TW508457B - Radiation sensitive composition and color liquid crystal display device - Google Patents
Radiation sensitive composition and color liquid crystal display device Download PDFInfo
- Publication number
- TW508457B TW508457B TW089125510A TW89125510A TW508457B TW 508457 B TW508457 B TW 508457B TW 089125510 A TW089125510 A TW 089125510A TW 89125510 A TW89125510 A TW 89125510A TW 508457 B TW508457 B TW 508457B
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- radiation
- acid
- meth
- acrylate
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- 239000000203 mixture Substances 0.000 title claims abstract description 131
- 230000005855 radiation Effects 0.000 title claims abstract description 106
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 43
- 239000000758 substrate Substances 0.000 claims abstract description 103
- 239000000178 monomer Substances 0.000 claims abstract description 88
- 239000010408 film Substances 0.000 claims abstract description 66
- 229920005989 resin Polymers 0.000 claims abstract description 31
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- 238000002161 passivation Methods 0.000 claims abstract description 8
- -1 maleic anhydride imine Chemical class 0.000 claims description 123
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 97
- 238000011049 filling Methods 0.000 claims description 55
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- 125000000954 2-hydroxyethyl group Chemical class [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
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- ZCZFEIZSYJAXKS-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] prop-2-enoate Chemical compound OCC(CO)(CO)COC(=O)C=C ZCZFEIZSYJAXKS-UHFFFAOYSA-N 0.000 claims 1
- SSOONFBDIYMPEU-UHFFFAOYSA-N [3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propyl] prop-2-enoate Chemical compound OCC(CO)(CO)COCC(CO)(CO)COC(=O)C=C SSOONFBDIYMPEU-UHFFFAOYSA-N 0.000 claims 1
- OYEHPCDNVJXUIW-UHFFFAOYSA-N plutonium atom Chemical compound [Pu] OYEHPCDNVJXUIW-UHFFFAOYSA-N 0.000 claims 1
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- 238000007738 vacuum evaporation Methods 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000001052 yellow pigment Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133509—Filters, e.g. light shielding masks
- G02F1/133512—Light shielding layers, e.g. black matrix
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
- G02F1/1362—Active matrix addressed cells
- G02F1/1368—Active matrix addressed cells in which the switching element is a three-electrode device
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
- H01L29/76—Unipolar devices, e.g. field effect transistors
- H01L29/772—Field effect transistors
- H01L29/78—Field effect transistors with field effect produced by an insulated gate
- H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2201/00—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00
- G02F2201/40—Arrangements for improving the aperture ratio
Landscapes
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Optics & Photonics (AREA)
- Power Engineering (AREA)
- Ceramic Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Computer Hardware Design (AREA)
- Materials For Photolithography (AREA)
Abstract
Description
508457 A7 B7 五、發明説明(1 ) 本發明係有關一種用於包含彩色液晶顯示裝置之畫素 .及/或黑色基質之著色層作爲薄膜電晶體(TFT)形式 彩色液晶顯示裝置之驅動基板上所使用之輻射敏感放射線 性組成物及彩色液晶顯示裝置之發明。 .一般使用薄膜電晶體(T F T )基板之彩色液晶顯示 裝置中,以往,多分別製作顯示彩色畫像之彩色濾膜基板 與,配置有(TFT)薄膜電晶體之驅動用基板後,再將 該彩色濾膜基板與該驅動用基板以相互貼合之方式製得。 但,此方式中,因貼合時位置之精確度較低,故黑色基質 之寬度需較寬,則會有開口率(即,可透過光之開口部的 比例)不易提高之缺點。 又,對應前記方式,復開發出一種於配置有薄膜電晶 體(TFT)之驅動用基板的表面上,直接形成或介由氮 化矽膜等鈍化膜所形成之著色膜,而將形成有此著色膜之 基板,與以濺鍍方式形成I T〇(塗布有錫之氧化銦)電 極之基板進行貼合之方法。此方法中,因驅動用基板上直 接形成含有畫素或黑色基質之著色層,故不需使用將彩色 濾膜基板與該驅動用基板進行貼合之步驟,故與前者相比 較時,可使開口率更向上提昇,而可得到具有明亮且具有 高精確度之顯示裝置。 但,使用後者之方式形成著色層時,因需導通著色層 上方濺射所得之I T 0電極與著色層下方之驅動用基板的 端子,故需形成1至15 左右之通孔或c字型凹孔。 以往,多會形成通孔或C字型凹孔,故目前於其後之 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) (請先閲讀背面之注意事項再填寫本頁) -•参 經濟部智慧財產局a(工消費合作社印製 -4- 508457 A7 B7 五、發明説明(2 (請先閲讀背面之注意事項再填寫本頁) I Τ〇電極的濺射步驟中,可兼得到I τ〇電極未形成斷 線形狀之著色層,且不會有顯像殘影、優良表面平滑性、 與驅動用基板或氮化矽膜等鈍化膜密著性極佳之輻射敏感 放射線性組成物仍未被公開於世。 又,於配置有薄膜電晶體(T F Τ )之驅動用基板之 表面上形成著色層之方式,一般多必須對驅動用基扳上所 設置之著色層的表面以I Τ 0進行濺射處理,以使所得 I Τ 0層依特定形狀形成圖型,而形成I τ〇電極。但, 於此I Τ〇層上形成圖型之步驟,一般多由塗布正型光阻 、照射放射線、顯像、對I Τ 0層進行蝕刻與將正型光阻 層剝離等一連串步驟所構成,而正型光阻之剝離方式多使 用剝離液進行。因此,若著色層對該剝離液之膨脹度較大 時,其上之IT〇電極將會產生斷裂,而會產生彩色液晶 顯不裝置機能障礙等問題。 此外,依此方式所得到之液晶顯示裝置,施加電壓之 部位會有未能正確地操作,或未施加電壓之畫素或有誤動 等顯示不良之情形產生,故就液晶顯示裝置之信賴度而言 爲一具有疑慮之處。 因此,本發明之目的,係提供一種不會引起通孔或C 字型凹孔,於I T〇成膜時不會有因斷線而生之顯示不良 情形,於著色層表面上形成電極時所使用之正型光阻不易 因剝離異而產生膨脹現象,施加電壓之部分不會有因操作 不佳所產生之顯示不佳,或未施加電壓之部分不會有因誤 動而造成顯示不良之情形,顯像時不會產生殘影,且具有 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -5 經濟部智慧財產局8工消費合作社印製 Lk 508457 A7 _ B7 五、發明説明(3 ) 優良表面平滑性,可形成與薄膜電晶體(T F T )中所配 置之驅動用基板或氮化矽膜等鈍化膜具有優良密著性之著 色層所使用之輻射敏感放射線性組成物。 本發明之另一目的,係提供一種具有由上記輻射敏感 放射線性組成物所形成之著色層的畫素所構成之彩色液晶 顯示裝置。 本發明之其他目的與優點可經由以下說明而了解。 依本發明之內容,本發明之目的與優點,第1點係爲 , ' 一種輻射敏感放射線性組成物,其係含有(A )著色 劑、(B )鹼可溶性樹脂、(C )多官能性單體與(D ) 光聚合起始劑,且其係用於形成薄膜電晶體(T F T )形 .式液晶顯示裝置的驅動用基板上之著色層者。 又,本發明之第2點係爲, 一種薄膜電晶體(T F T )形式之液晶顯示裝置,其 係於驅動基板上具有直接或介由鈍化膜所形成之著色層, 且該著色層係由本發明之上記輻射敏感放射線性組成物所 形成者。 本發明中,所稱「放射線」係含有可見光、紫外光、 遠紫外光、電子線、X線等之意義。 以下,將對本發明作更詳細之敘述。 著色劑 本發明之著色劑,對於色調並未有特別之限定,可依 本紙張尺度適用中周國家標準(CNS ) A4規格(210X297公釐) (請先閲讀背面之注意事項再填寫本頁) 508457 經濟部智慧財產局B工消费合作社印製 A7 B7 五、發明説明(4 ) 製得之濾色片用途作適當之選擇,且可爲顏料、染料或天 然色素等。 濾色片多尋求具有高精密之發色性與耐熱性,故本發 明之者色劑以使用發色性較高,且具有耐熱性較高之著色 劑、或耐熱分解性較高之著色劑爲佳,一般以使用顏料, 特別是使用有機顏料及/或碳黑爲較佳。 前記有機顏料,例如彩色係數S〇ciety of Dyers and Colounm公司發行,以下同。)中分類爲顏料 (Pigment )之化合物,具體而言,例如、下記附有色彩係數 (C · I ·)編號者。 C· I ·顏料黃83、C· I ·顏料黃128、 C. I ·顏料黃138、C· I ·顏料黃工39、 C · I ·顏料黃1 5 〇、C · I ·顏料黃1 5 1、 c· 1 ·顏料黃152、C· I ·顏料黃153、 C· I ·顏料黃154、C· I ·顏料黃工55、 C. I ·顏料黃156、C· I ·顏料黃166、 C.I·顏料黃168、C·I·顏料黃175、 C · I ·顏料黃1 8 5 ; C·I·顏料紫19、C·I·顏料紫23、 C·I·顏料紫29、c·I·顏料紫32、c·I·顏 料紫36、C.i·顏料紫38; (:.1.顔料紅177、(:.1.顏料紅2〇2、 C · I ·顏料紅2 〇 6、C · I ·顏料紅2 〇 7、 C · I ·顏料紅2 〇 8、C · I ·顏料紅2 〇 9、 本紙張尺度適用中國國家榡準(CNS〉A4規格(2丨0X297公釐) -----0^------、玎----- (請先閎讀背面之注意事項再填寫本頁) 508457 A7 B7 五、發明説明(5 ) C . I , ,顏料紅2 1 5 > C . I .顏料紅2 1 6、 C . I . ,顏料紅2 2 0 、(:· I .顏料紅2 2 4、 C . I , .顏料紅2 2 6 > C . I .顏料紅2 4 2、 C . I .顏料紅2 4 3 、(:· I .顏料紅2 4 5、 C · I .顏料紅2 5 4 > C . I .顏料紅2 5 5、 C . I .顏料紅2 6 4 > C . I :.顏料紅2 6 5 ; C • I ·顏料藍 1 5、C · I .顏料藍 1 5:3 C , .I .顏料藍1 5 4、C . I .顏料藍 1 5:6 C • I ·顏料綠7 > C . I :.顏料綠3 6 C • I ·顏料黑 1 ' C . 1 :.顏料黑7 〇 (請先閲讀背面之注意事項再填寫本頁)508457 A7 B7 V. Description of the invention (1) The present invention relates to a pixel for a color liquid crystal display device, and / or a black matrix colored layer as a driving substrate for a color liquid crystal display device in the form of a thin film transistor (TFT). Inventions of the radiation-sensitive radiation composition used and the color liquid crystal display device. Generally, in a color liquid crystal display device using a thin film transistor (TFT) substrate, in the past, a color filter film substrate for displaying a color image and a driving substrate equipped with a (TFT) thin film transistor were separately prepared, and then the color was changed. The filter substrate and the driving substrate are produced by being bonded to each other. However, in this method, since the accuracy of the position at the time of bonding is low, the width of the black substrate needs to be wide, and there is a disadvantage that the aperture ratio (that is, the proportion of openings that can transmit light) is difficult to increase. In response to the foregoing method, a colored film formed directly on the surface of a driving substrate on which a thin film transistor (TFT) is arranged or formed by a passivation film such as a silicon nitride film is developed. A method for bonding a colored film substrate to a substrate on which an IT0 (tin-coated indium oxide) electrode is formed by sputtering. In this method, since a colored layer containing pixels or a black matrix is directly formed on the driving substrate, the step of bonding the color filter substrate and the driving substrate is not required. Therefore, when compared with the former, it is possible to make The aperture ratio is further increased to obtain a bright and highly accurate display device. However, when using the latter method to form the colored layer, the IT 0 electrode obtained by sputtering above the colored layer and the terminal of the driving substrate below the colored layer need to be turned on, so it is necessary to form a through hole or a c-shaped recess of about 1 to 15 hole. In the past, through-holes or C-shaped recessed holes were often formed, so the current paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page) -• Participated in the Intellectual Property Bureau of the Ministry of Economy a (printed by the Industrial and Consumer Cooperatives -4- 508457 A7 B7 V. Description of the invention (2 (Please read the precautions on the back before filling this page) I In the sputtering step of the Τ〇 electrode It can also obtain a colored layer where the I τ〇 electrode does not form a broken line, and there is no image sticking, excellent surface smoothness, and radiation sensitivity with excellent adhesion to a passivation film such as a driving substrate or a silicon nitride film. The radiation composition has not been disclosed to the world. In addition, in the method of forming a coloring layer on the surface of a driving substrate on which a thin film transistor (TF T) is disposed, it is generally necessary to set the coloring layer provided on the driving substrate. The surface of I is sputtered with I TO to form a pattern of the obtained I TO layer according to a specific shape to form an I τ〇 electrode. However, the steps of forming a pattern on this I TO layer are generally performed by Coating positive type photoresist, radiation irradiation, imaging The I TO layer is formed by a series of steps such as etching and stripping the positive photoresist layer, and the stripping method of the positive photoresist is mostly performed using a stripping solution. Therefore, if the coloring layer has a large degree of expansion of the stripping solution, The IT0 electrode thereon will be broken, which will cause problems such as the malfunction of the color liquid crystal display device. In addition, the liquid crystal display device obtained in this way may not operate correctly at the place where the voltage is applied, or Pixels with no voltage applied or display failures such as malfunction may occur, so there is a doubt in terms of the reliability of the liquid crystal display device. Therefore, the object of the present invention is to provide a through hole or The C-shaped recessed hole does not have any display failure due to disconnection during IT0 film formation. The positive photoresist used when forming the electrode on the surface of the colored layer is not easy to cause expansion due to peeling. The voltage part will not have poor display due to poor operation, or the part to which voltage is not applied will not cause poor display due to misoperation. There will be no residual image during development. This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -5 Printed by the 8th Industrial Cooperative Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Lk 508457 A7 _ B7 V. Description of the invention (3) Excellent surface smoothness, which can be formed with A radiation-sensitive radiation composition used in a coloring layer having a good adhesion with a driving substrate or a passivation film such as a silicon nitride film disposed in a thin film transistor (TFT). Another object of the present invention is to provide A color liquid crystal display device composed of pixels of a coloring layer formed by the radiation-sensitive radiation composition described above. Other objects and advantages of the present invention can be understood through the following description. According to the content of the present invention, the object and advantage of the present invention The first point is, 'A radiation-sensitive radiation composition comprising (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a photopolymerization initiator, And it is used for forming a coloring layer on a driving substrate of a thin film transistor (TFT) type liquid crystal display device. In addition, the second aspect of the present invention is a liquid crystal display device in the form of a thin film transistor (TFT), which has a colored layer formed directly or through a passivation film on a driving substrate, and the colored layer is formed by the present invention. Record the formation of radiation-sensitive radioactive composition. In the present invention, the term "radiation" includes the meaning of visible light, ultraviolet light, far ultraviolet light, electron rays, X-rays, and the like. Hereinafter, the present invention will be described in more detail. Coloring agent The coloring agent of the present invention is not particularly limited in color tone, and can be applied to the National Standard (CNS) A4 specification (210X297 mm) according to the paper size (please read the precautions on the back before filling this page) 508457 Printed by A, B7, and Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (4) The color filter produced is suitable for selection, and can be pigments, dyes or natural pigments. Most color filters are required to have high-precision color development and heat resistance. Therefore, the colorants of the present invention use coloring agents with high color development and high heat resistance, or colorants with high thermal decomposition resistance. Preferably, pigments are used, especially organic pigments and / or carbon black. The aforementioned organic pigments are, for example, issued by the Society of Dyers and Colounm company, and the same applies hereinafter. ) Compounds classified as pigments in), specifically, for example, those with color coefficient (C · I ·) numbers attached below. C · I · Pigment Yellow 83, C · I · Pigment Yellow 128, C. I · Pigment Yellow 138, C · I · Pigment Yellow 39, C · I · Pigment Yellow 1 50, C · I · Pigment Yellow 1 5 1. c · 1 · Pigment Yellow 152, C · I · Pigment Yellow 153, C · I · Pigment Yellow 154, C · I · Pigment Yellow 55, C.I · Pigment Yellow 156, C · I · Pigment Yellow 166, CI · Pigment Yellow 168, C · I · Pigment Yellow 175, C · I · Pigment Yellow 1 8 5; C · I · Pigment Purple 19, C · I · Pigment Purple 23, C · I · Pigment Purple 29, c · I · Pigment Violet 32, c · I · Pigment Violet 36, Ci · Pigment Violet 38; (: .1.Pigment Red 177, (: .1.Pigment Red 202, C · I · Pigment Red 2 〇 6. C · I · Pigment Red 2 〇07, C · I · Pigment Red 2 〇8, C · I · Pigment Red 2 〇9, This paper size applies to China National Standard (CNS> A4 specification (2 丨 0X297) (%) ----- 0 ^ ------, 玎 ----- (Please read the notes on the back before filling out this page) 508457 A7 B7 V. Description of the invention (5) C. I, , Pigment Red 2 1 5 > C. I. Pigment Red 2 1 6, C. I., Pigment Red 2 2 0, (: · I. Pigment Red 2 2 4, C. I,. Pigment Red 2 2 6 > C. I. Pigment Red 2 4 2, C. I. Pigment Red 2 4 3, (: · I. Pigment Red 2 4 5, C · I. Pigment Red 2 5 4 > C. I. Pigment Red 2 5 5, C. I. Pigment Red 2 6 4 > C. I:. Pigment Red 2 6 5; C • I · Pigment Blue 1 5, C · I. Pigment Blue 1 5: 3 C,. I. Pigment Blue 15 4, C. I. Pigment Blue 1 5: 6 C • I · Pigment Green 7 > C. I: .Pigment Green 3 6 C • I · Pigment Black 1 'C. 1: .Pigment Black 7 〇 (Please read the precautions on the back before filling in this page)
經濟部智慧財產局8工消費合作社印製 ___L 此些有機顏料可單獨使用或將2種以上混合使用皆可 0 前記有機顏料,例如可使用硫酸再結晶法、溶劑洗淨 法或其組合等方式再精製使用。 由本發明之輻射敏感放射線性組成物所形成之著色層 之體積電阻係數極高,故在使用上記精製後使不純物量減 少之有機顏料時,可使著色層之體積電阻係數更加提高。 又,無機顏料之具體例,例如氧化鈦、氧化鋇、碳酸 鈣、鋅白、硫酸鉛、黃色鉛、鋅黃、氧化鐵紅(紅色氧化 鐵(m ))、鎘紅、群青、深藍、氧化鉻綠、鈷綠、琥珀 、鈦黑、合成鐵黑、碳黑等顏料。 此些無機顏料可單獨使用或將2種以上混合使用皆可 〇 使用本發明之輻射敏感放射線性組成物作作爲形成畫 本紙張尺度適用中國國家榡準(CNS )八4規格(210X297公釐) ' ~ -8 - 經濟部智慧財產局S工消費合作社印製 508457 A7 ____B7__ 五、發明説明(6 ) 素使用時,較佳係使用1種以上之有機顏料作爲著色劑, 又作爲形成碳黑使用時,較佳係使用2種以上有機顏料及 /或碳黑作爲著色劑爲宜。 又,由本發明之輻射敏感放射線性組成物所形成之著 色層,係具有極低之介電係數値,且該著色層中之含量, 係與後述(B )〜(D )成分或添加劑成分之使用量相關 ,較佳爲1至6 0重量%,更佳爲3至3 5重量%,最佳 爲5至1 5重量%時,可得到更低値之介電係數。 又,本發明中,前記各顏料可彳衣所期待之目的,對該 粒子表面使用聚合物進行改質後使用。可對顏料粒子表面 進行改質之聚合物,例如特開平8 — 2 5 9 8 7 6號公報 等所記載之聚合物或,市售之各種顏料分散用之聚合物或 低聚物等。 本發明之著色劑可依所期望之目的而與分散劑共同使 用。 前記分散劑,例如陽離子、陽離子、質子、兩性、聚 矽氧烷、氟系等界面活性劑。 前記界面活性劑之例示,如聚氧乙烯月桂基醚、聚氧 乙烯硬脂基醚、聚氧乙烯油基醚等聚氧乙烯烷基醚;聚氧 乙烯η -辛苯基醚、聚氧乙烯n 一壬苯基醚等聚氧乙烯烷 苯基醚;聚乙二醇二月桂酸酯、聚乙二醇二硬脂酸酯等聚 乙烯二酯類;山梨糖醇酐脂肪酸酯類;脂肪酸變性聚酯類 ;第3級胺變性聚尿烷類;聚乙烯亞胺類等以外,尙包含 商品名表示之Κ Ρ (信越化學工業公司製)、波利伏(共 本紙張尺度適用中國國家標準(CNS ) Α4規格(210X 297公釐) 1^-------»衣------1Τ------·% (請先閱讀背面之注意事項再填寫本頁) -9 - 508457 A7 _____B7____ 五、發明説明(7 ) (請先閲讀背面之注意事項再填寫本頁) 榮社化學公司製)、耶普多(托卡化學工業公司製)、美 格福(大日本油墨化學公司製)、福利拉(住友3 Μ公司 製)、阿沙皮、沙福隆(以上,旭硝子公司製)、 Disperbyk(比克化學公司(ΒΥΚ)製)、Solsperse (瑞內 卡公司(ZENEKA )製)、EFKA (艾富卡化學公司( EFKA )製)等。 此些界面活性劑,可單獨或將2種以上混合使用皆可 〇 界面活性劑之使用量,以對著色劑1 〇 〇重量份,較 佳添加5 0重量份以下,更佳爲3 0重量份以下。 (B )鹼可溶件樹脂 經濟部智慧財產局員工消費合作社印製 本發明之驗可溶性樹脂,以對(A )著色劑具有膠黏 劑之作用,且於製造濃色片時,對於顯像步驟中所使用之 顯像液,更佳爲對鹼顯像液具有可溶性者爲佳。例如殘基 、苯酚性羥基與磺酸基等具有酸性官能基之光聚合性不飽 和單體與其他可共聚之不飽和單體(以下,簡稱爲「共聚 合性不飽和單體」)之共聚合物等。 含殘基之光聚合性不飽和單體,(以下,簡稱「含竣 基之不I包和單體」)例如,(甲基)丙燦酸、巴豆酸、α -氯基丙烯酸、桂皮酸等不飽和羧酸類;馬來酸、馬來酸 酉干、虽馬酸、虽馬酸酉干、依康酸、依康酸酐、檬康酸、檬 康酸酐、中康酸等不飽和羧酸或其酸酐類;3價以上不飽 和多元羧酸或其酸酐類;琥珀酸一〔2〜(甲基)丙嫌醯 本紙張尺度適用中國國家榡準(CNS ) Α4規格(210X 297公釐) ^〜-- -10- 508457 Α7 Β7 五、發明説明(8 ) 氧基乙酯〕、琥珀酸一(2 —(甲基)丙烯醯氧基乙酯) 等2價以上多元羧酸之一〔(甲基)丙烯醯氧烷基〕酯類 ;ω〜羧基聚己內醯一(甲基)丙烯酸酯等二末端具有羧 基與羥基之聚合物的一(甲基)丙醯酸酯類等等。 此些含羧基之不飽和單體中,又以(甲基)丙烯酸、 琥珀酸一〔2 —(甲基)丙烯醯氧基乙酯〕爲佳。 又,前記含羧基之不飽和單體可單獨或將2種以上一 起使用皆可。 又具有苯酚性羥基之光聚合性不飽和單體,例如, 〇 —羥基苯乙烯、m -羥基苯乙烯、ρ -羥基苯乙烯 、〇 —羥基一 α —羥基苯乙烯、m —羥基一α —甲基苯乙 烯、Ρ —羥基一 α —甲基苯乙烯、Ν — 〇 —羥基苯基馬來 酸酐縮亞胺、Ν — m -羥苯基馬來酸酐縮亞胺、Ν - ρ -羥苯基馬來酸酐縮亞胺等。 此些具有苯酚性羥基之光聚合性不飽和單體,其可單 獨使用或將2種以上一起使用。 又,具有磺酸基之光聚合性不飽和單體,例如異戊二 烯磺酸、P —苯乙烯磺酸等。 此些具有磺酸基之光聚合性不飽和單體,其可單獨使 用或將2種以上一起使用。 而共聚性不飽和單體例如,聚苯乙烯、聚甲基(甲基 )丙烯酸酯、聚一 η -丁基(甲基)丙烯酸酯、聚矽氧烷 等聚合物分子鏈末端具有一(甲基)丙烯醯氧基之巨單體 類(以下簡稱「巨單體」類):Ν -苯基馬來酸酐縮亞胺 本紙張尺度適用中國國家標準(CNS ) Α4規格(21〇Χ29:7公釐) ---------衣-- (請先閱讀背面之注意事項再填寫本頁) 訂 ▼線 經濟部智慧財產局S工消費合作社印製 508457 A7 B7 五、發明説明(9 ) (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印災 、N — 〇 —羥苯基馬來酸酐縮亞胺、N — m —羥苯基馬來 酸酐縮亞胺、N - p -羥苯基馬來酸酐縮亞胺、N - 〇 — 甲苯基馬來酸酐縮亞胺、N - 〇 -甲氧基苯基馬來酸酐縮 亞胺、N - m —甲氧基苯基馬來酸酐縮亞胺、N — P —甲 氧基酸酐亞胺等N -(取代)芳基馬來酸酐縮亞胺或N -環己基馬來酸酐縮亞胺等N位-取代馬來酸酐縮亞胺;苯 乙嫌、α —甲基苯乙嫌、〇 —乙嫌基甲苯、m —乙儲基甲 苯、P —乙烯基甲苯、P —氯基苯乙烯、〇 —甲氧基苯乙 烯、m —甲氧基苯乙烯、p —甲氧基苯乙烯、〇 一乙烯苄 基甲基酸、m —乙嫌基;基甲基酸、p —乙嫌基爷基甲基 醚、〇 -乙烯基苄基縮水甘油醚、m —乙烯基苄基縮水甘 油醚、p —乙烯基苄基縮水甘油醚等芳香族乙烯基化合物 ;茚、1 —甲基茚等茚類;甲基(甲基)丙烯酸酯、乙基 (甲基)丙嫌酸酯、η -丙基(甲基)丙嫌酸酯、i 一丙 基(甲基)丙烯酸酯、η -丁基(甲基)丙烯酸酯、i 一 丁基(甲基)丙烯酸酯、s e c —丁基(甲基)丙烯酸酯 、t 一丁基(甲基)丙烯酸酯、2〜羥基乙基(甲基)丙 烯酸酯、2 -羥基丙基(甲基)丙烯酸酯、3 一羥基丙基 (甲基)丙烯酸酯、2 —羥基丁基(甲基)丙烯酸酯、3 一羥基丁基(甲基)丙烯酸酯、4〜羥基丁基(甲基)丙 烯酸酯、烯丙基(甲基)丙烯酸酯、苄基(甲基)丙烯酸 酯、環己基(甲基)丙燒酸酯、苯基(甲基)丙嫌酸酯、 2 —甲氧乙基(甲基)丙烯酸酯、2 —苯氧乙基(甲基) 丙烯酸酯、甲氧基二乙二醇基(甲基)丙烯酸酯、甲氧基 本紙張尺度適用中國國家標準(CNS ) A4規格(210X 297公釐) *-- -12- 508457 A7 ___B7__ 五、發明説明(1〇) 三乙二醇基(甲基)丙烯酸酯、甲氧基丙二醇基(甲基) 丙烯酸酯、甲氧基二甘油基(甲基)丙烯酸酯、異冰片基 (甲基)丙烯酸酯、三環〔5 8 -基(甲基)丙烯酸酯、2 羥基 .0 2 · 6〕癸烷一 3 —苯氧丙基(甲 基)丙烯酸酯、下記式(1 )所示甘油基(甲基)丙烯酸 酯等不飽和羧酸酯類; h2c=ccoo-Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, 8th Industrial Cooperative, ___L These organic pigments can be used alone or in combination of two or more types. 