JP6405818B2 - Film for electronic circuit board and electronic circuit board - Google Patents
Film for electronic circuit board and electronic circuit board Download PDFInfo
- Publication number
- JP6405818B2 JP6405818B2 JP2014187635A JP2014187635A JP6405818B2 JP 6405818 B2 JP6405818 B2 JP 6405818B2 JP 2014187635 A JP2014187635 A JP 2014187635A JP 2014187635 A JP2014187635 A JP 2014187635A JP 6405818 B2 JP6405818 B2 JP 6405818B2
- Authority
- JP
- Japan
- Prior art keywords
- electronic circuit
- film
- circuit board
- liquid crystal
- less
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Production Of Multi-Layered Print Wiring Board (AREA)
- Manufacturing Of Printed Wiring (AREA)
Description
本発明は、レーザー照射部分に選択的に金属をめっきする方法により微細な電子回路を形成可能なものであり、且つ誘電特性に極めて優れた電子回路基板用フィルムと、当該電子回路基板用フィルムに電子回路を形成したものである電子回路基板に関するものである。 The present invention is capable of forming a fine electronic circuit by a method of selectively plating a metal on a laser-irradiated portion, and has an extremely excellent dielectric property, and the electronic circuit board film. The present invention relates to an electronic circuit board on which an electronic circuit is formed.
従来、電子回路基板を作製するには、一般的に、材料基板に銅箔などの金属箔を熱融着したり接着剤を用いて貼り付けたり、また、スパッタや蒸着、無電解めっき法などで材料基板上に金属層を形成した後に、回路パターン以外の部分を化学エッチングにより除去して電子回路を形成していた。 Conventionally, in order to produce an electronic circuit board, generally, a metal foil such as a copper foil is thermally fused or bonded with an adhesive to a material board, or sputtering, vapor deposition, electroless plating method, etc. After forming the metal layer on the material substrate, the part other than the circuit pattern was removed by chemical etching to form an electronic circuit.
しかし、上記の方法では高精細回路パターンを形成することが難しく、また、コスト面での問題もあった。さらに、材料基板に電子回路を形成した後に曲げ加工や絞り加工して立体基板とする場合には、金属層が切断されてしまうことがあった。 However, in the above method, it is difficult to form a high-definition circuit pattern, and there is a problem in terms of cost. Furthermore, when a three-dimensional substrate is formed by bending or drawing after forming an electronic circuit on a material substrate, the metal layer may be cut.
そこで、ＬＤＳ法（Ｌａｓｅｒ Ｄｉｒｅｃｔ Ｓｔｒｕｃｔｕｒｉｎｇ法）など、基板中にレーザー照射で活性化される金属酸化物結晶を分散させ、当該基板の回路形成部分にレーザーを照射することにより選択的にめっき性を付与した後、レーザー照射部分に金属をめっきする方法が開発されている（特許文献１〜５）。 Therefore, metal oxide crystals activated by laser irradiation are dispersed in the substrate such as LDS method (Laser Direct Structure method) and the circuit forming portion of the substrate is irradiated with laser to selectively impart plating properties. After that, a method of plating a metal on the laser irradiated portion has been developed (Patent Documents 1 to 5).
また、特許文献６には、触媒顆粒を含み且つ犠牲層を含む複合材料誘電層を基板上に積層し、触媒顆粒を選択的に活性化して導線層を形成した後に犠牲層を除去することにより回路基板を作製する方法が開示されている。 Patent Document 6 discloses that a composite dielectric layer including catalyst granules and a sacrificial layer is stacked on a substrate, and the catalyst granules are selectively activated to form a conductive layer, and then the sacrificial layer is removed. A method of making a circuit board is disclosed.
上述したように、ＬＤＳ法など、レーザーを用いて高精細パターンを低コストで形成できる方法が開発されている。 As described above, a method capable of forming a high-definition pattern at low cost using a laser, such as an LDS method, has been developed.
しかし、ＬＤＳ法などに適用される従来の電子回路基板用フィルムは、電子回路を形成すべき基板に光活性金属酸化物結晶を分散させる必要があり、また、基材フィルムの配向を緩和する目的で無機物フィラーを比較的多量に配合する必要があるため、電子回路基板全体の誘電特性が低下してしまい、高周波回路に適用することができないという問題がある。 However, the conventional film for an electronic circuit board applied to the LDS method needs to disperse the photoactive metal oxide crystal on the substrate on which the electronic circuit is to be formed, and also has the purpose of relaxing the orientation of the base film. However, since it is necessary to mix a relatively large amount of the inorganic filler, the dielectric characteristics of the entire electronic circuit board are deteriorated, and there is a problem that it cannot be applied to a high frequency circuit.
そこで本発明は、ＬＤＳ法などにより微細な電子回路を形成可能なものであり、且つ誘電特性に極めて優れた電子回路基板用フィルムと、当該電子回路基板用フィルムに電子回路を形成したものである電子回路基板を提供することを主たる目的とする。 Therefore, the present invention is capable of forming a fine electronic circuit by an LDS method or the like, and has an extremely excellent dielectric property, and an electronic circuit is formed on the electronic circuit board film. The main object is to provide an electronic circuit board.
本発明者らは、上記課題を解決するために鋭意研究を重ねた。その結果、液晶ポリマーからなる基材フィルム中にＬＤＳ法などのための光活性金属酸化物結晶を所定量分散させ、且つ平面方向において特定の線膨張係数と配向性を示す液晶ポリマー基材フィルムを用いることにより、ＬＤＳ法などにより電子回路を形成できるのみならず、高性能アンテナなどへの使用に耐え得るレベルまで誘電特性に優れた電子回路基板用フィルムが得られることを見出して、本発明を完成した。 The inventors of the present invention have made extensive studies to solve the above problems. As a result, a liquid crystal polymer base film in which a predetermined amount of photoactive metal oxide crystals for the LDS method or the like are dispersed in a base film made of a liquid crystal polymer and has a specific linear expansion coefficient and orientation in the plane direction is obtained. By using the present invention, it has been found that an electronic circuit board film excellent in dielectric characteristics can be obtained not only to form an electronic circuit by an LDS method or the like but also to a level that can be used for a high performance antenna or the like. completed.
以下、本発明を示す。 Hereinafter, the present invention will be described.
［１］ 液晶ポリマーから成形される基材フィルム中に光活性金属酸化物結晶が分散している構成を有し、
全体に対する上記光活性金属酸化物結晶の割合が５質量％以上、２０質量％以下であり、
上記基材フィルムの平面方向の線膨張係数が３ｐｐｍ／℃以上、３０ｐｐｍ／℃以下であり、且つ、平面方向の一方向での線膨張係数と当該方向に直交する方向の線膨張係数との比が０．４以上、２．５以下であることを特徴とする電子回路基板用フィルム。
[1] A structure in which photoactive metal oxide crystals are dispersed in a base film formed from a liquid crystal polymer,
The ratio of the photoactive metal oxide crystal to the whole is 5 mass% or more and 20 mass% or less
The ratio of the linear expansion coefficient in the plane direction of the substrate film to 3 ppm / ° C. or more and 30 ppm / ° C. or less, and the linear expansion coefficient in one direction of the plane direction and the linear expansion coefficient in the direction orthogonal to the direction. Is a film for electronic circuit boards, characterized by being 0.4 or more and 2.5 or less.
