TW201936856A - Temperature-sensitive adhesive, temperature-sensitive adhesive sheet and temperature-sensitive adhesive tape - Google Patents
Temperature-sensitive adhesive, temperature-sensitive adhesive sheet and temperature-sensitive adhesive tape Download PDFInfo
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- TW201936856A TW201936856A TW108103311A TW108103311A TW201936856A TW 201936856 A TW201936856 A TW 201936856A TW 108103311 A TW108103311 A TW 108103311A TW 108103311 A TW108103311 A TW 108103311A TW 201936856 A TW201936856 A TW 201936856A
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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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本發明關於感溫性黏著劑、感溫性黏著片及感溫性黏著帶。 The invention relates to a temperature sensitive adhesive, a temperature sensitive adhesive sheet and a temperature sensitive adhesive tape.
已知具有會因應溫度變化而可逆地顯示結晶狀態與流動狀態之感溫性之感溫性樹脂。例如日本特表平6-510548號公報揭示含有此種樹脂之感溫性黏著劑。感溫性黏著劑中存在加溫剝離型(warm-off type)黏著劑,該加溫剝離型黏著劑可在感溫性樹脂之熔點以下的溫度發揮固定力,並且在感溫性樹脂之熔點以上的溫度時黏著力會顯著降低而剝離。 A temperature sensitive resin having a temperature sensitive property in which a crystal state and a flow state are reversibly displayed in response to a temperature change is known. For example, Japanese Laid-Open Patent Publication No. Hei 6-510548 discloses a temperature sensitive adhesive containing such a resin. In the temperature sensitive adhesive, there is a warm-off type adhesive which can exert a fixing force at a temperature below the melting point of the temperature sensitive resin and at a melting point of the temperature sensitive resin. At the above temperatures, the adhesion is significantly reduced and peeled off.
對於不銹鋼板及玻璃等無機系被黏著物、或者聚醯胺系被黏著物、聚甲醛系被黏著物、聚對苯二甲酸乙二酯系被黏著物、聚甲基丙烯酸甲酯系被黏著物、聚碳酸酯系被黏著物等有機系被黏著物,以往的加溫剝離型黏著劑在感溫性樹脂之熔點以上的溫度時黏著力會顯著降低,可容易地剝離。然而,有機系被黏著物之中,尤其對於聚醯亞胺系被黏著物,即使在感溫性樹脂之熔點以上的溫度,黏著力仍不降低。其結果,若對聚醯亞胺系被黏著物使用以往的加溫剝離型黏著劑,則難以剝離黏著劑。 For inorganic adhesives such as stainless steel sheets and glass, or polyimide-based adhesives, polyoxymethylene-based adhesives, polyethylene terephthalate-based adhesives, and polymethyl methacrylate An organic-based adhesive such as a polycarbonate or a polycarbonate-based adhesive is used. When the conventional heat-releasing adhesive is at a temperature equal to or higher than the melting point of the temperature-sensitive resin, the adhesive strength is remarkably lowered, and the adhesive can be easily peeled off. However, among the organic adherends, especially for the polyimide-based adhesive, the adhesive strength does not decrease even at a temperature higher than the melting point of the temperature sensitive resin. As a result, when a conventional heat-peelable adhesive is used for the polyimide-based adhesive, it is difficult to peel off the adhesive.
本發明之課題係提供一種感溫性黏著劑以及含此種感溫性黏著劑之感溫性黏著片及感溫性黏著帶,其中,對於聚醯亞胺系被黏著物,該感溫性黏著劑在室溫下可堅固地接著,並且在感溫性樹脂之熔點以上的溫度時黏著力會降低,可容易地剝離。 An object of the present invention is to provide a temperature sensitive adhesive and a temperature sensitive adhesive sheet and a temperature sensitive adhesive tape containing the temperature sensitive adhesive, wherein the temperature sensitivity is applied to a polyimide-based adhesive. The adhesive can be firmly adhered at room temperature, and the adhesive force is lowered at a temperature higher than the melting point of the temperature sensitive resin, and the adhesive can be easily peeled off.
本發明者等為了解決上述課題而精心檢討的結果,發現含下述構成之解決手段,完成本發明。 The inventors of the present invention have found a solution including the following configuration in order to solve the above problems and have completed the present invention.
(1)一種感溫性黏著劑,係包含基本樹脂(A)及不含羧基之側鏈結晶性聚合物(B),其中,基本樹脂(A)為含有含羧基之乙烯性不飽和單體(A1)及具有碳數4至7之烴基之(甲基)丙烯酸酯(A2)之單體混合物的共聚物,不含羧基之側鏈結晶性聚合物(B)為以含有具有碳數14至30之直鏈狀烷基之(甲基)丙烯酸酯(B1)之單體成分作為構成單元之聚合物,該感溫性黏著劑在不含羧基之側鏈結晶性聚合物(B)之熔點以上的溫度時,對聚醯亞胺系被黏著物之黏著力降低。 (1) A temperature sensitive adhesive comprising a base resin (A) and a carboxyl group-free side chain crystalline polymer (B), wherein the base resin (A) is a carboxyl group-containing ethylenically unsaturated monomer a copolymer of a monomer mixture of (A1) and a (meth) acrylate (A2) having a hydrocarbon group of 4 to 7 and a carboxyl group-free side chain crystalline polymer (B) having a carbon number of 14 a monomer component of a (meth) acrylate (B1) of a linear alkyl group of up to 30, which is a polymer of a constituent unit, and the temperature sensitive adhesive is a side chain crystalline polymer (B) containing no carboxyl group. When the temperature is higher than the melting point, the adhesion to the polyimide-based adhesive is lowered.
(2)如上述(1)所述之感溫性黏著劑,其中,不含羧基之側鏈結晶性聚合物(B)之單體成分係以30至70質量%之比率含有(甲基)丙烯酸酯(B1),並以30至70質量%之比率更再含有具有碳數1至6之烷基之(甲基)丙烯酸酯(B2)。 (2) The temperature sensitive adhesive according to the above (1), wherein the monomer component of the carboxyl group-free side chain crystalline polymer (B) is contained in a ratio of 30 to 70% by mass (meth) The acrylate (B1) further contains a (meth) acrylate (B2) having an alkyl group having 1 to 6 carbon atoms in a ratio of 30 to 70% by mass.
(3)如上述(1)或(2)所述之感溫性黏著劑,其中,不含羧基之側鏈結晶性聚合物(B)係具有3000至30000之重量平均分子量。 (3) The temperature sensitive adhesive according to the above (1) or (2), wherein the side chain crystalline polymer (B) having no carboxyl group has a weight average molecular weight of from 3,000 to 30,000.
(4)如上述(1)至(3)中任一項所述之感溫性黏著劑,更含有交聯劑。 (4) The temperature sensitive adhesive according to any one of the above (1) to (3), further comprising a crosslinking agent.
(5)如上述(1)至(4)中任一項所述之感溫性黏著劑,其中,對於聚醯亞胺系被黏著物,在23℃時具有2N/25mm以上之黏著強度,在側鏈結晶性聚合物之熔點以上的溫度時則具有0.05N/25mm以下之黏著強度。 (5) The temperature-sensitive adhesive according to any one of the above-mentioned (1), wherein the polyimide-based adherend has an adhesive strength of 2 N/25 mm or more at 23 ° C. When the temperature is higher than the melting point of the side chain crystalline polymer, it has an adhesive strength of 0.05 N/25 mm or less.
