよい。 In one embodiment of the resin composition, the content of the light stabilizer may be 150 mass ppm or more, and the content of the antioxidant is 150 mass ppm, based on the total amount of the polypropylene resin, the light stabilizer, and the antioxidant. or more, and the total content of the light stabilizer and antioxidant may be 2500 mass ppm or less.
　本発明の一側面に係るポリプロピレンフィルムは、上記樹脂組成物から製膜される。 A polypropylene film according to one aspect of the present invention is formed from the above resin composition.
　ポリプロピレンフィルムの一態様において、メルトフローレート（ＪＩＳ　Ｋ６９２１－２準拠、温度２３０℃、荷重２．１６ｋｇ）は２０．０ｇ／１０ｍｉｎ以下であってよい。 In one embodiment of the polypropylene film, the melt flow rate (according to JIS K6921-2, temperature 230° C., load 2.16 kg) may be 20.0 g/10 min or less.
　本発明の一側面に係る積層体は、上記フィルムを備える。 A laminate according to one aspect of the present invention includes the above film.
　本発明によれば、添加剤使用量を抑えつつ、製膜時の加工安定性及び製膜後の長期熱安定性を発現できる、ポリプロピレンフィルム形成用樹脂組成物を提供することができる。また本発明によれば、当該樹脂組成物を用いて得られるポリプロピレンフィルム、及び当該ポリプロピレンフィルムを備える積層体を提供することができる。 According to the present invention, it is possible to provide a resin composition for forming a polypropylene film that can exhibit processing stability during film formation and long-term thermal stability after film formation while suppressing the amount of additives used. Further, according to the present invention, it is possible to provide a polypropylene film obtained using the resin composition and a laminate including the polypropylene film.
　以下、本発明の好適な実施形態について説明するが、本発明は以下の実施形態にのみ限定されるものではない。実施形態に例示された各種態様は適宜組み合わせてよい。 Hereinafter, preferred embodiments of the present invention will be described, but the present invention is not limited only to the following embodiments. Various aspects illustrated in the embodiments may be combined as appropriate.
＜ポリプロピレンフィルム形成用樹脂組成物＞
　ポリプロピレンフィルム形成用樹脂組成物は、ポリプロピレン樹脂と、炭素ラジカルを捕捉する機能を有するヒンダードアミン系の光安定剤と、一次酸化防止機能及び二次酸化防止機能を有するヒドロキシルアミン系の酸化防止剤と、を含む。以下、ポリプロピレンフィルム形成用樹脂組成物を、単に樹脂組成物と言うことがある。 <Resin composition for forming polypropylene film>
The polypropylene film-forming resin composition includes a polypropylene resin, a hindered amine light stabilizer that has a function of capturing carbon radicals, and a hydroxylamine-based antioxidant that has a primary antioxidant function and a secondary antioxidant function. including. Hereinafter, the resin composition for forming a polypropylene film may be simply referred to as a resin composition.
（ポリプロピレン樹脂）
　ポリプロピレン樹脂としては、プロピレンのみの重合体であるホモポリマー（プロピレン単独重合体）、プロピレン及びエチレンの共重合体であるランダムコポリマー（プロピレン・エチレンランダム共重合体）、ホモポリマーの中にエチレン－プロピレン重合体が点在した構造を有しているブロックコポリマー（プロピレン・エチレンブロック共重合体）等が挙げられ、いずれのポリマーにおいても上記光安定剤及び酸化防止剤による効果を享受できる。また、ポリプロピレン樹脂の立体規則性は、アイソタクチック、シンジオタクチック、及びアタクチックのいずれであっても良い。ポリプロピレン樹脂の重合の際には、Ｚｉｅｇｌｅｒ－Ｎａｔｔａ触媒、メタロセン触媒等の既知の任意の触媒を選択することができ、また既知の任意の製造方法を用いて良い。 (Polypropylene resin)
Polypropylene resins include homopolymer (propylene homopolymer), which is a polymer of only propylene, random copolymer (propylene/ethylene random copolymer), which is a copolymer of propylene and ethylene, and ethylene-propylene in homopolymer. Examples include block copolymers (propylene/ethylene block copolymers) having a structure in which polymers are interspersed, and any of the polymers can enjoy the effects of the light stabilizer and antioxidant. Further, the stereoregularity of the polypropylene resin may be any of isotactic, syndiotactic, and atactic. When polymerizing the polypropylene resin, any known catalyst such as a Ziegler-Natta catalyst or metallocene catalyst may be selected, and any known production method may be used.
（光安定剤）
　光安定剤としては、ポリプロピレン樹脂の酸化劣化のサイクルにおいて、炭素ラジカル（Ｒ・）を捕捉する機能を有する、ヒンダードアミン系の光安定剤を用いる。ヒンダードアミン系光安定剤は、低温域（約１５０℃以下）において炭素ラジカルを捕捉する機能を発現することが知られており、フィルム製膜後の長期熱安定性を発揮し易い。 (light stabilizer)
As the light stabilizer, a hindered amine light stabilizer is used which has a function of capturing carbon radicals (R.) during the oxidative deterioration cycle of polypropylene resin. Hindered amine light stabilizers are known to exhibit the function of capturing carbon radicals in a low temperature range (approximately 150° C. or lower), and are likely to exhibit long-term thermal stability after film formation.
　光安定剤は、重量平均分子量が２０００未満であるヒンダードアミン系の光安定剤を含むことが好ましい。このような光安定剤が含まれる樹脂組成物を用いて製膜されたフィルムでは、光安定剤がフィルム内部を移行し易い。そのため、フィルム表層付近の光安定剤が消費された際に新たな光安定剤が補充され易く、長期熱安定性をより発揮し易くなる。この観点から、重量平均分子量は１５００以下とすることができ、１０００以下であってもよく、５００以下であってもよい。 The light stabilizer preferably includes a hindered amine light stabilizer having a weight average molecular weight of less than 2000. In a film formed using a resin composition containing such a light stabilizer, the light stabilizer easily migrates inside the film. Therefore, when the light stabilizer near the film surface layer is consumed, new light stabilizer is easily replenished, making it easier to exhibit long-term thermal stability. From this viewpoint, the weight average molecular weight can be 1500 or less, may be 1000 or less, or may be 500 or less.
　光安定剤は、重量平均分子量が２０００未満であるヒンダードアミン系の光安定剤に加えて、重量平均分子量が２０００以上のヒンダードアミン系の光安定剤をさらに含んでいてもよい。これにより、光安定剤がフィルム表面にブリードアウトし難くなり、押出機や引取機等の設備の汚損、後工程の際のトラブルを防ぎ易くなる。ただし、長期熱安定性を発揮し易い観点から、光安定剤に含まれる、重量平均分子量が２０００未満であるヒンダードアミン系の光安定剤の量は、２０質量％以上、５０質量％以上又は８０質量％以上であることが好ましく、１００質量％であってもよい。重量平均分子量の下限は、長期熱安定性を発現し易い観点から５００以上とすることができる。 In addition to the hindered amine light stabilizer having a weight average molecular weight of less than 2000, the light stabilizer may further include a hindered amine light stabilizer having a weight average molecular weight of 2000 or more. This makes it difficult for the light stabilizer to bleed out onto the film surface, making it easier to prevent staining of equipment such as an extruder and take-off machine and troubles during post-processes. However, from the viewpoint of easily exhibiting long-term thermal stability, the amount of hindered amine light stabilizer with a weight average molecular weight of less than 2000 contained in the light stabilizer should be 20% by mass or more, 50% by mass or more, or 80% by mass. % or more, and may be 100% by mass. The lower limit of the weight average molecular weight can be set to 500 or more from the viewpoint of easily developing long-term thermal stability.
