CN107531857A - Thermally reactive composition - Google Patents

Thermally reactive composition Download PDF

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Publication number
CN107531857A
CN107531857A CN201680025737.6A CN201680025737A CN107531857A CN 107531857 A CN107531857 A CN 107531857A CN 201680025737 A CN201680025737 A CN 201680025737A CN 107531857 A CN107531857 A CN 107531857A
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group
wavelength
carbon atoms
heat
resin
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CN201680025737.6A
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Chinese (zh)
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前田洋介
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株式会社艾迪科
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Priority to JP2015156398 priority
Application filed by 株式会社艾迪科 filed Critical 株式会社艾迪科
Priority to PCT/JP2016/072507 priority patent/WO2017022708A1/en
Publication of CN107531857A publication Critical patent/CN107531857A/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02Physical, chemical or physicochemical properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/12Polymers provided for in subclasses C08C or C08F
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS, OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/20Filters
    • G02B5/26Reflecting filters
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS, OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/20Filters
    • G02B5/28Interference filters

Abstract

A thermally reactive composition contains at least one kind of cyanine compound ([alpha]), a resin ([beta]) having at least an ethylenically unsaturated bond and a hydrophilic group, and a thermal polymerization initiator ([gamma]). It is preferable that the resin ([beta]) has a unit represented by general formula (I-1), a unit represented by general formula (I-2) and a unit represented by generalformula (I-3). It is also preferable that the thermal polymerization initiator ([gamma]) is an azo thermal polymerization initiator. Refer to the description for the definitions of Y1, X1 and R1-R4 in the formulae.

Description

热反应性组合物 Heat-reactive composition

技术领域 FIELD

[0001] 本发明涉及含有花青化合物、一分子内具有烯键式不饱和键和亲水性基团的树脂和热聚合引发剂的热反应性组合物、和使用了该热反应性组合物的波长截止滤光器。 [0001] The present invention relates to a cyanine compound, a resin having in one molecule an ethylenically unsaturated bond and a hydrophilic group and a thermal polymerization initiator composition heat reactive agents, and the use of thermally reactive composition wavelength cut filter.

背景技术 Background technique

[0002] 数码相机、摄像机、手机用照相机等中使用的固体摄像元件(CCD和C-MOS等)的感度从光的波长的紫外区域直到红外区域。 [0002] Digital cameras, camcorders, mobile phones with a solid state imaging device (CCD and C-MOS, etc.) or the like used in the camera sensitivity wavelength region from ultraviolet light until the infrared region. 另一方面,人的视见度仅为光的波长的可见区域。 On the other hand, only the visible region of visibility of light having a wavelength of people. 因此,通过在摄像镜头与固体摄像元件之间设置红外线截止滤光器,以与人的视见度接近的方式校正了固体摄像元件的感度。 Thus, by providing the infrared cut filter between the imaging lens and the solid-state imaging device, with the visibility of the person to approach the corrected sensitivity of the solid-state imaging device.

[0003] 作为红外线截止滤光器,已知将含有不具有吸收特性的物质的层组合而层叠成多层并利用了它们的折射率之差的反射型滤光器、或使透明基板含有或结合了光吸收剂的吸收型滤光器。 [0003] As the infrared cut filter, there is known a combination of a layer containing a substance having no absorption characteristics and laminated multilayered reflective filter utilizes the difference in refractive index thereof, or the transparent substrate containing or It combines light absorber absorbing filter.

[0004] 特别是对于吸收型滤光器来说,存在因制造时的加热处理等而引起光吸收剂的劣化,导致红外线遮断能力下降的问题。 [0004] Especially for absorbing filter, a heat treatment or the like due to the presence during production due to deterioration of the light absorber, an infrared blocking problems resulting in reduced ability.

[0005] 专利文献1和2中记载了含有热聚合引发剂的热反应性组合物。 [0005] Patent Documents 1 and 2 describes a thermal polymerization initiator containing a thermally reactive composition. 另外,专利文献3中记载了含有花青化合物、一分子内具有烯键式不饱和键和亲水性基团的树脂和光聚合引发剂的组合物。 Further, Patent Document 3 discloses a composition containing a cyanine compound, a resin having an ethylenically unsaturated bond and a hydrophilic group and a photopolymerization initiator within the molecule.

[0006] 现有技术文献[0007] 专利文献 [0006] The prior art document [0007] Patent Document

[0008] 专利文献1:日本特开2007-256865号公报 [0008] Patent Document 1: Japanese Laid-Open Patent Publication No. 2007-256865

[0009] 专利文献2:US2010051883A1 [0009] Patent Document 2: US2010051883A1

[0010] 专利文献3:日本特开2013-173848号公报 [0010] Patent Document 3: Japanese Laid-Open Patent Publication No. 2013-173848

发明内容 SUMMARY

[0011] 发明所要解决的课题 [0011] Problem to be solved by the invention

[0012] 可是,专利文献1〜3中记载的组合物在耐热性方面并不充分。 [0012] However, the composition described in Patent Document 1 ~ 3 are not sufficient in heat resistance.

[0013] 因此,本发明的目的是提供一种耐热性优良的热反应性组合物。 [0013] Accordingly, an object of the present invention is to provide an excellent heat resistance of the heat-reactive composition. 另外,本发明的另一个目的是提供一种使用了上述热反应性组合物的波长截止滤光器。 Further, another object of the present invention is to provide a thermal reaction using a wavelength of the composition cutoff filter.

[0014] 用于解决课题的手段 [0014] Means for Solving the Problem

[0015] 本发明人反复进行了深入研究,结果发现,使用含有花青化合物、一分子内具有烯键式不饱和键和亲水性基团的树脂、以及热聚合引发剂的热反应性组合物而得到的波长截止滤光器的耐热性不会下降,适合于固体摄像装置等中使用的波长截止滤光器,从而完成了本发明。 [0015] The present inventors have conducted intensive studies and found, containing a cyanine compound, a resin having an ethylenically unsaturated bond and a hydrophilic group in the molecule, and a thermal polymerization initiator, a combination of thermally reactive agent was obtained by a wavelength cut-off filter does not decrease the heat resistance, suitable for use in wavelength solid-state imaging device or the like cut filter, thereby completing the present invention.

[0016] 本发明提供一种热反应性组合物,其含有:花青化合物中的至少一种(α)、至少具有烯键式不饱和键和亲水性基团的树脂(β)、以及热聚合引发剂(γ)。 [0016] The present invention provides a thermally reactive composition, comprising: at least one cyanine compound ([alpha]), the resin having at least ethylenically unsaturated bond and a hydrophilic group (beta]), and a thermal polymerization initiator (γ).

[0017] 另外,本发明提供一种使用上述热反应性组合物而得到的波长截止滤光器、以及使用了它的固体摄像装置和照相机模块。 Wavelength [0017] Further, the present invention provides a thermal reaction using the composition obtained cut filter, and the use of its solid state imaging device and a camera module.

[0018] 发明效果 [0018] Effect of the Invention

[0019] 含有花青化合物、一分子内具有烯键式不饱和键和亲水性基团的树脂以及热聚合引发剂的本发明的热反应性组合物具有优良的耐热性。 [0019] The cyanine compound containing, in one molecule, and a resin having a thermally polymerizable ethylenically unsaturated bond and a hydrophilic group initiator heat-reactive composition of the present invention has excellent heat resistance. 另外,其固化物适合于波长截止滤光器。 Further, a cured product suitable for wavelength cutoff filter.

附图说明 BRIEF DESCRIPTION

[0020] 图1是表示本发明的波长截止滤光器的层构造的一例的示意截面图。 [0020] FIG. 1 is a schematic sectional view showing an example of the present invention, a wavelength cut filter layer configuration.

[0021] 图2是表示本发明的波长截止滤光器的层构造的另一例的示意截面图。 [0021] FIG. 2 is a schematic sectional view showing another embodiment of the layer configuration of the present invention is a wavelength cut-off filter.

[0022] 图3是表示作为本发明的固体摄像装置之一的照相机模块的构成的一个形态的截面图。 [0022] FIG. 3 is a sectional view showing one aspect of one configuration of a camera module according to the present invention, the solid-state imaging device.

