TW202043341A - Curable composition, cured object, and product provided with cured object - Google Patents
Curable composition, cured object, and product provided with cured object Download PDFInfo
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- TW202043341A TW202043341A TW109102867A TW109102867A TW202043341A TW 202043341 A TW202043341 A TW 202043341A TW 109102867 A TW109102867 A TW 109102867A TW 109102867 A TW109102867 A TW 109102867A TW 202043341 A TW202043341 A TW 202043341A
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- -1 cured object Substances 0.000 title description 27
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- 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
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Abstract
Description
本發明涉及硬化性組成物、硬化性組成物之硬化物、具備硬化物之製品。The present invention relates to a curable composition, a cured product of the curable composition, and a product having a cured product.
近年，除了剛性顯示器面板以外，還開發了一種具有彎曲性或撓曲性的撓性顯示器面板。
撓性顯示器面板具備例如撓性積層體，該撓性積層體係於有機EL(Electronic Luminescent：電致發光)顯示器面板等之撓性顯示器面板本體，透過黏著層而積層有光學薄膜或保護薄膜等撓性構件。
專利文獻1、2中，針對適合用來形成撓性積層體之黏著劑，記載了一包含具有特定單體組成之(甲基)丙烯酸酯共聚物及交聯劑的組成物。In recent years, in addition to rigid display panels, a flexible display panel with bendability or flexibility has been developed.
The flexible display panel has, for example, a flexible laminate. The flexible laminate system is used in the body of a flexible display panel such as an organic EL (Electronic Luminescent) display panel. An optical film or a protective film is laminated through an adhesive layer. Sexual components.
先前技術文獻 專利文獻 專利文獻1：日本專利特開2017-95654號公報 專利文獻2：國際公開第2018/173896號Prior art literature Patent literature Patent Document 1: Japanese Patent Laid-Open No. 2017-95654 Patent Document 2: International Publication No. 2018/173896
發明欲解決之課題
隨著周邊技術發達，對構成撓性顯示器面板之撓性積層體的要求特性不斷升級。舉例而言，希望彎折耐久性優異，亦即不易因彎折而發生白化、剝落、浮凸、裂痕等缺陷，以及希望形狀回復性優異，亦即即使彎曲或受拉伸應力也不易變形。
然而，使用專利文獻1、2中記載之黏著劑所形成的撓性積層體，該等特性都稱不上充分。
本發明目的在於提供一種可形成彎折耐久性及形狀回復性優異之撓性積層體的硬化性組成物、硬化性組成物之硬化物及具備硬化物之製品。Problems to be solved by the invention
With the development of peripheral technology, the required characteristics of the flexible laminate that constitute the flexible display panel are continuously upgraded. For example, it is desirable to have excellent bending durability, that is, it is not easy to cause defects such as whitening, peeling, embossing, and cracks due to bending, and it is desirable to have excellent shape recovery, that is, it is not easy to deform even if it is bent or subjected to tensile stress.
However, the flexible laminates formed using the adhesives described in
用以解決課題之手段 本發明具有下述態樣。 [1]一種硬化性組成物，包含(甲基)丙烯酸酯聚合物與第1單體； 前述聚合物之數量平均分子量為4萬~75萬； 前述第1單體係分子量為35,000以下之單體，其於1分子中具有1個以上聚氧伸烷基鏈及1個(甲基)丙烯醯基；並且 相對於前述聚合物100質量份，前述第1單體之含量為10~50質量份。 [2]如[1]記載之硬化性組成物，其中前述第1單體之分子量為數量平均分子量。 [3]如[1]或[2]記載之硬化性組成物，其中前述第1單體之玻璃轉移溫度為-55℃以下。 [4]如[1]~[3]中任一項記載之硬化性組成物，其中前述第1單體之分子量分布為1.03~1.2。 [5]如[1]~[4]中任一項記載之硬化性組成物，其中前述第1單體含有相對於單體總量為0.3~1.9質量%之胺甲酸乙酯鍵。 [6]如[1]~[5]中任一項記載之硬化性組成物，其中以示差掃描熱量計分析獲得之前述聚合物的玻璃轉移溫度為-75~-40℃。 [7]如[1]~[6]中任一項記載之硬化性組成物，其更含有交聯劑。 [8]如[1]~[7]中任一項記載之硬化性組成物，其更含有光聚合引發劑。 [9]如[1]~[8]中任一項記載之硬化性組成物，其中相對於硬化性組成物之總量，前述聚合物與前述第1單體之合計含量為80質量%以上。 [10]一種硬化物，係如[1]~[9]中任一項記載之硬化性組成物的硬化物。 [11]如[10]記載之硬化物，其動態黏彈性之tanδ尖峰溫度、即玻璃轉移溫度為-35℃以下。 [12]一種黏著片材，包含黏著層，該黏著層係由如[10]或[11]記載之硬化物所構成。 [13]如[12]記載之黏著片材，其中前述黏著層之厚度為10~150μm。 [14]一種積層體，具有由如[10]或[11]記載之硬化物所構成的黏著層及透過前述黏著層積層的撓性構件。 [15]如[14]記載之積層體，其中前述黏著層之厚度為10~150μm。 [16]如[14]或[15]記載之積層體，其中前述撓性構件係選自於由表面保護面板、光學薄膜、觸控面板及顯示面板本體所構成群組中之至少1者。 [17]一種撓性顯示器，具備如[14]~[16]中任一項記載之積層體。Means to solve the problem The present invention has the following aspects. [1] A curable composition comprising a (meth)acrylate polymer and a first monomer; The number average molecular weight of the aforementioned polymers is 40,000 to 750,000; The aforementioned first monomer having a molecular weight of 35,000 or less, which has more than one polyoxyalkylene chain and one (meth)acrylic acid group in one molecule; and The content of the first monomer is 10-50 parts by mass relative to 100 parts by mass of the polymer. [2] The curable composition according to [1], wherein the molecular weight of the first monomer is a number average molecular weight. [3] The curable composition according to [1] or [2], wherein the glass transition temperature of the first monomer is -55°C or lower. [4] The curable composition according to any one of [1] to [3], wherein the molecular weight distribution of the first monomer is 1.03 to 1.2. [5] The curable composition according to any one of [1] to [4], wherein the first monomer contains 0.3 to 1.9% by mass of urethane bonds relative to the total amount of monomers. [6] The curable composition according to any one of [1] to [5], wherein the glass transition temperature of the aforementioned polymer obtained by differential scanning calorimeter analysis is -75 to -40°C. [7] The curable composition according to any one of [1] to [6], which further contains a crosslinking agent. [8] The curable composition according to any one of [1] to [7], which further contains a photopolymerization initiator. [9] The curable composition according to any one of [1] to [8], wherein the total content of the polymer and the first monomer relative to the total amount of the curable composition is 80% by mass or more . [10] A cured product, which is a cured product of the curable composition described in any one of [1] to [9]. [11] The hardened product as described in [10] has a dynamic viscoelastic tanδ peak temperature, that is, a glass transition temperature of -35°C or less. [12] An adhesive sheet comprising an adhesive layer composed of the hardened material as described in [10] or [11]. [13] The adhesive sheet as described in [12], wherein the thickness of the adhesive layer is 10 to 150 μm. [14] A laminate having an adhesive layer composed of the hardened material described in [10] or [11] and a flexible member through the adhesive layer laminated layer. [15] The laminate as described in [14], wherein the thickness of the adhesive layer is 10 to 150 μm. [16] The laminate according to [14] or [15], wherein the flexible member is at least one selected from the group consisting of a surface protection panel, an optical film, a touch panel, and a display panel body. [17] A flexible display having a laminate as described in any one of [14] to [16].
發明效果 根據本發明，可獲得一種可形成彎折耐久性及形狀回復性優異之撓性積層體的硬化性組成物、硬化性組成物之硬化物及具備硬化物之製品。Invention effect According to the present invention, a curable composition capable of forming a flexible laminate with excellent bending durability and shape recovery, a cured product of the curable composition, and a product having a cured product can be obtained.
在本說明書中，式(1)所示化合物表記為化合物1。以其他式表示之化合物亦以同樣方式表記。 本說明書中之用語定義如下。 「單元」意指藉由單體之聚合直接形成的原子團。 「(甲基)丙烯酸酯」意指丙烯酸酯及甲基丙烯酸酯中之任一者或兩者。 「官能基數」在未特別說明時，係表示1分子中之(甲基)丙烯醯氧基之數量。 「平均官能基數」在未特別說明時，係表示根據化學式所得之式量表示的每分子量或數量平均分子量為1單位之1分子中的平均(甲基)丙烯醯氧基之數量。 「指數」係將異氰酸酯化合物之異氰酸酯基之莫耳數除以氧伸烷基聚合物之羥基之莫耳數所得之值，乘100倍後所得之值。亦稱「NCO/OH比」。 「片材」概念上係包含薄片、薄膜、帶狀物者。 「撓性」意指可撓曲或彎曲之性狀，包含例如摺疊成撓曲半徑小於3mm仍可回復形狀之性狀(Foldable：可摺的)、例如彎折或捲曲成撓曲半徑3mm以上仍可回復形狀之性狀(Rollable：可捲的)、固定在彎曲狀態下仍不會破損之性狀(Bendable：可彎的)。In this specification, the compound represented by formula (1) is represented as compound 1. Compounds represented by other formulas are also represented in the same way. The terms used in this manual are defined as follows. "Unit" means a group of atoms directly formed by the polymerization of monomers. "(Meth)acrylate" means either or both of acrylate and methacrylate. The "number of functional groups" means the number of (meth)acryloxy groups in one molecule, unless otherwise specified. "Average number of functional groups", unless otherwise specified, means the number of average (meth)acryloxy groups per molecule represented by the formula weight obtained from the chemical formula or number average molecular weight of 1 unit. "Index" is the value obtained by dividing the number of moles of isocyanate groups of the isocyanate compound by the number of moles of hydroxyl groups of the oxyalkylene polymer, and multiplying the value by 100 times. Also known as "NCO/OH ratio". "Sheet" conceptually includes sheets, films, and ribbons. "Flexibility" refers to the properties that can be bent or bent, including, for example, the properties that can be folded into a shape that can be restored with a deflection radius of less than 3mm (Foldable: Foldable), such as bending or curling to a deflection radius of 3mm or more. The property of restoring shape (Rollable: rollable), the property of being fixed in a bent state without breaking (Bendable: bendable).
多元醇之羥值係藉由以JIS K1557(2007年版)為依據之測定而獲得。 羥基換算分子量係將羥值套用至「{56100/(羥值)}×(引發劑之羥基數)」之算式中所算出。 數量平均分子量及質量平均分子量係使用用已知分子量之標準聚苯乙烯試料做成的檢量曲線，以凝膠滲透層析術(GPC)測定所得之聚苯乙烯換算分子量。分子量分布係指將質量平均分子量(以下稱Mw)除以數量平均分子量(以下稱Mn)後所得之值(Mw/Mn)。至於在GPC測定中出現未反應之低分子量成分(單體等)的尖峰時，係排除該尖峰後來求算數量平均分子量及質量平均分子量。 即使已用Mn規定，但在不存在分子量分布之情況下，則以根據化學式所得之式量表示之分子量來替代。The hydroxyl value of the polyol is obtained by measurement based on JIS K1557 (2007 edition). The hydroxyl-converted molecular weight is calculated by applying the hydroxyl value to the formula "{56100/(hydroxyl value)}×(hydroxyl number of initiator)". The number-average molecular weight and mass-average molecular weight are polystyrene-converted molecular weights measured by gel permeation chromatography (GPC) using a calibration curve made with standard polystyrene samples of known molecular weight. The molecular weight distribution refers to the value (Mw/Mn) obtained by dividing the mass average molecular weight (hereinafter referred to as Mw) by the number average molecular weight (hereinafter referred to as Mn). As for the peak of unreacted low molecular weight components (monomers, etc.) in the GPC measurement, the number average molecular weight and the mass average molecular weight are calculated after excluding the peak. Even though Mn has been specified, if there is no molecular weight distribution, the molecular weight expressed by the formula weight obtained from the chemical formula is used instead.
在本發明中，硬化物之玻璃轉移溫度係其在動態黏彈性測定中所得之tanδ尖峰溫度。 在本發明中，聚合物之玻璃轉移溫度係藉由示差掃描熱量計(DSC)分析所得之玻璃轉移溫度。 在本發明中，單體之玻璃轉移溫度是僅對目標單體添加光聚合引發劑並使其硬化後，在動態黏彈性測定中所得之tanδ尖峰溫度。In the present invention, the glass transition temperature of the cured product is the peak temperature of tanδ obtained in the dynamic viscoelasticity measurement. In the present invention, the glass transition temperature of the polymer is the glass transition temperature obtained by differential scanning calorimeter (DSC) analysis. In the present invention, the glass transition temperature of the monomer is the tanδ peak temperature obtained in the dynamic viscoelasticity measurement after only adding a photopolymerization initiator to the target monomer and curing it.
本實施形態之硬化性組成物包含聚合物(以下亦稱聚合物A)與第1單體(以下亦稱單體B)。The curable composition of this embodiment contains a polymer (hereinafter also referred to as polymer A) and a first monomer (hereinafter also referred to as monomer B).
＜聚合物A＞ 聚合物A係具有以(甲基)丙烯酸酯為主體之單元且數量平均分子量為4萬~75萬之均聚物或共聚物。硬化性組成物中之聚合物A可為1種，亦可為2種以上。 用於製造聚合物A之單體可舉如：國際公開第2018/173896號之[0095]~[0110]中記載的(甲基)丙烯酸烷基酯、含羧基單體、含羥基單體、含胺基單體、含環氧基單體、含醯胺基單體、乙烯基單體、巨單體。 單體可為1種，亦可組合2種以上。＜Polymer A＞ Polymer A is a homopolymer or copolymer with a (meth)acrylate as the main unit and a number average molecular weight of 40,000-750,000. The polymer A in the curable composition may be one type or two or more types. The monomers used in the production of polymer A include, for example, alkyl (meth)acrylates, carboxyl group-containing monomers, hydroxyl group-containing monomers, as described in [0095]~[0110] of International Publication No. 2018/173896 Amine group-containing monomers, epoxy group-containing monomers, amide group-containing monomers, vinyl monomers, macromonomers. The monomer may be one type, or two or more types may be combined.
