JP7371710B2 - Prepreg for coreless substrates, method and apparatus for producing prepreg for coreless substrates, coreless substrates and methods for producing the same - Google Patents
Prepreg for coreless substrates, method and apparatus for producing prepreg for coreless substrates, coreless substrates and methods for producing the same Download PDFInfo
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- JP7371710B2 JP7371710B2 JP2022017484A JP2022017484A JP7371710B2 JP 7371710 B2 JP7371710 B2 JP 7371710B2 JP 2022017484 A JP2022017484 A JP 2022017484A JP 2022017484 A JP2022017484 A JP 2022017484A JP 7371710 B2 JP7371710 B2 JP 7371710B2
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- prepreg
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- coreless substrate
- aggregate
- coreless
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- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- QLAGHGSFXJZWKY-UHFFFAOYSA-N triphenylborane;triphenylphosphane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QLAGHGSFXJZWKY-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
Description
本発明はコアレス基板用プリプレグ、コアレス基板用プリプレグの製造方法及び製造装置、並びにコアレス基板及びその製造方法に関する。 The present invention relates to a prepreg for a coreless substrate, a method and apparatus for manufacturing the prepreg for a coreless substrate, and a coreless substrate and a method for manufacturing the same.
ＦＲＰ（Fiber Reinforced Plastics；繊維強化プラスチック）は、ファイバー等の弾性率の高い材料を骨材とし、その骨材を、プラスチック等の母材（マトリックス）の中に入れて強度を向上させた複合材料である。ＦＲＰは、耐候性、耐熱性、耐薬品性及び軽量性を生かした、安価かつ軽量で耐久性に優れる複合材料であり、特に、その絶縁性を生かして、プリント配線板用のプリプレグとして使用されている。 FRP (Fiber Reinforced Plastics) is a composite material that uses materials with high elastic modulus such as fiber as aggregate and places the aggregate in a base material (matrix) such as plastic to improve strength. It is. FRP is an inexpensive, lightweight, and durable composite material that takes advantage of its weather resistance, heat resistance, chemical resistance, and light weight.In particular, it is used as a prepreg for printed wiring boards because of its insulating properties. ing.
近年の電子機器の小型化及び高性能化により、プリント配線板には従来にも増して配線密度の高度化及び高集積化と共に、基板の薄型化が求められている。
これらの要求を踏まえたパッケージ構造として、例えば、特許文献１及び特許文献２には、コア基板を有さず、高密度配線化が可能なビルドアップ層を主体としたコアレス基板が提案されている。このコアレス基板は、金属板等の支持体（コア基板）上にビルドアップ層を形成した後、該支持体（コア基板）を除去することにより得られる、ビルドアップ層のみから構成される基板となる。
2. Description of the Related Art Due to the miniaturization and higher performance of electronic devices in recent years, printed wiring boards are required to have higher wiring density and higher integration than ever before, as well as thinner substrates.
As a package structure based on these requirements, for example, Patent Document 1 and Patent Document 2 propose a coreless board that does not have a core substrate and is mainly composed of a build-up layer that enables high-density wiring. . This coreless board is a board consisting only of a build-up layer, which is obtained by forming a build-up layer on a support (core board) such as a metal plate and then removing the support (core board). Become.
コアレス基板は、支持体（コア基板）を除去することによる薄型化によって剛性が低下するため、半導体素子を搭載してパッケージ化した際に半導体パッケージが反るという問題がより顕著になる。反りは、半導体素子とプリント配線板との接続不良を引き起こす要因の１つとされており、コアレス基板においては、より一層効果的な反りの低減が切望されている。 Since coreless substrates have reduced rigidity due to thinning by removing the support body (core substrate), the problem of warping of the semiconductor package when a semiconductor element is mounted and packaged becomes more pronounced. Warpage is considered to be one of the causes of poor connection between semiconductor elements and printed wiring boards, and there is a strong desire for even more effective reduction of warpage in coreless boards.
従来のプリント配線板用のプリプレグの多くが、ハンドレイアップ（Hand Lay-up）法で製造されている。ハンドレイアップ法は、塗工機等を用いて、樹脂を溶解したワニスを骨材に塗布した後、乾燥及び熱硬化する方法である（特許文献３）。 Most conventional prepregs for printed wiring boards are manufactured by the hand lay-up method. The hand lay-up method is a method in which a varnish in which a resin is dissolved is applied to aggregate using a coating machine or the like, and then dried and thermally cured (Patent Document 3).
基板の薄型化に伴い、骨材として従来よりも厚さが薄い繊維基材が用いられつつある。このような薄い繊維基材は、機械強度が弱いため、ハンドレイアップ法によって、ワニスを塗布、乾燥等する際に、自重が繊維基材の耐荷重を上回り、繊維基材が切れてしまう場合があった。また、繊維基材に塗布する樹脂量を調整するためにコーターのギャップを狭くした際にも、千切れてしまったりする等、作業性に劣る問題があった。
また、積層後の厚みの高精度性と、内層回路パターンへの樹脂の充填性（成型性）とを両立させるため、骨材に付着させる樹脂量が数質量％異なるもの、熱硬化性樹脂の硬化時間を変えたもの、それらを組合せたもの等、１種類の骨材で複数種類のプリプレグを製造しなければならず、煩雑である。さらに、各々塗工条件を変えて製造するために、製造に用いる材料のロスも大きい。
さらには、従来のプリプレグは、配線板を形成した際の厚みのばらつきが大きく、また、配線板と半導体装置とをはんだ接合する際の熱履歴によって発生する寸法変化も大きいため、これらに起因して反りが発生し、コアレス基板に求められる水準の反りの低減が達成されていなかった。
As substrates become thinner, fiber base materials that are thinner than before are being used as aggregates. Such thin fiber base materials have low mechanical strength, so when applying varnish and drying using the hand lay-up method, the weight may exceed the load capacity of the fiber base material and the fiber base material may break. was there. Further, even when the coater gap was narrowed to adjust the amount of resin applied to the fiber base material, there were problems with poor workability, such as tearing.
In addition, in order to achieve both high precision of the thickness after lamination and the ability to fill the inner layer circuit pattern with resin (moldability), we have developed products that differ in the amount of resin attached to the aggregate by a few percent by mass, and thermosetting resins. It is complicated to manufacture multiple types of prepregs using one type of aggregate, such as those with different curing times or a combination of these. Furthermore, since each coating is manufactured under different coating conditions, there is a large loss of materials used in manufacturing.
Furthermore, conventional prepregs have large variations in thickness when wiring boards are formed, and also have large dimensional changes caused by thermal history when soldering the wiring board and semiconductor device. Warpage occurred, and the level of warpage reduction required for coreless substrates was not achieved.
本発明の課題は、作業性が良好であり、優れた厚み精度及び寸法安定性を有するコアレス基板用プリプレグが得られるコアレス基板用プリプレグの製造方法及び製造装置、該製造方法により得られるコアレス基板用プリプレグ、並びに該コアレス基板用プリプレグを用いたコアレス基板及びその製造方法を提供することである。 An object of the present invention is to provide a method and apparatus for manufacturing a prepreg for coreless substrates that can obtain prepregs for coreless substrates that have good workability and excellent thickness accuracy and dimensional stability, and a method and apparatus for producing prepregs for coreless substrates that can be obtained by the manufacturing method. An object of the present invention is to provide a prepreg, a coreless board using the coreless board prepreg, and a method for manufacturing the same.
本発明者らは、精鋭研究した結果、作業性に優れる常圧下において、熱硬化性樹脂組成物を含んでなる樹脂フィルムを骨材に圧接する製造方法により、作業性及び生産性良く厚み精度及び寸法安定性に優れるプリプレグが得られることを見出し、本発明に到達した。すなわち、本発明は、以下の［１］～［１５］に関する。
［１］シート状骨材の少なくとも一方の表面に、熱硬化性樹脂組成物を含んでなる樹脂フィルム（Ｉ）を貼付する、コアレス基板用プリプレグの製造方法であって、
前記貼付を、常圧下において、前記樹脂フィルム（Ｉ）を、前記シート状骨材の少なくとも一方の表面に圧接するフィルム圧接工程により行う、コアレス基板用プリプレグの製造方法。
［２］前記フィルム圧接工程が、前記樹脂フィルム（Ｉ）を、前記シート状骨材の両方の表面に圧接する工程である、上記［１］に記載のコアレス基板用プリプレグの製造方法。
［３］前記フィルム圧接工程が、前記樹脂フィルム（Ｉ）を、前記樹脂フィルム（Ｉ）の最低溶融粘度温度のマイナス４０℃からプラス２０℃の範囲に加熱しながら、前記シート状骨材の少なくとも一方の表面に圧接する工程である、上記［１］又は［２］に記載のコアレス基板用プリプレグの製造方法。
［４］前記樹脂フィルム（Ｉ）が、１分子中に少なくとも２個のＮ－置換マレイミド基を有するマレイミド化合物（ａ）、１分子中に少なくとも２個の１級アミノ基を有するアミン化合物（ｂ）、及び熱可塑性エラストマー（ｃ）を含有する熱硬化性樹脂組成物を含んでなるものである、上記［１］～［３］のいずれかに記載のコアレス基板用プリプレグの製造方法。
［５］前記樹脂フィルム（Ｉ）が、１分子中に少なくとも２個のＮ－置換マレイミド基を有するマレイミド化合物（ａ）と、１分子中に少なくとも２個の１級アミノ基を有するアミン化合物（ｂ）と、の反応物である変性ポリイミド（Ｘ）と、熱可塑性エラストマー（ｃ）と、を含有する熱硬化性樹脂組成物を含んでなるものである、上記［１］～［３］のいずれかに記載のコアレス基板用プリプレグの製造方法。
［６］前記熱硬化性樹脂組成物が、さらに、熱硬化性樹脂（ｄ）を含有する、上記［４］又は［５］に記載のコアレス基板用プリプレグの製造方法。
［７］上記［１］～［６］のいずれかに記載のコアレス基板用プリプレグの製造方法に用いられるコアレス基板用プリプレグの製造装置であって、
常圧下において、前記樹脂フィルム（Ｉ）を、前記シート状骨材の少なくとも一方に圧接させて貼付するフィルム圧接手段を有する、コアレス基板用プリプレグの製造装置。
［８］上記［１］～［６］のいずれかに記載のコアレス基板用プリプレグの製造方法により製造されたコアレス基板用プリプレグ。
［９］下記測定方法に従って測定したエッチング後の寸法変化率（i）が、－８．０～＋８．０％であり、かつ１７０℃１時間加熱後の寸法変化率（ii）が、－４．０～＋４．０％である、上記［８］に記載のコアレス基板用プリプレグ。
＜寸法変化率の測定方法＞
プリプレグの両表面に厚さ１２μｍの電解銅箔を有する２５０ｃｍ角の銅張積層板を評価基板とし、その４角から縦に１ｃｍ、横に１ｃｍの部分に基準穴を合計４つ設け、隣接する穴間同士の距離の平均値を基準寸法とし、
該評価基板を銅エッチング液に浸漬することにより銅箔を取り除いた後の、隣接する穴間同士の距離の平均値をエッチング後寸法とし、
エッチング後の評価基板を、１７０℃で１時間加熱した後の、隣接する穴間同士の距離の平均値を加熱後寸法として、下記式に基づき計算する。
寸法変化率（i）（％）＝（エッチング後寸法－基準寸法）×１００／基準寸法
寸法変化率（ii）（％）＝（加熱後寸法－エッチング後寸法）×１００／エッチング後寸法
［１０］下記測定方法に従って測定した厚み精度の値が、１０％以下である、上記［８］又は［９］に記載のコアレス基板用プリプレグ。
＜厚み精度の測定方法＞
プリプレグの両表面に厚さ１２μｍの電解銅箔を有する銅張積層板の幅方向の中心から５０ｍｍ単位で幅方向に計１１点、前記１１点を各々起点として長さ方向に５０ｍｍ単位で１０点の厚さを測定し、その最大厚さ、最小厚さ及び平均厚さを求め、下記式に基づいて、平均厚さに対する最大厚さの変化率及び平均厚さに対する最小厚さの変化率を各々求め、いずれか大きい値を厚み精度の値とする。
最大厚さの変化率（％）＝（最大厚さ－平均厚さ）×１００／平均厚さ
最小厚さの変化率（％）＝（平均厚さ－最小厚さ）×１００／平均厚さ
［１１］硬化物の弾性率が、１０～２０ＧＰａである、上記［８］～［１０］のいずれかに記載のコアレス基板用プリプレグ。
［１２］硬化物の熱膨張率が、５．０～６．５ｐｐｍ／℃である、上記［８］～［１１］のいずれかに記載のコアレス基板用プリプレグ。
［１３］上記［８］～［１２］のいずれかに記載のコアレス基板用プリプレグを用いて形成された絶縁層を含有する、コアレス基板。
［１４］上記［１３］に記載のコアレス基板に半導体素子を搭載してなる半導体パッケージ。
［１５］支持体の上に、導体層と絶縁層とが交互に積層されてなるビルドアップ層を形成した後、該ビルドアップ層を前記支持体から分離するコアレス基板の製造方法であって、前記絶縁層の少なくとも１層を、上記［１］～［６］に記載のコアレス基板用プリプレグの製造方法により製造したコアレス基板用プリプレグを用いて形成する、コアレス基板の製造方法。
As a result of intensive research, the present inventors have found that a manufacturing method in which a resin film containing a thermosetting resin composition is pressure-bonded to aggregate under normal pressure, which has excellent workability, has good workability and productivity, and has achieved thickness accuracy and We have discovered that a prepreg with excellent dimensional stability can be obtained, and have arrived at the present invention. That is, the present invention relates to the following [1] to [15].
[1] A method for producing a prepreg for a coreless substrate, which comprises attaching a resin film (I) containing a thermosetting resin composition to at least one surface of a sheet-like aggregate, the method comprising:
A method for manufacturing a prepreg for a coreless substrate, wherein the pasting is carried out by a film pressure contact step of press-contacting the resin film (I) to at least one surface of the sheet-like aggregate under normal pressure.
[2] The method for producing a prepreg for a coreless substrate according to [1] above, wherein the film press-contacting step is a step of press-contacting the resin film (I) to both surfaces of the sheet-like aggregate.
[3] In the film pressure welding step, at least one of the sheet-like aggregates is heated while heating the resin film (I) to a range of -40°C to +20°C above the lowest melt viscosity temperature of the resin film (I). The method for manufacturing a prepreg for a coreless substrate according to the above [1] or [2], which is a step of press-contacting one surface.
[4] The resin film (I) contains a maleimide compound (a) having at least two N-substituted maleimide groups in one molecule, an amine compound (b) having at least two primary amino groups in one molecule. ), and a thermosetting resin composition containing a thermoplastic elastomer (c), the method for producing a prepreg for a coreless substrate according to any one of [1] to [3] above.
[5] The resin film (I) contains a maleimide compound (a) having at least two N-substituted maleimide groups in one molecule, and an amine compound having at least two primary amino groups in one molecule ( The thermosetting resin composition of [1] to [3] above, which comprises a thermosetting resin composition containing a modified polyimide (X) which is a reaction product of b), and a thermoplastic elastomer (c). A method for producing a prepreg for a coreless board according to any one of the above.
[6] The method for producing a prepreg for a coreless substrate according to [4] or [5] above, wherein the thermosetting resin composition further contains a thermosetting resin (d).
[7] A coreless substrate prepreg manufacturing apparatus used in the method for manufacturing coreless substrate prepreg according to any one of [1] to [6] above,
An apparatus for manufacturing a prepreg for coreless substrates, comprising a film press-contacting means for press-contacting and pasting the resin film (I) on at least one of the sheet-like aggregates under normal pressure.
[8] A prepreg for a coreless substrate manufactured by the method for manufacturing a prepreg for a coreless substrate according to any one of [1] to [6] above.
[9] The dimensional change rate (i) after etching measured according to the following measurement method is -8.0 to +8.0%, and the dimensional change rate (ii) after heating at 170°C for 1 hour is -4 The prepreg for coreless substrates according to [8] above, which has a content of .0 to +4.0%.
<Measurement method of dimensional change rate>
The evaluation board was a 250 cm square copper-clad laminate with 12 μm thick electrolytic copper foil on both surfaces of the prepreg, and a total of 4 reference holes were provided at 1 cm vertically and 1 cm horizontally from the four corners, and adjacent The average value of the distance between holes is used as the standard dimension,
After removing the copper foil by immersing the evaluation board in a copper etching solution, the average value of the distance between adjacent holes is taken as the post-etching dimension,
After heating the evaluation board after etching at 170° C. for 1 hour, the average value of the distance between adjacent holes is calculated based on the following formula as the dimension after heating.
Dimensional change rate (i) (%) = (dimension after etching - standard dimension) x 100 / standard dimension Dimensional change rate (ii) (%) = (dimension after heating - dimension after etching) x 100 / dimension after etching [10 ] The prepreg for coreless substrates according to [8] or [9] above, wherein the thickness accuracy value measured according to the following measurement method is 10% or less.
<Measurement method of thickness accuracy>
A total of 11 points in the width direction in 50 mm increments from the center of the width direction of a copper-clad laminate having electrolytic copper foil with a thickness of 12 μm on both surfaces of the prepreg, and 10 points in 50 mm increments in the length direction from the 11 points above as starting points. Measure the thickness, find the maximum thickness, minimum thickness, and average thickness, and calculate the rate of change of the maximum thickness with respect to the average thickness and the rate of change of the minimum thickness with respect to the average thickness based on the following formula. Find each value, and use the larger value as the thickness accuracy value.
Rate of change in maximum thickness (%) = (Maximum thickness - Average thickness) x 100/Average thickness Rate of change in minimum thickness (%) = (Average thickness - Minimum thickness) x 100/Average thickness [11] The prepreg for coreless substrates according to any one of [8] to [10] above, wherein the cured product has an elastic modulus of 10 to 20 GPa.
[12] The prepreg for coreless substrates according to any one of [8] to [11] above, wherein the cured product has a coefficient of thermal expansion of 5.0 to 6.5 ppm/°C.
[13] A coreless substrate containing an insulating layer formed using the coreless substrate prepreg according to any one of [8] to [12] above.
[14] A semiconductor package comprising a semiconductor element mounted on the coreless substrate according to [13] above.
[15] A method for manufacturing a coreless substrate, which comprises forming a build-up layer in which a conductor layer and an insulating layer are alternately laminated on a support, and then separating the build-up layer from the support, A method for producing a coreless substrate, wherein at least one of the insulating layers is formed using a prepreg for a coreless substrate produced by the method for producing a prepreg for a coreless substrate according to [1] to [6] above.
本発明によると、作業性が良好であり、優れた厚み精度及び寸法安定性を有するコアレス基板用プリプレグが得られるコアレス基板用プリプレグの製造方法及び製造装置、該製造方法により得られるコアレス基板用プリプレグ、並びに該コアレス基板用プリプレグを用いたコアレス基板及びその製造方法を提供することができる。 According to the present invention, there is provided a method and apparatus for manufacturing a prepreg for coreless substrates, which can obtain a prepreg for coreless substrates that has good workability and excellent thickness accuracy and dimensional stability, and a prepreg for coreless substrates obtained by the manufacturing method. , and a coreless substrate using the prepreg for coreless substrates and a method for manufacturing the same.
［コアレス基板用プリプレグの製造方法及び製造装置］
本発明のコアレス基板用プリプレグ（以下、単に「プリプレグ」ともいう）の製造方法は、シート状骨材（以下、単に「骨材」ともいう）の少なくとも一方の表面に、熱硬化性樹脂組成物を含んでなる樹脂フィルム（Ｉ）（以下、単に「樹脂フィルム（Ｉ）」ともいう）を貼付するコアレス基板用プリプレグの製造方法であって、前記貼付を、常圧下において、前記樹脂フィルム（Ｉ）を、前記シート状骨材の少なくとも一方の表面に圧接するフィルム圧接工程により行う、コアレス基板用プリプレグの製造方法である。
また、本発明のコアレス基板用プリプレグの製造装置は、本発明のコアレス基板用プリプレグの製造方法に用いられるコアレス基板用プリプレグの製造装置であって、常圧下において、前記樹脂フィルム（Ｉ）を、前記シート状骨材の少なくとも一方に圧接させて貼付するフィルム圧接手段を有する、コアレス基板用プリプレグの製造装置である。
ここで、「貼付」とは、樹脂フィルム（Ｉ）の熱硬化性樹脂組成物と骨材とが接している状態の他、樹脂フィルム（Ｉ）の熱硬化性樹脂組成物が骨材中の空隙部へ入り込んでいる状態も含み、特に後者の状態にあることが好ましい。
前記フィルム圧接工程は、前記樹脂フィルム（Ｉ）を、前記シート状骨材の一方の表面に圧接する工程であってもよく、前記シート状骨材の両方の表面に圧接する工程であってもよいが、生産性の観点からは、前記シート状骨材の両方の表面に圧接する工程であることが好ましい。
[Manufacturing method and manufacturing device for prepreg for coreless substrates]
The method for producing prepreg for coreless substrates (hereinafter also simply referred to as "prepreg") of the present invention includes a thermosetting resin composition on at least one surface of sheet-like aggregate (hereinafter also simply referred to as "aggregate"). A method for producing a prepreg for a coreless board, in which a resin film (I) (hereinafter also simply referred to as "resin film (I)") comprising: ) is a method for producing a prepreg for a coreless substrate, which is carried out by a film press-contact step of press-contacting at least one surface of the sheet-like aggregate.
