TWI711680B - Adhesive composition - Google Patents

Adhesive composition Download PDF

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TWI711680B
TWI711680B TW105120025A TW105120025A TWI711680B TW I711680 B TWI711680 B TW I711680B TW 105120025 A TW105120025 A TW 105120025A TW 105120025 A TW105120025 A TW 105120025A TW I711680 B TWI711680 B TW I711680B
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polymer
adhesive composition
cyanoacrylate
acid
aforementioned
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TW105120025A
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Chinese (zh)
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TW201702331A (en
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石謙一
安藤裕史
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日商東亞合成股份有限公司
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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
    • 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
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • 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
    • C09J169/00—Adhesives based on polycarbonates; Adhesives based on derivatives of polycarbonates
    • 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
    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • C09J171/02—Polyalkylene oxides
    • 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
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09J201/10—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

提供具有柔韌性、同時呈現優良黏著持久性的黏著劑組成物。 Provides an adhesive composition with flexibility and excellent adhesion durability.

含有(a)2-氰基丙烯酸酯、和(b)具有水解性 (hydrolyzability)矽烷基(silyl)的聚合物、和(c)彈性塑料(elastomer)、和(d)酸催化劑、和(e)特定之鎓鹽的黏著劑組成物；前述(b)、(c)、(d)和(e)成分的含量，將前述(a)成分當作100質量部分的情形時，分別是5~200質量部分、5~50質量部分、0.0005~0.5質量部分、及0.001~5質量部分的黏著劑組成物。 Contains (a) 2-cyanoacrylate, and (b) hydrolyzable (hydrolyzability) silyl polymer, and (c) elastomer, and (d) acid catalyst, and (e) specific onium salt adhesive composition; the aforementioned (b), (c) ), (d) and (e) components, when the aforementioned (a) component is regarded as 100 mass parts, they are 5~200 mass parts, 5-50 mass parts, 0.0005~0.5 mass parts, and 0.001 ~5 mass parts of adhesive composition.

Description

黏著劑組成物 Adhesive composition

本發明係有關於黏著劑組成物(Adhesive composition)；更詳細地說，本發明係有關於含有2-氰基丙烯酸酯(2-cyanoacrylate ester)的黏著劑組成物，具有柔韌性(pliability)，同時呈現優良黏著持久性(adhesive durability)的黏著劑組成物。 The present invention relates to an adhesive composition; more specifically, the present invention relates to an adhesive composition containing 2-cyanoacrylate ester, which has pliability, At the same time, an adhesive composition exhibiting excellent adhesive durability.

含有2-氰基丙烯酸酯(2-cyanoacrylate ester)的黏著劑組成物(adhesive compopsition)，由於主成分2-氰基丙烯酸酯具有的獨特陰離子聚合性(anionic polymerization)，藉著附在被黏物體表面的些許水分等的微弱陰離子就可起始聚合，在很短時間內可以牢固黏合各種材料；因此，作為所謂的瞬間黏著劑，廣泛應用在工業、醫療及家庭等領域。但是，這種黏著劑組成物，因為其硬化物硬而易碎，具有優良的剪切黏接強度(shearing adhesive strength)的反面，就是剝離黏接 強度(peeling adhesive strength)和撞擊黏接強度(impact adhesive strength)很低，特別是在異類被黏物之間具有低劣的耐冷熱循環性(thermal cycle resistance)的問題。又，使用此黏著劑組成物黏合有柔韌性被黏物的情形時，也產生會損害該被黏物具有的柔韌性的問題。 Adhesive composition containing 2-cyanoacrylate ester (adhesive composition), due to the unique anionic polymerization of the main component 2-cyanoacrylate ester, by attaching to the adherend Weak anions such as a little water on the surface can initiate polymerization, and can bond various materials firmly in a short time; therefore, as a so-called instant adhesive, it is widely used in industries, medical and household fields. However, this adhesive composition, because its hardened material is hard and fragile, has excellent shearing adhesive strength, which is the opposite of peeling bonding. Peeling adhesive strength and impact adhesive strength are very low, especially the poor thermal cycle resistance between different types of adherends. In addition, when using this adhesive composition to bond a flexible adherend, there is a problem that the flexibility of the adherend is impaired.

一直以來，為了改善這種問題，調配加入各種塑化劑(plasticizer)和彈性塑料(elastomer)等的改善性質方法一直有人提出來《例如，專利文獻1、2和3》；再者，也有人提出調配加入極微溶性橡膠(slightly soluble gum)或彈性塑料粒子的方法《例如，專利文獻4》。更進一步，使用2-氰基丙烯酸酯和常溫濕氣硬化型黏著劑(room temperature moisture curing type adhesive)的兩種黏著劑，在短時間達到臨時固定(temporal tacking)，同時，經過一定時間後，就可以得到充分的黏合強度的黏著方法也被揭示出來《例如，專利文獻5》。 In order to alleviate this problem, a method of improving properties by adding various plasticizers and elastomers has been proposed in "Patent Documents 1, 2 and 3, for example"; A method of compounding and adding slightly soluble gum or elastic plastic particles "for example, Patent Document 4" is proposed. Furthermore, the use of two adhesives, 2-cyanoacrylate and room temperature moisture curing type adhesive, achieves temporary tacking in a short time. At the same time, after a certain period of time, An adhesion method that can obtain sufficient adhesion strength is also disclosed "For example, Patent Document 5".

另一方面，為了改善該當黏著劑的耐水性(water resistance)，在2-氰基丙烯酸酯中調配單矽烷(monosilane)化合物或二矽烷(disilane)化合物，這樣的作法已有人揭示《例如，專利文獻6》。 On the other hand, in order to improve the water resistance of the adhesive, a monosilane compound or a disilane compound is blended into 2-cyanoacrylate. Such a method has been disclosed in "For example, the patent Literature 6.

【先前技術文獻】 【Prior Technical Literature】 【專利文獻】 【Patent Literature】

【專利文獻1】特開平2-34678號公報 [Patent Document 1] JP 2-34678 A

【專利文獻2】特開平6-145605號公報 [Patent Document 2] JP 6-145605 A

【專利文獻3】特開平6-57214號公報 [Patent Document 3] Japanese Patent Laid-Open No. 6-57214

【專利文獻4】特開平6-240209號公報 [Patent Document 4] JP 6-240209 A

【專利文獻5】特開昭63-12677號公報 [Patent Document 5] Japanese Patent Laid-Open No. 63-12677

【專利文獻6】美國專利申請公開第20130174981號說明書 [Patent Document 6] Specification of US Patent Application Publication No. 20130174981

但是，前述專利文獻1所記載的改善性質方法中，雖然賦予柔韌性，但在不同種類的被黏物之間，卻有耐冷熱循環性不充分，還有塑化劑從硬化物滲出(bleed out)，黏著強度隨著時間而降低的問題。又，前述專利文獻2~4中所揭示的黏著劑組成物，雖然有提高黏著強度的情形，但卻有硬化物變硬，柔韌性變壞的問題。再者，專利文獻5中所揭示的黏合方法，因為使用二液型黏著劑，因此作業性不好，生產性也很低，還有，因為不是二液互相混合後塗覆，對於黏著劑硬化物全體，又有柔韌性不足的問題。另一方面，專利文獻6中揭示的黏著劑組成物中，雖然含有矽烷化合物，但由於該當矽烷化合物係低分子量化合物，無法得到應化物的柔韌性。 However, in the method for improving properties described in Patent Document 1, although flexibility is imparted, between different types of adherends, the resistance to cold and heat cycles is insufficient, and plasticizers bleed from the hardened material. out), the problem that the adhesive strength decreases with time. In addition, although the adhesive composition disclosed in the aforementioned Patent Documents 2 to 4 may increase the adhesive strength, there is a problem that the cured product becomes hard and the flexibility deteriorates. Furthermore, the bonding method disclosed in Patent Document 5 uses a two-component adhesive, so the workability is not good, and the productivity is also low. In addition, because the two-components are not mixed with each other and then coated, the adhesive is hardened The whole thing has the problem of insufficient flexibility. On the other hand, the adhesive composition disclosed in Patent Document 6 contains a silane compound, but since the silane compound is a low-molecular-weight compound, the flexibility of the applied product cannot be obtained.

本發明有鑑於前述之過去狀況，提供含有2-氰基丙烯酸酯(2-cyanoacrylate ester)的黏著劑組成物(adhesive compopsition)，具有柔韌性(pliability)，同時呈現優良黏著持久性(adhesive durability)的黏著劑組成物，以此作為目的。 In view of the foregoing past situation, the present invention provides an adhesive composition containing 2-cyanoacrylate ester (adhesive composition), which has pliability and at the same time exhibits excellent adhesive durability. The adhesive composition is used as the purpose.

本發明團隊為了解決前述課題而深入研究之結果，發現：含有2-氰基丙烯酸酯、具有水解性(hydrolyzability)矽烷基(silyl)的聚合物、彈性塑料(elastomer)、酸催化劑(acid catalyst)及特定的鎓鹽(onium salt)的黏著劑組成物，併具柔韌性和黏著持久性，本發明就此完成。 In order to solve the aforementioned problems, the team of the present invention has conducted in-depth research and found that: polymers containing 2-cyanoacrylate, hydrolyzability silyl groups, elastomers, and acid catalysts And a specific onium salt (onium salt) adhesive composition, and has flexibility and adhesion durability, the present invention is completed.

亦即，本發明，依據其一個面向，係含有(a)2-氰基丙烯酸酯、和(b)具有水解性(hydrolyzability)矽烷基(silyl)的聚合物、和(c)彈性塑料(elastomer)、和(d)酸催化劑、 和(e)含有下述化學式(1)所表之鎓鹽；前述(a)成分當作100質量部分的情形時，前述(b)成分的含量為5~200質量部分，前述(c)成分的含量為5~50質量部分，前述(d)成分的含量為0.0005~0.5質量部分，前述(e)成分的含量為0.001~5質量部分，提供以此為特徵的黏著劑。 That is, the present invention, according to one aspect thereof, contains (a) 2-cyanoacrylate, and (b) a polymer having hydrolyzability (silyl), and (c) an elastomer (elastomer). ), and (d) acid catalyst, And (e) contains an onium salt represented by the following chemical formula (1); when the aforementioned component (a) is regarded as 100 parts by mass, the content of the aforementioned component (b) is 5 to 200 parts by mass, and the aforementioned component (c) The content of the component is 5-50 parts by mass, the content of the aforementioned component (d) is 0.0005-0.5 parts by mass, and the content of the aforementioned component (e) is 0.001-5 parts by mass, providing an adhesive characterized by this.

C+A-……(1) C + A - ...... (1)

《化學式(1)中，C+係鎓鹽陽離子(onium cation)；A-係雙(氟磺醯)亞胺陰離子(bis(fluorosulfonyl)imide anion)》。 "In the chemical formula (1), C + is the onium cation; A - is the bis(fluorosulfonyl) imide anion".

依據本發明的理想態樣，前述(b)具有水解性矽烷基(silyl)的聚合物，係選自氧化烯(oxyalkylene)類聚合物、乙烯基(vinyl)類聚合物、聚酯(polyester)類聚合物、聚氨酯(polyurethane)類聚合物、和聚碳酸酯(polycarbonate)類聚合物所成群類中至少一種的聚合物。 According to an ideal aspect of the present invention, the aforementioned (b) polymer with hydrolyzable silyl group is selected from oxyalkylene type polymers, vinyl type polymers, polyesters At least one polymer from the group consisting of a type polymer, a polyurethane type polymer, and a polycarbonate type polymer.

依據本發明的另一的理想態樣，前述(b)具有水解性矽烷基(silyl)的聚合物的數目平均分子量(number average molecular weight)係500~50000。 According to another ideal aspect of the present invention, the number average molecular weight of the aforementioned (b) polymer having a hydrolyzable silyl group is 500 to 50,000.

依據本發明的又另一的理想態樣，前述(c)彈性塑料(elastomer)係使用在2-氰基丙烯酸酯中極微溶性(slightly soluble)的聚合物所形成之單體物(monomer)、與在2-氰基丙烯酸酯中可溶性的聚合物所形成之單體物所作成的共聚物。 According to yet another ideal aspect of the present invention, the aforementioned (c) elastomer is a monomer formed by a slightly soluble polymer in 2-cyanoacrylate, Copolymer with monomers formed by polymers that are soluble in 2-cyanoacrylate.

依據本發明的又另一的理想態樣，前述(c)彈性塑料(elastomer) 係使用在2-氰基丙烯酸酯中極微溶性(slightly soluble)的聚合物所形成之單體物(monomer)、在2-氰基丙烯酸酯中可溶性的聚合物所形成之單體物、及含有羧基(carboxyl)的單體物所作成的共聚物。 According to yet another ideal aspect of the present invention, the aforementioned (c) elastic plastic (elastomer) It is a monomer formed by a polymer that is slightly soluble in 2-cyanoacrylate, a monomer formed by a polymer that is soluble in 2-cyanoacrylate, and contains A copolymer made from carboxyl monomers.

依據本發明的又另一的理想態樣，前述在2-氰基丙烯酸酯中極微溶性的聚合物所形成之單體物，係乙烯(ethylene)、丙烯(propylene)、異戊二烯(isoprene)和丁二烯(butadiene)中的至少一種；在2-氰基丙烯酸酯中可溶性的聚合物所形成之單體物，係丙烯酸酯(acrylate ester)和甲基丙烯酸酯(methacrylate ester)中的至少一者。 According to yet another ideal aspect of the present invention, the monomers formed by the slightly soluble polymer in 2-cyanoacrylate are ethylene, propylene, and isoprene ) And at least one of butadiene (butadiene); a monomer formed by a polymer that is soluble in 2-cyanoacrylate, which is one of acrylate ester and methacrylate ester At least one.

依據本發明的又另一的理想態樣，前述(d)酸催化劑係在25℃時的酸解離常數(pKa；acid dissociation constant)在4以下的酸。 According to yet another ideal aspect of the present invention, the aforementioned (d) acid catalyst is an acid with an acid dissociation constant (pKa; acid dissociation constant) below 4 at 25°C.

依據本發明的又另一的理想態樣，前述(d)酸催化劑係選自磺酸(sulfonic acid)、磷酸(phosphoric acid)、磷酸單酯(phosphoric mono)、磷酸二酯(phosphoric diester)、亞磷酸(phosphorous acid)、及亞磷酸酯(phosphorous ester)所成群類中至少一種的酸。 According to yet another ideal aspect of the present invention, the aforementioned (d) acid catalyst system is selected from sulfonic acid, phosphoric acid, phosphoric monoester, phosphoric diester, Phosphorous acid and at least one acid in the group of phosphorous esters.

依據本發明的又另一的理想態樣，前述(e)鎓鹽陽離子係選自四級銨陽離子(quaternary ammonium cation)、咪唑鎓陽離子(imidazolium cation)、吡啶鎓陽離子(pyridinium cation)、及三級硫鎓陽離子(tertiary sulfonium catiion)所成群類中至少一種的鎓鹽陽離子。 According to yet another ideal aspect of the present invention, the aforementioned (e) onium salt cation is selected from quaternary ammonium cation, imidazolium cation, pyridinium cation, and three At least one onium salt cation in the group of tertiary sulfonium catiion.

本發明之黏著劑組成物，含有2-氰基丙烯酸酯、具有水解性(hydrolyzability)矽烷基(silyl)的聚合物、彈性塑料(elastomer)、酸催化劑、和特定之鎓鹽，因此，硬化物具有柔韌性，同時，耐冷熱循環性和耐熱水性(resistance to hot water)等的黏著持久性也極優。 The adhesive composition of the present invention contains 2-cyanoacrylate, a hydrolyzability (silyl) polymer, an elastomer, an acid catalyst, and a specific onium salt. Therefore, the cured product It has flexibility, and at the same time, it has excellent adhesion and durability such as resistance to hot and cold cycles and resistance to hot water.

以下，針對本發明之黏著劑組成物，加以詳細說明。 Hereinafter, the adhesive composition of the present invention will be described in detail.

本發明之黏著劑組成物，係含有(a)2-氰基丙烯酸酯、(b)具有水解性矽烷基(silyl)的聚合物、(c)彈性塑料(elastomer)、(d)酸催化劑、和(e)含有特定量的下述化學式(1)所表之鎓鹽的黏著劑組成物。 The adhesive composition of the present invention contains (a) 2-cyanoacrylate, (b) a polymer with hydrolyzable silyl group, (c) elastomer, (d) acid catalyst, And (e) an adhesive composition containing a specific amount of an onium salt represented by the following chemical formula (1).

C+A-……(1) C + A - ...... (1)

《化學式(1)中，C+係鎓鹽陽離子(onium cation)；A-係雙(氟磺醯)亞胺陰離子(bis(fluorosulfonyl)imide anion)》。 "In the chemical formula (1), C + is the onium cation; A - is the bis(fluorosulfonyl) imide anion".

作為前述『(a)2-氰基丙烯酸酯』《本說明書中，也可略稱為『(a) 成分』》，可以使用一般通用於此種黏著劑組成物中的2-氰基丙烯酸酯，並無特別的限制。作為此種2-氰基丙烯酸酯，可列舉使用的有：2-氰基丙烯酸甲酯、乙酯、氯乙酯(chloroethyl)、正-丙酯、異-丙酯、烯丙酯(allyl)、炔丙酯(propargyl)、正-丁酯、異-丁酯、正-戊酯(n-pentyl)、正-己酯、環己酯、苯基酯、四氫呋喃酯(tetrahydrofurfuryl)、庚酯(heptyl)、2-乙基己酯、正-辛酯(octyl)、2-辛酯、正-壬酯(n-nonyl)、氧代壬酯(oxononyl)、正-癸酯(decyl)、正-十二烷酯(dodecyl)、甲氧基乙酯(methoxyethyl)、甲氧基丙酯、甲氧基異丙酯、甲氧基丁酯、乙氧基乙酯、乙氧基丙酯、乙氧基異丙酯、丙氧基甲酯(propoxymethyl)、丙氧基乙酯、異丙氧基乙酯、丙氧基丙酯、丁氧基甲酯(butoxymethyl)、丁氧基乙酯、丁氧基丙酯、丁氧基異丙酯、丁氧基丁酯、2,2,2-三氟乙酯(2,2,2-trifluoroethyl)和六氟異丙酯(hexafluoroisopropyl)等的酯類。 As the aforementioned "(a) 2-cyanoacrylate" "In this specification, it may also be referred to as "(a) Ingredients", 2-cyanoacrylate commonly used in such adhesive compositions can be used, and there is no particular limitation. Examples of such 2-cyanoacrylates include methyl 2-cyanoacrylate, ethyl ester, chloroethyl, n-propyl ester, iso-propyl ester, and allyl ester (allyl). , Propargyl, n-butyl, iso-butyl, n-pentyl, n-hexyl, cyclohexyl, phenyl, tetrahydrofurfuryl, heptyl heptyl), 2-ethylhexyl ester, n-octyl ester (octyl), 2-octyl ester, n-nonyl ester (n-nonyl), oxononyl ester (oxononyl), n-decyl ester (decyl), -Dodecyl, methoxyethyl, methoxypropyl, methoxyisopropyl, methoxybutyl, ethoxyethyl, ethoxypropyl, ethyl Propoxymethyl, propoxymethyl, propoxyethyl, isopropoxyethyl, propoxypropyl, butoxymethyl, butoxyethyl, butyl Esters such as oxypropyl, butoxyisopropyl, butoxybutyl, 2,2,2-trifluoroethyl (2,2,2-trifluoroethyl) and hexafluoroisopropyl (hexafluoroisopropyl) .

