TW202323043A - Laminate body, epoxy film and wound body - Google Patents

Laminate body, epoxy film and wound body Download PDF

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Publication number
TW202323043A
TW202323043A TW111138004A TW111138004A TW202323043A TW 202323043 A TW202323043 A TW 202323043A TW 111138004 A TW111138004 A TW 111138004A TW 111138004 A TW111138004 A TW 111138004A TW 202323043 A TW202323043 A TW 202323043A
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Taiwan
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epoxy resin
epoxy
compound
laminate according
film
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TW111138004A
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Chinese (zh)
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光田祥貢
田村信人
塩田龍之介
三輪靖
桃平覚
土井伊織
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日商三菱化學股份有限公司
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Publication of TW202323043A publication Critical patent/TW202323043A/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/02Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B29C41/20Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles incorporating preformed parts or layers, e.g. moulding inserts or for coating articles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/34Component parts, details or accessories; Auxiliary operations
    • B29C41/52Measuring, controlling or regulating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/26Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/38Layered products comprising a layer of synthetic resin comprising epoxy resins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22Di-epoxy compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62Alcohols or phenols
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Epoxy Resins (AREA)
  • Laminated Bodies (AREA)
  • Moulding By Coating Moulds (AREA)

Abstract

This laminate body is provided at least with an epoxy resin layer, which is obtained by curing an epoxy resin composition that contains an epoxy resin (A) and an isocyanate compound (B), and a separation film. The epoxy resin (A) contains substantially no tri- or more functional epoxy resin, and when measuring the epoxy resin layer with DSC measurement, the temperature is increased to 20-250 DEG C at 10 DEG C/min, is then is decreased to 0 DEG C at 10 DEG C/min and is again increased to 0-250 DEG C at 10 DEG C/min, and the difference (T2-T1) between the glass transition temperature (T2) when increasing the temperature the second time and the glass transition temperature (T1) when increasing the temperature (T1) the first time is within 3 DEG C. An epoxy film can be achieved with good productivity and without problems occurring in post-processing.

Description

積層體、環氧膜及捲繞體Laminates, epoxy films and rolls

本發明係關於一種積層體、環氧膜及捲繞體。The present invention relates to a laminated body, an epoxy film and a winding body.

環氧樹脂由於耐熱性、接著性、耐水性、機械強度及電特性等優異,因此用於塗料、土木、接著、電子構件等各種領域。Epoxy resins are used in various fields such as paints, civil engineering, adhesives, and electronic components because of their excellent heat resistance, adhesiveness, water resistance, mechanical strength, and electrical properties.

例如,專利文獻1中揭示有一種使用特定高分子聚醚多元醇樹脂、3官能以上之環氧樹脂及環氧樹脂硬化劑之硬化性樹脂組合物,且記載有使該組合物硬化而成之硬化物由於耐熱性及耐彎曲性優異,因此可應用於可摺疊OLED(organic light emitting diode,有機發光二級體)顯示器。 先前技術文獻 專利文獻 For example, Patent Document 1 discloses a curable resin composition using a specific polymer polyether polyol resin, a trifunctional or more functional epoxy resin, and an epoxy resin hardener, and describes a method obtained by curing the composition. Since the cured product has excellent heat resistance and bending resistance, it can be applied to a foldable OLED (organic light emitting diode, organic light emitting diode) display. prior art literature patent documents

專利文獻1:國際公開第2020/080292號Patent Document 1: International Publication No. 2020/080292

[發明所欲解決之問題][Problem to be solved by the invention]

然而,上述專利文獻1中記載之硬化性樹脂組合物由於硬化時間長達1小時,因此於生產性方面需要進一步改善。However, the curable resin composition described in the above-mentioned Patent Document 1 needs to be further improved in terms of productivity because the curing time is as long as 1 hour.

另一方面,於將包含環氧樹脂之膜用於電子構件等之情形時,有時會在後續步驟中於該膜上設置硬塗層等功能層或設置配線。因此,要求該膜之表面對功能層或配線之潤濕性良好。 然而,可知根據膜之材料及其製作方法,有該膜表面之水滴接觸角變高,於後續步驟中產生密接性不良等不良情況之情形。 On the other hand, when a film containing an epoxy resin is used for an electronic component or the like, functional layers such as a hard coat layer or wiring may be provided on the film in a subsequent step. Therefore, the surface of the film is required to have good wettability to the functional layer or wiring. However, depending on the material of the film and its production method, it can be seen that the water droplet contact angle on the surface of the film may become high, and problems such as poor adhesion may occur in subsequent steps.

因此,本發明之課題在於獲得一種生產性良好且於後續步驟中不會產生不良情況之環氧膜。 [解決問題之技術手段] Therefore, the object of the present invention is to obtain an epoxy film which is good in productivity and does not cause troubles in the subsequent steps. [Technical means to solve the problem]

本發明人發現,於利用將包含環氧樹脂組合物之塗佈液塗佈於離型膜之方法製膜之情形時,藉由實質上不含3官能以上之環氧樹脂及併用異氰酸酯化合物,可縮短環氧膜硬化所需之時間,結果可降低與離型面接觸之時間,可解決上述問題。The inventors of the present invention have found that, in the case of forming a film by applying a coating liquid containing an epoxy resin composition to a release film, by substantially not containing an epoxy resin having a trifunctional or higher function and using an isocyanate compound in combination, It can shorten the time required for the hardening of the epoxy film, and as a result, the contact time with the release surface can be reduced, which can solve the above problems.

即,本發明具有以下態樣。 [1]一種積層體,其至少具備使含有環氧樹脂(A)及異氰酸酯化合物(B)之環氧樹脂組合物硬化而成之環氧樹脂層、及離型膜,且 上述環氧樹脂(A)實質上不含3官能以上之環氧樹脂, 藉由DSC(differential scanning calorimetry,示差掃描熱量測定法)測定,自20℃至250℃以10℃/min進行升溫,其後,以10℃/min降溫至0℃,再自0℃至250℃以10℃/min進行再升溫而測定上述環氧樹脂層時,再升溫時之玻璃轉移溫度(T2)與升溫時之玻璃轉移溫度(T1)之差(T2-T1)為3℃以內。 [2]如上述[1]所記載之積層體,其中上述環氧樹脂(A)係環氧化合物與酚系化合物反應而成之樹脂。 [3]如上述[2]所記載之積層體,其中上述環氧化合物係分子內具有2個以內環氧基之化合物。 [4]如上述[2]或[3]所記載之積層體,其中上述酚系化合物係具有2個以上與芳香環鍵結之羥基之化合物。 [5]如上述[1]至[4]中任一項所記載之積層體,其中上述環氧樹脂(A)之分子量為2,000~300,000。 [6]如上述[1]至[5]中任一項所記載之積層體,其中上述異氰酸酯化合物(B)係以脂肪族異氰酸酯為主骨架之化合物。 [7]如上述[1]至[6]中任一項所記載之積層體,其中上述環氧樹脂組合物含有調平劑。 [8]如上述[7]所記載之積層體,其中上述調平劑包含矽酮骨架及聚醚骨架。 [9]如上述[7]或[8]所記載之積層體,其中上述調平劑不含丙烯酸骨架。 [10]如上述[1]至[9]中任一項所記載之積層體,其中上述環氧樹脂層之玻璃轉移溫度為100℃以上。 [11]一種如上述[1]至[10]中任一項所記載之積層體之製造方法,其係藉由80℃~160℃之一次加熱處理及比一次加熱處理溫度高40~120℃之120~200℃之二次加熱處理,使上述環氧樹脂組合物硬化。 [12]一種環氧膜,其中包含上述含有環氧樹脂(A)及異氰酸酯化合物(B)之環氧樹脂組合物之環氧樹脂層的兩表面之水滴接觸角均為84度以下。 [13]如上述[12]所記載之環氧膜,其於至少一面具有功能層。 [14]一種捲繞體,其係將如上述[1]至[10]中任一項所記載之積層體或者如上述[12]或[13]所記載之環氧膜捲繞於芯體而成。 [15]如上述[1]至[10]中任一項所記載之積層體,其用於顯示器。 [16]如上述[12]或[13]所記載之環氧膜,其用於顯示器。 [發明之效果] That is, the present invention has the following aspects. [1] A laminate comprising at least an epoxy resin layer formed by curing an epoxy resin composition containing an epoxy resin (A) and an isocyanate compound (B), and a release film, and The epoxy resin (A) does not substantially contain a trifunctional or higher epoxy resin, Measured by DSC (differential scanning calorimetry, differential scanning calorimetry), the temperature is raised from 20°C to 250°C at 10°C/min, and then the temperature is lowered to 0°C at 10°C/min, and then from 0°C to 250°C When measuring the above-mentioned epoxy resin layer by reheating at 10°C/min, the difference (T2-T1) between the glass transition temperature (T2) during reheating and the glass transition temperature (T1) during heating is within 3°C. [2] The laminate according to the above [1], wherein the epoxy resin (A) is a resin obtained by reacting an epoxy compound and a phenol compound. [3] The laminate according to the above [2], wherein the epoxy compound is a compound having two or less epoxy groups in a molecule. [4] The laminate according to the above [2] or [3], wherein the phenolic compound is a compound having two or more hydroxyl groups bonded to an aromatic ring. [5] The laminate according to any one of the above [1] to [4], wherein the epoxy resin (A) has a molecular weight of 2,000 to 300,000. [6] The laminate according to any one of [1] to [5] above, wherein the isocyanate compound (B) is a compound having an aliphatic isocyanate as a main skeleton. [7] The laminate according to any one of the above [1] to [6], wherein the epoxy resin composition contains a leveling agent. [8] The laminate according to the above [7], wherein the leveling agent includes a silicone skeleton and a polyether skeleton. [9] The laminate according to the above [7] or [8], wherein the leveling agent does not contain an acrylic skeleton. [10] The laminate according to any one of [1] to [9] above, wherein the glass transition temperature of the epoxy resin layer is 100° C. or higher. [11] A method for producing the laminate as described in any one of [1] to [10] above, which comprises a heat treatment at 80°C to 160°C and a temperature 40 to 120°C higher than that of the heat treatment at the first time The second heat treatment at 120-200°C hardens the above-mentioned epoxy resin composition. [12] An epoxy film in which the water droplet contact angles on both surfaces of the epoxy resin layer comprising the epoxy resin composition containing the epoxy resin (A) and the isocyanate compound (B) are 84 degrees or less. [13] The epoxy film as described in [12] above, which has a functional layer on at least one surface. [14] A wound body in which the laminate described in any one of [1] to [10] above or the epoxy film described in [12] or [13] above is wound around a core made. [15] The laminate according to any one of [1] to [10] above, which is used for a display. [16] The epoxy film as described in [12] or [13] above, which is used for a display. [Effect of Invention]

根據本發明,可獲得一種生產性良好且於後續步驟中不會產生不良情況之環氧膜。According to the present invention, it is possible to obtain an epoxy film which is good in productivity and does not cause problems in subsequent steps.

以下,對本發明之一實施方式進行說明。然而,本發明並不限定於下述實施方式,可於不脫離本發明之主旨之範圍內進行各種變化。One embodiment of the present invention will be described below. However, this invention is not limited to the following embodiment, Various changes are possible in the range which does not deviate from the summary of this invention.

<<積層體(1)>> 本發明之一實施方式之積層體(1)(以下亦稱為「本積層體(1)」)係如下積層體:至少具備使含有環氧樹脂(A)及異氰酸酯化合物(B)之環氧樹脂組合物硬化而成之環氧樹脂層、及離型膜,且上述環氧樹脂(A)實質上不含3官能以上之環氧樹脂,藉由DSC測定,自20℃至250℃以10℃/min進行升溫,其後,以10℃/min降溫至0℃,再自0℃至250℃以10℃/min進行再升溫而測定上述環氧樹脂層時,再升溫時之玻璃轉移溫度(T2)與升溫時之玻璃轉移溫度(T1)之差(T2-T1)為3℃以內。 本積層體(1)中,環氧樹脂組合物含有異氰酸酯化合物(B)作為交聯劑,且上述環氧樹脂(A)實質上不含3官能以上之環氧樹脂,因此硬化所需之時間較短,生產性較高。又,本積層體(1)之環氧樹脂層之兩表面之水滴接觸角較佳為均為84度以下,即使於後續步驟中設置功能層或配線,亦不易產生密接性不良等不良情況。 再者,本發明中,環氧樹脂層之兩表面之水滴接觸角為84度以下之原因雖不明確,但認為其原因在於:由於環氧樹脂組合物之硬化時間較短,因此防止離型膜中所含之疏水性成分轉印,或環氧樹脂組合物中所含之疏水性基偏析等。 <<Laminate (1)>> A laminate (1) (hereinafter also referred to as "this laminate (1)") according to one embodiment of the present invention is a laminate comprising at least epoxy resin (A) and isocyanate compound (B). The epoxy resin layer and the release film formed by hardening the resin composition, and the above-mentioned epoxy resin (A) does not substantially contain the epoxy resin with more than three functionalities, measured by DSC, from 20°C to 250°C at 10 ℃/min to heat up, then cool down to 0°C at 10°C/min, then reheat at 10°C/min from 0°C to 250°C to measure the glass transition temperature of the above epoxy resin layer when reheating The difference (T2-T1) between (T2) and the glass transition temperature (T1) at the time of heating is within 3°C. In this laminate (1), the epoxy resin composition contains the isocyanate compound (B) as a crosslinking agent, and the above-mentioned epoxy resin (A) does not substantially contain a trifunctional or higher functional epoxy resin, so the time required for curing Shorter and more productive. In addition, the water droplet contact angles of both surfaces of the epoxy resin layer of the laminate (1) are preferably 84 degrees or less, so that even if functional layers or wiring are installed in subsequent steps, it is difficult to cause problems such as poor adhesion. Furthermore, in the present invention, although the reason why the water droplet contact angle on both surfaces of the epoxy resin layer is 84 degrees or less is not clear, it is considered that the reason is that the hardening time of the epoxy resin composition is relatively short, so the release of the epoxy resin composition is prevented. Transfer of hydrophobic components contained in the film, or segregation of hydrophobic groups contained in epoxy resin compositions, etc.

