TW201816028A - Adhesive composition, cured object, electronic component, and assembly component - Google Patents

Adhesive composition, cured object, electronic component, and assembly component Download PDF

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TW201816028A
TW201816028A TW106126906A TW106126906A TW201816028A TW 201816028 A TW201816028 A TW 201816028A TW 106126906 A TW106126906 A TW 106126906A TW 106126906 A TW106126906 A TW 106126906A TW 201816028 A TW201816028 A TW 201816028A
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adhesive composition
meth
acrylate
weight
moisture
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TW106126906A
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TWI826355B (en
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玉川智一
木田拓身
結城彰
高橋徹
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日商積水化學工業股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Combinations Of Printed Boards (AREA)

Abstract

A purpose of the present invention is to provide an adhesive composition which has excellent adhesiveness and which facilitates low-temperature reworking. Another purpose of the present invention is to provide a cured object obtained from the adhesive composition and an electronic component and an assembly component both including a cured object obtained from the adhesive composition. The adhesive composition of the present invention comprises a moisture-curable resin and a blowing agent.

Description

接著劑組成物、硬化體、電子零件及組裝零件    Adhesive composition, hardened body, electronic part and assembly part   

本發明係關於一種接著性優異且低溫下之二次加工容易的接著劑組成物。又，本發明係關於一種該接著劑組成物之硬化體以及具有該接著劑組成物之硬化體的電子零件及組裝零件。 The present invention relates to an adhesive composition which is excellent in adhesiveness and easy in secondary processing at low temperatures. The present invention also relates to a hardened body of the adhesive composition, and an electronic component and an assembled component having the hardened body of the adhesive composition.

近年來，廣泛利用液晶顯示元件、有機EL顯示元件等作為具有薄型、輕量、低消耗電力等特徵之顯示元件。於該等顯示元件中，通常將光硬化型樹脂組成物用於液晶或發光層之密封、基板、光學膜、保護膜等各種構件之接著等。又，於行動電話、攜帶型遊戲機等各種附顯示元件之移動設備普及之現代，要求最多之課題為顯示元件之小型化，作為小型化之方法，進行有使圖像顯示部窄邊緣化(以下，亦稱為窄邊緣設計)。 In recent years, liquid crystal display elements, organic EL display elements, and the like have been widely used as display elements having characteristics such as thinness, light weight, and low power consumption. In these display elements, a photocurable resin composition is generally used for sealing of liquid crystal or a light-emitting layer, bonding of various members such as a substrate, an optical film, and a protective film. Moreover, in the modernization of the spread of mobile devices with display elements such as mobile phones and portable game consoles, the most requested issue is miniaturization of display elements. As a method of miniaturization, narrowing of the image display portion has been performed ( Hereinafter, it is also referred to as narrow edge design.)

然而，隨著顯示元件之小型化，有將光硬化型樹脂組成物塗佈於光未充分地到達之部分之情況，其結果存在塗佈於光未到達之部分的光硬化型樹脂組成物硬化不足之問題。該問題於窄邊緣設計之顯示元件中尤為顯著。因此，雖亦進行：使用光熱硬化型樹脂組成物作為即便於塗佈於光未到達之部分之情形時亦可充分地硬化之樹脂組成物而將光硬化與熱硬化併 用；但有因高溫下之加熱而導致對元件等造成不良影響之虞。 However, with the miniaturization of display elements, a photocurable resin composition may be applied to a portion where light does not reach sufficiently. As a result, a photocurable resin composition applied to a portion where light does not reach may harden. Inadequacy. This problem is particularly noticeable in display elements with narrow edge designs. Therefore, although a photothermosetting resin composition is used as a resin composition that can be sufficiently cured even when it is applied to a portion where light does not reach, photocuring and heat curing are used in combination; Heating may cause adverse effects on the components and the like.

又，近年來，於半導體晶片等電子零件中，要求高積體化、小型化，例如進行有經由接著劑層將多個較薄之半導體晶片接合而製成半導體晶片之積層體。此種半導體晶片之積層體例如係藉由如下方法等而製造：於將接著劑塗佈於一個半導體晶片上後，經由該接著劑積層另一半導體晶片，其後，使接著劑硬化之方法；將接著劑填充至隔開一定間隔而保持之半導體晶片間，其後使接著劑硬化之方法。 Furthermore, in recent years, electronic components such as semiconductor wafers have been required to be highly integrated and miniaturized. For example, a laminated body in which a plurality of thinner semiconductor wafers are bonded through an adhesive layer to form a semiconductor wafer is performed. Such a laminated body of a semiconductor wafer is produced, for example, by a method of applying an adhesive on one semiconductor wafer, laminating another semiconductor wafer through the adhesive, and then hardening the adhesive; A method of filling an adhesive between semiconductor wafers held at regular intervals and then curing the adhesive.

作為用於此種電子零件之接著的接著劑，例如於專利文獻1中揭示有一種含有數量平均分子量為600~1000之環氧化合物之熱硬化型之接著劑。然而，如專利文獻1所揭示之熱硬化型之接著劑並不適合可能會因熱而導致損傷之電子零件之接著。 As a bonding agent for such electronic parts, for example, Patent Literature 1 discloses a thermosetting type bonding agent containing an epoxy compound having a number average molecular weight of 600 to 1,000. However, the heat-curable adhesive as disclosed in Patent Document 1 is not suitable for bonding electronic components that may be damaged by heat.

作為不進行高溫下之加熱地使樹脂組成物硬化之方法，正在研究使用濕氣硬化型樹脂組成物之方法。例如，於專利文獻2中揭示有一種藉由使樹脂中之異氰酸酯基與空氣中或被接著體中之濕氣(水分)反應而交聯硬化之濕氣硬化型樹脂組成物。然而，如專利文獻1所揭示之熱硬化型之接著劑不適合可能會因熱而導致損傷之電子零件之接著。又，熱硬化型之接著劑若長時間受到較大之負載，則接著特性容易降低，故而難以獲得可靠性較高之接著劑，尤其是於窄邊緣設計之顯示元件中為較大之問題。 As a method for curing the resin composition without heating at a high temperature, a method using a moisture-curable resin composition is being studied. For example, Patent Document 2 discloses a moisture-curable resin composition that is crosslinked and cured by reacting an isocyanate group in a resin with moisture (water) in the air or an adherend. However, the heat-curable adhesive as disclosed in Patent Document 1 is not suitable for bonding electronic parts that may be damaged by heat. In addition, if a thermosetting adhesive is subjected to a large load for a long period of time, the adhesive properties are likely to be reduced, so it is difficult to obtain a highly reliable adhesive. This is particularly a problem in display devices with a narrow edge design.

專利文獻1：日本特開2000-178342號公報 Patent Document 1: Japanese Patent Application Laid-Open No. 2000-178342

專利文獻2：日本特開2002-212534號公報 Patent Document 2: Japanese Patent Application Laid-Open No. 2002-212534

如今，本發明人等雖獲得了賦予二次加工性之新型濕氣硬化型樹脂組成物之構思，但如上述之濕氣硬化型樹脂組成物難以兼顧接著性與二次加工性(再剝離性)。尤其是由於存在「當在高溫條件下實施二次加工時會使電子零件等損傷」之問題，故而必須研究如下樹脂組成物，即，於固定時無需高溫下之加熱便可硬化而具有優異之接著性，且於二次加工時可利用低溫條件下之加熱而容易地剝離之樹脂組成物。 Nowadays, although the present inventors have obtained a concept of a new moisture-curable resin composition that imparts secondary processability, it is difficult for the moisture-curable resin composition as described above to achieve both adhesiveness and secondary processability (repeelability). ). In particular, due to the problem of "damaging electronic parts and the like when secondary processing is performed under high temperature conditions", it is necessary to study the following resin composition, which can be hardened without heating at high temperature during fixing and has excellent properties. Resin composition that can be easily peeled off by heating under low temperature conditions during secondary processing.

本發明之目的在於提供一種接著性優異且低溫下之二次加工容易的接著劑組成物。又，本發明之目的在於提供一種該接著劑組成物之硬化體以及具有該接著劑組成物之硬化體的電子零件及組裝零件。 An object of the present invention is to provide an adhesive composition having excellent adhesion and easy secondary processing at low temperatures. Another object of the present invention is to provide a hardened body of the adhesive composition, and an electronic component and an assembled component having the hardened body of the adhesive composition.

本發明係含有濕氣硬化型樹脂與發泡劑之接著劑組成物。以下，對本發明進行詳細說明。 The present invention is an adhesive composition containing a moisture-curable resin and a foaming agent. Hereinafter, the present invention will be described in detail.

本發明人等發現，藉由於濕氣硬化型樹脂組成物中摻合發泡劑，可獲得接著性優異且低溫下之二次加工容易之接著劑組成物，從而完成了本發明。 The present inventors have found that by blending a foaming agent into the moisture-curable resin composition, an adhesive composition having excellent adhesion and easy secondary processing at low temperature can be obtained, and completed the present invention.

本發明之接著劑組成物係一種所謂之熱剝離型接著劑組成物，其於作為接著劑使用後具有牢固之接著力，但於二次加工時，可藉由於相對低溫下進行加熱而使接著部分剝離。 The adhesive composition of the present invention is a so-called heat-peelable adhesive composition, which has a strong adhesive force after being used as an adhesive, but can be adhered by heating at a relatively low temperature during secondary processing. Partial peeling.

本發明之接著劑組成物含有發泡劑。藉由含有上述發泡劑， 本發明之接著劑組成物成為低溫下之二次加工性優異者。 The adhesive composition of the present invention contains a foaming agent. By containing the said foaming agent, the adhesive composition of this invention becomes a thing excellent in the secondary processability at low temperature.

作為上述「發泡劑」，例如可列舉無機發泡劑、有機發泡劑、熱膨脹性粒子等。上述發泡劑之形狀並無特別限定，較佳為粒子形狀。 Examples of the "foaming agent" include inorganic foaming agents, organic foaming agents, and thermally expandable particles. The shape of the foaming agent is not particularly limited, but a particle shape is preferred.

再者，上述「無機發泡劑」及上述「有機發泡劑」意指藉由利用加熱而進行之分解等作用產生氣體者。又，上述「熱膨脹性粒子」意指於由熱塑性樹脂構成之外殼內內包低沸點化合物作為核劑，藉由加熱使核劑揮發而外殼內之氣壓增加，構成外殼之熱塑性樹脂軟化而體積增大之粒子。 In addition, the said "inorganic foaming agent" and the said "organic foaming agent" mean those which generate | occur | produce by the action, such as decomposition | disassembly by heating. The term "thermally expandable particles" means that a low-boiling-point compound is contained in a shell made of a thermoplastic resin as a nucleating agent. The nucleating agent is volatilized by heating and the pressure in the shell increases. The thermoplastic resin constituting the shell softens and increases volume. Big particles.

作為上述無機發泡劑，例如可列舉：重碳酸鈉、碳酸銨、重碳酸銨、亞硝酸銨等，或聚磷酸醯胺、聚磷酸銨、磷酸三聚氰胺等，或鎂粉末、鋁粉末等輕金屬，或硼氫化鈉、氫化鈉等氫化物，或疊氮化鈉等疊氮化物等。 Examples of the inorganic foaming agent include sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, ammonium nitrite, etc., or ammonium polyphosphate, ammonium polyphosphate, melamine phosphate, and the like, or light metals such as magnesium powder and aluminum powder. Or hydrides such as sodium borohydride and sodium hydride, or azides such as sodium azide.

作為上述有機發泡劑，例如可列舉：偶氮二甲醯胺、偶氮二異丁腈等偶氮化合物，或N,N'-二亞硝基五亞甲基四胺、N,N'-二亞硝基-N,N'-二甲基對苯二甲醯胺等亞硝基化合物，或對甲苯磺醯肼、p,p'-氧基雙(苯磺醯肼)、伸肼基甲醯胺等醯肼化合物，或疊氮化對甲苯磺酸、丙酮-對磺醯基腙、三聚氰胺、脲、雙氰胺、澱粉、纖維素、糖類、二新戊四醇等。 Examples of the organic foaming agent include azo compounds such as azodimethylamine and azobisisobutyronitrile, or N, N'-dinitrosopentamethylenetetramine, and N, N ' -Nitroso compounds such as dinitroso-N, N'-dimethyl-p-xylylenediamine, or p-toluenesulfonylhydrazine, p, p'-oxybis (benzenesulfonylhydrazine), hydrazine A hydrazine compound such as methylformamide, or p-toluenesulfonic acid azide, acetone-p-sulfohydrazone, melamine, urea, dicyandiamide, starch, cellulose, sugars, dipentaerythritol, and the like.

作為構成上述熱膨脹性粒子之外殼之熱塑性樹脂，例如可列舉：聚乙烯、聚丙烯等聚烯烴，或乙烯-乙酸乙烯酯共聚物、聚氯乙烯、聚苯乙烯、乙烯-甲基丙烯酸甲酯共聚物、聚偏二氯乙烯、聚甲基丙烯酸甲酯、甲基丙烯酸甲酯-丙烯腈共聚物、偏二氯乙烯-丙烯腈共聚物、聚丙烯腈等。其中，較佳為偏二氯乙烯-丙烯腈共聚物、甲基丙烯酸甲酯- 丙烯腈共聚物。 Examples of the thermoplastic resin constituting the shell of the thermally expandable particles include polyolefins such as polyethylene and polypropylene, or ethylene-vinyl acetate copolymers, polyvinyl chloride, polystyrene, and ethylene-methyl methacrylate copolymers. Materials, polyvinylidene chloride, polymethyl methacrylate, methyl methacrylate-acrylonitrile copolymer, vinylidene chloride-acrylonitrile copolymer, polyacrylonitrile, and the like. Among these, vinylidene chloride-acrylonitrile copolymer and methyl methacrylate-acrylonitrile copolymer are preferable.

就抑制濕氣所導致之外殼之軟化之觀點而言，上述熱膨脹性粒子亦可為外殼之表面之一部分或全部由上述熱塑性樹脂以外之材料被覆。作為被覆之態樣，例如可列舉藉由無機材料及/或有機材料而進行之薄膜塗佈或藉由微粒子而進行之表面被覆等。 From the viewpoint of suppressing the softening of the casing caused by moisture, the thermally expandable particles may be partly or entirely covered with a material other than the thermoplastic resin. Examples of the coating state include thin film coating with an inorganic material and / or organic material, and surface coating with a fine particle.

作為藉由上述無機材料及/或有機材料而進行之薄膜塗佈，例如可列舉藉由電解鍍覆或無電鍍覆而進行之表面被覆、藉由矽烷偶合劑而進行之表面被覆等。 Examples of the thin film coating using the inorganic material and / or organic material include surface coating using electrolytic plating or electroless plating, and surface coating using a silane coupling agent.

作為用於上述電解鍍覆或上述無電鍍覆之鍍覆材料，例如可列舉銅、鋁、金、銀、鎳、鉛、焊料等金屬材料。其中，就成本之觀點而言，較佳為銅、鎳。藉由上述電解鍍覆或上述無電鍍覆而形成之鍍層可為單層，亦可為多層。 Examples of the plating material used for the electrolytic plating or the electroless plating include metal materials such as copper, aluminum, gold, silver, nickel, lead, and solder. Among these, copper and nickel are preferred from the viewpoint of cost. The plating layer formed by the above-mentioned electrolytic plating or the above-mentioned electroless plating may be a single layer or a plurality of layers.

藉由利用上述無機材料及/或有機材料而進行之薄膜塗佈而形成之被覆層之厚度的較佳下限為10nm，較佳之上限為10μm。藉由使上述被覆層之厚度之範圍為該範圍，可充分地抑制濕氣所導致之外殼之軟化，且可適當地控制熱膨脹性粒子之發泡。上述被覆層之厚度之更佳下限為100nm，更佳之上限為4μm。 The lower limit of the thickness of the coating layer formed by thin film coating using the inorganic material and / or the organic material is preferably 10 nm, and the upper limit is preferably 10 μm. By setting the range of the thickness of the coating layer to this range, it is possible to sufficiently suppress the softening of the casing caused by moisture, and to appropriately control the foaming of the thermally expandable particles. A more preferable lower limit of the thickness of the coating layer is 100 nm, and a more preferable upper limit is 4 μm.

