JP2018076398A - Adhesive for sealant and film for lid material - Google Patents

Adhesive for sealant and film for lid material Download PDF

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JP2018076398A
JP2018076398A JP2016217279A JP2016217279A JP2018076398A JP 2018076398 A JP2018076398 A JP 2018076398A JP 2016217279 A JP2016217279 A JP 2016217279A JP 2016217279 A JP2016217279 A JP 2016217279A JP 2018076398 A JP2018076398 A JP 2018076398A
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vinyl acetate
weight
adhesive
ethylene
sealant
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JP2018076398A5 (en
JP6841001B2 (en
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功 森下
Isao Morishita
功 森下
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Tosoh Corp
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Priority to CN201711071513.1A priority patent/CN108070330B/en
Priority to TW106138291A priority patent/TWI751221B/en
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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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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

PROBLEM TO BE SOLVED: To provide: an adhesive for sealant used for a lid material of an A-PET container, which is excellent in moldability and satisfies sealing strength and adhesive strength to the A-PET container; and a film for the lid material.SOLUTION: There are provided: an adhesive for lid material sealant of a container, which contains 10-50 pts.wt. of an ethylene-vinyl acetate copolymer (A) of which a vinyl acetate content is 3-15 wt.%, 10-50 pts.wt. an ethylene-vinyl acetate copolymer (B) of which a vinyl acetate content is 8-25 wt.%, and 5-40 pts.wt. of a tackifier resin (C) (the total of (A), (B) and (C) is 100 pts.wt.), where a 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 3-20 wt.%; and a film for the lid material.SELECTED DRAWING: None

Description

本発明は容器の蓋材に用いられるフィルムに関し、より詳細には、成形加工性に優れ、高い封緘強度と接着強度が得られ、耐熱性に優れた非晶性ポリエチレンテレフタレート（以下Ａ−ＰＥＴ）製容器の蓋材に用いられるシーラント用接着剤、及び蓋材用フィルムに関するものである。   The present invention relates to a film used for a container lid, and more specifically, amorphous polyethylene terephthalate (hereinafter referred to as A-PET) having excellent moldability, high sealing strength and adhesive strength, and excellent heat resistance. The present invention relates to an adhesive for a sealant used for a lid for a container and a film for a lid.

従来から、飲食品、医薬品、工業用部品などの包装にはポリエチレンやポリプロピレン、ポリスチレンなどのプラスチック容器や紙を主体とした紙製容器が使用されており、その蓋材には内容物の保護性のための安定した接着強度、且つ剥離時には適度な強度にて開封可能な易剥離性能を持つ易剥離性フィルムが使用されている。これまで、ポリプロピレンやポリスチレンなどの容器に対しては既に多くの材料が知られているが、近年、安価で透明性と耐寒性に優れるＡ−ＰＥＴ製容器に対しては、実用上優れた易剥離性フィルムは見出されていない。従来の易剥離性フィルムは、Ａ−ＰＥＴ製容器の蓋材に用いた場合、接着強度が弱い為輸送や保管時の振動や落下により蓋が開いてしまう問題や、高い接着強度を得ようとしてヒートシール温度を高く設定せざるを得ないため、容器が変形しで密封性が低下する問題があった。また、接着後に低温環境にて保管すると、シール強度が低下するという欠点もあり、実用上使用するには問題があった。一般に、蓋材シーラント用接着剤としては、ポリエリレンやエチレン−酢酸ビニル共重合体と粘着付与剤とからなる混合物が知られているが、このような材料ではＡ−ＰＥＴ製容器に対して十分な接着強度が得られない。また、エチレン・α−オレフィン共重合体とオレフィン系エラストマー及び／又はスチレン系エラストマーと粘着付与剤からなる樹脂組成物（例えば特許文献１参照。）、エチレン・α−オレフィン共重合体とエチレン・極性モノマー共重合体、Ａ−Ｂ−Ａ型ブロック共重合体、粘着付与剤からなるシール材料（例えば特許文献２参照。）が使用されているが、成形加工性、封緘強度と接着強度の全てを満足できるものではなかった。   Conventionally, plastic containers such as polyethylene, polypropylene, and polystyrene, and paper containers mainly made of paper have been used for packaging food and drinks, pharmaceuticals, and industrial parts. For this reason, an easily peelable film having stable adhesive strength and easy peelability that can be opened with an appropriate strength at the time of peeling is used. Up to now, many materials are already known for containers such as polypropylene and polystyrene, but in recent years, it is practically excellent for A-PET containers that are inexpensive and excellent in transparency and cold resistance. No peelable film has been found. The conventional easy peelable film, when used as a lid for containers made of A-PET, has a low adhesive strength, so the problem is that the lid will open due to vibration or dropping during transportation or storage, and high adhesive strength. Since the heat sealing temperature has to be set high, there is a problem that the sealing performance is lowered due to deformation of the container. In addition, when stored in a low-temperature environment after bonding, there is a disadvantage that the sealing strength is lowered, and there is a problem in practical use. In general, as an adhesive for a lid sealant, a mixture composed of polyerylene or an ethylene-vinyl acetate copolymer and a tackifier is known, but such a material is sufficient for an A-PET container. Adhesive strength cannot be obtained. In addition, a resin composition comprising an ethylene / α-olefin copolymer and an olefin elastomer and / or a styrene elastomer and a tackifier (see, for example, Patent Document 1), an ethylene / α-olefin copolymer and ethylene / polarity. A sealing material comprising a monomer copolymer, an ABA block copolymer, and a tackifier (see, for example, Patent Document 2) is used. However, all of molding processability, sealing strength and adhesive strength are used. It was not satisfactory.

特開１９９９−２６９３１９号公報JP 1999-269319 A 特許第４４３８１０８号公報Japanese Patent No. 4438108

しかし、上記のいずれの方法も、成形加工性、Ａ−ＰＥＴ製容器に対する封緘強度、接着強度を十分に満足できるものではなかった。   However, none of the above methods can sufficiently satisfy the moldability, the sealing strength with respect to the A-PET container, and the adhesive strength.

本発明は、成形加工性に優れ、Ａ−ＰＥＴ製容器に対する封緘強度、接着強度を満足するＡ−ＰＥＴ容器の蓋材に用いられるシーラント用接着剤及び蓋材用フィルムを提供することを目的とする。   An object of the present invention is to provide an adhesive for a sealant and a film for a lid material, which are used for a lid material of an A-PET container, which has excellent moldability and satisfies sealing strength and adhesive strength for an A-PET container. To do.

本発明者らは、上記課題に対し鋭意検討した結果、特定の２種類のエチレン−酢酸ビニル共重合体、粘着付与剤を含むシーラント用接着剤が成形加工性に優れ、Ａ−ＰＥＴ製容器に対する封緘強度や接着強度に優れることを見出し、本発明を完成させるに至った。
即ち、本発明は、酢酸ビニル含量が３〜１５重量％であるエチレン−酢酸ビニル共重合体（Ａ）１０〜５０重量部、酢酸ビニル含量８〜２５重量％であるエチレン−酢酸ビニル共重合体（Ｂ）１０〜５０重量部、および粘着付与剤樹脂（Ｃ）５〜４０重量部（（Ａ），（Ｂ）及び（Ｃ）の合計は１００重量部）を含み、エチレン−酢酸ビニル共重合体（Ａ）の酢酸ビニル含量とエチレン−酢酸ビニル共重合体（Ｂ）の酢酸ビニル含量の差が３〜２０重量％、エチレン−酢酸ビニル共重合体（Ａ）の酢酸ビニル含量はエチレン−酢酸ビニル共重合体（Ｂ）の酢酸ビニル含量より小さいものであることを特徴とする容器の蓋材シーラント用接着剤、及び蓋材用フィルムに関するものである。 As a result of intensive studies on the above problems, the present inventors have found that an adhesive for sealant containing two specific types of ethylene-vinyl acetate copolymers and a tackifier is excellent in molding processability, and is suitable for an A-PET container. The inventors have found that the sealing strength and the adhesive strength are excellent, and have completed the present invention.
That is, the present invention relates to an ethylene-vinyl acetate copolymer (A) having a vinyl acetate content of 3 to 15% by weight and an ethylene-vinyl acetate copolymer having a vinyl acetate content of 8 to 25% by weight. (B) 10 to 50 parts by weight and tackifier resin (C) 5 to 40 parts by weight (total of (A), (B) and (C) is 100 parts by weight) The difference between the vinyl acetate content of the blend (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 ethylene-acetic acid The present invention relates to an adhesive for a lid material sealant for a container, and a film for a lid material, which is smaller than the vinyl acetate content of the vinyl copolymer (B).

以下に本発明を詳細に説明する。   The present invention is described in detail below.

本発明の容器の蓋材シーラント用接着剤は、酢酸ビニル含量が３〜１５重量％であるエチレン−酢酸ビニル共重合体（Ａ）１０〜５０重量部、酢酸ビニル含量８〜２５重量％であるエチレン−酢酸ビニル共重合体（Ｂ）１０〜５０重量部、および粘着付与剤樹脂（Ｃ）５〜４０重量部（（Ａ），（Ｂ）及び（Ｃ）の合計は１００重量部）を含み、エチレン−酢酸ビニル共重合体（Ａ）の酢酸ビニル含量とエチレン−酢酸ビニル共重合体（Ｂ）の酢酸ビニル含量の差が３〜２０重量％、エチレン−酢酸ビニル共重合体（Ａ）の酢酸ビニル含量はエチレン−酢酸ビニル共重合体（Ｂ）の酢酸ビニル含量より小さいものであるものである。   The adhesive for a sealant of a container of the present invention has an ethylene-vinyl acetate copolymer (A) having a vinyl acetate content of 3 to 15% by weight, and a vinyl acetate content of 8 to 25% by weight. 10-50 parts by weight of ethylene-vinyl acetate copolymer (B) and 5-40 parts by weight of tackifier resin (C) (total of (A), (B) and (C) is 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) is 3 to 20% by weight of the ethylene-vinyl acetate copolymer (A). The vinyl acetate content is smaller than the vinyl acetate content of the ethylene-vinyl acetate copolymer (B).

