TWI491675B - Polyoxometallic compositions containing freejunction groups - Google Patents

Polyoxometallic compositions containing freejunction groups Download PDF

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TWI491675B
TWI491675B TW102114070A TW102114070A TWI491675B TW I491675 B TWI491675 B TW I491675B TW 102114070 A TW102114070 A TW 102114070A TW 102114070 A TW102114070 A TW 102114070A TW I491675 B TWI491675 B TW I491675B
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TW201402700A (en
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Yuka Sasaki
Toru Katsumata
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Asahi Kasei E Materials Corp
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    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups

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Description

含自由交聯基之聚矽氧烷組合物Polyoxane composition containing free crosslinking group

本發明係關於一種含自由交聯基之聚矽氧烷組合物、及使該聚矽氧烷組合物硬化而得之硬化物或透明絕緣膜，上述含自由交聯基之聚矽氧烷組合物係作為較佳地用於顯示裝置中之絕緣材料而較佳地用於半導體裝置中之表面保護膜、層間絕緣膜、α射線遮蔽膜等之形成，及搭載有影像感測器或微機械、或微致動器之半導體裝置等中。The present invention relates to a polyoxoxane composition containing a free crosslinking group, and a cured product or a transparent insulating film obtained by hardening the polyoxyalkylene composition, the above-mentioned polyoxane combination containing a free crosslinking group The substrate is preferably used for forming a surface protective film, an interlayer insulating film, an alpha ray shielding film, or the like in a semiconductor device as an insulating material in a display device, and is equipped with an image sensor or a micromachine. Or a semiconductor device of a microactuator or the like.

於電子零件之絕緣材料以及半導體裝置之表面保護膜、層間絕緣膜及α射線遮蔽膜等用途中，廣泛使用兼具優異之耐熱性、電氣特性及機械特性之聚醯亞胺樹脂。該聚醯亞胺樹脂具有如下特徵：其通常係以感光性聚醯亞胺前驅物組合物之形態提供，且將其塗佈於基材上，實施軟烤，介隔所需之圖案化光罩照射活性光線(曝光)、顯影，並實施熱硬化處理，藉此可容易地形成包含耐熱性聚醯亞胺樹脂之硬化凸紋圖案(例如參照以下之專利文獻1)。Polyurethane resins having excellent heat resistance, electrical properties, and mechanical properties are widely used for applications such as insulating materials for electronic components and surface protective films, interlayer insulating films, and α-ray shielding films for semiconductor devices. The polyimine resin is characterized in that it is usually provided in the form of a photosensitive polyimide intermediate composition, and is applied to a substrate, and soft baked to separate the desired patterned light. The cover is irradiated with active light (exposure), developed, and subjected to a heat hardening treatment, whereby a hardened relief pattern containing a heat-resistant polyimide resin can be easily formed (see, for example, Patent Document 1 below).

另一方面，具有如上所述之優異特性之聚醯亞胺於500nm~400nm附近具有來源於聚醯亞胺環之吸收，故不適於如顯示裝置或光學系材料般之必需高透明性之用途。On the other hand, the polyimine having the excellent characteristics as described above has an absorption derived from a polyimide ring in the vicinity of 500 nm to 400 nm, and thus is not suitable for use as high transparency as a display device or an optical material. .

又，主要自構成要素之材質或結構設計上之理由出發，對可於更低之溫度下進行熱硬化處理之材料之要求提高。然而，於先前之聚醯亞胺樹脂前驅物組合物之情況下，若降低硬化處理溫度，則無法完成熱醯亞胺化，各種硬化膜物性降低，故硬化處理溫度之下限為 300℃左右。Further, the requirements for the material which can be thermally hardened at a lower temperature are mainly increased from the viewpoint of the material or structural design of the constituent elements. However, in the case of the prior polyimine resin precursor composition, if the hardening treatment temperature is lowered, the thermal imidization cannot be completed, and the physical properties of the various cured films are lowered, so the lower limit of the hardening treatment temperature is Around 300 °C.

此外，以下之專利文獻2中揭示有一種可進行低溫硬化之感光性矽氧烷系材料。Further, Patent Document 2 below discloses a photosensitive siloxane-based material which can be cured at a low temperature.

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

[專利文獻1]日本專利特開平6-342211號公報[Patent Document 1] Japanese Patent Laid-Open No. Hei 6-342211

[專利文獻2]國際公開第2010/061744號說明書[Patent Document 2] International Publication No. 2010/061744

於形成顯示裝置或光學材料時，形成有圖案之樹脂係數次暴露於高溫下，且成為最終產品後，受到由周圍環境之變化所致之溫度衝擊，故必需較高之耐龜裂性。然而得知，於使用專利文獻2所揭示之技術之情形時，於必要之厚膜之情況下，關於耐龜裂性尚有改善之餘地。又，於如顯示裝置或光學系材料般之必需高透明性及低溫硬化性之領域中，尚未發現滿足厚膜情況下之耐龜裂性之感光性成膜材料。When a display device or an optical material is formed, the resin coefficient in which the pattern is formed is exposed to a high temperature, and after being a final product, it is subjected to a temperature shock caused by a change in the surrounding environment, so that high crack resistance is required. However, it has been found that in the case of using the technique disclosed in Patent Document 2, there is still room for improvement in crack resistance in the case of a thick film as necessary. Further, in the field of high transparency and low-temperature curability which are required for a display device or an optical material, a photosensitive film-forming material which satisfies the crack resistance in the case of a thick film has not been found.

鑒於該先前技術之現狀，本發明所欲解決之課題在於提供一種含自由交聯基之聚矽氧烷組合物，其可獲得透明性較高、且對由溫度衝擊所致之龜裂的耐性優異之硬化物，並且可進行低溫硬化。In view of the current state of the art, the object of the present invention is to provide a polyoxyalkylene composition containing a free crosslinking group which is capable of obtaining high transparency and resistance to cracking caused by temperature shock. Excellent hardened material and low temperature hardening.

本發明者等人為了解決上述課題而進行了銳意研究並反覆實驗，結果意外地發現，藉由使用特定之含自由交聯基之聚矽氧烷組合物，可解決上述課題，從而完成了本發明。即，本發明如以下所述。The inventors of the present invention have conducted intensive studies and repeated experiments in order to solve the above problems, and as a result, unexpectedly found that the above problems can be solved by using a specific polyoxyalkylene composition containing a free crosslinking group, thereby completing the present invention. invention. That is, the present invention is as follows.

[1]一種含自由交聯基之聚矽氧烷組合物，其於大氣下、24℃、常壓及遮蔽波長為400nm以下之光的條件下靜置24小時後，使用電子自旋共振(ESR，electron spin resonance)裝置進行測定時，具有g值為2.034~1.984之波峰，且相對於組合物中之總固形物成分100質量份， 含有0.1×10-6 mol/g~120×10-6 mol/g之自由基。[1] A polyoxane composition containing a free crosslinking group, which is subjected to electron spin resonance after standing at 24 ° C, atmospheric pressure, and shielding light having a wavelength of 400 nm or less for 24 hours. The ESR (electron spin resonance) device has a peak with a g value of 2.034 to 1.984, and contains 0.1×10 -6 mol/g to 120×10 - relative to 100 parts by mass of the total solid content in the composition . 6 mol/g of free radicals.

[2]如上述[1]之含自由交聯基之聚矽氧烷組合物，其具有下述結構： [2] The polyoxyalkylene composition containing a free crosslinking group according to the above [1], which has the following structure:

{式中，R1 、R2 、R3 及R4 分別獨立地表示氫原子及/或碳數1~10之一價有機基，而且R1 與R2 、或R3 與R4 可相互鍵結而形成環結構}。In the formula, R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom and/or a monovalent organic group having 1 to 10 carbon atoms, and R 1 and R 2 or R 3 and R 4 may mutually Bonding to form a ring structure}.

[3]如上述[1]或[2]之含自由交聯基之聚矽氧烷組合物，其進而含有鹼可溶性基。[3] The polyoxosiloxane composition containing a free crosslinking group according to [1] or [2] above, which further contains an alkali-soluble group.

一種聚矽氧烷組合物，其進而含有(B)光自由基起始劑。A polyoxyalkylene composition further comprising (B) a photoradical initiator.

[5]如上述[4]之聚矽氧烷組合物，其中相對於上述聚矽氧烷組合物中之總固形物成分100質量份，含有(A)1質量份~99質量份之含自由交聯基之聚矽氧烷、0.01質量份~15質量份之(B)光自由基起始劑及0.005質量份~2質量份之(C)硝醯基化合物。[5] The polyoxyalkylene composition according to the above [4], which contains (A) 1 part by mass to 99 parts by mass, based on 100 parts by mass of the total solid content of the polyoxyalkylene composition. The crosslinked polyoxyalkylene, 0.01 parts by mass to 15 parts by mass of the (B) photoradical initiator, and 0.005 parts by mass to 2 parts by mass of the (C) nitroguanidine compound.

[6]如上述[5]之聚矽氧烷組合物，其中上述(C)硝醯基化合物係由下述通式表示： [6] The polyoxyalkylene composition according to the above [5], wherein the above (C) nitrate-based compound is represented by the following formula:

{式中，R5 表示氫原子、碳數1~12之烷基、羥基、胺基、羧酸 基、氰基、雜原子取代烷基，或者經由醚、酯、醯胺或胺基甲酸酯鍵而鍵結之一價有機基，R6 表示二或三價有機基，n1 及m1 為滿足1≦n1 +m1 ≦2之整數，n2 及m2 為滿足1≦n2 +m2 ≦2之整數，n3 及m3 為滿足1≦n3 +m3 ≦2之整數，而且1為2或3之整數}。In the formula, R 5 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a hydroxyl group, an amine group, a carboxylic acid group, a cyano group, a hetero atom-substituted alkyl group, or an ether, an ester, a guanamine or an aminocarboxylic acid. The ester bond is bonded to a monovalent organic group, R 6 represents a divalent or trivalent organic group, n 1 and m 1 are integers satisfying 1≦n 1 +m 1 ≦2, and n 2 and m 2 are satisfying 1≦n An integer of 2 + m 2 ≦ 2, n 3 and m 3 are integers satisfying 1 ≦ n 3 + m 3 ≦ 2, and 1 is an integer of 2 or 3.

[7]如上述[1]至[6]中任一項之聚矽氧烷組合物，其中上述(A)含自由交聯基之聚矽氧烷係含有(甲基)丙烯醯基及/或苯乙烯基之聚矽氧烷。[A] The polyoxyalkylene composition according to any one of the above [1] to [6] wherein the (A) polyoxyalkylene containing a free crosslinking group contains (meth) acrylonitrile and/or Or a styryl polyoxyalkylene.

[8]如上述[1]至[7]中任一項之聚矽氧烷組合物，其中相對於上述聚矽氧烷組合物中之總固形物成分100質量份，進而含有5質量份~45質量份之(D)具有光聚合性雙鍵之化合物。[8] The polyoxyalkylene composition according to any one of the above [1] to [7] wherein the total solid content in the polyoxyalkylene composition is 100 parts by mass, and further contains 5 parts by mass. 45 parts by mass of (D) a compound having a photopolymerizable double bond.

[9]如上述[1]至[8]中任一項之聚矽氧烷組合物，其中相對於上述聚矽氧烷組合物中之總固形物成分100質量份，進而含有0.01質量份~10質量份之(E)紫外線吸收劑。[9] The polyoxyalkylene composition according to any one of the above [1] to [8] wherein, in addition to 100 parts by mass of the total solid content in the polyoxyalkylene composition, 0.01 parts by mass is further contained. 10 parts by mass of (E) ultraviolet absorber.

[10]如上述[1]至[9]中任一項之聚矽氧烷組合物，其中相對於上述聚矽氧烷組合物中之總固形物成分100質量份，進而含有1質量份~50質量份之(F)酸值為10~200mgKOH/g之鹼可溶性樹脂。[10] The polyoxyalkylene composition according to any one of the above [1] to [9] wherein the total solid content in the polyoxyalkylene composition is 100 parts by mass, and further contains 1 part by mass. 50 parts by mass of the (F) alkali-soluble resin having an acid value of 10 to 200 mgKOH/g.

[11]如上述[1]至[10]中任一項之聚矽氧烷組合物，其中上述(A)含自由交聯基之聚矽氧烷具有下述通式所表示之結構： [11] The polyoxyalkylene composition according to any one of the above [1] to [10] wherein the (A) polyfluorene oxide having a free crosslinking group has a structure represented by the following formula:

{式中，Ph表示苯基}。In the formula, Ph represents a phenyl group}.

[12]一種硬化物，其係使如上述[1]至[11]中任一項之聚矽氧烷組合物硬化而得。[12] A cured product obtained by hardening the polyoxyalkylene composition according to any one of the above [1] to [11].

[13]一種透明絕緣膜，其係使如上述[1]至[11]中任一項之聚矽氧烷組合物硬化而得。[13] A transparent insulating film obtained by hardening the polyoxyalkylene composition according to any one of the above [1] to [11].

[14]一種含自由交聯基之聚矽氧烷組合物，其具有下述結構： [14] A polyoxyalkylene composition containing a free crosslinking group having the following structure:

{式中，R1 、R2 、R3 及R4 分別獨立地表示氫原子及/或碳數1~10之一價有機基，並且R1 與R2 、或R3 與R4 可相互鍵結而形成環結構}。Wherein R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom and/or a monovalent organic group having 1 to 10 carbon atoms, and R 1 and R 2 or R 3 and R 4 may mutually Bonding to form a ring structure}.

[15]如上述[14]之含自由交聯基之聚矽氧烷組合物，其進而含有鹼可溶性基。[15] The polyoxosiloxane composition containing a free crosslinking group according to [14] above, which further contains an alkali-soluble group.

[16]一種聚矽氧烷組合物，其進而含有(B)光自由基起始劑。[16] A polyoxyalkylene composition further comprising (B) a photoradical initiator.

[17]如上述[16]之聚矽氧烷組合物，其中相對於上述聚矽氧烷組合物中之總固形物成分100質量份，含有1質量份~99質量份之(A)含自由交聯基之聚矽氧烷、0.01質量份~15質量份之(B)光自由基起始劑及0.005質量份~2質量份之(C)硝醯基化合物。[17] The polyoxyalkylene composition according to the above [16], wherein the (A) content is contained in an amount of from 1 part by mass to 99 parts by mass per 100 parts by mass of the total solid content of the polyoxoxane composition. The crosslinked polyoxyalkylene, 0.01 parts by mass to 15 parts by mass of the (B) photoradical initiator, and 0.005 parts by mass to 2 parts by mass of the (C) nitroguanidine compound.

[18]如上述[17]之聚矽氧烷脂組合物，其中上述(C)硝醯基化合物係由下述通式表示： [18] The polyoxyalkylene ester composition according to [17] above, wherein the (C) nitrate compound is represented by the following formula:

{式中，R5 表示氫原子、碳數1~12之烷基、羥基、胺基、羧酸基、氰基、雜原子取代烷基，或者經由醚、酯、醯胺或胺基甲酸酯鍵而鍵結之一價有機基，R6 表示二或三價有機基，n1 及m1 為滿足1≦n1 +m1 ≦2之整數，n2 及m2 為滿足1≦n2 +m2 ≦2之整數，n3 及m3 為滿足1≦n3 +m3 ≦2之整數，而且1為2或3之整數}。In the formula, R 5 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a hydroxyl group, an amine group, a carboxylic acid group, a cyano group, a hetero atom-substituted alkyl group, or an ether, an ester, a guanamine or an aminocarboxylic acid. The ester bond is bonded to a monovalent organic group, R 6 represents a divalent or trivalent organic group, n 1 and m 1 are integers satisfying 1≦n 1 +m 1 ≦2, and n 2 and m 2 are satisfying 1≦n An integer of 2 + m 2 ≦ 2, n 3 and m 3 are integers satisfying 1 ≦ n 3 + m 3 ≦ 2, and 1 is an integer of 2 or 3.

[19]如上述[14]至[18]中任一項之聚矽氧烷組合物，其中上述(A)含自由交聯基之聚矽氧烷係含有(甲基)丙烯醯基及/或苯乙烯基之聚矽氧烷。[19] The polyoxyalkylene composition according to any one of [14] to [18] wherein the (A) polyoxyalkylene containing a free crosslinking group contains (meth) acrylonitrile and/or Or a styryl polyoxyalkylene.

[20]如上述[14]至[19]中任一項之聚矽氧烷脂組合物，其中相對於上述聚矽氧烷組合物中之總固形物成分100質量份，進而含有5質量份~45質量份之(D)具有光聚合性雙鍵之化合物。[20] The polyoxyalkylene oxide composition according to any one of the above [14], wherein the total solid content in the polyoxyalkylene composition is 100 parts by mass, and further contains 5 parts by mass. ~45 parts by mass of (D) a compound having a photopolymerizable double bond.

[21]如上述[14]至[20]中任一項之聚矽氧烷組合物，其中相對於上述聚矽氧烷組合物中之總固形物成分100質量份，進而含有0.01質量份~10質量份之(E)紫外線吸收劑。[21] The polyoxyalkylene composition according to any one of the above [14] to [20] wherein, in addition to 100 parts by mass of the total solid content in the polyoxyalkylene composition, 0.01 parts by mass is further contained. 10 parts by mass of (E) ultraviolet absorber.

[22]如上述[14]至[21]中任一項之聚矽氧烷組合物，其中相對於上述聚矽氧烷組合物中之總固形物成分100質量份，進而含有1質量份~50質量份之(F)酸值為10~200mgKOH/g之鹼可溶性樹脂。[22] The polyoxyalkylene composition according to any one of [14] to [21] wherein the total solid content in the polyoxyalkylene composition is 100 parts by mass, and further contains 1 part by mass. 50 parts by mass of the (F) alkali-soluble resin having an acid value of 10 to 200 mgKOH/g.

[23]如上述[14]至[22]中任一項之聚矽氧烷組合物，其中上述(A)含自由交聯基之聚矽氧烷具有下述通式所表示之結構： [23] The polyoxyalkylene composition according to any one of [14] to [22] wherein the (A) polyfluorene oxide having a free crosslinking group has a structure represented by the following formula:

{式中，Ph表示苯基}。In the formula, Ph represents a phenyl group}.

[24]一種硬化物，其係使如上述[14]至[22]中任一項之聚矽氧烷 組合物硬化而得。[24] A cured product obtained by the polyoxyalkylene of any one of the above [14] to [22] The composition is obtained by hardening.

[25]一種透明絕緣膜，其係使如上述[14]至[22]中任一項之聚矽氧烷組合物硬化而得。[25] A transparent insulating film obtained by hardening the polyoxyalkylene composition according to any one of [14] to [22] above.

根據本發明，提供一種含自由交聯基之聚矽氧烷組合物，其可獲得透明性較高、且對由溫度衝擊所致之龜裂的耐性優異之硬化物，並且可進行低溫硬化。According to the present invention, there is provided a polyoxyalkylene composition containing a free crosslinking group, which can obtain a cured product having high transparency and excellent resistance to cracks caused by temperature shock, and can be cured at a low temperature.

圖1係丙酮之電子自旋共振(ESR)測定結果。Figure 1 shows the results of electron spin resonance (ESR) measurement of acetone.

圖2係4-羥基-TEMPO之ESR測定結果。Figure 2 shows the results of ESR measurement of 4-hydroxy-TEMPO.

圖3係對ESR中之g值之計算方法加以說明的圖。Fig. 3 is a diagram for explaining a method of calculating the g value in the ESR.

圖4係實施例1~8、12~27及比較例5之樹脂組合物之ESR測定結果。Fig. 4 shows the results of ESR measurement of the resin compositions of Examples 1 to 8, 12 to 27 and Comparative Example 5.

圖5係實施例19之聚矽氧烷組合物之ESR測定結果。Figure 5 is a graph showing the results of ESR measurement of the polyoxyalkylene composition of Example 19.

圖6係實施例10之聚矽氧烷組合物之ESR測定結果。Figure 6 is a graph showing the results of ESR measurement of the polyoxyalkylene composition of Example 10.

圖7係實施例11之聚矽氧烷組合物之ESR測定結果。Figure 7 is a graph showing the results of ESR measurement of the polyoxyalkylene composition of Example 11.

圖8係實施例12之聚矽氧烷組合物之ESR測定結果。Figure 8 is a graph showing the results of ESR measurement of the polyoxyalkylene composition of Example 12.

圖9係比較例1~3之樹脂組合物之ESR測定結果。Fig. 9 shows the results of ESR measurement of the resin compositions of Comparative Examples 1 to 3.

圖10係比較例4之樹脂組合物之ESR測定結果。Fig. 10 shows the results of ESR measurement of the resin composition of Comparative Example 4.

以下，對用以實施本發明之形態(以下簡稱為「實施形態」)進行詳細說明。再者，本發明不限定於實施形態，可於其主旨之範圍內加以各種變形而實施。Hereinafter, the form for carrying out the invention (hereinafter simply referred to as "embodiment") will be described in detail. The present invention is not limited to the embodiments, and various modifications can be made without departing from the spirit and scope of the invention.

<含自由交聯基之聚矽氧烷組合物><Polyoxane composition containing free crosslinking group>

具體而言，本實施形態之含自由交聯基之聚矽氧烷組合物包含以下成分： (A)含自由交聯基之聚矽氧烷、及(B)光自由基起始劑，且視需要而包含其他成分。Specifically, the polyfluorene oxide composition containing a free crosslinking group of the present embodiment contains the following components: (A) a polyoxyalkylene containing a free crosslinking group, and (B) a photoradical initiator, and containing other components as needed.

如以下將說明般，上述(A)含自由交聯基之聚矽氧烷可為包含含自由交聯基之聚矽氧烷與(C)硝醯基化合物者。As described below, the above (A) polyfluorene oxide containing a free crosslinking group may be a polysiloxane containing a free crosslinking group and (C) a cerium-based compound.

以下，對藉由使含自由交聯基之聚矽氧烷組合物硬化而得之硬化物等加以說明。Hereinafter, a cured product obtained by curing a polyoxyalkylene composition containing a free crosslinking group will be described.

其中，於本實施形態中，硝醯基化合物係提供以下自由基結構者之例示，本發明無意限定於此，上述自由基結構係於大氣下、24℃、常壓及遮蔽波長為400nm以下之光的條件下靜置24小時後，使用電子自旋共振(ESR)裝置進行測定時，具有g值為2.034~1.984之波峰。In the present embodiment, the nitroxide-based compound is exemplified by the following radical structure, and the present invention is not intended to be limited thereto. The radical structure is in the atmosphere, at 24 ° C, at normal pressure, and at a shielding wavelength of 400 nm or less. After standing for 24 hours under light conditions, the measurement was carried out using an electron spin resonance (ESR) apparatus, and had a peak having a g value of 2.034 to 1.984.

即，於以下將說明之(A)含自由交聯基之聚矽氧烷、與例如作為(C)成分之硝醯基化合物共存之狀態下將該等加熱之情形時，該聚矽氧烷(A)成分與該(C)成分之一部分鍵結，此時存在以下物質之混合狀態：含自由交聯基之聚矽氧烷單體；於大氣下、24℃、常壓及遮蔽波長為400nm以下之光的條件下靜置24小時後，使用電子自旋共振(ESR)裝置進行測定時，具有g值為2.034~1.984之波峰之自由基；以及該聚矽氧烷與自由基鍵結而成者。本發明中，將該混合狀態表述為「於大氣下、24℃、常壓及遮蔽波長為400nm以下之光的條件下靜置24小時後，使用電子自旋共振(ESR)裝置進行測定時，具有g值為2.034~1.984之波峰的含自由交聯基之聚矽氧烷組合物」。或者，含自由交聯基之聚矽氧烷可進而含有如下基，該基產生於大氣下、24℃、常壓及遮蔽波長為400nm以下之光的條件下靜置24小時後，使用電子自旋共振(ESR)裝置進行測定時，具有g值2.034~1.984之波峰的自由基。於該情形時，聚矽氧烷單體具有上述特定之波峰。即，所謂「於 大氣下、24℃、常壓及遮蔽波長為400nm以下之光的條件下靜置24小時後，使用電子自旋共振(ESR)裝置進行測定時，具有g值為2.034~1.984之波峰的含自由交聯基之聚矽氧烷組合物」，包含以下兩種情況：含自由交聯基之聚矽氧烷單體含有上述自由基產生基之情況；與含自由交聯基之聚矽氧烷單體不含上述自由基產生基，但例如與硝醯基化合物共存時產生之聚矽氧烷單體、自由基及該等鍵結而成者之混合狀態之情況。That is, in the case where (A) a polyoxyalkylene containing a free crosslinking group is used in the presence of, for example, a cerium-based compound as a component (C), the polyoxyalkylene is heated. The component (A) is partially bonded to one of the components (C), and a mixed state of the following materials is present: a polyoxyalkylene monomer containing a free crosslinking group; under atmospheric pressure, 24 ° C, atmospheric pressure, and shielding wavelength are After standing for 24 hours under light of 400 nm or less, the radical having a peak of g of 2.034 to 1.984 is measured by an electron spin resonance (ESR) apparatus; and the polysiloxane is bonded to a radical. Founder. In the present invention, the mixed state is expressed as "after standing for 24 hours under conditions of atmospheric light, 24 ° C, normal pressure, and light having a shielding wavelength of 400 nm or less, and then measured by an electron spin resonance (ESR) device. A polyoxane composition containing a free crosslinking group having a g value of from 2.034 to 1.984. Alternatively, the polyoxyalkylene containing a free crosslinking group may further contain a group which is allowed to stand under the atmosphere, at 24 ° C, at a normal pressure, and under a light having a shielding wavelength of 400 nm or less for 24 hours, using electrons. When measured by a cyclone resonance (ESR) device, it has a radical with a peak of g value of 2.034 to 1.984. In this case, the polyoxyalkylene monomer has the above specific peak. That is, In the atmosphere, 24 ° C, normal pressure, and shielding light having a wavelength of 400 nm or less, after standing for 24 hours, when measured by an electron spin resonance (ESR) device, the freeness of the peak having a g value of 2.034 to 1.984 a crosslinked polyoxyalkylene composition, comprising the following two cases: a polyoxyalkylene monomer containing a free crosslinking group containing the above radical generating group; and a polyoxyalkylene containing a free crosslinking group The monomer does not contain the above-mentioned radical generating group, but may be, for example, a mixed state of a polyoxyalkylene monomer, a radical, and a bond which are generated when the nitroxide compound is present.

再者，同樣地，所謂「上述含自由交聯基之聚矽氧烷組合物進而含有鹼可溶性基」，包含以下兩種情況：該聚矽氧烷本身含有鹼可溶性基之情況；與該含有聚矽氧烷之組合物含有鹼可溶性樹脂，結果該聚矽氧烷組合物含有鹼可溶性基之情況。In the same manner, the "polyoxane group containing a free crosslinking group further contains an alkali-soluble group" includes the following two cases: the polyoxyalkylene itself contains an alkali-soluble group; The composition of polyoxyalkylene contains an alkali-soluble resin, and as a result, the polyoxyalkylene composition contains an alkali-soluble group.

<自由基含量><free radical content>

為了於本實施形態中獲得對由溫度衝擊所致之龜裂的耐性優異之硬化物，較佳為相對於組合物中之固形物成分1g，含有0.1×10-6 莫耳以上之如下自由基，該自由基於大氣下、24℃、常壓及遮蔽波長為400nm以下之光的條件下靜置24小時後，使用電子自旋共振(ESR)裝置進行測定時，具有g值為2.034~1.984之波峰，上述自由基進而佳為0.15×10-6 莫耳以上。另一方面，就圖案形成之觀點而言，較佳為120×10-6 莫耳以下，進而佳為60×10-6 莫耳以下。In order to obtain a cured product excellent in resistance to cracks due to temperature shock in the present embodiment, it is preferred to contain 0.1 × 10 -6 mol or more of the following free radicals relative to 1 g of the solid content component in the composition. The freeness is determined by using an electron spin resonance (ESR) device after standing for 24 hours under conditions of 24 ° C, normal pressure, and light having a shielding wavelength of 400 nm or less, and having a g value of 2.034 to 1.984. In the peak, the above radical is further preferably 0.15 × 10 -6 mol or more. On the other hand, from the viewpoint of pattern formation, it is preferably 120 × 10 -6 mTorr or less, and more preferably 60 × 10 -6 mol or less.

含自由交聯基之聚矽氧烷組合物中之總固形物成分量例如可使用TGA(thermogravimetric analyzer，熱重測定裝置)進行測定。The total solid content of the polyoxane composition containing a free crosslinking group can be measured, for example, using a TGA (thermogravimetric analyzer).

自由基量可使用ESR(電子自旋共振裝置)進行測定。可將4-羥基-TEMPO(4-羥基-2,2,6,6-四甲基哌啶-1-氧自由基)作為每1莫耳含有1莫耳自由基之標準品，製作校準曲線，由此測定組合物中之自由基量，並與由TGA測定之固形物成分量合併，藉此算出組合物中之固形物成分每1g中所含之自由基含量。The amount of radicals can be measured using an ESR (electron spin resonance device). 4-hydroxy-TEMPO (4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl radical) can be used as a standard for 1 mole of 1 mole of free radicals. Thus, the amount of radicals in the composition was measured and combined with the amount of the solid component measured by TGA, thereby calculating the amount of radicals contained per 1 g of the solid content in the composition.

再者，於以下將所說明，本實施態樣之聚矽氧烷組合物中，硝醯基化合物0.0017質量份相當於自由基量0.1×10-6 mol/g，硝醯基化合物0.005質量份相當於自由基量0.29×10-6 mol/g，硝醯基化合物0.009質量份相當於自由基量0.523×10-6 mol/g，硝醯基化合物1質量份相當於自由基量58×10-6 mol/g，且硝醯基化合物2質量份相當於自由基量116×10-6 mol/g。Further, as will be described below, in the polyoxyalkylene composition of the present embodiment, 0.0017 parts by mass of the nitroxide compound corresponds to a radical amount of 0.1 × 10 -6 mol/g, and a nitroxide compound of 0.005 parts by mass. Corresponding to the amount of free radicals 0.29×10 -6 mol/g, 0.009 parts by mass of nitroxide-based compound corresponds to the amount of radicals 0.523×10 -6 mol/g, and 1 part by mass of nitroxide-based compound corresponds to the amount of free radicals 58×10 -6 mol/g, and 2 parts by mass of the nitrate-based compound correspond to a radical amount of 116×10 -6 mol/g.

