TWI794234B - Adhesive composition, adhesive sheet and sealing body - Google Patents

Adhesive composition, adhesive sheet and sealing body Download PDF

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TWI794234B
TWI794234B TW107118487A TW107118487A TWI794234B TW I794234 B TWI794234 B TW I794234B TW 107118487 A TW107118487 A TW 107118487A TW 107118487 A TW107118487 A TW 107118487A TW I794234 B TWI794234 B TW I794234B
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component
adhesive
adhesive composition
adhesive sheet
parts
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TW201903100A (en
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西嶋健太
長谷川樹
樫尾幹広
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日商琳得科股份有限公司
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/06Non-macromolecular additives organic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/26Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/40Adhesives in the form of films or foils characterised by release liners
    • GPHYSICS
    • G09EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09FDISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05BELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00Electroluminescent light sources
    • H05B33/02Details
    • H05B33/04Sealing arrangements, e.g. against humidity
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00Additional features of adhesives in the form of films or foils
    • C09J2301/30Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Theoretical Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

本發明黏著劑組合物,係含有:(A)成分:改質聚烯烴系樹脂、及(B)成分:未具芳香環的多官能基環氧化合物的黏著劑組合物,其特徵在於:將該黏著劑組合物成形為厚度10μm薄片狀,接著再使硬化並進行測色時,JIS Z 8729-1994所規定CIE L*a*b*表色系的b*值係-2.0~+2.0。本發明亦提供具有使用該黏著劑組合物所形成黏著劑層的黏著薄片、以及密封物經利用上述黏著薄片密封的密封體。根據本發明,可提供可輕易成形為薄片狀、且能成為無色透明性優異之硬 化物的黏著劑組合物,並可提供具有使用該黏著劑組合物所形成黏著劑層的黏著薄片、以及密封物經利用上述黏著薄片密封的密封體。The adhesive composition of the present invention is an adhesive composition containing: (A) component: modified polyolefin resin, and (B) component: polyfunctional epoxy compound without aromatic ring, characterized in that: When the adhesive composition is formed into a sheet with a thickness of 10 μm, and then hardened and measured for color, the b* value of the CIE L*a*b* color system specified in JIS Z 8729-1994 is -2.0~+2.0. The present invention also provides an adhesive sheet having an adhesive layer formed using the adhesive composition, and a sealed body in which a sealant is sealed with the adhesive sheet. According to the present invention, it is possible to provide an adhesive composition that can be easily molded into a sheet and can be a cured product with excellent colorless transparency, and an adhesive sheet having an adhesive layer formed using the adhesive composition, and a sealant A sealing body in which objects are sealed by using the above-mentioned adhesive sheet.

Description

黏著劑組合物、黏著薄片及密封體Adhesive composition, adhesive sheet and sealing body

本發明係關於由容易成形為薄片狀、且能成為優異無色透明性硬化物的黏著劑組合物、具有使用該黏著劑組合物所形成黏著劑層的黏著薄片、以及被密封物經利用上述黏著薄片密封的密封體。The present invention relates to an adhesive composition that can be easily formed into a sheet and can be an excellent colorless and transparent cured product, an adhesive sheet having an adhesive layer formed using the adhesive composition, and an object to be sealed by using the above-mentioned adhesive composition. Lamellar sealing body.

近年,有機EL元件因為利用低電壓直流驅動便可高亮度發光的發光元件,故備受矚目。 但是,有機EL元件會有隨時間經過,容易出現發光亮度、發光效率、發光均勻性等發光特性降低的問題。 該發光特性降低的問題原因可認為因氧、水分等滲入有機EL元件內部,導致電極、有機層劣化的緣故所致。所以,採行使用密封材將有機EL元件施行密封,俾防止氧與水分的滲入。 此種密封材之形成方法,已知有利用熱硬化性樹脂薄片的方法。In recent years, organic EL elements have attracted attention because they are light-emitting elements that can emit light with high brightness even when driven by low-voltage direct current. However, the organic EL element tends to suffer from a problem in that light-emitting characteristics such as light-emitting brightness, light-emitting efficiency, and light-emitting uniformity decrease over time. The cause of this problem of lowering the luminescence characteristics is considered to be that oxygen, moisture, etc. permeate into the organic EL element to degrade electrodes and organic layers. Therefore, the organic EL element is sealed by using a sealing material to prevent the infiltration of oxygen and moisture. As a method for forming such a sealing material, a method using a thermosetting resin sheet is known.

例如專利文獻1有記載:含有:(A)聚異丁烯樹脂、(B)具有能與環氧基產生反應之官能基的聚異戊二烯樹脂及/或聚異丁烯樹脂、(C)賦黏樹脂、以及(D)環氧樹脂的樹脂組合物;以及含有該樹脂組合物的樹脂組合物薄片等。 專利文獻1亦有記載:該樹脂組合物可輕易薄片化,所獲得樹脂組合物薄片頗適用於有機EL元件的密封。 [先行技術文獻] [專利文獻]For example, Patent Document 1 records: (A) polyisobutylene resin, (B) polyisoprene resin and/or polyisobutylene resin having functional groups capable of reacting with epoxy groups, (C) tackifying resin , and (D) a resin composition of an epoxy resin; and a resin composition sheet containing the resin composition; and the like. Patent Document 1 also records that the resin composition can be easily formed into sheets, and the obtained resin composition sheets are quite suitable for sealing organic EL elements. [Prior Art Documents] [Patent Documents]

[專利文獻1]WO2011/062167號(US2012/0283375 A1)[Patent Document 1] WO2011/062167 (US2012/0283375 A1)

(發明所欲解決之課題)(Problem to be solved by the invention)

根據本發明者等的檢討,得知專利文獻1的實施例所記載黏著劑組合物之硬化物會有偏黃的傾向。故期待能形成更優異無色透明性硬化物的黏著劑組合物。According to the examination of the present inventors, it is known that the cured product of the adhesive composition described in the examples of Patent Document 1 tends to be yellowish. Therefore, an adhesive composition capable of forming a more excellent colorless and transparent cured product is expected.

本發明係有鑑於上述實情而完成,目的在於提供:能提供可輕易成形為薄片狀、且能提供優異無色透明性硬化物的黏著劑組合物,以及具有使用該黏著劑組合物所形成黏著劑層的黏著薄片,及被密封物經利用上述黏著薄片密封的密封體。 (解決課題之手段)The present invention has been accomplished in view of the above facts, and aims to provide: an adhesive composition that can be easily formed into a sheet and can provide an excellent colorless and transparent cured product; A layered adhesive sheet, and a sealing body in which the object to be sealed is sealed by the above-mentioned adhesive sheet. (means to solve the problem)

本發明者等為解決上述課題而進行深入鑽研,結果發現組合使用改質聚烯烴系樹脂、與未具有芳香環的多官能基環氧樹脂,且未使用具苯氧基構造的化合物、或降低使用量,便可獲得能提供可輕易成形為薄片狀、且能提供優異無色透明性硬化物的黏著劑組合物,遂完成本發明。The inventors of the present invention conducted in-depth studies to solve the above-mentioned problems, and found that a combination of modified polyolefin-based resin and polyfunctional epoxy resin not having an aromatic ring was used, and a compound with a phenoxy structure was not used, or reduced The amount used can provide an adhesive composition that can be easily formed into a thin sheet and can provide an excellent colorless and transparent hardened product, thus completing the present invention.

緣是,根據本發明將提供下述(1)~(9)之黏著劑組合物、(10)~(12)之黏著薄片、以及(13)、(14)之密封體。 (1)一種黏著劑組合物,係含有下述(A)成分、及(B)成分的黏著劑組合物,其特徵在於:將該黏著劑組合物成形為厚度10μm薄片狀,接著再使硬化並進行測色時,JIS Z 8729-1994所規定CIE L*a*b*表色系的b*值係-2.0~+2.0。 (A)成分:改質聚烯烴系樹脂 (B)成分:未具芳香環的多官能基環氧化合物 (2)如(1)所記載的黏著劑組合物,其中,上述(A)成分係酸改質聚烯烴系樹脂。 (3)如(1)所記載的黏著劑組合物,其中,相對於上述(A)成分100質量份,上述(B)成分的含有量係1~200質量份。 (4)如(1)所記載的黏著劑組合物,其中,更進一步含有下述(C)成分。 (C)成分:軟化點達80℃以上的賦黏劑 (5)如(4)所記載的黏著劑組合物,其中,相對於上述(A)成分100質量份,上述(C)成分的含有量係1~200質量份。 (6)如(1)所記載的黏著劑組合物,其中,更進一步含有下述(D)成分。 (D)成分:咪唑系硬化觸媒 (7)如(6)所記載的黏著劑組合物,其中,相對於上述(B)成分100質量份,上述(D)成分的含有量係1~10質量份。 (8)如(1)所記載的黏著劑組合物,其中,更進一步含有下述(E)成分。 (E)成分:矽烷偶合劑 (9)如(8)所記載的黏著劑組合物,其中,相對於上述(A)成分100質量份,上述(E)成分的含有量係0.01~10質量份。 (10)一種黏著薄片,係具黏著劑層的黏著薄片,其中,上述黏著劑層係使用(1)~(9)中任一項所記載的黏著劑組合物形成。 (11)如(10)所記載的黏著薄片,其中,黏著劑層的厚度係5~25μm。 (12)如(10)所記載的黏著薄片,其中,更進一步設有剝離薄膜。 (13)一種密封體,係被密封物使用(10)~(12)中任一項所記載的黏著薄片進行密封。 (14)如(13)所記載的密封體,其中,上述被密封物係有機EL元件、有機EL顯示器元件、液晶顯示器元件、或太陽電池元件。 [發明效果]The reason is that according to the present invention, the following adhesive compositions (1)-(9), adhesive sheets (10)-(12), and sealing bodies of (13) and (14) are provided. (1) An adhesive composition comprising the following (A) component and (B) component, characterized in that the adhesive composition is formed into a sheet with a thickness of 10 μm, and then hardened And when measuring the color, the b* value of the CIE L*a*b* color system specified in JIS Z 8729-1994 is -2.0~+2.0. Component (A): modified polyolefin resin (B) component: polyfunctional epoxy compound without aromatic ring (2) The adhesive composition as described in (1), wherein the above-mentioned component (A) is Acid modified polyolefin resin. (3) The adhesive composition as described in (1) whose content of the said (B) component is 1-200 mass parts with respect to 100 mass parts of said (A) components. (4) The adhesive composition as described in (1) which contains the following (C)component further. Component (C): Tackifier having a softening point of 80° C. or higher (5) The adhesive composition as described in (4), wherein the content of the component (C) is 100 parts by mass of the component (A) The amount is 1 to 200 parts by mass. (6) The adhesive composition as described in (1) which contains the following (D) component further. (D) Component: imidazole-based hardening catalyst (7) The adhesive composition as described in (6), wherein the content of the above-mentioned (D) component is 1 to 10 parts by mass with respect to 100 parts by mass of the above-mentioned (B) component parts by mass. (8) The adhesive composition as described in (1) which contains the following (E) component further. Component (E): silane coupling agent (9) The adhesive composition described in (8), wherein the content of the component (E) is 0.01 to 10 parts by mass relative to 100 parts by mass of the component (A) . (10) An adhesive sheet having an adhesive layer, wherein the adhesive layer is formed using the adhesive composition described in any one of (1) to (9). (11) The adhesive sheet according to (10), wherein the thickness of the adhesive layer is 5 to 25 μm. (12) The adhesive sheet as described in (10), which is further provided with a release film. (13) A sealing body, which is sealed by using the adhesive sheet described in any one of (10) to (12). (14) The sealed body according to (13), wherein the object to be sealed is an organic EL element, an organic EL display element, a liquid crystal display element, or a solar cell element. [Invention effect]