(6)一種感溫性黏著片,係含有上述(1)至(5)中任一項所述之感溫性黏著劑。 (6) A temperature sensitive adhesive sheet comprising the temperature sensitive adhesive according to any one of the above (1) to (5).
(7)一種感溫性黏著帶,係在基材之至少一面形成有含有上述(1)至(5)中任一項所述之感溫性黏著劑之黏著劑層。 (7) A temperature sensitive adhesive tape comprising an adhesive layer containing the temperature sensitive adhesive according to any one of the above (1) to (5), formed on at least one surface of the substrate.
依據本發明,對於聚醯亞胺系被黏著物,在室溫下可堅固地接著,並且在感溫性樹脂之熔點以上的溫度時黏著力會降低,可容易地剝離。亦即,如室溫下之類的未達感溫性樹脂之熔點的溫度,藉由基本樹脂(A)之黏著性及不含羧基之側鏈結晶性聚合物(B)之凝聚力而發揮堅固的黏著性。另一方面,於感溫性樹脂之熔點以上的溫度,表面自由能會依聚醯亞胺系被黏著物與感溫性樹脂之接觸角的改變而改變。因此,聚醯亞胺系被黏著物與感溫性樹脂之界面交互作用變小而剝離性提升,且應力會集中在分散於基本樹脂表面之經熔融的感溫性樹脂,故界面容易剝離。 According to the present invention, the adhesive of the polyimide-based adhesive can be firmly adhered at room temperature, and at a temperature equal to or higher than the melting point of the temperature-sensitive resin, the adhesive strength is lowered, and the adhesive can be easily peeled off. That is, the temperature at which the melting point of the temperature sensitive resin is not reached at room temperature is exhibited by the adhesion of the base resin (A) and the cohesive force of the side chain-chain crystalline polymer (B) which does not contain a carboxyl group. Adhesiveness. On the other hand, at a temperature higher than the melting point of the temperature sensitive resin, the surface free energy changes depending on the contact angle of the polyimide and the temperature sensitive resin. Therefore, the interfacial interaction between the polyimide-based adhesive and the temperature-sensitive resin is small, the peeling property is improved, and the stress is concentrated on the molten temperature-sensitive resin dispersed on the surface of the base resin, so that the interface is easily peeled off.
詳細說明本發明之一實施形態之感溫性黏著劑。一實施形態之感溫性黏著劑係包含基本樹脂(A)及不含羧基之側鏈結晶性聚合物(B),且在不含羧 基之側鏈結晶性聚合物(B)(相當於感溫性樹脂)之熔點以上的溫度時黏著力降低。本說明書中,「(甲基)丙烯酸」意指「丙烯酸」或「甲基丙烯酸」。 A temperature sensitive adhesive according to an embodiment of the present invention will be described in detail. The temperature sensitive adhesive according to one embodiment comprises a base resin (A) and a carboxyl group-free side chain crystalline polymer (B), and a side chain crystalline polymer (B) having no carboxyl group (equivalent to a feeling) When the temperature above the melting point of the warm resin) is lowered, the adhesion is lowered. In the present specification, "(meth)acrylic" means "acrylic acid" or "methacrylic acid".
基本樹脂(A)為含有含羧基之乙烯性不飽和單體(A1)及具有碳數4至7之烴基之(甲基)丙烯酸酯(A2)為單體混合物的共聚物。藉由使用此種特定共聚物作為基本樹脂(A),可對聚醯亞胺系被黏著物發揮特別的黏著性及剝離性。 The base resin (A) is a copolymer containing a carboxyl group-containing ethylenically unsaturated monomer (A1) and a (meth) acrylate (A2) having a hydrocarbon group of 4 to 7 carbon atoms as a monomer mixture. By using such a specific copolymer as the base resin (A), it is possible to exhibit special adhesion and releasability to the polyimide-based adherend.
就含羧基之乙烯性不飽和單體(A1)而言,可列舉例如不飽和單羧酸、不飽和二羧酸、含羧基之不飽和酯等。 The carboxyl group-containing ethylenically unsaturated monomer (A1) may, for example, be an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid or a carboxyl group-containing unsaturated ester.
就不飽和單羧酸而言,可列舉例如丙烯酸、甲基丙烯酸、巴豆酸等。就不飽和二羧酸而言,可列舉例如伊康酸、順丁烯二酸、反丁烯二酸等。就含羧基之不飽和酯而言,可列舉例如丙烯酸β-羧基乙酯等。含羧基之乙烯性不飽和單體(A1)可僅用1種,亦可併用2種以上。含羧基之乙烯性不飽和單體(A1)之中,從更提升對聚醯亞胺系被黏著物之黏著性且剝離時更容易剝離之觀點而言,較佳係丙烯酸、甲基丙烯酸、丙烯酸β-羧基乙酯。在單體混合物中,較佳係以0.1至30質量%之比率,更佳係以1至20質量%之比率含有含羧基之乙烯性不飽和單體(A1)。 Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid and the like. Examples of the unsaturated dicarboxylic acid include, for example, itaconic acid, maleic acid, and fumaric acid. The carboxyl group-containing unsaturated ester may, for example, be β-carboxyethyl acrylate or the like. The carboxyl group-containing ethylenically unsaturated monomer (A1) may be used alone or in combination of two or more. Among the carboxyl group-containing ethylenically unsaturated monomers (A1), acrylic acid and methacrylic acid are preferred from the viewpoint of further improving the adhesion to the polyimide-based adherend and peeling off more easily during peeling. Beta-carboxyethyl acrylate. In the monomer mixture, the carboxyl group-containing ethylenically unsaturated monomer (A1) is preferably contained in a ratio of from 0.1 to 30% by mass, more preferably from 1 to 20% by mass.
就具有碳數4至7之烴基之(甲基)丙烯酸酯(A2)而言,無特別限定,可列舉例如:(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸正戊酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸第三戊酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸異己酯、(甲基)丙烯酸第三己酯、(甲基)丙烯酸正庚酯、(甲基)丙烯酸異庚酯、(甲基)丙烯酸苯甲酯、(甲基)丙烯酸環己酯等。具有碳數4至7之烴基之(甲基)丙烯酸酯(A2)可僅用1種,亦可併用2種以上。具有碳數4至7之烴基之(甲基)丙烯酸酯(A2)之中,從更提升對聚醯亞胺系被黏 著物之黏著性且剝離時更容易剝離之觀點而言,較佳係丙烯酸正丁酯、丙烯酸異丁酯、丙烯酸第三丁酯。在單體混合物中,較佳係以70至99.9質量%之比率,更佳係以80至99質量%之比率含有具有碳數4至7之烴基之(甲基)丙烯酸酯(A2)。 The (meth) acrylate (A2) having a hydrocarbon group having 4 to 7 carbon atoms is not particularly limited, and examples thereof include n-butyl (meth)acrylate and isobutyl (meth)acrylate. Base) tert-butyl acrylate, n-amyl (meth)acrylate, isoamyl (meth)acrylate, third amyl (meth)acrylate, n-hexyl (meth)acrylate, (meth)acrylic acid Ester, third hexyl (meth)acrylate, n-heptyl (meth)acrylate, isoheptyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, and the like. The (meth) acrylate (A2) having a hydrocarbon group having 4 to 7 carbon atoms may be used alone or in combination of two or more. Among the (meth) acrylates (A2) having a hydrocarbon group having 4 to 7 carbon atoms, it is preferred from the viewpoint of further improving the adhesion to the polyimide-based adherend and peeling off more easily during peeling. N-butyl acrylate, isobutyl acrylate, and tert-butyl acrylate. In the monomer mixture, it is preferred to contain the (meth) acrylate (A2) having a hydrocarbon group having 4 to 7 carbon atoms in a ratio of 70 to 99.9% by mass, more preferably 80 to 99% by mass.
