WO2020110829A1 - シーラント用樹脂組成物、積層体、包装材料、及び包装体 - Google Patents
シーラント用樹脂組成物、積層体、包装材料、及び包装体 Download PDFInfo
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- WO2020110829A1 WO2020110829A1 PCT/JP2019/045273 JP2019045273W WO2020110829A1 WO 2020110829 A1 WO2020110829 A1 WO 2020110829A1 JP 2019045273 W JP2019045273 W JP 2019045273W WO 2020110829 A1 WO2020110829 A1 WO 2020110829A1
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- resin
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- sealant
- ethylene
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2433/00—Presence of (meth)acrylic polymer
- C09J2433/006—Presence of (meth)acrylic polymer in the substrate
Definitions
- the present disclosure relates to a sealant resin composition, a laminate, a packaging material, and a packaging body.
- the sealant resin composition is also referred to as a sealant resin composition.
- Japanese Patent Application Laid-Open No. 2008-95044 discloses that it is suitable as a heat-sealing material used for a plastic container, particularly a container made of impact-resistant polystyrene, and has a peeling strength in a more appropriate range than a conventional product for a container body constituent material.
- this type of heat seal material such as the sealing protection of the contents of containers such as foods, it has higher heat resistance and lower temperature than conventional products.
- ethylene-vinyl ester copolymer resin (A) 30 to 80 parts by mass, ethylene-(meth)acrylic acid ester 1 to 45 parts by mass of the copolymer resin (B) and 3 to 30 parts by mass of the tackifying resin (C) (however, the total amount of the (A), (B) and (C) resins is 100 parts by mass).
- Resin compositions for sealing materials are known.
- the resin composition for a sealing material that is, the resin composition for a sealant
- JP-A-2008-95044 is required to further improve the heat sealing strength with respect to the substrate.
- An object of the first aspect of the present disclosure is to provide a resin composition for a sealant, which has excellent heat seal strength with respect to a base material and has a reduced elution amount into normal heptane.
- An object of the second aspect of the present disclosure is to provide a laminate that includes a base material layer and a sealant layer, is excellent in heat seal strength with respect to the base material, and has a reduced elution amount of the sealant layer into normal heptane. That is.
- An object of the third aspect of the present disclosure is to provide a packaging material that is provided with the above-mentioned laminated body, is excellent in heat seal strength with respect to a base material, and has a reduced elution amount of a sealant layer to normal heptane. ..
- An object of the fourth aspect of the present disclosure is to include a base material, a laminate including a base material layer and a sealant layer, and an article to be packaged, which is excellent in heat seal strength between the base material and the laminate, and , A sealant layer having a reduced elution amount into normal heptane is provided.
- a resin (A) which is an ethylene/(meth)acrylic acid ester copolymer having a content of (meth)acrylic acid ester units of 10% by mass or more and 25% by mass or less, Tackifying resin (B), Containing
- the content of the resin (A) is more than 45 mass% with respect to the total amount of the resin component in the resin composition for sealant,
- the resin composition for sealants wherein the content of the tackifying resin (B) is 0.1% by mass or more and 10% by mass or less based on the total amount of the resin components in the resin composition for sealants.
- the resin composition for a sealant according to ⁇ 1> further containing a resin (C) which is an ethylene/vinyl ester copolymer.
- a resin (D) which is at least one selected from the group consisting of an ethylene/ ⁇ -olefin copolymer elastomer, a styrene elastomer, and polyethylene.
- ⁇ 4> The resin composition for a sealant according to ⁇ 3>, wherein the content of the resin (D) is 5% by mass or more and 40% by mass or less based on the total amount of the resin components in the resin composition for a sealant.
- ⁇ 5> The resin composition for a sealant according to any one of ⁇ 1> to ⁇ 4>, which is used as a sealant for a packaging material.
- ⁇ 6> The sealant resin composition according to ⁇ 5>, wherein the packaging material is a packaging material for skin pack packaging.
- base material layer A sealant layer containing the resin composition for sealant according to any one of ⁇ 1> to ⁇ 6>, A laminate including.
- ⁇ 8> The laminate according to ⁇ 7>, wherein the base material layer contains at least one selected from the group consisting of an ionomer of an ethylene/unsaturated carboxylic acid copolymer and an ethylene/unsaturated ester copolymer. ..
- ⁇ 9> The laminate according to ⁇ 7> or ⁇ 8>, having a thickness of 40 ⁇ m or more and 300 ⁇ m or less.
- a packaging material comprising the laminate according to any one of ⁇ 7> to ⁇ 9>.
- a resin composition for a sealant which has excellent heat-sealing strength with respect to a substrate and has a reduced elution amount into normal heptane.
- a laminate including a base material layer and a sealant layer, which is excellent in heat seal strength with respect to the base material and has a reduced elution amount of the sealant layer into normal heptane.
- a packaging material including the above-mentioned laminate, having excellent heat-sealing strength with respect to the base material, and having a reduced elution amount of the sealant layer into normal heptane.
- a base material, a laminate including a base material layer and a sealant layer, and an article to be packaged are provided, and excellent heat seal strength between the base material and the laminate, and Provided is a package in which the amount of the sealant layer eluted into normal heptane is reduced.
- the numerical range indicated by using “to” indicates the range including the numerical values before and after “to” as the minimum value and the maximum value, respectively.
- the amount of each component in the composition means the total amount of the plurality of substances present in the composition, unless otherwise specified, when there are a plurality of substances corresponding to each component in the composition. To do.
- the upper limit value or the lower limit value described in a certain numerical range may be replaced with the upper limit value or the lower limit value of another stepwise described numerical range, or , May be replaced with the values shown in the examples.
- (meth)acrylic acid is a concept that includes both acrylic acid and methacrylic acid
- (meth)acrylic acid ester is a concept that includes both acrylic acid ester and methacrylic acid ester. Is.
- the resin composition for a sealant includes a resin (A) that is an ethylene/(meth)acrylic acid ester copolymer having a content of (meth)acrylic acid ester units of 10% by mass or more and 25% by mass or less,
- the tackifying resin (B) is contained, and the content of the resin (A) is more than 45% by mass with respect to the total amount of the resin component in the resin composition for a sealant, and the tackifying resin (B) is contained.
- the amount is 0.1% by mass or more and 10% by mass or less based on the total amount of the resin component in the resin composition for sealant.
- the resin composition for a sealant according to the present disclosure has excellent heat seal strength with respect to a substrate.
- the resin composition for a sealant according to the present disclosure has a reduced elution amount into normal heptane, which is one of the indicators of hygiene. The reason why such an effect is exhibited is presumed as follows.
- the effect of excellent heat seal strength to the base material is:
- the content of the (meth)acrylic acid ester unit in the resin (A) (that is, ethylene/(meth)acrylic acid ester copolymer) is 10% by mass or more
- the content of the resin (A) (hereinafter, also simply referred to as “content of the resin (A)”) with respect to the total amount of the resin component in the sealant resin composition is more than 45% by mass
- the tackifying resin It is considered that the content of B) is 0.1 mass% or more to contribute.
- the content of the tackifying resin (B) with respect to the total amount of the resin component in the resin composition for a sealant (hereinafter, also simply referred to as "content of the tackifying resin (B)") is 10% by mass or less, and , It is considered that the content of the (meth)acrylic acid ester unit in the resin (A) (that is, the ethylene/(meth)acrylic acid ester copolymer) is 25% by mass or less is considered to contribute.
- the resin composition for a sealant of the present disclosure is particularly suitable for resins such as polyethylene (PE), polypropylene (PP), polystyrene (PS), high impact polystyrene (HIPS), polyethylene terephthalate (PET), polyethylene (PE) and A mixture of polybutene (PB), a mixture of polyethylene (PE) and polypropylene (PP)] is excellent in adhesion to a substrate.
- the base material containing the resin may further contain a filler and the like.
- the film may be a stretched film or a non-stretched film.
- examples of the base material containing a mixture of PE and PB or PE and PP include cohesive failure type films.
- a base material containing polypropylene (PP) is a base material that is relatively difficult to secure heat seal strength with other objects.
- the resin composition for a sealant according to the present disclosure is excellent in heat seal strength even with respect to a substrate containing such polypropylene (PP) (see Examples below).
- the resin composition for sealants of the present disclosure contains the resin (A).
- the resin (A) is an ethylene/(meth)acrylic acid ester in which the content of the (meth)acrylic acid ester unit (that is, the structural unit derived from the (meth)acrylic acid ester) is 10% by mass or more and 25% by mass or less. It is a copolymer.
- the content of the (meth)acrylic acid ester unit is the content based on the total amount of the ethylene/(meth)acrylic acid ester copolymer (that is, the resin (A)) ((meth)acrylic in the resin (A)). When two or more acid ester units are contained, it is the total content).
- the resin (A) contained in the resin composition for a sealant of the present disclosure may be only one type, or may be two or more types.
- the (meth)acrylic acid ester unit contained in the resin (A) may be only one type, or may be two or more types.
- the content of the (meth)acrylic acid ester unit in the resin (A) is 10% by mass or more, so that the heat seal strength of the resin composition for a sealant with respect to the base material is improved. .. From the viewpoint of further improving the heat-sealing strength with respect to the substrate, the content of the (meth)acrylic acid ester unit in the resin (A) is preferably 15% by mass or more, and more preferably 18% by mass or more.
- the content of the (meth)acrylic acid ester unit in the resin (A) is 25% by mass or less, so that the amount of the resin composition for a sealant eluted into normal heptane is reduced. It From the viewpoint of reducing the elution amount of the resin composition for sealants to normal heptane, the content of the (meth)acrylic acid ester unit in the resin (A) is preferably 24% by mass or less, and more preferably 22% by mass. It is below.
- the content of ethylene units (that is, structural units derived from ethylene) in the resin (A) is preferably 75% by mass or more and 90% by mass or less.
- the content of the ethylene unit is the content with respect to the total amount of the ethylene/(meth)acrylic acid ester copolymer (that is, the resin (A)).
- the content of the ethylene unit in the resin (A) is 90% by mass or less, so that the heat seal strength of the resin composition for a sealant with respect to the base material is improved. From the viewpoint of further improving the heat-sealing strength of the resin composition for a sealant with respect to the substrate, the content of the ethylene unit in the resin (A) is preferably 85% by mass or less, more preferably 82% by mass or less.
- the content of the ethylene unit in the resin (A) is 75% by mass or more, so that the amount of the resin composition for a sealant eluted into normal heptane is reduced.
- the content of ethylene units in the resin (A) is preferably 76% by mass or more, and more preferably 78% by mass or more.
- the ethylene/(meth)acrylic acid ester copolymer (that is, the resin (A)) may or may not contain any other structural unit other than the ethylene unit and the (meth)acrylic acid ester unit. May be.
- the total content of ethylene units and (meth)acrylic acid ester units in the resin (A) is preferably 80% by mass or more, and more preferably 90% by mass or more, based on the total amount of the resin (A).
- a (meth)acrylic acid alkyl ester is preferable, and an alkyl (meth)acrylic acid having an alkyl ester moiety (that is, an alkoxy group) having 1 to 10 carbon atoms. Esters are more preferred.
- the carbon number of the alkyl ester moiety is more preferably 1-8, further preferably 1-6, and further preferably It is 1 to 4, and more preferably 1 or 2.
- Examples of the monomer for forming the (meth)acrylic acid ester unit include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and (meth)acrylic. Acid n-butyl, (meth)acrylic acid isobutyl, (meth)acrylic acid n-hexyl, (meth)acrylic acid isohexyl, (meth)acrylic acid n-octyl, (meth)acrylic acid isooctyl, (meth)acrylic acid- 2-ethylhexyl and the like can be mentioned.
