TW202007720A - Photosensitive composition, infrared light-cutting filter, and solid-state imaging device - Google Patents
Photosensitive composition, infrared light-cutting filter, and solid-state imaging device Download PDFInfo
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- TW202007720A TW202007720A TW108121002A TW108121002A TW202007720A TW 202007720 A TW202007720 A TW 202007720A TW 108121002 A TW108121002 A TW 108121002A TW 108121002 A TW108121002 A TW 108121002A TW 202007720 A TW202007720 A TW 202007720A
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Images
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C—CHEMISTRY; METALLURGY
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- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
- H01L27/144—Devices controlled by radiation
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Abstract
Description
本發明係關於一種感光性組成物、紅外光截止濾波器及固體攝像元件。The invention relates to a photosensitive composition, an infrared cut filter and a solid-state imaging element.
在視訊攝影機、數位相機及帶有相機功能之行動電話等中使用彩色圖像的固體攝像元件。該等固體攝像元件在其受光部使用對紅外線(紅外光)具有靈敏度之矽光二極體,因此需要進行發光度校正,多使用紅外光截止濾波器。 在專利文獻1中,作為用於形成紅外光截止濾波器之組成物,揭示有一種包含既定的鎢氧化物和/或複合鎢氧化物之感光性組成物。 [先前技術文獻] [專利文獻]Solid-state imaging elements that use color images in video cameras, digital cameras, and mobile phones with camera functions. These solid-state imaging devices use silicon photodiodes that are sensitive to infrared rays (infrared light) in their light-receiving parts. Therefore, luminosity correction is required and infrared cut-off filters are often used. Patent Document 1 discloses a photosensitive composition containing predetermined tungsten oxide and/or composite tungsten oxide as a composition for forming an infrared light cut filter. [Prior Technical Literature] [Patent Literature]
[專利文獻1]國際公開第2011/067998號[Patent Literature 1] International Publication No. 2011/067998
在使用感光性組成物來形成圖案時,要求圖案的截面形狀的矩形性優異。 又,使用感光性組成物而形成之硬化膜要求即使在實施加熱處理之後亦不易產生透射率的變化。尤其,即使在各種濾色器和上述硬化膜相鄰而配置之情況下,亦期望在實施加熱處理之後難以產生上述透射率的變化。以下,將在加熱處理之後透射率難以變化之情況稱為耐熱性優異。 本發明人等使用專利文獻1中所記載之感光性組成物評價了上述特性,其結果,無法平衡良好地滿足兩者的特性。When forming a pattern using a photosensitive composition, it is required that the cross-sectional shape of the pattern is excellent in rectangularity. In addition, it is required that the cured film formed using the photosensitive composition hardly change the transmittance even after the heat treatment. In particular, even in the case where various color filters are arranged adjacent to the cured film, it is expected that the above-mentioned change in transmittance is unlikely to occur after the heat treatment is performed. Hereinafter, the case where the transmittance is difficult to change after the heat treatment is referred to as excellent heat resistance. The present inventors evaluated the above-mentioned characteristics using the photosensitive composition described in Patent Document 1, and as a result, the characteristics of both could not be satisfactorily satisfied.
本發明鑑於上述情況,其課題為提供一種能夠形成截面形狀的矩形性優異之圖案且能夠形成耐熱性優異之硬化膜之感光性組成物。 又,本發明的課題為還提供一種使用感光性組成物而形成之紅外光截止濾波器及包含紅外光截止濾波器之固體攝像元件。In view of the above circumstances, the object of the present invention is to provide a photosensitive composition capable of forming a pattern with excellent rectangularity in cross-sectional shape and capable of forming a cured film having excellent heat resistance. In addition, an object of the present invention is to provide an infrared light cut filter formed using a photosensitive composition and a solid-state imaging element including the infrared light cut filter.
本發明人等對以往技術的問題點進行了深入研究,其結果,發現了藉由以下構成能夠解決上述課題。The present inventors have conducted intensive studies on the problems of the conventional technology, and as a result, they have found that the above-mentioned problems can be solved by the following configuration.
(1)一種感光性組成物,其包含含有金屬之鎢氧化物粒子、聚合性化合物、聚合起始劑、紫外線吸收劑及聚合抑制劑,該感光性組成物中 紫外線吸收劑的含量相對於聚合抑制劑的含量之質量比為0.08~330。 (2)如(1)所述之感光性組成物,其中含有金屬之鎢氧化物粒子的表面由金屬氧化物被覆。 (3)如(2)所述之感光性組成物,其中金屬氧化物係包含選自包括Si、Ti、Zr及Al之群組中之至少1種以上的元素之氧化物。 (4)如(1)至(3)中任一項所述之感光性組成物,其中紫外線吸收劑係在熱質量測定中於150℃下之質量減少率為5%以下且於220℃下之質量減少率為40%以上的紫外線吸收劑。 (5)如(1)至(4)中任一項所述之感光性組成物,其中紫外線吸收劑係選自二苯甲醯甲烷系化合物及胺基丁二烯系化合物中之至少1種。 (6)如(1)至(5)中任一項所述之感光性組成物,其包含2種以上的聚合抑制劑。 (7)如(6)所述之感光性組成物,其中聚合抑制劑係選自包括受阻酚系化合物、受阻酚系化合物以外的酚系化合物、苯醌系化合物及氫醌系化合物之群組中之至少2種以上。 (8)如(7)所述之感光性組成物,其中聚合抑制劑包含選自包括受阻酚系化合物、苯醌系化合物及氫醌系化合物之群組中之1種以上的第1聚合抑制劑和受阻酚系化合物以外的酚系化合物。 (9)如(8)所述之感光性組成物,其中受阻酚系化合物以外的酚系化合物的含量相對於第1聚合抑制劑的合計含量之質量比為0.0009~0.17。 (10)如(1)至(9)中任一項所述之感光性組成物,其進一步包含具有雙鍵基之鹼可溶性黏合劑。 (11)一種紅外光截止濾波器,其使用(1)至(10)中任一項所述之感光性組成物而形成。 (12)一種固體攝像元件,其包含(11)所述之紅外光截止濾波器。 [發明效果](1) A photosensitive composition containing metal-containing tungsten oxide particles, a polymerizable compound, a polymerization initiator, an ultraviolet absorber, and a polymerization inhibitor, in the photosensitive composition The mass ratio of the content of the ultraviolet absorber to the content of the polymerization inhibitor is 0.08 to 330. (2) The photosensitive composition according to (1), wherein the surface of the metal-containing tungsten oxide particles is coated with metal oxide. (3) The photosensitive composition according to (2), wherein the metal oxide is an oxide containing at least one kind of element selected from the group consisting of Si, Ti, Zr, and Al. (4) The photosensitive composition according to any one of (1) to (3), wherein the ultraviolet absorber has a mass reduction rate at 150°C of 5% or less and at 220°C in thermal mass measurement The ultraviolet absorbing agent whose mass reduction rate is more than 40%. (5) The photosensitive composition according to any one of (1) to (4), wherein the ultraviolet absorber is at least one selected from the group consisting of dibenzoylmethane-based compounds and aminobutadiene-based compounds . (6) The photosensitive composition according to any one of (1) to (5), which contains two or more kinds of polymerization inhibitors. (7) The photosensitive composition according to (6), wherein the polymerization inhibitor is selected from the group consisting of hindered phenol compounds, hindered phenol compounds, phenol compounds, benzoquinone compounds, and hydroquinone compounds At least two of them. (8) The photosensitive composition according to (7), wherein the polymerization inhibitor includes one or more first polymerization inhibitors selected from the group consisting of hindered phenol compounds, benzoquinone compounds, and hydroquinone compounds Phenolic compounds other than agents and hindered phenolic compounds. (9) The photosensitive composition according to (8), wherein the mass ratio of the content of the phenolic compound other than the hindered phenolic compound to the total content of the first polymerization inhibitor is 0.0009 to 0.17. (10) The photosensitive composition according to any one of (1) to (9), further including an alkali-soluble binder having a double bond group. (11) An infrared light cut filter formed using the photosensitive composition described in any one of (1) to (10). (12) A solid-state imaging element including the infrared light cut filter described in (11). [Effect of the invention]
依本發明,能夠提供一種能夠形成截面形狀的矩形性優異之圖案且能夠形成耐熱性優異之硬化膜之感光性組成物。 又,依本發明,還能夠提供一種使用感光性組成物而形成之紅外光截止濾波器及包含紅外光截止濾波器之固體攝像元件。According to the present invention, it is possible to provide a photosensitive composition capable of forming a pattern with excellent cross-sectional rectangularity and capable of forming a cured film having excellent heat resistance. In addition, according to the present invention, it is also possible to provide an infrared light cut filter formed using a photosensitive composition and a solid-state imaging element including the infrared light cut filter.
以下,對本發明的感光性組成物、紅外光截止濾波器及固體攝像元件的較佳態樣進行詳細敘述。 在本說明書中之基團(原子團)的標記中,未記有經取代及未經取代之標記包含不具有取代基者,並且還包含具有取代基者。例如,“烷基”不僅包含不具有取代基之烷基(未經取代之烷基),還包含具有取代基之烷基(經取代之烷基)。本說明書中,“~”係以將其前後所記載之數值作為下限值及上限值而包含之含義來使用。 本說明書中,“(甲基)丙烯酸酯”表示丙烯酸酯及甲基丙烯酸酯,“(甲基)丙烯酸基”表示丙烯酸基及甲基丙烯酸基,“(甲基)丙烯醯基”表示丙烯醯基及甲基丙烯醯基。 又,本說明書中,“單量體”與“單體”的含義相同。單量體與低聚物及聚合物有區別,係指重量平均分子量為2,000以下的化合物。 本說明書中,聚合性化合物係指具有聚合性官能基之化合物,可以為單量體,亦可以為聚合物。聚合性官能基係指參與聚合反應之基團。 本說明書中,“總固體成分”係指從組成物的所有組成中去除溶劑之後之成分的總質量。本發明中之固體成分係於25℃下之固體成分。Hereinafter, preferred aspects of the photosensitive composition, infrared cut filter, and solid-state imaging element of the present invention will be described in detail. In the label of the group (atomic group) in this specification, the label which is not described as substituted and unsubstituted includes those without a substituent, and also includes those with a substituent. For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups), but also substituted alkyl groups (substituted alkyl groups). In this specification, "~" is used with the meaning including the numerical value described before and after it as a lower limit value and an upper limit value. In this specification, "(meth)acrylate" means acrylate and methacrylate, "(meth)acrylate" means acrylic and methacrylic, and "(meth)acryl" means acrylic. Group and methacrylic group. In addition, in this specification, "single body" and "monomer" have the same meaning. Monomers are different from oligomers and polymers, and refer to compounds with a weight average molecular weight of 2,000 or less. In this specification, a polymerizable compound refers to a compound having a polymerizable functional group, and may be a single substance or a polymer. The polymerizable functional group refers to a group participating in a polymerization reaction. In this specification, "total solid content" refers to the total mass of components after removing the solvent from all the components of the composition. The solid content in the present invention is a solid content at 25°C.
首先,作為本發明的特徵點,可以舉出調整紫外線吸收劑與聚合抑制劑的質量比這一點。發現了藉由將上述質量比調整在既定的範圍,能夠以更優異之平衡來兼顧耐熱性和圖案矩形性(所形成之圖案的矩形性)。First, as a characteristic point of the present invention, the point of adjusting the mass ratio of the ultraviolet absorber to the polymerization inhibitor can be mentioned. It was found that by adjusting the above-mentioned mass ratio within a predetermined range, it is possible to balance heat resistance and pattern rectangularity (rectangularity of the formed pattern) with a more excellent balance.
感光性組成物包含含有金屬之鎢氧化物粒子、聚合性化合物、聚合起始劑、紫外線吸收劑及聚合抑制劑。 以下,對感光性組成物(以後,亦簡稱為“組成物”)中所包含之各成分進行詳細敘述。The photosensitive composition contains metal-containing tungsten oxide particles, a polymerizable compound, a polymerization initiator, an ultraviolet absorber, and a polymerization inhibitor. Hereinafter, each component included in the photosensitive composition (hereinafter, also simply referred to as "composition") will be described in detail.
(含有金屬之鎢氧化物粒子) 含有金屬之鎢氧化物粒子(以後,亦稱為“特定粒子”。)係包含金屬原子之鎢氧化物粒子。 特定粒子依晶體結構選擇性地遮蔽紅外光(波長為約800~1200nm的光),因此具有作為紅外線吸收劑之效能。因此,包含特定粒子之紅外光截止濾波器在紅外區域中遮光性高,且在可見光區域中之透光性高。 又,特定粒子對於比用於圖像形成中之高壓汞燈、KrF及ArF等的曝光中所使用之可見區域短波的光之吸收亦小。因此,如後述,本發明的感光性組成物具有優異之圖案形成性,能夠微細地控制紅外光截止濾波器的形狀。(Tungsten oxide particles containing metal) Tungsten oxide particles containing metal (hereinafter, also referred to as "specific particles") are tungsten oxide particles containing metal atoms. The specific particles selectively block infrared light (light with a wavelength of about 800-1200 nm) according to the crystal structure, and thus have an effect as an infrared absorber. Therefore, the infrared light cut filter including specific particles has high light-shielding property in the infrared region and high light permeability in the visible light region. In addition, the specific particles also have a smaller absorption of short-wavelength light than the visible region used in the exposure of high-pressure mercury lamps, KrF, and ArF used in image formation. Therefore, as described later, the photosensitive composition of the present invention has excellent pattern formability and can finely control the shape of the infrared light cut filter.
特定粒子中所包含之金屬原子的種類並不受特別限制,在紅外光的遮蔽性更優異之觀點上,可以舉出鹼金屬。 上述特定粒子由下述通式(組成式)(I)表示為較佳。 Mx Wy Oz ......(I) M表示鹼金屬,W表示鎢,O表示氧。 0.001≤x/y≤1.1 2.2≤z/y≤3.0The type of metal atoms contained in the specific particles is not particularly limited, and from the viewpoint of more excellent infrared light shielding properties, alkali metals can be cited. The specific particles are preferably represented by the following general formula (composition formula) (I). M x W y O z (I) M represents alkali metal, W represents tungsten, and O represents oxygen. 0.001≤x/y≤1.1 2.2≤z/y≤3.0
M的鹼金屬可以為1種,亦可以為2種以上。 作為M的鹼金屬,Rb或Cs為較佳,Cs為更佳。 藉由x/y為0.001以上,能夠充分遮蔽紅外光,藉由為1.1以下,能夠進一步避免在特定粒子中生成雜質相。 藉由z/y為2.2以上,能夠進一步提高作為材料之化學穩定性,藉由為3.0以下,能夠進一步遮蔽紅外光。The alkali metal of M may be one kind or two or more kinds. As the alkali metal of M, Rb or Cs is preferable, and Cs is more preferable. When x/y is 0.001 or more, infrared light can be sufficiently blocked, and when it is 1.1 or less, it is possible to further avoid generation of an impurity phase in specific particles. When z/y is 2.2 or more, the chemical stability as a material can be further improved, and if it is 3.0 or less, infrared light can be further blocked.
作為上述通式(I)所表示之含有鹼金屬之特定粒子的具體例,可以舉出Cs0.33 WO3 、Rb0.33 WO3 、K0.33 WO3 等,Cs0.33 WO3 或Rb0.33 WO3 為較佳,Cs0.33 WO3 為更佳。Specific examples of the alkali metal-containing specific particles represented by the general formula (I) include Cs 0.33 WO 3 , Rb 0.33 WO 3 , K 0.33 WO 3 and the like, and Cs 0.33 WO 3 or Rb 0.33 WO 3 are preferred Yes, Cs 0.33 WO 3 is even better.
在本發明的效果更優異之觀點上,含有金屬之鎢氧化物粒子的表面由金屬氧化物被覆為較佳。亦即,感光性組成物係包含含有金屬之鎢氧化物粒子和以覆蓋含有金屬之鎢氧化物粒子的表面之方式配置之金屬氧化物之被覆粒子為較佳。 金屬氧化物的種類並不受特別限制,包含選自包括Si、Ti、Zr及Al之群組中之至少1種以上的元素之氧化物為較佳。 金屬氧化物可以以覆蓋含有金屬之鎢氧化物粒子的表面全面之方式配置,亦可以以覆蓋一部分之方式配置。From the viewpoint that the effect of the present invention is more excellent, it is preferable that the surface of the metal-containing tungsten oxide particles be coated with metal oxide. That is, the photosensitive composition preferably contains metal-containing tungsten oxide particles and metal oxide-coated particles arranged so as to cover the surface of the metal-containing tungsten oxide particles. The type of metal oxide is not particularly limited, and oxides containing at least one element selected from the group consisting of Si, Ti, Zr, and Al are preferred. The metal oxide may be arranged to cover the entire surface of the metal-containing tungsten oxide particles, or may be arranged to cover a part of it.
特定粒子的平均粒徑並不受特別限制,但800nm以下為較佳,400nm以下為更佳,200nm以下為進一步較佳。若平均粒徑在上述範圍,則特定粒子因光散射而難以阻斷可見光,因此在可見光區域中之透光性更優異。從避免光散射之觀點而言,平均粒徑越小越為較佳,但出於製造時之易處理性等原因,特定粒子的平均粒徑係1nm以上為較佳。 另外,作為平均粒徑的測定方法,係利用公知的電子顯微鏡(例如,透射型電子顯微鏡)測定至少50個特定粒子的粒徑(直徑)並將該等進行算術平均而得到之值。另外,當特定粒子不是真圓時,將長徑作為粒徑而進行測定。The average particle size of the specific particles is not particularly limited, but it is preferably 800 nm or less, more preferably 400 nm or less, and further preferably 200 nm or less. If the average particle diameter is in the above range, it is difficult for specific particles to block visible light due to light scattering, and therefore, the light transmittance in the visible light region is more excellent. From the viewpoint of avoiding light scattering, the smaller the average particle diameter, the better. However, for ease of handling during manufacturing and the like, the average particle diameter of the specific particles is preferably 1 nm or more. In addition, as a method of measuring the average particle diameter, a particle diameter (diameter) of at least 50 specific particles is measured using a known electron microscope (for example, a transmission electron microscope), and these are arithmetically averaged. In addition, when the specific particle is not a true circle, the long diameter is measured as the particle diameter.
感光性組成物中之特定粒子的含量並不受特別限制,但在紅外光的遮蔽性更優異之觀點上,相對於感光性組成物總質量,1~20質量%為較佳,3~15質量%為更佳。 又,特定粒子能夠使用2種以上,在該情況下,合計含量在上述範圍為較佳。The content of specific particles in the photosensitive composition is not particularly limited, but from the viewpoint of more excellent infrared light shielding properties, it is preferably 1 to 20% by mass relative to the total mass of the photosensitive composition, and 3 to 15 Quality% is better. In addition, two or more types of specific particles can be used. In this case, the total content is preferably in the above range.