這些化合物中，為了得到硬化性優良的黏著劑組成物，具有碳數1~4的烷基(alkyl)的2-氰基丙烯酸烷酯(2-cyanoacrylate alkyl ester)是較為理想的。這些2-氰基丙烯酸酯，可以單獨使用一種，也可以二種以上合併使用。 Among these compounds, in order to obtain an adhesive composition with excellent curability, 2-cyanoacrylate alkyl ester having an alkyl group with 1 to 4 carbon atoms is preferable. These 2-cyanoacrylates may be used alone or in combination of two or more.

本發明之黏著劑組成物，含有『(b)具有水解性矽烷基(silyl)的聚合物』《本說明書中，也可略稱為『(b)成分』》。依據本發明，因為含有具有水解性矽烷基的聚合物，因此可以提高耐冷熱循環性和耐熱水性等的黏著持久性；又，因為含有該當聚合物，對於含有2-氰基丙烯酸酯的黏著劑組成物，可以賦與柔韌性。 The adhesive composition of the present invention contains "(b) a polymer having a hydrolyzable silyl group" "in this specification, it may also be abbreviated as "the (b) component"". According to the present invention, because it contains a polymer with hydrolyzable silyl groups, it is possible to improve the adhesion durability of heat and cold cycle resistance and hot water resistance, etc.; and, because it contains the appropriate polymer, it is suitable for adhesives containing 2-cyanoacrylate The composition can impart flexibility.

前述(b)成分中所含有的水解性矽烷基，係具有矽原子、和與此矽原子鍵結的羥基(hydroxyl)及/或水解性功能基，藉著水解而形成矽氧烷鍵結(siloxane bond)的同時也形成交聯結構(cross linking structure)，所得到的化學基。作為水解性矽烷基，並無特別的限制，下述化學式(2)所表之化學基是較合於理想的。 The hydrolyzable silyl group contained in the aforementioned component (b) has a silicon atom, a hydroxyl group and/or a hydrolyzable functional group bonded to the silicon atom, and forms a siloxane bond by hydrolysis ( The siloxane bond also forms a cross-linking structure, the resulting chemical group. The hydrolyzable silyl group is not particularly limited, but the chemical group represented by the following chemical formula (2) is more preferable.

Figure 105120025-A0305-02-0011-2
Figure 105120025-A0305-02-0011-2

《化學式(2)中，R1各自獨立，係烴基(hydrocarbon group)；X各自獨立，係選自鹵素原子、氫原子、羥基、烷氧基(alkoxy)、醯氧基(acyloxyl)、羰游氧基配對(ketoxymate)、醯胺基(amide)、酸醯胺 基(acid amide)、巰基(mercapto group)、鏈烯氧基(alkenyloxy)和氨氧基(aminooxy)之反應性基團(reactive group)；n係0、1或2。》 In the chemical formula (2), R 1 is independent of each other and is a hydrocarbon group; X is independent of each other and is selected from a halogen atom, a hydrogen atom, a hydroxyl group, an alkoxy group, an acyloxyl group, and a carbonyl group. The reactive groups of ketoxymate, amide, acid amide, mercapto group, alkenyloxy and aminooxy group); n is 0, 1, or 2. 》

前述化學式(2)中，R1較為理想的是碳數1~20的烷基(alkyl)、碳數6~20的芳基(aryl group)或碳數7~20的芳代脂烷基(aralkyl)；n=2的時候，複數的R1，可以互相一致，也可以互相不同；又，n=0或1的時候，複數的X，可以互相一致，也可以互相不同；前述化學式(2)中的X，較為理想的是烷氧基(alkoxy)。 In the aforementioned chemical formula (2), R 1 is preferably an alkyl group with 1 to 20 carbons, an aryl group with 6 to 20 carbons, or an aryl group with 7 to 20 carbons ( aralkyl); when n=2, the plural R 1 can be the same as each other or different from each other; and when n=0 or 1, the plural X can be the same or different from each other; the aforementioned chemical formula (2 The X in) is preferably alkoxy.

前述(b)成分的聚合物，一旦含有水解性矽烷基，則因為水解縮合(hydrolysis condensation)的結果，形成Si-O-Si鍵結，可以形成具有優良強度的薄膜等的硬化物。前述化學式(2)中的X是烷氧基時的水解性矽烷基，係烷氧基矽烷基(alkoxy silyl)，例如三甲氧基矽烷基(trimethoxysilyl)、甲基二甲氧基矽烷基(methyl dimethoxysilyl)、二甲基甲氧基矽烷基、三乙氧基矽烷基(triethoxysilyl)、甲基二乙氧基矽烷基、甲基二個(2-甲氧基乙氧基)矽烷基(methyl bis(2-methoxyethoxy)silyl)等可列舉使用；這些化合物中，從硬化速度和柔韌性的平衡來 看，三甲氧基矽烷基和甲基二甲氧基矽烷基是特別合於理想的。 Once the polymer of the aforementioned component (b) contains a hydrolyzable silyl group, as a result of hydrolysis condensation, a Si-O-Si bond is formed, and a cured product such as a thin film with excellent strength can be formed. When X in the aforementioned chemical formula (2) is an alkoxy group, the hydrolyzable silyl group is an alkoxy silyl group, such as trimethoxysilyl and methyldimethoxysilyl. dimethoxysilyl), dimethylmethoxysilyl, triethoxysilyl, methyldiethoxysilyl, methyl two (2-methoxyethoxy) silyl (methyl bis (2-methoxyethoxy)silyl), etc. can be used; among these compounds, the balance between hardening speed and flexibility It appears that trimethoxysilyl and methyldimethoxysilyl are particularly desirable.

前述(b)成分的一個分子中所含有的水解性矽烷基的數目的平均值，從黏著性和硬化物的柔韌性的觀點來看，較理想的是1~4個，更理想的是1.5~3個；水解性矽烷基的數目的平均值是1~4個的情形時，可以得到具備充分硬化性的黏著劑組成物，並且，也得到具備柔韌性的黏著劑組成物。 The average value of the number of hydrolyzable silyl groups contained in one molecule of the aforementioned component (b) is preferably 1 to 4, and more preferably 1.5 from the viewpoint of adhesiveness and flexibility of the cured product. ~3; When the average number of hydrolyzable silyl groups is 1 to 4, an adhesive composition with sufficient curability can be obtained, and an adhesive composition with flexibility can also be obtained.

再者，(b)成分中所含有的水解性矽烷基的位置，並無特別的限制，可以放在聚合物的支鏈或末端。 In addition, the position of the hydrolyzable silyl group contained in the component (b) is not particularly limited, and it can be placed at the branch or terminal of the polymer.

前述(b)具有水解性矽烷基(silyl)的聚合物，較理想的是選自氧化烯類(oxyalkylene)聚合物、乙烯類(vinyl)聚合物、聚酯類聚合物、聚氨酯類聚合物、和聚碳酸酯類聚合物所成群類中至少一者的聚合物；這些聚合物中，從黏著劑硬化物的柔韌性、以及與2-氰基丙烯酸酯的混合穩定性之點來看，氧化烯類聚合物和乙烯類聚合物是更合 於理想的。又，前述聚合物，直鏈狀聚合物或分枝狀聚合物的任一者都可以，還有，這些組合起來使用也可以。 The aforementioned (b) polymer having a hydrolyzable silyl group (silyl) is preferably selected from oxyalkylene polymers, vinyl polymers, polyester polymers, polyurethane polymers, A polymer of at least one of the group of polycarbonate polymers; among these polymers, from the point of view of the flexibility of the hardened adhesive and the stability of mixing with 2-cyanoacrylate, Oxyalkylene polymers and ethylene polymers are more compatible To the ideal. In addition, the aforementioned polymer may be either a linear polymer or a branched polymer, and these may be used in combination.

前述氧化烯類(oxyalkylene)聚合物，只要是含有下述化學式(3)所表之重複單元(repeating units)之聚合物即可，並無特別的限制。 The aforementioned oxyalkylene polymer is not particularly limited as long as it contains repeating units represented by the following chemical formula (3).

-O-R2-……(3) -OR 2 -……(3)

《化學式(3)中，R2係2價的烴基。》 In the chemical formula (3), R 2 is a divalent hydrocarbon group. 》

作為前述化學式(3)中R2，可列舉使用的有：-CH(CH3)-CH2-、-CH(C2H5)-CH2-、-C(CH3)2-CH2-、-CH2CH2CH2CH2-等；這些R2之中，-CH(CH3)-CH2-是較合於理想的。又，前述氧化烯類聚合物，可以含有單獨一種前述重複單元，也可以含有二種以上前述重複單元的組合。 Examples of R 2 in the aforementioned chemical formula (3) include: -CH(CH 3 )-CH 2 -, -CH(C 2 H 5 )-CH 2 -, -C(CH 3 ) 2 -CH 2 -, -CH 2 CH 2 CH 2 CH 2 -etc. Among these R 2 , -CH(CH 3 )-CH 2 -is more desirable. In addition, the oxyalkylene-based polymer may contain a single kind of the repeating unit, or a combination of two or more kinds of the repeating unit.

前述氧化烯類聚合物的製造方法，並沒有特別的限制，可列舉的有：藉由鹼催化劑如氫氧化鉀(KOH)的製造方法、藉由過渡金屬化 合物(transition metal compound)卟啉(porphyrin)絡合催化劑(complex catalyst)的製造方法、藉由複合金屬氰化物(composite metal cyanide)絡合催化劑的製造方法、使用磷腈類(phosphazene)的製造方法等。這些方法之中，藉由複合金屬氰化物絡合催化劑的製造方法，係高分子量，而且適合於得到分子量分布範圍狹窄的聚合物，使用這種聚合物，因為黏著劑組成物的黏度和硬化物的斷襲伸度(break elongation)的平衡極為優良而較合於理想。 The production method of the aforementioned oxyalkylene polymer is not particularly limited. Examples include: production method by alkali catalyst such as potassium hydroxide (KOH), by transition metalization Transition metal compound (transition metal compound) porphyrin (porphyrin) complex catalyst (complex catalyst) production method, by composite metal cyanide (composite metal cyanide) production method of complex catalyst, production using phosphazene (phosphazene) Methods etc. Among these methods, the manufacturing method of a composite metal cyanide complex catalyst is a high molecular weight polymer and is suitable for obtaining a polymer with a narrow molecular weight distribution range. This polymer is used because of the viscosity of the adhesive composition and the hardened material The balance of break elongation is excellent and ideal.

又，前述乙烯類聚合物，只要是具有自由基(radical)聚合性的乙烯類單體物聚合而成之化合物，並無特別限制。乙烯類單體物，可列舉使用的有：(偏)丙烯酸((meta)acrylic acid)、(偏)丙烯酸甲酯(methyl(meta)acrylate)、(偏)丙烯酸乙酯、(偏)丙烯酸正-丙酯、(偏)丙烯酸異丙酯、(偏)丙烯酸正-丁酯、(偏)丙烯酸異丁酯、(偏)丙烯酸特-丁酯、(偏)丙烯酸正-戊酯、(偏)丙烯酸正-己酯、(偏)丙烯酸環己酯、(偏)丙烯酸正-庚酯、(偏)丙烯酸正-辛酯、(偏)丙烯酸2-乙基己酯、(偏)丙烯酸壬酯(nonyl(meta)acrylate)、(偏)丙烯酸癸酯(decyl(meta)acrylate)、(偏)丙烯酸十二烷酯(dodecyl(meta)acrylate)、(偏)丙烯酸苯酯(phenyl(meta)acrylate)、(偏)丙烯酸甲苯酯(toluyl(meta)acrylate )、(偏)丙烯酸苄酯(benzyl(meta)acrylate)、(偏)丙烯酸2-甲氧基乙酯、(偏)丙烯酸3-甲氧基丙酯、(偏)丙烯酸2-羥基乙酯(2-hydroxyethyl(meta)acrylate)、(偏)丙烯酸2-羥基丙酯、(偏)丙烯酸十八烷酯(stearyl(meta)acrylate)、(偏)丙烯酸的環氧乙烷加成物(ethylene oxide additive of(meta)acrylate)、(偏)丙烯酸三氟甲基甲酯(trifluorome thylmethyl(meta)acrylate)、(偏)丙烯酸2-三氟甲基乙酯、(偏)丙烯酸2-全氟乙基乙酯(2-perfluoroethylethyl(meta)acrylate)、(偏)丙烯酸2-全氟乙基-2-全氟丁基乙酯(2-perfluoroethyl-2-perfluorobutylethyl(meta)acrylate)、(偏)丙烯酸2-全氟乙酯(2-perfluoroethyl(meta)acrylate)、(偏)丙烯酸全氟甲酯、(偏)丙烯酸二全氟甲基甲酯(diperfluoromethylmethyl(meta)acrylate)、(偏)丙烯酸2-全氟甲基-2-全氟乙基甲酯、(偏)丙烯酸2-全氟己基乙酯、(偏)丙烯酸2-全氟癸基乙酯、(偏)丙烯酸2-全氟十六烷基乙酯(2-perfluorohexadecylethyl(meta)acrylate)等的(偏)丙烯酸類單體物；乙烯(styrene)、乙烯基甲苯(vinyltoluene)、α-甲基苯乙烯(α-methyl styrene)、氯苯乙烯(chlorostyrene)、苯乙烯磺酸(styrene sulfonic acid)及其鹽類等的苯乙烯類單體物；全氟乙烯(perfluoroethylene)、全氟丙烯、氟化亞乙烯(vinylidene fluoride)等的含氟元素乙烯單體物；馬來酸酐(maleic anhydride)、馬來酸(maleic acid)、馬來酸的單烷基酯(monoalkylester)和二烷基酯；富馬 酸(fumaric acid)、富馬酸的單烷基酯和二烷基酯；馬來醯亞胺(maleimide)、甲基馬來醯亞胺、乙基馬來醯亞胺、丙基馬來醯亞胺、丁基馬來醯亞胺、己基馬來醯亞胺、辛基馬來醯亞胺、十二烷基馬來醯亞胺、十八烷基馬來醯亞胺(Stearyl maleimide)、苯基馬來醯亞胺、環己基馬來醯亞胺等的馬來醯亞胺類單體物；丙烯腈(acrylonitrile)、甲基丙烯腈(methacrylonitrile)等的含腈(nitrile)乙烯類單體物；丙烯醯胺(acrylamide)、甲基丙烯醯胺(methacrylamide)等的含醯胺基(amide)乙烯類單體物；醋酸乙烯酯(vinyl acetate)、丙酸乙烯酯(vinyl propionate)、特戊丙酸乙烯酯(pivalic acid vinyl ester)、苯甲酸乙烯酯(vinyl benzoate)、肉桂酸乙烯酯(vinyl cinnamate)等的乙烯酯類；乙烯、丙烯等的烯烴類(alkene)；丁二烯(buta diene)、異戊二烯(isoprene)等的共軛二烯類(conjugated diene)；氯化乙烯(vinyl chloride)、氯化亞乙烯(vinylidene chloride)、氯化丙烯(allyl chloride)、烯丙醇(allyl alcohol)等。這些化合物，可以單獨使用，也可以複數個共聚合使用；再者，於前述的表示形式中，例如所謂(偏)丙烯酸係表示丙烯酸或甲基丙烯酸。 In addition, the aforementioned vinyl polymer is not particularly limited as long as it is a compound obtained by polymerizing a vinyl monomer having radical polymerizability. Ethylene monomers, including (meta) acrylic acid, (meta) methyl (meta) acrylate, (meta) ethyl acrylate, (meta) acrylic acid -Propyl ester, (meta) isopropyl acrylate, (meta) n-butyl acrylate, (meta) isobutyl acrylate, (meta) t-butyl acrylate, (meta) pentyl acrylate, (meta) N-hexyl acrylate, cyclohexyl (meta) acrylate, n-heptyl (meta) acrylate, n-octyl (meta) acrylate, 2-ethylhexyl (meta) acrylate, nonyl (meta) acrylate ( nonyl(meta)acrylate, decyl(meta)acrylate, dodecyl(meta)acrylate, phenyl(meta)acrylate , Toluyl(meta)acrylate ), benzyl(meta)acrylate, 2-methoxyethyl (meta)acrylate, 3-methoxypropyl (meta)acrylate, 2-hydroxyethyl (meta)acrylate ( 2-hydroxyethyl(meta)acrylate, 2-hydroxypropyl (meta)acrylate, stearyl(meta)acrylate, ethylene oxide adducts of (meta)acrylate additive of (meta)acrylate, trifluorome thylmethyl(meta)acrylate, 2-trifluoromethyl ethyl (meta)acrylate, 2-perfluoroethyl (meta)acrylate Ethyl (2-perfluoroethylethyl(meta)acrylate), (meta)acrylate 2-perfluoroethyl-2-perfluorobutylethyl(meta)acrylate, (meta)acrylate 2 -Perfluoroethyl(meta)acrylate, perfluoromethyl (meta)acrylate, diperfluoromethylmethyl(meta)acrylate, 2-perfluoromethyl(meta)acrylate (meta)acrylate Fluoromethyl-2-perfluoroethyl methyl ester, 2-perfluorohexylethyl (meta)acrylate, 2-perfluorodecylethyl (meta)acrylate, 2-perfluorohexadecyl (meta)acrylate (Meta)acrylic monomers such as ethyl (2-perfluorohexadecylethyl(meta)acrylate); ethylene (styrene), vinyl toluene (vinyltoluene), α-methyl styrene (α-methyl styrene), chlorostyrene (chlorostyrene), styrene sulfonic acid (styrene sulfonic acid) and its salts and other styrene monomers; perfluoroethylene (perfluoroethylene), perfluoropropylene, vinylidene fluoride (vinylidene fluoride) and other fluorine-containing elements Ethylene monomers; maleic anhydride, maleic acid, monoalkylester and dialkyl esters of maleic acid; fumar Fumaric acid, mono- and di-alkyl esters of fumaric acid; maleimide, methyl maleimide, ethyl maleimide, propyl maleimide Imine, butyl maleimide, hexyl maleimide, octyl maleimide, dodecyl maleimide, stearyl maleimide (Stearyl maleimide), Maleimide monomers such as phenylmaleimide and cyclohexylmaleimide; nitrile vinyl monomers such as acrylonitrile and methacrylonitrile Body; acrylamide, methacrylamide, and other amide-containing vinyl monomers; vinyl acetate, vinyl propionate, Vinyl esters such as pivalic acid vinyl ester, vinyl benzoate, and vinyl cinnamate; alkene such as ethylene and propylene; butadiene (buta diene), isoprene (isoprene) and other conjugated dienes (conjugated diene); chlorinated ethylene (vinyl chloride), chlorinated vinylene (vinylidene chloride), chlorinated propylene (allyl chloride), olefin Allyl alcohol and so on. These compounds can be used singly or in multiple copolymerizations; furthermore, in the aforementioned representation form, for example, the so-called (meta)acrylic system means acrylic acid or methacrylic acid.