　重量平均分子量が２０００未満のヒンダードアミン系の光安定剤としては、セバシン酸ビス（２，２，６，６－テトラメチル－４－ピペリジル）（分子量：４８０．７２）、マロン酸ビス（１，２，２，６，６－ペンタメチル－４－ピペリジニル）－［［３，５－ビス（１，１－ジメチルエチル）－４－ヒドロキシフェニル］メチル］ブチル（分子量：６８５）、Ｎ，Ｎ’－ビス（２，２，６，６－テトラメチル－４－ピペリジル）－Ｎ，Ｎ’－ジホルミルヘキサメチレンジアミン（分子量：４５１）等が挙げられる。
　重量平均分子量が２０００以上のヒンダードアミン系の光安定剤としては、Ｎ，Ｎ’，４，７－テトラキス｛４，６－ビス［Ｎ－ブチル－Ｎ－（１，２，２，６，６－ペンタメチル－４－ピペリジル）アミノ］－１，３，５－トリアジン－２－イル｝－４，７－ジアザデカン－１，１０－ジアミン（分子量：２２８５．６１）、コハク酸ジメチルと１－（２－ヒドロキシエチル）－４－ヒドロキシ－２，２，６，６－テトラメチル－４－ピペリジンとの重縮合物（分子量：３１００～４０００）、ポリ［［６－［（１，１，３，３－テトラメチルブチル）アミノ］－１，３，５－トリアジン－２，４－ジイル］［（２，２，６，６－テトラメチル－４－ピペリジニル）イミノ］－１，６－ヘキサンジイル［（２，２，６，６－テトラメチル－４－ピペリジニル）イミノ］］（分子量：２０００～３１００）、１，６－ヘキサンジアミン，Ｎ，Ｎ’－ビス（２，２，６，６－テトラメチル－４－ピペリジン－イル），２，４，６－トリクロロ－１，３，５－トリアジン，Ｎ－ブチル－１－ブチルアミン，およびＮ－ブチル－２，２，６，６－テトラメチル－４－ピペリジンアミンの反応物（分子量：２６００～３４００）等が挙げられる。 Examples of hindered amine light stabilizers with a weight average molecular weight of less than 2000 include bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (molecular weight: 480.72) and bis(1,2 malonate). ,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butyl (molecular weight: 685), N,N'-bis (2,2,6,6-tetramethyl-4-piperidyl)-N,N'-diformylhexamethylene diamine (molecular weight: 451) and the like.
As a hindered amine light stabilizer having a weight average molecular weight of 2000 or more, N,N',4,7-tetrakis{4,6-bis[N-butyl-N-(1,2,2,6,6- pentamethyl-4-piperidyl)amino]-1,3,5-triazin-2-yl}-4,7-diazadecane-1,10-diamine (molecular weight: 2285.61), dimethyl succinate and 1-(2- Polycondensate with (hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethyl-4-piperidine (molecular weight: 3100-4000), poly[[6-[(1,1,3,3- tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexanediyl[(2 ,2,6,6-tetramethyl-4-piperidinyl)imino]] (molecular weight: 2000-3100), 1,6-hexanediamine, N,N'-bis(2,2,6,6-tetramethyl- 4-piperidin-yl), 2,4,6-trichloro-1,3,5-triazine, N-butyl-1-butylamine, and N-butyl-2,2,6,6-tetramethyl-4-piperidine Examples include reactants of amines (molecular weight: 2,600 to 3,400).
（酸化防止剤）
　一次酸化防止機能及び二次酸化防止機能を有する（併せ持つ）酸化防止剤としては、ヒドロキシルアミン系の酸化防止剤を用いる。ヒドロキシルアミン系の酸化防止剤は、ポリプロピレン樹脂の酸化劣化のサイクルにおいて、パーオキシラジカル（ＲＯＯ・）を捕捉する機能及びハイドロパーオキサイド（ＲＯＯＨ）を分解する機能を併せ持つ。上記光安定剤と、このようなヒドロキシルアミン系の酸化防止剤とを併用することで、従来と比較してこれら添加剤の使用量を低く抑えつつ、フィルム製膜時の加工安定性及び製膜後の長期熱安定性を得ることができる。 (Antioxidant)
As the antioxidant that has (also has) a primary antioxidant function and a secondary antioxidant function, a hydroxylamine-based antioxidant is used. Hydroxylamine-based antioxidants have both the function of capturing peroxy radicals (ROO.) and the function of decomposing hydroperoxides (ROOH) in the cycle of oxidative deterioration of polypropylene resin. By using the above-mentioned light stabilizer together with such a hydroxylamine-based antioxidant, the amount of these additives used can be kept low compared to conventional methods, and processing stability and film formation during film formation can be improved. Later long-term thermal stability can be obtained.
　ヒドロキシルアミン系の酸化防止剤としては、ヒドロキシルアミンの窒素原子に炭化水素基が二つ付加した、ジアルキルヒドロキシルアミンを用いることが好ましい。ジアルキルヒドロキシルアミンはポリプロピレン樹脂との相溶性が良好であり、ポリプロピレン樹脂内で一様に分散し易いため、ポリプロピレン樹脂の酸化防止機能をより効果的に発揮できる。酸化防止剤がフィルム表面にブリードアウトすることを抑制し易い観点から、炭化水素基は飽和直鎖炭化水素基であることが好ましく、炭化水素基に含まれる炭素数は１２以上であることが好ましい。炭化水素基としては、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基等が挙げられる。 As the hydroxylamine-based antioxidant, it is preferable to use dialkylhydroxylamine, which has two hydrocarbon groups added to the nitrogen atom of hydroxylamine. Dialkylhydroxylamine has good compatibility with polypropylene resin and is easily dispersed uniformly within the polypropylene resin, so that it can more effectively exhibit the antioxidant function of the polypropylene resin. From the viewpoint of easily suppressing the antioxidant from bleeding out onto the film surface, the hydrocarbon group is preferably a saturated linear hydrocarbon group, and the number of carbon atoms contained in the hydrocarbon group is preferably 12 or more. . Examples of the hydrocarbon group include dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, and the like.
　ジアルキルヒドロキシルアミンとしては、ビス－オクタデシルヒドロキシルアミンを用いることが特に好ましい。ビス－オクタデシルヒドロキシルアミンを用いることで、ポリプロピレン樹脂の酸化劣化を防ぐ機能に加えて、製膜されたフィルムにガンマ線等の放射線や電子線を照射した際に、フィルムの変色及びポリプロピレン樹脂の分解を防ぐ機能を付与できる。 As the dialkylhydroxylamine, it is particularly preferable to use bis-octadecylhydroxylamine. By using bis-octadecylhydroxylamine, in addition to the function of preventing oxidative deterioration of polypropylene resin, it also prevents discoloration of the film and decomposition of polypropylene resin when the formed film is irradiated with radiation such as gamma rays or electron beams. A function to prevent this can be added.