<(A)含自由交聯基之聚矽氧烷><(A) Polyoxane containing free crosslinking group>

(A)含自由交聯基之聚矽氧烷含有可於聚矽氧烷中藉由自由基而交聯之基，可飛躍性地提高硬化膜之硬度。(A) The polyoxyalkylene containing a free crosslinking group contains a group which can be crosslinked by a radical in a polyoxyalkylene, and the hardness of the cured film can be dramatically improved.

自由交聯基可為含有光聚合性不飽和鍵(例如雙鍵)之基。作為含有光聚合性不飽和鍵之基，並無特別限制，例如就交聯性之觀點而言，較佳為乙烯基、苯乙烯基、(甲基)丙烯醯基等。(A)含自由交聯基之聚矽氧烷可含有兩種以上之該等基。又，作為(A)含自由交聯基之聚矽氧烷，就硬化性之觀點而言，更佳為至少含有(甲基)丙烯醯基及/或苯乙烯基。The free crosslinking group may be a group containing a photopolymerizable unsaturated bond such as a double bond. The group containing a photopolymerizable unsaturated bond is not particularly limited. For example, from the viewpoint of crosslinkability, a vinyl group, a styryl group, a (meth) acrylonitrile group or the like is preferable. (A) The polyoxyalkylene containing a free crosslinking group may contain two or more kinds of such groups. Further, as the (A) polyoxyalkylene having a free crosslinking group, it is more preferable to contain at least a (meth)acryl fluorenyl group and/or a styryl group from the viewpoint of curability.

就圖案之密接性、膜之硬度及耐龜裂性之觀點而言，(A)含自由交聯基之聚矽氧烷中之光聚合性不飽和鍵結基之莫耳濃度較佳為0.01mmol/g以上，更佳為0.1mmol/g以上，進而佳為0.5mmol/g以上。另一方面，就減少顯影時之殘渣之觀點而言，該莫耳濃度較佳為10.0mmol/g以下，更佳為7.5mmol/g以下，進而佳為5.0mmol/g以下。The molar concentration of the photopolymerizable unsaturated bond group in the (A) polyoxyalkylene containing a free crosslinking group is preferably 0.01 in terms of the adhesion of the pattern, the hardness of the film, and the crack resistance. The amount of mmol/g or more is more preferably 0.1 mmol/g or more, and further preferably 0.5 mmol/g or more. On the other hand, the molar concentration is preferably 10.0 mmol/g or less, more preferably 7.5 mmol/g or less, and still more preferably 5.0 mmol/g or less from the viewpoint of reducing the residue at the time of development.

(A)含自由交聯基之聚矽氧烷中之光聚合性不飽和鍵結基之含量可藉由測定所得之聚合物之碘值而算出。(A) The content of the photopolymerizable unsaturated bonding group in the polyoxyalkylene containing a free crosslinking group can be calculated by measuring the iodine value of the obtained polymer.

(A)含自由交聯基之聚矽氧烷較佳為於一分子內含有鹼可溶性基。作為鹼可溶性基，並無特別限制，例如就提高聚矽氧烷之鹼溶性、且抑制顯影後之殘渣之產生的觀點而言，較佳為羧基、二羧酸酐基、或二羧酸酐基之殘基等。(A) The polyoxyalkylene having a free crosslinking group preferably contains an alkali-soluble group in one molecule. The alkali-soluble group is not particularly limited. For example, from the viewpoint of improving the alkali solubility of polyoxyalkylene and suppressing the generation of residue after development, a carboxyl group, a dicarboxylic anhydride group, or a dicarboxylic anhydride group is preferred. Residues, etc.

關於(A)含自由交聯基之聚矽氧烷中之羧基、二羧酸酐基、或二羧酸酐基之殘基之含量，只要(A)含自由交聯基之聚矽氧烷含有該等基，則並無特別限制，就顯影後之殘渣之減少及硬化膜之耐龜裂性之觀點而言，(A)含自由交聯基之聚矽氧烷之酸值較佳為10mgKOH/g以上，更佳為15mgKOH/g以上，進而佳為20mgKOH/g以上。另一方面，就圖案之密接性之觀點而言，該酸值較佳為200mgKOH/g以下，更佳為190mgKOH/g莫耳以下，進而佳為180mgKOH/g以下。The content of the residue of the carboxyl group, the dicarboxylic anhydride group or the dicarboxylic anhydride group in (A) the polyoxyalkylene containing a free crosslinking group, as long as (A) the polyoxyalkylene containing a free crosslinking group contains the content The isocratic group is not particularly limited. From the viewpoint of the reduction of the residue after development and the crack resistance of the cured film, (A) the acid value of the polyoxyalkylene having a free crosslinking group is preferably 10 mgKOH/ More preferably, it is 15 mgKOH/g or more, and further preferably 20 mgKOH/g or more. On the other hand, the acid value is preferably 200 mgKOH/g or less, more preferably 190 mgKOH/g mole or less, and still more preferably 180 mgKOH/g or less from the viewpoint of the adhesion of the pattern.

又，於含自由交聯基之聚矽氧烷組合物含有2種以上(A)含自由交聯基之聚矽氧烷之情形時，較佳為至少一種以具有上述所說明之範圍內之酸值般的含量而含有羧基、二羧酸酐基、或二羧酸酐基之殘基。Further, in the case where the polyoxane composition containing a free crosslinking group contains two or more kinds of (A) polyoxyalkylene having a free crosslinking group, at least one of them is preferably within the range described above. The acid group-like content contains a carboxyl group, a dicarboxylic anhydride group, or a residue of a dicarboxylic anhydride group.

再者，於本說明書中，所謂酸值，係指中和1g試樣中之羧基所必需的氫氧化鉀之毫克數。In the present specification, the acid value means the number of milligrams of potassium hydroxide necessary for neutralizing the carboxyl group in 1 g of the sample.

測定酸值之方法之一例如下所述：精確稱量3g之試樣，溶解於20ml乙醇中。於室溫下攪拌所得之溶液，進而加入5g之純化水，進一步於室溫下攪拌1小時。其後，添加幾滴作為指示劑之酚酞之甲醇溶液，以1/2當量之氫氧化鉀水溶液進行中和滴定，根據所使用之氫氧化鉀水溶液量算出酸值。One of the methods for determining the acid value is as follows: A sample of 3 g is accurately weighed and dissolved in 20 ml of ethanol. The resulting solution was stirred at room temperature, and further 5 g of purified water was added, and the mixture was further stirred at room temperature for 1 hour. Thereafter, a few drops of a methanol solution of phenolphthalein as an indicator were added, and a neutralization titration was carried out with a 1/2 equivalent potassium hydroxide aqueous solution, and an acid value was calculated from the amount of the potassium hydroxide aqueous solution used.

本實施形態中，就樹脂設計及製作方法之容易性之觀點而言，(A)含自由交聯基之聚矽氧烷較佳為藉由使用下述通式(I)：R7 R8 a1 Si(R9 )3-a1 In the present embodiment, from the viewpoint of easiness of resin design and production method, (A) the polyoxyalkylene having a free crosslinking group is preferably obtained by using the following general formula (I): R 7 R 8 A1 Si(R 9 ) 3-a1

{式中，R7 表示含有光聚合性不飽和鍵結基(例如雙鍵基)之碳數2~20之一價有機基，R8 分別獨立地表示可含有取代基之碳數1~20之直鏈狀或支鏈狀之有機基、芳基、或烷基芳基，R9 分別獨立地表示羥基、可水解之脫離基或鹵素原子，而且a1為0~2之整數}所表示之至少一種矽烷化合物之反應而得者。In the formula, R 7 represents a carbon number of 2 to 20 one-valent organic group containing a photopolymerizable unsaturated bond group (for example, a double bond group), and R 8 each independently represents a carbon number of 1 to 20 which may have a substituent. a linear or branched organic group, an aryl group or an alkylaryl group, wherein R 9 independently represents a hydroxyl group, a hydrolyzable leaving group or a halogen atom, and a1 is an integer of 0 to 2} A reaction of at least one decane compound.

上述通式(I)中，作為R9 ，較佳為選自由羥基、碳數1~12之直鏈 狀或支鏈狀之烷氧基、苯氧基、烷基羰氧基、氯(Cl)或溴(Br)所組成之群中之至少一種一價基，更佳為羥基、甲氧基、乙氧基、正丙氧基、或異丙氧基，就反應性之觀點而言，進而佳為羥基、甲氧基、或乙氧基。In the above formula (I), R 9 is preferably selected from the group consisting of a hydroxyl group, a linear or branched alkoxy group having 1 to 12 carbon atoms, a phenoxy group, an alkylcarbonyloxy group, and a chlorine (Cl). Or at least one monovalent group of the group consisting of bromine (Br), more preferably a hydroxyl group, a methoxy group, an ethoxy group, a n-propoxy group or an isopropoxy group, from the viewpoint of reactivity, Further preferably, it is a hydroxyl group, a methoxy group or an ethoxy group.

上述通式(I)中，作為R7 ，較佳為含有不飽和鍵(例如雙鍵)之碳數2~17之一價有機基，具體而言，例如可列舉：乙烯基、苯乙烯基、(甲基)丙烯酸基、3-(甲基)丙烯醯氧基丙基、2-(甲基)丙烯醯氧基乙基、(甲基)丙烯醯氧基甲基等。其中，較佳為苯乙烯基、或3-(甲基)丙烯醯氧基丙基。又，本說明書中，所謂(甲基)丙烯酸基，表示丙烯酸基及甲基丙烯酸基。In the above formula (I), R 7 is preferably a one-valent organic group having 2 to 17 carbon atoms which contains an unsaturated bond (for example, a double bond), and specific examples thereof include a vinyl group and a styryl group. (meth)acrylic acid group, 3-(meth)acryloxypropyl group, 2-(meth)acryloxyethyl group, (meth)acryloxymethyl group, and the like. Among them, a styryl group or a 3-(meth)acryloxypropyl group is preferred. In the present specification, the (meth)acrylic group means an acryl group and a methacryl group.

其他實施形態中，(A)含自由交聯基之聚矽氧烷亦可含有鹼可溶性基，故就樹脂設計及製作方法之容易性之觀點而言，較佳為藉由使用上述通式(I)所表示之至少一種矽烷化合物與下述通式(II)：R10 R11 a2 Si(R9 )3-a2 In other embodiments, (A) the polyoxyalkylene containing a free crosslinking group may also contain an alkali-soluble group, and therefore, from the viewpoint of easiness of resin design and production method, it is preferred to use the above formula ( I) at least one decane compound represented by the following formula (II): R 10 R 11 a2 Si(R 9 ) 3-a2

{式中，R9 如上述通式(I)中所定義，R10 表示鹼可溶性基，R11 分別獨立地表示可含有取代基之碳數1~20之直鏈狀或支鏈狀之有機基、芳基、或烷基芳基，而且a2為0~2之整數}所表示之至少一種矽烷化合物之反應而得者。In the formula, R 9 is as defined in the above formula (I), R 10 represents an alkali-soluble group, and R 11 each independently represents a linear or branched organic group having 1 to 20 carbon atoms which may have a substituent. A reaction of at least one decane compound represented by a group, an aryl group, or an alkylaryl group, and a2 is an integer of 0 to 2.

上述通式(II)中，R10 只要含有羧基、二羧酸酐基、或二羧酸酐基之殘基，則並無特別限制，具體而言，較佳為自由下述通式(II-1)所表示之一價有機基所組成之群中選擇。In the above formula (II), R 10 is not particularly limited as long as it contains a residue of a carboxyl group, a dicarboxylic anhydride group or a dicarboxylic anhydride group, and specifically, it is preferably free from the following formula (II-1). ) is selected from the group consisting of one of the organic groups.

[化7] [Chemistry 7]

{式中，Rx為碳原子數為1~6之直鏈狀或支鏈狀之二價有機基，Ry及Rz分別獨立為選自由甲基、乙基、丙基、異丙基及氫所組成之群中之至少一種，Ry與Rz中之一者或兩者為氫，Ra為碳原子數為2~16之直鏈狀、支鏈狀或環狀之二價有機基，Rs為碳原子數為1~20之直鏈狀、支鏈狀或環狀之二價有機基，Rt為碳原子數為1~18之直鏈狀、支鏈狀或環狀之二價有機基，且Ru及Rv分別獨立為碳原子數為1~20之直鏈狀、支鏈狀或環狀之一價有機基，或者下述通式(II-2)所表示之一價有機基}Wherein Rx is a linear or branched divalent organic group having 1 to 6 carbon atoms, and Ry and Rz are independently selected from the group consisting of methyl, ethyl, propyl, isopropyl and hydrogen. At least one of the group consisting of, one or both of Ry and Rz is hydrogen, and Ra is a linear, branched or cyclic divalent organic group having 2 to 16 carbon atoms, and Rs is carbon a linear, branched or cyclic divalent organic group having 1 to 20 atoms, and Rt is a linear, branched or cyclic divalent organic group having 1 to 18 carbon atoms, and Ru and Rv are each independently a linear, branched or cyclic one-valent organic group having 1 to 20 carbon atoms, or a monovalent organic group represented by the following formula (II-2)}

{式中，Rw為碳原子數為1~16之直鏈狀、支鏈狀或環狀之二價有機基，Rb為碳原子數為1~20之直鏈狀、支鏈狀或環狀之一價有機基或含有光聚合性不飽和雙鍵基之一價有機基，而且Rc為下述通式(II-3)所表示之基或氫原子}In the formula, Rw is a linear, branched or cyclic divalent organic group having 1 to 16 carbon atoms, and Rb is a linear, branched or cyclic group having 1 to 20 carbon atoms. a monovalent organic group or a monovalent organic group containing a photopolymerizable unsaturated double bond group, and Rc is a group represented by the following formula (II-3) or a hydrogen atom}

{式中，Ra為碳原子數為2~16之直鏈狀、支鏈狀或環狀之二價有機基}In the formula, Ra is a linear, branched or cyclic divalent organic group having 2 to 16 carbon atoms.

上述通式(II)中，作為R10 中所含之有機基之較佳例，可列舉：琥珀酸酐基(R10 -1)、環己烷二羧酸酐基(R10 -2)、4-甲基-環己烷二羧酸酐基(R10 -3)、5-甲基-環己烷二羧酸酐基(R10 -4)、二環庚烷二羧酸酐基(R10 -5)、7-氧雜-二環庚烷二羧酸酐基(R10 -6)、鄰苯二甲酸酐基(R10 -7)、琥珀酸基或其半酯基(R10 -8)、環己烷二羧酸基或其半酯基(R10 -9)、4-甲基-環己烷二羧酸基或其半酯基(R10 -10)、5-甲基-環己烷二羧酸基或其半酯基(R10 -11)、二環庚烷二羧酸基或其半酯基(R10 -12)、7-氧雜-二環庚烷二羧酸基或其半酯基(R10 -13)、鄰苯二甲酸基或其半酯基(R10 -14)、藉由胺基與二羧酸酐之反應而含有醯胺鍵之基(R10 -15)、含有異三聚氰酸骨架之基(R10 -16)等。R10 可分別單獨含有該等基，或 可組合含有2種以上。In the above formula (II), preferred examples of the organic group contained in R 10 include a succinic anhydride group (R 10 -1), a cyclohexane dicarboxylic anhydride group (R 10 -2), and 4 -methyl-cyclohexanedicarboxylic anhydride group (R 10 -3), 5-methyl-cyclohexanedicarboxylic anhydride group (R 10 -4), dicycloheptanedicarboxylic anhydride group (R 10 -5) , 7-oxa-bicycloheptanedicarboxylic anhydride group (R 10 -6), phthalic anhydride group (R 10 -7), succinic acid group or its half ester group (R 10 -8), Cyclohexanedicarboxylic acid group or its half ester group (R 10 -9), 4-methyl-cyclohexanedicarboxylic acid group or its half ester group (R 10 -10), 5-methyl-cyclohexane An alkanedicarboxylic acid group or a half ester group thereof (R 10 -11), a dicycloheptanedicarboxylic acid group or a half ester group thereof (R 10 -12), 7-oxa-bicycloheptanedicarboxylic acid group Or a half ester group thereof (R 10 -13), a phthalic acid group or a half ester group thereof (R 10 -14), a group containing a guanamine bond by reaction of an amine group with a dicarboxylic acid anhydride (R 10 - 15) A group containing an iso-cyanuric acid skeleton (R 10 -16) or the like. R 10 may be contained alone or in combination of two or more.

上述通式(II-1)中，Rx為碳原子數為1~6之直鏈狀或支鏈狀之二價有機基。其中，就合成時之容易性之觀點而言，Rx較佳為烴基。作為烴基，例如可列舉：亞甲基、伸乙基、伸丙基、伸異丙基、伸正丁基、伸異丁基、伸第二丁基、伸第三丁基、伸正戊基、伸異戊基、伸新戊基、伸第三戊基。該等基可含有雙鍵及/或三鍵，可分別單獨使用，或可組合使用2種以上。其中，最佳為伸丙基。In the above formula (II-1), Rx is a linear or branched divalent organic group having 1 to 6 carbon atoms. Among them, Rx is preferably a hydrocarbon group from the viewpoint of easiness in synthesis. Examples of the hydrocarbon group include a methylene group, an ethylidene group, a propyl group, an isopropyl group, an exobutyl group, an exobutyl group, a dibutyl group, a thirylene group, a pentyl group, and a stretching group. Isoamyl, neopentyl, and third amyl. These groups may contain a double bond and/or a triple bond, and they may be used alone or in combination of two or more. Among them, the best is propyl.

上述通式(II-1)中，含有醯胺鍵之基(R10 -15)係藉由胺基與二羧酸酐之反應而得之含有羧基之基。又，Rs為碳原子數為1~20之直鏈狀、支鏈狀或環狀之二價有機基。又，作為上述通式(II-1)所表示之二羧酸酐，例如可列舉：琥珀酸酐、環己烷二羧酸酐、4-甲基-環己烷二羧酸酐、5-甲基-環己烷二羧酸酐、二環庚烷二羧酸酐、7-氧雜二環庚烷二羧酸酐、四氫鄰苯二甲酸酐、偏苯三甲酸酐、均苯四甲酸酐、己二酸酐、鄰苯二甲酸酐、(3-三甲氧基矽烷基丙基)琥珀酸酐、(3-三乙氧基矽烷基丙基)琥珀酸酐等多元酸酐。該等可分別單獨使用，或可組合使用2種以上。In the above formula (II-1), the group containing a guanamine bond (R 10 -15) is a group having a carboxyl group obtained by a reaction of an amine group and a dicarboxylic acid anhydride. Further, Rs is a linear, branched or cyclic divalent organic group having 1 to 20 carbon atoms. In addition, examples of the dicarboxylic acid anhydride represented by the above formula (II-1) include succinic anhydride, cyclohexane dicarboxylic anhydride, 4-methyl-cyclohexane dicarboxylic anhydride, and 5-methyl-ring. Hexanedicarboxylic anhydride, dicycloheptane dicarboxylic anhydride, 7-oxabicycloheptane dicarboxylic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic anhydride, ortho A polybasic acid anhydride such as phthalic anhydride, (3-trimethoxydecylpropyl) succinic anhydride or (3-triethoxydecylpropyl) succinic anhydride. These may be used alone or in combination of two or more.

上述通式(II-1)中，含有異三聚氰酸骨架之基(R10 -16)係自含有縮水甘油基之異三聚氰酸骨架，經由利用與羧基或羥基之反應的縮水甘油基之開環反應，使二羧酸酐與所產生之羥基反應而得之含有羧基之基。In the above formula (II-1), the group containing the iso-cyanuric acid skeleton (R 10 -16) is a glycidyl group derived from a glycidyl group-containing isocyanuric acid group by using a reaction with a carboxyl group or a hydroxyl group. The ring-opening reaction causes the dicarboxylic acid anhydride to react with the generated hydroxyl group to obtain a carboxyl group-containing group.

上述通式(II)中，作為R10 而最佳之基為丙基琥珀酸酐基(R10 -1)、丙基琥珀酸基、或其半甲酯基、或其半乙酯基(R10 -8)。In the above formula (II), the group most preferred as R 10 is a propyl succinic anhydride group (R 10 -1), a propyl succinic acid group, or a half-methyl ester group thereof, or a semi-ester group thereof (R) 10 -8).

其他實施形態中，就樹脂設計及製作方法之容易性之觀點而言，(A)含自由交聯基之聚矽氧烷較佳為藉由除了使用上述通式(I)所表示之至少一種矽烷化合物及上述通式(II)所表示之至少一種矽烷化合物以外，還使用下述通式(III)： R12 a3 Si(R9 )4-a3 In other embodiments, from the viewpoint of easiness of resin design and production method, (A) the polyoxyalkylene having a free crosslinking group is preferably at least one selected by using the above formula (I). In addition to the decane compound and at least one decane compound represented by the above formula (II), the following formula (III) is also used: R 12 a3 Si(R 9 ) 4-a3

{式中，R9 如上述通式(I)中所定義，R12 分別獨立地表示可含有取代基之碳數1~20之直鏈狀或支鏈狀之有機基、芳基、烷基芳基，而且a3為0~3之整數}所表示之至少一種矽烷化合物之反應而得者。In the formula, R 9 is as defined in the above formula (I), and R 12 each independently represents a linear or branched organic group, aryl group or alkyl group having 1 to 20 carbon atoms which may have a substituent. An aryl group, and a3 is a reaction of at least one decane compound represented by an integer of 0 to 3.

作為上述通式(I)所表示之矽烷化合物，具體可列舉：3-(甲基)丙烯醯氧基丙基三甲氧基矽烷、3-(甲基)丙烯醯氧基丙基三乙氧基矽烷、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、對苯乙烯基三甲氧基矽烷、對苯乙烯基三乙氧基矽烷、對(1-丙烯基苯基)三甲氧基矽烷、對(1-丙烯基苯基)三乙氧基矽烷、對(2-丙烯基苯基)三甲氧基矽烷、對(2-丙烯基苯基)三乙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷等。Specific examples of the decane compound represented by the above formula (I) include 3-(meth)acryloxypropyltrimethoxydecane and 3-(methyl)acryloxypropyltriethoxylate. Decane, 3-(meth)acryloxypropylmethyldimethoxydecane, 3-(methyl)propenyloxypropylmethyldiethoxydecane, p-styryltrimethoxydecane , p-styryltriethoxydecane, p-(1-propenylphenyl)trimethoxynonane, p-(1-propenylphenyl)triethoxydecane, p-(2-propenylphenyl)trimethyl Oxydecane, p-(2-propenylphenyl)triethoxydecane, vinyltrimethoxydecane, vinyltriethoxydecane, and the like.

關於上述通式(II)所表示之矽烷化合物，含有羧基、二羧酸酐基、或二羧酸酐基之半酯基之烷氧基矽烷化合物中，最佳之化合物為(3-三甲氧基矽烷基丙基)琥珀酸酐、(3-三乙氧基矽烷基丙基)琥珀酸酐、(3-三甲氧基矽烷基丙基)琥珀酸、(3-三乙氧基矽烷基丙基)琥珀酸、(3-三甲氧基矽烷基丙基)琥珀酸之半甲酯、(3-三乙氧基矽烷基丙基)琥珀酸之半甲酯、(3-三甲氧基矽烷基丙基)琥珀酸之半乙酯及(3-三乙氧基矽烷基丙基)琥珀酸之半乙酯。In the alkane compound represented by the above formula (II), an alkoxydecane compound containing a carboxyl group, a dicarboxylic acid anhydride group or a half ester group of a dicarboxylic anhydride group, the most preferable compound is (3-trimethoxydecane). Propyl anhydride, (3-triethoxydecylpropyl) succinic anhydride, (3-trimethoxydecylpropyl) succinic acid, (3-triethoxydecylpropyl) succinic acid , a half methyl ester of (3-trimethoxydecylpropyl) succinic acid, a half methyl ester of (3-triethoxydecylpropyl) succinic acid, (3-trimethoxydecylpropyl) amber A half ethyl ester of acid and a half ethyl ester of (3-triethoxydecylpropyl) succinic acid.

上述通式(III)所表示之矽烷化合物之具體例中，作為含有聚合性環狀醚鍵基之化合物，例如可列舉：3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷、3-縮水甘油氧基丙基甲基二甲氧基矽烷、3-縮水甘油氧基丙基甲基二乙氧基矽烷、2-(3,4-環氧環己基)三甲氧基矽烷、2-(3,4-環氧環己基)三乙氧基矽烷、2-(3,4-環氧環己基)甲基二甲氧基矽烷、2-(3,4-環氧環己基)甲基二乙氧基矽烷等。In the specific example of the decane compound represented by the above formula (III), examples of the compound containing a polymerizable cyclic ether bond group include 3-glycidoxypropyltrimethoxydecane and 3-glycidyloxygen. Propyltriethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 2-(3,4-epoxy Cyclohexyl)trimethoxydecane, 2-(3,4-epoxycyclohexyl)triethoxydecane, 2-(3,4-epoxycyclohexyl)methyldimethoxydecane, 2-(3 , 4-epoxycyclohexyl)methyldiethoxydecane, and the like.

作為上述含有聚合性環狀醚鍵基之化合物以外之上述通式(III)所 表示之矽烷化合物之具體例，可列舉：甲基三甲氧基矽烷、甲基三乙氧基矽烷、二甲基二甲氧基矽烷、二甲基二乙氧基矽烷、乙基三甲氧基矽烷、乙基三乙氧基矽烷、二乙基二甲氧基矽烷、二乙基二乙氧基矽烷、環己基三甲氧基矽烷、環己基三乙氧基矽烷、環己基甲基二甲氧基矽烷、環己基甲基二乙氧基矽烷、苯基三甲氧基矽烷、苯基三乙氧基矽烷、苯基甲基二甲氧基矽烷、苯基甲基二乙氧基矽烷、二環戊基二甲氧基矽烷、二環戊基二乙氧基矽烷、二苯基二甲氧基矽烷、二苯基二乙氧基矽烷、十八烷基三甲氧基矽烷、十八烷基三乙氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三甲氧基矽烷、N-2-(胺基乙基)-3-胺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-胺基丙基甲基二乙氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-胺基丙基甲基二甲氧基矽烷、3-胺基丙基二乙氧基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷、N-苯基-3-胺基丙基三乙氧基矽烷、N-(乙烯基苄基)-2-胺基乙基-3-胺基丙基三甲氧基矽烷之鹽酸鹽、3-巰基丙基三甲氧基矽烷、3-巰基丙基三乙氧基矽烷、3-巰基丙基甲基二甲氧基矽烷、3-巰基丙基甲基二乙氧基矽烷、甲基三氯矽烷、苯基三氯矽烷、二甲基二氯矽烷、三甲基氯矽烷、三乙基氯矽烷、第三丁基二甲基氯矽烷、三異丙基氯矽烷等。該等可分別單獨使用，或可組合使用2種以上。The above formula (III) other than the compound containing a polymerizable cyclic ether bond group Specific examples of the decane compound shown include methyltrimethoxydecane, methyltriethoxydecane, dimethyldimethoxydecane, dimethyldiethoxydecane, and ethyltrimethoxydecane. , ethyl triethoxy decane, diethyl dimethoxy decane, diethyl diethoxy decane, cyclohexyl trimethoxy decane, cyclohexyl triethoxy decane, cyclohexyl methyl dimethoxy Decane, cyclohexylmethyldiethoxydecane, phenyltrimethoxydecane, phenyltriethoxydecane, phenylmethyldimethoxydecane, phenylmethyldiethoxydecane, dicyclopentane Dimethoxy decane, dicyclopentyl diethoxy decane, diphenyl dimethoxy decane, diphenyl diethoxy decane, octadecyl trimethoxy decane, octadecyl triethyl Oxydecane, N-2-(aminoethyl)-3-aminopropyltrimethoxydecane, N-2-(aminoethyl)-3-aminopropyltriethoxydecane, N -2-(Aminoethyl)-3-aminopropylmethyldimethoxydecane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxydecane, 3 -Aminopropyltrimethoxydecane, 3-aminopropyl Triethoxydecane, 3-aminopropylmethyldimethoxydecane, 3-aminopropyldiethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N- Phenyl-3-aminopropyltriethoxydecane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxydecane hydrochloride, 3-mercaptopropyl Trimethoxy decane, 3-mercaptopropyltriethoxy decane, 3-mercaptopropylmethyldimethoxydecane, 3-mercaptopropylmethyldiethoxydecane, methyltrichlorodecane, benzene Trichloro decane, dimethyl dichloro decane, trimethyl chloro decane, triethyl chloro decane, tert-butyl dimethyl chloro decane, triisopropyl chloro decane, and the like. These may be used alone or in combination of two or more.

(A)含自由交聯基之聚矽氧烷可藉由任意方法合成，例如可藉由以下方式獲得：藉由添加水及觸媒，將通式(I)所表示之矽烷化合物、通式(II)所表示之矽烷化合物及通式(III)所表示之矽烷化合物水解後，於溶劑之存在下或不存在溶劑之條件下使所得之水解物縮合。(A) The polyoxyalkylene containing a free crosslinking group can be synthesized by any method, for example, by obtaining a decane compound represented by the general formula (I) by adding water and a catalyst. After the decane compound represented by (II) and the decane compound represented by the formula (III) are hydrolyzed, the obtained hydrolyzate is condensed in the presence of a solvent or in the absence of a solvent.

水解反應係藉由花費1分鐘~180分鐘於溶劑中之矽烷化合物中添加酸性觸媒及水而進行。就水解之反應性之觀點而言，獲得水解物之過程之溫度較佳為10℃以上，更佳為20℃以上，另一方面，就保護 官能基之觀點而言，較佳為150℃以下，更佳為120℃以下。就水解之反應性之觀點而言，獲得加水分解物之過程之反應時間較佳為0.1小時以上，更佳為0.5小時以上，另一方面，就保護官能基之觀點而言，較佳為10小時以下，更佳為5小時以下。The hydrolysis reaction is carried out by adding an acidic catalyst and water to the decane compound in a solvent for from 1 minute to 180 minutes. From the viewpoint of the reactivity of the hydrolysis, the temperature of the process of obtaining the hydrolyzate is preferably 10 ° C or more, more preferably 20 ° C or more, and on the other hand, protection From the viewpoint of the functional group, it is preferably 150 ° C or lower, more preferably 120 ° C or lower. From the viewpoint of the reactivity of the hydrolysis, the reaction time for obtaining the hydrolyzate is preferably 0.1 hour or longer, more preferably 0.5 hour or longer, and on the other hand, from the viewpoint of protecting the functional group, it is preferably 10 Below the hour, more preferably less than 5 hours.

