JP2005119075A - Multilayered film, lid material of container and bag - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a multilayered film not bringing about the sudden lowering of interlaminar strength and re-sealing strength even if exposed to a high temperature at the time of heat cooking, keeping in summer or the like, capable of keeping good re-sealability and excellent in heat-resistant re-sealability, the lid material of a container and a bag comprising the multilayered film. <P>SOLUTION: This multilayered film is constituted by laminating a surface resin layer (A) containing a thermoplastic resin (a), a self-adhesive resin layer (B) containing an amorphous olerfinic resin (b1) wherein the content of a 3 or above C α-olefin originating component is 50 mol% or above and a heat-sealable resin layer (C) containing a thermoplastic resin (c) in the order of (A)/(B)/(C). When the heat-sealable resin layer (C) is heat-sealed to a resin layer of the same composition and peeled therefrom, the self-adhesive resin layer (B) is exposed in a re-sealable state on the surface of a heat-sealable region. The lid material of the container and the bag made of this film are also disclosed. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a re-sealable multilayer film having good thermal stability and film formability during processing and having good adhesiveness even under high temperature and high humidity, and a container lid and bag using the same. .

  A conventional multilayer film that can be resealed is a flexible packaging material comprising a base layer, a pressure-sensitive adhesive layer adjacent to the base layer, and a skin layer covering the pressure-sensitive adhesive layer. Each surface has a coefficient of friction that allows the material to be machined in the packaging machine, which material is sealed to itself by the sealing jaws of the packaging machine and remains closed during normal handling For initial opening, a package having a seal that can be easily separated by hand can be formed. Flexible packaging material that is exposed at the surface of the sealing area so that the packaging material can be sealed against itself in the area of the sealing by the application of hand pressure only to reclose the package Known (e.g., see Patent Document 1.).

  Furthermore, as a multilayer film that can be resealed, hydrogenation of a surface resin layer (A) containing a thermoplastic resin (a), and a rubbery block copolymer containing a styrene block and a diene block The adhesive resin layer (B) containing the product (b1) and the tackifier (b2), and the heat seal resin layer (C) containing the thermoplastic resin (c) are (A) / (B) / (C) is a multilayer film laminated in the order of heat sealing the heat seal resin layer (C) and the heat seal resin layer (C) and a heat sealable thermoplastic resin layer. Then, when peeled off, the heat seal resin layer (C) and the adhesive resin layer (B) are broken and the adhesive resin layer (B) and the surface resin layer (A) are separated from each other. B) Viscosity that can be resealed in the heat seal area Multilayer film exposed in the state is also known (e.g., see Patent Document 2.).

  Examples of the resin for the adhesive adhesive layer of the flexible packaging material described in Patent Document 1 include elastomers such as styrene / butadiene copolymers, styrene / isoprene copolymers, and ethylene / vinyl acetate copolymers, and adhesives such as terpene resins and petroleum hydrocarbon resins. A pressure sensitive adhesive which is a mixture of an imparting agent is exemplified, and examples of the resin for the adhesive resin layer of the multilayer film described in Patent Document 2 include a hydrogenated styrene-butadiene block copolymer (SB), styrene A hydrogenated rubber block copolymer such as a hydrogenated butadiene-styrene block copolymer (SBS), a hydrogenated styrene-isoprene-styrene block copolymer (SIS), a rosin resin, A mixture of a terpene resin and a petroleum resin tackifier is illustrated.

  All of the packagings using these multilayer films as lids and bags have appropriate delamination strength (easy opening strength) and resealing strength at the time of opening at room temperature, but left in warehouses and delivery vehicles in the summer, When stored, when cooking in a microwave oven, etc., in the state where the package is exposed to high temperature, such as when adding hot water like a cup noodle container and resealing and steaming, the adhesive adhesive layer And the adhesive resin layer softens, and the delamination strength and reseal strength suddenly decrease, so the content protection of the package before opening may spill out or cause air leaks. It is easy to occur, and after opening, there is a drawback that the resealed lid material is turned over and steaming cooking becomes incomplete. For this reason, even when exposed to high temperatures such as cooking and summer storage, there is no sudden drop in delamination strength and reseal strength, it has an appropriate easy-open strength, and maintains good resealability A multilayer film having excellent heat resealability that can be produced has been desired.

Japanese National Publication No. 04-502588 (page 2-3) JP2003-175567 (page 4-7)

  The problem of the present invention is that there is no sudden drop in delamination strength and resealing strength even during storage in summer or when exposed to high temperatures such as cooking, and it has an appropriate easy opening strength and good resealability. It is providing the multilayer film excellent in heat-resealability which can maintain property, the cover material of the container which consists of this multilayer film, and a bag.

  As a result of intensive studies, the present inventors have laminated the surface resin layer (A), the adhesive resin layer (B), and the heat seal resin layer (C) in the order of (A) / (B) / (C), Resealable multilayer in which the adhesive resin layer (B) is exposed in a resealable state on the surface of the heat seal area when the heat seal resin layer (C) is heat sealed and peeled off from the resin layer of the same composition A resin layer, which is a film and contains an amorphous olefin resin (b1) having an α-olefin-derived component having 3 or more carbon atoms and a content of 50 mol% or more, is used as the adhesive resin layer (B). It is found that the multilayer film has good heat resealability, solves the problems of the present invention, and is suitable for packaging various foods as a container lid or bag and completes the present invention. It came to do.

  That is, the present invention relates to a surface resin layer (A) containing a thermoplastic resin (a) and an amorphous olefin system having a content of an α-olefin-derived component having 3 or more carbon atoms of 50 mol% or more. An adhesive resin layer (B) containing the resin (b1) and a heat seal resin layer (C) containing the thermoplastic resin (c) are (A) / (B) / (C). It is a multilayer film that is laminated in order, and when the heat seal resin layer (C) is heat sealed with a resin layer of the same composition and peeled off, the adhesive resin layer (B) is resealed on the surface of the heat seal region The present invention provides a multilayer film characterized by being exposed in a possible state.

  Furthermore, the present invention provides a bag made of the multilayer film, and a bag formed by heat-sealing the heat-seal layers of the multilayer film superimposed on each other. It is to provide.

  The multilayer film of the present invention, and the lid and bag of the container of the present invention using this multilayer film are excellent in easy-openability and resealability, and can be exposed to high temperatures during cooking and storage in summer. The delamination strength and reseal strength are not drastically reduced, and there is an effect of having an appropriate easy-open strength and maintaining good resealability.

  The multilayer film of the present invention is a multilayer film in which the resin layers (A) to (C) are laminated in the order of (A) / (B) / (C), and the heat seal resin layer (C) is the same. The adhesive resin layer (B) may be a multilayer film that is exposed in a resealable state on the surface of the heat seal region when the resin layer is heat-sealed and peeled off, and the adhesive resin layer (B) There are no particular limitations on the mechanism exposed in the adhesive state that can be resealed on the surface of the heat seal region, the production method of the multilayer film, and the like.

  As such a multilayer film of the present invention, for example, when the heat seal resin layer (C) is heat sealed with a resin layer having the same composition and peeled off, the heat seal resin layer (C) is broken and an adhesive resin In the layer (B), the multilayer film (I) exposed in an adhesive state that can be re-sealed on the surface of the heat seal region is peeled off, and the heat seal resin layer (C) is broken and the adhesive resin layer (B ) And the heat seal resin layer (C) are peeled off, and the adhesive resin layer (B) is exposed in an adhesive state that can be resealed on the surface of the heat seal region (II), the adhesive resin layer (B) And the heat seal resin layer (C) is broken and the surface resin layer (A) and the adhesive resin layer (B) are separated from each other, so that the adhesive resin layer (B) can be resealed on the surface of the heat seal region. Exposed in state That although the multilayer film (III), and the like, among which co-extrusion multi-layer films are preferred. Further, among these multilayer films (I), (II), and (III), there is little roughness of the peeled surface, and the adhesive strength at the time of resealing is strong and stable. Film (III) is preferred.

  The surface resin layer (A) of the multilayer film of the present invention may be a resin layer containing the thermoplastic resin (a) as a main component, and may be a single layer resin layer or a multilayer resin layer. It may be. Examples of the thermoplastic resin (a) used herein include olefin resins such as ethylene resins and propylene resins, styrene resins, ester resins, and amide resins and imide resins when oxygen barrier properties are to be maintained. Examples thereof include a resin, a saponified resin of ethylene-vinyl acetate copolymer, and the like, and it is used for a single layer structure or a multilayer structure by mixing two or more kinds.

