TWI628074B - Laminated body, laminated board, printed wiring board, and method for manufacturing laminated body and laminated board - Google Patents
Laminated body, laminated board, printed wiring board, and method for manufacturing laminated body and laminated board Download PDFInfo
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- C08L79/00—Compositions of 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 C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/061—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of metal
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- 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
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- 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
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- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
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- C08G73/1075—Partially aromatic polyimides
- C08G73/1082—Partially aromatic polyimides wholly aromatic in the tetracarboxylic moiety
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- 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
- C08G73/14—Polyamide-imides
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- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C09D179/00—Coating compositions 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 C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
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- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/12—Mountings, e.g. non-detachable insulating substrates
- H01L23/14—Mountings, e.g. non-detachable insulating substrates characterised by the material or its electrical properties
- H01L23/145—Organic substrates, e.g. plastic
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- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/12—Mountings, e.g. non-detachable insulating substrates
- H01L23/14—Mountings, e.g. non-detachable insulating substrates characterised by the material or its electrical properties
- H01L23/15—Ceramic or glass substrates
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- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
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- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
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- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
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- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
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- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
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Abstract
本發明的目的在於提供一種積層體、積層板、以及該積層體及積層板的製造方法,其中,該積層體及積層板中,玻璃基板層與樹脂組成物層的黏著性、及耐熱性充分。另外,本發明的目的在於提供一種使用該積層體或積層板而成的印刷線路板。 An object of the present invention is to provide a laminate, a laminate, and a method for producing the laminate and the laminate, wherein the laminate and the laminate have sufficient adhesion and heat resistance of the glass substrate layer and the resin composition layer. . Further, an object of the present invention is to provide a printed wiring board using the laminated body or laminated board.
為了達成上述目的,本發明的積層體具有1層以上的樹脂組成物層及1層以上的玻璃基板層,其中,前述樹脂組成物層包含聚醯胺醯亞胺樹脂與環氧樹脂。另外,本發明提供一種積層板及印刷線路板,該積層板是將該積層體的樹脂組成物層硬化而成,該印刷線路板使用該等積層體或積層板而成。 In order to achieve the above object, the laminate of the present invention has one or more resin composition layers and one or more glass substrate layers, wherein the resin composition layer contains a polyimide film and an epoxy resin. Further, the present invention provides a laminated board and a printed wiring board obtained by curing a resin composition layer of the laminated body, and the printed wiring board is formed using the laminated body or the laminated board.
Description
本發明關於一種積層體、積層板以及該積層體、積層板的製造方法、與印刷線路板,該積層體、積層板,適合用於半導體封裝體和印刷線路板。 The present invention relates to a laminate, a laminate, a laminate, a method for producing a laminate, and a printed wiring board, which is suitable for use in a semiconductor package and a printed wiring board.
線路板被要求縮小線路間距,實現高密度的線路。作為因應高密度線路之半導體的構裝方法,目前廣泛地採用倒裝晶片連接方式(flip-chip bonding method),取代以往的引線接合方式(wire bonding method)。 The board is required to reduce the line spacing to achieve high density lines. As a method of arranging a semiconductor for a high-density line, a flip-chip bonding method has been widely used in place of the conventional wire bonding method.
倒裝晶片連接方式,是一種不使用金屬線,而利用焊料球來連接線路板和半導體的方法。該方法中,在設置成彼此相對的線路板與半導體之間配置焊料球,並對整體加熱,使焊料回焊(熔融連接),藉此使線路板和半導體連接並構裝。 The flip chip connection method is a method of connecting a wiring board and a semiconductor using a solder ball without using a metal wire. In this method, solder balls are disposed between a wiring board and a semiconductor which are disposed to face each other, and the whole is heated to reflow (melt-bond) the solder, whereby the wiring board and the semiconductor are connected and assembled.
該方法中,焊料回焊時,接近300℃之熱量將施加在線路板等之上。因此,線路板等需要具備高耐熱性。 In this method, when the solder is reflowed, heat of approximately 300 ° C is applied to the wiring board or the like. Therefore, a circuit board or the like needs to have high heat resistance.
另一方面,對於電子設備的薄型化、輕質化之要求越來越強烈,半導體封裝體和印刷線路板的薄型化、高密度 化不斷發展。為了將因應半導體封裝體和印刷線路板的薄型化、高密度化的電子零件穩定地構裝,抑制構裝時產生之翹曲變得重要。構裝時,半導體封裝體產生翹曲之主要原因之一,是半導體封裝體所使用之積層板與構裝於該積層板的表面上的矽晶片之間具有熱膨脹係數差。因此,使半導體封裝體用積層板的熱膨脹係數,接近矽晶片的熱膨脹係數,亦即努力降低半導體封裝體用積層板的熱膨脹係數,並且作出如下嘗試:使用玻璃膜,作為具有與矽晶片的熱膨脹係數大致相符的熱膨脹係數之層,並藉由加壓將樹脂與玻璃膜積層,藉此來減輕熱衝擊應力(專利文獻1);但所使用之樹脂與玻璃基板的黏著性較低,高溫時由熱膨脹係數差所產生之應力會 On the other hand, there is an increasing demand for thinner and lighter electronic devices, and thinner and higher density of semiconductor packages and printed wiring boards. Continuous development. In order to stably mount electronic components that are thinner and higher in density in accordance with the semiconductor package and the printed wiring board, it is important to suppress warpage generated during the mounting. One of the main causes of warpage of the semiconductor package during the mounting is that the laminated board used in the semiconductor package has a difference in thermal expansion coefficient between the germanium wafer mounted on the surface of the laminated board. Therefore, the thermal expansion coefficient of the laminate for a semiconductor package is made close to the thermal expansion coefficient of the tantalum wafer, that is, the thermal expansion coefficient of the laminate for a semiconductor package is reduced, and an attempt is made to use a glass film as a thermal expansion with a tantalum wafer. A layer having a coefficient of thermal expansion that substantially matches the coefficient, and laminating the resin and the glass film by pressurization, thereby reducing thermal shock stress (Patent Document 1); however, the resin used has a low adhesion to the glass substrate, and at a high temperature The stress caused by the difference in thermal expansion coefficient
導致樹脂層與玻璃基板層之間剝離,因此回焊耐熱性並不充分。 This results in peeling between the resin layer and the glass substrate layer, so the reflow heat resistance is not sufficient.
專利文獻1:日本特許第4657554號公報 Patent Document 1: Japanese Patent No. 4675554
如上所述,玻璃基板與以往的樹脂組成物層之間缺乏黏著性,會於焊料回焊時產生剝離,構裝時的耐熱性不充分。 As described above, the glass substrate and the conventional resin composition layer lack adhesiveness, and peeling occurs during solder reflow, and the heat resistance during the assembly is insufficient.
根據以上所述,本發明的目的在於提供一種積層體及積層板、以及該積層體及積層板的製造方法,其中,該積層體 及積層板中,玻璃基板層與樹脂組成物層的黏著性、及耐熱性良好。另外,本發明的目的在於提供一種印刷線路板,該印刷線路板使用該積層體或積層板而成。 According to the above, an object of the present invention is to provide a laminated body and a laminated board, and a method of manufacturing the laminated body and the laminated board, wherein the laminated body In the laminate, the adhesion between the glass substrate layer and the resin composition layer and the heat resistance are good. Further, it is an object of the invention to provide a printed wiring board which is formed using the laminated body or laminated board.
本發明人為了解決上述問題而進行研究,結果發現,藉由使形成樹脂組成物層之樹脂組成物中含有聚醯胺醯亞胺樹脂與環氧樹脂,可解決該問題。亦即,本發明如下所述。 In order to solve the above problems, the inventors of the present invention have found that the problem can be solved by including a polyamidoximine resin and an epoxy resin in the resin composition forming the resin composition layer. That is, the present invention is as follows.
[1]一種積層體,其具有1層以上的樹脂組成物層及1層以上的玻璃基板層,其中,前述樹脂組成物層包含聚醯胺醯亞胺樹脂與環氧樹脂。 [1] A laminate comprising one or more resin composition layers and one or more glass substrate layers, wherein the resin composition layer comprises a polyimide film and an epoxy resin.
[2]如[1]所述之積層體,其中,前述聚醯胺醯亞胺樹脂於全部樹脂成分中為50~85質量%。 [2] The laminate according to [1], wherein the polyamidoximine resin is 50 to 85% by mass based on the total of the resin components.
[3]如[1]或[2]所述之積層體,其中,前述環氧樹脂於一分子中具有2個以上的環氧基。 [3] The laminate according to [1], wherein the epoxy resin has two or more epoxy groups in one molecule.
[4]如[1]至[3]中任一項所述之積層體,其中,包含一分子中具有3個以上的與環氧樹脂反應的官能基之樹脂。 [4] The laminate according to any one of [1] to [3] wherein a resin having three or more functional groups reactive with an epoxy resin in one molecule is contained.
[5]如[4]所述之積層體,其中,前述環氧樹脂於全部樹脂成分中含有10~30質量%,前述一分子中具有3個以上的與環氧基反應的官能基之樹脂於全部樹脂成分中含有5%以上。 [5] The laminate according to the above [4], wherein the epoxy resin contains 10 to 30% by mass of the entire resin component, and the resin having three or more epoxy group-reactive functional groups in the above molecule It contains 5% or more of all resin components.
[6]如[4]或[5]所述之積層體,其中,以不超過前述環氧樹脂的固體成分量的範圍,含有前述一分子中具有3個以上的與環氧基反應的官能基之樹脂。 [6] The layered body according to the above [4], wherein, in a range not exceeding the solid content of the epoxy resin, three or more functional groups reactive with an epoxy group are contained in the one molecule. Base resin.
[7]如[1]至[6]中任一項所述之積層體,其中,前述聚醯胺醯亞胺樹脂是使下述通式(1)~通式(3)所示之二羧酸衍生物的至少1種、與通式(4)所示之芳香族二異氰酸酯的至少1種反應而獲得:
[8]如[1]至[7]中任一項所述之積層體,其中,前述環氧樹脂為具有脂環式骨架之環氧樹脂。 [8] The laminate according to any one of [1] to [7] wherein the epoxy resin is an epoxy resin having an alicyclic skeleton.
[9]如[1]至[8]中任一項所述之積層體,其中,前述玻璃基板層的厚度為30~200μm。 [9] The laminate according to any one of [1] to [8] wherein the thickness of the glass substrate layer is 30 to 200 μm.
[10]如[1]至[9]中任一項所述之積層體,其中,前述樹脂組成物層及前述玻璃基板層之合計厚度為40~300μm。 [10] The laminated body according to any one of [1] to [9] wherein the total thickness of the resin composition layer and the glass substrate layer is 40 to 300 μm.
[11]一種積層板,其包含1層以上的樹脂硬化物層及1層以上的玻璃基板層,其中,該積層板是將如[1]至[10]中任一項所述之積層體進行硬化處理而獲得。 [11] A laminate comprising one or more layers of a resin cured layer and one or more layers of a glass substrate, wherein the laminate is a laminate according to any one of [1] to [10] Obtained by hardening treatment.
[12]一種印刷線路板,其是於如[11]所述之積層板的至少一個面上設置線路而成。 [12] A printed wiring board formed by providing a wiring on at least one surface of a laminated board according to [11].
[13]如[12]所述之印刷線路板,其中,該印刷線路板包含複數個積層板,並且至少1個積層板為如[11]所述之前述積層板。 [13] The printed wiring board according to [12], wherein the printed wiring board comprises a plurality of laminated boards, and at least one of the laminated boards is the aforementioned laminated board according to [11].
[14]一種積層體的製造方法,其將包含聚醯胺醯亞胺樹脂與環氧樹脂之樹脂組成物塗佈於玻璃基板的表面上,形成樹脂 組成物層。 [14] A method for producing a laminate, which comprises applying a resin composition comprising a polyimide film and an epoxy resin onto a surface of a glass substrate to form a resin Composition layer.
[15]如[14]所述之積層體的製造方法,其中,形成前述樹脂組成物層之後,實施乾燥處理。 [15] The method for producing a laminate according to [14], wherein the resin composition layer is formed and then subjected to a drying treatment.