該エチレン−酢酸ビニル共重合体（Ａ）は、酢酸ビニル含量が３〜１５重量％、好ましくは５〜１０重量％からなるものである。酢酸ビニル含量が３重量％未満の場合、得られるシーラント用接着剤は低温ヒートシール性に劣るため好ましくない。一方、酢酸ビニル含量が１５重量％を超える場合、得られるシーラント用接着剤は成形加工性に劣るため好ましくない。なお、エチレン−酢酸ビニル共重合体中の酢酸ビニル含量は、ＪＩＳ Ｋ ６９２４−１に準拠し測定した方法により測定することができる。   The ethylene-vinyl acetate copolymer (A) has a vinyl acetate content of 3 to 15% by weight, preferably 5 to 10% by weight. When the vinyl acetate content is less than 3% by weight, the obtained adhesive for sealant is not preferable because it is inferior in low-temperature heat sealability. On the other hand, when the vinyl acetate content exceeds 15% by weight, the obtained adhesive for sealant is not preferable because of poor molding processability. In addition, the vinyl acetate content in an ethylene-vinyl acetate copolymer can be measured by the method measured based on JISK6924-1.

また、該エチレン−酢酸ビニル共重合体（Ａ）は、ＪＩＳ Ｋ ６９２４−１に準拠して温度１９０℃、荷重２１．１８Ｎで測定したメルトフローレイトが１〜３０ｇ／１０分の範囲にあるものが好ましく、特に３〜１５ｇ／１０分であることが好ましい。メルトフローレイトが１ｇ／１０分以上の場合、得られるシーラント用接着剤は、成形加工性と接着強度が優れるため好ましい。一方、メルトフローレイトが３０ｇ／１０分以下の場合、得られるシーラント用接着剤は、成形加工安定性に優れるため好ましい。   The ethylene-vinyl acetate copolymer (A) has a melt flow rate measured in accordance with JIS K 6924-1 at a temperature of 190 ° C. and a load of 21.18 N in a range of 1 to 30 g / 10 minutes. Is preferable, and 3 to 15 g / 10 min is particularly preferable. When the melt flow rate is 1 g / 10 min or more, the obtained adhesive for sealant is preferable because of excellent molding processability and adhesive strength. On the other hand, when the melt flow rate is 30 g / 10 min or less, the obtained adhesive for sealant is preferable because of excellent molding process stability.

該エチレン−酢酸ビニル共重合体（Ａ）は、公知の製造方法により得ることができ、また市販されているものを用いてもよい。具体的例示としては、例えば（商品名）ウルトラセン５１５、ウルトラセン５３７、ウルトラセン５４０、ウルトラセン５４１（東ソー株式会社製）等を挙げることができる。   The ethylene-vinyl acetate copolymer (A) can be obtained by a known production method, or a commercially available product may be used. Specific examples include (trade name) Ultrasen 515, Ultrasen 537, Ultrasen 540, Ultrasen 541 (manufactured by Tosoh Corporation), and the like.

該エチレン−酢酸ビニル共重合体（Ｂ）は、酢酸ビニル含量が８〜２５重量％、好ましくは、１０〜２０重量％からなるものである。酢酸ビニル含量が８重量％未満の場合、得られるシーラント用接着剤は低温ヒートシール性、接着強度に劣るため好ましくない。一方、酢酸ビニル含量が２５重量％を超える場合、得られるシーラント用接着剤は成形加工性、ブロッキング性に劣るため好ましくない。なお、エチレン−酢酸ビニル共重合体中の酢酸ビニル含量は、ＪＩＳ Ｋ ６９２４−１に準拠し測定した方法により測定することができる。   The ethylene-vinyl acetate copolymer (B) has a vinyl acetate content of 8 to 25% by weight, preferably 10 to 20% by weight. When the vinyl acetate content is less than 8% by weight, the obtained adhesive for sealant is unfavorable because it is inferior in low-temperature heat sealability and adhesive strength. On the other hand, when the vinyl acetate content exceeds 25% by weight, the obtained adhesive for sealant is not preferable because it is inferior in moldability and blocking property. In addition, the vinyl acetate content in an ethylene-vinyl acetate copolymer can be measured by the method measured based on JISK6924-1.

また、該エチレン−酢酸ビニル共重合体（Ｂ）は、ＪＩＳ Ｋ ６９２４−１に準拠して温度１９０℃、荷重２１．１８Ｎで測定したメルトフローレイトが１〜３０ｇ／１０分の範囲にあるものが好ましく、特に３〜２０ｇ／１０分であることが好ましい。メルトフローレイトが１ｇ／１０分以上の場合、得られるシーラント用接着剤は、成形加工性と接着強度が優れるため好ましい。一方、メルトフローレイトが３０ｇ／１０分以下の場合、得られるシーラント用接着剤は、成形加工安定性に優れるため好ましい。   The ethylene-vinyl acetate copolymer (B) has a melt flow rate measured in accordance with JIS K 6924-1 at a temperature of 190 ° C. and a load of 21.18 N in a range of 1 to 30 g / 10 minutes. Is preferable, and 3 to 20 g / 10 min is particularly preferable. When the melt flow rate is 1 g / 10 min or more, the obtained adhesive for sealant is preferable because of excellent molding processability and adhesive strength. On the other hand, when the melt flow rate is 30 g / 10 min or less, the obtained adhesive for sealant is preferable because of excellent molding process stability.

該エチレン−酢酸ビニル共重合体（Ｂ）は、公知の製造方法により得ることができ、また市販されているものを用いてもよい。具体的例示としては、例えば（商品名）ウルトラセン５４１、ウルトラセン６２６、ウルトラセン６２５、ウルトラセン６３３（東ソー株式会社製）等を挙げることができる。   The ethylene-vinyl acetate copolymer (B) can be obtained by a known production method, or a commercially available product may be used. Specific examples include (trade name) Ultrasen 541, Ultrasen 626, Ultrasen 625, Ultrasen 633 (manufactured by Tosoh Corporation), and the like.

本発明を構成するエチレン−酢酸ビニル共重合体（Ａ）の酢酸ビニル含量とエチレン−酢酸ビニル共重合体（Ｂ）の酢酸ビニル含量の差が３〜２０重量％であるもの、好ましくは３〜１５重量％であるものである。酢酸ビニル含量の差が３重量％未満の場合、得られるシーラント用接着剤の接着強度が劣るため好ましくない。一方、２０重量％を超える場合、得られるシーラント用接着剤は、成形加工安定性が劣るため好ましくない。   The difference between the vinyl acetate content of the ethylene-vinyl acetate copolymer (A) constituting the present invention and the vinyl acetate content of the ethylene-vinyl acetate copolymer (B) is 3 to 20% by weight, preferably 3 to It is 15% by weight. When the difference in vinyl acetate content is less than 3% by weight, the adhesive strength of the resulting sealant adhesive is inferior, which is not preferable. On the other hand, when it exceeds 20% by weight, the obtained adhesive for sealant is not preferable because the molding process stability is poor.

本発明を構成する粘着付与剤（Ｃ）は、粘着付与剤の範疇に属するものであれば如何なるものを用いることも可能であり、例えば合成石油樹脂系粘着付与剤である石油樹脂系、クマロン樹脂系、スチレン系などや、天然樹脂系粘着付与剤であるロジン系樹脂、メチルエステル系樹脂、グリセリンエステル系樹脂、ペンタエリストールエステル系樹脂、テルペン系樹脂及びそれらの変性物、などが挙げられる。これらの粘着付与剤のうち、合成石油樹脂系粘着付与剤には脂肪族系石油樹脂、脂肪族系水添石油樹脂、芳香族系石油樹脂、芳香族系水添石油樹脂、脂環族系石油樹脂、脂環族系水添石油樹脂、共重合系水添石油樹脂などがある。これらの中では、芳香族系水添石油樹脂や脂環族系水添石油樹脂の使用が好ましい。特に、脂肪族系石油樹脂、芳香族系石油樹脂、脂環族系水添石油樹脂及び共重合系石油樹脂からなる群から選ばれる少なくとも１種類を５０〜９０％部分水添したものが、封緘強度と接着強度に優れるために好ましい。これらは、単独、又は２種以上を併用して使用できる。   As the tackifier (C) constituting the present invention, any one can be used as long as it belongs to the category of tackifiers. For example, petroleum resin-based and coumarone resins that are synthetic petroleum resin-based tackifiers. And rosin resin, methyl ester resin, glycerin ester resin, pentaerythrester resin, terpene resin, and modified products thereof, which are natural resin tackifiers. Among these tackifiers, synthetic petroleum resin tackifiers include aliphatic petroleum resins, aliphatic hydrogenated petroleum resins, aromatic petroleum resins, aromatic hydrogenated petroleum resins, and alicyclic petroleum oils. Examples thereof include resins, alicyclic hydrogenated petroleum resins, and copolymerized hydrogenated petroleum resins. Among these, it is preferable to use an aromatic hydrogenated petroleum resin or an alicyclic hydrogenated petroleum resin. In particular, 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 is 50% to 90% partially hydrogenated. It is preferable because of its excellent strength and adhesive strength. These can be used alone or in combination of two or more.

該粘着付与剤（Ｃ）は、環球法で測定した軟化点が９０〜１４０℃の範囲にあるものが好ましく、特に１００〜１３５℃であることが好ましい。軟化点が９０℃未満の場合は、耐ブロッキング性が劣り、１４０℃を超える場合は、低温環境下での接着強度保持性が劣る。   The tackifier (C) preferably has a softening point measured by the ring-and-ball method in the range of 90 to 140 ° C, particularly preferably 100 to 135 ° C. When the softening point is less than 90 ° C., the blocking resistance is inferior, and when it exceeds 140 ° C., the adhesive strength retention in a low temperature environment is inferior.

該粘着付与剤（Ｃ）は、市販されているものが用いられる。具体的例示としては、例えば（商品名） アルコンＭ９０、アルコンＭ１１５、アルコンＭ１３５、アルコンＰ１００、アルコンＰ１２５、アイマーブＳ１１０、アイマーブＰ１２５、Ｔ−ＲＥＺ ＲＣ１１５、Ｔ−ＲＥＺ ＨＡ１２５、パインクリスタルＫＥ−３１１、ＹＳレジンＰＸ１１５０、ＹＳレジンＰＸ１１５０Ｎ等を挙げることができる。   As the tackifier (C), a commercially available one is used. Specific examples include, for example, (trade names) Archon M90, Archon M115, Archon M135, Archon P100, Archon P125, Imarve S110, Imarve P125, T-REZ RC115, T-REZ HA125, Pine Crystal KE-311, YS Resin PX1150, YS resin PX1150N, etc. can be mentioned.