水解反應較佳為於酸性觸媒之存在下進行。作為酸性觸媒，較佳為含有鹽酸、硝酸、硫酸、甲酸、乙酸或磷酸之酸性水溶液。就水解之反應性之觀點而言，相對於水解反應時所使用之所有矽烷化合物，該等酸性觸媒之較佳含量較佳為0.01mol%以上，就保護官能基之觀點而言，較佳為10mol%以下。The hydrolysis reaction is preferably carried out in the presence of an acidic catalyst. As the acidic catalyst, an acidic aqueous solution containing hydrochloric acid, nitric acid, sulfuric acid, formic acid, acetic acid or phosphoric acid is preferred. From the viewpoint of the reactivity of the hydrolysis, the preferred content of the acidic catalyst is preferably 0.01 mol% or more with respect to all the decane compounds used in the hydrolysis reaction, and from the viewpoint of protecting the functional group, it is preferred. It is 10 mol% or less.

較佳為於藉由矽烷化合物之水解反應而獲得矽烷醇化合物後，直接將反應液於50℃以上、所使用之溶劑之沸點以下加熱1小時~100小時，進行縮合反應。又，為了提高(A)含自由交聯基之聚矽氧烷之聚合度，亦可進行再加熱及/或減壓及/或添加鹼性觸媒。Preferably, after the stanol compound is obtained by a hydrolysis reaction of a decane compound, the reaction solution is directly heated at 50 ° C or higher and the boiling point of the solvent to be used for 1 hour to 100 hours to carry out a condensation reaction. Further, in order to increase the degree of polymerization of (A) the polyoxyalkylene containing a free crosslinking group, reheating and/or depressurization and/or addition of a basic catalyst may be carried out.

用於矽烷化合物之水解反應及該水解物之縮合反應中之溶劑並無特別限定，可考慮樹脂組合物之穩定性、潤濕性、揮發性等而適當選擇。又，亦可將溶劑組合2種以上，或於不存在溶劑之條件下進行該等反應。The solvent used in the hydrolysis reaction of the decane compound and the condensation reaction of the hydrolyzate is not particularly limited, and may be appropriately selected in consideration of stability, wettability, volatility, and the like of the resin composition. Further, two or more kinds of solvents may be combined or may be carried out in the absence of a solvent.

作為溶劑之具體例，可列舉：甲醇、乙醇、丙醇、異丙醇、丁醇、異丁醇、第三丁醇、戊醇、異戊醇、二丙酮醇等醇類；乙二醇、丙二醇等二醇類；乙二醇單甲醚、乙二醇單***、丙二醇單甲醚、丙二醇單***、乙二醇二甲醚、乙二醇二***等醚類；甲基乙基酮、乙醯丙酮、甲基丙基酮、甲基丁基酮、甲基異丁基酮、環戊酮等酮類；乙二醇單***乙酸酯、丙二醇單***乙酸酯、乳酸甲酯、乳酸乙酯、乳酸丁酯等乙酸酯類；γ-丁內酯、N-甲基-2-吡咯啶酮、二甲基亞碸、二甲基乙醯胺等。Specific examples of the solvent include alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, pentanol, isoamyl alcohol, and diacetone alcohol; ethylene glycol; a glycol such as propylene glycol; an ether such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol dimethyl ether or ethylene glycol diethyl ether; methyl ethyl ketone; Ketones such as acetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, and cyclopentanone; ethylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate, methyl lactate, Acetate such as ethyl lactate or butyl lactate; γ-butyrolactone, N-methyl-2-pyrrolidone, dimethyl hydrazine, dimethyl acetamide, and the like.

於因水解反應生成溶劑之情形時，亦可於不存在溶劑之條件下 進行水解。亦較佳為於水解反應結束後，藉由進一步添加溶劑而調整為作為樹脂組合物而合適之濃度。又，亦可根據樹脂組合物之用途，於水解後、於加熱及/或減壓下，將生成醇等適量地蒸餾去除，其後添加較佳之溶劑。When a solvent is formed by a hydrolysis reaction, it may be in the absence of a solvent. Hydrolysis is carried out. It is also preferred to adjust the concentration to a suitable concentration as a resin composition by further adding a solvent after completion of the hydrolysis reaction. Further, depending on the use of the resin composition, an appropriate amount of alcohol or the like may be distilled off after hydrolysis, under heating and/or reduced pressure, and then a preferred solvent may be added.

相對於所有矽烷化合物100質量份，水解反應中使用之溶劑之量較佳為80質量份以上、500質量份以下。The amount of the solvent used in the hydrolysis reaction is preferably 80 parts by mass or more and 500 parts by mass or less based on 100 parts by mass of all the decane compounds.

又，水解反應中所用之水較佳為離子交換水。水之量可任意選擇，相對於水解反應中所用之矽烷化合物1莫耳，較佳為1.0莫耳~4.0莫耳之範圍。Further, the water used in the hydrolysis reaction is preferably ion-exchanged water. The amount of water can be arbitrarily selected, and is preferably in the range of 1.0 mol to 4.0 mol with respect to 1 mol of the decane compound used in the hydrolysis reaction.

本實施形態中，(A)含自由交聯基之聚矽氧烷之製造方法除上述反應以外，於處理矽烷醇時因矽烷醇彼此之脫水縮合而產生水，故亦可不添加水，而且可於處理氯矽烷時不添加水及觸媒而進行反應。In the present embodiment, (A) a method for producing a polyoxyalkylene containing a free crosslinking group, in addition to the above reaction, is produced by dehydration condensation of decyl alcohol with each other in the treatment of stanol, so that water may not be added. The reaction is carried out without adding water and a catalyst when treating chlorodecane.

關於存在於(A)含自由交聯基之聚矽氧烷中、且不參與縮合之矽烷醇(殘留矽烷醇)，就降低烘烤時之縮合所致之收縮，減少由縮合產生之水、醇之排氣之觀點而言，較佳為少量，較佳為幾乎不存在。Regarding the stanol (residual stanol) which is present in (A) a polyoxyalkylene containing a free crosslinking group and does not participate in condensation, the shrinkage caused by condensation at the time of baking is lowered, and water produced by condensation is reduced, From the viewpoint of the exhaust of the alcohol, it is preferably a small amount, preferably almost no.

(A)含自由交聯基之聚矽氧烷較佳為殘留矽烷醇較少，或幾乎不存在殘留矽烷醇，例如係藉由如下方法而得：於觸媒之存在下，至少使上述通式(I)所表示之矽烷化合物、上述通式(II)所表示之矽烷化合物及下述通式(IV)：R13 2 Si(OH)2 (A) The polyoxyalkylene having a free crosslinking group preferably has less residual stanol or almost no residual stanol, for example, by the following method: at least in the presence of a catalyst a decane compound represented by the formula (I), a decane compound represented by the above formula (II), and the following formula (IV): R 13 2 Si(OH) 2

{式中，R13 為碳原子數為6~20之芳基、碳原子數為2~20之烷基芳基、碳原子數為1~20之烷基、或碳原子數為5~20之環烷基，可彼此相同亦可不同，且亦可經由共價鍵而相互鍵結}所表示之矽烷二醇化合物反應，或較佳為不積極地添加水而進行縮合。In the formula, R 13 is an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 2 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or a carbon number of 5 to 20 The cycloalkyl groups may be the same or different from each other, and may be bonded to each other by a covalent bond, or preferably condensed by not actively adding water.

上述通式(IV)中，作為R13 ，例如可列舉：苯基、甲苯基、二甲苯基、三甲苯基、萘基、甲基、乙基、環戊基及環己基。In the above formula (IV), examples of R 13 include a phenyl group, a tolyl group, a xylyl group, a trimethylphenyl group, a naphthyl group, a methyl group, an ethyl group, a cyclopentyl group, and a cyclohexyl group.

作為上述通式(IV)所表示之矽烷二醇化合物之具體例，可列舉：二苯基矽烷二醇、二對甲苯甲醯基矽烷二醇、二-二甲苯基矽烷二醇、二-三甲苯基矽烷二醇、二對苯乙烯基矽烷二醇、二萘基矽烷二醇、二環戊基矽烷二醇、環己基甲基矽烷二醇等，就共聚合及耐熱性之觀點而言，尤佳為二苯基矽烷二醇、二環戊基矽烷二醇及環己基甲基矽烷二醇。Specific examples of the decanediol compound represented by the above formula (IV) include diphenylnonanediol, dip-tolylmethylmercaptodiol, di-dimethylphenylnonanediol, and di-three. Tolyl decanediol, di-p-styryl decane diol, dinaphthyl decane diol, dicyclopentyl decane diol, cyclohexylmethyl decane diol, etc., from the viewpoints of copolymerization and heat resistance, More preferred are diphenylnonanediol, dicyclopentyldecanediol and cyclohexylmethyldecanediol.

就縮合之反應性之觀點而言，不積極地添加水而進行縮合之反應之溫度較佳為40℃以上，更佳為50℃以上，另一方面，就保護官能基之觀點而言，較佳為150℃以下，更佳為130℃以下。From the viewpoint of the reactivity of the condensation, the temperature at which the reaction is carried out without actively adding water is preferably 40° C. or higher, more preferably 50° C. or higher, and on the other hand, from the viewpoint of protecting the functional group, Preferably, it is 150 ° C or less, more preferably 130 ° C or less.

就縮合之反應性之觀點而言，不積極地添加水而進行縮合之反應之時間較佳為0.5小時以上，更佳為1小時以上，另一方面，就保護官能基之觀點而言，較佳為48小時以下，更佳為30小時以下。From the viewpoint of the reactivity of the condensation, the reaction time for performing the condensation without actively adding water is preferably 0.5 hours or longer, more preferably 1 hour or longer, and on the other hand, from the viewpoint of protecting the functional group, It is preferably 48 hours or less, more preferably 30 hours or less.

不積極地添加水而進行縮合之反應中使用觸媒，且不積極地添加水。作為觸媒，可使用鹼性觸媒或酸性觸媒。A catalyst is used in the reaction in which condensation is not actively added, and water is not actively added. As the catalyst, an alkaline catalyst or an acidic catalyst can be used.

作為鹼性觸媒，可使用三價或四價金屬烷氧化物。具體而言，作為鹼性觸媒，可列舉：三甲氧基鋁、三乙氧基鋁、三正丙氧基鋁、三異丙氧基鋁、三正丁氧基鋁、三異丁氧基鋁、三-第二丁氧基鋁、三-第三丁氧基鋁、三甲氧基硼、三乙氧基硼、三正丙氧基硼、三異丙氧基硼、三正丁氧基硼、三異丁氧基硼、三-第二丁氧基硼、三-第三丁氧基硼、四甲氧基矽烷、四乙氧基矽烷、四正丙氧基矽烷、四異丙氧基矽烷、四正丁氧基矽烷、四異丁氧基矽烷、四-第二丁氧基矽烷、四-第三丁氧基矽烷、四甲氧基鍺、四乙氧基鍺、四正丙氧基鍺、四異丙氧基鍺、四正丁氧基鍺、四異丁氧基鍺、四-第二丁氧基鍺、四-第三丁氧基鍺、四甲氧基鈦、四乙氧基鈦、四正丙氧基鈦、四異丙氧基鈦、四正丁氧基鈦、四異丁氧基鈦、四-第二丁氧基鈦、四-第三丁氧基鈦、四甲氧基鋯、四乙氧基鋯、四正丙氧基鋯、四異 丙氧基鋯、四正丁氧基鋯、四異丁氧基鋯、四-第二丁氧基鋯、四-第三丁氧基鋯等。As the basic catalyst, a trivalent or tetravalent metal alkoxide can be used. Specifically, examples of the basic catalyst include trimethoxy aluminum, triethoxy aluminum, tri-n-propoxy aluminum, aluminum triisopropoxide, aluminum tri-n-butoxide, and triisobutoxy group. Aluminum, tri-second butoxide aluminum, tri-t-butoxide aluminum, trimethoxy boron, triethoxy boron, tri-n-propoxy boron, triisopropoxy boron, tri-n-butoxy Boron, triisobutoxy boron, tri-second butoxide boron, tri-t-butoxy boron, tetramethoxydecane, tetraethoxydecane, tetra-n-propoxy decane, tetraisopropoxy Base decane, tetra-n-butoxy decane, tetraisobutoxy decane, tetra-second butoxy decane, tetra-butoxy decane, tetramethoxy fluorene, tetraethoxy fluorene, tetra-n-propyl Oxime, tetraisopropoxy fluorene, tetra-n-butoxy fluorene, tetra-isobutoxy fluorene, tetra-second butoxy fluorene, tetra-tert-butoxy fluorene, tetramethoxy titanium, tetra Titanium ethoxide, titanium tetra-n-propoxide, titanium tetraisopropoxide, titanium tetra-n-butoxide, titanium tetra-isobutoxide, titanium tetra-second butoxide, titanium tetra-butoxybutoxide , tetramethoxy zirconium, tetraethoxy zirconium, tetra-n-propoxy zirconium, tetra-iso Zirconium propoxide, zirconium tetra-n-butoxide, zirconium tetraisobutoxide, zirconium tetra-butoxide, zirconium tetra-butoxybutoxide, and the like.

又，亦可使用鹼金屬之氫氧化物或鹼土金屬之氫氧化物、例如氫氧化鋇、氫氧化鈉、氫氧化鉀、氫氧化鍶、氫氧化鈣及氫氧化鎂作為鹼性觸媒。又，亦可使用NH4 F(氟化銨)作為鹼性觸媒。其中，較佳為氫氧化鋇、氫氧化鈉、氫氧化鍶、四-第三丁氧基鈦及四異丙氧基鈦。為了達成迅速且均勻之聚合反應，較佳為鹼性觸媒於反應溫度範圍內為液狀。Further, an alkali metal hydroxide or an alkaline earth metal hydroxide such as barium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide or magnesium hydroxide may be used as the basic catalyst. Further, NH 4 F (ammonium fluoride) can also be used as the basic catalyst. Among them, preferred are barium hydroxide, sodium hydroxide, barium hydroxide, titanium tetra-butoxide, and titanium tetraisopropoxide. In order to achieve a rapid and uniform polymerization reaction, it is preferred that the basic catalyst be in a liquid state within the reaction temperature range.

相對於所有矽烷化合物，就縮合反應性之觀點而言，該等鹼性觸媒之較佳含量較佳為0.01mol%以上，另一方面，就保護官能基之觀點而言，較佳為10mol%以下。The preferred content of the basic catalyst is preferably 0.01 mol% or more with respect to all the decane compounds, and on the other hand, from the viewpoint of protecting the functional group, it is preferably 10 mol. %the following.

作為酸性觸媒，可使用不含水之有機酸性觸媒。具體而言，作為酸性觸媒，可列舉：乙酸、三氟乙酸、丙烯酸、甲基丙烯酸、檸檬酸、蘋果酸、琥珀酸、鄰苯二甲酸、(3-三甲氧基矽烷基丙基)琥珀酸、或其半酯及(3-三乙氧基矽烷基丙基)琥珀酸、或其半酯等。As the acidic catalyst, an organic acid catalyst which does not contain water can be used. Specifically, examples of the acidic catalyst include acetic acid, trifluoroacetic acid, acrylic acid, methacrylic acid, citric acid, malic acid, succinic acid, phthalic acid, and (3-trimethoxydecylpropyl)amber. An acid, or a half ester thereof, and (3-triethoxydecylpropyl) succinic acid, or a half ester thereof.

相對於所有矽烷化合物，就縮合反應性之觀點而言，該等酸性觸媒之較佳含量較佳為0.01mol%以上，另一方面，就保護官能基之觀點而言，較佳為10mol%以下。The preferred content of the acidic catalyst is preferably 0.01 mol% or more from the viewpoint of the condensation reactivity with respect to all the decane compounds, and on the other hand, from the viewpoint of protecting the functional group, it is preferably 10 mol%. the following.

於合成(A)含自由交聯基之聚矽氧烷時，就保護交聯基之觀點而言，亦可於合成時添加聚合抑制劑。In the case of synthesizing (A) a polyoxyalkylene containing a free crosslinking group, a polymerization inhibitor may be added at the time of synthesis from the viewpoint of protecting the crosslinking group.

又，本實施形態中，就耐熱性之觀點而言，較佳為(A)含自由交聯基之聚矽氧烷亦具有下述結構： Further, in the present embodiment, from the viewpoint of heat resistance, it is preferred that (A) the polyoxyalkylene having a free crosslinking group also has the following structure:

{式中，Ph表示苯基}。In the formula, Ph represents a phenyl group}.

(A)含自由交聯基之聚矽氧烷之矽原子中，具有上述結構之比率較佳為10mol%~80mol%，更佳為30mol%~70mol%，進而佳為40mol%~60mol%。(A) In the ruthenium atom of the polyoxyalkylene having a free crosslinking group, the ratio of the above structure is preferably from 10 mol% to 80 mol%, more preferably from 30 mol% to 70 mol%, still more preferably from 40 mol% to 60 mol%.

本實施形態中，(A)含自由交聯基之聚矽氧烷之含量並無特別限制，可根據所需之膜厚或用途而任意選擇，就耐熱透明性之觀點而言，相對於感光性樹脂組合物中之總固形物成分100質量份，較佳為1質量份以上，更佳為10質量份以上，進而佳為15質量份以上，另一方面，就耐龜裂性之觀點而言，較佳為99質量份以下，更佳為90質量份以下，進而佳為85質量份以下。In the present embodiment, the content of the (A) polyoxyalkylene containing a free crosslinking group is not particularly limited, and may be arbitrarily selected depending on the desired film thickness or use, and is relative to the photosensitive material from the viewpoint of heat-resistant transparency. 100 parts by mass of the total solid content in the resin composition is preferably 1 part by mass or more, more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, and on the other hand, from the viewpoint of crack resistance. In other words, it is preferably 99 parts by mass or less, more preferably 90 parts by mass or less, and still more preferably 85 parts by mass or less.

<(B)光自由基(聚合)起始劑><(B) Photoradical (polymerization) initiator>

為了對聚矽氧烷組合物賦予感光性圖案之形成性，重要的是將(B)光自由基起始劑添加至聚矽氧烷組合物中。In order to impart formability to the photosensitive pattern to the polyoxyalkylene composition, it is important to add (B) a photoradical initiator to the polyoxyalkylene composition.

作為(B)光自由基起始劑，可列舉下述(1)~(10)之光自由基起始劑：Examples of the (B) photoradical initiator include the following photoradical initiators (1) to (10):

(1)二苯甲酮衍生物：例如二苯甲酮、鄰苯甲醯基苯甲酸甲酯、4-苯甲醯基-4'-甲基二苯基酮、二苄基酮、茀酮(1) Benzophenone derivatives: for example, benzophenone, methyl ortho-benzoylbenzoate, 4-benzylidene-4'-methyldiphenyl ketone, dibenzyl ketone, anthrone

(2)苯乙酮衍生物：例如2,2'-二乙氧基苯乙酮、2-羥基-2-甲基苯丙酮、2,2-二甲氧基-1,2-二苯乙烷-1-酮(BASF公司製造，IRGACURE651)、1-羥基環己基苯基酮(BASF公司製造，IRGACURE184)、2-甲基-1-[4-(甲硫基)苯基]-2-啉基丙烷-1-酮(BASF公司製造，IRGACURE907)、2-羥基-1-{4-[4-(2-羥基-2-甲基丙醯基)-苄基]-苯基}-2-甲基丙烷-1-酮(BASF公司製造，IRGACURE127)、苯基乙醛酸甲酯(2) Acetophenone derivatives: for example, 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethyl Alkan-1-one (manufactured by BASF Corporation, IRGACURE 651), 1-hydroxycyclohexyl phenyl ketone (manufactured by BASF Corporation, IRGACURE 184), 2-methyl-1-[4-(methylthio)phenyl]-2- Lolinylpropan-1-one (manufactured by BASF Corporation, IRGACURE 907), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropenyl)-benzyl]-phenyl}-2 -methylpropan-1-one (manufactured by BASF, IRGACURE 127), methyl phenylglyoxylate

(3)9-氧硫衍生物：例如9-氧硫、2-甲基-9-氧硫、2- 異丙基-9-氧硫、二乙基-9-氧硫 (3) 9-oxygen sulfur Derivatives: for example, 9-oxosulfur 2-methyl-9-oxosulfur 2-isopropyl-9-oxosulfur Diethyl-9-oxosulfur

(4)苯偶醯衍生物：例如苯偶醯、苯偶醯二甲基縮酮、苯偶醯-β-甲氧基乙基縮醛(4) Benzene oxime derivatives: for example, benzoin, benzoin dimethyl ketal, benzoin-β-methoxyethyl acetal

(5)安息香衍生物：例如安息香、安息香甲醚、2-羥基-2-甲基-1苯基丙烷-1-酮(BASF公司製造，DAROCURE1173)(5) Benzoin derivatives: for example, benzoin, benzoin methyl ether, 2-hydroxy-2-methyl-1phenylpropan-1-one (manufactured by BASF Corporation, DAROCURE 1173)

(6)肟系化合物：例如1-苯基-1,2-丁二酮-2-(O-甲氧基羰基)肟、1-苯基-1,2-丙二酮-2-(O-甲氧基羰基)肟、1-苯基-1,2-丙二酮-2-(O-乙氧基羰基)肟、1-苯基-1,2-丙二酮-2-(O-苯甲醯基)肟、1,3-二苯基丙三酮-2-(O-乙氧基羰基)肟、1-苯基-3-乙氧基丙三酮-2-(O-苯甲醯基)肟、1,2-辛二酮，1-[4-(苯硫基)-2-(O-苯甲醯基肟)](BASF公司製造，IRGACURE OXE01)、乙酮，1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(O-乙醯基肟)(BASF公司製造，IRGACURE OXE02)(6) Lanthanide compounds: for example, 1-phenyl-1,2-butanedione-2-(O-methoxycarbonyl)anthracene, 1-phenyl-1,2-propanedione-2-(O -methoxycarbonyl)anthracene, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)anthracene, 1-phenyl-1,2-propanedione-2-(O -benzimidyl)anthracene, 1,3-diphenylpropanetrione-2-(O-ethoxycarbonyl)anthracene, 1-phenyl-3-ethoxypropanetrione-2-(O- Benzopyridinium), 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzylidenehydrazine)] (manufactured by BASF Corporation, IRGACURE OXE01), ethyl ketone, 1-[9-Ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O-ethenylhydrazine) (manufactured by BASF Corporation, IRGACURE OXE02)

(7)α-羥基酮系化合物：例如2-羥基-2-甲基-1-苯基丙烷-1-酮、1-[4-(2-羥基乙氧基)苯基]-2-羥基-2-甲基-1-丙烷-1-酮、2-羥基-1-{4-[4-(2-羥基-2-甲基丙醯基)-苄基]苯基}-2-甲基丙烷(7) α-hydroxyketone-based compound: for example, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxyl -2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropenyl)-benzyl]phenyl}-2-yl Propane

(8)α-胺基烷基苯酮系化合物：例如2-苄基-2-二甲基胺基-1-(4-啉基苯基)-丁酮-1(BASF公司製造，IRGACURE369)、2-二甲基胺基-2-(4-甲基苄基)-1-(4-啉-4-基-苯基)丁烷-1-酮(BASF公司製造，IRGACURE379)(8) α-Aminoalkylphenone-based compound: for example, 2-benzyl-2-dimethylamino-1-(4- Polinylphenyl)-butanone-1 (manufactured by BASF Corporation, IRGACURE 369), 2-dimethylamino-2-(4-methylbenzyl)-1-(4- Porphyrin-4-yl-phenyl)butan-1-one (manufactured by BASF Corporation, IRGACURE379)

(9)氧化膦系化合物：例如雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦(BASF公司製造，IRGACURE819)、雙(2,6-二甲氧基苯甲醯基)-2,4,4-三甲基-戊基氧化膦、2,4,6-三甲基苯甲醯基-二苯基-氧化膦(BASF公司製造，Lucirin TPO)(9) a phosphine oxide-based compound: for example, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide (manufactured by BASF Corporation, IRGACURE 819), bis(2,6-dimethoxybenzamide) Indenyl)-2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide (manufactured by BASF, Lucirin TPO)

(10)二茂鈦化合物：例如雙(η5-2,4-環戊二烯-1-基)-雙(2,6-二氟-3-(1H-吡咯-1-基)苯基)鈦(BASF公司製造，IRGACURE784)(10) Titanocene compound: for example, bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl) Titanium (manufactured by BASF, IRGACURE784)

上述(1)~(10)之光自由基起始劑可分別單獨使用，亦可組合使用 2種以上。The above photoactive radical initiators of (1) to (10) may be used alone or in combination. 2 or more types.

上述(1)~(10)之光自由基起始劑中，尤其是就提高光感度及透明性之觀點而言，更佳為(5)安息香衍生物或(9)氧化膦系化合物。The photoradical initiator of the above (1) to (10) is more preferably a (5) benzoin derivative or a (9) phosphine oxide compound from the viewpoint of improving light sensitivity and transparency.

就獲得充分之感度之觀點而言，相對於聚矽氧烷組合物中之總固形物成分100質量份，(B)光自由基起始劑之含量較佳為0.01質量份以上，更佳為0.1質量份以上，另一方面，就使感光性樹脂層底之部分充分硬化之觀點而言，較佳為15質量份以下，更佳為10質量份以下。From the viewpoint of obtaining sufficient sensitivity, the content of the (B) photoradical initiator is preferably 0.01 parts by mass or more, more preferably 100 parts by mass based on the total solid content of the polyoxyalkylene composition. From the viewpoint of sufficiently curing a portion of the bottom of the photosensitive resin layer, it is preferably 15 parts by mass or less, and more preferably 10 parts by mass or less.

<(C)硝醯基化合物><(C)Nitrate-based compound>

(C)硝醯基化合物係含有下述通式(V)： (C) The nitroxide compound contains the following general formula (V):

{式中，R1 、R2 、R3 及R4 分別獨立地表示氫原子或碳數1~10之一價有機基，且R1 與R2 、或R3 與R4 可相互鍵結而形成環結構}所表示之結構之化合物。R1 、R2 、R3 及R4 較佳為碳數1~10之一價有機基。本實施態樣之聚矽氧烷組合物藉由含有(C)硝醯基化合物，於氮氣環境下硬化後之耐龜裂性優異。Wherein R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, and R 1 and R 2 or R 3 and R 4 may be bonded to each other. The compound which forms the structure represented by the ring structure}. R 1 , R 2 , R 3 and R 4 are preferably a one-valent organic group having 1 to 10 carbon atoms. The polyoxyalkylene composition of the present embodiment is excellent in crack resistance after being cured under a nitrogen atmosphere by containing the (C) cerium-based compound.

上述通式(V)中，R1 、R2 、R3 及R4 可分別獨立為烷基或經雜原子取代之烷基。作為烷基，較佳可列舉甲基、乙基、丙基等，而且作為雜原子，較佳可列舉鹵素、氧、硫、氮等。In the above formula (V), R 1 , R 2 , R 3 and R 4 each independently may be an alkyl group or an alkyl group substituted with a hetero atom. The alkyl group is preferably a methyl group, an ethyl group or a propyl group, and examples of the hetero atom include halogen, oxygen, sulfur, nitrogen and the like.

作為本實施形態中所用之(C)硝醯基化合物，例如較佳為二-第三丁基氮氧化物、二-1,1-二甲基丙基氮氧化物、二-1,2-二甲基丙基氮氧 化物、二-2,2-二甲基丙基氮氧化物及下述通式(VI)、(VII)或(VIII)所表示之化合物。其中，就於氮氣環境下硬化後之耐龜裂性之觀點而言，更佳為下述通式(VI)、(VII)或(VIII)所表示之化合物。As the (C) nitrate-based compound used in the present embodiment, for example, di-tert-butyl oxynitride, di-1,1-dimethylpropyl oxynitride, bis-1,2- are preferable. Dimethyl propyl nitrox a compound, a di-2,2-dimethylpropyl oxynitride, and a compound represented by the following formula (VI), (VII) or (VIII). Among them, from the viewpoint of crack resistance after hardening in a nitrogen atmosphere, a compound represented by the following formula (VI), (VII) or (VIII) is more preferable.

{式中，R5 表示氫原子、碳數1~12之烷基、羥基、胺基、羧酸基、氰基、雜原子取代烷基，或經由醚、酯、醯胺或胺基甲酸酯鍵而鍵結之一價有機基，R6 表示二或三價有機基，n1 及m1 為滿足1≦n1 +m1 ≦2之整數，n2 及m2 為滿足1≦n2 +m2 ≦2之整數，n3 及m3 為滿足1≦n3 +m3 ≦2之整數，而且1為2或3之整數}In the formula, R 5 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a hydroxyl group, an amine group, a carboxylic acid group, a cyano group, a hetero atom-substituted alkyl group, or an ether, an ester, a guanamine or an aminocarboxylic acid. The ester bond is bonded to a monovalent organic group, R 6 represents a divalent or trivalent organic group, n 1 and m 1 are integers satisfying 1≦n 1 +m 1 ≦2, and n 2 and m 2 are satisfying 1≦n An integer of 2 + m 2 ≦ 2, n 3 and m 3 are integers satisfying 1≦n 3 + m 3 ≦ 2, and 1 is an integer of 2 or 3}

作為上述通式(VI)所表示之化合物，具體可列舉下述化合物。Specific examples of the compound represented by the above formula (VI) include the following compounds.

[化13] [Chemistry 13]

{式中，R20 分別獨立地表示碳數1~20之直鏈狀或支鏈狀之烷基、芳香族基、或脂環式基，而且R20 亦可含有其他取代基}In the formula, R 20 each independently represents a linear or branched alkyl group, an aromatic group or an alicyclic group having 1 to 20 carbon atoms, and R 20 may further contain other substituents}

作為上述通式(VII)所表示之化合物，具體可列舉下述化合物。Specific examples of the compound represented by the above formula (VII) include the following compounds.

[化14] [Chemistry 14]

作為上述通式(VIII)所表示之化合物，具體可列舉下述化合物。Specific examples of the compound represented by the above formula (VIII) include the following compounds.

