JP2022035328A - Liquid crystal polymer composition, method for producing liquid crystal polymer composition, molding, film, copper-clad laminate, and method for producing molding - Google Patents
Liquid crystal polymer composition, method for producing liquid crystal polymer composition, molding, film, copper-clad laminate, and method for producing molding Download PDFInfo
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- JP2022035328A JP2022035328A JP2020139564A JP2020139564A JP2022035328A JP 2022035328 A JP2022035328 A JP 2022035328A JP 2020139564 A JP2020139564 A JP 2020139564A JP 2020139564 A JP2020139564 A JP 2020139564A JP 2022035328 A JP2022035328 A JP 2022035328A
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Landscapes
- Graft Or Block Polymers (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、グラフト変性ポリオレフィンと架橋剤と液晶ポリマーとを含む液晶ポリマー組成物と、当該液晶ポリマー組成物の製造方法と、当該液晶ポリマー組成物からなる成形品及びフィルムと、当該液晶ポリマー組成物からなるフィルムを含む銅張積層板とに関する。 The present invention comprises a liquid crystal polymer composition containing a graft-modified polyolefin, a cross-linking agent, and a liquid crystal polymer, a method for producing the liquid crystal polymer composition, a molded product and a film comprising the liquid crystal polymer composition, and the liquid crystal polymer composition. It relates to a copper-clad laminate containing a film made of.
近年、スマートフォン等の通信機器や、次世代テレビ等の電子機器において、大容量のデータを高速に送受信することが要求されている。これに伴い、電気信号の高周波数化が進んでいる。具体的には、無線通信分野では、２０２０年頃に、第５世代移動通信システム（５Ｇ）の導入が見込まれる。第５世代移動通信システムの導入に際して、１０ＧＨｚ以上の高周波数帯域の使用が検討されている。 In recent years, communication devices such as smartphones and electronic devices such as next-generation televisions are required to transmit and receive large amounts of data at high speed. Along with this, the frequency of electric signals is increasing. Specifically, in the field of wireless communication, the introduction of the 5th generation mobile communication system (5G) is expected around 2020. When introducing the 5th generation mobile communication system, the use of a high frequency band of 10 GHz or more is being considered.
しかしながら、使用される信号の周波数が高くなるに伴い、情報の誤認識を招きうる出力信号の品質低下、すなわち、伝送損失が大きくなる。この伝送損失は、導体に起因する導体損失と、電子機器や通信機器における基板等の電気電子部品を構成する絶縁用の樹脂に起因する誘電損失とからなるが、導体損失は使用する周波数の０．５乗、誘電損失は周波数の１乗に比例するため、高周波帯、とりわけＧＨｚ帯においては、この誘電損失による影響が非常に大きくなる。 However, as the frequency of the signal used increases, the quality of the output signal, which can lead to misrecognition of information, deteriorates, that is, the transmission loss increases. This transmission loss consists of a conductor loss caused by a conductor and a dielectric loss caused by an insulating resin constituting an electric / electronic component such as a substrate in an electronic device or a communication device. The conductor loss is 0 at the frequency used. Since the fifth power and the dielectric loss are proportional to the first power of the frequency, the influence of this dielectric loss becomes very large in the high frequency band, particularly in the GHz band.
このため、伝送損失を低減するために、誘電損失に係る因子である比誘電率と、誘電正接とが低い低誘電材料が求められている。このような事情から、高周波数帯域で使用される低誘電材料として、例えば、液晶ポリマーの使用が検討されている（特許文献１を参照）。 Therefore, in order to reduce the transmission loss, there is a demand for a low-dielectric material having a low relative permittivity and a dielectric loss tangent, which are factors related to the dielectric loss. Under these circumstances, for example, the use of a liquid crystal polymer as a low-dielectric material used in a high frequency band has been studied (see Patent Document 1).
しかしながら、液晶ポリマー等の低誘電樹脂又はその組成物について、伝送損失のさらなる低減のために、さらなる低誘電特性が求められている。そして、低誘電特性に優れる材料の好ましい用途としては、フレキシブルプリント配線板が挙げられる。フレキシブルプリント配線板において、低誘電特性を有する材料は、通常、フィルム又はシートとして使用される。 However, a low-dielectric resin such as a liquid crystal polymer or a composition thereof is required to have further low-dielectric properties in order to further reduce the transmission loss. A flexible printed wiring board is a preferred use of a material having excellent low dielectric properties. In flexible printed wiring boards, materials with low dielectric properties are usually used as films or sheets.
しかし、液晶ポリマーには、その異方性に起因してフィルム化又はシート化のような溶融加工が困難である問題がある。例えば、液晶ポリマーを、代表的なフィルム製造方法である押出法によりフィルム化する場合、ダイから吐出される溶融した液晶ポリマーが、吐出方向のせん断力による溶融粘度の低下に起因してすぐに垂れてしまい、フィルムの引き取りが困難である。 However, the liquid crystal polymer has a problem that melting processing such as film formation or sheet formation is difficult due to its anisotropy. For example, when a liquid crystal polymer is formed into a film by an extrusion method, which is a typical film manufacturing method, the melted liquid crystal polymer discharged from the die immediately drips due to a decrease in melt viscosity due to a shearing force in the discharge direction. It is difficult to pick up the film.
仮にフィルムを引き取ることができたとしても、フィルムにおける液晶ポリマーの配向に起因して、得られるフィルムは非常に裂けやすい。 Even if the film could be picked up, the resulting film would be very liable to tear due to the orientation of the liquid crystal polymer in the film.
液晶ポリマーが有する優れた低誘電特性を損なうことなく、液晶ポリマーの溶融加工の困難さを解消する方法として、低誘電特性及び溶融加工性に優れるポリオレフィンを液晶ポリマーにブレンドすることが考えられる。 As a method of eliminating the difficulty of melt processing of the liquid crystal polymer without impairing the excellent low dielectric property of the liquid crystal polymer, it is conceivable to blend the polyolefin having excellent low dielectric property and melt processability with the liquid crystal polymer.
しかし、液晶ポリマーとポリオレフィンとは、互いに相溶しにくく、両者を混合して均一な組成物を形成しにくい問題がある。また、液晶ポリマーとポリオレフィンとを均一に混合できても、ポリオレフィンは耐熱性に劣るため、得られた液晶ポリマー組成物も耐熱性に劣る問題がある。 However, there is a problem that the liquid crystal polymer and the polyolefin are difficult to be compatible with each other and it is difficult to mix them to form a uniform composition. Further, even if the liquid crystal polymer and the polyolefin can be uniformly mixed, since the polyolefin is inferior in heat resistance, there is a problem that the obtained liquid crystal polymer composition is also inferior in heat resistance.
フレキシブルプリント配線基板の材料には、通常、鉛フリーはんだに対応するために高い耐熱性が望まれる。フレキシブルプリント配線板は、通常、銅張積層板（ＣＣＬ）であることが多い。フレキシブルプリント配線板の耐熱性は、基板の材料としての樹脂の耐熱性のみでは決まらず、熱膨張による基板の変形や皺の発生、及び加熱による銅膜の剥離の生じにくさ等も考慮して判断される。 The material of the flexible printed wiring board is usually desired to have high heat resistance in order to be compatible with lead-free solder. The flexible printed wiring board is usually a copper-clad laminated board (CCL) in many cases. The heat resistance of the flexible printed wiring board is not determined only by the heat resistance of the resin used as the material of the substrate, but also considers the deformation and wrinkles of the substrate due to thermal expansion, and the difficulty of peeling of the copper film due to heating. Judged.
本発明は、上記の課題に鑑みなされたものであって、低誘電特性、及びフレキシブルプリント配線板用途における耐熱性に優れる成形品を与え、且つ押出法により良好にフィルム化可能である液晶ポリマー組成物と、当該液晶ポリマー組成物の製造方法と、前述の液晶ポリマー組成物からなる成形品と、前述の液晶ポリマー組成物からなるフィルムを含む銅張積層板と、電子線架橋された前述の成形品の製造方法とを提供することを目的とする。 The present invention has been made in view of the above problems, and is a liquid crystal polymer composition that provides a molded product having low dielectric properties and excellent heat resistance in flexible printed wiring board applications, and can be satisfactorily formed into a film by an extrusion method. A product, a method for producing the liquid crystal polymer composition, a molded product made of the above-mentioned liquid crystal polymer composition, a copper-clad laminate containing a film made of the above-mentioned liquid crystal polymer composition, and the above-mentioned molding subjected to electron beam cross-linking. It is an object of the present invention to provide a method for manufacturing an article.
本発明者らは、上記課題を解決するために鋭意検討した結果、本発明を完成するに至った。 As a result of diligent studies to solve the above problems, the present inventors have completed the present invention.
すなわち、本発明は、以下の（１）～（１５）を提供する。
（１）液晶ポリマー（Ａ）と、極性基を有するグラフト変性ポリオレフィン（Ｂ）と、架橋剤（Ｃ）とを含み、
グラフト変性ポリオレフィン（Ｂ）が、モノエンのみを重合したポリオレフィンのグラフト変性物である、液晶ポリマー組成物。
（２）架橋剤（Ｃ）が、トリアリルシアヌレート、トリアリルイソシアヌレート、及びトリメタリルイソシアヌレートからなる群から選ばれる１種以上である、（１）に記載の液晶ポリマー組成物。
（３）架橋剤（Ｃ）の含有量が、グラフト変性ポリオレフィン（Ｂ）１００質量部に対して、１質量部以上１００質量部以下である、（１）又は（２）に記載の液晶ポリマー組成物。
（４）グラフト変性ポリオレフィン（Ｂ）が、グリシジル（メタ）アクリレートと、スチレンとによってグラフト変性されたポリオレフィンである、（１）～（３）のいずれか１つに記載の液晶ポリマー組成物。
（５）グラフト変性ポリオレフィン（Ｂ）の融点が２００℃以上である、（１）～（４）のいずれか１つに記載の液晶ポリマー組成物。
（６）グラフト変性ポリオレフィン（Ｂ）が、ポリメチルペンテンのグラフト変性体である、（１）～（５）のいずれか１つに記載の液晶ポリマー組成物。
（７）液晶ポリマー（Ａ）の融点が２５０℃以上である、（１）～（６）の１つに記載の液晶ポリマー組成物。
（８）液晶ポリマー（Ａ）と、グラフト変性ポリオレフィン（Ｂ）と、架橋剤（Ｃ）とを溶融混錬する、（１）～（７）のいずれか１つに記載の液晶ポリマー組成物の製造方法。
（９）（１）～（７）のいずれか１つに記載の液晶ポリマー組成物からなる成形品。
（１０）架橋剤（Ｃ）による架橋処理が施された、（９）に記載の成形品。
（１１）周波数１０ＧＨｚにおける誘電率が２．８以下であり、周波数１０ＧＨｚにおける誘電正接が、０．００２５以下である、（１０）に記載の成形品。
（１２）フィルムである、（９）～（１１）のいずれか１つに記載の成形品。
（１３）フィルムである（１２）に記載の成形品を含む、銅張積層板。
（１４）（１）～（７）のいずれか１つに記載の液晶ポリマー組成物を成形して成形品を得ることと、
成形品に電子線を照射して、成形品に対して架橋剤（Ｃ）による架橋処理を施すことと、を含む、成形品の製造方法。
（１５）電子線の線量が、１００ｋＧｙ以上１２００ｋＧｙ以下である、（１４）に記載の成形品の製造方法。
That is, the present invention provides the following (1) to (15).
(1) Containing a liquid crystal polymer (A), a graft-modified polyolefin (B) having a polar group, and a cross-linking agent (C).
A liquid crystal polymer composition in which the graft-modified polyolefin (B) is a graft-modified product of a polyolefin obtained by polymerizing only monoene.
(2) The liquid crystal polymer composition according to (1), wherein the cross-linking agent (C) is at least one selected from the group consisting of triallyl cyanurate, triallyl isocyanurate, and trimetalyl isocyanurate.
(3) The liquid crystal polymer composition according to (1) or (2), wherein the content of the cross-linking agent (C) is 1 part by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the graft-modified polyolefin (B). thing.
(4) The liquid crystal polymer composition according to any one of (1) to (3), wherein the graft-modified polyolefin (B) is a polyolefin graft-modified with glycidyl (meth) acrylate and styrene.
(5) The liquid crystal polymer composition according to any one of (1) to (4), wherein the graft-modified polyolefin (B) has a melting point of 200 ° C. or higher.
(6) The liquid crystal polymer composition according to any one of (1) to (5), wherein the graft-modified polyolefin (B) is a graft-modified form of polymethylpentene.
(7) The liquid crystal polymer composition according to one of (1) to (6), wherein the liquid crystal polymer (A) has a melting point of 250 ° C. or higher.
(8) The liquid crystal polymer composition according to any one of (1) to (7), wherein the liquid crystal polymer (A), the graft-modified polyolefin (B), and the cross-linking agent (C) are melt-kneaded. Production method.
(9) A molded product comprising the liquid crystal polymer composition according to any one of (1) to (7).
(10) The molded product according to (9), which has been subjected to a cross-linking treatment with a cross-linking agent (C).
(11) The molded product according to (10), wherein the dielectric constant at a frequency of 10 GHz is 2.8 or less, and the dielectric loss tangent at a frequency of 10 GHz is 0.0025 or less.
(12) The molded product according to any one of (9) to (11), which is a film.
(13) A copper-clad laminate comprising the molded product according to (12), which is a film.
(14) To obtain a molded product by molding the liquid crystal polymer composition according to any one of (1) to (7).