單體混合物中,可含有可與含羧基之乙烯性不飽和單體(A1)及具有碳數4至7之烴基之(甲基)丙烯酸酯(A2)共聚合之其他單體。就此種其他單體而言,可列舉例如:具有羥基之乙烯性不飽和單體、具有環氧基之乙烯性不飽和單體、具有異氰酸基之乙烯性不飽和單體、具有碳數8以上之烷基之(甲基)丙烯酸酯、具有碳數8以上之環式烴基之(甲基)丙烯酸酯、具有氧基伸乙基之(甲基)丙烯酸酯、具有氧基伸丙基之(甲基)丙烯酸酯、分子內具有氟原子之(甲基)丙烯酸酯、(甲基)丙烯醯胺等。 The monomer mixture may contain other monomers copolymerizable with the carboxyl group-containing ethylenically unsaturated monomer (A1) and the (meth) acrylate (A2) having a hydrocarbon group of 4 to 7 carbon atoms. Examples of such other monomers include an ethylenically unsaturated monomer having a hydroxyl group, an ethylenically unsaturated monomer having an epoxy group, an ethylenically unsaturated monomer having an isocyanate group, and having a carbon number. a (meth) acrylate having 8 or more alkyl groups, a (meth) acrylate having a cyclic hydrocarbon group having 8 or more carbon atoms, a (meth) acrylate having an oxyethyl group, and an oxypropyl group ( Methyl) acrylate, (meth) acrylate having a fluorine atom in the molecule, (meth) acrylamide or the like.
就具有羥基之乙烯性不飽和單體而言,可列舉例如(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸2-羥基己酯、2-羥基乙基丙烯醯胺等。就具有環氧基之乙烯性不飽和單體而言,可列舉例如(甲基)丙烯酸環氧丙酯等。就具有異氰酸基之乙烯性不飽和單體而言,可列舉例如(甲基)丙烯酸2-異氰酸基乙酯等。就具有氧基伸乙基之(甲基)丙烯酸酯而言,可列舉例如(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸乙氧基乙氧基乙酯、(甲基)丙烯酸甲氧基三乙二醇酯、(甲基)丙烯酸苯氧基乙酯等。就具有氧基伸丙基之(甲基)丙烯酸酯而言,可列舉例如(甲基)丙烯酸聚丙二醇酯等。就分子內具有氟原子之(甲基)丙烯酸酯而言,可列舉例如(甲基)丙烯酸2,2,2-三氟乙酯、(甲基)丙烯酸2,2,3,3-四氟丙酯、(甲基)丙烯酸1H,1H,5H-八氟戊酯等。就具有碳數8以上之烷基之(甲基)丙烯酸酯而言,可列舉例如(甲基)丙烯酸乙基己 酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸鯨蠟酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸二十二酯等。就具有碳數8以上之環式烴基之(甲基)丙烯酸酯而言,可列舉例如(甲基)丙烯酸異莰酯等。 Examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. 2-hydroxyhexyl methacrylate, 2-hydroxyethyl acrylamide, and the like. Examples of the ethylenically unsaturated monomer having an epoxy group include glycidyl (meth)acrylate and the like. The ethylenically unsaturated monomer having an isocyanate group may, for example, be 2-isocyanatoethyl (meth)acrylate. Examples of the (meth) acrylate having an oxyethyl group include methoxyethyl (meth)acrylate, ethoxyethoxyethyl (meth)acrylate, and (meth)acrylic acid. Oxyethylene triethylene glycol ester, phenoxyethyl (meth)acrylate, and the like. The (meth) acrylate having an oxypropyl group may, for example, be a polypropylene glycol (meth)acrylate or the like. Examples of the (meth) acrylate having a fluorine atom in the molecule include 2,2,2-trifluoroethyl (meth)acrylate and 2,2,3,3-tetrafluoro(meth)acrylate. Propyl ester, 1H, 1H, 5H-octafluoropentyl (meth)acrylate, and the like. Examples of the (meth) acrylate having an alkyl group having 8 or more carbon atoms include ethyl hexyl (meth) acrylate, lauryl (meth) acrylate, and cetyl (meth) acrylate. Stearyl methacrylate, behenyl (meth) acrylate, and the like. The (meth) acrylate having a cyclic hydrocarbon group having 8 or more carbon atoms may, for example, be isodecyl (meth)acrylate.
就用以得到基本樹脂(A)之單體混合物的聚合方法而言,無特別限定,可列舉例如溶液聚合法、塊狀聚合法、懸浮聚合法、乳化聚合法等。例如採用溶液聚合法時,將單體混合物與溶劑混合,視需要而添加聚合起始劑、鏈轉移劑,一邊攪拌一邊在50至100℃左右反應1至24小時左右即可。 The polymerization method for obtaining the monomer mixture of the base resin (A) is not particularly limited, and examples thereof include a solution polymerization method, a bulk polymerization method, a suspension polymerization method, and an emulsion polymerization method. For example, when the solution polymerization method is used, the monomer mixture and the solvent are mixed, and if necessary, a polymerization initiator and a chain transfer agent are added, and the mixture is reacted at about 50 to 100 ° C for about 1 to 24 hours while stirring.
此種基本樹脂(A)之重量平均分子量(Mw)無特別限定。基本樹脂(A)較佳係具有10萬至200萬之重量平均分子量,更佳係具有20萬至100萬之重量平均分子量。 The weight average molecular weight (Mw) of such a base resin (A) is not particularly limited. The base resin (A) preferably has a weight average molecular weight of from 100,000 to 2,000,000, more preferably from 200,000 to 1,000,000.
不含羧基之側鏈結晶性聚合物(B)(以下,有時簡稱為「側鏈結晶性聚合物(B)」)為分子內不具有羧基之聚合物。側鏈結晶性聚合物(B)係以含有具有碳數14至30之直鏈狀烷基之(甲基)丙烯酸酯(B1)之單體成分作為構成單元。就具有碳數14至30之直鏈狀烷基之(甲基)丙烯酸酯(B1)而言,可列舉例如(甲基)丙烯酸鯨蠟酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸二十酯、(甲基)丙烯酸二十二酯、(甲基)丙烯酸二十三酯等。此種(甲基)丙烯酸酯(A)之中,較佳係具有碳數18至22之直鏈狀烷基之(甲基)丙烯酸酯。具有碳數14至30之直鏈狀烷基之(甲基)丙烯酸酯(B1)可僅用1種,亦可併用2種以上。 The carboxyl group-free side chain crystalline polymer (B) (hereinafter, simply referred to as "side chain crystalline polymer (B)") is a polymer having no carboxyl group in the molecule. The side chain crystalline polymer (B) is a monomer component containing a (meth) acrylate (B1) having a linear alkyl group having 14 to 30 carbon atoms as a constituent unit. Examples of the (meth) acrylate (B1) having a linear alkyl group having 14 to 30 carbon atoms include, for example, cetyl (meth) acrylate, stearyl (meth) acrylate, and (methyl). Ethylene acrylate, behenyl (meth)acrylate, tris (meth)acrylate, and the like. Among such (meth) acrylates (A), a (meth) acrylate having a linear alkyl group having 18 to 22 carbon atoms is preferred. The (meth) acrylate (B1) having a linear alkyl group having 14 to 30 carbon atoms may be used alone or in combination of two or more.
