JP6855820B2 - Crosslinked ethylene-vinyl acetate copolymer saponified product, hot melt adhesive resin composition, adhesive and molded article thereof - Google Patents

Crosslinked ethylene-vinyl acetate copolymer saponified product, hot melt adhesive resin composition, adhesive and molded article thereof Download PDF

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JP6855820B2
JP6855820B2 JP2017017705A JP2017017705A JP6855820B2 JP 6855820 B2 JP6855820 B2 JP 6855820B2 JP 2017017705 A JP2017017705 A JP 2017017705A JP 2017017705 A JP2017017705 A JP 2017017705A JP 6855820 B2 JP6855820 B2 JP 6855820B2
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vinyl acetate
resin composition
acetate copolymer
melt adhesive
adhesive resin
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真都 大嶽
真都 大嶽
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Tosoh Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/12—Hydrolysis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10697—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer being cross-linked
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10788—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing ethylene vinylacetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
    • C08L23/0861—Saponified vinylacetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L93/00—Compositions of natural resins; Compositions of derivatives thereof
    • C08L93/04—Rosin
    • 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
    • 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
    • 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
    • C09J123/0861—Saponified 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
    • C09J131/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Adhesives based on derivatives of such polymers
    • C09J131/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C09J131/04—Homopolymers or copolymers of vinyl acetate
    • 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
    • C09J7/10—Adhesives in the form of films or foils without carriers

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Joining Of Glass To Other Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Laminated Bodies (AREA)

Description

本発明は、架橋エチレン−酢酸ビニル共重合体ケン化物、これを含むホットメルト接着剤樹脂組成物及びこれらよりなる接着剤、成形体に関するものである。 The present invention relates to a crosslinked ethylene-vinyl acetate copolymer saponified product, a hot melt adhesive resin composition containing the crosslinked ethylene-vinyl acetate copolymer, an adhesive comprising these, and a molded product.

エチレン−酢酸ビニル共重合体は、側鎖にアセトキシ基を有していることから、ポリエチレンと比較して、柔軟性、接着性に優れており、食品や工業用の接着剤として幅広く利用されている。エチレン−酢酸ビニル共重合体のアセトキシ基の量が多くなると、柔軟性や接着性が良好になるものの、融解温度が下がるため、耐熱性が要求される用途では実用上の問題が生じることがある。そこで、耐熱性を確保するために分子間の架橋を形成させ耐熱性を向上させる樹脂組成物や架橋方法として、エチレン−酢酸ビニル共重合体に有機過酸化物を配合して溶融混練による加熱又は高周波誘導加熱により架橋する方法、エチレン−酢酸ビニル共重合体よりも耐熱性がある他の樹脂と有機過酸化物を配合し加熱処理にて架橋させる方法、成形体に電子線やガンマ線などを照射して架橋させる方法が提案されている（例えば特許文献１〜４参照）。また、エチレン−酢酸ビニル共重合体ケン化物は、側鎖に水酸基を有していることから、エチレン−酢酸ビニル共重合体と比較して金属、プラスチック、ガラス等との接着性に優れおり、ホットメルト系接着剤として利用されている。エチレン−酢酸ビニル共重合体ケン化物は、アセトキシ基に対し水酸基の量が多くなると、結晶性が増して透明性や接着性が低下するため、両者のバランスを確保する目的でエチレン−酢酸ビニル共重合体ケン化物に不飽和カルボン酸をグラフトさせた酸変性物が提案されている（例えば特許文献５参照）。合わせガラス中間膜に用いられる接着剤は、低温接着性、透明性、耐貫通性などの特性に加えて、建材、車両、電子デバイス向けの用途や使用環境に応じて耐熱性、耐水性、耐湿熱性などの耐久性が求められる。これら一連の要求特性を満足する樹脂組成物を構成する材料として、エチレン−酢酸ビニル共重合体やエチレン−酢酸ビニル共重合体ケン化物が利用されている。 Since the ethylene-vinyl acetate copolymer has an acetoxy group in the side chain, it has excellent flexibility and adhesiveness as compared with polyethylene, and is widely used as an adhesive for foods and industries. There is. When the amount of acetoxy groups in the ethylene-vinyl acetate copolymer is large, the flexibility and adhesiveness are improved, but the melting temperature is lowered, which may cause practical problems in applications requiring heat resistance. .. Therefore, as a resin composition for improving heat resistance by forming crosslinks between molecules in order to secure heat resistance, or as a cross-linking method, an organic peroxide is blended with an ethylene-vinyl acetate copolymer and heated by melt-kneading. A method of cross-linking by high-frequency induction heating, a method of blending an organic peroxide with another resin having heat resistance than an ethylene-vinyl acetate copolymer and cross-linking by heat treatment, and irradiating a molded body with electron beams or gamma rays. (See, for example, Patent Documents 1 to 4). Further, since the ethylene-vinyl acetate copolymer saponified product has a hydroxyl group in the side chain, it has excellent adhesiveness to metals, plastics, glass, etc. as compared with the ethylene-vinyl acetate copolymer. It is used as a hot melt adhesive. When the amount of hydroxyl groups in the ethylene-vinyl acetate copolymer saponified product is large with respect to the acetoxy group, the crystallinity increases and the transparency and adhesiveness decrease. Therefore, both ethylene-vinyl acetate are used for the purpose of ensuring a balance between the two. An acid-modified product obtained by grafting an unsaturated carboxylic acid onto a polymer saponified product has been proposed (see, for example, Patent Document 5). The adhesive used for the laminated glass interlayer film has properties such as low temperature adhesiveness, transparency, and penetration resistance, as well as heat resistance, water resistance, and moisture resistance depending on the application and usage environment for building materials, vehicles, and electronic devices. Durability such as heat is required. Ethylene-vinyl acetate copolymers and ethylene-vinyl acetate copolymer saponified products are used as materials for constituting resin compositions that satisfy these series of required properties.

特開平７−１１８０３８号公報（例えば特許請求の範囲参照）JP-A-7-118038 (see, for example, claims) 特開２００８−１５９８５６号公報（例えば特許請求の範囲参照）Japanese Unexamined Patent Publication No. 2008-159856 (see, for example, claims) 特開２００１−３１０４１８号公報（例えば特許請求の範囲参照）Japanese Unexamined Patent Publication No. 2001-310418 (see, for example, claims) 特開２００１−２０６９９３号公報（例えば特許請求の範囲参照）Japanese Unexamined Patent Publication No. 2001-2099993 (see, for example, claims) 特開平３−１１２８３６号公報（例えば特許請求の範囲参照）JP-A-3-112836 (see, for example, claims)

特許文献１〜３で提案されている樹脂組成物や成形体は、エチレン−酢酸ビニル共重合体の耐熱性は向上するものの、長期間にわたる湿熱環境下において白化を生じ外観変化に加えて、透明性が低下する問題がある。特許文献４では、電子線照射で架橋したエチレン−酢酸ビニル共重合体からなる成形体の提案があるが、架橋度が高いと耐熱性は優れたものになるものの、ガラス等の被着体に対する接着性が低下したり、照射にかかるコストの問題もある。また、特許文献５で提案されている酸変性物は、ガラスとラミネートする温度が高いとガラス端面より溶融した酸変性物がはみ出して、工程上のハンドリングを悪化させる問題が生じたり、ラミネート後の合わせガラスを９０〜１１０℃で再加熱すると、酸変性物が軟化してガラス同士にズレや剥離が生じたり、ガラス端面から軟化した酸変性物がはみ出して外観上の問題が生じるなど耐熱性が十分とはいえない。そこで、本発明では上記課題を解決し、得られる樹脂組成物がガラス等の被着体への低温接着が可能であり、耐熱性に加え、高温高湿熱環境下におかれても優れた透明性、接着性を有するホットメルト接着剤樹脂組成物、接着剤及びそれよりなる成形体を提供しようとするものである。 The resin compositions and molded articles proposed in Patent Documents 1 to 3 have improved heat resistance of the ethylene-vinyl acetate copolymer, but cause whitening in a moist heat environment for a long period of time, and in addition to changing the appearance, they are transparent. There is a problem of reduced sex. Patent Document 4 proposes a molded product made of an ethylene-vinyl acetate copolymer crosslinked by electron beam irradiation. Although the heat resistance becomes excellent when the degree of crosslinking is high, it is applied to an adherend such as glass. There is also the problem of reduced adhesiveness and the cost of irradiation. Further, in the acid-modified product proposed in Patent Document 5, if the temperature at which the glass is laminated is high, the melted acid-modified product protrudes from the end face of the glass, causing a problem of deteriorating handling in the process, or after laminating. When the laminated glass is reheated at 90 to 110 ° C., the acid-modified product softens and the glasses are displaced or peeled off, or the softened acid-modified product protrudes from the end face of the glass, causing an appearance problem. Not enough. Therefore, the present invention solves the above problems, and the obtained resin composition can be adhered to an adherend such as glass at a low temperature, and in addition to heat resistance, it is excellently transparent even when placed in a high temperature and high humidity environment. An object of the present invention is to provide a hot melt adhesive resin composition having properties and adhesiveness, an adhesive, and a molded product comprising the same.

そこで、本発明者らは、上記課題に対し鋭意検討した結果、特定の架橋エチレン−酢酸ビニル共重合体ケン化物を用いることにより、低温接着性、透明性、耐熱性、耐湿熱性に優れた接着性樹脂組成物、接着剤及びそれよりなる成形体が得られることを見出し、本発明を完成するに至った。 Therefore, as a result of diligent studies on the above problems, the present inventors have excellent adhesion at low temperature, transparency, heat resistance, and moisture heat resistance by using a specific crosslinked ethylene-vinyl acetate copolymer saponified product. They have found that a sex resin composition, an adhesive, and a molded product made of the same can be obtained, and have completed the present invention.

即ち、本発明は、特定の架橋エチレン−酢酸ビニル共重合体ケン化物及びこれを含むことを特徴とするホットメルト接着剤樹脂組成物、接着剤及びそれよりなる成形体に関するものである。 That is, the present invention relates to a specific crosslinked ethylene-vinyl acetate copolymer saponified product, a hot melt adhesive resin composition containing the same, an adhesive, and a molded product comprising the same.

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

本発明の架橋エチレン−酢酸ビニル共重合体ケン化物（Ａ）は、エチレン残基単位７５．４〜９４．６モル％、酢酸ビニル残基単位２．２〜２２．１モル％、ビニルアルコール残基単位０．５〜１４．７モル％を含み、ゲル分が０．００１〜０．５％、動的粘弾性測定にて得られる周波数１０Ｈｚの弾性率において、ＪＩＳ Ｋ６９２４−２で測定した融点より２０〜５０℃高い温度における弾性率（Ｅ’）が１０５Ｐａ以上で、温度に対する弾性率の傾き（ｌｏｇ│ΔＥ’／ΔＴ│）が５以下、ＪＩＳ Ｋ６９２４−１で測定したメルトマスフローレイトが０．０１〜１００ｇ／１０分を満たすものである。 The crosslinked ethylene-vinyl acetate copolymer saponified product (A) of the present invention has an ethylene residue unit of 75.4 to 94.6 mol%, a vinyl acetate residue unit of 2.2 to 22.1 mol%, and a vinyl alcohol residue. The melting point measured by JIS K6924-2 at the elastic modulus of a frequency of 10 Hz obtained by dynamic viscoelasticity measurement, containing 0.5 to 14.7 mol% of the group unit and 0.001 to 0.5% of gel content. 'in the 10 5 Pa or more, the slope of elastic modulus with respect to temperature (Log￨derutaE more 20 to 50 ° C. elastic modulus at high temperatures (E)' / ΔT│) of 5 or less, melt mass flow rate measured by JIS K6924-1 Satisfies 0.01 to 100 g / 10 minutes.