- the melt flow rate (MFR: measured according to JIS K7210-1999, 190° C., 2160 g load) of the resin (A) is preferably 0.1 g from the viewpoint of the characteristics and processability of the resin composition for sealant. /10 minutes to 100 g/10 minutes, more preferably 1 g/10 minutes to 50 g/10 minutes, still more preferably 1 g/10 minutes to 30 g/10 minutes.
- the method for synthesizing the resin (A) is not particularly limited, and a known method can be applied.
- the descriptions in paragraphs 0020 to 0023 of JP 2008-95044 A can be appropriately referred to.
- the ethylene/(meth)acrylic acid ester copolymer (resin (A)) it is particularly preferable to use a copolymer resin produced by a tubular high pressure polymerization method. ..
- the copolymer resin obtained by this method has a copolymer composition and an average molecular weight which are higher than those of an ethylene/(meth)acrylic acid ester copolymer produced by another method such as a usual radical polymerization method. Even though they are the same, they have a high melting point, and yet, thermal properties such as viscoelastic behavior in the molten state from softening and other attributes are different. Therefore, the composition obtained by blending them is as described above. The characteristics of the composition of the present disclosure can be better expressed.
- the tubular high-pressure polymerization method is a method in which a tubular reactor is used and radical polymerization is carried out at a high pressure using a free radical catalyst.
- a method described in JP-A-62-273214 is exemplified. it can.
- the tubular high-pressure polymerization method uses (a) a tubular reactor and (b) a reactor inlet pressure of 2300 to 3000 kg/cm 2 , preferably 2400 to 2800 kg/cm 2 , (c).
- the average reaction temperature (TAV) in the reactor is in the range of 190° C. ⁇ TAV ⁇ 230° C.
- ethylene is introduced from the inlet of the reactor, or the inlet and at least one side, and
- the total amount of ethyl acrylate, which is the body, is introduced from the inlet, and radical polymerization is carried out in the presence of a free radical catalyst, a chain transfer agent and, if necessary, an auxiliary agent.
- the copolymer obtained by the above polymerization method has a relationship between the (meth)acrylic acid ester content: E (% by weight) and the melting point of the copolymer: T (° C.) represented by the following formula (I), ⁇ 0.8 ⁇ E+115 ⁇ T ⁇ 0.8 ⁇ E+109 (I) It has a high melting point and excellent heat resistance as compared with a copolymer having a corresponding composition obtained by another polymerization method.
- the copolymer obtained by the above-mentioned polymerization method has less random arrangement of ethylene units and (meth)acrylic acid ester units, that is, non-uniform arrangement, as compared with the copolymer having good randomness by the usual radical polymerization method. It has high properties and has a polymer structure and physical properties somewhat similar to those of block copolymers. Therefore, it is considered that the melting point and the ester unit content have the above relationship.
- the content of the resin (A) with respect to the total amount of the resin components in the resin composition for a sealant of the present disclosure (hereinafter, also simply referred to as “content of the resin (A)”) is more than 45% by mass. Thereby, the heat-sealing strength of the resin composition for a sealant with respect to the base material is improved. From the viewpoint of further improving the heat-sealing strength of the resin composition for a sealant with respect to the substrate, the content of the resin (A) is preferably 46% by mass or more, more preferably 47% by mass or more, and further preferably It is 50 mass% or more.
- the upper limit of the content of the resin (A) depends on the content of other components such as the tackifying resin (B).
- the upper limit of the content of the resin (A) is 99.9 mass% in principle.
- the resin component includes at least the resin (A) and the tackifying resin (B) described below.
- the resin component also includes the resin (C).
- the resin component also includes the resin (D).
- the total content of the resin components in the sealant resin composition of the present disclosure is preferably 80% by mass or more, and more preferably 90% by mass or more, based on the total amount of the sealant resin composition.
- the sealant resin composition of the present disclosure contains a tackifying resin (B).
- the tackifying resin (B) contained in the resin composition for a sealant may be only one type, or may be two or more types.
- tackifying resin (B) examples include aliphatic hydrocarbon resins, alicyclic hydrocarbon resins, aromatic hydrocarbon resins, styrene resins, terpene resins and rosins.
- Examples of the aliphatic hydrocarbon resin include polymers of monomer raw materials mainly containing C 4 to C 5 mono- or diolefins such as 1-butene, isobutylene, butadiene, 1,3-pentadiene, isoprene and piperylene. ..
- Examples of the alicyclic hydrocarbon resin include a resin obtained by polymerizing a diene component in a spent C 4 to C 5 fraction after cyclization dimerization, a resin obtained by polymerizing a cyclic monomer such as cyclopentadiene, and an aromatic hydrocarbon. Examples thereof include a resin obtained by hydrogenating a resin in the nucleus.
- Examples of the aromatic hydrocarbon resins include polymers of monomer raw materials containing C 9 to C 10 vinyl aromatic hydrocarbons as a main component, such as vinyltoluene, indene, and ⁇ -methylstyrene.
- styrene resin examples include polymers of monomer raw materials whose main components are styrene, vinyltoluene, ⁇ -methylstyrene, isopropenyltoluene and the like.
- terpene resin examples include ⁇ -pinene polymer, ⁇ -pinene polymer, dipentene polymer, terpene-phenol copolymer, ⁇ -pinene-phenol copolymer, hydrogenated terpene resin and the like.
- rosins examples include rosin, polymerized rosin, hydrogenated rosin, rosin ester, rosin phenol resin, and rosin phenol resin ester.
- an alicyclic hydrocarbon resin an aliphatic hydrocarbon resin, or a hydrogenated terpene resin is preferable, and an alicyclic hydrocarbon resin is more preferable.
- the ring-and-ball method softening point of the tackifier resin is preferably 70° C. or higher and 150° C. or lower, and more preferably 100° C. or higher and 130° C. or lower.
- the ring-and-ball method softening point means a value measured according to JIS K6863 (1994).
- the content of the tackifying resin (B) with respect to the total amount of the resin components in the resin composition for a sealant of the present disclosure (hereinafter, also simply referred to as “content of the tackifying resin (B)”) is 0.1% by mass or more. It is 10 mass% or less. In the resin composition for a sealant of the present disclosure, the content of the tackifying resin (B) is 0.1% by mass or more, so that the heat seal strength of the resin composition for a sealant with respect to the base material is improved.
- the content of the tackifying resin (B) is preferably 0.5% by mass or more, more preferably 1% by mass or more, More preferably, it is 1.5 mass% or more.
- the content of the tackifying resin (B) is 10% by mass or less, the elution amount of the resin composition for sealant to normal heptane is reduced.
- the content of the tackifying resin (B) is preferably 5% by mass or less, more preferably 3% by mass or less, It is more preferably less than 3% by mass, and particularly preferably 2.5% by mass or less.
- the resin composition for a sealant of the present disclosure preferably further contains a resin (C) which is an ethylene/vinyl ester copolymer.
- the resin (C) contained may be only one type, or may be two or more types.
- the resin composition for a sealant of the present disclosure further contains a resin (C)
- in the case of producing a film-shaped laminate as a laminate described below roll stick during production is reduced, Are advantageous in that mutual mutual contact is reduced.
- the resin (C) (that is, ethylene-vinyl ester copolymer) contains an ethylene unit (that is, a structural unit derived from ethylene) and a vinyl ester unit (that is, a structural unit derived from a vinyl ester).
- ethylene unit that is, a structural unit derived from ethylene
- vinyl ester unit that is, a structural unit derived from a vinyl ester.
- vinyl ester for forming the vinyl ester unit vinyl acetate or vinyl propionate is preferable, and vinyl acetate is more preferable.
- the content of vinyl ester units (hereinafter, also simply referred to as “content of vinyl ester units”) based on the total amount of the resin (C) (that is, ethylene/vinyl ester copolymer) is preferably 2% by mass or more and 30% by mass or more. Or less, more preferably 5% by mass or more and 25% by mass or less, further preferably 6% by mass or more and 19% by mass or less, and further preferably 7% by mass or more and 13% by mass or less.
- the content of the vinyl ester is 2% by mass or more, the heat seal strength of the resin composition for a sealant with respect to the base material is further improved.
- the heat seal strength of the resin composition for sealant with respect to the base material is further improved, and the elution amount of the resin composition for sealant to normal heptane is further reduced. To be done.
- the content of ethylene units (hereinafter, also simply referred to as “content of ethylene units”) relative to the total amount of the resin (C) (that is, ethylene/vinyl ester copolymer) is preferably 70% by mass or more and 98% by mass or less. It is more preferably 75% by mass or more and 95% by mass or less, further preferably 81% by mass or more and 94% by mass or less, and further preferably 87% by mass or more and 93% by mass or less.
- the content of the ethylene unit is 98% by mass or less, the heat seal strength of the sealant resin composition to the substrate is further improved.
- the heat-sealing strength of the sealant resin composition with respect to the base material is further improved, and the elution amount of the sealant resin composition into normal heptane is further reduced. To be done.
- the resin (C) (that is, the ethylene/vinyl ester copolymer) may or may not contain any other structural unit other than the ethylene unit and the vinyl ester unit.
- the total content of ethylene units and vinyl ester units in the resin (C) is preferably 80% by mass or more, and more preferably 90% by mass or more, based on the total amount of the resin (C).
- the melt flow rate (MFR: measured according to JIS K7210-1999, 190° C., 2160 g load) of the resin (C) is preferably 0.1 g from the viewpoints of characteristics and processability as the resin composition for sealant. /10 minutes to 100 g/10 minutes, more preferably 1 g/10 minutes to 50 g/10 minutes, still more preferably 1 g/10 minutes to 30 g/10 minutes.
- the content of the resin (C) with respect to the total amount of the resin components in the resin composition for a sealant (hereinafter, simply “content of the resin (C)”).
- content of the resin (C) is preferably 1% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 45% by mass or less, and further preferably 15% by mass or more and 45% by mass or less.
- the content of the resin (C) is 50% by mass or less, the heat seal strength of the resin composition for a sealant with respect to the base material is further improved.
- the content of the resin (C) is 1% by mass or more, in the case of producing a film-shaped laminate as a laminate described below, roll stick during production is reduced, and mutual adhesion between films is It is advantageous in that it is reduced.
- the resin composition for a sealant according to the present disclosure preferably further contains at least one resin (D) selected from the group consisting of an ethylene/ ⁇ -olefin copolymer elastomer, a styrene elastomer, and polyethylene. ..
- the resin composition for a sealant of the present disclosure further contains the resin (D)
- the heat seal strength of the resin composition for a sealant with respect to the base material is further improved.
- the resin (D) further preferably contains at least one selected from the group consisting of ethylene/ ⁇ -olefin copolymer elastomers and styrene elastomers.
- the ethylene/ ⁇ -olefin copolymer elastomer is an elastomer containing ethylene units and ⁇ -olefin units (that is, structural units derived from ⁇ -olefins).
- the carbon number of the ⁇ -olefin for forming the ⁇ -olefin unit is preferably 3 to 10, more preferably 3 to 8.
- Examples of the ⁇ -olefin for forming the ⁇ -olefin unit include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene and the like.
- the ethylene/ ⁇ -olefin copolymer elastomer is preferably an ethylene/1-butene copolymer elastomer, an ethylene/propylene copolymer elastomer, or an ethylene/1-octene copolymer elastomer.
- the ethylene/ ⁇ -olefin copolymer elastomer is obtained by randomly copolymerizing ethylene and ⁇ -olefin in the presence of a combination catalyst of a transition metal compound (eg, vanadium compound, zirconium compound, etc.) and an organic aluminum compound. Manufactured by.
- a transition metal compound eg, vanadium compound, zirconium compound, etc.
- the ethylene/ ⁇ -olefin copolymer elastomer has an X-ray crystallinity of preferably 1% to 20% (more preferably 3% to 15%).
- the method for obtaining the ethylene/ ⁇ -olefin copolymer elastomer having the above crystallinity is, for example, by changing the copolymerization ratio of the ⁇ -olefin to 7 mol% to Examples of 20 mol% (preferably 8 mol% to 16 mol%) include a method of copolymerizing ethylene and ⁇ -olefin.
