TWI636878B - Thermoplastic resin film substrate for photo-fired, conductive circuit substrate using the same, and manufacturing method thereof - Google Patents
Thermoplastic resin film substrate for photo-fired, conductive circuit substrate using the same, and manufacturing method thereof Download PDFInfo
- Publication number
- TWI636878B TWI636878B TW103111737A TW103111737A TWI636878B TW I636878 B TWI636878 B TW I636878B TW 103111737 A TW103111737 A TW 103111737A TW 103111737 A TW103111737 A TW 103111737A TW I636878 B TWI636878 B TW I636878B
- Authority
- TW
- Taiwan
- Prior art keywords
- substrate
- photo
- fired
- resin
- resin film
- Prior art date
Links
Classifications
-
- 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
- B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
-
- H—ELECTRICITY
- 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
- H05K1/036—Multilayers with layers of different types
-
- H—ELECTRICITY
- 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
- H05K1/0393—Flexible materials
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
- H05K3/1283—After-treatment of the printed patterns, e.g. sintering or curing methods
-
- 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
- B32B2457/08—PCBs, i.e. printed circuit boards
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- 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
- H05K2201/01—Dielectrics
- H05K2201/0104—Properties and characteristics in general
- H05K2201/0129—Thermoplastic polymer, e.g. auto-adhesive layer; Shaping of thermoplastic polymer
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- 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
- H05K2201/01—Dielectrics
- H05K2201/0183—Dielectric layers
- H05K2201/0195—Dielectric or adhesive layers comprising a plurality of layers, e.g. in a multilayer structure
Abstract
本發明提供一種即使進行光燒成，表面上所形成之電路圖型亦不會發生斷線或龜裂之光燒成用熱塑性樹脂薄膜基材，使用其之導電電路基板及其製造方法。 The present invention provides a conductive resin substrate and a method for producing the same, which are used for photo-fired thermoplastic resin film substrates which are not broken or cracked even when photo-fired.
本發明提供一種於基材(1)之表層上形成具有交聯結構之樹脂層(5)之光燒成用熱塑性樹脂薄膜基材。此外，導電電路基板係於上述光燒成用熱塑性樹脂薄膜基材上形成電路圖型索成。再者，導電電路基板之製造方法係於上述光燒成用熱塑性樹脂薄膜基材上形成電路圖型後，使電路圖型進行光燒成。 The present invention provides a thermoplastic resin film substrate for photo-baking having a resin layer (5) having a crosslinked structure formed on a surface layer of a substrate (1). Further, the conductive circuit substrate is formed into a circuit pattern on the above-mentioned thermoplastic resin film substrate for photo-fired. Further, in the method of producing a conductive circuit substrate, a circuit pattern is formed on the thermoplastic resin film substrate for photo-fired, and then the circuit pattern is photo-fired.
Description
本發明係關於光燒成用熱塑性樹脂薄膜基材(以下亦簡稱為「基材」)、導電電路基板及導電電路基板之製造方法，詳言之，係關於即使進行光燒成，於表面上所形成之電路圖型仍不會發生斷線或龜裂之光燒成用熱塑性樹脂薄膜基材、使用其之導電電路基板及其製造方法。 The present invention relates to a method for producing a thermoplastic resin film substrate for photo-baking (hereinafter also referred to simply as "substrate"), a conductive circuit substrate, and a method for producing a conductive circuit substrate, and more specifically, on the surface, even if photo-firing is performed. A thermoplastic resin film substrate for light-fired, which is not broken or cracked, and a conductive circuit substrate using the same, and a method for producing the same.
過去，將熱硬化型之導電性樹脂組成物塗佈或印刷於薄膜基板或玻璃基板等上，藉由使之加熱硬化，形成電阻膜方式觸控面板之電極或印刷配線板之電路圖型等。此外，電漿顯示器面板、螢光顯示管、電子零件等中之導體圖型之形成一般係使用含有極大量之金屬粉末或玻璃粉末之導電性膏以網版印刷法進行圖型形成。 In the past, a thermosetting conductive resin composition is applied or printed on a film substrate, a glass substrate, or the like, and is heated and cured to form an electrode of a resistive film type touch panel or a circuit pattern of a printed wiring board. Further, the formation of a conductor pattern in a plasma display panel, a fluorescent display tube, an electronic component or the like is generally formed by screen printing using a conductive paste containing a very large amount of metal powder or glass powder.
然而，該等方法由於需要在高溫之加熱或燒成，故具有基板須限於不受高溫影響之材料之困難點。例如，纖維素(紙)、聚對苯二甲酸乙二酯(PET)、聚酯 及其他多種塑膠等之成本較低、或可撓性基板大多無法耐受該等溫度。同樣地，有機半導體等基板上之其他成分亦有在高溫下會分解之虞。 However, since such methods require heating or firing at a high temperature, it is difficult to have a substrate that is limited to materials that are not affected by high temperatures. For example, cellulose (paper), polyethylene terephthalate (PET), polyester And many other plastics and the like are low in cost, or most of the flexible substrates cannot withstand such temperatures. Similarly, other components on a substrate such as an organic semiconductor may also decompose at a high temperature.
作為解決該問題之手段近年來已開發所謂的光燒成技術而備受矚目。例如，專利文獻1中提案將至少含粒徑未達1μm之奈米粒子之分散體圖型印刷於基材上，並照射脈衝發光，藉此使含大部分金屬奈米粒子之一部分奈米粒子顯示成為所謂的黑體之舉動、顯示高的電磁波吸收率，且因粒子之熱質量小故粒子急速加熱、熔融且硬化而形成電路圖型之方法。該方法之情況下，因基板之熱傳導率較差，且脈衝長度較短，因此僅最小限度之能量被傳遞到基板，故可解決過去利用熱硬化或燒成之方法的問題。 As a means for solving this problem, in recent years, so-called photo-firing technology has been developed and has attracted attention. For example, Patent Document 1 proposes to print a dispersion pattern containing at least nano particles having a particle diameter of less than 1 μm on a substrate, and irradiate pulsed light to thereby form a part of nano particles containing most of the metal nanoparticles. A method of forming a circuit pattern by displaying a so-called black body behavior, exhibiting a high electromagnetic wave absorptivity, and rapidly heating, melting, and hardening the particles due to the small thermal mass of the particles. In the case of this method, since the thermal conductivity of the substrate is poor and the pulse length is short, only a minimum amount of energy is transmitted to the substrate, so that the problem of the method using thermal hardening or firing in the past can be solved.
[專利文獻] [Patent Literature]
專利文獻1：日本特表2008-522369號公報 Patent Document 1: Japanese Patent Publication No. 2008-522369
然而，使用如專利文獻1所記載之光燒成技術於塑膠等可撓性基材上形成電路圖型時，會有可撓性基材燒成時遭受損害而於電路圖型誘發龜裂或斷線之情況。因此，目前於塑膠等可撓性基材上使用光燒成技術形成電路圖型時，不得不解決該等問題。 However, when a circuit pattern is formed on a flexible substrate such as a plastic using the photo-firing technique described in Patent Document 1, the flexible substrate is damaged during firing, and cracking or disconnection is induced in the circuit pattern. The situation. Therefore, when forming a circuit pattern using a photo-firing technique on a flexible substrate such as plastic, it is necessary to solve such problems.
因此，本發明之目的係提供一種即使進行光燒成於表面上所形成之電路圖型仍不會發生斷線或龜裂之光燒成用熱塑性樹脂薄膜基材、使用其之導電電路基板及其製造方法。 Accordingly, an object of the present invention is to provide a thermoplastic resin film substrate for photo-fired, a conductive circuit substrate using the same, and a conductive resin substrate using the same, which is not broken or cracked even when the pattern is formed by photo-firing on the surface. Production method.
