CN108070330B - Adhesive for sealant and film for lid material - Google Patents
Adhesive for sealant and film for lid material Download PDFInfo
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- CN108070330B CN108070330B CN201711071513.1A CN201711071513A CN108070330B CN 108070330 B CN108070330 B CN 108070330B CN 201711071513 A CN201711071513 A CN 201711071513A CN 108070330 B CN108070330 B CN 108070330B
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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
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/08—Copolymers of ethene
- C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C09J123/0853—Vinylacetate
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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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
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/08—Copolymers of ethene
- C09J123/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C09J123/0815—Copolymers of ethene with aliphatic 1-olefins
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
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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
- C09J2423/00—Presence of polyolefin
- C09J2423/04—Presence of homo or copolymers of ethene
-
- 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
- C09J2423/00—Presence of polyolefin
- C09J2423/04—Presence of homo or copolymers of ethene
- C09J2423/046—Presence of homo or copolymers of ethene in the substrate
-
- 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
- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
Abstract
The invention aims to provide an adhesive for a sealant which has excellent forming processability and satisfies sealing strength and bonding strength to an A-PET container and can be used for a cover material of the A-PET container, and a film for the cover material. The adhesive for the sealant of the cover material of the container comprises: 10 to 50 parts by weight of an ethylene-vinyl acetate copolymer (A) having a vinyl acetate content of 3 to 15% by weight, 10 to 50 parts by weight of an ethylene-vinyl acetate copolymer (B) having a vinyl acetate content of 8 to 25% by weight, and 5 to 40 parts by weight of a tackifier resin (C) (the total amount of (A), (B) and (C) being 100 parts by weight), the difference between the vinyl acetate content of the ethylene-vinyl acetate copolymer (A) and the vinyl acetate content of the ethylene-vinyl acetate copolymer (B) being 3 to 20% by weight.
Description
Technical Field
The present invention relates to a film for a lid material of a container, and more particularly, to an adhesive for a sealant which is excellent in moldability, can obtain high seal strength and adhesive strength, and is excellent in heat resistance, and is used for a lid material of a container made of amorphous polyethylene terephthalate (hereinafter referred to as a-PET), and a film for a lid material.
Background
Conventionally, plastic containers such as polyethylene, polypropylene, and polystyrene, or paper containers mainly made of paper have been used for packaging drinks, pharmaceuticals, industrial parts, and the like, and an easy-peel film having stable adhesive strength for protecting the contents and easy-peel property that can be opened with moderate strength at the time of peeling has been used as a lid material. Although a large number of materials have been known for containers made of polypropylene, polystyrene, etc., an easy-to-peel film excellent in practical use has not been found for a-PET container which is inexpensive and excellent in transparency and cold resistance in recent years. When a conventional easy-peeling film is used as a lid material for a container made of a-PET, the adhesion strength is weak, and therefore, there is a problem that the lid is opened due to vibration or dropping during transportation or storage, or a problem that the container is deformed and the sealing property is degraded due to setting the heat-sealing temperature high in order to obtain high adhesion strength. Further, there is a disadvantage that storage in a low temperature environment after bonding causes a decrease in sealing strength, and there is a problem in practical use. Generally, as a lid material sealant adhesive, a mixture containing polyethylene, an ethylene-vinyl acetate copolymer, and a tackifier is known, but in such a material, sufficient adhesive strength cannot be obtained with respect to an a-PET container. Further, resin compositions comprising an ethylene- α -olefin copolymer, a tackifier, and an olefinic elastomer and/or a styrenic elastomer (see, for example, patent document 1), and sealing materials comprising an ethylene- α -olefin copolymer, an ethylene-polar monomer copolymer, an a-B-a type block copolymer, and a tackifier (see, for example, patent document 2) have been used, but these materials do not satisfy all the characteristics of molding processability, sealing strength, and adhesive strength.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 1999-269319
Patent document 2: japanese patent No. 4438108
Disclosure of Invention
Problems to be solved by the invention
However, none of the above methods sufficiently satisfies the molding processability, the sealing strength to a-PET containers, and the adhesion strength.
The purpose of the present invention is to provide an adhesive for a sealant used for a lid material of an A-PET container, which has excellent moldability and satisfies the sealing strength and adhesive strength to the A-PET container, and a film for the lid material.
Means for solving the problems
The present inventors have conducted extensive studies to solve the above problems, and as a result, have found that an adhesive for sealants comprising specific 2 ethylene-vinyl acetate copolymers and a tackifier is excellent in moldability and excellent in sealing strength and adhesive strength to a-PET containers, and have completed the present invention.
That is, the present invention relates to an adhesive for a lid material sealant for a container and a film for a lid material, the adhesive for a lid material sealant for a container comprising: 10 to 50 parts by weight of an ethylene-vinyl acetate copolymer (A) having a vinyl acetate content of 3 to 15% by weight, 10 to 50 parts by weight of an ethylene-vinyl acetate copolymer (B) having a vinyl acetate content of 8 to 25% by weight, and 5 to 40 parts by weight of a tackifier resin (C) (the total amount of (A), (B) and (C) being 100 parts by weight), the difference between the vinyl acetate content of the ethylene-vinyl acetate copolymer (A) and the vinyl acetate content of the ethylene-vinyl acetate copolymer (B) being 3 to 20% by weight, the vinyl acetate content of the ethylene-vinyl acetate copolymer (A) being smaller than the vinyl acetate content of the ethylene-vinyl acetate copolymer (B).
The present invention will be described in detail below.
