TW202413543A - Composition, film, optical filter, solid-state imaging element, image display device, infrared sensor, camera module, compound, and infrared absorbing agent - Google Patents
Composition, film, optical filter, solid-state imaging element, image display device, infrared sensor, camera module, compound, and infrared absorbing agent Download PDFInfo
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- TW202413543A TW202413543A TW112134425A TW112134425A TW202413543A TW 202413543 A TW202413543 A TW 202413543A TW 112134425 A TW112134425 A TW 112134425A TW 112134425 A TW112134425 A TW 112134425A TW 202413543 A TW202413543 A TW 202413543A
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- 239000010937 tungsten Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/34—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
- C09B23/08—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines
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- Optical Filters (AREA)
Abstract
Description
本發明係有關一種聚次甲基化合物、以及包含該聚次甲基化合物之組成物及紅外線吸收劑。又,本發明係有關一種使用包含聚次甲基化合物的組成物之膜、濾光器、固體攝像元件、圖像顯示裝置、紅外線感測器及相機模組。The present invention relates to a polymethine compound, a composition containing the polymethine compound, and an infrared absorber. In addition, the present invention relates to a film, a filter, a solid-state imaging element, an image display device, an infrared sensor, and a camera module using the composition containing the polymethine compound.
在視訊攝影機、數位相機、附相機功能之行動電話等中使用彩色圖像的固體攝像元件亦即CCD(電荷耦合元件)或CMOS(互補金屬氧化膜半導體)。該等固體攝像元件在其受光部使用對紅外線具有靈敏度之矽光二極體。因此,有時會設置紅外線截止濾波器進行光度因數(luminosity factor)校正。Solid-state imaging devices that use color images in video cameras, digital cameras, and mobile phones with camera functions are CCDs (charge-coupled devices) or CMOSs (complementary metal oxide semiconductors). These solid-state imaging devices use silicon photodiodes that are sensitive to infrared rays in their light-receiving parts. Therefore, infrared cutoff filters are sometimes set to perform luminosity factor correction.
紅外線截止濾波器使用包含紅外線吸收劑之組成物製造。作為紅外線吸收劑,已知有聚次甲基化合物等。Infrared cut filters are manufactured using a composition containing an infrared absorber. Polymethine compounds and the like are known as infrared absorbers.
專利文獻1中記載有使用包含特定聚次甲基化合物等之組成物來製造紅外線截止濾波器等之內容。Patent document 1 discloses that an infrared cut filter and the like are manufactured using a composition containing a specific polymethine compound and the like.
[專利文獻1]國際公開第2021/085372號[Patent Document 1] International Publication No. 2021/085372
聚次甲基化合物的耐光性往往較低。因此,使用包含該等化合物之組成物來獲得之膜的耐光性存在進一步改善的餘地。Polymethine compounds tend to have low light resistance. Therefore, there is room for further improvement in the light resistance of a film obtained using a composition containing these compounds.
又,關於包含聚次甲基化合物的組成物,在組成物的保管中,聚次甲基化合物凝聚而容易析出凝聚物,使用保管後的組成物形成膜時,膜中容易產生異物等。因此,包含聚次甲基化合物的組成物的保存穩定性存在進一步改善的餘地。In addition, regarding the composition containing a polymethine compound, the polymethine compound is aggregated during storage of the composition and aggregates are easily precipitated. When a film is formed using the stored composition, foreign matter is easily generated in the film. Therefore, there is room for further improvement in the storage stability of the composition containing a polymethine compound.
因此,本發明的目的在於提供一種能夠形成保存穩定性優異且耐光性優異的膜之組成物。又,本發明提供一種膜、濾光器、固體攝像元件、圖像顯示裝置、紅外線感測器、相機模組、化合物及紅外線吸收劑。Therefore, the object of the present invention is to provide a composition capable of forming a film having excellent storage stability and excellent light resistance. In addition, the present invention provides a film, a filter, a solid-state imaging element, an image display device, an infrared sensor, a camera module, a compound, and an infrared absorber.
本發明提供以下內容。 <1>一種組成物,其含有由式(1)表示之化合物、硬化性化合物及溶劑, [化學式1] 式(1)中,X 1及X 2分別獨立地表示氧原子、硫原子、硒原子、碲原子或-NR X1-, R X1表示氫原子、鹵素原子、烷基、芳基、雜環基或醯基, R 1及R 2分別獨立地表示烷基、烷氧基、醯基、醯氧基、烷氧基羰基、芳基、雜環基、-SR 41、-SO 2R 42、-OSO 2R 43或-NR 44R 45, R 41~R 43分別獨立地表示烷基、芳基或雜環基, R 44及R 45分別獨立地表示氫原子、鹵素原子、烷基、芳基、雜環基、醯基或烷氧基羰基,R 44與R 45可以連結而形成環, R 3~R 5、R 11~R 14、R 21~R 24、R 31及R 32分別獨立地表示氫原子、鹵素原子、磺基、羥基、氰基、硝基、羧基、磷酸基、烷基、芳基、雜環基、烷氧基、醯氧基、-SR 51、-SO 2R 52、-OSO 2R 53或-NR 54R 55, R 51~R 53分別獨立地表示氫原子、烷基、芳基或雜環基, R 54及R 55分別獨立地表示氫原子、鹵素原子、烷基、芳基、雜環基、醯基或烷氧基羰基,R 54與R 55可以連結而形成環, R 3~R 5、R 11~R 14、R 21~R 24中相鄰的2個可以彼此連結而形成5~8員環, R 31與R 32可以連結而形成5~8員環, R 11與R 31可以連結而形成5~8員環, R 21與R 32可以連結而形成5~8員環, m及n分別獨立地表示1~10的整數, A -表示陰離子。 <2>如<1>所述之組成物,其中 上述式(1)的m及n分別獨立地為2或3。 <3>如<1>或<2>所述之組成物,其中 上述式(1)的m和n為相同的整數。 <4>如<1>至<3>之任一項所述之組成物,其中 上述式(1)的X 1及X 2分別獨立地表示氧原子或硫原子。 <5>如<1>至<3>之任一項所述之組成物,其中 上述式(1)的X 1及X 2為氧原子。 <6>如<1>至<5>之任一項所述之組成物,其進一步包含由上述式(1)表示之化合物以外的紅外線吸收劑。 <7>一種膜,其使用<1>至<6>之任一項所述之組成物來獲得。 <8>一種濾光器,其具有<7>所述之膜。 <9>一種固體攝像元件,其具有<7>所述之膜。 <10>一種圖像顯示裝置,其具有<7>所述之膜。 <11>一種紅外線感測器,其具有<7>所述之膜。 <12>一種相機模組,其具有<7>所述之膜。 <13>一種化合物,其由式(1)表示, [化學式2] 式(1)中,X 1及X 2分別獨立地表示氧原子、硫原子、硒原子、碲原子或-NR X1-, R X1表示氫原子、鹵素原子、烷基、芳基、雜環基或醯基, R 1及R 2分別獨立地表示烷基、烷氧基、醯基、醯氧基、烷氧基羰基、芳基、雜環基、-SR 41、-SO 2R 42、-OSO 2R 43或-NR 44R 45, R 41~R 43分別獨立地表示烷基、芳基或雜環基, R 44及R 45分別獨立地表示氫原子、鹵素原子、烷基、芳基、雜環基、醯基或烷氧基羰基,R 44與R 45可以連結而形成環, R 3~R 5、R 11~R 14、R 21~R 24、R 31及R 32分別獨立地表示氫原子、鹵素原子、磺基、羥基、氰基、硝基、羧基、磷酸基、烷基、芳基、雜環基、烷氧基、醯氧基、-SR 51、-SO 2R 52、-OSO 2R 53或-NR 54R 55, R 51~R 53分別獨立地表示氫原子、烷基、芳基或雜環基, R 54及R 55分別獨立地表示氫原子、鹵素原子、烷基、芳基、雜環基、醯基或烷氧基羰基,R 54與R 55可以連結而形成環, R 3~R 5、R 11~R 14、R 21~R 24中相鄰的2個可以彼此連結而形成5~8員環, R 31與R 32可以連結而形成5~8員環, R 11與R 31可以連結而形成5~8員環, R 21與R 32可以連結而形成5~8員環, m及n分別獨立地表示1~10的整數, A -表示陰離子。 <14>一種紅外線吸收劑,其包含<13>所述之化合物。 [發明效果] The present invention provides the following contents. <1> A composition comprising a compound represented by formula (1), a curable compound and a solvent, [Chemical formula 1] In formula (1), X1 and X2 each independently represent an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or -NRX1- , RX1 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group or an acyl group, R1 and R2 each independently represent an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an alkoxycarbonyl group , an aryl group, a heterocyclic group, -SR41 , -SO2R42 , -OSO2R43 or -NR44R45 , R41 to R43 each independently represent an alkyl group, an aryl group or a heterocyclic group, R44 and R45 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group or an alkoxycarbonyl group, and R44 and R45 may be linked to form a ring. R 3 to R 5 , R 11 to R 14 , R 21 to R 24 , R 31 and R 32 each independently represent a hydrogen atom, a halogen atom, a sulfone group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphate group, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an acyl group, -SR 51 , -SO 2 R 52 , -OSO 2 R 53 or -NR 54 R 55 , R 51 to R 53 each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, R 54 and R 55 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group or an alkoxycarbonyl group, R 54 and R 55 may be linked to form a ring, R 3 to R 5 , R Adjacent two of R 11 to R 14 and R 21 to R 24 may be linked to each other to form a 5-8 membered ring, R 31 and R 32 may be linked to form a 5-8 membered ring, R 11 and R 31 may be linked to form a 5-8 membered ring, R 21 and R 32 may be linked to form a 5-8 membered ring, m and n each independently represent an integer of 1 to 10, and A - represents an anion. <2> The composition as described in <1>, wherein m and n in the above formula (1) are each independently 2 or 3. <3> The composition as described in <1> or <2>, wherein m and n in the above formula (1) are the same integer. <4> The composition as described in any one of <1> to <3>, wherein X 1 and X 2 in the above formula (1) each independently represent an oxygen atom or a sulfur atom. <5> A composition as described in any one of <1> to <3>, wherein X1 and X2 in the above formula (1) are oxygen atoms. <6> A composition as described in any one of <1> to <5>, further comprising an infrared absorber other than the compound represented by the above formula (1). <7> A film obtained using the composition as described in any one of <1> to <6>. <8> A filter having the film described in <7>. <9> A solid-state imaging element having the film described in <7>. <10> An image display device having the film described in <7>. <11> An infrared sensor having the film described in <7>. <12> A camera module having the film described in <7>. <13> A compound represented by formula (1), [Chemical Formula 2] In formula (1), X1 and X2 each independently represent an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or -NRX1- , RX1 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group or an acyl group, R1 and R2 each independently represent an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an alkoxycarbonyl group , an aryl group, a heterocyclic group, -SR41 , -SO2R42 , -OSO2R43 or -NR44R45 , R41 to R43 each independently represent an alkyl group, an aryl group or a heterocyclic group, R44 and R45 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group or an alkoxycarbonyl group, and R44 and R45 may be linked to form a ring. R 3 to R 5 , R 11 to R 14 , R 21 to R 24 , R 31 and R 32 each independently represent a hydrogen atom, a halogen atom, a sulfone group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphate group, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an acyl group, -SR 51 , -SO 2 R 52 , -OSO 2 R 53 or -NR 54 R 55 , R 51 to R 53 each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, R 54 and R 55 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group or an alkoxycarbonyl group, R 54 and R 55 may be linked to form a ring, R 3 to R 5 , R Adjacent two of R11 to R14 and R21 to R24 may be linked to each other to form a 5-8 membered ring, R31 and R32 may be linked to form a 5-8 membered ring, R11 and R31 may be linked to form a 5-8 membered ring, R21 and R32 may be linked to form a 5-8 membered ring, m and n each independently represent an integer of 1 to 10, and A- represents an anion. <14> An infrared absorber comprising the compound described in <13>. [Effects of the invention]
根據本發明,能夠提供一種能夠形成保存穩定性優異且耐光性優異的膜之組成物。又,本發明能夠提供一種膜、濾光器、固體攝像元件、圖像顯示裝置、紅外線感測器、相機模組、化合物及紅外線吸收劑。According to the present invention, a composition capable of forming a film having excellent storage stability and excellent light resistance can be provided. In addition, the present invention can provide a film, a filter, a solid-state imaging element, an image display device, an infrared sensor, a camera module, a compound, and an infrared absorber.
以下,對本發明的內容進行詳細說明。 本說明書中,“~”以將記載於其前後之數值作為下限值及上限值而包括之含義來使用。 本說明書中的基團(原子團)的標記中,未標有經取代及未經取代之標記包括不具有取代基之基團(原子團)的同時包括具有取代基之基團(原子團)。例如,“烷基”不僅包括不具有取代基之烷基(未經取代之烷基),亦包括具有取代基之烷基(經取代之烷基)。 本說明書中,“曝光”只要沒有特別指定,不僅包括使用光之曝光,使用電子束、離子束等粒子束之描繪亦包括在曝光中。又,作為曝光中所使用之光,可舉出水銀燈的明線光譜、以準分子雷射為代表之遠紫外線、極紫外線(EUV光)、X射線、電子束等活性光線或放射線。 本說明書中,“(甲基)丙烯酸酯”表示丙烯酸酯及甲基丙烯酸酯兩者或任一者,“(甲基)丙烯酸”表示丙烯酸及甲基丙烯酸兩者或任一者,“(甲基)丙烯醯基”表示丙烯醯基及甲基丙烯醯基兩者或任一者。 本說明書中,將重量平均分子量及數量平均分子量定義為利用凝膠滲透層析法(GPC)測定之聚苯乙烯換算值。 本說明書中,化學式中的Me表示甲基,Et表示乙基,Bu表示丁基,Ph表示苯基。 本說明書中,紅外線表示波長700~2500nm的光(電磁波)。 本說明書中,總固體成分係指從組成物的所有成分中去除溶劑之成分的總質量。 本說明書中,“步驟”這一用語,不僅包括獨立的步驟,即使在無法與其他步驟明確區分的情況下,只要實現該步驟所期待的作用,則亦包括在本用語中。 The content of the present invention is described in detail below. In this specification, "~" is used to mean that the numerical values recorded before and after it are included as lower limits and upper limits. In the marking of groups (atomic groups) in this specification, the markings not marked with substituted and unsubstituted include groups (atomic groups) without substituents and groups (atomic groups) with substituents. For example, "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups). In this specification, "exposure" includes not only exposure using light, but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. In addition, as the light used in the exposure, there can be cited the bright line spectrum of mercury lamp, far ultraviolet light represented by excimer laser, extreme ultraviolet light (EUV light), X-rays, active light or radiation such as electron beams. In this specification, "(meth)acrylate" means both or either acrylate and methacrylate, "(meth)acrylic acid" means both or either acrylic acid and methacrylic acid, and "(meth)acryloyl" means both or either acryl and methacryloyl. In this specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene conversion values measured by gel permeation chromatography (GPC). In this specification, Me in the chemical formula represents methyl, Et represents ethyl, Bu represents butyl, and Ph represents phenyl. In this specification, infrared light means light (electromagnetic wave) with a wavelength of 700 to 2500 nm. In this specification, the total solid content refers to the total mass of the components excluding the solvent from all the components of the composition. In this specification, the term "step" includes not only independent steps, but also steps that achieve the expected effect of the step even if they cannot be clearly distinguished from other steps.
<組成物> 本發明的組成物的特徵為包含由式(1)表示之化合物、硬化性化合物及溶劑。 <Composition> The composition of the present invention is characterized by comprising a compound represented by formula (1), a curable compound and a solvent.
本發明的組成物能夠形成保存穩定性優異且長期保管後異物等的產生仍得到抑制的膜。又,本發明能夠形成耐光性優異的膜。獲得此類效果之理由可推測為如下。 亦即,推測本發明的組成物中包含之由式(1)表示之化合物與組成物中包含之溶劑或硬化性化合物的相溶性良好,其結果,能夠形成保存穩定性優異的組成物。又,推測由式(1)表示之化合物由於式(1)中的R 1及R 2為烷基、烷氧基、醯基、醯氧基、芳基、雜環基或-NR 41R 42,因此次甲基部位的位阻變高,藉由光照射能夠抑制次甲基部位的切斷等。因此,藉由使用本發明的組成物,能夠形成耐光性優異的膜。 The composition of the present invention can form a film having excellent storage stability and in which the generation of foreign matter and the like is suppressed even after long-term storage. In addition, the present invention can form a film having excellent light resistance. The reason for obtaining such an effect can be inferred as follows. That is, it is inferred that the compound represented by formula (1) contained in the composition of the present invention has good compatibility with the solvent or curable compound contained in the composition, and as a result, a composition having excellent storage stability can be formed. In addition, it is inferred that the compound represented by formula (1) has high steric hindrance at the methine site because R 1 and R 2 in formula (1) are alkyl, alkoxy, acyl, acyloxy, aryl, heterocyclic or -NR 41 R 42 , and thus the cleavage of the methine site can be suppressed by light irradiation. Therefore, by using the composition of the present invention, a film having excellent light resistance can be formed.
本發明的組成物能夠用作濾光器用組成物。作為濾光器的種類,可舉出紅外線截止濾波器及紅外線透射濾波器等。由式(1)表示之化合物的可見光透射性及紅外線遮蔽性優異,因此,本發明的組成物尤其較佳地用作紅外線截止濾波器用組成物。The composition of the present invention can be used as a composition for an optical filter. Examples of optical filters include infrared cut filters and infrared transmission filters. The compound represented by formula (1) has excellent visible light transmittance and infrared shielding properties, and therefore, the composition of the present invention is particularly preferably used as a composition for an infrared cut filter.
以下,對本發明的組成物中所使用之各成分進行說明。Hereinafter, each component used in the composition of the present invention will be described.
<<特定化合物(由式(1)表示之化合物)>> 本發明的組成物包含由式(1)表示之化合物。由式(1)表示之化合物亦為本發明的化合物。以下,將由式(1)表示之化合物亦稱為特定化合物。 <<Specific compound (compound represented by formula (1))>> The composition of the present invention includes a compound represented by formula (1). The compound represented by formula (1) is also a compound of the present invention. Hereinafter, the compound represented by formula (1) is also referred to as a specific compound.
[化學式3] 式(1)中,X 1及X 2分別獨立地表示氧原子、硫原子、硒原子、碲原子或-NR X1-, R X1表示氫原子、鹵素原子、烷基、芳基、雜環基或醯基, R 1及R 2分別獨立地表示烷基、烷氧基、醯基、醯氧基、烷氧基羰基、芳基、雜環基、-SR 41、-SO 2R 42、-OSO 2R 43或-NR 44R 45, R 41~R 43分別獨立地表示烷基、芳基或雜環基, R 44及R 45分別獨立地表示氫原子、鹵素原子、烷基、芳基、雜環基、醯基或烷氧基羰基,R 44與R 45可以連結而形成環, R 3~R 5、R 11~R 14、R 21~R 24、R 31及R 32分別獨立地表示氫原子、鹵素原子、磺基、羥基、氰基、硝基、羧基、磷酸基、烷基、芳基、雜環基、烷氧基、醯氧基、-SR 51、-SO 2R 52、-OSO 2R 53或-NR 54R 55, R 51~R 53分別獨立地表示氫原子、烷基、芳基或雜環基, R 54及R 55分別獨立地表示氫原子、鹵素原子、烷基、芳基、雜環基、醯基或烷氧基羰基,R 54與R 55可以連結而形成環, R 3~R 5、R 11~R 14、R 21~R 24中相鄰的2個可以彼此連結而形成5~8員環, R 31與R 32可以連結而形成5~8員環, R 11與R 31可以連結而形成5~8員環, R 21與R 32可以連結而形成5~8員環, m及n分別獨立地表示1~10的整數, A -表示陰離子。 [Chemical formula 3] In formula (1), X1 and X2 each independently represent an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or -NRX1- , RX1 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group or an acyl group, R1 and R2 each independently represent an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an alkoxycarbonyl group , an aryl group, a heterocyclic group, -SR41 , -SO2R42 , -OSO2R43 or -NR44R45 , R41 to R43 each independently represent an alkyl group, an aryl group or a heterocyclic group, R44 and R45 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group or an alkoxycarbonyl group, and R44 and R45 may be linked to form a ring. R 3 to R 5 , R 11 to R 14 , R 21 to R 24 , R 31 and R 32 each independently represent a hydrogen atom, a halogen atom, a sulfone group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphate group, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an acyl group, -SR 51 , -SO 2 R 52 , -OSO 2 R 53 or -NR 54 R 55 , R 51 to R 53 each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, R 54 and R 55 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group or an alkoxycarbonyl group, R 54 and R 55 may be linked to form a ring, R 3 to R 5 , R Adjacent two of R 11 to R 14 and R 21 to R 24 may be linked to each other to form a 5-8 membered ring, R 31 and R 32 may be linked to form a 5-8 membered ring, R 11 and R 31 may be linked to form a 5-8 membered ring, R 21 and R 32 may be linked to form a 5-8 membered ring, m and n each independently represent an integer of 1 to 10, and A - represents an anion.
式(1)的X 1及X 2分別獨立地表示氧原子或硫原子為較佳,氧原子為更佳。根據該態樣,能夠進一步提高耐光性及保存穩定性。進而,亦能夠提高可見透明性及紅外線遮蔽性。 In formula (1), X1 and X2 are preferably independently an oxygen atom or a sulfur atom, and more preferably an oxygen atom. According to this aspect, light resistance and storage stability can be further improved. Furthermore, visible transparency and infrared shielding properties can also be improved.
式(1)的X 1及X 2所表示之-NR X1-的R X1為氫原子或烷基為較佳。 In the formula (1), R X1 in -NR X1 - represented by X1 and X2 is preferably a hydrogen atom or an alkyl group.
式(1)的R 1及R 2分別獨立地表示烷基、烷氧基、醯基、醯氧基、烷氧基羰基、芳基、雜環基、-SR 41、-SO 2R 42、-OSO 2R 43或-NR 44R 45,R 41~R 43分別獨立地表示烷基、芳基或雜環基,R 44及R 45分別獨立地表示氫原子、鹵素原子、烷基、芳基、雜環基、醯基或烷氧基羰基。 In formula (1), R1 and R2 each independently represent an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an alkoxycarbonyl group, an aryl group , a heterocyclic group, -SR41 , -SO2R42 , -OSO2R43 or -NR44R45 ; R41 to R43 each independently represent an alkyl group, an aryl group or a heterocyclic group; and R44 and R45 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group or an alkoxycarbonyl group.
上述烷基的碳數為1~30為較佳。下限為2以上為較佳,3以上為更佳。上限為20以下為較佳。烷基可以為直鏈、支鏈及環狀中的任一種,支鏈或環狀為較佳。又,環狀烷基可以為單環的環狀烷基,亦可以為多環的環狀烷基。作為烷基的具體例,可舉出甲基、乙基、正丙基、異丙基、正丁基、異丁基、二級丁基、三級丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基、正十一基、正十二基、正十三基、正十四基、正十五基、正十六基、正十七基、正十八基、正十九基、正二十基、環戊基、環丁基、環己基、降莰基、三環癸基、四環十二基、金剛烷基、甲基金剛烷基、乙基金剛烷基、丁基金剛烷基等。上述烷基可以具有取代基,亦可以未經取代。作為取代基,可舉出後述取代基T中舉出的基團,鹵素原子、芳基或烷氧基為較佳。The carbon number of the alkyl group is preferably 1 to 30. The lower limit is preferably 2 or more, and more preferably 3 or more. The upper limit is preferably 20 or less. The alkyl group may be any of a straight chain, a branched chain, and a cyclic group, and a branched chain or a cyclic group is preferred. In addition, the cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. As specific examples of the alkyl group, there can be mentioned methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, dibutyl, tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecayl, n-tetradecyl, n-pentadecayl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecayl, n-eicosyl, cyclopentyl, cyclobutyl, cyclohexyl, norbornyl, tricyclodecyl, tetracyclododecyl, adamantyl, methyladamantyl, ethyladamantyl, butyladamantyl, etc. The above alkyl groups may have a substituent or may be unsubstituted. As the substituent, there can be mentioned the groups listed in the substituent T described later, preferably a halogen atom, an aryl group or an alkoxy group.
上述烷氧基的碳數為1~20為較佳,1~15為更佳,1~8為進一步較佳。烷氧基為直鏈或支鏈為較佳。R 1及R 2所表示之烷氧基可以具有取代基,亦可以未經取代。作為取代基,可舉出後述取代基T中舉出的基團,鹵素原子、芳基或烷氧基為較佳。 The carbon number of the alkoxy group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 8. The alkoxy group is preferably a straight chain or a branched chain. The alkoxy group represented by R1 and R2 may have a substituent or may be unsubstituted. As the substituent, the groups listed in the substituent T described below can be cited, and a halogen atom, an aryl group or an alkoxy group is preferred.
上述醯基、醯氧基及烷氧基羰基的碳數為2~30為較佳,2~15為更佳,2~8為進一步較佳。醯基、醯氧基及烷氧基羰基可以具有取代基,亦可以未經取代。作為取代基,可舉出後述取代基T中舉出的基團,鹵素原子、芳基或烷氧基為較佳。The carbon number of the acyl group, acyloxy group and alkoxycarbonyl group is preferably 2 to 30, more preferably 2 to 15, and even more preferably 2 to 8. The acyl group, acyloxy group and alkoxycarbonyl group may have a substituent or may be unsubstituted. As the substituent, the groups listed in the substituent T described below can be cited, and a halogen atom, an aryl group or an alkoxy group is preferred.
上述芳基的碳數為6~30為較佳,2~20為更佳,6~12為進一步較佳。芳基可以具有取代基,亦可以未經取代。作為取代基,可舉出後述取代基T中舉出的基團,鹵素原子、烷基或烷氧基為較佳。The carbon number of the aryl group is preferably 6 to 30, more preferably 2 to 20, and even more preferably 6 to 12. The aryl group may have a substituent or may be unsubstituted. As the substituent, the groups listed in the substituent T described below can be cited, and a halogen atom, an alkyl group, or an alkoxy group is preferred.
上述雜環基為5員環或6員環的雜環基為較佳。又,雜環基為單環的雜環基或縮合數為2~8的縮合環的雜環基為較佳,單環的雜環基或縮合數為2~4的縮合環的雜環基為更佳。構成雜環基的環之雜原子為氮原子、氧原子或硫原子為較佳。構成雜環基的環之雜原子數為1~3為較佳,1~2為更佳。構成雜環基的環之碳原子數為1~30為較佳,1~18為更佳,1~12為進一步較佳。R 1及R 2所表示之雜環基可以具有取代基,亦可以未經取代。作為取代基,可舉出後述取代基T中舉出的基團,鹵素原子、烷基或烷氧基為較佳。 The above-mentioned heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group. Furthermore, the heterocyclic group is preferably a monocyclic heterocyclic group or a condensed heterocyclic group having a condensation number of 2 to 8, and more preferably a monocyclic heterocyclic group or a condensed heterocyclic group having a condensation number of 2 to 4. The hetero atom constituting the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. The number of hetero atoms constituting the heterocyclic group is preferably 1 to 3, and more preferably 1 to 2. The number of carbon atoms in the ring constituting the heterocyclic group is preferably 1 to 30, more preferably 1 to 18, and even more preferably 1 to 12. The heterocyclic group represented by R1 and R2 may have a substituent or may be unsubstituted. As the substituent, the groups listed in the substituent T described below can be cited, and a halogen atom, an alkyl group, or an alkoxy group is preferred.
作為上述鹵素原子,可舉出氟原子、氯原子、溴原子、碘原子。Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
由-NR 44R 45表示之基團的R 44及R 45可以連結而形成環。所形成之環為5~8員環為較佳,5員環或6員環為更佳。 R 44 and R 45 of the group represented by -NR 44 R 45 may be linked to form a ring. The formed ring is preferably a 5- to 8-membered ring, more preferably a 5- or 6-membered ring.
從能夠進一步提高耐光性的理由考慮,式(1)的R 1及R 2分別獨立地為烷基或芳基為較佳,從進一步提高可見透明性的理由考慮,烷基為更佳。 From the viewpoint of further improving light resistance, R1 and R2 in formula (1) are preferably independently an alkyl group or an aryl group, and from the viewpoint of further improving visible transparency, an alkyl group is more preferred.
式(1)的R 3~R 5、R 11~R 14、R 21~R 24、R 31及R 32分別獨立地表示氫原子、鹵素原子、磺基、羥基、氰基、硝基、羧基、磷酸基、烷基、芳基、雜環基、烷氧基、醯氧基、-SR 51、-SO 2R 52、-OSO 2R 53或-NR 54R 55, R 51~R 53分別獨立地表示氫原子、烷基、芳基、雜環基, R 54及R 55分別獨立地表示氫原子、鹵素原子、烷基、芳基、雜環基、醯基或烷氧基羰基。 In formula (1), R 3 to R 5 , R 11 to R 14 , R 21 to R 24 , R 31 and R 32 each independently represent a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphate group, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an acyl group, -SR 51 , -SO 2 R 52 , -OSO 2 R 53 or -NR 54 R 55 , R 51 to R 53 each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R 54 and R 55 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group or an alkoxycarbonyl group.
R 3~R 5、R 11~R 14、R 21~R 24、R 31及R 32所表示之上述基團可舉出作為R 1及R 2所表示之該等基團說明的基團,較佳範圍亦相同。 The above-mentioned groups represented by R 3 to R 5 , R 11 to R 14 , R 21 to R 24 , R 31 and R 32 may be the same groups as those described for the groups represented by R 1 and R 2 , and the preferred ranges are the same.