[0023] 图4是表示照相机模块的构成的另一个形态的截面图。 [0023] FIG. 4 is a sectional view of another aspect of the configuration of the camera module.

[0024] 图5是表示照相机模块的构成的又一个形态的截面图。 [0024] FIG. 5 is a sectional view showing another aspect of the configuration of the camera module.

[0025] 图6是表示照相机模块的构成的又一个形态的截面图。 [0025] FIG. 6 is a sectional view showing another aspect of the configuration of the camera module.

具体实施方式 Detailed ways

[0026] 以下,基于优选的实施形态对本发明的热反应性组合物进行说明。 [0026] Hereinafter, a preferred embodiment of the heat-reactive composition of the present invention will be described.

[0027] 本发明的热反应性组合物含有:花青化合物中的至少一种(α)(以下也称作花青化合物⑷)、至少具有烯键式不饱和键和亲水性基团的树脂(β)(以下也称作树脂(β))、热聚合引发剂(Y)、以及根据需要进一步添加的具有不饱和键的单体(ω)和溶剂(〇)。 [0027] The heat-reactive composition of the present invention comprises: at least one cyanine compound ([alpha]) (hereinafter also referred to as cyanine compound ⑷), having at least ethylenically unsaturated bond and a hydrophilic group resin (beta]) (hereinafter referred to as resin (β)), a thermal polymerization initiator (Y), and monomer ([omega]) and a solvent (square) having an unsaturated bond is further added as needed. 以下对各成分依次说明。 The following description of each component in turn.

[0028] 〈花青化合物(α) > [0028] <cyanine compound (α)>

[0029] 本发明的热反应性组合物中使用的花青化合物(α)没有特别限制,可以使用以往公知的花青化合物,但从获得容易性的观点出发,优选由下述通式(II)表示的化合物。 [0029] The heat-reactive composition of the present invention is used in the cyanine compound ([alpha]) is not particularly limited, and conventionally known cyanine compounds, but easy availability viewpoint, preferably by the following formula (II ) a compound represented by.

[0030] [化1] [0030] [Formula 1]

[0031] [0031]

Figure CN107531857AD00051

[0032] (式中,环A和环Α'分别独立地表示苯环、萘环、菲环或吡啶环, [0032] (wherein ring A and ring Α 'each independently represent a benzene ring, a naphthalene ring, a phenanthrene ring or a pyridine ring,

[0033] R11和R11'分别独立地表示羟基、卤原子、硝基、氰基、-S03H、羧基、氨基、酰胺基、茂金属基(metallocenyl)、碳原子数为6〜30的芳基、碳原子数为7〜30的芳烧基或碳原子数为1〜8的烧基, [0033] R11 and R11 'each independently represents a hydroxyl group, a halogen atom, nitro, cyano, -S03H, a carboxyl group, an amino group, an amide group, a metallocene group (metallocenyl), 6~30 carbon atoms, an aryl group, burn carbon atoms, an aryl group of 7~30 carbon atoms or is a group 1~8 of burning,

[0034] X11和X11'分别独立地表示氧原子、硫原子、硒原子、-CR23R24-、碳原子数为3〜6的环链烧_1,1_二基或_NR25-, [0034] X11 and X11 'each independently represent an oxygen atom, a sulfur atom, a selenium atom, -CR23R24-, 3 ~ 6 carbon atoms in the chain or burning _1,1_ diyl _NR25-,

[0035] R21、R22、R23、R24和R25分别独立地表示氢原子、羟基、齒原子、硝基、氰基、-S03H、羧基、氨基、酰胺基、茂金属基、碳原子数为6〜30的芳基、碳原子数为7〜30的芳烷基或碳原子数为1〜8的烷基, [0035] R21, R22, R23, R24 and R25 each independently represent a hydrogen atom, a hydroxyl group, teeth atoms, nitro, cyano, -S03H, a carboxyl group, an amino group, an amide group, a metallocene group, 6 ~ carbon atoms, aralkyl group or an aryl group of carbon atoms, 30 carbon atoms, as for 7~30 1~8 alkyl group,

[0036] Y11和Y11'分别独立地表示氢原子、或可以被羟基、卤原子、硝基、氰基、_S03H、羧基、 氨基、酰胺基或茂金属基取代的碳原子数为6〜30的芳基、碳原子数为7〜30的芳烷基或碳原子数为1〜8的烷基, [0036] Y11 and Y11 'each independently represent a hydrogen atom, or may be a hydroxyl group, carbon atoms and a halogen atom, a nitro group, a cyano group, _S03H, a carboxyl group, an amino group, an amide group or a group substituted for the metallocene of 6~30 aralkyl group or an aryl group of carbon atoms, having a carbon number of 7~30 1~8 alkyl group,

[0037] 上述R11、R11'、Y11、Y11 '、R21、R22、R23、R24和R25中的芳基、芳烧基和烧基有时也被轻基、齒原子、硝基、氰基、-S03H、羧基、氨基、酰胺基或茂金属基取代,上述R'RH'J'Y11'、 r21、r22、r23、r24^pr25中的芳烧基和烧基中的亚甲基有时也被s-、-C〇_、-⑶〇_、-〇c〇_、- S〇2_、_NH-、-CONH-、-NHCO-、-N=CH-或碳-碳双键置换, [0037] The R11, R11 ', Y11, Y11', R21, R22, R23, R24 and R25 are aryl, the aryl group, and burn burn sometimes light-yl group, a tooth atoms, nitro, cyano, - S03H, a carboxyl group, an amino group, an amide group or a group substituted metallocene said R'RH'J'Y11 ', r21, r22, r23, r24 ^ pr25 burned in the aryl group, and a methylene group burning sometimes s -, - C〇 _, - ⑶〇 _, - 〇c〇 _, - S〇2 _, _ NH -, - CONH -, - NHCO -, - N = CH- or a carbon - carbon double bond is replaced

[0038] Q表示构成碳原子数为1〜9的次甲基链、并且链中可以含有环结构的连接基,该次甲基链中的氢原子也可以被羟基、卤原子、氰基、-NRR'、芳基、芳烷基或烷基取代,该-NRR'、 芳基、芳烷基和烷基还可以进一步被羟基、卤原子、氰基或-NRR'取代,也可以被-0-、-5-、-CO-、-COO-、-0C0-、-SO2-、-NH-、-CONH-、-NHCO-、-N=CH-或-CH=CH-中断, [0038] Q represents the number of carbon atoms constituting the methine chain 1~9, and the linker chain may contain a ring structure, hydrogen atoms of the methine chain may be a hydroxyl group, a halogen atom, a cyano group, -NRR ', aryl group, aralkyl group or alkyl substituted, the -NRR', aryl, aralkyl, and alkyl may further be substituted with a hydroxyl group, a halogen atom, a cyano group, or -NRR ', it may also be - 0 -, - 5 -, - CO -, - COO -, - 0C0 -, - SO2 -, - NH -, - CONH -, - NHCO -, - N = CH- or -CH = CH- interrupted,

[0039] R和R'表示芳基、芳烷基或烷基, [0039] R and R 'represent an aryl group, or aralkyl group,

[0040] r和r'表示0或在环A和环A'上可取代的数量, [0040] r and r 'represents 0 or Ring A and ring A' can be substituted on the quantity,

[0041] Antr表示q价的阴离子,q表示1或2,p表示将电荷保持为中性的系数。 [0041] Antr represents a q-valent anion, q represents 1 or 2, p represents a coefficient to maintain neutral electric charge. )

[0042] 作为上述通式(II)中的Rn、Rn'以及X11和X11'中的R23、R24和R25所表示的卤原子、以及可以对!^、!^'、!^、!^、!^、,、,'所表示的芳基〜芳烷基^基进行取代的卤原子河以列举出氟原子、氯原子、溴原子、碘原子。 [0042] In the general formula Rn (II) is halogen atom Rn of 'and X11 and X11' are R23, R24 and R25 are represented by and may! ^! ^ '! ^! ^, ! ^ ,,,, 'aryl ^ ~ aralkyl group represented by halogen atom is substituted at the river include fluorine atom, chlorine atom, bromine atom, iodine atom.