根據本發明能提供可輕易成形為薄片狀、且能提供優異無色透明性硬化物的黏著劑組合物、具有使用該黏著劑組合物所形成黏著劑層的黏著薄片、及被密封物經利用上述黏著薄片密封的密封體。 本發明所謂「能提供優異無色透明性硬化物」係指提供光線穿透率高、霧度值小的硬化物,且將該黏著劑組合物成形為厚度10μm薄片狀,接著再使硬化並進行測色時,JIS Z 8729-1994所規定CIE L*a*b*表色系的b*值係-2.0~+2.0。According to the present invention, there can be provided an adhesive composition that can be easily formed into a sheet and can provide a cured product with excellent colorless transparency, an adhesive sheet having an adhesive layer formed using the adhesive composition, and an object to be sealed by using the above-mentioned Adhesive sheet-sealed sealing body. The so-called "providing a cured product with excellent colorless transparency" in the present invention refers to providing a cured product with a high light transmittance and a small haze value, and forming the adhesive composition into a sheet with a thickness of 10 μm, and then hardening and carrying out When measuring color, the b* value of the CIE L*a*b* color system specified in JIS Z 8729-1994 is -2.0~+2.0.

以下,針對本發明分開1)黏著劑組合物、2)黏著薄片、及3)密封體進行詳細說明。Hereinafter, 1) the adhesive composition, 2) the adhesive sheet, and 3) the sealing body of the present invention will be described in detail.

1)黏著劑組合物 本發明的黏著劑組合物係含有下述(A)成分、及(B)成分的黏著劑組合物,其中,將該黏著劑組合物成形為厚度10μm薄片狀,接著再使硬化並進行測色時,JIS Z 8729-1994所規定CIE L*a*b*表色系的b*值係-2.0~+2.0。 (A)成分:改質聚烯烴系樹脂 (B)成分:未具芳香環的多官能基環氧化合物1) Adhesive composition The adhesive composition of the present invention is an adhesive composition containing the following (A) component and (B) component, wherein the adhesive composition is shaped into a sheet with a thickness of 10 μm, and then When hardening and measuring the color, the b* value of the CIE L*a*b* color system specified in JIS Z 8729-1994 is -2.0~+2.0. (A) component: modified polyolefin resin (B) component: polyfunctional epoxy compound without aromatic ring

(A)成分:改質聚烯烴系樹脂 本發明黏著劑組合物係含有(A)成分之改質聚烯烴系樹脂。 本發明的黏著劑組合物係藉由含有改質聚烯烴系樹脂,便使黏著強度優異。又,藉由使用含有改質聚烯烴系樹脂的黏著劑組合物,便可效率佳形成較薄的黏著劑層。Component (A): modified polyolefin resin The adhesive composition of the present invention is a modified polyolefin resin containing component (A). The adhesive composition of the present invention is excellent in adhesive strength by containing the modified polyolefin resin. Also, by using an adhesive composition containing a modified polyolefin resin, a thinner adhesive layer can be efficiently formed.

改質聚烯烴系樹脂係經導入官能基的聚烯烴樹脂。改質聚烯烴系樹脂係對先質的聚烯烴樹脂使用改質劑施行改質處理便可獲得。The modified polyolefin resin is a polyolefin resin introduced with functional groups. The modified polyolefin resin can be obtained by modifying the precursor polyolefin resin with a modifying agent.

所謂「聚烯烴樹脂」係指含有由烯烴系單體所衍生重複單元的聚合體。聚烯烴樹脂係可由烯烴系單體所衍生重複單元一種或二種構成的聚合體,亦可由烯烴系單體所衍生重複單元一種或二種以上、與由能和烯烴系單體進行共聚合之單體所衍生重複單元一種或二種以上構成的聚合體。又,聚烯烴樹脂為共聚物的情況,該共聚物的聚合形態並無特別的限定,可為嵌段共聚物、亦可為無規共聚物。The so-called "polyolefin resin" refers to a polymer containing repeating units derived from olefinic monomers. Polyolefin resins can be polymers composed of one or two repeating units derived from olefinic monomers, or can be composed of one or more repeating units derived from olefinic monomers, and can be copolymerized with olefinic monomers. A polymer composed of one or more repeating units derived from a monomer. In addition, when the polyolefin resin is a copolymer, the polymerization form of the copolymer is not particularly limited, and may be a block copolymer or a random copolymer.

烯烴系單體較佳係碳數2~8之α-烯烴,更佳係乙烯、丙烯、1-丁烯、異丁烯、或1-己烯,特佳係乙烯或丙烯。該等烯烴系單體係可單獨使用1種、或組合使用2種以上。 能與烯烴系單體進行共聚合的單體係可舉例如:醋酸乙烯酯、(甲基)丙烯酸酯、苯乙烯等。此處,「(甲基)丙烯酸」係指丙烯酸或甲基丙烯酸的含義(以下亦同)。 能與烯烴系單體進行共聚的單體係可單獨使用1種、或組合使用2種以上。The olefin-based monomer is preferably an α-olefin having 2 to 8 carbon atoms, more preferably ethylene, propylene, 1-butene, isobutene, or 1-hexene, and particularly preferably ethylene or propylene. These olefin-based monomers may be used alone or in combination of two or more. Monomers that can be copolymerized with olefinic monomers include, for example, vinyl acetate, (meth)acrylate, styrene, and the like. Here, "(meth)acryl" means acryl or methacryl (the same applies hereinafter). The monomer system copolymerizable with the olefin-based monomer may be used alone or in combination of two or more.

聚烯烴樹脂係可舉例如:超低密度聚乙烯(VLDPE)、低密度聚乙烯(LDPE)、中密度聚乙烯(MDPE)、高密度聚乙烯(HDPE)、直鏈狀低密度聚乙烯、聚丙烯(PP)、乙烯-丙烯共聚物、烯烴系彈性體(TPO)、乙烯-醋酸乙烯酯共聚物(EVA)、乙烯-(甲基)丙烯酸共聚物、乙烯-(甲基)丙烯酸酯共聚物等。Examples of polyolefin resins include: ultra-low-density polyethylene (VLDPE), low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), linear low-density polyethylene, poly Propylene (PP), ethylene-propylene copolymer, olefin-based elastomer (TPO), ethylene-vinyl acetate copolymer (EVA), ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylate copolymer wait.

聚烯烴樹脂進行改質處理時所使用的改質劑,係分子內具有官能基的化合物。 官能基係可舉例如:羧基、羧酸酐基、羧酸酯基、羥基、環氧基、醯胺基、銨基、腈基、胺基、醯亞胺基、異氰酸酯基、乙醯基、硫醇基、醚基、硫醚基、磺基、膦基、硝基、胺酯基、鹵原子等。該等之中,較佳係羧基、羧酸酐基、羧酸酯基、羥基、銨基、胺基、醯亞胺基、異氰酸酯基,更佳係羧酸酐基、烷氧矽烷基,特佳係羧酸酐基。 具官能基的化合物亦可在分子內具有2種以上的官能基The modifier used for modifying polyolefin resin is a compound with functional groups in the molecule. Examples of functional groups include: carboxyl group, carboxylic anhydride group, carboxylate group, hydroxyl group, epoxy group, amido group, ammonium group, nitrile group, amine group, imide group, isocyanate group, acetyl group, sulfur Alcohol group, ether group, thioether group, sulfo group, phosphino group, nitro group, urethane group, halogen atom, etc. Among them, carboxyl group, carboxylic acid anhydride group, carboxylate group, hydroxyl group, ammonium group, amino group, imide group, isocyanate group are preferred, carboxylic anhydride group and alkoxysilyl group are more preferred, especially Carboxylic anhydride group. Compounds with functional groups can also have two or more functional groups in the molecule

改質聚烯烴系樹脂係可舉例如:酸改質聚烯烴系樹脂、矽烷改質聚烯烴系樹脂,就從獲得本發明更優異效果的觀點,較佳係酸改質聚烯烴系樹脂。Modified polyolefin resins include, for example, acid-modified polyolefin resins and silane-modified polyolefin resins, and acid-modified polyolefin resins are preferred from the viewpoint of obtaining better effects of the present invention.

所謂「酸改質聚烯烴系樹脂」係指針對聚烯烴樹脂利用酸進行接枝改質者。例如使聚烯烴樹脂、與不飽和羧酸或不飽和羧酸酐(以下亦將該等統稱為「不飽和羧酸等」)進行反應,而導入羧基或羧酸酐基者(接枝改質)。The so-called "acid-modified polyolefin-based resin" refers to a polyolefin resin that is graft-modified with an acid. For example, polyolefin resin is reacted with unsaturated carboxylic acid or unsaturated carboxylic acid anhydride (hereinafter, these are also collectively referred to as "unsaturated carboxylic acid, etc.") to introduce carboxyl group or carboxylic anhydride group (graft modification).