エチレン−酢酸ビニル共重合体（Ａ）、エチレン−酢酸ビニル共重合体（Ｂ）及び粘着付与剤（Ｃ）の配合量は、以下のとおりであり、（Ａ），（Ｂ）及び（Ｃ）の合計は１００重量部である。   The blending amounts of the ethylene-vinyl acetate copolymer (A), the ethylene-vinyl acetate copolymer (B) and the tackifier (C) are as follows: (A), (B) and (C) Is 100 parts by weight.

エチレン−酢酸ビニル共重合体（Ａ）の配合割合は、１０〜５０重量部、特に接着強度、成形加工性のバランスに優れたシーラント用接着剤となることから２０〜４０重量部であることが好ましい。１０重量部未満の場合、得られるシーラント用接着剤の成形加工安定性が劣るため好ましくない。一方、５０重量部を超える場合、得られるシーラント用接着剤は、接着強度が不十分となるため好ましくない。   The blending ratio of the ethylene-vinyl acetate copolymer (A) is 10 to 50 parts by weight, particularly 20 to 40 parts by weight because it becomes an adhesive for sealants excellent in the balance of adhesive strength and moldability. preferable. When the amount is less than 10 parts by weight, the molding process stability of the obtained sealant adhesive is inferior. On the other hand, when it exceeds 50 parts by weight, the obtained adhesive for sealant is not preferable because the adhesive strength becomes insufficient.

エチレン−酢酸ビニル共重合体（Ｂ）の配合割合は、１０〜５０重量部、特に接着強度、成形加工性のバランスに優れたシーラント用接着剤となることから２０〜４０重量部であることが好ましい。１０重量部未満の場合、得られるシーラント用接着剤の接着強度が劣るため好ましくない。一方、５０重量部を超える場合、得られるシーラント用接着剤は、成形加工安定性が劣り、ブロッキング性にも劣るため好ましくない。   The blending ratio of the ethylene-vinyl acetate copolymer (B) is 10 to 50 parts by weight, particularly 20 to 40 parts by weight because it becomes an adhesive for sealants excellent in the balance of adhesive strength and moldability. preferable. When the amount is less than 10 parts by weight, the adhesive strength of the obtained sealant adhesive is inferior, which is not preferable. On the other hand, when the amount exceeds 50 parts by weight, the obtained adhesive for sealant is not preferable because the molding process stability is poor and the blocking property is also poor.

該粘着付与剤（Ｃ）の配合量は、５〜４０重量部、特に１５〜３０重量部であることが好ましい。５重量部未満の場合、得られるシーラント用接着剤は封緘強度と接着強度が劣るため好ましくない。一方、４０重量部を超える場合、成形加工時のロールリリース性が劣り、また巻ブロッキングが発生するものとなるため好ましくない。   The compounding amount of the tackifier (C) is preferably 5 to 40 parts by weight, particularly 15 to 30 parts by weight. When the amount is less than 5 parts by weight, the obtained adhesive for sealant is not preferable because of poor sealing strength and adhesive strength. On the other hand, when the amount exceeds 40 parts by weight, roll release properties during molding are inferior and winding blocking occurs, which is not preferable.

本発明のシーラント用接着剤は、特に低温シール性と封緘強度に優れるものとなることから、ＪＩＳ Ｋ６９２２−１（１９９８年）で測定した密度が８６０〜９１０ｋｇ／ｍ３の範囲にあるエチレン・α−オレフィン共重合体（Ｄ）を配合したものであることが好ましい。そして、その際の配合量としては、該エチレン−酢酸ビニル共重合体（Ａ）、該エチレン−酢酸ビニル共重合体（Ｂ）、該粘着付与剤樹脂（Ｃ）の合計量１００重量部に対し、該エチレン・α−オレフィン共重合体（Ｄ）１０〜５０重量部が好ましく、特に２０〜４０重量部であることが好ましい。 The adhesive for sealant of the present invention is particularly excellent in low-temperature sealability and sealing strength, so that the density measured by JIS K6922-1 (1998) is in the range of 860 to 910 kg / m 3. -It is preferable that the olefin copolymer (D) is blended. And as a compounding quantity in that case, with respect to 100 weight part of total amounts of this ethylene-vinyl acetate copolymer (A), this ethylene-vinyl acetate copolymer (B), and this tackifier resin (C). The ethylene / α-olefin copolymer (D) is preferably 10 to 50 parts by weight, particularly preferably 20 to 40 parts by weight.

該エチレン・α−オレフィン共重合体（Ｄ）としては、一般にエチレン・α−オレフィン共重合体と称される範疇に属するものであれば如何なるものを用いることも可能である。α−オレフィンとしては特に限定はないものの、炭素数３〜１２のプロペン、１−ブテン、１−ペンテン、１−ヘキセン、４−メチル−１−ペンテン、１−オクテン、１−デセン、１−ドデカン等が例示できる。これらのエチレン・α−オレフィン共重合体（Ｄ）はチーグラー系触媒またはクロム系触媒、メタロセン触媒を使用して、エチレンとα−オレフィンを共重合することにより、好適に製造することができる。重合方法としては、溶液重合法、高圧重合法、気相重合法等が挙げられる。さらに、このエチレン・α−オレフィン共重合体（Ｄ）は、ゲル浸透クロマトグラフィを用いて、以下に示す条件下で、単分散ポリスチレンでユニバーサルな検量線を測定し、直鎖のポリエチレンの分子量として計算した重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）の比（Ｍｗ／Ｍｎ）が３以下であることが、低温ヒートシール性と封緘強度に優れるため好ましい。   Any ethylene / α-olefin copolymer (D) may be used as long as it belongs to a category generally referred to as an ethylene / α-olefin copolymer. Although there is no limitation in particular as an alpha olefin, C3-C12 propene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecane Etc. can be exemplified. These ethylene / α-olefin copolymers (D) can be suitably produced by copolymerizing ethylene and α-olefin using a Ziegler catalyst, a chromium 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. Furthermore, this ethylene / α-olefin copolymer (D) was measured as a molecular weight of linear polyethylene by measuring a universal calibration curve with monodisperse polystyrene using gel permeation chromatography under the conditions shown below. It is preferable that the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) is 3 or less because of excellent low-temperature heat sealability and sealing strength.

機種：ウォーターズ社製 １５０Ｃ ＡＬＣ／ＧＰＣ
溶媒：１，２，４−トリクロロベンゼン
流速：１ｍｌ／ｍｉｎ
温度：１４０℃
測定濃度：３０ｍｇ／３０ｍｌ
注入量：１００μｌ
カラム：東ソー（株）製 ＴＳＫｇｅｌ ＧＭＨ ＨＲ−Ｈ ３本
また、このエチレン・α−オレフィン共重合体（Ｄ）は、示差走査型熱量計による昇温測定において得られる吸熱曲線の最大ピーク位置の温度（Ｔｍ（℃））と赤外線吸収スペクトルの測定から求められる炭素数１０００個当りの短鎖分岐数（ＳＣＢ）とが（１）式の関係を満たすものであると、エチレン・α−オレフィン共重合体の組成分布が狭く、低温ヒートシール性を悪化させる低密度（高短鎖分岐数）成分が少なく、好ましい。これは、エチレン・α−オレフィン共重合体は炭素数１０００個当りの短鎖分岐数（ＳＣＢ）が多いほど密度が低くなり融点が低くなる関係がある。融点を低くするために短鎖分岐数を増しても、低分子量の部分に短鎖分岐数が多く導入され、低密度（高短鎖分岐数）を多く含むエチレン・α−オレフィン共重合体の融点は高いものとなる。一方、同じ短鎖分岐数のエチレン・α−オレフィン共重合体であっても、低分子量から高分子量分まで均一に短鎖分岐を導入したものは、低密度（高短鎖分岐数）を多く含むエチレン・α−オレフィン共重合体と比較し融点が低いものとなる。 Model: 150C ALC / GPC manufactured by Waters
Solvent: 1,2,4-trichlorobenzene Flow rate: 1 ml / min
Temperature: 140 ° C
Measurement concentration: 30 mg / 30 ml
Injection volume: 100 μl
Column: 3 TSKgel GMH HR-H manufactured by Tosoh Corporation In addition, this ethylene / α-olefin copolymer (D) is the temperature at the maximum peak position of the endothermic curve obtained in the temperature rise measurement with a differential scanning calorimeter. (Tm (° C.)) and the number of short chain branches per 1,000 carbon atoms (SCB) determined from the measurement of infrared absorption spectrum satisfy the relationship of the formula (1). The composition distribution of the coalescence is narrow, and there are few low density (high and short chain branching) components that deteriorate the low temperature heat sealability, which is preferable. This is because the ethylene / α-olefin copolymer has a lower density and lower melting point as the number of short chain branches (SCB) per 1000 carbon atoms increases. Even if the number of short chain branches is increased in order to lower the melting point, an ethylene / α-olefin copolymer containing a large amount of low density (high number of short chain branches) is introduced into the low molecular weight portion. The melting point is high. On the other hand, even ethylene / α-olefin copolymers with the same number of short-chain branches, in which short-chain branches are uniformly introduced from a low molecular weight to a high molecular weight, have a low density (high number of short-chain branches). The melting point is lower than that of the containing ethylene / α-olefin copolymer.

Ｔｍ＜−１．８×ＳＣＢ＋１４０ （１）
このようなエチレン・α−オレフィン共重合体（Ｄ）は、例えば、以下に例示するような公報に開示されている方法によって製造することができる。 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.