[0043] 作为上述通式(II)中的Rn、Rn'以及X11和X11'中的R23、R24和R25所表示的氨基、以及可以对!^、!^'、!^、!^、^、,、,'所表示的芳基〜芳烷基^基进行取代的氨基河以列举出氨基、乙基氨基、二甲基氨基、二乙基氨基、丁基氨基、环戊基氨基、2-乙基己基氨基、十二烧基氨基、苯胺基、氯苯基氨基、甲苯氨基、甲氧苯胺基、N-甲基-苯胺基、二苯基氨基、萘基氨基、2-吡啶基氨基、甲氧基羰基氨基、苯氧基羰基氨基、乙酰基氨基、苯甲酰基氨基、甲酰基氨基、三甲基乙酰基氨基、月桂酰基氨基、氨基甲酰基氨基、N,N-二甲基氨基羰基氨基、N, N-二乙基氨基羰基氨基、吗啉代羰基氨基、甲氧基羰基氨基、乙氧基羰基氨基、叔丁氧基羰基氨基、正十八烷氧基羰基氨基、N-甲基-甲氧基羰基氨基、苯氧基羰基氨基、氨磺酰基氨基、N,N-二甲基氨基磺酰基氨基、甲 [0043] Examples of the amino group of the general formula (II) in Rn, Rn 'and X11 and X11' are R23, R24 and R25 are represented by and may! ^! ^ '! ^! ^, ^ ,,,, 'aryl ^ ~ aralkyl group represented by r to perform a substituted amino group include amino, ethylamino, dimethylamino, diethylamino, butylamino, cyclopentylamino, 2 - ethylhexyl group, dodecyl group burning, an anilino group, chlorophenyl group, tolyl group, a methoxy anilino, N- methyl - anilino, diphenylamino, naphthylamino, 2-pyridylamino , methoxycarbonyl group, phenoxycarbonyl group, an acetyl group, a benzoyl group, formyl group, pivaloyl group, lauroyl group, a carbamoylamino group, N, N- dimethylamino amino carbonyl, N, N- diethylamino carbonyl amino group, morpholino carbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group, a tert-butoxycarbonyl group, n-octadecyloxy carbonyl amino, N- methyl - methoxycarbonyl group, phenoxycarbonyl group, a sulfamoyl group, N, N- dimethylamino sulfonylamino, A 磺酰基氨基、丁基磺酰基氨基、苯基磺酰基氨基等。 Sulfonylamino group, butylsulfonyl group, a phenylsulfonyl group and the like.

[0044] 作为上述通式(II)中的Rn、Rn'以及X11和X11'中的R23、R24和R25所表示的酰胺基、以及可以对!^、!^'、!^、!^、!^、,、,'所表示的芳基〜芳烷基^基进行取代的酰胺基河以列举出甲酰胺基、乙酰胺基、乙基酰胺基、异丙基酰胺基、丁基酰胺基、辛基酰胺基、壬基酰胺基、癸基酰胺基、十一烷基酰胺基、十二烷基酰胺基、十六烷基酰胺基、十八烷基酰胺基、 (2-乙基己基)酰胺基、苯甲酰胺基、三氟乙酰胺基、五氟苯甲酰胺基、二甲酰胺基、二乙酰胺基、二乙基酰胺基、二异丙基酰胺基、二丁基酰胺基、二辛基酰胺基、二壬基酰胺基、二癸基酰胺基、二(十一烷基)酰胺基、二(十二烷基)酰胺基、二(2-乙基己基)酰胺基、二苯甲酰胺基、二(三氟乙酰)胺基、二(五氟苯甲酰)胺基等。 [0044] In the general formula Rn (II) in the amide group Rn of 'and X11 and X11' are R23, R24 and R25 are represented by and may! ^! ^ '! ^! ^, ! ^ ,,,, 'aryl ^ ~ aralkyl group represented by is substituted amide groups to include river carboxamido, acetamido, diethylamide group, diisopropylamide group, an amide group-butyl , an amide group octyl, nonyl amide, decyl amide group, an amide group undecyl, dodecyl amide, hexadecyl amide, stearyl amide group, (2-ethylhexyl ) an amide group, a benzoyl group, trifluoroacetyl group, pentafluorobenzoyl group, a dimethylamide group, diacetyl group, diethylamide group, diisopropylamide group, a dibutyl amide group , dioctyl amide group, an amide group dinonyl, didecyl amide group, di (undecyl) amido, di (dodecyl) amido, di (2-ethylhexyl) amide, dibenzoyl group, bis (trifluoroacetyl) amino, di (pentafluorobenzoyl) amino and the like.

[0045] 作为上述通式(II)中的Rn、Rn'以及X11和X11'中的R23、R24和R25所表示的茂金属基、 以及可以对!^、!^'、!^、!^、!^、,、一'所表示的芳基〜芳烷基^基进行取代的茂金属基, 可以列举出二茂铁基、二茂镍基、二茂锆基、二茂钛基、二茂铪基等。 [0045] As the metallocene-based formula (II) in Rn, Rn 'and X11 and X11' are R23, R24 and R25 are represented by and may! ^! ^ '! ^! ^ ,! ,,, ^ a 'aryl ^ ~ aralkyl group represented metallocene group is substituted, include ferrocenyl, ferrocene nickel-based, group zirconocene, titanocene group, di hafnocene group.

[0046] 作为上述通式(II)中的Rn、Rn'、211、212、213和¥11、¥11'以及乂11和乂11'中的妒3、1?24和R25所表示的碳原子数为6〜30的芳基,可以列举出苯基、萘基、2-甲基苯基、3-甲基苯基、4- 甲基苯基、4-乙稀基苯基、3-异丙基苯基、4-异丙基苯基、4-丁基苯基、4-异丁基苯基、4-叔丁基苯基、4-己基苯基、4-环己基苯基、4-辛基苯基、4-(2-乙基己基)苯基、4-硬脂酰基苯基、2,3-二甲基苯基、2,4_二甲基苯基、2,5-二甲基苯基、2,6_二甲基苯基、3,4_二甲基苯基、3,5-二甲基苯基、2,4-二叔丁基苯基、2,5-二叔丁基苯基、2,6-二叔丁基苯基、2,4-二叔戊基苯基、2,5-二叔戊基苯基、2,5-二叔辛基苯基、2,4-二枯基苯基、4-环己基苯基、(1,1' -联苯基)-4-基、2,4,5-三甲基苯基、二茂铁基等。 Carbon [0046] Examples of the formula (II) in Rn, Rn ', 211,212,213 and ¥ 11, ¥ 11' and 11 and qe qe 11 'Jealous 3,1? 24 and R25 are represented by atoms of 6~30 aryl group may include phenyl, naphthyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-phenyl ethylene group, 3- isopropylphenyl, 4-isopropylphenyl, 4-butylphenyl, 4-isobutylphenyl, 4-tert-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4- (2-ethylhexyl) phenyl, 4-stearoyl-phenyl, 2,3-dimethylphenyl, 2,4_ dimethylphenyl, 2,5 - dimethylphenyl, dimethylphenyl 2,6_, 3,4_ dimethylphenyl, 3,5-dimethylphenyl, 2,4-di-t-butylphenyl, 2, 3,5-di-tert-butylphenyl, 2,6-di-t-butylphenyl, 2,4-di-t-amyl phenyl, 2,5-di-tert-amyl phenyl, 2,5-di-tert-octyl phenyl, 2,4-dicumyl-phenyl, 4-cyclohexyl-phenyl, (1,1 '- biphenyl) -4-yl, 2,4,5-trimethylphenyl, ferrocene group.

[0047] 作为上述通式(II)中的Rn、Rn'和Yn、Yn'以及X11和X11'中的R23、R24和R25所表示的碳原子数为7〜30的芳烷基,可以列举出苄基、苯乙基、2-苯基丙烷-2-基、二苯基甲基、三苯基甲基、苯乙稀基、肉桂基、^茂铁基甲基、^.茂铁基丙基等。 [0047] Examples of the formula (II) in Rn, carbon atoms, Rn 'and Yn, Yn', and X11 and X11 'are R23, R24 and R25 are as indicated 7~30 aralkyl group include a benzyl group, phenethyl group, 2-phenyl-2-yl, diphenylmethyl, triphenylmethyl, phenylethyl dilute group, cinnamyl group, ferrocenyl-ylmethyl ^, ^. ferrocenyl propyl and the like.