　酸化防止剤は、ヒドロキシルアミン系の酸化防止剤に加えて、一次酸化防止機能又は二次酸化防止機能を有する他の酸化防止剤を更に含んでいてもよい。他の酸化防止剤として、例えばヒンダードフェノール系の酸化防止剤のような、パーオキシラジカル（ＲＯＯ・）を捕捉する一次酸化防止機能を有する酸化防止剤、リン系酸化防止剤、イオウ系酸化防止剤等のような、ハイドロパーオキサイド（ＲＯＯＨ）を分解する二次酸化防止機能を有する二次酸化防止剤などが挙げられる。このような酸化防止剤を用いることで、ポリプロピレン樹脂の酸化劣化のサイクルの進行をより抑制し易くなる。ただし、添加剤の加水分解反応抑制や、添加剤の合計含有量を低く抑える観点から、酸化防止剤に含まれる、ヒドロキシルアミン系の酸化防止剤の量は、５０質量％以上又は８０質量％以上であることが好ましく、１００質量％であってもよい。 In addition to the hydroxylamine-based antioxidant, the antioxidant may further contain another antioxidant having a primary antioxidant function or a secondary antioxidant function. Other antioxidants include antioxidants that have a primary antioxidant function that captures peroxy radicals (ROO), such as hindered phenol antioxidants, phosphorus antioxidants, and sulfur antioxidants. Examples include secondary antioxidants having a secondary antioxidant function of decomposing hydroperoxide (ROOH) such as ROOH. By using such an antioxidant, it becomes easier to suppress the progress of the cycle of oxidative deterioration of the polypropylene resin. However, from the viewpoint of suppressing the hydrolysis reaction of additives and keeping the total content of additives low, the amount of hydroxylamine-based antioxidant contained in the antioxidant should be 50% by mass or more or 80% by mass or more. is preferable, and may be 100% by mass.
　ヒンダードフェノール系の酸化防止剤としては、２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノール、３－（３，５－ジ－ｔｅｒｔ－ブチル－４―ヒドロキシフェニル）プロピオン酸ステアリル、テトラキス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオン酸］ペンタエリトリトール等が挙げられる。 Examples of hindered phenol antioxidants include 2,6-di-tert-butyl-4-methylphenol, stearyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and tetrakis[ Examples include pentaerythritol (3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid).
　ポリプロピレン樹脂、光安定剤、及び酸化防止剤の全量を基準として、光安定剤の含有量は１５０質量ｐｐｍ以上であると好ましく、酸化防止剤の含有量は１５０質量ｐｐｍ以上であると好ましい。これにより、ポリプロピレン樹脂の酸化劣化を防ぐ効果が得られ易い。この観点から、光安定剤の含有量は２５０質量ｐｐｍ以上、又は５００質量ｐｐｍ以上であるとより好ましく、酸化防止剤の含有量は２５０質量ｐｐｍ以上又は５００質量ｐｐｍ以上であるとより好ましい。
　また、ポリプロピレン樹脂、光安定剤、及び酸化防止剤の全量を基準として、光安定剤及び酸化防止剤の合計含有量は２５００質量ｐｐｍ以下であると好ましい。これにより、フィルム表面への光安定剤及び酸化防止剤、あるいはそれらの分解物等のブリードアウト、押出機や引取機等の設備の汚損、後工程の際のトラブル等を抑制し易い。この観点から、光安定剤及び酸化防止剤の合計含有量は２０００質量ｐｐｍ以下、又は１５００質量ｐｐｍ以下であるとより好ましい。同様の観点から、光安定剤の含有量は１２５０質量ｐｐｍ以下とすることができ、酸化防止剤の含有量は１２５０質量ｐｐｍ以下とすることができる。 The content of the light stabilizer is preferably 150 mass ppm or more, and the antioxidant content is preferably 150 mass ppm or more, based on the total amount of the polypropylene resin, light stabilizer, and antioxidant. Thereby, it is easy to obtain the effect of preventing oxidative deterioration of the polypropylene resin. From this viewpoint, the content of the light stabilizer is more preferably 250 mass ppm or more or 500 mass ppm or more, and the antioxidant content is more preferably 250 mass ppm or more or 500 mass ppm or more.
Further, the total content of the light stabilizer and antioxidant is preferably 2500 mass ppm or less based on the total amount of the polypropylene resin, light stabilizer, and antioxidant. This makes it easy to suppress bleed-out of light stabilizers and antioxidants or their decomposed products onto the film surface, staining of equipment such as extruders and take-off machines, and troubles during post-processing. From this viewpoint, the total content of the light stabilizer and antioxidant is more preferably 2000 mass ppm or less, or 1500 mass ppm or less. From the same viewpoint, the content of the light stabilizer can be 1250 mass ppm or less, and the antioxidant content can be 1250 mass ppm or less.
　酸化防止剤の含有量に対する光安定剤の含有量の質量比（光安定剤の含有量／酸化防止剤の含有量）は、０．１～２であることが好ましく、０．２～１であることがより好ましい。これにより、ポリプロピレン樹脂の酸化劣化を防ぐ効果が得られ易い。 The mass ratio of the light stabilizer content to the antioxidant content (light stabilizer content/antioxidant content) is preferably 0.1 to 2, and preferably 0.2 to 1. It is more preferable that there be. Thereby, it is easy to obtain the effect of preventing oxidative deterioration of the polypropylene resin.
（その他の成分）
　樹脂組成物は、その他の成分として、触媒残渣を中和するための中和剤、ポリプロピレンの結晶化の際の核となる核剤、フィルム表面の摩擦係数を低下させるための滑剤、フィルムを巻き取った状態で保管する際のブロッキングを防止するアンチブロッキング剤、フィルム表面への異物の付着やフィルムが帯電して加工機や他のフィルムに付着することを防ぐ帯電防止剤、等の成分（他の添加剤）を、実際の使用用途に応じて適宜含有することができる。 (Other ingredients)
The resin composition contains, as other components, a neutralizing agent to neutralize catalyst residue, a nucleating agent to act as a core during crystallization of polypropylene, a lubricant to reduce the coefficient of friction on the film surface, and a film to be wound. Ingredients such as anti-blocking agents to prevent blocking when stored in the removed state, anti-static agents to prevent foreign matter from adhering to the film surface and the film from being charged and adhering to processing machines and other films (other additives) may be included as appropriate depending on the actual use.
＜ポリプロピレンフィルム＞
　ポリプロピレンフィルムは、上記ポリプロピレンフィルム形成用樹脂組成物から製膜される。ポリプロピレンフィルムの製膜方法としては、例えば熱プレス、押出成形、キャスティング成形、カレンダー成形等の各種方法を適宜選択できる。ポリプロピレンフィルムには、１軸延伸、逐次２軸延伸、同時２軸延伸、多段延伸等の各種延伸加工が施されてもよい。 <Polypropylene film>
A polypropylene film is formed from the above resin composition for forming a polypropylene film. As a method for forming a polypropylene film, various methods such as hot pressing, extrusion molding, casting molding, and calender molding can be appropriately selected. The polypropylene film may be subjected to various stretching processes such as uniaxial stretching, sequential biaxial stretching, simultaneous biaxial stretching, and multistage stretching.