特定粒子能夠以市售品獲得,能夠藉由在惰性氣體氛圍或還元性氣體氛圍中對含有鹼金屬之鎢化合物進行熱處理之方法來得到(參閱日本專利4096205號)。 又,例如亦能夠以SumitomoMetal Mining Co.,Ltd.製造之YMF-02A、YMS-01A-2、YMF-10A-1等含有鹼金屬之鎢氧化物的微粒的分散物獲得。The specific particles can be obtained as a commercially available product, and can be obtained by heat-treating a tungsten compound containing an alkali metal in an inert gas atmosphere or a reducing gas atmosphere (see Japanese Patent No. 4096205). Also, for example, it can be obtained as a dispersion of fine particles of tungsten oxide containing alkali metal, such as YMF-02A, YMS-01A-2, and YMF-10A-1 manufactured by Sumitomo Metal Mining Co., Ltd.
(聚合性化合物) 作為聚合性化合物,只要為在分子內具有聚合性基(藉由酸、自由基及熱中的至少1種而進行反應之基團)之化合物,則可以使用任何聚合性化合物,在分子內具有複數個聚合性基之多官能聚合性化合物為較佳。 作為具有在酸、自由基及熱中的至少任1種的作用下進行反應之聚合性基之聚合性化合物,可以舉出具有不飽和酯官能基(例如,丙烯醯基及甲基丙烯醯基)、不飽和醯胺基、乙烯醚基及烯丙基等乙烯性不飽和基之含乙烯性不飽和基化合物;羥甲基化合物;雙順丁烯二醯亞胺化合物;苯并環丁烯化合物;雙烯丙基納迪克醯亞胺化合物;苯并㗁𠯤化合物等。(Polymerizable compound) As the polymerizable compound, any compound can be used as long as it has a polymerizable group (a group that reacts with at least one of acid, radicals, and heat) in the molecule, and has a plural number in the molecule A multifunctional polymerizable compound with one polymerizable group is preferred. Examples of the polymerizable compound having a polymerizable group that reacts under the action of at least any one of acid, radical, and heat include unsaturated ester functional groups (for example, acryloyl and methacryloyl) , Unsaturated amide group, vinyl ether group and allyl and other ethylenic unsaturated group-containing ethylenically unsaturated group-containing compound; methylol compound; bis-cis-butadiene diimide compound; benzocyclobutene compound ; Diallyl Nadic amide imine compounds; benzo 㗁𠯤 compounds and so on.
聚合性化合物可以為單體,亦可以為聚合物。 作為聚合性化合物,自由基聚合性化合物為較佳,具有乙烯性不飽和雙鍵之化合物為更佳。 作為聚合性化合物,可以舉出不飽和羧酸(例如,丙烯酸、甲基丙烯酸、衣康酸、巴豆酸、異巴豆酸及順丁烯二酸等)、其酯類及其醯胺類,不飽和羧酸酯、不飽和羧酸與脂肪族多元醇化合物的酯、或不飽和羧酸與脂肪族多元胺化合物的醯胺為較佳。 尤其,不飽和羧酸與脂肪族多元醇化合物的酯在曝光部中能夠顯現出高的疏水性,因此在藉由鹼顯影容易形成具有所期望之形狀之圖案,又,可得到耐久性高的圖案之觀點上為較佳。 又,作為聚合性化合物,可以舉出具有羥基、胺基及巰基等親核性取代基之不飽和羧酸酯或醯胺與單官能或多官能異氰酸酯類或環氧類的加成反應物。 另外,作為聚合性化合物,還可以舉出上述不飽和羧酸酯或醯胺與單官能或多官能的羧酸的脫水縮合反應物。The polymerizable compound may be a monomer or a polymer. As the polymerizable compound, a radical polymerizable compound is preferred, and a compound having an ethylenically unsaturated double bond is more preferred. Examples of the polymerizable compound include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid, etc.), esters and amides thereof. Saturated carboxylic acid esters, esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, or amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds are preferred. In particular, the ester of the unsaturated carboxylic acid and the aliphatic polyhydric alcohol compound can exhibit high hydrophobicity in the exposed portion, so that it is easy to form a pattern having a desired shape by alkali development, and high durability can be obtained. The pattern is preferred from the viewpoint. In addition, examples of the polymerizable compound include addition reactants of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amine groups, and mercapto groups, and monofunctional or polyfunctional isocyanates or epoxy compounds. In addition, examples of the polymerizable compound include a dehydration condensation reaction product of the above-mentioned unsaturated carboxylic acid ester or amide and a monofunctional or polyfunctional carboxylic acid.
作為不飽和羧酸酯,可以舉出甲基丙烯酸酯、衣康酸酯、巴豆酸酯、異巴豆酸酯及順丁烯二酸酯。Examples of the unsaturated carboxylic acid ester include methacrylate, itaconic acid ester, crotonic acid ester, isocrotonic acid ester and maleic acid ester.
作為聚合性化合物,使用異氰酸酯與羥基的加成反應而製造之胺基甲酸酯系加成聚合性化合物亦為較佳,作為其具體例,例如可以舉出日本特公昭48-041708號公報中所記載之在1個分子中含有2個以上的聚合性乙烯基之乙烯基胺基甲酸酯(vinyl urethane)化合物,該乙烯基胺基甲酸酯係使下述通式(E)所表示之具有羥基之乙烯基單體與在1分個子中具有2個以上的異氰酸酯基之聚異氰酸酯化合物加成而成。 CH2 =C(R4 )COOCH2 CH(R5 )OH (E) 〔其中,R4 及R5 各自獨立地表示H或CH3 。〕As the polymerizable compound, a urethane-based addition polymerizable compound produced by the addition reaction of isocyanate and hydroxyl group is also preferable, and specific examples thereof include, for example, Japanese Patent Publication No. 48-041708 A vinyl urethane compound containing two or more polymerizable vinyl groups in one molecule is described. The vinyl urethane is represented by the following general formula (E) The vinyl monomer having a hydroxyl group is added to a polyisocyanate compound having two or more isocyanate groups in one cent. CH 2 =C(R 4 )COOCH 2 CH(R 5 )OH(E) [wherein R 4 and R 5 each independently represent H or CH 3 . 〕
自由基聚合性化合物中的乙烯性不飽和雙鍵的數量並不受特別限制,從硬化靈敏度的觀點而言,2個以上為較佳,3個以上為更佳,4個以上為進一步較佳。上限並不受特別限制,但10個以下的情況較多。The number of ethylenically unsaturated double bonds in the radical polymerizable compound is not particularly limited. From the viewpoint of curing sensitivity, two or more are preferable, three or more are more preferable, and four or more are still more preferable . The upper limit is not particularly limited, but there are many cases of 10 or less.
又,從硬化靈敏度及未曝光部的顯影性的觀點而言,作為聚合性化合物,包含EO(環氧乙烷)改質體之聚合性化合物為較佳。 又,從硬化靈敏度及曝光部強度的觀點而言,作為聚合性化合物,包含胺基甲酸酯鍵之化合物為較佳。 另外,從圖案形成時的顯影性的觀點而言,作為聚合性化合物,具有酸基之化合物為較佳。In addition, from the viewpoint of curing sensitivity and developability of the unexposed portion, as the polymerizable compound, a polymerizable compound containing an EO (ethylene oxide) modified body is preferable. In addition, from the viewpoint of curing sensitivity and intensity of the exposed portion, a compound containing a urethane bond is preferred as the polymerizable compound. In addition, from the viewpoint of developability at the time of pattern formation, the polymerizable compound is preferably a compound having an acid group.
作為聚合性化合物,可以舉出雙酚A二丙烯酸酯、雙酚A二丙烯酸酯EO改質體、三羥甲基丙烷三丙烯酸酯、三羥甲基丙烷三(丙烯醯氧基丙基)醚、三羥甲基乙烷三丙烯酸酯、四乙二醇二丙烯酸酯、新戊四醇二丙烯酸酯、新戊四醇三丙烯酸酯、新戊四醇四丙烯酸酯、二新戊四醇四丙烯酸酯、二新戊四醇五丙烯酸酯、二新戊四醇六丙烯酸酯酯、山梨糖醇三丙烯酸酯、山梨糖醇四丙烯酸酯、山梨糖醇五丙烯酸酯、山梨糖醇六丙烯酸酯酯、三(丙烯醯氧基乙基)異氰脲酸酯、新戊四醇四丙烯酸酯EO改質體、二新戊四醇六丙烯酸酯EO改質體及三環癸烷二甲醇二丙烯酸酯等。 其中,雙酚A二丙烯酸酯EO改質體、新戊四醇三丙烯酸酯、新戊四醇四丙烯酸酯、二新戊四醇五丙烯酸酯、二新戊四醇六丙烯酸酯酯、三(丙烯醯氧基乙基)異氰脲酸酯、新戊四醇四丙烯酸酯EO改質體或二新戊四醇六丙烯酸酯EO改質體為較佳。Examples of the polymerizable compound include bisphenol A diacrylate, bisphenol A diacrylate EO modified form, trimethylolpropane triacrylate, and trimethylolpropane tris(acryloxypropyl) ether. , Trimethylolethane triacrylate, tetraethylene glycol diacrylate, neopentyl alcohol diacrylate, neopentyl alcohol triacrylate, neopentyl alcohol tetraacrylate, di neopentyl alcohol tetraacrylate Ester, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, Tris(acryloyloxyethyl)isocyanurate, neopentyl tetraol tetraacrylate EO modified body, dipentaerythritol hexaacrylate EO modified body, tricyclodecane dimethanol diacrylate, etc. . Among them, bisphenol A diacrylate EO modified body, neopentaerythritol triacrylate, neopentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tri( Acryloyloxyethyl) isocyanurate, neopentaerythritol tetraacrylate EO modified form or dipentaerythritol hexaacrylate EO modified form is preferred.
又,作為市售品,可以舉出胺基甲酸酯低聚物UAS-10、UAB-140(以上為Sanyo Kokusaku Pulp Co.,Ltd.製造)、KAYARAD RP-1040、DPHA-40H、KAYARAD RP-1040、KAYARAD DPHA、KAYARAD DPCA-20(以上為Nippon Kayaku Co.,Ltd.製造)、UA-306H、UA-306T、UA-306I、AH-600、T-600、AI-600、DCP-A(以上為KYOEISHA CHEMICAL Co.,LTD.製造)、NK Ester A-BPE-20、A-DCP、NK Ester A-TMMT、NK Ester A-DPH-12E(以上為Shin-Nakamura Chemical Co.,Ltd.製造)、TO-756、TO-1382、M-305、ARONIX M-510(以上為TOAGOSEI CO.,LTD.製造)及OGSOL EA-0300(Osaka Gas Chemicals Co.,Ltd.製造)。Further, as commercially available products, urethane oligomers UAS-10, UAB-140 (above manufactured by Sanyo Kokusaku Pulp Co., Ltd.), KAYARAD RP-1040, DPHA-40H, KAYARAD RP can be mentioned. -1040, KAYARAD DPHA, KAYARAD DPCA-20 (above manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600, DCP-A (Above manufactured by KYOEISHA CHEMICAL Co., LTD.), NK Ester A-BPE-20, A-DCP, NK Ester A-TMMT, NK Ester A-DPH-12E (above is Shin-Nakamura Chemical Co., Ltd. Manufacturing), TO-756, TO-1382, M-305, ARONIX M-510 (above manufactured by TOAGOSEI CO., LTD.) and OGSOL EA-0300 (manufactured by Osaka Gas Chemicals Co., Ltd.).
感光性組成物中之聚合性化合物的含量並不受特別限制,但在紅外光截止濾波器的強度更優異之觀點上,相對於感光性組成物總質量,1~20質量%為較佳,3~10質量%為更佳。 聚合性化合物可以單獨使用1種,亦可以併用2種以上。其中,在圖案矩形性更優異之觀點上,併用2種以上為較佳。The content of the polymerizable compound in the photosensitive composition is not particularly limited, but from the viewpoint that the intensity of the infrared light cut filter is more excellent, it is preferably 1 to 20% by mass relative to the total mass of the photosensitive composition. 3 to 10% by mass is better. The polymerizable compound may be used alone or in combination of two or more. Among them, from the viewpoint of more excellent pattern rectangularity, it is preferable to use two or more kinds.
(聚合起始劑) 作為聚合起始劑,可以舉出光聚合起始劑及熱聚合起始劑,光聚合起始劑為較佳。 另外,光聚合起始劑係具有對光感光而引發聚合之能力之化合物,對紫外光區域至可見光區域具有感光性為較佳。 熱聚合起始劑係具有藉由熱引發聚合之能力之化合物,於150~250℃下發生分解之起始劑為較佳。(Polymerization initiator) Examples of the polymerization initiator include photopolymerization initiators and thermal polymerization initiators, and photopolymerization initiators are preferred. In addition, the photopolymerization initiator is a compound which has the ability to initiate polymerization by being sensitive to light, and is preferably sensitive to ultraviolet to visible light. The thermal polymerization initiator is a compound having the ability to initiate polymerization by heat, and an initiator that decomposes at 150 to 250°C is preferable.
作為聚合起始劑,至少具有芳香族基之化合物為較佳,例如可以舉出醯基膦化合物、苯乙酮化合物、α-胺基酮化合物、二苯甲酮化合物、苯偶姻醚化合物、硫雜蒽酮化合物、肟化合物、六芳基雙咪唑化合物、三鹵甲基化合物、偶氮化合物、有機過氧化物、重氮化合物、錪化合物、鋶化合物、吖嗪鎓化合物、苯偶姻醚化合物、縮酮衍生物化合物、鎓鹽化合物、有機硼鹽化合物及二碸化合物。 從靈敏度的觀點而言,肟化合物、羥基苯乙酮化合物、胺基苯乙酮化合物、醯基膦化合物、α-胺基酮化合物、三鹵甲基化合物、六芳基雙咪唑化合物或硫醇化合物為較佳,肟化合物為更佳。 作為羥基苯乙酮化合物,可以舉出IRGACURE-184、DAROCUR-1173、IRGACURE-500、IRGACURE-2959及IRGACURE-127(商品名:均為BASF公司製造)。 作為胺基苯乙酮化合物,可以舉出IRGACURE-907、IRGACURE-369及IRGACURE-379(商品名:均為BASF公司製造)。 作為醯基膦化合物,可以舉出IRGACURE-819及DAROCUR-TPO(商品名:均為BASF公司製造)。 作為肟化合物,可以舉出IRGACURE OXE 01(1,2-辛二酮,1-[4-(苯硫基)-,2-(o-苯甲醯肟)])及IRGACURE OXE 02(乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-1-(o-乙醯肟))、IRGACUREOXE03(商品名:BASF公司製造)、IRGACUREOXE04(商品名:BASF公司製造)。 作為肟化合物,能夠參閱日本特開2012-208494號公報的段落0513(對應之美國專利申請公開第2012/235099號說明書的<0632>)以後的式(OX-1)、(OX-2)或(OX-3)所表示之化合物的說明,該等的內容被編入本申請說明書中。As the polymerization initiator, a compound having at least an aromatic group is preferred, and examples thereof include an acylphosphine compound, an acetophenone compound, an α-aminoketone compound, a benzophenone compound, and a benzoin ether compound. Thioxanthone compounds, oxime compounds, hexaarylbisimidazole compounds, trihalomethyl compounds, azo compounds, organic peroxides, diazo compounds, iodonium compounds, arsenic compounds, azinium compounds, benzoin ethers Compounds, ketal derivative compounds, onium salt compounds, organic boron salt compounds, and dioxin compounds. From the viewpoint of sensitivity, the oxime compound, hydroxyacetophenone compound, aminoacetophenone compound, acetylphosphine compound, α-aminoketone compound, trihalomethyl compound, hexaarylbisimidazole compound or thiol Compounds are preferred, and oxime compounds are more preferred. Examples of hydroxyacetophenone compounds include IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names: all manufactured by BASF). Examples of the aminoacetophenone compounds include IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF). Examples of the acetylphosphine compound include IRGACURE-819 and DAROCUR-TPO (trade names: all manufactured by BASF Corporation). Examples of the oxime compound include IRGACURE OXE 01 (1,2-octanedione, 1-[4-(phenylthio)-, 2-(o-benzoyl oxime)]) and IRGACURE OXE 02 (ethanone , 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-1-(o-acetoxime)), IRGACUREOXE03 (trade name: BASF company Manufacturing), IRGACUREOXE04 (trade name: manufactured by BASF). As the oxime compound, the following formulas (OX-1), (OX-2) or (OX-2) of paragraph 0513 (corresponding to <0632> of US Patent Application Publication No. 2012/235099) can be referred to The description of the compound represented by (OX-3), and such contents are incorporated in the specification of this application.
作為肟化合物,可以舉出日本特開2012-113104號公報的段落0092~0096中所記載之聚合起始劑,該等的內容被編入本申請說明書中。 又,作為肟化合物的市售品,可以舉出TRONLY TR-PBG-304、TRONLY TR-PBG-309及TRONLY TR-PBG-305(常州強力電子新材料有限公司(CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO.,LTD)製造)。Examples of the oxime compound include the polymerization initiators described in paragraphs 0092 to 0096 of Japanese Patent Laid-Open No. 2012-113104, and the contents thereof are incorporated in the specification of the present application. In addition, as commercial products of oxime compounds, TRONLY TR-PBG-304, TRONLY TR-PBG-309, and TRONLY TR-PBG-305 (CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD) manufacturing).
感光性組成物中之聚合起始劑的含量並不受特別限制,但在耐乾燥性優異之觀點上,相對於感光性組成物總質量,0.1~10質量%為較佳,0.5~5.0質量%為更佳。 聚合起始劑可以單獨使用1種,亦可以併用2種以上。The content of the polymerization initiator in the photosensitive composition is not particularly limited, but from the viewpoint of excellent drying resistance, it is preferably 0.1 to 10% by mass relative to the total mass of the photosensitive composition, and 0.5 to 5.0 mass % Is better. One type of polymerization initiator may be used alone, or two or more types may be used in combination.
