TW202022017A - Resin composition, prepreg using same, film with resin, metal foil with resin, metal-clad laminated board, and wiring board - Google Patents
Resin composition, prepreg using same, film with resin, metal foil with resin, metal-clad laminated board, and wiring board Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
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- 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
Abstract
Description
本發明涉及一種樹脂組成物、以及使用其之預浸體、附樹脂之薄膜、附樹脂之金屬箔、覆金屬積層板及配線基板。The present invention relates to a resin composition, and a prepreg, a resin-coated film, a resin-coated metal foil, a metal-clad laminate and a wiring board using the resin composition.
發明背景 近年來，各種電子機器伴隨著資訊處理量大增，可裝設之半導體裝置的高積體化、配線高密度化及多層化等的安裝技術正急速發展。對於用以構成可在各種電子機器中使用之印刷配線板基材的基板材料，要求介電係數及介電正切要低，以提高訊號傳輸速度、降低訊號傳輸時之損失。Background of the invention In recent years, as the amount of information processing of various electronic devices has increased greatly, mounting technologies such as higher integration of mountable semiconductor devices, higher wiring density, and multilayering have been rapidly developed. For substrate materials used to form printed wiring board substrates that can be used in various electronic devices, the dielectric constant and dielectric tangent are required to be low to increase the signal transmission speed and reduce the loss during signal transmission.
針對所述要求，有使用一種含有經末端改質之聚苯醚(PPE)化合物的樹脂組成物作為電特性優異之材料(譬如，專利文獻1及2)。報告還指出以含有PPE化合物之樹脂組成物構成的配線板等具有優異的傳輸特性。In response to these requirements, a resin composition containing a terminal-modified polyphenylene ether (PPE) compound is used as a material with excellent electrical characteristics (for example,
另一方面，作為基板材料等成形材料利用時，不僅要求低介電特性優異，還要求其硬化物具有高玻璃轉移溫度(Tg)或具有耐熱性及密著性。On the other hand, when it is used as a molding material such as a substrate material, it is required not only to be excellent in low dielectric properties, but also to have a high glass transition temperature (Tg) or heat resistance and adhesion of the cured product.
然而，關於上述專利文獻1記載之樹脂組成物，以為可獲得低介電特性，但經由本發明人等研究得出受到進行末端改質(二乙烯基苄基化改質)時使用之氯離子殘渣的影響，使用前述樹脂組成物來製作印刷配線板時，有無法確保充分的絕緣可靠性之情況。尤其，在設有導體電路間之距離小的導體電路圖案的配線板中，該影響相當明顯。However, with regard to the resin composition described in
另一方面，只有上述專利文獻2中所使用之改質PPE時，反應性差，因此有Tg降低的問題。為了解決該問題，需要反應引發劑，但有電特性(低介電特性及傳輸特性)受該引發劑影響而變差的缺點。On the other hand, only the modified PPE used in the above-mentioned
本發明係有鑑於所述情事所為者，其目的在於提供一種兼具樹脂組成物之硬化物的低介電特性(低介電常數及介電正切)、高Tg及絕緣可靠性的樹脂組成物。又，本發明目的在於提供一種使用有前述樹脂組成物的預浸體、附樹脂之薄膜、附樹脂之金屬箔、覆金屬積層板及配線基板。The present invention is made in view of the above circumstances, and its object is to provide a resin composition that has both low dielectric properties (low dielectric constant and dielectric tangent), high Tg, and insulation reliability of a cured resin composition . Furthermore, an object of the present invention is to provide a prepreg using the aforementioned resin composition, a film with resin, a metal foil with resin, a metal-clad laminate, and a wiring board.
先前技術文獻 專利文獻 專利文獻1：日本專利特開2011-68713號公報 專利文獻2：日本專利特開2004-511580號公報Prior technical literature Patent Literature Patent Document 1: Japanese Patent Laid-Open No. 2011-68713 Patent Document 2: Japanese Patent Laid-Open No. 2004-511580
發明概要 本發明一態樣之樹脂組成物的特徵在於含有：聚苯醚化合物，其於分子末端具有下述式(1)所示之基；及下述交聯劑中之至少任一者：於分子中具有碳-碳不飽和雙鍵之交聯劑或可與前述聚苯醚化合物反應使其硬化之交聯劑；並且，前述聚苯醚化合物中之氯化物離子量在250ppm以下。Summary of the invention The resin composition of one aspect of the present invention is characterized by containing: a polyphenylene ether compound having a group represented by the following formula (1) at the molecular end; and at least any one of the following crosslinking agents: A crosslinking agent having a carbon-carbon unsaturated double bond or a crosslinking agent that can react with the aforementioned polyphenylene ether compound to harden; and the amount of chloride ion in the aforementioned polyphenylene ether compound is 250 ppm or less.
[化學式1]
[式(1)中，R1 表示氫原子或碳數1~10之烷基，R2 表示碳數1~10之伸烷基]。[In formula (1), R 1 represents a hydrogen atom or an alkyl group having 1 to 10 carbons, and R 2 represents an alkylene group having 1 to 10 carbons].
發明效果 根據本發明，可提供一種兼具樹脂組成物之硬化物的低介電特性、高Tg及優異絕緣可靠性的樹脂組成物。並且根據本發明，藉由使用前述樹脂組成物，可提供具有優異性能的預浸體、附樹脂之薄膜、附樹脂之金屬箔、覆金屬積層板及配線基板。Effect of invention According to the present invention, it is possible to provide a resin composition having the low dielectric properties, high Tg, and excellent insulation reliability of a cured resin composition. Furthermore, according to the present invention, by using the aforementioned resin composition, it is possible to provide prepregs, resin-coated films, resin-coated metal foils, metal-clad laminates, and wiring boards with excellent performance.
用以實施發明之形態 本發明實施形態之樹脂組成物的特徵在於含有：聚苯醚化合物，其於分子末端具有下述式(1)所示之基；及下述交聯劑中之至少任一者：於分子中具有碳-碳不飽和雙鍵之交聯劑或可與前述聚苯醚化合物反應使其硬化之交聯劑；並且，前述聚苯醚化合物中之氯化物離子量在250ppm以下。Forms for carrying out the invention The resin composition of the embodiment of the present invention is characterized by containing: a polyphenylene ether compound having a group represented by the following formula (1) at the end of the molecule; and at least any one of the following crosslinking agents: in the molecule A crosslinking agent having carbon-carbon unsaturated double bonds or a crosslinking agent that can react with the aforementioned polyphenylene ether compound to harden; and the amount of chloride ion in the aforementioned polyphenylene ether compound is less than 250 ppm.
[化學式2]
[式(1)中，R1 表示氫原子或碳數1~10之烷基，R2 表示碳數1~10之伸烷基]。 以下具體說明本實施形態之樹脂組成物的各成分。[In formula (1), R 1 represents a hydrogen atom or an alkyl group having 1 to 10 carbons, and R 2 represents an alkylene group having 1 to 10 carbons]. Hereinafter, each component of the resin composition of this embodiment will be specifically described.
(聚苯醚化合物) 本實施形態中使用之聚苯醚化合物只要是於分子末端具有上述式(1)所示之基且氯化物(Cl- )離子量在250ppm以下的聚苯醚化合物，即無特別限定。藉由使用所述聚苯醚化合物，可抑制離子遷移的發生，而可獲得優異的絕緣可靠性。又，本實施形態之聚苯醚化合物無需使用反應引發劑即可與後述之交聯劑產生反應，因此不受反應引發劑影響。所以，吾等認為本實施形態之樹脂組成物可維持優異的絕緣可靠性及低介電常數與介電正切，同時可獲得更高的玻璃轉移溫度(Tg)及密著性。Use of (polyphenylene ether compound) of the present embodiment, as long as the polyphenylene ether compound having a group of the above formula (1) and chloride (Cl -) ions at the molecular terminal in the amount of polyphenylene ether compound of 250ppm or less, i.e., There is no particular limitation. By using the polyphenylene ether compound, the occurrence of ion migration can be suppressed, and excellent insulation reliability can be obtained. Moreover, the polyphenylene ether compound of this embodiment can react with the crosslinking agent mentioned later without using a reaction initiator, and is therefore not affected by the reaction initiator. Therefore, we believe that the resin composition of this embodiment can maintain excellent insulation reliability and low dielectric constant and dielectric tangent, while achieving higher glass transition temperature (Tg) and adhesion.
就材料特性而言，硬化物之Tg高的材料會是耐熱性(焊接耐熱性等)更為提升的主因之一。而且，在硬化物中，Tg高的材料還具有材料在較高溫區域中之熱膨脹係數的值較小的優點。因為一般而言，在高於玻璃轉移溫度之溫度下，熱膨脹會急遽變大。亦即，玻璃轉移溫度若低，熱膨脹係數在高於其玻璃轉移溫度之高溫區域中會變大。玻璃轉移溫度若低，在較高溫區域中熱膨脹會變大，致使配線基板中之譬如層間連接可靠性(發生貫通孔(through hole)之孔壁斷裂(barrel crack)等)變差，而恐無法作為印刷板發揮作用。吾等認為此乃因為在基板內之由樹脂組成物之硬化物所構成的絕緣層與由金屬構成之貫通孔的材質間，高溫下之熱膨脹係數之差變大，而於由金屬構成之貫通孔的壁面產生裂痕，使連接可靠性變差所致。In terms of material properties, materials with a high Tg of the hardened material will be one of the main reasons for higher heat resistance (welding heat resistance, etc.). Moreover, in the hardened product, the material with high Tg also has the advantage that the thermal expansion coefficient of the material in the higher temperature region is smaller. Generally speaking, at a temperature higher than the glass transition temperature, the thermal expansion will suddenly increase. That is, if the glass transition temperature is low, the thermal expansion coefficient becomes larger in the high temperature region higher than the glass transition temperature. If the glass transition temperature is low, the thermal expansion will increase in the higher temperature area, resulting in the deterioration of interlayer connection reliability (barrel cracks where through holes occur) in the wiring substrate, which may not Functions as a printing plate. We believe that this is because the difference in thermal expansion coefficient at high temperature between the insulating layer made of the hardened resin composition and the material of the through hole made of metal in the substrate becomes larger, and the difference in the thermal expansion coefficient of the through hole made of metal becomes larger. Cracks on the wall of the hole make the connection reliability worse.
聚苯醚化合物中之Cl- 離子(以下亦僅稱Cl離子)量只要在250ppm以下即無特別限定，惟在200ppm以下較佳。前述Cl離子量愈少愈佳，但在以上述式(1)所示之基使聚苯醚化合物之分子末端改質時會無法避免地混入某程度的Cl離子，因此要降低前述Cl離子量有耗費成本之虞。所以，從成本面來看，聚苯醚化合物中之Cl離子量宜在5ppm以上。較宜在10ppm以上，且以在15ppm以上較佳，更宜在30ppm以上。The amount of Cl - ion (hereinafter also referred to as Cl ion) in the polyphenylene ether compound is not particularly limited as long as it is 250 ppm or less, but it is preferably 200 ppm or less. The smaller the amount of Cl ions, the better, but when the molecular end of the polyphenylene ether compound is modified with the group represented by the above formula (1), a certain degree of Cl ions will inevitably be mixed in, so the amount of Cl ions must be reduced There is a risk of cost. Therefore, from the perspective of cost, the amount of Cl ion in the polyphenylene ether compound should be above 5 ppm. It is more preferably 10 ppm or more, more preferably 15 ppm or more, and more preferably 30 ppm or more.
另，聚苯醚化合物中之Cl離子量可以後述之實施例中記載的方法等進行測定。In addition, the amount of Cl ion in the polyphenylene ether compound can be measured by the method described in the below-mentioned Examples.
並且，於本實施形態之聚苯醚化合物中，除上述Cl離子以外，有時還會含有溴化物離子(Br- )、硝酸根離子(NO3 - )、硫酸根離子(SO4 - )、亞硝酸根離子(NO2 - )、磷酸根離子(PO4 3- )、鈉離子(Na+ )、銨離子(NH4 + )等離子性不純物。該等不純物並無特別限定，但濃度宜盡可能低，且含有該等離子性不純物時，溴化物離子(Br- )、硝酸根離子(NO3 - )、硫酸根離子(SO4 - )、亞硝酸根離子(NO2 - )、磷酸根離子(PO4 3- )、鈉離子(Na+ )、銨離子(NH4 + )宜各別在50ppm以下。Further, in the polyphenylene ether compound in the present aspect of the embodiment, in addition to the above Cl ions, sometimes containing a bromide ion (Br -), nitrate ion (NO 3 -), sulfate ion (SO 4 -), nitrite ion (NO 2 -), phosphate ion (PO 4 3-), sodium ion (Na +), ions of ammonium ion (NH 4 +) and other impurities. When such impurities is not particularly limited, but the concentration should be as low as possible, and containing such ionic impurities, bromide ion (Br -), nitrate ion (NO 3 -), sulfate ion (SO 4 -), ethylene nitrate ion (2 NO -), phosphate ion (PO 4 3-), sodium ion (Na +), ammonium ion (NH 4 +) in respective appropriate 50ppm or less.
前述式(1)中，R1 表示氫原子或碳數1~10之烷基。碳數1~10之烷基只要是碳數1~10之烷基即無特別限定，可為直鏈狀，亦可為支鏈狀。具體上，可舉甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基、戊基、異戊基、新戊基及己基等。該等中又以氫原子為宜。In the aforementioned formula (1), R 1 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms is not particularly limited as long as it is an alkyl group having 1 to 10 carbon atoms, and it may be linear or branched. Specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, etc. . Among these, hydrogen atoms are suitable.
又，前述式(1)中，R2 表示碳數1~10之伸烷基。碳數1~10之伸烷基只要是碳數1~10之伸烷基即無特別限定，可舉：亞甲基、伸乙基、伸丙基、伸丁基、伸戊基、伸己基、伸庚基、伸辛基、伸壬基及伸癸基等。其中又亞甲基為宜。In addition, in the aforementioned formula (1), R 2 represents an alkylene group having 1 to 10 carbon atoms. The alkylene having 1 to 10 carbon atoms is not particularly limited as long as it is an alkylene having 1 to 10 carbon atoms. Examples include: methylene, ethylene, propylene, butylene, pentylene, and hexylene , Heptyl, octyl, nonyl and decyl, etc. Among them, methylene is suitable.
前述式(1)所示之基並無特別限定，宜具有選自對乙烯基苄基、間乙烯基苄基、鄰乙烯基苄基中之至少1種乙烯基苄基(ethenyl benzyl/vinyl benzyl)。更宜具有選自對乙烯基苄基、間乙烯基苄基、鄰乙烯基苄基中之至少2種以上。The group represented by the aforementioned formula (1) is not particularly limited, and preferably has at least one vinyl benzyl group selected from the group consisting of p-vinyl benzyl, m-vinyl benzyl, and o-vinyl benzyl (ethenyl benzyl/vinyl benzyl). ). It is more preferable to have at least two selected from p-vinylbenzyl, m-vinylbenzyl, and o-vinylbenzyl.
尤其，本實施形態之樹脂組成物從更確實獲得上述效果之觀點來看，聚苯醚化合物宜包含有具有下述式(2)所示結構的聚苯醚化合物。In particular, the resin composition of the present embodiment preferably contains a polyphenylene ether compound having a structure represented by the following formula (2) from the viewpoint of obtaining the above-mentioned effects more reliably.
[化學式3]
在上述式(2)中，R3 ~R10 分別獨立。即，R3 ~R10 可分別為相同基，亦可為互異之基。又，R3 ~R10 表示氫原子、烷基、烯基、炔基、甲醯基、烷基羰基、烯基羰基或炔基羰基。其中又以氫原子及烷基為宜。In the above formula (2), R 3 to R 10 are independent of each other. That is, R 3 to R 10 may each be the same group or may be mutually different groups. In addition, R 3 to R 10 represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a methanoyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group. Among them, a hydrogen atom and an alkyl group are suitable.
關於R3 ~R10 ，就上述所列舉之各官能基，具體上可舉以下之物。Regarding R 3 to R 10 , specific examples of the functional groups listed above include the following.
烷基並無特別限定，譬如宜為碳數1~18之烷基，且碳數1~10之烷基較佳。具體上可舉如甲基、乙基、丙基、己基及癸基等。The alkyl group is not particularly limited. For example, an alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable. Specific examples include methyl, ethyl, propyl, hexyl and decyl.