A method for producing a molded product, which comprises irradiating the molded product with an electron beam and subjecting the molded product to a cross-linking treatment with a cross-linking agent (C).
(15) The method for producing a molded product according to (14), wherein the dose of the electron beam is 100 kGy or more and 1200 kGy or less.
本発明によれば、本発明は、上記の課題に鑑みなされたものであって、低誘電特性、及びフレキシブルプリント配線板用途における耐熱性に優れる成形品を与え、且つ押出法により良好にフィルム化可能である液晶ポリマー組成物と、当該液晶ポリマー組成物の製造方法と、前述の液晶ポリマー組成物からなる成形品と、前述の液晶ポリマー組成物からなるフィルムを含む銅張積層板と、電子線架橋された前述の成形品の製造方法とを提供することができる。 According to the present invention, the present invention has been made in view of the above problems, and provides a molded product having low dielectric properties and excellent heat resistance in flexible printed wiring board applications, and is satisfactorily formed into a film by an extrusion method. A possible liquid crystal polymer composition, a method for producing the liquid crystal polymer composition, a molded product made of the above-mentioned liquid crystal polymer composition, a copper-clad laminate containing a film made of the above-mentioned liquid crystal polymer composition, and an electron beam. It is possible to provide the above-mentioned method for producing a crosslinked molded product.
≪液晶ポリマー組成物≫
液晶ポリマー組成物は、液晶ポリマー（Ａ）とともに、極性基を有するグラフト変性ポリオレフィン（Ｂ）、及び架橋剤（Ｃ）を含む。グラフト変性ポリオレフィン（Ｂ）は、モノエンのみを重合したポリオレフィンのグラフト変性物である。
ポリオレフィンがモノエンのみの重合体である、つまりジエン等のポリエンを含まないモノマーの重合体であることによって、グラフト変性時にゲル化のような望まない副反応が生じ難く、液晶ポリマー組成物を用いて均一なフィルムを製膜しやすい。
≪Liquid crystal polymer composition≫
The liquid crystal polymer composition contains a graft-modified polyolefin (B) having a polar group and a cross-linking agent (C) together with the liquid crystal polymer (A). The graft-modified polyolefin (B) is a graft-modified product of a polyolefin obtained by polymerizing only monoene.
Since the polyolefin is a polymer containing only monoene, that is, a polymer of a monomer containing no polyene such as diene, undesired side reactions such as gelation are unlikely to occur during graft modification, and a liquid crystal polymer composition is used. Easy to form a uniform film.
上記の液晶ポリマー組成物は、液晶ポリマー（Ａ）と、グラフト変性ポリオレフィン（Ｂ）との混合比率、液晶ポリマー（Ａ）の融点、グラフト変性ポリオレフィン（Ｂ）の融点、液晶ポリマー（Ａ）の融点とグラフト変性ポリオレフィン（Ｂ）の融点との差、液晶ポリマー（Ａ）と、グラフト変性ポリオレフィン（Ｂ）とを混合する際の温度、グラフト変性ポリオレフィン（Ｂ）の変性率等の様々な条件に応じて、種々の相状態を形成し得る。 The above liquid crystal polymer composition has a mixing ratio of the liquid crystal polymer (A) and the graft-modified polyolefin (B), a melting point of the liquid crystal polymer (A), a melting point of the graft-modified polyolefin (B), and a melting point of the liquid crystal polymer (A). Depending on various conditions such as the difference between the melting point of the graft-modified polyolefin (B) and the melting point of the graft-modified polyolefin (B), the temperature at which the liquid crystal polymer (A) and the graft-modified polyolefin (B) are mixed, and the modification rate of the graft-modified polyolefin (B). Therefore, various phase states can be formed.
液晶ポリマー組成物において、少なくとも一部に、液晶ポリマー（Ａ）と、グラフト変性ポリオレフィン（Ｂ）とからなる海島構造が形成されているのが好ましい。海島構造について、液晶ポリマー（Ａ）と、グラフト変性ポリオレフィン（Ｂ）とのいずれが海成分であってもよい。 In the liquid crystal polymer composition, it is preferable that a sea-island structure composed of the liquid crystal polymer (A) and the graft-modified polyolefin (B) is formed at least in a part thereof. Regarding the sea-island structure, either the liquid crystal polymer (A) or the graft-modified polyolefin (B) may be a sea component.
かかる相状態である場合、液晶ポリマー（Ａ）の性質に由来する異方性が緩和され、液晶ポリマー組成物の溶融加工性が良好である。 In such a phase state, the anisotropy derived from the properties of the liquid crystal polymer (A) is alleviated, and the melt processability of the liquid crystal polymer composition is good.
液晶ポリマー組成物において上記の海島構造が形成されている場合、液晶ポリマー組成物が、液晶ポリマー（Ａ）が海成分である海島構造を含むか、海島構造とともに、液晶ポリマー（Ａ）とグラフト変性ポリオレフィン（Ｂ）とがともに連続相を形成する共連続構造を含むのが好ましい。 When the above-mentioned sea-island structure is formed in the liquid crystal polymer composition, the liquid crystal polymer composition contains a sea-island structure in which the liquid crystal polymer (A) is a sea component, or is graft-modified with the liquid crystal polymer (A) together with the sea-island structure. It preferably contains a co-continuous structure in which the polyolefin (B) forms a continuous phase together.
この場合、液晶ポリマー（Ａ）が、海成分、又は共連続構造における連続相を形成していることによって、液晶ポリマー組成物が液晶ポリマー（Ａ）に由来する優れた耐熱性を発現しやすい。 In this case, since the liquid crystal polymer (A) forms a continuous phase in a sea component or a co-continuous structure, the liquid crystal polymer composition tends to exhibit excellent heat resistance derived from the liquid crystal polymer (A).
極性基を有するグラフト変性ポリオレフィン（Ｂ）、及び架橋剤（Ｃ）と液晶ポリマー（Ａ）とがブレンドされると、液晶ポリマー（Ａ）と、極性基を有するグラフト変性ポリオレフィン（Ｂ）とが、海島構造や、液晶ポリマー（Ａ）とグラフト変性ポリオレフィン（Ｂ）とがともに連続相を形成する共連続構造を容易に形成できる。 When the graft-modified polyolefin (B) having a polar group and the cross-linking agent (C) and the liquid crystal polymer (A) are blended, the liquid crystal polymer (A) and the graft-modified polyolefin (B) having a polar group are formed. It is possible to easily form a sea-island structure or a co-continuous structure in which the liquid crystal polymer (A) and the graft-modified polyolefin (B) both form a continuous phase.
上記の液晶ポリマー組成物は、低誘電特性を活かし、高周波数帯域で使用される電気、電子部品、情報通信装置、当該情報通信装置の部品等の用途において好適に使用される。 The liquid crystal polymer composition described above makes use of its low dielectric property and is suitably used in applications such as electric and electronic parts, information communication devices, and parts of the information communication device used in a high frequency band.
液晶ポリマー組成物の製造方法は特に限定されない。液晶ポリマー組成物は、液晶ポリマー（Ａ）と、グラフト変性ポリオレフィン（Ｂ）と、架橋剤（Ｃ）とを混合することにより製造され得る。 The method for producing the liquid crystal polymer composition is not particularly limited. The liquid crystal polymer composition can be produced by mixing the liquid crystal polymer (A), the graft-modified polyolefin (B), and the cross-linking agent (C).
液晶ポリマー（Ａ）と、グラフト変性ポリオレフィン（Ｂ）及び架橋剤（Ｃ）とを混合する方法は特に限定されない。好ましい混合方法としては、一軸押出機や二軸押出機等の溶融混練装置を用いる方法が挙げられる。性状の異なる複数の樹脂等を一定比率で混合するため、搬送性や混練性に優れた二軸押出機を用いる方法が特に好ましい。 The method of mixing the liquid crystal polymer (A) with the graft-modified polyolefin (B) and the cross-linking agent (C) is not particularly limited. As a preferable mixing method, a method using a melt-kneading device such as a single-screw extruder or a twin-screw extruder can be mentioned. Since a plurality of resins having different properties are mixed at a constant ratio, a method using a twin-screw extruder having excellent transportability and kneading property is particularly preferable.
混合条件は、液晶ポリマー（Ａ）と、グラフト変性ポリオレフィン（Ｂ）と、架橋剤（Ｃ）とを均一に混合でき、液晶ポリマー組成物に含まれる各成分が、過度に熱分解したり、昇華したりしない条件であれば特に限定されない。溶融混練装置を用いる場合、例えば、液晶ポリマー（Ａ）の融点と、グラフト変性ポリオレフィン（Ｂ）の融点とのうちの高い方の融点よりも、好ましくは５℃以上１００℃以下高い温度、より好ましくは１０℃以上５０℃以下高い温度で溶融混練が行われる。 As the mixing conditions, the liquid crystal polymer (A), the graft-modified polyolefin (B), and the cross-linking agent (C) can be uniformly mixed, and each component contained in the liquid crystal polymer composition is excessively thermally decomposed or sublimated. It is not particularly limited as long as it does not do so. When a melt-kneading device is used, for example, a temperature higher than the melting point of the liquid crystal polymer (A) and the melting point of the graft-modified polyolefin (B), preferably 5 ° C. or higher and 100 ° C. or lower, more preferably. Is melt-kneaded at a high temperature of 10 ° C. or higher and 50 ° C. or lower.
液晶ポリマー組成物における、液晶ポリマー（Ａ）の量及びグラフト変性ポリオレフィン（Ｂ）の量は、本発明の目的を阻害しない範囲でそれぞれ特に限定されない。
加工性改良に関する所望する効果を得つつ耐熱性に優れる液晶ポリマー組成物を得やすい点から、グラフト変性ポリオレフィン（Ｂ）の質量は、液晶ポリマー（Ａ）の質量とグラフト変性ポリオレフィン（Ｂ）の質量との合計に対して１０質量％以上７０質量％以下が好ましく、１０質量％以上６０質量％以下が好ましい。
The amount of the liquid crystal polymer (A) and the amount of the graft-modified polyolefin (B) in the liquid crystal polymer composition are not particularly limited as long as they do not impair the object of the present invention.
The mass of the graft-modified polyolefin (B) is the mass of the liquid crystal polymer (A) and the mass of the graft-modified polyolefin (B) from the viewpoint that it is easy to obtain a liquid crystal polymer composition having excellent heat resistance while obtaining a desired effect for improving processability. It is preferably 10% by mass or more and 70% by mass or less, and preferably 10% by mass or more and 60% by mass or less with respect to the total of.
以下、液晶ポリマー組成物が含み得る、必須、又は任意の成分について説明する。 Hereinafter, essential or arbitrary components that may be contained in the liquid crystal polymer composition will be described.
＜グラフト変性ポリオレフィン（Ｂ）＞
グラフト変性ポリオレフィンは、モノエンのみを重合したポリオレフィンがグラフト変性された樹脂であって、極性基を有する樹脂であれば特に限定されない。
<Graft-modified polyolefin (B)>
The graft-modified polyolefin is a resin obtained by graft-modifying a polyolefin obtained by polymerizing only monoene, and is not particularly limited as long as it is a resin having a polar group.
ここで極性基とは、極性のある原子団のことで、この基が有機化合物中に存在すると、その化合物が極性をもつ基のことである。グラフトによりポリオレフィンに導入され得る極性基の具体例としては、アクリル酸、メタクリル酸、マレイン酸、フマル酸、テトラヒドロフタル酸、イタコン酸、シトラコン酸、クロトン酸、及びイソクロトン酸等の不飽和カルボン酸に由来するカルボキシ基；酸無水物、酸ハライド、アミド、イミド、及びエステル等の前述の不飽和カルボン酸の誘導体に由来する酸無水物基、ハロカルボニル基、カルボン酸アミド基、イミド基、及びカルボン酸エステル基；メタクリル酸グリシジル、アクリル酸グリシジル、マレイン酸モノグリシジル、マレイン酸ジグリシジル、イタコン酸モノグリシジル、イタコン酸ジグリシジル、アリルコハク酸モノグリシジル、アリルコハク酸ジグリシジル、ｐ－スチレンカルボン酸グリシジル、アリルグリシジルエーテル、メタクリルグリシジルエーテル、スチレン－ｐ－グリシジルエーテル、ｐ－グリシジルスチレン、３，４－エポキシ－１－ブテン、３，４－エポキシ－３－メチル－１－ブテン、及びビニルシクロヘキセンモノオキシド等のエポキシ基含有ビニル単量体に由来するエポキシ基等が挙げられる。これらの極性基の中では、グラフト変性ポリオレフィン（Ｂ）を液晶ポリマー（Ａ）に配合した場合に、好ましい相状態の液晶ポリマー組成物を得やすいことや、液晶ポリマー組成物を他の材料と接触させて用いる場合に、液晶ポリマー組成物と他の材料との密着性が良好であること等からエポキシ基を含有することが好ましい。 Here, the polar group is a group of polar atoms, and when this group is present in an organic compound, the compound is a group having polarity. Specific examples of polar groups that can be introduced into polyolefins by grafting include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, and isocrotonic acid. Derived carboxy group; acid anhydride group, halocarbonyl group, carboxylic acid amide group, imide group, and carboxylic acid derived from the above-mentioned unsaturated carboxylic acid derivatives such as acid anhydride, acid halide, amide, imide, and ester. Acid ester group; glycidyl methacrylate, glycidyl acrylate, monoglycidyl maleate, diglycidyl maleate, monoglycidyl itaconate, diglycidyl itaconate, monoglycidyl allyl succinate, diglycidyl allyl succinate, glycidyl p-styrene carboxylic acid, allyl glycidyl ether, Contains epoxy groups such as methacrylglycidyl ether, styrene-p-glycidyl ether, p-glycidylstyrene, 3,4-epoxy-1-butene, 3,4-epoxy-3-methyl-1-butene, and vinylcyclohexene monooxide. Examples thereof include an epoxy group derived from a vinyl monomer. Among these polar groups, when the graft-modified polyolefin (B) is blended with the liquid crystal polymer (A), it is easy to obtain a liquid crystal polymer composition in a preferable phase state, and the liquid crystal polymer composition is brought into contact with other materials. It is preferable to contain an epoxy group because the liquid crystal polymer composition has good adhesion to other materials when used in combination.