(聚合抑制劑) 作為聚合抑制劑,可以舉出公知的聚合抑制劑。推測聚合抑制劑具有捕捉對與硬化層相鄰而配置之濾色器進行加熱處理時所產生之自由基之功能。 例如,可以舉出酚系化合物、受阻胺系化合物、磷系化合物及啡噻嗪系化合物。 其中,在本發明的效果更優異之觀點上,受阻酚系化合物、受阻酚系化合物以外的酚系化合物、苯醌系化合物或氫醌系化合物為較佳。 另外,受阻酚系化合物係在酚性羥基的2個鄰位的至少一方具有氫原子以外的取代基之酚系化合物。作為取代基,例如可以舉出烷基(較佳為甲基以外的烷基)、烯基、炔基、芳基、雜環式基、烷氧基、芳氧基、胺基、取代胺基、烷硫基、苯硫基及鹵素原子。(Polymerization inhibitor) As a polymerization inhibitor, a well-known polymerization inhibitor can be mentioned. It is speculated that the polymerization inhibitor has a function of capturing free radicals generated when the color filter disposed adjacent to the hardened layer is heated. For example, phenol compounds, hindered amine compounds, phosphorus compounds, and phenothiazine compounds may be mentioned. Among them, a hindered phenol compound, a phenol compound other than the hindered phenol compound, a benzoquinone compound, or a hydroquinone compound is preferable from the viewpoint that the effect of the present invention is more excellent. In addition, the hindered phenol compound is a phenol compound having a substituent other than a hydrogen atom in at least one of two ortho positions of the phenolic hydroxyl group. Examples of the substituent include an alkyl group (preferably an alkyl group other than methyl), alkenyl group, alkynyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, amine group, and substituted amine group , Alkylthio, phenylthio and halogen atoms.
作為受阻酚系化合物,式(X)所表示之化合物為較佳。As the hindered phenol compound, the compound represented by formula (X) is preferred.
[化學式1] [Chemical Formula 1]
式(X)中,R1 及R2 分別獨立地表示取代基。取代基的定義如上所述,其中烷基、烯基、炔基或芳基為較佳,碳數4以上的烷基為更佳。 R3 表示取代基。取代基的定義如上所述,其中烷基、烯基、炔基或芳基為較佳,烷基為較佳。當n為2以上時,複數個R3 可以相同,亦可以不同。 n表示0~3的整數。其中1為較佳。In formula (X), R 1 and R 2 each independently represent a substituent. The definition of the substituent is as described above, among which alkyl, alkenyl, alkynyl or aryl is preferred, and alkyl having 4 or more carbon atoms is more preferred. R 3 represents a substituent. The definition of the substituent is as described above, wherein alkyl, alkenyl, alkynyl or aryl is preferred, and alkyl is preferred. When n is 2 or more, a plurality of R 3 may be the same or different. n represents an integer of 0 to 3. Among them, 1 is better.
作為受阻酚系化合物以外的酚系化合物,式(Y)所表示之化合物為較佳。As the phenol compound other than the hindered phenol compound, the compound represented by the formula (Y) is preferable.
[化學式2] [Chemical Formula 2]
式(Y)中,R4 表示取代基。取代基的定義如上所述,其中烷基、烯基、炔基、芳基或烷氧基為較佳,烷氧基為更佳。 m表示0~3的整數。其中1為較佳。In formula (Y), R 4 represents a substituent. The definition of the substituent is as described above, wherein alkyl, alkenyl, alkynyl, aryl or alkoxy is preferred, and alkoxy is more preferred. m represents an integer of 0 to 3. Among them, 1 is better.
作為苯醌系化合物,式(Z)所表示之化合物為較佳。As the benzoquinone compound, the compound represented by formula (Z) is preferred.
[化學式3] [Chemical Formula 3]
式(Z)中,R5 ~R8 分別獨立地表示氫原子或取代基。取代基的定義如上所述,其中芳基、胺基、經取代之胺基或鹵素原子為較佳。 作為苯醌系化合物,例如可以舉出鄰苯醌及對苯醌。In formula (Z), R 5 to R 8 each independently represent a hydrogen atom or a substituent. The definition of the substituent is as described above, and aryl, amine, substituted amine or halogen atom is preferred. Examples of benzoquinone compounds include o-benzoquinone and p-benzoquinone.
作為氫醌系化合物,式(V)所表示之化合物為較佳。As the hydroquinone compound, the compound represented by formula (V) is preferred.
[化學式4] [Chemical Formula 4]
式(V)中,R9 表示取代基。取代基的定義如上所述,其中烷基、烯基、炔基、芳基或烷氧基為較佳,烷基為更佳。當p為2以上時,複數個R9 可以相同,亦可以不同。 p表示0~4的整數。其中1為較佳。In formula (V), R 9 represents a substituent. The definition of the substituent is as described above, wherein alkyl, alkenyl, alkynyl, aryl or alkoxy is preferred, and alkyl is more preferred. When p is 2 or more, a plurality of R 9 may be the same or different. p represents an integer of 0-4. Among them, 1 is better.
聚合抑制劑可以單獨使用1種,亦可以併用2種以上。其中,在本發明的效果更優異之觀點上,感光性組成物包含2種以上的聚合抑制劑為較佳。 又,當感光性組成物包含2種以上的聚合抑制劑時,聚合抑制劑係選自包括受阻酚系化合物、受阻酚系化合物以外的酚系化合物、苯醌系化合物及氫醌系化合物之群組中之至少2種以上為較佳。 又,在本發明的效果更優異之觀點上,聚合抑制劑包含選自包括受阻酚系化合物、苯醌化合物及氫醌化合物之群組中之1種以上的第1聚合抑制劑和受阻酚系化合物以外的酚系化合物為較佳。 另外,受阻酚系化合物以外的酚系化合物的含量相對於第1聚合抑制劑的合計含量之質量比並不受特別限制,但在本發明的效果更優異之觀點上,0.0009~0.17為較佳。One type of polymerization inhibitor may be used alone, or two or more types may be used in combination. Among them, from the viewpoint that the effect of the present invention is more excellent, it is preferable that the photosensitive composition contains two or more kinds of polymerization inhibitors. In addition, when the photosensitive composition contains two or more kinds of polymerization inhibitors, the polymerization inhibitor is selected from the group consisting of hindered phenol compounds, hindered phenol compounds, phenol compounds, benzoquinone compounds, and hydroquinone compounds. At least two or more of the groups are preferred. In addition, from the viewpoint that the effect of the present invention is more excellent, the polymerization inhibitor includes one or more first polymerization inhibitors and hindered phenols selected from the group consisting of hindered phenol compounds, benzoquinone compounds, and hydroquinone compounds. Phenolic compounds other than compounds are preferred. In addition, the mass ratio of the content of the phenol compound other than the hindered phenol compound to the total content of the first polymerization inhibitor is not particularly limited, but from the viewpoint that the effect of the present invention is more excellent, 0.0009 to 0.17 is preferable .
感光性組成物中之聚合抑制劑的含量並不受特別限制,但在本發明的效果更優異之觀點上,相對於感光性組成物總質量,0.0001~0.30質量%為較佳,0.002~0.20質量%為更佳。The content of the polymerization inhibitor in the photosensitive composition is not particularly limited, but from the viewpoint that the effect of the present invention is more excellent, it is preferably 0.0001 to 0.30% by mass relative to the total mass of the photosensitive composition, and 0.002 to 0.20 Quality% is better.
(紫外線吸收劑) 紫外線吸收劑係指不具有藉由光或熱引發聚合性化合物的聚合之功能(亦即,不符合聚合起始劑)者。在此,“不具有引發聚合性化合物的聚合之功能”係指即使紫外線吸收劑實際上受到光或熱的能量,亦不會產生用於引發聚合性化合物的聚合之活性種。(UV absorber) The ultraviolet absorber refers to one that does not have the function of initiating the polymerization of the polymerizable compound by light or heat (that is, it does not meet the polymerization initiator). Here, "does not have the function of initiating the polymerization of the polymerizable compound" means that even if the ultraviolet absorber actually receives light or heat energy, no active species for initiating the polymerization of the polymerizable compound will be generated.
紫外線吸收劑係不僅不具有引發聚合性化合物的聚合之功能,而且亦不具有後述的增感劑的特性者為較佳。在此,增感劑的特性係指藉由將本身吸收光而得到之能量轉移到其他物質(聚合起始劑等)而引發聚合之特性。It is preferable that the ultraviolet absorber system not only does not have the function of initiating the polymerization of the polymerizable compound, but also does not have the characteristics of the sensitizer described below. Here, the characteristics of the sensitizer refer to the characteristics of initiating polymerization by transferring the energy obtained by absorbing light itself to other substances (polymerization initiator, etc.).
紫外線吸收劑在波長300~430nm的範圍具有極大吸收波長為較佳,在波長330~420nm的範圍具有極大吸收波長為更佳。 紫外線吸收劑在(I)波長340~380nm的範圍、(II)波長380~420nm的範圍及(III)波長420~450nm的範圍中的至少任1個範圍具有極大吸收波長為進一步較佳。The ultraviolet absorber preferably has a maximum absorption wavelength in the range of 300-430 nm, and more preferably has a maximum absorption wavelength in the range of 330-420 nm. It is further preferable that the ultraviolet absorber has a maximum absorption wavelength in at least one of (I) wavelength range of 340 to 380 nm, (II) wavelength range of 380 to 420 nm, and (III) wavelength range of 420 to 450 nm.
當進行了紫外線吸收劑的熱質量測定時,於150℃下之質量減少率係5%以下為較佳,3%以下為更佳。下限並不受特別限制,可以舉出0%。若於150℃下之質量減少率在上述範圍內,則在後述的曝光時紫外線吸收劑難以發生分解,容易發揮作為紫外線吸收劑之功能。 又,當進行了紫外線吸收劑的熱質量測定時,於220℃下之質量減少率係40%以上為較佳,超過40%為更佳,70%以上為進一步較佳。上限並不受特別限制,可以舉出100%。若於220℃下之質量減少率在上述範圍內,則在曝光後實施之加熱處理時紫外線吸收劑發生分解,可抑制來自紫外線吸收劑之著色。 紫外線吸收劑的熱質量測定的條件如下。 亦即,在氮氣的氛圍下,將紫外線吸收劑以升溫速度10℃/分鐘的條件從25℃的狀態升溫至100℃。於100℃下保持30分鐘之後,將紫外線吸收劑以升溫速度10℃/分鐘的條件升溫至220℃,並於220℃下保持30分鐘。 將於100℃下保持30分鐘紫外線吸收劑時之、從保持開始之後24~29分鐘的紫外線吸收劑的質量的平均值作為紫外線吸收劑的質量的基準值(100%),測定於150℃時點及於220℃下加熱30分鐘之後之紫外線吸收劑的質量,根據下述式計算質量減少率。 於150℃下之質量減少率(%)=100-(於150℃下之紫外線吸收劑的質量/紫外線吸收劑的質量的基準值)×100 於220℃下之質量減少率(%)=100-(於220℃下加熱30分鐘之後之紫外線吸收劑的質量/紫外線吸收劑的質量的基準值)×100When the thermal mass of the ultraviolet absorber is measured, the mass reduction rate at 150°C is preferably 5% or less, and more preferably 3% or less. The lower limit is not particularly limited, and 0% can be cited. If the mass reduction rate at 150° C. is within the above range, the ultraviolet absorber hardly decomposes during exposure to be described later, and it easily functions as an ultraviolet absorber. In addition, when the thermal mass of the ultraviolet absorber is measured, the mass reduction rate at 220° C. is preferably 40% or more, more than 40% is more preferable, and 70% or more is still more preferable. The upper limit is not particularly limited, and 100% can be cited. If the mass reduction rate at 220°C is within the above range, the ultraviolet absorber will decompose during the heat treatment performed after exposure, and coloration from the ultraviolet absorber can be suppressed. The conditions for measuring the thermal mass of the ultraviolet absorber are as follows. That is, under a nitrogen atmosphere, the ultraviolet absorber was heated from a state of 25°C to 100°C at a temperature increase rate of 10°C/min. After maintaining at 100°C for 30 minutes, the ultraviolet absorber was heated to 220°C at a temperature increase rate of 10°C/min and held at 220°C for 30 minutes. When the ultraviolet absorber is held at 100°C for 30 minutes, the average value of the mass of the ultraviolet absorber from 24 to 29 minutes after the start of the retention is taken as the reference value (100%) of the mass of the ultraviolet absorber, measured at 150°C And the mass of the ultraviolet absorber after heating at 220°C for 30 minutes, the mass reduction rate was calculated according to the following formula. Mass reduction rate (%) at 150°C=100-(Quality value of the mass of UV absorber at 150°C/mass of UV absorber)×100 Mass reduction rate (%) at 220°C=100-(mass value of ultraviolet absorber after heating at 220°C for 30 minutes/reference value of mass of ultraviolet absorber)×100
紫外線吸收劑的種類並不受特別限制,例如可以舉出二苯甲醯甲烷系化合物、胺基丁二烯系化合物、水楊酸酯系化合物、二苯甲酮系化合物、苯并三唑系化合物、經取代之丙烯腈系化合物及三嗪系化合物,其中二苯甲醯甲烷系化合物或胺基丁二烯系化合物為較佳。 作為二苯甲醯甲烷系化合物(二苯甲醯甲烷系紫外線吸收劑),可以舉出2-甲基二苯甲醯甲烷、4-甲基二苯甲醯甲烷、4-異丙基二苯甲醯甲烷、4-第三丁基二苯甲醯甲烷、2,4-二甲基二苯甲醯甲烷、2,5-二甲基二苯甲醯甲烷、4,4’-二異丙基二苯甲醯甲烷、4,4’-二甲氧基二苯甲醯甲烷、4-第三丁基-4’-甲氧基二苯甲醯甲烷(亞佛苯酮(avobenzone))、2-甲基-5-異丙基-4’-甲氧基二苯甲醯甲烷、2-甲基-5-第三丁基-4’-甲氧基二苯甲醯甲烷及2,4-二甲基-4’-甲氧基二苯甲醯甲烷、2,6-二甲基-4-第三丁基-4’-甲氧基二苯甲醯甲烷。 作為胺基丁二烯系化合物(胺基丁二烯系紫外線吸收劑),可以舉出具有式(1)所表示之部分結構之化合物。式(1)中,*表示鍵結位置。The type of ultraviolet absorber is not particularly limited, and examples thereof include dibenzoylmethane-based compounds, aminobutadiene-based compounds, salicylate-based compounds, benzophenone-based compounds, and benzotriazole-based compounds. Among the compounds, substituted acrylonitrile-based compounds and triazine-based compounds, dibenzoylmethane-based compounds or aminobutadiene-based compounds are preferred. Examples of the dibenzoylmethane-based compound (dibenzoylmethane-based ultraviolet absorber) include 2-methyldibenzoylmethane, 4-methyldibenzoylmethane, and 4-isopropyldibenzene Methane, 4-tert-butyldibenzoylmethane, 2,4-dimethyldibenzoylmethane, 2,5-dimethyldibenzoylmethane, 4,4'-diisopropyl Dibenzoylmethane, 4,4'-dimethoxydibenzoylmethane, 4-third butyl-4'-methoxydibenzoylmethane (avobenzone), 2-methyl-5-isopropyl-4'-methoxydibenzoylmethane, 2-methyl-5-third butyl-4'-methoxydibenzoylmethane and 2,4 -Dimethyl-4'-methoxydibenzoylmethane, 2,6-dimethyl-4-third butyl-4'-methoxydibenzoylmethane. Examples of the aminobutadiene-based compound (aminobutadiene-based ultraviolet absorber) include compounds having a partial structure represented by formula (1). In formula (1), * represents the bonding position.
[化學式5] [Chemical Formula 5]
作為水楊酸酯系化合物(水楊酸酯系紫外線吸收劑),可以舉出水楊酸苯酯、水楊酸對辛基苯酯及水楊酸對第三丁基苯酯。
作為二苯甲酮系化合物(二苯甲酮系紫外線吸收劑),可以舉出2,2’-二羥基-4-甲氧基二苯甲酮、2,2’-二羥基-4,4’-二甲氧基二苯甲酮、2,2’,4,4’-四羥基二苯甲酮、2-羥基-4-甲氧基二苯甲酮、2,4-二羥基二苯甲酮及2-羥基-4-辛氧基二苯甲酮。
作為苯并三唑系化合物(苯并三唑系紫外線吸收劑),可以舉出2-(2’-羥基-3’,5’-二-第三丁基苯基)-5-氯苯并三唑、2-(2’-羥基-3’-第三丁基-5’-甲基苯基)-5-氯苯并三唑、2-(2’-羥基-3’-第三戊基-5’-異丁基苯基)-5-氯苯并三唑、2-(2’-羥基-3’-異丁基-5’-甲基苯基)-5-氯苯并三唑、2-(2’-羥基-3’-異丁基-5’-丙基苯基)-5-氯苯并三唑、2-(2’-羥基-3’,5’-二-第三丁基苯基)苯并三唑、2-(2’-羥基-5’-甲基苯基)苯并三唑及2-[2’-羥基-5’-(1,1,3,3-四甲基)苯基]苯并三唑。
作為經取代之丙烯腈系化合物(經取代之丙烯腈系紫外線吸收劑),可以舉出2-氰基-3,3-二苯基丙烯酸乙酯及2-氰基-3,3-二苯基丙烯酸2-乙基己酯。
作為三嗪系化合物(三嗪系紫外線吸收劑),可以舉出2-[4-[(2-羥基-3-十二烷氧基丙基)氧基]-2-羥基苯基]-4,6-雙(2,4-二甲基苯基)-1,3,5-三嗪、2-[4-[(2-羥基-3-十三烷氧基丙基)氧基]-2-羥基苯基]-4,6-雙(2,4-二甲基苯基)-1,3,5-三嗪、2-(2,4-二羥基苯基)-4,6-雙(2,4-二甲基苯基)-1,3,5-三嗪等單(羥基苯基)三嗪化合物;2,4-雙(2-羥基-4-丙氧基苯基)-6-(2,4-二甲基苯基)-1,3,5-三嗪、2,4-雙(2-羥基-3-甲基-4-丙氧基苯基)-6-(4-甲基苯基)-1,3,5-三嗪、2,4-雙(2-羥基-3-甲基-4-己氧基苯基)-6-(2,4-二甲基苯基)-1,3,5-三嗪等雙(羥基苯基)三嗪化合物;2,4-雙(2-羥基-4-丁氧基苯基)-6-(2,4-二丁氧基苯基)-1,3,5-三嗪、2,4,6-三(2-羥基-4-辛氧基苯基)-1,3,5-三嗪、2,4,6-三[2-羥基-4-(3-丁氧基-2-羥基丙氧基)苯基]-1,3,5-三嗪等三(羥基苯基)三嗪化合物。
除了上述以外,還可以舉出二乙基胺基-苯基磺醯基-戊二烯酸酯系紫外線吸收劑(FUJIFILM Finechemicals Co.,Ltd.製造,商品名:DPO)。
又,能夠參閱日本特開2012-032556號公報的段落0103(對應之WO2012/015076號說明書的第30頁))以後的通式(1)~(8)中的任一個所表示之化合物或其具體例(1-1)~(8-3),該等的內容被編入本申請說明書中。Examples of the salicylate-based compound (salicylate-based ultraviolet absorber) include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate.