[化15] [化15]

作為進而佳之(C)硝醯基化合物，就耐龜裂性之觀點而言，可列舉：2,2,6,6-四甲基哌啶-1-氧自由基、4-羥基-2,2,6,6-四甲基哌啶-1-氧自由基、4-胺基-2,2,6,6-四甲基哌啶-1-氧自由基、4-羧基-2,2,6,6-四甲 基哌啶-1-氧自由基、4-氰基-2,2,6,6-四甲基哌啶-1-氧自由基、4-甲基丙烯酸-2,2,6,6-四甲基哌啶-1-氧自由基、4-丙烯酸-2,2,6,6-四甲基哌啶-1-氧自由基、4-側氧基-2,2,6,6-四甲基哌啶-1-氧自由基、3-羧基-2,2,5,5-四甲基吡咯啶-1-氧自由基、4-乙醯胺-2,2,6,6-四甲基哌啶-1-氧自由基、4-(2-氯乙醯胺)-2,2,6,6-四甲基哌啶-1-氧自由基、4-羥基-2,2,6,6-四甲基哌啶-1-氧基苯甲酸酯自由基、4-異硫氰基-2,2,6,6-四甲基哌啶-1-氧自由基、4-(2-碘乙醯胺)-2,2,6,6-四甲基哌啶-1-氧自由基、4-甲氧基-2,2,6,6-四甲基哌啶-1-氧自由基。(C)硝醯基化合物可單獨使用，亦可組合使用2種以上。Further, as a further preferred (C) nitrate-based compound, from the viewpoint of crack resistance, 2,2,6,6-tetramethylpiperidine-1-oxyl radical, 4-hydroxy-2, 2,6,6-tetramethylpiperidine-1-oxyl radical, 4-amino-2,2,6,6-tetramethylpiperidine-1-oxyl radical, 4-carboxy-2,2 ,6,6-four Isopiperidin-1-oxyl radical, 4-cyano-2,2,6,6-tetramethylpiperidine-1-oxyl radical, 4-methacrylic acid-2,2,6,6-tetra Methylpiperidine-1-oxyl radical, 4-acrylic acid-2,2,6,6-tetramethylpiperidine-1-oxyl radical, 4-sided oxy-2,2,6,6-tetra Methylpiperidine-1-oxyl radical, 3-carboxy-2,2,5,5-tetramethylpyrrolidine-1-oxyl radical, 4-acetamide-2,2,6,6-tetra Methylpiperidine-1-oxyl radical, 4-(2-chloroethylammonium)-2,2,6,6-tetramethylpiperidine-1-oxyl radical, 4-hydroxy-2,2, 6,6-Tetramethylpiperidin-1-oxobenzoate free radical, 4-isothiocyanato-2,2,6,6-tetramethylpiperidine-1-oxyl radical, 4- (2-iodoacetamide)-2,2,6,6-tetramethylpiperidine-1-oxyl radical, 4-methoxy-2,2,6,6-tetramethylpiperidine-1 - Oxygen free radicals. (C) The nitroxide compound may be used singly or in combination of two or more.

(C)硝醯基化合物只要於聚矽氧烷組合物中微量含有即可，就耐龜裂性之觀點而言，相對於聚矽氧烷組合物中之總固形物成分100質量份，(C)硝醯基化合物之含量較佳為0.005質量份以上，更佳為0.009質量份以上，另一方面，就透明性之觀點而言，較佳為2質量份以下，更佳為1質量份以下。(C) The cerium-based compound may be contained in a trace amount in the polyoxyalkylene composition, and is 100 parts by mass based on the total solid content in the polyoxyalkylene composition from the viewpoint of crack resistance. C) The content of the nitroxide-based compound is preferably 0.005 parts by mass or more, more preferably 0.009 parts by mass or more, and on the other hand, from the viewpoint of transparency, it is preferably 2 parts by mass or less, more preferably 1 part by mass. the following.

<(D)含有光聚合性雙鍵之化合物><(D) Compound containing photopolymerizable double bond>

本實施形態中，就耐龜裂性之觀點而言，較佳為聚矽氧烷組合物進而含有(D)含有光聚合性雙鍵之化合物。(D)含有光聚合性雙鍵之化合物係於一分子內含有至少一個光聚合性雙鍵基之聚合性單體。In the present embodiment, from the viewpoint of crack resistance, the polyoxyalkylene composition further preferably contains (D) a compound containing a photopolymerizable double bond. (D) The compound containing a photopolymerizable double bond is a polymerizable monomer containing at least one photopolymerizable double bond group in one molecule.

作為(D)含有光聚合性雙鍵之化合物，例如可列舉：聚乙二醇二(甲基)丙烯酸酯[乙二醇單元數2~20]、聚(1,2-丙二醇)二(甲基)丙烯酸酯[1,2-丙二醇單元數2~20]、聚(1,4-丁二醇)二(甲基)丙烯酸酯[1,4-丁二醇單元數2~10]、三-2-羥基乙基異氰尿酸酯三(甲基)丙烯酸酯、亞甲基雙丙烯醯胺、乙二醇二縮水甘油醚-(甲基)丙烯酸加成物、甘油二縮水甘油醚-(甲基)丙烯酸加成物、雙酚A二縮水甘油醚-(甲基)丙烯酸加成物、N,N'-雙(2-甲基丙烯醯氧基乙基)脲琥珀酸改性季戊四醇三(甲基)丙烯酸酯、鄰苯二甲酸改性季戊四醇三(甲基)丙烯酸酯、間苯 二甲酸改性季戊四醇三(甲基)丙烯酸酯、對苯二甲酸改性季戊四醇三(甲基)丙烯酸酯、於雙酚A之兩端分別加成平均2莫耳之環氧丙烷與平均6莫耳之環氧乙烷而成之聚伸烷基二醇之二甲基丙烯酸酯、於雙酚A之兩端分別加成平均5莫耳之環氧乙烷而成之聚乙二醇之二甲基丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、3-甲基-1,5-戊二醇二(甲基)丙烯酸酯、2-丁基-2-乙基-1,3-丙二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、1,10-癸二醇二(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、三環癸烷二甲醇(甲基)丙烯酸酯、1,4-環己二醇二(甲基)丙烯酸酯、2-二(對羥基苯基)丙烷二(甲基)丙烯酸酯、甘油三(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、聚氧基丙基三羥甲基丙烷三(甲基)丙烯酸酯、聚氧基乙基三羥甲基丙烷三丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、三羥甲基丙烷三縮水甘油醚三(甲基)丙烯酸酯、雙酚A二縮水甘油醚二(甲基)丙烯酸酯、及β-羥基丙基-β'-(丙烯醯氧基)丙基鄰苯二甲酸酯、苯氧基聚乙二醇(甲基)丙烯酸酯、壬基苯氧基聚乙二醇(甲基)丙烯酸酯、壬基苯氧基聚伸烷基二醇(甲基)丙烯酸酯、聚丙二醇單(甲基)丙烯酸酯、(甲基)丙烯酸-2-羥基乙酯、(甲基)丙烯酸-3-羥基丙酯、(甲基)丙烯酸-4-羥基丁酯、甘油單(甲基)丙烯酸酯、4-羥基乙烯基苯、丙烯酸-2-羥基-3-苯氧基丙酯或該等單體之己內酯加成物等。Examples of the (D) compound containing a photopolymerizable double bond include polyethylene glycol di(meth)acrylate [ethylene glycol unit number 2 to 20] and poly(1,2-propanediol) di(a). Acrylate [1,2-propanediol unit number 2-20], poly(1,4-butanediol) di(meth)acrylate [1,4-butanediol unit number 2~10], three 2-hydroxyethyl isocyanurate tri(meth)acrylate, methylenebis acrylamide, ethylene glycol diglycidyl ether-(meth)acrylic acid adduct, glycerol diglycidyl ether (Meth)acrylic acid adduct, bisphenol A diglycidyl ether-(meth)acrylic acid adduct, N,N'-bis(2-methacryloxyethyl)urea succinic acid modified pentaerythritol Tris(meth)acrylate, phthalic acid modified pentaerythritol tri(meth)acrylate, m-benzene Dicarboxylic acid modified pentaerythritol tri (meth) acrylate, terephthalic acid modified pentaerythritol tri (meth) acrylate, respectively added to the two ends of bisphenol A with an average of 2 moles of propylene oxide and an average of 6 Mo a dimethacrylate of a polyalkylene glycol formed by the ethylene oxide of the ear, and a polyethylene glycol of an average of 5 moles of ethylene oxide at both ends of the bisphenol A. Methacrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylic acid Ester, 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(a) Acrylate, glycerol di(meth)acrylate, tricyclodecane dimethanol (meth) acrylate, 1,4-cyclohexanediol di(meth) acrylate, 2-di(p-hydroxybenzene) Propane di(meth)acrylate, tris(meth)acrylate, trimethylolpropane tri(meth)acrylate, polyoxypropyltrimethylolpropane tri(meth)acrylate , polyoxyethyl trimethylolpropane triacrylate, pentaerythritol four ( Acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane triglycidyl ether tri(meth) acrylate, bisphenol A diglycidyl ether di(meth) acrylate, and β- Hydroxypropyl-β'-(propylene decyloxy)propyl phthalate, phenoxy polyethylene glycol (meth) acrylate, nonyl phenoxy polyethylene glycol (meth) acrylate Ester, nonylphenoxy polyalkylene glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylate -3- Hydroxypropyl ester, 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, 4-hydroxyvinylbenzene, 2-hydroxy-3-phenoxypropyl acrylate or such monomers A caprolactone adduct or the like.

又，(D)含有光聚合性雙鍵之化合物亦可進而含有羧基。作為進而含有羧酸之(D)含有光聚合性雙鍵之化合物，例如可列舉：(甲基)丙烯酸、(甲基)丙烯酸羧基乙酯、(甲基)丙烯酸羧基戊酯、2-(甲基)丙烯醯氧基乙基琥珀酸、2-(甲基)丙烯醯氧基乙基六氫鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基鄰苯二甲酸、2,2,2-三丙烯醯氧基甲基乙基琥珀酸等。該等可分別單獨使用，亦可組合使用2種以上。Further, (D) the compound containing a photopolymerizable double bond may further contain a carboxyl group. Examples of the compound containing a photopolymerizable double bond of (D) containing a carboxylic acid include (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, and 2-(A). Acryloxyethyl succinic acid, 2-(methyl) propylene methoxyethyl hexahydrophthalic acid, 2-(methyl) propylene methoxyethyl phthalate, 2, 2 2-tripropylene methoxymethylethyl succinic acid or the like. These may be used alone or in combination of two or more.

就使各成分充分交聯而發揮對基板之密接性之觀點而言，相對 於聚矽氧烷組合物中之總固形物成分100質量份，(D)含有光聚合性雙鍵之化合物之含量較佳為5質量份以上，更佳為10質量份以上，另一方面，就減少顯影後之殘渣之觀點而言，較佳為45質量份以下，更佳為40質量份以下。In terms of making the components sufficiently crosslinked to exert adhesion to the substrate, The content of the compound containing a photopolymerizable double bond in (D) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, based on 100 parts by mass of the total solid content of the polyoxyalkylene composition. From the viewpoint of reducing the residue after development, it is preferably 45 parts by mass or less, more preferably 40 parts by mass or less.

<(E)紫外線吸收劑><(E) UV absorber>

本實施形態中，為了提高聚矽氧烷組合物之耐光性，減少顯影時之殘渣，較佳為於聚矽氧烷組合物中含有(E)紫外線吸收劑。又，藉由將(E)紫外線吸收劑與(C)硝醯基化合物組合使用，可大幅度地提高聚矽氧烷組合物之解析性，故而較佳。作為(E)紫外線吸收劑，例如可列舉苯并***系化合物、二苯甲酮系化合物等。具體而言，作為(E)紫外線吸收劑，例如可列舉：2-(2,4-二羥基苯基)-4,6-雙(2,4-二甲基苯基)-1,3,5-三與(2-乙基己基)-縮水甘油酸酯之反應產物(BASF公司製造，TINUVIN405)、2-(2H苯并***-2-基)苯酚、2-(2H苯并***-2-基)-4,6-第三戊基苯酚、2-(2H苯并***-2-基)-4-(1,1,3,3-四甲基丁基)苯酚、2-(2H苯并***-2-基)-6-十二烷基-4-甲基苯酚、2-(2'-羥基-5'-甲基丙烯醯氧基乙基苯基)-2H-苯并***、2-羥基-4-甲氧基二苯甲酮等。In the present embodiment, in order to increase the light resistance of the polyoxyalkylene composition and to reduce the residue during development, it is preferred to contain (E) an ultraviolet absorber in the polyoxyalkylene composition. Further, by using the (E) ultraviolet absorbing agent in combination with the (C) cerium sulfhydryl compound, the resolution of the polyoxyalkylene composition can be greatly improved, which is preferable. Examples of the (E) ultraviolet absorber include a benzotriazole-based compound and a benzophenone-based compound. Specifically, examples of the (E) ultraviolet absorber include 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3. 5-three Reaction product with (2-ethylhexyl)-glycidyl ester (manufactured by BASF Corporation, TINUVIN 405), 2-(2H benzotriazol-2-yl)phenol, 2-(2H benzotriazole-2- -4,6-third amyl phenol, 2-(2H benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2H Benzotriazol-2-yl)-6-dodecyl-4-methylphenol, 2-(2'-hydroxy-5'-methacryloxyethylphenyl)-2H-benzo Triazole, 2-hydroxy-4-methoxybenzophenone, and the like.

於將(E)紫外線吸收劑添加至聚矽氧烷組合物中之情形時，就防止未曝光部分之硬化之觀點而言，相對於聚矽氧烷組合物中之總固形物成分100質量份，(E)紫外線吸收劑之含量較佳為0.01質量份以上，更佳為0.1質量份以上，另一方面，就由曝光時之自由基產生所得的圖案形成性之觀點而言，較佳為10質量份以下，更佳為5質量份以下。In the case where (E) the ultraviolet absorber is added to the polyoxyalkylene composition, 100 parts by mass relative to the total solid content in the polyoxynitride composition from the viewpoint of preventing hardening of the unexposed portion The content of the (E) ultraviolet absorber is preferably 0.01 parts by mass or more, more preferably 0.1 part by mass or more. On the other hand, from the viewpoint of pattern formation property due to radical generation during exposure, it is preferably 10 parts by mass or less, more preferably 5 parts by mass or less.

<(F)鹼可溶性樹脂><(F) alkali soluble resin>

本實施形態中，聚矽氧烷組合物較佳為進而含有(F)鹼可溶性樹脂。又，於含自由交聯基之聚矽氧烷含有鹼可溶性基、且可實現聚矽 氧烷組合物之鹼顯影之情形時，較佳為將(F)鹼可溶性樹脂添加至聚矽氧烷組合物中。In the present embodiment, the polyoxyalkylene composition preferably further contains (F) an alkali-soluble resin. Further, the polyoxyalkylene containing a free crosslinking group contains an alkali-soluble group and can be polymerized. In the case of alkali development of the oxyalkylene composition, it is preferred to add (F) an alkali-soluble resin to the polyoxyalkylene composition.

又，所謂(F)鹼可溶性樹脂，係指含有鹼可溶性基、且酸值為10~200mgKOH/g之鹼可溶性樹脂。Moreover, the (F) alkali-soluble resin means an alkali-soluble resin containing an alkali-soluble group and having an acid value of 10 to 200 mgKOH/g.

就相溶性之觀點而言，(F)鹼可溶性樹脂之酸值較佳為接近(A)含自由交聯基之聚矽氧烷，就減少顯影時之殘渣之觀點而言，較佳為10mgKOH/g以上，更佳為20mgKOH/g以上，另一方面，就圖案之密接性之觀點而言，較佳為200mgKOH/g以下，更佳為190mgKOH/g以下。From the viewpoint of compatibility, the acid value of the (F) alkali-soluble resin is preferably close to (A) a polyoxyalkylene having a free crosslinking group, and from the viewpoint of reducing the residue at the time of development, it is preferably 10 mgKOH. More preferably, it is 20 mgKOH/g or more, and on the other hand, from the viewpoint of the adhesion of the pattern, it is preferably 200 mgKOH/g or less, more preferably 190 mgKOH/g or less.

(F)鹼可溶性樹脂只要含有鹼可溶性基，且酸值為10~200mgKOH/g，則並無特別限制，較佳為於一分子中含有羧基、二羧酸酐基、或二羧酸酐基之殘基。聚矽氧烷組合物藉由於(F)鹼可溶性樹脂中含有羧基，而維持耐熱透明性並且表現出鹼溶性，可獲得良好之膜物性。(F) The alkali-soluble resin is not particularly limited as long as it contains an alkali-soluble group and has an acid value of 10 to 200 mgKOH/g, and preferably contains a carboxyl group, a dicarboxylic anhydride group, or a dicarboxylic anhydride group in one molecule. base. The polyoxyalkylene composition can maintain good film physical properties by maintaining heat-resistant transparency and exhibiting alkali solubility by containing a carboxyl group in the (F) alkali-soluble resin.

(F)鹼可溶性樹脂之含量並無特別限制，可根據所需之膜厚或用途而任意選擇，就耐熱龜裂性之觀點而言，相對於聚矽氧烷組合物中之總固形物成分100質量份，較佳為1質量份以上，更佳為5質量份以上，進而佳為10質量份以上，另一方面，就耐熱透明性之觀點而言，較佳為50質量份以下，更佳為45質量份以下，進而佳為40質量份以下。(F) The content of the alkali-soluble resin is not particularly limited and may be arbitrarily selected depending on the desired film thickness or use, and the total solid content in the polyoxyalkylene composition is from the viewpoint of heat crack resistance. 100 parts by mass, preferably 1 part by mass or more, more preferably 5 parts by mass or more, further preferably 10 parts by mass or more, and from the viewpoint of heat-resistant transparency, it is preferably 50 parts by mass or less. It is preferably 45 parts by mass or less, and more preferably 40 parts by mass or less.

(F)鹼可溶性樹脂較佳為含有鹼可溶性基，而且為選自由下述(1)~(5)：(1)以聚合性雙鍵之反應物為主體而構成之乙烯基聚合物、(2)以環氧基與羥基之加成反應物為主體而構成之環氧聚合物、(3)以酚與甲醛之反應物為主體而構成之芳香族亞甲基聚合物、(4)以二醇與二異氰酸酯之反應物為主體而構成之胺基甲酸酯聚 合物、及(5)以二羧酸與二環氧化物之反應物為主體而構成之酯聚合物(F) The alkali-soluble resin preferably contains an alkali-soluble group, and is a vinyl polymer selected from the group consisting of the following (1) to (5): (1) a polymerizable double bond; 2) an epoxy polymer mainly composed of an addition reaction product of an epoxy group and a hydroxyl group; (3) an aromatic methylene polymer mainly composed of a reactant of a phenol and formaldehyde, and (4) A urethane polymer composed of a reactant of a diol and a diisocyanate And (5) an ester polymer mainly composed of a reactant of a dicarboxylic acid and a diepoxide

所組成之群中之至少一種聚合物。再者，上述聚合物(1)~(5)中，所謂主體，係指分子內含有70莫耳%以上之該成分。At least one polymer of the group formed. In the above polymers (1) to (5), the term "main body" means that the molecule contains 70 mol% or more of the component.

上述聚合物(1)~(5)中，以下特別對(1)、(3)加以詳細說明。Among the above polymers (1) to (5), (1) and (3) will be specifically described below.

(1)以聚合性雙鍵之反應物為主體而構成之乙烯基聚合物(1) A vinyl polymer mainly composed of a reactant of a polymerizable double bond

例如可列舉下述通式(4)或下述通式(6)所表示之含羧基之乙烯基聚合物。For example, a carboxyl group-containing vinyl polymer represented by the following formula (4) or the following formula (6) can be mentioned.

[式中，Rd為碳原子數為0~20之直鏈狀、支鏈狀或環狀之二價有機基，Re為下述通式(5)： [wherein, Rd is a linear, branched or cyclic divalent organic group having 0 to 20 carbon atoms, and Re is a following general formula (5):

{式中，Rb為碳原子數為1~20之直鏈狀、支鏈狀或環狀之一價有機基、或者含有光聚合性雙鍵基之一價有機基，而且Rc為下述通式(3)：[化18] In the formula, Rb is a linear, branched or cyclic one-valent organic group having 1 to 20 carbon atoms, or a monovalent organic group containing a photopolymerizable double bond group, and Rc is the following Formula (3): [Chem. 18]

(式中，Ra為碳原子數為2~16之直鏈狀、支鏈狀或環狀之二價有機基)所表示之基、或氫}所表示之一價有機基、或氫，Rf為碳原子數1~20之直鏈狀、支鏈狀或環狀之一價有機基，Rh分別獨立為甲基或氫，m為選自1~500之整數，而且n為選自10~1,000中之整數](wherein, Ra is a group represented by a linear, branched or cyclic divalent organic group having 2 to 16 carbon atoms), or a monovalent organic group represented by hydrogen, or hydrogen, Rf Is a linear, branched or cyclic one-valent organic group having 1 to 20 carbon atoms, Rh is independently methyl or hydrogen, m is an integer selected from 1 to 500, and n is selected from 10~ Integer of 1,000]

{式中，Rb為碳原子數為1~20之直鏈狀、支鏈狀或環狀之一價有機基、或者含有光聚合性雙鍵基之一價有機基，Rc為上述通式(5)所表示之基或氫，Rd為碳原子數為0~20之直鏈狀、支鏈狀或環狀之二價有機基、或者可含有光聚合性雙鍵之二價有機基，Rf為碳原子數1~20之直鏈狀、支鏈狀或環狀之一價有機基，Rh為甲基或氫，m為選自1~500中之整數，而且n為選自10~1,000中之整數}In the formula, Rb is a linear, branched or cyclic one-valent organic group having 1 to 20 carbon atoms, or a monovalent organic group containing a photopolymerizable double bond group, and Rc is the above formula ( 5) a hydrogen or a hydrogen atom, and Rd is a linear, branched or cyclic divalent organic group having 0 to 20 carbon atoms or a divalent organic group which may contain a photopolymerizable double bond, Rf Is a linear, branched or cyclic one-valent organic group having 1 to 20 carbon atoms, Rh is a methyl group or hydrogen, m is an integer selected from 1 to 500, and n is selected from 10 to 1,000. Integer}

作為獲得含羧基之乙烯基聚合物之方法，例如可列舉以下3種方法：As a method of obtaining a carboxyl group-containing vinyl polymer, for example, the following three methods are mentioned:

(i)使選自α,β-不飽和羧酸中之至少一種化合物(a)，與選自(甲基)丙烯酸烷基酯、(甲基)丙烯酸羥基烷基酯、(甲基)丙烯醯胺與將其氮上之氫取代為烷基或烷氧基而成之化合物、苯乙烯及苯乙烯衍生物、 (甲基)丙烯腈及(甲基)丙烯酸縮水甘油酯中之至少一種化合物(b)進行乙烯基共聚合之方法。(i) at least one compound (a) selected from the group consisting of α,β-unsaturated carboxylic acids, and alkyl (meth)acrylate, hydroxyalkyl (meth)acrylate, (meth) propylene a guanamine and a compound obtained by substituting a hydrogen on the nitrogen for an alkyl group or an alkoxy group, a styrene and a styrene derivative, A method of vinyl copolymerization of at least one compound (b) of (meth)acrylonitrile and glycidyl (meth)acrylate.

(ii)使上述化合物(a)與上述化合物(b)進行乙烯基共聚合後，使乙烯基聚合物之羧基與選自一分子中含有環氧基與(甲基)丙烯酸基之化合物中之至少一種化合物(c)進行加成反應之方法。(ii) after copolymerizing the above compound (a) with the above compound (b), the carboxyl group of the vinyl polymer and a compound selected from the group consisting of an epoxy group and a (meth)acrylic group in one molecule A method in which at least one compound (c) is subjected to an addition reaction.

(iii)使上述化合物(b)與上述化合物(c)進行乙烯基聚合後，使乙烯基聚合物之環氧基與上述化合物(a)進行加成反應，進而使二羧酸酐(d)與所生成之羥基進行加成反應之方法。(iii) after the compound (b) and the compound (c) are subjected to vinyl polymerization, an epoxy group of the vinyl polymer is subjected to an addition reaction with the compound (a), and the dicarboxylic anhydride (d) is further A method in which the generated hydroxyl group is subjected to an addition reaction.

作為可用於製備含羧基之乙烯基聚合物之上述化合物(a)，例如可列舉：(甲基)丙烯酸、(甲基)丙烯酸、(甲基)丙烯酸羧基乙酯、(甲基)丙烯酸羧基戊酯、2-(甲基)丙烯醯氧基乙基琥珀酸、2-(甲基)丙烯醯氧基乙基六氫鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基鄰苯二甲酸、反丁烯二酸、桂皮酸、丁烯酸、伊康酸及順丁烯二酸半酯等。該等可分別單獨使用，亦可組合使用2種以上。Examples of the above compound (a) which can be used for preparing a carboxyl group-containing vinyl polymer include (meth)acrylic acid, (meth)acrylic acid, carboxyethyl (meth)acrylate, and carboxypentyl (meth)acrylate. Ester, 2-(meth) propylene methoxyethyl succinic acid, 2-(methyl) propylene methoxyethyl hexahydrophthalic acid, 2-(methyl) propylene oxiranyl ethyl benzene Dicarboxylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid and maleic acid half ester. These may be used alone or in combination of two or more.

作為可用於製備含羧基之乙烯基聚合物之上述化合物(b)，例如可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸-2-乙基己酯、(甲基)丙烯酸-2-羥基乙酯、(甲基)丙烯酸-2-羥基丙酯、(甲基)丙烯酸-4-羥基丁酯、己內酯(甲基)丙烯酸酯、壬基苯氧基聚丙二醇(甲基)丙烯酸酯、聚乙二醇單(甲基)丙烯酸酯、聚丙二醇單(甲基)丙烯酸酯、(甲基)丙烯醯胺、N-羥甲基丙烯醯胺、N-丁氧基甲基丙烯醯胺、苯乙烯、α-甲基苯乙烯、對甲基苯乙烯、對氯苯乙烯、(甲基)丙烯酸苄酯、(甲基)丙烯酸-4-羥基苄酯、(甲基)丙烯酸-4-甲氧基苄酯、(甲基)丙烯酸-4-甲基苄酯、(甲基)丙烯酸-4-氯苄酯、(甲基)丙烯腈、(甲基)丙烯酸縮水甘油酯、3-甲基-3-(甲基)丙烯酸酯、3-乙基-3-(甲基)丙烯醯氧基甲基氧雜環丁烷、(甲基)丙烯 酸六氟丙酯、3-(甲基)丙烯醯基丙基三甲氧基矽烷、3-(甲基)丙烯醯基丙基三乙氧基矽烷等。該等可分別單獨使用，亦可組合使用2種以上。As the above compound (b) which can be used for the preparation of the carboxyl group-containing vinyl polymer, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, (methyl) ) lauryl acrylate, cyclohexyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (a) 2-hydroxypropyl acrylate, 4-hydroxybutyl (meth) acrylate, caprolactone (meth) acrylate, nonyl phenoxy polypropylene glycol (meth) acrylate, polyethylene glycol Mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, (meth) acrylamide, N-methylol acrylamide, N-butoxy methacrylamide, styrene, alpha -methylstyrene, p-methylstyrene, p-chlorostyrene, benzyl (meth)acrylate, 4-hydroxybenzyl (meth)acrylate, 4-methoxybenzyl (meth)acrylate , 4-methylbenzyl (meth)acrylate, 4-chlorobenzyl (meth)acrylate, (meth)acrylonitrile, glycidyl (meth)acrylate, 3-methyl-3-( Methyl) acrylate, 3-ethyl-3-(methyl) propylene oxime Methyl oxetane, (meth) acrylamide Hexafluoropropyl acrylate, 3-(methyl) propylene decyl propyl trimethoxy decane, 3-(methyl) propylene decyl propyl triethoxy decane, and the like. These may be used alone or in combination of two or more.

可用於製備含羧基之乙烯基聚合物之上述化合物(c)只要為藉由利用常法使含有2個環氧基之環氧樹脂與(甲基)丙烯酸反應而得之環氧(甲基)丙烯酸酯之半酯，則並無特別限定。作為上述化合物(c)，例如可列舉：(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸-3,4-環氧環己基甲酯、(甲基)丙烯酸-3,4-環氧環己基乙酯、單氧化乙烯基環己烯；對苯二酚二縮水甘油醚、鄰苯二酚二縮水甘油醚、間苯二酚二縮水甘油醚等苯基二縮水甘油醚與(甲基)丙烯酸之半酯；雙酚-A型環氧樹脂、雙酚-F型環氧樹脂、雙酚-S型環氧樹脂、2,2-雙(4-羥基苯基)-1,1,1,3,3,3-六氟丙烷之環氧化合物等雙酚型環氧化合物與(甲基)丙烯酸之半酯；氫化雙酚-A型環氧樹脂、氫化雙酚-F型環氧樹脂、氫化雙酚-S型環氧樹脂、氫化2,2-雙(4-羥基苯基)-1,1,1,3,3,3-六氟丙烷之環氧化合物等氫化雙酚型環氧化合物與(甲基)丙烯酸之半酯；環己烷二甲醇二縮水甘油醚化合物等脂環式二縮水甘油醚化合物與(甲基)丙烯酸之半酯；1,6-己二醇二縮水甘油醚、1,4-丁二醇二縮水甘油醚、二乙二醇二縮水甘油醚等脂肪族二縮水甘油醚化合物與(甲基)丙烯酸之半酯等。該等可分別單獨使用，亦可組合使用2種以上。The above compound (c) which can be used for the preparation of the carboxyl group-containing vinyl polymer is an epoxy (methyl) obtained by reacting an epoxy resin having two epoxy groups with (meth)acrylic acid by a usual method. The acrylate half ester is not particularly limited. Examples of the above compound (c) include glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, and 3,4-epoxy ring (meth)acrylate. Hexylethyl ester, monooxyethylene cyclohexene; phenyl diglycidyl ether such as hydroquinone diglycidyl ether, catechol diglycidyl ether, resorcinol diglycidyl ether, and (methyl) Acrylic acid half ester; bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, bisphenol-S type epoxy resin, 2,2-bis(4-hydroxyphenyl)-1,1,1 , bisphenol type epoxy compound such as epoxy compound of 3,3,3-hexafluoropropane and half ester of (meth)acrylic acid; hydrogenated bisphenol-A type epoxy resin, hydrogenated bisphenol-F type epoxy resin Hydrogenated bisphenol ring such as hydrogenated bisphenol-S type epoxy resin or hydrogenated 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane epoxy compound a half ester of an oxygen compound and (meth)acrylic acid; an alicyclic diglycidyl ether compound such as a cyclohexane dimethanol diglycidyl ether compound and a half ester of (meth)acrylic acid; 1,6-hexanediol condensed water Glycerol ether, 1,4-butanediol diglycidyl ether, diethylene glycol dihydrate Petroleum ether, an aliphatic diglycidyl ether compound with (meth) acrylic acid ester of a half. These may be used alone or in combination of two or more.