エポキシ基は、フェノール性水酸基やカルボキシ基等の液晶ポリマー（Ａ）が有する官能基と反応し得る。このため極性基としてエポキシ基を有するグラフト変性ポリオレフィン（Ｂ）を液晶ポリマー（Ａ）に配合すると、液晶ポリマー組成物中において両ポリマーが適度に親和し、例えば、海島構造のような好ましい相構造を容易に形成し得る。 The epoxy group can react with a functional group of the liquid crystal polymer (A) such as a phenolic hydroxyl group or a carboxy group. Therefore, when the graft-modified polyolefin (B) having an epoxy group as a polar group is blended with the liquid crystal polymer (A), both polymers have an appropriate affinity in the liquid crystal polymer composition, and a preferable phase structure such as a sea-island structure is obtained. Can be easily formed.
典型的には、グラフト変性ポリオレフィン（Ｂ）は、ポリオレフィンが、ラジカル重合開始剤の存在下で、極性基を有するビニル単量体でグラフト変性された樹脂である。 Typically, the graft-modified polyolefin (B) is a resin in which the polyolefin is graft-modified with a vinyl monomer having a polar group in the presence of a radical polymerization initiator.
グラフト変性ポリオレフィン（Ｂ）は、極性基を有するビニル単量体、及び芳香族ビニル単量体によりグラフト変性されたポリオレフィンであるのが好ましく、グリシジル（メタ）アクリレートと、スチレンとによってグラフト変性されたポリオレフィンであるのがより好ましい。 The graft-modified polyolefin (B) is preferably a polyolefin graft-modified with a vinyl monomer having a polar group and an aromatic vinyl monomer, and is graft-modified with glycidyl (meth) acrylate and styrene. More preferably, it is a polyolefin.
ポリオレフィンとしては、例えば、ポリエチレン、ポリプロピレン、ポリ－１－ブテン、ポリイソブチレン、ポリメチルペンテン、プロピレン－エチレン共重合体、エチレン／ブテン－１共重合体、及びエチレン／オクテン共重合体等の鎖状ポリオレフィンが挙げられる。 Examples of the polyolefin include chains such as polyethylene, polypropylene, poly-1-butene, polyisobutylene, polymethylpentene, propylene-ethylene copolymer, ethylene / butene-1 copolymer, and ethylene / octene copolymer. Polyolefins can be mentioned.
これらのポリオレフィンの中でも、変性反応が容易であることから、ポリメチルペンテン、ポリエチレン、ポリプロピレン、及びプロピレン－エチレン共重合体が好ましく、耐熱性及び低誘電特性の点から、ポリメチルペンテンがより好ましい。 Among these polyolefins, polymethylpentene, polyethylene, polypropylene, and propylene-ethylene copolymers are preferable because the modification reaction is easy, and polymethylpentene is more preferable from the viewpoint of heat resistance and low dielectric properties.
ポリオレフィンをグラフト変性する際に使用し得るラジカル重合開始剤としては、例えば、メチルエチルケトンパーオキサイド、及びメチルアセトアセテートパーオキサイド等のケトンパーオキサイド；１，１－ビス（ｔｅｒｔ－ブチルパーオキシ）－３，３，５－トリメチルシクロヘキサン、１，１－ビス（ｔｅｒｔ－ブチルパーオキシ）シクロヘキサン、ｎ－ブチル－４，４－ビス（ｔｅｒｔ－ブチルパーオキシ）バレレート、及び２，２－ビス（ｔｅｒｔ－ブチルパーオキシ）ブタン等のパーオキシケタール；パーメタンハイドロパーオキサイド、１，１，３，３－テトラメチルブチルハイドロパーオキサイド、ジイソプロピルベンゼンハイドロパーオキサイド、及びクメンハイドロパーオキサイド等のハイドロパーオキサイド；ジクミルパーオキサイド、２，５－ジメチル－２，５－ジ（ｔｅｒｔ－ブチルパーオキシ）ヘキサン、α，α’－ビス（ｔｅｒｔ－ブチルパーオキシ－ｍ－イソプロピル）ベンゼン、ｔｅｒｔ－ブチルクミルパーオキサイド、ジ－ｔｅｒｔ－ブチルパーオキサイド、及び２，５－ジメチル－２，５－ジ（ｔｅｒｔ－ブチルパーオキシ）ヘキシン－３等のジアルキルパーオキサイド；ベンゾイルパーオキサイド等のジアシルパーオキサイド；ジ（３－メチル－３－メトキシブチル）パーオキシジカーボネート、及びジ－２－メトキシブチルパーオキシジカーボネート等のパーオキシジカーボネート、ｔｅｒｔ－ブチルパーオキシオクテート、ｔｅｒｔ－ブチルパーオキシイソブチレート、ｔｅｒｔ－ブチルパーオキシラウレート、ｔｅｒｔ－ブチルパーオキシ－３，５，５－トリメチルヘキサノエート、ｔｅｒｔ－ブチルパーオキシイソプロピルカーボネート、２，５－ジメチル－２，５－ジ（ベンゾイルパーオキシ）ヘキサン、ｔｅｒｔ－ブチルパーオキシアセテート、ｔｅｒｔ－ブチルパーオキシベンゾエート、及びジ－ｔｅｒｔ－ブチルパーオキシイソフタレート等のパーオキシエステル等が挙げられる。上記のラジカル重合開始剤は、単独又は２種以上を混合して用いることができる。 Examples of radical polymerization initiators that can be used for graft modification of polyolefins include ketone peroxides such as methyl ethyl ketone peroxide and methyl acetoacetate peroxide; 1,1-bis (tert-butylperoxy) -3, 3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, and 2,2-bis (tert-butylperoxy). Oxy) Peroxyketal such as butane; hydroperoxides such as permethanehydroperoxide, 1,1,3,3-tetramethylbutylhydroperoxide, diisopropylbenzenehydroperoxide, and cumenehydroperoxide; dicumylper Oxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, α, α'-bis (tert-butylperoxy-m-isopropyl) benzene, tert-butylcumyl peroxide, di- Dialkyl peroxides such as tert-butyl peroxide and 2,5-dimethyl-2,5-di (tert-butylperoxy) hexin-3; diacyl peroxides such as benzoyl peroxide; di (3-methyl-3). -Methoxybutyl) peroxydicarbonate and peroxydicarbonate such as di-2-methoxybutylperoxydicarbonate, tert-butylperoxyoctate, tert-butylperoxyisobutyrate, tert-butylperoxylau Rate, tert-butylperoxy-3,5,5-trimethylhexanoate, tert-butylperoxyisopropyl carbonate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, tert-butylperoxy Examples thereof include peroxy esters such as acetate, tert-butyl peroxybenzoate, and di-tert-butyl peroxyisophthalate. The above radical polymerization initiator may be used alone or in combination of two or more.
ラジカル重合開始剤の使用量は、グラフト変性反応が良好に進行する限り特に限定されない。ラジカル重合開始剤の使用量は、ポリオレフィン１００質量部に対して、０．０１質量部以上１０質量部以下が好ましく、０．２質量部以上５質量部以下がより好ましい。 The amount of the radical polymerization initiator used is not particularly limited as long as the graft modification reaction proceeds well. The amount of the radical polymerization initiator used is preferably 0.01 parts by mass or more and 10 parts by mass or less, and more preferably 0.2 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the polyolefin.
グラフト変性に使用され得る極性基を有するビニル単量体としては、アクリル酸、メタクリル酸、マレイン酸、フマル酸、テトラヒドロフタル酸、イタコン酸、シトラコン酸、クロトン酸、及びイソクロトン酸等の不飽和カルボン酸；酸無水物、酸ハライド、アミド、イミド、及びエステル等のこれらの不飽和カルボン酸の誘導体；メタクリル酸グリシジル、アクリル酸グリシジル、マレイン酸モノグリシジル、マレイン酸ジグリシジル、イタコン酸モノグリシジル、イタコン酸ジグリシジル、アリルコハク酸モノグリシジル、アリルコハク酸ジグリシジル、ｐ－スチレンカルボン酸グリシジル、アリルグリシジルエーテル、メタクリルグリシジルエーテル、スチレン－ｐ－グリシジルエーテル、ｐ－グリシジルスチレン、３，４－エポキシ－１－ブテン、３，４－エポキシ－３－メチル－１－ブテン、及びビニルシクロヘキセンモノオキシド等のエポキシ基含有ビニル単量体が挙げられる。 The vinyl monomer having a polar group that can be used for graft modification includes unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, and isocrotonic acid. Acids; Derivatives of these unsaturated carboxylic acids such as acid anhydrides, acid halides, amides, imides, and esters; glycidyl methacrylate, glycidyl acrylate, monoglycidyl maleate, diglycidyl maleate, monoglycidyl itaconate, itaconic acid. Diglycidyl, monoglycidyl allyl succinate, diglycidyl allyl succinate, p-styrene carboxylic acid glycidyl, allyl glycidyl ether, methacryl glycidyl ether, styrene-p-glycidyl ether, p-glycidyl styrene, 3,4-epoxy-1-butene, 3, Examples thereof include epoxy group-containing vinyl monomers such as 4-epoxy-3-methyl-1-butene and vinylcyclohexene monooxide.
これらの中でも、エポキシ基含有ビニル単量体が好ましく、メタクリル酸グリシジル、アクリル酸グリシジルがより好ましく、メタクリル酸グリシジルが特に好ましい。 Among these, an epoxy group-containing vinyl monomer is preferable, glycidyl methacrylate and glycidyl acrylate are more preferable, and glycidyl methacrylate is particularly preferable.
上記の極性基を有するビニル単量体は、単独又は２種以上を混合して用いることができる。 The above-mentioned vinyl monomer having a polar group can be used alone or in combination of two or more.
ポリオレフィンのグラフト変性に使用される極性基を有するビニル単量体の添加量は、ポリオレフィン１００質量部に対して、０．１質量部以上１２質量部以下が好ましく、０．５質量部以上１０質量部以下がより好ましく、１質量部以上８質量部以下が特に好ましい。 The amount of the vinyl monomer having a polar group used for the graft modification of the polyolefin is preferably 0.1 part by mass or more and 12 parts by mass or less, and 0.5 parts by mass or more and 10 parts by mass with respect to 100 parts by mass of the polyolefin. It is more preferably 1 part by mass or less, and particularly preferably 1 part by mass or more and 8 parts by mass or less.
かかる範囲内の量の極性基を有するビニル単量体を用いて変性されたポリオレフィンを用いることで、グラフト変性ポリオレフィン（Ｂ）を液晶ポリマー（Ａ）に配合した場合に、好ましい相状態であり、所望する低誘電特性を示す液晶ポリマー組成物を得やすい。 By using a polyolefin modified with a vinyl monomer having a polar group in an amount within such a range, a preferred phase state is obtained when the graft-modified polyolefin (B) is blended with the liquid crystal polymer (A). It is easy to obtain a liquid crystal polymer composition exhibiting desired low dielectric properties.
前述の通りグラフト変性ポリオレフィン（Ｂ）は、極性基を有するビニル単量体、及び芳香族ビニル単量体によりグラフト変性されたポリオレフィンであるのが好ましい。 As described above, the graft-modified polyolefin (B) is preferably a vinyl monomer having a polar group and a polyolefin graft-modified with an aromatic vinyl monomer.
極性基を有するビニル単量体と、芳香族ビニル単量体とを併用することにより、グラフト反応が安定化することによって、極性基を有するビニル単量体を所望する量グラフトさせやすいためである。 This is because the combined use of the vinyl monomer having a polar group and the aromatic vinyl monomer stabilizes the graft reaction, so that the vinyl monomer having a polar group can be easily grafted in a desired amount. ..