[0048] 作为上述通式(II)中的R11、Rn'和Y11、Y11 '以及X11和X11'中的R23、R24和R25所表示的碳原子数为1〜8的烷基,可以列举出甲基、乙基、丙基、异丙基、丁基、仲丁基、叔丁基、异丁基、戊基、异戊基、叔戊基、己基、2-己基、3-己基、环己基、1-甲基环己基、庚基、2-庚基、3-庚基、异庚基、叔庚基、1-辛基、异辛基、叔辛基等。 [0048] Examples of the formula (II) in R11, carbon atoms, Rn 'and Y11, Y11' and X11 and X11 'are R23, R24 and R25 are as indicated 1~8 alkyl group, include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, pentyl, isopentyl, tert-pentyl, hexyl, 2-hexyl, 3-hexyl, ring hexyl group, 1-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, iso-heptyl group, a tert-heptyl, 1-octyl, iso-octyl, t-octyl and the like.

[0049] 作为上述R11、R11'和Y11、Y11 '以及X11和X11'中的R23、R24和R25中的、可以被羟基、卤原子、硝基、氰基、-SO3H基、羧基、氨基、酰胺基或茂金属基取代的碳原子数为6〜30的芳基、碳原子数为7〜30的芳烷基和碳原子数为1〜20的烷基,可以列举出在上述R11等的说明中所列举的芳基、芳烷基、烷基和这些基团中的氢原子被羟基、卤原子、硝基、氰基、-SO3H基、羧基、 氨基、酰胺基或茂金属基取代后的基团,这些取代基的位置和数量没有限制。 [0049] Examples of the R11, R11 'and Y11, Y11' and X11 and X11 'are R23, R24 and R25 are, can be a hydroxyl group, a halogen atom, a nitro group, a cyano group, -SO3H group, a carboxyl group, an amino group, carbon atoms, an amide group or a metallocene-substituted aryl group of 6~30, 7~30 carbon atoms and an aralkyl group having a carbon number of 1~20 alkyl group R11 include the above and the like after the description recited aryl group, an aralkyl group, an alkyl group and a hydrogen atom of these groups is a hydroxyl group, a halogen atom, a nitro group, a cyano group, -SO3H group, a carboxyl group, an amino group, an amide group or a group substituted metallocene a group of these positions and the number of substituents is not limited.

[0050] 另外,当上述Rn、Rn'和Yn、Yn'以及X11和X11'中的R23、R24和R25中的芳烷基和烷基中的亚甲基被-0-、-S-、-CO-、-COO-、-0C0-、-SO2-、-NH-、-⑶NH-、-NHCO-、-N = CH-或碳-碳双键置换时,这些置换的数量和位置是任意的。 [0050] Further, when the above Rn, Rn 'and Yn, Yn', and X11 and X11 'are R23, R24 and R25 are aralkyl group and an alkyl methylene group is -0 -, - S-, -CO -, - COO -, - 0C0 -, - SO2 -, - NH -, - ⑶NH -, - NHCO -, - N = CH- or a carbon - carbon double bond substituted, such substitutions number and positions are arbitrary of.

[0051] 例如,作为上述碳原子数为1〜8的烷基被卤原子取代的基团,可以列举出例如氯甲基、二氯甲基、三氯甲基、氟甲基、二氟甲基、三氟甲基、九氟丁基等。 [0051] For example, as the number of carbon atoms of 1~8 alkyl group substituted with a halogen atom group, may include, for example, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl , trifluoromethyl, nonafluorobutyl like.

[0052] 作为上述碳原子数为1〜8的烷基被-0-中断的基团,可以列举出甲氧基、乙氧基、 异丙氧基、丙氧基、丁氧基、戊氧基、异戊氧基、己氧基、庚氧基、辛氧基、2-乙基己氧基等烧氧基、以及2-甲氧基乙基、2-(2-甲氧基)乙氧基乙基、2-乙氧基乙基、2-丁氧基乙基、4-甲氧基丁基、3-甲氧基丁基等烷氧基烷基等。 [0052] Examples of the carbon atoms of 1~8 alkyl interrupted by -0- group may include methoxy, ethoxy, isopropoxy, propoxy, butoxy, pentoxy group, iso-pentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy group and the like burning, and 2-methoxyethyl, 2- (2-methoxy) acetate methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, 4-methoxybutyl, 3-methoxybutyl alkyloxyalkyl etc. and the like.

[0053] 作为上述碳原子数为1〜8的烷基被卤原子取代、并且被-0-中断的基团,可以列举出例如氯代甲氧基、二氯甲氧基、三氯甲氧基、氟代甲氧基、二氟甲氧基、三氟甲氧基、九氟丁氧基等。 [0053] Examples of the carbon atoms of 1~8 alkyl group substituted by a halogen atom, and groups interrupted by -0-, may, for example chloromethoxy, dichloromethoxy group, a trichloromethoxy group, fluoromethoxy group, difluoromethoxy group, trifluoromethoxy group, nonafluorobutoxy like.

[0054] 上述通式(II)中,作为X11和X11'所表示的碳原子数为3〜6的环链烷-1,1_二基,可以列举出环丙烷-1,1-二基、环丁烷-1,1-二基、2,4_二甲基环丁烷-1,1-二基、3,3_二甲基环丁烷-1,1-二基、环戊烷1,1-二基、环己烷-1,1-二基等。 In [0054] the above formula (II), as X11 and X11 'number of carbon atoms represented by 3 ~ 6 cycloalkane-diyl -1,1_, include cyclopropane-1,1-diyl cyclobutane-1,1-diyl, 2,4_-dimethyl-cyclobutane-1,1-diyl, 3,3_-dimethyl-cyclobutane-1,1-diyl, cyclopentyl, 1,1-diyl, cyclohexane-1,1-diyl and the like.

[0055] 作为上述通式(II)中的Q所表示的、构成碳原子数为1〜9的次甲基链、并且链中可以含有环结构的连接基,下述(QI)〜(Q-Il)中的任一个表示的基团由于容易制造,因而是优选的。 [0055] Examples of the formula (II) is represented by Q, 1~9 carbon atoms constituting the methine chain, and the chain connecting group may contain a ring structure, the following (QI) ~ (Q any group -IL) of a representation of the ease of manufacture because, which is preferable. 关于碳原子数为1〜9的次甲基链中的碳原子数,不包括将次甲基链或次甲基链中含有的环结构进一步取代的基团的碳原子(例如,连接基(QI)中的两末端的碳原子、下述R14〜R19、Z'的碳原子)。 Carbon atoms on carbon atoms of 1~9 methine chain, excluding the carbon atoms in the ring structure, or a methine chain methine chain containing the group further substituted (e.g., linker ( both ends of the carbon atoms QI) is, following R14~R19, Z 'carbon atoms).

[0056] [化2] [0056] [Formula 2]

[0057] [0057]

Figure CN107531857AD00081

[0058] (式中,R14、R15、R16、R17、R18、R19和Z'分另Ij独立地表示氢原子、羟基、卤原子、氰基、-NRR'、芳基、芳烷基或烷基,该-NRR'、芳基、芳烷基和烷基也可以被羟基、卤原子、氰基或-NRR' 取代,也可以被-0-、-S-、-CO-、-COO-、-0C0-、-SO2-、-NH-、-CONH-、-NHCO-、-N=CH-或-CH=CH-中断,R和R'表示芳基、芳烷基或烷基。) [0058] (wherein, R14, R15, R16, R17, R18, R19 and Z 'are the other points Ij independently represent a hydrogen atom, a hydroxyl group, a halogen atom, a cyano, -NRR', aryl, arylalkyl or alkylaryl group, which -NRR ', aryl, aralkyl and alkyl group may be a hydroxyl group, a halogen atom, a cyano group, or -NRR' substituents, may also be -0 -, - S -, - CO -, - COO- , -0C0 -, - SO2 -, - NH -, - CONH -, - NHCO -, - N = CH- or -CH = CH- interruption, R and R 'represent an aryl group, an aralkyl group or an alkyl group).