　ポリプロピレンフィルムの（すなわちポリプロピレンフィルムを構成するポリプロピレン樹脂の）メルトフローレート（ＪＩＳ　Ｋ６９２１－２準拠、温度２３０℃、荷重２．１６ｋｇ）は、２０．０ｇ／１０ｍｉｎ以下であると好ましい。このことは、光安定剤及び酸化防止剤が充分に機能し、フィルムを製膜する際の押出機の熱によってポリプロピレン樹脂の酸化劣化が進行し難い傾向があることを示す。メルトフローレートは、１３．０ｇ／１０ｍｉｎ以下であるとより好ましい。メルトフローレートが２０．０ｇ／１０ｍｉｎを超える場合は、ポリプロピレン樹脂の溶融粘度が低く、Ｔダイからの吐出量が安定し難いため、製膜されるフィルムの膜厚が変動し易い傾向がある。さらに、製膜されたフィルムの耐衝撃性が低下し易い傾向がある。メルトフローレートの下限は特に限定されないが、上述したポリプロピレン樹脂を用いる場合は、３．０ｇ／１０ｍｉｎ以上とすることができる。 The melt flow rate (according to JIS K6921-2, temperature 230° C., load 2.16 kg) of the polypropylene film (that is, the polypropylene resin constituting the polypropylene film) is preferably 20.0 g/10 min or less. This indicates that the light stabilizer and antioxidant function sufficiently and that oxidative deterioration of the polypropylene resin tends to be difficult to progress due to the heat of the extruder during film formation. The melt flow rate is more preferably 13.0 g/10 min or less. When the melt flow rate exceeds 20.0 g/10 min, the melt viscosity of the polypropylene resin is low and the discharge amount from the T-die is difficult to stabilize, so the thickness of the film formed tends to fluctuate easily. Furthermore, the impact resistance of the formed film tends to decrease. The lower limit of the melt flow rate is not particularly limited, but when using the above-mentioned polypropylene resin, it can be set to 3.0 g/10 min or more.
　ポリプロピレンフィルム中の光安定剤及び酸化防止剤の種類及びその量は、例えば溶出試験（フィルムを溶媒に浸して酸化防止剤等の添加剤を抽出する方法）により特定することができる。 The type and amount of the light stabilizer and antioxidant in the polypropylene film can be determined, for example, by an elution test (a method in which the film is immersed in a solvent to extract additives such as the antioxidant).
　ポリプロピレンフィルム中において、光安定剤及び酸化防止剤が充分に機能するためには、これらの添加剤の分解が進行し難いことが必要である。添加剤の分解により添加剤本来の機能低下が生じるだけでなく、分解物の種類や量が法規制上好ましくない場合がある。ポリプロピレンフィルム中での添加剤の安定性（分解の程度）は、例えば以下のようにして評価することができる。以下に示すピーク面積値比（（Ｂ－Ｂ’）／（Ａ－Ａ’））が１．０以上１．６未満であると、添加剤の分解が進行し難く、添加剤が安定して存在するポリプロピレンフィルムであるということができる。ピーク面積値比は、好ましくは１．５以下、より好ましくは１．４以下である。
＜ピーク面積値比算出方法＞
　ポリプロピレンフィルムをＡ４サイズ（幅方向２１０ｍｍ×流れ方向２９１ｍｍ）に切り出し、恒温機にて、設定温度１５０℃で６０日間保管する。これにより、ポリプロピレンフィルムに劣化処理を行う。
　劣化処理前後のフィルムをそれぞれ１０ｃｍ角に切り出し、短冊状にカットしてバイアル瓶に入れ、エタノールを１０ｍｌ加えて密封する。フィルムがエタノールと接する面積（接液面積）は０.０５ｍｌ／ｃｍ２以下となるように調整する。
　バイアル瓶を６０℃に設定したドライオーブンに１０日間保管する。
　得られたエタノール抽出液を回収し、ＧＣ／ＭＳ分析に供する。
　ＧＣ／ＭＳ分析により、得られたトータルイオンクロマトグラムを解析する。劣化処理前のフィルム抽出液のトータルイオンクロマトグラムから、保持時間６～４０分までのピークに対してベースラインを引いて合計のピーク面積値（Ａ）を求めた後、炭化水素（ポリプロピレン樹脂由来）のピーク面積値（Ａ’）を差し引いた（Ａ－Ａ’）を算出する。炭化水素のピークは添加剤不使用のポリプロピレンフィルムで検出されたピークと比較し、保持時間とマススペクトルが同じピークを対象とする。
　劣化処理後のフィルム抽出液についても上記と同様に合計ピーク面積値（Ｂ）を求めた後、炭化水素のピーク面積値（Ｂ’）を差し引いて（Ｂ－Ｂ’）を算出する。
　これらの結果から、ピーク面積値比（（Ｂ－Ｂ’）／（Ａ－Ａ’））を算出する。 In order for the light stabilizer and antioxidant to function satisfactorily in the polypropylene film, it is necessary that these additives are difficult to decompose. Decomposition of the additive not only causes a decline in the original function of the additive, but also the type and amount of the decomposed product may be unfavorable in terms of laws and regulations. The stability (degree of decomposition) of the additive in the polypropylene film can be evaluated, for example, as follows. When the peak area value ratio ((BB')/(AA')) shown below is 1.0 or more and less than 1.6, the decomposition of the additive is difficult to proceed and the additive is stable. It can be said that it is a polypropylene film that exists. The peak area value ratio is preferably 1.5 or less, more preferably 1.4 or less.
<Peak area value ratio calculation method>
A polypropylene film is cut into A4 size (width direction 210 mm x flow direction 291 mm) and stored in a constant temperature machine at a set temperature of 150° C. for 60 days. This performs a deterioration treatment on the polypropylene film.
The films before and after the deterioration treatment are each cut into 10 cm square pieces, cut into strips, placed in a vial, and 10 ml of ethanol is added and sealed. The area of the film in contact with ethanol (liquid contact area) is adjusted to be 0.05 ml/cm 2 or less.
Store the vial in a dry oven set at 60°C for 10 days.
The obtained ethanol extract is collected and subjected to GC/MS analysis.
The obtained total ion chromatogram is analyzed by GC/MS analysis. From the total ion chromatogram of the film extract before deterioration treatment, the baseline was subtracted from the peaks at retention times of 6 to 40 minutes to determine the total peak area value (A). ) is calculated by subtracting the peak area value (A') of (AA'). The hydrocarbon peaks are compared with the peaks detected in the polypropylene film without additives, and the peaks with the same retention time and mass spectrum are targeted.
After determining the total peak area value (B) for the film extract after the deterioration treatment in the same manner as above, the peak area value (B') of hydrocarbons is subtracted to calculate (BB').
From these results, the peak area value ratio ((BB')/(AA')) is calculated.
　ポリプロピレンフィルムの厚さは特に制限されないが、１０～３００μｍとすることができる。厚さが１０μｍ以上であると、製膜後の工程やフィルム取扱い中における破断や引裂等のトラブルが発生し難く、厚さが３００μｍ以下であると、製膜後の巻き取りの際に、フィルムに巻き癖が付いたり、張力が不十分で緩く巻かれたりといったトラブルが発生し難い。 The thickness of the polypropylene film is not particularly limited, but can be 10 to 300 μm. If the thickness is 10 μm or more, troubles such as breakage or tearing during the process after film formation or during film handling will be less likely to occur, and if the thickness is 300 μm or less, the film will not be easily damaged during winding after film formation. Troubles such as curling or loose winding due to insufficient tension are less likely to occur.
＜積層体＞
　積層体は上記ポリプロピレンフィルムを備える。ポリプロピレンフィルムは単層フィルムとして製膜されてもよいが、複数の押出機を使用し、同一の又は異なる種類のポリプロピレン樹脂をフィードブロック法又はマルチマニホールド法により共押出することで、２層以上の多層フィルムとして製膜されてもよい。すなわち積層体は、同一の又は異なる種類の複数のポリプロピレンフィルムを備えることができる。 <Laminated body>
The laminate includes the polypropylene film described above. A polypropylene film may be produced as a single layer film, but it can be made into two or more layers by using multiple extruders and coextruding the same or different types of polypropylene resin by a feed block method or a multi-manifold method. It may also be formed as a multilayer film. That is, the laminate can include a plurality of polypropylene films of the same or different types.
