TWI449724B - Alkali-soluble resin and method for producing the same, and a photosensitive resin composition using an alkali-soluble resin - Google Patents

Alkali-soluble resin and method for producing the same, and a photosensitive resin composition using an alkali-soluble resin Download PDF

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TWI449724B
TWI449724B TW099106342A TW99106342A TWI449724B TW I449724 B TWI449724 B TW I449724B TW 099106342 A TW099106342 A TW 099106342A TW 99106342 A TW99106342 A TW 99106342A TW I449724 B TWI449724 B TW I449724B
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alkali
acid
general formula
represented
soluble resin
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TW201043647A (en
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Takashi Konno
Hiroaki Yamada
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Nippon Steel & Sumikin Chem Co
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • G02F1/133514—Colour filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0381—Macromolecular compounds which are rendered insoluble or differentially wettable using a combination of a phenolic resin and a polyoxyethylene resin
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
    • Y10S430/1055—Radiation sensitive composition or product or process of making

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Mathematical Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Materials For Photolithography (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Optical Filters (AREA)

Description

鹼可溶性樹脂及其製造方法、以及使用鹼可溶性樹脂之感光性樹脂組成物Alkali-soluble resin, method for producing the same, and photosensitive resin composition using alkali-soluble resin

本發明係藉由照射紫外線或電子線予以硬化，可藉由鹼顯影處理形成圖案之鹼可溶性樹脂及其製造方法，以及使用該鹼可溶性樹脂之感光性樹脂組成物，更詳言之，係有關為適合於製造濾色器用光阻時之感光性樹脂組成物。The present invention relates to an alkali-soluble resin which can be patterned by alkali development treatment by irradiation with ultraviolet rays or electron beams, a method for producing the same, and a photosensitive resin composition using the alkali-soluble resin, and more specifically, It is a photosensitive resin composition suitable for the manufacture of the photoresist for color filters.

彩色液晶顯示裝置，係以控制光之透過量或反射量之液晶部與濾色器為構成要素，該濾色器之製造方法通常使用在玻璃、塑膠片等透明基板的表面上形成黑色矩陣，然後，順序使紅、綠、藍等不同的色相形成條狀或嵌鑲狀等之顏色圖案之方法。近數年來，在液晶電視、液晶螢幕、彩色液晶手機等之範圍中使用彩色液晶顯示裝置，濾色器係左右此等液晶顯示裝置之視認性的重要構件之一。圖案尺寸係視濾色器之用途以及各顏色而不同，使紅、綠、藍之畫素予以細線化為100μm～50μm以下，使黑色矩陣予以細線化為20μm～10μm以下。因此，感光性樹脂組成物被要求藉由高尺寸精度形成圖案。The color liquid crystal display device is composed of a liquid crystal portion and a color filter for controlling the amount of light transmitted or reflected, and a method for manufacturing the color filter is generally used to form a black matrix on the surface of a transparent substrate such as glass or plastic sheet. Then, a method of forming a color pattern such as a strip shape or a mosaic shape in a different hue such as red, green, or blue is sequentially performed. In recent years, color liquid crystal display devices have been used in the range of liquid crystal televisions, liquid crystal screens, color liquid crystal mobile phones, etc., and color filters are one of important members of the visibility of such liquid crystal display devices. The pattern size is different depending on the use of the color filter and the color, and the red, green, and blue pixels are thinned to 100 μm to 50 μm or less, and the black matrix is thinned to 20 μm to 10 μm or less. Therefore, the photosensitive resin composition is required to be patterned by high dimensional accuracy.

一般而言，該用途之感光性樹脂組成物，係使用具有聚合性不飽和鍵之多官能光硬化性單體、鹼可溶性之黏合劑樹脂、及組合此等與光聚合引發劑之組成物。例如，於日本特開昭61-213213號公報(專利文獻1)或特開平1-152449號公報(專利文獻2)中揭示，作為濾色器用材料之應用所例示的作為黏合劑樹脂之具羧基的(甲基)丙烯酸或(甲基)丙烯酸酯、馬來酸酐與其他聚合性單體之共聚物。然而，此處所揭示的共聚物，由於為無規共聚物，在光照射部分內以及光未照射部分內產生鹼溶解速度之分布，顯影操作時之範圍狹窄，且不易得到銳角的圖案形狀或微細圖案。特別是含有高濃度的顏料時，會顯著降低曝光感度、且無法製得微細的負型圖案。而且，於日本特開平4-340965號公報(專利文獻3)中揭示，有關在1分子中具有聚合性不飽和雙鍵與羧基之鹼可溶性不飽和化合物，於濾色器等之負型圖案形成時有效。推測由於具有鹼可溶性之分子藉由光照射不溶化，與組合前述黏合劑樹脂及多官能聚合性單體相比時，形成高感度，此處所例示的化合物，係在苯酚低聚物之羥基任意加成聚合性不飽和基之丙烯酸與酸酐者，為該提案時，由於分子組成之不均勻性，形成鹼溶解速度分布寬廣，亦不易形成微細的負型圖案。In general, the photosensitive resin composition for the purpose of use is a polyfunctional photocurable monomer having a polymerizable unsaturated bond, an alkali-soluble binder resin, and a combination of these and a photopolymerization initiator. A carboxyl group as a binder resin exemplified as a material for a color filter is disclosed in JP-A-61-213213 (Patent Document 1) or JP-A-1-52449 (Patent Document 2). Copolymer of (meth)acrylic acid or (meth) acrylate, maleic anhydride and other polymerizable monomers. However, since the copolymer disclosed herein has a distribution of alkali dissolution rate in the light-irradiated portion and the light-irradiated portion due to the random copolymer, the range in the developing operation is narrow, and it is difficult to obtain an acute-angle pattern shape or fineness. pattern. In particular, when a pigment having a high concentration is contained, the exposure sensitivity is remarkably lowered, and a fine negative pattern cannot be obtained. In the case of the alkali-soluble unsaturated compound having a polymerizable unsaturated double bond and a carboxyl group in one molecule, a negative pattern formation in a color filter or the like is disclosed in JP-A-4-340965 (Patent Document 3). It is valid. It is presumed that since the alkali-soluble molecule is insolubilized by light irradiation, when compared with the combination of the above-mentioned binder resin and the polyfunctional polymerizable monomer, high sensitivity is formed, and the compound exemplified here is added to the hydroxyl group of the phenol oligomer. In the case of the acrylic acid and the acid anhydride which are a polymerizable unsaturated group, in the case of this proposal, the alkali dissolution rate distribution is broad, and it is difficult to form a fine negative pattern due to the non-uniformity of the molecular composition.

另外，於日本特開平4-345673號公報(專利文獻4)、特開平4-345608號公報(專利文獻5)、特開平4-355450號公報(專利文獻6)、及特開平4-363311號公報(專利文獻7)中揭示，使用具有雙酚芴構造之(甲基)丙烯酸環氧酯與酸酐之反應生成物的液狀樹脂。然而，藉由此等所例示的樹脂，由於(甲基)丙烯酸酯與酸酐之反應生成物時，分子量小。因此，化合物之感度低，無法形成微細的圖案。Japanese Patent Publication No. 4-345673 (Patent Document 4), JP-A-4-345608 (Patent Document 5), JP-A-4-355450 (Patent Document 6), and JP-A-4-363311 In the publication (Patent Document 7), a liquid resin having a reaction product of a (meth)acrylic acid epoxy ester having a bisphenol fluorene structure and an acid anhydride is used. However, the resin exemplified by the above has a small molecular weight due to a reaction product of a (meth) acrylate and an acid anhydride. Therefore, the sensitivity of the compound is low, and a fine pattern cannot be formed.

此外，於日本特開平5-339356號公報(專利文獻8)、特開平5-146132號公報(專利文獻9)、及WO94/00801號手冊(專利文獻10)中揭示，藉由丙烯酸二羥基丙酯化合物與酸二酐共聚合之鹼顯影性不飽和樹脂組成物、或藉由酸酐及酸二酐與丙烯酸二羥基丙酯化合物進行共聚合之鹼顯影性不飽和樹脂組成物。此時，進行酸二酐與丙烯酸二羥基丙酯化合物進行共聚合而製得聚合物。然而，丙烯基側鏈長對聚合物主鏈長而言為短，以光聚合形成的交聯點引起立體障害而妨礙聚合，交聯變得不發達，結果光硬化變得不充分。因此，在高濃度顏料下會有不易形成細線圖案的情形，尚有待改善之處。Japanese Patent Laid-Open No. Hei 5-339356 (Patent Document 8), JP-A No. 5-146132 (Patent Document 9), and WO 94/00801 (Patent Document 10) disclose that dihydroxypropyl acrylate is used. An alkali-developable unsaturated resin composition in which an ester compound and an acid dianhydride are copolymerized, or an alkali-developable unsaturated resin composition obtained by copolymerizing an acid anhydride and an acid dianhydride with a dihydroxypropyl acrylate compound. At this time, a polymer was obtained by copolymerizing an acid dianhydride and a dihydroxypropyl acrylate compound. However, the propylene-based side chain length is short for the polymer main chain length, and the cross-linking point formed by photopolymerization causes steric hindrance to hinder polymerization, and crosslinking becomes undeveloped, and as a result, photohardening becomes insufficient. Therefore, there is a case where it is difficult to form a fine line pattern under a high concentration of pigment, and there is still room for improvement.

而且，於日本特開平9-325494號公報(專利文獻11)中揭示，增加含有羧基之共聚物的分子量，進行鹼可溶性樹脂組成物之多官能化。然而，此時與前述之專利文獻相同地，由於對聚合物主鏈而言丙烯基側鏈長為短，會有光硬化變得不充分的可能性。In JP-A-H09-325494 (Patent Document 11), it is disclosed that the molecular weight of the copolymer containing a carboxyl group is increased, and the alkali-soluble resin composition is polyfunctionalized. However, in this case, similarly to the above-mentioned patent documents, since the propylene-based side chain length is short for the polymer main chain, photohardening may be insufficient.

[習知技術文獻][Practical Technical Literature]

[專利文獻][Patent Literature]

[專利文獻1]日本特開昭61-213213號公報[Patent Document 1] JP-A-61-213213

[專利文獻2]日本特開平1-152449號公報[Patent Document 2] Japanese Patent Laid-Open No. Hei 1-152449

[專利文獻3]日本特開平4-340965號公報[Patent Document 3] Japanese Patent Laid-Open No. 4-340965

[專利文獻4]日本特開平4-345673號公報[Patent Document 4] Japanese Patent Laid-Open No. 4-345673

[專利文獻5]日本特開平4-345608號公報[Patent Document 5] Japanese Patent Laid-Open No. 4-345608

[專利文獻6]日本特開平4-355450號公報[Patent Document 6] Japanese Patent Laid-Open No. 4-355450

[專利文獻7]日本特開平4-363311號公報[Patent Document 7] Japanese Patent Laid-Open No. 4-363311

[專利文獻8]日本特開平5-339356號公報[Patent Document 8] Japanese Patent Laid-Open No. Hei 5-339356

[專利文獻9]日本特開平5-146132號公報[Patent Document 9] Japanese Patent Laid-Open No. Hei 5-146132

[專利文獻10]WO94/00801號手冊[Patent Document 10] WO94/00801 manual

[專利文獻11]日本特開平9-325494號公報[Patent Document 11] Japanese Patent Laid-Open Publication No. Hei 9-325494

因此，本發明人等為解決如前述習知的感光性樹脂組成物之課題時，再三深入硏究檢討的結果，發現使含有特定聚合性不飽和基之二醇化合物、與四羧酸或其酸二酐及二羧酸、三羧酸或此等之酸酐進行反應所得的樹脂，適合形成感光性樹脂組成物。所以，藉由使用該鹼可溶性樹脂，可成功地控制對鹼顯影液之溶解性，且促進光硬化處理，硬化部或未硬化部對鹼顯影液之溶解度變大，可形成美麗的細線圖案，同時可以高感度製得顯影密接範圍寬廣的感光性樹脂組成物。Therefore, the inventors of the present invention have found that the diol compound containing a specific polymerizable unsaturated group, and a tetracarboxylic acid or the like, or the like, have been intensively examined in order to solve the problem of the photosensitive resin composition as described above. A resin obtained by reacting an acid dianhydride, a dicarboxylic acid, a tricarboxylic acid or an acid anhydride thereof is suitable for forming a photosensitive resin composition. Therefore, by using the alkali-soluble resin, the solubility in the alkali developing solution can be successfully controlled, and the photo-curing treatment can be promoted, and the solubility of the hardened portion or the uncured portion to the alkali developing solution becomes large, and a beautiful fine line pattern can be formed. At the same time, a photosensitive resin composition having a wide range of development adhesion can be obtained with high sensitivity.

所以，本發明之目的係提供一種適合作為形成微細圖案時優異的濾色器用材料之感光性樹脂組成物、及形成該感光性樹脂組成物之鹼可溶性樹脂。Therefore, an object of the present invention is to provide a photosensitive resin composition suitable as a material for a color filter which is excellent in forming a fine pattern, and an alkali-soluble resin which forms the photosensitive resin composition.

此外，本發明之另一目的係提供一種使用前述之高感度感光性樹脂組成物所形成的塗膜(硬化物)及濾色器。Further, another object of the present invention is to provide a coating film (cured material) and a color filter formed using the above-described high-sensitivity photosensitive resin composition.