使與聚烯烴樹脂進行反應的不飽和羧酸等,係可舉例如:順丁烯二酸、反丁烯二酸、衣康酸、檸康酸、戊烯二酸、四氫酞酸、烏頭酸等不飽和羧酸;順丁烯二酸酐、衣康酸酐、戊烯二酸酐、檸康酸酐、烏頭酸酐、降烯二羧酸酐、四氫酞酸酐等不飽和羧酸酐。 該等係可單獨使用1種、或組合使用2種以上。 該等之中,就從容易獲得更優異黏著強度之黏著劑組合物的觀點,較佳係順丁烯二酸酐。Unsaturated carboxylic acids reacted with polyolefin resins, such as maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, aconitum Unsaturated carboxylic acids such as acid; maleic anhydride, itaconic anhydride, glutaconic anhydride, citraconic anhydride, aconitic anhydride, nor-alkenedicarboxylic anhydride, tetrahydrophthalic anhydride and other unsaturated carboxylic anhydrides. These can be used individually by 1 type or in combination of 2 or more types. Among these, maleic anhydride is preferable from the viewpoint of being easy to obtain an adhesive composition having a higher adhesive strength.

使與聚烯烴樹脂進行反應不飽和羧酸等之量,相對於聚烯烴樹脂100質量份,較佳係0.1~5質量份、更佳係0.2~3質量份、特佳係0.2~1.0質量份。藉由使進行反應的不飽和羧酸等之量在上述範圍內,含有所獲得酸改質聚烯烴系樹脂的黏著劑組合物,便可成為黏著強度更優異。The amount of unsaturated carboxylic acid or the like to react with the polyolefin resin is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 3 parts by mass, and most preferably 0.2 to 1.0 parts by mass relative to 100 parts by mass of the polyolefin resin . When the amount of the unsaturated carboxylic acid or the like to be reacted is within the above-mentioned range, the adhesive composition containing the obtained acid-modified polyolefin-based resin can become more excellent in adhesive strength.

酸改質聚烯烴系樹脂亦可使用市售物。市售物係可舉例如:ADMER(註冊商標)(三井化學公司製)、UNISTOLE(註冊商標)(三井化學公司製)、BondyRam(Polyram公司製)、orevac(註冊商標)(ARKEMA公司製)、MODIC(註冊商標)(三菱化學公司製)等。As the acid-modified polyolefin-based resin, a commercially available one can also be used. Commercially available products include, for example, ADMER (registered trademark) (manufactured by Mitsui Chemicals), UNISTOLE (registered trademark) (manufactured by Mitsui Chemicals), Bondy Ram (manufactured by Polyram), orevac (registered trademark) (manufactured by ARKEMA), MODIC (registered trademark) (manufactured by Mitsubishi Chemical Corporation) and the like.

所謂「矽烷改質聚烯烴系樹脂」係指利用不飽和矽烷化合物,對聚烯烴樹脂施行接枝改質者。矽烷改質聚烯烴系樹脂係具有在主鏈的聚烯烴樹脂上,接枝共聚合屬於側鏈的不飽和矽烷化合物之構造。例如:矽烷改質聚乙烯樹脂及矽烷改質乙烯-醋酸乙烯酯共聚物。其中,較佳係:矽烷改質低密度聚乙烯、矽烷改質超低密度聚乙烯、矽烷改質直鏈狀低密度聚乙烯等矽烷改質聚乙烯樹脂。The so-called "silane-modified polyolefin-based resin" refers to the graft modification of polyolefin resin by using unsaturated silane compound. The silane-modified polyolefin resin has a structure in which unsaturated silane compounds belonging to side chains are grafted and copolymerized on the main chain polyolefin resin. For example: silane-modified polyethylene resin and silane-modified ethylene-vinyl acetate copolymer. Among them, preferred are silane-modified polyethylene resins such as silane-modified low-density polyethylene, silane-modified ultra-low-density polyethylene, and silane-modified linear low-density polyethylene.

使與上述聚烯烴樹脂進行反應的不飽和矽烷化合物,係可舉例如:乙烯矽烷化合物;烯丙基三甲氧基矽烷、烯丙基三乙氧基矽烷等烯丙基矽烷化合物;3-丙烯醯氧丙基三甲氧基矽烷、3-甲基丙烯醯氧丙基三甲氧基矽烷等(甲基)丙烯氧基含有矽烷化合物等,就從通用性、黏著性等觀點,較佳係乙烯矽烷化合物。此處,(甲基)丙烯氧基係表示丙烯醯氧基或甲基丙烯醯氧基(以下亦同)。Unsaturated silane compounds that react with the above-mentioned polyolefin resins include, for example, vinyl silane compounds; allyl silane compounds such as allyl trimethoxysilane and allyl triethoxysilane; 3-acryl (Meth)acryloxy-containing silane compounds such as oxypropyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane are preferred vinyl silane compounds from the viewpoints of versatility and adhesiveness. . Here, (meth)acryloxy means acryloxy or methacryloxy (the same applies hereinafter).

乙烯矽烷化合物係可舉例如:乙烯三甲氧基矽烷、乙烯三乙氧基矽烷、乙烯三丙氧基矽烷、乙烯三異丙氧基矽烷、乙烯三丁氧基矽烷、乙烯三戊氧基矽烷、乙烯三苯氧基矽烷、乙烯三苄氧基矽烷、乙烯三亞甲二氧基矽烷、乙烯三伸乙二氧基矽烷、乙烯丙醯氧基矽烷、乙烯三乙醯氧基矽烷、乙烯三羧基矽烷等。該等係可單獨使用1種、或組合使用2種以上。 當使不飽和矽烷化合物進行接枝聚合於屬於主鏈的聚烯烴樹脂時,條件係可採取公知接枝聚合的常法。Examples of vinyl silane compounds include: vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tripropoxysilane, vinyl triisopropoxysilane, vinyl tributoxysilane, vinyl tripentoxysilane, Ethylenetriphenoxysilane, Ethylenetribenzyloxysilane, Ethylenetrimethylenedioxysilane, Ethylenetriethylenedioxysilane, Ethylenetrioxysilane, Ethylenetriacetyloxysilane, Ethylenetricarboxysilane wait. These can be used individually by 1 type or in combination of 2 or more types. When graft-polymerizing the unsaturated silane compound to the polyolefin resin belonging to the main chain, the condition is that a well-known conventional method of graft polymerization can be adopted.

使與聚烯烴樹脂進行反應的不飽和矽烷化合物量,相對於聚烯烴樹脂100質量份,較佳係0.1~10質量份、更佳係0.3~7質量份、特佳係0.5~5質量份。藉由進行反應的不飽和矽烷化合物量在上述範圍內,則含有所獲得矽烷改質聚烯烴系樹脂的黏著劑便成為黏著強度更優異。The amount of the unsaturated silane compound to react with the polyolefin resin is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 7 parts by mass, and most preferably 0.5 to 5 parts by mass based on 100 parts by mass of the polyolefin resin. When the amount of the unsaturated silane compound to be reacted is within the above range, the adhesive containing the obtained silane-modified polyolefin-based resin becomes more excellent in adhesive strength.

矽烷改質聚烯烴系樹脂亦可使用市售物。市售物係可例如:LINKLON(註冊商標)(三菱化學公司製)等。尤其較佳係可使用低密度聚乙烯系的LINKLON、直鏈狀低密度聚乙烯系的LINKLON、超低密度聚乙烯系的LINKLON、以及乙烯-醋酸乙烯酯共聚物系的LINKLON。As the silane-modified polyolefin-based resin, a commercially available one can also be used. Commercially available products include, for example, LINKLON (registered trademark) (manufactured by Mitsubishi Chemical Corporation) and the like. In particular, low-density polyethylene-based LINKLON, linear low-density polyethylene-based LINKLON, ultra-low-density polyethylene-based LINKLON, and ethylene-vinyl acetate copolymer-based LINKLON can be used.

改質聚烯烴系樹脂係可單獨使用1種、或組合使用2種以上。The modified polyolefin-based resins may be used alone or in combination of two or more.

改質聚烯烴系樹脂的數量平均分子量(Mn),就從輕易獲得本發明效果等理由,較佳係10,000~2,000,000、更佳係20,000~1,500,000。 改質聚烯烴系樹脂的數量平均分子量(Mn)係溶劑使用四氫呋喃(THF),施行凝膠滲透色層分析(GPC),便可求取標準聚苯乙烯換算值。The number average molecular weight (Mn) of the modified polyolefin-based resin is preferably 10,000-2,000,000, more preferably 20,000-1,500,000, for the reasons of easily obtaining the effect of the present invention. The number average molecular weight (Mn)-based solvent of the modified polyolefin-based resin uses tetrahydrofuran (THF) and performs gel permeation chromatography (GPC) to obtain a standard polystyrene-equivalent value.

(B)成分:未具芳香環的多官能基環氧化合物 本發明黏著劑組合物係含有(B)成分之未具芳香環的多官能基環氧化合物。 因為本發明的黏著劑組合物含有多官能基環氧化合物,因而其硬化物成為水蒸氣阻斷性優異。 再者,因為本發明所使用的(B)成分係未具芳香環的多官能基環氧化合物,因而含有其的黏著劑組合物便能提供優異透明性的硬化物。即,相較於具芳香環的多官能基環氧化合物之下,未具芳香環的多官能基環氧化合物與(A)成分的改質聚烯烴樹脂的相溶性較高。因而,藉由將多官能基環氧化合物使用為(B)成分,便可獲得能提供光線穿透率更高、且霧度小之硬化物的黏著劑組合物。 就從此觀點,本發明的黏著劑組合物最好未含有具芳香環之多官能基環氧化合物。特別係如後述,本發明黏著劑組合物的硬化物之b*值最好接近0,因而更佳係分子內未含有具苯氧基構造之多官能基環氧化合物。 此處所謂「苯氧基構造」係指下述(a)、(b)所示的部分構造(以下亦同):Component (B): polyfunctional epoxy compound without aromatic ring The adhesive composition of the present invention is a polyfunctional epoxy compound without aromatic ring containing component (B). Since the adhesive composition of the present invention contains a multifunctional epoxy compound, its cured product has excellent water vapor barrier properties. Furthermore, since the component (B) used in the present invention is a polyfunctional epoxy compound without an aromatic ring, the adhesive composition containing it can provide a cured product with excellent transparency. That is, the polyfunctional epoxy compound which does not have an aromatic ring has higher compatibility with the modified polyolefin resin of (A) component than the polyfunctional epoxy compound which has an aromatic ring. Therefore, by using the polyfunctional epoxy compound as the component (B), an adhesive composition capable of providing a cured product with higher light transmittance and less haze can be obtained. From this point of view, the adhesive composition of the present invention preferably does not contain a polyfunctional epoxy compound having an aromatic ring. In particular, as described later, the b* value of the hardened product of the adhesive composition of the present invention is preferably close to 0, so it is more preferable that the molecule does not contain a polyfunctional epoxy compound with a phenoxy structure. The term "phenoxy structure" here refers to the partial structures shown in (a) and (b) below (the same applies hereinafter):