[16]一種積層板的製造方法,其先製作由含有聚醯胺醯亞胺樹脂及環氧樹脂之樹脂組成物所構成之膜,並使用真空層疊機或輥層疊機將前述膜積層於玻璃基板上之後,對前述膜實施硬化處理。 [16] A method for producing a laminate, which comprises first forming a film composed of a resin composition containing a polyimide film and an epoxy resin, and laminating the film on a glass using a vacuum laminator or a roll laminator. After the substrate, the film is subjected to a hardening treatment.
[17]如[16]所述之積層板的製造方法,其中,於積層前述膜之後且實施前述硬化處理之前,實施壓製處理。 [17] The method for producing a laminated board according to [16], wherein the pressing treatment is performed after the film is laminated and before the hardening treatment is performed.
根據本發明,可提供一種積層體及積層板、以及該積層體及積層板的製造方法,其中,該積層體及積層板中樹脂組成物層與玻璃基板層的黏著性、耐熱性良好。另外,可提供一種印刷線路板,該印刷線路板使用該積層體或積層板而成。 According to the present invention, there is provided a laminated body and a laminated board, and a method for producing the laminated body and the laminated board, wherein the resin composition layer and the glass substrate layer have good adhesion and heat resistance in the laminated body and the laminated board. Further, a printed wiring board which is formed using the laminated body or the laminated board can be provided.
以下,就本發明之積層體、積層板、與該積層體、積層板的製造方法、以及印刷線路板進行詳細說明。 Hereinafter, the laminated body, the laminated board, the laminated body, the manufacturing method of the laminated board, and the printed wiring board of this invention are demonstrated in detail.
再者,本說明書中,所謂「積層體」,意指作為其樹脂組成物中的構成成分也就是熱硬化性樹脂(多官能的環氧樹脂) 是未硬化或半硬化之物;所謂「積層板」,意指作為其構成成分也就是熱硬化性樹脂硬化、或者熱硬化性樹脂的90%以上硬化之物。另外,熱硬化性樹脂的硬化度可藉由反應率來測定,該反應率由示差掃描熱析儀測定。 In the present specification, the term "layered body" means a thermosetting resin (polyfunctional epoxy resin) as a constituent component in the resin composition. It is an unhardened or semi-hardened material; the term "laminated board" means a material which is a constituent component, that is, a thermosetting resin is cured, or a thermosetting resin is cured by 90% or more. Further, the degree of hardening of the thermosetting resin can be measured by a reaction rate which is measured by a differential scanning calorimeter.
[積層體] [layered body]
本發明之積層體,具有1層以上的樹脂組成物層及1層以上的玻璃基板層,並且前述樹脂組成物層包含聚醯胺醯亞胺樹脂與環氧樹脂。 The laminate of the present invention has one or more resin composition layers and one or more glass substrate layers, and the resin composition layer contains a polyimide film and an epoxy resin.
此處,本發明之樹脂組成物層,在成為線路板用積層板或多層線路板一部分的層之前,是以未硬化或半硬化狀態(B階段(B-Stage)狀態)存在於支持體上或玻璃基板上等。 Here, the resin composition layer of the present invention is present on the support in an uncured or semi-hardened state (B-Stage state) before being a layer of a wiring board for a wiring board or a part of a multilayer wiring board. Or on a glass substrate.
另外,本發明之積層板是藉由下述方式獲得:將本發明之積層體加熱,藉此使樹脂組成物層硬化,形成樹脂硬化物層,從而獲得本發明之積層板。 Further, the laminate of the present invention is obtained by heating the laminate of the present invention to thereby harden the resin composition layer to form a resin cured layer, thereby obtaining a laminate of the present invention.
此處,藉由使用與矽晶片為相同程度的低熱膨脹係數且高彈性模數之玻璃基板層,翹曲得以被抑制,且不易產生破裂。 尤其,此種積層板藉由具備耐熱性較高之玻璃基板層,可於100℃~未達樹脂硬化物的玻璃轉移溫度(Tg)之溫度範圍內具有顯著的低熱膨脹性。另外,藉由使樹脂硬化物層中含有無機填充材料,樹脂硬化物層具有低熱膨脹性且具有高彈性,並且,包含該樹脂硬化物層之積層板,熱膨脹性更低且彈性模數更高。 Here, by using a glass substrate layer having a low thermal expansion coefficient and a high elastic modulus which is the same degree as the tantalum wafer, warpage is suppressed and cracking is less likely to occur. In particular, such a laminate has a glass substrate layer having high heat resistance, and has a remarkable low thermal expansion property in a temperature range of from 100 ° C to a glass transition temperature (Tg) of the cured resin. Further, by including the inorganic filler in the resin cured layer, the cured resin layer has low thermal expansion and high elasticity, and the laminate including the cured resin layer has lower thermal expansion and higher modulus of elasticity .
另外,亦可於本發明之樹脂硬化物層與導體層之間設置輔助黏著層,以提高樹脂硬化物層與導體層的黏著性。 Further, an auxiliary adhesive layer may be provided between the cured resin layer of the present invention and the conductor layer to improve the adhesion between the cured resin layer and the conductor layer.
(樹脂組成物) (resin composition)
以下,就本發明之樹脂組成物層中所使用之樹脂組成物,進行詳細說明。 Hereinafter, the resin composition used in the resin composition layer of the present invention will be described in detail.
本發明之樹脂組成物,包含聚醯胺醯亞胺樹脂與環氧樹脂。於樹脂組成物中,就玻璃黏著性之觀點而言,用來保證玻璃黏著性之基底樹脂也就是聚醯胺醯亞胺樹脂的調配量,較佳為於全部樹脂成分中為50~85質量%,更佳為50~80質量%。另外,就耐熱性之觀點而言,聚醯胺醯亞胺樹脂的調配量,較佳為50~75質量%。聚醯胺醯亞胺樹脂的調配量,較佳為於全部樹脂成分中為50~90質量%,更佳為55~85質量%,特佳為60~85質量%。若以上述範圍來調配聚醯胺醯亞胺樹脂,則表現出源自於聚醯胺醯亞胺樹脂之玻璃黏著性,因此較佳。 The resin composition of the present invention comprises a polyamidoximine resin and an epoxy resin. In the resin composition, from the viewpoint of glass adhesion, the amount of the base resin for ensuring the adhesion of the glass, that is, the polyimide amine imide resin, is preferably 50 to 85 mass in all the resin components. %, more preferably 50 to 80% by mass. Further, the blending amount of the polyamidoximine resin is preferably from 50 to 75% by mass in terms of heat resistance. The blending amount of the polyamidoximine resin is preferably from 50 to 90% by mass, more preferably from 55 to 85% by mass, particularly preferably from 60 to 85% by mass, based on the total of the resin component. When the polyamidoximine resin is blended in the above range, it exhibits a glass adhesive property derived from a polyamidoximine resin, which is preferable.
環氧樹脂的調配量,較佳為於全部樹脂成分中為10~30質量%,更佳為12~28質量%,特佳為15~25質量%。若以上述範圍來調配環氧樹脂,則交聯密度充分,獲得良好的耐熱性。並且,環氧樹脂與聚醯胺醯亞胺樹脂較難產生相分離。 The blending amount of the epoxy resin is preferably from 10 to 30% by mass, more preferably from 12 to 28% by mass, particularly preferably from 15 to 25% by mass, based on the total of the resin component. When the epoxy resin is blended in the above range, the crosslinking density is sufficient, and good heat resistance is obtained. Moreover, epoxy resins and polyamidoximine resins are more difficult to phase separate.
本發明之聚醯胺醯亞胺樹脂,是主鏈中具有醯胺基和醯亞胺基之聚合物。 The polyamidoximine resin of the present invention is a polymer having a mercaptoamine group and a quinone imine group in the main chain.
作為本發明之聚醯胺醯亞胺樹脂,較佳為使下述通式(1)
~通式(3)所示之二羧酸衍生物的至少1種,與通式(4)所示之芳香族二異氰酸酯的至少1種反應而獲得的聚醯胺醯亞胺樹脂:
本發明之聚醯胺醯亞胺樹脂,可藉由包含以下步驟之方法來合成:藉由二胺與偏苯三甲酸酐之反應,生成二羧酸衍生物之步驟;及,使二羧酸衍生物與二異氰酸酯反應,生成聚醯胺醯亞胺樹脂之步驟。本發明之聚醯胺醯亞胺樹脂,可藉由上述方法而較佳地獲得,但只要不脫離本發明的主旨,並不限定於藉由上述方法獲得的樹脂。例如,本發明之聚醯胺醯亞胺樹脂,亦可以是藉由使偏苯三甲酸酐與二胺反應亦即醯氯法而獲得的樹脂。 The polyamidoximine resin of the present invention can be synthesized by a method comprising the steps of: reacting a diamine with trimellitic anhydride to form a dicarboxylic acid derivative; and, deriving a dicarboxylic acid The step of reacting with a diisocyanate to form a polyamidoximine resin. The polyamidoximine resin of the present invention can be preferably obtained by the above method, but is not limited to the resin obtained by the above method, without departing from the gist of the present invention. For example, the polyamidoximine resin of the present invention may be a resin obtained by reacting trimellitic anhydride with a diamine, that is, a ruthenium chloride method.
作為合成二羧酸衍生物所使用之二胺,較佳為脂環式二胺、脂肪族二胺、矽氧烷二胺。 The diamine used for the synthesis of the dicarboxylic acid derivative is preferably an alicyclic diamine, an aliphatic diamine or a decane diamine.
作為脂環式二胺,例如,可列舉具有以下結構式之脂環式二胺。 Examples of the alicyclic diamine include an alicyclic diamine having the following structural formula.
此種脂環式二胺,較佳為例如4,4'-二胺基二環己基甲烷等。作為可在市場上獲得之脂環式二胺,可列舉Wondamine HM(胺當量為100以上,新日本理化股份有限公司製造,商品名)等。 Such an alicyclic diamine is preferably, for example, 4,4'-diaminodicyclohexylmethane or the like. Examples of the alicyclic diamine which is commercially available include Wondamine HM (amine equivalent of 100 or more, manufactured by Shin Nippon Chemical Co., Ltd., trade name).
作為脂肪族二胺,較佳為氧丙烯二胺。市售的脂肪族二胺可列舉例如:Jeffamine D-230(三井精細化學股份有限公司(Mitsui Fine Chemicals,Inc.),胺當量:115,商品名)、Jeffamine D-400(三井精細化學股份有限公司,胺當量:200,商品名)、Jeffamine D-2000(三井精細化學股份有限公司,胺當量:1000,商品名)、Jeffamine D-4000(三井精細化學股份有限公司,胺當量:2000,商品名)等。 As the aliphatic diamine, oxypropylene diamine is preferred. Commercially available aliphatic diamines include, for example, Jeffamine D-230 (Mitsui Fine Chemicals, Inc., amine equivalent: 115, trade name), Jeffamine D-400 (Mitsui Fine Chemical Co., Ltd.) Company, amine equivalent: 200, trade name), Jeffamine D-2000 (Mitsui Fine Chemical Co., Ltd., amine equivalent: 1000, trade name), Jeffamine D-4000 (Mitsui Fine Chemical Co., Ltd., amine equivalent: 2000, commodity Name) and so on.
矽氧烷二胺,是具有矽氧烷骨架之二胺,可列舉具有例如以下結構式之二胺。 The oxime diamine is a diamine having a siloxane skeleton, and examples thereof include a diamine having the following structural formula.
