TWI535569B - Organic semiconductor components - Google Patents

Organic semiconductor components Download PDF

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TWI535569B
TWI535569B TW104113969A TW104113969A TWI535569B TW I535569 B TWI535569 B TW I535569B TW 104113969 A TW104113969 A TW 104113969A TW 104113969 A TW104113969 A TW 104113969A TW I535569 B TWI535569 B TW I535569B
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organic
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acid
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TW104113969A
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TW201601932A (en
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Junichi Takeya
Junji Iwasa
Kazuhisa Kumazawa
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Nippon Soda Co
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • 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
    • H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76—Unipolar devices, e.g. field effect transistors
    • H01L29/772—Field effect transistors
    • H01L29/78—Field effect transistors with field effect produced by an insulated gate
    • H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
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  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Silicon Polymers (AREA)
  • Thin Film Transistor (AREA)
  • Laminated Bodies (AREA)

Description

有機半導體元件 Organic semiconductor component

本發明係關於一種形成於樹脂基材上之有機半導體元件、尤其是有機薄膜電晶體。本案係對2014年5月9日提出申請之日本專利申請第2014-97826號主張優先權，將其內容援用於此。 The present invention relates to an organic semiconductor element, particularly an organic thin film transistor, formed on a resin substrate. The present application claims priority to Japanese Patent Application No. 2014-97826, filed on May 9, 2014, the content of which is incorporated herein.

有機薄膜電晶體於其製造中無需高溫製程，可藉由印刷、塗佈於具有柔軟性之樹脂基材而製作大面積積體電路，因此作為期待應用於軟性顯示器或RFID(Radio Frequency Identification，射頻識別)標籤等之新一代電子技術受到關注。 The organic thin film transistor does not require a high-temperature process in its production, and can be applied to a flexible resin substrate by printing or coating it to produce a large-area integrated circuit. Therefore, it is expected to be applied to a flexible display or RFID (Radio Frequency Identification). A new generation of electronic technologies such as identification tags are receiving attention.

然而，於在樹脂基材上形成薄膜電晶體(TFT)元件之電極、或絕緣體層之情形時，存在與玻璃基材相比接著性較差之問題。尤其是使用將金屬薄膜進行圖案化所製作之電極的TFT元件存在作為電晶體之特性下降且該傾向於有機TFT中較明顯之問題。針對該等問題，已知如下有機薄膜電晶體元件，其特徵在於：於樹脂基材上具有含有選自無機氧化物及無機氮化物中之化合物之底塗層，以與該底塗層接觸之方式具有電極，進而隔著閘極絕緣體層具有電極。進而已知作為該底塗層使用聚酯、聚碳酸酯、纖維素、丙烯酸系樹脂、聚乙烯樹脂等聚合物，進而亦已知於包含聚合物之底塗層上進而設置選自無機氧化物及無機氮化物中之化合物之層。(專利文獻1) However, in the case where an electrode of a thin film transistor (TFT) element or an insulator layer is formed on a resin substrate, there is a problem that the adhesion is inferior to that of the glass substrate. In particular, a TFT element using an electrode formed by patterning a metal thin film has a problem that the characteristics of the transistor are lowered and this tends to be more noticeable in the organic TFT. In view of the above problems, an organic thin film transistor element is known which has an undercoat layer containing a compound selected from an inorganic oxide and an inorganic nitride on a resin substrate to be in contact with the undercoat layer. The method has electrodes and further has electrodes across the gate insulator layer. Further, it is known that a polymer such as polyester, polycarbonate, cellulose, acrylic resin, or polyethylene resin is used as the undercoat layer, and is further known as a primer layer containing a polymer and further selected from an inorganic oxide. And a layer of a compound in the inorganic nitride. (Patent Document 1)

先前技術文獻 Prior technical literature 專利文獻 Patent literature

專利文獻1：日本專利特開2004-200365號公報 Patent Document 1: Japanese Patent Laid-Open Publication No. 2004-200365

然而，即便設置如上所述之底塗層，亦存在無法獲得充分之載子移動率之問題。 However, even if the undercoat layer as described above is provided, there is a problem that a sufficient carrier mobility cannot be obtained.

本發明之目的在於提供一種具有實用性移動率之樹脂基材之有機薄膜電晶體。 It is an object of the present invention to provide an organic thin film transistor having a resin substrate having a practical mobility.

本發明者為了解決上述課題經過努力研究，結果發現藉由於形成有特定薄膜之樹脂基材上設置有機半導體層而可解決上述課題，從而完成本發明。 In order to solve the above problems, the inventors of the present invention have found that the above problems can be solved by providing an organic semiconductor layer on a resin substrate on which a specific film is formed, and the present invention has been completed.

即，本發明係關於 That is, the present invention relates to

(1) (1)

一種有機半導體元件，其係於形成有下述(A)或(B)之薄膜之樹脂基材上設置有有機半導體層者，(A)含有以下之a)及b)之有機無機複合薄膜：a)式(I)所表示之有機矽化合物之至少1種以上之縮合物，RnSiX4-n (I) An organic semiconductor element which is provided with an organic semiconductor layer on a resin substrate on which a film of the following (A) or (B) is formed, and (A) an organic-inorganic composite film containing the following a) and b): a) at least one or more condensates of the organic hydrazine compound represented by the formula (I), R n SiX 4-n (I)

(式中，R表示碳原子直接鍵結於式中之Si上之有機基，X表示羥基或水解性基；n表示1或2，於n為2時，各R可相同亦可不同，於(4-n)為2以上時，各X可相同亦可不同) (wherein R represents an organic group in which a carbon atom is directly bonded to Si in the formula, X represents a hydroxyl group or a hydrolyzable group; n represents 1 or 2, and when n is 2, each R may be the same or different, When (4-n) is 2 or more, each X may be the same or different)

b)熱硬化性化合物之硬化物及/或電磁射線硬化性化合物之硬化物；(B)含有以下之d)、e)及f)之有機矽烷薄膜：d)含環氧基之三烷氧基矽烷之水解縮合物，e)聚胺類或咪唑類， f)f-1)正戊醇、或者f-2)25℃下之pKa為2.0~6.0之範圍之有機酸、或具有全氟烷基或全氟伸烷基之碳數2~5之醇類； b) a cured product of a thermosetting compound and/or a cured product of an electromagnetic ray curable compound; (B) an organic germane film containing d), e) and f): d) an epoxy group-containing trialkoxy a hydrolyzed condensate of decane, e) a polyamine or an imidazole, f) f-1) n-pentanol, or f-2) an organic acid having a pKa in the range of 2.0 to 6.0 at 25 ° C, or an alcohol having a perfluoroalkyl group or a perfluoroalkyl group having 2 to 5 carbon atoms class;

(2) (2)

如(1)記載之有機半導體元件，其中式(I)所表示之有機矽化合物係藉由Fedors之推算法所求出之R之溶解度參數(SP1)較藉由Fedors之推算法所求出之熱硬化性化合物或電磁射線硬化性化合物之溶解度參數(SP2)小1.6以上者； The organic semiconductor device according to (1), wherein the organic germanium compound represented by the formula (I) is a solubility parameter (SP1) of R determined by a Fedors' algorithm, which is obtained by a Fedors algorithm. The solubility parameter (SP2) of the thermosetting compound or the electromagnetic ray curable compound is less than 1.6;

(3) (3)

如(1)記載之有機半導體元件，其中式(I)所表示之有機矽化合物之縮合物為滿足下述數式(1)之量之式(I-I)所表示之有機矽化合物之至少1種以上與式(I-2)所表示之有機矽化合物之至少1種以上的水解縮合物，R1 nSiX4-n (I-1) The organic semiconductor device according to the above (1), wherein the condensate of the organic ruthenium compound represented by the formula (I) is at least one of the organic ruthenium compounds represented by the formula (II) satisfying the following formula (1). At least one or more kinds of hydrolysis condensates of the above organic hydrazine compound represented by the formula (I-2), R 1 n SiX 4-n (I-1)

(式中，n表示1或2，於n為2時，R1相互可相同亦可不同，R1為碳原子直接鍵結於式中之Si上之有機基，R1中之1個以上表示含乙烯基之烴基；X表示羥基或水解性基，相互可相同亦可不同) (wherein, n represents 1 or 2, and when n is 2, R 1 may be the same or different, and R 1 is an organic group in which a carbon atom is directly bonded to Si in the formula, and one or more of R 1 A hydrocarbon group containing a vinyl group; X represents a hydroxyl group or a hydrolyzable group, and may be the same or different from each other)

R2 nSiX4-n (I-2) R 2 n SiX 4-n (I-2)

(式中，n表示1或2，於n為2時，R2可相同亦可不同，R2表示碳原子直接鍵結於式中之Si上之除含乙烯基之烴基以外之有機基；X表示羥基或水解性基，相互可相同亦可不同) (wherein, n represents 1 or 2, and when n is 2, R 2 may be the same or different, and R 2 represents an organic group other than a vinyl group-containing hydrocarbon group in which a carbon atom is directly bonded to Si in the formula; X represents a hydroxyl group or a hydrolyzable group, and may be the same or different from each other)

30莫耳%≦{[式(I-1)之化合物]}/{[式(I-1)之化合物]+[式(I-2)之化合物]}×100<100莫耳% (1)； 30 mol % ≦ {[Compound of the formula (I-1)]} / {[Compound of the formula (I-1)] + [Compound of the formula (I-2)]} × 100 < 100 mol% (1 );

(4) (4)

如(1)記載之有機半導體元件，其中式(I)所表示之有機矽化合物之縮合物為式(I-1)所表示之有機矽化合物之至少1種以上與式(I-2)所 表示之有機矽化合物之至少1種以上的縮合物，且滿足數式(2)，R1 nSiX4-n (I-1) The organic semiconductor device according to the above (1), wherein the condensate of the organic ruthenium compound represented by the formula (I) is at least one or more of the organic ruthenium compound represented by the formula (I-1) and the formula (I-2). At least one or more condensates of the organic hydrazine compound, and satisfying the formula (2), R 1 n SiX 4-n (I-1)

(式中，n表示1或2，於n為2時，R1相互可相同亦可不同，R1為碳原子直接鍵結於式中之Si上之有機基，R1中之1個以上表示含乙烯基之烴基；X表示羥基或水解性基，相互可相同亦可不同) (wherein, n represents 1 or 2, and when n is 2, R 1 may be the same or different, and R 1 is an organic group in which a carbon atom is directly bonded to Si in the formula, and one or more of R 1 A hydrocarbon group containing a vinyl group; X represents a hydroxyl group or a hydrolyzable group, and may be the same or different from each other)

R2 nSiX4-n (I-2) R 2 n SiX 4-n (I-2)

(式中，n表示1或2，於n為2時，R2可相同亦可不同，R2表示碳原子直接鍵結於式中之Si上之除含乙烯基之烴基以外之有機基；X表示羥基或水解性基，相互可相同亦可不同) (wherein, n represents 1 or 2, and when n is 2, R 2 may be the same or different, and R 2 represents an organic group other than a vinyl group-containing hydrocarbon group in which a carbon atom is directly bonded to Si in the formula; X represents a hydroxyl group or a hydrolyzable group, and may be the same or different from each other)

30莫耳%≦{[縮合物中之源自式(I-1)之化合物之單元]}/{[縮合物中之源自式(I-1)之化合物之單元]+[縮合物中之源自式(I-2)之化合物之單元]}×100<100莫耳% (2)； 30 mol % ≦ {[unit of the compound derived from the formula (I-1) in the condensate]} / {[unit of the compound derived from the formula (I-1) in the condensate] + [condensate The unit derived from the compound of the formula (I-2)]}×100<100 mol% (2);

(5) (5)

如(1)至(4)中任一項記載之有機半導體元件，其中於上述樹脂基材上進而設置有有機單分子膜；及 The organic semiconductor device according to any one of (1) to (4), wherein an organic monomolecular film is further provided on the resin substrate;

(6) (6)

如(1)至(5)中任一項記載之有機半導體元件，其中有機半導體元件為有機薄膜電晶體。 The organic semiconductor device according to any one of (1) to (5) wherein the organic semiconductor device is an organic thin film transistor.

本發明之形成於樹脂基材上之有機半導體元件表現出可用於有機薄膜電晶體用途之載子移動率。 The organic semiconductor element formed on the resin substrate of the present invention exhibits a carrier mobility which can be used for an organic thin film transistor.

圖1係表示實施例1之有機薄膜電晶體之傳遞特性的曲線圖。 Fig. 1 is a graph showing the transfer characteristics of the organic thin film transistor of Example 1.

圖2係表示實施例1之有機薄膜電晶體之於線性區域之場效遷移率之閘極電壓依存性的曲線圖。 Fig. 2 is a graph showing gate voltage dependence of field effect mobility of the organic thin film transistor of Example 1 in a linear region.

圖3表示實施例1之有機薄膜電晶體之飽和區域之特性，表示飽 和區域即施加有Vd=-100V之源極/汲極電壓時之Id-Vg之電晶體特性。 Figure 3 is a graph showing the characteristics of the saturated region of the organic thin film transistor of Example 1, showing saturation And the region is the transistor characteristic of Id-Vg when the source/drain voltage of Vd=-100V is applied.

圖4係表示實施例1之有機薄膜電晶體之於飽和區域之場效遷移率之閘極電壓依存性的曲線圖。 Fig. 4 is a graph showing gate voltage dependence of field effect mobility of the organic thin film transistor of Example 1 in a saturated region.

圖5係表示實施例1之有機薄膜電晶體之輸出特性的曲線圖。 Fig. 5 is a graph showing the output characteristics of the organic thin film transistor of Example 1.

圖6係表示實施例2之有機薄膜電晶體之傳遞特性的曲線圖。 Fig. 6 is a graph showing the transfer characteristics of the organic thin film transistor of Example 2.

圖7係表示實施例2之有機薄膜電晶體之於線性區域之場效遷移率之閘極電壓依存性的曲線圖。 Fig. 7 is a graph showing the gate voltage dependence of the field effect mobility of the organic thin film transistor of Example 2 in the linear region.

圖8表示實施例2之有機薄膜電晶體之飽和區域之特性，表示飽和區域即施加有Vd=-100V之源極/汲極電壓時之Id-Vg之電晶體特性。 Fig. 8 is a graph showing the characteristics of the saturated region of the organic thin film transistor of Example 2, and shows the crystal characteristics of the saturated region, i.e., Id-Vg when the source/drain voltage of Vd = -100 V is applied.

圖9係表示實施例2之有機薄膜電晶體之於飽和區域之場效遷移率之閘極電壓依存性的曲線圖。 Fig. 9 is a graph showing gate voltage dependence of field effect mobility of the organic thin film transistor of Example 2 in a saturated region.

圖10係表示實施例2之有機薄膜電晶體之輸出特性的曲線圖。 Fig. 10 is a graph showing the output characteristics of the organic thin film transistor of Example 2.

本發明之有機半導體元件係於樹脂基材上設置有有機半導體層者。 The organic semiconductor device of the present invention is one in which an organic semiconductor layer is provided on a resin substrate.

作為本發明之有機半導體元件之例，可列舉作為有機半導體電晶體之有機場效電晶體(有機FET)。有機FET一般而言具有：閘極電極、閘極絕緣膜(絕緣體層)、源極電極、汲極電極、有機半導體層及樹脂基材。本發明之特徵在於：使用於樹脂上形成有特定薄膜之樹脂基材作為上述有機FET等中之樹脂基材。 An example of the organic semiconductor device of the present invention is an organic field effect transistor (organic FET) which is an organic semiconductor transistor. The organic FET generally has a gate electrode, a gate insulating film (insulator layer), a source electrode, a gate electrode, an organic semiconductor layer, and a resin substrate. The present invention is characterized in that a resin substrate on which a specific film is formed on a resin is used as a resin substrate in the above organic FET or the like.

以下對本發明之有機半導體元件進行詳細說明。 Hereinafter, the organic semiconductor device of the present invention will be described in detail.

[樹脂基材] [Resin substrate]

本發明之樹脂基材係於樹脂上形成有下述(A)或(B)之薄膜者。 The resin substrate of the present invention is formed by forming a film of the following (A) or (B) on a resin.

(A)含有以下之a)及b)之有機無機複合薄膜： a)RnSiX4-n所表示之有機矽化合物之至少1種以上之縮合物，(式中，R表示碳原子直接鍵結於式中之Si上之有機基，X表示羥基或水解性基。n表示1或2，於n為2時，各R可相同亦可不同，於(4-n)為2以上時，各X可相同亦可不同) (A) an organic-inorganic composite film comprising the following a) and b): a) at least one or more condensates of an organic ruthenium compound represented by R n SiX 4-n (wherein R represents a direct bond of a carbon atom) An organic group on the Si in the formula, X represents a hydroxyl group or a hydrolyzable group. n represents 1 or 2. When n is 2, each R may be the same or different, and when (4-n) is 2 or more, Each X can be the same or different)

b)熱硬化性化合物之硬化物及/或電磁射線硬化性化合物之硬化物；(B)含有以下之d)、e)及f)之有機矽烷薄膜：d)含環氧基之三烷氧基矽烷之水解縮合物，e)聚胺類或咪唑類，f)f-1)正戊醇、或者f-2)25℃下之pKa為2.0~6.0之範圍之有機酸、或具有全氟烷基或全氟伸烷基之碳數2~5之醇類 b) a cured product of a thermosetting compound and/or a cured product of an electromagnetic ray curable compound; (B) an organic germane film containing d), e) and f): d) an epoxy group-containing trialkoxy a hydrolyzed condensate of decane, e) a polyamine or an imidazole, f) f-1) n-pentanol, or f-2) an organic acid having a pKa in the range of 2.0 to 6.0 at 25 ° C, or having perfluoro Alkyl or perfluoroalkylene group having 2 to 5 carbon atoms

(1)樹脂 (1) Resin

本發明之樹脂只要可形成本發明之薄膜則並無限制，具體而言，可列舉：聚對苯二甲酸乙二酯(PET)、聚萘二甲酸乙二酯(PEN)、聚醚碸(PES)、聚醚醯亞胺、聚醚醚酮、聚苯硫醚、聚芳酯、聚醯亞胺、聚碳酸酯(PC)、三乙酸纖維素(TAC)、乙酸丙酸纖維素(CAP)等。尤佳為聚萘二甲酸乙二酯(PEN)、聚醯亞胺(PI)。其形狀可為膜狀、片狀、板狀等任意形狀，尤佳為膜狀樹脂。 The resin of the present invention is not limited as long as it can form the film of the present invention, and specific examples thereof include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polyether oxime ( PES), polyether oximine, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimine, polycarbonate (PC), cellulose triacetate (TAC), cellulose acetate propionate (CAP) )Wait. Particularly preferred is polyethylene naphthalate (PEN), polyimine (PI). The shape may be any shape such as a film shape, a sheet shape, or a plate shape, and is preferably a film-like resin.

膜狀樹脂可為包含未延伸膜者，亦可為包含延伸膜者。又，可為單層膜，亦可為藉由層壓、塗佈等方法使兩層以上積層而成之積層膜。 The film-like resin may be one containing an unstretched film or may be a film containing a stretched film. Further, it may be a single layer film, or a laminate film in which two or more layers are laminated by lamination or coating.

膜狀樹脂之厚度並無特別限制，通常為1~1000μm，較佳為3~500μm。 The thickness of the film-like resin is not particularly limited, but is usually 1 to 1000 μm, preferably 3 to 500 μm.

(2)有機無機複合薄膜 (2) Organic-inorganic composite film

本發明之有機無機複合薄膜含有有機矽化合物之縮合物、及熱 硬化性化合物之硬化物及/或電磁射線硬化性化合物之硬化物。 The organic-inorganic composite film of the present invention contains a condensate of an organic cerium compound, and heat A cured product of a curable compound and/or a cured product of an electromagnetic ray curable compound.

1)有機矽化合物之縮合物 1) Condensate of organic hydrazine compound

本發明之有機矽化合物之縮合物係以下之式(I)所表示之有機矽化合物之至少1種以上之縮合物。 The condensate of the organic hydrazine compound of the present invention is at least one condensate of the organic hydrazine compound represented by the following formula (I).

RnSiX4-n (I) R n SiX 4-n (I)

式中，R表示碳原子直接鍵結於式中之Si上之有機基，X表示羥基或水解性基。n表示1或2，於n為2時，各R可相同亦可不同，於(4-n)為2以上時，各X可相同亦可不同。 In the formula, R represents an organic group in which a carbon atom is directly bonded to Si in the formula, and X represents a hydroxyl group or a hydrolyzable group. n represents 1 or 2. When n is 2, each R may be the same or different. When (4-n) is 2 or more, each X may be the same or different.

此處，作為R所表示之「碳原子直接鍵結於Si上之有機基」，可列舉：可經取代之烴基、包含聚合物部分之烴基等。 Here, examples of the "organic group in which a carbon atom is directly bonded to Si" include a hydrocarbon group which may be substituted, a hydrocarbon group containing a polymer moiety, and the like.

作為上述「可經取代之烴基」之烴基，通常為碳數1~30之烴基，例如可列舉：烷基、環烷基、環烷基烷基、烯基、炔基、芳基、芳基烷基、芳基烯基等。 The hydrocarbon group of the above-mentioned "hydrocarbon group which may be substituted" is usually a hydrocarbon group having 1 to 30 carbon atoms, and examples thereof include an alkyl group, a cycloalkyl group, a cycloalkylalkyl group, an alkenyl group, an alkynyl group, an aryl group and an aryl group. Alkyl, arylalkenyl, and the like.

又，上述「烴基」亦可包含氧原子、氮原子或矽原子。 Further, the above "hydrocarbon group" may also contain an oxygen atom, a nitrogen atom or a ruthenium atom.

烷基較佳為碳數1~10之直鏈或支鏈烷基，具體而言，可列舉：甲基、乙基、正丙基、異丙基、正丁基、異丁基、第三丁基、正戊基、異戊基、新戊基、正己基、異己基、正庚基、正辛基、正壬基、異壬基、正癸基等，進而作為碳數超過10之長鏈烷基，可列舉：月桂基、十三烷基、肉豆蔻基、十五烷基、棕櫚基、十七烷基、硬脂基等。 The alkyl group is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a third group. Butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, n-heptyl, n-octyl, n-decyl, isodecyl, n-decyl, etc., and further as a carbon number of more than 10 The alkyl group may, for example, be a lauryl group, a tridecyl group, a myristyl group, a pentadecyl group, a palmity group, a heptadecyl group or a stearyl group.