具有水解性矽烷基的乙烯類聚合物的製造方法，可以應用一般 習知的方法，例如，特開昭59-122541號、特開昭60-31556號、特開昭63-112642號、特開平6-172631號各公報所揭示者。 The method for producing ethylene polymers with hydrolyzable silyl groups can be applied to general Conventional methods are disclosed in, for example, JP-A No. 59-122541, JP-A 60-31556, JP-A 63-112642, and JP-A 6-172631.

又，作為水解性矽烷基之聚合物，可以使用具有氧烷基矽烷基(alkoxysilyl)的接枝共聚物(graft copolymer)，這一類共聚物，例如國際公開WO2007/023669號所揭示者。 In addition, as the polymer of the hydrolyzable silyl group, a graft copolymer having an alkoxysilyl group can be used. This type of copolymer, for example, is disclosed in International Publication No. WO2007/023669.

再進一步，本發明中所使用之具水解性矽烷基聚合物，可以在分子內含有極性要素(polar element)部分。此處，所謂極性要素部分係指尿烷鍵結(urethane linkage)、硫代尿烷鍵結(thiourethane linkage)、尿素鍵結(urea linkage)、硫代尿素鍵結、取代尿素鍵結(substituent urea linkage)、取代硫代尿素鍵結、醯胺鍵結(amide linkage)、和硫化物鍵結(sulfide linkage)等。像這種在分子內含有極性要素部分的硬化性樹脂的製造方法，揭示在特開2000-169544號公報等。 Furthermore, the hydrolyzable silyl polymer used in the present invention may contain a polar element part in the molecule. Here, the so-called polar element part means urethane linkage, thiourethane linkage, urea linkage, thiourea linkage, and substituent urea linkage. linkage), substituted thiourea bonding, amide linkage, and sulfide linkage, etc. Such a method for producing a curable resin containing a polar element part in the molecule is disclosed in JP 2000-169544 A and the like.

前述(b)具有水解性矽烷基的聚合物的數目平均分子量，較合於理想的是500~50000，更合於理想的是1000~40000，又更合於理想的是3000~35000。前述數目平均分子量若是500~50000的話，硬化物的柔韌性良好，可以做成呈現優良耐冷熱循環性和耐熱水性的黏著劑組成物。 The number average molecular weight of the aforementioned (b) polymer having a hydrolyzable silyl group is preferably 500 to 50,000, more preferably 1,000 to 40,000, and more preferably 3,000 to 35,000. If the number average molecular weight is 500 to 50,000, the cured product has good flexibility and can be made into an adhesive composition exhibiting excellent resistance to cold and heat cycles and hot water resistance.

黏著劑組成物中的前述(b)具有水解性矽烷基的聚合物的含量，將2-氰基丙烯酸酯當作100質量部分的話，係5~20質量部分。前述含量，較合於理想的是10~150質量部分，更合於理想的是15~100質量部分。前述聚合物的含量若是5~20質量部分的話，則可得到耐冷熱循環性和耐熱水性等的黏著持久性優良的黏著劑組成物，而且得到充分具有柔韌性的黏著劑組成物。 The content of the aforementioned (b) polymer having a hydrolyzable silyl group in the adhesive composition is 5-20 parts by mass when 2-cyanoacrylate is regarded as 100 parts by mass. The aforementioned content is preferably 10 to 150 parts by mass, and more preferably 15 to 100 parts by mass. If the content of the aforementioned polymer is 5 to 20 parts by mass, an adhesive composition having excellent adhesion durability such as heat and cold cycle resistance and hot water resistance can be obtained, and an adhesive composition having sufficient flexibility can be obtained.

所謂前述『(c)彈性塑料(elastomer)』《本說明書中，也可略稱為『(c)成分』》係指在常溫《20℃±15℃》附近具有橡膠(gum)狀彈性之物；只要是能溶解於(a)2-氰基丙烯酸酯和(b)具有水解性矽烷基(silyl)的聚合物二者之物即可，並無特別的限制。前述(a)2-氰基丙烯 酸酯和前述(b)具有水解性矽烷基(silyl)的聚合物，無論相溶或不相容，因為前述彈性塑料的存在，可以穩定地相容。 The so-called "(c) elastic plastic (elastomer)" "in this manual may also be abbreviated as "(c) component"" refers to a substance with rubber (gum)-like elasticity near normal temperature "20℃±15℃" ; As long as it is soluble in both (a) 2-cyanoacrylate and (b) a polymer having a hydrolyzable silyl group (silyl), it is not particularly limited. The aforementioned (a) 2-cyanopropene The acid ester and the aforementioned (b) polymer having hydrolyzable silyl groups, regardless of being compatible or incompatible, can be stably compatible due to the existence of the aforementioned elastic plastic.

作為此彈性塑料，可列舉使用的有：丙烯酸酯類共聚物、丙烯腈-苯乙烯類共聚物(acrylonitrile-styrene copolymer)、丙烯腈-丁二烯類共聚物(acrylonitrile-butadiene copolymer)、丙烯腈-丁二烯-苯乙烯類共聚物、苯乙烯-丁二烯類共聚物、苯乙烯-異戊二烯類共聚物(styrene-isoprene copolymer)、乙烯-丙烯酸酯類共聚物(ethylene-acrylate ester copolymer)、乙烯-丙烯類共聚物(ethylene-propylene copolymer)、乙烯-醋酸乙烯酯類共聚物(ethylene-vinyl acetate copolymer)、聚氨酯類共聚物、聚酯類共聚物、氟元素類共聚物、聚異戊二烯類共聚物、氯丁二烯類(chloroprene)共聚物等。這些化合物可以單獨使用一種、也可以二種以上併用。 As this elastic plastic, there can be cited: acrylic ester copolymers, acrylonitrile-styrene copolymers, acrylonitrile-butadiene copolymers, and acrylonitrile-styrene copolymers. -Butadiene-styrene copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, ethylene-acrylate ester copolymer copolymer), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, polyurethane copolymer, polyester copolymer, fluorine element copolymer, poly Isoprene copolymers, chloroprene copolymers, etc. These compounds may be used alone or in combination of two or more kinds.

又，這些彈性塑料之中，作為特別合於理想者，係使用在2-氰基丙烯酸酯中極微溶性的聚合物所形成之單體物(monomer)、與在2-氰基丙烯酸酯中可溶性的聚合物所形成之單體物《但是，含有下述羧基(carboxyl)之單體物除外》所作成的共聚物。此共聚物，具備了在2-氰基丙烯酸酯中極微溶性的聚合物所形成之單體物聚合而成的 極微溶性段片(segment)、和在2-氰基丙烯酸酯中可溶性的聚合物所形成之單體物聚合而成的可溶性段片。於本發明中，『2-氰基丙烯酸酯中極微溶性的聚合物』，與『2-氰基丙烯酸酯中可溶性的聚合物』相比，只要是對2-氰基丙烯酸酯的溶解度較差之物即可。 In addition, among these elastic plastics, as particularly desirable ones, monomers formed from polymers that are very slightly soluble in 2-cyanoacrylate and monomers that are soluble in 2-cyanoacrylate are used. The monomers formed by the polymer "except for the monomers containing the following carboxyl groups". This copolymer is formed by polymerization of monomers formed by a polymer that is very slightly soluble in 2-cyanoacrylate Very slightly soluble segment and a soluble segment formed by polymerization of monomers formed by a polymer soluble in 2-cyanoacrylate. In the present invention, the "very slightly soluble polymer in 2-cyanoacrylate" is compared with the "polymer soluble in 2-cyanoacrylate" as long as the solubility to 2-cyanoacrylate is poorer Things can be.

在2-氰基丙烯酸酯中極微溶性的聚合物所形成之單體物並無特別的限制，可列舉使用的有：乙烯(ethylene)、丙烯(propylene)、異戊二烯(isoprene)、丁二烯(butadiene)、氯丁二烯(chloroprene)、1-己烯(1-hexene)和環戊烯(cyclopentene)等。這些單體物可以單獨使用一種，也可以二種以上合併使用。作為極微溶性的聚合物所形成之單體物，大多使用乙烯、丙烯、異戊二烯、丁二烯和氯丁二烯，其中，乙烯、丙烯、異戊二烯和丁二烯之中至少有一種的話，會特別合於理想。 The monomers formed by the very slightly soluble polymer in 2-cyanoacrylate are not particularly limited. Examples of the monomers used are: ethylene, propylene, isoprene, butylene Diene (butadiene), chloroprene (chloroprene), 1-hexene (1-hexene) and cyclopentene (cyclopentene) and so on. These monomers may be used alone or in combination of two or more. As monomers formed by very slightly soluble polymers, ethylene, propylene, isoprene, butadiene and chloroprene are mostly used, among which ethylene, propylene, isoprene and butadiene are at least There is one kind of words that would be particularly ideal.

又，在2-氰基丙烯酸酯中可溶性的聚合物所形成之單體物並無特別的限制，可列舉使用的有：丙烯酸酯、甲基丙烯酸酯(methacrylate ester)、氯乙烯(vinyl chloride)、醋酸乙烯酯(vinyl acetate)、乙烯基 醚(vinyl ether)、苯乙烯和丙烯腈(acrylonitrile)等，其中丙烯酸酯和甲基丙烯酸酯中至少有一者會特別合於理想；作為丙烯酸酯，例如，可列舉使用的有：丙烯酸甲酯(methyl acrylate)、丙烯酸乙酯、丙烯酸正-丙酯、丙烯酸異-丙酯、丙烯酸正-丁酯、丙烯酸異-丁酯、丙烯酸正-己酯、丙烯酸正-庚酯、丙烯酸正-辛酯、丙烯酸2-乙基己酯、丙烯酸甲氧基乙酯、丙烯酸甲氧基丙酯、丙烯酸乙氧基乙酯和丙烯酸乙氧基丙酯等。這些單體物可以單獨使用一種，也可以二種以上合併使用。 In addition, there are no particular restrictions on the monomers formed by the polymers soluble in 2-cyanoacrylate. Examples include acrylic esters, methacrylate esters, and vinyl chloride. , Vinyl acetate, vinyl Ether (vinyl ether), styrene and acrylonitrile (acrylonitrile), etc., wherein at least one of acrylate and methacrylate is particularly desirable; as the acrylate, for example, the use of: methyl acrylate ( methyl acrylate), ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, n-hexyl acrylate, n-heptyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate, methoxypropyl acrylate, ethoxyethyl acrylate and ethoxypropyl acrylate, etc. These monomers may be used alone or in combination of two or more.

再者，作為甲基丙烯酸酯，例如，可列舉使用的有：甲基丙烯酸甲酯(methyl methacrylate)、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、甲基丙烯酸正-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、甲基丙烯酸甲氧基乙酯、甲基丙烯酸甲氧基丙酯、甲基丙烯酸乙氧基乙酯、和甲基丙烯酸乙氧基丙酯等。這些單體物可以單獨使用一種，也可以二種以上合併使用。還有，也可以併用丙烯酸酯和甲基丙烯酸酯。 Furthermore, as the methacrylate, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, methyl N-butyl methacrylate, iso-butyl methacrylate, n-hexyl methacrylate, n-heptyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, methyl methacrylate Methoxy ethyl acrylate, methoxy propyl methacrylate, ethoxy ethyl methacrylate, and ethoxy propyl methacrylate. These monomers may be used alone or in combination of two or more. In addition, acrylate and methacrylate may be used in combination.

極微溶性的聚合物所形成之單體物聚合而成的極微溶性段片、和可溶性的聚合物所形成之單體物聚合而成的可溶性段片的比例，並無特別的限制，這些段片合計作為100%莫耳的情形時，極微溶性段片係5~90%莫耳，較合於理想的是10~80%莫耳；可溶性段片係10~95%莫耳，若是20~90%莫耳的話，較合於理想。此比例，極微溶性段片30~80%莫耳、可溶性段片20~70%莫耳；特別是極微溶性段片40~80%莫耳、可溶性段片20~60%莫耳；再者，極微溶性段片50~75%莫耳、可溶性段片25~50%莫耳，則更合於理想。如果極微溶性段片是5~90%莫耳、可溶性段片10~95%莫耳的話，特別是極微溶性段片為30~80%莫耳、可溶性段片為20~70%莫耳的話，共聚物可以在2-氰基丙烯酸酯中適當地溶解，就可以作成具有很高剪切黏接強度等、並且具有優良的耐冷熱循環性的黏著劑組成物。 The ratio of the very slightly soluble segment formed by the polymerization of the monomer formed by the very slightly soluble polymer and the soluble segment formed by the polymerization of the monomer formed by the soluble polymer is not particularly limited. These segments When the total is 100% mol, the very slightly soluble segment is 5~90% mol, and the ideal is 10~80% mol; the soluble segment is 10~95% mol, if it is 20~90 %Mole is more ideal. This ratio is 30-80% mol for very slightly soluble tablets, 20-70% mol for soluble tablets; especially 40-80% mol for very slightly soluble tablets and 20-60% mol for soluble tablets; Very slightly soluble tablets of 50-75% mol, and soluble tablets of 25-50% mol are more ideal. If the very slightly soluble segment is 5 to 90% mol and the soluble segment is 10 to 95% mol, especially the very slightly soluble segment is 30 to 80% mol, and the soluble segment is 20 to 70% mol, The copolymer can be appropriately dissolved in 2-cyanoacrylate, and it can be made into an adhesive composition with high shear bonding strength and excellent resistance to cold and heat cycles.

各個段片的比例，利用質子核磁共振法(Proton Nuclear Magnetic Resonance；proton NMR)《以下，以『1H-NMR』表記》測定的質子的統合值(integrated value)為基礎，可以計算出來。 The proportion of respective segments sheet by proton nuclear magnetic resonance (Proton Nuclear Magnetic Resonance; proton NMR ) "Hereinafter," 1 H-NMR "token" integration value of protons measured (integrated value) basis, can be calculated.

再者，前述彈性塑料中特別合於理想者，也列舉有：使用在2- 氰基丙烯酸酯中可溶性的聚合物所形成之單體物、和2-氰基丙烯酸酯中極微溶性的聚合物所形成之單體物、和含有羧基(carboxyl)之單體物，所作成的共聚物；通常，此共聚物中，如果含有少量具羧基之單體物的話，是好的。含有羧基之單體物並無特別的限制，可列舉的有：丙烯酸、甲基丙烯酸、馬來酸(maleic acid)、富馬酸(fumaric acid)、衣康酸(itaconic acid)、巴豆酸(crotonic acid)、和肉桂酸(cinnamic acid)等，這些單體物可以單獨使用一種，也可以二種以上合併使用。含有羧基之單體物，大多使用丙烯酸和甲基丙烯酸，可以使用這些單體物的其中一者，也可以二種以上併用。這種含有羧基之單體物聚合而成的含有羧基之段片，可以變成在親水性高的2-氰基丙烯酸酯中的可溶性段片。該當彈性塑料因為是含有羧基之共聚物，可以做成呈現更優良黏著持久性的黏著劑組成物。 Furthermore, among the aforementioned elastic plastics that are particularly ideal, there are also listed as follows: Monomers formed by soluble polymers in cyanoacrylate, monomers formed by very slightly soluble polymers in 2-cyanoacrylate, and monomers containing carboxyl groups. Copolymer: Generally, this copolymer is good if it contains a small amount of monomers with carboxyl groups. The monomers containing carboxyl groups are not particularly limited. Examples include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, and crotonic acid ( Crotonic acid), cinnamic acid, etc., these monomers can be used alone or in combination of two or more. The carboxyl group-containing monomers often use acrylic acid and methacrylic acid, and one of these monomers may be used, or two or more of them may be used in combination. The carboxyl group-containing segment formed by polymerization of such a carboxyl group-containing monomer can be transformed into a soluble segment in the highly hydrophilic 2-cyanoacrylate. As the elastic plastic is a copolymer containing carboxyl groups, it can be made into an adhesive composition with better adhesion durability.

含有羧基之段片的比例，並無特別的限制，但極微溶性段片、可溶性段片、和含有羧基段片之合計，當成100%莫耳的情形時，係0.1~5%莫耳為理想，特別是0.3~4%莫耳更為理想，更進而0.4~3%莫耳又更為理想。還有，此含量以0.5~2.5%莫耳為理想，而0.5~2.3%莫耳更為理想。含有羧基之段片如果是0.1~5%莫耳，尤其是0.5~ 2.5%莫耳的話，可以作成塗覆在被黏物後，很快就硬化，並且具有很優良的耐冷熱循環性和耐熱水性的黏著劑組成物。 The proportion of carboxyl-containing segments is not particularly limited, but when the total of very slightly soluble segments, soluble segments, and carboxyl-containing segments is 100% mol, 0.1~5% mol is ideal , Especially 0.3~4% mol is more ideal, and 0.4~3% mol is even more ideal. In addition, the content is preferably 0.5 to 2.5% mol, and 0.5 to 2.3% mol is more desirable. If the segment containing carboxyl group is 0.1~5% mol, especially 0.5~ With 2.5% mole, it can be made into an adhesive composition that hardens quickly after being coated on the adherend, and has excellent resistance to cold and heat cycles and hot water resistance.

含有羧基之段片的比例，以日本工業標準(Japanese Industrial Standard；JIS)K0070為準則，藉由電位滴定法(potentiometric titration method)或指示劑滴定法(indicator titration method)可以測定。 The ratio of the segments containing carboxyl groups can be determined by potentiometric titration method or indicator titration method based on Japanese Industrial Standard (JIS) K0070.