芳香族ビニル単量体の具体例としては、スチレン；ｏ－メチルスチレン、ｍ－メチルスチレン、ｐ－メチルスチレン、α－メチルスチレン、β－メチルスチレン、ジメチルスチレン、及びトリメチルスチレン等のアルキルスチレン類；ｏ－クロロスチレン、ｍ－クロロスチレン、ｐ－クロロスチレン、α－クロロスチレン、β－クロロスチレン、ジクロロスチレン、及びトリクロロスチレン等のクロロスチレン類；ｏ－ブロモスチレン、ｍ－ブロモスチレン、ｐ－ブロモスチレン、ジブロモスチレン、及びトリブロモスチレン等のブロモスチレン類；ｏ－フルオロスチレン、ｍ－フルオロスチレン、ｐ－フルオロスチレン、ジフルオロスチレン、及びトリフルオロスチレン等のフルオロスチレン類；ｏ－ニトロスチレン、ｍ－ニトロスチレン、ｐ－ニトロスチレン、ジニトロスチレン、及びトリニトロスチレン等のニトロスチレン類；ｏ－ヒドロキシスチレン、ｍ－ヒドロキシスチレン、ｐ－ヒドロキシスチレン、ジヒドロキシスチレン、及びトリヒドロキシスチレン等のヒドロキシスチレン類；ｏ－ジビニルベンゼン、ｍ－ジビニルベンゼン、ｐ－ジビニルベンゼン、ｏ－ジイソプロペニルベンゼン、ｍ－ジイソプロペニルベンゼン、及びｐ－ジイソプロペニルベンゼン等のジアルケニルベンゼン類等が挙げられる。 Specific examples of aromatic vinyl monomers include styrene; alkyl styrenes such as o-methyl styrene, m-methyl styrene, p-methyl styrene, α-methyl styrene, β-methyl styrene, dimethyl styrene, and trimethyl styrene. Chlorostyrenes such as o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, α-chlorostyrene, β-chlorostyrene, dichlorostyrene, and trichlorostyrene; o-bromostyrene, m-bromostyrene, p- Bromostyrenes such as bromostyrene, dibromostyrene, and tribromostyrene; fluorostyrenes such as o-fluorostyrene, m-fluorostyrene, p-fluorostyrene, difluorostyrene, and trifluorostyrene; o-nitrostyrene, m. -Nitrostyrenes such as nitrostyrene, p-nitrostyrene, dinitrostyrene, and trinitrostyrene; hydroxystyrenes such as o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, dihydroxystyrene, and trihydroxystyrene; Examples thereof include dialkenylbenzenes such as o-divinylbenzene, m-divinylbenzene, p-divinylbenzene, o-diisopropenylbenzene, m-diisopropenylbenzene, and p-diisopropenylbenzene.
これら芳香族ビニル単量体の中でも、スチレン、α－メチルスチレン、ｐ－メチルスチレン、ｏ－ジビニルベンゼン、ｍ－ジビニルベンゼン、ｐ－ジビニルベンゼン、又はジビニルベンゼン異性体混合物が、安価な点で好ましく、特にスチレンが好ましい。 Among these aromatic vinyl monomers, styrene, α-methylstyrene, p-methylstyrene, o-divinylbenzene, m-divinylbenzene, p-divinylbenzene, or a mixture of divinylbenzene isomers is preferable in terms of low cost. , Especially styrene is preferable.
芳香族ビニル単量体は、単独又は２種以上を混合して用いることができる。 The aromatic vinyl monomer can be used alone or in combination of two or more.
ポリオレフィンのグラフト変性に使用される極性基を有する芳香族ビニル単量体の量は、ポリオレフィン１００質量部に対して、０．１質量部以上１２質量部以下が好ましく、０．５質量部以上１０質量部以下がより好ましく、１質量部以上８質量部以下が特に好ましい。 The amount of the aromatic vinyl monomer having a polar group used for the graft modification of the polyolefin is preferably 0.1 part by mass or more and 12 parts by mass or less, and 0.5 parts by mass or more and 10 parts by mass with respect to 100 parts by mass of the polyolefin. It is more preferably 1 part by mass or less, and particularly preferably 1 part by mass or more and 8 parts by mass or less.
グラフト変性ポリオレフィン（Ｂ）の融点は、特に限定されない。グラフト変性ポリオレフィン（Ｂ）の融点は、８０℃以上が好ましく、１００℃以上がより好ましく、１２０℃以上２４０℃以下がさらに好ましい。
成形品の耐熱性の点から、グラフト変性ポリメチルペンテン（Ｂ）の融点は、２００℃以上であるのもの好ましい。
グラフト変性ポリオレフィン（Ｂ）の融点が、上記の温度であることにより、グラフト変性ポリオレフィン組成物、及び後述する液晶ポリマー組成物からなる成形品に良好な耐熱性を付与できる。
また、グラフト変性ポリオレフィン（Ｂ）の融点が２４０℃以下であると、液晶ポリマー組成物を調製したり使用したりする際の、架橋剤（Ｃ）の分解や昇華を抑制しやすい。
The melting point of the graft-modified polyolefin (B) is not particularly limited. The melting point of the graft-modified polyolefin (B) is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and even more preferably 120 ° C. or higher and 240 ° C. or lower.
From the viewpoint of heat resistance of the molded product, the melting point of the graft-modified polymethylpentene (B) is preferably 200 ° C. or higher.
When the melting point of the graft-modified polyolefin (B) is the above temperature, good heat resistance can be imparted to the molded product composed of the graft-modified polyolefin composition and the liquid crystal polymer composition described later.
Further, when the melting point of the graft-modified polyolefin (B) is 240 ° C. or lower, it is easy to suppress the decomposition and sublimation of the cross-linking agent (C) when preparing or using the liquid crystal polymer composition.
＜架橋剤（Ｃ）＞
液晶ポリマー組成物は、架橋剤（Ｃ）を含む。架橋剤（Ｃ）は、グラフト変性ポリオレフィン（Ｂ）と液晶ポリマー（Ａ）とがブレンドされた際の、液晶ポリマー組成物の耐熱性や機械的特性の向上に寄与する。
<Crosslinking agent (C)>
The liquid crystal polymer composition contains a cross-linking agent (C). The cross-linking agent (C) contributes to the improvement of heat resistance and mechanical properties of the liquid crystal polymer composition when the graft-modified polyolefin (B) and the liquid crystal polymer (A) are blended.
架橋剤（Ｃ）が有する後述の反応性官能基の種類に応じて選択される、加熱や電子線照射等の架橋処理によって、架橋剤（Ｃ）は、液晶ポリマー（Ａ）同士、グラフト変性ポリオレフィン（Ｂ）同士、又は液晶ポリマー（Ａ）とグラフト変性ポリオレフィン（Ｂ）とを架橋させる。 By cross-linking treatment such as heating or electron beam irradiation, which is selected according to the type of the reactive functional group described below of the cross-linking agent (C), the cross-linking agent (C) is a graft-modified polyolefin between the liquid crystal polymers (A). Crosslink between (B) or between the liquid crystal polymer (A) and the graft-modified polyolefin (B).
架橋剤（Ｃ）は、同一分子内に反応性官能基を２個以上有する化合物である。液晶ポリマー組成物からなる成形品において、架橋剤（Ｃ）による分子架橋を生じさせることにより特に耐熱性に優れる成形品を得やすい。 The cross-linking agent (C) is a compound having two or more reactive functional groups in the same molecule. In a molded product made of a liquid crystal polymer composition, it is easy to obtain a molded product having particularly excellent heat resistance by causing molecular cross-linking with the cross-linking agent (C).
架橋剤（Ｃ）が有する反応性官能基としては炭素－炭素二重結合含有基、ハロゲン原子、ジカルボン酸無水物基、カルボキシ基、アミノ基、シアノ基、及び水酸基が挙げられる。架橋剤の同一分子内に有する複数の反応性官能基は互いに同じであってもよく、異なっていてもよい。
上記の反応性官能基の中では、架橋反応性と、架橋後の架橋構造の安定性とが優れることから、炭素－炭素二重結合含有基が好ましい。
炭素－炭素二重結合含有基としては、ビニル基、アリル基、及びメタリル基等のアルケニル基、アクリロイル基、メタクリロイル基等の不飽和アシル基、マレイミド基等が挙げられる。好ましい炭素－炭素二重結合含有基は炭素数２～４のアルケニル基であり、特にアリル基が特に好ましい。
Examples of the reactive functional group of the cross-linking agent (C) include a carbon-carbon double bond-containing group, a halogen atom, a dicarboxylic acid anhydride group, a carboxy group, an amino group, a cyano group, and a hydroxyl group. The plurality of reactive functional groups contained in the same molecule of the cross-linking agent may be the same or different from each other.
Among the above-mentioned reactive functional groups, a carbon-carbon double bond-containing group is preferable because the cross-linking reactivity and the stability of the cross-linked structure after cross-linking are excellent.
Examples of the carbon-carbon double bond-containing group include an alkenyl group such as a vinyl group, an allyl group and a metallicyl group, an unsaturated acyl group such as an acryloyl group and a methacryloyl group, and a maleimide group. A preferred carbon-carbon double bond-containing group is an alkenyl group having 2 to 4 carbon atoms, and an allyl group is particularly preferable.
架橋剤（Ｃ）の好適な具体例としては、トリアリルシアヌレート、トリアリルイソシアヌレート、トリメタリルイソシアヌレート、トリメチロールプロパントリ（メタ）アクリレート、１，３，５－トリアクリロイルヘキサヒドロ－１，３，５－トリアジン、トリアリルトリメリテート、ｍ－フェニレンジアミンビスマレイミド、ｐ－キノンジオキシム、ｐ，ｐ’－ジベンゾイルキノンジオキシム、ジプロパルギルテレフタレート、ジアリルフタレート、Ｎ，Ｎ’，Ｎ’’，Ｎ’’’－テトラアリルテレフタルアミド、並びにポリメチルビニルシロキサン、及びポリメチルフェニルビニルシロキサン等のビニル基含有ポリシロキサン等が挙げられる。 Suitable specific examples of the cross-linking agent (C) include triallyl cyanurate, triallyl isocyanurate, trimetalyl isocyanurate, trimethylolpropanetri (meth) acrylate, 1,3,5-triacrylloylhexahydro-1, 3,5-triazine, triallyl trimerinate, m-phenylenediamine bismaleimide, p-quinonedioxime, p, p'-dibenzoylquinonedioxime, dipropargyl terephthalate, diallylphthalate, N, N', N' Examples thereof include', N'''-tetraallyl terephthalamide, and vinyl group-containing polysiloxanes such as polymethylvinylsiloxane and polymethylphenylvinylsiloxane.
これらの中では、トリアリルシアヌレート、トリアリルイソシアヌレート、トリメタリルイソシアヌレート、及びトリメチロールプロパントリ（メタ）アクリレートからなる群より選ばれる１種以上がより好ましい。特に架橋反応性の点で、架橋剤（Ｃ）がトリアリルイソシアヌレート（ＴＡＩＣ）、及び／又はトリメチロールプロパントリ（メタ）アクリレート（ＴＭＰＴＭＡ）を含むのが好ましく、架橋剤（Ｃ）がＴＡＩＣであるのが特に好ましい。 Among these, one or more selected from the group consisting of triallyl cyanurate, triallyl isocyanurate, trimetalyl isocyanurate, and trimethylolpropane tri (meth) acrylate is more preferable. Particularly in terms of cross-linking reactivity, the cross-linking agent (C) preferably contains triallyl isocyanurate (TAIC) and / or trimethylolpropane tri (meth) acrylate (TMPTMA), and the cross-linking agent (C) is TAIC. It is particularly preferable to have it.
架橋剤（Ｃ）の使用量は、本発明の目的を阻害しない範囲で特に限定されない。架橋剤（Ｃ）の使用量は、液晶ポリマー組成物の組成を勘案して適宜決定できる。 The amount of the cross-linking agent (C) used is not particularly limited as long as it does not impair the object of the present invention. The amount of the cross-linking agent (C) used can be appropriately determined in consideration of the composition of the liquid crystal polymer composition.
グラフト変性ポリオレフィン組成物における、架橋剤（Ｃ）の使用量は、例えば、グラフト変性ポリオレフィン１００質量部に対して、１質量部以上１００質量部以下が好ましく、５質量部以上８０質量部以下がより好ましく、１０質量部以上５０質量部以下がさらに好ましい。 The amount of the cross-linking agent (C) used in the graft-modified polyolefin composition is, for example, preferably 1 part by mass or more and 100 parts by mass or less, and more preferably 5 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the graft-modified polyolefin. It is preferable, and more preferably 10 parts by mass or more and 50 parts by mass or less.
＜液晶ポリマー（Ａ）＞
液晶ポリマー（Ａ）は、溶融時に光学的異方性を示すポリマーであって、当業者にサーモトロピック液晶ポリマーと認識されているポリマーを特に制限なく用いることができる。溶融時の光学的異方性は、直交偏光子を利用した慣用の偏光検査方法により確認することができる。
<Liquid crystal polymer (A)>
The liquid crystal polymer (A) is a polymer that exhibits optical anisotropy when melted, and a polymer recognized by those skilled in the art as a thermotropic liquid crystal polymer can be used without particular limitation. The optical anisotropy at the time of melting can be confirmed by a conventional polarization inspection method using an orthogonal polarizing element.
液晶ポリマー（Ａ）は、典型的にはフェノール性水酸基を有するモノマーのアシル化物を含むモノマー混合物を重縮合することにより製造される。重縮合は、触媒の存在下に行われるのが好ましい。触媒の例としては、酢酸マグネシウム、酢酸第一錫、テトラブチルチタネート、酢酸鉛、酢酸ナトリウム、酢酸カリウム、三酸化アンチモン等の金属化合物や、１－メチルイミダゾール等の含窒素複素環式化合物が挙げられる。 The liquid crystal polymer (A) is typically produced by polycondensing a monomer mixture containing an acylated product of a monomer having a phenolic hydroxyl group. The polycondensation is preferably carried out in the presence of a catalyst. Examples of the catalyst include metal compounds such as magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate and antimony trioxide, and nitrogen-containing heterocyclic compounds such as 1-methylimidazole. Be done.
触媒の使用量は、例えば、モノマー混合物の量１００質量部に対し、０．１質量部以下が好ましい。 The amount of the catalyst used is, for example, preferably 0.1 part by mass or less with respect to 100 parts by mass of the amount of the monomer mixture.
前述の通り、モノマー混合物は、フェノール性水酸基を有するモノマーのアシル化物を含むモノマーの混合物である。モノマー混合物は、テレフタル酸やイソフタル酸に代表される芳香族ジカルボン酸等のフェノール性水酸基を持たないモノマーを含んでいてもよい。 As described above, the monomer mixture is a mixture of monomers containing an acylated product of a monomer having a phenolic hydroxyl group. The monomer mixture may contain a monomer having no phenolic hydroxyl group such as an aromatic dicarboxylic acid typified by terephthalic acid or isophthalic acid.