作為可用於製備含羧基之乙烯基聚合物之上述化合物(d)，例如可列舉：琥珀酸酐、環己烷二羧酸酐、4-甲基-環己烷二羧酸酐、5-甲基-環己烷二羧酸酐、二環庚烷二羧酸酐、7-氧雜二環庚烷二羧酸酐、四氫鄰苯二甲酸酐、偏苯三甲酸酐、均苯四甲酸酐、己二酸酐、鄰苯二甲酸酐、(3-三甲氧基矽烷基丙基)琥珀酸酐、(3-三乙氧基矽烷基丙基)琥珀酸酐等多元酸酐。該等可分別單獨使用，亦可組合使用2種以上。Examples of the above compound (d) which can be used for preparing a carboxyl group-containing vinyl polymer include succinic anhydride, cyclohexane dicarboxylic anhydride, 4-methyl-cyclohexane dicarboxylic anhydride, and 5-methyl-ring. Hexanedicarboxylic anhydride, dicycloheptane dicarboxylic anhydride, 7-oxabicycloheptane dicarboxylic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic anhydride, ortho A polybasic acid anhydride such as phthalic anhydride, (3-trimethoxydecylpropyl) succinic anhydride or (3-triethoxydecylpropyl) succinic anhydride. These may be used alone or in combination of two or more.

含羧基之乙烯基聚合物之製備中之乙烯基共聚合可藉由常法進行，可為溶液聚合、懸浮聚合法、乳化聚合法等已知之方法，就操作之容易性而言，較佳為溶液聚合。作為此時可使用之聚合起始劑，較佳為10小時半生期溫度為60℃~120℃之範圍內者。作為此種聚合起始劑，例如可列舉：2,2'-偶氮二異丁腈、2,2'-偶氮雙(2,4-二甲基戊腈)、2,2'-偶氮雙(2-甲基丁基腈)、2,2'-偶氮雙(2-丙酸甲酯)、2,2'-偶氮雙(N-氰基己基-2-甲基丙醯胺)、2,2'-偶氮雙(N-(2-丙烯基)-2-甲基丙醯胺)等偶氮類；過氧化(2-乙基己酸)1,1,3,3-四甲基丁酯、過氧化-2-乙基己酸第三己酯、過氧化-2-乙基己酸第三戊酯、過氧化-2-乙基己酸第三丁酯、過氧化異丁酸第三丁酯、第三丁基過氧化順丁烯二酸、過氧化-3,5,5-三甲基己酸第三戊酯、過氧化月桂酸第三丁酯、過氧化苯甲酸第三己酯、過氧化乙酸第三丁酯、過氧化間甲苯甲醯基苯甲酸第三丁酯、過氧化苯甲酸第三丁酯等過氧酯類；過氧化異丙基單碳酸第三己酯、過氧化異丙基單碳酸第三丁酯、過氧化-2-乙基己基單碳酸第三丁酯等過氧化單碳酸酯類；雙-3,5,5-三甲基己醯基過氧化物、辛醯基過氧化物、月桂醯基過氧化物、苯甲醯基過氧化物、對氯苯甲醯基過氧化物等二醯基過氧化物類等；二異丙苯過氧化物、第三丁基異丙苯過氧化物等二烷基過氧化物類等。該等可分別單獨使用，亦可組合使用2種以上。The vinyl copolymerization in the preparation of the carboxyl group-containing vinyl polymer can be carried out by a usual method, and can be a known method such as solution polymerization, suspension polymerization method, emulsion polymerization method, etc., and in terms of ease of handling, it is preferably Solution polymerization. As the polymerization initiator which can be used at this time, it is preferred that the 10-hour half-life temperature is in the range of 60 ° C to 120 ° C. Examples of such a polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-couple. Nitrogen bis(2-methylbutyl nitrile), 2,2'-azobis(2-propionic acid methyl ester), 2,2'-azobis(N-cyanohexyl-2-methylpropionamidine) Amines such as amines, 2,2'-azobis(N-(2-propenyl)-2-methylpropionamide); (2-ethylhexanoic acid) 1,1,3, 3-tetramethylbutyl ester, third hexyl peroxy-2-ethylhexanoate, third amyl peroxy-2-ethylhexanoate, tert-butyl peroxy-2-ethylhexanoate, Third butyl peroxybutyrate, tert-butyl peroxy maleic acid, third amyl peroxy-3,5,5-trimethylhexanoate, third butyl laurate, Peroxy esters such as third hexyl peroxybenzoate, tert-butyl peroxyacetate, tert-butyl peroxytolylbenzoic acid, and tert-butyl peroxybenzoate; isopropyl peroxide Peroxymonocarbonate such as trihexyl monocarbonate, tert-butyl peroxydicarbonate, and tert-butyl peroxy-2-ethylhexyl monocarbonate; double-3,5,5-three Methyl hexyl peroxide, octyl peroxide , laurel-based peroxide, benzamidine peroxide, p-chlorobenzamide peroxide, etc.; dicumyl peroxide, tert-butyl cumene Dialkyl peroxides such as peroxides. These may be used alone or in combination of two or more.

含羧基之乙烯基聚合物之製備中的羧基與含有環氧基及(甲基)丙烯酸基之化合物的加成反應較佳為使用聚合抑制劑及觸媒於溶劑中進行反應，且較佳為於反應溫度50℃~120℃下進行。The addition reaction of the carboxyl group in the preparation of the carboxyl group-containing vinyl polymer with the epoxy group-containing and (meth)acrylic group-containing compound is preferably carried out by using a polymerization inhibitor and a catalyst in a solvent, and is preferably It is carried out at a reaction temperature of 50 ° C to 120 ° C.

作為反應溶劑，例如可列舉：甲基乙基酮、環己酮等酮類；甲苯、二甲苯、四甲基苯等芳香族烴類；乙二醇單***、乙二醇單甲醚、乙二醇單丁醚、二乙二醇單***、二乙二醇單甲醚、二乙二醇單丁醚、丙二醇單甲醚、丙二醇單***、二丙二醇二***、三乙二醇單 ***等二醇醚類；乙酸乙酯、乙酸丁酯、乙二醇單***乙酸酯、乙二醇單丁醚乙酸酯、二乙二醇單***乙酸酯、二乙二醇單丁醚乙酸酯、丙二醇單甲醚乙酸酯、二丙二醇單甲醚乙酸酯等乙酸酯類；乙醇、丙醇、乙二醇、丙二醇等醇類；辛烷、癸烷等脂肪族烴；石油醚、石油精、氫化石油精、溶劑石腦油等石油系溶劑等。該等可分別單獨使用，亦可組合使用2種以上。Examples of the reaction solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, and ethyl acetate. Glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol single Glycol ethers such as diethyl ether; ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl Acetate such as ether acetate, propylene glycol monomethyl ether acetate or dipropylene glycol monomethyl ether acetate; alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; and aliphatic hydrocarbons such as octane and decane; Petroleum ether, petroleum spirit, hydrogenated petroleum spirit, solvent naphtha and other petroleum solvents. These may be used alone or in combination of two or more.

作為含羧基之乙烯基聚合物之製備中之上述反應的反應觸媒，例如可列舉：三乙胺等三級胺，氯化三乙基苄基銨等四級銨鹽，2-乙基-4-甲基咪唑等咪唑化合物，三苯基膦等磷化合物，環烷酸、月桂酸、硬脂酸、油酸或辛烯酸之鋰鹽、鉻鹽、鋯鹽、鉀鹽、鈉鹽等有機酸之金屬鹽等。該等可分別單獨使用，亦可組合使用2種以上。Examples of the reaction catalyst for the above reaction in the preparation of the carboxyl group-containing vinyl polymer include a tertiary amine such as triethylamine, a quaternary ammonium salt such as triethylbenzylammonium chloride, and 2-ethyl- An imidazole compound such as 4-methylimidazole, a phosphorus compound such as triphenylphosphine, a lithium salt of a naphthenic acid, lauric acid, stearic acid, oleic acid or octenoic acid, a chromium salt, a zirconium salt, a potassium salt, a sodium salt, etc. Metal salts of organic acids, etc. These may be used alone or in combination of two or more.

作為含羧基之乙烯基聚合物之製備中之聚合抑制劑，例如可列舉：對苯二酚、甲基對苯二酚、對苯二酚單甲醚、鄰苯二酚、鄰苯三酚、啡噻等。該等可分別單獨使用，亦可組合使用2種以上。Examples of the polymerization inhibitor in the preparation of the carboxyl group-containing vinyl polymer include hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, catechol, and pyrogallol. Thiophene Wait. These may be used alone or in combination of two or more.

進而，可於上述反應產物之羥基上局部加成二羧酸酐，反應溫度較佳為50~120℃。Further, a dicarboxylic acid anhydride may be locally added to the hydroxyl group of the above reaction product, and the reaction temperature is preferably from 50 to 120 °C.

(3)以酚與甲醛之反應物為主體而構成之芳香族亞甲基聚合物(3) An aromatic methylene polymer mainly composed of a reactant of phenol and formaldehyde

作為聚合物(3)，例如可列舉下述通式(9)所表示之酚醛清漆型酚聚合物。The polymer (3) is, for example, a novolac type phenol polymer represented by the following formula (9).

{式中，Rb為碳原子數為1~20之直鏈狀、支鏈狀或環狀之一價有機基、或者含有光聚合性雙鍵基之一價有機基，Rc為上述通式(5)所表示之基或氫，Rj為甲基、羥基或氫，Rk為上述通式(5)或以下之通式(8)： In the formula, Rb is a linear, branched or cyclic one-valent organic group having 1 to 20 carbon atoms, or a monovalent organic group containing a photopolymerizable double bond group, and Rc is the above formula ( 5) The group or hydrogen represented, Rj is a methyl group, a hydroxyl group or a hydrogen, and Rk is a formula (8) of the above formula (5) or below:

所表示之一價有機基、或氫，m為選自0~100之整數，而且n為選自4~1,000之整數}The one-valent organic group or hydrogen is represented, m is an integer selected from 0 to 100, and n is an integer selected from 4 to 1,000}

本實施形態中所使用之酚醛清漆型酚聚合物係使酚與甲醛之縮合反應物與表鹵醇反應而得。進而，亦可使上述反應物之環氧基與含有羧基或羥基之(甲基)丙烯酸酯化合物進行加成反應，繼而使上述反應物之羥基與二羧酸酐反應。The novolac type phenol polymer used in the present embodiment is obtained by reacting a condensation reaction product of a phenol and formaldehyde with an epihalohydrin. Further, the epoxy group of the above reactant may be subjected to an addition reaction with a (meth) acrylate compound having a carboxyl group or a hydroxyl group, and then the hydroxyl group of the reactant may be reacted with a dicarboxylic anhydride.

作為可用於製備酚醛清漆型酚聚合物之酚的例子，可列舉苯酚、甲酚、二甲苯酚、三甲基苯酚等。該等可分別單獨使用，亦可組合使用2種以上。Examples of the phenol which can be used for the preparation of the novolac type phenol polymer include phenol, cresol, xylenol, and trimethylphenol. These may be used alone or in combination of two or more.

作為酚醛清漆型酚聚合物中所用之表鹵醇之例，可列舉表氯醇、表溴醇。該等可分別單獨使用，亦可組合使用2種以上。Examples of the epihalohydrin used in the novolac type phenol polymer include epichlorohydrin and epibromohydrin. These may be used alone or in combination of two or more.

作為可用於製備酚醛清漆型酚聚合物之一分子內含有羧基與(甲基)丙烯酸酯基之化合物之例，可列舉(甲基)丙烯酸、(甲基)丙烯酸、(甲基)丙烯酸羧基乙酯、(甲基)丙烯酸羧基戊酯、2-(甲基)丙烯醯氧基乙基琥珀酸、2-(甲基)丙烯醯氧基乙基六氫鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基鄰苯二甲酸、反丁烯二酸、桂皮酸、丁烯酸、伊康酸及順丁烯二酸半酯等。該等可分別單獨使用，亦可組合使用2種以上。Examples of the compound which can be used for the preparation of a compound containing a carboxyl group and a (meth) acrylate group in one of the novolac type phenol polymers include (meth)acrylic acid, (meth)acrylic acid, and (meth)acrylic acid carboxyl group. Ester, carboxypentyl (meth)acrylate, 2-(methyl)propenyloxyethyl succinic acid, 2-(methyl)propenyloxyethylhexahydrophthalic acid, 2-(methyl Propylene methoxyethyl phthalic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid and maleic acid half ester. These may be used alone or in combination of two or more.

作為可用於製備酚醛清漆型酚聚合物之一分子內含有羥基與(甲基)丙 烯酸酯化合物之例，可列舉：(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、單(甲基)丙烯酸甘油酯、4-羥基乙烯基苯、(甲基)丙烯酸2-羥基-3-苯氧基丙酯、甘油二(甲基)丙烯酸酯、三羥甲基丙烷二(甲基)丙烯酸酯、甘油甲基丙烯酸酯丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、該等單體之己內酯加成物等。As a kind of phenolic phenol polymer which can be used to prepare phenolic polymers, it contains hydroxyl groups and (meth) propyl groups. Examples of the enoate compound include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and glycerol mono(meth)acrylate. Ester, 4-hydroxyvinylbenzene, 2-hydroxy-3-phenoxypropyl (meth)acrylate, glycerol di(meth)acrylate, trimethylolpropane di(meth)acrylate, glycerol A acrylate acrylate, a pentaerythritol tri(meth) acrylate, a caprolactone adduct of the monomers, and the like.

又，作為環氧基經(甲基)丙烯酸酯改性而成之環氧(甲基)丙烯酸酯化合物之例，可列舉：對苯二酚二縮水甘油醚、鄰苯二酚二縮水甘油醚、間苯二酚二縮水甘油醚等苯基二縮水甘油醚之環氧(甲基)丙烯酸酯；雙酚-A型環氧樹脂、雙酚-F型環氧樹脂、雙酚-S型環氧樹脂、2,2-雙(4-羥基苯基)-1,1,1,3,3,3-六氟丙烷之環氧化合物等雙酚型環氧化合物之環氧(甲基)丙烯酸酯；氫化雙酚-A型環氧樹脂、氫化雙酚-F型環氧樹脂、氫化雙酚-S型環氧樹脂、氫化2,2-雙(4-羥基苯基)-1,1,1,3,3,3-六氟丙烷之環氧化合物等氫化雙酚型環氧化合物之環氧(甲基)丙烯酸酯；環己烷二甲醇二縮水甘油醚化合物等脂環式二縮水甘油醚化合物之環氧(甲基)丙烯酸酯；1,6-己二醇二縮水甘油醚、1,4-丁二醇二縮水甘油醚、二乙二醇二縮水甘油醚等脂肪族二縮水甘油醚化合物之環氧(甲基)丙烯酸酯等。Further, examples of the epoxy (meth) acrylate compound obtained by modifying an epoxy group with a (meth) acrylate include hydroquinone diglycidyl ether and catechol diglycidyl ether. Epoxy (meth) acrylate of phenyl diglycidyl ether such as resorcinol diglycidyl ether; bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, bisphenol-S type ring Epoxy (meth)acrylic acid of bisphenol epoxy compound such as epoxy resin, epoxy compound of 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane Ester; hydrogenated bisphenol-A epoxy resin, hydrogenated bisphenol-F epoxy resin, hydrogenated bisphenol-S epoxy resin, hydrogenated 2,2-bis(4-hydroxyphenyl)-1,1, Epoxy (meth) acrylate of hydrogenated bisphenol type epoxy compound such as epoxy compound of 1,3,3,3-hexafluoropropane; alicyclic diglycidyl ester such as cyclohexane dimethanol diglycidyl ether compound Epoxy (meth) acrylate of ether compound; aliphatic diglycidyl alcohol such as 1,6-hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, diethylene glycol diglycidyl ether Epoxy (meth) acrylate of an ether compound, and the like.

作為可用於製備酚醛清漆型酚聚合物之二羧酸酐，可列舉：琥珀酸酐、環己烷二羧酸酐、4-甲基-環己烷二羧酸酐、5-甲基-環己烷二羧酸酐、二環庚烷二羧酸酐、7-氧雜二環庚烷二羧酸酐、四氫鄰苯二甲酸酐、偏苯三甲酸酐、均苯四甲酸酐、己二酸酐、鄰苯二甲酸酐、(3-三甲氧基矽烷基丙基)琥珀酸酐、(3-三乙氧基矽烷基丙基)琥珀酸酐等多元酸酐。該等可分別單獨使用，亦可組合使用2種以上。Examples of the dicarboxylic acid anhydride which can be used for the preparation of the novolac type phenol polymer include succinic anhydride, cyclohexane dicarboxylic anhydride, 4-methyl-cyclohexane dicarboxylic anhydride, and 5-methyl-cyclohexane dicarboxylic acid. Anhydride, bicycloheptane dicarboxylic anhydride, 7-oxabicycloheptane dicarboxylic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic anhydride, phthalic anhydride A polybasic acid anhydride such as (3-trimethoxydecylpropyl) succinic anhydride or (3-triethoxydecylpropyl) succinic anhydride. These may be used alone or in combination of two or more.

於進行酚醛清漆型酚聚合物之製備中的酚與甲醛之縮合反應之情形時，較佳為使用酸觸媒，作為酸觸媒，可使用各種者，較佳為鹽酸、硫酸、對甲苯磺酸、草酸、三氟化硼、無水氯化鋁、氯化鋅等， 尤佳為對甲苯磺酸、硫酸及鹽酸。In the case of performing a condensation reaction of a phenol with formaldehyde in the preparation of a novolac type phenol polymer, it is preferred to use an acid catalyst, and as the acid catalyst, various ones may be used, preferably hydrochloric acid, sulfuric acid or p-toluene. Acid, oxalic acid, boron trifluoride, anhydrous aluminum chloride, zinc chloride, etc. Especially preferred are p-toluenesulfonic acid, sulfuric acid and hydrochloric acid.

酚與甲醛之縮合反應可於不存在溶劑之條件下或於有機溶劑之存在下進行。作為使用有機溶劑之情形時之具體例，可列舉甲基賽路蘇、乙基賽路蘇、甲苯、二甲苯、甲基異丁基酮等。相對於添加原料之總質量，有機溶劑之使用量通常為50質量%~300質量%，較佳為100質量%~250質量%。反應溫度通常為40℃~180℃，反應時間通常為1小時~10小時。該等溶劑類可分別單獨使用，亦可組合使用2種以上。The condensation reaction of phenol with formaldehyde can be carried out in the absence of a solvent or in the presence of an organic solvent. Specific examples of the case of using an organic solvent include methyl sirolius, ethyl sirolius, toluene, xylene, and methyl isobutyl ketone. The amount of the organic solvent used is usually 50% by mass to 300% by mass, preferably 100% by mass to 250% by mass based on the total mass of the added raw materials. The reaction temperature is usually from 40 ° C to 180 ° C, and the reaction time is usually from 1 hour to 10 hours. These solvents may be used alone or in combination of two or more.

反應結束後，進行水洗處理直至反應混合物之水清洗液之pH值達到3~7、較佳為5~7。於進行水洗處理之情形時，亦可使用如下各種鹼性物質等作為中和劑進行處理：氫氧化鈉、氫氧化鉀等鹼金屬氫氧化物，氫氧化鈣、氫氧化鎂等鹼土金屬氫氧化物，氨、磷酸二氫鈉，進而二乙三胺、三乙四胺、苯胺、苯二胺等有機胺等。又，於水洗處理之情形時，按照常法進行即可。例如，可於反應混合物中加入溶解有上述中和劑之水，反覆進行分液萃取操作，於減壓加熱下將溶劑蒸餾去除而獲得產物。After completion of the reaction, the water washing treatment is carried out until the pH of the water washing solution of the reaction mixture reaches 3 to 7, preferably 5 to 7. In the case of the water washing treatment, various alkaline substances such as the following may be used as a neutralizing agent: an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, or an alkaline earth metal hydroxide such as calcium hydroxide or magnesium hydroxide. Ammonia, sodium dihydrogen phosphate, and further organic amines such as diethylenetriamine, triethylenetetramine, aniline, phenylenediamine, and the like. Further, in the case of the water washing treatment, it may be carried out according to a usual method. For example, water in which the above neutralizing agent is dissolved may be added to the reaction mixture, and a liquid separation extraction operation may be repeatedly performed, and the solvent may be distilled off under reduced pressure to obtain a product.

於上述反應所得之酚與甲醛之縮合物與表氯醇、表溴醇等表鹵醇之溶解混合物中添加氫氧化鈉、氫氧化鉀等鹼金屬氫氧化物，或一面添加一面於20℃~120℃下反應1小時~10小時，藉此可獲得環氧樹脂。將該等環氧化反應之反應物水洗後或不加水洗，於加熱減壓下、110℃~250℃及壓力10mmHg以下之條件下去除表鹵醇或其他添加溶劑等。又，為了進一步製成水解性鹵素較少之環氧樹脂，亦可將獲得之環氧樹脂再次溶解於甲苯、甲基異丁基酮等溶劑中，加入氫氧化鈉、氫氧化鉀等鹼金屬氫氧化物之水溶液進一步進行反應，從而確實地閉環。反應溫度通常為50℃~120℃，反應時間通常為0.5小時~2小時。An alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to the dissolved mixture of the phenol and formaldehyde condensate obtained by the above reaction and an epihalohydrin such as epichlorohydrin or epibromohydrin, or one side is added at 20 ° C. The reaction is carried out at 120 ° C for 1 hour to 10 hours, whereby an epoxy resin can be obtained. After the reactants of the epoxidation reaction are washed with water or without water, the epihalohydrin or other added solvent is removed under the conditions of heating under reduced pressure, 110 ° C to 250 ° C and a pressure of 10 mmHg or less. Further, in order to further prepare an epoxy resin having less hydrolyzable halogen, the obtained epoxy resin may be redissolved in a solvent such as toluene or methyl isobutyl ketone, and an alkali metal such as sodium hydroxide or potassium hydroxide may be added. The aqueous solution of the hydroxide is further reacted to be surely closed. The reaction temperature is usually from 50 ° C to 120 ° C, and the reaction time is usually from 0.5 hour to 2 hours.

反應結束後，藉由過濾、水洗等去除所生成之鹽，進而於加熱減壓下將甲苯、甲基異丁基酮等溶劑蒸餾去除，藉此可獲得本發明之環氧化合物。After completion of the reaction, the salt formed is removed by filtration, washing with water, or the like, and a solvent such as toluene or methyl isobutyl ketone is distilled off under heating and reduced pressure to obtain an epoxy compound of the present invention.

酚醛清漆型酚聚合物之製備中的環氧基與含有羧基或羥基及(甲基)丙烯酸基之化合物之加成反應較佳為使用聚合抑制劑及觸媒於溶劑中進行反應，且較佳為於反應溫度為50℃~120℃下進行。The addition reaction of the epoxy group in the preparation of the novolac type phenol polymer with the compound having a carboxyl group or a hydroxyl group and a (meth)acryl group is preferably carried out by using a polymerization inhibitor and a catalyst in a solvent, and is preferably. It is carried out at a reaction temperature of 50 ° C to 120 ° C.

酚醛清漆型酚聚合物之製備中，作為反應溶劑、反應觸媒及聚合抑制劑，分別可使用與上述(1)以聚合性不飽和雙鍵之反應物為主體而構成之乙烯基聚合物之製備中所說明之反應溶劑、反應觸媒及聚合抑制劑相同者。In the preparation of the novolac type phenol polymer, as the reaction solvent, the reaction catalyst, and the polymerization inhibitor, a vinyl polymer mainly composed of the above (1) reactant having a polymerizable unsaturated double bond can be used. The reaction solvent, reaction catalyst, and polymerization inhibitor described in the preparation are the same.

進而，可於上述反應產物之羥基上局部加成二羧酸酐，反應溫度較佳為50℃~120℃。Further, a dicarboxylic acid anhydride may be locally added to the hydroxyl group of the above reaction product, and the reaction temperature is preferably from 50 ° C to 120 ° C.

就成為聚合物之主體的反應物之耐熱性之觀點而言，鹼可溶性樹脂較佳為選自由以下聚合物所組成之群中的至少一種聚合物：以聚合性不飽和雙鍵之反應物為主體而構成之乙烯基聚合物、以環氧基與羥基之加成反應物為主體而構成之環氧聚合物、以酚與甲醛之反應物為主體而構成之芳香族亞甲基聚合物、以二羧酸與二環氧化物之反應物為主體而構成之酯聚合物。The alkali-soluble resin is preferably at least one polymer selected from the group consisting of polymers having a polymerizable unsaturated double bond, from the viewpoint of heat resistance of the reactant which is a main component of the polymer. a vinyl polymer composed mainly of a main component, an epoxy polymer mainly composed of an addition reaction product of an epoxy group and a hydroxyl group, an aromatic methylene polymer mainly composed of a reaction product of a phenol and formaldehyde, An ester polymer mainly composed of a reactant of a dicarboxylic acid and a diepoxide.

就(A)含自由交聯基之聚矽氧烷與(F)鹼可溶性樹脂之由極性所得的相溶性之觀點而言，含自由交聯基之聚矽氧烷之酸值(A)(mgKOH/g)與鹼可溶性樹脂之酸值(F)(mgKOH/g)之比、即酸值(A)/酸值(F)較佳為0.1以上，更佳為0.2以上，進而佳為0.3以上，另一方面，該比較佳為5.0以下，更佳為4.0以下，進而佳為3.0以下。The acid value (A) of the polyoxyalkylene containing a free crosslinking group from the viewpoint of compatibility of (A) a polyoxyalkylene having a free crosslinking group and (F) an alkali-soluble resin. The ratio of the acid value (F) (mgKOH/g) of the alkali-soluble resin, that is, the acid value (A)/acid value (F) is preferably 0.1 or more, more preferably 0.2 or more, and further preferably 0.3. On the other hand, the comparison is preferably 5.0 or less, more preferably 4.0 or less, and still more preferably 3.0 or less.

<(G)矽烷偶合劑><(G)decane coupling agent>

為了提高聚矽氧烷組合物之曝光、顯影後之硬化膜與基板之密接性，可於聚矽氧烷組合物中添加矽烷偶合劑。例如可列舉：3-(甲 基)丙烯醯氧基丙基三甲氧基矽烷、3-(甲基)丙烯醯氧基丙基三乙氧基矽烷、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、對苯乙烯基三甲氧基矽烷、對苯乙烯基三乙氧基矽烷、對(1-丙烯基苯基)三甲氧基矽烷、對(1-丙烯基苯基)三乙氧基矽烷、對(2-丙烯基苯基)三甲氧基矽烷、對(2-丙烯基苯基)三乙氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷、3-縮水甘油氧基丙基甲基二甲氧基矽烷、3-縮水甘油氧基丙基甲基二乙氧基矽烷、2-(3,4-環氧環己基)三甲氧基矽烷、2-(3,4-環氧環己基)三乙氧基矽烷、2-(3,4-環氧環己基)甲基二甲氧基矽烷、2-(3,4-環氧環己基)甲基二乙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三甲氧基矽烷、N-2-(胺基乙基)-3-胺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-胺基丙基甲基二乙氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-胺基丙基甲基二甲氧基矽烷、3-胺基丙基二乙氧基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷、N-苯基-3-胺基丙基三乙氧基矽烷、N-(乙烯基苄基)-2-胺基乙基-3-胺基丙基三甲氧基矽烷之鹽酸鹽、3-脲基丙基三甲氧基矽烷、3-脲基丙基三乙氧基矽烷、3-巰基丙基三甲氧基矽烷、3-巰基丙基三乙氧基矽烷、3-巰基丙基甲基二甲氧基矽烷、3-巰基丙基甲基二乙氧基矽烷、雙(三甲氧基矽烷基丙基)四硫化物、雙(三乙氧基矽烷基丙基)四硫化物、3-異氰酸酯基丙基三甲氧基矽烷、3-異氰酸酯基丙基三乙氧基矽烷、3-三甲氧基矽烷基丙基琥珀酸酐、3-三乙氧基矽烷基丙基琥珀酸酐等。In order to improve the adhesion between the cured film of the polyoxyalkylene composition and the cured film after development, a decane coupling agent may be added to the polyoxyalkylene composition. For example, can be cited: 3- (A Acryloxypropyltrimethoxydecane, 3-(meth)acryloxypropyltriethoxydecane, 3-(methyl)propenyloxypropylmethyldimethoxydecane , 3-(meth)acryloxypropylmethyldiethoxydecane, p-styryltrimethoxydecane, p-styryltriethoxydecane, p-(1-propenylphenyl)trimethyl Oxydecane, p-(1-propenylphenyl)triethoxydecane, p-(2-propenylphenyl)trimethoxynonane, p-(2-propenylphenyl)triethoxydecane, 3- Glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 3-glycidoxypropyl A Diethoxy decane, 2-(3,4-epoxycyclohexyl)trimethoxynonane, 2-(3,4-epoxycyclohexyl)triethoxydecane, 2-(3,4-ring Oxycyclohexyl)methyldimethoxydecane, 2-(3,4-epoxycyclohexyl)methyldiethoxydecane, vinyltrimethoxydecane, vinyltriethoxydecane, N-2 -(Aminoethyl)-3-aminopropyltrimethoxydecane, N-2-(aminoethyl)-3-aminopropyltriethyl Baseline, N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxylate Baseline, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-aminopropylmethyldimethoxydecane, 3-aminopropyldiethoxy Decane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, N-(vinylbenzyl)-2-aminoethyl 3-aminopropyltrimethoxydecane hydrochloride, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, 3-mercaptopropyltrimethoxydecane, 3 - mercaptopropyltriethoxydecane, 3-mercaptopropylmethyldimethoxydecane, 3-mercaptopropylmethyldiethoxydecane, bis(trimethoxydecylpropyl)tetrasulfide, Bis(triethoxydecylpropyl)tetrasulfide, 3-isocyanatepropyltrimethoxydecane, 3-isocyanatepropyltriethoxydecane, 3-trimethoxydecylpropyl succinic anhydride, 3-triethoxydecylpropyl succinic anhydride or the like.