Furthermore, the apparatus for producing prepreg for coreless substrates of the present invention is an apparatus for producing prepreg for coreless substrates used in the method for producing prepreg for coreless substrates of the present invention, in which the resin film (I) is produced under normal pressure. The present invention is an apparatus for manufacturing a prepreg for coreless substrates, which has a film pressing means for pressing and pasting a film onto at least one of the sheet-like aggregates.
Here, "affixing" refers to the state in which the thermosetting resin composition of the resin film (I) and the aggregate are in contact with each other, as well as the state in which the thermosetting resin composition of the resin film (I) is in contact with the aggregate. The latter state is particularly preferred, including the state in which it has entered the void.
The film pressing step may be a step of pressing the resin film (I) onto one surface of the sheet-like aggregate, or a step of pressing the resin film (I) onto both surfaces of the sheet-like aggregate. However, from the viewpoint of productivity, it is preferable that the process be in pressure contact with both surfaces of the sheet-like aggregate.
以下、図１を参照しながら、本発明のプリプレグの製造方法及びプリプレグの製造装置１の好ましい一実施態様について具体的に説明する。
なお、プリプレグの製造装置１は、一対の樹脂フィルム（Ｉ）５４を、それぞれ、シート状骨材４０の両面に溶融貼付する装置として説明するが、１つの樹脂フィルム（Ｉ）５４をシート状骨材４０の一方の表面にのみ貼付する装置としてもよい。この場合、図１において、骨材４０より下側（又は上側）にある、一方の樹脂フィルム送出装置３、保護フィルム剥がし機構４及び保護フィルム巻取装置５は不要である。
Hereinafter, a preferred embodiment of the prepreg manufacturing method and prepreg manufacturing apparatus 1 of the present invention will be specifically described with reference to FIG. 1.
The prepreg manufacturing apparatus 1 will be described as an apparatus that melts and attaches a pair of resin films (I) 54 to both sides of the sheet-shaped aggregate 40, but one resin film (I) 54 is attached to the sheet-shaped aggregate 40. It is also possible to use a device that attaches only to one surface of the material 40. In this case, the resin film delivery device 3, the protective film peeling mechanism 4, and the protective film winding device 5, which are located below (or above) the aggregate 40 in FIG. 1, are unnecessary.
本発明のプリプレグの製造方法は、プリプレグの製造装置１で行うことができる。
なお、プリプレグの製造装置１は、作業性の観点から、常圧下に置かれる。ここで、本明細書中、「常圧下」は「大気圧下」と同義である。当該方法によってプリプレグを製造する場合、例えば、真空ラミネーター等を採用した場合に生じ易い作業性の問題が生じない傾向にあり、優れた作業性が得られる。
The prepreg manufacturing method of the present invention can be carried out using the prepreg manufacturing apparatus 1.
Note that the prepreg manufacturing apparatus 1 is placed under normal pressure from the viewpoint of workability. Here, in this specification, "under normal pressure" is synonymous with "under atmospheric pressure". When a prepreg is manufactured by this method, problems with workability that tend to occur when, for example, a vacuum laminator or the like is employed tend not to occur, and excellent workability can be obtained.
プリプレグの製造装置１は、骨材送出装置２と、一対の樹脂フィルム送出装置３及び３と、シート加熱加圧装置（フィルム圧接手段）６と、プリプレグ巻取装置８と、を備える。プリプレグの製造装置１は、さらに、シート加圧冷却装置７と、一対の保護フィルム剥がし機構４及び４と、一対の保護フィルム巻取装置５及び５と、を備えることが好ましい。 The prepreg manufacturing apparatus 1 includes an aggregate delivery device 2, a pair of resin film delivery devices 3 and 3, a sheet heating and pressing device (film pressure welding means) 6, and a prepreg winding device 8. Preferably, the prepreg manufacturing apparatus 1 further includes a sheet pressure cooling device 7, a pair of protective film peeling mechanisms 4 and 4, and a pair of protective film winding devices 5 and 5.
骨材送出装置２は、シート状の骨材４０が巻かれたロールを巻き方向とは反対方向に回転させて、ロールに巻かれた骨材４０を送り出す装置である。図１において、骨材送出装置２は、骨材４０をローラの下側からシート加熱加圧装置６に向けて送り出している。 The aggregate delivery device 2 is a device that rotates a roll around which sheet-like aggregate 40 is wound in a direction opposite to the winding direction, and sends out the aggregate 40 wound around the roll. In FIG. 1, the aggregate delivery device 2 sends the aggregate 40 toward the sheet heating and pressing device 6 from below the roller.
一対の樹脂フィルム送出装置３及び３は、保護フィルム付き樹脂フィルム（Ｉ）５０が巻かれたロールと、送り出される保護フィルム付き樹脂フィルム（Ｉ）５０に所定の張力を付与させながらロールを回転可能に支持する支持機構とを有し、保護フィルム付き樹脂フィルム（Ｉ）５０が巻かれたロールを巻き方向とは反対方向に回転させて、ロールに巻かれた保護フィルム付き樹脂フィルム（Ｉ）５０を送り出す装置である。後述するように、保護フィルム付き樹脂フィルム（Ｉ）５０は、樹脂フィルム（Ｉ）５４と、樹脂フィルム（Ｉ）５４の片方の骨材側フィルム表面（樹脂フィルム（Ｉ）５４の両表面のうち、骨材４０側の表面）５４ａに積層された保護フィルム５２とを含むシート状のフィルムである。
なお、前記保護フィルム付き樹脂フィルム（Ｉ）５０において、樹脂フィルム（Ｉ）の、保護フィルム５２が付いている面とは反対側の面には、通常、支持体が付いている。つまり、支持体／樹脂フィルム（Ｉ）／保護フィルムという構成になっている。なお、樹脂フィルム（Ｉ）が、支持体及び保護フィルムからなる群から構成される１つ以上を有している場合、熱硬化性樹脂組成物を層形成してなる層を「樹脂層」と称する場合がある。
The pair of resin film delivery devices 3 and 3 can rotate the roll while applying a predetermined tension to the roll around which the resin film with protective film (I) 50 is wound and the resin film with protective film (I) 50 to be sent out. The resin film (I) 50 with a protective film wound around the roll is rotated in the opposite direction to the winding direction. It is a device that sends out. As described later, the resin film (I) 50 with a protective film has a resin film (I) 54 and one aggregate side film surface of the resin film (I) 54 (out of both surfaces of the resin film (I) 54). It is a sheet-like film including a protective film 52 laminated on a surface (surface on the aggregate 40 side) 54a.
In the protective film-attached resin film (I) 50, a support is usually attached to the surface of the resin film (I) opposite to the surface on which the protective film 52 is attached. In other words, the structure is support/resin film (I)/protective film. In addition, when the resin film (I) has one or more of the group consisting of a support and a protective film, the layer formed by layering the thermosetting resin composition is referred to as a "resin layer". Sometimes referred to as
一対の樹脂フィルム送出装置３及び３は、それぞれ、送り出された骨材４０の表面４０ａ側及び裏面４０ｂ側に位置する。
一方の樹脂フィルム送出装置３は、送り出された骨材４０の表面４０ａ側に位置し、保護フィルム５２が、送り出された骨材４０側になるように、一方の保護フィルム付き樹脂フィルム（Ｉ）５０をローラの下側から一方の保護フィルム剥がし機構４に向けて送り出す装置である。
同様に、他方の樹脂フィルム送出装置３は、送り出された骨材４０の裏面４０ｂ側に位置し、保護フィルム５２が、送り出された骨材４０側になるように、他方の保護フィルム付き樹脂フィルム（Ｉ）５０をローラの上側から他方の保護フィルム剥がし機構４に向けて送り出す装置である。
A pair of resin film delivery devices 3 and 3 are located on the front surface 40a side and the back surface 40b side of the sent-out aggregate 40, respectively.
One resin film delivery device 3 is located on the surface 40a side of the delivered aggregate 40, and one resin film with a protective film (I) is placed so that the protective film 52 is on the delivered aggregate 40 side. 50 from below the roller toward one of the protective film peeling mechanisms 4.
Similarly, the other resin film delivery device 3 is located on the back surface 40b side of the delivered aggregate 40, and the other resin film with protective film is placed so that the protective film 52 is on the delivered aggregate 40 side. (I) This is a device that sends out the film 50 from above the roller toward the other protective film peeling mechanism 4.
一対の保護フィルム剥がし機構４及び４は、それぞれ、送り出された骨材４０の表面４０ａ側及び裏面４０ｂ側に位置する転向ローラである。
一方の保護フィルム剥がし機構４は、一方の樹脂フィルム送出装置３から送り出され、一方の保護フィルム剥がし機構４に向けて進む保護フィルム付き樹脂フィルム（Ｉ）５０を、回転する転向ローラの表面で受け、一方の保護フィルム付き樹脂フィルム（Ｉ）５０のうち一方の樹脂フィルム（Ｉ）５４をシート加熱加圧装置６に向けて進ませると共に、一方の保護フィルム５２を一方の保護フィルム巻取装置５に向けて進ませることにより、一方の保護フィルム付き樹脂フィルム（Ｉ）５０から一方の保護フィルム５２を剥がす機構である。これにより、一方の樹脂フィルム（Ｉ）５４の骨材側フィルム表面５４ａが露出する。
同様に他方の保護フィルム剥がし機構４は、他方の樹脂フィルム送出装置３から送り出され、他方の保護フィルム剥がし機構４に向けて進む他方の保護フィルム付き樹脂フィルム（Ｉ）５０を、回転する転向ローラの表面で受け、他方の保護フィルム付き樹脂フィルム（Ｉ）５０のうち他方の樹脂フィルム（Ｉ）５４をシート加熱加圧装置６に向けて進ませると共に、他方の保護フィルム５２を他方の保護フィルム巻取装置５に向けて進ませることにより、他方の保護フィルム付き樹脂フィルム（Ｉ）５０から他方の保護フィルム５２を剥がす機構である。これにより、他方の樹脂フィルム（Ｉ）５４の骨材側フィルム表面５４ａが露出する。
The pair of protective film peeling mechanisms 4 and 4 are turning rollers located on the front surface 40a side and the back surface 40b side of the sent-out aggregate 40, respectively.
One protective film peeling mechanism 4 receives on the surface of a rotating turning roller a resin film with a protective film (I) 50 sent out from one resin film sending device 3 and advancing toward one protective film peeling mechanism 4. , one of the resin films (I) 54 with a protective film is advanced toward the sheet heating and pressing device 6, and one of the protective films 52 is advanced toward the one protective film winding device 5. This is a mechanism for peeling off one of the protective films 52 from the other protective film-attached resin film (I) 50 by moving the protective film toward. As a result, the aggregate side film surface 54a of one resin film (I) 54 is exposed.
Similarly, the other protective film peeling mechanism 4 moves the other protective film-attached resin film (I) 50, which is sent out from the other resin film sending device 3 and advances toward the other protective film peeling mechanism 4, by a rotating turning roller. The other resin film (I) 54 of the other resin film (I) 50 with a protective film is advanced toward the sheet heating and pressing device 6, and the other protective film 52 is This is a mechanism for peeling off the other protective film 52 from the other protective film-attached resin film (I) 50 by moving it toward the winding device 5. This exposes the aggregate side film surface 54a of the other resin film (I) 54.
一対の保護フィルム巻取装置５及び５は、それぞれ、送り出された骨材４０の表面４０ａ側及び裏面４０ｂ側に位置し、一対の保護フィルム剥がし機構４及び４で剥がされた、保護フィルム５２及び５２を巻き取る巻取装置である。 A pair of protective film winding devices 5 and 5 are respectively located on the front surface 40a side and the back surface 40b side of the sent-out aggregate 40, and the protective film 52 and 5 are peeled off by the pair of protective film peeling mechanisms 4 and 4. This is a winding device that winds up 52.
シート加熱加圧装置６は、一対の加熱圧縮ローラと、一対の加熱圧縮ローラに圧縮力を付与する圧縮力付与機構（図示せず）とを有する。一対の加熱圧縮ローラは、所定の設定された温度で加熱ができるよう、内部に加熱体を有する。
シート加熱加圧装置６は、入り込んだ骨材４０に樹脂フィルム（Ｉ）５４及び５４を回転する一対の加熱圧縮ローラで圧接させてシート状のプリプレグ６０を形成する（フィルム圧接工程）と共に、プリプレグ６０をシート加圧冷却装置７に向けて送り出す。具体的には、骨材送出装置２から送り出された骨材４０の表面４０ａ及び裏面４０ｂに、それぞれ、一対の保護フィルム剥がし機構４及び４から送り出された樹脂フィルム（Ｉ）５４及び５４が積層するように、骨材送出装置２から送り出された骨材４０と、一対の保護フィルム剥がし機構４及び４からそれぞれ送り出された樹脂フィルム（Ｉ）５４及び５４とが、一対の加熱圧縮ローラの間に入り込む。
このとき、一方の樹脂フィルム（Ｉ）５４の骨材側フィルム表面５４ａ側が骨材４０の表面４０ａ側に接着するように、一方の樹脂フィルム（Ｉ）５４が骨材４０に積層し、また、他方の樹脂フィルム（Ｉ）５４の骨材側フィルム表面５４ａ側が骨材４０の裏面４０ｂ側に接着するように、他方の樹脂フィルム（Ｉ）５４が骨材４０に積層してプリプレグ６０が形成される。シート加熱加圧装置６から送り出されたプリプレグ６０は高温状態である。
The sheet heating and pressing device 6 includes a pair of heating compression rollers and a compression force applying mechanism (not shown) that applies compression force to the pair of heating compression rollers. The pair of heating compression rollers has a heating body inside so that they can be heated at a predetermined set temperature.
The sheet heating and pressing device 6 presses the resin films (I) 54 and 54 onto the aggregate 40 that has entered with a pair of rotating heating compression rollers to form a sheet-like prepreg 60 (film pressing process), and 60 is sent out toward the sheet pressure cooling device 7. Specifically, resin films (I) 54 and 54 sent out from a pair of protective film peeling mechanisms 4 and 4 are laminated on the front surface 40a and back surface 40b of the aggregate 40 sent out from the aggregate delivery device 2, respectively. As shown in FIG. Get into it.
At this time, one of the resin films (I) 54 is laminated on the aggregate 40 such that the aggregate-side film surface 54a of the one resin film (I) 54 adheres to the surface 40a of the aggregate 40, and The prepreg 60 is formed by laminating the other resin film (I) 54 on the aggregate 40 such that the aggregate-side film surface 54a of the other resin film (I) 54 adheres to the back surface 40b of the aggregate 40. Ru. The prepreg 60 sent out from the sheet heating and pressing device 6 is in a high temperature state.
シート加圧冷却装置７は、一対の冷却圧縮ローラと、一対の冷却圧縮ローラに圧縮力を付与する圧縮力付与機構（図示せず）とを有する。一対の冷却圧縮ローラは、シート加熱加圧装置６から送り出された、高温のプリプレグ６０を回転する一対の冷却圧縮ローラで圧縮すると共に冷却し、プリプレグ巻取装置８に送り出す。 The sheet pressurizing and cooling device 7 includes a pair of cooling compression rollers and a compression force applying mechanism (not shown) that applies compression force to the pair of cooling compression rollers. The pair of cooling compression rollers compresses and cools the high-temperature prepreg 60 sent out from the sheet heating and pressing device 6 with the pair of rotating cooling compression rollers, and sends it out to the prepreg winding device 8.
プリプレグ巻取装置８は、シート加圧冷却装置７から送り出されたシート状のプリプレグ６０を巻き取るロールと、ロールを回転させる駆動機構（図示せず）とを有する。
ローララミネート後は冷却圧縮ローラで冷却し、不要な熱の除去と製品の平坦化を行うことが好ましい。
The prepreg winding device 8 includes a roll that winds up the sheet-like prepreg 60 sent out from the sheet pressure cooling device 7, and a drive mechanism (not shown) that rotates the roll.
After roller lamination, it is preferable to cool the product using a cooling compression roller to remove unnecessary heat and flatten the product.
以上のプリプレグの製造装置１は、以下のように動作する。
まず、骨材送出装置２からシート状の骨材４０を、シート加熱加圧装置６に向けて送り出す。このとき、骨材４０の表面４０ａ及び裏面４０ｂは、露出している。
The prepreg manufacturing apparatus 1 described above operates as follows.
First, a sheet-shaped aggregate 40 is sent out from the aggregate delivery device 2 toward the sheet heating and pressing device 6 . At this time, the front surface 40a and back surface 40b of the aggregate 40 are exposed.
他方、保護フィルム５２が、送り出された骨材４０側になるように、一方の保護フィルム付き樹脂フィルム（Ｉ）５０を一方の樹脂フィルム送出装置３のローラの下側から一方の保護フィルム剥がし機構４に向けて送り出している。また、保護フィルム５２が、送り出された骨材４０側になるように、他方の保護フィルム付き樹脂フィルム（Ｉ）５０を他方の樹脂フィルム送出装置３のローラの上側から他方の保護フィルム剥がし機構４に向けて送り出している。 On the other hand, one protective film peeling mechanism removes one protective film-attached resin film (I) 50 from below the roller of one resin film sending device 3 so that the protective film 52 is on the fed-out aggregate 40 side. We are sending it out for the 4th. Further, the other protective film-attached resin film (I) 50 is removed from the upper side of the roller of the other resin film sending device 3 to the other protective film peeling mechanism 4 so that the protective film 52 is on the fed-out aggregate 40 side. It is being sent towards.
次に、送り出された一方の保護フィルム付き樹脂フィルム（Ｉ）５０は、一方の保護フィルム剥がし機構４である転向ローラに架けられ転向する際に、骨材側フィルム表面５４ａが露出するように、一方の保護フィルム付き樹脂フィルム（Ｉ）５０から一方の保護フィルム５２を剥がして一方の樹脂フィルム（Ｉ）５４をシート加熱加圧装置６に向けて進ませる。これにより、一方の樹脂フィルム（Ｉ）５４の骨材側フィルム表面５４ａが露出する。同様に、送り出された他方の保護フィルム付き樹脂フィルム（Ｉ）５０は、他方の保護フィルム剥がし機構４である転向ローラに架けられ転向する際に、骨材側フィルム表面５４ａが露出するように、他方の保護フィルム付き樹脂フィルム（Ｉ）５０から他方の保護フィルム５２を剥がして他方の樹脂フィルム（Ｉ）５４をシート加熱加圧装置６に向けて進ませる。これにより、他方の樹脂フィルム（Ｉ）５４の骨材側フィルム表面５４ａが露出する。
剥がされた一対の保護フィルム５２及び５２は、それぞれ、一対の保護フィルム巻取装置５及び５で巻き取られる。
Next, when the sent-out resin film (I) 50 with a protective film is hung on a turning roller that is one of the protective film peeling mechanisms 4 and turned, the film surface 54a on the aggregate side is exposed. One protective film 52 is peeled off from one protective film-attached resin film (I) 50, and one resin film (I) 54 is advanced toward the sheet heating and pressing device 6. As a result, the aggregate side film surface 54a of one resin film (I) 54 is exposed. Similarly, when the sent out resin film (I) 50 with a protective film is hung on the turning roller that is the other protective film peeling mechanism 4 and turned, the film surface 54a on the aggregate side is exposed. The other protective film 52 is peeled off from the other protective film-attached resin film (I) 50, and the other resin film (I) 54 is advanced toward the sheet heating and pressing device 6. This exposes the aggregate side film surface 54a of the other resin film (I) 54.
The pair of peeled protective films 52 and 52 are wound up by a pair of protective film winding devices 5 and 5, respectively.