構成側鏈結晶性聚合物(B)之單體成分若含有(甲基)丙烯酸酯(B1),則無特別限定。但為了使側鏈結晶性聚合物(B)之分子內不具有羧基,不採用例如(甲基)丙烯酸等之類的上述之含羧基之乙烯性不飽和單體作為單體成 分。單體成分中,除了(甲基)丙烯酸酯(B1)以外,亦可含有例如具有碳數1至6之烷基之(甲基)丙烯酸酯(B2)等。 The monomer component constituting the side chain crystalline polymer (B) is not particularly limited as long as it contains the (meth) acrylate (B1). However, in order to prevent the carboxyl group-containing polymer (B) from having a carboxyl group in the molecule, the above-mentioned carboxyl group-containing ethylenically unsaturated monomer such as (meth)acrylic acid or the like is not used as the monomer component. In addition to the (meth) acrylate (B1), the monomer component may contain, for example, a (meth) acrylate (B2) having an alkyl group having 1 to 6 carbon atoms.
就具有碳數1至6之烷基之(甲基)丙烯酸酯(B2)而言,可列舉例如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸丁酯等。 Examples of the (meth) acrylate (B2) having an alkyl group having 1 to 6 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate. Isopropyl (meth)acrylate, butyl (meth)acrylate, and the like.
在構成側鏈結晶性聚合物(B)之單體成分中,較佳係以30至70質量%之比率,更佳係以40至60質量%之比率含有具有碳數14至30之直鏈狀烷基之(甲基)丙烯酸酯(B1)。較佳係以30至70質量%之比率,更佳係以40至60質量%之比率含有具有碳數1至6之烷基之(甲基)丙烯酸酯(B2)。 The monomer component constituting the side chain crystalline polymer (B) preferably contains a linear chain having a carbon number of 14 to 30 in a ratio of 30 to 70% by mass, more preferably 40 to 60% by mass. Alkyl (meth) acrylate (B1). It is preferable to contain the (meth) acrylate (B2) having an alkyl group having 1 to 6 carbon atoms in a ratio of 30 to 70% by mass, more preferably 40 to 60% by mass.
就用以得到側鏈結晶性聚合物(B)之單體成分的聚合方法而言,無特別限定,可列舉例如溶液聚合法、塊狀聚合法、懸浮聚合法、乳化聚合法等。例如採用溶液聚合法時,將單體成分與溶劑混合,視需要而添加聚合起始劑、鏈轉移劑,一邊攪拌一邊在50至100℃左右反應1至6小時左右即可。 The polymerization method for obtaining the monomer component of the side chain crystalline polymer (B) is not particularly limited, and examples thereof include a solution polymerization method, a bulk polymerization method, a suspension polymerization method, and an emulsion polymerization method. For example, when the solution polymerization method is used, the monomer component and the solvent are mixed, and if necessary, a polymerization initiator or a chain transfer agent is added, and the reaction is carried out at about 50 to 100 ° C for about 1 to 6 hours while stirring.
此種側鏈結晶性聚合物(B)之重量平均分子量(Mw)無特別限定。側鏈結晶性聚合物(B)較佳係具有3000至30000之重量平均分子量,更佳係具有6000至15000之重量平均分子量。 The weight average molecular weight (Mw) of the side chain crystalline polymer (B) is not particularly limited. The side chain crystalline polymer (B) preferably has a weight average molecular weight of from 3,000 to 30,000, more preferably from 6,000 to 15,000.
側鏈結晶性聚合物(B)在熔點(Tm)以上的溫度時黏著力會降低。亦即,側鏈結晶性聚合物(B)在未達熔點的溫度結晶化,且在熔點以上的溫度會相轉移而顯示流動性。側鏈結晶性聚合物之熔點無特別限定。側鏈結晶性聚合物較佳係具有70℃以下之熔點,更佳係具有60℃以下之熔點。本說明書中,「熔點」係意指依據某平衡程序,以最初為有序排列整合之聚合物的特定部分成為 無序狀態之溫度,並且可藉由示差掃描熱析儀(DSC)以10℃/分鐘之條件測定而得到。 When the side chain crystalline polymer (B) has a temperature higher than the melting point (Tm), the adhesion is lowered. That is, the side chain crystalline polymer (B) crystallizes at a temperature not reaching the melting point, and the phase transition at a temperature higher than the melting point exhibits fluidity. The melting point of the side chain crystalline polymer is not particularly limited. The side chain crystalline polymer preferably has a melting point of 70 ° C or less, more preferably a melting point of 60 ° C or less. In the present specification, "melting point" means a temperature at which a specific portion of the polymer which is initially integrated in order is disordered according to a certain balancing procedure, and can be 10 ° C by a differential scanning calorimeter (DSC). The condition of /min is determined by measurement.
本發明之一實施形態之感溫性黏著劑係以任意比例含有基本樹脂(A)及側鏈結晶性聚合物(B),較佳係相對於基本樹脂(A)100質量份,以1至30質量份之比例含有側鏈結晶性聚合物(B),更佳係以3至20質量份之比例含有側鏈結晶性聚合物(B)。本發明之一實施形態之感溫性黏著劑係藉由將基本樹脂(A)及側鏈結晶性聚合物(B)混合並攪拌而得。 The temperature sensitive adhesive according to an embodiment of the present invention contains the base resin (A) and the side chain crystalline polymer (B) in an arbitrary ratio, preferably 100 parts by mass based on the base resin (A). The ratio of 30 parts by mass contains the side chain crystalline polymer (B), and more preferably contains the side chain crystalline polymer (B) in a proportion of 3 to 20 parts by mass. The temperature sensitive adhesive according to an embodiment of the present invention is obtained by mixing and stirring a base resin (A) and a side chain crystalline polymer (B).
再者,本發明之一實施形態之感溫性黏著劑可為了提升凝聚力而含有交聯劑。就交聯劑而言,無特別限定,可列舉例如氮雜環丙烷(aziridine)系化合物、環氧系化合物、金屬螫合物系化合物、金屬烷氧化物系化合物、異氰酸酯系化合物等。其中,以金屬螫合物系化合物為合適。藉由使用金屬螫合物系化合物,在高溫區域之剝離能量的散逸受到抑制,且容易抑制剝離時之阻力。 Further, the temperature sensitive adhesive according to an embodiment of the present invention may contain a crosslinking agent for enhancing the cohesive force. The crosslinking agent is not particularly limited, and examples thereof include an aziridine compound, an epoxy compound, a metal chelate compound, a metal alkoxide compound, and an isocyanate compound. Among them, a metal chelate compound is suitable. By using the metal chelate compound, the dissipation of the peeling energy in the high temperature region is suppressed, and the resistance at the time of peeling is easily suppressed.