Examples of the benzophenone-based compound (benzophenone-based ultraviolet absorber) include 2,2'-dihydroxy-4-methoxybenzophenone and 2,2'-dihydroxy-4,4 '-Dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone Methone and 2-hydroxy-4-octyloxybenzophenone.
As the benzotriazole-based compound (benzotriazole-based ultraviolet absorber), 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzo Triazole, 2-(2'-hydroxy-3'-third butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-third pentan Group-5'-isobutylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole Azole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di- Third butylphenyl) benzotriazole, 2-(2'-hydroxy-5'-methylphenyl) benzotriazole and 2-[2'-hydroxy-5'-(1,1,3 ,3-tetramethyl)phenyl]benzotriazole.
Examples of the substituted acrylonitrile-based compound (substituted acrylonitrile-based ultraviolet absorber) include 2-cyano-3,3-diphenyl acrylate and 2-cyano-3,3-diphenyl 2-ethylhexyl acrylate.
Examples of the triazine-based compound (triazine-based ultraviolet absorber) include 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4 ,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]- 2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6- Bis(2,4-dimethylphenyl)-1,3,5-triazine and other mono(hydroxyphenyl)triazine compounds; 2,4-bis(2-hydroxy-4-propoxyphenyl) -6-(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-3-methyl-4-propoxyphenyl)-6- (4-methylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-di Bis(hydroxyphenyl)triazine compounds such as methylphenyl)-1,3,5-triazine; 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4 -Dibutoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2, 4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine and other tris(hydroxyphenyl)triazine compounds.
In addition to the above, a diethylamino-phenylsulfonyl-pentadienoate ultraviolet absorber (manufactured by FUJIFILM Finechemicals Co., Ltd., trade name: DPO) can also be mentioned.
Also, refer to the compound represented by any one of the general formulas (1) to (8) or the following paragraphs 0103 of Japanese Patent Application Laid-Open No. 2012-032556 (corresponding to
感光性組成物中之紫外線吸收劑的含量並不受特別限制,但相對於感光性組成物總質量,0.01~10.0質量%為較佳,0.05~1.50質量%為更佳。 紫外線吸收劑可以單獨使用1種,亦可以併用2種以上。The content of the ultraviolet absorber in the photosensitive composition is not particularly limited, but relative to the total mass of the photosensitive composition, 0.01 to 10.0 mass% is preferable, and 0.05 to 1.50 mass% is more preferable. One type of ultraviolet absorber may be used alone, or two or more types may be used in combination.
在感光性組成物中,紫外線吸收劑的含量相對於聚合抑制劑的含量之質量比為0.08~330,在本發明的效果更優異之觀點上,0.1~200為較佳,3~30為更佳。另外,從矩形性優異之觀點而言,20以上為進一步較佳。In the photosensitive composition, the mass ratio of the content of the ultraviolet absorber to the content of the polymerization inhibitor is 0.08 to 330. From the viewpoint that the effect of the present invention is more excellent, 0.1 to 200 is preferable, and 3 to 30 is more good. In addition, from the viewpoint of excellent rectangularity, 20 or more is more preferable.
感光性組成物中可以包含上述成分以外的其他成分,例如可以舉出樹脂黏合劑、增感劑、溶劑、界面活性劑、分散劑、交聯劑及硬化促進劑。 以下,對各個成分進行詳細敘述。The photosensitive composition may contain components other than the above-mentioned components, and examples thereof include resin binders, sensitizers, solvents, surfactants, dispersants, crosslinking agents, and hardening accelerators. Hereinafter, each component will be described in detail.
(樹脂黏合劑) 作為樹脂黏合劑,例如可以舉出(甲基)丙烯酸系樹脂、胺基甲酸酯系樹脂、聚乙烯醇、聚乙烯醇縮丁醛、聚乙烯醇縮甲醛、聚醯胺、聚酯、聚醯亞胺及聚苯并㗁唑,(甲基)丙烯酸系樹脂或胺基甲酸酯系樹脂為較佳。 又,作為樹脂黏合劑,鹼可溶性黏合劑(鹼可溶性樹脂)亦為較佳。當感光性組成物包含鹼可溶性黏合劑時,在對由感光性組成物得到之塗膜進行了曝光之情況下,用鹼顯影液能夠容易去除未曝光部。 作為鹼可溶性黏合劑,例如可以舉出(甲基)丙烯酸系樹脂、胺基甲酸酯系樹脂、聚乙烯醇、聚乙烯醇縮丁醛、聚乙烯醇縮甲醛、聚醯胺、聚酯、聚醯亞胺或其前驅體及聚苯并㗁唑或其前驅體,(甲基)丙烯酸系樹脂或胺基甲酸酯系樹脂為較佳。 作為聚醯亞胺或其前驅體及聚苯并㗁唑或其前驅體,能夠參閱WO2011/067998號公報的段落0012~0046的說明及日本特開2013-050593號公報的段落0020~0054中所記載之聚醯亞胺樹脂的說明,該等的內容被編入本申請說明書中。(Resin adhesive) Examples of the resin binder include (meth)acrylic resins, urethane resins, polyvinyl alcohol, polyvinyl butyral, polyvinyl formal, polyamide, polyester, and poly Acetylene imide and polybenzoxazole, (meth)acrylic resin or urethane resin are preferred. In addition, as a resin binder, an alkali-soluble binder (alkali-soluble resin) is also preferable. When the photosensitive composition contains an alkali-soluble binder, when the coating film obtained from the photosensitive composition is exposed, the unexposed portion can be easily removed with an alkali developer. Examples of the alkali-soluble adhesives include (meth)acrylic resins, urethane resins, polyvinyl alcohol, polyvinyl butyral, polyvinyl formal, polyvinyl amide, polyester, Polyimide or its precursor and polybenzoxazole or its precursor are preferably (meth)acrylic resins or urethane resins. As polyimide or its precursor and polybenzoxazole or its precursor, see the description of paragraphs 0012 to 0046 of WO2011/067998 and paragraphs 0020 to 0054 of Japanese Patent Laid-Open No. 2013-050593 The description of the described polyimide resin, and such contents are incorporated in the specification of this application.
鹼可溶性黏合劑具有酸基為較佳。 作為酸基,可以舉出羧酸基、磺酸基、膦酸基、磷酸基及磺醯胺基,從獲得原料之觀點而言,羧酸基為較佳。 作為具有酸基之鹼可溶性黏合劑,使用具有酸基之聚合性化合物而得到之聚合物為較佳,從調節酸值之觀點而言,藉由將具有酸基之聚合性化合物和不具有酸基之聚合性化合物進行共聚合而得到之共聚物為更佳。 作為具有酸基之聚合性化合物,例如可以舉出丙烯酸、甲基丙烯酸、衣康酸、巴豆酸、異巴豆酸、順丁烯二酸及對羧基苯乙烯,丙烯酸、甲基丙烯酸或對羧基苯乙烯為較佳。It is preferable that the alkali-soluble adhesive has an acid group. Examples of the acid group include a carboxylic acid group, a sulfonic acid group, a phosphonic acid group, a phosphoric acid group, and a sulfonamide group. From the viewpoint of obtaining a raw material, a carboxylic acid group is preferred. As the alkali-soluble binder having an acid group, a polymer obtained by using a polymerizable compound having an acid group is preferable. From the viewpoint of adjusting the acid value, by combining the polymerizable compound having an acid group and a non-acid The copolymer obtained by copolymerizing the base polymerizable compound is more preferable. Examples of the polymerizable compound having an acid group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid and p-carboxystyrene, acrylic acid, methacrylic acid or p-carboxybenzene Ethylene is preferred.
作為不具有酸基之聚合性化合物,例如可以舉出(甲基)丙烯酸酯(烷基酯、芳基酯及芳烷基酯等)。 (甲基)丙烯酸酯的烷基酯部位中之烷基可以為直鏈狀,亦可以為支鏈狀,碳數1~10的烷基為較佳,碳數1~6的烷基為更佳。 作為(甲基)丙烯酸酯的芳基酯部位中之芳基,碳數6~14的芳基為較佳,碳數6~10的芳基為更佳。 作為(甲基)丙烯酸酯的芳烷基酯部位中之芳烷基,碳數7~20的芳烷基為較佳,碳數7~12的芳烷基為更佳。Examples of the polymerizable compound having no acid group include (meth)acrylates (alkyl esters, aryl esters, and aralkyl esters). The alkyl group in the alkyl ester portion of the (meth)acrylate may be linear or branched. The alkyl group having 1 to 10 carbon atoms is preferred, and the alkyl group having 1 to 6 carbon atoms is more preferred. good. As the aryl group in the aryl ester portion of the (meth)acrylate, aryl groups having 6 to 14 carbon atoms are preferred, and aryl groups having 6 to 10 carbon atoms are more preferred. As the aralkyl group in the aralkyl ester portion of the (meth)acrylate, an aralkyl group having 7 to 20 carbon atoms is preferred, and an aralkyl group having 7 to 12 carbon atoms is more preferred.
鹼可溶性黏合劑中之酸基的含量並沒有特別限制,但從鹼顯影性及所得到之硬化膜的強度的觀點而言,0.5~4.0meq/g為較佳,0.5~3.0meq/g為更佳。The content of acid groups in the alkali-soluble adhesive is not particularly limited, but from the viewpoint of alkali developability and the strength of the resulting cured film, 0.5 to 4.0 meq/g is preferred, and 0.5 to 3.0 meq/g is Better.
鹼可溶性黏合劑進一步具有交聯性基為較佳。藉此,尤其能夠提高曝光部的硬化性和未曝光部的鹼顯影性雙方,又,可得到耐久性高的圖案。 交聯性基係指在對由感光性組成物得到之塗膜進行曝光或加熱時在塗膜中產生之聚合反應的過程中使樹脂黏合劑交聯之基團。作為交聯性基,例如可以舉出聚合性基(例如,作為能夠加成聚合反應之官能基之乙烯性不飽和鍵結基)、胺基及環氧基等。其中,雙鍵基為較佳,乙烯性不飽和雙鍵基為更佳。 又,作為交聯性基,亦可以為藉由光照射能夠成為自由基之官能基,例如可以舉出硫醇基及鹵素基。 其中,作為交聯性基,乙烯性不飽和雙鍵基為較佳。作為乙烯性不飽和雙鍵基,苯乙烯基、(甲基)丙烯醯基或烯丙基為較佳,(甲基)丙烯醯基為更佳。It is preferable that the alkali-soluble adhesive further has a crosslinkable group. In this way, in particular, both the curability of the exposed portion and the alkali developability of the unexposed portion can be improved, and a pattern with high durability can be obtained. The crosslinkable group refers to a group that crosslinks the resin binder during the polymerization reaction that occurs in the coating film when the coating film obtained from the photosensitive composition is exposed or heated. Examples of the crosslinkable group include a polymerizable group (for example, an ethylenically unsaturated bonding group as a functional group capable of addition polymerization reaction), an amine group, and an epoxy group. Among them, the double bond group is preferable, and the ethylenically unsaturated double bond group is more preferable. In addition, the crosslinkable group may be a functional group capable of becoming a radical by light irradiation, and examples thereof include a thiol group and a halogen group. Among them, as the crosslinkable group, an ethylenically unsaturated double bond group is preferred. As the ethylenically unsaturated double bond group, styryl, (meth)acryloyl or allyl is preferred, and (meth)acryloyl is more preferred.
鹼可溶性黏合劑中之交聯性基的含量並沒有特別限制,但0.5~3.0meq/g為較佳,1.0~3.0meq/g為更佳,1.5~2.8meq/g為特佳。 在此,含量(meq/g)例如能夠藉由碘值滴定來進行測定。 具有交聯性基之鹼可溶性黏合劑詳細記載於日本特開2003-262958號公報,亦能夠將其中所記載之化合物用於本發明。The content of the crosslinkable group in the alkali-soluble adhesive is not particularly limited, but 0.5 to 3.0 meq/g is preferred, 1.0 to 3.0 meq/g is more preferred, and 1.5 to 2.8 meq/g is particularly preferred. Here, the content (meq/g) can be measured by, for example, iodine value titration. The alkali-soluble adhesive having a crosslinkable group is described in detail in Japanese Patent Application Publication No. 2003-262958, and the compounds described therein can also be used in the present invention.
作為鹼可溶性黏合劑的較佳態樣之一,可以舉出將包含下述通式(ED)所表示之化合物(以下,亦稱為“醚二聚物”。)之單量體成分聚合而成之聚合物(以下,亦稱為“特定聚合物”。)。若使用特定聚合物,則紅外光截止濾波器的圖案形成性更優異。As one of the preferable forms of the alkali-soluble binder, a single-volume component containing a compound represented by the following general formula (ED) (hereinafter, also referred to as "ether dimer") can be exemplified The resulting polymer (hereinafter, also referred to as "specific polymer."). If a specific polymer is used, the infrared light cut filter has more excellent pattern formability.
[化學式6] [Chemical Formula 6]
通式(ED)中,R1 及R2 分別表示氫原子或可以具有取代基之碳數1~25的烴基。 作為R1 及R2 所表示之可以具有取代基之碳數1~25的烴基,可以舉出直鏈狀或支鏈狀的烷基;芳基;脂環式基;經烷氧基取代之烷基;經苄基等芳基取代之烷基;等。 其中,在取代基的耐熱性優異之觀點上,甲基、乙基、環己基或苄基為較佳。In the general formula (ED), R 1 and R 2 each represent a hydrogen atom or a C 1-25 hydrocarbon group which may have a substituent. Examples of the hydrocarbon groups having 1 to 25 carbon atoms which may have substituents represented by R 1 and R 2 include linear or branched alkyl groups; aryl groups; alicyclic groups; and alkoxy-substituted Alkyl; alkyl substituted by aryl such as benzyl; etc. Among them, a methyl group, an ethyl group, a cyclohexyl group, or a benzyl group is preferred from the viewpoint of excellent heat resistance of the substituent.
作為醚二聚物的具體例,可以舉出日本特開2012-208494號公報的段落0565(對應之美國專利申請公開第2012/235099號說明書的段落0694)中所記載之醚二聚物的具體例,該等的內容被編入本申請說明書中。 其中,二甲基-2,2’-[氧基雙(亞甲基)]雙-2-丙酸酯、二乙基-2,2’-[氧基雙(亞甲基)]雙-2-丙酸酯、二環己基-2,2’-[氧基雙(亞甲基)]雙-2-丙酸酯或二苄基-2,2’-[氧基雙(亞甲基)]雙-2-丙酸酯為較佳。 該等醚二聚物可以僅為1種,亦可以為2種以上。來自通式(ED)所表示之化合物之結構體可以使其他單量體共聚合。As specific examples of the ether dimer, specific examples of the ether dimer described in paragraph 0565 of Japanese Patent Application Laid-Open No. 2012-208494 (corresponding to paragraph 0694 of US Patent Application Publication No. 2012/235099) For example, such content is incorporated into the specification of this application. Among them, dimethyl-2,2'-[oxybis(methylene)]bis-2-propionate, diethyl-2,2'-[oxybis(methylene)]bis- 2-propionate, dicyclohexyl-2,2'-[oxybis(methylene)]bis-2-propionate or dibenzyl-2,2'-[oxybis(methylene )] Bis-2-propionate is preferred. These ether dimers may be only one kind or two or more kinds. The structure derived from the compound represented by the general formula (ED) can copolymerize other monomers.
來自特定聚合物中之醚二聚物之重複單元的含量相對於鹼可溶性黏合劑中的所有重複單元,1~50莫耳%為較佳,1~20莫耳%為更佳。 亦可以與醚二聚物一同使其他單量體共聚合。 作為其他單量體,例如可以舉出用於導入酸基之單量體、用於導入自由基聚合性雙鍵之單量體、用於導入環氧基之單量體及該等以外的其他能夠共聚合之單量體。 該等單量體可以僅使用1種,亦可以使用2種以上。The content of the repeating unit derived from the ether dimer in a specific polymer is preferably 1 to 50 mol%, and more preferably 1 to 20 mol% relative to all the repeating units in the alkali-soluble binder. It is also possible to copolymerize other monomers together with the ether dimer. Examples of other single bodies include a single body for introducing an acid group, a single body for introducing a radically polymerizable double bond, a single body for introducing an epoxy group, and others other than these Monomer capable of copolymerization. Only one type may be used for these single masses, or two or more types may be used.
作為用於導入酸基之單量體,例如可以舉出(甲基)丙烯酸及衣康酸等具有羧基之單體、N-羥基苯基順丁烯二醯亞胺等具有酚性羥基之單體、以及順丁烯二酸酐及衣康酸酐等具有羧酸酐基之單體。其中,(甲基)丙烯酸為較佳。 又,用於導入酸基之單量體可以為在聚合後能夠賦予酸基之單量體,例如可以舉出(甲基)丙烯酸2-羥基乙酯等具有羥基之單量體、(甲基)丙烯酸縮水甘油酯等具有環氧基之單量體及2-異氰酸酯(甲基)丙烯酸乙酯等具有異氰酸酯基之單量體。 當使用在聚合後能夠賦予酸基之單量體時,需要進行在聚合後賦予酸基之處理。作為在聚合後賦予酸基之處理,例如若為使用具有羥基之單量體之情況,則可以舉出使琥珀酸酐、四氫鄰苯二甲酸酐及順丁烯二酸酐的酸酐加成之處理。Examples of the single unit for introducing an acid group include monomers having a carboxyl group such as (meth)acrylic acid and itaconic acid, and monomers having a phenolic hydroxyl group such as N-hydroxyphenyl maleimide. Monomers such as maleic anhydride and itaconic anhydride. Among them, (meth)acrylic acid is preferred. In addition, the single body for introducing an acid group may be a single body capable of imparting an acid group after polymerization, for example, a single body having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate, (methyl ) Monomers with epoxy groups such as glycidyl acrylate and isocyanate groups such as 2-isocyanate (meth)ethyl acrylate. When a single unit capable of imparting an acid group after polymerization is used, it is necessary to perform a treatment for imparting an acid group after polymerization. As a treatment for giving an acid group after polymerization, for example, in the case of using a single body having a hydroxyl group, a treatment for adding an acid anhydride of succinic anhydride, tetrahydrophthalic anhydride, and maleic anhydride may be mentioned. .