モノマー混合物の調製方法としては、コストや製造時間の点で、フェノール性水酸基を有するモノマーを含むモノマー混合物をアシル化して、フェノール性水酸基を有するモノマーのアシル化物を含むモノマー混合物を得る方法が好ましい。 As a method for preparing a monomer mixture, a method of acylating a monomer mixture containing a monomer having a phenolic hydroxyl group to obtain a monomer mixture containing an acylated product of a monomer having a phenolic hydroxyl group is preferable in terms of cost and production time.
液晶ポリマー（Ａ）を構成する構成単位としては、芳香族オキシカルボニル単位、芳香族ジカルボニル単位、芳香族ジオキシ単位、芳香族アミノオキシ単位、芳香族ジアミノ単位、芳香族アミノカルボニル単位、及び脂肪族ジオキシ単位等が挙げられる。 The constituent units constituting the liquid crystal polymer (A) include an aromatic oxycarbonyl unit, an aromatic dicarbonyl unit, an aromatic dioxy unit, an aromatic aminooxy unit, an aromatic diamino unit, an aromatic aminocarbonyl unit, and an aliphatic. Examples include dioxy units.
なお、液晶ポリマー（Ａ）は、エステル結合以外の結合として、アミド結合やチオエステル結合を含んでいてもよい。 The liquid crystal polymer (A) may contain an amide bond or a thioester bond as a bond other than the ester bond.
芳香族オキシカルボニル単位は、芳香族ヒドロキシカルボン酸に由来する単位である。 The aromatic oxycarbonyl unit is a unit derived from an aromatic hydroxycarboxylic acid.
芳香族ヒドロキシカルボン酸の好適な具体例としては、ｐ－ヒドロキシ安息香酸、ｍ－ヒドロキシ安息香酸、ｏ－ヒドロキシ安息香酸、６－ヒドロキシ－２－ナフトエ酸、５－ヒドロキシ－２－ナフトエ酸、３－ヒドロキシ－２－ナフトエ酸、４’－ヒドロキシフェニル－４－安息香酸、３’－ヒドロキシフェニル－４－安息香酸、４’－ヒドロキシフェニル－３－安息香酸、これらのアルキル、アルコキシ又はハロゲン置換体が挙げられる。 Suitable specific examples of aromatic hydroxycarboxylic acids include p-hydroxybenzoic acid, m-hydroxybenzoic acid, o-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 5-hydroxy-2-naphthoic acid, 3 -Hydroxy-2-naphthoic acid, 4'-hydroxyphenyl-4-benzoic acid, 3'-hydroxyphenyl-4-benzoic acid, 4'-hydroxyphenyl-3-benzoic acid, alkyl, alkoxy or halogen substituents thereof. Can be mentioned.
芳香ヒドロキシカルボン酸のエステル誘導体、酸ハロゲン化物等のエステル形成性誘導体も、芳香族ヒドロキシカルボン酸と同様に好適に使用できる。 Ester derivatives of aromatic hydroxycarboxylic acids, ester-forming derivatives such as acid halides can also be suitably used in the same manner as aromatic hydroxycarboxylic acids.
得られる液晶ポリマー（Ａ）の機械的特性や融点を調製しやすいことから、これらの芳香族ヒドロキシカルボン酸の中では、ｐ－ヒドロキシ安息香酸、及び６－ヒドロキシ－２－ナフトエ酸が好ましい。 Among these aromatic hydroxycarboxylic acids, p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid are preferable because the mechanical properties and melting point of the obtained liquid crystal polymer (A) can be easily prepared.
芳香族ジカルボニル繰返し単位は、芳香族ジカルボン酸に由来する単位である。 The aromatic dicarbonyl repeating unit is a unit derived from an aromatic dicarboxylic acid.
芳香族ジカルボン酸の好適な具体例としては、テレフタル酸、イソフタル酸、２，６－ナフタレンジカルボン酸、１，６－ナフタレンジカルボン酸、２，７－ナフタレンジカルボン酸、１，４－ナフタレンジカルボン酸、及び４，４’－ジカルボキシビフェニル等の芳香族ジカルボン酸、これらのアルキル、アルコキシ又はハロゲン置換体が挙げられる。 Suitable specific examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, and the like. And aromatic dicarboxylic acids such as 4,4'-dicarboxybiphenyl, alkyl, alkoxy or halogen substituents thereof.
芳香族ジカルボン酸のエステル誘導体、酸ハロゲン化物等のエステル形成性誘導体も、芳香族ジカルボン酸と同様に好適に使用できる。 Ester-forming derivatives such as an ester derivative of an aromatic dicarboxylic acid and an acid halide can also be preferably used in the same manner as the aromatic dicarboxylic acid.
得られる液晶ポリマー（Ａ）の機械物性、耐熱性、融点温度、成形性を適度なレベルに調整しやすいことから、これらの芳香族ジカルボン酸中ではテレフタル酸、及び２，６－ナフタレンジカルボン酸が好ましい。 Among these aromatic dicarboxylic acids, terephthalic acid and 2,6-naphthalenedicarboxylic acid are included because it is easy to adjust the mechanical properties, heat resistance, melting point temperature, and moldability of the obtained liquid crystal polymer (A) to appropriate levels. preferable.
芳香族ジオキシ繰返し単位は、芳香族ジオールに由来する単位である。 The aromatic dioxy repeating unit is a unit derived from an aromatic diol.
芳香族ジオールの好適な具体例としては、ハイドロキノン、レゾルシン、２，６－ジヒドロキシナフタレン、２，７－ジヒドロキシナフタレン、１，６－ジヒドロキシナフタレン、１，４－ジヒドロキシナフタレン、４，４’－ジヒドロキシビフェニル、３，３’－ジヒドロキシビフェニル、３，４’－ジヒドロキシビフェニル、４，４’－ジヒドロキシビフェニルエーテル、これらのアルキル、アルコキシ又はハロゲン置換体等が挙げられる。 Suitable specific examples of aromatic diols include hydroquinone, resorcin, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, and 4,4'-dihydroxybiphenyl. , 3,3'-Dihydroxybiphenyl, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl ether, alkyl, alkoxy or halogen substituents thereof and the like.
重縮合時の反応性、及び得られる液晶ポリマー（Ａ）の特性等の点から、これらの芳香族ジオールの中ではハイドロキノン、レゾルシン、及び４，４’－ジヒドロキシビフェニルが好ましい。 Among these aromatic diols, hydroquinone, resorcin, and 4,4'-dihydroxybiphenyl are preferable from the viewpoint of reactivity at the time of polycondensation and the characteristics of the obtained liquid crystal polymer (A).
芳香族アミノオキシ単位は、芳香族ヒドロキシアミンに由来する単位である。 Aromatic aminooxy units are units derived from aromatic hydroxyamines.
芳香族ヒドロキシアミンの好適な具体例としては、ｐ－アミノフェノール、ｍ－アミノフェノール、４－アミノ－１－ナフトール、５－アミノ－１－ナフトール、８－アミノ－２－ナフトール、４－アミノ－４’－ヒドロキシビフェニル等の芳香族ヒドロキシアミン、これらのアルキル、アルコキシ又はハロゲン置換体等が挙げられる。 Suitable specific examples of aromatic hydroxyamines are p-aminophenol, m-aminophenol, 4-amino-1-naphthol, 5-amino-1-naphthol, 8-amino-2-naphthol, 4-amino-. Aromatic hydroxyamines such as 4'-hydroxybiphenyl, alkyl, alkoxy or halogen substituents thereof and the like can be mentioned.
芳香族ジアミノ単位は、芳香族ジアミンに由来する単位である。 Aromatic diamino units are units derived from aromatic diamines.
芳香族ジアミンの好適な具体例としては、ｐ－フェニレンジアミン、ｍ－フェニレンジアミン、１，５－ジアミノナフタレン、１，８－ジアミノナフタレン等の芳香族ジアミン、これらのアルキル、アルコキシ又はハロゲン置換体が挙げられる。 Suitable specific examples of aromatic diamines include aromatic diamines such as p-phenylenediamine, m-phenylenediamine, 1,5-diaminonaphthalene and 1,8-diaminonaphthalene, and alkyl, alkoxy or halogen substituents thereof. Can be mentioned.
芳香族アミノカルボニル単位は、芳香族アミノカルボン酸に由来する単位である。 The aromatic aminocarbonyl unit is a unit derived from an aromatic aminocarboxylic acid.
芳香族アミノカルボン酸の好適な具体例としては、ｐ－アミノ安息香酸、ｍ－アミノ安息香酸、６－アミノ－２－ナフトエ酸等の芳香族アミノカルボン酸、これらのアルキル、アルコキシ又はハロゲン置換体が挙げられる。 Suitable specific examples of aromatic aminocarboxylic acids include aromatic aminocarboxylic acids such as p-aminobenzoic acid, m-aminobenzoic acid, 6-amino-2-naphthoic acid, and alkyl, alkoxy or halogen substituents thereof. Can be mentioned.
芳香族アミノカルボン酸のエステル誘導体、酸ハロゲン化物等のエステル形成性誘導体も液晶ポリマー製造用のモノマーとして好適に使用できる。 Ester derivatives of aromatic aminocarboxylic acids, ester-forming derivatives such as acid halides can also be suitably used as monomers for producing liquid crystal polymers.
脂肪族ジオキシ単位を与える単量体の具体例としては、例えばエチレングリコール、１，４－ブタンジオール、１，６－ヘキサンジオール等の脂肪族ジオール、並びにそれらのアシル化物が挙げられる。 Specific examples of the monomer giving an aliphatic dioxy unit include aliphatic diols such as ethylene glycol, 1,4-butanediol, and 1,6-hexanediol, and acylated products thereof.
また、ポリエチレンテレフタレートや、ポリブチレンテレフタレート等の脂肪族ジオキシ単位を含有するポリマーを、前術の芳香族オキシカルボン酸、芳香族ジカルボン酸、芳香族ジオール、及びそれらのアシル化物、エステル誘導体、酸ハロゲン化物等と反応させることによっても、脂肪族ジオキシ単位を含む液晶ポリマー（Ａ）を得ることができる。 Further, a polymer containing an aliphatic dioxy unit such as polyethylene terephthalate or polybutylene terephthalate can be used as an aromatic oxycarboxylic acid, an aromatic dicarboxylic acid, an aromatic diol, and an acylated product thereof, an ester derivative, or an acid halogen. The liquid crystal polymer (A) containing an aliphatic dioxy unit can also be obtained by reacting with a compound or the like.
液晶ポリマー（Ａ）は、チオエステル結合を含むものであってもよい。このような結合を与える単量体としては、メルカプト芳香族カルボン酸、芳香族ジチオール、及びヒドロキシ芳香族チオール等が挙げられる。 The liquid crystal polymer (A) may contain a thioester bond. Examples of the monomer giving such a bond include mercapto aromatic carboxylic acid, aromatic dithiol, hydroxy aromatic thiol and the like.
これらの単量体の使用量は、芳香族オキシカルボニル繰返し単位、芳香族ジカルボニル繰返し単位、芳香族ジオキシ繰返し単位、芳香族アミノオキシ繰返し単位、芳香族ジアミノ繰返し単位、芳香族アミノカルボニル繰り返し単位、芳香族オキシジカルボニル繰返し単位、及び脂肪族ジオキシ繰返し単位を与える単量体の合計量に対して１０モル％以下であるのが好ましい。 The amount of these monomers used is aromatic oxycarbonyl repeating unit, aromatic dicarbonyl repeating unit, aromatic dioxy repeating unit, aromatic aminooxy repeating unit, aromatic diamino repeating unit, aromatic aminocarbonyl repeating unit, It is preferably 10 mol% or less with respect to the total amount of the aromatic oxydicarbonyl repeating unit and the monomer giving the aliphatic dioxy repeating unit.