<環氧樹脂層> 本實施方式中之環氧樹脂層係使含有環氧樹脂(A)及異氰酸酯化合物(B)之環氧樹脂組合物硬化而成。 <Epoxy resin layer> The epoxy resin layer in this embodiment hardens the epoxy resin composition containing an epoxy resin (A) and an isocyanate compound (B).

[環氧樹脂組合物] 以下,對構成環氧樹脂組合物之各成分進行說明。 [Epoxy resin composition] Hereinafter, each component which comprises an epoxy resin composition is demonstrated.

1.環氧樹脂(A) 作為本實施方式中之環氧樹脂(A),例如可例舉:醇型環氧樹脂、雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚C型環氧樹脂、雙酚S型環氧樹脂、萘型環氧樹脂、苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、雙酚A酚醛清漆型環氧樹脂、聯苯型環氧樹脂、三苯甲烷型環氧樹脂、二環戊二烯型環氧樹脂、縮水甘油酯型環氧樹脂、縮水甘油胺型環氧樹脂、酚型環氧樹脂、脂肪族環氧樹脂、脂環式環氧樹脂、雜環式環氧樹脂、及該等結構任意組合而成之環氧樹脂等。 本實施方式中之環氧樹脂(A)可僅使用以上所例示之環氧樹脂中之一種,亦可以任意組合及比率併用兩種以上。 1. Epoxy resin (A) As the epoxy resin (A) in this embodiment, for example, alcohol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol C type epoxy resin, bisphenol S type epoxy resin, naphthalene type epoxy resin, phenol novolak type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin, biphenyl type epoxy resin, triphenylmethane type Epoxy resin, dicyclopentadiene epoxy resin, glycidyl ester epoxy resin, glycidylamine epoxy resin, phenolic epoxy resin, aliphatic epoxy resin, alicyclic epoxy resin, hetero Cyclic epoxy resin, and epoxy resin with any combination of these structures, etc. The epoxy resin (A) in this embodiment may use only 1 type of the epoxy resin illustrated above, and may use 2 or more types together in arbitrary combinations and ratios.

其中,作為本實施方式中之環氧樹脂(A),較佳為使用具有苯基骨架(酚骨架)、萘骨架、茀骨架、聯苯骨架、蒽骨架、芘骨架、𠮿

Figure 111138004-A0304-1
骨架、金剛烷骨架及二環戊二烯骨架中之至少一種骨架之環氧樹脂,就耐熱性之觀點而言,更佳為使用具有苯基骨架、茀骨架及聯苯骨架中之至少一種之環氧樹脂,就製造之容易性及耐熱性之觀點而言,進而較佳為使用具有雙酚A骨架、雙酚F骨架及聯苯骨架中之至少一種骨架之環氧樹脂。 環氧樹脂(A)之種類及骨架可藉由NMR(Nuclear Magnetic Resonance Spectroscopy,核磁共振光譜法)、IR(infrared radiation,紅外光譜法)、SEM(scanning electron microscope,掃描式電子顯微鏡)分析、IPC(高頻感應耦合電漿)發射光譜分析法、TGA(thermogravimetric analysis,熱重量分析)、DSC(differential scanning calorimetry,示差掃描熱量測定)及各種層析法等進行確認。 Among them, as the epoxy resin (A) in the present embodiment, it is preferable to use a resin having a phenyl skeleton (phenol skeleton), a naphthalene skeleton, a fennel skeleton, a biphenyl skeleton, an anthracene skeleton, a pyrene skeleton, a
Figure 111138004-A0304-1
As the epoxy resin having at least one skeleton among the skeleton, the adamantane skeleton, and the dicyclopentadiene skeleton, it is more preferable to use one having at least one of the phenyl skeleton, the fennel skeleton, and the biphenyl skeleton from the viewpoint of heat resistance. As the epoxy resin, it is more preferable to use an epoxy resin having at least one skeleton of a bisphenol A skeleton, a bisphenol F skeleton, and a biphenyl skeleton from the viewpoint of easiness of manufacture and heat resistance. The type and skeleton of the epoxy resin (A) can be analyzed by NMR (Nuclear Magnetic Resonance Spectroscopy, nuclear magnetic resonance spectroscopy), IR (infrared radiation, infrared spectroscopy), SEM (scanning electron microscope, scanning electron microscope), IPC (High-frequency inductively coupled plasma) emission spectroscopic analysis, TGA (thermogravimetric analysis, thermogravimetric analysis), DSC (differential scanning calorimetry, differential scanning calorimetry) and various chromatography methods for confirmation.

作為本實施方式中之環氧樹脂(A),較佳為以下所示之環氧樹脂(α)。As the epoxy resin (A) in this embodiment, the epoxy resin (α) shown below is preferable.

(環氧樹脂(α)) 環氧樹脂(α)係使環氧化合物與酚系化合物反應而成。 (epoxy resin (α)) The epoxy resin (α) is formed by reacting an epoxy compound and a phenolic compound.

=環氧化合物= 作為本實施方式中之環氧化合物,較佳為分子內具有2個以內環氧基之化合物。作為該化合物,可例舉2官能環氧化合物。 =Epoxy compound= As an epoxy compound in this Embodiment, the compound which has 2 or less epoxy groups in a molecule|numerator is preferable. As this compound, a bifunctional epoxy compound is mentioned.

作為2官能環氧化合物,例如可例舉:雙酚A二縮水甘油醚、雙酚F二縮水甘油醚、雙酚E二縮水甘油醚、雙酚C二縮水甘油醚、雙酚Z二縮水甘油醚、雙酚S二縮水甘油醚、雙酚AD二縮水甘油醚、雙酚苯乙酮二縮水甘油醚、雙酚三甲基環己烷二縮水甘油醚、雙酚茀二縮水甘油醚、四甲基雙酚A二縮水甘油醚、四甲基雙酚F二縮水甘油醚、四-第三丁基雙酚A二縮水甘油醚、四甲基雙酚S二縮水甘油醚等雙酚系二縮水甘油醚類;聯苯酚二縮水甘油醚、四甲基聯苯酚二縮水甘油醚、二甲基聯苯酚二縮水甘油醚、四-第三丁基聯苯酚二縮水甘油醚等聯苯酚系二縮水甘油醚類;對苯二酚二縮水甘油醚、甲基對苯二酚二縮水甘油醚、二丁基對苯二酚二縮水甘油醚、間苯二酚二縮水甘油醚、甲基間苯二酚二縮水甘油醚等苯二酚系二縮水甘油醚類;二氫蒽對苯二酚二縮水甘油醚、二羥基二苯醚二縮水甘油醚、硫代聯苯酚二縮水甘油醚、二羥基萘二縮水甘油醚等。Bifunctional epoxy compounds include, for example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol E diglycidyl ether, bisphenol C diglycidyl ether, bisphenol Z diglycidyl ether Ether, bisphenol S diglycidyl ether, bisphenol AD diglycidyl ether, bisphenol acetophenone diglycidyl ether, bisphenol trimethylcyclohexane diglycidyl ether, bisphenol trimethylcyclohexane diglycidyl ether, bisphenol fennel diglycidyl ether, four Methyl bisphenol A diglycidyl ether, tetramethyl bisphenol F diglycidyl ether, tetra-tertiary butyl bisphenol A diglycidyl ether, tetramethyl bisphenol S diglycidyl ether, etc. Glycidyl ethers; biphenol diglycidyl ether, tetramethyl biphenol diglycidyl ether, dimethyl biphenol diglycidyl ether, tetra-tertiary butyl biphenol diglycidyl ether, etc. Glyceryl ethers; Hydroquinone diglycidyl ether, methyl hydroquinone diglycidyl ether, dibutylhydroquinone diglycidyl ether, resorcinol diglycidyl ether, methyl resorcinol Diphenol-based diglycidyl ethers such as phenol diglycidyl ether; dihydroanthracene hydroquinone diglycidyl ether, dihydroxydiphenyl ether diglycidyl ether, thiobiphenol diglycidyl ether, dihydroxynaphthalene diglycidyl ether etc.

又,亦可例舉:於以上所例示之2官能環氧化合物之芳香環添加氫而得之環氧化合物;由己二酸、琥珀酸、鄰苯二甲酸(phthalic acid)、四氫鄰苯二甲酸、甲基六氫鄰苯二甲酸、對苯二甲酸、間苯二甲酸、鄰苯二甲酸(orthophthalic acid)、聯苯二羧酸、二聚酸等各種羧酸類與表鹵醇製造之環氧化合物;由二胺基二苯甲烷、胺基苯酚、苯二甲胺等各種胺化合物與表鹵醇製造之環氧化合物;僅包含乙二醇二縮水甘油醚、聚乙二醇二縮水甘油醚、丙二醇二縮水甘油醚、聚丙二醇二縮水甘油醚、1,4-丁二醇二縮水甘油醚、聚1,4-丁二醇二縮水甘油醚、1,5-戊二醇二縮水甘油醚、聚1,5-戊二醇二縮水甘油醚、1,6-己二醇二縮水甘油醚、聚1,6-己二醇二縮水甘油醚、1,7-庚二醇二縮水甘油醚、聚1,7-庚二醇二縮水甘油醚、1,8-辛二醇二縮水甘油醚、1,10-癸二醇二縮水甘油醚、2,2-二甲基-1,3-丙二醇二縮水甘油醚等鏈狀結構之(聚)伸烷基二醇二縮水甘油醚;具有1,4-環己烷二甲醇二縮水甘油醚等環狀結構之伸烷基二醇二縮水甘油醚等。In addition, it can also be exemplified: an epoxy compound obtained by adding hydrogen to the aromatic ring of the bifunctional epoxy compound exemplified above; adipic acid, succinic acid, phthalic acid, tetrahydrophthalic acid Formic acid, methylhexahydrophthalic acid, terephthalic acid, isophthalic acid, orthophthalic acid, biphenyl dicarboxylic acid, dimer acid and other carboxylic acids and epihalohydrin production ring Oxygen compounds; epoxy compounds made from various amine compounds such as diaminodiphenylmethane, aminophenol, xylylenediamine and epihalohydrin; only ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, poly-1,4-butanediol diglycidyl ether, 1,5-pentanediol diglycidyl ether Ether, poly-1,5-pentanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, poly-1,6-hexanediol diglycidyl ether, 1,7-heptanediol diglycidyl ether ether, poly 1,7-heptanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3 -(poly)alkylene glycol diglycidyl ether with a chain structure such as propylene glycol diglycidyl ether; alkylene glycol diglycidyl ether with a ring structure such as 1,4-cyclohexanedimethanol diglycidyl ether Glyceryl ether etc.

本實施方式中之環氧化合物可僅使用以上所例示之環氧化合物中之一種,亦可以任意組合及比率併用兩種以上。 其中,就抑制反應時之凝膠化,並且獲得具有適合膜化之分子量之共聚物之觀點而言,較佳為2官能環氧化合物,就環氧樹脂層之透明性之觀點而言,更佳為雙酚系二縮水甘油醚類,其中,就環氧樹脂層之透明性及耐熱性之觀點而言,進而較佳為雙酚A二縮水甘油醚。 As the epoxy compound in this embodiment, only one of the epoxy compounds exemplified above may be used, or two or more of them may be used in any combination and ratio. Among these, bifunctional epoxy compounds are preferred from the viewpoint of suppressing gelation during the reaction and obtaining a copolymer having a molecular weight suitable for film formation, and more preferably from the viewpoint of transparency of the epoxy resin layer. Bisphenol-based diglycidyl ethers are preferable, and among them, bisphenol A diglycidyl ether is more preferable from the viewpoint of transparency and heat resistance of the epoxy resin layer.

又,環氧樹脂(A)必須實質上不含3官能以上之環氧樹脂。此處,「實質上不含」意指相對於2官能以內之環氧樹脂100質量份,含有2.0質量份以下之3官能以上環氧樹脂,較佳為1.5質量份以下,其中特佳為1.0質量份以下,最佳為0.5質量份以下。 藉由滿足上述範圍,環氧樹脂之硬化反應迅速進行,可獲得具有所需特性(膜表面之潤濕性、耐彎曲性)之環氧膜。 In addition, the epoxy resin (A) must not substantially contain a trifunctional or higher epoxy resin. Here, "substantially free" means containing 2.0 parts by mass or less of a trifunctional or higher epoxy resin, preferably 1.5 parts by mass or less, particularly preferably 1.0 parts by mass, with respect to 100 parts by mass of epoxy resins within a bifunctionality. It is not more than 0.5 parts by mass, preferably not more than 0.5 parts by mass. By satisfying the above range, the curing reaction of the epoxy resin proceeds rapidly, and an epoxy film having desired properties (wettability of the film surface, bending resistance) can be obtained.

=酚系化合物= 本實施方式中之酚系化合物較佳為具有2個以上與芳香環鍵結之羥基之化合物。 =Phenolic compound= The phenolic compound in this embodiment is preferably a compound having two or more hydroxyl groups bonded to an aromatic ring.