The adhesive for a lid material sealant of a container of the present invention comprises: 10 to 50 parts by weight of an ethylene-vinyl acetate copolymer (A) having a vinyl acetate content of 3 to 15% by weight, 10 to 50 parts by weight of an ethylene-vinyl acetate copolymer (B) having a vinyl acetate content of 8 to 25% by weight, and 5 to 40 parts by weight of a tackifier resin (C) (the total amount of (A), (B) and (C) being 100 parts by weight), the difference between the vinyl acetate content of the ethylene-vinyl acetate copolymer (A) and the vinyl acetate content of the ethylene-vinyl acetate copolymer (B) being 3 to 20% by weight, the vinyl acetate content of the ethylene-vinyl acetate copolymer (A) being smaller than the vinyl acetate content of the ethylene-vinyl acetate copolymer (B).
The ethylene-vinyl acetate copolymer (A) has a vinyl acetate content of 3 to 15 wt%, preferably 5 to 10 wt%. When the vinyl acetate content is less than 3% by weight, the resultant adhesive for sealants is not good in low-temperature heat sealability. On the other hand, when the vinyl acetate content exceeds 15% by weight, the resultant adhesive for sealants is not satisfactory in moldability. The vinyl acetate content of the ethylene-vinyl acetate copolymer can be measured by a method based on JIS K6924-1.
The ethylene-vinyl acetate copolymer (A) preferably has a melt flow rate, as measured at 190 ℃ under a load of 21.18N, in the range of 1 to 30g/10 min, particularly preferably 3 to 15g/10 min, in accordance with JIS K6924-1. When the melt flow rate is 1g/10 min or more, the resultant adhesive for sealants is excellent in moldability and adhesive strength, and therefore, it is preferable. On the other hand, a melt flow rate of 30g/10 min or less is preferred because the molding stability of the resulting adhesive for sealants is excellent.
The ethylene-vinyl acetate copolymer (a) can be obtained by a known production method, and commercially available ones can be used. Specific examples thereof include Ultracene 515, Ultracene 537, Ultracene 540, Ultracene 541 (manufactured by Tosoh Corp.), and the like.
The ethylene-vinyl acetate copolymer (B) has a vinyl acetate content of 8 to 25 wt%, preferably 10 to 20 wt%. When the vinyl acetate content is less than 8% by weight, the resultant adhesive for sealants is not satisfactory in low-temperature heat sealability and adhesive strength. On the other hand, when the vinyl acetate content exceeds 25% by weight, the resultant adhesive for sealants is not satisfactory in moldability and blocking resistance. The vinyl acetate content of the ethylene-vinyl acetate copolymer can be measured by a method based on JIS K6924-1.
The ethylene-vinyl acetate copolymer (B) preferably has a melt flow rate, as measured at 190 ℃ under a load of 21.18N according to JIS K6924-1, in the range of 1 to 30g/10 min, and particularly preferably 3 to 20g/10 min. When the melt flow rate is 1g/10 min or more, the resultant adhesive for sealants is excellent in moldability and adhesive strength, and therefore, it is preferable. On the other hand, a melt flow rate of 30g/10 min or less is preferred because the molding stability of the resulting adhesive for sealants is excellent.
The ethylene-vinyl acetate copolymer (B) can be obtained by a known production method, and commercially available ones can be used. Specific examples thereof include Ultracene 541, Ultracene 626, Ultracene 625 and Ultracene 633 (manufactured by Tosoh Corp.), which are trade names.
The difference between the vinyl acetate content of the ethylene-vinyl acetate copolymer (A) and the vinyl acetate content of the ethylene-vinyl acetate copolymer (B) is 3 to 20% by weight, preferably 3 to 15% by weight. When the difference in vinyl acetate content is less than 3% by weight, the adhesive strength of the resulting adhesive for sealants is not good, which is not preferable. On the other hand, if the content exceeds 20% by weight, the resultant adhesive for sealants is not satisfactory in molding stability.
Any tackifier may be used as the tackifier (C) constituting the present invention as long as it falls within the category of tackifiers, and examples thereof include: petroleum resins, coumarone resins, styrenes, and the like as synthetic petroleum resin tackifiers; rosin resins, methyl ester resins, glycerin ester resins, pentaerythritol ester resins, terpene resins, and modified products thereof, which are natural resin tackifiers. Among these tackifiers, synthetic petroleum resin-based tackifiers include: aliphatic petroleum resins, aliphatic hydrogenated petroleum resins, aromatic hydrogenated petroleum resins, alicyclic hydrogenated petroleum resins, copolymerized hydrogenated petroleum resins, and the like. Among them, aromatic hydrogenated petroleum resins and alicyclic hydrogenated petroleum resins are preferably used. In particular, a resin obtained by partially hydrogenating 50 to 90% of at least one selected from the group consisting of an aliphatic petroleum resin, an aromatic petroleum resin, an alicyclic hydrogenated petroleum resin and a copolymer petroleum resin is preferable because it is excellent in sealing strength and adhesive strength. These tackifiers may be used alone or in combination of two or more.
The thickener (C) is preferably a thickener having a softening point of 90 to 140 ℃ as measured by a ring and ball method, and particularly preferably 100 to 135 ℃. If the softening point is less than 90 ℃, blocking resistance is poor, and if it exceeds 140 ℃, adhesion strength retention in a low-temperature environment is poor.