作為此種矽氧烷二胺,可使用市售品,例如,可列舉:「KF-8010」(胺當量430)、「X-22-161A」(胺當量800)、「X-22-161B」(胺當量1500)、「KF-8012」(胺當量2200)、「KF-8008」(胺當量5700)、「X-22-9409」(胺當量700)、 「X-22-1660B-3」(胺當量2200)(以上,由信越化學工業股份有限公司(Shin-Etsu Chemical Co.,Ltd.)製造);「BY-16-853U」(胺當量460)、「BY-16-853」(胺當量650)、「BY-16-853B」(胺當量2200)(以上,由道康寧東麗股份有限公司(Dow Corning Toray Co.,Ltd.)製造)等。該等矽氧烷二胺可單獨使用,或混合2種以上而使用。 A commercially available product can be used as the oxirane diamine. For example, "KF-8010" (amine equivalent 430), "X-22-161A" (amine equivalent 800), and "X-22-161B" can be used. (amine equivalent 1500), "KF-8012" (amine equivalent 2200), "KF-8008" (amine equivalent 5700), "X-22-9409" (amine equivalent 700), "X-22-1660B-3" (amine equivalent 2200) (above, manufactured by Shin-Etsu Chemical Co., Ltd.); "BY-16-853U" (amine equivalent 460) "BY-16-853" (amine equivalent 650), "BY-16-853B" (amine equivalent 2200) (above, manufactured by Dow Corning Toray Co., Ltd.), and the like. These oxirane diamines may be used singly or in combination of two or more.
該等二胺類可單獨使用1種,或者組合2種以上來使用。二羧酸衍生物之合成中,合成二羧酸衍生物所使用之二胺的5~100質量%,較佳是使用上述二胺來進行合成。若使用以此種方式合成之二羧酸衍生物,所獲得之聚醯胺醯亞胺樹脂會滿足數種特性。其中,若使用矽氧烷二胺,所獲得之聚醯胺醯亞胺樹脂會顯示良好的耐熱性和低彈性模數,因此更佳。 These diamines may be used alone or in combination of two or more. In the synthesis of the dicarboxylic acid derivative, 5 to 100% by mass of the diamine used in the synthesis of the dicarboxylic acid derivative is preferably synthesized by using the above diamine. When a dicarboxylic acid derivative synthesized in this manner is used, the obtained polyamidoximine resin satisfies several characteristics. Among them, if a nonoxyldiamine is used, the obtained polyamidoximine resin exhibits good heat resistance and a low modulus of elasticity, and thus is more preferable.
另外,視需要,除上述二胺類以外,亦可使用芳香族二胺。作為芳香族二胺,例如,可列舉:對、間、鄰苯二胺、2,4-二胺基甲苯、2,5-二胺基甲苯、2,4-二胺基二甲苯、二胺基荰(diaminodurene)、1,5-二胺基萘、2,6-二胺基萘、聯苯胺、4,4'-二胺基聯三苯、4,4'''-二胺基聯四苯、4,4'-二胺基二苯基甲烷、1,2-雙(苯胺基)乙烷、4,4'-二胺基二苯醚、二胺基二苯碸、2,2-雙(對胺基苯基)丙烷、2,2-雙(對胺基苯基)六氟丙烷、2,6-二胺基萘、3,3-二甲基聯苯胺、3,3'-二甲基-4,4'-二胺基二苯醚、3,3'-二甲基-4,4'-二胺基二苯基甲烷、二胺基甲苯、二 胺基三氟甲苯、1,4-雙(對胺基苯氧基)苯、4,4'-雙(對胺基苯氧基)聯苯、2,2'-雙[4-(對胺基苯氧基)苯基]丙烷、二胺基蒽醌、4,4'-雙(3-胺基苯氧基苯基)二苯碸、1,3-雙(苯胺基)六氟丙烷、1,4-雙(苯胺基)八氟丁烷、1,5-雙(苯胺基)十氟戊烷、1,7-雙(苯胺基)十氟丁烷、2,2-雙[4-(對胺基苯氧基)苯基]六氟丙烷、2,2-雙[4-(3-胺基苯氧基)苯基]六氟丙烷、2,2-雙[4-(2-胺基苯氧基)苯基]六氟丙烷、2,2-雙[4-(4-胺基苯氧基)-3,5-二甲基苯基]六氟丙烷、2,2-雙[4-(4-胺基苯氧基)-3,5-二-三氟甲基苯基]六氟丙烷、對雙(4-胺基-2-三氟甲基苯氧基)苯、4,4'-雙(4-胺基-2-三氟甲基苯氧基)聯苯、4,4'-雙(4-胺基-3-三氟甲基苯氧基)聯苯、4,4'-雙(4-胺基-2-三氟甲基苯氧基)二苯碸、4,4'-雙(3-胺基-5-三氟甲基苯氧基)二苯碸、2,2-雙[4-(4-胺基-3-三氟甲基苯氧基)苯基]六氟丙烷等。芳香族二胺,可視需要於合成二羧酸衍生物所使用之二胺類的0~95質量%之範圍內使用。 Further, an aromatic diamine may be used in addition to the above diamines, as needed. Examples of the aromatic diamine include p-, m-, o-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,4-diaminoxylene, and diamine. Diaminodurene, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, benzidine, 4,4'-diaminotriphenyl, 4,4'''-diamine linkage Tetraphenyl, 4,4'-diaminodiphenylmethane, 1,2-bis(anilino)ethane, 4,4'-diaminodiphenyl ether, diaminodiphenyl hydrazine, 2,2 - bis(p-aminophenyl)propane, 2,2-bis(p-aminophenyl)hexafluoropropane, 2,6-diaminonaphthalene, 3,3-dimethylbenzidine, 3,3' - dimethyl-4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, diaminotoluene, two Aminotrifluorotoluene, 1,4-bis(p-aminophenoxy)benzene, 4,4'-bis(p-aminophenoxy)biphenyl, 2,2'-bis[4-(p-amine) Phenoxy group) phenyl] propane, diamino hydrazine, 4,4'-bis(3-aminophenoxyphenyl)diphenyl hydrazine, 1,3-bis(anilino)hexafluoropropane, 1,4-bis(anilino)octafluorobutane, 1,5-bis(anilino)decafluoropentane, 1,7-bis(anilino)decafluorobutane, 2,2-bis[4- (p-Aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2- Aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-double [4-(4-Aminophenoxy)-3,5-di-trifluoromethylphenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl hydrazine, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl Anthracene, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, and the like. The aromatic diamine may be used in an amount of from 0 to 95% by mass based on the diamine used in the synthesis of the dicarboxylic acid derivative.
可使用如上所述之矽氧烷二胺、脂環式二胺、脂肪族二胺、及視需要使用之芳香族二胺之二胺類,與偏苯三甲酸酐,來合成二羧酸衍生物。二胺類與偏苯三甲酸酐的莫耳比,較佳為1:2左右,例如,可藉由下述方式來合成二羧酸衍生物:使用N-甲基-2-吡咯啶酮(N-methyl-2-pyrrolidone,NMP)等溶劑,於50~90℃下使二胺類與偏苯三甲酸酐反應,繼而,於120~180℃下進行醯亞胺環閉環反應,藉此合成二羧酸衍 生物。然後,使用該二羧酸衍生物,與二異氰酸酯反應,可合成聚醯胺醯亞胺樹脂。 The dicarboxylic acid derivative can be synthesized by using the above-mentioned oxirane diamine, alicyclic diamine, aliphatic diamine, and optionally diamine of an aromatic diamine, and trimellitic anhydride. . The molar ratio of the diamine to the trimellitic anhydride is preferably about 1:2. For example, the dicarboxylic acid derivative can be synthesized by using N-methyl-2-pyrrolidone (N). -methyl-2-pyrrolidone, NMP) and other solvents, the diamines are reacted with trimellitic anhydride at 50-90 ° C, and then the ring-opening reaction of the quinone ring is carried out at 120-180 ° C to synthesize dicarboxylic acid Acid derivative biological. Then, using the dicarboxylic acid derivative and reacting with a diisocyanate, a polyamidoximine resin can be synthesized.
再者,合成二羧酸衍生物時,矽氧烷二胺、脂環式二胺、脂肪族二胺,可分別單獨地用於反應,或者組合2種以上用於反應。當組合3種來使用時,就黏著性以及與環氧樹脂之相溶性方面而言,矽氧烷二胺、脂環式二胺、脂肪族二胺的調配量,較佳是分別在30~70莫耳%、5~60莫耳%、10~40莫耳%左右的範圍內。 Further, in the case of synthesizing the dicarboxylic acid derivative, the nonanediamine diamine, the alicyclic diamine, and the aliphatic diamine may be used alone or in combination of two or more kinds. When the three types are used in combination, the blending amount of the oxirane diamine, the alicyclic diamine, and the aliphatic diamine is preferably 30% in terms of adhesion and compatibility with the epoxy resin. 70% of the moles, 5 to 60% of the moles, and 10 to 40% of the moles.
作為反應中所使用之二異氰酸酯,可列舉如通式(4)所示之芳香族二異氰酸酯,該芳香族二異氰酸酯是藉由芳香族二胺與光氣等的反應所獲得。作為芳香族二異氰酸酯,例如,可列舉:甲苯二異氰酸酯、二苯基甲烷二異氰酸酯、萘二異氰酸酯、二苯醚二異氰酸酯、伸苯基-1,3-二異氰酸酯等。 The diisocyanate used in the reaction is, for example, an aromatic diisocyanate represented by the formula (4), which is obtained by a reaction of an aromatic diamine with phosgene or the like. Examples of the aromatic diisocyanate include toluene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, diphenyl ether diisocyanate, and phenyl-1,3-diisocyanate.
上述芳香族二異氰酸酯中,就耐熱性方面而言,較佳為例如:1,4-甲苯二異氰酸酯、2,6-甲苯二異氰酸酯、二苯基甲烷二異氰酸酯、雙(甲基苯基)甲烷二異氰酸酯、萘二異氰酸酯。 Among the above aromatic diisocyanates, in terms of heat resistance, for example, 1,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, bis(methylphenyl)methane is preferable. Diisocyanate, naphthalene diisocyanate.
聚醯胺醯亞胺的聚合反應,通常在以下溶劑中進行:N-甲基-2-吡咯啶酮(NMP)、N,N-二甲基甲醯胺(N,N-dimethylformamide,DMF)、N,N-二甲基乙醯胺(N,N-dimethylacetamide,DMAC)、二甲基亞碸(dimethyl sulfoxide,DMSO)、硫酸二甲酯、環丁碸、γ-丁內酯、甲酚、苯酚、鹵化苯酚、環己烷、二噁烷等。反應溫度,較佳為200℃ 以下。另外,就控制分子量方面而言,二異氰酸酯與二羧酸衍生物的莫耳比,較佳為1:2左右。 The polymerization of polyamidoximine is usually carried out in the following solvents: N-methyl-2-pyrrolidone (NMP), N,N-dimethylformamide (DMF) , N,N-dimethylacetamide (DMAC), dimethyl sulfoxide (DMSO), dimethyl sulfate, cyclobutyl hydrazine, γ-butyrolactone, cresol , phenol, halogenated phenol, cyclohexane, dioxane, and the like. Reaction temperature, preferably 200 ° C the following. Further, in terms of controlling the molecular weight, the molar ratio of the diisocyanate to the dicarboxylic acid derivative is preferably about 1:2.
本發明之樹脂組成物中使用之環氧樹脂,較佳為一分子中具有2個以上的環氧基之環氧樹脂。另外,就環氧樹脂於聚醯胺醯亞胺樹脂中之溶解性方面而言,較佳為一分子中具有2~5個環氧基之環氧樹脂。特佳為具有與聚醯胺醯亞胺樹脂使用之二胺的骨架結構相近之結構的環氧樹脂,例如當聚醯胺醯亞胺樹脂是使用氧丙烯二胺所得時,就獲得良好的溶解性方面而言,上述環氧樹脂較佳為脂肪族環氧樹脂,考慮到樹脂組成物的耐熱性,更佳為脂環式環氧樹脂。作為此種脂肪族環氧樹脂,可列舉雙環戊二烯酚型環氧樹脂HP7200(大日本油墨化學工業股份有限公司(Dainippon Ink & Chemicals,Inc.)製造,商品名)等。 The epoxy resin used in the resin composition of the present invention is preferably an epoxy resin having two or more epoxy groups in one molecule. Further, in terms of solubility of the epoxy resin in the polyamidoximine resin, an epoxy resin having 2 to 5 epoxy groups in one molecule is preferred. Particularly preferred is an epoxy resin having a structure similar to that of a diamine used in a polyamide amine imide resin, for example, when a polyamidoximine resin is obtained using oxypropylene diamine, good dissolution is obtained. In terms of properties, the epoxy resin is preferably an aliphatic epoxy resin, and more preferably an alicyclic epoxy resin in view of heat resistance of the resin composition. Examples of such an aliphatic epoxy resin include a dicyclopentadiene phenol type epoxy resin HP7200 (manufactured by Dainippon Ink & Chemicals, Inc., trade name).
