TW201736145A - Method for producing laminate, and utilization thereof - Google Patents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B43/00—Operations specially adapted for layered products and not otherwise provided for, e.g. repairing; Apparatus therefor
- B32B43/006—Delaminating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
- C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
- C09J5/02—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving pretreatment of the surfaces to be joined
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
Abstract
Description
本發明係關於層合體之製造方法、及其之利用。 The present invention relates to a method of producing a laminate and use thereof.
聚醯亞胺樹脂被廣泛使用作為平板顯示器或觸碰面板等之電子設備中使用之可撓性基板。 Polyimine resins are widely used as flexible substrates used in electronic devices such as flat panel displays or touch panels.
例如，專利文獻1中對下述高分子膜層合基板進行了記載，其中，該高分子膜層合基板為於無機基板之至少單面之一部分上連續或不連續地形成薄膜，於薄膜上連續或不連續地形成矽烷偶合劑層，進一步於矽烷偶合劑層上層合高分子膜層而得到之高分子膜層合基板。 For example, Patent Document 1 describes a polymer film laminated substrate in which a film is formed continuously or discontinuously on at least one side of at least one side of an inorganic substrate, on the film. A polymer film laminated substrate obtained by continuously or discontinuously forming a decane coupling agent layer and further laminating a polymer film layer on a decane coupling agent layer.
[專利文獻1]日本特開2014-237270號公報(2014年12月18日公開) [Patent Document 1] Japanese Laid-Open Patent Publication No. 2014-237270 (published on Dec. 18, 2014)
然而，如專利文獻1中記載之高分子膜層合基板般，不論是否具有薄膜，均具備有高耐熱性，且均可將經由聚醯亞胺樹脂形成之基板順利地從支撐體剝離之層合體之製造方法，可於該基板上形成各種電路，為有用的。 However, as in the case of the polymer film laminated substrate described in Patent Document 1, the substrate having the high heat resistance and the substrate formed of the polyimide resin can be smoothly peeled off from the support regardless of whether or not the film is provided. A method of manufacturing a combination can be useful in forming various circuits on the substrate.
本發明鑒於上述之問題點而成，其目的在於，提供一種具備有高耐熱性，且可將經由聚醯亞胺樹脂形成之基板順利地剝離之新穎的層合體之製造方法、及、其相關技術。 The present invention has been made in view of the above problems, and an object of the invention is to provide a novel method for producing a novel laminate which has high heat resistance and can be smoothly peeled off from a substrate formed of a polyimide resin. technology.
為了解決上述問題，本發明之一實施方式之層合體之製造方法為將經由聚醯亞胺樹脂形成之基板、與支撐上述基板之支撐體藉由接著層進行層合而成之層合體之製造方法，其特徵在於，包含：水解步驟，使存在於上述基板之兩個平面部中之一個平面部之醯亞胺鍵之一部分水解；與接著層形成步驟，於上述支撐體上形成包含具有下述式(1)所示之構成單位之聚醯胺酸而成之接著層，
(上述式(1)中，R1為4價之有機基，且為碳原子數為2以上、11以下的芳香族基、脂肪族基、或脂環式基；R2為2價之有機基，除碳原子及氫原子之外亦可包含選自由氮原子、氧原子、硫原子、及、鹵素所成之群中之原子，且為碳原子數為2以上、50以下之芳香族基、脂肪族基、或脂環式基；n為1以上)；與黏貼步驟，以使上述醯亞胺鍵進行了水解之平面部與上述支撐體相對之方式，藉由上述接著層將上述基板與上述支撐體黏貼並加熱。 (In the above formula (1), R 1 is a tetravalent organic group, and is an aromatic group, an aliphatic group or an alicyclic group having 2 or more and 11 or less carbon atoms; and R 2 is a divalent organic group; The group may include an atom selected from a group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, and a halogen, in addition to a carbon atom and a hydrogen atom, and is an aromatic group having 2 or more and 50 or less carbon atoms. Or an aliphatic group or an alicyclic group; n is 1 or more; and the adhesion step is such that the planar portion of the yttrium imine bond is hydrolyzed to face the support, and the substrate is formed by the adhesive layer Adhered to and heated with the above support.
另外，本發明之一實施方式之層合體為將經由聚醯亞胺樹脂所成之基板、與支撐上述基板之支撐體藉由接著層進行層合而成之層合體，其特徵在於，具有來自於下述胺基與下述羧基之醯胺鍵，所述胺基為存在於上述基板之與上述支撐體相對之平面部之聚醯亞胺樹脂所具有之胺基、與所述羧基為具有下述式(1)所示之構成單位之聚醯胺酸所具有之羧基，
(上述式(1)中，R1為4價之有機基，且為碳原子數為2以上、11以下之芳香族基、脂肪族基、或脂環式基；R2為2價之有機基，除碳原子及氫原子之外亦可含有選自由氮原子、氧原子、硫原子、及、鹵素所成之群中之原子，且為碳原子數為2以上、50以下之芳香族基、脂肪族基、或脂環式基；n為1以上)。 (In the above formula (1), R 1 is a tetravalent organic group, and is an aromatic group, an aliphatic group or an alicyclic group having 2 or more and 11 or less carbon atoms; and R 2 is a divalent organic group; The group may contain, in addition to a carbon atom and a hydrogen atom, an atom selected from a group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, and a halogen, and is an aromatic group having 2 or more and 50 or less carbon atoms. , an aliphatic group, or an alicyclic group; n is 1 or more).
根據本發明，可獲得可提供具備有高耐熱性，且可將經由聚醯亞胺樹脂形成之基板順利地剝離之新穎的層合體之製造方法、及、其相關技術之效果。 According to the present invention, it is possible to obtain a novel method for producing a novel laminate which is provided with a high heat resistance and which can be smoothly peeled off from a substrate formed of a polyimide resin, and the related art effects.
1‧‧‧基板 1‧‧‧Substrate
2‧‧‧支撐板(支撐體) 2‧‧‧Support plate (support)
3‧‧‧接著層 3‧‧‧Next layer
10‧‧‧層合體 10‧‧‧Layer
[圖1]係對本發明之一實施形態之層合體之製造方法、層合體、及基板之處理方法之概要進行說明之圖。 Fig. 1 is a view for explaining an outline of a method for producing a laminate, a laminate, and a method for treating a substrate according to an embodiment of the present invention.
以下，對一實施形態之層合體之製造方法進行更詳細之說明。 Hereinafter, a method of producing a laminate according to an embodiment will be described in more detail.
如圖1之(a)所示，本實施形態之層合體之製造方法包含：對經由聚醯亞胺樹脂形成之基板1之平面部進行水解處理之水解步驟(圖1之(a)及(b))、與於支撐板(support plate)(支撐體)2上形成接著層3之接著層形成步驟(圖1之(c)及(d))、與藉由接著層3將基板1與支撐板2黏貼並加熱之黏貼步驟(圖1之(e))。 As shown in Fig. 1(a), the method for producing a laminate according to the present embodiment includes a hydrolysis step of hydrolyzing a flat portion of a substrate 1 formed of a polyimide resin (Fig. 1(a) and (Fig. 1(a) and b)), forming an adhesive layer forming step of the bonding layer 3 on the support plate (support) 2 ((c) and (d) of FIG. 1), and bonding the substrate 1 with the bonding layer 3 The bonding step of the support plate 2 is adhered and heated ((e) of Fig. 1).
又，若水解步驟(圖1的(b))、及、接著層形成步驟(圖1之(d))於黏貼步驟(圖1之(e))之前，則既可同時進行或可先進行某一者。 Further, if the hydrolysis step (Fig. 1 (b)) and the subsequent layer formation step (Fig. 1 (d)) are before the pasting step (Fig. 1 (e)), they may be performed simultaneously or may be performed first. Someone.
如圖1之(a)及(b)所示，水解步驟中，經由對存在於經由聚醯亞胺樹脂形成之基板1之平面部之醯亞胺鍵之一部分進行水解，從而使之開裂，形成胺基與羧基。此等胺基與羧基存在於開裂後之聚醯亞胺樹脂中之分子鏈之末端。 As shown in (a) and (b) of FIG. 1, in the hydrolysis step, a part of the quinone bond which is present in the plane portion of the substrate 1 formed through the polyimide resin is hydrolyzed to cause cracking. An amine group and a carboxyl group are formed. These amine groups and carboxyl groups are present at the end of the molecular chain in the cracked polyimine resin.