0 The organic pigments mentioned above can be used, for example, sulfuric acid recrystallization method, solvent washing method, or a combination thereof. The way is refined again. The volume resistivity of the colored layer formed by the radiation-sensitive radioactive composition of the present invention is extremely high. Therefore, when the organic pigment that reduces the amount of impurities after the above-mentioned purification is used, the volume resistivity of the colored layer can be further increased. Specific examples of the inorganic pigment include titanium oxide, barium oxide, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, iron oxide red (red iron oxide (m)), cadmium red, ultramarine blue, dark blue, and oxidation. Chrome green, cobalt green, amber, titanium black, synthetic iron black, carbon black and other pigments. These inorganic pigments can be used singly or in combination of two or more types. The radiation-sensitive radiation composition of the present invention is used as the format of the drawing paper. The size of the paper is applicable to China National Standards (CNS) 84 (210X297 mm). '~ -8-Printed by 508457 A7 of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 ____B7__ 5. Description of the Invention (6) When using pigments, it is preferred to use more than one organic pigment as a colorant, and also to form carbon black In this case, it is preferable to use two or more organic pigments and / or carbon black as a colorant. In addition, the colored layer formed by the radiation-sensitive radiation composition of the present invention has a very low dielectric constant 値, and the content in the colored layer is the same as that of the components (B) to (D) or additives described later. The amount used is preferably 1 to 60% by weight, more preferably 3 to 35% by weight, and most preferably 5 to 15% by weight, a lower dielectric constant can be obtained. Moreover, in the present invention, each pigment described above can be coated with the desired purpose, and the surface of the particles is modified with a polymer and then used. Polymers that can modify the surface of pigment particles are, for example, polymers described in Japanese Patent Application Laid-Open No. 8-2 5 9 8 7 6 or polymers or oligomers for various pigment dispersions that are commercially available. The coloring agent of the present invention can be used together with a dispersing agent according to a desired purpose. The foregoing dispersing agents include, for example, cationic, cationic, proton, amphoteric, polysiloxane, and fluorine-based surfactants. Examples of the foregoing surfactants, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and other polyoxyethylene alkyl ethers; polyoxyethylene η-octylphenyl ether, polyoxyethylene n Polyoxyethylene alkyl phenyl ethers such as monononyl ether; polyethylene diesters such as polyethylene glycol dilaurate, polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid denaturation Polyesters; Grade 3 amine denatured polyurethanes; Polyethyleneimines, etc., including KP (produced by Shin-Etsu Chemical Industry Co., Ltd.), Polyvolt (common paper standards apply to Chinese national standards) (CNS) Α4 specification (210X 297 mm) 1 ^ ------- »Cloth ------ 1Τ ------ ·% (Please read the precautions on the back before filling this page) -9-508457 A7 _____B7____ 5. Description of the invention (7) (Please read the notes on the back before filling out this page) Sakae Chemical Co., Ltd.), Yepdor (Toka Chemical Industry Co., Ltd.), Mageford (Da (Manufactured by Japan Ink Chemical Co., Ltd.), Fola (manufactured by Sumitomo 3M), Asapi, Sapphire (above, manufactured by Asahi Glass Co., Ltd.), D isperbyk (manufactured by BAK), Solsperse (manufactured by ZENEKA), EFKA (manufactured by EFKA), and the like. These surfactants may be used singly or in combination of two or more kinds. The amount of the surfactant is preferably 100 parts by weight of the colorant, preferably 50 parts by weight or less, more preferably 30 parts by weight. The following. (B) Alkali soluble resin Resin of the Intellectual Property Bureau, Ministry of Economic Affairs, Employees' Cooperative, printed the soluble resin of the present invention to act as an adhesive for (A) colorants, and for the development of dense color films, The developing solution used in the step is more preferably one having solubility in an alkali developing solution. For example, residues, phenolic hydroxyl groups, sulfonic acid groups, and other photopolymerizable unsaturated monomers having an acidic functional group are copolymerized with other copolymerizable unsaturated monomers (hereinafter, referred to as "copolymerizable unsaturated monomers"). Polymer, etc. Residual-containing photopolymerizable unsaturated monomers (hereinafter, referred to as "unsaturated monomers and monomers"), for example, (meth) propanoic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid And other unsaturated carboxylic acids; maleic acid, dried maleic acid, dried maleic acid, although dried maleic acid, dried maleic acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid and other unsaturated carboxylic acids Or its anhydrides; unsaturated polycarboxylic acids or their anhydrides with a valence of 3 or more; succinic acid [2 ~ (meth) acrylic acid] The size of this paper applies to China National Standard (CNS) A4 (210X 297 mm) ^ ~--10- 508457 A7 B7 V. Description of the invention (8) Oxyethyl ester], succinic acid mono (2- (meth) propenyloxyethyl), etc. (Meth) acryloyloxyalkyl] esters; ω ~ carboxy polycaprolactone mono (meth) acrylates, etc. Mono (meth) propionate esters of polymers having a carboxyl group and a hydroxyl group at both ends, etc. . Among these carboxyl group-containing unsaturated monomers, (meth) acrylic acid and succinic acid [2- (meth) acryloxyethyl] are more preferred. In addition, the aforementioned carboxyl group-containing unsaturated monomer may be used alone or in combination of two or more kinds. Photopolymerizable unsaturated monomers having phenolic hydroxyl groups, for example, 0-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 0-hydroxy-α-hydroxystyrene, m-hydroxy-α- Methylstyrene, P-hydroxy-α-methylstyrene, N-O-hydroxyphenylmaleic anhydride imine, N-m-hydroxyphenylmaleic anhydride imine, N-ρ-hydroxybenzene Maleic anhydride, imine, and the like. These photopolymerizable unsaturated monomers having a phenolic hydroxyl group can be used alone or in combination of two or more kinds. Examples of the photopolymerizable unsaturated monomer having a sulfonic acid group include isoprenesulfonic acid and P-styrenesulfonic acid. These photopolymerizable unsaturated monomers having a sulfonic acid group can be used alone or in combination of two or more kinds. Copolymerically unsaturated monomers such as polystyrene, polymeth (meth) acrylate, poly-n-butyl (meth) acrylate, polysiloxane, etc. Based) Macromonomers of propyleneoxy (hereinafter referred to as "macromonomers"): N-phenylmaleic anhydride imide This paper is sized to the Chinese National Standard (CNS) A4 specification (21〇 × 29: 7 (Mm) --------- Clothing-(Please read the notes on the back before filling out this page) Order ▼ Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, S Industrial Consumer Cooperative, 508457 A7 B7 V. Description of the invention ( 9) (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, N-〇-hydroxyphenylmaleic anhydride imine, N-m-hydroxyphenylmaleic anhydride Imine, N-p-hydroxyphenylmaleic anhydride imine, N-〇-tolyl maleic anhydride imine, N-〇-methoxyphenyl maleic anhydride imine, N-m —N- (substituted) aryl maleic anhydride imine, such as —methoxyphenylmaleic anhydride imine, N — P —methoxyanhydride imine, etc. N-Cyclohexylmaleic anhydride imine and other N-substituted maleic anhydride imine; phenethylbenzene, α-methylphenethylbenzene, 0-ethylbenzenetoluene, m-ethylhexyltoluene, P- Vinyltoluene, P-chlorostyrene, 0-methoxystyrene, m-methoxystyrene, p-methoxystyrene, 0-vinylbenzyl methyl acid, m-ethanyl; Aromatic vinyl groups such as methyl methyl acid, p-ethenyl methyl ether, 0-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether Compounds; indene such as indene, 1-methylindene; methyl (meth) acrylate, ethyl (meth) propanoate, η-propyl (meth) propanoate, i-propyl (Meth) acrylate, η-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate , 2 ~ hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-monohydroxypropyl (meth) acrylate, 2-hydroxybutyl (Meth) acrylate, 3 monohydroxybutyl (meth) acrylate, 4 to hydroxybutyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, Cyclohexyl (meth) propionate, phenyl (meth) propionate, 2-methoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxy Diethylene glycol (meth) acrylate, methoxy This paper is sized to the Chinese National Standard (CNS) A4 (210X 297 mm) *--12- 508457 A7 ___B7__ 5. Description of the invention (1〇) Triethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, methoxydiglyceryl (meth) acrylate, isobornyl (meth) acrylate, tricyclic [ 5 8 -yl (meth) acrylate, 2 hydroxy. 0 2 · 6] decane-3 -phenoxypropyl (meth) acrylate, glyceryl (meth) acrylate represented by the following formula (1) And other unsaturated carboxylic acid esters; h2c = ccoo-
严2 CHOH (1) —-------裝-- (請先閱讀背面之注意事項再填寫本頁)Yan 2 CHOH (1) --------- install-(Please read the precautions on the back before filling this page)
CH2〇H 〔式(1 )中,R 1爲氫原子或甲基〕 訂 經濟部智慧財/i局g〔工消骨合作钍印災 2 —胺乙基(甲基)丙烯酸酯、2 —二甲基胺乙基( 甲基)丙烯酸酯、2 -胺丙基(甲基)丙烯酸酯、2 -二 甲基胺丙基(甲基)丙烯酸酯、3 —胺丙基(甲基)丙烯 酸酯、3 —二甲基胺丙基(甲基)丙烯酸酯等不飽和羧酸 類胺烷基酯類;縮水甘油基(甲基)丙烯酸酯等不飽和羧 酸縮水甘油酯類;乙酸乙酯、丙酸乙酯、丁酸乙酯、苯甲 酸乙酯等羧酸乙酯類; 乙烯基甲醚、乙烯基乙醚、烯丙基縮水甘油醚等不飽 和醚類: (甲基)丙烯腈、α —氯基丙烯腈、氰化亞乙基等氰 化乙烯基化合物; 甲基)丙烯醯胺 一氯基丙烯醯胺、Ν-2-經 乙基(甲基)丙烯醯胺等不飽和醯胺類; 本紙張尺度適用中國國家標準(CNS ) A4規格(210X 297公釐) -13- 508457 A7 ____ _B7_ 五、發明説明(11 ) 1, 3-丁二烯、異戊二烯、氯基戊二烯等脂肪族共 軛二烯類等。 此些共聚合性不飽和單體,可單獨使用或將2種以上 混合使用皆可。 前記共聚性不飽和單體中,以巨單體、N位-取代馬 來酸酐縮亞胺、2 —羥乙基(甲基)丙烯酸酯、苄基(甲 基)丙烯酸酯、甘油基(甲基)丙烯酸酯等爲佳。又,巨 單體中以聚苯乙烯巨單體、聚甲基(甲基)丙烯酸酯聚單 體爲最佳,N位-取代馬來酸酐縮亞胺·中以N -苯基馬來 酸酐縮亞胺、N -環己基馬來酸酐縮亞胺爲最佳。 本發明中,較佳之鹼可溶性樹脂,例如含羧基之不飽 和性單體與共聚性不飽和單體之共聚物(以下簡稱「含羧 基之共聚物」)等。 含羧基之共聚合物,以含有①含羧基之不飽和單體與, ②由聚苯乙烯巨單體、聚甲基(甲基)丙烯酸酯巨單體、N -苯基馬來酸酐縮亞胺、N -環己基馬來酸酐縮亞胺、2 -羥乙基(甲基)丙烯酸酯、苄基(甲基)丙烯酸酯與甘 油基(甲基)丙烯酸酯選出之至少1種,或必要時,可再 含有③由苯乙烯、甲基(甲基)丙烯酸酯、烯丙烯(甲基) 丙烯酸酯、苯基(甲基)丙烯酸酯中所選出之至少丨種的 單體混合物所得之共聚物(以下簡稱「含羧基之共聚物( I )」)爲佳。特別是,以含有Φ以(甲基)丙烯酸爲必須 成份,或必要時,可再含有琥珀酸一〔2 -(甲基)丙烯 醯氧基乙基〕之含羧基不飽和單體與,②由聚苯乙烯巨單體 本紙張尺度適用中國國家標準(CNS ) A4規格(210X 297公釐) II丨丨丨— ·丨丨 (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局工消費合作社印製 -14 - 經濟部智慧財產局員工消费合作社印製 508457 Μ _Β7_____^_ 五、發明説明(12 ) 、聚甲基(甲基)丙嫌酸酯巨單體、Ν —苯基馬來酸酐縮 亞胺、Ν -環己基馬來酸酐縮亞胺、2 —羥乙基(甲基) 丙烯酸酯、苄基(甲基)丙烯酸酯與甘油基(甲基)丙烯 酸酯選出之至少1種,或必要時,可再含有③由苯乙烯、甲 基(甲基)丙烯酸酯、烯丙烯(甲基)丙烯酸酯、苯基( 甲基)丙烯酸酯中所選出之至少1種的單體混合物所得之 共聚物(以下簡稱「含羧基之共聚物(Π )」)爲佳。 含羧基之共聚合物(I )之具體例如, (甲基)丙烯酸/苄基(甲基-)丙烯酸酯/聚苯乙烯 巨單體共聚物、 (甲基)丙烯酸/苄基(甲基)丙烯酸酯/聚甲基( 甲基)丙烯酸酯巨單體共聚物、 (甲基)丙烯酸/ Ν -苯基馬來酸酐縮亞胺_/苄基( 甲基)丙烯酸酯/苯乙烯共聚物、 (甲基)丙烯酸/琥珀酸一〔2 —(甲基)丙烯醯氧 乙基〕/ Ν -苯基馬來酸酐縮亞胺/苯乙烯/烯丙基(甲 基)丙烯酸酯共聚物、 (甲基)丙烯酸/琥珀酸一〔2 —(甲基)丙烯醯氧 乙基〕/Ν-苯基馬來酸酐縮亞胺/苄基(甲基)丙嫌酸 酯/苯乙烯共聚物、 (甲基)丙烯酸/Ν-環己基馬來酸酐縮亞胺/苄基 (甲基)丙烯酸酯/苯乙烯共聚物、 (甲基)丙烯酸/琥珀酸一〔2 —(甲基)丙烯醯氧 乙基〕/Ν -環己基馬來酸酐縮亞胺/苯乙烯/烯丙基( I:-----1——!参衣------1Τ----- (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -15- 經濟部智慧財產局員工消費合作社印製 508457 A7 _B7__ 五、發明説明(13) 甲基)丙烯酸酯共聚物、 (甲基)丙烯酸/琥珀酸一〔2 —(甲基)丙烯醯氧 乙基〕/N -環己基馬來酸酐縮亞胺/苄基(甲基)丙烯 酸酯/苯乙烯共聚物、 (甲基)丙烯酸/苄基(甲基)丙烯酸酯/甘油基一 (甲基)丙烯酸酯共聚物、 (甲基)丙烯酸/琥珀酸一〔2 —(甲基)丙烯醯氧 乙基〕/苄基(甲基)丙烯酸酯/甘油基一(甲基)丙烯 酸酯共聚物、 - _ (甲基)丙烯酸/2 —羥乙基(甲基)丙烯酸酯共聚 物、 (甲基)丙烯酸/ 2 -羥乙基(甲基.)丙烯酸酯/苯 乙烯共聚物、 (甲基)丙烯酸/2 —羥乙基(甲基)丙烯酸酯/苄 基(甲基)丙烯酸酯共聚物、 (甲基)丙烯酸/2 -羥乙基(甲基)丙烯酸酯/苯 基(甲基)丙烯酸酯共聚物、 (甲基)丙烯酸/2 —羥乙基(甲基)丙烯酸酯/苄 基(甲基)丙烯酸酯/聚苯乙烯巨單體共聚物、 (甲基)丙烯酸/2 —羥乙基(甲基)丙烯酸酯/苄 基(甲基)丙烯酸酯/聚甲基(甲基)丙烯酸酯巨單體共 聚物、 (甲基)丙烯酸/ N -苯基馬來酸酐縮亞胺/苄基( 甲基)丙烯酸酯/甘油基一(甲基)丙烯酸酯/苯乙烯共 本紙張尺度適用中國國家標準(CNS ) A4規格(210Χ297公釐) 丨:-----1 — _♦费------1T-----费 (請先閱讀背面之注意事項再填寫本頁) -16 - 508457 A7 ___B7_ 五、發明説明(14) 聚物, 等。 含羧基共聚合物中含羧基之不飽和單體之共聚比例, 較佳爲5至5 0重量%,更佳爲1 0至4 0重量%。此情 形中,含羧基之不飽和單體之共聚比例若低於5重量%時 ,則所得輻射敏感放射線性組成物對鹼顯像液之溶解性會 有降低之傾向;又,超過5 0重量%時,因對鹼顯像液之 溶解性過大,故使用鹼顯像液顯像時,會有較易由形成有 畫素之基板上脫落,或畫素表面之粗糙度未能達到較低程 度之傾向。 又,本發明中,鹼可溶性樹脂之凝膠滲透色層分析法 (G P C,溶出溶媒:四氫呋喃)測定所得之以苯乙烯換 算之重量平均分子量(以下,簡稱「Mw」)較佳爲 3, 000至300, 000,更佳爲5, 000至 1〇〇,0 0 0 。 又,本發明中,鹼可溶性樹脂之凝膠滲透色層分析法 (G P C,溶出溶媒:四氫呋喃)測定所得之以苯乙烯換 算之數平均分子量(以下,簡稱「Μη」)較佳爲 3, 0〇〇至60, 000,更佳爲5, 000至 2 5,0 0 0° 使用此一具有特定之M w或Μ η之鹼可溶性樹脂,可 得到具有優良顯像性之輻射敏感放射線性組成物,並依此 可以形成具有明確蝕刻圖型之畫素外,於顯像時在未曝光 之基板上與遮光層上亦極不易產生殘渣、地面污染、膜殘 本紙張尺度適用中國國家標準(CNS ) Α4規格(210X297公釐) ————」?丨 (請先閲讀背面之注意事項再填寫本頁) 訂 ·線 經濟部智慧財產局員工消費合作社印製 -17- 508457 A7 ___B7_ 五、發明説明(15) 留等現象。 又,本發明中鹼可溶性樹脂之M w與Μ η之比(M w /Μη)較佳爲1至5,更佳爲1至4。 使用此一具有特定之M w或Μ η之鹼可溶性樹脂,可 得到具有優良顯像性之輻射敏感放射線性組成物,並依此 可以形成具有明確蝕刻圖型之畫素外,因存在於該組成物 所形成著色層之開口部的垂直截面形狀上,其底邊之長度 較上邊長度爲短,故於IT 0成膜時可形成不會有斷線之 圖型,此外,於顯像時在未曝光之基板上與遮光層上亦極 不易產生殘渣、地面污染、膜殘留等現象。 本發明中,鹼可溶性樹脂可單獨使用或將2種以上混 合使用。 本發明中,鹼可溶性樹脂之使用量,對(A )著色劑 100重量份而言,較佳爲10至1,000重量份,更 佳爲2 0至5 0 0重量份。此情形中,鹼可溶性樹脂之使 用量若低於1 0重量份時,例如會造成鹼顯像性降低,或 會有污染或膜殘留於未曝光部基板上或遮光層上之疑慮, 又,超過1,0 0 0重量份時,因相對著色劑濃度會有降 低情形,故不易達到以薄膜爲目的顏色濃度。 (C )冬官能件單體 本發明之多官能性單體,係由具有2個以上可聚合之 不飽和鍵結的單體所構成。 此多官能性單體,於本發明中,可分爲含羧基之多官 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) —丨丨丨—丨?丨 (請先閱讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 -18 - 經濟部智慧財產局員工消費合作社印製 508457 A7 ______B7_ 五、發明説明(16 ) 能性單體與不含羧基之多官能性單體(以下,·稱爲「其他 多官能性單體」)。 前記含羧基之多官能性單體,例如,2價以上之多元 醇與,具有2個以上羧基之聚合性不飽和羧酸之含游離竣 基之多官能性酯化合物; 3價以上多元醇與具有1個以上羧基之聚合性不飽和 羧酸之含游離經基之多B㉟酯類與,二殘酸類之含游離竣 基之多官能性酯化合物(以下簡稱「( C 1 )多官能性單 體」); 4 - 3價以上多元羧酸類與具有1個以上羥基之聚合性不 飽和化合物之含游離羧基之多官能性酯化合物(以下簡稱 「( C 2 )多官能性單體」); (C 1 )多官能性單體中,2價以上多元醇之例如乙 二醇、丙二醇、聚乙二醇、聚丙二醇等。又,具有2個以 上羧基之聚合性不飽和羧酸例如馬來酸、富馬酸、依康酸 、檬康酸、中康酸等。 (C 1 )多官能性單體中,3價以上多元醇之例如甘 油、三羥甲基丙烷、季戊四醇基、二季戊四醇基等。具有 1個以上羧基之聚合性不飽和羧酸,例如,(甲基)丙嫌 酸、巴豆酸、α —氯基丙烯酸、桂皮酸、馬來酸、富馬酸 、依康酸、檬康酸、中康酸等。又,二羧酸類例如草酸、 丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬 二酸、癸二酸、巴豆二酸、甲基丙二酸、乙基丙二酸、二 甲基丙二酸、甲基琥珀酸、四甲基琥珀酸、環己烷一1 , 本紙張尺度適用中國國家標準(CNS ) Α4規格(210X 297公釐) I------------—1Τ----- (請先閱讀背面之注意事項再填寫本頁) -19- 508457 A7 _B7 五、發明説明(17 ) 2 -二羧酸、環己烷—1, 3 —二羧酸、環己烷一 1, 4 一二羧酸、鄰苯二酸、間苯二酸、對苯二酸類等。 _1:丨||·費—I (請先閱讀背面之注意事項再填寫本頁) 又,(C 2 )多官能性單體中,3價以上多元羧酸之 例如丙烷一 1,2,3 -三羧酸(丙三羧酸)、丁烷一 1 ,2, 4一三羧酸、烏頭酸、樟腦三酸、環己烷一1, 2 ,3 -三羧酸、環己烷—1, 2,4 —三羧酸、環己烷一 1, 3, 5-三羧酸、苯一1, 2, 3—三羧酸、偏苯三 酸、均苯三酸、偏苯四酸、均苯四酸等。又,具有1個以 上羥基之聚合性不飽和化合物例如甲基)烯丙醇、2 -羥乙基(甲基)丙烯酸酯、2 —羥丙基(甲基)丙烯酸酯 、3 -羥丙基(甲基)丙烯酸酯等。 本發明中較佳之(C 1 )多官能性單體與(C 2 )多 .官能性單體之例示,具體而言例如三羥甲基丙烷二(甲基 )丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇 五(甲基)丙烯酸酯等含一羥基之低(甲基)丙烯酸酯與 ,丙二酸、琥珀酸、戊二酸、對苯二酸等二羧酸類之含游 離羧酸基之單酯化合物; 經濟部智慧財產局員工消費合作社印製 丙烷一1, 2, 3-三羧酸(丙三羧酸)、丁烷一1 ,2, 4一三羧酸、苯一1, 2, 3-三羧酸、偏苯三酸 、均苯三酸等三羧酸與,2 -羥乙基(甲基)丙烯酸酯、 2 -羥丙基(甲基)丙烯酸酯等單羥烷基(甲基)丙烯酸 酯之含游離羧基之低酯化合物等。 此些(C 1 )多官能性單體與(C 2 )多官能性單體 中,特別是以下記式(2 )之含有季戊四醇三丙烯酸酯與 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -20- 508457 A7 B7 五、發明説明(18) (請先閲讀背面之注意事項再填寫本頁) 琥珀酸之含游離羧基之單酯化合物(以下,簡稱「多官能 性丙烯酸酯(1)」),下記式(3)所示之季戊四醇三 甲基丙烯酸酯與琥珀酸之含游離羧基之單酯化合物(以下 ,簡稱「多官能性丙烯酸酯(2 )」)爲佳。 CH2OCOCH=CH2 h2c=chcooch2 CH2OCOCH2CH2COOH (2) ch2ococh=ch2 ch3CH2〇H [In the formula (1), R 1 is a hydrogen atom or a methyl group] Ordered by the Ministry of Economic Affairs and Intellectual Property / i Bureau [Industrial and Cooperative Cooperation 2 —Amine ethyl (meth) acrylate, 2 — Dimethylaminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate Esters, unsaturated carboxylic acid amine alkyl esters such as 3-dimethylaminopropyl (meth) acrylate; unsaturated glycidyl esters of unsaturated carboxylic acids such as glycidyl (meth) acrylate; ethyl acetate, Ethyl carboxylates such as ethyl propionate, ethyl butyrate, ethyl benzoate; unsaturated ethers such as vinyl methyl ether, vinyl ether, allyl glycidyl ether: (meth) acrylonitrile, α —Vinyl cyanide compounds such as chloroacrylonitrile, ethylene cyanide, etc .; Unsaturated fluorene amines such as methacrylamide, chloroacrylamide, N-2-via ethyl (meth) acrylamide This paper size applies to Chinese National Standard (CNS) A4 specification (210X 297 mm) -13- 508457 A7 ____ _B7_ V. Description of invention (11) 1, Aliphatic conjugated dienes such as 3-butadiene, isoprene, and chloropentadiene. These copolymerizable unsaturated monomers may be used alone or in combination of two or more. Among the aforementioned copolymerizable unsaturated monomers, macromonomers, N-substituted maleic anhydride imines, 2-hydroxyethyl (meth) acrylates, benzyl (meth) acrylates, glyceryl (methyl Acrylate) is preferred. Among the macromonomers, polystyrene macromonomers and polymeth (meth) acrylate polymonomers are the most preferable. N-substituted maleic anhydride imine · N-phenylmaleic anhydride Imines and N-cyclohexylmaleic anhydride imines are most preferred. In the present invention, preferred alkali-soluble resins are, for example, copolymers of carboxyl-containing unsaturated monomers and copolymerizable unsaturated monomers (hereinafter referred to as "carboxyl-containing copolymers") and the like. Copolymers containing carboxyl groups are composed of ① unsaturated monomers containing carboxyl groups and ② polystyrene macromonomers, polymeth (meth) acrylate macromonomers, and N-phenylmaleic anhydride. At least one selected from amine, N-cyclohexylmaleic anhydride imine, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate and glyceryl (meth) acrylate, or necessary In this case, it may further contain ③ copolymerization obtained from at least one kind of monomer mixture selected from styrene, meth (meth) acrylate, propylene (meth) acrylate, and phenyl (meth) acrylate. (Hereinafter referred to as "carboxyl-containing copolymer (I)"). In particular, if (meth) acrylic acid is contained as an essential component containing Φ, or if necessary, a carboxyl-containing unsaturated monomer containing succinic acid [2- (meth) acryloxyethyl] may be further added, ② Made of polystyrene macromonomer This paper size applies Chinese National Standard (CNS) A4 specification (210X 297mm) II 丨 丨 丨-· 丨 丨 (Please read the precautions on the back before filling this page) Order the wisdom of the Ministry of Economic Affairs Printed by the Industrial and Commercial Cooperatives of the Property Bureau-14-Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 508457 Μ_Β7 _____ ^ _ V. Description of the Invention (12), Polymethyl (meth) propionate macromonomer, N — Selected from phenylmaleic anhydride imine, N-cyclohexylmaleic anhydride imine, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, and glyceryl (meth) acrylate At least one of them, or if necessary, it may further contain at least one selected from styrene, meth (meth) acrylate, allyl (meth) acrylate, and phenyl (meth) acrylate Copolymers (hereinafter referred to as " Carboxyl copolymer ([pi) ") is preferred. Specific examples of the carboxyl group-containing copolymer (I) include (meth) acrylic acid / benzyl (meth-) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / benzyl (methyl) Acrylate / poly (meth) acrylate macromonomer copolymer, (meth) acrylic acid / N-phenylmaleic anhydride imine_ / benzyl (meth) acrylate / styrene copolymer, (Meth) acrylic acid / succinic acid mono- [2- (meth) acryloxyethyl] / N-phenylmaleic anhydride imine / styrene / allyl (meth) acrylate copolymer, ( (Meth) acrylic acid / succinic acid mono [2- (meth) acrylic acid oxyethyl] / N-phenylmaleic anhydride imine / benzyl (meth) propionic acid ester / styrene copolymer, ( (Meth) acrylic acid / N-cyclohexylmaleic anhydride imine / benzyl (meth) acrylate / styrene copolymer, (meth) acrylic acid / succinic acid mono- [2- (meth) acrylic acid oxyethyl Group] / N-cyclohexylmaleic anhydride imine / styrene / allyl (I: ----- 1——! Senyi ------ 1T ----- (Please read first Note on the back then fill out this page ) This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm). -15- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 508457 A7 _B7__ V. Description of the invention (13) Methacrylic acid copolymer, ( (Meth) acrylic acid / succinic acid mono- [2- (meth) acryloxyethyl] / N-cyclohexylmaleic anhydride imine / benzyl (meth) acrylate / styrene copolymer, (methyl ) Acrylic acid / benzyl (meth) acrylate / glyceryl mono (meth) acrylate copolymer, (meth) acrylic acid / succinic acid [[2- (meth) acrylic acid oxyethyl] / benzyl ( (Meth) acrylate / glyceryl mono (meth) acrylate copolymer,-(meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, (meth) acrylic acid / 2-hydroxyethyl (Meth.) Acrylate / styrene copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer, (meth) acrylic acid / 2 -Hydroxyethyl (meth) acrylate / phenyl (meth) acrylate copolymer, (meth) Acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / Benzyl (meth) acrylate / poly (meth) acrylate macromonomer copolymer, (meth) acrylic acid / N-phenylmaleic anhydride imine / benzyl (meth) acrylate / Glyceryl mono (meth) acrylate / styrene co-paper size is applicable to Chinese National Standard (CNS) A4 specification (210 × 297 mm) 丨: ----- 1 — _ ♦ fee ------ 1T- ---- Fees (Please read the notes on the back before filling this page) -16-508457 A7 ___B7_ V. Description of the invention (14) Polymer, etc. The copolymerization ratio of the carboxyl group-containing unsaturated monomer in the carboxyl group-containing copolymer is preferably 5 to 50% by weight, and more preferably 10 to 40% by weight. In this case, if the copolymerization ratio of the carboxyl group-containing unsaturated monomer is less than 5% by weight, the solubility of the obtained radiation-sensitive radiation composition to the alkali imaging solution tends to decrease; more than 50% by weight %, Because the solubility of the alkali imaging solution is too large, when using the alkali imaging solution for development, it will be easier to fall off from the substrate on which the pixels are formed, or the roughness of the surface of the pixels will not reach a lower level Degree of tendency. In the present invention, the weight-average molecular weight (hereinafter referred to as "Mw") in terms of styrene obtained by a gel permeation chromatography (GPC, dissolution solvent: tetrahydrofuran) measurement of the alkali-soluble resin is preferably 3,000. To 300,000, more preferably 5,000 to 10,000. In the present invention, the number-average molecular weight (hereinafter referred to as "Mη") in terms of styrene measured by gel permeation chromatography (GPC, dissolution solvent: tetrahydrofuran) of the alkali-soluble resin is preferably 3.0. 