此處，作為共聚物，例如，乙烯/丙烯酸甲酯共聚物、乙烯/丙烯酸甲酯/丙烯酸丁酯共聚物、乙烯/甲基丙烯酸甲酯共聚物、乙烯/醋酸乙烯酯共聚物、丁二烯/丙烯酸甲酯共聚物、丁二烯/丙烯腈共聚物、丁二烯/丙烯腈/丙烯酸酯共聚物、和丁二烯/苯乙烯/丙烯腈/丙烯酸甲酯共聚物等，可以列舉使用。這些共聚物，以乙烯/丙烯酸甲酯共聚物、乙烯/丙烯酸甲酯/丙烯酸丁酯共聚物特別合於理想；又，也可以使用在前述各種共聚物裡的單體物、和丙烯酸及/或甲基丙烯酸等的含羧基單體物聚合而成的共聚物。這些共聚物可以單獨使用一種，也可以二種以上合併使用，也可以併用未使用含羧基單體物之聚合物和使用含羧基單體物之聚合物。 Here, as the copolymer, for example, ethylene/methyl acrylate copolymer, ethylene/methyl acrylate/butyl acrylate copolymer, ethylene/methyl methacrylate copolymer, ethylene/vinyl acetate copolymer, butadiene /Methyl acrylate copolymer, butadiene/acrylonitrile copolymer, butadiene/acrylonitrile/acrylate copolymer, and butadiene/styrene/acrylonitrile/methyl acrylate copolymer, etc., can be cited and used. Among these copolymers, ethylene/methyl acrylate copolymers and ethylene/methyl acrylate/butyl acrylate copolymers are particularly desirable; in addition, monomers in the aforementioned various copolymers, and acrylic acid and/or A copolymer formed by polymerizing carboxyl group-containing monomers such as methacrylic acid. These copolymers may be used alone, or two or more of them may be used in combination, or a polymer that does not use a carboxyl group-containing monomer and a polymer that uses a carboxyl group-containing monomer may be used in combination.

彈性塑料的平均分子量並無特別的限制，但是數目平均分子量(Mn)以5000~500000為理想，尤其是15000~150000、更進而20000~100000更合於理想。彈性塑料的數目平均分子量若是5000~500000的話，彈性塑料很容易溶解於2-氰基丙烯酸酯之中，特別是可以作成耐冷熱循環性試驗後的高黏著強度的黏著劑組成物。又，彈性塑料的重量平均分子量(weight-average molecular weight；Mw)以5000~1000000為理想，尤其是10000~1000000更合於理想；Mw/Mn以1.00~10.0為理想，尤其是1.00~9.0更合於理想。 The average molecular weight of the elastic plastic is not particularly limited, but the number average molecular weight (Mn) is preferably 5,000 to 500,000, especially 15,000 to 150,000, and more preferably 20,000 to 100,000. If the number average molecular weight of the elastic plastic is 5,000 to 500,000, the elastic plastic is easily dissolved in 2-cyanoacrylate, and it can be especially made into an adhesive composition with high adhesive strength after the thermal cycle resistance test. In addition, the weight-average molecular weight (Mw) of the elastic plastic is ideally 5000~1000000, especially 10000~1000000 is more ideal; Mw/Mn is ideally 1.00~10.0, especially 1.00~9.0. In line with ideals.

黏著劑組成物中的前述(c)彈性塑料的含量，以2-氰基丙烯酸酯當作100質量部分的情形時，其含量為5~50質量部分。彈性塑料的含量也因為2-氰基丙烯酸酯和具有水解性矽烷基的聚合物的種類而定，10~45質量部分是合於理想的，15~40質量部分會更合於理想。彈性塑料的含量如果是5~50質量部分的話，則可以與2-氰基丙烯酸酯和具有水解性矽烷基的聚合物安定地相容，其結果，可以作成具有優良黏著功能的黏著劑組成物。 The content of the aforementioned (c) elastic plastic in the adhesive composition is 5-50 parts by mass when 2-cyanoacrylate is taken as 100 parts by mass. The content of the elastic plastic also depends on the type of 2-cyanoacrylate and the polymer with hydrolyzable silyl group. The 10~45 mass part is ideal, and the 15~40 mass part is more ideal. If the content of the elastic plastic is 5-50 parts by mass, it can be stably compatible with 2-cyanoacrylate and the polymer with hydrolyzable silyl group. As a result, an adhesive composition with excellent adhesive function can be made .

前述『(d)酸催化劑』《本說明書中，也可略稱為『(d)成分』》係前述(b)具水解性矽烷基的聚合物的硬化催化劑。作為酸催化，以25℃時酸解離常數4以下的酸是合於理想的，前述酸解離常數3.0以下者更合於理想。若是酸解離常數4以下的酸的話，實際應用時，黏著劑組成物可以在適當速度下硬化。此酸催化劑的具體實例有自磺酸(sulfonic acid)、磷酸(phosphoric acid)、磷酸單酯(phosphoric mono)、磷酸二酯(phosphoric diester)、亞磷酸(phosphorous acid)、及亞磷酸酯(phosphorous ester)等可列舉使用。這些酸中，從硬化性觀點來看，磺酸、磷酸、磷酸單酯、及磷酸二酯是較合於理想的。 The aforementioned "(d) acid catalyst" "In this specification, it may also be abbreviated as ""(d) component""" is a curing catalyst for the aforementioned (b) polymer having a hydrolyzable silyl group. As acid catalysis, an acid with an acid dissociation constant of 4 or less at 25°C is ideal, and an acid with an acid dissociation constant of 3.0 or less is more desirable. If it is an acid with an acid dissociation constant of 4 or less, the adhesive composition can be cured at an appropriate speed in practical applications. Specific examples of this acid catalyst include sulfonic acid, phosphoric acid, phosphoric monoester, phosphoric diester, phosphorous acid, and phosphorous acid. Ester) etc. can be listed and used. Among these acids, sulfonic acid, phosphoric acid, phosphoric acid monoester, and phosphoric acid diester are more preferable from the viewpoint of curability.

黏著劑組成物中前述(d)酸催化劑的含量，將2-氰基丙烯酸酯當作100質量部分的情形時，係0.0005~0.5質量部分；酸催化劑的含量為0.001~0.4質量部分是合於理想的、0.0015~0.3質量部分是更合於理想的。酸催化劑的含量為0.0005~0.5質量部分的話，可以得到良好的硬化性，並且，對於黏著劑組成物的貯存穩定性不會有很大的不良影響。 The content of the aforementioned (d) acid catalyst in the adhesive composition, when 2-cyanoacrylate is regarded as 100 parts by mass, is 0.0005 to 0.5 parts by mass; the content of acid catalyst is 0.001 to 0.4 by mass. The ideal, 0.0015~0.3 mass part is more ideal. If the content of the acid catalyst is 0.0005 to 0.5 parts by mass, good hardenability can be obtained, and the storage stability of the adhesive composition will not be greatly adversely affected.

前述『(e)含有下述化學式(1)所表之鎓鹽』《本說明書中，也可略稱為『(e)成分』》，作為黏著劑組成物的硬化促進劑的功能，同時也使貯存穩定性提高。 The aforementioned "(e) contains an onium salt represented by the following chemical formula (1)" "In this specification, it may also be abbreviated as "component (e)"", which functions as a hardening accelerator for the adhesive composition and also Improve storage stability.

C+A-……(1) C + A - ...... (1)

《化學式中，C+係鎓鹽陽離子(onium cation)；A-係兩個(氟磺醯基)醯亞銨(bis(fluorosulfonyl)imide)陰離子。》 In the chemical formula, C + is an onium cation; A - is two (fluorosulfonyl) imide anions. 》

作為前述鎓鹽陽離子，例如，下述化學式(4)所表示之鎓鹽陽離子、咪唑鹽陽離子(imidazolium cation)、吡啶陽離子(pyridinium cation)、和化學式(5)所表之鎓鹽陽離子，可列舉使用。 As the aforementioned onium salt cation, for example, the onium salt cation represented by the following chemical formula (4), imidazolium cation, pyridinium cation, and the onium salt cation represented by the chemical formula (5) include: use.

Figure 105120025-A0305-02-0028-3
《化學式(4)中，R3~R6係各自獨立，選自烷基、環烷基、芳基、芳代脂烷基(aralkyl)、烯基(alkenyl)、及炔基(alkynyl)所成群類的化學基，前述化學基也可以用取代基取代；或者R3~R6的一部分或全部，與A所示的原子結合在一起，作成無取代或取代的3~10個原 子的環〔此處，該環也可以包含氧(O)、硫(S)等的異(hetero)原子〕，與該環之作成無關的R3~R6係如前述之定義；因此，A係表示氮原子或磷原子。再者，前述取代的烷基的具體實例，如烷氧基(alkoxy)和烷醯基(alkanoyl)可列舉使用。前述烷基的碳數較理想的是1~20，更理想的是1~16；又，R3~R6的一部分作成環的情形時，通常，R3~R6之中的二或三個作成環；R3~R6的二個作成環的化學式(4)化合物的具體實例，可列舉的有：哌啶鎓(piperidinium)陽離子、嗎啉鎓(morpholinium)陽離子、吡咯烷鎓(pyrrolidinium)陽離子等。》
Figure 105120025-A0305-02-0028-3
 In the chemical formula (4), R 3 ~ R 6 are each independently selected from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, alkenyl, and alkynyl. Groups of chemical groups, the aforementioned chemical groups may also be substituted with substituents; or part or all of R 3 to R 6 may be combined with the atoms shown in A to form unsubstituted or substituted 3-10 atoms Ring [here, the ring may also contain hetero atoms such as oxygen (O), sulfur (S), etc.], and R 3 to R 6 irrelevant to the formation of the ring are as defined above; therefore, the A system Represents a nitrogen atom or a phosphorus atom. Furthermore, specific examples of the aforementioned substituted alkyl groups such as alkoxy and alkanoyl can be cited and used. The carbon number of the aforementioned alkyl group is preferably 1 to 20, and more preferably 1 to 16. In addition, when a part of R 3 to R 6 forms a ring, usually, two or three of R 3 to R 6 Specific examples of the compound of formula (4) in which two of R 3 to R 6 are formed into a ring include: piperidinium cation, morpholinium cation, pyrrolidinium ) Cation etc. 》

Figure 105120025-A0305-02-0029-4
《化學式(5)中，R7~R9係各自獨立，選自烷基、環烷基、芳基、芳代脂烷基(aralkyl)、烯基(alkenyl)、和炔基(alkynyl)所成群類的化學基，前述化學基也可以用取代基取代；或者R7~R9的一部分或全部，與硫原子結合在一起，作成無取代或取代的3~10個原子的環〔此處，該環也可以包含氧(O)、硫(S)等的異(hetero)原子〕，與該環之作成無關的R7~R9係如前述之定義；再者，前述取代的烷基的具體實例，如烷氧基(alkoxy)和烷醯基(alkanoyl)可列舉使用。前述烷基的碳 數較理想的是1~20，更理想的是1~16。》
Figure 105120025-A0305-02-0029-4
 In the chemical formula (5), R 7 ~ R 9 are each independently selected from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, alkenyl, and alkynyl. Groups of chemical groups, the aforementioned chemical groups may also be substituted with substituents; or part or all of R 7 to R 9 are combined with sulfur atoms to form an unsubstituted or substituted ring of 3 to 10 atoms [here Where, the ring may also contain hetero atoms such as oxygen (O), sulfur (S), etc.], and R 7 to R 9 irrelevant to the formation of the ring are defined as described above; in addition, the aforementioned substituted alkane Specific examples of the group, such as alkoxy and alkanoyl can be cited and used. The carbon number of the aforementioned alkyl group is preferably 1-20, and more preferably 1-16. 》

前述化學式(4)所表示之鎓鹽陽離子的代表實例，可列舉使用的有：四級銨陽離子(quaternary ammonium cation)、四級膦陽離子(quaternary phosphonium cation)等。 Representative examples of the onium salt cation represented by the aforementioned chemical formula (4) include quaternary ammonium cation, quaternary phosphonium cation, and the like.

四級銨陽離子(quaternary ammonium cation)的具體實例，可列舉使用的有：四甲基銨(tetramethyl ammonium)、乙基三甲基銨、二乙基二甲基銨、三乙基甲基銨、四乙基銨、四-正-丁基銨、三甲基正-丙基銨(trimethyl n-propyl ammonium)、三甲基異丙基銨、正-丁基三甲基銨、異丁基三甲基銨、特-丁基三甲基銨(t-butyl trimethyl ammonium)、正-己基三甲基銨、二甲基二正-丙基銨、二甲基二異丙基銨、二甲基-正-丙基異丙基銨、甲基三-正-丙基銨、甲基三異丙基銨、甲基二-正-丙基異丙基銨、甲基-正-丙基二異丙基銨、甲基三-正-辛基銨(methyl tri-n-octyl ammonium)、三乙基-正-丙基銨、三乙基異丙基銨、正-丁基三乙基銨、三乙基異丁基銨、特-丁基三乙基銨、二-正-丁基二甲基銨、二異丁基二甲基銨、二-特-丁基二甲基銨、正-丁 基乙基二甲基銨、異丁基乙基二甲基銨、特-丁基乙基二甲基銨、正-丁基異丁基二甲基銨、正-丁基-特-丁基二甲基銨、特-丁基異丁基二甲基銨、二乙基二-正-丙基銨、二乙基二異丙基銨、二乙基-正-丙基異丙基銨、乙基三-正-丙基銨、乙基三異丙基銨、乙基異丙基二-正-丙基銨、乙基二異丙基-正-丙基銨、二乙基甲基-正-丙基銨、乙基二甲基-正-丙基銨、乙基甲基二-正-丙基銨、二乙基異丙基甲基銨、乙基異丙基二甲基銨、乙基二異丙基甲基銨、乙基甲基-正-丙基異丙基銨、四-正-丙基銨、四異丙基銨、三異丙基-正-丙基銨、二異丙基二-正-丙基銨、異丙基三-正-丙基銨、丁基三甲基銨、三甲基戊基銨(trimethyl pentyl ammonium)、己基三甲基銨(hexyl trimethyl ammonium)、庚基三甲基銨(heptyl trimethyl ammonium)、三甲基辛基銨(trimethyl octyl ammonium)、三甲基壬基銨(trimethyl nonyl ammonium)、癸基三甲基銨(decyl trimethyl ammonium)、三甲基十一烷基(trimethyl undecyl ammonium)、十二烷基三甲基銨(dodecyl trimethyl ammonium)、二癸基二甲基銨、二月桂基二甲基銨(dilauryl dimethyl ammonium)、二甲基二苯乙烯基銨(dimethyl distyryl ammonium)、二甲基二(十八烷基)銨(dimethyl dioctadecyl ammonium)、二甲基二辛基銨(dimethyl dioctyl ammonium)、二甲基二棕櫚基銨(dimethyl dipalmityl ammonium)、乙基十六烷基二甲基銨(ethyl hexadecyl dimethyl ammonium)、己基二甲基辛基銨、十二烷基(二茂鐵基甲基)二甲基銨(dodecyl(ferrocenylmethyl)dimethyl ammonium)、N-甲基後馬托品(N-Methyl homatropininium)等的四烷基銨陽離子(tetraalkyl ammonium cation)；苄基三甲基銨(benzyl trimethyl ammonium)、苄基三丁基銨、苄基十二烷基二甲基銨等的芳香族烷基取代銨陽離子；三甲基苯基銨(trimethylphenyl ammonium)、四苯基銨等的芳香族取代銨陽離子；吡咯烷鎓(pyrrolidinium)《例如，1,1-二甲基吡咯烷鎓、1-乙基-1-甲基吡咯烷鎓、1,1-二乙基吡咯烷鎓、1,1-四甲撐吡咯烷鎓(1,1-tetramethylene pyrrolidinium)、1-甲基-1-丙基吡咯烷鎓、1-乙基-1-丙基吡咯烷鎓、1-丁基-1-甲基吡咯烷鎓》、啶鎓(piperidinium)《例如，1,1-二甲基哌啶鎓、1-乙基-1-甲基哌啶鎓、1,1-二乙基哌啶鎓、1-甲基-1-丙基哌啶鎓、1-乙基-1-丙基哌啶鎓、1-丁基-1-甲基哌啶鎓》、嗎啉鎓(morpholinium)《例如，1,1-二甲基嗎啉鎓、1-乙基-1-甲基嗎啉鎓、1,1-二乙基嗎啉鎓》等的脂肪族環狀銨陽離子等。 Specific examples of quaternary ammonium cation include: tetramethyl ammonium, ethyl trimethyl ammonium, diethyl dimethyl ammonium, triethyl methyl ammonium, Tetraethyl ammonium, tetra-n-butyl ammonium, trimethyl n-propyl ammonium, trimethyl isopropyl ammonium, n-butyl trimethyl ammonium, isobutyl tri Methyl ammonium, t-butyl trimethyl ammonium, n-hexyl trimethyl ammonium, dimethyl di-n-propyl ammonium, dimethyl diisopropyl ammonium, dimethyl ammonium -N-propyl isopropyl ammonium, methyl tri-n-propyl ammonium, methyl triisopropyl ammonium, methyl di-n-propyl isopropyl ammonium, methyl-n-propyl diiso Propylammonium, methyl tri-n-octyl ammonium, triethyl-n-propylammonium, triethylisopropylammonium, n-butyltriethylammonium, Triethylisobutylammonium, tert-butyltriethylammonium, di-n-butyldimethylammonium, diisobutyldimethylammonium, di-tert-butyldimethylammonium, n- Ding Ethyl ethyl dimethyl ammonium, isobutyl ethyl dimethyl ammonium, tert-butyl ethyl dimethyl ammonium, n-butyl isobutyl dimethyl ammonium, n-butyl-tert-butyl Dimethylammonium, tert-butylisobutyldimethylammonium, diethyldi-n-propylammonium, diethyldiisopropylammonium, diethyl-n-propylisopropylammonium, Ethyl tri-n-propyl ammonium, ethyl triisopropyl ammonium, ethyl isopropyl di-n-propyl ammonium, ethyl diisopropyl-n-propyl ammonium, diethyl methyl- N-propylammonium, ethyldimethyl-n-propylammonium, ethylmethyldi-n-propylammonium, diethylisopropylmethylammonium, ethylisopropyldimethylammonium, Ethyl diisopropyl methyl ammonium, ethyl methyl-n-propyl isopropyl ammonium, tetra-n-propyl ammonium, tetraisopropyl ammonium, triisopropyl-n-propyl ammonium, two Isopropyl di-n-propyl ammonium, isopropyl tri-n-propyl ammonium, butyl trimethyl ammonium, trimethyl pentyl ammonium, hexyl trimethyl ammonium ), heptyl trimethyl ammonium, trimethyl octyl ammonium, trimethyl nonyl ammonium, decyl trimethyl ammonium, Trimethyl undecyl ammonium, dodecyl trimethyl ammonium, didecyl dimethyl ammonium, dilauryl dimethyl ammonium, dimethyl ammonium Dimethyl distyryl ammonium (dimethyl distyryl ammonium), dimethyl dioctadecyl ammonium (dimethyl dioctadecyl ammonium), dimethyl dioctyl ammonium (dimethyl dioctyl ammonium), dimethyl dipalmityl ammonium ( dimethyl dipalmityl ammonium), ethyl cetyl dimethyl ammonium (ethyl hexadecyl dimethyl ammonium), hexyl dimethyl octyl ammonium, dodecyl (ferrocenyl methyl) dimethyl ammonium (dodecyl (ferrocenyl methyl) dimethyl ammonium), N-methyl homatropine (N-Methyl tetraalkyl ammonium cation such as homatropininium; aromatic alkyl groups such as benzyl trimethyl ammonium, benzyl tributyl ammonium, benzyl dodecyl dimethyl ammonium, etc. Substituted ammonium cation; aromatic substituted ammonium cations such as trimethylphenyl ammonium and tetraphenyl ammonium; pyrrolidinium (for example, 1,1-dimethylpyrrolidinium, 1-ethyl 1-methylpyrrolidinium, 1,1-diethylpyrrolidinium, 1,1-tetramethylene pyrrolidinium (1,1-tetramethylene pyrrolidinium), 1-methyl-1-propylpyrrole Alkanium, 1-ethyl-1-propylpyrrolidinium, 1-butyl-1-methylpyrrolidinium", piperidinium"For example, 1,1-dimethylpiperidinium, 1 -Ethyl-1-methylpiperidinium, 1,1-diethylpiperidinium, 1-methyl-1-propylpiperidinium, 1-ethyl-1-propylpiperidinium, 1 -Butyl-1-methylpiperidinium", morpholinium"For example, 1,1-dimethylmorpholinium, 1-ethyl-1-methylmorpholinium, 1,1- Aliphatic cyclic ammonium cations such as diethylmorpholinium.

