TW201811967A - Ultraviolet curable adhesive, cured products, adhesive sheets having low-temperature softness and high-temperature retentivity - Google Patents
Ultraviolet curable adhesive, cured products, adhesive sheets having low-temperature softness and high-temperature retentivity Download PDFInfo
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- TW201811967A TW201811967A TW106130342A TW106130342A TW201811967A TW 201811967 A TW201811967 A TW 201811967A TW 106130342 A TW106130342 A TW 106130342A TW 106130342 A TW106130342 A TW 106130342A TW 201811967 A TW201811967 A TW 201811967A
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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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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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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- 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
- C09J7/22—Plastics; Metallised plastics
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
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- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
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Abstract
Description
本發明，係關於紫外線硬化型黏著劑及其硬化物、以及將該硬化物作為黏著層之黏著片材。 The present invention relates to an ultraviolet-curable adhesive, a cured product thereof, and an adhesive sheet using the cured product as an adhesive layer.
近年來，行動電話、攜帶式遊戲機、汽車導航等之數位資訊機器係使用觸控面板等之顯示裝置。此外，相關之顯示裝置係廣泛使用液晶元件或發光二極體元件、有機電致發光元件等之光學部材。 In recent years, digital information equipment such as a mobile phone, a portable game machine, and a car navigation system are display devices using a touch panel or the like. In addition, related display devices are widely used optical components such as liquid crystal elements, light-emitting diode elements, and organic electroluminescent elements.
在顯示裝置之製造時，為了達到將顯示裝置與前述光學部材，或將光學部材彼此貼合之目的，係使用透明之兩面黏著片材。相關之兩面黏著片材，被要求具透明性或耐候性、金屬腐蝕防止性等之性能。 In the manufacture of a display device, in order to achieve the purpose of bonding the display device and the aforementioned optical members, or bonding the optical members to each other, a transparent two-sided adhesive sheet is used. The related two-sided adhesive sheet is required to have properties such as transparency or weather resistance, and metal corrosion prevention.
此外，觸控面板之中，為了提升設計性，會於框架部施予裝飾印刷。由於裝飾印刷，在印刷部與非印刷部之間會產生段差，兩面黏著片材之黏著層，被要求具填補相關印刷段差之順應性(以下，稱為段差吸收性)。若段差吸收性不足，則段差附近之黏著劑層會產生浮起，而有因此而發生光的反射損失之虞。 In addition, in the touch panel, in order to improve the design, decorative printing is applied to the frame portion. Due to the decorative printing, a step difference will occur between the printed portion and the non-printed portion, and the adhesive layer on both sides of the adhesive sheet is required to have compliance (hereinafter, referred to as step difference absorption) to fill the related printing step difference. If the step absorptivity is insufficient, the adhesive layer in the vicinity of the step difference may float, and there is a possibility that a reflection loss of light may occur.
具備段差吸收性之黏著片材，作為其之黏著層，已有提案使用含有非交聯性(甲基)丙烯酸酯單位與交聯性丙烯酸單體單位所成基礎 聚合物之活性能量射線硬化性及熱硬化性之黏著劑(參照專利文獻1)。然而此黏著劑，為了解決厚壁端部軟化之製造上的問題而設計為含有多量溶劑，故必須在製作黏著片材時進行去除溶劑之步驟，生產效率較低。 Adhesive sheets having step-absorptivity have been proposed as the adhesive layer using active energy ray-hardening properties of a base polymer containing non-crosslinkable (meth) acrylate units and crosslinkable acrylic monomer units. And thermosetting adhesive (see Patent Document 1). However, this adhesive is designed to contain a large amount of solvent in order to solve the problem of softening of the thick-walled end. Therefore, the solvent removal step must be performed when making the adhesive sheet, and the production efficiency is low.
另一方面，近年來，觸控面板開始重視設計性，由傳統之平板形狀至曲面形狀的要求提升。進一步薄膜形狀之觸控面板亦被探討研究，藉由使用柔性有機EL顯示器使顯示裝置可折疊或捲繞。 On the other hand, in recent years, touch panels have begun to pay attention to design, and the requirements from a traditional flat plate shape to a curved shape have increased. Further film-shaped touch panels have also been investigated, and display devices can be folded or rolled by using flexible organic EL displays.
曲面形狀或薄膜形狀之觸控面板所使用之黏著片材，其黏著層被要求具有高柔軟性，特別係，必須具備因溫度變化所致柔軟性(儲能模量)的變化較少之特性。黏著層之柔軟性不足時，貼合之基材會剝離，有因此而發生視認性及耐久性降低之虞。 Adhesive sheets for curved or film-shaped touch panels are required to have a high degree of flexibility in the adhesive layer. In particular, they must have the characteristics of less change in flexibility (storage modulus) due to temperature changes. . When the flexibility of the adhesive layer is insufficient, the bonded substrate may peel off, which may cause deterioration in visibility and durability.
著重於黏著層之儲能模量的接著片材可列舉如專利文獻2。該接著片材係具有所定之活性能量射線硬化型熱可塑性聚胺酯層(A)、及其他之聚胺酯層(B)之二層構造的物品，藉由相互補足地設定層(A)之儲能模量與層(B)之儲能模量，從而可確保段差吸收性。然而，由於層(A)所賦予之黏著劑及層(B)所有者任一者皆含有多量之溶劑，在製作接著片材時，必須進行去除溶劑之步驟。此外，必須進行將層(A)所具備之片材及層(B)所具備之片材的二枚接著片材貼合之步驟，故生產效率亦較低。 An adhesive sheet focusing on the storage modulus of the adhesive layer can be exemplified by Patent Document 2. The adhesive sheet is an article having a two-layer structure of a predetermined active energy ray-curable thermoplastic polyurethane layer (A) and other polyurethane layers (B). The storage mode of the layer (A) is set to complement each other. And the storage modulus of layer (B), so as to ensure the step absorbency. However, since both the adhesive provided by the layer (A) and the owner of the layer (B) contain a large amount of a solvent, it is necessary to perform a step of removing the solvent when producing an adhesive sheet. In addition, a step of laminating two sheets of the sheet provided in the layer (A) and two sheets of the sheet provided in the layer (B) must be performed, so the production efficiency is also low.
提升段差順應性及柔軟性之黏著劑，已提案有一種熱硬化性之紫外線硬化型黏著劑，其包含：含有甲基丙烯酸酯單體之基礎聚合物及可塑劑(參照專利文獻3)。然而，由於其係使用低軟化點之可塑劑，故有在高溫時保持力低下之虞。此外，由於該紫外線硬化型黏著劑含有多量之 溶劑，故在製作黏著片材時，必須進行去除溶劑之步驟。 As a pressure-sensitive adhesive for improving step compliance and softness, a thermosetting UV-curable adhesive has been proposed, which includes a base polymer containing a methacrylate monomer and a plasticizer (see Patent Document 3). However, since it uses a plasticizer with a low softening point, there is a concern that the holding force is low at high temperatures. In addition, since this ultraviolet-curable adhesive contains a large amount of a solvent, it is necessary to perform a step of removing the solvent when producing an adhesive sheet.
【專利文獻1】國際公開WO2013/061938號公報 [Patent Document 1] International Publication No. WO2013 / 061938
【專利文獻2】日本特開2016-74750號公報 [Patent Document 2] Japanese Patent Laid-Open No. 2016-74750
【專利文獻3】日本特開2015-105329號公報 [Patent Document 3] Japanese Patent Laid-Open No. 2015-105329
本發明之課題，主要係提供一種黏著劑之課題，其係實質性無溶劑類型之透明紫外線硬化型黏著劑，可形成即使為單一層仍可兼具低溫柔軟性及高溫保持力，且亦可奏效優異之段差順應性之黏著層。 The problem of the present invention is mainly the problem of providing an adhesive, which is a substantially solvent-free transparent UV-curable adhesive, which can be formed to have both low-temperature flexibility and high-temperature retention even if it is a single layer. Excellent adhesion layer with poor compliance.
經本發明者深入研究之結果，發現藉由滿足特定條件之紫外線硬化型接著劑組成物可解決前述課題，從而完成本發明。亦即本發明，係關於以下之紫外線硬化型黏著劑及硬化物。 As a result of intensive research by the present inventors, it was found that the aforementioned problems can be solved by an ultraviolet curing adhesive composition that satisfies a specific condition, thereby completing the present invention. That is, this invention relates to the following ultraviolet curable adhesives and hardened | cured material.
1．一種紫外線硬化型黏著劑，其特徵係含有：(A)(a1)聚醚多元醇、(a2)聚異氰酸酯、以及(a3)含羥基單(甲基)丙烯酸酯或含異氰酸酯基單(甲基)丙烯酸酯之反應物的聚胺酯(甲基)丙烯酸 酯；(B)不含羥基聚合單體，均聚物時之玻璃轉化溫度係-70℃以上0℃未達；(C)不含羥基聚合單體，均聚物時之玻璃轉化溫度係0℃以上150℃未達；(D)一級含羥基單(甲基)丙烯酸酯；及(E)光聚合引發劑，並且，(A)成分、(B)成分、(C)成分及(D)成分之合計為100質量%時，各使用比率依序係10~50質量%、10~70質量%、0~10質量%、及20~79．9質量%，並且，(E)成分之使用比率，相對於(A)成分、(B)成分、(C)成分及(D)成分之合計質量，係0．1~5質量%，並且，溶劑含有量係1質量%未達，並且，加德納色度係1以下。 1. A UV-curable adhesive, characterized in that it contains (A) (a1) polyether polyol, (a2) polyisocyanate, and (a3) hydroxyl-containing mono (meth) acrylate or isocyanate-containing mono (methyl) ) Polyurethane (meth) acrylates of acrylate reactants; (B) does not contain hydroxyl polymerizable monomers, and the glass transition temperature for homopolymers is not higher than -70 ° C and 0 ° C; (C) does not contain hydroxyl polymerization The glass transition temperature of monomers and homopolymers is not higher than 0 ° C and lower than 150 ° C; (D) the first-stage hydroxyl-containing mono (meth) acrylate; and (E) the photopolymerization initiator, and (A) the component, When the total of (B) component, (C) component and (D) component is 100% by mass, each use ratio is 10 to 50% by mass, 10 to 70% by mass, 0 to 10% by mass, and 20 to 79 .9% by mass, and the usage ratio of the (E) component is 0.1 to 5% by mass relative to the total mass of the (A) component, (B) component, (C) component, and (D) component, and The solvent content is less than 1% by mass, and the Gardner chromaticity is 1 or less.