〇〇 ~ 60,000, more preferably 5,000 ~ 2 5,0 0 ° By using this alkali-soluble resin having a specific Mw or Mn, a radiation-sensitive radiation composition with excellent imaging properties can be obtained In addition to this, pixels with a clear etching pattern can be formed, and residues, ground pollution, and film residues on the unexposed substrate and the light-shielding layer during development are extremely unlikely to produce Chinese paper standards ( CNS) Α4 specification (210X297 mm) ———— "?丨 (Please read the precautions on the back before filling this page) Order · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -17- 508457 A7 ___B7_ V. Description of the Invention (15) Retention and other phenomena. The ratio Mw to Mη of the alkali-soluble resin in the present invention (Mw / Mη) is preferably from 1 to 5, more preferably from 1 to 4. Using this alkali-soluble resin with a specific M w or M η, a radiation-sensitive radioactive composition having excellent developability can be obtained, and a pixel having a clear etching pattern can be formed accordingly, because it exists in the In the vertical cross-sectional shape of the opening of the colored layer formed by the composition, the length of the bottom side is shorter than the length of the upper side. Therefore, a pattern without disconnection can be formed when filming at IT 0. In addition, during development, It is also extremely difficult to cause residues, ground pollution, and film residue on unexposed substrates and light-shielding layers. In the present invention, the alkali-soluble resin may be used alone or in combination of two or more. In the present invention, the amount of the alkali-soluble resin used is preferably 10 to 1,000 parts by weight, and more preferably 20 to 500 parts by weight, based on 100 parts by weight of the (A) colorant. In this case, if the amount of the alkali-soluble resin is less than 10 parts by weight, for example, the alkali developability may be reduced, or there may be a concern that the film may remain on the substrate of the unexposed portion or the light-shielding layer. When it exceeds 1,000 parts by weight, the relative colorant concentration may be reduced, so it is difficult to achieve a color concentration for a film. (C) Winter functional monomer The polyfunctional monomer of the present invention is composed of a monomer having two or more polymerizable unsaturated bonds. This polyfunctional monomer can be divided into carboxyl-containing multi-functional monomers in the present invention. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) — 丨 丨 丨 — 丨?丨 (Please read the notes on the back before filling this page) Order printed by the Employees 'Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-18-Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 508457 A7 ______B7_ V. Description of Invention (16) A monomer and a polyfunctional monomer having no carboxyl group (hereinafter, referred to as "other polyfunctional monomer"). The above-mentioned carboxyl group-containing polyfunctional monomers, for example, a polyvalent alcohol having more than two valences and a polymerizable unsaturated carboxylic acid having two or more carboxyl groups and a polyfunctional ester compound containing a free end; Polymerizable unsaturated carboxylic acids having more than one carboxyl group, polybasic esters containing free radicals, and polyfunctional ester compounds containing free radicals containing diacids (hereinafter referred to as "(C 1) polyfunctional monofunctional ”); 4-3 or more polyvalent carboxylic acids and polymerizable unsaturated compounds having one or more hydroxyl groups, polyfunctional ester compounds containing free carboxyl groups (hereinafter referred to as" (C 2) polyfunctional monomers "); (C 1) Among the polyfunctional monomers, examples of the polyvalent or higher polyhydric alcohol include ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol. Examples of the polymerizable unsaturated carboxylic acid having two or more carboxyl groups include maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and the like. (C 1) Polyfunctional monomers, such as glycerol, trimethylolpropane, pentaerythritol group, dipentaerythritol group, and the like, for example, trivalent or higher polyhydric alcohols. Polymerizable unsaturated carboxylic acid having one or more carboxyl groups, for example, (meth) propionic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid , Zhongkang acid and so on. Dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, crotonic acid, methylmalonic acid, and ethyl Methyl malonic acid, dimethyl malonic acid, methyl succinic acid, tetramethyl succinic acid, cyclohexane-1, this paper size applies to China National Standard (CNS) A4 specification (210X 297 mm) I-- ----------— 1Τ ----- (Please read the notes on the back before filling out this page) -19- 508457 A7 _B7 V. Description of the invention (17) 2-Dicarboxylic acid, ring Hexane-1,3-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, etc. _1: 丨 || ·· Fee-I (Please read the precautions on the back before filling this page) Also, (C 2) polyfunctional monomers, such as propane-1,2,3 -Tricarboxylic acid (malonic acid), butane-1,2,4-tricarboxylic acid, aconitic acid, camphortriic acid, cyclohexane-1,2,3-tricarboxylic acid, cyclohexane-1 , 2,4-tricarboxylic acid, cyclohexane-1, 3, 5-tricarboxylic acid, benzene-1, 2, 3-tricarboxylic acid, trimellitic acid, trimesic acid, trimellitic acid, Pyromellitic acid and so on. Also, polymerizable unsaturated compounds having one or more hydroxyl groups such as methyl) allyl alcohol, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (Meth) acrylates and the like. Preferred (C 1) polyfunctional monomers and (C 2) polyfunctional monomers in the present invention. Examples of functional monomers, specifically, trimethylolpropane di (meth) acrylate, pentaerythritol tri (methyl) ) Acrylate, dipentaerythritol penta (meth) acrylate and other low-hydroxy (meth) acrylates containing a hydroxyl group, and malonic acid, succinic acid, glutaric acid, terephthalic acid and other dicarboxylic acids containing free carboxylic acid Acid-based monoester compounds; propane-1,2,3-tricarboxylic acid (malonic acid), butane-1,2,4-tricarboxylic acid, benzene-1 Tricarboxylic acids such as 1, 2, 3-tricarboxylic acid, trimellitic acid, trimesic acid, and monocarboxylic acids such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate Low alkyl compounds containing free carboxyl groups such as hydroxyalkyl (meth) acrylates. Among these (C 1) polyfunctional monomers and (C 2) polyfunctional monomers, in particular, pentaerythritol triacrylate containing the following formula (2) and the paper size are applicable to Chinese National Standard (CNS) A4 specifications (210X297 mm) -20- 508457 A7 B7 V. Description of the invention (18) (Please read the notes on the back before filling this page) Monoester compounds containing succinic acid containing free carboxyl groups (hereinafter referred to as "multifunctional acrylic acid" The ester (1) ") is preferably a pentaerythritol trimethacrylate represented by the following formula (3) and a free carboxyl-containing monoester compound (hereinafter, referred to as" polyfunctional acrylate (2) ") represented by the following formula (3). CH2OCOCH = CH2 h2c = chcooch2 CH2OCOCH2CH2COOH (2) ch2ococh = ch2 ch3
I ch3 ch2ococ=ch2 H2c=J:HCOOCH2 CH20C0CH2CH2C00H (3) ch7ococh=ch9I ch3 ch2ococ = ch2 H2c = J: HCOOCH2 CH20C0CH2CH2C00H (3) ch7ococh = ch9
I ch3 經濟部智慧財產局員工消費合作社印製 任一種多官能性丙烯酸酯(1 )或多官能性丙烯酸酯 (2 ),皆可製得具有高畫素強度與優良的表面平滑性, 且不會污染畫素形成區域以外之區域亦極不易產生膜殘留 之輻射敏感放射線性組成物。 本發明中,含羧基之多官能性單體對輻射敏感放射線 性組成物之鹼性顯像液而言,可改善溶解特性且具有抑制 顯像後之未溶解物的殘留等作用。此點於後述作爲添加劑 之有機酸成分亦顯示相同出之作用。 其次,其他多官能性單體例如, 乙二醇、丙二醇等烷二醇之二(甲基)丙烯酸酯; 本紙浪尺度適用中國國家標準(CNS ) A4規格(210X297公釐) " -21 - 經濟部智慧財產局員工消費合作社印製 508457 A7 B7 五、發明説明(19 ) 聚乙二醇、聚丙二醇等聚烷二醇之二(甲基)丙烯酸 酯; 丙三醇、三羥甲基丙院、季戊四醇基、二季戊四醇基 等3價以上多元醇之聚(甲基)丙烯酸酯; 聚酯、環氧樹脂、尿烷樹脂、醇酸樹脂、聚矽氧烷樹 脂、螺烷樹脂等低(甲基)丙烯酸酯; 兩末端羥基聚一 1,3 - 丁二烯、兩末端羥基聚異丁 烯、兩末端羥基聚己內醯胺等兩末端羥基化聚合物之二( 甲基)丙烯酸酯或; - 三〔2 -(甲基)丙烯醯氧乙基〕膦化物等化合物。 此些多官能基單體中,以3價以上之多元醇之聚(甲 基)丙烯酸酯爲佳,具體而言,例如三羥甲基丙烷三(甲 .基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇 四(甲基)丙烯酸酯、二季戊四醇基五(甲基)丙烯酸酯 、二季戊四醇基六(甲基)丙烯酸酯等爲佳,特別是三羥 甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯與二季戊四醇 基六丙烯酸酯等以具有高畫素強度,優良畫素表面平滑性 ,且不易污染未曝光之基板與遮光層區域,或產生殘留膜 等缺點。 本發明中,多官能性單體,可單獨使用或將2種以上 混合使用皆可,又可與含羧基之多官能性單體與其他多官 能性單體合倂使用。本發明之輻射敏感放射線性組成物於 作爲形成薄膜電晶體(T F T )方式彩色液晶顯示裝置之 驅動用基板的著色層使用的感應放射性性組成物時,可具 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) I-------•衣------1T-----·$ (請先閲讀背面之注意事項再填寫本頁) -22- 508457 A7 B7 五、發明説明(20) (請先閱讀背面之注意事項再填寫本頁) 有充分之解像度,且於形成著色層時可形成具有所需尺寸 之導通路。又,多官能性單體之一部份或全部作爲含羧基 之多官能性單體使用時,導通路之尺寸可配合光罩所對應 之圖型作適當之選擇。 本發明中,作爲含羧基之多官能性單體使用時,對多 官能性單體之使用比例較佳爲5至9 5重量% ,更佳爲 1 0至8 0重量% ,最佳爲1 0至5 0重量%。此情形中 ,含羧基之多官能性單體之使用比例若低於5重量%時, 作爲輻射敏感放射線性組成物之組成內容時,特別是未使 用後述(E )含羧基之單官能性單體時,將具有不易形成 所需導通路之傾向,又,超過9 5重量%時,因鹼顯像亦 極易浸滲於著色層中,故顯像時著色層會有脫落之情形產 生。 經濟部智慧財產局員工消費合作社印製 本發明中,多官能基單體之使用量,對(B)鹼可溶 性樹脂1 0 0重量份而言,一般爲5至5 0 0重量份,較 佳爲2 0至3 0 0重量份。此情形中,多官能性單體之使 用量若低於5重量份時,畫素強度或畫素表面之平滑性會 有降低之情形,又,超過5 0 0重量份時,例如會造成鹼 顯像性降低,或會有污染未曝光之基板與遮光層區域,或 產生殘留膜等缺點。 又,本發明中,多官能性單體可與具有1個聚合性不 飽和鍵結的單官能性單體共同使用。 前記單官能性單體例如,前記(B )鹼可溶性樹脂所 例示的含羧基之不飽和單體、共聚性不飽和單體或,N - 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -23- 508457 A7 _B7_ _ 五、發明説明(21 ) (請先閲讀背面之注意事項再填寫本頁) 乙烯基琥珀銑酵亞胺、N -乙烯基吡咯啉酮、N -乙烯基 酞醯亞胺、N —乙烯基一 2 —哌啶酮、N -乙烯基、N-乙烯基一 ε 一己內醯胺、N —乙烯基吡咯、N —乙烯基吡 咯院、Ν —乙嫌基咪哩、Ν —乙嫌基咪哇啉、Ν —乙燦基 吲哚、Ν —乙烯基吲哚啉、Ν —乙烯基苯駢咪唑、Ν —乙 烯基咔唑、Ν —乙烯基哌啶、Ν —乙烯基哌嗪、Ν -乙烯 基嗎啉、Ν —乙儲基酣Β惡嗪等Ν —乙嫌基衍生物類;Ν — (甲基)丙烯醯氧基嗎啉外,市售物例如Μ - 5 3 0 0、 Μ — 5 4 0 0、Μ — 5 6 0 0 (商-品名·,東亞合成股份有 限公司製)等。 此些單官能性單體之使用量,以對多官能性單體與單 官能性之合計量而言,較佳爲9 0重量%以下,更佳爲 5 0重量%以下。此時,若單官能性單體之使用比例超過 9 0重量%時,畫素或黑色基質之強度或表面平滑性會有 降低之傾向。 (D )光聚合起始劑 經濟部智慧財產局員工消費合作社印^ 本發明所使用之光聚合起始劑,係由可經由可見光、 紫外光、遠紫外光、電子線、X線等放射線之照射(以下 稱爲「曝光」),使前記(C )多官能性單體與必要時使 用之單官能性單體開始進行聚合等的活性之化合物。 此些光聚合起始劑,例如下記之苯乙酮化合物、聯二 咪唑化合物、三嗪化合物、苯偶因化合物、二苯甲酮化合 物、α -二酮化合物、多核苯酮化合物、咕噸酮化合物、 本紙張尺度適用中國國家標準(CNS ) Α4規格(210X297公釐) -24- 508457 經濟部智慧財產局員工消費合作社印奴 A7 _____B7_^_五、發明説明(22 ) 二偶氮化合物等化合物。 本發明中,光聚合起始劑可單獨使用1種或將2種以 上混合使用皆可。光聚合起始劑例如由苯乙酮化合物、聯 二咪唑化合物與三嗪化合物群中所選出之至少1種爲佳。 本發明中,光聚合起始劑之使用量,一般以對(C ) 多官能性單體與必要時使用之單官能性單體之合計量爲 1 0 0重量份時,較佳爲0 . 0 1至8 0重量份,更佳爲 1至6 0重量份,光聚合起始劑之使用量若低於0 · 0 1 重量份時,曝光部分會有硬化不足之疑慮,且對於畫素圖 型而言,將不容易得到所需要之畫素陣列,又,超過8 0 重量份時,所形成之畫素於顯像時會有極容易由基板脫落 之傾向。 本發明之較佳光聚合起始劑中,苯乙酮化合物之具體 例如, 2 -羥基—2 —甲基—1—苯基丙烷一 1 一酮、 2 —甲基一 1 一〔4 一(甲硫基)苯基〕一 2 —嗎啉 丙酮—1、 2 -苄基一 2 -二甲基胺基—1— (4 一嗎啉苯基) 丁酮一 1、 1 —羥基環己基•苯基酮、 2,2 —二甲氧基一1, 2 —二苯基乙院一 1 一酬 等化合物。 此些化合中,又以2 —甲基一 1 一〔 4 一 (甲硫基) 苯基〕—2 —嗎啉丙酮一1、2 -苄基一 2 —二甲基胺基 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) (請先閱讀背面之注意事項再填寫本頁) 衣· 訂 ·線 -25- 508457 A7 ___ —_B7__ 五、發明説明(23 ) 一 1 — ( 4 一嗎啉苯基)丁酮一 1爲佳。前記苯乙酮化合 物可以單獨或將2種以上混合使用。 (請先閱讀背面之注意事項再填寫本頁) # @合起始劑中苯乙酮化合物之使用量,以對(C ) 多官能性單體與單官能性單體之合計1 〇 〇重量份時,較 it胃0*〇1至80重量份,更佳爲1至60重量份,最 佳爲1S3 〇重量份。苯乙酮化合物之使用量若低於 0·01重量份時,曝光引起之硬化會有不足之疑慮,而 著不容易形成特定之畫素陣列,又,超過8 0重量 份時,會有使所形成之著色 '層於顯像時容易由基板脫落之 傾向。 前記聯二咪唑系化合物之具體例如,2 , 2 / -雙( 2 —氯苯基)一 4,4', 5, 5 — —四(4 一乙氧羰基 苯基)—1, 2 / -聯二咪唑、2, 2 / -雙(2 —氯苯 基)一 4,4>, 5, —四(4 一乙氧羰基苯基)— 1,2 ^-聯二咪唑、2,2 — -雙(2 -氯苯基)一 4 ,4 / , 5,5 > - 四苯基-1 , 2,一聯二咪唑、2, 2^ —雙(2,4 一二氯苯基)一 4,4>,5, 5 ^ - 經濟部智慧財產局員工消f合作社印製 四苯基一 1, 2 / —聯二咪唑、2, 2 > —雙(2,4, 6 —三氯苯基)一4,4' 5, 5> —四苯基—1, 2 / -聯二咪唑、2, 2…一雙(2 -溴苯基)一 4, 4' 5, 5 / —四苯基-1, —聯二咪唑、2, -雙(2,4 —二溴苯基)—4,4>,5, 四苯基一 1 , 2 / -聯二咪唑、2 , 2 / —雙(2 , 4 , 6 -三氯苯基)一 4, 4' 5, 5> —四苯基一 1, 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) ~ -26 - 經濟部智慧財產局員工消費合作社印製 508457 A7 ___ B7 _ _ 五、發明説明(24) 2 / —聯二咪唑等化合物。其中又以2,2 > -雙(2 -氯苹基)—4,4 ^ , 5, 5 > —四(4 —乙氧鑛基苯基 )—1,-聯二咪唑、2,—雙(2 —氯苯基) —4,4>, 5, 5> —四苯基—1,2> —聯二咪唑、 2,2 -雙(2,4 —二氯苯基)—4,4 ,5, 5> —四苯基—1., 2 / —聯二咪唑、2, —雙(2 ,4,6 -三氯苯基)一 4,4 ^ , 5 , 5> —四苯基一 1, 2 > —聯二咪唑爲較佳。又以2,2 > —雙(2,4 —一氯苯基)一 4,4', 5, 5'—四苯基一 1,2 一聯二咪唑爲最佳。 上述聯二咪唑化合物,對於溶劑具有優良溶解性,故 不會產生未溶解物、結晶物等異物,此外,亦具有高感度 ,僅需使用少量能量之曝光即可充分進行硬化反應,反差 亦較高,未曝光部分不致產生硬化反應,故曝光後之塗膜 可充分地區隔出對顯像液不溶之硬化部分與對顯像液具有 高溶解性之未硬化部分,因此可形成不會斷線之依所需要 方式配置之高精密度畫素陣列。 前記聯二咪唑化合物可單獨或將2種以上混合使用皆 可〇 前記光聚合起始劑之聯二咪唑化合物之使用量,以對 (C )多官能性單體與單官能性單體之合計1 0 0重量份 時,較佳爲0.01至40重量份,更佳爲1至30重量 份,最佳爲1至2 0重量份。聯二咪唑化合物之使用量若 低於0.01重量份時,曝光引起之硬化會有不足之疑慮 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 訂 (請先閲讀背面之注意事項再填寫本頁) -27- 經濟部智慧財產局員工消費合作社印製 508457 A7 B7 五、發明説明(25) ,而著色層將不容易形成特定之畫素陣列,又,超過4〇 重量份時,則於顯像中會有使所形成之著色層由基板脫落 或造成畫素表面之膜產生裂痕等傾向。 氫供應體 本發明中,使用光聚合起始劑之聯二咪唑化合物時, 在倂用下記氫供應體下,可使感度再予提昇。 此處所稱「氫供應體」係指對經曝光後之聯二咪唑化 合物所產生之自由基而言,提供氫原子之化合物。 本發明中之氫供應體,以使用硫醇化合物與胺化合物 爲佳。 前記硫醇化合物,係爲以苯環或雜環爲母核,且與該 母核直接鍵結之氫硫基爲1個以上,較佳爲1至3個,更 佳爲1至2個之化合物(以下,簡稱「硫醇氫供應體」) 所構成者。 前記胺化合物,係爲以苯環或雜環爲母核,且與該母 核直接鍵結之胺基爲1個以上,較佳爲1至3個,更佳爲 1至2個之化合物(以下,簡稱「胺氫供應體」)所構成 者。 此些氫供應體,可同時存在有氫硫基與胺基。 以下,將對此些氫供應體作更具體之說明。 硫醇氫供應體,可具有1個以上之苯環或雜環,或同 時具有苯環與雜環皆可。又,具有2個以上此些環時,其 可形成或未形成縮合環皆可。 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 丨 訂 ~ (請先閲讀背面之注意事項再填寫本頁) -28- 經濟部智慧財產局員工消費合作社印製 508457 A7 _ B7 五、發明説明(26 ) 又,硫醇氫供應體,於具有2個以上氫硫基時,係以 至少殘存有1個以上游離氫硫基之方式爲條件,其他之氫 硫基受1個以上烷基、芳烷基或芳基所取代者亦可。又, 於至少殘存有1個以上游離氫硫基之方式爲條件時,亦可 具有2個硫原子夾有伸烷基等2價有機基所得之構造單位 ,或2個硫原子以二硫醚之形式鍵結所得之構造單位等。 此外,硫醇氫供應體,於氫硫基以外之部分亦可受羧 基、烷氧羰基、經取代之烷氧羰基、苯氧羰基、經取代之 苯氧羰基、硝基等所取代。 此些硫醇氫供應體之具體例,例如2 -氫硫基苯駢噻 唑、2 —氫硫基苯駢噁唑、2 —氫硫基苯駢咪唑、2,5 一氮硫基一 1,3,4 一硫一嗤、2 —氨硫基—2,5 .—二甲基胺吡啶等。 此些硫醇供應體中,以2 -氫硫基苯駢噻唑、2 —氫 硫基本餅d惡π坐爲佳,又以2 -氨硫基苯餅嚷哩爲最佳。 胺氫供應體,可具有1個以上之苯環或雜環,或同時 具有苯環與雜環皆可。又,具有2個以上此些環時,其可 形成或未形成縮合環皆可。 又,胺氫供應體,1個以上胺基可受烷基或經取代之 院基所取代,或胺基以外之部分亦可受羧基、烷氧羰基、 經取代之烷氧羰基、苯氧羰基、經取代之苯氧羰基、硝基 等所取代。 此些胺氫供應體之具體例如4 , 4 > 一雙(二甲基胺 )二苯甲酮、4, 4 — 一雙(二乙基胺)二苯甲酮、4 一 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) — 訂 ~ (請先閲讀背面之注意事項再填寫本頁) -29- 508457 A7 __ B7 五、發明説明(27) 二乙基胺苯乙酮、4 一二甲基胺苯丙酮、乙基一 4 —二甲 基胺苯甲酸酯、4 一二甲基胺苯甲酸、4 —二甲基胺苯甲 臆。 其中,此些氫供應體中又以4, 4 — 一雙(二甲基胺 )二苯甲酮、4,4 > —雙(二乙基胺)二苯甲酮爲佳, 特別是以4,4 > 一雙(二乙基胺)二苯甲酮爲最佳。 胺氫供應體,於聯二咪唑化合物以外之光聚合起始劑 中,亦具有作爲增感劑之作用。 氫供應體可單獨或將2種以上混合一起使用。將1種 以上硫醇氫供應體與1種以上之胺氫供應體組合使用時, 所形成之著色層於顯像時將不易由基板脫落,又可提高著 色層之強度與感度之強度。 將硫醇氫供應體與胺氫供應體組合之具體例如,2 -氫硫基苯駢噻唑/4,4/ —雙(二甲基胺)二苯甲酮、 2 —氫硫基苯駢噻唑/4,4 > 一雙(二乙基胺)二苯甲 酮、2 -氫硫基苯駢噁唑/ 4,4 / 一雙(二甲基胺)二 苯甲酮、2 —氫硫基苯駢噁唑/4,4 > —雙(二乙基胺 )二苯甲酮等。更佳之組合爲2 -氫硫基苯駢噻唑/4, 4 > —雙(二乙基胺)二苯甲酮、2 —氫硫基苯駢噁唑/ 4,4 / 一雙(二乙基胺)二苯甲酮,最佳之組合爲2 — 氫硫基苯駢噻唑/4,4/ 一雙(二乙基胺)二苯甲酮。 硫醇氫供應體與胺氫供應體之組合中,硫醇氫供應體 與胺氫供應體之重量比較佳爲1 : 1至1 : 4,更佳爲 1 ·· 1 至 1 ·· 3。 本紙張尺度適用中國國家標準(CNS ) A4規格(210X 297公釐) I! — — — #! (請先閱讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 -30- 經濟部智慧財產局員工消費合作社印製 508457 A7 ___ B7 五、發明説明(28 ) 本發明中,倂用聯二咪唑化合物時之氫供應體的使用 量,以對(C )多官能性單體與單官能性單體之合計 100重量份時,較佳爲〇 . 0 1至40重量份,更佳爲 1至30重量份,最佳爲1至20重量份。氫供應體之使 用量若低於0 · 0 1重量份時,對感度之改良效果將會有 降低之傾向,又,超過4 0重量份時,所形成之著色層於 顯像時會有容易由基板脫落之傾向。 又,光聚合起始劑之前記三三嗪系化合物之具體例如 2,4,6 —三(三氯甲基)一 s —三嗪、 2 —甲基一 4,6 —雙(三氯甲基)一 s —三嗪、 2 —〔2— (5 —甲基呋喃一 2 —基)次乙基〕一4 ,6 —雙(三氯甲基)一s —三嗪、 2 —〔2 —(呋喃一 2 —基)次乙基〕一4, 6 —雙 (三氯甲基)一s—三嗪、 2 —〔 2 —(4 一 一乙基胺基一 2 —甲基苯基)次乙 基〕—4,6 —雙(三氯甲基)一s —三嗪、 2 —〔2 — (3, 4 一二甲氧基苯基)次乙基〕一4 ,6 —雙(三氯甲基)一s —三嗪、 2 —(4 一甲氧基苯基)一 4,6 —雙(三氯甲基) 一 s —三嗪、 2 —(4 —乙氧基苯乙烯基)一 4, 6 —雙(三氯甲 基)一 s —三嗪、 2 — (4 - η — 丁氧苯基)—4, 6 -雙(三氯甲基 本紙張尺度適用中國國家標準(CNS ) Α4規格(210Χ29?