液晶ポリマー（Ａ）の好適な例としては、以下の１）～２５）が挙げられる。
１）４－ヒドロキシ安息香酸／２－ヒドロキシ－６－ナフトエ酸共重合体
２）４－ヒドロキシ安息香酸／テレフタル酸／４，４’－ジヒドロキシビフェニル共重合体
３）４－ヒドロキシ安息香酸／テレフタル酸／イソフタル酸／４，４’－ジヒドロキシビフェニル共重合体
４）４－ヒドロキシ安息香酸／テレフタル酸／イソフタル酸／４，４’－ジヒドロキシビフェニル／ハイドロキノン共重合体
５）４－ヒドロキシ安息香酸／テレフタル酸／ハイドロキノン共重合体
６）４－ヒドロキシ安息香酸／テレフタル酸／４，４’－ジヒドロキシビフェニル／ハイドロキノン共重合体
７）２－ヒドロキシ－６－ナフトエ酸／テレフタル酸／ハイドロキノン共重合体
８）４－ヒドロキシ安息香酸／２－ヒドロキシ－６－ナフトエ酸／テレフタル酸／４，４’－ジヒドロキシビフェニル共重合体
９）２－ヒドロキシ－６－ナフトエ酸／テレフタル酸／４，４’－ジヒドロキシビフェニル共重合体
１０）４－ヒドロキシ安息香酸／２－ヒドロキシ－６－ナフトエ酸／テレフタル酸／ハイドロキノン共重合体
１１）４－ヒドロキシ安息香酸／２－ヒドロキシ－６－ナフトエ酸／テレフタル酸／ハイドロキノン／４，４’－ジヒドロキシビフェニル共重合体
１２）４－ヒドロキシ安息香酸／２，６－ナフタレンジカルボン酸／４，４’－ジヒドロキシビフェニル共重合体
１３）４－ヒドロキシ安息香酸／テレフタル酸／２，６－ナフタレンジカルボン酸／ハイドロキノン共重合体
１４）４－ヒドロキシ安息香酸／２，６－ナフタレンジカルボン酸／ハイドロキノン共重合体
１５）４－ヒドロキシ安息香酸／２－ヒドロキシ－６－ナフトエ酸／２，６－ナフタレンジカルボン酸／ハイドロキノン共重合体
１６）４－ヒドロキシ安息香酸／テレフタル酸／２，６－ナフタレンジカルボン酸／ハイドロキノン／４，４’－ジヒドロキシビフェニル共重合体
１７）４－ヒドロキシ安息香酸／テレフタル酸／４－アミノフェノール共重合体
１８）２－ヒドロキシ－６－ナフトエ酸／テレフタル酸／４－アミノフェノール共重合体
１９）４－ヒドロキシ安息香酸／２－ヒドロキシ－６－ナフトエ酸／テレフタル酸／４－アミノフェノール共重合体
２０）４－ヒドロキシ安息香酸／テレフタル酸／４，４’－ジヒドロキシビフェニル／４－アミノフェノール共重合体
２１）４－ヒドロキシ安息香酸／テレフタル酸／エチレングリコール共重合体
２２）４－ヒドロキシ安息香酸／テレフタル酸／４，４’－ジヒドロキシビフェニル／エチレングリコール共重合体
２３）４－ヒドロキシ安息香酸／２－ヒドロキシ－６－ナフトエ酸／テレフタル酸／エチレングリコール共重合体
２４）４－ヒドロキシ安息香酸／２－ヒドロキシ－６－ナフトエ酸／テレフタル酸／４，４’－ジヒドロキシビフェニル／エチレングリコール共重合体
２５）４－ヒドロキシ安息香酸／テレフタル酸／２，６－ナフタレンジカルボン酸／４，４’－ジヒドロキシビフェニル共重合体。
Preferable examples of the liquid crystal polymer (A) include the following 1) to 25).
1) 4-Hydroxybenzoic acid / 2-hydroxy-6-naphthoic acid copolymer 2) 4-Hydroxybenzoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl copolymer 3) 4-hydroxybenzoic acid / terephthalic acid / Isophthalic acid / 4,4'-dihydroxybiphenyl copolymer 4) 4-hydroxybenzoic acid / terephthalic acid / isophthalic acid / 4,4'-dihydroxybiphenyl / hydroquinone copolymer 5) 4-hydroxybenzoic acid / terephthalic acid / Hydroquinone copolymer 6) 4-hydroxybenzoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl / hydroquinone copolymer 7) 2-hydroxy-6-naphthoic acid / terephthalic acid / hydroquinone copolymer 8) 4- Hydroxybenzoic acid / 2-hydroxy-6-naphthic acid / terephthalic acid / 4,4'-dihydroxybiphenyl copolymer 9) 2-hydroxy-6-naphthoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl copolymer 10) 4-Hydroxybenzoic acid / 2-hydroxy-6-naphthoic acid / terephthalic acid / hydroquinone copolymer 11) 4-hydroxybenzoic acid / 2-hydroxy-6-naphthoic acid / terephthalic acid / hydroquinone / 4,4' -Dihydroxybiphenyl copolymer 12) 4-hydroxybenzoic acid / 2,6-naphthalenedicarboxylic acid / 4,4'-dihydroxybiphenyl copolymer 13) 4-hydroxybenzoic acid / terephthalic acid / 2,6-naphthalenedicarboxylic acid / Hydroquinone copolymer 14) 4-hydroxybenzoic acid / 2,6-naphthalenedicarboxylic acid / Hydroquinone copolymer 15) 4-hydroxybenzoic acid / 2-hydroxy-6-naphthoic acid / 2,6-naphthalenedicarboxylic acid / Hydroquinone copolymer 16) 4-hydroxybenzoic acid / terephthalic acid / 2,6-naphthalenedicarboxylic acid / hydroquinone / 4,4'-dihydroxybiphenyl copolymer 17) 4-hydroxybenzoic acid / terephthalic acid / 4-aminophenol Copolymer 18) 2-Hydroxy-6-naphthoic acid / terephthalic acid / 4-aminophenol copolymer 19) 4-hydroxybenzoic acid / 2-hydroxy-6-naphthoic acid / terephthalic acid / 4-aminophenol co-weight Combined 20) 4-hydroxybenzoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl / 4-aminophenol copolymer 21) 4-hydroxybenzoic acid / terephthalic acid / ethylene glycol copolymer 22) 4-hi Droxybenzoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl / ethylene glycol copolymer 23) 4-hydroxybenzoic acid / 2-hydroxy-6-naphthoic acid / terephthalic acid / ethylene glycol copolymer 24) 4-hydroxy Benzoic acid / 2-hydroxy-6-naphthic acid / terephthalic acid / 4,4'-dihydroxybiphenyl / ethylene glycol copolymer 25) 4-hydroxybenzoic acid / terephthalic acid / 2,6-naphthalenedicarboxylic acid / 4,4 '-Dihydroxybiphenyl copolymer.
前述の通り、フェノール性水酸基を有するモノマーを含むモノマー混合物をアシル化して、フェノール性水酸基を有するモノマーのアシル化物を含むモノマー混合物を得るのが好ましい。アシル化は、フェノール性水酸基と、脂肪酸無水物とを反応させることにより行われるのが好ましい。脂肪酸無水物としては、例えば、無水酢酸、及び無水プロピオン酸等を用いること出来る。価格と取り扱い性の点から、無水酢酸が好ましく使用される。 As described above, it is preferable to acylate a monomer mixture containing a monomer having a phenolic hydroxyl group to obtain a monomer mixture containing an acylated product of a monomer having a phenolic hydroxyl group. Acylation is preferably carried out by reacting a phenolic hydroxyl group with a fatty acid anhydride. As the fatty acid anhydride, for example, acetic anhydride, propionic anhydride and the like can be used. Acetic anhydride is preferably used from the standpoint of price and handleability.
脂肪酸無水物の使用量は、フェノール性水酸基の量に対して、１．０倍当量以上１．１５倍当量以下が好ましく、１．０３倍当量以上１．１０倍当量以下がより好ましい。 The amount of the fatty acid anhydride used is preferably 1.0 times or more and 1.15 times or less, and more preferably 1.03 times or more and 1.10 times or less with respect to the amount of phenolic hydroxyl groups.
フェノール性水酸基を有するモノマーを含むモノマー混合物と、上記の脂肪酸無水物とを混合して加熱することによりアシル化して、フェノール性水酸基を有するモノマーのアシル化物を含むモノマー混合物が得られる。 A monomer mixture containing a monomer having a phenolic hydroxyl group and the above-mentioned fatty acid anhydride are mixed and acylated to obtain a monomer mixture containing an acylated product of the monomer having a phenolic hydroxyl group.
以上のようにして得られたフェノール性水酸基を有するモノマーのアシル化物を含むモノマー混合物を加熱するとともに、重縮合により副生する脂肪酸を留去することにより液晶ポリマー（Ａ）が得られる。 The liquid crystal polymer (A) is obtained by heating the monomer mixture containing the acylated product of the monomer having a phenolic hydroxyl group obtained as described above and distilling off the fatty acid produced as a by-product by polycondensation.
溶融重縮合のみにより液晶ポリマー（Ａ）を製造する場合、溶融重縮合の温度は、１５０℃以上４００℃以下が好ましく、２５０℃以上３７０℃以下が好ましい。 When the liquid crystal polymer (A) is produced only by melt polycondensation, the temperature of melt polycondensation is preferably 150 ° C. or higher and 400 ° C. or lower, and preferably 250 ° C. or higher and 370 ° C. or lower.
溶融重縮合と、後述する固相重合との二段階で液晶ポリマー（Ａ）を製造する場合、溶融重縮合の温度は１２０℃以上３５０℃以下が好ましく、２００℃以上３００℃以下が好ましい。重縮合反応の時間は、所望する融点、又は所望する分子量の液晶ポリマー（Ａ）が得られる限り特に限定されない。例えば、重縮合の反応時間としては３０分以上５時間以下が好ましい。 When the liquid crystal polymer (A) is produced in two steps of melt polycondensation and solid phase polymerization described later, the temperature of melt polycondensation is preferably 120 ° C. or higher and 350 ° C. or lower, and preferably 200 ° C. or higher and 300 ° C. or lower. The time of the polycondensation reaction is not particularly limited as long as the liquid crystal polymer (A) having a desired melting point or a desired molecular weight can be obtained. For example, the reaction time of polycondensation is preferably 30 minutes or more and 5 hours or less.
上記方法により製造される液晶ポリマー（Ａ）は、必要に応じて、さらに高分子量化するために、固化された状態（固相）で加熱する重縮合に供されてもよい。 The liquid crystal polymer (A) produced by the above method may be subjected to polycondensation by heating in a solidified state (solid phase), if necessary, in order to further increase the molecular weight.
上記方法により、液晶ポリマー（Ａ）が得られる。液晶ポリマー（Ａ）の融点は、本発明の目的を阻害しない範囲で特に限定されない。液晶ポリマー（Ａ）の融点は、２５０℃以上が好ましく、２８０℃以上がより好ましい。他方、加工性の観点や、液晶ポリマー組成物製造時のグラフト変性ポリオレフィン（Ｂ）、及び架橋剤（Ｃ）の分解の抑制の点等から、液晶ポリマー（Ａ）の融点は、４００℃以下が好ましく、３５０℃以下がより好ましい。 The liquid crystal polymer (A) is obtained by the above method. The melting point of the liquid crystal polymer (A) is not particularly limited as long as it does not impair the object of the present invention. The melting point of the liquid crystal polymer (A) is preferably 250 ° C. or higher, more preferably 280 ° C. or higher. On the other hand, the melting point of the liquid crystal polymer (A) is 400 ° C. or lower from the viewpoint of processability and the suppression of decomposition of the graft-modified polyolefin (B) and the cross-linking agent (C) during the production of the liquid crystal polymer composition. It is preferably 350 ° C. or lower, more preferably 350 ° C. or lower.
なお、液晶ポリマー（Ａ）の融点は、例えば、示差走査熱量計（Ｄｉｆｆｅｒｅｎｔｉａｌ ｓｃａｎｎｉｎｇ ｃａｌｏｒｉｍｅｔｅｒ、以下ＤＳＣと略す）によって、昇温速度２０℃／ｍｉｎで測定した際の結晶融解ピークから求めた温度である。より具体的には、液晶ポリマー（Ａ）の試料を、室温から２０℃／分の昇温条件で測定した際に観測される吸熱ピーク温度（Ｔｍ１）の観測後、Ｔｍ１より２０℃以上５０℃以下高い温度で１０分間保持し、次いで、２０℃／分の降温条件で室温まで試料を冷却した後に、再度２０℃／分の昇温条件で測定した際の吸熱ピークを観測し、そのピークトップを示す温度を液晶ポリマー（Ａ）の融点とする。測定用機器としては、例えば、ＴＡ Ｉｎｓｔｒｕｍｅｎｔｓ社製ＤＳＣ Ｑ１０００等を使用することができる。 The melting point of the liquid crystal polymer (A) is, for example, the temperature obtained from the crystal melting peak measured at a heating rate of 20 ° C./min by a differential scanning calorimeter (hereinafter abbreviated as DSC). .. More specifically, after observing the heat absorption peak temperature (Tm1) observed when the sample of the liquid crystal polymer (A) is measured at a temperature rising condition of 20 ° C./min from room temperature, the temperature is 20 ° C. or higher and 50 ° C. from Tm1. After holding the sample at a high temperature for 10 minutes and then cooling the sample to room temperature under a temperature decrease condition of 20 ° C./min, the heat absorption peak was observed again when measured under a temperature rise condition of 20 ° C./min, and the peak top was observed. Let the temperature indicating the above be the melting point of the liquid crystal polymer (A). As the measuring device, for example, DSC Q1000 manufactured by TA Instruments can be used.
液晶ポリマー組成物は、本発明の目的を阻害しない範囲で、液晶ポリマー（Ａ）、及びグラフト変性ポリオレフィン（Ｂ）以外のその他の樹脂を含んでいてもよい。液晶ポリマー組成物に含まれる樹脂成分の全質量に対する、液晶ポリマー（Ａ）の質量とグラフト変性ポリオレフィン（Ｂ）の質量との合計の割合は、典型的には、８０質量％が好ましく、９０質量％以上がより好ましく、９５質量％以上がさらに好ましく、１００質量％が特に好ましい。 The liquid crystal polymer composition may contain other resins other than the liquid crystal polymer (A) and the graft-modified polyolefin (B) as long as the object of the present invention is not impaired. The total ratio of the mass of the liquid crystal polymer (A) and the mass of the graft-modified polyolefin (B) to the total mass of the resin component contained in the liquid crystal polymer composition is typically 80% by mass, preferably 90% by mass. % Or more is more preferable, 95% by mass or more is further preferable, and 100% by mass is particularly preferable.