又，烯基並無特別限定，譬如宜為碳數2~18之烯基，且碳數2~10之烯基較佳。具體上可舉如乙烯基、烯丙基及3-丁烯基等。In addition, the alkenyl group is not particularly limited. For example, it is preferably an alkenyl group having 2 to 18 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms is preferred. Specific examples include vinyl, allyl and 3-butenyl.
又，炔基並無特別限定，譬如宜為碳數2~18之炔基，且碳數2~10之炔基較佳。具體上可舉如乙炔基及丙-2-炔-1-基(prop-2-yn-1-yl；炔丙基)等。In addition, the alkynyl group is not particularly limited. For example, an alkynyl group having 2 to 18 carbon atoms is preferable, and an alkynyl group having 2 to 10 carbon atoms is preferable. Specific examples include ethynyl and prop-2-yn-1-yl (prop-2-yn-1-yl; propargyl).
又，烷基羰基只要是業經烷基取代之羰基即無特別限定，譬如宜為碳數2~18之烷基羰基，且碳數2~10之烷基羰基較佳。具體上可舉如乙醯基、丙醯基、丁醯基、異丁醯基、三甲基乙醯基、己醯基、辛醯基及環己基羰基等。In addition, the alkylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkyl group. For example, it is preferably an alkylcarbonyl group having 2 to 18 carbon atoms, and an alkylcarbonyl group having 2 to 10 carbon atoms is preferred. Specific examples include acetyl, propyl, butyryl, isobutyryl, trimethyl acetyl, hexyl, octyl, cyclohexylcarbonyl, and the like.
另，烯基羰基只要是業經烯基取代之羰基即無特別限定，譬如宜為碳數3~18之烯基羰基，且碳數3~10之烯基羰基較佳。具體上可舉如丙烯醯基、甲基丙烯醯基及巴豆醯基等。In addition, the alkenylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkenyl group. For example, an alkenylcarbonyl group having 3 to 18 carbon atoms is preferable, and an alkenylcarbonyl group having 3 to 10 carbon atoms is preferable. Specifically, acryloyl, methacryloyl, crotonyl and the like can be mentioned.
又，炔基羰基只要是業經炔基取代之羰基即無特別限定，譬如宜為碳數3~18之炔基羰基，且碳數3~10之炔基羰基較佳。具體上可舉如炔丙醯基等。In addition, the alkynylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkynyl group. For example, an alkynylcarbonyl group having 3 to 18 carbon atoms is preferred, and an alkynylcarbonyl group having 3 to 10 carbon atoms is preferred. Specific examples include propargyl groups.
另，在上述式(2)中，A為下述式(3)所示結構，B為下述式(4)所示結構：In addition, in the above formula (2), A is the structure represented by the following formula (3), and B is the structure represented by the following formula (4):
[化學式4]
[化學式5]
式(3)及(4)中，重複單元之m及n分別表示0~20之整數。In formulas (3) and (4), m and n of the repeating unit each represent an integer of 0-20.
R11 ~R18 分別獨立。即，R11 ~R18 可分別為相同基，亦可為互異之基。又，在本實施形態中，R11 ~R18 為氫原子或烷基。R 11 ~R 18 are independent. That is, R 11 to R 18 may each be the same group or may be mutually different groups. In addition, in this embodiment, R 11 to R 18 are hydrogen atoms or alkyl groups.
並且，上述式(2)中，Y可舉碳數20以下之直鏈狀、支鏈狀或環狀的烴。較具體而言，為下述式(5)所示結構：In addition, in the above formula (2), Y may be a linear, branched, or cyclic hydrocarbon having a carbon number of 20 or less. More specifically, it is the structure represented by the following formula (5):
[化學式6]
式(5)中，R19 及R20 分別獨立表示氫原子或烷基。前述烷基可舉如甲基等。又，式(5)所示之基可舉如亞甲基、甲基亞甲基及二甲基亞甲基等。In formula (5), R 19 and R 20 each independently represent a hydrogen atom or an alkyl group. Examples of the aforementioned alkyl group include methyl group and the like. In addition, the group represented by formula (5) includes methylene, methylmethylene, dimethylmethylene and the like.
在本實施形態中，聚苯醚化合物之重量平均分子量(Mw)無特別限定，譬如宜為1000~5000，1000~4000較佳。另，在此，重量平均分子量只要以一般分子量測定方法測得即可，具體上可舉使用凝膠滲透層析術(GPC)測得之值等。又，聚苯醚化合物於分子中具有重複單元(m、n)時，該等重複單元宜為聚苯醚化合物之重量平均分子量可成為所述範圍內之數值。In this embodiment, the weight average molecular weight (Mw) of the polyphenylene ether compound is not particularly limited. For example, it is preferably 1000 to 5000, preferably 1000 to 4000. In addition, here, the weight average molecular weight may be measured by a general molecular weight measurement method. Specifically, a value measured by gel permeation chromatography (GPC) can be mentioned. In addition, when the polyphenylene ether compound has repeating units (m, n) in the molecule, these repeating units are preferably the weight average molecular weight of the polyphenylene ether compound, which can be a value within the aforementioned range.
聚苯醚化合物之重量平均分子量若在該範圍內，即具有聚苯醚骨架所具備之優異的低介電特性，且硬化物之耐熱性更優異，不僅如此，成形性也相當良好。吾等以為其理由如下。與一般的聚苯醚相較下，重量平均分子量若在如上述之範圍內，即為分子量較低之物，故而有硬化物之耐熱性降低的傾向。關於這點，吾等認為本實施形態之聚苯醚化合物於末端具有上述式(1)所示之結構，所以具有高反應性，可製得硬化物之耐熱性充分高者。又，聚苯醚化合物之重量平均分子量若在所述範圍內，與苯乙烯或二乙烯基苯相較下為高分子量，但比起一般的聚苯醚，分子量則較低，因此成形性亦佳。因此，吾等認為藉由使用所述聚苯醚化合物，可製得不僅硬化物之耐熱性更優異且成形性亦佳者。If the weight average molecular weight of the polyphenylene ether compound is within this range, it has the excellent low-dielectric properties of the polyphenylene ether skeleton, and the heat resistance of the cured product is more excellent. Not only that, but also the moldability is quite good. Our reasons are as follows. Compared with general polyphenylene ether, if the weight average molecular weight is within the above-mentioned range, the molecular weight is lower, so the heat resistance of the hardened product tends to decrease. In this regard, we believe that the polyphenylene ether compound of the present embodiment has the structure represented by the above formula (1) at the end, so it has high reactivity and can produce a cured product with sufficiently high heat resistance. In addition, if the weight average molecular weight of the polyphenylene ether compound is within the above range, it is a high molecular weight compared with styrene or divinylbenzene, but compared with general polyphenylene ether, the molecular weight is lower, so the moldability is also good. good. Therefore, we believe that by using the polyphenylene ether compound, it is possible to obtain not only the heat resistance of the cured product, but also the moldability.
另，在本實施形態中使用之聚苯醚化合物中，改質聚苯醚於每1分子之分子末端具有的前述X取代基之平均個數(末端官能基數)並無特別限定。具體上，宜為1~5個，1~3個較佳。該末端官能基數若太少，有不易製得就硬化物之耐熱性而言夠充分之物的傾向。又，末端官能基數若太多，反應性會變得太高，有可能會發生譬如樹脂組成物之保存性降低、或樹脂組成物之流動性降低等不良情況。即，如果使用所述改質聚苯醚，有可能因流動性不足等，而發生譬如於多層成形時產生孔隙等的成形不良，從而發生不易製得可靠性高的印刷配線板等成形性之問題。In addition, in the polyphenylene ether compound used in this embodiment, the average number of the aforementioned X substituents (the number of terminal functional groups) that the modified polyphenylene ether has per molecule terminal of 1 molecule is not particularly limited. Specifically, it is preferably 1 to 5, preferably 1 to 3. If the number of the terminal functional groups is too small, it tends to be difficult to obtain a substance sufficient for the heat resistance of the cured product. In addition, if the number of terminal functional groups is too large, the reactivity will become too high, which may cause problems such as a decrease in the storage properties of the resin composition or a decrease in the fluidity of the resin composition. That is, if the modified polyphenylene ether is used, it is possible that due to insufficient fluidity, etc., molding defects such as voids generated during multilayer molding may occur, and it may be difficult to produce highly reliable printed wiring boards and other moldability. problem.
另，聚苯醚化合物之末端官能基數，可舉表示聚苯醚化合物1莫耳中存在之所有聚苯醚化合物每1分子的前述取代基之平均值的數值等。該末端官能基數譬如可藉由測定所得聚苯醚化合物中剩餘之羥基數，再從改質前的聚苯醚之羥基數算出減少量而測得。從該改質前的聚苯醚之羥基數減少的減少量，即為末端官能基數。而且，聚苯醚化合物中剩餘之羥基數的測定方法，可藉由於聚苯醚化合物之溶液中添加能與羥基聚集之四級銨鹽(氫氧化四乙銨)，並測定該混合溶液之UV吸光度而求得。In addition, the number of terminal functional groups of the polyphenylene ether compound may be a numerical value representing the average value of the aforementioned substituents per molecule of all the polyphenylene ether compounds present in 1 mole of the polyphenylene ether compound. The number of terminal functional groups can be measured, for example, by measuring the number of hydroxyl groups remaining in the obtained polyphenylene ether compound, and then calculating the reduction from the number of hydroxyl groups of the polyphenylene ether before modification. The reduction in the number of hydroxyl groups of the polyphenylene ether before the modification is the number of terminal functional groups. Moreover, the method for measuring the number of remaining hydroxyl groups in the polyphenylene ether compound can be achieved by adding a quaternary ammonium salt (tetraethylammonium hydroxide) that can aggregate with hydroxyl groups in the solution of the polyphenylene ether compound, and measuring the UV of the mixed solution. Obtained by absorbance.
另，本實施形態中使用之聚苯醚化合物的固有黏度並無特別限定。具體而言為0.03~0.12dl/g即可，不過宜為0.04~0.11dl/g，且0.06~0.095dl/g較佳。該固有黏度若太低，有分子量低之傾向，從而有不易獲得低介電常數或低介電正切等低介電性的傾向。又，固有黏度若太高，有黏度高、無法獲得充分的流動性，而硬化物之成形性降低的傾向。因此，聚苯醚化合物之固有黏度若在上述範圍內，即可實現優異的硬化物之耐熱性及成形性。In addition, the inherent viscosity of the polyphenylene ether compound used in this embodiment is not particularly limited. Specifically, it is sufficient to be 0.03 to 0.12 dl/g, but it is preferably 0.04 to 0.11 dl/g, and 0.06 to 0.095 dl/g is more preferable. If the inherent viscosity is too low, the molecular weight tends to be low, so that it is difficult to obtain low dielectric properties such as low dielectric constant or low dielectric tangent. In addition, if the inherent viscosity is too high, the viscosity will be high, sufficient fluidity will not be obtained, and the moldability of the hardened product will tend to decrease. Therefore, if the inherent viscosity of the polyphenylene ether compound is within the above range, excellent heat resistance and moldability of the cured product can be achieved.
另，此處的固有黏度係在25℃之二氯甲烷中測得的固有黏度，更具體而言，譬如係以黏度計測定0.18g/45ml之二氯甲烷溶液(液溫25℃)所得之值等。該黏度計可舉如Schott公司製AVS500 Visco System等。In addition, the intrinsic viscosity here is the intrinsic viscosity measured in dichloromethane at 25°C, more specifically, it is obtained by measuring 0.18g/45ml of methylene chloride solution (liquid temperature 25°C) with a viscometer. Value etc. Examples of the viscometer include the AVS500 Visco System manufactured by Schott Corporation.
另，本實施形態之樹脂組成物亦可含有如上述之聚苯醚化合物以外的熱硬化性樹脂。譬如，可舉可使用之環氧樹脂、酚樹脂、胺樹脂、不飽和聚酯樹脂、熱硬化性聚醯亞胺樹脂、馬來亞醯胺化合物等之其他熱硬化性樹脂。前述馬來亞醯胺化合物可為改質馬來亞醯胺化合物，具體上可舉如分子中之至少一部分業經聚矽氧化合物改質之馬來亞醯胺化合物及業經胺化合物改質之馬來亞醯胺化合物等。In addition, the resin composition of this embodiment may contain thermosetting resins other than the above-mentioned polyphenylene ether compound. For example, usable epoxy resin, phenol resin, amine resin, unsaturated polyester resin, thermosetting polyimide resin, maleimide compound and other thermosetting resins can be mentioned. The aforementioned maleimide compound may be a modified maleimide compound, specifically, for example, a maleimide compound in which at least a part of the molecule has been modified by a polysiloxane compound and a horse modified by an amine compound. Leimide compounds and so on.
另，本實施形態中適宜使用之聚苯醚化合物的合成方法，只要是可合成業經如上述之取代基X行末端改質且所得化合物之氯化物離子量在250ppm以下的改質聚苯醚化合物的方法，即無特別限定。具體而言，可舉如使鍵結有取代基X與鹵素原子之化合物對聚苯醚起反應的方法等。In addition, the method for synthesizing the polyphenylene ether compound suitable for use in this embodiment can synthesize a modified polyphenylene ether compound that has been modified by the above-mentioned substituent X line and whose chloride ion content is 250 ppm or less. The method is not particularly limited. Specifically, for example, a method of reacting polyphenylene ether with a compound to which the substituent X and a halogen atom are bonded is used.
關於前述式(1)所示之取代基X，具有碳-碳不飽和雙鍵之基的位置可任為p(對)、m(間)、o(鄰)。較具體而言，前述合成方法中使用之鍵結有取代基X與鹵素原子的化合物譬如可為對氯甲基苯乙烯、間氯甲基苯乙烯、鄰氯甲基苯乙烯等，可單獨使用該等化合物中之一者，亦可併用2種~3種來使用。從對氯甲基苯乙烯、間氯甲基苯乙烯、鄰氯甲基苯乙烯中併用2種以上使用時，其使用比例(質量比)並無特別限定，若列舉使用例，併用對氯甲基苯乙烯及間氯甲基苯乙烯時，其使用比例(質量比，以下皆同)宜為對氯甲基苯乙烯：間氯甲基苯乙烯=5~95：95~5左右。另，併用對氯甲基苯乙烯及鄰氯甲基苯乙烯時，其使用比例宜為對氯甲基苯乙烯：鄰氯甲基苯乙烯=5~95：95~5左右；使用間氯甲基苯乙烯與鄰氯甲基苯乙烯時，其使用比例宜為間氯甲基苯乙烯：鄰氯甲基苯乙烯=5~95：95~5左右。並且，併用3者時，其使用比例宜為對氯甲基苯乙烯：間氯甲基苯乙烯：鄰氯甲基苯乙烯=20~90：40~5：40~5左右。Regarding the substituent X represented by the aforementioned formula (1), the position of the group having a carbon-carbon unsaturated double bond can be any of p (pair), m (m), or o (ortho). More specifically, the compound bonded with the substituent X and the halogen atom used in the aforementioned synthesis method can be, for example, p-chloromethylstyrene, m-chloromethylstyrene, o-chloromethylstyrene, etc., and can be used alone One of these compounds can also be used in combination of two to three types. When two or more of p-chloromethyl styrene, m-chloromethyl styrene, and o-chloromethyl styrene are used in combination, the use ratio (mass ratio) is not particularly limited. If the use examples are listed, p-chloromethyl is used in combination In the case of methyl styrene and m-chloromethyl styrene, the use ratio (mass ratio, the following are the same) is preferably p-chloromethyl styrene: m-chloromethyl styrene=5~95: about 95~5. In addition, when p-chloromethyl styrene and o-chloromethyl styrene are used in combination, the use ratio should be p-chloromethyl styrene: o-chloromethyl styrene=5~95: 95~5; use m-chloromethyl When methyl styrene and o-chloromethyl styrene, the use ratio should be m-chloromethyl styrene: o-chloromethyl styrene=5~95:95~5. In addition, when the three are used in combination, the ratio of use should be p-chloromethylstyrene: m-chloromethylstyrene: o-chloromethylstyrene=20~90:40~5:40~5.