公釐) ----------0^-------1Τ—---- (請先閲讀背面之注意事項再填寫本頁) -31 - 508457 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明(29) )一 S -三嗪、 下記式(4 )所示化合物(以下,簡稱「三嗪化合物I ch3 Any type of multifunctional acrylate (1) or polyfunctional acrylate (2) printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs can be produced with high pixel strength and excellent surface smoothness, without Radiation-sensitive radioactive compositions that can contaminate areas other than the pixel formation area are also less likely to produce film residue. In the present invention, the carboxyl group-containing polyfunctional monomer can improve the dissolution characteristics of the alkaline imaging solution of the radiation-sensitive radioactive composition, and has the effects of suppressing the residue of undissolved matter after development. This point also shows the same effect as the organic acid component described later as an additive. Secondly, other polyfunctional monomers such as ethylene glycol, propylene glycol and other alkanediol di (meth) acrylates; this paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm) " -21- Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 508457 A7 B7 V. Description of the invention (19) Poly (ethylene) acrylates such as polyethylene glycol, polypropylene glycol, and other poly (meth) acrylates; glycerol, trimethylolpropane Poly (meth) acrylates of polyhydric alcohols of 3 or more valences, such as alumina, pentaerythritol group, dipentaerythritol group; polyester, epoxy resin, urethane resin, alkyd resin, polysiloxane resin, spiro resin etc. (Meth) acrylic acid esters; two (meth) acrylic acid esters of two terminal hydroxylated polymers such as polyterminal 1,3-butadiene, two terminal hydroxyl polyisobutylene, two terminal hydroxypolycaprolactam, and the like; -Compounds such as tris [2- (meth) acryloyloxyethyl] phosphide. Among these polyfunctional monomers, poly (meth) acrylates of polyhydric alcohols having a valence of 3 or more are preferred. Specifically, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (methyl) Base) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are preferred, especially trimethylolpropane triacrylate, Pentaerythritol triacrylate and dipentaerythritol hexaacrylate have the disadvantages of high pixel strength, excellent pixel surface smoothness, and less contamination of unexposed substrates and light-shielding layer regions, or residual films. In the present invention, the polyfunctional monomer may be used singly or in combination of two or more kinds, and may be used in combination with a carboxyl-containing polyfunctional monomer and other polyfunctional monomers. When the radiation-sensitive radioactive composition of the present invention is used as an inductive radioactive composition for forming a coloring layer of a driving substrate of a thin-film transistor (TFT) -type color liquid crystal display device, the paper size can be applied to Chinese national standards (CNS ) A4 size (210X297mm) I ------- • Cloth ------ 1T ----- · $ (Please read the precautions on the back before filling this page) -22- 508457 A7 B7 V. Description of the invention (20) (Please read the notes on the back before filling in this page) It has sufficient resolution, and can form a conductive path with the required size when forming the coloring layer. In addition, when a part or all of the polyfunctional monomer is used as a carboxyl-containing polyfunctional monomer, the size of the conducting path can be appropriately selected according to the pattern corresponding to the photomask. In the present invention, when used as a carboxyl group-containing polyfunctional monomer, the use ratio of the polyfunctional monomer is preferably 5 to 95% by weight, more preferably 10 to 80% by weight, and most preferably 1 0 to 50% by weight. In this case, if the use ratio of the carboxyl group-containing polyfunctional monomer is less than 5% by weight, when the content of the radiation-sensitive radioactive composition is used, in particular, the later-mentioned (E) carboxyl group-containing monofunctional monomer is not used. When it is in the body, it tends to be difficult to form a desired conduction path, and when it exceeds 95% by weight, the coloring layer is easily impregnated because of alkali development, so the coloring layer may fall off during development. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs in the present invention, the amount of the polyfunctional monomer used is generally 5 to 500 parts by weight for (B) 100 parts by weight of the alkali-soluble resin, preferably It is 20 to 300 parts by weight. In this case, if the used amount of the polyfunctional monomer is less than 5 parts by weight, the pixel strength or the smoothness of the pixel surface may be reduced. When it exceeds 500 parts by weight, for example, alkali may be caused. Degradability, may have the disadvantage of contaminating unexposed substrates and light-shielding layer areas, or generating residual films. In the present invention, a polyfunctional monomer can be used in combination with a monofunctional monomer having one polymerizable unsaturated bond. Former monofunctional monomers, for example, carboxyl-containing unsaturated monomers, copolymerizable unsaturated monomers, or N as exemplified in the aforementioned (B) alkali-soluble resin, or N-This paper applies the Chinese National Standard (CNS) A4 specification (210X297) (Mm) -23- 508457 A7 _B7_ _ V. Description of the invention (21) (Please read the notes on the back before filling out this page) Vinyl amber milled imine, N-vinyl pyrrolidone, N-vinyl Phthamidimine, N-vinyl-2-piperidone, N-vinyl, N-vinyl-ε-caprolactam, N-vinylpyrrole, N-vinylpyrrole, N-ethylenyl Imide, Ν—ethoxyimidazoline, Ν—ethenyl indole, Ν—vinyl indololine, NH—vinylbenzimidazole, NH—vinylcarbazole, NH—vinylpiperidine, N—vinylpiperazine, N—vinylmorpholine, N—ethoxybenzyl oxazine, and other N—ethanoyl derivatives; N— (meth) acrylic acid oxymorpholine, commercially available For example, M-5300, M-5400, M-5600 (commercial-product name, manufactured by Toa Synthesis Co., Ltd.), and the like. The amount of these monofunctional monomers is preferably 90% by weight or less, and more preferably 50% by weight or less, based on the total amount of the polyfunctional monomer and monofunctionality. At this time, if the use ratio of the monofunctional monomer exceeds 90% by weight, the strength or surface smoothness of the pixels or the black matrix tends to decrease. (D) Photopolymerization initiator Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ^ The photopolymerization initiator used in the present invention is made of visible light, ultraviolet light, far ultraviolet light, electron rays, X-rays, etc. Irradiation (hereinafter referred to as "exposure") is a reactive compound that starts polymerization of the polyfunctional monomer (C) and the monofunctional monomer used as necessary to start polymerization. Such photopolymerization initiators are, for example, the following acetophenone compounds, biimidazole compounds, triazine compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear benzophenone compounds, and xanthones Compounds and sizes of this paper are applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) -24-508457 Employees' Cooperatives of Intellectual Property Bureau, Ministry of Economic Affairs Consumer Cooperative Indo A7 _____ B7 _ ^ _ V. Description of Invention (22) Diazo compounds and other compounds . In the present invention, the photopolymerization initiator may be used singly or in combination of two or more kinds. The photopolymerization initiator is preferably at least one selected from the group consisting of an acetophenone compound, a biimidazole compound, and a triazine compound group. In the present invention, the amount of the photopolymerization initiator is generally used when the total amount of the (C) polyfunctional monomer and the monofunctional monomer used when necessary is 100 parts by weight, preferably 0. 0 1 to 80 parts by weight, more preferably 1 to 60 parts by weight. If the amount of the photopolymerization initiator used is less than 0 · 0 1 parts by weight, there may be a concern of insufficient hardening in the exposed portion, and for pixels In terms of pattern, it will not be easy to obtain the required pixel array, and when it exceeds 80 parts by weight, the formed pixels tend to fall off easily from the substrate during development. In the preferred photopolymerization initiator of the present invention, specific examples of the acetophenone compound include 2-hydroxy-2-methyl-1-phenylpropane-1, 1-ketone, 2-methyl-1, 1- [4, ( (Methylthio) phenyl] -1 2-morpholine acetone-1, 2-benzyl-2-dimethylamino-1 (4-monomorpholinephenyl) butanone-1, 1-hydroxycyclohexyl • Phenyl ketone, 2,2-dimethoxy-1,2-diphenylethyl, etc. In these compounds, the basic paper size of 2-methyl-1 1- [4-mono (methylthio) phenyl] -2-morpholine acetone-1, 2-benzyl-1 2-dimethylamine is applicable to China. National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page) Clothing · Order · Thread -25- 508457 A7 ___ —_B7__ 5. Description of the invention (23) 1 1 — (4 Monomorpholinephenyl) butanone-1 is preferred. The aforementioned acetophenone compound may be used alone or as a mixture of two or more. (Please read the precautions on the back before filling this page) # @ 合 Starter The amount of acetophenone compound used is based on the total weight of (C) polyfunctional monomers and monofunctional monomers. When serving, it is preferably from 0 to 〇1 to 80 parts by weight, more preferably from 1 to 60 parts by weight, and most preferably from 1 to 300 parts by weight. If the amount of acetophenone compound is less than 0.01 parts by weight, there is a concern that the hardening caused by exposure will be insufficient, and it will not be easy to form a specific pixel array. When it exceeds 80 parts by weight, The formed colored layer tends to be easily detached from the substrate during development. Specific examples of the aforementioned biimidazole-based compounds include 2, 2 / -bis (2-chlorophenyl) -4,4 ', 5,5--tetrakis (4-ethoxycarbonylphenyl) -1, 2 /- Biimidazole, 2, 2 / -bis (2-chlorophenyl) -1,4 >, 5,4-tetrakis (4-ethoxycarbonylphenyl) — 1, 2 ^ -biimidazole, 2, 2 — -Bis (2-chlorophenyl) -4,4 /, 5,5 >-Tetraphenyl-1, 2, bibiimidazole, 2, 2 ^ —bis (2,4-dichlorophenyl) -1,4 >, 5,5 ^-Tetraphenyl-1, 2 / -bi-imidazole, 2, 2 >-bis (2, 4, 6-3) printed by employees of the Intellectual Property Bureau of the Ministry of Economy (Chlorophenyl) -1,4,4'5,5> -tetraphenyl-1, 2 / -biimidazole, 2, 2 ...-bis (2-bromophenyl) -4, 4 '5, 5 /- Tetraphenyl-1, -biimidazole, 2, -bis (2,4-dibromophenyl) -4,4 >, 5, tetraphenyl-1, 2 / -biimidazole, 2, 2 / —Bis (2, 4, 6-trichlorophenyl) -1, 4, 4 '5, 5 > —Tetraphenyl-1, This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) ~ -26 -Ministry of Economy Intellectual Property Co-op staff printed 508457 A7 ___ B7 _ _ V. Description of the Invention (24) 2 / - biimidazole compounds and the like. Among them, 2,2 > -bis (2-chloropentyl) -4,4 ^, 5,5 > -tetrakis (4-ethoxyminylphenyl) -1, -biimidazole, 2, —Bis (2-chlorophenyl) —4,4>, 5, 5> —tetraphenyl—1,2,> —biimidazole, 2,2-bis (2,4-dichlorophenyl) —4 , 4,5,5 > —tetraphenyl-1., 2 / —biimidazole, 2, —bis (2,4,6-trichlorophenyl) —4,4 ^, 5, 5> Phenyl-1,2 > -biimidazole is preferred. And 2,2 > -bis (2,4-monochlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2-biimidazole is the best. The above-mentioned biimidazole compound has excellent solubility in solvents, so it does not produce foreign matters such as undissolved matter and crystals. In addition, it also has high sensitivity, and requires only a small amount of energy for exposure to sufficiently harden the reaction. High, the unexposed part does not cause hardening reaction, so the coating film after exposure can sufficiently separate the hardened part that is insoluble in the developing solution and the unhardened part that has high solubility in the developing solution, so it can form no breaks A high-precision pixel array configured in the required way. The pre-biimidazole compound may be used alone or in combination of two or more. The amount of the bi-imidazole compound used in the pre-photopolymerization initiator is based on the total of (C) the polyfunctional monomer and the monofunctional monomer. When it is 100 parts by weight, it is preferably 0.01 to 40 parts by weight, more preferably 1 to 30 parts by weight, and most preferably 1 to 20 parts by weight. If the amount of biimidazole compound is less than 0.01 parts by weight, there is a concern of insufficient hardening caused by exposure. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm). (Please read the precautions on the back first (Please fill in this page again) -27- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 508457 A7 B7 V. Description of the invention (25), and the color layer will not easily form a specific pixel array, and when it exceeds 40 parts by weight In the development, there is a tendency that the colored layer formed is peeled off from the substrate or the film on the pixel surface is cracked. Hydrogen donor In the present invention, when a biimidazole compound is used as a photopolymerization initiator, the sensitivity can be further improved by using a hydrogen donor as described below. The "hydrogen donor" as used herein refers to a compound that provides a hydrogen atom to the radicals produced by the exposed biimidazole compound. The hydrogen supplier in the present invention is preferably a thiol compound and an amine compound. The foregoing thiol compound is a benzene ring or heterocyclic ring as a mother core, and the number of hydrogen thio groups directly bonded to the mother core is one or more, preferably one to three, more preferably one to two. Compounds (hereinafter referred to as "thiol hydrogen supplier"). The aforementioned amine compound is a compound having a benzene ring or a heterocyclic ring as a mother core, and one or more amine groups directly bonded to the mother core, preferably 1 to 3, more preferably 1 to 2 ( Hereinafter referred to as "amine hydrogen supplier"). These hydrogen suppliers may have both a hydrogen sulfide group and an amine group. Hereinafter, these hydrogen suppliers will be described in more detail. The thiol hydrogen supplier may have more than one benzene ring or heterocyclic ring, or both benzene ring and heterocyclic ring. When there are two or more of these rings, it may or may not form a condensed ring. This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 丨 Order ~ (Please read the precautions on the back before filling out this page) -28- Printed by the Intellectual Property Bureau Employee Consumer Cooperative of the Ministry of Economic Affairs 508457 A7 _ B7 V. Description of the invention (26) In addition, when the thiol hydrogen supplier has two or more hydrogen sulfide groups, the condition is that at least one free hydrogen sulfide group remains, and the other hydrogen sulfide groups are subject to one. The above alkyl, aralkyl or aryl groups may be substituted. In addition, when the condition that at least one free hydrogen sulfide group remains is a condition, it may have a structural unit obtained by interposing a divalent organic group such as an alkylene group with two sulfur atoms, or a disulfide with two sulfur atoms. The structural unit obtained by the form bonding. In addition, the thiol hydrogen supplier, other than the hydrogenthio group, may be substituted by a carboxyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a phenoxycarbonyl group, a substituted phenoxycarbonyl group, a nitro group, and the like. Specific examples of these thiol hydrogen suppliers are, for example, 2-hydrothiobenzimidazole, 2-hydrothiobenzimidazole, 2-hydrothiobenzimidazole, 2,5-nitrosulfanyl-1, 3,4-monothio-amidine, 2-aminothio-2,5.-dimethylaminopyridine, etc. Among these thiol suppliers, 2-hydrothiobenzidine thiazole and 2-hydrosulfide basic cake are preferred, and 2-aminothiobenzene cake is the best. The amine hydrogen supplier may have more than one benzene ring or heterocyclic ring, or both a benzene ring and a heterocyclic ring. When there are two or more of these rings, it may or may not form a condensed ring. Moreover, in the amine hydrogen supplier, more than one amine group may be substituted by an alkyl group or a substituted academic group, or a part other than the amine group may also be substituted by a carboxyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, and a phenoxycarbonyl group. , Substituted by substituted phenoxycarbonyl, nitro, etc. Specific examples of these amine hydrogen suppliers are 4, 4 > bis (dimethylamine) benzophenone, 4, 4-bis (diethylamine) benzophenone, 4 a paper size applicable China National Standard (CNS) A4 Specification (210X297 mm) — Order ~ (Please read the notes on the back before filling this page) -29- 508457 A7 __ B7 V. Description of the Invention (27) Diethylamine Acetophenone , 4-dimethylamine phenylacetone, ethyl 4-dimethylamine benzoate, 4-dimethylamine benzoic acid, 4-dimethylamine benzamidine. Among them, 4, 4-bis (dimethylamine) benzophenone and 4,4 > -bis (diethylamine) benzophenone are more preferred, especially based on 4,4 > Monobis (diethylamine) benzophenone is the best. The amine hydrogen donor also functions as a sensitizer in photopolymerization initiators other than biimidazole compounds. The hydrogen supplier can be used alone or as a mixture of two or more kinds. When one or more thiol hydrogen suppliers and one or more amine hydrogen suppliers are used in combination, the formed colored layer will not be easily peeled off from the substrate during development, and the strength and sensitivity of the colored layer can be improved. Specific examples of combining a thiol hydrogen supplier with an amine hydrogen supplier, for example, 2-hydrothiobenzophenothiazole / 4,4 / -bis (dimethylamine) benzophenone, 2-hydrothiobenzophenthiazole / 4,4 > bis (diethylamine) benzophenone, 2-hydrothiobenzoxazole / 4,4 / bis (dimethylamine) benzophenone, 2-hydrosulfide Benzoxazole / 4,4 > -bis (diethylamine) benzophenone and the like. A more preferred combination is 2-hydrothiobenzoxazole / 4,4 > -bis (diethylamine) benzophenone, 2-hydrothiobenzoxazole / 4,4 / one bis (diethyl Methyl amine) benzophenone, the best combination is 2-hydrothiobenzimidazole / 4,4 / monobis (diethylamine) benzophenone. In the combination of a thiol hydrogen supplier and an amine hydrogen supplier, the weight ratio of the thiol hydrogen supplier and the amine hydrogen supplier is preferably 1: 1 to 1: 4, and more preferably 1 ·· 1 to 1 ·· 3. This paper size applies to China National Standard (CNS) A4 specification (210X 297 mm) I! — — — #! (Please read the precautions on the back before filling this page) Order printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperatives- 30- Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 508457 A7 ___ B7 V. Description of the invention (28) In the present invention, the amount of hydrogen supplier used when using biimidazole compounds is used for (C) polyfunctionality When the total of the monomer and the monofunctional monomer is 100 parts by weight, it is preferably 0.01 to 40 parts by weight, more preferably 1 to 30 parts by weight, and most preferably 1 to 20 parts by weight. If the amount of the hydrogen supplier is less than 0. 0 1 parts by weight, the sensitivity improvement effect tends to decrease, and when it exceeds 40 parts by weight, the colored layer formed may be easily developed during development. The tendency to fall off from the substrate. Specific examples of the tritriazine-based compound described before the photopolymerization initiator include 2,4,6-tris (trichloromethyl) -s-triazine, and 2-methyl-4,6-bis (trichloromethyl). ) -S-triazine, 2- [2- (5-methylfuran-2-yl) ethylidene] -4,6-bis (trichloromethyl) -s-triazine, 2— [2 — (Furan-2-yl) ethynyl] —4, 6—bis (trichloromethyl) —s—triazine, 2— [2— (4-monoethylamino—2-methylphenyl) ) Ethylene] -4,6-bis (trichloromethyl) -s-triazine, 2- [2— (3,4-dimethoxyphenyl) ethynyl] -4,6-bis (Trichloromethyl) -s-triazine, 2- (4-monomethoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxybenzene Vinyl) -4, 6-bis (trichloromethyl) -s-triazine, 2— (4-η-butoxyphenyl) -4, 6-bis (trichloromethyl) This paper applies Chinese national standards (CNS) Α4 specification (210 × 29? Mm) ---------- 0 ^ ------- 1T —---- (Please read the Please fill in this page on matters needing attention) -31-508457 A7 B7 Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economy Triazine compound