その他の樹脂の例としては、グラフト変性されていないポリオレフィン、ポリエチレンテレフタレートやポリブチレンテレフタレート等の非液晶性のポリエステル、ポリアミド、ポリエステルアミド、ポリイミド、ポリアミドイミド、ポリカーボネート、ポリアセタール、ポリフェニレンサルファイド、ポリフェニレンエーテル、ポリスルホン、ポリエーテルスルホン、ポリエーテルイミド、シリコーン樹脂、及びフッ素樹脂等が挙げられる。 Examples of other resins include ungrafted polyolefins, non-liquid polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyamides, polyesteramides, polyimides, polyamideimides, polycarbonates, polyacetals, polyphenylene sulfides, polyphenylene ethers, polysulfones. , Polyethersulfone, polyetherimide, silicone resin, fluororesin and the like.
液晶ポリマー組成物には、必要に応じて、無機充填剤を配合できる。無機充填剤としては、炭酸カルシウム、タルク、クレー、シリカ、炭酸マグネシウム、硫酸バリウム、酸化チタン、アルミナ、モンモリロナイト、石膏、ガラスフレーク、ガラス繊維、ミルドガラス繊維、炭素繊維、アルミナ繊維、シリカアルミナ繊維、ホウ酸アルミニウムウィスカ、及びチタン酸カリウム繊維等が挙げられる。無機充填剤は、単独で使用されてもよく、２種以上を組み合わせて使用されてもよい。 Inorganic fillers can be added to the liquid crystal polymer composition, if necessary. Inorganic fillers include calcium carbonate, talc, clay, silica, magnesium carbonate, barium sulfate, titanium oxide, alumina, montmorillonite, gypsum, glass flakes, glass fiber, milled glass fiber, carbon fiber, alumina fiber, silica alumina fiber, Examples thereof include aluminum borate whisker and potassium titanate fiber. The inorganic filler may be used alone or in combination of two or more.
これらの無機充填剤の使用量は、液晶ポリマー組成物の低誘電特性を損なわない範囲で、液晶ポリマー組成物の用途に応じて適宜決定される。例えば、液晶ポリマー組成物を用いてフィルムを形成する場合には、フィルムの機械強度を著しく損なわない範囲で、無機充填剤の使用量の上限が定められる。 The amount of these inorganic fillers used is appropriately determined according to the use of the liquid crystal polymer composition as long as the low dielectric property of the liquid crystal polymer composition is not impaired. For example, when a film is formed using a liquid crystal polymer composition, the upper limit of the amount of the inorganic filler used is set within a range that does not significantly impair the mechanical strength of the film.
液晶ポリマー組成物には、必要に応じて、さらに、有機充填剤、酸化防止剤、熱安定剤、光安定剤、難燃剤、滑剤、帯電防止剤、着色剤、防錆剤、架橋剤、発泡剤、蛍光剤、表面平滑剤、表面光沢改良剤、及び離型改良剤等の各種の添加剤を配合できる。 If necessary, the liquid crystal polymer composition may further include an organic filler, an antioxidant, a heat stabilizer, a light stabilizer, a flame retardant, a lubricant, an antistatic agent, a colorant, a rust preventive, a cross-linking agent, and foaming. Various additives such as agents, fluorescent agents, surface smoothing agents, surface gloss improving agents, and mold release improving agents can be blended.
これらの添加剤は、単独で使用されてもよく、２種以上を組み合わせて使用されてもよい。 These additives may be used alone or in combination of two or more.
以上説明した液晶ポリマー組成物は、射出成形、押出成形、ブロー成形等の公知の種々の製造方法により種々の成形品に加工される。 The liquid crystal polymer composition described above is processed into various molded products by various known production methods such as injection molding, extrusion molding, and blow molding.
液晶ポリマー組成物からなる成形品に対して、架橋剤（Ｃ）による架橋処理が施されるのが好ましい。架橋処理の方法は特に限定されず、架橋剤（Ｃ）が有する反応性官能基の種類に応じて適宜選択される。架橋処理の方法としては、電子線照射、加熱、光照射等が挙げられる。
加熱により架橋する方法では、架橋温度が過度に高いと、成形品を架橋させる際に成形品が熱劣化したり変形したりするおそれがある。逆に架橋温度が過度に低いと、押出機内で液晶ポリマー組成物が架橋してしまうおそれがある。この場合、液晶ポリマー組成物の押出機内での増粘により成形品の外観不良が生じやすいため、液晶ポリマー組成物の成形方法として、溶融成形法の適用が難しい。光照射による方法では、特別な場合以外は、光酸発生剤等の開始剤が液晶ポリマー組成物に添加される必要がある。しかし、このような開始剤は、高温の押出機内で分解しやすい。以上の点を考慮すると、種々の不具合を生じさせることなく、フィルム等の成形品に架橋構造を容易に形成可能である点で電子線照射が好ましい。
つまり、架橋剤（Ｃ）により架橋処理された成形品の製造方法としては、
前述の液晶ポリマー組成物を上述の方法等により成形して成形品を得ることと、
得られた成形品に電子線を照射して、成形品に対して架橋剤（Ｃ）による架橋処理を行うことと、を含む方法が好ましい。
電子線照射を行う場合の電子線の線量としては、１００ｋＧｙ以上１２００ｋＧｙ以下が好ましく、２００ｋＧｙ以上８００ｋＧｙ以下がより好ましい。
It is preferable that the molded product made of the liquid crystal polymer composition is subjected to a cross-linking treatment with a cross-linking agent (C). The method of the cross-linking treatment is not particularly limited, and is appropriately selected depending on the type of the reactive functional group of the cross-linking agent (C). Examples of the method of cross-linking treatment include electron beam irradiation, heating, light irradiation and the like.
In the method of cross-linking by heating, if the cross-linking temperature is excessively high, the molded product may be thermally deteriorated or deformed when the molded product is cross-linked. On the contrary, if the cross-linking temperature is excessively low, the liquid crystal polymer composition may be cross-linked in the extruder. In this case, it is difficult to apply the melt molding method as a molding method for the liquid crystal polymer composition because the appearance of the molded product tends to be poor due to the thickening of the liquid crystal polymer composition in the extruder. In the light irradiation method, an initiator such as a photoacid generator needs to be added to the liquid crystal polymer composition, except in special cases. However, such initiators are prone to decomposition in high temperature extruders. Considering the above points, electron beam irradiation is preferable in that a crosslinked structure can be easily formed on a molded product such as a film without causing various problems.
That is, as a method for producing a molded product crosslinked with the crosslinking agent (C),
By molding the above-mentioned liquid crystal polymer composition by the above-mentioned method or the like to obtain a molded product,
A method including irradiating the obtained molded product with an electron beam and subjecting the molded product to a cross-linking treatment with a cross-linking agent (C) is preferable.
The dose of the electron beam in the case of electron beam irradiation is preferably 100 kGy or more and 1200 kGy or less, and more preferably 200 kGy or more and 800 kGy or less.
以上説明した液晶ポリマー組成物は、高周波帯域における低誘電特性と、フィルム等を加工する際の溶融加工性とに優れるため、好ましくはフィルムに加工され、当該フィルムを含む銅張積層板を用いて伝送損失の少ないフレキシブルプリント配線板が製造される。 Since the liquid crystal polymer composition described above is excellent in low dielectric property in a high frequency band and melt processability when processing a film or the like, it is preferably processed into a film, and a copper-clad laminate containing the film is used. Flexible printed wiring boards with low transmission loss are manufactured.
また、液晶ポリマー組成物からなる成形品に架橋剤（Ｃ）による架橋処理を施すことにより、良好な低誘電特性を示し、且つフレキシブルプリント配線板として好適な耐熱性を有するフィルムやシート等の成形品が得られる。 Further, by subjecting a molded product made of a liquid crystal polymer composition to a cross-linking treatment with a cross-linking agent (C), a film, a sheet or the like exhibiting good low-dielectric properties and having heat resistance suitable for a flexible printed wiring board can be molded. Goods are obtained.
架橋処理を施された成形品の１０ＧＨｚにおける比誘電率は、液晶ポリマー（Ａ）の周波数１０ＧＨｚにおける比誘電率より低い値であるのが好ましい。また、架橋処理をほどこされた成形品の１０ＧＨｚにおける誘電正接は、液晶ポリマー（Ａ）とグラフト変性ポリオレフィン（Ｂ）の周波数１０ＧＨｚにおける誘電正接のうちの低い値以下であるのが好ましい。 The relative permittivity of the crosslinked molded article at 10 GHz is preferably lower than the relative permittivity of the liquid crystal polymer (A) at a frequency of 10 GHz. Further, the dielectric loss tangent of the crosslinked molded article at 10 GHz is preferably lower than the lower value of the dielectric loss tangent of the liquid crystal polymer (A) and the graft-modified polyolefin (B) at a frequency of 10 GHz.
また、架橋処理を施された成形品の１０ＧＨｚにおける誘電正接は、０．００２５以下が好ましい。 Further, the dielectric loss tangent at 10 GHz of the crosslinked molded product is preferably 0.0025 or less.
架橋処理を施された成形品の周波数１０ＧＨｚにおける比誘電率は、好ましくは２．８以下である。 The relative permittivity of the crosslinked molded article at a frequency of 10 GHz is preferably 2.8 or less.
以下に、実施例を挙げて本発明をさらに詳しく説明するが、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
〔製造例１〕
（変性ポリオレフィン１（ｍＰＯ１）の製造）
（ａ１）ポリメチルペンテン樹脂（三井化学製ＴＰＸグレードＭＸ００２）１００質量部、（ｂ１）１，３－ジ（ｔｅｒｔ－ブチルパーオキシイソプロピル）ベンゼン（日油製：パーブチルＰ）０．５質量部を、ホッパー口より、シリンダー温度２３０℃、スクリュー回転数１５０ｒｐｍに設定した二軸押出機（４６ｍｍφ、Ｌ／Ｄ＝６３、神戸製鋼社製）に供給して溶融混練を行う際に、シリンダー途中より（ｃ１）スチレン１質量部、（ｄ１）グリシジルメタクリレート１質量部を加えた。その後、ベント口から真空脱揮することにより変性ポリオレフィン樹脂のペレットを得た。
[Manufacturing Example 1]
(Manufacturing of Modified Polyolefin 1 (mPO1))
(A1) 100 parts by mass of polymethylpentene resin (TPX grade MX002 manufactured by Mitsui Chemicals), (b1) 0.5 parts by mass of 1,3-di (tert-butylperoxyisopropyl) benzene (manufactured by NOF Corporation: Perbutyl P) , From the middle of the cylinder when supplying to a twin-screw extruder (46 mmφ, L / D = 63, manufactured by Kobe Steel, Ltd.) set to a cylinder temperature of 230 ° C and a screw rotation speed of 150 rpm from the hopper mouth. c1) 1 part by mass of styrene and (d1) 1 part by mass of glycidyl methacrylate were added. Then, the modified polyolefin resin pellets were obtained by vacuum devolatile from the vent port.
得られた樹脂ペレットを１３０℃でキシレンに溶解させた後、再び常温に冷却した際に析出した再結晶樹脂を用いて、ＪＩＳ Ｋ７２３６に準拠し電位差自動滴定装置（京都電子工業製ＡＴ７００）でグリシジルメタクリレート変性量を測定した。変性ポリオレフィン１（ｍＰＯ１）のグリシジルメタクリレート変性量は０．７５質量％だった。 After dissolving the obtained resin pellets in xylene at 130 ° C., using the recrystallized resin precipitated when cooled to room temperature again, glycidyl was used in a potential difference automatic titrator (AT700 manufactured by Kyoto Electronics Industry Co., Ltd.) in accordance with JIS K7236. The amount of methacrylate denaturation was measured. The amount of glycidyl methacrylate modification of the modified polyolefin 1 (mPO1) was 0.75% by mass.
〔製造例２〕
（変性ポリオレフィン２（ｍＰＯ２）の製造）
（ａ１）α－オレフィンコポリマー樹脂（三井化学製ＡＢＳＯＲＴＯＭＥＲ（商標）ＥＰ１０１３）１００質量部、（ｂ１）１，３－ジ（ｔｅｒｔ－ブチルパーオキシイソプロピル）ベンゼン（日油製：パーブチルＰ）０．５質量部を、ホッパー口より、シリンダー温度２３０℃、スクリュー回転数１５０ｒｐｍに設定した二軸押出機（４６ｍｍφ、Ｌ／Ｄ＝６３、神戸製鋼社製）に供給して溶融混練を行う際に、シリンダー途中より（ｃ１）スチレン１質量部、（ｄ１）グリシジルメタクリレート１質量部を加えた。その後、ベント口から真空脱揮することにより変性ポリオレフィン樹脂のペレットを得た。
[Manufacturing Example 2]
(Manufacturing of Modified Polyolefin 2 (mPO2))
(A1) α-olefin copolymer resin (ABSORTOMER ™ EP1013 manufactured by Mitsui Chemicals, Inc.) 100 parts by mass, (b1) 1,3-di (tert-butylperoxyisopropyl) benzene (NOF Corporation: Perbutyl P) 0.5 When the mass part is supplied from the hopper mouth to a twin-screw extruder (46 mmφ, L / D = 63, manufactured by Kobe Steel, Ltd.) set to a cylinder temperature of 230 ° C. and a screw rotation speed of 150 rpm to perform melt kneading, the cylinder is used. From the middle, 1 part by mass of (c1) styrene and 1 part by mass of (d1) glycidyl methacrylate were added. Then, the modified polyolefin resin pellets were obtained by vacuum devolatile from the vent port.