[化1]

Figure 02_image001
[chemical 1]
Figure 02_image001

上述式(a)、(b)中,A1 係表示無取代(或具取代基)的芳基;A2 係表示無取代(或具取代基)的伸芳基。 無取代(或具取代基)的芳基中,芳基係可舉例如:苯基、1-萘基、2-萘基等。 無取代(或具取代基)的伸芳基中,伸芳基係可舉例如:1,4-伸苯基、1,3-伸苯基、1,2-伸苯基、1,5-伸萘基、2,6-伸萘基等。 具取代基的芳基、及具取代基的伸芳基中,取代基係表示:甲基、異丙基、第三丁基等碳數1~6之烷基;甲氧基、異丙氧基、第三丁氧基等碳數1~6之烷氧基;氟原子、氯原子、溴原子等鹵原子等。In the above formulas (a) and (b), A 1 represents an unsubstituted (or substituted) aryl group; A 2 represents an unsubstituted (or substituted) aryl group. Among the unsubstituted (or substituted) aryl groups, the aryl group includes, for example, phenyl, 1-naphthyl, 2-naphthyl and the like. Among the unsubstituted (or substituent) aryl groups, the aryl groups include, for example: 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, 1,5- Naphthyl, 2,6-naphthyl, etc. Among aryl groups with substituents and aryl groups with substituents, the substituents represent: methyl, isopropyl, tertiary butyl and other alkyl groups with 1 to 6 carbons; methoxy, isopropoxy C1-6 alkoxy group, tertiary butoxy group, etc.; halogen atom such as fluorine atom, chlorine atom, bromine atom, etc.

所謂「多官能基環氧化合物」係指分子內具有2以上環氧基的化合物。 (B)成分係可舉例如:氫化雙酚A型環氧樹脂、氫化雙酚F型環氧樹脂、氫化雙酚S型環氧樹脂、氫化雙酚A二環氧丙醚、氫化雙酚F二環氧丙醚、氫化雙酚S二環氧丙醚、季戊四醇聚環氧丙醚、1,6-己二醇二環氧丙醚、六氫酞酸二環氧丙基酯、新戊二醇二環氧丙醚、三羥甲基丙烷聚環氧丙醚、2,2-雙(3-環氧丙基-4-環氧丙氧基苯基)丙烷、二羥甲基三環癸烷二環氧丙醚、二環戊二烯二甲醇二環氧丙醚等。 多官能基環氧化合物係可單獨使用1種、或組合使用2種以上。 (B)成分的多官能基環氧化合物之數量平均分子量(Mn),就從能輕易獲得本發明效果等理由,較佳係100~3,000、更佳係200~1,500。The so-called "polyfunctional epoxy compound" refers to a compound having two or more epoxy groups in the molecule. (B) The component system can be, for example: hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, hydrogenated bisphenol S type epoxy resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F Diglycidyl ether, Hydrogenated Bisphenol S Diglycidyl Ether, Pentaerythritol Polyglycidyl Ether, 1,6-Hexanediol Diglycidyl Ether, Diglycidyl Hexahydrophthalate, Neopentyl Diglycidyl Ether Alcohol Diglycidyl Ether, Trimethylolpropane Polyglycidyl Ether, 2,2-Bis(3-Epoxypropyl-4-Glycidyloxyphenyl)propane, Dimethyloltricyclodecane Alkane Diglycidyl Ether, Dicyclopentadiene Dimethanol Diglycidyl Ether, etc. The polyfunctional epoxy compound system can be used individually by 1 type or in combination of 2 or more types. The number average molecular weight (Mn) of the polyfunctional epoxy compound of the component (B) is preferably 100-3,000, more preferably 200-1,500, for reasons such as the effect of the present invention can be easily obtained.

(B)成分的多官能基環氧化合物之環氧當量,較佳係100g/eq以上且500g/eq以下、更佳係150g/eq以上且300g/eq以下。藉由使用含有環氧當量100g/eq以上且500g/eq以下之(B)成分多官能基環氧化合物的黏著劑組合物,便可效率佳形成低逸氣性密封材。The epoxy equivalent of the polyfunctional epoxy compound of the component (B) is preferably from 100 g/eq to 500 g/eq, more preferably from 150 g/eq to 300 g/eq. The low outgassing sealing material can be efficiently formed by using the adhesive composition containing the polyfunctional epoxy compound of the component (B) having an epoxy equivalent weight of not less than 100 g/eq and not more than 500 g/eq.

本發明的黏著劑組合物係除上述(A)成分、(B)成分之外,尚亦可含有(C)成分之軟化點達80℃以上的賦黏劑。 含有(C)成分的黏著劑組合物,係可輕易保持一定形狀、能效率更佳地形成薄片狀黏著劑層。The adhesive composition of the present invention may contain, in addition to the above-mentioned components (A) and (B), an adhesive agent having a softening point of (C) of 80° C. or higher. The adhesive composition containing the component (C) can easily maintain a certain shape, and can form a sheet-shaped adhesive layer more efficiently.

(C)成分的賦黏劑係在軟化點達80℃以上的賦黏劑前提下,其餘並無特別的限制。可例如:聚合松脂、聚合松脂酯、松脂衍生物等松脂系樹脂;聚萜烯樹脂、芳香族改質萜烯樹脂及其氫化物、萜烯酚樹脂等萜烯系樹脂;香豆酮-茚樹脂;脂肪族石油系樹脂、芳香族系石油樹脂及其氫化物、脂肪族/芳香族共聚物石油樹脂等石油樹脂;苯乙烯或取代苯乙烯的低分子量聚合體;α-甲基苯乙烯單聚系樹脂、α-甲基苯乙烯/苯乙烯共聚合系樹脂、苯乙烯系單體/脂肪族系單體共聚合系樹脂、苯乙烯系單體/α-甲基苯乙烯/脂肪族系單體共聚合系樹脂、苯乙烯系單體單聚系樹脂、苯乙烯系單體/芳香族系單體共聚合系樹脂等苯乙烯系樹脂等等。該等賦黏劑係可單獨使用1種、或組合使用2種以上。 該等之中,較佳係苯乙烯系樹脂、更佳係苯乙烯系單體/脂肪族系單體共聚合系樹脂。The tackifier of component (C) is provided that the tackifier has a softening point of 80° C. or higher, and the rest are not particularly limited. For example: rosin-based resins such as polymerized rosin, polymerized rosin ester, and rosin derivatives; terpene-based resins such as polyterpene resins, aromatic modified terpene resins and their hydrogenated products, and terpene phenol resins; coumarone-indene Resins; petroleum resins such as aliphatic petroleum resins, aromatic petroleum resins and their hydrogenated products, aliphatic/aromatic copolymer petroleum resins; low molecular weight polymers of styrene or substituted styrene; α-methylstyrene Polymer resin, α-methylstyrene/styrene copolymer resin, styrene monomer/aliphatic monomer copolymer resin, styrene monomer/α-methylstyrene/aliphatic Monomer copolymer resin, styrene monomer monopolymer resin, styrene monomer/aromatic monomer copolymer resin, and other styrene resins. These tackifiers can be used alone or in combination of two or more. Among these, styrene-based resins are preferred, and styrene-based monomer/aliphatic monomer copolymerized resins are more preferred.

(C)成分係軟化點達80℃以上的賦黏劑。藉由使用軟化點達80℃以上的賦黏劑,便可獲得高溫時的黏著性優異之黏著劑組合物。又,將黏著劑組合物成形為薄片狀時的作業性亦獲提升。Component (C) is a tackifier with a softening point of 80°C or higher. By using a tackifier having a softening point of 80° C. or higher, an adhesive composition excellent in tackiness at high temperatures can be obtained. In addition, workability when forming the adhesive composition into a sheet shape is also improved.

本發明的黏著劑組合物含有(C)成分時,其含有量相對於上述(A)成分100質量份,較佳係1~200質量份、更佳係10~150質量份。當含有(C)成分的情況,若(C)成分的含有量過少,則會有黏著劑組合物較難成形為薄片狀的可能性。另一方面,若(C)成分的含有量過多,則會有黏著劑層變脆的可能性。When the adhesive composition of this invention contains (C)component, the content is preferably 1-200 mass parts with respect to 100 mass parts of said (A) components, More preferably, it is 10-150 mass parts. When containing (C)component, if the content of (C)component is too small, it may become difficult to shape an adhesive composition into a sheet shape. On the other hand, when there is too much content of (C)component, there exists a possibility that an adhesive agent layer may become brittle.

本發明的黏著劑組合物係除上述(A)成分、(B)成分之外,尚亦可含有(D)成分之咪唑系硬化觸媒。 藉由使用含有咪唑系硬化觸媒的黏著劑組合物,便可輕易獲得即便高溫時仍具有優異黏著性的硬化物。The adhesive composition of the present invention may contain an imidazole-based hardening catalyst of the component (D) in addition to the above-mentioned components (A) and (B). By using an adhesive composition containing an imidazole-based curing catalyst, a cured product having excellent adhesiveness even at high temperatures can be easily obtained.

咪唑系硬化觸媒係可舉例如:2-甲基咪唑、2-苯基咪唑、2-十一烷基咪唑、2-十七烷基咪唑、2-乙基-4-甲基咪唑、2-苯基-4-甲基咪唑、2-苯基-4-甲基-5-羥甲基咪唑、2-苯基-4,5-二羥甲基咪唑等。該等之中,較佳係2-乙基-4-甲基咪唑。 該等咪唑系硬化觸媒係可單獨使用1種、或組合使用2種以上。Examples of imidazole-based hardening catalysts include: 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2 -Phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dimethylimidazole and the like. Among them, 2-ethyl-4-methylimidazole is preferred. These imidazole-based curing catalysts may be used alone or in combination of two or more.