又，在併用對氯甲基苯乙烯、間氯甲基苯乙烯、鄰氯甲基苯乙烯中之2種以上來使用時，至少其中一者宜使用對氯甲基苯乙烯。此外，宜在相對於使用之氯甲基苯乙烯總量為40重量%以上來使用對氯甲基苯乙烯，更宜在50重量%以上來使用對氯甲基苯乙烯，又更宜在60重量%以上來使用對氯甲基苯乙烯。In addition, when two or more types of p-chloromethylstyrene, m-chloromethylstyrene, and o-chloromethylstyrene are used in combination, at least one of them is preferably used. In addition, it is preferable to use p-chloromethyl styrene at 40% by weight or more relative to the total amount of chloromethyl styrene used, more preferably to use p-chloromethyl styrene at 50% by weight or more, and more preferably at 60% by weight. P-chloromethylstyrene is used for weight% or more.
另外，在併用選自對氯甲基苯乙烯、間氯甲基苯乙烯、鄰氯甲基苯乙烯中之2種以上來合成具有式(1)所示之基之聚苯醚化合物，且該聚苯醚化合物中之式(1)包含如R1
為氫原子且R2
為碳數1之伸烷基的乙烯基苄基時，合成後之具有式(1)所示之取代基的聚苯醚化合物中，對乙烯基苄基、間乙烯基苄基、鄰乙烯基苄基之比例分別以其平均個數之比例表示。In addition, two or more selected from p-chloromethyl styrene, m-chloromethyl styrene, and o-chloromethyl styrene are used in combination to synthesize a polyphenylene ether compound having a group represented by formula (1), and the When the formula (1) in the polyphenylene ether compound contains a vinylbenzyl group in which R 1 is a hydrogen atom and R 2 is an alkylene group with
具體上，併用2種時，在併用對氯甲基苯乙烯及間氯甲基苯乙烯的情況下，合成後之具有前述式(1)所示之基的聚苯醚化合物中之各基平均個數之比例(平均個數比，以下皆同)宜為對乙烯基苄基：間乙烯基苄基=5~95：95~5左右。又，在併用對氯甲基苯乙烯及鄰氯甲基苯乙烯時，前述式(1)所示之聚苯醚化合物中之各基平均個數之比例宜為對乙烯基苄基：鄰乙烯基苄基=5~95：95~5左右；使用間氯甲基苯乙烯與鄰氯甲基苯乙烯時，各基平均個數之比例宜為間乙烯基苄基：鄰乙烯基苄基=5~95：95~5左右。並且，併用對氯甲基苯乙烯、間氯甲基苯乙烯、鄰氯甲基苯乙烯之3者時，合成後之具有前述式(1)所示之基的聚苯醚化合物中，對乙烯基苄基、間乙烯基苄基、鄰乙烯基苄基之平均個數比例比宜為對乙烯基苄基：間乙烯基苄基：鄰乙烯基苄基=20~90：40~5：40~5左右。又，當具有前述式(1)所示之基之聚苯醚化合物含有對乙烯基苄基、間乙烯基苄基、鄰乙烯基苄基中之2種以上時，較宜含有對乙烯基苄基，並且，相對於具有前述式(1)所示之基之聚苯醚化合物中所含乙烯基苄基總數，對乙烯基苄基之比率宜在40%以上，更宜在50%以上，又更宜在60%以上較佳。Specifically, when two types are used in combination, when p-chloromethyl styrene and m-chloromethyl styrene are used in combination, each group in the polyphenylene ether compound having the group represented by the aforementioned formula (1) after synthesis is averaged The ratio of the numbers (average number ratio, the following is the same) is preferably p-vinylbenzyl: m-vinylbenzyl=5~95: 95~5. In addition, when p-chloromethylstyrene and o-chloromethylstyrene are used in combination, the ratio of the average number of groups in the polyphenylene ether compound represented by the above formula (1) is preferably p-vinylbenzyl: o-ethylene Benzyl=5~95: About 95~5; when using m-chloromethylstyrene and o-chloromethylstyrene, the ratio of the average number of groups should be m-vinylbenzyl: o-vinylbenzyl= 5~95: Around 95~5. In addition, when three of p-chloromethylstyrene, m-chloromethylstyrene, and o-chloromethylstyrene are used in combination, in the polyphenylene ether compound having the group represented by the aforementioned formula (1) after synthesis, p-ethylene The ratio of the average number of phenylbenzyl, m-vinylbenzyl, and o-vinylbenzyl should be p-vinylbenzyl: m-vinylbenzyl: o-vinylbenzyl=20~90:40~5:40 ~5 or so. In addition, when the polyphenylene ether compound having the group represented by the aforementioned formula (1) contains two or more of p-vinylbenzyl, m-vinylbenzyl, and o-vinylbenzyl, it is more preferable to contain p-vinylbenzyl The ratio of vinylbenzyl groups to vinylbenzyl groups is preferably 40% or more, more preferably 50% or more, relative to the total number of vinylbenzyl groups contained in the polyphenylene ether compound having the group represented by the aforementioned formula (1), More preferably, it is more than 60%.
屬原料之聚苯醚只要是最後可合成預定改質聚苯醚者，即無特別限定。具體而言，可舉以由2,6-二甲基酚與2官能酚及3官能酚中之至少任一者所構成之聚苯醚或聚(2,6-二甲基-1,4-氧化苯)等聚苯醚為主成分者等。又，2官能酚係指於分子中具有2個酚性羥基之酚化合物，可舉如四甲基雙酚A等。另，3官能酚係指於分子中具有3個酚性羥基之酚化合物。The polyphenylene ether as a raw material is not particularly limited as long as it can finally synthesize the intended modified polyphenylene ether. Specifically, polyphenylene ether or poly(2,6-dimethyl-1,4) composed of 2,6-dimethylphenol and at least any one of bifunctional phenol and trifunctional phenol can be mentioned. -Benzene oxide) and other polyphenylene ether as the main component. In addition, the bifunctional phenol refers to a phenol compound having two phenolic hydroxyl groups in the molecule, and examples thereof include tetramethylbisphenol A and the like. In addition, the trifunctional phenol refers to a phenol compound having three phenolic hydroxyl groups in the molecule.
聚苯醚化合物之合成方法一例，譬如在如上述式(2)所示之聚苯醚化合物的情況下，具體上係使如上述之聚苯醚及鍵結有取代基X與鹵素原子之化合物(具有取代基X之化合物)溶解於溶劑中並予以攪拌。如此一來，聚苯醚與具有取代基X之化合物即會反應而可獲得本實施形態之上述式(2)所示改質聚苯醚。An example of the method for synthesizing polyphenylene ether compounds, for example, in the case of the polyphenylene ether compound represented by the above formula (2), specifically, the above polyphenylene ether and a compound bonded with a substituent X and a halogen atom (The compound with substituent X) is dissolved in the solvent and stirred. In this way, the polyphenylene ether and the compound having the substituent X will react to obtain the modified polyphenylene ether represented by the above formula (2) in this embodiment.
又，進行該反應時宜在鹼金屬氫氧化物存在下進行。藉此，吾等認為該反應可順利進行。此乃因為鹼金屬氫氧化物係作為脫鹵氫劑發揮作用，具體上係作為脫鹽酸劑發揮作用之故。即，鹼金屬氫氧化物會從聚苯醚之酚基與具有取代基X之化合物使鹵化氫脫離，藉此，取代基X將代替聚苯醚之酚基的氫原子而與酚基之氧原子鍵結。In addition, it is preferable to carry out this reaction in the presence of an alkali metal hydroxide. With this, we believe that the reaction can proceed smoothly. This is because the alkali metal hydroxide system functions as a dehydrohalogenating agent, specifically, it functions as a hydrochloric acid dehydrating agent. That is, the alkali metal hydroxide will dissociate the hydrogen halide from the phenolic group of the polyphenylene ether and the compound having the substituent X, whereby the substituent X will replace the hydrogen atom of the phenolic group of the polyphenylene ether and interact with the oxygen of the phenolic group. Atomic bonding.
又，鹼金屬氫氧化物只要是可作為脫鹵劑發揮作用者，即無特別限定，可舉如氫氧化鈉等。又，鹼金屬氫氧化物通常係在水溶液狀態下做使用，具體上可以氫氧化鈉水溶液做使用。In addition, the alkali metal hydroxide is not particularly limited as long as it can function as a dehalogenation agent, and examples thereof include sodium hydroxide. In addition, the alkali metal hydroxide is usually used in the state of an aqueous solution, and specifically, it can be used as an aqueous sodium hydroxide solution.
另，反應時間及反應溫度等反應條件雖因具有取代基X之化合物等而異，但只要是可使上述反應順利進行的條件，即無特別限定。具體上，反應溫度宜為室溫~100℃，且30~100℃較佳。又，反應時間宜為0.5~20小時，且0.5~10小時較佳。In addition, the reaction conditions such as the reaction time and the reaction temperature vary depending on the compound having the substituent X and the like, but are not particularly limited as long as they are conditions that allow the aforementioned reaction to proceed smoothly. Specifically, the reaction temperature is preferably from room temperature to 100°C, and preferably from 30 to 100°C. Furthermore, the reaction time is preferably 0.5 to 20 hours, and preferably 0.5 to 10 hours.
又，反應時所用溶劑只要是可使聚苯醚與具有取代基X之化合物溶解，且不會阻礙聚苯醚與具有取代基X之化合物的反應者，即無特別限定。具體上可舉甲苯等。In addition, the solvent used in the reaction is not particularly limited as long as it can dissolve the polyphenylene ether and the compound having the substituent X and does not hinder the reaction of the polyphenylene ether and the compound having the substituent X. Specifically, toluene and the like can be mentioned.
另，上述反應宜在不僅有鹼金屬氫氧化物，且相轉移觸媒亦存在之狀態下進行反應。即，上述反應宜在鹼金屬氫氧化物及相轉移觸媒存在下進行反應。藉此，吾等認為上述反應可順利進行。吾等以為其理由如下。因為，相轉移觸媒係一種具有可組入鹼金屬氫氧化物之功能、而可溶於水之類極性溶劑之相及有機溶劑之類非極性溶劑之相的二種相中並可在該等相間轉移的觸媒。具體上，在使用氫氧化鈉水溶液作為鹼金屬氫氧化物，且使用與水不相溶之甲苯等有機溶劑作為溶劑時，即使將氫氧化鈉水溶液滴至供於反應使用的溶劑，溶劑與氫氧化鈉水溶液也會呈現分離，而氫氧化鈉不易移動至溶劑中。如此一來，作為鹼金屬氫氧化物所添加的氫氧化鈉水溶液就很難對促進反應有所貢獻。針對此，吾等認為若在鹼金屬氫氧化物及相轉移觸媒存在下使其反應，鹼金屬氫氧化物即可以被相轉移觸媒組入之狀態移動至溶劑中，於是氫氧化鈉水溶液可易助於促進反應。因此，若在鹼金屬氫氧化物及相轉移觸媒之存在下使其反應，上述反應能更順利進行。In addition, the above reaction is preferably carried out in the presence of not only alkali metal hydroxides but also phase transfer catalysts. That is, the above reaction is preferably carried out in the presence of an alkali metal hydroxide and a phase transfer catalyst. In this way, we believe that the above reaction can proceed smoothly. Our reasons are as follows. Because the phase transfer catalyst has the function of being incorporated into alkali metal hydroxides, and is soluble in polar solvents such as water and non-polar solvents such as organic solvents. The catalyst for phase transfer. Specifically, when an aqueous sodium hydroxide solution is used as the alkali metal hydroxide and an organic solvent such as toluene that is incompatible with water is used as the solvent, even if the aqueous sodium hydroxide solution is dropped onto the solvent used for the reaction, the solvent and hydrogen The sodium oxide aqueous solution will also be separated, and the sodium hydroxide will not easily move into the solvent. In this way, the sodium hydroxide aqueous solution added as an alkali metal hydroxide hardly contributes to the acceleration of the reaction. In view of this, we believe that if it is reacted in the presence of an alkali metal hydroxide and a phase transfer catalyst, the alkali metal hydroxide can be incorporated into the phase transfer catalyst and move into the solvent, so sodium hydroxide aqueous solution Can easily help promote the reaction. Therefore, if it is reacted in the presence of an alkali metal hydroxide and a phase transfer catalyst, the above reaction can proceed more smoothly.
又，相轉移觸媒並無特別限定，可舉如溴化四正丁銨等四級銨鹽等。In addition, the phase transfer catalyst is not particularly limited, and examples thereof include quaternary ammonium salts such as tetra-n-butylammonium bromide.
並且在反應結束後，於反應液中投入甲醇等醇類使產物再沉澱後，將該沉澱物過濾並取出。藉由反覆數次(宜2次以上)將之洗淨之步驟，可使獲得之聚苯醚化合物的氯化物離子量在250ppm以下。And after the completion of the reaction, after adding alcohols such as methanol to the reaction solution to re-precipitate the product, the precipitate is filtered and taken out. By repeating the steps of washing it several times (preferably more than two times), the chloride ion content of the obtained polyphenylene ether compound can be kept below 250 ppm.
(交聯劑) 接下來說明本實施形態中使用之交聯劑。本實施形態中使用之交聯劑只要是於分子中具有碳-碳不飽和雙鍵之交聯劑、或可與前述聚苯醚化合物起反應而使其硬化之交聯劑，即無特別限定。(Crosslinking agent) Next, the crosslinking agent used in this embodiment will be explained. The cross-linking agent used in this embodiment is not particularly limited as long as it is a cross-linking agent having a carbon-carbon unsaturated double bond in the molecule, or a cross-linking agent that can react with the aforementioned polyphenylene ether compound to harden it. .
本實施形態之交聯劑是於分子中具有碳-碳不飽和雙鍵或是於分子中具有至少一個以上有助於與前述聚苯醚化合物行反應之官能基的化合物，因此可有效率地與前述聚苯醚化合物進行反應。所以，本實施形態之樹脂組成物可確保高Tg及密著性。The crosslinking agent of this embodiment is a compound that has a carbon-carbon unsaturated double bond in the molecule or has at least one functional group in the molecule that facilitates the reaction with the aforementioned polyphenylene ether compound, so it can efficiently It reacts with the aforementioned polyphenylene ether compound. Therefore, the resin composition of this embodiment can ensure high Tg and adhesion.
可在本實施形態中使用之交聯劑其交聯劑每1分子之碳-碳不飽和鍵的平均個數(末端雙鍵數)、或是有助於與前述化合物(A)行反應之官能基之交聯型硬化劑每1分子的平均個數(官能基數)，會依交聯劑之重量平均分子量等而異。末端雙鍵數或官能基數譬如宜為1~20個，2~18個較佳。該末端雙鍵數或官能基數若太少，有硬化物之耐熱性難以充分之傾向。又，末端雙鍵數或官能基數若太多，交聯劑之反應性會變太高。所以，會發生譬如樹脂組成物之保存性降低、或樹脂組成物之流動性降低等不良情況，而有所得硬化物之成形性降低之虞。The cross-linking agent that can be used in this embodiment has the average number of carbon-carbon unsaturated bonds per molecule of the cross-linking agent (the number of terminal double bonds), or it helps to react with the aforementioned compound (A) The average number of functional groups per molecule (number of functional groups) of the crosslinking hardener of functional groups varies depending on the weight average molecular weight of the crosslinking agent. For example, the number of terminal double bonds or functional groups is preferably 1-20, preferably 2-18. If the number of terminal double bonds or functional groups is too small, the heat resistance of the cured product tends to be insufficient. Furthermore, if the number of terminal double bonds or the number of functional groups is too large, the reactivity of the crosslinking agent will become too high. Therefore, disadvantages such as a decrease in the storage properties of the resin composition or a decrease in the fluidity of the resin composition may occur, and the moldability of the obtained cured product may decrease.