As the tackifier (C), those commercially available can be used. Specific examples thereof include: (trade name) Alcon M90, Alcon M115, Alcon M135, Alcon P100, Alcon P125, I-MARV S110, I-MARV P125, T-REZ RC115, T-REZ HA125, Pine Crystal KE-311, YS Resin PX1150N, etc.
The blending amounts of the ethylene-vinyl acetate copolymer (a), the ethylene-vinyl acetate copolymer (B) and the tackifier (C) are as follows, and the total amount of (a), (B) and (C) is 100 parts by weight.
The ethylene-vinyl acetate copolymer (A) is preferably used in an amount of 10 to 50 parts by weight, and particularly, in an amount of 20 to 40 parts by weight, because it can form an adhesive for sealants having an excellent balance between adhesive strength and moldability. When the amount is less than 10 parts by weight, the resulting adhesive for sealants is not good in molding stability. On the other hand, when the amount is more than 50 parts by weight, the adhesive strength of the adhesive for sealants obtained is not sufficient, which is not preferable.
The ethylene-vinyl acetate copolymer (B) is preferably contained in an amount of 10 to 50 parts by weight, and particularly, in order to form an adhesive for sealants having an excellent balance between adhesive strength and moldability, 20 to 40 parts by weight. When the amount is less than 10 parts by weight, the adhesive strength of the adhesive for sealants obtained is not good, which is not preferable. On the other hand, when the amount is more than 50 parts by weight, the resultant adhesive for sealants is not good in molding stability and blocking resistance, and thus is not preferable.
The amount of the thickener (C) is 5 to 40 parts by weight, and particularly preferably 15 to 30 parts by weight. When the amount is less than 5 parts by weight, the resulting adhesive for sealants is not preferable because the sealing strength and the adhesive strength are poor. On the other hand, when the amount exceeds 40 parts by weight, the roll-releasing property during molding is not good and blocking of the roll occurs, which is not preferable.
In order to obtain an adhesive having excellent sealing strength particularly at low temperatures, it is preferable to blend an adhesive for a sealant of the present invention with a density of 860 to 910kg/m measured in accordance with JIS K6922-1 (1998)3A range of ethylene-alpha-olefin copolymers (D). In addition, the amount of the ethylene- α -olefin copolymer (D) blended in this case is preferably 10 to 50 parts by weight, and particularly preferably 20 to 40 parts by weight, based on 100 parts by weight of the total amount of the ethylene-vinyl acetate copolymer (a), the ethylene-vinyl acetate copolymer (B), and the tackifier resin (C).
As the ethylene- α -olefin copolymer (D), any one may be used as long as it falls within the category generally referred to as ethylene- α -olefin copolymers. The α -olefin is not particularly limited, but includes: propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, etc., having 3 to 12 carbon atoms. These ethylene- α -olefin copolymers (D) can be suitably produced by copolymerizing ethylene and an α -olefin using a ziegler-based catalyst, a chromium-based catalyst, or a metallocene catalyst. Examples of the polymerization method include a solution polymerization method, a high pressure polymerization method, and a gas phase polymerization method. Further, the ethylene- α -olefin copolymer (D) is preferable because it has excellent low-temperature heat sealability and seal strength when the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) calculated as the molecular weight of the linear polyethylene is 3 or less using gel permeation chromatography under the conditions shown below using a calibration curve commonly used in the measurement of monodisperse polystyrene.
The machine is as follows: 150C ALC/GPC manufactured by Waters corporation
Solvent: 1,2, 4-trichlorobenzene
Flow rate: 1ml/min
Temperature: 140 deg.C
And (3) measuring the concentration: 30mg/30ml
Injection amount: 100 μ l
A chromatographic column: TSKgel GMH HR-H3 root made by Tosoh
In addition, the ethylene- α -olefin copolymer (D) is preferably such that when the temperature (Tm (° c)) at the maximum peak position of the endothermic curve obtained by temperature rise measurement using a differential scanning calorimeter and the number of Short Chain Branches (SCB) corresponding to 1000 carbon atoms determined by measurement of infrared absorption spectrum satisfy the relationship of formula (1), the composition distribution of the ethylene- α -olefin copolymer is narrow, and the low density (high short chain branch number) component that causes deterioration of low temperature heat sealability is small. This is due to the following relationship for ethylene- α -olefin copolymers: the greater the number of carbon atoms per 1000 corresponding Short Chain Branches (SCB), the lower the density and the lower the melting point. Even if the number of short chain branches is increased in order to lower the melting point, the melting point of an ethylene- α -olefin copolymer containing a large amount of low density (high number of short chain branches) is increased by introducing a large amount of short chain branches into a low molecular weight portion. On the other hand, even for an ethylene- α -olefin copolymer having the same short chain branch number, an ethylene- α -olefin copolymer in which short chain branches are uniformly introduced into a portion ranging from a low molecular weight to a high molecular weight has a lower melting point than an ethylene- α -olefin copolymer containing a large amount of low density (high short chain branch number).
Tm＜-1.8×SCB+140(1)
Such an ethylene- α -olefin copolymer (D) can be produced, for example, by the method disclosed in the following publications.