特開昭６０−３５００６号公報、特開昭６０−３５００７号公報、特開昭６０−３５００８号公報、特開平３−１６３０８８号公報、特開昭６１−２９６００８号公報、特開昭６３−２２８０４号公報、特開昭５８−１９３０９号公報、特開昭６３−６１０１０号公報、特開昭６３−１５２６０８号公報、特開昭６３−２６４６０６号公報、特開昭６３−２８０７０３号公報、特開昭６４−６００３号公報、特開平１−９５１１０号公報、特開平３−６２８０６号公報、特開平１−２５９００４号公報、特開昭６４−４５４０６号公報、特開昭６０−１０６８０８号公報、特開昭６０−１３７９１１号公報、特開昭６１−２９６００８号公報、特許公表６３−５０１３６９号公報、特開昭６１−２２１２０７号公報、特開平２−２２３０７号公報、特開平２−１７３１１０号公報、特開平２−３０２４１０号公報、特開平１−１２９００３号公報、特開平１−２１０４０４号公報、特開平３−６６７１０号公報、特開平３−７０７１０号公報、特開平１−２０７２４８号公報、特開昭６３−２２２１７７号公報、特開昭６３−２２２１７８号公報、特開昭６３−２２２１７９号公報、特開平１−１２４０７号公報、特開平１−３０１７０４号公報、特開平１−３１９４８９号公報、特開平３−７４４１２号公報、特開昭６１−２６４０１０号公報、特開平１−２７５６０９号公報、特開昭６３−２５１４０５号公報、特開昭６４−７４２０２号公報、特開平２−４１３０３号公報、特開平１−３１４８８号公報、特開平３−５６５０８号公報、特開平３−７０７０８号公報、特開平３−７０７０９号公報などが挙げられる。
また、該エチレン・α−オレフィン共重合体（Ｄ）は、市販品であっても良い。 JP-A-60-35006, JP-A-60-35007, JP-A-60-35008, JP-A-3-163888, JP-A-61-296008, JP-A-62-28044 JP, 58-19309, JP 63-61010, JP 63-152608, JP 63-264606, JP 63-280703, JP JP-A 64-6003, JP-A-1-95110, JP-A-3-62806, JP-A-1-259004, JP-A 64-45406, JP-A 60-106808, JP 60-137911, JP 61-296008, JP 63-501369, JP 61-221207, JP 22-22307 JP-A-2-173110, JP-A-2-302410, JP-A-1-129003, JP-A-1-210404, JP-A-3-66710, JP-A-3-70710, JP-A-1-207248, JP-A-63-222177, JP-A-63-222178, JP-A-63-222179, JP-A-1-12407, JP-A-1-301704 JP-A-1-319489, JP-A-3-74412, JP-A-61-264010, JP-A-1-275609, JP-A-63-251405, JP-A-64-74202. JP, 4-41303, JP-A-1-31488, JP-A-3-56508, JP-A-3-70708, JP Such -70709 discloses the like.
The ethylene / α-olefin copolymer (D) may be a commercially available product.

本発明のシーラント用接着剤は、特に封緘強度と接着強度に優れるものとなることから、ビニル芳香族炭化水素とオレフィン又はジオレフィンとの熱可塑性ブロック共重合体（Ｅ）を配合したものであることが好ましい。そして、その際の配合量としては、該エチレン−酢酸ビニル共重合体（Ａ）、該エチレン−酢酸ビニル共重合体（Ｂ）、該粘着付与剤樹脂（Ｃ）の合計量１００重量部、又は該エチレン−酢酸ビニル共重合体（Ａ）、該エチレン−酢酸ビニル共重合体（Ｂ）、該粘着付与剤樹脂（Ｃ）の合計量１００重量部に該エチレン・α−オレフィン共重合体（Ｄ）を配合したものに対し、該ビニル芳香族炭化水素とオレフィン又はジオレフィンとの熱可塑性ブロック共重合体（Ｅ）０．５〜５重量部であることが好ましく、特に１〜４重量部であることが好ましい。   Since the adhesive for sealants of the present invention is particularly excellent in sealing strength and adhesive strength, it is a blend of a thermoplastic block copolymer (E) of vinyl aromatic hydrocarbon and olefin or diolefin. It is preferable. And as a compounding quantity in that case, the total amount of this ethylene-vinyl acetate copolymer (A), this ethylene-vinyl acetate copolymer (B), this tackifier resin (C) is 100 weight part, or The ethylene / α-olefin copolymer (D) was added to 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). ) Is preferably 0.5 to 5 parts by weight of the thermoplastic block copolymer (E) of the vinyl aromatic hydrocarbon and olefin or diolefin, particularly 1 to 4 parts by weight. Preferably there is.

本発明を構成するビニル芳香族炭化水素とオレフィン又はジオレフィンとの熱可塑性ブロック共重合体（Ｅ）は、一般式（Ａ−Ｂ）ｎ、（Ａ−Ｂ）ｎ−Ａ´または（Ａ−Ｂ）ｍ−Ｘ（但し、式中ＡおよびＡ′はビニル芳香族炭化水素重合体ブロック、Ｂはオレフィン又はジオレフィン重合体ブロック、ｎは１〜５の整数、ｍは２〜７の整数、Ｘはｍ価の多官能性化合物を表す。）で表される直鎖構造、放射構造または分岐構造からなる少なくとも片末端がビニル芳香族炭化水素重合体ブロックであるブロック構造を有する重合体であり、その水添物であっても良い。ここで用いられるビニル芳香族炭化水素の例として、スチレン、α−メチルスチレン、ビニルトルエン、ｐ−ｔｅｒｔ−ブチルスチレン、ビニルキシレン、エチルビニルキシレン、ビニルナフタレンおよびこれらの混合物等が挙げられる。これらのうちではスチレンが特に好ましい。一方、オレフィンの例としてはエチレン、プロピレン、１−ブテン等のα−オレフィン等、ジオレフィンの例としては、ブタジエン、イソプレン等の共役ジオレフィンが挙げられる。また、該ビニル芳香族炭化水素とジオレフィンとの熱可塑性ブロック共重合体（Ｅ）として、共役ジオレフィンを重合した重合体ブロックに水素添加したものを用いてもよく、更に、ブロックＢはオレフィン単位が優勢である限り、共役ジオレフィンとビニル芳香族炭化水素との共重合体を用いてもよい。これらのうち本発明においては両末端にビニル芳香族炭化水素重合体ブロックを有するビニル芳香族炭化水素とオレフィン又はジオレフィンとの熱可塑性ブロック共重合体が好ましく、ポリスチレン−ポリブタジエン−ポリスチレンブロック共重合体の水素添加物（スチレン−エチレン／ブチレン−スチレントリブロック共重合体、以下ＳＥＢＳ）が熱安定性の向上の点から特に好ましく用いられる。   The thermoplastic block copolymer (E) of a vinyl aromatic hydrocarbon and an olefin or diolefin constituting the present invention has a general formula (AB) n, (AB) n-A 'or (A- B) m-X (where A and A ′ are vinyl aromatic hydrocarbon polymer blocks, B is an olefin or diolefin polymer block, n is an integer of 1 to 5, m is an integer of 2 to 7, X represents an m-valent polyfunctional compound.) A polymer having a block structure in which at least one terminal having a linear structure, a radial structure or a branched structure represented by (ii) is a vinyl aromatic hydrocarbon polymer block. The hydrogenated product may be used. Examples of the vinyl aromatic hydrocarbon used here include styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, vinylxylene, ethylvinylxylene, vinylnaphthalene, and mixtures thereof. Of these, styrene is particularly preferred. On the other hand, examples of olefins include α-olefins such as ethylene, propylene, and 1-butene, and examples of diolefins include conjugated diolefins such as butadiene and isoprene. Further, as the thermoplastic block copolymer (E) of the vinyl aromatic hydrocarbon and the diolefin, a hydrogenated polymer block obtained by polymerizing a conjugated diolefin may be used, and the block B may be an olefin. As long as the unit is dominant, a copolymer of a conjugated diolefin and a vinyl aromatic hydrocarbon may be used. Among these, in the present invention, a thermoplastic block copolymer of a vinyl aromatic hydrocarbon having a vinyl aromatic hydrocarbon polymer block at both ends and an olefin or a diolefin is preferable, and a polystyrene-polybutadiene-polystyrene block copolymer. The hydrogenated product (styrene-ethylene / butylene-styrene triblock copolymer, hereinafter referred to as SEBS) is particularly preferably used from the viewpoint of improving thermal stability.

また、該ビニル芳香族炭化水素とオレフィン又はジオレフィンとの熱可塑性ブロック共重合体（Ｅ）は、２００℃、５．０ｋｇ荷重におけるメルトフローレイトが１０〜７０ｇ／１０分の範囲にあるものが好ましく、特に１２〜６５ｇ／１０分であることが好ましい。   In addition, the thermoplastic block copolymer (E) of the vinyl aromatic hydrocarbon and olefin or diolefin has a melt flow rate in the range of 10 to 70 g / 10 min at 200 ° C. and 5.0 kg load. Particularly preferred is 12 to 65 g / 10 min.

また、該ビニル芳香族炭化水素とオレフィン又はジオレフィンとの熱可塑性ブロック共重合体（Ｅ）は、成形加工性と接着強度に優れたシーラント用接着剤となることから、水素添加スチレン−ブタジエン−ジブロック共重合体と水素添加スチレン−ブタジエン−スチレン−トリブロック共重合体の混合物であり、その混合比が５／５〜９／１であることが好ましく、スチレン含量が２０〜５０重量％であることが好ましい。   Further, since the thermoplastic block copolymer (E) of the vinyl aromatic hydrocarbon and the olefin or diolefin is an adhesive for sealant excellent in molding processability and adhesive strength, the hydrogenated styrene-butadiene- It is a mixture of a diblock copolymer and a hydrogenated styrene-butadiene-styrene-triblock copolymer, preferably a mixing ratio of 5/5 to 9/1, and a styrene content of 20 to 50% by weight. Preferably there is.

該ビニル芳香族炭化水素とオレフィン又はジオレフィンとの熱可塑性ブロック共重合体（Ｅ）は、市販されているものが用いられる。具体的例示としては、例えば（商品名）クレイトン（Ｋｒａｔｏｎ）Ｇ１７２６ＭＳ（クレイトンポリマー株式会社製）等を挙げることができる。   What is marketed is used for the thermoplastic block copolymer (E) of this vinyl aromatic hydrocarbon and an olefin or a diolefin. Specific examples include (trade name) Kraton G1726MS (manufactured by Kraton Polymer Co., Ltd.) and the like.

本発明のシーラント用接着剤は、本発明の効果を損なわない範囲で、他の熱可塑性樹脂やゴム、及び光安定剤、紫外線吸収剤、造核剤、滑剤、酸化防止剤、ブロッキング防止剤、流動性改良剤、離型剤、難燃剤、着色剤、無機系中和剤、塩酸吸収剤、充填剤導電剤等が用いられても良い。   The adhesive for sealant of the present invention is within the range not impairing the effects of the present invention, other thermoplastic resins and rubbers, and light stabilizers, ultraviolet absorbers, nucleating agents, lubricants, antioxidants, antiblocking agents, Fluidity improvers, mold release agents, flame retardants, colorants, inorganic neutralizers, hydrochloric acid absorbents, filler conductive agents, and the like may be used.