　積層体は、単層又は多層のポリプロピレンフィルムの片面又は両面に、包装材料として既知の各種の層を備えることができる。そのような層としては、シーラント層、金属箔層、蒸着層（アルミ蒸着層、アルミナ蒸着層、シリカ蒸着層等）、印刷層、接着層、表面保護層等が挙げられる。それらの層は、ドライラミネート、熱接着、フィルム表面への印刷、塗工、蒸着等の既知の方法により積層することができる。なお、ポリプロピレンフィルムに対して蒸着層を設けることで、酸化防止剤の含有量を抑制しつつ、バリア安定性を持つフィルムとして好適に使用できる。 The laminate can include various layers known as packaging materials on one or both sides of a single-layer or multi-layer polypropylene film. Examples of such layers include a sealant layer, a metal foil layer, a vapor deposition layer (aluminum vapor deposition layer, alumina vapor deposition layer, silica vapor deposition layer, etc.), a printing layer, an adhesive layer, a surface protection layer, and the like. These layers can be laminated by known methods such as dry lamination, thermal adhesion, printing on the film surface, coating, vapor deposition, and the like. Note that by providing a vapor deposited layer on a polypropylene film, it can be suitably used as a film having barrier stability while suppressing the antioxidant content.
　積層体の例として、例えば以下のようなものが挙げられる。
　上記ポリプロピレン樹脂とポリエチレン樹脂とを共押出した、ポリプロピレン（２０μｍ）／ポリエチレン（６０μｍ）の層構成を有する積層体。
　上記ポリプロピレン樹脂とエチレン－ビニルアルコール共重合体樹脂とポリエチレン樹脂とを共押出した、ポリプロピレン（２０μｍ）／エチレン－ビニルアルコール共重合体（１５μｍ）／ポリエチレン（６０μｍ）の層構成を有する積層体。
　表面にアルミ蒸着層を有するポリエチレンテレフタラートフィルムに対して、上記ポリプロピレン樹脂及びポリエチレン樹脂を押出ラミネートした、ポリプロピレン（２０μｍ）／アルミ蒸着ポリエチレンテレフタラート（１２μｍ）／ポリエチレン（６０μｍ）の層構成を有する積層体。 Examples of the laminate include the following.
A laminate having a layer structure of polypropylene (20 μm)/polyethylene (60 μm), which is obtained by coextruding the above polypropylene resin and polyethylene resin.
A laminate having a layer structure of polypropylene (20 μm)/ethylene-vinyl alcohol copolymer (15 μm)/polyethylene (60 μm), which is obtained by coextruding the above polypropylene resin, ethylene-vinyl alcohol copolymer resin, and polyethylene resin.
A laminate having a layer structure of polypropylene (20 μm)/aluminum deposited polyethylene terephthalate (12 μm)/polyethylene (60 μm), which is obtained by extrusion laminating the above polypropylene resin and polyethylene resin on a polyethylene terephthalate film having an aluminum vapor deposited layer on the surface. body.
＜本実施形態の概要＞
［発明１］
　ポリプロピレン樹脂と、
　炭素ラジカルを捕捉する機能を有するヒンダードアミン系の光安定剤と、
　一次酸化防止機能及び二次酸化防止機能を有するヒドロキシルアミン系の酸化防止剤と、を含む、ポリプロピレンフィルム形成用樹脂組成物。
［発明２］
　前記ヒドロキシルアミン系の酸化防止剤がジアルキルヒドロキシルアミンである、発明１に記載の樹脂組成物。
［発明３］
　前記ヒドロキシルアミン系の酸化防止剤がビス－オクタデシルヒドロキシルアミンである、発明２に記載の樹脂組成物。
［発明４］
　前記ヒンダードアミン系の光安定剤の重量平均分子量が２０００未満である、発明１～３のいずれか一に記載の樹脂組成物。
［発明５］
　前記ヒンダードアミン系の光安定剤がセバシン酸ビス（２，２，６，６－テトラメチル－４－ピペリジル）である、発明４に記載の樹脂組成物。
［発明６］
　前記ポリプロピレン樹脂、前記光安定剤及び前記酸化防止剤の全量を基準として、前記光安定剤の含有量が１５０質量ｐｐｍ以上であり、前記酸化防止剤の含有量が１５０質量ｐｐｍ以上であり、前記光安定剤及び前記酸化防止剤の合計含有量が２５００質量ｐｐｍ以下である、発明１～５のいずれか一に記載の樹脂組成物。
［発明７］
　発明１～６のいずれか一に記載の樹脂組成物から製膜されるポリプロピレンフィルム。
［発明８］
　メルトフローレート（ＪＩＳ　Ｋ６９２１－２準拠、温度２３０℃、荷重２．１６ｋｇ）が２０．０ｇ／１０ｍｉｎ以下である、発明７に記載のフィルム。
［発明９］
　発明７又は８に記載のフィルムを備える積層体。 <Overview of this embodiment>
[Invention 1]
polypropylene resin,
A hindered amine light stabilizer that has the function of capturing carbon radicals,
A resin composition for forming a polypropylene film, comprising a hydroxylamine-based antioxidant having a primary antioxidant function and a secondary antioxidant function.
[Invention 2]
The resin composition according to invention 1, wherein the hydroxylamine-based antioxidant is dialkylhydroxylamine.
[Invention 3]
The resin composition according to invention 2, wherein the hydroxylamine-based antioxidant is bis-octadecylhydroxylamine.
[Invention 4]
The resin composition according to any one of inventions 1 to 3, wherein the hindered amine light stabilizer has a weight average molecular weight of less than 2,000.
[Invention 5]
The resin composition according to invention 4, wherein the hindered amine light stabilizer is bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate.
[Invention 6]
Based on the total amount of the polypropylene resin, the light stabilizer, and the antioxidant, the content of the light stabilizer is 150 mass ppm or more, the content of the antioxidant is 150 mass ppm or more, and the The resin composition according to any one of inventions 1 to 5, wherein the total content of the light stabilizer and the antioxidant is 2500 mass ppm or less.
[Invention 7]
A polypropylene film produced from the resin composition according to any one of inventions 1 to 6.
[Invention 8]
The film according to invention 7, which has a melt flow rate (according to JIS K6921-2, temperature 230° C., load 2.16 kg) of 20.0 g/10 min or less.
[Invention 9]
A laminate comprising the film according to invention 7 or 8.
　以下、本発明に基づく実施例を説明するが、本発明は以下の実施例に限定されるものではない。 Examples based on the present invention will be described below, but the present invention is not limited to the following examples.
（実施例１）
　ポリプロピレン樹脂の原料として、サンアロマー株式会社製のＰＸ６００Ｎ（プロピレン単独重合体）を用いた。また、光安定剤として、ヒンダードアミン系の光安定剤である、Ｃｈｉｔｅｃ　Ｔｅｃｈｎｏｌｏｇｙ株式会社製のＣｈｉｇｕａｒｄ７７０（主成分：セバシン酸ビス（２，２，６，６－テトラメチル－４－ピペリジル））を、酸化防止剤として、一次酸化防止機能及び二次酸化防止機能を有するヒドロキシルアミン系の酸化防止剤である、ビス－オクタデシルヒドロキシルアミンを用いた。 (Example 1)
PX600N (propylene homopolymer) manufactured by Sun Allomer Co., Ltd. was used as a raw material for the polypropylene resin. In addition, as a light stabilizer, Chiguard 770 (main component: bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate) manufactured by Chitec Technology Co., Ltd., which is a hindered amine light stabilizer, was oxidized. As the inhibitor, bis-octadecylhydroxylamine, which is a hydroxylamine-based antioxidant having a primary antioxidant function and a secondary antioxidant function, was used.