上述被覆層之被覆率之較佳下限為30%。藉由使上述被覆層之被覆率為30%以上，可充分地抑制濕氣所導致之外殼之軟化，且可適當地控制熱膨脹性粒子之發泡。上述被覆層之被覆率之更佳下限為60%。上述被覆層之被覆率之實質性上限為100%。 The lower limit of the coverage of the coating layer is preferably 30%. By making the coverage of the above-mentioned coating layer 30% or more, it is possible to sufficiently suppress the softening of the casing caused by moisture, and to appropriately control the foaming of the thermally expandable particles. The lower limit of the coverage of the coating layer is preferably 60%. The substantial upper limit of the coverage of the coating layer is 100%.

於藉由上述微粒子進行表面被覆之情形時，作為該微粒子， 例如可列舉二氧化矽、氧化鋁、氧化鋯、氧化鎂等。其中，就成本之觀點而言，較佳為二氧化矽、氧化鋁。 When the surface is covered with the fine particles, examples of the fine particles include silicon dioxide, aluminum oxide, zirconia, and magnesium oxide. Among these, silicon dioxide and aluminum oxide are preferred from the viewpoint of cost.

上述微粒子之平均粒徑之較佳下限為10nm，較佳之上限為1μm。藉由使上述微粒子之平均粒徑為該範圍，可充分地抑制濕氣所導致之外殼之軟化，且可適當地控制熱膨脹性粒子之發泡。上述微粒子之平均粒徑之更佳之下限為20nm，更佳之上限為500nm。 The preferable lower limit of the average particle diameter of the fine particles is 10 nm, and the preferable upper limit is 1 μm. By setting the average particle diameter of the fine particles to be in this range, it is possible to sufficiently suppress the softening of the shell due to moisture, and to appropriately control the foaming of the thermally expandable particles. A more preferable lower limit of the average particle diameter of the fine particles is 20 nm, and a more preferable upper limit is 500 nm.

再者，上述微粒子之平均粒徑可藉由雷射繞射散射法進行測定。雷射繞射散射法例如可使用Mastersizer Hydro 2000SM(Malvern公司製造)等。 The average particle diameter of the fine particles can be measured by a laser diffraction scattering method. As the laser diffraction scattering method, for example, Mastersizer Hydro 2000SM (manufactured by Malvern) can be used.

上述微粒子之被覆率之較佳下限為30%。藉由使上述微粒子之被覆率為30%以上，可充分地抑制濕氣所導致之外殼之軟化，且可適當地控制熱膨脹性粒子之發泡。上述微粒子之被覆率之更佳下限為60%。上述微粒子之被覆率之實質性上限為100%。 The lower limit of the coverage of the fine particles is preferably 30%. By making the coverage ratio of the above fine particles 30% or more, it is possible to sufficiently suppress the softening of the shell due to moisture, and to appropriately control the foaming of the thermally expandable particles. A more preferable lower limit of the coverage of the fine particles is 60%. The substantial upper limit of the coverage of the fine particles is 100%.

作為成為上述熱膨脹性粒子之核劑之低沸點化合物，例如可列舉：乙烷、丙烷、正丁烷、異丁烷、正戊烷、異戊烷、新戊烷、正己烷、正庚烷、異辛烷、環己烷等低分子量之烴，或四甲基矽烷、三甲基乙基矽烷等四烷基矽烷，或偶氮二甲醯胺等。其中，較佳為異丁烷、異戊烷、異辛烷等單體或混合物。 Examples of the low-boiling-point compound used as a nucleus of the thermally expandable particles include ethane, propane, n-butane, isobutane, n-pentane, isopentane, neopentane, n-hexane, n-heptane, Low-molecular-weight hydrocarbons such as isooctane and cyclohexane, or tetraalkylsilanes such as tetramethylsilane and trimethylethylsilane, or azomethoxamine. Among these, monomers or mixtures such as isobutane, isopentane, and isooctane are preferred.

上述熱膨脹性粒子中上述低沸點化合物之含量之較佳下限為5重量%，較佳之上限為50重量%。藉由使上述低沸點化合物之含量為5重量%以上，所獲得之熱膨脹性粒子之發泡性能變得更優異。藉由使上述低沸點化合物之含量為50重量%以下，所獲得之熱膨脹性粒子之外殼之強度變得更優異，從而能以更高之發泡倍率進行發泡。上述熱膨脹性粒子中 上述低沸點化合物之含量之更佳下限為10重量%，更佳之上限為30重量%。 A preferable lower limit of the content of the low-boiling-point compound in the thermally expandable particles is 5% by weight, and a preferable upper limit is 50% by weight. When the content of the low-boiling compound is 5 wt% or more, the foaming performance of the obtained thermally expandable particles becomes more excellent. By setting the content of the low-boiling compound to 50% by weight or less, the strength of the shell of the obtained heat-expandable particles becomes more excellent, so that foaming can be performed at a higher expansion ratio. A more preferable lower limit of the content of the low-boiling-point compound in the thermally expandable particles is 10% by weight, and a more preferable upper limit is 30% by weight.

作為上述熱膨脹性粒子中之市售者，例如可列舉：031-DU-40、031-WUF-40、051-DU-40、551-DU-40、053-DU-40、053-WU-40、007-WUF-40、461-DU-40、461-DU-20(均為Akzo Nobel公司製造)、F-30、F-36、F-36LV、F-48、FN-80GS、F-50、F-65(均為松本油脂製藥公司製造)等。 Examples of the commercially available thermally expandable particles include 031-DU-40, 031-WUF-40, 051-DU-40, 551-DU-40, 053-DU-40, and 053-WU-40. 007-WUF-40, 461-DU-40, 461-DU-20 (all manufactured by Akzo Nobel), F-30, F-36, F-36LV, F-48, FN-80GS, F-50 , F-65 (all manufactured by Matsumoto Oil & Fat Pharmaceutical Co., Ltd.), etc.

上述發泡劑之發泡起始溫度之較佳下限為60℃，較佳之上限為130℃。藉由使上述發泡劑之發泡起始溫度為60℃以上，所獲得之接著劑組成物之接著性變得更優異。藉由使上述發泡劑之發泡起始溫度為130℃以下，所獲得之接著劑組成物之低溫下之二次加工性變得更優異。上述發泡劑之發泡起始溫度之更佳之下限為70℃，更佳之上限為110℃，進而較佳之上限為100℃。 A preferable lower limit of the foaming starting temperature of the above-mentioned blowing agent is 60 ° C, and a preferable upper limit is 130 ° C. By setting the foaming start temperature of the foaming agent to 60 ° C. or higher, the adhesiveness of the obtained adhesive composition becomes more excellent. By setting the foaming start temperature of the foaming agent to 130 ° C. or lower, the secondary processability at low temperature of the obtained adhesive composition becomes more excellent. A more preferable lower limit of the foaming starting temperature of the above-mentioned blowing agent is 70 ° C, a more preferable upper limit is 110 ° C, and a more preferable upper limit is 100 ° C.

再者，上述發泡劑之發泡起始溫度意指於利用熱機械分析裝置(TMA)對上述發泡劑進行加熱時，高度方向之位移向正方向移動時之溫度。 In addition, the foaming starting temperature of the foaming agent means a temperature at which the displacement in the height direction moves to the positive direction when the foaming agent is heated by a thermomechanical analysis device (TMA).

於上述發泡劑為粒子形狀之情形時，上述發泡劑之平均粒徑之較佳下限為5μm，較佳之上限為20μm。藉由使上述發泡劑之平均粒徑為5μm以上，所獲得之接著劑組成物中之發泡劑之發泡效率較高，故而接著劑組成物之剝離性變得優異。藉由使上述發泡劑之平均粒徑為20μm以下，所獲得之接著劑組成物之接著力變得優異。上述發泡劑之平均粒徑之更佳上限為18μm。於上述發泡劑為熱膨脹性粒子之情形時，顯著確認到該平均粒徑之效果。 In the case where the foaming agent has a particle shape, a preferable lower limit of the average particle diameter of the foaming agent is 5 μm, and a preferable upper limit is 20 μm. By setting the average particle diameter of the foaming agent to 5 μm or more, the foaming efficiency of the foaming agent in the obtained adhesive composition is high, so that the peelability of the adhesive composition becomes excellent. By making the average particle diameter of the said foaming agent 20 micrometers or less, the adhesive force of the obtained adhesive composition becomes excellent. A more preferable upper limit of the average particle diameter of the foaming agent is 18 μm. When the said foaming agent is a heat-expandable particle, the effect of this average particle diameter was confirmed remarkably.

再者，上述發泡劑之平均粒徑可藉由雷射繞射散射法進行測定。雷射 繞射散射法例如可使用Mastersizer Hydro 2000SM(Malvern公司製造)等。 The average particle diameter of the foaming agent can be measured by a laser diffraction scattering method. As the laser diffraction scattering method, for example, Mastersizer Hydro 2000SM (manufactured by Malvern) can be used.

本發明之接著劑組成物100重量份中上述發泡劑之含量之較佳下限為1重量份，較佳上限為50重量份。藉由使上述發泡劑之含量為該範圍，所獲得之接著劑組成物兼顧接著性與二次加工性之效果變得更優異。上述發泡劑之含量之更佳下限為5重量份，更佳之上限為40重量份，進而較佳之上限為20重量份。 A preferable lower limit of the content of the foaming agent in 100 parts by weight of the adhesive composition of the present invention is 1 part by weight, and a preferable upper limit is 50 parts by weight. When the content of the foaming agent is within this range, the obtained adhesive composition is more excellent in the effect of achieving both adhesiveness and secondary processability. The more preferable lower limit of the content of the foaming agent is 5 parts by weight, the more preferable upper limit is 40 parts by weight, and the more preferable upper limit is 20 parts by weight.

本發明之接著劑組成物含有濕氣硬化型樹脂。作為上述濕氣硬化型樹脂，例如可列舉濕氣硬化型胺酯樹脂、含水解性矽基之樹脂等。其中，較佳為濕氣硬化型胺酯樹脂。 The adhesive composition of the present invention contains a moisture-curable resin. Examples of the moisture-curable resin include a moisture-curable urethane resin and a hydrolyzable silicon group-containing resin. Among them, a moisture-curable urethane resin is preferred.

上述濕氣硬化型胺酯樹脂具有胺酯鍵與異氰酸酯基，分子內之異氰酸酯基與空氣中或被接著體中之水分反應而硬化。 The moisture-curable amine ester resin has an amine ester bond and an isocyanate group, and the isocyanate group in the molecule reacts with moisture in the air or an adherend to be hardened.

上述濕氣硬化型胺酯樹脂可於1分子中僅具有1個異氰酸酯基，亦可具有2個以上。其中，較佳為於分子之主鏈兩末端具有異氰酸酯基。 The moisture-curable urethane resin may have only one isocyanate group in one molecule, or may have two or more. Among them, it is preferable to have isocyanate groups at both ends of the main chain of the molecule.

上述濕氣硬化型胺酯樹脂可藉由使1分子中具有2個以上之羥基之多元醇化合物與1分子中具有2個以上之異氰酸酯基之多異氰酸酯化合物反應而獲得。 The moisture-curable amine ester resin can be obtained by reacting a polyol compound having two or more hydroxyl groups in one molecule and a polyisocyanate compound having two or more isocyanate groups in one molecule.

上述多元醇化合物與多異氰酸酯化合物之反應通常係於多元醇化合物中之羥基(OH)與多異氰酸酯化合物中之異氰酸酯基(NCO)之莫耳比[NCO]/[OH]=2.0~2.5之範圍進行。 The reaction between the above-mentioned polyol compound and the polyisocyanate compound is usually based on the molar ratio [NCO] / [OH] = 2.0 ~ 2.5 of the hydroxyl group (OH) in the polyol compound and the isocyanate group (NCO) in the polyisocyanate compound. get on.

作為成為上述濕氣硬化型胺酯樹脂之原料之多元醇化合物，可使用通常用於製造聚胺酯之公知之多元醇化合物，例如可列舉聚酯 多元醇、聚醚多元醇、聚伸烷基多元醇、聚碳酸酯多元醇等。該等多元醇化合物可單獨使用，亦可將2種以上組合使用。 As the polyol compound used as a raw material of the moisture-curable urethane resin, a well-known polyol compound generally used in the production of polyurethanes can be used, and examples thereof include polyester polyols, polyether polyols, and polyalkylene polyols. , Polycarbonate polyols, etc. These polyol compounds may be used alone or in combination of two or more kinds.

作為上述聚酯多元醇，例如可列舉：藉由多元羧酸與多元醇之反應而獲得之聚酯多元醇、使ε-己內酯開環聚合而獲得之聚-ε-己內酯多元醇等。 Examples of the polyester polyol include a polyester polyol obtained by a reaction of a polycarboxylic acid and a polyol, and a poly-ε-caprolactone polyol obtained by ring-opening polymerization of ε-caprolactone. Wait.

作為成為上述聚酯多元醇之原料之上述多元羧酸，例如可列舉：對苯二甲酸、間苯二甲酸、1,5-萘二甲酸、2,6-萘二甲酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、十亞甲基二羧酸(decamethylene-dicarboxylic acid)、十二亞甲基二羧酸等。 Examples of the polycarboxylic acid used as a raw material of the polyester polyol include terephthalic acid, isophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, succinic acid, and glutaric acid. Acids, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decamethylene-dicarboxylic acid, dodecamethylene dicarboxylic acid, and the like.

作為成為上述聚酯多元醇之原料之上述多元醇，例如可列舉：乙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、新戊二醇、1,5-戊二醇、1,6-己二醇、二乙二醇、環己二醇等。 Examples of the polyol that serves as a raw material for the polyester polyol include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, and 1,5 -Pentanediol, 1,6-hexanediol, diethylene glycol, cyclohexanediol, etc.

作為上述聚醚多元醇，例如可列舉：乙二醇、丙二醇、四氫呋喃之開環聚合物、3-甲基四氫呋喃之開環聚合物及該等或者其衍生物之無規共聚物或嵌段共聚物、雙酚型之聚氧伸烷基改質體等。 Examples of the polyether polyol include ethylene glycol, propylene glycol, ring-opening polymer of tetrahydrofuran, ring-opening polymer of 3-methyltetrahydrofuran, and random copolymers or block copolymers of these or their derivatives. Compounds, polyoxyalkylene modified bodies of bisphenol type, etc.

上述雙酚型之聚氧伸烷基改質體係使環氧烷(例如環氧乙烷、環氧丙烷、環氧丁烷、環氧異丁烷等)與雙酚型分子骨架之活性氫部分進行加成反應而獲得之聚醚多元醇，可為無規共聚物，亦可為嵌段共聚物。上述雙酚型之聚氧伸烷基改質體較佳為於雙酚型分子骨架之兩末端加成有1種或2種以上之環氧烷。作為雙酚型，並無特別限定，可列舉A型、F型、S型等，較佳為雙酚A型。 The above-mentioned bisphenol-type polyoxyalkylene modification system makes alkylene oxides (such as ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, etc.) and the active hydrogen portion of the bisphenol-type molecular skeleton The polyether polyol obtained by the addition reaction may be a random copolymer or a block copolymer. The bisphenol-type polyoxyalkylene modified body is preferably one or two or more kinds of alkylene oxides added to both ends of the bisphenol-type molecular skeleton. The bisphenol type is not particularly limited, and examples thereof include A type, F type, and S type, and a bisphenol A type is preferred.

作為上述聚伸烷基多元醇，例如可列舉聚丁二烯多元醇、氫 化聚丁二烯多元醇、氫化聚異戊二烯多元醇等。 Examples of the polyalkylene polyol include polybutadiene polyol, hydrogenated polybutadiene polyol, and hydrogenated polyisoprene polyol.

作為上述聚碳酸酯多元醇，例如可列舉聚六亞甲基碳酸酯多元醇、聚環己烷二亞甲基碳酸酯多元醇等。 Examples of the polycarbonate polyol include polyhexamethylene carbonate polyol, polycyclohexane dimethylene carbonate polyol, and the like.

作為成為上述濕氣硬化型胺酯樹脂之原料之多異氰酸酯化合物，可較佳地使用芳香族多異氰酸酯化合物、脂肪族多異氰酸酯化合物。 As the polyisocyanate compound that is a raw material of the moisture-curable urethane resin, an aromatic polyisocyanate compound and an aliphatic polyisocyanate compound can be preferably used.