作為酚系化合物,例如可例舉:雙酚A、雙酚F、雙酚E、雙酚C、雙酚Z、雙酚S、雙酚AD、雙酚苯乙酮、雙酚三甲基環己烷、雙酚茀、四甲基雙酚A、四甲基雙酚F、四-第三丁基雙酚A、四甲基雙酚S等雙酚類;聯苯酚、四甲基聯苯酚、二甲基聯苯酚、四-第三丁基聯苯酚等聯苯酚類;對苯二酚、甲基對苯二酚、二丁基對苯二酚、間苯二酚、甲基間苯二酚等苯二酚類;二氫蒽對苯二酚等二氫蒽對苯二酚類;二羥基二苯醚等二羥基二苯醚類;硫代聯苯酚等硫代聯苯酚類;二羥基萘等二羥基萘類;二羥基茋等二羥基茋類;苯酚酚醛清漆樹脂類、甲酚酚醛清漆樹脂類、雙酚A酚醛清漆樹脂等雙酚系酚醛清漆樹脂類;萘酚酚醛清漆樹脂、苯酚芳烷基樹脂、萜酚樹脂、二環戊二烯苯酚樹脂、苯酚聯伸苯樹脂、酚改性二甲苯樹脂等各種酚樹脂類、及藉由該等各種酚類與羥基苯甲醛、巴豆醛、乙二醛等各種醛類之縮合反應而得之多酚樹脂類;重油或瀝青類、酚類及甲醛類之共縮合樹脂等各種酚系化合物等。Examples of phenolic compounds include bisphenol A, bisphenol F, bisphenol E, bisphenol C, bisphenol Z, bisphenol S, bisphenol AD, bisphenol acetophenone, bisphenol trimethylcyclo Bisphenols such as hexane, bisphenol fennel, tetramethylbisphenol A, tetramethylbisphenol F, tetra-tertiary butylbisphenol A, tetramethylbisphenol S; biphenol, tetramethylbiphenol , dimethyl biphenol, tetra-tertiary butyl biphenol and other biphenols; hydroquinone, methyl hydroquinone, dibutyl hydroquinone, resorcinol, methyl resorcinol Dihydroquinones such as phenol; dihydroanthracene hydroquinones such as dihydroanthracene hydroquinone; dihydroxydiphenyl ethers such as dihydroxydiphenyl ether; thiobiphenols such as thiobiphenol; Dihydroxynaphthalene such as naphthalene; dihydroxystilbene such as dihydroxystilbene; bisphenol novolac resin such as phenol novolac resin, cresol novolak resin, bisphenol A novolak resin; naphthol novolac resin, Various phenol resins such as phenol aralkyl resins, terpene phenol resins, dicyclopentadiene phenol resins, phenol biphenyl resins, phenol-modified xylene resins, and hydroxybenzaldehyde, croton, etc. Polyphenol resins obtained by the condensation reaction of various aldehydes such as aldehydes and glyoxal; various phenolic compounds such as co-condensation resins of heavy oil or asphalt, phenols and formaldehyde, etc.

本實施方式中之酚系化合物可僅使用以上所例示之酚系化合物中之一種,亦可以任意組合及比率併用兩種以上。 其中,就抑制與上述縮水甘油醚反應時凝膠化,並且獲得具有適合膜化之分子量之共聚物之觀點、以及環氧樹脂層之透明性及耐熱性之觀點而言,較佳為雙酚類。 As the phenolic compound in this embodiment, only one of the above-exemplified phenolic compounds may be used, or two or more of them may be used in any combination and ratio. Among them, bisphenol is preferable from the viewpoint of suppressing gelation when reacting with the above-mentioned glycidyl ether, and obtaining a copolymer having a molecular weight suitable for film formation, and the transparency and heat resistance of the epoxy resin layer. kind.

=環氧化合物及酚系化合物之使用量= 製備環氧樹脂(α)時,相對於環氧化合物1.00莫耳,酚系化合物之使用量較佳為0.05莫耳以上,更佳為0.10莫耳以上,進而較佳為0.15莫耳以上,進而更佳為0.20莫耳以上。 另一方面,相對於環氧化合物1.00莫耳,酚系化合物之使用量較佳為1.25莫耳以下,更佳為1.20莫耳以下,進而較佳為1.15莫耳以下,進而更佳為1.10莫耳以下。 若酚系化合物之使用量為上述下限值以上,則分子量增長,就該方面而言較佳。尤其是於該範圍內,當想要獲得低分子量之環氧化合物時,可減少酚系化合物之量,當想要獲得高分子量之環氧化合物時,可增加酚系化合物。另一方面,若為上述上限值以下,則容易獲得硬化性良好之環氧化合物,故而較佳。 =Amount of epoxy compound and phenolic compound used= When preparing the epoxy resin (α), the amount of the phenolic compound used is preferably 0.05 mole or more, more preferably 0.10 mole or more, more preferably 0.15 mole or more, and more preferably 0.15 mole or more, relative to 1.00 mole of the epoxy compound. More preferably, it is 0.20 mol or more. On the other hand, with respect to 1.00 mol of the epoxy compound, the use amount of the phenolic compound is preferably 1.25 mol or less, more preferably 1.20 mol or less, further preferably 1.15 mol or less, still more preferably 1.10 mol below the ears. When the usage-amount of a phenolic compound is more than the said lower limit, molecular weight will increase, and it is preferable in this point. Especially within this range, when it is desired to obtain a low molecular weight epoxy compound, the amount of the phenolic compound can be reduced, and when it is desired to obtain a high molecular weight epoxy compound, the amount of the phenolic compound can be increased. On the other hand, since it is easy to obtain the epoxy compound with favorable curability as it is below the said upper limit, it is preferable.

=觸媒= 製備環氧樹脂(α)時,可使用觸媒使上述環氧化合物與上述酚系化合物反應。製造環氧樹脂(α)時使用之觸媒並無特別限定,只要為具有促進環氧基與酚性羥基、醇性羥基或羧基反應之催化能力之化合物即可。作為觸媒,例如可例舉:鹼金屬化合物、有機磷化合物、三級胺、四級銨鹽、環狀胺類、咪唑類等。 =Catalyst= When producing an epoxy resin (α), the above-mentioned epoxy compound and the above-mentioned phenolic compound can be reacted using a catalyst. The catalyst used in the production of the epoxy resin (α) is not particularly limited, as long as it is a compound capable of promoting the reaction of epoxy groups with phenolic hydroxyl groups, alcoholic hydroxyl groups or carboxyl groups. As a catalyst, an alkali metal compound, an organophosphorus compound, a tertiary amine, a quaternary ammonium salt, cyclic amines, imidazoles etc. are mentioned, for example.

作為上述鹼金屬化合物,例如可例舉:氫氧化鈉、氫氧化鋰、氫氧化鉀等鹼金屬氫氧化物;碳酸鈉、碳酸氫鈉、氯化鈉、氯化鋰、氯化鉀等鹼金屬鹽;甲醇鈉、乙醇鈉等鹼金屬烷氧化物;鹼金屬苯氧化物;氫化鈉、氫化鋰等鹼金屬之氫化物;乙酸鈉、硬脂酸鈉等有機酸之鹼金屬鹽等。Examples of the alkali metal compound include: alkali metal hydroxides such as sodium hydroxide, lithium hydroxide, and potassium hydroxide; alkali metals such as sodium carbonate, sodium bicarbonate, sodium chloride, lithium chloride, and potassium chloride; Salts; alkali metal alkoxides such as sodium methoxide and sodium ethoxide; alkali metal phenoxides; alkali metal hydrides such as sodium hydride and lithium hydride; alkali metal salts of organic acids such as sodium acetate and sodium stearate, etc.

作為上述有機磷化合物之具體例,可例舉:三正丙基膦、三正丁基膦、三苯基膦、溴化四甲基鏻、碘化四甲基鏻、氫氧化四甲基鏻、氯化三甲基環己基鏻、溴化三甲基環己基鏻、氯化三甲基苄基鏻、溴化三甲基苄基鏻、溴化四苯基鏻、溴化三苯基甲基鏻、碘化三苯基甲基鏻、氯化三苯基乙基鏻、溴化三苯基乙基鏻、碘化三苯基乙基鏻、氯化三苯基苄基鏻、溴化三苯基苄基鏻等。Specific examples of the above organophosphorus compounds include: tri-n-propylphosphine, tri-n-butylphosphine, triphenylphosphine, tetramethylphosphonium bromide, tetramethylphosphonium iodide, tetramethylphosphonium hydroxide , Trimethylcyclohexylphosphonium chloride, Trimethylcyclohexylphosphonium bromide, Trimethylbenzylphosphonium chloride, Trimethylbenzylphosphonium bromide, Tetraphenylphosphonium bromide, Triphenylmethyl bromide Phosphonium, triphenylmethylphosphonium iodide, triphenylethylphosphonium chloride, triphenylethylphosphonium bromide, triphenylethylphosphonium iodide, triphenylbenzylphosphonium chloride, bromide Triphenylbenzylphosphonium, etc.

作為上述三級胺類,例如可例舉:三乙胺、三正丙胺、三正丁胺、三乙醇胺、二甲苄胺等。As said tertiary amines, triethylamine, tri-n-propylamine, tri-n-butylamine, triethanolamine, dimethylbenzylamine, etc. are mentioned, for example.

作為上述四級銨鹽,例如可例舉:氯化四甲基銨、溴化四甲基銨、氫氧化四甲基銨、氯化三乙基甲基銨、氯化四乙基銨、溴化四乙基銨、碘化四乙基銨、溴化四丙基銨、氫氧化四丙基銨、氯化四丁基銨、溴化四丁基銨、碘化四丁基銨、氯化苄基三甲基銨、溴化苄基三甲基銨、氫氧化苄基三甲基銨、氯化苄基三丁基銨、氯化苯基三甲基銨等。As the above-mentioned quaternary ammonium salt, for example, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium hydroxide, triethylmethylammonium chloride, tetraethylammonium chloride, bromine Tetraethylammonium chloride, tetraethylammonium iodide, tetrapropylammonium bromide, tetrapropylammonium hydroxide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium chloride Benzyltrimethylammonium, benzyltrimethylammonium bromide, benzyltrimethylammonium hydroxide, benzyltributylammonium chloride, phenyltrimethylammonium chloride, and the like.

作為上述環狀胺類,例如可例舉:1,8-二氮雜雙環(5,4,0)-7-十一烯、1,5二氮雜雙環(4,3,0)-5-壬烯等。Examples of the cyclic amines include: 1,8-diazabicyclo(5,4,0)-7-undecene, 1,5-diazabicyclo(4,3,0)-5 - Nonene etc.

作為上述咪唑類,例如可例舉:2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑等。As said imidazoles, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole etc. are mentioned, for example.

再者,本實施方式中之其他觸媒可僅使用以上所例示之化合物中之一種,亦可以任意組合及比率併用兩種以上。In addition, as other catalysts in this embodiment, only one of the compounds exemplified above may be used, or two or more of them may be used in any combination and ratio.

反應固形物成分中,觸媒之使用量通常較佳為0.001~1質量%。藉由使觸媒之使用量為上述下限值以上,容易實現高分子量化,且藉由使觸媒之使用量為上述上限值以下,容易抑制凝膠化。再者,反應固形物成分係指反應體系內除溶劑以外之反應基質之合計。In the reaction solids, the amount of the catalyst used is generally preferably 0.001 to 1% by mass. When the usage-amount of a catalyst is more than the said lower limit, it becomes easy to achieve high molecular weight, and when the usage-amount of a catalyst is below the said upper limit, it becomes easy to suppress gelation. Furthermore, the reaction solid content refers to the total of the reaction substrates in the reaction system except the solvent.

=溶劑= 製備環氧樹脂(α)時,上述環氧化合物與上述酚系化合物之反應步驟中可使用溶劑。 上述溶劑並無特別限定,只要為使環氧化合物、酚系化合物及其他原料溶解者即可,通常為有機溶劑,例如可例舉:芳香族系溶劑、酮系溶劑、醯胺系溶劑、二醇醚系溶劑等。 =Solvent= When preparing an epoxy resin (α), a solvent may be used in the step of reacting the epoxy compound and the phenolic compound. The above-mentioned solvent is not particularly limited, as long as it dissolves epoxy compounds, phenolic compounds and other raw materials, it is usually an organic solvent, for example, aromatic solvents, ketone solvents, amide solvents, Alcohol ether solvents, etc.

作為上述芳香族系溶劑,例如可例舉:苯、甲苯、二甲苯等。 作為上述酮系溶劑,例如可例舉:丙酮、甲基乙基酮、甲基異丁基酮、2-庚酮、4-庚酮、2-辛酮、環戊酮、環己酮、乙醯丙酮等。 作為上述醯胺系溶劑,例如可例舉:甲醯胺、N-甲基甲醯胺、N,N-二甲基甲醯胺、乙醯胺、N-甲基乙醯胺、N,N-二甲基乙醯胺、2-吡咯啶酮、N-甲基吡咯啶酮等。 作為上述二醇醚系溶劑,例如可例舉:乙二醇單甲醚、乙二醇單乙醚、乙二醇單正丁醚、乙二醇二甲醚、乙二醇單乙醚乙酸酯、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單正丁醚、二乙二醇二甲醚、二乙二醇單乙醚乙酸酯、丙二醇單甲醚、丙二醇單正丁醚、丙二醇單甲醚乙酸酯等。 As said aromatic solvent, benzene, toluene, xylene, etc. are mentioned, for example. Examples of the above-mentioned ketone-based solvent include: acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, 4-heptanone, 2-octanone, cyclopentanone, cyclohexanone, ethyl Acetone, etc. Examples of the above-mentioned amide-based solvents include formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N - Dimethylacetamide, 2-pyrrolidone, N-methylpyrrolidone and the like. Examples of the glycol ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol mono-n-butyl ether Butyl ether, propylene glycol monomethyl ether acetate, etc.

再者,本實施方式中之溶劑可僅使用以上所例示之溶劑中之一種,亦可以任意組合及比率併用兩種以上。In addition, as the solvent in this embodiment, only one of the solvents exemplified above may be used, or two or more of them may be used in any combination and ratio.

=反應條件= 上述環氧化合物與上述酚系化合物之反應可藉由公知方法進行。 反應體系可為常壓、加壓、減壓之任意條件。 又,反應溫度通常為80~240℃,較佳為100~220℃,更佳為120~200℃。若反應溫度為上述下限以上,則反應容易進行,故而較佳。又,若反應溫度為上述上限以下,則副反應不易進行,獲得高純度之環氧化合物,就該觀點而言較佳。 反應時間並無特別限定,通常為0.5~24小時,較佳為1~22小時,進而較佳為1.5~20小時。若反應時間為上述上限值以下,則提高生產效率,就該方面而言較佳,若為上述下限值以上,則可減少未反應成分,就該方面而言較佳。 =Reaction Condition= The reaction of the said epoxy compound and the said phenolic compound can be performed by a well-known method. The reaction system can be under any conditions of normal pressure, increased pressure, or reduced pressure. In addition, the reaction temperature is usually 80 to 240°C, preferably 100 to 220°C, more preferably 120 to 200°C. Since reaction is easy to progress that reaction temperature is more than the said minimum, it is preferable. Moreover, when reaction temperature is below the said upper limit, a side reaction will not progress easily, and it is preferable from this viewpoint to obtain a high-purity epoxy compound. The reaction time is not particularly limited, but is usually 0.5 to 24 hours, preferably 1 to 22 hours, and more preferably 1.5 to 20 hours. If the reaction time is not more than the above-mentioned upper limit, it is preferable in terms of improving production efficiency, and when it is more than the above-mentioned lower limit, it is preferable in that point that unreacted components can be reduced.