特別理想之單體可舉下述單體a1、a2、a3。 單體a1：於(甲基)丙烯醯氧基鍵結有碳數4~18烷基的(甲基)丙烯酸烷基酯。 單體a2：具有羧基且可與單體a1共聚之單體。 單體a3：具有有機官能基且可與單體a1共聚之單體。Particularly desirable monomers include the following monomers a1, a2, and a3. Monomer a1: (meth)acrylic acid alkyl ester with a carbon number of 4 to 18 bonded to a (meth)acryloyloxy group. Monomer a2: a monomer having a carboxyl group and copolymerizable with monomer a1. Monomer a3: a monomer having an organic functional group and copolymerizable with monomer a1.
單體a1之鍵結於(甲基)丙烯醯氧基的碳數4~18烷基宜為直鏈或支鏈。單體a1可舉如：(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸新戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸異硬脂酯。 若使用於(甲基)丙烯醯氧基鍵結有碳數4~12之直鏈或支鏈烷基的單體a1，本實施形態之硬化性組成物的硬化物容易變軟。以鍵結有碳數4~12之直鏈或支鏈烷基的單體a1為佳，(甲基)丙烯酸丁酯、(甲基)丙烯酸2-乙基己酯或(甲基)丙烯酸月桂酯較佳。The alkyl group with 4 to 18 carbon atoms bonded to the (meth)acryloyloxy group of monomer a1 is preferably linear or branched. Monomer a1 may include: n-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, third butyl (meth)acrylate, (meth)acrylic acid Amyl ester, isoamyl (meth)acrylate, neopentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, heptyl (meth)acrylate, (meth) 2-ethylhexyl acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, isodecyl (meth)acrylate, isostearyl (meth)acrylate. If the monomer a1 in which a (meth)acryloyloxy group is bonded to a linear or branched chain alkyl group having 4 to 12 carbon atoms is used, the cured product of the curable composition of this embodiment tends to become soft. The monomer a1 bonded with a straight or branched chain alkyl group with 4 to 12 carbons is preferred, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate or laurel (meth)acrylate Esters are preferred.
單體a2之例可舉：(甲基)丙烯酸、2-(甲基)丙烯醯氧基乙基六氫苯二甲酸、2-(甲基)丙烯醯氧基丙基六氫苯二甲酸、2-(甲基)丙烯醯氧基乙基苯二甲酸、2-(甲基)丙烯醯氧基丙基苯二甲酸、2-(甲基)丙烯醯氧基乙基馬來酸、2-(甲基)丙烯醯氧基丙基馬來酸、2-(甲基)丙烯醯氧基乙基琥珀酸、2-(甲基)丙烯醯氧基丙基琥珀酸、巴豆酸、延胡索酸、馬來酸、伊康酸。 若使用單體a2，在高溫高濕度之條件下，硬化物便不易白濁(耐濕熱性)，且容易提升黏著力。尤以(甲基)丙烯酸為佳。Examples of monomer a2 include: (meth)acrylic acid, 2-(meth)acryloxyethylhexahydrophthalic acid, 2-(meth)acryloxypropylhexahydrophthalic acid, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxypropyl phthalic acid, 2-(meth)acryloyloxyethyl maleic acid, 2- (Meth)acryloxypropylmaleic acid, 2-(meth)acryloxypropylmaleic acid, 2-(meth)acryloxypropylsuccinic acid, crotonic acid, fumaric acid, horse Tonic acid, itaconic acid. If monomer a2 is used, under the conditions of high temperature and high humidity, the hardened product will not become cloudy (damp and heat resistance), and it will be easy to improve the adhesion. Especially (meth)acrylic acid is preferred.
單體a3之有機官能基宜為羥基或醯胺基，羥基較佳。單體a3之例可舉：(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸2-羥丙酯、(甲基)丙烯酸3-羥丙酯、(甲基)丙烯酸2-羥丁酯、(甲基)丙烯酸4-羥丁酯、(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、N-丁基(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、N-羥甲丙烷(甲基)丙烯醯胺、N-甲氧基甲基(甲基)丙烯醯胺、N-丁氧基甲基(甲基)丙烯醯胺、二丙酮(甲基)丙烯醯胺、馬來醯胺、馬來醯亞胺。 若使用單體a3，容易提升耐濕熱性。尤以(甲基)丙烯酸羥烷基酯為佳，(甲基)丙烯酸4-羥丁酯較佳。The organic functional group of monomer a3 is preferably a hydroxyl group or an amide group, preferably a hydroxyl group. Examples of monomer a3 include: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate Ester, 4-hydroxybutyl (meth)acrylate, (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-butyl(meth)acrylamide, N- Hydroxymethyl(meth)acrylamide, N-hydroxymethylpropane(meth)acrylamide, N-methoxymethyl(meth)acrylamide, N-butoxymethyl(methyl) Acrylamide, diacetone (meth)acrylamide, maleamide, maleimide. If monomer a3 is used, it is easy to improve heat and humidity resistance. Particularly, hydroxyalkyl (meth)acrylate is preferred, and 4-hydroxybutyl (meth)acrylate is preferred.
例如，宜為下述態樣：相對於聚合物A之總單元，以單體a1為主體之單元為50~99.9質量%，以單體a2為主體之單元為0.1~5.0質量%，且該等合計為50.1~100質量%。 或宜為下述態樣：相對於聚合物A之總單元，以單體a1為主體之單元為50~99.0質量%，以單體a3為主體之單元為1.0~20.0質量%，且該等合計為51.0~100質量%。For example, the following aspect is preferable: relative to the total units of the polymer A, the unit with monomer a1 as the main body is 50 to 99.9% by mass, and the unit with monomer a2 as the main body is 0.1 to 5.0% by mass, and The total etc. are 50.1-100% by mass. Or preferably the following aspect: relative to the total units of the polymer A, the unit based on monomer a1 is 50-99.0% by mass, and the unit based on monomer a3 is 1.0-20.0% by mass, and these The total is 51.0-100% by mass.
聚合物A之Mw宜為30萬~150萬，40萬~140萬較佳，45萬~130萬更佳，50~120萬尤佳。若為上述範圍之下限值以上，潛變回復率及捲曲殘存率會變得更佳；若為上限值以下，因為低黏度，所以容易獲得良好的塗敷性。 聚合物A之Mn為4萬~75萬，7萬~70萬為佳，10萬~50萬較佳，14萬~30萬更佳。若為上述範圍之下限值以上，潛變回復率及捲曲殘存率容易變佳；若為上限值以下，因為低黏度，所以容易獲得良好的塗敷性。 硬化性組成物中包含2種以上聚合物A時，各Mn宜分別在上述範圍內。 聚合物A之分子量分布宜為2.0~8.0，2.1~7.5較佳，2.2~7.0更佳。若為上述範圍之下限值以上，黏著力容易變佳；若為上限值以下，潛變回復率更為優異。 硬化性組成物中包含2種以上聚合物A時，各分子量分布宜分別在上述範圍內。The Mw of polymer A is preferably 300,000 to 1.5 million, preferably 400,000 to 1.4 million, more preferably 450,000 to 1.3 million, and more preferably 500,000 to 1.2 million. If it is more than the lower limit of the above range, the creep recovery rate and curl retention rate will become better; if it is less than the upper limit, because of the low viscosity, it is easy to obtain good coating properties. The Mn of polymer A is 40,000 to 750,000, preferably 70,000 to 700,000, preferably 100,000 to 500,000, and even more preferably 140,000 to 300,000. If it is more than the lower limit of the above range, the creep recovery rate and curl remaining rate are likely to be improved; if it is less than the upper limit, because of the low viscosity, it is easy to obtain good coating properties. When two or more types of polymer A are contained in the curable composition, each Mn is preferably within the aforementioned range. The molecular weight distribution of polymer A is preferably 2.0 to 8.0, preferably 2.1 to 7.5, and more preferably 2.2 to 7.0. If it is above the lower limit of the above range, the adhesive force is likely to become better; if it is below the upper limit, the creep recovery rate is more excellent. When two or more types of polymer A are contained in the curable composition, each molecular weight distribution is preferably within the aforementioned range.
聚合物A之玻璃轉移溫度宜為-75~-40℃，-70~-45℃較佳，-68~-50℃更佳。若在上述範圍內，在低溫下之彎曲試驗中就不易產生剝落。 硬化性組成物中包含2種以上聚合物A時，各玻璃轉移溫度宜分別在上述範圍內。The glass transition temperature of polymer A is preferably -75~-40°C, preferably -70~-45°C, more preferably -68~-50°C. If it is within the above range, peeling will not easily occur in the bending test at low temperature. When two or more types of polymer A are contained in the curable composition, each glass transition temperature is preferably within the aforementioned range.
＜單體B＞ 單體B之分子量為35,000以下，於1分子中具有1個以上使開環加成聚合有環氧烷之聚氧伸烷基鏈，且於1分子中具有1個(甲基)丙烯醯氧基。硬化性組成物中之單體B可為1種，亦可為2種以上。 單體B有助於降低本實施形態之硬化性組成物於硬化時收縮，而有助於降低硬化物之彈性模數。藉由將本實施形態之硬化性組成物之硬化物作為積層體之黏著層使用，可提升積層體之彎折耐久性及形狀回復性。而且單體B具有1個(甲基)丙烯醯氧基，所以在硬化物之穩定性佳，不易發生溢出。 基於硬化速度的觀點，單體B宜具有丙烯醯氧基。＜Monomer B＞ Monomer B has a molecular weight of 35,000 or less, has more than one polyoxyalkylene chain with alkylene oxide through ring-opening addition polymerization in one molecule, and has one (meth)acrylic acid in one molecule base. The monomer B in the curable composition may be one type or two or more types. Monomer B helps reduce the shrinkage of the curable composition of this embodiment during curing, and also helps reduce the elastic modulus of the cured product. By using the cured product of the curable composition of this embodiment as the adhesive layer of the laminate, the bending durability and shape recovery of the laminate can be improved. In addition, the monomer B has one (meth)acryloyloxy group, so it has good stability in the hardened product and is unlikely to overflow. From the viewpoint of curing speed, monomer B preferably has an acryloxy group.
單體B宜為具有聚氧伸烷基鏈及胺甲酸乙酯鍵之寡聚物。具有胺甲酸乙酯鍵之寡聚物之1分子中的胺甲酸乙酯鍵數宜為1個以上。在容易減少硬化時之收縮而易降低硬化後之彈性模數的觀點下，以1個較佳。 相對於單體B之總量，胺甲酸乙酯鍵之含量宜為0.3~1.9質量%，0.32~1.6質量%較佳，0.35~1.3質量%更佳。若在上述範圍內，容易獲得良好的黏著性。 相對於單體B之總量，胺甲酸乙酯鍵之含量是將製造單體B時使用之異氰酸酯化合物中所存在的異氰酸酯基全部視為形成有胺甲酸乙酯鍵(分子量59)，並藉由以下計算式算出。 胺甲酸乙酯鍵之含量(單位：質量%)={Mi×59/Wb}×100 Wb：單體B之總質量 Mi：製造質量Wb之單體B所使用的異氰酸酯化合物中存在之異氰酸酯基的總莫耳數Monomer B is preferably an oligomer having a polyoxyalkylene chain and a urethane bond. The number of urethane bonds in one molecule of the oligomer having urethane bonds is preferably one or more. From the viewpoint that it is easy to reduce the shrinkage during hardening and the elastic modulus after hardening, one is preferred. Relative to the total amount of monomer B, the content of the urethane bond is preferably 0.3 to 1.9% by mass, preferably 0.32 to 1.6% by mass, and more preferably 0.35 to 1.3% by mass. If it is within the above range, good adhesiveness is easily obtained. Relative to the total amount of monomer B, the content of urethane bonds is based on the fact that all isocyanate groups present in the isocyanate compound used in the production of monomer B are considered to have urethane bonds (molecular weight 59), and It is calculated by the following calculation formula. The content of urethane bond (unit: mass%)={Mi×59/Wb}×100 Wb: Total mass of monomer B Mi: The total number of moles of isocyanate groups present in the isocyanate compound used in monomer B of manufacturing quality Wb
在單體B之製造步驟中，有在產物(以下亦稱「產物B」)中生成單體B以外的副產物之情形。 為了充分發揮作為單體B之功能，產物B中之單體B的含量相對於產物B之總量宜為80質量%以上，85~100質量%較佳。產物B以上述含量包含單體B時，可充分發揮單體B之功能，因此可將產物B視為單體B。In the production step of monomer B, by-products other than monomer B may be generated in the product (hereinafter also referred to as "product B"). In order to give full play to the function of the monomer B, the content of the monomer B in the product B relative to the total amount of the product B should be 80% by mass or more, preferably 85-100% by mass. When the product B contains the monomer B in the above content, the function of the monomer B can be fully exerted, so the product B can be regarded as the monomer B.
當可將產物B視為單體B時，從產物B之Mn及官能基數求算之產物B的平均官能基數可視為單體B之平均官能基數。此時，產物B之平均官能基數宜為0.8~1.3，且0.9~1.2較佳。產物B之平均官能基數若在上述範圍內，便容易充分發揮單體B之功能。產物B之平均官能基數可藉由單體B之製造原料中所含不純物量及後述指數來調整。另，在本說明書中，(甲基)丙烯醯氧基之平均數可使用後述原料之平均官能基數及指數經由計算求得。When product B can be regarded as monomer B, the average number of functional groups of product B calculated from the Mn and number of functional groups of product B can be regarded as the average number of functional groups of monomer B. At this time, the average number of functional groups of product B is preferably 0.8 to 1.3, and preferably 0.9 to 1.2. If the average number of functional groups of product B is within the above-mentioned range, the function of monomer B can be fully exerted. The average number of functional groups of the product B can be adjusted by the amount of impurities contained in the raw materials of the monomer B and the index described later. In addition, in this specification, the average number of (meth)acryloxy groups can be calculated using the average number of functional groups and the index of the raw materials described later.