［２］ 上記基材フィルム中に光活性金属酸化物結晶に加えて光非活性無機物が分散している構成を有し、全体に対する上記光活性金属酸化物結晶と上記光非活性無機物との合計の割合が２５質量％以下である上記［１］に記載の電子回路基板用フィルム。光非活性無機物により、例えば、液晶ポリマーを溶融加工する際に生じる分子配向の異方性など、必須成分である液晶ポリマーや光活性金属酸化物結晶に由来する欠点を克服することができ、また、光活性金属酸化物結晶と光非活性無機物の量を所定量とすることにより、液晶ポリマー由来の優れた誘電特性も維持することが可能になる。 [2] A structure in which a photoinactive inorganic substance is dispersed in addition to the photoactive metal oxide crystal in the base film, and the total of the photoactive metal oxide crystal and the photoinactive inorganic substance with respect to the whole The film for electronic circuit boards according to the above [1], wherein the ratio of is 25 mass% or less. The photo-inactive inorganic material can overcome the disadvantages derived from the liquid crystal polymer and photoactive metal oxide crystals, which are essential components, such as the anisotropy of molecular orientation that occurs when the liquid crystal polymer is melt processed, By setting the amounts of the photoactive metal oxide crystal and the photoinactive inorganic substance to a predetermined amount, it is possible to maintain excellent dielectric properties derived from the liquid crystal polymer.
［３］ 比誘電率が３．７以下で且つ誘電正接が０．００７以下である上記［１］または［２］に記載の電子回路基板用フィルム。 [3] The film for an electronic circuit board according to the above [1] or [2], wherein the relative dielectric constant is 3.7 or less and the dielectric loss tangent is 0.007 or less.
［４］ 厚さが１０μｍ以上、１０００μｍ以下である上記［１］〜［３］のいずれかに記載の電子回路基板用フィルム。当該厚さが１０μｍ以上であれば、基板としての強度を十分に確保することができ、また、多層板にした場合などにおける層間絶縁性も確保することができる。一方、厚過ぎると電子回路基板全体が重くなってしまったり、絞り加工などし難くなるおそれがあり得るので、１０００μｍ以下が好ましい。 [4] The film for electronic circuit boards according to any one of [1] to [3], wherein the thickness is 10 μm or more and 1000 μm or less. If the said thickness is 10 micrometers or more, the intensity | strength as a board | substrate can fully be ensured and the interlayer insulation in the case of using a multilayer board etc. can also be ensured. On the other hand, if it is too thick, the entire electronic circuit board may become heavy or it may be difficult to perform drawing or the like, so 1000 μm or less is preferable.
［５］ 上記液晶ポリマーがＩ型液晶ポリマーまたはＩＩ型液晶ポリマーである上記［１］〜［４］のいずれかに記載の電子回路基板用フィルム。Ｉ型液晶ポリマーまたはＩＩ型液晶ポリマーは、耐熱性や耐加水分解性により一層優れる。 [5] The electronic circuit board film according to any one of [1] to [4], wherein the liquid crystal polymer is an I-type liquid crystal polymer or an II-type liquid crystal polymer. I-type liquid crystal polymer or II-type liquid crystal polymer is more excellent in heat resistance and hydrolysis resistance.
［６］ 吸水率が０．２％以下である上記［１］〜［５］のいずれかに記載の電子回路基板用フィルム。吸水率を当該範囲に調整することで、吸湿に起因する誘電特性の変動や、配線間のショート現象（イオンマイグレーション）、はんだ実装時の基板膨れ不良などを発生し難くすることができる。 [6] The film for electronic circuit boards according to any one of [1] to [5], wherein the water absorption is 0.2% or less. By adjusting the water absorption rate within this range, it is possible to make it difficult to cause variations in dielectric characteristics due to moisture absorption, short-circuiting phenomenon (ion migration) between wirings, defective board swelling during solder mounting, and the like.
［７］ 上記［１］〜［６］のいずれかに記載の電子回路基板用フィルムの片面に回路が形成されたものであることを特徴とする電子回路基板。 [7] An electronic circuit board, wherein a circuit is formed on one side of the film for electronic circuit board according to any one of [1] to [6].
［８］ 上記［１］〜［６］のいずれかに記載の電子回路基板用フィルムの両面に回路が形成されたものであることを特徴とする電子回路基板。 [8] An electronic circuit board, wherein circuits are formed on both sides of the electronic circuit board film according to any one of [1] to [6].
［９］ 上記［７］または［８］に記載の電子回路基板が２以上積層されたものであることを特徴とする多層電子回路基板。 [9] A multilayer electronic circuit board, wherein two or more electronic circuit boards according to the above [7] or [8] are laminated.
本発明に係る電子回路基板用フィルムには、ＬＤＳ法などにより電子回路を形成可能であるため、電子回路形成のために銅箔などを積層する必要がない。また、平面方向において特定の線膨張係数と配向性を示す液晶ポリマー基材フィルムを用いることから、配向緩和を目的とする無機物フィラーの使用量を抑制できるため、本発明に係る電子回路基板用フィルムの誘電特性は非常に優れている。よって、本発明に係る電子回路基板用フィルムから製造される電子回路基板は、１ＧＨｚ以上といった高周波でも伝送損失が抑制されており、高周波製品に用いるアンテナ基板や伝送路基板として非常に有用である。 Since an electronic circuit can be formed on the electronic circuit board film according to the present invention by an LDS method or the like, it is not necessary to laminate a copper foil or the like for forming the electronic circuit. In addition, since the liquid crystal polymer base film showing a specific linear expansion coefficient and orientation in the planar direction is used, the amount of inorganic filler used for the purpose of orientation relaxation can be suppressed, so the film for electronic circuit boards according to the present invention The dielectric properties are very good. Therefore, the electronic circuit board manufactured from the film for an electronic circuit board according to the present invention has a suppressed transmission loss even at a high frequency of 1 GHz or more, and is very useful as an antenna substrate or a transmission path substrate used for a high-frequency product.
また、本発明の電子回路基板用フィルムは、絞り加工などした後にＬＤＳ法などを適用することにより、三次元の立体電子回路基板とすることもできる。さらに、本発明の電子回路基板用フィルムは、複数枚重ね合わせて熱プレスで液晶ポリマーを熱融着させ一体化させることができるので、一括多層工法による電子回路基板の材料としても好適なものである。 In addition, the electronic circuit board film of the present invention can be made into a three-dimensional three-dimensional electronic circuit board by applying an LDS method after drawing or the like. Furthermore, since the electronic circuit board film of the present invention can be laminated and integrated by heat-sealing the liquid crystal polymer by hot pressing, it is also suitable as a material for an electronic circuit board by a batch multilayer method. is there.
本発明に係る電子回路基板用フィルムは、液晶ポリマーからなる基材フィルム中に光活性金属酸化物結晶が分散している構成を有する。 The film for electronic circuit boards according to the present invention has a configuration in which photoactive metal oxide crystals are dispersed in a base film made of a liquid crystal polymer.
液晶ポリマーには、溶融状態で液晶性を示すサーモトロピック液晶ポリマーと、溶液状態で液晶性を示すレオトロピック液晶ポリマーとがある。本発明では何れの液晶ポリマーも用い得るが、耐熱性や難燃性がより優れることから、サーモトロピック液晶ポリマーを好適に用いる。 The liquid crystal polymer includes a thermotropic liquid crystal polymer exhibiting liquid crystallinity in a molten state and a rheotropic liquid crystal polymer exhibiting liquid crystallinity in a solution state. In the present invention, any liquid crystal polymer can be used, but a thermotropic liquid crystal polymer is preferably used because it is more excellent in heat resistance and flame retardancy.