2．如前述項1之紫外線硬化型黏著劑，其中，(a1)成分係包含聚丙二醇。 2. The ultraviolet-curable adhesive according to the aforementioned item 1, wherein the component (a1) contains polypropylene glycol.
3．如前述項1或2之紫外線硬化型黏著劑，其中，(a1)成分之數平均分子量係700~10000。 3． The ultraviolet curable adhesive according to the aforementioned item 1 or 2, wherein the number average molecular weight of the component (a1) is 700 to 10,000.
4．如前述項1~3中任一項之紫外線硬化型黏著劑，其中，(a2)成分係脂肪族雙異氰酸酯及/或脂環族雙異氰酸酯。 4． The ultraviolet-curable adhesive according to any one of the aforementioned items 1 to 3, wherein the component (a2) is an aliphatic diisocyanate and / or an alicyclic diisocyanate.
5．如前述項1~4中任一項之紫外線硬化型黏著劑，其中，含羥基單(甲基)丙烯酸酯係全碳數5~10之含羥基單(甲基)丙烯酸酯。 5． The ultraviolet curable adhesive according to any one of the foregoing items 1 to 4, wherein the hydroxyl-containing mono (meth) acrylate is a hydroxyl-containing mono (meth) acrylate having a total carbon number of 5 to 10.
6．如前述項1~5中任一項之紫外線硬化型黏著劑，其中，含異氰酸酯基單(甲基)丙烯酸酯係包含2-異氰酸乙基(甲基)丙烯酸酯及/或1，1-二(丙烯醯氧基甲基)乙基異氰酸酯。 6. The ultraviolet-curable adhesive according to any one of the foregoing items 1 to 5, wherein the isocyanate group-containing mono (meth) acrylate system includes 2-isocyanate ethyl (meth) acrylate and / or 1,1 -Bis (propenyloxymethyl) ethyl isocyanate.
7．如前述項1~6中任一項之紫外線硬化型黏著劑，其中，(A)成分之(甲基)丙烯醯基之平均個數係1．5~4。 7. The ultraviolet-curable adhesive according to any one of the aforementioned items 1 to 6, wherein the average number of (meth) acrylfluorenyl groups of the component (A) is 1.5 to 4.
8．如前述項1~7中任一項之紫外線硬化型黏著劑，其中，(A)成分之重量平均分子量係10，000~90，000。 8. The ultraviolet-curable adhesive according to any one of the aforementioned items 1 to 7, wherein the weight average molecular weight of the component (A) is 10,000 to 90,000.
9．如前述項1~8中任一項之紫外線硬化型黏著劑，其中，(B)成分，係包含烷基之碳數為4~18之烷基單(甲基)丙烯酸酯。 9. The ultraviolet-curable adhesive according to any one of the foregoing items 1 to 8, wherein the component (B) is an alkyl mono (meth) acrylate having an alkyl group having 4 to 18 carbon atoms.
10．如前述項1~9中任一項之紫外線硬化型黏著劑，其中，(C)成分，係包含脂環族單(甲基)丙烯酸酯。 10． The ultraviolet-curable adhesive according to any one of the aforementioned items 1 to 9, wherein the component (C) contains an alicyclic mono (meth) acrylate.
11．如前述項1~10中任一項之紫外線硬化型黏著劑，其中，(D)成分，係包含2-羥基乙基(甲基)丙烯酸酯及/或4-羥基丁基(甲基)丙烯酸酯。 11. The ultraviolet-curable adhesive according to any one of the aforementioned items 1 to 10, wherein the component (D) contains 2-hydroxyethyl (meth) acrylate and / or 4-hydroxybutyl (meth) acrylate ester.
12．如前述項1~11中任一項之紫外線硬化型黏著劑，其中，係進一步包含(F)可塑劑，其相對於(A)成分、(B)成分、(C)成分及(D)成分之合計質量，係0~10質量%。 12. The ultraviolet-curable adhesive according to any one of the aforementioned items 1 to 11, further comprising (F) a plasticizer, which is more than (A) component, (B) component, (C) component, and (D) component The total mass is 0 to 10% by mass.
13．一種硬化物，其特徵係由前述項1~12中任一項之紫外線硬化型黏著劑所成。 13. A hardened product characterized by being formed from the ultraviolet-curable adhesive according to any one of the items 1 to 12 above.
14．如前述項13之硬化物，其中，-20℃及1Hz中儲能模量G’係1×106Pa以下，並且，100℃及1Hz中儲能模量G’係1×104Pa以上。 14. The hardened product according to the aforementioned item 13, wherein the storage modulus G 'at -20 ° C and 1 Hz is 1 × 10 6 Pa or less, and the storage modulus G ′ at 100 ° C and 1 Hz is 1 × 10 4 Pa or more .
15．一種黏著片材，其特徵係於塑料薄膜之至少單面上具有前述項13或14之硬化物。 15. An adhesive sheet characterized by having a hardened product of the aforementioned item 13 or 14 on at least one side of a plastic film.
由於本發明之紫外線硬化型黏著劑係透明，且實質性無溶劑，故可省略在製作黏著片材時之去除溶劑步驟。此外，該組成物所成黏著層(硬化物)即使係單一層，仍可兼具低溫時之黏著力(低溫柔軟性)及高溫時之黏著力(高溫保持力)，且奏效優異之段差順應性。此外，該黏著層係無色透明，再剝離性亦良好，加熱處理後之耐久性及保持力亦優異。 Since the ultraviolet-curable adhesive of the present invention is transparent and substantially solvent-free, the step of removing the solvent when making an adhesive sheet can be omitted. In addition, even if the adhesive layer (hardened material) formed by the composition is a single layer, it can still have both low-temperature adhesion (low-temperature flexibility) and high-temperature adhesion (high-temperature retention). Sex. In addition, the adhesive layer is colorless and transparent, has good re-peelability, and has excellent durability and retention after heat treatment.
本發明之紫外線硬化型黏著劑係適宜地用在光學用途上。例如，可適用於數位顯示裝置中多層構造之顯示面板。此外，由於如前述在低溫~高溫之範圍中黏著力皆優異，且段差順應性亦良好，故例如適用於觸控面板用之兩面黏著片材時，即使在該面板上貼合裝飾板或圖標片材，抑或將静電容量方式觸控面板中形成透明電極之透明基板及透明板貼合時，氣泡難以產生。此外，適用於柔性有機EL顯示器時，該柔性有機EL可折疊或輥狀的捲曲。 The ultraviolet-curable adhesive of the present invention is suitably used for optical applications. For example, the present invention is applicable to a display panel having a multilayer structure in a digital display device. In addition, as mentioned above, the adhesive force is excellent in the range of low temperature to high temperature, and the step compliance is also good. Therefore, for example, it is suitable for a two-sided adhesive sheet for a touch panel, even if a decorative plate or icon is attached to the panel. It is difficult to generate air bubbles when a sheet or a transparent substrate on which a transparent electrode is formed in a capacitive touch panel is bonded to a transparent substrate. In addition, when applied to a flexible organic EL display, the flexible organic EL can be folded or rolled.
本發明之紫外線硬化型黏著劑(以下，稱為黏著劑)，係含有：所定之(A)聚胺酯(甲基)丙烯酸酯(以下，稱為(A)成分)；(B)不含羥基聚合單體，均聚物時之玻璃轉化溫度為-70℃以上0℃未達(以下，稱為(B)成分)；(D)一級含羥基單(甲基)丙烯酸酯(以下，稱為(D)成分)及(E)光聚合引發劑(以下，稱為(E)成分)，並且因應必要含有(C)不含羥基聚合單體，均聚物時之玻璃轉化溫度為0℃以上150℃未達(以下，稱為(C)成分)；(F)可塑劑(以下，稱為(F) 成分)；並係透明且實質性無溶劑型之組成物。 The ultraviolet-curable adhesive (hereinafter, referred to as an adhesive) of the present invention contains: a predetermined (A) polyurethane (meth) acrylate (hereinafter, referred to as (A) component); (B) hydroxyl-free polymerization Monomer and homopolymer have a glass transition temperature of -70 ° C or higher and 0 ° C or lower (hereinafter, referred to as (B) component); (D) first-order hydroxyl-containing mono (meth) acrylate (hereinafter, referred to as ( (D) component) and (E) photopolymerization initiator (hereinafter, referred to as (E) component), and if necessary, (C) does not contain a hydroxyl polymerizable monomer, and the glass transition temperature at the time of homopolymer is 0 ° C or higher 150 The temperature is not reached (hereinafter, referred to as (C) component); (F) plasticizer (hereinafter, referred to as (F) component); and is a transparent and substantially solvent-free composition.
(A)成分，係將分子內具有(甲基)丙烯醯基之聚胺酯，(a1)聚醚多元醇(以下，稱為(a1)成分)、(a2)聚異氰酸酯(以下，稱為(a2)成分)、以及(a3)含羥基單(甲基)丙烯酸酯或含異氰酸酯基單(甲基)丙烯酸酯進行反應所得者。 The component (A) is a polyurethane having a (meth) acrylfluorene group in the molecule, (a1) a polyether polyol (hereinafter, referred to as the (a1) component), and (a2) a polyisocyanate (hereinafter, referred to as (a2) Component)), and (a3) a hydroxyl group-containing mono (meth) acrylate or an isocyanate group-containing mono (meth) acrylate is reacted.
(a1)成分，可無特別限制地使用各種習知的聚醚多元醇。可列舉例如，聚乙烯乙二醇、聚丙二醇及聚四亞甲基乙二醇等，可二種以上併用。市售品，可列舉例如，艾迪科聚醚多元醇1000；艾迪科聚醚多元醇2000(以上，ADEKA(股)製)；PTMG650、PTMG1000、PTMG2000(以上，三菱化學(股)製)等。(a1)成分，特別係根據低溫柔軟性之觀點，以聚丙二醇為佳。 (a1) As the component, various conventional polyether polyols can be used without particular limitation. Examples include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, and two or more of them may be used in combination. Commercially available products include, for example, Aidike polyether polyol 1000; Aidike polyether polyol 2000 (above, manufactured by ADEKA (stock)); PTMG650, PTMG1000, PTMG2000 (above, manufactured by Mitsubishi Chemical (stock)) Wait. The (a1) component is particularly preferably polypropylene glycol from the viewpoint of low-temperature flexibility.