由-NR 54R 55表示之基團的R 54及R 55可以連結而形成環。所形成之環為5~8員環為較佳,5員環或6員環為更佳。 R 54 and R 55 of the group represented by -NR 54 R 55 may be linked to form a ring. The formed ring is preferably a 5- to 8-membered ring, more preferably a 5- or 6-membered ring.
式(1)的R 3~R 5分別獨立地為氫原子或烷基為較佳,氫原子為更佳。 In formula (1), R 3 to R 5 are each independently a hydrogen atom or an alkyl group, preferably a hydrogen atom.
式(1)的R 11~R 14、R 21~R 24分別獨立地表示氫原子或烷基為較佳。 In the formula (1), R 11 to R 14 and R 21 to R 24 each independently represent a hydrogen atom or an alkyl group.
式(1)的R 31及R 32分別獨立地為氫原子或烷基為較佳,氫原子為更佳。 In formula (1), R 31 and R 32 are each independently preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.
式(1)中,R 3~R 5、R 11~R 14、R 21~R 24中相鄰的2個可以彼此連結而形成5~8員環,R 31與R 32可以彼此連結而形成5~8員環。所形成之環為5員環或6員環為較佳。所形成之環可以為脂肪族環,亦可以為芳香族環。所形成之環為芳香族環為較佳,苯環為更佳。所形成之環可以具有取代基。作為取代基,可舉出後述取代基T中舉出的基團,鹵素原子、烷基或芳基為較佳。 In formula (1), two adjacent groups of R 3 to R 5 , R 11 to R 14 , and R 21 to R 24 may be linked to each other to form a 5- to 8-membered ring, and R 31 and R 32 may be linked to each other to form a 5- to 8-membered ring. The formed ring is preferably a 5- or 6-membered ring. The formed ring may be an aliphatic ring or an aromatic ring. The formed ring is preferably an aromatic ring, and a benzene ring is more preferably. The formed ring may have a substituent. As the substituent, the groups listed in the substituent T described later may be cited, and a halogen atom, an alkyl group, or an aryl group is preferred.
式(1)中,R 11與R 31可以連結而形成5~8員環,R 21與R 32可以連結而形成5~8員環。所形成之環為5員環或6員環為較佳。所形成之環可以具有取代基。作為取代基,可舉出後述取代基T中舉出的基團,鹵素原子、烷基或芳基為較佳。 In formula (1), R11 and R31 may be linked to form a 5- to 8-membered ring, and R21 and R32 may be linked to form a 5- to 8-membered ring. The formed ring is preferably a 5- or 6-membered ring. The formed ring may have a substituent. As the substituent, the groups listed in the substituent T described below can be cited, and a halogen atom, an alkyl group or an aryl group is preferred.
作為式(1)中的R 11~R 14、R 21~R 24的較佳之一態樣,可舉出R 12、R 13、R 22及R 23分別獨立地為烷基且R 11、R 14、R 21及R 24為氫原子之態樣。 As a preferred embodiment of R 11 to R 14 and R 21 to R 24 in formula (1), there can be mentioned an embodiment in which R 12 , R 13 , R 22 and R 23 are each independently an alkyl group and R 11 , R 14 , R 21 and R 24 are a hydrogen atom.
作為式(1)中的R 11~R 14、R 21~R 24的別的較佳之一態樣,可舉出R 11及R 21為氫原子、R 12及R 22分別獨立地為烷基、R 13與R 14連結而形成苯環且R 23與R 24連結而形成苯環之態樣。 Another preferred embodiment of R11 to R14 and R21 to R24 in formula (1) includes an embodiment in which R11 and R21 are hydrogen atoms, R12 and R22 are independently alkyl groups, R13 and R14 are linked to form a benzene ring, and R23 and R24 are linked to form a benzene ring.
作為式(1)中的R 11~R 14、R 21~R 24的較佳之另一態樣,可舉出R 14及R 24為氫原子、R 13及R 23分別獨立地為烷基、R 11與R 12連結而形成苯環且R 21與R 22連結而形成苯環之態樣。 Another preferred embodiment of R11 to R14 and R21 to R24 in formula (1) includes an embodiment in which R14 and R24 are hydrogen atoms, R13 and R23 are independently alkyl groups, R11 and R12 are linked to form a benzene ring, and R21 and R22 are linked to form a benzene ring.
式(1)的m及n分別獨立地表示1~10的整數,1~3的整數為較佳,2或3為更佳,2為進一步較佳。 又,從進一步提高保存穩定性及耐光性的理由考慮,式(1)的m和n為相同的整數為較佳。 m and n in formula (1) are independently integers of 1 to 10, preferably integers of 1 to 3, more preferably 2 or 3, and even more preferably 2. In addition, m and n in formula (1) are preferably the same integer for the purpose of further improving storage stability and light resistance.
式(1)的A -表示陰離子。作為陰離子,並沒有特別限制。可以為有機陰離子,亦可以為無機陰離子。作為陰離子,可舉出由式(AN1)表示之陰離子、由式(AN2)表示之陰離子、由式(AN3)表示之陰離子、由式(AN4)表示之陰離子、由式(AN5)表示之陰離子、氟陰離子、氯陰離子、溴陰離子、碘陰離子、氰化物離子、過氯酸陰離子、羧酸陰離子、磺酸陰離子、磷酸陰離子等。 [化學式4] A- in formula (1) represents an anion. There is no particular limitation on the anion. It may be an organic anion or an inorganic anion. Examples of the anion include anions represented by formula (AN1), anions represented by formula (AN2), anions represented by formula (AN3), anions represented by formula (AN4), anions represented by formula (AN5), fluorine anions, chlorine anions, bromine anions, iodine anions, cyanide anions, perchloric acid anions, carboxylic acid anions, sulfonic acid anions, and phosphoric acid anions. [Chemical Formula 4]
式(AN1)中,R AN1及R AN2分別獨立地表示鹵素原子或烷基,R AN1與R AN2可以鍵結而形成環; 式(AN2)中,R AN3~R AN5分別獨立地表示鹵素原子或烷基,R AN3與R AN4、R AN4與R AN5或R AN3與R AN5可以鍵結而形成環; 式(AN3)中,R AN6~R AN9分別獨立地表示鹵素原子、烷基、芳基、烷氧基、芳氧基或氰基; 式(AN4)中,R AN10表示可以藉由具有氮原子或氧原子之連結基連結之鹵化烴基; 式(AN5)中,R AN11~R AN16分別獨立地表示鹵素原子或鹵化烴基。 In formula (AN1), R AN1 and R AN2 each independently represent a halogen atom or an alkyl group, and R AN1 and R AN2 may be bonded to form a ring; In formula (AN2), R AN3 to R AN5 each independently represent a halogen atom or an alkyl group, and R AN3 and R AN4 , R AN4 and R AN5 , or R AN3 and R AN5 may be bonded to form a ring; In formula (AN3), R AN6 to R AN9 each independently represent a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a cyano group; In formula (AN4), R AN10 represents a halogenated alkyl group that may be linked via a linking group having a nitrogen atom or an oxygen atom; In formula (AN5), R AN11 to R AN16 each independently represent a halogenated alkyl group.
作為式(AN1)的R AN1及R AN2所表示之鹵素原子、式(AN2)的R AN3~R AN5所表示之鹵素原子及式(AN3)的R AN6~R AN9所表示之鹵素原子,可舉出氟原子、氯原子、溴原子、碘原子,氟原子為較佳。 Examples of the halogen atom represented by R AN1 and R AN2 of the formula (AN1), the halogen atom represented by R AN3 to R AN5 of the formula (AN2), and the halogen atom represented by R AN6 to R AN9 of the formula (AN3) include fluorine atom, chlorine atom, bromine atom and iodine atom, with fluorine atom being preferred.
式(AN1)的R AN1及R AN2所表示之烷基、式(AN2)的R AN3~R AN5所表示之烷基及式(AN3)的R AN6~R AN9所表示之烷基的碳數為1~10為較佳,1~6為更佳,1~3為進一步較佳。烷基可舉出直鏈、支鏈、環狀,直鏈或支鏈為較佳,直鏈為更佳。烷基可以具有取代基,亦可以未經取代。烷基為具有鹵素原子作為取代基之烷基為較佳,具有氟原子作為取代基之烷基(氟烷基)為更佳。又,氟烷基為全氟烷基為較佳。 The alkyl groups represented by R AN1 and R AN2 of formula (AN1), the alkyl groups represented by R AN3 to R AN5 of formula (AN2), and the alkyl groups represented by R AN6 to R AN9 of formula (AN3) preferably have 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms. The alkyl group may be a straight chain, a branched chain, or a ring. A straight chain or a branched chain is preferred, and a straight chain is more preferred. The alkyl group may have a substituent or may be unsubstituted. The alkyl group is preferably an alkyl group having a halogen atom as a substituent, and more preferably an alkyl group having a fluorine atom as a substituent (fluoroalkyl group). Furthermore, the fluoroalkyl group is preferably a perfluoroalkyl group.
式(AN3)的R AN6~R AN9所表示之芳基的碳數為6~20為較佳,6~12為更佳,6為進一步較佳。芳基可以具有取代基,亦可以未經取代。作為取代基,可舉出鹵素原子及烷基。作為鹵素原子,氟原子為較佳。作為烷基,氟烷基為較佳。 The number of carbon atoms in the aryl group represented by R AN6 to R AN9 in the formula (AN3) is preferably 6 to 20, more preferably 6 to 12, and even more preferably 6. The aryl group may have a substituent or may be unsubstituted. Examples of the substituent include a halogen atom and an alkyl group. As the halogen atom, a fluorine atom is preferred. As the alkyl group, a fluoroalkyl group is preferred.
式(AN3)的R AN6~R AN9所表示之烷氧基的碳數為1~10為較佳,1~6為更佳,1~3為進一步較佳。烷氧基可舉出直鏈、支鏈、環狀,直鏈或支鏈為較佳,直鏈為更佳。烷氧基可以具有取代基,亦可以未經取代。作為取代基,可舉出鹵素原子及烷基。作為鹵素原子,氟原子為較佳。作為烷基,氟烷基為較佳。 The carbon number of the alkoxy group represented by R AN6 to R AN9 in the formula (AN3) is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3. The alkoxy group may be a straight chain, a branched chain, or a ring. A straight chain or a branched chain is preferred, and a straight chain is more preferred. The alkoxy group may have a substituent or may be unsubstituted. As the substituent, a halogen atom and an alkyl group may be cited. As the halogen atom, a fluorine atom is preferred. As the alkyl group, a fluoroalkyl group is preferred.
式(AN3)的R AN6~R AN9所表示之芳氧基的碳數為6~20為較佳,6~12為更佳,6為進一步較佳。芳氧基可以具有取代基,亦可以未經取代。作為取代基,可舉出鹵素原子及烷基。作為鹵素原子,氟原子為較佳。作為烷基,氟烷基為較佳。 The carbon number of the aryloxy group represented by R AN6 to R AN9 in formula (AN3) is preferably 6 to 20, more preferably 6 to 12, and even more preferably 6. The aryloxy group may have a substituent or may be unsubstituted. Examples of the substituent include a halogen atom and an alkyl group. As the halogen atom, a fluorine atom is preferred. As the alkyl group, a fluoroalkyl group is preferred.
式(AN1)的R AN1與R AN2可以鍵結而形成環。式(AN2)的R AN3與R AN4、R AN4與R AN5或R AN3與R AN5可以鍵結而形成環。 In formula (AN1), R AN1 and R AN2 may bond to form a ring. In formula (AN2), R AN3 and R AN4 , R AN4 and R AN5 , or R AN3 and R AN5 may bond to form a ring.
式(AN4)的R AN10表示可以藉由具有氮原子或氧原子之連結基連結之鹵化烴基。鹵化烴基係指被鹵素原子取代之1價烴基,被氟原子取代之1價烴基為較佳。作為烴基,可舉出烷基、芳基等。被鹵素原子取代之1價烴基可以進一步具有取代基。作為具有氮原子或氧原子之連結基,可舉出-O-、―CO-、-COO-、-CO-NH-等。 R AN10 in formula (AN4) represents a halogenated alkyl group which may be linked via a linking group having a nitrogen atom or an oxygen atom. The halogenated alkyl group refers to a monovalent alkyl group substituted by a halogen atom, and a monovalent alkyl group substituted by a fluorine atom is preferred. Examples of the alkyl group include an alkyl group, an aryl group, and the like. The monovalent alkyl group substituted by a halogen atom may further have a substituent. Examples of the linking group having a nitrogen atom or an oxygen atom include -O-, -CO-, -COO-, -CO-NH-, and the like.
式(AN5)的R AN11~R AN16分別獨立地表示鹵素原子或鹵化烴基。作為鹵素原子,可舉出氟原子、氯原子、溴原子、碘原子,氟原子為較佳。作為鹵化烴基,具有鹵素原子作為取代基之烷基為較佳,具有氟原子作為取代基之烷基為更佳。 R AN11 to R AN16 in formula (AN5) each independently represents a halogen atom or a halogenated alkyl group. Examples of the halogenated alkyl group include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, with a fluorine atom being preferred. As the halogenated alkyl group, an alkyl group having a halogen atom as a substituent is preferred, and an alkyl group having a fluorine atom as a substituent is more preferred.
-關於取代基T- 作為取代基T,可舉出以下基團。鹵素原子(例如,氟原子、氯原子、溴原子、碘原子)、烷基(較佳為碳數1~30的烷基)、烯基(較佳為碳數2~30的烯基)、炔基(較佳為碳數2~30的炔基)、芳基(較佳為碳數6~30的芳基)、雜環基(較佳為碳數1~30的雜環基)、胺基(較佳為碳數0~30的胺基)、烷氧基(較佳為碳數1~30的烷氧基)、芳氧基(較佳為碳數6~30的芳氧基)、雜環氧基(較佳為碳數1~30的雜環氧基)、醯基(較佳為碳數2~30的醯基)、烷氧基羰基(較佳為碳數2~30的烷氧基羰基)、芳氧基羰基(較佳為碳數7~30的芳氧基羰基)、雜環氧基羰基(較佳為碳數2~30的雜環氧基羰基)、醯氧基(較佳為碳數2~30的醯氧基)、醯胺基(較佳為碳數2~30的醯胺基)、胺基羰基胺基(較佳為碳數2~30的胺基羰基胺基)、烷氧基羰基胺基(較佳為碳數2~30的烷氧基羰基胺基)、芳氧基羰基胺基(較佳為碳數7~30的芳氧基羰基胺基)、胺磺醯基(較佳為碳數0~30的胺磺醯基)、胺磺醯基胺基(較佳為碳數0~30的胺磺醯基胺基)、胺甲醯基(較佳為碳數1~30的胺甲醯基)、烷硫基(較佳為碳數1~30的烷硫基)、芳硫基(較佳為碳數6~30的芳硫基)、雜環硫基(較佳為碳數1~30的雜環硫基)、烷基磺醯基(較佳為碳數1~30的烷基磺醯基)、烷基磺醯基胺基(較佳為碳數1~30的烷基磺醯基胺基)、芳基磺醯基(較佳為碳數6~30的芳基磺醯基)、芳基磺醯基胺基(較佳為碳數6~30的芳基磺醯基胺基)、雜環磺醯基(較佳為碳數1~30的雜環磺醯基)、雜環磺醯基胺基(較佳為碳數1~30的雜環磺醯基胺基)、烷基亞磺醯基(較佳為碳數1~30的烷基亞磺醯基)、芳基亞磺醯基(較佳為碳數6~30的芳基亞磺醯基)、雜環亞磺醯基(較佳為碳數1~30的雜環亞磺醯基)、脲基(較佳為碳數1~30的脲基)、羥基、硝基、羧基、磺基、磷酸基、羧酸醯胺基、磺酸醯胺基、醯亞胺基、膦基、巰基、氰基、烷基亞磺酸基、芳基亞磺酸基、芳基偶氮基、雜環偶氮基、氧膦基、氧膦基氧基、氧膦基胺基、矽基、肼基、亞胺基。該等基團為能夠進一步取代之基團時,可以進一步具有取代基。作為取代基,可舉出在上述取代基T中說明之基團。 -About substituent T- As substituent T, the following groups can be cited. a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group (preferably an alkyl group having 1 to 30 carbon atoms), an alkenyl group (preferably an alkenyl group having 2 to 30 carbon atoms), an alkynyl group (preferably an alkynyl group having 2 to 30 carbon atoms), an aryl group (preferably an aryl group having 6 to 30 carbon atoms), a heterocyclic group (preferably a heterocyclic group having 1 to 30 carbon atoms), an amino group (preferably an amino group having 0 to 30 carbon atoms), an alkoxy group (preferably an alkoxy group having 1 to 30 carbon atoms), an aryloxy group (preferably an aryloxy group having 6 to 30 carbon atoms), a heterocyclicoxy group (preferably a heterocyclicoxy group having 1 to 30 carbon atoms), an acyl group (preferably an acyl group having 2 to 30 carbon atoms), an alkoxycarbonyl group (preferably The present invention is an alkoxycarbonyl group having 2 to 30 carbon atoms), an aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 30 carbon atoms), a heterocyclic oxycarbonyl group (preferably a heterocyclic oxycarbonyl group having 2 to 30 carbon atoms), an acyloxy group (preferably an acyloxy group having 2 to 30 carbon atoms), an amide group (preferably an amide group having 2 to 30 carbon atoms), an aminocarbonylamino group (preferably an aminocarbonylamino group having 2 to 30 carbon atoms), an alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 30 carbon atoms), an aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 30 carbon atoms), an aminesulfonyl group (preferably an aminesulfonyl group having 0 to 30 carbon atoms), an aminesulfonylamino group (preferably a aminesulfonyl group having 0 to 30 carbon atoms), a aminesulfonylamino group (preferably a aminesulfonyl group having 0 to 30 carbon atoms), a aminesulfonylamino group (preferably a aminesulfonyl group having 0 to 30 carbon atoms), a aminesulfonylamino group (preferably a aminesulfonyl group having 0 to 30 carbon atoms), a aminesulfonylamino group (preferably a aminesulfonylamino ...carbonylamino group (preferably a aminecarbonylamino group having 0 to 30 carbon atoms), a ~30 aminosulfonylamino), carbamoyl (preferably carbamoyl with 1 to 30 carbon atoms), alkylthio (preferably alkylthio with 1 to 30 carbon atoms), arylthio (preferably arylthio with 6 to 30 carbon atoms), heterocyclic thio (preferably heterocyclic thio with 1 to 30 carbon atoms), alkylsulfonyl (preferably ), alkylsulfonylamino (preferably an alkylsulfonylamino having 1 to 30 carbon atoms), arylsulfonyl (preferably an arylsulfonylamino having 6 to 30 carbon atoms), arylsulfonylamino (preferably an arylsulfonylamino having 6 to 30 carbon atoms), heterocyclic sulfonyl (preferably a heterocyclic sulfonyl having 1 to 30 carbon atoms) , heterocyclic sulfonylamine (preferably a heterocyclic sulfonylamine with 1 to 30 carbon atoms), alkylsulfinyl (preferably an alkylsulfinyl with 1 to 30 carbon atoms), arylsulfinyl (preferably an arylsulfinyl with 6 to 30 carbon atoms), heterocyclic sulfinyl (preferably a heterocyclic sulfinyl with 1 to 30 carbon atoms), urea (preferably Preferably, the group is a urea group having 1 to 30 carbon atoms), a hydroxyl group, a nitro group, a carboxyl group, a sulfo group, a phosphate group, a carboxylic acid amide group, a sulfonic acid amide group, an imide group, a phosphino group, a sulfonyl group, a cyano group, an alkylsulfinic acid group, an arylsulfinic acid group, an arylazo group, a heterocyclic azo group, an oxyphosphinyl group, an oxyphosphinyl amine group, a silyl group, a hydrazine group, and an imino group. When these groups are groups that can be further substituted, they may further have substituents. As substituents, the groups described in the above substituent T can be cited.
作為特定化合物的具體例,可舉出以下所示之結構的化合物。作為特定化合物的具體例,亦可舉出該等化合物的共振結構體。再者,以下所示之結構式中的Me為甲基,Et為乙基,nPr為正丙基,iPr為異丙基,nBu為正丁基,tBu為三級丁基,Hex為己基,Cy為環己基,Ad為金剛烷基,Ph為苯基,Ac為乙醯基。As specific examples of specific compounds, compounds having the structures shown below can be cited. As specific examples of specific compounds, resonance structures of these compounds can also be cited. In the structural formula shown below, Me is a methyl group, Et is an ethyl group, nPr is an n-propyl group, iPr is an isopropyl group, nBu is an n-butyl group, tBu is a tertiary butyl group, Hex is a hexyl group, Cy is a cyclohexyl group, Ad is an adamantyl group, Ph is a phenyl group, and Ac is an acetyl group.
[表1] [化學式5] [表2] [表3] [表4] [表5] [Table 1] [Chemical formula 5] [Table 2] [table 3] [Table 4] [table 5]
特定化合物的極大吸收波長存在於波長650~1500nm的範圍內為較佳,存在於波長680~1200的範圍內為更佳,存在於波長700~1000nm的範圍內為進一步較佳。The maximum absorption wavelength of the specific compound is preferably in the range of 650 to 1500 nm, more preferably in the range of 680 to 1200 nm, and even more preferably in the range of 700 to 1000 nm.
特定化合物較佳地用作紅外線吸收劑。Certain compounds are preferably used as infrared absorbers.
組成物的總固體成分中特定化合物(由式(1)表示之化合物)的含量為0.1質量%以上為較佳,0.5質量%以上為更佳,3質量%以上為進一步較佳,5質量%以上為特佳。又,紅外線吸收劑的含量的上限為50質量%以下為較佳,40質量%以下為更佳,30質量%以下為進一步較佳。本發明的組成物可以僅含有1種特定化合物,亦可以含有2種以上。包含2種以上時,該等的合計量在上述範圍內為較佳。The content of the specific compound (the compound represented by formula (1)) in the total solid content of the composition is preferably 0.1 mass % or more, more preferably 0.5 mass % or more, further preferably 3 mass % or more, and particularly preferably 5 mass % or more. In addition, the upper limit of the content of the infrared absorber is preferably 50 mass % or less, more preferably 40 mass % or less, and further preferably 30 mass % or less. The composition of the present invention may contain only one specific compound or two or more. When containing two or more, the total amount of the specific compounds is preferably within the above range.
<<硬化性化合物>> 本發明的組成物含有硬化性化合物。作為硬化性化合物,可舉出聚合性化合物、樹脂等。樹脂可以為非聚合性樹脂(不具有聚合性基之樹脂),亦可以為聚合性樹脂(具有聚合性基之樹脂)。作為聚合性基,可舉出含有乙烯性不飽和鍵之基團、環狀醚基、羥甲基、烷氧基甲基等。作為含有乙烯性不飽和鍵之基團,可舉出乙烯基、乙烯基苯基、(甲基)烯丙基、(甲基)丙烯醯基、(甲基)丙烯醯氧基、(甲基)丙烯醯基醯胺基等,(甲基)烯丙基、(甲基)丙烯醯基及(甲基)丙烯醯氧基為較佳,(甲基)丙烯醯氧基為更佳。作為環狀醚基,可舉出環氧基、氧環丁烷基等,環氧基為較佳。 <<Hardening compound>> The composition of the present invention contains a curing compound. Examples of the curing compound include polymerizable compounds, resins, and the like. The resin may be a non-polymerizable resin (a resin having no polymerizable group) or a polymerizable resin (a resin having a polymerizable group). Examples of the polymerizable group include groups containing ethylenic unsaturated bonds, cyclic ether groups, hydroxymethyl groups, alkoxymethyl groups, and the like. Examples of the group containing ethylenic unsaturated bonds include vinyl, vinylphenyl, (meth)allyl, (meth)acryloyl, (meth)acryloyloxy, (meth)acryloylamide, and the like. (Meth)allyl, (meth)acryloyl, and (meth)acryloyloxy are preferred, and (meth)acryloyloxy is more preferred. Examples of the cyclic ether group include an epoxy group, an oxycyclobutane group, etc., and an epoxy group is preferred.
作為硬化性化合物,使用至少含有樹脂者為較佳。又,將本發明的組成物作為光微影用組成物時,作為硬化性化合物,使用樹脂和聚合性化合物(較佳為作為單體類型聚合性化合物的聚合性單體)為較佳,使用樹脂和具有含有乙烯性不飽和鍵之基團之聚合性單體(單體類型聚合性化合物)為更佳。As the curable compound, it is preferred to use a compound containing at least a resin. Furthermore, when the composition of the present invention is used as a composition for photolithography, it is preferred to use a resin and a polymerizable compound (preferably a polymerizable monomer that is a monomer-type polymerizable compound) as the curable compound, and it is more preferred to use a resin and a polymerizable monomer having a group containing an ethylenic unsaturated bond (monomer-type polymerizable compound).
(聚合性化合物) 作為聚合性化合物,可舉出具有含有乙烯性不飽和鍵的基團之化合物、具有環狀醚基之化合物、具有羥甲基之化合物、具有烷氧基甲基之化合物等。具有含有乙烯性不飽和鍵的基團之化合物能夠較佳地用作自由基聚合性化合物。又,具有環狀醚基之化合物能夠較佳地用作陽離子聚合性化合物。 (Polymerizable compound) As polymerizable compounds, compounds having a group containing an ethylenic unsaturated bond, compounds having a cyclic ether group, compounds having a hydroxymethyl group, compounds having an alkoxymethyl group, etc. can be cited. Compounds having a group containing an ethylenic unsaturated bond can be preferably used as free radical polymerizable compounds. In addition, compounds having a cyclic ether group can be preferably used as cationic polymerizable compounds.
作為樹脂類型聚合性化合物,可舉出包含具有聚合性基之重複單元之樹脂等。Examples of the resin type polymerizable compound include resins containing repeating units having a polymerizable group.
單體類型聚合性化合物(聚合性單體)的分子量未達2000為較佳,1500以下為更佳。聚合性單體的分子量的下限為100以上為較佳,200以上為更佳。樹脂類型的聚合性化合物的重量平均分子量(Mw)為2000~2000000為較佳。重量平均分子量的上限為1000000以下為較佳,500000以下為更佳。重量平均分子量的下限為3000以上為較佳,5000以上為更佳。The molecular weight of the monomer type polymerizable compound (polymerizable monomer) is preferably less than 2000, and more preferably 1500 or less. The lower limit of the molecular weight of the polymerizable monomer is preferably 100 or more, and more preferably 200 or more. The weight average molecular weight (Mw) of the resin type polymerizable compound is preferably 2000 to 2000000. The upper limit of the weight average molecular weight is preferably 1000000 or less, and more preferably 500000 or less. The lower limit of the weight average molecular weight is preferably 3000 or more, and more preferably 5000 or more.
作為聚合性單體的具有含有乙烯性不飽和鍵的基團之化合物為3~15官能的(甲基)丙烯酸酯化合物為較佳,3~6官能的(甲基)丙烯酸酯化合物為更佳。作為具體例,可舉出日本特開2009-288705號公報的0095~0108段、日本特開2013-029760號公報的0227段、日本特開2008-292970號公報的0254~0257段、日本特開2013-253224號公報的0034~0038段、日本特開2012-208494號公報的0477段、日本特開2017-048367號公報、日本專利第6057891號公報、日本專利第6031807號公報、日本特開2017-194662號公報中記載之化合物,該等內容編入本說明書中。The compound having a group containing an ethylenically unsaturated bond as a polymerizable monomer is preferably a tri- to penta-functional (meth)acrylate compound, and more preferably a tri- to hexa-functional (meth)acrylate compound. As specific examples, there can be cited the compounds described in paragraphs 0095 to 0108 of Japanese Patent Application No. 2009-288705, paragraph 0227 of Japanese Patent Application No. 2013-029760, paragraphs 0254 to 0257 of Japanese Patent Application No. 2008-292970, paragraphs 0034 to 0038 of Japanese Patent Application No. 2013-253224, paragraph 0477 of Japanese Patent Application No. 2012-208494, Japanese Patent Application No. 2017-048367, Japanese Patent No. 6057891, Japanese Patent No. 6031807, and Japanese Patent Application No. 2017-194662, and the contents thereof are incorporated into this specification.