又，當交聯劑之重量平均分子量小於500(譬如在100以上且小於500)時，交聯劑之末端雙鍵數或官能基數宜為1~4個。又，當交聯劑之重量平均分子量在500以上(譬如在500以上且在5000以下)時，交聯劑之末端雙鍵數或官能基數宜為3~20個。在上述各個情況下，末端雙鍵數或官能基數若少於上述範圍之下限值，交聯劑之反應性恐降低，造成樹脂組成物之硬化物的交聯密度降低，而無法充分提高耐熱性或Tg。另一方面，末端雙鍵數或官能基數若多於上述範圍之上限值，樹脂組成物有容易膠化之疑慮。In addition, when the weight average molecular weight of the crosslinking agent is less than 500 (for example, more than 100 and less than 500), the number of terminal double bonds or functional groups of the crosslinking agent is preferably 1 to 4. Moreover, when the weight average molecular weight of the crosslinking agent is above 500 (for example, above 500 and below 5000), the number of terminal double bonds or functional groups of the crosslinking agent is preferably 3-20. In each of the above cases, if the number of terminal double bonds or the number of functional groups is less than the lower limit of the above range, the reactivity of the crosslinking agent may decrease, resulting in a decrease in the crosslinking density of the cured resin composition, and the heat resistance cannot be sufficiently improved. Sex or Tg. On the other hand, if the number of terminal double bonds or the number of functional groups exceeds the upper limit of the above range, the resin composition may easily gel.
另，此處的末端雙鍵數或官能基數可從使用之交聯劑的產品規格值得知。此處的末端雙鍵數或官能基數，具體上可舉如表示交聯劑1莫耳中存在之所有交聯劑每1分子的雙鍵數或官能基數之平均值的數值等。In addition, the number of terminal double bonds or the number of functional groups here can be known from the product specification value of the crosslinking agent used. Here, the number of terminal double bonds or the number of functional groups specifically includes a value representing the average value of the number of double bonds or the number of functional groups per molecule of all crosslinking agents present in 1 mole of the crosslinking agent.
具體的交聯劑宜為分子中具有2個以上碳-碳雙鍵之化合物，可舉如：譬如苯乙烯、苯乙烯共聚物、苯乙烯衍生物、分子中具有丙烯醯基之化合物、分子中具有甲基丙烯醯基之化合物、分子中具有乙烯基之化合物、分子中具有烯丙基之化合物、分子中具有馬來亞醯胺基之化合物、分子中具有苊結構之化合物及分子中具有三聚異氰酸酯基之三聚異氰酸酯化合物等。吾等認為，若使用該等化合物，利用硬化反應可更順利地形成交聯，從而可進一步提高本實施形態中使用之樹脂組成物之硬化物的耐熱性。The specific cross-linking agent is preferably a compound with more than two carbon-carbon double bonds in the molecule, such as styrene, styrene copolymer, styrene derivative, compound with acryl group in the molecule, Compounds with a methacrylic acid group, compounds with a vinyl group in the molecule, compounds with an allyl group in the molecule, compounds with a maleimide group in the molecule, compounds with an acenaphthene structure in the molecule, and three in the molecule Trimeric isocyanate compound of polyisocyanate group, etc. We believe that if these compounds are used, the curing reaction can be used to form cross-links more smoothly, thereby further improving the heat resistance of the cured resin composition used in this embodiment.
前述苯乙烯衍生物可舉如溴苯乙烯及二溴苯乙烯等。Examples of the aforementioned styrene derivatives include bromostyrene and dibromostyrene.
前述分子中具有丙烯醯基之化合物為丙烯酸酯化合物。前述丙烯酸酯化合物可舉分子中具有1個丙烯醯基之單官能丙烯酸酯化合物、及分子中具有2個以上丙烯醯基之多官能丙烯酸酯化合物。前述單官能丙烯酸酯化合物可舉如丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯及丙烯酸丁酯等。前述多官能丙烯酸酯化合物可舉如三環癸烷二甲醇二丙烯酸酯等。The aforementioned compound having an acryl group in the molecule is an acrylate compound. The aforementioned acrylate compound includes a monofunctional acrylate compound having one acryl group in the molecule, and a multifunctional acrylate compound having two or more acryl groups in the molecule. Examples of the aforementioned monofunctional acrylate compound include methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate. Examples of the aforementioned polyfunctional acrylate compound include tricyclodecane dimethanol diacrylate.
前述分子中具有甲基丙烯醯基之化合物為甲基丙烯酸酯化合物。前述甲基丙烯酸酯化合物可舉分子中具有1個甲基丙烯醯基之單官能甲基丙烯酸酯化合物、及分子中具有2個以上甲基丙烯醯基之多官能甲基丙烯酸酯化合物。前述單官能甲基丙烯酸酯化合物可舉如甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯及甲基丙烯酸丁酯等。前述多官能甲基丙烯酸酯化合物可舉如三環癸烷二甲醇二甲基丙烯酸酯等。The compound having a methacryl group in the molecule is a methacrylate compound. Examples of the aforementioned methacrylate compound include a monofunctional methacrylate compound having one methacrylic acid group in the molecule, and a multifunctional methacrylate compound having two or more methacrylic acid groups in the molecule. Examples of the aforementioned monofunctional methacrylate compound include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate. Examples of the aforementioned polyfunctional methacrylate compound include tricyclodecane dimethanol dimethacrylate and the like.
前述分子中具有乙烯基之化合物為乙烯基化合物。前述乙烯基化合物可舉分子中具有1個乙烯基之單官能乙烯基化合物(單乙烯基化合物)、及分子中具有2個以上乙烯基之多官能乙烯基化合物。前述多官能乙烯基化合物可舉多官能芳香族乙烯基化合物、多官能脂肪族乙烯基化合物、含有源自多官能芳香族乙烯基化合物之結構的聚合物或共聚物、含有源自多官能脂肪族乙烯基化合物之結構的聚合物或共聚物，可舉例如二乙烯基苯、二乙烯基苯共聚物、聚丁二烯、丁二烯共聚物等。The aforementioned compound having a vinyl group in the molecule is a vinyl compound. The aforementioned vinyl compound includes a monofunctional vinyl compound (monovinyl compound) having one vinyl group in the molecule, and a multifunctional vinyl compound having two or more vinyl groups in the molecule. The aforementioned polyfunctional vinyl compound may include polyfunctional aromatic vinyl compounds, polyfunctional aliphatic vinyl compounds, polymers or copolymers containing structures derived from polyfunctional aromatic vinyl compounds, and containing polyfunctional aliphatic vinyl compounds. Examples of polymers or copolymers with the structure of vinyl compounds include divinylbenzene, divinylbenzene copolymers, polybutadiene, butadiene copolymers, and the like.
前述分子中具有烯丙基之化合物為烯丙基化合物。前述烯丙基化合物可舉分子中具有1個烯丙基之單官能烯丙基化合物、及分子中具有2個以上烯丙基之多官能烯丙基化合物。前述多官能烯丙基化合物可舉如酞酸二烯丙酯(DAP)等。The aforementioned compound having an allyl group in the molecule is an allyl compound. Examples of the aforementioned allyl compound include monofunctional allyl compounds having one allyl group in the molecule, and polyfunctional allyl compounds having two or more allyl groups in the molecule. Examples of the aforementioned polyfunctional allyl compound include diallyl phthalate (DAP) and the like.
前述分子中具有馬來亞醯胺基之化合物為馬來亞醯胺化合物。前述馬來亞醯胺化合物可舉分子中具有1個馬來亞醯胺基之單官能馬來亞醯胺化合物、及分子中具有2個以上馬來亞醯胺基之多官能馬來亞醯胺化合物。此外，前述馬來亞醯胺化合物亦可為：分子中一部分經胺化合物改質之改質馬來亞醯胺化合物、分子中一部分經聚矽氧化合物改質之改質馬來亞醯胺化合物、及分子中一部分經胺化合物及聚矽氧化合物改質之改質馬來亞醯胺化合物等。The compound having a maleimide group in the aforementioned molecule is a maleimide compound. The aforementioned maleimide compound can include a monofunctional maleimide compound having one maleimide group in the molecule, and a multifunctional maleimide compound having two or more maleimide groups in the molecule. Amine compound. In addition, the aforementioned maleimide compound may also be: modified maleimide compound in which part of the molecule is modified by an amine compound, and modified maleimide compound in which part of the molecule is modified by polysiloxane compound , And modified maleimide compounds in which part of the molecule is modified by amine compounds and silicone compounds.
前述分子中具有苊結構之化合物為苊化合物。前述苊化合物可舉如苊、烷基苊類、鹵化苊類及苯基苊類等。前述烷基苊類可舉如1-甲基苊、3-甲基苊、4-甲基苊、5-甲基苊、1-乙基苊、3-乙基苊、4-乙基苊、5-乙基苊等。前述鹵化苊類可舉如1-氯苊、3-氯苊、4-氯苊、5-氯苊、1-溴苊、3-溴苊、4-溴苊、5-溴苊等。前述苯基苊類可舉如1-苯基苊、3-苯基苊、4-苯基苊、5-苯基苊等。前述苊化合物可為如前述之分子中具有1個苊結構之單官能苊化合物，亦可為分子中具有2個以上苊結構之多官能苊化合物。The compound having an acenaphthene structure in the aforementioned molecule is an acenaphthene compound. Examples of the aforementioned acenaphthene compounds include acenaphthene, alkyl acenaphthenes, halogenated acenaphthenes, and phenylacenaphthenes. The aforementioned alkyl acenaphthene may include 1-methyl acenaphthene, 3-methyl acenaphthene, 4-methyl acenaphthene, 5-methyl acenaphthene, 1-ethyl acenaphthene, 3-ethyl acenaphthene, 4-ethyl acenaphthene, 5-ethylacenaphthene and so on. Examples of the aforementioned halogenated acenaphthene include 1-chloroacenaphthene, 3-chloroacenaphthene, 4-chloroacenaphthene, 5-chloroacenaphthene, 1-bromoacenaphthene, 3-bromoacenaphthene, 4-bromoacenaphthene, 5-bromoacenaphthene and the like. Examples of the aforementioned phenylacenaphthene include 1-phenylacenaphthene, 3-phenylacenaphthene, 4-phenylacenaphthene, 5-phenylacenaphthene and the like. The aforementioned acenaphthene compound may be a monofunctional acenaphthene compound having one acenaphthene structure in the molecule as described above, or a multifunctional acenaphthene compound having two or more acenaphthene structures in the molecule.
前述分子中具有三聚異氰酸酯基之化合物為三聚異氰酸酯化合物。前述三聚異氰酸酯化合物可舉分子中更具有烯基之化合物(三聚異氰酸烯基酯化合物)等，可舉例如三聚異氰酸三烯丙酯(TAIC)等三聚異氰酸三烯基酯化合物等。The compound having a trimeric isocyanate group in the aforementioned molecule is a trimeric isocyanate compound. The aforementioned trimeric isocyanate compound may include compounds having more alkenyl groups in the molecule (trimeric isocyanate alkenyl ester compound), etc., for example, trimeric isocyanate compounds such as triallyl isocyanate (TAIC) Alkenyl ester compounds, etc.
前述交聯劑在上述中，又譬如宜為分子中具有2個以上丙烯醯基之多官能丙烯酸酯化合物、分子中具有2個以上甲基丙烯醯基之多官能甲基丙烯酸酯化合物、分子中具有2個以上乙烯基之多官能乙烯基化合物、苯乙烯衍生物、分子中具有烯丙基之烯丙基化合物、分子中具有馬來亞醯胺基之馬來亞醯胺化合物、分子中具有苊結構之苊化合物、及分子中具有三聚異氰酸酯基之三聚異氰酸酯化合物。Among the above-mentioned crosslinking agents, for example, a multifunctional acrylate compound having two or more acryloyl groups in the molecule, a multifunctional methacrylate compound having two or more methacryloyl groups in the molecule, or Multifunctional vinyl compounds having two or more vinyl groups, styrene derivatives, allyl compounds having allyl groups in the molecule, maleimide compounds having a maleimide group in the molecule, and Acenaphthene compounds with acenaphthene structure and trimer isocyanate compounds with trimer isocyanate groups in the molecule.
前述交聯劑可將上述交聯劑單獨使用，亦可將2種以上組合使用。另，就交聯劑而言，亦可併用於分子中具有2個以上碳-碳不飽和鍵之化合物與於分子中具有1個碳-碳不飽和鍵之化合物。The aforementioned crosslinking agent may be used alone or in combination of two or more kinds. In addition, as for the crosslinking agent, it can also be used in combination with a compound having two or more carbon-carbon unsaturated bonds in the molecule and a compound having one carbon-carbon unsaturated bond in the molecule.
(含量、含有比) 在本實施形態之樹脂組成物中，相對於聚苯醚化合物與交聯劑之合計100質量份，前述聚苯醚化合物之含量宜為30~90質量份，且50~90質量份較佳。又，相對於前述聚苯醚化合物與交聯劑之合計100質量份，前述交聯劑之含量宜為10~70質量份，且10~50質量份較佳。即，前述聚苯醚化合物與交聯劑之含有比例，以質量比計宜為90：10~30：70，且90：10~50：50較佳。聚苯醚及交聯劑之各含量只要是滿足上述比例之含量，改質聚苯醚與交聯劑之硬化反應即可順利進行。所以，可形成交聯物之耐熱性及阻燃性更佳的樹脂組成物。(Content, content ratio) In the resin composition of the present embodiment, the content of the polyphenylene ether compound is preferably 30 to 90 parts by mass, and more preferably 50 to 90 parts by mass relative to 100 parts by mass of the total of the polyphenylene ether compound and the crosslinking agent. Moreover, the content of the crosslinking agent is preferably 10 to 70 parts by mass, and more preferably 10 to 50 parts by mass relative to the total of 100 parts by mass of the polyphenylene ether compound and the crosslinking agent. That is, the content ratio of the aforementioned polyphenylene ether compound to the crosslinking agent is preferably 90:10 to 30:70 in terms of mass ratio, and preferably 90:10 to 50:50. As long as the contents of the polyphenylene ether and the crosslinking agent satisfy the above ratio, the hardening reaction of the modified polyphenylene ether and the crosslinking agent can proceed smoothly. Therefore, a resin composition with better heat resistance and flame retardancy of the cross-linked product can be formed.
(其他成分) 另，本實施形態之樹脂組成物只要是含有前述聚苯醚化合物與前述交聯劑者即無特別限定，亦可進一步含有其他成分。(Other ingredients) In addition, the resin composition of the present embodiment is not particularly limited as long as it contains the polyphenylene ether compound and the crosslinking agent, and may further contain other components.
譬如，本實施形態之樹脂組成物可進一步含有充填材。充填材可舉用以提高樹脂組成物之硬化物之耐熱性及阻燃性而添加之物等，並無特別限定。又，藉由使其含有充填材，可進一步提高耐熱性及阻燃性等。充填材具體上可舉球狀二氧化矽等二氧化矽、氧化鋁、氧化鈦及雲母等金屬氧化物、氫氧化鋁、氫氧化鎂等金屬氫氧化物、滑石、硼酸鋁、硫酸鋇及碳酸鈣等。且，就充填材而言，其中又以二氧化矽、雲母及滑石為宜，球狀二氧化矽較佳。又，充填材可單獨使用1種，亦可將2種以上組合使用。而且充填材可直接使用，亦可使用業經環氧矽烷型、乙烯基矽烷型、甲基丙烯醯基矽烷型或胺基矽烷型的矽烷耦合劑進行表面處理之物。該矽烷耦合劑亦可以整體摻混法替代預先對充填材進行表面處理之方法來添加使用。For example, the resin composition of this embodiment may further contain a filler. The filler may be added to improve the heat resistance and flame retardancy of the cured product of the resin composition, and it is not particularly limited. In addition, by including a filler, heat resistance, flame retardancy, etc. can be further improved. Specifically, the filling material includes spherical silica and other metal oxides such as silica, aluminum oxide, titanium oxide, and mica, and metal hydroxides such as aluminum hydroxide and magnesium hydroxide, talc, aluminum borate, barium sulfate, and carbonic acid. Calcium etc. Moreover, as for the filling material, among them, silica, mica and talc are preferred, and spherical silica is preferred. Moreover, the filler may be used individually by 1 type, and may be used in combination of 2 or more types. Moreover, the filling material can be used directly, or it can be surface-treated with a silane coupling agent of epoxy silane type, vinyl silane type, methacryl silane type or amino silane type. The silane coupling agent can also be added and used by the overall blending method instead of the surface treatment of the filling material in advance.
並且，在含有充填材時，其含量宜相對於前述聚苯醚化合物與前述交聯劑之合計100質量份為10~200質量份，30~150質量份更佳。In addition, when the filler is contained, its content is preferably 10 to 200 parts by mass, more preferably 30 to 150 parts by mass relative to 100 parts by mass of the total of the polyphenylene ether compound and the crosslinking agent.