若本發明的黏著劑組合物含有(D)成分的情況,其含有量相對於上述(A)成分100質量份,較佳係1~10質量份、更佳係2~5質量份。咪唑系硬化觸媒含有量在該範圍內的黏著劑組合物之硬化物,即便在高溫時仍具有優異的黏著性。When the adhesive composition of the present invention contains the component (D), the content is preferably 1 to 10 parts by mass, more preferably 2 to 5 parts by mass, based on 100 parts by mass of the above-mentioned component (A). The cured product of the adhesive composition containing the imidazole-based curing catalyst in this range has excellent adhesiveness even at high temperatures.

本發明的黏著劑組合物係除上述(A)成分、(B)成分之外,尚亦可含有(E)成分之矽烷偶合劑。 藉由使用含有矽烷偶合劑的黏著劑組合物,便可輕易獲得在常溫及高溫環境下的黏著強度更優異之硬化物。The adhesive composition of the present invention may contain a silane coupling agent (E) in addition to the above-mentioned (A) and (B) components. By using an adhesive composition containing a silane coupling agent, it is possible to easily obtain a cured product with better adhesive strength under normal temperature and high temperature environments.

矽烷偶合劑係可使用公知矽烷偶合劑。其中,較佳係分子內至少具有1個烷氧矽烷基的有機矽化合物。 矽烷偶合劑係可舉例如:乙烯三甲氧基矽烷、乙烯三乙氧基矽烷、3-(甲基)丙烯氧丙基三甲氧基矽烷等含聚合性不飽和基之矽化合物;3-環氧丙氧基丙基三甲氧基矽烷、8-環氧丙氧基辛基三甲氧基矽烷、2-(3,4-環氧基環己基)乙基三甲氧基矽烷等具環氧構造的矽化合物;3-胺丙基三甲氧基矽烷、N-(2-胺乙基)-3-胺丙基三甲氧基矽烷、N-(2-胺乙基)-8-胺辛基三甲氧基矽烷、N-(2-胺乙基)-3-胺丙基甲基二甲氧基矽烷等含胺基之矽化合物;3-氯丙基三甲氧基矽烷;3-異氰酸酯基丙基三乙氧基矽烷、3-巰基丙基三甲氧基矽烷、3-三甲氧基矽烷基丙基琥珀酸酐等。 該等矽烷偶合劑係可單獨使用1種、或組合使用2種以上。As the silane coupling agent, known silane coupling agents can be used. Among them, organosilicon compounds having at least one alkoxysilyl group in the molecule are preferred. Silane coupling agents can include, for example, silicon compounds containing polymerizable unsaturated groups such as ethylene trimethoxysilane, ethylene triethoxysilane, 3-(meth)acryloxypropyl trimethoxysilane; 3-epoxy Silicone with epoxy structure such as propoxypropyltrimethoxysilane, 8-glycidoxyoctyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc. Compounds; 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-8-aminooctyltrimethoxy Amino-containing silicon compounds such as silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane; 3-chloropropyltrimethoxysilane; 3-isocyanatopropyltriethyl Oxysilane, 3-mercaptopropyltrimethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride, etc. These silane coupling agents may be used alone or in combination of two or more.

當本發明的黏著劑組合物含有矽烷偶合劑的情況,其含有量相對於上述(A)成分100質量份,較佳係0.01~10質量份、更佳係0.02~5質量份。When the adhesive composition of the present invention contains a silane coupling agent, its content is preferably 0.01 to 10 parts by mass, more preferably 0.02 to 5 parts by mass relative to 100 parts by mass of the above-mentioned component (A).

本發明的黏著劑組合物亦可含有溶劑。 溶劑係可舉例如:苯、甲苯等芳香族烴系溶劑;醋酸乙酯、醋酸丁酯等酯系溶劑;丙酮、甲乙酮、甲基異丁酮等酮系溶劑;正戊烷、正己烷、正庚烷等脂肪族烴系溶劑;環戊烷、環己烷、甲基環己烷等脂環式烴系溶劑等。 該等溶劑係可單獨使用1種、或組合使用2種以上。 溶劑含有量係可經考慮塗佈性等之後再行適當決定。The adhesive composition of this invention may also contain a solvent. Examples of solvent systems include aromatic hydrocarbon solvents such as benzene and toluene; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; n-pentane, n-hexane, n- Aliphatic hydrocarbon solvents such as heptane; alicyclic hydrocarbon solvents such as cyclopentane, cyclohexane, and methylcyclohexane, etc. These solvents may be used alone or in combination of two or more. The solvent content can be appropriately determined in consideration of applicability and the like.

本發明的黏著劑組合物係在不致妨礙本發明效果之範圍內,亦可含有其他成分。 該其他成分係可舉例如:紫外線吸收劑、抗靜電劑、光安定劑、抗氧化劑、樹脂安定劑、填充劑、顏料、增量劑、軟化劑等添加劑。 該等係可單獨使用1種、或組合使用2種以上。 當本發明的黏黏著劑組合物含有該等添加劑的情況,含有量係可配合目的再行適當決定。The adhesive composition of the present invention may contain other components within the range not to inhibit the effects of the present invention. The other components include, for example, additives such as ultraviolet absorbers, antistatic agents, light stabilizers, antioxidants, resin stabilizers, fillers, pigments, extenders, and softeners. These can be used individually by 1 type or in combination of 2 or more types. When the adhesive composition of the present invention contains these additives, the content can be appropriately determined according to the purpose.

本發明的黏著劑組合物係藉由將既定成分依照常法,施行適當混合‧攪拌便可製備。The adhesive composition of the present invention can be prepared by properly mixing and stirring predetermined components according to a conventional method.

本發明的黏著劑組合物係當成形為厚度10μm薄片狀,接著再使硬化並進行測色時,JIS Z 8729-1994所規定CIE L*a*b*表色系的b*值係-2.0~+2.0。 上述測色時,相關將黏著劑組合物成形為薄片狀的方法、以及硬化方法,係可使用後述方法。When the adhesive composition of the present invention is formed into a thin sheet with a thickness of 10 μm, and then hardened and subjected to color measurement, the b* value of the CIE L*a*b* color system specified in JIS Z 8729-1994 is -2.0 ~+2.0. In the above-mentioned color measurement, the method described below can be used for the method of forming the adhesive composition into a sheet and the method of hardening it.

L*a*b*表色系中,L*係表示明度,a*及b*係表示色相與彩度。a*為正值的情況係表示紅方向的色彩與彩度,a*為負值的情況係表示綠方向的色彩與彩度,b*為正值的情況係表示黃方向的色彩與彩度,b*為負值的情況係表示藍方向的色彩與彩度。隨a*、b*的絕對值變小,逐漸成為無色。 本發明黏著劑組合物的硬化物之b*值係-2.0~+2.0、較佳係-1.0~+2.0、更佳係0.0~2.0、特佳係0.0~1.0。本發明黏著劑組合物的硬化物係不管黃方向(+b*)、或藍方向(-b*)均較少偏移。能提供b*在上述範圍的硬化物之黏著劑組合物,具有全光線穿透率高、霧度值低、且著色非常少的優點,頗適用為有機EL元件等發光裝置的密封材。 CIE L*a*b*表色系中,b*值係可利用實施例所記載方法進行測定。In the L*a*b* color system, the L* system represents lightness, and the a* and b* systems represent hue and chroma. When a* is positive, it means the color and chroma in the red direction; when a* is negative, it means the color and chroma in the green direction; when b* is positive, it means the color and chroma in the yellow direction , when b* is a negative value, it represents the color and chroma in the blue direction. As the absolute values of a* and b* become smaller, it gradually becomes colorless. The b* value of the hardened product of the adhesive composition of the present invention is -2.0~+2.0, preferably -1.0~+2.0, more preferably 0.0~2.0, and most preferably 0.0~1.0. The cured system of the adhesive composition of the present invention is less deviated in either the yellow direction (+b*) or the blue direction (-b*). The adhesive composition that can provide a cured product with b* in the above range has the advantages of high total light transmittance, low haze value, and very little coloring, and is quite suitable as a sealing material for light-emitting devices such as organic EL elements. In the CIE L*a*b* color system, the b* value can be measured by the method described in the examples.

上述硬化物的b*值會受到黏著劑組合物中所含具芳香環(苯氧基構造)之化合物的影響。所以,能提供b*值-2.0~+2.0之硬化物的黏著劑組合物,藉由未使用具芳香環(苯氧基構造)的化合物、或減少使用量,便可效率佳且輕易地製備。 本發明的黏著劑組合物較佳係未含有具芳香環(苯氧基構造)的化合物、或具芳香環(苯氧基構造)的化合物含有量少(相對於黏著劑組合物全體,依固形份量計在5質量%以下),更佳係未含有具芳香環(苯氧基構造)的化合物。The b* value of the above cured product is affected by the compound having an aromatic ring (phenoxy structure) contained in the adhesive composition. Therefore, an adhesive composition that can provide a cured product with a b* value of -2.0~+2.0 can be efficiently and easily prepared by not using a compound with an aromatic ring (phenoxy structure) or reducing the amount of use. . The adhesive composition of the present invention preferably does not contain a compound having an aromatic ring (phenoxy structure), or contains a small amount of a compound having an aromatic ring (phenoxy structure) (relative to the entire adhesive composition, depending on the solid 5% by weight or less), more preferably no compound having an aromatic ring (phenoxy structure).

本發明的黏著劑組合物係將成形為厚度10μm薄片狀,接著再使其硬化而成為測試片,當測定全光線穿透率與霧度值時,全光線穿透率較佳係85%以上、更佳係90%以上。全光線穿透率的上限並無特別限制,通常係95%以下。又,霧度值較佳係1.4%以下、更佳係1%以下。霧度值得下限並無特別限制,通常係0.5%以上。 全光線穿透率係可根據JIS K7361:1997進行測定。霧度值係可根據JIS K7136:2000進行測定。The adhesive composition of the present invention will be formed into a thin sheet with a thickness of 10 μm, and then hardened to become a test piece. When measuring the total light transmittance and haze value, the total light transmittance is preferably more than 85%. , preferably more than 90%. The upper limit of the total light transmittance is not particularly limited, and is usually below 95%. Also, the haze value is preferably at most 1.4%, more preferably at most 1%. The lower limit of the haze value is not particularly limited, and is usually 0.5% or more. The total light transmittance can be measured in accordance with JIS K7361:1997. The haze value can be measured based on JIS K7136:2000.