本発明のシーラント用接着剤の調製方法としては、シーラント用接着剤の調製が可能であれば如何なる方法であってもよく、例えば該エチレン−酢酸ビニル共重合体（Ａ）、該エチレン−酢酸ビニル共重合体（Ｂ）、該粘着付与剤樹脂（Ｃ）を同時にヘンシェルミキサー又はタンブラー等の混合機により予備ブレンドしておき、単軸又は二軸の押出機で溶融混練する方法が挙げられる。   The method for preparing the sealant adhesive of the present invention may be any method as long as the sealant adhesive can be prepared. For example, the ethylene-vinyl acetate copolymer (A), the ethylene-vinyl acetate. Examples include a method in which the copolymer (B) and the tackifier resin (C) are simultaneously pre-blended with a mixer such as a Henschel mixer or a tumbler and melt-kneaded with a single-screw or twin-screw extruder.

本発明のシーラント用接着剤は容器の蓋材シーラント用接着剤として用いられる。容器としては、ポリエチレンテレフタレートを主成分であるものに適している。   The sealant adhesive of the present invention is used as an adhesive for container lid sealants. As a container, it is suitable for the thing which has a polyethylene terephthalate as a main component.

本発明の蓋材用フィルムは、支持基材層と上記シーラント用接着剤層の少なくとも２層を含む構成からなる。支持基材層を構成する支持基材としては、自己支持性を有するものであれば良く、例えば、ポリエチレン、ポリプロピレン、エチレン−酸共重合樹脂などのオレフィン系樹脂、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレートなどのポリエステル系樹脂、ポリアミド系樹脂等の熱可塑性樹脂で構成されたプラスチックフィルム、和紙、複合紙などの紙、アルミニウムなどの金属で構成された金属箔、これらの単独又は積層体などが挙げられる。支持基材層の厚みは、機械的強度、作業性などが損なわれない範囲で用途に応じて選択できるが、一般的には５〜１００μｍ程度、好ましくは１０〜５０μｍである。   The film for a lid material of the present invention comprises a structure including at least two layers of a support base material layer and the above adhesive layer for sealant. The supporting substrate constituting the supporting substrate layer may be any material having self-supporting properties, for example, olefinic resins such as polyethylene, polypropylene, ethylene-acid copolymer resin, polyethylene terephthalate, polybutylene terephthalate, polyethylene. Polyester resin such as naphthalate, plastic film composed of thermoplastic resin such as polyamide resin, paper such as Japanese paper and composite paper, metal foil composed of metal such as aluminum, single or laminated body of these Can be mentioned. Although the thickness of a support base material layer can be selected according to a use in the range in which mechanical strength, workability | operativity, etc. are not impaired, Generally it is about 5-100 micrometers, Preferably it is 10-50 micrometers.

シーラント用接着剤層の厚みは、接着性、作業性などが損なわれない範囲で用途に応じて選択できるが、一般的には５〜５０μｍ程度、好ましくは１５〜３０μｍである。   The thickness of the adhesive layer for sealant can be selected according to the application within a range where the adhesiveness and workability are not impaired, but is generally about 5 to 50 μm, preferably 15 to 30 μm.

本発明では、前記支持基材層とシーラント用接着剤層との間に、両層の密着性を高めるため、中間層を設けることもできる。この中間層は、ポリオレフィンなどの熱可塑性樹脂、熱可塑性エラストマーなどの成分で構成でき、これらの成分は単独又は２種以上混合して使用できる。例えば、ポリオレフィンとしては、ポリエチレンやエチレン共重合体（エチレン・α−オレフィン共重合体、プロピレン−エチレン共重合体、エチレン−アクリル酸共重合体、エチレン−メタクリル酸共重合体、エチレン−アクリル酸メチル共重合体など）やその変性物などが挙げられる。中間層には、本発明の効果を損なわない範囲で、各種添加剤、例えば、酸化防止剤、滑剤、帯電防止剤、導電剤、アンチブロッキング剤、粘着付与剤等が用いられても良い。   In the present invention, an intermediate layer may be provided between the support base material layer and the adhesive layer for sealant in order to improve the adhesion between the two layers. This intermediate layer can be composed of components such as a thermoplastic resin such as polyolefin, a thermoplastic elastomer, and the like, and these components can be used alone or in combination of two or more. Examples of polyolefins include polyethylene and ethylene copolymers (ethylene / α-olefin copolymers, propylene-ethylene copolymers, ethylene-acrylic acid copolymers, ethylene-methacrylic acid copolymers, ethylene-methyl acrylates). Copolymer) and modified products thereof. Various additives such as an antioxidant, a lubricant, an antistatic agent, a conductive agent, an antiblocking agent, and a tackifier may be used in the intermediate layer as long as the effects of the present invention are not impaired.

中間層の厚みは、作業性などが損なわれない範囲で用途に応じて選択できるが、一般的には５〜３０μｍ程度である。   Although the thickness of an intermediate | middle layer can be selected according to a use in the range which does not impair workability | operativity etc., generally it is about 5-30 micrometers.

本発明では、前記支持基材層とシーラント用接着剤層との間、又は上記支持基材層と中間層との間に、両層の密着性を高めるためポリウレタン等のアンカーコート層を設けることもできる。   In the present invention, an anchor coat layer such as polyurethane is provided between the support base material layer and the adhesive layer for sealant or between the support base material layer and the intermediate layer in order to improve adhesion between the two layers. You can also.

本発明の蓋材用フィルムは、Ａ−ＰＥＴ用容器の蓋材として好適であり、封緘性と易剥離性を有する。   The film for lids of the present invention is suitable as a lid for containers for A-PET, and has sealing properties and easy peelability.

該蓋材用フィルムの製造方法としては、特に限定はしないが、シーラント用接着剤と支持基材層をラミネートする方法、シーラント用接着剤と支持基材層を共押出する方法などが挙げられる。ラミネートする方法としては、例えば、（１）支持基材層にアンカーコート剤を塗布し、接着剤層を溶融押出する押出ラミネート方法、（２）支持基材層にアンカーコート剤を塗布し、中間層を溶融押出した後、その上にシーラント用接着剤層を溶融押出する押出ラミネート方法、（３）支持基材層に、支持基材との接着性に優れた中間層を溶融押出した後、その上にシーラント用接着剤層を溶融押出する押出ラミネート方法、（４）支持基材層にアンカーコート剤を塗布し、中間層と接着剤層を同時に溶融押出する共押出ラミネート方法、（５）予めインフレーション成形法やキャスト成形法によりシーラント接着剤を少なくとも１層含むフィルムを成形し、アンカーコート剤を塗布した支持基材層と貼り合わせるドライラミネート法、（６）アンカーコート剤を塗布した支持基材層とシーラント接着剤を少なくとも１層含むフィルムを押出ラミネートを用いて中間層を溶融押出すことにより積層する押出ラミネート方法などが挙げられる。一方、共押出する方法としては、共押出インフレーション法や共押出Ｔダイ法などを例示することができる。   Although it does not specifically limit as a manufacturing method of this film for lid | cover materials, The method of laminating the adhesive agent for sealants and a support base material layer, the method of coextruding the adhesive agent for sealants, and a support base material layer, etc. are mentioned. Examples of the laminating method include: (1) an extrusion laminating method in which an anchor coating agent is applied to a supporting base material layer, and an adhesive layer is melt-extruded; (2) an anchor coating agent is applied to the supporting base material layer; After the layer is melt-extruded, an extrusion laminating method in which an adhesive layer for sealant is melt-extruded thereon, (3) after melt-extruding an intermediate layer excellent in adhesiveness to the support substrate to the support substrate layer, (4) An extrusion laminating method in which an adhesive layer for sealant is melt-extruded, (4) a co-extrusion laminating method in which an anchor coating agent is applied to a support base material layer, and an intermediate layer and an adhesive layer are melt-extruded simultaneously. A dry laminating method in which a film containing at least one layer of a sealant adhesive is formed in advance by an inflation molding method or a cast molding method, and bonded to a support base material layer to which an anchor coating agent is applied, ( ) Such as extrusion lamination method of laminating by to melt extrusion of the intermediate layer using an extrusion laminating a film comprising at least one layer of the supporting substrate layer coated with the anchor coating agent and the sealant adhesive. On the other hand, examples of the coextrusion method include a coextrusion inflation method and a coextrusion T-die method.

本発明の容器の蓋材シーラント用接着剤は、成形加工性に優れ、高い封緘強度と接着強度が得られ、耐熱性に優れたＡ−ＰＥＴ製容器の蓋材に用いられ、蓋材用フィルムとして有用である。   The container sealant adhesive for containers of the present invention is excellent in molding processability, has high sealing strength and adhesive strength, and is used as a cover material for A-PET containers excellent in heat resistance. Useful as.

以下、実施例に基づいて本発明を更に具体的に説明するが、本発明はこれら実施例に限定されるものではない。   EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited to these Examples.

〜メルトフローレイト（ＭＦＲ）〜
エチレン−酢酸ビニル共重合体（Ａ）、エチレン−酢酸ビニル共重合体（Ｂ）のＭＦＲは、ＪＩＳ Ｋ６９２４−１に準拠して測定した。 ~ Melt flow rate (MFR) ~
The MFR of the ethylene-vinyl acetate copolymer (A) and the ethylene-vinyl acetate copolymer (B) was measured according to JIS K6924-1.

実施例により得られたシーラント用接着剤について以下に示す方法にて、成形加工性を評価した。   The molding processability of the adhesive for sealants obtained in the examples was evaluated by the method described below.

〜成形加工安定性〜
押出ラミネーター（プラコー（株）社製 スクリュー径２５ｍｍφ）を用い、本接着剤ペレットを加工温度２３０℃で押出ラミネーションしシーラント用接着剤層厚み２５μｍのフィルムを採取した。判定は、ラミネート加工後のフィルム厚みに３μｍ以上の偏差がないもの（△、及び○）を良好とした。 ~ Molding stability ~
Using an extrusion laminator (Placo Co., Ltd., screw diameter 25 mmφ), the adhesive pellets were subjected to extrusion lamination at a processing temperature of 230 ° C., and a film having a sealant adhesive layer thickness of 25 μm was collected. Judgment made the thing ((triangle | delta) and (circle)) which does not have a deviation of 3 micrometers or more in the film thickness after a lamination process favorable.