本發明人為解決上述課題而積極檢討之結果，終於獲得以下之見解。圖5為於過去之基材上形成電路圖型時之光燒成前後之基材剖面圖，(a)為光燒成前，(b)為光燒成後。在塑膠等可撓性基材1上形成電路圖型時，若對基材1上以導電性組成物形成之電路圖型之塗膜2進行光燒成，則導電性組成物中之導電性物質之粒子急速加熱、熔融且在基材1上固化，並依據電路圖型形成導體3。此時，導體3同時因熱而收縮。另一方面，隨著導體3之溫度上升，基材1之溫度亦上升，故使用塑膠等可撓性基材1時，基材1之溫度上升至熔點以上時，隨著導體3之收縮，基材1本身亦收縮。 The inventors of the present invention have finally obtained the following findings in order to solve the above problems and actively review the results. Fig. 5 is a cross-sectional view of the substrate before and after photo-fire formation in the case of forming a circuit pattern on a conventional substrate, wherein (a) is before photo-fire and (b) is after photo-firing. When a circuit pattern is formed on a flexible substrate 1 such as a plastic, if the coating film 2 of the circuit pattern formed of the conductive composition on the substrate 1 is photo-fired, the conductive material in the conductive composition is The particles are rapidly heated, melted and solidified on the substrate 1, and the conductor 3 is formed in accordance with the circuit pattern. At this time, the conductor 3 is simultaneously contracted by heat. On the other hand, as the temperature of the conductor 3 rises, the temperature of the substrate 1 also rises. Therefore, when the flexible substrate 1 such as plastic is used, when the temperature of the substrate 1 rises above the melting point, the conductor 3 shrinks. The substrate 1 itself also shrinks.
圖示例中，導體3之邊緣部附近之基材1隨著導體3之收縮而拉伸，產生凹陷4，使基材1遭受損害。因此，認為在可撓性基材1上形成之電路圖型會發生斷線。本發明人基於該見解，進一步積極檢討之結果，發現藉由於基材之表層設置具有交聯結構之樹脂層可解決上述課題，因而完成本發明。 In the illustrated example, the substrate 1 in the vicinity of the edge portion of the conductor 3 is stretched as the conductor 3 contracts, and the recess 4 is generated to damage the substrate 1. Therefore, it is considered that the circuit pattern formed on the flexible substrate 1 is broken. Based on this finding, the present inventors have further actively reviewed the results and found that the above problems can be solved by providing a resin layer having a crosslinked structure on the surface layer of the substrate, and thus the present invention has been completed.
亦即，本發明之光燒成用熱塑性樹脂薄膜基 材之特徵為於基材之表層上形成具有交聯結構之樹脂層而成者。所謂交聯結構為具有交聯基之同一高分子間、不同高分子間、高分子-低分子間、及同一或不同之低分子間，藉由熱、光等電磁能等，相互鍵結而形成之三次元網目結構。藉由形成交聯結構，使高分子等具有之熔點消失，且在表觀上之分子量變無限大，故流動性或溶解度引起變化而顯示耐藥品性、耐溶劑性、耐候性、耐熱性、耐熱老化性等優異之特性。又，本說明書中所示之玻璃轉移溫度可藉習知慣用之測定方法測定，但較好以示差掃描熱量測定(DSC：Differential Scanning Calorimetry)測定之值。 That is, the thermoplastic resin film base for photo-firing of the present invention The material is characterized in that a resin layer having a crosslinked structure is formed on the surface layer of the substrate. The cross-linking structure is such that the same polymer, a different polymer, a polymer-low molecule, and the same or different low molecules having a crosslinking group are bonded to each other by electromagnetic energy such as heat or light. The three-dimensional mesh structure formed. By forming a crosslinked structure, the melting point of the polymer or the like disappears, and the apparent molecular weight becomes infinite, so that the fluidity or solubility changes to exhibit chemical resistance, solvent resistance, weather resistance, heat resistance, Excellent characteristics such as heat aging resistance. Further, the glass transition temperature shown in the present specification can be measured by a conventional measurement method, but is preferably a value measured by Differential Scanning Calorimetry (DSC).
本發明之薄膜基材中，前述樹脂層較好係藉由活性能量線的照射使其硬化所成者。 In the film substrate of the present invention, the resin layer is preferably cured by irradiation with an active energy ray.
且，本發明之導電電路基板之特徵係於上述本發明之光燒成用熱塑性樹脂薄膜基材上形成電路圖型所成者。 Further, the conductive circuit board of the present invention is characterized in that a circuit pattern is formed on the thermoplastic resin film substrate for photo-fired of the present invention.
再者，本發明之導電電路基板的製造方法為上述本發明之導電電路基板之製造方法，其特徵為於前述光燒成用熱塑性樹脂薄膜基材上形成電路圖型後，將該電路圖型進行光燒成。 Furthermore, the method for producing a conductive circuit substrate according to the present invention is the method for producing a conductive circuit substrate according to the present invention, characterized in that the circuit pattern is formed on the thermoplastic resin film substrate for photo-fired. Burnt.
依據本發明，可提供即使進行光燒成，表面上所形成之電路圖型亦不會發生斷線或龜裂之光燒成用熱 塑性樹脂薄膜基材、使用其之導電電路基板及其製造方法。 According to the present invention, it is possible to provide heat for light burning without causing breakage or cracking of a circuit pattern formed on the surface even when photo-firing is performed. A plastic resin film substrate, a conductive circuit substrate using the same, and a method for producing the same.
1‧‧‧基材 1‧‧‧Substrate
2‧‧‧塗膜 2‧‧·coating film
3‧‧‧導體 3‧‧‧Conductors
4‧‧‧凹陷 4‧‧‧ dent
5‧‧‧樹脂層 5‧‧‧ resin layer
圖1係於本發明之基材上形成電路圖型時之光燒成前後之基材的剖面圖，(a)為光燒成前，(b)為光燒成後。 Fig. 1 is a cross-sectional view showing a substrate before and after photo-fire formation when a circuit pattern is formed on a substrate of the present invention, wherein (a) is before photo-fire and (b) is after photo-firing.
圖2係實施例1之導電電路基板之電路圖型之一部分的電子顯微鏡照片。 Fig. 2 is an electron micrograph of a portion of a circuit pattern of the conductive circuit substrate of the first embodiment.
圖3係實施例2之導電電路基板之電路圖型之一部分之電子顯微鏡照片。 Fig. 3 is an electron micrograph of a portion of a circuit pattern of the conductive circuit substrate of the second embodiment.
圖4係比較例之導電電路基板之電路圖型之一部分的電子顯微鏡照片。 Fig. 4 is an electron micrograph of a portion of a circuit pattern of a conductive circuit substrate of a comparative example.
圖5係於過去之基材上形成電路圖型時之光燒成前後之基材之剖面圖，(a)為光燒成前，(b)為光燒成後。 Fig. 5 is a cross-sectional view showing a substrate before and after photo-fire formation in forming a circuit pattern on a conventional substrate, wherein (a) is before photo-fire and (b) is after photo-firing.
以下，針對本發明之實施形態詳細加以說明。 Hereinafter, embodiments of the present invention will be described in detail.
本發明之光燒成用熱塑性樹脂薄膜基材係於基材之表層上形成具有交聯結構之樹脂層者。圖1係於本發明之基 材上形成電路圖型時之光燒成前後之基材的剖面圖，(a)為光燒成前，(b)為光燒成後。如圖所示，本發明之基材係於基材1之表層上設置具有交聯結構之樹脂層5。藉由該樹脂層5，在光燒成時即使導體3收縮，基材1亦不會收縮，可防止光燒成時之電路圖型之龜裂或斷線。為良好獲得該效果，於基材之表層上形成之具有交聯結構之樹脂層之玻璃轉移溫度較好為100℃以上，更好為140℃以上且250℃以下。 The thermoplastic resin film substrate for photo-fired of the present invention is formed by forming a resin layer having a crosslinked structure on the surface layer of the substrate. Figure 1 is based on the basis of the present invention A cross-sectional view of the substrate before and after the light is fired when the circuit pattern is formed on the material, (a) before the light is fired, and (b) after the light is fired. As shown in the figure, the substrate of the present invention is provided with a resin layer 5 having a crosslinked structure on the surface layer of the substrate 1. According to the resin layer 5, even when the conductor 3 is shrunk during photo-fire, the substrate 1 does not shrink, and cracking or disconnection of the circuit pattern at the time of firing can be prevented. In order to obtain this effect well, the glass transition temperature of the resin layer having a crosslinked structure formed on the surface layer of the substrate is preferably 100 ° C or more, more preferably 140 ° C or more and 250 ° C or less.