本發明之一實施形態之感溫性黏著劑可視需要而添加塑化劑、賦黏劑(tackifier)、填料、抗氧化劑等。例如就賦黏劑而言,可列舉特殊松香酯系、萜烯酚系、石油樹脂系、高羥基價松香酯系、氫化松香酯系等。再者,為了更提升與聚醯亞胺系被黏著物之密接性,可添加丙烯酸系、橡膠系等一般的感壓性黏著劑。 A temperature sensitive adhesive according to an embodiment of the present invention may be added with a plasticizer, a tackifier, a filler, an antioxidant, or the like as needed. Examples of the tackifier include a special rosin ester system, a terpene phenol system, a petroleum resin system, a high hydroxyl value rosin ester system, and a hydrogenated rosin ester system. Further, in order to further improve the adhesion to the polyimide-based adhesive, a general pressure-sensitive adhesive such as an acrylic or rubber-based adhesive may be added.
本發明之一實施形態之感溫性黏著劑較佳係對於聚醯亞胺系被黏著物,在23℃時具有2N/25mm以上之黏著強度且在側鏈結晶性聚合物(B)之熔點以上的溫度時具有0.05N/25mm以下之黏著強度。本說明書中,黏著強度係依據JIS Z0237且以300mm/分鐘測定,係對於聚醯亞胺系被黏著物而言之值。感溫性黏著劑若具有如此範圍之黏著強度,則在室溫(未達側鏈結晶性聚合物(B) 之熔點的溫度)可更堅固地黏附聚醯亞胺系被黏著物,且在側鏈結晶性聚合物(B)之熔點以上的溫度更容易使黏著劑從聚醯亞胺系被黏著物剝離。感溫性黏著劑更佳係在23℃時具有5N/25mm以上之黏著強度且在側鏈結晶性聚合物(B)之熔點以上的溫度時具有0.05N/25mm以下之黏著強度。 The temperature sensitive adhesive according to an embodiment of the present invention preferably has a bonding strength of 2N/25 mm or more at 23 ° C and a melting point of the side chain crystalline polymer (B) for the polyimide-based adhesive. The above temperature has an adhesive strength of 0.05 N/25 mm or less. In the present specification, the adhesion strength is measured in accordance with JIS Z0237 and measured at 300 mm/min, and is a value for a polyimide-based adhesive. If the temperature sensitive adhesive has such a range of adhesive strength, the polyimide-based adhesive can be more strongly adhered at room temperature (the temperature at which the melting point of the side chain crystalline polymer (B) is not reached), and The temperature above the melting point of the side chain crystalline polymer (B) is more likely to cause the adhesive to be peeled off from the polyimide-based adherend. The temperature sensitive adhesive preferably has an adhesive strength of 5 N/25 mm or more at 23 ° C and an adhesive strength of 0.05 N/25 mm or less at a temperature higher than the melting point of the side chain crystalline polymer (B).
剝離感溫性黏著劑時,大多會以較JIS所規定之速度更高速(例如3000mm/分鐘左右)剝離。一般以高速剝離時,有剝離強度變高之傾向。然而,在JIS所規定之300mm/分鐘之剝離強度充分低到0.05N/25mm以下時,即使以高速剝離,剝離強度仍難以上昇。因此,一實施形態之感溫性黏著劑與剝離速度無關,可在不對聚醯亞胺系被黏著物造成損傷的狀況下剝離。 When the temperature sensitive adhesive is peeled off, it is often peeled off at a higher speed (for example, about 3000 mm/min) than the speed specified by JIS. Generally, when peeling at a high speed, the peeling strength tends to become high. However, when the peel strength of 300 mm/min prescribed by JIS is sufficiently low to 0.05 N/25 mm or less, even if peeling is performed at a high speed, peeling strength hardly rises. Therefore, the temperature sensitive adhesive of one embodiment can be peeled off without causing damage to the polyimide-based adherend regardless of the peeling speed.
本發明之一實施形態之感溫性黏著劑的使用方法無特別限定,例如可將感溫性黏著劑塗佈於對象之聚醯亞胺系被黏著物而使用,亦可將感溫性黏著劑成形為片狀而如無基材帶(tape)般地使用。 The method of using the temperature sensitive adhesive according to the embodiment of the present invention is not particularly limited. For example, the temperature sensitive adhesive can be applied to the target polyimide-based adhesive, and the temperature sensitive adhesive can be adhered. The agent is formed into a sheet shape and used as a substrate without a tape.
或者,也能以在基材之至少一面形成有含有本發明之一實施形態之感溫性黏著劑之黏著劑層之感溫性黏著帶的形態使用。基材較佳係膜狀,膜狀也包含片狀。就基材之構成材料而言,可列舉例如:聚乙烯、聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚丙烯、聚酯、聚醯胺、聚醯亞胺、聚醯胺醯亞胺、聚碳酸酯、乙烯乙酸乙烯酯共聚物、乙烯丙烯酸乙酯共聚物、乙烯聚丙烯共聚物、聚氯乙烯、聚醚醚酮等合成樹脂。 Alternatively, it may be used in the form of a temperature sensitive adhesive tape having an adhesive layer containing a temperature sensitive adhesive according to an embodiment of the present invention formed on at least one side of the substrate. The substrate is preferably in the form of a film, and the film also includes a sheet. The constituent material of the substrate may, for example, be polyethylene, polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyester, polyamine, polyimine, polyfluorene. A synthetic resin such as an amine imine, a polycarbonate, an ethylene vinyl acetate copolymer, an ethylene ethyl acrylate copolymer, an ethylene polypropylene copolymer, a polyvinyl chloride or a polyether ether ketone.
基材可具有單層構造,亦可具有多層構造。基材通常具有5至500μm左右之厚度。再者,為了提高對黏著劑層之密接性之目的,可對基材施以例如電暈放電處理、電漿處理、噴砂處理、化學蝕刻處理、底漆(primer)處理等表面處理。 The substrate may have a single layer construction or a multilayer construction. The substrate usually has a thickness of about 5 to 500 μm. Further, in order to improve the adhesion to the adhesive layer, the substrate may be subjected to surface treatment such as corona discharge treatment, plasma treatment, sandblasting treatment, chemical etching treatment, primer treatment or the like.
在基材之至少一表面形成含有感溫性黏著劑之黏著劑層的方法無特別限定。可列舉例如將已視需要而於感溫性黏著劑中添加有溶劑之塗佈液,藉由塗佈器等而塗佈於基材之單面或雙面並乾燥之方法等。就塗佈器而言,可列舉例如刀式塗佈器、輥塗佈器、壓延塗佈器(calender coater)、逗式塗佈器、凹版塗佈器、桿塗佈器等。黏著劑層之厚度無特別限定。黏著劑層較佳係具有1至500μm左右之厚度,更佳係具有5至60μm左右之厚度。 The method of forming the pressure-sensitive adhesive layer containing the temperature sensitive adhesive on at least one surface of the substrate is not particularly limited. For example, a coating liquid in which a solvent is added to a temperature sensitive adhesive as needed, and a method of applying it to one side or both sides of a substrate by an applicator or the like and drying it may be mentioned. The applicator may, for example, be a knife coater, a roll coater, a calender coater, a slap coater, a gravure coater, a rod coater or the like. The thickness of the adhesive layer is not particularly limited. The adhesive layer preferably has a thickness of about 1 to 500 μm, more preferably a thickness of about 5 to 60 μm.