於聚矽氧烷組合物中添加矽烷偶合劑之情形時，就表現出與基板之密接性之觀點而言，相對於聚矽氧烷組合物中之總固形物成分100質量份，矽烷偶合劑之含量較佳為0.1質量份以上，更佳為0.5質量 份以上，另一方面，就聚矽氧烷組合物之硬化反應性之觀點而言，較佳為20質量份以下，更佳為15質量份以下。When a decane coupling agent is added to the polyoxyalkylene composition, from the viewpoint of exhibiting adhesion to the substrate, the decane coupling agent is 100 parts by mass based on the total solid content of the polyoxyalkylene composition. The content is preferably 0.1 parts by mass or more, more preferably 0.5 mass. On the other hand, from the viewpoint of the curing reactivity of the polyoxyalkylene composition, it is preferably 20 parts by mass or less, more preferably 15 parts by mass or less.

<(I)溶劑><(I) Solvent>

本實施形態中，就調整塗佈膜厚之觀點而言，較佳為於聚矽氧烷組合物中添加溶劑，調整其黏度。作為較佳之溶劑，可列舉下述(1)~(6)之溶劑：In the present embodiment, from the viewpoint of adjusting the coating film thickness, it is preferred to add a solvent to the polyoxyalkylene composition to adjust the viscosity. Preferred solvents include the following solvents (1) to (6):

(1)脂肪族醇：甲醇、乙醇、正丙醇、異丙醇、正丁醇、異丁醇、第二丁醇、第三丁醇、1-戊醇、異戊醇、第二戊醇、第三戊醇、2-甲基-1-丁醇、1-己醇、2-乙基-1-丁醇、4-甲基-2-戊醇、異己醇、甲基-1-戊醇、第二己醇、1-庚醇、異庚醇、2,3-二甲基-1-戊醇、1-辛醇、2-乙基己醇、異辛醇、2-辛醇、3-辛醇、1-壬醇、異壬醇、3,5,5-三甲基己醇、1-癸醇、異癸醇、3,7-二甲基-1-辛醇、1-十一醇、1-十二醇、異十二醇、烯丙醇、炔丙醇、己炔醇(1) Aliphatic alcohols: methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, second butanol, third butanol, 1-pentanol, isoamyl alcohol, second pentanol , third pentanol, 2-methyl-1-butanol, 1-hexanol, 2-ethyl-1-butanol, 4-methyl-2-pentanol, isohexanol, methyl-1-pentyl Alcohol, second hexanol, 1-heptanol, isoheptanol, 2,3-dimethyl-1-pentanol, 1-octanol, 2-ethylhexanol, isooctanol, 2-octanol, 3-octanol, 1-nonanol, isodecyl alcohol, 3,5,5-trimethylhexanol, 1-nonanol, isodecyl alcohol, 3,7-dimethyl-1-octanol, 1- Undecyl alcohol, 1-dodecanol, isododecyl alcohol, allyl alcohol, propargyl alcohol, hexynyl alcohol

(2)芳香族醇：苄醇、(2-羥基苯基)甲醇、(甲氧基苯基)甲醇、(3,4-二羥基苯基)甲醇、4-(羥基甲基)苯-1,2-二醇、(4-羥基-3-甲氧基苯基)甲醇、(3,4-二甲氧基苯基)甲醇、(4-異丙基苯基)甲醇、2-苯基乙醇、1-苯基乙醇、2-苯基-1-丙醇、對甲基苄醇、2-(4-羥基-3-甲氧基苯基)乙烷-1-醇、2-(3,4-二甲氧基苯基)乙烷-1-醇、3-苯基丙烷-1-醇、2-苯基丙烷-2-醇、桂皮醇、3-(4-羥基-3-甲氧基苯基)-2-丙烯-1-醇、3-(4-羥基-3,5-甲氧基苯基)-2-丙烯-1-醇、二苯基甲醇、三苯甲醇、1,2-二苯乙烷-1,2-二醇、1,1,2,2-四苯乙烷-1,2-二醇、苯-1,2-二甲醇、苯-1,3-二甲醇、苯-1,4-二甲醇(2) Aromatic alcohols: benzyl alcohol, (2-hydroxyphenyl)methanol, (methoxyphenyl)methanol, (3,4-dihydroxyphenyl)methanol, 4-(hydroxymethyl)benzene-1 , 2-diol, (4-hydroxy-3-methoxyphenyl)methanol, (3,4-dimethoxyphenyl)methanol, (4-isopropylphenyl)methanol, 2-phenyl Ethanol, 1-phenylethanol, 2-phenyl-1-propanol, p-methylbenzyl alcohol, 2-(4-hydroxy-3-methoxyphenyl)ethane-1-ol, 2-(3 , 4-dimethoxyphenyl)ethane-1-ol, 3-phenylpropan-1-ol, 2-phenylpropan-2-ol, cinnamyl alcohol, 3-(4-hydroxy-3-methyl Oxyphenyl)-2-propen-1-ol, 3-(4-hydroxy-3,5-methoxyphenyl)-2-propen-1-ol, diphenylmethanol, triphenylmethanol, 1 ,2-diphenylethane-1,2-diol, 1,1,2,2-tetraphenylethane-1,2-diol, benzene-1,2-dimethanol, benzene-1,3- Dimethanol, benzene-1,4-dimethanol

(3)脂環式醇：環己醇、甲基環己醇、呋喃甲醇、四氫呋喃甲醇、四氫-2-呋喃甲醇(3) alicyclic alcohol: cyclohexanol, methylcyclohexanol, furan methanol, tetrahydrofuran methanol, tetrahydro-2-furan methanol

(4)二醇或其衍生物：例如乙二醇、乙二醇單烷基(碳原子數1~8)醚、乙二醇單乙烯醚、乙二醇單苯基醚、二烷、二乙二醇單烷基 (碳原子數1~6)醚、二乙二醇單乙烯醚、二乙二醇單苯基醚、三乙二醇單烷基(碳原子數1~3)醚、三乙二醇單乙烯醚、三乙二醇單苯基醚、四乙二醇單苯基醚、丙二醇、丙二醇單烷基(碳原子數1~4)醚、丙二醇單苯基醚、二丙二醇單烷基(碳原子數1~3)醚、乙二醇單乙酸酯、丙二醇單丙烯酸酯、丙二醇單乙酸酯(4) a diol or a derivative thereof: for example, ethylene glycol, ethylene glycol monoalkyl (carbon number 1-8) ether, ethylene glycol monovinyl ether, ethylene glycol monophenyl ether, two Alkane, diethylene glycol monoalkyl (carbon number 1 to 6) ether, diethylene glycol monovinyl ether, diethylene glycol monophenyl ether, triethylene glycol monoalkyl (carbon number 1 to 3) Ether, triethylene glycol monovinyl ether, triethylene glycol monophenyl ether, tetraethylene glycol monophenyl ether, propylene glycol, propylene glycol monoalkyl (carbon number 1-4) ether, propylene glycol monophenyl ether , dipropylene glycol monoalkyl (carbon number 1-3) ether, ethylene glycol monoacetate, propylene glycol monoacrylate, propylene glycol monoacetate

(5)酮化合物：丙酮、甲基乙基酮、3-丁炔-2-酮、甲基正丙基酮、甲基異丙基酮、3-戊炔-2-酮、甲基異丙烯基酮、甲基正丁基酮、甲基異丁基酮、異亞丙基丙酮、4-羥基-4-甲基-2-戊酮、甲基正戊基酮、甲基異戊基酮、乙基正丁基酮、二正丙酮、二異丙酮、2-辛酮、3-辛酮、5-甲基-3-庚酮、5-壬酮、二異丁酮、三甲基壬酮、2,4-戊二酮、2,5-己二酮、環戊酮、環己酮、甲基環己酮、苯乙酮、苯丙酮、異佛爾酮(5) Ketone compounds: acetone, methyl ethyl ketone, 3-butyn-2-one, methyl n-propyl ketone, methyl isopropyl ketone, 3-pentyne-2-one, methyl isopropene Ketone, methyl n-butyl ketone, methyl isobutyl ketone, isopropylidene acetonide, 4-hydroxy-4-methyl-2-pentanone, methyl n-amyl ketone, methyl isoamyl ketone , ethyl n-butyl ketone, di-n-acetone, di-isopropanone, 2-octanone, 3-octanone, 5-methyl-3-heptanone, 5-nonanone, diisobutyl ketone, trimethyl hydrazine Ketone, 2,4-pentanedione, 2,5-hexanedione, cyclopentanone, cyclohexanone, methylcyclohexanone, acetophenone, propiophenone, isophorone

(6)其他：N,N-二甲基甲醯胺、N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮、N,N-二甲基乙醯胺、二甲基亞碸、吡啶、γ-丁內酯、α-乙醯基-γ-丁內酯、四甲基脲、1,3-二甲基-2-咪唑啉酮、N-環己基-2-吡咯啶酮(6) Others: N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, two Methyl hydrazine, pyridine, γ-butyrolactone, α-ethinyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolidinone, N-cyclohexyl-2 -pyrrolidone

該等可單獨或以兩種以上之組合而使用。該等中，就加熱塗佈膜而使溶劑蒸發之觀點而言，較佳為丙二醇單甲醚乙酸酯、乳酸乙酯、γ-丁內酯、二乙二醇單甲醚、二乙二醇二甲醚、丙二醇單甲醚等。These may be used singly or in combination of two or more. Among these, from the viewpoint of heating the coating film to evaporate the solvent, propylene glycol monomethyl ether acetate, ethyl lactate, γ-butyrolactone, diethylene glycol monomethyl ether, and diethylene glycol are preferred. Alcohol dimethyl ether, propylene glycol monomethyl ether, and the like.

該等溶劑可根據塗佈膜厚及黏度而於聚矽氧烷組合物中適當添加，相對於聚矽氧烷組合物中之固形物成分所有成分100質量份，較佳為以50~1,000質量份之範圍使用。These solvents may be appropriately added to the polyoxyalkylene composition in accordance with the coating film thickness and viscosity, and are preferably 100 to 1,000 parts by mass based on 100 parts by mass of all components of the solid content component in the polyoxyalkylene composition. The scope of use is used.

<界面活性劑><Surfactant>

本實施形態中，為了確保聚矽氧烷組合物之塗佈適性及乾燥後之膜平滑性，亦可於聚矽氧烷組合物中含有界面活性劑。作為界面活 性劑，例如可列舉：聚氧乙烯月桂基醚、聚氧乙烯硬脂基醚、聚氧乙烯油基醚等聚氧乙烯烷基醚類；或聚氧乙烯辛基苯基醚、聚氧乙烯壬基苯基醚等聚氧乙烯芳基烷基醚類；或聚氧乙烯氧乙烯二月桂酸酯、聚氧乙烯二硬脂酸酯等聚氧乙烯二烷基酯類；Megafac F171、172、173(大日本油墨製造)，Fluorad FC430、431(Sumitomo 3M製造)，AsahiGuard AG710、Surflon S-382、SC-101、102、103、104、105(旭硝子製造)等氟系界面活性劑；DBE-712、DBE821(Daicel-Cytec公司製造)等聚矽氧系界面活性劑等。In the present embodiment, in order to ensure the coating suitability of the polyoxyalkylene composition and the film smoothness after drying, a surfactant may be contained in the polyoxyalkylene composition. As a interface Examples of the agent include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; or polyoxyethylene octylphenyl ether and polyoxyethylene. a polyoxyethylene aryl alkyl ether such as nonylphenyl ether; or a polyoxyethylene dialkyl ester such as polyoxyethylene oxyethylene dilaurate or polyoxyethylene distearate; Megafac F171, 172, 173 (made by Dainippon Ink), Fluorad FC430, 431 (manufactured by Sumitomo 3M), fluorine-based surfactant such as AsahiGuard AG710, Surflon S-382, SC-101, 102, 103, 104, 105 (manufactured by Asahi Glass); DBE- 712, a polysiloxane surfactant such as DBE821 (manufactured by Daicel-Cytec Co., Ltd.).

就塗佈適性及減少殘渣之觀點而言，相對於聚矽氧烷組合物中之總固形物成分100質量份，該等界面活性劑之含量較佳為0.01質量份以上，更佳為0.1質量份以上，另一方面，就顯影後之圖案密接性之觀點而言，較佳為10質量份以下，更佳為5質量份以下。The content of the surfactant is preferably 0.01 parts by mass or more, more preferably 0.1% by mass based on 100 parts by mass of the total solid content in the polyoxyalkylene composition, from the viewpoint of coating suitability and reduction of residue. On the other hand, from the viewpoint of the pattern adhesion after development, it is preferably 10 parts by mass or less, more preferably 5 parts by mass or less.

<聚合抑制劑><Polymerization inhibitor>

為了提高聚矽氧烷組合物之熱穩定性及保存穩定性，亦可於聚矽氧烷組合物中含有聚合抑制劑(例如自由基聚合抑制劑)。作為聚合抑制劑，例如可使用：對苯二酚、N-亞硝基二苯胺、對第三丁基鄰苯二酚、啡噻、N-苯基萘胺、乙二胺四乙酸、1,2-環己二胺四乙酸、二醇醚二胺四乙酸、2,6-二-第三丁基-對甲基苯酚、5-亞硝基-8-羥基喹啉、1-亞硝基-2-萘酚、2-亞硝基-1-萘酚、2-亞硝基-5-(N-乙基-N-磺丙基胺基)苯酚、N-亞硝基-N-苯基羥胺銨鹽、N-亞硝基-N-苯基羥胺銨鹽、N-亞硝基-N-(1-萘基)羥胺銨鹽、雙(4-羥基-3,5-二-第三丁基)苯基甲烷等。In order to improve the thermal stability and storage stability of the polyoxyalkylene composition, a polymerization inhibitor (for example, a radical polymerization inhibitor) may be contained in the polyoxyalkylene composition. As the polymerization inhibitor, for example, hydroquinone, N-nitrosodiphenylamine, p-tert-butyl catechol, and thiophene can be used. , N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diamine tetraacetic acid, 2,6-di-t-butyl-p-methylphenol, 5 -nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfonate Propylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N-(1-naphthyl)hydroxylamine Ammonium salt, bis(4-hydroxy-3,5-di-t-butyl)phenylmethane, and the like.

於聚矽氧烷組合物中添加聚合抑制劑之情形時，就表現出抑制光聚合性雙鍵之聚合的效果之觀點而言，相對於聚矽氧烷組合物中之總固形物成分100質量份，聚合抑制劑之含量較佳為0.001質量份以上，更佳為0.01質量份以上，另一方面，就由曝光時之自由基產生所 得之圖案形成性之觀點而言，較佳為5質量份以下，更佳為1質量份以下。When a polymerization inhibitor is added to the polyoxyalkylene composition, the mass of the total solid content in the polysiloxane composition is 100% from the viewpoint of suppressing the effect of polymerization of the photopolymerizable double bond. The content of the polymerization inhibitor is preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more, and on the other hand, by radical generation during exposure. From the viewpoint of the pattern formation property, it is preferably 5 parts by mass or less, more preferably 1 part by mass or less.

<(H)抗氧化劑><(H)Antioxidant>

本實施形態中，為了提高氧存在下之聚矽氧烷組合物之熱穩定性，可於聚矽氧烷組合物中添加抗氧化劑。作為此種抗氧化劑，例如可列舉受阻酚系、磷系、內酯系、維生素E系、硫系者等。In the present embodiment, in order to increase the thermal stability of the polyoxyalkylene composition in the presence of oxygen, an antioxidant may be added to the polyoxyalkylene composition. Examples of such an antioxidant include a hindered phenol type, a phosphorus type, a lactone type, a vitamin E type, and a sulfur type.

具體而言，作為抗氧化劑，並無限定，可列舉：三乙二醇-雙[3-(3-第三丁基-5-甲基-4-羥基苯基)丙酸酯](BASF公司製造，IRGANOX245)、1,6-己二醇-雙[3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯](BASF公司製造，IRGANOX259)、2,4-雙-(正辛硫基)-6-(4-羥基-3,5-二-第三丁基苯胺基)-1,3,5-三(BASF公司製造，IRGANOX565)、季戊四醇基-四[3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯)(BASF公司製造，IRGANOX1010)、2,2-硫代-二伸乙基雙[3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯](BASF公司製造，IRGANOX1035)、十八烷基-3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯(BASF公司製造，IRGANOX1076)、N,N'-六亞甲基雙(3,5-二-第三丁基-4-羥基-苯丙醯胺)(BASF公司製造，IRGANOX1098)、3,5-二-第三丁基-4-羥基苄基膦酸-二乙酯(BASF公司製造，IRGAMOD295)、1,3,5-三甲基-2,4,6-三(3,5-二-第三丁基-4-羥基苄基)苯(BASF公司製造，IRGANOX1330)、三(3,5-二-第三丁基-4-羥基苄基)-異氰尿酸酯(BASF公司製造，IRGANOX3114)、辛基化二苯胺(BASF公司製造，IRGANOX5057)、2,4-雙[(辛硫基)甲基)-間甲酚(BASF公司製造，IRGANOX1520L)、異辛基-3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯(BASF公司製造，IRGANOX1135)、2,4-雙(十二烷基硫基甲基)-6-甲基苯酚(BASF公司製造，IRGANOX1726)、2,5,7,8-四甲基-2-(4,8,12-三甲基十三烷基)烷-6-醇(BASF公司製造，IRGANOX E201)、5,7-二-第三丁基-3-(3,4- 二甲基苯基)苯并呋喃-2(3H)-酮(IRGANOX HP-136)、三(2,4-二-第三丁基苯基)亞磷酸酯(BASF公司製造，IRGAFOS168)、三[2-[[2,4,8,10-四(1,1-二甲基乙基)二苯并[d,f][1,3,2]二磷環庚烷-6-基]氧基]乙基]胺(BASF公司製造，IRGAFOS12)、雙(2,4-二-第三丁基-6-甲基苯基)乙基亞磷酸酯(BASF公司製造，IRGAFOS38)、3,3-硫代二丙酸二(十二烷基)酯(BASF公司製造，IRGANOX PS800)、3,3-硫代二丙酸二(十八烷基)酯(BASF公司製造，IRGANOX PS802)等。Specifically, the antioxidant is not limited, and examples thereof include triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate] (BASF Corporation) Manufacture, IRGANOX245), 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (manufactured by BASF Corporation, IRGANOX 259), 2, 4 - bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-three (manufactured by BASF Corporation, IRGANOX 565), pentaerythritol-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate (manufactured by BASF Corporation, IRGANOX 1010), 2,2-sulfur代-二伸ethyl bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (manufactured by BASF Corporation, IRGANOX 1035), octadecyl-3-(3, 5-Di-t-butyl-4-hydroxyphenyl)propionate (manufactured by BASF Corporation, IRGANOX 1076), N,N'-hexamethylenebis(3,5-di-t-butyl-4- Hydroxy-phenylpropanamide) (manufactured by BASF Corporation, IRGANOX 1098), 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid-diethyl ester (manufactured by BASF Corporation, IRGAMOD 295), 1, 3, 5 - Trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene (manufactured by BASF, IRGANOX 1330), three (3,5-di-third) 4-hydroxybenzyl)-isocyanurate (manufactured by BASF Corporation, IRGANOX 3114), octylated diphenylamine (manufactured by BASF Corporation, IRGANOX 5057), 2,4-bis[(octylthio)methyl)- M-cresol (manufactured by BASF Corporation, IRGANOX 1520L), isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate (manufactured by BASF Corporation, IRGANOX 1135), 2,4- Bis(dodecylthiomethyl)-6-methylphenol (manufactured by BASF Corporation Manufacture, IRGANOX1726), 2,5,7,8-tetramethyl-2-(4,8,12-trimethyltridecyl) Alkanol-6-ol (manufactured by BASF Corporation, IRGANOX E201), 5,7-di-t-butyl-3-(3,4-dimethylphenyl)benzofuran-2(3H)-one (IRGANOX) HP-136), tris(2,4-di-t-butylphenyl)phosphite (manufactured by BASF Corporation, IRGAFOS168), three [2-[[2,4,8,10-four (1,1) -dimethylethyl)dibenzo[d,f][1,3,2] Phosphocycloheptan-6-yl]oxy]ethyl]amine (manufactured by BASF Corporation, IRGAFOS12), bis(2,4-di-t-butyl-6-methylphenyl)ethyl phosphite ( Manufactured by BASF, IRGAFOS38), 3,3-thiodipropionate di(dodecyl) ester (manufactured by BASF, IRGANOX PS800), 3,3-thiodipropionate dioctadecyl ester (Manufactured by BASF, IRGANOX PS802), etc.

又，具體而言，作為抗氧化劑，並無限定，可列舉：3,9-雙[2-[3-(3-第三丁基-4-羥基-5-甲基苯基)丙醯氧基]-1,1-二甲基乙基]-2,4,8,10-四氧雜螺[5,5]十一烷(住友化學公司製造，SUMILIZER GA-80)、2,2'-亞甲基雙(6-第三丁基-4-甲基苯酚)(住友化學公司製造，SUMILIZER MDP-S)、4,4'-亞丁基雙(6-第三丁基-3-甲基苯酚)(住友化學公司製造，SUMILIZER BBM-S)、4,4'-硫代雙(6-第三丁基-3-甲基苯酚)(住友化學公司製造，SUMILIZER WX-R)、季戊四醇基-四(3-月桂基硫代丙酸酯)(住友化學公司製造，SUMILIZER TP-D)、2-巰基苯并咪唑(住友化學公司製造，SUMILIZER MB)、聯苯-4,4'-二基-雙[雙(2,4-二-第三丁基-5-甲基苯氧基)膦](大崎工業公司製造，GSY-P101)、環己烷與過氧化N-丁基-2,2,6,6-四甲基-4-哌啶胺-2,4,6-三氯-1,3,5-三之反應產物及與2-胺基乙醇之反應產物(BASF公司製造，TINUVIN152)等。Further, specifically, the antioxidant is not limited, and examples thereof include 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propaneoxyl 1,1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane (Sumitomo Chemical Co., Ltd., SUMILIZER GA-80), 2, 2' -methylenebis(6-tert-butyl-4-methylphenol) (SUMILIZER MDP-S, manufactured by Sumitomo Chemical Co., Ltd.), 4,4'-butylene bis(6-tert-butyl-3-methyl) Phenol) (SUMILIZER BBM-S, manufactured by Sumitomo Chemical Co., Ltd.), 4,4'-thiobis(6-tert-butyl-3-methylphenol) (SUMILIZER WX-R, manufactured by Sumitomo Chemical Co., Ltd.), pentaerythritol Base-tetrakis(3-laurylthiopropionate) (SUMILIZER TP-D, manufactured by Sumitomo Chemical Co., Ltd.), 2-mercaptobenzimidazole (SUMILIZER MB, Sumitomo Chemical Co., Ltd.), biphenyl-4,4'- Diki-bis[bis(2,4-di-t-butyl-5-methylphenoxy)phosphine] (manufactured by Osaki Industries Co., Ltd., GSY-P101), cyclohexane and N-butyl peroxide- 2,2,6,6-tetramethyl-4-piperidinamine-2,4,6-trichloro-1,3,5-three The reaction product and the reaction product with 2-aminoethanol (manufactured by BASF Corporation, TINUVIN 152) and the like.

該等抗氧化劑可單獨或以2種以上之混合物之形式使用。於聚矽氧烷組合物中添加抗氧化劑之情形時，就表現出氧存在下之熱穩定性效果之觀點而言，相對於聚矽氧烷組合物中之總固形物成分100質量份，抗氧化劑之含量較佳為0.001質量份以上，更佳為0.01質量份以上，進而佳為0.1質量份以上，另一方面，就由曝光時之自由基產生所得之圖案形成性之觀點而言，較佳為15質量份以下，更佳為10質量 份以下，進而佳為5質量份以下。These antioxidants may be used singly or in the form of a mixture of two or more. In the case where an antioxidant is added to the polyoxyalkylene composition, it is resistant to 100 parts by mass of the total solid content in the polyoxyalkylene composition from the viewpoint of exhibiting the heat stability effect in the presence of oxygen. The content of the oxidizing agent is preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more, still more preferably 0.1 part by mass or more, and on the other hand, from the viewpoint of pattern formation property due to radical generation during exposure, Better than 15 parts by mass, more preferably 10 parts by mass The remainder is preferably 5 parts by mass or less.

<塑化劑><Plasticizer>

進而，於聚矽氧烷組合物中，視需要亦可含有塑化劑等添加劑。作為此種添加劑，例如可列舉：鄰苯二甲酸二乙酯等鄰苯二甲酸酯類、鄰甲苯磺醯胺、對甲苯磺醯胺、檸檬酸三丁酯、檸檬酸三乙酯、乙醯基檸檬酸三乙酯、乙醯基檸檬酸三正丙酯、乙醯基檸檬酸三正丁酯、聚丙二醇、聚乙二醇、聚乙二醇烷基醚、聚丙二醇烷基醚等。於聚矽氧烷組合物中添加塑化劑之情形時，就提高膜之柔軟性之觀點而言，相對於聚矽氧烷組合物中之總固形物成分100質量份，塑化劑之含量較佳為0.1質量份以上，更佳為0.5質量份以上，進而佳為0.7質量份以上，另一方面，就玻璃轉移溫度之觀點而言，較佳為10質量份以下，更佳為8質量份以下，進而佳為5質量份以下。Further, the polyoxyalkylene composition may contain an additive such as a plasticizer as needed. Examples of such an additive include phthalic acid esters such as diethyl phthalate, o-toluenesulfonamide, p-toluenesulfonamide, tributyl citrate, triethyl citrate, and acetamidine. Triethyl citrate, tri-n-propyl ethyl citrate, tri-n-butyl citrate, polypropylene glycol, polyethylene glycol, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether and the like. In the case where a plasticizer is added to the polyoxyalkylene composition, the content of the plasticizer is 100 parts by mass relative to the total solid content in the polyoxynitride composition from the viewpoint of improving the flexibility of the film. It is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and still more preferably 0.7 parts by mass or more. On the other hand, from the viewpoint of the glass transition temperature, it is preferably 10 parts by mass or less, more preferably 8 parts by mass. The remainder is preferably 5 parts by mass or less.

就顯影後之殘渣之減少、硬化膜之耐龜裂性之觀點而言，本實施形態中所用之聚矽氧烷組合物之酸值較佳為0.1mgKOH/g以上，更佳為1mgKOH/g以上，進而佳為5mgKOH/g以上，另一方面，就圖案之密接性之觀點而言，較佳為200mgKOH/g以下，更佳為170mgKOH/g莫耳以下，進而佳為150mgKOH/g以下。The acid value of the polyoxymethane composition used in the present embodiment is preferably 0.1 mgKOH/g or more, more preferably 1 mgKOH/g, from the viewpoint of the reduction of the residue after development and the crack resistance of the cured film. In the above, the adhesion of the pattern is preferably at least 200 mgKOH/g, more preferably 170 mgKOH/g mole or less, and still more preferably 150 mgKOH/g or less.

<感光性樹脂組合物之硬化物><Cured product of photosensitive resin composition>

藉由使本實施形態中所用之聚矽氧烷組合物硬化而得之硬化物中，厚度10μm之該硬化物於大氣下、220℃及烘烤3小時後之400nm之波長下的光之透射率較佳為70%以上。又，亦較佳為藉由使本發明中所用之聚矽氧烷組合物硬化而獲得透明絕緣膜。The cured product obtained by curing the polyoxyalkylene composition used in the present embodiment has a light transmittance of 10 μm in thickness of the cured product under the atmosphere at 220 ° C and a wavelength of 400 nm after baking for 3 hours. The rate is preferably 70% or more. Further, it is also preferred to obtain a transparent insulating film by curing the polyoxyalkylene composition used in the present invention.

關於硬化物中之自由基含量，相對於硬化物1g，較佳為含有0.1×10-6 莫耳以上，進而佳為0.15×10-6 莫耳以上。另一方面，就圖案形成之觀點而言，較佳為120×10-6 莫耳以下，進而佳為60×10-6 莫耳以下。硬化物中之自由基含量之測定方法與前文關於聚矽氧烷組合物所 說明者相同。The content of the radical in the cured product is preferably 0.1 × 10 -6 mol or more, more preferably 0.15 × 10 -6 mol or more, per 1 g of the cured product. On the other hand, from the viewpoint of pattern formation, it is preferably 120 × 10 -6 mTorr or less, and more preferably 60 × 10 -6 mol or less. The method for determining the free radical content of the hardened material is the same as that described above for the polyoxyalkylene composition.

以下，對使用上述聚矽氧烷組合物形成硬化凸紋圖案之方法之較佳例進行說明。Hereinafter, a preferred embodiment of a method of forming a hardened relief pattern using the above polyoxyalkylene composition will be described.

形成硬化凸紋圖案之方法包括：於基板上塗佈聚矽氧烷組合物之第一步驟、照射活性光線之第二步驟、利用顯影液去除未硬化部分之第三步驟、進一步進行加熱硬化之第四步驟。The method for forming a hardened relief pattern includes: a first step of coating a polyoxyalkylene composition on a substrate, a second step of irradiating the active light, a third step of removing the unhardened portion by the developer, and further performing heat hardening The fourth step.

首先，將上述聚矽氧烷組合物塗佈於矽晶圓、陶瓷基板、鋁基板等所需之各種基材上。作為塗佈裝置或塗佈方法，可利用旋轉塗佈機、模塗佈機、噴塗機、浸漬、印刷、刮刀塗佈機、輥塗等。將所塗佈之基材於80℃~200℃下軟烤1分鐘~15分鐘後，使用接觸式對準機、鏡面投影曝光機、步進機等曝光投影裝置，介隔所需之光罩照射活性光線。First, the polyoxyalkylene composition is applied onto various substrates required for a silicon wafer, a ceramic substrate, an aluminum substrate, or the like. As the coating device or the coating method, a spin coater, a die coater, a spray coater, a dipping, a printing, a knife coater, a roll coating, or the like can be used. After the coated substrate is soft baked at 80 ° C ~ 200 ° C for 1 minute ~ 15 minutes, use a contact projection machine, mirror projection exposure machine, stepper and other exposure projection device, to separate the required mask Irradiating active light.