本發明之基材中，設置於基材1表面上之樹脂層5只要具有交聯結構者，較好玻璃轉移溫度係滿足上述範圍者，則無特別限制，但較好為藉活性能量線之照射而硬化者。其理由為具有交聯結構之樹脂層5可藉由於基材1上塗佈成為樹脂層5之樹脂組成物且藉由活性能量線之照射使之硬化，而容易地形成。 In the substrate of the present invention, the resin layer 5 provided on the surface of the substrate 1 is not particularly limited as long as it has a crosslinked structure, and the glass transition temperature is preferably in the above range, but it is preferably an active energy ray. Hardened by irradiation. The reason for this is that the resin layer 5 having a crosslinked structure can be easily formed by coating the resin composition of the resin layer 5 on the substrate 1 and curing it by irradiation with an active energy ray.
如上述，形成本發明基材之樹脂層5之樹脂組成物只要為以樹脂層5之狀態具有交聯結構者即無特別限制，然而，作為形成本發明基材之樹脂層5之樹脂組成物較好為活性能量線硬化性樹脂組成物，至於活性能量線硬化性樹脂較好為一分子中具有一個以上之乙烯性不飽和鍵之化合物。列舉為例如環氧(甲基)丙烯酸酯、胺基甲酸酯丙烯酸酯、聚酯丙烯酸酯、聚醚丙烯酸酯、於丙烯酸樹脂之側鏈導入乙烯性不飽和雙鍵之改質丙烯酸樹脂等。其中，更好為具有兩個以上之乙烯性不飽和鍵之化合物，進而最好為苯二甲酸二烯丙酯樹脂。形成本發明基材之樹 脂層5之樹脂組成物含有(A)苯二甲酸二烯丙酯樹脂、(B)多官能單體、與(C)光聚合起始劑。以下，針對具有(A)苯二甲酸二烯丙酯樹脂、(B)多官能單體、與(C)光聚合起始劑之樹脂組成物加以詳細說明。 As described above, the resin composition of the resin layer 5 which forms the substrate of the present invention is not particularly limited as long as it has a crosslinked structure in the state of the resin layer 5, however, it is a resin composition of the resin layer 5 which forms the substrate of the present invention. The active energy ray-curable resin composition is preferably a compound having one or more ethylenically unsaturated bonds in one molecule. For example, epoxy (meth) acrylate, urethane acrylate, polyester acrylate, polyether acrylate, a modified acrylic resin which introduces an ethylenically unsaturated double bond to the side chain of an acrylic resin, etc. are mentioned. Among them, a compound having two or more ethylenically unsaturated bonds is more preferable, and more preferably a diallyl phthalate resin. a tree forming the substrate of the present invention The resin composition of the lipid layer 5 contains (A) diallyl phthalate resin, (B) a polyfunctional monomer, and (C) a photopolymerization initiator. Hereinafter, the resin composition having (A) diallyl phthalate resin, (B) polyfunctional monomer, and (C) photopolymerization initiator will be described in detail.
又，本說明書中，所謂(甲基)丙烯酸酯為丙烯酸酯、甲基丙烯酸酯及該等之混合物總稱之用語，其他類似之表達亦相同。 In the present specification, the term "(meth)acrylate" is a generic term for acrylate, methacrylate, and the like, and other similar expressions are also the same.
形成本發明基材之樹脂層5之樹脂組成物中，苯二甲酸二烯丙酯樹脂只要是含有苯二甲酸二烯丙酯系重複單位者，則可為苯二甲酸二烯丙酯系單體之均聚物、2種以上之苯二甲酸二烯丙酯系單體之共聚物、以及苯二甲酸二烯丙酯系單體與可與該單體共聚合之其他單體(例如具有乙烯性雙鍵之芳香族化合物、具有乙烯性雙鍵之脂肪族化合物、或(甲基)丙烯酸化合物)之共聚物。苯二甲酸二烯丙酯系單體與可與該單體共聚合之其他單體之共聚物通常係以苯二甲酸二烯丙酯系重複單位作為主體。 In the resin composition of the resin layer 5 forming the substrate of the present invention, the diallyl phthalate resin may be a diallyl phthalate series as long as it contains a diallyl phthalate-based repeating unit. a homopolymer of a body, a copolymer of two or more diallyl phthalate monomers, and a diallyl phthalate monomer and other monomers copolymerizable with the monomer (for example, A copolymer of an aromatic compound having an ethylenic double bond, an aliphatic compound having an ethylenic double bond, or a (meth)acrylic compound. The copolymer of a diallyl phthalate-based monomer and another monomer copolymerizable with the monomer is usually mainly composed of a diallyl phthalate-based repeating unit.
為苯二甲酸二烯丙酯樹脂之原料的苯二甲酸二烯丙酯系單體係選自鄰苯二甲酸二烯丙酯單體、間苯二甲酸二烯丙酯單體、及對苯二甲酸二烯丙酯單體之化合物。使用該等化合物之1種或2種以上之苯二甲酸二烯丙酯樹脂之合成，及使用該等苯二甲酸二烯丙酯系單體與可與該單體聚合之其他單體之苯二甲酸二烯丙酯樹脂之合成 只要使用已知方法即可，例如，可採用日本特公平2-024850號公報、日本特開平11-147917號公報等所記載之聚合反應。 The diallyl phthalate system of the raw material of the diallyl phthalate resin is selected from the group consisting of diallyl phthalate monomer, diallyl isophthalate monomer, and para-benzene. A compound of diallyl dicarboxylate monomer. The use of one or more of these compounds to synthesize a diallyl phthalate resin, and the use of the diallyl phthalate-based monomer and other monomers polymerizable with the monomer Synthesis of diallyl dicarboxylate resin For example, the polymerization reaction described in JP-A No. 2-024850, JP-A-H11-147917, and the like can be used.
形成本發明基材之樹脂層5之樹脂組成物所用之苯二甲酸二烯丙酯樹脂較好為為例如諸如DAISO公司製之「DAP-A」(註冊商標)之均聚物的間苯二甲酸二烯丙酯樹脂、如DAISO公司製之「ISODAP」(註冊商標)之間苯二甲酸二烯丙酯樹脂、對苯二甲酸二烯丙酯樹脂，更好為鄰苯二甲酸二烯丙酯樹脂及間苯二甲酸二烯丙酯樹脂。 The diallyl phthalate resin used for forming the resin composition of the resin layer 5 of the substrate of the present invention is preferably, for example, isophthalic acid such as a homopolymer of "DAP-A" (registered trademark) manufactured by DAISO Corporation. A diallyl carboxylic acid resin, such as "DIDAP" (registered trademark) manufactured by DAISO, is a diallyl phthalate resin, a diallyl terephthalate resin, and more preferably a diallyl phthalate. Ester resin and diallyl isophthalate resin.
形成本發明基材之樹脂層5之樹脂組成物中，可較好使用之苯二甲酸二烯丙酯樹脂以GPC(凝膠滲透層析法)測定之重量平均分子量(聚苯乙烯換算)為20,000~60,000，更好為50,000~60,000。係因為若重量平均分子量超過60,000則有硬化性變差之虞，若未達20,000則有耐熱性變差之虞。 In the resin composition of the resin layer 5 forming the substrate of the present invention, the weight average molecular weight (in terms of polystyrene) measured by GPC (gel permeation chromatography) which is preferably used as the diallyl phthalate resin is 20,000 to 60,000, more preferably 50,000 to 60,000. It is because if the weight average molecular weight exceeds 60,000, the hardenability deteriorates, and if it does not reach 20,000, the heat resistance deteriorates.