骨材送出装置２から送り出され、表面４０ａ及び裏面４０ｂが骨材４０に、それぞれ、骨材側フィルム表面５４ａ及び５４ａが溶融した樹脂フィルム（Ｉ）５４及び５４が積層するように、骨材送出装置２から送り出された骨材４０と、一対の保護フィルム剥がし機構４及び４からそれぞれ送り出された樹脂フィルム（Ｉ）５４及び５４とが一対の加熱圧縮ローラ６の間に入り込む。さらに、常圧下において、一対の樹脂フィルム（Ｉ）５４及び５４の骨材側フィルム表面５４ａ及び５４ａを、それぞれ、表面４０ａ及び裏面４０ｂが骨材４０に、シート加熱加圧装置６で圧接させてプリプレグ６０を得る（フィルム圧接工程）。このとき、一対の加熱圧縮ローラの内部にある加熱体の温度制御をすることにより、一対の加熱圧縮ローラを所定の温度に維持し、フィルム圧接工程をする際に加熱しながら加圧をする。 The aggregate is sent out from the aggregate sending device 2, and the aggregate is sent out so that the front surface 40a and the back surface 40b are stacked on the aggregate 40, and the resin films (I) 54 and 54, in which the aggregate side film surfaces 54a and 54a are melted, are laminated, respectively. The aggregate 40 sent out from the device 2 and the resin films (I) 54 and 54 sent out from the pair of protective film peeling mechanisms 4 and 4, respectively, enter between the pair of heated compression rollers 6. Further, under normal pressure, the aggregate side film surfaces 54a and 54a of the pair of resin films (I) 54 and 54 are brought into pressure contact with the aggregate 40 with the front surface 40a and the back surface 40b, respectively, using the sheet heating and pressing device 6. A prepreg 60 is obtained (film pressure bonding process). At this time, by controlling the temperature of the heating body inside the pair of heating compression rollers, the pair of heating compression rollers are maintained at a predetermined temperature, and pressure is applied while heating during the film pressing process.
骨材に樹脂フィルム（Ｉ）を加熱加圧接着する際、加熱圧縮ローラの温度は、樹脂フィルム（Ｉ）の形成に使用する熱硬化性樹脂組成物をレオメータで測定した最低溶融粘度温度のマイナス４０℃からプラス２０℃の範囲が好ましい。つまり、フィルム圧接工程は、樹脂フィルム（Ｉ）を、樹脂フィルム（Ｉ）の最低溶融粘度温度のマイナス４０℃からプラス２０℃の範囲に加熱しながら、前記シート状骨材の少なくとも一方の表面に圧接する工程であることが好ましい。
なお、熱硬化性樹脂組成物の最低溶融粘度温度は、プリプレグの生産性の観点から、６０～１５０℃が好ましく、８０～１４０℃がより好ましく、１００～１３０℃がさらに好ましい。
When bonding the resin film (I) to the aggregate under heat and pressure, the temperature of the heated compression roller is set to a temperature minus the lowest melt viscosity temperature of the thermosetting resin composition used to form the resin film (I) measured with a rheometer. The temperature range is preferably from 40°C to +20°C. In other words, in the film pressure welding step, the resin film (I) is heated to a temperature in the range of -40°C to +20°C, which is the lowest melt viscosity temperature of the resin film (I), and is applied to at least one surface of the sheet-like aggregate. It is preferable that the process involves pressure contact.
Note that the minimum melt viscosity temperature of the thermosetting resin composition is preferably 60 to 150°C, more preferably 80 to 140°C, and even more preferably 100 to 130°C, from the viewpoint of prepreg productivity.
シート加熱加圧装置６から送り出されたプリプレグ６０を、シート加圧冷却装置７により、さらに加圧し、また、冷却する。
シート加圧冷却装置７から送り出されたプリプレグ６０を、プリプレグ巻取装置８により、巻き取る。
The prepreg 60 sent out from the sheet heating and pressing device 6 is further pressurized and cooled by the sheet pressing and cooling device 7.
The prepreg 60 sent out from the sheet pressure cooling device 7 is wound up by the prepreg winding device 8.
次に、本発明のプリプレグの製造方法で使用される、シート状骨材及び樹脂フィルム（Ｉ）について、順に説明をする。 Next, the sheet-like aggregate and resin film (I) used in the prepreg manufacturing method of the present invention will be explained in order.
＜シート状骨材＞
シート状骨材としては、無機繊維基材、有機繊維基材等を、単体で又は混合して使用した織布、不織布等が挙げられる。
無機繊維基材としては、Ｅガラス、Ｄガラス、Ｓガラス、Ｑガラス等のガラス、カーボンなどの繊維基材が挙げられ、有機繊維基材としては、ポリイミド、ポリエステル、テトラフルオロエチレン、アラミド、セルロール等の繊維基材が挙げられる。
骨材としては、織布、不織布、ロービンク、チョップドストランドマット、サーフェシングマット等の形状を有するものを使用できる。これらの中でも、織布又は不織布が好ましい。
骨材の材質及び形状は、目的とする成形物の用途、性能等により適宜選択され、必要により、１種の材質及び１種の形状からなる繊維基材であってもよいし、２種以上の材質からなる骨材であってもよいし、２種以上の形状を有する骨材であってもよい。
骨材の厚さは、例えば、０．００２～０．５ｍｍであり、基板の薄型化及び高密度配線を可能にする観点からは、４～１００μｍが好ましく、６～５０μｍがより好ましく、８～２０μｍがさらに好ましく、８～１５μｍが特に好ましい。
骨材は、耐熱性、耐湿性、加工性等の観点から、シランカップリング剤等で表面処理したもの、機械的に開繊処理を施したものが好ましい。
<Sheet aggregate>
Examples of the sheet-like aggregate include woven fabrics, non-woven fabrics, etc. using inorganic fiber base materials, organic fiber base materials, etc. alone or in combination.
Examples of inorganic fiber base materials include glass such as E glass, D glass, S glass, and Q glass, and fiber base materials such as carbon. Examples of organic fiber base materials include polyimide, polyester, tetrafluoroethylene, aramid, and cellulose. Examples include fiber base materials such as.
As the aggregate, materials having shapes such as woven fabric, non-woven fabric, raw binder, chopped strand mat, surfacing mat, etc. can be used. Among these, woven fabrics or nonwoven fabrics are preferred.
The material and shape of the aggregate are appropriately selected depending on the intended use and performance of the molded product, and if necessary, it may be a fiber base material consisting of one type of material and one type of shape, or it may be a fiber base material consisting of one type of material and one type of shape, or two or more types of aggregate. The aggregate may be made of the following materials, or may have two or more shapes.
The thickness of the aggregate is, for example, 0.002 to 0.5 mm, and from the viewpoint of making the board thinner and enabling high-density wiring, it is preferably 4 to 100 μm, more preferably 6 to 50 μm, and 8 to 50 μm. 20 μm is more preferred, and 8 to 15 μm is particularly preferred.
From the viewpoints of heat resistance, moisture resistance, processability, etc., the aggregate is preferably one that has been surface-treated with a silane coupling agent or the like, or one that has been mechanically opened.
＜樹脂フィルム（Ｉ）＞
樹脂フィルム（Ｉ）は、熱硬化性樹脂組成物を含んでなる樹脂フィルムである。
樹脂フィルム（Ｉ）は、該樹脂フィルム（Ｉ）の一方の表面に支持体が付いている「支持体付き樹脂フィルム（Ｉ）」の状態であることが好ましく、更に樹脂フィルム（Ｉ）の他方の面に保護フィルムが付いている「支持体及び保護フィルム付き樹脂フィルム（Ｉ）」の状態であってもよい。
<Resin film (I)>
The resin film (I) is a resin film containing a thermosetting resin composition.
The resin film (I) is preferably in the state of a "resin film with support (I)" in which a support is attached to one surface of the resin film (I), and the resin film (I) is further It may be in the state of "resin film (I) with support and protective film" with a protective film attached to the surface thereof.
樹脂フィルム（Ｉ）が含んでなる熱硬化性樹脂組成物は、耐熱性、低熱膨張性、誘電特性及び寸法安定性の観点から、１分子中に少なくとも２個のＮ－置換マレイミド基を有するマレイミド化合物（ａ）（以下、「（ａ）成分」又は「マレイミド化合物（ａ）」ともいう）、１分子中に少なくとも２個の１級アミノ基を有するアミン化合物（ｂ）（以下、「（ｂ）成分」又は「アミン化合物（ｂ）」ともいう）を含有することが好ましい。
また、熱硬化性樹脂組成物は、同様の観点から、１分子中に少なくとも２個のＮ－置換マレイミド基を有するマレイミド化合物（ａ）と、１分子中に少なくとも２個の１級アミノ基を有するアミン化合物（ｂ）と、の反応物である変性ポリイミド（Ｘ）を含有することが好ましい。
以下、熱硬化性樹脂組成物を構成する各成分について説明する。
The thermosetting resin composition that the resin film (I) contains is a maleimide having at least two N-substituted maleimide groups in one molecule, from the viewpoint of heat resistance, low thermal expansion, dielectric properties, and dimensional stability. Compound (a) (hereinafter also referred to as "component (a)" or "maleimide compound (a)"), amine compound (b) having at least two primary amino groups in one molecule (hereinafter referred to as "(b) ) component" or "amine compound (b)").
In addition, from the same viewpoint, the thermosetting resin composition contains a maleimide compound (a) having at least two N-substituted maleimide groups in one molecule and at least two primary amino groups in one molecule. It is preferable to contain a modified polyimide (X) which is a reaction product of the amine compound (b).
Each component constituting the thermosetting resin composition will be explained below.
（１分子中に少なくとも２個のＮ－置換マレイミド基を有するマレイミド化合物（ａ））
マレイミド化合物（ａ）は、１分子中に少なくとも２個のＮ－置換マレイミド基を有するマレイミド化合物であれば特に限定されない。マレイミド化合物（ａ）は１種を単独で用いても２種類以上を混合して用いてもよい。
マレイミド化合物（ａ）としては、１分子中に２個のＮ－置換マレイミド基を有するマレイミド化合物が好ましく、下記一般式（ａ－１）で表される化合物がより好ましい。
(Maleimide compound (a) having at least two N-substituted maleimide groups in one molecule)
The maleimide compound (a) is not particularly limited as long as it is a maleimide compound having at least two N-substituted maleimide groups in one molecule. The maleimide compound (a) may be used alone or in combination of two or more.
As the maleimide compound (a), a maleimide compound having two N-substituted maleimide groups in one molecule is preferable, and a compound represented by the following general formula (a-1) is more preferable.
（一般式（ａ－１）中、Ｘａ１は、下記一般式（ａ１－１）、（ａ１－２）、（ａ１－３）又は（ａ１－４）で表される基である。）
(In the general formula (a-1), X a1 is a group represented by the following general formula (a1-1), (a1-2), (a1-3) or (a1-4).)
（一般式（ａ１－１）中、Ｒａ１は各々独立に、炭素数１～５の脂肪族炭化水素基又はハロゲン原子である。ｐは０～４の整数である。）
(In the general formula (a1-1), each R a1 is independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. p is an integer of 0 to 4.)
（一般式（ａ１－２）中、Ｒａ２及びＲａ３は各々独立に、炭素数１～５の脂肪族炭化水素基又はハロゲン原子である。Ｘａ２は炭素数１～５のアルキレン基、炭素数２～５のアルキリデン基、エーテル基、スルフィド基、スルホニル基、カルボニルオキシ基、ケト基、単結合又は下記一般式（ａ１－２－１）で表される基である。ｑ及びｒは各々独立に０～４の整数である。）
(In the general formula (a1-2), R a2 and R a3 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. X a2 is an alkylene group having 1 to 5 carbon atoms, a carbon 2 to 5 alkylidene groups, ether groups, sulfide groups, sulfonyl groups, carbonyloxy groups, keto groups, single bonds, or groups represented by the following general formula (a1-2-1). q and r are each (Independently an integer from 0 to 4.)
（一般式（ａ１－２－１）中、Ｒａ４及びＲａ５は各々独立に、炭素数１～５の脂肪族炭化水素基又はハロゲン原子である。Ｘａ３は炭素数１～５のアルキレン基、炭素数２～５のアルキリデン基、エーテル基、スルフィド基、スルホニル基、カルボニルオキシ基［－Ｏ－Ｃ（＝Ｏ）－］、ケト基又は単結合である。ｓ及びｔは各々独立に０～４の整数である。）
(In the general formula (a1-2-1), R a4 and R a5 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. X a3 is an alkylene group having 1 to 5 carbon atoms. , an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group [-OC(=O)-], a keto group, or a single bond. s and t are each independently 0 It is an integer between ~4.)
（一般式（ａ１－３）中、ｎは１～１０の整数である。）
(In general formula (a1-3), n is an integer from 1 to 10.)
（一般式（ａ１－４）中、Ｒａ６及びＲａ７は各々独立に、水素原子又は炭素数１～５の脂肪族炭化水素基である。ｕは１～８の整数である。）
(In general formula (a1-4), R a6 and R a7 are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. u is an integer of 1 to 8.)
前記一般式（ａ１－１）中、Ｒａ１が表す脂肪族炭化水素基としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔ－ブチル基、ｎ－ペンチル基等が挙げられる。該脂肪族炭化水素基としては、好ましくは炭素数１～３の脂肪族炭化水素基であり、より好ましくはメチル基である。また、ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられる。
以上の中でも、Ｒａ１としては炭素数１～５の脂肪族炭化水素基が好ましい。
ｐは０～４の整数であり、入手容易性の観点から、好ましくは０～２の整数、より好ましくは０又は１、さらに好ましくは０である。ｐが２以上の整数である場合、複数のＲａ１同士は同一であっても異なっていてもよい。
In the general formula (a1-1), the aliphatic hydrocarbon group represented by R a1 includes methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n -pentyl group, etc. The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably a methyl group. Further, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.
Among the above, R a1 is preferably an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
p is an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0 from the viewpoint of availability. When p is an integer of 2 or more, the plural R a1s may be the same or different.
前記一般式（ａ１－２）中、Ｒａ２及びＲａ３が表す炭素数１～５の脂肪族炭化水素基、ハロゲン原子としては、前記Ｒａ１の場合と同じものが挙げられる。該脂肪族炭化水素基としては、好ましくは炭素数１～３の脂肪族炭化水素基、より好ましくはメチル基及びエチル基、さらに好ましくはエチル基である。
Ｘａ２が表す炭素数１～５のアルキレン基としては、メチレン基、１，２－ジメチレン基、１，３－トリメチレン基、１，４－テトラメチレン基、１，５－ペンタメチレン基等が挙げられる。該アルキレン基としては、耐熱性及び低熱膨張性の観点から、好ましくは炭素数１～３のアルキレン基であり、より好ましくはメチレン基である。
Ｘａ２が表す炭素数２～５のアルキリデン基としては、エチリデン基、プロピリデン基、イソプロピリデン基、ブチリデン基、イソブチリデン基、ペンチリデン基、イソペンチリデン基等が挙げられる。これらの中でも、耐熱性及び低熱膨張性の観点から、イソプロピリデン基が好ましい。
Ｘａ２としては、上記選択肢の中でも、炭素数１～５のアルキレン基、炭素数２～５のアルキリデン基が好ましい。より好ましいものは前述のとおりである。
ｑ及びｒは各々独立に０～４の整数であり、入手容易性の観点から、いずれも、好ましくは０～２の整数、より好ましくは０又は２である。ｑ又はｒが２以上の整数である場合、複数のＲａ２同士又はＲａ３同士は、それぞれ同一であっても異なっていてもよい。
In the general formula (a1-2), the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R a2 and R a3 include the same ones as in the case of R a1 . The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably an ethyl group.
Examples of the alkylene group having 1 to 5 carbon atoms represented by X a2 include methylene group, 1,2-dimethylene group, 1,3-trimethylene group, 1,4-tetramethylene group, 1,5-pentamethylene group, etc. It will be done. The alkylene group is preferably an alkylene group having 1 to 3 carbon atoms, more preferably a methylene group, from the viewpoint of heat resistance and low thermal expansion.
Examples of the alkylidene group having 2 to 5 carbon atoms represented by X a2 include ethylidene group, propylidene group, isopropylidene group, butylidene group, isobutylidene group, pentylidene group, isopentylidene group, and the like. Among these, isopropylidene group is preferred from the viewpoint of heat resistance and low thermal expansion.
Among the above options, as X a2 , an alkylene group having 1 to 5 carbon atoms and an alkylidene group having 2 to 5 carbon atoms are preferable. More preferred ones are as described above.
q and r are each independently an integer of 0 to 4, and from the viewpoint of availability, both are preferably integers of 0 to 2, more preferably 0 or 2. When q or r is an integer of 2 or more, the plurality of R a2s or R a3s may be the same or different.
前記一般式（ａ１－２－１）中、Ｒａ４及びＲａ５が表す炭素数１～５の脂肪族炭化水素基、ハロゲン原子としては、前記Ｒａ２及びＲａ３の場合と同じものが挙げられ、好ましいものも同じである。
Ｘａ３が表す炭素数１～５のアルキレン基、炭素数２～５のアルキリデン基としては、前記Ｘａ２が表す炭素数１～５のアルキレン基、炭素数２～５のアルキリデン基と同じものが挙げられ、好ましいものも同じである。
Ｘａ３としては、上記選択肢の中でも、好ましくは炭素数２～５のアルキリデン基であり、より好ましいものは前述のとおりである。
ｓ及びｔは０～４の整数であり、入手容易性の観点から、いずれも、好ましくは０～２の整数、より好ましくは０又は１、さらに好ましくは０である。ｓ又はｔが２以上の整数である場合、複数のＲａ４同士又はＲａ５同士は、それぞれ同一であっても異なっていてもよい。
前記一般式（ａ１－２－１）は、下記一般式（ａ１－２－１’）で表されることが好ましい。
In the general formula (a1-2-1), the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R a4 and R a5 include the same ones as in the case of R a2 and R a3 . , preferred ones are also the same.
The alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X a3 are the same as the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X a2 . The preferred ones are also the same.
Among the above options, X a3 is preferably an alkylidene group having 2 to 5 carbon atoms, and the more preferable ones are as described above.
s and t are integers of 0 to 4, and from the viewpoint of availability, both are preferably integers of 0 to 2, more preferably 0 or 1, and even more preferably 0. When s or t is an integer of 2 or more, the plurality of R a4s or R a5s may be the same or different.
The general formula (a1-2-1) is preferably represented by the following general formula (a1-2-1').
（一般式（ａ１－２－１’）中のＸａ３、Ｒａ４、Ｒａ５、ｓ及びｔは、一般式（ａ１－２－１）中のものと同じであり、好ましいものも同じである。）
(X a3 , R a4 , R a5 , s and t in general formula (a1-2-1') are the same as in general formula (a1-2-1), and preferred ones are also the same. .)
前記一般式（ａ１－２）で表される基は、下記一般式（ａ１－２’）で表される基であることが好ましく、下記（ａ１－ｉ）～（ａ１－iii）のいずれかで表される基であることがより好ましく、下記（ａ１－ｉ）又は（ａ１－iii）で表される基であることがさらに好ましい。 The group represented by the general formula (a1-2) is preferably a group represented by the following general formula (a1-2'), and any one of the following (a1-i) to (a1-iii) A group represented by the following is more preferable, and a group represented by the following (a1-i) or (a1-iii) is even more preferable.
（一般式（ａ１－２’）中のＸａ２、Ｒａ２、Ｒａ３、ｑ及びｒは、一般式（ａ１－２）中のものと同じであり、好ましいものも同じである。）
(X a2 , R a2 , R a3 , q and r in general formula (a1-2') are the same as those in general formula (a1-2), and preferred ones are also the same.)
前記一般式（ａ１－３）中、ｎは、１～１０の整数であり、入手容易性の観点から、好ましくは１～５の整数、より好ましくは１～３の整数である。
前記一般式（ａ１－４）中、Ｒａ６及びＲａ７が表す炭素数１～５の脂肪族炭化水素基、ハロゲン原子としては、前記一般式（ａ１－１）中のＲａ１の場合と同じものが挙げられ、好ましいものも同じである。ｕは１～８の整数であり、好ましくは１～３の整数、より好ましくは１である。
In the general formula (a1-3), n is an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, from the viewpoint of availability.
In the general formula (a1-4), the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R a6 and R a7 are the same as in the case of R a1 in the general formula (a1-1). The preferred ones are also the same. u is an integer of 1 to 8, preferably an integer of 1 to 3, more preferably 1.
前記一般式（ａ－１）中、Ｘａ１は、前記一般式（ａ１－１）、（ａ１－２）、（ａ１－３）又は（ａ１－４）で表される基のいずれであってもよく、これらの中でも、低反り性、寸法安定性、耐熱性及び入手容易性の観点から、（ａ１－２）で表される基であることが好ましい。 In the general formula (a-1), X a1 is any group represented by the general formula (a1-1), (a1-2), (a1-3) or (a1-4); Among these, the group represented by (a1-2) is preferred from the viewpoint of low warpage, dimensional stability, heat resistance, and easy availability.
