TWI509704B - Semiconductor device substrate manufacturing method - Google Patents

Semiconductor device substrate manufacturing method Download PDF

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TWI509704B
TWI509704B TW100106840A TW100106840A TWI509704B TW I509704 B TWI509704 B TW I509704B TW 100106840 A TW100106840 A TW 100106840A TW 100106840 A TW100106840 A TW 100106840A TW I509704 B TWI509704 B TW I509704B
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TW201145399A (en
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Akihiro Tanabe
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Zeon Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/66007—Multistep manufacturing processes
    • H01L29/66075—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials
    • H01L29/66227—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials the devices being controllable only by the electric current supplied or the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched, e.g. three-terminal devices
    • H01L29/66409—Unipolar field-effect transistors
    • H01L29/66477—Unipolar field-effect transistors with an insulated gate, i.e. MISFET
    • H01L29/66742—Thin film unipolar transistors
    • H01L29/6675—Amorphous silicon or polysilicon transistors
    • H01L29/66765—Lateral single gate single channel transistors with inverted structure, i.e. the channel layer is formed after the gate
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
    • H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
    • H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
    • H01L27/1248—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs with a particular composition or shape of the interlayer dielectric specially adapted to the circuit arrangement

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Thin Film Transistor (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Formation Of Insulating Films (AREA)

Description

半導體元件基板之製造方法Semiconductor element substrate manufacturing method

本發明係關於一種對於半導體層來進行氫電漿處理並且形成使用有機材料之鈍化膜之半導體元件基板之製造方法。The present invention relates to a method of manufacturing a semiconductor element substrate which is subjected to hydrogen plasma treatment for a semiconductor layer and which forms a passivation film using an organic material.

半導體元件基板係廣泛地使用在電子製品。例如薄膜電晶體係具有稱為閘極電極、源極電極及汲極電極之端子之開關元件，廣泛地應用在主動矩陣型液晶顯示器或有機EL等之顯示元件之主動矩陣基板之主動元件等。Semiconductor element substrates are widely used in electronic products. For example, a thin film electro-crystal system has a switching element called a gate of a gate electrode, a source electrode, and a drain electrode, and is widely used as an active element of an active matrix substrate of an active matrix liquid crystal display or a display element such as an organic EL.

在習知之薄膜電晶體，在半導體元件或者是包含於半導體元件之半導體層表面，藉著濺鍍法、蒸鍍法、CVD法而形成由氮化矽膜(SiNx膜)所組成之鈍化膜。此外，以SiNx膜和由a-Si所組成之半導體層之密合性之提升，作為目的而對於半導體層之表面，來施行處理。In a conventional thin film transistor, a passivation film composed of a tantalum nitride film (SiNx film) is formed on a surface of a semiconductor element or a semiconductor layer included in a semiconductor element by a sputtering method, a vapor deposition method, or a CVD method. Further, the adhesion of the SiNx film and the semiconductor layer composed of a-Si is improved, and the surface of the semiconductor layer is treated for the purpose.

例如在專利文獻1，揭示：在對於半導體層來進行氫電漿處理之後，進行氮電漿處理，達到半導體層和鈍化膜之密合性之提升以及截止漏電流之減少。但是，正如專利文獻1所示，在鈍化膜使用無機材料之狀態下，必須在真空中，以材料呈電漿化或離子化之狀態，來進行成膜，有所謂設備成為大規模而操作變得煩雜之問題發生。For example, Patent Document 1 discloses that after performing hydrogen plasma treatment on a semiconductor layer, nitrogen plasma treatment is performed to improve adhesion of the semiconductor layer and the passivation film and to reduce leakage current. However, as shown in Patent Document 1, in the state where the passivation film is made of an inorganic material, it is necessary to form a film in a state in which the material is in a state of being plasmaized or ionized in a vacuum, and the so-called device becomes large-scale and operates. The troublesome problem occurs.

此外，在該狀態下，在氫電漿處理後而不進行氮電漿處理之時，有所謂發生蝕刻不良之問題產生，因此，必須在氫電漿處理之後，進行氮電漿處理。此外，在鈍化膜使用無機材料時，在形成接點孔之際，需要阻劑，因此，比起在鈍化膜使用有機材料之狀態，製程變得比較多。也就是說，需要塗佈阻劑之製程以及在亁式蝕刻之後而剝離阻劑之製程。相對於此，在鈍化膜使用有機材料之狀態下，不需要使用阻劑，因此，可以達到製程數之削減。此外，在使用無機材料之狀態下，限制可以形成在特定層上之鈍化膜之厚度，不容易形成平坦之鈍化膜。Further, in this state, when the plasma treatment is not performed after the hydrogen plasma treatment, there is a problem that etching failure occurs. Therefore, it is necessary to perform the nitrogen plasma treatment after the hydrogen plasma treatment. Further, when an inorganic material is used for the passivation film, a resist is required at the time of forming the contact hole, and therefore, the process becomes more complicated than when the organic material is used for the passivation film. That is to say, a process of applying a resist and a process of peeling off the resist after the etch etching are required. On the other hand, in the state where the organic material is used for the passivation film, it is not necessary to use a resist, and therefore, the number of processes can be reduced. Further, in the state where the inorganic material is used, the thickness of the passivation film which can be formed on the specific layer is restricted, and it is not easy to form a flat passivation film.

此外，在非專利文獻1，揭示：可以在鈍化膜，使用SiNx，進行電漿處理，抑制初期之截止漏電流。但是，在該半導體元件基板使用於顯示元件之主動矩陣基板之狀態下，要求高度之可靠性。也就是說，要求不僅是初期之截止漏電流，並且，即使是在過於嚴酷之條件下而使用之狀態，也抑制截止漏電流而達到TFT壽命之提升。Further, Non-Patent Document 1 discloses that it is possible to perform plasma treatment using SiNx on a passivation film to suppress an initial off-leakage current. However, in the state in which the semiconductor element substrate is used for the active matrix substrate of the display element, high reliability is required. In other words, it is required to achieve not only the initial off-state leakage current, but also the state in which it is used under too severe conditions, and the leakage current is suppressed to achieve an increase in the life of the TFT.

此外，SiNx係具有終止懸掛鏈之功能(例如參考專利文獻2)，因此，專利文獻1及非專利文獻1之電漿處理係並非終止懸掛鏈，來作為主目的。Further, since the SiNx has a function of terminating the suspension chain (for example, refer to Patent Document 2), the plasma processing systems of Patent Document 1 and Non-Patent Document 1 do not terminate the suspension chain as a main purpose.

【先前技術文獻】[Previous Technical Literature] 【專利文獻】[Patent Literature]

【專利文獻1】日本特開2003-37269號公報[Patent Document 1] Japanese Patent Laid-Open Publication No. 2003-37269

【專利文獻2】國際公開第2009/057444號[Patent Document 2] International Publication No. 2009/057444

【非專利文獻】[Non-patent literature]

【非專利文獻】Pei Ming Chen, Wan Yu Lo, Chuan Sheng Wei, Jing Jie Shih, Chih Hung Shih, Mao Song Chen, Feng Yuan Gen, and Tom Huang, “The effects of back-channel treatment on electrical characteristic of a-Si:H TFT device”, International Display Workshop’ 07, p1951-1953[Non-patent literature] Pei Ming Chen, Wan Yu Lo, Chuan Sheng Wei, Jing Jie Shih, Chih Hung Shih, Mao Song Chen, Feng Yuan Gen, and Tom Huang, “The effects of back-channel treatment on electrical characteristic of a-Si:H TFT device”, International Display Workshop’ 07, p1951-1953

本發明之目的係提供一種可以製造高可靠性之半導體元件基板之半導體元件基板製造方法。An object of the present invention is to provide a method of manufacturing a semiconductor element substrate which can manufacture a highly reliable semiconductor element substrate.

本發明人們係為了解決前述目的，因此，全心重複地進行研究，結果發現：可以藉由在半導體元件基板之製造方法，對於半導體元件之表面或者是包含於半導體元件之半導體層表面，來進行電漿處理，而終止懸掛鏈，藉由對於進行電漿處理之半導體元件表面或者是包含於半導體元件表面之半導體層表面，來形成包含有機材料之鈍化膜，而即使是在高溫高濕度下，也可以抑制截止漏電流之上升，具有良好之元件可靠性。In order to solve the above-mentioned object, the inventors of the present invention have conducted intensive studies and found that the surface of the semiconductor element or the surface of the semiconductor layer included in the semiconductor element can be formed by the method of manufacturing the semiconductor element substrate. Plasma treatment, and the suspension chain is terminated, and a passivation film containing an organic material is formed by a surface of a semiconductor element subjected to plasma treatment or a surface of a semiconductor layer included in a surface of the semiconductor element, even under high temperature and high humidity, It is also possible to suppress an increase in the off-leakage current and to have good component reliability.

也就是說，如果藉由本發明的話，則(1)：一種半導體元件基板之製造方法，係包含：對於半導體元件之表面或者是包含於前述半導體元件之半導體層表面來進行電漿處理之製程；以及在進行前述電漿處理之前述半導體元件表面或前述半導體層表面來形成由有機材料而組成之鈍化膜之製程來構成；(2)：一種(1)記載之半導體元件基板之製造方法，前述電漿處理係氫電漿處理；That is, according to the present invention, (1): a method of manufacturing a semiconductor device substrate, comprising: a process of performing plasma treatment on a surface of a semiconductor element or a surface of a semiconductor layer included in the semiconductor element; And a process for forming a passivation film made of an organic material on the surface of the semiconductor device or the surface of the semiconductor layer subjected to the plasma treatment, and (2) a method for producing a semiconductor device substrate according to (1), wherein Plasma treatment is hydrogen plasma treatment;

(3)：一種(1)或(2)記載之半導體元件基板之製造方法，前述半導體元件或前述半導體層係藉由包含在基板上形成閘極電極、閘極絕緣膜、半導體層和源極‧汲極電極之製程以及形成通道區域之製程的製程而進行製造；(3) The method of manufacturing a semiconductor device substrate according to the above aspect, wherein the semiconductor element or the semiconductor layer is formed by forming a gate electrode, a gate insulating film, a semiconductor layer, and a source on the substrate. ‧ manufacturing of the electrode of the drain electrode and the process of forming the channel region;

(4)：一種(1)至(3)中任一項所記載之半導體元件基板之製造方法，前述有機材料係含有樹脂之樹脂組成物；(4) The method for producing a semiconductor device substrate according to any one of (1) to (3), wherein the organic material is a resin composition containing a resin;

(5)：一種(1)至(4)中任一項所記載之半導體元件基板之製造方法，前述電漿處理係1～10分鐘之處理時間。(5) The method for producing a semiconductor device substrate according to any one of (1) to (4), wherein the plasma treatment is performed for 1 to 10 minutes.

如果藉由本發明之半導體元件基板之製造方法的話，則可以製造高可靠性之半導體元件基板。According to the method of manufacturing a semiconductor element substrate of the present invention, a highly reliable semiconductor element substrate can be manufactured.

在以下，參考圖式而就本發明之半導體元件基板之製造方法，來進行說明。此外，附件之圖式係不過是在能夠理解發明之程度，呈概略地顯示構成要素之形狀、大小及配置，並非藉此而特別限定本發明。因此，在本發明之說明，省略不必要之要素，並且，圖示之各要素之形狀、尺寸比等係也不一定反映實際。此外，所謂本發明在不脫離記載於申請專利範圍之本發明技術思想之範圍內而進行各種形態之置換、變形及變更，係對於具有該技術領域之通常知識者而言，為理所當然。Hereinafter, a method of manufacturing a semiconductor element substrate of the present invention will be described with reference to the drawings. In addition, the drawings of the attached drawings are merely illustrative of the shape, size, and arrangement of the constituent elements to the extent that the invention can be understood, and the present invention is not particularly limited thereto. Therefore, in the description of the present invention, unnecessary elements are omitted, and the shapes and dimensional ratios of the respective elements shown in the drawings do not necessarily reflect actuality. In addition, it is a matter of course that those skilled in the art will be able to make various substitutions, modifications, and alterations of the present invention without departing from the scope of the invention.

首先，正如圖1(a)所示，在玻璃基板等之絕緣性基板21之上，藉由濺鍍法而形成閘極電極22。接著，以光阻劑(未圖示)作為遮罩，藉由乾式蝕刻或濕式蝕刻而正如圖1(b)所示，對於閘極電極22進行圖案化。接著，正如圖1(c)所示，藉由CVD法而依序地堆積閘極絕緣膜23、由非結晶矽所組成之半導體層24和不純物添加半導體層25。接著，正如圖1(d)所示，藉由以光阻劑(未圖示)作為遮罩，以乾式蝕刻或濕式蝕刻，對於半導體層24和不純物添加半導體層25，進行圖案化，而形成由半導體層24和不純物添加半導體層25所構成之島狀之半導體構造。First, as shown in FIG. 1(a), the gate electrode 22 is formed on the insulating substrate 21 such as a glass substrate by sputtering. Next, using a photoresist (not shown) as a mask, the gate electrode 22 is patterned by dry etching or wet etching as shown in FIG. 1(b). Next, as shown in FIG. 1(c), the gate insulating film 23, the semiconductor layer 24 composed of amorphous germanium, and the impurity-added semiconductor layer 25 are sequentially deposited by a CVD method. Next, as shown in FIG. 1(d), by using a photoresist (not shown) as a mask, the semiconductor layer 25 is added to the semiconductor layer 24 and the impurity by dry etching or wet etching, and patterning is performed. An island-like semiconductor structure composed of the semiconductor layer 24 and the impurity-added semiconductor layer 25 is formed.

(歐姆層)(ohm layer)

接著，正如圖2(a)所示，藉由濺鍍法而形成源極‧汲極電極26。接著，以光阻劑(未圖示)作為遮罩，藉由蝕刻而正如圖2(b)所示，對於源極‧汲極電極26進行圖案化，形成源極電極27和汲極電極28。也就是說，源極電極27和汲極電極28係藉由圖案化而分離源極‧汲極電極26來形成，源極‧汲極電極26、源極電極27和汲極電極28係全部藉由相同之材料而構成。一般而言，源極‧汲極電極之蝕刻係藉由濕式蝕刻而進行，但是，也可以是乾式蝕刻。Next, as shown in FIG. 2(a), the source ‧ 汲 electrode 26 is formed by sputtering. Next, a photoresist (not shown) is used as a mask, and as shown in FIG. 2(b), the source electrode ‧ the drain electrode 26 is patterned to form the source electrode 27 and the drain electrode 28 . That is, the source electrode 27 and the drain electrode 28 are formed by patterning and separating the source ‧th pole electrode 26, and the source ‧th pole electrode 26, the source electrode 27 and the drain electrode 28 are all borrowed It consists of the same material. In general, the etching of the source ‧ 电极 electrode is performed by wet etching, but it may be dry etching.

接著，仍然直接地使用藉由源極‧汲極電極26之圖案化而減膜之未圖示之光阻劑，來作為遮罩，蝕刻不純物添加半導體層25。形成圖2(c)所示之通道區域。一般而言，不純物添加半導體層之蝕刻係藉由乾式蝕刻而進行，但是，也可以是濕式蝕刻。在此，所謂通道區域係表示源極電極27和位處於源極電極存在之區域之不純物添加半導體層30之閘極電極側端部以及汲極電極28和位處於汲極電極存在之區域之不純物添加半導體層31之閘極電極側端部之間之夾住之部分之半導體層。也就是說，藉由夾住於圖2(c)之點線之箭號而顯示之部分之半導體層係通道區域29。Next, the photoresist (not shown) which is reduced by the patterning of the source ‧ 电极 electrode 26 is used as a mask, and the semiconductor layer 25 is etched with impurities. The channel area shown in Fig. 2(c) is formed. In general, the etching in which the impurity is added to the semiconductor layer is performed by dry etching, but may be wet etching. Here, the channel region means the source electrode 27 and the gate electrode side end portion of the impurity-added semiconductor layer 30 in the region where the source electrode exists, and the drain electrode 28 and the impurity in the region where the gate electrode exists. A semiconductor layer sandwiched between the gate electrode side end portions of the semiconductor layer 31 is added. That is, a portion of the semiconductor layer channel region 29 which is displayed by the arrow of the dotted line of Fig. 2(c).

接著，使用剝離液而除去利用於圖案化時之光阻劑(未圖示)。可能會在除去時，發生在基板上殘留有機物殘渣或者是污染等，因此，可以適度地組合：在使用剝離液而剝離光阻劑之後，使用UV照射之洗淨製程；或者是，以氧作為主體，使用混合CF4 或N2 等之氣體，產生電漿，使用生成之氧自由基之去光阻劑(ashing)製程；或者是這些之組合之製程等。Next, the photoresist (not shown) used for patterning is removed using a peeling liquid. There may be residual organic residue or contamination on the substrate during removal. Therefore, it may be combined in a moderate manner: after the photoresist is peeled off using the stripping solution, a UV irradiation cleaning process is used; or, oxygen is used as the cleaning process. The main body uses a gas obtained by mixing a CF 4 or N 2 gas to generate a plasma, an ashing process using the generated oxygen radicals, or a combination of these processes.

接著，對於通道區域29，進行氫電漿處理，終止懸掛鏈。氫電漿處理係最好是進行1~10分鐘，可以在進行氫電漿處理之際，施加數百W以下、最好是200W以下之偏壓。此外，在接著於進行電漿處理之製程而包含還藉由氟酸來對於前述電漿處理面進行表面處理之製程時，有更加地提升薄膜電晶體之可靠性之狀態發生，因此，變得理想。Next, for the channel region 29, hydrogen plasma treatment is performed to terminate the suspension chain. The hydrogen plasma treatment is preferably carried out for 1 to 10 minutes, and a bias voltage of several hundred W or less, preferably 200 W or less, may be applied during the hydrogen plasma treatment. Further, in the process of performing the plasma treatment, including the process of surface-treating the plasma-treated surface by hydrofluoric acid, the state in which the reliability of the thin-film transistor is further improved occurs, and thus, ideal.

接著，進行由有機材料而組成之鈍化膜之形成。在本發明，由有機材料而組成之鈍化膜係並無特別限定，但是，可以藉由電漿CVD法或蒸鍍法、薄膜層積法、塗佈法等而進行成膜。即使是在其中，也可以呈簡便且有效率地形成膜，因此，最好是薄膜層積法或塗佈法，更加理想是塗佈法。Next, formation of a passivation film composed of an organic material is performed. In the present invention, the passivation film composed of an organic material is not particularly limited, but may be formed by a plasma CVD method, a vapor deposition method, a thin film deposition method, a coating method, or the like. Even in this case, the film can be formed simply and efficiently. Therefore, a film deposition method or a coating method is preferable, and a coating method is more preferable.

在藉著塗佈法而進行由有機材料來組成之鈍化膜之成膜時，能夠以簡便且短時間之製程，來製作具有高可靠性之薄膜電晶體。此外，最好是藉由含有樹脂和有機溶媒之樹脂組成物而形成膜。When a film of a passivation film composed of an organic material is formed by a coating method, a thin film transistor having high reliability can be produced in a simple and short-time process. Further, it is preferred to form a film by a resin composition containing a resin and an organic solvent.

塗佈法係在形成經過通道區域之半導體層表面之氧化膜之除去之製程為止之薄膜電晶體之基板上而塗佈樹脂組成物之後，來除去溶媒之方法。作為樹脂組成物塗佈於前述基板上之方法係可以列舉例如噴射法、旋轉塗佈法、壓輥塗佈法、模塗佈法、刮刀法、旋轉塗佈法、桿條塗佈法、網版印刷法等。溶媒之除去係藉由乾燥塗佈膜、最好是加熱及乾燥塗佈膜而進行。在該狀態下，乾燥溫度係可以配合各種成分之種類或練合劑而適度地選擇，但是，通常是30～250℃。乾燥時間係可以配合各種成分之種類或練合之比例而適度地選擇，但是，通常是0.5～150分鐘。The coating method is a method of removing a solvent after applying a resin composition on a substrate of a thin film transistor formed by a process of removing an oxide film on a surface of a semiconductor layer in a channel region. Examples of the method in which the resin composition is applied onto the substrate include a spray method, a spin coating method, a roll coating method, a die coating method, a doctor blade method, a spin coating method, a bar coating method, and a web. Printing method, etc. The removal of the solvent is carried out by drying the coating film, preferably by heating and drying the coating film. In this state, the drying temperature can be appropriately selected in accordance with the type of the various components or the compounding agent, but it is usually 30 to 250 °C. The drying time can be appropriately selected in accordance with the kinds of the various components or the ratio of the ingredients, but it is usually 0.5 to 150 minutes.

薄膜層積法係樹脂組成物，塗佈於樹脂薄膜或金屬薄膜等之B階段薄膜形成用基板上，除去溶媒，得到B階段薄膜，接著，該B階段薄膜層積於前述基板上之方法。溶媒之除去係藉由乾燥、最好是加熱‧乾燥在塗佈後之B階段薄膜形成用基板而進行。在該狀態下，乾燥條件係可以配合各種成分之種類或練合之比例而適度地選擇，乾燥溫度係通常是30～150℃，乾燥時間係通常是0.5～90分鐘。薄膜之層積係可以使用加壓層合機、沖床、真空層合機、真空沖床、壓輥層合機等之壓合機而進行。The film-layering resin composition is applied to a B-stage film-forming substrate such as a resin film or a metal film, and a solvent is removed to obtain a B-stage film, and then the B-stage film is laminated on the substrate. The removal of the solvent is carried out by drying, preferably heating, and drying the coated B-stage film-forming substrate. In this state, the drying conditions can be appropriately selected in accordance with the types of the various components or the ratio of the kneading ratio. The drying temperature is usually 30 to 150 ° C, and the drying time is usually 0.5 to 90 minutes. The lamination of the film can be carried out using a press machine such as a pressure laminator, a punch press, a vacuum laminator, a vacuum press, or a press roll laminator.

藉著以上，而在形成薄膜電晶體之基板上，成膜由有機材料所組成之鈍化膜。鈍化膜之厚度係通常為0.1～100μm、最好是0.5～50μm、更加理想是0.5～30μm、最加理想是0.5～10μm。可以藉由鈍化膜之膜厚位處於前述範圍，而即使是在過於嚴酷之氣氛下，也能夠簡便地製造具有高可靠性之薄膜電晶體。在鈍化膜之膜厚過度薄之時，降低保護性能而惡化可靠性，或者是在製造時之微粒等成為原因而惡化良品率，不良品率變高。在過度厚之時，由於增加鈍化膜之應力而降低保護性能，惡化可靠性。By the above, a passivation film composed of an organic material is formed on the substrate on which the thin film transistor is formed. The thickness of the passivation film is usually 0.1 to 100 μm, preferably 0.5 to 50 μm, more preferably 0.5 to 30 μm, and most preferably 0.5 to 10 μm. The film thickness of the passivation film can be in the above range, and a thin film transistor having high reliability can be easily manufactured even in an atmosphere that is too harsh. When the film thickness of the passivation film is excessively thin, the protective performance is lowered to deteriorate the reliability, or the fine particles or the like at the time of production deteriorates the yield, and the defective product rate becomes high. When it is excessively thick, the protective performance is lowered due to the stress of the passivation film, and the reliability is deteriorated.

此外，在由無機材料而組成之鈍化膜之狀態下，膜厚係限制為200～400nm。因此，正如圖3(a)所示，由有機材料而組成之鈍化膜32係可以比起圖3(b)所示之由無機材料而組成之鈍化膜33，還更加達到平坦化。Further, in the state of a passivation film composed of an inorganic material, the film thickness is limited to 200 to 400 nm. Therefore, as shown in FIG. 3(a), the passivation film 32 composed of an organic material can be further flattened than the passivation film 33 composed of an inorganic material as shown in FIG. 3(b).

在使用於本發明且由有機材料而組成之鈍化膜係最好是藉由含有樹脂(A)和有機溶媒(B)之樹脂組成物而形成。The passivation film used in the present invention and composed of an organic material is preferably formed by a resin composition containing the resin (A) and the organic solvent (B).

在本發明，樹脂(A)係並無特別限定，列舉例如環狀烯烴樹脂、丙烯樹脂、丙烯醯胺樹脂、聚矽氧烷、環氧樹脂、苯酚樹脂、軸節樹脂、聚醯亞胺、聚醯胺醯亞胺、聚碳酸酯、聚乙烯對苯二甲酸酯、包含藉由下列之通式(1)所表示之單體單位之樹脂等。即使是在其中，也最好是包含由環狀烯烴樹脂、丙烯樹脂、軸節樹脂、聚矽氧烷和聚醯亞胺樹脂而組成之群組來選出之至少一種，即使是在這些當中，也由薄膜電晶體之可靠性之觀點來看的話，則更加理想是環狀烯烴樹脂，作為環狀烯烴樹脂係特別最好是具有質子性極性基之環狀烯烴樹脂或者是包含藉由通式(1)所表示之單體單位(e)之樹脂。In the present invention, the resin (A) is not particularly limited, and examples thereof include a cyclic olefin resin, an acrylic resin, an acrylamide resin, a polyoxyalkylene oxide, an epoxy resin, a phenol resin, a shaft resin, and a polyimine. Polyamidolimine, polycarbonate, polyethylene terephthalate, a resin containing a monomer unit represented by the following formula (1), and the like. Even in the case, it is preferable to include at least one selected from the group consisting of a cyclic olefin resin, a propylene resin, a shaft resin, a polysiloxane, and a polyimide resin, even among them, Further, from the viewpoint of the reliability of the thin film transistor, a cyclic olefin resin is more preferable, and as the cyclic olefin resin, a cyclic olefin resin having a protic polar group is particularly preferable or a general formula is included. (1) Resin of the monomer unit (e) represented.

(在前述化學式(1)中，R1 係表示碳數5～16之支鏈狀烷基。)(In the above chemical formula (1), R 1 represents a branched alkyl group having 5 to 16 carbon atoms.)

這些樹脂係可以分別獨立地使用，或者是也可以併用2種以上。These resins may be used independently of each other, or two or more types may be used in combination.

所謂質子性極性基係表示包含在屬於週期表第15族或第16族之原子呈直接地鍵結氫原子之原子之基。屬於週期表第15族或第16族之原子係最好是屬於週期表第15族或第16族之第1或第2週期之原子，更加理想是氧原子、氮原子或硫原子，特別最好是氧原子。The protic polar group means a group which is contained in an atom belonging to Group 15 or Group 16 of the periodic table and which directly bonds a hydrogen atom. The atomic system belonging to Group 15 or Group 16 of the periodic table is preferably an atom belonging to the first or second cycle of Group 15 or Group 16 of the periodic table, more preferably an oxygen atom, a nitrogen atom or a sulfur atom, particularly Good is the oxygen atom.