圖1之(b)為對本實施形態之層合體之製造方法所包含之水解步驟之概要進行說明之圖。如圖1之(b)所示，於本實施形態之層合體之製造方法中，於水解步驟中，例如，經由於充滿有含有鹼化合物與水之處理 液之處理槽50中浸漬基板1，從而使基板1之表面之聚醯亞胺樹脂水解。 (b) of FIG. 1 is a view for explaining an outline of a hydrolysis step included in the method for producing a laminate of the present embodiment. As shown in FIG. 1(b), in the method for producing a laminate according to the present embodiment, in the hydrolysis step, for example, it is filled with a treatment containing an alkali compound and water. The substrate 1 is immersed in the liquid treatment tank 50 to hydrolyze the polyimide resin on the surface of the substrate 1.
於處理液中之浸漬條件可根據形成基板1之聚醯亞胺樹脂之種類、處理液之種類或濃度等而適當設計，沒有特別限定，例如，可於20℃以上、50℃以下之範圍內之溫度條件下，以1分鐘以上、10分鐘以下的範圍內之時間進行浸漬處理即可。由此，可於基板1之平面部中形成胺基，並且還可防止由於聚醯亞胺基板過度水解而導致基板1發生溶解、膜厚發生變化。 The immersion conditions in the treatment liquid are appropriately designed depending on the type of the polyimide resin to be formed on the substrate 1, the type or concentration of the treatment liquid, and the like, and are not particularly limited. For example, it can be in the range of 20 ° C or higher and 50 ° C or lower. Under the temperature conditions, the immersion treatment may be performed for a period of time of 1 minute or longer and 10 minutes or shorter. Thereby, an amine group can be formed in the planar portion of the substrate 1, and it is also possible to prevent the substrate 1 from being dissolved and the film thickness from being changed due to excessive hydrolysis of the polyimide substrate.
水解步驟中，將基板1浸漬於處理液中，在將存在於該基板1之平面部之醯亞胺鍵水解之後，將該基板1從處理槽50中提起，進行水洗。之後，將基板1於90℃~100℃之溫度條件下加熱5分鐘~20分鐘，由此從基板1中除去水分。 In the hydrolysis step, the substrate 1 is immersed in the treatment liquid, and after the hydrazine bond present in the plane portion of the substrate 1 is hydrolyzed, the substrate 1 is lifted from the treatment tank 50 and washed with water. Thereafter, the substrate 1 is heated at a temperature of 90 ° C to 100 ° C for 5 minutes to 20 minutes to remove moisture from the substrate 1 .
如圖1之(a)所示，基板1由預先形成為膜狀之聚醯亞胺樹脂形成，典型的情況為使用作為膜基板及可撓性基板等之基板。關於基板1，於層合至層合體10之狀態下，經由進行各種步驟而形成佈線等，安裝積體電路等之構造物。 As shown in FIG. 1( a ), the substrate 1 is formed of a polyimide resin which is formed in a film shape in advance, and typically a substrate such as a film substrate or a flexible substrate is used. In the state in which the substrate 1 is laminated to the laminate 10, a wiring or the like is formed by performing various steps, and a structure such as an integrated circuit is mounted.
基板1係厚度為10μm~100μm左右之聚醯亞胺樹脂之膜，可為例如利用雙軸拉伸法等進行了拉伸成形之基板。又，膜基板之尺寸無特別限定，但本實施形態之 層合體之製造方法中，使用俯視之形狀為例如長方形之A3尺寸(即，297mm×420mm)之膜基板。 The substrate 1 is a film of a polyimide resin having a thickness of about 10 μm to 100 μm, and may be, for example, a substrate which is stretch-molded by a biaxial stretching method or the like. Further, the size of the film substrate is not particularly limited, but the embodiment is In the method for producing a laminate, a film substrate having a shape of a plan view of, for example, a rectangular A3 size (that is, 297 mm × 420 mm) is used.
使用於形成基板1之聚醯亞胺樹脂若是通用的，則對其種類無限定，更佳為具有耐熱性之聚醯亞胺樹脂。對於聚醯亞胺樹脂，可舉出經由將芳香族酸二酐與芳香族二胺聚合而得到之芳香族聚醯亞胺樹脂、經由將脂環式酸二酐與脂環式二胺聚合而得到之脂環式聚醯亞胺樹脂、及、具有芳香族結構與脂環式結構兩者之半芳香族聚醯亞胺樹脂等。另外，對於聚醯亞胺樹脂，可根據需要摻和顏料等。 The polyimine resin used for forming the substrate 1 is not particularly limited as long as it is versatile, and more preferably a heat-resistant polyimide resin. The polyimine resin is an aromatic polyimine resin obtained by polymerizing an aromatic acid dianhydride and an aromatic diamine, and polymerizing an alicyclic acid dianhydride and an alicyclic diamine. The obtained alicyclic polyimine resin, and a semi-aromatic polyimide resin having both an aromatic structure and an alicyclic structure. Further, as the polyimine resin, a pigment or the like may be blended as needed.
處理液經由將存在於經由聚醯亞胺樹脂形成之基板1之表面之醯亞胺鍵進行水解而使之開裂，形成胺基。處理液包含有機鹼化合物、及、水，更佳進一步包含水溶性有機溶劑。 The treatment liquid is hydrolyzed by hydrazide bonds present on the surface of the substrate 1 formed through the polyimide resin to form an amine group. The treatment liquid contains an organic base compound and water, and more preferably further contains a water-soluble organic solvent.
處理液中，有機鹼化合物之濃度可根據有機鹼化合物之種類而適當設計，因此無限定，但較佳於1重量%以上、25重量%以下之範圍內，更佳於1重量%以上、10重量%以下之範圍內，最佳於2重量%以上、5重量%以下之範圍內。另外，關於溶解有機鹼化合物之溶劑，水與水溶性有機溶劑之比例較佳於9：1至1：9之範圍內，更佳於8：2~3：7之範圍內。如這般，經由使用包含有機鹼化合物、水、及、水溶性有機溶劑之處理液， 可將存在於基板1之表面之醯亞胺鍵均勻地水解。因此，可使層合體10中之基板1之剝離強度變得均勻。 In the treatment liquid, the concentration of the organic alkali compound can be appropriately designed depending on the type of the organic base compound, and is not limited, but is preferably in the range of 1% by weight or more and 25% by weight or less, more preferably 1% by weight or more, or 10%. In the range of % by weight or less, it is preferably in the range of 2% by weight or more and 5% by weight or less. Further, as for the solvent for dissolving the organic base compound, the ratio of water to the water-soluble organic solvent is preferably in the range of from 9:1 to 1:9, more preferably in the range of from 8:2 to 3:7. As such, by using a treatment liquid containing an organic base compound, water, and a water-soluble organic solvent, The quinone imine bond present on the surface of the substrate 1 can be uniformly hydrolyzed. Therefore, the peel strength of the substrate 1 in the laminate 10 can be made uniform.
有機鹼化合物較佳為含氮有機化合物，可更佳使用4級銨氫氧化物(quaternary ammonium hydroxide)。對於4級銨氫氧化物，可舉出氫氧化四甲銨、氫氧化四乙銨、氫氧化四丙銨、氫氧化四丁銨、乙基三甲基氫氧化銨、二甲基二乙基氫氧化銨、甲基三乙基氫氧化銨、甲基三丙基氫氧化銨、甲基三丁基氫氧化銨、苄基三甲基氫氧化銨、及(2-羥乙基)三甲基氫氧化銨等，最佳使用氫氧化四甲銨。此等有機鹼化合物可同時使用2種以上。 The organic base compound is preferably a nitrogen-containing organic compound, and a quaternary ammonium hydroxide can be more preferably used. Examples of the fourth-order ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ethyltrimethylammonium hydroxide, and dimethyldiethylate. Ammonium hydroxide, methyltriethylammonium hydroxide, methyltripropylammonium hydroxide, methyltributylammonium hydroxide, benzyltrimethylammonium hydroxide, and (2-hydroxyethyl)trimethyl As the ammonium hydroxide or the like, tetramethylammonium hydroxide is preferably used. These organic base compounds may be used in combination of two or more kinds.
如這般，從可抑制基板1中之聚醯亞胺樹脂之水解過度進行，並且於基板1之表層中使醯亞胺鍵適宜地水解之觀點考慮，將於利用光刻步驟等形成電路時所使用之有機鹼化合物使用於基板1之處理液為有效的。 As described above, from the viewpoint of suppressing excessive hydrolysis of the polyimide resin in the substrate 1 and appropriately hydrolyzing the quinone bond in the surface layer of the substrate 1, the circuit will be formed by a photolithography step or the like. The organic alkali compound used is effective for the treatment liquid of the substrate 1.