Examples thereof include: japanese patent laid-open Nos. 60-35006, 60-35007, 60-35008, 3-163088, 61-296008, 63-22804, 58-19309, 63-61010, 63-152608, 63-264606, 63-280703, 64-6003, 1-95110, 3-62806, 1-259004, 64-45406, 60-106808, 60-137911, 61-296008, Japanese patent publication No. 63-501369, Japanese patent publication No. 61-221207, Japanese patent publication No. 2-22307, Japanese patent publication No. 2-173110, Japanese patent publication No. 2-302410, Japanese patent publication No. 1-129003, Japanese patent publication No. 1-210404, Japanese patent publication No. 3-66710, Japanese patent publication No. 3-70710, Japanese patent publication No. 1-207248, Japanese patent publication No. 63-222177, Japanese patent publication No. 63-222178, Japanese patent publication No. 63-222179, Japanese patent publication No. 1-12407, Japanese patent publication No. 1-301704, Japanese patent publication No. 1-319489, Japanese patent publication No. 3-74412, Japanese patent publication No. 61-264010, Japanese patent publication No. 1-275609, Japanese patent laid-open Nos. 63-251405, 64-74202, 2-41303, 1-31488, 3-56508, 3-70708 and 3-70709.
The ethylene- α -olefin copolymer (D) may be a commercially available product.
Since an adhesive having excellent sealing strength and adhesive strength is obtained, it is preferable to blend the thermoplastic block copolymer (E) of a vinyl aromatic hydrocarbon and an olefin or diene in the adhesive for sealants of the present invention. In addition, the amount of the thermoplastic block copolymer (E) of a vinyl aromatic hydrocarbon and an olefin or diene is preferably 0.5 to 5 parts by weight, particularly preferably 1 to 4 parts by weight, based on 100 parts by weight of the total amount of the ethylene-vinyl acetate copolymer (a), the ethylene-vinyl acetate copolymer (B), and the tackifier resin (C) or based on 100 parts by weight of the total amount of the ethylene-vinyl acetate copolymer (a), the ethylene-vinyl acetate copolymer (B), and the tackifier resin (C) in which the ethylene- α -olefin copolymer (D) is blended.
The thermoplastic block copolymer (E) of a vinyl aromatic hydrocarbon and an olefin or diene of the present invention is a polymer having a block structure, which is represented by a general formula (a-B) n, (a-B) n-a 'or (a-B) m-X (wherein a and a' in the formula represent a vinyl aromatic hydrocarbon polymer block, B represents an olefin or diene polymer block, n represents an integer of 1 to 5, m represents an integer of 2 to 7, and X represents a polyfunctional compound having a valence of m), and which has a linear structure, a radial structure or a branched structure, and at least one terminal of which is a vinyl aromatic hydrocarbon polymer block, and may be a hydrogenated product thereof. Examples of the vinyl aromatic hydrocarbon used herein include: styrene, alpha-methylstyrene, vinyltoluene, p-tert-butylstyrene, vinylxylene, ethylvinylxylene, vinylnaphthalene, mixtures thereof, and the like. Of these, styrene is particularly preferable. On the other hand, examples of the olefin include α -olefins such as ethylene, propylene, and 1-butene, and examples of the diene include conjugated dienes such as butadiene and isoprene. As the thermoplastic block copolymer (E) of a vinyl aromatic hydrocarbon and a diene, a copolymer obtained by hydrogenating a polymer block obtained by polymerizing a conjugated diene may be used, and when an olefin unit is dominant in the block B, a copolymer of a conjugated diene and a vinyl aromatic hydrocarbon may be used. Among these, in the present invention, a thermoplastic block copolymer of a vinyl aromatic hydrocarbon and an olefin or diene having a vinyl aromatic hydrocarbon polymer block at both ends is preferable, and from the viewpoint of improving thermal stability, a hydrogenated product of a polystyrene-polybutadiene-polystyrene block copolymer (styrene-ethylene/butylene-styrene triblock copolymer, hereinafter referred to as SEBS) is particularly preferably used.
The melt flow rate of the thermoplastic block copolymer (E) of a vinyl aromatic hydrocarbon and an olefin or diene under a load of 5.0kg at 200 ℃ is preferably in the range of 10 to 70g/10 min, and particularly preferably 12 to 65g/10 min.
Further, since an adhesive for sealants excellent in moldability and adhesive strength is obtained, it is preferable that the thermoplastic block copolymer (E) of a vinyl aromatic hydrocarbon and an olefin or diene is a mixture of a hydrogenated styrene-butadiene-diblock copolymer and a hydrogenated styrene-butadiene-styrene-triblock copolymer, and the mixing ratio thereof is 5/5 to 9/1, preferably the styrene content is 20 to 50% by weight.
As the thermoplastic block copolymer (E) of a vinyl aromatic hydrocarbon and an olefin or diene, those commercially available can be used. Specific examples thereof include (trade name) Kraton G1726MS (manufactured by Kraton Polymer Co., Ltd.).
Other thermoplastic resins or rubbers, and light stabilizers, ultraviolet absorbers, nucleating agents, lubricants, antioxidants, antiblocking agents, fluidity improvers, mold release agents, flame retardants, colorants, inorganic neutralizing agents, hydrochloric acid absorbers, fillers, conductive agents, and the like may be used in the adhesive for sealants of the present invention within a range that does not impair the effects of the present invention.
The method for producing the adhesive for sealants of the present invention may be any method as long as it can produce the adhesive for sealants, and examples thereof include a method in which the ethylene-vinyl acetate copolymer (a), the ethylene-vinyl acetate copolymer (B), and the tackifier resin (C) are pre-blended together in a mixer such as a henschel mixer or a tumbler mixer, and melt-kneaded in a single-screw or twin-screw extruder.
The adhesive for sealants of the present invention can be used as an adhesive for sealants for lid materials of containers. The container is preferably a container containing polyethylene terephthalate as a main component.