單體B之分子量為35,000以下，3,000~30,000為佳，4,000~28,000較佳，5,000~26,000更佳。單體B之分子量可為Mn，此時，Mn為35,000以下，3,000~30,000為佳，4,000~28,000較佳，5,000~26,000更佳。單體B之分子量或Mn若在上述範圍內，便容易調整硬化性組成物之黏度；若為下限值以上，硬化物容易變軟。 硬化性組成物中包含2種以上單體B時，各Mn宜分別在上述範圍內。 單體B之分子量分布宜為1.03~1.2，1.05~1.15較佳。 硬化性組成物中包含2種以上單體B時，各分子量分布宜分別在上述範圍內。 單體B之玻璃轉移溫度宜為-55℃以下，-58℃以下較佳，-60℃以下更佳。若為上述範圍之上限值以下，在低溫下之彎曲耐久性便更為優異。在容易提升潛變回復率之觀點下，下限值宜為-85℃以上，-80℃以上較佳。例如，單體B之玻璃轉移溫度宜為-85℃~-55℃，-85℃~-58℃較佳，-80℃~-58℃更佳，-80℃~-60℃尤佳。 硬化性組成物中包含2種以上單體B時，各玻璃轉移溫度宜分別在上述範圍內。The molecular weight of monomer B is 35,000 or less, preferably 3,000 to 30,000, more preferably 4,000 to 28,000, and more preferably 5,000 to 26,000. The molecular weight of monomer B can be Mn. In this case, Mn is 35,000 or less, preferably 3,000 to 30,000, preferably 4,000 to 28,000, and more preferably 5,000 to 26,000. If the molecular weight or Mn of the monomer B is within the above range, it is easy to adjust the viscosity of the curable composition; if it is above the lower limit, the hardened product is likely to become soft. When two or more types of monomer B are contained in the curable composition, each Mn is preferably within the aforementioned range. The molecular weight distribution of monomer B is preferably 1.03 to 1.2, preferably 1.05 to 1.15. When two or more types of monomer B are contained in the curable composition, each molecular weight distribution is preferably within the above-mentioned range. The glass transition temperature of monomer B is preferably -55°C or less, preferably -58°C or less, and more preferably -60°C or less. If it is less than the upper limit of the above range, the bending durability at low temperature is more excellent. From the viewpoint that it is easy to increase the creep recovery rate, the lower limit is preferably -85°C or higher, preferably -80°C or higher. For example, the glass transition temperature of monomer B is preferably -85°C~-55°C, preferably -85°C~-58°C, more preferably -80°C~-58°C, and particularly preferably -80°C~-60°C. When two or more types of monomer B are contained in the curable composition, each glass transition temperature is preferably within the above range.
在本實施形態之硬化性組成物中，相對於聚合物A之100質量份，單體B之含量為10~50質量份，宜為11~45質量份，12~40質量份較佳，13~30質量份更佳。若為上述範圍之下限值以上，便容易獲得硬化物在低溫下之彎曲耐久性，且容易變軟；若為上限值以下，耐熱性便更為優異。In the curable composition of this embodiment, relative to 100 parts by mass of polymer A, the content of monomer B is 10-50 parts by mass, preferably 11-45 parts by mass, preferably 12-40 parts by mass, 13 ~30 parts by mass is better. If it is more than the lower limit of the above range, it is easy to obtain the bending durability of the hardened product at low temperature and it is easy to become soft; if it is less than the upper limit, the heat resistance is more excellent.
單體B之具體例可舉以下所示單體B-1、單體B-2、單體B-3。該等可單獨使用1種，亦可併用2種以上。Specific examples of monomer B include monomer B-1, monomer B-2, and monomer B-3 shown below. These may be used individually by 1 type, and may use 2 or more types together.
尤其，單體B宜包含選自於由單體B-1及單體B-2所構成群組中之1種以上。 相對於單體B之總量，單體B-1與單體B-2之合計含量宜為50質量%以上，80質量%以上較佳，100質量%尤佳。單體B-1與單體B-2之合計含量若為上述範圍之下限值以上，便容易降低硬化收縮率，且硬化物容易變軟。表示單體B-1與單體B-2之質量比的(B-1)：(B-2)宜為1：0~1：1。In particular, monomer B preferably contains one or more selected from the group consisting of monomer B-1 and monomer B-2. Relative to the total amount of monomer B, the total content of monomer B-1 and monomer B-2 is preferably 50% by mass or more, preferably 80% by mass or more, and particularly preferably 100% by mass. If the total content of the monomer B-1 and the monomer B-2 is more than the lower limit of the above-mentioned range, the curing shrinkage rate is easily reduced, and the cured product is likely to become soft. (B-1): (B-2), which represents the mass ratio of monomer B-1 to monomer B-2, is preferably 1:0~1:1.
[單體B-1] 單體B-1係聚氧伸烷基單元醇與具有異氰酸酯基及(甲基)丙烯醯氧基之化合物的等莫耳反應物。 聚氧伸烷基單元醇係使環氧烷對具有含活性氫基且活性氫數為1個的引發劑進行開環加成聚合獲得而具有引發劑殘基、聚氧伸烷基鏈及與引發劑之活性氫數相對應之羥基的化合物。 環氧烷以碳數2~4之環氧烷為宜，具體例可舉：環氧丙烷、環氧乙烷、1,2-環氧丁烷、2,3-環氧丁烷。 引發劑所具有之含活性氫基可舉如羥基、羧基、具有1個鍵結於氮原子之氫原子的胺基，且以羥基及羧基為宜。作為羥基，則以醇性羥基較佳。 活性氫數為1個之引發劑可舉：一元醇、一元酚、一元羧酸、具有1個鍵結於氮原子之氫原子的胺化合物。引發劑宜為脂肪族一元醇及脂肪族一元羧酸。並且，可將分子量比目標聚氧伸烷基單元醇更低之聚氧伸烷基單元醇作為引發劑使用。 引發劑之脂肪族一元醇的碳數宜為1~20，2~8較佳。引發劑之脂肪族一元羧酸之碳數包含羧基之碳原子，且宜為2~20，2~8較佳。 聚氧伸烷基單元醇中之氧伸烷基宜為僅由氧伸丙基構成或由氧伸丙基與其以外之基的組合構成，且氧伸丙基以外之氧伸烷基宜為氧伸乙基。聚氧伸烷基單元醇中之氧伸丙基相對於全部氧伸烷基的含量宜為50~100質量%，80~100質量%較佳。聚氧伸烷基單元醇中包含氧伸烷基時，聚氧伸烷基單元醇中之氧伸乙基相對於全部氧伸烷基的含量宜為1質量%以上且小於50質量%，5質量%以上且小於20質量%更佳。另，當引發劑為分子量比目標聚氧伸烷基單元醇更低的聚氧伸烷基單元醇時，引發劑中之氧伸烷基可視為所得聚氧伸烷基單元醇中之氧伸烷基。[Monomer B-1] Monomer B-1 is an isomolar reaction product of a polyoxyalkylene unit alcohol and a compound having an isocyanate group and a (meth)acryloxy group. The polyoxyalkylene unit alcohol is obtained by ring-opening addition polymerization of an alkylene oxide to an initiator having an active hydrogen group and an active hydrogen number of one, and has an initiator residue, a polyoxyalkylene chain, and The active hydrogen number of the initiator corresponds to the hydroxyl compound. The alkylene oxide is preferably an alkylene oxide having a carbon number of 2 to 4. Specific examples include: propylene oxide, ethylene oxide, 1,2-butylene oxide, and 2,3-butylene oxide. Examples of the active hydrogen-containing group possessed by the initiator include a hydroxyl group, a carboxyl group, and an amino group having one hydrogen atom bonded to a nitrogen atom, and a hydroxyl group and a carboxyl group are preferred. As the hydroxyl group, an alcoholic hydroxyl group is preferred. Examples of initiators having one active hydrogen include monohydric alcohols, monohydric phenols, monocarboxylic acids, and amine compounds having one hydrogen atom bonded to a nitrogen atom. The initiator is preferably aliphatic monoalcohol and aliphatic monocarboxylic acid. In addition, a polyoxyalkylene unit alcohol having a lower molecular weight than the target polyoxyalkylene unit alcohol can be used as an initiator. The carbon number of the aliphatic monohydric alcohol of the initiator is preferably 1-20, preferably 2-8. The carbon number of the aliphatic monocarboxylic acid of the initiator includes the carbon atoms of the carboxyl group, and is preferably 2-20, preferably 2-8. The oxyalkylene group in the polyoxyalkylene unit alcohol is preferably composed only of oxypropylene group or a combination of oxypropylene group and other groups, and the oxyalkylene group other than oxypropylene group is preferably oxygen Ethylene. The content of the oxyalkylene group in the polyoxyalkylene unit alcohol relative to the total oxyalkylene group is preferably 50-100% by mass, preferably 80-100% by mass. When the polyoxyalkylene unit alcohol contains an oxyalkylene group, the content of the oxyalkylene group in the polyoxyalkylene unit alcohol relative to the total oxyalkylene group is preferably 1% by mass or more and less than 50% by mass. More preferably, it is greater than or equal to 20% by mass and less than 20% by mass. In addition, when the initiator is a polyoxyalkylene unit alcohol with a lower molecular weight than the target polyoxyalkylene unit alcohol, the oxyalkylene group in the initiator can be regarded as the oxygen extension in the obtained polyoxyalkylene unit alcohol. alkyl.
低羥值(亦即高分子量)聚氧伸烷基單元醇可在複合金屬氰化物錯合物觸媒存在下，使碳數3以上之環氧烷(尤其是環氧丙烷)對引發劑進行開環加成聚合來製造。
具有氧伸乙基之低羥值聚氧伸烷基單元醇亦可以具有氧伸乙基之高羥值(50mgKOH/g以上為佳)聚氧伸烷基單元醇作為引發劑，在複合金屬氰化物錯合物觸媒存在下，使碳數3以上之環氧烷(尤其是環氧丙烷)進行開環加成聚合來製造。高羥值聚氧伸烷基單元醇可在KOH等鹼觸媒存在下，使碳數3以上之環氧烷對引發劑進行開環加成聚合來製造。
用來製造單體B-1的聚氧伸烷基單元醇亦可為2種以上聚氧伸烷基單元醇之混合物。此時，各聚氧伸烷基單元醇宜皆為上述範疇中所含之聚氧伸烷基單元醇。
在製造聚氧伸烷基單元醇時，要投入反應系統內之引發劑或環氧烷通常係使用藉由減壓脫氣等去除水分後之水分少者。通常，製造聚氧伸烷基單元醇時之引發劑的水分量越少越佳，500質量ppm以下較佳，300質量ppm以下更佳。水分量若在該範圍內，便可抑制由水生成之聚氧伸烷基二醇之生成量，從而可抑制最終來自該聚氧伸烷基二醇之副產物的生成量，而易將所得聚氧伸烷基單元醇之平均羥基數之上限調整為1.3以下。
並且，作為原料使用的聚氧伸烷基單元醇中之水分量愈少愈佳，相對於聚氧伸烷基單元醇宜為300質量ppm以下，250質量ppm以下較佳，50~200質量ppm尤佳。水分量若在上述範圍內，屬水分與含異氰酸酯基化合物之反應產物的副產物之生成便少，而可提升反應產物之穩定性。並且，容易抑制包含反應產物之硬化性組成物歷時性的外觀變化，而硬化物之彈性模數容易變佳。Low hydroxyl value (that is, high molecular weight) polyoxyalkylene unit alcohols can cause alkylene oxides (especially propylene oxide) with
具有異氰酸酯基及(甲基)丙烯醯氧基的化合物，以具有1個異氰酸酯基之(甲基)丙烯酸酯為佳，且以異氰酸酯烷基(甲基)丙烯酸酯較佳。
具有1個異氰酸酯基與(甲基)丙烯醯氧基之化合物，以具有鍵結於脂肪族烴基或脂環族烴基之異氰酸酯基的(甲基)丙烯酸酯為佳，異氰酸酯烷基(甲基)丙烯酸酯尤佳。異氰酸酯基烷基之異氰酸酯基除外的烷基之碳數宜為8以下，4以下較佳。
具有異氰酸酯基及(甲基)丙烯醯氧基之化合物的具體例，可舉2-異氰酸酯乙基(甲基)丙烯酸酯、異氰酸酯甲基甲基丙烯酸酯。市售物可舉Karenz-AOI、Karenz-MOI(皆為昭和電工公司製品名)。
單體B-1之Mn的理想範圍與前述單體B相同。
單體B-1宜為後述化合物3。單體B-1宜為藉由使後述化合物3a與後述化合物3b反應而獲得的單體。The compound having an isocyanate group and a (meth)acryloxy group is preferably a (meth)acrylate having one isocyanate group, and more preferably an isocyanate alkyl (meth)acrylate.
The compound having an isocyanate group and a (meth)acryloyloxy group is preferably a (meth)acrylate having an isocyanate group bonded to an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, isocyanate alkyl (methyl) Acrylic is particularly preferred. The number of carbon atoms of the alkyl group other than the isocyanate group of the isocyanate group alkyl group is preferably 8 or less, preferably 4 or less.
Specific examples of the compound having an isocyanate group and a (meth)acryloxy group include 2-isocyanate ethyl (meth)acrylate and isocyanate methacrylate. Commercially available products include Karenz-AOI and Karenz-MOI (both are product names of Showa Denko).
The ideal range of Mn of the monomer B-1 is the same as that of the aforementioned monomer B.