作為上述芳香族多異氰酸酯化合物，例如可列舉二苯甲烷二異氰酸酯、二苯甲烷二異氰酸酯之液狀改質物、聚合MDI(polymeric MDI)、甲苯二異氰酸酯、萘-1,5-二異氰酸酯等。 Examples of the aromatic polyisocyanate compound include diphenylmethane diisocyanate, liquid modification of diphenylmethane diisocyanate, polymerized MDI (polymeric MDI), toluene diisocyanate, naphthalene-1,5-diisocyanate, and the like.

作為上述脂肪族多異氰酸酯化合物，例如可列舉六亞甲基二異氰酸酯、三甲基六亞甲基二異氰酸酯、離胺酸二異氰酸酯、降莰烷二異氰酸酯、反式環己烷-1,4-二異氰酸酯、異佛酮二異氰酸酯、氫化苯二甲基二異氰酸酯、氫化二苯甲烷二異氰酸酯、環己烷二異氰酸酯、雙(異氰酸基甲基)環己烷、二環己基甲烷二異氰酸酯等。 Examples of the aliphatic polyisocyanate compound include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, and transcyclohexane-1,4- Diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, cyclohexane diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, etc. .

作為上述多異氰酸酯化合物，尤其是就蒸氣壓及毒性較低之方面、處理容易性之方面而言，較佳為二苯甲烷二異氰酸酯及其改質物。 As said polyisocyanate compound, the diphenylmethane diisocyanate and its modification are preferable especially from the point of low vapor pressure and toxicity, and a point of easy handling.

上述多異氰酸酯化合物可單獨使用，亦可將2種以上組合使用。 These polyisocyanate compounds may be used alone or in combination of two or more kinds.

又，上述濕氣硬化型胺酯樹脂較佳為使用具有下述式(1)所表示之結構之多元醇化合物而獲得者。藉由使用具有下述式(1)所表示之結構之多元醇化合物，可獲得接著性優異之組成物及柔軟且伸長率良好之硬化物，且與上述自由基聚合性化合物之相溶性變得優異。其中，較佳為使用由丙二醇、四氫呋喃(THF)化合物之開環聚合化合物或具有甲基等取代基之四氫呋喃化合物之開環聚合化合物構成之聚醚多元醇者。 The moisture-curable urethane resin is preferably obtained by using a polyol compound having a structure represented by the following formula (1). By using a polyhydric alcohol compound having a structure represented by the following formula (1), a composition having excellent adhesion and a hardened material having good elongation can be obtained, and the compatibility with the above radical polymerizable compound becomes Excellent. Among these, a polyether polyol composed of a ring-opening polymerization compound of propylene glycol, a tetrahydrofuran (THF) compound, or a ring-opening polymerization compound of a tetrahydrofuran compound having a substituent such as a methyl group is preferably used.

式(1)中，R表示氫原子、甲基或乙基，l表示0~5之整數，m為1~500之整數，n為1~10之整數。l較佳為0~4，m較佳為50~200，n較佳為1~5。 In formula (1), R represents a hydrogen atom, a methyl group, or an ethyl group, l represents an integer of 0 to 5, m is an integer of 1 to 500, and n is an integer of 1 to 10. l is preferably 0 to 4, m is preferably 50 to 200, and n is preferably 1 to 5.

再者，l為0之情形意指與R鍵結之碳直接與氧鍵結之情形。 Furthermore, the case where l is 0 means a case where the carbon bonded to R is directly bonded to oxygen.

上述含水解性矽基之樹脂之分子內之水解性矽基與空氣中或被接著體中之水分反應而硬化。 The hydrolyzable silicon group in the molecule of the hydrolyzable silicon group-containing resin reacts with moisture in the air or the adherend to harden.

上述含水解性矽基之樹脂可於1分子中僅具有1個水解性矽基，亦可具有2個以上。其中，較佳為於分子之主鏈兩末端具有水解性矽基。 The above-mentioned hydrolyzable silicon group-containing resin may have only one hydrolyzable silicon group per molecule, or may have two or more. Among these, it is preferable that the both ends of the main chain of the molecule have a hydrolyzable silicon group.

上述水解性矽基係由下述式(2)所表示。 The hydrolyzable silicon group is represented by the following formula (2).

-SiR1 3-aXa (2) -SiR 1 3-a X a (2)

式(2)中，R1分別獨立地表示可經取代之碳數1以上且20以下之烷基、碳數6以上且20以下芳基、碳數7以上且20以下之芳烷基或-OSiR2 3(R2分別獨立地表示碳數1以上且20以下之烴基)所表示之三有機矽烷氧基。又，式(2)中，X分別獨立地為羥基或水解性基。進而，式(2)中，a為1~3之整數。 In formula (2), R 1 each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or- The triorganosiloxy group represented by OSiR 2 3 (R 2 each independently represents a hydrocarbon group having 1 to 20 carbon atoms). In Formula (2), X is each independently a hydroxyl group or a hydrolyzable group. Furthermore, in Formula (2), a is an integer of 1-3.

上述水解性基並無特別限定，例如可列舉：氫原子、鹵素原子、烷氧基、烯氧基、芳氧基、醯氧基、酮肟酯(ketoximate)基、胺基、 醯胺基、酸醯胺基、胺基氧基、巰基等。其中，就活性較高之方面而言，較佳為鹵素原子、烷氧基、烯氧基、醯氧基，就水解性穩定而容易處理之方面而言，更佳為甲氧基、乙氧基等烷氧基，進而較佳為甲氧基、乙氧基。又，就安全性之觀點而言，較佳為藉由反應而脫離之化合物分別為乙醇、丙酮之乙氧基、異丙烯氧基。 The hydrolyzable group is not particularly limited, and examples thereof include a hydrogen atom, a halogen atom, an alkoxy group, an alkenyl group, an aryloxy group, a fluorenyloxy group, a ketoximate group, an amine group, a fluorenylamino group, Acid amido, amino, mercapto and the like. Among them, a halogen atom, an alkoxy group, an alkenyloxy group, and a fluorenyl group are preferable in terms of high activity, and a methoxy group and ethoxy group are more preferable in terms of stable hydrolyzability and easy handling. An alkoxy group such as a group is more preferably a methoxy group or an ethoxy group. From the viewpoint of safety, it is preferable that the compounds to be removed by the reaction are ethanol, ethoxy group of acetone, and isopropenyloxy group, respectively.

上述羥基或上述水解性基可以1~3個之範圍鍵結於1個矽原子。於2個以上之上述羥基或上述水解性基鍵結於1個矽原子之情形時，該等基可相同，亦可不同。 The hydroxyl group or the hydrolyzable group may be bonded to one silicon atom in a range of 1 to 3. When two or more of the above-mentioned hydroxyl group or the above-mentioned hydrolyzable group are bonded to one silicon atom, the groups may be the same or different.

就硬化性之觀點而言，上述式(2)中之a較佳為2或3，尤佳為3。又，就保存穩定性之觀點而言，a較佳為2。 From the viewpoint of hardenability, a in the formula (2) is preferably 2 or 3, and particularly preferably 3. From the viewpoint of storage stability, a is preferably 2.

又，作為上述式(2)中之R1，例如可列舉：甲基、乙基等烷基、環己基等環烷基、苯基等芳基、苄基等芳烷基、三甲基矽烷氧基、氯甲基、甲氧基甲基等。其中，較佳為甲基。 Examples of R 1 in the formula (2) include an alkyl group such as methyl and ethyl, a cycloalkyl group such as cyclohexyl, an aryl group such as phenyl, an aralkyl group such as benzyl, and trimethylsilane Oxy, chloromethyl, methoxymethyl and the like. Among them, methyl is preferred.

作為上述水解性矽基，例如可列舉：甲基二甲氧基矽基、三甲氧基矽基、三乙氧基矽基、三(2-丙烯基氧基)矽基、三乙醯氧基矽基、(氯甲基)二甲氧基矽基、(氯甲基)二乙氧基矽基、(二氯甲基)二甲氧基矽基、(1-氯乙基)二甲氧基矽基、(1-氯丙基)二甲氧基矽基、(甲氧基甲基)二甲氧基矽基、(甲氧基甲基)二乙氧基矽基、(乙氧基甲基)二甲氧基矽基、(1-甲氧基乙基)二甲氧基矽基、(胺基甲基)二甲氧基矽基、(N,N-二甲胺基甲基)二甲氧基矽基、(N,N-二乙胺基甲基)二甲氧基矽基、(N,N-二乙胺基甲基)二乙氧基矽基、(N-(2-胺基乙基)胺基甲基)二甲氧基矽基、(乙醯氧基甲基)二甲氧基矽基、(乙醯氧基甲基)二 乙氧基矽基等。 Examples of the hydrolyzable silicon group include methyldimethoxysilyl group, trimethoxysilyl group, triethoxysilyl group, tris (2-propenyloxy) silyl group, and triethylfluorenyloxy group. Silyl, (chloromethyl) dimethoxysilyl, (chloromethyl) diethoxysilyl, (dichloromethyl) dimethoxysilyl, (1-chloroethyl) dimethoxy Silyl, (1-chloropropyl) dimethoxysilyl, (methoxymethyl) dimethoxysilyl, (methoxymethyl) diethoxysilyl, (ethoxy (Methyl) dimethoxysilyl, (1-methoxyethyl) dimethoxysilyl, (aminomethyl) dimethoxysilyl, (N, N-dimethylaminomethyl) ) Dimethoxysilyl, (N, N-diethylaminomethyl) dimethoxysilyl, (N, N-diethylaminomethyl) diethoxysilyl, (N- ( 2-Aminoethyl) aminomethyl) dimethoxysilyl, (ethoxymethyl) dimethoxysilyl, (ethoxymethyl) diethoxysilyl, and the like.

作為上述含水解性矽基之樹脂，例如可列舉：含水解性矽基之(甲基)丙烯酸樹脂、於分子鏈末端或分子鏈末端部位具有水解性矽基之有機聚合物、含水解性矽基之聚胺酯樹脂等。 Examples of the hydrolyzable silicon group-containing resin include (meth) acrylic resin containing a hydrolyzable silicon group, an organic polymer having a hydrolyzable silicon group at a molecular chain end or a molecular chain end portion, and hydrolyzable silicon Based polyurethane resins and the like.

上述含水解性矽基之(甲基)丙烯酸樹脂較佳為於主鏈具有源自含水解性矽基之(甲基)丙烯酸酯與(甲基)丙烯酸烷基酯之重複結構單元。 The hydrolyzable silicon group-containing (meth) acrylic resin preferably has a repeating structural unit derived from the hydrolyzable silicon group-containing (meth) acrylate and an alkyl (meth) acrylate in the main chain.

作為上述含水解性矽基之(甲基)丙烯酸酯，例如可列舉：(甲基)丙烯酸3-(三甲氧基矽基)丙酯、(甲基)丙烯酸3-(三乙氧基矽基)丙酯、(甲基)丙烯酸3-(甲基二甲氧基矽基)丙酯、(甲基)丙烯酸2-(三甲氧基矽基)乙酯、(甲基)丙烯酸2-(三乙氧基矽基)乙酯、(甲基)丙烯酸2-(甲基二甲氧基矽基)乙酯、(甲基)丙烯酸三甲氧基矽基甲酯、(甲基)丙烯酸三乙氧基矽基甲酯、(甲基)丙烯酸(甲基二甲氧基矽基)甲酯等。 Examples of the hydrolyzable silicon group-containing (meth) acrylate include 3- (trimethoxysilyl) propyl (meth) acrylate and 3- (triethoxysilyl) (meth) acrylate. ) Propyl ester, 3- (methyldimethoxysilyl) propyl (meth) acrylate, 2- (trimethoxysilyl) ethyl (meth) acrylate, 2- (tri) (meth) acrylate Ethoxysilyl) ethyl ester, 2- (methyldimethoxysilyl) ethyl (meth) acrylate, trimethoxysilyl methyl (meth) acrylate, triethoxy (meth) acrylate Methylsilyl methyl, (meth) methacrylate (methyldimethoxysilyl) methyl, and the like.

作為上述(甲基)丙烯酸烷基酯，例如可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸正戊酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸正庚酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸正壬酯、(甲基)丙烯酸正癸酯、(甲基)丙烯酸正十二烷基酯、(甲基)丙烯酸硬脂酯等。 Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, ( N-butyl methacrylate, isobutyl (meth) acrylate, third butyl (meth) acrylate, n-amyl (meth) acrylate, n-hexyl (meth) acrylate, (meth) acrylic ring Hexyl ester, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate , N-dodecyl (meth) acrylate, stearyl (meth) acrylate, and the like.

作為製造上述含水解性矽基之(甲基)丙烯酸樹脂之方法， 具體而言，例如可列舉國際公開第2016/035718號所記載之含水解性矽基之(甲基)丙烯酸酯系聚合物之合成方法等。 As a method for producing the hydrolyzable silicon group-containing (meth) acrylic resin, specifically, for example, a hydrolyzable silicon group-containing (meth) acrylate polymer described in International Publication No. 2016/035718 Synthesis method, etc.

上述於分子鏈末端或分子鏈末端部位具有水解性矽基之有機聚合物於主鏈之末端及側鏈之末端之至少一者具有水解性矽基。 The organic polymer having a hydrolyzable silicon group at a molecular chain end or a molecular chain terminal portion has a hydrolyzable silicon group in at least one of a terminal of a main chain and a terminal of a side chain.

上述主鏈之骨架結構並無特別限定，例如可列舉飽和烴系聚合物、聚氧伸烷基系聚合物、(甲基)丙烯酸酯系聚合物等。 The backbone structure of the main chain is not particularly limited, and examples thereof include a saturated hydrocarbon polymer, a polyoxyalkylene polymer, a (meth) acrylate polymer, and the like.

作為上述聚氧伸烷基系聚合物，例如可列舉具有聚氧伸乙基結構、聚氧伸丙基結構、聚氧伸丁基結構、聚氧四亞甲基結構、聚氧乙烯-聚氧丙烯共聚物結構、聚氧丙烯-聚氧丁烯共聚物結構之聚合物等。 Examples of the polyoxyalkylene-based polymer include a polyoxyethylene structure, a polyoxypropylene structure, a polyoxybutylene structure, a polyoxytetramethylene structure, and a polyoxyethylene-polyoxy group. Polymers of propylene copolymer structure, polyoxypropylene-polyoxybutene copolymer structure, etc.

作為製造上述於分子鏈末端或分子鏈末端部位具有水解性矽基之有機聚合物之方法，具體而言，例如可列舉國際公開第2016/035718號所記載之僅於分子鏈末端或分子鏈末端部位具有交聯性矽基的有機聚合物之合成方法。又，作為製造上述於分子鏈末端或分子鏈末端部位具有水解性矽基之有機聚合物之另一方法，例如可列舉國際公開第2012/117902號所記載之含反應性矽基之聚氧伸烷基系聚合物之合成方法等。 As a method for producing the above-mentioned organic polymer having a hydrolyzable silicon group at a molecular chain end or a molecular chain end portion, specifically, for example, the molecular chain end or the molecular chain end described in International Publication No. 2016/035718 may be mentioned. Method for synthesizing an organic polymer having a crosslinkable silicon group at a site. In addition, as another method for producing the organic polymer having a hydrolyzable silicon group at the molecular chain end or the molecular chain end portion, for example, a reactive silicon group-containing polyoxygenate described in International Publication No. 2012/117902 can be cited. Synthetic methods of alkyl polymers.

作為製造上述含水解性矽基之聚胺酯樹脂之方法，例如可列舉於使多元醇化合物與多異氰酸酯化合物反應而製造聚胺酯樹脂時，進而使矽烷偶合劑等含矽基之化合物反應之方法等。具體而言，例如可列舉日本特開2017-48345號公報所記載之具有水解性矽基之胺酯低聚物之合成方法等。 Examples of a method for producing the hydrolyzable silicon group-containing polyurethane resin include a method for reacting a polyhydric alcohol compound with a polyisocyanate compound to produce a polyurethane resin, and further reacting a silicon group-containing compound such as a silane coupling agent. Specifically, for example, a method for synthesizing the amine ester oligomer having a hydrolyzable silicon group described in Japanese Patent Application Laid-Open No. 2017-48345 can be mentioned.