The film for a cover material of the present invention comprises at least 2 layers of the support base layer and the adhesive layer for a sealant. The support base material constituting the support base material layer may be any material having self-supporting properties, and examples thereof include: plastic films made of olefin resins such as polyethylene, polypropylene and ethylene-acid copolymer resins, polyester resins such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate, thermoplastic resins such as polyamide resins, paper such as japanese paper and composite paper, metal foils made of metals such as aluminum, and individual or laminated products of these materials. The thickness of the support base material layer may be selected according to the application within a range that does not impair mechanical strength, workability, and the like, but is usually about 5 to 100 μm, and preferably 10 to 50 μm.
The thickness of the adhesive layer for sealant can be selected according to the application within the range that does not deteriorate the adhesiveness, workability, etc., but is usually about 5 to 50 μm, preferably 15 to 30 μm.
In the present invention, an intermediate layer may be provided between the support base layer and the sealant adhesive layer in order to improve adhesion between the two layers. The intermediate layer may be composed of a thermoplastic resin such as polyolefin, a thermoplastic elastomer, or the like, and these components may be used alone or in combination of 2 or more. Examples of the polyolefin include polyethylene, ethylene copolymers (e.g., ethylene- α -olefin copolymers, propylene-ethylene copolymers, ethylene-acrylic acid copolymers, ethylene-methacrylic acid copolymers, and ethylene-methyl acrylate copolymers), and modified products thereof. Various additives such as an antioxidant, a lubricant, an antistatic agent, a conductive agent, an antiblocking agent, a tackifier, and the like can be used in the intermediate layer within a range not to impair the effects of the present invention.
The thickness of the intermediate layer may be selected according to the application within a range not to impair workability, but is usually about 5 to 30 μm.
In the present invention, a primer layer such as polyurethane may be provided between the support base layer and the sealant adhesive layer or between the support base layer and the intermediate layer in order to improve adhesion between the two layers.
The film for a lid material of the present invention is suitable as a lid material for a container for a-PET, and has sealability and releasability.
The method for producing the film for a lid material is not particularly limited, and examples thereof include a method of laminating the adhesive for a sealant and the support base layer, and a method of co-extruding the adhesive for a sealant and the support base layer. Examples of the method of lamination include: (1) an extrusion lamination method in which a primer is applied to a support base layer and the adhesive layer is melt-extruded; (2) an extrusion lamination method in which after a primer is applied on a support base layer and an intermediate layer is melt-extruded, an adhesive layer for a sealant is melt-extruded thereon; (3) an extrusion lamination method in which an intermediate layer having excellent adhesion to a support base material layer is melt-extruded on the support base material layer, and then an adhesive layer for a sealant is melt-extruded thereon; (4) a coextrusion lamination method in which a primer is applied to the support base layer and the intermediate layer and the adhesive layer are simultaneously melt-extruded; (5) a dry lamination method in which a film containing at least 1 layer of sealant adhesive is formed in advance by a blow molding method or a cast molding method and is bonded to a support base layer coated with a primer; (6) and an extrusion lamination method in which the support base layer coated with the primer and a film containing at least 1 sealant adhesive are laminated by melt-extruding the intermediate layer using an extrusion laminator. On the other hand, as a method of coextrusion, a coextrusion blow molding method, a coextrusion T-die method, and the like can be cited.
ADVANTAGEOUS EFFECTS OF INVENTION
The adhesive for a lid material sealant of a container of the present invention is useful as a lid material film, and is useful for obtaining a lid material of an a-PET container having excellent moldability, high seal strength and adhesive strength, and excellent heat resistance.
Examples
The present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
Melt Flow Rate (MFR) c
MFR of the ethylene-vinyl acetate copolymer (A) and the ethylene-vinyl acetate copolymer (B) was measured in accordance with JIS K6924-1.
The resultant adhesive for sealants was evaluated for moldability by the following methods using examples.
About shaping processing stability &
Using an extrusion laminator (Placo screw diameter
) The adhesive pellets were extrusion-laminated at a processing temperature of 230 ℃ to obtain a film having an adhesive layer for a sealant of 25 μm thickness. In the determination, it is considered that the case (Δ and ∘) where no variation of 3 μm or more in film thickness after the lamination processing was present was good.
O: the fluctuation and the left-right shaking of the melting film do not exist, and the thickness deviation is less than 3 mu m;
and (delta): pulsation and left-right shaking of the molten film exist, but the thickness deviation is less than 3 μm;
x: the molten film pulsates and oscillates left and right, and the thickness variation is 5 μm or more.
Anti-sticking roller
Using an extrusion laminator (Placo screw diameter
) The adhesive pellets were extrusion-laminated at a processing temperature of 230 ℃ so that the thickness of the adhesive layer for a sealant became 25 μm, and the releasability from a non-polishing cooling roll (mat roll) was evaluated. In the determination, the case where the film surface had no peeling mark when peeled from the roller (∘) was considered to be good.
O: no peeling mark exists;
x: there was a peel mark.
The obtained film for a lid material was measured for sealing strength and adhesive strength by the following methods.
Determination of sealing strength
The adhesive surface of the film was laminated with an A-PET Cup (215 ml capacity), and heat-pressure bonded at 160 ℃ for 1 second at 40 Kgf/Cup using a Cup sealer (model UF-500 manufactured by Sunny Cup). After natural cooling, the rupture strength was measured using a sealing tester (model FKT-100J, manufactured by Sun Chemical Co., Ltd.) under the condition that the air injection amount was 0.8L/min. For the determination, 25kPa or more is considered to be good.