- the melt flow rate (MFR: measured according to JIS K7210-1999, 190° C., 2160 g load) of the ethylene/ ⁇ -olefin copolymer elastomer is preferably 0.1 g/10 min to 100 g/10 min, It is more preferably 1 g/10 minutes to 50 g/10 minutes, and further preferably 1 g/10 minutes to 30 g/10 minutes.
- the density of the ethylene/ ⁇ -olefin copolymer elastomer is preferably 850 kg/m 3 or more and less than 900 kg/m 3 , more preferably 860 kg/m 3 to 890 kg/m 3 , and even more preferably 860 kg/m 3. ⁇ 880 kg/m 3 .
- styrene elastomers examples include ABA type block copolymers (wherein A represents a styrene polymer block and B represents an alkylene copolymer block).
- A represents a styrene polymer block
- B represents an alkylene copolymer block
- the styrene polymer block refers to a polystyrene moiety
- the alkylene copolymer block refers to an alkylene copolymer moiety in which two or more alkenes are copolymerized.
- alkylene copolymer block examples include an ethylene/butene copolymer block and an ethylene/propylene copolymer block.
- Such a block copolymer is obtained by hydrogenating a butadiene polymer unit or an isoprene polymer unit of a styrene-butadiene-styrene block copolymer or a styrene-isoprene-styrene block copolymer.
- ABA type block copolymer examples include polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer (SEBS) and polystyrene-poly(ethylene-propylene)-polystyrene triblock copolymer (SEPS). , And the like.
- ABA type block copolymer examples include Kraton G1657 manufactured by Kraton Japan Co., Ltd. and Tuftec H1221 manufactured by Asahi Kasei Corporation.
- the melt flow rate (measured according to MFR: JIS K7210-1999, 230° C., 5000 g load) of the styrene elastomer is preferably 0.1 g/10 min. To 100 g/10 minutes, more preferably 1 g/10 minutes to 50 g/10 minutes, and further preferably 1 g/10 minutes to 30 g/10 minutes.
- polyethylene examples include high density polyethylene (HDPE), low density polyethylene (LDPE), medium density polyethylene (MDPE), and linear low density polyethylene (LLDPE).
- the density of polyethylene depends on the type of polyethylene, but is preferably 900 kg/m 3 or more, more preferably 910 kg/m 3 or more.
- the upper limit of the density of polyethylene is not particularly limited, but the upper limit is, for example, 960 kg/m 3 .
- the density of HDPE is preferably not 942kg / m 3 or more, more preferably 942kg / m 3 or more 960 kg / m 3 or less.
- the density of MDPE is preferably less than 930 kg / m 3 or more 942kg / m 3.
- the density of LDPE is preferably less than 910 kg / m 3 or more 930 kg / m 3.
- the density of LLDPE is preferably less than 900 kg / m 3 or more 930 kg / m 3.
- the melt flow rate of polyethylene (MFR: measured according to JIS K7210-1999, 190° C., 2160 g load) is preferably 0.1 g/10 minutes to 100 g/10 minutes, more preferably 1 g/10 minutes to It is 50 g/10 minutes, more preferably 1 g/10 minutes to 30 g/10 minutes.
- the content of the resin (D) with respect to the total amount of the resin components in the resin composition for a sealant (hereinafter, simply “content of the resin (D)”).
- content of the resin (D) is preferably 1% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 40% by mass or less, and further preferably 10% by mass or more and 30% by mass or less.
- the content of the resin (D) is 1% by mass or more, the heat seal strength of the sealant resin composition with respect to the base material is further improved.
- the content of the resin (D) is 50% by mass or less, the heat seal strength of the resin composition for a sealant against the base material is further suppressed from becoming excessive.
- the resin composition for a sealant according to the present disclosure may contain other components other than the components described above.
- examples of other components include additives such as slip agents and release agents.
- additives include: Various amides such as palmitic acid amide, stearic acid amide, behenic acid amide, oleic acid amide, erucic acid amide, oleyl palmitamide, stearyl palmitamide, methylene bis stearyl amide, methylene bis oleyl amide, ethylene bis erucic acid amide ; Polyalkylene glycols such as polyethylene glycol and polypropylene glycol; Hydrogenated castor oil; Inorganic additives such as silica, talc, zeolite; Etc.
- the content of the additive is preferably 0.01% by mass to 3% by mass with respect to the total amount of the resin component.
- the total content of the resin components in the sealant resin composition of the present disclosure is preferably 80% by mass or more, and more preferably 90% by mass or more, based on the total amount of the resin composition for sealants.
- the resin component includes at least the resin (A) and the tackifying resin (B).
- the resin component further includes the resin (C).
- the resin composition for a sealant of the present disclosure contains a resin (A), a tackifying resin (B), and a resin (C) as a resin component, and the total amount of the resin component in the resin composition for a sealant is the same.
- the content of the resin (A) is more than 45% by mass
- the content of the tackifying resin (B) is 0.1% by mass or more and 10% by mass or less
- the content of the resin (C) is It is also a preferable embodiment that the content is 1% by mass or more and 50% by mass or less.
- the resin component further includes the resin (D).
- the sealant resin composition of the present disclosure contains a resin (A), a tackifying resin (B), a resin (C), and a resin (D) as resin components.
- the resin (A) content is more than 45% by mass
- the tackifying resin (B) content is 0.1% by mass or more and 10% by mass or less
- the content of the resin (D) is 1% by mass or more and 50% by mass or less.
- the resin composition for a sealant according to the present disclosure can be applied to any application that requires heat seal strength for a base material and reduction of the elution amount to normal heptane.
- the use of the resin composition for a sealant of the present disclosure is not particularly limited, but it is preferably used as a sealant for packaging materials.
- packaging material examples include packaging materials for packaging foods, toys, stationery, household goods, cosmetics, pharmaceuticals, quasi drugs, medical instruments, and the like.
- the packaging material is preferably a packaging material for food.
- examples of the food include meat, meat products, meat dishes, seafood, seafood dishes, processed marine products, side dishes, cooked pasta, processed milk products, and the like.
- Ministry of Health and Welfare Notification No. 370 (“Standards for foods, additives, etc.”) can be referred to.
- the packaging material is preferably a packaging material for skin pack packaging.
- the skin pack packaging means a vacuum packaging in which at least a part of the packaging material is in close contact with the article to be packaged while following the shape of the article to be packaged.
- a sealant is used to realize the vacuum packaging of the above aspect. Since a packaging material for skin pack packaging often includes a base material (for example, a container, a tray, etc.), a sealant for such a packaging material is often required to have heat seal strength with respect to the base material.
- packaging materials for skin pack packaging are often required to have hygiene (for example, reduction of elution amount to normal heptane) in order to maintain the quality of the packaging object.
- the sealant is required to reduce the elution amount to normal heptane.
- the packaging material to which the sealant resin composition of the present disclosure is applied is preferably a packaging material for skin pack packaging.
- the laminate of the present disclosure includes a base material layer and a sealant layer containing the above-described resin composition for a sealant of the present disclosure. Since the laminate of the present disclosure includes the sealant layer containing the above-described resin composition for a sealant of the present disclosure, it has excellent heat seal strength with respect to the base material, and the elution amount of the sealant layer to normal heptane is reduced. ..
- the base material layer is a layer in which a sealant layer containing the above-described resin composition for a sealant of the present disclosure is laminated directly or via another layer to secure the strength as a packaging material.
- the material of the base material layer is not particularly limited.
- the material of the base material layer is a stretched or non-stretched film, for example, polyester such as polyethylene terephthalate; polyamide; polyolefin such as polypropylene or polyethylene; ethylene/vinyl acetate copolymer, ethylene/unsaturated carboxylic acid ester.
- Ethylene/unsaturated ester copolymer such as copolymer; ethylene/unsaturated carboxylic acid copolymer or its ionomer; ethylene/vinyl alcohol copolymer; paper; aluminum foil; aluminum, silica, alumina, magnesia, etc.
- the film include a film coated with a gas barrier material such as polyvinylidene chloride and polyvinyl alcohol.
- the structure of the base material layer may be a single layer structure or a laminated structure composed of two or more layers.
- the base material layer preferably contains a resin.
- the resin is preferably a thermoplastic resin.
- the thermoplastic resin is not particularly limited, and examples thereof include polyesters such as polyethylene terephthalate; polyamides; polyolefins such as polypropylene and polyethylene; ethylene/vinyl acetate copolymers, ethylene/unsaturated carboxylic acid ester copolymers, and other ethylene/unsaturated polymers. Examples thereof include saturated ester copolymers; ethylene/unsaturated carboxylic acid copolymers or ionomers thereof; ethylene/vinyl alcohol copolymers.
- the base material layer more preferably contains at least one selected from the group consisting of an ionomer of an ethylene/unsaturated carboxylic acid copolymer and an ethylene/unsaturated ester copolymer.
- the stretchability of the laminate is improved.
- the extensibility is a property that can be required when the laminate is used as a packaging material, for example.
- the laminate having excellent extensibility is used as a packaging material for skin pack packaging, the conformability to the shape of the packaged object and the adhesion to the packaged object are further improved.
- the base material layer may contain at least one ionomer of an ethylene/unsaturated carboxylic acid copolymer.
- the base material layer contains an ionomer of an ethylene/unsaturated carboxylic acid copolymer, not only the extensibility of the laminate but also the puncture strength of the laminate is improved.
- the puncture strength is also a property that can be required when the laminate is used as a packaging material (particularly, a packaging material for skin pack packaging).
- an ionomer of an ethylene/unsaturated carboxylic acid copolymer means that at least a part of acidic groups (that is, carboxy groups) in the ethylene/unsaturated carboxylic acid copolymer as a base polymer is a metal ion. It means a compound that has been neutralized.
- the ethylene/unsaturated carboxylic acid copolymer as a base polymer is a copolymer obtained by copolymerizing at least ethylene and an unsaturated carboxylic acid, and is an ethylene unit (that is, a structural unit derived from ethylene. ) And an unsaturated carboxylic acid unit (that is, a structural unit derived from an unsaturated carboxylic acid).
- the ethylene/unsaturated carboxylic acid copolymer may be any of a block copolymer, a random copolymer and a graft copolymer. From the viewpoint of industrial availability, the ethylene/unsaturated carboxylic acid copolymer is preferably a random copolymer.
- unsaturated carboxylic acid units examples include (meth)acrylic acid units, fumaric acid units, and maleic acid units.
- the unsaturated carboxylic acid unit is preferably a (meth)acrylic acid unit, more preferably a methacrylic acid unit.
- the content of unsaturated carboxylic acid units in the ethylene/unsaturated carboxylic acid copolymer as the base polymer is preferably 1% by mass or more and 25% by mass or less, and 3% by mass or more and 20% by mass or less with respect to the total amount of the copolymer. The following is more preferable, and 5% by mass or more and 15% by mass or less is further preferable.
- the content of ethylene units in the ethylene/unsaturated carboxylic acid copolymer as the base polymer is preferably 75% by mass or more and 99% by mass or less, more preferably 80% by mass or more and 97% by mass or less, based on the total amount of the copolymer. It is preferably 85% by mass or more and 95% by mass or less.
- the ethylene/unsaturated carboxylic acid copolymer as the base polymer may or may not contain any other structural unit other than the ethylene unit and the unsaturated carboxylic acid unit.
- Other structural units include unsaturated carboxylic acid ester units.
- the preferred embodiment of the unsaturated carboxylic acid ester unit is the same as the preferred embodiment of the (meth)acrylic acid ester unit in the resin (A) described above.
- the total content of ethylene units and unsaturated carboxylic acid units in the ethylene/unsaturated carboxylic acid copolymer is preferably 80% by mass or more, and more preferably based on the total amount of the ethylene/unsaturated carboxylic acid copolymer. Is 90% by mass or more.