處理液較佳進一步含有水溶性有機溶劑。由此，可於基板1之表面上均勻地將聚醯亞胺樹脂水解。作為水溶性有機溶劑之適合之例子，可舉出醇類、多元醇類與其衍生物、亞碸類、碸類、醯胺類、內醯胺類、內酯類、咪唑啉酮類、及、烷醇胺類，更佳使用醇類。 The treatment liquid preferably further contains a water-soluble organic solvent. Thereby, the polyimine resin can be uniformly hydrolyzed on the surface of the substrate 1. Suitable examples of the water-soluble organic solvent include alcohols, polyhydric alcohols and derivatives thereof, anthraquinones, anthraquinones, decylamines, indoleamines, lactones, imidazolinones, and Alkanolamines, more preferably alcohols.
對於醇類，可舉出例如甲醇、乙醇、正丙醇、及異丙醇。對於多元醇類與其衍生物，可舉出例如乙二醇、乙二醇單甲醚、乙二醇單***、乙二醇單丁醚、乙二醇單乙酸酯、乙二醇單甲醚乙酸酯、乙二醇單***乙酸酯、二甘醇、二甘醇單乙酸酯、二甘醇單甲醚、二甘醇單 ***、二甘醇單丁醚、丙二醇、丙二醇單甲醚、丙二醇單***、丙二醇單丙醚、二丙二醇單甲醚、丙三醇、1,2-丁二醇、1,3-丁二醇、及、2,3-丁二醇等。對於亞碸類，可舉出例如二甲基亞碸等，對於碸類，可舉出例如二甲基碸、二乙基碸、雙(2-羥乙基)碸、及、環丁碸(tetramethylene sulfone)等。對於醯胺類，可舉出例如N,N-二甲基甲醯胺、N-甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基乙醯胺、及、N,N-二乙基乙醯胺等。對於內醯胺類，可舉出例如N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、N-羥甲基-2-吡咯烷酮、及、N-羥乙基-2-吡咯烷酮等。對於內酯類，可舉出β-丙內酯、γ-丁內酯、γ-戊內酯、δ-戊內酯、γ-己內酯、及、ε-己內酯等。對於咪唑啉酮類，可舉出1,3-二甲基-2-咪唑啉酮、1,3-二乙基-2-咪唑啉酮、及、1,3-二異丙基-2-咪唑啉酮等。對於烷醇胺類，可舉出例如單乙醇胺、二乙醇胺、三乙醇胺、2-(2-胺基乙氧基)乙醇、N,N-二甲基乙醇胺、N,N-二乙基乙醇胺、N,N-二丁基乙醇胺、N-甲基乙醇胺、N-乙基乙醇胺、N-丁基乙醇胺、N-甲基二乙醇胺、單異丙醇胺、雙異丙醇胺、及、三異丙醇胺等。又，關於親水性有機溶劑，可將2種以上混合使用。 Examples of the alcohols include methanol, ethanol, n-propanol, and isopropyl alcohol. Examples of the polyols and derivatives thereof include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoacetate, and ethylene glycol monomethyl ether. Acetate, ethylene glycol monoethyl ether acetate, diethylene glycol, diethylene glycol monoacetate, diethylene glycol monomethyl ether, diethylene glycol single Ether, diethylene glycol monobutyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, glycerol, 1,2-butanediol, 1,3-butanediol , and, 2,3-butanediol and the like. Examples of the anthracene include dimethyl anthracene, and the like, and examples of the anthracene include dimethyl hydrazine, diethyl hydrazine, bis(2-hydroxyethyl) fluorene, and cyclobutyl hydrazine ( Tetramethylene sulfone) and the like. Examples of the guanamines include N,N-dimethylformamide, N-methylformamide, N,N-dimethylacetamide, N-methylacetamide, and N. , N-diethylacetamide and the like. Examples of the indoleamines include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-hydroxymethyl-2-pyrrolidone, and N-hydroxyethyl-2-pyrrolidone. . Examples of the lactones include β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, and ε-caprolactone. Examples of the imidazolinones include 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, and 1,3-diisopropyl-2- Imidazolinone and the like. Examples of the alkanolamines include monoethanolamine, diethanolamine, triethanolamine, 2-(2-aminoethoxy)ethanol, N,N-dimethylethanolamine, and N,N-diethylethanolamine. N,N-dibutylethanolamine, N-methylethanolamine, N-ethylethanolamine, N-butylethanolamine, N-methyldiethanolamine, monoisopropanolamine, diisopropanolamine, and triiso Propanolamine and the like. Further, the hydrophilic organic solvent may be used in combination of two or more kinds.
另外，處理液可根據需要包含表面活性劑等。 Further, the treatment liquid may contain a surfactant or the like as needed.
如圖1之(d)所示，於接著層形成步驟中，將包含聚醯胺酸之接著劑塗佈於支撐板2上，經由加熱該支撐板2而形成接著層3。 As shown in FIG. 1(d), in the subsequent layer forming step, an adhesive containing polyamic acid is applied onto the support plate 2, and the support layer 2 is heated to form the adhesive layer 3.
對於在支撐板2上塗佈接著劑之方法，可舉出例如旋塗、浸漬、輥式刮刀(roller blade)、噴塗、狹縫塗佈等方法。 Examples of the method of applying the adhesive to the support plate 2 include spin coating, dipping, roller blade, spray coating, and slit coating.
接著層3之厚度可根據作為黏貼物件之基板1及支撐板2之種類、對黏貼後之基板1進行之處理等而適當設定即可，但較佳於1nm~1μm之範圍內，更佳於1nm~200nm之範圍內。 The thickness of the layer 3 may be appropriately set according to the type of the substrate 1 and the support plate 2 as the adhesive member, the treatment of the substrate 1 after the adhesion, and the like, but it is preferably in the range of 1 nm to 1 μm, more preferably Within the range of 1 nm to 200 nm.
接著層形成步驟中，經由將塗佈了接著劑之支撐板2於150℃以上、220℃以下之溫度加熱1分鐘~10分鐘、較佳為3分鐘~5分鐘，從而除去接著劑之聚醯胺酸中所包含之溶劑、及水分。由此，於後續之步驟(例如，包含本發明說明書中之[其他步驟])中，在對層合體10加熱時，可防止由於接著層3中殘留之溶劑及水之蒸發而在基板1與支撐板2之間產生空隙。 In the layer forming step, the support sheet 2 coated with the adhesive is heated at a temperature of 150 ° C or more and 220 ° C or less for 1 minute to 10 minutes, preferably 3 minutes to 5 minutes, thereby removing the aggregation of the adhesive. The solvent and water contained in the amine acid. Thus, in the subsequent step (for example, including [other steps] in the specification of the present invention), when the laminate 10 is heated, the evaporation of the solvent and water remaining in the adhesive layer 3 can be prevented on the substrate 1 and A gap is created between the support plates 2.
支撐板(支撐體)2為支撐基板1之支撐體(圖1之(c))。支撐板2藉由接著層3而黏貼於基板1。支撐板2具有為了於基板1之搬送、及、針對基板1進行之電路等之安裝等工藝時防止基板1之破損或變形所必要之強度即可，可使用由玻璃、或矽所成之支撐板等。 The support plate (support) 2 is a support for supporting the substrate 1 ((c) of Fig. 1). The support plate 2 is adhered to the substrate 1 by the adhesive layer 3. The support plate 2 may have strength necessary for preventing damage or deformation of the substrate 1 during the process of transporting the substrate 1 and mounting the circuit or the like on the substrate 1, and may be supported by glass or crucible. Board and so on.
又，本實施形態之層合體之製造方法中，使用了與基板1相同A3尺寸之玻璃製支撐板。本實施形態之層合體之製造方法中，可以於此種大型之支撐板2之平面部以均勻的厚度形成接著層3。因此，可於基板1之平面部之整個面中均勻地提高針對接著層3之密著性。如這般，可使用大型之支撐板2、對大型之基板1進行處理亦為本實施形態之層合體之製造方法的優點之一。 Further, in the method for producing a laminate of the present embodiment, a glass support plate having the same A3 size as the substrate 1 is used. In the method for producing a laminate according to the present embodiment, the adhesive layer 3 can be formed in a uniform thickness on the flat portion of the large-sized support plate 2. Therefore, the adhesion to the adhesive layer 3 can be uniformly increased over the entire surface of the planar portion of the substrate 1. As such, the use of the large support plate 2 for processing the large substrate 1 is also one of the advantages of the method for manufacturing the laminate of the present embodiment.