換言之，本發明係有關一種鹼可溶性樹脂，其特徵為以一般式(1)所表示的在分子內具有羧基及聚合性不飽和基之鹼可溶性樹脂。In other words, the present invention relates to an alkali-soluble resin characterized by having an alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in the molecule represented by the general formula (1).

【化1】【化1】

(其中，W係表示以下述一般式(2)所表示的雙酚類衍生物；Y係表示4價羧酸殘基。G係表示下述一般式(3)或(4)所表示的取代基；Z係表示氫原子或以一般式(5)所表示的取代基；n係表示1～20之數)(W) represents a bisphenol derivative represented by the following general formula (2); Y represents a tetravalent carboxylic acid residue; and G represents a substitution represented by the following general formula (3) or (4). The Z system represents a hydrogen atom or a substituent represented by the general formula (5); the n system represents a number of 1 to 20)

【化2】[Chemical 2]

(其中，R1 、R2 、R3 及R4 係獨立表示氫原子、碳數1～6之烷基、鹵素原子或苯基；X係表示-CO-、-SO2 -、-C(CF3 )2 -、-Si(CH3 )2 -、-CH2 -、-C(CH3 )2 -、-S-、-O-、9,9-芴二基或直接鍵結；m係表示0～10之數)(wherein R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a halogen atom or a phenyl group; and X represents -CO-, -SO 2 -, -C ( CF 3 ) 2 -, -Si(CH 3 ) 2 -, -CH 2 -, -C(CH 3 ) 2 -, -S-, -O-, 9,9-fluorenyl or direct bonding; m Is the number from 0 to 10)

【化3】[化3]

(其中，R8 係表示碳數2～20之2價脂肪族或芳香族烴基；R6 係表示碳數2～22之2價伸烷基或烷基亞芳基；R7 係表示氫原子或甲基；p係表示0～60之數)(wherein R 8 represents a divalent aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms; R 6 represents a divalent alkylene group or an alkylarylene group having 2 to 22 carbon atoms; and R 7 represents a hydrogen atom; Or methyl; p is the number from 0 to 60)

【化4】【化4】

(其中，L係表示2或3價羧酸殘基；q係表示1或2)(wherein L represents a 2 or 3 carboxylic acid residue; q represents 1 or 2)

另外，本發明係有關一種鹼可溶性樹脂，其特徵為使含有以下述一般式(6)所表示之聚合性不飽和基的二醇化合物(A)、與四羧酸或其酸二酐(a)及二羧酸、三羧酸或此等之酸酐(b)以(A):(a):(b)=1:0.2～0.5:0.2～1.0之莫耳比的範圍進行反應所得者。Further, the present invention relates to an alkali-soluble resin characterized by comprising a diol compound (A) having a polymerizable unsaturated group represented by the following general formula (6), and a tetracarboxylic acid or an acid dianhydride thereof (a) And the dicarboxylic acid, the tricarboxylic acid or the acid anhydride (b) is obtained by reacting the molar ratio of (A): (a): (b) = 1:0.2 to 0.5: 0.2 to 1.0.

【化5】【化5】

(其中，R1 、R2 、R3 、R4 、G、X及m係與前述記載的規定相同)(wherein R 1 , R 2 , R 3 , R 4 , G, X and m are the same as those described above)

此外，本發明係有關一種感光性樹脂組成物，其特徵為含有(i)前述之鹼可溶性樹脂、(ii)不具羧酸殘基而至少具有1個以上聚合性不飽和基之光聚合性單體、及(iii)光聚合引發劑作為必須成分。Further, the present invention relates to a photosensitive resin composition characterized by comprising (i) the above-mentioned alkali-soluble resin, (ii) a photopolymerizable single having at least one polymerizable unsaturated group without a carboxylic acid residue The body and (iii) a photopolymerization initiator are essential components.

而且，本發明係有關使前述之感光性樹脂組成物予以硬化所得的硬化物。另外，本發明係有關一種濾色器，其特徵為藉由塗佈前述之感光性樹脂組成物，予以硬化所得的硬化物所形成者。Further, the present invention relates to a cured product obtained by curing the above-mentioned photosensitive resin composition. Further, the present invention relates to a color filter characterized by being formed by applying the above-mentioned photosensitive resin composition and curing the obtained cured product.

於下述中，詳細說明有關本發明。In the following, the present invention will be described in detail.

本發明之感光性樹脂組成物，係含有以一般式(1)所示之鹼可溶性樹脂為主成份之樹脂組成物。以一般式(1)所示之鹼可溶性樹脂，除由於具有以式(3)及(4)所示之來自(甲基)丙烯酸的聚合性不飽和基時，具有游離基聚合性以外，由於含有來自二羧酸、三羧酸或此等之酸酐及四羧酸或其酸二酐的羧酸殘基時，具有鹼可溶性。The photosensitive resin composition of the present invention contains a resin composition containing an alkali-soluble resin represented by the general formula (1) as a main component. The alkali-soluble resin represented by the general formula (1) has a radical polymerizable property in addition to the polymerizable unsaturated group derived from (meth)acrylic acid represented by the formulas (3) and (4), When it contains a carboxylic acid residue derived from a dicarboxylic acid, a tricarboxylic acid, or the like, and a tetracarboxylic acid or its acid dianhydride, it has alkali solubility.

一般式(1)之鹼可溶性樹脂，如下詳述，使以一般式(6)所示之具有聚合性不飽和基的二醇化合物(A)、與四羧酸或其酸二酐(a)及二羧酸、三羧酸或此等之酸酐(b)進行反應，以製造含有羧基之交互共聚物時有利。一般式(1)之鹼可溶性樹脂，由於同時具有聚合性不飽和基與羧酸殘基時，可賦予鹼顯影型感光性樹脂組成物具有優異的光硬化性、良顯影性、圖案特性，且可提高保護膜、遮光膜、紅、綠、藍等各畫素之物性。The alkali-soluble resin of the general formula (1), as described in detail below, the diol compound (A) having a polymerizable unsaturated group represented by the general formula (6), and a tetracarboxylic acid or its acid dianhydride (a) It is advantageous to carry out a reaction with a dicarboxylic acid, a tricarboxylic acid or an acid anhydride (b) to produce a cross-copolymer having a carboxyl group. When the alkali-soluble resin of the general formula (1) has both a polymerizable unsaturated group and a carboxylic acid residue, the alkali-developable photosensitive resin composition can have excellent photocurability, good developability, and pattern characteristics. The physical properties of the protective film, the light-shielding film, the red, green, and blue pixels can be improved.

詳細說明有關以一般式(1)所示之鹼可溶性樹脂的較佳製造方法。首先，以一般式(6)所示之具有聚合性不飽和基的二醇化合物，可藉由雙酚類與環氧氯丙烷等進行反應所得的具有2個環氧丙醚基之環氧化合物，更佳者藉由以下述一般式(7)所示之環氧化合物、與以下述一般式(8)及/或(9)所示之末端為羥基或羧基的(甲基)丙烯酸衍生物進行反應製得。A preferred method for producing the alkali-soluble resin represented by the general formula (1) will be described in detail. First, a diol compound having a polymerizable unsaturated group represented by the general formula (6), an epoxy compound having two glycidyl ether groups obtained by reacting a bisphenol with epichlorohydrin or the like More preferably, the epoxy compound represented by the following general formula (7) and the (meth)acrylic acid derivative having a hydroxyl group or a carboxyl group at the terminal represented by the following general formula (8) and/or (9) The reaction is carried out.

【化6】【化6】

於前述一般式(7)中，R1 、R2 、R3 、R4 係表示獨立的氫原子、碳數1～6之烷基、鹵素原子或苯基，較佳者為氫原子、碳數1～6之烷基、或苯基，更佳者為氫原子。而且，X係表示-CO-、-SO2 -、-C(CF3 )2 -、-Si(CH3 )2 -、-CH2 -、-C(CH3 )2 -、-S-、-O-、9,9-芴二基或直接鍵結；m係表示0～10之數，以9,9-芴二基較佳。In the above general formula (7), R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a halogen atom or a phenyl group, preferably a hydrogen atom or a carbon. The alkyl group having 1 to 6 or a phenyl group is more preferably a hydrogen atom. Further, X represents -CO-, -SO 2 -, -C(CF 3 ) 2 -, -Si(CH 3 ) 2 -, -CH 2 -, -C(CH 3 ) 2 -, -S-, -O-, 9,9-fluorenyl or direct bonding; m means 0 to 10, and 9,9-fluorenyl is preferred.

此外，與以前述一般式(7)所示之環氧化合物進行反應的末端為羥基或羧基之(甲基)丙烯酸衍生物，以下述一般式(8)及(9)所示。Further, the (meth)acrylic acid derivative having a hydroxyl group or a carboxyl group at the terminal which is reacted with the epoxy compound represented by the above general formula (7) is represented by the following general formulas (8) and (9).

【化7】【化7】

於前述一般式(8)及(9)中，R8 係碳數2～20之脂肪族或芳香族烴基，R6 係碳數2～22之2價伸烷基，R7 係氫原子或甲基，p係0～60之數。In the above general formulas (8) and (9), R 8 is an aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms, R 6 is a divalent alkyl group having 2 to 22 carbon atoms, and R 7 is a hydrogen atom or Methyl, p is the number from 0 to 60.

該環氧化合物與(甲基)丙烯酸衍生物之反應，可使用習知的方法，例如相對於1莫耳環氧化合物而言使用約2莫耳之(甲基)丙烯酸衍生物進行，就製造而言為有利。以該反應所得的反應物係含有聚合性不飽和基之二醇化合物(A)，以前述一般式(6)所示。The reaction of the epoxy compound with the (meth)acrylic acid derivative can be carried out by a conventional method, for example, by using about 2 mol of a (meth)acrylic acid derivative with respect to a 1 mol epoxy compound. Words are favorable. The reactant obtained by this reaction is a diol compound (A) containing a polymerizable unsaturated group, and is represented by the above general formula (6).

賦予一般式(1)之鹼可溶性樹脂的較佳雙酚類，例如下所述者。例如雙(4-羥基苯基)酮、雙(4-羥基-3,5-二甲基苯基)酮、雙(4-羥基-3,5-二氯苯基)酮、雙(4-羥基苯基)碸、雙(4-羥基-3,5-二甲基苯基)碸、雙(4-羥基-3,5-二氯苯基)碸、雙(4-羥基苯基)六氟丙烷、雙(4-羥基-3,5-二甲基苯基)六氟丙烷、雙(4-羥基-3,5-二氯苯基)六氟丙烷、雙(4-羥基苯基)二甲基矽烷、雙(4-羥基-3,5-二甲基苯基)二甲基矽烷、雙(4-羥基-3,5-二氯苯基)二甲基矽烷、雙(4-羥基苯基)甲烷、雙(4-羥基-3,5-二氯苯基)甲烷、雙(4-羥基-3,5-二溴苯基)甲烷、2,2-雙(4-羥基苯基)丙烷、2,2-雙(4-羥基-3,5-二甲基苯基)丙烷、2,2-雙(4-羥基-3,5-二氯苯基)丙烷、2,2-雙(4-羥基-3-甲基苯基)丙烷、2,2-雙(4-羥基-3-氯苯基)丙烷、雙(4-羥基苯基)醚、雙(4-羥基-3,5-二甲基苯基)醚、雙(4-羥基-3,5-二氯化苯基)醚等。而且，X以9,9-芴基之9,9-雙(4-羥基苯基)芴、9,9-雙(4-羥基-3-甲基苯基)芴、9,9-雙(4-羥基-3-氯化苯基)芴、9,9-雙(4-羥基-3-溴化苯基)芴、9,9-雙(4-羥基-3-氟化苯基)芴、9,9-雙(4-羥基-3,5-二甲基苯基)芴、9,9-雙(4-羥基-3,5-二氯化苯基)芴、9,9-雙(4-羥基-3,5-二溴化苯基)芴等較佳。更佳者為4,4’-雙酚、3,3’-雙酚等。Preferred bisphenols which are imparted to the alkali-soluble resin of the general formula (1) are as described below. For example, bis(4-hydroxyphenyl)one, bis(4-hydroxy-3,5-dimethylphenyl)one, bis(4-hydroxy-3,5-dichlorophenyl)one, bis (4- Hydroxyphenyl)anthracene, bis(4-hydroxy-3,5-dimethylphenyl)anthracene, bis(4-hydroxy-3,5-dichlorophenyl)anthracene, bis(4-hydroxyphenyl)hexa Fluoropropane, bis(4-hydroxy-3,5-dimethylphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dichlorophenyl)hexafluoropropane, bis(4-hydroxyphenyl) Dimethyl decane, bis(4-hydroxy-3,5-dimethylphenyl)dimethyl decane, bis(4-hydroxy-3,5-dichlorophenyl)dimethyl decane, bis (4- Hydroxyphenyl)methane, bis(4-hydroxy-3,5-dichlorophenyl)methane, bis(4-hydroxy-3,5-dibromophenyl)methane, 2,2-bis(4-hydroxybenzene) Propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2 - bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, bis(4-hydroxyphenyl)ether, bis(4-hydroxy- 3,5-Dimethylphenyl)ether, bis(4-hydroxy-3,5-dichlorophenyl)ether, and the like. Moreover, X is 9,9-fluorenyl 9,9-bis(4-hydroxyphenyl)anthracene, 9,9-bis(4-hydroxy-3-methylphenyl)anthracene, 9,9-bis ( 4-hydroxy-3-chlorophenyl)anthracene, 9,9-bis(4-hydroxy-3-brominated phenyl)anthracene, 9,9-bis(4-hydroxy-3-fluorinated phenyl)anthracene 9,9-bis(4-hydroxy-3,5-dimethylphenyl)anthracene, 9,9-bis(4-hydroxy-3,5-dichlorophenyl)anthracene, 9,9-double (4-Hydroxy-3,5-dibrominated phenyl) hydrazine or the like is preferred. More preferably, it is 4,4'-bisphenol, 3,3'-bisphenol or the like.