僅於基材之一表面形成有含有感溫性黏著劑之黏著劑層之感溫性黏著帶,於另一表面例如可形成感壓接著劑之層,亦可形成含有感溫性黏著劑及感壓接著劑之層。就感壓接著劑而言,可列舉例如天然橡膠接著劑、合成橡膠接著劑、苯乙烯-丁二烯乳膠基底接著劑、嵌段共聚物型之熱塑性橡膠、丁基橡膠、聚異丁烯、丙烯酸接著劑、乙烯基醚系共聚物等。感壓接著劑可使用市售品。 a temperature sensitive adhesive tape having a pressure sensitive adhesive layer on one surface of the substrate alone, and a pressure sensitive adhesive layer on the other surface, for example, or a temperature sensitive adhesive and A layer of pressure sensitive adhesive. The pressure-sensitive adhesive may, for example, be a natural rubber adhesive, a synthetic rubber adhesive, a styrene-butadiene latex base adhesive, a block copolymer type thermoplastic rubber, a butyl rubber, a polyisobutylene, or an acrylic acid. Agent, vinyl ether copolymer, and the like. Commercially available products can be used as the pressure-sensitive adhesive.
依據本發明之一實施形態之感溫性黏著劑,對於聚醯亞胺系被黏著物,在感溫性樹脂之熔點以上的溫度時黏著力顯著降低,可容易地剝離。亦即,對聚醯亞胺系被黏著物可發揮特別的黏著性及剝離性。因此,藉由使用本發明之一實施形態之感溫性黏著劑,可在室溫固定聚醯亞胺系被黏著物並對聚醯亞胺系被黏著物施以加工。加工後,藉由昇溫到感溫性黏著劑所含之側鏈結晶性聚合物(B)之熔點以上的溫度,可容易地從聚醯亞胺系被黏著物剝離感溫性黏著劑。使用有本發明之一實施形態之感溫性黏著劑之感溫性黏著片及感溫性黏著帶亦同。 According to the temperature-sensitive adhesive of the embodiment of the present invention, the adhesion of the polyimide-based adhesive to the temperature above the melting point of the temperature sensitive resin is remarkably lowered, and the adhesive can be easily peeled off. That is, it exhibits special adhesion and peelability to the polyimide-based adhesive. Therefore, by using the temperature sensitive adhesive of one embodiment of the present invention, the polyimide-based adherend can be fixed at room temperature and the polyimide-based adherend can be processed. After the processing, the temperature-sensitive adhesive can be easily peeled off from the polyimide-based adhesive by raising the temperature to a temperature equal to or higher than the melting point of the side chain crystalline polymer (B) contained in the temperature sensitive adhesive. The temperature sensitive adhesive sheet and the temperature sensitive adhesive tape having the temperature sensitive adhesive of one embodiment of the present invention are also used.
本發明之一實施形態之感溫性黏著劑、感溫性黏著片及感溫性黏著帶被使用在例如承載帶(carrier tape)或遮罩帶(masking tape)、或者切割(dicing)時的固定、轉印製程時的固定等。 The temperature sensitive adhesive, the temperature sensitive adhesive sheet, and the temperature sensitive adhesive tape according to an embodiment of the present invention are used, for example, in a carrier tape, a masking tape, or a dicing. Fixation, fixing during transfer process, etc.
以下,雖列舉實施例及比較例具體說明本發明,但本發明不受限於此等實施例。 Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited to the examples.
(合成例A1:基本樹脂之合成) (Synthesis Example A1: Synthesis of Basic Resin)
如表1所示,將92質量%之丙烯酸正丁酯與8質量%之丙烯酸混合,得到單體混合物。相對於此單體混合物100質量份,依比例而添加作為聚合起始劑之PERBUTYL ND(日油(股)製)0.5質量份、及作為溶劑之乙酸甲酯230質量份,於55℃聚合4小時。其後,昇溫至80℃,相對於單體混合物100質量份,依比例而添加作為聚合起始劑之PERHEXYL PV(日油(股)製)0.5質量份。添加後聚合2小時,得到共聚物(基本樹脂)。所得之基本樹脂具有約40萬之重量平均分子量(Mw)。 As shown in Table 1, 92% by mass of n-butyl acrylate was mixed with 8% by mass of acrylic acid to obtain a monomer mixture. 0.5 parts by mass of PERBUTYL ND (manufactured by Nippon Oil Co., Ltd.) as a polymerization initiator and 230 parts by mass of methyl acetate as a solvent were added in proportion to 100 parts by mass of the monomer mixture, and polymerization was carried out at 55 ° C. hour. Then, the temperature was raised to 80 ° C, and 0.5 parts by mass of PERHEXYL PV (manufactured by Nippon Oil Co., Ltd.) as a polymerization initiator was added in proportion to 100 parts by mass of the monomer mixture. After the addition, the polymerization was carried out for 2 hours to obtain a copolymer (base resin). The resulting base resin had a weight average molecular weight (Mw) of about 400,000.
(合成例A2至A6:基本樹脂之合成) (Synthesis Examples A2 to A6: Synthesis of Base Resin)
除了依表1所記載之比率使用表1所記載之單體成分以外,其餘以與合成例A1相同之步驟得到共聚物(基本樹脂)。將各基本樹脂之Mw示於表1。 A copolymer (base resin) was obtained in the same manner as in Synthesis Example A1 except that the monomer components described in Table 1 were used in the ratios shown in Table 1. The Mw of each of the base resins is shown in Table 1.
(比較合成例A1至A3:基本樹脂之合成) (Comparative Synthesis Examples A1 to A3: Synthesis of Basic Resin)
除了依表1所記載之比率使用表1所記載之單體成分以外,其餘以與合成例A1相同之步驟得到共聚物(基本樹脂)。將各基本樹脂之Mw示於表1。 A copolymer (base resin) was obtained in the same manner as in Synthesis Example A1 except that the monomer components described in Table 1 were used in the ratios shown in Table 1. The Mw of each of the base resins is shown in Table 1.