依如上述,本發明的黏著劑組合物係將改質聚烯烴系樹脂使用為(A)成分,更將與該(A)成分呈高相溶性之多官能基環氧化合物的未具芳香環的多官能基環氧化合物使用為(B)成分。結果,本發明黏著劑組合物的硬化物便成為全光線穿透率高、且霧度值小。As mentioned above, the adhesive composition of the present invention uses a modified polyolefin resin as the component (A), and uses a polyfunctional epoxy compound that is highly compatible with the component (A) without an aromatic ring. A polyfunctional epoxy compound is used as (B) component. As a result, the hardened product of the adhesive composition of the present invention has a high total light transmittance and a small haze value.

本發明的黏著劑組合物係容易成形為薄片狀、且無色透明性優異。所以,本發明的黏著劑組合物頗適用於光學用途。The adhesive composition of the present invention is easy to form into a sheet shape, and has excellent colorless transparency. Therefore, the adhesive composition of the present invention is quite suitable for optical applications.

2)黏著薄片 本發明的黏著薄片係具有黏著劑層的黏著薄片,而,上述黏著劑層係使用本發明的黏著劑組合物形成。2) Adhesive sheet The adhesive sheet of the present invention is an adhesive sheet having an adhesive layer, and the adhesive layer is formed using the adhesive composition of the present invention.

黏著薄片的黏著劑層厚度並無特別的限定,通常係5~25μm、較佳係10~20μm。 厚度在上述範圍內的黏著劑層頗適用為密封材。The thickness of the adhesive layer of the adhesive sheet is not particularly limited, and is usually 5-25 μm, preferably 10-20 μm. The adhesive layer whose thickness is within the above range is suitable as a sealing material.

本發明的黏著薄片亦可設有剝離薄膜。 剝離薄膜係在黏著薄片的製造步驟中發揮支撐體的功能,且直到使用黏著薄片為止的期間內,均發揮黏著劑層之保護片的功能。 在使用本發明黏著薄片時,通常剝離薄膜會被剝離除去。The adhesive sheet of the present invention may also be provided with a release film. The release film functions as a support in the production steps of the adhesive sheet, and functions as a protective sheet for the adhesive layer until the adhesive sheet is used. When using the adhesive sheet of the present invention, the release film is usually peeled off.

剝離薄膜係可利用習知公知物。例如在剝離薄膜用基材上,設有經利用剝離劑施行剝離處理的剝離層。 剝離薄膜用的基材係可舉例如:玻璃紙、銅版紙、高級紙等紙基材;在該等紙基材上層壓著聚乙烯等熱可塑性樹脂的層壓紙;以及聚對苯二甲酸乙二酯樹脂、聚對苯二甲酸丁二酯樹脂、聚萘二甲酸乙二酯樹脂、聚丙烯樹脂、聚乙烯樹脂等塑膠薄膜等。 剝離劑係可舉例如:聚矽氧系樹脂、烯烴系樹脂、異戊二烯系樹脂、丁二烯系樹脂等橡膠系彈性體;長鏈烷基系樹脂、醇酸系樹脂、氟系樹脂等。As the release film, conventionally known ones can be used. For example, a release layer subjected to a release treatment with a release agent is provided on a base material for a release film. Examples of substrates for release films include paper substrates such as cellophane, coated paper, and high-grade paper; laminated paper in which thermoplastic resins such as polyethylene are laminated on these paper substrates; and polyethylene terephthalate. Plastic films such as diester resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polypropylene resin, polyethylene resin, etc. The release agent system can include, for example, rubber-based elastomers such as silicone-based resins, olefin-based resins, isoprene-based resins, and butadiene-based resins; long-chain alkyl-based resins, alkyd-based resins, and fluorine-based resins. wait.

當發明黏著薄片具有剝離薄膜時,剝離薄膜的片數係可為1片、亦可為2片,通常在黏著劑層二側分別設有1片(合計2片)剝離薄膜。此時2片剝離薄膜係可為相同、亦可為不同,但最好2片剝離薄膜具有不同剝離力。藉由2片剝離薄膜的剝離力不同,黏著薄片在使用時便不易發生問題。即,藉由將2片剝離薄膜的剝離力設為不同,便可效率佳執行最初進行剝離薄膜撕開的步驟。When the inventive adhesive sheet has a release film, the number of release films may be one or two, and usually one (total two) release films are respectively provided on both sides of the adhesive layer. At this time, the two peeling films may be the same or different, but it is preferable that the two peeling films have different peeling forces. Since the peeling force of the two peeling films is different, problems are less likely to occur when the adhesive sheet is used. That is, by setting the peeling forces of the two peeling films differently, the step of tearing the peeling film first can be performed efficiently.

黏著薄片的製造方法並無特別的限定。例如使用澆鑄法便可製造黏著薄片。 黏著薄片的製造方法並無特別的限定。例如使用澆鑄法便可製造黏著薄片。 利用澆鑄法製造黏著薄片時,藉由使用公知方法,將本發明的黏著劑組合物塗佈於剝離薄膜的剝離處理面,藉由將所獲得塗膜施行乾燥,而製造具剝離薄膜的黏著劑層,接著藉由將另一片剝離薄膜重疊於黏著劑層上,便可獲得黏著薄片。The method for producing the adhesive sheet is not particularly limited. Adhesive sheets can be produced, for example, by casting. The method for producing the adhesive sheet is not particularly limited. Adhesive sheets can be produced, for example, by casting. When producing an adhesive sheet by a casting method, by using a known method, the adhesive composition of the present invention is applied to the release-treated surface of the release film, and the obtained coating film is dried to produce an adhesive with a release film. layer, and then by superimposing another peel-off film on the adhesive layer, an adhesive sheet can be obtained.

黏著劑組合物施行塗佈的方法係可舉例如:旋塗法、噴塗法、棒塗法、刀塗法、輥塗法、刮刀塗佈法、模具塗佈法、凹版塗佈法等。 塗膜施行乾燥時的乾燥條件係可例如:乾燥溫度80~150℃、乾燥時間30秒至5分鐘。 塗膜施行乾燥時的乾燥條件係可例如:乾燥溫度80~150℃、乾燥時間30秒至5分鐘。The method of coating the adhesive composition includes, for example, spin coating, spray coating, bar coating, knife coating, roll coating, knife coating, die coating, and gravure coating. The drying conditions when drying the coating film can be, for example: a drying temperature of 80-150° C., and a drying time of 30 seconds to 5 minutes. The drying conditions when drying the coating film can be, for example: a drying temperature of 80-150° C., and a drying time of 30 seconds to 5 minutes.

本發明黏著薄片的黏著劑層係具有熱硬化性。 使黏著劑層進行熱硬化時的條件並無特別的限定。 加熱溫度通常係80~200℃、較佳係90~150℃。 加熱時間通常係30分鐘至12小時、較佳係1~6小時。 本發明黏著劑層經熱硬化後的狀態,係指使硬化至能使用為被密封物密封程度的狀態。The adhesive layer system of the adhesive sheet of the present invention has thermosetting properties. The conditions for thermosetting the adhesive layer are not particularly limited. The heating temperature is usually 80~200°C, preferably 90~150°C. The heating time is usually 30 minutes to 12 hours, preferably 1 to 6 hours. The thermally hardened state of the adhesive layer of the present invention refers to the state of hardening to the extent that it can be used as a sealant.

經硬化處理後的黏著劑層之23℃撕開黏著強度,通常係1~100N/25mm、較佳係10~50N/25mm,且,85℃撕開黏著強度通常係1~100N/25mm、較佳係5~50N/25mm。 23℃撕開黏著強度係根據JIS Z0237:2009,在溫度23℃、相對濕度50%環境下、與溫度85℃(無控制濕度)環境下,分別依剝離角度180°的條件施行剝離測試,便可測定。 23℃撕開黏著強度係根據JIS Z0237:2009,在溫度23℃、相對濕度50%環境下、與溫度85℃(無控制濕度)環境下,分別依剝離角度180°的條件施行剝離測試,便可測定。 經硬化處理後的黏著劑層之水蒸氣穿透率,通常係0.1~200g‧m-2 ‧day-1 、較佳係1~150g‧m-2 ‧day-1 。水蒸氣穿透率係使用公知水蒸氣穿透率測定裝置(例如LYSSY公司製的穿透率測定機「L80-5000」),於40℃、90%RH條件下便可測定。The 23°C tearing adhesive strength of the hardened adhesive layer is usually 1~100N/25mm, preferably 10~50N/25mm, and the 85°C tearing adhesive strength is usually 1~100N/25mm, relatively The best is 5~50N/25mm. The tear adhesion strength at 23°C is based on JIS Z0237: 2009, in the environment of temperature 23°C, relative humidity 50%, and temperature 85°C (uncontrolled humidity), the peeling test is carried out according to the peeling angle of 180°, respectively. measurable. The tear adhesion strength at 23°C is based on JIS Z0237: 2009, in the environment of temperature 23°C, relative humidity 50%, and temperature 85°C (uncontrolled humidity), the peeling test is carried out according to the peeling angle of 180°, respectively. measurable. The water vapor transmission rate of the hardened adhesive layer is usually 0.1~200g‧m -2 ‧day -1 , preferably 1~150g‧m -2 ‧day -1 . The water vapor transmission rate can be measured under the conditions of 40° C. and 90% RH using a known water vapor transmission rate measuring device (for example, the transmission rate measuring machine “L80-5000” manufactured by LYSSY Co., Ltd.).

如上述,本發明黏著薄片的黏著劑層之硬化物係無色透明性優異。所以,本發明的黏著薄片頗適用於將例如有機EL元件、有機EL顯示器元件、液晶顯示器元件、太陽電池元件等施行密封時。As mentioned above, the cured product of the adhesive layer of the adhesive sheet of the present invention is excellent in colorless transparency. Therefore, the adhesive sheet of the present invention is suitable for sealing, for example, organic EL elements, organic EL display elements, liquid crystal display elements, solar cell elements, and the like.