マレイミド化合物（ａ）の具体例としては、ビス（４－マレイミドフェニル）メタン、ポリフェニルメタンマレイミド、ビス（４－マレイミドフェニル）エーテル、ビス（４－マレイミドフェニル）スルホン、３，３’－ジメチル－５，５’－ジエチル－４，４’－ジフェニルメタンビスマレイミド、４－メチル－１，３－フェニレンビスマレイミド、ｍ－フェニレンビスマレイミド、２，２－ビス［４－（４－マレイミドフェノキシ）フェニル］プロパン等が挙げられる。
これらの中でも、反応性が高く、より高耐熱性化できるという観点から、ビス（４－マレイミドフェニル）メタン、ビス（４－マレイミドフェニル）スルホン、３，３’－ジメチル－５，５’－ジエチル－４，４’－ジフェニルメタンビスマレイミド、２，２－ビス［４－（４－マレイミドフェノキシ）フェニル］プロパンが好ましく、溶媒への溶解性の観点から、３，３’－ジメチル－５，５’－ジエチル－４，４’－ジフェニルメタンビスマレイミド、ビス（４－マレイミドフェニル）メタンがより好ましく、製造コストの観点から、ビス（４－マレイミドフェニル）メタンがさらに好ましい。
Specific examples of the maleimide compound (a) include bis(4-maleimidophenyl)methane, polyphenylmethanemaleimide, bis(4-maleimidophenyl)ether, bis(4-maleimidophenyl)sulfone, 3,3'-dimethyl- 5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, m-phenylene bismaleimide, 2,2-bis[4-(4-maleimidophenoxy)phenyl] Examples include propane.
Among these, bis(4-maleimidophenyl)methane, bis(4-maleimidophenyl)sulfone, and 3,3'-dimethyl-5,5'-diethyl have high reactivity and can achieve higher heat resistance. -4,4'-diphenylmethanebismaleimide and 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane are preferred, and from the viewpoint of solubility in solvents, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide and bis(4-maleimidophenyl)methane are more preferred, and from the viewpoint of production cost, bis(4-maleimidophenyl)methane is even more preferred.
熱硬化性樹脂組成物がマレイミド化合物（ａ）を含有する場合、その含有量は、低反り性、寸法安定性、厚み精度、低熱膨張性及び低弾性の観点から、熱硬化性樹脂組成物中の樹脂成分の固形分１００質量部に対して、２０～９０質量部が好ましく、３０～８５質量部がより好ましく、４０～８０質量部がさらに好ましい。
ここで、本実施形態における固形分とは、水分、後述する溶媒等の揮発する物質以外の熱硬化性樹脂組成物中の成分を意味する。すなわち、固形分は、２５℃付近の室温で液状、水飴状又はワックス状のものも含み、必ずしも固体であることを意味するものではない。
熱硬化性樹脂組成物中の樹脂成分の固形分は、例えば、熱硬化性樹脂組成物が、マレイミド化合物（ａ）、アミン化合物（ｂ）、後述する熱可塑性エラストマー（ｃ）、後述する熱硬化性樹脂（ｄ）からなる群から選ばれる１種以上を含有する場合、これらの総量に相当する。なお、後述する硬化促進剤（ｅ）は、樹脂成分には含めないものとする。
When the thermosetting resin composition contains the maleimide compound (a), its content is determined in the thermosetting resin composition from the viewpoint of low warpage, dimensional stability, thickness accuracy, low thermal expansion, and low elasticity. It is preferably 20 to 90 parts by weight, more preferably 30 to 85 parts by weight, and even more preferably 40 to 80 parts by weight, based on 100 parts by weight of the solid content of the resin component.
Here, the solid content in this embodiment means components in the thermosetting resin composition other than water and volatile substances such as the solvent described below. That is, the solid content includes those that are liquid, syrupy, or waxy at room temperature around 25°C, and does not necessarily mean solid.
The solid content of the resin component in the thermosetting resin composition is, for example, if the thermosetting resin composition contains a maleimide compound (a), an amine compound (b), a thermoplastic elastomer (c) described below, and a thermosetting resin described below. When containing one or more types selected from the group consisting of polyester resins (d), this corresponds to the total amount thereof. Note that the curing accelerator (e) described later is not included in the resin component.
（１分子中に少なくとも２個の１級アミノ基を有するアミン化合物（ｂ））
アミン化合物（ｂ）は、１分子中に少なくとも２個の１級アミノ基を有するアミン化合物であれば特に限定されない。アミン化合物（ｂ）は１種を単独で用いても２種類以上を混合して用いてもよい。
アミン化合物（ｂ）としては、１分子中に２個の１級アミノ基を有するアミン化合物が好ましく、下記一般式（ｂ－１）で表されるジアミン化合物がより好ましい。
(Amine compound (b) having at least two primary amino groups in one molecule)
The amine compound (b) is not particularly limited as long as it has at least two primary amino groups in one molecule. The amine compound (b) may be used alone or in combination of two or more.
As the amine compound (b), an amine compound having two primary amino groups in one molecule is preferable, and a diamine compound represented by the following general formula (b-1) is more preferable.
（一般式（ｂ－１）中、Ｘｂ１は、下記一般式（ｂ１－１）又は（ｂ１－２）で表される基である。）
(In the general formula (b-1), X b1 is a group represented by the following general formula (b1-1) or (b1-2).)
（一般式（ｂ１－１）中、Ｒｂ１は各々独立に、炭素数１～５の脂肪族炭化水素基又はハロゲン原子である。ｐは０～４の整数である。）
(In the general formula (b1-1), each R b1 is independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. p is an integer of 0 to 4.)
（一般式（ｂ１－２）中、Ｒｂ２及びＲｂ３は各々独立に、炭素数１～５の脂肪族炭化水素基又はハロゲン原子である。Ｘｂ２は炭素数１～５のアルキレン基、炭素数２～５のアルキリデン基、エーテル基、スルフィド基、スルホニル基、カルボオキシ基、ケト基、単結合又は下記一般式（ｂ１－２－１）で表される基である。ｑ及びｒは各々独立に０～４の整数である。）
(In the general formula (b1-2), R b2 and R b3 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. X b2 is an alkylene group having 1 to 5 carbon atoms, 2 to 5 alkylidene groups, ether groups, sulfide groups, sulfonyl groups, carboxyl groups, keto groups, single bonds, or groups represented by the following general formula (b1-2-1). q and r are each independently is an integer from 0 to 4.)
（一般式（ｂ１－２－１）中、Ｒｂ４及びＲｂ５は各々独立に、炭素数１～５の脂肪族炭化水素基又はハロゲン原子である。Ｘｂ３は炭素数１～５のアルキレン基、炭素数２～５のアルキリデン基、エーテル基、スルフィド基、スルホニル基、カルボオキシ基、ケト基又は単結合である。ｓ及びｔは各々独立に０～４の整数である。）
(In the general formula (b1-2-1), R b4 and R b5 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. X b3 is an alkylene group having 1 to 5 carbon atoms. , an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carboxyl group, a keto group, or a single bond. s and t are each independently an integer of 0 to 4.)
前記一般式（ｂ１－１）中、Ｒｂ１が表す脂肪族炭化水素基としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔ－ブチル基、ｎ－ペンチル基等が挙げられる。該脂肪族炭化水素基としては、好ましくは炭素数１～３の脂肪族炭化水素基であり、より好ましくはメチル基である。また、ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられる。
以上の中でも、Ｒｂ１としては炭素数１～５の脂肪族炭化水素基が好ましい。
ｐは０～４の整数であり、入手容易性の観点から、好ましくは０～２の整数、より好ましくは２である。ｐが２以上の整数である場合、複数のＲｂ１同士は同一であっても異なっていてもよい。
In the general formula (b1-1), the aliphatic hydrocarbon group represented by R b1 includes methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n -pentyl group, etc. The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably a methyl group. Further, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.
Among the above, R b1 is preferably an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
p is an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 2 from the viewpoint of availability. When p is an integer of 2 or more, the plurality of R b1 's may be the same or different.
前記一般式（ｂ１－２）中、Ｒｂ２及びＲｂ３が表す炭素数１～５の脂肪族炭化水素基、ハロゲン原子としては、前記Ｒｂ１の場合と同じものが挙げられる。該脂肪族炭化水素基としては、好ましくは炭素数１～３の脂肪族炭化水素基、より好ましくはメチル基及びエチル基、さらに好ましくはエチル基である。
Ｘｂ２が表す炭素数１～５のアルキレン基としては、メチレン基、１，２－ジメチレン基、１，３－トリメチレン基、１，４－テトラメチレン基、１，５－ペンタメチレン基等が挙げられる。該アルキレン基としては、耐熱性及び低熱膨張性の観点から、好ましくは炭素数１～３のアルキレン基であり、より好ましくはメチレン基である。
Ｘｂ２が表す炭素数２～５のアルキリデン基としては、エチリデン基、プロピリデン基、イソプロピリデン基、ブチリデン基、イソブチリデン基、ペンチリデン基、イソペンチリデン基等が挙げられる。これらの中でも、耐熱性及び低熱膨張性の観点から、イソプロピリデン基が好ましい。
Ｘｂ２としては、上記選択肢の中でも、炭素数１～５のアルキレン基、炭素数２～５のアルキリデン基が好ましい。より好ましいものは前述のとおりである。
ｑ及びｒは各々独立に０～４の整数であり、入手容易性の観点から、いずれも、好ましくは０～２の整数、より好ましくは０又は２である。ｑ又はｒが２以上の整数である場合、複数のＲｂ２同士又はＲｂ３同士は、それぞれ同一であっても異なっていてもよい。
In the general formula (b1-2), the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R b2 and R b3 include the same ones as in the case of R b1 . The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably an ethyl group.
Examples of the alkylene group having 1 to 5 carbon atoms represented by X b2 include methylene group, 1,2-dimethylene group, 1,3-trimethylene group, 1,4-tetramethylene group, 1,5-pentamethylene group, etc. It will be done. The alkylene group is preferably an alkylene group having 1 to 3 carbon atoms, more preferably a methylene group, from the viewpoint of heat resistance and low thermal expansion.
Examples of the alkylidene group having 2 to 5 carbon atoms represented by X b2 include ethylidene group, propylidene group, isopropylidene group, butylidene group, isobutylidene group, pentylidene group, isopentylidene group, and the like. Among these, isopropylidene group is preferred from the viewpoint of heat resistance and low thermal expansion.
Among the above options, X b2 is preferably an alkylene group having 1 to 5 carbon atoms or an alkylidene group having 2 to 5 carbon atoms. More preferred ones are as described above.
q and r are each independently an integer of 0 to 4, and from the viewpoint of availability, both are preferably integers of 0 to 2, more preferably 0 or 2. When q or r is an integer of 2 or more, a plurality of R b2s or R b3s may be the same or different.
前記一般式（ｂ１－２－１）中、Ｒｂ４及びＲｂ５が表す炭素数１～５の脂肪族炭化水素基、ハロゲン原子としては、前記Ｒｂ２及びＲｂ３の場合と同じものが挙げられ、好ましいものも同じである。
Ｘｂ３が表す炭素数１～５のアルキレン基、炭素数２～５のアルキリデン基としては、前記Ｘｂ２が表す炭素数１～５のアルキレン基、炭素数２～５のアルキリデン基と同じものが挙げられ、好ましいものも同じである。
Ｘｂ３としては、上記選択肢の中でも、好ましくは炭素数２～５のアルキリデン基であり、より好ましいものは前述のとおりである。
ｓ及びｔは０～４の整数であり、入手容易性の観点から、いずれも、好ましくは０～２の整数、より好ましくは０又は１、さらに好ましくは０である。ｓ又はｔが２以上の整数である場合、複数のＲｂ４同士又はＲｂ５同士は、それぞれ同一であっても異なっていてもよい。
前記一般式（ｂ１－２－１）は、下記一般式（ｂ１－２－１’）で表されることが好ましい。
In the general formula (b1-2-1), the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R b4 and R b5 include the same ones as in the case of R b2 and R b3 . , preferred ones are also the same.
The alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X b3 are the same as the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X b2 . The preferred ones are also the same.
Among the above options, X b3 is preferably an alkylidene group having 2 to 5 carbon atoms, and the more preferable ones are as described above.
s and t are integers of 0 to 4, and from the viewpoint of availability, both are preferably integers of 0 to 2, more preferably 0 or 1, and even more preferably 0. When s or t is an integer of 2 or more, the plurality of R b4s or R b5s may be the same or different.
The general formula (b1-2-1) is preferably represented by the following general formula (b1-2-1').
（一般式（ｂ１－２－１’）中のＸｂ３、Ｒｂ４、Ｒｂ５、ｓ及びｔは、一般式（ｂ１－２－１）中のものと同じであり、好ましいものも同じである。）
(X b3 , R b4 , R b5 , s and t in general formula (b1-2-1') are the same as in general formula (b1-2-1), and preferred ones are also the same. .)
前記一般式（ｂ１－２）で表される基は、下記一般式（ｂ１－２’）で表される基であることが好ましく、下記式（ｂ１－i）～（ｂ１－iii）のいずれかで表される基であることがより好ましく、（ｂ１－ii）で表される基であることがさらに好ましい。 The group represented by the general formula (b1-2) is preferably a group represented by the following general formula (b1-2'), and any of the following formulas (b1-i) to (b1-iii) A group represented by (b1-ii) is more preferable, and a group represented by (b1-ii) is even more preferable.
（一般式（ｂ１－２’）中のＸｂ２、Ｒｂ２、Ｒｂ３、ｑ及びｒは、一般式（ｂ１－２）中のものと同じであり、好ましいものも同じである。）
(X b2 , R b2 , R b3 , q and r in general formula (b1-2') are the same as in general formula (b1-2), and preferred ones are also the same.)
アミン化合物（ｂ）としては、ジアミノベンジジン、ジアミノジフェニルメタン、ジアミノジフェニルエーテル、ジアミノジフェニルスルホン、３，３’－ジメトキシ－４，４’－ジアミノビフェニル、３，３’－ジメチル－４，４’－ジアミノビフェニル、３，３’－ジクロロ－４，４’－ジアミノビフェニル、３，３’－ジメチル－４，４’－ジアミノビフェニル－６，６’－ジスルホン酸、２，２’，５，５’－テトラクロロ－４，４’－ジアミノビフェニル、４，４’－メチレン－ビス（２－クロロアニリン）、１，３’－ビス（４－アミノフェノキシ）ベンゼン、２，２’－ビス［４－（４－アミノフェノキシ）フェニル］プロパン、ビス［４－（４－アミノフェノキシ）フェニル］スルホン、ビス［４－（３－アミノフェノキシ）フェニル］スルホン、４，４’－ビス（４－アミノフェノキシ）ビフェニル、２，２’－ビス［４－（４－アミノフェノキシ）フェニル］ヘキサフルオロプロパン、１，４’－ビス（４－アミノフェノキシ）ベンゼン、４，４’－ジアミノジフェニルスルフィド、２，２’－ジメチル－４，４’－ジアミノビフェニル、４，４’－ジアミノ－３，３’－ビフェニルジオール、９，９’－ビス（４－アミノフェニル）フルオレン、ｏ‐トリジンスルホン等が挙げられる。 Examples of the amine compound (b) include diaminobenzidine, diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenylsulfone, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl. , 3,3'-dichloro-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl-6,6'-disulfonic acid, 2,2',5,5'-tetra Chloro-4,4'-diaminobiphenyl, 4,4'-methylene-bis(2-chloroaniline), 1,3'-bis(4-aminophenoxy)benzene, 2,2'-bis[4-(4 -aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 4,4'-bis(4-aminophenoxy)biphenyl, 2,2'-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4'-bis(4-aminophenoxy)benzene, 4,4'-diaminodiphenyl sulfide, 2,2'-dimethyl -4,4'-diaminobiphenyl, 4,4'-diamino-3,3'-biphenyldiol, 9,9'-bis(4-aminophenyl)fluorene, o-tolidinesulfone and the like.
また、アミン化合物（ｂ）は、低熱膨張性及び弾性率の観点から、１分子中に少なくとも２個の１級アミノ基を有するシロキサン化合物であることが好ましく、１分子中に２個の１級アミノ基を有するシロキサン化合物であることがより好ましく、両末端に１級アミノ基を有するシロキサン化合物であることがさらに好ましい。
アミン化合物（ｂ）としては、１分子中に２個の１級アミノ基を有するアミン化合物が好ましく、下記一般式（ｂ－１）で表されるジアミン化合物がより好ましい。
In addition, from the viewpoint of low thermal expansion and elastic modulus, the amine compound (b) is preferably a siloxane compound having at least two primary amino groups in one molecule; A siloxane compound having an amino group is more preferable, and a siloxane compound having a primary amino group at both ends is even more preferable.
As the amine compound (b), an amine compound having two primary amino groups in one molecule is preferable, and a diamine compound represented by the following general formula (b-1) is more preferable.
（式中、Ｒｂ６及びＲｂ７は、各々独立に、アルキル基、フェニル基又は置換フェニル基を示し、ｍは、１～１００の整数を示す。）
（式中、Ｒｂ６、Ｒｂ７、Ｒｂ８及びＲｂ９は、各々独立に、アルキル基、フェニル基又は置換フェニル基を示し、Ｘｂ４及びＸｂ５は、各々独立に、２価の有機基を示す。ｍ’は１～１００の整数を示す。）
(In the formula, R b6 and R b7 each independently represent an alkyl group, a phenyl group, or a substituted phenyl group, and m represents an integer of 1 to 100.)
(In the formula, R b6 , R b7 , R b8 and R b9 each independently represent an alkyl group, phenyl group or substituted phenyl group, and X b4 and X b5 each independently represent a divalent organic group. (m' indicates an integer from 1 to 100.)
前記一般式（ｂ－２）及び（ｂ－３）中、Ｒｂ６、Ｒｂ７、Ｒｂ８及びＲｂ９が表すアルキル基としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔ－ブチル基、ｎ－ペンチル基等が挙げられる。該アルキル基としては、炭素数１～５のアルキル基が好ましく、炭素数１～３のアルキル基がより好ましく、メチル基がさらに好ましい。
置換フェニル基におけるフェニル基が有する置換基としては、炭素数１～５のアルキル基、炭素数２～５のアルケニル基、炭素数２～５のアルキニル基等が挙げられる。該炭素数１～５のアルキル基としては、前記したものと同じものが挙げられる。該炭素数２～５のアルケニル基としては、ビニル基、アリル基等が挙げられる。炭素数２～５のアルキニル基としては、エチニル基、プロパルギル基等が挙げられる。
Ｒｂ６、Ｒｂ７、Ｒｂ８及びＲｂ９は、いずれも炭素数１～５のアルキル基であることが好ましく、メチル基であることがより好ましい。
ｍ及びｍ’は、低熱膨張性の観点から、１～１００の整数であり、相溶性及び高弾性化の観点から、５～５０の整数が好ましく。１０～４０の整数がさらに好ましい。
前記一般式（ｂ－３）中、Ｘｂ４及びＸｂ５が表す２価の有機基としては、アルキレン基、アルケニレン基、アルキニレン基、アリーレン基、－Ｏ－又はこれらが組み合わされた２価の連結基等が挙げられる。該アルキレン基としては、メチレン基、１，２－ジメチレン基、１，３－トリメチレン基、１，４－テトラメチレン基、１，５－ペンタメチレン基等の炭素数１～１０のアルキレン基が挙げられる。該アルケニレン基としては、炭素数２～１０のアルケニレン基が挙げられる。該アルキニレン基としては、炭素数２～１０のアルキニレン基が挙げられる。該アリーレン基としては、フェニレン基、ナフチレン基等の炭素数６～２０のアリーレン基が挙げられる。これらの中でも、Ｘｂ４及びＸｂ５が表す２価の有機基は、アルキレン基が好ましく、１，３－トリメチレン基がより好ましい。
In the general formulas (b-2) and (b-3), the alkyl groups represented by R b6 , R b7 , R b8 and R b9 include methyl group, ethyl group, n-propyl group, isopropyl group, n- Examples include butyl group, isobutyl group, t-butyl group, n-pentyl group, and the like. The alkyl group is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably a methyl group.
Examples of the substituent of the phenyl group in the substituted phenyl group include an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkynyl group having 2 to 5 carbon atoms, and the like. Examples of the alkyl group having 1 to 5 carbon atoms include those mentioned above. Examples of the alkenyl group having 2 to 5 carbon atoms include a vinyl group and an allyl group. Examples of the alkynyl group having 2 to 5 carbon atoms include ethynyl group and propargyl group.
R b6 , R b7 , R b8 and R b9 are all preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group.
m and m' are integers of 1 to 100 from the viewpoint of low thermal expansion, and preferably integers of 5 to 50 from the viewpoint of compatibility and high elasticity. An integer of 10 to 40 is more preferred.
In the general formula (b-3), the divalent organic group represented by X b4 and X b5 is an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O- or a divalent linkage of these Examples include groups. Examples of the alkylene group include alkylene groups having 1 to 10 carbon atoms such as methylene group, 1,2-dimethylene group, 1,3-trimethylene group, 1,4-tetramethylene group, and 1,5-pentamethylene group. It will be done. Examples of the alkenylene group include alkenylene groups having 2 to 10 carbon atoms. Examples of the alkynylene group include alkynylene groups having 2 to 10 carbon atoms. Examples of the arylene group include arylene groups having 6 to 20 carbon atoms such as phenylene group and naphthylene group. Among these, the divalent organic group represented by X b4 and X b5 is preferably an alkylene group, and more preferably a 1,3-trimethylene group.