○：溶融膜の脈動や横揺れが無く、厚み偏差３μｍ未満 、△：溶融膜の脈動や横揺れはあるが、厚み偏差３μｍ未満、×：溶融膜の脈動や横揺れがあり、厚み偏差５μｍ以上
〜ロールリリース性〜
押出ラミネーター（プラコー（株）社製 スクリュー径２５ｍｍφ）を用い、本接着剤ペレットを加工温度２３０℃でシーラント用接着剤層厚み２５μｍとなるように押出ラミネーションし、冷却用マットロールとのリリース性を評価した。判定は、フィルム表面にロールと剥離した際の剥離痕が無いもの（○）を良好とした。 ○: There is no pulsation or roll of the molten film and the thickness deviation is less than 3 μm. Δ: There is pulsation or roll of the molten film, but the thickness deviation is less than 3 μm. X: There is pulsation or roll of the molten film, and the thickness deviation is 5 μm. that's all
~ Roll release properties ~
Using an extrusion laminator (Placo Co., Ltd., screw diameter 25 mmφ), this adhesive pellet is extruded and laminated so that the adhesive layer thickness for sealant is 25 μm at a processing temperature of 230 ° C. evaluated. Judgment made the thing ((circle)) with no peeling trace at the time of peeling with a roll on the film surface favorable.

○：剥離痕なし 、×：剥離痕あり
実施例により得られた蓋材用フィルムついて以下に示す方法にて、封緘強度、接着強度を測定した。 ○: no peeling mark, ×: peeling mark
Sealing strength and adhesive strength of the film for a lid material obtained in the examples were measured by the methods described below.

〜封緘強度の測定〜
フィルムの接着剤面とＡ−ＰＥＴカップ（容量２１５ｍｌ）とを重ね合わせカップシール機（サニーカップ社製、型式ＵＦ−５００型）を用いて１６０℃、４０Ｋｇｆ／カップ、１秒の条件で加圧加熱接着した。放冷後に、シールテスター（サン化学社製、型式 ＦＫＴ−１００Ｊ）を用いて 空気注入量０．８Ｌ／分の条件にて破裂強度を測定した。判定は２５ｋＰａ以上を良好とした。 ~ Measurement of sealing strength ~
The adhesive side of the film and A-PET cup (capacity: 215 ml) are overlapped and pressurized using a cup sealer (Sunny Cup, model UF-500 type) at 160 ° C., 40 Kgf / cup for 1 second. Heat bonded. After standing to cool, the burst strength was measured using a seal tester (manufactured by Sun Chemical Co., Ltd., model FKT-100J) under conditions of an air injection rate of 0.8 L / min. Judgment made 25 kPa or more favorable.

○：２５ｋＰａ以上 、×：２５ｋＰａ未満
〜接着強度の測定〜
フィルムの接着剤面とＡ−ＰＥＴシート（ポリテック社製）とを重ね合わせヒートシールテスター（テスター産業社製、ＴＰ−７０１型）を用いて１６０℃、０．２ＭＰａ、１秒の条件で加圧加熱接着した。放冷後に、剥離角度１８０度、剥離速度３００ｍｍ／分の条件にてシール強度を測定した。判定は、１０Ｎ／１５ｍｍ幅以上を良好とした。 ○: 25 kPa or more, x: less than 25 kPa -Measurement of adhesive strength-
The adhesive surface of the film and A-PET sheet (manufactured by Polytech Co., Ltd.) are overlaid and pressed using a heat seal tester (manufactured by Tester Sangyo Co., Ltd., TP-701 type) at 160 ° C., 0.2 MPa for 1 second Heat bonded. After standing to cool, the seal strength was measured under the conditions of a peeling angle of 180 degrees and a peeling speed of 300 mm / min. Judgment made 10N / 15mm width or more favorable.

○：１０Ｎ／１５ｍｍ以上 、×：１０Ｎ／１５ｍｍ未満
実施例１
エチレン−酢酸ビニル共重合体（Ａ）として、酢酸ビニル含量６％、メルトマスフローレイトが８．５ｇ／１０分である樹脂（Ａ１）（東ソー（株）製 商品名ウルトラセン５３７）４０重量部、エチレン−酢酸ビニル共重合体（Ｂ）として、酢酸ビニル含量１５％、メルトマスフローレイトが３．０ｇ／１０分である樹脂（Ｂ１）（東ソー（株）製 商品名ウルトラセン６２６）４０重量部、粘着付与剤樹脂（Ｃ）として、部分水添石油樹脂（Ｃ１）（荒川化学（株）社製 商品名アルコンＭ１１５； 軟化温度１１５℃、水添率約６０％（ＮＭＲ法））２０重量部をタンブラー混合機で予備ブレンドした後、二軸押出機を用い１８０℃で溶融混練しシーラント用接着剤のペレットを得た。エチレン−酢酸ビニル共重合体（Ａ１）の酢酸ビニル含量とエチレン−酢酸ビニル共重合体（Ｂ１）の酢酸ビニル含量の差は９重量％である。尚、シーラント用接着剤には、熱安定性を考慮し、フェノール系酸化防止剤（ＢＡＳＦ（株）社製、商品名イルガノックス１０１０）をシーラント用接着剤１００重量部に対し０．０５重量部、スリップ剤（ライオンアクゾ（株）社製、製品名アーモワックスＥ）を０．２重量部添加した。
得られたシーラント用接着剤のＭＦＲは、１５ｇ／１０分であった。 ○: 10 N / 15 mm or more, ×: less than 10 N / 15 mm Example 1
As ethylene-vinyl acetate copolymer (A), 40 parts by weight of resin (A1) (trade name Ultrasen 537, manufactured by Tosoh Corporation) having a vinyl acetate content of 6% and a melt mass flow rate of 8.5 g / 10 min. As ethylene-vinyl acetate copolymer (B), 40 parts by weight of resin (B1) (trade name Ultrasen 626, manufactured by Tosoh Corporation) having a vinyl acetate content of 15% and a melt mass flow rate of 3.0 g / 10 min. As a tackifier resin (C), 20 parts by weight of partially hydrogenated petroleum resin (C1) (trade name Alcon M115 manufactured by Arakawa Chemical Co., Ltd .; softening temperature 115 ° C., hydrogenation rate of about 60% (NMR method)) After pre-blending with a tumbler mixer, the mixture was melt-kneaded at 180 ° C. using a twin screw extruder to obtain an adhesive pellet for sealant. 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) is 9% by weight. In view of thermal stability, the sealant adhesive is 0.05 parts by weight of a phenolic antioxidant (BASF Corp., trade name: Irganox 1010) with respect to 100 parts by weight of the sealant adhesive. 0.2 parts by weight of a slip agent (product name: Armowax E, manufactured by Lion Akzo Co., Ltd.) was added.
The MFR of the obtained sealant adhesive was 15 g / 10 minutes.

その後、予め支持基材層である二軸延伸ポリエステルフィルム（１２μｍ厚み）に中間層である低密度ポリエチレン（２５μｍ厚み、東ソー（株）社製 商品名ペトロセン２０３）を押出ラミネートした多層フィルムの低密度ポリエチレン表面に、押出ラミネーター（プラコー（株）社製 スクリュー径２５ｍｍφ）を用い、本接着剤ペレットを加工温度２３０℃で押出ラミネーションしシーラント用接着剤層厚み２５μｍの蓋材用フィルムを得た。   Thereafter, a low-density multi-layer film obtained by extruding and laminating a low-density polyethylene (25 μm thickness, trade name Petrocene 203 manufactured by Tosoh Corporation) as an intermediate layer to a biaxially stretched polyester film (12 μm thickness) as a supporting base material layer. This adhesive pellet was extrusion-laminated at a processing temperature of 230 ° C. using an extrusion laminator (screw diameter: 25 mmφ manufactured by Plako Co., Ltd.) on the polyethylene surface to obtain a film for a lid material having an adhesive layer thickness of 25 μm.

得られたシーラント用接着剤、及び蓋材用フィルムの評価結果を表３に示す。   Table 3 shows the evaluation results of the obtained sealant adhesive and lid film.

実施例２
エチレン−酢酸ビニル共重合体（Ａ１）４０重量部の代わりに、エチレン−酢酸ビニル共重合体（Ａ１）３５重量部、エチレン−酢酸ビニル共重合体（Ｂ１）４０重量部の代わりにエチレン−酢酸ビニル共重合体（Ｂ１）３５重量部、粘着付与剤樹脂（Ｃ）として、部分水添石油樹脂（Ｃ１）２０重量部の代わりに、完全水添石油樹脂（Ｃ２）（荒川化学（株）社製 商品名アルコンＰ１２５； 軟化温度１２５℃、水添率約９５％（ＮＭＲ法））３０重量部、エチレン・α−オレフィン共重合体（Ｄ）として、密度が８６０ｋｇ／ｍ３であるエチレン・α−オレフィン共重合体（Ｄ１）（三井化学（株）社製、商品名タフマーＰ−０３７５）４０重量部とした以外は、実施例１と同様にしてシーラント用接着剤、及び蓋材用フィルムを得た。エチレン−酢酸ビニル共重合体（Ａ１）の酢酸ビニル含量とエチレン−酢酸ビニル共重合体（Ｂ１）の酢酸ビニル含量の差は９重量％である。 Example 2
Instead of 40 parts by weight of ethylene-vinyl acetate copolymer (A1), 35 parts by weight of ethylene-vinyl acetate copolymer (A1) and ethylene-acetic acid instead of 40 parts by weight of ethylene-vinyl acetate copolymer (B1) Instead of 20 parts by weight of partially hydrogenated petroleum resin (C1), 35 parts by weight of vinyl copolymer (B1) and tackifier resin (C), fully hydrogenated petroleum resin (C2) (Arakawa Chemical Co., Ltd.) Product name Alcon P125; softening temperature 125 ° C., hydrogenation rate of about 95% (NMR method) 30 parts by weight, ethylene / α-olefin copolymer (D) having a density of 860 kg / m 3 -Olefin copolymer (D1) (trade name TAFMER P-0375, manufactured by Mitsui Chemicals, Inc.) Except for 40 parts by weight, the adhesive for sealant and the film for lid material were the same as in Example 1. Obtained. 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) is 9% by weight.

接着剤配合を表１に示す。得られたシーラント用接着剤のＭＦＲは、９ｇ／１０分であった。   Table 1 shows the adhesive formulation. The MFR of the obtained adhesive for sealants was 9 g / 10 minutes.

得られたシーラント用接着剤、及び蓋材用フィルムの評価結果を表３に示す。   Table 3 shows the evaluation results of the obtained sealant adhesive and lid film.