  Examples of the ethylene resin include ethylene resins such as very low density polyethylene (VLDPE), linear low density polyethylene (LLDPE), low density polyethylene (LDPE), medium density polyethylene (MDPE), and high density polyethylene (HDPE); Ethylene-vinyl acetate copolymer (EVA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl acrylate (EMA) copolymer, ethylene-ethyl acrylate- Ethylene copolymers such as maleic anhydride copolymer (E-EA-MAH), ethylene-acrylic acid copolymer (EAA), ethylene-methacrylic acid copolymer (EMAA); and ethylene-acrylic acid copolymer Of metal neutralized polymer, ethylene-methacrylic acid copolymer Genus in the hydrate, and the like.

  Examples of the propylene resin include propylene homopolymers, copolymers of propylene and other α-olefins such as ethylene and butene, and the copolymers include random copolymers and block copolymers. Either can be used. Examples of the propylene homopolymer include isotactic polypropylene, syndiotactic polypropylene, and attack polypropylene. Among them, isotactic polypropylene is preferable.

  These thermoplastic resins (a) are preferably ethylene-based resins and propylene-based resins because they are inexpensive and excellent in moldability. Among them, the adhesive resin layer (B) and the heat seal resin layer (C) are broken, and the surface resin layer (A) and the adhesive resin layer (B) are separated from each other, so that the adhesive resin layer (B) is heat sealed. When the multilayer film is exposed in a re-sealable state on the surface of the region, the interlayer adhesive strength between the surface resin layer (A) and the adhesive resin layer (B) is appropriate and easily peeled off, and the heat seal portion is The surface-resin layer (A) and adhesive resin layer (B) when peeled off have little roughness on the delamination surface, and the resealing strength when repeated opening and resealing is high. Preferred are ethylene- (meth) acrylic acid copolymers such as coalesced (EAA), ethylene-methacrylic acid copolymer (EMAA) and / or metal neutralized products thereof, and metals of ethylene- (meth) acrylic acid copolymers Neutralized product is particularly preferredAs the metal neutralized product of the ethylene- (meth) acrylic acid copolymer, for example, at least 10 mol%, preferably 10 to 60 mol% of the carboxyl group is a metal ion such as sodium or zinc. One that has been summed up.

  Furthermore, for the surface resin layer (A), if necessary, an antifogging agent, an antistatic agent, a thermal stabilizer, a nucleating agent, an antioxidant, a lubricant, an antiblocking agent, a release agent, an ultraviolet absorber, You may add components, such as a coloring agent, in the range which does not impair the objective of this invention.

  The adhesive resin layer (B) of the multilayer film of the present invention is a resin layer comprising an amorphous olefin resin (b1) in which the content of an α-olefin-derived component having 3 or more carbon atoms is 50 mol% or more. And what is necessary is just a resin layer which has adhesiveness.

  The amorphous olefin-based resin (b1) may have an α-olefin-derived component content of 3 or more carbon atoms as long as it is 50 mol% or more, and in particular, an α-olefin-derived component of 3 to 20 carbon atoms. Is preferably an amorphous olefin resin having a content of 50 mol% or more, more preferably an amorphous olefin resin having an α-olefin-derived component having 3 to 12 carbon atoms and a content of 80 mol% or more. Most preferred is an amorphous olefin resin in which the content of the α-olefin-derived component having 3 to 4 atoms is 80 mol% or more.

  As the amorphous olefin-based resin (b1), for example, even if it is a homopolymer of an α-olefin having 3 or more carbon atoms, two or more kinds of α-olefins having 3 or more carbon atoms are used. It may be a polymer, a copolymer of an α-olefin having 3 or more carbon atoms and another monomer, or a mixture thereof. Specific examples of the amorphous olefin resin (b1) include homopolymers such as amorphous polypropylene and amorphous poly-1-butene, 50 mol% or more of 1-butene and other α-olefins, For example, a copolymer with propylene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-dexene, etc., 50 mol% or more of propylene and other α-olefins, for example, 1 And copolymers with -butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-dexene, etc., and amorphous propylene homopolymer, amorphous 1-butene Homopolymer, amorphous propylene-1-butene copolymer having a propylene-derived component content of 50 mol% or more, amorphous 1-butene-propylene copolymer having a 1-butene-derived component content exceeding 50 mol% Coalescence etc. An amorphous 1-butene-propylene copolymer having a 1-butene-derived component content of more than 60 mol% is particularly preferred.

  The number average molecular weight of the amorphous olefin resin (b1) is preferably 100,000 to 500,000, and when the amorphous olefin resin (b1) is a copolymer, a random copolymer Any of block copolymers may be used, but random copolymers are preferred.

  Commercially available products that can be used as the amorphous olefin-based resin (b1) include, for example, “RETAX” manufactured by Huntsman, Inc., “Cataloy” manufactured by Sun Allomer, “UBETAC” manufactured by Ube Lexellen, and Ube Industries, Ltd. “CAP” can be mentioned.

  In the present invention, the amorphous property of the amorphous olefin resin (b1) was measured by a differential scanning calorimeter (DSC) using a 5 mg sample at a temperature increase rate of 10 ° C./min from 20 ° C. to 230 ° C. In this case, the melting peak is not observed, and the heat of fusion of the maximum peak in the endothermic curve is 0.7 J / g or less.

  Amorphous olefin resin (b1) has a lot of low molecular weight and is sticky, and resin pellets tend to adhere to each other. Therefore, they are clogged in the piping section for delivery to the extruder, and adhere to the meter when blending. Although there is a problem in raw material handling such that accurate formulation is difficult, the content of other olefin-based resins, for example, α-olefin-derived components having 3 or more carbon atoms is 50 mol% in order to improve raw material handling. Olefin-based resin (b4) other than the above-described amorphous olefin-based resin (b1) [hereinafter abbreviated as other olefin-based resin (b4). ] Are preferably used in combination. As a method of using the amorphous olefin resin (b1) and the other olefin resin (b4) in combination, the amorphous olefin resin (b1) and the other olefin resin (b4) are mixed with a twin screw extruder or the like. It is preferable to heat knead and pelletize in advance. When the amorphous olefin resin (b1) and the other olefin resin (b4) are used in combination, the weight ratio (b1) / (b4) is preferably 95/5 to 60/40, and 90/10 to 70/30. Is more preferable.

  The pressure-sensitive adhesive resin layer (B) contains a non-crystalline olefin resin (b1) and a rubbery thermoplastic resin (b2) because the resin layer has a good balance between pressure-sensitive adhesiveness and heat resealability. A resin layer comprising an amorphous olefin resin (b1), a rubbery thermoplastic resin (b2) and a tackifier (b3) is particularly preferred. In this case, the other olefin resin (b4) can be used in combination for improving the raw material handling of the amorphous olefin resin (b1), and the weight ratio (b1) / (b4) is 95 / 5-60 / 40 is preferable and 90 / 10-70 / 30 is more preferable.

  When the resin layer (B) is a resin layer containing an amorphous olefin resin (b1) and further containing a rubbery thermoplastic resin (b2) if necessary, these (b1) and (b2) ) Is preferably such that the weight ratio (b1) / (b2) is 20/80 to 100/0, and in particular, the resin layer has a good balance between adhesiveness and heat resealability. Therefore, it is more preferable that the weight ratio (b1) / (b2) is a ratio of 30/70 to 80/20.

  When the resin layer (B) is a resin layer comprising an amorphous olefin resin (b1), a rubbery thermoplastic resin (b2), and a tackifier (b3), these (b1) , (B2) and (b3) are used at a weight ratio (b1) / (b2) of 20/80 to 100/0 and a weight ratio (b1 + b2) / (b3) of 50/50 to 98 / It is preferable that the ratio is 2; in particular, since the resin layer has a good balance between adhesiveness and heat resealability, the weight ratio (b1) / (b2) is 30/70 to 80/20, and The weight ratio (b1 + b2) / (b3) is more preferably 60/40 to 90/10.

  In the adhesive resin layer (B), when the amorphous olefin resin (b1) and the other olefin resin (b4) are used in combination, the amorphous olefin resin (b1) and the other olefin resin ( It is preferable that b4) be melt-kneaded and then pelletized for use. The melt index (measured at 230 ° C. according to MI, JIS K-7210) of the pellets is preferably 0.1 to 30 g / 10 minutes because flow disturbance is unlikely to occur. More preferably, it is 5 to 20 g / 10 minutes.

  In addition, when the rubbery thermoplastic resin (b2) and the tackifier (b3) are used in combination in the adhesive resin layer (B), the rubbery thermoplastic resin (b2) and the tackifier (b3) are melted. It is preferable to use after kneading and pelletizing.

  The other olefin-based resin (b4) may be an olefin-based resin other than the amorphous olefin-based resin (b1) in which the content of the α-olefin-derived component having 3 or more carbon atoms is 50 mol% or more. For example, propylene-based resin, 1-butene-based resin, trimethylpentene-1 (TPX) and the like can be mentioned. Among them, propylene-based resin is preferable because it has heat resistance, has a high melting point, and is easily available.