[0059] 作为上述1?14、1?15、1?16、1?17、1?18、1?19和2'表示的卤原子、芳基、芳烷基或烷基,可以列举出在R11等的说明中所列举的基团,作为R和R'表示的芳基、芳烷基或烷基,可以列举出在Rn等的说明中所列举的基团。 [0059] Examples of the 1? 14,1? 15,1? 16,1? 17,1? 18, 1? 19, and 2 'denotes a halogen atom, an aryl group, or aralkyl group, it may include in DESCRIPTION R11 and the like groups exemplified as R and R 'aryl, aralkyl or a group represented may include a group described in Rn and the like recited.

[0060] 作为上述通式(II)中的pAn『所表示的q价的阴离子,可以列举出甲磺酸阴离子、十二烷基磺酸阴离子、苯磺酸阴离子、甲苯磺酸阴离子、三氟甲磺酸阴离子、萘磺酸阴离子、二苯基胺-4-磺酸阴离子、2-氨基-4-甲基-5-氯苯磺酸阴离子、2-氨基-5-硝基苯磺酸阴离子、 萘二磺酸阴离子、萘酚磺酸阴离子、双(三氟甲磺酰)亚胺酸阴离子、日本特开平10-235999 号公报、日本特开平10-337959号公报、日本特开平11-102088号公报、日本特开2000-108510号公报、日本特开2000-168223号公报、日本特开2001-209969号公报、日本特开2001-322354号公报、日本特开2006-248180号公报、日本特开2006-297907号公报、日本特开平8-253705号公报、日本特表2004-503379号公报、日本特开2005-336150号公报、国际公开2006/28006号公报等中记载的磺酸阴离子等有机磺酸阴离子,此外还可以列举出氯化物离子、溴化 [0060] q-valent anion pAn the above general formula "(II) is represented by the acid anion include, lauryl sulfonic acid anion, benzenesulfonic acid anion, toluenesulfonic acid anion, trifluoromethanesulfonic methanesulfonic acid anion, a naphthalenesulfonic acid anion, a diphenylamine-4-sulfonic acid anion, 2-amino-5-chloro-4-methyl benzenesulfonate anion, 2-amino-5-nitrobenzene sulfonic acid anion , naphthalene disulfonic acid anion, naphthol sulfonic acid anion, bis (trifluoromethanesulfonyl) imidic acid anion, JP 10-235999, Japanese Patent Laid-Open No. 10-337959, Japanese Patent Laid-Open 11-102088 No. bulletin, JP 2000-108510, Japanese Patent Laid-open No. 2000-168223, Japanese Patent Laid-open No. 2001-209969, Japanese Patent Laid-open No. 2001-322354, Japanese Patent Laid-open No. 2006-248180 and JP open Patent Publication No. 2006-297907 acid anion, Japanese Unexamined Patent Publication No. 8-253705, Japanese Unexamined Patent Publication No. 2004-503379, Japanese Patent Publication Laid-open No. 2005-336150, international Publication No. 2006/28006, and the like described in JP organic sulfonic acid anion, in addition may further include a chloride ion, bromide 离子、碘化物离子、氟化物离子、氯酸离子、硫氰酸离子、六氟磷酸离子、六氟锑酸离子、四氟硼酸离子、辛基磷酸离子、十二烷基磷酸离子、十八烷基磷酸离子、苯基磷酸离子、壬基苯基磷酸离子、2,2' -亚甲基双(4,6-二叔丁基苯基)膦酸离子、四(五氟苯基)硼酸离子、具有使处于激发状态的活性分子去激发(淬灭)的功能的淬灭剂阴离子、在环戊二烯环上具有羧基或膦酸基、磺酸基等阴离子性基团的二茂铁、二茂钌等茂金属化合物阴离子等。 Ion, iodide ion, fluoride ion, perchlorate ion, thiocyanate ion, hexafluorophosphate ion, hexafluoroantimonate ion, tetrafluoroborate ion, octyl phosphate ion, dodecyl phosphate ion, octadecyl phosphoric acid ion, phenyl phosphate ion, nonylphenyl phosphate ion, 2,2 '- methylene bis (4,6-di-tert-butylphenyl) phosphonate ion, tetrakis (pentafluorophenyl) borate ion quencher anion active molecule in an excited state with de-excitation (quenched) function in the cyclopentadienyl ring having ferrocenyl anionic carboxyl group or a phosphonic acid group, a sulfonic acid group, ruthenocene metallocene compound anion and the like.

[0061] 作为本发明中使用的花青化合物(α)的具体例,可以列举出下述化合物No. 1〜 104。 Cyanine compound ([alpha]) used in the present invention [0061] Specific examples include the following compounds No. 1~ 104. 此外,以下的例子中,用省略了阴离子的花青阳离子来表示。 In the following examples, with the omitted cationic cyanine anions represented. [化3] [Formula 3]

[0062] [0062]

Figure CN107531857AD00091

[0063][化4] [0063] [Chemical Formula 4]

[0064] [0064]

Figure CN107531857AD00101

[0065] [化5] [0065] [Formula 5]

[0066] [0066]

Figure CN107531857AD00111

[0067][化6] [0067] [Formula 6]

Figure CN107531857AD00121

Figure CN107531857AD00131

Figure CN107531857AD00141

Figure CN107531857AD00151

Figure CN107531857AD00161

Figure CN107531857AD00171

Figure CN107531857AD00181

Figure CN107531857AD00191

[0083] 上述通式(II)表示的化合物中,优选以下的化合物。 Compound [0083] the above formula (II), the compound is preferably less.

[0084] 环A或环A'为苯环或萘环的化合物。 [0084] ring A or ring A 'is a benzene ring or a naphthalene ring-containing compound.

[0085] r或r'为0〜2的化合物。 Compound of 0 to 2 [0085] r or r 'is.

[0086] 当r或r'为1以上时,R11和R11'为卤原子、硝基、羧基、二茂铁基、无取代的碳原子数为1〜8 (特别是1〜4)的烷基或碳原子数为1〜8 (特别是1〜4)的卤代烷基的化合物。 [0086] When r or r 'when less than 1, R11 and R11' is a halogen atom, a nitro group, a carboxyl group, a ferrocenyl group, an unsubstituted carbon atoms of 1~8 (especially 1 ~ 4) alkoxy or a group of 1~8 carbon atoms (especially 1 ~ 4) haloalkyl compound.

[0087] X11和X11'为氧原子、硫原子、-CR23R24〔特别是,R23和R24为无取代或有时被卤原子取代、也有时被碳-碳双键置换的碳原子数为1〜8 (特别是1〜4)的烷基、无取代或有时被卤原子取代、也有时被碳-碳双键置换的碳原子数为7〜20 (特别是7〜15)的芳烷基〕或碳原子数为3〜6的环链烷-1,1-二基的化合物。 [0087] X11 and X11 'is an oxygen atom, a sulfur atom, -CR23R24 [in particular, R23 and R24 may be unsubstituted or substituted with a halogen atom, sometimes also a carbon - carbon double bond carbon atoms is replaced with 1~8 (especially ~ 4) alkyl, unsubstituted or may be substituted with a halogen atom, sometimes also a carbon - carbon double bond carbon atoms is substituted with 7~20 (particularly 7~15) aralkyl group] or 3 ~ 6 carbon atoms, a cycloalkane-1,1-diyl compounds. 进而,更优选氧原子、硫原子、-CR23R24-〔特别是,R23和R24为无取代的碳原子数为1〜4的烷基〕。 Further, more preferably an oxygen atom, a sulfur atom, -CR23R24- [in particular, R23 and R24 are carbon atoms unsubstituted alkyl group of 1 ~ 4].