サーモトロピック液晶ポリマーのうちサーモトロピック液晶ポリエステル（以下、単に「液晶ポリエステル」という）とは、例えば、芳香族ヒドロキシカルボン酸を必須のモノマーとし、芳香族ジカルボン酸や芳香族ジオールなどのモノマーと反応させることにより得られる芳香族ポリエステルであって、溶融時に液晶性を示すものである。その代表的なものとしては、パラヒドロキシ安息香酸（ＰＨＢ）と、フタル酸と、４，４’−ビフェノールから合成されるＩ型［下式（１）］、ＰＨＢと２，６−ヒドロキシナフトエ酸から合成されるＩＩ型［下式（２）］、ＰＨＢと、テレフタル酸と、エチレングリコールから合成されるＩＩＩ型［下式（３）］が挙げられる。 Among the thermotropic liquid crystal polymers, a thermotropic liquid crystal polyester (hereinafter simply referred to as “liquid crystal polyester”) is, for example, an aromatic hydroxycarboxylic acid as an essential monomer and reacted with a monomer such as an aromatic dicarboxylic acid or aromatic diol. It is an aromatic polyester obtained by this, and exhibits liquid crystallinity when melted. Typical examples thereof include type I [Formula (1)] synthesized from parahydroxybenzoic acid (PHB), phthalic acid, and 4,4′-biphenol, PHB and 2,6-hydroxynaphthoic acid. Type II [Formula (2)] synthesized from the above, Type III [Formula (3)] synthesized from PHB, terephthalic acid, and ethylene glycol.
本発明においては、耐熱性や耐加水分解性により優れることから、上記のうちＩ型液晶ポリエステルとＩＩ型液晶ポリエステルが好ましい。 In the present invention, among them, I-type liquid crystal polyester and II-type liquid crystal polyester are preferable because they are superior in heat resistance and hydrolysis resistance.
上記式（１）において、フタル酸としてはイソフタル酸が好ましい。 In the above formula (1), isophthalic acid is preferable as phthalic acid.
基材フィルムの厚さは適宜調整すればよいが、１０μｍ以上、１０００μｍ以下が好ましい。当該厚さが１０μｍ以上であれば、基板としての強度を十分に確保することができ、また、多層板にした場合などにおける層間絶縁性も確保することができる。一方、厚さの上限は特に制限されないが、厚過ぎると電子回路基板全体が重くなってしまったり、絞り加工などし難くなるおそれがあり得るので、１０００μｍ以下が好ましい。当該厚さとしては２０μｍ以上がより好ましく、また、５００μｍ以下がより好ましく、３００μｍ以下がさらに好ましい。 The thickness of the base film may be appropriately adjusted, but is preferably 10 μm or more and 1000 μm or less. If the said thickness is 10 micrometers or more, the intensity | strength as a board | substrate can fully be ensured and the interlayer insulation in the case of using a multilayer board etc. can also be ensured. On the other hand, the upper limit of the thickness is not particularly limited, but if it is too thick, the entire electronic circuit board may become heavy or it may be difficult to perform drawing or the like, and is preferably 1000 μm or less. The thickness is more preferably 20 μm or more, more preferably 500 μm or less, and further preferably 300 μm or less.
液晶ポリマーフィルムの誘電特性は一般的に優れているといえる。しかし本発明では、電子回路基板用フィルムまたは電子回路基板の全体での誘電特性の改善を課題の一つとしているため、特に誘電特性に優れた液晶ポリマーフィルムを基材として用いることが好ましい。具体的には、液晶ポリマー基材フィルムの比誘電率としては３．４以下が好ましく、誘電正接としては０．００３以下が好ましい。 It can be said that the dielectric properties of the liquid crystal polymer film are generally excellent. However, in the present invention, since improvement of dielectric characteristics of the electronic circuit board film or the entire electronic circuit board is one of the problems, it is particularly preferable to use a liquid crystal polymer film having excellent dielectric characteristics as the base material. Specifically, the dielectric constant of the liquid crystal polymer base film is preferably 3.4 or less, and the dielectric loss tangent is preferably 0.003 or less.
本発明に係る電子回路基板用フィルムでは、ＬＤＳ法などによる電子回路の形成を可能にするために、液晶ポリマー基材フィルム中に光活性金属酸化物結晶が分散している構成を有する。 The film for an electronic circuit board according to the present invention has a configuration in which photoactive metal oxide crystals are dispersed in a liquid crystal polymer base film in order to enable formation of an electronic circuit by an LDS method or the like.
光活性金属酸化物結晶は、レーザー照射により二価金属原子と酸素原子との間の結合が切断されて活性化し、当該二価金属原子にめっき金属が付着できるようになるものであり、例えば、以下の化学式で表され且つスピネル型結晶構造を有するものを挙げることができる。
ＡＢ2Ｏ4またはＢＡＢＯ4
［式中、Ａは、カドミウム、亜鉛、銅、コバルト、マグネシウム、スズ、チタン、鉄、アルミニウム、ニッケル、マンガンおよびクロムからなる群から選択される二価金属を示し；Ｂは、カドミウム、マンガン、ニッケル、亜鉛、銅、コバルト、マグネシウム、スズ、チタン、鉄、アルミニウムおよびクロムからなる群から選択される三価金属を示す］
The photoactive metal oxide crystal is activated by cutting the bond between the divalent metal atom and the oxygen atom by laser irradiation, and allows the plating metal to adhere to the divalent metal atom. Examples thereof include those represented by the following chemical formula and having a spinel crystal structure.
AB 2 O 4 or BABO 4
Wherein A represents a divalent metal selected from the group consisting of cadmium, zinc, copper, cobalt, magnesium, tin, titanium, iron, aluminum, nickel, manganese and chromium; B represents cadmium, manganese, Indicates a trivalent metal selected from the group consisting of nickel, zinc, copper, cobalt, magnesium, tin, titanium, iron, aluminum and chromium]
光活性金属酸化物結晶の平均粒子径は適宜調整すればよいが、樹脂フィルム中への分散のし易さや調製のし易さなどの観点から、５０ｎｍ以上、１０μｍ以下が好ましい。 The average particle size of the photoactive metal oxide crystal may be adjusted as appropriate, but is preferably 50 nm or more and 10 μm or less from the viewpoint of ease of dispersion in the resin film and ease of preparation.
本発明に係る電子回路基板用フィルムにおいては、全体に対する光活性金属酸化物結晶の割合を５質量％以上、２０質量％以下とする。上記割合を５質量％以上とすることにより、ＬＤＳ法などによる電子回路の形成をより容易かつ確実に行えるようにする。一方、光活性金属酸化物結晶は誘電特性を貶めるので、上記割合を２０質量％以下にすることにより、フィルム全体の誘電特性を優れたものにすることができる。 In the film for electronic circuit boards according to the present invention, the ratio of the photoactive metal oxide crystal to the whole is 5 mass% or more and 20 mass% or less. By setting the ratio to 5% by mass or more, an electronic circuit can be formed more easily and reliably by the LDS method or the like. On the other hand, since the photoactive metal oxide crystal gives up the dielectric properties, the dielectric properties of the entire film can be made excellent by setting the above ratio to 20% by mass or less.
本発明に係る電子回路基板用フィルムでは、フィルム加工性の向上、絶縁性の向上、レーザー吸収性の向上などの目的で、液晶ポリマー基材フィルム中に光活性を示さない無機物を分散させてもよい。かかる無機物としては、例えば、酸化珪素、窒化珪素、酸化アルミニウム、酸化チタンなどからなる無機物フィラーを挙げることができる。当該無機物フィラーの形状は特に制限されず、例えば、球状、板状、棒状、針状、不定形状などを挙げることができ、また、当該無機フィラーの大きさとしては５０ｎｍ以上、１０μｍ以下が好ましい。なお、当該無機フィラーの大きさは、その拡大写真における各無機フィラーの最長部を測定してもよいし、また、粒度分布測定から求めた体積平均粒子径や個数平均粒子径としてもよい。 In the electronic circuit board film according to the present invention, an inorganic substance that does not exhibit photoactivity may be dispersed in the liquid crystal polymer base film for the purpose of improving film processability, improving insulation, and improving laser absorption. Good. Examples of such an inorganic substance include inorganic fillers made of silicon oxide, silicon nitride, aluminum oxide, titanium oxide, and the like. The shape of the inorganic filler is not particularly limited, and examples thereof include a spherical shape, a plate shape, a rod shape, a needle shape, and an indefinite shape, and the size of the inorganic filler is preferably 50 nm or more and 10 μm or less. In addition, the magnitude | size of the said inorganic filler may measure the longest part of each inorganic filler in the enlarged photograph, and is good also as a volume average particle diameter and number average particle diameter calculated | required from the particle size distribution measurement.