當包含通式(ED)所表示之化合物之單量體成分包含用於導入酸基之單量體時,用於導入酸基之單量體的含量相對於單量體成分總質量,5~70質量%為較佳,10~60質量%為更佳。When the single body component containing the compound represented by the general formula (ED) contains a single body for introducing acid groups, the content of the single body for introducing acid groups is 5 to 5 relative to the total mass of the
作為用於導入自由基聚合性雙鍵之單量體,例如可以舉出(甲基)丙烯酸及衣康酸等具有羧基之單體;順丁烯二酸酐及衣康酸酐等具有羧酸酐基之單體;(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸3,4-環氧環己基甲酯及鄰-(或間-或對-)乙烯基苄基縮水甘油醚等具有環氧基之單體。 當使用用於導入自由基聚合性雙鍵之單量體時,需要進行在聚合後賦予自由基聚合性雙鍵之處理。作為在聚合後用於賦予自由基聚合性雙鍵之處理,例如若為使用具有羧基之單體之情況,則可以舉出使(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸3,4-環氧環己基甲酯及鄰-(或間-或對-)乙烯基苄基縮水甘油醚等具有環氧基和自由基聚合性雙鍵之化合物加成之處理。Examples of the monomers for introducing radical polymerizable double bonds include monomers having a carboxyl group such as (meth)acrylic acid and itaconic acid; those having a carboxylic acid anhydride group such as maleic anhydride and itaconic anhydride Monomer; glycidyl (meth)acrylate, 3,4-epoxycyclohexyl methyl (meth)acrylate and o-(or m-or p-) vinylbenzyl glycidyl ether etc. have epoxy groups Of monomers. When using a single volume for introducing radically polymerizable double bonds, it is necessary to perform a treatment for imparting radically polymerizable double bonds after polymerization. As a treatment for imparting radical polymerizable double bonds after polymerization, for example, when a monomer having a carboxyl group is used, glycidyl (meth)acrylate, 3,4 (meth)acrylic acid -Addition treatment of epoxy cyclohexyl methyl ester and o-(or m- or p-) vinylbenzyl glycidyl ether and other compounds with epoxy group and free radical polymerizable double bond.
當包含通式(ED)所表示之化合物之單量體成分包含用於導入自由基聚合性雙鍵之單量體時,用於導入自由基聚合性雙鍵之單量體的含量相對於單量體成分總質量,5~70質量%為較佳,10~60質量%為更佳。When the single body component containing the compound represented by the general formula (ED) contains a single body for introducing radical polymerizable double bonds, the content of the single body for introducing radical polymerizable double bonds is The total mass of the body composition is preferably 5 to 70% by mass, and more preferably 10 to 60% by mass.
作為用於導入環氧基之單量體,例如可以舉出(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸3,4-環氧環己基甲酯及鄰-(或間-或對-)乙烯基苄基縮水甘油醚。 當包含通式(ED)所表示之化合物之單量體成分包含用於導入環氧基之單量體時,用於導入環氧基之單量體的含量相對於單量體成分總質量,5~70質量%為較佳,10~60質量%為更佳。Examples of the single-quantity body for introducing epoxy groups include glycidyl (meth)acrylate, 3,4-epoxycyclohexyl methyl (meth)acrylate, and o-(or m-or p- ) Vinyl benzyl glycidyl ether. When the single body component containing the compound represented by the general formula (ED) contains the single body for introducing the epoxy group, the content of the single body for introducing the epoxy group relative to the total mass of the single body component, It is preferably 5 to 70% by mass, and more preferably 10 to 60% by mass.
當將包含通式(ED)所表示之化合物之單量體成分聚合而成之聚合物包含其他能夠共聚合之單量體時,其含有比例並不受特別限制,但95質量%以下為較佳,85質量%以下為更佳。When a polymer obtained by polymerizing a single component containing a compound represented by the general formula (ED) contains other single components capable of copolymerization, the content ratio is not particularly limited, but 95% by mass or less is Good, 85% by mass or less is even better.
特定聚合物的重量平均分子量並不受特別限制,但從由感光性組成物形成之塗膜的耐熱性的觀點而言,2000~200000為較佳,5000~100000為更佳,5000~20000為進一步較佳。 又,當特定聚合物具有酸基時,酸值係30~500mgKOH/g為較佳,50~400mgKOH/g為更佳。The weight-average molecular weight of the specific polymer is not particularly limited, but from the viewpoint of the heat resistance of the coating film formed of the photosensitive composition, 2,000 to 200,000 are preferred, 5,000 to 100,000 are more preferred, and 5,000 to 20,000 are Further preferred. In addition, when the specific polymer has an acid group, the acid value is preferably 30 to 500 mgKOH/g, and more preferably 50 to 400 mgKOH/g.
作為適用於特定聚合物的合成中之聚合方法,能夠採用以往公知的各種聚合方法,溶液聚合法為較佳。詳細而言,例如遵照日本特開2004-300204號公報中所記載之聚合物(a)的合成方法,能夠合成將包含通式(ED)所表示之化合物之單量體成分聚合而成之聚合物。As a polymerization method suitable for the synthesis of a specific polymer, various conventionally known polymerization methods can be used, and a solution polymerization method is preferred. In detail, for example, in accordance with the method of synthesizing the polymer (a) described in Japanese Patent Laid-Open No. 2004-300204, it is possible to synthesize a polymer obtained by polymerizing a single component containing a compound represented by the general formula (ED) Thing.
以下,示出特定聚合物的例示化合物,但本發明並不限定於該等。 下述所示之例示化合物的組成比為莫耳%。作為市售品,例如可以舉出Acrycure RD-F8(丙烯酸系樹脂)(NIPPON SHOKUBAI CO.,LTD.製造)等。Hereinafter, exemplary compounds of specific polymers are shown, but the present invention is not limited to these. The composition ratio of the exemplified compounds shown below is mole %. Examples of commercially available products include Acrycure RD-F8 (acrylic resin) (manufactured by NIPPON SHOKUBAI CO., LTD.) and the like.
[化學式7] [Chemical Formula 7]
[化學式8] [Chemical Formula 8]
感光性組成物中之樹脂黏合劑(尤其是鹼可溶性黏合劑)的含量並不受特別限制,但在紅外光截止濾波器的強度更優異且改善光微影性及殘渣之觀點上,相對於感光性組成物總質量,5~50質量%為較佳,10~25質量%為更佳。The content of the resin binder (especially alkali-soluble binder) in the photosensitive composition is not particularly limited, but from the viewpoint that the strength of the infrared light cut filter is more excellent and the photolithography and residue are improved, relative to The total mass of the photosensitive composition is preferably 5-50% by mass, and more preferably 10-25% by mass.
(溶劑) 溶劑的種類並不受特別限制,可以舉出水及有機溶劑。 作為溶劑,可以舉出在1個大氣壓下之沸點為170~200℃的溶劑A。 溶劑A的沸點為170~200℃,180~193℃為較佳。(Solvent) The type of solvent is not particularly limited, and water and organic solvents can be mentioned. Examples of the solvent include solvent A having a boiling point of 170 to 200°C at 1 atmosphere. The boiling point of the solvent A is 170 to 200°C, preferably 180 to 193°C.
作為溶劑A的較佳態樣之一,在溶劑A中,在分子內包含3個以上的氧原子為較佳,氧原子的數量係3~5為更佳,3為進一步較佳。 作為溶劑A的較佳態樣,可以舉出以下式(X)或式(Y)所表示之溶劑。 式(X) R1 O-(L-O)n -R2 式(Y) R1 O-(L-O)m -CO-R2 式(X)及式(Y)中,R1 表示氫原子或烷基。烷基中所包含之碳數並不受特別限制,但1~3為較佳,1為更佳。 R2 表示烷基。烷基中所包含之碳數係1~3為較佳,1為更佳。 L表示伸烷基。伸烷基中所包含之碳數係3~5為較佳,3為更佳。 n表示2~4的整數。 m表示1~2的整數。 作為溶劑A的具體例,可以舉出二丙二醇單甲醚(沸點188℃)、環己醇乙酸酯(沸點173℃)、二丙二醇二甲醚(沸點171℃)、乙二醇單丁醚乙酸酯(沸點192℃)、二乙二醇二乙醚(沸點189℃)、二乙二醇單甲醚(沸點194℃)、丙二醇二乙酸酯(沸點190℃)、3-甲氧基丁基乙酸酯(沸點171℃)、丙二醇正丁醚(沸點170℃)、二乙二醇乙基甲醚(沸點176℃)及二乙二醇異丙基甲醚(沸點179℃)。 另外,作為溶劑A的較佳態樣之一,在溶劑A中包含上述式(X)或式(Y)所表示之溶劑作為主成分為較佳。主成分係指相對於溶劑A總質量,式(X)或式(Y)所表示之溶劑的含量超過50質量%。 另外,作為溶劑A的其他較佳態樣之一,在溶劑A中包含作為上述溶劑A的具體例而舉出之溶劑(例如,二丙二醇單甲醚)作為主成分為較佳。主成分係指相對於溶劑A總質量,作為上述溶劑A的具體例而舉出之溶劑的含量超過50質量%。As one of the preferable aspects of the solvent A, in the solvent A, it is preferable to include 3 or more oxygen atoms in the molecule, the number of oxygen atoms is preferably 3 to 5, and 3 is still more preferable. As a preferable aspect of the solvent A, a solvent represented by the following formula (X) or formula (Y) may be mentioned. Formula (X) R 1 O-(LO) n -R 2 Formula (Y) R 1 O-(LO) m -CO-R 2 In formula (X) and formula (Y), R 1 represents a hydrogen atom or an alkane base. The number of carbons contained in the alkyl group is not particularly limited, but 1 to 3 is preferred, and 1 is more preferred. R 2 represents an alkyl group. The number of carbons included in the alkyl group is preferably 1 to 3, and 1 is more preferable. L represents alkylene. The number of carbons contained in the alkylene group is preferably 3 to 5, and 3 is more preferable. n represents an integer of 2 to 4. m represents an integer of 1-2. Specific examples of the solvent A include dipropylene glycol monomethyl ether (boiling point 188°C), cyclohexanol acetate (boiling point 173°C), dipropylene glycol dimethyl ether (boiling point 171°C), ethylene glycol monobutyl ether Acetate (boiling point 192°C), diethylene glycol diethyl ether (boiling point 189°C), diethylene glycol monomethyl ether (boiling point 194°C), propylene glycol diacetate (boiling point 190°C), 3-methoxy Butyl acetate (boiling point 171℃), propylene glycol n-butyl ether (boiling point 170℃), diethylene glycol ethyl methyl ether (boiling point 176℃) and diethylene glycol isopropyl methyl ether (boiling point 179℃). In addition, as one of the preferable aspects of the solvent A, it is preferable that the solvent A contains the solvent represented by the above formula (X) or formula (Y) as a main component. The main component means that the content of the solvent represented by formula (X) or formula (Y) exceeds 50% by mass relative to the total mass of the solvent A. In addition, as one of other preferable aspects of the solvent A, it is preferable that the solvent A include a solvent (for example, dipropylene glycol monomethyl ether) mentioned as a specific example of the solvent A as the main component. The main component means that the content of the solvent mentioned as a specific example of the solvent A exceeds 50% by mass relative to the total mass of the solvent A.
感光性組成物中之溶劑A的含量相對於感光性組成物總質量,0.1~20質量%為較佳,0.3~5.0質量%為更佳。The content of the solvent A in the photosensitive composition relative to the total mass of the photosensitive composition is preferably 0.1 to 20% by mass, and more preferably 0.3 to 5.0% by mass.
感光性組成物包含選自包括在1個大氣壓下之沸點為100~130℃的溶劑B1及在1個大氣壓下之沸點超過130℃且小於170℃的溶劑B2之群組中之溶劑B為較佳。 溶劑B1在1個大氣壓下之沸點為100~130℃,120~130℃為較佳。 溶劑B2在1個大氣壓下之沸點超過130℃且小於170℃,140~150℃為較佳。The photosensitive composition includes a solvent B1 selected from the group consisting of a solvent B1 having a boiling point of 100 to 130°C at 1 atmosphere and a solvent B2 having a boiling point of more than 130°C and less than 170°C at 1 atmosphere. good. The boiling point of the solvent B1 at 1 atm is 100 to 130°C, preferably 120 to 130°C. The boiling point of the solvent B2 at 1 atmosphere pressure exceeds 130°C and less than 170°C, preferably 140 to 150°C.
作為溶劑B1,可以舉出乙酸丁酯(沸點126℃)、乙二醇單甲醚(沸點125℃)、甲基正丁基酮(沸點127℃)及四氫呋喃(沸點126℃)。 作為溶劑B2,可以舉出丙二醇1-單甲醚2-乙酸酯(沸點145℃)、乙二醇單甲醚乙酸酯(沸點145℃)、乳酸乙酯(沸點155℃)、二乙二醇二甲醚(沸點162℃)、3-甲氧基丁醇(沸點161℃)及丙二醇正丙醚(沸點150℃)。Examples of the solvent B1 include butyl acetate (boiling point 126°C), ethylene glycol monomethyl ether (boiling point 125°C), methyl n-butyl ketone (boiling point 127°C), and tetrahydrofuran (boiling point 126°C). Examples of the solvent B2 include propylene glycol 1-monomethyl ether 2-acetate (boiling point 145°C), ethylene glycol monomethyl ether acetate (boiling point 145°C), ethyl lactate (boiling point 155°C), diethyl ether Glycol dimethyl ether (boiling point 162°C), 3-methoxybutanol (boiling point 161°C) and propylene glycol n-propyl ether (boiling point 150°C).
感光性組成物中之溶劑B的含量相對於感光性組成物總質量,20~90質量%為較佳,40~70質量%為更佳。 感光性組成物中之溶劑A與溶劑B的質量比(溶劑A的質量/溶劑B的質量)係0.005~0.500為較佳,0.010~0.200為更佳。 當在感光性組成物中包含溶劑B1時,感光性組成物中之溶劑B1的含量相對於感光性組成物總質量,0.1~10質量%為較佳,0.5~5.0質量%為更佳。 當在感光性組成物中包含溶劑B2時,感光性組成物中之溶劑B1的含量相對於感光性組成物總質量,20~80質量%為較佳,30~70質量%為更佳。 溶劑B可以僅使用1種,亦可以併用2種以上。其中,在本發明的效果更優異之觀點上,併用上述溶劑B1及上述溶劑B2為較佳。 當併用溶劑B1及溶劑B2時,溶劑B1與溶劑B2的質量比(溶劑B1的質量/溶劑B2的質量)係0.005~0.500為較佳,0.010~0.200為更佳。The content of the solvent B in the photosensitive composition relative to the total mass of the photosensitive composition is preferably 20 to 90% by mass, and more preferably 40 to 70% by mass. The mass ratio of solvent A to solvent B in the photosensitive composition (mass of solvent A/mass of solvent B) is preferably 0.005 to 0.500, and more preferably 0.010 to 0.200. When the solvent B1 is included in the photosensitive composition, the content of the solvent B1 in the photosensitive composition is preferably 0.1 to 10% by mass, and more preferably 0.5 to 5.0% by mass relative to the total mass of the photosensitive composition. When the solvent B2 is included in the photosensitive composition, the content of the solvent B1 in the photosensitive composition is preferably 20 to 80% by mass and more preferably 30 to 70% by mass relative to the total mass of the photosensitive composition. Solvent B may use only 1 type, and may use 2 or more types together. Among them, from the viewpoint that the effect of the present invention is more excellent, it is preferable to use the solvent B1 and the solvent B2 together. When the solvent B1 and the solvent B2 are used together, the mass ratio of the solvent B1 and the solvent B2 (the mass of the solvent B1/the mass of the solvent B2) is preferably 0.005 to 0.500, and more preferably 0.010 to 0.200.
(界面活性劑) 從進一步提高塗佈性之觀點而言,在感光性組成物中可以包含界面活性劑。又,藉由界面活性劑包含於感光性組成物中,圖案矩形性更優異。 作為界面活性劑,可以舉出氟系界面活性劑、非離子系界面活性劑、陽離子系界面活性劑、陰離子系界面活性劑及矽酮系界面活性劑,氟系界面活性劑或矽酮系界面活性劑為較佳。(Surfactant) From the viewpoint of further improving coatability, a surfactant may be included in the photosensitive composition. In addition, when the surfactant is contained in the photosensitive composition, the pattern rectangularity is more excellent. Examples of the surfactant include fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants and silicone-based surfactants, fluorine-based surfactants or silicone-based interfaces Active agents are preferred.
作為氟系界面活性劑,例如可以舉出Megafac F171、Megafac F172、Megafac F173、Megafac F176、Megafac F177、Megafac F141、Megafac F142、Megafac F143、Megafac F144、Megafac R30、Megafac F437、MegafacF475、Megafac F479、Megafac F482、Megafac F554、Megafac F780、Megafac F781、Megafac F781F(以上為DIC CORPORATION製造)、Fluorad FC430、Fluorad FC431、Fluorad FC171(以上為Sumitomo 3M Limited製造)、Surflon S-382、Surflon SC-101、Surflon SC-103、Surflon SC-104、Surflon SC-105、Surflon SC-1068、Surflon SC-381、Surflon SC-383、Surflon S-393、Surflon KH-40(以上為Asahi Glass Co.,Ltd.製造)、PF636、PF656、PF6320、PF6520、PF7002(OMNOVA Solutions Inc.製造)等。又,可以舉出日本特開2012-208494號公報的段落0552(對應之美國專利申請公開第2012/0235099號說明書的<0678>)等中所記載之界面活性劑,該等的內容被編入本申請說明書中。 作為非離子系界面活性劑,可以舉出聚氧乙烯烷基醚、聚氧乙烯烷基烯丙醚、聚氧乙烯脂肪酸酯、脫水山梨糖醇脂肪酸酯、聚氧乙烯脫水山梨糖醇脂肪酸酯、聚氧乙烯烷基胺、甘油脂肪酸酯、氧乙烯-氧丙烯嵌段共聚物、炔二醇系界面活性劑及乙炔系聚氧環氧乙烷。 作為陽離子系界面活性劑,可以舉出日本特開2012-208494號公報的段落0554(對應之美國專利申請公開第2012/0235099號說明書的<0680>)中所記載之陽離子系界面活性劑,該等的內容被編入本申請說明書中。 作為陰離子系界面活性劑,可以舉出W004、W005、W017(Yusho Co.,Ltd.製造)。 作為矽酮系界面活性劑,可以舉出日本特開2012-208494號公報的段落0556(對應之美國專利申請公開第2012/0235099號說明書的<0682>)等中所記載之矽酮系界面活性劑,該等的內容被編入本申請說明書中。Examples of fluorine-based surfactants include Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, Megafac F141, Megafac F142, Megafac F143, Megafac F144, Megafac R30, Megafac F437, Megafac F475, Megafac F475, Megafac F482, Megafac F554, Megafac F780, Megafac F781, Megafac F781F (made by DIC CORPORATION above), Fluorad FC430, Fluorad FC431, Fluorad FC171 (made by Sumitomo 3M Limited above), Surflon S-382, Surflon SC-101, Surflon SC -103, Surflon SC-104, Surflon SC-105, Surflon SC-1068, Surflon SC-381, Surflon SC-383, Surflon S-393, Surflon KH-40 (above manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc.), etc. In addition, the surfactants described in paragraph 0552 of Japanese Patent Laid-Open No. 2012-208494 (corresponding to <0678> in the specification of US Patent Application Publication No. 2012/0235099) and the like can be cited. In the application manual. Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, and polyoxyethylene sorbitan fats. Acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester, oxyethylene-oxypropylene block copolymer, acetylene glycol-based surfactant, and acetylene-based polyoxyethylene oxide. Examples of the cationic surfactants include the cationic surfactants described in paragraph 0554 of Japanese Patent Laid-Open No. 2012-208494 (corresponding to <0680> of US Patent Application Publication No. 2012/0235099), which The contents of etc. are incorporated into the specification of this application. Examples of the anionic surfactants include W004, W005, and W017 (manufactured by Yusho Co., Ltd.). Examples of silicone-based surfactants include those described in paragraph 0556 of Japanese Patent Laid-Open No. 2012-208494 (corresponding to <0682> of US Patent Application Publication No. 2012/0235099) and the like. Agents, and such contents are incorporated into the specification of this application.