作為具有含有乙烯性不飽和鍵的基團之化合物,可舉出二新戊四醇三(甲基)丙烯酸酯(市售品為KAYARAD D-330;Nippon Kayaku Co., Ltd.製)、二新戊四醇四(甲基)丙烯酸酯(市售品為KAYARAD D-320;Nippon Kayaku Co., Ltd.製)、二新戊四醇五(甲基)丙烯酸酯(市售品為KAYARAD D-310;Nippon Kayaku Co., Ltd.製)、二新戊四醇六(甲基)丙烯酸酯(市售品為KAYARAD DPHA;Nippon Kayaku Co., Ltd.製NK ESTER A-DPH-12E;SHIN-NAKAMURA CHEMICAL Co., Ltd.製)及該等化合物的(甲基)丙烯醯基經由乙二醇及/或丙二醇殘基鍵結之結構的化合物(例如,SARTOMER Company,Inc.的市售品SR454、SR499)等。又,作為具有含有乙烯性不飽和鍵的基團之化合物,亦能夠使用二甘油EO(環氧乙烷)改質(甲基)丙烯酸酯(市售品為M-460;TOAGOSEI CO., LTD.製)、新戊四醇四丙烯酸酯(SHIN-NAKAMURA CHEMICAL Co., Ltd.製NK ESTER A-TMMT)、1,6-己二醇二丙烯酸酯(Nippon Kayaku Co., Ltd.製KAYARAD HDDA)、RP-1040(Nippon Kayaku Co., Ltd.製)、ARONIX TO-2349(TOAGOSEI CO., LTD.製)、NK Oligo UA-7200(SHIN-NAKAMURA CHEMICAL Co., Ltd.製)、8UH-1006、8UH-1012(Taisei Fine Chemical Co., Ltd.製)、LIGHT ACRYLATE POB-A0(KYOEISHA CHEMICAL Co., LTD.製)等。Examples of the compound having a group containing an ethylenic unsaturated bond include dipentatriol tri(meth)acrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentatriol tetra(meth)acrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentatriol penta(meth)acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentatriol hexa(meth)acrylate (commercially available as KAYARAD DPHA; NK ESTER A-DPH-12E manufactured by Nippon Kayaku Co., Ltd.; SHIN-NAKAMURA CHEMICAL Co., Ltd. Ltd.) and compounds having a structure in which the (meth)acryloyl group of these compounds is bonded via an ethylene glycol and/or propylene glycol residue (for example, commercially available products SR454 and SR499 from SARTOMER Company, Inc.). As the compound having a group containing an ethylenic unsaturated bond, diglycerol EO (ethylene oxide) modified (meth) acrylate (commercially available as M-460; manufactured by TOAGOSEI CO., LTD.), pentaerythritol tetraacrylate (NK ESTER A-TMMT manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.), 1,6-hexanediol diacrylate (KAYARAD HDDA manufactured by Nippon Kayaku Co., Ltd.), RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), ARONIX TO-2349 (manufactured by TOAGOSEI CO., LTD.), NK Oligo UA-7200 (manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.), 8UH-1006, 8UH-1012 (manufactured by Taisei Fine Chemical Co., Ltd.), LIGHT ACRYLATE POB-A0 (made by KYOEISHA CHEMICAL Co., LTD.), etc.
又,作為具有含有乙烯性不飽和鍵的基團之化合物,使用三羥甲基丙烷三(甲基)丙烯酸酯、三羥甲基丙烷環氧丙烷改質三(甲基)丙烯酸酯、三羥甲基丙烷環氧乙烷改質三(甲基)丙烯酸酯、異三聚氰酸環氧乙烷改質三(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯等3官能(甲基)丙烯酸酯化合物亦較佳。作為3官能(甲基)丙烯酸酯化合物的市售品,可舉出ARONIX M-309、M-310、M-321、M-350、M-360、M-313、M-315、M-306、M-305、M-303、M-452、M-450(TOAGOSEI CO., LTD.製)、NK ESTER A9300、A-GLY-9E、A-GLY-20E、A-TMM-3、A-TMM-3L、A-TMM-3LM-N、A-TMPT、TMPT(SHIN-NAKAMURA CHEMICAL Co., Ltd.製)、KAYARAD GPO-303、TMPTA、THE-330、TPA-330、PET-30(Nippon Kayaku Co., Ltd.製)等。Furthermore, as the compound having a group containing an ethylenic unsaturated bond, a trifunctional (meth)acrylate compound such as trihydroxymethylpropane tri(meth)acrylate, trihydroxymethylpropane propylene oxide modified tri(meth)acrylate, trihydroxymethylpropane ethylene oxide modified tri(meth)acrylate, isocyanurate ethylene oxide modified tri(meth)acrylate, or pentaerythritol tri(meth)acrylate is also preferably used. Commercially available products of the trifunctional (meth)acrylate compound include ARONIX M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, M-305, M-303, M-452, and M-450 (manufactured by TOAGOSEI CO., LTD.), NK ESTER A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, and TMPT (manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, and PET-30 (manufactured by Nippon Kayaku Co., Ltd.).
具有含有乙烯性不飽和鍵的基團之化合物可以進一步具有羧基、磺基、磷酸基等酸基。作為此類化合物的市售品,可舉出ARONIX M-305、M-510、M-520、ARONIX TO-2349(TOAGOSEI CO., LTD.製)等。The compound having a group containing an ethylenically unsaturated bond may further have an acid group such as a carboxyl group, a sulfonic group, or a phosphoric acid group. Examples of commercially available products of such compounds include ARONIX M-305, M-510, M-520, and ARONIX TO-2349 (manufactured by TOAGOSEI CO., LTD.).
作為具有含有乙烯性不飽和鍵的基團之化合物,亦能夠使用具有己內酯結構之化合物。關於具有己內酯結構之化合物,能夠參考日本特開2013-253224號公報的0042~0045段的記載,該內容編入本說明書中。關於具有己內酯結構之化合物,例如,可舉出Nippon Kayaku Co., Ltd.的市售品DPCA-20、DPCA-30、DPCA-60、DPCA-120等。As the compound having a group containing an ethylenic unsaturated bond, a compound having a caprolactone structure can also be used. For the compound having a caprolactone structure, reference can be made to paragraphs 0042 to 0045 of Japanese Patent Application Publication No. 2013-253224, which is incorporated into this specification. For example, commercial products DPCA-20, DPCA-30, DPCA-60, and DPCA-120 of Nippon Kayaku Co., Ltd. can be cited as examples of the compound having a caprolactone structure.
作為具有含有乙烯性不飽和鍵的基團之化合物,亦能夠使用具有含有乙烯性不飽和鍵之基團及伸烷氧基之化合物。此類化合物為具有含有乙烯性不飽和鍵之基團及乙烯氧基和/或伸丙基氧基之化合物為較佳,具有含有乙烯性不飽和鍵之基團及乙烯氧基之化合物為更佳,具有4~20個乙烯氧基之3~6官能(甲基)丙烯酸酯化合物為進一步較佳。作為市售品,例如可舉出SARTOMER Company,Inc.製具有4個乙烯氧基之4官能(甲基)丙烯酸酯SR-494、Nippon Kayaku Co., Ltd.製具有3個伸異丁氧基之3官能(甲基)丙烯酸酯KAYARAD TPA-330等。As the compound having a group containing an ethylenic unsaturated bond, a compound having a group containing an ethylenic unsaturated bond and an alkoxy group can also be used. Such a compound is preferably a compound having a group containing an ethylenic unsaturated bond and an ethyleneoxy group and/or an alkyloxy group, more preferably a compound having a group containing an ethylenic unsaturated bond and an ethyleneoxy group, and further preferably a tri- to hexa-functional (meth)acrylate compound having 4 to 20 ethyleneoxy groups. Examples of commercially available products include SR-494, a tetrafunctional (meth)acrylate having 4 ethyleneoxy groups manufactured by SARTOMER Company, Inc., and KAYARAD TPA-330, a trifunctional (meth)acrylate having 3 isobutyloxy groups manufactured by Nippon Kayaku Co., Ltd.
作為具有含有乙烯性不飽和鍵的基團之化合物,亦能夠使用具有茀骨架之聚合性化合物。作為市售品,可舉出OGSOL EA-0200、EA-0300(Osaka Gas Chemicals Co., Ltd.製具有茀骨架之(甲基)丙烯酸酯單體)等。As the compound having a group containing an ethylenically unsaturated bond, a polymerizable compound having a fluorene skeleton can also be used. Examples of commercially available products include OGSOL EA-0200 and EA-0300 (a (meth)acrylate monomer having a fluorene skeleton manufactured by Osaka Gas Chemicals Co., Ltd.).
作為具有含有乙烯性不飽和鍵的基團之化合物,使用實質上不含有甲苯等環境管制物質之化合物亦較佳。作為此類化合物的市售品,可舉出KAYARAD DPHA LT、KAYARAD DPEA-12 LT(Nippon Kayaku Co., Ltd.製)等。As the compound having a group containing an ethylenically unsaturated bond, it is also preferable to use a compound that does not substantially contain environmentally regulated substances such as toluene. Examples of commercially available products of such a compound include KAYARAD DPHA LT and KAYARAD DPEA-12 LT (manufactured by Nippon Kayaku Co., Ltd.).
作為具有環狀醚基之化合物,可舉出具有環氧基之化合物、具有氧環丁烷基之化合物等,較佳為具有環氧基之化合物。作為具有環氧基之化合物,可舉出在1分子內具有1~100個環氧基之化合物。環氧基數的上限例如能夠設定為10個以下,亦能夠設定為5個以下。環氧基數的下限較佳為2個以上。As the compound having a cyclic ether group, there can be mentioned a compound having an epoxy group, a compound having an oxetane group, etc., and preferably a compound having an epoxy group. As the compound having an epoxy group, there can be mentioned a compound having 1 to 100 epoxy groups in one molecule. The upper limit of the number of epoxy groups can be set to, for example, 10 or less, or 5 or less. The lower limit of the number of epoxy groups is preferably 2 or more.
具有環狀醚基之化合物可以為低分子化合物(例如,分子量未達1000),亦可以為高分子化合物(macromolecule)(例如,分子量為1000以上,聚合物的情況下,重量平均分子量為1000以上)。環狀醚基的重量平均分子量為200~100000為較佳,500~50000為更佳。重量平均分子量的上限為10000以下為較佳,5000以下為更佳,3000以下為進一步較佳。The compound having a cyclic ether group may be a low molecular weight compound (e.g., a molecular weight of less than 1000) or a high molecular weight compound (e.g., a molecular weight of 1000 or more, and in the case of a polymer, a weight average molecular weight of 1000 or more). The weight average molecular weight of the cyclic ether group is preferably 200 to 100,000, more preferably 500 to 50,000. The upper limit of the weight average molecular weight is preferably 10,000 or less, more preferably 5,000 or less, and even more preferably 3,000 or less.
作為具有環狀醚基之化合物,亦能夠使用日本特開2013-011869號公報的0034~0036段中記載之化合物、日本特開2014-043556號公報的0147~0156段中記載之化合物、日本特開2014-089408號公報的0085~0092段中記載之化合物、日本特開2017-179172號公報中記載之化合物。As the compound having a cyclic ether group, the compounds described in paragraphs 0034 to 0036 of JP-A-2013-011869, the compounds described in paragraphs 0147 to 0156 of JP-A-2014-043556, the compounds described in paragraphs 0085 to 0092 of JP-A-2014-089408, and the compounds described in JP-A-2017-179172 can also be used.
作為具有環狀醚基之化合物的市售品,可舉出DENACOL EX-212L、EX-212、EX-214L、EX-214、EX-216L、EX-216、EX-321L、EX-321、EX-850L、EX-850(以上為Nagase ChemteX Corporation製)、ADEKA RESIN EP-4000S、EP-4003S、EP-4010S、EP-4011S(以上為ADEKA CORPORATION製)、NC-2000、NC-3000、NC-7300、XD-1000、EPPN-501、EPPN-502(以上為ADEKA CORPORATION製)、CELLOXIDE 2021P、CELLOXIDE 2081、CELLOXIDE 2083、CELLOXIDE 2085、EHPE3150、EPOLEAD PB 3600、PB 4700(以上為Daicel Corporation製)、CYCLOMER P ACA 200M、ACA 230AA、ACA Z250、ACA Z251、ACA Z300、ACA Z320(以上為Daicel Corporation製)、jER1031S、jER157S65、jER152、jER154、jER157S70(以上為Mitsubishi Chemical Corporation製)、ARONE OXETANE OXT-121、OXT-221、OX-SQ、PNOX(以上為TOAGOSEI CO., LTD.製)、ADEKA GLYCIROL ED-505(ADEKA CORPORATION製含環氧基單體)、Marproof G-0150M、G-0105SA、G-0130SP、G-0250SP、G-1005S、G-1005SA、G-1010S、G-2050M、G-01100、G-01758(NOF CORPORATION製含環氧基聚合物)、OXT-101、OXT-121、OXT-212、OXT-221(以上為TOAGOSEI CO., LTD.製含氧環丁烷基單體)、OXE-10、OXE-30(以上為OSAKA ORGANIC CHEMICAL INDUSTRY LTD.製含氧環丁烷基單體)等。Examples of commercially available compounds having a cyclic ether group include DENACOL EX-212L, EX-212, EX-214L, EX-214, EX-216L, EX-216, EX-321L, EX-321, EX-850L, EX-850 (all manufactured by Nagase ChemteX Corporation), ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (all manufactured by ADEKA CORPORATION), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (all manufactured by ADEKA CORPORATION), CELLOXIDE 2021P, CELLOXIDE 2081, CELLOXIDE 2083, CELLOXIDE 2085, EHPE3150, EPOLEAD PB 3600, PB 4700 (all manufactured by Daicel Corporation), CYCLOMER P ACA 200M, ACA 230AA, ACA Z250, ACA Z251, ACA Z300, ACA Z320 (all manufactured by Daicel Corporation), jER1031S, jER157S65, jER152, jER154, jER157S70 (all manufactured by Mitsubishi Chemical Corporation), ARONE OXETANE OXT-121, OXT-221, OX-SQ, PNOX (all manufactured by TOAGOSEI CO., LTD.), ADEKA GLYCIROL ED-505 (epoxy-containing monomer manufactured by ADEKA CORPORATION), Marproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (epoxy-containing polymers manufactured by NOF CORPORATION), OXT-101, OXT-121, OXT-212, OXT-221 (oxycyclobutane-containing monomers manufactured by TOAGOSEI CO., LTD.), OXE-10, OXE-30 (oxycyclobutane-containing monomers manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.), etc.
作為具有羥甲基之化合物(以下,亦稱為羥甲基化合物),可舉出羥甲基與氮原子或形成芳香族環之碳原子鍵結之化合物。又,作為具有烷氧基甲基之化合物(以下,亦稱為烷氧基甲基化合物),可舉出烷氧基甲基與氮原子或形成芳香族環之碳原子鍵結之化合物。作為烷氧基甲基或羥甲基與氮原子鍵結之化合物,烷氧基甲基化三聚氰胺、羥甲基化三聚氰胺、烷氧基甲基化苯并胍胺、羥甲基化苯并胍胺、烷氧基甲基化甘脲、羥甲基化甘脲、烷氧基甲基化脲及羥甲基化脲等為較佳。又,亦能夠使用日本特開2004-295116號公報的0134~0147段、日本特開2014-089408號公報的0095~0126段中記載之化合物。As the compound having a hydroxymethyl group (hereinafter, also referred to as a hydroxymethyl compound), there can be mentioned a compound in which a hydroxymethyl group is bonded to a nitrogen atom or a carbon atom forming an aromatic ring. Furthermore, as the compound having an alkoxymethyl group (hereinafter, also referred to as an alkoxymethyl compound), there can be mentioned a compound in which an alkoxymethyl group is bonded to a nitrogen atom or a carbon atom forming an aromatic ring. As the compound in which an alkoxymethyl group or a hydroxymethyl group is bonded to a nitrogen atom, alkoxymethylated melamine, hydroxymethylated melamine, alkoxymethylated benzoguanamine, hydroxymethylated benzoguanamine, alkoxymethylated glycoluril, hydroxymethylated glycoluril, alkoxymethylated urea, and hydroxymethylated urea are preferred. Furthermore, compounds described in paragraphs 0134 to 0147 of JP-A-2004-295116 and paragraphs 0095 to 0126 of JP-A-2014-089408 can also be used.
(樹脂) 本發明的組成物能夠使用樹脂作為硬化性化合物。硬化性化合物使用至少包含樹脂者為較佳。樹脂例如以在組成物中分散顏料等之用途、黏合劑的用途調配。再者,將主要用於在組成物中分散顏料等之樹脂亦稱為分散劑。然而,樹脂的此類用途為一例,亦能夠以此類用途以外的用途為目的使用樹脂。再者,具有聚合性基之樹脂亦相當於聚合性化合物。 (Resin) The composition of the present invention can use a resin as a curable compound. It is preferred that the curable compound contains at least a resin. The resin is formulated, for example, for the purpose of dispersing a pigment in a composition or for the purpose of an adhesive. Furthermore, a resin mainly used for dispersing a pigment in a composition is also referred to as a dispersant. However, this use of the resin is an example, and the resin can also be used for purposes other than this use. Furthermore, a resin having a polymerizable group is also equivalent to a polymerizable compound.
樹脂的重量平均分子量為3000~2000000為較佳。上限為1000000以下為較佳,500000以下為更佳。下限為4000以上為較佳,5000以上為更佳。The weight average molecular weight of the resin is preferably 3,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less, and the lower limit is preferably 4,000 or more, more preferably 5,000 or more.
作為樹脂,可舉出(甲基)丙烯酸樹脂、環氧樹脂、烯-硫醇樹脂、聚碳酸酯樹脂、聚醚樹脂、聚芳酯樹脂、聚碸樹脂、聚醚碸樹脂、聚苯樹脂、聚伸芳基醚氧化膦樹脂、聚醯亞胺樹脂、聚醯胺樹脂、聚醯胺醯亞胺樹脂、聚烯烴樹脂、環烯烴樹脂、聚酯樹脂、苯乙烯樹脂、乙酸乙烯酯樹脂、聚乙烯醇樹脂、聚乙烯縮醛樹脂、聚胺酯樹脂、聚脲樹脂等。在該等樹脂中,可以單獨使用1種,亦可以混合使用2種以上。作為環烯烴樹脂,從提高耐熱性的觀點考慮,降莰烯樹脂為較佳。作為降莰烯樹脂的市售品,例如,可舉出JSR Corporation製ARTON系列(例如,ARTON F4520)等。又,作為樹脂,亦能夠使用國際公開第2022/065215號的0091~0099段中記載之樹脂、日本特開2016-222891號公報中記載之嵌段聚異氰酸酯樹脂、日本特開2020-122052號公報中記載之樹脂、日本特開2020-111656號公報中記載之樹脂、日本特開2020-139021號公報中記載之樹脂、日本特開2017-138503號公報中記載之包含主鏈具有環結構之結構單元和側鏈具有聯苯基之結構單元之樹脂、日本特開2020-186373號公報的0199~0233段中記載之樹脂、日本特開2020-186325號公報中記載之鹼可溶性樹脂、韓國公開專利第10-2020-0078339號公報中記載之由式1表示之樹脂、國際公開第2022/030445號中記載之包含環氧基和酸基之共聚物、日本特開2020-186373號公報的0199~0233段中記載之樹脂、日本特開2020-186325號公報中記載之鹼可溶性樹脂、韓國公開專利第10-2020-0078339號公報中記載之由式1表示之樹脂、日本特開2021-134350號公報中記載之樹脂。又,作為樹脂,亦能夠較佳地使用具有茀骨架之樹脂。作為具有茀骨架之樹脂,可舉出美國專利申請公開第2017/0102610號說明書中記載之樹脂。Examples of the resin include (meth)acrylic resins, epoxy resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfide resins, polyethersulfide resins, polyphenylene resins, polyarylether phosphine oxide resins, polyimide resins, polyamide resins, polyamideimide resins, polyolefin resins, cycloolefin resins, polyester resins, styrene resins, vinyl acetate resins, polyvinyl alcohol resins, polyvinyl acetal resins, polyurethane resins, polyurea resins, etc. These resins may be used alone or in combination of two or more. As a cycloolefin hydrocarbon resin, from the perspective of improving heat resistance, norbornene resin is preferred. As commercially available products of norbornene resins, for example, the ARTON series manufactured by JSR Corporation (for example, ARTON F4520) and the like can be cited. In addition, as the resin, the resin described in paragraphs 0091 to 0099 of International Publication No. 2022/065215, the blocked polyisocyanate resin described in Japanese Patent Gazette No. 2016-222891, the resin described in Japanese Patent Gazette No. 2020-122052, and the resin described in Japanese Patent Gazette No. 2020-11165 can also be used. A resin described in Japanese Patent Publication No. 6, a resin described in Japanese Patent Publication No. 2020-139021, a resin containing a structural unit having a ring structure in the main chain and a structural unit having a biphenyl group in the side chain described in Japanese Patent Publication No. 2017-138503, paragraphs 0199 to 0233 of Japanese Patent Publication No. 2020-186373 The resin described in , the alkali-soluble resin described in Japanese Patent Publication No. 2020-186325, the resin represented by Formula 1 described in Korean Patent Publication No. 10-2020-0078339, the copolymer containing an epoxy group and an acid group described in International Publication No. 2022/030445, Japanese Patent Publication No. 2020-1 The resin described in paragraphs 0199 to 0233 of the Gazette of 86373, the alkali-soluble resin described in the Gazette of Japanese Patent No. 2020-186325, the resin represented by Formula 1 described in the Gazette of Korean Patent No. 10-2020-0078339, and the resin described in the Gazette of Japanese Patent No. 2021-134350. In addition, as a resin, a resin having a fluorene skeleton can also be preferably used. As a resin having a fluorene skeleton, a resin described in the specification of U.S. Patent Application Publication No. 2017/0102610 can be cited.
作為樹脂,使用具有酸基之樹脂為較佳。作為酸基,例如,可舉出羧基、磷酸基、磺基、酚性羥基等。該等酸基可以僅為1種,亦可以為2種以上。具有酸基之樹脂亦能夠用作分散劑。具有酸基之樹脂的酸值為30~500mgKOH/g為較佳。下限為50mgKOH/g以上為較佳,70mgKOH/g以上為更佳。上限為400mgKOH/g以下為較佳,200mgKOH/g以下為更佳,150mgKOH/g以下為進一步較佳,120mgKOH/g以下為最佳。As the resin, it is preferred to use a resin having an acid group. As the acid group, for example, a carboxyl group, a phosphoric acid group, a sulfonic group, a phenolic hydroxyl group, etc. can be cited. Such acid groups can be only one kind, or can be two or more kinds. The resin having an acid group can also be used as a dispersant. The acid value of the resin having an acid group is preferably 30 to 500 mgKOH/g. The lower limit is preferably 50 mgKOH/g or more, and 70 mgKOH/g or more is more preferred. The upper limit is preferably 400 mgKOH/g or less, 200 mgKOH/g or less is more preferred, 150 mgKOH/g or less is further preferred, and 120 mgKOH/g or less is the best.
作為樹脂,使用具有聚合性基之樹脂亦較佳。聚合性基為含有乙烯性不飽和鍵之基團及環狀醚基為較佳,含有乙烯性不飽和鍵之基團為更佳。As the resin, a resin having a polymerizable group is also preferably used. The polymerizable group is preferably a group containing an ethylenic unsaturated bond and a cyclic ether group, and more preferably a group containing an ethylenic unsaturated bond.
樹脂包含作為分散劑的樹脂為亦較佳。作為分散劑,可舉出酸性分散劑(酸性樹脂)、鹼性分散劑(鹼性樹脂)。在此,酸性分散劑(酸性樹脂)表示酸基的量多於鹼基的量之樹脂。作為酸性分散劑(酸性樹脂),將酸基的量和鹼基的量的合計量設定為100莫耳%時,酸基的量為70莫耳%以上之樹脂為較佳。酸性分散劑(酸性樹脂)所具有之酸基較佳為羧基。酸性分散劑(酸性樹脂)的酸值為10~105mgKOH/g為較佳。又,鹼性分散劑(鹼性樹脂)表示鹼基的量多於酸基的量之樹脂。作為鹼性分散劑(鹼性樹脂),將酸基的量與鹼基的量的合計量設定為100莫耳%時,鹼基的量超過50莫耳%以上的樹脂為較佳。鹼性分散劑所具有之鹼基為胺基為較佳。The resin preferably includes a resin as a dispersant. As the dispersant, an acidic dispersant (acidic resin) and an alkaline dispersant (alkaline resin) can be cited. Here, the acidic dispersant (acidic resin) refers to a resin in which the amount of acid groups is greater than the amount of alkaline groups. As the acidic dispersant (acidic resin), when the total amount of the amount of acid groups and the amount of alkaline groups is set to 100 mol%, a resin in which the amount of acid groups is 70 mol% or more is preferred. The acid group possessed by the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably 10 to 105 mgKOH/g. In addition, an alkaline dispersant (alkaline resin) refers to a resin in which the amount of alkaline groups is greater than the amount of acidic groups. As an alkaline dispersant (alkaline resin), when the total amount of acidic groups and alkaline groups is set to 100 mol%, a resin in which the amount of alkaline groups exceeds 50 mol% is preferred. The alkaline groups possessed by the alkaline dispersant are preferably amine groups.
用作分散劑之樹脂為接枝樹脂亦較佳。關於接枝樹脂的詳細內容,能夠參考日本特開2012-255128號公報的0025~0094段的記載,該內容編入本說明書中。The resin used as the dispersant is preferably a grafted resin. For details of the grafted resin, reference can be made to paragraphs 0025 to 0094 of Japanese Patent Application Laid-Open No. 2012-255128, which is incorporated herein by reference.
用作分散劑之樹脂為在主鏈及側鏈中的至少一個上包含氮原子之聚亞胺系分散劑亦較佳。作為聚亞胺系分散劑,具有主鏈及側鏈且在主鏈及側鏈中的至少一個上具有鹼性氮原子之樹脂為較佳,該主鏈包含具有pKa14以下的官能基之部分結構,該側鏈的原子數為40~10000。鹼性氮原子只要為呈鹼性之氮原子,則並沒有特別限制。聚亞胺系分散劑能夠參考日本特開2012-255128號公報的0102~0166段的記載,該內容編入本說明書中。The resin used as the dispersant is preferably a polyimine-based dispersant containing nitrogen atoms in at least one of the main chain and the side chain. As the polyimine-based dispersant, a resin having a main chain and a side chain and having a basic nitrogen atom in at least one of the main chain and the side chain is preferred, the main chain containing a partial structure having a functional group with a pKa of 14 or less, and the number of atoms in the side chain is 40 to 10,000. There is no particular limitation on the basic nitrogen atom as long as it is alkaline. The polyimine-based dispersant can be described in paragraphs 0102 to 0166 of Japanese Patent Application Publication No. 2012-255128, and the content is incorporated into this specification.
用作分散劑之樹脂為在核部鍵結有複數個聚合物鏈之結構的樹脂亦較佳。作為此類樹脂,例如,可舉出樹枝狀聚合物(包括星型聚合物)。又,作為樹枝狀聚合物的具體例,可舉出日本特開2013-043962號公報的0196~0209段中記載之高分子化合物C-1~C-31等。The resin used as the dispersant is preferably a resin having a structure in which a plurality of polymer chains are bonded to the core. Examples of such resins include dendritic polymers (including star polymers). Specific examples of dendritic polymers include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of Japanese Patent Application Publication No. 2013-043962.
用作分散劑之樹脂為包含側鏈具有含有乙烯性不飽和鍵之基團之重複單元之樹脂亦較佳。側鏈具有含有乙烯性不飽和鍵之基團之重複單元的含量在樹脂的所有重複單元中為10莫耳%以上為較佳,10~80莫耳%為更佳,20~70莫耳%為進一步較佳。The resin used as the dispersant is also preferably a resin containing repeating units having a group containing an ethylenically unsaturated bond in the side chain. The content of the repeating units having a group containing an ethylenically unsaturated bond in the side chain is preferably 10 mol% or more, more preferably 10 to 80 mol%, and even more preferably 20 to 70 mol% in all the repeating units of the resin.
作為分散劑,亦能夠使用日本特開2018-087939號公報中記載之樹脂、日本專利第6432077號公報的0219~0221段中記載之嵌段共聚物(EB-1)~(EB-9)、國際公開第2016/104803號中記載之具有聚酯側鏈之聚乙烯亞胺、國際公開第2019/125940號中記載之嵌段共聚物、日本特開2020-066687號公報中記載之具有丙烯醯胺結構單元之嵌段聚合物、日本特開2020-066688號公報中記載之具有丙烯醯胺結構單元之嵌段聚合物等。As the dispersant, the resin described in Japanese Patent Publication No. 2018-087939, the block copolymers (EB-1) to (EB-9) described in paragraphs 0219 to 0221 of Japanese Patent Publication No. 6432077, the polyethyleneimine having a polyester side chain described in International Publication No. 2016/104803, the block copolymer described in International Publication No. 2019/125940, the block polymer having an acrylamide structural unit described in Japanese Patent Publication No. 2020-066687, the block polymer having an acrylamide structural unit described in Japanese Patent Publication No. 2020-066688, etc. can also be used.
分散劑亦能夠作為市售品獲得,作為此類具體例,可舉出BYK-Chemie GmbH製DISPERBYK系列、Japan Lubrizol Corporation製SOLSPERSE系列、BASF公司製Efka系列、Ajinomoto Fine-Techno Co., Inc.製Ajispar系列等。又,亦能夠使用日本特開2012-137564號公報的0129段中記載之產品、日本特開2017-194662號公報的0235段中記載之產品作為分散劑。Dispersants can also be obtained as commercial products, and specific examples thereof include DISPERBYK series manufactured by BYK-Chemie GmbH, SOLSPERSE series manufactured by Japan Lubrizol Corporation, Efka series manufactured by BASF, and Ajispar series manufactured by Ajinomoto Fine-Techno Co., Inc. In addition, the product described in paragraph 0129 of Japanese Patent Application Publication No. 2012-137564 and the product described in paragraph 0235 of Japanese Patent Application Publication No. 2017-194662 can also be used as the dispersant.
組成物的總固體成分中硬化性化合物的含量為1~95質量%為較佳。下限為2質量%以上為較佳,5質量%以上為更佳,7質量%以上為進一步較佳,10質量%以上為特佳。上限為94質量%以下為較佳,90質量%以下為更佳,85質量%以下為進一步較佳,80質量%以下為特佳。The content of the curable compound in the total solid content of the composition is preferably 1 to 95 mass %. The lower limit is preferably 2 mass % or more, more preferably 5 mass % or more, further preferably 7 mass % or more, and particularly preferably 10 mass % or more. The upper limit is preferably 94 mass % or less, more preferably 90 mass % or less, further preferably 85 mass % or less, and particularly preferably 80 mass % or less.