環烷基較佳為碳數3~8之環烷基，具體而言，可列舉：環丙基、環丁基、環戊基、環己基、環庚基、環辛基等。 The cycloalkyl group is preferably a cycloalkyl group having 3 to 8 carbon atoms, and specific examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

烯基較佳為碳數2~10之直鏈或支鏈烯基，具體而言，可列舉：乙烯基、1-丙烯-1-基、2-丙烯-1-基、1-丙烯-2-基、1-丁烯-1-基、2-丁烯-1-基、3-丁烯-1-基、1-丁烯-2-基、3-丁烯-2-基、1-戊烯-1-基、4-戊烯-1-基、1-戊烯-2-基、4-戊烯-2-基、3-甲基-1-丁烯-1-基、1-己烯 1-基、5-己烯-1-基、1-庚烯-1-基、6-庚烯-1-基、1-辛烯-1-基、7-辛烯-1-基等。 The alkenyl group is preferably a linear or branched alkenyl group having 2 to 10 carbon atoms, and specific examples thereof include a vinyl group, a 1-propen-1-yl group, a 2-propen-1-yl group, and a 1-propene-2. -yl, 1-buten-1-yl, 2-buten-1-yl, 3-buten-1-yl, 1-buten-2-yl, 3-buten-2-yl, 1- Penten-1-yl, 4-penten-1-yl, 1-penten-2-yl, 4-penten-2-yl, 3-methyl-1-buten-1-yl, 1- Hexene 1-Base, 5-hexen-1-yl, 1-hepten-1-yl, 6-hepten-1-yl, 1-octen-1-yl, 7-octene-1-yl and the like.

環烯基意指碳數3~8之環狀烯基，較佳為碳數3~8之環烯基，具體而言，可列舉：1-環戊烯-1-基、2-環戊烯-1-基、1-環己烯-1-基、2-環己烯-1-基、3-環己烯-1-基等。 The cycloalkenyl group means a cyclic alkenyl group having 3 to 8 carbon atoms, preferably a cycloalkenyl group having 3 to 8 carbon atoms, and specific examples thereof include 1-cyclopenten-1-yl group and 2-cyclopentyl group. Alken-1-yl, 1-cyclohexen-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl and the like.

炔基較佳為碳數2~10之炔基，具體而言，可列舉：乙炔基、1-丙炔-1-基、2-丙炔-1-基、1-丁炔-1-基、3-丁炔-1-基、1-戊炔-1-基、4-戊炔-1-基、1-己炔-1-基、5-己炔-1-基、1-庚炔-1-基、1-辛炔-1-基、7-辛炔-1-基等。 The alkynyl group is preferably an alkynyl group having 2 to 10 carbon atoms, and specific examples thereof include an ethynyl group, a 1-propyn-1-yl group, a 2-propyn-1-yl group, and a 1-butyn-1-yl group. , 3-butyn-1-yl, 1-pentyn-1-yl, 4-pentyn-1-yl, 1-hexyn-1-yl, 5-hexyn-1-yl, 1-heptyne -1-yl, 1-octyn-1-yl, 7-octyn-1-yl and the like.

作為環烷基烷基，可列舉：碳數3~10之環烷基與碳數1~10之烷基鍵結而成之基。 Examples of the cycloalkylalkyl group include a group in which a cycloalkyl group having 3 to 10 carbon atoms is bonded to an alkyl group having 1 to 10 carbon atoms.

芳基意指單環或多環芳基，於多環芳基之情形時，亦包括除完全不飽和環以外亦具有部分飽和環之基。具體而言，可列舉：苯基、萘基、薁基、茚基、二氫茚基、四氫萘基等，較佳為碳數6~10之芳基。 An aryl group means a monocyclic or polycyclic aryl group, and in the case of a polycyclic aryl group, it also includes a group having a partially saturated ring in addition to the fully unsaturated ring. Specific examples thereof include a phenyl group, a naphthyl group, an anthracenyl group, an anthracenyl group, a dihydroindenyl group, and a tetrahydronaphthyl group, and an aryl group having 6 to 10 carbon atoms is preferable.

作為芳基烷基，可列舉：碳數6~10之芳基與碳數1~10之烷基鍵結而成之基。作為芳基烯基，可列舉：碳數6~10之芳基與碳數2~10之烯基鍵結而成之基。 Examples of the arylalkyl group include a group in which an aryl group having 6 to 10 carbon atoms is bonded to an alkyl group having 1 to 10 carbon atoms. Examples of the arylalkenyl group include a group in which an aryl group having 6 to 10 carbon atoms is bonded to an alkenyl group having 2 to 10 carbon atoms.

作為「具有氧原子之烴基」，可列舉：烷氧基烷基；環氧基、環氧烷基、縮水甘油氧基烷基等具有環氧乙烷環(環氧基)之基；丙烯醯氧基甲基、甲基丙烯醯氧基甲基等。 Examples of the "hydrocarbon group having an oxygen atom" include an alkoxyalkyl group; a group having an oxirane ring (epoxy group) such as an epoxy group, an alkylene oxide group or a glycidoxyalkyl group; and an acrylonitrile group; Oxymethyl group, methacryloxymethyl group, and the like.

此處，作為烷氧基烷基，可列舉：碳數1~6之烷氧基與碳數1~6之烷基鍵結而成之基。作為碳數1~6之烷氧基，可列舉：甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、異丁氧基、第三丁氧基等，作為碳數1~6之烷基，可例示與上述烷基相同者。 Here, examples of the alkoxyalkyl group include a group in which an alkoxy group having 1 to 6 carbon atoms is bonded to an alkyl group having 1 to 6 carbon atoms. Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, and a third butoxy group. The alkyl group having 1 to 6 carbon atoms can be exemplified by the same as the above alkyl group.

作為環氧烷基，較佳為碳數3~10之直鏈或支鏈環氧烷基，具體 而言，可列舉：縮水甘油基、縮水甘油基甲基、2-縮水甘油基乙基、3-縮水甘油基丙基、4-縮水甘油基丁基、3,4-環氧丁基、4,5-環氧戊基、5,6-環氧己基等包含環氧基之直鏈狀烷基；β-甲基縮水甘油基、β-乙基縮水甘油基、β-丙基縮水甘油基、2-縮水甘油基丙基、2-縮水甘油基丁基、3-縮水甘油基丁基、2-甲基-3-縮水甘油基丙基、3-甲基-2-縮水甘油基丙基、3-甲基-3,4-環氧丁基、3-乙基-3,4-環氧丁基、4-甲基-4,5-環氧戊基、5-甲基-5,6-環氧己基等包含環氧基之支鏈狀烷基等。 As the epoxyalkyl group, a linear or branched alkylene group having a carbon number of 3 to 10 is preferred. Examples thereof include glycidyl group, glycidylmethyl group, 2-glycidylethyl group, 3-glycidylpropyl group, 4-glycidylbutyl group, 3,4-epoxybutyl group, and 4 a linear alkyl group containing an epoxy group such as 5-epoxypentyl or 5,6-epoxyhexyl; β-methylglycidyl, β-ethyl glycidyl, β-propyl glycidyl , 2-glycidylpropyl, 2-glycidylbutyl, 3-glycidylbutyl, 2-methyl-3-glycidylpropyl, 3-methyl-2-glycidylpropyl , 3-methyl-3,4-epoxybutyl, 3-ethyl-3,4-epoxybutyl, 4-methyl-4,5-epoxypentyl, 5-methyl-5, A branched alkyl group or the like containing an epoxy group such as 6-epoxyhexyl.

作為縮水甘油氧基烷基，具體而言，可列舉：縮水甘油氧基甲基、縮水甘油氧基丙基等。 Specific examples of the glycidoxyalkyl group include a glycidoxymethyl group and a glycidoxypropyl group.

作為「具有氮原子之烴基」，可列舉：具有-NR'2(式中，R'表示氫原子、烷基或芳基，各R'相互可相同亦可不同)之烴基、或具有-N=CR"2(式中，R"表示氫原子、烷基或芳基，各R"相互可相同亦可不同)之烴基。 The "hydrocarbon group having a nitrogen atom" may be a hydrocarbon group having -NR' 2 (wherein R' represents a hydrogen atom, an alkyl group or an aryl group, and each R' may be the same or different), or has -N =CR" 2 (wherein R" represents a hydrogen atom, an alkyl group or an aryl group, and each R" may be the same or different from each other.

例如作為具有-NR'2之基，具體而言，可列舉：-CH2NH2基、-CH2(CH2)2NH2基、-CH2NHCH3基等。作為具有-N=CR"2之基，具體而言，可列舉：-CH2N=CHCH3基、-CH2N=C(CH3)2基、-CH2CH2N=CHCH3基、-CH2N=CHPh基、-CH2N=C(Ph)CH3基等。 For example, as the group having -NR' 2 , specifically, a -CH 2 NH 2 group, a -CH 2 (CH 2 ) 2 NH 2 group, a -CH 2 NHCH 3 group, or the like can be given. Specific examples of the group having -N=CR" 2 include -CH 2 N=CHCH 3 group, -CH 2 N=C(CH 3 ) 2 group, and -CH 2 CH 2 N=CHCH 3 group. , -CH 2 N=CHPh group, -CH 2 N=C(Ph)CH 3 group, and the like.

作為上述「可經取代」之取代基，可列舉：鹵基、烷基、烯基、芳基、甲基丙烯醯氧基等。作為烷基、烯基、芳基，可列舉與R中者相同之烴基。 Examples of the substituent which may be substituted include a halogen group, an alkyl group, an alkenyl group, an aryl group, a methacryloxy group and the like. Examples of the alkyl group, the alkenyl group and the aryl group include the same hydrocarbon groups as those of R.

上述中，乙烯基、具有環氧乙烷環之基、具有-NR'2之基或具有-N=CR"2之基就有機無機複合薄膜表面之無機化之觀點而言為較佳基。 Among the above, a vinyl group, a group having an oxirane ring, a group having -NR' 2 or a group having -N=CR" 2 is preferred from the viewpoint of inorganication of the surface of the organic-inorganic composite film.

又，式(I)中，n表示1或2，尤佳為n為1者。於n為2時，各R可相同亦可不同。 Further, in the formula (I), n represents 1 or 2, and particularly preferably n is 1. When n is 2, each R may be the same or different.

式(I)中，X表示羥基或水解性基。於式(I)之(4-n)為2以上時，各X可相同亦可不同。所謂水解性基意指例如藉由於無觸媒、過量水之共存下在25℃~100℃下加熱而發生水解，從而可生成矽烷醇基之基或可形成矽氧烷縮合物之基，可列舉：烷氧基、醯氧基、鹵基、異氰酸酯基、胺基或取代胺基等，較佳為碳數1~4之烷氧基或碳數1~6之醯氧基。 In the formula (I), X represents a hydroxyl group or a hydrolyzable group. When (4-n) of the formula (I) is 2 or more, each X may be the same or different. The hydrolyzable group means, for example, hydrolysis by heating at 25 ° C to 100 ° C in the coexistence of no catalyst or excess water, whereby a stanol group group or a base of a oxane condensate can be formed. The alkoxy group, the decyloxy group, the halogen group, the isocyanate group, the amine group or the substituted amine group are preferably an alkoxy group having 1 to 4 carbon atoms or a decyloxy group having 1 to 6 carbon atoms.

作為碳數1~4之烷氧基，具體而言，可列舉：甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、異丁氧基、第三丁氧基等，作為碳數1~6之醯氧基(其中，碳數中不包含羰基之碳)，具體而言，可列舉：乙醯氧基、苯甲醯氧基等。作為鹵基，具體而言，可列舉：氟基、氯基、溴基、碘基等。 Specific examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, and a third butoxy group. Examples of the oxime group having a carbon number of 1 to 6 (the carbon having no carbon atom in the carbon number) may, for example, be an ethoxycarbonyl group or a benzamidine group. Specific examples of the halogen group include a fluorine group, a chlorine group, a bromine group, and an iodine group.

作為式(I)所表示之有機矽化合物，具體而言，可列舉：甲基三氯矽烷、甲基三甲氧基矽烷、甲基三乙氧基矽烷、甲基三丁氧基矽烷、乙基三甲氧基矽烷、乙基三異丙氧基矽烷、乙基三丁氧基矽烷、丁基三甲氧基矽烷、五氟苯基三甲氧基矽烷、苯基三甲氧基矽烷、九氟丁基乙基二甲氧基矽烷、三氟甲基三甲氧基矽烷、二甲基二胺基矽烷、二甲基二氯矽烷、二甲基二乙醯氧基矽烷、二甲基二甲氧基矽烷、二苯基二甲氧基矽烷、二丁基二甲氧基矽烷、乙烯基三甲氧基矽烷、3-(甲基)丙烯醯氧基丙基三甲氧基矽烷、3-(3-甲基-3-氧雜環丁烷甲氧基)丙基三甲氧基矽烷、4-氧雜環己基三甲氧基矽烷、甲基三[(甲基)丙烯醯氧基]矽烷、甲基三[2-(甲基)丙烯醯氧基乙氧基]矽烷、甲基-三縮水甘油醚氧基矽烷、甲基三(3-甲基-3-氧雜環丁烷甲氧基)矽烷、乙烯基三氯矽烷、乙烯基三乙氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-縮水甘油氧基-正丙基三甲氧基矽烷、3-縮水甘油氧基-正丙基甲基二乙氧基矽烷、3-縮水甘油氧基-正丙基三乙氧基矽烷、對苯乙烯基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二甲氧基 矽烷、3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三乙氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-三乙氧基矽烷基-N-(1,3-二甲基-亞丁基)丙基胺、3-苯胺基丙基三甲氧基矽烷等。 Specific examples of the organic hydrazine compound represented by the formula (I) include methyltrichlorodecane, methyltrimethoxydecane, methyltriethoxydecane, methyltributoxydecane, and ethyl. Trimethoxy decane, ethyl triisopropoxy decane, ethyl tributoxy decane, butyl trimethoxy decane, pentafluorophenyl trimethoxy decane, phenyl trimethoxy decane, nonafluorobutyl B Dimethoxy decane, trifluoromethyl trimethoxy decane, dimethyl diamino decane, dimethyl dichloro decane, dimethyl diethoxy decane, dimethyl dimethoxy decane, Diphenyldimethoxydecane, dibutyldimethoxydecane, vinyltrimethoxydecane, 3-(methyl)propenyloxypropyltrimethoxydecane, 3-(3-methyl- 3-oxetanylmethoxy)propyltrimethoxydecane, 4-oxecyclohexyltrimethoxydecane, methyltris[(methyl)propenyloxy]decane, methyltris[2- (Meth) propylene methoxy ethoxy] decane, methyl-triglycidyl ether decane, methyl tris(3-methyl-3-oxetanyl methoxy) decane, vinyl three Chlorodecane, ethylene Triethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-glycidoxy-n-propyltrimethoxydecane, 3-glycidoxy-n-propyl Methyl diethoxy decane, 3-glycidoxy-n-propyl triethoxy decane, p-styryl trimethoxy decane, 3-methyl propylene methoxy propyl methyl dimethoxy Decane, 3-methacryloxypropylmethyldiethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, N-(2-aminoethyl)-3-amine Propylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropyl Triethoxy decane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-triethoxydecyl-N-(1,3-dimethyl-arylene Base) propylamine, 3-anilinopropyltrimethoxydecane, and the like.

所謂R為包含聚合物部分之烴基的有機矽化合物，表示使具有聚合性官能基之有機矽化合物視需要與其他具有聚合性官能基之單體進行共聚所獲得之聚合物，可列舉使3-甲基丙烯醯氧基丙基三甲氧基矽烷與甲基丙烯酸甲酯、甲基丙烯酸丁酯等甲基丙烯酸酯或甲基丙烯酸等進行共聚所獲得之聚合物等。 The R is an organic ruthenium compound containing a hydrocarbon group of a polymer moiety, and is a polymer obtained by copolymerizing an organic ruthenium compound having a polymerizable functional group with another monomer having a polymerizable functional group, and is exemplified by 3- A polymer obtained by copolymerizing methacryloxypropyltrimethoxydecane with a methacrylate such as methyl methacrylate or butyl methacrylate or methacrylic acid.

又，作為R為包含聚合物部分之烴基的有機矽化合物之其他例，表示利用高分子反應導入有機矽部分所獲得之聚合物，可列舉：使聚甲基丙烯酸與3-縮水甘油氧基丙基三甲氧基矽烷反應而於側鏈導入烷氧基矽烷部位所得之聚合物、於1,2-聚丁二烯側鏈雙鍵藉由利用三甲氧基氫矽烷等之矽氫化導入矽烷基所得之聚合物等。 Further, as another example of the organic ruthenium compound in which R is a hydrocarbon group containing a polymer moiety, a polymer obtained by introducing an organic oxime moiety by a polymer reaction is exemplified by polymethacrylic acid and 3-glycidoxypropyl group. a polymer obtained by reacting a trimethoxy decane to a side chain to introduce an alkoxy decane moiety, and a 1,2-polybutadiene side chain double bond is obtained by hydrogenation of a decyl group using trimethylhydrohydrohalane or the like. Polymers, etc.

作為具有聚合性官能基之可與有機矽化合物共聚之單體，具體而言，可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸環己酯等(甲基)丙烯酸酯；(甲基)丙烯酸、伊康酸、反丁烯二酸等羧酸及順丁烯二酸酐等酸酐；(甲基)丙烯酸縮水甘油酯等環氧化合物；(甲基)丙烯酸二乙基胺基乙酯、胺基乙基乙烯醚等胺基化合物；(甲基)丙烯醯胺、伊康酸二醯胺、α-乙基丙烯醯胺、丁烯醯胺、反丁烯二酸二醯胺、順丁烯二酸二醯胺、N-丁氧基甲基(甲基)丙烯醯胺等醯胺化合物；丙烯腈、苯乙烯、α-甲基苯乙烯、氯乙烯、乙酸乙烯酯、丙酸乙烯酯、雙酚A型環氧樹脂、酚系酚醛清漆型環氧樹脂、三縮水甘油基異氰尿酸酯等。 Specific examples of the monomer copolymerizable with the organic ruthenium compound having a polymerizable functional group include methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate. (meth) acrylate such as 2-ethylhexyl acrylate or cyclohexyl (meth) acrylate; carboxylic acid and maleic anhydride such as (meth)acrylic acid, itaconic acid, and fumaric acid An acid anhydride; an epoxy compound such as glycidyl (meth)acrylate; an amine compound such as diethylaminoethyl (meth)acrylate or aminoethyl vinyl ether; (meth) acrylamide, Ikon Diamine, α-ethyl acrylamide, butenylamine, diammonium methacrylate, diammonium maleate, N-butoxymethyl (meth) acrylamide Isoprene compound; acrylonitrile, styrene, α-methylstyrene, vinyl chloride, vinyl acetate, vinyl propionate, bisphenol A epoxy resin, phenolic novolak epoxy resin, triglycidyl Isocyanurate and the like.

又，作為可藉由高分子反應而導入有機矽部分之聚合物，具體而言，可列舉：聚(甲基)丙烯酸、對羥基苯乙烯、聚丁二烯等。 In addition, examples of the polymer which can be introduced into the organic oxime portion by a polymer reaction include poly(meth)acrylic acid, p-hydroxystyrene, and polybutadiene.

再者，本發明之有機無機複合薄膜中之成為主成分之有機矽化合物之縮合物意指該等有機矽化合物之縮合物及/或有機矽化合物之縮合物之進一步之縮合物。 Further, the condensate of the organic ruthenium compound which is a main component in the organic-inorganic composite film of the present invention means a further condensate of the condensate of the organic ruthenium compound and/or the condensate of the organic ruthenium compound.

關於有機矽化合物之縮合物之調配量，相對於有機無機複合薄膜整體之固形物成分(有機矽化合物之縮合物、熱硬化性化合物之硬化物或電磁射線硬化性化合物之硬化物及視需要調配之其他成分的總質量)而為2~98質量%，較佳為5~50質量%，更佳為5~30質量%。 The amount of the condensate of the organic ruthenium compound is adjusted to the solid content of the organic-inorganic composite film (the condensate of the organic ruthenium compound, the cured product of the thermosetting compound, or the cured product of the electromagnetic ray-curable compound, and if necessary) The total mass of the other components is 2 to 98% by mass, preferably 5 to 50% by mass, and more preferably 5 to 30% by mass.

本發明中使用之有機矽化合物之縮合物之較佳態樣係滿足下述數式(1)之量之式(I-1)所表示之有機矽化合物之至少1種以上與式(I-2)所表示之有機矽化合物之至少1種以上的縮合物。 The preferred embodiment of the condensate of the organic hydrazine compound used in the present invention is at least one of the organic hydrazine compounds represented by the formula (I-1) satisfying the following formula (1) and the formula (I- 2) At least one or more condensates of the organic hydrazine compound represented.

R1 nSiX4-n (I-1) R 1 n SiX 4-n ( I-1)

R2 nSiX4-n (I-2) R 2 n SiX 4-n (I-2)

30莫耳%≦{[式(I-1)之化合物]}/{[式(I-1)之化合物]+[式(I-2)之化合物]}×100<100莫耳% (1) 30 mol % ≦ {[Compound of the formula (I-1)]} / {[Compound of the formula (I-1)] + [Compound of the formula (I-2)]} × 100 < 100 mol% (1 )

式(I-1)中，n表示1或2，於n為2時，R1相互可相同亦可不同，R1為碳原子直接鍵結於式中之Si上之有機基，R1中之1個以上表示含乙烯基之烴基；X表示羥基或水解性基，相互可相同亦可不同。 In the formula (I-1), n represents 1 or 2. When n is 2, R 1 may be the same or different, and R 1 is an organic group in which a carbon atom is directly bonded to Si in the formula, in R 1 One or more of them represent a hydrocarbon group containing a vinyl group; and X represents a hydroxyl group or a hydrolyzable group, and may be the same or different from each other.

式(I-2)中，n表示1或2，於n為2時，R2可相同亦可不同，R2表示碳原子直接鍵結於式中之Si上之除含乙烯基之烴基以外之有機基；X表示羥基或水解性基，相互可相同亦可不同。 In the formula (I-2), n represents 1 or 2. When n is 2, R 2 may be the same or different, and R 2 represents a carbon atom directly bonded to the vinyl group other than the vinyl group in the formula. The organic group; X represents a hydroxyl group or a hydrolyzable group, and may be the same or different from each other.

上述數式(1)表示製備有機矽化合物之縮合物時式(I-1)所表示之有機矽化合物與式(I-2)所表示之有機矽化合物的調配比。 The above formula (1) represents the compounding ratio of the organic hydrazine compound represented by the formula (I-1) and the organic hydrazine compound represented by the formula (I-2) in the preparation of the condensate of the organic hydrazine compound.

再者，式(I-1)及式(I-2)所表示之有機矽化合物亦可包含縮合物。於包含縮合物之情形時，數式(1)中之式(I-1)及式(I-2)所表示之有機矽 化合物分別可被換作包含縮合物者。 Further, the organic ruthenium compound represented by the formula (I-1) and the formula (I-2) may further contain a condensate. In the case of containing a condensate, the organic oxime represented by the formula (I-1) and the formula (I-2) in the formula (1) The compounds can each be exchanged for inclusion of a condensate.