本発明に係る電子回路基板用フィルムにおいては、全体に対する光活性金属酸化物結晶と光非活性無機物との合計の割合が２５質量％以下とする。当該割合を２５質量％以下とすることにより、フィルム全体の誘電特性を優れたものにすることができる。また、本発明では液晶ポリマー基材フィルムの平面方向における線膨張係数と配向性を規定しているので、光非活性無機物の配合量を上記範囲に抑制しても、電子回路基板用途における本発明フィルムの特性は十分である。一方、上記割合の下限は特に制限されず、また、光非活性無機物が必要でなければ光活性金属酸化物結晶のみを使用してもよい。 In the film for an electronic circuit board according to the present invention, the total ratio of the photoactive metal oxide crystal and the photoinactive inorganic substance to the whole is 25% by mass or less. By setting the proportion to 25% by mass or less, the dielectric properties of the entire film can be made excellent. In the present invention, since the linear expansion coefficient and orientation in the plane direction of the liquid crystal polymer base film are defined, the present invention for use in electronic circuit boards can be used even if the amount of the photo-inactive inorganic substance is suppressed to the above range. The film properties are sufficient. On the other hand, the lower limit of the above ratio is not particularly limited, and only photoactive metal oxide crystals may be used unless a photoinactive inorganic substance is required.
液晶ポリマー基材フィルムへの光活性金属酸化物結晶や光非活性無機物の分散方法は特に限定されず、常法を用いることができる。例えば、熱可塑性樹脂である液晶ポリマーを融点以上に加熱して溶融させた後、光活性金属酸化物結晶や光非活性無機物を加えて十分に混練すればよい。分散のための装置としては、例えばニーダーなどを用いることができる。得られた混合物は、ペレット化してフィルムの原料として用いてもよい。 The method for dispersing the photoactive metal oxide crystal or the photoinactive inorganic substance in the liquid crystal polymer base film is not particularly limited, and a conventional method can be used. For example, a liquid crystal polymer that is a thermoplastic resin may be heated to a melting point or higher and melted, and then a photoactive metal oxide crystal or a photoinactive inorganic substance may be added and kneaded sufficiently. As a device for dispersion, for example, a kneader can be used. The obtained mixture may be pelletized and used as a raw material for the film.
本発明に係る電子回路基板用フィルムは、上記混合物を用い、常法により製造することができる。例えば、上記混合物をフィルム状に溶融押出成形したりインフレーション成形すればよい。但し、液晶ポリマー分子は剛直な高分子であるため、成形方向に配向してしまい、平面方向で異方性を示す傾向があるので、二軸延伸によりかかる異方性を解消することが好ましい。 The film for electronic circuit boards according to the present invention can be produced by a conventional method using the above mixture. For example, the mixture may be melt-extruded or blown into a film. However, since the liquid crystal polymer molecule is a rigid polymer, it is oriented in the molding direction and tends to exhibit anisotropy in the planar direction. Therefore, it is preferable to eliminate such anisotropy by biaxial stretching.
本発明に係る電子回路基板用フィルムの平面方向の線膨張係数としては３ｐｐｍ／℃以上、３０ｐｐｍ／℃以下とし、また、平面方向の一方向での線膨張係数と、当該方向に直交する方向の線膨張係数との比が０．４以上、２．５以下とする。線膨張係数や上記比が上記範囲を外れる場合は、平面方向で熱応力、機械的強度、誘電率が異なっていたり、また、めっきにより電子回路を形成した場合などにおいて反りが発生し得るなど、電子回路基板の材料として使い難くなるおそれがあり得、また、これら欠点を補うためにフィルム全体の誘電特性が犠牲になるほどの量の光非活性無機物を配合する必要が生じる。なお、平面方向の線膨張係数を測定する方向は特に制限されないが、液晶ポリマーフィルムを溶融押出した後に押出方向（ＭＤ方向）と直交する方向（ＴＤ方向）に延伸して異方性を低減した場合には、通常、ＭＤ方向の線膨張係数が平面方向で最も小さくなる。しかし延伸倍率を高めた場合には、ＴＤ方向の線膨張係数が最小になり、ＭＤ方向が最大になることもあり得る。このように、液晶ポリマーフィルムの平面方向ではＭＤ方向またはＴＤ方向で線膨張係数が最大または最小となるので、線膨張係数はＭＤ方向とＴＤ方向で測定することが好ましい。また、線膨張係数や上記比は、延伸操作により調整可能である。 The linear expansion coefficient in the plane direction of the film for electronic circuit boards according to the present invention is 3 ppm / ° C. or more and 30 ppm / ° C. or less, and the linear expansion coefficient in one direction of the plane direction and the direction orthogonal to the direction. The ratio to the linear expansion coefficient is 0.4 or more and 2.5 or less. When the linear expansion coefficient or the ratio is out of the above range, the thermal stress, mechanical strength, dielectric constant is different in the plane direction, and warping may occur when an electronic circuit is formed by plating, etc. It may be difficult to use as an electronic circuit board material, and in order to compensate for these drawbacks, it is necessary to add a photo-inactive inorganic substance in such an amount that the dielectric properties of the entire film are sacrificed. The direction in which the linear expansion coefficient in the planar direction is measured is not particularly limited, but after the liquid crystal polymer film is melt-extruded, it is stretched in the direction (TD direction) perpendicular to the extrusion direction (MD direction) to reduce anisotropy. In some cases, the linear expansion coefficient in the MD direction is usually the smallest in the plane direction. However, when the draw ratio is increased, the linear expansion coefficient in the TD direction is minimized and the MD direction may be maximized. Thus, since the linear expansion coefficient is maximized or minimized in the MD direction or the TD direction in the plane direction of the liquid crystal polymer film, the linear expansion coefficient is preferably measured in the MD direction and the TD direction. Further, the linear expansion coefficient and the ratio can be adjusted by a stretching operation.
本発明に係る電子回路基板用フィルムは、誘電特性に優れる液晶ポリマーからなるフィルムを基材フィルムとしている上に、ＬＤＳ法などでめっき性を発現させるために必要ではあるが誘電特性を貶める光活性金属酸化物結晶や、配向緩和などのための光非活性無機物の配合量を抑制していることから、全体として誘電特性に優れている。液晶ポリマーは溶融成形する際に樹脂の流れ方向に強い配向を示すため、従来は液晶ポリマー中に、例えば３０〜５０質量％程度といった多量の光非活性無機物を配合しておく必要があり、特にこの光非活性無機物が基材フィルム全体の誘電特性を悪化させていた。本発明では二軸延伸することで液晶ポリマーフィルムの平面内の配向を均一化しているため、光非活性無機物を充填しないか或いは少量の充填に留めることができ、基材フィルム全体の誘電特性の低下を抑えることを可能にしている。 The film for an electronic circuit board according to the present invention uses a film made of a liquid crystal polymer having excellent dielectric properties as a base film, and is also a photoactive material that gives up the dielectric properties although it is necessary to develop plating properties by the LDS method or the like. Since the compounding amount of the metal oxide crystal and the photo-inactive inorganic substance for orientation relaxation is suppressed, the dielectric property as a whole is excellent. Since the liquid crystal polymer exhibits strong alignment in the flow direction of the resin when melt-molded, conventionally, a large amount of a photo-inactive inorganic material such as about 30 to 50% by mass must be blended in the liquid crystal polymer. This photo-inactive inorganic substance deteriorated the dielectric properties of the entire base film. In the present invention, since the orientation in the plane of the liquid crystal polymer film is made uniform by biaxial stretching, it can be filled with a non-light-inactive inorganic substance or can be kept in a small amount, and the dielectric properties of the entire base film can be reduced. It is possible to suppress the decline.