本發明的組成物包含聚合性化合物作為硬化性化合物時,組成物的總固體成分中聚合性化合物的含量為1~85質量%為較佳。下限為2質量%以上為較佳,3質量%以上為更佳,5質量%以上為進一步較佳。上限為80質量%以下為較佳,70質量%以下為更佳。When the composition of the present invention contains a polymerizable compound as a curable compound, the content of the polymerizable compound in the total solid content of the composition is preferably 1 to 85 mass %. The lower limit is preferably 2 mass % or more, more preferably 3 mass % or more, and even more preferably 5 mass % or more. The upper limit is preferably 80 mass % or less, and more preferably 70 mass % or less.
本發明的組成物包含聚合性單體作為硬化性化合物時,組成物的總固體成分中聚合性單體的含量為1~50質量%為較佳。下限為2質量%以上為較佳,3質量%以上為更佳,5質量%以上為進一步較佳。上限為30質量%以下為較佳,20質量%以下為更佳。When the composition of the present invention contains a polymerizable monomer as a curable compound, the content of the polymerizable monomer in the total solid content of the composition is preferably 1 to 50 mass %. The lower limit is preferably 2 mass % or more, more preferably 3 mass % or more, and even more preferably 5 mass % or more. The upper limit is preferably 30 mass % or less, and more preferably 20 mass % or less.
本發明的組成物包含具有含有乙烯性不飽和鍵的基團之化合物作為硬化性化合物時,組成物的總固體成分中具有含有乙烯性不飽和鍵的基團之化合物的含量為1~70質量%為較佳。下限為2質量%以上為較佳,3質量%以上為更佳,5質量%以上為進一步較佳。上限為65質量%以下為較佳,60質量%以下為更佳。When the composition of the present invention contains a compound having a group containing an ethylenically unsaturated bond as a curable compound, the content of the compound having a group containing an ethylenically unsaturated bond in the total solid content of the composition is preferably 1 to 70% by mass. The lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. The upper limit is preferably 65% by mass or less, and more preferably 60% by mass or less.
本發明的組成物包含具有環狀醚基之化合物作為硬化性化合物時,組成物的總固體成分中具有環狀醚基之化合物的含量為1~95質量%為較佳。下限為2質量%以上為較佳,3質量%以上為更佳,5質量%以上為進一步較佳。上限為80質量%以下為較佳,70質量%以下為更佳,60質量%以下為進一步較佳。When the composition of the present invention contains a compound having a cyclic ether group as a curable compound, the content of the compound having a cyclic ether group in the total solid content of the composition is preferably 1 to 95% by mass. The lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less.
本發明的組成物包含樹脂作為硬化性化合物時,組成物的總固體成分中樹脂的含量為1~85質量%為較佳。下限為2質量%以上為較佳,5質量%以上為更佳,7質量%以上為進一步較佳,10質量%以上為特佳。上限為80質量%以下為較佳,75質量%以下為更佳,70質量%以下為進一步較佳,40質量%以下為特佳。When the composition of the present invention contains a resin as a curable compound, the content of the resin in the total solid content of the composition is preferably 1 to 85 mass %. The lower limit is preferably 2 mass % or more, more preferably 5 mass % or more, even more preferably 7 mass % or more, and particularly preferably 10 mass % or more. The upper limit is preferably 80 mass % or less, more preferably 75 mass % or less, even more preferably 70 mass % or less, and particularly preferably 40 mass % or less.
本發明的組成物含有作為分散劑的樹脂時,組成物的總固體成分中作為分散劑的樹脂的含量為0.1~40質量%為較佳。上限為25質量%以下為較佳,20質量%以下為進一步較佳。下限為0.5質量%以上為較佳,1質量%以上為進一步較佳。又,作為分散劑的樹脂的含量相對於顏料100質量份為1~100質量份為較佳。上限為80質量份以下為較佳,75質量份以下為更佳。下限為2.5質量份以上為較佳,5質量份以上為更佳。When the composition of the present invention contains a resin as a dispersant, the content of the resin as a dispersant in the total solid content of the composition is preferably 0.1 to 40 mass %. The upper limit is preferably 25 mass % or less, and 20 mass % or less is further preferably. The lower limit is preferably 0.5 mass % or more, and 1 mass % or more is further preferably. In addition, the content of the resin as a dispersant is preferably 1 to 100 mass parts relative to 100 mass parts of the pigment. The upper limit is preferably 80 mass parts or less, and 75 mass parts or less is more preferably. The lower limit is preferably 2.5 mass parts or more, and 5 mass parts or more is more preferably.
本發明的組成物可以僅包含1種硬化性化合物,亦可以包含2種以上。包含2種以上的硬化性化合物時,該等的合計量在上述範圍內為較佳。The composition of the present invention may contain only one curable compound or may contain two or more curable compounds. When containing two or more curable compounds, the total amount thereof is preferably within the above range.
<<溶劑>> 本發明的組成物含有溶劑。作為溶劑,可舉出水、有機溶劑,有機溶劑為較佳。作為有機溶劑,可舉出酯系溶劑、酮系溶劑、醇系溶劑、醯胺系溶劑、醚系溶劑、烴系溶劑等。關於該等的詳細內容,能夠參考國際公開第2015/166779號的0223段,該內容編入本說明書中。又,亦能夠較佳地使用經環狀烷基取代之酯系溶劑、經環狀烷基取代之酮系溶劑。作為有機溶劑的具體例,可舉出聚乙二醇單甲醚、二氯甲烷、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙基賽路蘇乙酸酯、乳酸乙酯、二乙二醇二甲醚、乙酸丁酯、3-甲氧基丙酸甲酯、2-庚酮、2-戊酮、3-戊酮、4-庚酮、環己酮、2-甲基環己酮、3-甲基環己酮、4-甲基環己酮、環庚酮、環辛酮、乙酸環己酯、環戊酮、乙基卡必醇乙酸酯、丁基卡必醇乙酸酯、丙二醇單甲醚、丙二醇單甲醚乙酸酯、3-甲氧基-N,N-二甲基丙醯胺、3-丁氧基-N,N-二甲基丙醯胺、丙二醇二乙酸酯、3-甲氧基丁醇、甲基乙基酮、γ-丁內酯、環丁碸、苯甲醚、1,4-二乙醯氧基丁烷、二乙二醇單乙醚乙酸酯、1,3-丁二醇二乙酸酯、二丙二醇甲醚乙酸酯、二丙酮醇(亦稱為4-羥基-4-甲基-2-戊酮)、2-甲氧基丙基乙酸酯、2-甲氧基-1-丙醇、異丙醇等。然而,有時出於環境方面等理由,減少作為有機溶劑之芳香族烴類(苯、甲苯、二甲苯、乙苯等)為較佳(例如,相對於有機溶劑總量,能夠設定為50質量ppm(parts per million:百萬分率)以下,亦能夠設定為10質量ppm以下,亦能夠設定為1質量ppm以下)。 <<Solvent>> The composition of the present invention contains a solvent. As the solvent, water and organic solvents can be cited, and organic solvents are preferred. As the organic solvent, ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, hydrocarbon solvents, etc. can be cited. For details of the above, reference can be made to paragraph 0223 of International Publication No. 2015/166779, which is incorporated into this specification. In addition, cyclic alkyl-substituted ester solvents and cyclic alkyl-substituted ketone solvents can also be preferably used. Specific examples of the organic solvent include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl celulose acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, 2-pentanone, 3-pentanone, 4-heptanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, Propylene glycol monomethyl ether acetate, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, propylene glycol diacetate, 3-methoxybutanol, methyl ethyl ketone, γ-butyrolactone, cyclobutane, anisole, 1,4-diethoxybutane, diethylene glycol monoethyl ether acetate, 1,3-butanediol diacetate, dipropylene glycol methyl ether acetate, diacetone alcohol (also known as 4-hydroxy-4-methyl-2-pentanone), 2-methoxypropyl acetate, 2-methoxy-1-propanol, isopropyl alcohol, etc. However, sometimes for environmental reasons, it is better to reduce the amount of aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) used as organic solvents (for example, relative to the total amount of organic solvents, it can be set to less than 50 mass ppm (parts per million), can be set to less than 10 mass ppm, and can also be set to less than 1 mass ppm).
本發明中,使用金屬含量少的有機溶劑為較佳,有機溶劑的金屬含量例如為10質量ppb(parts per billion:十億分率)以下為較佳。可以根據需要使用質量ppt(parts per trillion:兆分率)級別的有機溶劑,此類有機溶劑例如由Toyo Gosei Co., Ltd提供(化學工業日報,2015年11月13日)。In the present invention, it is preferred to use an organic solvent with a low metal content. For example, the metal content of the organic solvent is preferably 10 ppb (parts per billion) or less. An organic solvent with a mass ppt (parts per trillion) level can be used as needed. Such an organic solvent is provided, for example, by Toyo Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015).
作為從有機溶劑中去除金屬等雜質之方法,例如能夠舉出蒸餾(分子蒸餾、薄膜蒸餾等)或使用了過濾器之過濾。作為用於過濾之過濾器的過濾器孔徑,10μm以下為較佳,5μm以下為更佳,3μm以下為進一步較佳。過濾器的材質較佳為聚四氟乙烯、聚乙烯或尼龍。As a method for removing impurities such as metals from an organic solvent, for example, distillation (molecular distillation, thin film distillation, etc.) or filtration using a filter can be cited. The pore size of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.
有機溶劑可以包含異構物(原子數相同,但結構不同的化合物)。又,異構物可以僅包含1種,亦可以包含複數種。The organic solvent may contain isomers (compounds having the same atomic number but different structures). The isomers may contain only one type or may contain a plurality of types.
過氧化物在有機溶劑中的含有率為0.8mmol/L以下為較佳,實質上不包含過氧化物為更佳。The content of peroxide in the organic solvent is preferably 0.8 mmol/L or less, and it is more preferred that the organic solvent contains substantially no peroxide.
溶劑在組成物中的含量為10~97質量%為較佳。下限為30質量%以上為較佳,40質量%以上為更佳,50質量%以上為進一步較佳,60質量%以上為更進一步較佳,70質量%以上為特佳。上限為96質量%以下為較佳,95質量%以下為更佳。組成物可以僅含有1種溶劑,亦可以含有2種以上。包含2種以上時,該等的合計量在上述範圍內為較佳。The content of the solvent in the composition is preferably 10 to 97% by mass. The lower limit is preferably 30% by mass or more, more preferably 40% by mass or more, further preferably 50% by mass or more, further preferably 60% by mass or more, and particularly preferably 70% by mass or more. The upper limit is preferably 96% by mass or less, and more preferably 95% by mass or less. The composition may contain only one solvent or two or more. When two or more solvents are included, the total amount thereof is preferably within the above range.
<<其他紅外線吸收劑>> 本發明的組成物能夠含有上述特定化合物以外的紅外線吸收劑(其他紅外線吸收劑)。藉由進一步含有其他紅外線吸收劑,能夠形成能夠遮蔽更廣波長範圍的紅外線之膜。其他紅外線吸收劑可以為染料,亦可以為顏料(粒子)。作為其他紅外線吸收劑,可舉出吡咯并吡咯化合物、聚次甲基化合物、方酸菁化合物、酞菁化合物、萘酞菁化合物、夸特銳烯(quaterrylene)化合物、部花青化合物、克酮鎓化合物、氧雜菁化合物、亞銨化合物、二硫醇化合物、三芳基甲烷化合物、吡咯亞甲基化合物、甲亞胺化合物、蒽醌化合物、二苯并呋喃酮化合物、二硫烯金屬錯合物、金屬氧化物、金屬硼化物等,選自方酸菁化合物及酞菁化合物中的至少一種為較佳。 <<Other infrared absorbers>> The composition of the present invention can contain infrared absorbers (other infrared absorbers) other than the above-mentioned specific compounds. By further containing other infrared absorbers, a film capable of shielding infrared rays in a wider wavelength range can be formed. Other infrared absorbers can be dyes or pigments (particles). As other infrared absorbers, pyrrolopyrrole compounds, polymethine compounds, squarylene compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterrylene compounds, merocyanine compounds, crotonium compounds, oxocyanine compounds, ammonium compounds, dithiol compounds, triarylmethane compounds, pyrrole methylene compounds, azomethine compounds, anthraquinone compounds, dibenzofuranone compounds, dithiolene metal complexes, metal oxides, metal borides, etc. are cited. At least one selected from squarylene compounds and phthalocyanine compounds is preferred.
作為吡咯并吡咯化合物,可舉出日本特開2009-263614號公報的0016~0058段中記載之化合物、日本特開2011-068731號公報的0037~0052段中記載之化合物、國際公開第2015/166873號的0010~0033段中記載之化合物等。作為方酸菁化合物,可舉出日本特開2011-208101號公報的0044~0049段中記載之化合物、日本專利第6065169號公報的0060~0061段中記載之化合物、國際公開第2016/181987號的0040段中記載之化合物、日本特開2015-176046號公報中記載之化合物、國際公開第2016/190162號的0072段中記載之化合物、日本特開2016-074649號公報的0196~0228段中記載之化合物、日本特開2017-067963號公報的0124段中記載之化合物、國際公開第2017/135359號中記載之化合物、日本特開2017-114956號公報中記載之化合物、日本專利6197940號公報中記載之化合物、國際公開第2016/120166號中記載之化合物等。作為聚次甲基化合物,可舉出日本特開2009-108267號公報的0044~0045段中記載之化合物、日本特開2002-194040號公報的0026~0030段中記載之化合物、日本特開2015-172004號公報中記載之化合物、日本特開2015-172102號公報中記載之化合物、日本特開2008-088426號公報中記載之化合物、國際公開第2016/190162號的0090段中記載之化合物、日本特開2017-031394號公報中記載之化合物、日本特開2021-134350號公報中記載之化合物、國際公開第2021/085372號中記載之化合物等。作為克酮鎓化合物,可舉出日本特開2017-082029號公報中記載之化合物。作為亞銨化合物,例如,可舉出日本特表2008-528706號公報中記載之化合物、日本特開2012-012399號公報中記載之化合物、日本特開2007-092060號公報中記載之化合物、國際公開第2018/043564號的0048~0063段中記載之化合物。作為酞菁化合物,可舉出日本特開2012-077153號公報的0093段中記載之化合物、日本特開2006-343631號公報中記載之酞菁氧鈦、日本特開2013-195480號公報的0013~0029段中記載之化合物、日本專利第6081771號公報中記載之釩酞菁化合物、國際公開第2020/071470號中記載之化合物。作為萘酞菁化合物,可舉出日本特開2012-077153號公報的0093段中記載之化合物。作為二硫烯金屬錯合物,可舉出日本專利第5733804號公報中記載之化合物。作為金屬氧化物,例如,可舉出氧化銦錫、氧化銻錫、氧化鋅、Al摻雜氧化鋅、氟摻雜二氧化錫、鈮摻雜二氧化鈦、氧化鎢等。關於氧化鎢的詳細內容,能夠參考日本特開2016-006476號公報的0080段,該內容編入本說明書中。作為金屬硼化物,可舉出硼化鑭等。作為硼化鑭的市售品,可舉出LaB 6-F(Japan New Metals Co., Ltd.製)等。又,作為金屬硼化物,亦能夠使用國際公開第2017/119394號中記載之化合物。作為氧化銦錫的市售品,可舉出F-ITO(DOWA HIGHTECH CO., LTD.製)等。 Examples of the pyrrolopyrrole compound include compounds described in paragraphs 0016 to 0058 of JP-A-2009-263614, compounds described in paragraphs 0037 to 0052 of JP-A-2011-068731, and compounds described in paragraphs 0010 to 0033 of International Publication No. 2015/166873. Examples of the squarylium compound include the compounds described in paragraphs 0044 to 0049 of Japanese Patent Publication No. 2011-208101, the compounds described in paragraphs 0060 to 0061 of Japanese Patent Publication No. 6065169, the compounds described in paragraph 0040 of International Publication No. 2016/181987, the compounds described in Japanese Patent Publication No. 2015-176046, the compounds described in paragraph 0072 of International Publication No. 2016/190162. Compounds described in paragraphs 0196 to 0228 of Japanese Patent Application Publication No. 2016-074649, compounds described in paragraph 0124 of Japanese Patent Application Publication No. 2017-067963, compounds described in International Publication No. 2017/135359, compounds described in Japanese Patent Application Publication No. 2017-114956, compounds described in Japanese Patent Application No. 6197940, compounds described in International Publication No. 2016/120166, etc. Examples of the polymethine compound include compounds described in paragraphs 0044 to 0045 of Japanese Patent Application Publication No. 2009-108267, compounds described in paragraphs 0026 to 0030 of Japanese Patent Application Publication No. 2002-194040, compounds described in Japanese Patent Application Publication No. 2015-172004, compounds described in Japanese Patent Application Publication No. 2015-172102. Compounds described in Japanese Patent Publication No. 2008-088426, compounds described in paragraph 0090 of International Publication No. 2016/190162, compounds described in Japanese Patent Publication No. 2017-031394, compounds described in Japanese Patent Publication No. 2021-134350, compounds described in International Publication No. 2021/085372, etc. As the crotonium compound, the compound described in Japanese Patent Publication No. 2017-082029 can be cited. Examples of the ammonium compound include compounds described in JP-A-2008-528706, compounds described in JP-A-2012-012399, compounds described in JP-A-2007-092060, and compounds described in paragraphs 0048 to 0063 of International Publication No. 2018/043564. Phthalocyanine compounds include compounds described in paragraph 0093 of Japanese Patent Application Laid-Open No. 2012-077153, titanium phthalocyanine described in Japanese Patent Application Laid-Open No. 2006-343631, compounds described in paragraphs 0013 to 0029 of Japanese Patent Application Laid-Open No. 2013-195480, vanadium phthalocyanine compounds described in Japanese Patent Application Laid-Open No. 6081771, and compounds described in International Publication No. 2020/071470. Naphthalocyanine compounds include compounds described in paragraph 0093 of Japanese Patent Application Laid-Open No. 2012-077153. Disulfide metal complexes include compounds described in Japanese Patent Application Laid-Open No. 5733804. As metal oxides, for example, indium tin oxide, antimony tin oxide, zinc oxide, Al-doped zinc oxide, fluorine-doped tin dioxide, niobium-doped titanium dioxide, tungsten oxide, etc. can be cited. For details of tungsten oxide, reference can be made to paragraph 0080 of Japanese Patent Publication No. 2016-006476, which is incorporated into this specification. As metal borides, titanium boride, etc. can be cited. As commercial products of titanium boride, LaB 6 -F (manufactured by Japan New Metals Co., Ltd.) can be cited. In addition, as metal borides, compounds described in International Publication No. 2017/119394 can also be used. Examples of commercially available indium tin oxide include F-ITO (manufactured by DOWA HIGHTECH CO., LTD.).
作為紅外線吸收劑,亦能夠使用日本特開2017-197437號公報中記載之方酸菁化合物、日本特開2017-025311號公報中記載之方酸菁化合物、國際公開第2016/154782號中記載之方酸菁化合物、日本專利第5884953號公報中記載之方酸菁化合物、日本專利第6036689號公報中記載之方酸菁化合物、日本專利第5810604號公報中記載之方酸菁化合物、國際公開第2017/213047號的0090~0107段中記載之方酸菁化合物、日本特開2018-054760號公報的0019~0075段中記載之含吡咯環化合物、日本特開2018-040955號公報的0078~0082段中記載之含吡咯環化合物、日本特開2018-002773號公報的0043~0069段中記載之含吡咯環化合物、日本特開2018-041047號公報的0024~0086段中記載之在醯胺α位具有芳香環之方酸菁化合物、日本特開2017-179131號公報中記載之醯胺連結型方酸菁化合物、日本特開2017-141215號公報中記載之具有吡咯雙型方酸菁骨架或克酮鎓骨架之化合物、日本特開2017-082029號公報中記載之二氫咔唑雙型方酸菁化合物、日本特開2017-068120號公報的0027~0114段中記載之非對稱型化合物、日本特開2017-067963號公報中記載之含吡咯環化合物(咔唑型)、日本專利第6251530號公報中記載之酞菁化合物等。As the infrared absorber, the squaryl cyanine compound described in Japanese Patent Publication No. 2017-197437, the squaryl cyanine compound described in Japanese Patent Publication No. 2017-025311, the squaryl cyanine compound described in International Publication No. 2016/154782, the squaryl cyanine compound described in Japanese Patent No. 5884953, and the squaryl cyanine compound described in Japanese Patent No. 6036689 can also be used. , the squarylium cyanine compound described in Japanese Patent No. 5810604, the squarylium cyanine compound described in paragraphs 0090 to 0107 of International Publication No. 2017/213047, the pyrrole ring-containing compound described in paragraphs 0019 to 0075 of Japanese Patent Publication No. 2018-054760, the pyrrole ring-containing compound described in paragraphs 0078 to 0082 of Japanese Patent Publication No. 2018-040955, the Japanese Patent Publication No. The pyrrole ring-containing compound described in paragraphs 0043 to 0069 of the Japanese Patent Publication No. 2018-002773, the squarylium compound having an aromatic ring at the amide α position described in paragraphs 0024 to 0086 of the Japanese Patent Publication No. 2018-041047, the amide-linked squarylium compound described in Japanese Patent Publication No. 2017-179131, the pyrrole bi-type squarylium compound described in Japanese Patent Publication No. 2017-141215 Compounds having a carboxycyanine skeleton or a crotonium skeleton, dihydrocarbazole bis-type squarylium compounds described in Japanese Patent Application Laid-Open No. 2017-082029, asymmetric compounds described in paragraphs 0027 to 0114 of Japanese Patent Application Laid-Open No. 2017-068120, pyrrole ring-containing compounds (carbazole type) described in Japanese Patent Application Laid-Open No. 2017-067963, phthalocyanine compounds described in Japanese Patent Application No. 6251530, etc.
作為其他紅外線吸收劑,亦能夠使用歐洲專利第3628645號說明書的0025段中記載之由下述式表示之氧化鎢。 M 1 aM 2 bW cO d(P(O) nR m) eM 1、M 2表示銨陽離子或金屬陽離子,a為0.01~0.5,b為0~0.5,c為1,d為2.5~3,e為0.01~0.75,n為1、2或3,m為1、2或3,R表示可具有取代基之烴基。 As another infrared absorber , tungsten oxide represented by the following formula described in paragraph 0025 of the specification of European Patent No. 3628645 can also be used. M1aM2bWcOd ( P(O) nRm ) eM1 and M2 represent ammonium cations or metal cations, a is 0.01 to 0.5, b is 0 to 0.5, c is 1, d is 2.5 to 3, e is 0.01 to 0.75, n is 1, 2 or 3, m is 1, 2 or 3, and R represents a hydrocarbon group which may have a substituent.
相對於上述特定化合物100質量份,其他紅外線吸收劑的含量為1~100質量份為較佳,3~60質量份為更佳,5~40質量份為進一步較佳。 組成物的總固體成分中上述特定化合物和其他紅外線吸收劑的合計含量為1質量%以上為較佳,3質量%以上為更佳,5質量%以上為進一步較佳。上述合計含量的上限為50質量%以下為較佳,40質量%以下為更佳,30質量%以下為進一步較佳。 The content of other infrared absorbers is preferably 1 to 100 parts by mass, preferably 3 to 60 parts by mass, and more preferably 5 to 40 parts by mass relative to 100 parts by mass of the above-mentioned specific compound. The total content of the above-mentioned specific compound and other infrared absorbers in the total solid content of the composition is preferably 1% by mass or more, more preferably 3% by mass or more, and more preferably 5% by mass or more. The upper limit of the above-mentioned total content is preferably 50% by mass or less, more preferably 40% by mass or less, and more preferably 30% by mass or less.
<<顏料衍生物>> 本發明的組成物能夠含有顏料衍生物。顏料衍生物可用作分散助劑。分散助劑係指用於在組成物中提高顏料的分散性之材料。 <<Pigment derivative>> The composition of the present invention can contain a pigment derivative. The pigment derivative can be used as a dispersing aid. A dispersing aid refers to a material used to improve the dispersibility of a pigment in a composition.
作為顏料衍生物,可舉出具有選自由色素結構及三𠯤結構組成之群組中的至少一種結構及酸基或鹼基之化合物。As the pigment derivative, there can be cited a compound having at least one structure selected from the group consisting of a pigment structure and a tribasic structure and an acid group or a base group.
作為上述色素結構,可舉出方酸菁色素結構、吡咯并吡咯色素結構、二酮基吡咯并吡咯色素結構、喹吖酮色素結構、蒽醌色素結構、二蒽醌色素結構、苯并異吲哚色素結構、噻𠯤靛藍色素結構、偶氮色素結構、喹啉黃色素結構、酞菁色素結構、萘酞菁色素結構、二㗁𠯤色素結構、苝色素結構、紫環酮色素結構、苯并咪唑啉酮色素結構、苯并噻唑色素結構、苯并咪唑色素結構及苯并㗁唑色素結構,方酸菁色素結構、吡咯并吡咯色素結構、二酮基吡咯并吡咯色素結構、酞菁色素結構、喹吖酮色素結構及苯并咪唑啉酮色素結構為較佳,方酸菁色素結構及吡咯并吡咯色素結構為更佳。Examples of the pigment structure include a squarylium pigment structure, a pyrrolopyrrole pigment structure, a diketopyrrolopyrrole pigment structure, a quinacridone pigment structure, an anthraquinone pigment structure, a dianthraquinone pigment structure, a benzisoindole pigment structure, a thiazolidine indigo pigment structure, an azo pigment structure, a quinoline yellow pigment structure, a phthalocyanine pigment structure, a naphthalocyanine pigment structure, a dithiazolidine pigment structure, and a perylene pigment structure. , purple ring ring pigment structure, benzimidazolone pigment structure, benzothiazole pigment structure, benzimidazole pigment structure and benzophenone pigment structure, squarylium pigment structure, pyrrolopyrrole pigment structure, diketopyrrolopyrrole pigment structure, phthalocyanine pigment structure, quinacridone pigment structure and benzimidazolone pigment structure are preferred, and squarylium pigment structure and pyrrolopyrrole pigment structure are more preferred.
作為顏料衍生物所具有之酸基,可舉出羧基、磺基、磷酸基、硼酸基、羧酸醯胺基、磺酸醯胺基、醯亞胺酸基及該等的鹽等。作為構成鹽之原子或原子團,可舉出鹼金屬離子(Li +、Na +、K +等)、鹼土類金屬離子(Ca 2+、Mg 2+等)、銨離子、咪唑鎓離子、吡啶鎓離子、鏻離子等。作為羧酸醯胺基,由-NHCOR y1表示之基團為較佳。作為磺酸醯胺基,由-NHSO 2R y2表示之基團為較佳。作為醯亞胺酸基,由-SO 2NHSO 2R y3、-CONHSO 2R y4、-CONHCOR y5或-SO 2NHCOR y6表示之基團為較佳,-SO 2NHSO 2R y3為更佳。R y1~R y6分別獨立地表示烷基或芳基。R y1~R y6所表示之烷基及芳基可以具有取代基。作為取代基,鹵素原子為較佳,氟原子為更佳。 Examples of the acid group possessed by the pigment derivative include carboxyl, sulfonic, phosphoric, boric, carboxylic acid amide, sulfonic acid amide, imidic acid and salts thereof. Examples of atoms or atomic groups constituting the salt include alkaline metal ions (Li + , Na + , K + , etc.), alkaline earth metal ions (Ca 2+ , Mg 2+ , etc.), ammonium ions, imidazolium ions, pyridinium ions, phosphonium ions, etc. As the carboxylic acid amide group, a group represented by -NHCOR y1 is preferred. As the sulfonic acid amide group, a group represented by -NHSO 2 R y2 is preferred. As the imidic acid group, a group represented by -SO 2 NHSO 2 R y3 , -CONHSO 2 R y4 , -CONHCOR y5 or -SO 2 NHCOR y6 is preferred, and -SO 2 NHSO 2 R y3 is more preferred. R y1 to R y6 each independently represent an alkyl group or an aryl group. The alkyl group and aryl group represented by R y1 to R y6 may have a substituent. As the substituent, a halogen atom is preferred, and a fluorine atom is more preferred.
作為顏料衍生物所具有之鹼基,可舉出胺基、吡啶基及其鹽、銨基的鹽以及酞醯亞胺甲基。作為構成鹽之原子或原子團,可舉出氫氧化物離子、鹵素離子、羧酸離子、磺酸離子、苯氧離子等。Examples of the base group of the pigment derivative include amino groups, pyridyl groups and their salts, ammonium salts, and phthalimide methyl groups. Examples of the atom or atom group constituting the salt include hydroxide ions, halogen ions, carboxylic acid ions, sulfonic acid ions, and phenoxy ions.
作為顏料衍生物的具體例,可舉出國際公開第2016/035695號的0037~0054段中記載之化合物、國際公開第2017/146092號的0061~0086段中記載之化合物、國際公開第2018/230387號的0017~0068段中記載之化合物、國際公開第2020/054718號的0085~0099段中記載之化合物、國際公開第2020/054718號的0099段中記載之化合物、國際公開第2022/085485號的0124段中記載之化合物、日本特開2018-168244號公報中記載之苯并咪唑酮化合物或該等的鹽、日本專利第6996282號中記載之具有通式(1)的異吲哚啉骨架之化合物等。Specific examples of pigment derivatives include the compounds described in paragraphs 0037 to 0054 of International Publication No. 2016/035695, the compounds described in paragraphs 0061 to 0086 of International Publication No. 2017/146092, the compounds described in paragraphs 0017 to 0068 of International Publication No. 2018/230387, and the compounds described in paragraphs 0085 to 0086 of International Publication No. 2020/054718. The compounds described in paragraph 099 of International Publication No. 2020/054718, the compounds described in paragraph 0124 of International Publication No. 2022/085485, the benzimidazolone compounds or salts thereof described in Japanese Patent Application Publication No. 2018-168244, and the compounds having an isoindoline skeleton of the general formula (1) described in Japanese Patent No. 6996282.