作為質子性極性基之具體例係列舉氫氧基、羧基(羥羰基)、磺酸基、磷酸基等之具有氧原子之極性基；伯胺基、仲胺基、伯醯胺基、仲醯胺基(醯亞胺基)等之具有氮原子之極性基；硫代基等之具有硫原子之極性基等。即使是在這些當中，也最好是具有氧原子，更加理想是羧基。Specific examples of the protic polar group include a polar group having an oxygen atom such as a hydroxyl group, a carboxyl group (hydroxycarbonyl group), a sulfonic acid group or a phosphoric acid group; a primary amino group, a secondary amino group, a primary amino group, and a secondary group; A polar group having a nitrogen atom such as an amino group (indenylene group); a polar group having a sulfur atom such as a thio group; and the like. Even among these, it is preferable to have an oxygen atom, and more preferably a carboxyl group.

在本發明，在鍵結於具有質子性極性基之環狀烯烴樹脂之質子性極性基之數目，並無特別限定，並且，可以包含不同種類之質子性極性基。In the present invention, the number of protic polar groups bonded to the cyclic olefin resin having a protic polar group is not particularly limited, and different types of protic polar groups may be contained.

在本發明之所謂環狀烯烴樹脂係具有脂環構造和碳-碳雙鍵之環狀烯烴單體之均聚物或共聚物。環狀烯烴樹脂係可以具有由環狀烯烴單體以外之單體而引導出之單位。The cyclic olefin resin of the present invention is a homopolymer or copolymer of a cyclic olefin monomer having an alicyclic structure and a carbon-carbon double bond. The cyclic olefin resin may have a unit which is guided out of a monomer other than the cyclic olefin monomer.

在環狀烯烴樹脂之全構造單位中，環狀烯烴單體單位之比例係通常為30～100重量%、最好是50～100重量%、更加理想是70～100重量%。In the total structural unit of the cyclic olefin resin, the ratio of the cyclic olefin monomer unit is usually 30 to 100% by weight, preferably 50 to 100% by weight, and more preferably 70 to 100% by weight.

在具有質子性極性基之環狀烯烴樹脂，質子性極性基係可以鍵結於環狀烯烴單體單位，也可以鍵結於環狀烯烴單體以外之單體單位，但是，最好是鍵結於環狀烯烴單體單位。In the cyclic olefin resin having a protic polar group, the protic polar group may be bonded to the cyclic olefin monomer unit or may be bonded to a monomer unit other than the cyclic olefin monomer, but it is preferably a bond. It is attached to a cyclic olefin monomer unit.

作為用以構成具有質子性極性基之環狀烯烴樹脂之單體係列舉具有質子性極性基之環狀烯烴單體(a)、具有質子性極性基以外之極性基之環狀烯烴單體(b)、不具有極性基之環狀烯烴單體(c)和環狀烯烴以外之單體(d)(在以下，這些單體僅稱為單體(a)～(d)。)。在此，單體(d)係可以具有質子性極性基或這個以外之極性基，也可以完全不具有極性基。The monomer olefin monomer (a) having a protic polar group and a cyclic olefin monomer having a polar group other than a protic polar group are exemplified as a monomer constituting a cyclic olefin resin having a protic polar group. b) a cyclic olefin monomer (c) having no polar group and a monomer (d) other than a cyclic olefin (hereinafter, these monomers are simply referred to as monomers (a) to (d)). Here, the monomer (d) may have a protic polar group or a polar group other than this, or may have no polar group at all.

在本發明，具有質子性極性基之環狀烯烴樹脂係最好是由單體(a)和單體(b)及/或單體(c)而構成，更加理想是由單體(a)和單體(b)而構成。In the present invention, the cyclic olefin resin having a protic polar group is preferably composed of the monomer (a) and the monomer (b) and/or the monomer (c), and more preferably the monomer (a). And monomer (b).

作為單體(a)之具體例係列舉5-羥基羰基二環[2. 2. 1]庚基-2-烯烴、5-甲基-5-羥基羰基二環[2. 2. 1]庚基-2-烯烴、5-羧基甲基-5-羥基羰基二環[2. 2. 1]庚基-2-烯烴、5,6-二羥基羰基二環[2. 2. 1]庚基-2-烯烴、9-羥基羰基四環[6. 2. 1. 13,6 . 02,7 ]十二-4-烯烴、9-甲基-9-羥基羰基四環[6. 2. 1. 13,6 . 02,7 ]十二-4-烯烴、9,10-二羥基羰基四環[6. 2. 1. 13,6 . 02,7 ]十二-4-烯烴等之含羧基環狀烯烴；5-(4-羥基苯基)二環[2. 2. 1]庚基-2-烯烴、5-甲基-5-(4-羥基苯基)二環[2. 2. 1]庚基-2-烯烴、9-(4-羥基苯基)四環[6. 2. 1. 13,6 . 02,7 ]十二-4-烯烴、9-甲基-9-(4-羥基苯基)四環[6. 2. 1. 13,6 .02,7 ]十二-4-烯烴等之含氫氧基環狀烯烴，即使是在其中，也最好是含羧基環狀烯烴。這些具有質子性極性基之環狀烯烴單體(a)係可以分別單獨地使用，也可以組合2種以上而使用。As a specific example of the monomer (a), a 5-hydroxycarbonylbicyclo[2.2.1]heptyl-2-olefin, 5-methyl-5-hydroxycarbonylbicyclo[2.2.1]g Benzene, 5-carboxymethyl-5-hydroxycarbonylbicyclo[2.2.1]heptyl-2-olefin, 5,6-dihydroxycarbonylbicyclo[2.2.1]heptyl 2-Olefin, 9-hydroxycarbonyltetracyclo[6. 2. 1. 1 3,6 . 2 2,7 ]dodec-4-olefin, 9-methyl-9-hydroxycarbonyltetracyclo[6. 2 1. 1 3,6 . 0 2,7 ]dodec-4-olefin, 9,10-dihydroxycarbonyltetracyclo[6. 2. 1. 1 3,6 . 0 2,7 ]12-4 a carboxyl group-containing cyclic olefin such as an olefin; 5-(4-hydroxyphenyl)bicyclo[2.2.1]heptyl-2-olefin, 5-methyl-5-(4-hydroxyphenyl)di Ring [2. 2. 1]heptyl-2-olefin, 9-(4-hydroxyphenyl)tetracyclo[6. 2. 1. 1 3,6 . 2 2,7 ] dode -4-olefin, a hydroxyl group-containing cyclic olefin such as 9-methyl-9-(4-hydroxyphenyl)tetracyclo[6. 2. 1. 3 3,6 .0 2,7 ]dodec-4-olefin, even Among them, it is also preferred to contain a carboxyl group-containing cyclic olefin. These cyclic olefin monomers (a) having a protic polar group may be used alone or in combination of two or more.

作為具有質子性極性基以外之極性基之環狀烯烴單體(b)具有之質子性極性基以外之極性基之具體例係列舉酯基(總括稱為烷氧基羰基和芳氧基羰基。)、N-取代醯亞胺基、環氧基、鹵素原子、氰基、羰基羥基羰基(二羧酸之酸酐殘基)、烷氧基、羰基、叔胺基、磺酸基、丙烯醯基等。即使是在其中，也最好是酯基、N-取代醯亞胺基和氰基，更加理想是酯基和N-取代醯亞胺基，特別最好是N-取代醯亞胺基。作為單體(b)之具體例係列舉例如以下之環狀烯烴。Specific examples of the polar group other than the protic polar group having the polar olefin monomer (b) having a polar group other than the protonic polar group are a series of ester groups (collectively referred to as an alkoxycarbonyl group and an aryloxycarbonyl group). , N-substituted quinone imine, epoxy, halogen atom, cyano group, carbonyl hydroxycarbonyl group (anhydride residue of dicarboxylic acid), alkoxy group, carbonyl group, tertiary amino group, sulfonic acid group, acrylonitrile group Wait. Even among them, an ester group, an N-substituted quinone group and a cyano group are preferable, and an ester group and an N-substituted quinone group are more preferable, and an N-substituted quinone group is particularly preferable. Specific examples of the monomer (b) include, for example, the following cyclic olefins.

作為具有酯基之環狀烯烴係列舉例如5-乙酸基二環[2. 2. 1]庚基-2-烯烴、5-甲氧基羰基二環[2. 2. 1]庚基-2-烯烴、5-甲基-5-甲氧基羰基二環[2. 2. 1]庚基-2-烯烴、9-乙酸基四環[6. 2. 1. 13,6 . 02,7 ]十二-4-烯烴、9-甲氧基羰基四環[6. 2. 1. 13,6 . 02,7 ]十二-4-烯烴、9-乙氧基羰基四環[6. 2. 1. 13,6 . 02,7 ]十二-4-烯烴、9-n-丙氧基羰基四環[6. 2. 1. 13,6 . 02,7 ]十二-4-烯烴、9-異氧基羰基四環[6. 2. 1. 13,6 . 02，7 ]十二-4-烯烴、9-n-丁氧基羰基四環[6. 2. 1. 13,6 . 02,7 ]十二-4-烯烴、9-甲基-9-甲氧基羰基四環[6. 2. 1. 13,6 . 02,7 ]十二-4-烯烴、9-甲基-9-乙氧基羰基四環[6. 2. 1. 13,6 . 02,7 ]十二-4-烯烴、9-甲基-9-n-丙氧基羰基四環[6. 2. 1. 13,6 . 02,7 ]十二-4-烯烴、9-甲基-9-異丙氧基羰基四環[6. 2. 1. 13,6 . 02,7 ]十二-4-烯烴、9-甲基-9-n-丁氧基羰基四環[6. 2. 1. 13,6 . 02,7 ]十二-4-烯烴、9-(2,2,2-三氟乙氧基羰基)四環[6. 2. 1. 13,6 . 02,7 ]十二-4-烯烴、9-甲基-9-(2,2,2-三氟乙氧基羰基)四環[6. 2. 1. 13,6 . 02,7 ]十二-4-烯烴等。As a series of cyclic olefins having an ester group, for example, 5-acetic acid bicyclo[2.2.1]heptyl-2-olefin, 5-methoxycarbonylbicyclo[2.2.1]heptyl-2 - olefin, 5-methyl-5-methoxycarbonylbicyclo[2.2.1]heptyl-2-olefin, 9-acetoxytetracyclo[6. 2. 1. 1 3,6 . 0 2 , 7 ] dode-4--4-olefin, 9-methoxycarbonyltetracyclo[6. 2. 1. 1 3,6 . 0 2,7 ]dodec-4-olefin, 9-ethoxycarbonyltetracyclo [6. 2. 1. 1 3,6 . 0 2,7 ] 12-4 -olefin, 9-n-propoxycarbonyltetracyclo[6. 2. 1. 1 3,6 . 0 2,7 ] 12-4-olefin, 9-isooxycarbonyltetracyclo[6. 2. 1. 1 3,6 . 0 2,7 ]dodec-4-olefin, 9-n-butoxycarbonyltetracyclic [6. 2. 1. 1 3,6 . 0 2,7 ] Dodec -4-olefin, 9-methyl-9-methoxycarbonyltetracyclo[6. 2. 1. 1 3,6 . 0 2,7 ]dodec-4-olefin, 9-methyl-9-ethoxycarbonyltetracyclo[6. 2. 1. 1 3,6 . 0 2,7 ]dodec-4-olefin, 9- Methyl-9-n-propoxycarbonyltetracyclo[6. 2. 1. 1 3,6 . 0 2,7 ]dodec-4-olefin, 9-methyl-9-isopropoxycarbonyltetra Ring [6. 2. 1. 1 3,6 . 0 2,7 ]dodec-4-olefin, 9-methyl-9-n-butoxycarbonyltetracyclo[6. 2. 1. 1 3, 6 . 0 2,7 ] 12-4 -olefin, 9-(2,2,2-trifluoroethoxy Cyclocarbonyl)tetracyclo[6. 2. 1. 1 3,6 . 0 2,7 ]dodec-4-olefin, 9-methyl-9-(2,2,2-trifluoroethoxycarbonyl) Tetracyclo[6. 2. 1. 1 3,6 . 0 2,7 ] 12-4 -olefin.

作為具有N-取代醯亞胺基之環狀烯烴係列舉例如N-苯基二環[2. 2. 1]庚基-5-烯烴-2,3-二羧基醯亞胺、N-(2-乙基己基)-1-異丙基-4-甲基二環[2. 2. 2]辛基-5-烯烴-2,3-二羧基醯亞胺、N-(2-乙基己基)-二環[2.2.1]庚基-5-烯烴-2,3-二羧基醯亞胺、N-[(2-乙基丁氧基)乙氧基丙基]-二環[2.2.1]庚基-5-烯烴-2,3-二羧基醯亞胺等。As a series of cyclic olefins having an N-substituted quinone imine group, for example, N-phenylbicyclo[2.2.1]heptyl-5-olefin-2,3-dicarboxy quinone imine, N-(2) -ethylhexyl)-1-isopropyl-4-methylbicyclo[2. 2. 2]octyl-5-olefin-2,3-dicarboxy quinone imine, N-(2-ethylhexyl) )-bicyclo[2.2.1]heptyl-5-olefin-2,3-dicarboxy quinone imine, N-[(2-ethylbutoxy)ethoxypropyl]-bicyclo[2.2. 1] Heptyl-5-olefin-2,3-dicarboxynonimine and the like.

作為具有氰基之環狀烯烴係列舉例如9-氰基四環[6.2.1.13,6 .02,7 ]十二-4-烯烴、9-甲基-9-氰基四環[6.2.1.13,6 .02,7 ]十二-4-烯烴、5-氰基二環[2.2.1]庚基-2-烯烴等。As a series of cyclic olefins having a cyano group, for example, 9-cyanotetracyclo[6.2.1.1 3,6 .0 2,7 ]dodec-4-olefin, 9-methyl-9-cyanotetracyclo[6.2 .1.1 3,6 .0 2,7 ]dodec-4-olefin, 5-cyanobicyclo[2.2.1]heptyl-2-olefin, and the like.

作為具有鹵素原子之環狀烯烴係列舉例如9-氯四環[6.2.1.13,6 .02,7 ]十二-4-烯烴、9-甲基-9-氯四環[6.2.1.13,6 .02,7 ]十二-4-烯烴等。As a series of cyclic olefins having a halogen atom, for example, 9-chlorotetracyclo[6.2.1.1 3,6 .0 2,7 ]dodec-4-olefin, 9-methyl-9-chlorotetracyclo[6.2.1.1 3,6 .0 2,7 ] 12-4 -olefins, etc.

這些具有質子性極性基以外之極性基之環狀烯烴單體(b)係可以分別單獨地使用，也可以組合2種以上而使用。The cyclic olefin monomer (b) having a polar group other than the protonic polar group may be used alone or in combination of two or more.

作為完全不具有極性基之環狀烯烴單體(c)之具體例係列舉二環[2.2.1]庚基-2-烯烴(也稱為「原菠烷」。)、5-乙基-二環[2.2.1]庚基-2-烯烴、5-丁基-二環[2.2.1]庚基-2-烯烴、5-乙叉-二環[2.2.1]庚基-2-烯烴、5-甲叉-二環[2.2.1]庚基-2-烯烴、5-乙烯基-二環[2.2.1]庚基-2-烯烴、三環[5.2.1.02,6 ]十-3,8-二烯烴(慣用名稱：二環戊二烯)、四環[10.2.1.02,11 .04,9 ]十五-4,6,8,13-四烯烴、四環[6.2.1.13,6 .02,7 ]十二-4-烯烴(也稱為「四環十二碳烯」。)、9-甲基-四環[6.2.1.13,6 .02,7 ]十二-4-烯烴、9-乙基-四環[6.2.1.13,6 .02,7 ]十二-4-烯烴、9-甲叉-四環[6. 2. 1. 13,6 . 02,7 ]十二-4-烯烴、9-乙叉-四環[6. 2. 1. 13,6 . 02,7 ]十二-4-烯烴、9-乙烯基-四環[6. 2. 1. 13,6 . 02,7 ]十二-4-烯烴、9-丙烯基-四環[6. 2. 1. 13,6 . 02,7 ]十二-4-烯烴、五環[9. 2. 1. 13,9 . 02,10 ]十五-5,12-二烯烴、環戊烯、環戊二烯、9-苯基-四環[6. 2. 1. 13,6 . 02,7 ]十二-4-烯烴、四環[9. 2. 1. 02,10 . 03,8 ]十四-3,5,7,12-四烯烴、五環[9. 2. 1. 13,9 . 02,10 ]十五-12-烯烴等。這些完全不具有極性基之環狀烯烴單體(c)係可以分別單獨地使用，也可以組合2種以上而使用。As a specific example of the cyclic olefin monomer (c) having no polar group at all, a bicyclo [2.2.1] heptyl-2-olefin (also referred to as "raw spinel"), 5-ethyl- Bicyclo [2.2.1] heptyl-2-olefin, 5-butyl-bicyclo[2.2.1]heptyl-2-olefin, 5-ethylidene-bicyclo[2.2.1]heptyl-2- Olefin, 5-methylidene-bicyclo[2.2.1]heptyl-2-olefin, 5-vinyl-bicyclo[2.2.1]heptyl-2-olefin, tricyclo[5.2.1.0 2,6 ] Dec-3,8-diolefin (common name: dicyclopentadiene), tetracyclo[10.2.1.0 2,11 .0 4,9 ] fifteen-4,6,8,13-tetraene, tetracyclic [6.2.1.1 3,6 .0 2,7 ] Dode-4--4-olefin (also known as "tetracyclododecene".), 9-methyl-tetracyclo[6.2.1.1 3,6 .0 2,7 ] dode-4--4 -olefin, 9-ethyl-tetracyclo[6.2.1.1 3,6 .0 2,7 ]dodec-4-olefin, 9-methylidene-tetracyclo[6. 1. 1 3,6 . 0 2,7 ]dodec-4-olefin, 9-ethylidene-tetracyclo[6. 2. 1. 1 3,6 . 2 2,7 ]dodec-4-ene, 9-vinyl-tetracyclo[6. 2. 1. 1 3,6 . 0 2,7 ]dodec-4-olefin, 9-propenyl-tetracyclo[ 6 . 2. 1. 1 3,6 . 0 2,7 ] 12-4 -olefin, pentacyclo[9. 2. 1. 1 3,9 . 0 2,10 ] fif-5-5,12-diolefin, cyclopentene, cyclopentadiene, 9-phenyl-tetracyclo[6. 2. 1. 1 3,6 . 0 2,7 ]12-4-olefin, tetracyclic [9. 2. 1. 0 2,10 . 0 3,8 ] fourteen-3,5,7,12-four Olefins, pentacyclic [9. 2. 1. 1 3 , 9. 2 2, 10 ] fifteen-12-olefins, and the like. These cyclic olefin monomers (c) having no polar group at all may be used singly or in combination of two or more.

作為環狀烯烴以外之單體(d)之具體例係列舉鏈狀烯烴。作為鏈狀烯烴係列舉例如乙烯；丙烯、1-丁烯、1-戊烯、1-己烯、3-甲基-1-丁烯、3-甲基-1-戊烯、3-乙基-1-戊烯、4-甲基-1-戊烯、4-甲基-1-己烯、4,4-二甲基-1-己烯、4,4-二甲基-1-戊烯、4-乙基-1-己烯、3-乙基-1-己烯、1-辛烯、1-癸烯、1-十二碳烯、1-十四碳烯、1-十六碳烯、1-十八碳烯、1-二十碳烯等之碳數2～20之α-烯烴；1,4-己二烯、4-甲基-1,4-己二烯、5-甲基-1,4-己二烯、1,7-辛二烯等之非共軛二烯等。這些環狀烯烴以外之單體(d)係可以分別單獨或者是組合2種以上而使用。Specific examples of the monomer (d) other than the cyclic olefin include a chain olefin. As the chain olefin series, for example, ethylene; propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl 1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentyl Alkene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexa a olefin having 2 to 20 carbon atoms such as carbene, 1-octadecene or 1-eicene; 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5 a non-conjugated diene such as methyl-1,4-hexadiene or 1,7-octadiene. The monomer (d) other than these cyclic olefins may be used alone or in combination of two or more.

使用於本發明之具有質子性極性基之環狀烯烴樹脂係藉由一起聚合單體(a)以及因為要求而由單體(b)～(d)選出之單體來得到。可以還對於藉由聚合而得到之聚合物，進行氫化。氫化之聚合物係也包含於使用在本發明之具有質子性極性基之環狀烯烴樹脂。The cyclic olefin resin having a protic polar group used in the present invention is obtained by polymerizing a monomer (a) together and a monomer selected from the monomers (b) to (d) as required. Hydrogenation can also be carried out on the polymer obtained by polymerization. The hydrogenated polymer is also included in the cyclic olefin resin having a protic polar group used in the present invention.

此外，使用在本發明之具有質子性極性基之環狀烯烴樹脂係可以在不具有質子性極性基之環狀烯烴樹脂，利用習知之變性劑，導入質子性極性基，即使是由於要求而藉由進行氫化之方法，也可以得到環狀烯烴樹脂。氫化係可以就在導入質子性極性基之前之聚合物而進行。此外，可以在具有質子性極性基之環狀烯烴樹脂，還進行變性而導入質子性極性基。不具有質子性極性基之聚合物係可以藉由任意地組合及聚合前述單體(b)～(d)而得到。Further, the cyclic olefin resin having a protic polar group in the present invention can be introduced into a cyclic olefin resin having no protic polar group, and a protonic polar group can be introduced by a known denaturant, even if it is required A cyclic olefin resin can also be obtained by a method of performing hydrogenation. The hydrogenation can be carried out just before the introduction of the protonic polar group. Further, a cyclic olefin resin having a protic polar group may be denatured to introduce a protic polar group. The polymer having no protic polar group can be obtained by arbitrarily combining and polymerizing the monomers (b) to (d).

作為用以導入質子性極性基之變性劑係通常使用在一分子內具有質子性極性基和反應性之碳-碳不飽和鍵之化合物。作為此種化合物之具體例係列舉丙烯酸、甲基丙烯酸、當歸酸、惕各酸、油酸、反油酸、芥酸、巴西烯酸、順丁烯二酸、富馬酸、檸康酸、中康酸、衣康酸、阿托酸、肉桂酸等之不飽和羧酸；烯丙基醇、甲基乙烯基甲醇、八豆基醇、甲代烯丙基醇、1-苯基乙烯-1-醇、2-丙烯-1-醇、3-丁烯-1-醇、3-丁烯-2-醇、3-甲基-3-丁烯-1-醇、3-甲基-2-丁烯-1-醇、2-甲基-3-丁烯-2-醇、2-甲基-3-丁烯-1-醇、4-戊烯-1-醇、4-甲基-4-戊烯-1-醇、2-己烯-1-醇等之不飽和醇等。使用該變性劑之環狀烯烴樹脂之變性反應係可以按照常法，通常進行於自由基發生劑之存在下。As the denaturing agent for introducing a protic polar group, a compound having a protic polar group and a reactive carbon-carbon unsaturated bond in one molecule is usually used. Specific examples of such compounds include acrylic acid, methacrylic acid, angelic acid, citric acid, oleic acid, elaidic acid, erucic acid, ebutyric acid, maleic acid, fumaric acid, citraconic acid, Unsaturated carboxylic acid such as mesaconic acid, itaconic acid, atropic acid, cinnamic acid, etc.; allyl alcohol, methyl vinyl methanol, octadecyl alcohol, methallyl alcohol, 1-phenylethylene - 1-alcohol, 2-propen-1-ol, 3-buten-1-ol, 3-buten-2-ol, 3-methyl-3-buten-1-ol, 3-methyl-2 -buten-1-ol, 2-methyl-3-buten-2-ol, 2-methyl-3-buten-1-ol, 4-penten-1-ol, 4-methyl- An unsaturated alcohol such as 4-penten-1-ol or 2-hexen-1-ol. The denaturation reaction of the cyclic olefin resin using the denaturing agent can be carried out in the presence of a radical generating agent in accordance with a usual method.

用以一起聚合單體(a)以及因為要求而由單體(b)～(d)來選出之單體之聚合方法係可以按照常法，例如採用開環聚合法或加成聚合法。The polymerization method for polymerizing the monomer (a) together and the monomer selected from the monomers (b) to (d) as required may be carried out according to a usual method, for example, a ring-opening polymerization method or an addition polymerization method.

作為聚合觸媒係適合使用例如鉬、釕、鋨等之金屬錯合物。這些聚合觸媒係可以分別單獨或者是組合2種以上而使用。聚合觸媒量係聚合觸媒中之金屬化合物：環狀烯烴之莫爾數比而通常成為1：100～1：2,000,000、最好是1：500～1：1,000,000更加理想是1：1,000～1：500,000之範圍。As the polymerization catalyst, a metal complex such as molybdenum, rhodium, ruthenium or the like is suitably used. These polymerization catalysts may be used alone or in combination of two or more. The polymerization catalyst amount is a metal compound in the polymerization catalyst: the molar ratio of the cyclic olefin is usually 1:100 to 1:2,000,000, preferably 1:500 to 1:1,000,000, more preferably 1:1,000 to 1 : Range of 500,000.

聚合各單體而得到之聚合物之氫化係通常使用氫化觸媒而進行。作為氫化觸媒係可以使用例如在烯烴化合物之氫化之際而一般使用者。具體地說，可以利用齊格勒(Ziegler)形式之均一系觸媒、貴金屬錯合物觸媒和附載型貴金屬系觸媒等。The hydrogenation of the polymer obtained by polymerizing each monomer is usually carried out using a hydrogenation catalyst. As the hydrogenation catalyst system, for example, a general user can be used at the time of hydrogenation of an olefin compound. Specifically, a uniform catalyst such as a Ziegler type, a noble metal complex catalyst, and a supported noble metal catalyst can be used.

在這些氫化觸媒中，由不引起官能基變性等之副反應而能夠呈選擇性地氫化聚合物中之主鏈之碳-碳不飽和鍵之方面來看的話，則最好是銠、釕等之貴金屬錯合物觸媒，特別最好是高電子給予性之含氮雜環式香芹烯化合物或膦類呈配位之釕觸媒。Among these hydrogenation catalysts, those which are capable of selectively hydrogenating a carbon-carbon unsaturated bond of a main chain in a polymer by a side reaction which does not cause denaturation of a functional group or the like are preferably ruthenium and osmium. The noble metal complex catalyst is particularly preferably a high electron donating nitrogen-containing heterocyclic carotenoid compound or a phosphine-based rhodium catalyst.