等具有鹵甲基之三嗪系化合物 等。 此些三嗪化合物中,以2 —〔 2 — ( 3 , 4 —二甲氧 基苯基)次乙基〕一 4, 6 —雙(三氯甲基)一 s —三嗪 、三嗪化合物(1 )爲佳。 前記三嗪化合物,可單獨使用或將2種以上混合使用 〇 光聚合起始劑之三嗪化合物的使用量,以對(C )多 官能性單體與單官能性單體之合計1 0 0重量份時,較佳 爲0 · 0 1至40重量份,更佳爲1至3 0重量份,最佳 爲1至20重量份。三嗪化合物之使用量若低於〇· 重量份時,曝光所引起之硬化將不充分,故著色層將會有· 不容易依所需要之排列方式得到畫素陣列之傾向,又,超 過40重量份時,所形成之著色層於顯像時會有容易^基 板脫落之傾向。 添加劑 (請先閲讀背面之注意事項再填寫本頁) 琴 訂 .1# 本紙張尺度適用中國國家標準(CNS) A4規格(2iOX297公釐) -32- 經濟部智慧財產局員工消費合作社印製 508457 A7 B7 五、發明説明(30 ) 本發明之彩色液晶顯示裝置用輻射敏感放射線性組成 物,必要時可再添加各種添加劑。 前記添加劑例如具有可改善輻射敏感放射線性組成物 於鹼顯像液中之溶解性,且可抑制顯像後未溶解物之殘留 情形,其例如有機酸或有機鋁化合物(惟,前記氫供應體 除外)等。 有機酴 前記有機酸例如分子.中具有1個以上羧基之分子量 1,0 0 0以下之脂肪族羧酸或含苯基之羧酸爲佳。 前脂肪族羧酸例如, 蟻酸、乙酸、丙酸、丁酸、戊酸、三甲基乙酸、己酸 、二乙基醋酸、庚酸'癸酸等脂肪族一羧酸類;' 草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、 辛二酸、壬二酸、癸二酸、巴豆二酸、甲基丙二酸、乙基 丙二酸、二甲基丙二酸、甲基琥珀酸、四甲基琥珀酸、環 己烷二羧酸、依康酸、檬康酸、馬來酸、富馬酸、中康酸 等二羧酸類等。 丙三羧酸、烏頭酸、樟腦三酸等三羧酸類。 又,前記含苯基之羧酸,例如羧基直接與苯基鍵結之 化合物或,羧基介由碳鏈與苯基鍵結之化合物等。 含苯基之羧酸之例如, 苯甲酸、甲苯酸、枯茗酸、二甲苯酸、二甲苯甲酸等 芳香族一羧酸類; 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) I---------------IT------ (請先閲讀背面之注意事項再填寫本頁) -33 - 508457 A7 B7 五、發明説明(31 ) 鄰苯二酸、間苯二酸、對苯二酸等芳香族二羧酸類; 偏苯三酸、均苯三酸、偏苯四酸、均苯四酸等3價以. 上之芳香族多羧酸類,或 苯乙酸、氫化阿托酸、氫化桂皮酸、苦杏仁酸、苯基 琥珀酸、阿托酸、桂皮酸、內桂皮酸、香豆酸、傘型酸等 化合物。 此些有機物中,就對鹼溶解性、後述之對溶媒溶解性 、防止污染未曝光部分之基板及遮光層或防止膜殘留等觀 點而言,脂肪族羧酸例如以脂肪族二羧酸爲佳,特別是以 丙二酸、己二酸、依康酸、檬康酸、富馬酸、中康酸等爲 更佳,又,含苯基之羧酸以芳香族二羧酸爲佳,特別是以 鄰苯二酸爲更佳。 前記有機酸可單獨使用或將2種以上混合使用皆可。 有機酸之使用量,以對輻射敏感放射線性組成物全體 而言,較佳爲1 5重量%以下,更佳爲1 〇重量%以下。 有機酸之使用量若超過1 5重量%時,所形成之著色層對 基板之密著性會有降低之傾向。 有機胺化合物 又,有機胺化合物係以使用分子中具有1個以上胺基 之分子量爲1 , 0 0 0以下隻脂肪族胺或含苯基之胺爲佳 。前記脂肪族胺之例如, η —丙胺、i —丙胺、n 一 丁胺、i — 丁胺、s e c —丁胺、t 一 丁胺、η—戊胺、n 一己胺、環己胺等單( 本紙張尺度適用中國國家標準(CNS ) A4規格(210x297公釐) — ——i — #! (請先閱讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 -34- 508457 經濟部智慧財產局員工消費合作社印製 A7 B7五、發明説明(32 ) 環)烷基胺; 甲基乙胺、二乙胺、甲基η —丙胺、乙基η —丙胺、 二一 η —丙胺、二—i —丙胺、二—η —丙胺、二—η — 丁胺、二一 i — 丁胺、二—s e c —丁胺、二一t — 丁胺 等二(環)烷基胺; 二甲基乙胺、甲基二乙胺、三乙胺、二甲基η —丙胺 、二乙基η —丙胺、甲基二一 η —丙胺、乙基二一 i 一丙 胺、三—η —丙胺、三—i —丙胺、三—η — 丁胺、三一 1 一丁胺、三一 s e c -丁胺、三—t 一丁胺等三(環) 烷基胺; 2 —胺基乙醇、3 —胺基—1 一丙醇、1 一胺基一 2 一丙醇、4 一胺基—1 — 丁醇等單(環)烷醇胺; 二乙醇胺、二一 η丙醇胺、二—i —丙醇胺、二一 η 一 丁醇胺、二一 i 一丁醇胺等二(環)烷醇胺; 三乙醇胺、三一 η丙醇胺、三一 i —丙醇胺、三一 η 一 丁醇胺、三一 1 一丁醇胺等三(環)烷醇胺; 3 -胺基一 1,2 —丙二醇、2 -胺基一 1,3 -丙 二醇、4 —胺基一 1,2 — 丁二醇、4 一胺基—1,3 -丁二醇、3 —二甲基胺基—1, 2 —丙二醇、3 —二乙基 胺基一 1, 2 —丙二醇、2 —甲基胺基一1, 3 —丙二醇 、2 -二乙基胺基—1,3 —丙二醇等胺基(環)烷二醇 /3 -丙胺酸、2—胺基丁酸、3—胺基丁酸、4一胺 基丁酸、2 -胺基異丁酸、3 -胺基異丁酸等胺基羧酸等 本紙張尺度適用中國國家標準( CNS ) Α4規格(210X 297公釐) ~ -35- (請先閱讀背面之注意事項再填寫本頁) 508457 A7 B7 五、發明説明(33 ) 〇 (請先閲讀背面之注意事項再填寫本頁) 又,含苯基之胺例如,胺基直接與苯基鍵結之化合物 ,胺基介由碳鏈與苯基鍵結之化合物等。 含苯基之胺例如, 苯胺、0 —甲基苯胺、m —甲基苯胺、P —甲基苯胺 、P —乙基苯胺、1 一萘基苯胺、2 -萘基苯胺、N, N —二甲基苯胺、N, N —二乙基苯胺、p —甲基一N, N -二甲基苯胺等芳香族胺; 〇 -胺基苄醇、m -胺基苄醇、p —胺基苄醇、p 一 二甲基胺基苄醇、p -二乙基胺基苄醇等胺基苄醇; 〇—胺基苯酚、m —胺基苯酚、p —胺基苯酚、p 一 二甲基胺基苯酚、p —二乙基胺基苯酚等胺基苯酚; m —胺基苯甲酸、p -胺基苯甲酸、p —二‘甲基胺基 苯甲酸、p —二乙基胺基苯甲酸等胺基苯甲酸(衍生物) 等。 經濟部智慧財產局員工消費合作社印製 此些有機胺化合物中,將後述之對溶媒的溶解性、防 止對未曝光部之基板或遮光層上產生污染或膜殘留等觀點 而言,脂肪族胺例如以使用單(環)烷醇胺與胺基(環) 烷醇二胺爲佳,特別是以2 —胺基乙醇、3 -胺基一 1 一 丙醇、5 —胺基一 1—戊醇、3 -胺基一 1,2 —丙二醇 、2 -胺基—1, 3 —丙二醇、4 一胺基—1,2〜丁二 醇等爲更佳。又含苯基之胺例如胺基苯酚爲佳,特別是◦ -胺基苯酹、m —胺基苯酣、p -胺基苯酣等爲更佳。 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -36 - 508457 經濟部智慧財產局員工消費合作社印製 A7 B7五、發明説明(34 ) 前記有機胺化合物可單獨使用或將2種以上混合使用 亦可。 有機胺化合物之使用量,以對輻射敏感放射線性組成 物全體而言,較佳爲5重量%以下,更佳爲10重量%以 下。有機胺化合物之使用量超過1 5重量%時,所形成之 著色層與基板之密著性會有降低之傾向。 又,前記有機酸以外之添加劑之例如, 銅酞菁衍生物等藍色顏料衍生物或黃色顏料衍生物等 分散助劑; 玻璃、氧化鋁等塡充劑; 聚乙二醇、聚乙二醇一烷基醚類、聚(氟烷基丙烯酸 酯)類等高分子化合物; 陰離子、陽離子、質子系之界面活性劑; 乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基 三(2 —甲氧乙氧基)矽烷、N —(2 —胺基乙基)一 3 —胺丙基•甲基•二甲氧基矽烷、N — ( 2 —胺基乙基) -3 -胺丙基三甲基基矽烷、3 -胺丙基三乙氧基矽烷、 3 -環氧丙氧基丙基三甲氧基矽烷、3 -環氧丙氧基丙基 •甲基•二甲氧基矽烷、2 —(3,4 一乙氧基環己基) 乙基三甲氧基矽烷、3 —氯丙基•甲基•二甲氧基矽烷、 3 -氯丙基三甲氧基矽烷、3 -甲基丙烯醯基丙基三甲氧 基矽烷、3 -氫硫基丙基三甲氧基矽烷等密著促進劑; 2 , 2 > —硫雙(4 一甲基一 6— t — 丁苯基)、2 ,6-二一t一丁基苯酚等氧化防止劑; 丨 訂 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -37- 508457 Α7 Β7 經濟部智慧財產局員工消費合作社印製 五、發明説明(35 ) 2—(3 — t 一丁基—5 —甲基一2—經苯基)—5 -氯基苯駢三唑、烷氧基聯苯酚類等紫外線吸收劑; 聚丙烯酸鈉等凝聚防止劑; 1, 1 一偶氮雙(環己烷—1 一碳基腈)、2 -苯基 偶氮一 4 —甲氧基一2,4 一二甲基戊腈等熱自由基產生 劑; 等添加劑。 溶齊 本發明之輻射敏感放射線性組成物,係以前記(A ) 著色劑、(B )鹼可溶性樹脂、(C )多官能性單體與( D )光聚合起始劑爲必須成分,較佳爲配合與溶劑以液狀 .組成物之方式使用。 前記溶劑,一般係爲可將前記輻射敏感放射線性組成 物之(A)至(D)成分或添加劑成分分散或溶解,或不 與此些成分進行反應,且具有適度揮發性之物,而可適當 地選擇使用。 此些溶劑例如 乙二醇一甲基醚、乙二醇一乙基醚、乙二醇——η-丙基醚、乙二醇一一 η — 丁基醚、二乙二醇一甲基醚、二 乙二醇一乙基醚、二乙二醇一—η —丙基醚、二乙二醇一 一 η - 丁基醚、三乙二醇一甲基醚、三乙二醇一乙基醚、 丙二醇一甲基醚、丙二醇一乙基醚、丙二醇一一 η -丙基 醚、丙二醇——η — 丁基醚、二丙二醇一甲基醚、二丙二 本紙張尺度適用中國國家標準(CNS ) Α4規格(210Χ297公釐) (請先閲讀背面之注意事項再填寫本頁) -38- 508457 Α7 Β7 經濟部智慧財產局員工消費合作社印製 五、發明説明(36 ) 醇一乙基醚、二丙二醇一 —η -丙基醚、丙二醇一 —^ — 丁基醚、三丙二醇一甲基醚、三丙二醇一乙基醚等(聚) 烷二醇一烷基醚; 乙二醇一甲基醚乙酸酯、乙二醇一乙基醚乙酸酯、二 乙二醇一甲基醚乙酸酯、二乙二醇一乙基醚乙酸酯、丙二 醇一甲基醚乙酸酯、丙二醇一乙基醚乙酸酯等(聚)烷醇 一烷基醚乙酸酯;二乙二醇二甲基醚、二乙二醇甲基乙基 醚、二乙二醇二乙基醚、四氫呋喃等其他醚類; 甲基乙酮、環己酮、2 —庚酮、3 —庚酮等酮類; 2 -羥基丙酸甲酯、2 —羥基丙酸乙酯等乳酸烷基酯 類; 2 —羥基一 2 —甲基丙酸乙酯、3 —甲氧基丙酸甲酯 、3 —甲氧基丙酸乙酯、3 —乙氧基丙酸甲酯、' 3 —乙氧 基丙酸乙酯、乙氧基乙酸乙酯、羥基乙酸乙酯、2 —羥基 一 3 —甲基丁酸甲酯、3 —甲基一 3 —甲氧基丁基乙酸酯 、3 —甲基一 3 —甲氧基丁基丙酸酯、乙酸乙酯、乙酸一 η —丙酯、乙酸一i —丙酯、乙酸—η —丁酯、乙酸一1 一丁酯、甲酸一 η —戊酯、乙酸—i 一戊酯、丙酸一 η — 丁酯、丁酸乙酯、丁酸η -丙酯、丁酸一 i 一丙酯、丁酸 一 η - 丁酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸一 η —丙 酯、乙醯乙酸甲酯、乙醯乙酸乙酯、2 —噁丁酸乙酯等其 他酯類; 甲苯、二甲苯等芳香族烴類; Ν—甲基吡咯烷酮、Ν, Ν—二甲基甲醯胺、Ν, Ν 本紙張尺度適用中國國家標準(CNS ) Α4規格(210Χ297公釐) I -------訂 ~^---- (請先閱讀背面之注意事項再填寫本頁) -39- 508457 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明(37 ) 一二甲基乙醯胺等羧酸醯胺類等。 . 前記溶劑中,就溶解性、顏料分散性、塗佈性等觀點 而言,以使用丙二醇一甲基醚、乙二醇一甲基醚乙酸酯、 丙二醇一甲基醚乙酸酯、丙二醇一乙基醚乙酸酯、二乙二 醇二甲基醚、二乙二醇甲基乙基醚、環己酮、2 —庚酮、 3 -庚酮、2 —羥基丙酸乙酯、3 —甲氧基丙酸乙酯、3 一乙氧基丙酸甲酯、3 —乙氧基丙酸乙酯、3 —甲基一 3 一甲氧基丁基丙酸酯、乙酸一 η —丁酯、乙酸一 i 一丁酯 、甲酸—i —戊酯、乙酸一 i〜戊酯、丙酸一 η — 丁酯、 丁酸乙酯、丁酸一 i 一丙酯、丁酸一 η - 丁酯、丙酮酸乙 酯等溶劑爲佳。 此些溶劑可單獨使用或將2種以上混合使用。 此外,前記溶劑中,可再倂用苄基乙醚、二己基醚、 丙酮基丙酮、異佛爾酮、己酸、辛酸、1 一辛醇、1 一壬 醇、苄醇、乙酸苄酯、苯甲酸乙酯、草酸二乙酯、馬來酸 二乙酯、r 一丁內酯、碳酸乙烯、碳酸丙烯、乙二醇一苯 基醚乙酸酯等高沸點之溶劑等。 此些高沸點溶劑可單獨使用或將2種以上合倂使用皆 可° 溶劑之使用量並未有特別之限定,但就所製得之輻射 敏感放射線性組成物之塗佈性、安定性等觀點而言,以對 該組成物溶劑以外之各成分之合計濃度,較佳爲5至5 0 重量%,最佳爲10至40重量%爲宜。 — ;----:1· — (請先閱讀背面之注意事項再填寫本頁) 訂 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -40 - 508457 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明(38) 蓋之製作方法 本發明之輻射敏感放射線性組成物,係用於以蝕刻印 刷法形成薄膜電晶體(τ F T )形式液晶顯示裝置的驅動 用基板上所設置之驅動用基板(以下,簡稱「T F T形式 驅動用基板」)之著色層者。此處所稱之著色層,係指顯 示用晝素、黑色基質,或包含此二者所具有之意義。 以下,將對於T F T液晶驅動用基板上形成著色層之 方法進行說明。 首先,於T F T型式液晶驅動用基板表面上,或於該 驅動基板之表面上形成如氮化矽膜之鈍化膜之基板表面上 ,依其必要性,對形成畫素圖型之部分形成遮光層後,於 此基板上塗佈以例如分散有紅色顏料之輻射敏感放射線性 組成物之液狀組成物後,進行預烘烤使溶劑蒸發,形成塗 膜。隨後,將此塗膜介由光罩進行曝光,再使用鹼顯像液 進行顯像處理,將塗膜之未曝光部份溶解去除,隨後進行 後曝光使紅色畫素依所訂圖型進行配置而得畫素陣列。此 時所使用之光罩,除具有形成畫素用之圖型外,亦設有可 形成通孔或C字型凹孔之圖型。 隨後,使用分散有綠色或藍色顏料之各輻射敏感放射 線性組成物之液狀組成物,依前記相同方法對各液狀組成 物進行塗佈、預烘烤、曝光、顯像處理與後曝光處理,而 綠色畫素陣列與藍色畫素陣列於同一基板上依序形成,而 得到配置有紅色、綠色與藍色三原色之畫素陣列之T F T 型式液晶驅動用基板,且可製得具有通孔或C字型凹孔之 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) ' -41 - 訂 (請先閱讀背面之注意事項再填寫本頁) 508457 A7 __ _ B7___ 五、發明説明(39) 彩色液晶顯示裝置。 又,黑色基質可依前記形成畫素陣列之相同方法製得 〇 (請先閲讀背面之注意事項再填寫本頁} 形成著色層時所使用之T F T型式液晶驅動用基板中 的基板,例如可使用玻璃、矽、聚碳酸酯、聚酯、芳香族 聚醯胺、聚醯胺、亞胺、聚亞胺等。此些基板,依必要性 ,可使用矽偶合劑等進行藥品處理、電漿處理、離子電鍍 處理、濺鍍處理、氣相反應法、真空蒸鍍法等前處理。 將輻射敏感放射線性組成物之液狀組成物塗佈於基板 時,可適當地使用迴轉塗佈、流動塗佈、滾筒塗佈等方法 〇 塗佈之厚度,以乾燥後之膜厚爲0 · 1至1 0 μ m, 線 較佳爲〇· · 2至5 μ m更佳爲〇 · 2至3 · 0 # m爲宜。· 形成著色層時所使用之放射線,例如可使用可見光、 紫外線、遠紫外線、電子線、X線等,以波長1 9 0至 4 5 0 n m範圍之放射線爲佳。 放射線之曝光能量較佳爲1 〇至1 〇,〇 〇 〇 J /m 2 〇 經濟部智慧財產局員工消費合作社印製 又,前記鹼顯像液例如可使用碳酸鈉、碳酸氫鈉、氫 氧化鈉、氫氧化鉀、四甲基銨氫氧化物、二甲基乙醇胺、 膽驗、1,8 —氮雜二環—〔5 · 4 · 0〕一 7 -十一碳 少布、1,5 -氣雑一環一〔4 · 3 · 0〕— 5 -壬嫌等化 合物之水溶液。 前記鹼顯像液,例如可適當添加甲醇、乙醇等水溶性 本紙張尺度適用中®國家標準( CNS ) A4規格(210X 297公釐) ~ 508457 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明(40 ) 有機溶劑或界面活性劑等。又,鹼顯像後一般係進行水洗 步驟.。 鹼顯像法例如可使用噴灑顯像法、噴霧顯像法、浸漬 顯像法、攪拌顯像法等,顯像條件一般爲常溫下5至 3 0 0 秒。 依此方式所形成之彩色液晶顯示裝置中導通路之尺寸 ,於配合光罩所對應之尺寸,較佳爲1〇 以下,更佳 爲5 //m以下,最佳爲1至5#.m之範圍。 存在於依上述方法所形成著色層開口部之垂直截面形 狀係爲,底邊長度較上邊長度爲短,由上部圖型邊緣與下 部圖型邊緣所連接之直線與開口部上邊所形成之角度(以 下,此角度簡稱「錐角」)爲3 0至6 0 °所構成梯型形 狀。錐角較佳爲4 0至6 0 °,更佳爲4 0至5 0 ° 。 錐角低於3 0°時,導通I TO電極與著色層下方之 驅動用基板端子間之通孔會有阻塞情形,又,超過6 0 ° 時,著色層截面上部之圖型邊緣與下部之圖型邊緣所聯成 之直線與底邊所形成之角度將會有超過9 0 °之情形,而 此部份之I T 0電極會有斷線之情形,故爲不佳。 本發明之輻射敏感放射線性組成物,於形成於乾燥塗 膜經曝光後所形成之硬化膜的設置於T F T型式液晶驅動 用基板上著色層表面之例如I T 0電極等電極時,對正型 光阻之剝離液之膨脹率較佳爲5 %以下,更佳爲4 %以下 ,最佳爲3 . 5 %以下之組成物爲宜。 具有此一膨脹率之組成物,於著色層上形成電極(例 (請先閱讀背面之注意事項再填寫本頁) 訂 ( CNS ) Λ4^ ( 21〇X297^ ) 508457 A7 B7 五、發明説明(41 ) 如I τ 〇電極)所必須於導電層上形成圖型之步驟上,即 使將其浸漬於剝離正型光阻使用之剝離液中,亦具有可抑 制圖型化電極之著色層位置因剝離液所產生膨脹現象,故 該電極不會產生斷裂現象,而可製得一具有極高信賴性之 液晶顯示裝置。 此處所稱之膨脹率,係指由輻射敏感放射線性組成物 所形成之硬化被膜於6 0。(:下,於設置於T F T型式液晶 驅動用基板上著色層表面形成電極時所使用的正型光阻之 剝離液中,將該硬化被膜浸置於該剝離液中至飽和狀態爲 止時,以數學式Triazine-based compounds having a halomethyl group and the like. Among these triazine compounds, 2- [2- (3,4-dimethoxyphenyl) ethylidene] -4,6-bis (trichloromethyl) -s-triazine, and triazine compounds (1) is better. The foregoing triazine compound may be used alone or in combination of two or more kinds. The amount of the triazine compound used as the photopolymerization initiator is to add (C) the total of the polyfunctional monomer and the monofunctional monomer to 100. In the case of parts by weight, it is preferably 0. 0 to 1 to 40 parts by weight, more preferably 1 to 30 parts by weight, and most preferably 1 to 20 parts by weight. If the amount of the triazine compound is less than 0 · parts by weight, the hardening caused by exposure will be insufficient, so the colored layer will have a tendency to not easily obtain a pixel array according to the required arrangement, and more than 40 In the case of parts by weight, the formed colored layer tends to easily fall off the substrate during development. Additives (please read the precautions on the back before filling this page) Qin Ding. 1 # This paper size applies to China National Standard (CNS) A4 specifications (2iOX297 mm) -32- Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 508457 A7 B7 V. Explanation of the invention (30) The radiation-sensitive radiation composition for the color liquid crystal display device of the present invention, and various additives may be added if necessary. The foregoing additives have, for example, improved solubility of the radiation-sensitive radioactive composition in the alkali imaging solution, and can suppress the residual condition of undissolved matter after development, such as organic acids or organic aluminum compounds (however, the foregoing hydrogen supplier Except)). Organic 酴 The organic acid described above is preferably an aliphatic carboxylic acid or a phenyl-containing carboxylic acid having a molecular weight of 1,000 or more in the molecule. For example, pre-aliphatic carboxylic acids include formic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trimethylacetic acid, hexanoic acid, diethylacetic acid, and heptanoic acid; Acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, crotonic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid Acid, methylsuccinic acid, tetramethylsuccinic acid, cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, mesaconic acid and other dicarboxylic acids. Tricarboxylic acids such as glyceric acid, aconitic acid, and camphoric acid. The phenyl-containing carboxylic acid described above is, for example, a compound in which a carboxyl group is directly bonded to a phenyl group or a compound in which a carboxyl group is bonded to a phenyl group through a carbon chain. Examples of carboxylic acids containing phenyl groups are aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, xylic acid, and xylic acid; This paper is dimensioned to the Chinese National Standard (CNS) A4 (210X297 mm) I --------------- IT ------ (Please read the notes on the back before filling out this page) -33-508457 A7 B7 V. Description of Invention (31) Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid; trimellitic acid, pyromellitic acid, trimellitic acid, pyromellitic acid, etc. are trivalent. Acids, or compounds such as phenylacetic acid, hydrogenated atoric acid, hydrogenated cinnamic acid, picric acid, phenylsuccinic acid, atropic acid, cinnamic acid, endocinnamic acid, coumaric acid, and umbellic acid. Among these organic substances, from the viewpoints of alkali solubility, solvent solubility to be described later, prevention of contamination of substrates and light-shielding layers of unexposed portions, and prevention of film residue, the aliphatic carboxylic acid is preferably an aliphatic dicarboxylic acid, for example. In particular, malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, etc. are more preferred, and phenyl-containing carboxylic acids are preferably aromatic dicarboxylic acids. Phthalic acid is more preferred. The aforementioned organic acids may be used alone or in combination of two or more. The amount of the organic acid used is preferably 15% by weight or less, and more preferably 10% by weight or less for the entire radiation-sensitive radiation composition. When the amount of the organic acid used exceeds 15% by weight, the adhesion of the colored layer formed to the substrate tends to decrease. Organic amine compound The organic amine compound is preferably an aliphatic amine or a phenyl-containing amine having a molecular weight of 1 or more in the molecule and a molecular weight of 1,000 or less. Examples of the aforementioned aliphatic amines include mono-amines such as η-propylamine, i-propylamine, n-butylamine, i-butylamine, sec-butylamine, t-butylamine, η-pentylamine, n-hexylamine, and cyclohexylamine ( This paper size applies to China National Standard (CNS) A4 specification (210x297 mm) — ——i — #! (Please read the precautions on the back before filling this page) Order printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperatives -34 -508457 A7 B7 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the Invention (32) Cyclo) alkylamines; Methylethylamine, diethylamine, methyleta-propylamine, ethyleta-propylamine, diamine η-propylamine, di-i-propylamine, di-η-propylamine, di-η-butylamine, di-i-butylamine, di-sec-butylamine, di-t-butylamine and other di (cyclo) alkyl groups Amine; dimethylethylamine, methyldiethylamine, triethylamine, dimethyleta-propylamine, diethyleta-propylamine, methyldieta-propylamine, ethyldiamine i-propylamine, tri-amine η-propylamine, tri-i-propylamine, tri-η-butylamine, tri-l-butylamine, tri-sec-butylamine, tri- t Tri (cyclo) alkylamines such as monobutylamine; 2-aminoethanol, 3-amino-1 monopropanol, 1 monoamino-2 dipropanol, 4-monoamino-1 monobutanol, etc. (Cyclo) alkanolamines; di (cyclo) alkanolamines such as diethanolamine, di-n-propanolamine, di-i-propanolamine, di-n-butanolamine, di-i-butanolamine; three Tri (cyclo) alkanolamines such as ethanolamine, tri-n-propanolamine, tri-i-propanolamine, tri-n-butanolamine, and tri-l-butanolamine; 3-amine-1,2- Propylene glycol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, 4-amino-1,3-butanediol, 3-dimethylamino-1, 2 —Amine (cyclo) alkane such as propylene glycol, 3-diethylamino-1,2-propanediol, 2-methylamino-1,3-propanediol, 2-diethylamino-1,3-propanediol Diol / 3-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-monoaminobutyric acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid, etc. This paper size applies to Chinese National Standard (CNS) Α4 size (210X 297 mm) ~ -35- (Please Read the notes on the back and fill in this page) 508457 A7 B7 V. Description of the invention (33) 〇 (Please read the notes on the back before filling out this page) Also, amines containing phenyl groups, for example, the amine group is directly bonded to the phenyl group Compounds such as amine groups and phenyl groups bonded via a carbon chain. Phenyl-containing amines such as aniline, 0-methylaniline, m-methylaniline, P-methylaniline, P-ethylaniline, 1-naphthylaniline, 2-naphthylaniline, N, N-diamine Aromatic amines such as methylaniline, N, N-diethylaniline, p-methyl-N, N-dimethylaniline; o-aminobenzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl Amino benzyl alcohols such as alcohol, p-dimethylaminobenzyl alcohol, p-diethylaminobenzyl alcohol; o-aminophenol, m-aminophenol, p-aminophenol, p-dimethyl Aminophenols such as aminophenol, p-diethylaminophenol; m-aminobenzoic acid, p-aminobenzoic acid, p-di'methylaminobenzoic acid, p-diethylaminobenzene Aminobenzoic acid (derivatives) such as formic acid. Among these organic amine compounds printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, aliphatic amines are described in terms of solubility in solvents and prevention of contamination or film residues on the substrate or light-shielding layer of the unexposed section. For example, the use of mono (cyclo) alkanolamine and amine (cyclo) alkanoldiamine is preferred, especially 2-aminoethanol, 3-amino-1, 1-propanol, 5-amino-1, 1-pentyl Alcohol, 3-amino-1,2-propylene glycol, 2-amino-1,3-propanediol, 4-monoamino-1,2-butanediol, etc. are more preferred. Phenyl-containing amines such as aminophenol are preferred, and especially -aminophenylhydrazone, m-aminophenylhydrazone, p-aminophenylhydrazone and the like are more preferred. This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) -36-508457 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (34) The organic amine compound can be used alone or the 2 It is also possible to mix and use more than one kind. The amount of the organic amine compound used is preferably 5% by weight or less, and more preferably 10% by weight or less for the entire radiation-sensitive radiation composition. When the amount of the organic amine compound used exceeds 15% by weight, the adhesion between the formed colored layer and the substrate tends to decrease. Examples of additives other than the organic acids mentioned above include dispersion aids such as blue pigment derivatives such as copper phthalocyanine derivatives and yellow pigment derivatives; fillers such as glass and alumina; and polyethylene glycol and polyethylene glycol. Monoalkyl ethers, poly (fluoroalkyl acrylates) and other polymer compounds; anionic, cationic, and protonic surfactants; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri ( 2 —methoxyethoxy) silane, N — (2-aminoethyl) —3-aminopropyl • methyl • dimethoxysilane, N— (2-aminoethyl) -3—amine Propyltrimethylsilyl, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl • methyl • dimethoxy Silane, 2- (3,4-monoethoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropyl • methyl • dimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methyl Adhesion promoters such as propylene propyl propyltrimethoxysilane and 3-hydrothiopropyltrimethoxysilane; 2, 2 > —thiobis (4 a Methyl-6-t-butylphenyl), 2,6-di-t-butylphenol and other oxidation inhibitors; 丨 Order (Please read the precautions on the back before filling this page) This paper size applies to Chinese national standards (CNS) A4 specification (210X297 mm) -37- 508457 Α7 Β7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (35) 2— (3 —t-butyl-5—methyl-1 2— Via phenyl) -5-chlorobenzoxantriazole, alkoxybiphenols and other UV absorbers; sodium polyacrylate aggregation inhibitors; 1, 1-azobis (cyclohexane-1-carbon nitrile) ), 2-phenylazo-4 -methoxy-2,4-dimethylvaleronitrile and other thermal radical generators; and other additives. The radiation-sensitive radioactive composition of the present invention is an essential component of the former (A) colorant, (B) alkali-soluble resin, (C) polyfunctional monomer, and (D) photopolymerization initiator. It is preferably used in the form of a liquid composition with a solvent. The foregoing solvent is generally a substance that can disperse or dissolve the components (A) to (D) or additive components of the foregoing radiation-sensitive radioactive composition, or does not react with these components, and has moderate volatility, but can be Use appropriately. Such solvents are, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol η-propyl ether, ethylene glycol η n-butyl ether, and diethylene glycol monomethyl ether. , Diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl Ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol-η-butyl ether, dipropylene glycol monomethyl ether, dipropylene. The national paper standard applies to this paper ( CNS) Α4 specification (210 × 297 mm) (Please read the notes on the back before filling this page) -38- 508457 Α7 