TW201700691A - Thermosensitive adhesive - Google Patents
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- TW201700691A TW201700691A TW105109167A TW105109167A TW201700691A TW 201700691 A TW201700691 A TW 201700691A TW 105109167 A TW105109167 A TW 105109167A TW 105109167 A TW105109167 A TW 105109167A TW 201700691 A TW201700691 A TW 201700691A
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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
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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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
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- 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
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
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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
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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
- C09J7/35—Heat-activated
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
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- C09J2433/00—Presence of (meth)acrylic polymer
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- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
Abstract
Description
本發明關於感溫性黏著劑。 The present invention relates to a temperature sensitive adhesive.
感溫性黏著劑是含有側鏈結晶性聚合物作為主成分，且在冷卻至未達側鏈結晶性聚合物的熔點的溫度時，由於側鏈結晶性聚合物結晶化而使黏著力降低的黏著劑。感溫性黏著劑被加工成片、帶等，在平板顯示器(Flat Panel Display：以下有時稱為「FPD」)等的製造步驟中，要暫時固定由玻璃、塑料等所構成的基板時使用(例如，參照專利文獻1)。用於這樣的用途的感溫性黏著劑，有時根據步驟的不同會曝露於100℃以上的高溫環境下，因此需要耐熱性。 The thermosensitive adhesive contains a side chain crystalline polymer as a main component, and when cooled to a temperature at which the melting point of the side chain crystalline polymer is not reached, the adhesion of the side chain crystalline polymer is lowered by the crystallization of the side chain crystalline polymer. Adhesive. The temperature-sensitive adhesive is processed into a sheet, a tape, etc., and is used in a manufacturing process such as a flat panel display (hereinafter sometimes referred to as "FPD") to temporarily fix a substrate made of glass or plastic. (For example, refer to Patent Document 1). The temperature sensitive adhesive used for such a purpose may be exposed to a high temperature environment of 100 ° C or higher depending on the steps, and thus heat resistance is required.
但是，以往的感溫性黏著劑被用於上述用途時，有時為了充分展現黏著力而需要加熱至50℃附近。另外，有時為了充分降低黏著力而需要冷卻至5℃附近。因此，在將以往的感溫性黏著劑用於上述用途的情況下，存在貼附及剝離時需要設備或環境、花費成本的問題。另外，若將以往的感溫性黏著劑在室溫下剝離時，則存在發生所謂的尖嘯(zipping)現象的問題。若發生尖嘯現象，則 由於會對被黏物局部施加負荷，而有可能使被黏物破損。 However, when the conventional temperature sensitive adhesive is used for the above-mentioned use, it is necessary to heat up to around 50 ° C in order to sufficiently exhibit the adhesive force. In addition, in order to sufficiently reduce the adhesion, it is necessary to cool to near 5 ° C. Therefore, when a conventional temperature sensitive adhesive is used for the above-mentioned use, there is a problem that equipment, an environment, and cost are required at the time of attachment and peeling. Further, when the conventional temperature sensitive adhesive is peeled off at room temperature, there is a problem that a so-called zipping phenomenon occurs. If a scream occurs, then Since the load is locally applied to the adherend, the adherend may be damaged.
[專利文獻1]日本特開2012-102212號公報 [Patent Document 1] Japanese Laid-Open Patent Publication No. 2012-102212
本發明的課題在於提供一種感溫性黏著劑，其耐熱性優異，並且能夠在室溫下進行對被黏物的貼附及剝離，且在室溫下剝離時能夠抑制尖嘯現象的發生。 An object of the present invention is to provide a temperature sensitive adhesive which is excellent in heat resistance and can be attached and peeled to an adherend at room temperature, and can suppress occurrence of squeaking when peeled off at room temperature.
本發明的感溫性黏著劑係含有在側鏈具有碳數為16以上的直鏈狀烷基的側鏈結晶性聚合物，在未達前述側鏈結晶性聚合物的熔點的溫度下黏著力會降低，其中，前述熔點為30至45℃，前述側鏈結晶性聚合物係以50至90重量%的比例聚合有具有前述碳數為16以上的直鏈狀烷基的(甲基)丙烯酸酯，前述感溫性黏著劑更含有具有23℃以下的軟化點的增黏劑。 The temperature sensitive adhesive of the present invention contains a side chain crystalline polymer having a linear alkyl group having a carbon number of 16 or more in a side chain, and is adhesive at a temperature which does not reach the melting point of the side chain crystalline polymer. In the case where the melting point is 30 to 45 ° C, the side chain crystalline polymer is polymerized in a ratio of 50 to 90% by weight with a (meth)acrylic acid having a linear alkyl group having a carbon number of 16 or more. The ester, the temperature sensitive adhesive further contains a tackifier having a softening point of 23 ° C or lower.
根據本發明，具有如下效果：耐熱性優異，並且能夠在室溫下進行對被黏物的貼附及剝離，且在室溫下剝離時能夠抑制尖嘯現象的發生。 According to the present invention, it is excellent in heat resistance, and it is possible to perform adhesion and peeling of the adherend at room temperature, and it is possible to suppress the occurrence of squeaking when peeling at room temperature.
以下，詳細說明本發明的一個實施形態涉及的感溫性黏著劑。本實施形態的感溫性黏著劑係含有側鏈結晶性聚合物。側鏈結晶性聚合物是具有熔點的聚合物。熔點是指通過某平衡程序使最初被整合為有秩序的排列的聚合物的特定部分成為無秩序狀態的溫度，且是利用差示熱掃描量熱儀(DSC)以10℃/分鐘的測定條件進行測定而得到的值。 Hereinafter, the temperature sensitive adhesive according to an embodiment of the present invention will be described in detail. The temperature sensitive adhesive of the present embodiment contains a side chain crystalline polymer. The side chain crystalline polymer is a polymer having a melting point. The melting point refers to a temperature at which a specific portion of the polymer which is initially integrated into an ordered arrangement is disordered by a certain balancing procedure, and is measured by a differential thermal scanning calorimeter (DSC) at a measurement condition of 10 ° C /min. The value obtained by the measurement.
側鏈結晶性聚合物在未達上述熔點的溫度下會結晶化，且在熔點以上的溫度下相轉移而顯示流動性。即，側鏈結晶性聚合物具有因應溫度變化而可逆地產生結晶狀態或流動狀態的感溫性。並且，本實施形態的感溫性黏著劑係以在未達熔點的溫度下側鏈結晶性聚合物發生結晶化時黏著力所降低的比例來含有側鏈結晶性聚合物。也就是說，本實施形態的感溫性黏著劑由於含有側鏈結晶性聚合物作為主成分，因此在將感溫性黏著劑從被黏物剝離時，若將感溫性黏著劑冷卻至未達側鏈結晶性聚合物的熔點的溫度，則由於側鏈結晶性聚合物發生結晶化而會使黏著力降低。 The side chain crystalline polymer crystallizes at a temperature that does not reach the above melting point, and phase shifts at a temperature higher than the melting point to exhibit fluidity. That is, the side chain crystalline polymer has a temperature sensitive property which reversibly generates a crystal state or a flow state in response to a temperature change. In addition, the temperature sensitive adhesive of the present embodiment contains a side chain crystalline polymer at a ratio at which the adhesion of the side chain crystalline polymer is lowered when the melting point of the side chain crystalline polymer is not reached. In other words, since the temperature sensitive adhesive of the present embodiment contains a side chain crystalline polymer as a main component, when the temperature sensitive adhesive is peeled off from the adherend, the temperature sensitive adhesive is cooled to no When the temperature of the melting point of the side chain crystalline polymer is reached, the adhesion of the side chain crystalline polymer is lowered to lower the adhesion.