有機矽化合物之縮合物中之源自式(I-1)之化合物之單元與源自式(I-2)之化合物之單元的存在比係與上述數式(1)同樣地以下述數式(2)表示。 In the condensate of the organic hydrazine compound, the ratio of the unit derived from the compound of the formula (I-1) to the unit derived from the compound of the formula (I-2) is the same as the above formula (1) by the following formula (2) indicates.

30莫耳%≦{[縮合物中之源自式(I-1)之化合物之單元]}/{[縮合物中之源自式(I-1)之化合物之單元]+[縮合物中之源自式(I-2)之化合物之單元]}×100<100莫耳% (2) 30 mol % ≦ {[unit of the compound derived from the formula (I-1) in the condensate]} / {[unit of the compound derived from the formula (I-1) in the condensate] + [condensate The unit derived from the compound of the formula (I-2)]}×100<100 mol% (2)

所謂有機矽化合物之縮合物係指有機矽化合物彼此進行縮合或水解縮合而形成矽氧烷鍵所得之二聚物等。有機矽化合物之縮合物可為僅式(I-1)或式(I-2)之化合物進行縮合所得者，亦可為式(I-1)之化合物與式(I-2)之化合物進行縮合所得者，亦可混合存有該等之2種以上。 The condensate of the organic hydrazine compound refers to a dimer obtained by condensing or hydrolyzing and condensing an organic hydrazine compound to form a decane bond. The condensate of the organic hydrazine compound may be obtained by condensation of a compound of the formula (I-1) or the formula (I-2), or a compound of the formula (I-1) and a compound of the formula (I-2). Two or more of these may be mixed and mixed.

作為上述R1及R2中之含乙烯基之烴基以外之有機基及水解性基，可列舉與式(I)中之含乙烯基之烴基以外之有機基及水解性基相同之基。 Examples of the organic group and the hydrolyzable group other than the vinyl group-containing hydrocarbon group in the above R 1 and R 2 include the same groups as the organic group and the hydrolyzable group other than the vinyl group-containing hydrocarbon group in the formula (I).

作為上述R1中之含乙烯基之烴基，可列舉：碳數2~10之直鏈或支鏈烯基、碳數3~8之環狀烯基等。 Examples of the vinyl group-containing hydrocarbon group in the above R 1 include a linear or branched alkenyl group having 2 to 10 carbon atoms and a cyclic alkenyl group having 3 to 8 carbon atoms.

作為式(I-1)所表示之化合物，具體而言，可列舉：乙烯基三甲氧基矽烷、乙烯基三氯矽烷、乙烯基三乙氧基矽烷、乙烯基三丁氧基矽烷、乙烯基三異丙氧基矽烷、烯丙基三甲氧基矽烷、3-丁烯基三甲氧基矽烷、2-環丙烯基三甲氧基矽烷、2-環戊烯基三甲氧基矽烷、2-環己烯基三甲氧基矽烷、二乙烯基二胺基矽烷、二乙烯基二氯矽烷、二乙烯基二乙醯氧基矽烷、二乙烯基二甲氧基矽烷、二烯丙基二甲氧基矽烷、二(3-丁烯基)二甲氧基矽烷、烯丙基乙基三乙氧基矽烷等。 Specific examples of the compound represented by the formula (I-1) include vinyl trimethoxy decane, vinyl trichloro decane, vinyl triethoxy decane, vinyl tributoxy decane, and vinyl. Triisopropoxy decane, allyl trimethoxy decane, 3-butenyl trimethoxy decane, 2-cyclopropenyl trimethoxy decane, 2-cyclopentenyl trimethoxy decane, 2-cyclohexane Alkenyl trimethoxy decane, divinyl diamino decane, divinyl dichloro decane, divinyl diethoxy decane, divinyl dimethoxy decane, diallyl dimethoxy decane , bis(3-butenyl)dimethoxydecane, allylethyltriethoxydecane, and the like.

作為式(I-2)所表示之化合物，具體而言，可列舉：甲基三氯矽烷、甲基三甲氧基矽烷、甲基三乙氧基矽烷、甲基三丁氧基矽烷、乙 基三甲氧基矽烷、乙基三異丙氧基矽烷、乙基三丁氧基矽烷、正丁基三甲氧基矽烷、五氟苯基三甲氧基矽烷、苯基三甲氧基矽烷、九氟丁基乙基三甲氧基矽烷、三氟甲基三甲氧基矽烷、二甲基二胺基矽烷、二甲基二氯矽烷、二甲基二乙醯氧基矽烷、二甲基二甲氧基矽烷、二苯基二甲氧基矽烷、二丁基二甲氧基矽烷、三甲基氯矽烷、3-(甲基)丙烯醯氧基-正丙基三甲氧基矽烷、3-縮水甘油氧基-正丙基三甲氧基矽烷、3-(3-甲基-3-氧雜環丁烷甲氧基)-正丙基三甲氧基矽烷、氧雜環己基三甲氧基矽烷、甲基三(甲基)丙烯醯氧基矽烷、甲基[2-(甲基)丙烯醯氧基乙氧基]矽烷、甲基-三縮水甘油醚氧基矽烷、甲基三(3-甲基-3-氧雜環丁烷甲氧基)矽烷等。 Specific examples of the compound represented by the formula (I-2) include methyltrichlorodecane, methyltrimethoxydecane, methyltriethoxydecane, methyltributoxydecane, and B. Trimethoxy decane, ethyl triisopropoxy decane, ethyl tributoxy decane, n-butyl trimethoxy decane, pentafluorophenyl trimethoxy decane, phenyl trimethoxy decane, nonafluorobutane Ethyltrimethoxydecane, trifluoromethyltrimethoxydecane, dimethyldiaminodecane, dimethyldichlorodecane, dimethyldiethoxydecane, dimethyldimethoxydecane , diphenyldimethoxydecane, dibutyldimethoxydecane, trimethylchlorodecane, 3-(methyl)propenyloxy-n-propyltrimethoxydecane, 3-glycidoxy - n-propyltrimethoxydecane, 3-(3-methyl-3-oxetanylmethoxy)-n-propyltrimethoxydecane, oxetanyltrimethoxydecane, methyltri Methyl) propylene decyl decane, methyl [2-(methyl) propylene methoxy ethoxy] decane, methyl-triglycidyl ether oxane, methyl tris(3-methyl-3- Oxetane methoxy) decane, and the like.

於將有機矽化合物組合使用之情形時，例如較佳為乙烯基三甲氧基矽烷與3-甲基丙烯醯氧基-正丙基三甲氧基矽烷之組合、乙烯基三甲氧基矽烷與3-縮水甘油氧基-正丙基三甲氧基矽烷之組合等。 In the case where an organic hydrazine compound is used in combination, for example, a combination of vinyltrimethoxynonane and 3-methacryloxy-n-propyltrimethoxydecane, vinyltrimethoxydecane and 3- are preferred. A combination of glycidoxy-n-propyltrimethoxydecane, and the like.

2)熱硬化性化合物或電磁射線硬化性化合物之硬化物 2) a cured product of a thermosetting compound or an electromagnetic ray curable compound

2-1)熱硬化性化合物之硬化物 2-1) Hardened compound of thermosetting compound

(熱硬化性化合物) (thermosetting compound)

本發明之熱硬化性化合物只要為具有可引起熱硬化之官能基之化合物則並無特別限定，可為熱硬化性樹脂亦可為熱硬化性低分子化合物。 The thermosetting compound of the present invention is not particularly limited as long as it has a functional group capable of causing thermal curing, and the thermosetting resin may be a thermosetting low molecular compound.

作為熱硬化性樹脂，具體而言，可列舉：苯酚酚醛清漆樹脂、甲酚酚醛清漆樹脂、雙酚A酚醛清漆樹脂等酚醛清漆型酚系樹脂，可溶酚醛型酚系樹脂等酚系樹脂；雙酚A環氧樹脂、雙酚F環氧樹脂等雙酚型環氧樹脂；酚醛清漆環氧樹脂、甲酚酚醛清漆環氧樹脂等酚醛清漆型環氧樹脂；聯苯型環氧樹脂、茋型環氧樹脂、三苯酚甲烷型環氧樹脂、烷基改性三苯酚甲烷型環氧樹脂、含三核之環氧樹脂、二環戊二烯改性酚型環氧樹脂等環氧樹脂；2,2-雙(4-縮水甘油氧基苯 基)丙烷等具有環氧基之化合物等。又，可列舉：尿素(urea)樹脂；三聚氰胺樹脂等具有三環之樹脂；不飽和聚酯樹脂；雙馬來醯亞胺樹脂；聚胺基甲酸酯樹脂；苯二甲酸二烯丙酯樹脂；聚矽氧樹脂；具有苯并環之樹脂；氰酸酯樹脂；烯烴樹脂等；可使用該等中之1種、或2種以上之混合物。 Specific examples of the thermosetting resin include a phenol novolak resin, a cresol novolak resin, a novolac type phenol resin such as a bisphenol A novolak resin, and a phenol resin such as a novolac type phenol resin; Bisphenol type epoxy resin, bisphenol type epoxy resin and other bisphenol type epoxy resin; novolac epoxy resin, cresol novolac epoxy resin and other novolak type epoxy resin; biphenyl type epoxy resin, bismuth Epoxy resin, trisphenol methane epoxy resin, alkyl modified trisphenol methane epoxy resin, containing three An epoxy resin such as a core epoxy resin or a dicyclopentadiene-modified phenol epoxy resin; a compound having an epoxy group such as 2,2-bis(4-glycidoxyphenyl)propane or the like. Further, examples thereof include: urea (urea) resin; melamine resin and the like have three Ring resin; unsaturated polyester resin; bismaleimide resin; polyurethane resin; diallyl phthalate resin; polyoxyn resin; The resin of the ring; the cyanate resin; the olefin resin; and the like; one of these or a mixture of two or more of them may be used.

又，作為熱硬化性低分子化合物，具體而言，可列舉(甲基)丙烯酸酯系化合物，可列舉：1,6-己二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、雙酚A之雙(丙烯醯氧基乙基)醚、3-甲基戊二醇二(甲基)丙烯酸酯等2官能性(甲基)丙烯酸酯化合物；三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯與酸酐之反應物、二季戊四醇五(甲基)丙烯酸酯與酸酐之反應物、己內酯改性季戊四醇四(甲基)丙烯酸酯、己內酯改性二季戊四醇五(甲基)丙烯酸酯、己內酯改性二季戊四醇六(甲基)丙烯酸酯、環氧乙烷改性季戊四醇四(甲基)丙烯酸酯、環氧乙烷改性二季戊四醇五(甲基)丙烯酸酯、環氧乙烷改性二季戊四醇六(甲基)丙烯酸酯、環氧丙烷改性二季戊四醇五(甲基)丙烯酸酯、環氧丙烷改性二季戊四醇六(甲基)丙烯酸酯等3官能以上之多官能性(甲基)丙烯酸酯化合物等；可使用該等中之1種、或2種以上之混合物。 Further, examples of the thermosetting low molecular compound include a (meth) acrylate compound, and examples thereof include 1,6-hexanediol di(meth)acrylate and ethylene glycol di(methyl). Acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, bisphenol A bis(acryloxyethyl)ether, 3-methylpentanediol a bifunctional (meth) acrylate compound such as di(meth)acrylate; trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, a reaction product of dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tri(meth) acrylate and an acid anhydride, dipentaerythritol penta (meth) acrylate and an acid anhydride, Lactone modified pentaerythritol tetra(meth)acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol hexa(meth) acrylate, ethylene oxide modified pentaerythritol Tetrakis (meth) acrylate, ethylene oxide modified dipentaerythritol penta (meth) acrylate, ring Ethylene-modified dipentaerythritol hexa(meth) acrylate, propylene oxide-modified dipentaerythritol penta (meth) acrylate, propylene oxide-modified dipentaerythritol hexa(meth) acrylate, etc. A (meth) acrylate compound or the like; one of these or a mixture of two or more kinds thereof may be used.

本發明中視需要可添加熱聚合起始劑。熱聚合起始劑係指藉由加熱而產生自由基之化合物，可列舉：有機過氧化物、偶氮化合物、氧化還原起始劑等公知之起始劑。 In the present invention, a thermal polymerization initiator may be added as needed. The thermal polymerization initiator refers to a compound which generates a radical by heating, and examples thereof include known initiators such as an organic peroxide, an azo compound, and a redox initiator.

關於熱聚合起始劑之調配量，相對於熱硬化性化合物，較佳為調配0.01~20質量%，更佳為0.1~10質量%。 The amount of the thermal polymerization initiator to be added is preferably 0.01 to 20% by mass, and more preferably 0.1 to 10% by mass based on the thermosetting compound.

關於熱硬化性化合物之調配量，相對於有機矽化合物之縮合物 與熱硬化性化合物的全部固形物成分而為2~98質量%，較佳為50~95質量%。 Regarding the amount of the thermosetting compound, the condensate relative to the organic cerium compound It is 2 to 98% by mass, preferably 50 to 95% by mass, based on the total solid content of the thermosetting compound.

2-2)電磁射線硬化性化合物之硬化物 2-2) Hardened compound of electromagnetic radiation curable compound

(電磁射線硬化性化合物) (electromagnetic ray hardening compound)

本發明之電磁射線硬化性化合物係指具有於視需要添加之聚合起始劑之存在下藉由電磁射線照射而引起聚合反應之官能基的化合物或樹脂。 The electromagnetic ray curable compound of the present invention refers to a compound or resin having a functional group which causes polymerization reaction by irradiation with electromagnetic rays in the presence of a polymerization initiator to be added as needed.

作為電磁射線，可使用紫外線、X射線、放射線、離子化放射線、游離放射線(α射線、β射線、γ射線、中子射線、電子束)，較佳為包含350nm以下之波長之光。 As the electromagnetic ray, ultraviolet rays, X-rays, radiation, ionized radiation, free radiation (α-ray, β-ray, γ-ray, neutron beam, or electron beam) can be used, and light having a wavelength of 350 nm or less is preferable.

電磁射線之照射可使用超高壓水銀燈、高壓水銀燈、低壓水銀燈、金屬鹵化物燈、準分子燈、碳弧燈、氙弧燈等公知之裝置進行，作為照射光源，較佳為包含150~350nm之範圍內之任一波長之光的光源，更佳為包含250~310nm之範圍內之任一波長之光的光源。 The irradiation of the electromagnetic ray may be performed by using a known device such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, an excimer lamp, a carbon arc lamp, a xenon arc lamp, or the like as an illumination source, preferably comprising 150 to 350 nm. The light source of light of any wavelength within the range is more preferably a light source containing light of any wavelength in the range of 250 to 310 nm.

又，用以使有機無機複合薄膜形成用組合物充分硬化所照射之光之照射光量為0.1~100J/cm2左右，若考慮到膜硬化效率(照射能量與膜硬化程度之關係)，較佳為1~10J/cm2左右，更佳為1~5J/cm2左右。 Moreover, the amount of light to be irradiated by the composition for sufficiently curing the composition for forming an organic-inorganic composite film is about 0.1 to 100 J/cm 2 , and in consideration of the film curing efficiency (the relationship between the irradiation energy and the degree of film hardening), it is preferred. It is about 1 to 10 J/cm 2 , more preferably about 1 to 5 J/cm 2 .

作為電磁射線硬化性化合物，具體而言，可列舉包含(甲基)丙烯酸酯系化合物之乙烯系化合物、環氧樹脂等。藉由電磁射線照射而引起聚合反應之官能基之數量只要為1個以上則並無特別限定。 Specific examples of the electromagnetic ray curable compound include a vinyl compound containing a (meth) acrylate compound, an epoxy resin, and the like. The number of the functional groups which cause the polymerization reaction by the irradiation of the electromagnetic rays is not particularly limited as long as it is one or more.

作為丙烯酸酯系化合物，具體而言，可列舉：聚(甲基)丙烯酸胺基甲酸酯、(甲基)丙烯酸聚酯、環氧(甲基)丙烯酸酯、聚醯胺基(甲基)丙烯酸酯、聚丁二烯(甲基)丙烯酸酯、聚苯乙烯(甲基)丙烯酸酯、聚碳酸酯二丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、己二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯 酸酯、具有(甲基)丙烯醯氧基之矽氧烷聚合物等，較佳為(甲基)丙烯酸聚酯、聚(甲基)丙烯酸胺基甲酸酯、環氧聚(甲基)丙烯酸酯，更佳為聚(甲基)丙烯酸胺基甲酸酯。 Specific examples of the acrylate-based compound include poly(meth)acrylic acid urethane, (meth)acrylic polyester, epoxy (meth) acrylate, and polyamidoamine (methyl). Acrylate, polybutadiene (meth) acrylate, polystyrene (meth) acrylate, polycarbonate diacrylate, tripropylene glycol di(meth) acrylate, hexane diol di(meth) acrylate Ester, trimethylolpropane tri(meth) acrylate, pentaerythritol tri(meth) propylene An acid ester, a siloxane polymer having a (meth) acryloxy group, and the like, preferably a (meth)acrylic polyester, a poly(meth)acrylic acid urethane, or an epoxy poly(methyl). The acrylate is more preferably a poly(meth)acrylic acid urethane.

環氧(甲基)丙烯酸酯可藉由低分子量之雙酚型環氧樹脂或酚醛清漆環氧樹脂之環氧乙烷環與丙烯酸之酯化反應而獲得。 Epoxy (meth) acrylate can be obtained by esterification of an oxirane ring of a low molecular weight bisphenol type epoxy resin or a novolak epoxy resin with acrylic acid.

(甲基)丙烯酸聚酯可藉由將使多元羧酸與多元醇縮合所獲得之兩末端具有羥基之聚酯低聚物之羥基利用丙烯酸進行酯化而獲得。又，可藉由將對多元羧酸加成環氧烷所獲得之低聚物之末端之羥基利用丙烯酸進行酯化而獲得。 The (meth)acrylic polyester can be obtained by esterifying a hydroxyl group of a polyester oligomer having a hydroxyl group at both terminals obtained by condensing a polyvalent carboxylic acid with a polyol with acrylic acid. Further, it can be obtained by esterifying a hydroxyl group at the terminal of the oligomer obtained by adding an alkylene oxide to a polyvalent carboxylic acid with acrylic acid.

(甲基)丙烯酸胺基甲酸酯係使多元醇與二異氰酸酯反應所獲得之異氰酸酯化合物、和具有羥基之丙烯酸酯單體的反應產物，作為多元醇，可列舉：聚酯多元醇、聚醚多元醇、聚碳酸酯二醇等。 The (meth)acrylic acid urethane is a reaction product of an isocyanate compound obtained by reacting a polyhydric alcohol with a diisocyanate and an acrylate monomer having a hydroxyl group, and examples of the polyhydric alcohol include polyester polyol and polyether. Polyol, polycarbonate diol, and the like.

又，作為丙烯酸酯系化合物以外之乙烯系化合物，可列舉：N-乙烯基吡咯啶酮、N-乙烯基己內醯胺、乙酸乙烯酯、苯乙烯、不飽和聚酯等，作為環氧樹脂，可列舉：氫化雙酚A二縮水甘油醚、3,4-環氧環己烷羧酸3,4-環氧環己基甲酯、2-(3,4-環氧環己基-5,5-螺-3,4-環氧)環己烷-間-二烷、雙(3,4-環氧環己基甲基)己二酸酯等。 In addition, examples of the vinyl compound other than the acrylate compound include N-vinylpyrrolidone, N-vinyl caprolactam, vinyl acetate, styrene, and unsaturated polyester. , for example, hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexanecarboxylic acid 3,4-epoxycyclohexyl methyl ester, 2-(3,4-epoxycyclohexyl-5,5 -spiro-3,4-epoxy)cyclohexane-m-two Alkane, bis(3,4-epoxycyclohexylmethyl)adipate, and the like.

關於化合物之分子量，只要可溶於有機無機複合薄膜形成用組合物中則並無限度，通常以質量平均分子量計為500~50,000，較佳為1,000~10,000。 The molecular weight of the compound is not particularly limited as long as it is soluble in the composition for forming an organic-inorganic composite film, and is usually 500 to 50,000, preferably 1,000 to 10,000, in terms of mass average molecular weight.

本發明中視需要可混合聚合起始劑。作為聚合起始劑，可列舉(a)藉由電磁射線照射而產生陽離子種之化合物及(b)藉由電磁射線照射而產生活性自由基種之化合物等公知之聚合起始劑。 In the present invention, a polymerization initiator may be mixed as needed. Examples of the polymerization initiator include a known polymerization initiator such as (a) a compound which generates a cationic species by electromagnetic radiation and (b) a compound which generates an active radical species by irradiation with electromagnetic rays.

3)基於溶解度參數之組合 3) Based on the combination of solubility parameters

本發明中使用之有機矽化合物較佳為藉由Fedors之推算法所求出之式(I)中之R之溶解度參數(SP1)較藉由Fedors之推算法所求出之熱硬 化性化合物或電磁射線硬化性化合物之溶解度參數(SP2)小1.6以上之有機矽化合物(Si1)。SP1與SP2之差值較佳為1.6~8.5，更佳為1.6~7.2。 The organic ruthenium compound used in the present invention is preferably a heat-hardness of the solubility parameter (SP1) of R in the formula (I) determined by the Fedors' push algorithm compared to the Fedors' push algorithm. The organic compound (Si1) having a solubility parameter (SP2) of 1.6 or more in the chemical compound or the electromagnetic ray curable compound. The difference between SP1 and SP2 is preferably 1.6 to 8.5, more preferably 1.6 to 7.2.

本發明中使用之有機矽化合物亦可進而包含SP1較SP2小1.6以下之有機矽化合物、或SP1大於SP2之有機矽化合物(Si2)，Si1與Si2之比(Si1：Si2)為5：5~10：0，較佳為9：1~10：0。 The organic ruthenium compound used in the present invention may further comprise an organic ruthenium compound having a SP1 smaller than SP2 of 1.6 or less, or an organic ruthenium compound (Si2) having an SP1 larger than SP2, and a ratio of Si1 to Si2 (Si1:Si2) of 5:5~. 10:0, preferably 9:1~10:0.

有機矽化合物根據熱硬化性化合物或電磁射線硬化性化合物之種類而有所不同。有機矽化合物及熱硬化性化合物或電磁射線硬化性化合物之溶解度參數(SP值)可根據Fedors之推算法進行計算，因此可基於預先算出之SP值而決定有機矽化合物與熱硬化性化合物或電磁射線硬化性化合物之組合。 The organic ruthenium compound differs depending on the type of the thermosetting compound or the electromagnetic ray curable compound. The solubility parameter (SP value) of the organic cerium compound and the thermosetting compound or the electromagnetic ray curable compound can be calculated according to the Fedors' calculation algorithm. Therefore, the organic cerium compound and the thermosetting compound or electromagnetic can be determined based on the previously calculated SP value. A combination of radiation curable compounds.