在紅外光截止濾波器的強度更優異之觀點上,感光性組成物中之界面活性劑的含量相對於感光性組成物總質量,0.0001~0.1000質量%為較佳,0.0010~0.0700質量%為更佳。From the viewpoint that the intensity of the infrared cut filter is more excellent, the content of the surfactant in the photosensitive composition is preferably 0.0001 to 0.1000% by mass relative to the total mass of the photosensitive composition, and more preferably 0.0010 to 0.0700% by mass. good.
(分散劑) 在感光性組成物中可以包含分散劑。藉由包含分散劑,在感光性組成物中的特定粒子的分散穩定性得到提高。另外,分散劑還作為上述黏合劑發揮功能。 作為分散劑,可以舉出高分子分散劑〔例如,聚醯胺胺及其鹽、多羧酸及其鹽、高分子量不飽和酸酯、改質聚胺酯、改質聚酯、改質聚(甲基)丙烯酸酯、(甲基)丙烯酸系共聚物及萘磺酸福馬林縮合物〕、聚氧乙烯烷基磷酸酯、聚氧乙烯烷基胺及烷醇胺。 作為高分子分散劑,可以舉出直鏈狀高分子、末端改質型高分子、接枝型高分子及嵌段型高分子。(Dispersant) A dispersant may be included in the photosensitive composition. By including a dispersant, the dispersion stability of specific particles in the photosensitive composition is improved. In addition, the dispersant also functions as the above-mentioned binder. Examples of the dispersant include polymer dispersants [for example, polyamidoamine and its salts, polycarboxylic acid and its salts, high molecular weight unsaturated acid esters, modified polyurethane esters, modified polyesters, and modified poly(A Base) acrylate, (meth)acrylic copolymer and formalin condensate of naphthalene sulfonate], polyoxyethylene alkyl phosphate, polyoxyethylene alkylamine and alkanolamine. Examples of the polymer dispersant include linear polymers, terminal modified polymers, graft polymers, and block polymers.
作為末端改質型高分子,例如可以舉出在末端具有磷酸基之高分子、在末端具有磺酸基之高分子、具有有機色素的部分骨架或雜環之高分子及利用在一末端具有羥基或胺基之低聚物或聚合物與酸酐進行改質而製造之高分子。
作為接枝型高分子,例如可以舉出聚(低級伸烷基亞胺)與聚酯的反應產物、聚烯丙胺與聚酯的反應產物、具有鹼性基和酸性基之兩性分散樹脂、具有有機色素的部分骨架或雜環之接枝型高分子及巨單體與含有酸基之單體的共聚物。
作為藉由自由基聚合製造接枝型高分子時所使用之巨單體,可以舉出公知的巨單體,可以舉出TOAGOSEI CO.,LTD.製造之巨單體AA-6(末端基為甲基丙烯醯基的聚甲基丙烯酸甲酯)、AS-6(末端基為甲基丙烯醯基的聚苯乙烯)、AN-6S(末端基為甲基丙烯醯基的苯乙烯與丙烯腈的共聚物)、AB-6(末端基為甲基丙烯醯基的聚丙烯酸丁酯)、Daicel Chemical Industries, Ltd.製造之PLACCEL FM5(甲基丙烯酸2-羥基乙酯的ε-己內酯5莫耳當量加成品)、FA10L(丙烯酸2-羥基乙酯的ε-己內酯10莫耳當量加成品)及日本特開平2-272009號公報中所記載之聚酯系巨單體等。其中,在柔軟性和親溶劑性優異之觀點上,聚酯系巨單體為較佳。
作為嵌段型高分子,日本特開2003-049110號公報、日本特開2009-052010號公報等中所記載之嵌段型高分子為較佳。Examples of the terminal-modified polymer include polymers having a phosphate group at the terminal, polymers having a sulfonic acid group at the terminal, polymers having a partial skeleton of organic dyes or heterocycles, and polymers having hydroxyl groups at one terminal. Or an amine-based oligomer or polymer modified with an acid anhydride to produce a polymer.
Examples of the graft-type polymer include a reaction product of poly(lower alkyleneimine) and polyester, a reaction product of polyallylamine and polyester, an amphoteric dispersion resin having a basic group and an acid group, and having Copolymers of grafted polymers and macromonomers with partial skeletons or heterocycles of organic pigments and monomers containing acid groups.
As the macromonomer used in the production of the graft-type polymer by radical polymerization, a known macromonomer can be mentioned, and the macromonomer AA-6 (terminal group is manufactured by TOAGOSEI CO., LTD. Methacryloyl-based polymethyl methacrylate), AS-6 (polystyrene with methacryloyl end groups), AN-6S (styrene and acrylonitrile with methacryloyl end groups) Copolymer), AB-6 (polybutyl acrylate with a terminal methacryloyl group), PLACCEL FM5 (ε-caprolactone 2-hydroxyethyl methacrylate 5) manufactured by Daicel Chemical Industries, Ltd. Molar equivalent plus product), FA10L (2-hydroxyethyl acrylate ε-
作為分散劑,例如可以舉出BYKChemie公司製造之“Disperbyk-101(聚醯胺胺磷酸鹽)、107(羧酸酯)、110(包含酸基之共聚物)、130(聚醯胺)、161、162、163、164、165、166、170(高分子共聚物)”、“BYK-P104、P105(高分子量不飽和多羧酸)”、EFKA公司製造之“EFKA4047、4050、4010(聚胺酯系)、EFKA4330、4340(嵌段共聚物)、4400~4402(改質聚丙烯酸酯)、5010(聚酯醯胺)、6220(脂肪酸聚酯)、6745(酞菁衍生物)”、Ajinomoto Fine-Techno Co.,Inc.製造之“AJISPER PB821、PB822、PB880、PB881”、KYOEISHA CHEMICAL Co.,LTD.製造之“Florene TG-710(胺基甲酸酯低聚物)”、“Plyfolw No. 50E、No. 300(丙烯酸系共聚物)”、Kusumoto Chemicals, Ltd.製造之“DISPARLON KS-860、873SN、874、#2150(脂肪族多元羧酸)、#7004(聚醚酯)、DA-703-50、DA-705、DA-725”、Kao Corporation製造之“DEMOL RN、N(萘磺酸福馬林縮聚物)、MS、C、SN-B(芳香族磺酸福馬林縮聚物)”、“HOMOGENOL L-18(高分子多羧酸)”、“Emalgen920、930、935、985(聚氧乙烯壬基苯基醚)”、“Acetamine 86(硬脂胺乙酸酯)”、Lubrizol Japan Ltd.製造之“SOLSPERSE 5000(酞菁衍生物)、13240(聚酯胺)、3000、17000、27000(在末端部具有功能部之高分子)、24000、28000、32000、38500(接枝型高分子)”、Nikko Chemicals Co.,Ltd.製造之“NIKKOL T106(聚氧乙烯脫水山梨糖醇單油酸酯)、MYS-IEX(聚氧乙烯單硬脂酸酯)”、Kawaken Fine Chemicals Co.,Ltd.製造之HINOACT T-8000E等、Shin-Etsu Chemical Co.,Ltd.製造之有機矽氧烷聚合物KP-341、Yusho Co.,Ltd.製造之“W001:陽離子系界面活性劑”、聚氧乙烯月桂基醚、聚氧乙烯硬脂基醚、聚氧乙烯油基醚、聚氧乙烯辛基苯基醚、聚氧乙烯壬基苯基醚、聚乙二醇二月桂酸酯、聚乙二醇二硬脂酸酯、脫水山梨糖醇脂肪酸酯等非離子系界面活性劑、“W004、W005、W017”等陰離子系界面活性劑、MORISHITA&CO.,LTD.製造之“EFKA-46、EFKA-47、EFKA-47EA、EFKA聚合物100、EFKA聚合物400、EFKA聚合物401、EFKA聚合物450”、SAN NOPCO LIMITED製造之“DISPERSE AID 6、DISPERSE AID 8、DISPERSE AID 15、DISPERSE AID 9100”等高分子分散劑、ADEKA CORPORATION製造之“ADEKA PLURONIC L31、F38、L42、L44、L61、L64、F68、L72、P95、F77、P84、F87、P94、L101、P103、F108、L121、P-123”及SANYO KASEI CO.,LTD.製造之“IONET(商品名)S-20”等。Examples of the dispersant include "Disperbyk-101 (polyamide amine phosphate), 107 (carboxylate), 110 (copolymer containing acid group), 130 (polyamide), 161 manufactured by BYK Chemie. , 162, 163, 164, 165, 166, 170 (polymer copolymer)", "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid)", "EFKA4047, 4050, 4010 (polyurethane series ), EFKA4330, 4340 (block copolymer), 4400~4402 (modified polyacrylate), 5010 (polyesteramide), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative)”, Ajinomoto Fine- "AJISPER PB821, PB822, PB880, PB881" manufactured by Techno Co., Inc., "Florene TG-710 (urethane oligomer)" manufactured by KYOEISHA CHEMICAL Co., LTD., "Plyfolw No. 50E , No. 300 (acrylic copolymer), "DISPARLON KS-860, 873SN, 874, #2150 (aliphatic polycarboxylic acid), #7004 (polyether ester), DA-703 manufactured by Kusumoto Chemicals, Ltd. -50, DA-705, DA-725", "DEMOL RN, N (formalin polycondensate of naphthalenesulfonic acid), MS, C, SN-B (formalin polycondensate of aromatic sulfonic acid)" manufactured by Kao Corporation, "HOMOGENOL L-18 (polymeric polycarboxylic acid)", "Emalgen920, 930, 935, 985 (polyoxyethylene nonylphenyl ether)", "Acetamine 86 (stearylamine acetate)", Lubrizol Japan Ltd .Manufactured "SOLSPERSE 5000 (phthalocyanine derivatives), 13240 (polyesteramine), 3000, 17000, 27000 (polymer with functional part at the end), 24000, 28000, 32000, 38500 (grafted polymer )”, “NIKKOL T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate)” manufactured by Nikko Chemicals Co., Ltd., Kawaken Fine Chemicals Co., Ltd.'s HINOACT T-8000E, etc., Shin-Etsu Chemical Co., Ltd.'s organosiloxane polymer KP-341, Yusho Co., Ltd.'s "W001: cationic surfactant", polymer oxygen Ethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol Nonionic surfactants such as alcohol distearate, sorbitan fatty acid esters, anionic surfactants such as "W004, W005, W017", "EFKA-46, EFKA-" manufactured by MORISHITA & CO., LTD. 47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450", "DISPERSE AID 6, DISPERSE AID 8, DISPERSE AID 15, DISPERSE AID 9100" manufactured by SAN NOPCO LIMITED, etc. Polymer dispersant, "ADEKA PLURONIC L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123" manufactured by ADEKA CORPORATION And "IONET (trade name) S-20" manufactured by SANYO KASEI CO., LTD., etc.
當使用分散劑時,首先,由特定粒子(及根據需要,其他紅外光遮蔽劑)和分散劑及適當的溶劑製備分散組成物之後,摻合於組成物中,這從提高分散性之觀點而言為較佳。 感光性組成物中之分散劑的含量相對於特定粒子總質量,10~70質量%為較佳,30~60質量%為更佳。When a dispersant is used, first, after preparing a dispersion composition from specific particles (and other infrared light shielding agents as needed) and a dispersant and an appropriate solvent, it is blended into the composition from the viewpoint of improving dispersibility Words are better. The content of the dispersant in the photosensitive composition is preferably 10 to 70% by mass, and more preferably 30 to 60% by mass relative to the total mass of specific particles.
(增感劑) 在感光性組成物中可以包含增感劑。藉由增感劑包含於感光性組成物中,圖案矩形性更優異。 作為增感劑,藉由電子移動機構或能量移動機構使上述光聚合起始劑增感者為較佳。 所使用之增感劑的種類並不受特別限制,例如可以舉出日本特開2012-122045號公報的段落0202中所例示之化合物。 感光性組成物中之增感劑的含量相對於感光性組成物中的總固體成分,0.01~10.0質量%為較佳,0.10~4.0質量%為更佳。(Sensitizer) A sensitizer may be included in the photosensitive composition. When the sensitizer is included in the photosensitive composition, the pattern rectangularity is more excellent. As the sensitizer, it is preferable to sensitize the photopolymerization initiator by an electron moving mechanism or an energy moving mechanism. The type of sensitizer used is not particularly limited, and examples thereof include compounds exemplified in paragraph 0202 of Japanese Patent Laid-Open No. 2012-122045. The content of the sensitizer in the photosensitive composition relative to the total solid content in the photosensitive composition is preferably 0.01 to 10.0% by mass, and more preferably 0.10 to 4.0% by mass.
(交聯劑) 在感光性組成物中可以包含交聯劑。藉由在感光性組成物中包含交聯劑,能夠期待提高紅外光截止濾波器的強度。 交聯劑係具有2個以上的交聯性基之化合物為較佳。作為交聯性基,可以舉出氧雜環丁烷基、氰酸酯基及與關於鹼可溶性黏合劑可具有之交聯性基而舉出者相同之基團,環氧基、氧雜環丁烷基或氰酸酯基為較佳。亦即,作為交聯劑,環氧化合物、氧雜環丁烷化合物或氰酸酯化合物為較佳。 所使用之交聯劑的種類並不受特別限制,例如可以舉出日本特開2012-122045號公報的段落0204~0209中所例示之化合物。(Crosslinking agent) A crosslinking agent may be included in the photosensitive composition. By including a cross-linking agent in the photosensitive composition, it is expected to increase the strength of the infrared light cut filter. The crosslinking agent is preferably a compound having two or more crosslinkable groups. Examples of the crosslinkable group include an oxetanyl group, a cyanate group, and the same groups as those mentioned for the crosslinkable group that the alkali-soluble binder can have, and epoxy groups and oxetane groups Butyl groups or cyanate groups are preferred. That is, as the crosslinking agent, epoxy compounds, oxetane compounds or cyanate compounds are preferred. The type of crosslinking agent used is not particularly limited, and examples thereof include compounds exemplified in paragraphs 0204 to 0209 of Japanese Patent Application Laid-Open No. 2012-122045.
(硬化促進劑) 在感光性組成物中可以包含硬化促進劑。 所使用之硬化促進劑的種類並不受特別限制,例如可以舉出日本特開2012-122045號公報的段落0211中所例示之化合物。(Hardening accelerator) A hardening accelerator may be included in the photosensitive composition. The type of hardening accelerator used is not particularly limited, and examples thereof include compounds exemplified in paragraph 0211 of Japanese Patent Laid-Open No. 2012-122045.
感光性組成物能夠混合上述各成分來進行製備。 感光性組成物的用途並不受特別限制,但用於形成紅外光遮蔽層為較佳,用於形成紅外光截止濾波器為更佳。亦即,使用感光性組成物而形成之硬化膜用於紅外光遮光層為較佳。 使用本發明的感光性組成物而形成之紅外光截止濾波器例如亦能夠用於固體攝像元件的受光側之紅外光截止濾波器及固體攝像元件的背面側(與受光側相反之一側)之紅外光截止濾波器。 又,亦可以將本發明的感光性組成物直接塗佈於濾色器上或平坦化層上而用於塗膜的形成。 本發明的感光性組成物能夠以能夠塗佈之狀態供給,因此在固體攝像元件的所期望之構件或位置能夠容易形成紅外光截止濾波器。The photosensitive composition can be prepared by mixing the above components. The use of the photosensitive composition is not particularly limited, but it is preferably used for forming an infrared light shielding layer, and more preferably used for forming an infrared light cut filter. That is, the cured film formed using the photosensitive composition is preferably used for the infrared light shielding layer. The infrared cut filter formed using the photosensitive composition of the present invention can also be used for, for example, an infrared cut filter on the light-receiving side of a solid-state imaging element and the back side (the side opposite to the light-receiving side) of the solid-state imaging element Infrared light cut filter. In addition, the photosensitive composition of the present invention may be directly applied to a color filter or a planarization layer and used for forming a coating film. Since the photosensitive composition of the present invention can be supplied in a state where it can be applied, the infrared light cut filter can be easily formed in a desired member or position of the solid-state imaging element.
<紅外光截止濾波器> 接著,對本發明的紅外光截止濾波器進行說明。 本發明的紅外光截止濾波器係使用上述本發明的感光性組成物而形成。 紅外光截止濾波器的膜厚能夠根據目的適當選擇,20μm以下為較佳,10μm以下為更佳,5μm以下為進一步較佳。為了維持遮光能力,膜厚的下限係0.1μm以上為較佳,0.2μm以上為更佳,0.3μm以上為進一步較佳。 紅外光截止濾波器的在波長400~1300nm下之最大透射率並不受特別限制,但60%以上為較佳,65%以上為更佳。 又,紅外光截止濾波器在波長900~1300nm下之最大透射率並不受特別限制,但20%以下為較佳,10%以下為更佳,5%以下為最佳。<Infrared cut filter> Next, the infrared cut filter of the present invention will be described. The infrared cut filter of the present invention is formed using the above-mentioned photosensitive composition of the present invention. The film thickness of the infrared light cut filter can be appropriately selected according to the purpose, preferably 20 μm or less, more preferably 10 μm or less, and further preferably 5 μm or less. In order to maintain the light-shielding ability, the lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and further preferably 0.3 μm or more. The maximum transmittance of the infrared light cut filter at a wavelength of 400 to 1300 nm is not particularly limited, but it is preferably 60% or more, and more preferably 65% or more. In addition, the maximum transmittance of the infrared light cut filter at a wavelength of 900 to 1300 nm is not particularly limited, but it is preferably 20% or less, more preferably 10% or less, and most preferably 5% or less.