一般式(1)之鹼可溶性樹脂，可由前述之雙酚類所衍生的環氧化合物製得，除該環氧化合物外，只要是苯酚酚醛清漆樹脂型環氧化合物、或甲酚酚醛清漆樹脂型環氧化合物等具有2個環氧丙醚基之化合物時，皆可使用。而且，使雙酚類進行環氧丙醚化時，混入以前述一般式(7)所示之低聚物單位形成時，該一般式(7)中m之平均值為0～10(較佳者為0～2之範圍)時，本樹脂組成物之性能沒有問題。The alkali-soluble resin of the general formula (1) can be obtained from an epoxy compound derived from the above-mentioned bisphenol, and the phenol novolak resin type epoxy compound or the cresol novolak type resin type other than the epoxy compound. When a compound having two glycidyl ether groups such as an epoxy compound is used, it can be used. Further, when the bisphenols are subjected to glycidyl etherification, when the oligomer units represented by the above general formula (7) are mixed, the average value of m in the general formula (7) is 0 to 10 (preferably When the ratio is in the range of 0 to 2, there is no problem in the performance of the present resin composition.

其次，詳細說明有關提供一般式(1)之鹼可溶性樹脂的來自前述一般式(8)及(9)之以前述一般式(3)或(4)所示的(甲基)丙烯酸衍生物。Next, the (meth)acrylic acid derivative represented by the above general formula (3) or (4) from the above general formulas (8) and (9) for providing the alkali-soluble resin of the general formula (1) will be described in detail.

一般式(3)、(4)、(8)及(9)係表示至少具有1個以上聚合性不飽和基之酯鍵，且於此等中R6 為碳數2～22之伸烷基或烷基亞芳基。有關該伸烷基可以為直鍵或支鏈中任何一種，例如伸乙基、伸丙基、異伸丙基、正伸丁基、異伸丁基、第2-伸丁基、第3-伸丁基、伸戊基、伸己基、伸庚基、伸辛基、伸壬基、伸癸基、伸十一烷基、伸十二烷基、伸十三烷基、伸十四烷基、伸十五烷基、伸十六烷基、伸十七烷基、伸十八烷基、伸十九烷基、伸二十烷基、伸二十一烷基、伸二十二烷基等，有關烷基亞芳基，只要是在碳數之範圍內者即可，亦可為未經取代亞芳基，例如-Ph-Ph-(2,2’-聯亞苯基)、-Ph-Ph-Ph-(三亞苯基)、Ph-(CH3 )2 -Ph-(如雙酚A之殘基等)[Ph係表示亞苯基]、o,m,p-亞苯基取代的亞甲苯基、亞羥甲苯基、乙基亞苯基、正丙基亞苯基、異丙基亞苯基、直鏈或支鏈的丁基亞苯基、戊基亞苯基、己基亞苯基、庚基亞苯基、辛基亞苯基、壬基亞苯基、癸基亞苯基、十一烷基亞苯基、十二烷基亞苯基、十三烷基亞苯基、十四烷基亞苯基、十五烷基亞苯基、十六烷基亞苯基等，另外，有關前述的烷基亞芳基、只要是不超過碳數之範圍內、亦可2～4個被取代，另外，伸烷基部位亦可被不飽和鍵、醚鍵、酯鍵、醯胺鍵或胺基甲酸酯鍵所中斷。The general formulae (3), (4), (8) and (9) represent an ester bond having at least one polymerizable unsaturated group, and wherein R 6 is a C 2 to 22 alkyl group. Or an alkylarylene group. The alkylene group may be any of a straight bond or a branched chain, such as an extended ethyl group, a propyl group, an exo-propyl group, a n-butyl group, an isobutylene group, a 2-butene butyl group, a third stretch. Butyl, pentyl, hexyl, heptyl, octyl, decyl, decyl, undecyl, dodecyl, thirteen, tetradecyl, Extending pentadecyl, hexadecyl, heptadecyl, octadecyl, hexadecyl, eicosyl, eicosyl, tetradecyl, etc. The alkylarylene group may be an unsubstituted arylene group as long as it is in the range of carbon numbers, for example, -Ph-Ph-(2,2'-biphenylene), -Ph -Ph-Ph-(triphenylene), Ph-(CH 3 ) 2 -Ph- (such as residues of bisphenol A, etc.) [Ph represents phenylene], o, m, p-phenylene substitution Ytylene, hydroxytolyl, ethylphenylene, n-propylphenylene, isopropylphenylene, linear or branched butyl phenylene, pentyl phenylene, hexyl Phenyl, heptylphenylene, octylphenylene, nonylphenylene, nonylphenylene, undecylphenylene, dodecyl phenylene a tridecyl phenylene group, a tetradecyl phenylene group, a pentadecyl phenylene group, a hexadecyl phenylene group or the like, and, in addition, the alkyl arylene group as described above, as long as it does not exceed the carbon number Within the range of 2 to 4, the alkyl group may be interrupted by an unsaturated bond, an ether bond, an ester bond, a guanamine bond or a urethane bond.

而且，R8 係表示碳數2～20之脂肪族或芳香族烴基，例如有關脂肪族烴基，直鏈或支鏈皆可，例如伸乙基、伸丙基、異伸丙基、正伸丁基、異伸丁基、第2-伸丁基、第3-伸丁基、伸戊基、伸己基、伸庚基、伸辛基、伸壬基、伸癸基、伸十一烷基、伸十二烷基、伸十三烷基、伸十四烷基、伸十五烷基、伸十六烷基、伸十七烷基、伸十八烷基、伸十九烷基、伸二十烷基等；有關芳香族烴基，只要是在碳數之範圍內即可，亦可為未經取代物，例如-Ph-Ph-(2,2’-聯亞苯基)、-Ph-Ph-Ph-(三亞苯基)、-Ph-(CH3 )2 -Ph-(如雙酚A之殘基等)「Ph係表示亞苯基」、o,m,p-亞苯基取代的亞甲苯基、亞羥甲苯基、乙基亞苯基、正丙基亞苯基、異丙基亞苯基、直鏈或支鏈的丁基亞苯基、戊基亞苯基、己基亞苯基、庚基亞苯基、辛基亞苯基、壬基亞苯基、癸基亞苯基、十一烷基亞苯基、十二烷基亞苯基、十三烷基亞苯基、十四烷基亞苯基等，另外，只要是不超過碳數之範圍內、亦可2～4個被取代，另外，伸烷基部位亦可被不飽和鍵、醚鍵、酯鍵、醯胺鍵或胺基甲酸酯鍵所中斷。Further, R 8 represents an aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms, and for example, an aliphatic hydrocarbon group may be used, and a straight chain or a branched chain may be used, for example, an ethyl group, a propyl group, an exo-propyl group, and a n-butyl group. , isobutylene, 2-tert-butyl, 3-butene, pentyl, hexyl, heptyl, octyl, thiol, decyl, undecyl, Dodecyl, thirteen, alkyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, hexadecyl, An alkyl group or the like; the aromatic hydrocarbon group may be an unsubstituted substance as long as it is in the range of carbon number, for example, -Ph-Ph-(2,2'-biphenylene), -Ph-Ph -Ph-(triphenylene), -Ph-(CH 3 ) 2 -Ph- (such as residues of bisphenol A, etc.) "Ph represents phenylene", o, m, p-phenylene substituted Methylene, hydroxytolyl, ethylphenylene, n-propylphenylene, isopropylphenylene, linear or branched butyl phenylene, pentyl phenylene, hexyl benzene Base, heptylphenylene, octylphenylene, nonylphenylene, nonylphenylene, undecylphenylene, twelve Further, the phenylene group, the tridecyl phenylene group, the tetradecyl phenylene group, and the like may be substituted in the range of not more than the carbon number, or may be substituted in the range of 2 to 4, and the alkyl group is also substituted. It can be interrupted by an unsaturated bond, an ether bond, an ester bond, a guanamine bond or a urethane bond.

而且，p係表示0～60之數，恐會因化合物而使分布為廣泛範圍，導致樹脂性能降低或無法使硬化物具有充分的硬化性，較佳者為0～40，更佳者為0～20之範圍時，可確實地保持作為本發明之樹脂的性能。Further, p is a number of from 0 to 60, and the distribution may be broad due to the compound, resulting in deterioration of resin properties or insufficient hardenability of the cured product, preferably from 0 to 40, more preferably from 0. When it is in the range of -20, the performance as the resin of the present invention can be surely maintained.

此外，有關前述一般式(6)所製造的二醇化合物及繼後製造本發明之鹼可溶性樹脂時所使用的溶劑、觸媒等之反應條件，沒有特別的限制，例如使用不具羥基、具有較反應溫度更高的沸點之溶劑作為反應溶劑，該溶劑可為乙基溶纖劑乙酸酯、丁基溶纖劑乙酸酯等之溶纖劑系溶劑、或二直鏈聚醚、乙基卡必醇乙酸酯、丁基卡必醇乙酸酯、丙二醇單甲醚乙酸酯等之高沸點醚系或酯系之溶劑、或環己酮、二異丁酮等之酮系溶劑等。另外，使用的觸媒例如使用溴化四乙銨、氯化三乙基苯甲銨等之銨鹽、三苯基膦、參(2,6-二甲氧基苯基)膦等之膦類等習知者。有關此等在前述專利文獻11等有詳細記載。Further, the reaction conditions of the diol compound produced by the above general formula (6) and the solvent, catalyst, and the like which are used in the subsequent production of the alkali-soluble resin of the present invention are not particularly limited, and for example, the use of a hydroxyl group is not preferable. A solvent having a higher boiling point of a reaction temperature is used as a reaction solvent, and the solvent may be a cellosolve solvent such as ethyl cellosolve acetate or butyl cellosolve acetate, or a two-linear polyether or an ethyl card. A high boiling point ether or ester solvent such as alcohol acetate, butyl carbitol acetate or propylene glycol monomethyl ether acetate, or a ketone solvent such as cyclohexanone or diisobutyl ketone. Further, as the catalyst to be used, for example, an ammonium salt such as tetraethylammonium bromide or triethylammonium chloride or a phosphine such as triphenylphosphine or bis(2,6-dimethoxyphenyl)phosphine is used. Such as the learner. These are described in detail in the aforementioned Patent Document 11 and the like.

另外，於以一般式(6)所示之二醇化合物(A)中反應的酸成份，可使用與二醇化合物(A)分子中之羥基進行反應所得的四羧酸或其酸二酐(a)及二羧酸、三羧酸或此等之酸酐(b)。該酸成份為飽和或不飽和中任何一種皆有效。其中，四羧酸或其酸二酐(a)及二羧酸、三羧酸或此等之酸酐(b)，可使用飽和直鏈烴基四羧酸之酸酐及酸二酐或脂環式四羧酸之酸酐及酸二酐、芳香族四羧酸之酸酐及酸二酐等。Further, in the acid component to be reacted in the diol compound (A) represented by the general formula (6), a tetracarboxylic acid obtained by reacting with a hydroxyl group in the molecule of the diol compound (A) or an acid dianhydride thereof can be used ( a) and a dicarboxylic acid, a tricarboxylic acid or such anhydride (b). The acid component is effective in any of saturating or unsaturated. Wherein, the tetracarboxylic acid or its acid dianhydride (a) and the dicarboxylic acid, the tricarboxylic acid or the anhydride (b) may be an anhydride of a saturated linear hydrocarbon tetracarboxylic acid and an acid dianhydride or an alicyclic four. An acid anhydride of an carboxylic acid, an acid dianhydride, an acid anhydride of an aromatic tetracarboxylic acid, and an acid dianhydride.

此處，飽和直鏈烴四羧酸或其酸二酐，例如丁烷四羧酸、戊烷四羧酸、己烷四羧酸或其酸二酐等，此外，飽和環狀烴亦可為經取代的飽和環狀四羧酸或其酸二酐。Here, a saturated linear hydrocarbon tetracarboxylic acid or an acid dianhydride thereof, for example, butane tetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid or an acid dianhydride thereof, or a saturated cyclic hydrocarbon may be used. Substituted saturated cyclic tetracarboxylic acid or its acid dianhydride.

此外，脂環式四羧酸或其酸二酐，例如環丁烷四羧酸、環戊烷四羧酸、環己烷四羧酸、環庚烷四羧酸、降冰片烷四羧酸或其酸二酐等，另外，飽和烴亦可為經取代的脂環式四羧酸或其酸二酐。而且，芳香族四羧酸或其酸二酐例如焦磷酸、二苯甲酮四羧酸、聯苯四羧酸、聯苯醚四羧酸、二苯基碸四羧酸或其酸二酐等。本發明之酸或其酸二酐，以聯苯四羧酸、二苯甲酮四羧酸、聯苯醚四羧酸或其酸二酐，更佳者為聯苯四羧酸、聯苯醚四羧酸或其酸二酐。此等酸或其酸二酐可以2種併用。Further, an alicyclic tetracarboxylic acid or an acid dianhydride thereof such as cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, norbornanetetracarboxylic acid or The acid dianhydride or the like may be a substituted alicyclic tetracarboxylic acid or an acid dianhydride thereof. Further, the aromatic tetracarboxylic acid or its acid dianhydride such as pyrophosphoric acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenyl ether tetracarboxylic acid, diphenylphosphonium tetracarboxylic acid or acid dianhydride thereof, etc. . The acid of the present invention or its acid dianhydride, which is biphenyltetracarboxylic acid, benzophenone tetracarboxylic acid, diphenyl ether tetracarboxylic acid or its acid dianhydride, more preferably biphenyltetracarboxylic acid or diphenyl ether. Tetracarboxylic acid or its acid dianhydride. These acids or their acid dianhydrides may be used in combination of two kinds.