例如於使用聚丁二烯(SP值8.5)作為熱硬化性化合物之情形時，作為SP值較聚丁二烯小1.6以上之有機矽化合物，具體而言，可列舉：甲基三氯矽烷、甲基三甲氧基矽烷、甲基三乙氧基矽烷、甲基三丁氧基矽烷、甲基三(甲基)丙烯醯氧基矽烷、甲基三[2-(甲基)丙烯醯氧基乙氧基]矽烷、甲基三縮水甘油醚氧基矽烷、甲基三(3-甲基-3-氧雜環丁烷甲氧基)矽烷、乙基三甲氧基矽烷、乙基三異丙氧基矽烷、乙基三(正丁氧基)矽烷、二甲基二氯矽烷、二甲基二甲氧基矽烷、二甲基二胺基矽烷、二甲基二乙醯氧基矽烷(該等之SP值均為6.9以下)。 For example, when a polybutadiene (SP value of 8.5) is used as the thermosetting compound, the organic ruthenium compound having an SP value smaller than 1.6 or more of polybutadiene may specifically be methyltrichloromethane or the like. Methyltrimethoxydecane, methyltriethoxydecane, methyltributoxydecane, methyltris(meth)propenyloxydecane,methyltris[2-(methyl)propenyloxy Ethoxy]decane, methyltriglycidyloxyoxydecane, methyltris(3-methyl-3-oxetanylmethoxy)decane, ethyltrimethoxydecane, ethyltriisopropyl Oxydecane, ethyl tri(n-butoxy)decane, dimethyldichlorodecane, dimethyldimethoxydecane, dimethyldiaminodecane, dimethyldiethoxydecane (this The SP values are equal to 6.9 or less).

又，作為SP值較聚丁二烯之SP值小1.6以下之有機矽化合物、或SP值大於聚丁二烯之SP值之有機矽化合物，具體而言，可列舉：三氟甲基三甲氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三氯矽烷、乙烯基三乙氧基矽烷、正丁基三甲氧基矽烷、五氟苯基三甲氧基矽烷、苯基三甲氧基矽烷、九氟-正丁基乙基二甲氧基矽烷、二苯基二甲氧基矽烷、二-正丁基二甲氧基矽烷、3-(甲基)丙烯醯氧基-正丙基三甲氧基矽烷、3-(3-甲基-3-氧雜環丁烷甲氧基)-正丙基三甲氧基矽烷、氧雜 環己基三甲氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-縮水甘油氧基-正丙基三甲氧基矽烷、3-縮水甘油氧基-正丙基甲基二乙氧基矽烷、3-縮水甘油氧基-正丙基三乙氧基矽烷、對苯乙烯基三甲氧基矽烷、3-甲基丙烯醯氧基-正丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基-正丙基三甲氧基矽烷、3-甲基丙烯醯氧基-正丙基甲基二乙氧基矽烷、3-甲基丙烯醯氧基-正丙基三乙氧基矽烷、3-丙烯醯氧基-正丙基三甲氧基矽烷、N-(2-胺基乙基)-3-胺基-正丙基甲基二甲氧基矽烷、N-(2-胺基乙基)-3-胺基-正丙基三甲氧基矽烷、N-(2-胺基乙基)-3-胺基-正丙基三乙氧基矽烷、3-胺基-正丙基三甲氧基矽烷、3-胺基-正丙基三乙氧基矽烷、3-N-(1,3-二甲基-亞丁基)胺基-正丙基三乙氧基矽烷、N-苯基-3-胺基-正丙基三甲氧基矽烷、具有包含聚合物部分之烴基的有機矽化合物(該等之SP值均大於6.9)。 Further, the organic ruthenium compound having an SP value smaller than the SP value of the polybutadiene by 1.6 or less, or the organic ruthenium compound having an SP value larger than the SP value of the polybutadiene, specifically, a trifluoromethyltrimethoxy group Base decane, vinyl trimethoxy decane, vinyl trichloro decane, vinyl triethoxy decane, n-butyl trimethoxy decane, pentafluorophenyl trimethoxy decane, phenyl trimethoxy decane, nonafluoro - n-butylethyldimethoxydecane, diphenyldimethoxydecane, di-n-butyldimethoxydecane, 3-(methyl)propenyloxy-n-propyltrimethoxydecane , 3-(3-methyl-3-oxetanylmethoxy)-n-propyltrimethoxydecane, oxa Cyclohexyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-glycidoxy-n-propyltrimethoxydecane, 3-glycidoxy-n-propyl Methyldiethoxydecane, 3-glycidoxy-n-propyltriethoxydecane, p-styryltrimethoxydecane, 3-methylpropenyloxy-n-propylmethyldimethyl Oxydecane, 3-methylpropenyloxy-n-propyltrimethoxydecane, 3-methylpropenyloxy-n-propylmethyldiethoxydecane, 3-methylpropenyloxy- N-propyltriethoxydecane, 3-propenyloxy-n-propyltrimethoxydecane, N-(2-aminoethyl)-3-amino-n-propylmethyldimethoxydecane , N-(2-Aminoethyl)-3-amino-n-propyltrimethoxydecane, N-(2-aminoethyl)-3-amino-n-propyltriethoxydecane, 3-amino-n-propyltrimethoxydecane, 3-amino-n-propyltriethoxydecane, 3-N-(1,3-dimethyl-butylene)amino-n-propyltri Ethoxy decane, N-phenyl-3-amino-n-propyltrimethoxynonane, organic hydrazine compound having a hydrocarbon group containing a polymer moiety (the SP values of these are all To 6.9).

例如於使用二季戊四醇六丙烯酸酯(SP值：10.4)作為電磁射線硬化性化合物之情形時，作為SP值較二季戊四醇六丙烯酸酯之SP值小1.6以上之有機矽化合物，具體而言，可列舉：甲基三氯矽烷、甲基三甲氧基矽烷、甲基三乙氧基矽烷、甲基三丁氧基矽烷、乙基三甲氧基矽烷、乙基三異丙氧基矽烷、乙基三(正丁氧基)矽烷、三氟甲基三甲氧基矽烷、二甲基二胺基矽烷、二甲基二氯矽烷、二甲基二乙醯氧基矽烷、二甲基二甲氧基矽烷、乙烯基三甲氧基矽烷、甲基三(甲基)丙烯醯氧基矽烷、甲基三[2-(甲基)丙烯醯氧基乙氧基]矽烷、甲基三縮水甘油醚氧基矽烷、甲基三(3-甲基-3-氧雜環丁烷甲氧基)矽烷、乙烯基三氯矽烷、乙烯基三乙氧基矽烷、正丁基三甲氧基矽烷、二-正丁基二甲氧基矽烷(該等之SP值均為8.8以下)。 For example, when dipentaerythritol hexaacrylate (SP value: 10.4) is used as the electromagnetic ray curable compound, the organic ruthenium compound having an SP value smaller than the SP value of dipentaerythritol hexaacrylate by 1.6 or more is specifically exemplified. Methyltrichloromethane, methyltrimethoxydecane, methyltriethoxydecane, methyltributoxydecane, ethyltrimethoxydecane, ethyltriisopropoxydecane, ethyltri n-Butyloxy)decane, trifluoromethyltrimethoxydecane, dimethyldiaminodecane, dimethyldichlorodecane, dimethyldiethoxydecane, dimethyldimethoxydecane, Vinyl trimethoxy decane, methyl tris(meth) propylene decyl decane, methyl tris[2-(methyl) propylene methoxy ethoxy] decane, methyl triglycidyl ether oxy decane, Methyl tris(3-methyl-3-oxetanylmethoxy)decane, vinyl trichlorodecane, vinyl triethoxydecane, n-butyltrimethoxydecane, di-n-butyl Methoxy decane (the SP values are all below 8.8).

於該情形時，有機矽化合物較佳為式(I)中之n為1且R具有碳數1~3之有機基者。 In this case, the organic ruthenium compound is preferably an organic group in which n in the formula (I) is 1 and R has a carbon number of 1 to 3.

又，作為SP值較二季戊四醇六丙烯酸酯之SP值小1.6以下之有機 矽化合物、或SP值大於二季戊四醇六丙烯酸酯之SP值之有機矽化合物，具體而言，可列舉：五氟苯基三甲氧基矽烷、苯基三甲氧基矽烷、九氟-正丁基乙基二甲氧基矽烷、二苯基二甲氧基矽烷、3-(甲基)丙烯醯氧基-正丙基三甲氧基矽烷、3-(3-甲基-3-氧雜環丁烷甲氧基)-正丙基三甲氧基矽烷、氧雜環己基三甲氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-縮水甘油醚氧基-正丙基三甲氧基矽烷、3-縮水甘油醚氧基-正丙基甲基二乙氧基矽烷、3-縮水甘油醚氧基-正丙基三乙氧基矽烷、對苯乙烯基三甲氧基矽烷、3-甲基丙烯醯氧基-正丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基-正丙基三甲氧基矽烷、3-甲基丙烯醯氧基-正丙基甲基二乙氧基矽烷、3-甲基丙烯醯氧基-正丙基三乙氧基矽烷、3-丙烯醯氧基-正丙基三甲氧基矽烷、N-(2-胺基乙基)-3-胺基-正丙基甲基二甲氧基矽烷、N-(2-胺基乙基)-3-胺基-正丙基三甲氧基矽烷、N-(2-胺基乙基)-3-胺基-正丙基三乙氧基矽烷、3-胺基-正丙基三甲氧基矽烷、3-胺基-正丙基三乙氧基矽烷、3-(N-1,3-二甲基-亞丁基)胺基-正丙基三乙氧基矽烷、N-苯基-3-胺基-正丙基三甲氧基矽烷、具有包含聚合物部分之烴基的有機矽化合物(該等之SP值均大於8.8)。 Moreover, as an SP value, the SP value of dipentaerythritol hexaacrylate is less than 1.6 The ruthenium compound or the organic ruthenium compound having an SP value greater than the SP value of dipentaerythritol hexaacrylate, specifically, pentafluorophenyltrimethoxydecane, phenyltrimethoxynonane, nonafluoro-n-butyl B Dimethoxy decane, diphenyl dimethoxy decane, 3-(methyl) propylene methoxy-n-propyl trimethoxy decane, 3-(3-methyl-3-oxetane Methoxy)-n-propyltrimethoxydecane, oxetanyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-glycidyloxy-positive Propyltrimethoxydecane, 3-glycidyloxy-n-propylmethyldiethoxydecane, 3-glycidyloxy-n-propyltriethoxydecane, p-styryltrimethoxy Decane, 3-methacryloxyl-n-propylmethyldimethoxydecane, 3-methylpropenyloxy-n-propyltrimethoxydecane, 3-methylpropenyloxy-n-propyl Methyldiethoxydecane, 3-methylpropenyloxy-n-propyltriethoxydecane, 3-propenyloxy-n-propyltrimethoxydecane, N-(2-Amino B 3-amino-n-propylmethyldimethoxy Alkyl, N-(2-aminoethyl)-3-amino-n-propyltrimethoxydecane, N-(2-aminoethyl)-3-amino-n-propyltriethoxydecane , 3-amino-n-propyltrimethoxydecane, 3-amino-n-propyltriethoxydecane, 3-(N-1,3-dimethyl-butylene)amino-n-propyl Triethoxy decane, N-phenyl-3-amino-n-propyltrimethoxydecane, an organic hydrazine compound having a hydrocarbon group containing a polymer moiety (all of these SP values are greater than 8.8).

4)有機無機複合薄膜之形成方法 4) Method for forming organic-inorganic composite film

4-1)有機無機複合薄膜形成用組合物之製備 4-1) Preparation of composition for forming an organic-inorganic composite film

本發明中之有機無機複合薄膜形成用組合物可將有機矽化合物、熱硬化性化合物或電磁射線硬化性化合物、除此以外之適宜之聚合起始劑、矽烷醇縮合觸媒、水及/或溶劑等進行混合而製備。 The composition for forming an organic-inorganic composite film of the present invention may be an organic ruthenium compound, a thermosetting compound or an electromagnetic ray-curable compound, a suitable polymerization initiator other than the above, a stanol condensation catalyst, water and/or A solvent or the like is prepared by mixing.

作為矽烷醇縮合觸媒，可列舉：金屬烷氧化物、金屬螯合化合物、有機酸金屬鹽或該等之水解縮合物等金屬化合物，具體而言，可列舉：四異丙醇鈦、雙乙醯丙酮二異丙醇鈦、或其(等)之水解縮合物等。 Examples of the decyl alcohol condensation catalyst include a metal alkoxide, a metal chelate compound, an organic acid metal salt, or a metal compound such as the hydrolysis condensate, and specific examples thereof include titanium tetraisopropoxide and double B. Acetone, titanium diisopropylate, or a hydrolyzed condensate thereof.

作為矽烷醇縮合觸媒，除上述金屬化合物以外，亦可列舉酸、鹼等。 Examples of the stanol condensation catalyst include an acid, a base, and the like in addition to the above metal compound.

作為酸，可列舉：有機酸、無機酸，例如作為有機酸，可列舉：乙酸、甲酸、草酸、碳酸、苯二甲酸、三氟乙酸、對甲苯磺酸、甲磺酸等；作為無機酸，可列舉：鹽酸、硝酸、硼酸、氟硼酸等。 Examples of the acid include an organic acid and an inorganic acid. Examples of the organic acid include acetic acid, formic acid, oxalic acid, carbonic acid, phthalic acid, trifluoroacetic acid, p-toluenesulfonic acid, methanesulfonic acid and the like. Examples thereof include hydrochloric acid, nitric acid, boric acid, and fluoroboric acid.

此處，作為酸，亦包含藉由光照射而產生酸之光酸產生劑，具體而言，六氟磷酸二苯基錪、六氟磷酸三苯基鏻等在內。 Here, the acid also includes a photoacid generator which generates an acid by light irradiation, specifically, diphenylphosphonium hexafluorophosphate or triphenylphosphonium hexafluorophosphate.

作為鹼，可列舉：四甲基胍、四甲基胍基丙基三甲氧基矽烷等強鹼類；有機胺類、有機胺之羧酸中和鹽、四級銨鹽等。 Examples of the base include strong bases such as tetramethylguanidine and tetramethylguanidinopropyltrimethoxydecane; organic amines, carboxylic acid neutralized salts of organic amines, and quaternary ammonium salts.

使用金屬化合物作為矽烷醇縮合觸媒情形時之製備方法並無特別限制，可列舉如下等製備方法，即，將金屬化合物混合於溶劑中，添加特定量之水而進行(部分)水解，繼而添加有機矽化合物而使之(部分)水解，另一方面，將熱硬化性化合物或電磁射線硬化性化合物溶解於溶劑中，視需要添加聚合起始劑或硬化劑，其後將兩溶液混合。 The preparation method in the case of using a metal compound as a decyl alcohol condensation catalyst is not particularly limited, and a preparation method such as mixing a metal compound in a solvent, adding a specific amount of water to carry out (partial) hydrolysis, and then adding The organic hydrazine compound is (partially) hydrolyzed. On the other hand, the thermosetting compound or the electromagnetic ray curable compound is dissolved in a solvent, and if necessary, a polymerization initiator or a curing agent is added, and then the two solutions are mixed.

該等四種成分亦可同時混合，又，關於有機矽化合物與金屬化合物之混合方法，可列舉：將有機矽化合物與金屬化合物混合後添加水而進行(部分)水解之方法、或將有機矽化合物及金屬化合物各自之經(部分)水解所得者進行混合之方法。並非必須添加水或溶劑，但較佳為添加水而形成(部分)水解物。作為特定量之水之量，取決於金屬化合物之種類，於金屬化合物為具有2以上之羥基或水解性基之金屬化合物之情形時，相對於金屬化合物1莫耳，較佳為使用0.5莫耳以上之水，更佳為使用0.5~2莫耳之水。又，於金屬化合物為金屬螯合化合物或有機酸金屬鹽之情形時，相對於金屬螯合化合物或有機酸金屬鹽1莫耳，較佳為使用5~100莫耳之水，更佳為使用5~20莫耳之水。 These four components may be mixed at the same time, and a method of mixing the organic ruthenium compound and the metal compound may be a method of performing (partial) hydrolysis by mixing an organic ruthenium compound with a metal compound, or adding an organic hydrazine. A method in which the compound and the metal compound are each subjected to (partial) hydrolysis to obtain a mixture. It is not necessary to add water or a solvent, but it is preferred to add water to form a (partial) hydrolyzate. The amount of the specific amount of water depends on the kind of the metal compound, and in the case where the metal compound is a metal compound having a hydroxyl group or a hydrolyzable group of 2 or more, 0.5 mol is preferably used with respect to the metal compound 1 mol. The above water is more preferably used in 0.5 to 2 moles of water. Further, in the case where the metal compound is a metal chelate compound or an organic acid metal salt, it is preferably used in an amount of 5 to 100 mTorr with respect to the metal chelate compound or the organic acid metal salt 1 mol, more preferably used. 5 to 20 moles of water.

作為本發明之有機矽化合物之縮合物，可採用使用公知之矽烷醇縮合觸媒而使有機矽化合物(部分)水解所得者。 As the condensate of the organic hydrazine compound of the present invention, those obtained by hydrolyzing an organic hydrazine compound (partially) using a known decyl alcohol condensation catalyst can be used.

縮合物之平均粒徑較佳為2nm~100nm，更佳為5nm~30nm。若平均粒徑大於100nm，則組合物出現白濁，組合物變得不穩定而易凝膠化。若平均粒徑小於2nm，則存在對塗膜性造成不良影響之情況。 The average particle diameter of the condensate is preferably from 2 nm to 100 nm, more preferably from 5 nm to 30 nm. If the average particle diameter is more than 100 nm, the composition becomes cloudy, and the composition becomes unstable and gels easily. When the average particle diameter is less than 2 nm, there is a case where the coating property is adversely affected.

作為本發明中之有機無機複合薄膜形成用組合物，較佳為除上述各成分以外亦含有水及/或有機溶劑。 The composition for forming an organic-inorganic composite film of the present invention preferably contains water and/or an organic solvent in addition to the above components.

作為所使用之有機溶劑，並無特別限制，例如可列舉：苯、甲苯、二甲苯等芳香族烴類；己烷、辛烷等脂肪族烴類；環己烷、環戊烷等脂環族烴類；丙酮、甲基乙基酮、環己酮等酮類；四氫呋喃、二烷等醚類；乙酸乙酯、乙酸丁酯等酯類；N,N-二甲基甲醯胺、N,N-二甲基乙醯胺等醯胺類；二甲基亞碸等亞碸類；甲醇、乙醇等醇類；乙二醇單甲醚、乙二醇單甲醚乙酸酯等多元醇衍生物類等。該等有機溶劑可單獨使用1種或將2種以上組合使用。 The organic solvent to be used is not particularly limited, and examples thereof include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane and octane; and alicyclic groups such as cyclohexane and cyclopentane. Hydrocarbons; ketones such as acetone, methyl ethyl ketone, cyclohexanone; tetrahydrofuran, Ethers such as alkyl ethers; esters such as ethyl acetate and butyl acetate; decylamines such as N,N-dimethylformamide and N,N-dimethylacetamide; Classes; alcohols such as methanol and ethanol; polyol derivatives such as ethylene glycol monomethyl ether and ethylene glycol monomethyl ether acetate. These organic solvents may be used alone or in combination of two or more.

本發明中之有機無機複合薄膜形成用組合物中之固形物成分為1~98質量%，較佳為10~60質量%，更佳為15~45質量%。 The solid content in the composition for forming an organic-inorganic composite film of the present invention is from 1 to 98% by mass, preferably from 10 to 60% by mass, more preferably from 15 to 45% by mass.

4-2)有機無機複合薄膜之形成方法 4-2) Method for forming organic-inorganic composite film

本發明之有機無機複合薄膜可藉由經過(A)將上述有機無機複合薄膜形成用組合物塗佈於樹脂基材上並進行乾燥及/或加熱之步驟、(B)實施電漿處理或UV(ultraviolet，紫外線)臭氧處理之步驟而形成。 The organic-inorganic composite film of the present invention can be subjected to a step (A) by applying the composition for forming an organic-inorganic composite film to a resin substrate, drying and/or heating, and (B) performing a plasma treatment or UV treatment. (ultraviolet, ultraviolet) formed by the step of ozone treatment.

本發明之有機無機複合薄膜由於在薄膜之表面部形成「有機矽化合物之縮合物經濃縮之層」，故而獲得表面部之無機成分之比率較高之硬化膜。於該情形時，有機成分之比率相對變低。此可通過藉由運用X射線光電子分光分析而測定深度方向之碳原子之濃度進行確認。此處，所謂「碳原子之濃度」意指將(所有金屬原子+氧原子+碳原子)設為100%時之碳原子之莫耳濃度。其他之氧原子及碳原子之濃度亦相同。該有機成分之比率較低之層中，矽原子之濃度變高。 In the organic-inorganic composite film of the present invention, a "concentrated layer of a condensate of an organic cerium compound" is formed on the surface of the film, whereby a cured film having a high ratio of inorganic components in the surface portion is obtained. In this case, the ratio of the organic components is relatively low. This can be confirmed by measuring the concentration of carbon atoms in the depth direction by X-ray photoelectron spectroscopy. Here, the "concentration of carbon atoms" means the molar concentration of carbon atoms when (all metal atoms + oxygen atoms + carbon atoms) is 100%. The concentrations of other oxygen atoms and carbon atoms are also the same. In the layer in which the ratio of the organic component is low, the concentration of the ruthenium atom becomes high.

並且，本發明之有機無機複合薄膜較佳為距離表面之深度為10nm之碳原子之濃度較距離表面之深度為100nm之碳原子之濃度小20%以上之膜。再者，可將有機無機複合薄膜之膜厚規定為於X射線光電子分光分析中進行濺鍍蝕刻時所算出之值。 Further, the organic-inorganic composite film of the present invention is preferably a film having a concentration of carbon atoms having a depth of 10 nm from the surface which is 20% or more smaller than a concentration of carbon atoms having a depth of 100 nm from the surface. Further, the film thickness of the organic-inorganic composite film can be defined as a value calculated by sputtering etching in X-ray photoelectron spectroscopy.

作為有機無機複合薄膜形成用組合物之塗佈方法，可使用公知之塗佈方法，例如可列舉：浸漬法、噴霧法、棒式塗佈法、輥式塗佈法、旋轉塗佈法、淋幕式塗佈法、凹版印刷法、絲網印刷法、噴墨法等。又，作為形成之膜厚，並無特別限制，例如為0.1~20μm左右。 As a coating method of the composition for forming an organic-inorganic composite film, a known coating method can be used, and examples thereof include a dipping method, a spray method, a bar coating method, a roll coating method, a spin coating method, and a shower method. Curtain coating method, gravure printing method, screen printing method, inkjet method, and the like. Moreover, the film thickness to be formed is not particularly limited, and is, for example, about 0.1 to 20 μm.