- the kind of metal ion for neutralizing the acidic group in the ethylene/unsaturated carboxylic acid copolymer (base polymer) is not particularly limited.
- the metal ion include: Alkali metal ions such as lithium ion, sodium ion, potassium ion, rubidium ion and cesium ion; Alkaline earth metal ions such as magnesium ion and calcium ion; Transition metal ions such as zinc ions; Various metal ions such as aluminum ions; And so on.
- the metal ion at least one selected from the group consisting of zinc (Zn) ion, magnesium (Mg) ion and sodium (Na) ion is preferable, at least one of zinc ion and sodium ion is more preferable, and sodium ion is More preferable.
- the number of metal ions for neutralizing the acidic groups in the base polymer may be only one, or may be two or more.
- the degree of neutralization of the ionomer of the ethylene/unsaturated carboxylic acid copolymer is preferably 90% or less, more preferably 5% to 80%, still more preferably 10% to 70%.
- the degree of neutralization is 90% or less, ion agglomeration can be appropriately suppressed, fluidity deterioration can be further suppressed, and moldability can be more preferably maintained.
- the degree of neutralization is 5% or more, the performance as an ionomer can be more effectively exhibited.
- neutralization degree (%) means the ratio of the carboxyl groups that have been neutralized by metal ions to the total carboxyl groups contained in the ethylene/unsaturated carboxylic acid copolymer (base polymer) (mol %).
- the melt flow rate (measured according to MFR: JIS K7210-1999, 190° C., 2160 g load) of the ionomer of the ethylene/unsaturated carboxylic acid copolymer is preferably 0.1 g/10 from the viewpoint of workability. Min to 100 g/10 min, more preferably 0.3 g/10 min to 50 g/10 min, still more preferably 0.5 g/10 min to 20 g/10 min.
- the base material layer may contain at least one ethylene/unsaturated ester copolymer.
- the ethylene/unsaturated ester copolymer contains an ethylene unit and an unsaturated ester unit (that is, a structural unit derived from an unsaturated ester).
- the ethylene/unsaturated ester copolymer may be any of a block copolymer, a random copolymer and a graft copolymer.
- the unsaturated ester for forming the unsaturated ester unit Vinyl esters such as vinyl acetate and vinyl propionate; (Meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, isobutyl (meth)acrylate, n-butyl (meth)acrylate, and isooctyl (meth)acrylate; Etc.
- the unsaturated ester is preferably at least one of vinyl acetate and (meth)acrylic acid ester.
- an ethylene/vinyl acetate copolymer or an ethylene/(meth)acrylic acid ester copolymer is preferable, and an ethylene/vinyl acetate copolymer is more preferable.
- the content of unsaturated ester units with respect to the total amount of the ethylene/unsaturated ester copolymer is preferably 1% by mass or more and 40% by mass or less, more preferably 2% by mass or more and 30% by mass or less, and further preferably It is 5% by mass or more and 25% by mass or less.
- the content of ethylene units with respect to the total amount of the ethylene/unsaturated ester copolymer is preferably 60% by mass or more and 99% by mass or less, more preferably 70% by mass or more and 98% by mass or less, and further preferably 75% by mass. % To 95% by mass.
- the ethylene/unsaturated ester copolymer may or may not contain another structural unit other than the ethylene unit and the unsaturated ester unit.
- the total content of ethylene units and unsaturated ester units in the ethylene/unsaturated ester copolymer is preferably 80% by mass or more, and more preferably 90% by mass, based on the total amount of the ethylene/unsaturated ester copolymer. % Or more.
- the ethylene/unsaturated ester copolymer in the base material layer preferably has a crosslinked structure. This further improves the puncture strength of the base material layer and the laminate.
- Examples of the method for forming a crosslinked structure include thermal crosslinking, electron beam crosslinking, and radiation crosslinking. Of these, electron beam crosslinking is preferable from the viewpoints of crosslinking efficiency and hygiene.
- the melt flow rate (MFR: measured according to JIS K7210-1999, 190° C., 2160 g load) of the ethylene/unsaturated ester copolymer is preferably 0.1 g/10 min to 100 g from the viewpoint of processability and the like. /10 minutes, more preferably 1 g/10 minutes to 50 g/10 minutes, still more preferably 1 g/10 minutes to 30 g/10 minutes.
- the base material layer is selected from the group consisting of an ionomer of an ethylene/unsaturated carboxylic acid copolymer and an ethylene/unsaturated ester copolymer having a crosslinked structure. It is preferable to contain at least one selected.
- the base material layer may contain other components such as additives.
- the total content of the ionomer of the ethylene/unsaturated carboxylic acid copolymer and the ethylene/unsaturated ester copolymer with respect to the entire base material layer is preferably 80% by mass or more based on the total amount of the base material layer, More preferably, it is 90 mass% or more.
- the sealant layer is a layer containing the above-described resin composition for sealant of the present disclosure.
- the structure of the sealant layer may be a single layer structure or a laminated structure composed of two or more layers.
- the sealant layer is produced, for example, by melt extrusion using the resin composition for a sealant of the present disclosure (and other components such as additives as necessary).
- the content of the sealant resin composition of the present disclosure in the sealant layer is preferably 80% by mass or more, and more preferably 90% by mass or more, based on the total amount of the sealant layer.
- the shape of the laminate of the present disclosure is not particularly limited, but, for example, a sheet shape (that is, a film shape) is suitable.
- the thickness of the laminate of the present disclosure is not particularly limited, but is preferably 40 ⁇ m or more and 300 ⁇ m or less, more preferably 50 ⁇ m or more and 300 ⁇ m or less, and further preferably 50 ⁇ m or more and 200 ⁇ m or less.
- the thickness of the sealant layer in the laminate is not particularly limited, but is preferably 1 ⁇ m or more and 500 ⁇ m or less, more preferably 2 ⁇ m or more and 30 ⁇ m or less, and further preferably 3 ⁇ m or more and 20 ⁇ m or less.
- the thickness of the base material layer in the laminate is not particularly limited, but is preferably 40 ⁇ m or more and 300 ⁇ m or less, more preferably 50 ⁇ m or more and 300 ⁇ m or less. And more preferably 50 ⁇ m or more and 200 ⁇ m or less.
- the laminate of the present disclosure can be manufactured using a known method.
- the method for producing the laminate include an extrusion lamination method, a coextrusion inflation method, a coextrusion T-die method, and the like.
- the coextrusion T-die method is preferable from the viewpoint of controlling the thickness of the laminate.
- ⁇ Preferred use of laminate> There are no particular restrictions on the use of the laminate of the present disclosure.
- the preferred use of the laminate of the present disclosure is the same as the preferred use of the resin composition for a sealant of the present disclosure described above.
- the packaging material of the present disclosure includes the above-described laminated body of the present disclosure. Therefore, the heat seal strength with the base material is excellent, and the elution amount of the sealant layer into normal heptane is reduced.
- the packaging material of the present disclosure preferably further comprises a substrate.
- Examples of the packaging material of this aspect include a packaging material that is a set including a base material and a laminate, an integral packaging material in which a part of the base material and a part of the sealant layer in the laminate are adhered, and the like. Be done.
- a base material containing a resin is preferable.
- the resin are as described in the section of “resin composition for sealant”, and examples thereof include polyethylene (PE), polypropylene (PP), polystyrene (PS), high impact polystyrene (HIPS), polyethylene terephthalate ( PET), a mixture of polyethylene (PE) and polybutene (PB), a mixture of polyethylene (PE) and polypropylene (PP), and the like, with polypropylene (PP) being preferred.
- the base material may contain other components such as fillers and additives.
- the content of the resin in the substrate is preferably 80% by mass or more, more preferably 90% by mass or more, based on the total amount of the substrate.
- the shape of the base material There is no particular limitation on the shape of the base material.
- the shape of the base material include a sheet shape (that is, a film shape), a container shape such as a tray shape, and the like.
- the film may be a stretched film or a non-stretched film.
- examples of the base material containing a mixture of PE and PB or PE and PP include cohesive failure type films.
- the structure of the base material may be a single layer structure or a laminated structure composed of two or more layers.
- the thickness of the base material (total thickness in the case of a laminated structure composed of two or more layers) is not particularly limited, but preferably 0.05 mm or more from the viewpoint of ensuring the performance when the base material is used as a container. And more preferably 0.1 mm or more, and further preferably 0.2 mm or more.
- the upper limit of the thickness of the base material is, for example, 5 mm or less, 3 mm or less, 2 mm or less, and the like.
- the thickness of the base material is preferably larger than the thickness of the laminate.
- the ratio of the thickness of the base material to the thickness of the laminate (that is, the ratio [the thickness of the base material/the thickness of the laminate]) is preferably 1.5 or more, more preferably 2.0 or more. Yes, and more preferably 3.0 or more.
- the upper limit of the ratio [thickness of base material/thickness of laminated body] is, for example, 30 or less, 20 or less, 15 or less, and the like.
- packaging material of the present disclosure There is no particular limitation on the use of the packaging material of the present disclosure.
- the preferred use of the packaging material of the present disclosure is the same as the preferable use of the resin composition for a sealant of the present disclosure described above.
- a package of the present disclosure includes the above-described base material, the above-described laminated body of the present disclosure, and an object to be packaged that is wrapped with the base material and the laminated body. Since the packaging material of the present disclosure includes the above-described laminate of the present disclosure, the elution amount of the sealant layer into normal heptane is reduced, and the heat-sealing strength between the base material and the laminate is excellent.
- the preferable aspects of the base material, the laminate, and the packaged article are as described above.
- the package of the present disclosure is particularly preferably a skin pack package (that is, a package obtained by skin pack packaging).
- melt flow rate was measured according to JIS K7210-1999.
- ethylene unit content methyl acrylate unit content
- vinyl acetate unit content respectively, the content of structural units derived from ethylene, the content of structural units derived from methyl acrylate, And the content of structural units derived from vinyl acetate.
- EMA1 (comparative resin): ethylene/methyl acrylate copolymer [ethylene unit content 91% by mass, methyl acrylate unit content 9% by mass (referred to as “MA9%” in Tables 1 and 2), MFR ( 190° C., 2160 g load) 6 g/10 min, produced by high pressure radical polymerization by tubular method]
- EMA2 ethylene/methyl acrylate copolymer [ethylene unit content 80% by mass, methyl acrylate unit content 20% by mass (referred to as “MA20%” in Table 1 and Table 2)), MFR (190°C, 2160 g) (Load) 8 g/10 minutes, manufactured by high pressure radical polymerization by the tubular method]
- -EMA3 ethylene/methyl acrylate copolymer [ethylene unit content 76% by mass, methyl acrylate unit content 24% by mass (referred to as "MA24%" in Table 1 and Table 2)), MFR (190°C, 2160 g) Load) 20
- EVA1 ethylene-vinyl acetate copolymer [ethylene unit content 94% by mass, vinyl acetate unit content 6% by mass (referred to as “VA6%” in Table 1 and Table 2)), MFR (190°C, 2160 g) Load) 7g/10 minutes]
- EVA2 ethylene/vinyl acetate copolymer [ethylene unit content 90% by mass, vinyl acetate unit content 10% by mass (referred to as “VA 10%” in Table 1 and Table 2)), MFR (190°C, 2160 g) Load) 9g/10 minutes]
- EVA3 ethylene/vinyl acetate copolymer [ethylene unit content 81% by mass, vinyl acetate unit content 19% by mass (referred to as "VA 19%” in Tables 1 and 2)), MFR (190°C, 2160 g) Load) 15g/10 minutes]
- Styrenic elastomer 1 polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer (SEBS) [density 900 kg/m 3 , MFR (230° C., 5000 g load) 22 g/10 minutes, manufactured by Kraton Japan Co., Ltd. Kraton G1657]
- Hi-Zex 3300F high-density polyethylene, density 950 kg/m 3 , MFR (190° C., 2160 g load) 1.1 g/10 minutes
- Ionomer Na-neutralized product of ethylene/methacrylic acid copolymer (ethylene unit content 90 mass %, methacrylic acid unit content 10 mass %) (Na neutralization degree 50%, MFR (190° C., 2160 g load) 1 (3g/10 minutes)
- the sealant layer is a layer derived from the resin composition for a sealant
- the HDPE layer is a layer derived from the HDPE
- the ionomer layer is a layer derived from the ionomer.