本発明の架橋エチレン−酢酸ビニル共重合体ケン化物（Ａ）の酢酸ビニル残基単位は、２．２〜２２．１モル％の範囲にあり、ホットメルト接着剤樹脂組成物とした場合に被着体に対する低温接着性や透明性がより優れたものとなることから、４．９〜１７．２モル％の範囲にあるものがより好ましい。ここで、酢酸ビニル残基量が２．２モル％未満の場合、得られる接着剤樹脂組成物やその成形体は低温接着性に劣るものとなる。一方、酢酸ビニル残基量が２２．１モル％を超える場合は、常温での粘着性が強く、軟化温度も低くなるため、得られる樹脂組成物や成形体は耐ブロッキング性に劣るものとなり、ハンドリング面に問題が生じる。また、ビニルアルコール残基単位は、０．５〜１４．７モル％の範囲であり、耐熱性、接着性、耐水性、耐湿熱性により優れたものとなることから、１．０〜９．５モル％がより好ましい。ビニルアルコール残基単位が０．５モル％未満の場合は、得られる接着剤樹脂組成物やその成形体の耐湿熱性が十分でなく、特に高温高湿熱環境下において膨潤による白化が生じて透明性が著しく低下したり、被着体との部分的な剥離が生じる等の問題がある。一方、ビニルアルコール残基単位が１４．７モル％を超える場合は、得られる樹脂組成物や成形体の結晶性が増して膨潤による白化は抑制されるものの、微結晶散乱による透明性の低下に加え、剛性が増して被着体との接着性が低下する問題が生じる。 The vinyl acetate residue unit of the crosslinked ethylene-vinyl acetate copolymer saponified product (A) of the present invention is in the range of 2.2 to 22.1 mol%, and is applied when it is used as a hot melt adhesive resin composition. It is more preferably in the range of 4.9 to 17.2 mol% because it has better low-temperature adhesiveness and transparency to the body. Here, when the amount of vinyl acetate residue is less than 2.2 mol%, the obtained adhesive resin composition and its molded product are inferior in low-temperature adhesiveness. On the other hand, when the amount of vinyl acetate residue exceeds 22.1 mol%, the adhesiveness at room temperature is strong and the softening temperature is low, so that the obtained resin composition or molded product is inferior in blocking resistance. There is a problem with the handling surface. The vinyl alcohol residue unit is in the range of 0.5 to 14.7 mol%, and is more excellent in heat resistance, adhesiveness, water resistance, and moisture heat resistance. Therefore, it is 1.0 to 9.5. More preferably mol%. When the vinyl alcohol residue unit is less than 0.5 mol%, the obtained adhesive resin composition and its molded product have insufficient moist heat resistance, and whitening due to swelling occurs particularly in a high temperature and high moist heat environment to cause transparency. There are problems such as a significant decrease in the amount of resin and partial peeling from the adherend. On the other hand, when the vinyl alcohol residue unit exceeds 14.7 mol%, the crystallinity of the obtained resin composition or molded product is increased and whitening due to swelling is suppressed, but the transparency is lowered due to fine crystal scattering. In addition, there arises a problem that the rigidity is increased and the adhesiveness with the adherend is lowered.

架橋エチレン−酢酸ビニル共重合体ケン化物（Ａ）の酢酸ビニル残基単位とビニルアルコール残基単位は、例えば、ＪＩＳ Ｋ６９２４−１で測定されるケン化前後の架橋エチレン−酢酸ビニル共重合体の酢酸ビニル含有率より求めることができる。 The vinyl acetate residue unit and vinyl alcohol residue unit of the crosslinked ethylene-vinyl acetate copolymer saponified product (A) are, for example, those of the crosslinked ethylene-vinyl acetate copolymer before and after saponification measured by JIS K6924-1. It can be obtained from the vinyl acetate content.

ゲル分は、架橋エチレン−酢酸ビニル共重合体ケン化物（Ａ）の耐熱性に関わる架橋度合いや被着体への接着性に加えて、成形時のフィッシュアイが少ない等品質上優れた成形体を得るために規定するものであり、０．００１〜０．５％の範囲であり、耐熱性、接着性、成形体外観の良好なバランスを得るために０．００５〜０．２％の範囲にあることがより好ましい。ゲル分が０．５％を超えると、成形体表面に存在するフィッシュアイが多くなる影響で被着体との密着性が低下したり、成形体の外観が劣るものとなる。また、ゲル分が０．００１％未満では、架橋の度合いが不十分であり、耐熱性に劣るものとなる。ここで示すゲル分は、架橋エチレン−酢酸ビニル共重合体ケン化物を７５℃、２時間キシレン中で加熱処理して溶解させた後、４００メッシュの金網で濾過した後の残分であり、処理前の重量に対する比率で示される。 The gel content is a molded product with excellent quality, such as the degree of cross-linking related to the heat resistance of the cross-linked ethylene-vinyl acetate copolymer (A) and the adhesiveness to the adherend, as well as less fish eyes during molding. The range is 0.001 to 0.5%, and the range is 0.005 to 0.2% in order to obtain a good balance between heat resistance, adhesiveness, and appearance of the molded product. It is more preferable to be in. When the gel content exceeds 0.5%, the adhesion to the adherend is lowered or the appearance of the molded body is deteriorated due to the influence of the increase in the number of fish eyes present on the surface of the molded body. If the gel content is less than 0.001%, the degree of cross-linking is insufficient and the heat resistance is inferior. The gel content shown here is the residue after the crosslinked ethylene-vinyl acetate copolymer saponified product was dissolved by heat treatment in xylene at 75 ° C. for 2 hours and then filtered through a 400 mesh wire mesh. Shown as a percentage of the previous weight.

弾性率（Ｅ’）は、架橋エチレン−酢酸ビニル共重合体ケン化物（Ａ）の長期に渡る耐熱性、耐湿熱性に関わる耐久性に優れたものを得るために規定するものであり、融解温度以上の温度に成形体が暴露されたり更には高湿環境下に曝される時の外観変化（変形など）が実用上問題のない優れた耐久性を得るため、ＪＩＳ Ｋ６９２４−２で測定した融解温度より２０〜５０℃高い温度における弾性率（Ｅ’）が１０５Ｐａ以上であり、温度に対する弾性率の傾き（ｌｏｇ│ΔＥ’／ΔＴ│）が５以下である。より高温で、かつ高湿下において、長期にわたる成形体の形状、外観維持がより優れたものとなることから、弾性率（Ｅ’）は１０５〜１０７Ｐａの範囲にあり、傾きは１から５の範囲であることがより好ましい。弾性率が１０５Ｐａ未満では、弾性率が低すぎて変形しやすく成形体の形状保持が不十分であり、傾きが５を超えると温度に対する弾性率の変化が著しく大きくなり、耐熱性が維持できる適用可能な環境温度が非常に狭くなり、実用上劣るものとなる。ここで示す弾性率とは、レオメーター等を用いて動的粘弾性測定で得られる固体の弾性率（Ｅ’）であり、周波数１０Ｈｚ、引張モードにて温度に対する弾性率を測定することにより得られるものである。弾性率の傾きは、ＪＩＳ Ｋ６９２４−２に準拠し測定して得られる架橋エチレン−酢酸ビニル共重合体ケン化物の融解温度に対し、２０〜５０℃高い温度範囲における弾性率の傾きを一次近似にて算出し、その絶対値の常用対数で表すことで得られる。 The elastic modulus (E') is defined in order to obtain a crosslinked ethylene-vinyl acetate copolymer saponified product (A) having excellent durability related to long-term heat resistance and moist heat resistance, and is defined as a melting temperature. Melting measured by JIS K6924-2 in order to obtain excellent durability with no practical problem in appearance changes (deformation, etc.) when the molded product is exposed to the above temperature or even in a high humidity environment. modulus at 20 to 50 ° C. higher than the temperature (E ') is not less 10 5 Pa or more, the slope of elastic modulus with respect to temperature (log│ΔE' / ΔT│) is 5 or less. At higher temperatures, and at high humidity, there shape of long moldings, since it becomes appearance maintain more excellent, in the range of elastic modulus (E ') is 10 5 to 10 7 Pa, the slope 1 More preferably, it is in the range of to 5. The elastic modulus of less than 10 5 Pa, is insufficient shape retention of the deformed easily molded body modulus too low, the slope is the change in modulus increases significantly for more than 5 temperature, heat resistance is maintained The applicable environmental temperature that can be applied becomes very narrow, which is inferior in practical use. The elastic modulus shown here is the elastic modulus (E') of a solid obtained by dynamic viscoelasticity measurement using a rheometer or the like, and is obtained by measuring the elastic modulus with respect to temperature in a tension mode at a frequency of 10 Hz. Is something that can be done. The slope of the elastic modulus is a first-order approximation of the slope of the elastic modulus in the temperature range 20 to 50 ° C higher than the melting temperature of the crosslinked ethylene-vinyl acetate copolymer saponified product obtained by measuring in accordance with JIS K6924-2. It is obtained by calculating it and expressing it as the common logarithm of its absolute value.

架橋エチレン−酢酸ビニル共重合体ケン化物（Ａ）のメルトマスフローレイト（ＭＦＲ）は、ＪＩＳ Ｋ ６９２４−１に準拠して温度１９０℃、荷重２１．１８Ｎで測定したメルトマスフローレイトが０．０１〜１００ｇ／１０分の範囲であり、押出し成形性により優れたものとするため、０．５〜４０ｇ／１０分の範囲にあることがより好ましい。メルトマスフローレイトが０．０１ｇ／１０分未満の場合、成形時の押出し負荷や樹脂圧力が高くなり加工性に劣るものとなり、１００ｇ／１０分を超えると、溶融時のドローダウン性が大きくなりコンパウンド時のハンドリングや賦形性に劣るものとなる。 The melt mass flow rate (MFR) of the crosslinked ethylene-vinyl acetate copolymer saponified product (A) has a melt mass flow rate of 0.01 to 0.01 as measured at a temperature of 190 ° C. and a load of 21.18 N in accordance with JIS K 6924-1. It is in the range of 100 g / 10 minutes, and is more preferably in the range of 0.5 to 40 g / 10 minutes in order to improve the extrusion moldability. If the melt mass flow rate is less than 0.01 g / 10 minutes, the extrusion load and resin pressure during molding will increase and the workability will be inferior. If it exceeds 100 g / 10 minutes, the drawdown property during melting will increase and the compound will be compounded. It will be inferior in handling and formability at the time.

本発明のホットメルト接着剤樹脂組成物は、前記架橋エチレン−酢酸ビニル共重合体ケン化物（Ａ）１００重量部にタッキファイヤー（Ｂ）５〜３０重量部を含むものである。ホットメルト接着剤樹脂組成物を構成するタッキファイヤー（Ｂ）は、主に透明性を向上させる目的で配合される。具体的には、脂肪族系炭化水素樹脂、脂環族系炭化水素樹脂、芳香族系炭化水素樹脂、ポリテルペン系樹脂、ロジン類が挙げられる。脂肪族系炭化水素樹脂としては、１−ブテン、ブタジエン、イソブチレン、１，３−ペンタジエン等のＣ４〜Ｃ５のモノまたはジオレフィンを主体とする重合体、脂環族系炭化水素樹脂としては、スペントＣ４〜Ｃ５留分中のジエン成分を環化二量体化後重合させた樹脂、シクロペンタジエン等の環状モノマーを重合させた樹脂、芳香族系炭化水素樹脂としては、ビニルトルエン、インデン、α−メチルトルエン等のＣ２ビニル芳香族系炭化水素樹脂を成分とした樹脂等、ポリテルペン系樹脂としては、α−ピネン重合体、β−ピネン重合体、ジペンテン重合体、テルペン−フェノール共重合体等、ロジン類としては、ロジン、重合ロジン、水添ロジン、ロジングリセリンエステルおよびその水添物または重合物、ロジンペンタエリスリトールおよびその水添物または重合物等が挙げられる。これらのタッキファイヤーの中では、架橋エチレン−酢酸ビニル共重合体ケン化物との相溶性や色相の点から、軟化温度が低い部分水素化した石油炭化水素樹脂や水素添加ロジンエステルがより好ましい。架橋エチレン−酢酸ビニル共重合体ケン化物（Ａ）１００重量部に対するタッキファイヤーの配合量は５〜３０重量部であり、成形体の透明性や常温における成形体のハンドリングをより優れたものとするため、１０〜２０重量部がより好ましい。タッキファイヤーの配合量が５重量部未満では透明性が改良されず、３０重量部を超えると溶融した樹脂組成物の粘着性が強くなり、押出しストランドのカッティングが安定せず、また得られる成形体のハンドリング性に劣るものとなる。 The hot melt adhesive resin composition of the present invention contains 5 to 30 parts by weight of tackfire (B) in 100 parts by weight of the crosslinked ethylene-vinyl acetate copolymer saponified product (A). The tack fire (B) constituting the hot melt adhesive resin composition is blended mainly for the purpose of improving transparency. Specific examples thereof include aliphatic hydrocarbon resins, alicyclic hydrocarbon resins, aromatic hydrocarbon resins, polyterpene resins, and rosins. As the aliphatic hydrocarbon resin, a polymer mainly composed of C4 to C5 mono or diolefin such as 1-butene, butadiene, isobutylene, 1,3-pentadien, and as an alicyclic hydrocarbon resin, Spent Resins obtained by polymerizing the diene component in the C4 to C5 distillates after cyclization dimerization, resins obtained by polymerizing cyclic monomers such as cyclopentadiene, and aromatic hydrocarbon resins include vinyltoluene, inden, and α-. Resins containing C2 vinyl aromatic hydrocarbon resins such as methyltoluene and other polyterpene resins include α-pinene polymer, β-pinene polymer, dipentene polymer, terpene-phenol copolymer and the like. Examples thereof include rosin, polymerized rosin, hydrocarbon rosin, rosing lyserin ester and its hydrogenated product or polymer, rosin pentaerythritol and its hydrocarbon or polymer, and the like. Among these tack fires, partially hydrogenated petroleum hydrocarbon resins and hydrogenated rosin esters having a low softening temperature are more preferable from the viewpoint of compatibility with crosslinked ethylene-vinyl acetate copolymer saponified products and hue. The compounding amount of the tack fire with respect to 100 parts by weight of the crosslinked ethylene-vinyl acetate copolymer saponified product (A) is 5 to 30 parts by weight, and the transparency of the molded product and the handling of the molded product at room temperature are further improved. Therefore, 10 to 20 parts by weight is more preferable. If the blending amount of the tack fire is less than 5 parts by weight, the transparency is not improved, and if it exceeds 30 parts by weight, the adhesiveness of the molten resin composition becomes strong, the cutting of the extruded strand is not stable, and the obtained molded product is obtained. It will be inferior in handleability.