作為塗佈有機無機複合薄膜形成用組合物所形成之膜之乾燥、加熱處理，例如較佳為於40~200℃下進行0.5~120分鐘左右，更佳為於60~160℃下進行1~60分鐘左右，進而較佳為於60~120℃下進行1~60分鐘左右。 The drying and heat treatment of the film formed by coating the composition for forming an organic-inorganic composite film is preferably carried out at 40 to 200 ° C for about 0.5 to 120 minutes, more preferably at 60 to 160 ° C for 1 to 1 hour. It is about 60 minutes, and further preferably about 60 to 120 ° C for about 1 to 60 minutes.

樹脂基材上形成有加熱後之薄膜時之由JIS K 5600-5-4鉛筆法所規定之鉛筆硬度為1H~4H左右，就與樹脂基材之密接性及硬度之方面而言，較佳為2H~4H。 When the heated film is formed on the resin substrate, the pencil hardness specified by the pencil method of JIS K 5600-5-4 is about 1H to 4H, which is preferable in terms of adhesion to the resin substrate and hardness. It is 2H~4H.

(3)有機矽烷薄膜 (3) Organic germane film

本發明之有機矽烷薄膜係含有以下之d)、e)及f)者。 The organodecane film of the present invention contains the following d), e) and f).

d)含環氧基之三烷氧基矽烷之水解縮合物；e)聚胺類；及f)f-1)正戊醇、或者f-2)25℃下之pKa為2.0~6.0之範圍之有機酸、或具有全氟烷基或全氟伸烷基之碳數2~5之醇類 d) a hydrolysis condensate of an epoxy group-containing trialkoxy decane; e) a polyamine; and f) f-1) n-pentanol, or f-2) a pKa of from 2.0 to 6.0 at 25 ° C An organic acid or an alcohol having a perfluoroalkyl group or a perfluoroalkyl group having 2 to 5 carbon atoms

本發明之有機矽烷薄膜可由含有上述d)、e)及f)之組合物(有機矽烷薄膜形成用組合物)形成。 The organodecane film of the present invention can be formed from a composition (organodecane film-forming composition) containing the above d), e) and f).

以下進行詳細說明。 The details are described below.

1)含環氧基之三烷氧基矽烷之水解縮合物 1) Hydrolyzed condensate of epoxy group-containing trialkoxy decane

上述d)所示之含環氧基之三烷氧基矽烷之水解縮合物係含環氧基之三烷氧基矽烷進行縮合所得之聚合物或低聚物。 The hydrolysis condensate of the epoxy group-containing trialkoxysilane shown in the above d) is a polymer or oligomer obtained by condensation of an epoxy group-containing trialkoxy decane.

組合物中之含環氧基之三烷氧基矽烷之水解縮合物等之固形物成分濃度並無特別限制，較佳為1.0~50質量%之範圍，更佳為1.0~10質量%或1.5~3.0質量%之範圍。 The concentration of the solid content component of the hydrolysis-condensation product of the epoxy group-containing trialkoxysilane in the composition is not particularly limited, but is preferably in the range of 1.0 to 50% by mass, more preferably 1.0 to 10% by mass or 1.5. ~3.0% by mass range.

關於固形物成分濃度，可於最初即調整為特定之固形物成分濃度，亦可以較濃之狀態製備組合物後進行稀釋而調整為特定之固形物成分濃度。 The concentration of the solid content component can be adjusted to a specific solid content concentration at the beginning, or the composition can be prepared in a relatively concentrated state and then diluted to adjust to a specific solid content concentration.

含環氧基之三烷氧基矽烷之水解縮合物之製備法並無特別限制，例如可利用以下之製備法1、2等方法製備。 The preparation method of the hydrolysis condensate of the epoxy group-containing trialkoxysilane is not particularly limited, and for example, it can be produced by the following methods 1, 2, and the like.

[製備法1] [Preparation method 1]

將含環氧基之三烷氧基矽烷及/或其水解縮合物與水、及聚胺類或咪唑類進行混合、攪拌。 The epoxy group-containing trialkoxy decane and/or its hydrolysis condensate is mixed with water, a polyamine or an imidazole, and stirred.

(作為原料之含環氧基之三烷氧基矽烷及/或其水解縮合物) (epoxy group-containing trialkoxy decane and/or its hydrolysis condensate as a raw material)

本發明中使用之含環氧基之三烷氧基矽烷只要為除會因水解等而轉化之官能基部分以外亦包含環氧基之三烷氧基矽烷，則其結構並無特別限制。 The epoxy group-containing trialkoxy decane used in the present invention is not particularly limited as long as it is a trialkoxy group containing an epoxy group in addition to a functional group which is converted by hydrolysis or the like.

若以通式表示，可列舉下述式(II)所表示之化合物。 The compound represented by the following formula (II) is represented by the formula.

R3-Si(OR4)3 (II) R 3 -Si(OR 4 ) 3 (II)

式中，R3表示具有環氧基或縮水甘油氧基之烴基，R4表示烷基。 In the formula, R 3 represents a hydrocarbon group having an epoxy group or a glycidyl group of glycerin, R 4 represents an alkyl group.

R3中只要包含1個以上之環氧基或縮水甘油氧基即可，較佳為具有1~3個，亦可包含環氧基、縮水甘油氧基兩者。 R 3 may contain one or more epoxy groups or glycidoxy groups, and preferably has 1 to 3, and may contain both an epoxy group and a glycidoxy group.

作為R3之「具有環氧基或縮水甘油氧基之烴基」之「烴基」，可列舉：烷基、環烷基、環烷基烷基、烯基、環烯基、炔基、芳基、芳基烷基、芳基烯基等。作為碳數，較佳為1~30個之範圍，更佳為1~10個之範圍，具體而言，可列舉式(I)之R所表示之烴基。 Examples of the "hydrocarbon group" of the "hydrocarbon group having an epoxy group or a glycidoxy group" of R 3 include an alkyl group, a cycloalkyl group, a cycloalkylalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, and an aryl group. , arylalkyl, arylalkenyl, and the like. The carbon number is preferably in the range of 1 to 30, more preferably in the range of 1 to 10, and specific examples thereof include a hydrocarbon group represented by R in the formula (I).

上述「烴基」中亦可具有除環氧基及縮水甘油氧基以外之取代基，作為此種取代基，可列舉：鹵基、烷基、烯基、烷氧基、(甲基)丙烯醯氧基等。 The above "hydrocarbon group" may have a substituent other than the epoxy group and the glycidoxy group, and examples of such a substituent include a halogen group, an alkyl group, an alkenyl group, an alkoxy group, and a (meth) propylene group. Oxyl and the like.

此處，作為鹵基，可列舉：氟基、氯基、溴基、碘基等。 Here, examples of the halogen group include a fluorine group, a chlorine group, a bromine group, and an iodine group.

作為烷氧基，可列舉：甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、異丁氧基、第三丁氧基等。 Examples of the alkoxy group include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, and a third butoxy group.

作為烷基、烯基，可列舉與上述R中之烷基、烯基相同之烴基。 Examples of the alkyl group and the alkenyl group include the same hydrocarbon groups as the alkyl group and the alkenyl group in the above R.

作為R4之「烷基」，可列舉與上述R中之烷基相同之烴基。 Examples of the "alkyl group" of R 4 include the same hydrocarbon group as the alkyl group in the above R.

上述「烷基」可具有取代基，作為此種取代基，可列舉：鹵基、烷氧基、(甲基)丙烯醯氧基等。 The above "alkyl group" may have a substituent, and examples of such a substituent include a halogen group, an alkoxy group, and a (meth)acryloxy group.

關於作為原料之含環氧基之三烷氧基矽烷或其水解縮合物，較佳為縮水甘油氧基烷基三烷氧基矽烷或縮水甘油氧基烯基烷氧基矽烷。該等可單獨使用1種或將2種以上混合使用。 As the epoxy group-containing trialkoxysilane or a hydrolysis condensate thereof, a glycidoxyalkyltrialkoxide or a glycidoxyalkenyl alkoxydecane is preferred. These may be used alone or in combination of two or more.

作為式(II)所表示之化合物，具體而言，可列舉：甲基-三縮水甘油醚氧基矽烷、甲基三(3-甲基-3-氧雜環丁烷甲氧基)矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-縮水甘油氧基-正丙基三甲氧基矽烷、3-縮水甘油氧基-正丙基甲基二乙氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷。 Specific examples of the compound represented by the formula (II) include methyl-triglycidyloxy decane and methyltris(3-methyl-3-oxetanylmethoxy)decane. 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-glycidoxy-n-propyltrimethoxydecane, 3-glycidoxy-n-propylmethyldiethoxy Decane, 3-glycidoxypropyltriethoxydecane.

(含環氧基之三烷氧基矽烷以外之烷氧基矽烷類) (alkoxy decane other than epoxy-containing trialkoxy decane)

本發明中，視需要可添加使用上述含環氧基之三烷氧基矽烷以外之烷氧基矽烷類。作為此種烷氧基矽烷類，可列舉：四烷氧基矽烷類、三烷氧基矽烷類、二烷氧基矽烷類等。進而亦可同樣地使用該等之部分水解縮合物。 In the present invention, an alkoxydecane other than the above-described epoxy group-containing trialkoxy decane may be added as needed. Examples of such alkoxy decanes include tetraalkoxy decanes, trialkoxy decanes, dialkoxy decanes, and the like. Further, these partial hydrolysis condensates may be used in the same manner.

(水) (water)

所使用之水之量只要為可使所使用之含環氧基之三烷氧基矽烷及/或其水解縮合物於一定程度上水解縮合之量以上，則並無特別限 制，相對於所使用之含環氧基之三烷氧基矽烷及/或其水解縮合物(其中，於將含環氧基之三烷氧基矽烷與其水解縮合物併用之情形時表示此兩者之合計，又，於併用含環氧基之三烷氧基矽烷以外之烷氧基矽烷之情形時亦表示該等全體之合計)1莫耳，較佳為0.5莫耳以上，更佳為1.0莫耳以上、2.0莫耳以上、5.0莫耳以上或10莫耳以上。 The amount of water to be used is not particularly limited as long as it can liquefy and condense the epoxy group-containing trialkoxy decane and/or its hydrolysis condensate to some extent. And the above-mentioned epoxy group-containing trialkoxy decane and/or its hydrolysis condensate (wherein, when the epoxy group-containing trialkoxy decane is used in combination with the hydrolysis condensate thereof) In the case of a combination of alkoxy decanes other than the epoxy group-containing trialkoxy decane, the total amount of the total is 1 mole, preferably 0.5 mole or more, more preferably 1.0 moles or more, 2.0 moles or more, 5.0 moles or more, or 10 moles or more.

(聚胺類) (polyamines)

所使用之聚胺類只要為1分子中具有2以上之鍵結有1個以上之氫原子之胺基或亞胺基的化合物，則並無特別限制，具體而言，可列舉：乙二胺、三亞甲基二胺、四亞甲基二胺、六亞甲基二胺、二伸乙基三胺、三伸乙基四胺、四伸乙基五胺、二伸丙基三胺、甲基胺基丙基胺、乙基胺基丙基胺、N,N'-二甲基六亞甲基二胺、雙(2-甲基胺基乙基)醚、薄荷烷二胺、異佛爾酮二胺、3,9-雙(3-胺基丙基)-2,4,8,10-四氧基螺(5,5)十一烷加成物、雙(4-胺基環己基)甲烷、鄰苯二胺、間苯二胺、對苯二胺、二胺基二苯基甲烷、二胺基二苯基碸、間苯二甲胺等。該等可單獨使用1種或將2種以上混合使用。其中，較佳為伸烷基聚胺、聚伸烷基聚胺、聚(伸苯基伸烷基)聚胺及(伸環烷基)烷基聚胺，尤佳為聚伸烷基聚胺。具體而言，可列舉：二伸乙基三胺、三伸乙基四胺、四伸乙基五胺、二伸丙基三胺等。 The polyamine to be used is not particularly limited as long as it is a compound having two or more amine groups or imine groups in which one or more hydrogen atoms are bonded in one molecule, and specific examples thereof include ethylenediamine. , trimethylene diamine, tetramethylene diamine, hexamethylene diamine, di-ethyltriamine, tri-ethyltetramine, tetra-ethylpentamine, di-propyltriamine, A Aminopropylamine, ethylaminopropylamine, N,N'-dimethylhexamethylenediamine, bis(2-methylaminoethyl)ether, menthanediamine, different Buddha Ketone diamine, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxyspiro(5,5) undecane adduct, bis(4-amino ring Hexyl) methane, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, diaminodiphenylmethane, diaminodiphenylphosphonium, m-xylylenediamine, and the like. These may be used alone or in combination of two or more. Among them, an alkylene polyamine, a polyalkylene polyamine, a poly(phenylene alkylene)polyamine, and a (cycloalkylene)alkylpolyamine are preferred, and a polyalkylene polyamine is preferred. Specific examples thereof include di-ethyltriamine, tri-extension ethyltetramine, tetra-extension ethylpentamine, di-propyltriamine, and the like.

所使用之聚胺類之量並無特別限制，相對於含環氧基之三烷氧基矽烷及/或其水解縮合物中之環氧基1莫耳，較佳為使用1/(聚胺類1分子中之所有氮原子上之氫原子總數)莫耳以上，較佳為1/(聚胺類1分子中之所有氮原子上之氫原子總數)之1.2倍~10倍莫耳之範圍、1.5倍~5倍莫耳或1.8倍~2.5倍莫耳之範圍。於小於1/(聚胺類1分子中之所有氮原子上之氫原子總數)莫耳之情形時，存在硬化不充分、無法獲得較高硬度之膜之情況，於大於1/(聚胺類1分子中之所有氮原子上之氫原子總數)之10倍莫耳之情形時，存在聚胺類殘留而無法形成硬度 充分之薄膜之情況。 The amount of the polyamine to be used is not particularly limited, and it is preferred to use 1/(polyamine) with respect to the epoxy group-containing trialkoxysilane and/or the epoxy group 1 molar thereof in the hydrolysis condensate thereof. The total number of hydrogen atoms on all nitrogen atoms in the class 1 molecule is greater than or equal to 2 moles per mole, preferably 1/(the total number of hydrogen atoms on all nitrogen atoms in the polyamine 1 molecule) 1.5 times to 5 times the molar or 1.8 times to 2.5 times the range of the molar. In the case of less than 1/(the total number of hydrogen atoms on all nitrogen atoms in the polyamine 1 molecule), there is a case where the hardening is insufficient and a film having a higher hardness cannot be obtained, which is greater than 1/(polyamine) When 10 times of the total number of hydrogen atoms on all nitrogen atoms in one molecule), polyamines remain and cannot form hardness. The case of a full film.

(咪唑類) (imidazole)

作為所使用之咪唑類，具體而言，可列舉：咪唑、2-乙基-4-甲基咪唑、2-苯基-4-甲基-5-羥基甲基咪唑等。該等可單獨使用1種或將2種以上混合使用。 Specific examples of the imidazole to be used include imidazole, 2-ethyl-4-methylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole. These may be used alone or in combination of two or more.

所使用之咪唑類之量只要為觸媒量以上則並無特別限制，相對於所使用之三烷氧基矽烷所含之環氧基1莫耳，較佳為0.001~1.0莫耳之範圍，更佳為0.001~0.5莫耳或0.01~0.1莫耳之範圍。 The amount of the imidazole to be used is not particularly limited as long as it is at least the amount of the catalyst, and is preferably in the range of 0.001 to 1.0 mol per mol of the epoxy group contained in the trialkoxysilane to be used. More preferably, it is in the range of 0.001 to 0.5 mol or 0.01 to 0.1 mol.

(酸) (acid)

於製備含環氧基之三烷氧基矽烷之水解縮合物時，較佳為視需要進而使酸共存而進行。 In the case of preparing a hydrolysis-condensation product of an epoxy group-containing trialkoxysilane, it is preferred to carry out the acid coexistence as needed.

作為所使用之酸，可列舉：有機酸、無機酸等，例如作為有機酸，可列舉：乙酸、甲酸、草酸、碳酸、苯二甲酸、三氟乙酸、對甲苯磺酸、甲磺酸等；作為無機酸，可列舉：鹽酸、硝酸、硼酸、氟硼酸等。其中，較佳為使用20℃下之pKa為2.0~6.0之範圍之有機酸。所使用之酸之量並無特別限制，相對於所使用之聚胺類或咪唑類1莫耳，較佳為0.3~1.2莫耳之範圍，更佳為0.5~1.0莫耳或0.6~0.9莫耳之範圍。 Examples of the acid to be used include an organic acid and an inorganic acid. Examples of the organic acid include acetic acid, formic acid, oxalic acid, carbonic acid, phthalic acid, trifluoroacetic acid, p-toluenesulfonic acid, and methanesulfonic acid; Examples of the inorganic acid include hydrochloric acid, nitric acid, boric acid, and fluoroboric acid. Among them, an organic acid having a pKa at 20 ° C in the range of 2.0 to 6.0 is preferably used. The amount of the acid to be used is not particularly limited, and is preferably in the range of 0.3 to 1.2 mol, more preferably 0.5 to 1.0 mol or 0.6 to 0.9 mol, relative to the polyamine or imidazole used. The range of the ear.

於少於0.3莫耳之情形時，存在組合物之保存穩定性下降之情況，於大於1.2莫耳之情形時，存在無法形成硬度充分之薄膜之情況。 In the case of less than 0.3 mol, there is a case where the storage stability of the composition is lowered, and when it is more than 1.2 mol, there is a case where a film having a sufficient hardness cannot be formed.

(有機溶劑) (Organic solvents)

於製備含環氧基之三烷氧基矽烷之水解縮合物時，視需要可使用有機溶劑。作為此種溶劑，只要為可於一定程度上保持溶液之均勻性、穩定性等之溶劑，則並無特別限定，可列舉：醇類、醚類、酮類、酯類、醯胺類等，較佳為碳數1~5之醇。該等可單獨使用1種或 將2種以上併用。碳數1~5之醇可於適當之碳上具有鹵基等取代基，作為此種醇，具體而言，可列舉：全氟乙醇、全氟戊醇等。 In the preparation of the hydrolysis condensate of the epoxy group-containing trialkoxysilane, an organic solvent can be used as needed. The solvent is not particularly limited as long as it can maintain the uniformity and stability of the solution to some extent, and examples thereof include alcohols, ethers, ketones, esters, and guanamines. It is preferably an alcohol having 1 to 5 carbon atoms. These can be used alone or Two or more types are used in combination. The alcohol having 1 to 5 carbon atoms may have a substituent such as a halogen group on a suitable carbon. Specific examples of the alcohol include perfluoroethanol and perfluoropentanol.

該等可單獨使用1種或將2種以上混合使用。於考慮到作業環境、及減少於薄膜中之殘留等之情形時，較佳為碳數1~3之醇，尤佳為異丙醇、正丙醇等。於考慮到水解縮合物之保存穩定性之情形時，較佳為使用正戊醇。 These may be used alone or in combination of two or more. When considering the working environment and reducing the residual in the film, it is preferably an alcohol having 1 to 3 carbon atoms, particularly preferably isopropanol or n-propanol. In the case where the storage stability of the hydrolysis condensate is considered, n-pentanol is preferably used.

作為其他溶劑，較佳為使用水，於該情形時，所使用之有機溶劑較佳為溶於水之有機溶劑。又，水與有機溶劑之比率較佳為於使用各自所需之量之基礎上實現均勻溶液的量比。於使用碳數1~3之醇等相對易於溶於水之有機溶劑之情形時，水與有機溶劑之質量比(水/有機溶劑)較佳為30/70~95/5之範圍，更佳為50/50~90/10、60/40~80/20或65/35~75/25之範圍。 As the other solvent, water is preferably used. In this case, the organic solvent used is preferably an organic solvent soluble in water. Further, the ratio of water to organic solvent is preferably such that the ratio of the homogeneous solution is achieved on the basis of the respective amounts required. When a relatively solvent-soluble organic solvent such as an alcohol having 1 to 3 carbon atoms is used, the mass ratio of water to organic solvent (water/organic solvent) is preferably in the range of 30/70 to 95/5, more preferably It is in the range of 50/50~90/10, 60/40~80/20 or 65/35~75/25.

又，於使用碳數4以上之醇等相對不易溶於水之有機溶劑之情形時，由於有機溶劑於水中之溶解度較低，故而所使用之水之量較佳為含環氧基之三烷氧基矽烷之水解所需之量以上且實現均勻溶液之範圍之量。 Further, in the case of using an organic solvent such as an alcohol having a carbon number of 4 or more and relatively insoluble in water, since the solubility of the organic solvent in water is low, the amount of water used is preferably an epoxy group-containing trioxane. The amount required for the hydrolysis of oxydecane is greater than the amount required to achieve a homogeneous solution.

所使用之溶劑量並無特別限制，考慮到使用包含藉由本發明之製備法所製備之水解縮合物之組合物所形成的薄膜之外觀、該組合物之塗佈性、硬化性、使用該組合物所形成之薄膜之性質、該組合物或水解縮合物之保存穩定性等，較佳為採用反應液中之固形物成分濃度成為1.0~50質量%之範圍之量，更佳為1.0~10質量%或1.0~3.0質量%之範圍。 The amount of the solvent to be used is not particularly limited, and the appearance of the film formed using the composition containing the hydrolysis condensate prepared by the production method of the present invention, the coatability and hardenability of the composition, and the use of the combination are considered. The nature of the film formed by the object, the storage stability of the composition or the hydrolysis condensate, and the like are preferably in the range of 1.0 to 50% by mass, more preferably 1.0 to 10, in the concentration of the solid content component in the reaction liquid. % by mass or in the range of 1.0 to 3.0% by mass.

(製備條件) (preparation conditions)

含環氧基之三烷氧基矽烷之水解縮合物可將含環氧基之三烷氧基矽烷及/或其水解縮合物與水、及聚胺類或咪唑類以及視需要之酸、有機溶劑進行混合、攪拌而製備。其混合順序及攪拌速度並無特 別限定，可設定任意之順序或任意之速度。混合時及攪拌時之溫度並無特別限定，較佳為於室溫至所使用之溶劑之沸點之範圍內進行，更佳為於室溫下進行。所謂室溫，於該情形時係指進行混合攪拌之場所之外部大氣溫度，較佳為15~35℃之範圍之溫度。 The hydrolysis condensate of the epoxy group-containing trialkoxy decane may be an epoxy group-containing trialkoxy decane and/or a hydrolysis condensate thereof and water, and a polyamine or imidazole and, if necessary, an acid or an organic The solvent is prepared by mixing and stirring. The mixing order and stirring speed are not special. Do not limit, you can set any order or any speed. The temperature at the time of mixing and stirring is not particularly limited, but it is preferably carried out at a temperature ranging from room temperature to the boiling point of the solvent to be used, and more preferably at room temperature. The room temperature is, in this case, the external atmospheric temperature at the place where the mixing is performed, preferably in the range of 15 to 35 °C.