C4A:丙烯酸正丁酯 C4A: n-butyl acrylate
AA:丙烯酸 AA: Acrylic
βCEA:丙烯酸β-羧基乙酯 βCEA: β-carboxyethyl acrylate
EHA:丙烯酸乙基己酯 EHA: ethylhexyl acrylate
C1A:丙烯酸甲酯 C1A: Methyl acrylate
HEA:丙烯酸2-羥基乙酯 HEA: 2-hydroxyethyl acrylate
(合成例B1:側鏈結晶性聚合物之合成) (Synthesis Example B1: Synthesis of Side Chain Crystalline Polymer)
如表2所示,將45質量%之丙烯酸二十二酯(日油(股)製)與55質量%之丙烯酸甲酯混合,得到單體混合物。相對於此單體混合物100質量份,依比例而添加作為聚合起始劑之PERHEXYL PV(日油(股)製)1質量份與十二基硫醇(東京化成工業(股)製)6質量份、及作為溶劑之甲苯100質量份,於80℃聚合3小時,得 到共聚物(側鏈結晶性聚合物)。所得之側鏈結晶性聚合物具有約8000之重量平均分子量(Mw),且具有約50℃之熔點(Tm)。 As shown in Table 2, 45 mass% of behenyl acrylate (manufactured by Nippon Oil Co., Ltd.) was mixed with 55 mass% of methyl acrylate to obtain a monomer mixture. 1 part by mass of PERHEXYL PV (manufactured by Nippon Oil Co., Ltd.) as a polymerization initiator and 1 part by mass of dodecyl mercaptan (manufactured by Tokyo Chemical Industry Co., Ltd.) were added in proportion to 100 parts by mass of the monomer mixture. The mixture and 100 parts by mass of toluene as a solvent were polymerized at 80 ° C for 3 hours to obtain a copolymer (side chain crystalline polymer). The resulting side chain crystalline polymer has a weight average molecular weight (Mw) of about 8,000 and a melting point (Tm) of about 50 °C.
(合成例B2及B3:側鏈結晶性聚合物之合成) (Synthesis Examples B2 and B3: Synthesis of Side Chain Crystalline Polymer)
除了依表2所記載之比率使用表2所記載之單體成分以外,其餘以與合成例B1相同之步驟得到共聚物(側鏈結晶性聚合物)。將各側鏈結晶性聚合物之Mw及Tm示於表2。 A copolymer (side chain crystalline polymer) was obtained in the same manner as in Synthesis Example B1 except that the monomer components described in Table 2 were used in the ratios shown in Table 2. The Mw and Tm of each side chain crystalline polymer are shown in Table 2.
(比較合成例B1及B2:側鏈結晶性聚合物之合成) (Comparative Synthesis Examples B1 and B2: Synthesis of Side Chain Crystalline Polymer)
除了依表2所記載之比率使用表2所記載之單體成分以外,其餘以與合成例B1相同之步驟得到共聚物(側鏈結晶性聚合物)。將各側鏈結晶性聚合物之Mw及Tm示於表2。 A copolymer (side chain crystalline polymer) was obtained in the same manner as in Synthesis Example B1 except that the monomer components described in Table 2 were used in the ratios shown in Table 2. The Mw and Tm of each side chain crystalline polymer are shown in Table 2.
C22A:丙烯酸二十二酯 C22A: behenyl acrylate
C1A:丙烯酸甲酯 C1A: Methyl acrylate
C18A:丙烯酸硬脂酯 C18A: stearyl acrylate
AA:丙烯酸 AA: Acrylic
(實施例1) (Example 1)
相對於合成例A1所得之基本樹脂100質量份,以5質量份之比例混合合成例B1所得之側鏈結晶性聚合物,得到感溫性黏著劑。將所得之感溫性黏著劑以使濃度成為30質量%之方式溶解於乙酸乙酯中,調製感溫性黏著劑溶液。於所得之溶液中,相對於基本樹脂100質量份,以1質量份之比例添加作為交聯劑之金屬螫合物交聯劑(三乙醯丙酮鋁,川研Fine Chemicals(股)製),得到感溫性黏著劑組成物。將所得之感溫性黏著劑組成物塗佈於基材(具有100μm之厚度之PET膜)的單面而形成黏著劑層。黏著劑層具有30μm之厚度。以如此方式得到感溫性黏著帶。 The side chain crystalline polymer obtained in Synthesis Example B1 was mixed in an amount of 5 parts by mass based on 100 parts by mass of the base resin obtained in Synthesis Example A1 to obtain a temperature sensitive adhesive. The temperature sensitive adhesive thus obtained was dissolved in ethyl acetate so as to have a concentration of 30% by mass to prepare a temperature sensitive adhesive solution. In the obtained solution, a metal ruthenium crosslinking agent (aluminum triacetate, manufactured by Kawasaki Fine Chemicals Co., Ltd.) as a crosslinking agent is added in an amount of 1 part by mass based on 100 parts by mass of the base resin. A temperature sensitive adhesive composition is obtained. The obtained temperature sensitive adhesive composition was applied to one side of a substrate (PET film having a thickness of 100 μm) to form an adhesive layer. The adhesive layer has a thickness of 30 μm. In this way, a temperature sensitive adhesive tape is obtained.
依據JIS Z0237來測定所得之感溫性黏著帶之黏著強度。具體而言,將感溫性黏著帶裁切成寬度25mm之長條狀,使用2kg的輥而貼附於由聚醯亞胺形成之被黏著物。於23℃靜置20分鐘而固定,使用測力器以300mm/分鐘之速度將感溫性黏著帶180°剝離,測定在黏著劑/被黏著物界面無殘膠地剝離之試樣在23℃時之接著強度。依下述基準評估所得之接著強度,屬於A或B時評估為具有充分的固定性。將結果示於表3。 The adhesion strength of the obtained temperature sensitive adhesive tape was measured in accordance with JIS Z0237. Specifically, the temperature sensitive adhesive tape was cut into a strip shape having a width of 25 mm, and attached to an adherend formed of polyimine using a 2 kg roller. The sample was allowed to stand at 23 ° C for 20 minutes, and the temperature-sensitive adhesive tape was peeled off at 180 ° using a force measuring device at a speed of 300 mm/min. The sample peeled off at the adhesive/adhered interface without residue was measured at 23 ° C. The strength of the time. The resulting strength was evaluated according to the following criteria, and it was evaluated as having sufficient fixation when belonging to A or B. The results are shown in Table 3.
A:接著強度為5N/25mm以上時。 A: When the strength is 5 N/25 mm or more.
B:接著強度為2N/25mm以上且未達5N/25mm時。 B: When the strength is 2 N/25 mm or more and less than 5 N/25 mm.
C:接著強度未達2N/25mm時。 C: When the strength is less than 2N/25mm.
其次,直到於23℃靜置20分鐘而固定的步驟為止皆以與上述相同步驟進行。其後,於60℃靜置20分鐘,使用測力器而以300mm/分鐘之速度 將感溫性黏著帶180°剝離,測定在60℃時之接著強度。依下述基準評估所得之接著強度,屬於A或B時評估為具有充分的剝離性。將結果示於表3。 Next, the steps up to stand at 20 ° C for 20 minutes were carried out in the same manner as described above. Thereafter, the mixture was allowed to stand at 60 ° C for 20 minutes, and the temperature-sensitive adhesive tape was peeled off at 180 ° using a force measuring device at a speed of 300 mm / minute, and the bonding strength at 60 ° C was measured. The resulting bond strength was evaluated according to the following criteria, and it was evaluated as having sufficient peelability when belonging to A or B. The results are shown in Table 3.
A:接著強度為0.05N/25mm以下時。 A: When the strength is 0.05 N/25 mm or less.
B:接著強度為超過0.05N/25mm且0.1N/25mm以下時。 B: When the strength is more than 0.05 N/25 mm and 0.1 N/25 mm or less.
C:接著強度超過0.1N/25mm時。 C: When the strength exceeds 0.1 N/25 mm.