具体的には、本発明に係る電子回路基板用フィルムの比誘電率としては３．７以下が好ましく、誘電正接としては０．００７以下が好ましい。 Specifically, the dielectric constant of the electronic circuit board film according to the present invention is preferably 3.7 or less, and the dielectric loss tangent is preferably 0.007 or less.
また、本発明に係る電子回路基板用フィルムの吸水率としては０．２％以下が好ましい。吸水率を低く調整することで、吸湿に起因する誘電特性の変動や、配線間のショート現象（イオンマイグレーション）、はんだ実装時の基板膨れ不良などを発生し難くすることができる。なお、かかる吸水率の測定方法はＪＩＳ Ｃ６４７１に示されている。 Moreover, as a water absorption rate of the film for electronic circuit boards which concerns on this invention, 0.2% or less is preferable. By adjusting the water absorption rate to a low level, it is possible to make it difficult to cause variations in dielectric characteristics due to moisture absorption, short-circuiting phenomenon between the wires (ion migration), poor board swelling during solder mounting, and the like. In addition, the measuring method of this water absorption is shown by JISC6471.
本発明に係る電子回路基板用フィルムには光活性金属酸化物結晶が分散しているので、その片面または両面にＬＤＳ法などにより電子回路を形成することが可能である。具体的には、形成すべき電子回路の回路パターンに沿ってレーザーを照射すると、液晶ポリマーが削れて光活性金属酸化物結晶が露出すると共に、レーザーのエネルギーにより光活性金属酸化物結晶が活性化され、二価金属原子またはそのイオンが露出する。その二価金属原子または二価イオンとめっき金属との親和性により、レーザー照射部位に選択的に導電性金属をめっきすることが可能になる。 Since the photoactive metal oxide crystal is dispersed in the electronic circuit board film according to the present invention, it is possible to form an electronic circuit on one or both sides by the LDS method or the like. Specifically, when the laser is irradiated along the circuit pattern of the electronic circuit to be formed, the liquid crystal polymer is scraped to expose the photoactive metal oxide crystal, and the photoactive metal oxide crystal is activated by the laser energy. The divalent metal atom or its ion is exposed. The affinity between the divalent metal atom or divalent ion and the plating metal makes it possible to selectively plate the conductive metal on the laser irradiation site.
ＬＤＳ法などで用いるレーザーとしては、波長が数百ｎｍの通常のイットリウム・アルミニウム・ガーネット（ＹＡＧ）レーザーを用いることができる。但し、フィルムをあまり掘削したくない場合には、波長１０６４ｎｍのレーザーを用いてもよい。 As a laser used in the LDS method or the like, a normal yttrium aluminum garnet (YAG) laser having a wavelength of several hundred nm can be used. However, a laser with a wavelength of 1064 nm may be used when not much excavating the film.
レーザー照射により活性化された部分をめっきする金属めっきの材料は、電気伝導性に優れ、比較的安価な金属材料である銅が好ましい。銅めっき回路パターンは、無電解銅めっき、電解銅めっきにより形成できる。めっき浴は一般に硫酸銅水溶液を用いる。 The metal plating material for plating the portion activated by laser irradiation is preferably copper, which is excellent in electrical conductivity and relatively inexpensive. The copper plating circuit pattern can be formed by electroless copper plating or electrolytic copper plating. As the plating bath, an aqueous copper sulfate solution is generally used.
本発明に係る電子回路基板用フィルムへの回路形成は、片面または両面に施すことができる。片面に回路形成した電子回路基板用フィルムは、一枚の基材において一方の面が電気伝導層（回路）、他方の面が液晶ポリマー基材フィルムからなる電気絶縁層となっている。よって、片面に回路形成した電子回路基板用フィルムを複数枚、同方向に重ねた多層基板を作製する際に、電気伝導層と電気絶縁層を交互に設けることができるため、多層基板用の基材として好都合である。また、両面に回路形成した電子回路基板用フィルムは、一枚の基材で２層の回路層を有していることから、一枚の基材のみで形成する両面回路形成基板や、多層基板の中央部に一層使用することで多層基材に使用する基材の枚数を減らすことができ、多層基板の薄型化に好都合である。 The circuit formation on the electronic circuit board film according to the present invention can be performed on one side or both sides. The film for an electronic circuit board in which a circuit is formed on one side is an electrically insulating layer composed of one surface of an electrically conductive layer (circuit) on one substrate and a liquid crystal polymer substrate film on the other surface. Therefore, when producing a multilayer board in which a plurality of films for an electronic circuit board having a circuit formed on one side are stacked in the same direction, an electrically conductive layer and an electrically insulating layer can be alternately provided. Convenient as a material. Moreover, since the film for an electronic circuit board in which circuits are formed on both sides has two circuit layers with a single base material, a double-sided circuit-formed board formed with only one base material or a multilayer board By using a single layer in the central portion of the substrate, the number of base materials used for the multilayer base material can be reduced, which is advantageous for thinning the multilayer substrate.
上記のようにして本発明に係る電子回路基板用フィルムに電子回路を形成した電子回路基板は、その２以上を積層することにより多層電子回路基板としてもよい。例えば、本発明に係る電子回路基板の縦方向（Ｚ方向）に層間を結合するための貫通孔を開け、当該貫通孔に導電ペーストを充填した後、２以上の電子回路基板を一括積層プレスする一括多層工法により多層電子回路基板を製造することができる。 The electronic circuit board in which the electronic circuit is formed on the electronic circuit board film according to the present invention as described above may be a multilayer electronic circuit board by laminating two or more thereof. For example, a through hole for joining layers is formed in the longitudinal direction (Z direction) of the electronic circuit board according to the present invention, and after filling the through hole with a conductive paste, two or more electronic circuit boards are collectively stacked and pressed. A multilayer electronic circuit board can be manufactured by a batch multilayer construction method.
本発明に係る電子回路基板用フィルムのマトリックス樹脂は、熱可塑性樹脂の液晶ポリマーである。よって、特に片面に電子回路が形成された本発明フィルムは、その複数枚を液晶ポリマー基材フィルムと電子回路層が交互になるように積層し、液晶ポリマーを熱融着することで一度の熱プレスで多層化することが可能である。かかる多層化方法は、一括多層工法と呼ばれる。 The matrix resin of the film for electronic circuit boards according to the present invention is a liquid crystal polymer of a thermoplastic resin. Therefore, the film of the present invention in which an electronic circuit is formed on one side in particular is formed by laminating a plurality of the films so that the liquid crystal polymer base film and the electronic circuit layer are alternated, and heat-sealing the liquid crystal polymer once. Multi-layering is possible with a press. Such a multilayering method is called a batch multilayer construction method.
銅箔などの金属箔を積層した後にエッチングなどにより電子回路パターンを形成する従来基板は、電子回路パターン形成後の基板を曲げ加工や絞り加工する際に電子回路パターンも一緒に曲げられたり伸ばされたりするために電子回路が断線し易く、立体成型が難しいという欠点がある。それに対して本発明に係る電子回路基板の電子回路パターンは、電子回路パターンを形成すべき部分にレーザー照射し、続いて上記のとおり立体成形した後、または、上記のとおり立体成形してから電子回路パターンを形成すべき部分にレーザーを照射した後に、めっきによりレーザー照射部分に選択的に電子回路パターンを形成できる。この際、電子回路パターンは曲げられたり伸ばされたりしないために断線し難く、立体基板を作製し易いという利点がある。 In conventional substrates that form an electronic circuit pattern by etching after laminating metal foil such as copper foil, the electronic circuit pattern is also bent or stretched together when bending or drawing the substrate after forming the electronic circuit pattern. Therefore, there is a drawback that the electronic circuit is easily disconnected and three-dimensional molding is difficult. On the other hand, the electronic circuit pattern of the electronic circuit board according to the present invention is obtained by irradiating a portion where the electronic circuit pattern is to be formed with a laser, and then performing three-dimensional molding as described above or after three-dimensional molding as described above. After irradiating a portion where a circuit pattern is to be formed with a laser, an electronic circuit pattern can be selectively formed on the portion irradiated with the laser by plating. At this time, since the electronic circuit pattern is not bent or stretched, it is difficult to disconnect, and there is an advantage that a three-dimensional substrate can be easily manufactured.