The monomer B-1 is preferably the
化合物3a與化合物3b中，存在於1分子中之可進行胺甲酸乙酯化反應之基各為1個，所以容易將單體B-1之1分子中之胺甲酸乙酯鍵控制為1個。單體B-1之1分子中之胺甲酸乙酯鍵數若少，黏度便容易降低。因此，在硬化性組成物為低黏度且易獲得柔軟性優異的硬化物的觀點下，單體B包含單體B-1較佳。In
[化學式1]
[化學式2]
在式3、3a、3b中，R11
為氫原子或甲基，且以氫原子為佳。R12
為碳數2~4伸烷基，且存在於1分子中之多個R12
可彼此相同亦可互異。1分子中存在2種以上R12
時，-OR12
-之鏈可為嵌段，亦可為隨機。R12
宜為伸乙基及/或伸丙基。R13
表示碳數1~20烷基，或者R13
及與R13
鍵結之氧原子一起表示碳數1~20之羧酸殘基。羧酸殘基係從包含羧基(-COOH)中之碳原子之碳數為1~20的單羧酸去除1個羧基中之氫原子後的1價基。在容易反應之觀點下，R13
宜為碳數1~20烷基，碳數2~8烷基更佳。b為1~8之整數，且1~4之整數為佳。c為20~600之整數，35~500之整數為佳，65~250之整數較佳。In
化合物3a為聚氧伸烷基單元醇，可藉由以下方法獲得：以醇或對醇開環加成聚合環氧烷後之化合物作為引發劑，使環氧烷開環加成聚合的已知方法；或使環氧烷對單羧酸之羧基進行開環加成聚合的已知方法。化合物3a之羥值宜為1.6~56.1mgKOH/g，3.7~14mgKOH/g較佳。羥基換算分子量宜為1,000~35,000，4,000~15,000較佳。
化合物3a之羥基換算分子量若在上述範圍內，便容易將單體B-1之Mn調整至1,000~35,000之範圍內。化合物3a之羥基換算分子量若在上述範圍內，便容易將所生成之單體B-1的平均官能基數調整為0.8~1.3。羥基換算分子量愈小，愈容易將平均官能基數之上限調整在1.3以下。
在化合物3a之製造中，不需要特別利用減壓脫氣等來去除水分，其可允許要投入反應系統內之原料等中一般所含有的水分量。例如，通常引發劑之水分量愈少愈佳，500ppm以下較佳，300ppm以下更佳。水分量若在上述範圍內，便可抑制由水生成之二元醇的生成量，因此最終可抑制於二元醇加成有(甲基)丙烯醯氧基之副產物的生成量，而容易將包含副產物與單體B之產物(以下稱「產物B-1」)的平均官能基數之上限調整在1.3以下。In the production of
化合物3b可使用市售物，可舉如：Karenz-AOI(式3b之R11
=H、b=1)、Karenz-MOI(式3b之R11
=CH3
、b=1)(皆為昭和電工公司製品名)。
化合物3a與化合物3b之反應為胺甲酸乙酯化反應，可使用已知的手法進行。使該等反應時，化合物3b相對於化合物3a之摻混比，以指數計宜為80~100，90~100較佳，100最佳。指數若在上述範圍內，便容易將產物B-1之平均官能基數調整在0.8~1.3之範圍內。Compound 3b can use commercially available products, such as: Karenz-AOI (R 11 =H, b=1 of formula 3b), Karenz-MOI (R 11 =CH 3 , b=1 of formula 3b) (all are Showa Electrician's product name). The reaction of
為了充分發揮作為單體B之功能，產物B-1中之單體B-1的含量宜為80質量%以上，85~100質量%較佳。產物B-1以上述含量包含單體B-1時，可充分發揮單體B之功能，因此可將產物B-1視為單體B-1。In order to fully exert its function as monomer B, the content of monomer B-1 in product B-1 is preferably 80% by mass or more, preferably 85-100% by mass. When the product B-1 contains the monomer B-1 in the above content, the function of the monomer B can be fully exerted, so the product B-1 can be regarded as the monomer B-1.
當可將產物B-1視為單體B-1時，從產物B-1之Mn及官能基數求算之平均官能基數可視為單體B-1之平均官能基數。此時，產物B-1之平均官能基數宜為0.8~1.3，且0.9~1.2較佳。若在上述範圍內，產物B-1便容易降低硬化時之收縮，而容易降低硬化物之彈性模數。When the product B-1 can be regarded as the monomer B-1, the average number of functional groups calculated from the Mn and the number of functional groups of the product B-1 can be regarded as the average number of functional groups of the monomer B-1. At this time, the average number of functional groups of the product B-1 is preferably 0.8 to 1.3, and preferably 0.9 to 1.2. If it is within the above range, the product B-1 will easily reduce the shrinkage during curing, and easily reduce the elastic modulus of the cured product.
單體B-1宜為化合物3且包含單體B-1-PO，該單體B-1-PO之存在於1分子中，相對於R12
的總量，伸丙基含量為50~100莫耳%。Monomer B-1 is preferably
在單體B-1-PO中，相對於R12 的總量，伸丙基含量為80~100莫耳%較佳，100莫耳%尤佳。存在於1分子中之R12 中，存在伸丙基以外之伸烷基時，伸丙基以外之伸烷基宜為伸乙基。在單體B-1-PO之R12 中包含伸乙基作為伸烷基時，相對於R12 之總量，伸乙基含量宜為1莫耳%以上且小於30莫耳%，1莫耳%以上且小於25莫耳%較佳。In the monomer B-1-PO, relative to the total amount of R 12 , the propylene content is preferably 80-100 mol%, and 100 mol% is particularly preferred. When there is an alkylene group other than propylidene in R 12 present in one molecule, the alkylene group other than propylene group is preferably an ethylene group. When R 12 of monomer B-1-PO contains ethylene group as an alkylene group, relative to the total amount of R 12 , the ethylene group content is preferably 1 mol% or more and less than 30 mol%, 1 mol% More than ear% and less than 25 mol% are preferred.
並且在使用單體B-1-PO時，單體B-1-PO相對於單體B的含量宜為50~100質量%，80~100質量%較佳。單體B-1-PO之含量若為上述範圍之下限值以上，硬化性組成物即為低黏度，硬化物之柔軟性佳。In addition, when using the monomer B-1-PO, the content of the monomer B-1-PO relative to the monomer B is preferably 50-100% by mass, preferably 80-100% by mass. If the content of the monomer B-1-PO is above the lower limit of the above range, the curable composition has low viscosity and the cured product has good flexibility.
[單體B-2] 單體B-2係聚氧伸烷基單元醇、二異氰酸酯及具有可與異氰酸酯基反應之基及(甲基)丙烯醯氧基之化合物的等莫耳反應產物。 單體B-2中之聚氧伸烷基單元醇與前述聚氧伸烷基單元醇相同。 具有可與異氰酸酯基反應之基及(甲基)丙烯醯氧基的化合物中之可與異氰酸酯基反應之基，可舉如：羥基、具有氫原子所鍵結之氮原子的胺基。可與異氰酸酯基反應之基中之羥基數或鍵結於氮原子之氫原子數宜為1個。可與異氰酸酯基反應之基宜為鍵結於脂肪族烴基或脂環族烴基之羥基。具有可與異氰酸酯基反應之基及(甲基)丙烯醯氧基的化合物，宜為(甲基)丙烯酸羥烷基酯及(甲基)丙烯酸羥環烷基酯，且羥烷基之碳數為8以下之(甲基)丙烯酸羥烷基酯尤佳。 具有可與異氰酸酯基反應之基及(甲基)丙烯醯氧基的化合物之具體例，可舉(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸2-羥丙酯、(甲基)丙烯酸2-羥丁酯、(甲基)丙烯酸4-羥丁酯、(甲基)丙烯酸6-羥己酯。市售物可舉：Lightester HO-250(N)、Lightester HOP(N)、Lightester HOA(N)、Lightester HOP-A(N)、Lightester HOB(N)(皆為共榮化學公司製品名)、4-HBA(大阪有機化學工業公司製品名)。 單體B-2之Mn的理想範圍與前述單體B相同。 單體B-2宜為後述化合物4。單體B-2宜為下述化合物：使後述化合物4a與後述化合物4b反應而獲得於末端具有異氰酸酯基之預聚物(異氰酸酯基末端胺甲酸乙酯預聚物)後，使化合物4c對所得預聚物之異氰酸酯基反應而獲得的化合物。[Monomer B-2] Monomer B-2 is an isomolar reaction product of a polyoxyalkylene unit alcohol, a diisocyanate, and a compound having a group capable of reacting with an isocyanate group and a (meth)acryloxy group. The polyoxyalkylene unit alcohol in monomer B-2 is the same as the aforementioned polyoxyalkylene unit alcohol. Among the compounds having a group reactive with an isocyanate group and a (meth)acryloxy group, the group reactive with an isocyanate group may include a hydroxyl group and an amino group having a nitrogen atom to which a hydrogen atom is bonded. The number of hydroxyl groups in a group that can react with an isocyanate group or the number of hydrogen atoms bonded to a nitrogen atom is preferably one. The group capable of reacting with the isocyanate group is preferably a hydroxyl group bonded to an aliphatic hydrocarbon group or an alicyclic hydrocarbon group. The compound having a group capable of reacting with an isocyanate group and a (meth)acryloyloxy group is preferably a hydroxyalkyl (meth)acrylate and a hydroxycycloalkyl (meth)acrylate, and the carbon number of the hydroxyalkyl group Hydroxyalkyl (meth)acrylate of 8 or less is particularly preferred. Specific examples of compounds having a group capable of reacting with an isocyanate group and a (meth)acryloyloxy group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (methyl) ) 2-hydroxybutyl acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate. Commercial products can include: Lightester HO-250(N), Lightester HOP(N), Lightester HOA(N), Lightester HOP-A(N), Lightester HOB(N) (all are the product names of Gongrong Chemical Company), 4-HBA (product name of Osaka Organic Chemical Industry Co., Ltd.). The ideal range of Mn of the monomer B-2 is the same as that of the aforementioned monomer B. The monomer B-2 is preferably the compound 4 described later. Monomer B-2 is preferably a compound: after reacting compound 4a described later with compound 4b described later to obtain a prepolymer having an isocyanate group at the end (isocyanate group-terminated urethane prepolymer), the compound 4c A compound obtained by reacting the isocyanate group of the prepolymer.
[化學式3]
[化學式4]
在式4、4a、4b、4c中，R21 為氫原子或甲基，且氫原子為佳。R22 為碳數2~4伸烷基，且存在於1分子中之多個R22 可彼此相同亦可互異。1分子中存在2種以上R22 時，-OR22 -之鏈可為嵌段，亦可為隨機。R22 宜為伸乙基及/或伸丙基。R23 表示碳數1~20烷基，或者R23 及與R23 鍵結之氧原子一起表示碳數1~20之羧酸殘基。羧酸殘基係從包含羧基中之碳原子之碳數為1~20的單羧酸去除1個羧基中之氫原子後的1價基。在容易反應之觀點下，R23 宜為碳數1~20烷基，碳數2~8烷基更佳。In formulas 4, 4a, 4b, and 4c, R 21 is a hydrogen atom or a methyl group, and a hydrogen atom is preferred. R 22 is an alkylene group having 2 to 4 carbon atoms, and a plurality of R 22 existing in one molecule may be the same or different from each other. When two or more types of R 22 are present in one molecule, the chain of -OR 22 -may be block or random. R 22 is preferably ethylene and/or ethylene. R 23 represents an alkyl group with 1 to 20 carbons, or R 23 and the oxygen atom bonded to R 23 together represent a carboxylic acid residue with 1 to 20 carbons. The carboxylic acid residue is a monovalent group obtained by removing one hydrogen atom in a carboxyl group from a monocarboxylic acid having carbon atoms of 1 to 20 carbon atoms in the carboxyl group. From the viewpoint of easy reaction, R 23 is preferably an alkyl group with 1 to 20 carbon atoms, and an alkyl group with 2 to 8 carbon atoms is more preferable.
R24 係已從化合物4b去除異氰酸酯基之2價基。化合物4b可舉如具有2個異氰酸酯基之化合物，宜為異佛酮二異氰酸酯、二異氰酸六亞甲酯。 d為1~8之整數，且1~4之整數為宜。e為20~600之整數，且35~500之整數為佳，65~250之整數較佳。R 24 is a divalent group in which the isocyanate group has been removed from compound 4b. The compound 4b may be a compound having two isocyanate groups, preferably isophorone diisocyanate and hexamethylene diisocyanate. d is an integer from 1 to 8, and an integer from 1 to 4 is suitable. e is an integer from 20 to 600, and an integer from 35 to 500 is preferred, and an integer from 65 to 250 is preferred.
化合物4a為聚氧伸烷基單元醇，可藉由以下方法獲得：以醇或對醇開環加成聚合環氧烷後之化合物作為引發劑，使環氧烷開環加成聚合的已知方法；或使環氧烷對單羧酸之羧基進行開環加成聚合的已知方法。化合物4a之羥值宜為1.6~56.1mgKOH/g，3.7~14mgKOH/g較佳。羥基換算分子量宜為1,000~35,000，4,000~15,000較佳。 化合物4a之羥基換算分子量若在上述範圍內，便可將單體B-2之Mn調整在1,000~35,000之範圍內。Compound 4a is a polyoxyalkylene unit alcohol, which can be obtained by the following method: using alcohol or a compound obtained after ring-opening addition polymerization of alkylene oxide to alcohol as an initiator, known as the ring-opening addition polymerization of alkylene oxide Method; or the known method of ring-opening addition polymerization of alkylene oxide to the carboxyl group of monocarboxylic acid. The hydroxyl value of compound 4a is preferably 1.6~56.1mgKOH/g, preferably 3.7~14mgKOH/g. The molecular weight in terms of hydroxyl group is preferably 1,000 to 35,000, preferably 4,000 to 15,000. If the hydroxyl-converted molecular weight of compound 4a is within the above range, the Mn of monomer B-2 can be adjusted in the range of 1,000 to 35,000.
製造化合物4a時之水分量及分子量，與化合物3a之情況相同。即使在製造化合物4a之情況下，亦與化合物3a之情況同樣地，會有獲得包含於由原料中所含之水生成的二元醇加成有(甲基)丙烯醯氧基之副產物與單體B-2的產物(以下亦稱「產物B-2」)之情形。The water content and molecular weight when producing compound 4a are the same as those of
使化合物4a與化合物4b反應而獲得於末端具有異氰酸酯基之預聚物(異氰酸酯基末端胺甲酸乙酯預聚物)的反應係胺甲酸乙酯化反應，可使用已知的手法進行。使該等反應時，化合物4b相對於化合物4a之摻混比，以指數計宜為100~200，180~200較佳，200最佳。指數若在上述範圍內，便容易將產物B-2之平均官能基數調整在0.8~1.3之範圍內。The urethane reaction of the prepolymer (isocyanate group-terminated urethane prepolymer) obtained by reacting the compound 4a with the compound 4b to obtain an isocyanate group-terminated prepolymer can be carried out using a known method. When making these reactions, the blending ratio of compound 4b to compound 4a is preferably 100-200 as an index, preferably 180-200, and 200 is the best. If the index is within the above range, it is easy to adjust the average number of functional groups of product B-2 within the range of 0.8 to 1.3.