作為活性光線，可利用X射線、電子束、紫外線、可見光等，本發明中，較佳為使用波長為200nm~500nm者。就圖案之解析度及操作性之方面而言，其光源波長尤佳為UV-i射線(365nm)，作為曝光投影裝置，尤佳為步進機。As the active light, X-rays, electron beams, ultraviolet rays, visible light, or the like can be used. In the present invention, those having a wavelength of 200 nm to 500 nm are preferably used. In terms of resolution and operability of the pattern, the wavelength of the light source is particularly preferably UV-i ray (365 nm), and is preferably a stepping machine as an exposure projection device.

其後，以提高光感度等為目的，視需要亦可實施任意溫度、時間之組合(較佳為溫度為40℃~200℃，而且時間為10秒~360秒)之曝光後烘烤(post-exposure bake，PEB)或顯影前烘烤。Thereafter, for the purpose of improving the light sensitivity, etc., a combination of any temperature and time (preferably a temperature of 40 ° C to 200 ° C and a time of 10 seconds to 360 seconds) may be applied as needed (post) -exposure bake, PEB) or bake before development.

繼而進行顯影，可自浸漬法、覆液法、淋浴法及旋轉噴霧法等方法中選擇而進行。作為顯影液，較佳為有機溶劑、鹼性顯影液。可單獨使用本發明之組合物之良溶劑，或可將良溶劑與不良溶劑適當混合而使用。Subsequent development can be carried out by a method such as a dipping method, a liquid coating method, a shower method, or a rotary spray method. As the developer, an organic solvent or an alkali developer is preferred. A good solvent of the composition of the present invention may be used alone, or a good solvent may be appropriately mixed with a poor solvent.

作為適合作為鹼性顯影液之例，例如可列舉：鹼金屬或鹼土金屬之碳酸鹽之水溶液，鹼金屬之氫氧化物之水溶液，氫氧化四乙基銨、氫氧化四丙基銨水溶液等氫氧化銨類，二乙胺、三乙胺、二乙醇 胺、三乙醇胺等胺類。尤佳為使用含有0.05質量%~10質量%之碳酸鈉、碳酸鉀、碳酸鋰等碳酸鹽、氫氧化四甲基銨、氫氧化四乙基銨等氫氧化銨類、二乙胺、二乙醇胺等胺類之弱鹼性水溶液，於20℃~35℃之溫度下進行顯影。Examples of suitable alkaline developing solutions include aqueous solutions of alkali metal or alkaline earth metal carbonates, aqueous solutions of alkali metal hydroxides, hydrogen tetraethylammonium hydroxide, and tetrapropylammonium hydroxide aqueous solutions. Ammonium Oxide, Diethylamine, Triethylamine, Diethanol Amines such as amines and triethanolamines. It is particularly preferable to use ammonium carbonates such as sodium carbonate, potassium carbonate, lithium carbonate, etc., ammonium tetramethylammonium hydroxide, tetraethylammonium hydroxide, etc., diethylamine, diethanolamine, etc., containing 0.05% by mass to 10% by mass. A weakly basic aqueous solution of an amine is developed at a temperature of from 20 ° C to 35 ° C.

作為有機溶劑之顯影液，例如二醇可列舉乙二醇、丙二醇等作為例，作為二醇之單烷基醚，可列舉乙二醇單甲醚、乙二醇單***、丙二醇單甲醚、丙二醇單***等作為例。作為其他有機溶劑之顯影液，可列舉N-甲基-2-吡咯啶酮、N-乙醯基-2-吡咯啶酮、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺、二甲基亞碸、γ-丁內酯、α-乙醯基-γ-丁內酯、環戊酮、環己酮等。Examples of the developing solution of the organic solvent include, for example, ethylene glycol and propylene glycol. Examples of the monoalkyl ether of the diol include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and propylene glycol monomethyl ether. Propylene glycol monoethyl ether or the like is exemplified. Examples of the developing solution of other organic solvents include N-methyl-2-pyrrolidone, N-ethinyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethyl Mercaptoamine, dimethyl hydrazine, γ-butyrolactone, α-ethinyl-γ-butyrolactone, cyclopentanone, cyclohexanone, and the like.

顯影結束後，藉由淋洗液進行清洗而去除顯影液，藉此可獲得附凸紋圖案之塗膜。作為淋洗液，可將蒸餾水、甲醇、乙醇、異丙醇、丙二醇單甲醚等單獨或適當混合而使用，或亦可將該等階段性地組合而使用。After the development is completed, the developer is removed by washing with an eluent, whereby a coating film having a relief pattern can be obtained. As the eluent, distilled water, methanol, ethanol, isopropyl alcohol, propylene glycol monomethyl ether or the like may be used singly or in an appropriate mixture, or may be used in combination in stages.

如此而獲得之凸紋圖案係於150℃~250℃等遠低於先前之聚醯亞胺前驅物組合物之硬化溫度下轉變為硬化凸紋圖案。該加熱硬化可使用加熱板、惰性烘箱、可設定溫控程式之升溫式烘箱等進行。作為加熱硬化時之環境氣體，可使用空氣，視需要亦可使用氮氣、氬氣等惰性氣體。The embossed pattern thus obtained is converted into a hardened relief pattern at a curing temperature of from 150 ° C to 250 ° C, which is much lower than that of the prior polyimine precursor composition. The heat curing can be carried out using a hot plate, an inert oven, a temperature-increasing oven capable of setting a temperature control program, or the like. As the ambient gas during heat curing, air may be used, and an inert gas such as nitrogen or argon may be used as needed.

可將上述硬化凸紋圖案用作選自由例如形成於矽晶圓、玻璃、膜、於該等上濺鍍有一種以上之金屬的基材等基材上的半導體裝置之表面保護膜、層間絕緣膜、α射線遮蔽膜及微透鏡陣列等微結構體與其封裝材料之間的支撐物(間隔壁)所組成之群中之任一者，其他步驟係應用周知之半導體裝置之製造方法，藉此可製造含有觸控面板、CMOS(Complementary Metal-Oxide-Semiconductor Transistor，互補型金屬氧化物半導體)影像感測器等光學元件之各種顯示裝置、半導體 裝置。又，可獲得含有塗膜之電子零件或半導體裝置，上述塗膜包含使上述聚矽氧烷組合物硬化而成之樹脂。The hardened relief pattern may be used as a surface protection film or interlayer insulation of a semiconductor device selected from a substrate such as a germanium wafer, a glass, a film, or a substrate on which one or more metals are sputtered. Any one of a group consisting of a support (a partition) between a microstructure such as a film, an alpha ray shielding film, and a microlens array and a packaging material thereof, and other steps are applied to a manufacturing method of a known semiconductor device. Various display devices and semiconductors including optical components such as a touch panel and a CMOS (Complementary Metal-Oxide-Semiconductor Transistor) image sensor can be manufactured. Device. Further, an electronic component or a semiconductor device including a coating film containing a resin obtained by curing the polyoxyalkylene composition can be obtained.

[實施例][Examples]

以下按照實施例對實施形態之方法進行具體說明，但本發明並不受以下之實施例所限定。Hereinafter, the method of the embodiment will be specifically described by way of examples, but the invention is not limited by the following examples.

(ESR之測定方法)(Method for measuring ESR) <使用裝置、條件><Usage device, condition>

使用日本電子公司製造之ESR(型號：JES-FE2XG)，於大氣下、24℃、常壓且遮蔽樣品不受波長為400nm以下之光的照射之狀態下測定ESR。作為標準樣品標記物，使用錳標記物(Mn2+ )。The ESR was measured using an ESR (Model: JES-FE2XG) manufactured by JEOL Ltd. under the atmosphere, at 24 ° C, atmospheric pressure, and shielding the sample from light having a wavelength of 400 nm or less. As a standard sample marker, a manganese marker (Mn 2+ ) was used.

以下示出裝置之測定條件。The measurement conditions of the device are shown below.

微波輸出：1mWMicrowave output: 1mW

調變磁場：1GModulated magnetic field: 1G

響應：0.03秒Response: 0.03 seconds

振幅：200以上Amplitude: 200 or more

磁場：3380GMagnetic field: 3380G

磁場掃描：±250GMagnetic field scan: ±250G

磁場掃描時間：4分鐘Magnetic field scan time: 4 minutes

<空白樣本之確認><Confirmation of blank sample>

調整ESR裝置後，於ESR試樣管(扁平型槽)中僅加入丙酮，將振幅設定為1000，進行測定，確認到如圖1所示般僅可見Mn2+ 之6個波峰。After the ESR device was adjusted, only acetone was added to the ESR sample tube (flat groove), and the amplitude was set to 1000. The measurement was carried out, and it was confirmed that only six peaks of Mn 2+ were observed as shown in Fig. 1 .

自Mn2+ 之低磁場側起計數，以第3個波峰作為標準波峰，設定為g3=2.034，於計算所測定之樣品之g值時使用。自低磁場側起計數之第4個波峰係設定為g4=1.981。The count was calculated from the low magnetic field side of Mn 2+ , and the third peak was used as the standard peak, and was set to g3 = 2.034, and was used when calculating the g value of the sample to be measured. The fourth peak system counted from the low magnetic field side was set to g4 = 1.981.

<感度之確認><Confirmation of sensitivity>

調整4-羥基-TEMPO(4-羥基-2,2,6,6-四甲基哌啶-1-氧自由基)(東京化成工業公司製造)之1ppm丙酮溶液，進行ESR測定，如圖2所示，確認觀察到4-羥基-TEMPO之波峰。The 1 ppm acetone solution of 4-hydroxy-TEMPO (4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl radical) (manufactured by Tokyo Chemical Industry Co., Ltd.) was adjusted for ESR measurement, as shown in Fig. 2. As shown, it was confirmed that a peak of 4-hydroxy-TEMPO was observed.

<g值之計算方法><calculation method of g value>

作為標準波峰，於Mn2+ 之6個波峰內，自低磁場側起計數，使用第3個波峰。將標準波峰之吸收磁場設定為Hs ，將gs 值設定為2.034，將測定試樣之吸收磁場設定為H0 。測定試樣之g值係藉由下式算出。As a standard peak, in the six peaks of Mn 2+ , counting from the low magnetic field side, the third peak was used. The absorption magnetic field of the standard peak was set to H s , the g s value was set to 2.034, and the absorption magnetic field of the measurement sample was set to H 0 . The g value of the measurement sample was calculated by the following formula.

g=gs +gs (Hs -H0 )/Hs g=g s +g s (H s -H 0 )/H s

<聚矽氧烷之測定><Measurement of polyoxyalkylene>

於20mL樣品管中稱量聚矽氧烷1g與9g之丙酮並使其溶解，加蓋。其後，於大氣下、24℃、常壓且遮蔽波長為400nm以下之光的狀態下靜置24小時後，測定ESR。1 g of polysiloxane and 9 g of acetone were weighed in a 20 mL sample tube and dissolved, and capped. Thereafter, the mixture was allowed to stand in the air at 24 ° C, normal pressure, and shielding light having a wavelength of 400 nm or less for 24 hours, and then the ESR was measured.

<樹脂組合物之測定><Measurement of Resin Composition>

於20mL樣品管內稱量樹脂組合物0.3g與丙酮9.7g置並加蓋。其後，於大氣下、24℃、常壓且遮蔽波長為400nm以下之光的狀態下靜置24小時後，測定ESR。0.3 g of the resin composition and 9.7 g of acetone were weighed and capped in a 20 mL sample tube. Thereafter, the mixture was allowed to stand in the air at 24 ° C, normal pressure, and shielding light having a wavelength of 400 nm or less for 24 hours, and then the ESR was measured.

<自由基濃度之分析><Analysis of free radical concentration>

使用4-羥基-TEMPO作為1莫耳分子含有1莫耳自由基之標準品，製作校準曲線，分析溶液中之自由基濃度。對於聚矽氧烷組合物及感光性樹脂組合物，使用TGA，測定將10mg之試樣於250℃下保持30分鐘後之熱重減少，以殘留質量作為固形物成分，分析固形物成分含有率。根據藉由樹脂組合物之測定而得之自由基濃度及固形物成分含有率，算出每1g固形物成分所含之自由基量。A 4-hydroxy-TEMPO was used as a standard for a 1 molar product containing 1 mole of free radicals, and a calibration curve was prepared to analyze the radical concentration in the solution. For the polyoxane composition and the photosensitive resin composition, the TGA was used to measure the thermal weight after 10 mg of the sample was kept at 250 ° C for 30 minutes, and the residual mass was used as the solid component to analyze the solid content. . The amount of radicals contained per 1 g of the solid content component was calculated from the radical concentration obtained by the measurement of the resin composition and the solid content of the solid content.

(評價方法)(evaluation method) 1.解析度之評價1. Evaluation of resolution

以烘烤後之膜厚達到15μm之方式將感光性樹脂組合物塗佈於經 鋁濺鍍之矽基板上，於95℃下在加熱板上烘烤4分鐘。The photosensitive resin composition is applied to the film by the film thickness after baking to 15 μm. The aluminum sputtered substrate was baked on a hot plate at 95 ° C for 4 minutes.

通過附有測試圖案之光罩，使用i射線步進機(Nikon製造，NSR2005 i8A)對上述具有塗佈膜之基板進行曝光。曝光係於大氣中進行，將焦距設定為-15，以30mJ/cm2 為單位自60mJ/cm2 進行照射直至1110mJ/cm2 為止。The substrate having the coating film was exposed by an i-ray stepper (manufactured by Nikon, NSR2005 i8A) through a photomask attached with a test pattern. System for exposure to the atmosphere, the focal length is set to -15 to 30mJ / cm 2 units from 60mJ / cm 2 for up to 1110mJ / date irradiated cm 2.

(關於實施例1~14、實施例16~27、比較例1~5)(Examples 1 to 14, Examples 16 to 27, and Comparative Examples 1 to 5)

繼曝光之後，使用鹼顯影液(AZ Electronic Materials公司製造之顯影液，2.38%氫氧化四甲基銨水溶液)，於23℃、30秒×2次之條件下進行顯影，藉由純水進行沖洗，去除塗膜之未曝光部。繼而，於經氮氣置換之烘箱中於220℃下將上述經圖案化之基板烘烤30分鐘而使其硬化。After the exposure, development was carried out at 23 ° C, 30 seconds × 2 times using an alkali developing solution (developing solution manufactured by AZ Electronic Materials, 2.38% aqueous solution of tetramethylammonium hydroxide), and rinsing with pure water. The unexposed portion of the coating film is removed. Then, the patterned substrate was baked at 220 ° C for 30 minutes in a nitrogen-substituted oven to be hardened.

(關於實施例15)(Regarding Example 15)

繼曝光之後，使用PGMEA(丙二醇單甲醚乙酸酯)，於23℃、30秒×2次之條件下進行顯影，去除塗膜之未曝光部。繼而，於經氮氣置換之烘箱中於220℃下將上述經圖案化之基板烘烤30分鐘而使其硬化。After the exposure, development was carried out using PGMEA (propylene glycol monomethyl ether acetate) under the conditions of 23 ° C and 30 seconds × 2 times, and the unexposed portion of the coating film was removed. Then, the patterned substrate was baked at 220 ° C for 30 minutes in a nitrogen-substituted oven to be hardened.

以光學顯微鏡觀察實施例1~27及比較例1~5中獲得之圖案之曝光量400mJ/cm2 的部分中以25μm×25μm之正方形遮光之部分，按照下述基準進行評價。The portion of the portion obtained by the patterns obtained in Examples 1 to 27 and Comparative Examples 1 to 5 at an exposure amount of 400 mJ/cm 2 was light-shielded with a square of 25 μm × 25 μm, and evaluated according to the following criteria.

○：並無殘渣而形成開口，圖案中未觀察到***或剝離○: No opening was formed, and no bulge or peeling was observed in the pattern.

△：雖形成開口但有一部分殘渣，圖案中未觀察到***或剝離△: Although an opening was formed but a part of the residue was formed, no bulging or peeling was observed in the pattern.

×：有殘渣且未形成開口，或圖案產生***或剝離×: There is residue and no opening is formed, or the pattern is raised or peeled off.

2.解析範圍之評價2. Evaluation of the scope of analysis

以光學顯微鏡觀察上述獲得之圖案，於以25μm×25μm之正方形遮光之部分中，將目測觀察並無殘渣而形成開口、且圖案未產生***或剝離之曝光量之範圍作為解析範圍，按照下述基準進行評價。The pattern obtained above was observed under an optical microscope, and a range in which an opening was formed without a residue and the pattern was not embossed or peeled off was visually observed in a portion of a square of 25 μm × 25 μm, as follows. Benchmarks are evaluated.

◎：解析範圍較420mJ/cm2 廣◎: The resolution range is wider than 420mJ/cm 2

○：解析範圍較300mJ/cm2 廣○: The resolution range is wider than 300mJ/cm 2

△：解析範圍較120mJ/cm2 廣△: The resolution range is wider than 120mJ/cm 2

×：解析範圍為120mJ/cm2 以下×: The analysis range is 120 mJ/cm 2 or less

3.耐龜裂性之評價3. Evaluation of crack resistance

以烘烤後之膜厚達到15μm之方式，將聚矽氧烷組合物塗佈於經鋁濺鍍之矽基板上，於95℃下在加熱板上烘烤4分鐘。The polyoxynitride composition was applied onto an aluminum sputtered ruthenium substrate in such a manner that the film thickness after baking reached 15 μm, and baked on a hot plate at 95 ° C for 4 minutes.

通過附有測試圖案之光罩，使用i射線步進機對上述具有塗佈膜之基板進行400mJ/cm2 曝光。曝光係於大氣中進行，且將焦距設定為-15。The substrate having the coating film was exposed to 400 mJ/cm 2 using an i-ray stepper through a photomask attached with a test pattern. The exposure was carried out in the atmosphere and the focal length was set to -15.

(關於實施例1~14、實施例16~27、比較例1~5)(Examples 1 to 14, Examples 16 to 27, and Comparative Examples 1 to 5)

繼曝光之後，使用鹼顯影液(AZ Electronic Materials公司製造之顯影液，2.38%氫氧化四甲基銨水溶液)，於23℃、30秒×2次之條件下進行顯影，藉由純水進行沖洗，去除塗膜之未曝光部。繼而，於經氮氣置換之烘箱中於220℃下將上述經圖案化之基板烘烤30分鐘而使其硬化。After the exposure, development was carried out at 23 ° C, 30 seconds × 2 times using an alkali developing solution (developing solution manufactured by AZ Electronic Materials, 2.38% aqueous solution of tetramethylammonium hydroxide), and rinsing with pure water. The unexposed portion of the coating film is removed. Then, the patterned substrate was baked at 220 ° C for 30 minutes in a nitrogen-substituted oven to be hardened.

(關於實施例15)(Regarding Example 15)

繼曝光之後，使用PGMEA於23℃、30秒×2次之條件下進行顯影，去除塗膜之未曝光部。繼而，於經氮氣置換之烘箱中於220℃下將上述經圖案化之基板烘烤30分鐘而使其硬化。After the exposure, development was carried out using PGMEA at 23 ° C for 30 seconds × 2 times to remove the unexposed portions of the coating film. Then, the patterned substrate was baked at 220 ° C for 30 minutes in a nitrogen-substituted oven to be hardened.

於經氮氣置換之烘箱中，將實施例1~27及比較例1~5獲得之經圖案化之基板進一步於300℃下烘烤30分鐘，繼而使用冷熱衝擊試驗機，以於-40℃下15分鐘、於120℃下15分鐘為一次，將該循環重複100次後，藉由目測、光學顯微鏡進行觀察，按照下述基準進行評價。The patterned substrates obtained in Examples 1 to 27 and Comparative Examples 1 to 5 were further baked at 300 ° C for 30 minutes in a nitrogen-substituted oven, followed by a thermal shock tester at -40 ° C. After 15 minutes at 120 ° C for 15 minutes, the cycle was repeated 100 times, and then observed by visual observation and optical microscopy, and evaluated according to the following criteria.

◎：5片基板內未確認到龜裂◎: No cracks were confirmed in the five substrates.

○：5片基板內產生1~5處龜裂○: 1 to 5 cracks occurred in 5 substrates

△：5片基板內產生6~15處龜裂△: 6 to 15 cracks occurred in 5 substrates

×：5片基板內產生16處以上龜裂×: 16 or more cracks were generated in 5 substrates

4.透射率之評價4. Evaluation of transmittance

以顯影後之膜厚達到10μm之方式將聚矽氧烷組合物塗佈於玻璃基板上。繼而使用i射線步進機，於大氣中對整個面進行400mJ/cm2 曝光。The polyoxyalkylene composition was applied onto a glass substrate so that the film thickness after development reached 10 μm. Then, using an i-ray stepper, the entire surface was exposed to 400 mJ/cm 2 in the atmosphere.

(關於實施例1~14、實施例16~27、比較例1~5)(Examples 1 to 14, Examples 16 to 27, and Comparative Examples 1 to 5)

繼曝光之後，使用鹼顯影液(AZ Electronic Materials公司製造之顯影液，2.38%氫氧化四甲基銨水溶液)，於23℃、30秒×2次之條件下進行顯影，藉由純水進行沖洗，去除塗膜表面。After the exposure, development was carried out at 23 ° C, 30 seconds × 2 times using an alkali developing solution (developing solution manufactured by AZ Electronic Materials, 2.38% aqueous solution of tetramethylammonium hydroxide), and rinsing with pure water. , remove the surface of the coating film.

(關於實施例15)(Regarding Example 15)

繼曝光之後，使用PGMEA於23℃、30秒×2次之條件下進行顯影，去除塗膜表面。After the exposure, development was carried out using PGMEA at 23 ° C for 30 seconds × 2 times to remove the surface of the coating film.

使用烘箱，將上述經顯影之基板於220℃、大氣下烘烤6小時。使用分光光度計UV-1600PC(島津公司製造)，於參考部上放置不具塗膜之玻璃基板，測定800nm~300nm之光透射率，確認400nm之光透射率。The developed substrate was baked at 220 ° C for 6 hours in an oven using an oven. Using a spectrophotometer UV-1600PC (manufactured by Shimadzu Corporation), a glass substrate having no coating film was placed on the reference portion, and the light transmittance at 800 nm to 300 nm was measured, and the light transmittance at 400 nm was confirmed.

[合成例1][Synthesis Example 1] (聚矽氧烷a-1之合成)(Synthesis of polyoxyalkylene a-1)

於1L之茄型燒瓶中加入攪拌子、(3-三甲氧基丙基)琥珀酸酐0.60莫耳(173.14g)(商品名X-12-967C，信越化學工業公司製造)、Ba(OH)2 ．H2 O粉末4.00毫莫耳(0.83g)(SIGMA-ALDRICH公司製造)、甲醇0.58莫耳(20.30g)，使用磁力攪拌器進行攪拌。安裝戴氏冷凝器使用油浴自室溫起升溫至75℃為止，回流2.5小時而使琥珀酸酐開環。To a 1 L eggplant type flask, a stirrer, (3-trimethoxypropyl) succinic anhydride 0.60 mol (173.14 g) (trade name X-12-967C, manufactured by Shin-Etsu Chemical Co., Ltd.), Ba(OH) 2 was added. . H 2 O powder 4.00 mmol (0.83 g) (manufactured by SIGMA-ALDRICH), methanol 0.58 mol (20.30 g), and stirred using a magnetic stirrer. The installation of the Daicel condenser was carried out by heating from room temperature to 75 ° C using an oil bath, and refluxing for 2.5 hours to open the succinic anhydride.

於2L之可分離式燒瓶中加入DPD(二苯基矽烷二醇)2.00莫耳 (432.52g)(信越化學工業公司製造)、MEMO(3-甲基丙烯醯氧基丙基三甲氧基矽烷)1.40莫耳(347.69g)、4-羥基-TEMPO(4-羥基-2,2,6,6-四甲基哌啶-1-氧自由基)0.61毫莫耳(0.10g)(東京化成工業公司製造)、上述所製備之(3-三甲氧基丙基)琥珀酸酐開環物之所有量，使用攪拌翼與三一馬達(three-one motor)進行攪拌。安裝戴氏冷凝器，使用油浴自室溫起升溫至95℃為止。1小時後，於繼續加熱之狀態下卸除戴氏冷凝器，連接於三向旋塞、冷阱、真空控制器、真空泵上，將甲醇去除。一面進行真空抽吸一面繼續加熱10小時後，回到常壓並冷卻至室溫為止，藉此獲得透明之聚矽氧烷(a-1，40℃下之黏度為83Poise)。對該聚矽氧烷(a-1)之ESR進行測定，結果觀察到g值=2.007之波峰。又，若算出固形物成分中之自由基濃度，則為0.56×10-6 mol/g。DAD (diphenyldecanediol) 2.00 mol (432.52 g) (manufactured by Shin-Etsu Chemical Co., Ltd.), MEMO (3-methacryloxypropyltrimethoxydecane) was added to a 2 L separable flask. 1.40 mol (347.69 g), 4-hydroxy-TEMPO (4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl radical) 0.61 mmol (0.10 g) (Tokyo Chemical Industry Co., Ltd.) All amounts of the (3-trimethoxypropyl)succinic acid anhydride ring-opening prepared above were stirred using a stirring wing and a three-one motor. A Daimler condenser was installed and the temperature was raised from room temperature to 95 ° C using an oil bath. After 1 hour, the Daimler condenser was removed while continuing to heat, and connected to a three-way cock, a cold trap, a vacuum controller, and a vacuum pump to remove methanol. After heating for 10 hours while performing vacuum suction, the mixture was returned to normal pressure and cooled to room temperature, whereby a transparent polyoxyalkylene (a-1, viscosity at 40 ° C of 83 Poise) was obtained. The ESR of the polyoxyalkylene (a-1) was measured, and as a result, a peak of g value = 2.007 was observed. Further, when the radical concentration in the solid content is calculated, it is 0.56 × 10 -6 mol/g.

[合成例2][Synthesis Example 2] (聚矽氧烷a-2之合成)(Synthesis of polyoxyalkylene a-2)

除了將合成例1中之DPD設定為DCPD(二環戊基矽烷二醇)以外，以與合成例1相同之方式獲得聚矽氧烷(a-2，40℃下之黏度為25Poise)。對該聚矽氧烷(a-2)之ESR進行測定，結果觀察到g值=2.007之波峰。又，若算出固形物成分中之自由基濃度，則為0.54×10-6 mol/g。Polyoxane (a-2, viscosity at 40 ° C of 25 Poise) was obtained in the same manner as in Synthesis Example 1, except that the DPD in Synthesis Example 1 was set to DCPD (dicyclopentyldecanediol). The ESR of the polyoxyalkylene (a-2) was measured, and as a result, a peak of g value = 2.007 was observed. Further, when the radical concentration in the solid content is calculated, it is 0.54 × 10 -6 mol/g.

[合成例3][Synthesis Example 3] (聚矽氧烷a-3之合成)(Synthesis of polyoxyalkylene a-3)

除了將合成例1中之MEMO設定為MEMO(3-甲基丙烯醯氧基丙基三甲氧基矽烷)1.00莫耳、苯基三甲氧基矽烷0.40莫耳以外，以與合成例1相同之方式獲得聚矽氧烷(a-3，40℃下之黏度為100Poise)。對該聚矽氧烷(a-3)之ESR進行測定，結果觀察到g值=2.007之波峰。又，若算出固形物成分中之自由基濃度，則為0.56×10-6 mol/g。The same procedure as in Synthesis Example 1 was carried out except that the MEMO in Synthesis Example 1 was set to MEMO (3-methacryloxypropyltrimethoxydecane) 1.00 mol and phenyltrimethoxydecane 0.40 mol. Polyoxyalkylene (a-3, viscosity at 40 ° C of 100 Poise) was obtained. The ESR of the polyoxyalkylene (a-3) was measured, and as a result, a peak of g value = 2.007 was observed. Further, when the radical concentration in the solid content is calculated, it is 0.56 × 10 -6 mol/g.

[合成例4][Synthesis Example 4] (聚矽氧烷a-4之合成)(Synthesis of polyoxyalkylene a-4)

除了將合成例1中之MEMO設定為MEMO(3-甲基丙烯醯氧基丙基三甲氧基矽烷)1.00莫耳、苯乙烯基三甲氧基矽烷(信越化學工業公司製造，KBM1403)0.40莫耳以外，以與合成例1相同之方式獲得聚矽氧烷(a-4，40℃下之黏度為90Poise)。若對該聚矽氧烷(a-4)之ESR進行測定，則觀察到g值=2.007之波峰。又，若算出固形物成分中之自由基濃度，則為0.53×10-6 mol/g。The MEMO in Synthesis Example 1 was set to MEMO (3-methacryloxypropyltrimethoxydecane) 1.00 mol, styryltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM1403) 0.40 mol A polysiloxane (a-4, viscosity at 40 ° C of 90 Poise) was obtained in the same manner as in Synthesis Example 1. When the ESR of the polyoxyalkylene (a-4) was measured, a peak of g value = 2.007 was observed. Further, when the radical concentration in the solid content is calculated, it is 0.53 × 10 -6 mol/g.

[合成例5][Synthesis Example 5] (聚矽氧烷a-5之合成)(Synthesis of polyoxyalkylene a-5)

於2L之可分離式燒瓶中加入DPD(二苯基矽烷二醇)2.00莫耳(432.52g)(信越化學工業公司製造)、MEMO(3-甲基丙烯醯氧基丙基三甲氧基矽烷)2.00莫耳(496.70g)、4-羥基-TEMPO 0.61毫莫耳(0.10g)(東京化成工業公司製造)、Ba(OH)2 ．H2 O粉末4.00毫莫耳(0.83g)(SIGMA-ALDRICH公司製造)，使用攪拌翼與三一馬達進行攪拌。安裝戴氏冷凝器，使用油浴自室溫起升溫至95℃為止。1小時後，於繼續加熱之狀態下卸除戴氏冷凝器，連接於三向旋塞、冷阱、真空控制器、真空泵上，將甲醇去除。一面進行真空抽吸一面繼續加熱10小時後，回到常壓並冷卻至室溫為止，藉此獲得透明之聚矽氧烷(a-5，40℃下之黏度為75Poise)。對該聚矽氧烷(a-5)之ESR進行測定，結果觀察到g值=2.007之波峰。又，若算出固形物成分中之自由基濃度，則為0.51×10-6 mol/g。DAD (diphenyldecanediol) 2.00 mol (432.52 g) (manufactured by Shin-Etsu Chemical Co., Ltd.), MEMO (3-methacryloxypropyltrimethoxydecane) was added to a 2 L separable flask. 2.00 mol (496.70 g), 4-hydroxy-TEMPO 0.61 mmol (0.10 g) (manufactured by Tokyo Chemical Industry Co., Ltd.), Ba(OH) 2 . H 2 O powder 4.00 mmol (0.83 g) (manufactured by SIGMA-ALDRICH Co., Ltd.) was stirred using a stirring blade and a tri-motor. A Daimler condenser was installed and the temperature was raised from room temperature to 95 ° C using an oil bath. After 1 hour, the Daimler condenser was removed while continuing to heat, and connected to a three-way cock, a cold trap, a vacuum controller, and a vacuum pump to remove methanol. After heating for 10 hours while performing vacuum suction, it was returned to normal pressure and cooled to room temperature, thereby obtaining a transparent polyoxyalkylene (a-5 having a viscosity of 75 Poise at 40 ° C). The ESR of the polyoxyalkylene (a-5) was measured, and as a result, a peak of g value = 2.007 was observed. Further, when the radical concentration in the solid content is calculated, it is 0.51 × 10 -6 mol/g.