(環氧樹脂(A)之分子量) 環氧樹脂(A)之分子量較佳為2,000~300,000,更佳為10,000~100,000。 若分子量為上述下限以上,則可獲得具有充分彈性及伸長率之環氧樹脂層。另一方面,若為上述上限以下,則可不限溶劑種類而獲得適合有效率之膜化之塗佈液。 再者,分子量係藉由如下方法進行測定:使用凝膠滲透層析法(GPC),確定為基於聚苯乙烯標準之換算值。 (Molecular weight of epoxy resin (A)) The molecular weight of the epoxy resin (A) is preferably from 2,000 to 300,000, more preferably from 10,000 to 100,000. An epoxy resin layer which has sufficient elasticity and elongation as a molecular weight is more than the said minimum is obtained. On the other hand, if it is below the said upper limit, the coating liquid suitable for efficient film formation can be obtained regardless of the kind of solvent. In addition, molecular weight was measured by the method which used the gel permeation chromatography (GPC), and determined it as the conversion value based on the polystyrene standard.

(環氧樹脂(A)之環氧當量) 環氧樹脂(A)之環氧當量較佳為100 g/eq以上,更佳為200 g/eq以上,進而較佳為300 g/eq以上,進而更佳為500 g/eq以上。 另一方面,環氧當量較佳為200,000 g/eq以下,更佳為150,000 g/eq以下,進而較佳為100,000 g/eq以下,進而更佳為50,000 g/eq以下。 若環氧當量為上述下限值以上,則就環氧化合物之可撓性之觀點而言較佳,若為上述上限值以下,則使下述含有環氧化合物之組合物硬化時,環氧基間之交聯點間密度變高,容易獲得硬化物性,就該方面而言較佳。 再者,本發明中,「環氧當量」定義為「含有1當量之環氧基之環氧化合物之質量」,可依據JIS K7236進行測定。 (Epoxy equivalent of epoxy resin (A)) The epoxy equivalent of the epoxy resin (A) is preferably at least 100 g/eq, more preferably at least 200 g/eq, further preferably at least 300 g/eq, still more preferably at least 500 g/eq. On the other hand, the epoxy equivalent is preferably at most 200,000 g/eq, more preferably at most 150,000 g/eq, further preferably at most 100,000 g/eq, still more preferably at most 50,000 g/eq. If the epoxy equivalent is more than the above-mentioned lower limit, then it is preferable from the viewpoint of the flexibility of the epoxy compound, and if it is below the above-mentioned upper limit, when the composition containing the epoxy compound described below is cured, the ring It is preferable in that the density between crosslinking points between oxygen groups becomes high, and hardening physical properties are easily obtained. In addition, in this invention, "epoxy equivalent" is defined as "the mass of the epoxy compound containing the epoxy group of 1 equivalent", and it can measure based on JISK7236.

2.異氰酸酯化合物(B) 藉由本實施方式中之環氧樹脂組合物含有異氰酸酯化合物(B)作為交聯劑,可加快硬化速度,光學特性及耐熱性、耐溶劑性良好。 再者,本發明中,「交聯劑」係指有助於環氧樹脂(A)之環氧基間之交聯反應及/或擴鏈反應之成分。 2. Isocyanate compound (B) When the epoxy resin composition in this embodiment contains an isocyanate compound (B) as a crosslinking agent, the hardening speed can be accelerated, and optical characteristics, heat resistance, and solvent resistance are favorable. Furthermore, in the present invention, "crosslinking agent" refers to a component that contributes to the crosslinking reaction and/or chain extension reaction between the epoxy groups of the epoxy resin (A).

作為本實施方式中之異氰酸酯化合物(B),例如可例舉:甲基環己烷二異氰酸酯、六亞甲基二異氰酸酯、氫化苯二甲基二異氰酸酯、二環己基甲烷二異氰酸酯、異佛爾酮二異氰酸酯、二聚酸二異氰酸酯、三甲基六亞甲基二異氰酸酯等脂肪族系異氰酸酯;甲苯二異氰酸酯、苯二甲基二異氰酸酯、二苯基甲烷二異氰酸酯等芳香族系異氰酸酯;離胺酸三異氰酸酯等。 又,亦可例舉:藉由以上所例示之異氰酸酯化合物與具有胺基、羥基、羧基、水等活性氫原子之化合物反應而得之異氰酸酯化合物(例如,異氰酸酯化合物之加成物、異氰酸酯化合物之縮二脲體等)、或以上所例示之異氰酸酯化合物之三~五聚物(例如,異氰酸酯化合物之異氰尿酸酯體等)等。 As the isocyanate compound (B) in this embodiment, for example, methylcyclohexane diisocyanate, hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexylmethane diisocyanate, isophor Aliphatic isocyanates such as ketone diisocyanate, dimer acid diisocyanate, and trimethylhexamethylene diisocyanate; aromatic isocyanates such as toluene diisocyanate, xylylene diisocyanate, and diphenylmethane diisocyanate; free amines acid triisocyanate, etc. Also, isocyanate compounds obtained by reacting the above-exemplified isocyanate compounds with compounds having active hydrogen atoms such as amine groups, hydroxyl groups, carboxyl groups, and water (for example, adducts of isocyanate compounds, isocyanate compounds Biuret, etc.), or tri-pentamers of the above-exemplified isocyanate compounds (for example, isocyanurate of isocyanate compounds, etc.), and the like.

本實施方式中之異氰酸酯化合物(B)可僅使用以上所例示之異氰酸酯化合物中之一種,亦可以任意組合及比率併用兩種以上。 其中,就膜之透明性、耐候性之觀點而言,較佳為以脂肪族異氰酸酯為主骨架之化合物,更佳為以六亞甲基二異氰酸酯為主骨架之化合物。 As the isocyanate compound (B) in this embodiment, only one of the isocyanate compounds exemplified above may be used, or two or more of them may be used in any combination and ratio. Among them, a compound having an aliphatic isocyanate as a main skeleton is preferable from the viewpoint of film transparency and weather resistance, and a compound having a hexamethylene diisocyanate as a main skeleton is more preferable.

相對於環氧樹脂(A)100質量份,本實施方式中之異氰酸酯化合物(B)之含量較佳為0.1~100質量份,更佳為1~80質量份,進而較佳為5~60質量份。The content of the isocyanate compound (B) in the present embodiment is preferably 0.1 to 100 parts by mass, more preferably 1 to 80 parts by mass, and still more preferably 5 to 60 parts by mass, based on 100 parts by mass of the epoxy resin (A). share.

3.其他成分 本實施方式中之環氧樹脂組合物可含有除上述環氧樹脂(A)及異氰酸酯化合物(B)以外之成分。 作為上述其他成分,例如可例舉:除上述異氰酸酯化合物(B)以外之交聯劑、調平劑、溶劑、硬化促進劑(但是,相當於上述交聯劑者除外)、偶合劑、阻燃劑、抗氧化劑、光穩定劑、塑化劑、反應性稀釋劑、填充顏料、無機填充材料、有機填充材料等。上述其他成分可根據環氧樹脂組合物所需之物性適當組合使用。 3. Other ingredients The epoxy resin composition in this embodiment may contain components other than the above-mentioned epoxy resin (A) and isocyanate compound (B). Examples of the above-mentioned other components include: crosslinking agents other than the above-mentioned isocyanate compound (B), leveling agents, solvents, hardening accelerators (except those corresponding to the above-mentioned crosslinking agents), coupling agents, flame retardants, etc. Agents, antioxidants, light stabilizers, plasticizers, reactive diluents, filler pigments, inorganic fillers, organic fillers, etc. The above-mentioned other components can be used in appropriate combination according to the required physical properties of the epoxy resin composition.

(交聯劑) 作為除上述異氰酸酯化合物(B)以外之交聯劑,例如可例舉:多官能酚類、胺系化合物、酸酐系化合物、咪唑系化合物、醯胺系化合物、陽離子聚合起始劑、有機膦類等。 (crosslinking agent) Examples of crosslinking agents other than the above-mentioned isocyanate compound (B) include polyfunctional phenols, amine compounds, acid anhydride compounds, imidazole compounds, amide compounds, cationic polymerization initiators, and organic phosphines. wait.

作為上述多官能酚類,例如可例舉:雙酚A、雙酚F、雙酚S、雙酚B、雙酚AD、雙酚Z、四溴雙酚A等雙酚類;4,4'-聯苯酚、3,3',5,5'-四甲基-4,4'-聯苯酚等聯苯酚類;鄰苯二酚、間苯二酚、對苯二酚、二羥基萘類;及與該等化合物之芳香環鍵結之氫原子經鹵基、烷基、芳基、醚基、酯基、包含硫、磷、矽等雜原子之有機取代基等非干擾性取代基取代者等。 又,亦可例舉以上所例示之酚類或苯酚、甲酚、烷基苯酚等單官能酚類與醛類之縮聚物即酚醛清漆類、可溶酚醛類等。 Examples of the polyfunctional phenols include bisphenols such as bisphenol A, bisphenol F, bisphenol S, bisphenol B, bisphenol AD, bisphenol Z, and tetrabromobisphenol A; 4,4′ -Biphenol, 3,3',5,5'-tetramethyl-4,4'-biphenol and other biphenols; catechol, resorcinol, hydroquinone, dihydroxynaphthalene; And the hydrogen atoms bonded to the aromatic rings of these compounds are substituted by non-interfering substituents such as halogen groups, alkyl groups, aryl groups, ether groups, ester groups, organic substituents including heteroatoms such as sulfur, phosphorus, and silicon wait. Also, novolaks, resols, etc., which are polycondensates of the phenols exemplified above or monofunctional phenols such as phenol, cresol, and alkylphenol, and aldehydes can also be mentioned.

作為上述胺系化合物,例如可例舉:脂肪族一級胺、二級胺、三級胺;芳香族一級胺、二級胺、三級胺;環狀胺;胍類;脲衍生物等,具體而言,可例舉:三乙四胺、二胺基二苯甲烷、二胺基二苯醚、間苯二甲胺、雙氰胺、1,8-二氮雜雙環(5,4,0)-7-十一烯、1,5-二氮雜雙環(4,3,0)-5-壬烯、二甲基脲、胍脲等。Examples of the above-mentioned amine compounds include: aliphatic primary amines, secondary amines, and tertiary amines; aromatic primary amines, secondary amines, and tertiary amines; cyclic amines; guanidines; urea derivatives, etc., specifically For example, triethylenetetramine, diaminodiphenylmethane, diaminodiphenyl ether, m-xylylenediamine, dicyandiamide, 1,8-diazabicyclo (5,4,0 )-7-undecene, 1,5-diazabicyclo(4,3,0)-5-nonene, dimethylurea, guanidine urea, etc.

作為上述酸酐系化合物,例如可例舉:鄰苯二甲酸酐、六氫鄰苯二甲酸酐、偏苯三甲酸酐、順丁烯二酸酐與不飽和化合物之縮合物等。As said acid anhydride type compound, the condensation product of phthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, maleic anhydride, and an unsaturated compound etc. are mentioned, for example.

作為上述咪唑系化合物,例如可例舉:1-異丁基-2-甲基咪唑、2-甲基咪唑、1-苄基-2-甲基咪唑、1-苄基-2-苯基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、苯并咪唑等。Examples of the imidazole-based compounds include: 1-isobutyl-2-methylimidazole, 2-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole , 2-ethyl-4-methylimidazole, 2-phenylimidazole, benzimidazole, etc.

作為上述醯胺系化合物,例如可例舉:雙氰胺及其衍生物、聚醯胺樹脂等。As said amide-type compound, dicyandiamide and its derivative(s), polyamide resin, etc. are mentioned, for example.

上述陽離子聚合起始劑係藉由熱或活性能量線照射而產生陽離子者,例如可例舉芳香族鎓鹽等。具體而言,可例舉包含SbF 6 -、BF 4 -、AsF 6 -、PF 6 -、CF 3SO 3、B(C 6F 5) 4-等陰離子成分及含有碘、硫、氮、磷等原子之芳香族陽離子成分的化合物等。其中,較佳為二芳基錪鹽、三芳基鋶鹽。 The above-mentioned cationic polymerization initiator is one that generates cations by heat or active energy ray irradiation, and examples thereof include aromatic onium salts and the like. Concretely, it includes anion components such as SbF 6 - , BF 4 - , AsF 6 - , PF 6 - , CF 3 SO 3 , B(C 6 F 5 ) 4- , and iodine, sulfur, nitrogen, and phosphorus. Compounds of equiatomic aromatic cation components, etc. Among them, diaryliumium salts and triaryliumium salts are preferred.

作為上述有機膦類,例如可例舉:三丁基膦、甲基二苯基膦、三苯基膦、二苯基膦、苯基膦等,作為鏻鹽,可例舉:四苯基硼酸四苯基鏻、乙基三苯基硼酸四苯基鏻、四丁基硼酸四丁基鏻等,作為四苯基硼鹽,可例舉:2-乙基-4-甲基咪唑四苯基硼酸鹽、N-甲基𠰌啉四苯基硼酸鹽等。Examples of the above-mentioned organic phosphines include tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, and phenylphosphine, and examples of the phosphonium salt include tetraphenylboronic acid. Tetraphenylphosphonium, tetraphenylphosphonium ethyl triphenyl borate, tetrabutyl phosphonium tetrabutyl borate, etc., as tetraphenyl boron salts, for example: 2-ethyl-4-methylimidazolium tetraphenyl Borate, N-methyl phylloline tetraphenyl borate, etc.