(a1)成分之物性雖無特別限定，但數平均分子量(藉由膠體滲透層析法所得聚苯乙烯換算值。以下，相同。)通常係700~4000。此外，(a1)成分之平均羥基數亦無特別限定，但通常係約1．5~3個。 (a1) Although the physical properties of the component are not particularly limited, the number-average molecular weight (polystyrene conversion value obtained by colloidal permeation chromatography. The same applies hereinafter) is usually 700 to 4000. The average number of hydroxyl groups of the component (a1) is not particularly limited, but it is usually about 1.5 to 3.
(a2)成分，可無特別限制地使用各種習知的聚異氰酸酯。可列舉例如，甲苯雙異氰酸酯、二苯基甲烷雙異氰酸酯、亞二甲苯雙異氰酸酯等之芳香族雙異氰酸酯；六亞甲基雙異氰酸酯、三甲基六亞甲基雙異氰酸酯、賴胺酸雙異氰酸酯等之脂肪族雙異氰酸酯；二環己基甲烷雙異氰酸酯、異佛爾酮雙異氰酸酯、1，4-環己烷雙異氰酸酯、氫化二甲苯雙異氰酸酯、氫化甲苯雙異氰酸酯等之脂環式雙異氰酸酯等，可二種以上併用。此等之中，特別係根據透明性或低溫柔軟性之觀點，以脂肪族雙 異氰酸酯及/或脂環族雙異氰酸酯為佳。 (a2) As the component, various conventional polyisocyanates can be used without particular limitation. Examples include aromatic diisocyanates such as toluene diisocyanate, diphenylmethane diisocyanate, and xylene diisocyanate; hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate. Aliphatic diisocyanates; alicyclic diisocyanates such as dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated toluene diisocyanate, etc. Use more than two kinds together. Among these, aliphatic bisisocyanate and / or alicyclic bisisocyanate are particularly preferred from the viewpoint of transparency or low-temperature flexibility.
(a3)成分，可無特別限制地使用各種習知的含羥基單(甲基)丙烯酸酯(以下，稱為(a3-1)成分)及/或含異氰酸酯基單(甲基)丙烯酸酯(以下，稱為(a3-2)成分)。 (a3) As the component, various conventional hydroxyl-containing mono (meth) acrylates (hereinafter, referred to as (a3-1) components) and / or isocyanate group-containing mono (meth) acrylates ( Hereinafter, it is called (a3-2) component).
(a3-1)成分，可列舉例如，2-羥基乙基(甲基)丙烯酸酯、2-羥基丙基(甲基)丙烯酸酯、3-羥基丙基丙烯酸酯、3-羥基丁基(甲基)丙烯酸酯、4-羥基丁基(甲基)丙烯酸酯、6-羥基己基丙烯酸酯等之含羥基單(甲基)丙烯酸酯等，可二種以上併用。此等之中，根據耐久性及低溫柔軟性之觀點，以全碳數5~10之含羥基單(甲基)丙烯酸酯，特別係2-羥基乙基(甲基)丙烯酸酯及4-羥基丁基(甲基)丙烯酸酯為佳。 (a3-1) Components include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropylacrylate, 3-hydroxybutyl (methyl Hydroxy-containing mono (meth) acrylates, such as methacrylate), 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexylacrylate, etc., may be used in combination of two or more kinds. Among these, from the viewpoints of durability and low-temperature flexibility, hydroxyl-containing mono (meth) acrylates having a total carbon number of 5 to 10, especially 2-hydroxyethyl (meth) acrylate and 4-hydroxy Butyl (meth) acrylate is preferred.
(a3-2)成分，可列舉例如，2-異氰酸乙基(甲基)丙烯酸酯、1，1-二(丙烯醯氧基甲基)乙基異氰酸酯、甲基丙烯酸酸2-(0-〔1′甲基丙基胺基〕羧基胺基)乙基等，特別係2-異氰酸乙基(甲基)丙烯酸酯及/或1，1-二(丙烯醯氧基甲基)乙基異氰酸酯為佳。 (a3-2) Components include, for example, 2-isocyanate ethyl (meth) acrylate, 1,1-bis (acryloxymethyl) ethyl isocyanate, and methacrylic acid 2- (0 -[1′methylpropylamino] carboxyamino) ethyl, etc., in particular, 2-isocyanate ethyl (meth) acrylate and / or 1,1-bis (acryloxymethyl) Ethyl isocyanate is preferred.
(A)成分之製造法並無特別限定，可採用各種習知的聚胺酯(甲基)丙烯酸酯之製法。以下，說明(a3)成分使用(a3-1)成分時所得之(A)成分(以下，稱為(A1)成分)；及(a3)成分使用(a3-2)成分時所得之(A)成分(以下，稱為(A2)成分)。 (A) The manufacturing method of a component is not specifically limited, Various conventional manufacturing methods of a polyurethane (meth) acrylate can be used. Hereinafter, the (A) component obtained when the (a3) component uses the (a3-1) component (hereinafter referred to as the (A1) component); and the (A) obtained when the (a3) component uses the (a3-2) component Component (hereinafter, referred to as (A2) component).
(A1)成分，係先使(a1)成分與(a2)成分反應而預先製造異氰酸酯基末端胺基甲酸酯預聚物(以下，稱為(A1’)成分)， 接著將(A1’)成分與(a3-1)成分反應而得者。反應溫度及反應時間並無特別限定，通常係約70~85℃，約1~5小時。此外，雖(a1)成分與(a2)成分之使用比率並無特別限定，前者之羥基的莫爾數(OH(a1))與後者之異氰酸酯基的莫爾數(NCO(a2))之比(NCO(a2)/OH(a1)只要係通常約1．01~2之範圍即可。此外，(A1’)成分與(a3-1)成分之比率並無特別限定，前者之異氰酸酯基的莫爾數(NCO(A1’))與後者之羥基的莫爾數(OH(a3-1))之比(NCO(A1’)/OH(a3-1))係通常約0．25~1之範圍即可。 The component (A1) is prepared by reacting the component (a1) with the component (a2) to prepare an isocyanate-terminated urethane prepolymer (hereinafter, referred to as (A1 ') component), and then (A1') The component is obtained by reacting with the component (a3-1). The reaction temperature and reaction time are not particularly limited, but are usually about 70 to 85 ° C. and about 1 to 5 hours. In addition, although the usage ratio of the (a1) component and the (a2) component is not particularly limited, the ratio of the Moire number (OH (a1) ) of the hydroxyl group of the former to the Moore number (NCO (a2) ) of the isocyanate group of the latter (NCO (a2) / OH (a1 ) is generally within the range of about 1.01 to 2. In addition, the ratio of the (A1 ') component to the (a3-1) component is not particularly limited. The former is isocyanate-based The ratio of the Moire number (NCO (A1 ') ) to the Moire number (OH (a3-1) ) of the latter hydroxyl group (NCO (A1') / OH (a3-1) ) is usually about 0.25 to 1 Range.
(A2)成分，只要係使(a1)成分與(a2)成分反應得到羥基末端胺基甲酸酯預聚物(以下，稱為(A2’)成分)後，將(A2’)成分與(a3-2)成分反應即可。反應溫度及反應時間係與(A1)成分之情形相同。此外，(a1)成分與(a2)成分之使用比率並無特別限定，只要(NCO(a2)/OH(a1)係通常約0．50~0．99之範圍即可。此外，(A2’)成分與(a3-2)成分之使用比率並無特別限定，只要前者之羥基的莫爾數(OH(A2’))與後者之異氰酸酯基的莫爾數(NCO(a3-2))之比(NCO(a3-2)/OH(A2’))係通常約0．5~1之範圍即可。 (A2) component, as long as the (a1) component and the (a2) component are reacted to obtain a hydroxy-terminated urethane prepolymer (hereinafter referred to as (A2 ') component), the (A2') component and ( a3-2) The components can be reacted. The reaction temperature and reaction time are the same as those of the component (A1). In addition, the use ratio of the (a1) component and the (a2) component is not particularly limited, as long as (NCO (a2) / OH (a1 ) is usually in the range of about 0.5 to 0.99. In addition, (A2 ' The use ratio of the) component and the (a3-2) component is not particularly limited, as long as the molar number of the hydroxyl group (OH (A2 ') ) of the former and the molar number of the isocyanate group of the latter (NCO (a3-2) ) The ratio (NCO (a3-2) / OH (A2 ') ) is usually in the range of about 0.5 to 1.
(A1)成分與(A2)成分的製造任一者皆可在無溶劑下進行，惟亦可在後述之(B)成分及/或(C)成分之存在下進行。 Either (A1) component or (A2) component can be produced without a solvent, but can also be performed in the presence of the (B) component and / or (C) component described later.
(A)成分可將(A1)成分與(A2)成分併用。 (A) component can use together (A1) component and (A2) component.
(A)成分中之(甲基)丙烯醯基之平均個數並無特別限制，通常係約1．5~4，較佳係約1．8~2．2。又，(A)成分之(甲基) 丙烯醯基之平均個數，係意指(A)成分之1分子中所存在之(甲基)丙烯醯基之平均個數。 The average number of (meth) acrylfluorenyl groups in the component (A) is not particularly limited, but is usually about 1.5 to 4, and preferably about 1.8 to 2.2. The average number of (meth) acrylfluorenyl groups in the component (A) means the average number of (meth) acrylfluorenyl groups present in one molecule of the (A) component.
(A)成分之物性雖無特別限定，但重量平均分子量通常係10，000~90，000為佳。此外，加德納色度亦無特別限定，但通常係1以下。 Although the physical properties of the component (A) are not particularly limited, the weight average molecular weight is usually preferably 10,000 to 90,000. In addition, Gardner chromaticity is not particularly limited, but is usually 1 or less.