3)密封體 本發明的密封體係被密封物使用本發明黏著薄片進行密封。 本發明的密封體係例如具備有:基板、形成於該基板上的元件(被密封物)、以及供密封該元件用的密封材,上述密封材係可例如源自本發明黏著薄片之黏著劑層者(黏著劑層的硬化物)。3) Sealed body The sealed object of the sealing system of the present invention is sealed using the adhesive sheet of the present invention. The sealing system of the present invention includes, for example: a substrate, an element (to-be-sealed object) formed on the substrate, and a sealing material for sealing the element. The above-mentioned sealing material can be derived from, for example, the adhesive layer of the adhesive sheet of the present invention. Those (the hardened product of the adhesive layer).

基板並無特別的限定,可使用各種基板材料。特別較佳係使用可見光穿透率高的基板材料。又,較佳係能阻止欲從元件外部滲入之水分與氣體的阻斷性能較高,且耐溶劑性與耐候性優異的材料。具體係可舉例如:石英、玻璃等透明無機材料;聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚碳酸酯、聚苯乙烯、聚乙烯、聚丙烯、聚苯硫醚、聚偏氟乙烯、醋酸纖維素、溴化苯氧基、芳醯胺類、聚醯亞胺類、聚苯乙烯類、聚芳酯類、聚碸類、聚烯烴類等透明塑膠;前述阻氣性薄膜等。 基板的厚度並無特別的限制,可經考量光穿透率、阻斷元件內外的性能之後,再行適當選擇。The substrate is not particularly limited, and various substrate materials can be used. It is particularly preferred to use a substrate material with high visible light transmittance. Also, it is preferable to use a material that has a high barrier performance against moisture and gas that may permeate from the outside of the device, and is excellent in solvent resistance and weather resistance. Specific systems include, for example: transparent inorganic materials such as quartz and glass; polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polystyrene, polyethylene, polypropylene, polyphenylene sulfide, Transparent plastics such as polyvinylidene fluoride, cellulose acetate, brominated phenoxy, aramids, polyimides, polystyrenes, polyarylates, polysulfones, polyolefins, etc.; the aforementioned gas barrier thin films, etc. The thickness of the substrate is not particularly limited, and can be properly selected after considering the light transmittance and the performance of blocking the inside and outside of the element.

被密封物係可舉例如:有機EL元件、有機EL顯示器元件、液晶顯示器元件、太陽電池元件等。The sealed object system may, for example, be an organic EL element, an organic EL display element, a liquid crystal display element, or a solar cell element.

本發明密封體的製造方法並無特別的限定。例如將本發明黏著薄片的黏著劑層重疊於被密封物上之後,施行加熱而使黏著薄片的黏著劑層與被密封物相黏著,接著,藉由使該黏著劑層硬化,便可製造本發明的密封體。The method for producing the sealing body of the present invention is not particularly limited. For example, after superimposing the adhesive layer of the adhesive sheet of the present invention on the object to be sealed, heating is applied to make the adhesive layer of the adhesive sheet adhere to the object to be sealed, and then the adhesive layer is hardened to produce the present invention. Invented seals.

使黏著薄片的黏著劑層與被密封物相黏著時的黏著條件並無特別的限定。黏著溫度係例如23~100℃、較佳40~80℃。該黏著處理亦可一邊加壓一邊實施。 使黏著劑層硬化時的硬化條件,係可利用前所說明的條件。Adhesion conditions when the adhesive layer of the adhesive sheet is adhered to the object to be sealed are not particularly limited. The sticking temperature is, for example, 23-100°C, preferably 40-80°C. This adhesion treatment can also be performed while applying pressure. The curing conditions for curing the adhesive layer can be the conditions described above.

本發明的密封體係被密封物經利用本發明黏著薄片進行密封。 所以,本發明的密封體係能長期維持被密封物的性能。 [實施例]The object to be sealed in the sealing system of the present invention is sealed by using the adhesive sheet of the present invention. Therefore, the sealing system of the present invention can maintain the performance of the sealed object for a long time. [Example]

以下,舉實施例針對本發明進行更詳細說明。惟,本發明並不受以下實施例的任何限定。 各例中的「份」及「%」在無特別聲明前提下,係質量基準。Hereinafter, examples are given to describe the present invention in more detail. However, the present invention is not limited by the following examples. The "parts" and "%" in each example are quality standards unless otherwise stated.

〔實施例1〕 將酸改質聚烯烴系樹脂(酸改質α-烯烴聚合體、三井化學公司製、商品名:UNISTOLEH-200、數量平均分子量:47,000)100份、多官能基環氧化合物(1)(氫化雙酚A型環氧樹脂、三菱化學公司製、商品名:YX8000、環氧當量:205g/eq)25份、咪唑系硬化觸媒(四國化成公司製、商品名:Curezol 2E4MZ、2-乙基-4-甲基咪唑)0.25份、及矽烷偶合劑(信越化學工業公司製、商品名:KBM6803)0.1份,溶解於甲乙酮中,而製備固形份濃度20%的黏著劑組合物1。 將該黏著劑組合物1塗佈於剝離薄膜(Lintec公司製、商品名:SP-PET382150)的剝離處理面上,再將所獲得塗膜依100℃施行2分鐘乾燥,而形成厚度10μm的黏著劑層,在其上面貼合另1片剝離薄膜(Lintec公司製、商品名:SP-PET381031)的剝離處理面而獲得黏著薄片1。[Example 1] 100 parts of acid-modified polyolefin resin (acid-modified α-olefin polymer, manufactured by Mitsui Chemicals, trade name: UNISTOLEH-200, number average molecular weight: 47,000), polyfunctional epoxy compound (1) 25 parts of (hydrogenated bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation, trade name: YX8000, epoxy equivalent: 205 g/eq), imidazole-based hardening catalyst (manufactured by Shikoku Chemicals Co., Ltd., trade name: Curezol) 2E4MZ, 0.25 parts of 2-ethyl-4-methylimidazole), and 0.1 part of silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM6803) were dissolved in methyl ethyl ketone to prepare an adhesive with a solid concentration of 20%. Composition 1. This adhesive composition 1 was coated on the release-treated surface of a release film (manufactured by Lintec Corporation, trade name: SP-PET382150), and the obtained coating film was dried at 100°C for 2 minutes to form an adhesive film with a thickness of 10 μm. The agent layer was bonded to the surface of another release film (manufactured by Lintec, trade name: SP-PET381031) on the release treatment surface to obtain an adhesive sheet 1 .

〔實施例2〕 除在實施例1中,取代多官能基環氧化合物(1),改為使用多官能基環氧化合物(2)(氫化雙酚A型環氧樹脂、三菱化學公司製、商品名:YX8034、環氧當量:270g/eq)之外,其餘均依照與實施例1同樣地製備黏著劑組合物2,並使用其獲得黏著薄片2。[Example 2] In Example 1, instead of the polyfunctional epoxy compound (1), a polyfunctional epoxy compound (2) (hydrogenated bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation, Except for product name: YX8034, epoxy equivalent: 270 g/eq), the adhesive composition 2 was prepared in the same manner as in Example 1, and the adhesive sheet 2 was obtained using it.

〔實施例3〕 除在實施例1中,取代多官能基環氧化合物(1),改為使用多官能基環氧化合物(3)(ADEKA公司製、商品名:EP-4088L、二環戊二烯二甲醇二環氧丙醚、環氧當量:165g/eq)之外,其餘均依照與實施例1同樣地製備黏著劑組合物3,並使用其獲得黏著薄片3。[Example 3] In Example 1, instead of the polyfunctional epoxy compound (1), a polyfunctional epoxy compound (3) (manufactured by ADEKA Corporation, trade name: EP-4088L, dicyclopentanyl Adhesive composition 3 was prepared in the same manner as in Example 1 except for diene dimethanol diglycidyl ether and epoxy equivalent: 165 g/eq), and an adhesive sheet 3 was obtained using it.

〔實施例4〕 將酸改質聚烯烴系樹脂(α-烯烴聚合體、三井化學公司製、商品名:UNISTOLEH-200、數量平均分子量:47,000)100份、多官能基環氧化合物(1)(氫化雙酚A型環氧樹脂、三菱化學公司製、商品名:YX8000)100份、賦黏劑(苯乙烯系單體/脂肪族系單體共聚合樹脂、三井化學公司製、商品名:FTR6100)50份、咪唑系硬化觸媒(四國化成公司製、商品名:Curezol 2E4MZ、2-乙基-4-甲基咪唑)1份、及矽烷偶合劑(信越化學工業公司製、商品名:KBM6803)0.1份,溶解於甲乙酮中,而製備得固形份濃度30%的黏著劑組合物4。 除取代黏著劑組合物1,改為使用黏著劑組合物4之外,其餘均依照與實施例1同樣地獲得黏著薄片4。[Example 4] 100 parts of acid-modified polyolefin resin (α-olefin polymer, manufactured by Mitsui Chemicals, trade name: UNISTOLEH-200, number average molecular weight: 47,000), polyfunctional epoxy compound (1) (Hydrogenated bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation, trade name: YX8000) 100 parts, tackifier (styrene monomer/aliphatic monomer copolymer resin, manufactured by Mitsui Chemicals Corporation, trade name: FTR6100) 50 parts, imidazole-based hardening catalyst (manufactured by Shikoku Chemicals Co., Ltd., trade name: Curezol 2E4MZ, 2-ethyl-4-methylimidazole) 1 part, and silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., trade name : KBM6803) 0.1 part, dissolved in methyl ethyl ketone, and prepared adhesive composition 4 with a solid content concentration of 30%. Adhesive sheet 4 was obtained in the same manner as in Example 1 except that adhesive composition 4 was used instead of adhesive composition 1.

〔實施例5〕 除在實施例4中,取代多官能基環氧化合物(1),改為使用多官能基環氧化合物(2)(氫化雙酚A型環氧樹脂、三菱化學公司製、商品名:YX8034)之外,其餘均依照與實施例4同樣地製備黏著劑組合物5,並使用其獲得黏著薄片5。[Example 5] Except in Example 4, instead of the polyfunctional epoxy compound (1), a polyfunctional epoxy compound (2) (hydrogenated bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation, Except for the product name: YX8034), the adhesive composition 5 was prepared in the same manner as in Example 4, and an adhesive sheet 5 was obtained using it.