紅外光截止濾波器用於具有吸收或截止紅外光之功能之透鏡(數位相機、行動電話及車載相機等相機用透鏡、以及f-θ透鏡及讀取(pick up)透鏡等光學透鏡)、半導體受光元件用光學濾波器、近接照度感測器用紅外光截止濾波器、以節能用阻斷熱線之紅外光截止濾波器或紅外光吸收板、以太陽光的選擇性利用為目的之農業用塗層、利用紅外光的吸收熱之記錄媒體、電子設備用或照片用近紅外光截止濾波器、保護眼鏡、太陽眼鏡、熱線阻斷薄膜、光學文字讀取記錄、機密文檔複印防止用、電子照片感光體及雷射焊接等。 尤其,對CCD(Charge Coupled Device(電荷耦合元件))相機用雜訊截止濾波器或CMOS(Complementary Metal Oxide Semiconductor(互補型金屬氧化物半導體))影像感測器用濾波器有用。Infrared cut-off filters are used for lenses that have the function of absorbing or cutting off infrared light (lenses for cameras such as digital cameras, mobile phones, and car cameras, and optical lenses such as f-θ lenses and pick-up lenses), and semiconductor light reception Optical filters for components, infrared cut-off filters for proximity illuminance sensors, infrared cut-off filters or infrared absorbers for energy-saving hot-line blocking, agricultural coatings for the purpose of selective utilization of sunlight, use Infrared light absorption heat recording media, near-infrared cutoff filters for electronic devices or photographs, protective glasses, sunglasses, hot-line blocking films, optical text reading records, confidential document copying prevention, electronic photoreceptors and Laser welding, etc. In particular, it is useful for noise-cut filters for CCD (Charge Coupled Device) cameras or filters for CMOS (Complementary Metal Oxide Semiconductor) image sensors.
紅外光截止濾波器的製造方法並不受特別限制,能夠經過藉由將本發明的感光性組成物塗佈於支撐體來形成塗膜之製程來進行製造。 又,如後述,亦可進一步進行形成圖案之製程。The method of manufacturing the infrared light cut filter is not particularly limited, and can be manufactured through a process of forming a coating film by applying the photosensitive composition of the present invention to a support. In addition, as will be described later, a patterning process may be further performed.
作為形成塗膜之方法,例如可以舉出藉由滴加法(滴鑄)、旋塗法、狹縫旋塗法、狹縫塗佈法、網版印刷法及敷抹器塗佈法將上述感光性組成物塗佈於支撐體之方法。 塗佈本發明的感光性組成物之支撐體可以為包含玻璃等之透明基板。又,亦可以為固體攝像元件中的各基材。又,亦可以為設置於固體攝像元件的受光側之另一基板。又,亦可以為設置於固體攝像元件的受光側之平坦化層等層。As a method of forming the coating film, for example, the above-mentioned photosensitive film can be exemplified by a drop method (drop casting), a spin coating method, a slit spin coating method, a slit coating method, a screen printing method, and an applicator coating method. A method of applying a sexual composition to a support. The support to which the photosensitive composition of the present invention is applied may be a transparent substrate containing glass or the like. Moreover, it may be each base material in a solid-state imaging element. In addition, it may be another substrate provided on the light-receiving side of the solid-state imaging element. In addition, it may be a layer such as a planarization layer provided on the light-receiving side of the solid-state imaging element.
作為製造圖案狀的紅外光截止濾波器之方法,例如可以舉出包括將本發明的感光性組成物塗佈於支撐體上而形成塗膜之製程、將塗膜以圖案狀進行曝光之製程及顯影去除未曝光部而形成圖案之製程之方法。 另外,曝光係以不僅包含各種波長的光還包含電子束及X射線等放射線照射之含義來使用。 曝光藉由放射線的照射來進行為較佳,作為放射線,可以舉出紫外光、可見光及電子束,更具體而言,可以舉出KrF、ArF、g射線、h射線及i射線。 作為曝光方式,可以舉出步進機曝光及基於高壓汞燈之曝光。 曝光量係5~3000mJ/cm2 為較佳,10~2000mJ/cm2 為更佳。As a method of manufacturing a pattern-shaped infrared light cut filter, for example, a process including applying the photosensitive composition of the present invention on a support to form a coating film, a process of exposing the coating film in a pattern, and A method of developing a patterning process that removes unexposed parts. In addition, exposure is used to mean not only light of various wavelengths but also radiation irradiation such as electron beams and X-rays. The exposure is preferably performed by irradiation of radiation. Examples of radiation include ultraviolet light, visible light, and electron beams, and more specifically, KrF, ArF, g-rays, h-rays, and i-rays. Examples of the exposure method include stepper exposure and exposure based on a high-pressure mercury lamp. The exposure amount is preferably 5 to 3000 mJ/cm 2, and more preferably 10 to 2000 mJ/cm 2 .
上述中,對藉由顯影處理來形成圖案之方法進行了敘述,但亦可以利用乾式蝕刻法來形成圖案。 在紅外光截止濾波器的製造方法中,可以包括其他製程。作為其他製程,例如可以舉出支撐體的表面處理製程、預加熱製程(預烘烤製程)及後加熱製程(後烘烤製程)。In the above, the method of forming the pattern by the development process has been described, but the dry etching method may also be used to form the pattern. In the manufacturing method of the infrared cut filter, other processes may be included. Examples of other processes include a surface treatment process of a support, a pre-heating process (pre-baking process), and a post-heating process (post-baking process).
預加熱製程中之加熱溫度係80~200℃為較佳,90~150℃為更佳。當使用了加熱板時,預加熱製程中之加熱時間係30~240秒鐘為較佳。The heating temperature in the preheating process is preferably 80 to 200°C, and more preferably 90 to 150°C. When a hot plate is used, the heating time in the pre-heating process is preferably 30 to 240 seconds.
後加熱製程中之加熱溫度係120℃~250℃為較佳,160℃~220℃為更佳。當使用了加熱板時,後加熱製程中之加熱時間係3分鐘~180分鐘為較佳。The heating temperature in the post-heating process is preferably 120°C to 250°C, and more preferably 160°C to 220°C. When a hot plate is used, the heating time in the post-heating process is preferably 3 minutes to 180 minutes.
<固體攝像元件>
上述紅外光截止濾波器能夠較佳地適用於固體攝像元件。
以下,使用圖1對本發明的固體攝像元件的一實施形態進行說明。
在圖1所示之固體攝像元件(紅外光感測器)100中,附圖序號110為固體攝像元件基板。
在固體攝像元件基板110上配置有紅外光截止濾波器111和濾色器112。
在紅外光透射濾波器(透射紅外光之濾色器)113與固體攝像元件基板110之間設置有區域114。在區域114中配置有透射了紅外光透射濾波器113之波長的光能夠透射之樹脂層(例如,透明樹脂層等)。在區域114中可以形成紅外光透射濾波器113。亦即,在固體攝像元件基板110上可以形成紅外光透射濾波器113。
在濾色器112及紅外光透射濾光片113的入射光hν側配置有微透鏡115。以覆蓋微透鏡115之方式形成有平坦化層116。
在圖1中,濾色器112的膜厚和紅外光透射濾波器113的膜厚相同,但兩者的膜厚亦可以不同。
在圖1中,濾色器112設置於比紅外光截止濾波器111更靠入射光hν側的位置,但亦可以將紅外光截止濾波器111和濾色器112的順序替換而將紅外光截止濾波器111設置於比濾色器112更靠入射光hν側的位置。在紅外光截止濾波器111與濾色器112之間可以形成其他層。
作為濾色器112,包含選自包括透射紅色的波長區域的光之濾色器、透射綠色的波長區域的光之濾色器及透射藍色的波長區域的光之濾色器之群組中之至少1個為較佳。
另外,可以在濾色器112中包含紅外光吸收物質而使濾色器112具有作為紅外光截止濾波器之功能。<Solid imaging element>
The infrared light cut filter described above can be suitably applied to a solid-state imaging element.
Hereinafter, an embodiment of the solid-state imaging element of the present invention will be described using FIG. 1.
In the solid-state imaging element (infrared light sensor) 100 shown in FIG. 1,
本發明的固體攝像元件在內部具備紅外光截止濾波器,因此不需要作為相機模組的構件之紅外光截止濾波器,能夠減少相機模組的組件件數,從而能夠實現相機模組的小型化。The solid-state imaging element of the present invention has an infrared cut-off filter inside, so the infrared cut-off filter that is a component of the camera module is not needed, and the number of components of the camera module can be reduced, thereby enabling miniaturization of the camera module .
作為濾色器112並沒有特別限定,能夠使用以往公知的像素形成用濾色器,例如能夠參閱日本特開2014-043556號公報的段落0214~0263的記載,其內容被編入本申請說明書中。
紅外光透射濾波器113根據其光源的發光波長而選擇其特性。The
作為固體攝像元件的較佳態樣之一,具備包含選自包括透射紅色的波長區域的光之濾色器(紅色濾色器)、透射綠色的波長區域的光之濾色器(綠色濾色器)、透射藍色的波長區域的光之濾色器(藍色濾色器)及透射紅外光之濾色器(紅外光透射濾波器)之群組中之至少一個之濾波器層和配置於比濾波器層更靠光入射側的位置之紅外光截止濾波器為較佳。
例如,可以舉出具備在同一平面上具有紅色濾色器、綠色濾色器、藍色濾色器及紅外光透射濾波器之濾波器層和配置於比濾波器層更靠光入射側之位置且配置於濾波器層全面之紅外光截止濾波器之固體攝像元件等。
另外,紅外光截止濾波器只要配置於比基板110更靠光入射側的位置即可。
例如,可以在紅色濾色器上、綠色濾色器上及藍色濾色器上配置有紅外光截止濾波器且在紅外光透射濾波器上配置有紅外光截止濾波器。
又,在上述濾波器層與紅外光截止濾波器之間可以配置有平坦化層。As one of the preferred aspects of the solid-state imaging device, a color filter (red color filter) including light selected from a wavelength region that transmits red light and a color filter (green color filter) that transmits light in a green wavelength region are provided Filter), at least one filter layer and arrangement in the group of a color filter (blue filter) that transmits light in the blue wavelength region and a color filter (infrared light transmission filter) that transmits infrared light An infrared light cut filter located closer to the light incident side than the filter layer is preferred.
For example, a filter layer having a red color filter, a green color filter, a blue color filter, and an infrared light transmission filter on the same plane, and a position closer to the light incident side than the filter layer can be given The solid-state imaging element of the infrared cut-off filter is arranged on the entire filter layer.
In addition, the infrared light cut filter may be disposed on the light incident side of the
接著,作為適用了本發明的固體攝像元件之例子,對攝像裝置(相機系統)進行說明。
圖2係攝像裝置的功能框圖。攝像裝置具備透鏡光學系統1、固體攝像元件10、信號處理部20、信號切換部30、控制部40、信號蓄積部50、發光控制部60、發出紅外光之發光元件的紅外LED(light emitting diode(發光二極體))70及圖像輸出部80及81。另外,作為固體攝像元件10,能夠使用上述固體攝像元件100。又,固體攝像元件10和透鏡光學系統1以外的構成的全部或其一部分亦能夠形成於同一個半導體基板上。關於攝像裝置的各構成,能夠參閱日本特開2011-233983號公報的段落0032~0036,其內容被編入本申請說明書中。
作為攝像裝置,存在動作感測器、近接感測器、手勢感測器等。
[實施例]Next, as an example to which the solid-state imaging element of the present invention is applied, an imaging device (camera system) will be described.
FIG. 2 is a functional block diagram of an imaging device. The imaging device includes a lens optical system 1, a solid-
以下,對本發明的實施例進行說明,但本發明並不受該等實施例的任何限定。另外,只要沒有特別指定,“份”、“%”為質量基準。Hereinafter, the embodiments of the present invention will be described, but the present invention is not limited by these embodiments. In addition, unless otherwise specified, "parts" and "%" are quality standards.
<組成物(感光性組成物)的製備> 將下述表1所示之成分溶解於該表所示之溶劑而製備出感光性組成物。<Preparation of composition (photosensitive composition)> The photosensitive composition was prepared by dissolving the components shown in Table 1 below in the solvents shown in the table.
[表1]
以下總結示出上述表1中所使用之各種成分。The following summarizes the various components used in Table 1 above.
(樹脂黏合劑) 樹脂A:NIPPON SHOKUBAI CO.,LTD.製造之Acrycure RD-F8(符合具有雙鍵基之鹼可溶性黏合劑) (聚合性化合物) DPHA:KAYARAD DPHA(Nippon Kayaku Co.,Ltd.製造) (聚合起始劑) IRGACURE 369:IRGACURE 369(BASF公司製造) (增感劑) DETX-S:Kayacure DETX-S(2,4-二乙基硫雜蒽酮)(SHOJI SANGYO Co.,Ltd.製造) (溶劑) PGMEA:1-甲氧基-2-丙醇乙酸酯 (界面活性劑) Megafac F-781-F(DIC Corporation製造)(Resin adhesive) Resin A: Acrycure RD-F8 manufactured by NIPPON SHOKUBAI CO., LTD. (conforming to alkali-soluble adhesives with double bond groups) (Polymerizable compound) DPHA: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) (Polymerization initiator) IRGACURE 369: IRGACURE 369 (made by BASF) (Sensitizer) DETX-S: Kayacure DETX-S (2,4-diethylthioxanthone) (manufactured by SHOJI SANGYO Co., Ltd.) (Solvent) PGMEA: 1-methoxy-2-propanol acetate (Surfactant) Megafac F-781-F (manufactured by DIC Corporation)
(UV吸收劑(紫外線吸收劑))(UV absorber (ultraviolet absorber))
[化學式9] [Chemical Formula 9]
另外,將進行了上述UV1~UV-6的熱質量測定之結果示於以下表2。In addition, the results of the thermal mass measurement of the above UV1 to UV-6 are shown in Table 2 below.
[表2]
(聚合抑制劑)(Polymerization inhibitor)
[化學式10] [Chemical Formula 10]
(特定粒子) 按照以下步驟製造出特定粒子1。 將鎢微粒(組成:Cs0.33 WO3 、平均粒徑:20nm)(100質量份)、矽酸乙酯(10質量份)及甲醇(90質量份)的混合物於0℃下攪拌10小時之後,於20℃下攪拌了20小時。從所得到之混合物中濾取固體成分,將所回收之固體成分於25℃下乾燥24小時,於100℃下乾燥10小時,於200℃下乾燥1小時之後,進行粉碎而得到了特定粒子1(由SiO2 被覆之鎢微粒)。 如後述的表3所示,變更了偶合劑的種類,除此以外,按照與上述相同之步驟製造出特定粒子2~4。特定粒子2為由TiO2 被覆之鎢微粒,特定粒子3為由Al2 O3 被覆之鎢微粒,特定粒子4為由ZrO2 被覆之鎢微粒。 另外,將未進行上述被覆之鎢微粒作為特定粒子5。(Specific particles) Specific particles 1 were produced in the following steps. After stirring a mixture of tungsten microparticles (composition: Cs 0.33 WO 3 , average particle diameter: 20 nm) (100 parts by mass), ethyl silicate (10 parts by mass), and methanol (90 parts by mass) at 0°C for 10 hours, Stirred at 20°C for 20 hours. The solid content was filtered from the resulting mixture, and the recovered solid content was dried at 25°C for 24 hours, at 100°C for 10 hours, and at 200°C for 1 hour, followed by pulverization to obtain specific particles 1. (Tungsten particles coated with SiO 2 ). As shown in Table 3 described later, except for changing the type of coupling agent, the specific particles 2 to 4 were produced in the same procedure as described above. The specific particles 2 are tungsten particles coated with TiO 2 , the specific particles 3 are tungsten particles coated with Al 2 O 3 , and the specific particles 4 are tungsten particles coated with ZrO 2 . In addition, the tungsten fine particles that have not been coated as described above are designated as the specific particles 5.
[表3]
另外,在上述組成物中進一步包含分散劑。分散劑具有分散上述特定粒子之功能。In addition, the above composition further contains a dispersant. The dispersant has the function of dispersing the above-mentioned specific particles.
使用上述中所得到之組成物實施了以下的各種測定。將結果總結示於下述表5。The following various measurements were performed using the composition obtained above. The results are summarized in Table 5 below.
<耐熱性評價> 以表4所示之比例(質量份)混合下述表4所示之原料之後,用孔徑0.45μm的尼龍製過濾器(Nihon Pall Ltd.製造)進行過濾而製備出Green(綠色)組成物、Red(紅色)組成物及Blue(藍色)組成物。 另外,表中的數值表示質量份。<Evaluation of heat resistance> After mixing the raw materials shown in Table 4 below at the ratio (parts by mass) shown in Table 4, it was filtered with a nylon filter (manufactured by Nihon Pall Ltd.) with a pore size of 0.45 μm to prepare a Green composition. Red (red) composition and Blue (blue) composition. In addition, the numerical values in the table represent parts by mass.
[表4]
另外,上述顏料分散液1為包含以下成分之組成物。 ・C.I.顏料綠58......11.4質量份 ・C.I.顏料黃185......2.3質量份 ・下述結構的化合物1......1.4質量份In addition, the pigment dispersion liquid 1 is a composition containing the following components. ・C.I. Pigment Green 58...... 11.4 parts by mass ・C.I. Pigment Yellow 185......2.3 parts by mass ・Compound 1 of the following structure...1.4 parts by mass
[化學式11] [Chemical Formula 11]
・分散劑1(下述結構的樹脂(酸值=49mgKOH/g、Mw=24000,主鏈中所附記之數值為莫耳比。))......7.2質量份・Dispersant 1 (resin of the following structure (acid value = 49 mgKOH/g, Mw = 24000, the value attached to the main chain is the molar ratio.)) 7.2 parts by mass
[化學式12] [Chemical Formula 12]
・丙二醇甲醚乙酸酯......81.9質量份・Propylene glycol methyl ether acetate......81.9 parts by mass
顏料分散液2為包含以下成分之組成物。 ・C.I.顏料紅254......11.4質量份 ・C.I.顏料黃139......2.3質量份 ・上述結構的化合物1......1.4質量份 ・上述分散劑1......7.2質量份 ・丙二醇甲醚乙酸酯......77.77質量份Pigment dispersion 2 is a composition containing the following components. ・C.I. Pigment Red 254...... 11.4 parts by mass ・C.I. Pigment Yellow 139......2.3 parts by mass ・Compound 1 of the above structure...1.4 parts by mass ・The above dispersant 1...7.2 parts by mass ・Propylene glycol methyl ether acetate......77.77 parts by mass
顏料分散液3為包含以下成分之組成物。 ・C.I.顏料藍15:6......11.4質量份 ・C.I.顏料紫23......2.3質量份 ・上述結構的化合物1......1.4質量份 ・上述分散劑1......7.2質量份 ・丙二醇甲醚乙酸酯......81.9質量份The pigment dispersion liquid 3 is a composition containing the following components. ・C.I. Pigment Blue 15:6...11.4 parts by mass ・C.I. Pigment Violet 23...2.3 parts by mass ・Compound 1 of the above structure...1.4 parts by mass ・The above dispersant 1...7.2 parts by mass ・Propylene glycol methyl ether acetate......81.9 parts by mass
・樹脂A:下述結構的樹脂(酸值=70mgKOH/g、Mw=11000,主鏈中所附記之數值為莫耳比。利用日本特開2012-173356號公報的段落0304~0307中所記載之方法進行了合成。)・Resin A: Resin of the following structure (acid value = 70 mgKOH/g, Mw = 11000, and the value appended to the main chain is the molar ratio. Use paragraphs 0304 to 0307 of Japanese Patent Laid-Open No. 2012-173356 Method was synthesized.)