形成本發明基材之樹脂層5之樹脂組成物中，多官能單體只要是1分子中具有至少2個以上之聚合性不飽和基之化合物，則可使用任一者。具體而言，可列舉為多元醇與α,β-不飽和羧酸縮合所得之化合物(例如乙二醇二(甲基)丙烯酸酯(二丙烯酸酯或二甲基丙烯酸酯之意，以下同)、三乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲 基)丙烯酸酯、二羥甲基丙烷六丙烯酸酯、三羥甲基丙烷二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、1,2-丙二醇二(甲基)丙烯酸酯、二(1,2-丙二醇)二(甲基)丙烯酸酯、三(1,2-丙二醇)二(甲基)丙烯酸酯、四(1,2-丙二醇)二(甲基)丙烯酸酯、(甲基)丙烯酸二甲胺基乙酯、(甲基)丙烯酸二乙胺基乙酯、(甲基)丙烯酸二甲胺基丙酯、(甲基)丙烯酸二乙胺基丙酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯等)、苯乙烯、二乙烯基苯、4-乙烯基甲苯、4-乙烯基吡啶、N-乙烯基吡咯啶酮、(甲基)丙烯酸2-羥基乙酯、1,3-(甲基)丙烯醯氧基-2-羥基丙烷、亞甲基雙丙烯醯胺、N,N-二甲基丙烯醯胺、N-羥甲基丙烯醯胺、新戊二醇二(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、四羥甲基丙烷四(甲基)丙烯酸酯等，更好為二羥甲基丙烷六丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、四羥甲基丙烷四(甲基)丙烯酸酯等3官能以上。形成本發明基材之樹脂層5之樹脂組成物中，該等可使用1種或組合2種以上使用。 In the resin composition of the resin layer 5 of the substrate of the present invention, any of the polyfunctional monomers may be any compound having at least two or more polymerizable unsaturated groups in one molecule. Specifically, a compound obtained by condensing a polyhydric alcohol with an α,β-unsaturated carboxylic acid (for example, ethylene glycol di(meth)acrylate (diacrylate or dimethacrylate, the same applies hereinafter) , triethylene glycol di(meth)acrylate, tetraethylene glycol di(a) Acrylate, dimethylolpropane hexaacrylate, trimethylolpropane di(meth) acrylate, trimethylolpropane tri(meth) acrylate, 1,2-propanediol di(methyl) Acrylate, di(1,2-propanediol) di(meth)acrylate, tris(1,2-propanediol) di(meth)acrylate, tetrakis(1,2-propanediol) di(meth)acrylate , dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminopropyl (meth)acrylate, 1 , 4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, pentaerythritol tri(meth)acrylate, etc.), styrene, divinylbenzene, 4- Vinyl toluene, 4-vinylpyridine, N-vinylpyrrolidone, 2-hydroxyethyl (meth)acrylate, 1,3-(methyl)propenyloxy-2-hydroxypropane, methylene Bisacrylamide, N,N-dimethylpropenamide, N-methylol acrylamide, neopentyl glycol di(meth) acrylate, pentaerythritol di(meth) acrylate, dipentaerythritol hexa Methyl) acrylate, tetramethylolpropane tetra(meth) acrylate And more preferably, it is dimethylolpropane hexaacrylate, trimethylolpropane tri(meth) acrylate, pentaerythritol tri(meth) acrylate, dipentaerythritol hexa(meth) acrylate, tetramethylol A trifunctional or higher functional group such as propane tetra(meth)acrylate. In the resin composition of the resin layer 5 which forms the base material of the present invention, these may be used alone or in combination of two or more.
形成本發明基材之樹脂層5之樹脂組成物中，多官能單體相對於苯二甲酸二烯丙酯樹脂100質量份，較好以1~100質量份之比例調配，更好在3~50質量份之範圍。脫離1~100質量份之範圍時，會有無法獲得本 發明所期待效果之情況而不佳。 In the resin composition of the resin layer 5 forming the substrate of the present invention, the polyfunctional monomer is preferably formulated in an amount of from 1 to 100 parts by mass, more preferably from 3 to 100 parts by mass, based on 100 parts by mass of the diallyl phthalate resin. A range of 50 parts by mass. If you leave the range of 1 to 100 parts by mass, you will not be able to obtain this. The situation of the expected effect of the invention is not good.
形成本發明基材之樹脂層5之樹脂組成物中，光聚合起始劑可使用可藉活性能量線之照射而產生自由基之習知化合物，可列舉為例如苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基-2-苯基苯乙酮、對-二甲胺基苯丙酮、二氯苯乙酮、三氯苯乙酮、對-第三丁基三氯苯乙酮、1-羥基環己基苯基酮、2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉基-丙-1-酮、2-苄基-2-二甲胺基-1-(4-嗎啉基苯基)-丁酮-1、N,N-二甲基胺基苯乙酮等苯乙酮類；二苯甲酮、甲基二苯甲酮、2-氯二苯甲酮、4,4’-二氯二苯甲酮、4,4’-雙二甲胺基二苯甲酮、4,4’-雙二乙胺基二苯甲酮、米氏(Michler's)酮、4-苯甲醯基-4’-甲基二苯基硫醚等二苯甲酮類；二苯基乙二酮(benzil)、苯偶因、苯偶因甲基醚、苯偶因乙基醚、苯偶因異丙基醚、苯偶因異丁基醚等苯偶因醚類；苯乙酮二甲基縮酮、苄基二甲基縮酮等縮酮類；噻噸酮、2-氯噻噸酮、2,4-二甲基噻噸酮、2,4-二乙基噻噸酮、2,4-二異丙基噻噸酮等噻噸酮類；2-甲基蒽醌、2-乙基蒽醌、2-第三丁基蒽醌、1-氯蒽醌、2-胺基蒽醌、2,3-二苯基蒽堃等蒽醌類；苯甲醯基過氧化物、異丙苯過氧化物等有機過氧化物；2,4,5-三芳基咪唑二聚物、核黃素四丁酯(riboflavin tetrabutyrate)、2-巰基苯并咪唑、2-巰基苯并噁唑、2-巰基苯并噻唑等硫醇化合物； 2,4,6-參-s-三嗪、2,2,2-三溴乙醇、三溴甲基苯基碸等有機鹵素化合物；2,4,6-三甲基苯甲醯基二苯基氧化膦等。且，其他例可列舉為吖啶化合物類、肟酯類等。形成本發明基材之樹脂層5之樹脂組成物中，該等可使用1種或組合2種以上使用。 In the resin composition of the resin layer 5 which forms the substrate of the present invention, the photopolymerization initiator may be a conventional compound which can generate a radical by irradiation with an active energy ray, and is exemplified by, for example, acetophenone, 2,2- Dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone , p-t-butyltrichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-propan-1 a ketone, ketoacetone such as 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, N,N-dimethylaminoacetophenone; Benzophenone, methylbenzophenone, 2-chlorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdimethylaminobenzophenone, 4,4 '-Di-diethylaminobenzophenone, Michler's ketone, 4-benzimidyl-4'-methyldiphenyl sulfide, benzophenones; diphenylethylenedione (diphenylethylenedione) Benzil), benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and other benzoin ethers; acetophenone dimethyl condensate a ketal such as a ketone or a benzyldimethylketal; Thiophenones such as thioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone; Anthracene such as 2-methylhydrazine, 2-ethylhydrazine, 2-tert-butylhydrazine, 1-chloroindole, 2-aminoindole, 2,3-diphenylfluorene; Organic peroxides such as benzammonium peroxide and cumene peroxide; 2,4,5-triarylimidazole dimer, riboflavin tetrabutyrate, 2-mercaptobenzimidazole a thiol compound such as 2-mercaptobenzoxazole or 2-mercaptobenzothiazole; Organohalogen compounds such as 2,4,6-para-s-triazine, 2,2,2-tribromoethanol, tribromomethylphenylhydrazine; 2,4,6-trimethylbenzhydryldiphenyl Phosphine oxide and the like. Further, examples of the other examples include acridine compounds and oxime esters. In the resin composition of the resin layer 5 which forms the base material of the present invention, these may be used alone or in combination of two or more.