於使用多官能酚類、胺系化合物、酸酐系化合物之情形時,較佳為以如下方式使用:相對於環氧樹脂組合物中之所有環氧基,按交聯劑中之官能基(多官能酚類之羥基、胺系化合物之胺基或酸酐系化合物之酸酐基)之當量比計成為0.01~1.5之範圍。 於使用咪唑系化合物之情形時,較佳為相對於所有環氧成分100質量份,以0.001~10質量份之範圍使用。 於使用醯胺系化合物之情形時,較佳為於環氧樹脂組合物100質量%中以0.001~20質量%之範圍使用。 於使用陽離子聚合起始劑之情形時,較佳為相對於所有環氧成分100質量份,以0.001~15質量份之範圍使用。 於使用有機膦類之情形時,較佳為於環氧樹脂組合物100質量%中以0.001~20質量%之範圍使用。 When using multifunctional phenols, amine compounds, and acid anhydride compounds, it is preferable to use them in the following manner: with respect to all epoxy groups in the epoxy resin composition, according to the functional groups in the crosslinking agent (poly The equivalent ratio of the hydroxyl group of the functional phenol, the amine group of the amine compound, or the acid anhydride group of the acid anhydride compound) is in the range of 0.01 to 1.5. When using an imidazole compound, it is preferable to use it in the range of 0.001-10 mass parts with respect to 100 mass parts of all epoxy components. When using an amide compound, it is preferable to use it in the range of 0.001-20 mass % in 100 mass % of epoxy resin compositions. When using a cationic polymerization initiator, it is preferable to use it in the range of 0.001-15 mass parts with respect to 100 mass parts of all epoxy components. When using an organic phosphine, it is preferable to use it in the range of 0.001-20 mass % in 100 mass % of epoxy resin compositions.

(調平劑) 為了使製成膜時之表面外觀良好,本實施方式中之環氧樹脂組合物可添加調平劑。若添加調平劑,則亦可控制環氧樹脂層表面之水滴接觸角。 作為調平劑,例如可例舉:矽烷偶合劑等矽酮系、聚丙烯酸酯系及全氟烷基系調平劑。調平劑可僅使用以上所例示者中之一種,亦可以任意組合及比率併用兩種以上。其中,作為調平劑,就表面外觀及控制環氧樹脂層表面之水滴接觸角之方面而言,較佳為使用聚醚改性矽酮、矽酮大分子單體改性丙烯酸酯、聚醚大分子單體改性丙烯酸酯、矽酮-聚醚大分子單體改性丙烯酸酯等。進而,就光學特性之方面而言,更佳為使用包含聚醚改性矽酮等矽酮骨架及聚醚骨架之調平劑。 又,為了防止膜乾燥過程中發生收縮,調平劑較佳為不含丙烯酸骨架。 相對於環氧樹脂100質量份,環氧樹脂組合物中之調平劑之含量較佳為0.01~3質量份之範圍,更佳為0.05~2質量份之範圍,進而較佳為0.1~1質量份之範圍。 (leveling agent) In order to improve the surface appearance when formed into a film, a leveling agent may be added to the epoxy resin composition in this embodiment. If a leveling agent is added, the contact angle of water droplets on the surface of the epoxy resin layer can also be controlled. As a leveling agent, silicone type, polyacrylate type, and perfluoroalkyl type leveling agents, such as a silane coupling agent, are mentioned, for example. As the leveling agent, only one of the above-exemplified ones may be used, or two or more of them may be used in any combination and ratio. Among them, as a leveling agent, it is preferable to use polyether-modified silicone, silicone macromer-modified acrylate, polyether Macromer modified acrylate, silicone-polyether macromer modified acrylate, etc. Furthermore, in terms of optical properties, it is more preferable to use a leveling agent containing a silicone skeleton such as polyether-modified silicone and a polyether skeleton. Also, in order to prevent the film from shrinking during drying, the leveling agent preferably does not contain an acrylic skeleton. The content of the leveling agent in the epoxy resin composition is preferably in the range of 0.01 to 3 parts by mass, more preferably in the range of 0.05 to 2 parts by mass, and further preferably in the range of 0.1 to 1 part by mass relative to 100 parts by mass of the epoxy resin. The range of parts by mass.

(溶劑) 本實施方式中之環氧樹脂組合物可添加溶劑而調整環氧樹脂組合物之固形物成分濃度。 作為溶劑,通常只要使環氧樹脂(A)、異氰酸酯化合物(B)及其他成分溶解即可,可使用與作為製備上述環氧樹脂(α)時使用之溶劑所例舉者相同者。 溶劑較佳為以環氧樹脂組合物之固形物成分濃度為10~90質量%之方式使用,更佳為以環氧樹脂組合物之固形物成分濃度為20~80質量%之方式使用。 (solvent) The epoxy resin composition in this embodiment can add a solvent to adjust the solid content concentration of the epoxy resin composition. As a solvent, what is necessary is just to dissolve an epoxy resin (A), an isocyanate compound (B), and other components normally, and what was mentioned as a solvent used for the said epoxy resin (α) preparation can be used as an example. The solvent is preferably used so that the solid content concentration of the epoxy resin composition is 10 to 90% by mass, more preferably used so that the solid content concentration of the epoxy resin composition is 20 to 80% by mass.

[硬化物(環氧樹脂層)] 環氧樹脂層係使上述環氧樹脂組合物硬化而成之硬化物。 再者,本發明中之「硬化」意指藉由熱及/或光等使環氧樹脂組合物刻意地硬化。硬化之程度可根據所需物性、用途進行選擇,於本發明中,就即使於後續步驟中進行熱處理,硬化物之物性亦不會發生變化之觀點而言,必須完全硬化。 關於環氧樹脂層是否完全硬化,可依據JIS K7121,藉由示差掃描熱量計測定玻璃轉移溫度,根據此時升溫時及再升溫時之玻璃轉移溫度來確認。於本發明中,將再升溫時之玻璃轉移溫度(T2)與升溫時之玻璃轉移溫度(T1)之差(T2-T1)為3℃以內的情形視為完全硬化。T2-T1較佳為2℃以內,進而較佳為1℃以內。 [cured product (epoxy resin layer)] The epoxy resin layer is a cured product obtained by curing the above-mentioned epoxy resin composition. In addition, "hardening" in this invention means hardening an epoxy resin composition intentionally by heat and/or light etc. The degree of hardening can be selected according to the desired physical properties and applications. In the present invention, it is necessary to be completely hardened from the viewpoint that the physical properties of the hardened product do not change even if heat treatment is performed in a subsequent step. Whether the epoxy resin layer is completely cured can be confirmed by measuring the glass transition temperature with a differential scanning calorimeter according to JIS K7121, and confirming it according to the glass transition temperature when the temperature is raised at this time and when the temperature is raised again. In the present invention, the case where the difference (T2-T1) between the glass transition temperature (T2) at the time of reheating and the glass transition temperature (T1) at the time of heating is within 3° C. is regarded as complete hardening. T2-T1 is preferably within 2°C, more preferably within 1°C.

環氧樹脂層較佳為兩表面之水滴接觸角均為84度以下,因此即使於後續步驟中設置功能層或配線,亦不易產生密接性不良等不良情況。就該觀點而言,環氧樹脂層之兩表面之水滴接觸角更佳為80度以下。 再者,水滴接觸角係藉由實施例記載之方法進行測定。 The epoxy resin layer is preferably such that the contact angles of water droplets on both surfaces are 84 degrees or less, so even if a functional layer or wiring is provided in a subsequent step, it is not easy to cause problems such as poor adhesion. From this viewpoint, the water droplet contact angle of both surfaces of the epoxy resin layer is more preferably 80 degrees or less. Furthermore, the water droplet contact angle was measured by the method described in the examples.

環氧樹脂層之厚度較佳為1~1000 μm,更佳為5~500 μm,進而較佳為10~300 μm。 若環氧樹脂層之厚度為上述範圍,則具有適度操作性及耐彎曲性,因此適合用於電子構件。 The thickness of the epoxy resin layer is preferably from 1 to 1000 μm, more preferably from 5 to 500 μm, and still more preferably from 10 to 300 μm. When the thickness of the epoxy resin layer is within the above-mentioned range, it has moderate handleability and bending resistance, so it is suitable for use in electronic components.

環氧樹脂層之玻璃轉移溫度較佳為100℃以上,更佳為110℃以上,進而較佳為115℃以上,進而更佳為120℃以上,特佳為126℃以上。 若玻璃轉移溫度為上述範圍,則環氧樹脂層之耐熱性良好。 尤其是於玻璃轉移溫度為126℃以上之情形時,有耐彎曲性亦變得良好之傾向。 玻璃轉移溫度之上限值並無特別限制,但就膜之可撓性之方面而言,較佳為220℃以下,進而較佳為190℃以下。 The glass transition temperature of the epoxy resin layer is preferably at least 100°C, more preferably at least 110°C, further preferably at least 115°C, still more preferably at least 120°C, particularly preferably at least 126°C. The heat resistance of an epoxy resin layer becomes favorable that a glass transition temperature is the said range. In particular, when the glass transition temperature is 126° C. or higher, bending resistance also tends to become favorable. The upper limit of the glass transition temperature is not particularly limited, but is preferably 220°C or lower, more preferably 190°C or lower, from the viewpoint of film flexibility.

於環氧樹脂層用於顯示器等電子構件之情形時,較佳為透明性較高。 就該觀點而言,環氧樹脂層於400 nm下之透光率較佳為75%以上,更佳為80%以上,進而較佳為85%以上,進而更佳為88%以上。 又,環氧樹脂層於650 nm下之透光率較佳為80%以上,更佳為85%以上,進而較佳為90%以上。 又,環氧樹脂層之霧度較佳為5%以下,更佳為3%以下,進而較佳為1%以下。 又,環氧樹脂層之黃度(YI)較佳為5以下,更佳為3以下,進而更佳為1以下。 再者,透光率及霧度係藉由實施例記載之方法進行測定。 When an epoxy resin layer is used for electronic components, such as a display, it is preferable that transparency is high. From this point of view, the light transmittance of the epoxy resin layer at 400 nm is preferably at least 75%, more preferably at least 80%, further preferably at least 85%, and even more preferably at least 88%. In addition, the light transmittance of the epoxy resin layer at 650 nm is preferably at least 80%, more preferably at least 85%, and still more preferably at least 90%. Moreover, the haze of the epoxy resin layer is preferably 5% or less, more preferably 3% or less, and still more preferably 1% or less. Moreover, the yellowness (YI) of an epoxy resin layer becomes like this. Preferably it is 5 or less, More preferably, it is 3 or less, More preferably, it is 1 or less. In addition, light transmittance and haze are measured by the method described in an Example.

於環氧樹脂層用於軟性顯示器等電子構件之情形時,較佳為具有耐彎曲性。 耐彎曲性係藉由於反覆彎曲試驗中例如進行20萬次反覆彎曲試驗時不會產生龜裂及折痕之最小彎曲半徑R進行評估。環氧樹脂層之R較佳為3 mm以下,更佳為2 mm以下,進而較佳為1.5 mm以下,進而更佳為1 mm以下。若最大彎曲半徑R為上述範圍,則用於軟性顯示器等電子構件之情形時之對彎曲之耐久性良好。 When the epoxy resin layer is used for electronic components such as flexible displays, it is preferable to have bending resistance. The bending resistance is evaluated by the minimum bending radius R that does not cause cracks and creases in repeated bending tests, for example, 200,000 times. The R of the epoxy resin layer is preferably at most 3 mm, more preferably at most 2 mm, further preferably at most 1.5 mm, even more preferably at most 1 mm. When the maximum bending radius R is within the above range, durability against bending when used in electronic components such as flexible displays is good.

<離型膜> 作為本實施方式中之離型膜,可例舉以紙、樹脂、金屬等為原料之片狀者。其中,就價格便宜,容易加工,又,容易廢棄及再利用之方面而言,較佳為紙或樹脂,就透明性之方面而言,更佳為樹脂。 <Release film> As the release film in the present embodiment, a sheet-like one made of paper, resin, metal, or the like may, for example, be mentioned. Among them, paper or resin is preferable in terms of low price, easy processing, and easy disposal and recycling, and resin is more preferable in terms of transparency.

作為紙,例如可使用高級紙、牛皮紙、玻璃紙、羊皮紙及超級壓光牛皮紙等表面經矽酮塗佈處理者。As paper, for example, high-grade paper, kraft paper, cellophane, parchment, and super-calendered kraft paper whose surface is treated with silicone coating can be used.

作為樹脂膜,例如可使用以聚乙烯、聚丙烯等聚烯烴、聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯等聚酯、聚醯亞胺或聚碳酸酯為主成分之膜。可於該等之表面塗佈矽酮樹脂離型劑等而調整剝離強度。 上述樹脂膜中,就外觀、加工容易性、耐久性、耐熱性、成本等方面而言,較佳為包含以聚酯為主成分之樹脂膜。只要不超出本發明之主旨即可,上述樹脂膜可為單層構成,亦可為兩層以上之多層構成。 再者,「主成分樹脂」意指構成基材之樹脂中含量最多之樹脂,具體而言,係指占50質量%以上、較佳為70質量%以上、更佳為80質量%以上、進而較佳為90質量%以上(包括100質量%)之樹脂。 As the resin film, for example, a film mainly composed of polyolefin such as polyethylene and polypropylene, polyester such as polyethylene terephthalate and polyethylene naphthalate, polyimide, or polycarbonate can be used. . The peeling strength can be adjusted by coating silicone resin release agent etc. on the surface. Among the above-mentioned resin films, a resin film containing polyester as a main component is preferable in terms of appearance, ease of processing, durability, heat resistance, cost, and the like. As long as it does not deviate from the spirit of the present invention, the above-mentioned resin film may be composed of a single layer or a multilayer structure of two or more layers. Furthermore, "main component resin" refers to the resin with the largest content among the resins constituting the base material, specifically, it refers to the resin accounting for 50% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, and furthermore More than 90% by mass (including 100% by mass) of resin is preferable.