作為上述矽烷偶合劑，例如可列舉：乙烯基三氯矽烷、乙烯基三乙氧基矽烷、乙烯基三(β-甲氧基-乙氧基)矽烷、β-(3,4-環氧 環己基)-乙基三甲氧基矽烷、γ-縮水甘油氧基丙基三甲氧基矽烷、γ-縮水甘油氧基丙基甲基二乙氧基矽烷、γ-甲基丙烯醯氧基丙基三甲氧基矽烷、N-(β-胺基乙基)-γ-胺基丙基三甲氧基矽烷、N-(β-胺基乙基)-γ-胺基丙基三甲基二甲氧基矽烷、N-苯基-γ-胺基丙基三甲氧基矽烷、γ-氯丙基三甲氧基矽烷、γ-巰基丙基三甲氧基矽烷、γ-胺基丙基三甲氧基矽烷、3-異氰酸基丙基三甲氧基矽烷(3-isocyanatepropyl trimethoxysilane)、3-異氰酸基丙基三乙氧基矽烷等。其中，較佳為γ-巰基丙基三甲氧基矽烷、3-異氰酸基丙基三甲氧基矽烷、3-異氰酸基丙基三乙氧基矽烷。該等矽烷偶合劑可單獨使用，亦可將2種以上組合使用。 Examples of the silane coupling agent include vinyltrichlorosilane, vinyltriethoxysilane, vinyltri (β-methoxy-ethoxy) silane, and β- (3,4-epoxy ring). (Hexyl) -ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethylsilane Oxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethyldimethoxy Silane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, 3 -3-isocyanatepropyl trimethoxysilane, 3-isocyanatepropyl trimethoxysilane, and the like. Among these, γ-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane are preferred. These silane coupling agents may be used alone or in combination of two or more kinds.

進而，上述濕氣硬化型樹脂亦可具有自由基聚合性官能基。作為上述濕氣硬化型樹脂亦可具有之自由基聚合性官能基，較佳為具有不飽和雙鍵之基，尤其是就反應性之方面而言，更佳為(甲基)丙烯醯基。 Furthermore, the said moisture-curable resin may have a radical polymerizable functional group. As the radically polymerizable functional group that the moisture-curable resin may have, a group having an unsaturated double bond is preferred, and in particular, a (meth) acrylfluorenyl group is more preferable in terms of reactivity.

再者，具有自由基聚合性官能基之濕氣硬化型樹脂並不包含於下述自由基聚合性化合物中，而是作為濕氣硬化型樹脂來處理。 The moisture-curable resin having a radically polymerizable functional group is not included in the radically polymerizable compound described below, but is treated as a moisture-curable resin.

上述濕氣硬化型樹脂之重量平均分子量並無特別限定，較佳之下限為800，較佳之上限為1萬。藉由使上述濕氣硬化型樹脂之重量平均分子量為該範圍，所獲得之接著劑組成物於硬化時交聯密度不會變得過高而柔軟性變得更優異，且塗佈性變得更優異。上述濕氣硬化型樹脂之重量平均分子量之更佳下限為2000，更佳之上限為8000，進而較佳之下限為2500，進而較佳之上限為6000。 The weight average molecular weight of the moisture-curable resin is not particularly limited, and a preferred lower limit is 800, and a preferred upper limit is 10,000. By setting the weight-average molecular weight of the moisture-curable resin to be in this range, the obtained adhesive composition does not become too high in cross-linking density at the time of curing, becomes more excellent in flexibility, and becomes more coatable. More excellent. A more preferable lower limit of the weight-average molecular weight of the moisture-curable resin is 2000, a more preferable upper limit is 8000, a more preferable lower limit is 2500, and a more preferable upper limit is 6,000.

再者，於本說明書中，上述重量平均分子量係利用凝膠滲透層析法(GPC)進行測定並藉由聚苯乙烯換算而求出之值。作為藉由GPC測定基 於聚苯乙烯換算之重量平均分子量時之管柱，例如可列舉Shodex LF-804(昭和電工公司製造)等。又，作為GPC所使用之溶劑，可列舉四氫呋喃等。 In addition, in this specification, the said weight average molecular weight is a value measured by gel permeation chromatography (GPC), and calculated | required by polystyrene conversion. Examples of the column used when measuring the weight-average molecular weight based on polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko). Examples of the solvent used for GPC include tetrahydrofuran.

本發明之接著劑組成物100重量份中上述濕氣硬化型樹脂之含量之較佳之下限為20重量份，較佳之上限為90重量份。藉由使上述濕氣硬化型樹脂之含量為該範圍，所獲得之接著劑組成物維持優異之耐候性或硬化物之柔軟性，並且濕氣硬化性變得更優異。上述濕氣硬化型樹脂之含量之更佳下限為30重量份，更佳之上限為70重量份。 A preferable lower limit of the content of the moisture-curable resin in 100 parts by weight of the adhesive composition of the present invention is 20 parts by weight, and a preferable upper limit is 90 parts by weight. By setting the content of the moisture-curable resin to be in this range, the obtained adhesive composition maintains excellent weather resistance or softness of the cured product, and furthermore, moisture-curability becomes more excellent. A more preferable lower limit of the content of the moisture-curable resin is 30 parts by weight, and a more preferable upper limit is 70 parts by weight.

本發明人等為了進一步提高兼顧接著性與二次加工性之效果，對下述情況進行研究：為了增加與被接著體接觸之每單位面積之發泡劑之量而使含有本發明之接著劑組成物之接著層增厚。 In order to further improve the effect of combining adhesiveness and secondary processability, the present inventors have studied the case where the adhesive of the present invention is contained in order to increase the amount of foaming agent per unit area in contact with the adherend. The adhesive layer of the composition is thickened.

圖1係表示(a)接著層之厚度較小之情形時及(b)較大之情形時之利用本發明之接著劑組成物的被接著體之接著狀態之示意圖。 FIG. 1 is a schematic diagram showing the state of adhesion of an adherend using the adhesive composition of the present invention when (a) the thickness of the adhesive layer is small and (b) when the thickness is large.

如圖1所示，由將被接著體1接著之接著劑組成物2構成之接著層之厚度3越大，每單位面積4之接著劑組成物2中存在之發泡劑5之量越多。因此，藉由於可維持接著性之限度內將接著層之厚度3設為較大之厚度，而兼顧接著性與二次加工性之效果進一步提高。於該情形時，為了維持接著層之厚度3，較佳為進行光硬化作為預處理。因此。為了表現出光硬化性，本發明之接著劑組成物較佳為含有自由基聚合性化合物及光自由基聚合起始劑。即，藉由含有上述自由基聚合性化合物及上述光自由基聚合起始劑而保證光硬化性與濕氣硬化性，從而接著性與二次加工性之兼顧變得更有效。此種本發明之接著劑組成物尤其可較佳地用於顯示元件用密封劑或窄 邊緣設計之殼體連接所使用之接著劑。 As shown in FIG. 1, the larger the thickness 3 of the adhesive layer composed of the adhesive composition 2 to which the adherend 1 is attached, the larger the amount of the foaming agent 5 present in the adhesive composition 2 per unit area 4. . Therefore, since the thickness 3 of the adhesive layer is set to a large thickness within the limit that the adhesiveness can be maintained, the effect of considering both adhesiveness and secondary workability is further improved. In this case, in order to maintain the thickness 3 of the adhesive layer, it is preferable to perform photohardening as a pretreatment. therefore. In order to exhibit photocurability, the adhesive composition of the present invention preferably contains a radical polymerizable compound and a photoradical polymerization initiator. That is, by including the radically polymerizable compound and the photoradical polymerization initiator, the photo-curability and moisture-curability are ensured, so that the balance between adhesion and secondary processability becomes more effective. Such an adhesive composition of the present invention is particularly preferably used as an adhesive for a display element sealant or a narrow-edge-designed case connection.

作為上述自由基聚合性化合物，只要為具有光聚合性之自由基聚合性化合物即可，只要為分子中具有自由基聚合性官能基之化合物，則並無特別限定。其中，具有不飽和雙鍵作為自由基聚合性官能基之化合物合適，尤其是就反應性之方面而言，具有(甲基)丙烯醯基之化合物(以下，亦稱為「(甲基)丙烯酸化合物」)合適。 The radical polymerizable compound is not particularly limited as long as it is a photopolymerizable radical polymerizable compound, and it is a compound having a radical polymerizable functional group in the molecule. Among them, a compound having an unsaturated double bond as a radical polymerizable functional group is suitable, and especially a compound having a (meth) acrylfluorenyl group (hereinafter, also referred to as "(meth) acrylic acid") in terms of reactivity. Compound ") is suitable.

再者，於本說明書中，上述「(甲基)丙烯醯基」意指丙烯醯基或甲基丙烯醯基，上述「(甲基)丙烯酸」意指丙烯酸或甲基丙烯酸。 In addition, in the present specification, the "(meth) acrylfluorenyl" means acrylfluorenyl or methacrylfluorenyl, and the "(meth) acrylic acid" means acrylic acid or methacrylic acid.

作為上述(甲基)丙烯酸化合物，例如可列舉：(甲基)丙烯酸酯化合物、(甲基)丙烯酸環氧酯、(甲基)丙烯酸胺酯等。 Examples of the (meth) acrylic compound include (meth) acrylate compounds, epoxy (meth) acrylates, and (meth) acrylates.

再者，於本說明書中，所謂上述「(甲基)丙烯酸酯」，意指丙烯酸酯或甲基丙烯酸酯。又，上述(甲基)丙烯酸胺酯不具有殘存異氰酸基。 In addition, in this specification, the "(meth) acrylate" means an acrylate or a methacrylate. The amine (meth) acrylate does not have a residual isocyanate group.

作為上述(甲基)丙烯酸酯化合物中之單官能者，例如可列舉：N-丙烯醯氧基乙基六氫鄰苯二甲醯亞胺等鄰苯二甲醯亞胺丙烯酸酯類；各種醯亞胺(甲基)丙烯酸酯、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸異肉豆著酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸4-羥基丁 酯、(甲基)丙烯酸2-甲氧基乙酯、(甲基)丙烯酸2-乙氧基乙酯、(甲基)丙烯酸2-丁氧基乙酯、甲氧基乙二醇(甲基)丙烯酸酯、甲氧基聚乙二醇(甲基)丙烯酸酯、乙基卡必醇(甲基)丙烯酸酯、(甲基)丙烯酸四氫糠酯、(甲基)丙烯酸2-苯氧基乙酯、苯氧基二乙二醇(甲基)丙烯酸酯、苯氧基聚乙二醇(甲基)丙烯酸酯、(甲基)丙烯酸2,2,2-三氟乙酯、(甲基)丙烯酸2,2,3,3-四氟丙酯、(甲基)丙烯酸1H,1H,5H-八氟戊酯、(甲基)丙烯酸二甲胺基乙酯、(甲基)丙烯酸二乙胺基乙酯、琥珀酸2-(甲基)丙烯醯氧基乙酯、六氫鄰苯二甲酸2-(甲基)丙烯醯氧基乙酯、鄰苯二甲酸2-(甲基)丙烯醯氧基乙基-2-羥基丙酯、(甲基)丙烯酸縮水甘油酯、磷酸2-(甲基)丙烯醯氧基乙酯等可列舉。 Examples of the monofunctional group in the (meth) acrylate compound include phthalimide acrylates such as N-acryloxyethylhexahydrophthalimide and the like Imine (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate , Third butyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isononyl (meth) acrylate, Isodecyl (meth) acrylate, lauryl (meth) acrylate, isomyristate (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) Isopropyl acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) 2-hydroxybutyl acrylate, 4-hydroxybutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2 (meth) acrylate -Butoxyethyl, methoxyethyl Glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethyl carbitol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (meth) acrylic acid 2-phenoxyethyl ester, phenoxy diethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, (meth) acrylate 2,2,2-trifluoroethyl Esters, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, (methyl) ) Diethylaminoethyl acrylate, 2- (meth) acryloxyethyl succinate, 2- (meth) acryloxyethyl hexahydrophthalate, 2-phthalate (Meth) acryloxyethyl-2-hydroxypropyl, glycidyl (meth) acrylate, 2- (meth) acryloxyethyl phosphate, etc. are mentioned.

又，作為上述(甲基)丙烯酸酯化合物中之2官能者，例如可列舉：1,3-丁二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、1,10-癸二醇二(甲基)丙烯酸酯、2-正丁基-2-乙基-1,3-丙二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、環氧乙烷加成雙酚A二(甲基)丙烯酸酯、環氧丙烷加成雙酚A二(甲基)丙烯酸酯、環氧乙烷加成雙酚F二(甲基)丙烯酸酯、二(甲基)丙烯酸二羥甲基二環戊二烯酯、新戊二醇二(甲基)丙烯酸酯、環氧乙烷改質異三聚氰酸二(甲基)丙烯酸酯、(甲基)丙烯酸2-羥基-3-(甲基)丙烯醯氧基丙酯、碳酸酯二醇二(甲基)丙烯酸酯、 聚醚二醇二(甲基)丙烯酸酯、聚酯二醇二(甲基)丙烯酸酯、聚己內酯二醇二(甲基)丙烯酸酯、聚丁二烯二醇二(甲基)丙烯酸酯等。 Examples of the bifunctional compound in the (meth) acrylate compound include 1,3-butanediol di (meth) acrylate and 1,4-butanediol di (meth) acrylate. , 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 2-n-butyl 2-ethyl-1,3-propanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (methyl) Base) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, ethylene oxide Alkane addition bisphenol A di (meth) acrylate, propylene oxide addition bisphenol A di (meth) acrylate, ethylene oxide addition bisphenol F di (meth) acrylate, bis (methyl) Group) Dimethylol dicyclopentadiene acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide modified isotricyanate di (meth) acrylate, (meth) acrylic acid 2-Hydroxy-3- (meth) propylene ethoxypropyl ester, carbonate diol di (meth) propylene Ester, polyether glycol di (meth) acrylate, polyester glycol di (meth) acrylate, polycaprolactone glycol di (meth) acrylate, polybutadiene glycol di (meth) ) Acrylate, etc.

又，作為上述(甲基)丙烯酸酯化合物中之3官能以上者，例如可列舉：三羥甲基丙烷三(甲基)丙烯酸酯、環氧乙烷加成三羥甲基丙烷三(甲基)丙烯酸酯、環氧丙烷加成三羥甲基丙烷三(甲基)丙烯酸酯、己內酯改質三羥甲基丙烷三(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、環氧乙烷加成異三聚氰酸三(甲基)丙烯酸酯、甘油三(甲基)丙烯酸酯、環氧丙烷加成甘油三(甲基)丙烯酸酯、磷酸三(甲基)丙烯醯氧基乙酯、二-三羥甲基丙烷四(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯等。 In addition, examples of the tri- or more functional group in the (meth) acrylate compound include trimethylolpropane tri (meth) acrylate, and ethylene oxide-added trimethylolpropane tri (methyl) ) Acrylate, propylene oxide addition trimethylolpropane tri (meth) acrylate, caprolactone modified trimethylolpropane tri (meth) acrylate, neopentaerythritol tri (meth) acrylic acid Ester, ethylene oxide addition isotricyanate tri (meth) acrylate, glycerol tri (meth) acrylate, propylene oxide addition glycerol tri (meth) acrylate, phosphate tri (meth) acrylate Acrylic ethoxyethyl, di-trimethylolpropane tetra (meth) acrylate, neopentaerythritol tetra (meth) acrylate, dinepentaerythritol penta (meth) acrylate, dineopentyl Tetraol hexa (meth) acrylate and the like.

作為上述(甲基)丙烯酸環氧酯，例如可列舉藉由依據常規方法使環氧化合物與(甲基)丙烯酸於鹼性觸媒之存在下反應而獲得者等。 Examples of the (meth) acrylate epoxy ester include those obtained by reacting an epoxy compound and (meth) acrylic acid in the presence of a basic catalyst in accordance with a conventional method.