若使用與聚醯胺醯亞胺樹脂不相溶之環氧樹脂(例如,聯苯酚醛清漆型環氧樹脂NC3000(日本化藥股份有限公司(Nippon Kayaku Co.,Ltd.)製造,商品名)),則環氧樹脂與聚醯胺醯亞胺樹脂產生相分離,溶解性成分容易滲透至耐鹼性較弱的聚醯胺醯亞胺樹脂中。另一方面,若使用具有相溶性之環氧樹脂,環氧樹脂則勻細地分散於聚醯胺醯亞胺樹脂中,藉此阻礙溶解性成分進入。因此,耐化學品性提高。 If an epoxy resin which is incompatible with the polyamide amide resin (for example, a biphenyl aldehyde varnish type epoxy resin NC3000 (manufactured by Nippon Kayaku Co., Ltd.), trade name) is used. ), the epoxy resin is phase-separated from the polyamidoximine resin, and the soluble component is easily infiltrated into the less alkali-resistant polyamide amine imide resin. On the other hand, when an epoxy resin having compatibility is used, the epoxy resin is uniformly dispersed in the polyamide amidoximine resin, thereby inhibiting the entry of the soluble component. Therefore, chemical resistance is improved.
本發明之樹脂組成物,就耐化學品性方面而言,較佳為包含下述樹脂,即一分子中具有3個以上的與環氧基反應 的官能基之樹脂。作為一分子中具有3個以上的與環氧基反應之官能基之樹脂,例如,可列舉:具有3個以上的環氧基之多官能環氧化合物、或多官能酚化合物、多官能胺、胺酯樹脂等。 The resin composition of the present invention preferably contains a resin having three or more reactive groups with an epoxy group in terms of chemical resistance. Functional resin. Examples of the resin having three or more functional groups reactive with an epoxy group in one molecule include a polyfunctional epoxy compound having three or more epoxy groups, a polyfunctional phenol compound, and a polyfunctional amine. Amine ester resin and the like.
作為具有3個以上的環氧基之多官能環氧化合物,例如,可列舉:使雙酚A、酚醛清漆型酚樹脂、鄰甲酚酚醛清漆型酚樹脂等多酚或1,4-丁二醇等多元醇與表氯醇反應所獲得之聚縮水甘油醚;使鄰苯二甲酸、六氫鄰苯二甲酸等多元酸與表氯醇反應所獲得之聚縮水甘油酯;具有胺基、醯胺基或雜環式含氮鹼基之化合物的N-縮水甘油基衍生物;脂環式環氧樹脂等。 Examples of the polyfunctional epoxy compound having three or more epoxy groups include polyphenols such as bisphenol A, novolac type phenol resins, and o-cresol novolac type phenol resins, or 1,4-butane. a polyglycidyl ether obtained by reacting a polyol such as an alcohol with epichlorohydrin; a polyglycidyl ester obtained by reacting a polybasic acid such as phthalic acid or hexahydrophthalic acid with epichlorohydrin; having an amine group and an anthracene An N-glycidyl derivative of an amine- or heterocyclic nitrogen-containing base compound; an alicyclic epoxy resin or the like.
作為多官能酚化合物,例如,可列舉:對苯二酚、間苯二酚、雙酚A和此等的鹵化物、以及與甲醛之縮合物也就是酚醛清漆型酚樹脂、甲階酚醛型酚樹脂等。 Examples of the polyfunctional phenol compound include hydroquinone, resorcin, bisphenol A, and halides thereof, and condensates with formaldehyde, that is, novolac type phenol resins, resol phenols. Resin, etc.
具有3個以上的與環氧基反應之官能基之樹脂的調配量,較佳為於全部樹脂成分中為5~30質量%,更佳為7~25質量%,特佳為8~20質量%。若以上述範圍,來調配具有3個以上的與環氧基反應之官能基之樹脂,則會兼具耐化學品性與黏著性。 The compounding amount of the resin having three or more functional groups reactive with an epoxy group is preferably from 5 to 30% by mass, more preferably from 7 to 25% by mass, particularly preferably from 8 to 20% by mass based on the entire resin component. %. When the resin having three or more functional groups reactive with an epoxy group is blended in the above range, it has both chemical resistance and adhesion.
本發明之樹脂組成物,亦可含有環氧樹脂之硬化劑、及硬化促進劑。作為環氧樹脂之硬化劑、及硬化促進劑,只要可與環氧樹脂反應,或者促進硬化,則並無限制,例如, 可使用胺類、咪唑類、酸酐類等。作為胺類,例如,可使用:二氰二胺、二胺基二苯基甲烷、胍脲等;作為酸酐類,例如,可使用:鄰苯二甲酸酐、二苯基酮四甲酸二酐、甲基降冰片烯二甲酸酐(methyl himic acid)等。作為硬化促進劑,例如,可使用:咪唑類的經烷基取代之咪唑、苯并咪唑等。 The resin composition of the present invention may further contain a curing agent for an epoxy resin and a curing accelerator. The curing agent for the epoxy resin and the curing accelerator are not limited as long as they can react with the epoxy resin or promote hardening, for example, Amines, imidazoles, acid anhydrides and the like can be used. As the amine, for example, dicyandiamide, diaminodiphenylmethane, guanidine or the like can be used, and as the acid anhydride, for example, phthalic anhydride or diphenyl ketone tetracarboxylic dianhydride can be used. Methyl norbornene (methyl himic acid) or the like. As the hardening accelerator, for example, an alkyl-substituted imidazole, benzimidazole or the like of an imidazole can be used.
本發明之樹脂組成物,亦可含有無機填充材料。藉由向樹脂組成物中調配無機填充材料,可使樹脂硬化物層低熱膨脹化、及高彈性化。作為無機填充材料,例如,可列舉:二氧化矽、氧化鋁、滑石、雲母、氫氧化鋁、氫氧化鎂、碳酸鈣、硼酸鋁、硼矽玻璃等。其中,就低熱膨脹性方面而言,較佳為二氧化矽,進而,更佳為球狀非晶形二氧化矽,該球狀非晶形二氧化矽的熱膨脹係數非常小,為0.6ppm/K左右,且大量填充於樹脂中時流動性下降較少。 The resin composition of the present invention may also contain an inorganic filler. By blending the inorganic filler with the resin composition, the cured resin layer can be made to have low thermal expansion and high elasticity. Examples of the inorganic filler include cerium oxide, aluminum oxide, talc, mica, aluminum hydroxide, magnesium hydroxide, calcium carbonate, aluminum borate, and borosilicate glass. Among them, in terms of low thermal expansion, it is preferably cerium oxide, and more preferably spherical amorphous cerium oxide, and the spherical amorphous cerium oxide has a very small thermal expansion coefficient of about 0.6 ppm/K. And the fluidity is less reduced when a large amount is filled in the resin.
另外,本發明之樹脂組成物,亦可含有以下添加劑:矽烷偶合劑、耐電蝕性改善劑、阻燃劑、防銹劑等。 Further, the resin composition of the present invention may further contain the following additives: a decane coupling agent, an electrolytic corrosion resistance improving agent, a flame retardant, a rust preventive agent, and the like.
將如上所述之聚醯胺醯亞胺樹脂及環氧樹脂等成分混合,獲得樹脂組成物,並將該樹脂組成物積層於玻璃基板上,形成樹脂組成物層,可製造積層體,關於製造方法,將於後文中記述。 The polyamidoximine resin and the epoxy resin and the like are mixed as described above to obtain a resin composition, and the resin composition is laminated on a glass substrate to form a resin composition layer, whereby a laminate can be produced. The method will be described later.
(玻璃基板層) (glass substrate layer)
作為構成玻璃基板層之玻璃基板,就積層體薄型化之目的及加工性之觀點而言,較佳為厚度30~200μm之薄型的玻璃 膜,考慮到操作的容易性等,厚度更佳為50~150μm。進一步,就積層體薄型化之觀點而言,較佳為厚度30~90μm。另外,作為玻璃基材的原料,可使用鹼性矽酸鹽系玻璃、無鹼玻璃、石英玻璃等玻璃;就低熱膨脹性及加工性之觀點而言,較佳為硼矽玻璃。 The glass substrate constituting the glass substrate layer is preferably a thin glass having a thickness of 30 to 200 μm from the viewpoint of the purpose of thinning the laminated body and workability. The film is preferably 50 to 150 μm in thickness in consideration of ease of handling and the like. Further, from the viewpoint of thinning the laminated body, the thickness is preferably from 30 to 90 μm. Further, as the raw material of the glass substrate, glass such as alkaline bismuth carbonate glass, alkali-free glass, or quartz glass can be used, and from the viewpoint of low thermal expansion property and workability, borosilicate glass is preferable.
再者,樹脂組成物層及玻璃基板層之合計厚度,較佳為40~300μm,更佳為100~250μm。藉由使樹脂組成物層及玻璃基板層之合計厚度為40~300μm,可實現印刷線路板等產品的薄型化。 Further, the total thickness of the resin composition layer and the glass substrate layer is preferably 40 to 300 μm, more preferably 100 to 250 μm. By making the total thickness of the resin composition layer and the glass substrate layer 40 to 300 μm, it is possible to reduce the thickness of products such as printed wiring boards.
另外,該玻璃基板層的熱膨脹係數,越接近於矽晶片的熱膨脹係數(3ppm/℃左右),則積層體或由該積層體獲得之積層板的翹曲越能得到抑制,因而較佳;該玻璃基板層的熱膨脹係數較佳為8ppm/℃以下,更佳為6ppm/℃以下,進而更佳為4ppm/℃以下。 Further, the closer the thermal expansion coefficient of the glass substrate layer is to the thermal expansion coefficient (about 3 ppm/° C.) of the tantalum wafer, the more the warpage of the laminated body or the laminated sheet obtained from the laminated body can be suppressed, which is preferable. The coefficient of thermal expansion of the glass substrate layer is preferably 8 ppm/° C. or lower, more preferably 6 ppm/° C. or lower, and still more preferably 4 ppm/° C. or lower.
該玻璃基板層於40℃下之動態儲存彈性模數越大越佳,較佳為20GPa以上,更佳為25GPa以上,進而更佳為30GPa以上。若玻璃基板層於40℃下之動態儲存彈性模數為20GPa以上,則積層體或由該積層體獲得之積層板的翹曲得到抑制,而獲得良好的結果。 The glass substrate layer preferably has a dynamic storage elastic modulus at 40 ° C, preferably 20 GPa or more, more preferably 25 GPa or more, and still more preferably 30 GPa or more. When the dynamic storage modulus of the glass substrate layer at 40 ° C is 20 GPa or more, warpage of the laminate or the laminate obtained from the laminate is suppressed, and good results are obtained.
作為積層板於40℃下之儲存彈性模數的測定方法,例如,可列舉如下方法。首先,自積層板切割出5mm×30mm的試片。使用覆銅積層板之情況下,藉由將覆銅積層板浸漬 於銅蝕刻液中,去除銅箔後,切割出試片。使用廣域黏彈性測定裝置(Rheology公司製造,DVE-V4型),於跨距20mm、頻率10Hz、振動位移1~3μm(減振)之條件下,可測定所切割出的試片於40℃下之拉伸儲存彈性模數。 As a method of measuring the storage elastic modulus of the laminate at 40 ° C, for example, the following method can be mentioned. First, a test piece of 5 mm × 30 mm was cut out from the laminate. In the case of using a copper clad laminate, the copper clad laminate is impregnated After removing the copper foil in the copper etching solution, the test piece was cut. Using a wide-area viscoelasticity measuring device (DVE-V4, manufactured by Rheology Co., Ltd.), the cut test piece can be measured at 40 ° C under the conditions of a span of 20 mm, a frequency of 10 Hz, and a vibration displacement of 1 to 3 μm (vibration reduction). The lower tensile storage elastic modulus.