此外，本實施形態之樹脂組成物亦可含有阻燃劑，阻燃劑可舉如溴系阻燃劑等鹵素系阻燃劑或磷系阻燃劑等。鹵素系阻燃劑之具體例可舉如五溴二苯基醚、八溴二苯基醚、十溴二苯基醚、四溴雙酚A、六溴環十二烷等溴系阻燃劑或氯化石蠟等氯系阻燃劑等。又，磷系阻燃劑之具體例可舉如縮合磷酸酯、環狀磷酸酯等磷酸酯；環狀膦氮烯化合物等膦氮烯化合物；二烷基次磷酸鋁鹽等次磷酸金屬鹽等之次磷酸鹽系阻燃劑；磷酸三聚氰胺及聚磷酸三聚氰胺等三聚氰胺系阻燃劑；具有二苯基膦氧化物基之膦氧化物化合物等。阻燃劑可單獨使用所例示之各阻燃劑，亦可將2種以上組合使用。In addition, the resin composition of the present embodiment may also contain a flame retardant. Examples of the flame retardant include halogen flame retardants such as bromine flame retardants or phosphorus flame retardants. Specific examples of halogen flame retardants include brominated flame retardants such as pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, tetrabromobisphenol A, and hexabromocyclododecane Or chlorine-based flame retardants such as chlorinated paraffin. In addition, specific examples of phosphorus-based flame retardants include phosphoric acid esters such as condensed phosphoric acid esters and cyclic phosphoric acid esters; phosphazene compounds such as cyclic phosphazene compounds; and metal hypophosphorous acid salts such as dialkyl aluminum hypophosphites. Hypophosphite-based flame retardants; melamine-based flame retardants such as melamine phosphate and melamine polyphosphate; phosphine oxide compounds with diphenylphosphine oxide groups. As the flame retardant, each of the illustrated flame retardants may be used alone, or two or more of them may be used in combination.
含有阻燃劑時，其含量宜相對於前述聚苯醚化合物與前述交聯劑之合計100質量份為10~40質量份，15~30質量份更佳。When a flame retardant is contained, its content is preferably 10-40 parts by mass, and more preferably 15-30 parts by mass relative to the total of 100 parts by mass of the polyphenylene ether compound and the crosslinking agent.
並且，本實施形態之樹脂組成物除上述以外，亦可含有各種添加劑。添加劑可舉如聚矽氧系消泡劑及丙烯酸酯系消泡劑等消泡劑、熱穩定劑、抗靜電劑、紫外線吸收劑、染料或顏料、滑劑、濕潤分散劑等分散劑等。In addition, the resin composition of this embodiment may contain various additives in addition to the above. Examples of additives include defoamers such as silicone defoamers and acrylate defoamers, heat stabilizers, antistatic agents, ultraviolet absorbers, dyes or pigments, slip agents, wetting dispersants, and other dispersants.
(預浸體、附樹脂之薄膜、覆金屬積層板、配線板及附樹脂之金屬箔) 接下來，說明使用本實施形態之樹脂組成物的預浸體、覆金屬積層板、配線板及附樹脂之金屬箔。另，以下說明之圖式中，各符號分別意義如下：1…預浸體、2…樹脂組成物或樹脂組成物之半硬化物、3…纖維質基材、11…覆金屬積層板、12…絕緣層、13…金屬箔、14…配線、21…配線基板、31…附樹脂之金屬箔、32及42…樹脂層、41…附樹脂之薄膜、43…支持薄膜。(Prepreg, film with resin, metal-clad laminate, wiring board and metal foil with resin) Next, a prepreg, a metal-clad laminate, a wiring board, and a metal foil with resin using the resin composition of this embodiment will be described. In addition, in the drawings described below, the respective symbols have the following meanings: 1...prepreg, 2...resin composition or semi-cured resin composition, 3...fibrous base material, 11...metal-clad laminate, 12 …Insulating layer, 13…metal foil, 14…wiring, 21…wiring board, 31…metal foil with resin, 32 and 42…resin layer, 41…film with resin, 43…support film.
圖1係顯示本發明實施形態之預浸體1之一例的概略截面圖。Fig. 1 is a schematic cross-sectional view showing an example of a
如圖1所示，本實施形態之預浸體1具備前述樹脂組成物或前述樹脂組成物之半硬化物2與纖維質基材3。該預浸體1可舉在前述樹脂組成物或其半硬化物2之中存在纖維質基材3者。即，該預浸體1具備前述樹脂組成物或其半硬化物、及存在於前述樹脂組成物或其半硬化物2之中的纖維質基材3。As shown in FIG. 1, the
在本實施形態之預浸體及後述的附樹脂之薄膜及附樹脂之金屬箔中，樹脂組成物或樹脂組成物之半硬化物中之Cl離子量宜為0ppm~40ppm左右。基於成本觀點，1ppm~40ppm較佳，2ppm~40ppm更佳。前述樹脂組成物或樹脂組成物之半硬化物中之Cl離子量可以後述實施例中記載之方法進行測定。In the prepreg of this embodiment, the film with resin and the metal foil with resin described later, the amount of Cl ion in the resin composition or the semi-hardened resin composition is preferably about 0 ppm to 40 ppm. From the viewpoint of cost, 1ppm-40ppm is better, and 2ppm-40ppm is even better. The amount of Cl ions in the aforementioned resin composition or the semi-hardened substance of the resin composition can be measured by the method described in the following Examples.
並且，於本實施形態之預浸體或後述的附樹脂之薄膜及附樹脂之金屬箔中之樹脂組成物或樹脂組成物之半硬化物，除上述Cl離子以外，有時還會含有溴化物離子(Br- )硝酸根離子(NO3 - )、硫酸根離子(SO4 - )、亞硝酸根離子(NO2 - )、磷酸根離子(PO4 3- )、鈉離子(Na+ )、銨離子(NH4 + )、鈣離子(Ca2+ )等離子性不純物。該等離子性不純物並無特別限定，但宜盡可能為低濃度，譬如在含有離子性不純物時，溴化物離子(Br- )硝酸根離子(NO3 - )、硫酸根離子(SO4 - )、亞硝酸根離子(NO2 - )、磷酸根離子(PO4 3- )、鈉離子(Na+ )、銨離子(NH4 + )、鈣離子(Ca2+ )宜各在30ppm以下。In addition, the resin composition or semi-cured resin composition in the prepreg of this embodiment, the film with resin and the metal foil with resin described later, may contain bromide in addition to the above-mentioned Cl ion. ion (Br -) nitrate ion (NO 3 -), sulfate ion (SO 4 -), nitrite ion (NO 2 -), phosphate ion (PO 4 3-), sodium ion (Na +), Ammonium ions (NH 4 + ) and calcium ions (Ca 2+ ) are ionic impurities. Such ionic impurities is not particularly limited, but the concentration should be as low as, for example, when the content of ionic impurities, bromide ion (Br -) nitrate ion (NO 3 -), sulfate ion (SO 4 -), nitrite ion (NO 2 -), phosphate ion (PO 4 3-), sodium ion (Na +), ammonium ion (NH 4 +), calcium ion (Ca 2+) in each should be 30ppm or less.
因此，本發明亦包含一種樹脂組成物，其特徵在於含有：於分子末端具有下述式(1)所示之基之聚苯醚化合物、及於分子中具有碳-碳不飽和雙鍵之交聯劑；Therefore, the present invention also includes a resin composition characterized by containing: a polyphenylene ether compound having a group represented by the following formula (1) at the end of the molecule, and a combination having a carbon-carbon unsaturated double bond in the molecule Coupling agent
[化學式7]
[式(1)中，R1 表示氫原子或碳數1~10之烷基，R2 表示碳數1~10之伸烷基]；並且 樹脂組成物或樹脂組成物之半硬化物中之氯化物離子量在40ppm以下。[In formula (1), R 1 represents a hydrogen atom or an alkyl group with 1 to 10 carbons, and R 2 represents an alkylene with 1 to 10 carbons]; and the resin composition or the semi-hardened resin composition The amount of chloride ion is below 40 ppm.
另，在本實施形態中，「半硬化物」意指使樹脂組成物在可進一步硬化之程度上硬化至中間狀態者。即，半硬化物係樹脂組成物呈半硬化狀態(經B階段化)者。譬如，樹脂組成物一經加熱，剛開始黏度會緩慢地下降，然後開始硬化後，黏度又緩慢地上升。此時，半硬化便可舉從黏度開始上升後至完全硬化之前之期間的狀態等。In addition, in this embodiment, "semi-cured material" means a resin composition that is cured to an intermediate state to the extent that it can be cured further. That is, the semi-cured resin composition is in a semi-cured state (B-staged). For example, once a resin composition is heated, its viscosity will slowly decrease at the beginning, and then after it begins to harden, the viscosity will slowly increase. At this time, the semi-curing can be the state from the time after the viscosity starts to rise to before the complete curing.
使用本實施形態之樹脂組成物製得的預浸體可以是如上述之具備前述樹脂組成物之半硬化物者，亦可以是具備未硬化之前述樹脂組成物本身者。即，可為具備前述樹脂組成物之半硬化物(B階段之前述樹脂組成物)與纖維質基材的預浸體，亦可為具備硬化前之前述樹脂組成物(A階段之前述樹脂組成物)與纖維質基材的預浸體。具體而言，可舉如在前述樹脂組成物之中存在纖維質基材者等。另，樹脂組成物或其半硬化物亦可為前述樹脂組成物經乾燥或加熱乾燥者。The prepreg prepared by using the resin composition of this embodiment may be a semi-cured product provided with the aforementioned resin composition as described above, or it may be provided with the aforementioned uncured resin composition itself. That is, it may be a prepreg comprising the semi-cured resin composition (the resin composition of the B stage) and a fibrous base material, or the resin composition before curing (the resin composition of the A stage)物) prepreg with fibrous base material. Specifically, for example, those having a fibrous base material in the aforementioned resin composition can be mentioned. In addition, the resin composition or the semi-cured product thereof may be those obtained by drying or heating and drying the aforementioned resin composition.
使用本實施形態之清漆狀樹脂組成物來製造本實施形態之預浸體1的方法，可舉如使樹脂清漆狀樹脂組成物2浸潤至纖維質基材3中後予以乾燥之方法。The method of manufacturing the
製造預浸體時使用的纖維質基材，具體上可舉如玻璃布、芳醯胺布、聚酯布、LCP(液晶聚合物)不織布、玻璃不織布、芳醯胺不織布、聚酯不織布、紙漿紙及棉絨紙。另，若使用玻璃布，可製得機械強度優異的積層板，尤以經過扁平處理加工的玻璃布為宜。本實施形態中使用之玻璃布並無特別限定，可舉如E玻璃、S玻璃、NE玻璃、Q玻璃或L玻璃等低介電係數玻璃布等。扁平處理加工具體上可藉由在適當壓力下以壓輥將玻璃布連續加壓，將線股壓縮成扁平來進行。另，纖維質基材之厚度譬如可普遍使用0.01~0.3mm之物。The fibrous substrate used in the manufacture of prepregs, specifically, glass cloth, aramid cloth, polyester cloth, LCP (liquid crystal polymer) non-woven fabric, glass non-woven fabric, aramid non-woven fabric, polyester non-woven fabric, pulp Paper and lint paper. In addition, if glass cloth is used, a laminated board with excellent mechanical strength can be produced, and glass cloth that has been flattened is particularly suitable. The glass cloth used in this embodiment is not particularly limited, and examples include low-dielectric glass cloth such as E glass, S glass, NE glass, Q glass, or L glass. Specifically, the flattening process can be performed by continuously pressing the glass cloth with a pressing roller under appropriate pressure to compress the strands into a flat shape. In addition, the thickness of the fibrous substrate can generally be 0.01~0.3mm, for example.
要將樹脂清漆(樹脂組成物2)浸潤至纖維質基材3中，可藉由浸漬及塗佈等進行。該浸潤可視需求多次反覆進行。又，此時，亦可用組成或濃度不同的多種樹脂清漆反覆浸潤，來調整成最後所希望的組成(含有比)及樹脂量。The impregnation of the resin varnish (resin composition 2) into the
將已浸潤樹脂清漆(樹脂組成物2)之纖維質基材3，在所期望之加熱條件譬如80℃以上且180℃以下，加熱1分鐘以上且10分鐘以下。藉由加熱，使溶劑從清漆揮發，減少或去除溶劑而製得硬化前(A階段)或半硬化狀態(B階段)之預浸體1。The
又，如圖4所示，本實施形態之附樹脂之金屬箔31具有含有上述樹脂組成物或前述樹脂組成物之半硬化物之樹脂層32與金屬箔13積層而成的構成。即，本實施形態之附樹脂之金屬箔可為具備含有硬化前之前述樹脂組成物(A階段之前述樹脂組成物)之樹脂層與金屬箔的附樹脂之金屬箔，亦可為具備含有前述樹脂組成物之半硬化物(B階段之前述樹脂組成物)之樹脂層與金屬箔的附樹脂之金屬箔。Moreover, as shown in FIG. 4, the
用以製造所述附樹脂之金屬箔31的方法，可舉如將如上述之樹脂清漆狀樹脂組成物塗佈於銅箔等金屬箔13之表面後予以乾燥的方法。前述塗佈方法可舉如棒塗機、刮刀逗式塗佈機或模塗機、輥塗機、凹版塗佈機等。As a method for manufacturing the said
前述金屬箔13可不作限定地使用用在覆金屬積層板或配線基板等的金屬箔，可舉如銅箔及鋁箔等。The
此外，如圖5所示，本實施形態之附樹脂之薄膜41具有含有上述樹脂組成物或前述樹脂組成物之半硬化物的樹脂層42與薄膜支持基材43積層而成的構成。即，本實施形態之附樹脂之薄膜可為具備硬化前之前述樹脂組成物(A階段之前述樹脂組成物)與薄膜支持基材的附樹脂之薄膜，亦可為具備前述樹脂組成物之半硬化物(B階段之前述樹脂組成物)與薄膜支持基材的附樹脂之薄膜。Moreover, as shown in FIG. 5, the
用以製造所述附樹脂之薄膜41的方法，譬如可將如上述之樹脂清漆狀樹脂組成物塗佈於薄膜支持基材43表面後，使溶劑從清漆揮發，減少溶劑或去除溶劑，而製得硬化前(A階段)或半硬化狀態(B階段)的附樹脂之薄膜。The method for manufacturing the resin-coated
前述薄膜支持基材可舉聚醯亞胺薄膜、PET(聚對苯二甲酸乙二酯)薄膜、聚酯薄膜、聚乙二醯脲薄膜、聚醚醚酮薄膜、聚伸苯硫薄膜、芳醯胺薄膜、聚碳酸酯薄膜、聚芳酯薄膜等電絕緣性薄膜等。The aforementioned film support substrate can include polyimide film, PET (polyethylene terephthalate) film, polyester film, polyethylene urea film, polyetheretherketone film, polyphenylene sulfide film, aromatic Electrically insulating films such as amide film, polycarbonate film, polyarylate film, etc.
另，以本實施形態之附樹脂之薄膜及附樹脂之金屬箔來說，亦與上述預浸體同樣地，樹脂組成物或其半硬化物亦可為前述樹脂組成物經乾燥或加熱乾燥者。In addition, in the case of the resin-attached film and the resin-attached metal foil of the present embodiment, the resin composition or its semi-cured product may also be the above-mentioned resin composition dried or heat-dried in the same way as the above-mentioned prepreg. .