接著層3為包含具有下述式(1)所示之構成單位之聚醯胺酸所成之層。 Next, the layer 3 is a layer comprising a polyamic acid having a constituent unit represented by the following formula (1).
於此，式(1)中，R1為4價的有機基，碳原子數為2以上、11以下之芳香族基、脂肪族基、或、脂環式基；R2為2價之有機基，除碳原子及氫原子之外亦可包含選自由氮原子、氧原子、硫原子、及、鹵素所成之群中之原子、碳原子數為2以上、50以下之芳香族基、脂肪族基、或、脂環式基；n為1以上。 Here, in the formula (1), R 1 is a tetravalent organic group, and an aromatic group, an aliphatic group or an alicyclic group having 2 or more and 11 or less carbon atoms; and R 2 is a divalent organic group; The base may contain, in addition to a carbon atom and a hydrogen atom, an atom selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, and a halogen, an aromatic group having 2 or more and 50 or less carbon atoms, and a fat. a group or an alicyclic group; n is 1 or more.
上述式(1)所示、聚醯胺酸可經由使以下說 明之四羧酸二酐成分與二胺成分於溶劑(有機溶劑)中反應來合成。 Polyacyl acid represented by the above formula (1) can be said to The tetracarboxylic dianhydride component and the diamine component are reacted in a solvent (organic solvent) to synthesize.
對合成聚醯胺酸時之四羧酸二酐成分及二胺成分之使用量無特別限定，但相對於1莫耳之四羧酸二酐成分，較佳使用0.50莫耳~1.50莫耳之二胺成分，更佳使用0.60莫耳~1.30莫耳之二胺成分，特別佳使用0.70莫耳~1.20莫耳之二胺成分。 The amount of the tetracarboxylic dianhydride component and the diamine component used in the synthesis of the polyamic acid is not particularly limited, but it is preferably 0.50 to 1.50 moles per 1 mole of the tetracarboxylic dianhydride component. The diamine component is more preferably a 0.60 mole to 1.30 mole diamine component, and particularly preferably a 0.70 mole to 1.20 mole diamine component.
對於合成聚醯胺酸時使用之溶劑之量，於不損害本發明之目的之範圍內，無特別限定。典型之情況下，相對於四羧酸二酐成分之量與二胺成分之量之合計100質量份而言，溶劑之使用量較佳為20質量份~2000質量份，更佳為100質量份~1500質量份，最佳為150質量份~1000質量份。 The amount of the solvent used in the synthesis of the polyamic acid is not particularly limited as long as it does not impair the object of the present invention. In a typical case, the amount of the solvent used is preferably from 20 parts by mass to 2,000 parts by mass, more preferably 100 parts by mass, per 100 parts by mass of the total amount of the tetracarboxylic dianhydride component and the amount of the diamine component. ~1500 parts by mass, preferably 150 parts by mass to 1000 parts by mass.
對於溶劑(有機溶劑)，可從以往於聚醯胺酸之合成中所使用之溶劑中適當選擇。對於這般溶劑，可舉出非質子性極性溶劑，作為非質子性極性溶劑，可舉出例如上述之(水溶性有機溶劑)之一欄中記載之亞碸類、碸類、醯胺類、內醯胺類、內酯類、及、咪唑啉酮類。在此等非質子性極性溶劑中，作為接著劑之溶劑，更佳使用N-甲基-2-吡咯烷酮(NMP)、N,N-二甲基甲醯胺(DMF)、二甲基乙醯胺(DMAC)、六甲基磷醯胺、及、1,3-二甲基-2-咪唑啉酮等。 The solvent (organic solvent) can be appropriately selected from the solvents conventionally used in the synthesis of polyamic acid. Examples of such a solvent include an aprotic polar solvent, and examples of the aprotic polar solvent include an anthracene, an anthracene, an guanamine, and the like, which are described in one of the above (water-soluble organic solvents). Indoleamines, lactones, and imidazolinones. Among these aprotic polar solvents, N-methyl-2-pyrrolidone (NMP), N,N-dimethylformamide (DMF), dimethylacetamidine are more preferably used as a solvent for the adhesive. Amine (DMAC), hexamethylphosphoniumamine, and 1,3-dimethyl-2-imidazolidinone.
對於使四羧酸二酐成分與二胺成分反應時之溫度，只要反應可良好地進行，則無特別限定。典型的情 況下，四羧酸二酐成分、與二胺成分之反應溫度較佳為-5℃~150℃，更佳為0℃~120℃，最佳為0℃~70℃。使四羧酸二酐成分、與二胺成分反應之時間根據反應溫度亦相異，典型的情況下，較佳為1小時~50小時，更佳為2小時~40小時，最佳為5小時~30小時。 The temperature at the time of reacting the tetracarboxylic dianhydride component with the diamine component is not particularly limited as long as the reaction proceeds satisfactorily. Typical situation The reaction temperature of the tetracarboxylic dianhydride component and the diamine component is preferably -5 ° C to 150 ° C, more preferably 0 ° C to 120 ° C, and most preferably 0 ° C to 70 ° C. The reaction time of the tetracarboxylic dianhydride component and the diamine component varies depending on the reaction temperature. Typically, it is preferably from 1 hour to 50 hours, more preferably from 2 hours to 40 hours, and most preferably 5 hours. ~30 hours.
對於作為聚醯胺酸之合成原料之四羧酸二酐成分，只要能經由與二胺成分反應從而形成聚醯胺酸即可，無特別限定。四羧酸二酐成分可從以往作為聚醯胺酸之合成原料而使用之四羧酸二酐中適當選擇。四羧酸二酐成分既可為芳香族四羧酸二酐或亦可為脂肪族四羧酸二酐。從所形成之接著層3之耐熱性之點考慮，四羧酸二酐成分較佳為芳香族四羧酸二酐。又，四羧酸二酐成分可組合使用2種以上。 The tetracarboxylic dianhydride component which is a synthetic raw material of polylysine is not particularly limited as long as it can react with the diamine component to form polyamic acid. The tetracarboxylic dianhydride component can be suitably selected from the conventional tetracarboxylic dianhydride used as a synthetic raw material of poly-proline. The tetracarboxylic dianhydride component may be an aromatic tetracarboxylic dianhydride or an aliphatic tetracarboxylic dianhydride. The tetracarboxylic dianhydride component is preferably an aromatic tetracarboxylic dianhydride from the viewpoint of heat resistance of the formed adhesive layer 3. Further, the tetracarboxylic dianhydride component may be used in combination of two or more kinds.
作為芳香族四羧酸二酐之合適之具體例，可舉出均苯四甲酸二酐、2,3,6,7-萘四甲酸二酐、1,4,5,8-萘四甲酸二酐等。於此等芳香族四羧酸二酐中，更佳使用均苯四甲酸二酐。另外，作為脂環式四羧酸二酐，可舉出1,2,3,4-環丁烷四甲酸二酐、1,2,3,4-環戊烷四甲酸二酐、及、1,2,4,5-環己烷四甲酸二酐等。 Specific examples of suitable aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, and 1,4,5,8-naphthalenetetracarboxylic acid Anhydride, etc. Among the aromatic tetracarboxylic dianhydrides, pyromellitic dianhydride is more preferably used. Further, examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, and 1 , 2,4,5-cyclohexanetetracarboxylic dianhydride, and the like.
對於作為聚醯胺酸之合成原料之二胺成分，只要能經 由與四羧酸二酐成分反應從而形成聚醯胺酸即可，沒有特別限定。二胺成分可從以往作為聚醯胺酸之合成原料而使用之二胺中適當選擇。二胺成分既可以是芳香族二胺或亦可為脂肪族二胺。從所形成之接著層3之耐熱性之點考慮，二胺成分更佳為芳香族二胺。二胺成分可組合使用2種以上。 For the diamine component which is a synthetic raw material of polylysine, as long as it can pass It is not particularly limited as long as it is reacted with a tetracarboxylic dianhydride component to form polyamic acid. The diamine component can be appropriately selected from the conventional diamine used as a synthetic raw material of polyamic acid. The diamine component may be either an aromatic diamine or an aliphatic diamine. The diamine component is more preferably an aromatic diamine from the viewpoint of heat resistance of the formed adhesive layer 3. Two or more types of diamine components can be used in combination.