所得異氰酸酯基末端胺甲酸乙酯預聚物與化合物4c之反應係胺甲酸乙酯化反應，可使用已知的手法進行。The reaction of the obtained isocyanate group-terminated urethane prepolymer and the compound 4c is the urethane reaction, which can be carried out by a known method.
使該等反應時，預聚物與化合物4c之摻混比，以該預聚物中之異氰酸酯基：化合物4c中之羥基的莫耳比為1：1.0~1.1為佳，1：1.0~1.05較佳。若在上述範圍內，便容易將產物B-2之平均官能基數調整在0.8~1.3之範圍。 為了充分發揮作為單體B之功能，產物B-2中之單體B-2的含量宜為80質量%以上，85~100質量%較佳。產物B-2以上述含量包含單體B-2時，可充分發揮單體B之功能，因此可將產物B-2視為單體B-2。When making these reactions, the blending ratio of the prepolymer and compound 4c is preferably 1:1.0~1.1, 1:1.0~1.05 for the molar ratio of isocyanate group in the prepolymer to the hydroxyl group in compound 4c. Better. If it is within the above range, it is easy to adjust the average number of functional groups of product B-2 in the range of 0.8 to 1.3. In order to fully exert its function as monomer B, the content of monomer B-2 in product B-2 is preferably 80% by mass or more, preferably 85-100% by mass. When the product B-2 contains the monomer B-2 in the above content, the function of the monomer B can be fully exerted, so the product B-2 can be regarded as the monomer B-2.
當可將產物B-2視為單體B-2時，從產物B-2之Mn及官能基數求算之平均官能基數可視為單體B-2之平均官能基數。此時，產物B-2之平均官能基數宜為0.8~1.3，且0.9~1.2較佳。若在上述範圍內，產物B-2便容易降低硬化時之收縮，而容易降低硬化物之彈性模數。When the product B-2 can be regarded as the monomer B-2, the average number of functional groups calculated from the Mn and the number of functional groups of the product B-2 can be regarded as the average number of functional groups of the monomer B-2. At this time, the average number of functional groups of product B-2 is preferably 0.8 to 1.3, and preferably 0.9 to 1.2. If it is within the above range, the product B-2 will easily reduce the shrinkage during curing, and easily reduce the elastic modulus of the cured product.
單體B-2宜為化合物4且包含單體B-2-PO，該單體B-2-PO之存在於1分子中，相對於R22 的總量，伸丙基含量為50~100莫耳%。Monomer B-2 is preferably compound 4 and contains monomer B-2-PO. The monomer B-2-PO is present in one molecule. Relative to the total amount of R 22 , the propylene content is 50-100 Mol%.
在單體B-2-PO中，相對於R22 的總量，伸丙基含量為80~100莫耳%較佳，100莫耳%尤佳。存在於1分子中之R22 中，存在伸丙基以外之伸烷基時，伸丙基以外之伸烷基宜為伸乙基。在單體B-2-PO之R22 中包含伸乙基作為伸烷基時，相對於R22 之總量，伸乙基含量宜為1莫耳%以上且小於30莫耳%，1莫耳%以上且小於25莫耳%較佳。In the monomer B-2-PO, relative to the total amount of R 22 , the propylene content is preferably 80-100 mol%, and 100 mol% is particularly preferred. When there is an alkylene group other than propylidene in R 22 in one molecule, the alkylene group other than propylene group is preferably an ethylene group. When R 22 of monomer B-2-PO contains ethylene group as an alkylene group, relative to the total amount of R 22 , the ethylene group content is preferably 1 mol% or more and less than 30 mol%, 1 mol% More than ear% and less than 25 mol% are preferred.
並且在使用單體B-2-PO時，單體B-2-PO相對於單體B的含量宜為50~100質量%，80~100質量%較佳。單體B-2-PO之含量若為上述範圍之下限值以上，硬化性組成物即為低黏度，硬化物之柔軟性佳。And when using the monomer B-2-PO, the content of the monomer B-2-PO relative to the monomer B is preferably 50-100% by mass, preferably 80-100% by mass. If the content of the monomer B-2-PO is above the lower limit of the above range, the curable composition has low viscosity and the cured product has good flexibility.
[單體B-3] 單體B-3係使後述化合物5a與前述化合物3b反應而獲得的官能基數為1之寡聚物。 單體B-3之Mn的理想範圍與前述單體B相同。[Monomer B-3] The monomer B-3 is an oligomer with 1 functional group obtained by reacting the compound 5a and the compound 3b described later. The ideal range of Mn of the monomer B-3 is the same as that of the aforementioned monomer B.
[化學式5]
在式5a中，R32 為碳數2~4伸烷基，存在於1分子中之多個R32 可彼此相同亦可互異。1分子中存在2種以上R32 時，-OR32 -之鏈可為嵌段，亦可為隨機。R32 宜為伸乙基及/或伸丙基。 相對於R32 之總量，伸丙基含量宜為50~100莫耳%，80~100莫耳%較佳。存在於1分子中之R32 中，存在伸丙基以外之伸烷基時，伸丙基以外之伸烷基宜為伸乙基。In formula 5a, R 32 is an alkylene group with 2 to 4 carbon atoms, and a plurality of R 32 in one molecule may be the same or different from each other. When two or more types of R 32 are present in one molecule, the chain of -OR 32 -may be block or random. R 32 is preferably ethylene and/or ethylene. Relative to the total amount of R 32 , the propylene content is preferably 50-100 mol%, preferably 80-100 mol%. When there is an alkylene group other than a propylene group in R 32 in one molecule, the alkylene group other than the propylene group is preferably an ethylene group.
式5a中之f為20~600之整數，且35~500之整數為佳，65~250之整數較佳。 f若在上述範圍內，便容易將單體B-3之Mn調整至1,000~35,000之範圍內。In formula 5a, f is an integer from 20 to 600, and an integer from 35 to 500 is preferred, and an integer from 65 to 250 is preferred. If f is in the above range, it is easy to adjust the Mn of monomer B-3 to the range of 1,000 to 35,000.
化合物5a與化合物3b之反應為胺甲酸乙酯化反應，可使用已知的手法進行。 在該反應中，化合物5a兩末端的羥基可與化合物3b進行反應，所以除了官能基數為1之寡聚物以外，有時就副產物，會獲得包含官能基數為2之寡聚物的產物(以下亦稱「產物B-3))。 產物B-3之平均官能基數宜為0.8~1.3，且0.9~1.2較佳。The reaction of compound 5a and compound 3b is a urethane reaction, which can be carried out using a known method. In this reaction, the hydroxyl groups at both ends of compound 5a can react with compound 3b, so in addition to oligomers with functional groups of 1, sometimes as by-products, products containing oligomers with functional groups of 2 are obtained ( Hereinafter, it is also referred to as "Product B-3)). The average number of functional groups of product B-3 is preferably 0.8 to 1.3, and preferably 0.9 to 1.2.
在該反應中，化合物3b相對於化合物5a之摻混比，以指數計宜為30~50，40~50較佳，50最佳。指數若在上述範圍內，便容易獲得化合物3b之1分子對化合物5a之1分子進行反應的化合物，而容易將產物B-3之平均官能基數調整在0.8~1.3之範圍內。In this reaction, the blending ratio of compound 3b to compound 5a is preferably 30-50 as an index, preferably 40-50, and 50 is the best. If the index is within the above range, it is easy to obtain a compound in which one molecule of compound 3b reacts with one molecule of compound 5a, and it is easy to adjust the average number of functional groups of product B-3 within the range of 0.8 to 1.3.
為了充分發揮作為單體B之功能，產物B-3中之單體B-3的含量宜為80質量%以上，85~100質量%較佳。產物B-3以上述含量包含單體B-3時，可充分發揮單體B之功能，因此可將產物B-3視為單體B-3。In order to give full play to the function of monomer B, the content of monomer B-3 in product B-3 is preferably 80% by mass or more, preferably 85-100% by mass. When the product B-3 contains the monomer B-3 in the above content, the function of the monomer B can be fully exerted, so the product B-3 can be regarded as the monomer B-3.
當可將產物B-3視為單體B-3時，從產物B-3之Mn及官能基數求算之平均官能基數可視為單體B-3之平均官能基數。此時，產物B-3之平均官能基數宜為0.8~1.3，且0.9~1.2較佳。若在上述範圍內，產物B-3便容易降低硬化時之收縮，而容易降低硬化物之彈性模數。When the product B-3 can be regarded as the monomer B-3, the average number of functional groups calculated from the Mn and the number of functional groups of the product B-3 can be regarded as the average number of functional groups of the monomer B-3. At this time, the average number of functional groups of product B-3 is preferably 0.8 to 1.3, and preferably 0.9 to 1.2. If it is within the above range, the product B-3 will easily reduce the shrinkage during curing, and easily reduce the elastic modulus of the cured product.
＜交聯劑＞
本實施形態之硬化性組成物宜包含交聯劑。交聯劑係具有2個以上可與單體B聚合之交聯性官能基的化合物。若摻混交聯劑，容易提升耐熱性及潛變回復率。
交聯性官能基宜選自(甲基)丙烯醯基、環氧基、異氰酸酯基、羧基、羥基、碳二亞胺基、
交聯劑宜為多官能(甲基)丙烯酸酯。可舉如國際公開第2018/173896號之[0136]中所記載的多官能(甲基)丙烯酸酯。 在容易提升潛變回復率的觀點上，宜為：1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、三羥甲丙烷三丙烯酸酯、新戊四醇三丙烯酸酯、乙氧化異三聚氰酸三丙烯酸酯。 交聯劑可使用1種，亦可併用2種以上。The crosslinking agent is preferably a multifunctional (meth)acrylate. Examples include the polyfunctional (meth)acrylates described in [0136] of International Publication No. 2018/173896. From the viewpoint of easy to improve the creep recovery rate, it is suitable to be: 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonane Alcohol di(meth)acrylate, trimethylolpropane triacrylate, neopentylerythritol triacrylate, ethoxylated isocyanuric acid triacrylate. One type of crosslinking agent may be used, or two or more types may be used in combination.
交聯劑之使用量，以相對於單體B之1莫耳，交聯劑之交聯性官能基為1~20莫耳之量為佳，2~15莫耳較佳，2.5~13莫耳更佳。若為上述範圍之下限值以上，硬化物之耐熱性便更優異；若為上限值以下，便容易提升潛變回復率。The amount of crosslinking agent used is 1 mol relative to monomer B, and the crosslinking functional group of the crosslinking agent is preferably 1-20 mol, preferably 2-15 mol, 2.5-13 mol Better ears. If it is above the lower limit of the above range, the heat resistance of the cured product will be more excellent; if it is below the upper limit, the creep recovery rate will be easily increased.
＜光聚合引發劑＞ 本實施形態之硬化性組成物可為光硬化性，亦可為熱硬化性。若從可在低溫下硬化、且硬化速度快的觀點來看，以光硬化性者為佳。 硬化性組成物為光硬化性時，宜含有光聚合引發劑。硬化性組成物若為光硬化性，例如在用於製造顯示裝置時就不需要高溫度，因此顯示器件因高溫而損傷之疑慮亦少。＜Photopolymerization initiator＞ The curable composition of this embodiment may be photocurable or thermosetting. From the standpoint of being able to harden at low temperatures and having a fast hardening speed, light hardening is preferred. When the curable composition is photocurable, it is preferable to contain a photopolymerization initiator. If the curable composition is photocurable, for example, when it is used in the manufacture of a display device, a high temperature is not required, so there is less concern about damage to the display device due to high temperature.
光聚合引發劑可發揮作為交聯劑之交聯反應中之反應引發助劑的功能。從容易控制交聯反應的觀點來看，以對波長380nm以下紫外線起反應之光聚合引發劑為佳。 光聚合引發劑之例，可舉國際公開第2018/173896號之[0147]~[0151]中所記載之光聚合引發劑。 光聚合引發劑宜為奪氫型光聚合引發劑，其係經光激發之引發劑與系統中之氫供體形成激發錯合物，使氫供體之氫轉移者。奪氫型光聚合引發劑之具體例可舉：二苯基酮、4-甲基-二苯基酮、2,4,6-三甲基二苯基酮、4-苯基二苯基酮、3,3'-二甲基-4-甲氧基二苯基酮、4-(甲基)丙烯醯氧基二苯基酮、4-[2-((甲基)丙烯醯氧基)乙氧基]二苯基酮、4-(甲基)丙烯醯氧基-4'-甲氧基二苯基酮、2-苯甲醯苯甲酸甲酯、苯甲醯甲酸甲酯。 光聚合引發劑可為1種，亦可併用2種以上。The photopolymerization initiator can function as a reaction initiation assistant in the crosslinking reaction of the crosslinking agent. From the viewpoint of easy control of the crosslinking reaction, a photopolymerization initiator that reacts to ultraviolet rays having a wavelength of 380 nm or less is preferred. Examples of photopolymerization initiators include the photopolymerization initiators described in [0147] to [0151] of International Publication No. 2018/173896. The photopolymerization initiator is preferably a hydrogen abstraction type photopolymerization initiator, which is a photo-excited initiator that forms an excited complex with the hydrogen donor in the system to transfer hydrogen from the hydrogen donor. Specific examples of hydrogen abstraction type photopolymerization initiators include: benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone , 3,3'-Dimethyl-4-methoxybenzophenone, 4-(meth)acryloxy benzophenone, 4-[2-((meth)acryloxy) Ethoxy] benzophenone, 4-(meth)acryloyloxy-4'-methoxy benzophenone, methyl 2-benzyl benzoate, methyl benzoate. The photopolymerization initiator may be one type, or two or more types may be used in combination.
相對於聚合物A之100質量份，光聚合引發劑之使用量宜為0.1~10質量份，0.3~5質量份較佳。光聚合引發劑之使用量若為上述範圍內，便容易對活性能量線獲得適度的反應敏感度。Relative to 100 parts by mass of polymer A, the amount of the photopolymerization initiator used is preferably 0.1-10 parts by mass, preferably 0.3-5 parts by mass. If the amount of the photopolymerization initiator used is within the above range, it is easy to obtain a moderate reaction sensitivity to active energy rays.