上述金屬箔13及薄膜支持基材43之厚度等可按所期望目的適宜設定。舉例而言，金屬箔13可使用0.2~70μm左右之物。譬如金屬箔厚度為10μm以下時等的情況下，為了提升處置性，亦可為具備剝離層及載體的附載體之銅箔。要將樹脂清漆應用在金屬箔13或薄膜支持基材43，可藉由塗佈等進行，並可視需求多次反覆進行。又，此時，亦可用組成或濃度不同的多種樹脂清漆反覆塗佈，來調整成最後所希望的組成(含有比)及樹脂量。The thickness of the
關於附樹脂之金屬箔31或樹脂薄膜41之製造方法中的乾燥或加熱乾燥條件，並無特別限定，將樹脂清漆狀樹脂組成物塗佈至上述金屬箔13或薄膜支持基材43以後，可在所期望之加熱條件譬如80~170℃下加熱1~10分鐘左右，使溶劑從清漆揮發以減少或去除溶劑，藉此可製得硬化前(A階段)或半硬化狀態(B階段)的附樹脂之金屬箔31或樹脂薄膜41。Regarding the drying or heating and drying conditions in the manufacturing method of the resin-coated
附樹脂之金屬箔31或樹脂薄膜41亦可視需求具備覆蓋薄膜等。藉由具備覆蓋薄膜，可防止異物混入等。覆蓋薄膜只要是可剝離而不會損害樹脂組成物之形態者即無特別限定，譬如可使用聚烯烴薄膜、聚酯薄膜、TPX薄膜以及於該等薄膜設置脫模劑層所形成的薄膜，甚至是紙基材上層合有該等薄膜而成的紙等。The
如圖2所示，本實施形態之覆金屬積層板11的特徵在於具有：包含上述樹脂組成物之硬化物或上述預浸體之硬化物的絕緣層12、與金屬箔13。另，用在覆金屬積層板11的金屬箔13，可使用與上述金屬箔13相同之物。As shown in FIG. 2, the metal-clad
又，本實施形態之覆金屬積層板13亦可用上述附樹脂之金屬箔31或樹脂薄膜41作成。In addition, the metal-clad
使用經上述方式製得的預浸體1、附樹脂之金屬箔31或樹脂薄膜41來製作覆金屬積層板的方法，可將預浸體1、附樹脂之金屬箔31或樹脂薄膜41單片或多片層疊後，進一步於其上下兩面或單面層疊銅箔等金屬箔13，再將其加熱加壓成形進行積層一體化，而製出雙面覆金屬箔之積層體或單面覆金屬箔之積層體。加熱加壓條件可根據要製造之積層板厚度及樹脂組成物種類等適當設定，譬如，溫度可設為170~220℃，壓力可設為1.5~5.0MPa，時間可設為60~150分鐘。The
另，覆金屬積層板11亦可不用預浸體1，而將薄膜狀樹脂組成物形成於金屬箔13上後進行加熱加壓來製作。In addition, the metal-clad
然後，如圖3所示，本實施形態之配線基板21具有：包含上述樹脂組成物之硬化物或上述預浸體之硬化物的絕緣層12、與配線14。Then, as shown in FIG. 3, the
本實施形態之樹脂組成物宜作為配線基板之層間絕緣層之材料使用。雖無特別限定，譬如宜用於具有10層以上、更宜具有15層以上電路層之多層配線板的層間絕緣層之材料。The resin composition of this embodiment is suitable for use as a material for the interlayer insulating layer of a wiring board. Although it is not particularly limited, it is suitable for use as a material for the interlayer insulating layer of a multilayer wiring board having 10 or more layers, and more preferably 15 or more circuit layers.
並且，上述層間絕緣層之材料宜使用多層由本實施形態之樹脂組成物構成之絕緣層。雖無特別限定，譬如宜以10層以上作使用。藉此，在多層配線板中可使導體電路圖案更加高密度化，從而可進一步提升在多層層間絕緣層之較低的介電特性與導體電路圖案間之絕緣可靠性、層間電路間之絕緣性。並且，還可獲得提高多層配線基板之訊號的傳輸速度、降低訊號傳輸時之損失等效果。In addition, it is preferable to use a plurality of insulating layers composed of the resin composition of this embodiment as the material of the aforementioned interlayer insulating layer. Although it is not particularly limited, for example, 10 layers or more are suitable for use. Thereby, the conductor circuit pattern can be more dense in the multilayer wiring board, thereby further improving the lower dielectric properties of the multilayer interlayer insulating layer, the insulation reliability between the conductor circuit patterns, and the insulation between the interlayer circuits. . In addition, the effects of increasing the signal transmission speed of the multilayer wiring board and reducing the loss during signal transmission can also be obtained.
所述配線基板21之製造方法，譬如可將上述所得覆金屬積層體13表面之金屬箔13進行蝕刻加工等形成電路(配線)，而製得於積層體表面設有導體圖案(配線14)作為電路的配線基板21。形成電路之方法除了上述記載之方法以外，還可舉如利用半加成法(SAP：Semi Additive Process)或改良半加成法(MSAP：Modified Semi Additive Process)來形成電路等。The method of manufacturing the
使用本實施形態之樹脂組成物，則在形成有如上述之電路的配線基板、亦即具有電路間之距離在150μm以下這類導體電路圖案的基板中，也能確保優異的絕緣可靠性。在此，電路間之距離意指如圖6所示般鄰接之二個配線(導體電路)(L)之間的距離(space)S。此外，在本實施形態之配線基板中，電路間之距離無須全部都在150μm以下，只要至少一部分具有電路間距離在150μm以下之處即可。The use of the resin composition of the present embodiment can ensure excellent insulation reliability even in wiring substrates on which circuits as described above are formed, that is, substrates having conductor circuit patterns such that the distance between circuits is 150 μm or less. Here, the distance between circuits means the distance (space) S between two adjacent wirings (conductor circuits) (L) as shown in FIG. 6. In addition, in the wiring board of the present embodiment, all the distances between circuits do not need to be 150 μm or less, as long as at least a part of the distance between circuits is 150 μm or less.
如所述，做成基板內具有導體電路圖案的基板且該導體電路圖案之至少一部分包含電路間距離在150μm以下之處，藉此更可使基板內之導體電路圖案成為高密度，而可縮小配線基板。並且，藉由包含導體電路寬度在150μm以下之導體電路圖案，可進一步使導體電路圖案高密度化。還可進一步縮短部分導體電路圖案的訊號線，使傳輸損失更低、達到更高速的傳輸。As mentioned above, a substrate with a conductive circuit pattern in the substrate is made and at least a part of the conductive circuit pattern includes a distance between circuits of 150 μm or less, so that the conductive circuit pattern in the substrate can be made high density and can be reduced. Wiring board. In addition, by including the conductor circuit pattern having a conductor circuit width of 150 μm or less, it is possible to further increase the density of the conductor circuit pattern. It can also further shorten the signal line of some conductor circuit patterns, so that the transmission loss is lower and the higher-speed transmission is achieved.
藉由使用本實施形態之樹脂組成物，即使在該電路距離更小的情況下，本實施形態之樹脂組成物依舊可發揮上述效果(絕緣性可靠性)。譬如，即使導體電路間之距離在150μm以下、或在100μm以下、在75μm以下、甚至在50μm以下，依舊可顯示絕緣可靠性。因此，本實施形態之樹脂組成物適合使用在配線間之距離狹窄的配線(電路)基板上。而且在配線基板中，在具備導電性貫通孔或/及導電性通孔(via hole)之多層配線基板，還可在形成於絕緣層之鄰接之導電性貫通孔間或/及導電性通孔間獲得優異的絕緣可靠性。By using the resin composition of this embodiment, even when the circuit distance is smaller, the resin composition of this embodiment can still exert the above-mentioned effect (insulation reliability). For example, even if the distance between conductor circuits is 150μm or less, 100μm or less, 75μm or less, or even 50μm or less, insulation reliability can still be displayed. Therefore, the resin composition of this embodiment is suitable for use on a wiring (circuit) board with a narrow distance between wirings. Moreover, in the wiring board, in a multilayer wiring board with conductive through holes or/and conductive via holes, it may be formed between adjacent conductive through holes or/and conductive through holes formed in the insulating layer Obtain excellent insulation reliability.
使用本實施形態之樹脂組成物製得的預浸體、附樹脂之薄膜、附樹脂之金屬箔兼具其硬化物之低介電特性、高Tg、絕緣可靠性等，因此於產業利用上非常有用。而且，包含其等之覆金屬積層板及配線基板亦具備低介電特性、高Tg及優異的絕緣可靠性。The prepreg, resin-coated film, and resin-coated metal foil made by using the resin composition of this embodiment have the low dielectric properties, high Tg, and insulation reliability of the cured product, so they are very useful in industrial applications. it works. Moreover, metal-clad laminates and wiring substrates including them also have low dielectric properties, high Tg, and excellent insulation reliability.
本說明書如上述揭示了各種態樣之技術，其中主要技術彙整如下。This specification discloses various types of technologies as described above, and the main technologies are summarized as follows.
本發明一態樣之樹脂組成物的特徵在於含有：聚苯醚化合物，其於分子末端具有下述式(1)所示之基；及下述交聯劑中之至少任一者：於分子中具有碳-碳不飽和雙鍵之交聯劑或可與前述聚苯醚化合物反應使其硬化之交聯劑；並且，前述聚苯醚化合物中之氯化物離子量在250ppm以下。The resin composition of one aspect of the present invention is characterized by containing: a polyphenylene ether compound having a group represented by the following formula (1) at the molecular end; and at least any one of the following crosslinking agents: A crosslinking agent having a carbon-carbon unsaturated double bond or a crosslinking agent that can react with the aforementioned polyphenylene ether compound to harden; and the amount of chloride ion in the aforementioned polyphenylene ether compound is 250 ppm or less.
[化學式8]
[式(1)中，R1 表示氫原子或碳數1~10之烷基，R2 表示碳數1~10之伸烷基]。 根據所述構成，可提供一種兼具硬化物之低介電特性、高Tg及優異絕緣可靠性的樹脂組成物。[In formula (1), R 1 represents a hydrogen atom or an alkyl group having 1 to 10 carbons, and R 2 represents an alkylene group having 1 to 10 carbons]. According to the above configuration, it is possible to provide a resin composition having the low dielectric properties of a cured product, high Tg, and excellent insulation reliability.
本發明之另一實施態樣之樹脂組成物，其特徵在於含有：聚苯醚化合物，其於分子末端具有下述式(1)所示之基；及下述交聯劑中之至少任一者：於分子中具有碳-碳不飽和雙鍵之交聯劑或可與前述聚苯醚化合物反應使其硬化之交聯劑；A resin composition according to another aspect of the present invention is characterized by containing: a polyphenylene ether compound having a group represented by the following formula (1) at the molecular end; and at least any one of the following crosslinking agents Those: a crosslinking agent that has a carbon-carbon unsaturated double bond in the molecule or a crosslinking agent that can react with the aforementioned polyphenylene ether compound to make it harden;
[化學式9]
[式(1)中，R1 表示氫原子或碳數1~10之烷基，R2 表示碳數1~10之伸烷基]；並且， 樹脂組成物或樹脂組成物之半硬化物中之氯化物離子量在40ppm以下。[In formula (1), R 1 represents a hydrogen atom or an alkyl group with 1 to 10 carbons, and R 2 represents an alkylene with 1 to 10 carbons]; and, the resin composition or the semi-cured material of the resin composition The chloride ion content is below 40ppm.
藉由所述構成，亦可提供一種兼具硬化物之低介電特性、高Tg及優異絕緣可靠性的樹脂組成物。With the above configuration, it is also possible to provide a resin composition that has the low dielectric properties of a cured product, high Tg, and excellent insulation reliability.
又，前述交聯劑宜含有選自於由以下所構成群組中之至少1種化合物：三聚異氰酸三烯基酯化合物、於分子中具有2個以上丙烯醯基之多官能丙烯酸酯化合物、於分子中具有2個以上甲基丙烯醯基之多官能甲基丙烯酸酯化合物、於分子中具有2個以上乙烯基之多官能乙烯基化合物、烯丙基化合物、馬來亞醯胺化合物及苊化合物。In addition, the aforementioned crosslinking agent preferably contains at least one compound selected from the group consisting of: a trienyl isocyanate compound, a polyfunctional acrylate having two or more acryl groups in the molecule Compounds, multifunctional methacrylate compounds having two or more methacrylic acid groups in the molecule, multifunctional vinyl compounds having two or more vinyl groups in the molecule, allyl compounds, and maleimide compounds And acenaphthene compounds.
吾等認為利用硬化反應可更順利地形成交聯，從而具有可進一步提高本實施形態中使用之樹脂組成物之硬化物的耐熱性的優點。We believe that the curing reaction can be used to form cross-links more smoothly, which has the advantage of further improving the heat resistance of the cured resin composition used in this embodiment.
並且，前述聚苯醚化合物宜具有下述式(2)所示結構。In addition, the aforementioned polyphenylene ether compound preferably has a structure represented by the following formula (2).
[化學式10]
(式(2)中，R3 ~R10 分別獨立表示氫原子、烷基、烯基、炔基、甲醯基、烷基羰基、烯基羰基或炔基羰基；X為前述式(1)所示之基)。(In formula (2), R 3 to R 10 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a methanoyl group, an alkylcarbonyl group, an alkenyl carbonyl group or an alkynyl carbonyl group; X is the aforementioned formula (1) The base shown).
又，式(2)中，A及B分別為下述式(3)及(4)所示結構：In addition, in formula (2), A and B are the structures represented by the following formulas (3) and (4):
[化學式11]
[化學式12]
(式(3)及(4)中，m及n分別表示0~20之整數；R11 ~R14 及R15 ~R18 分別獨立表示氫原子或烷基)。 並且，式(2)中，Y為下述式(5)所示結構：(In formulas (3) and (4), m and n each represent an integer from 0 to 20; R 11 to R 14 and R 15 to R 18 each independently represent a hydrogen atom or an alkyl group). And, in the formula (2), Y is the structure represented by the following formula (5):
[化學式13]
(式(5)中，R19 及R20 分別獨立表示氫原子或烷基)。(In formula (5), R 19 and R 20 each independently represent a hydrogen atom or an alkyl group).
吾等認為藉由所述構成，可更確實地獲得如上述之效果。We believe that the above-mentioned effects can be obtained more reliably by the above-mentioned configuration.
另，前述樹脂組成物宜為設有導體電路圖案之配線板用樹脂組成物，且該導體電路圖案之導體電路間之距離至少一部分在100μm以下。吾等認為在這類用途上，更能發揮本發明之效果。In addition, the aforementioned resin composition is preferably a resin composition for a wiring board provided with a conductor circuit pattern, and at least a part of the distance between the conductor circuits of the conductor circuit pattern is 100 μm or less. We believe that the effect of the present invention can be more exerted in such applications.
本發明之另一態樣之預浸體的特徵在於：具有上述樹脂組成物或前述樹脂組成物之半硬化物、與纖維質基材。Another aspect of the prepreg of the present invention is characterized by having the above-mentioned resin composition or the semi-cured product of the above-mentioned resin composition, and a fibrous base material.
本發明之另一態樣之附樹脂之薄膜的特徵在於：具有包含上述樹脂組成物或前述樹脂組成物之半硬化物的樹脂層、與支持薄膜。A film with resin according to another aspect of the present invention is characterized by having a resin layer including the above-mentioned resin composition or a semi-cured product of the above-mentioned resin composition, and a support film.
本發明之另一態樣之附樹脂之金屬箔的特徵在於：具有包含上述樹脂組成物或前述樹脂組成物之半硬化物的樹脂層、與金屬箔。The metal foil with resin according to another aspect of the present invention is characterized by having a resin layer containing the above-mentioned resin composition or a semi-cured product of the above-mentioned resin composition, and a metal foil.
本發明之另一態樣之覆金屬積層板的特徵在於：具有包含上述樹脂組成物之硬化物或上述預浸體之硬化物的絕緣層、與金屬箔。A metal-clad laminated board according to another aspect of the present invention is characterized by having an insulating layer including a cured product of the resin composition or a cured product of the prepreg, and a metal foil.
又，本發明之另一態樣之配線基板的特徵在於：具有包含上述樹脂組成物之硬化物或上述預浸體之硬化物的絕緣層、與配線。In addition, a wiring board according to another aspect of the present invention is characterized by having an insulating layer including a cured product of the resin composition or a cured product of the prepreg, and wiring.
根據上述之構成，可獲得一種可製得具有低介電特性與高Tg、具有更優異之絕緣可靠性之基板的預浸體、附樹脂之薄膜、附樹脂之金屬箔、覆金屬積層板、配線基板等。According to the above-mentioned structure, a prepreg, a resin-coated film, a resin-coated metal foil, a metal-clad laminate, a prepreg that can produce a substrate with low dielectric properties, high Tg, and better insulation reliability can be obtained. Wiring boards, etc.
以下將以實施例更具體說明本發明，惟本發明之範圍不受該等限定。 實施例The following examples will illustrate the present invention in more detail, but the scope of the present invention is not limited by these. Example
首先，在本實施例中，針對調製樹脂組成物時使用之成分加以說明。First, in this embodiment, the components used when preparing the resin composition will be described.