又，四級膦陽離子(quaternary phosphonium cation)的具體實例，可列舉使用的有：四甲基膦(tetramethyl phosphonium)、三乙基甲基膦、 四乙基膦等的陽離子。 In addition, specific examples of quaternary phosphonium cation include: tetramethyl phosphonium, triethylmethyl phosphine, Cations such as tetraethylphosphine.

咪唑鎓(imidazolium)陽離子(cation)的具體實例，可列舉使用的有：1,3-二甲基咪唑鎓、1,2,3-三甲基咪唑鎓、1-乙基-3-甲基咪唑鎓、1-乙基-2,3-二甲基咪唑鎓、1-甲基-3-正-辛基咪唑鎓、1-己基-3-甲基咪唑鎓、1,3-二乙基咪唑鎓、1,2-二乙基-3-甲基咪唑鎓、1,3-二乙基-2-甲基咪唑鎓、1,2-二甲基-3-正-丙基咪唑鎓、1-正-丁基-3-甲基咪唑鎓、1-正-丁基-2,3-二甲基咪唑鎓、1,2,4-三甲基-3-正-丙基咪唑鎓、1,2,3,4-四甲基咪唑鎓、1,2,3,4,5-五甲基咪唑鎓、2-乙基-1,3-二甲基咪唑鎓、1,3-二甲基-2-正-丙基咪唑鎓、1,3-二甲基-2-正-戊基咪唑鎓、2-正-庚基-1,3-二甲基咪唑鎓、1,3,4-三甲基咪唑鎓、2-乙基-1,3,4-三甲基咪唑鎓、1,3-二甲基苯並咪唑鎓(1,3-dimethyl benzoimidazolium)、3-甲基-1-苯基咪唑鎓(3-methyl-1-phenyl imidazole)、1-苄基-3-甲基咪唑鎓(1-benzyl-3-methyl imidazole)、2,3-二甲基-1-苯基咪唑鎓、1-苄基-2,3-二甲基咪唑鎓、1,3-二甲基-2-苯基咪唑鎓、2-苄基-1,3-二甲基咪唑鎓、1,3-二甲基-2-正-十一烷基咪唑鎓、1,3-二甲基-2-正-十七烷基咪唑鎓等的陽離子。 Specific examples of imidazolium cations include: 1,3-dimethylimidazolium, 1,2,3-trimethylimidazolium, 1-ethyl-3-methyl Imidazolium, 1-ethyl-2,3-dimethylimidazolium, 1-methyl-3-n-octylimidazolium, 1-hexyl-3-methylimidazolium, 1,3-diethyl Imidazolium, 1,2-diethyl-3-methylimidazolium, 1,3-diethyl-2-methylimidazolium, 1,2-dimethyl-3-n-propylimidazolium, 1-n-butyl-3-methylimidazolium, 1-n-butyl-2,3-dimethylimidazolium, 1,2,4-trimethyl-3-n-propylimidazolium, 1,2,3,4-tetramethylimidazolium, 1,2,3,4,5-pentamethylimidazolium, 2-ethyl-1,3-dimethylimidazolium, 1,3-di Methyl-2-n-propylimidazolium, 1,3-dimethyl-2-n-pentylimidazolium, 2-n-heptyl-1,3-dimethylimidazolium, 1,3, 4-trimethylimidazolium, 2-ethyl-1,3,4-trimethylimidazolium, 1,3-dimethyl benzoimidazolium (1,3-dimethyl benzoimidazolium), 3-methyl- 1-phenyl imidazole (3-methyl-1-phenyl imidazole), 1-benzyl-3-methyl imidazole (1-benzyl-3-methyl imidazole), 2,3-dimethyl-1-benzene 1-benzyl-2,3-dimethylimidazolium, 1,3-dimethyl-2-phenylimidazolium, 2-benzyl-1,3-dimethylimidazolium, 1 , 3-dimethyl-2-n-undecylimidazolium, 1,3-dimethyl-2-n-heptadecylimidazolium and other cations.

吡啶鎓陽離子(pyridinium cation)的具體實例，可列舉使用的有：1-甲基吡啶鎓、1-乙基吡啶鎓、1-正-丙基吡啶鎓、1-異丙基吡啶鎓、1-正-丁基吡啶鎓、1-丁基-3-甲基吡啶鎓等的陽離子。 Specific examples of pyridinium cation include: 1-methylpyridinium, 1-ethylpyridinium, 1-n-propylpyridinium, 1-isopropylpyridinium, 1- Cations such as n-butylpyridinium and 1-butyl-3-methylpyridinium.

前述化學式(5)所表示之三級硫鎓陽離子(tertiary sulfonium cation)的具體實例，可列舉使用的有：三甲基硫鎓、三乙基硫鎓、三丙基硫鎓、三苯基硫鎓等的陽離子。 Specific examples of tertiary sulfonium cation represented by the aforementioned chemical formula (5) include: trimethylsulfonium, triethylsulfonium, tripropylsulfonium, and triphenylsulfonium. Cations such as onium.

前述鎓陽離子之中，對2-氰基丙烯酸酯的溶解度優良、以及促進硬化的性能和黏著劑組成物的貯存安定性的平衡的觀點來看，四級銨陽離子、咪唑鎓陽離子、吡啶鎓陽離子或三級硫鎓陽離子較合於理想，而四級銨陽離子、咪唑鎓陽離子或吡啶鎓陽離子又更合於理想。 Among the aforementioned onium cations, quaternary ammonium cations, imidazolium cations, and pyridinium cations are excellent in solubility for 2-cyanoacrylate, and in terms of the balance between the performance of promoting hardening and the storage stability of the adhesive composition. Or tertiary sulfonium cations are more ideal, while quaternary ammonium cations, imidazolium cations or pyridinium cations are more ideal.

其次，前述鎓鹽的陰離子，係兩個(氟磺醯基)醯亞銨(bis(fluorosulfonyl)imide)陰離子。由於兩個(氟磺醯基)醯亞銨陰離子 幾乎沒有親核性(nucleophilicity)，作為鎓鹽，即使存在於黏著劑組成物中，對於黏著劑組成物的貯存安定性不會有壞的影響；另一方面，因為該當陰離子的共軛酸(conjugate acid)是強酸，藉由與被黏物質表面些許的鹽類發生反應，顯示親核性，使可能是2-氰基丙烯酸酯的聚合起始劑的陰離子游離出來，結果，即使被黏物質是金屬及/或極性很低的熱可塑性彈性塑料的情形下，也可以呈現優良的黏著速度。 Second, the anion of the aforementioned onium salt is two (fluorosulfonyl) imide anions. Due to the two (fluorosulfonyl) iminium anions Almost no nucleophilicity (nucleophilicity), as an onium salt, even if it exists in the adhesive composition, it will not have a bad effect on the storage stability of the adhesive composition; on the other hand, because the conjugate acid ( Conjugate acid) is a strong acid. By reacting with some salts on the surface of the adherend, it shows nucleophilicity and frees the anion of the polymerization initiator that may be 2-cyanoacrylate. As a result, even the adherend In the case of metal and/or thermoplastic elastic plastics with very low polarity, it can also exhibit excellent adhesion speed.

本發明中所使用之鎓鹽，只要是前述陽離子和陰離子組合的話，並無特別的限制。鎓鹽的具體實例，可列舉使用的有四乙基銨兩個(氟磺醯基)醯亞胺(tetraethyl ammonium bis(fluorosulfonyl)imide)、四-正-丁基銨兩個(氟磺醯基)醯亞胺、甲基三-正-辛基銨兩個(氟磺醯基)醯亞胺、戊基三乙基銨兩個(氟磺醯基)醯亞胺、環己基三甲基銨兩個(氟磺醯基)醯亞胺、1-乙基-3-甲基咪唑鎓兩個(氟磺醯基)醯亞胺(1-ethyl-3-methyl imidazolium bis(fluorosulfonyl)imide)、1-乙基-2,3-二甲基咪唑鎓兩個(氟磺醯基)醯亞胺、1-丁基-3-甲基咪唑鎓兩個(氟磺醯基)醯亞胺、1-丁基-2,3-二甲基咪唑鎓兩個(氟磺醯基)醯亞胺、1-甲基-3-正-辛基咪唑鎓兩個(氟磺醯基)醯亞胺、1-己基-3-甲基咪唑鎓兩個(氟磺醯基)醯亞胺、2-乙基-1,3-二甲基咪唑鎓兩個(氟磺醯基)醯亞胺、1,3- 二甲基-2-正-丙基咪唑鎓兩個(氟磺醯基)醯亞胺、1,3-二甲基-2-正-戊基咪唑鎓兩個(氟磺醯基)醯亞胺、2-正-庚基-1,3-二甲基咪唑鎓兩個(氟磺醯基)醯亞胺、1-乙基-1-甲基哌啶鎓兩個(氟磺醯基)醯亞胺(1-ethyl-1-methyl piperidinium bis(fluorosulfonyl)imide)、1-丁基-1-甲基哌啶鎓兩個(氟磺醯基)醯亞胺、1-甲基-1-丙基哌啶鎓兩個(氟磺醯基)醯亞胺、1-乙基-1-丙基哌啶鎓兩個(氟磺醯基)醯亞胺、四正丁基銨兩個(氟磺醯基)醯亞胺(tetra-n-butyl ammonium bis(fluorosulfonyl)imide)、三甲基辛基銨兩個(氟磺醯基)醯亞胺、甲基三-正-辛基銨兩個(氟磺醯基)醯亞胺、苄基三丁基銨兩個(氟磺醯基)醯亞胺(benzyl tributyl ammonium bis(fluorosulfonyl)imide)、1-乙基-1-甲基吡咯烷鎓雙(三氟甲烷磺醯基)醯亞胺(1-ethyl-1-methyl pyrrolidinium bis(fluorosulfonyl)imide)、1-丁基-1-甲基吡咯烷鎓兩個(氟磺醯基)醯亞胺、1-甲基-1-丙基吡咯烷鎓兩個(氟磺醯基)醯亞胺、1-乙基-1-丙基吡咯烷鎓兩個(氟磺醯基)醯亞胺、1-乙基吡啶鎓兩個(氟磺醯基)醯亞胺(1-ethyl pyridinium bis(fluorosulfonyl)imide)、1-乙基-3-甲基吡啶鎓兩個(氟磺醯基)醯亞胺、1-丁基-3-甲基吡啶鎓兩個(氟磺醯基)醯亞胺、1-乙基-4-甲基吡啶鎓兩個(氟磺醯基)醯亞胺、1-丁基吡啶鎓兩個(氟磺醯基)醯亞胺、1-丁基-4-甲基吡啶鎓兩個(氟磺醯基)醯亞胺、四乙基膦兩個(氟磺醯基)醯亞胺(tetraethyl phosphonium bis(fluorosulfonyl)imide)、三乙基硫鎓兩 個(氟磺醯基)醯亞胺(triethylsulfonium bis(fluorosulfonyl)imide)、三乙基甲基膦兩個(氟磺醯基)醯亞胺等。這些鎓鹽，可以單獨使用一種，也可以二種以上合併使用。 The onium salt used in the present invention is not particularly limited as long as it is a combination of the aforementioned cation and anion. Specific examples of onium salts include tetraethyl ammonium bis (fluorosulfonyl) imide and tetra-n-butyl ammonium two (fluorosulfonyl) imide. ) Imines, two methyl tri-n-octyl ammonium (fluorosulfonyl) imines, two pentyl triethyl ammonium (fluorosulfonyl) imines, cyclohexyl trimethyl ammonium Two (fluorosulfonyl) imide, 1-ethyl-3-methyl imidazolium two (fluorosulfonyl) imide (1-ethyl-3-methyl imidazolium bis(fluorosulfonyl) imide), Two 1-ethyl-2,3-dimethylimidazolium (fluorosulfonyl) imides, 1-butyl-3-methylimidazolium two (fluorosulfonyl) imides, 1 -Butyl-2,3-dimethylimidazolium two (fluorosulfonyl) imide, 1-methyl-3-n-octyl imidazolium two (fluorosulfonyl) imide, Two 1-hexyl-3-methylimidazolium (fluorosulfonyl) imines, 2-ethyl-1,3-dimethylimidazolium two (fluorosulfonyl) imides, 1, 3- Two dimethyl-2-n-propylimidazolium (fluorosulfonyl) imines, 1,3-dimethyl-2-n-pentylimidazolium two (fluorosulfonyl) imides Amine, two 2-n-heptyl-1,3-dimethylimidazolium (fluorosulfonyl) imine, two 1-ethyl-1-methylpiperidinium (fluorosulfonyl) 1-ethyl-1-methyl piperidinium bis(fluorosulfonyl)imide, 1-butyl-1-methyl piperidinium two (fluorosulfonyl) imide, 1-methyl-1- Two propylpiperidinium (fluorosulfonyl) imines, two 1-ethyl-1-propylpiperidinium (fluorosulfonyl) imines, two tetra-n-butylammonium (fluoro Tetra-n-butyl ammonium bis (fluorosulfonyl) imide, two trimethyl octyl ammonium (fluorosulfonyl) imide, two methyl tri-n-octyl ammonium (Fluorosulfonyl) imide, benzyl tributyl ammonium two (benzyl tributyl ammonium bis(fluorosulfonyl) imide), 1-ethyl-1-methylpyrrolidinium Bis (trifluoromethanesulfonyl) imide (1-ethyl-1-methyl pyrrolidinium bis (fluorosulfonyl) imide), 1-butyl-1-methyl pyrrolidinium two (fluorosulfonyl) imide Amine, two 1-methyl-1-propylpyrrolidinium (fluorosulfonyl) imide, 1-ethyl-1-propylpyrrolidinium two (fluorosulfonyl) imide, 1-ethyl pyridinium bis(fluorosulfonyl) imide, 1-ethyl pyridinium bis(fluorosulfonyl) imide, 1-ethyl-3-methylpyridinium two (fluorosulfonyl) imide Amine, 1-butyl-3-methylpyridinium two (fluorosulfonyl) imines, 1-ethyl-4-methylpyridinium two (fluorosulfonyl) imides, 1- Two butylpyridinium (fluorosulfonyl) imines, 1-butyl-4-methylpyridinium two (fluorosulfonyl) imines, two tetraethyl phosphine (fluorosulfonyl) ) Tetraethyl phosphonium bis (fluorosulfonyl) imide, triethyl sulfonium two One (fluorosulfonyl) imide (triethylsulfonium bis (fluorosulfonyl) imide), triethylmethyl phosphine and two (fluorosulfonyl) imide. These onium salts may be used singly or in combination of two or more kinds.

本發明之鎓鹽，可以依照一般習知的方法製造，舉例來說，Hiroyuki Ohno等人發表於J.Am.Chem.Soc.,2005,27,2398-2399或Peter Wasserscheid等人發表於Green Chemistry,2002,4,134-138之內容，從對應的鎓鹽重點可以製造出來。 The onium salt of the present invention can be produced according to a generally known method. For example, Hiroyuki Ohno et al. published in J. Am. Chem. Soc., 2005, 27, 2398-2399 or Peter Wasserscheid et al. in Green Chemistry. , 2002, 4, 134-138, can be manufactured from the corresponding onium salt.

黏著劑組成物中的前述(e)鎓鹽的含量，將(a)2-氰基丙烯酸酯設為100質量部分的情形時，則鎓鹽含量為0.001~5質量部分，前述含量為0.005~3質量部分是合於理想的，更合於理想的是0.01~2質量部分。鎓鹽含量為0.001~5質量部分的話，則可以作為硬化促進劑，同時對黏著劑組成物的貯存穩定性不會有不良影響。 When the content of the aforementioned (e) onium salt in the adhesive composition is 100 parts by mass of (a) 2-cyanoacrylate, the content of onium salt is 0.001 to 5 parts by mass, and the aforementioned content is 0.005~ The 3 mass part is ideal, and the more ideal is 0.01~2 mass part. If the content of onium salt is 0.001 to 5 parts by mass, it can be used as a hardening accelerator and will not adversely affect the storage stability of the adhesive composition.