作為成為用以合成上述(甲基)丙烯酸環氧酯之原料之環氧化合物，例如可列舉：雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、2,2'-二烯丙基雙酚A型環氧樹脂、氫化雙酚型環氧樹脂、環氧丙烷加成雙酚A型環氧樹脂、間苯二酚型環氧樹脂、聯苯型環氧樹脂、硫醚型環氧樹脂、二苯醚型環氧樹脂、二環戊二烯型環氧樹脂、萘型環氧樹脂、苯酚酚醛清漆型環氧樹脂、鄰甲酚酚醛清漆型環氧樹脂、二環戊二烯酚醛清漆型環氧樹脂、聯苯酚醛清漆型環氧樹脂、萘酚酚醛清漆型環氧樹脂、縮水甘油胺型環氧樹脂、烷基多元醇型環氧樹脂、橡膠改質型環氧樹脂、縮水甘油酯化合物、雙酚A型環硫樹脂等。 Examples of the epoxy compound used as a raw material for the synthesis of the (meth) acrylic epoxy ester include bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, 2 , 2'-diallyl bisphenol A epoxy resin, hydrogenated bisphenol epoxy resin, propylene oxide addition bisphenol A epoxy resin, resorcinol epoxy resin, biphenyl ring Oxygen resin, thioether type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, o-cresol novolac type epoxy resin Resin, dicyclopentadiene novolac epoxy resin, biphenol novolac epoxy resin, naphthol novolac epoxy resin, glycidylamine epoxy resin, alkyl polyol epoxy resin, rubber Modified epoxy resin, glycidyl ester compound, bisphenol A episulfide resin, etc.

作為上述(甲基)丙烯酸環氧酯中之市售者，例如可列舉：EBECRYL860、EBECRYL3200、EBECRYL3201、EBECRYL3412、EBECRYL3600、EBECRYL3700、EBECRYL3701、EBECRYL3702、EBECRYL3703、EBECRYL3800、EBECRYL6040、EBECRYL RDX63182(均為Daicel-Allnes公司製造)、EA-1010、EA-1020、EA-5323、EA-5520、EA-CHD、EMA-1020(均為新中村化學工業公司製造)、Epoxy Ester M-600A、Epoxy Ester 40EM、Epoxy Ester 70PA、Epoxy Ester 200PA、Epoxy Ester 80MFA、Epoxy Ester 3002M、Epoxy Ester 3002A、Epoxy Ester 1600A、Epoxy Ester 3000M、Epoxy Ester 3000A、Epoxy Ester 200EA、Epoxy Ester 400EA(均為共榮社化學公司製造)、Denacol Acrylate DA-141、Denacol Acrylate DA-314、Denacol Acrylate DA-911(均為Nagase chemteX公司製造)等。 As the marketers of the aforementioned (meth) acrylic epoxy esters, for example, EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3800, EBECRYL6040, and EBECRYD Rcel63182 (Manufactured by the company), EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (all manufactured by Shin Nakamura Chemical Industry Co., Ltd.), Epoxy Ester M-600A, Epoxy Ester 40EM, Epoxy Ester 70PA, Epoxy Ester 200PA, Epoxy Ester 80MFA, Epoxy Ester 3002M, Epoxy Ester 3002A, Epoxy Ester 1600A, Epoxy Ester 3000M, Epoxy Ester 3000A, Epoxy Ester 200EA, Epoxy Ester 400EA (all manufactured by Kyoeisha Chemical Co., Ltd.), Denacol Acrylate DA-141, Denacol Acrylate DA-314, Denacol Acrylate DA-911 (all manufactured by Nagase chemteX), and the like.

上述(甲基)丙烯酸胺酯例如可藉由使具有羥基之(甲基)丙烯酸衍生物於觸媒量之錫系化合物存在下與異氰酸酯化合物反應而獲得。 The (meth) acrylic acid amine ester can be obtained, for example, by reacting a (meth) acrylic acid derivative having a hydroxyl group with an isocyanate compound in the presence of a catalyst-based tin-based compound.

作為上述異氰酸酯化合物，例如可列舉：異佛酮二異氰酸酯、2,4-甲苯二異氰酸酯、2,6-甲苯二異氰酸酯、六亞甲基二異氰酸酯、三甲基六亞甲基二異氰酸酯、二苯甲烷-4,4'-二異氰酸酯(MDI)、氫化MDI、聚合MDI、1,5-萘二異氰酸酯、降莰烷二異氰酸酯、聯甲苯胺二異氰酸酯、苯二甲基二異氰酸酯(XDI)、氫化XDI、離胺酸二異氰酸酯、三苯甲烷三異氰酸酯、硫代磷酸三(異氰酸基苯基)酯、四甲基苯二甲基二異氰酸酯、1,6,11-十一烷三異氰酸酯等。 Examples of the isocyanate compound include isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and diphenyl Methane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, benzylamine diisocyanate, xylylene diisocyanate (XDI), hydrogenation XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanophenyl) thiophosphate, tetramethylxylylene diisocyanate, 1,6,11-undecane triisocyanate, etc. .

又，作為上述異氰酸酯化合物，亦可使用藉由多元醇與過剩之異氰酸酯化合物之反應而獲得之經鏈延長的異氰酸酯化合物。 As the isocyanate compound, a chain-extended isocyanate compound obtained by reacting a polyol with an excess isocyanate compound can also be used.

作為上述多元醇，例如可列舉乙二醇、丙二醇、甘油、山梨糖醇、三羥甲基丙烷、碳酸酯二醇、聚醚二醇、聚酯二醇、聚己內酯二醇等。 Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, and polycaprolactone diol.

作為上述具有羥基之(甲基)丙烯酸衍生物，例如可列舉：乙二醇、丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、聚乙二醇等二元醇之單(甲基)丙烯酸酯，或三羥甲基乙烷、三羥甲基丙烷、甘油等三元醇之單(甲基)丙烯酸酯或二(甲基)丙烯酸酯，或雙酚A型(甲基)丙烯酸環氧酯等(甲基)丙烯酸環氧酯等。 Examples of the (meth) acrylic acid derivative having a hydroxyl group include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol. Mono (meth) acrylates of diols, or mono (meth) acrylates or di (meth) acrylates of triols such as trimethylolethane, trimethylolpropane, glycerol, or bis Epoxy (meth) acrylate such as phenol A type (meth) acrylate and the like.

作為上述(甲基)丙烯酸胺酯中之市售者，例如可列舉：M-1100、M-1200、M-1210、M-1600(均為東亞合成公司製造)、EBECRYL230、EBECRYL270、EBECRYL4858、EBECRYL8402、EBECRYL8411、EBECRYL8412、EBECRYL8413、EBECRYL8804、EBECRYL8803、EBECRYL8807、EBECRYL9260、EBECRYL1290、EBECRYL5129、EBECRYL4842、EBECRYL210、EBECRYL4827、EBECRYL6700、EBECRYL220、EBECRYL2220、KRM7735、KRM-8295(均為Daicel-Allnes公司製造)、Artresin UN-9000H、Artresin UN-9000A、Artresin UN-7100、Artresin UN-1255、Artresin UN-330、Artresin UN-3320HB、Artresin UN-1200TPK、Artresin SH-500B(均為根上工業公司製造)、U-2HA、U-2PHA、U-3HA、U-4HA、U-6H、U-6LPA、U-6HA、U-10H、U-15HA、U-122A、U-122P、U-108、U-108A、U-324A、U-340A、U-340P、U-1084A、U-2061BA、UA-340P、 UA-4100、UA-4000、UA-4200、UA-4400、UA-5201P、UA-7100、UA-7200、UA-W2A(均為新中村化學工業公司製造)、AI-600、AH-600、AT-600、UA-101I、UA-101T、UA-306H、UA-306I、UA-306T(均為共榮社化學公司製造)等。 Examples of commercially available amine (meth) acrylates include M-1100, M-1200, M-1210, and M-1600 (all manufactured by Toa Synthesis), EBCRYL230, EBCRYL270, EBCRYL4858, and EBCRYL8402 , EBECRYL8411, EBECRYL8412, EBECRYL8413, EBECRYL8804, EBECRYL8803, EBECRYL8807, EBECRYL9260, EBECRYL1290, EBECRYL5129, EBECRYL4842, EBECRYL210, EBECRYL4, EBECRYL6700, ECECRYL22-KRM, EBECRYL220, KEB , Artresin UN-9000A, Artresin UN-7100, Artresin UN-1255, Artresin UN-330, Artresin UN-3320HB, Artresin UN-1200TPK, Artresin SH-500B (all manufactured by Kogen Industrial Co., Ltd.), U-2HA, U- 2PHA, U-3HA, U-4HA, U-6H, U-6LPA, U-6HA, U-10H, U-15HA, U-122A, U-122P, U-108, U-108A, U-324A, U-340A, U-340P, U-1084A, U-2061BA, UA-340P, UA-4100, UA-4000, UA-4200, UA-4400, UA-5201P, UA-7100, UA-7200, UA- W2A (all manufactured by Shin Nakamura Chemical Industry Co., Ltd.), AI-600, AH-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I UA-306T (both manufactured by Kyoeisha Chemical Company) and so on.

又，亦可適當使用上述以外之其他自由基聚合性化合物。 Moreover, other radically polymerizable compounds other than the above may be used appropriately.

作為上述其他自由基聚合性化合物，例如可列舉：N,N-二甲基(甲基)丙烯醯胺、N-(甲基)丙烯醯基嗎福啉、N-羥基乙基(甲基)丙烯醯胺、N,N-二乙基(甲基)丙烯醯胺、N-異丙基(甲基)丙烯醯胺、N,N-二甲胺基丙基(甲基)丙烯醯胺等(甲基)丙烯醯胺化合物；苯乙烯、α-甲基苯乙烯、N-乙烯基-2-吡咯啶酮、N-乙烯基-ε-己內醯胺等乙烯化合物等。 Examples of the other radically polymerizable compound include N, N-dimethyl (meth) acrylamide, N- (meth) acrylfluorenylmorpholine, and N-hydroxyethyl (methyl) Acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, etc. (Meth) acrylamide compounds; ethylene compounds such as styrene, α-methylstyrene, N-vinyl-2-pyrrolidone, N-vinyl-ε-caprolactam, and the like.

就調整硬化性等之觀點而言，上述自由基聚合性化合物較佳為含有單官能自由基聚合性化合物與多官能自由基聚合性化合物。藉由含有上述單官能自由基聚合性化合物與上述多官能自由基聚合性化合物，所獲得之接著劑組成物之硬化性及觸黏性變得更優異。其中，較佳為將作為上述多官能自由基聚合性化合物之(甲基)丙烯酸胺酯與上述單官能自由基聚合性化合物組合使用。又，上述多官能自由基聚合性化合物較佳為2官能或3官能，更佳為2官能。 From the viewpoint of adjusting the hardenability, it is preferable that the radical polymerizable compound contains a monofunctional radical polymerizable compound and a polyfunctional radical polymerizable compound. By containing the said monofunctional radically polymerizable compound and the said polyfunctional radically polymerizable compound, the hardened | cured property and the tackiness of the adhesive composition obtained are more excellent. Among these, it is preferable to use the amine (meth) acrylate which is the said polyfunctional radically polymerizable compound in combination with the said monofunctional radically polymerizable compound. The polyfunctional radically polymerizable compound is preferably difunctional or trifunctional, and more preferably difunctional.

於上述自由基聚合性化合物含有上述單官能自由基聚合性化合物與上述多官能自由基聚合性化合物之情形時，上述多官能自由基聚合性化合物之含量相對於上述單官能自由基聚合性化合物與上述多官能自由基聚合性化合物之合計100重量份，較佳之下限為2重量份，較佳之上 限為45重量份。藉由使上述多官能自由基聚合性化合物之含量為該範圍，所獲得之接著劑組成物之硬化性及觸黏性變得更優異。上述多官能自由基聚合性化合物之含量之更佳下限為5重量份，更佳之上限為35重量份。 When the said radically polymerizable compound contains the said monofunctional radically polymerizable compound and the said polyfunctional radically polymerizable compound, content of the said polyfunctional radically polymerizable compound with respect to the said monofunctional radically polymerizable compound and The total of the above-mentioned polyfunctional radical polymerizable compound is 100 parts by weight, with a preferred lower limit of 2 parts by weight and a preferred upper limit of 45 parts by weight. When the content of the polyfunctional radical polymerizable compound is within this range, the obtained adhesive composition becomes more excellent in hardenability and tackiness. A more preferable lower limit of the content of the polyfunctional radical polymerizable compound is 5 parts by weight, and a more preferable upper limit is 35 parts by weight.

本發明之接著劑組成物100重量份中上述自由基聚合性化合物之含量之較佳下限為10重量份，較佳之上限為80重量份。藉由使上述自由基聚合性化合物之含量為該範圍，所獲得之接著劑組成物之光硬化性與濕氣硬化性之兩者變得更優異。上述自由基聚合性化合物之含量之更佳下限為30重量份，更佳之上限為59重量份。 A preferable lower limit of the content of the radical polymerizable compound in 100 parts by weight of the adhesive composition of the present invention is 10 parts by weight, and a preferable upper limit is 80 parts by weight. When the content of the radically polymerizable compound is within this range, both the photo-curing property and the moisture-curing property of the obtained adhesive composition become more excellent. A more preferable lower limit of the content of the radical polymerizable compound is 30 parts by weight, and a more preferable upper limit is 59 parts by weight.

作為上述光自由基聚合起始劑，例如可列舉：二苯甲酮系化合物、苯乙酮系化合物、醯基氧化膦系化合物、二茂鈦系化合物、肟酯系化合物、安息香醚系化合物、9-氧硫(thioxanthone)等。 Examples of the photoradical polymerization initiator include benzophenone-based compounds, acetophenone-based compounds, fluorenylphosphine oxide-based compounds, titanocene-based compounds, oxime ester-based compounds, benzoin ether-based compounds, and the like. 9-oxysulfur (thioxanthone), etc.

作為上述光自由基聚合起始劑中之市售者，例如可列舉：IRGACURE184、IRGACURE369、IRGACURE379、IRGACURE651、IRGACURE784、IRGACURE819、IRGACURE907、IRGACURE2959、IRGACURE OXE01、Lucirin TPO(均為BASF公司製造)、安息香甲醚、安息香***、安息香異丙醚(均為東京化成工業公司製造)等。 Examples of the commercially available photoradical polymerization initiator include IRGACURE184, IRGACURE369, IRGACURE379, IRGACURE651, IRGACURE784, IRGACURE819, IRGACURE907, IRGACURE2959, IRGACURE OXE01, Lucirin TPO (all manufactured by BASF), and benzoin Ether, benzoin ether, benzoin isopropyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.), and the like.

上述光自由基聚合起始劑之含量相對於上述自由基聚合性化合物100重量份，較佳之下限為0.01重量份，較佳之上限為10重量份。藉由使上述光自由基聚合起始劑之含量為該範圍，所獲得之接著劑組成物之光硬化性及保存穩定性變得更優異。上述光自由基聚合起始劑之含量之更佳下限為0.1重量份，更佳之上限為5重量份。 Content of the said photo-radical polymerization initiator is 100 weight part with respect to the said radically polymerizable compound, Preferably a minimum is 0.01 weight part, and a preferable upper limit is 10 weight part. When the content of the photo-radical polymerization initiator is in this range, the photocuring property and storage stability of the obtained adhesive composition become more excellent. A more preferable lower limit of the content of the photo-radical polymerization initiator is 0.1 part by weight, and a more preferable upper limit is 5 parts by weight.

本發明之接著劑組成物較佳為含有蠟。 The adhesive composition of the present invention preferably contains a wax.

藉由含有上述蠟，本發明之接著劑組成物藉由二次加工時之加熱而發泡劑發泡，並且硬化體軟化，故而二次加工性變得更優異。再者，於本說明書中，所謂上述「蠟」，意指23℃下為固體且藉由加熱而成為液體之有機物。 By containing the above-mentioned wax, the adhesive composition of the present invention foams the foaming agent by heating during the secondary processing, and the hardened body is softened, so that the secondary processability is more excellent. In addition, in this specification, the said "wax" means the organic substance which is solid at 23 degreeC and becomes liquid by heating.

上述蠟之熔點之較佳下限為60℃，較佳之上限為130℃。藉由使上述蠟之熔點為該範圍，所獲得之接著劑組成物兼顧接著性與二次加工性之效果變得更優異。上述蠟之熔點之更佳下限為75℃，更佳之上限為100℃。 The preferable lower limit of the melting point of the wax is 60 ° C, and the preferable upper limit is 130 ° C. By setting the melting point of the wax to be in this range, the obtained adhesive composition has an excellent effect of achieving both adhesiveness and secondary processability. A more preferable lower limit of the melting point of the wax is 75 ° C, and a more preferable upper limit is 100 ° C.

再者，上述蠟之熔點可藉由示差掃描熱量測定而求出。 The melting point of the wax can be determined by differential scanning calorimetry.