本発明のホットメルト接着剤樹脂組成物は、さらに、少なくともエポキシ基、アクリル基、メタクリル基又はイソシナネート基の何れかの有機官能基を有するシラン化合物（Ｃ）０．０１〜１重量部及び／又は酸変性エチレン−酢酸ビニル共重合体（Ｄ）１〜２０重量部を含んでいても良い。 The hot melt adhesive resin composition of the present invention further comprises 0.01 to 1 part by weight of a silane compound (C) having an organic functional group of at least an epoxy group, an acrylic group, a methacryl group or an isocinate group and / or It may contain 1 to 20 parts by weight of the acid-modified ethylene-vinyl acetate copolymer (D).

本発明のホットメルト接着剤樹脂組成物を構成するシラン化合物（Ｃ）の具体的例示としては、エポキシ基を有するものとしては、２−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、３−グリシドキシプロピルメチルジメトキシシラン、３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルメチルジエトキシシラン、３−グリシドキシプロピルトリエトキシシラン、メタクリル基を有するものとしては、３−メタクリロキシプロピルメチルジメトキシシラン、３−メタクリロキシプロピルトリメトキシシラン、３−メタクリロキシプロピルメチルジエトキシシラン、３−メタクリロキシプロピルトリエトキシシラン、アクリル基を有するものとしては、３−アクリロキシプロピルトリメトキシシラン、イソシアネート基を有するものとしては、３−イソシアネートプロピルトリエトキシシランが挙げられる。このようなシラン化合物（Ｃ）の具体的商品としては、例えば、「ＫＢＭ−３０３」、「ＫＢＭ−４０２」、「ＫＢＭ−４０３」、「ＫＢＭ−５０３」、「ＫＢＭ−５１０３」、「ＫＢＥ−９００７」（商品名、信越シリコーン社製）、「Ｚ−６０４０」、「Ｚ−６０４４」、「Ｚ−６０３０」（商品名、東レ・ダウコーニング社製）、などを挙げることができる。ガラスとの接着性に優れ、特に湿熱環境下、水への浸漬環境下における接着性に優れる樹脂組成物が得られることから、エポキシ系、メタクリル系、アクリル系、イソシアネート系のシランカップリング剤が好ましい。 As a specific example of the silane compound (C) constituting the hot melt adhesive resin composition of the present invention, 2- (3,4-epylcyclohexyl) ethyltrimethoxysilane, 3- Glycydoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methacry as having a methacryl group Loxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane as having an acrylic group Examples of those having an isocyanate group include 3-isocyanate propyltriethoxysilane. Specific products of such a silane compound (C) include, for example, "KBM-303", "KBM-402", "KBM-403", "KBM-503", "KBM-5103", "KBE-". 9007 ”(trade name, manufactured by Shin-Etsu Silicone Co., Ltd.),“ Z-6040 ”,“ Z-6044 ”,“ Z-6030 ”(trade name, manufactured by Toray Dow Corning Co., Ltd.), and the like. Epoxy-based, methacrylic-based, acrylic-based, and isocyanate-based silane coupling agents can be used because a resin composition having excellent adhesiveness to glass and particularly excellent adhesiveness in a moist heat environment and an environment immersed in water can be obtained. preferable.

シラン化合物（Ｃ）の含有量としては、架橋エチレン−酢酸ビニル共重合体ケン化物（Ａ）１００重量部に対して０．０１〜１重量部が好ましく、得られる樹脂組成物の湿熱環境下、水への浸漬環境下における接着の維持、自己縮合によるゲル化防止の点において物性や品質がより向上することから、０．０５〜０．７重量部であることがより好ましい。また、シラン化合物（Ｃ）は、得られる組成物に求められる特性を阻害しない範囲であれば１種類でもよく、または２種類以上併用してもよい。 The content of the silane compound (C) is preferably 0.01 to 1 part by weight with respect to 100 parts by weight of the crosslinked ethylene-vinyl acetate copolymer saponified product (A) under a moist heat environment of the obtained resin composition. The amount is more preferably 0.05 to 0.7 parts by weight because the physical properties and quality are further improved in terms of maintaining adhesion in an environment immersed in water and preventing gelation due to self-condensation. Further, the silane compound (C) may be used alone or in combination of two or more as long as it does not impair the properties required for the obtained composition.

本発明のホットメルト接着剤樹脂組成物を構成する酸変性エチレン−酢酸ビニル共重合体（Ｄ）は、エチレン−酢酸ビニル共重合体を酸変性したものであり、具体的には、高圧でエチレンと酢酸ビニルと不飽和カルボン酸またはその無水物とをラジカル重合する方法、不飽和カルボン酸またはその無水物を該エチレン−酢酸ビニル共重合体にグラフトする方法が挙げられる。不飽和カルボン酸またはその無水物としては、アクリル酸、フマル酸、メタクリル酸、マレイン酸、イタコン酸、シトラコン酸、メサコン酸、無水マレイン酸、無水シトラコン酸、無水イタコン酸、４−メチルシクロヘキサ−４−エン−１，２−ジカルボン酸無水物、ビシクロ（２，２，２）オクタ−５−エン−２，３−ジカルボン酸無水物等が挙げられ、これらの物が単独または混合物として用いられる。グラフトする方法としては、例えば、有機過酸化物を触媒として、溶融押出法あるいは該エチレン系共重合体を適当な溶媒中に懸濁または溶解した溶液法によりグラフトする方法が挙げられ、この酸変性物は、特開平６−９９３２号公報に記載されている方法等によって製造される。酸変性エチレン−酢酸ビニル共重合体（Ｄ）の配合量は、１〜２０重量部であることが好ましく、耐熱性、透明性、接着性のバランスをより優れたものとするために５〜１５重量部がより好ましい。 The acid-modified ethylene-vinyl acetate copolymer (D) constituting the hot-melt adhesive resin composition of the present invention is an acid-modified ethylene-vinyl acetate copolymer, and specifically, ethylene at high pressure. A method of radically polymerizing vinyl acetate and an unsaturated carboxylic acid or an anhydride thereof, and a method of grafting an unsaturated carboxylic acid or an anhydride thereof on the ethylene-vinyl acetate copolymer. As unsaturated carboxylic acid or its anhydride, acrylic acid, fumaric acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, maleic anhydride, citraconic anhydride, itaconic anhydride, 4-methylcyclohexa- Examples thereof include 4-ene-1,2-dicarboxylic acid anhydride, bicyclo (2,2,2) octa-5-ene-2,3-dicarboxylic acid anhydride, and these are used alone or as a mixture. .. Examples of the method of grafting include a method of grafting using an organic peroxide as a catalyst by a melt extrusion method or a solution method in which the ethylene-based copolymer is suspended or dissolved in an appropriate solvent, and this acid modification is used. The product is manufactured by the method described in JP-A-6-9932. The blending amount of the acid-modified ethylene-vinyl acetate copolymer (D) is preferably 1 to 20 parts by weight, and 5 to 15 in order to improve the balance between heat resistance, transparency and adhesiveness. Parts by weight are more preferred.

本発明の架橋エチレン−酢酸ビニル共重合体ケン化物（Ａ）は、例えば高圧法、乳化法など公知の製造法によって得られるエチレン−酢酸ビニル共重合体を有機過酸化物等にて架橋させた後にケン化して得られる方法、高圧法、乳化法など公知の製造法によって得られるエチレン−酢酸ビニル共重合体をケン化した後有機過酸化物等にて架橋する方法が挙げられ、架橋体の耐熱性が優れることから、架橋させた後にケン化する方法が好ましい。有機過酸化物の他に電子線やガンマ線照射による方法も挙げられるが、生産性やコストの面で有機過酸化物による架橋方法好ましい。有機過酸化物は、エチレン−酢酸ビニル共重合体の融解温度を考慮して、１分間の半減期を得る温度が１００〜１８０℃が適している。具体的には、シクロヘキサノンペルオキシド、ジクミルペルオキシド、ｔ−ブチルクミルペルオキシド、ジアシルペルオキシド、ジプロピオニルペルオキシド、ジデカノイルペルオキシド、ジラウロイルペルオキシド、ビス（３，５，５−トリメチルヘキサノイル）ペルオキシド、ベンゾイルペルオキシド、ｍ−トルイルペルオキシド、２，４−ジクロロベンゾイルペルオキシド、１，１−ジ−ｔ−ブチルペルオキシシクロヘキサン、１，１−ジ（ｔ−ブチルペルオキシ）−３，５−トリメチルシクロヘキサン、２，５−ジメチル−２，５−ジ（ｔ−ブチルペルオキシ）ヘキサン、１，３−ジ（ｔ−ブチルペルオキシイソプロピル）ベンゼン、２，５−ジメチル−２，５−ジベンゾイルペルオキシヘキサン、ｎ−ブチル−４，４−ビス（ｔ−ブチルペルオキシ）バレレート、ｔ−ブチルペルオキシアセテート、ｔ−ブチルペルオキシイソブチレート、ｔ−ブチルペルオキシピバレート、ｔ−ブチルペルオキシネオデカノエート、ｔ−ブチルペルオキシ−３，５，５−トリメチルヘキサノエート、ｔ−ブチルペルオキシ−２−エチルヘキサノエート、ｔ−ブチルペルオキシラウレート、ｔ−ブチルペルオキシベンゾエート、ジ（ｔ−ブチルペルオキシ）イソフタレート、ｔ−ブチルペルオキシマレート、メチルエチルケトンペルオキシド等が挙げられる。これらの有機過酸化物のうち、少なくとも一種以上を用いることができる。また、必要により架橋助剤としてエチレングリコールジメタクリレート、トリメチロールプロパントリメタクリレート、トリアリルシアヌレート、トリアリルイソシアヌレート等の多官能性モノマー、１，２−ポリブタジエン等の多官能性ポリマー、硫黄化合物等を配合しても良い。架橋エチレン−酢酸ビニル共重合体の製造方法としては、如何なる方法を用いてもよく、例えばミキサー、ロールミル、単軸押出機、２軸押出機などの混練機を用い混合する方法などを挙げることができる。 The crosslinked ethylene-vinyl acetate copolymer saponified product (A) of the present invention is obtained by cross-linking an ethylene-vinyl acetate copolymer obtained by a known production method such as a high pressure method or an emulsification method with an organic peroxide or the like. Examples thereof include a method obtained by later saponification, a method obtained by saponifying an ethylene-vinyl acetate copolymer obtained by a known production method such as a high pressure method and an emulsification method, and then cross-linking with an organic peroxide or the like. Since it has excellent heat resistance, a method of cross-linking and then saponifying is preferable. In addition to the organic peroxide, a method using electron beam or gamma ray irradiation can be mentioned, but a cross-linking method using an organic peroxide is preferable in terms of productivity and cost. The temperature at which the half-life of 1 minute is obtained is preferably 100 to 180 ° C. in consideration of the melting temperature of the ethylene-vinyl acetate copolymer. Specifically, cyclohexanone peroxide, dicumyl peroxide, t-butylcumyl peroxide, diacyl peroxide, dipropionyl peroxide, didecanoyl peroxide, dilauroyl peroxide, bis (3,5,5-trimethylhexanoyl) peroxide, benzoyl. Peroxide, m-toluyl peroxide, 2,4-dichlorobenzoyl peroxide, 1,1-di-t-butylperoxycyclohexane, 1,1-di (t-butylperoxy) -3,5-trimethylcyclohexane, 2,5- Dimethyl-2,5-di (t-butylperoxy) hexane, 1,3-di (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-dibenzoylperoxyhexane, n-butyl-4, 4-Bis (t-butylperoxy) valerate, t-butylperoxyacetate, t-butylperoxyisobutyrate, t-butylperoxypivalate, t-butylperoxyneodecanoate, t-butylperoxy-3,5 5-trimethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate, di (t-butylperoxy) isophthalate, t-butylperoxymalate, methylethylketone Peroxide and the like can be mentioned. Of these organic peroxides, at least one or more can be used. If necessary, polyfunctional monomers such as ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, triallyl cyanurate, and triallyl isocyanurate, polyfunctional polymers such as 1,2-polybutadiene, and sulfur compounds are used as cross-linking aids. May be blended. Any method may be used for producing the crosslinked ethylene-vinyl acetate copolymer, and examples thereof include a method of mixing using a kneader such as a mixer, a roll mill, a single-screw extruder, or a twin-screw extruder. it can.