アミン化合物（ｂ）は、市販品を用いることができる。アミン化合物（ｂ）の市販品としては、例えば、両末端にアミノ基を有するシロキサン化合物である「ＰＡＭ－Ｅ」（アミノ基の官能基当量１３０）、「ＫＦ－８０１０」（アミノ基の官能基当量４３０）、「Ｘ－２２－１６１Ａ」（アミノ基の官能基当量８００）、「Ｘ－２２－１６１Ｂ」（アミノ基の官能基当量１，５００）、「ＫＦ－８０１２」（アミノ基の官能基当量２，２００）、「ＫＦ－８００８」（アミノ基の官能基当量５，７００）〔以上、信越化学工業株式会社製〕、「ＢＹ１６－８７１」（アミノ基の官能基当量１３０）、「ＢＹ１６－８５３Ｕ」（アミノ基の官能基当量４６０）〔以上、東レダウコーニング株式会社製〕等が挙げられる（アミノ基の官能基当量の単位はｇ／ｍｏｌである。）。 A commercially available product can be used as the amine compound (b). Examples of commercially available amine compounds (b) include "PAM-E" (functional group equivalent of amino group: 130), which is a siloxane compound having amino groups at both ends, "KF-8010" (functional group equivalent of amino group: 130), "X-22-161A" (functional group equivalent of amino group 800), "X-22-161B" (functional group equivalent of amino group 1,500), "KF-8012" (functional group equivalent of amino group 1,500), "KF-8012" (functional group equivalent of amino group 800), "KF-8008" (functional group equivalent of amino group 5,700) [manufactured by Shin-Etsu Chemical Co., Ltd.], "BY16-871" (functional group equivalent of amino group 130), " BY16-853U'' (functional group equivalent of amino group: 460) [manufactured by Dow Corning Toray Co., Ltd.] (the unit of functional group equivalent of amino group is g/mol).
熱硬化性樹脂組成物がアミン化合物（ｂ）を含有する場合、その含有量は、低反り性、寸法安定性、厚み精度、低熱膨張性及び低弾性の観点から、熱硬化性樹脂組成物中の樹脂成分の固形分１００質量部に対して、５～５０質量部が好ましく、１０～４０質量部がより好ましく、１２～３０質量部がさらに好ましい。 When the thermosetting resin composition contains the amine compound (b), the content in the thermosetting resin composition is determined from the viewpoints of low warpage, dimensional stability, thickness accuracy, low thermal expansion, and low elasticity. It is preferably 5 to 50 parts by weight, more preferably 10 to 40 parts by weight, and even more preferably 12 to 30 parts by weight, based on 100 parts by weight of the solid content of the resin component.
（変性ポリイミド（Ｘ））
変性ポリイミド（Ｘ）は、（ａ）成分と（ｂ）成分とを反応させて得られるものであり、（ａ）成分由来の構造単位（ａ’）と、（ｂ）成分由来の構造単位（ｂ’）と、を含有するものである。
変性ポリイミド（Ｘ）は１種を単独で用いても２種類以上を混合して用いてもよい。
（ａ）成分と（ｂ）成分との反応方法に特に制限はない。反応温度は、生産性及び十分に反応を進行させる観点から、７０～２００℃が好ましく、１００～１３０℃がより好ましい。また、反応時間は、０．５～１０時間が好ましく、１～６時間がより好ましい。
(Modified polyimide (X))
Modified polyimide (X) is obtained by reacting component (a) and component (b), and contains a structural unit (a') derived from component (a) and a structural unit (a') derived from component (b). b').
The modified polyimide (X) may be used alone or in combination of two or more.
There is no particular restriction on the method of reaction between component (a) and component (b). The reaction temperature is preferably 70 to 200°C, more preferably 100 to 130°C, from the viewpoint of productivity and sufficient progress of the reaction. Further, the reaction time is preferably 0.5 to 10 hours, more preferably 1 to 6 hours.
（ａ）成分と（ｂ）成分との反応は、有機溶媒中で行うことが好ましい。有機溶媒としては、エタノール、プロパノール、ブタノール、メチルセロソルブ、ブチルセロソルブ、プロピレングリコールモノメチルエーテル等のアルコール系溶媒；アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶媒；酢酸エチルエステル、γ－ブチロラクトン等のエステル系溶媒；テトラヒドロフラン等のエーテル系溶媒；トルエン、キシレン、メシチレン等の芳香族系溶媒；ジメチルホルムアミド、ジメチルアセトアミド、Ｎ－メチルピロリドン等の窒素原子含有溶媒；ジメチルスルホキシド等の硫黄原子含有溶媒などが挙げられる。
これらの中でも、溶解性の観点から、シクロヘキサノン、プロピレングリコールモノメチルエーテル、メチルセロソルブ、γ－ブチロラクトンが好ましく、低毒性であるという観点及び揮発性が高く残溶媒として残り難いという観点から、シクロヘキサノン、プロピレングリコールモノメチルエーテル、ジメチルアセトアミドが好ましく、プロピレングリコールモノメチルエーテルがより好ましい。
The reaction between component (a) and component (b) is preferably carried out in an organic solvent. Examples of organic solvents include alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; acetic acid ethyl ester, γ-butyrolactone, etc. Ester solvents; ether solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene, and mesitylene; nitrogen-containing solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; sulfur-containing solvents such as dimethyl sulfoxide, etc. Can be mentioned.
Among these, from the viewpoint of solubility, cyclohexanone, propylene glycol monomethyl ether, methyl cellosolve, and γ-butyrolactone are preferable, and from the viewpoint of low toxicity and high volatility, it is unlikely to remain as a residual solvent, cyclohexanone, propylene glycol Monomethyl ether and dimethylacetamide are preferred, and propylene glycol monomethyl ether is more preferred.
前記反応における、（ａ）成分由来のマレイミド基の当量と、（ｂ）成分由来の１級アミノ基の当量との比［（ａ）／（ｂ）］は、ゲル化の防止及び耐熱性の観点から、１を超えることが好ましく、５～３５がより好ましく、１２～３０がさらに好ましい。 In the above reaction, the ratio [(a)/(b)] between the equivalent of the maleimide group derived from component (a) and the equivalent of the primary amino group derived from component (b) is important for preventing gelation and for heat resistance. From this point of view, it is preferably greater than 1, more preferably 5 to 35, and even more preferably 12 to 30.
変性ポリイミド（Ｘ）中における構造単位（ａ’）の含有量は、低反り性、寸法安定性、厚み精度、低熱膨張性及び低弾性の観点から、３０～９５質量％が好ましく、４０～９０質量％がより好ましく、６０～８５質量％がさらに好ましい。
変性ポリイミド（Ｘ）中における構造単位（ｂ’）の含有量は、低反り性、寸法安定性、厚み精度、低熱膨張性及び低弾性の観点から、５～７０質量％が好ましく、１０～６０質量％がより好ましく、１５～４０質量％がさらに好ましい。
熱硬化性樹脂組成物中の樹脂成分の固形分１００質量部を基準とした場合における、熱硬化性樹脂組成物中の構造単位（ａ’）、構造単位（ｂ’）の好適な含有量は、各々、前記熱硬化性樹脂組成物中における（ａ）成分、（ｂ）成分の含有量の好適な態様と同じである。
但し、熱硬化性樹脂組成物が、変性ポリイミド（Ｘ）とは別に、さらに（ａ）成分及び（ｂ）成分からなる群から選ばれる１種以上を含有する場合、各成分と各成分由来の構造単位との合計含有量が、前記した熱硬化性樹脂組成物中における（ａ）成分、（ｂ）成分の含有量の好適な態様となることが好ましい。
The content of the structural unit (a') in the modified polyimide (X) is preferably 30 to 95% by mass, and 40 to 90% by mass from the viewpoint of low warpage, dimensional stability, thickness accuracy, low thermal expansion, and low elasticity. % by mass is more preferred, and 60 to 85% by mass is even more preferred.
The content of the structural unit (b') in the modified polyimide (X) is preferably 5 to 70% by mass, and 10 to 60% by mass from the viewpoint of low warpage, dimensional stability, thickness accuracy, low thermal expansion, and low elasticity. % by mass is more preferred, and 15 to 40% by mass is even more preferred.
The preferred content of the structural unit (a') and structural unit (b') in the thermosetting resin composition is based on 100 parts by mass of the solid content of the resin component in the thermosetting resin composition. , respectively, are the same as the preferred embodiments of the content of component (a) and component (b) in the thermosetting resin composition.
However, if the thermosetting resin composition further contains one or more selected from the group consisting of component (a) and component (b) in addition to modified polyimide (X), each component and the components derived from each component It is preferable that the total content with the structural unit corresponds to a preferable aspect of the content of the components (a) and (b) in the thermosetting resin composition described above.
熱硬化性樹脂組成物が変性ポリイミド（Ｘ）を含有する場合、その含有量は、低反り性、寸法安定性、厚み精度、低熱膨張性及び低弾性の観点から、熱硬化性樹脂組成物中の樹脂成分の固形分１００質量部に対して、４０～１００質量部が好ましく、５０～９５質量部がより好ましく、６０～９２質量部がさらに好ましい。 When the thermosetting resin composition contains modified polyimide (X), its content in the thermosetting resin composition is determined from the viewpoints of low warpage, dimensional stability, thickness accuracy, low thermal expansion, and low elasticity. It is preferably 40 to 100 parts by weight, more preferably 50 to 95 parts by weight, and even more preferably 60 to 92 parts by weight, based on 100 parts by weight of the solid content of the resin component.
（熱可塑性エラストマー（ｃ））
熱硬化性樹脂組成物は、さらに、熱可塑性エラストマー（ｃ）を含有することが好ましい。つまり、樹脂フィルム（Ｉ）は、（ａ）成分、（ｂ）成分及び熱可塑性エラストマー（ｃ）を含有する熱硬化性樹脂組成物を含んでなるもの、又は（ａ）成分と（ｂ）成分との反応物である変性ポリイミド（Ｘ）と、熱可塑性エラストマー（ｃ）と、を含有する熱硬化性樹脂組成物を含んでなるものであることが好ましい。
熱可塑性エラストマー（ｃ）は１種を単独で用いても２種類以上を混合して用いてもよい。
熱可塑性エラストマー（ｃ）としては、スチレン系熱可塑性エラストマー、オレフィン系熱可塑性エラストマー、ウレタン系熱可塑性エラストマー、ポリエステル系熱可塑性エラストマー、ポリアミド系熱可塑性エラストマー、アクリル系熱可塑性エラストマー、シリコーン系熱可塑性エラストマー、これらのエラストマーの誘導体等が挙げられる。これらは、通常、ハードセグメント成分とソフトセグメント成分とからなり立っており、一般に前者が耐熱性及び強度に、後者が柔軟性及び強靭性に寄与している。
これらの中でも、耐熱性及び絶縁信頼性の観点からは、スチレン系熱可塑性エラストマーが好ましく、銅箔との接着性を良好に保ちながら熱硬化性樹脂組成物の弾性率を低減することができるという観点からは、アクリル系熱可塑性エラストマーが好ましい。
(Thermoplastic elastomer (c))
It is preferable that the thermosetting resin composition further contains a thermoplastic elastomer (c). That is, the resin film (I) includes a thermosetting resin composition containing component (a), component (b), and thermoplastic elastomer (c), or component (a) and component (b). It is preferable that the composition comprises a thermosetting resin composition containing a modified polyimide (X) which is a reaction product with a thermoplastic elastomer (c).
The thermoplastic elastomer (c) may be used alone or in combination of two or more.
Examples of the thermoplastic elastomer (c) include styrene thermoplastic elastomer, olefin thermoplastic elastomer, urethane thermoplastic elastomer, polyester thermoplastic elastomer, polyamide thermoplastic elastomer, acrylic thermoplastic elastomer, and silicone thermoplastic elastomer. , derivatives of these elastomers, and the like. These usually consist of a hard segment component and a soft segment component, with the former generally contributing to heat resistance and strength, and the latter contributing to flexibility and toughness.
Among these, styrene-based thermoplastic elastomers are preferred from the viewpoint of heat resistance and insulation reliability, and are said to be able to reduce the elastic modulus of the thermosetting resin composition while maintaining good adhesion to copper foil. From this point of view, acrylic thermoplastic elastomers are preferred.
スチレン系熱可塑性エラストマーは、少なくともスチレンに由来する構造単位を含む分子で形成される重合体である。スチレン系熱可塑性エラストマーが有するスチレン由来の構造単位以外の構造単位としては、ブタジエン由来の構造単位、イソプレン由来の構造単位、マレイン酸由来の構造単位、無水マレイン酸由来の構造単位等が挙げられる。これらは単独で又は２種以上含まれていてもよい。
前記ブタジエン由来の構造単位及び前記イソプレン由来の構造単位は、水素添加されていることが好ましい。水素添加されている場合、ブタジエン由来の構造単位はエチレン単位とブチレン単位とが混合した構造単位となり、イソプレン由来の構造単位はエチレン単位とプロピレン単位とが混合した構造単位となる。
A styrenic thermoplastic elastomer is a polymer formed of molecules containing at least a structural unit derived from styrene. Structural units other than styrene-derived structural units included in the styrenic thermoplastic elastomer include butadiene-derived structural units, isoprene-derived structural units, maleic acid-derived structural units, maleic anhydride-derived structural units, and the like. These may be contained alone or in combination of two or more.
The structural unit derived from butadiene and the structural unit derived from isoprene are preferably hydrogenated. When hydrogenated, the structural unit derived from butadiene becomes a structural unit in which an ethylene unit and a butylene unit are mixed, and the structural unit derived from isoprene becomes a structural unit in which an ethylene unit and a propylene unit are mixed.
スチレン系熱可塑性エラストマーとしては、低熱膨張性、金属回路との接着強度、耐熱性、弾性率及び高周波特性の観点から、スチレン－ブタジエン－スチレンブロック共重合体の水素添加物、スチレン－イソプレン－スチレンブロック共重合体の水素添加物が好ましく、スチレン－ブタジエン－スチレンブロック共重合体の水素添加物がより好ましい。
なお、スチレン－ブタジエン－スチレンブロック共重合体の水素添加物としては、炭素－炭素二重結合の水素添加率が通常９０％以上（好ましくは９５％以上）であるＳＥＢＳと、ブタジエンブロック中の１，２－結合部位の炭素－炭素二重結合が部分的に水素添加されたＳＢＢＳ（全体の炭素－炭素二重結合に対する水素添加率はおよそ６０～８５％）とがある。これらの中でも、ＳＥＢＳがより好ましい。
Styrene-based thermoplastic elastomers include hydrogenated styrene-butadiene-styrene block copolymers, styrene-isoprene-styrene, etc., from the viewpoints of low thermal expansion, adhesive strength with metal circuits, heat resistance, elastic modulus, and high frequency properties. Hydrogenated products of block copolymers are preferred, and hydrogenated products of styrene-butadiene-styrene block copolymers are more preferred.
In addition, as the hydrogenated material of the styrene-butadiene-styrene block copolymer, SEBS whose hydrogenation rate of carbon-carbon double bonds is usually 90% or more (preferably 95% or more) and 1 in the butadiene block are used. , SBBS in which the carbon-carbon double bond at the 2-bond site is partially hydrogenated (the hydrogenation rate with respect to the entire carbon-carbon double bond is approximately 60 to 85%). Among these, SEBS is more preferred.
アクリル系熱可塑性エラストマーは、少なくともアクリル酸エステルに由来する構造単位を含む分子で形成される重合体である。アクリル酸エステルに由来する構造単位とは、アクリル酸エステル単量体を重合させたときに形成される構造単位のことを意味する。
アクリル系熱可塑性エラストマーは、分子中に異なる複数種のアクリル酸エステルに由来する繰り返し構造単位を含み、さらに、１種又は２種以上のアクリル酸エステル以外の単量体に由来する繰り返し構造単位を含んでもよい。あるいは、アクリル系熱可塑性エラストマーは、分子中に異なる複数種のアクリル酸エステルに由来する繰り返し構造単位からなるものであってもよい。
Acrylic thermoplastic elastomer is a polymer formed of molecules containing at least a structural unit derived from an acrylic ester. The structural unit derived from an acrylic ester means a structural unit formed when an acrylic ester monomer is polymerized.
Acrylic thermoplastic elastomers contain repeating structural units derived from multiple different types of acrylic esters in their molecules, and further contain repeating structural units derived from one or more types of monomers other than acrylic esters. May include. Alternatively, the acrylic thermoplastic elastomer may have repeating structural units derived from a plurality of different acrylic esters in the molecule.
アクリル酸エステルとしては、アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸イソプロピル、アクリル酸ブチル、アクリル酸イソブチル、アクリル酸ｔ－ブチル、アクリル酸ペンチル、アクリル酸ヘキシル、アクリル酸シクロヘキシル、アクリル酸オクチル、アクリル酸デシル、アクリル酸ラウリル、アクリル酸ベンジル等が挙げられる。
アクリル酸エステル以外の単量体としては、アクリロニトリル、アクリルアミド、アクリル酸、メタクリル酸、メタクリル酸エステル、スチレン、エチレン、プロピレン、ブタジエン等のビニル系単量体が挙げられる。
Examples of acrylic esters include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, t-butyl acrylate, pentyl acrylate, hexyl acrylate, cyclohexyl acrylate, and acrylic acid. Examples include octyl, decyl acrylate, lauryl acrylate, and benzyl acrylate.
Examples of monomers other than acrylic esters include vinyl monomers such as acrylonitrile, acrylamide, acrylic acid, methacrylic acid, methacrylic esters, styrene, ethylene, propylene, and butadiene.
アクリル系熱可塑性エラストマーの重量平均分子量（Ｍｗ）は、１，０００～２００，０００が好ましく、２，０００～１５０，０００がより好ましい。重量平均分子量（Ｍｗ）が前記下限値以上であると、低弾性性に優れ、前記上限値以下であると、相溶性、及び流動性に優れる。
なお、重量平均分子量（Ｍｗ）は、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）により測定を行い、標準ポリスチレンを用いて作製した検量線により換算したものである。
The weight average molecular weight (Mw) of the acrylic thermoplastic elastomer is preferably 1,000 to 200,000, more preferably 2,000 to 150,000. When the weight average molecular weight (Mw) is at least the above lower limit, it has excellent low elasticity, and when it is at most the above upper limit, it has excellent compatibility and fluidity.
Note that the weight average molecular weight (Mw) is measured by gel permeation chromatography (GPC) and converted using a calibration curve prepared using standard polystyrene.
熱可塑性エラストマー（ｃ）は、分子末端及び分子鎖中のうち少なくとも一方に反応性官能基を有していてもよい。反応性官能基としては、エポキシ基、水酸基、カルボキシ基、アミノ基、アミド基、イソシアナト基、アクリル基、（メタ）アクリル基、ビニル基等が挙げられる。反応性官能基を有することにより、他の樹脂成分との相溶性が向上し、熱硬化性樹脂組成物の硬化時に発生する内部応力をより効果的に低減することができ、結果として、コアレス基板の反りを顕著に低減することが可能となる。特に、低熱膨張性及び金属回路との接着強度の観点からは、エポキシ基、水酸基、カルボキシ基、アミノ基及びアミド基からなる群から選ばれる１種以上を有することが好ましく、耐熱性及び絶縁信頼性の観点から、エポキシ基、水酸基及びカルボキシ基からなる群から選ばれる１種以上を有することがより好ましい。 The thermoplastic elastomer (c) may have a reactive functional group at least one of the molecular terminal and the molecular chain. Examples of the reactive functional group include an epoxy group, a hydroxyl group, a carboxy group, an amino group, an amide group, an isocyanato group, an acrylic group, a (meth)acrylic group, and a vinyl group. Having a reactive functional group improves compatibility with other resin components, making it possible to more effectively reduce the internal stress that occurs during curing of the thermosetting resin composition, and as a result, coreless substrates This makes it possible to significantly reduce warpage. In particular, from the viewpoint of low thermal expansion and adhesive strength with metal circuits, it is preferable to have one or more types selected from the group consisting of epoxy groups, hydroxyl groups, carboxyl groups, amino groups, and amide groups. From the viewpoint of properties, it is more preferable to have one or more selected from the group consisting of epoxy groups, hydroxyl groups, and carboxy groups.
熱硬化性樹脂組成物が熱可塑性エラストマー（ｃ）を含有する場合、その含有量は、他の樹脂成分との相溶性を良好にし、硬化物の低硬化収縮性及び低熱膨張性を効果的に発現させる観点から、熱硬化性樹脂組成物中の樹脂成分の固形分１００質量部に対して、１～６０質量部が好ましく、２～５０質量部がより好ましく、４～２５質量部がさらに好ましい。 When the thermosetting resin composition contains a thermoplastic elastomer (c), the content thereof is determined to improve compatibility with other resin components and effectively improve low curing shrinkage and low thermal expansion of the cured product. From the viewpoint of expression, the solid content of the resin component in the thermosetting resin composition is preferably 1 to 60 parts by mass, more preferably 2 to 50 parts by mass, and even more preferably 4 to 25 parts by mass. .