- the HDPE layer/ionomer layer portion is a base material layer.
- the sealant layer is a layer derived from the resin composition for a sealant
- the EVA layer 2 is a layer derived from the EVA 2 (specifically, obtained by performing electron beam crosslinking after cast molding).
- the EVA layer 3 is a layer derived from the above EVA 3 (specifically, a layer obtained by performing electron beam crosslinking after cast molding).
- the EVA layer 2/EVA layer 3 portion is a base material layer.
- Test sample 1 having a layer structure of base material layer/sealant layer/base material by heat-sealing under the conditions of 0.2 MPa, heating temperature 120° C., and heating time 1.0 second, and then left standing at room temperature for 24 hours.
- a test piece having a width of 15 mm was cut out from the obtained test sample 1.
- the base material side and the base material layer side of the cut out test piece were pulled in opposite directions (that is, in the T-type peeling direction), and the peel strength (N/15 mm) was obtained.
- the peel strength (N/15 mm) indicates the heat-sealing strength of the resin composition for sealants with respect to the base material.
- the peel strength (N/15 mm) is preferably 3 N/15 mm or more from the viewpoint of the heat-sealing strength of the sealant resin composition to the substrate.
- a film having a layer constitution C of 100 ⁇ m and having the following layer constitution C is obtained by using the above resin composition for sealant and the following LDPE as a raw material, and performing cast molding at a processing speed of 25 m/min by a cast molding machine of 40 mm ⁇ 3 types 3 layers.
- a test sample 2 having a shape was obtained.
- LDPE low-density polyethylene, density 917 kg/m 3 , MFR (190°C, 2160 g load) 3.7 g/10 minutes (Mitsui DuPont Polychemical Co., Ltd. Mirason 16P)
- the sealant layer is a layer derived from the resin composition for a sealant
- the LDPE layer is a layer derived from the LDPE.
- the LDPE layer/LDPE layer portion is the base material layer.
- the elution amount ( ⁇ g/mL) of the sealant layer (that is, the resin composition for sealant) per 1 mL of normal heptane is calculated based on the obtained value. did.
- the elution amount ( ⁇ g/mL) is preferably 30 ⁇ g/mL or less.
- a resin (A) which is an ethylene/(meth)acrylic acid ester copolymer having a content of (meth)acrylic acid ester units of 10% by mass or more and 25% by mass or less
- a tackifying resin (B) the content of the resin (A) is more than 45% by mass
- the content of the tackifying resin (B) is 0.1% by mass or more and 10% by mass or less
- the sealant resin compositions of Examples 1 to 10 had a reduced elution amount in normal heptane and were excellent in heat seal strength with respect to the substrate.
- the resin composition for sealant of Comparative Example 1 which does not contain the tackifying resin (B), had insufficient heat seal strength for the substrate.
- the resin composition for a sealant of Comparative Example 2 in which the content of the (meth)acrylic acid ester unit in the ethylene/(meth)acrylic acid ester copolymer is less than 10% by mass is insufficient in heat seal strength for the base material.
- the resin compositions for sealants of Comparative Examples 3 and 4 in which the content of the resin (A) was less than 45% by mass also had insufficient heat seal strength with respect to the base material.
- the resin composition for a sealant of Comparative Example 5 in which the content of the tackifying resin (B) was more than 10% by mass, the elution amount in normal heptane was excessive.
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Abstract
Description
例えば、特開2008-95044号公報には、プラスチック製容器、特に、耐衝撃性ポリスチレンの容器に用いるヒートシール材として好適で、容器本体構成材に対し従来品に比べより適正な範囲の剥離強度を有すると共に、食品等容器内容物の密封保護性等、この種のヒートシール材として必要とされる諸物性を従来品とほぼ同等に保持し、然も従来品に比べより高い耐熱性と低温でのヒートシール処理でも剥離時にスムーズで且つ快適な剥離感を呈するヒートシール性樹脂組成物として、エチレン・ビニルエステル共重合体樹脂(A)30~80質量部、エチレン・(メタ)アクリル酸エステル共重合体樹脂(B)1~45質量部及び粘着付与樹脂(C)3~30質量部(但し(A)、(B)、(C)樹脂の合計量は100質量部)を含んでなるシール材用樹脂組成物が知られている。
また、シーラント用樹脂組成物に対し、衛生性の観点から、ノルマルへプタンへの溶出量を低減することが求められる場合がある。
本開示の第1態様の課題は、基材に対するヒートシール強度に優れ、かつ、ノルマルへプタンへの溶出量が低減されているシーラント用樹脂組成物を提供することである。
本開示の第2態様の課題は、基材層及びシーラント層を含み、基材に対するヒートシール強度に優れ、かつ、シーラント層のノルマルへプタンへの溶出量が低減されている積層体を提供することである。
本開示の第3態様の課題は、上記積層体を備え、基材に対するヒートシール強度に優れ、かつ、シーラント層のノルマルへプタンへの溶出量が低減されている包装材料を提供することである。
本開示の第4態様の課題は、基材と、基材層及びシーラント層を含む積層体と、被包装物と、を備え、上記基材と上記積層体とのヒートシール強度に優れ、かつ、シーラント層のノルマルへプタンへの溶出量が低減されている包装体を提供することである。
<1> (メタ)アクリル酸エステル単位の含有量が10質量%以上25質量%以下であるエチレン・(メタ)アクリル酸エステル共重合体である樹脂(A)と、
粘着付与樹脂(B)と、
を含有し、
前記樹脂(A)の含有量が、シーラント用樹脂組成物中の樹脂成分の全量に対し、45質量%超であり、
前記粘着付与樹脂(B)の含有量が、シーラント用樹脂組成物中の樹脂成分の全量に対し、0.1質量%以上10質量%以下であるシーラント用樹脂組成物。
<2> 更に、エチレン・ビニルエステル共重合体である樹脂(C)を含有する<1>に記載のシーラント用樹脂組成物。
<3> 更に、エチレン・α-オレフィン共重合体エラストマー、スチレン系エラストマー、及びポリエチレンからなる群から選択される少なくとも1種である樹脂(D)を含有する<1>又は<2>に記載のシーラント用樹脂組成物。
<4> 前記樹脂(D)の含有量が、シーラント用樹脂組成物中の樹脂成分の全量に対し、5質量%以上40質量%以下である<3>に記載のシーラント用樹脂組成物。
<5> 包装材料用のシーラントとして用いられる<1>~<4>のいずれか1つに記載のシーラント用樹脂組成物。
<6> 前記包装材料が、スキンパック包装用の包装材料である<5>に記載のシーラント用樹脂組成物。
<7> 基材層と、
<1>~<6>のいずれか1つに記載のシーラント用樹脂組成物を含むシーラント層と、
を含む積層体。
<8> 前記基材層が、エチレン・不飽和カルボン酸共重合体のアイオノマー及びエチレン・不飽和エステル共重合体からなる群から選択される少なくとも1種を含有する<7>に記載の積層体。
<9> 厚さが40μm以上300μm以下である<7>又は<8>に記載の積層体。
<10> <7>~<9>のいずれか1つに記載の積層体を備える包装材料。
<11> 基材を更に備える<10>に記載の包装材料。
<12> 前記基材がポリプロピレンを含む<11>に記載の包装材料。
<13> 基材と、
<7>~<9>のいずれか1つに記載の積層体と、
前記基材及び前記積層体によって包装された被包装物と、
を備える包装体。
本開示の第2態様によれば、基材層及びシーラント層を含み、基材に対するヒートシール強度に優れ、かつ、シーラント層のノルマルへプタンへの溶出量が低減されている積層体が提供される。
本開示の第3態様によれば、上記積層体を備え、基材に対するヒートシール強度に優れ、かつ、シーラント層のノルマルへプタンへの溶出量が低減されている包装材料が提供される。
本開示の第4態様によれば、基材と、基材層及びシーラント層を含む積層体と、被包装物と、を備え、上記基材と上記積層体とのヒートシール強度に優れ、かつ、シーラント層のノルマルへプタンへの溶出量が低減されている包装体が提供される。