  The rubbery thermoplastic resin (b2) is not particularly limited as long as it is a rubbery thermoplastic resin. For example, a styrene-butadiene block copolymer (SB), a hydrogenated product thereof, styrene-butadiene- Styrene block copolymer (SBS), its hydrogenated product, styrene-isoprene-styrene block copolymer (SIS), its hydrogenated product, styrene-isoprene block copolymer (SI), its hydrogenated product styrene-ethylene -Rubber block copolymer containing styrene block such as propylene block copolymer (SEP) and its hydrogenated product; ethylene-propylene copolymer (EP), ethylene-butene-1 copolymer (EB) ), Ethylene-octene copolymer (EO), propylene-butadiene copolymer (PB), ethylene- Acid vinyl copolymer (EVA) rubber copolymer the ethylene was obtained as an essential component as such, and the like.

  Among these rubbery thermoplastic resins (b2), a rubbery block copolymer containing a styrene block and a diene block, and its hydrogenated product are preferred, have low odor, gel, fish eye, fluid disturbance, etc. Since there is no appearance defect and a co-pressed film that can be continuously produced for a long time and has good resealability is obtained, a hydrogenated styrene-butadiene block copolymer (SB), styrene-butadiene-styrene block Styrene block and diene block such as hydrogenated copolymer (SBS), hydrogenated styrene-isoprene-styrene block copolymer (SIS), hydrogenated styrene-isoprene block copolymer (SI) More preferred is a hydrogenated rubber block copolymer containing styrene-butadiene block copolymer (S ) Hydrogenated product (HSBR), styrene-butadiene-styrene block copolymer (SBS) hydrogenated product (SEBS), styrene-isoprene-styrene block copolymer (SIS) hydrogenated product (styrene-ethylene- Propylene-styrene block copolymer (SEPS) is most preferred.

  The hydrogenation ratio of the hydrogenated product of the rubbery copolymer is usually 10 to 100 mol%, and preferably 30 to 100 mol%. Further, the melt index (measured at 190 ° C. in accordance with MI, JIS K-7210) is preferably 2 to 30 g / 10 minutes because flow disturbance is unlikely to occur.

  Examples of the tackifier (b3) include resins having an adhesive property at room temperature made of natural resin or synthetic resin, such as natural resin rosin, polymerized rosin, hydrogenated rosin, glycerinster rosin, and pentaerythritol. Rosin resin; Terpene resin such as terpene, aromatic modified terpene, terpene phenol, hydrogenated terpene; Petroleum resin such as aliphatic petroleum resin, aromatic petroleum resin, hydrogenated alicyclic petroleum resin; Examples thereof include liquid polybutadiene, polyisoprene which is liquid at normal temperature, and polyisobutylene which is liquid at normal temperature, among which rosin resin, terpene resin and petroleum resin are preferable.

  If necessary, various additives such as softeners, oils (mineral oils), stabilizers (antioxidants, etc.), surfactants, liquid paraffin, etc. are added to the adhesive resin layer (B). Also good.

  The heat seal resin layer (C) of the multilayer film of the present invention may be a heat sealable resin layer containing a thermoplastic resin (c). Examples of the thermoplastic resin (c) used here include: Olefin resins such as ethylene resins and propylene resins, styrene resins, and ester resins can be used, and heat sealing is possible depending on the material of the heat seal part of the adherend such as a container for heat sealing the multilayer film. A suitable resin may be selected as appropriate.

  Examples of the ethylene resin used as the thermoplastic resin (c) in the heat seal resin layer (C) include the ethylene resins exemplified as the thermoplastic resin (a). Examples of the propylene resin include propylene and Copolymers with other α-olefins, such as propylene-ethylene copolymers and propylene-butene copolymers, can be mentioned. As these propylene-based copolymers, any of random copolymers and block copolymers can be used, but random copolymers are preferred.

  Examples of the styrene resin used as the thermoplastic resin (c) in the heat seal resin layer (C) include a small amount of rubber and other vinyl monomers copolymerized with polystyrene and styrene monomer. Examples thereof include styrene copolymers. Examples of other vinyl monomers include styrene monomers such as α-methylstyrene and p-methylstyrene, acrylonitrile, methyl acrylate, methyl methacrylate, acrylic acid, methacrylic acid, and maleic anhydride. Can be mentioned. Moreover, the usage-amount of a rubber part is 0.1 to 20 weight% normally, and the usage-amount of another vinyl monomer is 0.1 to 30 weight%. Preferable examples of the styrene resin used as the thermoplastic resin (c) include high impact polystyrene (HIPS) which is a copolymer of polystyrene and diene rubber and styrene.

  Examples of the ester resin used as the thermoplastic resin (c) in the heat seal resin layer (C) include ester resins such as polyethylene terephthalate and polybutylene terephthalate, and polyethylene terephthalate is particularly preferable.

  The multilayer film of the present invention is an adherend having a resin layer (adhesive resin layer) having the same composition as the heat seal resin layer (C) of the multilayer film, for example, a resin layer having the same composition as the heat seal resin layer (C). When the container or film having the heel surface is heat-sealed and peeled off, the adhesive resin layer (B) is exposed in a resealable state on the surface of the heat-sealed region, and such a multilayer film As mentioned above, the coextruded multilayer films (I), (II), (III) and the like can be mentioned as described above.

  In the case of the multilayer film (I), as the heat seal resin layer (C), it is not necessary to select a resin for peeling the interlayer from the adhesive resin layer (B) like the multilayer film (II), A heat-sealable resin, preferably the same kind of resin, can be selected and used according to the material of the heat-sealing part of the adherend such as a container. For example, when the material of the heat seal portion is based on ethylene resin, any of the above-described ethylene resins can be used as the thermoplastic resin (c) used for the heat seal resin layer (C).

  In the multilayer film (I), for example, when the material of the heat seal part is based on propylene resin, the thermoplastic resin (c) used for the heat seal resin layer (C) is inexpensive and has a molding process. The propylene-based resin described above can be used because of its excellent properties, sealability, etc., among which propylene-ethylene copolymers, for example, propylene-ethylene copolymers having an ethylene-derived component content of 2 to 10% by weight are preferred. .

  In the multilayer film (I), for example, when the material of the heat seal part is based on a styrene resin, the thermoplastic resin (c) used for the heat seal resin layer (C) is inexpensive, moldability, From the viewpoint of excellent heat sealability and the like, the above-described styrene resin or ethylene resin having adhesiveness with the styrene resin is preferable.

  Examples of the ethylene resin having adhesiveness with the styrene resin include, for example, ethylene-vinyl acetate copolymer (EVA), very low density polyethylene (VLDPE), linear low density polyethylene (LLDPE), low density polyethylene ( LDPE), modified polyethylene obtained by mixing and modifying rosin, hydrogenated rosin, rosin ester derivatives, polymerized rosin, terpene, modified terpene resin, aliphatic petroleum resin, maleic anhydride and the like to these ethylene resins.

  In the multilayer film (I), for example, when the material of the heat seal portion is based on an ester resin, the thermoplastic resin (c) used for the heat seal resin layer (C) may be moldability, seal Since it is excellent in aptitude etc., the above-mentioned ester-type resin or ethylene-type resin which has adhesiveness with ester-type resin is preferable.

  Examples of the ethylene resin having adhesiveness with the ester resin include those similar to the ethylene resin described above as the ethylene resin having adhesiveness with the styrene resin.

  In the case of the multilayer film (II), when the heat seal resin layer (C) is heat sealed with a resin layer having the same composition and peeled off, the interlayer between the adhesive resin layer (B) and the heat seal resin layer (C) is It is necessary to select the resin configuration of the heat seal resin layer (C) so that it can be easily peeled off. For this reason, as an adherend such as a container, it is necessary to select an adherend having a heat sealable heat seal portion.

  In the multilayer film (II), as the combination in which the adhesive resin layer (B) and the heat seal resin layer (C) are easily separated, the interlayer adhesive strength is 2 to 20 N / 15 mm, and the surface resin The combination which becomes smaller than the interlayer adhesive strength of a layer (A) and an adhesive resin layer (B) can be mentioned. This interlayer adhesive strength is a strength that can maintain the function as a multilayer film, and is a strength that allows relatively easy delamination. To do this, the heat seal resin layer (C) has a moderate adhesiveness with the adhesive resin layer (B), and the adhesive strength between these layers is reduced to about 2 to 20 N / 15 mm. May be selected and combined with the adhesive resin layer (B). As such a heat seal resin layer, for example, ethylene- (meth) acrylic acid such as ethylene-acrylic acid copolymer (EAA), ethylene-methacrylic acid copolymer (EMAA) as the thermoplastic resin (c). A copolymer and / or a metal neutralized product thereof is preferable, and a resin layer formed using a metal-neutralized ethylene- (meth) acrylic acid copolymer is composed of an adhesive resin layer (B) and a heat seal resin layer (C When the heat-sealed part is peeled off and the heat-sealed part is peeled off, the delamination surface of the adhesive resin layer (B) and the heat-seal resin layer (C) is less rough. This is particularly preferable because the resealing strength when sealing is repeated is high.