(A)成分之使用比率，在(A)成分、(B)成分、(C)成分及(D)成分之合計為100質量%時，係10~50質量%。若(A)成分未達10質量%，有硬化性及黏著力降低之傾向，超過50質量%時，則本發明之黏著劑的操作性有惡化之傾向。根據相關之觀點，(A)成分之使用比率，較佳係20~45質量%。 The usage ratio of (A) component is 10 to 50 mass% when the total of (A) component, (B) component, (C) component, and (D) component is 100 mass%. When the component (A) is less than 10% by mass, there is a tendency that the hardenability and the adhesive force are reduced. When it exceeds 50% by mass, the handleability of the adhesive of the present invention tends to be deteriorated. According to a related viewpoint, the use ratio of the component (A) is preferably 20 to 45 mass%.
(B)成分，係不含羥基聚合單體，均聚物時之玻璃轉化溫度係-70℃以上0℃未達，可無特別限制地使用各種習知者。可列舉例如，2-乙基己基(甲基)丙烯酸酯、n-辛基(甲基)丙烯酸酯、異辛基(甲基)丙烯酸酯、壬基(甲基)丙烯酸酯、異壬基(甲基)丙烯酸酯、癸基(甲基)丙烯酸酯、異癸基(甲基)丙烯酸酯、十二烷基(甲基)丙烯酸酯、十六烷基(甲基)丙烯酸酯、異十八烷基(甲基)丙烯酸酯，可二種以上併用。此等之中，根據低溫柔軟性及段差順應性之觀點，係烷基之碳數為4~18之烷基單(甲基)丙烯酸酯為佳，特別係，該烷基係分支者為佳。 The component (B) is a hydroxyl-free polymerizable monomer, and the glass transition temperature during homopolymerization is -70 ° C or higher and 0 ° C or lower, and various conventional ones can be used without particular limitation. Examples include 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl ( (Meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, isodecyl The alkyl (meth) acrylate may be used in combination of two or more kinds. Among these, from the viewpoints of low-temperature flexibility and step compliance, alkyl mono (meth) acrylates having 4 to 18 carbon atoms are preferred, and particularly, those having alkyl branching are preferred. .
(B)成分之使用比率，在(A)成分、(B)成分、(C)成分及(D)成分之合計為100質量%時，係10~70質量%。若(B)成分未達10質量%，本發明之硬化物之低溫柔軟性有削減之傾向，超過 70質量%時，則有黏著力降低之傾向。根據相關之觀點，(B)成分之比率，較佳係20~40質量%。 The use ratio of (B) component is 10 to 70% by mass when the total of (A) component, (B) component, (C) component, and (D) component is 100% by mass. If the component (B) is less than 10% by mass, the low-temperature flexibility of the cured product of the present invention tends to decrease, and when it exceeds 70% by mass, the adhesive force tends to decrease. From a related viewpoint, the ratio of the (B) component is preferably 20 to 40% by mass.
(C)成分，係目的在於提升高溫保持力而可利用之任意成分，其若為不含羥基聚合單體，均聚物時之玻璃轉化溫度係0℃以上150℃未達，可無特別限制地使用各種習知者。可列舉例如，環己基丙烯酸酯、4-t-丁基環己基丙烯酸酯、異冰片基丙烯酸酯、3，3，5-三甲基環己基丙烯酸酯及雙環戊烷丙烯酸酯等之脂環族單(甲基)丙烯酸酯。 Component (C) is any component that can be used for the purpose of improving high-temperature holding power. If it is a hydroxyl-free polymer monomer, the glass transition temperature during homopolymerization is not higher than 0 ° C and not higher than 150 ° C. To use a variety of knowledge. Examples include cycloaliphatics such as cyclohexyl acrylate, 4-t-butylcyclohexyl acrylate, isobornyl acrylate, 3,3,5-trimethylcyclohexyl acrylate, and dicyclopentane acrylate. Mono (meth) acrylate.
(C)成分之使用比率，根據本發明之黏著劑的黏著能提升作用，與其硬化物之低溫柔軟性的平衡性之觀點，在(A)成分、(B)成分、(C)成分及(D)成分之合計為100質量%時，係0~10質量%。此外較佳係5質量%。 The use ratio of the component (C) is based on the viewpoint of the balance between the adhesion-enhancing effect of the adhesive of the present invention and the low-temperature flexibility of the cured product. The components (A), (B), (C), and ( D) When the total of the components is 100% by mass, it is 0 to 10% by mass. In addition, it is preferably 5% by mass.
(B)成分及(C)成分中，「均聚物時之玻璃轉化溫度」，係採用Wiley-Interscience之「聚合物手冊(Polymer Handbook)」所記載之值。例如，2-乙基己基丙烯酸酯之Tg係-70℃，n-丁基丙烯酸酯之Tg係-54℃，甲基丙烯酸甲酯之Tg係105℃。 Among the components (B) and (C), the "glass transition temperature at the time of homopolymer" is the value described in "Polymer Handbook" of Wiley-Interscience. For example, the Tg of 2-ethylhexyl acrylate is -70 ° C, the Tg of n-butyl acrylate is -54 ° C, and the Tg of methyl methacrylate is 105 ° C.
(D)成分，可無特別限制地使用各種習知的一級含羥基單(甲基)丙烯酸酯。可列舉例如，2-羥基乙基(甲基)丙烯酸酯、4-羥基丁基(甲基)丙烯酸酯、環己烷二甲醇單(甲基)丙烯酸酯等，可二種以上併用。此等之中，根據低溫柔軟性之觀點，以2-羥基乙基(甲基)丙烯酸酯及/或4-羥基丁基(甲基)丙烯酸酯為佳。 (D) As the component, various conventional primary hydroxyl-containing mono (meth) acrylates can be used without particular limitation. Examples thereof include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, and the like, and two or more of them may be used in combination. Among these, from the viewpoint of low-temperature flexibility, 2-hydroxyethyl (meth) acrylate and / or 4-hydroxybutyl (meth) acrylate is preferred.
(D)成分之使用比率，在(A)成分，(B)成分，(C) 成分及(D)成分之合計為100質量%時，係20~79．9質量%。若(D)成分未達20質量%，本發明之黏著劑的硬化性及耐久性有降低之傾向，超過79．9質量%時，亦有耐久性降低之傾向。根據相關之觀點，(D)成分之比率，較佳係20~50質量%。 The usage ratio of (D) component is 20 to 79.9% by mass when the total of (A) component, (B) component, (C) component and (D) component is 100% by mass. When the component (D) is less than 20% by mass, the hardenability and durability of the adhesive of the present invention tend to decrease, and when it exceeds 79.9% by mass, the durability tends to decrease. From a related viewpoint, the ratio of the (D) component is preferably 20 to 50% by mass.
(E)成分，可無特別限制地使用各種習知的光聚合引發劑。可列舉例如，二苯乙醇酮化合物、苯乙酮化合物、醯基氧化膦化合物、二茂鈦化合物、噻噸酮化合物、肟酯化合物等之光聚合引發劑、胺或醌等之光增感劑等，可列舉例如，2，2-二甲氧基-1，2-二苯基乙烷-1-酮、1-羥基-環己基苯基酮、2-羥基-2-甲基-1-苯基-丙烷-1-酮、1-〔4-(2-羥基乙氧基)-苯基〕-2-羥基-2-甲基-1-丙烷-1-酮、2-羥基-1-〔4-〔4-(2-羥基-2-甲基-丙醯基)-芐基〕苯基〕-2-甲基-丙烷-1-酮、2-甲基-1-(4-甲基苯硫基)-2-嗎啉丙烷-1-酮、2-(雙甲基胺基)-2-〔(4-甲基苯基)甲基〕-1-〔4-(4-嗎啉)苯基〕-1-丁酮、2，4，6-三甲基苯甲醯基-二苯基氧化膦、二(2，4，6-三甲基苯甲醯基)-苯基氧化膦、二(η5-2，4-環戊二烯-1-基)-二(2，6-二氟-3-(1H-吡咯-1-基)-苯基)鈦、1，2-辛烷二酮1-〔4-(苯硫基)-2-(o-苯甲醯基肟)〕、乙酮1-〔9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基〕-1-(o-乙醯肟)等，可單獨使用1種，亦可2種以上併用。此等之中，根據黏著力之觀點，以2，4，6-三甲基苯甲醯基-二苯基氧化膦為佳。 As the component (E), various conventional photopolymerization initiators can be used without particular limitation. Examples thereof include photoinitiators such as acetophenone compounds, acetophenone compounds, fluorenylphosphine oxide compounds, titanocene compounds, thioxanthone compounds, oxime ester compounds, and photosensitizers such as amines and quinones. Examples include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexylphenyl ketone, and 2-hydroxy-2-methyl-1- Phenyl-propane-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propanyl) -benzyl] phenyl] -2-methyl-propane-1-one, 2-methyl-1- (4-methyl Phenylthio) -2-morpholinopropane-1-one, 2- (bismethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-? (Porphyrin) phenyl] -1-butanone, 2,4,6-trimethylbenzylidene-diphenylphosphine oxide, bis (2,4,6-trimethylbenzylidene) -phenyl Phosphine oxide, bis (η 5 -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1-yl) -phenyl) titanium, 1, 2-octanedione 1- [4- (phenylthio) -2- (o-benzylideneoxime)], ethyl ketone 1- [9-ethyl-6- (2-methylbenzidine ) -9H-carbazol-3-yl] -1- (o-acetamoxime), etc. It may be used alone, and two kinds or more may also be used. Among these, from the viewpoint of adhesion, 2,4,6-trimethylbenzylidene-diphenylphosphine oxide is preferred.
(E)成分之使用比率，相對於(A)成分、(B)成分、(C) 成分及(D)成分之合計質量，係0．1~5質量%。若未達0．1質量%，本發明之黏著劑之硬化性有降低之傾向，超過5質量%時，則有耐久性降低之傾向。根據相關之觀點，(E)成分之比率，較佳係0．5~2質量%。 The use ratio of the (E) component is 0.1 to 5% by mass based on the total mass of the (A) component, (B) component, (C) component, and (D) component. If it is less than 0.1% by mass, the hardenability of the adhesive of the present invention tends to decrease, and if it exceeds 5% by mass, the durability tends to decrease. From a related viewpoint, the ratio of the (E) component is preferably 0.5 to 2% by mass.