[0088] Y11和Y11'为有时被卤原子、硝基、羧基或二茂铁基取代、也有时被氧原子或-CO-置换的碳原子数为6〜30 (特别是6〜12)的芳基、碳原子数为7〜30 (特别是7〜15)的芳烷基或碳原子数为1〜8的烷基的化合物。 [0088] Y11 and Y11 'is sometimes a halogen atom, a nitro group, a carboxyl group or substituted ferrocenyl group, an oxygen atom or sometimes carbon atoms and -CO- is replaced with 6~30 (particularly 6~12) of or an alkyl group of 1~8 carbon atoms, aralkyl group an aryl group having 7~30 carbon atoms, (especially 7~15) for. 进而,有时被卤原子取代、也有时被氧原子置换的碳原子数为7〜30 (特别是7〜15)的芳烷基或碳原子数为1〜8的烷基是更优选的。 Further, sometimes substituted with a halogen atom, it is also sometimes the number of carbon atoms is replaced with an oxygen atom 7~30 (particularly 7~15) aralkyl group or an alkyl group of 1~8 carbon atoms is more preferable.

[0089] Q构成碳原子数为7或9的次甲基链的化合物。 [0089] Q is methine chain composed of compound 7 or 9 carbon atoms. 另外,构成碳原子数为7或9的次甲基链、并且该次甲基链中的氢原子被羟基、卤原子、氰基或芳基取代的化合物。 Further, carbon atoms constituting the methine chain of 7 or 9, and a hydrogen atom of the methine chain is a hydroxyl group, a halogen atom, a cyano group or a substituted aryl compound. 另外,构成碳原子数为7或9的次甲基链、并且链中具有环结构的化合物。 Further, carbon atoms constituting the methine chain of 7 or 9, and a compound having a cyclic structure in the chain.

[0090] 本发明中使用的花青化合物(α)的制造方法没有特别限定,可以通过利用了众所周知的一般的反应的方法来获得,例如可以列举出像日本特开2010-209191号公报中记载的路径那样,通过具有相应的结构的化合物与亚胺衍生物的反应来合成的方法。 [0090] The method for producing the cyanine compound ([alpha]) of the present invention is not particularly limited, and may be obtained by using a method generally known reaction, and examples include as Japanese Unexamined Patent Publication No. 2010-209191 discloses path as synthesized by the reaction of a compound having a corresponding structure and imine derivatives.

[0091] 本发明中使用的花青化合物(α)的涂膜的最大吸收波长(Amax)优选为650〜 1200nm、更优选为650〜900nm。 [0091] The maximum absorption wavelength of the cyanine compound coating film ([alpha]) used in the present invention (Amax) is preferably 650~ 1200nm, more preferably 650~900nm. 涂膜的最大吸收波长(Amax)如果为本发明的1200nm以上,贝Ij 不能发挥本发明的效果,如果低于650nm,则会吸收可见光,因而不优选。 Film maximum absorption wavelength (Amax) of the present invention if more than 1200nm, shellfish can not play Ij effect of the invention, is less than 650nm, it will absorb visible light, which is not preferable.

[0092] 本发明的热反应性组合物中,上述花青化合物(α)的含量按照单独或多种的合计, 相对于后述的树脂〇3)的固体成分100质量份,花青化合物中的至少一种(α)的合计为0.01 〜1 〇质量份。 [0092] The heat-reactive composition of the present invention, the content of the cyanine compound ([alpha]) in accordance with a variety of aggregate alone or the resin 〇3) described later after the solid content with respect to 100 parts by mass of the cyanine compound at least one ([alpha]) the total of 0.01 parts by mass of ~ 1 billion. 花青化合物(α)的含量如果小于0.01质量份,则在本发明的固化物中,有时无法获得充分的红外线遮蔽功能,如果大于10质量份,则有时在热反应性组合物中发生花青化合物(α)的析出。 Content of the cyanine compound ([alpha]) If less than 0.01 part by mass, then the cured product of the present invention may not be obtained a satisfactory infrared shielding function, if it exceeds 10 parts by mass, the heat may occur in the reactive cyanine composition precipitated compound ([alpha]) in.

[0093] 〈树脂(β) > [0093] <Resin (β)>

[0094] 作为上述树脂(β),只要是一分子内具有烯键式不饱和键和亲水性基团的树脂,就可以无特别限定地使用以往使用的树脂。 [0094] The resin (beta]), as long as a resin having an ethylenically unsaturated bond and a hydrophilic group in the molecule, can be used without particular limitation resins conventionally used.

[0095] 作为亲水性基团,可以列举出羟基、硫醇基、羧基、磺基、氨基、酰胺基或其盐等,羟基和羧基由于可使树脂Φ)在碱中的溶解性高,因而是优选的。 [0095] Examples of the hydrophilic group include a hydroxyl group, a thiol group, a carboxyl group, a sulfo group, an amino group, an amide group or salts thereof, hydroxyl and carboxyl groups since the resin can [Phi]) high solubility in alkali, hence it preferred.

[0096] 树脂(β)中的亲水性基团的优选的官能团当量(含有亲水性基团1当量的树脂的质量)为50〜10000。 [0096] Preferred functional group equivalent weight (mass of the resin containing a hydrophilic group 1 equivalent) resin (beta]) the hydrophilic group is 50~10000.

[0097] 树脂(β)的优选的质均分子量为1000〜500000。 [0097] Preferred crystalline resin (beta]) average molecular weight of 1000~500000.

[0098] 上述树脂〇3)中,具有下述通式(II)表示的单元、下述通式(1-2)表示的单元和下述通式(1-3)表示的单元的树脂由于显影性和耐热性高,因而是优选的。 Unit, unit unit, and a resin following general formula the following formula (1-2) (1-3) [0098] The resin 〇3) having the following general formula (II), due to developability and high heat resistance, which is preferable.

[0099] [化14] [0099] [Formula 14]

Figure CN107531857AD00211

[0101] (式中,X1表示氢原子或甲基,Y1为二价的结合基,R1表示碳原子数为1〜20的烷基、 碳原子数为6〜30的芳基或碳原子数为7〜30的芳烷基,该烷基、芳基和芳烷基有时也被卤原子、羟基或硝基取代,该烷基和芳烷基中的亚甲基有时也被-〇-、-s-、-co-、-rao-、-oco-或-NH-、或它们的组合的结合基置换,R2、R3和R4分别独立地为氢原子或甲基。) [0101] (wherein, the X1 represents a hydrogen atom or a methyl group, Y1 is a divalent bonding group, Rl represents an alkyl group of 1~20 carbon atoms, carbon atoms, an aryl group of 6~30 carbon atoms, or 7~30 aralkyl group, which alkyl, aryl and aralkyl groups are sometimes also halogen atom, a nitro group or a substituted hydroxyl group, the alkyl group and the aralkyl group is sometimes -〇- methylene, -s -, - co -, - rao -, - oco- or -NH-, or combinations thereof in conjunction with the substitution, R2, R3 and R4 are each independently a hydrogen atom or a methyl group).

[0102] 作为上述通式(1-2)中的Y1所表示的二价的结合基,可以列举出下述通式⑴表示的结构。 [0102] Examples of the divalent binding group of the general formula (1-2) is represented by Y1 include a structure represented by the following formula ⑴.

[0103] [化15] [0103] [Formula 15]

[0104] ^-Z1-X2-Z2-* (1) [0104] ^ -Z1-X2-Z2- * (1)

[0105] (式中,X2表示-CR5R6-、-NR7-、二价的碳原子数为1〜35的链状烃基、二价的碳原子数为3〜35的脂环式烃基、二价的碳原子数为6〜35的芳香族烃基、二价的碳原子数为2〜35 的含杂环的基团、或下述(1-1)〜(1-3)表示的任一个取代基,R5和R6表示氢原子、碳原子数为1〜8的烷基、碳原子数为6〜20的芳基或碳原子数为7〜30的芳烷基,Z1和Z2分别独立地表示直接键合、-0-、-3-、-302-、-30-、-置7-或-?1?8-,1?7和1?8表示氢原子、碳原子数为1〜8的烷基、碳原子数为6〜30的芳基或碳原子数为7〜30的芳烷基。 [0105] (wherein, an X2 represents -CR5R6 -, - NR7-, carbon atoms, a divalent chain-like hydrocarbon group of 1~35 carbon atoms, a divalent alicyclic of 3~35 hydrocarbon group, a divalent carbon atoms of the aromatic hydrocarbon group 6~35 carbon atoms, a divalent heterocyclic group containing 2~35 or following (1-1) to (1-3) represented by a substituent group, R5 and R6 represent a hydrogen atom, an alkyl group of 1~8 carbon atoms, carbon atoms, or an aryl group having a carbon number of 7~30 6~20 aralkyl, Zl and Z2 each independently represent a a direct bond, from 0 -, - 3 -, --302--, - 30 -, - 7- or counter -??? 18-, 17 and 18 represent a hydrogen atom, 1~8 carbon atoms? or an aryl group of carbon atoms, having a carbon number of 7~30 6~30 aralkyl.