　ＰＸ６００Ｎに、ポリプロピレン樹脂、光安定剤及び酸化防止剤の全量を基準として、Ｃｈｉｇｕａｒｄ７７０を２５０質量ｐｐｍ、ビス－オクタデシルヒドロキシルアミンを２５０質量ｐｐｍ添加した。この樹脂組成物を押出機に供給して加熱溶融し、Ｔダイから吐出させ、ニップ圧力を付加しながら冷却ロールに接触させてフィルムを製膜した。押出機の設定温度は、供給部を２３０℃、圧縮部、計量部及びＴダイを２５０℃とした。フィルムの厚さは６０μｍとした。 To PX600N, 250 mass ppm of Chiguard 770 and 250 mass ppm of bis-octadecylhydroxylamine were added, based on the total amount of polypropylene resin, light stabilizer, and antioxidant. This resin composition was supplied to an extruder, heated and melted, discharged from a T-die, and brought into contact with a cooling roll while applying nip pressure to form a film. The set temperature of the extruder was 230° C. for the supply section, and 250° C. for the compression section, measuring section, and T-die. The thickness of the film was 60 μm.
（実施例２～４、比較例１～４）
　Ｃｈｉｇｕａｒｄ７７０及びビス－オクタデシルヒドロキシルアミンの量を表１のとおり変更したこと以外は、実施例１と同様にフィルムを製膜した。 (Examples 2-4, Comparative Examples 1-4)
A film was formed in the same manner as in Example 1, except that the amounts of Chiguard 770 and bis-octadecylhydroxylamine were changed as shown in Table 1.
（比較例５）
　Ｃｈｉｇｕａｒｄ７７０及びビス－オクタデシルヒドロキシルアミンに代えて、一次酸化防止機能を有する（一次酸化防止剤としての機能のみを有する）、ヒンダードフェノール系の酸化防止剤である、ＢＡＳＦジャパン株式会社製のＩｒｇａｎｏｘ１０１０（主成分：テトラキス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオン酸］ペンタエリトリトール）を１０００質量ｐｐｍ、二次酸化防止機能を有する（二次酸化防止剤としての機能のみを有する）、リン系の酸化防止剤であるＢＡＳＦジャパン株式会社製のＩｒｇａｆｏｓ１６８を２０００質量ｐｐｍ添加したこと以外は、実施例１と同様にフィルムを製膜した。 (Comparative example 5)
In place of Chiguard 770 and bis-octadecylhydroxylamine, Irganox 1010 (mainly manufactured by BASF Japan Co., Ltd.), which is a hindered phenol antioxidant that has a primary antioxidant function (has only the function of a primary antioxidant), is used. Ingredients: 1000 ppm by mass of tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol), which has a secondary antioxidant function (only functions as a secondary antioxidant) A film was formed in the same manner as in Example 1, except that 2000 mass ppm of Irgafos 168 manufactured by BASF Japan Co., Ltd., which is a phosphorus-based antioxidant, was added.
（比較例６）
　Ｉｒｇａｎｏｘ１０１０及びＩｒｇａｆｏｓ１６８の量を表１のとおり変更したこと以外は、比較例５と同様にフィルムを製膜した。 (Comparative example 6)
A film was formed in the same manner as in Comparative Example 5, except that the amounts of Irganox 1010 and Irgafos 168 were changed as shown in Table 1.
（評価：メルトフローレート測定）
　各例のフィルムについて、株式会社東洋精機製作所製のメルトインデックサ（Ｆ－Ｆ－０１）を使用し、ＪＩＳ　Ｋ６９２１－２準拠のメルトフローレート（Ｍｅｌｔ　Ｆｌｏｗ　Ｒａｔｅ；ＭＦＲ）を測定した。メルトインデックサの設定温度は２３０℃とした。各例のフィルムをそれぞれ５ｍｍ角程度のサイズに切り出してサンプルとした。サンプルの重量は約５ｇ（５±１ｇ程度）であった。このサンプルをメルトインデックサに投入し、２．１６ｋｇの荷重を印加した状態で３０秒間に吐出される樹脂の質量を測定した。この測定値を２０倍してＭＦＲの値を算出した。結果を表１に示す。 (Evaluation: Melt flow rate measurement)
The melt flow rate (MFR) of each film in accordance with JIS K6921-2 was measured using a melt indexer (FF-01) manufactured by Toyo Seiki Seisakusho Co., Ltd. The set temperature of the melt indexer was 230°C. The film of each example was cut into a size of about 5 mm square to prepare a sample. The weight of the sample was approximately 5 g (approximately 5±1 g). This sample was placed in a melt indexer, and the mass of resin discharged in 30 seconds was measured with a load of 2.16 kg applied. This measured value was multiplied by 20 to calculate the MFR value. The results are shown in Table 1.
（評価：フィルム耐久性）
　各例のフィルムをＡ４サイズ（幅方向２１０ｍｍ×流れ方向２９１ｍｍ）に切り出し、エスペック株式会社製の恒温機（ＨＴ３１０）にて、設定温度１５０℃で６０日間保管した。各例のフィルムが酸化劣化して脆くなる（軽く触れたり曲げたりしただけで割れて粉々になる）までの日数を記録することで、フィルムの耐久性を評価した。結果を表１に示す。 (Evaluation: Film durability)
The film of each example was cut into an A4 size (210 mm in the width direction x 291 mm in the machine direction) and stored in a constant temperature machine (HT310) manufactured by ESPEC Co., Ltd. at a set temperature of 150° C. for 60 days. The durability of each film was evaluated by recording the number of days until the film of each example deteriorated due to oxidation and became brittle (it would crack and shatter with just a light touch or bending). The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　炭素ラジカルを捕捉する機能を有する光安定剤であるＣｈｉｇｕａｒｄ７７０と、一次酸化防止機能及び二次酸化防止機能を併せ持つビス－オクタデシルヒドロキシルアミンとを添加して製膜した実施例のフィルムは、光安定剤及び酸化防止剤を添加せずに製膜した比較例１のフィルム、並びにＣｈｉｇｕａｒｄ７７０のみを添加して製膜した比較例２及び比較例３のフィルムと比較して、メルトフローレートの値が低く抑えられていた。実施例は、押出機の熱によるポリプロピレン樹脂の酸化劣化が比較的進行し難く、加工安定性が良好であることを示している。 The film of the example was formed by adding Chiguard 770, a light stabilizer that has the function of capturing carbon radicals, and bis-octadecylhydroxylamine, which has both primary and secondary antioxidant functions. The melt flow rate value was kept low compared to the film of Comparative Example 1, which was formed without adding any antioxidant, and the films of Comparative Example 2 and Comparative Example 3, which were formed by adding only Chiguard 770. It was getting worse. The examples show that the oxidative deterioration of the polypropylene resin due to the heat of the extruder is relatively difficult to progress, and the processing stability is good.