形成本發明基材之樹脂層5之樹脂組成物中，如上述之光聚合起始劑可使用N,N-二甲基胺基苯甲酸乙酯、N,N-二甲基胺基苯甲酸異戊酯、4-二甲胺基苯甲酸戊酯、三乙胺、三乙醇胺等三級胺類、及β-硫代二醇等硫醚類、(酮)香豆素、噻噸等增感色素類、及花菁、羅丹明、藏紅(Safranin)、孔雀綠(Malachite Green)、甲基藍等烷基硼酸鹽之光增感劑或促進劑之1種或2種以上之組合。 In the resin composition of the resin layer 5 which forms the substrate of the present invention, as the photopolymerization initiator described above, N,N-dimethylaminobenzoic acid ethyl ester and N,N-dimethylaminobenzoic acid can be used. Isoamyl esters, amylamines such as 4-dimethylaminobenzoic acid, tertiary amines such as triethylamine and triethanolamine, and thioethers such as β-thiodiol, (keto) coumarin, and thioxantate A combination of a sensitizing dye and a light sensitizer or an accelerator of an alkyl borate such as cyanine, rhodamine, safranin, malachite green or methyl blue, or a combination of two or more thereof.
光聚合起始劑之較佳組合可列舉為2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉基-丙烷-1-酮(例如日本BASF公司製之IRGACURE-907)、與2-氯噻噸酮(例如日本化藥(股)製之KAYACURE-CTX)或2,4-二乙基噻噸酮(例如，日本化藥(股)製之KAYACURE-DETX)、2-異丙基噻噸酮、4-苯甲醯基-4’-甲基二苯基硫化物等之組合。 A preferred combination of the photopolymerization initiators is 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-propan-1-one (for example, IRGACURE manufactured by BASF Corporation of Japan) -907), with 2-chlorothioxanthone (such as KAYACURE-CTX manufactured by Nippon Kayaku Co., Ltd.) or 2,4-diethylthioxanthone (for example, KAYACURE-DETX manufactured by Nippon Kayaku Co., Ltd.) a combination of 2-isopropylthioxanthone, 4-benzylidene-4'-methyldiphenyl sulfide, and the like.
形成本發明基材之樹脂層5之樹脂組成物中，光聚合起始劑之添加量之較佳範圍相對於苯二甲酸二烯丙酯樹脂100質量份為0.01~30質量份，較好為0.1~20質量份。光聚合起始劑之調配比例未達0.01質量份時光 硬化性變差，另一方面，多於30質量份時硬化塗膜之特性變差，且，保存安定性變差而不佳。 The resin composition of the resin layer 5 of the substrate of the present invention has a preferred range of the amount of the photopolymerization initiator added in an amount of 0.01 to 30 parts by mass based on 100 parts by mass of the diallyl phthalate resin, preferably 0.1 to 20 parts by mass. The proportion of the photopolymerization initiator is less than 0.01 parts by mass. On the other hand, when the amount is more than 30 parts by mass, the properties of the cured coating film are deteriorated, and the storage stability is deteriorated.
形成本發明基材之樹脂層5之樹脂組成物中，除上述(A)~(C)外，只要不損及本發明所期望之效果，亦可添加其他添加劑。添加劑可列舉為例如聚矽氧系、氟系消泡劑、調平劑、習知慣用之熱聚合抑制劑、紫外線吸收劑、矽烷偶合劑、可塑劑、發泡劑、難燃劑、抗靜電劑、抗老化劑、抗菌．防黴劑等。 In addition to the above (A) to (C), the resin composition of the resin layer 5 forming the substrate of the present invention may be added with other additives as long as the desired effects of the present invention are not impaired. The additives may, for example, be polyfluorene-based, fluorine-based antifoaming agents, leveling agents, conventionally used thermal polymerization inhibitors, ultraviolet absorbers, decane coupling agents, plasticizers, foaming agents, flame retardants, antistatic agents. Agent, anti-aging agent, antibacterial. Mold inhibitors, etc.
本發明基材之樹脂層5中可使用習知慣用之無機或有機填料，但尤其以硫酸鋇、球狀二氧化矽較佳，球狀二氧化矽較好為平均一次粒徑係1~100nm者。此處，所謂平均一次粒徑係以雷色散射法測定之值。具體而言，係將奈米二氧化矽分散於溶劑中，捕捉雷射光碰到該分散溶劑所得之散射光，藉由運算所得之平均粒徑。奈米二氧化矽可使用以矽烷偶合劑施以表面處理者、未處理者之任一種。此外，亦可使用於具有2個以上之乙烯性不飽和基之化合物或多官能環氧樹脂中分散有奈米二氧化矽之Hanse-Chemie公司製之NANOCRYL(商品名)XP 0396、XP 0596、XP 0733、XP 0746、XP 0765、XP 0768、XP 0953、XP 0954、XP 1045(均為製品等級名)、或Hanse- Chemie公司製之NANOPOX(商品名)XP 0516、XP 0525、XP 0314(均為製品等級名)。該等填料可單獨調配或調配2種以上。該等填料可抑制塗膜之硬化收縮，且提高密著性、硬度等基本特性。 In the resin layer 5 of the substrate of the present invention, conventionally used inorganic or organic fillers may be used, but in particular, barium sulfate and spherical cerium oxide are preferred, and spherical cerium oxide is preferably an average primary particle size of 1 to 100 nm. By. Here, the average primary particle diameter is a value measured by a lightning scattering method. Specifically, the nano cerium oxide is dispersed in a solvent to capture the scattered light obtained by the laser light hitting the dispersion solvent, and the obtained average particle diameter is calculated. As the nano cerium oxide, any one of a surface treatment agent and an untreated person may be used as the decane coupling agent. Further, it can also be used in a compound having two or more ethylenically unsaturated groups or a polyfunctional epoxy resin, NANOCRYL (trade name) XP 0396, XP 0596 manufactured by Hanse-Chemie Co., Ltd. in which nano antimony is dispersed. XP 0733, XP 0746, XP 0765, XP 0768, XP 0953, XP 0954, XP 1045 (all product grade names), or Hanse- NANOPOX (trade name) XP 0516, XP 0525, XP 0314 (both product grade names) manufactured by Chemie. These fillers may be formulated or formulated in combination of two or more kinds. These fillers can suppress the hardening shrinkage of the coating film and improve basic characteristics such as adhesion and hardness.
本發明基材之樹脂層5中，該等填料之調配量相對於(A)苯二甲酸二烯丙酯樹脂100質量份較好為0.1~300質量份，更好為0.1~150質量份。填料之調配量未達0.1質量份時，硬化塗膜特性降低故不佳。另一方面，超過300質量份時，組成物之黏度變高、印刷性下降、且硬化物變脆而不佳。 In the resin layer 5 of the substrate of the present invention, the amount of the filler is preferably 0.1 to 300 parts by mass, more preferably 0.1 to 150 parts by mass, per 100 parts by mass of the (A) diallyl phthalate resin. When the amount of the filler is less than 0.1 part by mass, the properties of the cured coating film are lowered, which is not preferable. On the other hand, when it exceeds 300 parts by mass, the viscosity of the composition becomes high, the printability is lowered, and the cured product becomes brittle.
形成本發明基材之樹脂層5之樹脂組成物中，視需要為了使樹脂組成物均勻溶解並調整黏度，亦可使用有機溶劑。有機溶劑只要可使各成分均勻溶解，且不與各成分反應者，則無特別限制。 In the resin composition of the resin layer 5 which forms the base material of the present invention, an organic solvent may be used in order to uniformly dissolve the resin composition and adjust the viscosity as needed. The organic solvent is not particularly limited as long as it can uniformly dissolve the components and does not react with the respective components.