Β7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (36) Alcohol monoethyl ether (Poly) alkylene glycol monoalkyl ethers such as dipropylene glycol mono-n-propyl ether, propylene glycol mono-^-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, etc .; ethylene glycol monomethyl ether Ether ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether ethyl (Poly) alkanol monoalkyl ether acetates such as esters, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl Ethers such as methyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and other ketones; 2-hydroxypropionate methyl ester, 2 — Alkyl lactates such as ethyl hydroxypropionate; 2-hydroxy- 2-methyl propionate, 3- methoxy propionate, 3- methoxy propionate, 3- ethoxy Methyl propionate, '3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxy Butyl acetate, 3-methyl-1, 3-methoxybutyl propionate, ethyl acetate, mono-n-propyl acetate, mono-i-propyl acetate, mono-n-butyl acetate, mono-acetic acid 1 monobutyl ester, mono-n-pentyl formate, i-pentyl acetic acid, mono-n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, butyric acid η-butyl ester, methyl pyruvate, Other esters such as ethyl ketoacetate, mono-propyl pyruvate, methyl acetate, ethyl acetate, ethyl 2-oxobutyrate; aromatic hydrocarbons such as toluene and xylene; Ν— 甲Pyrrolidone, Ν, Ν—dimethylformamide, Ν, Ν This paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) I ------- order ~ ^ ---- ( Please read the precautions on the back before filling out this page) -39- 508457 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the Invention (37) Dimethylacetamide and other carboxylic acid amines. In the foregoing solvent, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol are used from the viewpoints of solubility, pigment dispersibility, and coatability. Monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl 2-hydroxypropionate, 3 —Ethyl methoxypropionate, 3-methyl ethoxypropionate, 3-ethyl ethoxypropionate, 3-methyl-3 methoxybutyric acid propionate, acetic acid η-butane Esters, i-butyl acetate, i-pentyl formate, i-pentyl acetate, i-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate Solvents such as esters and ethyl pyruvate are preferred. These solvents can be used alone or in combination of two or more. In addition, benzyl ether, dihexyl ether, acetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, benzene High boiling point solvents such as ethyl formate, diethyl oxalate, diethyl maleate, r-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate, etc. These high boiling point solvents can be used singly or in combination of two or more degrees. The amount of the solvent used is not particularly limited, but the coating properties and stability of the prepared radiation-sensitive radiation composition are not limited. From the viewpoint, the total concentration of the components other than the solvent of the composition is preferably 5 to 50% by weight, and most preferably 10 to 40% by weight. —; ----: 1 · — (Please read the notes on the back before filling out this page) The size of the paper is applicable to China National Standard (CNS) A4 (210X297 mm) -40-508457 Intellectual Property Bureau, Ministry of Economic Affairs Printed by employees' consumer cooperatives A7 B7 V. Description of the invention (38) Method of making the cover The radiation-sensitive radiation composition of the present invention is used to drive a liquid crystal display device in the form of a thin film transistor (τ FT) by etching printing. A coloring layer of a driving substrate (hereinafter referred to as "TFT-type driving substrate") provided on the substrate. The coloring layer referred to here refers to the meaning of using day pigment, black matrix, or both. Hereinafter, a method for forming a colored layer on a T F T liquid crystal driving substrate will be described. First, a light-shielding layer is formed on the surface of the TFT-type liquid crystal driving substrate or on the surface of the driving substrate on which a passivation film such as a silicon nitride film is formed. Then, a liquid composition such as a radiation-sensitive radiation composition in which a red pigment is dispersed is coated on the substrate, and then a pre-baking is performed to evaporate the solvent to form a coating film. Subsequently, this coating film is exposed through a photomask, and then an alkali developing solution is used for development processing. The unexposed part of the coating film is dissolved and removed, and then post-exposure is performed to arrange the red pixels according to the predetermined pattern And get a pixel array. In addition to the pattern used to form pixels, the photomask used at this time is also provided with a pattern capable of forming through holes or C-shaped recessed holes. Subsequently, each liquid composition is coated, pre-baked, exposed, developed, and post-exposed using the liquid composition of each radiation-sensitive radiation composition dispersed with green or blue pigments in the same manner as described above. Processing, and the green pixel array and the blue pixel array are sequentially formed on the same substrate to obtain a TFT-type liquid crystal driving substrate configured with pixel arrays of three primary colors of red, green, and blue. The paper size of the hole or C-shaped recessed hole is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) '-41-Order (please read the precautions on the back before filling this page) 508457 A7 __ _ B7___ V. DESCRIPTION OF THE INVENTION (39) A color liquid crystal display device. In addition, the black matrix can be prepared in the same way as the pixel array described above (please read the precautions on the back before filling in this page). The substrate of the TFT-type liquid crystal driving substrate used when forming the coloring layer can be used, for example, Glass, silicon, polycarbonate, polyester, aromatic polyamide, polyimide, imine, polyimide, etc. For these substrates, if necessary, silicon coupling agents can be used for pharmaceutical treatment and plasma treatment. , Ion plating treatment, sputtering treatment, vapor phase reaction method, vacuum evaporation method, etc. When coating the liquid composition of radiation-sensitive radiation composition on the substrate, spin coating, flow coating can be used appropriately Methods such as cloth, roller coating, etc. The thickness of the coating is such that the film thickness after drying is 0 · 1 to 10 μm, and the line is preferably 0 · · 2 to 5 μm, more preferably 0 · 2 to 3 · 0 # m is preferred. · The radiation used in forming the coloring layer can be visible light, ultraviolet light, far ultraviolet light, electron rays, X-rays, etc., preferably in the wavelength range of 190 to 450 nm. The exposure energy is preferably 10 to 100. 〇〇〇J / m 2 〇 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. For example, sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, and tetramethylammonium hydroxide can be used as the alkali developing solution. , Dimethylethanolamine, bile test, 1,8 —azabicyclo — [5 · 4 · 0]-7-eleven carbon less cloth, 1, 5-air tritium ring [4 · 3 · 0] — 5-Aqueous solution of compounds such as non-aqueous. The aforementioned alkali developing solution, such as methanol, ethanol, etc., can be appropriately added. Water-soluble grades of this paper are applicable. National Standard (CNS) A4 specification (210X 297 mm) ~ 508457 A7 B7 Ministry of Economic Affairs Printed by the Intellectual Property Bureau's Consumer Cooperatives 5. Description of the Invention (40) Organic solvents or surfactants, etc. In addition, the alkaline imaging method is generally followed by a water washing step. For the alkaline imaging method, for example, a spray imaging method or a spray imaging method can be used. Imaging method, immersion developing method, agitating developing method, etc., the developing conditions are generally 5 to 300 seconds at normal temperature. The size of the guide path in the color liquid crystal display device formed in this way corresponds to that of the photomask. The size is preferably 10 or less, and more preferably 5 // m or less, preferably in the range of 1 to 5 # .m. The vertical cross-sectional shape of the opening of the coloring layer formed according to the above method is such that the length of the bottom edge is shorter than the length of the upper edge, and The angle formed by the straight line connected to the lower edge of the figure and the upper edge of the opening (hereinafter, this angle is referred to as the "taper angle") is a ladder shape composed of 30 to 60 °. The taper angle is preferably 40 to 60 °, more preferably 40 to 50 °. When the taper angle is less than 30 °, the through hole between the conductive I TO electrode and the driving substrate terminal under the colored layer may be blocked, and when it exceeds 60 ° The angle formed by the straight line and the bottom edge formed by the upper and lower edge of the cross section of the colored layer will exceed 90 °, and the IT 0 electrode in this part will be broken. The situation is not good. When the radiation-sensitive radiation composition of the present invention is formed on a hardened film formed after exposure of a dry coating film and is disposed on an electrode such as an IT 0 electrode on the surface of a colored layer on a TFT-type liquid crystal driving substrate, the light is directed toward the light. The expansion rate of the resist peeling liquid is preferably 5% or less, more preferably 4% or less, and most preferably a composition of 3.5% or less. The composition with this expansion ratio forms an electrode on the colored layer (for example (please read the precautions on the back before filling this page). Order (CNS) Λ4 ^ (21〇X297 ^) 508457 A7 B7 V. Description of the invention ( 41) As in the step of forming a pattern on the conductive layer such as the I τ 〇 electrode, even if it is immersed in the stripping solution used for stripping the positive photoresist, it has the effect of suppressing the position of the colored layer of the patterned electrode. The swelling phenomenon produced by the stripping solution does not cause the electrode to break, and a liquid crystal display device with extremely high reliability can be manufactured. The expansion rate referred to here refers to the hardened coating formed by radiation-sensitive radioactive composition at 60. (: Below, in the stripping solution of a positive photoresist used when forming an electrode on the surface of a colored layer on a TFT-type liquid crystal driving substrate, the cured film is immersed in the stripping solution to a saturated state. Mathematical formula
Sw - (Vb-Va) xlOO/Va (其中,S w爲膨脹率(% ),V a爲硬化膜膨脹前 之體積,V b爲硬化膜膨脹後之體積) 所定義。 又,測定膨脹率S w時之曝光條件,於本發明之輻身寸 敏感放射線性組成物中,與採用以齡刻印刷法對了 p· T型 式液晶驅動用基板形成著色層之條件相同。 測定膨脹率S w所使用之剝離液,例如 ① 二甲基亞硕與N -甲基吡咯烷酮之混合物, ② 有機溶劑與二甲基亞碾之混合物, ®有機溶劑與胺化合物之混合物, ④有機溶劑與苯酚與烷基苯磺酸之混合物, 等。 剝離液之成分例如所使用之有機機溶劑,例女口 ^ 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) (請先閱讀背面之注意事項再填寫本頁) 訂 ♦線 經濟部智慧財產局員工消費合作社印製 -44 - 508457 A7 _____ B7____ 五、發明説明(42) 苯、甲苯、二甲苯、一氯苯、二氯苯等芳香族烴; (請先閲讀背面之注意事項再填寫本頁) 乙二醇一甲基醚、乙二醇一乙基醚、乙二醇——n — 丙基醚、乙二醇——η — 丁基醚、乙二醇二甲基醚、乙二 醇二乙基醚、乙二醇二一 η —丙基醚、乙二醇二一 η —丁 基酸、二乙二醇一甲基醚、二乙二醇一乙基醚、二乙二醇 一〜π —丙基醚、二乙二醇一一 η — 丁基醚、二乙二醇二 甲基醚、二乙二醇二乙基醚、二乙二醇二一 η —丙基醚、 二乙二醇二一 η — 丁基醚、三乙二醇一甲基醚、三乙二醇 一乙基醚 '三乙二醇——η —丙基醚、三乙二醇——η — 丁基醚、三乙二醇二甲基醚、三乙二醇二乙基醚、三乙二 醇二一 η —丙基醚、三乙二醇二一 η — 丁基醚等烷基醚類 全氯乙烯等鹵化烴; 等。 又,作爲剝離液成分使用之胺化合物,例如一乙醇胺 、二乙醇胺、三乙醇胺、三乙胺、三一 η — 丁胺、1,8 一一氮雜一 7 -十一碳烯等。 經濟部智慧財產局員工消費合作社印製 又,作爲剝離液成分使用之前記烷基苯磺酸例如,ρ —η —羊基苯礦酸、ρ — π —壬基苯礦酸、ρ — η -癸基 苯磺酸、ρ — η - ~f--院基苯磺酸、p-n -十二基苯磺 酸、ρ — η -十三院基苯擴酸、ρ - η -十四院基苯碼酸 等。 此些剝離液之具體例如,二甲基亞硕與Ν —甲基吡咯 烷酮之混合物(重量比二6 0 / 4 0 )、二乙醇一一 η - 本纸張尺度適用中國國家標準(CNS ) Α4規格(210Χ297公釐) " '~~ -45 - 508457 經濟部智慧財產局員工消費合作社印製 A7 B7五、發明説明(43 ) 丁基醚與二甲基亞硕之混合物(重量比二4 0/6 0 )、 二乙二醇——η - 丁基醚與一乙醇胺之混合物(重量比= 6 5/ 3 5 ) 、〇 -二氯苯與苯酚與烷基苯磺酸之混合物 (重量比=55/25/20或60/20/20)、全 氯乙烯與〇 -二氯苯與苯酚與烷基苯磺酸之混合物(重量 比=10/50/20/20)等。 測定膨脹率S w時,硬化膜受剝離液影響而膨脹到飽 和狀態之時間,依輻射敏感放射線性組成之組成內容、剝 離液之種類而有所不同,一般於6 〇 °C時,較佳爲5至 6 0分鐘左右。 由本發明之輻射敏感放射線性組成物所形成著色膜之 介電係數較佳爲1 0以下,更佳爲7以下,最佳爲5以下 。具有此介電係數之著色層的薄膜電晶體(T F T )形式 彩色液晶顯示裝置,其施加電壓部分並不會產生因未能正 確動作而造成顯示不佳等情形,而爲一具有高度信賴性之 顯示裝置。 又,由本發明之輻射敏感放射線性組成物所形成之著 色層的體積電阻係數,較佳爲1 0 1 2 Ω以上,更佳爲 1013Ω以上,最佳爲1〇14Ω以上。具有此一著色層之 薄Θ吴電晶體(T F Τ )形式彩色液晶顯不裝置,未施加電 壓之畫素並不會產生誤動而引起顯示不良,而爲一具有高 度信賴性之顯示裝置。 著色層之介電係數與體積電阻係數,例如可依下記$ 法測定。 ir.----r — I嘹! (請先閲讀背面之注意事項再填寫本頁) 、11 零線 本紙張尺度適用中國國家標準(CNS ) Α4規格(210X297公釐) -46 - 508457 經濟部智慧財產局員工消費合作社印製 A7 _ B7五、發明説明(44 ) 於被覆有鉻或鋁等金屬薄膜之基板上,依上記方法塗 佈輻射敏感放射線性組成物,並進行預烘烤而形成塗膜。 隨後,對塗膜進行全面曝光後,進行後烘烤以於基板上形 成著色層。 隨後,於所得之著色層上對適當大小之鋁等金屬薄膜 進行蒸鍍以形成上部電極。又,將未形成上部電極之一部 分著色層削除而露出下部金屬膜,作爲下部電極。對兩電 極間之靜電容量或電阻値進行測定,並由其數値分別計算 該著色層之介電係數與體積電阻係數。 由本發明輻射敏感放射線性組成物所形成之紅色、綠 色與藍色各畫素,其表面粗度係在50A以下,故具有極 優良之表面平滑性。 其中所稱「表面粗度」係爲依下式所定義之R a。 Ra s Ε ϊ 〇 ly |dx (5) 〔其中,R a爲畫素中心線之平均粗度(A ) ,L爲 測定之長度(m ) , y爲由畫素中心線至粗度曲線之距 離(A ),X爲所測定長度方向之位置座標〕 上式中所測定之長度L可採用適當之數値,較佳爲1 至15 μιη範圍之長度。 本發明中,畫素之粗度Ra較佳爲40Α以下,最佳 爲3 5 A以下。又本發明中畫素之表面粗度R a之下限値 ,係依輻射敏感放射線性組成物中(A )著色劑之濃度、 (請先閱讀背面之注意事項再填寫本頁) 本紙掁尺度適用中國國家標準(CNS ) A4規格(210X 297公釐) -47- 508457 經濟部智慧財產局員工消費合作社印製 A7 __ B7 __五、發明説明(45 ) 著色劑中顏料之粒徑、光聚合起始劑之量,(B )鹼可溶 性樹脂,(C )多官能性單體之使用量等因素而改變,故 不具有特定之範圍,但較佳約爲1 0 A左右。 本發明中,彩色薄膜用輻射敏感放射線性組成物所形 成之晝素之表面粗度R a於5 0 A以下時,可抑制(1 ) 畫素與液晶接觸面積過大時所產生之著色層之不純物向液 晶滲出,(2 )因畫素表面粗糙所引起之液晶定向不佳等 不良影響,而可製得不致產生燒附不佳或顯示斑點等顯示 不良的液晶顯示元件。 依此方式所製得之具有畫素及/或黑色基質之彩色液 晶顯示裝置,其可爲透過型或反射型,又本發明之彩色液 晶顯示裝置用輻射敏感放射線性組成物,對於薄膜電晶體 (TFT)形式之彩色印象管元件或彩色感應器極爲有用 〇 以下將以實施例對本發明之實施形態作更具體之說明 ,但本發明並不受下記實施粒所限定。 實施例 實施例1 將(A )作爲著色劑之C · I ·顏料紅1 7 7與 C · I ·顏料紅2 2 4以6 5 / 3 5 (重量比)混合物 1 0 0重量份,(B )鹼可溶性樹脂之甲基丙嫌酸/ n -苯基馬來酸酐縮亞胺/苄基甲基丙烯酸酯/乙二醇一甲基 丙烯酸酯/苯乙烯共聚物(共聚合重量比=1 ^ / 2 5 / 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) ~ ~ — :----l· — ·! (請先閱讀背面之注意事項再填寫本頁) 訂 ·線 508457 Α7 Β7 經濟部智慧財產局員工消費合作社印製 五、發明説明(46 ) 35/10/15, Mw二30, 〇〇〇, Mn= 1 0 , 0 0 0 ) ( C )多官能性單體之二季戊四醇基六丙 烯酸酯80重量份,(D)光聚合起始劑之2-苄基一2 〜二甲基胺基一 1 一(4 —嗎啉苯基)丁酮一 1 50重 纛份與作爲溶劑之丙二醇一甲基醚乙酸酯1,〇〇〇重量 份混合,以製作感放射線性組成物之液狀組成物(R 1 ) 〇 (畫素陣列之形成與評估) 使用此液狀組成物(R 1 )於T F T形式液晶驅動用 基板上之形成有氮化矽膜之基板表面,於旋轉塗佈後,於 9〇t之無塵烤箱中進行1 0分鐘之預烘烤,而製得膜厚 1 · 7 // m之塗膜。 隨後,將基板冷卻至室溫下,使用高壓水銀燈介由光 罩以含有波長365nm、4〇5nm與43 6 nm之紫 外線施以2,0 0 0 J /m 2曝光量進行曝光。再將基板浸 漬於2 3 °C下之含0 · 1重量%四甲基銨氫氧化物水溶液 中1分鐘以進行顯像處理,再以超純水洗淨、風乾後,於 2 2 0 °C之無塵烤箱中施以2 5分鐘之後烘烤處理,而於 基板上形成紅色條狀陣列。 將所得之畫素陣列使用光學顯微鏡觀察結果,並未發 現未曝光之基板上具有顯像殘留情形。且1 0 // m寬之通 孔亦爲開口狀態,又所得畫素與基板之密著性亦極佳。使 用S E Μ對存在於著色層之開口部的截面形狀進行觀察結 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準(CNS ) Α4規格(210X29?公釐) 508457 經濟部智慧財產局員工消費合作社印製 Μ ______Β7 _ 五、發明説明(47) 果,得知其錐角爲5 5 ° 。 又,使用觸針式表面粗度計(可耶魯公司製「阿爾法 斯5 〇 〇」),以測定長度爲1 〇 π) m下測定所得之.表面 粗糙度R a爲2 5 A,又,畫素表面以光學顯微鏡觀察結 果並未發現具有表面粗糙情形,畫素表面具有優良表面平 滑性。 此畫素陣列,浸漬於6 0 °C下之二甲基亞碾與N —甲 基吡咯烷酮之混合物(重量比=6 〇 / 4 0 )(東京應化 工業公可製)後,其浸漬1 0分鐘之膨脹濾S w爲3 . 4 %。 將依上記相同方法形成之畫素陣列,與具有以濺鍍法 形成I T 0電極之基板貼合而得的面板上,施以電流後, 並未發現顯示不佳而具有良好的顯示特性。 實施例2 將(A )作爲著色劑之C · I .顏料紅.1 7 7與 C · I ·顏料紅2 2 4以6 5 / 3 5 (重量比)混合物 1 0 0重量份,(B )驗可溶性樹脂之甲基丙烯酸/N — 苯基馬來酸酐縮亞胺/苄基甲基丙烯酸酯/乙二醇一甲基 丙烯酸酯/苯乙烯共聚物(共聚合重量比=1 5/2 5/ 35/10/15, Mw二30, 000, Mn= 10, 000)(C)多官能性單體之二季戊四醇基六丙 烯酸酯80重量份,(D)光聚合起始劑之2 -甲基一 1 一 〔4 —(甲基硫基)苯基〕一 2 —嗎啉丙酮一 1 2〇 — l·.----K丨.^曹-----,— I、玎!———费 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準(CNS ) A4規格(210 X 297公釐) -50- 508457 經濟部智慧財產局員工消費合作社印製 A7 B7五、發明説明(48 ) 重量份與增感劑之4, 4 > —雙(二乙胺)二苯甲酮15 重量份,與作爲溶劑之丙二醇一甲基醚乙酸酯1,00〇 重量份混合,以製作感放射線性組成物之液狀組成物( R 2 )。 (畫素陣列之形成與評估) 除將液狀組成物(R 1 )以液狀組合物(R 2 )替代 外,其他皆依實施例1相同方法,於基板上形成紅色條狀 畫素陣列,並進行評估。 將所得之畫素陣列使用光學顯微鏡觀察結果,並未發 現未曝光之基板上具有顯像殘留情形。且1 0 V m寬、5 # m寬之通孔亦爲開口狀態,又所得畫素與基板之密著性 .亦極佳。使用S E Μ對存在於著色層之開口部的截面形狀 進行觀察結果,得知其錐角爲4 0 ° 。 又,依實施例1相同方法測得表面粗糙度R a爲3〇 A,又,畫素表面以光學顯微鏡觀察結果並未發現具有表 面粗糙情形,畫素表面具有優良表面平滑性。 此畫素陣列,浸漬於6 0 t下之二甲基亞硕與N —甲 基吡咯烷酮之混合物(重量比=6 0 / 4 0 )(東京應化 工業公司製)後,其浸漬1 0分鐘之膨脹濾S w爲2 . 9 %。 將依上記相同方法形成之畫素陣列,與具有以濺鍍法 ~ 形成I T 0電極之基板貼合而得的面板上,施以電流後, 並未發現顯示不佳而具有良好的顯示特性。 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) ~-51 - ― ^^衣.^ 訂 . (請先閲讀背面之注意事項再填寫本頁) 川8457 A7 B7 五、 發明説明(49 (請先閱讀背面之注意事項再填寫本頁) 將(A)作爲著色劑之C · I ·顏料藍15 : 6與 C · I ·顏料紫23以95/5 (重量比)混合物55重 最份,(B )鹼可溶性樹脂之甲基丙嫌酸/ 2 -羥乙基( 甲基)丙烯酸酯/苄基甲基丙烯酸酯共聚物(共聚合重量 比=15/15/70,Mw=25,〇 0 0 , Μ π = 1〇, 000) 75重量份(C)多官能性單體之二季戊 _醇基六丙烯酸酯7 5重量份,(D )光聚合起始劑之2 ’ —雙(2 —氯苯基)—4,4' 5, 5,一四苯 墓〜1,2 ' -聯二咪唑6重量份與氫硫基系氫供應體之 2〜氫硫基苯駢噻唑3重量份,與作爲溶劑之丙二醇一甲 _醚乙酸酯7 0 0重量份與環己酮3 0 0重量份混合,以 _作感放射線性組成物之液狀組成物(B 1 )。 (畫素陣列之形成與評估) 經濟部智慧財產局員工消費合作社印製 除將液狀組成物(R 1 )以液狀組合物(B 1 )替代 外,其他皆依實施例1相同方法,於基板上形成藍色條狀 畫素陣列,並進行評估。 將所得之畫素陣列使用光學顯微鏡觀察結果,並未發 現未曝光之基板上具有顯像殘留情形。且1 〇 A m寬之通 孔亦爲開口狀態,又所得畫素與基板之密著性亦極佳。使 -用S EM對存在於著色層之開口部的截面形狀進行觀察結 果,得知其錐角爲5 0 ° 。 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 508457 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明(50 ) 又’依實施例1相同方法測得表面粗糙度R a爲3 0 A’並未發現具有表面粗糙情形,晝素表面具有優良表面 平滑性。 此畫素陣列,浸漬於6 〇它下之二甲基亞硕與N 一甲 基_略院酮之混合物(重量比=6 〇 / 4 〇 )(東京應化 工業公司製)後,其浸漬1 〇分鐘之膨脹濾s w爲2 · 7 % ° 將依上記相同方法形成之畫素陣列,與具有以濺鍍法 形成I T 0電極之基板貼合而得的面板上,施以電流後, 並来發現顯示不佳,而具有良好的顯示特性。 實施例4 將(A )作爲著色劑之C · I ·顏料紫3 6與 C · I .顏料黃1 5以6 5 / 3 5 (重量比)混合物 100重量份,(B)鹼可溶性樹脂之甲基丙烯酸/2-羥乙S (甲基)丙烯酸酯/苄基甲基丙烯酸酯共聚物(共 聚合重量比=15/15/70, Mw二25, 000, Mn=l〇,000) 75重量份(C)多官能性單體之 二季戊四醇基六丙烯酸酯75重量份,(D)光聚合起始 劑之三嗪系化合物(1 ) 1 〇重量份,與作爲溶劑之丙二 醇一甲基醚乙酸酯7 0 0重量份與環己酮3 0 0重量份混 合,以製作感放射線性組成物之液狀組成物(G 1 )。 (畫素陣列之形成與評估) (請先閲讀背面之注意事項再填寫本頁) 本紙浪尺度適用中國國家標準(CNS ) A4規格(210X 297公釐) -53- 508457 經濟部智慧財產局員工消費合作社印製 A7 _____B7五、發明説明(51 ) 除將液狀組成物(R 1 )以液狀組合物(G 1 )替代 外,其他皆依實施例1 .相同方法,於基板上形成綠色條狀 畫素陣列,並進行評估。 將所得之畫素陣列使用光學顯微鏡觀察結果,並未發 現未曝光之基板上具有顯像殘留情形。且1 〇 // m寬之通 孔亦爲開口狀態,又所得畫素與基板之密著性亦極佳。使 用S E Μ對存在於著色層之開口部的截面形狀進行觀察結 果,得知其錐角爲5 0 ° 。 又,依實施例1相同方法測得表面粗糙度R a爲3 0 A,並未發現具有表面粗糙情形,畫素表面具有優良表面 平滑性。 此畫素陣列,浸漬於6 0°C下之二甲基亞硕與N —甲 基吡咯烷酮之混合物(重量比=6 0 / 4 0 )(東京應化 工業公司製)後,其浸漬1 〇分鐘之膨脹濾S w爲3 · 1 將依上記相同方法形成之畫素陣列,與具有以濺鍍法 形成I T 0電極之基板貼合而得的面板上,施以電流後, 並未發現顯示不佳,而具有良好的顯示特性。 實施例5 於實施例1中,除再加入多官能性丙烯酸酯(1 ) 1 0重量份以外,其他皆依實施例1相同方法,製作輻射 敏感放射線性組成物之液狀組成物(r 3 )。 I--------^^衣-- (請先閱讀背面之注意事項再填寫本頁)Sw-(Vb-Va) x 100 / Va (where S w is the expansion ratio (%), Va is the volume before the expansion of the cured film, and V b is the volume after the expansion of the cured film). The exposure conditions at the time of measuring the swelling coefficient S w are the same as those in the radiation sensitive radiation composition of the present invention, in which the colored layer is formed on the p · T type liquid crystal driving substrate by the age printing method. The stripping liquid used to measure the swelling ratio S w, for example ① a mixture of dimethylasco and N-methylpyrrolidone, ② a mixture of organic solvent and dimethylmethylene, ® a mixture of organic solvent and amine compound, ④ organic Solvents and mixtures of phenol and alkylbenzene sulfonic acids, etc. The composition of the peeling liquid is, for example, the organic organic solvent used, such as the female mouth ^ This paper size is applicable to China National Standard (CNS) A4 size (210X297 mm) (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperatives of the Ministry of Intellectual Property Bureau -44-508457 A7 _____ B7____ V. Description of the Invention (42) Aromatic hydrocarbons such as benzene, toluene, xylene, monochlorobenzene, dichlorobenzene; (Please read the notes on the back first (Fill in this page again) Ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, Ethylene glycol-n-propyl ether, Ethylene glycol-η-butyl ether, Ethylene glycol dimethyl ether , Ethylene glycol diethyl ether, ethylene glycol di-n-propyl ether, ethylene glycol di-n-butyl acid, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, two Ethylene glycol mono-π-propyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-propylene Ether, diethylene glycol di-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether 'triethylene glycol-η- Ether, triethylene glycol——η-butyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol di-n-propyl ether, triethylene glycol di Mono-ether ethers such as alkyl ethers such as perchloroethylene; halogenated hydrocarbons; etc. In addition, the amine compound used as a component of the peeling liquid includes, for example, monoethanolamine, diethanolamine, triethanolamine, triethylamine, trin-n-butylamine, 1,8-azaaza-7-undecene, and the like. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, and used as the stripping liquid component before the alkylbenzene sulfonic acid. For example, ρ — η — sheep benzene mineral acid, ρ — π — nonylbenzene mineral acid, ρ — η- Decylbenzenesulfonic acid, ρ — η-~ f--Rhobic benzenesulfonic acid, pn -Dodecylbenzenesulfonic acid, ρ — η -Tridecylbenzene sulfonic acid, ρ-η -Tetradecylbenzene Code acid and so on. Specific examples of these stripping liquids are a mixture of dimethyl asus and N-methylpyrrolidone (weight ratio of 2 60/4 0), diethanol-1 η-this paper size applies Chinese National Standard (CNS) Α4 Specifications (210 × 297 mm) " '~~ -45-508457 Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs V. Description of the invention (43) Mixture of butyl ether and dimethylasyl (weight ratio 2 to 4) 0/6 0), diethylene glycol——a mixture of η-butyl ether and monoethanolamine (weight ratio = 6 5/3 5), a mixture of 0-dichlorobenzene and phenol and alkylbenzenesulfonic acid (weight Ratio = 55/25/20 or 60/20/20), a mixture of perchloroethylene and 0-dichlorobenzene with phenol and alkylbenzenesulfonic acid (weight ratio = 10/50/20/20), etc. When measuring the swelling ratio S w, the time for the cured film to expand to the saturated state under the influence of the stripping solution varies depending on the composition of the radiation-sensitive radiation composition and the type of the stripping solution. Generally, it is better at 60 ° C. It is about 5 to 60 minutes. The dielectric constant of the colored film formed by the radiation-sensitive radiation composition of the present invention is preferably 10 or less, more preferably 7 or less, and most preferably 5 or less. A thin-film transistor (TFT) type color liquid crystal display device having a coloring layer having this dielectric coefficient does not cause a poor display due to failure to operate under a voltage application portion, and is a highly reliable device. Display device. The volume resistivity of the colored layer formed from the radiation-sensitive radiation composition of the present invention is preferably 10 1 2 Ω or more, more preferably 1013 Ω or more, and most preferably 1014 Ω or more. The thin Θ Wutong crystal (T F T) type color liquid crystal display device having such a coloring layer does not cause a pixel to malfunction due to a pixel to which a voltage is not applied and causes poor display, and is a highly reliable display device. The dielectric constant and volume resistivity of the colored layer can be measured, for example, by the following method. ir .---- r — I 嘹! (Please read the precautions on the back before filling this page). 11 The paper size of the zero-line paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -46-508457 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 _ B7 V. Description of the invention (44) The radiation-sensitive radiation composition is coated on the substrate coated with a metal film such as chromium or aluminum according to the method described above, and pre-baking is performed to form a coating film. Subsequently, after the coating film is fully exposed, post-baking is performed to form a colored layer on the substrate. Subsequently, a metal film such as aluminum of a suitable size is deposited on the obtained colored layer to form an upper electrode. In addition, a part of the colored layer where the upper electrode was not formed was removed to expose the lower metal film as a lower electrode. The capacitance or resistance 値 between the two electrodes is measured, and the dielectric constant and volume resistivity of the colored layer are calculated from the numbers 値. The red, green, and blue pixels formed by the radiation-sensitive radiation composition of the present invention have a surface roughness of less than 50A, and therefore have excellent surface smoothness. The "surface roughness" referred to herein is R a defined by the following formula. Ra s ϊ 〇 ly | dx (5) [where Ra is the average thickness (A) of the pixel centerline, L is the measured length (m), and y is the distance from the pixel centerline to the roughness curve The distance (A), X is the position coordinate of the measured length direction] The length L measured in the above formula can be an appropriate number, preferably a length in the range of 1 to 15 μm. In the present invention, the roughness Ra of the pixel is preferably 40 A or less, and most preferably 3 5 A or less. The lower limit of the surface roughness R a of the pixels in the present invention depends on the concentration of the (A) colorant in the radiation-sensitive radioactive composition. (Please read the precautions on the back before filling this page.) China National Standard (CNS) A4 specification (210X 297 mm) -47- 508457 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 __ B7 __ V. Description of the invention (45) Particle size and photopolymerization of pigments in colorants The amount of the initiator, the amount of the (B) alkali-soluble resin, and the amount of the (C) polyfunctional monomer used vary, and therefore do not have a specific range, but preferably about 10 A. In the present invention, when the surface roughness R a of the daytime element formed by the radiation-sensitive radiation composition for a color film is less than 50 A, it is possible to suppress (1) the coloring layer generated when the contact area between the pixel and the liquid crystal is too large. Impurities ooze out to the liquid crystal, and (2) a bad liquid crystal orientation caused by rough pixel surface and other bad effects, and a liquid crystal display element that does not cause poor display such as poor adhesion or display spots can be produced. The color liquid crystal display device with pixels and / or black matrix prepared in this way may be a transmission type or a reflection type, and the radiation sensitive radiation composition for the color liquid crystal display device of the present invention is suitable for a thin film transistor. A color impression tube element or a color sensor in the form of a (TFT) is extremely useful. The embodiments of the present invention will be described in more detail with reference to the following examples, but the present invention is not limited by the following embodiments. EXAMPLES Example 1 (A) C · I · Pigment Red 1 7 7 and C · I · Pigment Red 2 2 4 as a colorant were mixed in a proportion of 6 5/3 5 (weight ratio) of 100 parts by weight, ( B) Methylpropionic acid / n-phenylmaleic anhydride imine / benzyl methacrylate / ethylene glycol monomethacrylate / styrene copolymer (copolymerization weight ratio = 1) of alkali-soluble resin ^ / 2 5 / This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) ~ ~ —: ---- l · — ·! (Please read the precautions on the back before filling out this page) Order · Line 508457 Α7 Β7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (46) 35/10/15, Mw 30, 00, Mn = 1 0, 0 0 0) (C) Multifunctionality 80 parts by weight of dipentaerythritol hexaacrylate of monomer, (D) 2-benzyl-2 to dimethylamino-1 of 1 (4-morpholinephenyl) butanone-1 50 A part by weight was mixed with 1,000 parts by weight of propylene glycol monomethyl ether acetate as a solvent to produce a liquid composition (R 1) of a radiation-sensitive composition. (Pixel array shape And evaluation) Using this liquid composition (R 1) on the surface of a substrate on which a silicon nitride film is formed on a substrate for driving a TFT-type liquid crystal, spin coating was performed in a 90 t dustless oven. Pre-baking in minutes, to obtain a coating film with a film thickness of 1 · 7 // m. Subsequently, the substrate was cooled to room temperature, and exposed using a high-pressure mercury lamp through a reticle at an exposure amount of 2,000 J / m2 with ultraviolet rays containing wavelengths of 365 nm, 4.05 nm, and 43 6 nm. The substrate was immersed in a 0.1% by weight tetramethylammonium hydroxide aqueous solution at 2 3 ° C for 1 minute to perform a development process, and then washed with ultrapure water and air-dried at 2 2 0 ° The baking process was performed in the dust-free oven of C for 25 minutes, and a red stripe array was formed on the substrate. The obtained pixel array was observed with an optical microscope, and no imaging residue was found on the unexposed substrate. And the through hole with a width of 10m is also open, and the adhesion between the obtained pixel and the substrate is also excellent. Use SE Μ to observe the cross-sectional shape of the openings in the colored layer (please read the precautions on the back before filling this page) This paper size applies the Chinese National Standard (CNS) Α4 size (210X29? Mm) 508457 Economy Printed by the Consumer Cooperatives of the Ministry of Intellectual Property Bureau ______B7 _ V. Description of the invention (47) As a result, the cone angle is 55 °. The surface roughness R a was 2 5 A using a stylus-type surface roughness meter ("Alfas 5000" manufactured by Yale Corporation) at a measurement length of 10 m). Observation of the pixel surface with an optical microscope showed no surface roughness, and the pixel surface had excellent surface smoothness. This pixel array is immersed in a mixture of dimethylimine and N-methylpyrrolidone (weight ratio = 60/40) at 60 ° C (made by Tokyo Yingka Kogyo Co., Ltd.). The swelling filter S w at 0 minutes was 3.4%. The pixel array formed in the same manner as above was bonded to a panel having a substrate having I T 0 electrodes formed by sputtering. After applying a current, no poor display was found and the display characteristics were good. Example 2 C · I.Pigment Red with (A) as a colorant. 1 7 7 and C · I · Pigment Red 2 2 4 were mixed with 6 5/3 5 (weight ratio) 100 parts by weight, (B ) Test soluble resin of methacrylic acid / N — phenylmaleic anhydride imine / benzyl methacrylate / ethylene glycol monomethacrylate / styrene copolymer (copolymerization weight ratio = 1 5/2 5 / 35/10/15, Mw 230,000, Mn = 10,000) (C) 80 parts by weight of dipentaerythritol hexaacrylate of the polyfunctional monomer, (D) 2 of the photopolymerization initiator- Methyl 1-[4- (methylthio) phenyl]-2 -morpholine acetone 1 2 0-l ..---- K 丨. ^ Cao -----, — I, 玎!! ——— Fees (Please read the notes on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -50- 508457 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (48) parts by weight and 4, 4 as a sensitizer >-15 parts by weight of bis (diethylamine) benzophenone, and propylene glycol monomethyl ether acetate 1 as a solvent, 00 parts by weight are mixed to prepare a liquid composition (R 2) of a radiation-sensitive composition. (Formation and Evaluation of Pixel Array) Except replacing the liquid composition (R 1) with the liquid composition (R 2), the same method as in Example 1 was used to form a red stripe pixel array on the substrate. And evaluate. The obtained pixel array was observed with an optical microscope, and no imaging residue was found on the unexposed substrate. And 10 V m wide and 5 # m wide through holes are also open, and the adhesion between the obtained pixels and the substrate is also excellent. As a result of observing the cross-sectional shape of the opening portion of the colored layer using S EM, it was found that the cone angle was 40 °. In addition, the surface roughness Ra was measured in the same manner as in Example 1 to be 30 A. Moreover, the surface of the pixel was not observed to have a rough surface by an optical microscope, and the surface of the pixel had excellent surface smoothness. This pixel array was immersed in a mixture (weight ratio = 60/40) of dimethyl arsenol and N-methylpyrrolidone (weight ratio = 60/40) (made by Tokyo Yingka Kogyo Co., Ltd.) at 60 t, and then immersed for 10 minutes. The swelling filter S w was 2.9%. The pixel array formed by the same method as described above was bonded to a panel having a substrate formed by sputtering to form an I T 0 electrode. After applying a current, no poor display was found and the display characteristics were good. This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) ~ -51-^^ 衣. ^ Order. (Please read the notes on the back before filling this page) Chuan 8457 A7 B7 V. Description of the invention (49 (Please read the precautions on the back before filling out this page) Mixing C · I · Pigment Blue 15: 6 with C · I · Pigment Violet at 95/5 (weight ratio) as a colorant 55 Most parts by weight, (B) Methacrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl methacrylate copolymer of alkali-soluble resin (copolymerization weight ratio = 15/15/70, Mw = 25, 0 0 0, Μ π = 10,000) 75 parts by weight (C) 75 parts by weight of dipentaminyl alcohol hexaacrylate of the polyfunctional monomer, (D) 2 of the photopolymerization initiator '—Bis (2-chlorophenyl) -4,4' 5,5,4-tetrabenzene tomb ~ 1,2,2'-biimidazole 6 parts by weight with hydrogen sulfur based hydrogen supplier 2 ~ hydrothiobenzene 3 parts by weight of panthiazole, solvated with propylene glycol monomethyl ether ether 700 parts by weight and 300 parts by weight of cyclohexanone, and used as a liquid composition (B 1 ). (Pixel Array Formation and Evaluation) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, except that the liquid composition (R 1) is replaced by the liquid composition (B 1). Color stripe pixel arrays were evaluated. The obtained pixel arrays were observed using an optical microscope, and no imaging residue was found on the unexposed substrate. And the through holes with a width of 10 A m were also open. The adhesion between the obtained pixel and the substrate is also excellent. Using S EM to observe the cross-sectional shape of the opening in the colored layer, it is found that the cone angle is 50 °. This paper scale is applicable to China National Standard (CNS) A4 specification (210X297 mm) 508457 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (50) The surface roughness R a measured by the same method as in Example 1 was 3 0 A 'has not been found to have a rough surface, and the surface of the day prime has excellent surface smoothness. This pixel array is immersed in a mixture of dimethylarsone and N-methyl- slightly ketone ketone (weight ratio = 6 〇 / 4 〇) (manufactured by Tokyo Yinghua Chemical Industry Co., Ltd.), the swelling filter sw for a 10-minute immersion was 2.7% ° and the pixel array to be formed in the same manner as described above and the substrate having the IT 0 electrode formed by the sputtering method After applying the electric current to the bonded panel, it was found that the display was not good, and it had good display characteristics. Example 4 C · I · Pigment Violet 3 6 and C · I using (A) as a colorant .Pigment Yellow 1 5 at 6 5/3 5 (weight ratio) 100 parts by weight of mixture, (B) Alkali soluble resin methacrylic acid / 2-hydroxyethyl S (meth) acrylate / benzyl methacrylate copolymerization (Copolymerization weight ratio = 15/15/70, Mw 25,000, Mn = 10,000) 75 parts by weight (C) 75 parts by weight of dipentaerythritol hexaacrylate of polyfunctional monomer, (D ) 10 parts by weight of the triazine-based compound (1) of the photopolymerization initiator is mixed with 700 parts by weight of propylene glycol monomethyl ether acetate as a solvent and 300 parts by weight of cyclohexanone to produce a feeling. Liquid composition (G 1) of the radiation composition. (Formation and Evaluation of Pixel Array) (Please read the notes on the back before filling out this page) This paper applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) -53- 508457 Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the consumer cooperative A7 _____B7 V. Description of the invention (51) Except replacing the liquid composition (R 1) with the liquid composition (G 1), the rest are in accordance with Example 1. The same method is used to form a green color on the substrate An array of stripe pixels and evaluated. The obtained pixel array was observed with an optical microscope, and no imaging residue was found on the unexposed substrate. And the through hole with a width of 〇 // m is also in an open state, and the adhesion between the obtained pixel and the substrate is also excellent. The observation result of the cross-sectional shape of the opening portion of the colored layer using S EM revealed that the cone angle was 50 °. In addition, the surface roughness Ra was measured in the same manner as in Example 1 to be 30 A. No surface roughness was found, and the pixel surface had excellent surface smoothness. This pixel array was immersed in a mixture (weight ratio = 60/40) of dimethyl arsenol and N-methylpyrrolidone (weight ratio = 60/40) (made by Tokyo Yingka Kogyo Co., Ltd.) at 60 ° C, and then immersed for 1 〇. The expansion filter S w for 3 minutes is 3 · 1 The pixel array formed in the same manner as above is bonded to a panel having a substrate with IT 0 electrodes formed by sputtering. After applying a current, no display is found. Poor, but with good display characteristics. Example 5 In Example 1, except that the polyfunctional acrylate (1) was added in an amount of 10 parts by weight, the liquid composition of the radiation-sensitive radiation composition (r 3) was prepared in the same manner as in Example 1. ). I -------- ^^ 衣-(Please read the precautions on the back before filling in this page)