（熱硬化性樹脂（ｄ））
熱硬化性樹脂組成物は、さらに、熱硬化性樹脂（ｄ）を含有することが好ましい。但し、該熱硬化性樹脂（ｄ）は、（ａ）成分及び（ｂ）成分を含まない。
熱硬化性樹脂（ｄ）としては、エポキシ樹脂、フェノール樹脂、不飽和イミド樹脂（但し、前記（ｂ）成分を含まない）、シアネート樹脂、イソシアネート樹脂、ベンゾオキサジン樹脂、オキセタン樹脂、アミノ樹脂（但し、前記（ａ）成分を含まない）、不飽和ポリエステル樹脂、アリル樹脂、ジシクロペンタジエン樹脂、シリコーン樹脂、トリアジン樹脂、メラミン樹脂等が挙げられる。これらの中でも、成形性及び電気絶縁性の観点、並びに金属回路との接着強度の観点から、エポキシ樹脂及びシアネート樹脂からなる群から選ばれる１種以上が好ましく、エポキシ樹脂がより好ましい。
熱硬化性樹脂（ｄ）は１種を単独で用いても２種類以上を混合して用いてもよい。
(Thermosetting resin (d))
It is preferable that the thermosetting resin composition further contains a thermosetting resin (d). However, the thermosetting resin (d) does not contain the (a) component and the (b) component.
Thermosetting resins (d) include epoxy resins, phenolic resins, unsaturated imide resins (but not containing the component (b)), cyanate resins, isocyanate resins, benzoxazine resins, oxetane resins, and amino resins (but not including the component (b)). , not containing component (a)), unsaturated polyester resins, allyl resins, dicyclopentadiene resins, silicone resins, triazine resins, melamine resins, and the like. Among these, from the viewpoint of moldability, electrical insulation, and adhesive strength with the metal circuit, one or more selected from the group consisting of epoxy resins and cyanate resins are preferred, and epoxy resins are more preferred.
The thermosetting resin (d) may be used alone or in combination of two or more.
エポキシ樹脂としては、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂等のビスフェノール型エポキシ樹脂；フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、α－ナフトール／クレゾールノボラック型エポキシ樹脂、ビスフェノールＡノボラック型エポキシ樹脂、ビスフェノールＦノボラック型エポキシ樹脂、アラルキルノボラック型エポキシ樹脂等のノボラック型エポキシ樹脂；スチルベン型エポキシ樹脂、トリアジン骨格含有エポキシ樹脂、フルオレン骨格含有エポキシ樹脂、トリフェノールメタン型エポキシ樹脂、ビフェニル型エポキシ樹脂、キシリレン型エポキシ樹脂、ナフタレン型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、脂環式エポキシ樹脂、多官能フェノール類及びアントラセン等の多環芳香族類のジグリシジルエーテル化合物、これらにリン化合物を導入したリン含有エポキシ樹脂などが挙げられる。これらの中でも、低反り性、寸法安定性、厚み精度、低熱膨張性及び低弾性の観点から、アラルキルノボラック型エポキシ樹脂、α－ナフトール／クレゾールノボラック型エポキシ樹脂が好ましい。アラルキルノボラック型エポキシ樹脂としては、ビフェニル骨格を有するアラルキルノボラック型エポキシ樹脂が好ましい。 Epoxy resins include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin; phenol novolac type epoxy resin, cresol novolac type epoxy resin, α-naphthol/cresol novolac type epoxy resin , bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin, aralkyl novolak type epoxy resin, etc.; stilbene type epoxy resin, triazine skeleton-containing epoxy resin, fluorene skeleton-containing epoxy resin, triphenolmethane type epoxy resin , biphenyl type epoxy resins, xylylene type epoxy resins, naphthalene type epoxy resins, dicyclopentadiene type epoxy resins, alicyclic epoxy resins, diglycidyl ether compounds of polyfunctional phenols and polycyclic aromatics such as anthracene, etc. Examples include phosphorus-containing epoxy resins into which phosphorus compounds are introduced. Among these, aralkyl novolac type epoxy resins and α-naphthol/cresol novolac type epoxy resins are preferred from the viewpoints of low warpage, dimensional stability, thickness accuracy, low thermal expansion, and low elasticity. As the aralkyl novolac type epoxy resin, an aralkyl novolac type epoxy resin having a biphenyl skeleton is preferable.
熱硬化性樹脂組成物が熱硬化性樹脂（ｄ）を含有する場合、その含有量は、低反り性、寸法安定性、厚み精度、低熱膨張性及び低弾性の観点から、熱硬化性樹脂組成物中の樹脂成分の固形分１００質量部に対して、１～４５質量部が好ましく、２～４０質量部がより好ましく、３～３５質量部がさらに好ましい。 When the thermosetting resin composition contains a thermosetting resin (d), its content is determined from the viewpoints of low warpage, dimensional stability, thickness accuracy, low thermal expansion, and low elasticity. It is preferably 1 to 45 parts by weight, more preferably 2 to 40 parts by weight, and even more preferably 3 to 35 parts by weight, based on 100 parts by weight of the solid content of the resin component in the product.
（硬化促進剤（ｅ））
熱硬化性樹脂組成物は、さらに、硬化促進剤（ｅ）を含有することが好ましい。
硬化促進剤（ｅ）としては、ナフテン酸亜鉛、ナフテン酸コバルト、オクチル酸スズ、オクチル酸コバルト、ビスアセチルアセトナートコバルト（ＩＩ）、トリスアセチルアセトナートコバルト（ＩＩＩ）等の有機金属塩；イミダゾール類及びその誘導体；有機リン系化合物；第二級アミン類；第三級アミン類；第四級アンモニウム塩などが挙げられる。これらの中でも、耐熱性、難燃性及び金属回路との接着強度の観点からは、イミダゾール類及びその誘導体が好ましく、低熱膨張性の観点からは、有機リン系化合物が好ましい。
硬化促進剤（ｅ）は１種を単独で用いても２種類以上を混合して用いてもよい。
熱硬化性樹脂組成物が硬化促進剤（ｅ）を含有する場合、その含有量は、熱硬化性樹脂組成物中の樹脂成分の固形分１００質量部に対して、０．１～１０質量部が好ましく、０．３～５質量部がより好ましく、０．７～１．５質量部がさらに好ましい。硬化促進剤（ｅ）の含有量が０．１質量部以上であると、耐熱性、難燃性及び銅箔接着性に優れる傾向にあり、１０質量部以下であると、耐熱性、経日安定性及びプレス成形性に優れる傾向にある。
(Curing accelerator (e))
It is preferable that the thermosetting resin composition further contains a curing accelerator (e).
As the curing accelerator (e), organic metal salts such as zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, cobalt bisacetylacetonate (II), cobalt trisacetylacetonate (III); imidazoles; and derivatives thereof; organic phosphorus compounds; secondary amines; tertiary amines; quaternary ammonium salts, and the like. Among these, imidazoles and derivatives thereof are preferred from the viewpoint of heat resistance, flame retardance, and adhesive strength with metal circuits, and organic phosphorus compounds are preferred from the viewpoint of low thermal expansion.
The curing accelerator (e) may be used alone or in combination of two or more.
When the thermosetting resin composition contains the curing accelerator (e), the content thereof is 0.1 to 10 parts by mass based on 100 parts by mass of the solid content of the resin component in the thermosetting resin composition. is preferable, 0.3 to 5 parts by weight is more preferable, and even more preferably 0.7 to 1.5 parts by weight. When the content of the curing accelerator (e) is 0.1 parts by mass or more, heat resistance, flame retardance, and copper foil adhesion tend to be excellent, and when it is 10 parts by mass or less, heat resistance and aging properties tend to be excellent. It tends to have excellent stability and press formability.
（無機充填材（ｆ））
熱硬化性樹脂組成物は、さらに、無機充填材（ｆ）を含有することが好ましい。
無機充填材（ｆ）としては、シリカ、アルミナ、タルク、マイカ、カオリン、水酸化アルミニウム、ベーマイト、水酸化マグネシウム、ホウ酸亜鉛、スズ酸亜鉛、酸化亜鉛、酸化チタン、窒化ホウ素、炭酸カルシウム、硫酸バリウム、ホウ酸アルミニウム、チタン酸カリウム、ガラス粉、中空ガラスビーズが好ましく挙げられる。ガラス粉としては、Ｅガラス、Ｔガラス、Ｄガラス等が挙げられる。
無機充填材（ｆ）は１種を単独で用いても２種類以上を混合して用いてもよい。
これらの中でも、誘電特性、耐熱性及び低熱膨張性の観点から、シリカが好ましい。シリカとしては、例えば、湿式法で製造され含水率の高い沈降シリカと、乾式法で製造され結合水等をほとんど含まない乾式法シリカが挙げられる。乾式法シリカは、さらに、製造法の違いにより、破砕シリカ、フュームドシリカ、溶融球状シリカ等に分類される。これらの中でも、低熱膨張性及び樹脂に充填した際の流動性の観点から、溶融球状シリカが好ましい。
(Inorganic filler (f))
It is preferable that the thermosetting resin composition further contains an inorganic filler (f).
Inorganic fillers (f) include silica, alumina, talc, mica, kaolin, aluminum hydroxide, boehmite, magnesium hydroxide, zinc borate, zinc stannate, zinc oxide, titanium oxide, boron nitride, calcium carbonate, and sulfuric acid. Preferred examples include barium, aluminum borate, potassium titanate, glass powder, and hollow glass beads. Examples of the glass powder include E glass, T glass, and D glass.
The inorganic filler (f) may be used alone or in combination of two or more.
Among these, silica is preferred from the viewpoint of dielectric properties, heat resistance, and low thermal expansion. Examples of silica include precipitated silica produced by a wet process and having a high water content, and dry process silica produced by a dry process and containing almost no bound water or the like. Dry process silica is further classified into crushed silica, fumed silica, fused spherical silica, etc. depending on the manufacturing method. Among these, fused spherical silica is preferred from the viewpoint of low thermal expansion and fluidity when filled into a resin.
無機充填材（ｆ）の平均粒子径は、０．１～１０μｍが好ましく、０．３～８μｍがより好ましく、０．３～３μｍがさらに好ましい。平均粒子径が０．１μｍ以上であると、樹脂に高充填した際の流動性を良好に保てる傾向にあり、１０μｍ以下であると、粗大粒子の混入確率を低減し、粗大粒子起因の不良の発生を抑えることができる傾向にある。ここで、平均粒子径とは、粒子の全体積を１００％として粒子径による累積度数分布曲線を求めたとき、体積５０％に相当する点の粒子径のことであり、レーザ回折散乱法を用いた粒度分布測定装置等で測定することができる。
無機充填材（ｆ）は、カップリング剤で表面処理されたものであってもよい。カップリング剤による表面処理の方式は、配合前の無機充填材（ｆ）に対して乾式又は湿式で表面処理する方式であってもよく、表面未処理の無機充填材（ｆ）を、他の成分に配合して組成物とした後、該組成物にシランカップリング剤を添加する、いわゆるインテグラルブレンド処理方式であってもよい。
カップリング剤としては、シラン系カップリング剤、チタネート系カップリング剤、シリコーンオリゴマー等が挙げられる。
The average particle diameter of the inorganic filler (f) is preferably 0.1 to 10 μm, more preferably 0.3 to 8 μm, and even more preferably 0.3 to 3 μm. When the average particle diameter is 0.1 μm or more, fluidity tends to be maintained well when resin is highly filled, and when it is 10 μm or less, the probability of coarse particles being mixed in is reduced, and defects caused by coarse particles are reduced. There is a tendency to be able to suppress the occurrence. Here, the average particle diameter is the particle diameter at a point corresponding to 50% of the volume when a cumulative frequency distribution curve based on the particle diameter is calculated with the total volume of the particles as 100%. It can be measured using a particle size distribution measuring device etc.
The inorganic filler (f) may be surface-treated with a coupling agent. The method of surface treatment using a coupling agent may be a dry or wet surface treatment method for the inorganic filler (f) before blending, and the surface-untreated inorganic filler (f) may be treated by other methods. A so-called integral blend processing method may be used, in which the silane coupling agent is added to the composition after being blended with the components to form a composition.
Examples of the coupling agent include silane coupling agents, titanate coupling agents, silicone oligomers, and the like.
熱硬化性樹脂組成物が無機充填材（ｆ）を含有する場合、その含有量は、成形性及び低熱膨張性の観点から、熱硬化性樹脂組成物中の樹脂成分の固形分１００質量部に対して、２０～３００質量部が好ましく、５０～２００質量部がより好ましく、７０～２００質量部がさらに好ましい。 When the thermosetting resin composition contains an inorganic filler (f), the content thereof is determined based on 100 parts by mass of the solid content of the resin component in the thermosetting resin composition from the viewpoint of moldability and low thermal expansion. On the other hand, it is preferably 20 to 300 parts by weight, more preferably 50 to 200 parts by weight, and even more preferably 70 to 200 parts by weight.
（その他の成分）
熱硬化性樹脂組成物は、本発明の効果を阻害しない範囲で、難燃剤、紫外線吸収剤、酸化防止剤、光重合開始剤、蛍光増白剤、接着性向上剤等を含有していてもよい。
(Other ingredients)
The thermosetting resin composition may contain flame retardants, ultraviolet absorbers, antioxidants, photopolymerization initiators, optical brighteners, adhesion improvers, etc., as long as they do not impede the effects of the present invention. good.
難燃剤としては、臭素、塩素等を含有する含ハロゲン系難燃剤；トリフェニルホスフェート、トリクレジルホスフェート、トリスジクロロプロピルホスフェート、リン酸エステル系化合物、赤リン等のリン系難燃剤；スルファミン酸グアニジン、硫酸メラミン、ポリリン酸メラミン、メラミンシアヌレート等の窒素系難燃剤；シクロホスファゼン、ポリホスファゼン等のホスファゼン系難燃剤；三酸化アンチモン等の無機系難燃剤などが挙げられる。 Examples of flame retardants include halogen-containing flame retardants containing bromine, chlorine, etc.; phosphorus flame retardants such as triphenyl phosphate, tricresyl phosphate, trisdichloropropyl phosphate, phosphoric acid ester compounds, and red phosphorus; guanidine sulfamate , nitrogen-based flame retardants such as melamine sulfate, melamine polyphosphate, and melamine cyanurate; phosphazene-based flame retardants such as cyclophosphazene and polyphosphazene; and inorganic flame retardants such as antimony trioxide.
紫外線吸収剤としては、ベンゾトリアゾール系紫外線吸収剤等が挙げられる。
酸化防止剤としては、ヒンダードフェノール系酸化防止剤、ヒンダードアミン系酸化防止剤等が挙げられる。
光重合開始剤としては、ベンゾフェノン類、ベンジルケタール類、チオキサントン系等の光重合開始剤が挙げられる。
蛍光増白剤としては、スチルベン誘導体の蛍光増白剤等が挙げられる。
接着性向上剤としては、尿素シラン等の尿素化合物、シラン系、チタネート系、アルミネート系等のカップリング剤が挙げられる。
Examples of the ultraviolet absorber include benzotriazole ultraviolet absorbers.
Examples of the antioxidant include hindered phenol antioxidants and hindered amine antioxidants.
Examples of the photopolymerization initiator include benzophenones, benzyl ketals, and thioxanthone photopolymerization initiators.
Examples of the fluorescent brightener include stilbene derivative fluorescent brighteners.
Examples of the adhesion improver include urea compounds such as urea silane, silane-based, titanate-based, aluminate-based coupling agents, and the like.
熱硬化性樹脂組成物は、樹脂フィルム（Ｉ）の製造に用い易いように、希釈溶剤として有機溶剤を使用し、各成分が有機溶媒中に溶解又は分散されたワニスの状態としてもよい。
有機溶媒としては、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶剤；メチルセロソルブ等のアルコール系溶剤；テトラヒドロフラン等のエーテル系溶剤；トルエン、キシレン、メシチレン等の芳香族系溶剤などが挙げられる。有機溶剤は１種を単独で用いても２種類以上を混合して用いてもよい。
ワニスの固形分濃度は、４０～９０質量％が好ましく、５０～８０質量％がより好ましい。ワニスの固形分濃度が前記範囲内であると、塗工性を良好に保ち、樹脂フィルム（Ｉ）の厚さ等を適切な範囲に調整し易くなる。
The thermosetting resin composition may be in the form of a varnish in which each component is dissolved or dispersed in the organic solvent using an organic solvent as a diluting solvent so that it can be easily used in producing the resin film (I).
Examples of organic solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohol solvents such as methyl cellosolve; ether solvents such as tetrahydrofuran; and aromatic solvents such as toluene, xylene, and mesitylene. . The organic solvents may be used alone or in combination of two or more.
The solid content concentration of the varnish is preferably 40 to 90% by mass, more preferably 50 to 80% by mass. When the solid content concentration of the varnish is within the above range, good coating properties can be maintained and the thickness etc. of the resin film (I) can be easily adjusted to an appropriate range.
（樹脂フィルム（Ｉ）の製造方法）
樹脂フィルム（Ｉ）は、例えば、前記熱硬化性樹脂組成物を支持体に塗布した後、乾燥及び半硬化（Ｂステージ化）させることで得ることができる。なお、半硬化（Ｂステージ化）は、熱硬化性樹脂組成物の粘度がラミネートの作業性が良い粘度になるように行うことが好ましい。乾燥条件としては、例えば、９０～１３０℃で１～１０分間である。
支持体としては、ポリエチレンテレフタレート（以下、「ＰＥＴ」ともいう）、二軸延伸ポリプロピレン、ポリエチレン、ポリビニルフルオレート、ポリイミド等の有機フィルム；銅、アルミニウム、これら金属の合金のフィルム；これらの有機フィルム又は金属フィルムの表面に離型剤で離型処理を行ったフィルムなどが挙げられる。これらの中でも、価格及び取り扱い性の観点から、ＰＥＴフィルムが好ましい。
支持体の厚さは、取扱い性の観点から、１０～１２０μｍが好ましく、１５～８０μｍがより好ましく、１５～７０μｍがさらに好ましい。
また、熱硬化性樹脂組成物を塗布し半硬化させた面に保護フィルムを積層して熱硬化性樹脂組成物を挟んで巻き取ると作業性が良い。保護フィルムは、支持体と同様の材料を使用することができる。
(Method for producing resin film (I))
The resin film (I) can be obtained, for example, by applying the thermosetting resin composition to a support, followed by drying and semi-curing (B-staging). In addition, it is preferable to perform semi-curing (B-staging) so that the viscosity of the thermosetting resin composition becomes a viscosity that provides good laminating workability. The drying conditions are, for example, 90 to 130° C. for 1 to 10 minutes.
Examples of the support include organic films such as polyethylene terephthalate (hereinafter also referred to as "PET"), biaxially oriented polypropylene, polyethylene, polyvinyl fluorate, and polyimide; films of copper, aluminum, and alloys of these metals; Examples include films in which the surface of a metal film is subjected to mold release treatment with a mold release agent. Among these, PET film is preferred from the viewpoint of price and ease of handling.
The thickness of the support is preferably 10 to 120 μm, more preferably 15 to 80 μm, and even more preferably 15 to 70 μm, from the viewpoint of handleability.
Further, workability is improved if a protective film is laminated on the surface on which the thermosetting resin composition has been applied and semi-cured, and then the thermosetting resin composition is sandwiched and rolled up. The protective film can be made of the same material as the support.
樹脂フィルム（Ｉ）の厚さ（支持体及び保護フィルムの厚さを除く）は、骨材等の厚さ等に応じて適宜決定すればよく、骨材の厚さより薄い樹脂フィルム（Ｉ）を用いる場合は、樹脂フィルム（Ｉ）を骨材にラミネートしたものに対して、再度、別の樹脂フィルム（Ｉ）をラミネートしてもよい。
なお、樹脂フィルム（Ｉ）を複数枚使用する場合、フィルム（Ｉ）の熱硬化度、配合組成等が異なるものを組み合わせて使用してもよい。
また、プリプレグ中における熱硬化性樹脂組成物の固形分含有量は、２０～９０質量％が好ましく、３０～８５質量％がより好ましく、４０～８０質量％がさらに好ましい。
The thickness of the resin film (I) (excluding the thickness of the support and protective film) may be appropriately determined depending on the thickness of the aggregate, etc. When used, another resin film (I) may be laminated again to the resin film (I) laminated to the aggregate.
In addition, when using a plurality of resin films (I), films (I) having different degrees of thermosetting, different compositions, etc. may be used in combination.