  The surface resin layer (A) in the multilayer film (II) may be a resin layer containing the thermoplastic resin (a) as a main component, but has an interlayer adhesive strength with the adhesive resin layer (B). The resin layer needs to be larger than the interlayer adhesive strength between the adhesive resin layer (B) and the heat seal resin layer (C). Therefore, as the thermoplastic resin (a) used in the surface resin layer (A), the interlayer adhesive strength between the surface resin layer (A) and the adhesive resin layer (B) is such that the adhesive resin layer (B) and the heat seal resin layer ( It is preferable to select an appropriate resin in consideration of being larger than the interlayer adhesive strength of C). For example, olefin resins such as ethylene resins and propylene resins, styrene resins, ester resins, ester resins, etc. Examples thereof include an ethylene resin having adhesiveness with a resin, a styrene resin, or an ethylene resin having adhesiveness with a styrene resin. Of these, ethylene resins are preferred.

  As the ethylene resin, the ethylene resin described above as the thermoplastic resin (a), or an ethylene resin having adhesiveness with a styrene resin or an ester resin can be used. Examples of the propylene-based resin include copolymers of propylene and other α-olefins, such as propylene-ethylene copolymers and propylene-butene copolymers. Further, in order to increase the interlayer adhesion strength between the surface resin layer (A) and the adhesive resin layer (B), a resin obtained by graft-polymerizing an adhesive resin such as maleic anhydride to an olefin, or the above-described tackifier ( An appropriate amount of b3) may be added.

  In the case of the multilayer film (III), the adhesive resin layer (B) and the heat seal resin layer (C) are broken when the heat seal resin layer (C) is heat sealed with the resin layer having the same composition and peeled off. At the same time, since the interlayer between the surface resin layer (A) and the adhesive resin layer (B) is peeled off, as the heat seal resin layer (C), the interlayer adhesive strength with the adhesive resin layer (B) is the same as that of the surface resin layer (A). The resin layer needs to be larger than the interlayer adhesive strength of the adhesive resin layer (B). For this reason, the thermoplastic resin (c) used in the heat seal resin layer (C) is a resin that can be heat sealed according to the material of the heat seal portion of the adherend such as a container, preferably an adhesive of the same type. It is preferable to select and use a resin having high interlayer adhesion strength with the resin layer (B), and any of the thermoplastic resins (c) described as the resin used for the heat seal resin layer (C) in the multilayer film (I) Can be used as well.

  With respect to such a heat seal resin layer (C), the surface resin layer (A) of the multilayer film (III) was peeled off by heat sealing the heat seal resin layer (C) with a resin layer having the same composition. In this case, it is necessary to select the resin configuration of the surface resin layer (A) so that the surface resin layer (A) and the adhesive resin layer (B) are easily separated from each other.

  In the multilayer film (III), as a combination in which the surface resin layer (A) and the adhesive resin layer (B) are easily separated, the interlayer adhesive strength is 2 to 23 N / 15 mm, and the adhesive resin layer The combination which becomes smaller than the interlayer adhesive strength of (B) and a heat seal resin layer (C) can be mentioned. This interlayer adhesive strength is a strength that can maintain the function as a multilayer film, and is a strength that allows relatively easy delamination. To do this, select a surface resin layer (A) that has moderate adhesiveness with the adhesive resin layer (B), and the adhesion strength between these layers is reduced to about 2 to 23 N / 15 mm. And may be combined with the adhesive resin layer (B). As such a surface resin layer, for example, an ethylene- (meth) acrylic acid copolymer such as an ethylene-acrylic acid copolymer (EAA) or an ethylene-methacrylic acid copolymer (EMAA) can be used as the thermoplastic resin (a). A polymer and / or a metal neutralized product thereof is preferable, and a resin layer using a metal neutralized product of an ethylene- (meth) acrylic acid copolymer has a surface resin layer (A) and an adhesive resin layer (B). When the heat-sealed part is peeled off, the surface resin layer (A) and the adhesive resin layer (B) have little roughness between the surfaces, and can be opened and resealed. It is particularly preferable because the resealability when repeated is high.

  In the multilayer film of the present invention described above, as the thermoplastic resin (c), an olefin resin such as an ethylene resin or a propylene resin, a styrene resin such as polystyrene or high impact polystyrene (HIPS), a polyethylene terephthalate, or the like. When using an ester resin, it is excellent in adhesion between the container and the lid, stability of the sealing strength, etc., and in accordance with JIS K-7210, it is 190 ° C. for ethylene resin and 210 ° C. for propylene resin. A styrene resin preferably has an MI (melt index) measured at 200 ° C. and an ester resin at 260 ° C. of 2 to 80 g / 10 minutes.

  The heat seal resin layer (C) has a friction coefficient of 0.7 or less, particularly 0.5 or less, considering the processability during film formation and the packaging suitability of the filling machine. It is desirable to be. For this reason, it is preferable to add a lubricant and an antiblocking agent to the heat seal resin layer (C) as appropriate.

  Further, on the surface of the heat seal resin layer (C), low molecular weight components and the like from the amorphous olefin resin (b1) and the tackifier (b3) in the adhesive resin layer (B) are blitted over time. Precipitation) may occur, and the problem of deterioration of slipperiness and film blocking tends to occur. As a solution, it is effective to emboss the surface of the multilayer film and to add a filler to the heat seal resin layer (C). As the filler, inorganic materials such as calcium carbonate and talc are desirable because they are in a state where large irregularities are expressed on the price and surface, and a good friction coefficient can be maintained.

  Furthermore, for the heat seal resin layer (C), an anti-fogging agent, an antistatic agent, a heat stabilizer, a nucleating agent, an antioxidant, a lubricant, an antiblocking agent, a release agent, and an ultraviolet absorber, if necessary. Further, a colorant and the like may be added within a range that does not impair the object of the present invention.

  In the case of the multilayer films (I) and (III), peeling does not occur between the adhesive resin layer (B) and the heat seal resin layer (C) when the heat seal portion is peeled off, Even when additives such as lubricants and antiblocking agents are added to the heat seal resin layer (C), there is no effect on the delamination due to the addition of lubricants and antiblocking agents, etc. There is an advantage that a multilayer film having a stable reseal adhesive strength can be obtained.

  Although it does not specifically limit as a method to manufacture the multilayer film of this invention, For example, (1) Amorphous olefin resin on the film for surface resin layers (A) containing a thermoplastic resin (a) (B1), and if necessary, a rubbery thermoplastic resin (b2), a tackifier (b3), an adhesive resin layer (B) containing other olefinic resin (b4), etc., and a thermoplastic resin ( (A) / (B) / (C) are laminated in the order of (A) / (B) / (C) by simultaneously heat-melt-extruding the heat-seal resin layer (C) containing c), and ( 2) A resin for the surface resin layer (A) containing the thermoplastic resin (a), an amorphous olefin resin (b1), and if necessary, a rubbery thermoplastic resin (b2), a tackifier ( b3), containing other olefinic resin (b4), etc. The resin for the adhesive resin layer (B) and the resin for the heat seal resin layer (C) containing the thermoplastic resin (c) are heated and melted in different extruders, respectively, Coextrusion method in which (A) / (B) / (C) is laminated in the melted state by a known method such as a feed block method and then coextrusion lamination is formed into a film by inflation, T-die chill roll method, etc. Among these, the coextrusion method of (2) is capable of adjusting the interlayer adhesive strength relatively freely, and can obtain a multilayer film having excellent hygiene and good cost performance. preferable. Further, in order to improve printing adhesiveness and laminating suitability, it is desirable to perform surface treatment on the surface resin layer (A).

  Examples of the surface treatment include corona treatment, plasma treatment, chromic acid treatment, flame treatment, hot air treatment, surface oxidation treatment such as ozone / ultraviolet treatment, and surface unevenness treatment such as sand blasting. is there.

  In the method for producing a multilayer film as described above, when the rubbery thermoplastic resin (b2) is used as the adhesive resin layer (B), the rubbery thermoplastic resin (b2) contains a styrene block and a diene block. It is preferable to use a hydrogenated rubber block copolymer because it is excellent in thermal stability and can be produced stably continuously for a long time. Further, in the multilayer film manufacturing method by this coextrusion method, since the adhesive resin layer (B) is sandwiched between the surface resin layer (A) and the heat seal resin layer (C), the temperature is usually higher than 200 ° C. There is an advantage that it is difficult to receive a direct heat history from a heated feed block, a die or the like, and that gel, fish eye, flow turbulence and the like are hardly generated in the adhesive resin layer (B).