[0106] 上述R5、R6、R7和R8中的烷基、芳基和芳烷基也可以被卤原子、羟基或硝基取代,上述R5、R6、R7和R8中的烷基和芳烷基中的亚甲基有时也被-0-、-S-、-CO-、-COO-、-0C0-或-NH-基置换。 [0106] The R5, R6, R7 and R8 alkyl, aryl and aralkyl groups may also be a halogen atom, a nitro group or a hydroxyl group substituted with the R5, R6, R7 and R8 and aralkyl methylene sometimes -0 -, - S -, - CO -, - COO -, - 0C0- or -NH- substitution. 不过,上述通式⑴表示的基团的碳原子数为1〜35的范围内。 However, the number of carbon atoms in the group represented by the general formula ⑴ in the range of 1~35. )

[0107] [化16] [0107] [Chemical Formula 16]

Figure CN107531857AD00212

[0109](上述式中,R71表示氢原子、可以具有取代基的苯基、或碳原子数为3〜10的环烷基,R72表示碳原子数为1〜10的烷基、碳原子数为1〜10的烷氧基、碳原子数为2〜10的链烯基或卤原子,上述烷基、烷氧基和链烯基也可以具有取代基,f为O〜5的整数。) [0109] (In the formulas, R71 represents a hydrogen atom, an optionally substituted phenyl group or a cycloalkyl group having a carbon number of 3~10, R72, represents an alkyl group of 1~10 carbon atoms, carbon atoms, alkoxy of 1~10 carbon atoms, an alkenyl group or a halogen atom 2~10, said alkyl, alkoxy and alkenyl groups may have a substituent group, f is an integer of O~5.)

[0110][化17] [0110] [Chemical Formula 17]

Figure CN107531857AD00221

[0114] (上述式中,R73和R74分别独立地表示可以具有取代基的碳原子数为1〜10的烷基、 可以具有取代基的碳原子数为6〜30的芳基、可以具有取代基的碳原子数为6〜30的芳氧基、可以具有取代基的碳原子数为6〜30的芳硫基、可以具有取代基的碳原子数为6〜30的芳基链烯基、可以具有取代基的碳原子数为7〜30的芳烷基、可以具有取代基的碳原子数为2〜20的含杂环的基团或卤原子,该烷基和芳烷基中的亚甲基也可以被不饱和键、-OSS-中断,关于R73,可以通过邻接的R73彼此而形成环,d表示0〜4的数,f表示0〜8的数,g表示0 〜4的数,h表示0〜4的数,g和h的数的合计为2〜4。) [0114] (In the formulas, R73 and R74 each independently represent carbon atoms which may have a substituent 1~10 alkyl group, carbon atoms and may have a substituent group is 6~30 aryl group may have a substituent carbon atoms and number of carbon atoms of 6~30 aryloxy group, carbon atoms and may have a substituent group, arylthio group having 6~30, and may have a substituent group, an alkenyl group, an aryl group of 6~30, carbon atoms which may have a substituent 7~30 aralkyl group may have a substituent group having a carbon number of a heterocyclic group or a halogen atom of 2~20, in the alkylene and aralkyl methyl may be an unsaturated bond, -OSS- interrupted on R73, may form a ring by abutting one another by R73, d represents the number of 0~4, f represents a number of 0~8, g represents a number of 0 ~ 4 , h represents a number of 0~4, g and h of the total of the number of 2 ~ 4.)

[0115] 作为上述通式(1-3)中的R1表示的碳原子数为6〜30的芳基或碳原子数为7〜30 (优选为7〜20)的芳烷基,可以列举出在上述(α)成分的花青化合物的说明中所列举的芳基或芳烷基。 Carbon atoms or an aryl group [0115] The number of carbon atoms in the general formula (1-3) is represented by R1 is 7~30 6~30 (preferably 7~20) of the aralkyl group include in the above described cyanine compound ([alpha]) ingredients enumerated aryl or aralkyl group.

[0116] 作为碳原子数为1〜20的烷基,除了在上述花青化合物⑷的说明中所列举的烷基以外,还可以列举出壬基、癸基、十一烷基、十二烷基、十三烷基、异十三烷基、十四烷基、十八烧基、十七烧基、十八烧基等。 [0116] Examples 1~20 carbon atoms, an alkyl group, an alkyl group in addition to the above-described cyanine compounds described in ⑷ listed, may also include a nonyl, decyl, undecyl, dodecyl , tridecyl, isotridecyl, tetradecyl, octadecyl burn group, seventeen burning base, eighteen burn group.

[0117] 上述通式⑴中,作为X2表示的二价的碳原子数为1〜35的链状烃基,可以列举出甲烷、乙烷、丙烷、异丙烷、丁烷、仲丁烷、叔丁烷、异丁烷、己烷、2-甲基己烷、3-甲基己烷、庚烷、2-甲基庚烷、3-甲基庚烷、异庚烷、叔庚烷、1-甲基辛烷、异辛烷、叔辛烷等被Z1和Z2取代后的基团。 [0117] In the above formula ⑴, as the number of carbon atoms of the divalent chain-like hydrocarbon group represented by X2 1~35 may include methane, ethane, propane, isobutane, propane, butane, sec-butane, tert-butyl alkoxy, isobutane, hexane, 2-methyl hexane, 3-methyl hexane, heptane, 2-methyl heptane, 3-heptane, isoheptane, tert-heptane, 1 methyl octane, isooctane, tert-octane is substituted with the groups Z1 and Z2.

[0118] 作为二价的碳原子数为3〜35的脂环式烃基,可以列举出环丙烷、环丁烷、环戊烷、 环己烷、环庚烷、2,4_二甲基环丁烷、4-甲基环己烷等被Z1和Z2取代后的基团等。 [0118] carbon atoms of the divalent alicyclic hydrocarbon group having 3~35 may include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, 2,4_ dimethylcyclohexyl butane, cyclohexane, methyl substituted with a group like Z1 and Z2.

[0119]作为二价的碳原子数为6〜35的芳香族经基,可以列举出亚苯基、亚萘基、联苯基等基团被Z1和Z2取代后的基团等。 [0119] carbon atoms of the divalent aromatic 6~35 by group include a group in which a phenylene group, naphthylene group, biphenyl group substituted with Z1 and Z2 and the like.

[0120]作为二价的碳原子数为3〜35的含杂环的基团,可以列举出吡啶、吡嗪、哌啶、哌嗪、嘧啶、哒嗪、三嗪、六氢三嗪、呋喃、四氢呋喃、色满、氧杂蒽、噻吩、四氢噻吩等被Z1和Z2取代后的基团,上述基团也可以多种组合。 [0120] carbon atoms of the divalent heterocyclic group containing 3~35 may include pyridine, pyrazine, piperidine, piperazine, pyrimidine, pyridazine, triazine, hexahydro-triazine, furan , tetrahydrofuran, chroman, xanthene, thiophene, tetrahydrothiophene the substituted groups Z1 and Z2 the group may also be various combinations. 另外,上述的链状烃基、脂环式烃基和芳香族烃基也可以被卤原子、羟基或硝基取代。 Further, the above chain hydrocarbon group, an alicyclic hydrocarbon group and aromatic hydrocarbon group may be a halogen atom, a nitro group or a substituted hydroxyl group. 另外,上述的链状烃基、脂环式烃基和芳香族烃基中的亚甲基有时也被-O-、-S-、-CO-、-coo-、-OCO-或-NH-基置换。 Further, the above chain hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon methylene sometimes -O -, - S -, - CO -, - coo -, - OCO- or -NH- substitution.