上述聚酯較佳為使芳香族二羧酸與脂肪族二醇縮聚而獲得者。聚酯可為包含一種芳香族二羧酸及一種脂肪族二醇之聚酯,亦可為進而與一種以上其他成分共聚而成之共聚聚酯。 作為芳香族二羧酸,可例舉:對苯二甲酸、2,6-萘二甲酸等,作為脂肪族二醇,可例舉:乙二醇、二乙二醇、1,4-環己烷二甲醇等。 另一方面,作為用作共聚聚酯之其他成分之二羧酸,可例舉:間苯二甲酸、鄰苯二甲酸、對苯二甲酸、2,6-萘二甲酸、癸二酸,作為二醇成分,可例舉:乙二醇、二乙二醇、丙二醇、丁二醇、1,4-環己烷二甲醇、新戊二醇等。又,亦可使用對羥基苯甲酸等羥基羧酸。 作為代表性聚酯,可例示:使對苯二甲酸與乙二醇縮聚而得之聚對苯二甲酸乙二酯、使2,6-萘二甲酸與乙二醇縮聚而得之聚萘二甲酸乙二酯等。 聚酯膜可為非延伸膜,亦可為延伸膜,就機械強度之觀點而言,較佳為延伸膜,更佳為雙軸延伸膜。又,可對聚酯膜預先實施電暈處理、電漿處理等表面處理。 The above-mentioned polyester is preferably obtained by polycondensing an aromatic dicarboxylic acid and an aliphatic diol. The polyester may be a polyester comprising an aromatic dicarboxylic acid and an aliphatic diol, or may be a copolyester obtained by further copolymerizing with one or more other components. Examples of aromatic dicarboxylic acids include terephthalic acid and 2,6-naphthalene dicarboxylic acid, and examples of aliphatic diols include ethylene glycol, diethylene glycol, and 1,4-cyclohexyl alkanedimethanol, etc. On the other hand, examples of dicarboxylic acids used as other components of the copolyester include isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalene dicarboxylic acid, and sebacic acid. As a diol component, ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, 1, 4- cyclohexanedimethanol, neopentyl glycol, etc. are mentioned, for example. In addition, hydroxycarboxylic acids such as p-hydroxybenzoic acid can also be used. Examples of typical polyesters include polyethylene terephthalate obtained by polycondensing terephthalic acid and ethylene glycol, and polyethylene naphthalate obtained by polycondensing 2,6-naphthalene dicarboxylic acid and ethylene glycol. Ethylene formate, etc. The polyester film may be an unstretched film or a stretched film, and is preferably a stretched film, more preferably a biaxially stretched film, from the viewpoint of mechanical strength. In addition, surface treatments such as corona treatment and plasma treatment may be given to the polyester film in advance.

又,離型膜可為如下構造:除上述樹脂膜以外,進而包含離型層作為與環氧樹脂層接觸之側之最表面層。藉由離型膜除樹脂膜以外進而包含離型層,環氧樹脂層與離型膜之剝離性良好。In addition, the release film may have a structure that further includes a release layer as the outermost layer on the side in contact with the epoxy resin layer in addition to the resin film described above. Since the release film further includes the release layer in addition to the resin film, the peelability between the epoxy resin layer and the release film becomes favorable.

離型層之構成成分並無特別限制,可含有矽酮化合物、氟化合物、蠟類、界面活性劑等。就價格與離型性之平衡性良好之方面而言,較佳為使用矽酮化合物。 進而,為了調整離型層之剝離性,可併用剝離控制劑。 The composition of the release layer is not particularly limited, and may contain silicone compounds, fluorine compounds, waxes, surfactants, and the like. It is preferable to use a silicone compound in terms of a good balance between price and releasability. Furthermore, in order to adjust the releasability of a release layer, a peel control agent can be used together.

作為可用作包含樹脂膜及離型層之離型膜之市售品獲取者,可例舉:Toyobo Film Solution股份有限公司製造之「Purex A31」;三菱化學股份有限公司製造之「MRF-38」、「MRF-75」;三井化學Tohcello股份有限公司製造之「SP-PET(註冊商標)」。Commercially available products that can be used as a release film including a resin film and a release layer include: "Purex A31" manufactured by Toyobo Film Solution Co., Ltd.; "MRF-38" manufactured by Mitsubishi Chemical Corporation. ", "MRF-75"; "SP-PET (registered trademark)" manufactured by Mitsui Chemicals Tohcello Co., Ltd.

<<積層體(1)之製造方法>> 本實施方式中之積層體(1)係藉由將包含上述環氧樹脂組合物之塗佈液塗佈於離型膜並使其硬化而獲得。 <<Manufacturing method of laminate (1)>> The laminate (1) in this embodiment is obtained by applying the coating liquid containing the said epoxy resin composition to a release film and hardening it.

將塗佈液塗佈於離型膜上之方法可為公知方法。作為該塗佈方法,例如可例舉:缺角輪塗佈法、凹版塗佈法、反向塗佈法、刮塗法、浸漬塗佈法、噴塗法、氣刀塗佈法、旋轉塗佈法、輥塗法、印刷法、斜板式塗佈法、淋幕式塗佈法、模嘴塗佈法、鑄造法、棒式塗佈法、擠壓塗佈法等。The method of applying a coating liquid to a release film may be a known method. Examples of such coating methods include chipping wheel coating, gravure coating, reverse coating, blade coating, dip coating, spray coating, air knife coating, and spin coating. Coating method, roll coating method, printing method, inclined plate coating method, curtain coating method, die coating method, casting method, rod coating method, extrusion coating method, etc.

塗佈液之硬化條件可根據組合物中之成分及調配量適當調整,較佳為於80~200℃下加熱1~180分鐘之條件。就減少硬化不良之方面而言,該加熱較佳為藉由兩個階段處理來進行,即於80~160℃下進行1~30分鐘之一次加熱、及於比一次加熱溫度高40~120℃之120~200℃下進行1~150分鐘之二次加熱。The hardening conditions of the coating liquid can be appropriately adjusted according to the ingredients and the compounding amount in the composition, and the conditions of heating at 80-200°C for 1-180 minutes are preferred. In terms of reducing poor hardening, the heating is preferably carried out by two-stage treatment, that is, the first heating at 80-160°C for 1-30 minutes, and the heating at a temperature 40-120°C higher than the first heating temperature. The second heating is carried out at 120-200°C for 1-150 minutes.

<<環氧膜>> 藉由將離型膜自本發明中之積層體(1)剝離,獲得環氧膜。 即,本發明之一實施方式之環氧膜包含含有環氧樹脂(A)及異氰酸酯化合物(B),且上述環氧樹脂(A)實質上不含3官能以上之環氧樹脂的環氧樹脂組合物,藉由DSC測定,自20℃至250℃以10℃/min進行升溫,其後,以10℃/min降溫至0℃,再自0℃至250℃以10℃/min進行再升溫而測定上述環氧樹脂層時,再升溫時之玻璃轉移溫度(T2)與升溫時之玻璃轉移溫度(T1)之差(T2-T1)為3℃以內。 如上所述,本發明之環氧膜之兩表面之水滴接觸角均為84度以下,因此即使於後續步驟中設置功能層或配線,亦不易產生密接性不良等不良情況。再者,水滴接觸角之測定方法如實施例所記載。 <<Epoxy film>> An epoxy film is obtained by peeling the release film from the laminate (1) in the present invention. That is, the epoxy film according to one embodiment of the present invention includes an epoxy resin containing an epoxy resin (A) and an isocyanate compound (B), and the epoxy resin (A) does not substantially contain a trifunctional or higher epoxy resin. The composition, measured by DSC, is heated from 20°C to 250°C at 10°C/min, then cooled to 0°C at 10°C/min, and then reheated at 10°C/min from 0°C to 250°C When measuring the above-mentioned epoxy resin layer, the difference (T2-T1) between the glass transition temperature (T2) and the glass transition temperature (T1) when the temperature is raised again is within 3°C. As mentioned above, the contact angles of water droplets on both surfaces of the epoxy film of the present invention are 84 degrees or less, so even if a functional layer or wiring is provided in a subsequent step, problems such as poor adhesion are not likely to occur. Furthermore, the measurement method of the water droplet contact angle is as described in the examples.

於在環氧膜之至少一面設置功能層之情形時,作為該功能層,可例舉:硬塗層、抗靜電層、防眩層、低反射層、抗反射層、防污層等。功能層可為單層且具有上述複數種功能,亦可積層兩層以上具有各功能之層。When a functional layer is provided on at least one side of the epoxy film, the functional layer may, for example, be a hard coat layer, an antistatic layer, an antiglare layer, a low reflection layer, an antireflection layer, or an antifouling layer. The functional layer may be a single layer having multiple functions as described above, or two or more layers having each function may be laminated.

(硬塗層) 若於環氧膜之至少一面設置硬塗層,則可對環氧膜之表面賦予耐損傷性、耐化學品性等。 硬塗層較佳為由硬化性樹脂組合物形成。上述硬化性樹脂組合物並無特別限定,例如只要為藉由照射電子束、放射線或紫外線等能量線而硬化者或藉由加熱而硬化者即可,就成形時間及生產性之觀點而言,較佳為紫外線硬化性樹脂組合物。 (hard coat) When a hard coat layer is provided on at least one surface of an epoxy film, damage resistance, chemical resistance, etc. can be provided to the surface of an epoxy film. The hard coat layer is preferably formed of a curable resin composition. The above-mentioned curable resin composition is not particularly limited, for example, as long as it is cured by irradiation with energy rays such as electron beams, radiation, or ultraviolet rays, or cured by heating. From the viewpoint of molding time and productivity, Preferable is an ultraviolet curable resin composition.

作為構成硬化性樹脂組合物之硬化性樹脂之較佳例,可例舉:丙烯酸酯化合物、胺基甲酸酯丙烯酸酯化合物、環氧丙烯酸酯化合物、羧基改性環氧丙烯酸酯化合物、聚酯丙烯酸酯化合物、共聚系丙烯酸酯、脂環式環氧樹脂、縮水甘油醚環氧樹脂、乙烯醚化合物及氧雜環丁烷化合物等。該等硬化性樹脂可單獨使用一種或組合使用兩種以上。 其中,作為賦予優異之表面硬度之硬化性樹脂,例如可例舉:多官能丙烯酸酯化合物、多官能胺基甲酸酯丙烯酸酯化合物或多官能環氧丙烯酸酯化合物等自由基聚合系硬化性化合物;及烷氧基矽烷或烷基烷氧基矽烷等熱聚合系硬化性化合物。 Preferred examples of the curable resin constituting the curable resin composition include acrylate compounds, urethane acrylate compounds, epoxy acrylate compounds, carboxyl-modified epoxy acrylate compounds, polyester Acrylate compounds, copolymerized acrylates, alicyclic epoxy resins, glycidyl ether epoxy resins, vinyl ether compounds, oxetane compounds, etc. These hardening resins can be used individually by 1 type or in combination of 2 or more types. Among them, examples of curable resins that impart excellent surface hardness include radically polymerizable curable compounds such as polyfunctional acrylate compounds, polyfunctional urethane acrylate compounds, and polyfunctional epoxy acrylate compounds. ; and thermally polymerizable hardening compounds such as alkoxysilanes or alkylalkoxysilanes.

進而,上述硬化性樹脂組合物可為上述硬化性樹脂中含有無機成分之有機、無機混合系硬化性樹脂組合物。作為上述有機、無機混合系硬化性樹脂組合物,可例舉包含上述硬化性樹脂中含有具有反應性官能基之無機成分之硬化性樹脂組合物者。利用此種具有反應性官能基之無機成分,例如使該無機成分與自由基聚合性單體共聚及交聯,藉此與有機黏合劑中僅含有無機成分之有機、無機複合系硬化性樹脂組合物相比,不易產生硬化收縮,且可表現出較高之表面硬度。進而,就減少硬化收縮之觀點而言,亦較佳為包含紫外線反應性膠體二氧化矽作為具有反應性官能基之無機成分之有機、無機混合系硬化性樹脂組合物。Furthermore, the above-mentioned curable resin composition may be an organic-inorganic hybrid curable resin composition containing an inorganic component in the above-mentioned curable resin. Examples of the above-mentioned organic-inorganic hybrid curable resin composition include curable resin compositions containing an inorganic component having a reactive functional group in the above-mentioned curable resin. Using such an inorganic component with a reactive functional group, for example, copolymerize and cross-link the inorganic component with a radically polymerizable monomer, thereby combining with an organic-inorganic composite curable resin containing only inorganic components in the organic binder Compared with materials, it is not easy to produce hardening shrinkage, and can exhibit higher surface hardness. Furthermore, an organic-inorganic hybrid curable resin composition containing ultraviolet-ray reactive colloidal silica as an inorganic component having a reactive functional group is also preferable from the viewpoint of reducing curing shrinkage.

形成硬塗層之硬化性樹脂組合物除上述硬化性樹脂以外,亦可包含調平劑、光聚合起始劑、折射率調整成分、潤滑劑、抗氧化劑、紫外線吸收劑、抗靜電劑、阻燃劑、填料、玻璃纖維及二氧化矽等。The curable resin composition for forming the hard coat layer may contain a leveling agent, a photopolymerization initiator, a refractive index adjusting component, a lubricant, an antioxidant, an ultraviolet absorber, an antistatic agent, an antistatic agent, and Combustion agent, filler, glass fiber and silicon dioxide, etc.

<<捲繞體>> 本發明中之積層體(1)及環氧膜可藉由捲繞於芯體而捲取成卷狀。 積層體(1)及環氧膜之長度並無特別限定,就後續步驟中之操作性之觀點而言,較佳為5 m以上,更佳為10 m以上,進而較佳為50 m以上。又,積層體(1)及環氧膜之長度較佳為10000 m以下。 <<Wound body>> The laminate (1) and the epoxy film in the present invention can be wound into a roll by being wound around a core. The length of the laminate (1) and the epoxy film is not particularly limited, but is preferably at least 5 m, more preferably at least 10 m, and still more preferably at least 50 m from the viewpoint of workability in the subsequent steps. Also, the length of the laminate (1) and the epoxy film is preferably 10000 m or less.