(F)成分，係目的在於提升低溫柔軟性及段差順應性而可利用之任意成分，只要係黏著片材可使用之可塑劑即可，可無特別限制地使用各種習知者。具體而言，可列舉例如，液狀松香誘導體、己二酸酯、戊二酸酯、非反應性低聚物或丙烯酸聚合物等，可二種以上併用。此等之中，根據黏著力與耐久性之觀點，以選自液狀松香誘導體、高溫連續聚合所得之非反應性液狀無溶劑丙烯酸聚合物所成群中至少一種為佳。 The component (F) is an arbitrary component that can be used for the purpose of improving low-temperature flexibility and step compliance, as long as it is a plasticizer that can be used for an adhesive sheet, various conventional ones can be used without particular limitation. Specific examples include liquid rosin inducers, adipic acid esters, glutaric acid esters, non-reactive oligomers, and acrylic polymers, and two or more of them may be used in combination. Among these, from the viewpoint of adhesion and durability, at least one selected from the group consisting of a liquid rosin inducer and a non-reactive liquid solventless acrylic polymer obtained by continuous high temperature polymerization is preferred.
(F)成分之使用量，並無特別限制，通常，相對於(A)成分、(B)成分、(C)成分及(D)成分之合計質量，係0~10質量%，較佳係5~10質量%。 The use amount of the (F) component is not particularly limited. Generally, it is 0 to 10% by mass relative to the total mass of the (A) component, (B) component, (C) component, and (D) component. 5 to 10% by mass.
本發明之紫外線硬化型黏著劑，因應必要，亦可含有各種添加劑。可列舉例如，表面調整劑、界面活性劑、紫外線吸收劑、氧化防止劑、光安定劑、黏著賦予劑、無機填料、矽烷偶聯劑、膠體二氧化矽、消泡劑、濕潤劑、防鏽劑等，可二種以上併用。 The ultraviolet curing adhesive of the present invention may contain various additives as necessary. Examples include surface modifiers, surfactants, ultraviolet absorbers, oxidation inhibitors, light stabilizers, adhesion-imparting agents, inorganic fillers, silane coupling agents, colloidal silica, defoamers, wetting agents, and rust preventives. Agents can be used in combination of two or more kinds.
本發明之紫外線硬化型黏著劑，係藉由將(A)成分、(B)成分、(D)成分及(E)成分、以及因應必要之(C)成分、(F)成分及選自前述添加劑所成群中至少一種混合而得。混合手段及混合順序並無特別限定。此外，使用(A)成分而將(B)成分及/或(C)成分作為反應性稀釋劑使用時，(A)成分之(B)成分及/或(C)成分之溶液， 只要將本發明之黏著劑之原料混合即可。 The ultraviolet-curable adhesive of the present invention is selected from the components (A), (B), (D), and (E), and (C), (F), and the components selected from the foregoing. The additive is obtained by mixing at least one of the groups of additives. The mixing means and mixing order are not particularly limited. In addition, when using component (A) and using component (B) and / or (C) as a reactive diluent, a solution of component (B) and / or (C) of component (A) The raw materials of the adhesive of the invention can be mixed.
本發明之紫外線硬化型黏著劑，加德納色度(JIS K5600)通常係1以下，較佳之Hazen色度(JIS K5600)係250以下，透明性優異。 The ultraviolet curing adhesive of the present invention generally has a Gardner color (JIS K5600) of 1 or less, preferably a Hazen color (JIS K5600) of 250 or less, and has excellent transparency.
本發明之紫外線硬化型黏著劑，係實質性無溶劑，溶劑含有量係未達1質量%，較佳係未達0．1質量%。又，在此之溶劑，可列舉例如：苯、甲苯、乙苯、n-丙苯、t-丁苯、o-二甲苯、m-二甲苯、p-二甲苯、四氫萘、十氫萘、芳香族石腦油等之芳香族烴類；n-己烷、n-庚烷、n-辛烷、i-辛烷、n-癸烷之脂肪族烴、環己烷等之脂環族烴；乙酸乙酯、乙酸n-丁酯、乙酸n-戊酯、乙酸2-羥乙酯、乙酸2-丁氧基乙酯、乙酸3-甲氧基丁酯、苯甲酸甲酯等之酯類；丙酮、甲基乙基酮、甲基-i-丁基酮、異佛爾酮、環己酮、甲基環己酮等之酮類；乙二醇單甲基醚、乙二醇單***、乙二醇單丁醚、雙乙二醇單甲基醚、雙乙二醇單***、雙乙二醇單丁醚之乙二醇醚類；抑或可列舉例如：甲醇、乙醇、n-丙醇、i-丙醇、n-丁醇、i-丁醇、s-丁醇、t-丁醇等之醇類等。 The ultraviolet curing adhesive of the present invention is substantially solvent-free, and the solvent content is less than 1% by mass, and preferably less than 0.1% by mass. Examples of the solvent include benzene, toluene, ethylbenzene, n-propylbenzene, t-butylbenzene, o-xylene, m-xylene, p-xylene, tetrahydronaphthalene, and decahydronaphthalene. , Aromatic naphtha and other aromatic hydrocarbons; n-hexane, n-heptane, n-octane, i-octane, n-decane aliphatic hydrocarbons, cyclohexane and other alicyclics Hydrocarbons; esters of ethyl acetate, n-butyl acetate, n-pentyl acetate, 2-hydroxyethyl acetate, 2-butoxyethyl acetate, 3-methoxybutyl acetate, methyl benzoate, etc. Ketones; acetone, methyl ethyl ketone, methyl-i-butyl ketone, isophorone, cyclohexanone, methyl cyclohexanone and other ketones; ethylene glycol monomethyl ether, ethylene glycol mono Diethyl ether, glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether glycol ethers; or, for example, methanol, ethanol, n- Alcohols such as propanol, i-propanol, n-butanol, i-butanol, s-butanol, t-butanol, and the like.
本發明之紫外線硬化型黏著劑之黏度(mPa‧s/25℃)並無特別限定，通常係約100~15000。黏度，係藉由E型黏度計(TVE-10(東機產業(股)製)所得之測定值(5分)。 The viscosity (mPa‧s / 25 ° C) of the ultraviolet-curable adhesive of the present invention is not particularly limited, but is usually about 100 to 15,000. The viscosity is a measured value (5 points) obtained by an E-type viscometer (TVE-10 (manufactured by Toki Sangyo Co., Ltd.)).
本發明之硬化物，係將本發明之紫外線硬化型黏著劑硬化者，發揮作為黏著層之機能。 The hardened product of the present invention is a hardened ultraviolet curing adhesive of the present invention, and functions as an adhesive layer.
本發明之硬化物之形成方法並無特別限定，可藉由將本發明 之黏著劑塗佈至各種塑料薄膜基材上，照射紫外線而得。紫外線光源，可列舉例如，具有氙氣燈、高壓水銀燈、金屬鹵化物燈之紫外線照射裝置。該裝置中，紫外線光量及光源、以及搬送速度等之條件並無特別限定，通常，光量通常係約80~160W/cm，搬送速度通常係約5~50m/分。 The method for forming the cured product of the present invention is not particularly limited, and can be obtained by applying the adhesive of the present invention to various plastic film substrates and irradiating ultraviolet rays. Examples of the ultraviolet light source include an ultraviolet irradiation device including a xenon lamp, a high-pressure mercury lamp, and a metal halide lamp. In this device, conditions such as the amount of ultraviolet light, the light source, and the conveyance speed are not particularly limited. Generally, the amount of light is usually about 80 to 160 W / cm, and the conveyance speed is usually about 5 to 50 m / min.
塑料薄膜基材，例如，可使用聚對苯二甲酸乙二酯薄膜(PET薄膜)、聚丙烯薄膜、聚丁烯薄膜、聚丁二烯薄膜、聚甲基戊烯薄膜、聚氯乙烯薄膜、氯乙烯共聚體薄膜、聚萘二甲酸乙二醇酯薄膜、聚對苯二甲酸丁二酯薄膜、聚胺酯薄膜、乙烯醋酸乙烯酯薄膜、離聚物樹脂薄膜、乙烯‧(甲基)丙烯酸共聚體薄膜、乙烯‧(甲基)丙烯酸酯共聚體薄膜、聚苯乙烯薄膜、聚碳酸酯薄膜、聚醯亞胺薄膜、氟樹脂薄膜等。此外，亦可使用此等之交聯薄膜。進一步，亦可係此等之積層薄膜。此等薄膜，可係施有輕~重剝離處理者，亦可係具備易接著層者。 Plastic film substrates, for example, polyethylene terephthalate film (PET film), polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, Vinyl chloride interpolymer film, polyethylene naphthalate film, polybutylene terephthalate film, polyurethane film, ethylene vinyl acetate film, ionomer resin film, ethylene (meth) acrylic acid copolymer Film, ethylene (meth) acrylate copolymer film, polystyrene film, polycarbonate film, polyimide film, fluororesin film, etc. In addition, these crosslinked films can also be used. Furthermore, these laminated films may be used. These films may be those having a light-to-heavy peeling treatment, or those having an easy adhesion layer.
本發明之硬化物，在-20℃及1Hz中之儲能模量G’(以下，稱為低溫G’)通常係1×106Pa以下，並且，在100℃及1Hz中之儲能模量G’(以下，稱為高溫G’)係1×104Pa以上。由於具有相關之特性，故可認為，該硬化物可兼具低溫時之黏著力(柔軟性)及高溫時之黏著力(保持力)，且奏效優異之段差順應性。根據相關效果之觀點，低溫G’較佳係1×106Pa以下，並且，高溫G’係1×104Pa以上。 The hardened product of the present invention has a storage modulus G '(hereinafter, referred to as low temperature G') at -20 ° C and 1 Hz, and is generally 1 × 10 6 Pa or less, and a storage modulus at 100 ° C and 1 Hz. The amount G '(hereinafter, referred to as high temperature G') is 1 × 10 4 Pa or more. Because of the related characteristics, it can be considered that the hardened product can have both the adhesive force (softness) at low temperature and the adhesive force (holding force) at high temperature, and it has excellent segment compliance. From the viewpoint of related effects, the low temperature G ′ is preferably 1 × 10 6 Pa or less, and the high temperature G ′ is 1 × 10 4 Pa or more.