本発明の架橋エチレン−酢酸ビニル共重合体ケン化物の製造方法としては、架橋させたエチレン−酢酸ビニル共重合体をアルカリあるいは酸を触媒として加水分解したものであり、例えば良溶媒に溶解させて溶液の状態で反応を行なう均一ケン化法、あるいはメタノール、エタノールのような貧溶媒中でペレットあるいは粉末のまま固液の状態で反応を行なう不均一ケン化法等が挙げられる。 The method for producing the crosslinked ethylene-vinyl acetate copolymer saponified product of the present invention is that the crosslinked ethylene-vinyl acetate copolymer is hydrolyzed using an alkali or an acid as a catalyst, and is dissolved in, for example, a good solvent. Examples thereof include a uniform saponification method in which the reaction is carried out in a solution state, and a non-uniform saponification method in which the reaction is carried out in a solid state as pellets or powder in a poor solvent such as methanol or ethanol.

本発明の架橋エチレン−酢酸ビニル共重合体ケン化物及びこれを含む接着剤樹脂組成物は、本発明の目的を逸脱しない範囲において、例えば酸化防止剤、滑剤、その他添加剤などを配合していてもよく、酸化防止剤としては、例えばｔ−ブチル−ヒドロキシトルエン、テトラキス−（メチレン−３−（３’−５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート）メタン、オクタデシル−３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート、１，３，５−トリス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）−１，３，５−トリアジン−２，４，６（１Ｈ，３Ｈ，５Ｈ）トリオン、１，３，５−トリメチル−２，４，６−トリス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）ベンゼン、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイトなどが挙げられる。滑剤としては、例えばラウリン酸、パルチミン酸、ステアリン酸等の脂肪酸、ラウリルアルコール、ミリスチルアルコール、パルミチルアルコール、ステアリルアルコール、ベヘニルアルコール等のアルコール、パラフィンワックス、ポリエチレンワックス等の炭化水素系ワックス、エチレンビスステアリン酸アミド、エルカ酸アミド、オレイン酸アミド、ステアリン酸アミド、エチレンビスオレイン酸アミド、エチレンビスエルカ酸アミド、エチレンビスラウリン酸アミド等の脂肪酸アミド、ステアリン酸亜鉛、ステアリン酸カルシウム、ステアリン酸マグネシウム、ラウリン酸亜鉛、ミリスチン酸亜鉛、ラウリン酸亜鉛等の金属石鹸、ステアリン酸モノグリセライド、ステアリン酸ブチル、ステアリルステアレート等が挙げられる。 The crosslinked ethylene-vinyl acetate copolymer saponified product of the present invention and the adhesive resin composition containing the same contain, for example, an antioxidant, a lubricant, and other additives within a range not deviating from the object of the present invention. Antioxidants include, for example, t-butyl-hydroxytoluene, tetrax- (methylene-3- (3'-5'-di-t-butyl-4'-hydroxyphenyl) propionate) methane, octadecyl-3. -(3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -1,3,5-triazine -2,4,6 (1H, 3H, 5H) trione, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris ( 2,4-di-t-butylphenyl) phosphite and the like can be mentioned. Examples of the lubricant include fatty acids such as lauric acid, partiminic acid and stearic acid, alcohols such as lauric alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol and behenyl alcohol, hydrocarbon waxes such as paraffin wax and polyethylene wax, and ethylene bisstearic acid. Fatty acid amides such as acid amides, erucic acid amides, oleic acid amides, stearic acid amides, ethylene bisoleic acid amides, ethylene bis-erucic acid amides, ethylene bislauric acid amides, zinc stearate, calcium stearate, magnesium stearate, lauric acid. Examples thereof include metal soaps such as zinc, zinc myristate and zinc laurate, monoglyceride stearate, butyl stearate, stearyl stearate and the like.

本発明の架橋エチレン−酢酸ビニル共重合体ケン化物は、賦形性、耐熱性、接着性、耐湿熱性に優れることから各種産業用途に用いることが可能であり、その中でも賦形性、耐熱性、接着性、耐湿熱性に優れることから耐久性が要求される接着剤として適したものである。例えば、本発明の架橋エチレン−酢酸ビニル共重合体ケン化物をホットメルトシール材として使用する場合は、使用する目的に応じて空冷、水冷インフレーション法、Ｔダイ法、カレンダー法、射出成形法、あるいは圧縮成形法等によりフィルムやシート状の成形体とした後、各種被着体と接着させる。この場合、これらの成形体を被着体間に挟み込み、次いで所定の温度（例えば１００〜１８０℃）で加熱することにより接着剤として使用する。また、その他の熱接着方法としては、該樹脂組成物を良溶媒に溶かした溶液を基材上に塗布し、５０〜１５０℃に加熱して溶媒を除去した後、他方の基材を熱圧着する方法、該樹脂組成物のパウダーを基材上に散布し、他方の基材を熱圧着する方法も用いられる。また押出コーティングにより、一方の基材上に該樹脂組成物をコーティングし、他方の基材を熱圧着する方法や押出ラミネーションにより少なくとも２種類の基材を積層する方法なども用いられる。該架橋エチレン−酢酸ビニル共重合体ケン化物は、適度の柔軟性を有していることから金属／該組成物からなる接着剤、金属／該組成物からなる接着剤／金属などの金属との複合材としても有効であり、金属は同じ材質でも異なる材質でも良い。 The crosslinked ethylene-vinyl acetate copolymer saponified product of the present invention is excellent in shapeability, heat resistance, adhesiveness, and moisture heat resistance, and can be used for various industrial applications. Among them, shapeability and heat resistance. It is suitable as an adhesive that requires durability because it has excellent adhesiveness and heat resistance to moisture and heat. For example, when the crosslinked ethylene-vinyl acetate copolymer saponified product of the present invention is used as a hot melt sealant, air-cooled, water-cooled inflation method, T-die method, calendar method, injection molding method, or After forming a film or sheet-shaped molded body by a compression molding method or the like, it is adhered to various adherends. In this case, these molded bodies are sandwiched between the adherends and then heated at a predetermined temperature (for example, 100 to 180 ° C.) to be used as an adhesive. As another heat bonding method, a solution of the resin composition dissolved in a good solvent is applied onto the base material, heated to 50 to 150 ° C. to remove the solvent, and then the other base material is thermocompression bonded. A method of spraying the powder of the resin composition on a base material and thermocompression bonding the other base material is also used. Further, a method of coating the resin composition on one base material by extrusion coating and thermocompression bonding of the other base material, a method of laminating at least two kinds of base materials by extrusion lamination, and the like are also used. Since the crosslinked ethylene-vinyl acetate copolymer saponified product has appropriate flexibility, it can be used with metals such as metals / adhesives made of the composition and metals / adhesives made of the composition / metals. It is also effective as a composite material, and the metal may be the same material or a different material.

本発明のホットメルト接着剤樹脂組成物は、低温接着性、耐熱性、耐湿熱性、透明性に優れることからガラス用接着剤、合わせガラスの中間膜としても適したものであり、例えば本発明のホットメルト接着剤樹脂組成物を合わせガラス中間膜として使用する際には、貫通強度、透明性に優れた合わせガラスとなることから、厚さ５０〜１５００μｍとすることが好ましく、特に１００〜１０００μｍとすることが好ましい。 The hot melt adhesive resin composition of the present invention is excellent in low temperature adhesiveness, heat resistance, moisture heat resistance, and transparency, and is therefore suitable as an adhesive for glass and an interlayer film of laminated glass. For example, the present invention. When the hot melt adhesive resin composition is used as a laminated glass interlayer film, the thickness is preferably 50 to 1500 μm, particularly 100 to 1000 μm, because the laminated glass has excellent penetration strength and transparency. It is preferable to do so.

本発明のホットメルト接着剤樹脂組成物からなる合わせガラス中間膜フィルムは、一対のガラスの間に中間層として挟み込み、例えば真空バッグのような治具を用いて減圧下で加熱したり、オートクレーブ装置を用いて加圧下で加熱することにより合わせガラスとすることが可能である。ホットメルト接着剤樹脂組成物をガラスと積層して積層体とすることができる。また、一対のガラスの間に２枚の中間膜を挿入し、その中間膜と中間膜の間に、例えば液晶フィルムを入れて同様な治具や装置を用いて１３０℃より低い温度で加熱することにより調光が可能な機能性を有した合わせガラスとすることが可能である。合わせガラスとする際には、ガラス以外に更に金属板、ポリカーボネート板、アクリル板などのプラスチック板、ポリエステルフィルム、ポリウレタンフィルムなどの高分子フィルム、紙などと積層し積層体とすることも可能である。該合わせガラスの層構成としては、例えば１）ガラス／中間膜／ガラス、２）ガラス／中間膜／プラスチック板、３）ガラス／中間膜／高分子フィルム、４）ガラス／中間層／プラスチック板／中間膜／ガラス、５）ガラス／中間膜／高分子フィルム／中間膜／ガラス、６）ガラス／中間膜／プラスチック板／中間膜／高分子フィルム／中間膜／ガラス、７）ガラス／中間膜／金属板／中間膜／ガラス、８）ガラス／中間膜／紙／中間膜／ガラスなどを挙げることができる。該プラスチック板、高分子フィルム、金属板、紙は着色しても良いし、またそれらの両面もしくは片面のいずれかに表面に印刷や金属被膜など処理を施しても良い。 The laminated glass interlayer film made of the hot melt adhesive resin composition of the present invention is sandwiched between a pair of glasses as an intermediate layer and heated under reduced pressure using a jig such as a vacuum bag, or an autoclave apparatus. It is possible to make a laminated glass by heating under pressure using the above. The hot melt adhesive resin composition can be laminated with glass to form a laminate. Further, two interlayer films are inserted between a pair of glasses, and for example, a liquid crystal film is inserted between the interlayer films and a liquid crystal film is inserted and heated at a temperature lower than 130 ° C. using the same jig or device. This makes it possible to obtain a laminated glass having functionality capable of dimming. In the case of laminated glass, in addition to glass, it is also possible to further laminate with a metal plate, a polycarbonate plate, a plastic plate such as an acrylic plate, a polymer film such as a polyester film or a polyurethane film, or paper to form a laminated body. .. The layer structure of the laminated glass includes, for example, 1) glass / interlayer / glass, 2) glass / interlayer / plastic plate, 3) glass / interlayer / polymer film, 4) glass / intermediate layer / plastic plate /. Intermediate film / glass, 5) Glass / Intermediate film / Polymer film / Intermediate film / Glass, 6) Glass / Intermediate film / Plastic plate / Intermediate film / Polymer film / Intermediate film / Glass, 7) Glass / Intermediate film / Examples include metal plate / interlayer film / glass, 8) glass / interlayer film / paper / interlayer film / glass, and the like. The plastic plate, polymer film, metal plate, and paper may be colored, or both sides or one side thereof may be subjected to a treatment such as printing or a metal coating on the surface.

本発明のホットメルト接着剤樹脂組成物からなる成形体は、接着界面の脱気性を向上させたり、成形時の離型性やハンドリング性を向上させる目的で成形体の表面に凹凸（エンボス）を施したものであり、例えば表面にエンボス加工を施した金型を用いて射出成形することにより得られるエンボス成形体やエンボス処理を施したチラーロールを用いてＴダイキャスト成形により得られるエンボスシート等を挙げることが出来る。エンボスは成形体の両面もしくは片面のいずれかに処理を施しても良い。 The molded product made of the hot-melt adhesive resin composition of the present invention has irregularities (embossing) on the surface of the molded product for the purpose of improving the degassing property of the adhesive interface and improving the mold releasability and handleability at the time of molding. For example, an embossed molded body obtained by injection molding using a mold having an embossed surface, an embossed sheet obtained by T-die casting using an embossed chiller roll, or the like. Can be mentioned. The embossing may be applied to either both sides or one side of the molded product.