作為芳香族二胺之合適之具體例，可舉出對苯二胺、間苯二胺、2,4-二胺基甲苯、4,4’-二胺基聯苯、4,4’-二胺基-2,2’-雙(三氟甲基)聯苯、3,3’-二胺基二苯甲酮、4,4’-二胺基二苯甲酮、3,3’-二胺基二苯碸、4,4’-二胺基二苯碸、4,4’-二胺基二苯硫醚、4,4’-二胺基二苯甲烷、4,4’-二胺基二苯醚、3,4’-二胺基二苯醚、3,3’-二胺基二苯醚、1,4-雙(4-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、1,3-雙(3-胺基苯氧基)苯、4,4’-雙(4-胺基苯氧基)聯苯、雙[4-(4-胺基苯氧基)苯基]碸、雙[4-(3-胺基苯氧基)苯基]碸、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷、2,2-雙[4-(4-胺基苯氧基)苯基]六氟丙烷、9,9-雙(4-胺基苯基)芴、9,9-雙(4-胺基-3-甲基苯基)芴、及4,4’-[1,4-伸苯基雙(1-甲基乙烷-1,1-二基)]二苯胺等。於此等芳香族二胺中，從價格、容易獲得等方面考慮，更佳使用對苯二胺、間苯二胺、2,4-二胺基甲苯及4,4’-二胺基二苯醚。 Specific examples of suitable aromatic diamines include p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 4,4'-diaminobiphenyl, and 4,4'-di. Amino-2,2'-bis(trifluoromethyl)biphenyl, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-di Aminodiphenyl hydrazine, 4,4'-diaminodiphenyl hydrazine, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylmethane, 4,4'-diamine Diphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 1,4-bis(4-aminophenoxy)benzene, 1,3-double (4-Aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-( 4-aminophenoxy)phenyl]anthracene, bis[4-(3-aminophenoxy)phenyl]anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl Propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)anthracene, 9,9-bis(4- Amino-3-methylphenyl)anthracene, and 4,4'-[1,4-phenylphenylbis(1-methylethane-1,1-diyl)]diphenylamine. Among these aromatic diamines, p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene and 4,4'-diaminodiphenyl are more preferably used in terms of price and availability. ether.
對於聚醯胺酸之合成而言，除了四羧酸二酐成分、二 胺成分、及、溶劑以外，作為其他成分，亦可包含聚合促進劑、及、二羧酸二酐。 For the synthesis of poly-proline, in addition to the tetracarboxylic dianhydride component, two Other than the amine component and the solvent, a polymerization accelerator and a dicarboxylic acid dianhydride may be contained as other components.
作為聚合促進劑，可以合適地使用例如咪唑、苯并咪唑、4-羥基吡啶，但不限於此。 As the polymerization accelerator, for example, imidazole, benzimidazole, or 4-hydroxypyridine can be suitably used, but is not limited thereto.
又，合成聚醯胺酸時，可同時使用四羧酸二酐與二羧酸酐。若同時使用此等羧酸酐，則有時生成之聚醯胺酸之特性進一步變好。作為二羧酸酐，可舉出例如馬來酸酐、琥珀酸酐、衣康酸酐、鄰苯二甲酸酐、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、甲基內亞甲基四氫鄰苯二甲酸酐、氯橋酸酐、甲基四氫鄰苯二甲酸酐、戊二酸酐、順式-4-環己烯-1,2-二甲酸酐等。 Further, in the case of synthesizing polyamic acid, tetracarboxylic dianhydride and dicarboxylic anhydride can be used at the same time. When these carboxylic anhydrides are used at the same time, the properties of the produced polyglycolic acid may be further improved. Examples of the dicarboxylic acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methyl endomethylenetetrahydrogen. Phthalic anhydride, chlorobridge anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride, cis-4-cyclohexene-1,2-dicarboxylic anhydride, and the like.
又，經由利用上述之非質子性極性溶劑將聚醯胺酸之濃度調整為1重量%以上、10重量%以下之範圍內，可得到用於形成接著層3之接著劑。作為接著劑中使用之非質子性極性溶劑，較佳使用例如N-甲基-2-吡咯烷酮(NMP)、N,N-二甲基甲醯胺(DMF)、及、二甲基乙醯胺(DMAC)等。 Further, by adjusting the concentration of the polyamic acid to 1% by weight or more and 10% by weight or less by using the aprotic polar solvent described above, an adhesive for forming the adhesive layer 3 can be obtained. As the aprotic polar solvent used in the adhesive, for example, N-methyl-2-pyrrolidone (NMP), N,N-dimethylformamide (DMF), and dimethylacetamide are preferably used. (DMAC), etc.
黏貼步驟中，以醯亞胺鍵進行了水解之平面部與支撐板2相對之方式，藉由接著層3黏貼基板1支撐板2。 In the pasting step, the plane portion which is hydrolyzed by the quinone bond is opposed to the support plate 2, and the substrate 2 is adhered to the substrate 1 by the adhesion layer 3.
關於黏貼步驟，可例如經由加壓、層壓及輥式層壓等一邊加熱一邊進行即可。黏貼步驟中，例如，藉由接著層3將基板1與支撐板2疊合，使用可經由商業途 徑獲得之層壓機裝置等，於40℃~100℃左右之溫度條件下進行加熱、黏貼。於此，利用層壓機裝置而施加至層合體10之壓力根據支撐板2之機械強度、及、層合體之大小等而適當調整即可。另外，黏貼步驟可於大氣壓條件下、或減壓條件下之任意條件下進行即可。又，於大氣壓條件下進行黏貼步驟時，更佳以基板1不吸收濕氣之方式，於調整了濕度之環境中進行。 The adhesion step may be carried out, for example, by heating, lamination, roll lamination, or the like. In the pasting step, for example, the substrate 1 and the support plate 2 are superposed by the adhesive layer 3, and the use can be carried out through a commercial route. The laminating machine device obtained by the diameter is heated and pasted at a temperature of about 40 ° C to 100 ° C. Here, the pressure applied to the laminate 10 by the laminator apparatus may be appropriately adjusted according to the mechanical strength of the support plate 2, the size of the laminate, and the like. Further, the pasting step may be carried out under any conditions of atmospheric pressure or under reduced pressure. Further, when the adhesion step is carried out under atmospheric pressure, it is more preferable to carry out the humidity in an environment in which the substrate 1 does not absorb moisture.
對於黏貼步驟中形成之層合體10，在其後之步驟中，可利用光刻法或等離子化學氣相沉積法(等離子CVD法)等而於基板1上形成電路等。於這般於基板1上形成電路等之步驟中，亦可進行經由等離子CVD法而於基板上沉積之非晶質矽之脫氫化、及、經由脫氫化而形成之矽層之多晶化等。在上述步驟中，層合體10在減壓環境下或氮、氬等非活性氣體環境下被供於200℃以上且400℃以下的範圍內的溫度條件。 In the subsequent step 10 of the bonding step, a circuit or the like can be formed on the substrate 1 by a photolithography method, a plasma chemical vapor deposition method (plasma CVD method) or the like in the subsequent step. In the step of forming a circuit or the like on the substrate 1, the dehydrogenation of the amorphous germanium deposited on the substrate by the plasma CVD method, and the polycrystallization of the germanium layer formed by dehydrogenation may be performed. . In the above step, the laminate 10 is supplied to a temperature condition in a range of 200 ° C or more and 400 ° C or less under a reduced pressure atmosphere or an inert gas atmosphere such as nitrogen or argon.
由此，可使於基板1上形成之胺基、與存在於接著層3之羧基適宜地縮合，可於基板1與接著層3之間形成醯胺鍵。另外，亦可於黏貼步驟後、於剝離步驟前，在200℃以上、400℃以下之範圍內之溫度條件下，對層合體10進行加熱，從而使形成了接著層3之聚醯胺酸進行醯亞胺化。由此，可提高接著層3與支撐板2之密著性。另外，可防止在基板1與支撐板2之間產生空隙。因 而，可使層合體10應對高溫處理工藝。 Thereby, the amine group formed on the substrate 1 can be appropriately condensed with the carboxyl group present in the adhesive layer 3, and a guanamine bond can be formed between the substrate 1 and the adhesive layer 3. In addition, the laminate 10 may be heated under the temperature conditions of 200 ° C or higher and 400 ° C or lower after the adhesion step to form the polyamine acid forming the adhesion layer 3 .醯imination. Thereby, the adhesion between the adhesive layer 3 and the support plate 2 can be improved. In addition, it is possible to prevent a gap from being generated between the substrate 1 and the support plate 2. because However, the laminate 10 can be subjected to a high temperature treatment process.