氫化之聚合物之主鏈之氫化率係通常為90%以上、最好是95%以上、更加理想是98%以上。在氫化率位處於該範圍時，樹脂(A)係特別是耐熱性良好而變得適當。樹脂(A)之氫化率係可以藉由1 H-NMR光譜而測定。例如可以成為氫化之碳-碳雙鍵莫爾數相對於氫化前之碳-碳雙鍵莫爾數之比例而求出。The hydrogenation ratio of the main chain of the hydrogenated polymer is usually 90% or more, preferably 95% or more, and more preferably 98% or more. When the hydrogenation rate is in this range, the resin (A) is particularly excellent in heat resistance and is suitable. The hydrogenation ratio of the resin (A) can be measured by 1 H-NMR spectrum. For example, it can be determined as a ratio of the number of carbon-carbon double bonds of hydrogenation to the molar number of carbon-carbon double bonds before hydrogenation.

在本發明，作為具有質子性極性基之環狀烯烴樹脂係特別適合具有藉由以下顯示之化學式(2)所表示之構造單位，更加理想是具有藉由化學式(2)所表示之構造單位和藉由化學式(3)所表示之構造單位。In the present invention, the cyclic olefin resin having a protic polar group is particularly preferably having a structural unit represented by the chemical formula (2) shown below, and more desirably has a structural unit represented by the chemical formula (2) and The structural unit represented by the chemical formula (3).

[在化學式(2)中，R1 ～R4 係分別獨立地成為氫原子或-Xn -R’基(X係2價之有機基；n係0或1；R’係可以具有取代基之烷基、可以具有取代基之芳香族基或質子性極性基。)。R1 ～R4 中之至少一個係R’為質子性極性基之-Xn -R’基。m係0～2之整數。][In the chemical formula (2), R 1 to R 4 each independently form a hydrogen atom or a -X n -R' group (X-based divalent organic group; n-form 0 or 1; R'-system may have a substituent An alkyl group, an aromatic group or a protic polar group which may have a substituent.). At least one of R 1 to R 4 is a —X n —R′ group of a protic polar group. m is an integer from 0 to 2. ]

[在化學式(3)中，R5 ～R8 係以任意之組合而形成一起包含這些鍵結之2個之碳原子和作為環構造原子之氧原子或氮原子之3～5員之雜環構造，該雜環係可以在該雜環，具有取代基。k係0～2之整數。][In the chemical formula (3), R 5 to R 8 are formed into a heterocyclic ring containing two carbon atoms of these bonds and three to five members of the oxygen atom or nitrogen atom as a ring structure atom in any combination. In the structure, the heterocyclic ring may have a substituent in the heterocyclic ring. k is an integer from 0 to 2. ]

在通式(2)中，作為藉由X所表示之2價之有機基之例子係列舉亞甲基、乙烯基和羰基等。In the general formula (2), examples of the divalent organic group represented by X include a methylene group, a vinyl group, a carbonyl group and the like.

藉由R’所表示且可以具有取代基之烷基係通常為直鏈或支鏈之碳數1～7之烷基，作為其例子係列舉甲基、乙基、n-丙基、異丙基等。可以具有取代基之芳香族基係通常為碳數6～10之芳香族基，作為其例子係列舉苯基、苄基等。作為這些烷基或芳香族基之取代基之例子係列舉甲基、乙基、n-丙基、異丙基、n-丁基、異丁基等之碳數1～4之烷基；苯基、二甲苯基、甲苯基、萘基等之碳數6～12之芳基等。The alkyl group represented by R' and which may have a substituent is usually a linear or branched alkyl group having 1 to 7 carbon atoms, and examples thereof include methyl, ethyl, n-propyl and isopropyl groups. Base. The aromatic group which may have a substituent is usually an aromatic group having 6 to 10 carbon atoms, and examples thereof include a phenyl group and a benzyl group. Examples of the substituent of the alkyl group or the aromatic group include a methyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group; An aryl group having 6 to 12 carbon atoms such as a group, a xylyl group, a tolyl group or a naphthyl group.

作為藉由R’所表示之質子性極性基係列舉前述基。在通式(3)，作為R5 ～R8 以任意之組合而一起形成這些鍵結之2個之碳原子之3員之雜環構造係列舉環氧構造等。此外，作為相同之5員之雜環構造之例子係列舉二羧酸酐構造[-C(=O)-O-C(=O)-]、二羧基醯亞胺構造[-C(=O)-N-C(=O)-]等。作為鍵結於該雜環之取代基之例子係列舉苯基、萘基、蒽基等。The above-mentioned group is mentioned as a series of protic polar groups represented by R'. In the general formula (3), a heterocyclic structure series of three members in which two carbon atoms of these bonds are formed together in any combination of R 5 to R 8 is an epoxy structure. In addition, as an example of a heterocyclic structure of the same five members, a dicarboxylic anhydride structure [-C(=O)-OC(=O)-], a dicarboxy quinone imine structure [-C(=O)-NC (=O)-] and so on. Examples of the substituent bonded to the hetero ring include a phenyl group, a naphthyl group, an anthracenyl group and the like.

使用於本發明之丙烯樹脂係並無特別限定，但是，最好是以由具有丙烯基之羧酸、具有丙烯基之羧酸酐或含環氧基丙烯酸酯化合物而選出之至少一個來作為單體之均聚物或共聚物。The propylene resin to be used in the present invention is not particularly limited, but is preferably one selected from at least one selected from the group consisting of a carboxylic acid having a propenyl group, a carboxylic acid anhydride having an acryl group, or an epoxy group-containing acrylate compound. a homopolymer or copolymer.

作為具有丙烯基之羧酸之具體例係列舉(甲基)丙烯酸、順丁烯二酸、富馬酸、檸康酸、中康酸、戊烯二酸等；作為具有丙烯基之羧酸酐之具體例係列舉順丁烯二酸酐、檸康酸酐等；作為含環氧基丙烯酸酯化合物之具體例係列舉丙烯酸環氧丙酯、甲基丙烯酸環氧丙酯、α-乙基丙烯酸環氧丙基、α-n-丙基丙烯酸環氧丙基、α-n-丁基丙烯酸環氧丙基、丙烯酸-3,4-環氧丁基、甲基丙烯酸-3,4-環氧丁基、丙烯酸-6,7-環氧庚基、甲基丙烯酸-6,7-環氧庚基、α-乙基丙烯酸-6,7-環氧庚基等。Specific examples of the carboxylic acid having a propylene group include (meth)acrylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, glutaconic acid, and the like; as a carboxylic acid anhydride having a propenyl group Specific examples include maleic anhydride, citraconic anhydride, etc.; as a specific example of the epoxy group-containing acrylate compound, propylene acrylate, propylene glycol methacrylate, and α-ethyl acrylate propylene Base, α-n-propyl acrylate epoxypropyl, α-n-butyl acrylate epoxy propyl, acrylate-3,4-epoxy butyl, methacrylic acid-3,4-epoxy butyl, Acetic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethyl acrylate-6,7-epoxyheptyl and the like.

在這些當中，最好是(甲基)丙烯酸、順丁烯二酸酐、甲基丙烯酸環氧丙酯、甲基丙烯酸-6,7-環氧庚基等。在本發明之所謂「(甲基)」係表示甲基丙烯和丙烯之任何一種。Among these, (meth)acrylic acid, maleic anhydride, glycidyl methacrylate, -6,7-epoxyheptyl methacrylate and the like are preferable. The term "(meth)" in the present invention means any one of methacrylic acid and propylene.

丙烯樹脂係可以是由不飽和羧酸、不飽和羧酸酐和含環氧基不飽和化合物而選出之至少一個單體以及其他之丙烯酸酯系單體或丙烯酸酯以外之可共聚之單體之共聚物。作為其他之丙烯酸酯系單體係最好是甲基(甲基)丙烯酸酯、異丙基(甲基)丙烯酸酯、丁基(甲基)丙烯酸酯、t-丁基(甲基)丙烯酸酯、乙基己基(甲基)丙烯酸酯、癸基(甲基)丙烯酸酯、十二烷基(甲基)丙烯酸酯、月桂基(甲基)丙烯酸酯、硬脂醯(甲基)丙烯酸酯等之烷基(甲基)丙烯酸酯；羥基乙基(甲基)丙烯酸酯、2-羥基丙基(甲基)丙烯酸酯、3-羥基丙基(甲基)丙烯酸酯等之羥基烷基(甲基)丙烯酸酯；苯氧基乙基(甲基)丙烯酸酯、2-羥基-3-苯氧基丙基(甲基)丙烯酸酯等之苯氧基烷基(甲基)丙烯酸酯；2-甲氧基乙基(甲基)丙烯酸酯、2-乙氧基乙基(甲基)丙烯酸酯等之烷氧基烷基(甲基)丙烯酸酯；聚乙烯乙二醇單(甲基)丙烯酸酯、乙氧基二乙烯乙二醇(甲基)丙烯酸酯、甲氧基聚乙烯乙二醇(甲基)丙烯酸酯、苯氧基聚乙烯乙二醇(甲基)丙烯酸酯等之聚烷撐乙二醇(甲基)丙烯酸酯；環己基(甲基)丙烯酸酯、4-丁基環己基(甲基)丙烯酸酯、二環戊烷基(甲基)丙烯酸酯、二環戊烯基(甲基)丙烯酸酯、二環戊二烯基(甲基)丙烯酸酯、冰片基(甲基)丙烯酸酯、異冰片基(甲基)丙烯酸酯、三環癸烷基(甲基)丙烯酸酯等之環烷基(甲基)丙烯酸酯；苄基(甲基)丙烯酸酯、四氫化糠基(甲基)丙烯酸酯等。在這些當中，最好是丁基(甲基)丙烯酸酯、乙基己基(甲基)丙烯酸酯、月桂基(甲基)丙烯酸酯、異癸基(甲基)丙烯酸酯和2-乙氧基乙基(甲基)丙烯酸酯等。The propylene resin may be a copolymer of at least one monomer selected from an unsaturated carboxylic acid, an unsaturated carboxylic anhydride, and an epoxy group-containing unsaturated compound, and other copolymerizable monomers other than the acrylate monomer or acrylate. Things. The other acrylate system is preferably methyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, t-butyl (meth) acrylate. Ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearic acid (meth) acrylate, etc. Alkyl (meth) acrylate; hydroxyalkyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, etc. a phenoxyalkyl (meth) acrylate such as phenoxyethyl (meth) acrylate or 2-hydroxy-3-phenoxypropyl (meth) acrylate; Alkoxyalkyl (meth) acrylate such as methoxyethyl (meth) acrylate or 2-ethoxyethyl (meth) acrylate; polyethylene glycol mono (meth) acrylate Polyalkane such as ester, ethoxy diethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate Ethylene glycol (meth) acrylate; Hexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentadiene a cycloalkyl (meth) acrylate such as a methacrylate, a borneol (meth) acrylate, an isobornyl (meth) acrylate or a tricyclodecyl (meth) acrylate; Benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and the like. Among these, preferred are butyl (meth) acrylate, ethyl hexyl (meth) acrylate, lauryl (meth) acrylate, isodecyl (meth) acrylate and 2-ethoxy group. Ethyl (meth) acrylate or the like.

作為丙烯酸酯以外之可共聚之單體係如果是可共聚於前述具有丙烯基之羧酸、具有丙烯基之羧酸酐或含環氧基丙烯酸酯化合物之化合物的話，則並無特別限制，但是，列舉例如乙烯基苄基甲基醚、乙烯基環氧丙基醚、苯乙烯、α-甲基苯乙烯、丁二烯、異戊二烯等之含乙烯基自由基聚合性化合物。這些化合物係可以分別單獨地使用，也可以組合2種以上而使用。前述單體之聚合方法係可以按照常法，例如採用懸濁聚合法、乳化聚合法、溶液聚合法等。The single system which is copolymerizable other than the acrylate is not particularly limited as long as it is copolymerizable with the above-mentioned carboxylic acid having a propenyl group, a carboxylic acid anhydride having a propenyl group or a compound containing an epoxy group-containing acrylate compound, but is not particularly limited. A vinyl group-containing radical polymerizable compound such as vinylbenzyl methyl ether, vinyl epoxypropyl ether, styrene, α-methylstyrene, butadiene or isoprene is exemplified. These compounds may be used alone or in combination of two or more. The polymerization method of the above monomers can be carried out according to a usual method, for example, a suspension polymerization method, an emulsion polymerization method, a solution polymerization method, or the like.

所謂軸節樹脂係具有軸節構造、也就是在構成環狀構造之4級碳原子來鍵結2個環狀構造之骨格構造之樹脂。一般之軸節構造係在芴環來鍵結苯環。The shaft joint resin has a shaft structure, that is, a resin having a skeleton structure in which two carbon atoms are formed in a ring structure to bond two annular structures. The general axon structure is bonded to the benzene ring in the anthracene ring.

作為在構成環狀構造之4級碳原子來鍵結2個環狀構造之骨格構造之具體例係列舉芴骨格、雙酚芴骨格、雙胺基苯基芴骨格、具有環氧基之芴骨格、具有丙烯基之芴骨格等。A series of specific examples of the skeleton structure in which two annular structures are bonded to the four-stage carbon atom constituting the annular structure, the sacral lattice, the bisphenol sorghum, the bisaminophenyl sorghum, and the cerium having an epoxy group. , with a propylene base and so on.

使用於本發明之軸節樹脂係藉由具有該軸節構造之骨格來鍵結於此之官能基間之反應等而進行聚合來形成。軸節樹脂係具有藉由1個元素而繫接主鏈和體積大之側鏈之構造(軸節構造)，在對於主鏈呈幾乎垂直之方向，具有環狀構造。The shaft resin used in the present invention is formed by polymerization by a reaction between the functional groups bonded thereto by the skeleton having the shaft structure. The shaft joint resin has a structure (a shaft joint structure) in which a main chain and a bulk side chain are connected by one element, and has an annular structure in a direction substantially perpendicular to the main chain.

在化學式(4)，顯示具有環氧環氧丙基醚構造之軸節構造之例子。In the chemical formula (4), an example of a shaft joint structure having an epoxyepoxypropyl ether structure is shown.

(在化學式(4)中，n係表示0～10之整數。)(In the chemical formula (4), n represents an integer of 0 to 10.)

具有軸節構造之單體係列舉例如雙(環氧丙基羥苯基)芴型環氧樹脂；雙酚芴型環氧樹脂和丙烯酸之縮合物；9,9-雙(4-羥基苯基)芴、9,9-雙(4-羥基-3-甲基苯基)芴等之含軸節構造雙酚類；9,9-雙(氰基甲基)芴等之9,9-雙(氰基烷基)芴類；9,9-雙(3-胺基丙基)芴等之9,9-雙(胺基烷基)芴類等。軸節樹脂係聚合具有軸節構造之單體而得到之聚合物，但是，可以是和其他之可共聚之單體之共聚物。前述單體之聚合方法係可以按照常法。A series of monomers having a shaft joint structure, for example, a bis(epoxypropyl hydroxyphenyl) fluorene type epoxy resin; a condensate of a bisphenol fluorene type epoxy resin and acrylic acid; 9,9-bis(4-hydroxyphenyl)芴, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, etc., containing bisphenols; 9,9-bis(cyanomethyl)anthracene 9,9-double (Cyanoalkyl) anthracene; 9,9-bis(aminoalkyl)anthracene or the like of 9,9-bis(3-aminopropyl)anthracene or the like. The shaft joint resin is a polymer obtained by polymerizing a monomer having a shaft joint structure, but may be a copolymer with other copolymerizable monomers. The polymerization method of the aforementioned monomers can be carried out in accordance with a conventional method.

使用於本發明之聚矽氧烷之構造係並無特別限定，但是，最好是列舉藉由混合‧反應以化學式(5)所表示之有機矽烷之1種以上而得到之聚矽氧烷。The structure of the polyoxyalkylene to be used in the present invention is not particularly limited, and it is preferable to use a polyoxyalkylene obtained by mixing one or more kinds of organic decane represented by the chemical formula (5) by mixing the ‧ reaction.

化學式(5)之R9 係表示氫、碳數1～10之烷基、碳數2～10之鏈烯基、碳數6～15之芳基之任何一種，複數個之R9 係可以分別相同或不同。此外，這些烷基、鏈烯基、芳基係皆可以具有取代基，並且，也可以是不具有取代基之無取代體，可以配合組成物之特性而進行選擇。作為烷基之具體例係列舉甲基、乙基、n-丙基、異丙基、n-丁基、t-丁基、n-己基、n-癸基、三氟甲基、2,2,2-三氟甲基、3,3,3-三氟丙基、3-環氧丙氧基丙基、2-(3,4-環氧環己基)乙基、3-胺基丙基、3-巰基丙基、3-異氰酸酯丙基。作為鏈烯基之具體例係列舉乙烯基、3-丙烯醯基丙基、3-甲基丙烯醯基丙基。作為芳基之具體例係列舉苯基、甲苯基、p-羥基苯基、1-(p-羥基苯基)乙基、2-(p-羥基苯基)乙基、4-羥基-5-(p-羥基苯基羰基羥基)戊基、萘基。R 9 of the formula (5) represents any one of hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an aryl group having 6 to 15 carbon atoms, and the plurality of R 9 groups may be respectively Same or different. Further, these alkyl groups, alkenyl groups, and aryl groups may have a substituent, and may be an unsubstituted body having no substituent, and may be selected in accordance with the characteristics of the composition. Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-hexyl, n-fluorenyl, trifluoromethyl, 2,2. , 2-trifluoromethyl, 3,3,3-trifluoropropyl, 3-glycidoxypropyl, 2-(3,4-epoxycyclohexyl)ethyl, 3-aminopropyl , 3-mercaptopropyl, 3-isocyanate propyl. Specific examples of the alkenyl group include vinyl, 3-propenylpropyl, and 3-methylpropenylpropyl. Specific examples of the aryl group include phenyl, tolyl, p-hydroxyphenyl, 1-(p-hydroxyphenyl)ethyl, 2-(p-hydroxyphenyl)ethyl, 4-hydroxy-5-. (p-Hydroxyphenylcarbonylhydroxy)pentyl, naphthyl.

化學式(5)之R10 係表示氫、碳數1～6之烷基、碳數1～6之醯基、碳數6～15之芳基之任何一種，複數個之R10 係可以分別相同或不同。此外，這些烷基、醯基係皆可以具有取代基，並且，也可以是不具有取代基之無取代體，可以配合組成物之特性而進行選擇。作為烷基之具體例係列舉甲基、乙基、n-丙基、異丙基、n-丁基。作為醯基之具體例係列舉乙醯基。作為芳基之具體例係列舉苯基。化學式(5)之n係表示由0至3之整數。在n=0之狀態下，成為4官能性矽烷，在n=1之狀態下，成為3官能性矽烷，在n=2之狀態下，成為2官能性矽烷，在n=3之狀態下，成為1官能性矽烷。R 10 of the formula (5) represents any one of hydrogen, an alkyl group having 1 to 6 carbon atoms, a fluorenyl group having 1 to 6 carbon atoms, and an aryl group having 6 to 15 carbon atoms, and the plurality of R 10 groups may be respectively the same. Or different. Further, these alkyl groups and fluorenyl groups may have a substituent, and may be an unsubstituted body having no substituent, and may be selected in accordance with the characteristics of the composition. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. As a specific example of the sulfhydryl group, it is exemplified. As a specific example of the aryl group, a phenyl group is mentioned. n of the chemical formula (5) represents an integer of from 0 to 3. In the state of n=0, the tetrafunctional decane is a trifunctional decane, and in the state of n=2, it becomes a bifunctional decane, and in the state of n=3, It becomes a monofunctional decane.

作為藉由化學式(5)所表示之有機矽烷之具體例係列舉四甲氧基矽烷、四乙氧基矽烷等之4官能性矽烷；甲基三甲氧基矽烷、甲基三乙氧基矽烷、乙基三甲氧基矽烷、乙基三乙氧基矽烷、乙基三異丙氧基矽烷、乙基三n-丁氧基矽烷、n-丙基三甲氧基矽烷、n-丁基三甲氧基矽烷、n-己基三甲氧基矽烷、n-己基三乙氧基矽烷、癸基三甲氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、3-甲基丙烯醯基丙基三甲氧基矽烷、3-丙烯醯基丙基三甲氧基矽烷、苯基三甲氧基矽烷、p-羥基苯基三甲氧基矽烷、2-(p-羥基苯基)乙基三甲氧基矽烷、4-羥基-5-(p-羥基苯基羰基羥基)戊基三甲氧基矽烷、三氟甲基三甲氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-巰基丙基三甲氧基矽烷等之3官能性矽烷；二甲基二甲氧基矽烷、二甲基二乙氧基矽烷、二甲基二乙酸基矽烷、二n-丁基二甲氧基矽烷、二苯基二甲氧基矽烷等之2官能性矽烷；三甲基甲氧基矽烷、三n-丁基乙氧基矽烷等之1官能性矽烷。Specific examples of the organodecane represented by the chemical formula (5) include tetrafunctional decane such as tetramethoxy decane or tetraethoxy decane; methyltrimethoxydecane and methyltriethoxydecane; Ethyltrimethoxydecane, ethyltriethoxydecane, ethyltriisopropoxydecane, ethyltri-n-butoxydecane, n-propyltrimethoxydecane, n-butyltrimethoxy Decane, n-hexyltrimethoxydecane, n-hexyltriethoxydecane, decyltrimethoxydecane,vinyltrimethoxydecane,vinyltriethoxydecane,3-methylpropenylpropyl Trimethoxy decane, 3-propenyl propyl trimethoxy decane, phenyl trimethoxy decane, p-hydroxyphenyl trimethoxy decane, 2-(p-hydroxyphenyl) ethyl trimethoxy decane, 4-hydroxy-5-(p-hydroxyphenylcarbonylhydroxy)pentyltrimethoxydecane, trifluoromethyltrimethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethyl 3 of oxydecane, 3-glycidoxypropyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, etc. Functional decane; dimethyl dimethoxy decane, dimethyl diethoxy decane, dimethyl diacetoxy decane, di n-butyl dimethoxy decane, diphenyl dimethoxy decane, etc. a bifunctional decane; a monofunctional decane such as trimethyl methoxy decane or tri-n-butyl ethoxy decane.

在這些有機矽烷中，由本發明之樹脂組成物來得到之樹脂膜之耐破裂性或硬度之方面來看的話，則最好是使用3官能性矽烷。此外，這些有機矽烷係可以單獨地使用，也可以組合2種以上而使用。Among these organic decanes, trifunctional decane is preferably used in view of the crack resistance or hardness of the resin film obtained from the resin composition of the present invention. Further, these organic decane systems may be used singly or in combination of two or more.

本發明之聚矽氧烷係藉由水解及部分縮合前述有機矽烷而得到。可以在水解及部分縮合，使用一般之方法。例如在混合物，添加溶媒、水以及配合需要之觸媒，進行加熱‧攪拌。可以在攪拌中，配合需要，藉由蒸餾而餾除水解副產物(甲醇等之醇)或縮合副產物(水)。The polyoxyalkylene of the present invention is obtained by hydrolyzing and partially condensing the aforementioned organodecane. The hydrolysis can be carried out and partial condensation can be carried out using a general method. For example, in a mixture, a solvent, water, and a catalyst to be blended are added, and heating and stirring are carried out. The hydrolysis by-product (alcohol of methanol or the like) or the condensation by-product (water) may be distilled off by distillation, if necessary, by distillation.

使用於本發明之聚醯亞胺係可以藉由對於以反應四羧酸酐和二胺而得到之聚醯亞胺先驅物，來進行熱處理而得到。作為用以得到聚醯亞胺樹脂之先驅物係有聚醯胺酸、聚醯胺酸酯、聚異醯亞胺、聚醯胺酸磺胺等。The polyimide used in the present invention can be obtained by heat-treating a polyimide precursor obtained by reacting a tetracarboxylic anhydride with a diamine. The precursors for obtaining the polyimide resin include polyglycolic acid, polyphthalamide, polyisodecimide, polysulfate sulfonamide, and the like.

作為可以使用成為聚醯亞胺原料之酸二酐係可以具體地列舉均苯四甲酸二酐、3,3’,4,4’-聯苯基四羧酸二酐、2,3,3’,4’-聯苯基四羧酸二酐、2,2’,3,3’-聯苯基四羧酸二酐、3,3’,4,4’-二苯甲酮四羧酸二酐、2,2’,3,3’-二苯甲酮四羧酸二酐、2,2-雙(3,4-二羧基苯基)丙烷二酐、2,2-雙(2,3-二羧基苯基)丙烷二酐、1,1-雙(3,4-二羧基苯基)乙烷二酐、1,1-雙(2,3-二羧基苯基)乙烷二酐、雙(3,4-二羧基苯基)甲烷二酐、雙(2,3-二羧基苯基)甲烷二酐、雙(3,4-二羧基苯基)碸二酐、雙(3,4-二羧基苯基)醚二酐、1,2,5,6-萘四羧酸二酐、2,3,6,7-萘四羧酸二酐、2,3,5,6-吡啶四羧酸二酐、3,4,9,10-二萘嵌苯四羧酸二酐、2,2-雙(3,4-二羧基苯基)六氟丙烷二酐等之芳香族四羧酸二酐或丁烷四羧酸二酐、1,2,3,4-環戊烷四羧酸二酐等之脂肪族四羧酸二酐等。這些酸二酐係可以單獨或者是組合2種以上而使用。Specific examples of the acid dianhydride which can be used as the raw material of the polyimine may be pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3'. , 4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid Anhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis (2,3) -dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, Bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)ruthenic anhydride, bis(3,4 -dicarboxyphenyl)ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridine four Aromatic tetracarboxylic acid such as carboxylic acid dianhydride, 3,4,9,10-perylene tetracarboxylic dianhydride or 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride An aliphatic tetracarboxylic dianhydride such as dianhydride or butane tetracarboxylic dianhydride or 1,2,3,4-cyclopentanetetracarboxylic dianhydride. These acid dianhydrides can be used individually or in combination of 2 or more types.