[化學式13] [Chemical Formula 13]
・單體A:M-350(TOAGOSEI CO.,LTD.) ・光聚合起始劑1:IRGACUREOXE03(BASF公司) ・光聚合起始劑2:IRGACUREOXE04(BASF公司) ・聚合抑制劑:對甲氧基苯酚 ・有機溶劑:PGMEA ・環氧化合物:EHPE-3105(Daicel Chemical Industries, Ltd.) ・界面活性劑:Megafac-781F(DIC Corporation)・Single A: M-350 (TOAGOSEI CO., LTD.) ・Photopolymerization initiator 1: IRGACUREOXE03 (BASF Corporation) ・Photopolymerization initiator 2: IRGACUREOXE04 (BASF Corporation) ・Polymerization inhibitor: p-methoxyphenol ・Organic solvent: PGMEA ・Epoxy compound: EHPE-3105 (Daicel Chemical Industries, Ltd.) ・Surfactant: Megafac-781F (DIC Corporation)
以製膜後的膜厚成為2.7μm之方式,利用旋塗法在玻璃晶片上塗佈實施例1的感光性組成物,然後,在加熱板上於100℃下加熱了2分鐘。然後,使用i射線步進機曝光裝置FPA-3000i5+(Canon Inc.製造),以1000mJ/cm2 對所得到之塗膜進行全面曝光,進而,在加熱板上於220℃下加熱5分鐘而得到了硬化層。 接著,以製膜後的膜厚成為1.5μm之方式,利用旋塗法將Green(綠色)組成物塗佈於上述硬化層上,然後,在加熱板上於100℃下加熱了2分鐘。然後,使用i射線步進機曝光裝置FPA-3000i5+(Canon Inc.製造),以1000mJ/cm2 對所得到之塗膜進行全面曝光,進而,在加熱板上於220℃下加熱5分鐘,並在硬化層上積層Green(綠色)膜而得到了包含硬化層和Green(綠色)膜之樣品G1。 代替Green(綠色)組成物而使用Red(紅色)組成物或Blue(藍色)組成物來得到了包含硬化層和Red(紅色)膜之樣品R1及包含硬化層和Blue(藍色)膜之樣品B1。 上述中代替實施例1的感光性組成物而使用其他實施例及比較例的感光性組成物來製作出各種樣品。The photosensitive composition of Example 1 was applied on a glass wafer by spin coating so that the film thickness after film formation became 2.7 μm, and then heated on a hot plate at 100° C. for 2 minutes. Then, using an i-ray stepper exposure device FPA-3000i5+ (manufactured by Canon Inc.), the obtained coating film was fully exposed at 1000 mJ/cm 2 , and further heated on a hot plate at 220° C. for 5 minutes to obtain Hardened layer. Next, the green composition was applied on the hardened layer by a spin coating method so that the film thickness after film formation became 1.5 μm, and then heated on a hot plate at 100° C. for 2 minutes. Then, using an i-ray stepper exposure device FPA-3000i5+ (manufactured by Canon Inc.), the obtained coating film was fully exposed at 1000 mJ/cm 2 , and further heated on a hot plate at 220° C. for 5 minutes, and A green film was laminated on the hardened layer to obtain a sample G1 including the hardened layer and the green film. Instead of the Green composition, a Red composition or a Blue composition was used to obtain a sample R1 containing a hardened layer and a Red film, and a sample containing a hardened layer and a Blue film B1. In the above, instead of the photosensitive composition of Example 1, the photosensitive compositions of other examples and comparative examples were used to prepare various samples.
使用紫外可見近紅外分光光度計U-4100(Hitachi High-Technologies Corporation製造),對所得到之樣品在波長400~1300nm的範圍測定了光透射率。 接著,在加熱板上於240℃下將所得到之樣品加熱300秒鐘,並測定加熱前後的在波長400~1300nm的範圍內的透射率變化(ΔT),將其作為耐熱性的指標。ΔT的值小的一方,耐熱性良好,判斷基準如下。 另外,上述ΔT表示在波長400~1300nm的範圍內顯示出最大透射率變化之波長下之透射率變化。實用上,A或B為較佳。 “A”:ΔT<2% “B”:2%≤ΔT%<5% “C”:ΔT%≥5% 另外,在後述的表5中示出使用Green(綠色)組成物、Red(紅色)組成物及Blue(藍色)組成物而形成之各樣品的結果。Using an ultraviolet-visible-near infrared spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation), the light transmittance of the obtained sample was measured in the wavelength range of 400 to 1300 nm. Next, the obtained sample was heated on a hot plate at 240° C. for 300 seconds, and the change in transmittance (ΔT) in the wavelength range of 400 to 1300 nm before and after heating was measured as an index of heat resistance. The smaller the value of ΔT, the better the heat resistance, and the criterion is as follows. In addition, the above ΔT represents a change in transmittance at a wavelength that shows the maximum change in transmittance in the wavelength range of 400 to 1300 nm. Practically, A or B is preferred. "A": ΔT<2% "B": 2%≤ΔT%<5% "C": ΔT%≥5% In addition, the results of each sample formed using the Green (red) composition, the Red (red) composition, and the Blue (blue) composition are shown in Table 5 described below.
<圖案矩形性評價>
在矽基板上分別塗佈各實施例及比較例的感光性組成物,並於100℃下實施2分鐘乾燥處理之後,使用曝光裝置UX3100-SR(Ushio Inc.製造)經由光遮罩(遮罩圖案:50μm線與縫隙)進行了光照射(曝光量:100-2000mJ/cm2
)。使用有機鹼性顯影液CD-2000(FUJIFILM Electronic Materials Co.,Ltd.製造)的60%水溶液,將經圖案曝光之塗佈膜於室溫下旋覆浸沒顯影60秒鐘之後,進而利用旋轉噴淋器,用純水進行了沖洗20秒鐘。然後,利用純水進行了水洗。然後,用高壓空氣將水滴飛出而使基板自然乾燥,並於220℃下在加熱板上後烘烤處理300秒鐘而形成了作為線部之硬化膜(厚度:2.7μm)。藉由所得到之線部的截面評價,評價了矩形性。具體而言,如圖3所示,求出線部202相對於矽基板200所成之角θ的值,按照以下基準進行了評價。實用上,A或B為較佳。
“A”:θ為80~100°
“B”:θ為70°以上且小於80°或超過100°且110°以下
“C”:θ小於70°或超過110°<Evaluation of pattern rectangularity> After applying the photosensitive compositions of each example and comparative example on a silicon substrate and drying at 100° C. for 2 minutes, the exposure device UX3100-SR (manufactured by Ushio Inc.) was used to pass The light mask (mask pattern: 50 μm line and gap) was irradiated with light (exposure amount: 100-2000 mJ/cm 2 ). Using a 60% aqueous solution of organic alkaline developer CD-2000 (manufactured by FUJIFILM Electronic Materials Co., Ltd.), the pattern-exposed coating film was spin-immersed and developed at room temperature for 60 seconds. The shower was rinsed with pure water for 20 seconds. Then, it was washed with pure water. Then, the water droplets were flown out with high-pressure air to naturally dry the substrate, and post-baking treatment was performed on a hot plate at 220° C. for 300 seconds to form a cured film (thickness: 2.7 μm) as a line portion. The rectangularity was evaluated by the obtained cross-sectional evaluation of the line portion. Specifically, as shown in FIG. 3, the value of the angle θ formed by the
[表5]
如上述表5所示,當使用了本發明的感光性組成物時,得到了既定的效果。 其中,如實施例1~9所示,在紫外線吸收劑的熱質量測定中,當於150℃下之質量減少率為5%以下且於220℃下之質量減少率為40%以上時,耐熱性優異。如實施例2~9所示,在紫外線吸收劑的熱質量測定中,當於150℃下之質量減少率為5%以下且於220℃下之質量減少率超過40%時,耐熱性特別優異。As shown in Table 5 above, when the photosensitive composition of the present invention is used, predetermined effects are obtained. Among them, as shown in Examples 1 to 9, in the thermal mass measurement of the ultraviolet absorber, when the mass reduction rate at 150°C is 5% or less and the mass reduction rate at 220°C is 40% or more, heat resistance Excellent. As shown in Examples 2 to 9, in the thermal mass measurement of the ultraviolet absorber, when the mass reduction rate at 150°C is 5% or less and the mass reduction rate at 220°C exceeds 40%, heat resistance is particularly excellent .
另外,在實施例6中,作為黏合劑而將樹脂A代替為樹脂B(下述結構),除此以外,藉由相同步驟製備感光性組成物並進行了各種評價,其結果,得到了與實施例6相同之結果。 樹脂B:下述結構。(酸值=95mgKOH/g、Mw=41000,主鏈中所附記之數值為莫耳比。)In addition, in Example 6, the resin A was replaced with the resin B (the following structure) as a binder, except that a photosensitive composition was prepared and subjected to various evaluations in the same procedure. As a result, Example 6 has the same result. Resin B: The following structure. (Acid value=95mgKOH/g, Mw=41000, the value attached in the main chain is the molar ratio.)
[化學式14] [Chemical Formula 14]
在實施例6中,作為黏合劑而將樹脂A代替為樹脂A與樹脂C(下述結構式)的混合物(樹脂A/樹脂C=7.85/7.85),除此以外,以相同之方式製備感光性組成物並進行了各種評價,其結果,得到了與實施例6相同之結果。 樹脂C:下述結構。(酸值=217mgKOH/g、Mw=11000,主鏈中所附記之數值為莫耳比。)In Example 6, the resin A was replaced with a mixture of resin A and resin C (the following structural formula) as a binder (resin A/resin C=7.85/7.85), except that the photosensitive was prepared in the same manner Various evaluations were performed on the sexual composition, and as a result, the same results as in Example 6 were obtained. Resin C: The following structure. (Acid value = 217mgKOH/g, Mw = 11000, the value attached to the main chain is the molar ratio.)
[化學式15] [Chemical Formula 15]
在實施例6中,作為聚合性化合物而將DPHA代替為ARONIX M-510(TOAGOSEI CO.,LTD.製造),除此以外,以相同之方式製備感光性組成物並進行了各種評價,其結果,得到了與實施例6相同之結果。In Example 6, except that DPHA was replaced with ARONIX M-510 (manufactured by TOAGOSEI CO., LTD.) as a polymerizable compound, a photosensitive composition was prepared in the same manner and various evaluations were carried out, as a result , The same results as in Example 6 were obtained.
在實施例6中,作為聚合性化合物而將DPHA代替為DPCA-20(Nippon Kayaku Co.,Ltd.製造),除此以外,以相同之方式製備感光性組成物並進行了各種評價,其結果,得到了與實施例6相同之結果。In Example 6, except that DPHA was replaced with DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.) as a polymerizable compound, a photosensitive composition was prepared in the same manner and various evaluations were performed, as a result , The same results as in Example 6 were obtained.
在實施例6中,作為聚合性化合物而將DPHA代替為OGSOL EA-0300(Osaka Gas Chemicals Co.,Ltd.製造),除此以外,以相同之方式製備感光性組成物並進行了各種評價,其結果,得到了與實施例6相同之結果。In Example 6, except that DPHA was replaced with OGSOL EA-0300 (manufactured by Osaka Gas Chemicals Co., Ltd.) as a polymerizable compound, a photosensitive composition was prepared in the same manner and various evaluations were performed, except that As a result, the same results as in Example 6 were obtained.
在實施例6中,作為聚合性化合物而將DPHA代替為DPHA與ARONIX M-510的混合物(DPHA:ARONIX M-510(質量比)=1:1),除此以外,以相同之方式製備感光性組成物並進行了各種評價,其結果,圖案矩形性比實施例6更優異。根據該結果認為,藉由使用2種以上的聚合性化合物,圖案矩形性進一步得到了提高。In Example 6, DPHA was replaced with a mixture of DPHA and ARONIX M-510 (DPHA: ARONIX M-510 (mass ratio) = 1:1) as the polymerizable compound, except that the photosensitive was prepared in the same manner Various evaluations were carried out on the composition, and as a result, the pattern rectangularity was more excellent than in Example 6. From this result, it is considered that the pattern rectangularity is further improved by using two or more kinds of polymerizable compounds.
在實施例6中,作為起始劑而將IRGACURE369代替為IRGACUREOXE01(BASF公司製造),除此以外,以相同之方式製備感光性組成物並進行了各種評價,其結果,圖案矩形性比實施例6更優異。根據該結果認為,藉由使用肟化合物(肟系起始劑),圖案矩形性進一步得到了提高。In Example 6, except that IRGACURE369 was replaced by IRGACUREOXE01 (manufactured by BASF) as an initiator, a photosensitive composition was prepared in the same manner and subjected to various evaluations. As a result, the pattern rectangularity was higher than in the example 6 is even better. Based on this result, it is considered that the pattern rectangularity is further improved by using an oxime compound (oxime-based initiator).
在實施例6中,作為起始劑而將IRGACURE369代替為IRGACUREOXE03(BASF公司製造),除此以外,以相同之方式製備感光性組成物並進行了各種評價,其結果,圖案矩形性比實施例6更優異。根據該結果認為,藉由使用肟化合物(肟系起始劑),圖案矩形性進一步得到了提高。In Example 6, except that IRGACURE369 was replaced with IRGACUREOXE03 (manufactured by BASF) as an initiator, a photosensitive composition was prepared in the same manner and subjected to various evaluations. As a result, the pattern rectangularity was higher than in the example 6 is even better. Based on this result, it is considered that the pattern rectangularity is further improved by using an oxime compound (oxime-based initiator).
在實施例6中,作為起始劑而將IRGACURE369代替為IRGACUREOXE04(BASF公司製造),除此以外,以相同之方式製備感光性組成物並進行了各種評價,其結果,圖案矩形性比實施例6更優異。根據該結果認為,藉由使用肟化合物(肟系起始劑),圖案矩形性進一步得到了提高。In Example 6, except that IRGACURE369 was replaced by IRGACUREOXE04 (manufactured by BASF Corporation) as the initiator, the photosensitive composition was prepared and subjected to various evaluations in the same manner. As a result, the pattern rectangularity was higher than in the example. 6 is even better. Based on this result, it is considered that the pattern rectangularity is further improved by using an oxime compound (oxime-based initiator).
在實施例6中,作為起始劑而將IRGACURE369代替為IRGACURE369與IRGACUREOXE04的混合物(IRGACURE369: IRGACUREOXE04(質量比)=0.75:0.75),除此以外,以相同之方式製備感光性組成物並進行了各種評價,其結果,圖案矩形性比實施例6更優異。根據該結果認為,藉由使用肟化合物(肟系起始劑),圖案矩形性進一步得到了提高。In Example 6, IRGACURE369 was replaced with a mixture of IRGACURE369 and IRGACUREOXE04 (IRGACURE369: IRGACUREOXE04 (mass ratio) = 0.75:0.75) as an initiator, except that a photosensitive composition was prepared and carried out in the same manner As a result of various evaluations, the pattern rectangularity was more excellent than in Example 6. Based on this result, it is considered that the pattern rectangularity is further improved by using an oxime compound (oxime-based initiator).
在實施例6中,未使用增感劑,除此以外,以相同之方式製備感光性組成物並進行了各種評價,其結果,除了圖案矩形性成為B以外,得到了相同之結果。認為藉由使用增感劑,圖案矩形性進一步得到了提高。In Example 6, except that the sensitizer was not used, the photosensitive composition was prepared in the same manner and subjected to various evaluations. As a result, the same results were obtained except that the pattern rectangularity became B. It is believed that by using a sensitizer, the rectangularity of the pattern is further improved.
在實施例6中,未使用界面活性劑,除此以外,以相同之方式製備感光性組成物並進行了各種評價,其結果,除了圖案矩形性成為B以外,得到了相同之結果。認為藉由使用界面活性劑,圖案矩形性進一步得到了提高。In Example 6, except that no surfactant was used, a photosensitive composition was prepared in the same manner and various evaluations were carried out. As a result, the same results were obtained except that the pattern rectangularity became B. It is thought that by using a surfactant, the rectangularity of the pattern is further improved.
在實施例6中,代替乙二醇單丁醚乙酸酯而使用了乙酸丁酯,除此以外,以相同之方式製備感光性組成物並進行了各種評價,其結果,得到了與實施例6相同之結果。In Example 6, instead of using ethylene glycol monobutyl ether acetate, but butyl acetate was used, a photosensitive composition was prepared in the same manner and various evaluations were carried out. 6 The same result.
在實施例6中,代替乙酸丁酯而使用了PGMEA,除此以外,以相同之方式製備感光性組成物並進行了各種評價,其結果,得到了與實施例6相同之結果。In Example 6, except for using PGMEA instead of butyl acetate, a photosensitive composition was prepared in the same manner and subjected to various evaluations. As a result, the same results as in Example 6 were obtained.
1‧‧‧透鏡光學系統
10‧‧‧固體攝像元件
20‧‧‧信號處理部
30‧‧‧信號切換部
40‧‧‧控制部
50‧‧‧信號蓄積部
60‧‧‧發光控制部
70‧‧‧紅外LED
80、81‧‧‧圖像輸出部
100‧‧‧固體攝像元件
110‧‧‧固體攝像元件基板
111‧‧‧紅外光截止濾波器
112‧‧‧濾色器
113‧‧‧紅外光透射濾波器
114‧‧‧區域
115‧‧‧微透鏡
116‧‧‧平坦化層
200‧‧‧矽基板
202‧‧‧線部
hν‧‧‧入射光
1‧‧‧Lens
圖1係表示本發明的固體攝像元件的一實施形態的構成之概略剖面圖。 圖2係適用了本發明的固體攝像元件之攝像裝置的功能框圖。 圖3係用於說明圖案矩形性評價之圖。FIG. 1 is a schematic cross-sectional view showing the configuration of an embodiment of the solid-state imaging element of the present invention. 2 is a functional block diagram of an imaging device to which the solid-state imaging element of the present invention is applied. FIG. 3 is a diagram for explaining pattern rectangularity evaluation.
Claims (12)
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