作為上述蠟，具體而言，例如可列舉：聚丙烯蠟、聚乙烯蠟、微晶蠟、氧化聚乙烯蠟等烯烴系蠟或烷烴系蠟；或巴西棕櫚蠟、沙索蠟(sasol wax)、褐煤酸酯蠟等脂肪族酯系蠟；或脫酸巴西棕櫚蠟或棕櫚酸、硬脂酸、褐煤酸(montanoic acid)等飽和脂肪族酸系蠟；或蕓苔酸、桐酸、十八碳四烯酸等不飽和脂肪族酸系蠟；或硬脂醇、芳烷基醇、山萮醇、巴西棕櫚醇、蠟醇、蜜蠟醇等飽和醇系蠟或脂肪族醇系蠟；或山梨糖醇等多元醇系蠟；或亞麻油酸醯胺、油酸醯胺、月桂酸醯胺等飽和脂肪醯胺系蠟；或亞甲基雙硬脂酸醯胺、伸乙基雙癸酸醯胺、伸乙基雙月桂酸醯胺、六亞甲基雙硬脂酸醯胺等飽和脂肪酸雙醯胺系蠟；或伸乙基雙油酸醯胺、六亞甲基雙油酸醯胺、N,N'-二油醯基己二酸醯胺、N,N'-二油醯基癸二酸醯胺等不飽和酸醯胺系蠟；或間二甲苯雙硬脂酸醯胺、N,N'-二硬脂基間苯二甲酸醯胺等芳香族雙醯胺系蠟；或使苯乙烯等乙烯系單體接枝聚合於聚烯烴而成之接枝改質蠟；或山萮酸單甘油酯等使脂肪酸與多元醇反應而成之偏酯 蠟；或使植物性油脂氫化而獲得之具有羥基之甲酯蠟；或乙烯成分之含有比例較高之乙烯-乙酸乙烯酯共聚物蠟；或丙烯酸等飽和丙烯酸硬脂酯蠟等長鏈丙烯酸烷基酯蠟；或丙烯酸苄酯蠟等芳香族丙烯酸酯蠟等。其中，較佳為烷烴系蠟、沙索蠟。 Specific examples of the wax include olefin-based waxes and alkane-based waxes such as polypropylene wax, polyethylene wax, microcrystalline wax, and oxidized polyethylene wax; or carnauba wax, sasol wax, Aliphatic ester waxes such as montan ester wax; or deacidified carnauba wax or saturated aliphatic acid waxes such as palmitic acid, stearic acid, montanic acid; or brassic acid, tungstic acid, octadecyl Unsaturated aliphatic acid waxes such as tetraenoic acid; or saturated alcohol waxes or aliphatic alcohol waxes such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauba alcohol, wax alcohol, and beesyl alcohol; or sorbus Polyol waxes such as sugar alcohols; or saturated fatty acid ammonium waxes such as ammonium linoleate, ammonium oleate, and ammonium laurate; or ammonium distearate and ethyl decanoate Amines, methylamine dilaurate, methylamine hexamethylenebisstearate, and other saturated fatty acid diamine waxes; or methylamine dioleate, methylamine hexamethylenebisoleate, Unsaturated acid ammonium waxes such as N, N'-diglyl adipate, N, N'-diglyl adipate, or m-xylylenestearate, N , N '-Distearyl isophthalamide and other aromatic bis-amine base waxes; or graft-modified waxes obtained by graft-polymerizing vinyl monomers such as styrene onto polyolefins; or behenic acid monomers Glycerides, such as partial ester waxes made by reacting fatty acids with polyols; or methyl ester waxes having hydroxyl groups obtained by hydrogenating vegetable fats or oils; or ethylene-vinyl acetate copolymer waxes with a high proportion of ethylene; Or long-chain alkyl acrylate waxes such as saturated acrylic stearate waxes such as acrylic acid; or aromatic acrylate waxes such as benzyl acrylate waxes. Among these, alkane-based wax and sasol wax are preferred.

作為上述蠟中之市售者，例如可列舉：HS CRYSTA-6100、HS CRYSTA-7100(均為豐國製油公司製造)、H1、H1N6、C105、H105、C80、spray30、spray105(均為Sasol公司製造)、ParaffinWax-155、ParaffinWax-150、ParaffinWax-145、ParaffinWax-140、HNP-3、HNP-9、HNP-51、SP-0165、Hi-Mic-2095、Hi-Mic-1090、Hi-Mic-1080、Hi-Mic-1070、NPS-6010、FT115、SX105、FNP-0090(均為日本精蠟公司製造)等。 As the marketers of the aforementioned waxes, for example, HS CRYSTA-6100, HS CRYSTA-7100 (all manufactured by Fengguo Oil Co., Ltd.), H1, H1N6, C105, H105, C80, spray30, spray105 (both Sasol) (Manufactured), ParaffinWax-155, ParaffinWax-150, ParaffinWax-145, ParaffinWax-140, HNP-3, HNP-9, HNP-51, SP-0165, Hi-Mic-2095, Hi-Mic-1090, Hi-Mic -1080, Hi-Mic-1070, NPS-6010, FT115, SX105, FNP-0090 (all manufactured by Nippon Seiki Corporation), etc.

本發明之接著劑組成物100重量份中上述蠟之含量之較佳下限為1重量份，較佳之上限為40重量份。藉由使上述蠟之含量為該範圍，所獲得之接著劑組成物兼顧接著性與二次加工性之效果變得更優異。上述蠟之含量之更佳下限為5重量份，更佳之上限為20重量份。 A preferable lower limit of the content of the wax in 100 parts by weight of the adhesive composition of the present invention is 1 part by weight, and a preferable upper limit is 40 parts by weight. When the content of the wax is within this range, the obtained adhesive composition has more excellent effects of achieving both adhesiveness and secondary processability. A more preferable lower limit of the content of the wax is 5 parts by weight, and a more preferable upper limit is 20 parts by weight.

本發明之接著劑組成物較佳為含有促進上述濕氣硬化型樹脂之濕氣硬化反應之觸媒。藉由含有上述觸媒，本發明之接著劑組成物之濕氣硬化性變得更優異。 The adhesive composition of the present invention preferably contains a catalyst that promotes the moisture curing reaction of the moisture curing resin. By containing the said catalyst, the moisture hardening property of the adhesive composition of this invention becomes more excellent.

作為上述觸媒，具體而言，例如可使用：二月桂酸二正丁基錫、二乙酸二正丁基錫、辛酸錫等錫化合物；三乙胺、U-CAT651M(SAN-APRO公司製造)、U-CAT660M(SAN-APRO公司製造)、U-CAT2041(SAN-APRO公司製造)、1,4-二氮雜雙環[2.2.2]辛烷、2,6,7-三甲基- 1,4-二氮雜雙環[2.2.2]辛烷等胺化合物；辛酸鋅、環烷酸鋅(zinc naphthenate)等鋅化合物；乙醯丙酮酸鋯、環烷酸銅、環烷酸鈷等。 Specific examples of the catalyst include tin compounds such as di-n-butyltin dilaurate, di-n-butyltin diacetate, and tin octoate; triethylamine, U-CAT651M (manufactured by SAN-APRO), and U-CAT660M. (Manufactured by SAN-APRO), U-CAT2041 (manufactured by SAN-APRO), 1,4-diazabicyclo [2.2.2] octane, 2,6,7-trimethyl-1,4-di Azabicyclo [2.2.2] amine compounds such as octane; zinc compounds such as zinc octoate and zinc naphthenate; zirconium acetamate pyruvate, copper naphthenate, cobalt naphthenate and the like.

本發明之接著劑組成物100重量份中上述觸媒之含量之較佳下限為0.01重量份，較佳之上限為5重量份。藉由使上述觸媒之含量為該範圍，不會使所獲得之接著劑組成物之保存穩定性等變差，而促進濕氣硬化反應之效果變得更優異。上述觸媒之含量之更佳之下限為0.25重量份，更佳之上限為3重量份。 A preferable lower limit of the content of the catalyst in 100 parts by weight of the adhesive composition of the present invention is 0.01 part by weight, and a preferable upper limit is 5 parts by weight. When the content of the catalyst is within this range, the storage stability and the like of the obtained adhesive composition are not deteriorated, and the effect of promoting the moisture curing reaction becomes more excellent. A more preferable lower limit of the content of the catalyst is 0.25 parts by weight, and a more preferable upper limit is 3 parts by weight.

本發明之接著劑組成物較佳為含有填充劑。 The adhesive composition of the present invention preferably contains a filler.

藉由含有上述填充劑，本發明之接著劑組成物成為具有適當之搖變性者，而可充分地保持塗佈後之形狀。 By including the above-mentioned filler, the adhesive composition of the present invention has a suitable shake property and can sufficiently maintain the shape after coating.

上述填充劑之一次粒徑之較佳下限為1nm，較佳之上限為50nm。藉由使上述填充劑之一次粒徑為該範圍，所獲得之接著劑組成物之塗佈性及塗佈後之形狀保持性變得更優異。上述填充劑之一次粒徑之更佳之下限為5nm，更佳之上限為30nm，進而較佳之下限為10nm，進而較佳之上限為20nm。 The preferred lower limit of the primary particle diameter of the filler is 1 nm, and the preferred upper limit is 50 nm. By setting the primary particle diameter of the filler to be in this range, the obtained adhesive composition is more excellent in coatability and shape retention after coating. The lower limit of the primary particle size of the filler is more preferably 5 nm, the more preferable upper limit is 30 nm, the more preferable lower limit is 10 nm, and the more preferable upper limit is 20 nm.

再者，上述填充劑之一次粒徑可使用NICOMP 380ZLS(PARTICLE SIZING SYSTEMS公司製造)，使上述填充劑分散於溶劑(水、有機溶劑等)中進行測定。 The primary particle diameter of the filler can be measured using NICOMP 380ZLS (manufactured by PARTICLE SIZING SYSTEMS), and dispersing the filler in a solvent (water, organic solvent, etc.).

又，上述填充劑存在以二次粒子(多個一次粒子聚集而成者)之形式存在於本發明之接著劑組成物中之情形，此種二次粒子之粒徑之較佳下限為5nm，較佳之上限為500nm，更佳之下限為10nm，更佳之上限為100nm。上述填充劑之二次粒子之粒徑可藉由使用穿透式電子顯微鏡(TEM) 對本發明之接著劑組成物或其硬化物進行觀察而測定。 In addition, the filler mentioned above may exist in the form of secondary particles (composed of a plurality of primary particles) in the adhesive composition of the present invention, and a preferable lower limit of the particle size of such secondary particles is 5 nm. A preferred upper limit is 500 nm, a more preferred lower limit is 10 nm, and a more preferred upper limit is 100 nm. The particle diameter of the secondary particles of the filler can be measured by observing the adhesive composition of the present invention or a cured product thereof using a transmission electron microscope (TEM).

作為上述填充劑，較佳為無機填充劑，例如可列舉二氧化矽、滑石、氧化鈦、氧化鋅、碳酸鈣等。其中，就所獲得之接著劑組成物之紫外線穿透性變得優異之方面而言，較佳為二氧化矽。該等填充劑可單獨使用，亦可將2種以上組合使用。 The filler is preferably an inorganic filler, and examples thereof include silicon dioxide, talc, titanium oxide, zinc oxide, and calcium carbonate. Among them, silicon dioxide is preferred in terms of the ultraviolet transmittance of the obtained adhesive composition being excellent. These fillers may be used alone or in combination of two or more.

上述填充劑較佳為進行了疏水性表面處理。藉由上述疏水性表面處理，所獲得之接著劑組成物之塗佈後之形狀保持性變得更優異。 The filler is preferably subjected to a hydrophobic surface treatment. By the above-mentioned hydrophobic surface treatment, the shape retention of the obtained adhesive composition after coating becomes more excellent.

作為上述疏水性表面處理，可列舉矽基化處理、烷基化處理、環氧化處理等。其中，就提高形狀保持性之效果優異之方面而言，較佳為矽基化處理，更佳為三甲基矽基化處理。 Examples of the hydrophobic surface treatment include silylation treatment, alkylation treatment, and epoxidation treatment. Among them, in terms of the effect of improving the shape retention property, a silicidation treatment is preferred, and a trimethylsilication treatment is more preferred.

作為對上述填充劑進行疏水性表面處理之方法，例如可列舉使用矽烷偶合劑等表面處理劑對填充劑之表面進行處理之方法等。 Examples of the method for the hydrophobic surface treatment of the filler include a method of treating the surface of the filler with a surface treatment agent such as a silane coupling agent.

具體而言，例如上述三甲基矽基化處理二氧化矽可藉由如下方法等製作：利用溶膠凝膠法等方法合成二氧化矽，並於使二氧化矽流動之狀態下對六甲基二矽氮烷進行噴霧之方法，或向醇、甲苯等有機溶劑中添加二氧化矽、六甲基二矽氮烷及水後，利用蒸發器使水與有機溶劑蒸發乾燥之方法。 Specifically, for example, the above-mentioned trimethyl silylated silicon dioxide can be produced by a method such as: synthesizing silicon dioxide by a method such as a sol-gel method, and hexamethyl The method of spraying disilazane, or adding silica, hexamethyldisilazane, and water to organic solvents such as alcohol and toluene, and then evaporating and drying the water and the organic solvent by using an evaporator.

本發明之接著劑組成物100重量份中上述填充劑之含量之較佳下限為1重量份，較佳之上限為20重量份。藉由使上述填充劑之含量為該範圍，所獲得之接著劑組成物之塗佈性及塗佈後之形狀保持性變得更優異。上述填充劑之含量之更佳下限為2重量份，更佳之上限為15重量份，進而較佳之下限為3重量份，進而較佳之上限為10重量份，尤佳之下限為 4重量份。 A preferable lower limit of the content of the filler in 100 parts by weight of the adhesive composition of the present invention is 1 part by weight, and a preferable upper limit is 20 parts by weight. When the content of the filler is in this range, the obtained adhesive composition is more excellent in coatability and shape retention after coating. The more preferable lower limit of the content of the filler is 2 parts by weight, the more preferable upper limit is 15 parts by weight, the more preferable lower limit is 3 parts by weight, the more preferable upper limit is 10 parts by weight, and the more preferable lower limit is 4 parts by weight.

本發明之接著劑組成物亦可含有遮光劑。 The adhesive composition of the present invention may contain a light-shielding agent.

藉由含有上述遮光劑，本發明之接著劑組成物之遮光性變得優異，例如於用於顯示元件之情形時，可防止漏光。又，使用摻合有上述遮光劑之本發明之接著劑組成物而製造之顯示元件由於接著劑組成物具有充分之遮光性，故而不存在漏光而具有較高之對比度，從而成為具有優異之圖像顯示品質者。 By containing the said light-shielding agent, the light-shielding property of the adhesive composition of this invention becomes excellent, and when it uses for a display element, for example, it can prevent light leakage. In addition, a display device manufactured by using the adhesive composition of the present invention in which the above-mentioned light-shielding agent is blended, has sufficient light-shielding properties, and therefore has a high contrast without light leakage, thereby providing an excellent image. Like display quality.

再者，於本說明書中，上述「遮光劑」意指具有使可見光區域之光難以穿透之能力之材料。 In addition, in the present specification, the "shielding agent" means a material having the ability to make it difficult to penetrate light in the visible light region.

作為上述遮光劑，例如可列舉氧化鐵、鈦黑、苯胺黑、花青黑(cyanine black)、富勒烯、碳黑、樹脂被覆型碳黑等。又，上述遮光劑亦可並非為呈黑色者，只要為具有使可見光區域之光難以穿透之能力之材料，則二氧化矽、滑石、氧化鈦等作為填充劑而列舉之材料等亦包含於上述遮光劑中。其中，較佳為鈦黑。 Examples of the light-shielding agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. In addition, the above-mentioned light-shielding agent may not be black. As long as it is a material having the ability to make it difficult to penetrate light in the visible light region, materials such as silicon dioxide, talc, and titanium oxide as fillers are also included in In the above sunscreen. Among these, titanium black is preferred.