如前述，本發明之黏著劑組成物含有成分(a)~(e)，伴隨著(a)2- 氰基丙烯酸酯和(b)具水解性矽烷基之聚合物的聚合，(a)2-氰基丙烯酸酯、(b)具水解性矽烷基之聚合物和(c)彈性塑料發生相分離(phase separation)，(a)2-氰基丙烯酸酯變成瀰散相(dispersed phase)，而(b)具水解性矽烷基之聚合物和(c)彈性塑料變成柔韌的連續相(continuous phase)，形成海島結構(sea-island structure)。此際，(b)具水解性矽烷基之聚合物由於三維交聯(three-dimensional cross-linked)所致，(a)2-氰基丙烯酸酯的聚合物在黏著持久性試驗後也就保留在瀰散相而被固定；像這樣的海島結構由於被固定，黏著劑硬化物，在耐熱性(heat resistance)、耐濕熱性(moist heat resistance)、耐熱水性、和耐冷熱循環性(thermal cycle resistance)等的持久性試驗後，也可以維持高黏著強度。又，黏著劑組成物可以得到柔韌性優良的硬化物。 As mentioned above, the adhesive composition of the present invention contains components (a) to (e), accompanied by (a) 2- The polymerization of cyanoacrylate and (b) polymer with hydrolyzable silyl group, (a) 2-cyanoacrylate, (b) polymer with hydrolyzable silyl group, and (c) elastomeric plastic phase separation ( phase separation), (a) 2-cyanoacrylate becomes a dispersed phase, and (b) a polymer with hydrolyzable silane groups and (c) an elastic plastic becomes a flexible continuous phase, forming Sea-island structure. At this time, (b) the polymer with hydrolyzable silyl group was caused by three-dimensional cross-linked, (a) the polymer of 2-cyanoacrylate remained after the adhesion durability test It is fixed in the dispersive phase; the sea-island structure like this is fixed, and the adhesive hardened material has the advantages of heat resistance, moist heat resistance, hot water resistance, and thermal cycle resistance. ) After the durability test, the high adhesive strength can be maintained. In addition, the adhesive composition can provide a cured product with excellent flexibility.

本發明之黏著劑組成物中，為了提高黏著性和貯存穩定性，也可以含有矽烷偶聯劑(silane coupling agent)，作為矽烷偶聯劑，可以廣泛使用一般熟知的矽烷偶聯劑，例如：γ-丙烯醯氧基丙基三甲氧基矽烷(γ-acryloxypropyl trimethoxy silane)、γ-丙烯醯氧基丙基三乙氧基矽烷、γ-丙烯醯氧基丙基甲基二甲氧基矽烷、γ-丙烯醯氧基丙基甲基二乙氧基矽烷等的丙烯醯基矽烷(acryl silane)；γ-巰基丙基三甲 氧基矽烷(γ-mercaptopropyl trimethoxy silane)、γ-巰基丙基三乙氧基矽烷等的-巰基矽烷；γ-醯脲丙基三乙氧基矽烷(γ-ureide propyl triethoxy silane)、甲基三甲氧基矽烷、乙烯基三甲氧基矽烷(vinyl trimethoxy silane)等可列舉使用。這些矽烷偶聯劑可以單獨使用一種，也可以二種以上合併使用。 In order to improve the adhesiveness and storage stability, the adhesive composition of the present invention may also contain a silane coupling agent. As the silane coupling agent, commonly known silane coupling agents can be widely used, such as: γ-acryloxypropyl trimethoxy silane (γ-acryloxypropyl trimethoxy silane), γ-acryloxypropyl trimethoxy silane, γ-acryloxypropyl methyl dimethoxy silane, acryl silane such as γ-acryloxypropyl methyl diethoxysilane; γ-mercaptopropyl trimethyl Γ-mercaptopropyl trimethoxy silane, γ-mercaptopropyl triethoxy silane, etc.-mercapto silane; γ-ureide propyl triethoxy silane (γ-ureide propyl triethoxy silane), methyl trimethyl Oxysilane, vinyl trimethoxy silane, etc. can be cited and used. These silane coupling agents may be used alone or in combination of two or more.

這些矽烷偶聯劑之中，乙烯基三甲氧基矽烷在貯存穩定性這點是較為理想的。矽烷偶聯劑的使用量，將(b)具水解性矽烷基的聚合物當作100質量部分，相對於此，理想的矽烷偶聯劑的量是0.1~20質量部分，更理想的是2~10質量部分。矽烷偶聯劑是0.1~20質量部分的話，因為可以得到高的黏著性和貯存穩定性而合於理想。 Among these silane coupling agents, vinyl trimethoxysilane is more ideal in terms of storage stability. The amount of silane coupling agent used is (b) the polymer with hydrolyzable silyl group as 100 parts by mass. In contrast, the ideal amount of silane coupling agent is 0.1-20 parts by mass, and more preferably 2 ~10 quality parts. If the silane coupling agent is 0.1-20 parts by mass, it is ideal because it can obtain high adhesiveness and storage stability.

又，本發明之黏著劑組成物中，除了前述成分之外，為了因應使用目的，至今仍使用而調配在含有2-氰基丙烯酸酯的黏著劑組成物中的陰離子聚合促進劑、安定劑(stabilizer)、增塑劑(plasticizer)、增稠劑(thickening agent)、白煙矽(fumed silica)、小顆粒(particle)、填充劑(filler)、著色劑(coloring agent)、香料(flavoring agent)、溶劑、增強劑(strengthening agent)等，於無損黏著劑組成物的硬化性和黏著強度等的範圍內，可以適量調配使用。 In addition, in the adhesive composition of the present invention, in addition to the aforementioned components, the anionic polymerization accelerator and stabilizer that are still used in accordance with the purpose of use are formulated into the adhesive composition containing 2-cyanoacrylate ( stabilizer, plasticizer, thickening agent, fumed silica, particle, filler, coloring agent, flavoring agent , Solvents, strengthening agents, etc., within the range of not impairing the curability and adhesive strength of the adhesive composition, it can be used in an appropriate amount.

作為陰離子聚合促進劑，可以列舉使用的有：聚環氧烷類(polyalkylene oxide)、冠狀醚類(crown ether)、硅冠狀醚類(sila crown ether)、杯芳烴類(calixarene)、環糊精類(cyclodextrin)和焦棓酚類(pyrogallol)環狀化合物類等。 As anionic polymerization accelerators, polyalkylene oxides, crown ethers, sila crown ethers, calixarenes, and cyclodextrins can be cited and used. Cyclodextrin and pyrogallol cyclic compounds.

聚環氧烷類(polyalkylene oxide)，係指聚環氧烷及其衍生物，舉例來說，可列舉使用的有：特公昭60-37836號公報、特公平1-43790號公報、特開昭63-128088號公報、特開平3-167279號公報、美國專利第4386193號說明書、美國專利第4424327號說明書等所揭示之化合物。具體來說，有：(1)二甘醇(diethylene glycol)、三甘醇(triethylene glycol)、聚乙二醇(polyethylene glycol)、聚丙二醇(polypropylene glycol)等聚環氧烷類；(2)聚乙二醇單烷基酯(polyethylene glycol monoalkyl ester)、聚乙二醇雙烷基酯(polyethylene glycol dialkyl ester)、聚丙二醇雙烷基酯(polypropylene glycol dialkyl ester)、二甘醇單烷基酯(diethylene glycol monoalkyl ester)、二甘醇雙烷基酯(diethylene glycol dialkyl ester)、雙丙甘醇單烷基酯(dipropylene glycol monoalkyl ester)、雙丙甘醇雙烷基酯(dipropylene glycol dialkyl ester)等的聚環氧烷類的衍生物等可列舉使用。 Polyalkylene oxide (polyalkylene oxide) refers to polyalkylene oxide and its derivatives. For example, the following can be listed and used: Japanese Patent Application Publication No. 60-37836, Japanese Patent Application Publication No. 1-43790, 63-128088, JP 3-167279, U.S. Patent No. 4386193, U.S. Patent No. 4424327, etc. Specifically, there are: (1) Polyalkylene oxides such as diethylene glycol, triethylene glycol, polyethylene glycol, and polypropylene glycol; (2) Polyethylene glycol monoalkyl ester, polyethylene glycol dialkyl ester, polypropylene glycol dialkyl ester, diethylene glycol monoalkyl ester (diethylene glycol monoalkyl ester), diethylene glycol dialkyl ester, dipropylene glycol monoalkyl ester, dipropylene glycol dialkyl ester Derivatives of polyalkylene oxides and the like can be listed and used.

所謂冠狀醚類(crown ether)，例如，可列舉使用的有：特公昭55-2236號公報、特開平3-167279號公報等所揭示之化合物。具體來說，有：12-冠醚-4(12-crown-4)、15-冠醚-5、18-冠醚-6、苯並-12-冠醚-4(benzo-12-crown-4)、苯並-15-冠醚-5、苯並-18-冠醚-6、二苯並-18-冠醚-6(dibenzo-18-crown-6)、二苯並-24-冠醚-8、二苯並-30-冠醚-10、三苯並-18-冠醚-6、不對稱-二苯並-22-冠醚-6(asym-dibenzo-22-crown-6)、二苯並-14-冠醚-4、二環己基-24-冠醚-8(dicyclohexyl-24-crown-8)、環己基-12-冠醚-4、1,2-二環癸-15-冠醚-5(1,2-decalyl-15-crown-5)、1,2-萘基-15-冠醚-5(1,2-naphth-15-crown-5)、3,4,5-萘基-16-冠醚-5(3,4,5-naphthyl-16-crown-5)、1,2-甲基苯並-18-冠醚-6、1,2-特-丁基-18-冠醚-6、1,2-乙烯基苯並-15-冠醚-5等可列舉使用。 The so-called crown ethers include, for example, compounds disclosed in Japanese Patent Publication No. 55-2236 and Japanese Patent Application Publication No. 3-167279. Specifically, there are: 12-crown-4 (12-crown-4), 15-crown-5, 18-crown-6, benzo-12-crown-4 (benzo-12-crown- 4), benzo-15-crown-5, benzo-18-crown-6, dibenzo-18-crown-6 (dibenzo-18-crown-6), dibenzo-24-crown Ether-8, dibenzo-30-crown-10, tribenzo-18-crown-6, asymmetric-dibenzo-22-crown-6 (asym-dibenzo-22-crown-6) , Dibenzo-14-crown-4, dicyclohexyl-24-crown-8 (dicyclohexyl-24-crown-8), cyclohexyl-12-crown-4, 1,2-dicyclodecane- 15-crown-5(1,2-decalyl-15-crown-5), 1,2-naphth-15-crown-5(1,2-naphth-15-crown-5), 3,4 ,5-naphthyl-16-crown-5 (3,4,5-naphthyl-16-crown-5), 1,2-methylbenzo-18-crown-6, 1,2-spec- Butyl-18-crown-6, 1,2-vinylbenzo-15-crown-5, etc. can be listed and used.

所謂硅冠狀醚類(sila crown ether)，例如，可列舉使用的有：特開昭60-168775號公報等所揭示之化合物。具體來說，有：二甲基硅-11-冠醚-4(dimethylsila-11-crown-4)、二甲基硅-14-冠醚-5、二甲基硅-17-冠醚-6等可列舉使用。 For the so-called sila crown ether, for example, compounds disclosed in JP 60-168775 A and the like can be cited and used. Specifically, there are: dimethylsila-11-crown-4 (dimethylsila-11-crown-4), dimethylsila-14-crown-5, dimethylsila-17-crown-6 Etc. can be cited and used.

所謂杯芳烴類(calixarene)，可列舉使用的例如：特開昭60-179482號公報、特開昭62-235379號公報、特開昭63-88152號公報等所揭示之化合物。具體來說，有：5,11,17,23,29,35-六-特-丁基-37,38,39,40,41,42-六羥杯[6]芳烴(5,11,17,23,29,35-hexa-tert-butyl- 37,38,39,40,41,42-hexahydroxy calyx[6]arene)、37,38,39,40,41,42-六羥杯[6]芳烴(37,38,39,40,41,42-hexahydroxy calyx[6]arene)、37,38,39,40,41,42-六-(2-氧基-2-乙氧基)-乙氧基杯[6]芳烴(37,38,30,40,41,42-hexa-(2-oxo-2-ethoxy)-ethoxy calyx[6]arene)、25,26,27,28-四-(2-氧基-2-乙氧基)-乙氧基杯[6]芳烴、4-特-丁基杯[4]芳烴-0,0’,0”,0”’-四醋酸乙基酯(4-tert-butyl calyx[4]arene-0,0’,0”,0”’-tetraacetic acid tetraethyl)等可列舉使用。 As for calixarenes, for example, compounds disclosed in Japanese Patent Application Publication No. 60-179482, Japanese Patent Application Publication No. 62-235379, and Japanese Patent Application Publication No. 63-88152 can be used. Specifically, there are: 5,11,17,23,29,35-hexa-ter-butyl-37,38,39,40,41,42-hexahydroxycalix[6]arene (5,11,17 ,23,29,35-hexa-tert-butyl- 37,38,39,40,41,42-hexahydroxy calyx[6]arene), 37,38,39,40,41,42-hexahydroxy calyx[6]arene (37,38,39,40,41, 42-hexahydroxy calyx[6]arene), 37,38,39,40,41,42-hexa-(2-oxy-2-ethoxy)-ethoxycalix[6]arene (37,38, 30,40,41,42-hexa-(2-oxo-2-ethoxy)-ethoxy calyx[6]arene), 25,26,27,28-tetra-(2-oxy-2-ethoxy) -Ethoxycalix[6]arene, 4-tert-butyl calix[4]arene-0,0',0”,0”'-tetraacetic acid ethyl ester (4-tert-butyl calyx[4]arene -0,0',0",0"'-tetraacetic acid tetraethyl) and the like can be listed and used.

所謂環糊精類(cyclodextrin)，例如，可列舉使用的有：特表平5-505835號等所揭示之物。具體來說，有：α-、β-或γ-環糊精類等可列舉使用。所謂焦棓酚類(pyrogallol)環狀化合物類，可列舉使用的有：特開2000-191600號等所揭示之物。具體來說，有：3,4,5,10,11,12,17,18,19,24,25,26-十二乙氧基甲酯基-C-1,C-8,C-15,C-22-四甲基[14]-間環芳(3,4,5,10,11,12,17,18,19,24,25,26-dodecaethoxy carbomethoxy-C-1,C-8,C-15,C-22-tetramethyl[14]-metacyclophane)等可列舉使用。 The so-called cyclodextrins (cyclodextrin) include, for example, those disclosed in JP 5-505835 and the like. Specifically, α-, β-, or γ-cyclodextrins can be cited and used. The cyclic compounds of pyrogallols include those disclosed in JP 2000-191600 and the like. Specifically, there are: 3,4,5,10,11,12,17,18,19,24,25,26-dodecethoxymethyl-C-1,C-8,C-15 ,C-22-Tetramethyl[14]-metacyclic aromatic (3,4,5,10,11,12,17,18,19,24,25,26-dodecaethoxy carbomethoxy-C-1,C-8 , C-15, C-22-tetramethyl[14]-metacyclophane), etc. can be cited and used.

這些陰離子聚合促進劑可以單獨使用一種，也可以二種以上合併使用。 These anionic polymerization accelerators may be used alone or in combination of two or more kinds.

又，作為安定劑，可列舉使用的有：(1)二氧化硫(sulfur dioxide)和甲烷磺酸(methanesulfonic acid)等的脂肪族磺酸、對-甲苯磺酸(p-toluenesulfonic acid)等的芳香族磺酸、三氟化硼甲醇(boron trifluoride methanol；trifluoro(methanol)boron)、和三氟化硼***(boron trifluoride diethyl ether)等的三氟化硼絡合物(boron trifluoride complex)、HBF4、及三烷基硼酸酯(鹽)(trialkyl borate)等的陰離子聚合抑制劑(polymerization-inhibitor)；(2)氫醌(hydroquinone)、氫醌一甲基醚(hydroquinone monomethyl ether)、特-丁基鄰苯二酚(t-butylcatechol)、鄰苯二酚(catechol)及焦酸(pyrogallol)等自由基(radical)聚合抑制劑等。這些安定劑可以單獨使用一種，也可以二種以上併用。 In addition, as a stabilizer, there can be used: (1) aliphatic sulfonic acids such as sulfur dioxide and methanesulfonic acid, and aromatics such as p-toluenesulfonic acid (p-toluenesulfonic acid) Sulfonic acid, boron trifluoride methanol (boron trifluoride methanol; trifluoro (methanol) boron), and boron trifluoride diethyl ether (boron trifluoride diethyl ether) and other boron trifluoride complex (boron trifluoride complex), HBF 4 , And trialkyl borate (trialkyl borate) and other anionic polymerization inhibitors (polymerization-inhibitor); (2) hydroquinone (hydroquinone), hydroquinone monomethyl ether (hydroquinone monomethyl ether), t-butyl Radical polymerization inhibitors such as t-butylcatechol, catechol and pyrogallol. These stabilizers may be used singly or in combination of two or more kinds.

增塑劑若是在無損本發明之效果的範圍內就可以使用，作為彈性塑料成分，特別是，在2-氰基丙烯酸酯中極微溶性的聚合物所成的單體物被大量使用而作成的共聚物，亦即極微溶性段片很多的共聚物《極微溶性段片的比例為65%莫耳以上的共聚物》，使用這種共聚物的時候，由於使其含有適量，可以提高溶解性。 The plasticizer can be used in a range that does not impair the effect of the present invention. As an elastic plastic component, especially, a monomer composed of a polymer that is very slightly soluble in 2-cyanoacrylate is used in large quantities. Copolymers, that is, copolymers with a lot of very slightly soluble segments "copolymers with very slightly soluble segments of 65% or more of mol". When using this type of copolymer, the solubility can be improved because it contains an appropriate amount.