[合成例6][Synthesis Example 6] (聚矽氧烷a-6之合成)(Synthesis of polyoxyalkylene a-6)

除了不添加合成例1中之4-羥基-TEMPO以外，以與合成例1相同之方式獲得聚矽氧烷(a-6，40℃下之黏度為83Poise)。對該聚矽氧烷 (a-6)之ESR進行測定，結果於g值2.034~1.984之範圍內未觀察到波峰。Polysiloxane (a-6, viscosity at 40 ° C of 83 Poise) was obtained in the same manner as in Synthesis Example 1, except that 4-hydroxy-TEMPO in Synthesis Example 1 was not added. Polypyroxy The ESR of (a-6) was measured, and as a result, no peak was observed in the range of g value of 2.034 to 1.984.

[合成例7][Synthesis Example 7] (聚矽氧烷a-7之合成)(Synthesis of polyoxyalkylene a-7)

於1L之茄型燒瓶中加入攪拌子、(3-三甲氧基丙基)琥珀酸酐0.30莫耳(86.57g)(商品名X-12-967C，信越化學工業公司製造)、Ba(OH)2 ．H2 O粉末2.00毫莫耳(0.41g)(SIGMA-ALDRICH公司製造)、甲醇0.29莫耳(10.15g)，使用磁力攪拌器進行攪拌。安裝戴氏冷凝器，使用油浴自室溫起升溫至75℃為止，回流2.5小時而使琥珀酸酐開環。To a 1 L eggplant type flask, a stir bar, (3-trimethoxypropyl) succinic anhydride 0.30 mol (86.57 g) (trade name X-12-967C, manufactured by Shin-Etsu Chemical Co., Ltd.), Ba(OH) 2 was added. . H 2 O powder 2.00 mmol (0.41 g) (manufactured by SIGMA-ALDRICH Co., Ltd.) and methanol 0.29 mol (10.15 g) were stirred using a magnetic stirrer. The Daimler condenser was installed, and the temperature was raised from room temperature to 75 ° C using an oil bath, and refluxed for 2.5 hours to open the succinic anhydride.

於2L之可分離式燒瓶中加入苯基三甲氧基矽烷1.00莫耳(198.29g)(東京化成工業公司製造)、MEMO(3-甲基丙烯醯氧基丙基三甲氧基矽烷)0.70莫耳(173.84g)、4-羥基-TEMPO(4-羥基-2,2,6,6-四甲基哌啶-1-氧自由基)0.30毫莫耳(0.05g)(東京化成工業公司製造)、上述所製備之(3-三甲氧基丙基)琥珀酸酐開環物之所有量、PGMEA(丙二醇單甲醚乙酸酯)400g，使用攪拌翼與三一馬達進行攪拌。To a 2 L separable flask, phenyltrimethoxydecane 1.00 mol (198.29 g) (manufactured by Tokyo Chemical Industry Co., Ltd.), MEMO (3-methacryloxypropyltrimethoxydecane) 0.70 mol was added. (173.84 g), 4-hydroxy-TEMPO (4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl radical) 0.30 mmol (0.05 g) (manufactured by Tokyo Chemical Industry Co., Ltd.) The amount of the (3-trimethoxypropyl)succinic anhydride ring-opening prepared above and 400 g of PGMEA (propylene glycol monomethyl ether acetate) were stirred using a stirring blade and a tri-motor.

繼而，滴加將蒸餾水36.00g與5mol/L之鹽酸4.67g混合而成者，攪拌30分鐘。Then, 36.00 g of distilled water and 4.67 g of 5 mol/L hydrochloric acid were added dropwise, and the mixture was stirred for 30 minutes.

安裝戴氏冷凝器，使用油浴自室溫起升溫至95℃為止。2小時後，於繼續加熱之狀態下卸除戴氏冷凝器，連接於三向旋塞、冷阱、真空控制器、真空泵上，去除甲醇、水、PGMEA。一面進行真空抽吸一面繼續加熱4小時後，回到常壓並冷卻至室溫為止，藉此獲得透明之聚矽氧烷(a-7，40℃下之黏度為50Poise)。對該聚矽氧烷(a-7)之ESR進行測定，結果觀察到g值=2.007之波峰。又，若算出固形物成分中之自由基濃度，則為0.60×10-6 mol/g。A Daimler condenser was installed and the temperature was raised from room temperature to 95 ° C using an oil bath. After 2 hours, the Daimler condenser was removed while continuing to heat, and connected to a three-way cock, a cold trap, a vacuum controller, and a vacuum pump to remove methanol, water, and PGMEA. Heating was continued for 4 hours while vacuum suction, and then returned to normal pressure and cooled to room temperature, thereby obtaining a transparent polyoxyalkylene (a-7, viscosity at 40 ° C of 50 Poise). The ESR of the polyoxyalkylene (a-7) was measured, and as a result, a peak of g value = 2.007 was observed. Further, when the radical concentration in the solid content is calculated, it is 0.60 × 10 -6 mol/g.

[合成例8][Synthesis Example 8] (聚矽氧烷a-8之合成)(Synthesis of polyoxyalkylene a-8)

於1L之茄型燒瓶中加入攪拌子、環庚烯二甲酸酐(東京化成工業公司製造)、三甲氧基矽烷(東京化成工業公司製造)、二甲苯，於攪拌下滴加鉑(0)-1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷錯合物溶液(Sigma-Aldrich公司製造)。安裝戴氏冷凝器，於80℃下加熱4小時後，進而於100℃下加熱4小時。冷卻後，藉由蒸餾進行純化，獲得對環庚烯二甲酸酐進行矽氫化而成之化合物A。To a 1 L eggplant type flask, a stir bar, cycloheptene dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), trimethoxy decane (manufactured by Tokyo Chemical Industry Co., Ltd.), xylene, and platinum (0) were added thereto with stirring. A solution of 1,3-divinyl-1,1,3,3-tetramethyldioxane complex (manufactured by Sigma-Aldrich Co., Ltd.). The Daimler condenser was installed, heated at 80 ° C for 4 hours, and further heated at 100 ° C for 4 hours. After cooling, it was purified by distillation to obtain a compound A obtained by subjecting cycloheptene dicarboxylic anhydride to hydrogenation.

於1L之茄型燒瓶中加入攪拌子、化合物A 0.60莫耳(171.81g)、Ba(OH)2 ．H2 O粉末4.00毫莫耳(0.83g)(SIGMA-ALDRICH公司製造)、甲醇0.58莫耳(20.30g)，使用磁力攪拌器進行攪拌。安裝戴氏冷凝器並使用油浴，自室溫起升溫至75℃為止，回流2.5小時而使琥珀酸酐開環。A stirrer, Compound A 0.60 mol (171.81 g), and Ba(OH) 2 were placed in a 1 L eggplant type flask. H 2 O powder 4.00 mmol (0.83 g) (manufactured by SIGMA-ALDRICH), methanol 0.58 mol (20.30 g), and stirred using a magnetic stirrer. The Dairy condenser was installed and an oil bath was used, and the temperature was raised from room temperature to 75 ° C, and refluxed for 2.5 hours to open the succinic anhydride.

於2L之可分離式燒瓶中加入DPD(二苯基矽烷二醇)2.00莫耳(432.52g)(信越化學工業公司製造)、MEMO(3-甲基丙烯醯氧基丙基三甲氧基矽烷)1.40莫耳(347.69g)、4-羥基-TEMPO(4-羥基-2,2,6,6-四甲基哌啶-1-氧自由基)0.61毫莫耳(0.10g)(東京化成工業公司製造)、上述所製備之(3-三甲氧基丙基)琥珀酸酐開環物之0.6莫耳，使用攪拌翼與三一馬達進行攪拌。安裝戴氏冷凝器，使用油浴自室溫起升溫至95℃為止。1小時後，於繼續加熱之狀態下卸除戴氏冷凝器，連接於三向旋塞、冷阱、真空控制器、真空泵上，將甲醇去除。一面進行真空抽吸一面繼續加熱10小時後，回到常壓並冷卻至室溫，藉此獲得透明之聚矽氧烷(a-8，40℃下之黏度為75Poise)。對該聚矽氧烷(a-8)之ESR進行測定，結果觀察到g值=2.007之波峰。又，若算出固形物成分中之自由基濃度，則為0.58×10-6 mol/g。DAD (diphenyldecanediol) 2.00 mol (432.52 g) (manufactured by Shin-Etsu Chemical Co., Ltd.), MEMO (3-methacryloxypropyltrimethoxydecane) was added to a 2 L separable flask. 1.40 mol (347.69 g), 4-hydroxy-TEMPO (4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl radical) 0.61 mmol (0.10 g) (Tokyo Chemical Industry Co., Ltd.) The company produced, 0.6 mol of the (3-trimethoxypropyl)succinic acid anhydride ring-opening prepared above, and stirred using a stirring blade and a tri-motor. A Daimler condenser was installed and the temperature was raised from room temperature to 95 ° C using an oil bath. After 1 hour, the Daimler condenser was removed while continuing to heat, and connected to a three-way cock, a cold trap, a vacuum controller, and a vacuum pump to remove methanol. After heating for 10 hours while performing vacuum suction, it was returned to normal pressure and cooled to room temperature, thereby obtaining a transparent polyoxyalkylene (a-8, viscosity at 40 ° C of 75 Poise). The ESR of the polyoxyalkylene (a-8) was measured, and as a result, a peak of g value = 2.007 was observed. Further, when the radical concentration in the solid content is calculated, it is 0.58 × 10 -6 mol/g.

[合成例9][Synthesis Example 9] (聚矽氧烷a-9之合成)(Synthesis of polyoxyalkylene a-9)

除了將環庚烯二甲酸酐變更為順式-4-環己烯-1,2-二羧酸酐(東京 化成工業公司製造)以外，以與聚矽氧烷a-8相同之方式獲得聚矽氧烷(a-9，40℃下之黏度為80Poise)。對該聚矽氧烷(a-9)之ESR進行測定，結果觀察到g值=2.007之波峰。又，若算出固形物成分中之自由基濃度，則為0.51×10-6 mol/g。Polyfluorene was obtained in the same manner as polyoxymethane a-8 except that the cycloheptene dicarboxylic anhydride was changed to cis-4-cyclohexene-1,2-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.). Oxyalkane (a-9, viscosity at 40 ° C is 80 Poise). The ESR of the polyoxyalkylene (a-9) was measured, and as a result, a peak of g value = 2.007 was observed. Further, when the radical concentration in the solid content is calculated, it is 0.51 × 10 -6 mol/g.

[合成例10][Synthesis Example 10] (聚矽氧烷a-10之合成)(Synthesis of polyoxyalkylene a-10)

除了將環庚烯二甲酸酐變更為伊康酸酐(東京化成工業公司製造)以外，以與聚矽氧烷a-8相同之方式獲得聚矽氧烷(a-10，40℃下之黏度為70Poise)。若對該聚矽氧烷(a-10)之ESR進行測定，則觀察到g值=2.007之波峰。又，若算出固形物成分中之自由基濃度，則為0.52×10-6 mol/g。In addition to the conversion of cycloheptene dicarboxylic anhydride to itaconic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), polyfluorene oxide (a-10, viscosity at 40 ° C was obtained in the same manner as polyoxyalkylene a-8) 70Poise). When the ESR of the polyoxyalkylene (a-10) was measured, a peak of g value = 2.007 was observed. Further, when the radical concentration in the solid content is calculated, it is 0.52 × 10 -6 mol/g.

[合成例11][Synthesis Example 11] (聚矽氧烷a-11之合成)(Synthesis of polyoxyalkylene a-11)

於1L之茄型燒瓶中加入攪拌子、(3-三甲氧基丙基)琥珀酸酐0.60莫耳(173.14g)(商品名X-12-967C，信越化學工業公司製造)、4-羥基-TEMPO(4-羥基-2,2,6,6-四甲基哌啶-1-氧自由基)0.61毫莫耳(0.10g)(東京化成工業公司製造)、Ba(OH)2 ．H2 O粉末4.00毫莫耳(0.83g)(SIGMA-ALDRICH公司製造)、甲醇0.58莫耳(20.30g)，使用磁力攪拌器進行攪拌。安裝戴氏冷凝器，使用油浴自室溫起升溫至75℃為止，回流2.5小時而使琥珀酸酐開環。To a 1 L eggplant type flask, a stirrer, (3-trimethoxypropyl) succinic anhydride 0.60 mol (173.14 g) (trade name X-12-967C, manufactured by Shin-Etsu Chemical Co., Ltd.), 4-hydroxy-TEMPO was added. (4-Hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl radical) 0.61 mmol (0.10 g) (manufactured by Tokyo Chemical Industry Co., Ltd.), Ba(OH) 2 . H 2 O powder 4.00 mmol (0.83 g) (manufactured by SIGMA-ALDRICH), methanol 0.58 mol (20.30 g), and stirred using a magnetic stirrer. The Daimler condenser was installed, and the temperature was raised from room temperature to 75 ° C using an oil bath, and refluxed for 2.5 hours to open the succinic anhydride.

於2L之可分離式燒瓶中加入DPD(二苯基矽烷二醇)2.00莫耳(432.52g)(信越化學工業公司製造)、MEMO(3-甲基丙烯醯氧基丙基三甲氧基矽烷)1.40莫耳(347.69g)、上述所製備之(3-三甲氧基丙基)琥珀酸酐開環物之所有量，使用攪拌翼與三一馬達進行攪拌。安裝戴氏冷凝器，使用油浴自室溫起升溫至95℃為止。1小時後，於繼續加熱之狀態下卸除戴氏冷凝器，連接於三向旋塞、冷阱、真空控制器、真 空泵上，將甲醇去除。一面進行真空抽吸一面繼續加熱10小時後，回到常壓並冷卻至室溫為止，藉此獲得透明之聚矽氧烷(a-11，40℃下之黏度為84Poise)。對該聚矽氧烷(a-11)之ESR進行測定，結果觀察到g值=2.007之波峰。又，若算出固形物成分中之自由基濃度，則為0.50×10-6 mol/g。DAD (diphenyldecanediol) 2.00 mol (432.52 g) (manufactured by Shin-Etsu Chemical Co., Ltd.), MEMO (3-methacryloxypropyltrimethoxydecane) was added to a 2 L separable flask. 1.40 moles (347.69 g), all of the above-prepared (3-trimethoxypropyl)succinic anhydride ring-openings were stirred using a stirring wing and a tri-motor. A Daimler condenser was installed and the temperature was raised from room temperature to 95 ° C using an oil bath. After 1 hour, the Daimler condenser was removed while continuing to heat, and connected to a three-way cock, a cold trap, a vacuum controller, and a vacuum pump to remove methanol. While continuing to heat for 10 hours while performing vacuum suction, it was returned to normal pressure and cooled to room temperature, thereby obtaining a transparent polyoxyalkylene (a-11, viscosity at 40 ° C of 84 Poise). The ESR of the polyoxyalkylene (a-11) was measured, and as a result, a peak of g value = 2.007 was observed. Further, when the radical concentration in the solid content is calculated, it is 0.50 × 10 -6 mol/g.

(聚矽氧烷組合物之製備)(Preparation of polyoxyalkylene composition) [實施例1][Example 1]

於廣口之樣品容器中加入合成例1獲得之聚矽氧烷(a-1)46.57g、IRGACURE819(BASF公司製造)0.79g、4-羥基-TEMPO(東京化成工業公司製造)(0.01g)、EA-1020(新中村化學工業公司製造，EA-1020)37.26g、TINUVIN 405(BASF公司製造)1.16g、EA-6340(新中村化學工業公司製造)9.31g(稀釋溶劑除外)、KBM5103(3-丙烯醯氧基丙基三甲氧基矽烷)4.66g、TINUVIN 152(BASF公司製造)0.23g、PGMEA(丙二醇單甲醚乙酸酯)28.87g，藉由波形轉子進行攪拌並混合。利用孔徑2.5微米之PP(Polypropylene，聚丙烯)製過濾器將其加壓過濾，從而獲得聚矽氧烷組合物。To the sample container of the wide mouth, 46.57 g of polyoxyalkylene (a-1) obtained in Synthesis Example 1, 0.79 g of IRGACURE 819 (manufactured by BASF Corporation), and 4-hydroxy-TEMPO (manufactured by Tokyo Chemical Industry Co., Ltd.) (0.01 g) were added. EA-1020 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., EA-1020) 37.26g, TINUVIN 405 (manufactured by BASF Corporation) 1.16g, EA-6340 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 9.31g (excluding dilution solvent), KBM5103 ( 3-hexyloxypropyltrimethoxydecane) 4.66 g, TINUVIN 152 (manufactured by BASF Corporation), 0.23 g, and PGMEA (propylene glycol monomethyl ether acetate) 28.87 g, which were stirred and mixed by a corrugated rotor. The filter was pressure-filtered using a PP (Polypropylene, polypropylene) filter having a pore size of 2.5 μm to obtain a polyoxyalkylene composition.

[實施例2~27及比較例1~5][Examples 2 to 27 and Comparative Examples 1 to 5]

關於實施例2~27及比較例1~5，按以下之表1、表2及表3所記載之比率使用該表中所記載之成分，除此以外，以與實施例1相同之方式獲得聚矽氧烷組合物或樹脂組合物。The examples 2 to 27 and the comparative examples 1 to 5 were obtained in the same manner as in Example 1 except that the components described in the tables are used in the ratios shown in Tables 1, 2 and 3 below. Polyoxyalkylene composition or resin composition.

又，關於實施例1~27之聚矽氧烷組合物及比較例1~5之樹脂組合物，將振幅設定為200，進行ESR之測定。Further, the polyoxynitride compositions of Examples 1 to 27 and the resin compositions of Comparative Examples 1 to 5 were set to an amplitude of 200 to measure ESR.

對於實施例1~8、12~27之聚矽氧烷組合物及比較例5之樹脂組合物而言，觀察到如圖4所示之g值為2.007之波峰。For the polyoxoxane compositions of Examples 1 to 8, 12 to 27 and the resin composition of Comparative Example 5, a peak having a g value of 2.007 as shown in Fig. 4 was observed.

對於實施例9之聚矽氧烷組合物而言，觀察到如圖5所示之g值為2.007之波峰。For the polyoxyalkylene composition of Example 9, a peak having a g value of 2.007 as shown in Fig. 5 was observed.

對於實施例10之聚矽氧烷組合物而言，觀察到如圖6所示之g值為2.007之波峰。For the polyoxyalkylene composition of Example 10, a peak having a g value of 2.007 as shown in Fig. 6 was observed.

對於實施例11之聚矽氧烷組合物而言，觀察到如圖7所示之g值為2.007之波峰。For the polyoxyalkylene composition of Example 11, a peak having a g value of 2.007 as shown in Fig. 7 was observed.

對於實施例12之聚矽氧烷組合物而言，觀察到如圖8所示之g值為2.007之波峰。For the polyoxyalkylene composition of Example 12, a peak having a g value of 2.007 as shown in Fig. 8 was observed.

對於比較例1~3之樹脂組合物而言，如圖9所示，於g值2.034~1.984之範圍內觀察到波峰，但自由基濃度為請求項規定之範圍外。With respect to the resin compositions of Comparative Examples 1 to 3, as shown in Fig. 9, peaks were observed in the range of g values of 2.034 to 1.984, but the radical concentration was outside the range specified in the claims.

對於比較例4之樹脂組合物而言，如圖10所示，觀察到g值為2.007之波峰。For the resin composition of Comparative Example 4, as shown in Fig. 10, a peak having a g value of 2.007 was observed.

將對實施例1~27之聚矽氧烷組合物及比較例1~5之樹脂組合物進行上述評價之結果示於以下之表1、表2及表3中。The results of the above evaluations of the polyoxyalkylene compositions of Examples 1 to 27 and the resin compositions of Comparative Examples 1 to 5 are shown in Tables 1, 2 and 3 below.

<(B)成分><(B) component>

Irgacure819：BASF公司製造Irgacure 819: manufactured by BASF

<(C)成分><(C) component>

c-1：含有下述式： C-1: Contains the following formula:

所表示之結構之4-羥基-TEMPO(東京化成工業公司製造)4-hydroxy-TEMPO (manufactured by Tokyo Chemical Industry Co., Ltd.)

c-2：含有下述式： C-2: Contains the following formula:

所表示之結構之TEMPO(東京化成工業公司製造)TEMPO (manufactured by Tokyo Chemical Industry Co., Ltd.)

c-3：含有下述式： C-3: Contains the following formula:

所表示之結構之4-側氧基-TEMPO(東京化成工業公司製造)4-sided oxy-TEMPO of the structure shown (manufactured by Tokyo Chemical Industry Co., Ltd.)

c-4：含有下述式： C-4: Contains the following formula:

所表示之結構之3-羧基-2,2,5,5-四甲基吡咯啶-1-氧自由基(東京化成工業公司製造)3-carboxy-2,2,5,5-tetramethylpyrrolidin-1-oxyl radical of the structure shown (manufactured by Tokyo Chemical Industry Co., Ltd.)

<(D)成分><(D) component>

EA-1020：新中村化學工業公司製造EA-1020: Manufactured by Shin-Nakamura Chemical Industry Co., Ltd.

A600：新中村化學工業公司製造A600: Manufactured by Shin-Nakamura Chemical Industry Co., Ltd.

<(E)成分><(E) component>

TINUVIN405：BASF公司製造TINUVIN405: manufactured by BASF

<(F)成分><(F) component>

EA-6340：新中村化學工業公司製造 酸值：85mgKOH/gEA-6340: Manufactured by Shin-Nakamura Chemical Industry Co., Ltd. Acid value: 85mgKOH/g

SPC1001：昭和電工公司製造 酸值：86mgKOH/gSPC1001: manufactured by Showa Denko Co., Ltd. Acid value: 86mgKOH/g

<(G)成分><(G) component>

KBM5103：信越化學工業股份有限公司製造KBM5103: manufactured by Shin-Etsu Chemical Co., Ltd.

<(H)成分><(H) component>

TINUVIN152：BASF公司製造TINUVIN152: manufactured by BASF

<(I)成分><(I) component>

PEGMEA：東京化成工業公司製造PEGMEA: manufactured by Tokyo Chemical Industry Co., Ltd.

關於實施例1~27之耐龜裂性，使用經Mo濺鍍之矽晶圓進行評價，結果實施例1~20及實施例24~27之圖案未產生剝離，亦未產生 龜裂，但實施例21~23之圖案產生了剝離。Regarding the crack resistance of Examples 1 to 27, evaluation was carried out using a silicon wafer sputtered with Mo. As a result, the patterns of Examples 1 to 20 and Examples 24 to 27 were not peeled off, nor were produced. The cracks were formed, but the patterns of Examples 21 to 23 were peeled off.

對比較例5進行曝光並顯影，結果膜未殘留，故無法進行評價。When Comparative Example 5 was exposed and developed, the film did not remain, and evaluation could not be performed.

[產業上之可利用性][Industrial availability]

本發明之含有鹼可溶性基之聚矽氧烷組合物可作為顯示裝置之絕緣材料而較佳地利用於半導體裝置中之表面保護膜、層間絕緣膜、α射線遮蔽膜等之形成，以及搭載有影像感測器或微機械、或微致動器之半導體裝置等及其形成。The alkali-soluble group-containing polyoxoxane composition of the present invention can be preferably used as an insulating material for a display device, and is preferably used for forming a surface protective film, an interlayer insulating film, an α-ray shielding film, and the like in a semiconductor device, and is equipped with Image sensor or micromechanical, or semiconductor device of microactuator, etc. and its formation.

Claims (13)

一種含自由交聯基之聚矽氧烷組合物，其於大氣下、24℃、常壓及遮蔽波長為400nm以下之光的條件下靜置24小時後，使用電子自旋共振(ESR)裝置進行測定時，具有g值為2.034~1.984之波峰，且相對於組合物中之固形物成分1g，含有0.1×10-6 ~120×10-6 莫耳之自由基。A polyoxane composition containing a free crosslinking group, which is subjected to an electron spin resonance (ESR) device after standing for 24 hours under the conditions of 24 ° C, normal pressure, and a light having a shielding wavelength of 400 nm or less. When the measurement is carried out, it has a peak having a g value of 2.034 to 1.984, and contains 0.1 × 10 -6 to 120 × 10 -6 mol of a radical with respect to 1 g of the solid content in the composition. 如請求項1之含自由交聯基之聚矽氧烷組合物，其具有下述結構： {式中，R1 、R2 、R3 及R4 分別獨立地表示氫原子及/或碳數1~10之一價有機基，而且R1 與R2 、或R3 與R4 可相互鍵結而形成環結構}。A polyoxane composition containing a free crosslinking group according to claim 1, which has the following structure: In the formula, R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom and/or a monovalent organic group having 1 to 10 carbon atoms, and R 1 and R 2 or R 3 and R 4 may mutually Bonding to form a ring structure}. 如請求項1或2之含自由交聯基之聚矽氧烷組合物，其進而含有鹼可溶性基。 A polyoxane composition containing a free crosslinking group according to claim 1 or 2, which further contains an alkali-soluble group. 如請求項1或2之含自由交聯基之聚矽氧烷組合物，其進而含有(B)光自由基起始劑。 A polyoxane composition containing a free crosslinking group according to claim 1 or 2, which further contains (B) a photoradical initiator. 如請求項4之聚矽氧烷組合物，其中相對於上述聚矽氧烷組合物中之總固形物成分100質量份，含有1質量份~99質量份之(A)含自由交聯基之聚矽氧烷、0.01質量份~15質量份之(B)光自由基起始劑及0.005質量份~2質量份之(C)硝醯基化合物。 The polyoxyalkylene composition according to claim 4, wherein the component (A) contains a free crosslinking group in an amount of from 1 part by mass to 99 parts by mass based on 100 parts by mass of the total solid content of the polyoxoxane composition. Polysiloxane, 0.01 parts by mass to 15 parts by mass of (B) photoradical initiator and 0.005 parts by mass to 2 parts by mass of (C) nitroguanidine compound. 如請求項5之聚矽氧烷組合物，其中上述(C)硝醯基化合物係由下 述通式表示： {式中，R5 表示氫原子、碳數1~12之烷基、羥基、胺基、羧酸基、氰基、雜原子取代烷基，或者經由醚、酯、醯胺或胺基甲酸酯鍵而鍵結之一價有機基，R6 表示二或三價有機基，n1 及m1 為滿足1≦n1 +m1 ≦2之整數，n2 及m2 為滿足1≦n2 +m2 ≦2之整數，n3 及m3 為滿足1≦n3 +m3 ≦2之整數，而且1為2或3之整數}。The polyoxyalkylene composition of claim 5, wherein the (C) nitrate compound is represented by the following formula: In the formula, R 5 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a hydroxyl group, an amine group, a carboxylic acid group, a cyano group, a hetero atom-substituted alkyl group, or an ether, an ester, a guanamine or an aminocarboxylic acid. The ester bond is bonded to a monovalent organic group, R 6 represents a divalent or trivalent organic group, n 1 and m 1 are integers satisfying 1≦n 1 +m 1 ≦2, and n 2 and m 2 are satisfying 1≦n An integer of 2 + m 2 ≦ 2, n 3 and m 3 are integers satisfying 1 ≦ n 3 + m 3 ≦ 2, and 1 is an integer of 2 or 3. 如請求項5之聚矽氧烷組合物，其中上述(A)含自由交聯基之聚矽氧烷係含有(甲基)丙烯醯基及/或苯乙烯基之聚矽氧烷。 The polyoxyalkylene composition according to claim 5, wherein the (A) polyoxyalkylene containing a free crosslinking group contains a (meth)acryl fluorenyl group and/or a styryl group polyoxyalkylene. 如請求項1之聚矽氧烷組合物，其中相對於上述聚矽氧烷組合物中之總固形物成分100質量份，進而含有5質量份~45質量份之(D)具有光聚合性雙鍵之化合物。 The polyoxyalkylene composition of claim 1, wherein the (D) photopolymerizable double is further contained in an amount of from 5 parts by mass to 45 parts by mass based on 100 parts by mass of the total solid content of the polyoxoxane composition. The compound of the bond. 如請求項1之聚矽氧烷組合物，其中相對於上述聚矽氧烷組合物中之總固形物成分100質量份，進而含有0.01質量份~10質量份之(E)紫外線吸收劑。 The polyoxyalkylene composition of claim 1, which further contains 0.01 parts by mass to 10 parts by mass of the (E) ultraviolet absorber relative to 100 parts by mass of the total solid content of the polyoxyalkylene composition. 如請求項1之聚矽氧烷組合物，其中相對於上述聚矽氧烷組合物中之總固形物成分100質量份，進而含有1質量份~50質量份之(F)酸值為10~200mgKOH/g之鹼可溶性樹脂。 The polyoxyalkylene composition according to claim 1, wherein the (F) acid value is from 10 parts by mass to 50 parts by mass per 100 parts by mass of the total solid content of the polyoxyalkylene composition. 200 mg KOH / g of alkali soluble resin. 如請求項5之聚矽氧烷組合物，其中上述(A)含自由交聯基之聚矽氧烷具有下述通式所表示之結構： {式中，Ph表示苯基}。The polyoxyalkylene composition of claim 5, wherein the (A) polyfluorene oxide having a free crosslinking group has a structure represented by the following formula: In the formula, Ph represents a phenyl group}. 一種硬化物，其係使如請求項1至11中任一項之聚矽氧烷組合物硬化而得。 A cured product obtained by hardening a polyoxyalkylene composition according to any one of claims 1 to 11. 一種透明絕緣膜，其係使如請求項1至11中任一項之聚矽氧烷組合物硬化而得。 A transparent insulating film obtained by hardening the polyoxyalkylene composition according to any one of claims 1 to 11.
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