較佳為於含環氧基之三烷氧基矽烷、水及聚胺類或咪唑類全體共存之狀態下在室溫下攪拌2小時至3小時。水解後視需要利用有機溶劑或水進行稀釋。 It is preferred to stir at room temperature for 2 hours to 3 hours in a state in which all of the epoxy group-containing trialkoxysilane, water, polyamine or imidazole are present. After the hydrolysis, it is diluted with an organic solvent or water as needed.

包含利用上述製備法所獲得之水解縮合物之組合物之固形物成分濃度並無特別限定，較佳為於1.0~50質量%之範圍內使用，更佳為1.0~10質量%或1.0~3.0質量%之範圍。 The concentration of the solid content component of the composition containing the hydrolysis-condensation product obtained by the above production method is not particularly limited, but is preferably used in the range of 1.0 to 50% by mass, more preferably 1.0 to 10% by mass or 1.0 to 3.0. The range of mass %.

於小於1.0質量%之情形時，存在難以均質地將膜成膜之情況，於大於50質量%之情形時，存在組合物之穩定性、薄膜之透明性、外觀、或塗膜性等出現問題之情況。關於固形物成分濃度，可於最初即調整為特定之固形物成分濃度，亦可以較濃之狀態製備組合物後進行稀釋而調整為特定之固形物成分濃度。 When it is less than 1.0% by mass, there is a case where it is difficult to form a film uniformly, and when it is more than 50% by mass, there are problems such as stability of the composition, transparency of the film, appearance, or coating property. The situation. The concentration of the solid content component can be adjusted to a specific solid content concentration at the beginning, or the composition can be prepared in a relatively concentrated state and then diluted to adjust to a specific solid content concentration.

[製備法2] [Preparation method 2]

於含環氧基之三烷氧基矽烷及/或其水解縮合物中添加水、視需要之矽烷醇縮合觸媒，於5~100℃、較佳為20~60℃下反應1分鐘~10天，較佳為30分鐘~24小時。 To the epoxy group-containing trialkoxy decane and/or its hydrolysis condensate, water, optionally a stanol condensation catalyst, is reacted at 5 to 100 ° C, preferably 20 to 60 ° C for 1 minute to 10 minutes. Days, preferably 30 minutes to 24 hours.

作為原料之含環氧基之三烷氧基矽烷及/或其水解縮合物可使用與製備法1中所示者相同者。又，亦可與製備法1所記載者同樣地使四烷氧基矽烷類、含環氧基之三烷氧基矽烷及/或其水解縮合物以外之三烷氧基矽烷、二烷氧基矽烷、或該等之部分水解縮合物共存而製備。 As the raw material, the epoxy group-containing trialkoxysilane and/or its hydrolysis condensate can be used in the same manner as those shown in Production Method 1. Further, in the same manner as described in the production method 1, a trialkoxy decane or a dialkoxy decane other than the epoxy group-containing trialkoxy decane and/or a hydrolysis condensate thereof may be used. The decane, or a partially hydrolyzed condensate thereof, is prepared by coexistence.

所使用之水之量只要為可使所使用之含環氧基之三烷氧基矽烷及/或其水解縮合物於某種程度上水解縮合之量以上，則並無特別限 制，相對於所使用之含環氧基之三烷氧基矽烷及/或其水解縮合物(其中，於將含環氧基之三烷氧基矽烷及其水解縮合物併用之情形時表示此兩者之合計，又，於併用含環氧基之三烷氧基矽烷以外之烷氧基矽烷之情形時亦表示該等全體之合計)1莫耳，較佳為0.5莫耳以上，更佳為1.0莫耳以上、2.0莫耳以上、5.0莫耳以上或10莫耳以上。 The amount of water to be used is not particularly limited as long as it can liquefy or condense the epoxy group-containing trialkoxysilane and/or its hydrolysis condensate to some extent. And the above-mentioned epoxy group-containing trialkoxy decane and/or its hydrolysis condensate (wherein, when the epoxy group-containing trialkoxy decane and its hydrolysis condensate are used in combination) In the case of a combination of alkoxy decanes other than the epoxy group-containing trialkoxy decane, the total of the total is also 1 mol, preferably 0.5 mol or more, more preferably It is 1.0 mol or more, 2.0 mol or more, 5.0 mol or more, or 10 mol or more.

矽烷醇縮合觸媒可單獨使用1種或將2種以上組合使用。於本發明之組合物中，使用聚胺類或咪唑類作為含環氧基之三烷氧基矽烷之硬化劑或硬化促進劑，因此較佳為亦使用聚胺類、咪唑類作為矽烷醇縮合觸媒。關於聚胺類及咪唑類之詳細說明如上文本發明之製備法1中所述。 The stanol-condensation catalyst may be used alone or in combination of two or more. In the composition of the present invention, a polyamine or an imidazole is used as a hardener or a hardening accelerator for an epoxy group-containing trialkoxysilane. Therefore, it is preferred to use a polyamine or an imidazole as a decanoic alcohol condensation. catalyst. A detailed description of the polyamines and imidazoles is as described in Preparation 1 of the invention of the above text.

所使用之矽烷醇縮合觸媒之量並無特別限制，相對於作為原料之含環氧基之三烷氧基矽烷及/或其水解縮合物中之全部以未縮合進行換算之三烷氧基矽烷基之量，以莫耳比(矽烷醇縮合觸媒/該矽烷基)計，較佳為0.001~1.0之範圍，更佳為0.01~1.0或0.1~0.5之範圍。 The amount of the decyl alcohol condensation catalyst to be used is not particularly limited, and the trialkoxy group is converted to all of the epoxy group-containing trialkoxy decane and/or its hydrolysis condensate as a raw material in terms of uncondensed. The amount of the alkyl group is preferably in the range of 0.001 to 1.0, more preferably 0.01 to 1.0 or 0.1 to 0.5, based on the molar ratio (the stanol condensation catalyst / the alkylene group).

本發明中使用之含環氧基之三烷氧基矽烷之水解縮合物之藉由動態光散射法所測得之z-平均粒徑較佳為5~50nm之範圍，更佳為5~30nm。於大於50nm之情形時，存在使用壽命較短、保存穩定性出現問題之情況，進而存在塗佈後出現塗佈不均之情況。又，於小於5nm之情形時，存在所獲得之薄膜之硬度不充分之情況。 The z-average particle diameter of the hydrolyzed condensate of the epoxy group-containing trialkoxy decane used in the present invention by dynamic light scattering is preferably in the range of 5 to 50 nm, more preferably 5 to 30 nm. . When it is larger than 50 nm, there is a case where the service life is short and the storage stability is problematic, and there is a case where coating unevenness occurs after coating. Further, in the case of less than 5 nm, the hardness of the obtained film may be insufficient.

2)聚胺類 2) Polyamines

作為上述e)所示之聚胺類，可列舉上述製法1中所示之聚胺類。所使用之聚胺類之量如上述製法1中所記載。 Examples of the polyamines represented by the above e) include the polyamines shown in the above Process 1. The amount of the polyamine to be used is as described in the above Process 1.

3)正戊醇 3) n-pentanol

藉由單獨使用或與其他有機溶劑併用正戊醇作為有機溶劑，可提高水解縮合物之保存穩定性。使用量與下述6)之有機矽烷薄膜形成用組合物之製備中所記載之有機溶劑之量相同。 The storage stability of the hydrolysis condensate can be improved by using it alone or in combination with other organic solvents and n-pentanol as an organic solvent. The amount used is the same as the amount of the organic solvent described in the preparation of the composition for forming an organic germane film of the following 6).

4)25℃下之pKa為2.0~6.0之範圍之有機酸 4) Organic acid having a pKa of from 2.0 to 6.0 at 25 ° C

上述f-2)所示之有機酸只要為25℃下之pKa為2.0~6.0之範圍、較佳為3.0~5.0之範圍之有機酸，則並無特別限制。具體而言，可列舉：甲酸、乙酸、丙酸、丁酸、異丁酸、戊酸、異戊酸、己酸、異己酸、氯乙酸、氟乙酸、溴乙酸、3-氯丙酸、2-溴丙酸、2-羥基丁酸、苯基乙酸、苯基丙酸、4-苯基丁酸、苯氧基乙酸、氰基乙酸、草酸、丙二酸、2,2-二甲基丙二酸、己二酸、琥珀酸、庚二酸、苯二甲酸、戊二酸、草醯乙酸、檸檬酸、異檸檬酸、環己烷-1,1-二羧酸、酒石酸、鄰大茴香酸、間大茴香酸、對大茴香酸、苯甲酸、鄰氯苯甲酸、間氟苯甲酸、2,3-二氟苯甲酸、鄰硝基苯甲酸、間硝基苯甲酸、對硝基苯甲酸、間胺基苯甲酸、對胺基苯甲酸、水楊酸、苯二甲酸、間苯二甲酸、反式桂皮酸、2-呋喃羧酸、乙醛酸、乙醇酸、丁烯酸、乳酸、2-羥基-2-甲基丙酸、丙酮酸、苦杏仁酸、蘋果酸、乙醯丙酸、2,6-吡啶二羧酸、煙鹼酸等，其中，較佳為脂肪族單羧酸、或苯甲酸或取代苯甲酸。 The organic acid represented by the above-mentioned f-2) is not particularly limited as long as it has an organic acid having a pKa of from 2.0 to 6.0, preferably from 3.0 to 5.0, at 25 °C. Specific examples thereof include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, caproic acid, isohexanoic acid, chloroacetic acid, fluoroacetic acid, bromoacetic acid, 3-chloropropionic acid, and 2 -Bromopropionic acid, 2-hydroxybutyric acid, phenylacetic acid, phenylpropionic acid, 4-phenylbutyric acid, phenoxyacetic acid, cyanoacetic acid, oxalic acid, malonic acid, 2,2-dimethylpropane Diacid, adipic acid, succinic acid, pimelic acid, phthalic acid, glutaric acid, oxalic acid, citric acid, isocitric acid, cyclohexane-1,1-dicarboxylic acid, tartaric acid, o-anis Acid, meta-anisic acid, anisic acid, benzoic acid, o-chlorobenzoic acid, m-fluorobenzoic acid, 2,3-difluorobenzoic acid, o-nitrobenzoic acid, m-nitrobenzoic acid, p-nitrobenzene Formic acid, m-aminobenzoic acid, p-aminobenzoic acid, salicylic acid, phthalic acid, isophthalic acid, trans cinnamic acid, 2-furancarboxylic acid, glyoxylic acid, glycolic acid, crotonic acid, lactic acid , 2-hydroxy-2-methylpropionic acid, pyruvic acid, mandelic acid, malic acid, acetopropionic acid, 2,6-pyridinedicarboxylic acid, nicotinic acid, etc., among which aliphatic monocarboxylic acid is preferred. Acid, or benzoic acid or substituted Formic acid.

所使用之有機酸之量並無特別限制，相對於所使用之聚胺類1莫耳，較佳為0.3~1.2莫耳之範圍，更佳為0.5~1.0莫耳或0.6~0.9莫耳之範圍。 The amount of the organic acid to be used is not particularly limited, and is preferably in the range of 0.3 to 1.2 mol, more preferably 0.5 to 1.0 mol or 0.6 to 0.9 mol, based on the polyamine 1 mole used. range.

於小於0.3莫耳之情形時，存在有機矽烷薄膜形成用組合物之保存穩定性下降之情況，於大於1.2莫耳之情形時，存在無法形成硬度充分之薄膜之情況。 When the content is less than 0.3 mol, the storage stability of the composition for forming an organic decane film may be lowered. When it is more than 1.2 mol, the film having a sufficient hardness may not be formed.

5)具有全氟烷基或全氟伸烷基之碳數2~5之醇類 5) Alcohols having a carbon number of 2 to 5 having a perfluoroalkyl group or a perfluoroalkylene group

作為上述f-2)所示之具有全氟烷基或全氟伸烷基之碳數2~5之醇類(以下稱為「全氟化醇類」)，具體而言，可列舉：三氟甲醇、2,2,2-三氟乙醇、1,1,2,2,2-五氟乙醇、3,3,3-三氟-1-丙醇、2,2,3,3,3-五氟-1-丙醇、1,1,2,2,3,3,3-七氟-1-丙醇、1,1,1,3,3,3-六氟-2-丙醇、2-三 氟甲基-2-丙醇、2-甲基-1,1,1,3,3,3-六氟-2-丙醇、2,2,3,3,4,4,4-七氟-1-丁醇、九氟-第三丁醇、2,2,3,3,4,4,5,5-八氟-1-戊醇等。 The alcohol having 2 to 5 carbon atoms (hereinafter referred to as "perfluorinated alcohol") having a perfluoroalkyl group or a perfluoroalkyl group as shown in the above-mentioned item f-2), specifically, Fluoromethanol, 2,2,2-trifluoroethanol, 1,1,2,2,2-pentafluoroethanol, 3,3,3-trifluoro-1-propanol, 2,2,3,3,3 - pentafluoro-1-propanol, 1,1,2,2,3,3,3-heptafluoro-1-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol , 2-three Fluoromethyl-2-propanol, 2-methyl-1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,4,4,4-heptafluoro 1-butanol, nonafluoro-t-butanol, 2,2,3,3,4,4,5,5-octafluoro-1-pentanol, and the like.

所使用之全氟化醇類之量並無特別限制，較佳為有機矽烷薄膜形成用組合物整體之30質量%以上，更佳為40質量%以上。於小於30質量%之情形時，存在組合物之長期保存穩定性下降之情況。 The amount of the perfluorinated alcohol to be used is not particularly limited, but is preferably 30% by mass or more, and more preferably 40% by mass or more based on the entire composition of the organic decane film-forming composition. In the case of less than 30% by mass, there is a case where the long-term storage stability of the composition is lowered.

6)有機矽烷薄膜形成用組合物之製備 6) Preparation of composition for forming organic decane film

有機矽烷薄膜形成用組合物可使用以下之方法製備。 The composition for forming an organic germane film can be produced by the following method.

i)將含環氧基之三烷氧基矽烷及/或其水解縮合物、矽烷醇縮合觸媒、水及視需要之有機溶劑於室溫下混合、攪拌，繼而添加聚胺類、視需要之有機酸或全氟化醇類，利用有機溶劑與視需要之水進行稀釋。 i) mixing the epoxy group-containing trialkoxy decane and/or its hydrolysis condensate, stanol condensation catalyst, water and optionally an organic solvent at room temperature, stirring, and then adding polyamines, as needed The organic acid or perfluorinated alcohol is diluted with an organic solvent and water as needed.

ii)將含環氧基之三烷氧基矽烷及/或其水解縮合物、水、有機溶劑、聚胺類於室溫下混合、攪拌，進而視需要添加有機酸或全氟化醇類，進而利用有機溶劑與視需要之水進行稀釋。 Ii) The epoxy group-containing trialkoxy decane and/or its hydrolysis condensate, water, organic solvent, and polyamine are mixed and stirred at room temperature, and an organic acid or a perfluorinated alcohol is added as needed. Further, it is diluted with an organic solvent and water as needed.

iii)將含環氧基之三烷氧基矽烷及/或其水解縮合物、水、作為溶劑之醇、聚胺類、視需要之有機酸或全氟化醇類於室溫下混合、攪拌，進而利用有機溶劑與視需要之水進行稀釋。 Iii) mixing and stirring the epoxy group-containing trialkoxy decane and/or its hydrolysis condensate, water, solvent alcohol, polyamine, optionally organic acid or perfluorinated alcohol at room temperature Further, it is diluted with an organic solvent and water as needed.

iv)將含環氧基之三烷氧基矽烷、水、作為溶劑之醇、聚胺類、視需要之有機酸或全氟化醇類於室溫下混合、攪拌。 Iv) The epoxy group-containing trialkoxy decane, water, a solvent alcohol, a polyamine, an optional organic acid or a perfluorinated alcohol are mixed and stirred at room temperature.

攪拌溫度並無特別限制，較佳為室溫~所使用之溶劑之沸點溫度的範圍，更佳為於室溫下進行。於該情形時，所謂室溫係指進行攪拌之場所之外部大氣溫度，較佳為15~35℃之範圍。 The stirring temperature is not particularly limited, and is preferably from room temperature to the boiling point temperature of the solvent to be used, and more preferably at room temperature. In this case, the room temperature means the outside air temperature at the place where the stirring is performed, and is preferably in the range of 15 to 35 °C.

(有機溶劑) (Organic solvents)

有機矽烷薄膜形成用組合物可使用有機溶劑以調整組合物中之固形物成分濃度。作為此種溶劑，只要為可保持溶液之均勻性、穩定性等之溶劑，則並無特別限定，可列舉：醇類、醚類、酮類、酯類、 醯胺類等，較佳為碳數1~5之醇。該等可單獨使用1種或將2種以上併用。 The composition for forming an organic germane film can use an organic solvent to adjust the concentration of the solid content in the composition. The solvent is not particularly limited as long as it can maintain the uniformity and stability of the solution, and examples thereof include alcohols, ethers, ketones, and esters. The guanamine or the like is preferably an alcohol having 1 to 5 carbon atoms. These may be used alone or in combination of two or more.

作為其他溶劑，較佳為使用水，於該情形時，所使用之有機溶劑較佳為溶於水之有機溶劑。又，水與有機溶劑之比率較佳為於使用各自所需之量之基礎上實現均勻溶液的量比。於使用碳數1~3之醇等相對易於溶於水之有機溶劑之情形時，水與有機溶劑之質量比(水/有機溶劑)較佳為30/70~95/5之範圍，更佳為50/50~90/10、60/40~80/20或65/35~75/25之範圍。 As the other solvent, water is preferably used. In this case, the organic solvent used is preferably an organic solvent soluble in water. Further, the ratio of water to organic solvent is preferably such that the ratio of the homogeneous solution is achieved on the basis of the respective amounts required. When a relatively solvent-soluble organic solvent such as an alcohol having 1 to 3 carbon atoms is used, the mass ratio of water to organic solvent (water/organic solvent) is preferably in the range of 30/70 to 95/5, more preferably It is in the range of 50/50~90/10, 60/40~80/20 or 65/35~75/25.

又，於使用碳數4以上之醇等相對不易溶於水之有機溶劑之情形時，由於有機溶劑於水中之溶解度較低，故而所使用之水之量較佳為三烷氧基矽烷之水解所需之量以上且實現均勻組合物之範圍之量。 Further, in the case where an organic solvent such as an alcohol having 4 or more carbon atoms is relatively insoluble in water, since the solubility of the organic solvent in water is low, the amount of water used is preferably hydrolysis of trialkoxydecane. The amount required is greater than the amount required to achieve a uniform composition.

(調配比率) (mixing ratio)

有機矽烷薄膜形成用組合物中之固形物成分濃度並無特別限制，考慮到薄膜之外觀、塗佈性、硬化性、薄膜之性質、組合物之保存穩定性等，較佳為使用成為0.5~50質量%之範圍之量，更佳為1.0~30質量%、1.0~20質量%、1.0~10質量%、1.5~5.0質量%或1.8~3質量%之範圍。 The concentration of the solid content component in the composition for forming an organic germane film is not particularly limited, and is preferably 0.5 to 0.5 in consideration of the appearance, coatability, hardenability, properties of the film, storage stability of the composition, and the like of the film. The amount in the range of 50% by mass is more preferably in the range of 1.0 to 30% by mass, 1.0 to 20% by mass, 1.0 to 10% by mass, 1.5 to 5.0% by mass or 1.8 to 3% by mass.

於小於0.5質量%之情形時，存在難以均質地成膜之情況，於大於50質量%之情形時，存在組合物之穩定性、薄膜之透明性、外觀、或塗佈性等出現問題之情況。 When it is less than 0.5% by mass, there is a case where it is difficult to form a film uniformly, and when it is more than 50% by mass, there are problems such as stability of the composition, transparency of the film, appearance, or coating property. .

關於所使用之有機溶劑及水之量，可於能夠調整為上述固形物成分濃度之範圍內亦考慮到所併用之全氟化醇類之量而適當決定。 The amount of the organic solvent to be used and the amount of water to be used can be appropriately determined in consideration of the amount of the perfluorinated alcohol to be used in combination with the concentration of the above-mentioned solid content.

(其他調配成分) (other blending ingredients)

可於有機矽烷薄膜形成用組合物中根據其用途添加其他成分，可列舉：膠體狀二氧化矽或膠體狀氧化鋁等無機微粒子、各種界面活性劑、染料、顏料、分散劑、撥水劑、增黏劑、香料、抗菌性成分 等。 The organic decane film-forming composition may be added with other components depending on the use thereof, and examples thereof include inorganic fine particles such as colloidal cerium oxide or colloidal alumina, various surfactants, dyes, pigments, dispersants, and water repellents. Adhesives, fragrances, antibacterial ingredients Wait.

6)有機矽烷薄膜之形成方法 6) Method for forming organic germanium film

本發明之有機矽烷薄膜可藉由於基材表面利用刷毛、噴霧、浸漬、旋轉塗佈、棒式塗佈、凹版印刷等公知之所有塗裝方法塗佈上述有機矽烷薄膜形成用組合物而形成。乾燥可藉由室溫乾燥及/或加熱而進行。具體而言，於20℃~250℃、較佳為20℃~150℃下進行10秒~24小時、較佳為30秒~10小時左右。 The organic decane film of the present invention can be formed by applying the composition for forming an organic decane film to the surface of the substrate by a known coating method such as bristles, spraying, dipping, spin coating, bar coating, or gravure printing. Drying can be carried out by drying and/or heating at room temperature. Specifically, it is carried out at 20 ° C to 250 ° C, preferably at 20 ° C to 150 ° C for 10 seconds to 24 hours, preferably 30 seconds to 10 hours.

所獲得之薄膜之膜厚並無特別限制，較佳為超過10nm且為5μm以下。 The film thickness of the obtained film is not particularly limited, but is preferably more than 10 nm and 5 μm or less.