又，對於於黏貼步驟後可於基板1上形成之電子裝置，可舉出例如主動元件、電子電路、及、其他元件。例如，對於主動元件，可舉出擔負電氣佈線之佈線基板、電晶體、及、二極體等，對於電子電路，可舉出電阻、電容器、及、感應器等之被動裝置。另外，作為其他元件，可舉出感應溫度、光、及濕度等之感測器元件、發光元件、液晶顯示、電泳顯示、自發光顯示等之圖像顯示元件、利用無線、有線之通信元件、運算元件、記憶元件、MEMS元件、太陽能電池、薄膜電晶體等。 Further, examples of the electronic device that can be formed on the substrate 1 after the bonding step include an active device, an electronic circuit, and other components. For example, the active element includes a wiring board, a transistor, a diode, and the like which are responsible for the electric wiring. Examples of the electronic circuit include a passive device such as a resistor, a capacitor, and an inductor. Further, examples of other elements include sensor elements such as sensor elements, light-emitting elements, liquid crystal display, electrophoretic display, and self-luminous display, which are inductive temperature, light, and humidity, and communication elements using wireless or wired, Computing elements, memory elements, MEMS elements, solar cells, thin film transistors, and the like.
層合體10為將經由聚醯亞胺樹脂預先形成為膜狀之基板1、與支撐基板1之支撐板2藉由包含上述式(1)所示之聚醯胺酸所成之接著層3進行層合所成之層合體，並且具有經由下述胺基、與聚醯胺酸所具有之羧基進行縮合而形成之醯胺鍵，所述胺基來自於存在於上述基板之與上述支撐體相對之平面部之聚醯亞胺樹脂。即，本發明之一實施形態之層合體於典型的情況下，為經由本發明的一實施形態之層合體之製造方法而製造之層合體10。 The laminate 10 is a substrate 1 which has been previously formed into a film shape via a polyimide resin, and a support layer 2 of the support substrate 1 is formed by a bonding layer 3 comprising a polyamic acid represented by the above formula (1). Laminating the formed laminate, and having a sulfhydryl bond formed by condensation with a carboxyl group of a polyamic acid via an amine group derived from the substrate and opposite to the support Polyimide resin in the flat portion. In other words, the laminate of one embodiment of the present invention is a laminate 10 produced by the method for producing a laminate according to an embodiment of the present invention.
由此，層合體10不同於使用丙烯酸樹脂形成接著層而得到之層合體，例如，於350℃左右之高溫條件下處理層合體10時，可防止由於接著層3發生熱分解而產生氣體。因此，加熱時，可防止於基板1與支撐板2之 間產生空隙。另外，層合體10不同於例如使用胺基矽烷等之偶合劑將基板與支撐體層合而成之層合體，適度地調整了層合體中的接著層3與支撐板2之密著性。因此，可將基板1與聚醯亞胺化了之接著層3一同從支撐板2良好地剝離。 Thus, the laminate 10 is different from the laminate obtained by forming an adhesive layer using an acrylic resin. For example, when the laminate 10 is treated under high temperature conditions of about 350 ° C, generation of gas due to thermal decomposition of the adhesive layer 3 can be prevented. Therefore, when heating, it can be prevented from being on the substrate 1 and the support plate 2 A gap is created between them. Further, the laminate 10 is different from, for example, a laminate in which a substrate and a support are laminated using a coupling agent such as an amino decane, and the adhesion between the adhesive layer 3 and the support sheet 2 in the laminate is appropriately adjusted. Therefore, the substrate 1 can be favorably peeled off from the support sheet 2 together with the polyimide layer which is polyimideized.
本發明之一實施形態之層合體之形成用套組具備有：本發明之一實施方式之層合體之製造方法所包含之水解步驟中所使用之處理液、與於接著層形成步驟中使用之接著劑。 The kit for forming a laminate according to an embodiment of the present invention includes the treatment liquid used in the hydrolysis step included in the method for producing the laminate according to the embodiment of the present invention, and the treatment liquid used in the step of forming the adhesive layer. Follow-up agent.
根據上述之構成，可適宜地進行本發明之一實施形態之層合體之製造方法。因此，本實施形態之層合體之製造用套組亦為本發明之範疇。 According to the above configuration, a method for producing a laminate according to an embodiment of the present invention can be suitably carried out. Therefore, the kit for manufacturing the laminate of the present embodiment is also within the scope of the invention.
以下，對本發明之一實施形態之基板之處理方法進行更詳細之說明。 Hereinafter, a method of processing a substrate according to an embodiment of the present invention will be described in more detail.
本實施形態之基板之處理方法包含：進行本發明之一實施形態之層合體之製造方法、層合體形成步驟(圖1之(a)~(e))、與將基板1從層合體10剝離之剝離步驟(圖1之(f)及(g))。又，對於層合體形成步驟，由於與上述之一實施形態之層合體之製造方法相同，因此省略其說明。又，對於圖1之(e)所示之層合 體10，於剝離步驟前，於基板1上形成各種佈線等，安裝積體電路等之構造物。 The method for processing a substrate according to the present embodiment includes a method for producing a laminate according to an embodiment of the present invention, a step of forming a laminate ((a) to (e) of FIG. 1), and peeling off the substrate 1 from the laminate 10. The stripping step ((f) and (g) of Figure 1). Further, the step of forming the laminate is the same as the method of manufacturing the laminate according to the above-described embodiment, and thus the description thereof will be omitted. Also, for the lamination shown in (e) of Fig. 1 In the body 10, various wirings and the like are formed on the substrate 1 before the peeling step, and a structure such as an integrated circuit is mounted.
用於將基板1從層合體10剝離之方法可根據基板1之種類、及、於基板1上形成之電路等之種類而適當選擇即可。例如，如圖1之(f)所示，剝離步驟中，將層合體10中之支撐板2例如吸附固定於載置台，在將基板1之一邊固定的狀態下，將該基板1之一邊提起，由此緩緩剝離。作為將層合體10中之基板的一邊固定的方法，可舉出經由鑷子等夾持之方法，黏貼膠帶之方法，及利用吸附部進行吸附固定的方法等。又，對於層合體10，也可以預先以基板1之邊緣部分之一部分從支撐板2露出之方式進行層合，然後夾持該一部分並提起基板1，由此將基板1剝離。 The method for peeling the substrate 1 from the laminate 10 may be appropriately selected depending on the type of the substrate 1 and the type of circuit formed on the substrate 1. For example, as shown in FIG. 1(f), in the peeling step, the support plate 2 in the laminate 10 is adsorbed and fixed to the mounting table, for example, and one side of the substrate 1 is lifted while one side of the substrate 1 is fixed. , and slowly stripped. Examples of the method of fixing one side of the substrate in the laminate 10 include a method of sandwiching a tape by a tweezers or the like, a method of adhering the tape, and a method of adsorbing and fixing by the adsorption portion. Moreover, the laminated body 10 may be laminated in such a manner that one of the edge portions of the substrate 1 is exposed from the support plate 2 in advance, and then the substrate 1 is lifted by sandwiching the portion and lifting the substrate 1.
剝離步驟中，在將基板1剝離之前，為了可以規定之大小將該基板1剝離，也可以預先在基板1中切出切口。作為用於在基板1中切出切口的方法，可舉出例如使鐳射相對於基板1而相對地掃描從而切出切口的方法；使水噴注(water jet)相對於基板1而相對地掃描從而切出切口之方法、及、利用半導體晶片之切割裝置從而切出切口之方法等。 In the peeling step, before the substrate 1 is peeled off, the substrate 1 may be cut out in a predetermined size, and the slit may be cut out in the substrate 1 in advance. As a method for cutting a slit in the substrate 1, for example, a method in which a laser is scanned relative to the substrate 1 to cut a slit; a water jet is relatively scanned with respect to the substrate 1 Thus, a method of cutting out the slit, a method of cutting out the slit by using a cutting device of the semiconductor wafer, and the like.