顏料衍生物的含量相對於顏料100質量份為1~50質量份為較佳。下限值為3質量份以上為較佳,5質量份以上為更佳。上限值為40質量份以下為較佳,30質量份以下為更佳。顏料衍生物可以僅使用1種,亦可以使用2種以上。使用2種以上時,合計量在上述範圍內為較佳。The content of the pigment derivative is preferably 1 to 50 parts by mass relative to 100 parts by mass of the pigment. The lower limit is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more. The upper limit is preferably 40 parts by mass or less, and more preferably 30 parts by mass or less. Only one type of the pigment derivative may be used, or two or more types may be used. When two or more types are used, the total amount is preferably within the above range.
<<光聚合起始劑>> 本發明的組成物包含聚合性化合物時,本發明的組成物進一步含有光聚合起始劑為較佳。作為光聚合起始劑,並沒有特別限制,能夠適當地選自公知的光聚合起始劑。例如,對紫外線區域至可見區域的光線具有感光性之化合物為較佳。光聚合起始劑為光自由基聚合起始劑為較佳。 <<Photopolymerization initiator>> When the composition of the present invention contains a polymerizable compound, it is preferred that the composition of the present invention further contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited and can be appropriately selected from known photopolymerization initiators. For example, a compound having photosensitivity to light in the ultraviolet region to the visible region is preferred. The photopolymerization initiator is preferably a photoradical polymerization initiator.
作為光聚合起始劑,可舉出鹵化烴衍生物(例如,具有三𠯤骨架之化合物、具有㗁二唑骨架之化合物等)、醯基膦化合物、六芳基雙咪唑化合物、肟化合物、有機過氧化物、硫化合物、酮化合物、芳香族鎓鹽、α-羥基酮化合物、α-胺基酮化合物等。從曝光靈敏度的觀點考慮,光聚合起始劑為三鹵甲基三𠯤化合物、苄基二甲基縮酮化合物、α-羥基酮化合物、α-胺基酮化合物、醯基膦化合物、氧化膦化合物、茂金屬化合物、肟化合物、六芳基雙咪唑化合物、鎓化合物、苯并噻唑化合物、二苯甲酮化合物、苯乙酮化合物、環戊二烯-苯-鐵錯合物、鹵甲基㗁二唑化合物及3-芳基取代香豆素化合物為較佳,選自肟化合物、α-羥基酮化合物、α-胺基酮化合物及醯基膦化合物中的化合物為更佳,肟化合物為進一步較佳。又,作為光聚合起始劑,可舉出日本特開2014-130173號公報的0065~0111段中記載之化合物、日本專利第6301489號公報中記載之化合物、MATERIAL STAGE 37~60p,vol.19,No.3,2019中記載之過氧化物系光聚合起始劑、國際公開第2018/221177號中記載之光聚合起始劑、國際公開第2018/110179號中記載之光聚合起始劑、日本特開2019-043864號公報中記載之光聚合起始劑、日本特開2019-044030號公報中記載之光聚合起始劑、日本特開2019-167313號公報中記載之過氧化物系起始劑、日本特開2020-055992號公報中記載之具有㗁唑烷基之胺基苯乙酮系起始劑、日本特開2013-190459號公報中記載之肟系光聚合起始劑、日本特開2020-172619號公報中記載之聚合物、國際公開第2020/152120號中記載之由式1表示之化合物、日本特開2021-181406號公報中記載之化合物、日本特開2022-013379號公報中記載之光聚合起始劑、日本特開2022-015747號公報中記載之由式(1)表示之化合物、日本特表2021-507058號公報中記載之含氟之茀肟酯系光起始劑、中國專利申請公開第110764367號說明書中記載之起始劑、日本特表2022-518535號公報中記載之起始劑、國際公開第2021/175855號中記載之起始劑等,該等內容編入本說明書中。As the photopolymerization initiator, there can be mentioned halogenated hydrocarbon derivatives (for example, compounds having a trioxane skeleton, compounds having a diazole skeleton, etc.), acylphosphine compounds, hexaarylbisimidazole compounds, oxime compounds, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, α-hydroxyketone compounds, α-aminoketone compounds, etc. From the viewpoint of exposure sensitivity, the photopolymerization initiator is preferably a trihalomethyl trioxane compound, a benzyl dimethyl ketal compound, an α-hydroxy ketone compound, an α-amino ketone compound, an acyl phosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a hexaarylbisimidazole compound, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound, a cyclopentadiene-benzene-iron complex, a halogenated methyl oxadiazole compound, and a 3-aryl substituted coumarin compound. A compound selected from the group consisting of an oxime compound, an α-hydroxy ketone compound, an α-amino ketone compound, and an acyl phosphine compound is more preferred, and an oxime compound is further preferred. In addition, as the photopolymerization initiator, there can be cited the compounds described in paragraphs 0065 to 0111 of Japanese Patent Publication No. 2014-130173, the compounds described in Japanese Patent Publication No. 6301489, the peroxide-based photopolymerization initiator described in MATERIAL STAGE 37 to 60p, vol. 19, No. 3, 2019, the photopolymerization initiator described in International Publication No. 2018/221177, the photopolymerization initiator described in International Publication No. 2018/110179, the photopolymerization initiator described in Japanese Patent Publication No. 2019-043864, and the photopolymerization initiator described in Japanese Patent Publication No. 2019 -044030, the peroxide-based initiator described in Japanese Patent Publication No. 2019-167313, the aminoacetophenone-based initiator having an oxazolidinyl group described in Japanese Patent Publication No. 2020-055992, the oxime-based photopolymerization initiator described in Japanese Patent Publication No. 2013-190459, the The polymer described in the publication No. 72619, the compound represented by formula 1 described in International Publication No. 2020/152120, the compound described in Japanese Patent Publication No. 2021-181406, the photopolymerization initiator described in Japanese Patent Publication No. 2022-013379, the compound represented by formula (1) described in Japanese Patent Publication No. 2022-015747 Compounds, fluorinated fluorine oxime ester-based photoinitiators described in Japanese Patent Publication No. 2021-507058, initiators described in the specification of Chinese Patent Application Publication No. 110764367, initiators described in Japanese Patent Publication No. 2022-518535, initiators described in International Publication No. 2021/175855, etc., the contents of which are incorporated into this specification.
作為六芳基雙咪唑化合物的具體例,可舉出2,2’,4-三(2-氯苯基)-5-(3,4-二甲氧基苯基)-4,5-二苯基-1,1’-雙咪唑等。Specific examples of the hexaarylbiimidazole compound include 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl-1,1'-biimidazole and the like.
作為α-羥基酮化合物的市售品,可舉出Omnirad 184、Omnirad 1173、Omnirad 2959、Omnirad 127(以上為IGM Resins B.V.公司製)、Irgacure 184、Irgacure 1173、Irgacure 2959、Irgacure 127(以上為BASF公司製)等。作為α-胺基酮化合物的市售品,可舉出Omnirad 907、Omnirad 369、Omnirad 369E、Omnirad 379EG(以上為IGM Resins B.V.公司製)、Irgacure 907、Irgacure 369、Irgacure 369E、Irgacure 379EG(以上為BASF公司製)等。作為醯基膦化合物的市售品,可舉出Omnirad 819、Omnirad TPO(以上為IGM Resins B.V.公司製)、Irgacure 819、Irgacure TPO(以上為BASF公司製)等。Examples of commercially available α-hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, and Omnirad 127 (all manufactured by IGM Resins B.V.), Irgacure 184, Irgacure 1173, Irgacure 2959, and Irgacure 127 (all manufactured by BASF). Examples of commercially available α-aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, and Omnirad 379EG (all manufactured by IGM Resins B.V.), Irgacure 907, Irgacure 369, Irgacure 369E, and Irgacure 379EG (all manufactured by BASF). Examples of commercially available acylphosphine compounds include Omnirad 819 and Omnirad TPO (both manufactured by IGM Resins B.V.), Irgacure 819 and Irgacure TPO (both manufactured by BASF).
作為肟化合物,可舉出國際公開第2022/085485號的0142段中記載之化合物、日本專利第5430746號中記載之化合物、日本專利第5647738號中記載之化合物、日本特開2021-173858號公報的由通式(1)表示之化合物或0022~0024段中記載之化合物、日本特開2021-170089號公報的由通式(1)表示之化合物或0117~0120段中記載之化合物等。作為肟化合物的具體例,可舉出3-苯甲醯氧基亞胺基丁-2-酮、3-乙醯氧基亞胺基丁-2-酮、3-丙醯氧基亞胺基丁-2-酮、2-乙醯氧基亞胺基戊-3-酮、2-乙醯氧基亞胺基-1-苯基丙-1-酮、2-苯甲醯氧基亞胺基-1-苯基丙-1-酮、3-(4-甲苯磺醯氧基)亞胺基丁-2-酮及2-乙氧基羰氧基亞胺基-1-苯基丙-1-酮等、1-[4-(苯硫基)苯基]-3-環己烷-丙-1,2-二酮-2-(O-乙醯肟)。作為市售品,可舉出Irgacure OXE01、Irgacure OXE02、Irgacure OXE03、Irgacure OXE04(以上為BASF公司製)、TR-PBG-301、TR-PBG-304、TR-PBG-327(TRONLY公司製)、Adeka Optomer N-1919(ADEKA CORPORATION製,日本特開2012-014052號公報中記載之光聚合起始劑2)。又,作為肟化合物,使用沒有著色性之化合物或透明性高且不易變色的化合物亦較佳。作為市售品,可舉出ADEKA ARKLS NCI-730、NCI-831、NCI-930(以上為ADEKA CORPORATION製)等。Examples of the oxime compound include compounds described in paragraph 0142 of International Publication No. 2022/085485, compounds described in Japanese Patent No. 5430746, compounds described in Japanese Patent No. 5647738, compounds represented by the general formula (1) or compounds described in paragraphs 0022 to 0024 of Japanese Patent Application Laid-Open No. 2021-173858, and compounds represented by the general formula (1) or compounds described in paragraphs 0117 to 0120 of Japanese Patent Application Laid-Open No. 2021-170089. Specific examples of the oxime compound include 3-benzoyloxyiminobutan-2-one, 3-acetyloxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetyloxyiminopentan-3-one, 2-acetyloxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, and the like, and 1-[4-(phenylthio)phenyl]-3-cyclohexane-propane-1,2-dione-2-(O-acetyl oxime). As commercial products, Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, Irgacure OXE04 (all manufactured by BASF), TR-PBG-301, TR-PBG-304, TR-PBG-327 (manufactured by TRONLY), Adeka Optomer N-1919 (manufactured by ADEKA CORPORATION, photopolymerization initiator 2 described in Japanese Patent Publication No. 2012-014052). In addition, as the oxime compound, it is also preferable to use a compound without coloring or a compound with high transparency and low color change. As commercial products, ADEKA ARKLS NCI-730, NCI-831, NCI-930 (all manufactured by ADEKA CORPORATION) and the like can be cited.
作為光聚合起始劑,亦能夠使用具有茀環之肟化合物、具有咔唑環的至少一個苯環成為萘環的骨架之肟化合物、具有氟原子之肟化合物、具有硝基之肟化合物、具有苯并呋喃骨架之肟化合物、在咔唑骨架上鍵結了具有羥基之取代基之肟化合物、國際公開第2022/085485號的0143~0149段中記載之化合物。As the photopolymerization initiator, an oxime compound having a fluorene ring, an oxime compound having a carbazole ring in which at least one benzene ring is a naphthalene ring skeleton, an oxime compound having a fluorine atom, an oxime compound having a nitro group, an oxime compound having a benzofuran skeleton, an oxime compound having a hydroxyl substituent bonded to the carbazole skeleton, and the compounds described in paragraphs 0143 to 0149 of International Publication No. 2022/085485 can also be used.
以下示出可較佳地用於本發明之肟化合物的具體例,但本發明並不限定於該等。Specific examples of oxime compounds that can be preferably used in the present invention are shown below, but the present invention is not limited thereto.
[化學式6] [化學式7] [化學式8] [化學式9] [Chemical formula 6] [Chemical formula 7] [Chemical formula 8] [Chemical formula 9]
肟化合物為在波長350~500nm的範圍內具有極大吸收波長之化合物為較佳,在波長360~480nm的範圍內具有極大吸收波長之化合物為更佳。又,從靈敏度的觀點考慮,肟化合物在波長365nm或波長405nm處的莫耳吸光係數高為較佳,1000~300000為更佳,2000~300000為進一步較佳,5000~200000為特佳。化合物的莫耳吸光係數能夠使用公知的方法測定。例如,藉由分光光度計(Varian公司製Cary-5分光光度計(spectrophotometer)),使用乙酸乙酯溶劑,以0.01g/L的濃度測定為較佳。The oxime compound is preferably a compound having a maximum absorption wavelength in the range of 350 to 500 nm, and more preferably a compound having a maximum absorption wavelength in the range of 360 to 480 nm. In addition, from the perspective of sensitivity, the oxime compound preferably has a high molar absorption coefficient at a wavelength of 365 nm or a wavelength of 405 nm, preferably 1000 to 300,000, more preferably 2000 to 300,000, and particularly preferably 5000 to 200,000. The molar absorption coefficient of the compound can be measured using a known method. For example, it is preferably measured by a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g/L.
作為光聚合起始劑,可以使用2官能或3官能以上的光自由基聚合起始劑。藉由使用此類光自由基聚合起始劑,從光自由基聚合起始劑的一分子產生2個以上的自由基,因此可獲得良好的靈敏度。又,在使用了非對稱結構的化合物時,結晶性下降而在溶劑等中的溶解性變高,隨時間的經過變得難以析出,藉此能夠提高組成物的經時穩定性。作為2官能或3官能以上的光自由基聚合起始劑的具體例,可舉出國際公開第2022/065215號的0148段中記載之化合物。As a photopolymerization initiator, a difunctional or trifunctional or higher photoradical polymerization initiator can be used. By using this type of photoradical polymerization initiator, two or more free radicals are generated from one molecule of the photoradical polymerization initiator, so that good sensitivity can be obtained. In addition, when a compound with an asymmetric structure is used, the crystallinity decreases and the solubility in a solvent or the like increases, and it becomes difficult to precipitate over time, thereby improving the time stability of the composition. As a specific example of a difunctional or trifunctional or higher photoradical polymerization initiator, the compound described in paragraph 0148 of International Publication No. 2022/065215 can be cited.
組成物的總固體成分中光聚合起始劑的含量為0.1~40質量%為較佳,0.5~35質量%為更佳,1~30質量%為進一步較佳。組成物可以僅含有1種光聚合起始劑,亦可以含有2種以上。包含2種以上時,該等的合計量在上述範圍內為較佳。The content of the photopolymerization initiator in the total solid content of the composition is preferably 0.1 to 40 mass %, more preferably 0.5 to 35 mass %, and even more preferably 1 to 30 mass %. The composition may contain only one photopolymerization initiator or two or more. When two or more photopolymerization initiators are contained, the total amount thereof is preferably within the above range.
<<硬化劑>> 本發明的組成物包含具有環狀醚基之化合物時,進一步包含硬化劑為較佳。作為硬化劑,例如,可舉出胺系化合物、酸酐系化合物、醯胺系化合物、酚化合物、多元羧酸、硫醇化合物等。作為硬化劑的具體例,可舉出琥珀酸、偏苯三甲酸、焦蜜石酸、N,N-二甲基-4-胺吡啶、新戊四醇四(3-巰基丙酸酯)等。硬化劑亦能夠使用日本特開2016-075720號公報的0072~0078段中記載之化合物、日本特開2017-036379號公報中記載之化合物。相對於具有環狀醚基之化合物的100質量份,硬化劑的含量為0.01~20質量份為較佳,0.01~10質量份為更佳,0.1~6.0質量份為進一步較佳。 <<Hardener>> When the composition of the present invention contains a compound having a cyclic ether group, it is preferable to further contain a hardener. As the hardener, for example, amine compounds, acid anhydride compounds, amide compounds, phenol compounds, polycarboxylic acids, thiol compounds, etc. can be cited. As specific examples of the hardener, succinic acid, trimellitic acid, pyromelitic acid, N,N-dimethyl-4-aminopyridine, pentaerythritol tetrakis (3-butyl propionate) and the like can be cited. The hardener can also use compounds described in paragraphs 0072 to 0078 of Japanese Patent Publication No. 2016-075720 and compounds described in Japanese Patent Publication No. 2017-036379. The content of the hardener is preferably 0.01 to 20 parts by mass, more preferably 0.01 to 10 parts by mass, and even more preferably 0.1 to 6.0 parts by mass relative to 100 parts by mass of the compound having a cyclic ether group.
<<彩色著色劑>> 本發明的組成物能夠含有彩色著色劑。作為彩色著色劑,可舉出紅色著色劑、綠色著色劑、藍色著色劑、黃色著色劑、紫色著色劑及橙色著色劑。彩色著色劑可以為顏料,亦可以為染料。可以同時使用顏料和染料。又,顏料可以為無機顏料、有機顏料中的任一種。又,顏料亦能夠使用將無機顏料或有機-無機顏料的一部分用有機發色團取代之材料。藉由將無機顏料或有機-無機顏料用有機發色團取代,能夠容易進行色相設計。 <<Color coloring agent>> The composition of the present invention can contain a color coloring agent. As the color coloring agent, red coloring agent, green coloring agent, blue coloring agent, yellow coloring agent, purple coloring agent and orange coloring agent can be cited. The color coloring agent can be a pigment or a dye. A pigment and a dye can be used at the same time. In addition, the pigment can be any of an inorganic pigment and an organic pigment. In addition, the pigment can also use a material in which a part of an inorganic pigment or an organic-inorganic pigment is replaced with an organic chromophore. By replacing an inorganic pigment or an organic-inorganic pigment with an organic chromophore, hue design can be easily performed.
顏料的平均一次粒徑為1~200nm為較佳。下限為5nm以上為較佳,10nm以上為更佳。上限為180nm以下為較佳,150nm以下為更佳,100nm以下為進一步較佳。再者,在本說明書中,顏料的一次粒徑能夠藉由透射式電子顯微鏡觀察顏料的一次粒子,並根據所獲得之圖像照片來求出。具體而言,求出顏料的一次粒子的投影面積,並算出與其相對應之等效圓直徑作為顏料的一次粒徑。又,將本說明書中的平均一次粒徑設定為針對400個顏料的一次粒子之一次粒徑的算數平均值。又,顏料的一次粒子係指未凝聚的獨立粒子。The average primary particle size of the pigment is preferably 1 to 200 nm. The lower limit is preferably 5 nm or more, and more preferably 10 nm or more. The upper limit is preferably 180 nm or less, more preferably 150 nm or less, and even more preferably 100 nm or less. Furthermore, in this specification, the primary particle size of the pigment can be obtained by observing the primary particles of the pigment under a transmission electron microscope and based on the image photographs obtained. Specifically, the projected area of the primary particles of the pigment is obtained, and the equivalent circular diameter corresponding thereto is calculated as the primary particle size of the pigment. In addition, the average primary particle size in this specification is set to the arithmetic mean of the primary particle sizes of 400 primary particles of the pigment. In addition, the primary particles of the pigment refer to independent particles that are not agglomerated.
彩色著色劑包含顏料為較佳。顏料在彩色著色劑中的含量為50質量%以上為較佳,70質量%以上為更佳,80質量%以上為進一步較佳,90質量%以上為特佳。作為顏料,可舉出以下所示者。The coloring agent preferably contains a pigment. The content of the pigment in the coloring agent is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and particularly preferably 90% by mass or more. Examples of the pigment include the following.
顏料索引(C.I.)顏料黃1、2、3、4、5、6、10、11、12、13、14、15、16、17、18、20、24、31、32、34、35、35:1、36、36:1、37、37:1、40、42、43、53、55、60、61、62、63、65、73、74、77、81、83、86、93、94、95、97、98、100、101、104、106、108、109、110、113、114、115、116、117、118、119、120、123、125、126、127、128、129、137、138、139、147、148、150、151、152、153、154、155、156、161、162、164、166、167、168、169、170、171、172、173、174、175、176、177、179、180、181、182、185、187、188、193、194、199、213、214、215、228、231、232(次甲基系)、233(喹啉系)、234(胺基酮系)、235(胺基酮系)、236(胺基酮系)等(以上為黃色顏料)、 C.I.顏料橙2、5、13、16、17:1、31、34、36、38、43、46、48、49、51、52、55、59、60、61、62、64、71、73等(以上為橙色顏料)、 C.I.顏料紅1、2、3、4、5、6、7、9、10、14、17、22、23、31、38、41、48:1、48:2、48:3、48:4、49、49:1、49:2、52:1、52:2、53:1、57:1、60:1、63:1、66、67、81:1、81:2、81:3、83、88、90、105、112、119、122、123、144、146、149、150、155、166、168、169、170、171、172、175、176、177、178、179、184、185、187、188、190、200、202、206、207、208、209、210、216、220、224、226、242、246、254、255、264、269、270、272、279、291、294(𠮿口星系,Organo Ultramarine(有機群青)、Bluish Red(藍紅))、295(單偶氮系)、296(二偶氮系)、297(胺基酮)等(以上為紅色顏料)、 C.I.顏料綠7、10、36、37、58、59、62、63、64(酞菁系)、65(酞菁系)、66(酞菁系)等(以上為綠色顏料)、 C.I.顏料紫1、19、23、27、32、37、42、60(三芳基甲烷系)、61(𠮿口星系)等(以上為紫色顏料)、 C.I.顏料藍1、2、15、15:1、15:2、15:3、15:4、15:6、16、22、29、60、64、66、79、80、87(單偶氮系)、88(次甲基系)等(以上為藍色顏料)。 Color Index (C.I.) Color Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128 、129、137、138、139、147、148、150、151、152、153、154、155、156、161、162、164、166、167、168、169、170、171、172、173、174、175、176、177、179、180、181、182、185、187、188、193、194、199、213、214、215、228、231、232 (methyl series), 233 (quinoline series), 234 (amino ketone series), 235 (amino ketone series), 236 (amino ketone series), etc. (the above are yellow pigments), C.I. pigment orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. (the above are orange pigments), C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149 、150、155、166、168、169、170、171、172、175、176、177、178、179、184、185、187、188、190、200、202、206、207、208、209、210、216、220、224、226、242、246、254、255、264、269、270、272、279、291、294 (𠮿口 Galaxy, Organo Ultramarine (organic ultramarine), Bluish Red (blue red), 295 (monoazo series), 296 (diazo series), 297 (amino ketone), etc. (the above are red pigments), C.I. pigment green 7, 10, 36, 37, 58, 59, 62, 63, 64 (phthalocyanine series), 65 (phthalocyanine series), 66 (phthalocyanine series), etc. (the above are green pigments), C.I. pigment purple 1, 19, 23, 27, 32, 37, 42, 60 (triarylmethane series), 61 (Phosphorus galaxy), etc. (the above are purple pigments), C.I. Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 29, 60, 64, 66, 79, 80, 87 (monoazo series), 88 (methine series), etc. (the above are blue pigments).
作為綠色著色劑,亦能夠使用在一分子中的鹵素原子數平均為10~14個、溴原子數平均為8~12個、氯原子數平均為2~5個之鹵化鋅酞菁顏料。作為具體例,可舉出國際公開第2015/118720號中記載之化合物。又,作為綠色著色劑,亦能夠使用國際公開第2022/085485號的0029段中記載之化合物、日本特開2020-070426號公報中記載之鋁酞菁化合物、日本特表2020-504758號公報中記載之二芳基甲烷化合物等。As a green colorant, a zinc phthalocyanine halide pigment having an average of 10 to 14 halogen atoms, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms in one molecule can also be used. As a specific example, the compound described in International Publication No. 2015/118720 can be cited. In addition, as a green colorant, the compound described in paragraph 0029 of International Publication No. 2022/085485, the aluminum phthalocyanine compound described in Japanese Patent Publication No. 2020-070426, and the diarylmethane compound described in Japanese Patent Publication No. 2020-504758 can also be used.
作為藍色著色劑,亦能夠使用具有磷原子之鋁酞菁化合物。作為具體例,可舉出日本特開2012-247591號公報的0022~0030段、日本特開2011-157478號公報的0047段中記載之化合物。As a blue coloring agent, an aluminum phthalocyanine compound having a phosphorus atom can also be used. Specific examples include compounds described in paragraphs 0022 to 0030 of Japanese Patent Application Laid-Open No. 2012-247591 and paragraph 0047 of Japanese Patent Application Laid-Open No. 2011-157478.
作為黃色著色劑,能夠使用國際公開第2022/085485號的0031~0033段中記載之化合物、日本特開2019-073695號公報中記載之次甲基染料、日本特開2019-073696號公報中記載之次甲基染料。As the yellow coloring agent, the compounds described in paragraphs 0031 to 0033 of International Publication No. 2022/085485, the methine dyes described in JP-A-2019-073695, and the methine dyes described in JP-A-2019-073696 can be used.
作為紅色著色劑,亦能夠使用國際公開第2022/085485號的0034段中記載之化合物、日本特開2020-085947號公報中記載之溴化二酮吡咯并吡咯化合物。As the red coloring agent, the compound described in paragraph 0034 of International Publication No. 2022/085485 and the brominated diketopyrrolopyrrole compound described in Japanese Patent Application Publication No. 2020-085947 can also be used.
彩色著色劑亦能夠使用染料。作為染料,並沒有特別限制,能夠使用公知的染料。例如,可舉出吡唑偶氮系染料、苯胺基偶氮系染料、三芳基甲烷系染料、蒽醌系染料、蒽吡啶酮系染料、亞苄基系染料、氧雜菁系染料、吡唑并三唑偶氮系染料、吡啶酮偶氮系染料、花青系染料、啡噻𠯤系染料、吡咯并吡唑甲亞胺系染料、𠮿口星系染料、酞菁系染料、苯并哌喃系染料、靛藍系染料、吡咯亞甲基系染料等。又,染料亦能夠使用日本特開2012-158649號公報中記載之噻唑化合物、日本特開2011-184493號公報中記載之偶氮化合物、日本特開2011-145540號公報中記載之偶氮化合物。The coloring agent may also be a dye. There is no particular limitation on the dye, and known dyes may be used. For example, pyrazole azo dyes, aniline azo dyes, triarylmethane dyes, anthraquinone dyes, anthrapyridone dyes, benzylidene dyes, oxocyanine dyes, pyrazolotriazole azo dyes, pyridone azo dyes, cyanine dyes, phenothiocyanate dyes, pyrrolopyrazole azoimine dyes, galaxy dyes, phthalocyanine dyes, benzopyran dyes, indigo dyes, pyrromethene dyes, etc. may be cited. Moreover, as the dye, the thiazole compound described in Japanese Patent Application Laid-Open No. 2012-158649, the azo compound described in Japanese Patent Application Laid-Open No. 2011-184493, and the azo compound described in Japanese Patent Application Laid-Open No. 2011-145540 can also be used.
作為彩色著色劑,亦能夠使用韓國公開專利第10-2020-0028160號公報中記載之三芳基甲烷染料聚合物、日本特開2020-117638號公報中記載之𠮿口星化合物、國際公開第2020/174991號中記載之酞菁化合物、日本特開2020-160279號公報中記載之異吲哚啉化合物或該等的鹽、韓國公開專利第10-2020-0069442號公報中記載之由式1表示之化合物、韓國公開專利第10-2020-0069730號公報中記載之由式1表示之化合物、韓國公開專利第10-2020-0069070號公報中記載之由式1表示之化合物、韓國公開專利第10-2020-0069067號公報中記載之由式1表示之化合物、韓國公開專利第10-2020-0069062號公報中記載之由式1表示之化合物、日本專利第6809649號公報中記載之鹵化鋅酞菁顏料、日本特開2020-180176號公報中記載之異吲哚啉化合物、日本特開2021-187913號公報中記載之啡噻𠯤系化合物、國際公開第2022/004261號中記載之鹵化鋅酞菁、國際公開第2021/250883號中記載之鹵化鋅酞菁、韓國公開專利第10-2020-0030759號公報的由式1表示之喹啉黃化合物、韓國公開專利第10-2020-0061793號公報中記載之高分子染料、日本特開2022-029701號公報中記載之著色劑、國際公開第2022/014635號中記載之異吲哚啉化合物、國際公開第2022/024926號中記載之鋁酞菁化合物、日本特開2022-045895號公報中記載之化合物、國際公開第2022/050051號中記載之化合物。彩色著色劑可以為輪烷,色素骨架可以用於輪烷的環狀結構,亦可以用於棒狀結構,亦可以用於環狀及棒狀結構兩者。As a coloring agent, triarylmethane dye polymers described in Korean Patent Publication No. 10-2020-0028160, phthalocyanine compounds described in Japanese Patent Publication No. 2020-117638, phthalocyanine compounds described in International Publication No. 2020/174991, isoindoline compounds or salts thereof described in Japanese Patent Publication No. 2020-160279, and phthalocyanine compounds described in Korean Patent Publication No. 10-2020-0069442 can also be used. The compound represented by formula 1, the compound represented by formula 1 described in Korean Publication No. 10-2020-0069730, the compound represented by formula 1 described in Korean Publication No. 10-2020-0069070, the compound represented by formula 1 described in Korean Publication No. 10-2020-0069067, the compound represented by formula 1 described in Korean Publication No. 10-2020-0069062, the compound represented by formula 1 described in Japanese Patent No. The zinc phthalocyanine halogenide pigment described in the publication No. 6809649, the isoindoline compound described in the publication No. 2020-180176, the thiophene thiocyanate compound described in the publication No. 2021-187913, the zinc phthalocyanine halogenide described in the publication No. 2022/004261, the zinc phthalocyanine halogenide described in the publication No. 2021/250883, the quinoline yellow pigment represented by formula 1 in the publication No. 10-2020-0030759 Compounds, polymer dyes described in Korean Patent Publication No. 10-2020-0061793, colorants described in Japanese Patent Publication No. 2022-029701, isoindoline compounds described in International Publication No. 2022/014635, aluminum phthalocyanine compounds described in International Publication No. 2022/024926, compounds described in Japanese Patent Publication No. 2022-045895, and compounds described in International Publication No. 2022/050051. The colorant may be a rotaxane, and the pigment skeleton may be used for the cyclic structure of the rotaxane, may be used for the rod-shaped structure, or may be used for both the cyclic and rod-shaped structures.