O: above 25 kPa;
x: less than 25kPa
Determination of adhesive strength-
The adhesive surface of the film was laminated with an A-PET sheet (manufactured by Polytec), and heat-pressure bonded at 160 ℃ for 1 second at 0.2MPa using a heat-seal Tester (TP-701 manufactured by Tester Sangyo). After natural cooling, the sealing strength was measured under the conditions of a peel angle of 180 degrees and a peel speed of 300 mm/min. For the determination, the amplitude of 10N/15mm or more is considered to be good.
O: 10N/15mm or more;
x: less than 10N/15mm
Example 1
An adhesive pellet for a sealant was obtained by pre-blending 40 parts by weight of a resin (A1) (trade name Ultracene 537, manufactured by Tosoh corporation) having a vinyl acetate content of 6% and a melt mass flow rate of 8.5g/10 min as an ethylene-vinyl acetate copolymer (A), 40 parts by weight of a resin (B1) (trade name Ultracene 626, manufactured by Tosoh corporation) having a vinyl acetate content of 15% and a melt mass flow rate of 3.0g/10 min as an ethylene-vinyl acetate copolymer (B), and 20 parts by weight of a partially hydrogenated petroleum resin (C1) (trade name Alcon M115, manufactured by Kawah chemical Co., Ltd., a softening temperature of 115 ℃ and a hydrogenation rate of about 60% (NMR method)) as a tackifier resin (C) with a tumbler, and then melt-kneading the pre-blended mixture at 180 ℃ using a twin-screw extruder. The difference between the vinyl acetate content of the ethylene-vinyl acetate copolymer (A1) and the vinyl acetate content of the ethylene-vinyl acetate copolymer (B1) was 9% by weight. In consideration of thermal stability, 0.05 part by weight of a phenolic antioxidant (Irganox 1010, product name, manufactured by BASF corporation) and 0.2 part by weight of a slip agent (Armowax E, product name, manufactured by Lion Akzo corporation) were added to 100 parts by weight of the adhesive for sealants.
The MFR of the resulting adhesive for sealants was 15g/10 min.
Then, a multi-layer film of low-density polyethylene (25 μm thick, product name of Petrocene 203 manufactured by Tosoh corporation) as an intermediate layer was extrusion-laminated on a biaxially oriented polyester film (12 μm thick) as a support base layer in advance, and an extrusion laminator (screw diameter manufactured by Placo corporation) was used for the surface of the low-density polyethylene
) The adhesive pellets were extrusion-laminated at a processing temperature of 230 ℃ to obtain a film for a lid material having an adhesive layer for a sealant and a thickness of 25 μm.
The evaluation results of the obtained adhesive for sealants and film for lid materials are shown in table 3.
Example 2
35 parts by weight of an ethylene-vinyl acetate copolymer (A1) was used in place of 40 parts by weight of an ethylene-vinyl acetate copolymer (A1), 35 parts by weight of an ethylene-vinyl acetate copolymer (B1) was used in place of 40 parts by weight of an ethylene-vinyl acetate copolymer (B1), 30 parts by weight of a fully hydrogenated petroleum resin (C2) (Alcon P125, a product of Mikawa chemical Co., Ltd., a softening temperature of 125 ℃ and a hydrogenation rate of about 95% (NMR method)) was used as a tackifier resin (C) in place of 20 parts by weight of a partially hydrogenated petroleum resin (C1), and 860 kg/m/g/m was used as an ethylene- α -olefin copolymer (D)3An adhesive for a sealant and a film for a lid material were obtained in the same manner as in example 1 except that 40 parts by weight of the ethylene- α -olefin copolymer (D1) (product of Mitsui chemical Co., Ltd., trade name: TAFMER P-0375) was used. Of ethylene-vinyl acetate copolymers (A1)The difference between the vinyl acetate content and the vinyl acetate content of the ethylene-vinyl acetate copolymer (B1) was 9% by weight.
The adhesive composition is shown in table 1. The MFR of the resulting adhesive for sealants was 9g/10 min.
The evaluation results of the obtained adhesive for sealants and film for lid materials are shown in table 3.
Example 3
An ethylene-vinyl acetate copolymer (B2) (trade name Ultracene 541, manufactured by Tosoh corporation) having a vinyl acetate content of 10 parts by weight and a melt mass flow rate of 9.0g/10 min was used as 35 parts by weight in place of 35 parts by weight of the ethylene-vinyl acetate copolymer (B1), a partially hydrogenated petroleum resin (C1) was used as the tackifier resin (C) in place of 30 parts by weight of the fully hydrogenated petroleum resin (C2), and a partially hydrogenated petroleum resin (C1) was used as the tackifier resin (C) in place of 40 parts by weight of the ethylene- α -olefin copolymer (D1) at a density of 885kg/m3An adhesive for a sealant and a film for a lid material were obtained in the same manner as in example 2 except that 40 parts by weight of the ethylene- α -olefin copolymer (D2) (product name LUMITAC BF300R, manufactured by Tosoh corporation) was used. The difference between the vinyl acetate content of the ethylene-vinyl acetate copolymer (A1) and the vinyl acetate content of the ethylene-vinyl acetate copolymer (B1) was 4% by weight.
The adhesive composition is shown in table 1. The MFR of the resulting adhesive for sealants was 13g/10 min.
The evaluation results of the obtained film for a lid material are shown in table 3.