＜其他成分＞ 本實施形態之硬化性組成物在聚合物A、單體B、交聯劑及光聚合引發劑以外之其他成分，可含有視需求之已知的成分。 其他成分可舉如：矽烷耦合劑、賦黏樹脂、抗氧化劑、光穩定化劑、金屬減活劑、防鏽劑、抗老化劑、吸濕劑、抗水解劑、抗靜電劑、消泡劑、無機粒子等。 亦可視需求含有反應觸媒(三級胺系化合物、四級銨系化合物或月桂酸錫化合物等)。 亦可視需求含有溶劑。 亦可視需求含有多官能異氰酸酯化合物。多官能異氰酸酯化合物之具體例可舉日本專利第6375467號之[0062]中記載的成分。＜Other ingredients＞ The curable composition of this embodiment may contain other components other than polymer A, monomer B, crosslinking agent, and photopolymerization initiator, as required, known components. Other ingredients can include: silane coupling agent, tackifying resin, antioxidant, light stabilizer, metal deactivator, rust inhibitor, anti-aging agent, moisture absorbent, anti-hydrolysis agent, antistatic agent, defoamer , Inorganic particles, etc. It can also contain reaction catalysts (tertiary amine compounds, quaternary ammonium compounds, tin laurate compounds, etc.) as required. It can also contain solvents as required. It can also contain a multifunctional isocyanate compound as required. Specific examples of the polyfunctional isocyanate compound include the components described in [0062] of Japanese Patent No. 6375467.
＜硬化性組成物＞ 本實施形態之硬化性組成物具有聚合物A、單體B、視需求之交聯劑、光聚合引發劑、其他成分。使該等混合物硬化，可獲得目標硬化物。 各成分之混合順序無限定。亦可於混合各成分後進行熱處理。 構成硬化性組成物之各成分可預先混合，亦可在即將要使其硬化前再行混合。例如，可於已預先混合有光聚合引發劑以外之成分的預混合物中，在即將使其硬化前添加光聚合引發劑。 本實施形態之硬化性組成物即便不含溶劑仍可使用。亦可視需求包含溶劑。溶劑宜在硬化時或硬化後去除。＜Curable composition＞ The curable composition of this embodiment has polymer A, monomer B, optionally a crosslinking agent, a photopolymerization initiator, and other components. The mixture is hardened to obtain the target hardened product. The mixing order of the ingredients is not limited. It is also possible to perform heat treatment after mixing the components. The components constituting the curable composition may be mixed in advance, or may be mixed just before hardening. For example, it is possible to add a photopolymerization initiator to a premix in which components other than the photopolymerization initiator have been mixed in advance, just before hardening. The curable composition of this embodiment can be used even if it does not contain a solvent. A solvent may also be included as required. The solvent should be removed during or after hardening.
相對於硬化性組成物之總量，聚合物A與單體B之合計含量宜為80質量%以上，85質量%以上較佳，90質量%以上更佳。With respect to the total amount of the curable composition, the total content of the polymer A and the monomer B is preferably 80% by mass or more, preferably 85% by mass or more, and more preferably 90% by mass or more.
＜硬化物＞ 本實施形態之硬化物可使本實施形態之硬化性組成物硬化而獲得。例如，將硬化性組成物成形為期望之形狀，並照射紫外線使其硬化。 硬化性組成物之成形方法，可舉如塗佈於基材上之方法、擠製成形之方法、注入模具中之方法。 紫外線之照射量宜為0.1~5J/cm2 ，0.3~4J/cm2 較佳，0.5~3J/cm2 更佳。若為上述範圍之下限值以上，耐熱性、潛變回復率會變得更佳；若為上限值以下，便不易著色。<Cured product> The cured product of this embodiment can be obtained by curing the curable composition of this embodiment. For example, the curable composition is formed into a desired shape and irradiated with ultraviolet rays to cure it. The method of forming the curable composition may be, for example, a method of coating on a substrate, a method of extrusion molding, and a method of injecting into a mold. The amount of ultraviolet radiation is preferably 0.1~5J/cm 2 , 0.3~4J/cm 2 is preferred, 0.5~3J/cm 2 is more preferred. If it is above the lower limit of the above range, the heat resistance and creep recovery rate will become better; if it is below the upper limit, it is difficult to color.
本實施形態之硬化物的動態黏彈性之tanδ尖峰溫度、即玻璃轉移溫度的上限值宜為-35℃，-37℃較佳，-38℃更佳。若為上述上限值以下，在低溫下之彎曲耐久性便更為優異。在捲曲殘存率容易變佳的觀點下，玻璃轉移溫度之下限值宜為-80℃，-70℃較佳，-60℃更佳。 本實施形態之硬化物的動態黏彈性之tanδ尖峰溫度、即玻璃轉移溫度宜為-80℃~-35℃，-70℃~-37℃較佳，-60℃~-38℃更佳。硬化物之玻璃轉移溫度若為上述範圍內，在低溫下之彎曲耐久性便更為優異。 本實施形態之硬化物在-20℃下之儲存彈性模數宜為150~1500，200~1000較佳，250~600更佳。若為上述範圍內，本發明之硬化物的硬化物在低溫下依舊容易維持柔軟性，用於積層體之黏著片材時，可更提升積層體之彎折耐久性及形狀回復性。 本實施形態之硬化物在25℃下之儲存彈性模數宜為80~700，100~500較佳，100~250更佳。若為上述範圍內，本發明之硬化物的硬化物即使在室溫附近依舊容易維持柔軟性，用於積層體之黏著片材時，可更提升積層體之彎折耐久性及形狀回復性。 本實施形態之硬化物在80℃下之儲存彈性模數宜為20~300，30~250較佳，45~200更佳。若為上述範圍內，本發明之硬化物的硬化物即使在高溫下依舊容易維持柔軟性，用於積層體之黏著片材時，可更提升積層體之彎折耐久性及形狀回復性。 本實施形態之硬化物之「E'(-20℃)/E'(80℃)」宜為1.0~9.0，1.0~8.0較佳，1.0~7.0更佳，該「E'(-20℃)/E'(80℃)」表示-20℃下之儲存彈性模數E'(-20℃)(kPa)相對於80℃下之儲存彈性模數E'(80℃)(kPa)的比值。若在上述範圍內，本發明之硬化物的彈性模數因溫度所引發的變化便少，容易維持柔軟性，在用於積層體之黏著片材時，可更提升積層體之彎折耐久性及形狀回復性。The upper limit of the tanδ peak temperature of the dynamic viscoelasticity of the cured product of this embodiment, that is, the glass transition temperature, is preferably -35°C, preferably -37°C, and more preferably -38°C. If it is below the above upper limit, the bending durability at low temperature will be more excellent. From the viewpoint that the curl remaining rate is likely to be better, the lower limit of the glass transition temperature is preferably -80°C, preferably -70°C, and more preferably -60°C. The tanδ peak temperature of the dynamic viscoelasticity of the cured product of this embodiment, that is, the glass transition temperature, is preferably -80°C to -35°C, preferably -70°C to -37°C, and more preferably -60°C to -38°C. If the glass transition temperature of the cured product is within the above range, the bending durability at low temperatures will be more excellent. The storage elastic modulus of the cured product of this embodiment at -20°C is preferably 150-1500, preferably 200-1000, and even more preferably 250-600. If it is within the above range, the cured product of the cured product of the present invention is easy to maintain flexibility at low temperatures, and when used for the adhesive sheet of the laminate, the bending durability and shape recovery of the laminate can be further improved. The storage elastic modulus of the cured product of this embodiment at 25°C is preferably 80-700, preferably 100-500, and more preferably 100-250. If it is within the above range, the cured product of the cured product of the present invention is easy to maintain flexibility even at around room temperature. When used in the adhesive sheet of the laminate, the bending durability and shape recovery of the laminate can be further improved. The storage elastic modulus of the cured product of this embodiment at 80°C is preferably 20 to 300, preferably 30 to 250, and more preferably 45 to 200. If it is within the above range, the cured product of the cured product of the present invention is easy to maintain flexibility even at high temperatures, and when used for the adhesive sheet of the laminate, the bending durability and shape recovery of the laminate can be further improved. The "E'(-20°C)/E'(80°C)" of the hardened product of this embodiment is preferably 1.0~9.0, 1.0~8.0 is better, 1.0~7.0 is even better, the "E'(-20°C) /E'(80°C)" means the ratio of the storage elastic modulus E'(-20°C)(kPa) at -20°C to the storage elastic modulus E'(80°C)(kPa) at 80°C. If it is within the above range, the change in the elastic modulus of the cured product of the present invention due to temperature is small, and it is easy to maintain flexibility. When used in the adhesive sheet of the laminate, the bending durability of the laminate can be improved. And shape recovery.
＜黏著片材＞ 本實施形態之硬化物可作為黏著層使用。本實施形態之黏著片材具有由本實施形態之硬化物所構成的片狀黏著層。宜將脫模薄膜設置成與黏著層之兩面相接。脫模薄膜可使用已知的脫模薄膜。 黏著片材例如可以下述方法製造：於第1脫模薄膜上塗佈硬化性組成物並使其硬化後，於其上積層第2脫模薄膜的方法；或於第1脫模薄膜上塗佈硬化性組成物，並於其上積層第2脫模薄膜後使其硬化的方法。＜Adhesive sheet＞ The cured product of this embodiment can be used as an adhesive layer. The adhesive sheet of this embodiment has a sheet-like adhesive layer composed of the cured product of this embodiment. It is advisable to set the release film to be in contact with both sides of the adhesive layer. As the release film, a known release film can be used. The adhesive sheet can be produced, for example, by a method of coating the curable composition on the first release film and curing it, and then laminating the second release film thereon; or coating on the first release film A method of laying a curable composition and laminating a second release film on it to harden it.
在本實施形態之黏著片材中，黏著層之厚度宜為10~150μm，20~120μm較佳，25~100μm更佳。若為上述範圍之下限值以上，黏著層就容易變平滑；若為上限值以下，反覆彎曲耐久性便更優異。In the adhesive sheet of this embodiment, the thickness of the adhesive layer is preferably 10 to 150 μm, preferably 20 to 120 μm, and more preferably 25 to 100 μm. If it is more than the lower limit of the above range, the adhesive layer is likely to be smooth; if it is less than the upper limit, the repeated bending durability is more excellent.
＜積層體＞ 本實施形態之積層體具備由本實施形態之硬化物所構成的黏著層與透過黏著層積層的撓性構件。 撓性構件可舉構成撓性顯示器面板之構件。撓性構件可舉如表面保護面板、光學薄膜、觸控面板、顯示面板本體。 表面保護面板可舉如薄板狀覆蓋玻璃、覆蓋薄膜。 光學薄膜係具有光學功能之構件。光學薄膜可舉如偏光薄膜、相位差薄膜、光學濾波器、抗反射薄膜、近紅外線截止薄膜、電磁波屏蔽膜。 觸控面板例如是於薄板狀玻璃基材或塑膠基材搭載有觸控感測器之構成。 顯示面板本體可舉如有機EL顯示器面板。＜Laminated body＞ The laminated body of this embodiment is equipped with the adhesive layer which consists of the hardened|cured material of this embodiment, and the flexible member laminated|stacked through the adhesive layer. The flexible member can be a member constituting a flexible display panel. Examples of flexible components include surface protection panels, optical films, touch panels, and display panel bodies. The surface protection panel can be, for example, a thin plate-shaped cover glass or a cover film. The optical film is a member with optical functions. Examples of optical films include polarizing films, retardation films, optical filters, anti-reflection films, near-infrared cut films, and electromagnetic wave shielding films. The touch panel is, for example, a structure in which a touch sensor is mounted on a thin glass substrate or a plastic substrate. The display panel body may be an organic EL display panel.
本實施形態之積層體為撓性，宜具有：即使在靜置狀態下固定成彎曲之形狀仍不會破損之性狀(Bendable：可彎的)、彎折或捲曲成撓曲半徑3mm以上仍可回復形狀之性狀(Rollable：可捲的)、或摺疊成撓曲半徑小於3mm仍可回復形狀之性狀(Foldable：可摺的)中之1種以上。The laminated body of this embodiment is flexible, and it is preferable to have: even if it is fixed into a curved shape in a static state, it will not be damaged (Bendable: bendable), and it can be bent or curled to a bending radius of 3mm or more. One or more of the properties of restoring shape (Rollable), or the properties of restoring the shape after being folded into a deflection radius of less than 3mm (Foldable).
在本實施形態之積層體中，黏著層之厚度宜為10~150μm，20~120μm較佳，25~100μm更佳。若為上述範圍之下限值以上，黏著層就容易變平滑；若為上限值以下，反覆彎曲耐久性便更優異。In the laminated body of this embodiment, the thickness of the adhesive layer is preferably 10 to 150 μm, preferably 20 to 120 μm, and more preferably 25 to 100 μm. If it is more than the lower limit of the above range, the adhesive layer is likely to be smooth; if it is less than the upper limit, the repeated bending durability is more excellent.
＜撓性顯示器＞ 本實施形態之撓性顯示器具備本實施形態之積層體。 本實施形態之硬化性組成物藉由包含聚合物A與單體B，可如後述實施例所示，降低硬化物之玻璃轉移溫度，而可降低彈性模數。所以，例如即使在用於用以構成撓性顯示器之構件間的黏著層時，仍可兼具彎折耐久性及形狀回復性。 撓性顯示器尤以具有可摺疊顯示畫面之結構的可摺式顯示器為佳。 實施例＜Flexible display＞ The flexible display of this embodiment includes the laminate of this embodiment. By containing the polymer A and the monomer B in the curable composition of the present embodiment, as shown in the following examples, the glass transition temperature of the cured product can be lowered, and the elastic modulus can be lowered. Therefore, even when used as an adhesive layer between members constituting a flexible display, it can still have both bending durability and shape recovery. The flexible display is particularly preferably a foldable display with a structure that can fold the display screen. Example
以下，以實施例來具體說明本發明，惟本發明不受該等實施例限定。Hereinafter, the present invention will be specifically described with examples, but the present invention is not limited by these examples.