本発明のホットメルト接着剤樹脂組成物を用いた合わせガラス中間膜フィルムの成形方法としては、特に限定されるものではないが、公知の方法、例えば、空冷インフレーション成形機、水冷インフレーション成形機、キャスト成形機、シート成形機、カレンダー成形機、圧縮成形機などを用いて成形加工することができる。 The method for forming the laminated glass interlayer film using the hot melt adhesive resin composition of the present invention is not particularly limited, but known methods such as an air-cooled inflation molding machine, a water-cooled inflation molding machine, and a cast Molding can be performed using a molding machine, a sheet molding machine, a calendar molding machine, a compression molding machine, or the like.

本発明の架橋エチレン−酢酸ビニル共重合体ケン化物は、賦形性、耐熱性、接着性、耐湿熱性に優れ、特にこれを含むホットメルト接着剤樹脂組成物は、ガラス等の被着体への低温接着が可能であり、耐熱性に加え、高湿熱環境下においても優れた透明性、接着性を有する。 The crosslinked ethylene-vinyl acetate copolymer saponified product of the present invention is excellent in formability, heat resistance, adhesiveness, and moist heat resistance, and a hot melt adhesive resin composition containing the same is particularly applied to an adherend such as glass. In addition to heat resistance, it has excellent transparency and adhesiveness even in a high humidity and heat environment.

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。 Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples.

以下に、透明性、接着性、耐熱性、耐湿熱性の測定方法を示す。
（１）透明性試験
板ガラス（北陸板ガラス株式会社製、商品名：ＦＬ２、厚み２ｍｍ、巾５０ｍｍ、長さ１００ｍｍ）の上に実施例により得られた中間膜用フィルム（厚み１．２ｍｍ、巾５０ｍｍ、長さ１００ｍｍ）を置き、更にその上にガラスを重ねて構成物を作製した。作製した構成物をアルミ真空袋の中に入れ、真空梱包機（株式会社ハギオス製、商品名：ＭＺＣ−３００Ｃ）を用いて３０トール以下になるまで減圧しながら構成物を真空パックした。次に、真空パックをそのまま１１０℃にセットしたギアオーブン（安田精機株式会社製、型式：Ｎｏ．１０２−ＳＨＦ−７７）に入れ３０分間加熱し、室温まで放冷後、真空パックからラミネート構成物取り出した。作製したガラス／中間膜フィルム／ガラスのラミネート構成物の曇り度をヘーズメーター（日本電色工業株式会社製、型式：３００Ａ）で測定した。また、ラミネート構成物の白濁感を目視により観察し、白濁感が無いものを良好、白濁感があるものを不良と判断した。
（２）接着性試験
板ガラス（北陸板ガラス株式会社製、商品名：ＦＬ３、厚み３ｍｍ、巾１００ｍｍ、長さ１００ｍｍ）の上に、つかみ部作製用として離型用ＰＥＴフィルム（厚み０．０７ｍｍ、巾１００ｍｍ、長さ５０ｍｍ）を置き、その上に実施例により得られた中間膜用フィルム（厚み０．４ｍｍ、巾１００ｍｍ、長さ１００ｍｍ）を重ね合わせた。更にその上に、支持体としてＰＥＴ（厚み０．１ｍｍ）とＬＬＤＰＥ（厚み０．０５ｍｍ）を予め接着剤で貼り合わせたラミネートフィルムのＬＬＤＰＥ面を下側にして重ね合わせた。このようにして作製した構成物をアルミ真空袋の中に入れ、真空梱包機（株式会社ハギオス製、商品名：ＭＺＣ−３００Ｃ）を用いて３０トール以下になるまで減圧しながら構成物を真空パックした。次に、真空パックをそのまま１１０℃にセットしたギアオーブンに入れ３０分間加熱し、室温まで放冷後、真空パックからラミネート構成物を取り出した。構成物を２５ｍｍ巾の短冊状に切断し、接着強度測定用試験片を得た。次に、引張試験機（ＯＲＩＥＮＴＥＣ社製ＲＴＥ−１２１０）を用いて、試験片の該加熱接着部分を剥離速度３００ｍｍ／分、剥離角度１８０度の条件で引張り、接着強度を測定した。
（３）耐熱性試験
板ガラス（北陸板ガラス株式会社製、商品名：ＦＬ２、厚み２ｍｍ、巾１００ｍｍ、長さ１００ｍｍ）の上に実施例により得られた中間膜用フィルム（厚み１．２ｍｍ、巾１００ｍｍ、長さ１００ｍｍ）を置き、更にその上にガラスを重ねて構成物を作製した。その構成物をアルミ真空袋の中に入れ、真空梱包機（株式会社ハギオス製、商品名：ＭＺＣ−３００Ｃ）を用いて３０トール以下になるまで減圧しながら構成物を真空パックした。次に、真空パックをそのまま１１０℃にセットしたギアオーブン（安田精機株式会社製、型式：Ｎｏ．１０２−ＳＨＦ−７７）に入れ３０分間加熱し、室温まで放冷後、真空パックからラミネート構成物取り出した。作製したガラス／中間膜フィルム／ガラスのラミネート構成物をギアオーブン（安田精機株式会社製、型式：Ｎｏ．１０２−ＳＨＦ−７７、条件：９０℃）に入れ１，０００ｈ処理した後に取り出した。作製したガラス／中間膜フィルム／ガラスのラミネート構成物及び中間膜の外観を観察した。ラミネート構成物の外観としては、２枚の板ガラスのズレが３ｍｍ以内のものは耐熱性良好とし、３ｍｍ以上生じたものは耐熱性が不良と判断し、中間膜の溶融によるガラス端面のはみ出しが３ｍｍ以内のものは耐熱性良好、３ｍｍ以上のものは不良と判断した。
（４）耐湿熱性試験
耐熱性試験の評価と同様の方法でガラス／中間膜フィルム／ガラスのラミネート構成物を作製した。作製したガラス／中間膜フィルム／ガラスのラミネート構成物を恒温恒湿槽（日立アプライアンス社製、型式：ＥＣ−２６ＭＨＨＰ、条件：８５℃／８５％Ｒｈ）に入れ１，０００ｈ処理した後に取り出した。ラミネート構成物の透明性として、曇り度をヘーズメーター（日本電色工業株式会社製、型式：３００Ａ）で測定した。また、ラミネート構成物の外観変化として、白化の状態を目視により観察し、白濁感が無いものを良好、白濁感があるものを不良と判断した。また、ラミネート構成物端部の全周を目視で観察し、収縮などによるヒケ（中間膜の欠け）や気泡の混入がガラス端部より５ｍｍ以内の場合を良好、５ｍｍを超えるものを不良とした。また、ガラスと中間膜の剥離の有無を確認し、剥離のないものを良好、部分的な剥離が生じたものを不良とした。 The methods for measuring transparency, adhesiveness, heat resistance, and moisture heat resistance are shown below.
(1) Transparency test An interlayer film (thickness 1.2 mm, width 50 mm) obtained by Examples on a plate glass (manufactured by Hokuriku Plate Glass Co., Ltd., trade name: FL2, thickness 2 mm, width 50 mm, length 100 mm). , Length 100 mm) was placed, and glass was further layered on it to prepare a composition. The prepared composition was placed in an aluminum vacuum bag, and the composition was vacuum-packed using a vacuum packing machine (manufactured by Hagios Co., Ltd., trade name: MZC-300C) while reducing the pressure to 30 toll or less. Next, the vacuum pack was placed in a gear oven (manufactured by Yasuda Seiki Co., Ltd., model: No. 102-SHF-77) set at 110 ° C. as it was, heated for 30 minutes, allowed to cool to room temperature, and then the vacuum pack was used as a laminate component. I took it out. The degree of fogging of the produced glass / interlayer film / glass laminate composition was measured with a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., model: 300A). Further, the white turbidity of the laminated composition was visually observed, and the one without the white turbidity was judged to be good, and the one with the white turbidity was judged to be defective.
(2) Adhesive test PET film for mold release (thickness 0.07 mm, width 0.07 mm, width) on plate glass (manufactured by Hokuriku Plate Glass Co., Ltd., trade name: FL3, thickness 3 mm, width 100 mm, length 100 mm) 100 mm, length 50 mm) was placed, and the interlayer film (thickness 0.4 mm, width 100 mm, length 100 mm) obtained in the examples was superposed on it. Further, PET (thickness 0.1 mm) and LLDPE (thickness 0.05 mm) were laminated on it with the LLDPE side facing down in advance with an adhesive. The composition produced in this manner is placed in an aluminum vacuum bag, and the composition is vacuum packed using a vacuum packing machine (manufactured by Hagios Co., Ltd., trade name: MZC-300C) while reducing the pressure to 30 toll or less. did. Next, the vacuum pack was placed in a gear oven set at 110 ° C. as it was, heated for 30 minutes, allowed to cool to room temperature, and then the laminated composition was taken out from the vacuum pack. The composition was cut into strips having a width of 25 mm to obtain test pieces for measuring adhesive strength. Next, using a tensile tester (RTE-1210 manufactured by ORIENTEC), the heat-bonded portion of the test piece was pulled under the conditions of a peeling speed of 300 mm / min and a peeling angle of 180 degrees, and the adhesive strength was measured.
(3) Heat resistance test An interlayer film (thickness 1.2 mm, width 100 mm) obtained by Examples on a plate glass (manufactured by Hokuriku Plate Glass Co., Ltd., trade name: FL2, thickness 2 mm, width 100 mm, length 100 mm). , Length 100 mm) was placed, and glass was further layered on it to prepare a composition. The composition was placed in an aluminum vacuum bag, and the composition was vacuum-packed using a vacuum packing machine (manufactured by Hagios Co., Ltd., trade name: MZC-300C) while reducing the pressure to 30 toll or less. Next, the vacuum pack was placed in a gear oven (manufactured by Yasuda Seiki Co., Ltd., model: No. 102-SHF-77) set at 110 ° C. as it was, heated for 30 minutes, allowed to cool to room temperature, and then the vacuum pack was used as a laminate component. I took it out. The prepared glass / interlayer film / glass laminate composition was placed in a gear oven (manufactured by Yasuda Seiki Co., Ltd., model: No. 102-SHF-77, condition: 90 ° C.), treated for 1,000 hours, and then taken out. The appearance of the prepared glass / interlayer film / glass laminate composition and interlayer film was observed. As for the appearance of the laminated structure, it is judged that the two plate glasses with a deviation of 3 mm or less have good heat resistance, and those with a deviation of 3 mm or more have poor heat resistance, and the protrusion of the glass end face due to the melting of the interlayer film is 3 mm. Those within 3 mm were judged to have good heat resistance, and those within 3 mm were judged to be defective.
(4) Moisture and heat resistance test A glass / interlayer film / glass laminated composition was prepared in the same manner as in the evaluation of the heat resistance test. The prepared glass / interlayer film / glass laminate composition was placed in a constant temperature and humidity chamber (manufactured by Hitachi Appliances, model: EC-26MHHP, condition: 85 ° C./85% Rh), treated for 1,000 hours, and then taken out. As the transparency of the laminated composition, the degree of cloudiness was measured with a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., model: 300A). Further, as a change in the appearance of the laminated structure, the whitening state was visually observed, and the one without the white turbidity was judged to be good, and the one with the white turbidity was judged to be bad. In addition, by visually observing the entire circumference of the edge of the laminated structure, sink marks (chips in the interlayer film) due to shrinkage, etc., and air bubbles mixed in were good when they were within 5 mm from the glass edge, and those over 5 mm were considered defective. .. In addition, the presence or absence of peeling between the glass and the interlayer film was confirmed, and the one without peeling was regarded as good, and the one with partial peeling was regarded as defective.