側鏈結晶性聚合物係在側鏈具有碳數為16以上的直鏈狀烷基。即，側鏈結晶性聚合物是在側鏈具有碳數為16以上的直鏈狀烷基的梳形的聚合物，該側鏈通過分子間力等而整合為有秩序的排列從而結晶化。 The side chain crystalline polymer has a linear alkyl group having a carbon number of 16 or more in the side chain. In other words, the side chain crystalline polymer is a comb-shaped polymer having a linear alkyl group having a carbon number of 16 or more in a side chain, and the side chain is integrated into an orderly arrangement by crystallization or the like to be crystallized.
本實施形態中，在向側鏈結晶性聚合物導 入碳數為16以上的直鏈狀烷基時，將具有碳數為16以上的直鏈狀烷基的(甲基)丙烯酸酯聚合作為結晶性成分。作為具有碳數為16以上的直鏈狀烷基的(甲基)丙烯酸酯，可舉出例如：(甲基)丙烯酸十六烷基酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸二十烷基酯、(甲基)丙烯酸二十二烷基酯等具有碳數為16至22的線狀烷基的(甲基)丙烯酸酯，此等可以使用1種或混合使用2種以上。需要說明的是，(甲基)丙烯酸酯是指丙烯酸酯或甲基丙烯酸酯。 In this embodiment, the crystalline polymer is guided to the side chain. When a linear alkyl group having 16 or more carbon atoms is added, a (meth) acrylate having a linear alkyl group having 16 or more carbon atoms is polymerized as a crystalline component. Examples of the (meth) acrylate having a linear alkyl group having 16 or more carbon atoms include, for example, cetyl (meth)acrylate, stearyl (meth)acrylate, and (methyl). A (meth) acrylate having a linear alkyl group having a carbon number of 16 to 22, such as an eicosyl acrylate or a behenyl (meth) acrylate, may be used alone or in combination of two. the above. It should be noted that (meth) acrylate means acrylate or methacrylate.
另外，除了具有碳數為16以上的直鏈狀烷基的(甲基)丙烯酸酯以外，亦可以進一步聚合具有碳數為1至12的烷基的(甲基)丙烯酸酯、極性單體、反應性氟化合物等。若進一步聚合具有碳數為1至12的烷基的(甲基)丙烯酸酯、極性單體，則能夠調整感溫性黏著劑的黏著物性。若進一步聚合反應性氟化合物，則不僅由於側鏈結晶性聚合物的結晶化而使黏著力降低，而且由於加上起因於反應性氟化合物造成的脫模性，由此能夠提高感溫性黏著劑的剝離性。 Further, in addition to the (meth) acrylate having a linear alkyl group having 16 or more carbon atoms, a (meth) acrylate having a C 1 to 12 alkyl group, a polar monomer, and the like may be further polymerized. Reactive fluorine compounds and the like. When the (meth) acrylate having a C 1 to 12 alkyl group or a polar monomer is further polymerized, the adhesive property of the temperature sensitive adhesive can be adjusted. When the reactive fluorine compound is further polymerized, the adhesive strength is lowered not only by the crystallization of the side chain crystalline polymer, but also the mold release property due to the reactive fluorine compound is added, whereby the temperature sensitive adhesive can be improved. Peelability of the agent.
作為具有碳數為1至12的烷基的(甲基)丙烯酸酯，可舉出例如：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸己酯、(甲基)丙烯酸月桂酯等，此等可以使用1種或混合使用2種以上。 Examples of the (meth) acrylate having an alkyl group having 1 to 12 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate. The hexyl acrylate, the lauryl (meth) acrylate, etc. may be used alone or in combination of two or more.
作為極性單體，可舉出例如：丙烯酸、甲基丙烯酸、丁烯酸、衣康酸、馬來酸、富馬酸等具有羧基的乙烯不飽和單體；(甲基)丙烯酸2-羥基乙酯、(甲基)丙 烯酸2-羥基丙酯、(甲基)丙烯酸2-羥基己酯等具有羥基的乙烯不飽和單體等，此等可以使用1種或混合使用2種以上。 Examples of the polar monomer include an ethylenically unsaturated monomer having a carboxyl group such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, or fumaric acid; 2-hydroxyethyl (meth)acrylate Ester, (meth) propyl Ethylene-unsaturated monomer having a hydroxyl group such as 2-hydroxypropyl acrylate or 2-hydroxyhexyl (meth)acrylate may be used alone or in combination of two or more.
反應性氟化合物是指具有顯示反應性的官能基的氟化合物。作為顯示反應性的官能基，可舉出例如：乙烯基、烯丙基、(甲基)丙烯酸基、(甲基)丙烯醯基、(甲基)丙烯醯氧基等具有乙烯性不飽和雙鍵的基團；環氧基(包括縮水甘油基及環氧環烷基)、巰基、甲醇基、羧基、矽烷醇基、酚基、胺基、羥基等。 The reactive fluorine compound means a fluorine compound having a functional group exhibiting reactivity. Examples of the functional group exhibiting reactivity include an ethylenic unsaturated double such as a vinyl group, an allyl group, a (meth)acrylic group, a (meth)acrylonitrile group or a (meth)acryloxy group. A group of a bond; an epoxy group (including a glycidyl group and an epoxycycloalkyl group), a mercapto group, a methyl group, a carboxyl group, a stanol group, a phenol group, an amine group, a hydroxyl group, and the like.
作為反應性氟化合物的具體例，可舉出下述通式(I)所示的化合物等。 Specific examples of the reactive fluorine compound include a compound represented by the following formula (I).
R1-CF3 (I)[式中，R1表示基CH2=CHCOOR2-或CH2=C(CH3)COOR2-(式中，R2表示伸烷基。)。] R 1 -CF 3 (I) [wherein R 1 represents a group CH 2 =CHCOOR 2 - or CH 2 =C(CH 3 )COOR 2 - (wherein R 2 represents an alkylene group.). ]
通式(I)中，作為R2所示的伸烷基，可舉出例如，亞甲基、伸乙基、三亞甲基、甲基伸乙基、伸丙基、四亞甲基、五亞甲基、六亞甲基等碳數為1至6的直鏈或支鏈的伸烷基等。 In the general formula (I), examples of the alkylene group represented by R 2 include a methylene group, an ethylidene group, a trimethylene group, a methyl ethyl group, a propyl group, a tetramethylene group, and a penta A linear or branched alkylene group having a carbon number of 1 to 6 such as a methylene group or a hexamethylene group.
作為通式(I)所示的化合物的具體例，可舉出下述式(Ia)、(Ib)所示的化合物等。 Specific examples of the compound represented by the formula (I) include compounds represented by the following formulas (Ia) and (Ib).
上述反應性氟化合物可以使用市售品。作為市售的反應性氟化合物，可舉出例如：均為大阪有機化學工業公司製的「Viscoat 3F」、「Viscoat 3FM」、「Viscoat 4F」、「Viscoat 8F」、「Viscoat 8FM」，共榮社化學股份有限公司製的「Light Ester M-3F」等。 A commercially available product can be used as the above reactive fluorine compound. As a commercially available reactive fluorine compound, for example, "Viscoat 3F", "Viscoat 3FM", "Viscoat 4F", "Viscoat 8F", and "Viscoat 8FM" manufactured by Osaka Organic Chemical Industry Co., Ltd. "Light Ester M-3F" manufactured by Seika Chemical Co., Ltd.