本發明之硬化物之厚度亦無特別限定，通常，乾燥後塗膜係約10~1000μm，較佳係在25~500μm之範圍內即可。該膜 厚之黏著層可適宜地發揮段差吸收性，此外，氣泡亦難以產生。 The thickness of the hardened material of the present invention is also not particularly limited. Generally, the coating film after drying is about 10 to 1000 μm, preferably 25 to 500 μm. This film-thick adhesive layer can appropriately exhibit the step absorbency, and it is also difficult to generate bubbles.
本發明之黏著片材，係於前述塑料薄膜之至少單面具有本發明之硬化物(黏著層)的物品。該片材亦可進行加工成為膠帶狀而使用。 The adhesive sheet of the present invention is an article having the cured product (adhesive layer) of the present invention on at least one side of the aforementioned plastic film. This sheet can also be processed into a tape shape and used.
以下，藉由實施例及比較例而具體說明本發明。但，並非因此限定本發明之技術範圍。實施例中之「份」及「%」只要未特別特定，則係質量基準。 Hereinafter, the present invention will be specifically described with reference to examples and comparative examples. However, this does not limit the technical scope of the present invention. "Part" and "%" in the examples are based on quality as long as they are not particularly specified.
各製造例中，基底樹脂之聚胺酯(甲基)丙烯酸酯之重量平均分子量，係藉由膠體滲透層析所得聚苯乙烯換算值，該測定條件如以下所述 In each production example, the weight average molecular weight of the polyurethane (meth) acrylate of the base resin is a polystyrene conversion value obtained by colloidal permeation chromatography, and the measurement conditions are as follows
測定裝置本體：製品名「HLC-8220GPC」，東曹(股)製 Measuring device body: Product name "HLC-8220GPC", manufactured by Tosoh Corporation
管柱：製品名「TSKGel G1000H」、「TSKGel G2000H」，任一者皆係東曹(股)製 Columns: Product names "TSKGel G1000H" and "TSKGel G2000H", either of which is manufactured by Tosoh Corporation
展開溶劑：四氫呋喃 Development solvent: tetrahydrofuran
製造例1 Manufacturing example 1
具備冷卻管、攪拌機及氮導入管之反應裝置中，加入數平均分子量2000之聚丙二醇(ADEKA(股)製，商品名「艾迪科聚醚P-2000」)(以下，稱為PPG2000)884份、異佛爾酮雙異氰酸酯(以下，稱為IPDI)106份、2-乙基己基丙烯酸酯(以下，稱為2-EHA)333份及辛基酸錫0．4份，升溫至80℃並保溫3小時後，得到中間體之異氰酸酯基末端胺基甲酸酯預聚物之2-EHA溶液。接 著，加入4-羥基丁基丙烯酸酯(以下，稱為4HBA)10份，在80℃下保溫2小時，藉由NCO測定而確認反應完結，從而得到重量平均分子量55，000，平均官能基數2．0之聚胺酯丙烯酸酯(以下，稱為(A-1)成分)之2-EHA溶液。 In a reaction device equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, polypropylene glycol (manufactured by ADEKA (trade name), "Edico Polyether P-2000") with a number average molecular weight of 2000 was added (hereinafter, referred to as PPG2000) 884 Parts, 106 parts of isophorone diisocyanate (hereinafter referred to as IPDI), 333 parts of 2-ethylhexyl acrylate (hereinafter referred to as 2-EHA), and 0.4 parts of tin octylate, and the temperature was raised to 80 ° C. After incubation for 3 hours, a 2-EHA solution of the intermediate isocyanate-terminated urethane prepolymer was obtained. Next, 10 parts of 4-hydroxybutyl acrylate (hereinafter referred to as 4HBA) was added, and the temperature was maintained at 80 ° C for 2 hours. The reaction was confirmed to be complete by NCO measurement, thereby obtaining a weight average molecular weight of 55,000 and an average number of functional groups of 2 0.0% 2-EHA solution of polyurethane acrylate (hereinafter, referred to as (A-1) component).
製造例2 Manufacturing example 2
在與製造例1相同之反應裝置中，加入PPG2000 910份、六亞甲基雙異氰酸酯(以下，稱為HDI)82份、2-EHA333份及辛基酸錫0．4份，升溫至80℃並保溫3小時後，得到中間體之異氰酸酯基末端胺基甲酸酯預聚物之2-EHA溶液。接著，加入2-羥基乙基丙烯酸酯(以下，稱為HEA)8份，在80℃下保溫2小時，藉由NCO測定而確認反應完結，從而得到重量平均分子量57，000，平均官能基數2．0之聚胺酯丙烯酸酯低聚物(以下，稱為(A-2)成分)之2-EHA溶液。 In the same reaction apparatus as in Manufacturing Example 1, 910 parts of PPG2000, 82 parts of hexamethylene diisocyanate (hereinafter referred to as HDI), 2-EHA333 parts, and 0.4 parts of tin octylate were added, and the temperature was raised to 80 ° C. After incubation for 3 hours, a 2-EHA solution of the intermediate isocyanate-terminated urethane prepolymer was obtained. Next, 8 parts of 2-hydroxyethyl acrylate (hereinafter referred to as HEA) was added, and the temperature was maintained at 80 ° C for 2 hours. The completion of the reaction was confirmed by NCO measurement to obtain a weight average molecular weight of 57,000 and an average number of functional groups of 2 0.0% of 2-EHA solution of polyurethane acrylate oligomer (hereinafter, referred to as (A-2) component).
製造例3 Manufacturing example 3
在與製造例1相同之反應裝置中，加入數平均分子量1000之聚丙二醇(ADEKA(股)製，商品名「艾迪科聚醚P-1000」)(以下，稱為PPG1000)840份、HDI149份、2-EHA333份及辛基酸錫0．4份，升溫至80℃並保溫3小時後，得到中間體之異氰酸酯基末端胺基甲酸酯預聚物之2-EHA溶液。接著，加入HEA11份，在80℃下保溫2小時，藉由NCO測定而確認反應完結，從而得到重量平均分子量68，000，平均官能基數2．0之聚胺酯丙烯酸酯低聚物(以下，稱為(A-3)成分)之2-EHA溶液。 In the same reaction apparatus as in Production Example 1, 840 parts of polypropylene glycol (manufactured by ADEKA Co., Ltd., trade name “Edico Polyether P-1000”) (hereinafter, referred to as PPG1000), and HDI149 were added. Parts, 2-EHA 333 parts, and tin octylate 0.4 parts. After heating to 80 ° C. and holding for 3 hours, a 2-EHA solution of the isocyanate-terminated urethane prepolymer of the intermediate was obtained. Next, 11 parts of HEA was added, and the temperature was maintained at 80 ° C for 2 hours. The completion of the reaction was confirmed by NCO measurement to obtain a polyurethane acrylate oligomer having a weight average molecular weight of 68,000 and an average number of functional groups of 2.0 (hereinafter referred to as (A-3) Ingredient) 2-EHA solution.
製造例4 Manufacturing Example 4
在與製造例1相同之反應裝置中，加入PPG2000 898份、IPDI 96份、2-EHA333份及辛基酸錫0．4份，升溫至80℃並保溫3小時後，得到中間體之羥基末端聚胺酯之2-EHA溶液。接著，加入2-異氰酸乙基甲基丙烯酸酯(昭和電工(股)製，商品名「Karenz MOI」)(以下，稱為MOI)6份，在80℃下保溫2小時，藉由NCO測定而確認反應完結，從而得到重量平均分子量55，000，平均官能基數2．0之聚胺酯甲基丙烯酸低聚物(以下，稱為(A-4)成分)之2-EHA溶液。 In the same reaction apparatus as in Manufacturing Example 1, 898 parts of PPG2000, 96 parts of IPDI, 333 parts of 2-EHA, and 0.4 parts of tin octylate were added, and the temperature was raised to 80 ° C and the temperature was maintained for 3 hours to obtain the hydroxyl end of the intermediate. 2-EHA solution of polyurethane. Next, 6 parts of 2-isocyanate ethyl methacrylate (manufactured by Showa Denko Corporation, trade name "Karenz MOI") (hereinafter referred to as MOI) was added, and the temperature was maintained at 80 ° C for 2 hours, and NCO was applied. The measurement confirmed the completion of the reaction, and a 2-EHA solution of a polyurethane methacrylic oligomer (hereinafter, referred to as (A-4) component) having a weight average molecular weight of 55,000 and an average number of functional groups of 2.0 was obtained.
比較製造例1 Comparative Manufacturing Example 1
在與製造例1相同之反應裝置中，加入數平均分子量18000之聚丙二醇(旭硝子(股)製，商品名「PREMINOL S 4318F」)(以下，稱為PPG18000)986份、IPDI 6份、及辛基酸錫0．3份，升溫至80℃並保溫2小時後，藉由NCO測定而確認反應完結，得到中間體之羥基末端聚胺酯低聚物。接著，加入MOI 8份，在80℃下保溫2小時，藉由NCO測定而確認反應完結，從而得到重量平均分子量62，000，平均官能基數2．0之聚胺酯甲基丙烯酸酯低聚物()(以下，稱為()成分)。 In the same reaction apparatus as in Production Example 1, 986 parts of polypropylene glycol (manufactured by Asahi Glass Co., Ltd., trade name "PREMINOL S 4318F") (hereinafter, referred to as PPG18000), 6 parts of IPDI, and 6 parts of propylene were added. After 0.3 parts of tin basal acid was heated to 80 ° C. and held for 2 hours, the reaction was confirmed to be complete by NCO measurement to obtain a hydroxyl-terminated polyurethane oligomer of an intermediate. Next, 8 parts of MOI was added, and the temperature was maintained at 80 ° C for 2 hours. The completion of the reaction was confirmed by NCO measurement to obtain a polyurethane methacrylate oligomer having a weight average molecular weight of 62,000 and an average number of functional groups of 2.0 ( ) (Hereinafter, referred to as ( )ingredient).