〔實施例6〕 除在實施例4中,取代多官能基環氧化合物(1),改為使用多官能基環氧化合物(4)(氫化雙酚A型環氧樹脂、三菱化學公司製、商品名:YX8040、環氧當量:1100g/eq)之外,其餘均依照與實施例4同樣地製備黏著劑組合物6,並使用其獲得黏著薄片6。[Example 6] Except in Example 4, instead of the polyfunctional epoxy compound (1), a polyfunctional epoxy compound (4) (hydrogenated bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation, Except product name: YX8040, epoxy equivalent: 1100g/eq), the adhesive agent composition 6 was prepared in the same manner as in Example 4, and the adhesive sheet 6 was obtained using it.

〔實施例7〕 除在實施例4中,取代多官能基環氧化合物(1),改為使用多官能基環氧化合物(3)(ADEKA公司製、商品名:EP-4088L)之外,其餘均依照與實施例4同樣地製備黏著劑組合物7,並使用其獲得黏著薄片7。[Example 7] Except that in Example 4, instead of the polyfunctional epoxy compound (1), a polyfunctional epoxy compound (3) (manufactured by ADEKA Corporation, trade name: EP-4088L) was used instead, For the rest, an adhesive composition 7 was prepared in the same manner as in Example 4, and an adhesive sheet 7 was obtained using it.

〔比較例1〕 除在實施例4中,取代多官能基環氧化合物(1),改為使用多官能基環氧化合物(5)(未氫化雙酚A型環氧樹脂、三菱化學公司製、商品名:jER828、環氧當量:190g/eq)之外,其餘均依照與實施例1同樣地製備黏著劑組合物8,並使用其獲得黏著薄片8。[Comparative Example 1] Except in Example 4, instead of the polyfunctional epoxy compound (1), a polyfunctional epoxy compound (5) (non-hydrogenated bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Co., Ltd. , trade name: jER828, epoxy equivalent: 190g/eq), and the rest were prepared in the same manner as in Example 1. Adhesive composition 8 was used to obtain adhesive sheet 8.

針對實施例1~7、比較例1所獲得黏著薄片1~8,施行以下的測試。結果如第1表所示。 〔全光線穿透率及霧度測定〕 撕開一片除去實施例或比較例所獲得黏著薄片的剝離薄膜,而使黏著劑層露出。依露出的黏著劑層相對向於鈉鈣玻璃的方式,將該黏著薄片放置於鈉鈣玻璃上,接著使用壓合機,依23℃將該等貼合。撕開除去另一片剝離薄膜後,該等經100℃加熱2小時而使黏著劑層硬化,便獲得測試片。 針對所獲得測試片,使用全光線穿透率測定裝置(日本電色工業公司製、製品名:NDH-5000)測定全光線穿透率及霧度。For the adhesive sheets 1-8 obtained in Examples 1-7 and Comparative Example 1, the following tests were performed. The results are shown in Table 1. [Measurement of Total Light Transmittance and Haze] One peeling film was torn off to remove the adhesive sheet obtained in the example or comparative example to expose the adhesive layer. Place the adhesive sheet on the soda-lime glass in such a way that the exposed adhesive layer faces the soda-lime glass, and then use a pressing machine to bond them together at 23°C. After tearing and removing the other peeling film, the adhesive layer was hardened by heating at 100°C for 2 hours to obtain a test piece. About the obtained test piece, the total light transmittance and haze were measured using the total light transmittance measuring apparatus (made by Nippon Denshoku Kogyo Co., Ltd., product name: NDH-5000).

〔測色〕 製作與全光線穿透率及霧度測定時所使用者同樣的測試片。 針對所獲得測試片,根據JIS Z 8729-1994,使用分光光度計(島津製作所公司製、UV-3200),測定由CIE1976L*a*b*表色系所規定的色彩值b*。〔Color measurement〕 Prepare the same test pieces as those used in the measurement of total light transmittance and haze. With respect to the obtained test piece, the color value b* specified by the CIE1976L*a*b* colorimetric system was measured using a spectrophotometer (manufactured by Shimadzu Corporation, UV-3200) according to JIS Z 8729-1994.

[表1]

Figure 107118487-A0304-0001
[Table 1]
Figure 107118487-A0304-0001

由第1表得知以下事項。 實施例1~7所獲得黏著薄片1~7的黏著劑層之硬化物,係全光線穿透率高、霧度值低。且,b*值係-2.0~+2.0。 另一方面,比較例1所獲得黏著薄片8的黏著劑層之硬化物,係霧度值大、透明性差。The following matters can be obtained from Table 1. The cured products of the adhesive layers of the adhesive sheets 1-7 obtained in Examples 1-7 have high total light transmittance and low haze value. And, the b* value is -2.0~+2.0. On the other hand, the hardened product of the adhesive layer of the adhesive sheet 8 obtained in Comparative Example 1 had a large haze value and poor transparency.

none

無。none.

無。none.

Claims (10)

一種黏著薄片,係由黏著劑層及2片剝離薄膜組成的黏著薄片,其中,上述剝離薄膜在上述接劑層兩側分別存在1片,上述黏著劑層係使用下述的黏著劑組合物1形成,且上述黏著劑層具有熱硬化性,(黏著劑組合物1)一種黏著劑組合物,係含有下述(A)成分、(B)成分、及(D)成分的黏著劑組合物,其特徵在於:將該黏著劑組合物成形為厚度10μm薄片狀,接著再使硬化並進行測色時,JIS Z 8729-1994所規定CIE L*a*b*表色系的b*值係-2.0~+2.0;(A)成分:酸改質聚烯烴系樹脂,使聚烯烴樹脂、與不飽和羧酸或不飽和羧酸酐進行反應而獲得,不飽和羧酸或不飽和羧酸酐之量,相對於聚烯烴樹脂100質量份,為0.2~3質量份;(B)成分:未具芳香環的多官能基環氧化合物,選自由氫化雙酚A型環氧樹脂、氫化雙酚F型環氧樹脂、氫化雙酚S型環氧樹脂、氫化雙酚A二環氧丙醚、氫化雙酚F二環氧丙醚、氫化雙酚S二環氧丙醚、季戊四醇聚環氧丙醚、1,6-己二醇二環氧丙醚、六氫酞酸二環氧丙基酯、新戊二醇二環氧丙醚、三羥甲基丙烷聚環氧丙醚、二羥甲基三環癸烷二環氧丙醚、二環戊二烯二甲醇二環氧丙醚所構成之群組中的1種或2種以上;(D)成分:咪唑系硬化觸媒。 An adhesive sheet is an adhesive sheet composed of an adhesive layer and two peeling films, wherein the peeling film is one on both sides of the adhesive layer, and the adhesive layer uses the following adhesive composition 1 (Adhesive composition 1) is an adhesive composition comprising the following (A) component, (B) component, and (D) component, and the above-mentioned adhesive layer has thermosetting properties, It is characterized in that: when the adhesive composition is formed into a thin sheet with a thickness of 10 μm , and then hardened to measure the color, the b* value of the CIE L*a*b* color system specified in JIS Z 8729-1994 System -2.0~+2.0; (A) component: acid modified polyolefin resin, obtained by reacting polyolefin resin with unsaturated carboxylic acid or unsaturated carboxylic acid anhydride, unsaturated carboxylic acid or unsaturated carboxylic anhydride Quantity, with respect to polyolefin resin 100 mass parts, be 0.2~3 mass parts; (B) component: the polyfunctional group epoxy compound that does not have aromatic ring, be selected from hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F Type epoxy resin, hydrogenated bisphenol S type epoxy resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, pentaerythritol polyglycidyl ether , 1,6-Hexanediol Diglycidyl Ether, Diglycidyl Hexahydrophthalate, Neopentyl Glycol Diglycidyl Ether, Trimethylolpropane Polyglycidyl Ether, Dimethylol One or more of the group consisting of tricyclodecane diglycidyl ether and dicyclopentadiene dimethanol diglycidyl ether; (D) component: an imidazole-based hardening catalyst. 如申請專利範圍第1項之黏著薄片,其中,相對於上述(A)成分 100質量份,上述(B)成分的含有量係1~200質量份。 Such as the adhesive sheet of item 1 of the scope of the patent application, wherein, relative to the above-mentioned (A) component 100 mass parts, the content of the said (B) component is 1-200 mass parts. 如申請專利範圍第1項之黏著薄片,其中,更進一步含有下述(C)成分:(C)成分:軟化點達80℃以上的賦黏劑。 Such as the adhesive sheet of item 1 of the scope of the patent application, which further contains the following (C) component: (C) component: a tackifier with a softening point of 80°C or higher. 如申請專利範圍第3項之黏著薄片,其中,相對於上述(A)成分100質量份,上述(C)成分的含有量係1~200質量份。 Such as the adhesive sheet of claim 3, wherein the content of the above-mentioned (C) component is 1 to 200 parts by mass relative to 100 parts by mass of the above-mentioned (A) component. 如申請專利範圍第1項之黏著薄片,其中,相對於上述(B)成分100質量份,上述(D)成分的含有量係1~10質量份。 Such as the adhesive sheet of claim 1, wherein the content of the above-mentioned (D) component is 1 to 10 parts by mass relative to 100 parts by mass of the above-mentioned (B) component. 如申請專利範圍第1項之黏著薄片,其中,更進一步含有下述(E)成分:(E)成分:矽烷偶合物。 Such as the adhesive sheet of item 1 of the scope of the patent application, which further contains the following (E) component: (E) component: silane coupling compound. 如申請專利範圍第6項之黏著薄片,其中,相對於上述(A)成分100質量份,上述(E)成分的含有量係0.01~10質量份。 Such as the adhesive sheet of claim 6, wherein the content of the above-mentioned component (E) is 0.01 to 10 parts by mass relative to 100 parts by mass of the above-mentioned component (A). 如申請專利範圍第1項之黏著薄片,其中,黏著劑層的厚度係5~25μm。 For example, the adhesive sheet of item 1 of the scope of application, wherein the thickness of the adhesive layer is 5-25 μm. 一種密封體,係被密封物使用申請專利範圍第1至8項中任一項之黏著薄片進行密封。 A sealing body is sealed by using the adhesive sheet in any one of items 1 to 8 of the patent application scope. 如申請專利範圍第9項之密封體,其中,上述被密封物係有機EL元件、有機EL顯示器元件、液晶顯示器元件、或太陽電池元件。 The sealed body according to claim 9 of the patent application, wherein the above-mentioned sealed object is an organic EL element, an organic EL display element, a liquid crystal display element, or a solar cell element.
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