又，於剝離步驟中，彼此相對的、基板1之平面部與支撐板2之平面部之間的角度不限於圖1之 (f)所示那樣的大致90°。剝離步驟中之基板1與支撐板2之間的角度考慮由於基板1被拉伸而施加的張力、及由於在基板1上形成之電路等被彎曲而施加的應力等，以使得基板1及電路等不發生破損進行適當調整即可。 Further, in the peeling step, the angle between the plane portion of the substrate 1 and the plane portion of the support plate 2 opposed to each other is not limited to that of FIG. (f) is approximately 90° as shown. The angle between the substrate 1 and the support plate 2 in the peeling step takes into consideration the tension applied due to the stretching of the substrate 1 and the stress applied due to the bending of the circuit formed on the substrate 1, etc., so that the substrate 1 and the circuit If it is not damaged, it can be adjusted appropriately.
對於層合體10，接著層3相對於支撐板2之剝離強度被適度地調整。更具體而言，關於接著層3相對於支撐板2之剝離強度，例如於0.75cm/秒之剝離速度條件下，該基板1之剝離強度為30g/cm~80g/cm左右，更佳為30g/cm~50g/cm左右。因此，如圖1之(g)所示，於剝離步驟中，可將一體化了之基板1與接著層3於接著層3與支撐板2之介面順利地剝離。因而，可防止安裝於基板1之電路等由於將基板1剝離時所施加之力而發生破損。 With respect to the laminate 10, the peel strength of the layer 3 with respect to the support plate 2 is moderately adjusted. More specifically, regarding the peeling strength of the adhesive layer 3 with respect to the support sheet 2, for example, at a peeling speed of 0.75 cm/sec, the peel strength of the substrate 1 is about 30 g/cm to 80 g/cm, more preferably 30 g. /cm~50g/cm or so. Therefore, as shown in FIG. 1(g), in the peeling step, the integrated substrate 1 and the adhesive layer 3 can be smoothly peeled off from the interface between the adhesive layer 3 and the support plate 2. Therefore, it is possible to prevent the circuit or the like mounted on the substrate 1 from being damaged by the force applied when the substrate 1 is peeled off.
此外，剝離步驟中，亦可以將基板1之一邊固定於曲率大之輥，利用該輥將基板1捲取從而剝離。 Further, in the peeling step, one side of the substrate 1 may be fixed to a roll having a large curvature, and the substrate 1 may be taken up by the roll to be peeled off.
本發明之一實施方式之層合體之製造方法不限於上述之實施形態。例如，於其他實施方式之層合體之製造方法中，於水解步驟中，於基板1中之2個平面部之中，僅對與接著層3相對側之一個面進行水解步驟。 The method for producing a laminate according to an embodiment of the present invention is not limited to the above embodiment. For example, in the method for producing a laminate according to another embodiment, in the hydrolysis step, only one surface on the side opposite to the subsequent layer 3 is subjected to a hydrolysis step among the two planar portions in the substrate 1.
在一實施形態之層合體之製造方法所包含之水解步驟中，例如，經由將附有接著劑之PET膜、PEN膜、烯烴膜、聚醯亞胺膜等之保護膜黏貼於基板1之一個 平面部並進行處理，從而僅對基板1之一個平面部進行水解處理。當然，經由該構成，亦可適度地提高基板1與接著層3之密著性。 In the hydrolysis step included in the method for producing a laminate according to the embodiment, for example, a protective film of a PET film, a PEN film, an olefin film, a polyimide film, or the like with an adhesive attached thereto is adhered to one of the substrates 1 The flat portion is processed to perform hydrolysis treatment only on one planar portion of the substrate 1. Of course, with this configuration, the adhesion between the substrate 1 and the adhesive layer 3 can be appropriately improved.
另外，在又一實施形態之層合體之製造方法中，例如，聚醯胺酸可以經由下述方式生成：將四羧酸二酐成分與二胺成分溶解於溶劑中，將所得到之溶液塗佈於支撐板2上，並對該支撐板2進行加熱。由此，可在支撐板2上形成包含聚醯胺酸而成之接著層3。因而，可適宜地實施本發明的一實施形態之層合體之製造方法。 Further, in the method for producing a laminate according to still another embodiment, for example, polylysine may be produced by dissolving a tetracarboxylic dianhydride component and a diamine component in a solvent, and coating the obtained solution. It is placed on the support plate 2 and the support plate 2 is heated. Thereby, the adhesive layer 3 containing polyamic acid can be formed on the support plate 2. Therefore, the method for producing a laminate according to an embodiment of the present invention can be suitably carried out.
另外，又一實施形態之層合體之製造方法中，例如，於水解步驟中，亦可利用真空等離子處理或UV臭氧處理從而使基板1之聚醯亞胺樹脂水解、開裂。於該構成中，亦可於基板1之平面部形成胺基。 Further, in the method for producing a laminate according to still another embodiment, for example, in the hydrolysis step, the polyimine resin of the substrate 1 may be hydrolyzed and cracked by vacuum plasma treatment or UV ozone treatment. In this configuration, an amine group can also be formed on the plane portion of the substrate 1.
對於本發明之層合體，來自於形成基板之聚醯亞胺樹脂之胺基不限於經由利用水解而使醯亞胺鍵開裂從而得到之胺基。即，若是來自於合成聚醯亞胺樹脂時所用之二胺成分之胺基，則基板所具有之胺基之來源沒有限定。此係由於，在該構成中，亦可經由使存在於基板之平面部的胺基、與接著層所包含之聚醯胺酸所具有之羧基進行縮合所成醯胺鍵。 In the laminate of the present invention, the amine group derived from the polyimide resin forming the substrate is not limited to the amine group obtained by cracking the quinone bond by hydrolysis. That is, in the case of an amine group derived from a diamine component used in the synthesis of a polyimide resin, the source of the amine group of the substrate is not limited. In this configuration, the amine group which is present in the planar portion of the substrate and the carboxyl group of the polyamic acid contained in the adhesive layer may be condensed to form a guanamine bond.
本發明不限於上述之各實施形態，可於請求項書所示之範圍內進行各種變更，將相異之實施型態中分 別公開之技術手段適當組合而得到之實施形態也包含於本發明之技術範圍內。 The present invention is not limited to the above-described embodiments, and various modifications can be made within the scope of the claims, and the different embodiments can be divided. The embodiments obtained by appropriately combining the technical means disclosed are also included in the technical scope of the present invention.
製作實施例1之層合體、及、比較例1~2之層合體，對各層合體進行耐熱性之評估、及、剝離性之評估。 The laminate of Example 1 and the laminates of Comparative Examples 1 and 2 were produced, and each laminate was evaluated for heat resistance and evaluation of peelability.
首先，對於實施例1，作為包含聚醯胺酸之接著劑，調製以樹脂之濃度成為2重量%之方式用NMP將Pyre-ML(註冊商標)RC-5019(聚(均苯四甲酸二酐-co-4,4’-二氨基二苯醚(Oxydianiline))醯胺酸溶液；NMP溶液，濃度15.0重量%~16.0重量%，Sigma-Aldrich公司制)稀釋而成之接著劑。接著，利用旋塗法將該包含聚醯胺酸之接著劑塗佈於10cm見方之玻璃支撐體，於170℃、3分鐘之條件下進行加熱，從而於玻璃支撐體上形成厚度200nm之接著層(接著層形成步驟)。 First, in Example 1, as a binder containing poly-proline, Pyre-ML (registered trademark) RC-5019 (poly(pyrenetetracarboxylic dianhydride) was prepared by NMP so that the concentration of the resin became 2% by weight. -co-4,4'-diaminodiphenyl ether (methine acid solution; NMP solution, concentration: 15.0% by weight to 16.0% by weight, manufactured by Sigma-Aldrich Co., Ltd.). Next, the adhesive containing polyamic acid was applied to a 10 cm square glass support by spin coating, and heated at 170 ° C for 3 minutes to form an adhesive layer having a thickness of 200 nm on the glass support. (Next layer formation step).
另外，以濃度成為4.5重量%之方式，將氫氧化四甲銨(TMAH)溶解於水與乙醇的重量比為6：4之混合液中，從而調製處理液。於調製之處理液中於23℃、3分鐘之條件下浸漬10cm見方之PI(聚醯亞胺)膜基板(製品名：聚醯亞胺膜Kapton H型，厚度：50μm，DU PONT-TORAY公司製)，之後提起，進行水洗及瀝淨，然後於90℃、5分鐘之條件下進行乾燥，除去水分(水解步驟)。 Further, tetramethylammonium hydroxide (TMAH) was dissolved in a mixed liquid having a weight ratio of water to ethanol of 6:4 so as to have a concentration of 4.5% by weight to prepare a treatment liquid. A 10 cm square PI (polyimine) film substrate was immersed in a treatment liquid at 23 ° C for 3 minutes (product name: polyimine film Kapton H type, thickness: 50 μm, DU) After PONT-TORAY Co., Ltd., it was lifted, washed with water, and drained, and then dried at 90 ° C for 5 minutes to remove water (hydrolysis step).