作為此種增塑劑，可列舉使用的有：乙醯基檸檬酸三乙基酯(triethyl acetylcitrate.)、乙醯基檸檬酸三丁基酯、己二酸二甲酯(adipic acid dimethyl ester)、己二酸二乙酯、癸二酸二甲酯(sebacic acid dimethyl ester)、酞酸二甲酯(dimethyl phthalate)、酞酸二乙酯、酞酸二丁酯、酞酸二異癸酯(diisodecyl phthalate)、酞酸二己酯、酞酸二庚酯、酞酸二辛酯(dioctyl phthalate)、酞酸二(2-乙基己基)酯(Bis(2-ethylhexyl)phthalate)、酞酸二異壬酯(diisononyl phthalat)、酞酸二異十三烷基酯(diisotridecyl phthalate)、酞酸二(十五烷基)酯(dipentadecyl phthalate)、對酞酸二辛酯(dioctyl terephthalate)、異酞酸二異壬酯(diisononyl isophthalat)、甲基苯甲酸癸酯(decyl toluate)、樟腦酸二個(2-乙基己基)酯(Bis(2-ethylhexyl)camphorate)、羧酸2-乙基己基環己基酯(2-ethylhexyl cyclohexyl carboxylate)、富馬酸二丁酯(dibutyl fumarate)、馬來酸二異丁酯(diisobutyl maleate)、己酸三酸甘油酯(caproic acid triglyceride)、安息香酸2-乙基己酯(2-ethylhexyl benzoate)、二安息香酸二丙二醇酯(dipropylene glycol dibenzoate)等。這些化合物中，從與2-氰基丙烯酸酯的相溶性優良、並且增塑化效率又很高的觀點來看，合於理想的是乙醯基檸檬酸三丁基酯、己二酸二甲酯、酞酸二甲酯、安息香酸2-乙基己酯、二安息香酸二丙二醇酯。這些增塑劑可以單獨使用一種，也可以合併二種以上使用。 Examples of such plasticizers include triethyl acetylcitrate (triethyl acetylcitrate.), tributyl acetylcitrate, dimethyl adipate (adipic acid dimethyl ester), diethyl adipate, dimethyl sebacic acid (sebacic acid dimethyl ester), dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dibutyl phthalate Diisodecyl phthalate, dihexyl phthalate, diheptyl phthalate, dioctyl phthalate, Bis(2-ethylhexyl)phthalate , Diisononyl phthalat (diisononyl phthalat), diisotridecyl phthalate (diisotridecyl phthalate), dipentadecyl phthalate (dipentadecyl phthalate), dioctyl terephthalate (dioctyl terephthalate) ), diisononyl isophthalat, decyl toluate, bis(2-ethylhexyl) camphorate, carboxylic acid 2 -Ethylhexyl cyclohexyl carboxylate (2-ethylhexyl cyclohexyl carboxylate), dibutyl fumarate (dibutyl fumarate), diisobutyl maleate (diisobutyl maleate), caproic acid triglyceride (caproic acid triglyceride), 2-ethylhexyl benzoate, dipropylene glycol dibenzoate, etc. Among these compounds, from the viewpoints of excellent compatibility with 2-cyanoacrylate and high plasticization efficiency, desirable ones are tributyl acetyl citrate and dimethyl adipate. Esters, dimethyl phthalate, 2-ethylhexyl benzoate, dipropylene glycol dibenzoate. These plasticizers may be used alone or in combination of two or more kinds.

又，增塑劑的含量並無特別限制，將2-氰基丙烯酸酯作為100質量部分的話，理想的係3~50質量部分，更理想的是10~45質量部 分，又更合於理想是20~40質量部分。增塑劑的含量若是3~50質量部分的話，特別是極微溶性段片很多的共聚物的時候，共聚物對2-氰基丙烯酸酯的溶解容易進行，特別是可以提高耐冷熱循環性試驗後的黏接強度的保持率。 In addition, the content of the plasticizer is not particularly limited. If 2-cyanoacrylate is used as 100 parts by mass, it is preferably 3-50 parts by mass, and more preferably 10~45 parts by mass. It is more ideal for 20-40 quality parts. If the content of the plasticizer is 3-50 parts by mass, especially when the copolymer has a lot of very slightly soluble segments, the copolymer can easily dissolve 2-cyanoacrylate, especially after the heat and cold cycle resistance test can be improved. The retention rate of bonding strength.

再者，作為增稠劑，可列舉使用的有：聚甲基丙烯酸甲酯(polymethyl methacrylate)、甲基丙烯酸甲酯和丙烯酸酯(acrylic ester)的共聚物、甲基丙烯酸甲酯和其他的甲基丙烯酸酯的共聚物、丙烯酸酯橡膠(acrylic rubber)、聚氯乙烯(polyvinyl chloride)、聚苯乙烯(polystyrene)、纖維素酯(cellulose ester)、聚烷基-2-氰基丙烯酸酯(polyalkyl-2-cyanoacrylate ester)以及乙烯乙酸酯共聚物(Ethylene-vinyl acetate copolymers)等。這些增稠劑可以單獨使用一種，也可以合併二種以上使用。 Furthermore, as the thickener, there can be listed and used: polymethyl methacrylate, a copolymer of methyl methacrylate and acrylic ester, methyl methacrylate and other methyl esters. -Based acrylate copolymer, acrylic rubber, polyvinyl chloride, polystyrene, cellulose ester, polyalkyl-2-cyanoacrylate -2-cyanoacrylate ester and Ethylene-vinyl acetate copolymers, etc. These thickeners may be used alone or in combination of two or more.

黏著劑組成物中也可以含有白煙矽(fumed silica)，此白煙矽是超微粉《初級粒子(primary particle)是500奈米(nm)以下，特別是1~200奈米》的無水二氧化矽；此種無水二氧化矽，例如，係以四氯 化矽(silicon tetrachloride)為原料，在高溫火燄中以氣相狀態經由氧化(oxidation)所生成的超微粉《初級粒子是500奈米以下，特別是1~200奈米》的無水二氧化矽，有親水性的高親水性二氧化矽和疏水性(hydrophobic)的高疏水性二氧化矽。作為此種白煙矽，可以使用任何一種，為了使2-氰基丙烯酸酯及其共聚物的分散性更佳，以疏水性二氧化矽較為理想。 The adhesive composition may also contain fumed silica. This fumed silica is an anhydrous powder of ultrafine powder "primary particles below 500 nanometers (nm), especially 1~200 nanometers". Silicon oxide; this kind of anhydrous silicon dioxide, for example, is based on tetrachloride Silica (silicon tetrachloride) as a raw material, in a high-temperature flame in the gas phase through oxidation (oxidation) generated ultrafine powder "the primary particles are below 500 nanometers, especially 1~200 nanometers" anhydrous silica, There are hydrophilic high-hydrophilic silica and hydrophobic (hydrophobic) high-hydrophobic silica. As such white fuming silica, any one can be used. In order to improve the dispersibility of 2-cyanoacrylate and its copolymer, hydrophobic silica is preferable.

又，作為彈性塑料，在2-氰基丙烯酸酯中可溶性的聚合物所成的單體物作成的共聚物，亦即，可溶性段片(segment)《含有包含羧基(carboxyl)段片》很多的共聚物，大量使用這種共聚物的情形時，則組合親水性二氧化矽來使用較為理想；在2-氰基丙烯酸酯中極微溶性的聚合物所成的單體物作成的共聚物，亦即，極微溶性段片很多的共聚物，大量使用這種共聚物的情形時，則組合疏水性二氧化矽來使用較為理想。 In addition, as an elastic plastic, a copolymer made of a monomer made of a polymer that is soluble in 2-cyanoacrylate, that is, a lot of soluble segments "containing carboxyl segments" Copolymers. When using this type of copolymer in large quantities, it is ideal to use it in combination with hydrophilic silica. A copolymer made of monomers made of a very slightly soluble polymer in 2-cyanoacrylate is also That is, a copolymer with a large number of very slightly soluble segments, and when a large amount of such a copolymer is used, it is preferable to use it in combination with hydrophobic silica.

作為親水性二氧化矽，可以使用是受的各種製品，舉例來說，AEROSIL 50、130、200、300及380《以上，係商品名，日本AEROSIL公司製造》可列舉使用。這些親水性二氧化矽的比表面積(specific surface area)，分別是50±15平方米/公克(m2/g)、130±25平方米 /公克、200±25平方米/公克、300±30平方米/公克、380±30平方米/公克。又，市售的親水性二氧化矽，可以使用REOLOSIL QS-10、QS-20、QS-30及QS-40《以上，係商品名，日本TOKUYAMA公司製造》，這些親水性二氧化矽的比表面積分別是140±20平方米/公克(m2/g)、220±20平方米/公克、300±30平方米/公克、380±30平方米/公克。此外，也可以使用CABOT公司製造的親水性二氧化矽。 As the hydrophilic silica, various acceptable products can be used. For example, AEROSIL 50, 130, 200, 300, and 380 "Above, the product name, manufactured by Japan AEROSIL company" can be used. The specific surface area of these hydrophilic silicas are 50±15 square meters/gram (m 2 /g), 130±25 square meters/gram, 200±25 square meters/gram, 300±30 Square meters/gram, 380±30 square meters/gram. In addition, commercially available hydrophilic silica can be used REOLOSIL QS-10, QS-20, QS-30 and QS-40 "above, the product name, manufactured by TOKUYAMA, Japan". The ratio of these hydrophilic silica The surface areas are 140±20 square meters/gram (m 2 /g), 220±20 square meters/gram, 300±30 square meters/gram, and 380±30 square meters/gram. In addition, hydrophilic silica manufactured by CABOT can also be used.

再者，作為疏水性二氧化矽，可以使用的製品，有：與親水性二氧化矽表面存在的羥基(hydroxyl)反應，形成疏水基，所得到之化合物；或，被吸附在親水性二氧化矽表面、在表面形成疏水性所得到之化合物，在有或無溶劑存在下，與親水性二氧化矽接觸，最好是經過加熱處理，藉由處理親水性二氧化矽的表面，所生成的製品。 Furthermore, as hydrophobic silica, the products that can be used include: reacting with the hydroxyl groups present on the surface of hydrophilic silica to form a hydrophobic group to form a compound; or, being adsorbed on the hydrophilic silica The silicon surface, the compound obtained by forming hydrophobicity on the surface, in contact with the hydrophilic silica in the presence or absence of a solvent, preferably after heat treatment, by treating the surface of the hydrophilic silica, the resulting Products.

親水性二氧化矽經表面處理而疏水化所使用的化合物，可列舉使用的，有：含有正-辛基三烷氧基矽烷(n-octyl trialkoxy silane)等疏水基的烷基(alkyl)、芳基(aryl)、芳代脂烷基(aralkyl)類的各種矽烷偶合劑(silane coupling agent)；甲基三氯矽烷(methyl trichlorosilane)、 二甲基二氯矽烷、六甲基矽氮烷(hexamethyl silazane)等的矽烷化試劑(silylating agent)；聚二甲基矽氧烷(polydimethylsiloxane)等的矽油(silicone oil)；十八烷醇(stearyl alcohol)等的高級醇；以及硬脂酸(stearic acid)等的高級脂肪酸等等。作為疏水性二氧化矽，也可以使用任何經疏水化的化合物作成的製品。 The compounds used for hydrophobization of hydrophilic silica after surface treatment include: alkyl containing n-octyl trialkoxy silane and other hydrophobic groups, Various silane coupling agents such as aryl and aralkyl; methyl trichlorosilane, Silylating agents such as dimethyl dichlorosilane and hexamethyl silazane; silicone oil such as polydimethylsiloxane; stearyl alcohol ( higher alcohols such as stearyl alcohol); and higher fatty acids such as stearic acid. As the hydrophobic silica, any product made of a hydrophobic compound can also be used.

市售的疏水性二氧化矽，可列舉使用的，例如：用矽油做表面處理，使其疏水化的REOLOSIL RY200、R202；用二甲基矽烷化試劑做表面處理，使其疏水化的REOLOSIL R974、R972、R976；用正-辛基三甲氧基矽烷(n-octyl trimethoxy silane)做表面處理，使其疏水化的REOLOSIL R805；用三甲基矽烷化試劑做表面處理，使其疏水化的REOLOSIL R811、R812《以上，係商品名，日本AEROSIL公司製造》及用甲基三氯矽烷做表面處理，使其疏水化的REOLOSIL MT-10《係商品名，日本TOKUYAMA公司製造》。這些疏水性二氧化矽的比表面積分別是100±20平方米/公克(m2/g)、100±20平方米/公克、170±20平方米/公克、110±20平方米/公克、250±25平方米/公克、150±20平方米/公克、150±20平方米/公克、260±20平方米/公克、120±10平方米/公克。 Commercially available hydrophobic silica can be listed and used, for example: REOLOSIL RY200 and R202 which are treated with silicone oil to make it hydrophobic; REOLOSIL R974 is used for surface treatment with a dimethyl silylation reagent to make it hydrophobic. , R972, R976; REOLOSIL R805 that uses n-octyl trimethoxy silane for surface treatment to make it hydrophobized; REOLOSIL that uses n-octyl trimethoxy silane for surface treatment to make it hydrophobized R811, R812 "Above, product name, manufactured by Japan AEROSIL company" and REOLOSIL MT-10 "product name, manufactured by Japan TOKUYAMA company" with surface treatment of methyltrichlorosilane to make it hydrophobic. The specific surface areas of these hydrophobic silicas are 100±20 square meters/gram (m 2 /g), 100±20 square meters/gram, 170±20 square meters/gram, 110±20 square meters/gram, 250 ±25 square meters/gram, 150±20 square meters/gram, 150±20 square meters/gram, 260±20 square meters/gram, 120±10 square meters/gram.

黏著劑組成物中的白煙矽的理想含量，將2-氰基丙烯酸酯當作100質量部分的情況下，係1~30質量部分。此白煙矽的理想含量，隨著2-氰基丙烯酸酯的種類、製造彈性塑料所用的單體物種類和比例、以及白煙矽的種類而有不同，但1~25質量部分是合於理想的，特別理想的是2~20質量部分。白煙矽含量是1~30質量部分的話，則無損黏著劑組成物的硬化性和黏著強度，可以作成施工性也很優良的黏著劑組成物。 The ideal content of white fuming silica in the adhesive composition is 1 to 30 parts by mass when 2-cyanoacrylate is regarded as 100 parts by mass. The ideal content of this white smoky silica varies with the type of 2-cyanoacrylate, the type and proportion of monomers used in the manufacture of elastic plastics, and the type of smoky silica, but the 1~25 mass part is suitable for Ideal, especially ideal is 2-20 mass parts. If the white smokysil content is 1-30 parts by mass, the hardening and adhesive strength of the adhesive composition will not be impaired, and an adhesive composition with excellent workability can be made.

【實施例】 [Example]

以實施例為基礎，更具體地說明本發明，但是並非侷限本發明與此範圍。再者，於下述中，『部份』及『%』，除非另有說明，係質量為基準。 Based on the embodiments, the present invention will be explained more specifically, but the present invention and the scope are not limited. Furthermore, in the following, "parts" and "%", unless otherwise specified, are based on quality.

1、評價方法 1. Evaluation method

(1)分子量 (1) Molecular weight

設備：Alliance 2695《Waters公司製造》 Equipment: Alliance 2695 "Made by Waters Company"

管柱：TSK gel SuperMultipore HZ-H二支、TSK gel Super HZ-2500二支聯結《TOSOH公司製造》 Column: two TSK gel SuperMultipore HZ-H, two TSK gel Super HZ-2500 connection "manufactured by TOSOH"

管柱溫度：40℃ Column temperature: 40℃

溶析液(eluent)：四氫呋喃(tetrahydrofuran)0.35毫升/分鐘(ml/Min) Eluent (eluent): tetrahydrofuran (tetrahydrofuran) 0.35 ml/min (ml/Min)

檢測器：折光率檢測器(refractive index detector；RI) Detector: Refractive index detector (RI)

藉由凝膠滲透光譜儀(gel permeation chromatograph；GPC)測定的分子量，以聚苯乙烯的分子量為基準，換算出來。 The molecular weight measured by a gel permeation chromatograph (GPC) is calculated based on the molecular weight of polystyrene.

(2)黏著速度 (2) Adhesion speed

日本工業標準(Japanese Industrial Standards；JIS)K 6861『α-氰基丙烯酸酯(鹽)類黏著劑試驗方法』為準據，在23℃、60%相對濕度(relative humidity；RH)的環境下，測量黏著速度。所使用之測試片係如下述。 Japanese Industrial Standards (JIS) K 6861 "Test Method for α-Cyanoacrylate (Salt) Adhesives" is the criterion. Under 23℃, 60% relative humidity (RH) environment, Measure the adhesion speed. The test pieces used are as follows.

◆ABS：宇部工業公司製造之丙烯腈-丁二烯-苯乙烯共聚物樹脂(ABS resin；acrylonitrile butadiene styrene copolymer)，商品名『GSE』 ◆ABS: ABS resin (acrylonitrile butadiene styrene copolymer) manufactured by Ube Industry Co., Ltd., trade name "GSE"

(3)耐冷熱循環性 (3) Resistance to cold and heat cycles

將鋁板《JIS A6061P所規定的材質》、與ABS樹脂《新神戶電機公司製，商品名『ABS-N-WN』，作為ABS樹脂》製的測試片，用實施例和比較例的黏著劑組成物，黏貼在一起，在23℃、60%相對濕度的環境下靜置7天，使其硬化(curing)後，以JIS K 6861為準則，測量拉伸剪切強度(tensile shear strength)《此為初期強度》；接下來，利用冷熱衝擊試驗機(Hot-cold shock testing equipment)，以在零下40℃維持一小時、然後在80℃維持一小時的冷熱循環作為一循環，經過10個循環後的拉伸剪切強度，用前述相同方法測出《此為測試後強度》，經由下述公式計算出保持率。 A test piece made of aluminum plate "Material specified by JIS A6061P" and ABS resin "manufactured by Shin Kobe Electric Co., Ltd., trade name "ABS-N-WN" as ABS resin", and composed of the adhesives of the examples and comparative examples Measure the tensile shear strength (tensile shear strength) according to the JIS K 6861 standard after being cured for 7 days at 23°C and 60% relative humidity. Is the initial strength>; Next, use a hot-cold shock testing equipment to maintain a cold-heat cycle at minus 40°C for one hour and then at 80°C for one hour as a cycle. After 10 cycles Measure the tensile shear strength of "This is the strength after the test" with the same method described above, and calculate the retention rate by the following formula.

保持率(%)=(測試後強度/初期強度)×100 Retention rate (%)=(strength after test/initial strength)×100

(4)耐熱水性 (4) Hot water resistance

將鋁板《JIS A6061P所規定的材質》、與ABS樹脂《新神戶電機公司製，商品名『ABS-N-WN』，作為ABS樹脂》製的測試片，使用實施例和比較例的黏著劑組成物，黏貼在一起，在23℃、60%相對濕度的環境下靜置7天，使其硬化(curing)後，以JIS K 6861為準則，測量拉伸剪切強度(tensile shear strength)《此為初期強度》；接下來， 在60℃的熱水中浸泡一週後的拉伸剪切強度，用前述相同方法測出《此為測試後強度》，經由下述公式計算出保持率。 A test piece made of aluminum plate "Material prescribed by JIS A6061P" and ABS resin "manufactured by Shin Kobe Electric Co., Ltd., trade name "ABS-N-WN" as ABS resin", using the adhesives of the examples and comparative examples Measure the tensile shear strength (tensile shear strength) according to the JIS K 6861 standard after being cured for 7 days at 23°C and 60% relative humidity. Is the initial strength"; next, After immersing in hot water at 60°C for one week, the tensile shear strength is measured by the same method as described above, "This is the strength after the test", and the retention rate is calculated by the following formula.