＜測定方法・評估方法＞ [測定分子量] 質量平均分子量(Mw)及數量平均分子量(Mn)可在以下條件，藉由凝膠滲透層析術(GPC)測定，且分子量分布(Mw/Mn)可從Mw及Mn之測定值算出。 ・分析裝置：HLC-8120GPC 東曹公司製品名 ・管柱：使用依序將G7000HXL(東曹公司製品名)與GMHXL(東曹公司製品名)與GMHXL(東曹公司製品名)並列連接而成者。 ・管柱尺寸：各7.8mmφ×30cm，計90cm ・管柱溫度：40℃ ・流量：0.8mL/min ・注入量：100μL ・溶析液：四氫呋喃 ・檢測器：示差折射計(RI) ・標準試料：聚苯乙烯＜Measurement method and evaluation method＞ [Determination of molecular weight] The mass average molecular weight (Mw) and number average molecular weight (Mn) can be measured by gel permeation chromatography (GPC) under the following conditions, and the molecular weight distribution (Mw/Mn) can be calculated from the measured values of Mw and Mn. ・Analysis device: HLC-8120GPC Tosoh product name ・Pipe string: Use the one that connects G7000HXL (product name of Tosoh Corporation), GMHXL (product name of Tosoh Corporation) and GMHXL (product name of Tosoh Corporation) in order. ・Column size: 7.8mmφ×30cm each, 90cm in total ・Column temperature: 40℃ ・Flow rate: 0.8mL/min ・Injection volume: 100μL ・Eluent: Tetrahydrofuran ・Detector: Differential Refractometer (RI) ・Standard sample: Polystyrene
[測定聚合物A之玻璃轉移溫度] 針對各例中所得聚合物A，使用示差掃描熱量計(EXSTAR 6000 DSC 6200，Seiko Instruments Inc.製品名)，在試樣量約10mg、升溫速度10℃/分鐘、溫度範圍-80~25℃之條件下測定玻璃轉移溫度。[Measure the glass transition temperature of polymer A] For the polymer A obtained in each example, a differential scanning calorimeter (EXSTAR 6000 DSC 6200, product name of Seiko Instruments Inc.) was used, with a sample amount of about 10 mg, a heating rate of 10°C/min, and a temperature range of -80~25°C. Measure the glass transition temperature under conditions.
[測定硬化物之儲存彈性模數、玻璃轉移溫度] 將各例製得之硬化性組成物倒入寬5mm×長15mm×厚2mm之聚矽氧模具中，在氮環境下使用傳輸帶型UV照射機(ORC公司製)，在HgXe燈、照度100mW/cm2 、累積光量1J/cm2 之條件下使其硬化。以所得硬化物作為試驗試樣。 針對試驗試樣，使用動態黏彈性測定裝置(EXSTAR 6000 DMS 6100，Seiko Instruments Inc.製品名)，以拉伸模式且-80℃~130℃之溫度範圍下，在升溫速度3℃/min、測定頻率1Hz、應變1%之條件下測定儲存彈性模數E'(kPa)。並且，以測定所得tanδ顯示最大值之溫度(tanδ尖峰溫度)作為玻璃轉移溫度。 測定結果係於表中列出-20℃、25℃及80℃下之儲存彈性模數E'、Tg、以及儲存彈性模數比(E'(-20℃)/E'(80℃))，該儲存彈性模數比(E'(-20℃)/E'(80℃))表示-20℃下之E'相對於80℃下之E'的比值。[Measure the storage elastic modulus and glass transition temperature of the hardened material] Pour the hardened composition prepared in each example into a polysilicon mold of width 5mm×length 15mm×thickness 2mm, and use conveyor-type UV in a nitrogen environment The irradiation machine (manufactured by ORC) was cured under the conditions of a HgXe lamp, an illuminance of 100 mW/cm 2 and a cumulative light quantity of 1 J/cm 2 . The obtained hardened product was used as the test sample. For the test sample, a dynamic viscoelasticity measuring device (EXSTAR 6000 DMS 6100, Seiko Instruments Inc. product name) was used to measure the temperature in a temperature range of -80°C to 130°C in a tensile mode at a temperature increase rate of 3°C/min. Measure the storage elastic modulus E'(kPa) under the conditions of 1Hz frequency and 1% strain. In addition, the temperature at which the measured tanδ shows the maximum value (tanδ peak temperature) is used as the glass transition temperature. The measurement results are listed in the table for storage elastic modulus E', Tg, and storage elastic modulus ratio (E'(-20°C)/E'(80°C)) at -20℃, 25℃ and 80℃ , The storage elastic modulus ratio (E'(-20°C)/E'(80°C)) represents the ratio of E'at -20°C to E'at 80°C.
[積層體之彎折耐久性、形狀回復性的評估方法] 使用以下薄膜。 ・聚矽氧處理PET：已施行聚矽氧處理(剝離處理)之厚度75μm的聚對苯二甲酸乙二酯薄膜(SP-PET-01-75BU，Mitsui Chemicals Tohcello.Inc.製品名)。 ・Kapton薄膜：200EN，DU PONT-TORAY CO.,LTD.製品名，厚度50μm。 ・電暈處理PET：已對厚度50μm之聚對苯二甲酸乙二酯薄膜(Lumirror S10，TORAY Industries, Inc. 製品名)施行電暈處理加工者。[Evaluation method of bending durability and shape recovery of laminates] Use the following films. ・Polysiloxane-treated PET: 75μm-thick polyethylene terephthalate film (SP-PET-01-75BU, product name of Mitsui Chemicals Tohcello. Inc.) that has been treated with polysiloxane (peeling treatment). ・Kapton film: 200EN, product name of DU PONT-TORAY CO., LTD., thickness 50μm. ・Corona-treated PET: Those who have applied corona treatment to polyethylene terephthalate film (Lumirror S10, product name of TORAY Industries, Inc.) with a thickness of 50μm.
(反覆彎曲試驗) 使用安裝有刮刀之自動塗敷機(PI1210自動塗敷機，TESTER SANGYO CO,. LTD.製品名)，將各例之硬化性組成物以硬化後之黏著層厚度成為25μm的方式，塗佈於聚矽氧處理PET之聚矽氧處理面。接著，在氮環境下使用傳輸帶型UV照射機(ORC公司製)，在HgXe燈、照度100mW/cm2 、累積光量1J/cm2 之條件下使其硬化而形成黏著層。將黏著層側貼合至Kapton薄膜。接著，剝去聚矽氧處理PET後，於露出的黏著層貼合電暈處理PET之電暈處理面，而製造出試驗用積層體。試驗用積層體為寬50mm、長100mm、厚0.125mm。 使用U字型面狀彎曲試驗機(DLDM111LH，Yuasa System Co., Ltd.製品名)，將所得試驗用積層體在大約長度方向的一半位置彎折並重複此操作。具體上，是以撓曲半徑成為1.5mm且Kapton薄膜側位於內側的方式彎折成U字型，接著放開彎折之力，以此操作(放開成180°)為1次操作，在每分鐘60次的速度下反覆進行10萬次操作。以肉眼觀察試驗後之試驗用積層體的外觀，並按下述基準進行評估。 A：未產生白化、剝落、浮凸及裂痕任一情況，全無外觀上之變化。 B：雖產生白化、剝落、浮凸或裂痕中之1者以上，但程度輕微，無實用上的問題。 C：明顯產生白化、剝落、浮凸或裂痕中之1者以上，實用上有問題。(Repetitive bending test) Using an automatic coating machine (PI1210 automatic coating machine, TESTER SANGYO CO,. LTD. product name) equipped with a doctor blade, the curable composition of each example was cured to a thickness of 25μm. Method, coating on the silicone treated surface of silicone treated PET. Next, using a conveyor belt type UV irradiation machine (manufactured by ORC) in a nitrogen environment, it was cured under the conditions of an HgXe lamp, an illuminance of 100 mW/cm 2 , and a cumulative light quantity of 1 J/cm 2 to form an adhesive layer. Attach the adhesive layer side to the Kapton film. Next, after peeling off the silicone-treated PET, the corona-treated surface of the corona-treated PET was attached to the exposed adhesive layer to produce a laminate for testing. The laminate for the test has a width of 50 mm, a length of 100 mm, and a thickness of 0.125 mm. Using a U-shaped surface bending tester (DLDM111LH, product name of Yuasa System Co., Ltd.), bend the obtained test laminate at approximately half of the length direction and repeat this operation. Specifically, the bending radius is 1.5mm and the Kapton film side is on the inside to bend into a U-shape, and then the bending force is released, and this operation (release to 180°) is one operation. 100,000 operations are repeated at a speed of 60 times per minute. The appearance of the test laminate after the test was visually observed, and the evaluation was made according to the following criteria. A: There is no whitening, peeling, embossing or cracking, and there is no change in appearance. B: Although more than one of whitening, peeling, embossing, or cracking occurs, the degree is slight and there is no practical problem. C: One or more of whitening, peeling, embossing, or cracks are clearly generated, and there is a practical problem.
(靜態彎曲試驗) 使用以與反覆彎曲試驗同樣方式作成的試驗用積層體作為靜態彎曲試驗用試樣。試驗用積層體為寬50mm、長100mm、厚0.125mm。沿著端面經加工成曲面(撓曲半徑1.5mm)之厚度3mm之板的外形，使靜態彎曲試驗用試樣以Kapton薄膜側為內側的方式密著並以膠帶固定。在-20℃或室溫(25℃)之條件下靜置20日後，以肉眼觀察試驗後之試驗用積層體的外觀，並以與反覆彎曲試驗同樣基準進行評估。(Static bending test) A test laminate prepared in the same manner as the repeated bending test was used as the static bending test sample. The laminate for the test has a width of 50 mm, a length of 100 mm, and a thickness of 0.125 mm. The shape of a 3mm thick plate is processed along the end surface into a curved surface (flexion radius of 1.5mm), and the static bending test specimen is adhered with the Kapton film side as the inside and fixed with tape. After standing at -20°C or room temperature (25°C) for 20 days, the appearance of the test laminate after the test was observed with the naked eye, and evaluated on the same basis as the repeated bending test.
(捲曲試驗、捲曲殘存率) 將以與反覆彎曲試驗同樣方式作成的試驗用積層體裁切成寬10mm、長50mm，作為捲曲試驗用試樣。沿著端面經加工成曲面(撓曲半徑2mm)之厚度4mm之板的外形，將捲曲試驗用試樣之長度方向之中心位置彎折並以膠帶固定後，在室溫下放置1日。接著，從板去除捲曲試驗用試樣，以彎折之面朝上並形成倒U字型的方式放置於水平面上，測定從水平面至彎折面之間的高度h(mm)。藉由下述式算出捲曲殘存率(單位：%)。捲曲殘存率愈低，形狀回復性愈佳。另，於試驗中產生剝落者表記為F。 捲曲殘存率(%)={h/25}×100(Curl test, residual rate of curl) The test laminate made in the same manner as the repeated bending test was cut into a width of 10 mm and a length of 50 mm, and used as a sample for the curl test. The shape of a plate with a thickness of 4mm, which is processed into a curved surface (flexion radius of 2mm) along the end surface, is bent at the center of the longitudinal direction of the crimp test sample and fixed with tape, and then it is left at room temperature for 1 day. Next, remove the sample for the curl test from the plate, place it on a horizontal surface with the bent surface facing up and forming an inverted U shape, and measure the height h (mm) from the horizontal surface to the bent surface. The curl remaining rate (unit: %) was calculated by the following formula. The lower the residual rate of curl, the better the shape recovery. In addition, those who peeled off during the test were marked as F. Survival rate of curl (%)={h/25}×100
(潛變回復率)
按與反覆彎曲試驗同樣程序製作圖1A中所示潛變試驗用試樣。圖中符號1為Kapton薄膜，2為黏著層，3為電暈處理PET。在剪切方向(X方向)上，Kapton薄膜1及電暈處理PET3的長度分別設為60mm，從Kapton薄膜1之端部1a起至電暈處理PET3之端部3a為止的長度(以下稱為X方向全長)之初始值設為110mm。黏著層2之厚度設為25μm。在與X方向及厚度方向兩者垂直之方向上，Kapton薄膜1及電暈處理PET3的寬度分別設為10mm。
將Kapton薄膜1之端部1a與電暈處理PET3之端部3a分別固定於拉伸試驗機，並沿X方向伸長至X方向全長比初始值長300μm後，放開伸長之力並以此操作為1次，反覆進行10次操作後，靜置1分鐘。圖1B是靜置後之潛變試驗用試樣之例。以光學顯微鏡(顯微鏡VHX‐1000，KEYENCE公司製品名)觀察靜置後之殘留應變量，並測定自初始位置偏移之偏移幅度(圖1B中之符號4)。藉由下述式算出潛變回復率(單位：%)。潛變回復率愈高，形狀回復性愈佳。
潛變回復率(%)={(300μm-自初始位置偏移之偏移幅度(μm))/300μm}×100(Creep recovery rate)
The sample for creep test shown in Figure 1A was made according to the same procedure as the repeated bending test. In the figure, symbol 1 is Kapton film, 2 is adhesive layer, and 3 is corona treated PET. In the shear direction (X direction), the lengths of the Kapton film 1 and the corona treated PET3 are each set to 60mm, and the length from the
[製造例1-1] 於具備攪拌機及氮導入管之耐壓反應器內加入六氰鈷酸鋅-第三丁基醇錯合物(以下稱為「DMC-TBA」)0.2g及正丁醇30g，在設為130℃之氮氣環境下，在恆定速度下耗時7小時投入環氧丙烷(以下稱為PO)3970g。接著，確認耐壓反應器之內壓停止下降後，取出產物而獲得羥值5.6mgKOH/g(羥基換算分子量：10,000)之聚氧伸烷基單元醇(單元醇1)4000g。[Manufacturing Example 1-1] Add 0.2 g of zinc hexacyanocobaltate-tertiary butyl alcohol complex (hereinafter referred to as "DMC-TBA") and 30 g of n-butanol into a pressure-resistant reactor equipped with a stirrer and a nitrogen introduction tube, and set it to 130 In a nitrogen atmosphere at ℃, 3970 g of propylene oxide (hereinafter referred to as PO) was added at a constant speed for 7 hours. Then, after confirming that the internal pressure of the pressure-resistant reactor stopped falling, the product was taken out to obtain 4000 g of polyoxyalkylene monool (monool 1) having a hydroxyl value of 5.6 mgKOH/g (hydroxyl conversion molecular weight: 10,000).