本發明的組成物含有彩色著色劑時,組成物的總固體成分中彩色著色劑的含量為1~50質量%為較佳。本發明的組成物含有2種以上的彩色著色劑時,該等的合計量在上述範圍內為較佳。When the composition of the present invention contains a coloring agent, the content of the coloring agent in the total solid content of the composition is preferably 1 to 50 mass %. When the composition of the present invention contains two or more coloring agents, the total amount of the coloring agents is preferably within the above range.
將本發明的組成物用作紅外線截止濾波器用途時,本發明的組成物實質上不含有彩色著色劑為較佳。再者,本發明的組成物實質上不含有彩色著色劑係指組成物的總固體成分中彩色著色劑的含量為0.5質量%以下,0.1質量%以下為較佳,不含有彩色著色劑為更佳。When the composition of the present invention is used as an infrared cutoff filter, it is preferred that the composition of the present invention substantially does not contain a coloring agent. Furthermore, the composition of the present invention substantially does not contain a coloring agent means that the content of the coloring agent in the total solid content of the composition is 0.5 mass% or less, preferably 0.1 mass% or less, and it is more preferred that the composition does not contain a coloring agent.
<<使紅外線透射且遮蔽可見光之色材>> 本發明的組成物亦能夠含有使紅外線透射且遮蔽可見光之色材(以下,亦稱為遮蔽可見光之色材)。包含遮蔽可見光之色材之組成物可較佳地用作紅外線透射濾波器形成用組成物。 <<Color material that transmits infrared light and blocks visible light>> The composition of the present invention can also contain a color material that transmits infrared light and blocks visible light (hereinafter, also referred to as a color material that blocks visible light). The composition containing the color material that blocks visible light can be preferably used as a composition for forming an infrared transmission filter.
遮蔽可見光之色材為吸收紫色至紅色的波長區域的光之色材為較佳。又,遮蔽可見光之色材為遮蔽波長450~650nm的波長區域的光之色材為較佳。又,遮蔽可見光之色材為使波長900~1500nm的光透射之色材為較佳。遮蔽可見光之色材滿足以下(A)及(B)中至少一個必要條件為較佳。 (A):含有2種以上的彩色著色劑,以2種以上的彩色著色劑的組合形成黑色。 (B):包含有機系黑色著色劑。 The color material that shields visible light is preferably a color material that absorbs light in the wavelength range of purple to red. In addition, the color material that shields visible light is preferably a color material that shields light in the wavelength range of 450 to 650 nm. In addition, the color material that shields visible light is preferably a color material that transmits light in the wavelength range of 900 to 1500 nm. The color material that shields visible light is preferably one that satisfies at least one of the following necessary conditions (A) and (B). (A): Contains two or more color colorants, and the combination of two or more color colorants forms black. (B): Contains an organic black colorant.
作為彩色著色劑,可舉出上述者。作為有機系黑色著色劑,例如,可舉出雙苯并呋喃酮化合物、甲亞胺化合物、苝化合物、偶氮化合物等,雙苯并呋喃酮化合物、苝化合物為較佳。作為雙苯并呋喃酮化合物,可舉出日本特表2010-534726號公報、日本特表2012-515233號公報、日本特表2012-515234號公報等中記載之化合物,例如,能夠作為BASF公司製“Irgaphor Black”獲得。作為苝化合物,可舉出日本特開2017-226821號公報的0016~0020段中記載之化合物、C.I.顏料黑31、32等。作為甲亞胺化合物,可舉出本日本特開平01-170601號公報、日本特開平02-034664號公報等中記載之化合物,例如能夠作為Dainichiseika Color & Chemicals Mfg.Co., Ltd.製“CHROMO FINE BLACK A1103”獲得。As color coloring agents, the above-mentioned ones can be cited. As organic black coloring agents, for example, bisbenzofuranone compounds, azomethine compounds, perylene compounds, azo compounds, etc. can be cited, and bisbenzofuranone compounds and perylene compounds are preferred. As bisbenzofuranone compounds, compounds described in Japanese Patent Publication No. 2010-534726, Japanese Patent Publication No. 2012-515233, Japanese Patent Publication No. 2012-515234, etc. can be cited, for example, they can be obtained as "Irgaphor Black" manufactured by BASF. As perylene compounds, compounds described in paragraphs 0016 to 0020 of Japanese Patent Publication No. 2017-226821, C.I. Pigment Black 31, 32, etc. can be cited. Examples of the azomethine compound include compounds described in Japanese Patent Application Laid-Open No. 01-170601 and Japanese Patent Application Laid-Open No. 02-034664. For example, it is available as "CHROMO FINE BLACK A1103" manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.
作為以2種以上的彩色著色劑的組合形成黑色時的彩色著色劑的組合,例如可舉出以下(1)~(8)的態樣。 (1)含有黃色著色劑、藍色著色劑、紫色著色劑及紅色著色劑之態樣。 (2)含有黃色著色劑、藍色著色劑及紅色著色劑之態樣。 (3)含有黃色著色劑、紫色著色劑及紅色著色劑之態樣。 (4)含有黃色著色劑及紫色著色劑之態樣。 (5)含有綠色著色劑、藍色著色劑、紫色著色劑及紅色著色劑之態樣。 (6)含有紫色著色劑及橙色著色劑之態樣。 (7)含有綠色著色劑、紫色著色劑及紅色著色劑之態樣。 (8)含有綠色著色劑及紅色著色劑之態樣。 As a combination of color colorants for forming black by combining two or more color colorants, for example, the following (1) to (8) can be cited. (1) A state in which a yellow colorant, a blue colorant, a purple colorant, and a red colorant are contained. (2) A state in which a yellow colorant, a blue colorant, and a red colorant are contained. (3) A state in which a yellow colorant, a purple colorant, and a red colorant are contained. (4) A state in which a yellow colorant and a purple colorant are contained. (5) A state in which a green colorant, a blue colorant, a purple colorant, and a red colorant are contained. (6) A state in which a purple colorant and an orange colorant are contained. (7) Samples containing green colorant, purple colorant and red colorant. (8) Samples containing green colorant and red colorant.
本發明的組成物含有遮蔽可見光之色材時,組成物的總固體成分中遮蔽可見光之色材的含量為1~50質量%為較佳。下限為5質量%以上為較佳,10質量%以上為更佳,20質量%以上為進一步較佳,30質量%以上為特佳。When the composition of the present invention contains a colorant that shields visible light, the content of the colorant that shields visible light in the total solid content of the composition is preferably 1 to 50% by mass. The lower limit is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, and particularly preferably 30% by mass or more.
將本發明的組成物用作紅外線截止濾波器用途時,本發明的組成物實質上不含有遮蔽可見光之色材為較佳。再者,本發明的組成物實質上不含有遮蔽可見光之色材係指組成物的總固體成分中遮蔽可見光之色材的含量為0.5質量%以下,0.1質量%以下為較佳,不含有遮蔽可見光之色材為更佳。When the composition of the present invention is used as an infrared cutoff filter, it is preferred that the composition of the present invention substantially does not contain a colorant that blocks visible light. Furthermore, the composition of the present invention substantially does not contain a colorant that blocks visible light means that the content of the colorant that blocks visible light in the total solid content of the composition is 0.5 mass % or less, preferably 0.1 mass % or less, and it is more preferred that the composition does not contain a colorant that blocks visible light.
<<界面活性劑>> 本發明的組成物能夠含有界面活性劑。作為界面活性劑,能夠使用氟系界面活性劑、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、聚矽氧系界面活性劑等各種界面活性劑。界面活性劑為聚矽氧系界面活性劑或氟系界面活性劑為較佳。關於界面活性劑,能夠參考國際公開第2015/166779號的0238~0245段中記載之界面活性劑,該內容編入本說明書中。 <<Surfactant>> The composition of the present invention can contain a surfactant. As the surfactant, various surfactants such as fluorine-based surfactants, non-ionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants can be used. The surfactant is preferably a silicone-based surfactant or a fluorine-based surfactant. For the surfactant, reference can be made to the surfactants described in paragraphs 0238 to 0245 of International Publication No. 2015/166779, which is incorporated into this specification.
作為氟系界面活性劑,能夠使用國際公開第2022/085485號的0167~0173段中記載之化合物。As the fluorine-based surfactant, the compounds described in paragraphs 0167 to 0173 of International Publication No. 2022/085485 can be used.
作非離子系界面活性劑,可舉出國際公開第2022/085485號的0174段中記載之化合物。As non-ionic surfactants, the compounds described in paragraph 0174 of International Publication No. 2022/085485 can be cited.
作為聚矽氧系界面活性劑,例如,可舉出SH8400、SH8400 FLUID、FZ-2122、67 Additive、74 Additive、M Additive、SF 8419 OIL(以上為Dow Corning Toray Co., Ltd.製)、TSF-4440、TSF-4300、TSF-4445、TSF-4460、TSF-4452(以上為Momentive Performance Materials Inc.製)、KP-341、KF-6000、KF-6001、KF-6002、KF-6003(以上為Shin-Etsu Chemical Co., Ltd.製)、BYK-307、BYK-322、BYK-323、BYK-330、BYK-3760、BYK-UV3510(以上為BYK-Chemie GmbH製)等。聚矽氧系界面活性劑中還能夠使用下述結構的化合物。 [化學式10] Examples of the silicone-based surfactant include SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, SF 8419 OIL (all manufactured by Dow Corning Toray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials Inc.), KP-341, KF-6000, KF-6001, KF-6002, KF-6003 (all manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-307, BYK-322, BYK-323, BYK-330, BYK-3760, BYK-UV3510 (all manufactured by BYK-Chemie GmbH) etc. The following compounds can also be used as polysilicone surfactants. [Chemical formula 10]
組成物的總固體成分中界面活性劑的含量為0.001~1質量%為較佳,0.001~0.5質量%為更佳,0.001~0.2質量%為進一步較佳。組成物可以僅含有1種界面活性劑,亦可以含有2種以上。包含2種以上時,該等的合計量在上述範圍內為較佳。The content of the surfactant in the total solid content of the composition is preferably 0.001 to 1 mass %, more preferably 0.001 to 0.5 mass %, and even more preferably 0.001 to 0.2 mass %. The composition may contain only one surfactant or two or more. When two or more surfactants are included, the total amount thereof is preferably within the above range.
<<聚合抑制劑>> 本發明的組成物能夠含有聚合抑制劑。作為聚合抑制劑,可舉出氫醌、對甲氧基苯酚、二-三級丁基-對甲酚、五倍子酚、三級丁基鄰苯二酚、苯醌、4,4’-硫代雙(3-甲基-6-三級丁基苯酚)、2,2’-亞甲基雙(4-甲基-6-三級丁基苯酚)、N-亞硝基苯基羥胺鹽(銨鹽、第一鈰鹽等),對甲氧基苯酚為較佳。 組成物的總固體成分中聚合抑制劑的含量為0.0001~5質量%為較佳。組成物可以僅含有1種聚合抑制劑,亦可以含有2種以上。包含2種以上時,該等的合計量在上述範圍內為較佳。 <<Polymerization inhibitor>> The composition of the present invention can contain a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, gallol, tert-butyl o-catechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxylamine salts (ammonium salts, first arsenic salts, etc.), and p-methoxyphenol is preferred. The content of the polymerization inhibitor in the total solid content of the composition is preferably 0.0001 to 5% by mass. The composition may contain only one polymerization inhibitor, or may contain two or more. When two or more types are included, the total amount thereof is preferably within the above range.
<<矽烷偶合劑>> 本發明的組成物能夠含有矽烷偶合劑。矽烷偶合劑為具有水解性基之矽烷化合物為較佳,具有水解性基及其以外的官能基之矽烷化合物為更佳。水解性基係指與矽原子直接鍵結,並能夠藉由水解反應及縮合反應中的至少一種而產生矽氧烷鍵之取代基。作為水解性基,例如,可舉出鹵素原子、烷氧基、醯氧基等,烷氧基為較佳。矽烷偶合劑為具有烷氧基矽基之化合物為較佳。又,作為水解性基以外的官能基,例如,可舉出乙烯基、苯乙烯基、(甲基)丙烯醯基、巰基、環氧基、氧環丁烷基、胺基、脲基、硫醚基、異氰酸酯基、苯基等,(甲基)丙烯醯基及環氧基為較佳。矽烷偶合劑可舉出日本特開2009-288703號公報的0018~0036段中記載之化合物、日本特開2009-242604號公報的0056~0066段中記載之化合物。組成物的總固體成分中矽烷偶合劑的含量為0.01~15.0質量%為較佳,0.05~10.0質量%為更佳。組成物可以僅含有1種矽烷偶合劑,亦可以含有2種以上。包含2種以上時,該等的合計量在上述範圍內為較佳。 <<Silane coupling agent>> The composition of the present invention can contain a silane coupling agent. The silane coupling agent is preferably a silane compound having a hydrolyzable group, and a silane compound having a hydrolyzable group and a functional group other than the hydrolyzable group is more preferred. The hydrolyzable group refers to a substituent that directly bonds to a silicon atom and can generate a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, and the like, with an alkoxy group being preferred. The silane coupling agent is preferably a compound having an alkoxysilyl group. In addition, as functional groups other than hydrolyzable groups, for example, vinyl, styryl, (meth)acryl, octyl, epoxy, oxobutyl, amino, urea, thioether, isocyanate, phenyl, etc. can be cited, and (meth)acryl and epoxy are preferred. The silane coupling agent can be exemplified by the compounds described in paragraphs 0018 to 0036 of Japanese Patent Application Publication No. 2009-288703 and the compounds described in paragraphs 0056 to 0066 of Japanese Patent Application Publication No. 2009-242604. The content of the silane coupling agent in the total solid content of the composition is preferably 0.01 to 15.0 mass %, and more preferably 0.05 to 10.0 mass %. The composition may contain only one silane coupling agent or two or more. When two or more silane coupling agents are included, the total amount thereof is preferably within the above range.
<<紫外線吸收劑>> 本發明的組成物能夠含有紫外線吸收劑。作為紫外線吸收劑,可舉出共軛二烯化合物、胺基二烯化合物、水楊酸酯化合物、二苯甲酮化合物、苯并三唑化合物、丙烯腈化合物、羥苯基三𠯤化合物、吲哚化合物、三𠯤化合物、二苯甲醯基化合物等。作為此類化合物的具體例,可舉出日本特開2009-217221號公報的0038~0052段、日本特開2012-208374號公報的0052~0072段、日本特開2013-068814號公報的0317~0334段、日本特開2016-162946號公報的0061~0080段、國際公開第2021/131355號的0052、0074段、國際公開第2021/132247號的0022~0024段中記載之化合物,該等內容編入本說明書中。作為紫外線吸收劑的市售品,可舉出BASF公司製Tinuvin系列、Uvinul系列等。又,作為苯并三唑化合物,可舉出MIYOSHI OIL & FAT CO., LTD.製MYUA系列(化學工業日報,2016年2月1日)。紫外線吸收劑亦能夠使用後述實施例中記載之化合物、日本專利第6268967號公報的0049~0059段、國際公開第2016/181987號的0059~0076段中記載之化合物。組成物的總固體成分中紫外線吸收劑的含量為0.01~30質量%為較佳,0.05~25質量%為更佳。組成物可以僅含有1種紫外線吸收劑,亦可以含有2種以上。包含2種以上時,該等的合計量在上述範圍內為較佳。 <<Ultraviolet absorber>> The composition of the present invention can contain an ultraviolet absorber. Examples of the ultraviolet absorber include conjugated diene compounds, amino diene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyl trisoxane compounds, indole compounds, trisoxane compounds, dibenzoyl compounds, and the like. As specific examples of such compounds, there are compounds described in paragraphs 0038 to 0052 of Japanese Patent Application No. 2009-217221, paragraphs 0052 to 0072 of Japanese Patent Application No. 2012-208374, paragraphs 0317 to 0334 of Japanese Patent Application No. 2013-068814, paragraphs 0061 to 0080 of Japanese Patent Application No. 2016-162946, paragraphs 0052 and 0074 of International Publication No. 2021/131355, and paragraphs 0022 to 0024 of International Publication No. 2021/132247, and the contents thereof are incorporated into this specification. As commercially available products of ultraviolet absorbers, there are Tinuvin series and Uvinul series manufactured by BASF. In addition, as benzotriazole compounds, the MYUA series manufactured by MIYOSHI OIL & FAT CO., LTD. can be cited (Chemical Industry Daily, February 1, 2016). The ultraviolet absorber can also use the compounds described in the embodiments described below, the compounds described in paragraphs 0049 to 0059 of Japanese Patent No. 6268967, and the compounds described in paragraphs 0059 to 0076 of International Publication No. 2016/181987. The content of the ultraviolet absorber in the total solid content of the composition is preferably 0.01 to 30% by mass, and more preferably 0.05 to 25% by mass. The composition may contain only one ultraviolet absorber, or may contain two or more. When two or more types are included, the total amount thereof is preferably within the above range.
<<抗氧化劑>> 本發明的組成物能夠含有抗氧化劑。作為抗氧化劑,可舉出酚系抗氧化劑、胺系抗氧化劑、磷系抗氧化劑、硫系抗氧化劑等。作為酚系抗氧化劑,可舉出受阻酚化合物。酚系抗氧化劑為在與酚性羥基相鄰的部位(鄰位)具有取代基之化合物為較佳。作為前述取代基,碳數1~22的經取代或未經取代之烷基為較佳。抗氧化劑為在同一分子內具有苯酚基和亞磷酸酯基之化合物亦較佳。作為磷系抗氧化劑,可舉出三[2-[[2,4,8,10-四(1,1-二甲基乙基)二苯并[d,f][1,3,2]二氧雜膦雜環庚二烯-6-基]氧基]乙基]胺、三[2-[(4,6,9,11-四-三級丁基二苯并[d,f][1,3,2]二氧雜膦雜環庚二烯-2-基)氧基]乙基]胺、亞磷酸雙(2,4-二-三級丁基-6-甲基苯基)乙酯、三(2,4-二-三級丁基苯基)亞磷酸酯等。作為抗氧化劑的市售品,例如,可舉出ADEKA STAB AO-20、ADEKA STAB AO-30、ADEKA STAB AO-40、ADEKA STAB AO-50、ADEKA STAB AO-50F、ADEKA STAB AO-60、ADEKA STAB AO-60G、ADEKA STAB AO-80、ADEKA STAB AO-330、ADEKA STAB AO-412S、ADEKA STAB 2112、ADEKA STAB PEP-36、ADEKA STAB HP-10(以上為ADEKA CORPORATION製)、JP-650(JOHOKU CHEMICAL CO., LTD.製)等。抗氧化劑亦能夠使用日本專利第6268967號公報的0023~0048段中記載之化合物、國際公開第2017/006600號中記載之化合物、國際公開第2017/164024號中記載之化合物、韓國公開專利第10-2019-0059371號公報中記載之化合物。組成物的總固體成分中抗氧化劑的含量為0.01~20質量%為較佳,0.3~15質量%為更佳。組成物可以僅含有1種抗氧化劑,亦可以含有2種以上。包含2種以上時,該等的合計量在上述範圍內為較佳。 <<Antioxidant>> The composition of the present invention can contain an antioxidant. As the antioxidant, phenolic antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, etc. can be cited. As the phenolic antioxidant, hindered phenol compounds can be cited. The phenolic antioxidant is preferably a compound having a substituent at a position adjacent to the phenolic hydroxyl group (adjacent position). As the aforementioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred. The antioxidant is also preferably a compound having a phenol group and a phosphite group in the same molecule. As the phosphorus-based antioxidant, there can be mentioned tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphinocycloheptadien-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetrakis-tert-butyldibenzo[d,f][1,3,2]dioxaphosphinocycloheptadien-2-yl)oxy]ethyl]amine, bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite, tris(2,4-di-tert-butylphenyl)phosphite, and the like. Examples of commercially available antioxidants include ADEKA STAB AO-20, ADEKA STAB AO-30, ADEKA STAB AO-40, ADEKA STAB AO-50, ADEKA STAB AO-50F, ADEKA STAB AO-60, ADEKA STAB AO-60G, ADEKA STAB AO-80, ADEKA STAB AO-330, ADEKA STAB AO-412S, ADEKA STAB 2112, ADEKA STAB PEP-36, ADEKA STAB HP-10 (all manufactured by ADEKA CORPORATION), and JP-650 (manufactured by JOHOKU CHEMICAL CO., LTD.). Antioxidants can also use compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967, compounds described in International Publication No. 2017/006600, compounds described in International Publication No. 2017/164024, and compounds described in Korean Publication No. 10-2019-0059371. The content of the antioxidant in the total solid content of the composition is preferably 0.01 to 20% by mass, and more preferably 0.3 to 15% by mass. The composition may contain only one antioxidant, or may contain two or more. When containing two or more, the total amount of the antioxidants is preferably within the above range.
<<其他成分>> 本發明的組成物亦可以根據需要含有增感劑、填料、熱硬化促進劑、塑化劑及其他助劑類(例如,導電性粒子、消泡劑、阻燃劑、調平劑、剝離促進劑、香料、表面張力調整劑、鏈轉移劑、潛在抗氧化劑等)。藉由適當地含有該等成分,能夠調節膜物性等性質。該等成分能夠使用國際公開第2022/085485號的0182段中記載之化合物。 <<Other ingredients>> The composition of the present invention may also contain sensitizers, fillers, thermosetting accelerators, plasticizers and other additives (e.g., conductive particles, defoamers, flame retardants, levelers, peeling accelerators, fragrances, surface tension modifiers, chain transfer agents, potential antioxidants, etc.) as needed. By appropriately containing these ingredients, the properties of the film can be adjusted. These ingredients can use the compounds described in paragraph 0182 of International Publication No. 2022/085485.
<收容容器> 作為本發明的組成物的收容容器,並沒有特別限制,能夠使用公知的收容容器。又,作為收容容器,能夠使用國際公開第2022/085485號的0187段中記載之容器。 <Storage container> The storage container for the composition of the present invention is not particularly limited, and a known storage container can be used. In addition, as a storage container, the container described in paragraph 0187 of International Publication No. 2022/085485 can be used.
<組成物的製備方法> 本發明的組成物能夠混合前述成分來製備。製備組成物時,可以將所有成分同時溶解或分散於溶劑中而製備組成物,亦可以根據需要預先製備適當調配了各成分之2份以上的溶液或分散液,並在使用時(塗布時)將該等混合而製備組成物。 <Method for preparing the composition> The composition of the present invention can be prepared by mixing the aforementioned components. When preparing the composition, all the components can be dissolved or dispersed in a solvent at the same time to prepare the composition, or two or more solutions or dispersions containing each component can be prepared in advance as needed, and these can be mixed to prepare the composition when used (when applied).
製備組成物時,可以包括顏料分散製程。在顏料分散製程中,作為用於分散顏料的機械力,可舉出壓縮、擠壓、衝擊、剪斷、孔蝕等。作為該等製程的具體例,可舉出珠磨、砂磨、輥磨、球磨、塗料攪拌、微射流、高速葉輪、混砂、噴流混合、高壓濕式微粒化、超聲波分散等。又,顏料在砂磨機(珠磨機)中的粉碎中,在藉由使用直徑小的微珠、增加微珠的填充率等來提高粉碎效率之條件下進行處理為較佳。又,粉碎處理後,藉由過濾、離心分離等去除粗粒子為較佳。又,關於顏料分散製程及分散機,能夠較佳地使用“分散技術大全集,JOHOKIKO CO., LTD.發行,2005年7月15日”或“以懸浮液(固體/液體分散體系)為中心之分散技術與工業上的實際應用 綜合資料集,經營開發中心出版部發行,1978年10月10日”、日本特開2015-157893號公報的0022段中記載之製程及分散機。又,在顏料分散製程中,可以藉由鹽磨步驟進行顏料的微細化處理。例如,在鹽磨步驟中使用之材料、裝置、處理條件等能夠參考日本特開2015-194521號公報、日本特開2012-046629號公報的記載。作為用於分散的微珠材料,可舉出二氧化鋯、瑪瑙、石英、二氧化鈦、碳化鎢、氮化矽、氧化鋁、不鏽鋼及玻璃。又,珠子亦能夠使用莫氏硬度為2以上的無機化合物。可以在組成物中包含1~10000ppm的上述珠子。When preparing the composition, a pigment dispersion process may be included. In the pigment dispersion process, as the mechanical force used to disperse the pigment, compression, extrusion, impact, shearing, erosion, etc. can be cited. As specific examples of such processes, bead milling, sand milling, roller milling, ball milling, paint stirring, micro jet, high-speed impeller, sand mixing, jet mixing, high-pressure wet micronization, ultrasonic dispersion, etc. can be cited. In addition, when the pigment is pulverized in a sand mill (bead mill), it is preferred to process it under the condition of improving the pulverization efficiency by using micro beads with a small diameter and increasing the filling rate of micro beads. In addition, after the pulverization process, it is preferred to remove coarse particles by filtering, centrifugal separation, etc. In addition, regarding the pigment dispersion process and the disperser, the process and the disperser described in paragraph 0022 of "Dispersion Technology Collection, JOHOKIKO CO., LTD., July 15, 2005" or "Dispersion Technology and Practical Industrial Applications Focusing on Suspension (Solid/Liquid Dispersion System), Business Development Center Publishing Department, October 10, 1978" and Japanese Patent Publication No. 2015-157893 can be preferably used. In addition, in the pigment dispersion process, the pigment can be finely processed by the salt grinding step. For example, the materials, devices, and treatment conditions used in the salt grinding step can refer to the descriptions of Japanese Patent Publication No. 2015-194521 and Japanese Patent Publication No. 2012-046629. As the microbead material used for dispersion, zirconia, agate, quartz, titanium dioxide, tungsten carbide, silicon nitride, aluminum oxide, stainless steel, and glass can be cited. In addition, the beads can also use inorganic compounds with a Mohs hardness of 2 or more. The above beads can be included in the composition at 1 to 10,000 ppm.
製備組成物時,以去除異物、減少缺陷等為目的,用過濾器過濾組成物為較佳。作為用於過濾之過濾器的種類及過濾方法,可舉出國際公開第2022/085485號的0196~0199段中記載之過濾器及過濾方法。When preparing a composition, it is preferred to filter the composition with a filter for the purpose of removing foreign matter, reducing defects, etc. As the type of filter used for filtering and the filtering method, the filter and filtering method described in paragraphs 0196 to 0199 of International Publication No. 2022/085485 can be cited.
<膜> 接著,對本發明的膜進行說明。本發明的膜為由上述本發明的組成物獲得之膜。本發明的膜能夠較佳地用作濾光器。濾光器的用途並沒有特別限定,可舉出紅外線截止濾波器、紅外線透射濾波器等。作為紅外線截止濾波器,例如,可舉出固體攝像元件的受光側的紅外線截止濾波器(例如,針對晶圓級別透鏡之紅外線截止濾波器用等)、固體攝像元件的背面側(與受光側相反的一側)的紅外線截止濾波器、環境光感測器用紅外線截止濾波器(例如,感知放置了情報終端裝置之環境的照度、色調而調整顯示器的色調之照度感測器、調整色調之色彩校正用感測器)等。尤其,能夠較佳地用作固體攝像元件的受光側的紅外線截止濾波器。作為紅外線透射濾波器,可舉出遮蔽可見光且能夠使特定波長以上的紅外線選擇性透射之濾波器。 <Membrane> Next, the membrane of the present invention is described. The membrane of the present invention is a membrane obtained from the composition of the present invention described above. The membrane of the present invention can be preferably used as an optical filter. The use of the optical filter is not particularly limited, and examples thereof include infrared cutoff filters, infrared transmission filters, etc. Examples of the infrared cut filter include an infrared cut filter on the light receiving side of a solid-state imaging device (e.g., an infrared cut filter for a wafer-level lens, etc.), an infrared cut filter on the back side (the side opposite to the light receiving side) of a solid-state imaging device, and an infrared cut filter for an ambient light sensor (e.g., an illuminance sensor that senses the illuminance and hue of the environment where an intelligence terminal device is placed and adjusts the hue of a display, a color correction sensor that adjusts the hue), etc. In particular, it can be preferably used as an infrared cut filter on the light receiving side of a solid-state imaging device. As an infrared transmission filter, a filter that blocks visible light and selectively transmits infrared light above a specific wavelength can be cited.
本發明的膜可以具有圖案,亦可以為不具有圖案之膜(平坦膜)。又,本發明的膜可以積層於支撐體上來使用,亦可以將本發明的膜從支撐體剝離來使用。作為支撐體,可舉出矽基板等半導體基材或透明基材。The film of the present invention may have a pattern or may be a film without a pattern (flat film). Furthermore, the film of the present invention may be used by being laminated on a support or by being peeled off from a support. As the support, a semiconductor substrate such as a silicon substrate or a transparent substrate may be cited.
可以在用作支撐體之半導體基材上形成有電荷耦合元件(CCD)、互補金屬氧化膜半導體(CMOS)、透明導電膜等。又,可以在半導體基材上形成有隔離各像素之黑矩陣。又,可以根據需要在半導體基材上設置有用於改善與上部層的密接性、防止物質的擴散或基板表面平坦化之底塗層。A charge coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, etc. may be formed on a semiconductor substrate used as a support. In addition, a black matrix for isolating each pixel may be formed on the semiconductor substrate. In addition, an undercoat layer may be provided on the semiconductor substrate as needed to improve adhesion with an upper layer, prevent diffusion of a substance, or flatten the substrate surface.