  In the multilayer film of the present invention, as a preferable combination of each resin layer, for example, a surface resin layer using an ethylene-based resin or a propylene-based resin, and a content of an α-olefin-derived component having 3 to 12 carbon atoms A hydrogenated rubber block copolymer containing 80% by mole or more of an amorphous olefin resin, a styrene block and a diene block, a tackifier (b3), and a pressure-sensitive resin layer using a propylene-based resin , Ethylene resin, propylene resin, styrene resin, or a combination of heat seal resin layers using an ethylene resin having adhesiveness with a styrene resin or an ester resin. Among these, as the tackifier (b3) in the adhesive resin layer (B), those using one or more resins selected from the group consisting of rosin resins, terpene resins and petroleum resins are particularly preferable.

  In addition, since the packaging material having resealability using the multilayer film of the present invention can prevent the risk of being resealed and displayed for sale after being opened, the trace at the time of opening can be easily identified. Preferably there is. As a method for leaving a trace at the time of opening, it is effective to add a colorant or a filler to the adhesive resin layer (B). As the filler, inorganic materials such as calcium carbonate and talc are desirable because the price and trace state are clear.

  In addition, in the multilayer film of the present invention, it is important to appropriately select a combination of resin layers in order to achieve a target interlayer adhesive strength. In this case, the interlayer adhesive strength also depends on the thickness of the resin layer. It is also necessary to consider that changes. Even if the adhesive resin layer (B) and the heat seal resin layer (C) are used in a combination that is relatively excellent in adhesion, for example, a heat seal resin comprising a metal neutralized ethylene- (meth) acrylic acid copolymer In the case of a layer, if the thickness is as small as 0.1 to 0.5 μm, the interlayer adhesive strength with the adhesive resin layer (B) is greatly reduced, and conversely if it is as large as 20 to 30 μm, the interlayer adhesive strength is reduced. It ’s a big value.

  The thickness of the multilayer film of the present invention includes a thickness usually referred to as a sheet, and is in the range of 20 to 500 μm, and particularly preferably in the range of 20 to 200 μm. For example, the one having a thickness of 50 to 200 μm is left as it is, and the one having a thickness of 20 to 100 μm is laminated on a stretched base film, etc., and can be suitably used as a cover material for various containers, respectively. Those having a length of 20 to 100 μm can be suitably used as various containers and the like after being laminated on a substrate sheet and the like. Further, the one having a thickness of 20 to 500 μm is left as it is or laminated to a stretched base film, etc., and then heat-melted and bonded with the heat seal resin layer (C) inside to form a bag. Those having a thickness exceeding 200 μm can be suitably molded and used as various containers. Among these, the one having a thickness of 50 to 200 μm is used as it is, or the one having a thickness of 20 to 100 μm is laminated on a stretched base film, etc., and used as a lid for various containers, respectively. Is particularly preferred.

  Among the multilayer films of the present invention, the multilayer film (I) is not delaminated. Therefore, the interlayer adhesive strength between the surface resin layer (A) and the adhesive resin layer (B), and the adhesive resin layer (B ) And the heat seal resin layer (C) preferably have an interlayer strength of 20 N / 15 mm or more.

  Moreover, as said multilayer film (II), it is preferable that the interlayer intensity | strength of an adhesive resin layer (B) and a heat seal resin layer (C) is 2-20N / 15mm, and it is 2-18N / 15mm especially. Is more preferable. In this case, the interlayer adhesive strength between the surface resin layer (A) and the adhesive resin layer (B) of the multilayer film (II) is 5 N / from the interlayer adhesive strength between the adhesive resin layer (B) and the heat seal resin layer (C). It is preferably 15 mm or more. The thickness of the heat seal resin layer (C) of the multilayer film (II) is preferably 0.6 to 10 μm, more preferably 1 to 10 μm, and most preferably 1 to 6 μm.

  Furthermore, as said multilayer film (III), it is preferable that the interlayer intensity | strength of a surface resin layer (A) and an adhesive resin layer (B) is 2-23 N / 15mm, and it is especially 2-18 N / 15mm. More preferred. In this case, the interlayer adhesive strength between the adhesive resin layer (B) and the heat seal resin layer (C) of the multilayer film (II) is 5 N / 15 mm from the interlayer strength between the surface resin layer (A) and the adhesive resin layer (B). It is preferable that it is larger. The total thickness of the adhesive resin layer (B) and the heat seal resin layer (C) of the multilayer film (III) is preferably 3 to 25 μm, more preferably 3.5 to 23 μm. Most preferably, it is ˜20 μm. The thickness of the heat seal resin layer (C) is preferably 0.6 to 10 μm, more preferably 1 to 10 μm, and most preferably 1 to 6 μm.

  The multilayer film of the present invention can be used as it is by sealing it with an adherend by thermal fusion, and when rigidity and heat resistance are required, an adhesive resin or adhesive is put on the surface resin layer (A). A base material can be laminated | stacked and it can be set as a laminate film or a laminate sheet. Examples of the base material include biaxially oriented polypropylene (OPP) film, biaxially oriented nylon (ONY) film, biaxially oriented polyethylene terephthalate (PET) film, aluminum (AL) foil, paper, and non-woven fabric. It is not limited to these.

  Examples of the method of laminating and bonding the multilayer film and the substrate include wet lamination, non-solvent lamination, dry lamination, extrusion lamination, thermal lamination, and the like. Examples of the dry lamination adhesive include a polyester-polyurethane adhesive and a polyether-polyurethane adhesive.

  Conventionally, foods, stationery, medicines, etc. that are used several times are either individually packaged or packaged in a zippered bag. In individual packaging, packaging materials and packaging processes are bulky, and there are problems in terms of environmental resources and costs. For zipper bag making products, it is necessary to install a device for attaching the zipper separately on the bag making machine, and a certain degree of rigidity is required for attaching, so a laminated film with a stretched substrate or a thick film is essential. There was a limited configuration.

  In addition, with regard to the remaining items after consumption of a certain amount of lightweight items, confectionery, bread, etc., the opening after opening may be tied with a rubber band to prevent dirt, dust, etc. and contamination with insects, etc. In addition, it does not need to be sealed as much as a zipper, and it only needs to be able to be resealed several times. It is costly to use such a packaging bag for such contents. This is also not preferable in terms of resource saving. In particular, when packaging confectionery bread, bread, etc., there has been a demand for a packaging material that can be easily resealed at low cost without using a binding tool so as to prevent contamination by foreign substances such as insects.

  Multi-layer films with a structure such as paper / aluminum / hot melt are used for the lids of instant food containers such as ramen cups. This structure is easy to open. Using the function and plastic deformation characteristics of aluminum, keep the lid turned up when pouring hot water, and keep the lid closed by folding the handle part of the lid during cooking time. Because. However, when thin aluminum is used or in the case of a film with aluminum removed, there are cases where the plastic deformability cannot be maintained and the original state cannot be restored. Is closed. Furthermore, there is a strong desire to suppress the use of aluminum for reasons such as the recent reduction of environmental impact and separation and collection, as well as the inspection of the contents with X-rays and the like to prevent foreign matter contamination and the use of defect detectors. . However, there is no material having plastic deformation performance equivalent to that of aluminum, and there are few materials that can easily maintain a resealed state during cooking. Furthermore, for the purpose of reducing the number of processing steps, a multilayer film that satisfies the above requirements has been desired. During cooking and heating under the above use conditions, the film is exposed to high temperature and high humidity.

  When the multilayer film of the present invention is used as a cover material, the heat seal resin layer (C) of the cover material and the heat seal resin layer of a container filled with an article such as food are overlaid and heat sealed. A resealable packaging container having airtightness and practical strength can be obtained. The resulting resealable packaging container is exposed to the surface with the adhesive resin layer (B) resealable on the peeled surface after opening, and can be resealed (resealed) only by pressure-sensitive adhesion by hand. It is. In addition, when pouring hot water into an instant food container such as a ramen cup and capping the container again during cooking time, the container is kept at high temperature and high humidity, but the lid material using the multilayer film of the present invention Is excellent in heat-sealing property, so that there is little decrease in resealing strength under high temperature and high humidity, and the lid does not open. Therefore, it is possible to keep the lid closed during cooking time without using a tack seal or the like when the container is covered again, and the plastic deformation performance of aluminum becomes unnecessary. The dealuminated film, which has long been requested, can be made, reducing the number of processing steps and contributing to the reduction of environmental burden.