作為可以使用成為聚醯亞胺原料之二胺之具體例係列舉3,4’-二胺基二苯基醚、4,4’-二胺基二苯基醚、3,4’-二胺基二苯基甲烷、4,4’-二胺基二苯基甲烷、3,4’-二胺基二苯基碸、4,4’-二胺基二苯基碸、3,4’-二胺基二苯基硫醚、4,4’-二胺基二苯基硫醚、1,4-雙(4-胺基苯氧基)苯、苯炔、m-苯撐二胺、p-苯撐二胺、1,5-萘二胺、2,6-萘二胺、雙(4-胺基苯氧基苯基)碸、雙(3-胺基苯氧基苯基)碸、雙(4-胺基苯氧基)聯苯基、雙{4-(4-胺基苯氧基)苯基}醚、1,4-雙(4-胺基苯氧基)苯、2,2’-二甲基-4,4’-二胺基聯苯基、2,2’-二乙基-4,4’-二胺基聯苯基、3,3’-二甲基-4,4’-二胺基聯苯基、3,3’-二乙基-4,4’-二胺基聯苯基、2,2’,3,3’-四甲基-4,4’-二胺基聯苯基、3,3’,4,4’-四甲基-4,4’-二胺基聯苯基、2,2’-二(三氟甲基)-4,4’-二胺基聯苯基、或者是在這些之芳香族環藉由烷基或鹵素原子而進行取代之化合物、或者是脂肪族之環己基二胺、亞甲基雙環己基胺等。這些二胺係可以單獨或者是組合2種以上而使用。As a specific example of a diamine which can be used as a raw material of a polyimine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diamine Diphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylanthracene, 4,4'-diaminodiphenylanthracene, 3,4'- Diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 1,4-bis(4-aminophenoxy)benzene, benzyne, m-phenylenediamine, p -phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxyphenyl)anthracene, bis(3-aminophenoxyphenyl)anthracene, Bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl}ether, 1,4-bis(4-aminophenoxy)benzene, 2, 2'-Dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4 , 4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4' -diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4 '-Diaminobiphenyl, or an aromatic ring in these by alkyl or halogen Substitution of compound atom, a cyclohexyl diamine or of an aliphatic, methylene dicyclohexyl amine and the like. These diamines can be used singly or in combination of two or more.

使用於本發明之聚醯亞胺係藉由習知之方法而進行合成。也就是說，呈選擇性地組合四羧酸二酐和二胺，藉由在N-甲基-2-吡咯烷酮、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺、二甲基亞碼、六甲基磷三醯胺、γ-丁內酯、環戊酮等之極性溶媒中進行反應等之習知方法而合成這些。The polyimine used in the present invention is synthesized by a conventional method. That is, the tetracarboxylic dianhydride and the diamine are selectively combined by using N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamidine. These are synthesized by a conventional method in which a reaction is carried out in a polar solvent such as an amine, a dimethyl subcode, hexamethylphosphoric acid triamide, γ-butyrolactone or cyclopentanone.

使用於本發明且包含藉由通式(1)所表示之單體之單位(e)之樹脂係包含藉由聚合以下列之通式(1)所表示之單體而得到之單位(e)來組成之環狀烯烴樹脂。The resin used in the present invention and comprising the unit (e) of the monomer represented by the general formula (1) contains a unit (e) obtained by polymerizing a monomer represented by the following general formula (1). To form a cyclic olefin resin.

(在前述化學式(1)中，R1 係表示碳數5～16之支鏈狀烷基。)(In the above chemical formula (1), R 1 represents a branched alkyl group having 5 to 16 carbon atoms.)

在前述通式(1)，R1 係碳數5～16之支鏈狀烷基，列舉例如1-甲基丁基、2-甲基丁基、1-甲基戊基、1-乙基丁基、2-甲基己基、2-乙基己基、4-甲基庚基、1-甲基壬基、1-甲基三癸基、1-甲基四癸基等。即使是在這些當中，也由於耐熱性和對於有機溶媒之溶解性而變得良好，因此，最好是碳數6～14之支鏈狀烷基，更加理想是碳數7～10之支鏈狀烷基。在碳數為4以下時，對於有機溶媒之溶解性變差，在碳數為17以上時，耐熱性變差，並且，還有所謂圖案化之樹脂膜由於熱而熔融來消失圖案之問題發生。In the above formula (1), R 1 is a branched alkyl group having 5 to 16 carbon atoms, and examples thereof include 1-methylbutyl group, 2-methylbutyl group, 1-methylpentyl group, and 1-ethyl group. Butyl, 2-methylhexyl, 2-ethylhexyl, 4-methylheptyl, 1-methylindenyl, 1-methyltridecyl, 1-methyltetradecyl, and the like. Even among these, since it is excellent in heat resistance and solubility in an organic solvent, it is preferably a branched alkyl group having 6 to 14 carbon atoms, more preferably a branch having 7 to 10 carbon atoms. Alkyl group. When the carbon number is 4 or less, the solubility in the organic solvent is deteriorated, and when the carbon number is 17 or more, the heat resistance is deteriorated, and the problem that the patterned resin film is melted by heat to disappear the pattern occurs. .

作為藉由前述通式(1)所表示之單體之具體例係列舉N-(1-甲基丁基)-二環[2.2.1]庚基-5-烯烴-2,3-二羧基醯亞胺、N-(2-甲基丁基)-二環[2.2.1]庚基-5-烯烴-2,3-二羧基醯亞胺、N-(1-甲基戊基)-二環[2.2.1]庚基-5-烯烴-2,3-二羧基醯亞胺、N-(2-甲基戊基)-二環[2.2.1]庚基-5-烯烴-2,3-二羧基醯亞胺、N-(1-乙基丁基)-二環[2.2.1]庚基-5-烯烴-2,3-二羧基醯亞胺、N-(2-乙基丁基)-二環[2.2.1]庚基-5-烯烴-2,3-二羧基醯亞胺、N-(1-甲基己基)-二環[2.2.1]庚基-5-烯烴-2,3-二羧基醯亞胺、N-(2-甲基己基)-二環[2.2.1]庚基-5-烯烴-2,3-二羧基醯亞胺、N-(3-甲基己基)-二環[2.2.1]庚基-5-烯烴-2,3-二羧基醯亞胺、N-(1-丁基戊基)-二環[2.2.1]庚基-5-烯烴-2,3-二羧基醯亞胺、N-(2-丁基戊基)-二環[2.2.1]庚基-5-烯烴-2,3-二羧基醯亞胺、N-(1-甲基庚基)-二環[2.2.1]庚基-5-烯烴-2,3-二羧基醯亞胺、N-(2-甲基庚基)-二環[2.2.1]庚基-5-烯烴-2,3-二羧基醯亞胺、N-(3-甲基庚基)-二環[2.2.1]庚基-5-烯烴-2,3-二羧基醯亞胺、N-(4-甲基庚基)-二環[2.2.1]庚基-5-烯烴-2,3-二羧基醯亞胺、N-(1-乙基己基)-二環[2.2.1]庚基-5-烯烴-2,3-二羧基醯亞胺、N-(2-乙基己基)-二環[2.2.1]庚基-5-烯烴-2,3-二羧基醯亞胺、N-(3-乙基己基)-二環[2.2.1]庚基-5-烯烴-2,3-二羧基醯亞胺、N-(1-丙基戊基)-二環[2.2.1]庚基-5-烯烴-2,3-二羧基醯亞胺、N-(2-丙基戊基)-二環[2.2.1]庚基-5-烯烴-2,3-二羧基醯亞胺、N-(1-甲基辛基)-二環[2.2.1]庚基-5-烯烴-2,3-二羧基醯亞胺、N-(2-甲基辛基)-二環[2.2.1]庚基-5-烯烴-2,3-二羧基醯亞胺、N-(3-甲基辛基)-二環[2.2.1]庚基-5-烯烴-2,3-二羧基醯亞胺、N-(4-甲基辛基)-二環[2.2.1]庚基-5-烯烴-2,3-二羧基醯亞胺、N-(1-乙基庚基)-二環[2.2.1]庚基-5-烯烴-2,3-二羧基醯亞胺、N-(2-乙基庚基)-二環[2.2.1]庚基-5-烯烴-2,3-二羧基醯亞胺、N-(3-乙基庚基)-二環[2.2.1]庚基-5-烯烴-2，3-二羧基醯亞胺、N-(4-乙基庚基)-二環[2.2.1]庚基-5-烯烴-2,3-二羧基醯亞胺、N-(1-丙基己基)-二環[2.2.1]庚基-5-烯烴-2,3-二羧基醯亞胺、N-(2-丙基己基)-二環[2.2.1]庚基-5-烯烴-2,3-二羧基醯亞胺、N-(3-丙基己基)-二環[2.2.1]庚基-5-烯烴-2,3-二羧基醯亞胺、N-(1-甲基壬基)-二環[2.2.1]庚基-5-烯烴-2,3-二羧基醯亞胺、N-(2-甲基壬基)-二環[2.2.1]庚基-5-烯烴-2,3-二羧基醯亞胺、N-(3-甲基壬基)-二環[2.2.1]庚基-5-烯烴-2,3-二羧基醯亞胺、N-(4-甲基壬基)-二環[2.2.1]庚基-5-烯烴-2,3-二羧基醯亞胺、N-(5-甲基壬基)-二環[2.2.1]庚基-5-烯烴-2,3-二羧基醯亞胺、N-(1-乙基辛基)-二環[2.2.1]庚基-5-烯烴-2,3-二羧基醯亞胺、N-(2-乙基辛基)-二環[2. 2. 1]庚基-5-烯烴-2,3-二羧基醯亞胺、N-(3-乙基辛基)-二環[2. 2. 1]庚基-5-烯烴-2,3-二羧基醯亞胺、N-(4-乙基辛基)-二環[2. 2. 1]庚基-5-烯烴-2,3-二羧基醯亞胺、N-(1-甲基癸基)-二環[2. 2. 1]庚基-5-烯烴-2,3-二羧基醯亞胺、N-(1-甲基十二烷基)-二環[2. 2. 1]庚基-5-烯烴-2,3-二羧基醯亞胺、N-(1-甲基十一烷基)-二環[2.2.1]庚基-5-烯烴-2,3-二羧基醯亞胺、N-(1-甲基十二烷基)-二環[2. 2. 1]庚基-5-烯烴-2,3-二羧基醯亞胺、N-(1-甲基十三烷基)-二環[2. 2. 1]庚基-5-烯烴-2,3-二羧基醯亞胺、N-(1-甲基十四烷基)-二環[2. 2. 1]庚基-5-烯烴-2,3-二羧基醯亞胺、N-(1-甲基十五烷基)-二環[2. 2. 1]庚基-5-烯烴-2,3-二羧基醯亞胺等。這些係可以分別單獨地使用或者是組合2種以上而使用。As a specific example of the monomer represented by the above formula (1), N-(1-methylbutyl)-bicyclo[2.2.1]heptyl-5-olefin-2,3-dicarboxyl Yttrium imine, N-(2-methylbutyl)-bicyclo[2.2.1]heptyl-5-olefin-2,3-dicarboxy quinone imine, N-(1-methylpentyl)- Bicyclo [2.2.1] heptyl-5-olefin-2,3-dicarboxy quinone imine, N-(2-methylpentyl)-bicyclo[2.2.1]heptyl-5-olefin-2 , 3-dicarboxy quinone imine, N-(1-ethylbutyl)-bicyclo[2.2.1]heptyl-5-olefin-2,3-dicarboxy quinone imine, N-(2-B Butyl)-bicyclo[2.2.1]heptyl-5-olefin-2,3-dicarboxy quinone imine, N-(1-methylhexyl)-bicyclo[2.2.1]heptyl-5 - olefin-2,3-dicarboxy quinone imine, N-(2-methylhexyl)-bicyclo[2.2.1]heptyl-5-olefin-2,3-dicarboxy quinone imine, N-( 3-methylhexyl)-bicyclo[2.2.1]heptyl-5-olefin-2,3-dicarboxy quinone imine, N-(1-butylpentyl)-bicyclo[2.2.1]g 5--5-olefin-2,3-dicarboxy quinone imine, N-(2-butylpentyl)-bicyclo[2.2.1]heptyl-5-olefin-2,3-dicarboxy quinone , N-(1-methylheptyl)-bicyclo[2.2.1]heptyl-5-olefin-2,3-dicarboxy quinone imine, N-(2-methylheptyl)-bicyclo[ 2.2.1] heptyl-5-olefin-2,3-dicarboxyl Base imine, N-(3-methylheptyl)-bicyclo[2.2.1]heptyl-5-olefin-2,3-dicarboxy quinone imine, N-(4-methylheptyl) -bicyclo[2.2.1]heptyl-5-olefin-2,3-dicarboxy quinone imine, N-(1-ethylhexyl)-bicyclo[2.2.1]heptyl-5-olefin-2 , 3-dicarboxy quinone imine, N-(2-ethylhexyl)-bicyclo[2.2.1]heptyl-5-olefin-2,3-dicarboxy quinone imine, N-(3-ethyl Hexyl)-bicyclo[2.2.1]heptyl-5-olefin-2,3-dicarboxy quinone imine, N-(1-propylpentyl)-bicyclo[2.2.1]heptyl-5- Olefin-2,3-dicarboxy quinone imine, N-(2-propylpentyl)-bicyclo[2.2.1]heptyl-5-olefin-2,3-dicarboxy quinone imine, N-( 1-methyloctyl)-bicyclo[2.2.1]heptyl-5-olefin-2,3-dicarboxy quinone imine, N-(2-methyloctyl)-bicyclo[2.2.1] Heptyl-5-olefin-2,3-dicarboxy quinone imine, N-(3-methyloctyl)-bicyclo[2.2.1]heptyl-5-olefin-2,3-dicarboxy fluorene Amine, N-(4-methyloctyl)-bicyclo[2.2.1]heptyl-5-olefin-2,3-dicarboxy quinone imine, N-(1-ethylheptyl)-bicyclo [2.2.1] Heptyl-5-olefin-2,3-dicarboxyindenine, N-(2-ethylheptyl)-bicyclo[2.2.1]heptyl-5-olefin-2,3 -Dicarboxy quinone imine, N-(3-ethylheptyl)-bicyclo[2.2.1]g -5-olefin-2,3-dicarboxy quinone imine, N-(4-ethylheptyl)-bicyclo[2.2.1]heptyl-5-olefin-2,3-dicarboxy quinone imine, N-(1-propylhexyl)-bicyclo[2.2.1]heptyl-5-olefin-2,3-dicarboxy quinone imine, N-(2-propylhexyl)-bicyclo[2.2.1 Heptyl-5-olefin-2,3-dicarboxy quinone imine, N-(3-propylhexyl)-bicyclo[2.2.1]heptyl-5-olefin-2,3-dicarboxy fluorene Amine, N-(1-methylindenyl)-bicyclo[2.2.1]heptyl-5-olefin-2,3-dicarboxy quinone imine, N-(2-methylindenyl)-bicyclo [2.2.1] Heptyl-5-olefin-2,3-dicarboxyindenine, N-(3-methylindenyl)-bicyclo[2.2.1]heptyl-5-olefin-2,3 -Dicarboxy quinone imine, N-(4-methylindolyl)-bicyclo[2.2.1]heptyl-5-olefin-2,3-dicarboxy quinone imine, N-(5-methyl hydrazine ))-bicyclo[2.2.1]heptyl-5-olefin-2,3-dicarboxy quinone imine, N-(1-ethyloctyl)-bicyclo[2.2.1]heptyl-5- Olefin-2,3-dicarboxy quinone imine, N-(2-ethyloctyl)-bicyclo[2.2.1]heptyl-5-olefin-2,3-dicarboxy quinone imine, N -(3-ethyloctyl)-bicyclo[2.2.1]heptyl-5-olefin-2,3-dicarboxyindolimine, N-(4-ethyloctyl)-bicyclo[ 2. 2. 1]heptyl-5-olefin-2,3-dicarboxy quinone imine, N-(1-癸 ))-bicyclo[2. 2. 1]heptyl-5-olefin-2,3-dicarboxy quinone imine, N-(1-methyldodecyl)-bicyclo[2. 2 . 1] heptyl-5-olefin-2,3-dicarboxy quinone imine, N-(1-methylundecyl)-bicyclo[2.2.1]heptyl-5-olefin-2,3 -Dicarboxy quinone imine, N-(1-methyldodecyl)-bicyclo[2.2.1]heptyl-5-olefin-2,3-dicarboxy quinone imine, N-(1 -methyltridecyl)-bicyclo[2.2.1]heptyl-5-olefin-2,3-dicarboxy quinone imine, N-(1-methyltetradecyl)-bicyclo [2. 2. 1]Heptyl-5-olefin-2,3-dicarboxyindolimine, N-(1-methylpentadecyl)-bicyclo[2.2.1]heptyl-5 - olefin-2,3-dicarboxy quinone imine, and the like. These systems may be used alone or in combination of two or more.

作為藉由前述通式(1)所表示之單體之製造方法係並無特別限定，但是，例如可以藉由對應之胺和5-原菠烷-2,3-二羧酸酐之醯胺化反應而得到。此外，得到之單體係能夠藉由以習知之方法，來分離‧精製醯胺化反應之反應液，而效率良好地進行離析。The method for producing the monomer represented by the above formula (1) is not particularly limited, but, for example, it can be amidated by a corresponding amine and 5-pronane-2,3-dicarboxylic anhydride. Obtained by reaction. Further, the obtained single system can be isolated by efficiently separating the reaction liquid of the hydrazine reaction by a conventional method.

樹脂(A)中之藉由前述通式(1)所表示之單體之單位(e)之含有比例係相對於全單體單位而最好是10～90莫爾%。在藉由前述通式(1)所表示之單體之單位(e)之含有比例過度少之時，恐怕會使得樹脂(A)對於有機溶媒之溶解性呈不充分，在過度多之時，恐怕會降低樹脂組成物之感應放射線性或者是在顯影時來發生溶解之殘留。The content ratio of the unit (e) of the monomer represented by the above formula (1) in the resin (A) is preferably from 10 to 90 mol% based on the total monomer unit. When the content ratio of the unit (e) of the monomer represented by the above formula (1) is excessively small, the solubility of the resin (A) in the organic solvent may be insufficient, and when it is excessively large, I am afraid that the induced radiation of the resin composition may be lowered or the residue may be dissolved during development.

此外，藉由前述通式(1)所表示之單體之單位(e)之含有比例之更加理想範圍係由於藉著本發明使用之樹脂組成物來構成之鈍化膜之種類而不同。具體地說，該鈍化膜係藉由包含感應放射線化合物之樹脂組成物而形成，在成為進行藉由光微影而造成之圖案化之鈍化膜之狀態下，藉由前述通式(1)所表示之單體之單位(e)之含有比例係更加理想是30～60莫爾%，特別最好是40～50莫爾%。另一方面，鈍化膜係在成為不進行藉由光微影而造成之圖案化之鈍化膜之狀態下，藉由前述通式(1)所表示之單體之單位(e)之含有比例係更加理想是20～80莫爾%，特別最好是30～70莫爾%。In addition, a more preferable range of the content ratio of the unit (e) of the monomer represented by the above formula (1) differs depending on the kind of the passivation film which is constituted by the resin composition used in the present invention. Specifically, the passivation film is formed by a resin composition containing an inductive radiation compound, and is in a state in which a passivation film which is patterned by photolithography is used, by the above formula (1) The content ratio of the unit (e) of the monomer to be represented is more preferably from 30 to 60 mol%, particularly preferably from 40 to 50 mol%. On the other hand, in the state in which the passivation film is a passivation film which is patterned by photolithography, the content ratio of the unit (e) of the monomer represented by the above formula (1) is More preferably, it is 20 to 80% by mole, and particularly preferably 30 to 70% by mole.

最好是對於可共聚於藉由前述通式(1)所表示之單體之單體單位，進行共聚。作為可共聚之單體係列舉前述具有質子性極性基之環狀烯烴單體(a)、具有除去藉由通式(1)所表示之單體以外之質子性極性基以外之極性基之環狀烯烴單體(b)、不具有極性基之環狀烯烴單體(c)以及環狀烯烴以外之單體(d)。It is preferred to carry out copolymerization for a monomer unit copolymerizable with the monomer represented by the above formula (1). The cyclic olefin monomer (a) having a protonic polar group and a ring having a polar group other than the protonic polar group other than the monomer represented by the general formula (1) The olefin monomer (b), the cyclic olefin monomer (c) having no polar group, and the monomer (d) other than the cyclic olefin.

此外，可以是對於藉由前述通式(1)所表示之單體中之至少一種以及配合需要而使用之可共聚之單體來進行開環‧聚合之開環聚合物。Further, it may be a ring-opening/polymerized ring-opening polymer which is a copolymerizable monomer which is used by at least one of the monomers represented by the above formula (1) and a compounding requirement.

作為聚合觸媒係適合使用例如前述鉬、釕、鋨等之金屬錯合物。這些聚合觸媒係可以分別單獨或者是組合2種以上而使用。As the polymerization catalyst, for example, a metal complex such as the above-mentioned molybdenum, rhodium, ruthenium or the like is preferably used. These polymerization catalysts may be used alone or in combination of two or more.

此外，可以使用氫化觸媒，對於聚合各單體而得到之聚合物，來進行氫化。作為氫化觸媒係正如前面之敘述，可以使用例如在烯烴化合物之氫化之際而一般使用者。具體地說，可以利用齊格勒(Ziegler)形式之均一系觸媒、貴金屬錯合物觸媒和附載型貴金屬系觸媒等。在這些氫化觸媒中，由不引起官能基變性等之副反應而能夠呈選擇性地氫化聚合物中之主鏈之碳-碳不飽和鍵之方面來看的話，則最好是銠、釕等之貴金屬錯合物觸媒，特別最好是高電子給予性之含氮雜環式香芹烯化合物或膦類呈配位之釕觸媒。Further, hydrogenation can be carried out by using a hydrogenation catalyst for the polymer obtained by polymerizing each monomer. As the hydrogenation catalyst system, as described above, for example, in the case of hydrogenation of an olefin compound, a general user can be used. Specifically, a uniform catalyst such as a Ziegler type, a noble metal complex catalyst, and a supported noble metal catalyst can be used. Among these hydrogenation catalysts, those which are capable of selectively hydrogenating a carbon-carbon unsaturated bond of a main chain in a polymer by a side reaction which does not cause denaturation of a functional group or the like are preferably ruthenium and osmium. The noble metal complex catalyst is particularly preferably a high electron donating nitrogen-containing heterocyclic carotenoid compound or a phosphine-based rhodium catalyst.

本發明使用之樹脂(A)之重量平均分子量(Mw)係通常為1,000～1,000,000，最好是1,500～100,000，更加理想是2,000～10,000之範圍。The weight average molecular weight (Mw) of the resin (A) used in the present invention is usually 1,000 to 1,000,000, preferably 1,500 to 100,000, more preferably 2,000 to 10,000.

樹脂(A)之分子量分布係以重量平均分子量/數平均分子量(Mw/Mn)之比值而通常成為4以下，最好是3以下，更加理想是2.5以下。The molecular weight distribution of the resin (A) is usually 4 or less, preferably 3 or less, more preferably 2.5 or less, in terms of a ratio of a weight average molecular weight to a number average molecular weight (Mw/Mn).

樹脂(A)之重量平均分子量(Mw)或分子量分布係可以使用凝膠滲透色譜法而進行測定。例如能夠以四氫化呋喃等之溶媒，作為溶離液，成為聚苯乙烯換算分子量而求出。The weight average molecular weight (Mw) or molecular weight distribution of the resin (A) can be measured by gel permeation chromatography. For example, a solvent such as tetrahydrofuran can be used as a solution to obtain a molecular weight in terms of polystyrene.

使用於本發明之有機溶媒(B)係並無特別限定。作為其具體例係列舉乙烯乙二醇、丙二醇、二乙烯乙二醇、三乙烯乙二醇、四乙烯乙二醇等之烷撐乙二醇類；乙烯乙二醇單乙基醚、丙二醇單乙基醚、二乙烯乙二醇單甲基醚、二乙烯乙二醇單乙基醚、二丙二醇單甲基醚、三乙烯乙二醇單甲基醚、三乙烯乙二醇單乙基醚等之烷撐乙二醇單醚類；二乙烯乙二醇二甲基醚、二乙烯乙二醇二乙基醚、二乙烯乙二醇乙基甲基醚、二丙二醇二甲基醚、二丙二醇二乙基醚、二丙二醇乙基甲基醚等之烷撐乙二醇二烷基醚類；丙二醇單甲基醚乙酸酯、二丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯等之烷撐乙二醇單烷基醚酯類；甲基乙基甲酮、環己酮、2-庚酮、4-羥基-4-甲基-2-庚酮、環己酮、環庚酮等之酮類；甲醇、乙醇、丙醇、丁醇、3-甲氧基-3-甲基丁醇等之醇類；四氫化呋喃、二噁烷等之環狀醚類；甲基乙二醇***乙酸酯、乙基乙二醇***乙酸酯等之乙二醇***酯類；苯、甲苯、二甲苯等之芳香族烴類；乙酸乙酯、乙酸丁酯、乳酸乙酯、2-羥基-2-甲基丙酸甲基、3-乙氧基丙酸乙基、3-乙氧基丙酸甲基、γ-丁內酯等之酯類；N-甲基甲醯胺、N,N-二甲基甲醯胺、N-甲基-2-吡咯烷酮、N-甲基乙醯胺、N,N-二甲基乙醯胺等之醯胺類；二甲基亞碼等之亞碼類等。即使是在其中，也最好是二乙烯乙二醇乙基甲基醚、丙二醇單甲基醚乙酸酯、環戊酮、N-甲基-2-吡咯烷酮。The organic solvent (B) to be used in the present invention is not particularly limited. As a specific example thereof, alkylene glycols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, etc.; ethylene glycol monoethyl ether, propylene glycol single Ethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether Ethylene glycol monoethers; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, dipropylene glycol dimethyl ether, two An alkylene glycol dialkyl ether such as propylene glycol diethyl ether or dipropylene glycol ethyl methyl ether; propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Alkenylene glycol monoalkyl ether esters such as acetate; methyl ethyl ketone, cyclohexanone, 2-heptanone, 4-hydroxy-4-methyl-2-heptanone, cyclohexanone a ketone such as cycloheptanone; an alcohol such as methanol, ethanol, propanol, butanol or 3-methoxy-3-methylbutanol; a cyclic ether such as tetrahydrofuran or dioxane; Methyl glycol Ethylene glycol esters such as ether acetate, ethyl glycol diethyl ether acetate; aromatic hydrocarbons such as benzene, toluene, xylene; ethyl acetate, butyl acetate, ethyl lactate, 2- Ester of hydroxy-2-methylpropionic acid methyl, 3-ethoxypropionic acid ethyl, 3-ethoxypropionic acid methyl, γ-butyrolactone, etc.; N-methylformamide, N , phthalamides such as N-dimethylformamide, N-methyl-2-pyrrolidone, N-methylacetamide, N,N-dimethylacetamide; dimethyl subcodes, etc. Subcodes, etc. Even among them, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether acetate, cyclopentanone, and N-methyl-2-pyrrolidone are preferable.