得られた樹脂ペレットを１３０℃でキシレンに溶解させた後、再び常温に冷却した際に析出した再結晶樹脂を用いて、ＪＩＳ Ｋ７２３６に準拠し電位差自動滴定装置（京都電子工業製ＡＴ７００）でグリシジルメタクリレート変性量を測定した。変性ポリオレフィン２（ｍＰＯ２）のグリシジルメタクリレート変性量は０．２３質量％だった。 After dissolving the obtained resin pellets in xylene at 130 ° C., using the recrystallized resin precipitated when cooled to room temperature again, glycidyl was used in a potential difference automatic titrator (AT700 manufactured by Kyoto Electronics Industry Co., Ltd.) in accordance with JIS K7236. The amount of methacrylate denaturation was measured. The amount of glycidyl methacrylate modification of the modified polyolefin 2 (mPO2) was 0.23% by mass.
〔実施例１～８、及び比較例１〕
実施例１～８、及び比較例１において、液晶ポリマー（Ａ）（（Ａ）成分）として、融点２８０℃の全芳香族液晶ポリエステル樹脂を用いた。
また、実施例１～８、及び比較例１において、グラフト変性ポリオレフィン（Ｂ）（（Ｂ）成分）として、製造例１及び製造例２で得た、変性ポリオレフィン１（ｍＰＯ１）、及び変性ポリオレフィン２（ｍＰＯ２）を用いた。
さらに、比較例１において、他の樹脂としてα－オレフィンコポリマー樹脂（三井化学製ＡＢＳＯＲＴＯＭＥＲ（商標）ＥＰ１０１３）を用いた。
[Examples 1 to 8 and Comparative Example 1]
In Examples 1 to 8 and Comparative Example 1, a total aromatic liquid crystal polyester resin having a melting point of 280 ° C. was used as the liquid crystal polymer (A) (component (A)).
Further, in Examples 1 to 8 and Comparative Example 1, as the graft-modified polyolefin (B) ((B) component), the modified polyolefin 1 (mPO1) and the modified polyolefin 2 obtained in Production Examples 1 and 2 were obtained. (MPO2) was used.
Further, in Comparative Example 1, an α-olefin copolymer resin (ABSORTOMER ™ EP1013 manufactured by Mitsui Chemicals, Inc.) was used as another resin.
表１に記載の量の液晶ポリマー（Ａ）と、表１に記載の種類及び量のポリオレフィンとを、シリンダー温度３００℃、スクリュー回転数１５０ｒｐｍに設定した二軸押出機（２５ｍｍφ、Ｌ／Ｄ＝４０、テクノベル製）にホッパー口から供給して、溶融混錬した。
次いで、溶融混錬された液晶ポリマー（Ａ）及びポリオレフィンと、表１に記載の量の架橋剤（Ｃ）（トリアリルイソシアヌレート）とを、シリンダー温度２３０℃、スクリュー回転数１５０ｒｐｍに設定した二軸押出機（２５ｍｍφ、Ｌ／Ｄ＝４０、テクノベル製）にホッパー口から供給して、溶融混錬して、液晶ポリマー組成物を得た。
A twin-screw extruder (25 mmφ, L / D =) in which the amount of the liquid crystal polymer (A) shown in Table 1 and the type and amount of polyolefin shown in Table 1 are set at a cylinder temperature of 300 ° C. and a screw rotation speed of 150 rpm. 40, manufactured by Technobel) was supplied from the hopper mouth and melt-kneaded.
Next, the melt-kneaded liquid crystal polymer (A) and polyolefin and the amount of the cross-linking agent (C) (triallyl isocyanurate) shown in Table 1 were set at a cylinder temperature of 230 ° C. and a screw rotation speed of 150 rpm. A shaft extruder (25 mmφ, L / D = 40, manufactured by Technobel) was supplied from the hopper port and melt-kneaded to obtain a liquid crystal polymer composition.
上記のようにして得られた実施例１～８の液晶ポリマー組成物、又は比較例１の液晶ポリマー組成物を２３０℃で溶融させ、溶融した液晶ポリマー組成物を１４０ｍｍ幅のＴダイから概ね１００μｍの厚さで押出して液晶ポリマー組成物からなるフィルムを得た。
さらに溶融させる温度を３００℃に変更した以外は同様にして参考例の液晶ポリマーフィルムを得た。
The liquid crystal polymer compositions of Examples 1 to 8 or the liquid crystal polymer composition of Comparative Example 1 obtained as described above were melted at 230 ° C., and the melted liquid crystal polymer composition was approximately 100 μm from a 140 mm wide T-die. Extruded to the thickness of to obtain a film consisting of a liquid crystal polymer composition.
Further, a liquid crystal polymer film of a reference example was obtained in the same manner except that the melting temperature was changed to 300 ° C.
得られたフィルムに、加速電圧２００ｋＶで吸収線量４００ｋＧｙの条件で電子線を照射して、架橋剤による架橋を行った。 The obtained film was irradiated with an electron beam under the condition of an acceleration voltage of 200 kV and an absorbed dose of 400 kGy to carry out cross-linking with a cross-linking agent.
架橋されたフィルムについて、以下の方法に従い、誘電特性（Ｄｋ（比誘電率）、Ｄｆ（誘電正接））、線膨張係数（ＣＴＥ）、耐熱性（ＤＭＡ）、及びリフロー耐熱性を評価した。これらの評価結果を表１に記す。 The crosslinked film was evaluated for dielectric properties (Dk (relative permittivity), Df (dielectric loss tangent)), linear expansion coefficient (CTE), heat resistance (DMA), and reflow heat resistance according to the following methods. The results of these evaluations are shown in Table 1.
［誘電特性（Ｄｋ（比誘電率）、Ｄｆ（誘電正接））］
測定装置として、空洞共振器摂動法複素誘電率評価装置を用い、得られたフィルムの比誘電率及び誘電正接を下記周波数で測定した。なお、参考例として、液晶ポリマーの誘電特性を表１に記す。
測定周波数：１０ＧＨｚ
測定条件：温度２２℃～２４℃、湿度４５％～５５％
測定試料：前記測定条件下で、２４時間放置した試料を使用した。
[Dielectric properties (Dk (relative permittivity), Df (dielectric loss tangent))]
As a measuring device, a cavity resonator permittivity complex dielectric constant evaluation device was used, and the relative permittivity and the dielectric loss tangent of the obtained film were measured at the following frequencies. As a reference example, the dielectric properties of the liquid crystal polymer are shown in Table 1.
Measurement frequency: 10GHz
Measurement conditions: temperature 22 ° C to 24 ° C, humidity 45% to 55%
Measurement sample: A sample left for 24 hours under the above measurement conditions was used.
［線膨張係数（ＣＴＥ）］
線膨張係数は、引張荷重法による熱機械分析装置（Ｂｒｕｋｅｒ社製、ＴＭＡ ４０００ＳＡ）で評価した。フィルムから１０ｍｍ×３ｍｍの試料をＴダイからの押出方向（ＭＤ）に平行に切り出した。この試料の長辺に２９．４ｍＮの荷重を加え、１０℃／分で２０℃から２００℃まで一旦昇温させた後、０℃まで冷却し、再び２００℃まで１０℃／ｍｉｎで昇温した。この２回目の昇温時の試料の５０℃と１５０℃の間の歪の変化量を線膨張係数とした。表１に記載の線膨張係数（ＣＴＥ）の単位はｐｐｍ／Ｋである。
[Line expansion coefficient (CTE)]
The linear expansion coefficient was evaluated by a thermomechanical analyzer (manufactured by Bruker, TMA 4000SA) by the tensile load method. A 10 mm × 3 mm sample was cut out from the film parallel to the extrusion direction (MD) from the T-die. A load of 29.4 mN was applied to the long side of this sample, the temperature was once raised from 20 ° C to 200 ° C at 10 ° C / min, cooled to 0 ° C, and then heated again to 200 ° C at 10 ° C / min. .. The amount of change in strain between 50 ° C and 150 ° C of the sample at the time of the second temperature rise was defined as the linear expansion coefficient. The unit of the linear expansion coefficient (CTE) shown in Table 1 is ppm / K.
［耐熱性（ＤＭＡ）］
測定装置として、動的粘弾性測定装置を用い、貯蔵弾性率が１０７ＭＰａ以下になる温度を測定した。測定条件の詳細は以下の通りである。
サンプル測定範囲：幅５ｍｍ、つかみ具間距離２０ｍｍ
測定温度範囲：２５℃～２６０℃
昇温速度：５℃／分
歪み振幅：０．１％
測定周波数：１Ｈｚ
最小張力／圧縮力：０．１ｇ
力振幅初期値：１００ｇ
[Heat resistance (DMA)]
A dynamic viscoelasticity measuring device was used as a measuring device, and the temperature at which the storage elastic modulus became 107 MPa or less was measured. The details of the measurement conditions are as follows.
Sample measurement range: width 5 mm, distance between grips 20 mm
Measurement temperature range: 25 ° C to 260 ° C
Temperature rise rate: 5 ° C / min Strain amplitude: 0.1%
Measurement frequency: 1Hz
Minimum tension / compressive force: 0.1 g
Initial force amplitude: 100 g
［リフロー耐熱試験］
銅張積層板としての耐熱性を評価するために、リフロー耐熱試験を行った。
フィルムの試料の両面を電解銅箔（ＣＦ－Ｔ４９Ａ－ＤＳ－ＨＤ２－１２（福田金属箔粉工業（株）社製））で挟み、１８０℃で真空プレスを行い模擬的な銅張積層板（ＣＣＬ）を作製した。
得られたＣＣＬを、鉛フリーはんだの使用を想定した条件で高温リフロー炉（アントム社、ＵＮＩ６１１６Ｓ）を通過させ、高温リフロー炉通過後のＣＣＬ試料を観察した。高温リフロー炉の通過条件は、ピーク温度２８８±３℃、通過時間６０秒、通過サイクル数３である。
観察の結果に基づき、以下の基準に従いリフロー耐熱性を評価した。リフロー耐熱性についての合格の許容範囲は、下記のＡ～Ｃ評価である。
Ａ：外観に変化なし
Ｂ：試料の端部にわずかにシワ発生
Ｃ：銅箔が部分的に剥離し、銅箔にわずかにシワ生成
Ｄ：銅箔が著しく剥離し銅箔表面に凹凸が生じ、フィルムにボイドが発生した。
[Reflow heat resistance test]
A reflow heat resistance test was conducted to evaluate the heat resistance of the copper-clad laminate.
Both sides of the film sample are sandwiched between electrolytic copper foils (CF-T49A-DS-HD2-12 (manufactured by Fukuda Metal Foil Powder Industry Co., Ltd.)) and vacuum pressed at 180 ° C. CCL) was prepared.
The obtained CCL was passed through a high temperature reflow oven (UNI6116S, Antom) under the condition assuming the use of lead-free solder, and the CCL sample after passing through the high temperature reflow oven was observed. The passing conditions of the high temperature reflow furnace are a peak temperature of 288 ± 3 ° C., a passing time of 60 seconds, and a number of passing cycles of 3.
Based on the observation results, the reflow heat resistance was evaluated according to the following criteria. The acceptable range of acceptance for reflow heat resistance is the following A to C evaluations.
A: No change in appearance B: Slight wrinkles are generated at the edge of the sample C: Copper foil is partially peeled off and slightly wrinkled on the copper foil D: Copper foil is remarkably peeled off and unevenness is generated on the surface of the copper foil , Voids occurred on the film.
実施例１～８より、極性基を有するグラフト変性ポリオレフィン（Ｂ）と架橋剤（Ｃ）と液晶ポリマー（Ａ）とを混合して得られる液晶ポリマー組成物は、良好にフィルム化できることが分かる。また、実施例１～８で得た液晶ポリマー組成物からなるフィルムを架橋することで、低誘電特性に優れるフィルムを含み、リフロー耐熱性に優れる銅張積層板（ＣＣＬ）を製造できることが分かる。
他方、比較例１によれば、極性基を有するグラフト変性ポリオレフィン（Ｂ）を液晶ポリマーと混合しても、リフロー耐熱性に優れる銅張積層板（ＣＣＬ）を製造できないことが分かる。
From Examples 1 to 8, it can be seen that the liquid crystal polymer composition obtained by mixing the graft-modified polyolefin (B) having a polar group, the cross-linking agent (C) and the liquid crystal polymer (A) can be satisfactorily formed into a film. Further, it can be seen that by cross-linking the films made of the liquid crystal polymer compositions obtained in Examples 1 to 8, a copper-clad laminate (CCL) containing a film having excellent low dielectric properties and having excellent reflow heat resistance can be produced.
On the other hand, according to Comparative Example 1, it can be seen that even if the graft-modified polyolefin (B) having a polar group is mixed with the liquid crystal polymer, a copper-clad laminate (CCL) having excellent reflow heat resistance cannot be produced.
Claims (15)
前記グラフト変性ポリオレフィン（Ｂ）が、モノエンのみを重合したポリオレフィンのグラフト変性物である、液晶ポリマー組成物。 It contains a liquid crystal polymer (A), a graft-modified polyolefin (B) having a polar group, and a cross-linking agent (C).
A liquid crystal polymer composition in which the graft-modified polyolefin (B) is a graft-modified product of a polyolefin obtained by polymerizing only monoene.
前記成形品に電子線を照射して、前記成形品に対して前記架橋剤（Ｃ）による架橋処理を施すことと、を含む、成形品の製造方法。 To obtain a molded product by molding the liquid crystal polymer composition according to any one of claims 1 to 7.
A method for producing a molded product, which comprises irradiating the molded product with an electron beam and subjecting the molded product to a cross-linking treatment with the cross-linking agent (C).
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| CN115109394B (en) * | 2022-07-14 | 2024-03-15 | 中广核俊尔(浙江)新材料有限公司 | High weld mark strength liquid crystal polymer composite material and preparation method thereof |
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