比較製造例2 Comparative Manufacturing Example 2
在與製造例1相同之反應裝置中，加入含羥基丙烯酸系聚合物之2-EHA溶液479份(根上工業(股)製，商品名「Paracron SY-1062KY」；丙烯酸系聚合物62wt%，重量平均分子量500000，2- EHA 38wt%)、MOI 3份、辛基酸錫0．2份，升溫至80℃，保溫4小時後，藉由NCO測定而確認反應完結，從而得到重量平均分子量500000之乙烯性不飽和鍵含有丙烯酸系聚合物()(以下，稱為()成分)之2-EHA溶液。 In the same reaction apparatus as in Production Example 1, 479 parts of a 2-EHA solution of a hydroxyl-containing acrylic polymer (manufactured by Negami Industries, Ltd., trade name "Paracron SY-1062KY") was added; the acrylic polymer was 62 wt%, and the weight was The average molecular weight is 500,000, 2-EHA (38 wt%), 3 parts of MOI, and 0.2 parts of tin octoate. The temperature is raised to 80 ° C, and after 4 hours of incubation, the reaction is confirmed by NCO measurement to obtain a weight average molecular weight of 500,000. The ethylenically unsaturated bond contains an acrylic polymer ( ) (Hereinafter, referred to as ( ) Ingredient) of 2-EHA solution.
實施例1 Example 1
藉由將(A-1)成分、(B)成分之2-EHA；(D)成分之4HBA；以及(E)成分之1-羥基環己基苯基酮(DKSH日本公司製，商品名「Luna200」(以下，稱為L200))及2，4，6-三甲基苯甲醯基-二苯基-氧化膦(Lambson Group Ltd．公司製，商品名「SPEEDCURE TPO」(以下，稱為TPO))以表1所示之質量%混合，得到紫外線硬化型黏著劑。溶劑含有率及加德納色度如表2所示(以下，相同)。 The component (A-1) and (B) 2-EHA; (D) 4HBA; and (E) 1-hydroxycyclohexylphenyl ketone (manufactured by DKSH Japan, trade name "Luna200" "(Hereinafter, referred to as L200) and 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide (manufactured by Lambson Group Ltd. under the trade name" SPEEDCURE TPO "(hereinafter, referred to as TPO )) It is mixed at the mass% shown in Table 1, and an ultraviolet curing adhesive is obtained. The solvent content and Gardner chromaticity are shown in Table 2 (hereinafter, the same).
實施例2~10、比較例1~6 Examples 2 to 10, Comparative Examples 1 to 6
藉由如表1所示之組成及質量%混合，得到個別之紫外線硬化型黏著劑。 By mixing the composition and mass% as shown in Table 1, individual ultraviolet curing adhesives were obtained.
※1：(E)成分之使用量(wt%)，係(A)成分、(B)成分、(C)成分及(D)成分之合計質量為1時之比率。 ※2：(F)成分之使用量(wt%)，係(A)成分、(B)成分、(C)成分及(D)成分之合計質量為1時之比率。 ※ 1: The amount (wt%) of (E) component is the ratio when the total mass of (A) component, (B) component, (C) component and (D) component is 1. ※ 2: The usage amount (wt%) of (F) component is the ratio when the total mass of (A) component, (B) component, (C) component and (D) component is 1.
表1中，各成分之簡稱係表示以下之化合物。 In Table 1, the abbreviations of the respective components refer to the following compounds.
<(B)成分> <(B) component>
‧2-EHA：2-乙基己基丙烯酸酯 ‧2-EHA: 2-ethylhexyl acrylate
‧ISTA：異十八烷基丙烯酸酯 ‧ISTA: Isooctadecyl acrylate
<(C)成分> <(C) component>
‧IBXA：異冰片丙烯酸酯 ‧IBXA: Isobornyl Acrylate
‧TMCHA：3，3，5-三甲基環己基丙烯酸酯 ‧TMCHA: 3,3,5-trimethylcyclohexyl acrylate
<(D)成分> <(D) component>
‧4HBA：4-羥基丁基丙烯酸酯 ‧4HBA: 4-hydroxybutyl acrylate
‧2HBA：2-羥基丁基丙烯酸酯 ‧2HBA: 2-hydroxybutyl acrylate
‧HEA：2-羥基乙基丙烯酸酯 ‧HEA: 2-hydroxyethyl acrylate
<(E)成分> <(E) component>
‧L200：1-羥基環己基苯基酮(DKSH日本公司製，商品名「Luna200」) ‧L200: 1-hydroxycyclohexyl phenyl ketone (made by DKSH Japan, trade name "Luna200")
‧TPO：2，4，6-三甲基苯甲醯基-二苯基-氧化膦(Lambson Group Ltd．公司製，商品名「SPEEDCURE TPO」) ‧TPO: 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide (manufactured by Lambson Group Ltd., trade name "SPEEDCURE TPO")
<(F)成分> <(F) component>
‧UH-2041：含羥基丙烯酸聚合物(商品名「ARUFON UH-2041」，東亞合成(股)製) ‧UH-2041: Hydroxyl-containing acrylic polymer (trade name "ARUFON UH-2041", manufactured by Toa Kosei Co., Ltd.)
‧DOA：己二酸二(2-乙基己基) ‧DOA: Di (2-ethylhexyl) adipate
實施例及比較例之各黏著劑，其等之相溶性、加德納色度、溶劑含有率及黏度係根據以下之基準及條件進行評估及測定。 For each of the adhesives of Examples and Comparative Examples, their compatibility, Gardner color, solvent content, and viscosity were evaluated and measured according to the following standards and conditions.
<相溶性> <Compatibility>
○：均勻且完全透明 ○: Uniform and completely transparent
×：確認到白濁、沈澱物、不溶解物及液相分離中任一者 ×: Any of white turbidity, precipitate, insoluble matter, and liquid phase separation were confirmed
<加德納色度> <Gardner Chroma>
以JIS K5600為基準所得之測定值。 Measured value based on JIS K5600.
<溶劑含有率> <Solvent content rate>
下述條件中氣相色譜儀裝置之測定值。 Measured value of the gas chromatograph device under the following conditions.
(分析裝置) (Analytical device)
GC：Agilent 6850(安捷倫‧科技(股)製) GC: Agilent 6850 (Agilent ‧ Technology (stock) system)
(GC測定條件) (GC measurement conditions)
GC管柱：HP-1(安捷倫‧科技(股)製) GC column: HP-1 (manufactured by Agilent Technologies)
管柱溫度：50℃(10min)→10℃/min→300℃(10min) Column temperature: 50 ℃ (10min) → 10 ℃ / min → 300 ℃ (10min)
管柱流量：2．0ml/min Column flow: 2.0ml / min
Carrier gas：氦 Carrier gas: Helium
注入方法：Split(50：1) Injection method: Split (50: 1)
檢出溫度：300℃ Detection temperature: 300 ℃
<黏度(mPa‧s)> <Viscosity (mPa‧s)>
以E型黏度計(TVE-10(東機產業(股)製)在25℃及5分之條件下的測定值。 Measured by an E-type viscosity meter (TVE-10 (manufactured by Toki Sangyo Co., Ltd.) at 25 ° C and 5 minutes.
對於實施例及比較例之各紫外線硬化型黏著劑實施以下之評估。又，未對比較例6進行評估。 The following evaluations were performed for each ultraviolet-curable adhesive of Examples and Comparative Examples. In addition, Comparative Example 6 was not evaluated.
1．黏著劑層之儲能模量(G’) 1. Storage modulus of the adhesive layer (G ’)
(1)黏著劑，在75μm厚之重剝離處理聚酯薄膜(PANAC(股)製，商品名「SP-PET-03-75BU」)上，塗佈成為硬化後之膜 厚係200μm，並將黏著劑組成物塗佈層與38μm厚之輕剝離處理聚酯薄膜(PANAC(股)製，商品名「SP-PET-01-38BU」)之剝離處理面貼合。接著，藉由對於所得之塗佈薄膜，在大氣中，以高壓水銀燈(100mW/cm2，900mJ/cm2)照射紫外線，從而製作含有黏著層之積層薄膜(輕剝離處理聚酯薄膜/黏著層/重剝離處理聚酯薄膜)。 (1) An adhesive is applied on a 75 μm thick peeled polyester film (manufactured by PANAC (stock), trade name “SP-PET-03-75BU”), and the cured film thickness is 200 μm, and The adhesive composition coating layer was bonded to the release-treated surface of a 38 μm-thick light release-treated polyester film (manufactured by PANAC (stock), trade name “SP-PET-01-38BU”). Next, the obtained coating film was irradiated with ultraviolet rays with a high-pressure mercury lamp (100 mW / cm 2 , 900 mJ / cm 2 ) in the air to produce a laminated film (light peeling treatment polyester film / adhesive layer) containing an adhesive layer. / Repeated polyester film).
(2)接著，由該試驗用積層薄膜裁切出1cm×1cm之試驗片。接著，從該試驗片將輕剝離處理聚酯薄膜與重剝離處理聚酯薄膜剝離，得到僅由黏著層(硬化物)所成之片材(以下，稱為黏著層片材)。 (2) Next, a test piece of 1 cm × 1 cm was cut out from the test laminated film. Next, the light release-treated polyester film and the heavy release-treated polyester film were peeled from this test piece to obtain a sheet (hereinafter, referred to as an adhesive layer sheet) made of only an adhesive layer (cured material).
(3)接著，將該黏著層片材，放置於市售之測定機(賽默飛世爾科技公司製，「HAAKE MARS II CTC(ARES)」)上，在以下之條件下測定其之動態黏彈性。並且，藉由測定結果，求得-20℃及100℃中之儲能模量G’。 (3) Next, the adhesive layer sheet was placed on a commercially available measuring machine ("HAAKE MARS II CTC (ARES)" manufactured by Thermo Fisher Scientific Corporation), and its dynamic adhesion was measured under the following conditions. elasticity. From the measurement results, the storage modulus G 'at -20 ° C and 100 ° C was determined.