>A成分：聚苯醚化合物> ・改質PPE-1：2官能乙烯基苄基改質PPE(Mw：1900) 首先，合成改質聚苯醚(改質PPE-1)。另，將聚苯醚每1分子之分子末端的酚性羥基平均個數表示為末端羥基數。>Component A: Polyphenylene ether compound> ・Modified PPE-1: 2-functional vinylbenzyl modified PPE (Mw: 1900) First, synthetic modified polyphenylene ether (modified PPE-1). In addition, the average number of phenolic hydroxyl groups per molecule of polyphenylene ether is expressed as the number of terminal hydroxyl groups.
使聚苯醚與氯甲基苯乙烯反應而製得改質聚苯醚1(改質PPE-1)。具體上，首先於具備溫度調節器、攪拌裝置、冷卻設備及滴下漏斗之1公升的3口燒瓶中，饋入聚苯醚(SABIC Innovative Plastics公司製SA90，固有黏度(IV)0.083dl/g，末端羥基數1.9個，重量平均分子量Mw1700)200g、對氯甲基苯乙烯與間氯甲基苯乙烯之質量比為50：50的混合物30g、作為相轉移觸媒之溴化四正丁銨1.227g及甲苯400g並予以攪拌。而且持續攪拌直到聚苯醚、氯甲基苯乙烯及溴化四正丁銨溶解於甲苯為止。這時，緩慢地加熱，並加熱到最後液溫成為75℃為止。接著，於該溶液中耗時20分鐘滴下作為鹼金屬氫氧化物之氫氧化鈉水溶液(氫氧化鈉20g/水20g)。然後進一步在75℃下攪拌4小時。接下來，以10質量%之鹽酸將燒瓶之內容物進行中和，然後投入大量的甲醇。如此一來，可於燒瓶內之液體中產生沉澱物。即，使燒瓶內之反應液所含產物再次沉澱。然後，利用過濾取出該沉澱物，以甲醇與水之質量比為80：20的混合液洗淨3次後，在減壓下以80℃乾燥3小時。The modified polyphenylene ether 1 (modified PPE-1) was prepared by reacting polyphenylene ether with chloromethyl styrene. Specifically, polyphenylene ether (SA90 manufactured by SABIC Innovative Plastics, intrinsic viscosity (IV) 0.083dl/g) was first put into a 1-liter 3-neck flask equipped with a temperature regulator, a stirring device, a cooling device, and a dropping funnel. The number of terminal hydroxyl groups is 1.9, the weight average molecular weight is Mw1700) 200g, the mass ratio of p-chloromethyl styrene and m-chloromethyl styrene is 50:50 30g, tetra-n-butylammonium bromide as a phase transfer catalyst 1.227 g and 400 g of toluene and stirred. And continue to stir until the polyphenylene ether, chloromethylstyrene and tetra-n-butylammonium bromide are dissolved in toluene. At this time, heat slowly until the final liquid temperature reaches 75°C. Next, an aqueous sodium hydroxide solution (20 g of sodium hydroxide/20 g of water) as an alkali metal hydroxide was dropped in this solution over 20 minutes. Then it was further stirred at 75°C for 4 hours. Next, the contents of the flask were neutralized with 10% by mass hydrochloric acid, and then a large amount of methanol was added. In this way, precipitates can be generated in the liquid in the flask. That is, the product contained in the reaction liquid in the flask is precipitated again. Then, the precipitate was taken out by filtration, washed three times with a mixture of methanol and water in a mass ratio of 80:20, and then dried at 80° C. for 3 hours under reduced pressure.
將所得固體以1 H-NMR(400MHz，CDCl3 ，TMS)進行分析。測定NMR之結果，於5~7ppm確認了源自乙烯基苄基的尖峰。藉此得以確認，所得固體係於分子末端具有式(1)所示之基的改質聚苯醚。具體而言，確認為經乙烯基苄基化之聚苯醚。The obtained solid was analyzed by 1 H-NMR (400 MHz, CDCl 3 , TMS). As a result of NMR measurement, a sharp peak derived from a vinylbenzyl group was confirmed at 5 to 7 ppm. This confirmed that the obtained solid was a modified polyphenylene ether having a group represented by formula (1) at the molecular end. Specifically, it was confirmed to be a vinyl benzyl polyphenylene ether.
又，以GPC測定改質聚苯醚之分子量分布。然後，從所得分子量分布算出重量平均分子量(Mw)，結果Mw得1900。In addition, the molecular weight distribution of the modified polyphenylene ether was measured by GPC. Then, the weight average molecular weight (Mw) was calculated from the obtained molecular weight distribution. As a result, Mw was 1900.
又，以以下方式測定改質聚苯醚之末端官能基數。In addition, the number of terminal functional groups of the modified polyphenylene ether was measured in the following manner.
首先，正確秤量改質聚苯醚。令此時的重量為X(mg)。然後，使該經秤量之改質聚苯醚溶解於25mL二氯甲烷中，並於該溶液中添加100μL之10質量%氫氧化四乙銨(TEAH)之乙醇溶液(TEAH：乙醇(體積比)=15：85)後，使用UV分光光度計(股份有限公司島津製作所製UV-1600)，測定318nm之吸光度(Abs)。接著，從該測定結果以下述式算出改質聚苯醚之末端羥基數。First, correctly weigh the modified polyphenylene ether. Let the weight at this time be X (mg). Then, the weighed modified polyphenylene ether was dissolved in 25 mL of dichloromethane, and 100 μL of a 10% by mass tetraethylammonium hydroxide (TEAH) ethanol solution (TEAH: ethanol (volume ratio)) was added to the solution. =15:85), using a UV spectrophotometer (UV-1600 manufactured by Shimadzu Corporation) to measure the absorbance (Abs) at 318 nm. Next, from the measurement result, the number of terminal hydroxyl groups of the modified polyphenylene ether was calculated by the following formula.
剩餘OH量(μmol/g)=[(25×Abs)/(ε×OPL×X)]×106 在此，ε表示吸光係數，為4700L/mol・cm。又，OPL為測試槽光徑長度，為1cm。Residual OH amount (μmol/g)=[(25×Abs)/(ε×OPL×X)]×106 Here, ε represents the absorption coefficient, which is 4700L/mol·cm. In addition, OPL is the optical path length of the test slot, which is 1 cm.
然後，由所算出之改質聚苯醚的剩餘OH量(末端羥基數)幾乎為零的結果可知，改質前之聚苯醚的羥基幾乎都已被改質。由此可知，從改質前之聚苯醚的末端羥基數減少的減少量，即為改質前之聚苯醚的末端羥基數。即可知，改質前之聚苯醚的末端羥基數為改質聚苯醚之末端官能基數。亦即，末端官能基數為2個。Then, from the calculated result that the remaining OH amount (the number of terminal hydroxyl groups) of the modified polyphenylene ether is almost zero, it can be seen that almost all the hydroxyl groups of the polyphenylene ether before the modification have been modified. From this, it can be seen that the decrease in the number of terminal hydroxyl groups of the polyphenylene ether before modification is the number of terminal hydroxyl groups of the polyphenylene ether before modification. That is, the number of terminal hydroxyl groups of the polyphenylene ether before modification is the number of terminal functional groups of the modified polyphenylene ether. That is, the number of terminal functional groups is two.
並且，改質聚苯醚化合物中之不純物離子量係於試料(所得之改質PPE-1)0.75g中投入純水15g，在125℃下萃取20小時後，利用離子層析分析(使用機種「ICS1500」Thermo Fisher公司製，分離管柱：Ionpac AS22，溶析液：4.5mmol/L Na2 CO3 /1.4mmol/L NaHCO3 ，溶析液流量：1.5mL/分鐘)進行測定。結果，改質PPE-1中之各種不純物離子量以固體成分換算計，Cl- 離子得1912ppm。並且，Cl- 離子以外之其他離子得：Br- 離子小於2ppm，NO3 - 離子為10ppm，SO4 - 離子為2ppm，NO2 - 離子小於2ppm，PO4 3- 離子小於2ppm，Na+ 離子小於2ppm，NH4 + 離子為12ppm。In addition, the amount of impurity ions in the modified polyphenylene ether compound is that 0.75g of the sample (the modified PPE-1 obtained) is put into 15g of pure water, and after extraction at 125°C for 20 hours, it is analyzed by ion chromatography (use model "ICS1500" manufactured by Thermo Fisher, separation column: Ionpac AS22, eluent: 4.5 mmol/L Na 2 CO 3 /1.4 mmol/L NaHCO 3 , eluent flow rate: 1.5 mL/min) for measurement. As a result, the amount of various impurity ions in the modified PPE-1 was calculated as solid content, and Cl - ions were 1912 ppm. In addition, other ions other than Cl - ion are: Br - ion is less than 2ppm, NO 3 - ion is 10ppm, SO 4 - ion is 2ppm, NO 2 - ion is less than 2ppm, PO 4 3- ion is less than 2ppm, Na + ion is less than 2ppm, NH 4 + ion is 12ppm.
・改質PPE-2：2官能乙烯基苄基改質PPE(Mw：1900)
除了反覆3次(3組)下述步驟以外，以與改質PPE-1同樣方式獲得改質PPE-2：投入甲醇使燒瓶內之液體產生沉澱物的步驟，亦即使燒瓶內之反應液中所含產物再次沉澱的步驟；及，將該沉澱物過濾並取出的步驟。・Modified PPE-2: 2-functional vinylbenzyl modified PPE (Mw: 1900)
Except for repeating the following
以與改質PPE-1同樣方式測定所得改質PPE-2中之各種不純物離子量的結果，以固體成分換算計得：Cl- 離子為42ppm，Br- 離子小於2ppm，NO3 - 離子為29ppm，SO4 - 離子為14ppm，NO2 - 離子小於2ppm，PO4 3- 離子小於2ppm，Na+ 離子小於2ppm，NH4 + 離子為27ppm。The result of measuring the amount of various impurity ions in the modified PPE-2 obtained in the same way as the modified PPE-1, calculated in terms of solid content: Cl - ion is 42ppm, Br - ion is less than 2ppm, NO 3 - ion is 29ppm , SO 4 - ion as 14ppm, NO 2 - ions is less than 2ppm, PO 4 3- ions is less than 2ppm, Na + ions is less than 2ppm, NH 4 + ions to 27ppm.
・改質PPE-3：2官能乙烯基苄基改質PPE(Mw：1900) 除了反覆2次(2組)下述步驟以外，以與改質PPE-1同樣方式獲得改質PPE-3：投入甲醇使燒瓶內之液體產生沉澱物的步驟，亦即使燒瓶內之反應液中所含產物再次沉澱的步驟；及，將該沉澱物過濾並取出的步驟。・Modified PPE-3: 2-functional vinylbenzyl modified PPE (Mw: 1900) Except for repeating the following steps twice (2 sets), the modified PPE-3 is obtained in the same way as the modified PPE-1: the step of adding methanol to precipitate the liquid in the flask, even if the reaction liquid in the flask The step of re-precipitating the contained product; and the step of filtering and taking out the precipitate.
以與改質PPE-1同樣方式測定所得改質PPE-3中之各種不純物離子量的結果，以固體成分換算計得：Cl- 離子為42ppm，Br- 離子為2ppm，NO3 - 離子為41ppm，SO4 - 離子小於2ppm，NO2 - 離子小於2ppm，PO4 3- 離子小於2ppm，Na離子+ 為8ppm，NH4 + 離子為20ppm。In the results of various of the PPE-3 of the resulting modified impurity ions determining the amount of the PPE-1 in the same manner modified to terms of solid content obtained: Cl - ions 42ppm, Br - ions 2ppm, NO 3 - ions 41ppm , SO 4 - ions is less than 2ppm, NO 2 - ions is less than 2ppm, PO 4 3- ions is less than 2ppm, Na + ions is 8ppm, NH 4 + ions to 20ppm.
・改質PPE-4：2官能乙烯基苄基改質PPE(Mw：1900)
除了反覆3次(3組)下述步驟以外，以與改質PPE-1同樣方式獲得改質PPE-4：於改質PPE合成步驟時，使用鄰氯甲基苯乙烯與對氯甲基苯乙烯與間氯甲基苯乙烯之質量比為20：10：70的混合物，來替代對氯甲基苯乙烯與間氯甲基苯乙烯之質量比為50：50的混合物，並投入甲醇而使燒瓶內之液體產生沉澱物的步驟，亦即使燒瓶內之反應液中所含產物再次沉澱的步驟；及，將該沉澱物過濾並取出的步驟。・Modified PPE-4: 2-functional vinylbenzyl modified PPE (Mw: 1900)
Except for repeating the following
以與改質PPE-1同樣方式測定所得改質PPE-4中之各種不純物離子量的結果，以固體成分換算計得Cl- 離子為31ppm。並且，其他離子為：Br- 離子小於2ppm，NO3 - 離子小於2ppm，SO4 - 離子小於2ppm，NO2 - 離子小於2ppm，PO4 3- 離子小於2ppm，Na+ 離子為8ppm，NH4 + 離子為10ppm。As a result of measuring the amount of various impurity ions in the obtained modified PPE-4 in the same manner as the modified PPE-1, the Cl - ion was 31 ppm in terms of solid content. In addition, the other ions are: Br - ion is less than 2ppm, NO 3 - ion is less than 2ppm, SO 4 - ion is less than 2ppm, NO 2 - ion is less than 2ppm, PO 4 3- ion is less than 2ppm, Na + ion is 8ppm, NH 4 + The ion is 10 ppm.
・SA-9000：2官能甲基丙烯酸酯改質PPE(Mw：1700，SABIC公司製，Cl離子量：小於2ppm) ・OPE-2St 2200：末端乙烯基苄基改質PPE(Mw：約3600，三菱瓦斯化學股份有限公司製，Cl離子量：1350ppm)・SA-9000: PPE modified by 2-functional methacrylate (Mw: 1700, manufactured by SABIC, Cl ion content: less than 2ppm) ・OPE-2St 2200: PPE modified with terminal vinylbenzyl (Mw: about 3600, manufactured by Mitsubishi Gas Chemical Co., Ltd., Cl ion content: 1350 ppm)
>B成分：交聯劑> ・TAIC：三聚異氰酸三烯丙酯(日本化成股份有限公司製) ・DVB810：二乙烯基苯(新日鐵住金化學股份有限公司) ・DCP：二環戊二烯型甲基丙烯酸酯(新中村化學工業股份有限公司製)>B component: crosslinking agent> ・TAIC: Triallyl isocyanate (manufactured by Nippon Kasei Co., Ltd.) ・DVB810: Divinylbenzene (Nippon Steel & Sumikin Chemical Co., Ltd.) ・DCP: Dicyclopentadiene methacrylate (manufactured by Shinnakamura Chemical Industry Co., Ltd.)
>其他成分> (無機充填材) ・SC2300-SVJ：經甲基丙烯醯基矽烷表面處理之球狀二氧化矽(股份有限公司Admatechs製) (阻燃劑) ・SAYTEX8010：溴系阻燃劑(Albemarle日本股份有限公司製)>Other ingredients> (Inorganic filler) ・SC2300-SVJ: Spherical silicon dioxide surface-treated with methacrylic silane (manufactured by Admatechs Co., Ltd.) (Flame retardant) ・SAYTEX8010: Brominated flame retardant (manufactured by Albemarle Japan Co., Ltd.)
>實施例1~5、比較例1~3> [調製方法] (樹脂清漆) 首先，將各成分以表1中記載之摻混比率(質量份)，以固體成分濃度成為約60質量%的方式添加至甲苯中並予以混合。將該混合物在30℃下攪拌60分鐘，藉以製得清漆狀樹脂組成物(清漆)。>Examples 1~5, Comparative Examples 1~3> [Modulation method] (Resin varnish) First, each component was added to toluene at a blending ratio (parts by mass) described in Table 1 so that the solid content concentration became approximately 60% by mass, and mixed. The mixture was stirred at 30°C for 60 minutes to prepare a varnish-like resin composition (varnish).
(製作預浸體) ・預浸體I 使各實施例及比較例之樹脂清漆浸潤至玻璃布(旭化成股份有限公司製#L2116型)中後，在130℃下加熱乾燥約3分鐘而獲得預浸體。屆時，將樹脂組成物含量(樹脂含量)相對於預浸體重量調整成約56質量%。(Making prepreg) ・Prepreg I After impregnating the resin varnish of each example and comparative example into glass cloth (#L2116 type manufactured by Asahi Kasei Co., Ltd.), it was heated and dried at 130°C for about 3 minutes to obtain a prepreg. At that time, the resin composition content (resin content) is adjusted to approximately 56% by mass relative to the weight of the prepreg.