[有機半導體層] [Organic Semiconductor Layer]

作為構成有機半導體元件之有機半導體層之材料係使用π共軛系材料，例如可使用：聚吡咯、聚(N-取代吡咯)、聚(3-取代吡咯)、聚(3,4-二取代吡咯)等聚吡咯類，聚噻吩、聚(3-取代噻吩)、聚(3,4-二取代噻吩)、蒽二噻吩、聚苯并噻吩等聚噻吩類，聚異苯并噻吩等聚異苯并噻吩類，聚伸噻吩基乙烯等聚伸噻吩基乙烯類，聚(對苯乙炔)等聚(對苯乙炔)類，聚苯胺、聚(N-取代苯胺)、聚(3-取代苯胺)、聚(2,3-取代苯胺)等聚苯胺類，聚乙炔等聚乙炔類，聚二乙炔等聚二乙炔類，聚薁等聚薁類，聚芘等聚芘類，聚咔唑、聚(N-取代咔唑)等聚咔唑類，聚硒吩等聚硒吩類，聚呋喃、聚苯并呋喃等聚呋喃類，聚對苯等聚對苯類，聚吲哚等聚吲哚類，聚嗒等聚嗒類，稠四苯、稠五苯、稠六苯、稠七苯、二苯并稠五苯、四苯并稠五苯、芘、二苯并芘、、苝、蔻、聯三芮、聯十苯、荂(quaterrylene)、循環蒽(circumanthracene)等多并苯類及將多并苯類之一部分碳取代為N、S、O等原子、羰基等官能基所得之衍生物(三苯基二、三苯基二噻、稠六苯-6,15-醌等)，聚乙烯基咔唑、聚苯硫醚、聚乙烯硫醚等聚合物。 As the material constituting the organic semiconductor layer of the organic semiconductor element, a π-conjugated material is used, and for example, polypyrrole, poly(N-substituted pyrrole), poly(3-substituted pyrrole), poly(3,4-disubstituted) can be used. Polypyrroles such as pyrrole), polythiophenes such as polythiophene, poly(3-substituted thiophene), poly(3,4-disubstituted thiophene), quinone dithiophene, polybenzothiophene, polyisobenzothiophene, etc. Benzothiophenes, polythiophene vinyls such as polythiophene ethylene, poly(p-phenylacetylene) such as poly(p-phenylacetylene), polyaniline, poly(N-substituted aniline), poly(3-substituted aniline) Polyaniline such as poly(2,3-substituted aniline), polyacetylene such as polyacetylene, polydiacetylene such as polydiacetylene, polyfluorene such as polyfluorene, polyfluorene such as polyfluorene, polycarbazole, Poly(carbazole) such as poly(N-substituted carbazole), polyselenene such as polyselenophene, polyfuran such as polyfuran and polybenzofuran, polyparaphenylene such as polyparaphenylene, polyfluorene or the like Ape Concentration Classes, condensed tetraphenyl, pentacene, hexabenzene, hexabenzene, dibenzo pentacene, tetrabenzo pentacene, anthracene, dibenzopyrene, , 苝, 蔻, 芮三芮, hexabenzene, quaterrylene, circummanthracene and other polyacenes and some of the polyacenes are substituted with N, S, O and other carbonyl groups. Derivative derivative (triphenyldiene) Triphenyldithiazide , thick hexaphenyl-6,15-fluorene, etc.), polyvinyl carbazole, polyphenylene sulfide, polyethylene sulfide and other polymers.

又，亦可較佳地使用具有與該等聚合物相同之重複單元之例如作為噻吩六聚物之α-六噻吩、α,ω-二己基-α-六噻吩、α,ω-二己基-α-四噻吩、α,ω-雙(3-丁氧基丙基)-α-六噻吩、苯乙烯基苯衍生物等低聚物。 Further, it is also preferred to use α-hexathiophene, α,ω-dihexyl-α-hexathiophene, α,ω-dihexyl as a thiophene hexamer having the same repeating unit as the polymers. Oligomers such as α-tetrathiophene, α,ω-bis(3-butoxypropyl)-α-hexathiophene, and styrylbenzene derivatives.

進而可列舉：酞菁銅等金屬酞菁類；萘四羧酸二醯亞胺類(萘1,4,5,8-四羧酸二醯亞胺，N,N'-雙(4-三氟甲基苄基)萘1,4,5,8-四羧酸二醯亞胺以及N,N'-雙(1H,1H-全氟辛基)、N,N'-雙(1H,1H-全氟丁基)及N,N'-二辛基萘1,4,5,8-四羧酸二醯亞胺衍生物，萘2,3,6,7-四羧酸二醯亞胺等)，及蒽2,3,6,7-四羧酸二醯亞胺等蒽四羧酸二醯亞胺類等縮合環四羧酸二醯亞胺類；C60、C70、C76、C78、C84等富勒烯類；SWNT(Single-wall nanotubes，單壁奈米碳管)等奈米碳管；部花青色素類、半花青素色素類等色素等。 Further, examples thereof include metal phthalocyanines such as copper phthalocyanine; diimine imines of naphthalene tetracarboxylic acid (naphthalene 1,4,5,8-tetracarboxylic acid diimide, N,N'-bis (4-three) Fluoromethylbenzyl)naphthalene 1,4,5,8-tetracarboxylic acid diimine and N,N'-bis(1H,1H-perfluorooctyl), N,N'-bis(1H,1H -perfluorobutyl) and N,N'-dioctylnaphthalene 1,4,5,8-tetracarboxylic acid diimine derivative, naphthalene 2,3,6,7-tetracarboxylic acid diimide Etc., and 蒽2,3,6,7-tetracarboxylic acid diimine and the like condensed cyclic tetracarboxylic acid diterpene imines such as dicarboxylic acid diterpenoids; C60, C70, C76, C78, Fullerene such as C84; carbon nanotubes such as SWNT (Single-wall nanotubes); pigments such as cyanine pigments and hemicyanin pigments.

該等π共軛系材料之中，較佳為選自噻吩、伸乙烯基、伸噻吩基伸乙烯基、伸苯基伸乙烯基、對伸苯基，以該等之取代體或該等之2種以上作為重複單元且該重複單元之數量為4~10之低聚物或者該重複單元之數量為20以上之聚合物，稠五苯等縮合多環芳香族化合物，富勒烯類，縮合環四羧酸二醯亞胺類，金屬酞菁所組成之群中之至少1種。 Among the π-conjugated materials, preferred are selected from the group consisting of thiophene, vinylene, thiophene extended vinyl, phenyl extended vinyl, phenyl extended, substituted with these or the like. The above is a repeating unit and the number of repeating units is 4 to 10 or the number of repeating units is 20 or more, condensed polycyclic aromatic compounds such as fused pentene, fullerene, condensed ring 4 At least one of a group consisting of dicarboxylic acid diamines and metal phthalocyanines.

又，作為其他有機半導體之材料，亦可使用四硫富瓦烯(TTF)-四氰基喹諾二甲烷(TCNQ)錯合物、雙(伸乙基二硫)四硫富瓦烯(BEDTTTF)-過氯酸錯合物、BEDTTTF-碘錯合物、TCNQ-碘錯合物等有機分子錯合物。進而，亦可使用聚矽烷、聚鍺烷等σ共軛系聚合物或碘化苯乙基銨錫等有機-無機混成材料。 Further, as a material of other organic semiconductors, tetrathiafulvalene (TTF)-tetracyanoquinolodimethane (TCNQ) complex, bis(ethylidene disulfide) tetrathiafulvalene (BEDTTTF) can also be used. An organic molecular complex such as a perchloric acid complex, a BEDTTTF-iodine complex, or a TCNQ-iodine complex. Further, an organic-inorganic hybrid material such as a σ-conjugated polymer such as polydecane or polydecane or a phenethyl ammonium iodide may be used.

本發明中，亦可使有機半導體層含有例如如丙烯酸、乙醯胺、具有二甲基胺基、氰基、羧基、硝基等官能基之材料、或苯醌衍生物、四氰基乙烯及四氰基喹諾二甲烷或該等之衍生物等般成為接受電 子之受體之材料，或者例如如具有胺基、三苯基、烷基、羥基、烷氧基、苯基等官能基之材料、苯二胺等取代胺類、蒽、苯并蒽、取代苯并蒽類、芘、取代芘、咔唑及其衍生物、四硫富瓦烯與其衍生物等般成為作為電子供與體之供體之材料而實施所謂摻雜處理。 In the present invention, the organic semiconductor layer may contain, for example, a material such as acrylic acid, acetamide, a functional group having a dimethylamino group, a cyano group, a carboxyl group or a nitro group, or a benzoquinone derivative or tetracyanoethylene. Tetracyanoquinolodimethane or such derivatives are accepted as electricity a material of the acceptor, or, for example, a material having a functional group such as an amine group, a triphenyl group, an alkyl group, a hydroxyl group, an alkoxy group, a phenyl group, a substituted amine such as phenylenediamine, an anthracene, a benzofluorene, or a substituent The so-called doping treatment is carried out as a material of a donor of an electron donor such as benzofluorenes, anthracenes, substituted anthracenes, carbazoles and derivatives thereof, tetrathiafulvalene and derivatives thereof.

上述所謂摻雜意指於該有機半導體層中導入電子授與性分子(受體)或電子供與性分子(供體)作為摻雜劑。因此，經過摻雜之有機半導體層為含有上述縮合多環芳香族化合物與摻雜劑之有機半導體層。作為本發明中使用之摻雜劑，可採用公知者。 The above-mentioned doping means that an electron-accepting molecule (receptor) or an electron-donating molecule (donor) is introduced as a dopant into the organic semiconductor layer. Therefore, the doped organic semiconductor layer is an organic semiconductor layer containing the above condensed polycyclic aromatic compound and a dopant. As the dopant used in the present invention, a known one can be used.

作為該等有機半導體層之製作法，可列舉：真空蒸鍍法、分子束磊晶生長法、離子團束法、低能量離子束法、離子鍍覆法、CVD(Chemical Vapor Deposition，化學氣相沈積)法、濺鍍法、電漿聚合法、電解聚合法、化學聚合法、噴塗法、旋轉塗佈法、刮刀塗佈法、浸漬塗佈法、澆鑄法、輥式塗佈法、棒式塗佈法、模嘴塗佈法或LB(Langmuir-Blodgett，朗繆爾-布洛傑特)法等，可根據材料而使用。其中，就生產性方面而言，較佳為可使用有機半導體之溶液而簡單且精密地形成有機半導體層之旋轉塗佈法、刮刀塗佈法、浸漬塗佈法、輥式塗佈法、棒式塗佈法、模嘴塗佈法或澆鑄法等。更佳為對構成有機半導體層之分子化合物之配向性加以控制之作為特殊澆鑄法之間隙澆鑄(gap cast)法或邊緣澆鑄(edge cast)法。 Examples of the method for producing the organic semiconductor layer include a vacuum vapor deposition method, a molecular beam epitaxy growth method, an ion beam method, a low energy ion beam method, an ion plating method, and a CVD (Chemical Vapor Deposition). Deposition method, sputtering method, plasma polymerization method, electrolytic polymerization method, chemical polymerization method, spray coating method, spin coating method, blade coating method, dip coating method, casting method, roll coating method, rod type A coating method, a die coating method, or an LB (Langmuir-Blodgett) method can be used depending on the material. Among them, in terms of productivity, a spin coating method, a knife coating method, a dip coating method, a roll coating method, and a rod which can form an organic semiconductor layer simply and precisely using a solution of an organic semiconductor are preferable. Coating method, die coating method, casting method, and the like. More preferably, it is a gap cast method or an edge cast method which is a special casting method for controlling the alignment of molecular compounds constituting the organic semiconductor layer.

該等有機半導體層之膜厚並無特別限制，由於在多數情況下所獲得之有機半導體元件之特性於較大程度上取決於有機半導體之活性層之膜厚，故而該膜厚一般而言為1μm以下，尤佳為10~300nm。 The film thickness of the organic semiconductor layers is not particularly limited, and since the characteristics of the organic semiconductor element obtained in many cases depend to a large extent on the film thickness of the active layer of the organic semiconductor, the film thickness is generally 1 μm or less, particularly preferably 10 to 300 nm.

[電極] [electrode]

本發明中，形成源極電極、汲極電極及閘極電極之材料只要為導電性材料則並無特別限定，可使用鉑、金、銀、鎳、鉻、銅、鐵、錫、含銻鉛、鉭、銦、鈀、碲、錸、銥、鋁、釕、鍺、鉬、鎢、氧化 錫銻、氧化銦錫(ITO)、摻氟氧化鋅、鋅、碳、石墨、玻璃石墨、銀漿及碳漿、鋰、鈹、鈉、鎂、鉀、鈣、鈧、鈦、錳、鋯、鎵、鈮、鈉、鈉-鉀合金、鎂、鋰、鋁、鎂/銅混合物、鎂/銀混合物、鎂/鋁混合物、鎂/銦混合物、鋁/氧化鋁混合物、鋰/鋁混合物等。 In the present invention, the material forming the source electrode, the drain electrode, and the gate electrode is not particularly limited as long as it is a conductive material, and platinum, gold, silver, nickel, chromium, copper, iron, tin, and antimony-containing lead can be used. , antimony, indium, palladium, ruthenium, osmium, iridium, aluminum, osmium, iridium, molybdenum, tungsten, oxidation Tin antimony, indium tin oxide (ITO), fluorine-doped zinc oxide, zinc, carbon, graphite, glass graphite, silver paste and carbon paste, lithium, barium, sodium, magnesium, potassium, calcium, barium, titanium, manganese, zirconium, Gallium, bismuth, sodium, sodium-potassium alloys, magnesium, lithium, aluminum, magnesium/copper mixtures, magnesium/silver mixtures, magnesium/aluminum mixtures, magnesium/indium mixtures, aluminum/alumina mixtures, lithium/aluminum mixtures, and the like.

尤佳為鉑、金、銀、銅、鋁、銦、ITO及碳。又，亦可使用藉由摻雜等提高導電率之公知之導電性聚合物，例如導電性聚苯胺、導電性聚吡咯、導電性聚噻吩、聚乙二氧基噻吩與聚苯乙烯磺酸之錯合物等。其中，較佳為於與有機半導體層之接觸面上之電阻較小者。 Especially preferred are platinum, gold, silver, copper, aluminum, indium, ITO and carbon. Further, a known conductive polymer which is improved in conductivity by doping or the like, such as conductive polyaniline, conductive polypyrrole, conductive polythiophene, polyethylenedioxythiophene, and polystyrenesulfonic acid can also be used. Complex and so on. Among them, it is preferred that the electric resistance at the contact surface with the organic semiconductor layer is smaller.

作為電極之形成方法有如下者：採用公知之光微影法或舉離法，將使用蒸鍍或濺鍍等方法以上述材料作為原料所形成之導電性薄膜形成為電極之方法；於鋁或銅等之金屬箔上以熱轉印、噴墨等方式使用抗蝕劑進行蝕刻之方法。進而亦可直接藉由噴墨將導電性聚合物之溶液或分散液、導電性微粒子之分散液圖案化，亦可由導電性薄膜藉由微影或雷射剝蝕等形成。進而亦可使用利用凸版、凹版、平版、網版印刷等印刷法將包含導電性聚合物或導電性微粒子之油墨、導電性漿料等圖案化之方法。 As a method of forming the electrode, a method of forming a conductive thin film formed by using the above material as a raw material by a method such as vapor deposition or sputtering using a known photolithography method or a lift-off method; A method of etching using a resist by thermal transfer, inkjet, or the like on a metal foil such as copper. Further, the solution or the dispersion of the conductive polymer or the dispersion of the conductive fine particles may be directly patterned by inkjet, or may be formed of a conductive film by lithography or laser ablation. Further, a method of patterning an ink containing a conductive polymer or conductive fine particles, a conductive paste, or the like by a printing method such as relief printing, gravure, lithography, or screen printing may be used.

作為上述導電性微粒子之製備方法，可列舉：氣相蒸發法、濺鍍法、金屬蒸氣合成法等物理生成法，或膠體法、共沈澱法等於液相下還原金屬離子而生成導電性微粒子之化學生成法等。將該等導電性微粒子之分散液藉由下述所示之方法等成形為層後，使溶劑乾燥，進而藉由於100~300℃、較佳為150~200℃之範圍內進行熱處理而使導電性微粒子熱融合，藉此形成電極。 Examples of the method for producing the conductive fine particles include a physical production method such as a vapor phase evaporation method, a sputtering method, and a metal vapor synthesis method, or a colloid method or a coprecipitation method, which is equivalent to reducing metal ions in a liquid phase to form conductive fine particles. Chemical production method, etc. The dispersion of the conductive fine particles is formed into a layer by a method described below, and then the solvent is dried, and further heat-treated in a range of 100 to 300 ° C, preferably 150 to 200 ° C to conduct electricity. The fine particles are thermally fused, thereby forming an electrode.

[絕緣體層] [insulator layer]

本發明中，形成絕緣體層之材料只要為絕緣體則可無限定地使用。尤佳為相對介電常數較高之無機氧化物。作為無機氧化物，具體而言，可列舉：氧化矽、氧化鋁、氧化鉭、氧化鈦、氧化錫、氧化 釩、鈦酸鋇鍶、鋯鈦酸鋇、鋯鈦酸鉛、鈦酸鉛鑭、鈦酸鍶、鈦酸鋇、氟化鋇鎂、鈦酸鉍、鈦酸鍶鉍、鉭酸鍶鉍、鉭鈮酸鉍、三氧化釔等。該等之中，更佳為氧化矽、氧化鋁、氧化鉭、氧化鈦。又，亦可使用氮化矽、氮化鋁等無機氮化物。 In the present invention, the material forming the insulator layer can be used without limitation as long as it is an insulator. It is especially preferred to be an inorganic oxide having a relatively high dielectric constant. Specific examples of the inorganic oxide include cerium oxide, aluminum oxide, cerium oxide, titanium oxide, tin oxide, and oxidation. Vanadium, barium titanate, barium zirconate titanate, lead zirconate titanate, lead barium titanate, barium titanate, barium titanate, barium magnesium fluoride, barium titanate, barium titanate, barium strontium titanate, barium Bismuth citrate, antimony trioxide, and the like. Among these, ruthenium oxide, aluminum oxide, ruthenium oxide, and titanium oxide are more preferable. Further, an inorganic nitride such as tantalum nitride or aluminum nitride can also be used.

作為上述絕緣體層之形成方法，可列舉：真空蒸鍍法、分子束磊晶生長法、離子團束法、低能量離子束法、離子鍍覆法、CVD法、濺鍍法、大氣壓電漿法等乾式製程，或噴塗法、旋轉塗佈法、刮刀塗佈法、浸漬塗佈法、澆鑄法、輥式塗佈法、棒式塗佈法、模嘴塗佈法等塗佈方法、印刷或噴墨等圖案化方法等濕式製程，可根據材料而使用。 Examples of the method for forming the insulator layer include a vacuum deposition method, a molecular beam epitaxy growth method, an ion beam method, a low energy ion beam method, an ion plating method, a CVD method, a sputtering method, and an atmospheric piezoelectric slurry method. Dry process, or spray coating method, spin coating method, knife coating method, dip coating method, casting method, roll coating method, bar coating method, die coating method, etc., printing method or A wet process such as a patterning method such as inkjet can be used depending on the material.

濕式製程可使用如下方法：塗佈使無機氧化物之微粒子(視需要使用界面活性劑等分散助劑)分散至任意之有機溶劑或水中而成之液並加以乾燥之方法，或者塗佈氧化物前驅物、例如烷氧化物之溶液並加以乾燥之所謂溶膠凝膠法。該等中較佳為大氣壓電漿法。 The wet process can be carried out by applying a method in which a fine particle of an inorganic oxide (such as a dispersing aid such as a surfactant) is dispersed in a liquid of any organic solvent or water and dried, or by coating. A so-called sol-gel method of a precursor of a substance, such as a solution of an alkoxide, and drying. Among these, the atmospheric piezoelectric slurry method is preferred.

閘極絕緣層較佳為由陽極氧化膜或由該陽極氧化膜與絕緣體層構成。進而，陽極氧化膜較佳為進行封孔處理。此處，陽極氧化膜係藉由利用公知方法對可陽極氧化之金屬進行陽極氧化處理而形成。 The gate insulating layer is preferably composed of an anodized film or an anodized film and an insulator layer. Further, the anodized film is preferably subjected to a plugging treatment. Here, the anodized film is formed by anodizing the anodizable metal by a known method.

作為可進行陽極氧化處理之金屬，可列舉鋁或鉭，陽極氧化處理之方法並無特別限制，可使用公知之方法。藉由進行陽極氧化處理可形成氧化被膜。作為可用於陽極氧化處理之電解液，只要為可形成多孔質氧化被膜者則可為任意，一般而言，可使用硫酸、磷酸、草酸、鉻酸、硼酸、胺基磺酸、苯磺酸等、或將該等2種以上進行組合而成之混酸或該等之鹽。陽極氧化處理之條件根據所使用之電解液而各種變化，因此不可一概而定，一般而言宜為如下範圍：電解液濃度1~80質量%，電解液溫度5~70℃，電流密度0.5~60A/dm2，電壓1~100V、電解時間10秒~5分鐘。較佳之陽極氧化處理係使用硫酸、 磷酸或硼酸之水溶液作為電解液並以直流電流進行處理之方法，亦可使用交流電流。該等酸之濃度較佳為5~45質量%，較佳為以電解液溫度20~50℃、電流密度0.5~20A/dm2進行20~250秒之電解處理。 Examples of the metal which can be anodized include aluminum or ruthenium, and the method of anodizing is not particularly limited, and a known method can be used. An oxidized film can be formed by performing anodizing treatment. The electrolytic solution which can be used for the anodizing treatment may be any one as long as it can form a porous oxide film, and generally, sulfuric acid, phosphoric acid, oxalic acid, chromic acid, boric acid, aminosulfonic acid, benzenesulfonic acid or the like can be used. Or a mixed acid or a salt of these two or more types. The conditions of the anodizing treatment vary depending on the electrolyte to be used, and therefore cannot be determined in general. Generally, the range is as follows: electrolyte concentration: 1 to 80% by mass, electrolyte temperature 5 to 70 ° C, current density 0.5 to 0.5 60A/dm 2 , voltage 1~100V, electrolysis time 10 seconds~5 minutes. The preferred anodizing treatment is a method in which an aqueous solution of sulfuric acid, phosphoric acid or boric acid is used as an electrolytic solution and treated with a direct current, and an alternating current can also be used. The concentration of the acid is preferably from 5 to 45% by mass, preferably from 20 to 250 seconds at an electrolyte temperature of 20 to 50 ° C and a current density of 0.5 to 20 A/dm 2 .

又，作為有機化合物被膜，可使用聚醯亞胺、聚醯胺、聚酯、聚丙烯酸酯、光自由基聚合系之光硬化性樹脂、光陽離子聚合系之光硬化性樹脂、含有丙烯腈成分之共聚物、聚乙烯酚、聚乙烯醇、酚醛清漆樹脂及氰乙基普魯蘭等。 Further, as the organic compound film, polyimide, polyimide, polyester, polyacrylate, photo-radical polymerization-based photocurable resin, photocationic polymerization-based photocurable resin, and acrylonitrile-containing component can be used. Copolymer, polyvinyl phenol, polyvinyl alcohol, novolak resin and cyanoethyl pullulan.

作為有機化合物被膜之形成方法，較佳為上述濕式製程。 As a method of forming the organic compound film, the above wet process is preferred.

可將無機氧化物被膜與有機氧化物被膜積層而併用。又，作為該等絕緣體層之膜厚，一般為100nm~1μm。 The inorganic oxide film and the organic oxide film may be laminated and used in combination. Further, the film thickness of the insulator layers is generally 100 nm to 1 μm.