該等有機溶劑可列舉為例如甲醇、乙醇等醇類；四氫呋喃等醚類；乙二醇單甲基醚、乙二醇單乙基醚等二醇醚類；甲基溶纖素乙酸酯、乙基溶纖素乙酸酯等乙二醇烷基醚乙酸酯類；二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇二甲基醚等二乙二醇類；丙二醇甲基醚、丙二醇乙基醚、丙二醇丙基醚、丙二醇丁基醚等丙二醇單烷基醚類；丙二醇甲基醚乙酸酯、丙二醇乙基醚乙酸酯、丙二醇丙基醚乙酸酯、丙二醇丁基醚乙酸酯等丙二醇烷基 醚乙酸酯類；丙二醇甲基醚丙酸酯、丙二醇乙基醚丙酸酯、丙二醇丙基醚丙酸酯、丙二醇丁基醚丙酸酯等丙二醇烷基醚乙酸酯類；甲苯、二甲苯等芳香族烴類；甲基乙基酮、4-羥基-4-甲基-2-戊酮等酮類；及乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸丁酯、2-羥基丙酸乙酯、2-羥基-2-甲基丙酸甲酯、2-羥基-2-甲基丙酸乙酯、羥基乙酸甲酯、羥基乙酸乙酯、羥基乙酸丁酯、乳酸甲酯、乳酸乙酯、乳酸丙酯、乳酸丁酯、3-羥基丙酸甲酯、3-羥基丙酸乙酯、3-羥基丙酸丙酯、3-羥基丙酸甲酯、3-丁氧基丙酸乙酯、3-丁氧基丙酸丙酯、3-丁氧基丙酸丁酯等酯類。 Examples of the organic solvent include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; and methyl cellosolve acetate; Ethylene glycol alkyl ether acetate such as ethyl cellosolve acetate; diethylene glycol such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether or diethylene glycol dimethyl ether Propylene glycol monoalkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether; propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether Propylene glycol alkyl ester such as acid ester or propylene glycol butyl ether acetate Ethyl acetate; propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate and other propylene glycol alkyl ether acetate; toluene, xylene, etc. Aromatic hydrocarbons; ketones such as methyl ethyl ketone and 4-hydroxy-4-methyl-2-pentanone; and methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2-hydroxypropionic acid Ethyl ester, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl glycolate, methyl lactate, lactate B Ester, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, methyl 3-hydroxypropionate, 3-butoxypropionic acid Esters such as esters, propyl 3-butoxypropionate, and butyl 3-butoxypropionate.
該等有機溶劑中，就溶解性、與各成份之反應性及塗膜形成容易性而言，可較好地使用二醇醚類、二醇烷基醚乙酸酯類、酯類及二乙二醇類。形成本發明基材之樹脂層5之樹脂組成物中，該等有機溶劑可使用1種亦可混合2種以上使用。 Among these organic solvents, glycol ethers, glycol alkyl ether acetates, esters, and diethylene glycol can be preferably used in terms of solubility, reactivity with each component, and ease of formation of a coating film. Alcohols. In the resin composition of the resin layer 5 which forms the base material of the present invention, these organic solvents may be used alone or in combination of two or more.
製造形成本發明基材之樹脂層5之樹脂組成物只要以上述苯二甲酸二烯丙酯樹脂作為主成分，於其中添加適當必要量之多官能單體及光聚合起始劑後，視需要添加上述添加劑並混合、攪拌即可。 The resin composition for producing the resin layer 5 of the substrate of the present invention is as long as the above-mentioned polydiene phthalate resin is used as a main component, and a suitable amount of the polyfunctional monomer and the photopolymerization initiator are added thereto, as needed. Add the above additives and mix and stir.
於基材1之表層上形成具有交聯結構之樹脂層5之方法可列舉為印刷法等濕式製程。濕式製程可採用浸漬塗佈法、流塗法、輥塗法、棒塗法、網版印刷法、簾塗法、凹 版印刷法、平版印刷法等已知方法。 A method of forming the resin layer 5 having a crosslinked structure on the surface layer of the substrate 1 can be exemplified by a wet process such as a printing method. Wet process can be dip coating, flow coating, roll coating, bar coating, screen printing, curtain coating, concave Known methods such as a printing method and a lithography method.
本發明之基材所用之基材1並無特別限制，可使用例如聚碳酸酯(PC)、聚對苯二甲酸乙二酯(PET)、聚醯亞胺(PI)、聚醚碸(PES)、聚萘二甲酸乙二酯(PEN)等可撓性塑膠膜及於該等膜上貼附氣體阻隔性、硬塗層之複合薄膜作為合成樹脂基材。 The substrate 1 used for the substrate of the present invention is not particularly limited, and for example, polycarbonate (PC), polyethylene terephthalate (PET), polyimine (PI), polyether oxime (PES) can be used. A flexible plastic film such as polyethylene naphthalate (PEN) and a composite film having a gas barrier property and a hard coat layer attached to the film as a synthetic resin substrate.
以活性能量線硬化性樹脂組成物形成本發明基材之樹脂層5時，照射光源可較好地使用低壓水銀燈、中壓水銀燈、高壓水銀燈、超高壓水銀燈、氙燈或金屬鹵素燈等。以活性能量線硬化性樹脂組成物以外之樹脂組成物形成本發明之薄膜基材1之樹脂層5時，除上述以外，亦可利用雷射光、電子束等作為活性能量線。 When the resin layer 5 of the substrate of the present invention is formed by the active energy ray-curable resin composition, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp or a metal halide lamp can be preferably used as the irradiation light source. When the resin layer 5 of the film substrate 1 of the present invention is formed of a resin composition other than the active energy ray-curable resin composition, laser light, an electron beam or the like may be used as the active energy ray.
接著，針對本發明之導電電路基板及其製造方法加以說明。本發明之導電電路基板係於上述本發明之基材上形成電路圖型者。 Next, a conductive circuit substrate and a method of manufacturing the same according to the present invention will be described. The conductive circuit substrate of the present invention is formed on the substrate of the present invention to form a circuit pattern.
本發明之導電電路基板之電路圖型之形成可例如利用塗佈、印刷等濕式製程形成導電性組成物。濕式製程可採用例如噴墨記錄法、網版印刷法、旋塗法、棒塗法、狹縫塗佈法、浸漬塗佈法、噴霧塗佈法、凹版印刷法、柔版印刷法、凹版平版法、凸版平版法、微接觸印刷法、凸版反轉印刷法等已知方法。 The circuit pattern of the conductive circuit substrate of the present invention can be formed by, for example, a wet process such as coating or printing to form a conductive composition. The wet process can employ, for example, an inkjet recording method, a screen printing method, a spin coating method, a bar coating method, a slit coating method, a dip coating method, a spray coating method, a gravure printing method, a flexographic printing method, and a gravure printing method. Known methods such as a lithography method, a relief lithography method, a microcontact printing method, and a letterpress reverse printing method.
形成本發明之導電電路基板之電路圖型時， 於採用印刷法時，作為導電性組成物可為例如於適當之溶劑中含有金、銀、銅、鎳、鋅、鋁、鈣、鎂、鐵、鉑、鈀、錫、鉻、鉛等金屬粒子及銀/鈀等之該等金屬之合金、氧化銀、有機銀、有機金等之在較低溫下熱分化而獲得導電性金屬之熱分解性金屬化合物、氧化鋅(ZnO)、氧化銦錫(ITO)等導電性金屬氧化物粒子作為導電性成分，亦可含聚乙二氧基噻吩/聚苯乙烯磺酸(PEDOT/PSS)、聚苯胺等導電性高分子。且，對於導電性組成物之溶劑種類可無限制地適當選擇適合導電性材料之溶解或分散之溶劑。可使用例如水、烴系、醇系、酮系、醚系、酯系、氟系等各種有機溶劑。 When forming the circuit pattern of the conductive circuit substrate of the present invention, When the printing method is employed, the conductive composition may contain, for example, metal particles such as gold, silver, copper, nickel, zinc, aluminum, calcium, magnesium, iron, platinum, palladium, tin, chromium, lead, etc. in a suitable solvent. And an alloy of such metals such as silver/palladium, a thermal decomposition metal compound such as silver oxide, organic silver or organic gold which is thermally differentiated at a relatively low temperature to obtain a conductive metal, zinc oxide (ZnO), or indium tin oxide ( Conductive metal oxide particles such as ITO) may contain a conductive polymer such as polyethylene oxide thiophene/polystyrene sulfonic acid (PEDOT/PSS) or polyaniline as a conductive component. Further, as the solvent type of the conductive composition, a solvent suitable for dissolving or dispersing the conductive material can be appropriately selected without limitation. For example, various organic solvents such as water, hydrocarbons, alcohols, ketones, ethers, esters, and fluorines can be used.