(支持體膜及保護膜) (Support body film and protective film)
本發明之積層體,亦可於表面具有支持體膜或保護膜。作為所使用之支持體膜,較佳為:聚對苯二甲酸乙二酯膜、聚萘二甲酸乙二酯膜、聚苯硫醚膜、鐵氟龍(Teflon)(註冊商標)膜、聚醯亞胺膜、未經粗糙化之銅箔或表面粗糙度(Ra)為0.4μm以下之低粗糙化銅箔、及鋁箔等。另外,該等支持體膜亦可使用表面經脫模處理的支持體膜,以容易與樹脂剝離。 The laminate of the present invention may have a support film or a protective film on the surface. As the support film to be used, a polyethylene terephthalate film, a polyethylene naphthalate film, a polyphenylene sulfide film, a Teflon (registered trademark) film, and a polycondensation are preferable. A ruthenium imide film, a copper foil which has not been roughened, or a low-roughened copper foil having a surface roughness (Ra) of 0.4 μm or less, and an aluminum foil. Further, as the support film, a support film having a surface-released treatment may be used to easily peel off from the resin.
作為保護膜,例如,可與支持基材相同,列舉:聚乙烯、聚丙烯等聚烯烴,聚對苯二甲酸乙二酯等聚酯,聚碳酸酯、氟系膜、脫模紙等。再者,上述保護膜的厚度更佳為20~100μm,亦可對保護膜實施消光處理(mat treatment)、電暈處理、脫模處理。關於該等支持體膜和保護膜,將於後述之積層體的製造方法的說明中詳細記載。 The protective film may be, for example, a polyolefin such as polyethylene or polypropylene, a polyester such as polyethylene terephthalate, a polycarbonate, a fluorine-based film, or a release paper. Further, the thickness of the protective film is preferably from 20 to 100 μm, and the protective film may be subjected to a mat treatment, a corona treatment, or a mold release treatment. The support film and the protective film will be described in detail in the description of the method for producing the laminated body to be described later.
[積層體的製造方法] [Manufacturing method of laminated body]
本發明之積層體的製造方法可藉由將樹脂組成物塗佈於玻璃基板上,或將由樹脂組成物而成之膜層疊於玻璃基板上等方式,來製造本發明之積層體。其中,就容易生產方面而言,較佳為藉由層疊而成之方法。 In the method for producing a laminate according to the present invention, the laminate of the present invention can be produced by coating a resin composition on a glass substrate or laminating a film made of a resin composition on a glass substrate. Among them, in terms of ease of production, it is preferably a method of lamination.
以下,詳細說明各製造方法。 Hereinafter, each manufacturing method will be described in detail.
[藉由塗佈而成之積層體的製造方法] [Manufacturing method of laminated body by coating]
藉由塗佈而成之製造方法,是將上述樹脂組成物塗佈於玻璃基板的表面上,形成樹脂組成物層來製造積層體的方法。例如,將上述樹脂組成物溶解於有機溶劑中,製備清漆。 將該清漆塗佈於玻璃基板上,藉由加熱或熱風吹附等方式,使有機溶劑乾燥,藉此,可形成樹脂組成物層。可將該樹脂組成物層,進一步半硬化。如此,可製造樹脂組成物層為未硬化或半硬化狀態(B階段狀態)之積層體。 The coating method by coating is a method in which the resin composition is applied onto the surface of a glass substrate to form a resin composition layer to produce a laminate. For example, the above resin composition is dissolved in an organic solvent to prepare a varnish. The varnish is applied onto a glass substrate, and the organic solvent is dried by heating or hot air blowing to form a resin composition layer. The resin composition layer can be further semi-hardened. Thus, a laminate in which the resin composition layer is in an unhardened or semi-hardened state (B-stage state) can be produced.
[藉由層疊而成之積層體的製造方法] [Manufacturing method of laminated body by lamination]
上述積層體可藉由下述方式製造:將使用本發明之樹脂組成物所成之黏著膜與玻璃基板層疊來製造。關於該黏著膜,將於後文中記述。另外,可使用市售的真空層疊機、輥層疊機來進行層疊。 The laminate can be produced by laminating an adhesive film formed using the resin composition of the present invention and a glass substrate. This adhesive film will be described later. Further, lamination can be carried out using a commercially available vacuum laminator or roll laminator.
再者,作為上述樹脂組成物中的環氧樹脂,較佳為使用如下環氧樹脂,亦即,該環氧樹脂可在小於等於層疊時溫度的溫度下熔融。例如,使用真空層疊機或輥層疊機來進行層疊之情況下,通常是於小於等於140℃之溫度下進行,因此,上述樹脂組成物中的環氧樹脂,較佳為在小於等於140℃之溫度下會熔融之環氧樹脂。 Further, as the epoxy resin in the resin composition, it is preferred to use an epoxy resin which can be melted at a temperature equal to or lower than the temperature at the time of lamination. For example, in the case of laminating using a vacuum laminator or a roll laminator, it is usually carried out at a temperature of 140 ° C or less. Therefore, the epoxy resin in the above resin composition is preferably 140 ° C or less. Epoxy resin that melts at temperature.
首先,對上述黏著膜進行說明,其次,說明使用該黏著膜之層疊方法。 First, the above-mentioned adhesive film will be described, and next, a lamination method using the adhesive film will be described.
使用真空層疊機或輥層疊機來製造積層體時,較佳為將上述樹脂組成物製成黏著膜。 When a laminate is produced by a vacuum laminator or a roll laminator, it is preferred to form the resin composition as an adhesive film.
作為本發明中所用之黏著膜,較佳為使用具有以下積層結構之黏著膜。 As the adhesive film used in the present invention, an adhesive film having the following laminated structure is preferably used.
另外,具有下述積層結構,即於上述(1)之積層結構中,進而積層有保護膜之積層結構之黏著膜亦可較佳地使用。 In addition, the adhesive film having the laminated structure of the above-mentioned (1) and the laminated structure of the protective film may be preferably used.
保護膜,是設置於設於支持體膜上之本發明樹脂組成物層的未設置支持體膜之面上。保護膜,可防止異物附著或損傷。 The protective film is provided on the surface of the resin composition layer of the present invention provided on the support film without the support film. Protective film prevents foreign matter from adhering or damaging.
再者,該等黏著膜移除支持體膜和保護膜後的部分,有時會被稱為黏著膜本體。 Further, the portions of the adhesive film after removing the support film and the protective film are sometimes referred to as an adhesive film body.
具有上述(1)及(2)之積層結構之黏著膜,可藉由對所屬技術領域中具有通常知識者而言為公知的方法來製造。 The adhesive film having the laminated structure of the above (1) and (2) can be produced by a method known to those skilled in the art.
作為製造上述(1)之黏著膜的一例,可將上述樹脂組成物溶解於有機溶劑中,製備清漆。繼而,以支持體膜作為支持體,塗佈該清漆,並藉由加熱或熱風吹附等方式,使有機溶劑乾燥,藉此,形成樹脂組成物層。 As an example of the production of the adhesive film of the above (1), the resin composition can be dissolved in an organic solvent to prepare a varnish. Then, the varnish is applied as a support by using a support film, and the organic solvent is dried by heating or hot air blowing to form a resin composition layer.
作為製造上述(2)之黏著膜的一例,可將上述樹脂組成物溶解於有機溶劑中,製備清漆。繼而,將該清漆塗佈於支持 體膜或保護膜的任一者,並於該清漆上配置支持體膜和保護膜的另一者,藉由加熱或熱風吹附等方式,使該清漆的有機溶劑乾燥,藉此,形成樹脂組成物層。 As an example of the production of the adhesive film of the above (2), the resin composition can be dissolved in an organic solvent to prepare a varnish. Then, the varnish is applied to the support Any one of the body film and the protective film, and the other of the support film and the protective film is disposed on the varnish, and the organic solvent of the varnish is dried by heating or hot air blowing, thereby forming a resin Composition layer.
作為該等樹脂組成物層的塗刷裝置,可使用對所屬技術領域中具有通常知識者而言為公知的塗刷裝置,例如,逗點式塗佈機(comma coater)、刮條式塗佈機(bar coater)、吻合式塗佈機(kiss coater)、輥式塗佈機(roll coater)、凹版塗佈機(gravure coater)、模具塗佈機(die coater)等,較佳為根據製作之膜厚,來適宜選擇塗刷裝置。 As the brushing device of the resin composition layer, a brushing device known to those skilled in the art, for example, a comma coater, a bar coater, can be used. Bar coater, kiss coater, roll coater, gravure coater, die coater, etc., preferably made according to a bar coater, a kiss coater, a roll coater, a die coater, etc. The film thickness is suitable for selecting a painting device.
再者,上述黏著膜中,樹脂組成物層亦可經半硬化。 Further, in the above adhesive film, the resin composition layer may be semi-hardened.
上述支持體膜,是製造黏著膜時之支持體,於製造多層印刷線路板時,通常,該支持體膜在最後會被剝離、或除去。 The support film is a support for producing an adhesive film. When a multilayer printed wiring board is produced, the support film is usually peeled off or removed at the end.
其次,說明使用上述黏著膜之層疊方法的一例。 Next, an example of a lamination method using the above adhesive film will be described.
當黏著膜具有保護膜時,將保護膜除去,然後,一面對黏著膜加壓及加熱,一面將黏著膜壓接至玻璃基板上。層疊條件如下:視需要將黏著膜及玻璃基板預熱,於壓接溫度(層疊溫度)較佳為60℃~140℃、壓接壓力較佳為1~11kgf/cm2之條件下進行層疊。另外,使用真空層疊機時,較佳為於空氣壓力為20mmHg(26.7hPa)以下的減壓條件下進行層疊。另外,層疊方法,可以是批次式,亦可以是利用輥之連續式。 When the adhesive film has a protective film, the protective film is removed, and then the adhesive film is pressure-bonded to the glass substrate while being pressed and heated toward the adhesive film. The lamination conditions are as follows: The adhesive film and the glass substrate are preheated as needed, and laminated at a pressure bonding temperature (lamination temperature) of preferably 60 to 140 ° C and a pressure contact pressure of preferably 1 to 11 kgf/cm 2 . Further, when a vacuum laminator is used, it is preferable to laminate under a reduced pressure condition of an air pressure of 20 mmHg (26.7 hPa) or less. Further, the lamination method may be a batch type or a continuous type using a roll.
如上所述,將黏著膜層疊至玻璃基板上之後,冷卻至室溫附近。視需要,將支持體膜剝離。 As described above, after the adhesive film is laminated on the glass substrate, it is cooled to near room temperature. The support film is peeled off as needed.
[積層板的製造方法] [Manufacturing method of laminated board]
其次,說明積層板的製造方法的具體例。 Next, a specific example of a method of manufacturing a laminated board will be described.
(藉由將積層體加熱硬化而實施之製造例) (Production example by heat-hardening a laminate)
將藉由前述之利用塗佈而成之積層體的製造方法所獲得之積層體,進行加熱硬化(硬化處理),藉此,可製造積層板。 The laminate obtained by the above-described method for producing a laminate obtained by coating is subjected to heat curing (hardening treatment), whereby a laminated sheet can be produced.
另外,對於上述藉由層疊而獲得之積層體,亦可視需要將支持體膜剝離之後,將樹脂組成物層加熱硬化而形成樹脂硬化物層,藉此製造積層板。 In addition, the laminate obtained by lamination may be subjected to a peeling of the support film as needed, and then the resin composition layer may be heat-cured to form a resin cured layer to produce a laminate.
加熱硬化的條件,可於150℃~220℃、20分鐘~80分鐘之範圍內選擇,更佳為於160℃~200℃下進行30分鐘~120分鐘。使用經實施脫模處理之支持體膜之情況下,亦可於加熱硬化之後,剝離支持體膜。 The conditions for heat curing can be selected from 150 ° C to 220 ° C for 20 minutes to 80 minutes, more preferably from 160 ° C to 200 ° C for 30 minutes to 120 minutes. When a support film which has been subjected to mold release treatment is used, the support film may be peeled off after heat curing.