  As a container used for such a resealable packaging container, for example, a styrene resin, a foamed styrene resin, a propylene resin, an ester resin or the like was manufactured by a molding method such as injection molding, vacuum molding, or pressure molding. Examples include cups and trays, and paper cups and paper trays formed by laminating olefinic resins such as polyethylene on paper. These containers have a heat seal portion with the lid material, for example, a bowl-shaped heat seal portion, and select the type of heat seal resin of the lid material according to the type of resin in this portion, and seal The strength can be adjusted.

  Moreover, the multilayer film of the present invention is slit into a tape shape and can be used as a tape-like adhesive film. At that time, the tape-like multilayer film may be adhered to the adherend in the course of being drawn out from the film roll as the film supply source of the bag making machine or the bag making filling machine and transferred to the bag making means. However, it may be processed separately after bag making. Alternatively, the tape and the adherend film may be adhered at the time of printing and laminating.

  As the bonding position and bonding method, the heat-sealing resin layer (C) of the tape-shaped multilayer film is melt-bonded by heat sealing on the film inner surface (sealing surface) side located at the opening of the adherend such as a bag, or the film Adhesive position and method for heat-sealing the outer surface of the film to be resealed (on the side opposite to the sealing surface) and the heat-sealing resin layer (C) of the tape-shaped multilayer film by heat sealing when the opening is folded. It is done. In addition, when processing the cover material for instant foods or the like, the heat seal resin layer (C) of the tape-shaped multilayer film is adhered with an adhesive on the seal surface side located in the cover material tab portion, or heat fusion is performed. After adhering by wearing, it can be punched into a predetermined shape to form a single wafer. That is, by peeling off the tape-shaped multilayer film adhered to the adherend, the adhesive resin (B) is exposed at the adhesive portion in an adhesive state capable of being resealed, and can be easily resealed only by hand pressure. Become a bag or lid.

  Further, when the surface resin layer (A) and the heat seal resin layer (C) of the tape using the multilayer film of the present invention are the same type of resin, the tape is sandwiched in an opening portion of an adherend such as a bag. After the bag is formed in an oval shape and filled with the contents, the resin layers (A) and (C) can be heat-sealed to the inner surface (seal layer) of the bag by heat sealing at the position where the tape is sandwiched. . That is, the opening can be sealed by heat sealing through the tape. In addition, when opening, the surface resin layer (A) and the adhesive resin layer (B) or the adhesive resin layer (B) and the heat seal resin layer (C) can be easily opened by delamination, and the adhesive resin layer The reseal function is also given from the exposure of (B).

  Using tape-like multilayer film for making bread, snack bread and snacks in sachets, and when filling bags makes it possible to manufacture re-sealed bags easily and at low cost. It is thought that the entrance and exit of moisture and moisture can be suppressed, and the protection of the contents after opening is increased.

  As a container using a lid material made of the multilayer film of the present invention, for example, a styrene resin, a foamed styrene resin, a propylene resin, an ester resin or the like is formed by a molding method such as injection molding, vacuum molding or pressure molding. Examples thereof include manufactured cups and trays, and paper cups and paper trays formed by laminating olefin-based resins such as polyethylene on paper. These containers can adjust the seal strength by selecting the type of heat seal resin of the tape according to the type of resin of the heat seal part with the lid.

  Furthermore, as a preferable use in using the multilayer film of the present invention, a light food, stationery, cosmetics and pharmaceuticals are filled in a bag and packaged. Numbers such as instant noodle containers or lids, breads, confectionery breads, snacks, chocolate confectionery, delicacy bags or lids, sliced ham etc. Examples include lids and bags for cosmetics and sanitary products that are packaged in individual units and opened and used each time, and lids and bags for pharmaceuticals such as ship medicines, emergency bandages, and throat candy. In these applications, it is not intentionally exposed to high temperatures, but it is assumed that it will become hot when left in the car in the summer or when it is stored in a warehouse, so it has excellent heat resealability. The multilayer film of the invention can be suitably used for container lids and bags.

Next, the present invention will be described in more detail with reference to examples and comparative examples.
Example 1
A medium density polyethylene resin having a density of 0.93 g / cm ³ is used as the resin for the surface resin layer (A), and an amorphous polypropylene resin [Ubetac UT2780 manufactured by Ube Lexellen Co., Ltd.] 80 is used as the resin for the adhesive resin layer (B). Pellets (1) obtained by melting and kneading 20 parts by weight of a propylene-ethylene copolymer (COPP) having a density of 0.90 g / cm ³ and an ethylene-derived component content of 3% by weight with a twin-screw extruder; , A selective hydrogenated product having a hydrogenation rate of 40 mol%, wherein a 1,2-bond portion of a styrene-butadiene-styrene block copolymer (SBS) is selectively hydrogenated [styrene-butadiene-butylene-styrene block copolymer Combined (SBBS)] 70 parts by weight and petroleum resin [Arakawa Chemical Co., Ltd. hydrogenated petroleum resin, Alcon P-125] 29.5 parts by weight and phenolic antioxidant Pellets (2) obtained by melting and kneading 0.5 parts by weight of the agent with a twin-screw extruder into pellets (1) and (2) having a weight ratio (1) / (2) of 50/50 An ethylene-methacrylic acid copolymer (EMAA) having a density of 0.94 g / cm ³ and a methacrylic acid-derived component content of 10% by weight as a heat seal resin layer (C) using a resin mixture (12) dry-blended at a ratio Using a resin mixture (3) in which erucic acid amide (lubricant) and natural silica (anti-blocking agent) were added and mixed at a ratio of erucic acid amide concentration of 1000 ppm and natural silica concentration of 2000 ppm, (A) extrusion for layer T-die / chill roll co-extrusion multilayer film having a machine (caliber 50 mm), (B) layer extruder (caliber 50 mm), (C) layer extruder (caliber 40 mm), and feed block Each of the extruders of the film manufacturing apparatus is supplied, and co-melt extrusion is performed under the conditions of a temperature of 200 to 230 ° C., a feed block and a T-die temperature of 270 ° C., and the average of each layer is composed of three layers of A / B / C. A coextruded multilayer film (X1) having a thickness of 40 μm / 5 μm / 5 μm, an overall thickness of 50 μm, and a friction coefficient of 0.6 on the surface of the heat seal resin layer (C) was obtained. Interlayer adhesion strength between the surface resin layer (A) and the adhesive resin layer (B) of the obtained coextruded multilayer film (X1) is 15 N / 15 mm, and interlayer adhesion strength between the adhesive resin layer (B) and the heat seal resin (C). Was 7 N / 15 mm. When the heat-seal resin (C) is heat-sealed with a resin layer having the same composition and peeled off, the co-extruded multilayer film (X1) breaks the heat-seal resin layer (C) and the adhesive resin layer (B). The interlayer of the heat seal resin layer (C) was peeled off, and the adhesive resin layer (B) was a multilayer film exposed in a resealable state on the surface of the heat seal region.

  In addition, when the amorphous propylene-based resin Ubetac UT2780 5 mg was used and measured at a temperature increase rate of 10 ° C./min from 20 ° C. to 230 ° C., no melting peak was observed, and the heat of fusion of the maximum peak in the endothermic curve was 0 0.7 J / g or less.

  Next, a biaxially stretched polyethylene terephthalate substrate (thickness 12 μm) was bonded to the surface resin layer (A) side of the obtained coextruded multilayer film (X1) by dry lamination to obtain a laminate film (Y1). At this time, a two-component curable adhesive (polyester adhesive LX63F and a curing agent KP90) manufactured by Dainippon Ink & Chemicals, Inc. was used as an adhesive for dry lamination.

  Using the obtained laminate film (Y1) as a lid material, the heat sealing conditions (seal temperature) shown in Table 1 are applied to the ridge portion of a round cup container having a ridge of 70 mm in outer shape and 5 mm in width made of the material shown in Table 1. , Sealing time, sealing pressure), and sealing strength was measured. Moreover, the feeling of opening at the time of opening was evaluated, and the film remaining state of the opened part was also evaluated visually. Further, after opening, hot water at 95 ° C. was put in, the lid material and the container were pressure-bonded again with fingers, and left for 5 minutes, and the seal strength (reseal strength) after 5 minutes was measured. The results are shown in Tables 2 and 3.

  The feeling of opening is when the lid is actually peeled from the container and the force required for peeling is constant and smooth peeling is easy, and the force required for peeling is not constant, and peeling is not smooth. X, and the film scraping condition is that the film remains on the seal surface of the buttock and lid after peeling and the state of flaking is visually observed. Some were evaluated as x.