Further, the solid content of the thermosetting resin composition in the prepreg is preferably 20 to 90% by mass, more preferably 30 to 85% by mass, and even more preferably 40 to 80% by mass.
［コアレス基板用プリプレグ］
本発明のコアレス基板用プリプレグは、本発明のコアレス基板用プリプレグの製造方法により製造されたコアレス基板用プリプレグである。
[Prepreg for coreless board]
The coreless substrate prepreg of the present invention is a coreless substrate prepreg manufactured by the method of manufacturing a coreless substrate prepreg of the present invention.
本発明のプリプレグは、パッケージ形成時の信頼性の観点から、下記測定方法に従って測定したエッチング後の寸法変化率（i）が、－８．０～＋８．０％であり、かつ１７０℃１時間加熱後の寸法変化率（ii）が、－４．０～＋４．０％であることが好ましく、エッチング後の寸法変化率（i）が、－５．０～＋５．０％であり、かつ１７０℃１時間加熱後の寸法変化率（ii）が、－２．５～＋２．５％であることがより好ましい。
＜寸法変化率の測定方法＞
プリプレグの両表面に厚さ１２μｍの電解銅箔を有する２５０ｃｍ角の銅張積層板を評価基板とし、その４角から縦に１ｃｍ、横に１ｃｍの部分に基準穴を合計４つ設け、隣接する穴間同士の距離の平均値を基準寸法とし、
該評価基板を銅エッチング液に浸漬することにより銅箔を取り除いた後の、隣接する穴間同士の距離の平均値をエッチング後寸法とし、
エッチング後の評価基板を、１７０℃で１時間加熱した後の、隣接する穴間同士の距離の平均値を加熱後寸法とし、
下記式に基づいて、エッチング後の寸法変化率（i）と、１７０℃１時間加熱後の寸法変化率（ii）を各々計算する。
寸法変化率（i）（％）＝（エッチング後寸法－基準寸法）×１００／基準寸法
寸法変化率（ii）（％）＝（加熱後寸法－エッチング後寸法）×１００／エッチング後寸法
From the viewpoint of reliability during package formation, the prepreg of the present invention has a dimensional change rate (i) of -8.0 to +8.0% after etching measured according to the following measurement method, and is heated at 170°C for 1 hour. It is preferable that the dimensional change rate (ii) after heating is -4.0 to +4.0%, the dimensional change rate (i) after etching is -5.0 to +5.0%, and It is more preferable that the dimensional change rate (ii) after heating at 170°C for 1 hour is -2.5 to +2.5%.
<Method for measuring dimensional change rate>
The evaluation board was a 250 cm square copper-clad laminate with 12 μm thick electrolytic copper foil on both surfaces of the prepreg, and a total of 4 reference holes were provided at 1 cm vertically and 1 cm horizontally from the four corners, and adjacent The average value of the distance between holes is used as the standard dimension,
After removing the copper foil by immersing the evaluation board in a copper etching solution, the average value of the distance between adjacent holes is taken as the post-etching dimension,
After heating the evaluation board after etching at 170 ° C. for 1 hour, the average value of the distance between adjacent holes is taken as the dimension after heating,
Based on the following equations, the dimensional change rate (i) after etching and the dimensional change rate (ii) after heating at 170° C. for 1 hour are calculated.
Dimensional change rate (i) (%) = (dimension after etching - standard dimension) x 100 / standard dimension Dimensional change rate (ii) (%) = (dimension after heating - dimension after etching) x 100 / dimension after etching
本発明のプリプレグは、歩留まり向上等の生産性の向上、及びパッケージの反り量低減の観点から、下記測定方法に従って測定した厚み精度の値が、１０％以下であることが好ましく、７．５％であることがより好ましい。
＜厚み精度の測定方法＞
プリプレグの両表面に厚さ１２μｍの電解銅箔を有する銅張積層板の幅方向の中心から５０ｍｍ単位で幅方向に計１１点、前記１１点を各々起点として長さ方向に５０ｍｍ単位で１０点の厚さを測定し、その最大厚さ、最小厚さ及び平均厚さを求め、下記式に基づいて、平均厚さに対する最大厚さの変化率及び平均厚さに対する最小厚さの変化率を各々求め、いずれか大きい方を、厚み精度の値とする。
最大厚さの変化率（％）＝（最大厚さ－平均厚さ）×１００／平均厚さ
最小厚さの変化率（％）＝（平均厚さ－最小厚さ）×１００／平均厚さ
なお、厚み精度は、より具体的には、実施例の記載の方法により測定することができる。
The prepreg of the present invention preferably has a thickness accuracy value of 10% or less, preferably 7.5%, measured according to the following measurement method, from the viewpoint of improving productivity such as improving yield and reducing the amount of warpage of the package. It is more preferable that
<Measurement method of thickness accuracy>
A total of 11 points in the width direction in 50 mm increments from the center of the width direction of a copper-clad laminate having electrolytic copper foil with a thickness of 12 μm on both surfaces of the prepreg, and 10 points in 50 mm increments in the length direction from the 11 points above as starting points. Measure the thickness, find the maximum thickness, minimum thickness, and average thickness, and calculate the rate of change of the maximum thickness with respect to the average thickness and the rate of change of the minimum thickness with respect to the average thickness based on the following formula. Find each of them, and use the larger one as the thickness accuracy value.
Rate of change in maximum thickness (%) = (Maximum thickness - Average thickness) x 100/Average thickness Rate of change in minimum thickness (%) = (Average thickness - Minimum thickness) x 100/Average thickness In addition, the thickness accuracy can be measured more specifically by the method described in Examples.
本発明のプリプレグは、パッケージの反り量低減の観点から、硬化物の弾性率が、８～３５ＧＰａであることが好ましく、１０～２０ＧＰａであることがより好ましい。
ここで、プリプレグの熱膨張率は、下記式（１）で示される、Ｓｃａｐｅｒｙ式に従うことが一般的に知られている。
Ａ≒（ＡｒＥｒＦｒ＋ＡｇＥｇＦｇ）／（ＥｒＦｒ＋ＥｇＦｇ） （１）
（上記（１）式において、Ａはプリプレグの熱膨張率、Ａｒは樹脂組成物の熱膨張率、Ｅｒは樹脂組成物の弾性率、Ｆｒは樹脂組成物の体積分率、Ａｇはガラスクロスの熱膨張率、Ｅｇはガラスクロスの弾性率、Ｆｇはガラスクロスの体積分率を表す。）
したがって、任意の体積分率において同一の物性のガラスクロスを使用した場合、樹脂組成物の弾性率及び熱膨張率を低減することが好ましい。
硬化物の弾性率は、実施例に記載の方法により測定することができる。
In the prepreg of the present invention, the cured product preferably has an elastic modulus of 8 to 35 GPa, more preferably 10 to 20 GPa, from the viewpoint of reducing the amount of warpage of the package.
Here, it is generally known that the coefficient of thermal expansion of the prepreg follows the Scapery equation, which is expressed by the following equation (1).
A≒(ArErFr+AgEgFg)/(ErFr+EgFg) (1)
(In the above equation (1), A is the coefficient of thermal expansion of the prepreg, Ar is the coefficient of thermal expansion of the resin composition, Er is the elastic modulus of the resin composition, Fr is the volume fraction of the resin composition, and Ag is the coefficient of thermal expansion of the glass cloth. The coefficient of thermal expansion, Eg is the elastic modulus of the glass cloth, and Fg is the volume fraction of the glass cloth.)
Therefore, when glass cloth having the same physical properties is used at a given volume fraction, it is preferable to reduce the elastic modulus and thermal expansion coefficient of the resin composition.
The elastic modulus of the cured product can be measured by the method described in Examples.
本発明のプリプレグは、パッケージの反り量低減の観点から、硬化物の熱膨張率が、３．０～６．７ｐｐｍ／℃であることが好ましく、４．０～６．５ｐｐｍ／℃であることがより好ましく、５．０～６．０ｐｐｍ／℃であることがさらに好ましい。
硬化物の熱膨張率は、実施例に記載の方法により測定することができる。
In the prepreg of the present invention, the thermal expansion coefficient of the cured product is preferably 3.0 to 6.7 ppm/°C, and preferably 4.0 to 6.5 ppm/°C, from the viewpoint of reducing the amount of warpage of the package. is more preferable, and even more preferably 5.0 to 6.0 ppm/°C.
The coefficient of thermal expansion of the cured product can be measured by the method described in Examples.
本発明のプリプレグ全体の厚さは、内層回路の厚さ等に応じて適宜調整すればよいが、基板の薄型化、成形性及び作業性の観点から、好ましくは１０μｍ以上、より好ましくは２０μｍ以上であり、そして、好ましくは７００μｍ以下、より好ましくは５００μｍ以下、さらに好ましくは２００μｍ以下、よりさらに好ましくは１００μｍ以下、よりさらに好ましくは８０μｍ以下、特に好ましくは５０μｍ以下、最も好ましくは４０μｍ以下である。 The overall thickness of the prepreg of the present invention may be adjusted appropriately depending on the thickness of the inner layer circuit, etc., but from the viewpoint of thinning the substrate, moldability, and workability, it is preferably 10 μm or more, more preferably 20 μm or more. and is preferably 700 μm or less, more preferably 500 μm or less, even more preferably 200 μm or less, even more preferably 100 μm or less, even more preferably 80 μm or less, particularly preferably 50 μm or less, and most preferably 40 μm or less.
［コアレス基板及びその製造方法］
本発明のコアレス基板は、本発明のコアレス基板用プリプレグを用いて形成された絶縁層を含有するものである。
本発明のコアレス基板は、例えば、支持体（コア基板）上に、本発明のプリプレグを用いて導体層と絶縁層とが交互に積層されてなるビルドアップ層を形成した後、前記支持体を分離する方法により製造することができる。ビルドアップ層の形成方法に特に制限はなく、公知の方法を採用できる。例えば、ビルドアップ層は次の方法によって形成できる（図２参照）。
まず、支持体（コア基板）１上に本発明のプリプレグ２を配置する。なお、前記支持体（コア基板）１上には接着層を配置した上で、プリプレグ２を配置してもよい。その後、プリプレグ２を加熱硬化して絶縁層とする。次いで、ドリル切削方法、又はＹＡＧレーザー、ＣＯ２レーザー等を用いるレーザー加工方法などによってビアホール３を形成した後、必要に応じて表面粗化処理及びデスミア処理を行なう。続いて、サブトラクティブ法、フルアディティブ法、セミアディティブ法（ＳＡＰ：Semi Additive Process）、モディファイドセミアディティブ法（ｍ－ＳＡＰ：modified Semi Additive Process）等によって回路パターン４を形成する。以上の過程を繰り返すことによって、ビルドアップ層５が形成される。形成したビルドアップ層５を、支持体（コア基板）１から分離することによって、コアレス基板が得られる。なお、ビスドアップ層５は、支持体（コア基板）１の片面に形成してもよいし、両面に形成してもよい。
本発明のコアレス基板は、本発明のプリプレグを硬化してなる絶縁層を１層以上含むものであり、本発明のプリプレグ以外のプリプレグ、樹脂フィルム等を硬化してなる絶縁層を含んでいてもよい。
本発明のコアレス基板の厚さは、コア基板を有していないために通常は小さく、具体的には、１５～２００ｍｍが好ましく、３０～１５０ｍｍがより好ましく、３５～１００ｍｍがさらに好ましい。
[Coreless board and its manufacturing method]
The coreless substrate of the present invention contains an insulating layer formed using the coreless substrate prepreg of the present invention.
In the coreless substrate of the present invention, for example, after forming a build-up layer in which a conductor layer and an insulating layer are alternately laminated using the prepreg of the present invention on a support (core substrate), the support is It can be produced by a separation method. There is no particular restriction on the method of forming the buildup layer, and any known method can be used. For example, the buildup layer can be formed by the following method (see FIG. 2).
First, the prepreg 2 of the present invention is placed on a support (core substrate) 1. Note that the prepreg 2 may be placed on the support body (core substrate) 1 after placing an adhesive layer thereon. Thereafter, the prepreg 2 is heated and cured to form an insulating layer. Next, a via hole 3 is formed by a drill cutting method or a laser processing method using a YAG laser, a CO 2 laser, etc., and then surface roughening treatment and desmear treatment are performed as necessary. Subsequently, a circuit pattern 4 is formed by a subtractive method, a full additive method, a semi-additive process (SAP), a modified semi-additive process (m-SAP), or the like. By repeating the above process, the buildup layer 5 is formed. By separating the formed buildup layer 5 from the support (core substrate) 1, a coreless substrate is obtained. Note that the screw-up layer 5 may be formed on one side or both sides of the support body (core substrate) 1.
The coreless substrate of the present invention includes one or more insulating layers formed by curing the prepreg of the present invention, and may also include an insulating layer formed by curing prepregs, resin films, etc. other than the prepreg of the present invention. good.
The thickness of the coreless substrate of the present invention is usually small because it does not have a core substrate, and specifically, it is preferably 15 to 200 mm, more preferably 30 to 150 mm, and even more preferably 35 to 100 mm.
［半導体パッケージ］
本発明の半導体パッケージは、本発明のコアレス基板に半導体素子を搭載してなるものであり、例えば、前記コアレス基板の所定の位置に半導体チップ、メモリ等の半導体素子を搭載し製造される。
[Semiconductor package]
The semiconductor package of the present invention is formed by mounting a semiconductor element on the coreless substrate of the present invention, and is manufactured by, for example, mounting a semiconductor element such as a semiconductor chip or a memory at a predetermined position on the coreless substrate.
次に、下記の実施例により本発明をさらに詳しく説明するが、これらの実施例は本発明を制限するものではない。 Next, the present invention will be explained in more detail with reference to the following examples, but these examples are not intended to limit the present invention.
［変性ポリイミド（Ｘ）の製造］
製造例Ｘ１：変性ポリイミド（Ｘ－１）の合成
温度計、攪拌装置及び還流冷却管付き水分定量器の付いた加熱及び冷却可能な容積２リットルの反応容器に、両末端ジアミン変性シロキサン（信越化学工業株式会社製、商品名：Ｘ－２２－１６１Ａ）を７２ｇと、ビス（４－マレイミドフェニル）メタン（日本化薬株式会社製、商品名：ＢＭＩ）を２５２ｇと、プロピレングリコールモノメチルエーテルを２７０．０ｇ入れ、１１０℃で３時間反応させて、変性ポリイミド（Ｘ－１）含有溶液を得た。
[Production of modified polyimide (X)]
Production Example 72 g of Kogyo Co., Ltd., trade name: 0 g was added and reacted at 110°C for 3 hours to obtain a solution containing modified polyimide (X-1).
製造例Ｘ２：変性ポリイミド（Ｘ－２）の合成
温度計、攪拌装置及び還流冷却管付き水分定量器の付いた加熱及び冷却可能な容積２リットルの反応容器に、両末端ジアミン変性シロキサン（信越化学工業株式会社製、商品名：Ｘ－２２－１６１Ｂ）を８５ｇと、２，２－ビス〔４－（４－マレイミドフェノキシ）フェニル〕プロパン（日本化薬株式会社製、商品名：ＢＭＩ－４０００）を２８９ｇと、プロピレングリコールモノメチルエーテルを２７０．０ｇ入れ、１１０℃で３時間反応させて、変性ポリイミド（Ｘ－２）含有溶液を得た。
Production Example 85 g of 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane (manufactured by Nippon Kayaku Co., Ltd., product name: BMI-4000) and 270.0 g of propylene glycol monomethyl ether were added and reacted at 110°C for 3 hours to obtain a solution containing modified polyimide (X-2).
［ワニスの作製］
製造例１～１２
以下に示す各成分を、第１表に示す配合割合（表中の数値は固形分の質量部であり、溶液又は分散液の場合は固形分換算量である。）で混合し、有機溶剤としてメチルエチルケトンを用いて、固形分濃度が６５質量％の均一なワニス状の熱硬化性樹脂組成物（以下、単に「ワニス」ともいう）を作製した。なお、各例で使用した成分の詳細は下記の通りである。
[Preparation of varnish]
Production examples 1 to 12
The components shown below are mixed at the proportions shown in Table 1 (the numbers in the table are parts by mass of solid content, and in the case of solutions or dispersions, the amount is equivalent to solid content), and as an organic solvent. A uniform varnish-like thermosetting resin composition (hereinafter also simply referred to as "varnish") having a solid content concentration of 65% by mass was prepared using methyl ethyl ketone. The details of the components used in each example are as follows.
〔変性ポリイミド（Ｘ）〕
・Ｘ－１：製造例Ｘ１で合成した変性ポリイミド（Ｘ－１）
・Ｘ－２：製造例Ｘ２で合成した変性ポリイミド（Ｘ－２）
[Modified polyimide (X)]
・X-1: Modified polyimide (X-1) synthesized in Production Example X1
・X-2: Modified polyimide (X-2) synthesized in Production Example X2
〔マレイミド化合物（ａ）〕
・ＢＭＩ：ビス（４－マレイミドフェニル）メタン〔ケイ・アイ化成株式会社製、商品名〕
・ＢＭＩ－４０００：２，２－ビス〔４－（４－マレイミドフェノキシ）フェニル〕プロパン〔大和化成工業株式会社製、商品名〕
[Maleimide compound (a)]
・BMI: Bis(4-maleimidophenyl)methane [manufactured by K.I. Kasei Co., Ltd., product name]
・BMI-4000: 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane [manufactured by Daiwa Kasei Kogyo Co., Ltd., product name]
〔アミン化合物（ｂ）〕
・Ｘ－２２－１６１Ａ：両末端ジアミン変性シロキサン〔信越化学工業株式会社製、商品名、アミノ基の官能基当量：８００ｇ／ｍｏｌ〕
・Ｘ－２２－１６１Ｂ：両末端ジアミン変性シロキサン〔信越化学工業株式会社製、商品名，アミノ基の官能基当量：１，５００ｇ／ｍｏｌ〕
[Amine compound (b)]
・X-22-161A: Diamine-modified siloxane at both ends [manufactured by Shin-Etsu Chemical Co., Ltd., trade name, functional group equivalent of amino group: 800 g/mol]
・X-22-161B: Diamine-modified siloxane at both ends [manufactured by Shin-Etsu Chemical Co., Ltd., trade name, functional group equivalent of amino group: 1,500 g/mol]
〔熱可塑性エラストマー（ｃ）〕
・エポフレンド（登録商標）ＣＴ－３１０：エポキシ変性スチレン－ブタジエン共重合樹脂〔株式会社ダイセル製、商品名〕
・タフテック（登録商標）Ｍ１９１３：カルボン酸変性水添スチレン－ブタジエン共重合樹脂〔旭化成ケミカルズ株式会社製、商品名〕
・ＳＧ－Ｐ３：エポキシ基含有アクリル系熱可塑性エラストマー〔ナガセケムテックス株式会社製、商品名〕
[Thermoplastic elastomer (c)]
・Epofriend (registered trademark) CT-310: Epoxy-modified styrene-butadiene copolymer resin [manufactured by Daicel Corporation, product name]
・Tuftec (registered trademark) M1913: Carboxylic acid modified hydrogenated styrene-butadiene copolymer resin [manufactured by Asahi Kasei Chemicals Co., Ltd., product name]
・SG-P3: Epoxy group-containing acrylic thermoplastic elastomer [manufactured by Nagase ChemteX Co., Ltd., product name]
〔熱硬化性樹脂（ｄ）〕
・ＮＣ－７０００－Ｌ：ナフタレン骨格含有型エポキシ樹脂（より詳細には、α－ナフトール／クレゾールノボラック型エポキシ樹脂）〔日本化薬株式会社製、商品名〕
・ＮＣ－３０００－Ｈ：ビフェニルアラルキル型エポキシ樹脂〔日本化薬株式会社製、商品名〕
[Thermosetting resin (d)]
・NC-7000-L: Naphthalene skeleton-containing epoxy resin (more specifically, α-naphthol/cresol novolak epoxy resin) [manufactured by Nippon Kayaku Co., Ltd., product name]
・NC-3000-H: Biphenylaralkyl epoxy resin [manufactured by Nippon Kayaku Co., Ltd., product name]
〔硬化促進剤（ｅ）〕
・Ｇ－８００９Ｌ：イソシアネートマスクイミダゾール〔第一工業製薬株式会社製、商品名〕
・ＴＰＰ－Ｓ：トリフェニルホスフィントリフェニルボラン〔北興化学株式会社製、商品名〕
[Curing accelerator (e)]
・G-8009L: Isocyanate mask imidazole [manufactured by Daiichi Kogyo Seiyaku Co., Ltd., product name]
・TPP-S: Triphenylphosphine triphenylborane [manufactured by Hokuko Chemical Co., Ltd., trade name]
〔無機充填材（ｆ）〕
・ＳＣ２０５０－ＫＮＫ：溶融シリカ（株式会社アドマテックス製、商品名、平均粒子径：０．５μｍ）
[Inorganic filler (f)]
・SC2050-KNK: Fused silica (manufactured by Admatex Co., Ltd., trade name, average particle size: 0.5 μm)
［プリプレグの作製：方法（Ａ）］
実施例１～６
上記で得られたワニスを、５８０ｍｍ幅のＰＥＴフィルム（帝人デュポンフィルム株式会社製、商品名：Ｇ２）に、塗布幅を５２５ｍｍ、乾燥後の樹脂層が所定の厚さになるように塗布量を調整して塗布し、１２０℃で３分間乾燥して、支持体付き樹脂フィルムを作製した。
次に、支持体付き樹脂フィルムを、骨材であるガラスクロスの両方の表面に、樹脂層がガラスクロスと対向するよう配置し、加圧ロールに挟み込むことにより、ガラスクロスの両方の表面に支持体付き樹脂フィルムを圧接して貼付し、ガラスクロス中に熱硬化性樹脂組成物を含浸させてなるプリプレグを作製した。その後、冷却ロールで冷却して、巻取りを行った。
加圧ロール条件は、ロール温度１００℃、線圧０．２ＭＰａ、速度２．０ｍ／分とした。
得られたプリプレグ中の熱硬化性樹脂組成物の含有量、ガラスクロスの厚さ、ガラスクロスの種類は、後述する測定方法の項に示す。
[Production of prepreg: method (A)]
Examples 1 to 6
The varnish obtained above was applied to a 580 mm wide PET film (manufactured by Teijin DuPont Films Ltd., product name: G2) at a coating width of 525 mm, and in an amount such that the resin layer after drying had a predetermined thickness. The coating was adjusted and applied, and dried at 120° C. for 3 minutes to produce a resin film with a support.