本開示において、組成物中の各成分の量は、組成物中に各成分に該当する物質が複数存在する場合は、特に断らない限り、組成物中に存在する複数の物質の合計量を意味する。
本開示に段階的に記載されている数値範囲において、ある数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよく、また、実施例に示されている値に置き換えてもよい。
本開示において、「(メタ)アクリル酸」は、アクリル酸及びメタクリル酸の両方を包含する概念であり、「(メタ)アクリル酸エステル」は、アクリル酸エステル及びメタクリル酸エステルの両方を包含する概念である。
本開示のシーラント用樹脂組成物は、(メタ)アクリル酸エステル単位の含有量が10質量%以上25質量%以下であるエチレン・(メタ)アクリル酸エステル共重合体である樹脂(A)と、粘着付与樹脂(B)と、を含有し、樹脂(A)の含有量が、シーラント用樹脂組成物中の樹脂成分の全量に対し、45質量%超であり、粘着付与樹脂(B)の含有量が、シーラント用樹脂組成物中の樹脂成分の全量に対し、0.1質量%以上10質量%以下である。
また、本開示のシーラント用樹脂組成物は、衛生性の指標の一つであるノルマルへプタンへの溶出量が低減されている。
かかる効果が奏される理由は、以下のように推測される。
樹脂(A)(即ち、エチレン・(メタ)アクリル酸エステル共重合体)における(メタ)アクリル酸エステル単位の含有量が10質量%以上であること、
シーラント用樹脂組成物中の樹脂成分の全量に対する樹脂(A)の含有量(以下、単に、「樹脂(A)の含有量」ともいう)が45質量%超であること、及び
粘着付与樹脂(B)の含有量が0.1質量%以上であること
が寄与していると考えられる。
シーラント用樹脂組成物中の樹脂成分の全量に対する粘着付与樹脂(B)の含有量(以下、単に、「粘着付与樹脂(B)の含有量」ともいう)が10質量%以下であること、及び、
樹脂(A)(即ち、エチレン・(メタ)アクリル酸エステル共重合体)における(メタ)アクリル酸エステル単位の含有量が25質量%以下であること
が寄与していると考えられる。
樹脂を含有する基材は、更に、フィラー等を含有していてもよい。
PE、PP、PS、HIPS、又はPETを含有する基材としてフィルムを用いる場合、フィルムは、延伸フィルムであってもよいし、無延伸フィルムであってもよい。
また、PE及びPBの混合物又はPE及びPPを含有する基材としては、凝集破壊タイプのフィルムが挙げられる。
上述した樹脂を含有する基材のうち、例えば、ポリプロピレン(PP)を含有する基材は、他の物体とのヒートシール強度の確保が比較的難しい基材である。本開示のシーラント用樹脂組成物は、かかるポリプロピレン(PP)を含有する基材に対しても、ヒートシール強度に優れる(後述の実施例参照)。
本開示のシーラント用樹脂組成物は、樹脂(A)を含有する。
樹脂(A)は、(メタ)アクリル酸エステル単位(即ち、(メタ)アクリル酸エステルに由来する構造単位)の含有量が10質量%以上25質量%以下であるエチレン・(メタ)アクリル酸エステル共重合体である。
ここで、(メタ)アクリル酸エステル単位の含有量は、エチレン・(メタ)アクリル酸エステル共重合体(即ち、樹脂(A))の全量に対する含有量(樹脂(A)中に(メタ)アクリル酸エステル単位が2種以上含まれる場合は総含有量)である。
本開示のシーラント用樹脂組成物に含有される樹脂(A)は、1種のみであってもよいし、2種以上であってもよい。
また、樹脂(A)に含有される(メタ)アクリル酸エステル単位は、1種のみであってもよいし、2種以上であってもよい。
シーラント用樹脂組成物のノルマルヘプタンへの溶出量を低減する観点から、樹脂(A)における(メタ)アクリル酸エステル単位の含有量は、好ましくは24質量%以下であり、より好ましくは22質量%以下である。
ここで、エチレン単位の含有量は、エチレン・(メタ)アクリル酸エステル共重合体(即ち、樹脂(A))の全量に対する含有量である。
シーラント用樹脂組成物のノルマルヘプタンへの溶出量を低減する観点から、樹脂(A)におけるエチレン単位の含有量は、好ましくは76質量%以上であり、より好ましくは78質量%以上である。
樹脂(A)における、エチレン単位及び(メタ)アクリル酸エステル単位の総含有量は、樹脂(A)の全量に対し、好ましくは80質量%以上であり、より好ましくは90質量%以上である。
(メタ)アクリル酸エステル単位を形成するためのモノマーにおける、アルキルエステル部分(即ち、アルコキシ基)の炭素数は、より好ましくは1~8であり、更に好ましくは1~6であり、更に好ましくは1~4であり、更に好ましくは1又は2である。
(メタ)アクリル酸エステル単位を形成するためのモノマーとしては、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸n-プロピル、(メタ)アクリル酸イソプロピル、(メタ)アクリル酸n-ブチル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸n-ヘキシル、(メタ)アクリル酸イソヘキシル、(メタ)アクリル酸n-オクチル、(メタ)アクリル酸イソオクチル、(メタ)アクリル酸-2-エチルヘキシル、等が挙げられる。
樹脂(A)の合成方法については、例えば、特開2008-95044号公報の段落0020~0023の記載を適宜参照できる。
この方法で得られた共重合体樹脂は、通常のラジカル重合法等の他の方法で製造されたエチレン・(メタ)アクリル酸エステル共重合体に比較して、例え共重合組成や平均分子量が同じものであっても融点が高く、然も、軟化から溶融状態での粘弾性挙動等の熱的諸物性やその他の属性が異なり、このためそれを配合して得られた組成物は前述した本開示の組成物の特性をより良好に発現することが出来る。
-0.8×E+115≧T≧-0.8×E+109…(I)
を満足することが特徴であって、他の重合法で得られた相当組成の共重合体に比べて融点が高く耐熱性に優れる。
上記重合法で得られた共重合体は通常のラジカル重合法によるランダム性良好な共重合体に比較して、エチレン単位や(メタ)アクリル酸エステル単位のランダム配列が少なく、即ち、配列不均一性が高く、ブロック共重合体にやや似た重合体構造、物性を有する。
このため融点とエステル単位含量が上記のような関係を有するものと考えられる。
シーラント用樹脂組成物の基材に対するヒートシール強度をより向上させる観点から、樹脂(A)の含有量は、好ましくは46質量%以上であり、より好ましくは47質量%以上であり、更に好ましくは50質量%以上である。
樹脂(A)の含有量の上限は、粘着付与樹脂(B)等の他の成分の含有量による。
樹脂(A)の含有量の上限は、原理的に99.9質量%である。樹脂(A)の含有量の上限としては、98.9質量%、98質量%、97.9質量%、90質量%、80質量%、70質量%、65質量%等も挙げられる。
本開示のシーラント用樹脂組成物が、後述する樹脂(C)を含有する場合、樹脂成分には樹脂(C)も含まれる。
本開示のシーラント用樹脂組成物が、後述する樹脂(D)を含有する場合、樹脂成分には樹脂(D)も含まれる。
本開示のシーラント用樹脂組成物は、粘着付与樹脂(B)を含有する。
シーラント用樹脂組成物に含有される粘着付与樹脂(B)は、1種のみであってもよいし、2種以上であってもよい。
脂環族炭化水素樹脂としては、スペントC4~C5留分中のジエン成分を環化二量体化後重合させた樹脂、シクロペンタジエンなどの環状モノマーを重合させた樹脂、芳香族炭化水素樹脂を核内水添した樹脂、等が挙げられる。
芳香族炭化水素樹脂の例としては、ビニルトルエン、インデン、α-メチルスチレンなどのC9~C10のビニル芳香族炭化水素を主成分とするモノマー原料の重合体等が挙げられる。
環球法軟化点は、JIS K6863(1994年)に準拠して測定された値を意味する。
本開示のシーラント用樹脂組成物では、粘着付与樹脂(B)の含有量が0.1質量%以上であることにより、シーラント用樹脂組成物の基材に対するヒートシール強度が向上する。シーラント用樹脂組成物の基材に対するヒートシール強度を向上させる観点から、粘着付与樹脂(B)の含有量は、好ましくは0.5質量%以上であり、より好ましくは1質量%以上であり、更に好ましくは1.5質量%以上である。
粘着付与樹脂(B)の含有量が10質量%以下であることにより、シーラント用樹脂組成物のノルマルへプタンへの溶出量が低減される。シーラント用樹脂組成物のノルマルへプタンへの溶出量をより低減する観点から、粘着付与樹脂(B)の含有量は、好ましくは5質量%以下であり、より好ましくは3質量%以下であり、さらに好ましくは3質量%未満であり、特に好ましくは2.5質量%以下である。
本開示のシーラント用樹脂組成物は、更に、エチレン・ビニルエステル共重合体である樹脂(C)を含有することが好ましい。
この場合、含有される樹脂(C)は、1種のみであってもよいし、2種以上であってもよい。
本開示のシーラント用樹脂組成物が、更に、樹脂(C)を含有することは、後述する積層体としてフィルム形状の積層体を製造する場合において、製造時のロールスティックが軽減される、フィルム間の互着が軽減される、等の点で有利である。
ビニルエステル単位を形成するためのビニルエステルとしては、酢酸ビニル又はプロピオン酸ビニルが好ましく、酢酸ビニルがより好ましい。
ビニルエステルの含有量が2質量%以上である場合には、シーラント用樹脂組成物の基材に対するヒートシール強度がより向上する。
ビニルエステルの含有量が30質量%以下である場合には、シーラント用樹脂組成物の基材に対するヒートシール強度がより向上し、かつ、シーラント用樹脂組成物のノルマルヘプタンへの溶出量がより低減される。
エチレン単位の含有量が98質量%以下である場合には、シーラント用樹脂組成物の基材に対するヒートシール強度がより向上する。
エチレン単位の含有量が70質量%以上である場合には、シーラント用樹脂組成物の基材に対するヒートシール強度がより向上し、かつ、シーラント用樹脂組成物のノルマルヘプタンへの溶出量がより低減される。
樹脂(C)におけるエチレン単位及びビニルエステル単位の総含有量は、樹脂(C)の全量に対し、好ましくは80質量%以上であり、より好ましくは90質量%以上である。
樹脂(C)の含有量が50質量%以下である場合には、シーラント用樹脂組成物の基材に対するヒートシール強度がより向上する。
樹脂(C)の含有量が1質量%以上である場合には、後述する積層体としてフィルム形状の積層体を製造する場合において、製造時のロールスティックが軽減される、フィルム間の互着が軽減される、等の点で有利である。
本開示のシーラント用樹脂組成物は、更に、エチレン・α-オレフィン共重合体エラストマー、スチレン系エラストマー、及びポリエチレンからなる群から選択される少なくとも1種である樹脂(D)を含有することが好ましい。
本開示のシーラント用樹脂組成物が、更に、樹脂(D)を含有する場合には、シーラント用樹脂組成物の基材に対するヒートシール強度がより向上する。
かかる効果をより効果的に得る観点から、樹脂(D)は、エチレン・α-オレフィン共重合体エラストマー及びスチレン系エラストマーからなる群から選択される少なくとも1種を含むことが更に好ましい。
α-オレフィン単位を形成するためのα-オレフィンの炭素数は、好ましくは3~10であり、より好ましくは3~8である。
α-オレフィン単位を形成するためのα-オレフィンとしては、プロピレン、1-ブテン、1-ペンテン、1-ヘキセン、1-オクテン、4-メチル-1-ペンテンなどが挙げられる。
使用する触媒又はα-オレフィンの種類によっても若干異なるが、上記結晶化度を有するエチレン・α-オレフィン共重合体エラストマーを得る方法としては、例えば、α-オレフィンの共重合比率を7モル%~20モル%(好ましくは8モル%~16モル%)として、エチレン及びα-オレフィンを共重合させる方法が挙げられる。
ここで、スチレン重合体ブロックとは、ポリスチレンの部位を指し、アルキレン共重合体ブロックとは、2以上のアルケンが共重合したアルキレン共重合体の部位を指す。
ポリエチレンの密度は、ポリエチレンの種類にもよるが、好ましくは900kg/m3以上であり、より好ましくは910kg/m3以上である。ポリエチレンの密度の上限には特に制限はないが、上限は、例えば960kg/m3である。
HDPEの密度は、好ましくは942kg/m3以上であり、より好ましくは942kg/m3以上960kg/m3以下である。
MDPEの密度は、好ましくは930kg/m3以上942kg/m3未満である。
LDPEの密度は、好ましくは910kg/m3以上930kg/m3未満である。
LLDPEの密度は、好ましくは900kg/m3以上930kg/m3未満である。
樹脂(D)の含有量が1質量%以上である場合には、シーラント用樹脂組成物の基材に対するヒートシール強度がより向上する。