実施例１
（１）架橋エチレン−酢酸ビニル共重合体ケン化物の製造方法
公知の高圧法プロセスを用いて製造したメルトフローレート１３ｇ／１０分、エチレン残基単位の含有量が８６．７モル％、酢酸ビニル残基単位の含有量が１３．３モル％であるエチレン−酢酸ビニル共重合体１００重量部に有機過酸化物として、１，１−ジ（ｔ−ブチルペルオキシ）シクロヘキサン（日油株式会社製、商品名：パーヘキサＣ）０．０８重量部をタンブラーブレンダーで混合し、その混合原料を２軸押出機（日本製鋼所製、型式：ＴＥＸ−３０α）を用いて、温度１９０℃、押出量１０ｋｇ／ｈの条件で溶融混練し架橋エチレン−酢酸ビニル共重合体を得た。次に該架橋エチレン−酢酸ビニル共重合体を２．６重量％の苛性ソーダを含有するメタノール溶液中で５５℃、６時間ケン化して、架橋エチレン−酢酸ビニル共重合体ケン化物（Ａ１）を得た。得られた架橋エチレン−酢酸ビニル共重合体ケン化物（Ａ１）の物性値を表１に示す。 Example 1
(1) Method for producing crosslinked ethylene-vinyl acetate copolymer saponified product Melt flow rate produced using a known high-pressure method for 13 g / 10 minutes, ethylene residue unit content is 86.7 mol%, vinyl acetate 1,1-Di (t-butylperoxy) cyclohexane (manufactured by Japan Steel Works, Ltd.) as an organic peroxide in 100 parts by weight of an ethylene-vinyl acetate copolymer having a residue unit content of 13.3 mol%. Product name: Perhexa C) 0.08 parts by weight are mixed with a tumbler blender, and the mixed raw material is used with a twin-screw extruder (manufactured by Japan Steel Works, model: TEX-30α) at a temperature of 190 ° C. and an extrusion rate of 10 kg / A crosslinked ethylene-vinyl acetate copolymer was obtained by melt-kneading under the condition of h. Next, the crosslinked ethylene-vinyl acetate copolymer was saponified at 55 ° C. for 6 hours in a methanol solution containing 2.6% by weight of caustic soda to obtain a crosslinked ethylene-vinyl acetate copolymer saponified product (A1). It was. Table 1 shows the physical characteristics of the obtained crosslinked ethylene-vinyl acetate copolymer saponified product (A1).

（２）ホットメルト接着剤樹脂組成物の製造方法
該架橋エチレン−酢酸ビニル共重合体ケン化物（Ａ１）１００重量部に対し、タッキファイヤー（Ｂ）として、部分水添Ｃ９石油樹脂（Ｂ１）（荒川化学工業社製、商品名：アルコンＭ９０）２０重量部をタンブラーブレンダーで混合し、その混合原料を２軸押出機（日本製鋼所製、型式：ＴＥＸ−３０α）を用いて、温度１８０℃、押出量１０ｋｇ／ｈの条件で溶融混練しホットメルト接着剤樹脂組成物を得た。 (2) Method for Producing Hot Melt Adhesive Resin Composition Partially hydrogenated C9 petroleum resin (B1) as a tack fire (B) with respect to 100 parts by weight of the crosslinked ethylene-vinyl acetate copolymer saponification (A1). Arakawa Chemical Industry Co., Ltd., trade name: Archon M90) 20 parts by weight are mixed with a tumbler blender, and the mixed raw material is mixed using a twin-screw extruder (manufactured by Japan Steel Works, model: TEX-30α) at a temperature of 180 ° C. A hot melt adhesive resin composition was obtained by melt-kneading under the condition of an extrusion rate of 10 kg / h.

（３）中間膜用フィルムの製造方法
得られたホットメルト接着剤樹脂組成物を自動プレス成形機（株式会社神藤金属工業所製、型式：ＡＷＦＡ５．０）を用いて厚さ０．４ｍｍと１．２ｍｍの中間膜用フィルムを得た。プレス成形は、該樹脂組成物を１８０℃にセットしたプレス金型の中に入れ、３分間予熱した後脱気操作を行ない、１８０℃、１０ＭＰａにて３分間加熱加圧しプレス金型から取り出した後、３０℃にセットした冷却用のプレス金型の中に入れ、１０ＭＰａで５分間加圧冷却を行ない脱圧し中間膜用フィルムを得た。得られたホットメルト系接着剤樹脂組成物の中間膜用フィルムを用いて透明性、接着性、耐熱性、耐湿熱性の評価を実施した。その結果を表２に示す。 (3) Method for manufacturing film for interlayer film The obtained hot melt adhesive resin composition was used in an automatic press molding machine (manufactured by Shinto Metal Industry Co., Ltd., model: AWFA5.0) to have a thickness of 0.4 mm and 1 A 2 mm interlayer film was obtained. For press molding, the resin composition was placed in a press die set at 180 ° C., preheated for 3 minutes, then degassed, heated and pressed at 180 ° C. and 10 MPa for 3 minutes, and removed from the press die. After that, it was placed in a cooling press die set at 30 ° C., pressure-cooled at 10 MPa for 5 minutes, and depressurized to obtain an interlayer film. The transparency, adhesiveness, heat resistance, and moist heat resistance were evaluated using the film for the interlayer film of the obtained hot-melt adhesive resin composition. The results are shown in Table 2.

実施例２
（１）架橋エチレン−酢酸ビニル共重合体ケン化物の製造方法
メルトフローレート５．５ｇ／１０分、エチレン残基単位の含有量が８８．８モル％、酢酸ビニル残基単位の含有量が１１．２モル％であるエチレン−酢酸ビニル共重合体（東ソー株式会社製、商品名：ウルトラセン７５１）１００重量部に有機過酸化物として１，１−ジ（ｔ−ブチルペルオキシ）シクロヘキサン（日油株式会社製、商品名：パーヘキサＣ）０．０６重量部をタンブラーブレンダーで混合し、混合原料を２軸押出機（日本製鋼所製、型式：ＴＥＸ−３０α）を用いて、温度１９０℃、押出量１０ｋｇ／ｈの条件で溶融混練し架橋エチレン−酢酸ビニル共重合体を得た。次に該架橋エチレン−酢酸ビニル共重合体を２．２重量％の苛性ソーダを含有するメタノール溶液中で５５℃、６時間ケン化して、架橋エチレン−酢酸ビニル共重合体ケン化物（Ａ２）を得た。得られた架橋エチレン−酢酸ビニル共重合体ケン化物（Ａ２）の物性値を表１に示す。 Example 2
(1) Method for producing crosslinked ethylene-vinyl acetate copolymer saponified product Melt flow rate 5.5 g / 10 minutes, ethylene residue unit content is 88.8 mol%, vinyl acetate residue unit content is 11 .2 mol% ethylene-vinyl acetate copolymer (manufactured by Toso Co., Ltd., trade name: Ultrasen 751) 100 parts by weight as an organic peroxide 1,1-di (t-butylperoxy) cyclohexane (Japan Steel Works) Made by Co., Ltd., trade name: Perhexa C) 0.06 parts by weight are mixed with a tumbler blender, and the mixed raw material is extruded at a temperature of 190 ° C. using a twin-screw extruder (manufactured by Japan Steel Works, model: TEX-30α). A crosslinked ethylene-vinyl acetate copolymer was obtained by melt-kneading under the condition of an amount of 10 kg / h. Next, the crosslinked ethylene-vinyl acetate copolymer was saponified at 55 ° C. for 6 hours in a methanol solution containing 2.2% by weight of caustic soda to obtain a crosslinked ethylene-vinyl acetate copolymer saponified product (A2). It was. Table 1 shows the physical characteristics of the obtained crosslinked ethylene-vinyl acetate copolymer saponified product (A2).

（２）ホットメルト接着剤樹脂組成物の製造方法
架橋エチレン−酢酸ビニル共重合体ケン化物（Ａ１）の代わりに架橋エチレン−酢酸ビニル共重合体ケン化物（Ａ２）１００重量部に対し、タッキファイヤー（Ｂ）として、部分水添Ｃ９石油樹脂（Ｂ１）（荒川化学工業社製、商品名：アルコンＭ９０）１０重量部とした以外は、実施例１と同様にして、ホットメルト接着剤樹脂組成物を得た。 (2) Method for Producing Hot Melt Adhesive Resin Composition Tuckfire with respect to 100 parts by weight of the crosslinked ethylene-vinyl acetate copolymer saponified product (A2) instead of the crosslinked ethylene-vinyl acetate copolymer saponified product (A1). The hot melt adhesive resin composition was the same as in Example 1 except that (B) was partially hydrogenated C9 petroleum resin (B1) (manufactured by Arakawa Chemical Industry Co., Ltd., trade name: Archon M90) in an amount of 10 parts by weight. Got

（３）中間膜用フィルムの製造方法
該ホットメルト接着剤樹脂組成物を用いて、実施例１と同様な方法で中間膜用フィルムを得た。 (3) Method for Producing Film for Intermediate Film Using the hot melt adhesive resin composition, a film for interlayer film was obtained in the same manner as in Example 1.

得られたホットメルト系接着剤樹脂組成物の中間膜用フィルムを用いて透明性、接着性、耐熱性、耐湿熱性の評価を実施した。その結果を表２に示す。 The transparency, adhesiveness, heat resistance, and moist heat resistance were evaluated using the film for the interlayer film of the obtained hot-melt adhesive resin composition. The results are shown in Table 2.

実施例３
架橋エチレン−酢酸ビニル共重合体ケン化物（Ａ１）の代わりに架橋エチレン−酢酸ビニル共重合体ケン化物（Ａ２）１００重量部に対し、タッキファイヤー（Ｂ）として、水添Ｃ９石油樹脂（Ｂ１）（荒川化学工業社製、商品名：アルコンＭ９０）１０重量部、シラン化合物（Ｃ）として、３−グリシドキシプロピルトリメトキシシラン（Ｃ１）（信越化学工業社製、商品名：ＫＢＭ４０３）０．５重量部とした以外は、実施例１と同様にして、ホットメルト接着剤樹脂組成物及び中間膜用フィルムを得た。 Example 3
Hydrolyzed C9 petroleum resin (B1) as a tack fire (B) with respect to 100 parts by weight of the crosslinked ethylene-vinyl acetate copolymer saponification (A2) instead of the crosslinked ethylene-vinyl acetate copolymer saponification (A1). (Manufactured by Arakawa Chemical Industry Co., Ltd., trade name: Archon M90) 10 parts by weight, as a silane compound (C), 3-glycidoxypropyltrimethoxysilane (C1) (manufactured by Shinetsu Chemical Industry Co., Ltd., trade name: KBM403) 0. A hot melt adhesive resin composition and a film for an interlayer film were obtained in the same manner as in Example 1 except that the weight was 5 parts by weight.

得られたホットメルト系接着剤樹脂組成物の中間膜用フィルムを用いて透明性、接着性、耐熱性、耐湿熱性の評価を実施した。その結果を表２に示す。 The transparency, adhesiveness, heat resistance, and moist heat resistance were evaluated using the film for the interlayer film of the obtained hot-melt adhesive resin composition. The results are shown in Table 2.

実施例４
架橋エチレン−酢酸ビニル共重合体ケン化物（Ａ１）の代わりに架橋エチレン−酢酸ビニル共重合体ケン化物（Ａ２）１００重量部に対し、タッキファイヤー（Ｂ）として、水添Ｃ９石油樹脂（Ｂ１）（荒川化学工業社製、商品名：アルコンＭ９０）１０重量部、シラン化合物（Ｃ）として、３−グリシドキシプロピルトリメトキシシラン（Ｃ１）（信越化学工業社製、商品名：ＫＢＭ４０３）０．５重量部、酸変性エチレン−酢酸ビニル共重合体（Ｄ）として、アクリル酸グラフトエチレン−酢酸ビニル共重合体（Ｄ１）（日油株式会社、商品名：モディパーＡ６６００）１０重量部とした以外は、実施例１と同様にして、ホットメルト接着剤樹脂組成物及び中間膜用フィルムを得た。 Example 4
Hydrogenated C9 petroleum resin (B1) as a tack fire (B) with respect to 100 parts by weight of the crosslinked ethylene-vinyl acetate copolymer saponified product (A2) instead of the crosslinked ethylene-vinyl acetate copolymer saponified product (A1). (Manufactured by Arakawa Chemical Industry Co., Ltd., trade name: Archon M90) 10 parts by weight, as a silane compound (C), 3-glycidoxypropyltrimethoxysilane (C1) (manufactured by Shinetsu Chemical Industry Co., Ltd., trade name: KBM403) 0. 5 parts by weight, except that the acid-modified ethylene-vinyl acetate copolymer (D) was 10 parts by weight of the acrylate-grafted ethylene-vinyl acetate copolymer (D1) (Nippon Oil Co., Ltd., trade name: Modiper A6600). , A hot melt adhesive resin composition and a film for an interlayer film were obtained in the same manner as in Example 1.

得られたホットメルト系接着剤樹脂組成物の中間膜用フィルムを用いて透明性、接着性、耐熱性、耐湿熱性の評価を実施した。その結果を表２に示す。 The transparency, adhesiveness, heat resistance, and moist heat resistance were evaluated using the film for the interlayer film of the obtained hot-melt adhesive resin composition. The results are shown in Table 2.