再者,芯體係指用於膜之捲取之圓柱形捲芯。芯體之材料並無特別限定,例如可例舉:紙、樹脂浸漬紙、丙烯腈-丁二烯-苯乙烯共聚物(ABS樹脂)、FRP(Fiber Reinforced Plastic,纖維強化塑膠)、酚樹脂、含無機物之樹脂。其中,就熱膨脹係數較小,剛性較高,對濕度之膨潤性較低,且捲繞性優異之觀點而言,較佳為包含丙烯腈-丁二烯-苯乙烯共聚物(ABS樹脂)、FRP、酚樹脂、含無機物之樹脂等樹脂。 於芯體之材料為紙之情形時,藉由尤其是利用樹脂等塗佈其表面,容易獲得所需特性。進而,就表面平滑性之觀點而言,芯體亦較佳為樹脂浸漬紙管。 Furthermore, the core system refers to a cylindrical core used for winding up of the film. The material of the core is not particularly limited, for example, paper, resin impregnated paper, acrylonitrile-butadiene-styrene copolymer (ABS resin), FRP (Fiber Reinforced Plastic, fiber reinforced plastic), phenolic resin, Resins containing inorganic substances. Among them, it is preferable to include acrylonitrile-butadiene-styrene copolymer (ABS resin), Resins such as FRP, phenolic resins, and resins containing inorganic substances. In the case where the material of the core is paper, desired characteristics are easily obtained by coating the surface thereof with, inter alia, resin or the like. Furthermore, the core is also preferably a resin-impregnated paper tube from the viewpoint of surface smoothness.

<<用途>> 本發明之積層體及環氧膜由於環氧樹脂層之兩表面之水滴接觸角較高,且與功能層或配線之密接性良好,因此可適宜用於顯示器、印刷配線板等電子構件用途。其中,特佳為顯示器。 [實施例] <<Application>> The laminate and epoxy film of the present invention can be suitably used for electronic components such as displays and printed wiring boards because the epoxy resin layer has a high water droplet contact angle on both surfaces and has good adhesion to functional layers or wiring. Among them, particularly preferred is a display. [Example]

其次,藉由實施例更詳細地說明本發明。然而,本發明並不限定於以下說明之實施例。Next, the present invention is described in more detail by examples. However, the present invention is not limited to the Examples described below.

<材料> 實施例及比較例中所用之材料如下所述。 <Material> Materials used in Examples and Comparative Examples are as follows.

[環氧樹脂] (A-1):使用雙酚A型環氧樹脂(三菱化學股份有限公司製造之「YL7852BT40」,重量平均分子量49,280,環氧當量6,740 g/eq)。 (A-2):使用雙酚A酚醛清漆型環氧樹脂(三菱化學股份有限公司製造之「jER157S65」,環氧當量208 g/eq)。 [epoxy resin] (A-1): A bisphenol A type epoxy resin ("YL7852BT40" manufactured by Mitsubishi Chemical Corporation, weight average molecular weight 49,280, epoxy equivalent 6,740 g/eq) was used. (A-2): A bisphenol A novolac type epoxy resin ("jER157S65" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 208 g/eq) was used.

[交聯劑] (B-1):使用以六亞甲基二異氰酸酯為主成分之聚異氰酸酯(東曹股份有限公司製造之「Coronate 2715」)。 (B-2):使用1-苄基-2-苯基咪唑(四國化成股份有限公司製造之「Curezol 1B2PZ」)。 (B-3):使用2-乙基-4(5)-甲基咪唑(三菱化學股份有限公司製造之「EMI-24」)。 [Crosslinking agent] (B-1): A polyisocyanate ("Coronate 2715" manufactured by Tosoh Corporation) mainly composed of hexamethylene diisocyanate was used. (B-2): 1-benzyl-2-phenylimidazole ("Curezol 1B2PZ" manufactured by Shikoku Chemicals Co., Ltd.) was used. (B-3): 2-Ethyl-4(5)-methylimidazole ("EMI-24" manufactured by Mitsubishi Chemical Corporation) was used.

[添加劑] (C-1):使用調平劑(BYK-Chemie Japan股份有限公司製造之「BYK-3566」,矽酮及聚醚大分子單體改性丙烯酸酯)。 (C-2):使用調平劑(BYK-Chemie Japan股份有限公司製造之「BYK-333」,聚醚改性矽酮)。 [additive] (C-1): A leveling agent ("BYK-3566" manufactured by BYK-Chemie Japan Co., Ltd., silicone and polyether macromonomer-modified acrylate) was used. (C-2): A leveling agent ("BYK-333" manufactured by BYK-Chemie Japan Co., Ltd., polyether-modified silicone) was used.

[溶劑] (D-1):甲苯 (D-2):甲基乙基酮 [solvent] (D-1): Toluene (D-2): Methyl ethyl ketone

[離型膜] 使用三井化學Tohcello股份有限公司製造之「SP-PET(註冊商標)O3-BU」(100 μm)作為包含聚酯膜及矽酮系離型層之離型膜。 [Release film] "SP-PET (registered trademark) O3-BU" (100 μm) manufactured by Mitsui Chemicals Tohcello Co., Ltd. was used as a release film including a polyester film and a silicone-based release layer.

<積層體之製作> [實施例1] 以表1記載之比率混合環氧樹脂(A-1)、交聯劑(B-1)及(B-2)、溶劑(D-1)及(D-2),製備塗佈液。 使用敷料器將塗佈液塗佈於離型膜上,使用恆溫乾燥機於80℃下一次加熱2分鐘,且於180℃下二次加熱5分鐘而進行硬化處理,自然冷卻至室溫(25℃),藉此形成環氧樹脂層,獲得實施例1之積層體。所得之環氧樹脂層之厚度為25 μm。 將所得之環氧樹脂層自離型膜剝離,測定玻璃轉移溫度。玻璃轉移溫度為130℃,再升溫時之玻璃轉移溫度為130℃,因此確認到完全硬化。 <Making of laminated body> [Example 1] Epoxy resin (A-1), crosslinking agents (B-1) and (B-2), and solvents (D-1) and (D-2) were mixed in the ratio described in Table 1 to prepare a coating liquid. Use an applicator to apply the coating liquid on the release film, heat it once at 80°C for 2 minutes using a constant temperature dryer, and heat it at 180°C for 5 minutes for a second time to harden, and cool it naturally to room temperature (25 °C), thereby forming an epoxy resin layer to obtain the laminate of Example 1. The resulting epoxy resin layer had a thickness of 25 μm. The obtained epoxy resin layer was peeled from the release film, and the glass transition temperature was measured. The glass transition temperature was 130°C, and the glass transition temperature at the time of reheating was 130°C, so complete hardening was confirmed.

[實施例2] 將添加劑(C-1)以表1記載之比率添加,除此以外,以與實施例1相同之條件形成環氧樹脂層,獲得實施例2之積層體。所得之環氧樹脂層之厚度為25 μm。 將所得之環氧樹脂層自離型膜剝離,測定玻璃轉移溫度。玻璃轉移溫度為128℃,再升溫時之玻璃轉移溫度為129℃,因此確認到完全硬化。 [Example 2] Except having added the additive (C-1) at the ratio described in Table 1, the epoxy resin layer was formed on the same conditions as Example 1, and the laminated body of Example 2 was obtained. The resulting epoxy resin layer had a thickness of 25 μm. The obtained epoxy resin layer was peeled from the release film, and the glass transition temperature was measured. The glass transition temperature was 128°C, and the glass transition temperature at the time of reheating was 129°C, so complete hardening was confirmed.

[實施例3] 將添加劑(C-2)以表1記載之比率添加,除此以外,以與實施例1相同之條件形成環氧樹脂層,獲得實施例3之積層體。所得之環氧樹脂層之厚度為25 μm。 將所得之環氧樹脂層自離型膜剝離,測定玻璃轉移溫度。玻璃轉移溫度為128℃,再升溫時之玻璃轉移溫度為129℃,因此確認到完全硬化。 [Example 3] Except having added the additive (C-2) at the ratio described in Table 1, the epoxy resin layer was formed on the same conditions as Example 1, and the laminated body of Example 3 was obtained. The resulting epoxy resin layer had a thickness of 25 μm. The obtained epoxy resin layer was peeled from the release film, and the glass transition temperature was measured. The glass transition temperature was 128°C, and the glass transition temperature at the time of reheating was 129°C, so complete hardening was confirmed.

[實施例4] 以表1記載之比率進行調配,除此以外,以與實施例3相同之條件形成環氧樹脂層,獲得實施例4之積層體。所得之環氧樹脂層之厚度為25 μm。 將所得之環氧樹脂層自離型膜剝離,測定玻璃轉移溫度。玻璃轉移溫度為125℃,再升溫時之玻璃轉移溫度為125℃,因此確認到完全硬化。 [Example 4] Except having prepared in the ratio described in Table 1, the epoxy resin layer was formed on the same conditions as Example 3, and the laminated body of Example 4 was obtained. The resulting epoxy resin layer had a thickness of 25 μm. The obtained epoxy resin layer was peeled from the release film, and the glass transition temperature was measured. The glass transition temperature was 125°C, and the glass transition temperature at the time of reheating was 125°C, so complete hardening was confirmed.

[比較例1] 以表1記載之比率混合環氧樹脂(A-1)及(A-2)、交聯劑(B-3)、溶劑(D-1)及(D-2),製備塗佈液。 使用敷料器將塗佈液塗佈於離型膜上,使用恆溫乾燥機於150℃下一次加熱30分鐘,且於170℃下二次加熱60分鐘而進行硬化處理,自然冷卻至室溫,藉此形成環氧樹脂層,獲得比較例1之積層體。所得之環氧樹脂層之厚度為25 μm。 將所得之環氧樹脂層自離型膜剝離,測定玻璃轉移溫度。玻璃轉移溫度為104℃,再升溫時之玻璃轉移溫度為103℃,因此確認到完全硬化。 [Comparative example 1] Epoxy resins (A-1) and (A-2), crosslinking agent (B-3), solvents (D-1) and (D-2) were mixed at the ratios described in Table 1 to prepare coating liquids. Use an applicator to apply the coating liquid on the release film, heat it once at 150°C for 30 minutes with a constant temperature dryer, and heat it again at 170°C for 60 minutes to harden, and cool it to room temperature naturally. This formed an epoxy resin layer, and the laminated body of the comparative example 1 was obtained. The resulting epoxy resin layer had a thickness of 25 μm. The obtained epoxy resin layer was peeled from the release film, and the glass transition temperature was measured. The glass transition temperature was 104°C, and the glass transition temperature when the temperature was raised again was 103°C, so complete hardening was confirmed.

[比較例2] 以表1記載之比率混合環氧樹脂(A-1)、(A-2)、交聯劑(B-3)、溶劑(D-1)及(D-2),製備塗佈液。 使用敷料器將塗佈液塗佈於離型膜上,使用恆溫乾燥機於80℃下一次加熱2分鐘,且於180℃下二次加熱5分鐘而進行硬化處理,自然冷卻至室溫(25℃),藉此形成環氧樹脂層,獲得比較例2之積層體。所得之環氧樹脂層之厚度為25 μm。 將所得之環氧樹脂層自離型膜剝離,測定玻璃轉移溫度。玻璃轉移溫度為96℃,再升溫時之玻璃轉移溫度為104℃,確認到未完全硬化。 [Comparative example 2] Epoxy resins (A-1), (A-2), crosslinking agent (B-3), solvents (D-1) and (D-2) were mixed at the ratios listed in Table 1 to prepare coating liquids. Use an applicator to apply the coating liquid on the release film, heat it once at 80°C for 2 minutes using a constant temperature dryer, and heat it at 180°C for 5 minutes for a second time to harden, and cool it naturally to room temperature (25 °C), thereby forming an epoxy resin layer, and obtaining a laminate of Comparative Example 2. The resulting epoxy resin layer had a thickness of 25 μm. The obtained epoxy resin layer was peeled from the release film, and the glass transition temperature was measured. The glass transition temperature was 96°C, and the glass transition temperature when the temperature was raised again was 104°C, and incomplete hardening was confirmed.

[比較例3] 以表1記載之比率混合環氧樹脂(A-1)、(A-2)、交聯劑(B-1)、(B-3)、溶劑(D-1)及(D-2),製備塗佈液。 使用敷料器將塗佈液塗佈於離型膜上,使用恆溫乾燥機於80℃下一次加熱2分鐘,且於180℃下二次加熱5分鐘而進行硬化處理,自然冷卻至室溫(25℃),藉此形成環氧樹脂層,獲得實施例1之積層體。所得之環氧樹脂層之厚度為25 μm。 將所得之環氧樹脂層自離型膜剝離,測定玻璃轉移溫度。玻璃轉移溫度為120℃,再升溫時之玻璃轉移溫度為125℃,確認到未完全硬化。 [Comparative example 3] Mix epoxy resins (A-1), (A-2), crosslinking agents (B-1), (B-3), solvents (D-1) and (D-2) in the ratios listed in Table 1, A coating liquid is prepared. Use an applicator to apply the coating liquid on the release film, heat it once at 80°C for 2 minutes using a constant temperature dryer, and heat it at 180°C for 5 minutes for a second time to harden, and cool it naturally to room temperature (25 °C), thereby forming an epoxy resin layer to obtain the laminate of Example 1. The resulting epoxy resin layer had a thickness of 25 μm. The obtained epoxy resin layer was peeled from the release film, and the glass transition temperature was measured. The glass transition temperature was 120°C, and the glass transition temperature when the temperature was raised again was 125°C, and incomplete hardening was confirmed.

<評估項目> (1)水滴接觸角 自積層體去除離型膜,使用協和界面科學股份有限公司製造之接觸角計「DropMaster 500」測定環氧樹脂層之水滴接觸角。測定時使用離子交換水。測定溫度為25℃,離子交換水之滴下量為2 μL,評估液滴接觸1秒後之水滴接觸角。測定環氧樹脂層之三處,算出平均值。 再者,表1中,將未與離型膜接觸之側之表面記為環氧樹脂層之「正面」,將與離型膜接觸之側之表面記為環氧樹脂層之「背面」。 <Evaluation items> (1) Water droplet contact angle The release film was removed from the laminate, and the water drop contact angle of the epoxy resin layer was measured using a contact angle meter "DropMaster 500" manufactured by Kyowa Interface Science Co., Ltd. Ion-exchanged water was used for the measurement. The measurement temperature was 25°C, and the drop volume of ion-exchanged water was 2 μL, and the water droplet contact angle after the droplet contacted for 1 second was evaluated. Three places of the epoxy resin layer were measured, and the average value was calculated. Furthermore, in Table 1, the surface on the side not in contact with the release film is marked as the "front" of the epoxy resin layer, and the surface on the side in contact with the release film is marked as the "back" of the epoxy resin layer.