、1T 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -54 - 508457 A7 B7 五、發明説明(52 ) (畫素陣列之形成與評估) 除將液狀組成物(R 1 )以液狀組合物(r 3 )替代 外,其他皆依實施例1相同方法,於基板上形成紅色條狀 畫素陣列,並進行評估。 將所得之畫素陣列使用光學顯微鏡觀察結果,並未發 現未曝光之基板上具有顯像殘留情形。且5 # m寬之通孔 亦爲開口狀態,又所得畫素與基板之密著性亦極佳。 實施例Θ 於實施例3中,除再加入多官能性丙烯酸酯(2 ) 1 0重量份以外,其他皆依實施例3相同方法,製作輻射 敏感放射線性組成物之液狀組成物(B 2 )。 (畫素陣列之形成與評估) 除將液狀組成物(B 1 )以液狀組合物(b 2 )替代 外,其他皆依實施例3相同方法,於基板上形成藍色條狀 畫素陣列,並進行評估。 將所得之畫素陣列使用光學顯微鏡觀察結果,並未發 現未曝光之基板上具有顯像殘留情形。且5 # m寬之通孔 亦爲開口狀態,又所得畫素與基板之密著性亦極佳。 實施例7 於實施例4中,除再加入多官能性丙烯酸酯(丄) 1〇重量份以外,其他皆依實施例4相同方法,製作幅射 本紙張尺度適用中國國家標準(CNS ) A4規格(210X 297公釐) '-— -55 - (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 508457 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明(53 ) 敏感放射線性組成物之液狀組成物(G 2 )。 (畫素陣列之形成與評估) 除將液狀組成物(G 1 )以液狀組合物(G 2 )替代 外,其他皆依實施例3相同方法,於基板上形成藍色條狀 畫素陣列,並進行評估。 將所得之畫素陣列使用光學顯微鏡觀察結果,並未發 現未曝光之基板上具有顯像殘留情形。且5 a m寬之通孔 亦爲開口狀態,又所得畫素與基板之密著性亦極佳。 實施例8 將(A )作爲著色劑之C · I ·顏料紅1 7 7與 C · I ·顏料紅2 2 4以6 5 / 3 5 (重量比)混合物 5 0重量份,(B )鹼可溶性樹脂之甲基丙烯酸/ N -苯 基馬來酸酐縮亞胺/苄基甲基丙烯酸酯/乙二醇一甲基丙 烯酸酯/苯乙烯共聚物(共聚合重量比=1 5/2 5/ 35/10/15, Mw=30, 000, Mn= 10,000) 140重量份(C)多官能性單體之二季 戊四醇基六丙烯酸酯1 6 0重量份,(D )光聚合起始劑 之2 —苄基一 2 —二甲基胺基一 1 一(4 一嗎啉苯基)丁 烷一 1 一酮5 0重量份,與作爲溶劑之丙二醇一甲基醚乙 酸酯1,0 0 0重量份混合,以製作感放射線性組成物之 液狀組成物(R 4 )。 隨後,將此液狀組成物(R 4 )依下記要點測定著色 —---------- (請先閲讀背面之注意事項再填寫本頁) 訂 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -56- 508457 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明(54 ) 膜所形成之介電係數與體積電阻係數,並一倂對以其他方 法形成畫素陣列之顯示性能進行評估。 (介電係數之測定) 將液狀組成物(R 4 )以旋轉塗佈方式塗覆於被覆有 鉻之鋁基板(直徑1 0 〇 · 2 m m、鉻膜厚〇.525 # m ,旭玻璃股份有限公司製)後,於9 0 °C之無塵烤箱 中進行1 0分鐘之預烘烤,使其形成1 · 5 // m之塗膜。 隨後,將基板冷卻至室溫下,使用高壓水銀燈對塗膜 全面以含有波長365nm、405nm與436nm之 紫外線施以2,0 0 0 J /m 2曝光量進行曝光。再將基板 於2 2 0 °C之無塵烤箱中施以2 5分鐘之後烘烤處理,而 於基板上形成著色膜。 其次,使用真空蒸鍍裝置(商品名PEC—A2,島 津製作所股份有限公司製)於所得之著色膜上形成直徑 1 m m之圓形鋁電極。又,於未形成鋁電極之部分削取 5mm平方之薄膜,使鉻表面露出。 再於所露出之鉻表面上,使用銀糊料將銅線黏附其上 ,並裝置靜電容量測定計(商品名L C R計4 2 8 4 A, HEWLETT PACKARD公司製),由其値算出介電係數。其 結果得知,著色層之介電係數爲4 . 3。 (體積電阻係數之測定) 於上記製得之覆有電極的著色膜裝設微量電流測定計 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) ~ -57- I--------衣-- (請先閲讀背面之注意事項再填寫本頁) 、言· ,線 508457 經濟部智慧財產局員工消費合作社印製 A7 B7五、發明説明(55 ) (商品名 P A 測定計 4 1 4 0 B,HEWLETT PACKARD 公 司製),測定施加有0 · 1 V直流電流時之電流値,並由 其値算出體積電阻係數。其結果得知,著色層之體積電阻 係數爲2·8xl014Qcm。 (畫素陣列之形成與顯示性能之評估) 將液狀組成物(R 4 )以旋轉塗佈方式塗覆於表面形 成有氮化矽膜之T F T形式液晶驅動用基板的表面後,於 9 0 t之無塵烤箱中進行1 0分鐘之預烘烤,使其形成 3 · 0 β m之塗膜。 隨後,將基板冷卻至室溫下,使用高壓水銀燈介由光 罩對塗膜全面以含有波長3 6 5 nm、4 0 5 nm與 4 3 6 n m之紫外線施以2,0 0 0 J / m 2曝光量進行曝 光。再將基板浸漬於2 3 °C下之含0 · 1重量%四甲基銨 氫氧化物水溶液中1分鐘以進行顯像處理,再以超純水洗 淨、風乾後,再將基板於2 2 0 °C之無塵烤箱中施以2 5 分鐘之後烘烤處理,而於基板上形成具有紅色畫素之晝素 陣列。 將依上記相同方法形成之基板,與具有以濺鍍法形成 I 丁 0電極之基板貼合而得的液晶顯示裝置,經進行操作 後,並未發現顯示不佳之情形。 實施例9 將(A )作爲著色劑之C · I .顏料紅1 7 7與 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) (請先閱讀背面之注意事項再填寫本頁) -58- 508457 A7 B7 五、發明説明(56 ) (請先閲讀背面之注意事項再填寫本頁) C · I .顏料紅2 2 4以6 5 / 3 5 (重量比)混合物 5〇重量份,(B )鹼可溶性樹脂之甲基丙烯酸/ N -苯 基馬來酸酐縮亞胺/苄基甲基丙烯酸酯/乙二醇一甲基丙 烯酸酯/苯乙烯共聚物(共聚合重量比=1 5/2 5/ 35/10/15, Mw=30, 000, Mn= 1 0 , 000) 140重量份(C)多官能性單體之二季 戊四醇基六丙烯酸酯160重量份,(D)光聚合起始劑 之1—〔4 一(甲硫基)苯基〕一 2 —甲基一 2 —嗎啉丙 烷一 1—酮20重量份與增感劑之4,4 > —雙(二乙基 胺基)二苯甲酮1 5重量份,與作爲溶劑之丙二醇一甲基 醚乙酸酯1,0 0 0重量份混合,以製作感放射線性組成 物之液狀組成物(R 5 )。 (介電係數之測定與畫素陣列之形成及顯示性能之評估) 經濟部智慧財產局員工消費合作社印製 除將液狀組成物(R 4 )以液狀組成物(R 5 )替代 外,其他皆依實施例8相同方法測定形成著色膜之介電係 數與體積電阻係數,或於基板上形成具有紅色條狀畫素之 畫素陣列後,對其顯示性能進行評估。 其結果得知,著色膜之介電係數爲4 . 5,體積電阻 係數爲2 · 5 X 1 0 1 4 Ω c m,且液晶顯示裝置於進行操 作後,並未發現顯示不佳之情形。 實施例1 0 將(A )作爲著色劑之C . I ·顏料藍1 5 : 6與 本紙張尺度適用中國國家標準(CNS ) A4規格(210X 297公釐) -59- 508457 A7 B7 五、發明説明(57 ) (請先閲讀背面之注意事項再填寫本頁) C · I •顏料紫2 3以9 5 / 5 (重量比)混合物3 5重 量份,(B)鹼可溶性樹脂之甲基丙烯酸/2 —羥乙基( 甲基)丙烯酸酯/苄基甲基丙烯酸酯共聚物(共聚合重量 比=15/15/70, Mw=25, 〇0〇, 10,000) 150重量份(C)多官能性單體之二季 戊四醇基六丙烯酸酯1 5 0重量份,(D )光聚合起始劑 之 2,2'—雙(2 -氯苯基)一 4,一 5,5' -四苯基一 1,2 / -聯二咪唑6重量份胺系氫供應體之4 ,4 > 一雙(二乙基胺基)二苯甲酮6重量份與硫醇系氫 供應體之2 -氫硫基苯駢噻唑3重量份,與作爲溶劑之丙 二醇一甲基醚乙酸酯7 0 0重量份與環己酮3 0 0重量份 混合,以製作感放射線性組成物之液狀組成物(B 3 )。 (介電係數之測定與畫素陣列之形成及顯示性能之評估) 經濟部智慧財產局員工消費合作社印製 除將液狀組成物(R 4 )以液狀組成物(B 3 )替代 外,其他皆依實施例8相同方法測定形成著色膜之介電係 數與體積電阻係數,或於基板上形成具有藍色條狀畫素之 畫素陣列後,對其顯示性能進行評估。 其結果得知,著色膜之介電係數爲4 . 8,體積電阻 係數爲1 · 8 X 1 0 1 4 Ω c m,且液晶顯示裝置於進行操 作後,並未發現顯不不佳之情形。 實施例1 1 將(A )作爲著色劑之C · I ·顏料綠3 6與 本纸張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 60- 508457 A7 B7 五、發明説明(58 ) c . I ·顏料黃1 5 0以6 5 / 3 5 (重量比)混合物 5 0重量份,(B )鹼可溶性樹脂之甲基丙烯酸/ 2 一羥 乙基(甲基)丙烯酸酯/苄基甲基丙烯酸酯共聚物(共聚 口重星比=15/15/7〇,]\4'\^=2 5,000, Mn=l〇, 0〇〇)15〇重量份,(C)多官能性單 體之二季戊四醇基六丙烯酸酯15〇重量份,(d)光聚 合起始劑之二嗪系化合物(1 ) 1 〇重量份,與作爲溶劑 之丙二醇一甲基醚乙酸酯7 〇 0重量份與環己酮3 〇 〇重 量份混合,以製作感放射線性組成物之液狀組成物(G 3 I----------I (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 (介電係數之測疋與畫素陣列之形成及顯示性能之評估) 除將液狀組成物(R 4 )以液狀組成物(G 3 )替代 外,其他皆依實施例8相同方法測定形成著色膜之介電係 數與體積電阻係數,或於基板上形成具有紅色條狀畫素之 畫素陣列後,對其顯示性能進行評估。 其結果得知,著色膜之介電係數爲4 · 7,體積電阻 係數爲4 · 1 X 1 0 1 4 Ω c m,且液晶顯示裝置於進行操 作後,並未發現顯示不佳之情形。 【發明之效果】 如上所述般,本發明之輻射敏感放射線性組成物,於 形成通孔或c字型凹孔外,顯像時液不會產生顯像殘留等 現象,且具有優良的與T F T形式液晶驅動用基板與氮化 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) ~ ^ 訂 508457 A7 B7五、發明説明(59 )、矽膜等鈍化膜之密著性。 — — ^----rL^i----!―,訂丨_.I丨费 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -62-、 1T This paper size applies Chinese National Standard (CNS) A4 (210X297mm) -54-508457 A7 B7 V. Description of the invention (52) (Formation and evaluation of pixel array) In addition to the liquid composition (R 1 ) Except replacing the liquid composition (r 3), the other methods are the same as those in Example 1, a red stripe pixel array is formed on the substrate and evaluated. The obtained pixel array was observed with an optical microscope, and no imaging residue was found on the unexposed substrate. And the 5 # m wide through hole is also open, and the adhesion between the obtained pixel and the substrate is also excellent. Example Θ In Example 3, except that the polyfunctional acrylate (2) 10 parts by weight was further added, the liquid composition (B 2 of the radiation-sensitive radiation composition) was prepared in the same manner as in Example 3 ). (Formation and Evaluation of the Pixel Array) Except replacing the liquid composition (B 1) with the liquid composition (b 2), the other methods are the same as those in Example 3 to form blue stripe pixels on the substrate. Array and evaluate. The obtained pixel array was observed with an optical microscope, and no imaging residue was found on the unexposed substrate. And the 5 # m wide through hole is also open, and the adhesion between the obtained pixel and the substrate is also excellent. Example 7 In Example 4, except that 10 parts by weight of the polyfunctional acrylate (i) was further added, the same method as in Example 4 was used to make the radiation. The paper size was adapted to the Chinese National Standard (CNS) A4 specification. (210X 297mm) '-— -55-(Please read the notes on the back before filling out this page) Order printed by the Intellectual Property Bureau employee consumer cooperative of the Ministry of Economic Affairs 508457 A7 B7 Printed by the employee property cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 2. Description of the invention (53) Liquid composition (G 2) of sensitive radiation composition. (Formation and Evaluation of Pixel Array) Except replacing the liquid composition (G 1) with the liquid composition (G 2), the other methods are the same as those in Example 3 to form blue stripe pixels on the substrate. Array and evaluate. The obtained pixel array was observed with an optical microscope, and no imaging residue was found on the unexposed substrate. And the 5 a m wide through hole is also open, and the adhesion between the obtained pixel and the substrate is also excellent. Example 8 C · I · Pigment Red 1 7 7 and C · I · Pigment Red 2 2 4 (A) as a coloring agent was mixed with 50 parts by weight of 6 5/3 5 (weight ratio), and (B) alkali Soluble resin of methacrylic acid / N-phenylmaleic anhydride imine / benzyl methacrylate / ethylene glycol monomethacrylate / styrene copolymer (copolymerization weight ratio = 1 5/2 5 / 35/10/15, Mw = 30,000, Mn = 10,000) 140 parts by weight (C) 160 parts by weight of dipentaerythritol hexaacrylate of polyfunctional monomer, (D) photopolymerization initiator 50 parts by weight of 2-benzyl-2-dimethylamino-1 1- (4-morpholinophenyl) butane-1 1-ketone, and propylene glycol monomethyl ether acetate 1,0 as a solvent 0 0 parts by weight are mixed to produce a liquid composition (R 4) of a radiation-sensitive composition. Then, measure the coloring of this liquid composition (R 4) according to the following points: ----------- (Please read the precautions on the back before filling this page) The paper size of the book is applicable to Chinese national standards ( CNS) A4 specifications (210X297 mm) -56- 508457 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (54) The dielectric constant and volume resistivity formed by the film are compared with other Methods The display performance of the pixel array was evaluated. (Measurement of Dielectric Coefficient) The liquid composition (R 4) was spin-coated on an aluminum substrate (diameter 10 mm · 2 mm, chromium film thickness 0.525 mm) coated with chromium, and Asahi glass Co., Ltd.), then pre-baked for 10 minutes in a dust-free oven at 90 ° C to form a coating film of 1 · 5 // m. Subsequently, the substrate was cooled to room temperature, and the coating film was exposed at an exposure amount of 2,000 J / m 2 with ultraviolet rays containing wavelengths of 365 nm, 405 nm, and 436 nm using a high-pressure mercury lamp. The substrate was baked in a dust-free oven at 220 ° C for 25 minutes, and then a colored film was formed on the substrate. Next, a circular aluminum electrode having a diameter of 1 m was formed on the obtained colored film using a vacuum evaporation apparatus (trade name PEC-A2, manufactured by Shimadzu Corporation). A 5 mm square film was cut from the portion where the aluminum electrode was not formed to expose the chromium surface. Then, the copper wire was adhered to the exposed chromium surface with a silver paste, and a capacitance measuring device (trade name: LCR meter 4 2 8 4 A, manufactured by HEWLETT PACKARD) was installed, and the dielectric constant was calculated from the 値. As a result, it was found that the dielectric constant of the colored layer was 4.3. (Measurement of volume resistivity) A micro-current meter is installed on the electrode-coated coloring film prepared above. The paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) ~ -57- I ---- ---- Clothing-(Please read the precautions on the back before filling this page), language, line 508457 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (55) (Product name PA determination Count 4 1 4 0 B (manufactured by HEWLETT PACKARD), measure the current 値 when a DC current of 0 · 1 V is applied, and calculate the volume resistivity from the 値. As a result, it was found that the volume resistivity of the colored layer was 2.8 × 1014 Qcm. (Formation of Pixel Array and Evaluation of Display Performance) After the liquid composition (R 4) was spin-coated on the surface of a TFT-type liquid crystal driving substrate having a silicon nitride film formed on the surface, Pre-bake for 10 minutes in a dust-free oven at t to form a 3 · 0 β m coating film. Subsequently, the substrate was cooled to room temperature, and the coating film was applied with a high-pressure mercury lamp through a photomask to ultraviolet rays containing wavelengths of 3 6 5 nm, 40 5 nm, and 4 3 6 nm at 2, 0 0 J / m. 2 exposures for exposure. Then the substrate was immersed in an aqueous solution containing 0.1% by weight of tetramethylammonium hydroxide at 2 3 ° C for 1 minute for development processing, and then washed with ultrapure water and air-dried. After baking in a dust-free oven at 20 ° C for 25 minutes, a daylight array with red pixels is formed on the substrate. A liquid crystal display device obtained by bonding a substrate formed in the same manner as described above to a substrate having I but 0 electrodes formed by sputtering was not found to have a poor display after operation. Example 9 C (I) with (A) as the colorant. Pigment Red 1 7 7 and this paper size apply the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page ) -58- 508457 A7 B7 V. Description of the invention (56) (Please read the notes on the back before filling in this page) C · I. Pigment red 2 2 4 at 6 5/3 5 (weight ratio) mixture 50 weight Parts, (B) methacrylic acid / N-phenylmaleic anhydride imine / benzyl methacrylate / ethylene glycol monomethacrylate / styrene copolymer (copolymerization weight ratio = 1 5/2 5 / 35/10/15, Mw = 30, 000, Mn = 1 000) 140 parts by weight (C) 160 parts by weight of dipentaerythritol hexaacrylate of a polyfunctional monomer, (D) 20 parts by weight of photopolymerization initiator 1- [4-mono (methylthio) phenyl] 2-methyl-2 2-morpholine propane 1-one and 4,4 of sensitizer > -bis ( 15 parts by weight of diethylamino) benzophenone, and 1,000 parts by weight of propylene glycol monomethyl ether acetate as a solvent are mixed to prepare a liquid composition of a radiation-sensitive composition ( R 5). (Determination of dielectric constant, formation of pixel array and evaluation of display performance) Printed by the Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs, except that the liquid composition (R 4) is replaced by the liquid composition (R 5). Others measured the dielectric constant and volume resistivity of the colored film in the same manner as in Example 8, or formed a pixel array with red stripe pixels on the substrate, and then evaluated its display performance. As a result, it was found that the dielectric constant of the coloring film was 4.5, and the volume resistivity was 2.5 x 1 0 1 4 Ω cm. After the liquid crystal display device was operated, no poor display was found. Example 10 C. I. Pigment Blue 1 5: 6 with (A) as colorant Applicable to Chinese National Standard (CNS) A4 Specification (210X 297 mm) -59- 508457 A7 B7 V. Invention Note (57) (Please read the precautions on the back before filling out this page) C · I • Pigment Violet 2 3 at 9 5/5 (weight ratio) mixture 3 5 parts by weight, (B) methacrylic acid of alkali soluble resin / 2-Hydroxyethyl (meth) acrylate / benzyl methacrylate copolymer (copolymerization weight ratio = 15/15/70, Mw = 250,000, 10,000) 150 parts by weight (C ) 150 parts by weight of dipentaerythritol hexaacrylate of polyfunctional monomer, (D) 2,2'-bis (2-chlorophenyl) -1,4-5,5'- of photopolymerization initiator 6 parts by weight of tetraphenyl-1, 2 / -biimidazole, 4 parts by weight of amine-based hydrogen supplier 4, > 6 parts by weight of bis (diethylamino) benzophenone, and that of thiol-based hydrogen supplier 3 parts by weight of 2-hydrothiobenzidine thiazole is mixed with 700 parts by weight of propylene glycol monomethyl ether acetate and 300 parts by weight of cyclohexanone as a solvent to make a liquid composition of a radiation-sensitive composition Composition (B 3). (Determination of dielectric constant, formation of pixel array and evaluation of display performance) Printed by the Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs, except that the liquid composition (R 4) is replaced by the liquid composition (B 3). Others measured the dielectric constant and volume resistivity of the colored film according to the same method as in Example 8, or formed a pixel array with blue stripe pixels on the substrate, and then evaluated its display performance. As a result, it was found that the dielectric constant of the coloring film was 4.8, and the volume resistivity was 1.8 × 10 14 Ω cm, and that the liquid crystal display device was not found to be inferior after being operated. Example 1 1 C (I) Pigment Green 3 (A) as a coloring agent and Chinese paper standard (CNS) A4 specification (210X297 mm) 60- 508457 A7 B7 as the coloring agent V. Description of the invention (58 ) c. I. Pigment yellow 1 50 to 6 5/3 5 (weight ratio) 50 parts by weight of the mixture, (B) alkali-soluble resin of methacrylic acid / 2 monohydroxyethyl (meth) acrylate / benzyl Methacrylate copolymer (copolymer weight-to-weight ratio = 15/15 / 7〇,] \ 4 '\ ^ = 25,000, Mn = 10, 00) 15 parts by weight, (C) 150 parts by weight of dipentaerythritol-based hexaacrylate of a polyfunctional monomer, (d) 10 parts by weight of a diazine compound (1) of a photopolymerization initiator, and propylene glycol monomethyl ether acetate as a solvent 7000 parts by weight and 3,000 parts by weight of cyclohexanone are mixed to produce a liquid composition (G 3 I ---------- I (Please read the note on the back first) Please fill in this page for further information.) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (measurement of dielectric constant and formation of pixel array and evaluation of display performance). Except the liquid composition (R 4) Except for the replacement of the G-shaped composition (G 3), the dielectric constant and volume resistivity of the colored film were measured in the same manner as in Example 8, or after forming a pixel array with red stripe pixels on the substrate, The display performance was evaluated. As a result, it was found that the dielectric constant of the colored film was 4 · 7, and the volume resistivity was 4 · 1 X 1 0 1 4 Ω cm, and after the liquid crystal display device was operated, no display failure was found. [Effects of the Invention] As described above, the radiation-sensitive radiation composition of the present invention does not form a phenomenon such as developing residues in the liquid during development outside the through-holes or c-shaped recesses, and has the following characteristics: Excellent substrates for TFT-type liquid crystal driving substrates and nitrided paper. Applicable to China National Standard (CNS) A4 specifications (210X297 mm) ~ ^ Order 508457 A7 B7 V. Description of the invention (59), passivation films such as silicon film ----- ^ ---- rL ^ i ----! ―, Ordering 丨 _.I 丨 fee (please read the notes on the back before filling this page) Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs This paper size applies Chinese National Standard (CNS) A4 specifications (210X297 mm) -62-
Claims (1)
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP34197699A JP2001154013A (en) | 1999-12-01 | 1999-12-01 | Radiation composition for color liquid crystal display device |
JP2000026031A JP2001215324A (en) | 2000-02-03 | 2000-02-03 | Radiation sensitive composition for color liquid crystal display device and color liquid crystal display device |
JP2000139829A JP2001318220A (en) | 2000-05-12 | 2000-05-12 | Radiation-sensitive composition for color liquid crystal display device, color filter and color liquid crystal display device |
JP2000143900A JP2001324611A (en) | 2000-05-16 | 2000-05-16 | Radiation sensitive composition for color liquid crystal display device and color liquid crystal display device |
JP2000303192A JP2002107533A (en) | 2000-10-03 | 2000-10-03 | Radiation sensitive composition for color liquid crystal display device and color liquid crystal display device |
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TW508457B true TW508457B (en) | 2002-11-01 |
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TW089125510A TW508457B (en) | 1999-12-01 | 2000-11-30 | Radiation sensitive composition and color liquid crystal display device |
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KR (1) | KR100483097B1 (en) |
SG (1) | SG85221A1 (en) |
TW (1) | TW508457B (en) |
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JP4393104B2 (en) * | 2003-05-07 | 2010-01-06 | 富士フイルム株式会社 | Curable green composition for LCD and color filter |
JP4127150B2 (en) * | 2003-07-31 | 2008-07-30 | Jsr株式会社 | Radiation-sensitive resin composition, interlayer insulating film and microlens, and production method thereof |
JP4954194B2 (en) * | 2006-03-14 | 2012-06-13 | 旭化成イーマテリアルズ株式会社 | Photosensitive resin laminate |
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JP2878039B2 (en) * | 1992-07-29 | 1999-04-05 | 東京応化工業株式会社 | Photosensitive resin composition |
EP0866367A3 (en) * | 1997-03-19 | 1998-10-28 | JSR Corporation | Radiation sensitive composition |
JP3867177B2 (en) * | 1997-04-30 | 2007-01-10 | Jsr株式会社 | Radiation sensitive composition for color filter |
US6140019A (en) * | 1997-07-24 | 2000-10-31 | Jsr Corporation | Radiation sensitive composition |
US6255034B1 (en) * | 1997-09-09 | 2001-07-03 | Jsr Corporation | Radiation sensitive composition |
-
2000
- 2000-11-29 SG SG200007088A patent/SG85221A1/en unknown
- 2000-11-30 KR KR10-2000-0071835A patent/KR100483097B1/en active IP Right Grant
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KR100483097B1 (en) | 2005-04-14 |
KR20010062002A (en) | 2001-07-07 |
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