Comparative Example 1
As the resin for the adhesive resin layer (B), instead of the resin mixture (12), a hydrogenation rate of selectively hydrogenating the 1,2-bond portion of the styrene-butadiene-styrene block copolymer (SBS) 40 Mole% selective hydrogenated product [styrene-butadiene-butylene-styrene block copolymer (SBBS)] 70 parts by weight and petroleum resin [Arakawa Chemical Co., Ltd. hydrogenated petroleum resin, Alcon P-125] 29.5 weight 3 layers of A / B / C in the same manner as in Example 1 except that pellets (2) obtained by melt-kneading and mixing 0.5 parts by weight of phenol-based antioxidant with a twin-screw extruder were used. A coextruded multilayer film (X1 ′) having an average thickness of 40 μm / 5 μm / 5 μm, an overall thickness of 50 μm, and a friction coefficient of 0.6 on the surface of the heat seal resin layer (C) was obtained. . The interlayer adhesive strength between the surface resin layer (A) and the adhesive resin layer (B) of the obtained coextruded multilayer film (X1 ′) is 16 N / 15 mm, and the interlayer between the adhesive resin layer (B) and the heat seal resin (C). The adhesive strength was 9 N / 15 mm. When this heat-extruded multilayer film (X1 ′) is peeled off by heat-sealing the heat-seal resin (C) with a resin layer having the same composition, the heat-seal resin layer (C) breaks and the adhesive resin layer (B) And the heat seal resin layer (C) were peeled off, and the adhesive resin layer (B) was a multilayer film exposed in a resealable state on the surface of the heat seal region.

  Next, a biaxially stretched polyethylene terephthalate substrate (thickness: 12 μm) was bonded to the surface resin layer (A) side of the obtained coextruded multilayer film (X1 ′) by dry lamination to obtain a laminate film (Y1 ′). It was. At this time, a two-component curable adhesive (polyester adhesive LX63F and a curing agent KP90) manufactured by Dainippon Ink & Chemicals, Inc. was used as an adhesive for dry lamination.

  Using the obtained laminate film (Y1 ′) as a lid material, the heat sealing conditions (seal) shown in Table 1 are applied to the ridge portion of a round cup container having a rim of 70 mm in outer shape and 5 mm width made of the material shown in Table 1. After heat sealing (temperature, sealing time, sealing pressure), the sealing strength was measured. Moreover, the feeling of opening at the time of opening was evaluated, and the film remaining state of the opened part was also evaluated visually. Further, after opening, hot water at 95 ° C. was put in, the lid material and the container were pressure-bonded again with fingers, and left for 5 minutes, and the seal strength (reseal strength) after 5 minutes was measured. The results are shown in Tables 2 and 3.

Example 2
Zinc neutralized product (ionomer resin) of ethylene-methacrylic acid copolymer having a density of 0.94 g / cm ³ is used as the resin for the surface resin layer (A), and amorphous resin is used as the resin for the adhesive resin layer (B). Biaxially, 80 parts by weight of propylene-based resin (Ubetac UT2780 manufactured by Ube Lexelen Co., Ltd.) and 20 parts by weight of propylene-ethylene copolymer (COPP) having a density of 0.90 g / cm ³ and an ethylene-derived component content of 3% by weight Pellets (1) melt-kneaded and pelletized with an extruder and hydrogenated styrene-butadiene-styrene block copolymer (SBS) [styrene-ethylene-butylene-styrene block copolymer (SEBS)] 70 weight Part and terpene resin [Yasuhara Chemical Co., Ltd. terpene resin, YS Resin PX1150] 28.5 parts by weight and phenolic antioxidant 0.5 A pellet (2) obtained by melting and kneading an amount of 1 part by weight of liquid paraffin with a twin-screw extruder into a pellet (2) has a weight ratio (1) / (2) of pellets (1) and (2) of 50/50. A propylene-ethylene copolymer having a density of 0.90 g / cm ³ and an ethylene-derived component content of 3% by weight as a resin for the heat seal resin layer (C) using a resin mixture (12) dry blended at a mixing ratio of COPP) is mixed with erucic acid amide (lubricant) and natural silica (anti-blocking agent) at a ratio of erucic acid amide concentration of 1000 ppm and natural silica concentration of 2000 ppm. A co-extruded multilayer film having a three-layer structure of A / B / C, an average thickness of each layer of 37 μm / 10 μm / 3 μm, and an overall thickness of 50 μm, as in Example 1. (X2) was obtained. The interlayer adhesive strength between the surface resin layer (A) and the adhesive resin layer (B) of the obtained coextruded multilayer film (X2) is 15 N / 15 mm, and the interlayer adhesion between the adhesive resin layer (B) and the heat seal resin (C) The strength was 20 N / 15 mm. When this heat-extruded multilayer film (X2) is peeled off by heat-sealing the heat-seal resin layer (C) with a resin layer having the same composition, the adhesive resin layer (B) and the heat-seal resin layer (C) are broken. In addition, the surface resin layer (A) and the adhesive resin layer (B) were separated from each other, and the adhesive resin layer (B) was exposed in a resealable state on the surface of the heat seal region.

Next, extrusion lamination was performed on the surface resin layer (A) of the obtained coextruded multilayer film (X2) by melt extrusion at 330 ° C. of low density polyethylene (LDPE) for lamination (MI = 10 g / min). And laminated with a paper substrate (basis weight 80 g / cm ² ) to obtain a laminated paper (Y2).

  Using the obtained laminated paper (Y2) as a lid material, heat sealing is performed on the ridge portion of a round cup container having a ridge of 70 mm in outer shape and 5 mm in width made of the material shown in Table 1 under the heat sealing conditions shown in Table 1. Then, in the same manner as in Example 1, evaluation and measurement of sealing strength, opening feeling, film remaining state, resealing strength, and resealing strength after filling with hot water were performed. The results are shown in Tables 2 and 3.

Example 3
As the resin for the surface resin layer (A), a sodium neutralized product (ionomer resin) of an ethylene-methacrylic acid copolymer having a density of 0.94 g / cm ³ is used, and as the resin for the adhesive resin layer (B), amorphous resin is used. Twin screw extruder of 80 parts by weight of polypropylene resin [Ubetac UT2780 manufactured by Ube Lexelen Co., Ltd.] and 20 parts by weight of propylene-ethylene copolymer (COPP) having a density of 0.90 g / cm ³ and an ethylene-derived component content of 3% by weight Pellets (1) melt-kneaded and pelletized with 60 parts by weight of hydrogenated product (HSB) of styrene-butadiene block copolymer (SB) and terpene resin [terpene resin, YS resin PX1150 manufactured by Yashara Chemical Co., Ltd.] A pellet (2) obtained by melt-kneading 38.5 parts by weight and 0.5 parts by weight of a phenolic antioxidant with a twin-screw extruder was pelletized. The resin mixture (12) dry-blended at a mixing ratio (1) / (2) (1) / (2) of 50/50 is used as a resin for the heat seal resin layer (C). Impact polystyrene (Dai Nippon Ink Chemical Co., Ltd. CR8300) was mixed with erucamide (lubricant) and natural silica (anti-blocking agent) at a ratio of erucamide concentration of 200 ppm and natural silica concentration of 2000 ppm. A resin mixture (3) was used, and each of these was used in the same manner as in Example 1, with a three-layer structure of A / B / C, the average thickness of each layer being 40 μm / 5 μm / 5 μm, and the overall thickness Was 50 μm, and a coextruded multilayer film (X3) having a friction coefficient of 0.6 on the surface of the heat seal resin layer (C) was obtained. The interlayer adhesion strength between the surface resin layer (A) and the adhesive resin layer (B) of the obtained coextruded multilayer film (X3) is 12 N / 15 mm, and the interlayer adhesion between the adhesive resin layer (B) and the heat seal resin (C). The strength was 20 N / 15 mm. When this heat-extruded multilayer film (X3) is peeled off by heat-sealing the heat-seal resin layer (C) with a resin layer having the same composition, the adhesive resin layer (B) and the heat-seal resin layer (C) are broken. In addition, the surface resin layer (A) and the adhesive resin layer (B) were separated from each other, and the adhesive resin layer (B) was exposed in a resealable state on the surface of the heat seal region.

Next, extrusion lamination was performed on the surface resin layer (A) of the obtained coextruded multilayer film (X3) by melt extrusion at 330 ° C. of laminating low density polyethylene (LDPE) (MI = 10 g / min). Then, a paper substrate (basis weight 80 g / cm ² ) was bonded to obtain a laminated paper (Y3).

  Using the obtained laminated paper (Y3) as a cover material, heat sealing was performed on the ridge portion of a round cup container having a ridge of 70 mm in outer shape and 5 mm in width made of the material shown in Table 1 under the heat sealing conditions shown in Table 1. Then, in the same manner as in Example 1, evaluation and measurement of sealing strength, opening feeling, film remaining state, resealing strength, and resealing strength after filling with hot water were performed. The results are shown in Tables 2 and 3.