上述鈦黑係與對波長300~800nm之光之平均透光率相比，對紫外線區域附近、尤其是波長370~450nm之光之透光率增高之物質。即，上述鈦黑係具有如下性質之遮光劑，即，具有藉由充分地遮蔽可見光區域之波長之光而對本發明之接著劑組成物賦予遮光性，另一方面，使紫外線區域附近之波長之光穿透之性質。因此，藉由使用可利用上述鈦黑之透光率增高之波長(370~450nm)之光而使反應起始者作為光自由基聚合起始劑，可使本發明之接著劑組成物之光硬化性進一步增大。又，另一方面，作為本發明之接著劑組成物中所含有之遮光劑，較佳為絕緣性較 高之物質，鈦黑亦適合作為絕緣性較高之遮光劑。 Compared with the average light transmittance of the above-mentioned titanium black to light having a wavelength of 300 to 800 nm, the material having a higher light transmittance to the vicinity of the ultraviolet region, particularly to light having a wavelength of 370 to 450 nm. That is, the above-mentioned titanium black is a light-shielding agent having a property of providing light-shielding properties to the adhesive composition of the present invention by sufficiently shielding light of a wavelength in a visible light region, and a light-shielding agent having a wavelength near a ultraviolet region. The nature of light transmission. Therefore, by using light having a wavelength (370 to 450 nm) in which the light transmittance of the above-mentioned titanium black is increased, the initiator of the reaction can be used as a photoradical polymerization initiator, and the light of the adhesive composition of the present invention can be made light. Hardenability is further increased. On the other hand, as the light-shielding agent contained in the adhesive composition of the present invention, a substance having high insulation properties is preferred, and titanium black is also suitable as a light-shielding agent having high insulation properties.

上述鈦黑之光學濃度(OD值)較佳為3以上，更佳為4以上。又，上述鈦黑之黑色度(L值)較佳為9以上，更佳為11以上。上述鈦黑之遮光性越高越好，上述鈦黑之OD值並未特別存在較佳之上限，通常成為5以下。 The optical density (OD value) of the titanium black is preferably 3 or more, and more preferably 4 or more. The blackness (L value) of the titanium black is preferably 9 or more, and more preferably 11 or more. The higher the light-shielding property of the titanium black, the better. The OD value of the titanium black does not particularly have a preferable upper limit, and is usually 5 or less.

上述鈦黑即便未經表面處理，亦發揮充分之效果，但亦可使用表面經偶合劑等有機成分處理者、由氧化矽、氧化鈦、氧化鍺、氧化鋁、氧化鋯、氧化鎂等無機成分被覆者等經表面處理之鈦黑。其中，就可進一步提高絕緣性之方面而言，較佳為經有機成分處理者。 The above-mentioned titanium black exhibits sufficient effects even without surface treatment, but it can also be treated with organic components such as coupling agents on the surface, and inorganic components such as silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconia, and magnesium oxide. Surface-treated titanium black. Among these, in terms of the ability to further improve the insulation properties, those treated with an organic component are preferred.

作為上述鈦黑中之市售者，例如可列舉12S、13M、13M-C、13R-N(均為Mitsubishi Materials公司製造)、Tilack D(Ako Kasei公司製造)等。 As a marketer of the said titanium black, 12S, 13M, 13M-C, 13R-N (all manufactured by Mitsubishi Materials), Tilack D (made by Ako Kasei), etc. are mentioned, for example.

上述鈦黑之比表面積之較佳下限為5m2/g，較佳之上限為40m2/g，更佳之下限為10m2/g，更佳之上限為25m2/g。又，於與樹脂混合之情形(摻合有70%)時，上述鈦黑之薄片電阻之較佳下限為109Ω/□，更佳之下限為1011Ω/□。 The preferred lower limit of the specific surface area of the titanium black is 5 m 2 / g, the preferred upper limit is 40 m 2 / g, the more preferred lower limit is 10 m 2 / g, and the more preferred upper limit is 25 m 2 / g. When mixed with resin (70% blended), the preferable lower limit of the sheet resistance of the titanium black is 10 9 Ω / □, and the more preferable lower limit is 10 11 Ω / □.

於本發明之接著劑組成物中，上述遮光劑之一次粒徑為顯示元件之基板間之距離以下等，可根據用途適當選擇，較佳之下限為30nm，較佳之上限為500nm。藉由使上述遮光劑之一次粒徑為該範圍，黏度及搖變性不會大幅增大，所獲得之接著劑組成物向基板之塗佈性及作業性變得更優異。上述遮光劑之一次粒徑之更佳之下限為50nm，更佳之上限為200nm。 In the adhesive composition of the present invention, the primary particle diameter of the light-shielding agent is equal to or less than the distance between the substrates of the display element, etc., and can be appropriately selected according to the application, with a preferred lower limit of 30 nm and a preferred upper limit of 500 nm. When the primary particle diameter of the light-shielding agent is in this range, viscosity and shake properties do not increase significantly, and the obtained adhesive composition has better applicability and workability to a substrate. The lower limit of the primary particle size of the above-mentioned sunscreen is more preferably 50 nm, and the more preferable upper limit is 200 nm.

再者，上述遮光劑之一次粒徑可以與上述填充劑之一次粒徑相同之方式進行測定。 The primary particle diameter of the light-shielding agent can be measured in the same manner as the primary particle diameter of the filler.

本發明之接著劑組成物100重量份中上述遮光劑之含量之較佳下限為0.05重量份，較佳之上限為10重量份。藉由使上述遮光劑之含量為該範圍，所獲得之接著劑組成物於維持優異之描繪性、對基板等之接著性及硬化後之強度之情況下遮光性變得更優異。上述遮光劑之含量之更佳下限為0.1重量份，更佳之上限為2重量份，進而較佳之上限為1重量份。 A preferable lower limit of the content of the light-shielding agent in 100 parts by weight of the adhesive composition of the present invention is 0.05 parts by weight, and a preferable upper limit is 10 parts by weight. When the content of the light-shielding agent is within this range, the obtained adhesive composition is more excellent in light-shielding properties while maintaining excellent drawability, adhesion to a substrate, and the like, and strength after curing. A more preferable lower limit of the content of the light-shielding agent is 0.1 part by weight, a more preferable upper limit is 2 parts by weight, and a more preferable upper limit is 1 part by weight.

本發明之接著劑組成物亦可視需要進而含有著色劑、離子液體、溶劑、含金屬之粒子、反應性稀釋劑等添加劑。 The adhesive composition of the present invention may further contain additives such as a colorant, an ionic liquid, a solvent, metal-containing particles, and a reactive diluent, if necessary.

作為製造本發明之接著劑組成物之方法，例如可列舉使用勻相分散機、均勻混合機、萬能混合機、行星式混合機、捏合機、三輥研磨機等混合機，將濕氣硬化型樹脂、發泡劑、視需要添加之自由基聚合性化合物及光自由基聚合起始劑或添加劑進行混合之方法等。 As a method for producing the adhesive composition of the present invention, for example, a moisture-hardening type is used by using a mixer such as a homogeneous disperser, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three-roll mill. A method of mixing a resin, a foaming agent, a radically polymerizable compound and a photoradical polymerization initiator or an additive if necessary.

本發明之接著劑組成物所含有之水分量較佳為100ppm以下。藉由使上述水分量為100ppm以下，可抑制保存中之上述濕氣硬化型樹脂與水分之反應，而使接著劑組成物之保存穩定性變得更優異。上述水分量更佳為80ppm以下。 The moisture content contained in the adhesive composition of the present invention is preferably 100 ppm or less. When the moisture content is 100 ppm or less, the reaction between the moisture-curable resin and moisture during storage can be suppressed, and the storage stability of the adhesive composition can be made more excellent. The water content is more preferably 80 ppm or less.

再者，上述水分量可藉由卡費雪水分測定裝置進行測定。 The moisture content can be measured by a Car-Fisher moisture measuring device.

本發明之接著劑組成物中之使用錐板型黏度計於25℃、1rpm之條件下所測得之黏度之較佳下限為50Pa‧s，較佳之上限為1000Pa‧s。藉由使上述黏度為該範圍，將接著劑組成物塗佈於基板等被接著體時之作業性變得更優異。上述黏度之更佳下限為80Pa‧s，更佳之上限為500 Pa‧s，進而較佳之上限為400Pa‧s。 In the adhesive composition of the present invention, a preferable lower limit of the viscosity measured at 25 ° C and 1 rpm using a cone-plate viscosity meter is 50 Pa · s, and a preferable upper limit is 1000 Pa · s. By making the said viscosity into this range, workability | operativity at the time of apply | coating an adhesive composition to a to-be-adhered body, such as a board | substrate, becomes more excellent. The better lower limit of the above viscosity is 80Pa‧s, the better upper limit is 500 Pa‧s, and the more preferable upper limit is 400Pa‧s.

再者，於本發明之接著劑組成物之黏度過高之情形時，於塗佈時，可藉由於發泡劑不會發泡之程度之低溫下進行加熱而提高塗佈性。 Furthermore, when the viscosity of the adhesive composition of the present invention is too high, the coating property can be improved by heating at a low temperature to the extent that the foaming agent does not foam during coating.

本發明之接著劑組成物之搖變指數之較佳下限為1.3，較佳之上限為5.0。藉由使上述搖變指數為該範圍，將接著劑組成物塗佈於基板等被接著體時之作業性變得更優異。上述搖變指數之更佳之下限為1.5，更佳之上限為4.0。 The preferable lower limit of the shake index of the adhesive composition of the present invention is 1.3, and the preferable upper limit is 5.0. By making the said shake index into this range, workability | operativity at the time of apply | coating an adhesive composition to a to-be-adhered body, such as a board | substrate, becomes more excellent. The better lower limit of the above shake index is 1.5, and the better upper limit is 4.0.

再者，於本說明書中，所謂上述搖變指數，意指使用錐板型黏度計於25℃、1rpm之條件下所測得之黏度除以使用錐板型黏度計於25℃、10rpm之條件下所測得之黏度所得之值。 Furthermore, in the present specification, the above-mentioned shake index means the viscosity measured at 25 ° C and 1 rpm using a cone-plate viscosity meter divided by 25 ° C and 10 rpm using a cone-plate viscosity meter. The value obtained from the measured viscosity.

本發明之接著劑組成物硬化後之厚度為1mm之硬化物其光學濃度(OD值)較佳為1以上。藉由使上述OD值為1以上而遮光性優異，於用於顯示元件之情形時可防止漏光而獲得較高之對比度。上述OD值更佳為1.5以上。 The hardened product having a thickness of 1 mm after curing of the adhesive composition of the present invention preferably has an optical density (OD value) of 1 or more. When the OD value is 1 or more and the light-shielding property is excellent, light leakage can be prevented and a high contrast can be obtained when used in a display element. The above OD value is more preferably 1.5 or more.

上述OD值越高越好，但若為了增高上述OD值而大量摻合遮光劑，則發生因增黏而導致的作業性降低等，因此為了取得與遮光劑之摻合量之平衡性，上述硬化體之OD值之較佳上限為4。 The higher the OD value, the better. However, if a large amount of a light-shielding agent is blended in order to increase the OD value, a decrease in workability due to thickening occurs. Therefore, in order to obtain a balance with the amount of the light-shielding agent, the above A preferable upper limit of the OD value of the hardened body is 4.

再者，上述接著劑組成物之硬化後之OD值可使用光學濃度計進行測定。 The OD value of the adhesive composition after curing can be measured using an optical densitometer.

本發明之接著劑組成物於硬化後，可藉由二次加工時之加熱而容易地剝離。 After hardening, the adhesive composition of the present invention can be easily peeled off by heating during secondary processing.

上述二次加工時之加熱溫度之較佳下限為60℃，較佳之上限為120℃。 藉由使上述加熱溫度為該範圍，不使電子零件等損傷便可將其容易地剝離。上述二次加工時之加熱溫度之更佳下限為75℃，更佳之上限為110℃。 A preferable lower limit of the heating temperature during the above-mentioned secondary processing is 60 ° C, and a preferable upper limit is 120 ° C. By making the said heating temperature into this range, an electronic component etc. can be peeled easily without being damaged. A more preferable lower limit of the heating temperature during the above-mentioned secondary processing is 75 ° C, and a more preferable upper limit is 110 ° C.

本發明之接著劑組成物之硬化體亦為本發明之一。硬化前之接著劑組成物中含有濕氣硬化型胺酯樹脂，因此本發明之硬化體具有脲鍵及/或胺酯鍵。本發明之硬化體中所含之成分係本發明之接著劑組成物中所含有之成分及該成分於本發明之接著劑組成物之硬化時藉由化學反應等變化後之成分。 The hardened body of the adhesive composition of the present invention is also one of the present invention. Since the adhesive composition before curing contains a moisture-curable amine ester resin, the cured body of the present invention has a urea bond and / or an amine ester bond. The component contained in the hardened body of the present invention is a component contained in the adhesive composition of the present invention and a component that is changed by a chemical reaction or the like when the adhesive composition of the present invention is hardened.

具有本發明之接著劑組成物之硬化體之電子零件亦為本發明之一。本發明之接著劑組成物尤其是於需要小型化或窄邊緣設計之電子零件中發揮上述優異之效果。 An electronic component having a hardened body of the adhesive composition of the present invention is also one aspect of the present invention. The adhesive composition of the present invention exhibits the above-mentioned excellent effects especially for electronic parts that require miniaturization or narrow-edge design.

於本發明之電子零件中，本發明之接著劑組成物主要用於被接著體之接著。 In the electronic component of the present invention, the adhesive composition of the present invention is mainly used for the adherend.

作為可使用本發明之接著劑組成物進行接著之被接著體，可列舉金屬、玻璃、塑膠等各種被接著體。 Examples of the adherend that can be adhered using the adhesive composition of the present invention include various adherends such as metal, glass, and plastic.

作為上述被接著體之形狀，例如可列舉膜狀、片狀、板狀、平板狀、盤狀、桿(棒狀體)狀、箱體狀、殼體狀等。 Examples of the shape of the adherend include a film shape, a sheet shape, a plate shape, a flat plate shape, a disk shape, a rod (rod-shaped body) shape, a box shape, and a shell shape.

作為上述金屬，例如可列舉鐵鋼、不鏽鋼、鋁、銅、鎳、鉻或其合金等。 Examples of the metal include iron steel, stainless steel, aluminum, copper, nickel, chromium, and alloys thereof.

作為上述玻璃，例如可列舉鹼玻璃、無鹼玻璃、石英玻璃等。 Examples of the glass include alkali glass, alkali-free glass, and quartz glass.

作為上述塑膠，例如可列舉：高密度聚乙烯、超高分子量聚乙烯、同排聚丙烯、對排聚丙烯、乙烯丙烯共聚物樹脂等聚烯烴系樹脂；尼龍6(N6)、尼龍66(N66)、尼龍46(N46)、尼龍11(N11)、尼龍12(N12)、尼龍 610(N610)、尼龍612(N612)、尼龍6/66共聚物(N6/66)、尼龍6/66/610共聚物(N6/66/610)、尼龍MXD6(MXD6)、尼龍6T、尼龍6/6T共聚物、尼龍66/PP共聚物、尼龍66/PPS共聚物等聚醯胺系樹脂；聚對苯二甲酸丁二酯(PBT)、聚對苯二甲酸乙二酯(PET)、聚間苯二甲酸乙二酯(PEI)、PET/PEI共聚物、聚芳酯(PAR)、聚萘二甲酸丁二酯(PBN)、液晶聚酯、聚氧伸烷基二醯亞胺二酸/聚對苯二甲酸丁二酯共聚物等芳香族聚酯系樹脂；聚丙烯腈(PAN)、聚甲基丙烯腈、丙烯腈/苯乙烯共聚物(AS)、甲基丙烯腈/苯乙烯共聚物、甲基丙烯腈/苯乙烯/丁二烯共聚物等聚腈系樹脂；聚碳酸酯、聚甲基丙烯酸甲酯(PMMA)、聚甲基丙烯酸乙酯等聚甲基丙烯酸酯系樹脂；乙烯/乙酸乙烯酯共聚物(EVA)、聚乙烯醇(PVA)、乙烯醇/乙烯共聚物(EVOH)、聚偏二氯乙烯(PVDC)、聚氯乙烯(PVC)、氯乙烯/偏二氯乙烯共聚物、偏二氯乙烯/丙烯酸甲酯共聚物等聚乙烯系樹脂等。 Examples of the plastic include polyolefin resins such as high-density polyethylene, ultra-high molecular weight polyethylene, in-row polypropylene, opposite-row polypropylene, and ethylene-propylene copolymer resin; nylon 6 (N6), and nylon 66 (N66 ), Nylon 46 (N46), nylon 11 (N11), nylon 12 (N12), nylon 610 (N610), nylon 612 (N612), nylon 6/66 copolymer (N6 / 66), nylon 6/66/610 Polyamide resins such as copolymers (N6 / 66/610), nylon MXD6 (MXD6), nylon 6T, nylon 6 / 6T copolymer, nylon 66 / PP copolymer, nylon 66 / PPS copolymer; polyparaphenylene terephthalate Butyl formate (PBT), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), PET / PEI copolymer, polyarylate (PAR), polybutylene naphthalate Aromatic polyester resins such as diester (PBN), liquid crystal polyester, polyoxyalkylene diimide diacid / polybutylene terephthalate copolymer; polyacrylonitrile (PAN), polymethyl Polyacrylonitrile resins such as acrylonitrile, acrylonitrile / styrene copolymer (AS), methacrylonitrile / styrene copolymer, methacrylonitrile / styrene / butadiene copolymer; polycarbonate, polymethyl Methyl acrylate (PMMA), polymethyl Polymethacrylate resins such as ethyl enoate; ethylene / vinyl acetate copolymer (EVA), polyvinyl alcohol (PVA), vinyl alcohol / ethylene copolymer (EVOH), polyvinylidene chloride (PVDC), Polyethylene resins such as polyvinyl chloride (PVC), vinyl chloride / vinylidene chloride copolymer, vinylidene chloride / methyl acrylate copolymer, and the like.