実施例５
（１）架橋エチレン−酢酸ビニル共重合体ケン化物の製造方法
メルトフローレート４．３ｇ／１０分、エチレン残基単位の含有量が８９．７モル％、酢酸ビニル残基単位の含有量が１０．３モル％であるエチレン−酢酸ビニル共重合体（東ソー株式会社製、商品名：ウルトラセン６３４）１００重量部に有機過酸化物として１，１−ジ（ｔ−ブチルペルオキシ）シクロヘキサン（日油株式会社製、商品名：パーヘキサＣ）０．０４重量部とした以外は実施例１と同様な方法で架橋エチレン−酢酸ビニル共重合体を得た。次に該架橋エチレン−酢酸ビニル共重合体を１．１重量％の苛性ソーダを含有するメタノール溶液中で５０℃、４時間ケン化して、架橋エチレン−酢酸ビニル共重合体ケン化物（Ａ３）を得た。得られた架橋エチレン−酢酸ビニル共重合体ケン化物（Ａ３）の物性値を表１に示す。 Example 5
(1) Method for producing crosslinked ethylene-vinyl acetate copolymer saponified product Melt flow rate 4.3 g / 10 minutes, ethylene residue unit content is 89.7 mol%, vinyl acetate residue unit content is 10. 1.3 mol% ethylene-vinyl acetate copolymer (manufactured by Toso Co., Ltd., trade name: Ultrasen 634) 1,1-di (t-butylperoxy) cyclohexane (Japanese oil) as an organic peroxide in 100 parts by weight A crosslinked ethylene-vinyl acetate copolymer was obtained in the same manner as in Example 1 except that the amount was 0.04 parts by weight (manufactured by Co., Ltd., trade name: Perhexa C). Next, the crosslinked ethylene-vinyl acetate copolymer was saponified at 50 ° C. for 4 hours in a methanol solution containing 1.1% by weight of caustic soda to obtain a crosslinked ethylene-vinyl acetate copolymer saponified product (A3). It was. Table 1 shows the physical characteristics of the obtained crosslinked ethylene-vinyl acetate copolymer saponified product (A3).

（２）ホットメルト接着剤樹脂組成物の製造方法
架橋エチレン−酢酸ビニル共重合体ケン化物（Ａ１）の代わりに架橋エチレン−酢酸ビニル共重合体ケン化物（Ａ３）１００重量部に対し、タッキファイヤー（Ｂ）として、水添ロジンエステル（Ｂ２）（荒川化学工業社製、商品名：パインクリスタルＫＥ３１１）１５重量部、シラン化合物（Ｃ）として、３−アクリロキシプロピルトリメトキシシラン（Ｃ２）（信越化学工業社製、商品名：ＫＢＭ５１０３）０．５重量部、酸変性エチレン−酢酸ビニル共重合体（Ｄ）として、アクリル酸グラフトエチレン−酢酸ビニル共重合体（Ｄ１）（日油株式会社、商品名：モディパーＡ６６００）５重量部とした以外は、実施例１と同様にして、ホットメルト接着剤樹脂組成物を得た。 (2) Method for Producing Hot Melt Adhesive Resin Composition Tuckfire with respect to 100 parts by weight of the crosslinked ethylene-vinyl acetate copolymer saponified product (A3) instead of the crosslinked ethylene-vinyl acetate copolymer saponified product (A1). As (B), 15 parts by weight of hydrogenated rosin ester (B2) (manufactured by Arakawa Chemical Industry Co., Ltd., trade name: Pine Crystal KE311), and as silane compound (C), 3-acryloxypropyltrimethoxysilane (C2) (Shinetsu). Made by Kagaku Kogyo Co., Ltd., trade name: KBM5103) 0.5 parts by weight, as an acid-modified ethylene-vinyl acetate copolymer (D), acrylate-grafted ethylene-vinyl acetate copolymer (D1) (Nippon Oil Co., Ltd., product) Name: Modiper A6600) A hot-melt adhesive resin composition was obtained in the same manner as in Example 1 except that the composition was 5 parts by weight.

（３）中間膜フィルムの製造方法
該ホットメルト接着剤樹脂組成物を用いて、実施例１と同様な方法で中間膜用フィルムを得た。 (3) Method for Producing Intermediate Film Film Using the hot melt adhesive resin composition, an interlayer film was obtained in the same manner as in Example 1.

得られたホットメルト系接着剤樹脂組成物の中間膜用フィルムを用いて透明性、接着性、耐熱性、耐湿熱性の評価を実施した。その結果を表２に示す。 The transparency, adhesiveness, heat resistance, and moist heat resistance were evaluated using the film for the interlayer film of the obtained hot-melt adhesive resin composition. The results are shown in Table 2.

比較例１
架橋エチレン−酢酸ビニル共重合体ケン化物（Ａ１）１００重量部に対し、タッキファイヤー（Ｂ）として、部分水添Ｃ９石油樹脂（Ｂ１）（荒川化学工業社製、商品名：アルコンＭ９０）１重量部とした以外は実施例１と同様にして、ホットメルト接着剤樹脂組成物及び中間膜用フィルムを得た。得られたホットメルト系接着剤樹脂組成物の中間膜用フィルムを用いて透明性、接着性、耐熱性、耐湿熱性の評価を実施した。その結果を表３に示す。得られたホットメルト接着剤樹脂組成物は透明性やガラスとの接着性、湿熱環境下における透明性、接着性に劣るものであった。 Comparative Example 1
1 weight of partially hydrogenated C9 petroleum resin (B1) (manufactured by Arakawa Chemical Industries, Ltd., trade name: Archon M90) as a tack fire (B) with respect to 100 parts by weight of the crosslinked ethylene-vinyl acetate copolymer saponified product (A1). A hot-melt adhesive resin composition and a film for an interlayer film were obtained in the same manner as in Example 1 except for the portion. The transparency, adhesiveness, heat resistance, and moist heat resistance were evaluated using the film for the interlayer film of the obtained hot-melt adhesive resin composition. The results are shown in Table 3. The obtained hot melt adhesive resin composition was inferior in transparency, adhesiveness to glass, transparency in a moist heat environment, and adhesiveness.

比較例２
架橋エチレン−酢酸ビニル共重合体ケン化物（Ａ１）の代わりに架橋エチレン−酢酸ビニル共重合体ケン化物（Ａ２）１００重量部に対し、タッキファイヤー（Ｂ）として、部分水添Ｃ９石油樹脂（Ｂ１）（荒川化学工業社製、商品名：アルコンＭ９０）４０重量部とした以外は実施例１と同様にして樹脂組成物の溶融混練を行なった。該組成物の溶融押出しストランド表面の粘着性が強く、ストランド同士が強固にブロッキングしたり、繰り出しロールに巻き付くなどペレット化が困難であり、中間膜フィルムは得られなかった。 Comparative Example 2
Partially hydrogenated C9 petroleum resin (B1) as a tack fire (B) with respect to 100 parts by weight of the crosslinked ethylene-vinyl acetate copolymer saponified product (A2) instead of the crosslinked ethylene-vinyl acetate copolymer saponified product (A1). ) (Manufactured by Arakawa Chemical Industry Co., Ltd., trade name: Archon M90) The resin composition was melt-kneaded in the same manner as in Example 1 except that the amount was 40 parts by weight. The surface of the melt-extruded strands of the composition was strongly adhesive, and it was difficult to pelletize the strands by blocking them tightly or wrapping them around a feeding roll, so that an interlayer film could not be obtained.

比較例３
（１）架橋エチレン−酢酸ビニル共重合体ケン化物の製造方法
メルトフローレート５．５ｇ／１０分、エチレン残基単位の含有量が８８．８モル％、酢酸ビニル残基単位の含有量が１１．２モル％であるエチレン−酢酸ビニル共重合体（東ソー株式会社製、商品名：ウルトラセン７５１）１００重量部に有機過酸化物として１，１−ジ（ｔ−ブチルペルオキシ）シクロヘキサン（日油株式会社製、商品名：パーヘキサＣ）０．０６重量部をタンブラーブレンダーで混合し、混合原料を２軸押出機（日本製鋼所製、型式：ＴＥＸ−３０α）を用いて、温度１９０℃、押出量１０ｋｇ／ｈの条件で溶融混練し架橋エチレン−酢酸ビニル共重合体を得た。次に未ケン化のまま架橋エチレン−酢酸ビニル共重合体ケン化物（Ａ４）として用いた。 Comparative Example 3
(1) Method for producing crosslinked ethylene-vinyl acetate copolymer saponified product Melt flow rate 5.5 g / 10 minutes, ethylene residue unit content is 88.8 mol%, vinyl acetate residue unit content is 11 .2 mol% ethylene-vinyl acetate copolymer (manufactured by Toso Co., Ltd., trade name: Ultrasen 751) 100 parts by weight as an organic peroxide 1,1-di (t-butylperoxy) cyclohexane (Japan Steel Works) Made by Co., Ltd., trade name: Perhexa C) 0.06 parts by weight are mixed with a tumbler blender, and the mixed raw material is extruded at a temperature of 190 ° C. using a twin-screw extruder (manufactured by Japan Steel Works, model: TEX-30α). A crosslinked ethylene-vinyl acetate copolymer was obtained by melt-kneading under the condition of an amount of 10 kg / h. Next, it was used as a crosslinked ethylene-vinyl acetate copolymer saponified product (A4) without being saponified.

（２）ホットメルト接着剤樹脂組成物の製造方法
架橋エチレン−酢酸ビニル共重合体ケン化物（Ａ１）の代わりに架橋エチレン−酢酸ビニル共重合体ケン化物（Ａ４）１００重量部に対し、タッキファイヤー（Ｂ）として、部分水添Ｃ９石油樹脂（Ｂ１）（荒川化学工業社製、商品名：アルコンＭ９０）２０重量部とした以外は、実施例１と同様にして、ホットメルト接着剤樹脂組成物を得た。 (2) Method for Producing Hot Melt Adhesive Resin Composition Tuckfire with respect to 100 parts by weight of crosslinked ethylene-vinyl acetate copolymer saponified product (A4) instead of crosslinked ethylene-vinyl acetate copolymer saponified product (A1). The hot melt adhesive resin composition was the same as in Example 1 except that (B) was partially hydrogenated C9 petroleum resin (B1) (manufactured by Arakawa Chemical Industry Co., Ltd., trade name: Archon M90) in an amount of 20 parts by weight. Got

（３）中間膜フィルムの製造方法
該ホットメルト接着剤樹脂組成物を用いて、実施例１と同様な方法で中間膜用フィルムを得た。 (3) Method for Producing Intermediate Film Film Using the hot melt adhesive resin composition, an interlayer film was obtained in the same manner as in Example 1.

得られたホットメルト系接着剤樹脂組成物の中間膜用フィルムを用いて透明性、接着性、耐熱性、耐湿熱性の評価を実施した。その結果を表３に示す。得られたホットメルト接着剤樹脂組成物は湿熱環境下において、膨潤による白化が生じ透明性が大きく劣るものであった。 The transparency, adhesiveness, heat resistance, and moist heat resistance were evaluated using the film for the interlayer film of the obtained hot-melt adhesive resin composition. The results are shown in Table 3. The obtained hot-melt adhesive resin composition was whitened due to swelling in a moist heat environment and was significantly inferior in transparency.

比較例４
（１）架橋エチレン−酢酸ビニル共重合体ケン化物の製造方法
メルトフローレート３．０ｇ／１０分、エチレン残基単位の含有量が９６．５モル％、酢酸ビニル残基単位の含有量が３．５モル％であるエチレン−酢酸ビニル共重合体（東ソー株式会社製、商品名：ウルトラセン５４０）１００重量部に有機過酸化物として１，１−ジ（ｔ−ブチルペルオキシ）シクロヘキサン（日油株式会社製、商品名：パーヘキサＣ）０．０２重量部とした以外は実施例１と同様な方法で架橋エチレン−酢酸ビニル共重合体を得た。次に該架橋エチレン−酢酸ビニル共重合体を１．４重量％の苛性ソーダを含有するメタノール溶液中で６０℃、７時間ケン化して、架橋エチレン−酢酸ビニル共重合体ケン化物（Ａ５）を得た。得られた架橋エチレン−酢酸ビニル共重合体ケン化物（Ａ５）の物性値を表１に示す。 Comparative Example 4
(1) Method for producing crosslinked ethylene-vinyl acetate copolymer saponified product Melt flow rate 3.0 g / 10 minutes, ethylene residue unit content is 96.5 mol%, vinyl acetate residue unit content is 3 1,1-Di (t-butylperoxy) cyclohexane (Japanese oil) as an organic peroxide in 100 parts by weight of an ethylene-vinyl acetate copolymer (manufactured by Toso Co., Ltd., trade name: Ultrasen 540) which is 5.5 mol%. A crosslinked ethylene-vinyl acetate copolymer was obtained in the same manner as in Example 1 except that the amount was 0.02 parts by weight (manufactured by Co., Ltd., trade name: Perhexa C). Next, the crosslinked ethylene-vinyl acetate copolymer was saponified at 60 ° C. for 7 hours in a methanol solution containing 1.4% by weight of caustic soda to obtain a crosslinked ethylene-vinyl acetate copolymer saponified product (A5). It was. Table 1 shows the physical characteristics of the obtained crosslinked ethylene-vinyl acetate copolymer saponified product (A5).