以下、実施例を挙げて本発明をより具体的に説明するが、本発明はもとより下記実施例によって制限を受けるものではなく、前・後記の趣旨に適合し得る範囲で適当に変更を加えて実施することも勿論可能であり、それらはいずれも本発明の技術的範囲に包含される。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, but may be appropriately modified within a range that can meet the purpose described above and below. Of course, it is possible to implement them, and they are all included in the technical scope of the present invention.
実施例１
液晶ポリマー樹脂（ポリプラスチックス社製「ＶＥＣＴＲＡ Ｃ９５０」）を９５質量％、ＣｕＣｒ2Ｏ4結晶粉末（Ｓｈｅｐｈｅｒｄ社製「２０Ｃ９８０」）を５質量％の割合で溶融混合し、コンパウンド樹脂ペレットを作製した。当該コンパウンド樹脂ペレットを使用して、ＣｕＣｒ2Ｏ4結晶粉末が全体に分散した二軸延伸液晶ポリマーコンパウンドフィルム（フィルム厚：１００μｍ）を作製した。熱機械分析装置（ＴＡ社製「Ｑ４００」）を使ってこのフィルムの平面内の線膨張係数を測定したところ、樹脂の押出し方向で１７ｐｐｍ／℃、その直交方向（延伸方向）で１７ｐｐｍ／℃であり、この後にこのフィルム上に形成する銅めっきパターンの線膨張係数（１６ｐｐｍ／℃）とほぼ同じ値であることを確認した。
Example 1
A liquid crystal polymer resin (“VECTRA C950” manufactured by Polyplastics) was melt-mixed at a ratio of 95% by mass and CuCr 2 O 4 crystal powder (“20C980” manufactured by Shepherd) was mixed at a ratio of 5% by mass to prepare compound resin pellets. . Using the compound resin pellet, a biaxially stretched liquid crystal polymer compound film (film thickness: 100 μm) in which the CuCr 2 O 4 crystal powder was dispersed throughout was produced. When the linear expansion coefficient in the plane of this film was measured using a thermomechanical analyzer (TA Corp. “Q400”), it was 17 ppm / ° C. in the resin extrusion direction and 17 ppm / ° C. in the orthogonal direction (stretching direction). After that, it was confirmed that it was almost the same value as the linear expansion coefficient (16 ppm / ° C.) of the copper plating pattern formed on this film.
上記シートに、レーザー照射装置（パナソニック社製「ＬＰ−Ｓ」）を用いてＹＡＧレーザーを照射することにより、１ｍｍ幅で長さ５０ｍｍの線上においてＣｕＣｒ2Ｏ4結晶粉末を活性化させてめっき性を発現させた後、当該積層体を硫酸銅溶液より成る銅めっき浴に浸漬して厚さ０．５μｍの無電解銅めっき層を形成した。続いて、電解銅めっきを行なって厚さ１２μｍの銅パターンを形成した。 By irradiating the sheet with a YAG laser using a laser irradiation apparatus (“LP-S” manufactured by Panasonic), the CuCr 2 O 4 crystal powder is activated on a line having a width of 1 mm and a length of 50 mm. Then, the laminate was immersed in a copper plating bath made of a copper sulfate solution to form an electroless copper plating layer having a thickness of 0.5 μm. Subsequently, electrolytic copper plating was performed to form a 12 μm thick copper pattern.
形成された回路パターンを光学顕微鏡（キーエンス社製「デジタルマイクロスコープＶＨＸ−５００」）で観察したところ、パターン幅に乱れは無く、１ｍｍ幅の回路が正確に形成されていた。 When the formed circuit pattern was observed with an optical microscope ("Digital Microscope VHX-500" manufactured by Keyence Corporation), the pattern width was not disturbed, and a 1 mm wide circuit was formed accurately.
また、形成された回路パターンの密着性を、引張試験機（東洋精機社製「ストログラフＥ５Ｄ」）を用いて評価した。具体的には、回路パターンの端部を剥離し、引張試験機のクランプに挟んで１８０°方向に剥離し、剥離強度を測定した。測定は５本の回路パターンにつき行い、平均値を算出した。その結果、剥離強度は０．５Ｎ／ｍｍと十分な剥離強度を有していた。 Further, the adhesion of the formed circuit pattern was evaluated using a tensile tester (“Strograph E5D” manufactured by Toyo Seiki Co., Ltd.). Specifically, the end portion of the circuit pattern was peeled off, and was peeled in a 180 ° direction by being sandwiched between clamps of a tensile tester, and the peel strength was measured. The measurement was performed for five circuit patterns, and the average value was calculated. As a result, the peel strength was a sufficient peel strength of 0.5 N / mm.
さらに、得られたシートの誘電特性を、ネットワークアナライザー（アジレントテクノロジ社製「Ｅ５０７１Ｃ」）を用い、測定周波数３ＧＨｚ、測定モードＴＥ011で、空洞共振器摂動法により評価した。その結果、比誘電率は３．４９、誘電正接は０．００２５と、上記積層体の誘電特性は極めて優れたものであることが証明された。 Furthermore, the dielectric properties of the obtained sheet were evaluated by a cavity resonator perturbation method using a network analyzer (“E5071C” manufactured by Agilent Technologies) at a measurement frequency of 3 GHz and a measurement mode TE 011 . As a result, the relative dielectric constant was 3.49 and the dielectric loss tangent was 0.0025, which proved that the dielectric properties of the laminate were extremely excellent.
実施例２
上記実施例１において、液晶ポリマー樹脂を９０質量％、ＣｕＣｒ2Ｏ4結晶粉末を１０質量％の割合にした以外は同様にして、電子回路基板を作製した。その特性評価結果を表１に示す。
Example 2
An electronic circuit board was produced in the same manner as in Example 1 except that the liquid crystal polymer resin was 90% by mass and the CuCr 2 O 4 crystal powder was 10% by mass. The characteristic evaluation results are shown in Table 1.
実施例３
上記実施例１において、液晶ポリマー樹脂を８０質量％、ＣｕＣｒ2Ｏ4結晶粉末を２０質量％の割合にした以外は同様にして、電子回路基板を作製した。その特性評価結果を表１に示す。
Example 3
An electronic circuit board was produced in the same manner as in Example 1, except that the liquid crystal polymer resin was 80% by mass and the CuCr 2 O 4 crystal powder was 20% by mass. The characteristic evaluation results are shown in Table 1.
実施例４
上記実施例１において、液晶ポリマー樹脂を７５質量％、ＣｕＣｒ2Ｏ4結晶粉末を２０質量％、さらに、酸化ケイ素フィラーを５質量％の割合で溶融混合した以外は同様にして、電子回路基板を作製した。その特性評価結果を表１に示す。
Example 4
An electronic circuit board was prepared in the same manner as in Example 1 except that the liquid crystal polymer resin was 75% by mass, the CuCr 2 O 4 crystal powder was 20% by mass, and the silicon oxide filler was melted and mixed at a rate of 5% by mass. Produced. The characteristic evaluation results are shown in Table 1.