若利用此種方法,則製造積層板時無須加壓,因此,可抑制於製造時產生破裂。 According to this method, since it is not necessary to pressurize the laminated sheet, it is possible to suppress cracking during production.
樹脂硬化物層的厚度,較佳為5~200μm。若該厚度為5μm以上,則可抑制積層板的破裂。若該厚度為200μm以下,則玻璃基板的厚度相對變大,可實現積層板的低熱膨脹係數化及高彈性模數化。就該觀點而言,樹脂硬化物層的厚度更佳為10~150μm,進而更佳為10~100μm。 The thickness of the cured resin layer is preferably 5 to 200 μm. When the thickness is 5 μm or more, cracking of the laminated board can be suppressed. When the thickness is 200 μm or less, the thickness of the glass substrate is relatively increased, and the low thermal expansion coefficient and the high elastic modulus of the laminated plate can be achieved. From this point of view, the thickness of the cured resin layer is more preferably from 10 to 150 μm, still more preferably from 10 to 100 μm.
但是,根據玻璃基板層的厚度或層數目、以及樹脂硬化物層的數目的不同,樹脂硬化物層的厚度的適當範圍也會有所不同,因此,並不限定於上述範圍。 However, depending on the thickness of the glass substrate layer, the number of layers, and the number of the cured resin layers, the appropriate range of the thickness of the cured resin layer is different, and therefore, it is not limited to the above range.
該樹脂硬化物層於40℃之儲存彈性模數,較佳為1~80GPa。若該儲存彈性模數為1GPa以上,則可保護玻璃基板,並抑制積層板的破裂。若該儲存彈性模數為80GPa以下,則可抑制由玻璃基板與樹脂硬化物層的熱膨脹係數之差所致之應力,且可抑制積層板的翹曲和破裂。就該觀點而言,樹脂硬化物層的儲存彈性模數更佳為3~70GPa,進而更佳為5~60GPa。 The resin cured layer has a storage elastic modulus at 40 ° C, preferably 1 to 80 GPa. When the storage elastic modulus is 1 GPa or more, the glass substrate can be protected and the crack of the laminated board can be suppressed. When the storage elastic modulus is 80 GPa or less, the stress caused by the difference in thermal expansion coefficient between the glass substrate and the cured resin layer can be suppressed, and warpage and cracking of the laminated plate can be suppressed. From this point of view, the storage elastic modulus of the resin cured layer is more preferably from 3 to 70 GPa, and still more preferably from 5 to 60 GPa.
進而,亦可於積層板的單面或兩面,具有銅或鋁等金屬箔。金屬箔只要是電絕緣材料用途中所使用之金屬箔即可,並無特別限制。 Further, a metal foil such as copper or aluminum may be provided on one or both sides of the laminate. The metal foil is not particularly limited as long as it is a metal foil used in the use of an electrical insulating material.
(藉由壓製法所成之製造例) (manufacturing example by suppression method)
另外,本發明之積層板,可藉由壓製法來製造。 Further, the laminated board of the present invention can be produced by a pressing method.
例如,可對上述藉由層疊而獲得之積層體,利用壓製法來加熱、加壓以進行硬化,藉此製造積層板。 For example, the laminated body obtained by laminating the above may be heated and pressed by a pressing method to be hardened, thereby producing a laminated board.
另外,亦可將上述黏著膜或者將自該黏著膜除去支持體膜和保護膜後所成之黏著膜本體、與玻璃基板重合,利用壓製法來加熱、加壓以進行硬化,藉此製造積層板。 In addition, the adhesive film or the adhesive film body formed by removing the support film and the protective film from the adhesive film may be superposed on the glass substrate, and heated and pressed by a pressing method to be cured, thereby producing a laminate. board.
進而,亦可將樹脂組成物塗刷,並乾燥而形成為B階段狀態,將該B階段狀態的樹脂組成物重合於玻璃基板上,利用壓製法來加熱、加壓以進行硬化,藉此製造積層板。此時,較佳為以120~300℃之範圍進行加熱,更佳為以150℃以上250℃以下之溫度進行加熱。若為120℃以上,則樹脂硬化物 層與玻璃基板的黏著性有變得良好的傾向,且當為300℃以下時,則抑制聚醯胺醯亞胺樹脂的熱分解,因此較佳。另外,較佳為以1~5MPa進行加壓,更佳為以2~5MPa進行加壓。 Further, the resin composition may be brushed and dried to form a B-stage state, and the resin composition in the B-stage state may be superposed on a glass substrate, and heated and pressed by a pressing method to be cured. Laminated board. In this case, it is preferred to carry out heating in a range of from 120 to 300 ° C, more preferably at a temperature of from 150 ° C to 250 ° C. If it is 120 ° C or more, the resin cured product The adhesion between the layer and the glass substrate tends to be good, and when it is 300 ° C or lower, thermal decomposition of the polyamide amide resin is suppressed, which is preferable. Further, it is preferred to pressurize at 1 to 5 MPa, and more preferably at 2 to 5 MPa.
[多層積層板及其製造方法] [Multilayer laminate and its manufacturing method]
本發明之多層積層板,包含複數個積層板,並且至少1個積層板為前述之本發明之積層板。 The multi-layer laminate of the present invention comprises a plurality of laminates, and at least one laminate is the aforementioned laminate of the present invention.
該多層積層板的製造方法並無特別限制。 The method for producing the multilayered laminate is not particularly limited.
例如,經由自上述黏著膜除去支持體膜和保護膜後所成之黏著膜本體,積層複數個上述積層板而使其多層化即可。 For example, a plurality of the laminated sheets formed by removing the support film and the protective film from the adhesive film may be laminated and multilayered.
另外,亦可藉由將數片(例如,2~20片)積層體重疊,並進行積層成形,而製造多層積層板。具體而言,可於下述條件下成形:使用多階段式層壓機、多階段式真空層壓機、連續成形機、高壓釜成形機等,於溫度100~250℃左右、壓力2~100MPa左右、及加熱時間0.1~5小時左右之範圍內進行成形。 Further, a plurality of laminated sheets can be produced by laminating a plurality of sheets (for example, 2 to 20 sheets) and laminating them. Specifically, it can be molded under the following conditions: a multi-stage laminator, a multi-stage vacuum laminator, a continuous molding machine, an autoclave molding machine, etc., at a temperature of about 100 to 250 ° C and a pressure of 2 to 100 MPa. The molding is carried out in the range of about 0.1 to 5 hours in the left and right and the heating time.
[印刷線路板及其製造方法] [Printed circuit board and its manufacturing method]
本發明之印刷線路板,是將線路設置於本發明之積層板的至少一面上而成。另外,本發明之印刷線路板,有時亦為包含複數個積層板之組成(多層印刷線路板),此時,其中至少有1個積層板是本發明之積層板。 The printed wiring board of the present invention is formed by providing a wiring on at least one surface of the laminated board of the present invention. Further, the printed wiring board of the present invention is sometimes composed of a plurality of laminated boards (multilayer printed wiring boards), and at this time, at least one of the laminated boards is a laminated board of the present invention.
其次,說明該印刷線路板的製造方法。 Next, a method of manufacturing the printed wiring board will be described.
(通路孔等之形成) (formation of via holes, etc.)
於上述積層板上,視需要利用鑽孔機、雷射、電漿、或該等之組合等方法來進行開孔,形成通路孔(via hole)或貫穿孔(through hole)。作為雷射,一般使用二氧化碳雷射或釔鋁石榴石雷射(yttrium-aluminum-garnet laser,YAG雷射)、紫外雷射(ultraviolet laser,UV雷射)、準分子雷射等。形成通路孔等之後,亦可使用氧化劑來進行除膠渣處理(desmear treatment)。作為氧化劑,較合適為過錳酸鹽(過錳酸鉀、過錳酸鈉等)、重鉻酸鹽、臭氧、過氧化氫/硫酸、硝酸;更合適為過錳酸鉀、過錳酸鈉等之氫氧化鈉水溶液(鹼性過錳酸水溶液)。 On the above laminated board, a hole, a via hole or a through hole is formed by a method such as a drill, a laser, a plasma, or a combination thereof. As the laser, a carbon dioxide laser or a yttrium-aluminum-garnet laser (YAG laser), an ultraviolet laser (UV laser), an excimer laser, or the like is generally used. After forming a via hole or the like, an oxidizing agent may also be used for desmear treatment. As the oxidizing agent, it is more suitable as permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide/sulfuric acid, nitric acid; more suitable is potassium permanganate or sodium permanganate. Aqueous sodium hydroxide solution (alkaline permanganic acid aqueous solution).
(線路圖案之形成) (formation of line pattern)
作為後續之圖案形成的方法,例如,可採用公知之減除法(subtractive process)、半加成法(semi-additive process)等方法。 As a method of forming the subsequent pattern, for example, a known method of a subtractive process, a semi-additive process, or the like can be employed.
於本發明之積層板或多層積層板的樹脂硬化物層上,藉由鍍敷法進行電路加工之情況下,首先,進行粗糙化處理。 作為此時的粗糙化液,可使用:鉻/硫酸粗糙化液、鹼性過錳酸粗糙化液、氟化鈉/鉻/硫酸粗糙化液、氟硼酸粗糙化液等氧化性粗糙化液。粗糙化處理,例如,可如下述方式進行:首先,將二乙二醇單丁醚與NaOH之水溶液作為膨潤液,加溫至70℃,將積層板或多層積層板進行5分鐘浸漬處理。其次,將KMnO4與NaOH之水溶液作為粗糙化液,加溫至80℃,進 行10分鐘浸漬處理。繼而,於中和液,例如氯化亞錫(SnCl2)之鹽酸水溶液中、室溫下進行5分鐘浸漬處理而加以中和。 In the case where the circuit is processed by the plating method on the resin cured layer of the laminated board or the multilayered laminated board of the present invention, first, the roughening treatment is performed. As the roughening liquid at this time, an oxidizing roughening liquid such as a chromium/sulfuric acid roughening liquid, an alkaline permanganic acid roughening liquid, a sodium fluoride/chromium/sulfuric acid roughening liquid, or a fluoroboric acid roughening liquid can be used. The roughening treatment can be carried out, for example, by first adding an aqueous solution of diethylene glycol monobutyl ether and NaOH as a swelling liquid to a temperature of 70 ° C, and immersing the laminate or the multilayer laminate for 5 minutes. Next, an aqueous solution of KMnO 4 and NaOH was used as a roughening liquid, and the mixture was heated to 80 ° C and immersed for 10 minutes. Then, it is neutralized by a immersion treatment in a neutralizing liquid, for example, a hydrochloric acid aqueous solution of stannous chloride (SnCl 2 ) at room temperature for 5 minutes.
粗糙化處理後,進行鍍敷觸媒賦予處理,以使鈀附著。鍍敷觸媒賦予處理,是浸漬於氯化鈀系之鍍敷觸媒液中而進行。繼而,浸漬於無電鍍敷液中,進行無電鍍敷處理,析出厚度為0.3~1.5μm之無電鍍敷層(導體層)。 After the roughening treatment, a plating catalyst application treatment is performed to adhere the palladium. The plating catalyst application treatment is carried out by immersing in a palladium chloride-based plating catalyst liquid. Then, it was immersed in an electroless plating solution, and subjected to electroless plating treatment to deposit an electroless plating layer (conductor layer) having a thickness of 0.3 to 1.5 μm.
繼而,形成鍍敷光阻後,進行電鍍處理,於所期望之部位形成所期望厚度之電路。無電鍍敷處理中使用之無電鍍敷液,可使用公知之無電鍍敷液,並無特別限制。鍍敷光阻亦可使用公知之鍍敷光阻,並無特別限制。另外,電鍍處理亦可採用公知之方法來實施,並無特別限制。該等鍍敷較佳為鍍銅。進而,蝕刻除去不需要的部位的無電鍍敷層,藉此可形成外層電路。 Then, after the plating resist is formed, a plating process is performed to form a circuit of a desired thickness at a desired portion. The electroless plating solution used in the electroless plating treatment may be a known electroless plating solution, and is not particularly limited. The plating resist can also be a known plating resist, and is not particularly limited. Further, the plating treatment can be carried out by a known method, and is not particularly limited. These platings are preferably copper plated. Further, an electroless plating layer of an unnecessary portion is removed by etching, whereby an outer layer circuit can be formed.