Example 4
An adhesive for a sealant and a film for a lid material were obtained in the same manner as in example 3 except that 40 parts by weight of the ethylene-vinyl acetate copolymer (a1) was used in place of 35 parts by weight of the ethylene-vinyl acetate copolymer (a1), 40 parts by weight of the ethylene-vinyl acetate copolymer (B2) was used in place of 35 parts by weight of the ethylene-vinyl acetate copolymer (B2), 20 parts by weight of a partially hydrogenated petroleum resin (C3) (trade name Alcon M135, softening temperature 135 ℃, hydrogenation rate of about 60% (NMR method), manufactured by seikagawa chemical corporation) was used as the tackifier resin (C) in place of 30 parts by weight of the partially hydrogenated petroleum resin (C1), and 20 parts by weight of the ethylene- α -olefin copolymer (D2) was used in place of 40 parts by weight of the ethylene- α -olefin copolymer (D2). The difference between the vinyl acetate content of the ethylene-vinyl acetate copolymer (A1) and the vinyl acetate content of the ethylene-vinyl acetate copolymer (B1) was 4% by weight.
The adhesive composition is shown in table 1. The MFR of the resulting adhesive for sealants was 10g/10 min.
The evaluation results of the obtained adhesive for sealants and film for lid materials are shown in table 3.
Example 5
As the tackifier resin (C), instead of 20 parts by weight of the partially hydrogenated petroleum resin (C3), 20 parts by weight of the partially hydrogenated petroleum resin (C1) was used, instead of 20 parts by weight of the ethylene- α -olefin copolymer (D2), 0 part by weight of the ethylene- α -olefin copolymer (D2) was used, and as the thermoplastic block copolymer of vinyl aromatic hydrocarbon and diene (E), 5 parts by weight of a thermoplastic block copolymer of vinyl aromatic hydrocarbon and diene (E1) (KratonG1726MS) having a melt flow rate of 65g/10 min at 200 ℃ under a 5.0kg load, a mixing ratio of the hydrogenated styrene-butadiene-diblock copolymer to the hydrogenated styrene-butadiene-styrene triblock copolymer of 7/3 and a styrene content of 30% by weight was used, in addition to the above, an adhesive for a sealant and a film for a lid material were obtained in the same manner as in example 4. The difference between the vinyl acetate content of the ethylene-vinyl acetate copolymer (A1) and the vinyl acetate content of the ethylene-vinyl acetate copolymer (B1) was 4% by weight.
The adhesive composition is shown in table 1. The MFR of the resulting sealant adhesive was 24g/10 min.
The evaluation results of the obtained adhesive for sealants and film for lid materials are shown in table 3.
Example 6
An adhesive for a sealant and a film for a cap material were obtained in the same manner as in example 5 except that 35 parts by weight of the ethylene-vinyl acetate copolymer (a1) was used instead of 40 parts by weight of the ethylene-vinyl acetate copolymer (a1), 35 parts by weight of the ethylene-vinyl acetate copolymer (B2) was used instead of 40 parts by weight of the ethylene-vinyl acetate copolymer (B2), 30 parts by weight of the partially hydrogenated petroleum resin (C1) was used instead of 20 parts by weight of the partially hydrogenated petroleum resin (C1), 40 parts by weight of the ethylene- α -olefin copolymer (D2) was used instead of 0 part by weight of the ethylene- α -olefin copolymer (D2), and 2 parts by weight of the thermoplastic block copolymer of vinyl aromatic hydrocarbon and diene (E1) was used instead of 5 parts by weight of the thermoplastic block copolymer of vinyl aromatic hydrocarbon and diene (E1). The difference between the vinyl acetate content of the ethylene-vinyl acetate copolymer (A1) and the vinyl acetate content of the ethylene-vinyl acetate copolymer (B1) was 4% by weight.
The adhesive composition is shown in table 1. The MFR of the resulting adhesive for sealants was 13g/10 min.
The evaluation results of the obtained adhesive for sealants and film for lid materials are shown in table 3.
Comparative example 1
An adhesive for a sealant and a film for a lid material were obtained in the same manner as in example 1 except that 80 parts by weight of the ethylene-vinyl acetate copolymer (a1) was used in place of 40 parts by weight of the ethylene-vinyl acetate copolymer (a1) and 0 part by weight of the ethylene-vinyl acetate copolymer (B1) was used in place of 40 parts by weight of the ethylene-vinyl acetate copolymer (B1).
The adhesive composition is shown in table 2. The MFR of the resulting adhesive for sealants was 23g/10 min.
The evaluation results of the obtained adhesive for sealants and film for lid materials are shown in table 4.
The obtained film for a lid material was poor in adhesive strength and sealing strength.
Comparative example 2
An adhesive for a sealant and a film for a lid material were obtained in the same manner as in example 2 except that 35 parts by weight of an ethylene-vinyl acetate copolymer (B2) (trade name: Ultracene 751, manufactured by Tosoh corporation) having a vinyl acetate content of 28% and a melt mass flow rate of 5.7g/10 min was used in place of 35 parts by weight of the ethylene-vinyl acetate copolymer (B1). The difference between the vinyl acetate content of the ethylene-vinyl acetate copolymer (A1) and the vinyl acetate content of the ethylene-vinyl acetate copolymer (B1) was 22% by weight.
The adhesive composition is shown in table 1. The MFR of the resulting adhesive for sealants was 23g/10 min.
The evaluation results of the obtained adhesive for sealants and film for lid materials are shown in table 4.
The resulting adhesive had poor molding stability and poor roll release properties, and thus a film for a cover material could not be obtained.