而且，飽和直鏈烴二羧酸及三羧酸(或此等之酸酐)例如琥珀酸、乙醯基琥珀酸、己二酸、壬二酸、檸蘋酸、丙二酸、戊二酸、檸檬酸、酒石酸、羰基戊二酸、庚二酸、癸二酸、辛二酸、二乙醇(或此等之酸酐)等，此外，烴基被取代的直鏈烴二羧酸及三羧酸(或此等之酸酐)。而且，飽和環狀烴二羧酸及三羧酸(或此等之酸酐)，例如六氫苯二甲酸、環丁烷二羧酸、環戊烷二羧酸、降冰片烷二羧酸、六氫偏苯三甲酸(或此等之酸酐)等，此外，亦可為飽和烴被取代的脂環式二羧酸及三羧酸(或此等之酸酐)。另外，不飽和二羧酸及三羧酸(或此等之酸酐)，例如馬來酸、衣康酸、苯二甲酸、四氫苯二甲酸、甲基原亞甲基四氫苯二甲酸、氯菌酸、偏苯三甲酸(或此等之酸酐)。於此等之中，較佳者為琥珀酸、衣康酸、四氫苯二甲酸、六氫偏苯三甲酸、苯二甲酸、偏苯三酸，更佳者為琥珀酸、衣康酸、四氫苯二甲酸。此等酸及其酸酐亦可2種以上使用。Further, saturated linear hydrocarbon dicarboxylic acids and tricarboxylic acids (or such anhydrides) such as succinic acid, acetyl succinic acid, adipic acid, sebacic acid, citramalic acid, malonic acid, glutaric acid, Citric acid, tartaric acid, carbonyl glutaric acid, pimelic acid, sebacic acid, suberic acid, diethanol (or such anhydrides), etc., in addition, hydrocarbyl-substituted linear hydrocarbon dicarboxylic acids and tricarboxylic acids ( Or such anhydrides). Furthermore, saturated cyclic hydrocarbon dicarboxylic acids and tricarboxylic acids (or such anhydrides), such as hexahydrophthalic acid, cyclobutane dicarboxylic acid, cyclopentane dicarboxylic acid, norbornane dicarboxylic acid, six Hydrogen trimellitic acid (or such anhydride), and the like, and may be a saturated hydrocarbon-substituted alicyclic dicarboxylic acid and a tricarboxylic acid (or such an acid anhydride). In addition, unsaturated dicarboxylic acids and tricarboxylic acids (or such anhydrides), such as maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, methyl ortho-methylenetetrahydrophthalic acid, Chloric acid, trimellitic acid (or such anhydrides). Among them, preferred are succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, trimellitic acid, and more preferably succinic acid, itaconic acid, Tetrahydrophthalic acid. These acids and their acid anhydrides can also be used in two or more types.

此外，有關前述之二醇化合物與酸成份反應的方法，沒有特別的限制，例如於前述專利文獻11中記載，可採用反應溫度為90～140℃下使二醇化合物與四羧酸二酐進行反應的習知方法。較佳者為如化合物之末端為羧酸基、以一般式(6)所示之具有聚合性不飽和基的二醇化合物(A)、與四羧酸或其酸二酐(a)、與二羧酸、三羧酸或其酸酐(b)之莫耳數比例，(A):(a):(b)=1:0.2～0.5:0.2～1.0下、定量進行反應為宜。四羧酸或其酸二酐(a)之莫耳比未達0.2時，恐會有未反應二醇化合物之含量增大，鹼可溶性樹脂組成物之經時安定性降低的情形。另外，莫耳比為0.5以上時，由於以一般式(6)所示之化合物的末端為酸酐，或由於未反應酸二酐之含有量增大而作為異物存在，故不具樹脂所期待的性能。而且，二羧酸、三羧酸或其酸酐(b)之莫耳比未達0.2時，恐會有未反應二醇化合物之含有量增大，鹼可溶性樹脂組成物之經時安定性降低。另外，莫耳比為1.0以上時，以一般式(6)所示之化合物的末端為來自該酸或酸酐，由於所得的樹脂之分子量降低，故不具樹脂所期待的性能。而且，在反應溫度為90～130℃下使加入的原料均勻地溶解，同時進行反應，然後在40～80℃下進行反應及熟成處理較佳。Further, the method for reacting the above-mentioned diol compound with an acid component is not particularly limited. For example, it is described in the above-mentioned Patent Document 11 that a diol compound and a tetracarboxylic dianhydride can be used at a reaction temperature of 90 to 140 °C. A known method of reaction. Preferred is a diol compound (A) having a carboxylic acid group at the terminal of the compound, a polymerizable unsaturated group represented by the general formula (6), a tetracarboxylic acid or an acid dianhydride thereof (a), and The molar ratio of the dicarboxylic acid, the tricarboxylic acid or the anhydride thereof (b), (A): (a): (b) = 1: 0.2 to 0.5: 0.2 to 1.0, and the reaction is quantitatively carried out. When the molar ratio of the tetracarboxylic acid or the acid dianhydride (a) is less than 0.2, the content of the unreacted diol compound may increase, and the stability of the alkali-soluble resin composition may decrease. In addition, when the molar ratio is 0.5 or more, since the terminal of the compound represented by the general formula (6) is an acid anhydride or the content of the unreacted acid dianhydride is increased as a foreign matter, the resin is expected to have no performance. . Further, when the molar ratio of the dicarboxylic acid, the tricarboxylic acid or the anhydride (b) thereof is less than 0.2, the content of the unreacted diol compound may increase, and the stability of the alkali-soluble resin composition may decrease with time. Further, when the molar ratio is 1.0 or more, the terminal of the compound represented by the general formula (6) is derived from the acid or acid anhydride, and since the molecular weight of the obtained resin is lowered, the desired properties of the resin are not obtained. Further, the raw material to be added is uniformly dissolved at a reaction temperature of 90 to 130 ° C while the reaction is carried out, and then the reaction is carried out at 40 to 80 ° C and the ripening treatment is preferred.

此外，本發明前述一般式(1)之鹼可溶性樹脂，藉由凝膠滲透色層分析法(GPC)測定之聚苯乙烯換算的數平均分子量以1000以上較佳。分子量較該範圍小時，會有耐鹼性惡化的可能性，光硬化處理後欠缺藉由鹼顯影之圖案，細線圖案之再現性顯著降低。Further, the alkali-soluble resin of the above general formula (1) of the present invention preferably has a polystyrene-equivalent number average molecular weight of 1,000 or more as measured by gel permeation chromatography (GPC). When the molecular weight is smaller than this range, the alkali resistance may be deteriorated, and after the photohardening treatment, the pattern developed by alkali is lacking, and the reproducibility of the fine line pattern is remarkably lowered.

而且，本發明之感光性樹脂組成物，含有前述一般式(1)之鹼可溶性樹脂作為樹脂成份之必須成份。此處，樹脂成份係指藉由聚合或硬化而形成樹脂之成份，含有除樹脂外之低聚物、單體。此外，作為必須成份含有時，係指一般式(1)之鹼可溶性樹脂在樹脂成份中含有20重量%以上，較佳者為30重量%以上，更佳者為50重量%以上。本發明之感光性樹脂組成物，含有以一般式(1)所示之鹼可溶性樹脂作為必須成分，除一般式(1)之樹脂以外的成分，可為樹脂成份，亦可為溶劑或填充材料或著色劑等之非樹脂成份。Further, the photosensitive resin composition of the present invention contains the alkali-soluble resin of the above general formula (1) as an essential component of the resin component. Here, the resin component means a component which forms a resin by polymerization or hardening, and contains an oligomer or a monomer other than the resin. Further, when it is contained as an essential component, the alkali-soluble resin of the general formula (1) is contained in the resin component in an amount of 20% by weight or more, preferably 30% by weight or more, and more preferably 50% by weight or more. The photosensitive resin composition of the present invention contains an alkali-soluble resin represented by the general formula (1) as an essential component, and may be a resin component or a solvent or a filler other than the resin of the general formula (1). Or a non-resin component such as a colorant.

為產生作為感光性樹脂組成物之特徵時，以含有下述(i)～(iii)成份作為必須成份較佳。換言之，含有(i)以前述一般式(1)所示之鹼可溶性樹脂、(ii)在不具羧酸殘基下、至少具有1個以上聚合性不飽和鍵之光聚合性單體、及(iii)光聚合引發劑作為必須成份。In order to produce a characteristic as a photosensitive resin composition, it is preferred to contain the following components (i) to (iii) as essential components. In other words, it contains (i) an alkali-soluble resin represented by the above general formula (1), (ii) a photopolymerizable monomer having at least one polymerizable unsaturated bond in the absence of a carboxylic acid residue, and Iii) A photopolymerization initiator is an essential component.

其中，(ii)成份之至少具有1個以上之聚合性不飽和鍵的光聚合性單體，例如(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸2-乙基己酯等之具有羥基的單體、或二(甲基)丙烯酸乙二醇酯、二(甲基)丙烯酸二乙二醇酯、二(甲基)丙烯酸三乙二醇酯、二(甲基)丙烯酸四乙二醇酯、二(甲基)丙烯酸四甲二醇酯、三(甲基)丙烯酸三羥甲基丙烷酯、三羥甲基乙烷三(甲基)丙烯酸酯、二(甲基)丙烯酸季戊四醇酯、三(甲基)丙烯酸季戊四醇酯、四(甲基)丙烯酸季戊四醇酯、四(甲基)丙烯酸二季戊四醇酯、六(甲基)丙烯酸二季戊四醇酯、(甲基)丙烯酸丙三醇酯等之(甲基)丙烯酸酯類。此等之化合物可使用1種或2種以上。而且，此等之化合物，數平均分子量皆以1000以下較佳。Wherein (ii) a photopolymerizable monomer having at least one polymerizable unsaturated bond of a component, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (A) a monomer having a hydroxyl group such as 2-ethylhexyl acrylate or ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, or triethylenedi(di)methacrylate Alcohol ester, tetraethylene glycol di(meth)acrylate, tetramethyl glycol di(meth)acrylate, trimethylolpropane tri(methyl)acrylate, trimethylolethane tris(methyl Acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate (meth)acrylates such as glycerol (meth)acrylate. These compounds may be used alone or in combination of two or more. Further, these compounds have a number average molecular weight of preferably 1,000 or less.

有關此等(ii)成份與(i)以一般式(1)所示之鹼可溶性樹脂的配合比例[(i)/(ii)]，可為20/80～95/5、較佳者為40/60～90/10。鹼可溶性樹脂之配合比例少時，會產生光硬化後之硬化物變脆，且由於未曝光部中塗膜之酸值降低，對鹼顯影液之溶解性降低，會產生圖案邊緣不清晰的問題。反之，鹼可溶性樹脂之配合比例多於前述範圍時，樹脂中所佔的光反應性官能基之比例少，交聯構造形成時不充分，且樹脂成份中酸值度過高，曝光部對鹼顯影液的溶解性變高，故所形成的圖案較目標之線寬更細，容易產生圖案缺損的問題。The ratio of the components (ii) to (i) the alkali-soluble resin represented by the general formula (1) [(i)/(ii)] may be 20/80 to 95/5, preferably 40/60~90/10. When the blending ratio of the alkali-soluble resin is small, the cured product after photohardening becomes brittle, and since the acid value of the coating film in the unexposed portion is lowered, the solubility to the alkali developing solution is lowered, and the problem that the pattern edge is unclear occurs. . On the other hand, when the blending ratio of the alkali-soluble resin is more than the above range, the proportion of the photoreactive functional group in the resin is small, the crosslinking structure is insufficiently formed, and the acid value in the resin component is too high, and the exposed portion is alkali Since the solubility of the developer becomes high, the pattern formed is thinner than the target line width, and the pattern defect is liable to occur.

另外，成份(iii)之光聚合引發劑，例如苯乙酮、2,2-二乙氧基苯乙酮、p-二甲基苯乙酮、p-二甲基胺基苯丙酮、二氯苯乙酮、三氯苯乙酮、p-第3-丁基苯乙酮等之苯乙酮類、二苯甲酮、2-氯二苯甲酮、p,p’-雙二甲基胺基二苯甲酮等之二苯甲酮類、苯甲基、苯偶因、苯偶因甲醚、苯偶因異丙醚、苯偶因異丁醚等之苯偶因醚類、2-(o-氯化苯基)-4,5-苯基二咪唑、2-(o-氯化苯基)-4,5-二(m-甲氧基苯基)二咪唑、2-(o-氟化苯基)-4,5-二苯基二咪唑、2-(o-甲氧基苯基)-4,5-二苯基二咪唑、2,4,5-三芳基二咪唑等之二咪唑系化合物類、2-三氯甲基-5-苯乙烯基-1,3,4-氧雜二唑、2-三氯甲基-5-(p-氰基苯乙烯基)-1,3,4-氧雜二唑、2-三氯化甲基-5-(p-甲氧基苯乙烯基)-1,3,4-氧雜二唑等之鹵化甲基噻唑化合物類、2,4,6-參(三氯化甲基)-1,3,5-三嗪、2-甲基-4,6-雙(三氯化甲基)-1,3,5-三嗪、2-苯基-4,6-雙(三氯化甲基)-1,3,5-三嗪、2-(4-氯化苯基)-4,6-雙(三氯化甲基)-1,3,5-三嗪、2-(4-甲氧基苯基)-4,6-雙(三氯化甲基)-1,3,5-三嗪、2-(4-甲氧基萘基)-4,6-雙(三氯化甲基)-1,3,5-三嗪、2-(4-甲氧基苯乙烯基)-4,6-雙(三氯化甲基)-1,3,5-三嗪、2-(3,4,5-三甲氧基苯乙烯基)-4,6-雙(三氯化甲基)-1,3,5-三嗪、2-(4-甲基硫代苯乙烯基)-4,6-雙(三氯化甲基)-1,3,5-三嗪等之鹵化甲基-s-三嗪系化合物類、2-(o-苯甲醯基肟)-1-[4-(苯硫基)苯基]-1,2-丁二酮、2-(o-苯甲醯基肟)-1-[4-(苯硫基)苯基]-1,2-戊二酮、2-(o-苯甲醯基肟)-1-[4-(苯硫基)苯基]-1,2-己二酮、2-(o-苯甲醯基肟)-1-[4-(苯硫基)苯基]-1,2-庚二酮、2-(o-苯甲醯基肟)-1-[4-(苯硫基)苯基]-1,2-辛二酮、2-(o-苯甲醯基肟)-1-[4-([甲基苯硫基)苯基]-1,2-丁二酮、2-(o-苯甲醯基肟)-1-[(4-乙基苯硫基)苯基]-1,2-丁二酮、2-(o-苯甲醯基肟)-1-[4-(丁基苯硫基)苯基]-1,2-丁二酮、1-(o-乙醯基肟)-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]乙酮、1-(o-乙醯基肟)-1-[9-甲基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]乙酮、1-(o-乙醯基肟)-1-[9-丙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]乙酮、1-(o-乙醯基肟)-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]乙酮等之o-醯基肟系化合物類、苯甲基二甲基縮酮、噻噸酮、2-氯化噻噸酮、2,4-二乙基噻噸酮、2-甲基噻噸酮、2-異丙基噻噸酮等之硫化合物、2-乙基蒽醌、八甲基蒽醌、1,2-苯并蒽醌、2,3-二苯基蒽醌等之蒽醌類、偶氮雙異丁腈、過氧化苯甲醯基、過氧化枯烯基等之有機過氧化物、2-巰基苯并咪唑、2-巰基苯并噁唑、2-巰基苯并噻唑等之硫醇化合物、三乙醇胺、三乙胺等之三級胺等。此等之光聚合引發劑可使用1種或2種以上。Further, a photopolymerization initiator of the component (iii), such as acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloro Acetophenones such as acetophenone, trichloroacetophenone, p-tert-butylacetophenone, benzophenone, 2-chlorobenzophenone, p,p'-bisdimethylamine Benzophenones such as benzophenones, benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc., 2- (o-chlorophenyl)-4,5-phenyldiimidazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)diimidazole, 2-(o -fluorinated phenyl)-4,5-diphenyldiimidazole, 2-(o-methoxyphenyl)-4,5-diphenyldiimidazole, 2,4,5-triaryldiimidazole, etc. Diimidazole compounds, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-cyanostyryl)- Halogenated methylthiazole compounds such as 1,3,4-oxadiazole, 2-trimethylmethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole , 2,4,6-gin (methyl chloride)-1,3,5-triazine, 2-methyl-4,6-bis(methyl chloride)-1,3,5-three Oxazine, 2-phenyl-4,6-bis (trichloride Methyl)-1,3,5-triazine, 2-(4-chlorophenyl)-4,6-bis(methyl chloride)-1,3,5-triazine, 2-(4 -Methoxyphenyl)-4,6-bis(methyl chloride)-1,3,5-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloro) Methyl)-1,3,5-triazine, 2-(4-methoxystyryl)-4,6-bis(methyl chloride)-1,3,5-triazine, 2 -(3,4,5-trimethoxystyryl)-4,6-bis(methyl chloride)-1,3,5-triazine, 2-(4-methylthiostyryl a halogenated methyl-s-triazine compound such as -4,6-bis(methyl chloride)-1,3,5-triazine, etc., 2-(o-benzhydrylhydrazine)-1 -[4-(phenylthio)phenyl]-1,2-butanedione, 2-(o-benzylidene fluorenyl)-1-[4-(phenylthio)phenyl]-1,2 -pentanedione, 2-(o-benzylidene fluorenyl)-1-[4-(phenylthio)phenyl]-1,2-hexanedione, 2-(o-benzylidene fluorenyl) 1-[4-(phenylthio)phenyl]-1,2-heptanedione, 2-(o-benzylidene fluorenyl)-1-[4-(phenylthio)phenyl]-1 ,2-octanedione, 2-(o-benzylidene fluorenyl)-1-[4-([methylphenylthio)phenyl]-1,2-butanedione, 2-(o-benzene Methyl hydrazide)-1-[(4-ethylphenylthio)phenyl]-1,2-butanedione, 2-(o-benzylidene fluorenyl)-1-[4-(butyl Phenylthio)phenyl]-1,2-butanedione, 1-(o-ethylindenyl)-1-[9 -ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]ethanone, 1-(o-ethylindolyl)-1-[9-methyl-6- (2-Methylbenzylidene)-9H-indazol-3-yl]ethanone, 1-(o-ethylindenyl)-1-[9-propyl-6-(2-methylbenzene Mercapto)-9H-indazol-3-yl]ethanone, 1-(o-ethylindolyl)-1-[9-ethyl-6-(2-methylbenzhydryl)-9H O-mercapto lanthanide compounds such as oxazol-3-yl]ethanone, benzyl dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethyl thiophene Sulfur compounds such as ketone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-ethylhydrazine, octamethylguanidine, 1,2-benzopyrene, 2,3- Organic peroxides such as diphenyl hydrazine and the like, azobisisobutyronitrile, benzammonium peroxide, cumenyl peroxide, etc., 2-mercaptobenzimidazole, 2-mercaptobenzoxime a thiol compound such as azole or 2-mercaptobenzothiazole, a tertiary amine such as triethanolamine or triethylamine, or the like. These photopolymerization initiators may be used alone or in combination of two or more.

(iii)成份之光聚合引發劑的使用量，係以(i)以一般式(1)所示之鹼可溶性樹脂及(ii)光聚合性單體之合計量100重量份為基準，為1～70重量份，較佳者為5～60重量份。(ii)成份之光聚合引發劑的配合比例少時，光聚合之速度變慢，感度降低。反之，過多時，恐會產生感度過強，對圖案光罩而言圖案線寬形成過粗的狀態，無法使線寬忠實地再現，或圖案邊緣不清晰的問題。而且，(iii)之光聚合引發劑中包含同時光增感作用者時，不一定必須另外添加光增感劑。(iii) The amount of the photopolymerization initiator to be used is (i) based on 100 parts by weight of the total of the alkali-soluble resin represented by the general formula (1) and (ii) the photopolymerizable monomer. ～70 parts by weight, preferably 5 to 60 parts by weight. When the mixing ratio of the photopolymerization initiator of the component (ii) is small, the speed of photopolymerization is slow, and the sensitivity is lowered. On the other hand, when there is too much, there is a fear that the sensitivity is too strong, the pattern line width is excessively thick in the pattern mask, the line width cannot be faithfully reproduced, or the pattern edges are not clear. Further, when the photopolymerization initiator of (iii) contains a simultaneous photosensitizing effect, it is not always necessary to additionally add a photosensitizer.

含有以(i)成份之以一般式(1)所示之鹼可溶性樹脂、(ii)成分之光聚合性單體、及(iii)成分之光聚合引發劑作為必須成分之感光性樹脂組成物，對於濾色器油墨、保護膜等之濾色器用材料等有用，視其所需可溶解於下述所記載的溶劑中，且配合各種添加劑使用。Photosensitive resin composition containing an alkali-soluble resin represented by the general formula (1), a photopolymerizable monomer of the component (ii), and a photopolymerization initiator of the component (iii) as an essential component It is useful for a color filter material such as a color filter ink or a protective film, and can be dissolved in a solvent described below as needed, and used in combination with various additives.

將本發明之感光性樹脂組成物使用於濾色器用等時，除前述各成份外，以使用溶劑較佳。溶劑例如甲醇、乙醇、正丙醇、異丙醇、乙二醇、丙二醇等之醇類、α-或β-萜品醇等之萜烯類、丙酮、甲基乙酮、環己酮、N-甲基-2-吡咯烷酮等之酮類、甲苯、二甲苯、四甲苯等之芳香族烴類、溶纖劑、甲基溶纖劑、乙基溶纖劑、卡必醇、甲基卡必醇、乙基卡必醇、丁基卡必醇、丙二醇單甲醚、丙二醇單***、二丙二醇單甲醚、二丙二醇單***、三乙二醇單甲醚、三乙二醇單***等之醇醚類、乙酸乙酯、乙酸丁酯、溶纖劑乙酸酯、乙基溶纖劑乙酸酯、丁基溶纖劑乙酸酯、卡必醇乙酸酯、乙基卡必醇乙酸酯、丁基卡必醇乙酸酯、丙二醇單甲醚乙酸酯、丙二醇單***乙酸酯等之乙酸酯等，使用此等，藉由溶解、混合，可形成均勻的溶液狀組成物。When the photosensitive resin composition of the present invention is used for a color filter or the like, it is preferred to use a solvent in addition to the above components. Solvents such as alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, terpenes such as α- or β-terpineol, acetone, methyl ethyl ketone, cyclohexanone, N -ketones such as methyl-2-pyrrolidone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, and methyl carbene Alcohol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, etc. Alcohol ethers, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate An acetate or the like such as butyl carbitol acetate, propylene glycol monomethyl ether acetate or propylene glycol monoethyl ether acetate can be used to form a uniform solution-like composition by dissolving and mixing.

而且，於本發明之感光性樹脂組成物中，視其所需可配合硬化促進劑、熱聚合禁止劑、可塑劑、填充材料、溶劑、整平劑、消泡劑等之添加劑。其中，熱聚合禁止劑例如氫醌、氫醌單甲醚、焦培酚、第3-丁基兒茶酚、吩噻嗪等。可塑劑例如苯二甲酸二丁酯、苯二甲酸二辛酯、三甲苯酚基等。填充材料例如玻璃纖維、二氧化矽、雲母、氧化鋁等。此外，消泡劑或整平劑例如矽系、氟系、丙烯酸系化合物。Further, in the photosensitive resin composition of the present invention, an additive such as a hardening accelerator, a thermal polymerization inhibiting agent, a plasticizer, a filler, a solvent, a leveling agent, an antifoaming agent or the like may be blended as needed. Among them, thermal polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, pyrophenol, 3-butyl catechol, phenothiazine and the like. Plasticizers such as dibutyl phthalate, dioctyl phthalate, trimethyl phenolate, and the like. Filling materials such as glass fiber, cerium oxide, mica, alumina, and the like. Further, an antifoaming agent or a leveling agent such as a lanthanide, a fluorine-based or an acrylic compound is used.

本發明之感光性樹脂組成物，係於除去溶劑之固成分(固成分包含硬化後形成固成分之單體)中，以一般式(1)所示之鹼可溶性樹脂、(ii)之光聚合性單體及(iii)光聚合引發劑，含有黑色或其他顏色之顏料時，合計量為含有10重量%以上(較佳者為20重量%以上、更佳者為30重量%以上)，不含顏料時含有30重量%以上(較佳者為40重量%以上、更佳者為50重量%以上)。溶劑之量係藉由目標之黏度予以變化，相對於全體量而言以20～80重量%之範圍為宜。本發明之感光性樹脂組成物作為濾色器用時，適合於保護膜用途。The photosensitive resin composition of the present invention is obtained by removing a solid component of a solvent (a solid component comprises a monomer which forms a solid component after curing), an alkali-soluble resin represented by the general formula (1), and (ii) photopolymerization. When the monomer and the photopolymerization initiator (iii) contain a pigment of black or other color, the total amount is 10% by weight or more (preferably 20% by weight or more, more preferably 30% by weight or more), When the pigment is contained, it is contained in an amount of 30% by weight or more (preferably 40% by weight or more, and more preferably 50% by weight or more). The amount of the solvent is changed by the viscosity of the target, and is preferably in the range of 20 to 80% by weight based on the total amount. When the photosensitive resin composition of the present invention is used as a color filter, it is suitable for use as a protective film.

本發明之塗膜(硬化物)，例如藉由在基板上塗佈前述之感光性樹脂組成物的溶液並予以乾燥，照射光(包含紫外線、放射線等)，予以硬化而製得。設置照射光的部分與未照射的部分，僅使照射光的部分進行硬化，使其他的部分以鹼溶液溶解時，可得所期待的圖案之塗膜。The coating film (cured material) of the present invention is obtained by, for example, applying a solution of the above-mentioned photosensitive resin composition onto a substrate, drying it, irradiating light (including ultraviolet rays, radiation, etc.), and curing it. The portion where the irradiation light is provided and the portion not irradiated are cured only when the portion irradiated with light is irradiated, and when the other portion is dissolved in the alkali solution, a coating film of a desired pattern can be obtained.

其次，說明有關使用感光性樹脂組成物之濾色器的製造方法。首先，在基板的表面上塗佈感光性樹脂組成物後，進行預烘烤以使溶劑蒸發，形成塗膜。然後，在該塗膜上經由光罩予以曝光後，使用鹼性顯影液進行顯影，使塗膜之未曝光部分溶解除去，再藉由後烘烤處理，製得在使形成畫素的部分分劃下所形成的黑色矩陣。在該基板上塗佈例如分散有紅色顏料之感光性樹脂組成物的液狀組成物後，進行預烘烤處理以使溶劑蒸發，形成塗膜。然後，在該塗膜上經由光罩進行曝光後，使用鹼性顯影液進行顯影，溶解除去塗膜之未曝光部分，然後，藉由後烘烤處理，形成以所定配列配置有紅色畫素圖案之畫素列。然後，藉由使用分散有綠色或藍色顏料的感光性樹脂組成物之液狀組成物，與前述相同地，進行各液狀組成物之塗佈、預烘烤、曝光、顯影及後烘烤處理，在同一基板上順序形成綠色畫素列及藍色畫素列，在基板上配置紅色、綠色及藍色等三原色之畫素列，然後，與前述相同地，於其上使作為保護膜之感光性樹脂組成物之液狀組成物進行各液狀組成物之塗佈、預烘烤、曝光、顯影及後烘烤處理，製得形成有保護膜之濾色器。Next, a method of producing a color filter using a photosensitive resin composition will be described. First, after coating the photosensitive resin composition on the surface of the substrate, prebaking is performed to evaporate the solvent to form a coating film. Then, after exposure on the coating film through a photomask, development is carried out using an alkaline developing solution to dissolve and remove the unexposed portion of the coating film, and then the post-baking treatment is performed to obtain a portion in which the pixel is formed. Draw down the resulting black matrix. A liquid composition such as a photosensitive resin composition in which a red pigment is dispersed is applied onto the substrate, and then pre-baked to evaporate the solvent to form a coating film. Then, after exposure to the coating film via a photomask, development is carried out using an alkaline developing solution to dissolve and remove the unexposed portion of the coating film, and then, by post-baking treatment, a red pixel pattern is arranged in a predetermined arrangement. The picture is prime. Then, by using a liquid composition of a photosensitive resin composition in which a green or blue pigment is dispersed, coating, prebaking, exposure, development, and post-baking of each liquid composition are carried out in the same manner as described above. In the process, a green pixel sequence and a blue pixel sequence are sequentially formed on the same substrate, and a pixel sequence of three primary colors such as red, green, and blue is disposed on the substrate, and then, as described above, a protective film is formed thereon. The liquid composition of the photosensitive resin composition is subjected to coating, prebaking, exposure, development, and post-baking treatment of each liquid composition to obtain a color filter in which a protective film is formed.

於基板上塗佈感光性樹脂組成物時，除習知的溶液浸漬法、噴霧法外、可採用滾筒塗佈機、溢料塗佈機或旋轉機的方法等之任何方法。藉由此等之方法，以所期待的厚度進行塗佈後，除去溶劑(預烘烤)，形成被膜。預烘烤處理可藉由烤箱、熱板等之加熱、真空乾燥或組合此等進行。預烘烤之加熱溫度及加熱時間，係視使用的溶劑予以適當選擇，例如在80～120℃之溫度下進行1～10分鐘。When the photosensitive resin composition is applied onto the substrate, any method such as a roll coater, a flash coater, or a rotary machine may be employed in addition to the conventional solution dipping method and spray method. After coating by the desired thickness, the solvent is removed (prebaking) to form a film. The prebaking treatment can be carried out by heating with an oven, a hot plate or the like, vacuum drying or a combination thereof. The heating temperature and the heating time of the prebaking are appropriately selected depending on the solvent to be used, for example, at a temperature of 80 to 120 ° C for 1 to 10 minutes.

製作濾色器時所使用的放射線，例如可使用可見光線、紫外線、遠紫外線、電子線、X光線等，以波長為250～450nm之範圍的放射線較佳。而且，適合該鹼顯影處理之顯影液，例如鹼金屬或鹼土類金屬之碳酸鹽水溶液、鹼金屬之氫氧化物水溶液等，特別是使用含有0.05～10重量%之碳酸鈉、碳酸鉀、碳酸鋰等碳酸鹽之弱鹼性水溶液，在20～30℃之溫度下進行顯影，使用市售的顯影機或超音波洗淨機等，精密地形成微細的影像。而且，通常於鹼顯影處理後進行水洗。顯影處理法可使用沖洗顯影法、噴霧顯影法、浸漬(dip)顯影法、漿料(液盛)顯影法等。顯影條件、以在常溫下進行10～120秒較佳。For the radiation used in the production of the color filter, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used, and radiation having a wavelength of 250 to 450 nm is preferable. Further, a developing solution suitable for the alkali development treatment, for example, an aqueous solution of an alkali metal or an alkaline earth metal carbonate, an aqueous solution of an alkali metal hydroxide, or the like, in particular, a sodium carbonate, potassium carbonate or lithium carbonate containing 0.05 to 10% by weight. The weakly alkaline aqueous solution of the carbonate is developed at a temperature of 20 to 30 ° C, and a fine image is precisely formed using a commercially available developing machine or an ultrasonic cleaner. Further, water washing is usually carried out after the alkali development treatment. As the development treatment method, a rinse development method, a spray development method, a dip development method, a slurry (liquid growth) development method, or the like can be used. The developing conditions are preferably 10 to 120 seconds at normal temperature.

於該顯影處理後，以180～250℃之溫度及20～100分鐘之條件進行熱處理(後烘烤)。該後烘烤處理以為提高經圖案化的塗膜與基板之密接性等為目的時進行。此係與預烘烤處理相同地，藉由烤箱、熱板等加熱予以進行。本發明之經圖案化的塗膜，經由藉由前述之微影術之各步驟予以形成。After the development treatment, heat treatment (post-baking) is carried out at a temperature of 180 to 250 ° C and a condition of 20 to 100 minutes. This post-baking treatment is performed for the purpose of improving the adhesion between the patterned coating film and the substrate. This is carried out by heating in an oven, a hot plate or the like in the same manner as the prebaking treatment. The patterned coating film of the present invention is formed by the respective steps of the aforementioned lithography.

形成具備畫素及/或黑色矩陣之濾色器時所使用的基板，例如玻璃、透明薄膜(例如聚碳酸酯、聚對苯二甲酸乙二酯、聚醚碸等)等。而且，在此等之基板上視其所需可實施賦予透明電極層、藉由矽烷偶合劑等之藥品處理、電漿處理、離子塗佈法、濺射法、氣相反應法、真空蒸鍍法等之適當的前處理。A substrate used for forming a color filter having a pixel and/or a black matrix, such as glass or a transparent film (for example, polycarbonate, polyethylene terephthalate, polyether oxime, etc.). Further, on these substrates, a transparent electrode layer, a drug treatment by a decane coupling agent, a plasma treatment, an ion coating method, a sputtering method, a gas phase reaction method, and a vacuum evaporation method can be carried out as needed. Appropriate pre-processing of the law.

[發明效果][Effect of the invention]

本發明之感光性樹脂組成物，由於含有以一般式(1)所示之鹼可溶性樹脂，與習知品相比時，對鹼顯影液之溶解性高，且對紫外線或電子線照射而言進行充分的光硬化處理。換言之，由於紫外線或電子線照射後之硬化部與未硬化部對鹼顯影液的溶解度差變大，即使於薄膜或高著色劑濃度中仍可形成微細的圖案。因此，本發明之感光性樹脂組成物適合使用於形成濾色器時，特別是適合作為濾色器保護膜材料。而且，如此所得的濾色器，例如於透過型、反射型、或半透過型彩色液晶顯示裝置、彩色攝影管元件、彩色感應器等極為有用。The photosensitive resin composition of the present invention contains an alkali-soluble resin represented by the general formula (1), and has a high solubility in an alkali developing solution when compared with a conventional product, and is sufficiently effective for ultraviolet light or electron beam irradiation. Light hardening treatment. In other words, since the difference in solubility between the hardened portion and the uncured portion after irradiation with ultraviolet rays or electron beams becomes large, a fine pattern can be formed even in the film or high colorant concentration. Therefore, the photosensitive resin composition of the present invention is suitably used as a color filter protective film material when it is used to form a color filter. Further, the color filter thus obtained is extremely useful, for example, in a transmissive, reflective, or transflective color liquid crystal display device, a color photographic tube element, a color sensor, and the like.

於下述中，以實施例及比較例為基準，更詳細地說明本發明。而且，本發明之範圍不受此等實施例及比較例所限制。此外，於下述實施例等之樹脂評估，沒有特別限制時，如下述進行。In the following, the present invention will be described in more detail on the basis of examples and comparative examples. Moreover, the scope of the invention is not limited by the embodiments and the comparative examples. Further, in the evaluation of the resin in the following examples and the like, there is no particular limitation, and the following is carried out.

[實施例][Examples]

[固成份濃度][solid concentration]

使1g實施例(包含比較例)所得的樹脂溶液(以下包含反應生成物或鹼可溶性樹脂)含浸於玻璃濾色器[重量：W0 (g)]中，予以稱重[W1 (g)]，由在160℃下進行加熱2小時後之重量，藉由下式求取。1 g of the resin solution (including the reaction product or the alkali-soluble resin) obtained in the example (including the comparative example) was impregnated into a glass filter [weight: W 0 (g)], and weighed [W 1 (g) ], the weight after heating at 160 ° C for 2 hours was obtained by the following formula.

固成份(%)=100×(W2 -W0 )/(W1 -W0 )Solid component (%) = 100 × (W 2 - W 0 ) / (W 1 - W 0 )

[酸值][acid value]

使樹脂溶液溶解於二噁烷中，以酚酞因作為指示劑，以1/10N-KOH水溶液進行滴定。The resin solution was dissolved in dioxane, and phenolphthalein was used as an indicator to titrate with a 1/10 N-KOH aqueous solution.

[分子量][molecular weight]

以四氫呋喃作為展開溶劑，以凝膠滲透色層分析法(GPC)、標準聚苯乙烯換算值所求得的數平均分子量(Mn)之值。The value of the number average molecular weight (Mn) obtained by gel permeation chromatography (GPC) and standard polystyrene conversion value using tetrahydrofuran as a developing solvent.

此外，實施例中使用的簡稱如下所述。Further, the abbreviations used in the examples are as follows.

BPFE：雙酚芴型環氧樹脂(一般式(7)中，R1 、R2 、R3 及R4 為氫原子，X為9,9-芴二基，m為0之化合物)BPFE: bisphenol fluorene type epoxy resin (in the general formula (7), R 1 , R 2 , R 3 and R 4 are a hydrogen atom, X is a 9,9-fluorenyl group, and m is a compound of 0)

HOA-MS:(共榮社化學公司製、LIGHT-ACRYLATE HOA-MS(一般式(9)中、R6 為伸乙基、R7 為氫原子、R8 為伸乙基、及p為1之化合物)HOA-MS: (produced by Kyoeisha Chemical Co., Ltd., LIGHT-ACRYLATE HOA-MS (in general formula (9), R 6 is an exoethyl group, R 7 is a hydrogen atom, R 8 is an exoethyl group, and p is 1 Compound)

HOA-HH:(共榮社化學公司製、LIGHT-ACRYLATE HOA-HH(一般式(9)中、R6 為伸乙基、R7 為氫原子、R8 為1,2-環伸己基、及p為1之化合物)HOA-HH: (produced by Kyoeisha Chemical Co., Ltd., LIGHT-ACRYLATE HOA-HH (in general formula (9), R 6 is an ethyl group, R 7 is a hydrogen atom, and R 8 is a 1,2-cyclohexyl group. And p is a compound of 1)

HOA-MPL:(共榮社化學公司製、LIGHT-ACRYLATE HOA-MPL(一般式(9)中、R6 為伸乙基、R7 為氫原子、R8 為1,2-亞苯基、及p為1之化合物)HOA-MPL: LIGHT-ACRYLATE HOA-MPL (general formula (9), R 6 is an ethyl group, R 7 is a hydrogen atom, and R 8 is a 1,2-phenylene group. And p is a compound of 1)

BPDA: 3,3’,4,4’-聯苯四羧酸二酐BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride

THPA: 1,2,3,6-四氫苯二甲酸酐THPA: 1,2,3,6-tetrahydrophthalic anhydride

TPP：三苯基膦TPP: triphenylphosphine

PGMEA：丙二醇單甲醚乙酸酯PGMEA: propylene glycol monomethyl ether acetate

[實施例1][Example 1]

在1000ml附有回流冷卻器之四口燒瓶中加入200.00g(0.44mol)之BPFE、186.96g(0.86mol)之HOA-MS、386.96g之PGMEA及1.14g之TPP，在90～100℃下加熱，進行加熱攪拌14小時，製得反應生成物(A)(二醇化合物)。200.00 g (0.44 mol) of BPFE, 186.96 g (0.86 mol) of HOA-MS, 386.96 g of PGMEA and 1.14 g of TPP were added to a 1000 ml four-necked flask equipped with a reflux cooler, and heated at 90 to 100 ° C. The mixture was heated and stirred for 14 hours to obtain a reaction product (A) (diol compound).

然後，在該反應生成物(A)中加入63.61g(0.22mol)之BPDA[(a)成份]及32.89g(0.22mol)之THPA[(b)成份]，在100～120℃下進行攪拌4小時予以反應，合成鹼可溶性樹脂(1)-1。所得的鹼可溶性樹脂之固成份為55.6%，酸值(固成份換算)為75.2mgKOH/g，藉由GPC分析之Mn為1400。而且，實施例1之鹼可溶性樹脂(1)-1合成時所使用的(A)、(a)及(b)成份及配合比例、以及所得的鹼可溶性樹脂(1)-1之數平均分子量及酸值，如表1所示(有關下述之實施例及參考例亦相同)。Then, 63.61 g (0.22 mol) of BPDA [(a) component] and 32.89 g (0.22 mol) of THPA [(b) component] were added to the reaction product (A), and the mixture was stirred at 100 to 120 °C. The reaction was carried out for 4 hours to synthesize an alkali-soluble resin (1)-1. The obtained alkali-soluble resin had a solid content of 55.6%, an acid value (converted solid content) of 75.2 mgKOH/g, and an Mn of 1400 by GPC analysis. Further, the components (A), (a) and (b) used in the synthesis of the alkali-soluble resin (1)-1 of Example 1 and the mixing ratio thereof, and the number average molecular weight of the obtained alkali-soluble resin (1)-1 The acid value is shown in Table 1 (the same applies to the following examples and reference examples).

[實施例2][Embodiment 2]

在1000ml附有回流冷卻器之四口燒瓶中加入200.00g(0.44mol)之BPFE、186.96g(0.86mol)之HOA-MS、386.96g之PGMEA及1.14g之TPP，在90～100℃下加熱，進行加熱攪拌14小時，製得反應生成物(A)(二醇化合物)。200.00 g (0.44 mol) of BPFE, 186.96 g (0.86 mol) of HOA-MS, 386.96 g of PGMEA and 1.14 g of TPP were added to a 1000 ml four-necked flask equipped with a reflux cooler, and heated at 90 to 100 ° C. The mixture was heated and stirred for 14 hours to obtain a reaction product (A) (diol compound).

然後，在該反應生成物(A)中加入25.44g(0.09mol)之BPDA[(a)成份]及32.89g(0.22mol)之THPA[(b)成份]，在100～120℃下進行攪拌4小時予以反應，合成鹼可溶性樹脂(1)-2。所得的鹼可溶性樹脂之固成份為53.6%，酸值(固成份換算)為49.0mgKOH/g，藉由GPC分析之Mn為1200。Then, 25.44 g (0.09 mol) of BPDA [(a) component] and 32.89 g (0.22 mol) of THPA [(b) component] were added to the reaction product (A), and the mixture was stirred at 100 to 120 °C. The reaction was carried out for 4 hours to synthesize an alkali-soluble resin (1)-2. The obtained alkali-soluble resin had a solid content of 53.6%, an acid value (solid content conversion) of 49.0 mgKOH/g, and an Mn of 1200 by GPC analysis.

[實施例3][Example 3]

在1000ml附有回流冷卻器之四口燒瓶中加入200.00g(0.44mol)之BPFE、186.96g(0.86mol)之HOA-MS、386.96g之PGMEA及1.14g之TPP，在90～100℃下加熱，進行加熱攪拌14小時，製得反應生成物(A)(二醇化合物)。200.00 g (0.44 mol) of BPFE, 186.96 g (0.86 mol) of HOA-MS, 386.96 g of PGMEA and 1.14 g of TPP were added to a 1000 ml four-necked flask equipped with a reflux cooler, and heated at 90 to 100 ° C. The mixture was heated and stirred for 14 hours to obtain a reaction product (A) (diol compound).

然後，在該反應生成物(A)中加入63.61g(0.22mol)之BPDA[(a)成份]及13.16g(0.22mol)之THPA[(b)成份]，在100～120℃下進行攪拌4小時予以反應，合成鹼可溶性樹脂(1)-3。所得的鹼可溶性樹脂之固成份為54.6%，酸值(固成份換算)為75.2mgKOH/g，藉由GPC分析之Mn為1400。Then, 63.61 g (0.22 mol) of BPDA [(a) component] and 13.16 g (0.22 mol) of THPA [(b) component] were added to the reaction product (A), and the mixture was stirred at 100 to 120 °C. The reaction was carried out for 4 hours to synthesize an alkali-soluble resin (1)-3. The obtained alkali-soluble resin had a solid content of 54.6%, an acid value (converted solid content) of 75.2 mgKOH/g, and an Mn of 1400 by GPC analysis.

[實施例4][Example 4]

在1000ml附有回流冷卻器之四口燒瓶中加入160.00g(0.35mol)之BPFE、186.99g(0.69mol)之HOA-HH、346.98g之PGMEA及0.91g之TPP，在90～100℃下加熱，進行加熱攪拌16小時，製得反應生成物(A)(二醇化合物)。In a 1000 ml four-necked flask equipped with a reflux cooler, 160.00 g (0.35 mol) of BPFE, 186.99 g (0.69 mol) of HOA-HH, 346.98 g of PGMEA and 0.91 g of TPP were added and heated at 90 to 100 °C. The mixture was heated and stirred for 16 hours to obtain a reaction product (A) (diol compound).

然後，在該反應生成物(A)中加入50.89g(0.17mol)之BPDA[(a)成份]及26.32g(0.17mol)之THPA[(b)成份]，在100～120℃下進行攪拌6小時予以反應，合成鹼可溶性樹脂(1)-4。所得的鹼可溶性樹脂之固成份為55.1%，酸值(固成份換算)為68.6mgKOH/g，藉由GPC分析之Mn為1510。Then, 50.89 g (0.17 mol) of BPDA [(a) component] and 26.32 g (0.17 mol) of THPA [(b) component] were added to the reaction product (A), and the mixture was stirred at 100 to 120 °C. The reaction was carried out for 6 hours to synthesize an alkali-soluble resin (1)-4. The obtained alkali-soluble resin had a solid content of 55.1%, an acid value (converted solid content) of 68.6 mgKOH/g, and an Mn of 1510 by GPC analysis.

[實施例5][Example 5]

在1000ml附有回流冷卻器之四口燒瓶中加入165.00g(0.36mol)之BPFE、188.52g(0.71mol)之HOA-MPL、353.52g之PGMEA及0.94g之TPP，在90～100℃下加熱，進行加熱攪拌16小時，製得反應生成物(A)(二醇化合物)。165.00 g (0.36 mol) of BPFE, 188.52 g (0.71 mol) of HOA-MPL, 353.52 g of PGMEA and 0.94 g of TPP were added to a 1000 ml four-necked flask equipped with a reflux condenser, and heated at 90 to 100 ° C. The mixture was heated and stirred for 16 hours to obtain a reaction product (A) (diol compound).

然後，在該反應生成物(A)中加入52.48g(0.18mol)之BPDA[(a)成份]及27.14g(0.18mol)之THPA[(b)成份]，在100～120℃下進行攪拌6小時予以反應，合成鹼可溶性樹脂(1)-5。所得的鹼可溶性樹脂之固成份為55.1%，酸值(固成份換算)為69.2mgKOH/g，藉由GPC分析之Mn為1570。Then, 52.48 g (0.18 mol) of BPDA [(a) component] and 27.14 g (0.18 mol) of THPA [(b) component] were added to the reaction product (A), and the mixture was stirred at 100 to 120 °C. The reaction was carried out for 6 hours to synthesize an alkali-soluble resin (1)-5. The obtained alkali-soluble resin had a solid content of 55.1%, an acid value (solid content conversion) of 69.2 mgKOH/g, and an Mn of 1570 by GPC analysis.

[參考例1][Reference Example 1]

在1000ml附有回流冷卻器之四口燒瓶中加入240.00g(0.52mol)之BPFE、74.78g(1.04mol)之丙烯酸、362.00g之PGMEA及1.36g之TPP，在90～100℃下加熱，進行加熱攪拌12小時，製得反應生成物(A)(二醇化合物)。In a 1000 ml four-necked flask equipped with a reflux condenser, 240.00 g (0.52 mol) of BPFE, 74.78 g (1.04 mol) of acrylic acid, 362.00 g of PGMEA and 1.36 g of TPP were added and heated at 90 to 100 ° C. The mixture was heated and stirred for 12 hours to obtain a reaction product (A) (diol compound).

然後，在該反應生成物(A)中加入76.31g(0.26mol)之BPDA[(a)成份]及39.46g(0.26mol)之THPA[(b)成份]，在100～120℃下進行攪拌4小時予以反應，合成鹼可溶性樹脂(參考例)-1。所得的鹼可溶性樹脂之固成份為54.8%，酸值(固成份換算)為106.8mgKOH/g，藉由GPC分析之Mn為1400。Then, 76.31 g (0.26 mol) of BPDA [(a) component] and 39.46 g (0.26 mol) of THPA [(b) component] were added to the reaction product (A), and the mixture was stirred at 100 to 120 °C. The reaction was carried out for 4 hours to synthesize an alkali-soluble resin (Reference Example)-1. The obtained alkali-soluble resin had a solid content of 54.8%, an acid value (converted solid content) of 106.8 mgKOH/g, and an Mn of 1400 by GPC analysis.

[實施例6～10、比較例1][Examples 6 to 10, Comparative Example 1]

其次，以製造濾色器之實施例及比較例為基準，具體地說明本發明。而且，本發明不受此等所限制。此處，製造實施例及比較例之濾色器時所使用的原料及簡稱如下所述。Next, the present invention will be specifically described on the basis of examples and comparative examples for producing a color filter. Moreover, the invention is not limited by these. Here, the raw materials and abbreviations used in the production of the color filters of the examples and the comparative examples are as follows.

(i)成分：(1)-1～(1)-5、及(參考)-1[以前述實施例1～5及參考例1所得的鹼可溶性樹脂](i) components: (1)-1 to (1)-5, and (reference)-1 [the alkali-soluble resin obtained by the above Examples 1 to 5 and Reference Example 1]

(ii)成分：六丙烯酸二季戊四醇酯(ii) Ingredients: dipentaerythritol hexaacrylate

(iii)成分：肟酯系光聚合引發劑(千葉‧日本製、IRGACURE OXE02)(iii) Component: oxime ester photopolymerization initiator (Chiba ‧ made in Japan, IRGACURE OXE02)

(iv)成分：四甲基聯苯型環氧樹脂(iv) Component: tetramethylbiphenyl type epoxy resin

溶劑：溶纖劑乙酸酯Solvent: cellosolve acetate

藉由以表2所示之比例配合前述配合成份[(i)、(ii)及(iii)]，調製使用前述實施例1～5所得的鹼可溶性樹脂之感光性樹脂組成物(實施例6～10)、及使用參考例1所得的鹼可溶性樹脂之感光性樹脂組成物(比較例1)。The photosensitive resin composition using the alkali-soluble resin obtained in the above Examples 1 to 5 was prepared by blending the above-mentioned compounding ingredients [(i), (ii) and (iii)] in the ratio shown in Table 2 (Example 6) ～10) and a photosensitive resin composition using the alkali-soluble resin obtained in Reference Example 1 (Comparative Example 1).

然後，使用旋轉塗佈器，在125mm×125mm之玻璃基板上、以後烘烤處理後之膜厚為2μm下塗佈前述實施例1～5所得的鹼可溶性樹脂之感光性樹脂組成物(實施例6～10)，在90℃下進行預烘烤處理2分鐘，作成塗佈板。然後，經由圖案光罩、以500W/cm2 之高壓水銀燈、波長365nm之照度10mW/cm2 之紫外線進行照射10秒，進行感光部分之光硬化反應。其次，使該經曝光完成的塗佈板在1重量%碳酸鈉水溶液中，於25℃下確認所期待的圖案後，再進行顯影處理20秒及水洗，除去塗膜之未曝光部分。然後，使用熱風乾燥機，在230℃下進行加熱乾燥處理30分鐘，製得試驗用濾色器。評估實施例6～10、及比較例1之試驗用濾色器之顯影性、顯影密接性等。具體而言，有關所得的試料，評估塗膜之乾燥性、對鹼水溶液之顯影性、曝光感度、塗膜硬度、與基板之密接性、耐熱性、耐藥品性。結果如表3所示。而且，以下述條件測定各種物性數據。Then, the photosensitive resin composition of the alkali-soluble resin obtained in the above Examples 1 to 5 was applied onto a glass substrate of 125 mm × 125 mm and a film thickness of 2 μm after the subsequent baking treatment using a spin coater (Example) 6 to 10), prebaking treatment was carried out at 90 ° C for 2 minutes to prepare a coating plate. Then, the photocuring reaction of the photosensitive portion was carried out by irradiating with a pattern mask, a high-pressure mercury lamp of 500 W/cm 2 , and an ultraviolet light having an illuminance of 10 mW/cm 2 at a wavelength of 365 nm for 10 seconds. Next, the exposed coating plate was confirmed to have a desired pattern in a 1% by weight aqueous sodium carbonate solution at 25° C., and then subjected to development treatment for 20 seconds and water washing to remove the unexposed portion of the coating film. Then, heat drying was performed at 230 ° C for 30 minutes using a hot air dryer to obtain a test color filter. The developability, development adhesion, and the like of the color filters for tests of Examples 6 to 10 and Comparative Example 1 were evaluated. Specifically, the obtained sample was evaluated for drying properties of the coating film, developability to an aqueous alkali solution, exposure sensitivity, coating film hardness, adhesion to a substrate, heat resistance, and chemical resistance. The results are shown in Table 3. Further, various physical property data were measured under the following conditions.

(1)　塗膜之乾燥性(1) Dryness of the coating film

塗膜之乾燥性係以JIS-K5400為基準進行評估。評估順序如下所述。The drying property of the coating film was evaluated based on JIS-K5400. The evaluation order is as follows.

○：完全沒有皺摺者○: No wrinkles at all

△：稍有皺摺者△: slightly wrinkled

×：有顯著皺摺者×: There are significant wrinkles

(2)　對鹼水溶液之顯影性(2) Developability of an aqueous alkali solution

在1重量%之碳酸鈉水溶液中，於25℃下使圖案顯影後，浸漬20秒以進行顯影處理。顯影後擴大40倍，以目視評估殘存的樹脂。評估順序如下所述。The pattern was developed in a 1% by weight aqueous sodium carbonate solution at 25 ° C, and then immersed for 20 seconds to carry out development treatment. After development, the magnification was 40 times, and the residual resin was visually evaluated. The evaluation order is as follows.

○：顯影性良好者(在玻璃上完全沒有光阻殘留者)○: Those with good developability (there is no photoresist remaining on the glass)

△：顯影性稍微不佳(在玻璃上僅稍有光阻殘留者)△: The developability is slightly poor (only a slight photoresist remains on the glass)

×：顯影性不佳(在玻璃上少許光阻殘留者)×: poor developability (a little photoresist residue on the glass)

(3)　曝光感度(3) Exposure sensitivity

使具有10μm細線圖案之曝光光罩與塗膜密接，使用500W高壓水銀燈，以100mJ/cm2 之光量進行照射，然後，以與對鹼水溶液之顯影性評估相同的操作方法，藉由顯影處理形成細線圖案，以測長顯微鏡測定細線之線寬(該評估法中，具有高感度時線寬變粗)。The exposure mask having a fine line pattern of 10 μm was adhered to the coating film, irradiated with a light amount of 100 mJ/cm 2 using a 500 W high pressure mercury lamp, and then formed by development processing in the same manner as the evaluation of the developability of the aqueous alkali solution. The thin line pattern is used to measure the line width of the thin line by a length measuring microscope (in this evaluation method, the line width becomes thick when there is a high sensitivity).

(4)　塗膜硬度(4) Film hardness

於曝光顯影後，在230℃下進行加熱30分鐘的塗膜之硬度以JIS-K5400之試驗法為基準，使用鉛筆硬度試驗機，施加1kg之荷重時之塗膜沒有刮傷之最高硬度表示。使用的鉛筆為「三菱Hi-Uni」。After the exposure and development, the hardness of the coating film which was heated at 230 ° C for 30 minutes was expressed by the pencil hardness tester using the pencil hardness tester, and the maximum hardness of the coating film without scratching when a load of 1 kg was applied. The pencil used is "Mitsubishi Hi-Uni".

(5)　與基板之密接性(5) Adhesion to the substrate

於後烘烤處理後，對在120℃、2氣壓下進行PCT處理5小時之塗膜而言，在至少作成100個棋盤格子之交叉切割，然後，使用Cellotape(註冊商標)進行剝離試驗，藉由目視評估棋盤格子之剝離狀態。評估順序如下所述。After the post-baking treatment, the coating film subjected to PCT treatment for 5 hours at 120 ° C and 2 atmospheres was cross-cut at least 100 checkerboard grids, and then peel test was performed using Cellotape (registered trademark). The peeling state of the checkerboard grid was visually evaluated. The evaluation order is as follows.

○：完全沒有剝離者○: There is no stripper at all

△：約半數被剝離者△: About half of the people who were stripped

×：沒有殘膜者×: no residual film

(6)　耐熱性(6) Heat resistance

於曝光顯影後，將在230℃下進行加熱的塗膜放入250℃之烤箱3小時，評估塗膜之狀態。評估順序如下所述。After the exposure and development, the coating film heated at 230 ° C was placed in an oven at 250 ° C for 3 hours, and the state of the coating film was evaluated. The evaluation order is as follows.

○：塗膜外觀沒有異常者○: There is no abnormality in the appearance of the coating film.

×：塗膜之外觀有割裂、剝離、著色情形×: The appearance of the coating film is split, peeled, and colored.

(7)　耐藥品性(7) Chemical resistance

於曝光顯影後，使在230℃下進行加熱30分鐘之塗膜，在下述之藥品中以下述條件浸漬，評估浸漬後之外觀及密接性。After exposure and development, a coating film which was heated at 230 ° C for 30 minutes was immersed in the following chemicals under the following conditions, and the appearance and adhesion after immersion were evaluated.

耐酸性試驗：5%HCl中24小時Acid resistance test: 24 hours in 5% HCl

耐鹼性試驗1：5%NaOH中浸漬24小時Alkali resistance test 1: immersion in 5% NaOH for 24 hours

耐鹼性試驗2：4%KOH中、50℃下浸漬10分鐘Alkali resistance test 2: 4% KOH, immersed for 10 minutes at 50 ° C

耐鹼性試驗3：1%NaOH中、80℃下浸漬5分鐘Alkali resistance test 3: 1% NaOH, immersed for 5 minutes at 80 ° C

耐溶劑性試驗1：NMP中、40℃下浸漬10分鐘Solvent resistance test 1: immersion in NMP for 10 minutes at 40 ° C

耐溶劑性試驗2：NMP中、80℃下浸漬5分鐘Solvent resistance test 2: immersion in NMP at 80 ° C for 5 minutes

[(注)NMP：N-甲基吡咯烷酮][(Note) NMP: N-methylpyrrolidone]

由前述表3之結果可知，實施例6~10與比較例1相比時，顯影性及密接性優異。換言之，藉由紫外線或電子線照射可使本發明之樹脂充分地進行光硬化處理，硬化部與未硬化部對鹼顯影液之溶解度的差變大，可提供具有良好顯影性、高密接性之硬化膜。As is clear from the results of the above Table 3, in Examples 6 to 10, when compared with Comparative Example 1, the developability and the adhesion were excellent. In other words, the resin of the present invention can be sufficiently subjected to photohardening treatment by ultraviolet light or electron beam irradiation, and the difference in solubility between the hardened portion and the uncured portion to the alkali developing solution becomes large, and excellent developability and high adhesion can be provided. Hardened film.

[產業上利用價值][Industry use value]

本發明之感光性樹脂組成物，與習知者相比時，對鹼顯影液之溶解性高，且對紫外線或電子線照射而言可進行充分的光硬化處理。換言之，由於紫外線或電子線照射後之硬化部或未硬化部對鹼顯影液之溶解度的差變大，即使於薄膜或高著色劑濃度中仍可形成微細圖案。因此，本發明之感光性樹脂組成物，適合使用於彩色液晶顯示裝置、彩色傳真機、影像感應器等之各種多色顯示體、或光學機器等所使用的濾色器用之著色油墨、及具有藉由此等所形成的黑色矩陣的濾色器、或電視、錄放影機螢幕、或電腦之顯示器等。特別是適合作為濾色器保護膜材料。而且，如此所得的濾色器，例如於透過型、反射型或半透過型之彩色液晶顯示裝置、彩色攝影管元件、彩色感應器等極為有用。When the photosensitive resin composition of the present invention is compared with a conventional one, the solubility in an alkali developing solution is high, and sufficient light hardening treatment can be performed on ultraviolet light or electron beam irradiation. In other words, since the difference in solubility between the hardened portion or the uncured portion after irradiation with ultraviolet rays or electron beams becomes large, a fine pattern can be formed even in the film or high colorant concentration. Therefore, the photosensitive resin composition of the present invention is suitable for use in various color display bodies such as color liquid crystal display devices, color facsimile machines, and image sensors, and coloring inks for color filters used in optical devices, and the like. A color filter of a black matrix formed by the like, or a television, a video recorder screen, or a display of a computer. It is especially suitable as a color filter protective film material. Further, the color filter thus obtained is extremely useful, for example, in a transmissive, reflective or semi-transmissive color liquid crystal display device, a color photographic tube element, a color sensor, and the like.

Claims (6)

一種鹼可溶性樹脂，其特徵為以一般式(1)所表示的在分子內具有羧基及聚合性不飽和基之鹼可溶性樹脂，【化1】 (其中，W係表示以下述一般式(2)所表示的雙酚類衍生物；Y係表示4價羧酸殘基；G係表示下述一般式(3)或(4)所表示的取代基；Z係表示氫原子或以一般式(5)所表示的取代基；n係表示1～20之數)【化2】 (其中，R1 、R2 、R3 及R4 係獨立表示氫原子、碳數1～6之烷基、鹵素原子或苯基；X係表示-CO-、-SO2 -、-C(CF3 )2 -、-Si(CH3 )2 -、-CH2 -、-C(CH3 )2 -、-S-、-O-、9,9-芴二基或直接鍵結；m係表示0～10之數)【化3】 (其中，R8 係表示碳數2～20之2價脂肪族或芳香族烴基；R6 係表示碳數2～22之2價伸烷基或烷基亞芳基；R7 係表示氫原子或甲基；p係表示0～60之數)【化4】 (其中，L係表示2或3價羧酸殘基；q係表示1或2)。An alkali-soluble resin characterized by having an alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in the molecule represented by the general formula (1), [Chemical Formula 1] (W) represents a bisphenol derivative represented by the following general formula (2); Y represents a tetravalent carboxylic acid residue; and G represents a substitution represented by the following general formula (3) or (4). The Z system represents a hydrogen atom or a substituent represented by the general formula (5); the n system represents a number of 1 to 20) [Chemical 2] (wherein R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a halogen atom or a phenyl group; and X represents -CO-, -SO 2 -, -C ( CF 3 ) 2 -, -Si(CH 3 ) 2 -, -CH 2 -, -C(CH 3 ) 2 -, -S-, -O-, 9,9-fluorenyl or direct bonding; m The system indicates the number from 0 to 10) [Chemical 3] (wherein R 8 represents a divalent aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms; R 6 represents a divalent alkylene group or an alkylarylene group having 2 to 22 carbon atoms; and R 7 represents a hydrogen atom; Or methyl; p system means 0 to 60) [Chemical 4] (wherein L represents a 2 or a trivalent carboxylic acid residue; q represents 1 or 2). 如申請專利範圍第1項之鹼可溶性樹脂，其中使含有以下述一般式(6)所表示之聚合性不飽和基的二醇化合物(A)、與四羧酸或其酸二酐(a)及二羧酸、三羧酸或此等之酸酐(b)以(A):(a):(b)=1:0.2～0.5:0.2～1.0之莫耳比的範圍進行反應所得者，【化5】 (其中，R1 、R2 、R3 、R4 、G、X及m係以與一般式(1)及(2)中相同的規定表示)。The alkali-soluble resin of the first aspect of the invention, wherein the diol compound (A) containing a polymerizable unsaturated group represented by the following general formula (6), and a tetracarboxylic acid or an acid dianhydride thereof (a) And a dicarboxylic acid, a tricarboxylic acid or an acid anhydride (b) obtained by reacting a molar ratio of (A):(a):(b)=1:0.2 to 0.5:0.2 to 1.0, [ 5 (wherein R 1 , R 2 , R 3 , R 4 , G, X and m are represented by the same rules as in the general formulae (1) and (2)). 如申請專利範圍第2項之鹼可溶性樹脂，其中含有以一般式(6)所表示的聚合性不飽和基之二醇化合物(A)係使以下述一般式(7)所表示的環氧化合物、與以下述一般式(8)或(9)所表示的(甲基)丙烯酸衍生物中任一者或兩者進行反應所得者，【化6】 (其中，式中之R1 、R2 、R3 、R4 、R6 、R7 、R8 、m及p係以與前述一般式(1)至(4)中相同的規定表示)。The alkali-soluble resin of the second aspect of the invention, wherein the diol compound (A) containing a polymerizable unsaturated group represented by the general formula (6) is an epoxy compound represented by the following general formula (7). And a reaction with any one or both of the (meth)acrylic acid derivatives represented by the following general formula (8) or (9), [Chem. 6] (wherein R 1 , R 2 , R 3 , R 4 , R 6 , R 7 , R 8 , m and p are represented by the same specifications as in the above general formulas (1) to (4)). 一種感光性樹脂組成物，其特徵為含有(i)申請專利範圍第1至3項中任一項之鹼可溶性樹脂、(ii)不具羧酸殘基而至少具有1個以上聚合性不飽和基之光聚合性單體、及(iii)光聚合引發劑作為必須成分。A photosensitive resin composition comprising (i) an alkali-soluble resin according to any one of claims 1 to 3, (ii) having at least one carboxylic acid residue and having at least one polymerizable unsaturated group The photopolymerizable monomer and (iii) a photopolymerization initiator are essential components. 一種硬化物，其特徵為使申請專利範圍第4項之感光性樹脂組成物予以硬化所得者。A cured product obtained by curing a photosensitive resin composition of the fourth application of the patent application. 一種濾色器，其特徵為藉由塗佈申請專利範圍第4項之感光性樹脂組成物，予以硬化所得的硬化物所形成者。A color filter characterized by coating a photosensitive resin composition of the fourth application of the patent application and curing the cured product.
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