導電性組成物中除了導電性材料以外，亦可視需要添加樹脂等黏結劑成分、抗氧化劑、皮膜形成促進用之各種觸媒、各種表面張力調整劑、調平劑、脫模促進劑等。該等導電性組成物中，將奈米銀例子分散於溶劑中，且混合低分子聚矽氧等脫模劑、氟系界面活性劑等表面張力調整劑而成之導電性組成物尤其適於凸版反轉印刷法，且顯示優異之圖型形成性及在低溫燒成下顯示高的導電性故而可較佳地使用。 In addition to the conductive material, the conductive composition may be added with a binder component such as a resin, an antioxidant, various catalysts for promoting film formation, various surface tension adjusters, a leveling agent, and a release promoter. In the conductive composition, a conductive composition in which a nano silver is dispersed in a solvent and a surface tension adjusting agent such as a low molecular weight polyfluorene or a fluorine-based surfactant is mixed is particularly suitable. The relief printing method can be preferably used because it exhibits excellent pattern formation properties and exhibits high conductivity at low temperature firing.
本發明之導電電路基板之製造方法中，於本發明之基材上形成之電路圖型之燒成係使用光燒成。光燒成較好使用閃光燈之光照射。閃光燈係藉由將發光氣體(Xe．Kr．Ar．Ne等)封入於石英或玻璃等管內之燈，在發光時間1μs~5000μs之極短時間發光者，而可藉 200nm至1100nm波長之廣帶域之光譜進行照射。封入Xe之氙氣閃光燈由於取得容易故較佳。 In the method for producing a conductive circuit substrate of the present invention, the firing of the circuit pattern formed on the substrate of the present invention is performed by photo-fire. The light is burned to better use the light of the flash. The flash lamp is a light that is enclosed in a tube such as quartz or glass by a luminescent gas (Xe.Kr.Ar.Ne, etc.), and emits light in a very short time of 1 μs to 5000 μs. The spectrum of the broad band of the wavelength of 200 nm to 1100 nm is irradiated. Xenon flash lamps enclosed in Xe are preferred because they are easy to obtain.
以下，使用實施例更詳細說明本發明。但，本發明並不受限於該等實施例。 Hereinafter, the present invention will be described in more detail by way of examples. However, the invention is not limited to the embodiments.
以下述表1所示之調配混合各成分(單位為質量份)，充分攪拌、混合各成分後，使用0.45μm之薄膜過濾器過濾，調製樹脂組成物。以棒塗佈器將所得樹脂組成物塗佈於基材的125μm厚之PET薄膜(東洋紡織公司製：COSMOSHINE A4300)上，在90℃加熱5分鐘，使溶劑揮發。隨後，使用高壓水銀燈以累積光量2,000mJ/cm2之活性能量線使樹脂組成物硬化，於基材上形成樹脂層而製造薄膜基材。硬化後之樹脂層之膜厚為2~3μm。 Each component (unit: mass parts) was mixed and mixed as shown in the following Table 1, and the components were thoroughly stirred and mixed, and then filtered using a 0.45 μm membrane filter to prepare a resin composition. The obtained resin composition was applied onto a 125 μm-thick PET film (COSMOSHINE A4300, manufactured by Toyobo Co., Ltd.) of a substrate by a bar coater, and heated at 90 ° C for 5 minutes to volatilize the solvent. Subsequently, the resin composition was cured by using a high-pressure mercury lamp to accumulate an active energy ray of 2,000 mJ/cm 2 to form a resin layer on the substrate to produce a film substrate. The film thickness of the cured resin layer is 2 to 3 μm.
使用網目數355(T355B：乳劑厚5μm)之網版利用網版印刷將作為導電性組成物之Ag膏(將平均粒徑20nm之銀粒子分散於松油醇(terpineol)中，銀含有率=40質量%之奈米銀膏)塗在以上述順序製作之基材上，形成膜厚1.0μm之電路圖型。以氙氣閃光燈(燈輸出：750V、脈衝長2300μ秒、2600μ秒、大氣下)對該電路圖型進行光燒成，製作導電電路基板。針對所得導電電 路基板，使用MiniOhm Hitester 3540(日置電機公司製)獲得之直線電阻值、使用Loresta GP(三菱化學分析公司製)之薄片電阻值，針對由直線電阻值與線寬、膜厚、配線長所計算之比電阻值進行評價。所得結果一併示於表1。又，圖2顯示實施例1之導電電路基板之電路圖型之一部份的電子顯微鏡照片，圖3顯示實施例2之導電電路基板之電路圖型的一部分之電子顯微鏡照片。依據該等電子顯微鏡照片，評價電極兩側之基材之凹陷。無凹陷且形狀亦良好者評價為○，無凹陷但電極產生龜裂者評價為△，兩側有凹陷者評價為×。 Using a screen of mesh number 355 (T355B: emulsion thickness: 5 μm), an Ag paste as a conductive composition was used by screen printing (silver particles having an average particle diameter of 20 nm were dispersed in terpineol, silver content = 40% by mass of nano silver paste was applied to the substrate prepared in the above procedure to form a circuit pattern having a film thickness of 1.0 μm. The circuit pattern was photo-fired by a xenon flash lamp (lamp output: 750 V, pulse length 2300 μsec, 2600 μsec, atmosphere) to prepare a conductive circuit substrate. For the resulting conductive electricity For the circuit board, the linear resistance value obtained by using MiniOhm Hitester 3540 (manufactured by Hioki Electric Co., Ltd.) and the sheet resistance value of Loresta GP (manufactured by Mitsubishi Chemical Corporation) are calculated for the linear resistance value, line width, film thickness, and wiring length. The specific resistance value was evaluated. The results obtained are shown together in Table 1. 2 shows an electron micrograph of a part of the circuit pattern of the conductive circuit substrate of the first embodiment, and FIG. 3 shows an electron micrograph of a part of the circuit pattern of the conductive circuit substrate of the second embodiment. Based on these electron micrographs, the depression of the substrate on both sides of the electrode was evaluated. Those who did not have a depression and had a good shape were evaluated as ○, and those who had no depression but had cracks in the electrode were evaluated as Δ, and those having depressions on both sides were evaluated as ×.
除基材上未設置樹脂層以外餘以與上述相同之順序製作導電電路基板，且以相同方法針對直線電阻值、薄片電阻值、比電阻值進行評價。所得結果一併記於表1。又，圖4顯示比較例之導電電路基板之電路圖型之一部分之電子顯微鏡照片。 A conductive circuit substrate was produced in the same order as described above except that the resin layer was not provided on the substrate, and the linear resistance value, the sheet resistance value, and the specific resistance value were evaluated in the same manner. The results obtained are shown in Table 1. Further, Fig. 4 shows an electron micrograph of a part of the circuit pattern of the conductive circuit substrate of the comparative example.
由上述表1可知，本發明之光燒成用熱塑性樹脂薄膜基材即使進行光燒成，表面上所形成之電路圖型亦不會產生龜裂或斷線。此外，實施例1中電極兩側之基材未見到凹陷且形狀亦良好，實施例2中電極兩側之基材雖未見到凹陷，但些許電極發生龜裂。可知比較例之電極兩側之基材有凹陷(參考圖2~4)。 As is apparent from the above Table 1, even if the thermoplastic resin film substrate for photo-fired of the present invention is photo-fired, the circuit pattern formed on the surface does not cause cracking or disconnection. Further, in the substrate of the first embodiment, the substrate on both sides of the electrode was not recessed and the shape was good. Although the substrate on both sides of the electrode in Example 2 showed no depression, some of the electrodes were cracked. It can be seen that the substrate on both sides of the electrode of the comparative example has a depression (refer to Figs. 2 to 4).