[多層印刷線路板及其製造方法] [Multilayer printed wiring board and method of manufacturing the same]
作為上述印刷線路板的一種形態,亦可積層複數個以上述方式形成線路圖案之積層板,作為多層印刷線路板。 As one form of the printed wiring board, a plurality of laminated boards in which the wiring pattern is formed as described above may be laminated as a multilayer printed wiring board.
製造該多層印刷線路板時,經由上述黏著膜本體,積層複數個上述形成線路圖案之積層板,藉此使其多層化。之後,藉由鑽孔加工或雷射加工來形成貫穿孔或盲通孔,且藉由鍍敷或導電膏來形成層間線路。如此,可製造多層印刷線路板。 When the multilayer printed wiring board is manufactured, a plurality of the laminated sheets forming the wiring pattern are laminated via the adhesive film main body to form a multilayer. Thereafter, through holes or blind via holes are formed by drilling or laser processing, and interlayer wiring is formed by plating or conductive paste. In this way, a multilayer printed wiring board can be manufactured.
[附金屬箔之積層板及多層積層板、以及該等的製造方法] [Laminated sheet and multi-layer laminated board with metal foil, and manufacturing method of the same]
本發明之積層板及使用本發明之積層板之多層積層板,亦可以是於單面或兩面具有銅或鋁等金屬箔之附金屬箔之積層板及多層積層板。 The laminated board of the present invention and the multi-layered laminated board using the laminated board of the present invention may be a laminated metal sheet and a multilayer laminated board having a metal foil such as copper or aluminum on one or both sides.
該附金屬箔之積層板的製造方法並無特別限制。例如,可如上所述般,藉由使用金屬箔作為支持體膜,可製造附金屬箔之積層板。另外,亦可藉由下述方式製造:上述藉由層疊或塗刷所得之積層體,使用1片或者將數片(例如2~20片)重疊,以其單面或兩面配置金屬箔的組成來進行積層成形,藉此製造附金屬箔之積層板。 The method for producing the metal foil-clad laminate is not particularly limited. For example, a metal foil-attached laminate can be produced by using a metal foil as a support film as described above. Alternatively, it may be produced by laminating or brushing the laminated body obtained by laminating or brushing, using one sheet or a plurality of sheets (for example, 2 to 20 sheets), and arranging the metal foil on one or both sides thereof. Lamination molding is carried out to thereby produce a laminate with a metal foil.
成形條件,可合宜地使用電絕緣材料用積層板或多層板之方法,例如,可以下述條件進行成形:使用多階段式層壓機、多階段式真空層壓機、連續成形機、高壓釜成形機等,於溫度100~250℃左右、壓力2~100MPa左右、及加熱時間0.1~5小時左右之範圍內進行成形。 The molding conditions can be suitably carried out by using a laminate or a multilayer laminate for an electrically insulating material, for example, molding can be carried out using a multi-stage laminator, a multi-stage vacuum laminator, a continuous molding machine, and an autoclave. The molding machine or the like is formed at a temperature of about 100 to 250 ° C, a pressure of about 2 to 100 MPa, and a heating time of about 0.1 to 5 hours.
其次,藉由實施例來具體地說明本發明,但本發明的範圍並不限定於該等實施例。 Next, the present invention will be specifically described by way of examples, but the scope of the invention is not limited to the examples.
(聚醯胺醯亞胺樹脂之合成) (Synthesis of polyamidoximine resin)
對安裝有熱電偶、攪拌機、氮氣送入口之500ml可分離式燒瓶中,一面流入約250ml/min之氮氣,一面加入X-22-161A(信越化學工業股份有限公司製造,商品名)32.0g、4,4'-二胺基二環己基甲烷(Wondamine HM(WHM),新日本理 化股份有限公司製造,商品名)0.935g、Jeffamine D2000(三井精細化學股份有限公司)40.0g、偏苯三甲酸酐(以下,簡稱為TMA)17.9g和N-甲基-2-吡咯啶酮250g,並攪拌,使之溶解。 於該溶液中添加甲苯100g,以150℃以上之溫度實施6小時的脫水回流而進行醯亞胺環閉環反應之後,蒸餾去除甲苯,冷卻後,添加4,4'-二苯基甲烷二異氰酸酯(MDI)13.4g,於150℃下反應2小時,合成聚醯胺醯亞胺樹脂。之後,添加TMA 1.6g,於80℃下攪拌1小時,合成聚醯胺醯亞胺樹脂溶液。 To a 500 ml separable flask equipped with a thermocouple, a stirrer, and a nitrogen gas inlet, a nitrogen gas of about 250 ml/min was introduced while adding X-22-161A (manufactured by Shin-Etsu Chemical Co., Ltd., trade name) 32.0 g, 4,4'-Diaminodicyclohexylmethane (Wondamine HM (WHM), New Japan Chemical Co., Ltd., trade name) 0.935g, Jeffamine D2000 (Mitsui Fine Chemical Co., Ltd.) 40.0g, trimellitic anhydride (hereinafter referred to as TMA) 17.9g and N-methyl-2-pyrrolidone 250g And stir to dissolve. 100 g of toluene was added to the solution, and dehydration reflux was carried out at a temperature of 150 ° C or higher for 6 hours to carry out a ring closure reaction of the imide ring, and then toluene was distilled off, and after cooling, 4,4'-diphenylmethane diisocyanate was added ( MDI) 13.4 g was reacted at 150 ° C for 2 hours to synthesize a polyamidoximine resin. Thereafter, 1.6 g of TMA was added, and the mixture was stirred at 80 ° C for 1 hour to synthesize a polyamidoximine resin solution.
(清漆A) (varnish A)
於固體成分為70g之聚醯胺醯亞胺樹脂溶液中,加入雙環戊二烯酚型環氧樹脂HP7200(DIC股份有限公司製造,商品名)20g、具有3個以上的與環氧基反應之官能基之樹脂EPPN-502H(日本化藥股份有限公司製造,商品名,多官能環氧樹脂)10g、硬化促進劑2E4MZ-CN(四國化成工業股份有限公司製造,商品名)0.15g,用NMP稀釋成固體成分濃度為30%,製備清漆A。 To a solution of a polyamidoxime imide resin having a solid content of 70 g, 20 g of a dicyclopentadiene phenol type epoxy resin HP7200 (manufactured by DIC Corporation, trade name) was added, and three or more reactive groups were reacted with an epoxy group. Resin-based resin EPPN-502H (manufactured by Nippon Kayaku Co., Ltd., trade name, polyfunctional epoxy resin) 10 g, hardening accelerator 2E4MZ-CN (manufactured by Shikoku Chemical Co., Ltd., trade name) 0.15 g, used The varnish A was prepared by diluting NMP to a solid concentration of 30%.
(清漆B~清漆C) (varnish B~ varnish C)
與清漆A同樣地,以表1的調配量來調配清漆B~清漆C。 In the same manner as the varnish A, the varnish B to the varnish C was prepared in the amount shown in Table 1.
(清漆D) (varnish D)
使用聯苯酚醛清漆型環氧樹脂NC3000(日本化藥股份有限公司製造,商品名),來代替環氧樹脂HP7200,除此以外,與清漆A同樣地調配清漆D。 A varnish D was prepared in the same manner as the varnish A except that the epoxy resin HP7200 was used instead of the epoxy resin HP3000 (manufactured by Nippon Kayaku Co., Ltd., trade name).
以上的調配例中,HP7200是一分子中具有2個以上的環氧基,並且與聚醯胺醯亞胺樹脂相溶之環氧樹脂;NC3000是一分子中具有2個以上的環氧基,並且與聚醯胺醯亞胺樹脂不相溶之環氧樹脂;EPPN-502H是一分子中具有3個以上的與環氧基反應的官能基之樹脂。 In the above formulation, HP7200 is an epoxy resin having two or more epoxy groups in one molecule and compatible with a polyamidoximine resin; and NC3000 has two or more epoxy groups in one molecule. And an epoxy resin which is incompatible with the polyamidoximine resin; EPPN-502H is a resin having three or more functional groups reactive with an epoxy group in one molecule.
(黏著膜之製造) (Manufacture of adhesive film)
使用刮條式塗佈機,將樹脂清漆A~樹脂清漆D,以乾燥後為5μm之方式,塗佈於厚度38μm且經脫模處理之聚對苯二甲酸乙二酯(PET)膜(PET-38X,琳得科股份有限公司(Lintec Corporation)製造,商品名)的脫模處理面上,並於140℃下乾燥15分鐘,形成樹脂組成物層,獲得黏著膜。 Resin varnish A to resin varnish D was applied to a polyethylene film (PET) film having a thickness of 38 μm and subjected to release treatment using a bar coater to a thickness of 5 μm. -38X, a release-treated surface of a product manufactured by Lintec Corporation (trade name), and dried at 140 ° C for 15 minutes to form a resin composition layer, thereby obtaining an adhesive film.
(輔助黏著層用膜之製造) (Manufacture of film for auxiliary adhesive layer)
於含酚性羥基之聚丁二烯改質聚醯胺(日本化藥股份有限公司製造,商品名:BPAM-155)10.2g中,調配N,N-二甲基乙醯胺(DMAc)91.4g後,添加聯苯基芳烷基型環氧樹脂(日本化藥股份有限公司製造,商品名:NC-3000H)40.0g、雙酚A酚醛清漆(三菱化學股份有限公司(Mitsubishi Chemical Corporation)製造,商品名:YLH129)12.6g、作為硬化促進劑 之2-苯基咪唑(四國化成工業股份有限公司(Shikoku Chemicals Corporation)製造,商品名:2PZ)0.4g、氣相二氧化矽(fumed silica,Nippon Aerosil股份有限公司製造,商品名:R972)3.6g,之後,以由DMAc及甲基乙基酮而成之混合溶劑(MEK/DMAc=7/3(質量比))加以稀釋(固體成分濃度約25質量%)。之後,使用分散機(Nanomizer,商品名,吉田機械興業股份有限公司(Yoshida Kikai Co.Ltd.)製造),獲得輔助黏著層用樹脂清漆。 Formulated with N,N-dimethylacetamide (DMAc) 91.4 in 10.2 g of polybutadiene modified polyamine (manufactured by Nippon Kayaku Co., Ltd., trade name: BPAM-155) containing phenolic hydroxyl group. After g, a biphenyl aralkyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: NC-3000H) 40.0 g, bisphenol A novolac (manufactured by Mitsubishi Chemical Corporation) was added. , trade name: YLH129) 12.6g, as a hardening accelerator 2-phenylimidazole (manufactured by Shikoku Chemicals Corporation, trade name: 2PZ) 0.4 g, fumed silica (manufactured by Nippon Aerosil Co., Ltd., trade name: R972) After 3.6 g, it was diluted with a mixed solvent of DMAc and methyl ethyl ketone (MEK/DMAc = 7/3 (mass ratio)) (solid content concentration: about 25% by mass). Thereafter, a resin varnish for an auxiliary adhesive layer was obtained using a disperser (Nanomizer, trade name, manufactured by Yoshida Kikai Co., Ltd.).
使用刮條式塗佈機,將輔助黏著層用樹脂清漆,以乾燥後為5μm之方式,塗佈於厚度20μm之銅箔(NC箔,古河電氣工業股份有限公司(Furukawa Electric Co.,Ltd.)製造)的光澤面上,並於140℃下乾燥10分鐘,製作輔助黏著層用樹脂膜。 Using a bar coater, the auxiliary adhesive layer was coated with a resin varnish to a thickness of 20 μm and applied to a copper foil having a thickness of 20 μm (NC foil, Furukawa Electric Co., Ltd.). The shiny surface of the manufactured) was dried at 140 ° C for 10 minutes to prepare a resin film for an auxiliary adhesive layer.