樹脂(D)の含有量が50質量%以下である場合には、シーラント用樹脂組成物の基材に対するヒートシール強度が過剰となることがより抑制される。
本開示のシーラント用樹脂組成物は、上述した成分以外のその他の成分を含有していてもよい。
その他の成分としては、スリップ剤、離ロール剤等の添加剤が挙げられる。
パルミチン酸アミド、ステアリン酸アミド、ベヘニン酸アミド、オレイン酸アミド、エルカ酸アミド、オレイルパルミトアミド、ステアリルパルミトアミド、メチレンビスステアリルアミド、メチレンビスオレイルアミド、エチレンビスエルカ酸アミドなどの各種アミド類;
ポリエチレングリコール、ポリプロピレングリコールなどのポリアルキレングリコール;
水添ひまし油;
シリカ、タルク、ゼオライトなどの無機質添加剤;
等が挙げられる。
添加剤の含有量は、樹脂成分の全量に対し、好ましくは0.01質量%~3質量%である。
本開示のシーラント用樹脂組成物が、樹脂(C)を含有する場合、樹脂成分には、更に樹脂(C)も含まれる。本開示のシーラント用樹脂組成物は、樹脂成分として、樹脂(A)と、粘着付与樹脂(B)と、樹脂(C)と、を含有し、シーラント用樹脂組成物中の樹脂成分の全量に対し、樹脂(A)の含有量が、45質量%超であり、粘着付与樹脂(B)の含有量が、0.1質量%以上10質量%以下であり、樹脂(C)の含有量が、1質量%以上50質量%以下であるのも好ましい一態様である。
本開示のシーラント用樹脂組成物が、樹脂(D)を含有する場合、樹脂成分には、更に樹脂(D)も含まれる。本開示のシーラント用樹脂組成物は、樹脂成分として、樹脂(A)と、粘着付与樹脂(B)と、樹脂(C)と、樹脂(D)と、を含有し、シーラント用樹脂組成物中の樹脂成分の全量に対し、樹脂(A)の含有量が、45質量%超であり、粘着付与樹脂(B)の含有量が、0.1質量%以上10質量%以下であり、樹脂(C)の含有量が、1質量%以上50質量%以下であり、樹脂(D)の含有量が、1質量%以上50質量%以下であるのも好ましい一態様である。
本開示のシーラント用樹脂組成物は、基材に対するヒートシール強度及びノルマルへプタンへの溶出量低減が要求される、あらゆる用途に適用できる。
本開示のシーラント用樹脂組成物の用途には特に制限はないが、好ましくは、包装材料用のシーラントとして用いられる。
包装材料としては、食品用の包装材料が好ましい。
食品としては、肉類、肉製品、肉料理、魚介類、魚介料理、水産加工食品、総菜、調理パスタ、乳加工食品、等が挙げられる。
食品については、厚生省告示第370号(「食品、添加物等の規格基準」)を参照できる。
ここで、スキンパック包装とは、包装材料の少なくとも一部が、被包装物の形状に追従しつつ被包装物に密着している態様の真空包装を意味する。
スキンパック包装では、上記態様の真空包装を実現するために、シーラントが用いられる。
スキンパック包装用の包装材料は、基材(例えば、容器、トレイ等)を含むことが多いため、かかる包装材料用のシーラントには、基材に対するヒートシール強度が要求されることが多い。また、スキンパック包装用の包装材料には、被包装物の品質を保つために衛生性(例えば、ノルマルへプタンへの溶出量の低減)が要求されることが多いため、かかる包装材料用のシーラントには、ノルマルへプタンへの溶出量低減が要求されることが多い。
これらの理由により、本開示のシーラント用樹脂組成物が適用される包装材料としては、スキンパック包装用の包装材料であることが好ましい。
本開示の積層体は、基材層と、上述した本開示のシーラント用樹脂組成物を含むシーラント層と、を含む。
本開示の積層体は、上述した本開示のシーラント用樹脂組成物を含むシーラント層を含むので、基材に対するヒートシール強度に優れ、かつ、シーラント層のノルマルへプタンへの溶出量が低減される。
基材層は、上述した本開示のシーラント用樹脂組成物を含むシーラント層が直接又は他の層を介して積層され、包装材料としての強度を確保する層である。
基材層の材質には特に制限はない。基材層の材質としては、延伸あるいは無延伸のフィルムであって、例えば、ポリエチレンテレフタレート等のポリエステル;ポリアミド;ポリプロピレン、ポリエチレン等のポリオレフィン;エチレン・酢酸ビニル共重合体、エチレン・不飽和カルボン酸エステル共重合体等のエチレン・不飽和エステル共重合体;エチレン・不飽和カルボン酸共重合体又はそのアイオノマー;エチレン・ビニルアルコール共重合体;紙;アルミ箔;アルミニウム、シリカ、アルミナ、マグネシアなどを蒸着したフィルム;ポリ塩化ビニリデンやポリビニルアルコールなどのガスバリア材をコーティングしたフィルムなどを例示することができる。また、基材層の構造は、単層構造であってもよいし、2層以上からなる積層構造であってもよい。
熱可塑性樹脂としては特に限定されないが、例えば、ポリエチレンテレフタレート等のポリエステル;ポリアミド;ポリプロピレン、ポリエチレン等のポリオレフィン;エチレン・酢酸ビニル共重合体、エチレン・不飽和カルボン酸エステル共重合体等のエチレン・不飽和エステル共重合体;エチレン・不飽和カルボン酸共重合体又はそのアイオノマー;エチレン・ビニルアルコール共重合体などを例示することができる。基材層は、エチレン・不飽和カルボン酸共重合体のアイオノマー及びエチレン・不飽和エステル共重合体からなる群から選択される少なくとも1種を含有することがより好ましい。
特に、基材層が、上記の群から選択される少なくとも1種を含有する場合には、積層体の伸長性が向上する。伸長性は、例えば、積層体を包装材料として用いる場合に求められ得る特性である。
特に、伸長性に優れた積層体を、スキンパック包装用の包装材料として用いた場合には、被包装物の形状への追従性、及び、被包装物に対する密着性がより向上する。
基材層は、エチレン・不飽和カルボン酸共重合体のアイオノマーを少なくとも1種含有し得る。
基材層が、エチレン・不飽和カルボン酸共重合体のアイオノマーを含有する場合には、積層体の伸長性だけでなく、積層体の突き刺し強度も向上する。
突き刺し強度も、積層体を包装材料(特に、スキンパック包装用の包装材料)として用いる場合に求められ得る性質である。
工業的に入手可能な観点から、エチレン・不飽和カルボン酸共重合体としては、ランダム共重合体であることが好ましい。
これらの中でも、不飽和カルボン酸単位としては、(メタ)アクリル酸単位が好ましく、メタクリル酸単位が更に好ましい。
その他の構造単位としては、不飽和カルボン酸エステル単位が挙げられる。不飽和カルボン酸エステル単位の好ましい態様は、前述した樹脂(A)における(メタ)アクリル酸エステル単位の好ましい態様と同様である。
エチレン・不飽和カルボン酸共重合体における、エチレン単位及び不飽和カルボン酸単位の総含有量は、エチレン・不飽和カルボン酸共重合体の全量に対し、好ましくは80質量%以上であり、より好ましくは90質量%以上である。
金属イオンとしては、例えば;
リチウムイオン、ナトリウムイオン、カリウムイオン、ルビジウムイオン、セシウムイオン等のアルカリ金属イオン;
マグネシウムイオン、カルシウムイオン等のアルカリ土類金属イオン;
亜鉛イオン等の遷移金属イオン;
アルミニウムイオン等の各種金属イオン;
などが挙げられる。
ベースポリマーにおける酸性基を中和するための金属イオンは、1種のみであってもよいし、2種以上であってもよい。
中和度が90%以下であると、イオン凝集を適度に抑制でき、かつ、流動性の低下をより抑制でき、成形加工性をより好適に維持できる。
中和度が5%以上であると、アイオノマーとしての性能をより効果的に発揮することが可能である。
ここで、「中和度(%)」とは、エチレン・不飽和カルボン酸共重合体(ベースポリマー)に含まれる全カルボキシル基のうち、金属イオンによって中和されているカルボキシル基の割合(モル%)を指す。
基材層は、エチレン・不飽和エステル共重合体を少なくとも1種含有し得る。
エチレン・不飽和エステル共重合体は、エチレン単位と不飽和エステル単位(即ち、不飽和エステルに由来する構造単位)とを含む。
エチレン・不飽和エステル共重合体は、ブロック共重合体、ランダム共重合体、及びグラフト共重合体のいずれであってもよい。
酢酸ビニル、プロピオン酸ビニル等のビニルエステル;
(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸n-ブチル、(メタ)アクリル酸イソオクチル等の(メタ)アクリル酸エステル;
等が挙げられる。
これらの中でも、不飽和エステルとしては、酢酸ビニル及び(メタ)アクリル酸エステルの少なくとも一方であることが好ましい。
エチレン・不飽和エステル共重合体における、エチレン単位及び不飽和エステル単位の総含有量は、エチレン・不飽和エステル共重合体の全量に対し、好ましくは80質量%以上であり、より好ましくは90質量%以上である。
架橋構造を形成する方法としては、熱架橋、電子線架橋、放射線架橋、等が挙げられる。中でも、架橋効率、衛生性の観点から、電子線架橋が好ましい。
基材層は、添加剤等のその他の成分を含有していてもよい。
基材層の全体に対する、エチレン・不飽和カルボン酸共重合体のアイオノマー及びエチレン・不飽和エステル共重合体の総含有量は、基材層の全量に対し、好ましくは80質量%以上であり、より好ましくは90質量%以上である。
シーラント層は、上述した本開示のシーラント用樹脂組成物を含む層である。
シーラント層の構造は、単層構造であってもよいし、2層以上からなる積層構造であってもよい。
シーラント層は、例えば、本開示のシーラント用樹脂組成物(及び、必要に応じ添加剤等の他の成分)を用いた溶融押出しによって製造される。
シーラント層における、本開示のシーラント用樹脂組成物の含有量は、シーラント層の全量に対し、好ましくは80質量%以上であり、より好ましくは90質量%以上である。
本開示の積層体は、公知の方法を用いて製造することができる。
積層体の製造方法としては、例えば、押出ラミネーション法、共押出インフレーション法、共押出Tダイ法等が挙げられる。
中でも、積層体の厚さ制御の点から、共押出Tダイ法が好ましい。
本開示の積層体の用途については特に制限はない。
本開示の積層体の好ましい用途は、前述した本開示のシーラント用樹脂組成物の好ましい用途と同様である。
本開示の包装材料は、上述した本開示の積層体を備える。
このため、基材とのヒートシール強度に優れ、かつ、シーラント層のノルマルへプタンへの溶出量が低減される。
かかる態様の包装材料として、基材と積層体とを備えるセットである包装材料、基材の一部と積層体におけるシーラント層の一部とが接着されている一体型の包装材料、等が挙げられる。
樹脂の例については、「シーラント用樹脂組成物」の項で説明したとおりであり、例えば、ポリエチレン(PE)、ポリプロピレン(PP)、ポリスチレン(PS)、耐衝撃性ポリスチレン(HIPS)、ポリエチレンテレフタレート(PET)、ポリエチレン(PE)及びポリブテン(PB)の混合物、ポリエチレン(PE)及びポリプロピレン(PP)の混合物、等が挙げられ、ポリプロピレン(PP)が好ましい。
基材における樹脂の含有量は、基材の全量に対し、好ましくは80質量%以上であり、より好ましくは90質量%以上である。
基材の形状としては、シート形状(即ち、フィルム形状)、トレー形状等の容器形状、等が挙げられる。PE、PP、PS、HIPS、又はPETを含有する基材としてフィルムを用いる場合、フィルムは、延伸フィルムであってもよいし、無延伸フィルムであってもよい。また、PE及びPBの混合物又はPE及びPPを含有する基材としては、凝集破壊タイプのフィルムが挙げられる。
また、基材の構造は、単層構造であってもよいし、2層以上からなる積層構造であってもよい。
基材の厚さの上限としては、例えば、5mm以下、3mm以下、2mm以下、等が挙げられる。
積層体の厚さに対する基材の厚さの比(即ち、比〔基材の厚さ/積層体の厚さ〕)が、好ましくは1.5以上であり、更に好ましくは2.0以上であり、更に好ましくは3.0以上である。
比〔基材の厚さ/積層体の厚さ〕の上限としては、例えば、30以下、20以下、15以下、等が挙げられる。
本開示の包装材料の好ましい用途は、前述した本開示のシーラント用樹脂組成物の好ましい用途と同様である。
本開示の包装体は、上述した基材と、上述した本開示の積層体と、基材及び積層体によって包装された被包装物と、を備える。
本開示の包装材料は、上述した本開示の積層体を備えるので、シーラント層のノルマルへプタンへの溶出量が低減され、かつ、基材と積層体とのヒートシール強度に優れる。
基材、積層体、及び被包装物の好ましい態様については、それぞれ前述したとおりである。
本開示の包装体は、スキンパック包装体(即ち、スキンパック包装によって得られる包装体)であることが特に好ましい。
以下、メルトフローレート(MFR)は、JISK7210-1999に準拠して測定した。