這些有機溶劑(B)係可以分別單獨地使用或者是併用2種以上。有機溶劑(B)之使用量係相對於樹脂100重量份而通常成為20～10,000重量份，最好是50～5,000重量份，更加理想是100～1,000重量份之範圍。These organic solvents (B) may be used alone or in combination of two or more. The amount of the organic solvent (B) to be used is usually 20 to 10,000 parts by weight, preferably 50 to 5,000 parts by weight, more preferably 100 to 1,000 parts by weight, per 100 parts by weight of the resin.

在使用於本發明之樹脂組成物，最好是還包含具有酸性基之化合物(C)。具有酸性基之化合物(C)係並無特別限定，但是，最好是脂肪族化合物、芳香族化合物、雜環化合物，更加理想是芳香族化合物、雜環化合物。這些化合物(C)係可以分別單獨或者是組合2種以上而使用。In the resin composition used in the present invention, it is preferred to further contain the compound (C) having an acidic group. The compound (C) having an acidic group is not particularly limited, but is preferably an aliphatic compound, an aromatic compound or a heterocyclic compound, and more preferably an aromatic compound or a heterocyclic compound. These compounds (C) can be used alone or in combination of two or more.

酸性基之數目係並無特別限定，但是，最好是具有2個以上之酸性基，特別最好是具有2個之酸性基。酸性基係可以相互地相同或不同。The number of the acidic groups is not particularly limited, but it is preferable to have two or more acidic groups, and it is particularly preferable to have two acidic groups. The acidic groups may be the same or different from each other.

酸性基係可以是酸性之官能基，作為其具體例係列舉磺酸基、磷酸基等之強酸性基；羧基、硫代基和羧基亞甲基硫代基等之弱酸性基。即使是在這些當中，也最好是羧基、硫代基或羧基亞甲基硫代基，特別最好是羧基。此外，即使是在這些酸性基中，也最好是酸解離常數pKa位處於3.5以上、5.0以下之範圍。此外，在酸性基為2個以上之狀態下，以第1解離常數pKa1，作為酸解離常數。此外，pKa係在稀薄水溶液條件下，成為酸解離常數Ka=[H3 O+ ][B- ]/[BH]。在此，BH係表示有機酸，B- 係表示有機酸之共軛鹼。pKa係成為pKa=-logKa。此外，pKa之測定方法係例如可以使用pH酸鹼度計，測定氫離子濃度，由該物質之濃度和氫離子濃度而算出。The acidic group may be an acidic functional group, and as a specific example thereof, a strong acidic group such as a sulfonic acid group or a phosphoric acid group; a weakly acidic group such as a carboxyl group, a thio group or a carboxymethylenethio group. Even among these, a carboxyl group, a thio group or a carboxymethylenethio group is preferred, and a carboxyl group is particularly preferred. Further, even in these acidic groups, it is preferable that the acid dissociation constant pKa position is in the range of 3.5 or more and 5.0 or less. Further, in the state where the acid group is two or more, the first dissociation constant pKa1 is used as the acid dissociation constant. Further, the pKa is an acid dissociation constant Ka = [H 3 O + ] [B - ] / [BH] under a dilute aqueous solution condition. Here, BH represents an organic acid-based, B - represents an organic acid-based conjugate base. The pKa system becomes pKa = -logKa. Further, the measurement method of pKa can be calculated, for example, by using a pH pH meter to measure the hydrogen ion concentration, and the concentration of the substance and the hydrogen ion concentration.

在本發明，藉由使用具有這些酸性基之化合物(C)，而使得由本發明之樹脂組成物來形成之鈍化膜，良好於薄膜電晶體之可靠性之提升。In the present invention, by using the compound (C) having these acidic groups, the passivation film formed from the resin composition of the present invention is improved in reliability of the thin film transistor.

在本發明，前述化合物(C)係可以具有酸性基以外之取代基。作為此種取代基係除了烷基、芳基等之烴基以外，還可以列舉鹵素原子；烷氧基、芳氧基、醯氧基、異環氧基；藉由烷基或芳基或雜環基而取代之胺基、醯胺基、脲基、氨磺醯胺基、烷氧基羰基胺基、芳氧基羰基胺基；烷基硫代基、芳基硫代基、異環硫代基等之不具有質子之極性基；藉由這些不具有質子之極性基而取代之烴基等。In the present invention, the above compound (C) may have a substituent other than an acidic group. Examples of such a substituent include a halogen atom, an alkoxy group, an aryloxy group, a decyloxy group, and an iso-epoxy group, in addition to a hydrocarbon group such as an alkyl group or an aryl group; and an alkyl group or an aryl group or a heterocyclic group; Substituted amine, amidino, ureido, amsulfamide, alkoxycarbonylamino, aryloxycarbonylamino; alkylthio, arylthio, isocyclic thio a polar group having no proton or the like; a hydrocarbon group or the like substituted by these polar groups having no proton.

作為化合物(C)之具體例係列舉甲烷酸、乙烷酸、丙烷酸、丁烷酸、戊烷酸、丁烷酸、戊烷酸、己烷酸、庚烷酸、辛烷酸、壬烷酸、癸烷酸、乙二醇酸、丙三醇酸、乙烷二酸(也稱為「草酸」。)、丙烷二酸(也稱為「丙二酸」。)、丁烷二酸(也稱為「琥珀酸」。)、戊烷二酸、己烷二酸(也稱為「己二酸」。)、1,2-環己烷二羧酸、2-氧丙烷酸、2-羥基丁烷二酸、2-羥基丙烷三羧酸、巰基琥珀酸、二巰基琥珀酸、2,3-二巰基-1-丙醇、1,2,,3-三巰基丙烷、2,3,4-三巰基-1-丁醇、2,4-二巰基-1,3-丁烷二醇、1,3,4-三巰基-2-丁醇、3,4-二巰基--1,2-丁烷二醇、1,5-二巰基-3-噻戊烷等之脂肪族化合物；安息香酸、p-羥基苯羧酸、o-羥基苯羧酸、2-萘羧酸、甲基安息香酸、二甲基安息香酸、三甲基安息香酸、3-苯基丙烷酸、2-羥基安息香酸、二羥基安息香酸、二甲氧基安息香酸、苯-1,2-二羧酸(也稱為「苯二甲酸」。)、苯-1,3-二羧酸(也稱為「間苯二甲酸」。)、苯-1,4-二羧酸(也稱為「對苯二甲酸」。)、苯-1,2,3-三羧酸、苯-1,2,4-三羧酸、苯-1,3,5-三羧酸、苯六羧酸、聯苯基-2,2’-二羧酸、2-(羧基甲基)安息香酸、3-(羧基甲基)安息香酸、4-(羧基甲基)安息香酸、2-(羧基羰基)安息香酸、3-(羧基羰基)安息香酸、4-(羧基羰基)安息香酸、2-巰基安息香酸、4-巰基安息香酸、2-巰基-6-萘羧酸、2-巰基-7-萘羧酸、1,2-二巰基苯、1,3-二巰基苯、1,4-二巰基苯、1,4-萘二硫代、1,5-萘二硫代、2,6-萘二硫代、2,7-萘二硫代、1,2,3-三巰基苯、1,2,4-三巰基苯、1,3,5-三巰基苯、1,2,3-三(巰基甲基)苯、1,2,4-三(巰基甲基)苯、1,3,5-三(巰基甲基)苯、1,2,3-三(巰基乙基)苯、1,2,4-三(巰基乙基)苯、1,3,5-三(巰基乙基)苯等之芳香族化合物；吡啶甲酸、異吡啶甲酸、2-糠酸、吡咯-2,3-二羧酸、吡咯-2,4-二羧酸、吡咯-2,5-二羧酸、吡咯-3,4-二羧酸、咪唑-2,4-二羧酸、咪唑-2,5-二羧酸、咪唑-4,5-二羧酸、吡唑-3,4-二羧酸、吡唑-3,5-二羧酸等之包含氮原子之5員雜環化合物；噻吩-2,3-二羧酸、噻吩-2,4-二羧酸、噻吩-2,5-二羧酸、噻吩-3,4-二羧酸、噻唑-2,4-二羧酸、噻唑-2,5-二羧酸、噻唑-4,5-二羧酸、異噻吩-3,4-二羧酸、異噻吩-3,5-二羧酸、1,2,4-噻二唑-2,5-二羧酸、1,3,4-噻二唑-2,5-二羧酸、3-胺基-5-巰基-1,2,4-噻二唑、2-胺基-5-巰基-1,3,4-噻二唑、3,5-二巰基-1,2,4-噻二唑、2,5-二巰基-1,3,4-噻二唑、3-(5-巰基-1,2,4-噻二唑-3-醯對氨苯磺醯基)琥珀酸、2-(5-巰基-1,3,4-噻二唑-2-醯對氨苯磺醯基)琥珀酸、(5-巰基-1,2,4-噻二唑-3-醯硫代)乙酸、(5-巰基-1,3,4-噻二唑-2-醯硫代)乙酸、3-(5-巰基-1,2,4-噻二唑-3-醯硫代)丙酸、2-(5-巰基-1,3,4-噻二唑-2-醯硫代)丙酸、3-(5-巰基-1,2,4-噻二唑-3-醯硫代)琥珀酸、2-(5-巰基-1,3,4-噻二唑-2-醯硫代)琥珀酸、4-(3-巰基-1,2,4-噻二唑-5-醯)硫代丁烷磺酸、4-(2-巰基-1,3,4-噻二唑-5-醯)硫代丁烷磺酸等之包含氮原子和硫原子之5員雜環化合物；吡啶-2,3-二羧酸、吡啶-2,4-二羧酸、吡啶-2,5-二羧酸、吡啶-2,6-二羧酸、吡啶-3,4-二羧酸、吡啶-3,5-二羧酸、噠嗪-3,4-二羧酸、噠嗪-3,5-二羧酸、噠嗪-3,6-二羧酸、噠嗪-4,5-二羧酸、嘧啶-2,4-二羧酸、嘧啶-2,5-二羧酸、嘧啶-4,5-二羧酸、嘧啶-4,6-二羧酸、吡嗪-2,3-二羧酸、吡嗪-2,5-二羧酸、吡嗪-2,6-二羧酸、三嗪-2,4-二羧酸、2-二乙基胺基-4,6-二巰基-s-三嗪、2-二丙基胺基-4,6-二巰基-s-三嗪、2-二丁基胺基-4,6-二巰基-s-三嗪、2-苯胺基-4,6-二巰基-s-三嗪、2,4,6-三巰基-s-三嗪等之包含氮原子之6員雜環化合物。即使是在這些當中，也由所謂薄膜電晶體之安定性更加地良好之觀點來看的話，則酸性基之數目係最好是2個以上，特別最好是2個。Specific examples of the compound (C) include methane acid, ethane acid, propane acid, butane acid, pentanoic acid, butanoic acid, pentanoic acid, hexane acid, heptanoic acid, octanoic acid, and decane. Acid, decanoic acid, glycolic acid, glycerol acid, ethane diacid (also known as "oxalic acid"), propane diacid (also known as "malonic acid"), butanedioic acid ( Also known as "succinic acid".), pentanedioic acid, hexanedioic acid (also known as "adipic acid".), 1,2-cyclohexanedicarboxylic acid, 2-oxopropionic acid, 2- Hydroxybutanedioic acid, 2-hydroxypropane tricarboxylic acid, mercapto succinic acid, dimercaptosuccinic acid, 2,3-dimercapto-1-propanol, 1,2,3-trimercaptopropane, 2,3, 4-trimethyl-1-butanol, 2,4-dimercapto-1,3-butanediol, 1,3,4-trimercapto-2-butanol, 3,4-dimercapto--1, An aliphatic compound such as 2-butanediol or 1,5-dimercapto-3-thiopentane; benzoic acid, p-hydroxybenzenecarboxylic acid, o-hydroxybenzenecarboxylic acid, 2-naphthalenecarboxylic acid, methyl Benzoic acid, dimethyl benzoic acid, trimethyl benzoic acid, 3-phenylpropanic acid, 2-hydroxybenzoic acid, dihydroxybenzoic acid, dimethoxybenzoic acid, benzene-1,2-dicarboxylate Acid (also known as "phthalic acid".), benzene-1,3-dicarboxylic acid (also known as "isophthalic acid".), benzene-1,4-dicarboxylic acid (also known as "pair" Phthalic acid.), benzene-1,2,3-tricarboxylic acid, benzene-1,2,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, benzenehexacarboxylic acid, biphenyl Base-2,2'-dicarboxylic acid, 2-(carboxymethyl)benzoic acid, 3-(carboxymethyl)benzoic acid, 4-(carboxymethyl)benzoic acid, 2-(carboxycarbonyl)benzoic acid, 3-(carboxycarbonyl)benzoic acid, 4-(carboxycarbonyl)benzoic acid, 2-mercaptobenzoic acid, 4-mercaptobenzoic acid, 2-mercapto-6-naphthalenecarboxylic acid, 2-mercapto-7-naphthalenecarboxylic acid, 1,2-dimercaptobenzene, 1,3-dioxylbenzene, 1,4-dioxylbenzene, 1,4-naphthalene dithio, 1,5-naphthalene dithio, 2,6-naphthalene dithio , 2,7-naphthalene dithio, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene, 1,2,3-trisyl Benzo, 1,2,4-tris(decylmethyl)benzene, 1,3,5-tris(decylmethyl)benzene, 1,2,3-tris(decylethyl)benzene, 1,2, An aromatic compound such as 4-tris(decylethyl)benzene or 1,3,5-tris(decylethyl)benzene; picolinic acid, isopicolinic acid, 2-decanoic acid, pyrrole-2,3-dicarboxylic acid Pyr -2,4-dicarboxylic acid, pyrrole-2,5-dicarboxylic acid, pyrrole-3,4-dicarboxylic acid, imidazole-2,4-dicarboxylic acid, imidazole-2,5-dicarboxylic acid, a 5-membered heterocyclic compound containing a nitrogen atom such as imidazole-4,5-dicarboxylic acid, pyrazole-3,4-dicarboxylic acid or pyrazole-3,5-dicarboxylic acid; thiophene-2,3-di Carboxylic acid, thiophene-2,4-dicarboxylic acid, thiophene-2,5-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, thiazole-2,4-dicarboxylic acid, thiazole-2,5-di Carboxylic acid, thiazole-4,5-dicarboxylic acid, isothiophene-3,4-dicarboxylic acid, isothiophene-3,5-dicarboxylic acid, 1,2,4-thiadiazole-2,5-di Carboxylic acid, 1,3,4-thiadiazole-2,5-dicarboxylic acid, 3-amino-5-mercapto-1,2,4-thiadiazole, 2-amino-5-mercapto-1 , 3,4-thiadiazole, 3,5-dimercapto-1,2,4-thiadiazole, 2,5-dimercapto-1,3,4-thiadiazole, 3-(5-fluorenyl- 1,2,4-thiadiazol-3-indole-aminobenzenesulfonyl)succinic acid, 2-(5-mercapto-1,3,4-thiadiazol-2-indole-aminobenzenesulfonyl) Succinic acid, (5-mercapto-1,2,4-thiadiazol-3-indolethio)acetic acid, (5-mercapto-1,3,4-thiadiazol-2-indolethio)acetic acid, 3 -(5-mercapto-1,2,4-thiadiazol-3-indole thio)propionic acid, 2-(5-mercapto-1,3,4-thiadiazol-2-indole thio)propionic acid , 3-(5-mercapto-1,2,4-thiadiazol-3-indole thio) a Peric acid, 2-(5-mercapto-1,3,4-thiadiazol-2-indole thio) succinic acid, 4-(3-indolyl-1,2,4-thiadiazole-5-indole) a 5-membered heterocyclic compound containing a nitrogen atom and a sulfur atom, such as thiobutanesulfonic acid, 4-(2-mercapto-1,3,4-thiadiazol-5-indole)thiobutanesulfonic acid; -2,3-dicarboxylic acid, pyridine-2,4-dicarboxylic acid, pyridine-2,5-dicarboxylic acid, pyridine-2,6-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, pyridine -3,5-dicarboxylic acid, pyridazine-3,4-dicarboxylic acid, pyridazine-3,5-dicarboxylic acid, pyridazine-3,6-dicarboxylic acid, pyridazine-4,5-di Carboxylic acid, pyrimidine-2,4-dicarboxylic acid, pyrimidine-2,5-dicarboxylic acid, pyrimidine-4,5-dicarboxylic acid, pyrimidine-4,6-dicarboxylic acid, pyrazine-2,3- Dicarboxylic acid, pyrazine-2,5-dicarboxylic acid, pyrazine-2,6-dicarboxylic acid, triazine-2,4-dicarboxylic acid, 2-diethylamino-4,6-di Mercapto-s-triazine, 2-dipropylamino-4,6-dimercapto-s-triazine, 2-dibutylamino-4,6-dimercapto-s-triazine, 2-aniline A 6-membered heterocyclic compound containing a nitrogen atom, such as a group of 4,6-dimercapto-s-triazine, 2,4,6-tridecyl-s-triazine. Even in these cases, the number of acidic groups is preferably two or more, and particularly preferably two, from the viewpoint that the stability of the thin film transistor is further improved.

作為具有2個酸性基之化合物係最好是乙烷二酸、丙烷二酸、丁烷二酸、戊烷二酸、己烷二酸、1,2-環己烷二羧酸、苯-1,2-二羧酸(也稱為「苯二甲酸」。)、苯-1,3-二羧酸(也稱為「間苯二甲酸」。)、苯-1,4-二羧酸(也稱為「對苯二甲酸」。)、聯苯基-2,2’-二羧酸、2-(羧基甲基)安息香酸、3-(羧基甲基)安息香酸、4-(羧基甲基)安息香酸、2-巰基安息香酸、4-巰基安息香酸、2-巰基-6-萘羧酸、2-巰基-7-萘羧酸、1,2-二巰基苯、1,3-二巰基苯、1,4-二巰基苯、1,4-萘二硫代、1,5-萘二硫代、2,6-萘二硫代、2,7-萘二硫代之具有2個酸性基之芳香族化合物；吡咯-2,3-二羧酸、吡咯-2,4-二羧酸、吡咯-2,5-二羧酸、吡咯-3,4-二羧酸、咪唑-2,4-二羧酸、咪唑-2,5-二羧酸、咪唑-4,5-二羧酸、吡唑-3,4-二羧酸、吡唑-3,5-二羧酸、噻吩-2,3-二羧酸、噻吩-2,4-二羧酸、噻吩-2,5-二羧酸、噻吩-3,4-二羧酸、噻唑-2,4-二羧酸、噻唑-2,5-二羧酸、噻唑-4,5-二羧酸、異噻吩-3,4-二羧酸、異噻吩-3,5-二羧酸、1,2,4-噻二唑-2,5-二羧酸、1,3,4-噻二唑-2,5-二羧酸、(5-巰基-1,2,4-噻二唑-3-醯硫代)乙酸、(5-巰基-1,3,4-噻二唑-2-醯硫代)乙酸、吡啶-2,3-二羧酸、吡啶-2,4-二羧酸、吡啶-2,5-二羧酸、吡啶-2,6-二羧酸、吡啶-3,4-二羧酸、吡啶-3,5-二羧酸、噠嗪-3,4-二羧酸、噠嗪-3,5-二羧酸、噠嗪-3,6-二羧酸、噠嗪-4,5-二羧酸、嘧啶-2,4-二羧酸、嘧啶-2,5-二羧酸、嘧啶-4,5-二羧酸、嘧啶-4,6-二羧酸、吡嗪-2,3-二羧酸、吡嗪-2,5-二羧酸、吡啶-2,6-二羧酸、三嗪-2,4-二羧酸之具有2個酸性基之雜環化合物。The compound having two acidic groups is preferably ethanedioic acid, propanedioic acid, butanedioic acid, pentanedioic acid, hexanedioic acid, 1,2-cyclohexanedicarboxylic acid, benzene-1. , 2-dicarboxylic acid (also known as "phthalic acid".), benzene-1,3-dicarboxylic acid (also known as "isophthalic acid".), benzene-1,4-dicarboxylic acid ( Also known as "terephthalic acid".), biphenyl-2,2'-dicarboxylic acid, 2-(carboxymethyl)benzoic acid, 3-(carboxymethyl)benzoic acid, 4-(carboxyl) Benzoic acid, 2-mercaptobenzoic acid, 4-mercaptobenzoic acid, 2-mercapto-6-naphthalenecarboxylic acid, 2-mercapto-7-naphthalenecarboxylic acid, 1,2-dimercaptobenzene, 1,3- Nonylbenzene, 1,4-didecylbenzene, 1,4-naphthalene dithio, 1,5-naphthalene dithio, 2,6-naphthalene dithio, 2,7-naphthalene dithio Acidic aromatic compound; pyrrole-2,3-dicarboxylic acid, pyrrole-2,4-dicarboxylic acid, pyrrole-2,5-dicarboxylic acid, pyrrole-3,4-dicarboxylic acid, imidazole-2 , 4-dicarboxylic acid, imidazole-2,5-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, pyrazole-3,4-dicarboxylic acid, pyrazole-3,5-dicarboxylic acid, thiophene -2,3-dicarboxylic acid, thiophene-2,4-dicarboxylic acid, thiophene-2,5-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, Thiazole-2,4-dicarboxylic acid, thiazole-2,5-dicarboxylic acid, thiazole-4,5-dicarboxylic acid, isothiophene-3,4-dicarboxylic acid, isothiophene-3,5-dicarboxylate Acid, 1,2,4-thiadiazole-2,5-dicarboxylic acid, 1,3,4-thiadiazole-2,5-dicarboxylic acid, (5-mercapto-1,2,4-thia Oxazol-3-indole thio)acetic acid, (5-mercapto-1,3,4-thiadiazol-2-indolethio)acetic acid, pyridine-2,3-dicarboxylic acid, pyridine-2,4- Dicarboxylic acid, pyridine-2,5-dicarboxylic acid, pyridine-2,6-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, pyridine-3,5-dicarboxylic acid, pyridazine-3,4 -dicarboxylic acid, pyridazine-3,5-dicarboxylic acid, pyridazine-3,6-dicarboxylic acid, pyridazine-4,5-dicarboxylic acid, pyrimidine-2,4-dicarboxylic acid, pyrimidine- 2,5-dicarboxylic acid, pyrimidine-4,5-dicarboxylic acid, pyrimidine-4,6-dicarboxylic acid, pyrazine-2,3-dicarboxylic acid, pyrazine-2,5-dicarboxylic acid, A heterocyclic compound having two acidic groups of pyridine-2,6-dicarboxylic acid or triazine-2,4-dicarboxylic acid.

可以藉由使用這些化合物，而得到所謂具有由樹脂組成物來形成之有機鈍化膜之薄膜電晶體之安定性更加地良好之效果。By using these compounds, it is possible to obtain an effect that the stability of the thin film transistor having the organic passivation film formed of the resin composition is further improved.

在本發明，使用之樹脂組成物之具有酸性基之化合物(C)之含有量係相對於樹脂(A)之100重量份而通常成為1～45重量份、最好是1.5～30重量份、更加理想是2～15重量份之範圍。如果具有酸性基之化合物(C)之使用量為該範圍的話，則即使是在製造後，保管樹脂組成物，也可以得到無發生樹脂組成物之物性變化成為原因而改變樹脂組成物之特性且液體狀安定性呈良好的樹脂組成物。In the present invention, the content of the compound (C) having an acidic group in the resin composition to be used is usually 1 to 45 parts by weight, preferably 1.5 to 30 parts by weight, per 100 parts by weight of the resin (A). More preferably, it is in the range of 2 to 15 parts by weight. When the amount of the compound (C) having an acidic group is in this range, even if the resin composition is stored after the production, the properties of the resin composition can be changed without causing a change in the physical properties of the resin composition. The liquid stability is a good resin composition.

在本發明，使用之樹脂組成物係最好是還具有由矽原子、鈦原子、鋁原子和鋯原子之中而選出之1個原子並且包含具有鍵結於該原子之氫化香芹羥基或羥基之化合物(D)來組成。In the present invention, the resin composition used preferably further has one atom selected from among a halogen atom, a titanium atom, an aluminum atom and a zirconium atom and contains a hydrogenated carnation hydroxyl group or a hydroxyl group bonded to the atom. The compound (D) is composed.

此外，即使是在前述化合物(D)之中，也最好是具有鍵結於矽原子或鈦原子之氫化香芹羥基之化合物。此外，前述氫化香芹羥基係最好是碳數1～18之氫化香芹羥基。Further, even among the aforementioned compound (D), a compound having a hydrogenated carnation hydroxyl group bonded to a ruthenium atom or a titanium atom is preferred. Further, the hydrogenated carvacnic hydroxyl group is preferably a hydrogenated carvacolidyl group having 1 to 18 carbon atoms.

此外，化合物(D)係在樹脂(A)具有質子性極性基之時，特別最好是具有可以反應於質子性極性基之官能基。該可以反應於質子性極性基之官能基係最好是異氰酸酯基、巰基、環氧基或胺基，更加理想是環氧基。Further, when the resin (A) has a protic polar group, the compound (D) is particularly preferably a functional group which can react with a protic polar group. The functional group which can be reacted with a protic polar group is preferably an isocyanate group, a fluorenyl group, an epoxy group or an amine group, and more preferably an epoxy group.