Next, a resin film with a support is placed on both surfaces of the glass cloth, which is the aggregate, so that the resin layer faces the glass cloth, and is supported on both surfaces of the glass cloth by sandwiching it between pressure rolls. A prepreg was produced by attaching a resin film with a body by pressing and impregnating a glass cloth with a thermosetting resin composition. Thereafter, it was cooled with a cooling roll and wound up.
The pressure roll conditions were a roll temperature of 100° C., a linear pressure of 0.2 MPa, and a speed of 2.0 m/min.
The content of the thermosetting resin composition in the obtained prepreg, the thickness of the glass cloth, and the type of glass cloth are shown in the measurement method section described later.
［プリプレグの作製：方法（Ｂ）］
比較例１～６
上記で得られたワニスを、骨材であるガラスクロスに塗工機を用いて塗布した後、１３０℃で１０分間乾燥して、溶剤を除去すると共に熱硬化性樹脂組成物を半硬化させて、プリプレグを作製した。なお、塗布量の調整はスクイズロール法で行った。
得られたプリプレグ中の熱硬化性樹脂組成物の含有量、ガラスクロスの厚さ、ガラスクロスの種類は、後述する測定方法の項に示す。
[Production of prepreg: method (B)]
Comparative examples 1 to 6
The varnish obtained above was applied to glass cloth as an aggregate using a coating machine, and then dried at 130°C for 10 minutes to remove the solvent and semi-cure the thermosetting resin composition. , prepared prepreg. The amount of coating was adjusted using the squeeze roll method.
The content of the thermosetting resin composition in the obtained prepreg, the thickness of the glass cloth, and the type of glass cloth are shown in the measurement method section described later.
［銅張積層板の作製］
上記で得られたプリプレグを用いて、銅張積層板を作製した。銅張積層板は、後述する評価項目に応じて決定される所定枚数のプリプレグと、その上下に電解銅箔（厚さ：１２μｍ）を配置し、圧力２．５ＭＰａ、温度２４０℃で６０分間プレスを行って作製した。
[Production of copper-clad laminate]
A copper-clad laminate was produced using the prepreg obtained above. The copper-clad laminate is made by placing a predetermined number of prepreg sheets determined according to the evaluation items described below and electrolytic copper foil (thickness: 12 μm) above and below them, and pressing them at a pressure of 2.5 MPa and a temperature of 240°C for 60 minutes. It was created by doing.
［測定方法］
以下に示す測定方法でプリプレグを評価した。評価結果を第１表に示す。
[Measuring method]
The prepreg was evaluated using the measurement method shown below. The evaluation results are shown in Table 1.
（１）寸法変化率
上記の銅張積層板の作製において、プリプレグとして、各例で得られたプリプレグ（樹脂組成物の含有量７８質量％、ガラスクロスの厚さ：９．６μｍ、ガラスクロスの種類：Ｅガラスクロス、プリプレグ全体の厚さ：２５μｍ）２枚を使用して、銅張積層板を得た。該銅張積層板を２５０ｃｍ角に切り出したものを評価基板とし、４角から縦に１ｃｍ、横に１ｃｍの部分に基準穴を合計４つ設け、ＣＮＣ画像測定機（株式会社ミツトヨ製、商品名：ＱＶ－Ｈ６０６Ｔ１Ｌ－Ｄ）を使用して、隣接する穴間同士の距離を測定し、その平均値を基準寸法とした。
次に、該評価基板を銅エッチング液（薬液の種類：過硫酸アンモニウム、温度：４０℃処理時間：５分間）に浸漬することにより銅箔を取り除いた後、同様の方法により、隣接する穴間同士の距離を測定し、その平均値をエッチング後寸法とした。
続いて、エッチングにより銅箔を取り除いた評価基板を、１７０℃で１時間、空気中で加熱した後、同様の方法により、隣接する穴間同士の距離を測定し、その平均値を加熱後寸法とした。
上記で得られた各寸法より、下記式に基づいて、エッチング後の寸法変化率（i）と、１７０℃１時間加熱後の寸法変化率（ii）を各々計算した。
寸法変化率（i）＝（エッチング後寸法－基準寸法）×１００／基準寸法
寸法変化率（ii）＝（加熱後寸法－エッチング後寸法）×１００／エッチング後寸法
(1) Dimensional change rate In the preparation of the above copper-clad laminate, the prepreg obtained in each example (resin composition content: 78% by mass, glass cloth thickness: 9.6 μm, glass cloth thickness: A copper-clad laminate was obtained using two sheets of type: E glass cloth (total prepreg thickness: 25 μm). A 250 cm square cut out of the copper clad laminate was used as an evaluation board, and a total of four reference holes were made at 1 cm vertically and 1 cm horizontally from each corner, and a CNC image measuring machine (manufactured by Mitutoyo Co., Ltd., product name: : QV-H606T1L-D), the distance between adjacent holes was measured, and the average value was taken as the reference dimension.
Next, after removing the copper foil by immersing the evaluation board in a copper etching solution (type of chemical solution: ammonium persulfate, temperature: 40°C, processing time: 5 minutes), the adjacent holes were The distance was measured, and the average value was taken as the dimension after etching.
Next, the evaluation board from which the copper foil was removed by etching was heated in air at 170°C for 1 hour, and then the distance between adjacent holes was measured using the same method, and the average value was calculated as the dimension after heating. And so.
From each dimension obtained above, the dimensional change rate (i) after etching and the dimensional change rate (ii) after heating at 170° C. for 1 hour were calculated based on the following formula.
Dimensional change rate (i) = (dimension after etching - standard dimension) x 100 / standard dimension Dimensional change rate (ii) = (dimension after heating - dimension after etching) x 100 / dimension after etching
（２）厚み精度
上記の銅張積層板の作製において、プリプレグとして、各例で得られたプリプレグ（樹脂組成物の含有量７８質量％、ガラスクロスの厚さ：９．６μｍ、ガラスクロスの種類：Ｅガラスクロス、プリプレグ全体の厚さ：２５μｍ）１枚を使用して、銅張積層板を得た。
得られた銅張積層板の幅方向の中心から５０ｍｍ単位で幅方向に計１１点、前記１１点を各々起点として長さ方向に５０ｍｍ単位で１０点（すなわち、１１点×１０点＝１１０点）の厚さを、アップライトゲージを用いて０．００１ｍｍ単位で測定し、その最大厚さ、最小厚さ及び平均厚さを求め、下記式に基づいて、平均厚さに対する最大厚さの変化率及び平均厚さに対する最小厚さの変化率を各々求め、いずれか大きい方を、厚み精度の値とする。
最大厚さの変化率（％）＝（最大厚さ－平均厚さ）×１００／平均厚さ
最小厚さの変化率（％）＝（平均厚さ－最小厚さ）×１００／平均厚さ
(2) Thickness accuracy In the production of the copper-clad laminate described above, the prepreg obtained in each example was used as the prepreg (resin composition content: 78% by mass, glass cloth thickness: 9.6 μm, type of glass cloth) :E glass cloth, total prepreg thickness: 25 μm) was used to obtain a copper-clad laminate.
A total of 11 points in the width direction in 50 mm increments from the center of the width direction of the obtained copper-clad laminate, and 10 points in 50 mm increments in the length direction starting from each of the 11 points (i.e., 11 points x 10 points = 110 points) ) using an upright gauge in units of 0.001 mm, find the maximum thickness, minimum thickness, and average thickness, and calculate the change in maximum thickness with respect to the average thickness based on the following formula. The rate of change of the minimum thickness with respect to the ratio and the average thickness are determined, and the larger one is taken as the value of the thickness accuracy.
Rate of change in maximum thickness (%) = (Maximum thickness - Average thickness) x 100/Average thickness Rate of change in minimum thickness (%) = (Average thickness - Minimum thickness) x 100/Average thickness
（３）熱膨張率
上記の銅張積層板の作製において、プリプレグとして、各例で得られたプリプレグ（樹脂組成物の含有量４８質量％、ガラスクロスの厚さ：０．１０ｍｍ、ガラスクロスの種類：Ｅガラスクロス、プリプレグ全体の厚さ：０．１１ｍｍ）４枚を使用して、銅張積層板を得た。該銅張積層板を銅エッチング液に浸漬することにより銅箔を取り除いた５ｍｍ角の評価基板を作製し、ＴＭＡ試験装置（デュポン社製、ＴＭＡ２９４０）を用いて圧縮法で熱機械分析を行った。評価基板を前記装置にＸ方向に装着後、荷重５ｇ、昇温速度１０℃／分の測定条件にて連続して２回測定した。２回目の測定における３０℃から１００℃までの平均熱膨張率を算出し、これを熱膨張率の値とした。
(3) Coefficient of thermal expansion In the production of the above-mentioned copper-clad laminate, the prepreg obtained in each example (resin composition content: 48% by mass, glass cloth thickness: 0.10 mm, glass cloth A copper-clad laminate was obtained using four sheets (type: E glass cloth, total prepreg thickness: 0.11 mm). A 5 mm square evaluation board from which the copper foil was removed was prepared by immersing the copper-clad laminate in a copper etching solution, and thermomechanical analysis was performed using a compression method using a TMA test device (manufactured by DuPont, TMA2940). . After mounting the evaluation board on the device in the X direction, measurements were performed twice continuously under the measurement conditions of a load of 5 g and a temperature increase rate of 10° C./min. The average coefficient of thermal expansion from 30°C to 100°C in the second measurement was calculated, and this was taken as the value of the coefficient of thermal expansion.
（４）曲げ弾性率
上記の銅張積層板の作製において、プリプレグとして、各例で得られたプリプレグ（樹脂組成物の含有量４８質量％、ガラスクロスの厚さ：０．１０ｍｍ、ガラスクロスの種類：Ｅガラスクロス、プリプレグ全体の厚さ：０．１１ｍｍ）４枚を使用して、銅張積層板を得た。該銅張積層板を銅エッチング液に浸漬することにより銅箔を取り除いた５０ｍｍ×２５ｍｍの評価基板を作製し、株式会社オリエンテック製の５トンテンシロンを用い、クロスヘッド速度１ｍｍ／ｍｉｎ、スパン間距離２０ｍｍの条件で曲げ弾性率を測定した。
(4) Flexural modulus In the preparation of the above copper-clad laminate, the prepreg obtained in each example (resin composition content: 48% by mass, glass cloth thickness: 0.10 mm, glass cloth A copper-clad laminate was obtained using four sheets (type: E glass cloth, total prepreg thickness: 0.11 mm). A 50 mm x 25 mm evaluation board from which the copper foil was removed was prepared by immersing the copper-clad laminate in a copper etching solution, and a 5-ton Tensilon manufactured by Orientec Co., Ltd. was used to create an evaluation board at a crosshead speed of 1 mm/min, between spans. The bending elastic modulus was measured at a distance of 20 mm.
第１表から、本発明の製造方法により得られた実施例１～６のプリプレグは寸法変化率が小さく、厚さばらつきが小さいことが分かる。また、曲げ弾性率を低減した場合における寸法変化率の増加の度合いが、本発明の製造方法により得られた実施例１～６のプリプレグは、従来の製造方法で製造した比較例１～６のプリプレグよりも、大幅に低減されていることが分かる。
以上の結果から、本発明の製造方法は作業性が良好であり、本発明の製造方法によって、優れた厚み精度及び寸法安定性を有するコアレス基板用プリプレグが得られることが分かる。
From Table 1, it can be seen that the prepregs of Examples 1 to 6 obtained by the manufacturing method of the present invention have a small dimensional change rate and a small variation in thickness. Furthermore, the degree of increase in the dimensional change rate when the bending modulus of elasticity is reduced is higher than that of the prepregs of Examples 1 to 6 obtained by the production method of the present invention than that of Comparative Examples 1 to 6 produced by the conventional production method. It can be seen that the reduction is significantly greater than that of prepreg.
From the above results, it can be seen that the manufacturing method of the present invention has good workability, and that a prepreg for coreless substrates having excellent thickness accuracy and dimensional stability can be obtained by the manufacturing method of the present invention.
１ プリプレグの製造装置
２ 骨材送出装置
３ 樹脂フィルム送出装置
４ 保護フィルム剥がし機構
５ 保護フィルム巻取装置
６ シート加熱加圧装置（フィルム圧接手段）
７ シート加圧冷却装置
８ プリプレグ巻取装置
４０ 骨材
４０ａ 骨材の表面（骨材の一方の表面、骨材両表面の一方）
４０ｂ 骨材の裏面（骨材の他方の表面、骨材両表面の他方）
５０ 保護フィルム付き樹脂フィルム（Ｉ）
５２ 保護フィルム
５４ 樹脂フィルム（Ｉ）
５４ａ 樹脂フィルム（Ｉ）の骨材側の表面（骨材側フィルム表面）
６０ プリプレグ
1 Prepreg manufacturing device 2 Aggregate delivery device 3 Resin film delivery device 4 Protective film peeling mechanism 5 Protective film winding device 6 Sheet heating and pressing device (film pressure welding means)
7 Sheet pressure cooling device 8 Prepreg winding device 40 Aggregate 40a Surface of aggregate (one surface of aggregate, one of both surfaces of aggregate)
40b Back side of aggregate (other surface of aggregate, other of both surfaces of aggregate)
50 Resin film with protective film (I)
52 Protective film 54 Resin film (I)
54a Aggregate side surface of resin film (I) (aggregate side film surface)
60 Prepreg
Claims (12)
前記貼付を、常圧下において、前記樹脂フィルム（Ｉ）を、前記シート状骨材の少なくとも一方の表面に圧接するフィルム圧接工程により行い、
前記コアレス基板用プリプレグは、圧力２．５ＭＰａ、温度２４０℃で６０分間プレスして得られる硬化物の弾性率が、２２．３～３５ＧＰａであり、
前記コアレス基板用プリプレグ中における前記熱硬化性樹脂組成物の固形分含有量が、２０～９０質量％である、コアレス基板用プリプレグの製造方法。 A method for producing a prepreg for a coreless substrate, the method comprising applying a resin film (I) containing a thermosetting resin composition to at least one surface of a sheet-like aggregate, the method comprising:
The pasting is carried out under normal pressure by a film pressure welding step in which the resin film (I) is brought into pressure contact with at least one surface of the sheet-like aggregate;
The coreless substrate prepreg has an elastic modulus of a cured product obtained by pressing at a pressure of 2.5 MPa and a temperature of 240° C. for 60 minutes of 22.3 to 35 GPa,
A method for producing a prepreg for a coreless substrate, wherein the solid content of the thermosetting resin composition in the prepreg for a coreless substrate is 20 to 90% by mass.
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| JP2022017484A JP7371710B2 (en) | 2017-03-28 | 2022-02-07 | Prepreg for coreless substrates, method and apparatus for producing prepreg for coreless substrates, coreless substrates and methods for producing the same |
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| JP2017063987A JP7095224B2 (en) | 2017-03-28 | 2017-03-28 | A prepreg for a coreless substrate, a method and an apparatus for manufacturing a prepreg for a coreless substrate, and a coreless substrate and a manufacturing method thereof. |
| JP2022017484A JP7371710B2 (en) | 2017-03-28 | 2022-02-07 | Prepreg for coreless substrates, method and apparatus for producing prepreg for coreless substrates, coreless substrates and methods for producing the same |
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| JP2022017484A Active JP7371710B2 (en) | 2017-03-28 | 2022-02-07 | Prepreg for coreless substrates, method and apparatus for producing prepreg for coreless substrates, coreless substrates and methods for producing the same |
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| JP7400258B2 (en) * | 2019-08-09 | 2023-12-19 | 株式会社レゾナック | FRP precursor manufacturing method, FRP precursor, laminate, multilayer printed wiring board, and semiconductor package |
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| JP2007152573A (en) | 2005-11-30 | 2007-06-21 | Yokohama Rubber Co Ltd:The | Method for producing prepreg and apparatus for method |
| JP2012045887A (en) | 2010-08-30 | 2012-03-08 | Sumitomo Bakelite Co Ltd | Metal clad laminated plate and method for manufacturing the same |
| JP2014017503A (en) | 2007-09-11 | 2014-01-30 | Ajinomoto Co Inc | Multilayer printed wiring board manufacturing method |
| WO2014104328A1 (en) | 2012-12-28 | 2014-07-03 | 日立化成株式会社 | Layered body with support substrate, method for fabricating same, and method for fabricating multi-layer wiring substrate |
| US20140374018A1 (en) | 2012-01-17 | 2014-12-25 | Gurit (Uk) Ltd. | Prepreg for manufacturing composite materials |
| JP2015086253A (en) | 2013-10-29 | 2015-05-07 | 日立化成株式会社 | Thermosetting resin composition, and prepreg, film with resin, laminate, printed wiring board and semiconductor package using the composition |
| WO2015122258A1 (en) | 2014-02-14 | 2015-08-20 | 古河電気工業株式会社 | Carrier-equipped ultrathin copper foil, and copper-clad laminate, printed circuit substrate and coreless substrate that are manufactured using same |
| JP2015200026A (en) | 2014-03-31 | 2015-11-12 | Jx日鉱日石金属株式会社 | Carrier-provided copper foil, printed wiring board, laminate, laminate sheet, electronic equipment and method of producing printed wiring board |
| WO2016178399A1 (en) | 2015-05-01 | 2016-11-10 | 日立化成株式会社 | Method for producing frp precursor and device for producing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2803272B2 (en) * | 1990-01-09 | 1998-09-24 | 東レ株式会社 | Manufacturing method of prepreg |
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| JP2007152573A (en) | 2005-11-30 | 2007-06-21 | Yokohama Rubber Co Ltd:The | Method for producing prepreg and apparatus for method |
| JP2014017503A (en) | 2007-09-11 | 2014-01-30 | Ajinomoto Co Inc | Multilayer printed wiring board manufacturing method |
| JP2012045887A (en) | 2010-08-30 | 2012-03-08 | Sumitomo Bakelite Co Ltd | Metal clad laminated plate and method for manufacturing the same |
| US20140374018A1 (en) | 2012-01-17 | 2014-12-25 | Gurit (Uk) Ltd. | Prepreg for manufacturing composite materials |
| WO2014104328A1 (en) | 2012-12-28 | 2014-07-03 | 日立化成株式会社 | Layered body with support substrate, method for fabricating same, and method for fabricating multi-layer wiring substrate |
| JP2015086253A (en) | 2013-10-29 | 2015-05-07 | 日立化成株式会社 | Thermosetting resin composition, and prepreg, film with resin, laminate, printed wiring board and semiconductor package using the composition |
| WO2015122258A1 (en) | 2014-02-14 | 2015-08-20 | 古河電気工業株式会社 | Carrier-equipped ultrathin copper foil, and copper-clad laminate, printed circuit substrate and coreless substrate that are manufactured using same |
| JP2015200026A (en) | 2014-03-31 | 2015-11-12 | Jx日鉱日石金属株式会社 | Carrier-provided copper foil, printed wiring board, laminate, laminate sheet, electronic equipment and method of producing printed wiring board |
| WO2016178399A1 (en) | 2015-05-01 | 2016-11-10 | 日立化成株式会社 | Method for producing frp precursor and device for producing same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2018165339A (en) | 2018-10-25 |
| JP2022060296A (en) | 2022-04-14 |
| JP7095224B2 (en) | 2022-07-05 |
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