作為聚合方法，沒有特別限定，可以採用例如溶液聚合法、本體聚合法、懸浮聚合法、乳液聚合法等。在採用溶液聚合法的情況下，將上述各單體加入溶劑並在40至90℃左右攪拌2至10小時左右即可。 The polymerization method is not particularly limited, and for example, a solution polymerization method, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, or the like can be employed. In the case of the solution polymerization method, each of the above monomers is added to a solvent and stirred at about 40 to 90 ° C for about 2 to 10 hours.
作為側鏈結晶性聚合物的重量平均分子量，較佳為40萬以上，更佳為50萬至100萬，進一步更佳為50萬至80萬，但不限於此等。重量平均分子量是通過凝膠滲透層析儀(GPC)進行測定，並對所得到的測定值進行聚苯乙烯換算的值。 The weight average molecular weight of the side chain crystalline polymer is preferably 400,000 or more, more preferably 500,000 to 1,000,000, still more preferably 500,000 to 800,000, but is not limited thereto. The weight average molecular weight is measured by a gel permeation chromatography (GPC), and the obtained measured value is a value in terms of polystyrene.
此處，本實施形態中，上述側鏈結晶性聚合物的熔點為30至45℃，較佳為35至45℃。藉此，能夠在室溫下使側鏈結晶性聚合物結晶化，能夠降低室溫下的黏著力。因此，能夠提高室溫剝離性，且能夠在室溫下剝離時抑制尖嘯現象的發生。室溫是指23℃±5℃。熔點係能夠通過調整側鏈結晶性聚合物的組成等而控制為所期望的值。 Here, in the present embodiment, the side chain crystalline polymer has a melting point of 30 to 45 ° C, preferably 35 to 45 ° C. Thereby, the side chain crystalline polymer can be crystallized at room temperature, and the adhesion at room temperature can be lowered. Therefore, the room temperature peeling property can be improved, and the occurrence of the squeaking phenomenon can be suppressed when peeling at room temperature. Room temperature means 23 ° C ± 5 ° C. The melting point can be controlled to a desired value by adjusting the composition of the side chain crystalline polymer or the like.
另外，本實施形態的側鏈結晶性聚合物中，以構成側鏈結晶性聚合物的單體的合計100重量%為基準，以50至90重量%、較佳為60至80重量%、更較佳 為65至75重量%的比例聚合上述具有碳數為16以上的直鏈狀烷基的(甲基)丙烯酸酯。藉此，能夠抑制將熔點設為30至45℃時導致的室溫貼附性的降低。即，若將熔點設為30至45℃，則如上所述，室溫下的黏著力降低，因此有室溫剝離性提高但室溫貼附性降低的傾向。本實施形態中，如上所述，以50至90重量%的比例聚合具有碳數為16以上的直鏈狀烷基的(甲基)丙烯酸酯。若以這樣的特定的比例聚合作為結晶性成分的具有碳數為16以上的直鏈狀烷基的(甲基)丙烯酸酯，則能夠提高所謂的黏性(tackiness)。因此，能夠抑制將熔點設為30至45℃時導致的室溫貼附性的降低。另外，若以上述特定比例聚合具有碳數為16以上的直鏈狀烷基的(甲基)丙烯酸酯，則能夠抑制黏著劑的凝聚力降低。結果，在將黏著劑剝離時，亦能抑制所謂的殘膠等發生。 In addition, in the side chain crystalline polymer of the present embodiment, 50 to 90% by weight, preferably 60 to 80% by weight, based on 100% by weight based on the total of the monomers constituting the side chain crystalline polymer, Better The (meth) acrylate having a linear alkyl group having 16 or more carbon atoms is polymerized in a ratio of 65 to 75% by weight. Thereby, it is possible to suppress a decrease in room temperature adhesion caused by setting the melting point to 30 to 45 °C. In other words, when the melting point is 30 to 45° C., since the adhesive strength at room temperature is lowered as described above, the room temperature peeling property is improved, but the room temperature adhesion property tends to be lowered. In the present embodiment, as described above, the (meth) acrylate having a linear alkyl group having 16 or more carbon atoms is polymerized in a ratio of 50 to 90% by weight. When a (meth) acrylate having a linear alkyl group having 16 or more carbon atoms as a crystalline component is polymerized in such a specific ratio, the so-called tackiness can be improved. Therefore, it is possible to suppress a decrease in room temperature adhesion caused by setting the melting point to 30 to 45 °C. In addition, when a (meth) acrylate having a linear alkyl group having 16 or more carbon atoms is polymerized in the above specific ratio, it is possible to suppress a decrease in cohesive force of the adhesive. As a result, when the adhesive is peeled off, the occurrence of so-called residual glue or the like can be suppressed.
需要說明的是，具有碳數為16以上的直鏈狀烷基的(甲基)丙烯酸酯以外的其它單體的聚合比例沒有特別限定。例如，由具有碳數為16以上的直鏈狀烷基的(甲基)丙烯酸酯、具有碳數為1至12的烷基的(甲基)丙烯酸酯及極性單體的共聚物構成側鏈結晶性聚合物時，只要將具有碳數為16以上的直鏈狀烷基的(甲基)丙烯酸酯以50至90重量%、將具有碳數為1至12的烷基的(甲基)丙烯酸酯以9至40重量%、將極性單體以1至10重量%的比例聚合即可，較佳係只要將具有碳數為16以上的直鏈狀烷基的(甲基)丙烯酸酯以50至70重量%、將具有碳數為1至12 的烷基的(甲基)丙烯酸酯以29至40重量%、將極性單體以1至10重量%的比例聚合即可。另外，例如，由具有碳數為16以上的直鏈狀烷基的(甲基)丙烯酸酯、具有碳數為1至12的烷基的(甲基)丙烯酸酯、極性單體及反應性氟化合物的共聚物構成側鏈結晶性聚合物時，只要將具有碳數為16以上的直鏈狀烷基的(甲基)丙烯酸酯以50至90重量%、將具有碳數為1至12的烷基的(甲基)丙烯酸酯以8至30重量%、將極性單體以1至10重量%、將反應性氟化合物以1至10重量%的比例聚合即可，較佳係只要將具有碳數為16以上的直鏈狀烷基的(甲基)丙烯酸酯以50至70重量%、將具有碳數為1至12的烷基的(甲基)丙烯酸酯以28至30重量%、將極性單體以1至10重量%、將反應性氟化合物以1至10重量%的比例聚合即可。 In addition, the polymerization ratio of the monomer other than the (meth) acrylate having a linear alkyl group having 16 or more carbon atoms is not particularly limited. For example, a side chain is composed of a (meth) acrylate having a linear alkyl group having 16 or more carbon atoms, a (meth) acrylate having an alkyl group having 1 to 12 carbon atoms, and a polar monomer. In the case of a crystalline polymer, a (meth) acrylate having a linear alkyl group having a carbon number of 16 or more is used as a (meth) acrylate having a carbon number of 1 to 12 at 50 to 90% by weight. The acrylate may be polymerized at a ratio of from 1 to 10% by weight of the polar monomer in an amount of from 9 to 40% by weight, preferably a (meth) acrylate having a linear alkyl group having a carbon number of 16 or more. 50 to 70% by weight, will have a carbon number of 1 to 12 The alkyl (meth) acrylate may be polymerized at a ratio of from 1 to 10% by weight based on the polar monomer. Further, for example, (meth) acrylate having a linear alkyl group having 16 or more carbon atoms, (meth) acrylate having an alkyl group having 1 to 12 carbon atoms, a polar monomer, and reactive fluorine When the copolymer of the compound constitutes a side chain crystalline polymer, the (meth) acrylate having a linear alkyl group having a carbon number of 16 or more may have a carbon number of 1 to 12 at 50 to 90% by weight. The alkyl (meth) acrylate may be polymerized in an amount of from 8 to 30% by weight, the polar monomer may be from 1 to 10% by weight, and the reactive fluorine compound may be used in an amount of from 1 to 10% by weight, preferably as long as it has a (meth) acrylate having a linear alkyl group having a carbon number of 16 or more and a (meth) acrylate having an alkyl group having a carbon number of 1 to 12 at 28 to 30% by weight, The polar monomer may be polymerized at a ratio of from 1 to 10% by weight and the reactive fluorine compound at a ratio of from 1 to 10% by weight.