作為化合物(D)之具體例係列舉四甲氧基矽烷、四乙氧基矽烷、四-n-丙氧基矽烷、四-i-丙氧基矽烷、四-n-丁氧基矽烷等之四烷氧基矽烷類、甲基三甲氧基矽烷、甲基三乙氧基矽烷、乙基三甲氧基矽烷、乙基三乙氧基矽烷、n-丙基三甲氧基矽烷、n-丙基三乙氧基矽烷、i-丙基三甲氧基矽烷、i-丙基三乙氧基矽烷、n-丁基三甲氧基矽烷、n-丁基三乙氧基矽烷、n-戊基三甲氧基矽烷、n-己基三甲氧基矽烷、n-庚基三甲氧基矽烷、n-辛基三甲氧基矽烷、n-癸基三甲氧基矽烷、p-苯乙烯基三甲氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、環己基三甲氧基矽烷、環己基三甲氧基矽烷、環己基三乙氧基矽烷、苯基三甲氧基矽烷、苯基三乙氧基矽烷、3-氯丙基三甲氧基矽烷、3-氯丙基三乙氧基矽烷、3,3,3-三氟丙基三甲氧基矽烷、3,3,3-三氟丙基三乙氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三甲氧基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷、2-羥基乙基三甲氧基矽烷、2-羥基乙基三乙氧基矽烷、2-羥基丙基三甲氧基矽烷、2-羥基丙基三乙氧基矽烷、3-羥基丙基三甲氧基矽烷、3-羥基丙基三乙氧基矽烷、3-巰基丙基三甲氧基矽烷、3-巰基丙基三乙氧基矽烷、3-異氰酸酯基丙基三甲氧基矽烷、3-異氰酸酯基丙基三乙氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷、2-(3,4-環氧基環己基)乙基三甲氧基矽烷、2-(3,4-環氧基環己基)乙基三乙氧基矽烷、3-(甲基)丙烯醯基丙基三甲氧基矽烷、3-(甲基)丙烯醯基丙基三乙氧基矽烷、3-脲基丙基三甲氧基矽烷、3-脲基丙基三乙氧基矽烷、3-乙基(三甲氧基甲矽烷基丙氧基甲基)氧雜環丁烷、3-乙基(三乙氧基甲矽烷基丙氧基甲基)氧雜環丁烷、3-三乙氧基甲矽烷基-N-(1,3-二甲基-丁叉)丙基胺、雙(三乙氧基甲矽烷基丙基)四硫醚等之三烷氧基矽烷類、二甲基二甲氧基矽烷、二甲基二乙氧基矽烷、二乙基二甲氧基矽烷、二乙基二乙氧基矽烷、二-n-丙基二甲氧基矽烷、二-n-丙基二乙氧基矽烷、二-i-丙基二甲氧基矽烷、二-i-丙基二乙氧基矽烷、二-n-丁基二甲氧基矽烷、二-n-戊基二甲氧基矽烷、二-n-戊基二乙氧基矽烷、二-n-己基二甲氧基矽烷、二-n-己基二乙氧基矽烷、二-n-庚基二甲氧基矽烷、二-n-庚基二乙氧基矽烷、二-n-辛基二甲氧基矽烷、二-n-辛基二乙氧基矽烷、二-n-環己基二甲氧基矽烷、二-n-環己基二乙氧基矽烷、二苯基二甲氧基矽烷、二苯基二乙氧基矽烷、3-環氧丙氧基丙基甲基二乙氧基矽烷、3-甲基丙烯醯基丙基甲基二甲氧基矽烷、3-丙烯醯基丙基甲基二甲氧基矽烷、3-甲基丙烯醯基丙基甲基二乙氧基矽烷、3-丙烯醯基丙基甲基二乙氧基矽烷、N-2-(胺基乙基)-3-胺基丙基甲基二甲氧基矽烷等之二烷氧基矽烷類以外、甲基三乙醯氧基矽烷、二甲基二乙醯氧基矽烷、商品名稱：X-12-414、KBP-44(信越化學工業股份有限公司製)、217FLAKE、220FLAKE、233FLAKE、z6018(東麗Dow Corning股份有限公司製)等之含矽原子化合物；(四-i-丙氧基鈦、四-n-丁氧基鈦、四(2-乙基己氧基)鈦、鈦-i-丙氧基辛烯乙醇酸酯、二-i-丙氧基‧雙(乙醯丙酮)鈦、丙烷二氧鈦雙(乙基乙醯乙酸酯)、三-n-丁氧基鈦單硬脂酸酯、二-i-丙氧基鈦二硬脂酸酯、鈦硬脂酸酯、二-i-丙氧基鈦二異硬脂酸酯、(2-n-丁氧基羰基苯醯氧基)三丁氧基鈦、二-n-丁氧基‧雙(三乙醇胺化)鈦以外、PLENACT系列(味之素精密技術股份有限公司製))等之含鈦原子化合物；(乙醯烷氧基鋁二異丙醇鹽)等之含鋁原子化合物；(四正丙氧基鋯、四正丁氧基鋯、鋯四乙醯基丙酮酸酯、鋯三丁氧基乙醯基丙酮酸酯、鋯單丁氧基乙醯基丙酮酸酯雙(乙基乙醯乙酸酯)、鋯二丁氧基雙(乙基乙醯乙酸酯)、鋯四乙醯基丙酮酸酯、鋯三丁氧基硬脂酸酯)等之含鋯原子化合物。Specific examples of the compound (D) include tetramethoxynonane, tetraethoxysilane, tetra-n-propoxydecane, tetra-i-propoxydecane, tetra-n-butoxydecane, and the like. Tetraalkoxydecanes, methyltrimethoxydecane, methyltriethoxydecane, ethyltrimethoxydecane, ethyltriethoxydecane, n-propyltrimethoxydecane, n-propyl Triethoxy decane, i-propyl trimethoxy decane, i-propyl triethoxy decane, n-butyl trimethoxy decane, n-butyl triethoxy decane, n-pentyl trimethoxy Baseline, n-hexyltrimethoxydecane, n-heptyltrimethoxydecane, n-octyltrimethoxydecane, n-fluorenyltrimethoxydecane, p-styryltrimethoxydecane,vinyl Trimethoxy decane, vinyl triethoxy decane, cyclohexyl trimethoxy decane, cyclohexyl trimethoxy decane, cyclohexyl triethoxy decane, phenyl trimethoxy decane, phenyl triethoxy decane, 3-chloropropyltrimethoxydecane, 3-chloropropyltriethoxydecane, 3,3,3-trifluoropropyltrimethoxydecane, 3,3,3-trifluoropropyltriethoxy Decane, 3-aminopropyl Trimethoxydecane, 3-aminopropyltriethoxydecane, N-2-(aminoethyl)-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyl Trimethoxydecane, 2-hydroxyethyltrimethoxydecane, 2-hydroxyethyltriethoxydecane, 2-hydroxypropyltrimethoxydecane, 2-hydroxypropyltriethoxydecane, 3-hydroxyl Propyltrimethoxydecane, 3-hydroxypropyltriethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxydecane, 3-isocyanatepropyltrimethoxydecane, 3-Iocyanatepropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 2-(3,4-epoxy Ethylcyclohexyl)ethyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, 3-(methyl)propenylpropyltrimethoxydecane, 3- (Meth) propylene decyl propyl triethoxy decane, 3-ureidopropyl trimethoxy decane, 3-ureidopropyl triethoxy decane, 3-ethyl (trimethoxymethyl decyl propyl Oxymethyl)oxetane, 3-ethyl(triethoxymethyldecylpropoxymethyl) Oxetane, 3-triethoxycarbamido-N-(1,3-dimethyl-butylidene)propylamine, bis(triethoxycarbamylpropyl)tetrasulfide Etousle alkoxy decane, dimethyl dimethoxy decane, dimethyl diethoxy decane, diethyl dimethoxy decane, diethyl diethoxy decane, di-n-propyl Dimethoxy decane, di-n-propyl diethoxy decane, di-i-propyl dimethoxy decane, di-i-propyl diethoxy decane, di-n-butyl Methoxydecane, di-n-pentyldimethoxydecane, di-n-pentyldiethoxydecane, di-n-hexyldimethoxydecane, di-n-hexyldiethoxydecane , bis-n-heptyldimethoxydecane, di-n-heptyldiethoxydecane, di-n-octyldimethoxydecane, di-n-octyldiethoxydecane, two -n-cyclohexyldimethoxydecane, di-n-cyclohexyldiethoxydecane, diphenyldimethoxydecane, diphenyldiethoxydecane, 3-glycidoxypropyl Methyldiethoxydecane, 3-methylpropenylpropylmethyldimethoxydecane, 3-propenylpropylmethyldimethoxydecane, 3-methylpropane Mercaptopropylmethyldiethoxydecane, 3-propenylmethylidene methyldiethoxydecane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxy Other than a dialkoxy decane such as decane, methyltriethoxy decane, dimethyldiethoxy decane, trade name: X-12-414, KBP-44 (manufactured by Shin-Etsu Chemical Co., Ltd.) ), 217FLAKE, 220FLAKE, 233FLAKE, z6018 (made by Toray Corning Co., Ltd.), etc.; (tetra-i-propoxy titanium, tetra-n-butoxy titanium, tetra (2-B) Hexyloxy)titanium, titanium-i-propoxyoctene glycolate, di-i-propoxy bis(acetonitrile) titanium, propane dioxy titanium bis(ethyl acetamidine acetate) , tri-n-butoxy titanium monostearate, di-i-propoxy titanium distearate, titanium stearate, di-i-propoxy titanium diisostearate, (2-n-butoxycarbonylphenyl hydroxy) titanium tributoxide, bis-n-butoxy bis (triethanol aminated) titanium, PLENACT series (manufactured by Ajinomoto Precision Technology Co., Ltd.) a compound containing a titanium atom; an aluminum atom-containing compound such as (acetoxy aluminum diisopropoxide) ; (tetra-n-propoxy zirconium, tetra-n-butoxy zirconium, zirconium tetraethenyl pyruvate, zirconium tributoxyacetate, zirconium monobutoxyacetate) Zirconium atom-containing compound such as ethyl acetoacetate), zirconium dibutoxy bis(ethyl acetonitrile acetate), zirconium tetraethyl acetonate, zirconium tributoxy stearate .

作為前述化合物(D)係即使是在這些當中，也最好是含矽原子化合物、含鈦原子化合物，特別最好是具有可以反應於質子性極性基之官能基。藉由具有前述官能基而使得薄膜電晶體之安定性更加地良好。The above compound (D) is preferably a ruthenium atom-containing compound or a titanium atom-containing compound, and particularly preferably has a functional group which can react with a protic polar group. The stability of the thin film transistor is made better by having the aforementioned functional group.

作為前述具有可以反應於質子性極性基之官能基之化合物係特別最好是3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、n-2-(胺基乙基)-3-胺基丙基三甲氧基矽烷、n-苯基-3-胺基丙基三甲氧基矽烷、3-巰基丙基三甲氧基矽烷、3-巰基丙基三乙氧基矽烷、3-異氰酸酯基丙基三甲氧基矽烷、3-異氰酸酯基丙基三乙氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷、2-(3,4-環氧基環己基)乙基三甲氧基矽烷、2-(3,4-環氧基環己基)乙基三乙氧基矽烷、3-脲基丙基三甲氧基矽烷、3-脲基丙基三乙氧基矽烷、3-三乙氧基甲矽烷基-n-(1,3-二甲基-丁叉)丙基胺、n-2-(胺基乙基)-3-胺基丙基甲基二甲氧基矽烷。這些化合物(D)係可以分別單獨或者是組合2種以上而使用。The above-mentioned compound having a functional group which can react with a protic polar group is particularly preferably 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, n-2-(amino group) Ethyl)-3-aminopropyltrimethoxydecane, n-phenyl-3-aminopropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxylate Decane, 3-isocyanatepropyltrimethoxydecane, 3-isocyanatepropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethyl Oxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, 3-ureidopropyl Trimethoxy decane, 3-ureidopropyl triethoxy decane, 3-triethoxymethyl sulfonyl-n-(1,3-dimethyl-butylidene) propylamine, n-2- (Aminoethyl)-3-aminopropylmethyldimethoxydecane. These compounds (D) may be used alone or in combination of two or more.

使用於本發明之樹脂組成物之化合物(D)之含有量係相對於黏合劑樹脂(A)之100重量份而通常成為1～40重量份、最好是3～30重量份、更加理想是5～25重量份之範圍。如果化合物(D)之使用量為該範圍的話，則可以使得薄膜電晶體之安定性更加地良好。The content of the compound (D) to be used in the resin composition of the present invention is usually 1 to 40 parts by weight, preferably 3 to 30 parts by weight, more preferably 100 parts by weight, based on 100 parts by weight of the binder resin (A). A range of 5 to 25 parts by weight. If the amount of the compound (D) used is in this range, the stability of the thin film transistor can be made more excellent.

最好是在使用於本發明之樹脂組成物，還含有感應放射線化合物(E)。It is preferably used in the resin composition of the present invention, and further contains an inductive radiation compound (E).

使用於本發明之感應放射線化合物(E)係可以藉由紫外線或電子線等之放射線之照射而引起化學反應之化合物。在本發明，感應放射線化合物(E)係最好是能夠控制由樹脂組成物來形成之樹脂膜之鹼溶解性。The radiation-inducing compound (E) to be used in the present invention is a compound which can cause a chemical reaction by irradiation with radiation such as ultraviolet rays or electron beams. In the present invention, the radiation-inducing compound (E) is preferably capable of controlling the alkali solubility of the resin film formed of the resin composition.

在本發明，作為感應放射線化合物(E)係最好是使用光酸產生劑。作為感應放射線化合物(E)係列舉例如乙醯苯化合物、三芳基鎏鹽、醌二疊氮基化合物等之疊氮基化合物等，但是，最好是疊氮基化合物，特別最好是醌二疊氮基化合物。In the present invention, it is preferred to use a photoacid generator as the radiation-inducing compound (E). Examples of the radiation-sensitive compound (E) include an azide compound such as an acetophenone compound, a triarylsulfonium salt, or a quinonediazide compound, but it is preferably an azide compound, and particularly preferably a ruthenium compound. Azido compound.

作為醌二疊氮基化合物係可以使用例如醌二疊氮基磺酸鹵化物和具有苯酚性氫氧基之化合物之酯化合物。作為醌二疊氮基磺酸鹵化物之具體例係列舉1,2-萘醌二疊氮基-5-磺酸氯化物、1,2-萘醌二疊氮基-4-磺酸氯化物、1,2-苯醌二疊氮基-5-磺酸氯化物等。作為具有苯酚性氫氧基之化合物之代表例係列舉1,1,3-三(2,5-二甲基-4-羥基苯基)-3-苯基丙烷、4,4’-[1-[4-[1-[4-羥基苯基]-1-甲基乙基]苯基]乙叉]雙酚等。作為這些以外之具有苯酚性氫氧基之化合物係列舉2,3,4-三羥基二苯甲酮、2,3,4,4’-四羥基二苯甲酮、2-雙(4-羥基苯基)丙烷、三(4-羥基苯基)甲烷、1,1,1-三(4-羥基-3-甲基苯基)乙烷、1,1,2,2-四(4-羥基苯基)乙烷、酚醛樹脂之寡聚物、共聚具有1個以上之苯酚性氫氧基之化合物和二環戊二烯而得到之寡聚物等。As the quinonediazide compound, for example, an ester compound of a quinonediazidesulfonic acid halide and a compound having a phenolic hydroxyl group can be used. As a specific example series of quinonediazidesulfonic acid halide, 1,2-naphthoquinonediazide-5-sulfonic acid chloride, 1,2-naphthoquinonediazide-4-sulfonic acid chloride 1,2-benzoquinonediazide-5-sulfonic acid chloride or the like. As a representative example of a compound having a phenolic hydroxyl group, 1,1,3-tris(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane, 4,4'-[1 -[4-[1-[4-Hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol. As a series of compounds having a phenolic hydroxyl group other than these, 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2-bis(4-hydroxyl) Phenyl)propane, tris(4-hydroxyphenyl)methane, 1,1,1-tris(4-hydroxy-3-methylphenyl)ethane, 1,1,2,2-tetrakis(4-hydroxyl An oligopolymer of phenyl) ethane or a phenol resin, an oligomer obtained by copolymerizing a compound having one or more phenolic hydroxyl groups, and dicyclopentadiene.

即使是在這些當中，也最好是1,2-萘醌二疊氮基-5-磺酸氯化物和具有苯酚性氫氧基之化合物之縮合物，更加理想是1,1,3-三(2,5-二甲基-4-羥基苯基)-3-苯基丙烷(1莫爾)和1,2-萘醌二疊氮基-5-磺酸氯化物(2.5莫爾)之縮合物。Even among these, a condensate of a 1,2-naphthoquinonediazide-5-sulfonic acid chloride and a compound having a phenolic hydroxyl group is preferable, and more preferably 1,1,3-three. (2,5-Dimethyl-4-hydroxyphenyl)-3-phenylpropane (1 moor) and 1,2-naphthoquinonediazide-5-sulfonate chloride (2.5 moor) Condensate.

作為光酸產生劑係除了醌二疊氮基化合物以外，還可以使用鎓鹽、鹵化有機化合物、α,α’-雙(磺醯)二偶氮基甲烷系化合物、α-羰基-α’-磺醯二偶氮基甲烷系化合物、碸化合物、有機酸酯化合物、有機酸醯胺化合物、有機酸醯亞胺化合物等之習知者。As the photoacid generator, in addition to the quinonediazide compound, an onium salt, a halogenated organic compound, an α,α'-bis(sulfonyl)diazomethane-based compound, or α-carbonyl-α'- can also be used. A sulfonium diazomethane-based compound, an anthracene compound, an organic acid ester compound, an organic acid decylamine compound, an organic acid quinone imine compound, or the like.

這些感應放射線化合物係可以分別單獨或者是組合2種以上而使用。使用於本發明之樹脂組成物之感應放射線化合物(E)之含有量係相對於樹脂(A)之100重量份而成為1～100重量份、最好是5～50重量份、更加理想是10～40重量份之範圍。如果感應放射線化合物(E)之使用量為該範圍的話，則在對於由形成在任意基板上之樹脂組成物而組成之樹脂膜來進行圖案化之際，對於放射線照射部和放射線未照射部之顯影液之溶解度差變大，由於顯影而造成之圖案化變得容易，並且，放射線感度也變高，因此，變得理想。These inductive radiation compounds may be used alone or in combination of two or more. The content of the radiation-inducing compound (E) to be used in the resin composition of the present invention is 1 to 100 parts by weight, preferably 5 to 50 parts by weight, more preferably 10 parts by weight based on 100 parts by weight of the resin (A). ～40 parts by weight. When the amount of the radiation-inducing compound (E) is in the range, the radiation is irradiated to the radiation-irradiating portion and the radiation-irradiated portion when the resin film composed of the resin composition formed on the substrate is patterned. The difference in solubility of the developer is increased, the patterning by development is facilitated, and the radiation sensitivity is also high, which is preferable.

在本發明，作為樹脂組成物之成分係最好是還含有交聯劑(F)。作為交聯劑(F)係使用在分子內而具有2個以上、最好是3個以上之可以反應於樹脂(A)之官能基。交聯劑(F)具有之官能基係如果是可以反應於黏合劑樹脂中之官能基或不飽和鍵等的話，則並無特別限定，但是，最好是可以反應於質子性極性基。In the present invention, it is preferable that the component of the resin composition further contains a crosslinking agent (F). The crosslinking agent (F) is used in the molecule and has two or more, preferably three or more, functional groups which can be reacted with the resin (A). The functional group of the crosslinking agent (F) is not particularly limited as long as it can react with a functional group or an unsaturated bond in the binder resin, but it is preferably reacted with a protic polar group.

作為此種官能基係列舉例如胺基、氫氧基、環氧基、異氰酸酯基等，更加理想是胺基、環氧基和異氰酸酯基，甚至最好是環氧基。As such a functional group, for example, an amine group, a hydroxyl group, an epoxy group, an isocyanate group or the like is preferable, and an amine group, an epoxy group and an isocyanate group are more preferable, and an epoxy group is even more preferable.

作為交聯劑(F)之具體例係可以列舉六亞甲基二胺等之脂肪族聚胺類；4,4’-二胺基二苯基醚、二胺基二苯基碸等之芳香族聚胺類；2,6-雙(4’-疊氮基苄叉)環己酮、4,4’-二疊氮基二苯基碸等之疊氮基類；耐綸、聚六亞甲基二胺對苯二甲醯胺、聚六亞甲基間苯二甲醯胺等之聚醯胺類；N,N,N’,N’,N”,N”-(六烷氧基甲基)三聚氰胺等之三聚氰胺類；N,N’,N”,N”’-(四烷氧基甲基)甘脲等之甘脲類；乙烯乙二醇二(甲基)丙烯酸酯等之丙烯酸酯化合物；六亞甲基二異氰酸酯系聚異氰酸酯、異佛爾酮二異氰酸酯系聚異氰酸酯、甲代苯撐二異氰酸酯系聚異氰酸酯、氫化二苯基甲烷二異氰酸酯等之異氰酸酯系化合物；1,4-二-(羥基甲基)環己烷、1,4-二-(羥基甲基)原菠烷；1,3,4-三羥基環己烷；雙酚A型環氧樹脂、雙酚F型環氧樹脂、苯酚醛型環氧樹脂、甲酚醛型環氧樹脂、聚苯酚型環氧樹脂、環狀脂肪族環氧樹脂、脂肪族環氧丙基醚、環氧丙烯酸酯聚合物等之環氧化合物。Specific examples of the crosslinking agent (F) include aliphatic polyamines such as hexamethylenediamine; and aromatics such as 4,4'-diaminodiphenyl ether and diaminodiphenyl hydrazine; a polyamines; azide groups such as 2,6-bis(4'-azidobenzylidene)cyclohexanone, 4,4'-diazidediphenylfluorene; nylon, polyhexa Polyamines such as methyldiamine-p-xylamine, polyhexamethylene meta-xylyleneamine; N,N,N',N',N",N"-(hexadecyloxy) Methyl) melamine such as melamine; glycoluril such as N, N', N", N"'-(tetraalkoxymethyl) glycoluril; ethylene glycol di(meth)acrylate, etc. An acrylate compound; an isocyanate compound such as hexamethylene diisocyanate polyisocyanate, isophorone diisocyanate polyisocyanate, phenylene diisocyanate polyisocyanate or hydrogenated diphenylmethane diisocyanate; 1,4 -di-(hydroxymethyl)cyclohexane, 1,4-bis-(hydroxymethyl)protopane; 1,3,4-trihydroxycyclohexane; bisphenol A epoxy resin, bisphenol F Epoxy resin, phenolic epoxy resin, cresol novolac epoxy resin, polyphenol An epoxy compound such as an epoxy resin, a cyclic aliphatic epoxy resin, an aliphatic epoxy propyl ether or an epoxy acrylate polymer.

作為此種環氧化合物之具體例係能夠列舉以二環戊二烯作為骨格之3官能性環氧化合物(商品名稱「XD-1000」、日本化藥公司製)、[2,2-雙(羥基甲基)1-丁醇之1,2-環氧-4-(2-環氧乙烷基)環己烷附加物(具有環己烷骨格和末端環氧基之15官能性之脂環式環氧樹脂、商品名稱「EHPE3150」、DAICEL化學工業公司製)、環氧-環己烯-1,2-二羧酸雙(3-環己烯基甲基)修飾ε-己內酯(脂肪族環狀3官能性之環氧樹脂、商品名稱「EPL GT301」、DAICEL化學工業公司製)、環氧化丁烷四羧酸四(3-環己烯基甲基)修飾ε-己內酯(脂肪族環狀4官能性之環氧樹脂、商品名稱「EPL GT401」、DAICEL化學工業公司製)、3,4-環氧基環己烯基甲基-3’,4’-環氧基環己烯羧酸酯(商品名稱「CEL 2021P」、DAICEL化學工業公司製)等之具有脂環構造之環氧化合物；芳香族胺型多官能環氧化合物(商品名稱「H-434」、東都化成工業公司製)、甲酚醛型多官能環氧化合物(商品名稱「EOCN-1020」、日本化藥公司製)、苯酚醛型多官能環氧化合物(Epikote 152、154、日本環氧樹脂公司製)、具有萘骨格之多官能環氧化合物(商品名稱「EXA-4700」、大日本油墨化學股份有限公司製)、鏈狀烷基多官能環氧化合物(商品名稱「SR-TMP」、坂本藥品工業公司製)、多官能環氧聚丁二烯(商品名稱「EPL PB3600」、DAICEL化學工業公司製)、丙三醇之環氧丙基聚醚化合物(商品名稱「SR-GLG」、阪本藥品工業股份有限公司製)、二丙三醇聚環氧丙基醚化合物(商品名稱「SR-DGE」、阪本藥品工業股份有限公司製)、聚丙三醇聚環氧丙基醚化合物(商品名稱「SR-4GL」、阪本藥品工業股份有限公司製)等之不具有脂環構造之環氧化合物。Specific examples of such an epoxy compound include a trifunctional epoxide having dicyclopentadiene as a skeleton (trade name "XD-1000", manufactured by Nippon Kayaku Co., Ltd.), and [2, 2-dual ( 1,2-epoxy-4-(2-oxiranyl)cyclohexane addenda of hydroxymethyl)1-butanol (15-functional alicyclic ring with cyclohexane backbone and terminal epoxy group) Epoxy resin, trade name "EHPE3150", manufactured by DAICEL Chemical Industry Co., Ltd.), epoxy-cyclohexene-1,2-dicarboxylic acid bis(3-cyclohexenylmethyl) modified ε-caprolactone ( An aliphatic cyclic trifunctional epoxy resin, trade name "EPL GT301", manufactured by DAICEL Chemical Co., Ltd.), epoxidized butane tetracarboxylic acid tetrakis(3-cyclohexenylmethyl) modified ε-caprolactone (aliphatic cyclic tetrafunctional epoxy resin, trade name "EPL GT401", manufactured by DAICEL Chemical Industry Co., Ltd.), 3,4-epoxycyclohexenylmethyl-3', 4'-epoxy group An epoxy compound having an alicyclic structure such as a cyclohexene carboxylate (trade name "CEL 2021P", manufactured by DAICEL Chemical Co., Ltd.); an aromatic amine type polyfunctional epoxy compound (trade name "H-434", Dongdu Chemical industry A phenolic polyfunctional epoxy compound (trade name "EOCN-1020", manufactured by Nippon Kayaku Co., Ltd.), a phenolic polyfunctional epoxy compound (Epikote 152, 154, manufactured by Nippon Epoxy Co., Ltd.), A polyfunctional epoxy compound (trade name "EXA-4700", manufactured by Dainippon Ink Co., Ltd.) and a chain alkyl polyfunctional epoxy compound (trade name "SR-TMP", Sakamoto Pharmaceutical Co., Ltd.) , polyfunctional epoxy polybutadiene (trade name "EPL PB3600", manufactured by DAICEL Chemical Industry Co., Ltd.), propylene glycol polyether polyether compound (trade name "SR-GLG", Sakamoto Pharmaceutical Industry Co., Ltd. Co., Ltd.), diglycerol polyepoxypropyl ether compound (trade name "SR-DGE", manufactured by Sakamoto Pharmaceutical Co., Ltd.), polyglycerol polyepoxypropyl ether compound (trade name "SR- An epoxy compound having no alicyclic structure, such as 4GL", manufactured by Sakamoto Pharmaceutical Co., Ltd.).