又，作為上述被接著體，亦可列舉表面具有金屬鍍層之複合材料，作為該複合材料之鍍層之基底材，例如可列舉上述金屬、玻璃、塑膠等。 Moreover, as the said adherend, the composite material which has a metal plating layer on the surface can be mentioned, and as a base material of the plating layer of this composite material, the said metal, glass, plastic, etc. are mentioned, for example.

進而，作為上述被接著體，亦可列舉藉由對金屬表面進行鈍態化處理而形成鈍態皮膜之材料，作為該鈍態化處理，例如可列舉加熱處理、陽極氧化處理等。尤其是於國際鋁合金名為編號6000之材質之鋁合金等之情形時，藉由進行硫酸耐酸鋁處理或磷酸耐酸鋁處理作為上述鈍態化處理，可提高接著性。 Further, examples of the adherend include a material that forms a passive film by subjecting a metal surface to a passive treatment. Examples of the passive treatment include a heat treatment and an anodizing treatment. In particular, in the case of an aluminum alloy such as the material number 6000 of the international aluminum alloy, the sulfuric acid-resistant aluminum phosphate treatment or the phosphoric acid-resistant aluminum oxide treatment is used as the passivation treatment to improve adhesion.

又，具有第1基板、第2基板及本發明之接著劑組成物之硬 化體且上述第1基板之至少一部分係經由上述接著劑組成物之硬化體與上述第2基板之至少一部分接合之組裝零件亦為本發明之一。 In addition, the first substrate, the second substrate, and the hardened body of the adhesive composition of the present invention, and at least a part of the first substrate is assembled by joining the hardened body of the adhesive composition to at least a part of the second substrate. Parts are also part of the invention.

上述第1基板及上述第2基板分別較佳為具有至少1個電子零件。 Each of the first substrate and the second substrate preferably includes at least one electronic component.

根據本發明，可提供一種接著性優異且低溫下之二次加工容易之接著劑組成物。又，根據本發明，可提供一種該接著劑組成物之硬化體以及具有該接著劑組成物之硬化體之電子零件及組裝零件。 According to the present invention, it is possible to provide an adhesive composition having excellent adhesiveness and easy secondary processing at a low temperature. According to the present invention, it is possible to provide a hardened body of the adhesive composition, and an electronic component and an assembled component having the hardened body of the adhesive composition.

1‧‧‧被接著體 1‧‧‧ was followed

2‧‧‧接著劑組成物 2‧‧‧ Adhesive composition

3‧‧‧接著層之厚度 3‧‧‧ thickness of the adhesive layer

4‧‧‧單位面積 4‧‧‧Unit area

5‧‧‧發泡劑 5‧‧‧Foaming agent

6‧‧‧鋁基板 6‧‧‧ aluminum substrate

7‧‧‧接著劑組成物 7‧‧‧ Adhesive composition

8‧‧‧玻璃板 8‧‧‧ glass plate

圖1係表示(a)接著層之厚度較小之情形時及(b)較大之情形時之利用本發明之接著劑組成物之被接著體之接著狀態之示意圖。 FIG. 1 is a schematic diagram showing the state of adhesion of the adherend using the adhesive composition of the present invention when (a) the thickness of the adhesive layer is small and (b) when the thickness is large.

圖2(a)係表示自上方觀察接著性評價用樣本之情形時之示意圖，(b)係表示自側面觀察接著性評價用樣本之情形時之示意圖。 FIG. 2 (a) is a schematic diagram when the sample for adhesion evaluation is viewed from above, and (b) is a schematic diagram when the sample for adhesion evaluation is viewed from the side.

以下，揭示實施例對本發明進而詳細地進行說明，但本發明並不僅限定於該等實施例。 Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

(合成例1(濕氣硬化型胺酯樹脂之製作)) (Synthesis example 1 (production of moisture-curable urethane resin))

將作為多元醇化合物之100重量份之聚四亞甲基醚二醇(三菱化學公司製造，「PTMG-2000」)與0.01重量份之二月桂酸二丁基錫加入至容量為500mL之可分離式燒瓶中，於真空下(20mmHg以下)、100℃下攪拌30分鐘進行混合。其後設為常壓，添加作為多異氰酸酯化合物之二苯甲烷 二異氰酸酯(日曹商事公司製造，「Pure MDI」)26.5重量份，於80℃攪拌3小時使其反應，獲得濕氣硬化型胺酯樹脂(重量平均分子量2700)。 100 parts by weight of polytetramethylene ether glycol (manufactured by Mitsubishi Chemical Corporation, "PTMG-2000") as a polyol compound and 0.01 parts by weight of dibutyltin dilaurate were added to a separable flask having a capacity of 500 mL. The mixture was stirred under vacuum (20 mmHg or less) at 100 ° C for 30 minutes. Thereafter, it was set to normal pressure, and 26.5 parts by weight of diphenylmethane diisocyanate (manufactured by Nissho Corporation, "Pure MDI") was added as a polyisocyanate compound, and the mixture was stirred at 80 ° C for 3 hours to react to obtain a moisture-curable amine. Ester resin (weight average molecular weight 2700).

(實施例1~7、比較例1~3) (Examples 1 to 7, Comparative Examples 1 to 3)

依據表1所記載之摻合比，利用行星式攪拌裝置(Thinky公司製造，「去泡攪拌太郎」)將各材料攪拌後，利用陶瓷三輥研磨機均勻地混合而獲得實施例1~7、比較例1~3之接著劑組成物。 According to the blending ratios described in Table 1, each material was stirred with a planetary stirring device ("Defoaming Stirred Taro" manufactured by Thinky), and then uniformly mixed with a ceramic three-roll mill to obtain Examples 1-7, The adhesive composition of Comparative Examples 1 to 3.

<評價> <Evaluation>

針對實施例及比較例中所獲得之各接著劑組成物進行以下之評價。將結果示於表1。再者，針對比較例3中所獲得之接著劑組成物，由於樹脂未硬化而未能製作各評價之樣品，故而未進行以下之評價。 The following evaluations were performed for each of the adhesive composition obtained in the examples and comparative examples. The results are shown in Table 1. In addition, regarding the adhesive composition obtained in Comparative Example 3, since the resin was not cured, samples for each evaluation could not be produced, and the following evaluations were not performed.

(接著性) (Adherence)

使用分液裝置將實施例及比較例中所獲得之各接著劑組成物以約1mm之寬度塗佈於鋁基板，並藉由使用UV-LED(波長365nm)照射1000mJ/cm2之紫外線而使之光硬化。繼而，將玻璃板貼合於該鋁基板，放置100g之砝碼並放置一夜，藉此使其濕氣硬化而獲得接著性評價用樣品。 Each adhesive composition obtained in the examples and comparative examples was coated on an aluminum substrate with a width of about 1 mm using a liquid separation device, and was irradiated with 1000 mJ / cm 2 of ultraviolet light using a UV-LED (wavelength 365 nm). The light hardens. Next, a glass plate was bonded to the aluminum substrate, and a weight of 100 g was placed and left overnight to cure the moisture to obtain a sample for adhesion evaluation.

於圖2中示出表示自上方觀察接著性評價用樣品之情形之示意圖(圖2(a))及表示自側面觀察接著性評價用樣品之情形之示意圖(圖2(b))。 Fig. 2 is a schematic diagram showing a case where the sample for adhesion evaluation is viewed from above (Fig. 2 (a)) and a schematic diagram showing a case where the sample for adhesion evaluation is viewed from the side (Fig. 2 (b)).

於25℃及80℃下使用拉伸試驗機(島津製作所公司製造，「Ez-Graph」)將所製作之接著性評價用樣品沿剪切方向以5mm/sec之速度拉伸，測定鋁基板與玻璃板剝落時之強度。 Using a tensile tester ("Ez-Graph", manufactured by Shimadzu Corporation) at 25 ° C and 80 ° C, the prepared adhesiveness evaluation sample was stretched at a speed of 5 mm / sec in the shearing direction, and the aluminum substrate and the substrate were measured. Strength when the glass plate is peeled off.

將所測得之強度為18N/cm2以上之情形作為「◎」、將未達18N/cm2且14N/cm2以上之情形作為「○」、將未達14N/cm2且10N/cm2以上之 情形作為「△」、將未達10N/cm2之情形作為「×」而對接著性進行評價。 The measured intensity of 2 or more of the circumstances 18N / cm as "◎" will be less than 18N / cm 2 and 14N / 2 cm above the situation as "○", will be less than 14N / cm 2 and 10N / cm A case of 2 or more was evaluated as "△", and a case of less than 10 N / cm 2 was evaluated as "×", and the adhesiveness was evaluated.

(可靠性) (Reliability)

以與上述「(接著性)」之評價中所製作之接著性評價用樣品相同之方式製作可靠性評價用樣品。 A sample for reliability evaluation was produced in the same manner as the sample for adhesiveness evaluation prepared in the evaluation of "(adhesion)" described above.

將所製作之可靠性評價用樣品相對於地面垂直地懸掛，並以於鋁基板之端懸掛有300g之砝碼之狀態放入80℃之烘箱中。將放入烘箱後經過72小時以上而鋁基板與玻璃亦未剝落之情形作為「◎」、將於24小時以上且未達72小時之期間內剝落之情形作為「○」、將於12小時以上且未達24小時之期間內剝落之情形作為「△」、將於未達12小時之期間內剝落之情形作為「×」而對可靠性進行評價。 The produced reliability evaluation sample was hung vertically with respect to the ground, and placed in an oven at 80 ° C. with a weight of 300 g suspended from the end of the aluminum substrate. The case where the aluminum substrate and glass have not peeled off after 72 hours or more after being placed in the oven is regarded as "◎", and the case where it is peeled off within 24 hours or more but less than 72 hours is regarded as "○" and will be performed for more than 12 hours In addition, the case of peeling within a period of less than 24 hours was regarded as "△", and the case of peeling within a period of less than 12 hours was regarded as "X", and the reliability was evaluated.

(二次加工性) (Secondary workability)

以與上述「(接著性)」之評價中所製作之接著性評價用樣品相同之方式獲得二次加工性評價用樣品。 A sample for secondary workability evaluation was obtained in the same manner as the sample for adhesiveness evaluation produced in the evaluation of "(adhesiveness)" described above.

於100℃下使用拉伸試驗機(島津製作所公司製造，「Ez-Graph」)將所製作之二次加工評價用樣品沿剪切方向以5mm/sec之速度拉伸，測定鋁基板與玻璃板剝落時之強度。 Using a tensile tester ("Ez-Graph", manufactured by Shimadzu Corporation) at 100 ° C, the prepared secondary processing evaluation sample was stretched at a speed of 5 mm / sec in the shear direction to measure the aluminum substrate and the glass plate. Strength when peeling.

將所測得之強度為5N/cm2以下之情形作為「◎」、將超過5N/cm2且10N/cm2以下之情形作為「○」、將超過10N/cm2且18N/cm2以下之情形作為「△」、將超過18N/cm2之情形作為「×」而對二次加工性進行評價。 The measured the intensity of 2 or less the situation 5N / cm as "◎", will be more than 2 or less of the situation 5N / cm 2 and 10N / cm as "○", will be more than 10N / cm 2 and 18N / cm 2 or less In the case of "△", the case of exceeding 18 N / cm 2 was evaluated as "×", and the secondary workability was evaluated.

[產業上之可利用性] [Industrial availability]

根據本發明，可提供一種接著性優異且低溫下之二次加工容易的接著劑組成物。又，根據本發明，可提供一種該接著劑組成物之硬化體以及具有該接著劑組成物之硬化體的電子零件及組裝零件。 According to the present invention, it is possible to provide an adhesive composition having excellent adhesion and easy secondary processing at a low temperature. Furthermore, according to the present invention, it is possible to provide a hardened body of the adhesive composition, and an electronic component and an assembled component having the hardened body of the adhesive composition.

Claims (11)

一種接著劑組成物，其含有濕氣硬化型樹脂與發泡劑。     An adhesive composition containing a moisture-curable resin and a foaming agent.     如申請專利範圍第1項之接著劑組成物，其中，上述發泡劑之發泡起始溫度為60℃~130℃。     For example, the adhesive composition of item 1 of the patent application range, wherein the foaming starting temperature of the foaming agent is 60 ° C to 130 ° C.     如申請專利範圍第1或2項之接著劑組成物，其中，上述發泡劑為粒子形狀，且平均粒徑為5~20μm。     For example, the adhesive composition according to item 1 or 2 of the patent application range, wherein the foaming agent has a particle shape and an average particle diameter is 5 to 20 μm.     如申請專利範圍第1、2或3項之接著劑組成物，其中，上述接著劑組成物100重量份中之發泡劑之含量為1~50重量份。     For example, the adhesive composition in the scope of claims 1, 2, or 3 of the patent application, wherein the content of the foaming agent in 100 parts by weight of the adhesive composition is 1 to 50 parts by weight.     如申請專利範圍第1、2、3或4項之接著劑組成物，其中，上述濕氣硬化型樹脂為濕氣硬化型胺酯樹脂。     For example, the adhesive composition according to item 1, 2, 3, or 4 of the application scope, wherein the moisture-curable resin is a moisture-curable amine ester resin.     如申請專利範圍第1、2、3、4或5項之接著劑組成物，其含有自由基聚合性化合物及光自由基聚合起始劑。     For example, the adhesive composition of claim 1, 2, 3, 4, or 5 contains a radical polymerizable compound and a photoradical polymerization initiator.     如申請專利範圍第1、2、3、4、5或6項之接著劑組成物，其含有蠟。     For example, the adhesive composition of claim 1, 2, 3, 4, 5, or 6 contains a wax.     一種硬化體，係申請專利範圍第1、2、3、4、5、6或7項之接著劑組成物之硬化體，並且具有脲鍵及/或胺酯鍵。     A hardened body is a hardened body of the adhesive composition of claim 1, 2, 3, 4, 5, 6, or 7 and has a urea bond and / or an amine ester bond.     一種電子零件，其具有申請專利範圍第1、2、3、4、5、6或7項之接著劑組成物的硬化體。     An electronic component having a hardened body of an adhesive composition of the scope of patent application No. 1, 2, 3, 4, 5, 6, or 7.     一種組裝零件，其具有第1基板、第2基板、及申請專利範圍第1、2、3、4、5、6或7項之接著劑組成物的硬化體，上述第1基板之至少一部分係經由上述接著劑組成物之硬化體而與上述第2基板之至少一部分接合。     An assembly part comprising a first substrate, a second substrate, and a hardened body of the adhesive composition of claim 1, 2, 3, 4, 5, 6, or 7; at least a part of the first substrate is It is bonded to at least a part of the second substrate via the hardened body of the adhesive composition.     如申請專利範圍第10項之組裝零件，其中，上述第1基板及上述第2 基板分別具有至少1個電子零件。     For example, as for the assembly part in the scope of application for patent No. 10, the first substrate and the second substrate each have at least one electronic component.    
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