以下、「エチレン単位含有量」、「メチルアクリレート単位含有量」、及び「酢酸ビニル単位含有量」は、それぞれ、エチレンに由来する構造単位の含有量、メチルアクリレートに由来する構造単位の含有量、及び酢酸ビニルに由来する構造単位の含有量を意味する。
<シーラント用樹脂組成物の作製>
以下の成分を、表1及び表2に示す配合割合で、仕込み量が10kgとなるように混合した。得られた混合物を、押出機(65mmφ、L/D=28、先端ダルメージフライトスクリュー)に投入し、加工温度160℃にて溶融混練することにより、各実施例及び各比較例のシーラント用樹脂組成物をそれぞれ得た。
表1及び表2における空欄は、該当する成分が含有されていないことを意味する。
・EMA1(比較樹脂):エチレン・メチルアクリレート共重合体〔エチレン単位含有量91質量%、メチルアクリレート単位含有量9質量%(表1及び表2中では「MA9%」と表記する)、MFR(190℃、2160g荷重)6g/10分、チューブラー法による高圧ラジカル重合で製造〕
・EMA2:エチレン・メチルアクリレート共重合体〔エチレン単位含有量80質量%、メチルアクリレート単位含有量20質量%(表1及び表2中では「MA20%」と表記する)、MFR(190℃、2160g荷重)8g/10分、チューブラー法による高圧ラジカル重合で製造〕
・EMA3:エチレン・メチルアクリレート共重合体〔エチレン単位含有量76質量%、メチルアクリレート単位含有量24質量%(表1及び表2中では「MA24%」と表記する)、MFR(190℃、2160g荷重)20g/10分、チューブラー法による高圧ラジカル重合で製造〕
・荒川化学工業(株)製「アルコン AM-1」(環球法軟化点115℃の脂環族炭化水素樹脂)
・EVA1:エチレン・酢酸ビニル共重合体〔エチレン単位含有量94質量%、酢酸ビニル単位含有量6質量%(表1及び表2中では「VA6%」と表記する)、MFR(190℃、2160g荷重)7g/10分〕
・EVA2:エチレン・酢酸ビニル共重合体〔エチレン単位含有量90質量%、酢酸ビニル単位含有量10質量%(表1及び表2中では「VA10%」と表記する)、MFR(190℃、2160g荷重)9g/10分〕
・EVA3:エチレン・酢酸ビニル共重合体〔エチレン単位含有量81質量%、酢酸ビニル単位含有量19質量%(表1及び表2中では「VA19%」と表記する)、MFR(190℃、2160g荷重)15g/10分〕
・PO-1:エチレン・1-ブテン共重合体〔密度885kg/m3、MFR(190℃、2160g荷重)3.7g/10分(三井化学(株)製タフマーA4085S)〕
・PO-2:エチレン・プロピレン共重合体〔密度875kg/m3、MFR(190℃、2160g荷重)2g/10分(三井化学(株)製タフマーP0275)〕
・PO-3:エチレン・1-オクテン共重合体〔密度870kg/m3、MFR(190℃、2160g荷重)5g/10分(三井化学(株)製タフマーH5030S)〕
・スチレン系エラストマー1:ポリスチレン-ポリ(エチレン-ブチレン)-ポリスチレントリブロック共重合体(SEBS)〔密度900kg/m3、MFR(230℃,5000g荷重)22g/10分、クレイトンジャパン(株)製クレイトンG1657〕
・スリップ剤としてのエルカ酸アミド(2質量部)と、シリカ(20質量部)と、ベースポリマーとしてのエチレン・酢酸ビニル共重合体(78質量部)と、の混合物(三井・デュポンポリケミカル(株)製M445)
(層構成Aの積層体の作製;実施例1~8及び10並びに比較例1~5)
上記シーラント用樹脂組成物、下記HDPE、及び下記アイオノマーを原料として用い、40mmφ3種3層のキャスト成形機により、加工速度25m/分の条件でキャスト成形を行うことにより、下記層構成Aを有する厚さ100μmのフィルム形状の積層体を得た。
・HDPE:プライムポリマー(株)製ハイゼックス3300F(高密度ポリエチレン、密度950kg/m3、MFR(190℃、2160g荷重)1.1g/10分)
・アイオノマー:エチレン・メタクリル酸共重合体(エチレン単位含有量90質量%、メタクリル酸単位含有量10質量%)のNa中和物(Na中和度50%、MFR(190℃,2160g荷重)1.3g/10分)
・層構成A:HDPE層/アイオノマー層/シーラント層(層比〔HDPE層/アイオノマー層/シーラント層〕=10/80/10又は10/85/5;詳細は表1及び表2参照)
層構成Aにおいて、HDPE層/アイオノマー層の部分は、基材層である。
上記シーラント用樹脂組成物、上述したEVA2、及び上述したEVA3を原料として用い、40mmφ3種3層のキャスト成形機により、加工速度25m/分の条件でキャスト成形を行い、3層構成のフィルム形状の成形体を得た。得られた成形体における、EVA2由来の層及びEVA3由来の層に対し、電子線架橋を施すことにより、下記層構成Bを有する厚さ100μmのフィルム形状の積層体を得た。
層構成B:EVA層2/EVA層3/シーラント層(層比〔EVA層2/EVA層3/シーラント層〕=30/60/10)
層構成Bにおいて、EVA層2/EVA層3の部分は、基材層である。
上記シーラント用樹脂組成物及び上記積層体を用い、以下の評価を実施した。
結果を表1及び表2に示す。
(試験用サンプル1の作製)
上記積層体を、基材としての厚さ0.4mmのポリプロピレン(PP)シート(プライムポリマー社製F317DV)上に、上記積層体におけるシーラント層と基材とが接触する向きで重ね、押圧力0.2MPa、加熱温度120℃、及び加熱時間1.0秒の条件でヒートシールし、次いで室温で24時間放置することにより、基材層/シーラント層/基材の層構成を有する試験用サンプル1を得た。
得られた試験用サンプル1から、15mm幅の試験片を切り出した。
切り出した試験片における基材側及び基材層側を、反対方向に(即ち、T型剥離の方向に)引張り、剥離強度(N/15mm)を求めた。
上記剥離強度(N/15mm)は、シーラント用樹脂組成物の基材に対するヒートシール強度を示している。
シーラント用樹脂組成物の基材に対するヒートシール強度の観点から、上記剥離強度(N/15mm)は、3N/15mm以上であることが好ましい。
(試験用サンプル2の作製)
上記シーラント用樹脂組成物及び下記LDPEを原料として用い、40mmφ3種3層のキャスト成形機により、加工速度25m/分の条件でキャスト成形を行うことにより、下記層構成Cを有する厚さ100μmのフィルム形状の試験用サンプル2を得た。
・LDPE:低密度ポリエチレン、密度917kg/m3、MFR(190℃、2160g荷重)3.7g/10分(三井・デュポンポリケミカル(株)製ミラソン16P)
・層構成C:LDPE層/LDPE層/シーラント層(層比〔LDPE層/LDPE層/シーラント層〕=10/80/10又は10/85/5;詳細は表1及び表2参照)
層構成Cにおいて、LDPE層/LDPE層の部分は、基材層である。
ノルマルヘプタンへの溶出量の評価において、積層体の層構成を層構成Cとした理由(即ち、基材層をLDPE層/LDPE層とした理由)は、基材層からのノルマルヘプタンへの溶出量を極力低減し、シーラント層からのノルマルヘプタンへの溶出量を適切に評価するためである。
厚生省告示370号試験に準拠し、試験用サンプル2におけるシーラント層にノルマルヘプタンを室温にて2時間接触させた後、上記のノルマルへプタンを回収した。
回収したノルマルヘプタンをエバポレーターで蒸発させ、次いで残留物を計量し、得られた値に基づき、シーラント層(即ち、シーラント用樹脂組成物)のノルマルヘプタン1mL当たりの溶出量(μg/mL)を算出した。
衛生性の観点から、溶出量(μg/mL)は、30μg/mL以下であることが好ましい。
また、エチレン・(メタ)アクリル酸エステル共重合体における(メタ)アクリル酸エステル単位の含有量が10質量%未満である比較例2のシーラント用樹脂組成物も、基材に対するヒートシール強度が不足していた。
また、樹脂(A)の含有量が45質量%未満である比較例3及び4のシーラント用樹脂組成物も、基材に対するヒートシール強度が不足していた。
また、粘着付与樹脂(B)の含有量が10質量%超である比較例5のシーラント用樹脂組成物は、ノルマルヘプタンへの溶出量が過剰であった。
実施例1~8及び10における層構成Aの積層体、並びに、実施例9における層構成Bの積層体の各々について、以下のようにしてスキンパック包装適性を確認した。
ポリプロピレン製のトレー上に、被包装物として、高さ2cm、面積50cm2(横10cm×縦5cm)の木片を配置し、その上に、被包装物及びトレーの全体を覆うようにして積層体を配置した。
この状態で、ムルチバック社製トレーシーラーT200を用い、設定温度130℃、加熱時間1秒、及び真空度10mbarの条件にて、包装材料としての積層体及びトレーによって被包装物をスキンパック包装した。
その結果、いずれの積層体を用いた場合にも、積層体に穴を生じることなく、積層体にシワを生じることもなく、積層体が被包装物の形状に追従及び密着しているスキンパック包装を行うことができた。
以上により、実施例1~8及び10における層構成Aの積層体、並びに、実施例9における層構成Bの積層体の各々は、スキンパック包装適性を備えることが確認された。
本明細書に記載されたすべての文献、特許出願、および技術規格は、個々の文献、特許出願、および技術規格が参照されることが具体的かつ個々に記された場合と同程度に、本明細書中に参照される。
Claims (13)
- (メタ)アクリル酸エステル単位の含有量が10質量%以上25質量%以下であるエチレン・(メタ)アクリル酸エステル共重合体である樹脂(A)と、
粘着付与樹脂(B)と、
を含有し、
前記樹脂(A)の含有量が、シーラント用樹脂組成物中の樹脂成分の全量に対し、45質量%超であり、
前記粘着付与樹脂(B)の含有量が、シーラント用樹脂組成物中の樹脂成分の全量に対し、0.1質量%以上10質量%以下であるシーラント用樹脂組成物。 - 更に、エチレン・ビニルエステル共重合体である樹脂(C)を含有する請求項1に記載のシーラント用樹脂組成物。
- 更に、エチレン・α-オレフィン共重合体エラストマー、スチレン系エラストマー、及びポリエチレンからなる群から選択される少なくとも1種である樹脂(D)を含有する請求項1又は請求項2に記載のシーラント用樹脂組成物。
- 前記樹脂(D)の含有量が、シーラント用樹脂組成物中の樹脂成分の全量に対し、5質量%以上40質量%以下である請求項3に記載のシーラント用樹脂組成物。
- 包装材料用のシーラントとして用いられる請求項1~請求項4のいずれか1項に記載のシーラント用樹脂組成物。
- 前記包装材料が、スキンパック包装用の包装材料である請求項5に記載のシーラント用樹脂組成物。
- 基材層と、
請求項1~請求項6のいずれか1項に記載のシーラント用樹脂組成物を含むシーラント層と、
を含む積層体。 - 前記基材層が、エチレン・不飽和カルボン酸共重合体のアイオノマー及びエチレン・不飽和エステル共重合体からなる群から選択される少なくとも1種を含有する請求項7に記載の積層体。
- 厚さが40μm以上300μm以下である請求項7又は請求項8に記載の積層体。
- 請求項7~請求項9のいずれか1項に記載の積層体を備える包装材料。
- 基材を更に備える請求項10に記載の包装材料。
- 前記基材がポリプロピレンを含む請求項11に記載の包装材料。
- 基材と、
請求項7~請求項9のいずれか1項に記載の積層体と、
前記基材及び前記積層体によって包装された被包装物と、
を備える包装体。
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CN201980073987.0A CN112969584B (zh) | 2018-11-30 | 2019-11-19 | 密封剂用树脂组合物、层叠体、包装材料、及包装体 |
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US17/293,504 US11898065B2 (en) | 2018-11-30 | 2019-11-19 | Resin composition for sealant, laminate, packaging material, and package |
EP19891212.3A EP3888910A4 (en) | 2018-11-30 | 2019-11-19 | RESIN COMPOSITION FOR SEALANT, LAMINATE, PACKING MATERIAL AND PACKING BODY |
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WO2022196297A1 (ja) * | 2021-03-18 | 2022-09-22 | 三井・ダウ ポリケミカル株式会社 | ヒートシール性樹脂組成物、ヒートシール材、包装材、蓋材及び包装容器 |
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