Example 4
A sodium neutralized ethylene-methacrylic acid copolymer having a density of 0.94 g / cm ³ is used as the resin for the surface resin layer (A), and an amorphous polypropylene resin [Ube as the resin for the adhesive resin layer (B). Ulexac UT2780 manufactured by Lexelene Co., Ltd.] 80 parts by weight and 20 parts by weight of a propylene-ethylene copolymer (COPP) having a density of 0.90 g / cm ³ and an ethylene-derived component content of 3% by weight in a twin screw extruder. Pellets (1), 30 parts by weight of hydrogenated product (HSB) of styrene-butadiene block copolymer (SB) and hydrogenated product of styrene-isoprene-styrene block copolymer (SIS) [styrene -30 parts by weight of ethylene-propylene-styrene block copolymer (SEPS) and terpene resin [terpene resin manufactured by Yashara Chemical Co., Ltd., S Resin PX1150] 38.5 parts by weight and 0.5 parts by weight of phenolic antioxidant were melt-kneaded in a twin-screw extruder to form pellets (2), and the weight ratio of pellets (1) and (2) Using a resin mixture (12) dry blended at a mixing ratio of (1) / (2) of 50/50, a polyester resin (PETG6763 manufactured by Eastman Kodak Company, density 1) as a resin for the heat seal resin layer (C) Erucic acid amide (lubricant) and natural silica (anti-blocking agent) were added to erucic acid in a resin mixture obtained by dry blending 80 parts by weight of 27 g / cm ³ ) and 20 parts by weight of acid-modified polyethylene [SF731 manufactured by Mitsui Chemicals, Inc.] Using a resin mixture (3) added and mixed at a ratio such that the amide concentration is 1000 ppm and the natural silica concentration is 2000 ppm, these are used respectively. Except for the above, in the same manner as in Example 1, a three-layer structure of A / B / C, the average thickness of each layer was 35 μm / 10 μm / 5 μm, the total thickness was 50 μm, and the surface of the heat seal resin layer (C) A coextruded multilayer film (X4) having a friction coefficient of 0.6 was obtained. The interlayer adhesion strength between the surface resin layer (A) and the adhesive resin layer (B) of the obtained coextruded multilayer film (X4) is 12 N / 15 mm, and the interlayer adhesion between the adhesive resin layer (B) and the heat seal resin (C). The strength was 20 N / 15 mm. When the heat-seal resin layer (C) is heat-sealed with a resin layer having the same composition and peeled off, the co-extruded multilayer film (X4) breaks the adhesive resin layer (B) and the heat-seal resin layer (C). In addition, the surface resin layer (A) and the adhesive resin layer (B) were separated from each other, and the adhesive resin layer (B) was exposed in a resealable state on the surface of the heat seal region.

  Next, a biaxially stretched polyethylene terephthalate film substrate (thickness 12 μm) was bonded to the surface resin layer (A) side of the obtained coextruded multilayer film (X4) by dry lamination to obtain a laminate film (Y4). . At this time, a two-component curable adhesive (polyester adhesive LX63F and a curing agent KP90) manufactured by Dainippon Ink & Chemicals, Inc. was used as an adhesive for dry lamination.

  Using the obtained laminate film (Y4) as a cover material, heat sealing is performed on the ridge portion of a round cup container having a rim of 70 mm in outer shape and 5 mm in width made of the material shown in Table 1 under the heat sealing conditions shown in Table 3. Then, in the same manner as in Example 1, evaluation and measurement of sealing strength, opening feeling, film remaining state, resealing strength, and resealing strength after filling with hot water were performed. The results are shown in Tables 2 and 3.

Claims (16)

Contains a surface resin layer (A) containing a thermoplastic resin (a) and an amorphous olefin resin (b1) having a content of α-olefin-derived component having 3 or more carbon atoms of 50 mol% or more. A multilayer in which an adhesive resin layer (B) formed and a heat seal resin layer (C) containing a thermoplastic resin (c) are laminated in the order of (A) / (B) / (C) When the heat-seal resin layer (C) is heat-sealed with a resin layer having the same composition and peeled off, the adhesive resin layer (B) is exposed in a resealable state on the surface of the heat-seal region A multilayer film characterized by that. When the heat seal resin layer (C) is heat sealed with a resin layer having the same composition and peeled off, the heat seal resin layer (C) breaks and the adhesive resin layer (B) and the heat seal resin layer (C) The interlayer is peeled and peeled, or the adhesive resin layer (B) and the heat seal resin layer (C) are ruptured, and the surface resin layer (A) and the adhesive resin layer (B) are separated from each other. The multilayer film according to claim 1, wherein (B) is exposed in a resealable state on the surface of the heat seal region. The multilayer film according to claim 2, wherein the adhesive resin layer (B) is a resin layer comprising an amorphous olefin resin (b1) and a rubbery thermoplastic resin (b2). The amorphous olefin-based resin (b1) is an amorphous olefin-based resin in which the content of the α-olefin-derived component having 3 to 12 carbon atoms is 80 mol% or more, and the rubber-like thermoplastic resin (b2) is a styrene block. The multilayer film according to claim 3, which is a hydrogenated product of a rubbery block copolymer containing a diene block. The multilayer film according to claim 2, wherein the adhesive resin layer (B) is a resin layer comprising an amorphous olefin resin (b1), a rubbery thermoplastic resin (b2), and a tackifier (b3). The amorphous olefin-based resin (b1) is an amorphous olefin-based resin in which the content of the α-olefin-derived component having 3 to 4 carbon atoms is 80 mol% or more, and the rubbery thermoplastic resin (b2) is a styrene block 6. The multilayer film according to claim 5, which is a hydrogenated product of a rubbery block copolymer containing a diene block. The multilayer film according to claim 6, wherein the tackifier (b3) is one or more resins selected from the group consisting of rosin resins, terpene resins and petroleum resins. The adhesive resin layer (B) comprises an amorphous polyolefin (b1), a rubbery thermoplastic resin (b2) and a tackifier (b3), and a weight ratio (b1) / (b2) of 30/70 to 80/20. The multilayer film according to claim 5, wherein the multilayer film is a resin layer that is contained at a weight ratio (b1 + b2) / (b3) of 60/40 to 90/10. The adhesive resin layer (B) further contains an olefin resin (b4) other than the amorphous olefin resin (b1) in which the content of the α-olefin-derived component having 3 or more carbon atoms is 50 mol% or more. The multilayer film according to claim 1, wherein the multilayer film is a resin layer. When the heat seal resin layer (C) is heat sealed with a resin layer having the same composition and peeled off, the heat seal resin layer (C) breaks and the adhesive resin layer (B) and the heat seal resin layer (C) It is a multilayer film in which the interlayer is peeled off and the adhesive resin layer (B) is exposed in a resealable state on the surface of the heat seal region, and the interlayer adhesion between the adhesive resin layer (B) and the heat seal resin layer (C) The strength is 2 to 20 N / 15 mm, which is smaller than the interlayer adhesive strength between the surface resin layer (A) and the adhesive resin layer (B), and the thickness of the heat seal resin layer (C) is 0.6 to 10 μm. The multilayer film according to claim 1, wherein the multilayer film is a coextruded multilayer film having a total thickness of 20 to 200 μm. The thermoplastic resin (a) is an ethylene resin or a propylene resin, and the thermoplastic resin (c) is an ethylene- (meth) acrylic acid copolymer and / or a metal neutralized product thereof. Multilayer film. When the heat-seal resin layer (C) is heat-sealed with a resin layer having the same composition and then peeled off, the adhesive resin layer (B) and the heat-seal resin layer (C) break and the surface resin layer (A) and the adhesive The interlayer of the resin layer (B) is peeled off, and the adhesive resin layer (B) is exposed in a resealable state on the surface of the heat seal region, and the surface resin layer (A) and the adhesive resin layer ( B) has an interlayer adhesive strength of 2 to 23 N / 15 mm, and is smaller than the interlayer adhesive strength of the adhesive resin layer (B) and the heat seal resin layer (C), and the adhesive resin layer (B) and the heat seal resin The multilayer film according to any one of claims 1 to 8, which is a coextruded multilayer film having a total thickness of 3 to 25 µm and a total thickness of 20 to 200 µm. The thermoplastic resin (a) is an ethylene- (meth) acrylic acid copolymer and / or a metal neutralized product thereof, and the thermoplastic resin (c) is an olefin resin, ester resin or styrene resin. Item 13. The multilayer film according to Item 12. A container lid material comprising the multilayer film according to any one of claims 1 to 13. A container lid material comprising a substrate laminated on the surface resin layer (A) of the multilayer film according to any one of claims 1 to 13. A bag formed by heat-sealing the heat-seal layers of the multilayer film according to any one of claims 1 to 13 superimposed on each other.