[玻璃黏著性評價用積層板(樹脂硬化物層/玻璃基板層/樹脂硬化物層)之製造] [Manufacture of laminated board for glass adhesion evaluation (resin cured layer / glass substrate layer / resin cured layer)]
使用日本電氣硝子股份有限公司(Nippon Electric Glass Co.,Ltd.)製造之極薄玻璃膜「OA-10G」(商品名,厚度100μm),作為玻璃基板。將所製作之黏著膜的樹脂組成物層,以接觸玻璃基板之方式,配置於該玻璃基板的兩面上,使用批次式的真空加壓層疊機「MVLP-500」(名機股份有限公司(Meiki Co.,Ltd.)製造,商品名)藉由層疊進行積層,而獲得積 層體。此時之真空度為30mmHg以下,溫度設定為120℃,壓力設定為0.5MPa。 An ultra-thin glass film "OA-10G" (trade name, thickness: 100 μm) manufactured by Nippon Electric Glass Co., Ltd. was used as a glass substrate. The resin composition layer of the produced adhesive film was placed on both surfaces of the glass substrate so as to contact the glass substrate, and a batch type vacuum pressure laminating machine "MVLP-500" (Ming Machine Co., Ltd.) was used. Manufactured by Meiki Co., Ltd.), which is laminated by lamination to obtain a product. Layer body. At this time, the degree of vacuum was 30 mmHg or less, the temperature was set to 120 ° C, and the pressure was set to 0.5 MPa.
冷卻至室溫後,剝離支持體膜,以光澤面與樹脂組成物層接觸之方式配置銅箔後,以185℃、3MPa、1小時之條件實施熱壓,藉此進行熱壓接。蝕刻銅箔,而獲得玻璃黏著性評價用積層板(樹脂硬化物層/玻璃基板層/樹脂硬化物層)。使用以清漆A~清漆D製成之黏著膜的玻璃黏著性評價用積層板,分別相當於實施例1~實施例4。 After cooling to room temperature, the support film was peeled off, and the copper foil was placed so that the gloss surface was in contact with the resin composition layer, and then hot pressed at 185 ° C, 3 MPa, and 1 hour to perform thermocompression bonding. The copper foil was etched to obtain a laminate (resin cured layer/glass substrate layer/resin cured layer) for evaluation of glass adhesion. The laminated sheets for glass adhesion evaluation using the adhesive film made from the varnish A~ varnish D correspond to Example 1 - Example 4, respectively.
使用日本電氣硝子股份有限公司製造之極薄玻璃膜「OA-10G」(商品名,厚度100μm),作為玻璃基板,將輔助黏著用樹脂膜,以樹脂層接觸玻璃基板之方式,配置於該玻璃基板的兩面上,以185℃、3MPa、1小時之條件實施熱壓,藉此進行熱壓接。繼而,蝕刻銅箔,而獲得玻璃黏著性評價用積層板(輔助黏著層/玻璃基板層/輔助黏著層)。 An ultra-thin glass film "OA-10G" (trade name, thickness: 100 μm) manufactured by Nippon Electric Glass Co., Ltd. is used as a glass substrate, and the resin film for auxiliary adhesion is placed on the glass so that the resin layer contacts the glass substrate. Hot pressing was performed on both surfaces of the substrate at 185 ° C, 3 MPa, and 1 hour, thereby performing thermocompression bonding. Then, the copper foil was etched to obtain a laminate (adhesive adhesion layer/glass substrate layer/auxiliary adhesion layer) for evaluation of glass adhesion.
其次,對實施例和參考例中獲得之玻璃黏著性評價用積層板,藉由以下方法,測定對於玻璃之黏著性,並進行評價。 Next, the adhesion sheets for glass adhesion evaluation obtained in the examples and the reference examples were measured and evaluated for adhesion to glass by the following method.
藉由橫割試驗,來評價黏著性。 Adhesion was evaluated by a cross-cut test.
橫割試驗:於所製成之積層板上,使用橫割導割規CCJ-1(Cotec股份有限公司製造,商品名),切割出棋盤狀的 切口,其橫豎分別為5條切線,且各切線間的寬度為2mm,觀察黏附TQC ISO附著帶並剝離該附著帶後之表面狀態,檢查25個方格中,未被剝離之方格數目。再者,實驗方法是以日本工業標準(JIS)K56005-6為依據。 Cross-cut test: Cut the checkerboard shape on the laminated board produced by using the cross-cutting guide CCJ-1 (manufactured by Cotec Co., Ltd., trade name) The slits were respectively five tangential lines in the horizontal and vertical directions, and the width between the tangential lines was 2 mm. The surface state after adhering the TQC ISO attachment tape and peeling off the adhesive tape was observed, and the number of squares which were not peeled out in the 25 squares was examined. Furthermore, the experimental method is based on the Japanese Industrial Standard (JIS) K56005-6.
實驗結果示於表2中。 The experimental results are shown in Table 2.
其次,使用輔助黏著層用樹脂膜,藉由一連串的步驟獲得焊料耐熱性評價用積層板,以評價構裝時的焊料耐熱性。 Next, a laminate for solder heat resistance evaluation was obtained by a series of steps using a resin film for an auxiliary adhesive layer to evaluate solder heat resistance at the time of mounting.
[焊料耐熱性評價用積層板之製造] [Manufacture of laminate for solder heat resistance evaluation]
使用日本電氣硝子股份有限公司製造之極薄玻璃膜「OA-10G」(商品名,厚度100μm),作為玻璃基板。將所製作之黏著膜的樹脂組成物層,以接觸玻璃基板之方式,配置於該玻璃基板的兩面上,使用批次式的真空加壓層疊機「MVLP-500」(名機股份有限公司製造,商品名),藉由層疊來進行積層。此時的真空度為30mmHg以下,溫度設定為120℃,壓力設定為0.5MPa。 A very thin glass film "OA-10G" (trade name, thickness: 100 μm) manufactured by Nippon Electric Glass Co., Ltd. was used as a glass substrate. The resin composition layer of the produced adhesive film was placed on both surfaces of the glass substrate so as to contact the glass substrate, and a batch type vacuum pressure laminating machine "MVLP-500" (manufactured by Nagoya Co., Ltd.) was used. , trade name), laminated by lamination. The degree of vacuum at this time was 30 mmHg or less, the temperature was set to 120 ° C, and the pressure was set to 0.5 MPa.
冷卻至室溫後,剝離黏著膜的支持體膜,並以輔助黏著層用樹脂膜的樹脂層,接觸已設置於玻璃基板上的樹脂組成物層之方式,配置輔助黏著層用樹脂膜後,以185℃、3MPa、1小時之條件實施熱壓,藉此進行熱壓接。之後,蝕刻銅箔,而獲得積層板。 After cooling to room temperature, the support film of the adhesive film is peeled off, and after the resin layer of the resin film for the auxiliary adhesive layer is brought into contact with the resin composition layer provided on the glass substrate, the resin film for the auxiliary adhesive layer is placed. The hot pressing was carried out under the conditions of 185 ° C, 3 MPa, and 1 hour, thereby performing thermocompression bonding. Thereafter, the copper foil was etched to obtain a laminate.
進行以下操作,以對所獲得之積層板進行化學粗糙 化:製作二乙二醇單丁醚為200ml/L、NaOH為5g/L之水溶液,來作為膨潤液,加溫至70℃,進行5分鐘浸漬處理。其次,製作KMnO4為60g/L、NaOH為40g/L之水溶液,來作為粗糙化液,加溫至80℃,進行10分鐘浸漬處理。繼而,於中和液(SnCl2:30g/L,HCl:300ml/L)之水溶液中、於室溫下浸漬處理5分鐘來進行中和。 The following operations were carried out to chemically roughen the obtained laminate: an aqueous solution of 200 ml/L of diethylene glycol monobutyl ether and 5 g/L of NaOH was prepared as a swelling liquid, and the mixture was heated to 70 ° C for 5 Minute immersion treatment. Next, an aqueous solution of 60 g/L of KMnO 4 and 40 g/L of NaOH was prepared, and the mixture was heated to 80 ° C as a roughening liquid, and immersed for 10 minutes. Then, neutralization was carried out by immersing in an aqueous solution of a neutralizing solution (SnCl 2 : 30 g/L, HCl: 300 ml/L) at room temperature for 5 minutes.
為了於經實施化學粗糙化之積層板上形成導體層,首先,於含有PdCl2之無電鍍敷用觸媒HS-202B(日立化成股份有限公司製造,商品名)中、室溫下進行10分鐘浸漬處理,並進行水洗,再於無電鍍銅用鍍敷液CUST-201(日立化成股份有限公司製造,商品名)中,於室溫下浸漬15分鐘,進一步進行硫酸銅電鍍。之後,於180℃下進行60分鐘退火,形成厚度25μm之導體層,而獲得焊料耐熱性評價用積層板。使用以清漆A~清漆D製成之黏著膜的焊料耐熱性評價用積層板,分別相當於實施例1~實施例4。 In order to form a conductor layer on a laminate which is subjected to chemical roughening, first, it is carried out for 10 minutes at room temperature in an electroless plating catalyst HS-202B (trade name, manufactured by Hitachi Chemical Co., Ltd.) containing PdCl 2 . After immersion treatment, it was washed with water, and further immersed in a plating solution for electroless copper plating CUST-201 (manufactured by Hitachi Chemical Co., Ltd., trade name) for 15 minutes at room temperature to further perform copper sulfate plating. Thereafter, annealing was performed at 180 ° C for 60 minutes to form a conductor layer having a thickness of 25 μm, thereby obtaining a laminate for evaluation of solder heat resistance. The laminate for solder heat resistance evaluation using an adhesive film made of varnish A to varnish D corresponds to Examples 1 to 4.
使用日本電氣硝子股份有限公司製造之極薄玻璃膜「OA-10G」(商品名,厚度100μm),作為玻璃基板,將輔助黏著用樹脂膜,以樹脂層接觸玻璃基板之方式,配置於該玻璃基板的兩面上,以185℃、3MPa、1小時之條件實施熱壓,藉此進行熱壓接。繼而,蝕刻銅箔,而獲得積層板(輔助黏著層/玻璃基板層/輔助黏著層)。然後,藉由與前述實施例同樣 之方法,於積層板上形成導體層,獲得焊料耐熱性評價用積層板。 An ultra-thin glass film "OA-10G" (trade name, thickness: 100 μm) manufactured by Nippon Electric Glass Co., Ltd. is used as a glass substrate, and the resin film for auxiliary adhesion is placed on the glass so that the resin layer contacts the glass substrate. Hot pressing was performed on both surfaces of the substrate at 185 ° C, 3 MPa, and 1 hour, thereby performing thermocompression bonding. Then, the copper foil was etched to obtain a laminate (auxiliary adhesive layer/glass substrate layer/auxiliary adhesive layer). Then, by the same as the previous embodiment In this method, a conductor layer is formed on a laminate, and a laminate for evaluation of solder heat resistance is obtained.
以如下述之方式,評價所獲得之焊料耐熱性評價用積層板的焊料耐熱性。 The solder heat resistance of the obtained laminate for solder heat resistance evaluation was evaluated as follows.
將各例中製作之焊料耐熱性評價用積層板切斷成25mm見方,漂浮於調整為265±2℃之焊料槽中,調查直到膨脹產生為止所花費之時間(秒)。結果示於表2。 The laminate for solder heat resistance evaluation prepared in each example was cut into 25 mm square, floated in a solder bath adjusted to 265 ± 2 ° C, and the time (seconds) taken until expansion occurred was examined. The results are shown in Table 2.
由表2可知,本發明之實施例1~實施例4中,樹脂組成物層與玻璃基板層的黏著性較高。另外可知,使用本發明之樹脂組成物層所製作之積層板,焊料耐熱性亦優異,因此可製造一種將環境考慮在內之線路板。 As is apparent from Table 2, in Examples 1 to 4 of the present invention, the adhesion between the resin composition layer and the glass substrate layer was high. Further, it has been found that the laminated sheet produced by using the resin composition layer of the present invention is excellent in solder heat resistance, and thus it is possible to manufacture a wiring board which takes the environment into consideration.
根據以上結果可知,利用本發明,可提供一種積層板,該積層板中樹脂組成物層與玻璃基板層的黏著性、及耐熱性優異。 According to the above results, according to the present invention, it is possible to provide a laminated board in which the resin composition layer and the glass substrate layer are excellent in adhesion and heat resistance.
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