　実施例のフィルムは、６０日間のフィルム耐久性評価を実施した際にフィルムの破断は見られなかった。これに対して、ビス－オクタデシルヒドロキシルアミンのみを添加して製膜した比較例４のフィルムでは、メルトフローレートの値が比較的低く抑えられているものの、フィルム耐久性評価を実施した際に恒温機投入後１日でフィルムの破断が見られ、長期熱安定性に乏しいことが確認された。 In the film of the example, no film breakage was observed when the film durability was evaluated for 60 days. On the other hand, in the film of Comparative Example 4, which was formed by adding only bis-octadecylhydroxylamine, although the melt flow rate value was kept relatively low, when the film durability was evaluated, The film was observed to break one day after being put into the machine, confirming that it had poor long-term thermal stability.
　一次酸化防止機能を有する酸化防止剤であるＩｒｇａｎｏｘ１０１０と、二次酸化防止機能を有する酸化防止剤であるＩｒｇａｆｏｓ１６８とを添加して製膜した比較例５のフィルムでは、メルトフローレートの値が低く抑えられており、６０日間のフィルム耐久性評価を実施した際にフィルムの破断は見られなかった。ただし、実施例のフィルムと比較して光安定剤及び酸化防止剤の含有量の合計が多かった。含有量が多いことで、フィルム表面に光安定剤及び酸化防止剤、あるいはそれらの分解物等がブリードアウトし、押出機や引取機等の設備の汚損、後工程の際のトラブル等のような不都合が生じる虞がある。 In the film of Comparative Example 5, which was formed by adding Irganox 1010, an antioxidant that has a primary antioxidant function, and Irgafos 168, an antioxidant that has a secondary antioxidant function, the melt flow rate value was kept low. No breakage of the film was observed when the film durability was evaluated for 60 days. However, the total content of light stabilizer and antioxidant was higher than that of the film of Example. If the content is high, light stabilizers, antioxidants, or their decomposition products may bleed out onto the film surface, resulting in contamination of equipment such as extruders and take-off machines, and troubles during post-processing. There is a possibility that inconvenience may occur.
　また、Ｉｒｇａｎｏｘ１０１０と、Ｉｒｇａｆｏｓ１６８とを、含有量の合計が実施例３と同様に１５００質量ｐｐｍとなるように製膜した比較例６のフィルムでは、６０日間のフィルム耐久性評価を実施した際にフィルムの破断は見られなかったが、メルトフローレートの値は実施例３のフィルムよりも大きく、加工安定性に乏しいことが確認された。 In addition, in the film of Comparative Example 6, in which Irganox 1010 and Irgafos 168 were formed into a film such that the total content was 1500 mass ppm as in Example 3, when the film durability was evaluated for 60 days, the film Although no breakage was observed, the melt flow rate value was higher than that of the film of Example 3, confirming that the film had poor processing stability.
（評価：添加剤安定性）
　各例のフィルムをＡ４サイズ（幅方向２１０ｍｍ×流れ方向２９１ｍｍ）に切り出し、エスペック株式会社製の恒温機（ＨＴ３１０）にて、設定温度１５０℃で６０日間保管した。これによりフィルムに劣化処理を行った。
　劣化処理前後の各例のフィルムを、それぞれ１０ｃｍ角に切り出し、短冊状にカットしてバイアル瓶に入れ、エタノール（関東化学製、試薬特級、９９．５％純度）を１０ｍｌ加えて密封した。なお、フィルムがエタノールと接する面積（接液面積）は０.０５ｍｌ／ｃｍ２以下となるように調整した。
　バイアル瓶を６０℃に設定したドライオーブン（アズワン製、ＤＯ－４５０Ａ）に１０日間保管した。その後、得られたエタノール抽出液を回収し、ＧＣ／ＭＳ分析に供した。 (Evaluation: Additive stability)
The film of each example was cut into an A4 size (210 mm in the width direction x 291 mm in the machine direction) and stored in a constant temperature machine (HT310) manufactured by ESPEC Co., Ltd. at a set temperature of 150° C. for 60 days. This subjected the film to deterioration treatment.
The films of each example before and after the deterioration treatment were cut into 10 cm square pieces, cut into strips, placed in a vial, and 10 ml of ethanol (manufactured by Kanto Kagaku, special reagent grade, 99.5% purity) was added and sealed. The area of the film in contact with ethanol (liquid contact area) was adjusted to be 0.05 ml/cm 2 or less.
The vial was stored in a dry oven (DO-450A manufactured by As One) set at 60° C. for 10 days. Thereafter, the obtained ethanol extract was collected and subjected to GC/MS analysis.
　ＧＣ／ＭＳ分析条件を下記に示す。
装置型番：ＧＣ６８９０／５９７３ＭＳＤ（Ａｇｉｌｅｎｔ　Ｔｅｃｈｎｏｌｏｇｉｅｓ製）
＜ＧＣ条件＞
カラム：ＨＰ－５ＭＳ　５％Ｐｈｅｎｙｌ　９５％Ｍｅｔｈｙｌ　Ｐｏｌｙ　Ｓｉｌｏｘａｎｅ、３０ｍ×０．２５ｍｍｉｄ（内径）×０．２５μｍ　（Ａｇｉｌｅｎｔ　Ｔｅｃｈｎｏｌｏｇｉｅｓ製）
カラム温度：４０℃（１ｍｉｎ．）→１０℃／ｍｉｎ．→３２０℃（１５ｍｉｎ．）
ランタイム：４４．００ｍｉｎ．
キャリアガス：Ｈｅ（コンスタントフローモード：１．０ｍｌ／ｍｉｎ．）
パルス圧力：２０ｐｓｉ
パルス時間：１．５ｍｉｎ．
注入量：２μｌ
注入法：パルスドスプリッドレス
注入口温度：２８０℃
溶媒待ち時間：６．０ｍｉｎ．
＜ＭＳ条件＞
インターフェイス温度：３００℃
イオン化法：ＥＩ
イオン化電圧：７０ｅＶ
イオン源温度：２３０℃
四重極温度１５０℃
マスレンジ：ｍ／ｚ＝３３～８００（ｓｃａｎモード） The GC/MS analysis conditions are shown below.
Device model number: GC6890/5973MSD (manufactured by Agilent Technologies)
<GC conditions>
Column: HP-5MS 5% Phenyl 95% Methyl Poly Siloxane, 30 m x 0.25 mm (inner diameter) x 0.25 μm (manufactured by Agilent Technologies)
Column temperature: 40°C (1 min.) → 10°C/min. →320℃ (15min.)
Runtime: 44.00min.
Carrier gas: He (constant flow mode: 1.0ml/min.)
Pulse pressure: 20psi
Pulse time: 1.5min.
Injection volume: 2μl
Injection method: Pulsed splitless Inlet temperature: 280℃
Solvent waiting time: 6.0min.