另一方面，本實施形態的感溫性黏著劑更含有具有23℃以下的軟化點的增黏劑。藉此，能夠抑制將具有碳數為16以上的直鏈狀烷基的(甲基)丙烯酸酯以50至90重量%的比例聚合所導致，亦即所謂的錨定效果，在室溫下剝離時能夠抑制尖嘯現象的發生。即，本實施形態中，將具有碳數為16以上的直鏈狀烷基的(甲基)丙烯酸酯以50至90重量%的比例聚合時，該比例是多於以往的側鏈結晶性聚合物的比例。具有碳數為16以上的直鏈狀烷基的(甲基)丙烯酸酯是結晶性成分，因此若具有碳數為16以上的直鏈狀烷基的(甲基)丙烯酸酯的比例變多，則在環境溫度下降時容易表現出錨定效果，在室溫下剝離時容易發 生尖嘯現象。本實施形態中，如上所述，更含有具有23℃以下的軟化點的增黏劑。若更含有具有這樣的特定軟化點的增黏劑，則能夠抑制上述的錨定效果，在室溫下剝離時能夠抑制尖嘯現象的發生。另外，室溫貼附性也有提高的傾向。並且，根據本實施形態，通過含有具有這樣的特定軟化點的增黏劑所帶來的上述效果、通過使熔點為30至45℃所帶來的上述效果、及通過以50至90重量%的比例將具有碳數為16以上的直鏈狀烷基的(甲基)丙烯酸酯聚合所帶來的上述效果之互相作用，能夠在室溫下進行對被黏物的貼附及剝離，在且室溫下剝離時能夠抑制尖嘯現象的發生。因此，根據本實施形態，能夠在23℃±5℃的環境溫度下進行對被黏物的貼附及剝離。另外，根據上述構成，亦能發揮優異的耐熱性。因此，根據本實施形態，能夠使在23℃±5℃的環境溫度下暫時固定的被黏物曝露於100℃以上、較佳為100至150℃的環境溫度後，在23℃±5℃的環境溫度下拆掉。因此，本實施形態的感溫性黏著劑能夠適宜地用於FPD的製造步驟中的基板的暫時固定用途。 On the other hand, the temperature sensitive adhesive of the present embodiment further contains a tackifier having a softening point of 23 ° C or lower. Thereby, it is possible to suppress the polymerization of the (meth) acrylate having a linear alkyl group having a carbon number of 16 or more in a ratio of 50 to 90% by weight, that is, a so-called anchoring effect, and peeling at room temperature. It can suppress the occurrence of screaming. In other words, in the present embodiment, when the (meth) acrylate having a linear alkyl group having 16 or more carbon atoms is polymerized at a ratio of 50 to 90% by weight, the ratio is more than that of the conventional side chain crystalline polymerization. The proportion of things. Since the (meth) acrylate having a linear alkyl group having a carbon number of 16 or more is a crystalline component, the proportion of the (meth) acrylate having a linear alkyl group having 16 or more carbon atoms is increased. It is easy to show anchoring effect when the ambient temperature drops, and it is easy to be released when peeling at room temperature. The screaming phenomenon. In the present embodiment, as described above, a tackifier having a softening point of 23 ° C or lower is further contained. When the tackifier having such a specific softening point is further contained, the anchoring effect described above can be suppressed, and the occurrence of squeaking can be suppressed at the time of peeling at room temperature. In addition, the adhesion at room temperature tends to increase. Further, according to the present embodiment, the above effects by the viscosity-increasing agent having such a specific softening point, the above-mentioned effects by melting the melting point of 30 to 45 ° C, and the passage of 50 to 90% by weight The ratio of the above effects by the polymerization of a (meth) acrylate having a linear alkyl group having 16 or more carbon atoms, and the adhesion and peeling of the adherend at room temperature can be performed. The occurrence of squeaking can be suppressed when peeling at room temperature. Therefore, according to the present embodiment, attachment and peeling of the adherend can be performed at an ambient temperature of 23 ° C ± 5 ° C. Further, according to the above configuration, excellent heat resistance can be exhibited. Therefore, according to the present embodiment, the adherend temporarily fixed at an ambient temperature of 23 ° C ± 5 ° C can be exposed to an ambient temperature of 100 ° C or higher, preferably 100 to 150 ° C, and then at 23 ° C ± 5 ° C. Removed at ambient temperature. Therefore, the temperature sensitive adhesive of the present embodiment can be suitably used for the temporary fixation of the substrate in the production process of the FPD.
需要說明的是，增黏劑的軟化點的下限值沒有特別限定。軟化點是根據JIS K 5902規定的環球法測定的值。 In addition, the lower limit of the softening point of a tackifier is not specifically limited. The softening point is a value measured according to the ring and ball method prescribed in JIS K 5902.
作為增黏劑，較佳為液態者。另外，作為增黏劑的組成，可舉出例如松香系樹脂等。松香系樹脂對於上述側鏈結晶性聚合物能發揮優異的相容性。作為松香系樹脂，可舉出例如松香酯等。 As the tackifier, it is preferably a liquid. Moreover, as a composition of a tackifier, a rosin-type resin etc. are mentioned, for example. The rosin-based resin exhibits excellent compatibility with the above-mentioned side chain crystalline polymer. Examples of the rosin-based resin include rosin esters and the like.
增黏劑的含量相對於側鏈結晶性聚合物100重量份較佳為5至30重量份，更佳為10至30重量份。若增加增黏劑的含量，則有室溫剝離性降低的傾向。另外，若減少增黏劑的含量，則有在室溫下剝離時難以抑制尖嘯現象的發生的傾向。 The content of the tackifier is preferably 5 to 30 parts by weight, more preferably 10 to 30 parts by weight, per 100 parts by weight of the side chain crystalline polymer. When the content of the tackifier is increased, the room temperature peeling property tends to be lowered. Further, when the content of the tackifier is reduced, it is difficult to suppress the occurrence of the screaming phenomenon when peeling at room temperature.
上述增黏劑可以使用市售品。作為市售的增黏劑，可舉出例如：荒川化學工業公司製的「SUPER ESTER A-18」等。 Commercially available products can be used as the above tackifier. As a commercially available tackifier, for example, "SUPER ESTER A-18" manufactured by Arakawa Chemical Industries Co., Ltd., and the like can be mentioned.