即使是在這些當中，也最好是環氧化合物，具有脂環構造之環氧化合物係使得具有由本樹脂組成物來形成之有機鈍化膜之薄膜電晶體之安定性更加地良好，因此，變得更加地理想。Even among these, an epoxy compound is preferable, and an epoxy compound having an alicyclic structure makes the film transistor having an organic passivation film formed of the resin composition more stable, and thus becomes More ideal.

交聯劑(F)之分子量係並無特別限定，但是，通常為1０0～100,000，最好是500～50,000，更加理想是1,000～10,000。交聯劑係可以分別單獨或者是組合2種以上而使用。The molecular weight of the crosslinking agent (F) is not particularly limited, but is usually from 100 to 100,000, preferably from 500 to 50,000, more preferably from 1,000 to 10,000. The crosslinking agent may be used singly or in combination of two or more kinds.

使用於本發明之樹脂組成物之交聯劑(F)之含有量係相對於樹脂(A)之100重量份而通常成為0.1～200重量份，最好是1～150重量份，更加理想是5～100重量份之範圍。如果交聯劑之使用量為該範圍的話，則得到充分之耐熱性，因此，變得理想。The content of the crosslinking agent (F) to be used in the resin composition of the present invention is usually 0.1 to 200 parts by weight, preferably 1 to 150 parts by weight, based on 100 parts by weight of the resin (A), more preferably A range of 5 to 100 parts by weight. When the amount of the crosslinking agent used is in this range, sufficient heat resistance is obtained, which is preferable.

在使用於本發明之樹脂組成物，如果是不妨礙本發明效果之範圍的話，則可以由於要求而含有增感劑、界面活性劑、潛在性酸產生劑、氧化防止劑、光安定劑、消泡劑、顏料、染料等之其他之練合劑等。The resin composition used in the present invention may contain a sensitizer, a surfactant, a latent acid generator, an oxidation preventive agent, a light stabilizer, or a consumer, if it does not impair the effects of the present invention. Other agents such as foaming agents, pigments, dyes, and the like.

作為增感劑之具體例係列舉2H-吡啶-(3,2-b)-1,4-噁嗪-3(4H)-酮類、10H-吡啶-(3,2-b)-1,4-苯并噻嗪類、尿唑類、乙內醯脲類、丙二醯脲酸類、甘胺酸酐類、1-羥基苯并***類、四氧嘧啶類、馬來酸酐縮亞胺類等。As a specific example of the sensitizer, 2H-pyridine-(3,2-b)-1,4-oxazin-3(4H)-one, 10H-pyridine-(3,2-b)-1, 4-benzothiazide, urinazole, carbendazim, propylene urate, glycine anhydride, 1-hydroxybenzotriazole, alloxan, maleic anhydride Wait.

在本發明，作為樹脂組成物之成分係最好是含有界面活性劑。In the present invention, it is preferable that the component of the resin composition contains a surfactant.

界面活性劑係由於條紋(塗佈條紋痕跡)之防止、顯影性之提升等之目的而使用。作為其具體例係列舉聚氧乙烯月桂基醚、聚氧乙烯硬脂醯醚、聚氧乙烯油烯基醚等之聚氧乙烯烷基醚類；聚氧乙烯辛基苯基醚、聚氧乙烯壬基苯基醚等之聚氧乙烯芳基醚類；聚氧乙烯二月桂酸酯、聚氧乙烯二硬脂酸酯等之聚氧乙烯二烷基酯類等之非離子系界面活性劑；氟系界面活性劑；矽酮系界面活性劑；甲基丙烯酸共聚物系界面活性劑；丙烯酸共聚物系界面活性劑等。The surfactant is used for the purpose of preventing streaks (coating streaks), improving developability, and the like. As a specific example thereof, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, etc.; polyoxyethylene octyl phenyl ether, polyoxyethylene a polyoxyethylene aryl ether such as nonylphenyl ether; a nonionic surfactant such as polyoxyethylene dialkyl ester such as polyoxyethylene dilaurate or polyoxyethylene distearate; Fluorine-based surfactant; anthrone-based surfactant; methacrylic copolymer-based surfactant; acrylic copolymer-based surfactant.

潛在性酸產生劑係由於提升本發明之樹脂組成物之耐熱性和耐藥品性之目的而使用。作為其具體例係列舉藉由加熱而產生酸之陽離子聚合觸媒之鎏鹽、苯并噻唑鹽、銨鹽、鏻鹽等。即使是在這些當中，也最好是鎏鹽和苯并噻唑鹽。The latent acid generator is used for the purpose of improving the heat resistance and chemical resistance of the resin composition of the present invention. As a specific example thereof, a phosphonium salt, a benzothiazole salt, an ammonium salt, a phosphonium salt or the like which is a cationic polymerization catalyst which generates an acid by heating is used. Even among these, it is preferable to use a phosphonium salt and a benzothiazole salt.

作為氧化防止劑係可以將使用在通常之聚合物之苯酚系氧化防止劑、磷系氧化防止劑、硫系氧化防止劑、內酯系氧化防止劑等予以採用。例如作為苯酚類係可以列舉2,6-二-t-丁基-4-甲基苯酚、p-甲氧基苯酚、苯乙烯化苯酚、n-十八烷基-3-(3’,5’-二-t-丁基-4’-羥基苯基)丙酸酯、2,2’-亞甲基-雙(4-甲基-6-t-丁基苯酚)、2-t-丁基-6-(3’-t-丁基-5’-甲基-2’-羥基苄基)-4-甲基苯基丙烯酸酯、4,4’-丁叉-雙-(3-甲基-6-t-丁基苯酚)、4,4’-硫代-雙(3-甲基-6-t-丁基苯酚)、季戊四醇四[3-(3,5-二-t-丁基-4-羥基苯基)丙酸酯]、烷基化雙酚等。作為磷系氧化防止劑係列舉亞磷酸三苯酯、磷酸三(壬基苯基)，作為硫系氧化防止劑係列舉硫代二丙酸二月桂酯等。As the oxidation preventing agent, a phenol-based oxidation inhibitor, a phosphorus-based oxidation inhibitor, a sulfur-based oxidation inhibitor, a lactone-based oxidation inhibitor, or the like which is used in a usual polymer can be used. Examples of the phenol type include 2,6-di-t-butyl-4-methylphenol, p-methoxyphenol, styrenated phenol, and n-octadecyl-3-(3',5. '-Di-t-butyl-4'-hydroxyphenyl)propionate, 2,2'-methylene-bis(4-methyl-6-t-butylphenol), 2-t-butyl -6-(3'-t-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate, 4,4'-butylidene-bis-(3-A -6-t-butylphenol), 4,4'-thio-bis(3-methyl-6-t-butylphenol), pentaerythritol tetrakis[3-(3,5-di-t-butyl) Alkyl-4-hydroxyphenyl)propionate], alkylated bisphenol, and the like. Examples of the phosphorus-based oxidation preventing agent include triphenyl phosphite and tris(nonylphenyl) phosphate. Examples of the sulfur-based oxidation preventing agent include dilauryl thiodipropionate.

在本發明，作為樹脂組成物之成分係最好是含有光安定劑。光安定劑係可以是二苯甲酮系、水楊酸酯系、苯并***系、氰基丙烯酸酯系、金屬錯合鹽系等之紫外線吸收劑、受阻胺系(HALS)等之捕捉由於光而產生之自由基等之任何一種。即使是在這些當中，HALS係也是具有哌啶構造之化合物，對於本發明組成物之著色變少，安定性呈良好，因此，變得理想。作為具體之化合物係列舉雙(2,2,6,6-四甲基-4-哌啶基)癸二酸酯、1,2,2,6,6-五甲基-4-哌啶基/十三烷基1,2,3,4-丁烷四羧酸酯、雙(1-辛氧基-2,2,6,6-四甲基-4-哌啶基)癸二酸酯等。In the present invention, it is preferable that the component of the resin composition contains a photostabilizer. The photosensitizer may be a UV absorber such as a benzophenone system, a salicylate system, a benzotriazole system, a cyanoacrylate system or a metal complex salt system, or a hindered amine system (HALS). Any of free radicals or the like generated by light. Among these, the HALS system is a compound having a piperidine structure, and the composition of the present invention has less coloration and good stability, and therefore it is preferable. As a specific series of compounds, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1,2,2,6,6-pentamethyl-4-piperidinyl /tridecyl 1,2,3,4-butane tetracarboxylate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate Wait.

使用於本發明之樹脂組成物之調製方法係並無特別限定，可以藉由習知之方法而混合樹脂組成物之各構造成分、也就是樹脂(A)和有機溶媒(B)以及由於要求而使用之其他成分。The preparation method of the resin composition used in the present invention is not particularly limited, and the respective structural components of the resin composition, that is, the resin (A) and the organic solvent (B) can be mixed by a conventional method, and used as required. Other ingredients.

混合之方法係並無特別限定，但是，最好是將樹脂組成物之各構造成分溶解或分散於有機溶媒(B)而得到之溶液或分散液予以混合。藉此而以溶液或分散液之形態，來得到本發明之樹脂組成物。The method of mixing is not particularly limited, but it is preferred to mix a solution or dispersion obtained by dissolving or dispersing each structural component of the resin composition in the organic solvent (B). Thereby, the resin composition of the present invention is obtained in the form of a solution or a dispersion.

本發明使用之樹脂組成物之各構造成分溶解或分散於有機溶媒(B)之方法係可以按照常法。具體地說，可以將使用攪拌子和磁性攪拌器之攪拌、高速度勻化器、分散器、遊星攪拌機、二軸攪拌機、球磨機、三條壓輥等予以使用而進行。此外，可以在各成分溶解或分散於有機溶媒(B)之後，使用例如孔徑0.5μm程度之過濾器等而進行過濾。The method of dissolving or dispersing the respective constituent components of the resin composition used in the present invention in the organic solvent (B) can be carried out according to a usual method. Specifically, it can be carried out by using a stirring, a high-speed homogenizer, a disperser, a star agitator, a two-axis agitator, a ball mill, three press rolls, or the like using a stirrer and a magnetic stirrer. Further, after each component is dissolved or dispersed in the organic solvent (B), filtration can be carried out using, for example, a filter having a pore size of about 0.5 μm.

在本發明使用之樹脂組成物之各構造成分溶解或分散於有機溶媒(B)時之固態成分濃度係通常為1～70重量%、最好是5～60重量%、更加理想是10～50重量%。如果固態成分濃度為該範圍的話，則可以呈高度地平衡溶解安定性、對於基板上之塗佈性或形成之樹脂膜之膜厚均一性、平坦性等。The solid content concentration of each of the structural components of the resin composition used in the present invention dissolved or dispersed in the organic solvent (B) is usually from 1 to 70% by weight, preferably from 5 to 60% by weight, more preferably from 10 to 50. weight%. When the solid content concentration is in this range, the solubility stability, the coating property on the substrate, the film thickness uniformity of the formed resin film, the flatness, and the like can be highly balanced.

在本發明，可以在具有經過除去通道區域之半導體層表面之氧化膜之製程之薄膜電晶體之基板上而形成鈍化膜之後，交聯該鈍化膜。In the present invention, the passivation film can be crosslinked after forming a passivation film on a substrate having a thin film transistor which is subjected to a process of removing an oxide film on the surface of the semiconductor layer of the channel region.

形成於前述基板上之鈍化膜之交聯係可以藉由樹脂(A)之交聯反應而進行，最好是使用交聯劑。交聯係可以配合交聯劑之種類而選擇適當之方法，但是，通常是藉由加熱而進行。加熱方法係例如可以使用加熱板、烤爐等而進行。加熱溫度係通常為180～250℃，加熱時間係由於鈍化膜之大小或厚度和使用機器等而適度地選擇，例如在使用加熱板之狀態下，通常為5～90分鐘，在使用烤爐之狀態下，通常為30～120分鐘之範圍。加熱係可以配合需要而進行於惰性氣體氣氛下。作為惰性氣體係可以不包含氧且不氧化鈍化膜，列舉例如氮、氬、氦、氖、氙、氪等。即使是在這些當中，也最好是氮和氬，特別最好是氮。特別是氧含有量為0.1體積%以下，最好是0.01體積%以下之惰性氣體，特別適合為氮。這些惰性氣體係可以分別單獨或者是組合2種以上而使用。The crosslinking of the passivation film formed on the above substrate can be carried out by a crosslinking reaction of the resin (A), and it is preferred to use a crosslinking agent. The cross-linking can be selected in accordance with the type of the cross-linking agent, but it is usually carried out by heating. The heating method can be performed, for example, using a hot plate, an oven, or the like. The heating temperature is usually 180 to 250 ° C, and the heating time is appropriately selected depending on the size or thickness of the passivation film and the use of a machine or the like. For example, in the state where a hot plate is used, it is usually 5 to 90 minutes, and the oven is used. In the state, it is usually in the range of 30 to 120 minutes. The heating system can be carried out under an inert gas atmosphere as needed. The inert gas system may contain no oxygen and does not oxidize the passivation film, and examples thereof include nitrogen, argon, helium, neon, krypton, xenon, and the like. Even among these, nitrogen and argon are preferred, and nitrogen is particularly preferred. In particular, an inert gas having an oxygen content of 0.1% by volume or less, preferably 0.01% by volume or less is particularly suitable as nitrogen. These inert gas systems can be used individually or in combination of 2 or more types.

在本發明，前述鈍化膜係可以進行圖案化。形成於基板上之鈍化膜之圖案化係可以藉由例如以光阻劑作為遮罩來進行乾式蝕刻之方法，或者是在樹脂組成物，含有感應放射線性物質，在使用該樹脂組成物來形成之樹脂膜，使用活性放射線，形成潛像圖案，使用顯影液，顯在化潛像圖案之方法等，而進行圖案化。In the present invention, the aforementioned passivation film can be patterned. The patterning of the passivation film formed on the substrate can be performed by, for example, dry etching using a photoresist as a mask, or in a resin composition containing an inductive radiation substance, and using the resin composition to form The resin film is patterned by using active radiation to form a latent image pattern, using a developing solution, and developing a latent image pattern.

作為活性放射線係如果是可以活化光酸產生劑而改變包含光酸產生劑之交聯性組成物之鹼可溶性的話，則並無特別限定。具體地說，可以使用紫外線、g射線或i射線等之單一波長紫外線、KrF準分子雷射光、ArF準分子雷射光等之光線；例如電子線之粒子線等。作為呈選擇性圖案狀地照射這些活性放射線而形成潛像圖案之方法係可以按照常法，可以使用例如藉由縮小投影曝光裝置等而透過要求之遮罩圖案來照射紫外線、g射線、i射線、KrF準分子雷射光、ArF準分子雷射光等之光線之方法、或者是藉由電子線等之粒子線而進行描繪之方法等。在使用光線來作為活性放射線之狀態下，可以是單一波長光，也可以是混合波長光。照射條件係配合使用之活性放射線而適度地選擇，但是，例如在使用波長200～450nm之光線之狀態下，照射量係通常為10～1,000mJ/cm2 ，最好是50～500mJ/cm2 之範圍，配合照射時間和照亮度而決定。在像這樣而照射活性放射線之後，配合需要而在60～130℃程度之溫度，對於樹脂膜，進行1～2分鐘程度之加熱處理。The active radiation system is not particularly limited as long as it is capable of activating the photoacid generator and changing the alkali solubility of the crosslinkable composition containing the photoacid generator. Specifically, light of a single wavelength such as ultraviolet light, g-ray or i-ray, KrF excimer laser light, ArF excimer laser light, or the like; for example, a particle line of an electron beam or the like can be used. As a method of forming the latent image pattern by selectively irradiating these active radiations in a selective pattern, ultraviolet rays, g rays, and i rays can be irradiated through a desired mask pattern by, for example, reducing a projection exposure apparatus or the like in accordance with a conventional method. A method of light such as KrF excimer laser light or ArF excimer laser light, or a method of drawing by a particle line such as an electron beam. In the state where light is used as the active radiation, it may be a single wavelength light or a mixed wavelength light. The irradiation conditions are appropriately selected in accordance with the active radiation to be used. However, for example, in the case of using light having a wavelength of 200 to 450 nm, the irradiation amount is usually 10 to 1,000 mJ/cm 2 , preferably 50 to 500 mJ/cm 2 . The range is determined by the irradiation time and the brightness. After the active radiation is irradiated as described above, the resin film is heated to a temperature of about 60 to 130 ° C for about 1 to 2 minutes.

接著，對於形成在鈍化膜之潛像圖案，進行顯影及顯在化。在本發明，將此種製程，稱為「圖案化」，將圖案化之鈍化膜，稱為「圖案化鈍化膜」。作為顯影液係通常使用鹼性化合物之水性溶液。作為鹼性化合物係可以使用例如鹼金屬鹽、胺、銨鹽。鹼性化合物係可以是無機化合物，也可以是有機化合物。作為這些化合物之具體例係列舉氫氧化鈉、氫氧化鉀、碳酸鈉、矽酸鈉、偏矽酸鈉等之鹼金屬鹽；氨水；乙胺、n-丙胺等之伯胺；二乙胺、二-n-丙胺等之仲胺；三乙胺、甲基二乙基胺等之叔胺；四甲基銨氫氧化物、四乙基銨氫氧化物、四丁基銨氫氧化物、膽鹼等之季銨鹽；二甲基乙醇胺、三乙醇胺等之醇胺；吡咯、哌啶、1,8-二吖二環[5. 4. 0]十一-7-烯烴、1,5-二吖二環[4. 3. 0]九-5-烯烴、N-甲基吡咯烷酮等之環狀胺類等。這些鹼性化合物係可以分別單獨或者是組合2種以上而使用。Next, the latent image pattern formed on the passivation film is developed and developed. In the present invention, such a process is referred to as "patterning", and the patterned passivation film is referred to as a "patterned passivation film." As the developer, an aqueous solution of a basic compound is usually used. As the basic compound, for example, an alkali metal salt, an amine or an ammonium salt can be used. The basic compound may be an inorganic compound or an organic compound. Specific examples of these compounds include alkali metal salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, and sodium metasilicate; aqueous ammonia; primary amines such as ethylamine and n-propylamine; diethylamine; a secondary amine such as bis-n-propylamine; a tertiary amine such as triethylamine or methyldiethylamine; tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, and cholesterium a quaternary ammonium salt such as a base; an alcohol amine such as dimethylethanolamine or triethanolamine; pyrrole, piperidine, 1,8-dioxane[5.4.0]undec-7-olefin, 1,5- a cyclic amine such as a diterpene ring [4.3.0] hex-5-olefin or N-methylpyrrolidone. These basic compounds may be used alone or in combination of two or more.

作為鹼性水溶液之水性媒體係可以使用水；甲醇、乙醇等之水溶性有機溶媒。鹼性水溶液係可以添加適當量之界面活性劑等。As the aqueous medium for the alkaline aqueous solution, water; a water-soluble organic solvent such as methanol or ethanol can be used. An alkaline aqueous solution may be added with an appropriate amount of a surfactant or the like.

作為在具有潛像圖案之鈍化膜來接觸顯影液之方法係例如使用漿式攪拌法、噴射法、浸漬法等之方法。顯影係通常為0～100℃、最好是5～55℃、更加理想是10～30℃之範圍，通常是在30～180秒鐘之範圍，適度地進行選擇。As a method of contacting the developing solution with a passivation film having a latent image pattern, for example, a method such as a slurry stirring method, a spraying method, a dipping method, or the like is used. The developing system is usually in the range of 0 to 100 ° C, preferably 5 to 55 ° C, more preferably 10 to 30 ° C, and is usually selected in an appropriate range of 30 to 180 seconds.

為了在像這樣而形成作為目的之圖案化鈍化膜之後，配合需要而除去基板上、基板背面及基板端部之顯影殘渣，因此，可以藉由漂洗液而漂洗基板。在漂洗處理後，藉由壓縮空氣或壓縮氮而除去殘留之漂洗液。In order to form the intended patterned passivation film in this manner, the development residue on the substrate, the back surface of the substrate, and the end portion of the substrate is removed as needed. Therefore, the substrate can be rinsed by the rinse liquid. After the rinsing treatment, the residual rinsing liquid is removed by compressing air or compressing nitrogen.

此外，為了配合需要而鈍化光酸產生劑，因此，也可以在具有圖案化鈍化膜之基板整個面，照射活性放射線。可以在活性放射線之照射，利用例舉於前述潛像圖案形成之方法。可以進行照射，同時或照射後，加熱鈍化膜。作為加熱方法係列舉例如藉由加熱板或烤爐內而加熱基板之方法。溫度係通常為100～300℃、最好是120～200℃之範圍。Further, since the photoacid generator is passivated in order to meet the needs, the active radiation may be irradiated on the entire surface of the substrate having the patterned passivation film. The method of forming the latent image pattern described above can be utilized for irradiation with active radiation. The irradiation can be performed while heating or after the irradiation, the passivation film is heated. As a series of heating methods, for example, a method of heating a substrate by means of a heating plate or an oven is used. The temperature system is usually in the range of 100 to 300 ° C, preferably 120 to 200 ° C.

在本發明，可以在基板上形成圖案化樹脂之後，進行圖案化樹脂之交聯反應。交聯係可以相同於形成在前述基板上之鈍化膜之交聯而進行。In the present invention, the cross-linking reaction of the patterned resin can be carried out after the patterning resin is formed on the substrate. The crosslinking can be carried out in the same manner as the crosslinking of the passivation film formed on the aforementioned substrate.

如果藉由本發明之半導體元件基板之製造方法的話，則可以製造高可靠性之半導體元件基板。According to the method of manufacturing a semiconductor element substrate of the present invention, a highly reliable semiconductor element substrate can be manufactured.

藉由本發明之製造方法而得到之薄膜電晶體係可以使用在主動矩陣型液晶顯示器或主動矩陣型有機EL等之顯示裝置。此外，藉由本發明之製造方法而製造之半導體元件係鈍化膜成為平坦，因此，可以在顯示裝置，達到亮度之提升。此外，可以達到消耗電力之減低。此外，可以達到薄膜電晶體之壽命提升。The thin film electrocrystallization system obtained by the production method of the present invention can be used in a display device such as an active matrix liquid crystal display or an active matrix organic EL. Further, since the passivation film of the semiconductor element manufactured by the manufacturing method of the present invention is flat, the brightness can be improved in the display device. In addition, the reduction in power consumption can be achieved. In addition, the life of the thin film transistor can be increased.

此外，包含有機材料而組成之鈍化膜係低介電常數，因此，可以抑制RC延遲。Further, the passivation film composed of an organic material is low in dielectric constant, and therefore, RC retardation can be suppressed.

【實施例】[Examples]

在以下，列舉實施例及比較例，就本發明而更加具體地進行說明。各例子中之「份」及「%」係並無特別限定，分別成為「重量份」及「重量%」。Hereinafter, the present invention will be more specifically described by way of examples and comparative examples. The "parts" and "%" in each of the examples are not particularly limited, and are "parts by weight" and "% by weight", respectively.

各特性係藉由以下之方法而進行評價。Each characteristic was evaluated by the following method.

(1)薄膜電晶體特性(1) Thin film transistor characteristics

使用半導體參數分析儀(Agilent公司製、4156A)，測定在製作即刻後之測定用試料(具有薄膜電晶體之基板)之源極‧汲極間電流相對於閘極電壓變化之變化。在源極電極和汲極電極之間，施加10V之電壓，使得在-10V～15V之範圍以0.2V之刻度來改變閘極電極時之源極‧汲極間電流之最小值，成為截止漏電流而進行觀測。接著，將測定用試料，設置在設定於溫度60℃濕度90%之恆溫恆濕槽(Espec公司製、Platinous PR-2KP)之中。在設置後，以每20小時而直到100小時為止，在超過100小時之後，以每100小時，藉由前述方法而測定截止漏電流值，以截止漏電流值達到至1.0×10-11 A之時間，作為薄膜電晶體特性而進行觀測。如果藉由該分析的話，則薄膜電晶體特性越長而薄膜電晶體之可靠性越高。Using a semiconductor parameter analyzer (manufactured by Agilent Co., Ltd., 4156A), the change in the source ‧ 汲-electrode current with respect to the gate voltage change of the sample for measurement immediately after the preparation of the sample (the substrate having the thin film transistor) was measured. A voltage of 10V is applied between the source electrode and the drain electrode, so that the minimum value of the current between the source and the drain of the gate electrode when the gate electrode is changed in the range of -10V to 15V becomes a cutoff leak. The current is observed. Next, the sample for measurement was placed in a constant temperature and humidity chamber (Platinous PR-2KP, manufactured by Espec Co., Ltd.) set at a temperature of 60 ° C and a humidity of 90%. After the setting, the off-leakage current value is measured by the above method every 100 hours after every 100 hours until 100 hours, and after 100 hours, the off-leakage current value reaches 1.0×10 -11 A. The time was observed as the characteristics of the thin film transistor. According to this analysis, the longer the film transistor characteristics are, the higher the reliability of the film transistor is.

(製造例1)(Manufacturing Example 1)

將由40莫爾%之N-(2-乙基己基)-二環[2. 2. 1]庚基-5-烯烴-5-2,3-二羧基醯亞胺(NEHI)和60莫爾%之8-羥基羰基四環[4. 4. 0. 12,5 . 17,10 ]十二-3-烯烴(TCDC)而組成之單體混合物100重量份、2重量份之1,5-己二烯、0.02重量份之(1,3-二甲基咪唑啉-2-叉)(三環己基膦)苄叉釕氯化物(藉由記載於Org. Lett.,第1卷、953頁、1999年之方法而進行合成)以及400重量份之二乙烯乙二醇甲基***，裝入至氮取代之玻璃製耐壓反應器，進行攪拌，並且，在80℃，進行4小時之反應，得到聚合反應液。接著，藉由將得到之聚合反應液，放入至高壓鍋，在150℃，以氫壓力4MPa，攪拌5小時，進行氫添加反應，而得到環狀烯烴樹脂之溶液。得到之溶液中之環狀烯烴樹脂之聚合轉化率係99.7%，重量平均分子量係7150，數平均分子量係4690，分子量分布係1.52，氫添加率係99.7%。Will be composed of 40 mol% N-(2-ethylhexyl)-bicyclo[2.2.1]heptyl-5-olefin-5-2,3-dicarboxyindenine (NEHI) and 60 moir 100 parts by weight and 2 parts by weight of a monomer mixture composed of 8% hydroxycarbonyltetracyclo[ 4.4.1 . 2 2,5,7,10 ] dode -3-olefin (TCDC), 5-hexadiene, 0.02 parts by weight of (1,3-dimethylimidazolin-2-yl)(tricyclohexylphosphine)benzylidene chloride (as described in Org. Lett., Vol. 1, The synthesis was carried out by the method of 953 and 1999), and 400 parts by weight of ethylene glycol methyl ether was charged into a nitrogen-substituted glass pressure-resistant reactor, stirred, and carried out at 80 ° C for 4 hours. The reaction was carried out to obtain a polymerization reaction liquid. Then, the obtained polymerization reaction liquid was placed in a pressure cooker, and stirred at 150 ° C for 4 hours under a hydrogen pressure of 4 MPa to carry out a hydrogen addition reaction to obtain a solution of a cyclic olefin resin. The polymerization conversion ratio of the cyclic olefin resin in the obtained solution was 99.7%, the weight average molecular weight was 7,150, the number average molecular weight was 4,690, the molecular weight distribution was 1.52, and the hydrogen addition rate was 99.7%.