作為可用作支撐體之透明基材,只要由至少能夠使可見光透射之材料構成,則並沒有特別限定。例如,可舉出由玻璃、樹脂等材質構成之基材。作為樹脂,可舉出聚對苯二甲酸乙二醇酯、聚對苯二甲酸丁二醇酯等聚酯樹脂、聚乙烯、聚丙烯、乙烯/乙酸乙烯酯共聚物等聚烯烴樹脂、降莰烯樹脂、聚丙烯酸酯、聚甲基丙烯酸甲酯等丙烯酸樹脂、胺基甲酸酯樹脂、氯乙烯樹脂、氟樹脂、聚碳酸酯樹脂、聚乙烯醇縮丁醛樹脂、聚乙烯醇樹脂等。作為玻璃,可舉出鈉鈣玻璃、硼矽酸玻璃、無鹼玻璃、石英玻璃、含銅玻璃等。作為含銅玻璃,可舉出含銅磷酸鹽玻璃、含銅氟磷酸鹽玻璃等。含銅玻璃亦能夠使用市售品。作為含銅玻璃的市售品,可舉出NF-50(AGC TECHNO GLASS Co., Ltd.製)等。As for the transparent substrate that can be used as a support, there is no particular limitation as long as it is made of a material that can at least transmit visible light. For example, substrates made of materials such as glass and resins can be cited. As resins, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyolefin resins such as polyethylene, polypropylene, and ethylene/vinyl acetate copolymers, norbornene resins, polyacrylates, acrylic resins such as polymethyl methacrylate, urethane resins, vinyl chloride resins, fluororesins, polycarbonate resins, polyvinyl butyral resins, polyvinyl alcohol resins, etc. can be cited. As glass, sodium calcium glass, borosilicate glass, alkali-free glass, quartz glass, copper-containing glass, etc. can be cited. Examples of the copper-containing glass include copper-containing phosphate glass and copper-containing fluorophosphate glass. Commercially available copper-containing glass may be used. Examples of commercially available copper-containing glass include NF-50 (manufactured by AGC TECHNO GLASS Co., Ltd.).
本發明的膜的厚度能夠根據目的適當調整。膜的厚度能夠設定為200μm以下,亦能夠設定為150μm以下,亦能夠設定為120μm以下,亦能夠設定為20μm以下,亦能夠設定為10μm以下,亦能夠設定為5μm以下。膜的厚度的下限為0.1μm以上為較佳,0.2μm以上為更佳。The thickness of the film of the present invention can be appropriately adjusted according to the purpose. The thickness of the film can be set to 200 μm or less, or 150 μm or less, or 120 μm or less, or 20 μm or less, or 10 μm or less, or 5 μm or less. The lower limit of the thickness of the film is preferably 0.1 μm or more, and more preferably 0.2 μm or more.
將本發明的膜用作紅外線截止濾波器時,本發明的膜在波長650~1500nm(較佳為波長660~1200nm,更佳為波長660~1000nm)的範圍內存在極大吸收波長為較佳。 又,波長700~720nm範圍內的平均透射率為10%以下為較佳,7%以下為更佳,4%以下為進一步較佳,2%以下為特佳。 又,波長420~550nm範圍內的平均透射率為86%以上為較佳,89%以上為更佳,92%以上為進一步較佳,95%以上為特佳。又,波長420~550nm的所有範圍內的透射率為50%以上為較佳,70%以上為更佳,80%以上為進一步較佳。 又,波長650~1500nm(較佳為波長660~1200nm,更佳為波長660~1000nm)的範圍內的至少1處的透射率為10%以下為較佳,7%以下為更佳,4%以下為進一步較佳,2%以下為特佳。 又,在將極大吸收波長處的吸光度設定為1時,本發明的膜在波長420~550nm範圍內的平均吸光度未達0.030為較佳,未達0.025為更佳。 When the film of the present invention is used as an infrared cutoff filter, it is preferred that the film of the present invention has a maximum absorption wavelength in the range of 650 to 1500 nm (preferably 660 to 1200 nm, and more preferably 660 to 1000 nm). In addition, the average transmittance in the range of 700 to 720 nm is preferably 10% or less, more preferably 7% or less, further preferably 4% or less, and particularly preferably 2% or less. In addition, the average transmittance in the range of 420 to 550 nm is preferably 86% or more, more preferably 89% or more, further preferably 92% or more, and particularly preferably 95% or more. Furthermore, the transmittance in the entire range of wavelengths from 420 to 550 nm is preferably 50% or more, more preferably 70% or more, and even more preferably 80% or more. Furthermore, the transmittance at at least one point in the range of wavelengths from 650 to 1500 nm (preferably wavelengths from 660 to 1200 nm, and even more preferably wavelengths from 660 to 1000 nm) is preferably 10% or less, more preferably 7% or less, even more preferably 4% or less, and particularly preferably 2% or less. Furthermore, when the absorbance at the maximum absorption wavelength is set to 1, the average absorbance of the film of the present invention in the range of wavelengths from 420 to 550 nm is preferably less than 0.030, and even more preferably less than 0.025.
將本發明的膜用作紅外線透射濾波器時,本發明的膜例如具有以下(i1)~(i3)中的任一種分光特性為較佳。 (i1):在波長400~850nm範圍內的透射率的最大值為20%以下(較佳為15%以下,更佳為10%以下)且在波長1000~1500nm範圍內的透射率的最小值為70%以上(較佳為75%以上,更佳為80%以上)之濾波器。具有此類分光特性之膜能夠遮蔽波長400~850nm的範圍內的光,使波長大於950nm的光透射。 (i2):在波長400~950nm範圍內的透射率的最大值為20%以下(較佳為15%以下,更佳為10%以下)且在波長1100~1500nm範圍內的透射率的最小值為70%以上(較佳為75%以上,更佳為80%以上)之濾波器。具有此類分光特性之膜能夠遮蔽波長400~950nm的範圍內的光且透射波長大於1050nm的光。 (i3):在波長400~1050nm範圍內的透射率的最大值為20%以下(較佳為15%以下,更佳為10%以下)且在波長1200~1500nm範圍內的透射率的最小值為70%以上(較佳為75%以上,更佳為80%以上)之濾波器。具有此類分光特性之膜能夠遮蔽波長400~1050nm的範圍內的光且透射波長大於1150nm的光。 When the film of the present invention is used as an infrared transmission filter, the film of the present invention preferably has any one of the following spectral characteristics (i1) to (i3). (i1): A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 850 nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1000 to 1500 nm. A film having such spectral characteristics can shield light in the wavelength range of 400 to 850 nm and transmit light with a wavelength greater than 950 nm. (i2): A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 950 nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1100 to 1500 nm. A film having such spectral characteristics can shield light in the wavelength range of 400 to 950 nm and transmit light with a wavelength greater than 1050 nm. (i3): A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 1050 nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1200 to 1500 nm. Films with this type of spectral properties can shield light in the wavelength range of 400 to 1050 nm and transmit light with a wavelength greater than 1150 nm.
本發明的膜亦可以與包含彩色著色劑之濾色器組合使用。濾色器能夠使用包含彩色著色劑之著色組成物來製造。將本發明的膜用作紅外線截止濾波器,且組合使用本發明的膜與濾色器時,在本發明的膜的光徑上配置有濾色器為較佳。例如,將本發明的膜與濾色器積層而用作積層體為較佳。在積層體中,本發明的膜與濾色器兩者在厚度方向上可以相鄰,亦可以不相鄰。本發明的膜與濾色器在厚度方向上不相鄰時,可以在與形成有濾色器之支撐體不同的支撐體上形成有本發明的膜,亦可以在本發明的膜與濾色器之間夾有構成固體攝像元件之其他構件(例如,微透鏡、平坦化層等)。The film of the present invention can also be used in combination with a filter containing a color coloring agent. The filter can be manufactured using a coloring composition containing a color coloring agent. When the film of the present invention is used as an infrared cutoff filter and the film of the present invention and the filter are used in combination, it is preferred that the filter is arranged on the optical path of the film of the present invention. For example, it is preferred that the film of the present invention and the filter are stacked and used as a laminate. In the laminate, the film of the present invention and the filter may be adjacent to each other in the thickness direction, or may not be adjacent to each other. When the film of the present invention and the color filter are not adjacent to each other in the thickness direction, the film of the present invention may be formed on a support body different from the support body on which the color filter is formed, or other components constituting a solid-state imaging element (for example, a microlens, a planarization layer, etc.) may be sandwiched between the film of the present invention and the color filter.
本發明的膜能夠用於CCD(電荷耦合元件)、CMOS(互補金屬氧化膜半導體)等固體攝像元件、紅外線感測器、圖像顯示裝置等各種裝置。The film of the present invention can be used in various devices such as solid-state imaging devices such as CCD (charge coupled device), CMOS (complementary metal oxide semiconductor), infrared sensors, and image display devices.
<膜的製造方法> 本發明的膜能夠經過塗布本發明的組成物之步驟來製造。 <Method for producing film> The film of the present invention can be produced by applying the composition of the present invention.
作為支撐體,可舉出上述者。作為組成物的塗布方法,能夠利用旋塗法等公知的方法。例如,能夠使用國際公開第2022/085485號的0207段中記載之塗布方法。As the support, the above-mentioned ones can be cited. As the coating method of the composition, a known method such as a spin coating method can be used. For example, the coating method described in paragraph 0207 of International Publication No. 2022/085485 can be used.
可以對塗布組成物形成之組成物層進行乾燥(預烘烤)。進行預烘烤時,預烘烤溫度為150℃以下為較佳,120℃以下為更佳,110℃以下為進一步較佳。下限例如能夠設定為50℃以上,亦能夠設定為80℃以上。預烘烤時間為10秒~3000秒為較佳,40~2500秒為更佳,80~220秒為進一步較佳。乾燥能夠利用加熱板、烘箱等來進行。The composition layer formed by the coating composition can be dried (pre-baked). When pre-baking, the pre-baking temperature is preferably below 150°C, more preferably below 120°C, and further preferably below 110°C. The lower limit can be set to, for example, above 50°C, and can also be set to above 80°C. The pre-baking time is preferably 10 seconds to 3000 seconds, more preferably 40 to 2500 seconds, and further preferably 80 to 220 seconds. Drying can be performed using a heating plate, an oven, etc.
膜的製造方法可以進一步包括圖案形成步驟。作為圖案形成方法,可舉出利用光微影法之圖案形成方法、利用乾式蝕刻法之圖案形成方法,利用光微影法之圖案形成方法為較佳。再者,將本發明的膜用作平坦膜時,可以不進行圖案形成步驟。以下,對圖案形成步驟進行詳細說明。The film manufacturing method may further include a pattern forming step. As the pattern forming method, a pattern forming method using photolithography and a pattern forming method using dry etching can be cited, and the pattern forming method using photolithography is preferred. Furthermore, when the film of the present invention is used as a flat film, the pattern forming step may not be performed. The pattern forming step is described in detail below.
(利用光微影法形成圖案的情況) 利用光微影法之圖案形成方法包括對塗布本發明的組成物形成之組成物層進行圖案狀曝光之步驟(曝光步驟)和顯影去除未曝光部的組成物層而形成圖案之步驟(顯影步驟)為較佳。可以根據需要設置對經顯影之圖案進行烘烤之步驟(後烘烤步驟)。以下,對各步驟進行說明。 (The case of forming a pattern by photolithography) The method of forming a pattern by photolithography includes a step of exposing the composition layer formed by applying the composition of the present invention in a pattern-like manner (exposure step) and a step of developing and removing the unexposed portion of the composition layer to form a pattern (development step). A step of baking the developed pattern (post-baking step) can be provided as needed. The following describes each step.
在曝光步驟中對組成物層進行圖案狀曝光。例如,使用步進曝光機或掃描曝光機等,隔著具有規定遮罩圖案之遮罩,對組成物層進行曝光,由此能夠以圖案狀進行曝光。藉此,能夠硬化曝光部分。In the exposure step, the component layer is exposed in a pattern. For example, a stepper or scanner is used to expose the component layer through a mask having a predetermined mask pattern, thereby exposing in a pattern. This allows the exposed portion to be cured.
作為能夠在曝光時使用之放射線(光),可舉出g射線、i射線等。又,亦能夠使用波長300nm以下的光(較佳為波長180~300nm的光)。作為波長300nm以下的光,可舉出KrF射線(波長248nm)、ArF射線(波長193nm)等,KrF射線(波長248nm)為較佳。又,亦能夠利用300nm以上的長波光源。As radiation (light) that can be used for exposure, g-ray, i-ray, etc. can be cited. In addition, light with a wavelength of 300nm or less (preferably light with a wavelength of 180 to 300nm) can also be used. As light with a wavelength of 300nm or less, KrF ray (wavelength 248nm), ArF ray (wavelength 193nm), etc. can be cited, and KrF ray (wavelength 248nm) is preferred. In addition, a long-wave light source of 300nm or more can also be used.
又,在曝光時,可以連續照射光而進行曝光,亦可以實施脈衝式照射而進行曝光(脈衝曝光)。再者,脈衝曝光係指以短時間(例如,毫秒級以下)週期,反覆進行光的照射和暫停而進行曝光之方式的曝光方法。Furthermore, during exposure, light may be irradiated continuously or in pulses (pulse exposure). Pulse exposure refers to an exposure method in which light is irradiated and paused repeatedly in a short period of time (e.g., less than milliseconds) to perform exposure.
照射量(曝光量)例如為0.03~2.5J/cm 2為較佳,0.05~1.0J/cm 2為更佳。曝光時的氧濃度能夠適當選擇,除了在大氣下進行以外,例如亦可以在氧濃度為19體積%以下的低氧氣氛下(例如,15體積%、5體積%或實質上無氧)進行曝光,亦可以在氧濃度超過21體積%之高氧氣氛下(例如,22體積%、30體積%或50體積%)進行曝光。又,曝光照度能夠適當設定,通常能夠從1000W/m 2~100000W/m 2(例如,5000W/m 2、15000W/m 2或35000W/m 2)的範圍內選擇。氧濃度和曝光照度的條件可以適當組合,例如能夠設定為氧濃度為10體積%且照度為10000W/m 2、氧濃度為35體積%且照度為20000W/m 2等。 The irradiation dose (exposure dose) is preferably 0.03 to 2.5 J/cm 2 , and more preferably 0.05 to 1.0 J/cm 2. The oxygen concentration during exposure can be appropriately selected. In addition to being performed in the atmosphere, exposure can be performed in a low oxygen atmosphere with an oxygen concentration of 19 volume % or less (for example, 15 volume %, 5 volume % or substantially oxygen-free), or in a high oxygen atmosphere with an oxygen concentration exceeding 21 volume % (for example, 22 volume %, 30 volume % or 50 volume %). The exposure illuminance can be appropriately set and can generally be selected from a range of 1000 W/m 2 to 100,000 W/m 2 (e.g., 5000 W/m 2 , 15000 W/m 2 or 35000 W/m 2 ). The conditions of oxygen concentration and exposure illuminance can be appropriately combined, for example, the conditions can be set to an oxygen concentration of 10 vol% and an illuminance of 10,000 W/m 2 , an oxygen concentration of 35 vol% and an illuminance of 20,000 W/m 2 , etc.
接著,顯影去除曝光後的組成物層的未曝光部的組成物層來形成圖案。未曝光部的組成物層的顯影去除能夠使用顯影液進行。藉此,曝光步驟中的未曝光部的組成物層溶出至顯影液中,在支撐體上僅殘留光硬化部分。顯影液的溫度例如為20~30℃為較佳。顯影時間為20~180秒為較佳。又,為了提高殘渣去除性,可以反覆進行複數次如下步驟:每隔60秒甩掉顯影液,進而供給新的顯影液之步驟。Next, the unexposed portion of the component layer after exposure is developed and removed to form a pattern. The development and removal of the unexposed portion of the component layer can be performed using a developer. Thereby, the unexposed portion of the component layer in the exposure step is dissolved into the developer, and only the light-hardened portion remains on the support. The temperature of the developer is preferably 20 to 30°C, for example. The developing time is preferably 20 to 180 seconds. In addition, in order to improve the removability of residues, the following steps can be repeated multiple times: the developer is discarded every 60 seconds, and a new developer is supplied.
顯影液可舉出有機溶劑、鹼顯影液等,可較佳地使用鹼顯影液。關於顯影液及顯影後的清洗(沖洗)方法,能夠使用國際公開第2022/085485號的0214段中記載之顯影液或清洗方法。The developer may be an organic solvent, an alkaline developer, etc., and an alkaline developer is preferably used. Regarding the developer and the cleaning (rinsing) method after development, the developer or cleaning method described in paragraph 0214 of International Publication No. 2022/085485 can be used.
顯影後,在實施乾燥之後進行追加曝光處理或加熱處理(後烘烤)為較佳。追加曝光處理或後烘烤為用於製成完全硬化者之顯影後硬化處理。例如,後烘烤中的加熱溫度為100~240℃為較佳,200~240℃為更佳。能夠以成為上述條件之方式,使用加熱板或對流烘箱(熱風循環式乾燥機)、高頻加熱機等加熱機構,以連續式或間歇式,對顯影後的膜進行後烘烤。進行追加曝光處理時,用於曝光之光為波長400nm以下的光為較佳。又,追加曝光處理可以藉由韓國公開專利第10-2017-0122130號公報中記載之方法進行。After development, it is preferred to perform additional exposure treatment or heat treatment (post-baking) after drying. Additional exposure treatment or post-baking is a post-development hardening treatment used to make a completely cured film. For example, the heating temperature in the post-baking is preferably 100 to 240°C, and 200 to 240°C is more preferred. The developed film can be post-baked continuously or intermittently using a heating mechanism such as a heating plate or a convection oven (hot air circulation dryer), a high-frequency heater, etc. in such a manner as to achieve the above conditions. When performing additional exposure treatment, it is preferred that the light used for exposure has a wavelength of less than 400nm. In addition, the additional exposure treatment can be performed by the method described in the Korean Patent Publication No. 10-2017-0122130.
(利用乾式蝕刻法形成圖案之情況) 藉由乾式蝕刻法形成圖案時,能夠藉由以下方法進行:對在支撐體上塗布上述組成物形成之組成物層進行硬化而形成硬化物層,接著在該硬化物層上形成經圖案化之光阻層,接著將經圖案化之光阻層作為遮罩,使用蝕刻氣體對硬化物層進行乾式蝕刻等。形成光阻層時,實施預烘烤處理為較佳。關於藉由乾式蝕刻法形成圖案的內容,能夠參考日本特開2013-064993號公報的0010~0067段的記載,該內容編入本說明書中。 (Forming a pattern by dry etching) When forming a pattern by dry etching, the following method can be used: a composition layer formed by coating the above-mentioned composition on a support is hardened to form a hardened layer, and then a patterned photoresist layer is formed on the hardened layer, and then the patterned photoresist layer is used as a mask to dry-etch the hardened layer using an etching gas. When forming the photoresist layer, it is preferred to perform a pre-baking treatment. For the content of forming a pattern by dry etching, reference can be made to paragraphs 0010 to 0067 of Japanese Patent Publication No. 2013-064993, and the content is incorporated into this specification.
<濾光器> 本發明的濾光器具有上述本發明的膜。作為濾光器的種類,可舉出紅外線截止濾波器及紅外線透射濾波器等。 <Optical filter> The optical filter of the present invention has the above-mentioned film of the present invention. As the type of the optical filter, there can be cited an infrared cut filter and an infrared transmission filter.
本發明的濾光器除了具有上述本發明的膜以外,可以進一步具有含銅層、介電體多層膜、紫外線吸收層等。作為紫外線吸收層,例如,可舉出國際公開第2015/099060號的0040~0070、0119~0145段中記載之吸收層。作為介電體多層膜,可舉出日本特開2014-041318號公報的0255~0259段中記載之介電體多層膜。作為含銅層,亦能夠使用由含銅玻璃構成之玻璃基板(含銅玻璃基板)、包含銅錯合物之層(含銅錯合物層)。作為含銅玻璃基板,可舉出含銅磷酸鹽玻璃、含銅氟磷酸鹽玻璃等。作為含銅玻璃的市售品,可舉出NF-50(AGC TECHNO GLASS Co., Ltd.製)、BG-60、BG-61(以上,Schott AG製)、CD5000(HOYA CORPORATION製)等。In addition to the above-mentioned film of the present invention, the filter of the present invention may further have a copper-containing layer, a dielectric multilayer film, an ultraviolet absorption layer, etc. As the ultraviolet absorption layer, for example, the absorption layer described in paragraphs 0040 to 0070 and 0119 to 0145 of International Publication No. 2015/099060 can be cited. As the dielectric multilayer film, the dielectric multilayer film described in paragraphs 0255 to 0259 of Japanese Patent Publication No. 2014-041318 can be cited. As the copper-containing layer, a glass substrate composed of copper-containing glass (copper-containing glass substrate) and a layer containing a copper complex (copper-containing complex layer) can also be used. Examples of the copper-containing glass substrate include copper-containing phosphate glass, copper-containing fluorophosphate glass, etc. Examples of commercially available copper-containing glass include NF-50 (manufactured by AGC TECHNO GLASS Co., Ltd.), BG-60, BG-61 (manufactured by Schott AG), and CD5000 (manufactured by HOYA CORPORATION).
<固體攝像元件> 本發明的固體攝像元件具有上述本發明的膜。作為固體攝像元件的結構,只要是具有本發明的膜之結構且作為固體攝像元件發揮作用之結構,則並沒有特別限定。例如,可舉出如下結構。 <Solid-state imaging device> The solid-state imaging device of the present invention has the above-mentioned film of the present invention. The structure of the solid-state imaging device is not particularly limited as long as it has the structure of the film of the present invention and functions as a solid-state imaging device. For example, the following structure can be cited.
上述結構為在支撐體上具有構成固體攝像元件的受光區域之由複數個光二極體及多晶矽等構成之傳輸電極、在光二極體及傳輸電極上具有僅在光二極體的受光部開口之由鎢等構成之遮光膜,在遮光膜上具有以覆蓋遮光膜整體及光二極體受光部之方式形成之由氮化矽等構成之元件保護膜,在元件保護膜上具有本發明的膜。再者,亦可以為在裝置保護膜上且在本發明的膜的下側(靠近支撐體的一側)具有聚光機構(例如,微透鏡等。以下相同)之結構或在本發明的膜上具有聚光機構之結構等。又,濾色器亦可以具有如下結構:例如在藉由隔壁分隔成方格狀之空間嵌入有形成各像素之膜。此時的隔壁的折射率比各像素低為較佳。作為具有此類結構之攝像裝置的例子,可舉出日本特開2012-227478號公報、日本特開2014-179577號公報中記載之裝置。The above structure is a structure in which a transmission electrode composed of a plurality of photodiodes and polysilicon, etc., constituting a light receiving area of a solid-state imaging element, is provided on a support, a light shielding film composed of tungsten, etc., which is opened only in the light receiving part of the photodiode, is provided on the photodiode and the transmission electrode, a device protection film composed of silicon nitride, etc., which is formed in a manner covering the entire light shielding film and the light receiving part of the photodiode, is provided on the light shielding film, and the film of the present invention is provided on the device protection film. Furthermore, it can also be a structure in which a focusing mechanism (for example, a micro lens, etc., the same below) is provided on the device protection film and on the lower side of the film of the present invention (the side close to the support), or a structure in which a focusing mechanism is provided on the film of the present invention. In addition, the color filter may have a structure in which, for example, a film forming each pixel is embedded in a space divided into a grid shape by a partition wall. In this case, the refractive index of the partition wall is preferably lower than that of each pixel. As examples of imaging devices having such a structure, devices described in Japanese Patent Publication No. 2012-227478 and Japanese Patent Publication No. 2014-179577 can be cited.
<圖像顯示裝置> 本發明的圖像顯示裝置具有本發明的膜。作為圖像顯示裝置,可舉出液晶顯示裝置、有機電致發光(有機EL)顯示裝置等。關於圖像顯示裝置的定義、詳細內容,例如記載於“電子顯示裝置(佐佐木昭夫著,Kogyo Chosakai Publishing Co., Ltd.,1990年發行)”、“顯示裝置(伊吹順章著,Sangyo Tosho Publishing Co., Ltd.,1989年發行)”等。又,關於液晶顯示裝置,例如記載於“下一代液晶顯示技術(內田龍男編輯,Kogyo Chosakai Publishing Co., Ltd.,1994年發行)”。能夠適用本發明之液晶顯示裝置並沒有特別限制,例如能夠適用於上述“下一代液晶顯示技術”中記載之各種方式的液晶顯示裝置。圖像顯示裝置可以具有白色有機EL元件。作為白色有機EL元件,串聯結構為較佳。關於有機EL元件的串聯結構,記載於日本特開2003-045676號公報、三上明義監修,“有機EL技術開發的最前沿-高亮度.高精度.長壽命化.技術集-”,TECHNICAL INFORMATION INSTITUTE CO., LTD.,326~328頁,2008年等。有機EL元件發出之白色光的光譜在藍色區域(430~485nm)、綠色區域(530~580nm)及黃色區域(580~620nm)具有較強的極大發光峰為較佳。除了該等發光峰以外,進一步在紅色區域(650~700nm)具有極大發光峰為更佳。 <Image display device> The image display device of the present invention has the film of the present invention. As the image display device, a liquid crystal display device, an organic electroluminescent (organic EL) display device, etc. can be cited. The definition and details of the image display device are described in, for example, "Electronic Display Device (written by Akio Sasaki, Kogyo Chosakai Publishing Co., Ltd., published in 1990)" and "Display Device (written by Junaki Ibuki, Sangyo Tosho Publishing Co., Ltd., published in 1989)". In addition, regarding the liquid crystal display device, it is described in, for example, "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, Kogyo Chosakai Publishing Co., Ltd., published in 1994)". There is no particular limitation on the liquid crystal display device to which the present invention can be applied. For example, it can be applied to various types of liquid crystal display devices described in the above-mentioned "Next Generation Liquid Crystal Display Technology". The image display device can have a white organic EL element. As a white organic EL element, a series structure is preferred. The series structure of the organic EL element is described in Japanese Patent Gazette No. 2003-045676, supervised by Akiyoshi Mikami, "The Cutting Edge of Organic EL Technology Development - High Brightness. High Precision. Long Life. Technology Collection -", TECHNICAL INFORMATION INSTITUTE CO., LTD., pp. 326-328, 2008, etc. The spectrum of white light emitted by organic EL elements preferably has strong maximum luminescence peaks in the blue region (430-485nm), green region (530-580nm) and yellow region (580-620nm). In addition to these luminescence peaks, it is even better to have a maximum luminescence peak in the red region (650-700nm).
<紅外線感測器> 本發明的紅外線感測器具有上述本發明的膜。作為紅外線感測器的結構,只要是作為紅外線感測器發揮作用之結構,則並沒有特別限定。以下,利用附圖對本發明的紅外線感測器的一實施形態進行說明。 <Infrared sensor> The infrared sensor of the present invention has the above-mentioned film of the present invention. The structure of the infrared sensor is not particularly limited as long as it is a structure that functions as an infrared sensor. Hereinafter, an embodiment of the infrared sensor of the present invention will be described using the attached drawings.
圖1中,符號110為固體攝像元件。在固體攝像元件110的攝像區域上配置有紅外線截止濾波器111和紅外線透射濾波器114。又,在紅外線截止濾波器111上配置有濾色器112。在濾色器112及紅外線透射濾波器114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。In FIG1 , reference numeral 110 denotes a solid-state imaging element. An infrared cut filter 111 and an infrared transmission filter 114 are disposed on the imaging region of the solid-state imaging element 110. A color filter 112 is disposed on the infrared cut filter 111. A microlens 115 is disposed on the incident light hv side of the color filter 112 and the infrared transmission filter 114. A planarization layer 116 is formed so as to cover the microlens 115.
紅外線截止濾波器111能夠使用本發明的組成物形成。濾色器112為形成有透射並吸收可見區域內的特定波長的光之像素之濾色器,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,可以使用形成有紅色(R)、綠色(G)、藍色(B)的像素之濾色器等。例如,能夠參考日本特開2014-043556號公報的0214~0263段的記載,該內容編入本說明書中。紅外線透射濾波器114可根據所使用之紅外LED的發光波長來選擇其特性。紅外線透射濾波器114能夠使用本發明的組成物來形成。The infrared cutoff filter 111 can be formed using the composition of the present invention. The color filter 112 is a color filter formed with pixels that transmit and absorb light of a specific wavelength in the visible region, and is not particularly limited, and a conventionally known color filter for forming pixels can be used. For example, a color filter formed with pixels of red (R), green (G), and blue (B) can be used. For example, reference can be made to paragraphs 0214 to 0263 of Japanese Patent Gazette No. 2014-043556, which are incorporated into this specification. The infrared transmission filter 114 can select its characteristics according to the emission wavelength of the infrared LED used. The infrared transmission filter 114 can be formed using the composition of the present invention.
圖1所示之紅外線感測器中,可以在平坦化層116上進一步配置有與紅外線截止濾波器111不同的紅外線截止濾波器(其他紅外線截止濾波器)。作為其他紅外線截止濾波器,可舉出具有含銅層及/或介電體多層膜者等。關於該等的詳細內容,可舉出上述者。又,作為其他紅外線截止濾波器,可以使用雙帶通濾波器。In the infrared sensor shown in FIG1 , an infrared cut filter (other infrared cut filter) different from the infrared cut filter 111 may be further arranged on the flattening layer 116. As other infrared cut filters, there may be cited those having a copper-containing layer and/or a dielectric multilayer film. For details thereof, the above-mentioned ones may be cited. In addition, as other infrared cut filters, dual-band pass filters may be used.