又，較佳為於閘極絕緣層與有機半導體層之間、或上述樹脂基材與上述有機半導體層之間設置有機單分子膜以提高有機半導體層之載子移動率，作為用以形成有機單分子膜之成分，具體而言，可列舉：十八烷基三氯矽烷、十八烷基三甲氧基矽烷、癸基三氯矽烷、癸基三甲氧基矽烷、β-苯乙基三氯矽烷、β-苯乙基三甲氧基矽烷(β-PTS)、三氯甲基矽氮烷、或烷烴磷酸、烷烴膦酸、烷烴磺酸、烷烴羧酸等。 Further, it is preferable that an organic monomolecular film is provided between the gate insulating layer and the organic semiconductor layer or between the resin substrate and the organic semiconductor layer to increase the carrier mobility of the organic semiconductor layer to form an organic Specific examples of the monomolecular film include octadecyltrichlorodecane, octadecyltrimethoxydecane, decyltrichlorodecane, decyltrimethoxydecane, and β-phenylethyltrichloride. Decane, β-phenethyltrimethoxydecane (β-PTS), trichloromethyl decazane, or alkane phosphoric acid, alkanephosphonic acid, alkane sulfonic acid, alkane carboxylic acid, and the like.

有機單分子膜較佳為自組單分子膜(SAM)。 The organic monomolecular film is preferably a self-assembled monomolecular film (SAM).

[有機半導體元件] [Organic Semiconductor Components]

又，本發明之有機半導體元件可用於例如軟性之片狀顯示裝置(例如電子紙)、液晶顯示元件及電致發光(EL)顯示元件等顯示元件，固有識別符號響應裝置(RFID)，作為有機薄膜電晶體之有機場效電晶體(有機FET)，整流元件，進行開關動作之閘流體、三端雙向可控矽開關及二端交流開關元件等。 Further, the organic semiconductor device of the present invention can be used for, for example, a flexible sheet-like display device (for example, electronic paper), a display element such as a liquid crystal display element and an electroluminescence (EL) display element, and an inherent identification symbol response device (RFID) as an organic The thin film transistor has an airport effect transistor (organic FET), a rectifying element, a gate fluid for switching operation, a three-terminal bidirectional controllable switch, and a two-terminal AC switch element.

以下，基於實施例更具體地說明本發明，但本發明並不受該等實施例之任何限定。 Hereinafter, the present invention will be more specifically described based on examples, but the present invention is not limited by the examples.

[製備例1](有機無機複合薄膜形成用組合物之製備) [Preparation Example 1] (Preparation of composition for forming an organic-inorganic composite film)

將二異丙氧基雙乙醯丙酮鈦(日本曹達股份有限公司製造，T-50，氧化鈦換算固形物成分量：16.5重量%)30.3g溶解於Solmix(註冊商標)AP-7(Japan Alcohol Trading(股份)公司製造)58.4g後，一面攪拌一面緩慢滴加離子交換水11.3g(相對於鈦而為10倍莫耳)而進行水解。1天後過濾溶液，獲得黃色透明之氧化鈦換算濃度5重量%之氧化鈦奈米分散液[A-1]。氧化鈦之平均粒徑為4.1nm且為單分散性。 30.3 g of diisopropoxy acetoacetone titanium (manufactured by Nippon Soda Co., Ltd., T-50, solid content of titanium oxide: 16.5 wt%) was dissolved in Solmix (registered trademark) AP-7 (Japan Alcohol) After 58.4 g of the company (manufactured by Trading Co., Ltd.), 11.3 g of ion-exchanged water (10-fold molar relative to titanium) was slowly added dropwise while stirring to carry out hydrolysis. After 1 day, the solution was filtered to obtain a titanium oxide nanoparticle dispersion [A-1] having a yellow transparent titanium oxide concentration of 5% by weight. The average particle diameter of titanium oxide is 4.1 nm and is monodisperse.

作為有機矽化合物，使用將乙烯基三甲氧基矽烷(信越化學工業股份有限公司製造，KBM-1003)與3-甲基丙烯醯氧基丙基三甲氧基矽烷(信越化學工業股份有限公司製造，KBM-503)以7/3(=乙烯基三甲氧基矽烷/3-甲基丙烯醯氧基丙基三甲氧基矽烷)之莫耳比進行混合所得之液[B-1]。 As the organic ruthenium compound, vinyl trimethoxy decane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-1003) and 3-methacryloxypropyltrimethoxy decane (manufactured by Shin-Etsu Chemical Co., Ltd.) were used. KBM-503) A liquid [B-1] obtained by mixing a molar ratio of 7/3 (=vinyltrimethoxydecane/3-methylpropenyloxypropyltrimethoxydecane).

以元素比(Ti/Si=1/9)之方式將上述[A-1]與[B-1]進行混合，攪拌12小時而製作液[C-1]。[C-1]之固形物成分為29.2重量%。 The above [A-1] and [B-1] were mixed in an element ratio (Ti/Si = 1/9), and stirred for 12 hours to prepare a liquid [C-1]. The solid content of [C-1] was 29.2% by weight.

作為紫外線硬化性化合物，使丙烯酸胺基甲酸酯低聚物(日本合成化學工業股份有限公司製造，紫光UV1700B)以成為40重量%之方式溶解於甲基異丁基酮(MIBK)。於該溶液中以相對於丙烯酸胺基甲酸酯低聚物之固形物成分而成為4重量%之方式溶解作為光聚合起始劑之1-羥基-環己基苯基酮(和光純藥工業股份有限公司製造)，製作溶液[D-1]。 As the ultraviolet curable compound, an urethane urethane oligomer (manufactured by Nippon Synthetic Chemical Co., Ltd., Violet UV 1700B) was dissolved in methyl isobutyl ketone (MIBK) so as to be 40% by weight. Dissolving 1-hydroxy-cyclohexyl phenyl ketone as a photopolymerization initiator in the solution in an amount of 4% by weight based on the solid content of the urethane amide oligomer (Wako Pure Chemical Industries Co., Ltd.) Co., Ltd.), making solution [D-1].

以固形物成分之比率成為10重量%/90重量%=[C-1]/[D-1]之方式將上述[C-1]液與[D-1]溶液進行混合，製作有機無機複合薄膜形成用組合物[E-1]。 The above-mentioned [C-1] liquid and [D-1] solution are mixed so that the ratio of the solid content becomes 10% by weight/90% by weight = [C-1] / [D-1], and an organic-inorganic composite is produced. Film forming composition [E-1].

[製備例2](有機矽烷薄膜形成用組合物之製備) [Preparation Example 2] (Preparation of composition for forming an organic germane film)

將2.0g之3-縮水甘油氧基-正丙基三甲氧基矽烷、0.5g之二伸乙基三胺、0.5g之苯甲酸、70.0g之水及28.0g之異丙醇加以混合後， 於室溫下攪拌2小時，製備以固形物成分之質量濃度換算計3%之有機矽烷薄膜形成用組合物[E-2]。 After mixing 2.0 g of 3-glycidoxy-n-propyltrimethoxydecane, 0.5 g of diethyltriamine, 0.5 g of benzoic acid, 70.0 g of water and 28.0 g of isopropyl alcohol, The mixture was stirred at room temperature for 2 hours to prepare a composition [E-2] for forming an organodecane film in an amount of 3% by mass of the solid content.

[實施例1] [Example 1]

使用微凹版塗佈機(速度4m/min)於聚萘二甲酸乙二酯(PEN)膜(Teijin Dupont Films股份有限公司製造，Teonex Q51DW，厚度100μm)上塗佈製備例1所製備之組合物[E-1]，加以乾燥(溫風乾燥，80℃，約1分鐘)，進行紫外線照射(集光型高壓水銀燈，160W/cm，燈高9.8cm，累計照射量約500mJ/cm2)而獲得膜厚5μm之薄膜。繼而，將形成有薄膜之PEN膜切成2.5×2.5cm2，使用UV臭氧清洗裝置(SEN LIGHTS公司製造)進行10分鐘之UV臭氧清洗，進而浸漬於β-苯乙基三氯矽烷(β-PTS)(信越化學製造之LP-1990)之甲苯稀釋溶液(β-PTS/己烷：10mM)中而於基材表面形成有機單分子膜。 The composition prepared in Preparation Example 1 was coated on a polyethylene naphthalate (PEN) film (manufactured by Teijin Dupont Films Co., Ltd., Teonex Q51DW, thickness: 100 μm) using a micro gravure coater (speed: 4 m/min). [E-1], dried (warm air drying, 80 ° C, about 1 minute), and irradiated with ultraviolet light (concentrated high-pressure mercury lamp, 160 W/cm, lamp height 9.8 cm, cumulative irradiation amount of about 500 mJ/cm 2 ) A film having a film thickness of 5 μm was obtained. Then, the PEN film formed with the film was cut into 2.5×2.5 cm 2 , and subjected to UV ozone cleaning for 10 minutes using a UV ozone cleaning device (manufactured by SEN LIGHTS Co., Ltd.), and further immersed in β-phenethyltrichloromethane (β-). An organic monomolecular film was formed on the surface of the substrate in a toluene dilution solution (β-PTS/hexane: 10 mM) of PTS) (LP-1990 manufactured by Shin-Etsu Chemical Co., Ltd.).

其次，依據本發明者等人所開發之塗佈法(邊緣澆鑄：Appl.Phys.Exp.2,111501(2009))，形成有機半導體層。即，於上述PEN膜上放置溶液保持用之矽碎片(以下亦稱為「溶液保持構造」)。一面使基材傾斜，一面將有機半導體溶液(PI-CRYSTAL公司製造，C10-DNBDT)於120℃下滴於溶液保持構造之邊緣。隨著溶劑之蒸發，結晶一面成長一面貼附於基材，數分鐘內完成結晶成長。以該狀態於減壓下、室溫下放置1小時，進而於減壓下60℃下放置，使有機半導體層完全乾燥(膜厚：10~100nm)。 Next, an organic semiconductor layer was formed in accordance with a coating method (edge casting: Appl. Phys. Exp. 2, 111501 (2009)) developed by the inventors of the present invention. That is, the crucible for holding the solution (hereinafter also referred to as "solution holding structure") is placed on the PEN film. An organic semiconductor solution (manufactured by PI-CRYSTAL Co., Ltd., C10-DNBDT) was dropped on the edge of the solution holding structure at 120 ° C while tilting the substrate. As the solvent evaporates, the crystal grows while adhering to the substrate, and crystal growth is completed in a few minutes. In this state, the mixture was allowed to stand under reduced pressure at room temperature for 1 hour, and further placed under reduced pressure at 60 ° C to completely dry the organic semiconductor layer (film thickness: 10 to 100 nm).

為了於該有機半導體層上製作源極/汲極電極，使用通道(L：1000μm，W：500μm)之蔽蔭遮罩以400Å之厚度蒸鍍金。 In order to fabricate the source/drain electrodes on the organic semiconductor layer, gold was vapor-deposited with a thickness of 400 Å using a mask (L: 1000 μm, W: 500 μm).

將CytopCLT-809M(旭硝子公司製造，CT-solv180，8倍稀釋：氟系溶劑)1mL展開於上述蒸鍍有電極之膜上，以4000rpm歷時20sec進行旋轉塗佈而形成Cytop絕緣體層。進而，使聚對二甲苯絕緣體(第三化成公司製造，diX-SR：對二甲苯系樹脂)於真空加熱(680℃)下進行 氣化聚合而於Cytop絕緣體層上積層聚對二甲苯絕緣體層。利用膜厚計(Alpha-Step500：Tencor公司製造)測定該聚對二甲苯絕緣體層之膜厚，結果為5850Å。 1 mL of Cytop CLT-809M (manufactured by Asahi Glass Co., Ltd., CT-solv 180, 8-fold dilution: fluorine-based solvent) was developed on the electrode on which the electrode was deposited, and spin-coated at 4000 rpm for 20 sec to form a Cytop insulator layer. Further, a parylene insulator (manufactured by Third Chemical Co., Ltd., diX-SR: p-xylene resin) was subjected to vacuum heating (680 ° C). Gasification polymerization to laminate a layer of parylene insulator on the Cytop insulator layer. The film thickness of the parylene insulating layer was measured by a film thickness meter (Alpha-Step 500: manufactured by Tencor Co., Ltd.) and found to be 5,850 Å.

於該絕緣體層上被覆寬200μm之蔽蔭遮罩，使用ULBAC公司製造之真空蒸鍍機「EX-400」(真空度：1.3×10-4Pa)，以700Å之厚度蒸鍍鋁而形成閘極電極，製作頂閘極、頂部接觸型之有機薄膜電晶體。 A mask having a width of 200 μm was coated on the insulator layer, and a vacuum vapor deposition machine "EX-400" (vacuum degree: 1.3 × 10 -4 Pa) manufactured by ULBAC Co., Ltd. was used, and aluminum was vapor-deposited to a thickness of 700 Å to form a gate. The electrode is made of a top gate and a top contact type organic thin film transistor.

對所製作之有機薄膜電晶體使用半導體參數分析儀(型號「keithley 4200」，Keithley Instruments股份有限公司製造)進行載子移動率及開/關比之測定。將其結果示於圖1~圖5。 The prepared organic thin film transistor was measured for carrier mobility and on/off ratio using a semiconductor parameter analyzer (model "keithley 4200", manufactured by Keithley Instruments, Inc.). The results are shown in Figs. 1 to 5 .

使用該有機薄膜電晶體，利用2個樣品測定移動率。 Using this organic thin film transistor, the mobility was measured using two samples.

圖3中顯示測定飽和區域之移動率所得之結果。汲極電壓(VD)係設為-100V，使閘極電壓(VG)於100V~-100V間變化而測定移動率。如圖4之點線所示，於飽和區域內可獲得約2.5cm2/Vs之移動率。 The results obtained by measuring the mobility of the saturated region are shown in FIG. The drain voltage (V D ) was set to -100 V, and the gate voltage (VG) was varied between 100 V and -100 V to measure the mobility. As shown by the dotted line in Fig. 4, a mobility of about 2.5 cm 2 /Vs is obtained in the saturated region.

又，圖1中顯示測定線性區域之移動率所得之結果。汲極電壓(VD)係設為-5V，使閘極電壓(VG)於40V~-100V間變化而測定移動率。如圖2之點線所示，於線性區域內可獲得約0.9cm2/Vs之移動率。 Further, the results obtained by measuring the mobility of the linear region are shown in Fig. 1. The drain voltage (V D ) was set to -5 V, and the gate voltage (VG) was varied between 40 V and -100 V to measure the mobility. As shown by the dotted line in Fig. 2 , a mobility of about 0.9 cm 2 /Vs is obtained in the linear region.

[實施例2] [Embodiment 2]

利用棒式塗佈機No.4於聚醯亞胺(PI)膜(TORAY-DUPONT公司製造，Kapton，膜厚125μm)上塗佈組合物[E-2]後，利用溫風循環乾燥器於100℃下進行10分鐘之加熱硬化，獲得膜厚0.3μm之薄膜。 The composition [E-2] was applied onto a polyimide (PI) film (manufactured by TORAY-DUPONT Co., Ltd., Kapton, film thickness: 125 μm) by a bar coater No. 4, and then subjected to a warm air circulation dryer. The film was heat-hardened at 100 ° C for 10 minutes to obtain a film having a film thickness of 0.3 μm.

以與實施例1相同之方式製作有機薄膜電晶體並以相同之方式測定其特性。將其結果示於圖6~圖10。 An organic thin film transistor was produced in the same manner as in Example 1 and its characteristics were measured in the same manner. The results are shown in Figs. 6 to 10 .

圖8中顯示測定飽和區域之移動率所得之結果。汲極電壓(VD)係設為-100V，使閘極電壓(VG)於100V~-100V間變化而測定移動率。於該實施例中，如圖9中之點線所示，亦於飽和區域內可獲得約2.5cm2/Vs之移動率。 The results obtained by measuring the mobility of the saturated region are shown in FIG. The drain voltage (VD) was set to -100 V, and the gate voltage (VG) was varied between 100 V and -100 V to measure the mobility. In this embodiment, as shown by the dotted line in Fig. 9, a mobility of about 2.5 cm 2 /Vs is also obtained in the saturated region.

Claims (6)

一種有機半導體元件，其係於形成有下述(A)或(B)之薄膜之樹脂基材上設置有有機半導體層者，(A)含有以下之a)及b)之有機無機複合薄膜：a)式(I)所表示之有機矽化合物之至少1種以上之縮合物，RnSiX4-n (I)(式中，R表示碳原子直接鍵結於式中之Si上之有機基，X表示羥基或水解性基；n表示1或2，於n為2時，各R可相同亦可不同，於(4-n)為2以上時，各X可相同亦可不同)b)熱硬化性化合物之硬化物及/或電磁射線硬化性化合物之硬化物；(B)含有以下之d)、e)及f)之有機矽烷薄膜：d)含環氧基之三烷氧基矽烷之水解縮合物，e)聚胺類或咪唑類，f)f-1)正戊醇、或者f-2)25℃下之pKa為2.0~6.0之範圍之有機酸、或具有全氟烷基或全氟伸烷基之碳數2~5之醇類。 An organic semiconductor element which is provided with an organic semiconductor layer on a resin substrate on which a film of the following (A) or (B) is formed, and (A) an organic-inorganic composite film containing the following a) and b): a) at least one or more condensates of the organic hydrazine compound represented by the formula (I), R n SiX 4-n (I) (wherein R represents an organic group in which a carbon atom is directly bonded to Si in the formula X represents a hydroxyl group or a hydrolyzable group; n represents 1 or 2. When n is 2, each R may be the same or different, and when (4-n) is 2 or more, each X may be the same or different) b) a cured product of a thermosetting compound and/or a cured product of an electromagnetic ray curable compound; (B) an organic decane film containing d), e) and f): d) an epoxy group-containing trialkoxy decane a hydrolysis condensate, e) a polyamine or an imidazole, f) f-1) n-pentanol, or f-2) an organic acid having a pKa in the range of 2.0 to 6.0 at 25 ° C, or a perfluoroalkyl group Or a perfluoroalkylene group having 2 to 5 carbon atoms. 如請求項1之有機半導體元件，其中式(I)所表示之有機矽化合物係藉由Fedors之推算法所求出之R之溶解度參數(SP1)較藉由Fedors之推算法所求出之熱硬化性化合物或電磁射線硬化性化合物之溶解度參數(SP2)小1.6以上者。 The organic semiconductor device of claim 1, wherein the organic germanium compound represented by the formula (I) is a solubility parameter (SP1) of R determined by a Fedors algorithm and a heat obtained by a Fedors algorithm. The solubility parameter (SP2) of the curable compound or the electromagnetic ray curable compound is less than 1.6. 如請求項1之有機半導體元件，其中式(I)所表示之有機矽化合物之縮合物為滿足下述數式(1)之量之式(I-1)所表示之有機矽化合物之至少1種以上與式(I-2)所表示之有機矽化合物之至少1種以上的縮合物， R1 nSiX4-n (I-1)(式中，n表示1或2，於n為2時，R1相互可相同亦可不同，R1為碳原子直接鍵結於式中之Si上之有機基，R1中之1個以上表示含乙烯基之烴基；X表示羥基或水解性基，相互可相同亦可不同)R2 nSiX4-n (I-2)(式中，n表示1或2，於n為2時，R2可相同亦可不同，R2表示碳原子直接鍵結於式中之Si上之除含乙烯基之烴基以外之有機基；X表示羥基或水解性基，相互可相同亦可不同)30莫耳%≦{[式(I-1)之化合物]}/{[式(I-1)之化合物]+[式(I-2)之化合物]}×100<100莫耳% (1)。 The organic semiconductor device according to claim 1, wherein the condensate of the organic ruthenium compound represented by the formula (I) is at least one of the organic ruthenium compounds represented by the formula (I-1) satisfying the following formula (1). At least one or more condensates of the above organic hydrazine compound represented by the formula (I-2), R 1 n SiX 4-n (I-1) (wherein n represents 1 or 2, and n is 2 When R 1 is the same or different, R 1 is an organic group in which a carbon atom is directly bonded to Si in the formula, and one or more of R 1 represents a hydrocarbon group containing a vinyl group; and X represents a hydroxyl group or a hydrolyzable group. R 2 n SiX 4-n (I-2) (wherein n represents 1 or 2, and when n is 2, R 2 may be the same or different, and R 2 represents a direct carbon atom. An organic group other than a vinyl group-containing hydrocarbon group bonded to Si in the formula; X represents a hydroxyl group or a hydrolyzable group, which may be the same or different from each other) 30 mol% ≦{[a compound of the formula (I-1) ]}/{[Compound of the formula (I-1)]+[Compound of the formula (I-2)]}×100<100 mol% (1). 如請求項1之有機半導體元件，其中式(I)所表示之有機矽化合物之縮合物為式(I-1)所表示之有機矽化合物之至少1種以上與式(I-2)所表示之有機矽化合物之至少1種以上的縮合物，且滿足數式(2)，R1 nSiX4-n (I-1)(式中，n表示1或2，於n為2時，R1相互可相同亦可不同，R1為碳原子直接鍵結於式中之Si上之有機基，R1中之1個以上表示含乙烯基之烴基；X表示羥基或水解性基，相互可相同亦可不同)R2 nSiX4-n (I-2)(式中，n表示1或2，於n為2時，R2可相同亦可不同，R2表示碳原子直接鍵結於式中之Si上之除含乙烯基之烴基以外之有機基；X表示羥基或水解性基，相互可相同亦可不同)30莫耳%≦{[縮合物中之源自式(I-1)之化合物之單元]}/{[縮合物中之源自式(I-1)之化合物之單元]+[縮合物中之源自式(I-2)之化合物之單元]}×100<100莫耳% (2)。 The organic semiconductor device of claim 1, wherein the condensate of the organic ruthenium compound represented by the formula (I) is at least one of the organic ruthenium compounds represented by the formula (I-1) and represented by the formula (I-2) At least one or more condensates of the organic cerium compound satisfy the formula (2), R 1 n SiX 4-n (I-1) (wherein n represents 1 or 2, and when n is 2, R 1 may be the same or different from each other, R 1 is an organic group in which a carbon atom is directly bonded to Si in the formula, and one or more of R 1 represents a hydrocarbon group containing a vinyl group; and X represents a hydroxyl group or a hydrolyzable group, and mutually R 2 n SiX 4-n (I-2) (wherein n represents 1 or 2, and when n is 2, R 2 may be the same or different, and R 2 represents a carbon atom directly bonded to An organic group other than a vinyl group-containing hydrocarbon group on the Si; X represents a hydroxyl group or a hydrolyzable group, which may be the same or different from each other) 30 mol% ≦ {[The condensate is derived from the formula (I-1) a unit of the compound]}/{[a unit derived from the compound of the formula (I-1) in the condensate] + [a unit derived from the compound of the formula (I-2) in the condensate]}×100< 100 moles % (2). 如請求項1至4中任一項之有機半導體元件，其中於上述樹脂基 材上進而設置有有機單分子膜。 The organic semiconductor device according to any one of claims 1 to 4, wherein the resin group is Further, an organic monomolecular film is provided on the material. 如請求項5之有機半導體元件，其中有機半導體元件為有機薄膜電晶體。 The organic semiconductor device of claim 5, wherein the organic semiconductor device is an organic thin film transistor.
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