<MS conditions>
Interface temperature: 300℃
Ionization method: EI
Ionization voltage: 70eV
Ion source temperature: 230℃
Quadrupole temperature 150℃
Mass range: m/z=33-800 (scan mode)
　上記分析条件にて各例のフィルム抽出液をＧＣ／ＭＳで分析し、得られたトータルイオンクロマトグラムをＭＳＤ　ＣｈｅｍＳｔａｔｉｏｎ（Ｅ．０２．０２．１４３１）を用いて解析した。劣化処理前におけるフィルム抽出液のトータルイオンクロマトグラムから、保持時間６～４０分までのピークに対してベースラインを引いて合計のピーク面積値（Ａ）を求めた後、炭化水素（ポリプロピレン樹脂由来）のピーク面積値（Ａ’）を差し引いた（Ａ－Ａ’）を算出した。この際、添加剤不使用のポリプロピレンフィルム（比較例１）で検出されたピークと比較し、保持時間とマススペクトルが同じピークを炭化水素のピークとした。
　劣化処理後のフィルム抽出液についても上記と同様に合計ピーク面積値（Ｂ）を求めた後、炭化水素のピーク面積値（Ｂ’）を差し引いて（Ｂ－Ｂ’）を算出した。
　これらの結果から、ピーク面積値比（（Ｂ－Ｂ’）／（Ａ－Ａ’））を算出した。
　一例として実施例１では、（Ａ－Ａ’）が55,220,614、（Ｂ－Ｂ’）が65,986,934であり、（Ｂ－Ｂ’）／（Ａ－Ａ’）の値は約１．２であった。全ての例のピーク面積値比を表２に示す。 The film extract of each example was analyzed by GC/MS under the above analysis conditions, and the resulting total ion chromatogram was analyzed using MSD ChemStation (E.02.02.1431). From the total ion chromatogram of the film extract before deterioration treatment, the baseline was subtracted from the peaks at retention times of 6 to 40 minutes to determine the total peak area value (A). ) was calculated by subtracting the peak area value (A') of (AA'). At this time, a peak detected in a polypropylene film without additives (Comparative Example 1) was compared, and a peak with the same retention time and mass spectrum was determined to be a hydrocarbon peak.
For the film extract after the deterioration treatment, the total peak area value (B) was determined in the same manner as above, and then the peak area value (B') of hydrocarbons was subtracted to calculate (BB').
From these results, the peak area value ratio ((BB')/(AA')) was calculated.
As an example, in Example 1, (AA') was 55,220,614, (BB') was 65,986,934, and the value of (BB')/(AA') was approximately 1.2. . The peak area value ratios of all examples are shown in Table 2.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　本開示におけるポリプロピレンフィルム形成用樹脂組成物は、フィルム製膜時及び製膜後の長期間にわたって、ポリプロピレン樹脂の酸化劣化を抑制することができる。当該樹脂組成物から製膜されるポリプロピレンフィルムは、各種軟包材、エレクトロニクス包材、医療・医薬品包材、トイレタリー製品、液体複合紙容器、チルド・冷凍食品包材等の分野における利用が期待できる。 The resin composition for forming a polypropylene film in the present disclosure can suppress oxidative deterioration of the polypropylene resin during film formation and over a long period of time after film formation. The polypropylene film produced from the resin composition can be expected to be used in various fields such as flexible packaging materials, electronics packaging materials, medical/pharmaceutical packaging materials, toiletry products, liquid composite paper containers, and chilled/frozen food packaging materials. .

Claims (10)

  1. 　ポリプロピレン樹脂と、
    　炭素ラジカルを捕捉する機能を有するヒンダードアミン系の光安定剤と、
    　一次酸化防止機能及び二次酸化防止機能を有するヒドロキシルアミン系の酸化防止剤と、を含む、ポリプロピレンフィルム形成用樹脂組成物。     polypropylene resin,
    A hindered amine light stabilizer that has the function of capturing carbon radicals,
    A resin composition for forming a polypropylene film, comprising a hydroxylamine-based antioxidant having a primary antioxidant function and a secondary antioxidant function.
  2. 　前記ヒドロキシルアミン系の酸化防止剤がジアルキルヒドロキシルアミンである、請求項１に記載の樹脂組成物。 The resin composition according to claim 1, wherein the hydroxylamine-based antioxidant is dialkylhydroxylamine.
  3. 　前記ヒドロキシルアミン系の酸化防止剤がビス－オクタデシルヒドロキシルアミンである、請求項２に記載の樹脂組成物。 The resin composition according to claim 2, wherein the hydroxylamine-based antioxidant is bis-octadecylhydroxylamine.
  4. 　前記ヒンダードアミン系の光安定剤の重量平均分子量が２０００未満である、請求項１又は２に記載の樹脂組成物。 The resin composition according to claim 1 or 2, wherein the hindered amine light stabilizer has a weight average molecular weight of less than 2,000.
  5. 　前記ヒンダードアミン系の光安定剤がセバシン酸ビス（２，２，６，６－テトラメチル－４－ピペリジル）である、請求項４に記載の樹脂組成物。 The resin composition according to claim 4, wherein the hindered amine light stabilizer is bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate.
  6. 　前記ポリプロピレン樹脂、前記光安定剤及び前記酸化防止剤の全量を基準として、前記光安定剤の含有量が１５０質量ｐｐｍ以上であり、前記酸化防止剤の含有量が１５０質量ｐｐｍ以上であり、前記光安定剤及び前記酸化防止剤の合計含有量が２５００質量ｐｐｍ以下である、請求項１又は２に記載の樹脂組成物。 Based on the total amount of the polypropylene resin, the light stabilizer, and the antioxidant, the content of the light stabilizer is 150 mass ppm or more, the content of the antioxidant is 150 mass ppm or more, and the The resin composition according to claim 1 or 2, wherein the total content of the light stabilizer and the antioxidant is 2500 mass ppm or less.
  7. 　請求項１又は２に記載の樹脂組成物から製膜されるポリプロピレンフィルム。 A polypropylene film produced from the resin composition according to claim 1 or 2.
  8. 　メルトフローレート（ＪＩＳ　Ｋ６９２１－２準拠、温度２３０℃、荷重２．１６ｋｇ）が２０．０ｇ／１０ｍｉｎ以下である、請求項７に記載のフィルム。 The film according to claim 7, having a melt flow rate (according to JIS K6921-2, temperature 230°C, load 2.16 kg) of 20.0 g/10 min or less.
  9. 　請求項７に記載のフィルムを備える積層体。 A laminate comprising the film according to claim 7.
  10. 　請求項８に記載のフィルムを備える積層体。 A laminate comprising the film according to claim 8.
PCT/JP2023/014906 2022-05-11 2023-04-12 Resin composition for forming polypropylene film, polypropylene film, and multilayer body WO2023218848A1 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60101132A (en) * 1983-10-11 1985-06-05 チバ‐ガイギー　アクチエンゲゼルシヤフト Polyolefin composition stabilized against degradation by useof hydroxylamine derivative
JPH11263886A (en) * 1997-12-18 1999-09-28 Montell North America Inc Ductile gamma-ray-resistant polyolefin composition and article produced therefrom
JP2005530002A (en) * 2002-06-13 2005-10-06 バーセル ポリオレフィン イタリア ソシエタ ペル アチオニ Preparation method of polyolefin nanocomposite
WO2020089268A1 (en) * 2018-10-30 2020-05-07 Borealis Ag A moulded article comprising a polypropylene composition suitable for gamma-ray sterilization

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60101132A (en) * 1983-10-11 1985-06-05 チバ‐ガイギー　アクチエンゲゼルシヤフト Polyolefin composition stabilized against degradation by useof hydroxylamine derivative
JPH11263886A (en) * 1997-12-18 1999-09-28 Montell North America Inc Ductile gamma-ray-resistant polyolefin composition and article produced therefrom
JP2005530002A (en) * 2002-06-13 2005-10-06 バーセル ポリオレフィン イタリア ソシエタ ペル アチオニ Preparation method of polyolefin nanocomposite
WO2020089268A1 (en) * 2018-10-30 2020-05-07 Borealis Ag A moulded article comprising a polypropylene composition suitable for gamma-ray sterilization

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