<相機模組> 本發明的相機模組具有上述本發明的膜。作為相機模組的結構,只要是具有本發明的膜之結構且作為相機模組發揮作用之結構,則並沒有特別限定。例如,作為相機模組,可舉出具有固體攝像元件、透鏡及處理從固體攝像元件獲得之影像的電路之結構。作為在相機模組中使用之透鏡及處理從上述固體攝像元件獲得之影像的電路,能夠使用公知者。作為相機模組的例子,能夠參考日本特開2016-006476號公報及日本特開2014-197190號公報中記載之相機模組,該等內容編入本說明書中。 <Camera module> The camera module of the present invention has the above-mentioned film of the present invention. As a structure of the camera module, there is no particular limitation as long as it has a structure of the film of the present invention and functions as a camera module. For example, as a camera module, a structure having a solid-state imaging element, a lens, and a circuit for processing an image obtained from the solid-state imaging element can be cited. As a lens used in the camera module and a circuit for processing an image obtained from the above-mentioned solid-state imaging element, known ones can be used. As an example of a camera module, the camera modules described in Japanese Patent Publication No. 2016-006476 and Japanese Patent Publication No. 2014-197190 can be referred to, and these contents are incorporated into this manual.
<化合物、紅外線吸收劑> 本發明的化合物為由上述式(1)表示之化合物(特定化合物)。又,本發明的紅外線吸收劑包含由上述式(1)表示之化合物(特定化合物)。本發明的紅外線吸收劑可以僅包含1種由上述式(1)表示之化合物,亦可以包含2種以上。 [實施例] <Compound, infrared absorber> The compound of the present invention is a compound (specific compound) represented by the above formula (1). In addition, the infrared absorber of the present invention includes a compound (specific compound) represented by the above formula (1). The infrared absorber of the present invention may include only one compound represented by the above formula (1), or may include two or more compounds. [Example]
以下,舉出實施例對本發明進行進一步詳細的說明。以下實施例所示之材料、使用量、比例、處理內容、處理順序等,只要不脫離本發明的主旨,則能夠適當變更。再者,以下所示之結構式中,Me為甲,Et為乙基,iPr為異丙基。The present invention is further described in detail below with reference to the following examples. The materials, usage amounts, ratios, treatment contents, treatment sequences, etc. shown in the following examples can be appropriately changed without departing from the gist of the present invention. In the structural formula shown below, Me is methyl, Et is ethyl, and iPr is isopropyl.
<合成例> (合成例1)化合物PM-a-4的合成 [步驟1] 參考日本特開2009-019145號公報的0113~0121段的記載,合成了化合物1。 [化學式11] <Synthesis Example> (Synthesis Example 1) Synthesis of Compound PM-a-4 [Step 1] Compound 1 was synthesized with reference to paragraphs 0113 to 0121 of JP-A-2009-019145. [Chemical Formula 11]
[步驟2] 參考國際公開第2012/054367號中記載之方法,按照以下方案,合成了化合物3。再者,DMF為二甲基甲醯胺。 [化學式12] [Step 2] Referring to the method described in International Publication No. 2012/054367, compound 3 was synthesized according to the following scheme. DMF is dimethylformamide. [Chemical Formula 12]
[步驟3] 在300ml的茄型燒瓶中放入步驟1中獲得之化合物1(17.8g,2mmol)、步驟2中獲得之化合物3(9.2g,4mmol)並溶解於100ml的吡啶之後,添加少量的三乙胺,使其加熱還流了1小時。反應結束後,將溶劑濃縮之後,藉由管柱層析(乙酸乙酯/二氯甲烷)進行純化來獲得了固體。將所獲得之固體再沉澱於己烷/二氯甲烷中,單離出了褐色固體(1.0g,0.8mmol,產率為41%)。 藉由MS及 19F NMR(核磁共振分析)鑑定所獲得之褐色固體,確認為化合物PM-a-4。 MS(Mass spectrometry:質譜法):m/z=609.47[M-B(C 6F 5) 4)] +在 19F-NMR(氟19核磁共振)中確認了源自B(C 6F 5) 4)的以下峰。 -132.4ppm(2F),-163.2ppm(1F),-166.8ppm(2F) [化學式13] [Step 3] Compound 1 (17.8 g, 2 mmol) obtained in step 1 and compound 3 (9.2 g, 4 mmol) obtained in step 2 were placed in a 300 ml eggplant-shaped flask and dissolved in 100 ml of pyridine. A small amount of triethylamine was added and the mixture was heated and refluxed for 1 hour. After the reaction was completed, the solvent was concentrated and purified by column chromatography (ethyl acetate/dichloromethane) to obtain a solid. The obtained solid was precipitated in hexane/dichloromethane to isolate a brown solid (1.0 g, 0.8 mmol, yield 41%). The obtained brown solid was identified by MS and 19 F NMR (nuclear magnetic resonance analysis) and confirmed to be compound PM-a-4. MS (Mass spectrometry): m/z = 609.47 [MB (C 6 F 5 ) 4 )] + The following peaks derived from B (C 6 F 5 ) 4 ) were confirmed in 19 F-NMR (fluorine 19 nuclear magnetic resonance). -132.4 ppm (2F), -163.2 ppm (1F), -166.8 ppm (2F) [Chemical formula 13]
<組成物的製造> 將下述表中記載之成分分別以下述表中記載之質量份混合並攪拌之後,利用孔徑0.45μm的尼龍製過濾器(Nihon Pall Ltd.製)過濾,由此製造了組成物。 <Production of composition> The components listed in the following table were mixed in the mass parts listed in the following table, stirred, and then filtered using a nylon filter with a pore size of 0.45 μm (manufactured by Nihon Pall Ltd.) to produce a composition.
[表6]
[表16]
[表18]
[表20]
上述表中記載之材料的詳細內容為如下。The details of the materials listed in the above table are as follows.
(紅外線吸收劑) PM-a-1~PM-a-25、PM-b-1~PM-b-15、PM-c-1~PM-c-15、PM-d-1~PM-d-15、PM-e-1~PM-e-15:上述特定化合物的具體例中示出的化合物PM-a-1~PM-a-25、PM-b-1~PM-b-15、PM-c-1~PM-c-15、PM-d-1~PM-d-15、PM-e-1~PM-e-15 (Infrared absorber) PM-a-1 to PM-a-25, PM-b-1 to PM-b-15, PM-c-1 to PM-c-15, PM-d-1 to PM-d-15, PM-e-1 to PM-e-15: the compounds PM-a-1 to PM-a-25, PM-b-1 to PM-b-15, PM-c-1 to PM-c-15, PM-d-1 to PM-d-15, PM-e-1 to PM-e-15 shown in the specific examples of the above-mentioned specific compounds
PM-x-1:下述結構的化合物(比較化合物) [化學式14] PM-x-1: Compound with the following structure (comparative compound) [Chemical formula 14]
A-1~A-4:下述結構的化合物(方酸菁化合物) [化學式15] A-1 to A-4: Compounds with the following structures (squarylium compounds) [Chemical formula 15]
B-1~B-3:下述結構的化合物(酞菁化合物) [化學式16] B-1 to B-3: Compounds with the following structures (phthalocyanine compounds) [Chemical formula 16]
(樹脂) C-1:藉由日本特開2021-134350號公報的樹脂合成例1中記載之方法合成之下述結構的樹脂(重量平均分子量137000、數量平均分子量32000、玻璃轉移溫度165℃) C-2:藉由日本特開2021-134350號公報的樹脂合成例2中記載之方法合成之下述結構的樹脂(重量平均分子量188000、數量平均分子量75000、玻璃轉移溫度285℃) C-3:藉由日本特開2021-134350號公報的樹脂合成例3中記載之方法合成之下述結構的樹脂(標註於主鏈之數值表示重複單元的莫耳比。玻璃轉移溫度310℃。對數黏度0.87) C-4:ACRYVIEWA(NIPPON SHOKUBAI CO., LTD.製丙烯酸樹脂) C-5:下述結構的樹脂(標註於主鏈之數值表示重複單元的質量比。重量平均分子量26100、數量平均分子量8600、環氧當量355g/eq、酸值163mgKOH/g、玻璃轉移溫度133℃) C-6:下述結構的樹脂(標註於主鏈之數值表示重複單元的質量比。重量平均分子量22900、數量平均分子量8800、環氧當量316g/eq、酸值130mgKOH/g、玻璃轉移溫度124℃) C-7:下述結構的樹脂(標註於主鏈之數值表示重複單元的質量比。重量平均分子量18300、數量平均分子量9100、環氧當量284g/eq、酸值98mgKOH/g、玻璃轉移溫度134℃) C-8:下述結構的樹脂(標註於主鏈之數值表示重複單元的質量比。重量平均分子量20000、數量平均分子量8300、環氧當量284g/eq、酸值130mgKOH/g、玻璃轉移溫度136℃) C-9:下述結構的樹脂(標註於主鏈之數值表示重複單元的質量比。重量平均分子量21100、數量平均分子量8500、環氧當量355g/eq、酸值157mgKOH/g、玻璃轉移溫度157℃) C-10:下述結構的樹脂(標註於主鏈之數值表示重複單元的質量比。重量平均分子量9500、數量平均分子量5800) C-11:下述結構的樹脂(標註於主鏈之數值表示重複單元的質量比。重量平均分子量23700、數量平均分子量10300、環氧當量284g/eq、玻璃轉移溫度83℃) C-12:EPICLON N-695(DIC Corporation製酚醛清漆型環氧樹脂) C-13:下述結構的樹脂(標註於主鏈之數值表示重複單元的莫耳比。重量平均分子量30000、數量平均分子量15100、酸值113mgKOH/g) C-14:下述結構的樹脂(標註於主鏈之數值表示重複單元的莫耳比。重量平均分子量9700、數量平均分子量5700、酸值130mgKOH/g) C-15:下述結構的樹脂(標註於主鏈之數值表示重複單元的莫耳比。重量平均分子量15100、數量平均分子量7000、酸值136mgKOH/g) C-16:下述結構的樹脂(標註於主鏈之數值表示重複單元的莫耳比。重量平均分子量17000、數量平均分子量7700、酸值32mgKOH/g) C-17:下述結構的樹脂(標註於主鏈之數值表示重複單元的莫耳比。重量平均分子量16000、數量平均分子量5800、酸值101mgKOH/g) C-18:下述結構的樹脂(標註於主鏈之數值表示重複單元的莫耳比。重量平均分子量10000、數量平均分子量3900、酸值69mgKOH/g) [化學式17] [化學式18] (Resin) C-1: A resin having the following structure synthesized by the method described in Resin Synthesis Example 1 of Japanese Patent Publication No. 2021-134350 (weight average molecular weight 137,000, number average molecular weight 32,000, glass transition temperature 165°C) C-2: A resin having the following structure synthesized by the method described in Resin Synthesis Example 2 of Japanese Patent Publication No. 2021-134350 (weight average molecular weight 188,000, number average molecular weight 75,000, glass transition temperature 285°C) C-3: A resin having the following structure synthesized by the method described in Resin Synthesis Example 3 of Japanese Patent Publication No. 2021-134350 (the numerical value annotated on the main chain represents the molar ratio of the repeating unit. Glass transition temperature 310°C. Logarithmic viscosity 0.87) C-4: ACRYVIEWA (acrylic resin manufactured by NIPPON SHOKUBAI CO., LTD.) C-5: Resin having the following structure (the values attached to the main chain represent the mass ratio of the repeating units. Weight average molecular weight 26100, number average molecular weight 8600, epoxy equivalent 355 g/eq, acid value 163 mgKOH/g, glass transition temperature 133°C) C-6: Resin having the following structure (the values attached to the main chain represent the mass ratio of the repeating units. Weight average molecular weight 22900, number average molecular weight 8800, epoxy equivalent 316 g/eq, acid value 130 mgKOH/g, glass transition temperature 124°C) C-7: Resin with the following structure (the values attached to the main chain represent the mass ratio of the repeating units. Weight average molecular weight 18300, number average molecular weight 9100, epoxy equivalent 284g/eq, acid value 98mgKOH/g, glass transition temperature 134℃) C-8: Resin with the following structure (the values attached to the main chain represent the mass ratio of the repeating units. Weight average molecular weight 20000, number average molecular weight 8300, epoxy equivalent 284g/eq, acid value 130mgKOH/g, glass transition temperature 136℃) C-9: Resin having the following structure (the values attached to the main chain represent the mass ratio of the repeating units. Weight average molecular weight 21100, number average molecular weight 8500, epoxy equivalent 355 g/eq, acid value 157 mgKOH/g, glass transition temperature 157°C) C-10: Resin having the following structure (the values attached to the main chain represent the mass ratio of the repeating units. Weight average molecular weight 9500, number average molecular weight 5800) C-11: Resin having the following structure (the values attached to the main chain represent the mass ratio of the repeating units. Weight average molecular weight 23700, number average molecular weight 10300, epoxy equivalent 284 g/eq, glass transition temperature 83°C) C-12: EPICLON N-695 (phenolic varnish type epoxy resin manufactured by DIC Corporation) C-13: Resin with the following structure (the values attached to the main chain represent the molar ratio of the repeating units. Weight average molecular weight 30000, number average molecular weight 15100, acid value 113 mgKOH/g) C-14: Resin with the following structure (the values attached to the main chain represent the molar ratio of the repeating units. Weight average molecular weight 9700, number average molecular weight 5700, acid value 130mgKOH/g) C-15: Resin with the following structure (The values attached to the main chain represent the molar ratio of the repeating units. Weight average molecular weight 15100, number average molecular weight 7000, acid value 136mgKOH/g) C-16: Resin with the following structure (The values attached to the main chain represent the molar ratio of the repeating units. Weight average molecular weight 17000, number average molecular weight 7700, acid value 32mgKOH/g) C-17: Resin with the following structure (The values attached to the main chain represent the molar ratio of the repeating units. Weight average molecular weight 16000, number average molecular weight 5800, acid value 101mgKOH/g) C-18: Resin with the following structure (the numbers attached to the main chain represent the molar ratio of repeating units. Weight average molecular weight 10000, number average molecular weight 3900, acid value 69 mgKOH/g) [Chemical formula 17] [Chemical formula 18]
(紫外線吸收劑) D-1:下述結構的化合物(二氯甲烷中的吸收極大波長394nm) D-2:Uvinul3050(BASF公司製下述結構的化合物) D-3:Tinuvin477(BASF公司製羥苯基三𠯤系紫外線吸收劑) D-4:Tinuvin326(BASF公司製下述結構的化合物) D-5:國際公開第2021/131355號中記載之化合物(2)-22(下述結構的化合物) D-6:國際公開第2021/131355號中記載之化合物(1)-46(下述結構的化合物) D-7:國際公開第2021/132247號中記載之化合物A-1(下述結構的化合物) D-8:NeoHeliopan357(Symrise AG製下述結構的化合物) D-9:下述結構的化合物 [化學式19] (Ultraviolet light absorber) D-1: Compound with the following structure (maximum absorption wavelength in dichloromethane is 394 nm) D-2: Uvinul 3050 (compound with the following structure manufactured by BASF) D-3: Tinuvin 477 (hydroxyphenyl trisulphonium-based ultraviolet light absorber manufactured by BASF) D-4: Tinuvin 326 (compound with the following structure manufactured by BASF) D-5: Compound (2)-22 described in International Publication No. 2021/131355 (compound with the following structure) D-6: Compound (1)-46 described in International Publication No. 2021/131355 (compound with the following structure) D-7: Compound A-1 described in International Publication No. 2021/132247 (compound with the following structure) D-8: NeoHeliopan 357 (Symrise AG: Compound of the following structure) D-9: Compound of the following structure [Chemical Formula 19]
(抗氧化劑) E-1:ADEKA STAB AO-60(ADEKA CORPORATION製下述結構的化合物) E-2:ADEKA STAB AO-80(ADEKA CORPORATION製下述結構的化合物) E-3:下述結構的化合物 E-4:ADEKA STAB 2112(ADEKA CORPORATION製下述結構的化合物) E-5:ADEKA STAB PEP-36(ADEKA CORPORATION製下述結構的化合物) E-6:ADEKA STAB HP-10(ADEKA CORPORATION製下述結構的化合物) E-7:ADEKA STAB AO-412S(ADEKA CORPORATION製下述結構的化合物) [化學式20] (Antioxidant) E-1: ADEKA STAB AO-60 (Compound with the following structure manufactured by ADEKA CORPORATION) E-2: ADEKA STAB AO-80 (Compound with the following structure manufactured by ADEKA CORPORATION) E-3: Compound with the following structure E-4: ADEKA STAB 2112 (Compound with the following structure manufactured by ADEKA CORPORATION) E-5: ADEKA STAB PEP-36 (Compound with the following structure manufactured by ADEKA CORPORATION) E-6: ADEKA STAB HP-10 (Compound with the following structure manufactured by ADEKA CORPORATION) E-7: ADEKA STAB AO-412S (Compound with the following structure manufactured by ADEKA CORPORATION) [Chemical formula 20]
(溶劑) F-1:二氯甲烷 F-2:N,N-二甲基乙醯胺 F-3:環己烷 F-4:二甲苯 F-5:環戊酮 F-6:環己酮 F-7:丙二醇單甲醚乙酸酯(PGMEA) F-8:丙二醇單甲醚(PGME) (Solvent) F-1: Dichloromethane F-2: N,N-dimethylacetamide F-3: Cyclohexane F-4: Xylene F-5: Cyclopentanone F-6: Cyclohexanone F-7: Propylene glycol monomethyl ether acetate (PGMEA) F-8: Propylene glycol monomethyl ether (PGME)
(界面活性劑) G-1:FTX-218D(Neos Corporation製氟系界面活性劑) G-2:MEGAFACE F-554(DIC Corporation製氟系界面活性劑) G-3:KF-6001(Shin-Etsu Chemical Co., Ltd.製聚矽氧系界面活性劑) G-4:下述結構的化合物(重量平均分子量14000,表示重複單元的比例之%的數值為莫耳%) [化學式21] (Surfactant) G-1: FTX-218D (fluorine-based surfactant manufactured by Neos Corporation) G-2: MEGAFACE F-554 (fluorine-based surfactant manufactured by DIC Corporation) G-3: KF-6001 (polysilicone-based surfactant manufactured by Shin-Etsu Chemical Co., Ltd.) G-4: Compound having the following structure (weight average molecular weight 14,000, % values representing the ratio of repeating units are molar %) [Chemical Formula 21]
(硬化劑) H-1:偏苯三甲酸 H-2:2-乙基-4-甲基咪唑 H-3:甲基四氫鄰苯二甲酸酐 (Hardener) H-1: trimellitic acid H-2: 2-ethyl-4-methylimidazole H-3: methyltetrahydrophthalic anhydride
(聚合性化合物) I-1:KAYARAD DPHA(Nippon Kayaku Co., Ltd.製二季戊四醇六丙烯酸酯與二季戊四醇五丙烯酸酯的混合物) I-2:KAYARAD RP-1040(Nippon Kayaku Co., Ltd.製環氧乙烷改質新戊四醇四丙烯酸酯) I-3:ARONIX M-510(TOAGOSEI CO., LTD.製多元酸改質丙烯酸寡聚物) (Polymerizable compound) I-1: KAYARAD DPHA (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate manufactured by Nippon Kayaku Co., Ltd.) I-2: KAYARAD RP-1040 (ethylene oxide-modified neopentylthritol tetraacrylate manufactured by Nippon Kayaku Co., Ltd.) I-3: ARONIX M-510 (polyacid-modified acrylic oligomer manufactured by TOAGOSEI CO., LTD.)
(光聚合起始劑) J-1:Irgacure OXE01(BASF公司製肟酯化合物) J-2:國際公開第2017/169819號中記載之化合物No.1(下述結構的化合物) J-3:國際公開第2017/169819號中記載之化合物No.10(下述結構的化合物) J-4:日本特開2019-168654號公報中記載之化合物No.5(下述結構的化合物) J-5:日本特開2019-168654號公報中記載之化合物No.73(下述結構的化合物) [化學式22] (Photopolymerization initiator) J-1: Irgacure OXE01 (oxime ester compound manufactured by BASF) J-2: Compound No. 1 described in International Publication No. 2017/169819 (compound having the following structure) J-3: Compound No. 10 described in International Publication No. 2017/169819 (compound having the following structure) J-4: Compound No. 5 described in Japanese Patent Publication No. 2019-168654 (compound having the following structure) J-5: Compound No. 73 described in Japanese Patent Publication No. 2019-168654 (compound having the following structure) [Chemical formula 22]
(聚合抑制劑) K-1:對甲氧基苯酚 (矽烷偶合劑) L-1、L-2:下述結構的化合物 [化學式23] (Polymerization inhibitor) K-1: p-methoxyphenol (silane coupling agent) L-1, L-2: Compounds with the following structure [Chemical formula 23]
<膜的製造> (製造例1)使用了實施例1~113、比較例1的組成物之膜的製造方法 將各組成物澆鑄在玻璃基板上,以20℃乾燥8小時之後,從玻璃基板剝離。將剝離的塗膜進一步在減壓下以100℃乾燥8小時,獲得了厚度0.1mm、縱60mm、橫60mm的膜。 <Production of film> (Production Example 1) Production method of film using the composition of Examples 1 to 113 and Comparative Example 1 Each composition was cast on a glass substrate, dried at 20°C for 8 hours, and then peeled off from the glass substrate. The peeled coating was further dried at 100°C for 8 hours under reduced pressure to obtain a film with a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm.
(製造例2)使用了實施例201~323、比較例2的組成物之膜的製造方法 藉由旋塗法,將各組成物塗布於玻璃基板上,之後利用加熱板以100℃加熱2分鐘,接著以200℃加熱8分鐘而進行硬化處理,由此獲得了厚度10μm的膜。 (Manufacturing Example 2) Method for manufacturing a film using the composition of Examples 201 to 323 and Comparative Example 2 Each composition was applied to a glass substrate by spin coating, and then heated at 100°C for 2 minutes using a heating plate, and then heated at 200°C for 8 minutes for hardening, thereby obtaining a film with a thickness of 10 μm.
(製造例3)使用了實施例401~528、比較例3的組成物之膜的製造方法 藉由旋塗法,將各組成物塗布於玻璃基板上,之後利用加熱板以100℃加熱2分鐘,由此獲得了組成物層。將所獲得之組成物層利用i射線步進曝光裝置FPA-3000i5+(Canon Inc.製),以500mJ/cm 2的曝光量進行了整面曝光。接著,利用加熱板,以200℃加熱曝光後的組成物層5分鐘而進行硬化處理,由此獲得了厚度1.0μm的膜。 (Manufacturing Example 3) Method for manufacturing a film using the composition of Examples 401 to 528 and Comparative Example 3 Each composition was applied to a glass substrate by spin coating, and then heated at 100°C for 2 minutes using a heating plate, thereby obtaining a composition layer. The obtained composition layer was fully exposed using an i-ray stepper exposure device FPA-3000i5+ (manufactured by Canon Inc.) at an exposure amount of 500mJ/ cm2 . Then, the exposed composition layer was heated at 200°C for 5 minutes using a heating plate to perform a curing treatment, thereby obtaining a film with a thickness of 1.0μm.
<性能評價> (紅外線遮蔽性的評價基準) 利用分光光度計U-4100(Hitachi High-Tech Corporation製)測定所獲得之膜在波長400~1100nm範圍內的吸光度及透射率,測定顯示出最大吸光度(Absλmax)之波長(λmax),按照以下基準評價了紅外線遮蔽性。 A:λmax±10nm範圍內的平均透射率≤2% B:2%<λmax±10nm範圍內的平均透射率≤4% C:4%<λmax±10nm範圍內的平均透射率≤7% D:7%<λmax±10nm範圍內的平均透射率≤10% E:10%<λmax±10nm範圍內的平均透射率 <Performance evaluation> (Evaluation criteria for infrared shielding properties) The absorbance and transmittance of the obtained film in the wavelength range of 400 to 1100 nm were measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Tech Corporation), and the wavelength (λmax) showing the maximum absorbance (Absλmax) was measured, and the infrared shielding properties were evaluated according to the following criteria. A: Average transmittance within the range of λmax±10nm ≤2% B: Average transmittance within the range of 2%<λmax±10nm ≤4% C: Average transmittance within the range of 4%<λmax±10nm ≤7% D: Average transmittance within the range of 7%<λmax±10nm ≤10% E: Average transmittance within the range of 10%<λmax±10nm
(可見光透射性的評價) 利用分光光度計U-4100(Hitachi High-Tech Corporation製)測定所獲得之膜在波長420~550nm範圍內的平均透射率,按照以下基準評價了可見光透射性。 A:波長420nm~550nm範圍內的平均透射率≥95% B:92%≤波長420nm~550nm範圍內的平均透射率<95% C:89%≤波長420nm~550nm範圍內的平均透射率<92% D:86%≤波長420nm~550nm範圍內的平均透射率<89% E:波長420nm~550nm範圍內的平均透射率<86% (Evaluation of visible light transmittance) The average transmittance of the obtained film in the wavelength range of 420 to 550 nm was measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Tech Corporation), and the visible light transmittance was evaluated according to the following criteria. A: Average transmittance in the wavelength range of 420 nm to 550 nm ≥ 95% B: 92% ≤ Average transmittance in the wavelength range of 420 nm to 550 nm < 95% C: 89% ≤ Average transmittance in the wavelength range of 420 nm to 550 nm < 92% D: 86% ≤ Average transmittance in the wavelength range of 420 nm to 550 nm < 89% E: Average transmittance in the wavelength range of 420 nm to 550 nm < 86%
(耐光性的評價) 利用Xe燈,透過紫外線截止濾波器對所獲得之膜照射5万勒克司的光20小時來進行耐光性試驗,利用色度計MCPD-1000(Otsuka Electronics Co., Ltd.製)測定了光照射前後的色差的ΔEab值。ΔEab值越小,表示耐光性越良好。再者,ΔEab值為由基於CIE1976(L*,a*,b*)空間表色系統之以下色差公式求得之值(日本色彩學會編 新編色彩科學手冊(1985年)266頁)。 ΔEab={(ΔL*) 2+(Δa*) 2+(Δb*) 2} 1/2A:ΔEab值<2.5 B:2.5≤ΔEab值<5 C:5≤ΔEab值<10 D:10≤ΔEab值<15 E:15≤ΔEab值 (Evaluation of light resistance) The obtained film was irradiated with 50,000 lux of light for 20 hours using a Xe lamp through an ultraviolet cutoff filter to conduct a light resistance test, and the ΔEab value of the color difference before and after light irradiation was measured using a colorimeter MCPD-1000 (manufactured by Otsuka Electronics Co., Ltd.). The smaller the ΔEab value, the better the light resistance. The ΔEab value is the value obtained by the following color difference formula based on the CIE1976 (L*, a*, b*) spatial color system (New Color Science Handbook compiled by the Japan Color Society (1985) page 266). ΔEab={(ΔL*) 2 +(Δa*) 2 +(Δb*) 2 } 1/2 A: ΔEab value < 2.5 B: 2.5 ≤ ΔEab value < 5 C: 5 ≤ ΔEab value < 10 D: 10 ≤ ΔEab value < 15 E: 15 ≤ ΔEab value
(保存穩定性的評價) 將各組成物在45℃的恆溫器中保管3天後,按照上述膜的製造方法製造了膜。利用掃描式電子顯微鏡觀察(測定倍率=10000倍)所獲得之膜,測定在10μm×15μm的範圍內存在的異物數,按照以下基準評價了保存穩定性。 A:在10μm×15μm的範圍內不存在異物 B:在10μm×15μm的範圍內存在的異物超出0個且50個以下 C:在10μm×15μm的範圍內存在的異物超出50個且100個以下 D:在10μm×15μm的範圍內存在的異物超出100個且200個以下 E:在10μm×15μm的範圍內存在的異物超出200個 (Evaluation of storage stability) After storing each composition in a thermostat at 45°C for 3 days, a membrane was produced according to the above membrane production method. The obtained membrane was observed using a scanning electron microscope (measurement magnification = 10,000 times), and the number of foreign matter present in the range of 10μm×15μm was measured, and the storage stability was evaluated according to the following criteria. A: No foreign matter exists within the range of 10μm×15μm B: The number of foreign matter within the range of 10μm×15μm exceeds 0 and is less than 50 C: The number of foreign matter within the range of 10μm×15μm exceeds 50 and is less than 100 D: The number of foreign matter within the range of 10μm×15μm exceeds 100 and is less than 200 E: The number of foreign matter within the range of 10μm×15μm exceeds 200
[表22]
[表25]
[表28]
如上述表所示,與比較例相比,實施例的可見光透射性、紅外線遮蔽性、耐光性及保存穩定性的評價優異。As shown in the above table, the examples were evaluated as being superior in terms of visible light transmittance, infrared shielding properties, light resistance, and storage stability compared to the comparative examples.
110:固體攝像元件 111:紅外線截止濾波器 112:濾色器 114:紅外線透射濾波器 115:微透鏡 116:平坦化層 110: Solid-state imaging element 111: Infrared cutoff filter 112: Color filter 114: Infrared transmission filter 115: Microlens 116: Flattening layer
圖1係表示紅外線感測器的一實施形態之概略圖。FIG1 is a schematic diagram showing an embodiment of an infrared sensor.
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JPS59146061A (en) * | 1983-02-09 | 1984-08-21 | Canon Inc | Organic film |
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JP6226842B2 (en) * | 2014-09-16 | 2017-11-08 | 富士フイルム株式会社 | Near-infrared absorbing composition, cured film, near-infrared absorbing filter, solid-state imaging device, infrared sensor, compound |
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