另一方面，側鏈結晶性聚合物較佳係通過交聯劑而交聯。作為交聯劑，可舉出例如：金屬螯合物、氮丙啶化合物、異氰酸酯化合物、環氧化合物等。此等之中，在進一步提高耐熱性的觀點而言，較佳為金屬螯合物。換言之，側鏈結晶性聚合物較佳係通過金屬螯合物而交聯。 On the other hand, the side chain crystalline polymer is preferably crosslinked by a crosslinking agent. The crosslinking agent may, for example, be a metal chelate compound, an aziridine compound, an isocyanate compound or an epoxy compound. Among these, a metal chelate compound is preferred from the viewpoint of further improving heat resistance. In other words, the side chain crystalline polymer is preferably crosslinked by a metal chelate.
作為金屬螯合物，可舉出例如：多價金屬的乙醯丙酮配位化合物、多價金屬的乙醯乙酸酯配位化合物等。作為多價金屬，可舉出例如鋁、鎳、鉻、鐵、鈦、鋅、鈷、錳、鋯等。作為金屬螯合物，較佳為鋁的乙醯丙酮配位化合物或乙醯乙酸酯配位化合物，更佳為三乙醯丙酮鋁。需要說明的是，金屬螯合物可以僅使用1種，也可以混合使用2種以上。 Examples of the metal chelate compound include an acetonitrile acetone complex compound of a polyvalent metal, an acetamidine acetate complex compound of a polyvalent metal, and the like. Examples of the polyvalent metal include aluminum, nickel, chromium, iron, titanium, zinc, cobalt, manganese, zirconium, and the like. As the metal chelate compound, an acetonitrile acetone complex compound or an acetamidine acetate complex compound of aluminum is preferred, and aluminum triethyl acetonate is more preferred. In addition, the metal chelate compound may be used alone or in combination of two or more.
作為交聯劑的添加量，較佳係相對於側鏈結晶性聚合物100重量份為0.1至20重量份。採用金屬螯合物作為交聯劑時，相對於側鏈結晶性聚合物100重量份，金屬螯合物的添加量較佳為5至15重量份，更佳為9 至11重量份。 The amount of the crosslinking agent added is preferably 0.1 to 20 parts by weight based on 100 parts by weight of the side chain crystalline polymer. When a metal chelate is used as the crosslinking agent, the metal chelate compound is preferably added in an amount of 5 to 15 parts by weight, more preferably 9 parts by weight based on 100 parts by weight of the side chain crystalline polymer. To 11 parts by weight.
交聯反應可以藉由在側鏈結晶性聚合物中加入交聯劑後，進行加熱乾燥來進行。作為加熱乾燥的條件，溫度為90至110℃左右，時間為1分鐘至20分鐘左右。 The crosslinking reaction can be carried out by heating and drying by adding a crosslinking agent to the side chain crystalline polymer. As a condition for heat drying, the temperature is about 90 to 110 ° C and the time is about 1 minute to 20 minutes.
作為上述的本實施形態的感溫性黏著劑的使用形態，可舉出例如無基材的片狀的形態。片狀並不僅限於片狀，只要不損害本實施形態的效果的範圍內，亦包括片狀或膜狀的概念。在使用感溫性黏著劑作為感溫性黏著片的情況下，其厚度較佳為15至400μm，更較佳為20至150μm。 The use form of the temperature sensitive adhesive of the present embodiment described above is, for example, a sheet-like form having no base material. The sheet shape is not limited to a sheet shape, and includes a sheet-like or film-like concept as long as it does not impair the effects of the embodiment. In the case where a temperature sensitive adhesive is used as the temperature sensitive adhesive sheet, the thickness thereof is preferably from 15 to 400 μm, more preferably from 20 to 150 μm.
另外，本實施形態的感溫性黏著劑也可以以帶狀的形態使用。在將感溫性黏著劑以感溫性黏著帶的形式使用的情況下，只要將包含本實施形態的感溫性黏著劑的黏著劑層積層於膜狀的基材的單面或雙面即可。所謂膜狀並不僅限定於膜狀，在不損害本實施形態的效果的範圍內，亦包括膜狀或片狀的概念。 Further, the temperature sensitive adhesive of the present embodiment may be used in the form of a belt. When the temperature sensitive adhesive is used in the form of a temperature sensitive adhesive tape, the adhesive containing the temperature sensitive adhesive of the present embodiment is laminated on one or both sides of the film-form substrate. can. The film shape is not limited to the film shape, and the concept of a film shape or a sheet shape is also included in the range which does not impair the effects of the present embodiment.
作為基材的構成材料，可舉出例如：聚乙烯、聚對苯二甲酸乙二酯、聚丙烯、聚酯、聚醯胺、聚醯亞胺、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、聚氯乙烯等合成樹脂。 The constituent material of the substrate may, for example, be polyethylene, polyethylene terephthalate, polypropylene, polyester, polyamine, polyimine, polycarbonate, ethylene-vinyl acetate copolymer. A synthetic resin such as an ethylene-ethyl acrylate copolymer, an ethylene-polypropylene copolymer, or a polyvinyl chloride.
基材可以為單層體或多層體中的任意一種，其厚度通常為5至500μm左右。從提高對黏著劑層的密著性的觀點而言，可以對基材實施例如電暈放電處 理、電漿處理、噴砂處理、化學蝕刻處理、底漆處理等表面處理。 The substrate may be either a single layer body or a multilayer body, and its thickness is usually about 5 to 500 μm. From the viewpoint of improving the adhesion to the adhesive layer, for example, a corona discharge can be applied to the substrate. Surface treatment such as chemical treatment, plasma treatment, sand blasting, chemical etching treatment, and primer treatment.
要在基材的單面或兩面積層黏著劑層時，只要利用塗布機等在基材的單面或兩面塗布由溶劑加入於感溫性黏著劑中而成的塗布液並進行乾燥即可。作為塗布機，可舉出例如刮刀塗布機、輥塗機、壓光塗布機、缺角輪塗布機、凹版塗布機、棒式塗布機等。 When the adhesive layer is applied to one side or two layers of the substrate, the coating liquid obtained by adding a solvent to the temperature sensitive adhesive on one side or both sides of the substrate by a coater or the like may be used and dried. Examples of the coater include a knife coater, a roll coater, a calender coater, a notch coater, a gravure coater, and a bar coater.
作為黏著劑層的厚度，較佳為5至60μm，更佳為10至60μm，進一步更佳為10至50μm。單面的黏著劑層的厚度與另一面的黏著劑層的厚度可以相同，也可以不同。 The thickness of the adhesive layer is preferably from 5 to 60 μm, more preferably from 10 to 60 μm, still more preferably from 10 to 50 μm. The thickness of the one-sided adhesive layer may be the same as or different from the thickness of the adhesive layer on the other side.
需要說明的是，本實施形態中，只要單面的黏著劑層包含上述感溫性黏著劑，則另一面的黏著劑層沒有特別限定。在例如由包含上述感溫性黏著劑的黏著劑層構成另一面的黏著劑層的情況下，其組成可以與單面的黏著劑層的組成相同，也可以不同。 In the present embodiment, the adhesive layer on the other side is not particularly limited as long as the one-side adhesive layer contains the temperature sensitive adhesive. In the case where the adhesive layer of the other surface is formed of, for example, an adhesive layer containing the above-mentioned temperature sensitive adhesive, the composition may be the same as or different from the composition of the adhesive layer on one side.