接著，在正如以上而得到之環狀烯烴樹脂之溶液(溶液中之環狀烯烴樹脂成為100重量份之量)，添加作為具有酸基之化合物之2重量份之吡嗪-2,3-二羧酸、作為感應放射線化合物之30重量份之1,1,3-三(2,5-二甲基-4-羥苯基)-3-苯基丙烷(1莫爾)和1,2-萘醌二疊氮基-5-磺酸氯化物(2莫爾)之縮合物(東洋合成工業公司製、「TS200」)之30重量份、作為交聯劑之30重量份之甲基醚化三聚氰胺樹脂(Cytec工業公司製、「Cymel 370」)、30重量份之3,4-環氧環己烯基甲基-3’,4’-環氧環己烯羧酸酯(DAICEL化學工業公司製、「CEL2021P」)和10重量份之環氧化丁烷四羧酸四(3-環己烯基甲基)修飾ε-己內酯(DAICEL化學工業公司製、「EPL GT401」)、作為氧化防止劑之1重量份之季戊四醇四[3-(3,5-二-t-丁基-4-羥苯基)丙酸酯(Ciba Specialty Chemicals(特殊化學)公司製、「IRGANOX 1010」)以及作為界面活性劑之溶液中濃度成為300ppm之量之矽酮系界面活性劑(信越矽酮公司製、「KP-341」)，並且，添加100重量份之二乙烯乙二醇甲基***，進行混合及攪拌。在攪拌30分鐘之後，藉由孔徑0.45μm之聚四氟乙烯製過濾器而過濾該溶液，調製包含環狀烯烴樹脂且具有感應放射線性之樹脂組成物(α)。Next, in the solution of the cyclic olefin resin obtained as described above (the amount of the cyclic olefin resin in the solution is 100 parts by weight), 2 parts by weight of pyrazine-2,3-di which is a compound having an acid group is added. a carboxylic acid, as an inductive radiation compound, 30 parts by weight of 1,1,3-tris(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane (1 mol) and 1,2- 30 parts by weight of a condensate of naphthoquinonediazide-5-sulfonic acid chloride (2 mole) ("TS200" manufactured by Toyo Synka Kogyo Co., Ltd.), and 30 parts by weight of methyl etherification as a crosslinking agent Melamine resin ("Cymel 370", manufactured by Cytec Industries, Inc.), 30 parts by weight of 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexene carboxylate (DAICEL Chemical Industry Co., Ltd.) And "10 parts by weight of epoxidized butane tetracarboxylic acid tetrakis(3-cyclohexenylmethyl)-modified ε-caprolactone ("EPL GT401", manufactured by DAICEL Chemical Industry Co., Ltd.), as oxidation 1 part by weight of pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate (manufactured by Ciba Specialty Chemicals Co., Ltd., "IRGANOX 1010") and Concentration in solution as a surfactant 300ppm is the amount of a silicone-based surfactant ketone (ketone by Shin-Etsu Silicone Co., Ltd., "KP-341"), and adding 100 parts by weight of diethylene glycol monomethyl ether were mixed and stirred. After stirring for 30 minutes, the solution was filtered through a filter made of polytetrafluoroethylene having a pore size of 0.45 μm to prepare a resin composition (α) containing a cyclic olefin resin and having an inductively linear property.

(製造例2)(Manufacturing Example 2)

將20重量份之苯乙烯、25重量份之丁基甲基丙烯酸酯、25重量份之2-乙基己基丙烯酸酯、30重量份之甲基丙烯酸、0.5重量份之2,2-偶氮二氮丁腈和300重量份之丙二醇單甲基醚乙酸酯，裝入至氮取代之玻璃製耐壓反應器，在氮氣流中，進行攪拌，同時，在80℃，進行4小時之反應。接著，藉由以旋轉式氣化器，來濃縮得到之反應溶液，而以固態成分濃度35%，來得到丙烯樹脂之溶液。得到之溶液中之丙烯樹脂之聚合轉化率係99%以上，重量平均分子量係15000，數平均分子量係6500，分子量分布係2.31。20 parts by weight of styrene, 25 parts by weight of butyl methacrylate, 25 parts by weight of 2-ethylhexyl acrylate, 30 parts by weight of methacrylic acid, 0.5 parts by weight of 2,2-azodiazepine Nitrile and 300 parts by weight of propylene glycol monomethyl ether acetate were placed in a nitrogen-substituted glass pressure-resistant reactor, stirred in a nitrogen stream, and reacted at 80 ° C for 4 hours. Next, the obtained reaction solution was concentrated by a rotary gasifier to obtain a solution of the propylene resin at a solid concentration of 35%. The polymerization conversion ratio of the propylene resin in the obtained solution was 99% or more, the weight average molecular weight was 15,000, the number average molecular weight was 6,500, and the molecular weight distribution was 2.31.

接著，在正如以上而得到之丙烯樹脂之溶液(溶液中之丙烯樹脂成為100重量份之量)，添加作為具有鍵結於矽原子之氫化香芹羥基之化合物之10重量份之3-環氧丙氧基丙基三甲氧基矽烷(東麗Dow Corning公司製、「SH-6040」)、作為感應放射線化合物之1,1,3-三(2,5-二甲基-4-羥苯基)-3-苯基丙烷(1莫爾)和1,2-萘醌二疊氮基-5-磺酸氯化物(2莫爾)之縮合物(東洋合成工業公司製、「TS200」)之30重量份、作為交聯劑之50重量份之甲基醚化三聚氰胺樹脂(Cytec工業公司製、「Cymel 370」)、作為氧化防止劑之1重量份之季戊四醇四[3-(3,5-二-t-丁基-4-羥苯基)丙酸酯(Ciba Specialty Chemicals(特殊化學)公司製、「IRGANOX 1010」)以及作為界面活性劑之溶液中濃度成為300重量ppm之量之矽酮系界面活性劑(信越矽酮公司製、「KP-341」)，並且，添加100重量份之丙二醇單甲基醚乙酸酯，進行混合及攪拌。在攪拌30分鐘之後，藉由孔徑0.45μm之聚四氟乙烯製過濾器而過濾該溶液，調製包含丙烯樹脂且具有感應放射線性之樹脂組成物(β)。Next, in the solution of the propylene resin obtained as above (the amount of the propylene resin in the solution is 100 parts by weight), 10 parts by weight of a 3-epoxy compound as a compound having a hydrogenated carnation hydroxyl group bonded to a ruthenium atom is added. Propyloxypropyltrimethoxydecane ("SH-6040", manufactured by Toray Corning Co., Ltd.), 1,1,3-tris(2,5-dimethyl-4-hydroxyphenyl) as an inductive radiation compound a condensate of -3-phenylpropane (1 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2 mol) (manufactured by Toyo Seiki Co., Ltd., "TS200") 30 parts by weight of methyl etherified melamine resin (Cymel 370) manufactured by Cytec Industries Co., Ltd. as a crosslinking agent, and 1 part by weight of pentaerythritol tetrakis [3-(3,5-) as an oxidation preventing agent. Di-t-butyl-4-hydroxyphenyl)propionate ("Igly Chemical Co., Ltd.", "IRGANOX 1010") and a solution of a surfactant as a surfactant in an amount of 300 ppm by weight of anthrone The surfactant ("KP-341", manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and 100 parts by weight of propylene glycol monomethyl ether acetate was added and mixed and stirred. After stirring for 30 minutes, the solution was filtered through a filter made of polytetrafluoroethylene having a pore size of 0.45 μm to prepare a resin composition (β) containing propylene resin and having inductive radiation.

(實施例1)(Example 1)

在玻璃基板(康寧公司、製品名稱：Corning 1737)之上，藉由濺鍍法而形成作為閘極電極之200nm厚度之鉻膜。接著，圖案化前述鉻膜而成為閘極電極，因此，藉由以旋轉塗佈法，將使用作為蝕刻用遮罩之正型光阻劑(日本Zeon公司製、ZPP-1800U3)，來塗佈於前述鉻膜上，使用加熱板，除去溶媒，而形成1.5μm之阻劑膜。接著，進行曝光製程、顯影製程而對於阻劑膜，進行圖案化。接著，在蝕刻液，使用硝酸二銨鈰，藉由濕式蝕刻而進行鉻膜之圖案化，形成閘極電極。接著，使用單乙醇胺(MEA)和二甲基亞碼(DMSO)之混合溶液(MEA/DMSO=7/3)之剝離液而除去阻劑膜。On the glass substrate (Corning, product name: Corning 1737), a chromium film having a thickness of 200 nm as a gate electrode was formed by sputtering. Then, the chrome film is patterned to form a gate electrode. Therefore, a positive photoresist (ZPP-1800U3, manufactured by Zeon Corporation, Japan) is used as a mask for etching by a spin coating method. On the chromium film, a heating plate was used to remove the solvent to form a 1.5 μm resist film. Next, an exposure process and a development process are performed, and the resist film is patterned. Next, in the etching liquid, a chromium film was patterned by wet etching using diammonium nitrate, and a gate electrode was formed. Next, the resist film was removed using a stripping solution of a mixed solution of monoethanolamine (MEA) and dimethylamethylene (DMSO) (MEA/DMSO = 7/3).

接著，分別藉由CVD法而依序地形成覆蓋閘極電極來成為閘極絕緣膜之450nm厚度之氮化矽物膜、成為半導體層之250nm厚度之a-Si層(非結晶矽層)以及成為不純物添加半導體層之50nm厚度之n+Si層。接著，呈島狀地圖案化前述半導體層和不純物添加半導體層，因此，藉由以旋轉塗佈法，將使用作為蝕刻用遮罩之正型光阻劑(日本Zeon公司製、ZPP-1800U3)，來塗佈於不純物添加半導體層上，使用加熱板，除去溶媒，而形成1.5μm之阻劑膜。接著，經過曝光製程、顯影製程而對於阻劑膜，進行圖案化。接著，藉由乾式蝕刻而呈島嶼狀地圖案化不純物添加半導體層和半導體層。接著，使用單乙醇胺(MEA)和二甲基亞碼(DMSO)之混合溶液(MEA/DMSO=7/3)之剝離液而除去阻劑膜。接著，藉由氫電漿處理用裝置(改良Dipole Ring Magnet[東京電子公司製]而成為可進行電漿處理之裝置)，以施加100W偏壓之狀態，而進行5分鐘之氫電漿處理。接著，藉由超純水，而對於經歷至前述製程為止之基板，進行30秒鐘之漂洗，利用氮而由基板之表面，來除去在漂洗時之附著之超純水。接著，藉由旋轉塗佈法而將成為包含有機材料所組成之鈍化膜之前述樹脂組成物(α)，塗佈於經歷前述製程之基板上，使用加熱板，在90℃進行2分鐘之加熱乾燥(預烘乾)，形成膜厚2.5μm之樹脂膜。接著，在該樹脂膜，透過10μm×10μm之孔洞圖案之遮罩，在40秒鐘、空氣中，照射365nm之光強度為5mW/cm2 之紫外線。接著，在使用0.4重量%之四甲基銨氫氧化物水溶液而在23℃進行90秒鐘之顯影處理之後，在藉由超純水而進行30秒鐘之漂洗來形成接點孔之圖案後，於230℃，進行60分鐘之加熱(後續烘乾)。藉此而得到形成圖案化之有機鈍化膜之薄膜電晶體。Then, a silicon nitride film having a thickness of 450 nm, which is a gate insulating film, and an a-Si layer (amorphous germanium layer) having a thickness of 250 nm which is a semiconductor layer, are sequentially formed by a CVD method. An n+Si layer having a thickness of 50 nm in which a semiconductor layer is added as an impurity. Then, the semiconductor layer and the impurity-added semiconductor layer are patterned in an island shape. Therefore, a positive photoresist used as a mask for etching (ZPP-1800U3, manufactured by Zeon Corporation, Japan) is used by a spin coating method. The film was applied to the impurity-added semiconductor layer, and a heating plate was used to remove the solvent to form a 1.5 μm resist film. Next, the resist film is patterned by an exposure process and a development process. Next, the semiconductor layer and the semiconductor layer are added by patterning the impurities in an island shape by dry etching. Next, the resist film was removed using a stripping solution of a mixed solution of monoethanolamine (MEA) and dimethylamethylene (DMSO) (MEA/DMSO = 7/3). Then, a hydrogen plasma treatment device (modified Dipole Ring Magnet (manufactured by Tokyo Electronics Co., Ltd.) was used as a device capable of performing plasma treatment), and a hydrogen plasma treatment was performed for 5 minutes while applying a bias of 100 W. Next, the substrate subjected to the above-described process was rinsed for 30 seconds by ultrapure water, and the ultrapure water adhered at the time of rinsing was removed from the surface of the substrate by nitrogen. Next, the resin composition (α) which is a passivation film containing an organic material is applied onto a substrate subjected to the above-described process by a spin coating method, and heated at 90 ° C for 2 minutes using a hot plate. Drying (pre-baking) to form a resin film having a film thickness of 2.5 μm. Next, the resin film was passed through a mask of a hole pattern of 10 μm × 10 μm, and ultraviolet rays having a light intensity of 5 mW/cm 2 at 365 nm were irradiated in the air for 40 seconds. Subsequently, after a development treatment of a 0.4% by weight aqueous solution of tetramethylammonium hydroxide at 23 ° C for 90 seconds, a pattern of contact holes was formed after rinsing for 30 seconds by ultrapure water. Heating at 230 ° C for 60 minutes (subsequent drying). Thereby, a thin film transistor in which a patterned organic passivation film is formed is obtained.

(實施例2)(Example 2)

除了在氫電漿處理而使得偏壓成為0W以外，其餘係藉由相同於實施例1之同樣方法而得到形成圖案化之有機鈍化膜之薄膜電晶體。A thin film transistor in which a patterned organic passivation film was formed was obtained in the same manner as in Example 1 except that the bias voltage was changed to 0 W in the hydrogen plasma treatment.

(實施例3)(Example 3)

除了使用樹脂組成物(β)來取代樹脂組成物(α)以外，其餘係藉由相同於實施例2之同樣方法而得到形成圖案化之有機鈍化膜之薄膜電晶體。A thin film transistor in which a patterned organic passivation film was formed was obtained in the same manner as in Example 2 except that the resin composition (β) was used instead of the resin composition (α).

(比較例1)(Comparative Example 1)

除了不進行氫電漿處理以外，其餘係相同於實施例1而製作形成圖案化之有機鈍化膜之薄膜電晶體，進行評價。A thin film transistor in which a patterned organic passivation film was formed in the same manner as in Example 1 except that the hydrogen plasma treatment was not performed was evaluated.

(比較例2)(Comparative Example 2)

除了將鈍化膜，變更成為藉由以矽烷氣體和銨氣體來作為原料之CVD法而成膜之氮化矽膜(SiNx膜)以外，其餘係相同於實施例1而製作薄膜電晶體，進行評價。A thin film transistor was produced in the same manner as in Example 1 except that the passivation film was changed to a tantalum nitride film (SiNx film) formed by a CVD method using decane gas and ammonium gas as a raw material. .

(比較例3)(Comparative Example 3)

除了不進行氫電漿處理以外，其餘係相同於比較例2而製作薄膜電晶體，進行評價。A thin film transistor was produced in the same manner as in Comparative Example 2 except that the hydrogen plasma treatment was not performed, and evaluation was performed.

(比較例4)(Comparative Example 4)

除了不進行氫電漿處理以外，其餘係相同於實施例3而製作形成圖案化之有機鈍化膜之薄膜電晶體，進行評價。A thin film transistor in which a patterned organic passivation film was formed in the same manner as in Example 3 except that the hydrogen plasma treatment was not performed was evaluated.

此外，在表1，也顯示關於以下之特性而進行評價之結果。Further, in Table 1, the results of evaluations regarding the following characteristics are also displayed.

(2)開口率(2) aperture ratio

將除去配線部和電晶體部以外之光來通過之部分之面積相對於製作之薄膜電晶體基板之面積之比例予以求出而作為開口率。開口率越高而亮度越加良好。The ratio of the area of the portion through which the light other than the wiring portion and the transistor portion was removed to the area of the thin film transistor substrate to be formed was determined as the aperture ratio. The higher the aperture ratio, the better the brightness.

(3)TFT製作後之鈍化膜製作製程數(3) Number of passivation film fabrication processes after TFT fabrication

在藉由圖1(a)～圖2(c)所示之製程而製作薄膜電晶體之後，進行直到得到形成圖案化鈍化膜之薄膜電晶體為止之必要之製程數之比較。After the thin film transistor is formed by the processes shown in FIGS. 1(a) to 2(c), the number of processes necessary until the thin film transistor forming the patterned passivation film is obtained is compared.

也就是說，在實施例1～3，需要(i)氫電漿處理、(ii)潔淨、(iii)塗佈、(iv)曝光、(v)顯影、(vi)烘乾之6個製程。此外，在比較例1及4，需要(i)潔淨、(ii)塗佈、(iii)曝光、(iv)顯影、(v)烘乾之5個製程。此外，在比較例2，需要(i)潔淨、(ii)藉由CVD法而形成SiNx膜、(iii)潔淨、(iv)塗佈、(v)曝光、(vi)顯影、(vii)烘乾、(viii)乾式蝕刻之8個製程。此外，在比較例3，需要(i)氫電漿處理、(ii)潔淨、(iii)藉由CVD法而形成SiNx膜、(iv)潔淨、(v)塗佈、(vi)曝光、(vii)顯影、(viii)烘乾、(ix)乾式蝕刻之9個製程。That is, in Examples 1 to 3, six processes of (i) hydrogen plasma treatment, (ii) clean, (iii) coating, (iv) exposure, (v) development, and (vi) drying are required. . Further, in Comparative Examples 1 and 4, five processes of (i) clean, (ii) coating, (iii) exposure, (iv) development, and (v) drying were required. Further, in Comparative Example 2, (i) clean, (ii) formation of SiNx film by CVD method, (iii) clean, (iv) coating, (v) exposure, (vi) development, (vii) baking Dry, (viii) 8 processes of dry etching. Further, in Comparative Example 3, (i) hydrogen plasma treatment, (ii) cleaning, (iii) formation of SiNx film by CVD method, (iv) cleaning, (v) coating, (vi) exposure, ( Vii) 9 processes for development, (viii) drying, and (ix) dry etching.

(4)比介電常數及RC延遲(4) Specific dielectric constant and RC delay

在藉由旋轉塗佈法而將在製造例1及2製作且包含有機材料所組成之樹脂組成物來塗佈於矽晶圓上之後，使用加熱板，在90℃進行2分鐘之加熱乾燥(預烘乾)，形成膜厚2.5μm之樹脂膜。接著，在230℃進行60分鐘之加熱，得到由形成包含有機材料之樹脂膜之矽晶圓而組成之試驗用試料。After coating the resin composition composed of the organic materials in the production examples 1 and 2 by spin coating, the resin composition was applied onto a tantalum wafer, and then heated and dried at 90 ° C for 2 minutes using a hot plate. Pre-baking), a resin film having a film thickness of 2.5 μm was formed. Next, heating was carried out at 230 ° C for 60 minutes to obtain a test sample composed of a tantalum wafer in which a resin film containing an organic material was formed.

此外，在矽晶圓上，形成藉由以矽烷氣體和銨氣體來作為原料之CVD法而成膜之氮化矽膜(SiNx膜)，使用加熱板，在90℃進行2分鐘之加熱乾燥(預烘乾)，形成膜厚120nm之樹脂膜。接著，在230℃進行60分鐘之加熱，得到由形成SiNx膜之矽晶圓而組成之試驗用試料。接著，使用得到之試驗用試料，按照JIS C6481，在10kHz(室溫)，測定樹脂膜和SiNx膜之比介電常數。比介電常數越低越好。Further, on the tantalum wafer, a tantalum nitride film (SiNx film) formed by a CVD method using decane gas and ammonium gas as a raw material was formed, and heated and dried at 90 ° C for 2 minutes using a hot plate ( Pre-baking), a resin film having a film thickness of 120 nm was formed. Next, heating was performed at 230 ° C for 60 minutes to obtain a test sample composed of a silicon wafer on which a SiNx film was formed. Next, using the obtained test sample, the specific dielectric constant of the resin film and the SiNx film was measured at 10 kHz (room temperature) in accordance with JIS C6481. The lower the specific dielectric constant, the better.

RC延遲係在65inch之全高畫質電視，藉由下列之公式而算出以輸入訊號為10V且直到97%之電壓到達至資料配線末端為止之時間，顯示成為RC延遲時間(DT)。The RC delay is a full-height TV of 65 inches. The time after the input signal is 10V and the voltage reaches 97% until the end of the data wiring is calculated by the following formula, the display becomes the RC delay time (DT).

V(t)=V(1-exp[t/RC])V(t)=V(1-exp[t/RC])

V：輸入電壓、t：時間、R：資料配線之電阻、C：資料配線之寄生電容V: input voltage, t: time, R: resistance of data wiring, C: parasitic capacitance of data wiring

由表1之結果而得知：進行氫電漿處理而在鈍化膜使用有機材料之薄膜電晶體係即使是在過於嚴酷之氣氛下，也不惡化其特性，具有非常高之可靠性。此外，使用包含有機材料而組成之鈍化膜之薄膜電晶體基板係比起使用包含作為無機材料之SiNx而組成之鈍化膜者，可以使得製程數變得比較少且更加簡便地進行製造。此外，包含有機材料之鈍化膜係開口率變高，因此，具有良好之亮度，並且，可以使得比介電常數變低而抑制RC延遲。As is apparent from the results of Table 1, the thin film electrocrystallization system in which the hydrogen plasma treatment is performed and the organic material is used in the passivation film does not deteriorate its characteristics even in an extremely harsh atmosphere, and has extremely high reliability. Further, a thin film transistor substrate using a passivation film composed of an organic material can be manufactured more easily and more easily than a passivation film comprising SiNx as an inorganic material. Further, the passivation film containing the organic material has a high aperture ratio, and therefore has good luminance, and can lower the specific dielectric constant to suppress the RC retardation.

21．．．基板twenty one. . . Substrate

22．．．閘極電極twenty two. . . Gate electrode

23．．．閘極絕緣膜twenty three. . . Gate insulating film

24．．．半導體層twenty four. . . Semiconductor layer

25．．．不純物添加半導體層25. . . Impurity added semiconductor layer

26．．．源極‧汲極電極26. . . Source ‧ bungee electrode

27．．．源極電極27. . . Source electrode

28．．．汲極電極28. . . Bipolar electrode

29．．．通道區域29. . . Channel area

30．．．位處於源極電極存在之區域之不純物添加半導體層30. . . Impurity added semiconductor layer in the region where the source electrode exists

31．．．位處於汲極電極存在之區域之不純物添加半導體層31. . . Impurity added semiconductor layer in the region where the drain electrode exists

32．．．包含有機材料而組成之鈍化膜32. . . Passivation film composed of organic materials

33．．．包含無機材料而組成之鈍化膜33. . . Passivation film composed of inorganic materials

圖1(a)~(d)係顯示本發明之實施形態之半導體元件基板之製造方法之製程之圖。1(a) to 1(d) are views showing a process of a method of manufacturing a semiconductor device substrate according to an embodiment of the present invention.

圖2(a)~(c)係顯示本發明之實施形態之半導體元件基板之製造方法之製程之圖。2(a) to 2(c) are views showing a process of a method of manufacturing a semiconductor device substrate according to an embodiment of the present invention.

圖3(a)、(b)係顯示本發明之實施形態之鈍化膜之圖。3(a) and 3(b) are views showing a passivation film according to an embodiment of the present invention.

Claims (4)

一種半導體元件基板之製造方法，包含：對於半導體元件之表面或者是包含於前述半導體元件之半導體層表面來進行氫氣電漿處理以終止懸掛鏈之製程；以及在進行前述氫氣電漿處理以終止懸掛鏈之前述半導體元件表面或前述半導體層表面來形成由有機材料而組成之鈍化膜之製程來構成。 A method of manufacturing a semiconductor device substrate, comprising: performing a hydrogen plasma treatment on a surface of a semiconductor element or a surface of a semiconductor layer of the semiconductor element to terminate a suspension chain; and performing the foregoing hydrogen plasma treatment to terminate the suspension The surface of the aforementioned semiconductor element of the chain or the surface of the aforementioned semiconductor layer is formed by a process of forming a passivation film composed of an organic material. 如申請專利範圍第1項之半導體元件基板之製造方法，其中，前述半導體元件或前述半導體層係藉由包含在基板上形成閘極電極、閘極絕緣膜、半導體層和源極˙汲極電極之製程以及形成通道區域之製程的製程而進行製造。 The method of manufacturing a semiconductor device substrate according to claim 1, wherein the semiconductor element or the semiconductor layer is formed by forming a gate electrode, a gate insulating film, a semiconductor layer, and a source drain electrode on the substrate. The manufacturing process is performed by a process of forming a process of forming a channel region. 如申請專利範圍第1或2項中任一項之半導體元件基板之製造方法，其中，前述有機材料係含有環狀烯烴樹脂之樹脂組成物。 The method for producing a semiconductor element substrate according to any one of the first aspect, wherein the organic material contains a resin composition of a cyclic olefin resin. 如申請專利範圍第1或2項中任一項之半導體元件基板之製造方法，其中，前述氫氣電漿處理係1~10分鐘之處理時間。 The method for producing a semiconductor device substrate according to any one of claims 1 to 2, wherein the hydrogen plasma treatment is a treatment time of 1 to 10 minutes.
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