保持率(%)=(測試後強度/初期強度)×100 Retention rate (%)=(strength after test/initial strength)×100

(5)剝離黏接強度(peeling adhesive strength) (5) Peeling adhesive strength

厚度0.1毫米(mm)的鋁箔《JIS 1N30所規定之材質》作為測試片，使用實施例和比較例的黏著劑組成物，黏貼在一起，在溫度23℃、60%相對濕度的環境下靜置7天，使其硬化(curing)後，以JIS K 6854-3為準則，測量T型剝離黏接強度。 Aluminum foil with a thickness of 0.1 millimeter (mm) "Material specified in JIS 1N30" is used as a test piece, using the adhesive composition of the examples and comparative examples, sticking together, and standing at a temperature of 23°C and a relative humidity of 60% After 7 days of curing (curing), the T-type peel adhesion strength was measured according to JIS K 6854-3.

(6)硬化物的柔韌性 (6) Flexibility of hardened material

製作1毫米的硬化物，藉由壓頭壓入超微小硬度計(indenter Ultra-Micro hardness testing machines)《Fischer Instrument公司製，商品名『H100CXYp』》，在壓陷荷載(indentation load)200毫牛頓(mN)、維持時間10秒的條件下，測量其通用硬度(universal hardness)。 Make a 1 mm hardened object, press indenter Ultra-Micro hardness testing machines "manufactured by Fischer Instrument, trade name "H100CXYp"" with an indenter, and apply an indentation load of 200 mm Under the conditions of Newton (mN) and a holding time of 10 seconds, the universal hardness is measured.

2、鎓鹽的合成 2. Synthesis of onium salt

＊合成例1《甲基三-正-辛基銨兩個(氟磺醯基)醯亞銨(methyl tri-n-octyl ammonium bis(fluorosulfonyl)imide)》 ＊Synthesis example 1 "methyl tri-n-octyl ammonium bis(fluorosulfonyl)imide"

50毫升茄形燒瓶(egg-plant shaped flask)中，放入氯化甲基三-正-辛基銨(methyl tri-n-octylammonium chloride)《試劑》4.041公克(g)《10.00毫莫耳(mmol)》、離子交換水5毫升，然後加入兩個(氟磺醯基醯亞銨)鉀(bis(fluorosulfonyl imide)potassium)5.313公克《10.00毫莫耳(mmol)》溶解於離子交換水10毫升所成溶液，在室溫下又攪拌247小時。將下層液分離，用離子交換水5毫升洗淨5次後，減壓下在60℃乾燥。得到無色液體5.166公克《鎓鹽A》。 In a 50 ml egg-plant shaped flask, put methyl tri-n-octylammonium chloride (methyl tri-n-octylammonium chloride) "Reagent" 4.041 grams (g) "10.00 millimoles ( mmol)”, 5 ml of ion-exchanged water, then add two (bis(fluorosulfonyl imide) potassium) 5.313 g of “10.00 millimoles (mmol)” and dissolve in 10 ml of ion-exchanged water The resulting solution was stirred for another 247 hours at room temperature. The lower layer was separated, washed 5 times with 5 ml of ion exchange water, and dried at 60°C under reduced pressure. 5.166 g of "Onium Salt A" was obtained as a colorless liquid.

＊合成例2《1-丁基-3-甲基吡啶鎓兩個(氟磺醯基)醯亞銨(1-butyl-3-methyl pyridinium bis(fluorosulfonyl)imide)》 ＊Synthesis example 2 "1-butyl-3-methyl pyridinium bis(fluorosulfonyl)imide"

將氯化甲基三-正-辛基銨(methyl tri-n-octylammonium chloride)用溴化1-丁基-3-甲基吡啶鎓(1-butyl-3-methyl pyridinium bromide)《試劑》2.302公克替代以外，進行與合成例1相同操作，得到無色液體3.105公克《鎓鹽B》。 Use methyl tri-n-octylammonium chloride with 1-butyl-3-methyl pyridinium bromide (reagent) 2.302 Except for the substitution of grams, the same operation as in Synthesis Example 1 was performed to obtain 3.105 grams of "Onium Salt B" as a colorless liquid.

＊合成例3《苄基三丁基銨兩個(氟磺醯基)醯亞銨(benzyl tributyl ammonium bis(fluorosulfonyl)imide)》 ＊Synthesis example 3 "benzyl tributyl ammonium bis(fluorosulfonyl)imide"

將氯化甲基三-正-辛基銨(methyl tri-n-octylammonium chloride)用溴化苄基三丁基銨(benzyl tributyl ammonium bromide)《試劑》3.564公克替代以外，進行與合成例1相同操作，得到無色液體4.151公克《鎓鹽C》。 Substituting methyl tri-n-octylammonium chloride with benzyl tributyl ammonium bromide "Reagent" 3.564 g, proceed as in Synthesis Example 1 After operation, 4.151 grams of "Onium Salt C" was obtained as a colorless liquid.

3、黏著劑組成物之製造 3. Manufacture of adhesive composition

＊實施例1 *Example 1

2-氰基丙烯酸乙酯(ethyl 2-cyanoacrylate)100部分中，調配二氧化硫(sulfur dioxide)20百萬單位(ppm)、對苯二酚(hydroquinone)1000百萬單位、甲烷磺酸(methane sulfonic acid)0.08部分；此混合物中更進一步調配表3所記載的彈性塑料《乙烯/丙烯酸甲酯共聚物，Du Pont Elastomer公司製，商品名「Vamac G」》20部分，使其溶解後，再調配預先混合有乙烯基三甲氧基矽烷(vinyl trimethoxy silane)《Momentive Performance Materials Japan公司製造，商品名『A-171』》1.5部分的具水解性矽烷基的聚合物50部分《KANEKA公司製造，商 品名「Cyril SAT200」》、1-乙基-3-甲基咪唑鎓兩個(氟磺醯基)醯亞銨(1-ethyl-3-methyl imidazolinium bis(fluorosulfonyl)imide)《第一工業製藥公司製造，商品名『ELEXCEL IL-110』》1.50部分，於溫度15~30℃、攪拌10分鐘，加以混合，製造黏著劑組成物。使用所得到之黏著劑組成物，進行前述評價，其結果顯示於表2。 In the 100 part of ethyl 2-cyanoacrylate, 20 million units of sulfur dioxide (ppm), 1,000 million units of hydroquinone, and methane sulfonic acid ) 0.08 part; this mixture is further blended with the elastomeric plastic "ethylene/methyl acrylate copolymer, manufactured by Du Pont Elastomer, trade name "Vamac G"" as described in Table 3, and the 20 part is dissolved and then blended in advance A polymer with a hydrolyzable silyl group mixed with vinyl trimethoxy silane "manufactured by Momentive Performance Materials Japan, trade name "A-171"" 1.5 part 50 part "manufactured by KANEKA, manufacturer Product name "Cyril SAT200", 1-ethyl-3-methyl imidazolinium bis (fluorosulfonyl) imide, First Industrial Pharmaceutical Company Manufacture, product name "ELEXCEL IL-110"" 1.50 part, stir for 10 minutes at a temperature of 15-30°C, and mix to manufacture an adhesive composition. Using the obtained adhesive composition, the aforementioned evaluation was performed, and the results are shown in Table 2.

Figure 105120025-A0305-02-0056-5
Figure 105120025-A0305-02-0056-5
Figure 105120025-A0305-02-0057-6
Figure 105120025-A0305-02-0057-6

Figure 105120025-A0305-02-0058-7
Figure 105120025-A0305-02-0058-7

＊實施例2~10 ＊Examples 2~10

2-氰基丙烯酸乙酯(ethyl 2-cyanoacrylate)《在實施例9和10中，與2-氰基丙烯酸異丁酯混合》中，如表1所記載一般，調配酸催化劑的種類和含量、彈性塑料的種類《Du Pont Elastomer公司製，商品名「Vamac」系列，參照表3》和含量、具水解性矽烷基的聚合物的種類和含量《KANEKA公司製造，商品名「Cyril」系列，參照表4》、鎓鹽的種類和含量，除此外，與實施例1進行相同操作，製造黏著劑組成物，加以評價，其結果顯示在表2。 Ethyl 2-cyanoacrylate (Ethyl 2-cyanoacrylate) "In Examples 9 and 10, mixed with isobutyl 2-cyanoacrylate", as described in Table 1, the type and content of the acid catalyst, Type of elastic plastic "manufactured by Du Pont Elastomer, brand name "Vamac" series, refer to Table 3" and content, type and content of polymer with hydrolyzable silyl group, "manufactured by KANEKA company, brand name "Cyril" series, refer to Table 4 ", the type and content of onium salt, except that the same operation as in Example 1 was performed to produce an adhesive composition, and the evaluation was performed. The results are shown in Table 2.

再者，於表3中，『E』係乙烯(ethylene)，『MA』係丙烯酸甲酯(methyl acrylate)，『AA』係丙烯酸，『BA』係丙烯酸丁酯。 Furthermore, in Table 3, "E" is ethylene, "MA" is methyl acrylate, "AA" is acrylic, and "BA" is butyl acrylate.

Figure 105120025-A0305-02-0059-8
Figure 105120025-A0305-02-0059-8

Figure 105120025-A0305-02-0059-9
Figure 105120025-A0305-02-0059-9

＊比較例1 ＊Comparative example 1

未調配彈性塑料，其他成分如表5所記載一般調配，除此外，與實施例1進行相同的製造，2-氰基丙烯酸酯和具水解性矽烷基聚合物無法混合，由於立即發熱、且凝膠化，無法完成評價。 The elastic plastic is not formulated, and the other components are generally formulated as described in Table 5. Except for this, the same manufacturing is performed as in Example 1. The 2-cyanoacrylate and the hydrolyzable silyl polymer cannot be mixed because they immediately generate heat and condense. Gelation, unable to complete evaluation.

＊比較例2 ＊Comparative example 2

未調配酸催化劑，其他成分如表5所記載一般調配，除此外，與 實施例1進行相同的製造，2-氰基丙烯酸酯和具水解性矽烷基聚合物雖然能夠混合，但由於立即增稠(thickening)、且凝膠化，無法完成評價。 No acid catalyst is formulated, other ingredients are generally formulated as described in Table 5, except for Example 1 was produced in the same manner. Although 2-cyanoacrylate and the hydrolyzable silane-based polymer can be mixed, the evaluation could not be completed due to immediate thickening and gelation.

＊比較例3 ＊Comparative example 3

未調配具水解性矽烷基聚合物，其他成分如表5所記載一般調配，除此外，與實施例1進行相同的製造，實施相同的評價，其結果顯示在表6。 The hydrolyzable silane-based polymer was not formulated, and the other components were generally formulated as described in Table 5. Except for this, the same production was performed as in Example 1, and the same evaluation was performed. The results are shown in Table 6.

＊比較例4 ＊Comparative example 4

未調配鎓鹽，其他成分如表5所記載一般調配，除此外，與實施例1進行相同的製造，實施相同的評價，其結果顯示在表6。 The onium salt was not blended, and other components were generally blended as described in Table 5, except that the same production was performed as in Example 1, and the same evaluation was performed. The results are shown in Table 6.

Figure 105120025-A0305-02-0061-10
Figure 105120025-A0305-02-0061-10

Figure 105120025-A0305-02-0061-11
Figure 105120025-A0305-02-0061-11

【產業方面的可能應用】 [Possible applications in industry]

本發明含有2-氰基丙烯酸酯(2-cyanoacrylate ester)，作為所謂瞬間黏著劑，可以應用在一般家庭、醫療領域等以外，在各種產業界的廣泛製品、技術領域中，也可應用；特別是在要求耐冷熱循環性(thermal cycle resistance)和耐熱水性等的黏著持久性之用途方面，極為有用。 The present invention contains 2-cyanoacrylate ester. As a so-called instant adhesive, it can be used in general households, medical fields, etc., as well as in a wide range of products and technical fields in various industries; especially It is extremely useful for applications that require thermal cycle resistance and hot water resistance and other adhesion durability.

Figure 105120025-A0305-02-0002-1
Figure 105120025-A0305-02-0002-1

Claims (9)

一種黏著劑組成物，包含：(a)2-氰基丙烯酸酯、和(b)具有水解性(hydrolyzability)矽烷基(silyl)的聚合物、和(c)彈性塑料(elastomer)、和(d)酸催化劑、和(e)含有下述化學式(1)所表之鎓鹽；前述(a)成分當作100質量部分的情形時，前述(b)成分的含量為5~200質量部分，前述(c)成分的含量為5~50質量部分，前述(d)成分的含量為0.0005~0.5質量部分，前述(e)成分的含量為0.001~5質量部分，以此為特徵的黏著劑組成物；C+A-……(1)《化學式(1)中，C+係鎓鹽陽離子(onium cation)；A-係雙(氟磺醯)亞胺陰離子(bis(fluorosulfonyl)imide anion)》。 An adhesive composition comprising: (a) 2-cyanoacrylate, and (b) a hydrolyzability (silyl) polymer, and (c) an elastic plastic (elastomer), and (d) ) An acid catalyst, and (e) contain an onium salt represented by the following chemical formula (1); when the aforementioned component (a) is regarded as 100 parts by mass, the content of the aforementioned component (b) is 5 to 200 parts by mass, The content of component (c) is 5-50 parts by mass, the content of component (d) is 0.0005-0.5 parts by mass, and the content of component (e) is 0.001-5 parts by mass, which is an adhesive composition characterized by ; C + A - ...... (1 ) " of the formula (1), C + onium salt-based cations (onium cation); A - Department of bis (fluoromethyl sulfonylurea) imide anion (bis (fluorosulfonyl) imide anion) ". 如申請專利範圍第1項所述之黏著劑組成物，其中前述(b)具有水解性矽烷基的聚合物，係選自氧化烯(oxyalkylene)類聚合物、乙烯基(vinyl)類聚合物、聚酯(polyester)類聚合物、聚氨酯(polyurethane)類聚合物、和聚碳酸酯(polycarbonate)類聚合物所成群類中至少一種的聚合物。 The adhesive composition described in item 1 of the scope of patent application, wherein the aforementioned (b) polymer with hydrolyzable silyl group is selected from oxyalkylene-based polymers, vinyl-based polymers, Polyester (polyester) type polymer, polyurethane (polyurethane) type polymer, and polycarbonate (polycarbonate) type polymer at least one type of polymer. 如申請專利範圍第1項或第2項所述之黏著劑組成物，其中前述(b)具有水解性矽烷基的聚合物的數目平均分子量係500~50000。 The adhesive composition described in item 1 or item 2 of the scope of patent application, wherein the number average molecular weight of the polymer having hydrolyzable silyl group (b) is 500 to 50,000. 如申請專利範圍第1項至第3項之任一項所述之黏著劑組成物，其中前 述(c)彈性塑料(elastomer)係使用在2-氰基丙烯酸酯中極微溶性(slightly soluble)的聚合物所形成之單體物(monomer)、與在2-氰基丙烯酸酯中可溶性的聚合物所形成之單體物所作成的共聚物。 The adhesive composition described in any one of items 1 to 3 of the scope of patent application, wherein the former The (c) elastomer is a monomer formed by a slightly soluble polymer in 2-cyanoacrylate, and a monomer that is soluble in 2-cyanoacrylate. A copolymer made of monomers formed by a substance. 如申請專利範圍第1項至第3項之任一項所述之黏著劑組成物，其中前述(c)彈性塑料(elastomer)係使用在2-氰基丙烯酸酯中極微溶性(slightly soluble)的聚合物所形成之單體物(monomer)、在2-氰基丙烯酸酯中可溶性的聚合物所形成之單體物、及含有羧基(carboxyl)的單體物所作成的共聚物。 The adhesive composition according to any one of items 1 to 3 in the scope of the patent application, wherein the aforementioned (c) elastic plastic (elastomer) is used slightly soluble in 2-cyanoacrylate A copolymer formed by a monomer formed by a polymer, a monomer formed by a polymer that is soluble in 2-cyanoacrylate, and a monomer containing a carboxyl group. 如申請專利範圍第4項或第5項所述之黏著劑組成物，其中前述在2-氰基丙烯酸酯中極微溶性的聚合物所形成之單體物係乙烯(ethylene)、丙烯(propylene)、異戊二烯(isoprene)和丁二烯(butadiene)之中至少一種；前述在2-氰基丙烯酸酯中可溶性的聚合物所形成之單體物係丙烯酸酯和甲基丙烯酸酯(methacrylate ester)之中至少一種。 The adhesive composition according to item 4 or item 5 of the scope of patent application, wherein the monomers formed by the polymer that is very slightly soluble in 2-cyanoacrylate are ethylene and propylene , At least one of isoprene and butadiene; the monomers formed by the polymer soluble in 2-cyanoacrylate are acrylate and methacrylate ester ) At least one of them. 如申請專利範圍第1項至第6項之任一項所述之黏著劑組成物，其中前述(d)酸催化劑係在25℃時的酸解離常數(pKa；acid dissociation constant)在4以下的酸。 The adhesive composition according to any one of items 1 to 6 of the scope of patent application, wherein the acid catalyst (d) has an acid dissociation constant (pKa; acid dissociation constant) of 4 or less at 25°C acid. 如申請專利範圍第1項至第7項之任一項所述之黏著劑組成物，其中 前述(d)酸催化劑係選自磺酸(sulfonic acid)、磷酸(phosphoric acid)、磷酸單酯(phosphoric mono)、磷酸二酯(phosphoric diester)、亞磷酸(phosphorous acid)、及亞磷酸酯(phosphorous ester)所成群類中至少一種的酸。 The adhesive composition described in any one of items 1 to 7 of the scope of patent application, wherein The aforementioned (d) acid catalyst is selected from the group consisting of sulfonic acid, phosphoric acid, phosphoric mono, phosphoric diester, phosphorous acid, and phosphite ( Phosphorous ester) at least one acid in the group. 如申請專利範圍第1項至第8項之任一項所述之黏著劑組成物，其中前述(e)鎓鹽陽離子係選自四級銨陽離子(quaternary ammonium cation)、咪唑鎓陽離子(imidazolium cation)、吡啶鎓陽離子(pyridinium cation)、及三級硫鎓陽離子(tertiary sulfonium catiion)所成群類中至少一種的鎓鹽陽離子。 The adhesive composition according to any one of items 1 to 8 in the scope of the patent application, wherein the (e) onium salt cation is selected from the group consisting of quaternary ammonium cation, imidazolium cation ), pyridinium cation, and tertiary sulfonium cation (tertiary sulfonium catiion) at least one onium salt cation.
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