另一面的黏著劑層例如也可以由包含感壓性黏接劑的黏著劑層構成。感壓性接著劑為具有黏合性的聚合物，可舉出例如：天然橡膠接著劑、合成橡膠接著劑、苯乙烯/丁二烯膠乳基接著劑、丙烯酸系接著劑等。 The adhesive layer on the other side may be composed of, for example, an adhesive layer containing a pressure-sensitive adhesive. The pressure-sensitive adhesive is a polymer having adhesiveness, and examples thereof include a natural rubber adhesive, a synthetic rubber adhesive, a styrene/butadiene latex-based adhesive, and an acrylic adhesive.
關於在上述本實施形態的感溫性黏著片及感溫性黏著帶的表面，較佳係積層脫模膜。作為脫模膜，可舉出例如在由聚對苯二甲酸乙二酯等形成的膜的表面塗布矽酮等脫模劑而成的膜等。 In the surface of the temperature sensitive adhesive sheet and the temperature sensitive adhesive tape of the present embodiment, it is preferred to form a release film. The release film is, for example, a film obtained by coating a release agent such as an anthrone or the like on the surface of a film formed of polyethylene terephthalate or the like.
以下，舉出實施例進一步詳細地說明本發明，但本發明並不限定於以下的實施例。 Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples.
[實施例1至8及比較例1至5] [Examples 1 to 8 and Comparative Examples 1 to 5]
<感溫性黏著片的製作> <Production of Temperature Sensitive Adhesive Sheet>
首先，以表1所示的比例(重量份)混合表1所示的單體，得到混合物。需要說明的是，將具有碳數為16以上的直鏈狀烷基的(甲基)丙烯酸酯的合計比例示於表1中的「C16以上」一欄。 First, the monomers shown in Table 1 were mixed in the proportion (parts by weight) shown in Table 1, to obtain a mixture. In addition, the total ratio of the (meth)acrylate which has a linear alkyl group of the carbon number 16 or more is shown in the column of "C16 or more" of Table 1.
使用的單體如下所示。 The monomers used are as follows.
C22A：丙烯酸二十二烷基酯 C22A: behenyl acrylate
C18A：丙烯酸硬脂酯 C18A: stearyl acrylate
C16A：丙烯酸十六烷基酯 C16A: Cetyl acrylate
C12A：丙烯酸月桂酯 C12A: Lauryl Acrylate
C1A：丙烯酸甲酯 C1A: Methyl acrylate
AA：丙烯酸 AA: Acrylic
RFC：大阪有機化學工業公司製的上述的式(Ia)所示的反應性氟化合物「Viscoat 3F」 RFC: Reactive fluorine compound "Viscoat 3F" represented by the above formula (Ia) manufactured by Osaka Organic Chemical Industry Co., Ltd.
接著，將所得到的混合物加入至乙酸乙酯：甲苯=8：2(重量比)的混合溶劑200重量份中，得到混合液。將所得到的混合液在55℃攪拌4小時，藉此使各單體聚合，得到側鏈結晶性聚合物。 Next, the obtained mixture was added to 200 parts by weight of a mixed solvent of ethyl acetate:toluene=8:2 (weight ratio) to obtain a mixed liquid. The obtained mixed liquid was stirred at 55 ° C for 4 hours to polymerize each monomer to obtain a side chain crystalline polymer.
接著，在所得到的側鏈結晶性聚合物中分別添加增黏劑及金屬螯合物，得到感溫性黏著劑。 Next, a tackifier and a metal chelate compound were added to each of the obtained side chain crystalline polymers to obtain a temperature sensitive adhesive.
相對於側鏈結晶性聚合物100重量份，增黏 劑係以固體成分換算計添加表1所示比例。使用的增黏劑為以下的A至C所示3種。 Thickening with respect to 100 parts by weight of the side chain crystalline polymer The ratios shown in Table 1 were added in terms of solid content. The tackifier used is three of the following A to C.
增黏劑 Tackifier
A：荒川化學工業公司製的軟化點為23℃以下的液態松香酯「SUPER ESTER A-18」 A: Liquid rosin ester "SUPER ESTER A-18" with a softening point of 23 ° C or less by Arakawa Chemical Industries Co., Ltd.
B：荒川化學工業公司製的軟化點為70至80℃的松香酯「SUPER ESTER A-75」 B: Rosin ester "SUPER ESTER A-75" having a softening point of 70 to 80 ° C manufactured by Arakawa Chemical Industries Co., Ltd.
C：荒川化學工業公司製的軟化點為140至160℃的聚合松香酯「Pensel D-160」 C: Polymerized rosin ester "Pensel D-160" having a softening point of 140 to 160 ° C manufactured by Arakawa Chemical Industries Co., Ltd.
相對於側鏈結晶性聚合物100重量份，金屬螯合物係以固體成分換算計10重量份的比例添加。使用的金屬螯合物如下。 The metal chelate compound was added in a ratio of 10 parts by weight in terms of solid content based on 100 parts by weight of the side chain crystalline polymer. The metal chelate used was as follows.
金屬螯合物：川研精細化學公司製的三乙醯丙酮鋁 Metal chelate: triethyl acetonide aluminum manufactured by Chuanyan Fine Chemical Co., Ltd.
接著，利用乙酸乙酯將所得到的感溫性黏著劑按照固體成分成為30重量%的方式調整，得到塗布液。並且，將所得到的塗布液塗布在脫模膜上，在110℃加熱3分鐘進行交聯反應，得到包含感溫性黏著劑的厚度為25μm的感溫性黏著片。需要說明的是，脫模膜係使用已在聚對苯二甲酸乙二酯膜的表面塗布了有機矽而成的厚度為50μm的膜。 Then, the obtained temperature sensitive adhesive was adjusted to have a solid content of 30% by weight with ethyl acetate to obtain a coating liquid. Further, the obtained coating liquid was applied onto a release film, and heated at 110 ° C for 3 minutes to carry out a crosslinking reaction to obtain a temperature sensitive adhesive sheet having a thickness of 25 μm including a temperature sensitive adhesive. In addition, as a release film, the film which the organic ruthenium was apply|coated on the surface of the polyethylene-
<評價> <evaluation>
對於所得到的感溫性黏著片，評價重量平均分子量、熔點、室溫貼附性、耐熱性、室溫剝離性及尖嘯現象的有無。將各評價方法示於以下，並且將其結果示於表1。 With respect to the obtained temperature sensitive adhesive sheet, the weight average molecular weight, the melting point, the room temperature adhesion property, the heat resistance, the room temperature peeling property, and the screaming phenomenon were evaluated. Each evaluation method is shown below, and the results are shown in Table 1.
(重量平均分子量) (weight average molecular weight)
用GPC測定在製作感溫性黏著片的過程中得到的側鏈結晶性聚合物，對其測定值進行聚苯乙烯換算，由此測定側鏈結晶性聚合物的重量平均分子量。將其結果是示於表1中的「MW」一欄。 The side chain crystalline polymer obtained in the process of producing the temperature sensitive adhesive sheet was measured by GPC, and the measured value was measured in terms of polystyrene to measure the weight average molecular weight of the side chain crystalline polymer. The results are shown in the column "MW" in Table 1.