実施例３
エチレン−酢酸ビニル共重合体（Ｂ１）３５重量部の代わりに、酢酸ビニル含量１０部、メルトマスフローレイトが９．０ｇ／１０分であるエチレン−酢酸ビニル共重合体（Ｂ２）（東ソー（株）製 商品名ウルトラセン５４１）３５重量部、粘着付与剤樹脂（Ｃ）として、完全水添石油樹脂（Ｃ２）３０重量部の代わりに、部分水添石油樹脂（Ｃ１）３０重量部、エチレン・α−オレフィン共重合体（Ｄ１）４０重量部の代わりに、密度が８８５ｋｇ／ｍ３であるエチレン・α−オレフィン共重合体（Ｄ２）（東ソー（株）社製、商品名ＬＵＭＩＴＡＣ ＢＦ３００Ｒ）４０重量部、とした以外は、実施例２と同様にしてシーラント用接着剤、及び蓋材用フィルムを得た。エチレン−酢酸ビニル共重合体（Ａ１）の酢酸ビニル含量とエチレン−酢酸ビニル共重合体（Ｂ１）の酢酸ビニル含量の差は４重量％である。 Example 3
Instead of 35 parts by weight of ethylene-vinyl acetate copolymer (B1), ethylene-vinyl acetate copolymer (B2) having a vinyl acetate content of 10 parts and a melt mass flow rate of 9.0 g / 10 min (Tosoh Corporation) Product name Ultrasen 541) 35 parts by weight, tackifier resin (C), 30 parts by weight of partially hydrogenated petroleum resin (C1) instead of 30 parts by weight of fully hydrogenated petroleum resin (C2), ethylene / α -Instead of 40 parts by weight of the olefin copolymer (D1), 40 parts by weight of an ethylene / α-olefin copolymer (D2) having a density of 885 kg / m 3 (trade name LUMITAC BF300R, manufactured by Tosoh Corporation) A sealant adhesive and a lid material film were obtained in the same manner as in Example 2 except that. 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) is 4% by weight.

接着剤配合を表１に示す。得られたシーラント用接着剤のＭＦＲは、１３ｇ／１０分であった。   Table 1 shows the adhesive formulation. The MFR of the obtained sealant adhesive was 13 g / 10 minutes.

得られた蓋材用フィルムの評価結果を表３に示す。   Table 3 shows the evaluation results of the obtained film for lid materials.

実施例４
エチレン−酢酸ビニル共重合体（Ａ１）３５重量部の代わりに、エチレン−酢酸ビニル共重合体（Ａ１）４０重量部、エチレン−酢酸ビニル共重合体（Ｂ２）３５重量部の代わりに、エチレン−酢酸ビニル共重合体（Ｂ２）４０重量部、粘着付与剤樹脂（Ｃ）として、部分水添石油樹脂（Ｃ１）３０重量部の代わりに、部分水添石油樹脂（Ｃ３）（荒川化学（株）社製 商品名アルコンＭ１３５； 軟化温度１３５℃、水添率約６０％（ＮＭＲ法））２０重量部、エチレン・α−オレフィン共重合体（Ｄ２）４０重量部の代わりに、エチレン・α−オレフィン共重合体（Ｄ２）２０重量部、とした以外は、実施例３と同様にしてシーラント用接着剤、及び蓋材用フィルムを得た。エチレン−酢酸ビニル共重合体（Ａ１）の酢酸ビニル含量とエチレン−酢酸ビニル共重合体（Ｂ１）の酢酸ビニル含量の差は４重量％である。 Example 4
Instead of 35 parts by weight of ethylene-vinyl acetate copolymer (A1), 40 parts by weight of ethylene-vinyl acetate copolymer (A1) and ethylene-vinyl acetate copolymer (B2) instead of 35 parts by weight of ethylene- Instead of 30 parts by weight of partially hydrogenated petroleum resin (C1), 40 parts by weight of vinyl acetate copolymer (B2) and tackifier resin (C), partially hydrogenated petroleum resin (C3) (Arakawa Chemical Co., Ltd.) Product name Alcon M135; softening temperature 135 ° C., hydrogenation rate of about 60% (NMR method) 20 parts by weight, ethylene / α-olefin copolymer (D2) 40 parts by weight instead of ethylene / α-olefin A sealant adhesive and a lid film were obtained in the same manner as in Example 3 except that the copolymer (D2) was 20 parts by weight. 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) is 4% by weight.

接着剤配合を表１に示す。得られたシーラント用接着剤のＭＦＲは、１０ｇ／１０分であった。   Table 1 shows the adhesive formulation. The MFR of the obtained adhesive for sealants was 10 g / 10 minutes.

得られたシーラント用接着剤、及び蓋材用フィルムの評価結果を表３に示す。   Table 3 shows the evaluation results of the obtained sealant adhesive and lid film.

実施例５
粘着付与剤樹脂（Ｃ）として、部分水添石油樹脂（Ｃ３）２０重量部の代わりに、部分水添石油樹脂（Ｃ１）２０重量部、エチレン・α−オレフィン共重合体（Ｄ２）２０重量部の代わりに、エチレン・α−オレフィン共重合体（Ｄ２）０重量部、ビニル芳香族炭化水素とジオレフィンとの熱可塑性ブロック共重合体（Ｅ）として、２００℃、５．０ｋｇ荷重におけるメルトフローレイトが６５ｇ／１０分、水素添加スチレン−ブタジエン−ジブロック共重合体と水素添加スチレン−ブタジエン−スチレン−トリブロック共重合体の混合比が７／３であり、スチレン含量が３０重量％であるビニル芳香族炭化水素とジオレフィンとの熱可塑性ブロック共重合体（Ｅ１）（ＫｒａｔｏｎＧ１７２６ＭＳ）５重量部とした以外は、実施例４と同様にしてシーラント用接着剤、及び蓋材用フィルムを得た。エチレン−酢酸ビニル共重合体（Ａ１）の酢酸ビニル含量とエチレン−酢酸ビニル共重合体（Ｂ１）の酢酸ビニル含量の差は４重量％である。 Example 5
As a tackifier resin (C), instead of 20 parts by weight of partially hydrogenated petroleum resin (C3), 20 parts by weight of partially hydrogenated petroleum resin (C1), 20 parts by weight of ethylene / α-olefin copolymer (D2) Instead of ethylene / α-olefin copolymer (D2) 0 part by weight, vinyl aromatic hydrocarbon and diolefin thermoplastic block copolymer (E) as a melt flow at 200 ° C. and 5.0 kg load The rate is 65 g / 10 minutes, the mixing ratio of hydrogenated styrene-butadiene-diblock copolymer and hydrogenated styrene-butadiene-styrene-triblock copolymer is 7/3, and the styrene content is 30% by weight. The same as in Example 4 except that 5 parts by weight of the thermoplastic block copolymer (E1) (Kraton G1726MS) of vinyl aromatic hydrocarbon and diolefin was used. Thus, an adhesive for sealant and a film for lid material were obtained. 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) is 4% by weight.

接着剤配合を表１に示す。得られたシーラント用接着剤のＭＦＲは、２４ｇ／１０分であった。   Table 1 shows the adhesive formulation. The MFR of the obtained sealant adhesive was 24 g / 10 minutes.

得られたシーラント用接着剤、及び蓋材用フィルムの評価結果を表３に示す。   Table 3 shows the evaluation results of the obtained sealant adhesive and lid film.

実施例６
エチレン−酢酸ビニル共重合体（Ａ１）４０重量部の代わりに、エチレン−酢酸ビニル共重合体（Ａ１）３５重量部、エチレン−酢酸ビニル共重合体（Ｂ２）４０重量部の代わりにエチレン−酢酸ビニル共重合体（Ｂ２）３５重量部、部分水添石油樹脂（Ｃ１）２０重量部の代わりに、部分水添石油樹脂（Ｃ１）３０重量部、エチレン・α−オレフィン共重合体（Ｄ２）０重量部の代わりに、エチレン・α−オレフィン共重合体（Ｄ２）４０重量部、ビニル芳香族炭化水素とジオレフィンとの熱可塑性ブロック共重合体（Ｅ１）５重量部の代わりにビニル芳香族炭化水素とジオレフィンとの熱可塑性ブロック共重合体（Ｅ１）２重量部とした以外は、実施例５と同様にしてシーラント用接着剤、及び蓋材用フィルムを得た。エチレン−酢酸ビニル共重合体（Ａ１）の酢酸ビニル含量とエチレン−酢酸ビニル共重合体（Ｂ１）の酢酸ビニル含量の差は４重量％である。 Example 6
Instead of 40 parts by weight of ethylene-vinyl acetate copolymer (A1), 35 parts by weight of ethylene-vinyl acetate copolymer (A1) and ethylene-acetic acid instead of 40 parts by weight of ethylene-vinyl acetate copolymer (B2) Instead of 35 parts by weight of vinyl copolymer (B2) and 20 parts by weight of partially hydrogenated petroleum resin (C1), 30 parts by weight of partially hydrogenated petroleum resin (C1), ethylene / α-olefin copolymer (D2) 0 40 parts by weight of ethylene / α-olefin copolymer (D2) instead of parts by weight, vinyl aromatic carbonization instead of 5 parts by weight of thermoplastic block copolymer of vinyl aromatic hydrocarbon and diolefin (E1) An adhesive for sealant and a film for lid material were obtained in the same manner as in Example 5 except that 2 parts by weight of the thermoplastic block copolymer (E1) of hydrogen and diolefin 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) is 4% by weight.

接着剤配合を表１に示す。得られたシーラント用接着剤のＭＦＲは、１３ｇ／１０分であった。   Table 1 shows the adhesive formulation. The MFR of the obtained sealant adhesive was 13 g / 10 minutes.

得られたシーラント用接着剤、及び蓋材用フィルムの評価結果を表３に示す。   Table 3 shows the evaluation results of the obtained sealant adhesive and lid film.

比較例１
エチレン−酢酸ビニル共重合体（Ａ１）４０重量部の代わりに、エチレン−酢酸ビニル共重合体（Ａ１）８０重量部、エチレン−酢酸ビニル共重合体（Ｂ１）４０重量部の代わりにエチレン−酢酸ビニル共重合体（Ｂ１）０重量部とした以外は、実施例１と同様にしてシーラント用接着剤、及び蓋材用フィルムを得た。 Comparative Example 1
Instead of 40 parts by weight of ethylene-vinyl acetate copolymer (A1), 80 parts by weight of ethylene-vinyl acetate copolymer (A1) and ethylene-acetic acid instead of 40 parts by weight of ethylene-vinyl acetate copolymer (B1) A sealant adhesive and a lid film were obtained in the same manner as in Example 1 except that the vinyl copolymer (B1) was changed to 0 part by weight.

接着剤配合を表２に示す。得られたシーラント用接着剤のＭＦＲは、２３ｇ／１０分であった。   Table 2 shows the adhesive formulation. The MFR of the obtained sealant adhesive was 23 g / 10 minutes.