(實施例2至8) (Examples 2 to 8)
除了依表3所示之比例使用表3所示之基本樹脂及側鏈結晶性聚合物以外,其餘以與實施例1相同之步驟得到感溫性黏著劑。除了分別使用所得之感溫性黏著劑以外,其餘以與實施例1相同之步驟得到感溫性黏著劑組成物。除了分別使用所得之感溫性黏著劑組成物以外,其餘以與實施例1相同之步驟得到感溫性黏著帶。感溫性黏著帶之黏著劑層具有30μm之厚度。針對實施例2至8所得之各感溫性黏著帶,以與實施例1相同之步驟測定在23℃及60℃時之接著強度。將結果示於表3。 A temperature sensitive adhesive was obtained in the same manner as in Example 1 except that the base resin and the side chain crystalline polymer shown in Table 3 were used in the proportions shown in Table 3. A temperature sensitive adhesive composition was obtained in the same manner as in Example 1 except that the obtained temperature sensitive adhesive was used. A temperature sensitive adhesive tape was obtained in the same manner as in Example 1 except that the obtained temperature sensitive adhesive composition was used. The adhesive layer of the temperature sensitive adhesive tape has a thickness of 30 μm. With respect to each of the temperature-sensitive adhesive tapes obtained in Examples 2 to 8, the adhesion strength at 23 ° C and 60 ° C was measured in the same manner as in Example 1. The results are shown in Table 3.
(比較例1至6) (Comparative Examples 1 to 6)
除了依表3所示之比例使用表3所示之基本樹脂及側鏈結晶性聚合物以外,其餘以與實施例1相同之步驟得到感溫性黏著劑。分別使用所得之感溫性黏著劑,以使濃度成為30質量%之方式溶解於乙酸乙酯中,相對於基本樹脂100質量份,在比較例1至3中以1質量份之比例,在比較例4至6中以2質量份之比例添加金屬螫合物交聯劑(三乙醯丙酮鋁,川研Fine Chemicals(股)製),得到感溫性黏著劑組成物。除了分別使用所得之感溫性黏著劑組成物以外,其餘以與實施例1相同之步驟得到感溫性黏著帶。感溫性黏著帶之黏著劑層具有30μm之 厚度。針對比較例1至6所得之各感溫性黏著帶,以與實施例1相同之步驟測定在23℃及60℃時之接著強度。將結果示於表3。 A temperature sensitive adhesive was obtained in the same manner as in Example 1 except that the base resin and the side chain crystalline polymer shown in Table 3 were used in the proportions shown in Table 3. The obtained temperature-sensitive adhesive was dissolved in ethyl acetate so as to have a concentration of 30% by mass, and compared with 100 parts by mass of the base resin in a ratio of 1 part by mass in Comparative Examples 1 to 3, In Examples 4 to 6, a metal ruthenium crosslinking agent (aluminum triacetate, manufactured by Kawasaki Fine Chemicals Co., Ltd.) was added in a ratio of 2 parts by mass to obtain a temperature sensitive adhesive composition. A temperature sensitive adhesive tape was obtained in the same manner as in Example 1 except that the obtained temperature sensitive adhesive composition was used. The adhesive layer of the temperature sensitive adhesive tape has a thickness of 30 μm. With respect to each of the temperature-sensitive adhesive tapes obtained in Comparative Examples 1 to 6, the adhesion strength at 23 ° C and 60 ° C was measured in the same manner as in Example 1. The results are shown in Table 3.
(比較例7及8) (Comparative Examples 7 and 8)
除了依表3所示之比例使用表3所示之基本樹脂及側鏈結晶性聚合物以外,其餘以與實施例1相同之步驟得到感溫性黏著劑。分別使用所得之感溫性黏著劑,以使濃度成為30質量%之方式溶解於乙酸乙酯中,相對於基本樹脂100質量份,以1質量份之比例添加異氰酸酯系交聯劑(Coronate L45,TOSOH(股)製),得到感溫性黏著劑組成物。除了分別使用所得之感溫性黏著劑組成物以外,其餘以與實施例1相同之步驟得到感溫性黏著帶。感溫性黏著帶之黏著劑層具有30μm之厚度。針對比較例1至8所得之各感溫性黏著帶,以與實施例1相同之步驟測定在23℃及60℃時之接著強度。將結果示於表3。 A temperature sensitive adhesive was obtained in the same manner as in Example 1 except that the base resin and the side chain crystalline polymer shown in Table 3 were used in the proportions shown in Table 3. The obtained temperature sensitive adhesive was dissolved in ethyl acetate so as to have a concentration of 30% by mass, and an isocyanate crosslinking agent (Coronate L45, was added in an amount of 1 part by mass based on 100 parts by mass of the base resin. TOSOH (stock) system, to obtain a temperature sensitive adhesive composition. A temperature sensitive adhesive tape was obtained in the same manner as in Example 1 except that the obtained temperature sensitive adhesive composition was used. The adhesive layer of the temperature sensitive adhesive tape has a thickness of 30 μm. With respect to each of the temperature-sensitive adhesive tapes obtained in Comparative Examples 1 to 8, the adhesion strength at 23 ° C and 60 ° C was measured in the same manner as in Example 1. The results are shown in Table 3.
如表3所示,可得知對於由聚醯亞胺形成之被黏著物,實施例1至8所得之感溫性黏著劑(感溫性黏著帶)在23℃(室溫)時具有充分的固定性,在60℃(側鏈結晶性聚合物之熔點以上的溫度)時具有充分的剝離性。因此,實施例1至8所得之感溫性黏著劑(感溫性黏著帶)在室溫時可充分地固定聚醯亞胺系被 黏著物,在側鏈結晶性聚合物之熔點以上的溫度時可容易從聚醯亞胺系被黏著物剝離。 As shown in Table 3, it was found that the temperature-sensitive adhesive (temperature-sensitive adhesive tape) obtained in Examples 1 to 8 was sufficient at 23 ° C (room temperature) for the adherend formed of polyimide. The fixability is sufficient at 60 ° C (temperature above the melting point of the side chain crystalline polymer). Therefore, the temperature sensitive adhesive (temperature sensitive adhesive tape) obtained in Examples 1 to 8 can sufficiently fix the polyimide-based adhesive at room temperature, and the temperature is higher than the melting point of the side chain crystalline polymer. It can be easily peeled off from the polyimide-based adhesive.
另一方面,比較例1未使用側鏈結晶性聚合物,比較例2、3、6及8使用分子內含羧基之側鏈結晶性聚合物,比較例4至8使用不含具有碳數4至7之烴基之(甲基)丙烯酸酯(A2)之單體混合物的共聚物作為基本樹脂。因此,可得知對於由聚醯亞胺形成之被黏著物,比較例1至8所得之感溫性黏著劑(感溫性黏著帶)之固定性及剝離性中至少一者不佳。 On the other hand, Comparative Example 1 did not use a side chain crystalline polymer, Comparative Examples 2, 3, 6 and 8 used a side chain crystalline polymer having a carboxyl group in the molecule, and Comparative Examples 4 to 8 did not contain a carbon number of 4. As a base resin, a copolymer of a monomer mixture of a (meth) acrylate (A2) to a hydrocarbon group of 7. Therefore, it was found that at least one of the fixability and the peeling property of the temperature sensitive adhesive (temperature sensitive adhesive tape) obtained in Comparative Examples 1 to 8 was poor for the adherend formed of polyimide.
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