実施例５
上記実施例１において、液晶ポリマー樹脂を７５質量％、ＣｕＣｒ2Ｏ4結晶粉末を５質量％、さらに、酸化ケイ素フィラーを２０質量％の割合で溶融混合した以外は同様にして、電子回路基板を作製した。その特性評価結果を表１に示す。
Example 5
An electronic circuit board was prepared in the same manner as in Example 1 except that 75% by mass of the liquid crystal polymer resin, 5% by mass of the CuCr 2 O 4 crystal powder, and 20% by mass of the silicon oxide filler were melt mixed. Produced. The characteristic evaluation results are shown in Table 1.
比較例１
上記実施例１において、液晶ポリマー樹脂を９７質量％、ＣｕＣｒ2Ｏ4結晶粉末を３質量％の割合にした以外は同様にして、電子回路基板用フィルムを作製した。その特性評価結果を表１に示す。但し、上記実施例１と同様にして回路を形成しようとしたが、無電解銅めっきは析出しなかった。
Comparative Example 1
A film for an electronic circuit board was produced in the same manner as in Example 1 except that the liquid crystal polymer resin was changed to 97% by mass and the CuCr 2 O 4 crystal powder was changed to 3% by mass. The characteristic evaluation results are shown in Table 1. However, although an attempt was made to form a circuit in the same manner as in Example 1, electroless copper plating did not deposit.
比較例２
上記実施例１において、液晶ポリマー樹脂を７０質量％、ＣｕＣｒ2Ｏ4結晶粉末を３０質量％の割合にした以外は同様にして、電子回路基板用フィルムを作製した。その特性評価結果を表１に示す。
Comparative Example 2
A film for an electronic circuit board was produced in the same manner as in Example 1 except that the liquid crystal polymer resin was 70% by mass and the CuCr 2 O 4 crystal powder was 30% by mass. The characteristic evaluation results are shown in Table 1.
比較例３
配向緩和目的で光非活性無機物フィラーを多く含む射出成形用液晶ポリマー樹脂（ポリプラスチックス社製「ＶＥＣＴＲＡ Ｃ１３０Ｍ」）を使用して射出成形フィルム（厚さ１００μｍ）を作製した。当該フィルムの表面を強アルカリ処理することによりめっき性を付与した上で、その片面の全面に無電解銅めっきにより厚さ０．５μｍの無電解銅めっき層を形成した後、電解銅めっきを行なって厚さ１２μｍの銅層を形成した。続いて、銅層の一部をエッチング法により除去して、上記実施例１と同様の銅パターンを形成した。得られた電子回路基板の特性評価結果を表１に示す。
Comparative Example 3
An injection-molded film (thickness: 100 μm) was prepared by using a liquid crystal polymer resin for injection molding (“VECTRA C130M” manufactured by Polyplastics Co., Ltd.) containing a large amount of a photo-inactive inorganic filler for the purpose of relaxing the orientation. After the surface of the film has been subjected to strong alkali treatment to provide plating properties, an electroless copper plating layer having a thickness of 0.5 μm is formed on the entire surface of one surface by electroless copper plating, and then electrolytic copper plating is performed. Thus, a copper layer having a thickness of 12 μm was formed. Subsequently, a part of the copper layer was removed by an etching method to form a copper pattern similar to that in Example 1. Table 1 shows the evaluation results of the characteristics of the obtained electronic circuit board.
参考例１
液晶ポリマー樹脂（ポリプラスチックス社製「ＶＥＣＴＲＡ Ｃ９５０」）を上記実施例１の条件と同様にて押出し、厚さ４００μｍのフィルムを得た。その特性評価結果を表１に示す。
Reference example 1
A liquid crystal polymer resin (“VECTRA C950” manufactured by Polyplastics) was extruded under the same conditions as in Example 1 to obtain a film having a thickness of 400 μm. The characteristic evaluation results are shown in Table 1.
比較例１のとおり光活性金属酸化物結晶の配合量が少ない場合、また、光活性金属酸化物結晶を含まない液晶ポリマーフィルム単体でも、レーザーを用いた電子回路形成はできなかった。比較例３のとおり、光活性金属酸化物結晶を含まなくても強アルカリ処理によりめっきは可能になるが、レーザーを用いた電子回路形成は当然にできないし、また、無機物フィラーを多く含むことから誘電特性が非常に劣るものであった。 When the blending amount of the photoactive metal oxide crystal was small as in Comparative Example 1, or even a liquid crystal polymer film alone containing no photoactive metal oxide crystal, it was not possible to form an electronic circuit using a laser. As in Comparative Example 3, although it is possible to plate by strong alkali treatment without including a photoactive metal oxide crystal, it is naturally impossible to form an electronic circuit using a laser, and it contains a lot of inorganic fillers. Dielectric properties were very poor.
また、比較例２の結果のとおり、光活性金属酸化物結晶の配合によりレーザーを用いた電子回路形成は可能になるが、無機物の配合量が所定量を超えると誘電特性は悪化した。 Moreover, as the result of the comparative example 2, although the electronic circuit formation using a laser became possible by the mixing | blending of the photoactive metal oxide crystal, when the compounding quantity of the inorganic substance exceeded predetermined amount, the dielectric characteristic deteriorated.
さらに、参考例１の結果のとおり、液晶ポリマー単体、即ち光非活性無機物フィラーなどが含まれてないニートレジンをフィルム状に押出成形した場合は、平面方向の線膨張係数が大きくバランスを失った。また、レーザー照射に続いて無電解銅めっきを行ったが、無電解銅めっきは当然ながら析出しなかった。 Furthermore, as shown in the result of Reference Example 1, when a neat resin that does not contain a liquid crystal polymer alone, that is, a photo-inactive inorganic filler, was extruded into a film, the linear expansion coefficient in the plane direction was greatly lost. . Moreover, although electroless copper plating was performed following laser irradiation, naturally electroless copper plating did not precipitate.
一方、光金属酸化物結晶を適量含む実施例１〜５では、レーザーを用いた電子回路形成は可能になる上に、誘電特性が優れていた。かかる結果より、本発明の電子回路基板用フィルムは、高周波製品に用いるアンテナ基板や伝送路基板の基材として非常に有用であることが明らかとなった。 On the other hand, in Examples 1 to 5 containing an appropriate amount of the photometal oxide crystal, it was possible to form an electronic circuit using a laser and excellent dielectric characteristics. From these results, it was found that the electronic circuit board film of the present invention is very useful as a base material for antenna boards and transmission path boards used in high-frequency products.