接著，使用設定為溫度80℃、層壓機輸送速度1.0m/分鐘的條件的層壓機裝置VA-700(大成層壓機股份有限公司製)，將水解處理後的PI膜基板、和形成了接著層的玻璃支撐體藉由接著層進行黏貼(黏貼步驟)。 Then, a laminate apparatus VA-700 (manufactured by Dacheng Laminator Co., Ltd.) set to a temperature of 80 ° C and a laminating machine conveying speed of 1.0 m/min was used to form a PI film substrate after hydrolysis treatment. The glass support of the subsequent layer is pasted by the adhesive layer (adhesion step).
接著，作為比較例1之層合體，以聚丙烯酸之濃度為4重量%之方式用水稀釋聚(丙烯酸)溶液(平均分子量~100,000，水溶液，濃度35重量%，Sigma-Aldrich公司製)，利用旋塗法塗佈於與實施例1使用之玻璃支撐體相同之玻璃支撐體上。接著，於100℃、3分鐘之條件下，加熱玻璃支撐體，形成厚度200nm之接著層。另外，於與實施例1相同之條件下，對PI膜基板進行水解處理，經由加熱進行乾燥。之後，於與實施例1相同之條件下，黏貼PI膜基板與玻璃支撐體。由此，製作比較例1之層合體。 Next, as a laminate of Comparative Example 1, a poly(acrylic acid) solution (having an average molecular weight of ~100,000, an aqueous solution, a concentration of 35 wt%, manufactured by Sigma-Aldrich Co., Ltd.) was diluted with water so that the concentration of the polyacrylic acid was 4% by weight. The coating method was applied to the same glass support as the glass support used in Example 1. Next, the glass support was heated at 100 ° C for 3 minutes to form an adhesive layer having a thickness of 200 nm. Further, under the same conditions as in Example 1, the PI film substrate was subjected to hydrolysis treatment and dried by heating. Thereafter, the PI film substrate and the glass support were adhered under the same conditions as in Example 1. Thus, the laminate of Comparative Example 1 was produced.
接著，作為比較例2的層合體，利用旋塗法將3-胺基丙基三乙氧基矽烷(APTES，偶合劑，信越化學公司製)塗佈於與實施例1使用之玻璃支撐體相同之玻璃支撐體 上。接著，於170℃、3分鐘之條件下，加熱玻璃支撐體。另外，於與實施例1相同的條件下，對PI膜基板進行水解處理，經由加熱進行乾燥。之後，於與實施例1相同之條件下，黏貼PI膜基板與玻璃支撐體。由此，製作比較例2之層合體。 Next, as a laminate of Comparative Example 2, 3-aminopropyltriethoxysilane (APTES, coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.) was applied by the spin coating method to the same glass support as used in Example 1. Glass support on. Next, the glass support was heated at 170 ° C for 3 minutes. Further, under the same conditions as in Example 1, the PI film substrate was subjected to hydrolysis treatment and dried by heating. Thereafter, the PI film substrate and the glass support were adhered under the same conditions as in Example 1. Thus, the laminate of Comparative Example 2 was produced.
以下之表1中表示出了實施例1之層合體及比較例1~2之層合體之構成。 The composition of the laminate of Example 1 and the laminate of Comparative Examples 1 and 2 is shown in Table 1 below.
接著，對於實施例1之層合體、及、比較例1~2之層合體，進行剝離性之評估。耐熱性及剝離性之評估條件如以下所示。 Next, the laminate of Example 1 and the laminate of Comparative Examples 1 and 2 were evaluated for peelability. The evaluation conditions of heat resistance and peelability are as follows.
將上述之製作時之各層合體置於立式烘烤爐TS8000MB(東京應化工業股份有限公司製)中，於氮環境下、350℃、1小時之條件下進行加熱，由此進行耐熱性之評估。對於加熱後之狀態，經由目視，評價PI膜基板與玻璃支撐體之間是否產生了空隙，將沒有產生空隙之層合體評估為“○”，將產生了空隙之層合體評估為“×”。將耐熱性之評估結果表示於以下之表1中。 The laminates prepared in the above-mentioned production were placed in a vertical baking oven TS8000MB (manufactured by Tokyo Ohka Kogyo Co., Ltd.), and heated under a nitrogen atmosphere at 350 ° C for 1 hour to carry out heat resistance. Evaluation. In the state after the heating, whether or not a void was generated between the PI film substrate and the glass support was evaluated by visual observation, the laminate having no voids was evaluated as "○", and the laminate in which the void was generated was evaluated as "X". The evaluation results of the heat resistance are shown in Table 1 below.
對於剝離性之評估，針對耐熱性評估後之各層合體， 於層合於玻璃支撐體之PI膜基板上切出1cm×9cm之尺寸之切口，在將層合體固定於水平之狀態下，把持PI膜基板之切出切口之部分中之長度方向的一端，評估以0.75cm/秒之速度朝向垂直方向向上側提起時之剝離強度。又，於剝離強度之測定中使用拉伸壓縮試驗機SV-55C-2H(今田製作所製)。剝離性之評估結果表示於已下之表1。 For the evaluation of the peelability, for each laminate after the heat resistance evaluation, Cutting a slit having a size of 1 cm × 9 cm on the PI film substrate laminated on the glass support, and holding the laminate at a horizontal position, holding one end of the portion of the PI film substrate cut out of the slit, The peel strength at the time of lifting up to the vertical direction at a speed of 0.75 cm/sec was evaluated. Further, a tensile compression tester SV-55C-2H (manufactured by Ikuta Seisakusho Co., Ltd.) was used for the measurement of the peel strength. The results of the evaluation of the peelability are shown in Table 1 below.
對於實施例1之層合體而言，即便於350℃、1小時之加熱條件下，亦未確認到空隙之產生。另外，對於實施例1之層合體而言，PI膜基板之剝離強度為45~47g/cm，並且可將PI膜基板順利地剝離而不使其破損。另外，接著層與PI膜基板一體化地從玻璃支撐體剝離。 With respect to the laminate of Example 1, no occurrence of voids was observed even under heating conditions of 350 ° C for 1 hour. Further, in the laminate of Example 1, the peel strength of the PI film substrate was 45 to 47 g/cm, and the PI film substrate was smoothly peeled off without being damaged. Further, the adhesive layer is peeled off from the glass support body integrally with the PI film substrate.
與此相對，對於比較例1之層合體而言，於耐熱性之評估中，於PI膜基板與玻璃支撐體之間確認到 空隙(×)。又，對於比較例1之層合體而言，PI膜基板立即發生了剝離，未可進行剝離強度之測定。 On the other hand, in the laminate of Comparative Example 1, it was confirmed between the PI film substrate and the glass support in the evaluation of heat resistance. Void (×). Further, in the laminate of Comparative Example 1, the PI film substrate was immediately peeled off, and the peel strength was not measured.
對於比較例2之層合體而言，雖然沒有產生空隙(○)，但結果是，PI膜基板之剝離強度高，於剝離時可形成於PI膜基板上之積體電路等之構造物可能發生破損。 In the laminate of Comparative Example 2, voids (○) were not produced, but as a result, the peel strength of the PI film substrate was high, and a structure such as an integrated circuit which can be formed on the PI film substrate during peeling may occur. damaged.
由以上的結果可確認，經由對PI膜基板進行水解處理、並使用聚醯胺酸將其黏貼於玻璃支撐體上，由此耐熱性提高，並且可將PI膜基板順利地剝離。 From the above results, it was confirmed that the PI film substrate was subjected to hydrolysis treatment and adhered to the glass support by using polyamic acid, whereby heat resistance was improved, and the PI film substrate was smoothly peeled off.
本發明可合適地用於例如微細化之半導體裝置之製造步驟中。 The present invention can be suitably used in, for example, a manufacturing step of a semiconductor device that is miniaturized.
1‧‧‧基板 1‧‧‧Substrate
2‧‧‧支撐板(支撐體) 2‧‧‧Support plate (support)
3‧‧‧接著層 3‧‧‧Next layer
10‧‧‧層合體 10‧‧‧Layer
50‧‧‧處理槽 50‧‧‧Processing tank
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