Comparative example 3
An adhesive for a sealant and a film for a lid material were obtained in the same manner as in example 1 except that 20 parts by weight of the ethylene-vinyl acetate copolymer (a1) was used in place of 40 parts by weight of the ethylene-vinyl acetate copolymer (a1), 20 parts by weight of the ethylene-vinyl acetate copolymer (B2) was used in place of 40 parts by weight of the ethylene-vinyl acetate copolymer (B1), and 60 parts by weight of the partially hydrogenated petroleum resin (C1) was used in place of 20 parts by weight of the partially hydrogenated petroleum resin (C1). The difference between the vinyl acetate content of the ethylene-vinyl acetate copolymer (A1) and the vinyl acetate content of the ethylene-vinyl acetate copolymer (B1) was 4% by weight.
The adhesive composition is shown in table 1. The MFR of the resulting adhesive for sealants was 70g/10 min.
The evaluation results of the obtained film for a lid material are shown in table 2.
The obtained adhesive was poor in roll release resistance and poor in sealing strength of the film for a lid material.
[ Table 1]
[ Table 2]
[ Table 3]
[ Table 4]
Claims (5)
1. An adhesive for a sealant for a lid material of a container, comprising: 10 to 50 parts by weight of an ethylene-vinyl acetate copolymer (A) having a vinyl acetate content of 3 to 15% by weight, 10 to 50 parts by weight of an ethylene-vinyl acetate copolymer (B) having a vinyl acetate content of 8 to 25% by weight, and 5 to 40 parts by weight of a tackifier resin (C), wherein the total amount of (A), (B) and (C) is 100 parts by weight,
and 2 to 5 parts by weight of a thermoplastic block copolymer (E) of a vinyl aromatic hydrocarbon and an olefin or diene, based on 100 parts by weight of the total amount of the components (A), (B) and (C),
the difference between the vinyl acetate content of the ethylene-vinyl acetate copolymer (A) and the vinyl acetate content of the ethylene-vinyl acetate copolymer (B) is 3 to 20% by weight, the vinyl acetate content of the ethylene-vinyl acetate copolymer (A) is less than the vinyl acetate content of the ethylene-vinyl acetate copolymer (B),
the thermoplastic block copolymer (E) of a vinyl aromatic hydrocarbon and an olefin or diene is a mixture of a hydrogenated styrene-butadiene-diblock copolymer and a hydrogenated styrene-butadiene-styrene-triblock copolymer, the mixing ratio thereof is 5/5 to 9/1, and the styrene content thereof is 20 to 50% by weight,
the container contains polyethylene terephthalate as a main component.
2. The adhesive for a lid material sealant according to claim 1, wherein a base material for sealing a lid material of a container according to JIS K6922-1: the density measured in 1998 is 860-910 kg/m3The ethylene-alpha-olefin copolymer (D) is in the range of 10 to 50 parts by weight.
3. The sealant adhesive for a lid material of a container as claimed in claim 2, wherein the ethylene- α -olefin copolymer (D) satisfies the following conditions (a) to (c):
(a) a ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of 3 or less;
(b) the temperature Tm at the maximum peak position of an endothermic curve obtained by temperature rise measurement using a differential scanning calorimeter and the short chain branch number SCB corresponding to 1000 carbon atoms obtained by measurement of infrared absorption spectrum satisfy the relationship of the formula (1):
Tm＜-1.8×SCB+140(1)
the temperature Tm is in units of;
(c) the alpha-olefin has 3 to 12 carbon atoms.
4. The adhesive for a sealing sealant of a lid material for a container according to claim 1 or 2, wherein the tackifier resin (C) is a resin obtained by partially hydrogenating 50 to 90% at least one selected from the group consisting of an aliphatic petroleum resin, an aromatic petroleum resin, an alicyclic hydrogenated petroleum resin and a copolymerized petroleum resin.
5. A film for a lid material of a container, comprising at least 2 layers of:
a layer formed of the adhesive for sealant as a lid material for a container according to any one of claims 1 to 4, and
and supporting the substrate layer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016217279A JP6841001B2 (en) | 2016-11-07 | 2016-11-07 | Sealant adhesive and lid film |
| JP2016-217279 | 2016-11-07 |
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| CN108070330A CN108070330A (en) | 2018-05-25 |
| CN108070330B true CN108070330B (en) | 2021-10-01 |
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| JP (1) | JP6841001B2 (en) |
| KR (1) | KR102333539B1 (en) |
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| JP2020158763A (en) * | 2019-03-25 | 2020-10-01 | 東ソー株式会社 | Resin composition and film for lid material |
| JP7340597B2 (en) * | 2019-03-28 | 2023-09-07 | 三井・ダウポリケミカル株式会社 | Resin compositions for sealants, laminates, packaging materials and packaging containers |
| JP7240067B2 (en) * | 2019-06-27 | 2023-03-15 | 東洋インキＳｃホールディングス株式会社 | Adhesive resin composition, sheet, lid material, member set for sealed container and container |
| JP6791420B1 (en) * | 2020-04-15 | 2020-11-25 | 東洋インキＳｃホールディングス株式会社 | Adhesive resin composition, sheet, lid material, member set and container using the composition |
| CN117043251A (en) | 2021-03-18 | 2023-11-10 | 三井-陶氏聚合化学株式会社 | Heat-sealable resin composition, heat-sealable material, packaging material, lid material, and packaging container |
| EP4310141A1 (en) | 2021-03-18 | 2024-01-24 | Dow-Mitsui Polychemicals Co., Ltd. | Heat sealing resin composition, heat sealable material, packaging material, cover material and packaging container |
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