（２）ホットメルト接着剤樹脂組成物の製造方法
架橋エチレン−酢酸ビニル共重合体ケン化物（Ａ１）の代わりに架橋エチレン−酢酸ビニル共重合体ケン化物（Ａ５）１００重量部、タッキファイヤー（Ｂ）として、部分水添Ｃ９石油樹脂（Ｂ１）（荒川化学工業社製、商品名：アルコンＭ９０）１０重量部、シラン化合物（Ｃ）として、３−グリシドキシプロピルトリメトキシシラン（Ｃ１）（信越化学工業社製、商品名：ＫＢＭ４０３）０．１重量部、酸変性エチレン−酢酸ビニル共重合体（Ｄ）として、アクリル酸グラフトエチレン−酢酸ビニル共重合体（Ｄ１）（日油株式会社製、商品名：モディパーＡ６６００）１０重量部とした以外は、実施例１と同様にして、ホットメルト接着剤樹脂組成物を得た。 (2) Method for Producing Hot Melt Adhesive Resin Composition 100 parts by weight of crosslinked ethylene-vinyl acetate copolymer saponified product (A5) instead of crosslinked ethylene-vinyl acetate copolymer saponified product (A1), tack fire (B) ), Partial hydrogenated C9 petroleum resin (B1) (manufactured by Arakawa Chemical Industry Co., Ltd., trade name: Archon M90), 10 parts by weight, and 3-glycidoxypropyltrimethoxysilane (C1) (Shinetsu) as the silane compound (C). Chemical Industry Co., Ltd., trade name: KBM403) 0.1 parts by weight, as an acid-modified ethylene-vinyl acetate copolymer (D), acrylate-grafted ethylene-vinyl acetate copolymer (D1) (manufactured by Nichiyu Co., Ltd., A hot melt adhesive resin composition was obtained in the same manner as in Example 1 except that the product name: Modiper A6600) was 10 parts by weight.

（３）中間膜フィルムの製造方法
該ホットメルト接着剤樹脂組成物を用いて、実施例１と同様な方法で中間膜用フィルムを得た。 (3) Method for Producing Intermediate Film Film Using the hot melt adhesive resin composition, an interlayer film was obtained in the same manner as in Example 1.

得られたホットメルト系接着剤樹脂組成物の中間膜用フィルムを用いて透明性、接着性、耐熱性、耐湿熱性の評価を実施した。その結果を表３に示す。得られたホットメルト接着剤樹脂組成物は透明性に劣るものであった。 The transparency, adhesiveness, heat resistance, and moist heat resistance were evaluated using the film for the interlayer film of the obtained hot-melt adhesive resin composition. The results are shown in Table 3. The obtained hot melt adhesive resin composition was inferior in transparency.

比較例５
（１）架橋エチレン−酢酸ビニル共重合体ケン化物の製造方法
メルトフローレート１６ｇ／１０分、エチレン残基単位の含有量が８８．８モル％、酢酸ビニル残基単位の含有量が６．７モル％、ビニルアルコール残基単位の含有量が４．５モル％であるエチレン−酢酸ビニル共重合体ケン化物（東ソー株式会社製、商品名：メルセンＨ６４１０）１００重量部に有機過酸化物として１，１−ジ（ｔ−ブチルペルオキシ）シクロヘキサン（日油株式会社製、商品名：パーヘキサＣ）０．０４重量部とした以外は実施例１と同様な方法で架橋エチレン−酢酸ビニル共重合体ケン化物（Ａ６）を得た。得られた架橋エチレン−酢酸ビニル共重合体ケン化物（Ａ６）の物性値を表１に示す。得られた架橋エチレン−酢酸ビニル共重合体ケン化物はゲル分や弾性率が低く、また弾性率の傾きも大きいことから、架橋の進行が十分でないものであった。 Comparative Example 5
(1) Method for producing crosslinked ethylene-vinyl acetate copolymer saponified product Melt flow rate 16 g / 10 minutes, ethylene residue unit content is 88.8 mol%, vinyl acetate residue unit content is 6.7 Ethylene-vinyl acetate copolymer saponified product (manufactured by Toso Co., Ltd., trade name: Mercen H6410) having a molar% content of 4.5 mol% of vinyl alcohol residue units as an organic peroxide in 100 parts by weight , 1-di (t-butylperoxy) cyclohexane (manufactured by Nichiyu Co., Ltd., trade name: Perhexa C) in the same manner as in Example 1 except that the amount was 0.04 parts by weight. A compound (A6) was obtained. Table 1 shows the physical characteristics of the obtained crosslinked ethylene-vinyl acetate copolymer saponified product (A6). The crosslinked ethylene-vinyl acetate copolymer saponified product obtained had a low gel content and elastic modulus, and had a large slope of elastic modulus, so that the progress of crosslinking was not sufficient.

（２）ホットメルト接着剤樹脂組成物の製造方法
該架橋エチレン−酢酸ビニル共重合体ケン化物（Ａ１）の代わりに架橋エチレン−酢酸ビニル共重合体ケン化物（Ａ６）１００重量部に対し、タッキファイヤー（Ｂ）として、水添ロジンエステル（Ｂ２）（荒川化学工業社製、商品名：パインクリスタルＫＥ３１１）１０重量部、シラン化合物（Ｃ）として、３−アクリロキシプロピルトリメトキシシラン（Ｃ２）（信越化学工業社製、商品名：ＫＢＭ５１０３）０．５重量部、酸変性エチレン−酢酸ビニル共重合体（Ｄ）として、アクリル酸グラフトエチレン−酢酸ビニル共重合体（Ｄ１）（日油株式会社製、商品名：モディパーＡ６６００）１０重量部とした以外は、実施例１と同様にして、ホットメルト接着剤樹脂組成物を得た。 (2) Method for Producing Hot Melt Adhesive Resin Composition Tacky with respect to 100 parts by weight of the crosslinked ethylene-vinyl acetate copolymer saponified product (A6) instead of the crosslinked ethylene-vinyl acetate copolymer saponified product (A1). As a fire (B), 10 parts by weight of a hydrogenated rosin ester (B2) (manufactured by Arakawa Chemical Industry Co., Ltd., trade name: Pine Crystal KE311), and as a silane compound (C), 3-acryloxypropyltrimethoxysilane (C2) ( Made by Shin-Etsu Chemical Industry Co., Ltd., trade name: KBM5103) 0.5 parts by weight, as an acid-modified ethylene-vinyl acetate copolymer (D), acrylic acid graft ethylene-vinyl acetate copolymer (D1) (manufactured by Nichiyu Co., Ltd.) , Trade name: Modiper A6600) A hot melt adhesive resin composition was obtained in the same manner as in Example 1 except that the amount was 10 parts by weight.

（３）中間膜フィルムの製造方法
該ホットメルト接着剤樹脂組成物を用いて、実施例１と同様な方法で中間膜用フィルムを得た。 (3) Method for Producing Intermediate Film Film Using the hot melt adhesive resin composition, an interlayer film was obtained in the same manner as in Example 1.

得られたホットメルト系接着剤樹脂組成物の中間膜用フィルムを用いて透明性、接着性、耐熱性、耐湿熱性の評価を実施した。その結果を表３に示す。得られたホットメルト接着剤樹脂組成物は耐熱性、耐湿熱性に劣るものであった。 The transparency, adhesiveness, heat resistance, and moist heat resistance were evaluated using the film for the interlayer film of the obtained hot-melt adhesive resin composition. The results are shown in Table 3. The obtained hot melt adhesive resin composition was inferior in heat resistance and moisture heat resistance.

Figure 0006855820
Figure 0006855820

Figure 0006855820
Figure 0006855820

Figure 0006855820
Figure 0006855820

本発明のホットメルト接着剤樹脂組成物は、特定の架橋エチレン−酢酸ビニル共重合体ケン化物に対し、タッキファイヤー、更にはシラン化合物、酸変性エチレン−酢酸ビニル共重合体を含む組成物からなり、ガラスとの低温接着性に加え、長期にわたる加熱、湿熱環境下においても実用上支障となる外観変化がなく、透明性、接着性に優れていることから、建材や輸送車両、電子デバイスなどの産業用合わせガラスの接着材料としての適用が期待されるものである。 The hot melt adhesive resin composition of the present invention comprises a composition containing a tack fire, a silane compound, and an acid-modified ethylene-vinyl acetate copolymer with respect to a specific crosslinked ethylene-vinyl acetate copolymer saponified product. In addition to low-temperature adhesiveness to glass, there is no change in appearance that would hinder practical use even in long-term heating and moist heat environments, and because of its excellent transparency and adhesiveness, it can be used for building materials, transportation vehicles, electronic devices, etc. It is expected to be applied as an adhesive material for industrial laminated glass.

Claims (8)

エチレン残基単位７５．４〜９４．６モル％、酢酸ビニル残基単位２．２〜２２．１モル％、ビニルアルコール残基単位０．５〜１４．７モル％を含み、ゲル分が０．００１〜０．５重量％以下、動的粘弾性測定にて得られる周波数１０Ｈｚの弾性率において、ＪＩＳ Ｋ６９２４−２で測定した融点より２０〜５０℃高い温度における弾性率（Ｅ’）が１０５Ｐａ以上で、温度に対する弾性率の傾き（ｌｏｇ│ΔＥ’／ΔＴ│）が５以下、ＪＩＳ Ｋ６９２４−１で測定したメルトマスフローレイトが０．０１〜１００ｇ／１０分からなる架橋エチレン−酢酸ビニル共重合体ケン化物（Ａ）１００重量部にタッキファイヤー（Ｂ）５〜３０重量部を含むことを特徴とするホットメルト接着剤樹脂組成物。 Contains 75.4-94.6 mol% of ethylene residue unit, 2.2-22.1 mol% of vinyl acetate residue unit, 0.5-14.7 mol% of vinyl alcohol residue unit, and 0 gel content. The elastic modulus (E') at a temperature 20 to 50 ° C. higher than the melting point measured by JIS K6924-2 is 10 at an elastic modulus of .001 to 0.5 % by weight or less and a frequency of 10 Hz obtained by dynamic viscoelasticity measurement. Cross-linked ethylene-vinyl acetate having a modulus of elastic modulus with respect to temperature (log│ΔE'/ ΔT│) of 5 or less and a melt mass flow rate of 0.01 to 100 g / 10 minutes measured by JIS K6924-1 at 5 Pa or more. A hot melt adhesive resin composition comprising 5 to 30 parts by weight of a tack fire (B) in 100 parts by weight of a saponified polymer (A). さらに、少なくともエポキシ基、アクリル基、メタクリル基又はイソシナネート基の何れかの有機官能基を有するシラン化合物（Ｃ）０．０１〜１重量部及び／又は酸変性エチレン−酢酸ビニル共重合体（Ｄ）１〜２０重量部を含むことを特徴とする請求項１に記載のホットメルト接着剤樹脂組成物。 Further, 0.01 to 1 part by weight of a silane compound (C) having an organic functional group of at least an epoxy group, an acrylic group, a methacryl group or an isocinate group and / or an acid-modified ethylene-vinyl acetate copolymer (D). The hot melt adhesive resin composition according to claim 1 , which comprises 1 to 20 parts by weight. 前記タッキファイヤーが部分水添石油樹脂又は水添ロジンエステルを含むことを特徴とする請求項１又は２に記載のホットメルト接着剤樹脂組成物。 The hot melt adhesive resin composition according to claim 1 or 2 , wherein the tack fire contains a partially hydrogenated petroleum resin or a hydrogenated rosin ester. 請求項１乃至３いずれか一項に記載のホットメルト接着剤樹脂組成物よりなるガラス用接着剤。 An adhesive for glass comprising the hot melt adhesive resin composition according to any one of claims 1 to 3. 請求項１乃至３いずれか一項に記載のホットメルト接着剤樹脂組成物からなる成形体。 A molded product made of the hot melt adhesive resin composition according to any one of claims 1 to 3. 請求項１乃至３いずれか一項に記載のホットメルト接着剤樹脂組成物からなる合わせガラス中間膜用フィルム。 A film for a laminated glass interlayer film comprising the hot melt adhesive resin composition according to any one of claims 1 to 3. 請求項１乃至３いずれか一項に記載のホットメルト接着剤樹脂組成物をガラスと積層してなる積層体。 A laminate obtained by laminating the hot melt adhesive resin composition according to any one of claims 1 to 3 with glass. 請求項１乃至３いずれか一項に記載のホットメルト接着剤樹脂組成物を一対のガラスで挟んでなる合わせガラス。 A laminated glass formed by sandwiching the hot melt adhesive resin composition according to any one of claims 1 to 3 between a pair of glasses.
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