Claims (4)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-073467 | 2013-03-29 | ||
| JP2013073467 | 2013-03-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201446505A TW201446505A (en) | 2014-12-16 |
| TWI636878B true TWI636878B (en) | 2018-10-01 |
Family
ID=51623824
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW103111737A TWI636878B (en) | 2013-03-29 | 2014-03-28 | Thermoplastic resin film substrate for photo-fired, conductive circuit substrate using the same, and manufacturing method thereof |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6441212B2 (en) |
| KR (1) | KR102292668B1 (en) |
| CN (1) | CN105073416B (en) |
| TW (1) | TWI636878B (en) |
| WO (1) | WO2014156844A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10899940B2 (en) * | 2017-01-25 | 2021-01-26 | Xerox Corporation | Interlayer printing process |
| CN109986599B (en) * | 2017-12-29 | 2020-10-02 | 北京纳米能源与***研究所 | Triboelectric intelligent skin, manipulator and robot |
| KR20220119375A (en) * | 2019-12-24 | 2022-08-29 | 디아이씨 가부시끼가이샤 | Laminates, printed wiring boards, flexible printed wiring boards, electromagnetic shields and molded products |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050165135A1 (en) * | 2004-01-23 | 2005-07-28 | Jacob Mozel | Liquid thermosetting ink |
| JP2012060084A (en) * | 2010-09-13 | 2012-03-22 | Toshiba Tec Corp | Method for forming conductive pattern and printed material |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03281622A (en) * | 1990-03-30 | 1991-12-12 | Hitachi Ltd | Photocurable diallyl phthalate resin composition and printed circuit board prepared by using the same |
| JPH0580521A (en) * | 1991-09-20 | 1993-04-02 | Hitachi Ltd | Photosetting resist composition and production of printed circuit board by using this composition and printed circuit board |
| JP2004223870A (en) | 2003-01-23 | 2004-08-12 | Nippon Zeon Co Ltd | Laminate and its use |
| CA2588343C (en) | 2004-11-24 | 2011-11-08 | Nanotechnologies, Inc. | Electrical, plating and catalytic uses of metal nanomaterial compositions |
| US10231344B2 (en) * | 2007-05-18 | 2019-03-12 | Applied Nanotech Holdings, Inc. | Metallic ink |
| JP2009124029A (en) * | 2007-11-16 | 2009-06-04 | Shinshu Univ | Method of manufacturing electronic circuit board using ink jetting |
| JP2009124032A (en) * | 2007-11-16 | 2009-06-04 | Shinshu Univ | Method of manufacturing printing type electronic circuit board |
| US9730333B2 (en) * | 2008-05-15 | 2017-08-08 | Applied Nanotech Holdings, Inc. | Photo-curing process for metallic inks |
| JP5505778B2 (en) * | 2009-12-24 | 2014-05-28 | 日本ゼオン株式会社 | Film for multilayer printed circuit boards |
| CN102398438A (en) * | 2010-09-15 | 2012-04-04 | 中国科学院化学研究所 | Method for preparing primary circuit by jet-printing metal conductive printing ink by virtue of laser or microwave processing |
| JP2012214870A (en) * | 2011-03-28 | 2012-11-08 | Mitsubishi Paper Mills Ltd | Method for forming metallic coating and metallic ultrafine particle-containing composition |
| JP5880100B2 (en) * | 2012-02-10 | 2016-03-08 | コニカミノルタ株式会社 | Manufacturing method of transparent electrode |
| JP5849834B2 (en) * | 2012-04-09 | 2016-02-03 | コニカミノルタ株式会社 | Transparent electrode, method for producing transparent electrode, and organic electronic device using the transparent electrode |
| KR102122749B1 (en) * | 2012-06-05 | 2020-06-15 | 쇼와 덴코 가부시키가이샤 | Substrate film and sintering method |
| JP5987493B2 (en) | 2012-06-22 | 2016-09-07 | 株式会社リコー | Pattern forming method and pattern and device formed thereby |
| JP5489305B2 (en) * | 2012-06-27 | 2014-05-14 | 石原ケミカル株式会社 | Circuit board and conductive film forming method |
-
2014
- 2014-03-18 KR KR1020157031158A patent/KR102292668B1/en active IP Right Grant
- 2014-03-18 CN CN201480019404.3A patent/CN105073416B/en active Active
- 2014-03-18 JP JP2015508372A patent/JP6441212B2/en active Active
- 2014-03-18 WO PCT/JP2014/057359 patent/WO2014156844A1/en active Application Filing
- 2014-03-28 TW TW103111737A patent/TWI636878B/en active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050165135A1 (en) * | 2004-01-23 | 2005-07-28 | Jacob Mozel | Liquid thermosetting ink |
| JP2012060084A (en) * | 2010-09-13 | 2012-03-22 | Toshiba Tec Corp | Method for forming conductive pattern and printed material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105073416A (en) | 2015-11-18 |
| JP6441212B2 (en) | 2018-12-19 |
| KR20150136530A (en) | 2015-12-07 |
| WO2014156844A1 (en) | 2014-10-02 |
| TW201446505A (en) | 2014-12-16 |
| KR102292668B1 (en) | 2021-08-24 |
| CN105073416B (en) | 2018-01-23 |
| JPWO2014156844A1 (en) | 2017-02-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI603374B (en) | Method for manufacturing conductive pattern, touch sensor, touch panel and display panel | |
| JP6176295B2 (en) | Method for forming conductive pattern | |
| WO2015040908A1 (en) | Photosensitive electroconductive paste, electroconductive thin film, magnetic circuit, and touch panel | |
| TWI636878B (en) | Thermoplastic resin film substrate for photo-fired, conductive circuit substrate using the same, and manufacturing method thereof | |
| JP2015184648A (en) | Photosensitive conductive paste, conductive thin film, electric circuit and touch panel | |
| CN111149056B (en) | Photosensitive conductive paste and conductive pattern forming film | |
| TW200407669A (en) | Photosensitive curable paste composition and sintered article pattern using the same | |
| WO2015152208A1 (en) | Photosensitive conductive paste, conductive thin film, electrical circuit and touch panel | |
| TW201439133A (en) | Composition for forming conductive film and method for producing conductive film with the same | |
| JP5412357B2 (en) | Membrane wiring board | |
| TW201502706A (en) | Curable resin composition, cured product thereof, printed circuit board comprising the same, and method for producing the cured product | |
| JP5916482B2 (en) | Photosensitive conductive paste and conductive circuit | |
| TWI550643B (en) | Conductive paste and conductive circuit | |
| JP2006272713A (en) | Method of manufacturing ceramic substrate | |
| JP2016071173A (en) | Photosensitive conductive paste, conductive thin film, electric circuit and touch panel | |
| JP5927004B2 (en) | Conductive paste and conductive circuit | |
| WO2021065331A1 (en) | Transfer film, laminate production method, laminate, touch panel sensor, and touch panel | |
| WO2014065112A1 (en) | Conductive composition, electrode, plasma display panel and touch panel | |
| WO2018138879A1 (en) | Photosensitive conductive film, conductive pattern formation method, conductive pattern substrate production method, conductive pattern substrate, and touch panel sensor | |
| WO2020044467A1 (en) | Photosensitive conductive film, layered body and method for manufacturing same, and touch panel sensor | |
| JP2016071172A (en) | Photosensitive conductive paste, conductive thin film, electric circuit and touch panel | |
| JP2009289712A (en) | Paste for electron emitting source | |
| JP2015219308A (en) | Photosensitive conductive film, photosensitive conductive laminate, method for forming conductive film, and conductive laminate | |
| JP2016191802A (en) | Photosensitive conductive paste, conductive thin film, and electric circuit | |
| WO2015062068A1 (en) | Patterning method and application for forming conductive functional pattern |