・預浸體II 使各實施例及比較例之樹脂清漆浸潤至玻璃布(旭化成股份有限公司製#L1078型)中後，在130℃下加熱乾燥約2分鐘而獲得預浸體。屆時，將樹脂組成物含量(樹脂含量)相對於預浸體重量調整成約70質量%。・Prepreg II After impregnating the resin varnish of each Example and Comparative Example into a glass cloth (#L1078 type manufactured by Asahi Kasei Co., Ltd.), it was heated and dried at 130°C for about 2 minutes to obtain a prepreg. At that time, the resin composition content (resin content) is adjusted to approximately 70% by mass relative to the weight of the prepreg.
(製作覆銅積層板) ・覆銅積層板I 將上述預浸體6片於其兩側配置厚12μm之銅箔(古河電氣工業股份有限公司製GT-MP)做成被壓體，在真空條件下，以溫度210℃且壓力30kgf/cm2 之條件加熱、加壓90分鐘而製得兩面接著有銅箔之厚度約0.75mm的覆銅積層板。(Production of copper-clad laminate) ・Copper-clad laminate I The six prepregs above are placed on both sides of copper foil (GT-MP manufactured by Furukawa Electric Co., Ltd.) with a thickness of 12 μm to be pressed. Under the conditions, heat and press for 90 minutes at a temperature of 210°C and a pressure of 30 kgf/cm 2 to prepare a copper-clad laminate with a thickness of about 0.75 mm with copper foil attached to both sides.
・積層板II
將上述預浸體-II 2片重疊並於其兩側配置厚18μm之銅箔(古河電氣工業股份有限公司製FV-WS)做成被壓體，在真空條件下，以溫度210℃且壓力30kgf/cm2
之條件加熱、加壓90分鐘而製得兩面接著有銅箔之厚度約0.18mm的覆銅積層板-II’。將所得積層板-II’使用乾膜進行曝光而形成包含導體電路寬度為100μm之處的電路圖案，並藉由氯化銅水溶液進行銅之蝕刻而獲得作成有導體電路的積層板-II”。作為前述導體電路圖案，製得了用以評估絕緣可靠性的梳狀型圖案(線條數：15條，線重疊部分：65mm)，該梳狀型圖案於內層包含以如圖7所示之L(導體電路寬度)/S(導體電路間之距離)：100μm/100μm的方式形成有導體電路51的電路圖案。相較於所得積層板-II”，將上述預浸體-II配置於上下兩側並更於其外側兩側配置厚度18μm之FV-WS銅箔，在真空條件下，以溫度210℃且壓力30kgf/cm2
之條件加熱、加壓90分鐘而獲得導體電路間之距離為100μm的積層板II。・Laminate Board II The above-mentioned prepreg-
>評估試驗> [介電特性(相對介電常數及介電正切)] 使用材料/阻抗分析儀(惠普公司製之HP4291A及HP16453A)測定評估基板在1GHz下的相對介電常數及介電正切。評估基板係使用已從上述覆銅積層板I去除銅箔的積層板。測定係以根據PC-TM-650 2.5.5.9之方法進行。>Evaluation Test> [Dielectric characteristics (relative dielectric constant and dielectric tangent)] A material/impedance analyzer (HP4291A and HP16453A manufactured by Hewlett-Packard Company) was used to measure the relative dielectric constant and dielectric tangent of the evaluation substrate at 1 GHz. As the evaluation substrate, a laminated board from which the copper foil was removed from the above-mentioned copper-clad laminated board I was used. The measurement was carried out in accordance with PC-TM-650 2.5.5.9.
[玻璃轉移溫度(Tg)] 將上述覆銅積層板I之外層銅箔整面蝕刻後，針對所得試樣使用示差掃描熱量計(DSC)測定玻璃轉移點(Tg)。測定係以根據IPC-TM-650 2.4.25之方法進行。[Glass transition temperature (Tg)] After the entire surface of the outer copper foil of the copper-clad laminate I was etched, the glass transition point (Tg) was measured for the obtained sample using a differential scanning calorimeter (DSC). The measurement is carried out according to the method of IPC-TM-650 2.4.25.
[絕緣可靠性] 使用上述積層板II，在85℃且濕度85%之環境下施加500小時100V之電壓，並每小時實施電阻值之連續測定。將即使施加500小時，電阻值也未曾電阻損耗至10＾7Ω以下者評估為合格(○)，電阻損耗至10＾7Ω以下者則評估為不合格(×)。[Insulation reliability] Using the above-mentioned laminated board II, apply a voltage of 100V for 500 hours under an environment of 85°C and 85% humidity, and carry out continuous measurement of the resistance value every hour. Even if it is applied for 500 hours, the resistance value does not have a resistance loss of 10＾7Ω or less as a pass (○), and the resistance loss is 10＾7Ω or less as a failure (×).
將以上結果列於以下表1。The above results are listed in Table 1 below.
[預浸體中之不純物離子量] 並針對實施例1-2及比較例1，亦測定了預浸體中之Cl離子量。具體上，是將上述預浸體I之樹脂成分過篩(100最小網目，200最大網目)，準備了0.75g。將之加至15g之純水中，在125℃下萃取20小時後，倒入離子層析分析儀(使用機種「ICS1500」Thermo Fisher公司製，分離管柱：Ionpac AS22，溶析液：4.5mmol/L Na2 CO3 / 1.4mmol/L NaHCO3 ，溶析液流量：1.5mL/分鐘)中，測定各種不純物離子量。使用上述離子層析分析機器可測出之不純物離子量數值的極限係至2ppm，檢測量比該值更小之不純物離子即小於2ppm。[The amount of impurity ions in the prepreg] For Example 1-2 and Comparative Example 1, the amount of Cl ions in the prepreg was also measured. Specifically, the resin component of the prepreg I was sieved (100 smallest mesh, 200 largest mesh), and 0.75 g was prepared. Add it to 15g of pure water, extract at 125°C for 20 hours, then pour it into an ion chromatography analyzer (use model "ICS1500" made by Thermo Fisher, separation column: Ionpac AS22, eluent: 4.5 mmol /L Na 2 CO 3 / 1.4mmol/L NaHCO 3 , eluent flow rate: 1.5 mL/min), measure the amount of various impurity ions. The limit of the amount of impurity ions that can be measured by the above ion chromatography analysis machine is 2ppm, and the amount of impurity ions that are smaller than this value is less than 2ppm.
其結果，各不純物離子量在實施例1中Cl- 離子為7ppm。並且，Cl- 離子以外之其他離子得：Br- 離子小於2ppm，NO3 - 離子為17ppm，SO4 - 離子為3ppm，NO2 - 離子小於2ppm，PO4 3- 離子小於2ppm，Na+ 離子小於2ppm，NH4 + 離子為10ppm，Ca離子為5ppm。As a result, in Example 1, the amount of each impurity ion was 7 ppm for Cl - ion. And, other ions other than Cl - ion are: Br - ion is less than 2ppm, NO 3 - ion is 17ppm, SO 4 - ion is 3ppm, NO 2 - ion is less than 2ppm, PO 4 3- ion is less than 2ppm, Na + ion is less than 2 ppm, NH 4 + ion is 10 ppm, and Ca ion is 5 ppm.
在實施例2中Cl- 離子為29ppm。並且，Cl- 離子以外之其他離子得：Br- 離子小於2ppm，NO3 - 離子為7ppm，SO4 - 離子為2ppm，NO2 - 離子小於2ppm，PO4 3- 離子小於2ppm，Na+ 離子小於2ppm，NH4 + 離子為9ppm，Ca2+ 離子為5ppm。In Example 2, the Cl - ion is 29 ppm. And, other ions other than Cl - ion are: Br - ion is less than 2ppm, NO 3 - ion is 7ppm, SO 4 - ion is 2ppm, NO 2 - ion is less than 2ppm, PO 4 3- ion is less than 2ppm, Na + ion is less than 2 ppm, NH 4 + ion is 9 ppm, and Ca 2+ ion is 5 ppm.
在實施例6中Cl- 離子為4ppm。並且，Cl- 離子以外之其他離子得：Br- 離子小於2ppm，NO3 - 離子為7ppm，SO4 - 離子為7ppm，NO2 - 離子小於2ppm，PO4 3- 離子小於2ppm，Na+ 離子為4ppm，NH4 + 離子為7ppm，Ca2+ 離子為6ppm。而，在比較例1中得：Cl- 離子為75ppm，Br- 離子小於2ppm，NO3 - 離子為15ppm，SO4 - 離子小於2ppm，NO2 - 離子小於2ppm，PO4 3- 離子小於2ppm，Na+ 離子小於2ppm，NH4 + 離子為7ppm，Ca2+ 離子小於2ppm。In Example 6, the Cl - ion is 4 ppm. And, other ions other than Cl - ion are: Br - ion is less than 2ppm, NO 3 - ion is 7ppm, SO 4 - ion is 7ppm, NO 2 - ion is less than 2ppm, PO 4 3- ion is less than 2ppm, Na + ion is 4 ppm, NH 4 + ion is 7 ppm, and Ca 2+ ion is 6 ppm. However, in Comparative Example 1: Cl - ions are 75 ppm, Br - ions are less than 2 ppm, NO 3 - ions are 15 ppm, SO 4 - ions are less than 2 ppm, NO 2 - ions are less than 2 ppm, and PO 4 3- ions are less than 2 ppm. Na + ions are less than 2 ppm, NH 4 + ions are 7 ppm, and Ca 2+ ions are less than 2 ppm.
[表1]
(考察) 如從表1所示結果明示，藉由本發明可提供一種兼具低介電特性(Dk：3.3以下，Df：0.0015以下)及高Tg以及優異絕緣可靠性的樹脂組成物。(Survey) As is clear from the results shown in Table 1, the present invention can provide a resin composition that has both low dielectric properties (Dk: 3.3 or less, Df: 0.0015 or less), high Tg, and excellent insulation reliability.
相對地，在比較例1及3中使用了Cl離子量多的聚苯醚化合物，無法獲得充分的絕緣可靠性。而且，在比較例2中使用了於分子末端不具上述式(1)所示之基的聚苯醚化合物，結果為Tg不佳。In contrast, in Comparative Examples 1 and 3, a polyphenylene ether compound having a large amount of Cl ions was used, and sufficient insulation reliability could not be obtained. In addition, in Comparative Example 2, a polyphenylene ether compound having no group represented by the above formula (1) at the molecular terminal was used, and as a result, the Tg was poor.
本申請案係以已於2018年9月19日提申之日本專利申請案特願2018-174980為基礎，且本申請案包含其內容。This application is based on Japanese Patent Application No. 2018-174980 filed on September 19, 2018, and this application includes its content.
為了闡述本發明，於前述中參照具體例及圖式等，同時透過實施形態適當且充分說明了本發明，惟應知悉，只要是熟知此項技藝之人士，可輕易地變更及/或改良前述實施形態。因此，熟知此項技藝之人士實施之變更形態或改良形態，只要未脫離申請專利範圍所載請求項的權利範圍，即可解釋為該請求項之權利範圍含括該變更形態或該改良形態。In order to illustrate the present invention, specific examples and drawings are referred to in the foregoing, and the present invention is adequately and fully explained through implementation forms. However, it should be understood that as long as a person familiar with the art can easily change and/or improve the foregoing Implementation form. Therefore, a modification or improvement implemented by a person familiar with the art, as long as it does not deviate from the scope of the claim contained in the patent application, can be interpreted as the scope of the claim including the modification or improvement.
產業上之可利用性 本發明在涉及電子材料及使用其之各種設備的技術領域中，具有廣泛的產業上之可利用性。Industrial availability The present invention has a wide range of industrial applicability in the technical field involving electronic materials and various devices using them.
1:預浸體
2:樹脂組成物或樹脂組成物之半硬化物
3:纖維質基材
11:覆金屬積層板
12:絕緣層
13:金屬箔
14:配線
21:配線基板
31:附樹脂之金屬箔
32、42:樹脂層
41:附樹脂之薄膜
43:支持薄膜
51:導體電路
L:導體電路寬度
S:導體電路間之距離1: Prepreg
2: Resin composition or semi-hardened resin composition
3: Fibrous substrate
11: Metal-clad laminate
12: Insulation layer
13: Metal foil
14: Wiring
21: Wiring board
31: Metal foil with
圖1係顯示本發明一實施形態之預浸體的構成之概略截面圖。 圖2係顯示本發明一實施形態之覆金屬積層板的構成之概略截面圖。 圖3係顯示本發明一實施形態之配線基板的構成之概略截面圖。 圖4係顯示本發明一實施形態之附樹脂之金屬箔的構成之概略截面圖。 圖5係顯示本發明一實施形態之樹脂薄膜的構成之概略截面圖。 圖6係顯示具有本發明一實施形態之導體電路圖案的基板中，相鄰之二個配線(導體電路)(L)之間之距離(space)S的概略圖。 圖7係顯示實施例中用以評估絕緣可靠性之梳狀型圖案的概略圖。Fig. 1 is a schematic cross-sectional view showing the structure of a prepreg according to an embodiment of the present invention. Fig. 2 is a schematic cross-sectional view showing the structure of a metal-clad laminate according to an embodiment of the present invention. Fig. 3 is a schematic cross-sectional view showing the structure of a wiring board according to an embodiment of the present invention. Fig. 4 is a schematic cross-sectional view showing the structure of a metal foil with resin according to an embodiment of the present invention. Fig. 5 is a schematic cross-sectional view showing the structure of a resin film according to an embodiment of the present invention. Fig. 6 is a schematic view showing the distance (space) S between two adjacent wirings (conductor circuits) (L) in a substrate having a conductor circuit pattern according to an embodiment of the present invention. FIG. 7 is a schematic diagram showing a comb-shaped pattern used to evaluate insulation reliability in the embodiment.
1:預浸體 1: Prepreg
2:樹脂組成物或樹脂組成物之半硬化物 2: Resin composition or semi-hardened resin composition
3:纖維質基材 3: Fibrous substrate
Claims (10)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018-174980 | 2018-09-19 | ||
| JP2018174980 | 2018-09-19 |
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|---|---|
| TW202022017A true TW202022017A (en) | 2020-06-16 |
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| Country | Link |
|---|---|
| JP (1) | JPWO2020059562A1 (en) |
| CN (1) | CN112469750A (en) |
| TW (1) | TW202022017A (en) |
| WO (1) | WO2020059562A1 (en) |
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| JP2023120458A (en) * | 2020-07-10 | 2023-08-30 | Ａｇｃ株式会社 | Resin composition, prepreg, metallic foil with resin, film with resin, metal-clad laminate, and wiring board, and method for producing modified polyphenylene ether |
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|---|---|---|---|---|
| EP2006318B1 (en) * | 2007-06-18 | 2014-04-30 | Mitsubishi Gas Chemical Company, Inc. | Process for the production of vinyl compound |
| JP4824658B2 (en) * | 2007-10-19 | 2011-11-30 | 第一工業製薬株式会社 | Method for producing vinylbenzylated polyphenylene ether compound |
| JP6147538B2 (en) * | 2013-03-28 | 2017-06-14 | 第一工業製薬株式会社 | Method for producing vinylbenzylated polyphenylene ether compound |
| JP6504386B2 (en) * | 2014-12-16 | 2019-04-24 | パナソニックＩｐマネジメント株式会社 | Polyphenylene ether resin composition, prepreg, metal-clad laminate and printed wiring board |
| JP6724305B2 (en) * | 2015-07-24 | 2020-07-15 | 三菱瓦斯化学株式会社 | Prepreg |
| US11078361B2 (en) * | 2016-10-17 | 2021-08-03 | Panasonic Intellectual Property Management Co., Ltd. | Resin composition, method for producing resin composition, prepreg, film with resin, metal foil with resin, metal-clad laminate, and wiring board |
| CN112020523B (en) * | 2018-04-27 | 2023-10-24 | 松下知识产权经营株式会社 | Resin composition, prepreg, resin-coated film, resin-coated metal foil, metal foil-clad laminate, and wiring board |
-
2019
- 2019-09-09 WO PCT/JP2019/035392 patent/WO2020059562A1/en active Application Filing
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