得られたシーラント用接着剤、及び蓋材用フィルムの評価結果を表４に示す。   Table 4 shows the evaluation results of the obtained sealant adhesive and lid film.

得られた蓋材用フィルムは、接着強度と封緘強度に劣るものであった。   The obtained film for lid materials was inferior in adhesive strength and sealing strength.

比較例２
エチレン−酢酸ビニル共重合体（Ｂ１）３５重量部の代わりに、酢酸ビニル含量２８％、メルトマスフローレイトが５．７ｇ／１０分であるエチレン−酢酸ビニル共重合体（Ｂ２）（東ソー（株）製 商品名ウルトラセン７５１）３５重量部とした以外は、実施例２と同様にしてシーラント用接着剤、及び蓋材用フィルムを得た。エチレン−酢酸ビニル共重合体（Ａ１）の酢酸ビニル含量とエチレン−酢酸ビニル共重合体（Ｂ１）の酢酸ビニル含量の差は２２重量％である。 Comparative Example 2
Instead of 35 parts by weight of ethylene-vinyl acetate copolymer (B1), ethylene-vinyl acetate copolymer (B2) having a vinyl acetate content of 28% and a melt mass flow rate of 5.7 g / 10 min (Tosoh Corporation) Product name Ultrasen 751) An adhesive for sealant and a film for lid material were obtained in the same manner as in Example 2 except that 35 parts by weight 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) is 22% by weight.

接着剤配合を表１に示す。得られたシーラント用接着剤のＭＦＲは、２３ｇ／１０分であった。   Table 1 shows the adhesive formulation. The MFR of the obtained sealant adhesive was 23 g / 10 minutes.

得られたシーラント用接着剤、及び蓋材用フィルムの評価結果を表４に示す。   Table 4 shows the evaluation results of the obtained sealant adhesive and lid film.

得られた接着剤は、成形加工安定性が悪く、ロールリリース性にも劣ったため、蓋材用フィルムは得られなかった。   Since the obtained adhesive was poor in molding process stability and inferior in roll release properties, a lid film could not be obtained.

比較例３
エチレン−酢酸ビニル共重合体（Ａ１）４０重量部の代わりに、エチレン−酢酸ビニル共重合体（Ａ１）２０重量部、エチレン−酢酸ビニル共重合体（Ｂ１）４０重量部の代わりに、エチレン−酢酸ビニル共重合体（Ｂ２）２０重量部、部分水添石油樹脂（Ｃ１）２０重量部の代わりに、部分水添石油樹脂（Ｃ１）６０重量部とした以外は、実施例１と同様にしてシーラント用接着剤、及び蓋材用フィルムを得た。エチレン−酢酸ビニル共重合体（Ａ１）の酢酸ビニル含量とエチレン−酢酸ビニル共重合体（Ｂ１）の酢酸ビニル含量の差は４重量％である。 Comparative Example 3
Instead of 40 parts by weight of the ethylene-vinyl acetate copolymer (A1), 20 parts by weight of the ethylene-vinyl acetate copolymer (A1) and 40% by weight of the ethylene-vinyl acetate copolymer (B1) Except for 20 parts by weight of the vinyl acetate copolymer (B2) and 20 parts by weight of the partially hydrogenated petroleum resin (C1), 60 parts by weight of the partially hydrogenated petroleum resin (C1) was used. An adhesive for sealant and a film for lid were obtained. 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) is 4% by weight.

接着剤配合を表１に示す。得られたシーラント用接着剤のＭＦＲは、７０ｇ／１０分であった。   Table 1 shows the adhesive formulation. The MFR of the obtained sealant adhesive was 70 g / 10 min.

得られた蓋材用フィルムの評価結果を表２に示す。   Table 2 shows the evaluation results of the obtained film for lid materials.

得られた接着剤は、ロールリリース性が悪く、蓋材用フィルムは封緘強度が劣るものであった。   The obtained adhesive had poor roll release properties, and the lid film had poor sealing strength.

Figure 2018076398
Figure 2018076398

Figure 2018076398
Figure 2018076398

Figure 2018076398
Figure 2018076398

Figure 2018076398
Figure 2018076398

Claims (8)

酢酸ビニル含量が３〜１５重量％であるエチレン−酢酸ビニル共重合体（Ａ）１０〜５０重量部、酢酸ビニル含量８〜２５重量％であるエチレン−酢酸ビニル共重合体（Ｂ）１０〜５０重量部、および粘着付与剤樹脂（Ｃ）５〜４０重量部（（Ａ），（Ｂ）及び（Ｃ）の合計は１００重量部）を含み、エチレン−酢酸ビニル共重合体（Ａ）の酢酸ビニル含量とエチレン−酢酸ビニル共重合体（Ｂ）の酢酸ビニル含量の差が３〜２０重量％、エチレン−酢酸ビニル共重合体（Ａ）の酢酸ビニル含量はエチレン−酢酸ビニル共重合体（Ｂ）の酢酸ビニル含量より小さいものであることを特徴とする容器の蓋材シーラント用接着剤。   10 to 50 parts by weight of an ethylene-vinyl acetate copolymer (A) having a vinyl acetate content of 3 to 15% by weight, and 10 to 50 parts of an ethylene-vinyl acetate copolymer (B) having a vinyl acetate content of 8 to 25% by weight. Acetic acid of ethylene-vinyl acetate copolymer (A) containing 5 parts by weight and tackifier resin (C) 5 to 40 parts by weight (total of (A), (B) and (C) is 100 parts by weight) The difference between the vinyl content 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 the ethylene-vinyl acetate copolymer (B The adhesive for sealants for container lids, which is smaller than the vinyl acetate content of 容器の蓋材シーラント用接着剤１００重量部に対し、ＪＩＳ Ｋ６９２２−１（１９９８年）で測定した密度が８６０〜９１０ｋｇ／ｍ３の範囲にあるエチレン・α−オレフィン共重合体（Ｄ）を１０〜５０重量部を配合したことを特徴とする請求項１に記載の容器の蓋材シーラント用接着剤。 10 ethylene / α-olefin copolymers (D) having a density measured in accordance with JIS K6922-1 (1998) in the range of 860 to 910 kg / m 3 with respect to 100 parts by weight of the adhesive for sealant for the lid of the container. The adhesive for a lid material sealant for a container according to claim 1, wherein -50 parts by weight is blended. 容器の蓋材シーラント用接着剤１００重量部に対し、ビニル芳香族炭化水素とオレフィン又はジオレフィンとの熱可塑性ブロック共重合体（Ｅ）０．５〜５重量部を配合したことを特徴とする請求項１〜３のいずれかに記載の容器の蓋材シーラント用接着剤。   It is characterized in that 0.5 to 5 parts by weight of a thermoplastic block copolymer (E) of a vinyl aromatic hydrocarbon and an olefin or diolefin is blended with 100 parts by weight of the adhesive for sealant of the container. The adhesive for lid | cover material sealants of the container in any one of Claims 1-3. 粘着付与剤樹脂（Ｃ）が、脂肪族系石油樹脂、芳香族系石油樹脂、脂環族系水添石油樹脂及び共重合系石油樹脂からなる群から選ばれる少なくとも１種類を５０〜９０％部分水添したものであることを特徴とする請求項１〜５のいずれかに記載の容器の蓋材シーラント用接着剤。   The tackifier resin (C) is 50 to 90% part of at least one selected from the group consisting of aliphatic petroleum resins, aromatic petroleum resins, alicyclic hydrogenated petroleum resins, and copolymerized petroleum resins. 6. The adhesive for sealing a sealant for a container according to any one of claims 1 to 5, wherein the adhesive is hydrogenated. エチレン・α−オレフィン共重合体（Ｄ）が、下記の（ａ）〜（ｃ）の要件を満たすことを特徴とする請求項１又は２に記載の容器の蓋材シーラント用接着剤。
（ａ）重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）の比（Ｍｗ／Ｍｎ）が３以下
（ｂ）示差走査型熱量計による昇温測定において得られる吸熱曲線の最大ピーク位置の温度（Ｔｍ（℃））と赤外線吸収スペクトルの測定から求められる炭素数１０００個当りの短鎖分岐数（ＳＣＢ）とが（１）式の関係を満たす
Ｔｍ＜−１．８×ＳＣＢ＋１４０ （１）
（ｃ）α−オレフィンの炭素数が３以上１２以下 The adhesive for sealing material sealant for containers according to claim 1 or 2, wherein the ethylene / α-olefin copolymer (D) satisfies the following requirements (a) to (c).
(A) The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 3 or less. (B) The temperature at the maximum peak position of the endothermic curve obtained in the temperature rise measurement with a differential scanning calorimeter ( Tm (° C.)) and the number of short chain branches per 1000 carbon atoms (SCB) obtained from the measurement of infrared absorption spectrum satisfy the relationship of the formula (1).
Tm <−1.8 × SCB + 140 (1)
(C) α-olefin has 3 to 12 carbon atoms ビニル芳香族炭化水素とオレフィン又はジオレフィンとの熱可塑性ブロック共重合体（Ｅ）が、水素添加スチレン−ブタジエン−ジブロック共重合体と水素添加スチレン−ブタジエン−スチレン−トリブロック共重合体の混合物であり、その混合比が５／５〜９／１であり、かつスチレン含量が２０〜５０重量％であることを特徴とする請求項１〜４のいずれかに記載の容器の蓋材シーラント用接着剤。   A thermoplastic block copolymer (E) of a vinyl aromatic hydrocarbon and an olefin or diolefin is a mixture of a hydrogenated styrene-butadiene-diblock copolymer and a hydrogenated styrene-butadiene-styrene-triblock copolymer. The mixture ratio is 5/5 to 9/1, and the styrene content is 20 to 50% by weight. The container cover material sealant according to any one of claims 1 to 4, adhesive. 容器がポリエチレンテレフタレートを主成分とすることを特徴とする請求項１〜６のいずれかに記載の容器の蓋材シーラント用接着剤。   The container is made of polyethylene terephthalate as a main component, and the container sealant sealant adhesive according to any one of claims 1 to 6. 請求項１〜７のいずれかに記載の容器の蓋材シーラント用接着剤からなる層、及び支持基材層の少なくとも２層を含む構成からなる容器の蓋材用フィルム。   A film for a lid material of a container, comprising a layer comprising an adhesive for a sealant for a lid material of a container according to any one of claims 1 to 7 and a support base material layer.
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