變形模式：捻 Deformation mode: twist
測定周波數：1Hz Measuring cycle number: 1Hz
昇溫速度：3℃/分 Heating rate: 3 ℃ / min
測定溫度：-50~100℃ Measurement temperature: -50 ~ 100 ℃
形狀：平行板20．0mmφ Shape: Parallel plate 20.0mmφ
2.黏著層之段差順應性 2. Segment compliance of the adhesive layer
(1)與項目1．(1)相同，使黏著層之膜厚成為100μm而製作試驗用積層薄膜，進一步剝離輕剝離處理聚酯薄膜，以50μm厚之聚酯薄膜(東洋紡績(股)製，商品名「COSMOSHINE A-4300」)取代 其並藉由2kg滾軸而貼合，放置2小時。接著，由此者裁切出8cm×8cm之試驗片，藉由剝離重剝離處理聚酯薄膜，從而製作單面黏著片材(COSMOSHINE A-4300/黏著層)。 (1) and item 1. (1) Similarly, a test laminated film was prepared by setting the film thickness of the adhesive layer to 100 μm, and the polyester film was lightly peeled off. A 50 μm-thick polyester film (manufactured by Toyobo Corporation, trade name “COSMOSHINE A- 4300 ") instead of this, and it was attached by a 2kg roller, and left for 2 hours. Then, a test piece of 8 cm × 8 cm was cut out by this method, and the polyester film was processed by peeling and re-peeling to produce a single-sided adhesive sheet (COSMOSHINE A-4300 / adhesive layer).
(2)另一方面，準備10cm×10cm×2mm之玻璃板，在其之上載置聚酯薄膜片(5cm×5cm×50μm)。 (2) On the other hand, a glass plate of 10 cm × 10 cm × 2 mm was prepared, and a polyester film sheet (5 cm × 5 cm × 50 μm) was placed thereon.
(3)接著，使該聚酯片完全被覆前述單面黏著片材，藉由2kg滾軸使其等密著，從而製作試驗用積層體(COSMOSHINE A-4300/黏著層(100μm厚)/聚酯薄膜片(50μm厚)/玻璃板)。 (3) Next, the polyester sheet was completely covered with the single-sided adhesive sheet, and the two sheets were uniformly adhered with a 2 kg roller to prepare a test laminate (COSMOSHINE A-4300 / adhesive layer (100 μm thick) / polymer) Ester film sheet (50 μm thick) / glass plate).
(4)接著，將該試驗用積層體，以高壓滅菌器在50℃、0．5MPa及20分之條件下處理後，在25℃、50%RH之條件下放置24小時後，於恆溫恆濕槽中，在85℃、85%RH及24小時之條件下放置。 (4) Next, the test laminate is treated in an autoclave at 50 ° C, 0.5 MPa, and 20 minutes, and then left at 25 ° C and 50% RH for 24 hours. Place in a wet tank at 85 ° C, 85% RH, and 24 hours.
(5)之後，前述黏著層之段差順應性，根據以下之基準以肉眼評估。 (5) After that, the step compliance of the aforementioned adhesive layer was evaluated with the naked eye based on the following criteria.
1：無觀察到沿著聚酯薄膜片之各邊的浮起，並且，亦未確認到氣泡 1: No floating along the sides of the Mylar sheet was observed, and no air bubbles were recognized
2：雖無觀察到沿著聚酯薄膜片之各邊的浮起，但可確認到以5個為限度之微細之氣泡 2: Although no floating was observed along each side of the polyester film sheet, 5 fine bubbles were confirmed to be limited
3：可觀察到沿著聚酯薄膜片之各邊有微寬幅之浮起，並且，亦可確認到以10個為限度之微細之氣泡 3: Slightly wide floating can be observed along each side of the polyester film sheet, and fine bubbles with a limit of 10 can also be confirmed
4：可觀察到沿著聚酯薄膜片之各邊有寬幅之浮起，並且，不僅微細之氣泡，亦可確認到複數之大氣泡 4: Wide floating is observed along each side of the polyester film sheet, and not only fine bubbles but also a plurality of large bubbles are also recognized
3．黏著力 3． Adhesion
(1)以2kg滾軸將前述項目2．(1)之單面黏著片材與玻璃板貼合而製作黏著試驗用積層體(COSMOSHINE A-4300/黏著層/玻璃板)，將此在25℃及50%RH之條件下放置24小時。 (1) Use the 2kg roller to move the item 2 above. (1) A single-sided adhesive sheet was bonded to a glass plate to produce a laminated body for adhesion test (COSMOSHINE A-4300 / adhesive layer / glass plate), and this was left to stand at 25 ° C and 50% RH for 24 hours.
(2)接著，藉由使該單面黏著片材從玻璃板以300mm/min之速度向180°方向剝離，從而測定黏著力(N/25mm) (2) Next, the single-sided adhesive sheet was peeled from the glass plate in a direction of 180 ° at a speed of 300 mm / min to measure the adhesive force (N / 25 mm).
(3)又，測定，係使用市售之機械(AND(股)製，TENSILON萬能材料試驗機)。 (3) Measurement was performed using a commercially available machine (manufactured by AND Corporation, TENSILON universal material testing machine).
4．黏著層之再剝離性 4． Re-peelability
根據以下之基準，以肉眼評估前述項目3.(2)之黏著力試驗實施後之玻璃板的殘膠狀態。 Based on the following criteria, the state of the adhesive residue of the glass plate after the implementation of the adhesion test of item 3. (2) was visually evaluated.
○：無殘膠 ○: No residue
△：部分有些微殘膠 △: Some slight residual glue
×：玻璃表面整面有殘膠 ×: There is residual glue on the entire surface of the glass surface
5．透明性 5． Transparency
使用村上色彩技術研究所製色度計，根據JIS K 5400為基準，測定前述項目3．(1)之黏著試驗用積層體之霧度值、及將此静置於溫度85℃及85%RH之恆溫恆濕槽中500小時後之霧度值。又，所得之霧度值，係包含基材(COSMOSHINE A-4300及玻璃板)之霧度值的值。 2. The aforementioned items were measured using a colorimeter manufactured by Murakami Color Technology Research Institute in accordance with JIS K 5400. (1) The haze value of the laminated body for adhesion test, and the haze value after 500 hours of standing in a constant temperature and humidity tank at a temperature of 85 ° C and 85% RH. The obtained haze value is a value including a haze value of a substrate (COSMOSHINE A-4300 and a glass plate).
6．黏著層之耐久性 6. Durability of the adhesive layer
將前述項目3．(1)之黏著試驗用積層體，靜置於溫度85℃及85%RH之恆溫恆濕槽中500小時後，根據以下之基準評估黏著層之耐久 性。 Put the aforementioned item 3. (1) The laminated body for adhesion test was left in a constant temperature and humidity tank at a temperature of 85 ° C and 85% RH for 500 hours, and then the durability of the adhesion layer was evaluated according to the following criteria.
○：基材之剝離、黏著層位置之偏移、黏著層中之氣泡、黏著層之破損任一者皆無 ○: None of the peeling of the substrate, the shift of the position of the adhesive layer, the bubbles in the adhesive layer, or the damage of the adhesive layer
×：基材之剝離、黏著層位置之偏移、黏著層中之氣泡、黏著層之破損中至少一者發生缺陷 ×: At least one of the peeling of the substrate, the displacement of the position of the adhesive layer, the bubbles in the adhesive layer, or the damage of the adhesive layer occurred.
7．保持力 7. Retentivity
將前述項目2．(1)之單面黏著片材，以2kg滾軸與不銹鋼板貼合，在25℃及50%RH之條件下放置24小時。接著，根據JISZ-1524為基準，於該單面黏著片材之一端向垂直方向負荷1kg之荷重，在附恆溫槽保持力試驗機(TESTER產業(股)製，應力緩和試驗機(附恆溫槽))中以100℃之條件，測定至黏著膠帶剝落為止之時間。 Put the aforementioned item 2. (1) The single-sided adhesive sheet is bonded to a stainless steel plate with a 2kg roller and left for 24 hours under the conditions of 25 ° C and 50% RH. Next, based on JISZ-1524, a load of 1 kg was applied to one end of the single-sided adhesive sheet in a vertical direction, and a thermostatic bath holding force tester (manufactured by TESTER Industries, Ltd.) and a stress relaxation tester (with thermostat) In)), the time until the peeling of the adhesive tape was measured at 100 ° C.
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| JP (1) | JP6969235B2 (en) |
| KR (1) | KR102378844B1 (en) |
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| JP6697359B2 (en) * | 2016-09-16 | 2020-05-20 | リンテック株式会社 | Adhesives for flexible displays, adhesive sheets, flexible laminated members and flexible displays |
| JP6969515B2 (en) * | 2017-07-24 | 2021-11-24 | 荒川化学工業株式会社 | UV curable adhesive, cured product, adhesive sheet |
| KR102323585B1 (en) * | 2018-09-03 | 2021-11-05 | 아라까와 가가꾸 고교 가부시끼가이샤 | Active energy ray-curable adhesive composition, cured product and adhesive sheet |
| JP6757479B2 (en) * | 2019-01-30 | 2020-09-16 | 日東電工株式会社 | Adhesive sheets, optical films with adhesive layers, laminates, and image displays |
| JP2020164840A (en) * | 2019-03-27 | 2020-10-08 | 荒川化学工業株式会社 | Ultraviolet curable adhesive composition for protective film, cured product, and protective sheet |
| JP7428494B2 (en) * | 2019-09-18 | 2024-02-06 | リンテック株式会社 | Repeated bending laminate member and repeatable bending device |
| WO2021067432A1 (en) * | 2019-09-30 | 2021-04-08 | Shurtape Technologies, Llc | Adhesive and methods of use |
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| JP7069234B2 (en) * | 2020-02-28 | 2022-05-17 | リンテック株式会社 | Adhesive sheet for flexible display, flexible laminated member and flexible display |
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| KR20220006900A (en) * | 2020-07-09 | 2022-01-18 | 동우 화인켐 주식회사 | Adhesive composition and adhesive film preparing from the same |
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| KR20170121153A (en) * | 2015-02-24 | 2017-11-01 | 아사히 가라스 가부시키가이샤 | Pressure-sensitive adhesive film, transparent sheet material with pressure-sensitive adhesive layer, and display device |
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| JP6969235B2 (en) | 2021-11-24 |
| KR102378844B1 (en) | 2022-03-24 |
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| JP2018039999A (en) | 2018-03-15 |
| CN107805478B (en) | 2021-06-11 |
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