Claims (9)
ＡＢ 2 Ｏ 4 またはＢＡＢＯ 4
［式中、Ａは、二価銅、または、二価銅と、カドミウム、亜鉛、コバルト、マグネシウム、スズ、チタン、鉄、アルミニウム、ニッケル、マンガンおよびクロムからなる群から選択される二価金属との組み合わせを示し；Ｂは、三価クロム、または、三価クロムと、カドミウム、マンガン、ニッケル、亜鉛、銅、コバルト、マグネシウム、スズ、チタン、鉄およびアルミニウムからなる群から選択される三価金属との組み合わせを示す］
全体に対する上記光活性金属酸化物結晶の割合が５質量％以上、２０質量％以下であり、
上記基材フィルムの平面方向の線膨張係数が３ｐｐｍ／℃以上、３０ｐｐｍ／℃以下であり、且つ、平面方向の一方向での線膨張係数と当該方向に直交する方向の線膨張係数との比が０．４以上、２．５以下であることを特徴とする電子回路基板用フィルム。 In a base film formed from a liquid crystal polymer , a photoactive metal oxide crystal represented by the following chemical formula and having a spinel crystal structure is dispersed,
AB 2 O 4 or BABO 4
[Wherein A is divalent copper or divalent copper and a divalent metal selected from the group consisting of cadmium, zinc, cobalt, magnesium, tin, titanium, iron, aluminum, nickel, manganese and chromium. B represents trivalent chromium or trivalent metal selected from the group consisting of trivalent chromium and cadmium, manganese, nickel, zinc, copper, cobalt, magnesium, tin, titanium, iron and aluminum Show combination with]
The ratio of the photoactive metal oxide crystal to the whole is 5 mass% or more and 20 mass% or less
The ratio of the linear expansion coefficient in the plane direction of the substrate film to 3 ppm / ° C. or more and 30 ppm / ° C. or less, and the linear expansion coefficient in one direction of the plane direction and the linear expansion coefficient in the direction orthogonal to the direction. Is a film for electronic circuit boards, characterized by being 0.4 or more and 2.5 or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014187635A JP6405818B2 (en) | 2014-09-16 | 2014-09-16 | Film for electronic circuit board and electronic circuit board |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014187635A JP6405818B2 (en) | 2014-09-16 | 2014-09-16 | Film for electronic circuit board and electronic circuit board |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2016062955A JP2016062955A (en) | 2016-04-25 |
| JP6405818B2 true JP6405818B2 (en) | 2018-10-17 |
Family
ID=55798172
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2014187635A Active JP6405818B2 (en) | 2014-09-16 | 2014-09-16 | Film for electronic circuit board and electronic circuit board |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6405818B2 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11258184B2 (en) | 2019-08-21 | 2022-02-22 | Ticona Llc | Antenna system including a polymer composition having a low dissipation factor |
| US11555113B2 (en) | 2019-09-10 | 2023-01-17 | Ticona Llc | Liquid crystalline polymer composition |
| US11637365B2 (en) | 2019-08-21 | 2023-04-25 | Ticona Llc | Polymer composition for use in an antenna system |
| US11646760B2 (en) | 2019-09-23 | 2023-05-09 | Ticona Llc | RF filter for use at 5G frequencies |
| US11721888B2 (en) | 2019-11-11 | 2023-08-08 | Ticona Llc | Antenna cover including a polymer composition having a low dielectric constant and dissipation factor |
| US11728559B2 (en) | 2021-02-18 | 2023-08-15 | Ticona Llc | Polymer composition for use in an antenna system |
| US11729908B2 (en) | 2020-02-26 | 2023-08-15 | Ticona Llc | Circuit structure |
| US11912817B2 (en) | 2019-09-10 | 2024-02-27 | Ticona Llc | Polymer composition for laser direct structuring |
| US11917753B2 (en) | 2019-09-23 | 2024-02-27 | Ticona Llc | Circuit board for use at 5G frequencies |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4116360A4 (en) * | 2020-03-06 | 2024-04-03 | Murata Manufacturing Co | Liquid crystal polymer film and method for producing same |
| WO2023228904A1 (en) * | 2022-05-27 | 2023-11-30 | 株式会社村田製作所 | Liquid crystal polymer pellets, liquid crystal polymer powder, liquid crystal polymer film and production methods of those |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4017394B2 (en) * | 1999-11-30 | 2007-12-05 | 大塚化学株式会社 | Resin composition and flexible printed wiring board |
| US7547849B2 (en) * | 2005-06-15 | 2009-06-16 | E.I. Du Pont De Nemours And Company | Compositions useful in electronic circuitry type applications, patternable using amplified light, and methods and compositions relating thereto |
| JP5088853B2 (en) * | 2005-09-20 | 2012-12-05 | 株式会社プライマテック | Method for predicting warpage of reinforcing plate for flexible circuit board by high-temperature reflow process, and reinforcing plate for flexible circuit board |
| JP2011157533A (en) * | 2010-02-04 | 2011-08-18 | Sumitomo Chemical Co Ltd | Liquid crystalline polyester composition and film of the same |
| CN102071424B (en) * | 2010-02-26 | 2012-05-09 | 比亚迪股份有限公司 | Plastic product and preparation method thereof |
| JP5674405B2 (en) * | 2010-09-30 | 2015-02-25 | 株式会社クラレ | Thermoplastic liquid crystal polymer film and transmission line using the same |
| JP6182856B2 (en) * | 2012-12-05 | 2017-08-23 | 株式会社村田製作所 | Method for producing liquid crystal polymer film |
-
2014
- 2014-09-16 JP JP2014187635A patent/JP6405818B2/en active Active
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11258184B2 (en) | 2019-08-21 | 2022-02-22 | Ticona Llc | Antenna system including a polymer composition having a low dissipation factor |
| US11637365B2 (en) | 2019-08-21 | 2023-04-25 | Ticona Llc | Polymer composition for use in an antenna system |
| US11705641B2 (en) | 2019-08-21 | 2023-07-18 | Ticoan Llc | Antenna system including a polymer composition having a low dissipation factor |
| US11555113B2 (en) | 2019-09-10 | 2023-01-17 | Ticona Llc | Liquid crystalline polymer composition |
| US11912817B2 (en) | 2019-09-10 | 2024-02-27 | Ticona Llc | Polymer composition for laser direct structuring |
| US11646760B2 (en) | 2019-09-23 | 2023-05-09 | Ticona Llc | RF filter for use at 5G frequencies |
| US11917753B2 (en) | 2019-09-23 | 2024-02-27 | Ticona Llc | Circuit board for use at 5G frequencies |
| US11721888B2 (en) | 2019-11-11 | 2023-08-08 | Ticona Llc | Antenna cover including a polymer composition having a low dielectric constant and dissipation factor |
| US11729908B2 (en) | 2020-02-26 | 2023-08-15 | Ticona Llc | Circuit structure |
| US11728559B2 (en) | 2021-02-18 | 2023-08-15 | Ticona Llc | Polymer composition for use in an antenna system |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2016062955A (en) | 2016-04-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6405818B2 (en) | Film for electronic circuit board and electronic circuit board | |
| JP6405817B2 (en) | Laminate for electronic circuit board and electronic circuit board | |
| TWI752205B (en) | Thermoplastic liquid crystal polymer and film thereof | |
| WO2020262255A1 (en) | Lcp extruded film, flexible laminate using same and method for producing same | |
| JP2018109090A (en) | Thermoplastic liquid crystal polymer film and circuit board using the same | |
| TWI753501B (en) | Liquid crystal polyester resin composition, layered product, method for producing layered product, and method for producing liquid crystal polyester resin film | |
| JP6930046B1 (en) | Manufacturing method of LCP film for circuit board and T-die melt extrusion LCP film for circuit board | |
| JP2000510639A (en) | Polymer composition having temperature stable dielectric constant | |
| WO2021106768A1 (en) | Lcp resin composition for circuit boards, lcp film for circuit boards and method for producing same | |
| TW201021655A (en) | Laminated product and production method thereof, and circuit substrate using the same | |
| WO2021187399A1 (en) | Resin composition, and resin molded article comprising said resin composition | |
| JP3896324B2 (en) | Liquid crystal polymer blend film | |
| WO2022065270A1 (en) | Insulating material for circuit substrate, and metal foil-clad laminate | |
| WO2022065285A1 (en) | Insulating material for circuit boards, method for producing same and metal foil-clad laminate | |
| KR20230142598A (en) | Liquid crystal polyester-based resin composition, liquid crystal polyester-based film using the composition, metal laminate film using the film, circuit board | |
| TWI742456B (en) | Resin composition capable of alleviating anisotropy by melting and resin molded article containing the resin composition | |
| JP6156079B2 (en) | Metal-clad laminate and method for producing the same, printed wiring board using the same, and method for producing the same | |
| TW202100608A (en) | Thermoplastic liquid crystal polymer film, multi-layered body and shaped article, and production methods thereof | |
| JP2022091493A (en) | Method for manufacturing lcp extrusion film | |
| KR20230121612A (en) | Liquid crystal polymer composite, liquid crystal polymer composite film, and metal clad laminate including the same | |
| TW202102087A (en) | Thermoplastic liquid crystal polymer film, multi-layered body and shaped article, and production methods thereof | |
| JP2004096040A (en) | Polyphenylenesulfide film for circuit board |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A711 Effective date: 20170403 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20170605 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20180219 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20180313 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20180425 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20180821 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20180903 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6405818 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |