TWI533085B - A hardened resin composition, a dry film, a hardened product, and a display member - Google Patents

A hardened resin composition, a dry film, a hardened product, and a display member Download PDF

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TWI533085B
TWI533085B TW103129705A TW103129705A TWI533085B TW I533085 B TWI533085 B TW I533085B TW 103129705 A TW103129705 A TW 103129705A TW 103129705 A TW103129705 A TW 103129705A TW I533085 B TWI533085 B TW I533085B
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resin composition
curable resin
resin
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TW201523131A (en
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Chiho Ueta
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Taiyo Ink Mfg Co Ltd
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Description

硬化性樹脂組成物、乾膜、硬化物及顯示器構件 Curable resin composition, dry film, cured product, and display member

本發明係關於硬化性樹脂組成物(以下有時僅稱為「組成物」)、乾薄膜、硬化物及顯示構件。 The present invention relates to a curable resin composition (hereinafter sometimes referred to simply as "composition"), a dry film, a cured product, and a display member.

對於行動電話或具有顯示等液晶顯示部之製品中，隱藏包圍顯示區域之觸控板，所謂形成擋板(額緣區域)之材料中，要求具備高遮光性、即具備高OD值(OD3以上)，故自過去一般使用含有碳黑系顏料之黑色樹脂組成物(專利文獻1、2、3)。然而，碳黑系顏料因可達到高OD值，高濃度添加之組成物會有絕緣性劣化的傾向，例如不適用於藉由觸控板之構成方式塗布於覆蓋玻璃之擋板部分直接形成導電膜之用途上。又，由感光材料之觀點來看，碳黑系顏料為在自紫外線區域至紅外線區域的廣泛波長範圍因顯示吸收性，故有光硬化時的曝光會由顏料吸收，使得光硬化無法充分進行的問題。 In a mobile phone or a product having a liquid crystal display unit such as a display, the touch panel surrounding the display area is hidden, and the material forming the baffle (frontal area) is required to have high light-shielding property, that is, to have a high OD value (OD3 or more). Therefore, a black resin composition containing a carbon black pigment is generally used in the past (Patent Documents 1, 2, and 3). However, since the carbon black pigment can reach a high OD value, the composition added at a high concentration tends to deteriorate in insulation, and for example, it is not suitable for directly forming a conductive portion by a baffle plate coated by a touch panel. The use of the film. Further, from the viewpoint of the photosensitive material, the carbon black pigment exhibits absorbability in a wide wavelength range from the ultraviolet region to the infrared region, so that exposure during photocuring is absorbed by the pigment, so that photohardening cannot be sufficiently performed. problem.

專利文獻4中進一步揭示含有將特定鈦黑粒子作為主要成分的顏料之黑色感光性樹脂組成物。然而，因鈦黑會因高濃度添加而在低黏度組成物中容易引起沈 澱，故即使單獨得到高OD值，其添加量有著極限。 Further, Patent Document 4 discloses a black photosensitive resin composition containing a pigment containing specific titanium black particles as a main component. However, titanium black is likely to cause sinking in low-viscosity compositions due to high concentration addition. Therefore, even if a high OD value is obtained alone, the amount of addition has a limit.

如上述，有關具有黑色之樹脂組成物，至今已有種種被提案，但隨著近年技術發展，期待實現維持高遮光性下，可具備高絕緣性，特別為可賦予光硬化特性之材料。 As described above, various types of resin compositions having a black color have been proposed. However, with the development of technology in recent years, it is expected to have high insulation properties while maintaining high light-shielding properties, and in particular, materials capable of imparting photocuring properties.

〔先行技術文獻〕 [prior technical literature] 〔專利文獻〕 [Patent Document]

〔專利文獻1〕特開平04-190362號公報(申請專利範圍等) [Patent Document 1] Japanese Patent Publication No. 04-190362 (Application No., etc.)

〔專利文獻2〕特表2010-519592號公報(申請專利範圍等) [Patent Document 2] Japanese Patent Laid-Open Publication No. 2010-519592 (Patent Patent Application, etc.)

〔專利文獻3〕WO2012/133148A1(申請專利範圍等) [Patent Document 3] WO2012/133148A1 (Application Patent Range, etc.)

〔專利文獻4〕特開2002-275343號公報(申請專利範圍等) [Patent Document 4] JP-A-2002-275343 (Application for Patent, etc.)

〔發明之概要〕 [Summary of the Invention]

本發明之目的為提供一種維持高遮光性下，可提高絕緣性，特別為亦可具備良好光硬化性之硬化性樹脂組成物。 An object of the present invention is to provide a curable resin composition which can improve insulation properties while maintaining high light-shielding properties, and particularly has good photocurability.

本發明者們進行詳細檢討結果，發現於組成物中添加近紅外線吸收劑、於特定波長範圍具有最大吸收值與最小吸收值之有機色材時，可解決上述課題，進而完成本發明。 As a result of a detailed review, the present inventors have found that the above-mentioned problems can be solved by adding a near-infrared ray absorbing agent to an organic color material having a maximum absorption value and a minimum absorption value in a specific wavelength range, and the present invention has been completed.

即，本發明之硬化性樹脂組成物係以含有(A)近紅外線吸收劑、(B)於可見光區域380~780nm中，於380~500nm具有最小吸收值，於500~780nm具有最大吸收值之有機色材、及(C)熱硬化性成分為特徵者。本發明之硬化性樹脂組成物以進一步含有(D)鹼可溶性樹脂、及(E)光聚合起始劑者為佳。又，本發明之硬化性樹脂組成物以進一步含有(F)感光性(甲基)丙烯酸酯化合物者為佳。 That is, the curable resin composition of the present invention contains (A) a near-infrared ray absorbing agent and (B) 380 to 780 nm in the visible light region, has a minimum absorption value at 380 to 500 nm, and has a maximum absorption value at 500 to 780 nm. The organic color material and (C) the thermosetting component are characteristic. The curable resin composition of the present invention preferably further contains (D) an alkali-soluble resin and (E) a photopolymerization initiator. Moreover, it is preferable that the curable resin composition of the present invention further contains (F) a photosensitive (meth) acrylate compound.

又，本發明的其他硬化性樹脂組成物係以含有(A)近紅外線吸收劑、(B)於可見光區域380~780nm中，於380~500nm具有最小吸收值，於500~780nm具有最大吸收值之有機色材、及(F)感光性(甲基)丙烯酸酯化合物為特徵者。 Further, the other curable resin composition of the present invention contains (A) a near-infrared ray absorbing agent and (B) a visible light region of 380 to 780 nm, a minimum absorption value at 380 to 500 nm, and a maximum absorption value at 500 to 780 nm. The organic color material and (F) photosensitive (meth) acrylate compound are characterized.

本發明之硬化性樹脂組成物中，前述(A)近紅外線吸收劑之最大吸收波長以500~1000nm為佳。又，作為前述(A)近紅外線吸收劑，可使用選自金屬錯體色素及縮合多環系色素的至少1種為佳。且本發明之硬化性樹脂組成物已呈現黑色者為佳，更適合使用於絕緣膜之形成上。 In the curable resin composition of the present invention, the maximum absorption wavelength of the (A) near-infrared ray absorbing agent is preferably 500 to 1000 nm. Further, as the near-infrared ray absorbing agent (A), at least one selected from the group consisting of a metal complex dye and a condensed polycyclic dye can be preferably used. Further, the curable resin composition of the present invention is preferably black, and is more suitably used for the formation of an insulating film.

且，本發明之硬化性樹脂組成物欲進行色調調整，以對感光性、分散性不產生影響之範圍下，可使用除(B)可見光區域380~780nm中，於380~500nm具有最小吸收值，於500~780nm具有最大吸收值之色材以外之色材。 Further, in the curable resin composition of the present invention, the color tone is adjusted so as to have a minimum absorption value at 380 to 500 nm in the range of 380 to 780 nm in the (B) visible light region, in the range which does not affect the photosensitivity and dispersibility. A color material other than the color material having the largest absorption value at 500 to 780 nm.

又，本發明之乾薄膜係以將上述本發明之硬化性樹脂組成物於載體薄膜上進行塗佈，並使其乾燥而得為特徵者。 Moreover, the dry film of the present invention is characterized in that the curable resin composition of the present invention is coated on a carrier film and dried.

且，本發明之硬化物的特徵為將上述本發明之硬化性樹脂組成物於基材上進行塗佈，並使其乾燥而得之乾燥塗膜、或硬化以下塗膜而得者，該塗膜為將前述硬化性樹脂組成物於載體薄膜上進行塗佈，並使其乾燥而得之乾薄膜層合於基材而成者。 Further, the cured product of the present invention is characterized in that the curable resin composition of the present invention is applied onto a substrate and dried to obtain a dried coating film, or the following coating film is cured. The film is obtained by coating the curable resin composition on a carrier film and drying the dried film to laminate the substrate.

且，本發明之遮光用構件的特徵為具備上述本發明之硬化物者。 Further, the member for light shielding of the present invention is characterized in that it has the above-described cured product of the present invention.

且本發明之顯示用構件的特徵為具備上述本發明之硬化物者。 Further, the member for display of the present invention is characterized in that it has the above-described cured product of the present invention.

藉由本發明可實現維持高遮光性下，提高絕緣性，特別為亦可具備良好光硬化性之硬化性樹脂組成物。 According to the present invention, it is possible to improve the insulating properties while maintaining high light-shielding properties, and in particular, a curable resin composition which can also have good photocurability.

〔實施發明之形態〕 [Formation of the Invention]

以下參考圖式對本發明之實施形態做詳細說明。 Embodiments of the present invention will be described in detail below with reference to the drawings.

本發明之硬化性樹脂組成物在含有(A)近紅外線吸收劑、及(B)於可見光區域380~780nm中，於380~500nm具有最小吸收值，於500~780nm具有最大吸收值之色材的同時，含有(C)熱硬化性成分、或(F)感光性(甲基)丙烯酸酯化合物作為必須成分之點上具有特徵。 The curable resin composition of the present invention contains (A) a near-infrared ray absorbing agent, and (B) a color material having a minimum absorption value at 380 to 500 nm in a visible light region of 380 to 780 nm and a maximum absorption value at 500 to 780 nm. At the same time, it is characterized by containing (C) a thermosetting component or (F) a photosensitive (meth) acrylate compound as an essential component.

對於含有(A)近紅外線吸收劑、及(B)於可見光區域380~780nm中，於380~500nm具有最小吸收值，於500~780nm具有最大吸收值之色材之同時，含有(C)熱硬化性成分作為必須成分之本發明之第二實施態樣之硬化性樹脂組成物，可得到高遮光性及熱硬化性與絕緣性。又，對於含有(A)近紅外線吸收劑、及(B)於可見光區域380~780nm中，於380~500nm具有最小吸收值，於500~780nm具有最大吸收值之色材之同時，含有(F)感光性(甲基)丙烯酸酯化合物作為必須成分之本發明之第一實施態樣之硬化性樹脂組成物，可得到高遮光性及光硬化性與絕緣性。 (C) heat containing (A) near-infrared ray absorbing agent and (B) 380 to 780 nm in the visible light region, having a minimum absorption value at 380 to 500 nm, and having a maximum absorption value at 500 to 780 nm The curable resin composition of the second embodiment of the present invention, which is an essential component, has high light-shielding property, thermosetting property, and insulating property. Further, it contains (A) a near-infrared ray absorbing agent and (B) a color material having a minimum absorption value at 380 to 500 nm in a visible light region of 380 to 780 nm and a maximum absorption value at 500 to 780 nm, and contains (F) In the curable resin composition of the first embodiment of the present invention, which is an essential component of the photosensitive (meth) acrylate compound, high light-shielding property, photocurability, and insulating property can be obtained.

即，本發明為於樹脂組成物中含有(A)近紅外線吸收劑、及(B)於可見光區域380~780nm中，於380~500nm具有最小吸收值，於500~780nm具有最大吸收值之色材(以下亦稱為「(B)特定色材」)時，即使在高濃度下添加色材，可使良好遮光性及感光性在不會產 生沈澱等分散性問題下實現。本發明之組成物，特別在可見光區域中，OD值較佳為3以上，較佳為3~5，特佳為5~7。本發明之硬化性樹脂組成物為藉由上述調配可呈現較佳黑色者。 That is, the present invention contains (A) a near-infrared ray absorbing agent in the resin composition, and (B) a minimum absorption value at 380 to 500 nm in the visible light region of 380 to 780 nm, and a maximum absorption value at 500 to 780 nm. When the material (hereinafter also referred to as "(B) specific color material"), even if the color material is added at a high concentration, good light-shielding properties and photosensitivity are not produced. Realized under the problem of dispersion such as precipitation. In the composition of the present invention, particularly in the visible light region, the OD value is preferably 3 or more, preferably 3 to 5, and particularly preferably 5 to 7. The curable resin composition of the present invention can be preferably black by the above formulation.

又，特別地依據本發明之硬化性樹脂組成物可得到與添加碳黑系顏料時的類似色調。如前述，在欲得到較高OD值而添加碳黑系顏料時，會有電阻值及感光性降低之問題，但併用上述(A)，(B)成分的本發明可同時達成高OD值及電阻值。本發明在要求較高OD值、遮蔽性之觸控板構件上為有用。 Further, in particular, according to the curable resin composition of the present invention, a similar color tone as when a carbon black pigment is added can be obtained. As described above, when a carbon black pigment is added to obtain a high OD value, there is a problem that the electric resistance value and the photosensitivity are lowered. However, the present invention using the above (A) and (B) components can simultaneously achieve a high OD value and resistance. The present invention is useful in touch panel members that require higher OD values and shielding properties.

〔(A)近紅外線吸收劑〕 [(A) Near Infrared Absorber]

作為使用於本發明之(A)近紅外線吸收劑，可使用於500~1000nm具有極大吸收之色素，較佳為使用最大吸收波長為700~1000nm，更佳為800~1000nm者。作為色素，可使用金屬錯體色素及縮合多環系色素，具體例如可舉出酞菁系色素、卟啉系色素、花菁系色素、Quaterrylene系色素、方酸菁系色素、偶氮系、銨系、蒽醌系、二亞銨系、萘酞菁系色素、鎳錯體色素、銅離子系色素、二硫醇金屬錯體、雜環系化合物等。其中亦以雜環系化合物、Quaterine系色素、酞菁、萘酞菁系色素等於可見光區域亦具有吸收者為佳。作為製品，可舉出SDO-C8、SDO-C33(以上為有本化學工業公司製)、Lumogen IR 765、Lumogen IR 788(以上為BASFJAPAN公司製) 等。又，於上述波長範圍內具有極大吸收，且可有效率地吸收光，具有增感作用及具有金屬錯體之色素為佳。可使用這些的1種或2種以上。 The (A) near-infrared ray absorbing agent used in the present invention can be used for a dye having a maximum absorption of 500 to 1000 nm, preferably a maximum absorption wavelength of 700 to 1000 nm, more preferably 800 to 1000 nm. As the dye, a metal-based dye and a condensed polycyclic dye can be used, and specific examples thereof include a phthalocyanine dye, a porphyrin dye, a cyanine dye, a Quaterrylene dye, a squaraine dye, and an azo system. Ammonium, anthraquinone, diammonium, naphthalocyanine dye, nickel complex dye, copper ion dye, dithiol metal complex, heterocyclic compound, and the like. Among them, a heterocyclic compound, a Quaterine dye, a phthalocyanine or a naphthalocyanine dye is preferably equal to the visible light region. Examples of the product include SDO-C8, SDO-C33 (the above is manufactured by Seiko Chemical Co., Ltd.), Lumogen IR 765, and Lumogen IR 788 (the above is manufactured by BASFJAPAN Co., Ltd.). Wait. Further, it is preferable to have a maximum absorption in the above wavelength range and to efficiently absorb light, and it is preferable to have a sensitizing effect and a dye having a metal complex. One type or two or more types of these can be used.

作為(A)近紅外線吸收劑之含有率，在硬化性樹脂組成物(固體成分)中，以0.001~50質量%為佳，以0.005~30質量%為較佳，以0.005~20質量%為更佳。將(A)近紅外線吸收劑在上述範圍下，併用(B)特定色材時，特別在可見光區域，可得到所望的較高OD值。又，可進一步提高所要求之可見光波長部分的吸收。 The content of the (A) near-infrared ray absorbing agent is preferably 0.001 to 50% by mass, preferably 0.005 to 30% by mass, and 0.005 to 20% by mass, based on the curable resin composition (solid content). Better. When the (A) near-infrared absorbing agent is in the above range and (B) the specific color material is used, particularly in the visible light region, a desired higher OD value can be obtained. Further, the absorption of the desired visible light wavelength portion can be further improved.

〔(B)特定色材〕 [(B) specific color material]

作為使用於本發明的(B)特定色材，僅為於可見光區域380~780nm中，於380~500nm具有最小吸收值，於500~780nm具有最大吸收值之色材即可。色材中雖有有機色材與無機色材，本發明中較佳為使用有機色材。作為使用於本發明的(B)特定色材，雖有顏料或染料，於此可為除天然存在者以外之化學合成所成者，有關有機(合成)染料雖有由蒽醌系合成染料、偶氮系合成染料、次甲基系合成染料、喹啉系合成染料、苝系合成染料、嗪系合成染料所成群之公知慣用的有機(合成)染料，但特別以單獨下具有優良遮光性者，其具體可例舉出具有吩嗪骨架之化合物所成的苯胺黑。特別為COLOR INDEX的C.I.No.Acid Black 2、Solvent Black 5、Solvent Black 7、Solvent Black 22、Solvent Black 27、Solvent Black 29、 Solvent Black 34等，特別以於骨架上鉻、鈷、鎳、銅、鐵等金屬經錯鹽化的金屬錯鹽染料，其由著色力或耐熱特性的層面上來看為佳。作為有機顏料，於可見光區域380~780nm中，於380~500nm具有最小吸收值，於500~780nm具有最大吸收值之公知慣用的有機顏料等可舉出，其中亦以光硬化性、著色性及可見光區域之遮蔽性優良的酞菁系、二噁嗪系、苝系為佳。具體可例舉出酞菁系之Pigment Blue 15：3、15：4、15：6、苝系之Lumogen Black FK4280、Lumogen Black FK4281、噁嗪系之PigmentViolet 23、37為佳，彼等中可單獨使用1種，或適宜地混合2種以上使用。又，作為無機色材，可舉出四三氧化鈷、鈦黑等，彼等中可單獨使用1種，或適宜混合2種以上者。 The (B) specific color material used in the present invention may be a color material having a minimum absorption value at 380 to 500 nm in the visible light region of 380 to 780 nm and a maximum absorption value at 500 to 780 nm. Although there are organic color materials and inorganic color materials in the color material, it is preferred to use an organic color material in the present invention. As the specific color material (B) used in the present invention, although there are pigments or dyes, it may be a chemical synthesis other than the naturally occurring one, and the organic (synthetic) dye may be composed of an anthraquinone synthetic dye, A well-known organic (synthetic) dye which is a group of azo synthetic dyes, methine-based synthetic dyes, quinoline-based synthetic dyes, fluorene-based synthetic dyes, and azine-based synthetic dyes, but has excellent light-shielding properties in particular. Specifically, the aniline black formed by the compound having a phenazine skeleton can be exemplified. Especially for COLOR INDEX C.I.No.Acid Black 2, Solvent Black 5, Solvent Black 7, Solvent Black 22, Solvent Black 27, Solvent Black 29, Solvent Black 34 and the like, in particular, a metal salt-salt dye which is subjected to a salt-salting metal such as chromium, cobalt, nickel, copper or iron on the skeleton, is preferably in the form of coloring power or heat resistance. The organic pigment is a known organic pigment having a maximum absorption value at 380 to 500 nm in the visible light region at 380 to 780 nm, and a maximum absorption value at 500 to 780 nm, and also photocurability and coloring property. The phthalocyanine system, the dioxazine system, and the oxime system which are excellent in the shielding property in the visible light region are preferred. Specific examples of the phthalocyanine-based Pigment Blue 15:3, 15:4, 15:6, lanthanide Lumogen Black FK4280, Lumogen Black FK4281, and oxazide-based PigmentViolet 23, 37 are preferred. One type is used, or two or more types are used as appropriate. In addition, as the inorganic color material, cobalt tetraoxide, titanium black, or the like may be mentioned, and one type may be used alone or two or more types may be suitably mixed.

本發明者經詳細研究結果，發現以下各點。即，發現有關色材雖有顏料或染料，但於此以天然存在者以外之經化學合成者為佳，這些與天然存在者相比較，其彩度與吸收波長及著色性、作為組成物之相溶特性的選擇性為多樣化，故可使高OD值之感光性組成物達成良好平衡性。 The inventors have found the following points after detailed research results. That is, it has been found that although the color material has a pigment or a dye, it is preferably a chemically synthesized person other than the naturally occurring one, and the chroma, the absorption wavelength, and the coloring property as a composition are compared with the naturally occurring one. Since the selectivity of the compatibility characteristics is varied, a good balance of the photosensitive composition having a high OD value can be achieved.

又，特別發現若為本發明所使用的(B)特定色材，藉由優良著色力可達成與碳黑一樣的較少添加量下達成高OD值，因具有作為目的之吸收特性，故可得到優良光硬化性。且，發現在本發明所使用的(B)特定色材之中，特別以有機染料具有優良光硬化性與著色性、及分 散性之平衡，可適用於遮蔽用硬化性樹脂組成物上。 Further, it has been found that, in the case of the (B) specific color material used in the present invention, a high OD value can be achieved with a small amount of addition similar to carbon black by an excellent coloring power, and it has an absorption property as a target. Excellent photohardenability is obtained. Further, it has been found that among the specific color materials (B) used in the present invention, in particular, organic dyes have excellent photocurability and coloring properties, and The balance of the bulkiness can be applied to the curable resin composition for masking.

因此，(B)特定色材中，由較少添加量下可得到高OD值之觀點來看，以有機染料為佳。其中亦以可得到較高OD值之觀點來看，具有縮合苯胺‧硝基苯之吩嗪骨架的苯胺黑化合物為較佳。此為苯胺或者苯胺之鹽酸鹽與硝基苯中加入鹽酸，在銅或鐵等觸媒下進行脫水、脫氨、氧化‧還原縮合反應(Redox Condensation)後所得之黑色縮合混合物，藉由縮合條件成為具有種種吩嗪骨架之化合物而成的多成分體。苯胺黑為藉由反應時間、裝入原料及裝入比，可作為種種相異化合物的混合物所生成者，被推測為下述化學式(I)或(II)所示三吩嗪噁嗪、下述化學式(III)~(VI)所示吩嗪嗪等嗪系化合物、及於彼等導入烷基取代基之化合物的混合物。 Therefore, in the specific color material (B), an organic dye is preferred from the viewpoint that a high OD value can be obtained in a small amount of addition. Among them, a nigrosine compound having a phenazine skeleton of condensed aniline ‧ nitrobenzene is preferred from the viewpoint of obtaining a higher OD value. This is a black condensation mixture obtained by adding hydrochloric acid to aniline or aniline hydrochloride and nitrobenzene, dehydrating, deamination, oxidation and redox Condensation under a catalyst such as copper or iron, by condensation. The condition is a multicomponent having a compound of various phenazine skeletons. Aniline black is produced by a reaction mixture, a raw material, and a charge ratio, and can be produced as a mixture of various compounds, and is presumed to be a triphenazine oxazine represented by the following chemical formula (I) or (II). A mixture of a azine compound such as phenazine and a compound in which an alkyl substituent is introduced, as shown in the above formulas (III) to (VI).

成為本發明中之有機染料的原料之苯胺黑可使用如COLOR INDEX中作為C.I.，例如作為Acid Black 2、C.I.Solvent Black 5、Solvent Black 7所記載之黑色嗪系縮 合混合物。其中亦以含有以下所示化學結構式的Solvent Black 5及Solvent Black 7的金屬錯鹽染料為較佳。 The aniline black which is a raw material of the organic dye in the present invention can be used, for example, as C.I. in COLOR INDEX, for example, as a methazine condensate described in Acid Black 2, C.I. Solvent Black 5, Solvent Black 7. Mixture. Among them, a metal salt-salt dye containing Solvent Black 5 and Solvent Black 7 having the chemical structural formula shown below is also preferred.

(Solvent Black 5) (Solvent Black 5)

(Solvent Black 7) (Solvent Black 7)

使用於本發明的(B)特定色材之配合量為，於組成物(固體成分)中，以0.05~80質量%為佳，以0.1~70質量%為較佳，以0.5~50質量%為更佳。若將(B)特定色材之配合量在上述範圍內時，特別在可見光區域中，可得到所期待的較高OD值。 The amount of the specific color material used in the (B) of the present invention is preferably 0.05 to 80% by mass, more preferably 0.1 to 70% by mass, and preferably 0.5 to 50% by mass based on the composition (solid content). For better. When the blending amount of the (B) specific color material is within the above range, particularly in the visible light region, a desired higher OD value can be obtained.

〔(C)熱硬化性成分〕 [(C) thermosetting component]

使用於本發明之(C)熱硬化性成分，其含有的目的在於對組成物賦予耐熱性，特佳為使用於分子中具有2個以上環狀醚基及環狀硫代醚基(以下簡稱為環狀(硫代)醚基)的至少任一種的(C)熱硬化性成分。使用熱硬化 性成分時，不僅可確認到耐熱性，亦可提高與基底之密著性。於此，對於本發明之第二實施態樣，(C)熱硬化性成分係為必須，但對於本發明之第一實施態樣而言，亦以添加(C)熱硬化性成分為佳，藉此可得到兼備光硬化性與熱硬化性之硬化性樹脂組成物。 The (C) thermosetting component to be used in the present invention is intended to impart heat resistance to the composition, and particularly preferably has two or more cyclic ether groups and cyclic thioether groups in the molecule (hereinafter referred to as (C) a thermosetting component which is at least one of a cyclic (thio)ether group). Using heat hardening In the case of a sexual component, not only heat resistance but also adhesion to a substrate can be improved. Here, in the second embodiment of the present invention, (C) a thermosetting component is essential, but in the first embodiment of the present invention, it is preferable to add (C) a thermosetting component. Thereby, a curable resin composition having both photocurability and thermosetting property can be obtained.

如此於分子中具有2個以上環狀(硫代)醚基的(C)熱硬化性成分為，於分子中具有2個以上3、4或5員環之環狀醚基或者環狀硫代醚基中任一方或雙方之化合物，例如可舉出於分子內具有至少2個以上環氧基之化合物，即多官能環氧化合物、於分子內具有至少2個以上氧雜環丁烷基之化合物，即多官能氧雜環丁烷化合物、於分子內具有2個以上硫代醚基之化合物，即環硫化物樹脂等。 The (C) thermosetting component having two or more cyclic (thio)ether groups in the molecule is a cyclic ether group or a cyclic thio group having two or more 3, 4 or 5 membered rings in the molecule. The compound of either or both of the ether groups may, for example, be a compound having at least two or more epoxy groups in the molecule, that is, a polyfunctional epoxy compound having at least two or more oxetanyl groups in the molecule. The compound, that is, a polyfunctional oxetane compound, a compound having two or more thioether groups in the molecule, that is, an episulfide resin or the like.

作為多官能環氧化合物，例如可舉出三菱化學公司製的EPICOAT828、EPICOAT834、EPICOAT1001、EPICOAT1004、DIC公司製的EPICLON840、EPICLON850、EPICLON1050、EPICLON2055、東都化成公司製的EpotohtoYD-011、YD-013、YD-127、YD-128、陶氏化學公司製的D.E.R.317、D.E.R.331、D.E.R.661、D.E.R.664、住友化學工業公司製的蘇米-環氧ESA-011、ESA-014、ELA-115、ELA-128、旭化成工業公司製的A.E.R.330、A.E.R.331、A.E.R.661、A.E.R.664等(皆為商品名)之雙酚A型環氧樹脂；三菱化學公司製的EPICOATYL903、DIC公司製的 EPICLON152、EPICLON165、東都化成公司製的EpotohtoYDB-400、YDB-500、陶氏化學公司製的D.E.R.542、住友化學工業公司製的蘇米-環氧ESB-400、ESB-700、旭化成工業公司製的A.E.R.711、A.E.R.714等(皆為商品名)之溴化環氧樹脂；三菱化學公司製的EPICOAT152、EPICOAT154、陶氏化學公司製的D.E.N.431、D.E.N.438、DIC公司製的EPICLONN-730、EPICLONN-770、EPICLONN-865、東都化成公司製的EpotohtoYDCN-701、YDCN-704、日本化藥公司製的EPPN-201、EOCN-1025、EOCN-1020、EOCN-104S、RE-306、住友化學工業公司製的蘇米-環氧ESCN-195X、ESCN-220、旭化成工業公司製的A.E.R.ECN-235、ECN-299等(皆為商品名)之酚醛清漆型環氧樹脂；DIC公司製的EPICLON830、三菱化學公司製的EPICOAT807、東都化成公司製的EpotohtoYDF-170、YDF-175、YDF-2004等(皆為商品名)之雙酚F型環氧樹脂；東都化成公司製的EpotohtoST-2004、ST-2007、ST-3000(商品名)等氫化雙酚A型環氧樹脂；三菱化學公司製的EPICOAT604、東都化成公司製的EpotohtoYH-434、住友化學工業公司製的蘇米-環氧ELM-120等(皆為商品名)之縮水甘油基胺型環氧樹脂；乙內醯脲型環氧樹脂；大賽璐化學工業公司製的CELLOXIDE2021等(皆為商品名)之脂環式環氧樹脂；三菱化學公司製的YL-933、陶氏化學公司製的T.E.N.、EPPN-501、EPPN-502等(皆為商品名)之三羥 基苯基甲烷型環氧樹脂；三菱化學公司製的YL-6056、YX-4000、YL-6121(皆為商品名)等雙二甲酚型或者雙酚型環氧樹脂或彼等混合物；日本化藥公司製EBPS-200、旭電化工業公司製EPX-30、DIC公司製的EXA-1514(商品名)等雙酚S型環氧樹脂；三菱化學公司製的EPICOAT157S(商品名)等雙酚A酚醛清漆型環氧樹脂；三菱化學公司製的EPICOATYL-931等(皆為商品名)之四酚乙烷型環氧樹脂；日產化學工業公司製的TEPIC等(皆為商品名)之雜環式環氧樹脂；日本油脂公司製的BLEMMERDGT等二縮水甘油基鄰苯二甲酸酯樹脂；東都化成公司製的ZX-1063等四縮水甘油基二甲苯醯基乙烷樹脂；新日鐵化學公司製的ESN-190、ESN-360、DIC公司製的HP-4032、EXA-4750、EXA-4700等含萘基環氧樹脂；DIC公司製的HP-7200、HP-7200H等具有二環戊二烯骨架之環氧樹脂；日本油脂公司製的CP-50S、CP-50M等縮水甘油基甲基丙烯酸酯共聚合系環氧樹脂；進一步可舉出環己基馬來醯亞胺與縮水甘油基甲基丙烯酸酯之共聚合環氧樹脂；環氧改性之聚丁二烯橡膠衍生物(例如大賽璐化學工業公司製PB-3600等)、CTBN改性環氧樹脂(例如東都化成公司製的YR-102、YR-450等)、日本化藥公司製的NC3000等含有聯苯基骨架之環氧樹脂等，但並未限定於此等。這些環氧樹脂可單獨使用亦可組合2種以上使用。彼等中特別以酚醛清漆型環氧樹脂、雜環式環氧樹脂、雙酚A型環氧樹脂或彼等混合物為 佳。 Examples of the polyfunctional epoxy compound include EPICOAT 828, EPICOAT 834, EPICOAT 1001, EPICOAT 1004 manufactured by Mitsubishi Chemical Corporation, EPICLON 840 manufactured by DIC Corporation, EPICLON 850, EPICLON 1050, EPICLON 2055, and Epotohto YD-011, YD-013, YD manufactured by Tosho Kasei Co., Ltd. -127, YD-128, DER317, DER331, DER661, DER664, manufactured by Dow Chemical Co., Ltd., Suomi-Epoxy ESA-011, ESA-014, ELA-115, ELA- manufactured by Sumitomo Chemical Industries, Ltd. 128. Aceiba A, AER331, AER661, AER664, etc. (both are trade names) bisphenol A type epoxy resin manufactured by Asahi Kasei Industrial Co., Ltd.; EPICOATYL903 manufactured by Mitsubishi Chemical Corporation, manufactured by DIC Corporation EPICLON 152, EPICLON 165, Epotohto YDB-400, YDB-500, manufactured by Tosho Kasei Co., Ltd., DER542 manufactured by Dow Chemical Co., Ltd., Suomi-Epoxy ESB-400, ESB-700, manufactured by Sumitomo Chemical Industries, Ltd., manufactured by Asahi Kasei Kogyo Co., Ltd. Brominated epoxy resin such as AER711, AER714, etc. (both trade names); EPICOAT152, EPICOAT154 manufactured by Mitsubishi Chemical Corporation, DEN431, DEN438 manufactured by The Dow Chemical Co., Ltd., EPICLONN-730, EPICLONN manufactured by DIC Corporation 770, EPICLONN-865, Epotohto YDCN-701, YDCN-704 manufactured by Dongdu Chemical Co., Ltd., EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, manufactured by Nippon Kayaku Co., Ltd., manufactured by Sumitomo Chemical Industries Co., Ltd. Sumi-epoxy ESCN-195X, ESCN-220, AERECN-235, ECN-299, etc. (all trade names) made of Asahi Kasei Kogyo Co., Ltd. (all are brand name) novolac type epoxy resin; DIC company's EPICLON830, Mitsubishi Chemical EPICOAT807 manufactured by the company, Epotohto YDF-170, YDF-175, YDF-2004, etc. (both trade names) made of bisphenol F-type epoxy resin, EpotohtoST-2004, ST-2007, manufactured by Dongdu Chemical Co., Ltd. Hydrogenated bisphenol A type epoxy such as ST-3000 (trade name) Lipid; EPICOAT604 manufactured by Mitsubishi Chemical Corporation, EpotohtoYH-434 manufactured by Tosho Chemical Co., Ltd., and Sumi-Epoxy ELM-120 manufactured by Sumitomo Chemical Industries Co., Ltd. (all are trade names) of glycidylamine epoxy resin; Internal ureia type epoxy resin; alicyclic epoxy resin of CELLOXIDE 2021 (all trade name) manufactured by Daicel Chemical Industry Co., Ltd.; YL-933 manufactured by Mitsubishi Chemical Corporation, TEN manufactured by Dow Chemical Co., Ltd., EPPN- 501, EPPN-502, etc. (all are trade names) Phenyl phenylmethane type epoxy resin; bis-xylenol type or bisphenol type epoxy resin or a mixture thereof such as YL-6056, YX-4000, YL-6121 (all trade names) manufactured by Mitsubishi Chemical Corporation; Japan EBPS-200 manufactured by Chemicals Co., Ltd., EPX-30 manufactured by Asahi Kasei Kogyo Co., Ltd., bisphenol S-type epoxy resin such as EXA-1514 (trade name) manufactured by DIC Corporation, and bisphenol such as EPICOAT157S (trade name) manufactured by Mitsubishi Chemical Corporation A novolac type epoxy resin; a tetraphenol ethane type epoxy resin such as EPICOATYL-931 manufactured by Mitsubishi Chemical Corporation (all are trade names); a heterocyclic ring of TEPIC (all are trade names) manufactured by Nissan Chemical Industries Co., Ltd. Epoxy resin; diglycidyl phthalate resin such as BLEMMERDGT manufactured by Nippon Oil & Fats Co., Ltd.; tetraglycidyl xylene decyl ethane resin such as ZX-1063 manufactured by Dongdu Chemical Co., Ltd.; Nippon Steel Chemical Co., Ltd. Ethylene-based epoxy resin such as ESN-190, ESN-360, HP-4032, EXA-4750, and EXA-4700 manufactured by DIC Corporation; HP-7200 and HP-7200H manufactured by DIC Corporation have dicyclopentylene Epoxy resin of olefin skeleton; copolymerization of glycidyl methacrylate such as CP-50S and CP-50M manufactured by Nippon Oil Co., Ltd. Epoxy resin; further, a copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; an epoxy-modified polybutadiene rubber derivative (for example, manufactured by Daicel Chemical Industry Co., Ltd.) PB-3600, etc., CTBN modified epoxy resin (for example, YR-102, YR-450, manufactured by Tosho Kasei Co., Ltd.), epoxy resin containing biphenyl skeleton, etc., such as NC3000 manufactured by Nippon Kayaku Co., Ltd. Not limited to this. These epoxy resins may be used alone or in combination of two or more. Among them, a novolak type epoxy resin, a heterocyclic epoxy resin, a bisphenol A type epoxy resin or a mixture thereof is used. good.

作為多官能氧雜環丁烷化合物，可舉出雙〔(3-甲基-3-氧雜環丁烷基甲氧基)甲基〕醚、雙〔(3-乙基-3-氧雜環丁烷基甲氧基)甲基〕醚、1,4-雙〔(3-甲基-3-氧雜環丁烷基甲氧基)甲基〕苯、1,4-雙〔(3-乙基-3-氧雜環丁烷基甲氧基)甲基〕苯、(3-甲基-3-氧雜環丁烷基)甲基丙烯酸酯、(3-乙基-3-氧雜環丁烷基)甲基丙烯酸酯、(3-甲基-3-氧雜環丁烷基)甲基甲基丙烯酸酯、(3-乙基-3-氧雜環丁烷基)甲基甲基丙烯酸酯或這些寡聚物或共聚物等多官能氧雜環丁烷類其他，亦可舉出氧雜環丁烷醇與酚醛清漆樹脂、聚(p-羥基苯乙烯)、醚酮型雙酚類、杯芳烴類、間苯二酚杯芳烴類、或倍半矽氧烷等與具有羥基之樹脂的醚化物等。其他亦可舉出具有氧雜環丁烷環之不飽和單體與烷基(甲基)丙烯酸酯之共聚物等。 The polyfunctional oxetane compound may, for example, be bis[(3-methyl-3-oxetanylmethoxy)methyl]ether or bis[(3-ethyl-3-oxa) Cyclobutane methoxy)methyl]ether, 1,4-bis[(3-methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3) -ethyl-3-oxetanylmethoxy)methyl]benzene, (3-methyl-3-oxetanyl)methacrylate, (3-ethyl-3-oxo Heterocyclobutane)methacrylate, (3-methyl-3-oxetanyl)methyl methacrylate, (3-ethyl-3-oxetanyl)methyl Examples of the methacrylate or the polyfunctional oxetane such as these oligomers or copolymers include oxetane and novolac resins, poly(p-hydroxystyrene), and ether ketones. An ether compound such as a bisphenol, a calixarene, a resorcinol calixarene or a sesquioxane or a resin having a hydroxyl group. Other examples thereof include a copolymer of an oxetane ring-containing unsaturated monomer and an alkyl (meth) acrylate.

作為於分子中具有2個以上環狀硫代醚基的化合物，例如可舉出日本環氧樹脂公司製的雙酚A型環硫化物樹脂YL7000等。又，使用同樣的合成方法，將酚醛清漆型環氧樹脂之環氧基的氧原子由硫原子取代的環硫化物樹脂等亦可使用。 Examples of the compound having two or more cyclic thioether groups in the molecule include bisphenol A type episulfide resin YL7000 manufactured by Nippon Epoxy Co., Ltd., and the like. Further, an episulfide resin or the like in which an oxygen atom of an epoxy group of a novolac type epoxy resin is replaced by a sulfur atom can be used by the same synthesis method.

(C)熱硬化性成分之配合量對於樹脂成分100質量份而言，以0.6~2.8當量為佳，較佳為0.8~2.5當量之範圍。使(C)熱硬化性成分之配合量在上述範圍時，可對組成物賦予良好耐熱性。 The amount of the thermosetting component (C) is preferably 0.6 to 2.8 equivalents, preferably 0.8 to 2.5 equivalents, per 100 parts by mass of the resin component. When the amount of the (C) thermosetting component is within the above range, good heat resistance can be imparted to the composition.

〔(D)鹼可溶性樹脂〕 [(D) alkali soluble resin]

本發明之組成物中，作為樹脂成分，可添加(D)鹼可溶性樹脂。作為(D)鹼可溶樹脂，使用含羧基樹脂或酚樹脂為佳。特別使用含羧基樹脂時，由顯像性的層面來看更佳。 In the composition of the present invention, (D) an alkali-soluble resin can be added as a resin component. As the (D) alkali-soluble resin, a carboxyl group-containing resin or a phenol resin is preferably used. When a carboxyl group-containing resin is particularly used, it is more preferable from the viewpoint of development.

作為含羧基樹脂，可使用於分子中具有羧基，且不具有乙烯性不飽和雙鍵(非感光性)、或具有此(感光性)的過去公知各種含羧基樹脂。 As the carboxyl group-containing resin, various carboxyl group-containing resins which have a carboxyl group in the molecule, do not have an ethylenically unsaturated double bond (non-photosensitive), or have such (photosensitivity) can be used.

本發明中，特別為於分子中不具有乙烯性不飽和雙鍵之非感光性含羧基樹脂由柔軟性提高，硬化收縮減低及密著性提高的層面來看為佳。 In the present invention, in particular, the non-photosensitive carboxyl group-containing resin having no ethylenically unsaturated double bond in the molecule is preferably improved in flexibility, reduced in hardening shrinkage, and improved in adhesion.

作為非感光性含羧基樹脂之具體例子，可舉出如以下之化合物(寡聚物及聚合物皆可)。 Specific examples of the non-photosensitive carboxyl group-containing resin include the following compounds (both oligomers and polymers).

(1)含有脂肪族二異氰酸酯、分支脂肪族二異氰酸酯、脂環式二異氰酸酯、芳香族二異氰酸酯等二異氰酸酯、與二羥甲基丙酸、二羥甲基丁烷酸等羧基的二醇化合物、具有聚碳酸酯系多元醇、聚醚系多元醇、聚酯系多元醇、聚烯烴系多元醇、雙酚A系環氧化物加成物二醇、酚性羥基及醇性羥基的化合物等二醇化合物之藉由聚加成反應的含羧基之胺基甲酸酯樹脂。 (1) A diol compound containing a diisocyanate such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate or an aromatic diisocyanate, or a carboxyl group such as dimethylolpropionic acid or dimethylolbutanoic acid. A polycarbonate-based polyol, a polyether-based polyol, a polyester-based polyol, a polyolefin-based polyol, a bisphenol A-based epoxide adduct diol, a phenolic hydroxyl group, and an alcoholic hydroxyl group. A carboxyl group-containing urethane resin which is subjected to a polyaddition reaction of a diol compound.

(2)藉由二異氰酸酯與含羧基二醇化合物的聚加成反應之含有羧基的胺基甲酸酯樹脂。 (2) A carboxyl group-containing urethane resin which is reacted by polyaddition of a diisocyanate and a carboxyl group-containing diol compound.

(3)藉由(甲基)丙烯酸等不飽和羧酸、與苯乙烯、α-甲基苯乙烯、低級烷基(甲基)丙烯酸酯、異 丁烯等含不飽和基化合物之共聚合所得之含羧基樹脂。 (3) by unsaturated carboxylic acid such as (meth)acrylic acid, with styrene, α-methylstyrene, lower alkyl (meth) acrylate, and A carboxyl group-containing resin obtained by copolymerization of an unsaturated group-containing compound such as butene.

(4)反應2官能環氧樹脂或2官能氧雜環丁烷樹脂與己二酸、鄰苯二甲酸、六氫鄰苯二甲酸等二羧酸，於所生成的羥基加成鄰苯二甲酸酐、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐等2鹼酸酐之含羧基聚酯樹脂。 (4) reacting a bifunctional epoxy resin or a bifunctional oxetane resin with a dicarboxylic acid such as adipic acid, phthalic acid or hexahydrophthalic acid to form an phthalic acid in the resulting hydroxyl group A carboxyl group-containing polyester resin of two alkali anhydrides such as an acid anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride.

(5)使環氧樹脂或氧雜環丁烷樹脂進行開環，所生成之羥基與多鹼酸酐進行反應所得之含羧基樹脂。 (5) A carboxyl group-containing resin obtained by subjecting an epoxy resin or an oxetane resin to ring-opening and reacting the resulting hydroxyl group with a polybasic acid anhydride.

(6)將於1分子中具有複數酚性羥基之化合物，即將聚酚化合物與環氧乙烷、環氧丙烷等環氧化物進行反應所得之多元醇樹脂等反應生成物再與多鹼酸酐進行反應所得之含羧基樹脂。 (6) A compound having a plurality of phenolic hydroxyl groups in one molecule, that is, a reaction product of a polyol resin obtained by reacting a polyphenol compound with an epoxide such as ethylene oxide or propylene oxide, and a polybasic acid anhydride The carboxyl group-containing resin obtained by the reaction.

且，對於本說明書，所謂(甲基)丙烯酸酯表示丙烯酸酯、甲基丙烯酸酯及彼等混合物。 Further, in the present specification, the (meth) acrylate means an acrylate, a methacrylate, and a mixture thereof.

作為非感光性含羧基樹脂，其中與使用未含有氯者相比，較佳為使用上述(1)、(2)、(6)。其中亦以由具有芳香環而具有優良熱循環之觀點來看，使用合併硬化收縮，對於所有特性皆有良好平衡之上述(6)為佳。 As the non-photosensitive carboxyl group-containing resin, it is preferred to use the above (1), (2), and (6) as compared with the case where chlorine is not used. Among them, the above (6) is also preferable in that it has a good balance of all the characteristics from the viewpoint of having an aromatic ring and having excellent thermal cycling, and using a combination hardening shrinkage.

又，作為感光性含羧基樹脂之具體例子，可舉出如以下之化合物(寡聚物及聚合物皆可)。且，含羧基樹脂中之乙烯性不飽和雙鍵，以丙烯酸或者甲基丙烯酸或來自此等衍生物者為佳。 Further, specific examples of the photosensitive carboxyl group-containing resin include the following compounds (oligomers and polymers). Further, the ethylenically unsaturated double bond in the carboxyl group-containing resin is preferably acrylic acid or methacrylic acid or a derivative derived therefrom.

(7)含有脂肪族二異氰酸酯、分支脂肪族二 異氰酸酯、脂環式二異氰酸酯、芳香族二異氰酸酯等二異氰酸酯、與二羥甲基丙酸、二羥甲基丁烷酸等羧基之二醇化合物、具有聚碳酸酯系多元醇、聚醚系多元醇、聚酯系多元醇、聚烯烴系多元醇、丙烯酸系多元醇、雙酚A系環氧化物加成物二醇、酚性羥基及醇性羥基之化合物等二醇化合物的聚加成反應所得之含有羧基感光性胺基甲酸酯樹脂。 (7) Containing aliphatic diisocyanate, branched aliphatic a diisocyanate such as an isocyanate, an alicyclic diisocyanate or an aromatic diisocyanate; a diol compound having a carboxyl group such as dimethylolpropionic acid or dimethylolbutanoic acid; and a polycarbonate-based polyol or a polyether-based polyol Polyaddition reaction of diol compounds such as alcohol, polyester polyol, polyolefin polyol, acrylic polyol, bisphenol A epoxide adduct diol, phenolic hydroxyl group and alcoholic hydroxyl group The obtained carboxyl group-containing photosensitive urethane resin was obtained.

(8)二異氰酸酯、與雙酚A型環氧樹脂、氫化雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、雙二甲酚型環氧樹脂、雙酚型環氧樹脂等2官能環氧樹脂之(甲基)丙烯酸酯或者該部分酸酐改性物與含羧基二醇化合物之聚加成反應所得之含有羧基的感光性胺基甲酸酯樹脂。 (8) Diisocyanate, bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisxylenol epoxy resin, double A (meth) acrylate having a bifunctional epoxy resin such as a phenol epoxy resin or a photosensitive urethane resin containing a carboxyl group obtained by a polyaddition reaction of the acid anhydride-modified compound with the carboxyl group-containing diol compound.

(9)於上述(7)或(8)之樹脂的合成中，加入羥基烷基(甲基)丙烯酸酯等於分子內具有1個羥基與1個以上(甲基)丙烯醯基之化合物，進行末端(甲基)丙烯酸化的含有羧基之感光性胺基甲酸酯樹脂。 (9) In the synthesis of the resin of the above (7) or (8), the addition of a hydroxyalkyl (meth) acrylate is equivalent to a compound having one hydroxyl group and one or more (meth) acryl fluorenyl groups in the molecule. A terminal (meth) acrylated carboxyl group-containing photosensitive urethane resin.

(10)於上述(8)或(9)之樹脂的合成中，加入異佛爾酮二異氰酸酯與季戊四醇三丙烯酸酯等莫耳反應物等於分子內具有1個異氰酸酯基與1個以上(甲基)丙烯醯基之化合物，進行末端(甲基)丙烯酸化之含有羧基的感光性胺基甲酸酯樹脂。 (10) In the synthesis of the resin of the above (8) or (9), a molar reactant such as isophorone diisocyanate and pentaerythritol triacrylate is added to have one isocyanate group and one or more (methyl group) in the molecule. A compound containing a carboxy group, which is a terminal (meth) acrylated carboxyl group-containing photosensitive urethane resin.

(11)2官能或此以上的多官能(固體)環氧樹脂與(甲基)丙烯酸進行反應，於存在於側鏈的羥基加 成2鹼酸酐之含有羧基的感光性樹脂。 (11) A bifunctional or higher polyfunctional (solid) epoxy resin is reacted with (meth)acrylic acid to form a hydroxyl group present in the side chain. A photosensitive resin containing a carboxyl group as a base acid anhydride.

(12)將2官能(固體)環氧樹脂的羥基進一步以環氧氯丙烷進行環氧化的多官能環氧樹脂與(甲基)丙烯酸進行反應，於所生成的羥基加成2鹼酸酐的含有羧基之感光性樹脂。 (12) A polyfunctional epoxy resin obtained by further epoxidizing a hydroxyl group of a bifunctional (solid) epoxy resin with epichlorohydrin is reacted with (meth)acrylic acid to form a hydroxyl group-added 2 alkali anhydride. A photosensitive resin of a carboxyl group.

(13)將2官能氧雜環丁烷樹脂與己二酸、鄰苯二甲酸、六氫鄰苯二甲酸等二羧酸進行反應，於所生成的1級羥基加成鄰苯二甲酸酐、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐等2鹼酸酐之含有羧基的聚酯感光性樹脂。 (13) reacting a bifunctional oxetane resin with a dicarboxylic acid such as adipic acid, phthalic acid or hexahydrophthalic acid to form phthalic anhydride at the first-order hydroxyl group formed, A carboxyl group-containing polyester photosensitive resin of two alkali anhydrides such as tetrahydrophthalic anhydride or hexahydrophthalic anhydride.

(14)將於1分子中具有複數酚性羥基的化合物，即將聚酚化合物與環氧乙烷、環氧丙烷等環氧化物進行反應得到多元醇樹脂等反應生成物，將此與(甲基)丙烯酸等含不飽和基單羧酸進行反應，將所得之反應生成物進一步與多鹼酸酐進行反應所得之含有羧基的感光性樹脂。 (14) A compound having a plurality of phenolic hydroxyl groups in one molecule, that is, a polyphenol compound is reacted with an epoxide such as ethylene oxide or propylene oxide to obtain a reaction product such as a polyol resin, and A photosensitive resin containing a carboxyl group obtained by reacting an unsaturated group-containing monocarboxylic acid such as acrylic acid and further reacting the obtained reaction product with a polybasic acid anhydride.

(15)將於1分子中具有複數酚性羥基之化合物與伸乙基碳酸酯、伸丙基碳酸酯等環狀碳酸酯化合物進行反應得到反應生成物，將此與含不飽和基單羧酸進行反應得到反應生成物，將此與多鹼酸酐進行反應所得之含有羧基的感光性樹脂。 (15) A compound having a plurality of phenolic hydroxyl groups in one molecule is reacted with a cyclic carbonate compound such as ethyl acrylate or propyl carbonate to obtain a reaction product, which is combined with an unsaturated group-containing monocarboxylic acid. The reaction product is obtained to obtain a reaction product, and a carboxyl group-containing photosensitive resin obtained by reacting the polybasic acid anhydride with the polybasic acid anhydride is obtained.

(16)於上述(7)~(15)之樹脂進一步加成於1分子內具有1個環氧基與1個以上(甲基)丙烯醯基之化合物所成的含有羧基之感光性樹脂。 (16) A resin containing a carboxyl group which is obtained by further adding a resin having one epoxy group to one or more (meth)acryl fluorenyl groups in one molecule to the resin of the above (7) to (15).

這些感光性含羧基樹脂除作為(7)~(16)所敘述以外者，可單獨使用1種類，亦可混合複數種使用。特別在含羧基樹脂之中具有芳香環之樹脂因解像性優良而較佳。 These photosensitive carboxyl group-containing resins may be used alone or in combination of plural kinds, as described in (7) to (16). Particularly, a resin having an aromatic ring among the carboxyl group-containing resins is preferred because of excellent resolution.

其中，亦以如含羧基樹脂(14)、(15)，將酚化合物作為起始原料所合成的含羧基樹脂因未含有氯，故絕緣性優良而可適用。 Among them, the carboxyl group-containing resin synthesized by using a phenol compound as a starting material such as a carboxyl group-containing resin (14) or (15) is excellent in insulating property because it does not contain chlorine.

上述含羧基樹脂不管為感光性或非感光性，皆可說明如下。即，於主幹‧聚合物之側鏈因具有多數羧基，可於稀鹼水溶液中顯像。 The above-mentioned carboxyl group-containing resin can be explained as follows, regardless of whether it is photosensitive or non-photosensitive. That is, the side chain of the backbone ‧ polymer can be visualized in a dilute aqueous alkali solution because it has a plurality of carboxyl groups.

又，含羧基樹脂之酸價以40~200mgKOH/g之範圍為適當，較佳為45~120mgKOH/g之範圍。含羧基樹脂之酸價若未達40mgKOH/g時，鹼顯像變的困難，一方面若超過200mgKOH/g時，因藉由顯像液會進行曝光部之溶解，故會使線條變細至必要以上，依情況下不管曝光部與未曝光部，會造成以顯像液之溶解剝離，正常的抗蝕圖型之繪圖變的困難而不佳。 Further, the acid value of the carboxyl group-containing resin is suitably in the range of 40 to 200 mgKOH/g, preferably in the range of 45 to 120 mgKOH/g. When the acid value of the carboxyl group-containing resin is less than 40 mgKOH/g, the alkali development becomes difficult. On the other hand, when it exceeds 200 mgKOH/g, since the exposure portion is dissolved by the developing solution, the line is tapered to If necessary, depending on the case, the exposed portion and the unexposed portion may cause dissolution and separation of the developing liquid, and the drawing of the normal resist pattern may be difficult.

又，上述含羧基樹脂的重量平均分子量因樹脂骨架而相異，但一般為2,000~150,000，且以5,000~100,000的範圍為佳。重量平均分子量若未達2,000時，無黏性性能會變差，無法得到曝光後之塗膜的耐顯像性，又解像性會變得非常差。另一方面，重量平均分子量若超過150,000時，顯像性會顯著變差。 Further, the weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, but is generally 2,000 to 150,000, and preferably 5,000 to 100,000. When the weight average molecular weight is less than 2,000, the non-stick property is deteriorated, and the development resistance of the coating film after exposure cannot be obtained, and the resolution is extremely poor. On the other hand, when the weight average molecular weight exceeds 150,000, the developability is remarkably deteriorated.

如此含羧基樹脂之配合量為，於硬化性樹脂 組成物中為20~60質量%，較佳為30~50質量%之範圍為適當。含羧基樹脂之配合量若比20質量%少時，因被膜強度會降低故不佳。另一方面，若比60質量%多時，硬化性樹脂組成物之黏性會變高，或對載體薄膜之塗佈性等會降低故不佳。 The amount of the carboxyl group-containing resin is such that the curable resin The composition is preferably in the range of 20 to 60% by mass, preferably 30 to 50% by mass. When the amount of the carboxyl group-containing resin is less than 20% by mass, the strength of the film is lowered, which is not preferable. On the other hand, when the amount is more than 60% by mass, the viscosity of the curable resin composition becomes high, or the coatability to the carrier film or the like is lowered, which is not preferable.

又，對於本發明，作為鹼可溶性樹脂，可使用感光性含羧基樹脂、及不具有感光性之含羧基樹脂中任一方，亦可使用彼等混合者，但使用混合感光性含羧基樹脂與未具有感光性之含羧基樹脂者為佳，此含有比例為(感光性含羧基樹脂：未具有感光性之含羧基樹脂)以固體成分質量基準時，以(1：9)~(9：1)為佳，較佳為(2：8)~(8：2)，更佳為(5：5)~(7：3)之範圍。若在該範圍時，特別可避開曝光量增大下，可得到解像性及密著性之雙方皆優良的樹脂組成物的硬化物及具有此的印刷電路板。 Further, in the present invention, as the alkali-soluble resin, one of a photosensitive carboxyl group-containing resin and a carboxyl group-containing resin having no photosensitivity may be used, or a mixture thereof may be used, but a mixed photosensitive carboxyl group-containing resin may be used. It is preferable to use a photosensitive carboxyl group-containing resin, and the content ratio (photosensitive carboxyl group-containing resin: carboxyl group-containing resin having no photosensitivity) is (1:9) to (9:1) based on the mass of the solid component. Preferably, it is preferably (2:8)~(8:2), more preferably (5:5)~(7:3). When it is in this range, in particular, it is possible to obtain a cured product of a resin composition excellent in both resolution and adhesion, and a printed circuit board having the same, while avoiding an increase in exposure amount.

感光性含羧基樹脂、及不具有感光性之含羧基樹脂可使用除上述以外者，各可單獨使用1種類，亦可混合複數種使用。含羧基樹脂之中，特別以具有芳香環之樹脂因折射率高且解像性優良而較佳，且具有酚醛清漆結構者其在解像性、PCT耐性及裂紋耐性之層面上為優良。 The photosensitive carboxyl group-containing resin and the carboxyl group-containing resin having no photosensitivity may be used alone or in combination of two or more. Among the carboxyl group-containing resins, a resin having an aromatic ring is preferable because of its high refractive index and excellent resolution, and a resin having a novolac structure is excellent in resolution, PCT resistance, and crack resistance.

作為酚樹脂，可使用具有酚性羥基之化合物，例如使用具有聯苯基骨架或者伸苯基骨架或其雙方骨架之化合物、或含酚性羥基化合物，例如可使用由使用酚、鄰甲酚、對甲酚、間甲酚、2,3-二甲酚、2,4-二甲 酚、2,5-二甲酚、2,6-二甲酚、3,4-二甲酚、3,5-二甲酚、鄰苯二酚、間苯二酚、氫醌、甲基氫醌、2,6-二甲基氫醌、三甲基氫醌、鄰苯三酚、間苯三酚等所合成的具有種種骨架之酚樹脂。 As the phenol resin, a compound having a phenolic hydroxyl group can be used, for example, a compound having a biphenyl skeleton or a phenylene skeleton or a skeleton thereof, or a phenolic hydroxy compound can be used, and for example, phenol or o-cresol can be used. P-cresol, m-cresol, 2,3-xylenol, 2,4-dimethyl Phenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, catechol, resorcinol, hydroquinone, methyl hydrogen A phenolic resin having various skeletons synthesized by ruthenium, 2,6-dimethylhydroquinone, trimethylhydroquinone, pyrogallol, and phloroglucinol.

例如可使用酚酚醛清漆樹脂、烷基酚酚醛清漆樹脂、雙酚A酚醛清漆樹脂、二環戊二烯型酚樹脂、Xylok型酚樹脂、萜烯改性酚樹脂、聚乙烯酚類、雙酚F、雙酚S型酚樹脂、聚-p-羥基苯乙烯、萘酚與醛類之縮合物、二羥基萘與醛類之縮合物等公知慣用的酚樹脂。 For example, a phenol novolak resin, an alkylphenol novolak resin, a bisphenol A novolac resin, a dicyclopentadiene type phenol resin, a Xylok type phenol resin, a terpene modified phenol resin, a polyvinyl phenol, a bisphenol can be used. F, a phenolic resin of a bisphenol S type, a poly-p-hydroxystyrene, a condensate of naphthol and an aldehyde, a condensate of a dihydroxy naphthalene and an aldehyde, and the like.

這些可單獨使用或組合2種以上使用。 These can be used individually or in combination of 2 or more types.

作為相關酚樹脂之市售品，可舉出HF1H60(明和化成公司製)、PHENOLITETD-2090、PHENOLITETD-2131(大日本印刷公司製)、BesumoruCZ-256-A(DIC公司製)、ShiyounoruBRG-555、ShiyounoruBRG-556(昭和電工公司製)、CGR-951(丸善石油公司製)、或、聚乙烯酚之CST70、CST90、S-1P、S-2P(丸善石油公司製)等。這些酚樹脂可單獨使用，或者適宜地組合2種類以上使用。 HF1H60 (made by Megumi Kasei Co., Ltd.), PHENOLITETD-2090, PHENOLITETD-2131 (made by Dainippon Printing Co., Ltd.), Besumoru CZ-256-A (made by DIC Corporation), Shiyounoru BRG-555, etc. are mentioned as a commercial item of the phenol resin. Shiyounoru BRG-556 (manufactured by Showa Denko KK), CGR-951 (manufactured by Maruzen Oil Co., Ltd.), or CST70, CST90, S-1P, S-2P (manufactured by Maruzen Oil Co., Ltd.) of polyvinyl phenol. These phenol resins may be used singly or in combination of two or more kinds as appropriate.

本發明中，作為(D)鹼可溶性樹脂，可使用含羧基樹脂及酚樹脂中任一方或這些混合物。 In the present invention, as the (D) alkali-soluble resin, either one of a carboxyl group-containing resin and a phenol resin or a mixture thereof can be used.

且，本發明之硬化性樹脂組成物中，作為(D)鹼可溶性樹脂使用未含乙烯性不飽和基之材料時，必須併用於分子中具有1個以上，較佳為具有2個以上乙烯性不飽和基的化合物，即必須併用光聚合性單體‧寡聚 物等光聚合性化合物。光聚合性化合物為藉由活性能量線照射進行光硬化，且可助長(D)鹼可溶性樹脂對鹼水溶液之溶解。此外使用含羧基樹脂時，以進一步促進光硬化為目的，可併用光聚合性化合物。 In the curable resin composition of the present invention, when a material containing no ethylenically unsaturated group is used as the (D) alkali-soluble resin, it is necessary to use one or more molecules in the molecule, and preferably two or more ethyl groups. An unsaturated group of compounds, that is, a photopolymerizable monomer must be used together A photopolymerizable compound such as a substance. The photopolymerizable compound is photocured by irradiation with an active energy ray, and can promote the dissolution of the (D) alkali-soluble resin into an aqueous alkali solution. Further, when a carboxyl group-containing resin is used, a photopolymerizable compound can be used in combination for the purpose of further promoting photocuring.

於任一情況皆可使用1種類或複數種類之光聚合性化合物。 One type or a plurality of types of photopolymerizable compounds can be used in either case.

〔(E)光聚合起始劑〕 [(E) Photopolymerization initiator]

本發明之組成物可含有(E)光聚合起始劑。作為(E)光聚合起始劑，可舉出二苯甲酮系、苯乙酮系、胺基苯乙酮系、安息香醚系、苯甲基縮酮系、醯基次膦氧化物系、肟醚系、肟酯系、茂鈦系等公知慣用化合物。 The composition of the present invention may contain (E) a photopolymerization initiator. Examples of the (E) photopolymerization initiator include a benzophenone type, an acetophenone type, an amino acetophenone type, a benzoin ether type, a benzyl ketal type, and a decylphosphinium oxide type. A known compound such as an oxime ether, an oxime ester or a titanocene.

作為(E)光聚合起始劑，以含有選自由以下含有所示一般式(I)所示結構部分的肟酯系、含有一般式(II)所示結構部分的α-胺基苯乙酮系、含有一般式(III)所示結構部分的醯基次膦氧化物系、及一般式(IV)所示茂鈦系所成群的1種或2種以上者為佳。 The (E) photopolymerization initiator contains α-aminoacetophenone selected from the group consisting of an oxime ester group having a structural moiety represented by the general formula (I) shown below and containing a structural moiety represented by the general formula (II). It is preferred that one or two or more kinds of the fluorenylphosphinyl oxide system having a structural moiety represented by the general formula (III) and the ferrocene-based compound represented by the general formula (IV) are present.

一般式(I)中，R1表示氫原子、苯基、烷基、環烷基、烷醯基或苯甲醯基。R2表示苯基、烷基、環烷基、烷醯基或苯甲醯基。 In the general formula (I), R 1 represents a hydrogen atom, a phenyl group, an alkyl group, a cycloalkyl group, an alkanoyl group or a benzamidine group. R 2 represents a phenyl group, an alkyl group, a cycloalkyl group, an alkano group or a benzyl group.

R1及R2所表示苯基可具有取代基，作為該取代基，例如可舉出碳數1~6的烷基、苯基、鹵素原子等。 The phenyl group represented by R 1 and R 2 may have a substituent. Examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a phenyl group, and a halogen atom.

作為R1及R2所表示烷基，以碳數1~20的烷基為佳，於烷基鏈中可含有1個以上氧原子。又，可由1個以上羥基所取代。 The alkyl group represented by R 1 and R 2 is preferably an alkyl group having 1 to 20 carbon atoms, and may have one or more oxygen atoms in the alkyl chain. Further, it may be substituted by one or more hydroxyl groups.

作為R1及R2所表示環烷基，以碳數5~8的環烷基為佳。 The cycloalkyl group represented by R 1 and R 2 is preferably a cycloalkyl group having 5 to 8 carbon atoms.

作為R1及R2所表示烷醯基，以碳數2~20的烷醯基為佳。 The alkyl fluorenyl group represented by R 1 and R 2 is preferably an alkyl fluorenyl group having 2 to 20 carbon atoms.

R1及R2所表示苯甲醯基可具有取代基，作為該取代基，例如可舉出碳數為1~6的烷基、苯基等。 The benzamidine group represented by R 1 and R 2 may have a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms and a phenyl group.

一般式(II)中，R3及R4各獨立表示碳數1 ~12的烷基或芳基烷基，R5及R6各獨立表示氫原子、或碳數1~6的烷基，或者2個結合可形成環狀烷基醚基。 In the general formula (II), R 3 and R 4 each independently represent an alkyl group or an arylalkyl group having 1 to 12 carbon atoms, and R 5 and R 6 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Or two combinations may form a cyclic alkyl ether group.

一般式(III)中，R7及R8各獨立表示碳數1~10的烷基、環己基、環戊基、芳基或可由鹵素原子、烷基或者烷氧基所取代之芳基、或碳數1~20的羰基(但，除去雙方為碳數1~20的羰基之情況)。 In the general formula (III), R 7 and R 8 each independently represent an alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl group or an aryl group which may be substituted by a halogen atom, an alkyl group or an alkoxy group, Or a carbonyl group having 1 to 20 carbon atoms (however, the case where both of them are a carbonyl group having 1 to 20 carbon atoms) is removed.

一般式(IV)中，R9及R10各獨立表示鹵素原子、芳基、鹵素化芳基、雜環含有鹵素化芳基。 In the general formula (IV), R 9 and R 10 each independently represent a halogen atom, an aryl group, a halogenated aryl group, and a heterocyclic ring contains a halogenated aryl group.

作為含有一般式(I)所示結構部分之肟酯系光聚合起始劑，可舉出1,2-辛烷二酮-1-〔4-(苯基硫基)-2-(O-苯甲醯肟)〕、乙酮,1-〔9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基〕-,1-(O-乙醯肟)、下述式(I-1)所示化合物、2-(乙醯氧基亞胺甲基)噻噸-9-酮、及下述一般式(I-2)所示化合物等。 The oxime ester photopolymerization initiator containing the structural moiety represented by the general formula (I) is exemplified by 1,2-octanedione-1-[4-(phenylthio)-2-(O- Benzamidine), ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O-acetamidine A compound represented by the following formula (I-1), 2-(ethyloxyiminomethyl)thioxanthene-9-one, and a compound represented by the following general formula (I-2).

一般式(I-2)中，R11與一般式(I)中之R1 同義，R12及R14各獨立與一般式(I)中之R2同義。R13表示氫原子、鹵素原子、碳數1~12的烷基、環戊基、環己基、苯基、苯甲基、苯甲醯基、碳數2~12的烷醯基、碳數2~12的烷氧基羰基(構成烷氧基之烷基碳數為2以上時，烷基可由1個以上羥基所取代，亦可於烷基鏈之中間具有1個以上氧原子)或苯氧基羧基。 In the general formula (I-2), R 11 is synonymous with R 1 in the general formula (I), and R 12 and R 14 are each independently synonymous with R 2 in the general formula (I). R 13 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzamyl group, an alkyl 2 group having 2 to 12 carbon atoms, and a carbon number of 2 ~12 alkoxycarbonyl group (when the alkyl group number of the alkoxy group is 2 or more, the alkyl group may be substituted by one or more hydroxyl groups, or may have one or more oxygen atoms in the middle of the alkyl chain) or phenoxy Carboxyl group.

彼等中亦以上述式(I-2)所示化合物為佳。 Among them, the compound represented by the above formula (I-2) is also preferred.

如此肟酯系光聚合起始劑，例如對於直接成像用的曝光，本發明之組成物因感度為高，具有優良解像性故較佳。 Such an oxime ester photopolymerization initiator is preferably used for direct imaging, for example, because the composition of the present invention has high sensitivity and excellent resolution.

特別以曝光為單獨波長的h線(405nm)之情況下，肟酯系光聚合起始劑以二量體為佳。 In particular, in the case where the exposure is h line (405 nm) of a single wavelength, the oxime ester photopolymerization initiator is preferably a dimer.

作為二量體之肟酯系光聚合起始劑，以下述一般式(I-3)所示化合物為較佳。 As the dimeric oxime ester photopolymerization initiator, a compound represented by the following general formula (I-3) is preferred.

一般式(I-3)中，R23表示氫原子、烷基、烷氧基、苯基、萘基。 In the general formula (I-3), R 23 represents a hydrogen atom, an alkyl group, an alkoxy group, a phenyl group or a naphthyl group.

R21、R22各獨立表示氫原子、烷基、烷氧基、鹵素基、苯基、萘基、蒽基、吡啶基、苯並呋喃基、苯並噻吩基。 R 21 and R 22 each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen group, a phenyl group, a naphthyl group, a fluorenyl group, a pyridyl group, a benzofuranyl group or a benzothienyl group.

Ar表示單鍵、或、碳數1~10的伸烷基、苯並噻吩基、伸苯基、雙伸苯基、伸吡啶基、亞萘基、伸蒽基、伸噻吩基、伸呋喃基、2,5-吡咯-二基、4,4’-芪-二基、4,2’-苯乙烯-二基。 Ar represents a single bond, or an alkylene group having 1 to 10 carbon atoms, a benzothienyl group, a phenylene group, a diphenylene group, a pyridyl group, a naphthylene group, a fluorenyl group, a thienyl group, and a furanyl group. 2,5-pyrrole-diyl, 4,4'-fluorenyl-diyl, 4,2'-styrene-diyl.

n表示0~1的整數。 n represents an integer from 0 to 1.

作為R23所表示烷基，以碳數1~17的烷基為佳。 The alkyl group represented by R 23 is preferably an alkyl group having 1 to 17 carbon atoms.

作為R23所表示烷氧基，以碳數1~8的烷氧基為佳。 The alkoxy group represented by R 23 is preferably an alkoxy group having 1 to 8 carbon atoms.

對於R23所表示苯基可具有取代基，作為該取代基，例如可舉出烷基(較佳為碳數1~17)、烷氧基(較佳為碳數1~8)、胺基、烷基胺基(較佳為烷基的碳數1~8)及二烷基胺基(較佳為烷基的碳數1~8)等。 The phenyl group represented by R 23 may have a substituent. Examples of the substituent include an alkyl group (preferably having 1 to 17 carbon atoms), an alkoxy group (preferably having 1 to 8 carbon atoms), and an amine group. And an alkylamino group (preferably having an alkyl group having 1 to 8 carbon atoms) and a dialkylamino group (preferably having an alkyl group having 1 to 8 carbon atoms).

對於R23所表示萘基可具有取代基，作為該取代基，可舉出與具有R23所表示苯基之上述取代基的相同基。 The naphthyl group represented by R 23 may have a substituent, and examples of the substituent include the same group as the above substituent of the phenyl group represented by R 23 .

作為R21及R22所表示烷基，以碳數1~17的烷基為佳。 The alkyl group represented by R 21 and R 22 is preferably an alkyl group having 1 to 17 carbon atoms.

作為R21及R22所表示烷氧基，以碳數1~8的烷氧基為佳。 The alkoxy group represented by R 21 and R 22 is preferably an alkoxy group having 1 to 8 carbon atoms.

對於R21及R22所表示苯基可具有取代基，作為該取代基，例如可舉出烷基(較佳為碳數1~17)、烷氧基(較佳為碳數1~8)、胺基、烷基胺基(較佳為烷基的碳數1~8)及二烷基胺基(較佳為烷基的碳數1~8)等。 The phenyl group represented by R 21 and R 22 may have a substituent. Examples of the substituent include an alkyl group (preferably having 1 to 17 carbon atoms) and an alkoxy group (preferably having 1 to 8 carbon atoms). And an amine group, an alkylamino group (preferably having an alkyl group having 1 to 8 carbon atoms) and a dialkylamino group (preferably having an alkyl group having 1 to 8 carbon atoms).

對於R21及R22所表示萘基可具有取代基，作為該取代基，可舉出與具有R21及R22所表示苯基的上述取代基之相同基。 The naphthyl group represented by R 21 and R 22 may have a substituent, and examples of the substituent include the same groups as the above substituents having a phenyl group represented by R 21 and R 22 .

且一般式(I-3)中，R21、R23各獨立為甲基或乙基，R22為甲基或苯基，Ar為單鍵或伸苯基、亞萘基或伸噻吩基，n為0時為佳。一般式(I-3)所示化合物中，亦以下述結構式所示者為較佳。 And in the general formula (I-3), R 21 and R 23 are each independently a methyl group or an ethyl group, R 22 is a methyl group or a phenyl group, and Ar is a single bond or a phenyl group, a naphthylene group or a thienylene group. When n is 0, it is preferable. Among the compounds represented by the general formula (I-3), those represented by the following structural formulas are also preferred.

使用如此肟酯系光聚合起始劑時，欲提高對曝光之感度，併用含有一般式(II)所示結構部分之α-胺基苯乙酮系光聚合起始劑等為佳。 When such an oxime ester photopolymerization initiator is used, it is preferred to use an α-aminoacetophenone photopolymerization initiator containing a structural moiety represented by the general formula (II), and the like.

作為含有一般式(II)所示結構部分的α-胺基苯乙酮系光聚合起始劑，可舉出2-甲基-1-〔4-(甲基硫基)苯基〕-2-嗎啉代丙酮-1、2-苯甲基-2-二甲基胺基-1-(4-嗎啉代苯基)-丁烷-1-酮、2-(二甲基胺基)-2-〔(4-甲基苯基)甲基〕-1-〔4-(4-嗎啉基)苯基〕-1-丁酮、N,N-二甲基胺基苯乙酮等。 The α-aminoacetophenone photopolymerization initiator containing the structural moiety represented by the general formula (II) includes 2-methyl-1-[4-(methylthio)phenyl]-2. -morpholinone-1,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-(dimethylamino) -2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, N,N-dimethylaminoacetophenone, etc. .

作為含有一般式(III)所示結構部分的醯基次膦氧化物系光聚合起始劑，可舉出2,4,6-三甲基苯甲醯基二苯基次膦氧化物、雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦、雙(2,6-二甲氧基苯甲醯基)-2,4,4-三甲基-戊基 氧化膦等。 The fluorenylphosphinic oxide-based photopolymerization initiator containing a structural moiety represented by the general formula (III) includes 2,4,6-trimethylbenzimidyldiphenylphosphinium oxide and a double (2,4,6-trimethylbenzylidene)-phenylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethyl-pentyl Phosphine oxide and the like.

作為一般式(IV)所示茂鈦系光聚合起始劑，可舉出雙(η5-2,4-環戊二烯-1-基)-雙(2,6-二氟-3-(1H-吡咯-1-基)-苯基)鈦。 As the titanocene photopolymerization initiator represented by the general formula (IV), bis(η 5 -2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-) (1H-pyrrol-1-yl)-phenyl)titanium.

如此(E)光聚合起始劑之配合率對於樹脂成分100質量份而言，較佳為0.01~100質量份，更佳為0.5~80質量份的比例。(E)光聚合起始劑的配合率對於樹脂成分100質量份而言未達0.01質量份時，光硬化性會不足，塗膜會剝離，且耐藥品性等塗膜特性會有降低之情形而不佳。另一方面，(E)光聚合起始劑的配合率對於樹脂成分100質量份而言超過100質量份時，藉由(E)光聚合起始劑之光吸收，深部硬化性會有降低的情況而不佳。 The blending ratio of the (E) photopolymerization initiator is preferably from 0.01 to 100 parts by mass, more preferably from 0.5 to 80 parts by mass, per 100 parts by mass of the resin component. (E) When the blending ratio of the photopolymerization initiator is less than 0.01 parts by mass based on 100 parts by mass of the resin component, the photocurability is insufficient, the coating film is peeled off, and the coating properties such as chemical resistance are lowered. Not good. On the other hand, when the blending ratio of the (E) photopolymerization initiator exceeds 100 parts by mass based on 100 parts by mass of the resin component, the deep curing property is lowered by the light absorption of the (E) photopolymerization initiator. The situation is not good.

且，本發明之硬化性樹脂組成物中可使用上述化合物以外的光聚合起始劑或光起始助劑及增感劑，例如可舉出安息香化合物、蒽醌化合物、噻噸酮化合物、縮酮化合物、二苯甲酮化合物、呫噸酮化合物、及、3級胺化合物等。 Further, a photopolymerization initiator or a photoinitiator and a sensitizer other than the above compounds may be used in the curable resin composition of the present invention, and examples thereof include a benzoin compound, an anthraquinone compound, and a thioxanthone compound. A ketone compound, a benzophenone compound, a xanthone compound, and a tertiary amine compound.

若要舉出安息香化合物的具體例子，例如有安息香、安息香甲基醚、安息香乙基醚、安息香異丙基醚。若要舉出苯乙酮化合物之具體例子，例如有苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基-2-苯基苯乙酮、1,1-二氯苯乙酮。若要舉出蒽醌化合物之具體例子，例如有2-甲基蒽醌、2-乙基蒽醌、2-t-丁基蒽醌、1-氯蒽 醌。若要舉出噻噸酮化合物之具體例子，例如有2,4-二甲基硫基呫噸酮、2,4-二乙基硫基呫噸酮、2-氯噻噸酮、2,4-二異丙基硫基呫噸酮。若要舉出縮酮化合物之具體例子，例如可舉出苯乙酮二甲基縮酮、苯甲基二甲基縮酮。若要舉出二苯甲酮化合物之具體例子，例如有二苯甲酮、4-苯甲醯基二苯基硫化物、4-苯甲醯基-4’-甲基二苯基硫化物、4-苯甲醯基-4’-乙基二苯基硫化物、4-苯甲醯基-4’-丙基二苯基硫化物。 Specific examples of the benzoin compound are exemplified by benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. Specific examples of acetophenone compounds, such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylphene Ketone, 1,1-dichloroacetophenone. Specific examples of the ruthenium compound are exemplified by 2-methyl hydrazine, 2-ethyl hydrazine, 2-t-butyl hydrazine, and 1-chloro hydrazine. Hey. Specific examples of the thioxanthone compound include, for example, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4 - Diisopropylthioxanthone. Specific examples of the ketal compound include acetophenone dimethyl ketal and benzyl dimethyl ketal. Specific examples of the benzophenone compound include benzophenone, 4-benzylidene diphenyl sulfide, 4-benzylidene-4'-methyldiphenyl sulfide, 4-Benzylmercapto-4'-ethyldiphenyl sulfide, 4-benzylidene-4'-propyldiphenyl sulfide.

若要舉出3級胺化合物之具體例子，例如有乙醇胺化合物、具有二烷基胺基苯結構之化合物，例如有4,4’-二甲基胺基二苯甲酮(日本曹達公司製NissokyuaMABP)、4,4’-二乙基胺基二苯甲酮(保土谷化學公司製EAB)等二烷基胺基二苯甲酮、7-(二乙基胺基)-4-甲基-2H-1-苯並吡喃-2-酮(7-(二乙基胺基)-4-甲基香豆素)等含有二烷基胺基之香豆素化合物、4-二甲基胺基安息香酸乙基(日本化藥公司製KayacureEPA)、2-二甲基胺基安息香酸乙基(International Bio-synthetics公司製Quantacure DMB)、4-二甲基胺基安息香酸(n-丁氧基)乙基(International Bio-synthetics公司製Quantacure BEA)、p-二甲基胺基安息香酸異戊基乙基酯(日本化藥公司製KayacureDMBI)、4-二甲基胺基安息香酸2-乙基己基(Van Dyk公司製Esolol 507)、4,4’-二乙基胺基二苯甲酮(保土谷化學公司製EAB)。 Specific examples of the tertiary amine compound, for example, an ethanolamine compound, a compound having a dialkylaminobenzene structure, for example, 4,4'-dimethylaminobenzophenone (Nissokyua MABP, manufactured by Nippon Soda Co., Ltd.) , 4,4'-diethylaminobenzophenone (EAB, manufactured by Hodogaya Chemical Co., Ltd.), etc., dialkylaminobenzophenone, 7-(diethylamino)-4-methyl- a dialkylamino group-containing coumarin compound, 4-dimethylamine, such as 2H-1-benzopyran-2-one (7-(diethylamino)-4-methylcoumarin) Kean acid ethyl ester (Kayacure EPA manufactured by Nippon Kayaku Co., Ltd.), 2-dimethylamino benzoic acid ethyl (Quantacure DMB manufactured by International Bio-synthetics), 4-dimethylamino benzoic acid (n-butoxy) Ethyl (International Bio-synthetics Quantacure BEA), p-dimethylamino benzoic acid isoamyl ethyl ester (Kayacure DMBI, manufactured by Nippon Kayaku Co., Ltd.), 4-dimethylamino benzoic acid 2- Ethylhexyl (Esolol 507, manufactured by Van Dyk Co., Ltd.), 4,4'-diethylaminobenzophenone (EAB, manufactured by Hodogaya Chemical Co., Ltd.).

作為3級胺化合物，以具有二烷基胺基苯結 構之化合物為佳，其中亦以二烷基胺基二苯甲酮化合物，最大吸收波長在350~410nm之含有二烷基胺基的香豆素化合物為特佳。作為二烷基胺基二苯甲酮化合物，因4,4’-二乙基胺基二苯甲酮的毒性亦較低故較佳。最大吸收波長在350~410nm之含有二烷基胺基之香豆素化合物的最大吸收波長在紫外線區域，故可提供使用著色劑，反映著色劑本身顏色的著色膜。特別以7-(二乙基胺基)-4-甲基-2H-1-苯並吡喃-2-酮因對波長400~410nm的雷射光顯示優良增感效果故較佳。 As a tertiary amine compound, having a dialkylamine benzene knot The compound is preferably a dialkylaminobenzophenone compound, and a coumarin compound having a dialkylamine group having a maximum absorption wavelength of 350 to 410 nm is particularly preferred. As the dialkylaminobenzophenone compound, 4,4'-diethylaminobenzophenone is preferred because it has a low toxicity. The maximum absorption wavelength of the dialkylamine-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm is in the ultraviolet region, so that a coloring film which uses a coloring agent and reflects the color of the coloring agent itself can be provided. Particularly, 7-(diethylamino)-4-methyl-2H-1-benzopyran-2-one is preferred because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.

〔(F)感光性(甲基)丙烯酸酯化合物〕 [(F) Photosensitive (meth) acrylate compound]

使用於本發明之(F)感光性(甲基)丙烯酸酯化合物，各藉由活性能量線照射而進行光硬化，使樹脂成分於鹼水溶液中不溶化，或幫助使其不溶化者。作為如此化合物，可使用慣用公知之聚酯(甲基)丙烯酸酯、聚醚(甲基)丙烯酸酯、胺基甲酸酯(甲基)丙烯酸酯、碳酸酯(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯等，具體可舉出2-羥基乙基丙烯酸酯、2-羥基丙基丙烯酸酯等之羥基烷基丙烯酸酯類；乙二醇、甲氧基四乙二醇、聚乙二醇、丙二醇等甘醇之二丙烯酸酯類；N,N-二甲基丙烯醯基、N-羥甲基丙烯醯基、N,N-二甲基胺基丙基丙烯醯基等之丙烯醯基類；N,N-二甲基胺基乙基丙烯酸酯、N,N-二甲基胺基丙基丙烯酸酯等之胺基烷基丙烯酸酯類；已二醇、三羥甲基丙烷、季戊四醇、二季戊四醇、參-羥基乙基異氰脲酸酯 等多價醇或這些環氧乙烷加成物、環氧丙烷加成物、或者ε-己內酯加成物等多價丙烯酸酯類；苯氧基丙烯酸酯、雙酚A二丙烯酸酯、及這些酚類之環氧乙烷加成物或者環氧丙烷加成物等多價丙烯酸酯類；甘油二縮水甘油基醚、甘油三縮水甘油基醚、三羥甲基丙烷三縮水甘油基醚、三縮水甘油基異氰脲酸酯等縮水甘油基醚之多價丙烯酸酯類；未限定於上述者，可舉出聚醚多元醇、聚碳酸酯二醇、羥基末端聚丁二烯、聚酯多元醇等多元醇經直接丙烯酸酯化、或者介著二異氰酸酯使其胺基甲酸酯丙烯酸酯化之丙烯酸酯類及三聚氰胺丙烯酸酯、奈米二氧化矽改性丙烯酸酯或異氰酸酯丙烯酸酯等機能性丙烯酸酯、及對應上述丙烯酸酯之各甲基丙烯酸酯類的至少任一種等。 The (F) photosensitive (meth) acrylate compound used in the present invention is photocured by irradiation with an active energy ray, and the resin component is insolubilized in an aqueous alkali solution or helps to insolubilize it. As such a compound, conventionally known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy can be used. Specific examples of the (meth) acrylate and the like include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; ethylene glycol, methoxytetraethylene glycol, and polyethyl b. a diacrylate of glycol such as diol or propylene glycol; propylene such as N,N-dimethylpropenyl, N-methylolpropenyl or N,N-dimethylaminopropylpropenyl Mercapto group; amine alkyl acrylates such as N,N-dimethylaminoethyl acrylate, N,N-dimethylaminopropyl acrylate; hexane, trimethylolpropane , pentaerythritol, dipentaerythritol, cis-hydroxyethyl isocyanurate a polyvalent alcohol or a polyvalent acrylate such as an ethylene oxide adduct, a propylene oxide adduct, or an ε-caprolactone adduct; a phenoxy acrylate, a bisphenol A diacrylate, And polyvalent acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols; glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether And a polyvalent acrylate such as a glycidyl ether such as triglycidyl isocyanurate; and not limited to the above, examples thereof include polyether polyol, polycarbonate diol, hydroxyl terminal polybutadiene, and poly Polyols such as ester polyols which are directly acrylated or acrylated with urethane via diisocyanate, melamine acrylate, nano cerium oxide modified acrylate or isocyanate acrylate The functional acrylate and at least any one of the methacrylates corresponding to the above acrylate.

又，可舉出甲酚酚醛清漆型環氧樹脂等多官能環氧樹脂與丙烯酸進行反應之環氧丙烯酸酯樹脂，或進一步將該環氧丙烯酸酯樹脂之羥基與季戊四醇三丙烯酸酯等羥基丙烯酸酯及異佛爾酮二異氰酸酯等二異氰酸酯的半胺基甲酸酯化合物進行反應之環氧胺基甲酸酯丙烯酸酯化合物等。如此環氧丙烯酸酯系樹脂無須降低指觸乾燥性，可提高光硬化性。 Further, an epoxy acrylate resin in which a polyfunctional epoxy resin such as a cresol novolac type epoxy resin is reacted with acrylic acid, or a hydroxyl group such as a hydroxyl group of the epoxy acrylate resin and pentaerythritol triacrylate may be mentioned. An epoxy urethane acrylate compound obtained by reacting a semi-carbamate compound of a diisocyanate such as isophorone diisocyanate. Such an epoxy acrylate-based resin can improve the photocurability without lowering the dryness of the touch.

(F)感光性(甲基)丙烯酸酯化合物之配合量對於樹脂成分100質量份而言，較佳為1~150質量份，更佳為5~120質量份之比例。將(F)感光性(甲基)丙烯酸酯化合物的配合量設定在上述範圍內時，可得到良好光硬化性，故較佳。 (F) The amount of the photosensitive (meth) acrylate compound is preferably from 1 to 150 parts by mass, more preferably from 5 to 120 parts by mass, per 100 parts by mass of the resin component. When the amount of the (F) photosensitive (meth) acrylate compound is within the above range, good photocurability is obtained, which is preferable.

〔其他色材〕 [other color materials]

本發明之組成物欲進一步進行色調調整等，可使用(B)特定色材以外，亦可使用(B)特定色材以外的公知慣用色材、有機顏料、無機顏料、有機染料、天然染料、其他色素中任一種。具體可舉出黑色著色劑、紅色著色劑、藍色著色劑、黃色著色劑、綠色著色劑、紫色著色劑、橘色著色劑、茶色著色劑、白色著色劑等。其中因黑色著色劑、藍色著色劑、有藍色之綠色著色劑及紫色著色劑的OD值較高而較佳。 In order to further adjust the color tone or the like, the composition of the present invention may be used in addition to (B) a specific color material, or (B) a known conventional color material other than the specific color material, an organic pigment, an inorganic pigment, an organic dye, a natural dye, or the like. Any of the pigments. Specific examples thereof include a black colorant, a red colorant, a blue colorant, a yellow colorant, a green colorant, a purple colorant, an orange colorant, a brown colorant, a white colorant, and the like. Among them, a black colorant, a blue colorant, a blue green colorant, and a purple colorant have a higher OD value.

(黑色著色劑) (black colorant)

作為黑色著色劑，可舉出C.I.Pigment black 6、7、9、18等碳黑系的顏料、C.I.Pigment black 8、10等黑鉛系的顏料、C.I.Pigment black 11、12、27，Pigment Brown 35等氧化鐵系的顏料；例如戸田工業公司製KN-370的氧化鐵、C.I.Pigment black 20等蒽醌系的顏料、C.I.Pigment black 13、25、29等氧化鈷系的顏料、C.I.Pigment black 15、28等氧化銅系的顏料、C.I.Pigment black 14、26等錳系的顏料、C.I.Pigment black 23等氧化銻系的顏料、C.I.Pigment black 30等氧化鎳系的顏料、C.I.Pigment black 31、32、BASFJAPAN公司製Lumogen Black FK4280的苝系的顏料(除去相當於(B)特定色材者)、Pigment Black 1的苯胺系的顏料及硫化鉬或硫化鉍 亦可作為適用顏料而可例示。這些顏料可單獨或適宜地組合後使用。 Examples of the black coloring agent include carbon black pigments such as CIPigment black 6, 7, 9, and 18, black lead pigments such as CIPigment black 8 and 10, and CIPigment black 11, 12, and 27, and Pigment Brown 35. An iron oxide-based pigment; for example, iron oxide of KN-370 manufactured by Putian Industrial Co., Ltd., an anthraquinone pigment such as CIPigment black 20, a cobalt oxide pigment such as CIPigment black 13, 25, 29, or CIPigment black 15, 28 such as copper oxide pigment, manganese dye such as CIPigment black 14, 26, cerium oxide pigment such as CIPigment black 23, nickel oxide pigment such as CIPigment black 30, CIPigment black 31, 32, BASFJAPAN Lumeng Black FK4280's lanthanide pigment (excluding (B) specific color material), Pigment Black 1 aniline pigment and molybdenum sulfide or strontium sulfide It can also be exemplified as a suitable pigment. These pigments can be used singly or in combination as appropriate.

(紅色著色劑) (red colorant)

作為紅色著色劑，可舉出單偶氮系、雙偶氮系、AZO LAKE(偶氮染料)系、苯並咪唑酮系、苝系、二酮吡咯並吡咯系、縮合偶氮系、蒽醌系、喹吖啶酮系等，具體可舉出如附有下述的顏色指數號碼表示者。 Examples of the red coloring agent include a monoazo type, a bisazo type, an AZO LAKE (azo dye) type, a benzimidazolone type, an anthraquinone type, a diketopyrrolopyrrole type, a condensed azo type, and an anthracene. The quinacridone system or the like is specifically exemplified by a color index number as follows.

單偶氮系：Pigment Red 1，2，3，4，5，6，8，9，12，14，15，16，17，21，22，23，31，32，112，114，146，147，151，170，184，187，188，193，210，245，253，258，266，267，268，269；雙偶氮系：Pigment Red 37，38，41；MONO AZO LAKE(偶氮染料)系：Pigment Red 48：1，48：2，48：3，48：4，49：1，49：2，50：1，52：1，52：2，53：1，53：2，57：1，58：4，63：1，63：2，64：1，68；苯並咪唑酮系：Pigment Red 171，175，176，185，208；苝系：Solvent Red 135，179，Pigment Red 123，149，166，178，179，190，194，224；二酮吡咯並吡咯系：Pigment Red 254，255，264，270，272；縮合偶氮系：Pigment Red 144，166，214，220， 221，242；蒽醌系：Pigment Red 168，177，216，Solvent Red 149，150，52，207；喹吖啶酮系：Pigment Red 122，202，206，207，209 Monoazo system: Pigment Red 1,2,3,4,5,6,8,9,12,14,15,16,17,21,22,23,31,32,112,114,146,147 ,151,170,184,187,188,193,210,245,253,258,266,267,268,269; bisazo system: Pigment Red 37,38,41;MONO AZO LAKE (azo dye) Department: Pigment Red 48:1,48:2,48:3,48:4,49:1,49:2,50:1,52:1,52:2,53:1,53:2,57: 1,58:4,63:1,63:2,64:1,68;benzimidazolone: Pigment Red 171,175,176,185,208; lanthanide: Solvent Red 135,179, Pigment Red 123 , 149, 166, 178, 179, 190, 194, 224; diketopyrrolopyrrole: Pigment Red 254, 255, 264, 270, 272; condensed azo system: Pigment Red 144, 166, 214, 220, 221,242; 蒽醌: Pigment Red 168, 177, 216, Solvent Red 149, 150, 52, 207; quinacridone: Pigment Red 122, 202, 206, 207, 209

(藍色著色劑) (blue colorant)

作為藍色著色劑，有分類為酞菁系(除去相當於(B)特定色材者)、蒽醌系、二噁嗪系(除去相當於(B)特定色材者)、鈷系等顏料系為色素(Pigment)、染料系為溶劑(Solvent)之化合物等，具體可舉出附有如下述顏色指數號碼者。又，除此等以外亦可使用金屬取代或者無取代之酞菁化合物(除去相當於(B)特定色材者)。 As a blue coloring agent, it is classified into a phthalocyanine system (excluding (B) specific color material), an anthraquinone system, a dioxin-based system (excluding (B) specific color material), and a cobalt-based pigment. The compound is a pigment, a dye is a solvent, and the like, and specifically, a color index number as described below is attached. Further, in addition to these, a metal-substituted or unsubstituted phthalocyanine compound (excluding the (B) specific color material) may be used.

顏料系：Pigment Blue 15，15：1，15：2，15：3，15：4，15：6，16，60；染料系：Solvent Blue 35，45，63，67，68，70，83，87，94，97，104，122，136 Pigment system: Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60; dye system: Solvent Blue 35, 45, 63, 67, 68, 70, 83, 87,94,97,104,122,136

(黃色著色劑) (yellow colorant)

作為黃色著色劑，有單偶氮系、雙偶氮系、縮合偶氮系、苯並咪唑酮系、異吲哚啉系、蒽醌系等，具體可舉出以下著色劑。 Examples of the yellow coloring agent include a monoazo type, a disazo type, a condensed azo type, a benzimidazolone type, an isoporphyrin type, and an anthraquinone type. Specific examples thereof include the following colorants.

單偶氮系：Pigment Yellow 1，2，3，4，5，6，9，10，12，61，62，62：1，65，73，74，75，97，100，101，104，105，111，116，167，168，169，182， 183；雙偶氮系：Pigment Yellow 12，13，14，16，17，55，63，81，83，87，126，127，152，170，172，174，176，188，198；縮合偶氮系：Pigment Yellow 93，94，95，128，155，166，180；苯並咪唑酮系：Pigment Yellow 120，151，154，156，175，181；異吲哚啉系：Pigment Yellow 109，110，139，179，185；蒽醌系：Solvent Yellow 163，Pigment Yellow 24，108，193，147，199，202； Monoazo system: Pigment Yellow 1,2,3,4,5,6,9,10,12,61,62,62:1,65,73,74,75,97,100,101,104,105 , 111, 116, 167, 168, 169, 182, 183; bisazo system: Pigment Yellow 12,13,14,16,17,55,63,81,83,87,126,127,152,170,172,174,176,188,198; condensed azo Line: Pigment Yellow 93,94,95,128,155,166,180;benzimidazolone: Pigment Yellow 120,151,154,156,175,181;isoporphyrin system:Pigment Yellow 109,110, 139, 179, 185; lanthanide: Solvent Yellow 163, Pigment Yellow 24, 108, 193, 147, 199, 202;

(綠色著色劑) (green colorant)

作為綠色著色劑，有酞菁系(除去相當於(B)特定色材者)、蒽醌系，具體可使用Pigment Green 7，36，Solvent Green 3，5，20，28等。上述以外亦可使用金屬取代或者無取代之酞菁化合物。 As the green coloring agent, there are a phthalocyanine system (excluding the (B) specific color material) and a lanthanoid system, and specifically, Pigment Green 7, 36, Solvent Green 3, 5, 20, 28 and the like can be used. A metal-substituted or unsubstituted phthalocyanine compound may also be used in addition to the above.

(紫色著色劑) (purple colorant)

作為紫色著色劑，具體可舉出Pigment Violet 19，29，32，36，38，42；Solvent Violet 13，36；Pigment Black 1、Pigment Black 7、Pigment Brown 25等。 Specific examples of the purple coloring agent include Pigment Violet 19, 29, 32, 36, 38, 42; Solvent Violet 13, 36; Pigment Black 1, Pigment Black 7, Pigment Brown 25 and the like.

(橘色著色劑) (orange colorant)

作為橘色著色劑，具體可舉出Pigment Orange 1，5，13，14，16，17，24，34，36，38，40，43，46，49，51，61，63，64，71，73等。 Specific examples of the orange coloring agent include Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71. 73 et al.

(茶色著色劑) (tea coloring agent)

作為茶色著色劑，具體可舉出Pigment brown23，25等。 Specific examples of the brown coloring agent include Pigment brown 23, 25 and the like.

(白色著色劑) (white colorant)

作為白色著色劑，可舉出Pigment white 4所示之酸化鋅、Pigment white 6所示之氧化鈦、Pigment white 7所示之硫化鋅，由著色力與無毒性的觀點來看特別以氧化鈦為佳，例如可舉出富士鈦工業公司製TR-600、TR-700、TR-750、TR-840、石原產業公司製R-550、R-580、R-630、R-820、CR-50、CR-60、CR-90、鈦工業公司製KR-270、KR-310、KR-380等金紅石型氧化鈦、富士鈦工業公司製TA-100、TA-200、TA-300、TA-500、石原產業公司製A100、A220、鈦工業公司製KA-15、KA-20、KA-35、KA-90等銳鈦礦型氧化鈦。少量白色著色劑下，例如於組成物中僅添加至0.1~3質量%，即可期待提高隱蔽性效果。 Examples of the white colorant include zinc acid represented by Pigment white 4, titanium oxide represented by Pigment white 6, and zinc sulfide represented by Pigment white 7. From the viewpoint of coloring power and non-toxicity, titanium oxide is particularly used. For example, TR-600, TR-700, TR-750, TR-840, and R-550, R-580, R-630, R-820, and CR-50 manufactured by Fujitsu Industries Co., Ltd. CR-60, CR-90, rutile type titanium oxide such as KR-270, KR-310, KR-380, etc., TA-100, TA-200, TA-300, TA-made by Fuji Titanium Industry Co., Ltd. 500. A100, A220 manufactured by Ishihara Sangyo Co., Ltd., anatase type titanium oxide such as KA-15, KA-20, KA-35, and KA-90 manufactured by Titanium Industry Co., Ltd. Under a small amount of a white coloring agent, for example, when the composition is added only to 0.1 to 3% by mass, it is expected to improve the concealing effect.

作為(B)特定色材以外之色材，可使用上述中至少任1種以上，但含有黑色著色劑、藍色著色劑、綠 色著色劑及紫色著色劑中至少任1種者為佳，藉此可得到一邊可得到較高OD值，一邊可調整微色相感之優點。又，其中亦以於500~900nm，特別為於500~800nm具有最大吸收波長，而含有380~500nm之吸收比此更低者時，因對OD值或光硬化性無影響故較佳。上述中，作為(B)特定色材以外之色材，具體以含有鈦黑、四三氧化鈷、或呈現黑色之合成無機顏料者為佳，藉此可一邊維持OD值或光硬化性下可一邊提高耐熱性。 As the color material other than the specific color material (B), at least one of the above may be used, but a black colorant, a blue colorant, and a green color may be used. It is preferable that at least one of a coloring agent and a purple coloring agent is preferable, whereby an advantage of being able to obtain a high OD value while adjusting a slight color sensation can be obtained. Further, in the case of 500 to 900 nm, in particular, 500 to 800 nm has a maximum absorption wavelength, and when the absorption of 380 to 500 nm is lower than this, it is preferable because it has no influence on the OD value or photocurability. In the above, as the color material other than the specific color material (B), it is preferable to contain titanium black, cobalt tetraoxide, or a synthetic inorganic pigment which exhibits black color, whereby the OD value or photocurability can be maintained. Improve heat resistance.

(B)特定色材以外的色材的配合量以與使用於本發明之(B)特定色材的比率下，以(A)：(A)以外的色材為99：1~10：90之範圍者為佳，以99：1~30：70的範圍者為較佳，以99：1~50：50的範圍者為更佳，以99：1~51：49的範圍者為特佳。將(B)特定色材以外的色材之配合量在上述範圍內時，特別對於OD值與光硬化性及耐光性而言，可得到平衡良好的硬化性樹脂組成物。 (B) the blending amount of the color material other than the specific color material is the ratio of the color material other than (A): (A) to the ratio of the specific color material used in (B) of the present invention: 99:1 to 10:90 The range is better, preferably in the range of 99:1 to 30:70, preferably in the range of 99:1 to 50:50, and especially in the range of 99:1 to 51:49. . When the blending amount of the color material other than the specific color material (B) is within the above range, a curable resin composition having a good balance can be obtained particularly for the OD value, the photocurability, and the light resistance.

〔熱硬化觸媒〕 [thermosetting catalyst]

對於本發明之硬化性樹脂組成物，進一步含有熱硬化觸媒者為佳。作為熱硬化觸媒，例如可舉出咪唑、2-甲基咪唑、2-乙基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、4-苯基咪唑、1-氰基乙基-2-苯基咪唑、1-(2-氰基乙基)-2-乙基-4-甲基咪唑等咪唑衍生物；二氰二醯胺、苯甲基二甲基胺、4-(二甲基胺基)-N,N-二甲基苯甲基胺、4-甲氧 基-N,N-二甲基苯甲基胺、4-甲基-N,N-二甲基苯甲基胺等胺化合物、己二酸二醯肼、癸二酸二醯肼等肼化合物；三苯基次膦等磷化合物等。又，作為被市售者，例如可舉出四國化成工業公司製的2MZ-A、2MZ-OK、2PHZ、2P4BHZ、2P4MHZ(皆為咪唑系化合物之商品名)、san-apro公司製的U-CAT3503N、U-CAT3502T(皆為二甲基胺之嵌段異氰酸酯化合物的商品名)、DBU、DBN、U-CATSA102、U-CAT5002(皆為二環式脒化合物及其鹽)等。且並未限定於此等，僅為可促進環氧樹脂或氧雜環丁烷化合物之熱硬化觸媒、或者環氧基及/或氧雜環丁烷基與羧基之反應者即可使用，這些可單獨使用，或混合2種以上使用。又，可使用胍胺、乙醯胍胺、苯並胍胺、三聚氰胺、2,4-二胺基-6-甲基丙烯醯氧乙基-S-三嗪、2-乙烯基-2,4-二胺基-S-三嗪、2-乙烯基-4,6-二胺基-S-三嗪‧異氰脲酸加成物、2,4-二胺基-6-甲基丙烯醯氧乙基-S-三嗪‧異氰脲酸加成物等S-三嗪衍生物，較佳為將這些可作為密著性賦予劑功能的化合物與熱硬化觸媒併用。 It is preferable that the curable resin composition of the present invention further contains a thermosetting catalyst. Examples of the thermosetting catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, and 1-cyanoquinone. Imidazole derivatives such as ethyl ethyl-2-phenylimidazole and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; dicyanodiamide, benzyldimethylamine, 4-(Dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy An amine compound such as benzyl-N,N-dimethylbenzylamine or 4-methyl-N,N-dimethylbenzylamine, anthracene compound such as diammonium adipate or diterpene sebacate a phosphorus compound such as triphenylphosphinium or the like. In addition, as a commercially available product, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, and 2P4MHZ (all are imidazole-based compounds) manufactured by Shikoku Chemicals Co., Ltd., and U manufactured by San-apro Co., Ltd. -CAT3503N, U-CAT3502T (all trade names of block isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all of which are bicyclic guanidine compounds and salts thereof). Further, it is not limited thereto, and can be used only for a thermosetting catalyst capable of promoting an epoxy resin or an oxetane compound, or a reaction of an epoxy group and/or an oxetane group with a carboxyl group. These can be used individually or in mixture of 2 or more types. Further, guanamine, acetamide, benzoguanamine, melamine, 2,4-diamino-6-methylpropenyloxyethyl-S-triazine, 2-vinyl-2,4 can be used. -diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine ‧ isocyanuric acid adduct, 2,4-diamino-6-methyl propylene hydride An S-triazine derivative such as an oxyethyl-S-triazine ‧ isocyanuric acid addition product is preferably used in combination with a thermosetting catalyst which is a function of the adhesion imparting agent.

熱硬化觸媒之配合量以一般使用的比例即充分，例如對於樹脂成分或(C)熱硬化性成分100質量份而言，較佳為0.1~20質量份，更佳為0.5~15.0質量份。 The amount of the thermosetting catalyst to be used is generally sufficient, for example, 0.1 to 20 parts by mass, more preferably 0.5 to 15.0 parts by mass, per 100 parts by mass of the resin component or (C) thermosetting component. .

〔其他配合成分〕 [Other ingredients]

又，本發明之組成物中，可進一步以提高硬化物之密 著性、機械性強度、線膨張係數等特性為目的下，添加無機填充材。作為如此無機填充材，例如可使用硫酸鋇、鈦酸鋇、氧化矽粉、微粉狀氧化矽、無定形二氧化矽、滑石、黏土、碳酸鎂、碳酸鈣、氧化鋁、氫氧化鋁、雲母粉等之公知慣用的無機填充劑。 Moreover, in the composition of the present invention, the hardness of the cured product can be further improved An inorganic filler is added for the purpose of properties such as properties, mechanical strength, and linear expansion coefficient. As such an inorganic filler, for example, barium sulfate, barium titanate, cerium oxide powder, fine powdered cerium oxide, amorphous cerium oxide, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica can be used. A well-known inorganic filler such as powder.

本發明之組成物中，進一步配合需要添加氫醌、氫醌單甲基醚、t-丁基鄰苯二酚、鄰苯三酚、吩噻嗪等之公知慣用之聚合禁止劑、微粉二氧化矽、有機膨潤土、蒙脫石等之公知慣用之增黏劑、聚矽氧系、氟系、高分子系等之消泡劑及塗平劑的至少任1種、如異氰酸酯系、咪唑系、噻唑系、***系等矽烷偶合劑、抗氧化劑、光聚合增感劑、光安定劑、分散劑、硬化促進劑、難燃劑、難燃助劑等之公知慣用的添加劑類。 In the composition of the present invention, a known conventional polymerization inhibitor, such as hydroquinone, hydroquinone monomethyl ether, t-butyl catechol, pyrogallol, phenothiazine, or the like, may be further added. At least one of a known tackifier, a polyfluorene-based, a fluorine-based, a polymer-based antifoaming agent, and a coating agent, such as an isocyanate or an imidazole, etc., such as an anthracene, an organic bentonite, or a montmorillonite. A well-known and customary additive such as a thiazole coupling agent such as a thiazole system or a triazole system, an antioxidant, a photopolymerization sensitizer, a photostabilizer, a dispersant, a hardening accelerator, a flame retardant, and a flame retardant auxiliary.

本發明之組成物可含有使用於組成物的調製或黏度調整時的有機溶劑。作為有機溶劑，例如可舉出甲基乙基酮、環己酮等酮類；甲苯、二甲苯、四甲基苯等芳香族烴類；溶纖劑、甲基溶纖劑、丁基溶纖劑、卡必醇、甲基卡必醇、丁基卡必醇、丙二醇單甲基醚、二丙二醇單甲基醚(DPM)、二丙二醇二乙基醚、三丙二醇單甲基醚等甘醇醚類；乙酸乙酯、乙酸丁酯、乳酸丁酯、溶纖劑乙酸酯、丁基溶纖劑乙酸酯、卡必醇乙酸酯、丁基卡必醇乙酸酯、丙二醇單甲基醚乙酸酯、二丙二醇單甲基醚乙酸酯、碳酸伸丙基等酯類；辛烷、癸烷等脂肪族烴類；石油醚、石腦油、溶劑腦油等石油系溶劑等。這些有機溶劑可 單獨使用，或組合2種類以上使用。 The composition of the present invention may contain an organic solvent used in the preparation of the composition for adjustment or viscosity adjustment. Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, and butyl cellosolve. Glycol ethers such as carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether (DPM), dipropylene glycol diethyl ether, tripropylene glycol monomethyl ether Ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate Esters such as esters, dipropylene glycol monomethyl ether acetate, and propylene carbonate; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, naphtha, and solvent brain oil. These organic solvents can Used alone or in combination of two or more types.

由上述配合成分所成的本發明之硬化性樹脂組成物，即使作為組成物，於可見光區域380~780nm中，於500~780nm具有最大吸收值，於380~500nm具有最小吸收值，但由可得到高OD值之感光性組成物的觀點來看為較佳，又以呈現黑色者為佳。藉由顯示黑色度的測色計，該硬化物之L*值由SCI方式表示時以30以下者為佳。又，a*值以-5~5，b*值以-5~5為佳。較佳為a*值為-2~2，b*值為-2~2。 The curable resin composition of the present invention which is formed of the above-mentioned compounding component has a maximum absorption value at 500 to 780 nm in the visible light region of 380 to 780 nm, and has a minimum absorption value at 380 to 500 nm. It is preferable from the viewpoint of obtaining a photosensitive composition having a high OD value, and it is preferable to exhibit a black color. It is preferable that the L* value of the cured product is 30 or less by the SCI method by the colorimeter displaying the blackness. Also, the a* value is -5 to 5, and the b* value is preferably -5 to 5. Preferably, the a* value is -2 to 2, and the b* value is -2 to 2.

本發明之硬化性樹脂組成物為具有高OD值之同時具有高絕緣性者，故作為絕緣膜形成用之材料為有用。又，本發明之硬化性樹脂組成物作為遮光用構件時亦為有用。進一步本發明之硬化性樹脂組成物可成為具有高OD值之同時具有優良感光性者，故藉由使用本發明之硬化性樹脂組成物，可得到高品質顯示用構件。本發明之硬化性樹脂組成物可使用於其他印刷墨水、噴墨墨水、光罩製作材料、印刷用防潮紙製作材料、蝕刻抗蝕、焊接抗蝕、電漿顯示板(PDP)之隔壁、介電體圖型、電極(導體回路)圖型、電子零件之配線圖型、導電糊、導電薄膜、黑色矩陣等遮蔽圖像等製作，特別為本發明之硬化性樹脂組成物可使用於提高使用於彩色液晶顯示裝置等的彩色濾器之顯示特性時，因於著色圖型的間隔部、周邊部分、及TFT之外光側等設有遮光圖像(含有黑色矩陣)，故可適用於觸控板用遮光膜。特佳為適用於液晶顯 示裝置、電漿顯示顯示裝置、具備無機EL之EL顯示裝置、CRT顯示裝置、設置於具備觸控板之顯示裝置的周邊之黑色邊緣(形成擋板)或作為紅、藍、綠之著色畫素間的格子狀或條紋狀黑色部分，更佳為使用於TFT遮光時的點狀或線狀黑色圖型等黑色矩陣使用。 Since the curable resin composition of the present invention has high OD value and high insulating property, it is useful as a material for forming an insulating film. Moreover, the curable resin composition of the present invention is also useful as a member for light shielding. Further, since the curable resin composition of the present invention has high OD value and excellent photosensitivity, a high-quality display member can be obtained by using the curable resin composition of the present invention. The curable resin composition of the present invention can be used for other printing inks, inkjet inks, mask manufacturing materials, moisture-proof paper making materials for printing, etching resists, solder resists, and plasma display panels (PDP). The electric pattern, the electrode (conductor loop) pattern, the wiring pattern of the electronic component, the conductive paste, the conductive film, the shading image such as a black matrix, etc., and the curable resin composition of the present invention can be used for improving the use. When the display characteristics of a color filter such as a color liquid crystal display device are provided, a light-shielding image (including a black matrix) is provided for the spacer portion, the peripheral portion, and the light side of the TFT, and thus the touch panel can be applied to the touch. The board uses a light-shielding film. Especially suitable for liquid crystal display Display device, plasma display display device, EL display device with inorganic EL, CRT display device, black edge (formed with a baffle) provided on the periphery of a display device having a touch panel, or as a red, blue, and green color painting The grid-like or striped black portion between the elements is preferably used for a black matrix such as a dot-like or linear black pattern when the TFT is shielded from light.

本發明之組成物可為塗布於載體薄膜(支持體)上並使其乾燥所得之乾薄膜的形態。進行此乾薄膜化時，將本發明之組成物以上述有機溶劑進行稀釋調整為適度黏度後，以缺角輪塗佈機、刮刀塗佈機、唇形塗佈機、桿塗佈機、擠壓塗佈機、逆向塗佈機、轉移輥塗機、凹印塗佈機、噴霧塗佈機等塗布於載體薄膜上成均勻厚度，一般以50~130℃之溫度進行1~30分鐘乾燥，可作為乾燥塗膜。對於塗佈膜厚並無特別限定，但一般為乾燥後膜厚以0.1~100μm為佳，較佳為適宜地選自0.5~50μm之範圍。 The composition of the present invention may be in the form of a dry film obtained by coating on a carrier film (support) and drying it. When the dry film formation is carried out, the composition of the present invention is diluted with the above organic solvent to adjust to a moderate viscosity, and then a notch wheel coater, a knife coater, a lip coater, a rod coater, and a squeeze Press coater, reverse coater, transfer roll coater, gravure coater, spray coater, etc. are applied to the carrier film to a uniform thickness, and are generally dried at a temperature of 50 to 130 ° C for 1 to 30 minutes. Can be used as a dry coating film. The coating film thickness is not particularly limited, but is generally preferably 0.1 to 100 μm after drying, and is preferably selected from the range of 0.5 to 50 μm.

作為載體薄膜，使用塑質薄膜，以使用聚乙烯對苯二甲酸乙二醇酯等聚酯薄膜、聚醯亞胺薄膜、聚醯胺醯亞胺薄膜、聚丙烯薄膜、聚苯乙烯薄膜等塑質薄膜為佳。對於載體薄膜之厚度並無特別限定，一般為選自0.1~150μm之範圍為佳。 As the carrier film, a plastic film is used, and a polyester film such as polyethylene terephthalate, a polyimide film, a polyimide film, a polypropylene film, a polystyrene film, or the like is used. A quality film is preferred. The thickness of the carrier film is not particularly limited, but is preferably selected from the range of 0.1 to 150 μm.

此時，於載體薄膜上進行塗布成膜後，以防止於塗膜表面上附著灰塵等目的，於塗膜表面進一步層合可剝離之覆蓋薄膜為佳。作為可剝離之覆蓋薄膜，例如可使用聚乙烯薄膜、聚四氟伸乙基薄膜、聚丙烯薄膜、經表 面處理之紙等，剝離覆蓋薄膜時，塗膜與覆蓋薄膜之接著力比塗膜與載體薄膜之接著力小者即可。 In this case, after the film is formed on the carrier film, it is preferable to further laminate the peelable cover film on the surface of the coating film for the purpose of preventing dust from adhering to the surface of the coating film. As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, and a watch can be used. When the cover film is peeled off, the adhesion between the coating film and the cover film may be smaller than the adhesion between the coating film and the carrier film.

又，將本發明之組成物調整為使用上述有機溶劑於塗佈方法的較佳黏度後，於基材上藉由浸塗法、流動塗布法、輥塗佈法、棒塗佈法、絲網印刷法、幕式塗佈法、模具塗佈法等方法進行塗佈，以約50℃~90℃之溫度將含於組成物中之有機溶劑揮發乾燥(假乾燥)後，可形成無黏性乾燥塗膜。又，將本發明之組成物塗布於載體薄膜上，經乾燥後作為薄膜捲成乾薄膜時，將此藉由層合體等，貼合於基材上使組成物之塗膜與基材接觸後，藉由剝開載體薄膜，基材上可形成塗膜之層。 Further, the composition of the present invention is adjusted to have a preferred viscosity of the above-mentioned organic solvent in the coating method, and then subjected to dip coating, flow coating, roll coating, bar coating, and wire mesh on the substrate. Coating by a printing method, a curtain coating method, a die coating method, etc., and the organic solvent contained in the composition is volatilized and dried (false drying) at a temperature of about 50 ° C to 90 ° C to form a non-stick property. Dry the film. Further, when the composition of the present invention is applied onto a carrier film and dried to form a film as a dry film, the film is bonded to the substrate by a laminate or the like to bring the coating film of the composition into contact with the substrate. By peeling off the carrier film, a layer of the coating film can be formed on the substrate.

將這些塗膜，例如藉由活性能量線照射使其光硬化，或於100℃~250℃之溫度下進行加熱使其熱硬化後可得到硬化物。 These coating films are photohardened by, for example, irradiation with an active energy ray, or heated at a temperature of from 100 ° C to 250 ° C to be thermally cured to obtain a cured product.

作為上述基材，可舉出先形成回路的印刷電路板或可撓性印刷電路板以外，亦可舉出使用紙酚、紙環氧、玻璃布環氧、玻璃聚醯亞胺、玻璃布/不纖布環氧、玻璃布/紙環氧、合成纖維環氧、氟樹脂‧聚乙烯‧聚伸苯基醚‧氰酸酯酯樹脂等之高頻率回路用銅張積層板等材質者之所有等級(FR-4等)的貼銅層合板，其他可舉出聚醯亞胺薄膜、PET薄膜、玻璃基板、陶瓷基板、晶圓板等。 Examples of the substrate include a printed circuit board or a flexible printed circuit board in which a circuit is formed first, and paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/ All materials such as non-fibrous epoxy, glass cloth/paper epoxy, synthetic fiber epoxy, fluororesin, polyethylene, polyphenylene ether, cyanate ester resin, etc. For the copper-clad laminate of the grade (FR-4, etc.), other examples include a polyimide film, a PET film, a glass substrate, a ceramic substrate, and a wafer plate.

塗布本發明之組成物後所進行的揮發乾燥可使用熱風循環式乾燥爐、IR爐、加熱板、對流烤箱等具 備藉由蒸氣的空氣加熱方式之熱源者，將乾燥機內之熱風進行向流接觸的方法、及可藉由噴嘴對支持體吹的方法而進行。 The volatilization drying carried out after coating the composition of the present invention can be carried out using a hot air circulating drying furnace, an IR furnace, a heating plate, a convection oven, etc. A heat source for the air heating method of steam is used to bring the hot air in the dryer into contact with the flow, and a method in which the support can be blown by the nozzle.

作為使用於活性能量線照射之曝光機，僅為配置高壓水銀燈、超高壓水銀燈、金屬鹵素燈、水銀短弧燈等，在350~450nm之範圍可照射紫外線之裝置即可，且亦可使用直接繪圖裝置(例如藉由自電腦之CAD數據直接照射活性能量線後描繪圖像直接成像之裝置)。作為直描機之光源，僅使用最大波長在350~410nm之範圍的光即可。使用於圖像形成之曝光量依據膜厚等而相異，但一般為20~1000mJ/cm2，較佳為20~800mJ/cm2之範圍內。 As an exposure machine for active energy ray irradiation, only a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a mercury short-arc lamp, or the like can be disposed, and a device that can irradiate ultraviolet rays in a range of 350 to 450 nm can be used, and can also be used directly. A drawing device (for example, a device that directly images an image by directly irradiating an active energy line from CAD data of a computer). As the light source of the direct drawing machine, only light having a maximum wavelength in the range of 350 to 410 nm can be used. The amount of exposure used for image formation differs depending on the film thickness and the like, but is generally in the range of 20 to 1000 mJ/cm 2 , preferably 20 to 800 mJ/cm 2 .

又，作為顯像方法，可藉由浸漬法、噴淋法、噴霧法、梳刷法等完成，作為顯像液可使用氫氧化鉀、氫氧化鈉、碳酸鈉、碳酸鉀、磷酸鈉、矽酸鈉、氨、胺類等鹼水溶液。 Further, as a developing method, it can be completed by a dipping method, a shower method, a spray method, a combing method, or the like, and potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, or barium can be used as the developing solution. An aqueous alkali solution such as sodium, ammonia or amine.

〔實施例〕 [Examples]

以下將本發明使用實施例做更詳細說明。 Hereinafter, the present invention will be described in more detail using an embodiment.

依據下述表1，2中所示調配，添加各成分並攪拌後以3根輥進行分散，調製出各組成物。且表1，2中之配合量表示質量份。 According to the mixing shown in the following Tables 1 and 2, each component was added, stirred, and dispersed by three rolls to prepare each composition. And the compounding quantity in Table 1, 2 shows the mass part.

〔合成例1〕 [Synthesis Example 1]

於二乙二醇單乙基醚乙酸酯700g中裝入鄰甲酚酚醛清漆型環氧樹脂(DIC公司製之EPICLON(EPICLON)N-695、軟化點95℃、環氧當量214、平均官能基數7.6)1070g(縮水甘油基數(芳香環總數)：5.0莫耳)、丙烯酸360g(5.0莫耳)、及氫醌1.5g，在100℃進行加熱攪拌後均勻溶解。 An o-cresol novolac type epoxy resin (EPICLON (EPICLON) N-695, manufactured by DIC Corporation, softening point 95 ° C, epoxy equivalent 214, average functional group) was placed in 700 g of diethylene glycol monoethyl ether acetate. Base 7.6) 1070 g (glycidyl group (total number of aromatic rings): 5.0 mol), 360 g of acrylic acid (5.0 mol), and 1.5 g of hydroquinone were uniformly dissolved by heating and stirring at 100 °C.

其次裝入三苯基次膦4.3g，於110℃加熱並進行2小時反應後，再追加三苯基次膦1.6g，升溫至120℃後，再進行12小時反應。於所得之反應液中，裝入芳香族系烴(SOLVESSO150)562g、四氫鄰苯二甲酸酐684g(4.5莫耳)，在110℃進行4小時反應。再於所得之反應液中裝入縮水甘油基甲基丙烯酸酯142.0g(1.0莫耳)，在115℃進行4小時反應後，得到感光性含羧基樹脂溶液。如此所得之樹脂溶液的固體成分為65%，固體成分之酸價為87mgKOH/g。 Next, 4.3 g of triphenylphosphinane was charged, and after heating at 110 ° C for 2 hours, 1.6 g of triphenylphosphinylphosphine was further added thereto, and the mixture was heated to 120 ° C, and further reacted for 12 hours. Into the obtained reaction liquid, 562 g of an aromatic hydrocarbon (SOLVESSO 150) and 684 g (4.5 mol) of tetrahydrophthalic anhydride were charged, and the reaction was carried out at 110 ° C for 4 hours. Further, 142.0 g (1.0 mol) of glycidyl methacrylate was placed in the obtained reaction liquid, and the reaction was carried out at 115 ° C for 4 hours to obtain a photosensitive carboxyl group-containing resin solution. The solid content of the resin solution thus obtained was 65%, and the acid value of the solid content was 87 mgKOH/g.

*3)HO(三菱人皂絲公司製)*4)N870(DIC公司製之改性酚醛清漆環氧樹脂)*5)1001(日本環氧樹脂公司製之雙酚環氧樹脂)*6)HF-1(明和化成公司製之酚樹脂)*7)828(日本環氧樹脂公司製之雙酚環氧樹脂)*8)NC3000H(日本化藥公司製之環氧樹脂)*9)S.B.7(Orient化學工業公司製 有機染料)(最大吸收值595nm，最小吸收值408nm) *10)P.V.37(BASFJAPAN公司製 有機顏料CTROMOPHTAL VIOLET D5700)*11)四三氧化鈷(合成無機顏料)*12)BYK-LPD20950(BYK‧JAPAN公司製)*13)BYK-354(BYK‧JAPAN公司製)*14)Polyflow No.99C(共榮公司化學公司製之丙烯酸聚合物系消泡劑)*15)Lumogen S0795(BASFJAPAN公司製)*16)碳黑(無機顏料)*17)化合物(A) *18)化合物B(2-苯甲基-2-二甲基胺基-1-(4-嗎啉代苯基)-丁烷-1-酮)*19)SDO-C33(有本化學工業公司製 雜環系化合物)*20)SIR-132(三井化學公司製)*21)YKR-5010(山本化成公司製)*22)LumogenIR765(BASFJAPAN公司製)*23)IRG-022(日本化藥公司製)*24)AEROSIL 380(Nippon Aerosil公司製之親水性氣相二氧化矽) *3) HO (manufactured by Mitsubishi Soap Co., Ltd.) *4) N870 (modified novolac epoxy resin manufactured by DIC Corporation) *5) 1001 (bisphenol epoxy resin manufactured by Nippon Epoxy Co., Ltd.)*6) HF-1 (phenol resin manufactured by Minghe Chemical Co., Ltd.)*7)828 (bisphenol epoxy resin manufactured by Nippon Epoxy Co., Ltd.)*8) NC3000H (epoxy resin manufactured by Nippon Kayaku Co., Ltd.)*9) SB7 ( Orient Chemical Industry Co., Ltd. organic dye) (maximum absorption value 595nm, minimum absorption value 408nm) *10) PV37 (organic pigment CTROMOPHTAL VIOLET D5700 made by BASFJAPAN)*11) Cobalt trioxide (synthetic inorganic pigment)*12) BYK-LPD20950 (made by BYK‧JAPAN)*13) BYK-354 (BYK‧JAPAN company *14) Polyflow No.99C (acrylic polymer defoamer manufactured by Kyoei Chemical Co., Ltd.)*15) Lumogen S0795 (manufactured by BASFJAPAN Co., Ltd.)*16) Carbon black (inorganic pigment)*17) Compound (A) ) *18) Compound B (2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one)*19) SDO-C33 (with this chemical industry) Company made heterocyclic compound) *20) SIR-132 (manufactured by Mitsui Chemicals, Inc.) *21) YKR-5010 (manufactured by Yamamoto Kasei Co., Ltd.) *22) Lumogen IR765 (manufactured by BASF JAPAN Co., Ltd.) *23) IRG-022 (Nippon Chemical Co., Ltd.) Company system)*24) AEROSIL 380 (hydrophilic gas phase cerium oxide manufactured by Nippon Aerosil Co., Ltd.)

對於所得之各實施例及比較例的組成物，依據以下進行評估。將該結果表示於下述表3，4所示。 The composition of each of the obtained Examples and Comparative Examples was evaluated in accordance with the following. The results are shown in Tables 3 and 4 below.

(OD值(光學濃度)) (OD value (optical density))

實施例1及比較例3，4於熱風循環式乾燥爐中160℃下進行30分鐘，實施例2及比較例1，2於80W3燈之高壓水銀燈UV輸送爐下1000mJ/cm2，實施例3~9及比較例5~8於熱風循環式乾燥爐中在80℃下進行10分鐘乾燥後形成乾燥塗膜，其次藉由設有Oak製作所公司製之金屬鹵素燈的曝光機，以成為感度7段之曝光量進行曝光。其後藉由1wt% Na2CO3水溶液以噴霧壓0.1MPa進行1分鐘顯像，其次使用熱風循環式乾燥爐在150℃施予60分鐘熱硬化處理後，製作出於玻璃上厚度10μm之硬化塗膜，以透過濃度計(X-Rite公司361T)進行測定。該裝置檢測出400~900nm之全波長，算出OD值。OD值由透過光量T並依據下述式算出。OD值越高，塗膜之遮光性月高為佳。組成物調整至OD3以上。 Example 1 and Comparative Examples 3 and 4 were carried out at 160 ° C for 30 minutes in a hot air circulating drying oven, and Example 2 and Comparative Examples 1 and 2 were placed at 1000 mJ/cm 2 under a high pressure mercury lamp UV transfer furnace of an 80 W3 lamp. Example 3 ~9 and Comparative Examples 5 to 8 were dried in a hot air circulating drying oven at 80 ° C for 10 minutes to form a dried coating film, and secondly by an exposure machine equipped with a metal halide lamp manufactured by Oak Co., Ltd., to become a sensitivity 7 The exposure amount of the segment is exposed. Thereafter, development was carried out by a 1 wt% Na 2 CO 3 aqueous solution at a spray pressure of 0.1 MPa for 1 minute, followed by a hot air circulating drying oven at 150 ° C for 60 minutes, and then hardened to a thickness of 10 μm on the glass. The coating film was measured by a transmission densitometer (X-Rite Co., Ltd. 361T). The device detects the full wavelength of 400 to 900 nm and calculates the OD value. The OD value is calculated from the transmitted light amount T according to the following formula. The higher the OD value, the better the opacity of the coating film. The composition was adjusted to be above OD3.

OD值=-Log10(T/100) OD value = -Log 10 (T/100)

(表面電阻值) (surface resistance value)

於將各組成物各洗淨之玻璃上，以絲網印刷全面塗布置乾燥後10μm，實施例1及比較例3，4為以熱風循環式乾燥爐在160℃下進行30分鐘，實施例2及比較例1，2為在80W3燈之高壓水銀燈UV輸送爐以1000mJ/cm2，實施例3~9及比較例5~8為在熱風循環式乾燥爐以80℃進行10分鐘乾燥，形成各乾燥塗膜，其次藉由裝有Oak 製作所公司製金屬鹵素燈之曝光機以成為感度7段之曝光量進行曝光。其後，藉由1wt% Na2CO3水溶液，以噴霧壓0.1MPa進行1分鐘顯像，其次使用熱風循環式乾燥爐，在150℃施予60分鐘熱硬化處理後得到硬化塗膜。各實施例及比較例之硬化性樹脂組成物的表面電阻值依據JIS K6911進行測定。 The glass of each of the compositions was washed by screen printing and dried to a thickness of 10 μm, and Example 1 and Comparative Examples 3 and 4 were subjected to a hot air circulating drying oven at 160 ° C for 30 minutes. Example 2 And Comparative Examples 1 and 2 were 1000 mJ/cm 2 in a high-pressure mercury lamp UV transfer furnace of 80 W3 lamps, and Examples 3 to 9 and Comparative Examples 5 to 8 were dried in a hot air circulating drying oven at 80 ° C for 10 minutes to form each. The coating film was dried, and then exposed by an exposure machine equipped with a metal halide lamp manufactured by Oak Co., Ltd. to obtain an exposure amount of 7 degrees of sensitivity. Thereafter, development was carried out by a 1 wt% Na 2 CO 3 aqueous solution at a spray pressure of 0.1 MPa for 1 minute, and then a hot air circulation type drying oven was used, and a heat-curing treatment was performed at 150 ° C for 60 minutes to obtain a cured coating film. The surface resistance value of the curable resin composition of each of the examples and the comparative examples was measured in accordance with JIS K6911.

(分光測色計) (Spectrophotometer)

對於由上述表面電阻值評估所得之硬化塗膜，使用分光測色計(Konica Minolta公司製，CM-2600d)，將塗膜上之L*a*b*表色系的值依據JIS Z 8729進行測定，表示明度指數之L*a*b*值作為黑色度的指標進行評估。該L*值越小，又a*、b*值同時越接近0時，表黑色度越優良。 For the hardened coating film obtained by the evaluation of the surface resistance value, a spectrophotometer (CM-2600d, manufactured by Konica Minolta Co., Ltd.) was used, and the value of the L*a*b* color system on the coating film was determined in accordance with JIS Z 8729. The measurement indicates that the L*a*b* value of the brightness index is evaluated as an indicator of blackness. The smaller the L* value is, the closer the a* and b* values are to 0, the better the blackness of the watch.

(感度) (Sensitivity)

將實施例3~9及比較例5~8的硬化性樹脂組成物於經洗淨之玻璃上以絲網印刷全面塗布置乾燥後成為10μm，於熱風循環式乾燥爐以80℃進行10分鐘乾燥。於該塗膜上以柯達公司製的Step tablet(21段)，藉由設有Oak製作所公司製金屬鹵素燈之曝光機以300mJ/cm2的曝光量進行曝光，藉由1wt% Na2CO3水溶液，以噴霧壓0.1MPa進行1分鐘顯像後，對其殘存段數進行調查。殘存段數越多，感度越良好而較佳。 The curable resin compositions of Examples 3 to 9 and Comparative Examples 5 to 8 were dried on a cleaned glass by screen printing, and dried to 10 μm, and dried in a hot air circulating drying oven at 80 ° C for 10 minutes. . On the coating film, a Step tablet (21-stage) manufactured by Kodak Co., Ltd. was exposed by an exposure machine equipped with a metal halide lamp manufactured by Oak Co., Ltd. at an exposure amount of 300 mJ/cm 2 by 1 wt% Na 2 CO 3 . The aqueous solution was developed for 1 minute at a spray pressure of 0.1 MPa, and the number of remaining segments was examined. The more the number of remaining segments, the better the sensitivity and the better.

( 100μm製圖) ( 100μm drawing)

將實施例3~9及比較例5~8之硬化性樹脂組成物於洗淨的玻璃上全面塗布置乾燥塗膜成為10μm，以熱風循環式乾燥爐在80℃進行10分鐘乾燥。於該塗膜上針對開口為 100μm之負型薄膜，藉由設有Oak製作所公司製的金屬鹵素燈之曝光機以成為感度7段之曝光量進行曝光，藉由1wt% Na2CO3水溶液以噴霧壓0.1MPa進行1分鐘顯像後之開口精度進行評估。評估基準如以下所示。 The curable resin compositions of Examples 3 to 9 and Comparative Examples 5 to 8 were uniformly coated on the cleaned glass to a dry coating film of 10 μm, and dried in a hot air circulating drying oven at 80 ° C for 10 minutes. On the coating film, the opening is A negative film of 100 μm was exposed by exposure to a metal halide lamp manufactured by Oak Co., Ltd., and exposed to a sensitivity of 7 stages, and a 1 wt% Na 2 CO 3 aqueous solution was sprayed at 0.1 MPa for 1 minute. The accuracy of the opening is evaluated as follows. The evaluation criteria are as follows.

○：銳利之解像度。 ○: Sharp resolution.

△：雖非銳利但得到負型尺寸之。 △: Although not sharp, it has a negative size. .

×：藉由光暈、底切無法得到解像性。 ×: Resolution cannot be obtained by halation and undercutting.

上述表中之結果確認到各實施例之組成物，與各比較例進行比較下，可得到高OD值，且黑色度亦優良者。又對於各實施例之組成物中，對於表面電阻值亦得到良好性能，亦不會產生經時性所引起的沈澱問題。特別確認到對於兼備光硬化性與熱硬化性之組成物的情況下，得到良好感度及良好製圖性。相對於此，未含有(B)特定色材之比較例中，無法得到高OD值，色調亦大幅度相異。 As a result of the above table, the composition of each example was confirmed, and compared with each comparative example, the high OD value was obtained, and the blackness was also excellent. Further, in the compositions of the respective examples, the surface resistance value was also excellent, and the precipitation problem caused by the lapse of time was not caused. In particular, in the case of a composition having both photocurability and thermosetting properties, it was confirmed that good sensitivity and good patterning property were obtained. On the other hand, in the comparative example which did not contain (B) a specific color material, the high OD value was not acquired, and the color tone differs greatly.

Claims (11)

一種硬化性樹脂組成物，其特徵為含有(A)最大吸收波長為800~1000nm之近紅外線吸收劑、(B)在可見光區域380~780nm中，於380~500nm具有最小吸收值，於500~780nm具有最大吸收值的色材、(C)熱硬化性成分，及(D)鹼可溶性樹脂；(A)近紅外線吸收劑之含有率係於組成物(固體成分)中為0.001~50質量%，(B)特定色材之配合量係於組成物(固體成分)中為0.05~80質量%，(C)熱硬化性成分之配合量係相對於樹脂成分100質量份為0.6~2.8當量。 A curable resin composition characterized by comprising (A) a near-infrared absorbing agent having a maximum absorption wavelength of 800 to 1000 nm, and (B) a minimum absorption value at 380 to 500 nm in a visible light region of 380 to 780 nm, at 500~ a color material having a maximum absorption value at 780 nm, (C) a thermosetting component, and (D) an alkali-soluble resin; (A) a content of the near-infrared absorbing agent is 0.001 to 50% by mass in the composition (solid content) (B) The amount of the specific color material is 0.05 to 80% by mass in the composition (solid content), and the amount of the (C) thermosetting component is 0.6 to 2.8 equivalents based on 100 parts by mass of the resin component. 如請求項1之硬化性樹脂組成物，其中進一步含有及(E)光聚合起始劑。 The curable resin composition of claim 1, which further comprises (E) a photopolymerization initiator. 如請求項2之硬化性樹脂組成物，其中進一步含有(F)感光性(甲基)丙烯酸酯化合物。 The curable resin composition of claim 2, which further contains (F) a photosensitive (meth) acrylate compound. 一種硬化性樹脂組成物，其特徵為含有(A)最大吸收波長為800~1000nm之近紅外線吸收劑、(B)在可見光區域380~780nm中，於380~500nm具有最小吸收值，於500~780nm具有最大吸收值之色材、及(F)感光性(甲基)丙烯酸酯化合物；(A)近紅外線吸收劑之含有率係於組成物(固體成分)中為0.001~50質量%，(B)特定色材之配合量係於組成物(固體成分)中 為0.05~80質量%，(F)感光性(甲基)丙烯酸酯化合物之配合量係相對於樹脂成分100質量份為1~150質量份。 A curable resin composition characterized by comprising (A) a near-infrared absorbing agent having a maximum absorption wavelength of 800 to 1000 nm, and (B) a minimum absorption value at 380 to 500 nm in a visible light region of 380 to 780 nm, at 500~ a color material having a maximum absorption value at 780 nm, and (F) a photosensitive (meth) acrylate compound; (A) a content ratio of the near-infrared ray absorbing agent is 0.001 to 50% by mass in the composition (solid content), ( B) The amount of the specific color material is in the composition (solid content) The amount of the photosensitive (meth) acrylate compound is from 1 to 150 parts by mass based on 100 parts by mass of the resin component, in an amount of from 0.05 to 80% by mass. 如請求項1至4中任一項之硬化性樹脂組成物，其中前述(A)近紅外線吸收劑為選自金屬錯體色素及縮合多環系色素中至少1種。 The curable resin composition according to any one of claims 1 to 4, wherein the (A) near-infrared ray absorbing agent is at least one selected from the group consisting of a metal complex dye and a condensed polycyclic dye. 如請求項1至4中任一項之硬化性樹脂組成物，其為呈現黑色。 The curable resin composition according to any one of claims 1 to 4, which is black. 如請求項1至4中任一項之硬化性樹脂組成物，其為使用於形成絕緣膜。 The curable resin composition according to any one of claims 1 to 4, which is used for forming an insulating film. 一種乾膜，其特徵為將如請求項1至7中任一項之硬化性樹脂組成物塗布於載體薄膜上，並使其乾燥而得。 A dry film obtained by applying the curable resin composition according to any one of claims 1 to 7 to a carrier film and drying it. 一種硬化物，其特徵為將如請求項1至7中任一項之硬化性樹脂組成物塗布於基材上，並使其乾燥而得之乾燥塗膜、或將前述硬化性樹脂組成物塗布於載體薄膜上，並使其乾燥而得之乾膜層合於基材所成的塗膜，進行硬化而得。 A cured product, which is characterized in that the curable resin composition according to any one of claims 1 to 7 is applied onto a substrate, dried to obtain a dried coating film, or the curable resin composition is coated. The dry film obtained by drying on a carrier film is laminated on a coating film formed of a substrate, and is obtained by hardening. 一種遮光用構件，其特徵為具備如請求項9之硬化物。 A light-shielding member characterized by comprising the cured product of claim 9. 一種顯示器用構件，其特徵為具備如請求項9之硬化物。 A member for a display characterized by having a cured product as claimed in claim 9.
TW103129705A 2013-09-27 2014-08-28 A hardened resin composition, a dry film, a hardened product, and a display member TWI533085B (en)

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