[製造例1-2] 除了令正丁醇為59g、PO為3941g以外，以與製造例1-1同樣方式，獲得羥值11.5mgKOH/g(羥基換算分子量：4,880)之聚氧伸烷基單元醇(單元醇2)4000g。[Manufacturing Example 1-2] Except that the n-butanol was 59 g and the PO was 3941 g, in the same manner as in Production Example 1-1, a polyoxyalkylene monool (monool 2) with a hydroxyl value of 11.5 mgKOH/g (hydroxyl conversion molecular weight: 4,880) was obtained 4000g.
[製造例1-3] 除了令正丁醇為21g、PO為3979g以外，以與製造例1-1同樣方式，獲得羥值4.1mgKOH/g(羥基換算分子量：13,680)之聚氧伸烷基單元醇(單元醇3)4000g。[Manufacturing Example 1-3] Except that n-butanol was 21 g and PO was 3979 g, in the same manner as in Production Example 1-1, a polyoxyalkylene monohydric alcohol (monohydric alcohol 3) having a hydroxyl value of 4.1 mgKOH/g (hydroxyl conversion molecular weight: 13,680) was obtained 4000g.
[製造例1-4] 於具備攪拌機及氮導入管之壓反應器內加入DMC-TBA 0.5g及正丁醇74g，在設為130℃之氮氣環境下，在恆定速度下耗時15小時投入PO 7941g與環氧乙烷(以下稱為EO)1985g之混合液。接著，確認耐壓反應器之內壓停止下降後，取出產物而獲得羥值5.2mgKOH/g(羥基換算分子量：10,790)之聚氧伸烷基單元醇(單元醇4)10000g。在單元醇4中，PO相對於PO與EO之合計的含量約75莫耳%。[Manufacturing Example 1-4] Add 0.5 g of DMC-TBA and 74 g of n-butanol into a pressure reactor equipped with a stirrer and a nitrogen introduction tube. Under a nitrogen environment set to 130°C, 7941 g of PO and ethylene oxide are added at a constant speed for 15 hours (Hereinafter referred to as EO) 1985g of mixed liquid. Then, after confirming that the internal pressure of the pressure-resistant reactor stopped falling, the product was taken out to obtain 10000 g of polyoxyalkylene monool (monool 4) having a hydroxyl value of 5.2 mgKOH/g (hydroxyl conversion molecular weight: 10,790). In unit alcohol 4, the content of PO relative to the total of PO and EO is about 75 mol%.
[製造例1-5] 除了令DMC-TBA為0.25g、PO為3743g、EO為1182g以外，以與製造例1-4同樣方式獲得羥值11.8mgKOH/g(羥基換算分子量：4,750)之聚氧伸烷基單元醇(單元醇5)5000g。在單元醇5中，PO相對於PO與EO之合計的含量約71莫耳%。[Manufacturing Example 1-5] Except that DMC-TBA was 0.25 g, PO was 3743 g, and EO was 1182 g, in the same manner as in Production Example 1-4, a polyoxyalkylene monool (hydroxyl value 11.8 mgKOH/g (hydroxyl conversion molecular weight: 4,750)) was obtained. Unit alcohol 5) 5000g. In unit alcohol 5, the content of PO relative to the total of PO and EO is about 71 mol%.
[製造例2-1] 於具備攪拌機及氮導入管之反應容器內添加單元醇1(平均羥基數：1.08)964.9g、及2-丙烯醯氧基乙基異氰酸酯(Karenz-AOI，昭和電工公司產品名。以下稱為AOI)13.1g，在2-乙基己酸鉍25%甲苯溶液0.08g之存在下，在70℃下攪拌3小時而獲得包含單體B1之產物。AOI之NCO基相對於單元醇1之OH基之比率(指數)為100。產物中之單體B1含量為84質量%。 將所得單體B1之Mn、Mw/Mn、平均官能基數、胺甲酸乙酯鍵之含量、玻璃轉移溫度(Tg)列於表中(以下相同)。[Manufacturing Example 2-1] Add 964.9 g of unit alcohol 1 (average number of hydroxyl groups: 1.08) and 2-acryloyloxyethyl isocyanate (Karenz-AOI, the product name of Showa Denko Co., Ltd.) into a reaction vessel equipped with a stirrer and a nitrogen introduction tube. Hereinafter referred to as AOI ) 13.1 g, in the presence of 0.08 g of bismuth 2-ethylhexanoate 25% toluene solution, stirred at 70° C. for 3 hours to obtain a product containing monomer B1. The ratio (index) of the NCO group of AOI to the OH group of the unit alcohol 1 is 100. The content of monomer B1 in the product was 84% by mass. The Mn, Mw/Mn, average number of functional groups, urethane bond content, and glass transition temperature (Tg) of the obtained monomer B1 are listed in the table (the same below).
[製造例2-2] 在製造例2-1中，除了使用單元醇2(平均羥基數：1.04)928.1g替代單元醇1，並將AOI設為26.8g以外，以同樣方式獲得包含單體B2之產物。產物中之單體B2含量為92質量%。[Manufacturing Example 2-2] In Production Example 2-1, except that 928.1 g of the unit alcohol 2 (average number of hydroxyl groups: 1.04) was used instead of the unit alcohol 1, and the AOI was set to 26.8 g, a product containing the monomer B2 was obtained in the same manner. The content of monomer B2 in the product was 92% by mass.
[製造例2-3] 在製造例2-1中，除了使用單元醇3(平均羥基數：1.11)928.1g替代單元醇1，並將AOI設為8.6g以外，以同樣方式獲得包含單體B3之產物。產物中之單體B3含量為80質量%。[Manufacturing Example 2-3] In Production Example 2-1, except that 928.1 g of the unit alcohol 3 (average number of hydroxyl groups: 1.11) was used instead of the unit alcohol 1, and the AOI was set to 8.6 g, a product containing the monomer B3 was obtained in the same manner. The content of monomer B3 in the product is 80% by mass.
[製造例2-4] 在製造例2-1中，除了使用單元醇4(平均羥基數：1.11)500.2g替代單元醇1，並將AOI設為6.6g以外，以同樣方式獲得包含單體B4之產物。產物中之單體B4含量為96質量%。[Manufacturing Example 2-4] In Production Example 2-1, except that 500.2 g of monoalcohol 4 (average number of hydroxyl groups: 1.11) was used instead of monoalcohol 1, and the AOI was set to 6.6 g, a product containing monomer B4 was obtained in the same manner. The content of monomer B4 in the product was 96% by mass.
[製造例2-5] 在製造例2-1中，除了使用單元醇5(平均羥基數：1.11)501.0g替代單元醇1，並將AOI設為14.9g以外，以同樣方式獲得包含單體B5之產物。產物中之單體B5含量為89質量%。[Manufacturing Example 2-5] In Production Example 2-1, a product containing monomer B5 was obtained in the same manner except that 501.0 g of unit alcohol 5 (average number of hydroxyl groups: 1.11) was used instead of unit alcohol 1, and the AOI was set to 14.9 g. The content of monomer B5 in the product was 89% by mass.
[製造例3-1] 於具備攪拌機及氮導入管之反應容器內加入乙酸乙酯200g，並保持在70℃。接著，將丙烯酸丁酯(以下稱BA)156.8g、丙烯酸(以下稱AA)4.0g、丙烯酸2-乙基己酯(以下稱2-EHA)39.2g及2,2'-偶氮雙(2,4-二甲基戊腈)(以下稱V-65)0.2g之混合液，在恆定速度下耗費2小時滴下至維持在70±2℃之反應容器內。滴下結束後，在70℃±2下保持2小時，然後在130℃下減壓脫氣2小時，去除乙酸乙酯及未反應單體而獲得聚合物A1。 將所得之聚合物A1之Mw、Mn、Mw/Mn、玻璃轉移溫度(Tg)列於表中(以下相同)。[Manufacturing Example 3-1] Add 200 g of ethyl acetate into a reaction vessel equipped with a stirrer and a nitrogen introduction tube, and keep it at 70°C. Next, 156.8 g of butyl acrylate (hereinafter referred to as BA), 4.0 g of acrylic acid (hereinafter referred to as AA), 39.2 g of 2-ethylhexyl acrylate (hereinafter referred to as 2-EHA), and 2,2'-azobis(2 , 4-Dimethylvaleronitrile) (hereinafter referred to as V-65) 0.2g of the mixed solution, it takes 2 hours to drop at a constant speed to the reaction vessel maintained at 70±2°C. After the dripping was completed, it was kept at 70°C±2 for 2 hours, and then degassed under reduced pressure at 130°C for 2 hours to remove ethyl acetate and unreacted monomers to obtain polymer A1. The Mw, Mn, Mw/Mn, and glass transition temperature (Tg) of the obtained polymer A1 are listed in the table (the same applies below).
[製造例3-2] 於具備攪拌機及氮導入管之反應容器內加入乙酸乙酯100g，並保持在70℃。接著，將2-EHA 196.0g、AA 4.0g及V-65 0.2g之混合液在恆定速度下耗費2小時滴下至保持在70±2℃之反應容器內。滴下結束後，在70±2℃下保持2小時，然後在130℃下減壓脫氣2小時，去除乙酸乙酯及未反應單體而獲得聚合物A2。[Manufacturing Example 3-2] Add 100 g of ethyl acetate into a reaction vessel equipped with a stirrer and a nitrogen introduction tube, and keep it at 70°C. Next, a mixture of 196.0 g of 2-EHA, 4.0 g of AA, and 0.2 g of V-65 was dropped at a constant speed for 2 hours into a reaction vessel kept at 70±2°C. After completion of the dropping, it was kept at 70±2°C for 2 hours, and then degassed under reduced pressure at 130°C for 2 hours to remove ethyl acetate and unreacted monomers to obtain polymer A2.
[製造例3-3] 於具備攪拌機及氮導入管之反應容器內加入乙酸乙酯100g，並保持在70℃。接著，將BA 184.0g、丙烯酸4-羥丁酯(以下稱4-HBA)16.0g及V-65 0.1g之混合液在恆定速度下耗費2小時滴下至保持在70±2℃之反應容器內。滴下結束後，在70±2℃下保持2小時，然後在130℃下減壓脫氣2小時，去除乙酸乙酯及未反應單體而獲得聚合物A3。[Manufacturing Example 3-3] Add 100 g of ethyl acetate into a reaction vessel equipped with a stirrer and a nitrogen introduction tube, and keep it at 70°C. Next, a mixture of 184.0 g of BA, 16.0 g of 4-hydroxybutyl acrylate (hereinafter referred to as 4-HBA), and 0.1 g of V-65 was dropped at a constant speed for 2 hours to a reaction vessel kept at 70±2°C . After completion of the dropping, it was kept at 70±2°C for 2 hours, and then degassed under reduced pressure at 130°C for 2 hours to remove ethyl acetate and unreacted monomers to obtain polymer A3.
[製造例3-4] 於具備攪拌機及氮導入管之反應容器內加入乙酸乙酯100g，並保持在70℃。接著，將BA 92.0g、2-EHA 92.0g、4-HBA 16.0g及V-65 0.1g之混合液在恆定速度下耗費2小時滴下至保持在70±2℃之反應容器內。滴下結束後，在70±2℃下保持2小時，然後在130℃下減壓脫氣2小時，去除乙酸乙酯及未反應單體而獲得聚合物A4。[Manufacturing Example 3-4] Add 100 g of ethyl acetate into a reaction vessel equipped with a stirrer and a nitrogen introduction tube, and keep it at 70°C. Next, a mixture of BA 92.0 g, 2-EHA 92.0 g, 4-HBA 16.0 g, and V-65 0.1 g was dropped at a constant speed over 2 hours until it was kept in a reaction vessel kept at 70±2°C. After completion of the dropping, it was kept at 70±2°C for 2 hours, and then degassed under reduced pressure at 130°C for 2 hours to remove ethyl acetate and unreacted monomers to obtain polymer A4.
[表1]
[表2]
[例1~21]
例1~14及21為實施例，例15~20為比較例。
以表3、4中所示摻混(單位：質量份)，使用行星式攪拌機(EMC公司製)將全部成分混合，製造出硬化性組成物。表中之交聯劑1為1,9-壬二醇二丙烯酸酯，交聯劑2為三羥甲丙烷三丙烯酸酯，光聚合引發劑1為4‐甲基二苯基酮。
以上述測定方法及評估方法針對表中所示項目進行測定或評估。茲將結果列於表中。[Example 1~21]
Examples 1-14 and 21 are examples, and examples 15-20 are comparative examples.
With the blending shown in Tables 3 and 4 (unit: parts by mass), all the components were mixed using a planetary mixer (manufactured by EMC Corporation) to produce a curable composition. In the table, crosslinking agent 1 is 1,9-nonanediol diacrylate,
[表3]
[表4]
如表3、4之結果所示，包含聚合物A與單體B之例1~例14，其硬化物之玻璃轉移溫度低，彈性模數低，且積層體之彎折耐久性及形狀回復性兩者皆佳。例21之硬化物的玻璃轉移溫度低，且積層體之彎折耐久性及形狀回復性兩者皆佳。As shown in the results in Tables 3 and 4, Examples 1 to 14 containing polymer A and monomer B have a low glass transition temperature, a low elastic modulus, and the bending durability and shape recovery of the laminate Both sex are good. The glass transition temperature of the cured product of Example 21 was low, and the bending durability and shape recovery of the laminate were excellent.
另，在此係援用已於2019年2月5日提申之日本專利申請案2019-18959號之說明書、申請專利範圍、摘要及圖式之全部內容並納入作為本發明說明書之揭示。In addition, the entire contents of the specification, application scope, abstract and drawings of Japanese Patent Application No. 2019-18959 filed on February 5, 2019 are cited here and incorporated as the disclosure of the specification of the present invention.
1:Kapton薄膜
1a:Kapton薄膜之端部
2:黏著層
3:電暈處理PET
3a:電暈處理PET之端部
4:自初始值偏移之偏移幅度
X:剪切方向1:
圖1A係用以說明潛變回復率之測定方法的示意圖，為拉伸試驗前之試樣一例的前視圖。 圖1B係用以說明潛變回復率之測定方法的示意圖，為拉伸試驗後之試樣一例的前視圖。Figure 1A is a schematic diagram for explaining the method of measuring creep recovery rate, and is a front view of an example of a sample before a tensile test. Figure 1B is a schematic diagram for explaining the method of measuring creep recovery rate, and is a front view of an example of a sample after a tensile test.
(無)(no)
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