(熔點) (melting point)
通過用DSC在10℃/分鐘的測定條件下測定感溫性黏著片，來測定側鏈結晶性聚合物的熔點。需要說明的是，測定中使用的感溫性黏著片除了未添加增黏劑以外，其餘以與上述的感溫性黏著片的製作同樣地方式所製作的感溫性黏著片。 The melting point of the side chain crystalline polymer was measured by measuring the temperature sensitive adhesive sheet with DSC under the measurement conditions of 10 ° C /min. In addition, the temperature sensitive adhesive sheet used for the measurement is a temperature sensitive adhesive sheet produced in the same manner as the above-described temperature sensitive adhesive sheet except that the tackifier is not added.
(室溫貼附性) (room temperature adhesion)
首先，在23℃的環境溫度下，使用橡膠輥將感溫性黏著片的單面貼附在玻璃基座上。接著，使用橡膠輥將厚度75μm的聚對苯二甲酸乙二酯膜貼附在感溫性黏著片的另一面而得到試驗片。 First, a single surface of the temperature sensitive adhesive sheet was attached to the glass base using a rubber roller at an ambient temperature of 23 °C. Next, a polyethylene terephthalate film having a thickness of 75 μm was attached to the other surface of the temperature sensitive adhesive sheet using a rubber roller to obtain a test piece.
並且，通過以目視觀察所得到的試驗片中的聚對苯二甲酸乙二酯膜的狀態，評價室溫貼附性。評價基準按照以下方式設定。 Further, the room temperature adhesion was evaluated by visually observing the state of the polyethylene terephthalate film in the obtained test piece. The evaluation criteria are set as follows.
○：在聚對苯二甲酸乙二酯膜及感溫性黏著片的界面上沒有氣泡，聚對苯二甲酸乙二酯膜沒有翹起。 ○: There were no bubbles at the interface between the polyethylene terephthalate film and the temperature sensitive adhesive sheet, and the polyethylene terephthalate film was not lifted.
△：在沒有實際使用上的問題的範圍內，在聚對苯二甲酸乙二酯膜及感溫性黏著片的界面的一部分有氣泡，或者聚對苯二甲酸乙二酯膜的一部分有翹起。 △: In the range where there is no problem in practical use, there is a bubble at a part of the interface between the polyethylene terephthalate film and the temperature sensitive adhesive sheet, or a part of the polyethylene terephthalate film is warped. Start.
×：在聚對苯二甲酸乙二酯膜及感溫性黏著片的界面的整面有氣泡，或者聚對苯二甲酸乙二酯膜的大部分有翹起。 ×: There is a bubble on the entire surface of the interface between the polyethylene terephthalate film and the temperature sensitive adhesive sheet, or most of the polyethylene terephthalate film is lifted.
(耐熱性) (heat resistance)
將以與上述的室溫貼附性同樣的方式所製作的試驗片在120℃的環境溫度下靜置60分鐘後，以目視觀察聚對苯二甲酸乙二酯膜的狀態，由此評價耐熱性。評價基準按照以下方式設定。 The test piece produced in the same manner as the room temperature adhesion described above was allowed to stand at an ambient temperature of 120 ° C for 60 minutes, and then the state of the polyethylene terephthalate film was visually observed to evaluate the heat resistance. Sex. The evaluation criteria are set as follows.
○：聚對苯二甲酸乙二酯膜沒有翹起、及剝落。 ○: The polyethylene terephthalate film was not lifted and peeled off.
×：聚對苯二甲酸乙二酯膜有翹起、或剝落。 ×: The polyethylene terephthalate film was lifted or peeled off.
(室溫剝離性) (room temperature peelability)
依據JIS Z0237測定在經過120℃的環境溫度後的23℃的環境溫度下的180°剝離強度，由此評價室溫剝離性。具體來說，首先，在23℃的環境溫度下，隔著感溫性黏著片將寬度25mm、厚度75μm的聚對苯二甲酸乙二酯膜固定在玻璃基座上。接著，將環境溫度從23℃提高到120℃，在該環境溫度下靜置60分鐘後，將環境溫度從120℃降低至23℃，在該環境溫度下靜置20分鐘後，使用測力計以300mm/分鐘的速度進行180°剝離，測定感溫性黏著片及聚對苯二甲酸乙二酯膜間的180°剝離強度。將其結果示於表1中的「室溫剝離性」的「N/25mm」一欄。 The room temperature peelability was evaluated by measuring the 180° peel strength at an ambient temperature of 23 ° C after passing through an ambient temperature of 120 ° C according to JIS Z0237. Specifically, first, a polyethylene terephthalate film having a width of 25 mm and a thickness of 75 μm was fixed to a glass base via a temperature sensitive adhesive sheet at an ambient temperature of 23 °C. Next, the ambient temperature was raised from 23 ° C to 120 ° C, and after standing at the ambient temperature for 60 minutes, the ambient temperature was lowered from 120 ° C to 23 ° C, and after standing at the ambient temperature for 20 minutes, the dynamometer was used. The 180° peeling was performed at a speed of 300 mm/min, and the 180° peel strength between the temperature sensitive adhesive sheet and the polyethylene terephthalate film was measured. The results are shown in the column "N/25 mm" of "room temperature peelability" in Table 1.
另外，按以下的基準評價上述180°剝離強度的測定結果。將其結果示於表1中的「室溫剝離性」的「評價」一欄。 Further, the measurement results of the above 180° peel strength were evaluated on the basis of the following criteria. The results are shown in the "Evaluation" column of "room temperature peelability" in Table 1.
○：23℃的環境溫度下的180°剝離強度未達0.30N/25mm。 ○: The 180° peel strength at an ambient temperature of 23 ° C was less than 0.30 N/25 mm.
×：23℃的環境溫度下的180°剝離強度為0.30N/25mm以上。 ×: The 180° peel strength at an ambient temperature of 23 ° C was 0.30 N/25 mm or more.
(尖嘯現象的有無) (The presence or absence of screaming phenomenon)
由測定上述180°剝離強度時的剝離狀態按以下的基準評價尖嘯現象的有無。將其結果示於表1中的「尖嘯」一欄。 The presence or absence of the squeaking phenomenon was evaluated based on the following criteria by measuring the peeling state at the 180° peel strength. The results are shown in the "Scream" column in Table 1.
○：沒有尖嘯現象。 ○: There is no screaming phenomenon.
△：在沒有實際使用上的問題的範圍內，有輕度的尖嘯現象。 △: There is a slight scream in the range where there is no problem in actual use.
×：有重度的尖嘯現象。 ×: There is a severe screaming phenomenon.
由表1可以明確得知，實施例1至8由於耐熱性均優異，並且室溫貼附性及室溫剝離性均優異，因此能夠在室溫下進行對被黏物的貼附及剝離，且在室溫下剝離時能夠抑制尖嘯現象的發生。 As is clear from Table 1, each of Examples 1 to 8 is excellent in heat resistance, and is excellent in both room temperature adhesion and room temperature peelability, so that adhesion and peeling of the adherend can be performed at room temperature. Moreover, the occurrence of squeaking can be suppressed when peeling at room temperature.
另一方面，熔點低於30℃的比較例1的室溫剝離性差，發生重度的尖嘯現象。另外，熔點高於45℃的比較例2顯示出室溫貼附性差的結果。具有碳數為16以上的直鏈狀烷基的(甲基)丙烯酸酯的比例少於50重量%的比較例3顯示出室溫貼附性差的結果。增黏劑的軟化點高於23℃的比較例4、5發生重度的尖嘯現象。另外，比較例4也顯示室溫剝離性差的結果。 On the other hand, in Comparative Example 1 in which the melting point was lower than 30 ° C, the room temperature peeling property was inferior, and a severe screaming phenomenon occurred. Further, Comparative Example 2 having a melting point higher than 45 ° C showed a result of poor adhesion at room temperature. Comparative Example 3 in which the proportion of the (meth) acrylate having a linear alkyl group having 16 or more carbon atoms was less than 50% by weight showed a result of poor adhesion at room temperature. In Comparative Examples 4 and 5 in which the softening point of the tackifier was higher than 23 ° C, a severe scream phenomenon occurred. Further, Comparative Example 4 also showed the result of poor room temperature peelability.