(2)硬化度 環氧樹脂層之硬化度係基於JIS K7121「塑膠之轉移溫度測定法」所記載者中之「中點玻璃轉移溫度:Tmg」進行測定。具體而言,使用PerkinElmer Japan股份有限公司製造之示差掃描熱量計「DSC8500」,自20℃至250℃以10℃/min進行升溫,其後,以10℃/min降溫至0℃,再自0℃至250℃以10℃/min進行再升溫而進行測定。當再升溫時之玻璃轉移溫度未比升溫時之玻璃轉移溫度上升3℃以上時,視為完全硬化。 (2) degree of hardening The curing degree of the epoxy resin layer is measured based on the "midpoint glass transition temperature: Tmg" described in JIS K7121 "Measuring method of transition temperature of plastics". Specifically, using a differential scanning calorimeter "DSC8500" manufactured by PerkinElmer Japan Co., Ltd., the temperature was raised from 20°C to 250°C at 10°C/min, and then cooled to 0°C at 10°C/min. The measurement was performed by reheating at 10°C/min from °C to 250°C. When the glass transition temperature at the reheating time is not higher than the glass transition temperature at the heating time by more than 3°C, it is considered to be completely hardened.

(3)光線透過率及霧度 使用日本電色工業股份有限公司製造之測霧計「NDH 7000II」測定環氧樹脂層於400 nm及650 nm下之光線透過率及霧度。 測定係依據JIS(全光線透過率:JIS K 7361-1,霧度:JIS K 7136)進行。 (3) Light transmittance and haze The light transmittance and haze of the epoxy resin layer at 400 nm and 650 nm were measured using a haze meter "NDH 7000II" manufactured by Nippon Denshoku Industries Co., Ltd. The measurement was performed in accordance with JIS (total light transmittance: JIS K 7361-1, haze: JIS K 7136).

(4)黃度(YI值) 依據ASTM E313使用日本電色工業股份有限公司製造之分光色彩計「SD6000」測定環氧樹脂層之黃度(YI值)。光源為C,視角為2°。 (4) Yellowness (YI value) The yellowness (YI value) of the epoxy resin layer was measured using a spectrocolorimeter "SD6000" manufactured by Nippon Denshoku Industries Co., Ltd. according to ASTM E313. The light source is C, and the viewing angle is 2°.

(5)耐彎曲性(R) 使用彎曲試驗機(YUASA SYSTEM機器股份有限公司製造,DLDMLH-FS),對環氧樹脂層進行20萬次彎曲試驗,評估不會產生龜裂及折痕之最小彎曲半徑R。再者,實施例1~4之環氧樹脂層即使R=1 mm亦不產生龜裂及折痕,因此於表1中記為「1 mm以下」。 (5) Bending resistance (R) Using a bending tester (manufactured by Yuasa System Co., Ltd., DLDMLH-FS), the epoxy resin layer was subjected to a bending test of 200,000 times, and the minimum bending radius R without cracks and creases was evaluated. In addition, since the epoxy resin layer of Examples 1-4 did not produce cracks and creases even if R=1 mm, it was recorded as "1 mm or less" in Table 1.

[表1] 表1    實施例1 實施例2 實施例3 實施例4 比較例1 比較例2 比較例3 環氧樹脂       (A-1) [質量份] 100 100 100 100 100 100 100 (A-2) [質量份] - - - - 2.1 2.1 2.1 交聯劑       (B-1) [質量份] 30 30 30 30 - - 30 (B-2) [質量份] 0.006 0.006 0.004 0.004 - -    (B-3) [質量份] - - - - 0.2 0.2 0.2 添加劑       (C-1) [質量份] - 0.4 - - - - - (C-2) [質量份] - - 0.4 0.33 - - - 溶劑       (D-1) [質量份] 27 27 27 33 6 6 6 (D-2) [質量份] 33 33 33 62 13 13 13 硬化度T2 130 129 129 129 104 104 125 T1 130 128 128 128 103 96 120 T2-T1 0 1 1 1 1 8 5 水滴接觸角 表面 [度] 80 80 81 76 79 83 80 背面(離型面側) [度] 82 60 75 80 112 93 85 400 nm透過率 [%] 89.0 88.9 89.5 89.3 87.9 88.6 89.0 650 nm透過率 [%] 90.1 90.8 90.6 90.6 90.4 90.2 90.4 霧度 [%] 0.80 0.8 0.6 0.6 1.8 0.9 0.8 YI值 - 0.6 0.6 0.6 0.6 0.7 0.7 0.6 R - 1 mm以下 1 mm以下 1 mm以下 1 mm以下 2.0 mm 2.0 mm 3.0 mm [Table 1] Table 1 Example 1 Example 2 Example 3 Example 4 Comparative example 1 Comparative example 2 Comparative example 3 epoxy resin (A-1) [parts by mass] 100 100 100 100 100 100 100 (A-2) [parts by mass] - - - - 2.1 2.1 2.1 crosslinking agent (B-1) [parts by mass] 30 30 30 30 - - 30 (B-2) [parts by mass] 0.006 0.006 0.004 0.004 - - (B-3) [parts by mass] - - - - 0.2 0.2 0.2 additive (C-1) [parts by mass] - 0.4 - - - - - (C-2) [parts by mass] - - 0.4 0.33 - - - solvent (D-1) [parts by mass] 27 27 27 33 6 6 6 (D-2) [parts by mass] 33 33 33 62 13 13 13 Hardness T2 130 129 129 129 104 104 125 T1 130 128 128 128 103 96 120 T2-T1 0 1 1 1 1 8 5 water droplet contact angle surface [Spend] 80 80 81 76 79 83 80 Back (release side) [Spend] 82 60 75 80 112 93 85 400 nm transmittance [%] 89.0 88.9 89.5 89.3 87.9 88.6 89.0 650 nm transmittance [%] 90.1 90.8 90.6 90.6 90.4 90.2 90.4 Haze [%] 0.80 0.8 0.6 0.6 1.8 0.9 0.8 YI value - 0.6 0.6 0.6 0.6 0.7 0.7 0.6 R - 1 mm or less 1 mm or less 1 mm or less 1 mm or less 2.0 mm 2.0 mm 3.0 mm

根據實施例1~實施例4,確認到藉由環氧樹脂組合物含有異氰酸酯系化合物(B)作為交聯劑,硬化所需之時間變短,生產性良好。又,確認到實施例1~實施例4之環氧樹脂層之兩表面之水滴接觸角為84度以下,具有適度潤濕性。 進而,根據實施例2~4,確認到藉由添加劑(調平劑)可調整水滴接觸角。認為其原因在於添加劑(調平劑)於環氧樹脂層與離型膜之界面發生偏析。藉由將水滴接觸角控制在84度以下,具有所需潤濕性,可期待提高後續步驟中之密接性之效果。 另一方面,比較例1中,完全硬化之前需要長時間加熱,因此生產性較差。又,由於硬化所需之時間較長,故環氧樹脂層之背面(離型膜側)之水滴接觸角變高,結果對後續步驟之適應性受損。 比較例2雖硬化時間與實施例1相同,但含有3官能之環氧樹脂,因此結果硬化反應非常慢,遠未達到完全硬化。可知比較例3係於比較例2中進而併用異氰酸酯之情形,雖稍微進行了硬化反應,但即使如此仍未達到完全硬化水準。 由以上情況可知,3官能以上之環氧樹脂大幅影響硬化反應速度。 又,由於比較例1~3之玻璃轉移溫度均未達126℃,低於實施例,故結果R值(耐彎曲性評估)比實施例差。 From Examples 1 to 4, it was confirmed that when the epoxy resin composition contained the isocyanate compound (B) as a crosslinking agent, the time required for curing became short and the productivity was good. Moreover, it was confirmed that the water droplet contact angle of both surfaces of the epoxy resin layer of Example 1-Example 4 was 84 degrees or less, and it had moderate wettability. Furthermore, from Examples 2-4, it was confirmed that the water droplet contact angle can be adjusted by an additive (leveling agent). This is considered to be due to segregation of the additive (leveling agent) at the interface between the epoxy resin layer and the release film. By controlling the water droplet contact angle to 84 degrees or less, the required wettability can be expected to improve the adhesion in the subsequent steps. On the other hand, in Comparative Example 1, it required a long time of heating until it was completely cured, so the productivity was poor. Also, since the time required for curing is long, the water droplet contact angle on the back side of the epoxy resin layer (release film side) becomes high, and as a result, the adaptability to the subsequent steps is impaired. Although the curing time of Comparative Example 2 is the same as that of Example 1, but it contains a trifunctional epoxy resin, the result is that the curing reaction is very slow, and it is far from being fully cured. It can be seen that Comparative Example 3 is a case where isocyanate was further used in combination with Comparative Example 2, and although the curing reaction proceeded a little, it did not reach the level of complete curing. From the above situation, it can be seen that the epoxy resin with more than three functionalities greatly affects the curing reaction speed. In addition, since the glass transition temperature of Comparative Examples 1 to 3 did not reach 126°C, which was lower than that of Examples, the resulting R value (evaluation of bending resistance) was worse than that of Examples.

Claims (16)

一種積層體,其至少具備使含有環氧樹脂(A)及異氰酸酯化合物(B)之環氧樹脂組合物硬化而成之環氧樹脂層、及離型膜,且 上述環氧樹脂(A)實質上不含3官能以上之環氧樹脂, 藉由DSC測定,自20℃至250℃以10℃/min進行升溫,其後,以10℃/min降溫至0℃,再自0℃至250℃以10℃/min進行再升溫而測定上述環氧樹脂層時,再升溫時之玻璃轉移溫度(T2)與升溫時之玻璃轉移溫度(T1)之差(T2-T1)為3℃以內。 A laminate comprising at least an epoxy resin layer formed by curing an epoxy resin composition containing an epoxy resin (A) and an isocyanate compound (B), and a release film, and The epoxy resin (A) does not substantially contain a trifunctional or higher epoxy resin, As measured by DSC, the temperature was raised from 20°C to 250°C at 10°C/min, and then the temperature was lowered to 0°C at 10°C/min, and then the temperature was raised again from 0°C to 250°C at 10°C/min to determine the above For the epoxy resin layer, the difference (T2-T1) between the glass transition temperature (T2) and the glass transition temperature (T1) at the time of heating up should be within 3°C. 如請求項1之積層體,其中上述環氧樹脂(A)係環氧化合物與酚系化合物反應而成之樹脂。The laminate according to claim 1, wherein the above-mentioned epoxy resin (A) is a resin obtained by reacting an epoxy compound and a phenolic compound. 如請求項2之積層體,其中上述環氧化合物係分子內具有2個以內環氧基之化合物。The laminate according to claim 2, wherein the above-mentioned epoxy compound is a compound having two or less epoxy groups in the molecule. 如請求項2或3之積層體,其中上述酚系化合物係具有2個以上與芳香環鍵結之羥基之化合物。The laminate according to claim 2 or 3, wherein the above-mentioned phenolic compound is a compound having two or more hydroxyl groups bonded to an aromatic ring. 如請求項1至4中任一項之積層體,其中上述環氧樹脂(A)之分子量為2,000~300,000。The laminate according to any one of claims 1 to 4, wherein the epoxy resin (A) has a molecular weight of 2,000 to 300,000. 如請求項1至5中任一項之積層體,其中上述異氰酸酯化合物(B)係以脂肪族異氰酸酯為主骨架之化合物。The laminate according to any one of Claims 1 to 5, wherein the above-mentioned isocyanate compound (B) is a compound having an aliphatic isocyanate as a main skeleton. 如請求項1至6中任一項之積層體,其中上述環氧樹脂組合物含有調平劑。The laminate according to any one of claims 1 to 6, wherein the epoxy resin composition contains a leveling agent. 如請求項7之積層體,其中上述調平劑包含矽酮骨架及聚醚骨架。The laminate according to claim 7, wherein the leveling agent includes a silicone skeleton and a polyether skeleton. 如請求項7或8之積層體,其中上述調平劑不含丙烯酸骨架。The laminate according to claim 7 or 8, wherein the leveling agent does not contain an acrylic skeleton. 如請求項1至9中任一項之積層體,其中上述環氧樹脂層之玻璃轉移溫度為100℃以上。The laminate according to any one of claims 1 to 9, wherein the glass transition temperature of the epoxy resin layer is 100°C or higher. 一種如請求項1至10中任一項之積層體之製造方法,其係藉由80℃~160℃之一次加熱處理及比一次加熱處理溫度高40~120℃之120~200℃之二次加熱處理,使上述環氧樹脂組合物硬化。A method for manufacturing a laminate according to any one of Claims 1 to 10, which is performed by a first heat treatment at 80°C to 160°C and a second heat treatment at 120 to 200°C that is 40 to 120°C higher than the first heat treatment temperature Heat treatment hardens the above-mentioned epoxy resin composition. 一種環氧膜,其包含上述含有環氧樹脂(A)及異氰酸酯化合物(B)之環氧樹脂組合物,且兩表面之水滴接觸角均為84度以下。An epoxy film comprising the above-mentioned epoxy resin composition containing epoxy resin (A) and isocyanate compound (B), and the water droplet contact angles on both surfaces are 84 degrees or less. 如請求項12之環氧膜,其於至少一面具有功能層。The epoxy film according to claim 12, which has a functional layer on at least one side. 一種捲繞體,其係將如請求項1至10中任一項之積層體或者如請求項12或13之環氧膜捲繞於芯體而成。A wound body formed by winding the laminate according to any one of claims 1 to 10 or the epoxy film according to claim 12 or 13 on a core. 如請求項1至10中任一項之積層體,其用於顯示器。The laminate according to any one of claims 1 to 10, which is used for a display. 如請求項12或13之環氧膜,其用於顯示器。The epoxy film according to claim 12 or 13, which is used for a display.
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