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| JP2015076443A JP6542562B2 (en) | 2015-04-03 | 2015-04-03 | Temperature sensitive adhesive |
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| TWI710615B (en) * | 2018-07-27 | 2020-11-21 | 南韓商Ｌｇ化學股份有限公司 | Adhesive composition, adhesive film comprising the same, and backplate film and plastic organic light emitting display comprising the adhesive film |
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| US10155062B2 (en) * | 2016-05-24 | 2018-12-18 | The Boeing Company | Thermoresponsive adhesive material, method of making the material and methods of use |
| JP6792509B2 (en) * | 2017-04-21 | 2020-11-25 | ニッタ株式会社 | Temperature sensitive adhesive |
| JP7045006B2 (en) * | 2017-09-01 | 2022-03-31 | ニッタ株式会社 | Temperature-sensitive resin and temperature-sensitive adhesive |
| JP7097225B2 (en) * | 2018-04-27 | 2022-07-07 | 株式会社日本触媒 | Adhesive composition and its use |
| KR102232046B1 (en) * | 2018-12-27 | 2021-03-25 | (주)이녹스첨단소재 | Heat-Sensitive Adhesive Composition and Heat-Sensitive Adhesive Tape Comprising the Same |
| JP7449138B2 (en) * | 2019-03-28 | 2024-03-13 | 積水化学工業株式会社 | Pressure sensitive adhesive composition and adhesive tape |
| WO2020250848A1 (en) * | 2019-06-12 | 2020-12-17 | ニッタ株式会社 | Temperature-sensitive pressure-sensitive adhesive |
| CN110655883B (en) * | 2019-09-24 | 2021-07-13 | 南京清尚新材料科技有限公司 | Cold-shut adhesive, preparation method thereof and preparation method of adhesive tape |
| JP7306560B1 (en) * | 2022-12-14 | 2023-07-11 | 東洋インキＳｃホールディングス株式会社 | PSA COMPOSITION FOR DECORATION SHEET, DECORATION SHEET USING THE SAME, DECORATION STRUCTURE CONTAINING THE DECORATION SHEET, AND MANUFACTURING METHOD THEREOF |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1990013420A1 (en) * | 1989-05-11 | 1990-11-15 | Landec Labs, Inc. | Temperature-activated adhesive assemblies |
| AU1441692A (en) * | 1991-02-12 | 1992-09-07 | Landec Corporation | Temperature zone specific pressure-sensitive adhesive compositions, and adhesive assemblies and methods of use associated therewith |
| JP3751046B2 (en) * | 1995-04-14 | 2006-03-01 | 日本カーバイド工業株式会社 | Pressure sensitive adhesive composition |
| JP4391623B2 (en) * | 1999-06-10 | 2009-12-24 | ニッタ株式会社 | Temporary adhesive tape for raw sheet for ceramic electronic component and method for manufacturing ceramic electronic component |
| JP2003138237A (en) * | 2001-10-31 | 2003-05-14 | Panac Co Ltd | Heat-sensitive pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet |
| JP4729268B2 (en) * | 2004-05-31 | 2011-07-20 | ニッタ株式会社 | Easy removal tape for wigs |
| KR101341405B1 (en) * | 2009-07-02 | 2014-01-02 | 니타 가부시키가이샤 | Inorganic sealing film-attached adhesive tape, and method for transferring inorganic sealing film |
| JP5639446B2 (en) | 2010-11-09 | 2014-12-10 | ニッタ株式会社 | Easy peelable adhesive sheet and easy peelable adhesive tape |
| JP5714349B2 (en) * | 2011-01-31 | 2015-05-07 | ニッタ株式会社 | Easy peelable adhesive sheet and easy peelable adhesive tape |
| JP5661537B2 (en) * | 2011-03-31 | 2015-01-28 | ニッタ株式会社 | Temperature sensitive adhesive |
| WO2014188840A1 (en) * | 2013-05-24 | 2014-11-27 | ニッタ株式会社 | Temperature-sensitive adhesive |
-
2015
- 2015-04-03 JP JP2015076443A patent/JP6542562B2/en active Active
-
2016
- 2016-03-24 TW TW105109167A patent/TWI589657B/en active
- 2016-03-28 CN CN201610181858.1A patent/CN106047231B/en active Active
- 2016-03-31 KR KR1020160038965A patent/KR101837533B1/en active IP Right Grant
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| TWI710614B (en) * | 2018-07-27 | 2020-11-21 | 南韓商Ｌｇ化學股份有限公司 | Adhesive composition, adhesive film comprising the same, backplate film comprising adhesive film and plastic organic light emitting display comprising adhesive film |
| TWI710615B (en) * | 2018-07-27 | 2020-11-21 | 南韓商Ｌｇ化學股份有限公司 | Adhesive composition, adhesive film comprising the same, and backplate film and plastic organic light emitting display comprising the adhesive film |
| US11993736B2 (en) | 2018-07-27 | 2024-05-28 | Lg Chem, Ltd. | Adhesive composition, adhesive film comprising adhesive composition, back plate film comprising adhesive film, and plastic organic light emitting display comprising adhesive film |
| US11993734B2 (en) | 2018-07-27 | 2024-05-28 | Lg Chem, Ltd. | Adhesive composition, adhesive film comprising same, backplate film comprising adhesive film, and plastic organic light-emitting display comprising adhesive film |
| US12006456B2 (en) | 2018-07-27 | 2024-06-11 | Lg Chem, Ltd. | Adhesive composition, adhesion film comprising same, backplate film comprising adhesion film, and plastic organic light-emitting display comprising adhesion film |
| US12006449B2 (en) | 2018-07-27 | 2024-06-11 | Lg Chem, Ltd. | Adhesive composition, adhesive film comprising same, back plate film comprising adhesive film and plastic organic light-emitting display comprising adhesive film |
| US12012535B2 (en) | 2018-07-27 | 2024-06-18 | Lg Chem, Ltd. | Adhesive composition, adhesive film comprising same, backplate film comprising adhesive film, and plastic organic light emitting display comprising adhesive film |
| US12018188B2 (en) | 2018-07-27 | 2024-06-25 | Lg Chem, Ltd. | Adhesive composition, adhesive film comprising same, backplate film comprising adhesive film, and plastic organic light emitting display comprising adhesive film |
| US12018190B2 (en) | 2018-07-27 | 2024-06-25 | Lg Chem, Ltd. | Adhesive composition, adhesive film comprising same, backplate film comprising adhesive film, and plastic organic light-emitting display comprising adhesive film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106047231B (en) | 2018-05-11 |
| KR101837533B1 (en) | 2018-03-12 |
| JP2016196544A (en) | 2016-11-24 |
| TWI589657B (en) | 2017-07-01 |
| CN106047231A (en) | 2016-10-26 |
| JP6542562B2 (en) | 2019-07-10 |
| KR20160118959A (en) | 2016-10-12 |
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