[0121] 作为上述通式(1)中的R5、R6、R7和R8表示的碳原子数为1〜8的烷基、碳原子数为6 〜30的芳基或碳原子数为7〜30的芳烷基,可以列举出在上述花青化合物(α)的说明中所列举的烷基、芳基、芳烷基。 Carbon atoms or an aryl group [0121] Examples of the general formula R5 (1) the number of carbon atoms in R6, R7 and R8 represents an alkyl group having a carbon number of 1~8 7~30 for 6 ~ 30 the aralkyl group include an alkyl group in the above described cyanine compound ([alpha]) as recited in, an aryl group, an aralkyl group.

[0122] 上述R5、R6、R7和R8中的烷基、芳基和芳烷基也可以被卤原子、羟基或硝基取代,上述R5、R6和R7中的烷基和芳烷基中的亚甲基也可以被-0-、-S-、-CO-、-COO-、-0C0-、-NH-或这些基团多种组合而成的基团中断,它们的取代位置和中断位置没有特别限制。 [0122] The R5, R6, R7 and R8 alkyl, aryl and aralkyl groups may also be a halogen atom, a nitro group or a substituted hydroxyl group, the above-mentioned R5, R6 and R7 are alkyl and aryl groups methylene may also be -0 -, - S -, - CO -, - COO -, - 0C0 -, - NH-, or a combination of these groups more radicals interrupted, substituted and interrupted position location There is no particular limitation.

[0123] 上述(1-1)表示的取代基中,作为Rn表示的碳原子数为3〜10的环烷基,可以列举出环丙基、环丁基、环戊基、环庚基、环辛基等。 Substituent group represented by the [0123] above (1-1), the carbon atoms of the cycloalkyl group represented by Rn 3~10 may include cyclopropyl, cyclobutyl, cyclopentyl, cycloheptyl, cyclooctyl and the like.

[0124] 作为R72表示的碳原子数为1〜10的烷基,可以列举出作为R1表示的碳原子数为1〜 40的烷基所列举的基团中满足规定的碳原子数的基团等。 [0124] Examples of carbon atoms represented by R72 1~10 alkyl group, the group may include the number of carbon atoms represented by R1 is 1 ~ 40 alkyl recited satisfying predetermined carbon atoms, a group Wait.

[0125] 作为R72表示的碳原子数为1〜10的烷氧基,可以列举出甲氧基、乙氧基、丙氧基、异丙氧基、丁氧基、仲丁氧基、叔丁氧基、异丁氧基、戊氧基、异戊氧基、叔戊氧基、己氧基、环己氧基、庚氧基、异庚氧基、叔庚氧基、正辛氧基、异辛氧基、叔辛氧基、2-乙基己氧基、壬氧基、 癸氧基等。 [0125] Examples of carbon atoms represented by R72 1~10 alkoxy group may include methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, tert-butoxy group, isobutoxy group, pentyloxy group, iso-pentyloxy, tert-pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, isoheptyloxy, tert-heptyloxy, n-octyloxy, isooctyl group, a tert-octyl group, a 2-ethylhexyl group, nonyl group, decyl group and the like.

[0126] 作为R72表示的烷基、烷氧基和链烯基可以具有的取代基,可以列举出卤原子、羟基、硝基。 [0126] As the alkyl, alkoxy and alkenyl group represented by R72 may have a substituent group, include a halogen atom, a hydroxyl group, a nitro group.

[0127] 上述(1-3)表示的基团中,作为R73和R74表示的可以具有取代基的碳原子数为1〜 10的烷基,可以列举出作为R1表示的碳原子数为1〜20的烷基所列举的基团中满足规定的碳原子数的基团等。 [0127] The (1-3) a group represented as R73 and R74 may have a substituent group represented by the number of carbon atoms is 1 ~ 10 alkyl group may include carbon atoms represented by R1 is 1 ~ number of carbon atoms of alkyl group 20 satisfies a predetermined recited groups and the like.

[0128] 作为R73和R74表示的可以具有取代基的碳原子数为6〜30的芳基,可以列举出作为R11等表示的碳原子数为6〜30的芳基所列举的基团等。 [0128] As represented by R73 and R74 may have a substituent group of carbon atoms of 6~30 aryl group may include a like number of carbon atoms as represented by R11 6~30 aryl group and the like exemplified.

[0129] 作为R73和R74表示的可以具有取代基的碳原子数为6〜30的芳氧基,可以列举出苯氧基、萘氧基、2-甲基苯氧基、3-甲基苯氧基、4-甲基苯氧基、4-乙烯基苯氧基、3-异丙基苯氧基、4-异丙基苯氧基、4-丁基苯氧基、4-叔丁基苯氧基、4-己基苯氧基、4-环己基苯氧基、 4_辛基苯氧基、4_ (2_乙基己基)苯氧基、2,3_二甲基苯氧基、2,4_二甲基苯氧基、2,5_二甲基苯氧基、2,6-二甲基苯氧基、3,4-二甲基苯氧基、3,5-二甲基苯氧基、2,4-二叔丁基苯氧基、2,5-二叔丁基苯氧基、2,6-二叔丁基苯氧基、2,4-二叔戊基苯氧基、2,5-叔戊基苯氧基、 4-环己基苯氧基、2,4,5-三甲基苯氧基、二茂铁氧基等基团。 Carbon atoms [0129] As R73 and R74 may have a substituent represented by is 6~30 aryloxy group include a phenoxy group, naphthyloxy group, 2-methylphenoxy, 3-methylphenyl group, 4-methylphenoxy, 4-vinyl-phenoxy, 3-isopropylphenoxy, 4-isopropylphenoxy, 4-butylphenoxy, 4-tert-butyl phenoxy, 4-methoxyphenoxy, 4-cyclohexyl-phenoxy, octylphenoxy 4_, 4_ (2_ ethylhexyl) phenoxy, dimethylphenoxy 2,3_, dimethylphenoxy 2,4_, 2,5_-dimethylphenoxy, 2,6-dimethylphenoxy, 3,4-dimethylphenoxy, 3,5 phenoxy, 2,4-di-t-butyl phenoxy, 2,5-di-t-butyl phenoxy, 2,6-di-t-butyl phenoxy, 2,4-di-t-amylphenoxy group, a 2,5-tert-amylphenoxy, 4-cyclohexyl-phenoxy, 2,4,5-trimethylphenoxy group, a ferrocenyl group, and like groups.

[0130] 作为R73和R74表示的可以具有取代基的碳原子数为6〜30的芳硫基,可以列举出上述可以具有取代基的碳原子数为6〜30的芳氧基的氧原子置换成硫原子后的基团等。 Carbon atoms [0130] As R73 and R74 may have a substituent represented by is 6~30 aryl group include the above-mentioned carbon atoms may have a substituent group is an oxygen atom substituted aryloxy group of 6~30 after a sulfur atom into a group and the like.

[0131] 作为R73和R74表示的可以具有取代基的碳原子数为8〜30的芳基链烯基,可以列举出上述可以具有取代基的碳原子数为6〜30的芳氧基的氧原子用乙烯基、烯丙基、1-丙烯基、异丙烯基、2-丁烯基、1,3_ 丁二烯基、2-戊烯基、2-辛烯基等链烯基置换后的基团等。 Carbon atoms [0131] As R73 and R74 may represent an aryl group having a substituent group 8~30 alkenyl group include the above-mentioned carbon atoms may have a substituent group is 6~30 aryloxy oxygen after atoms with vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, 1,3_ butadienyl, 2-pentenyl, 2-octenyl and the like alkenyl substituted group and the like.

[0132] 作为R73和R74表示的碳原子数为7〜30的芳烷基,可以列举出作为R71和R72表示的碳原子数为7〜30的芳烷基所列举的基团等。 [0132] R73 and the carbon atoms represented by R74 7~30 aralkyl, R71 can be exemplified as the number of carbon atoms represented by R72 is a group recited 7~30 aralkyl, and the like.

[0133] 作为R73和R74表示的可以具有取代基的碳原子数为2〜20的含杂环的基团,可以列举出吡啶、吡嗪、哌啶、哌嗪、嘧啶、哒嗪、三嗪、六氢三嗪、呋喃、四氢呋喃、色满、氧杂蒽、噻吩、四氢噻吩等。 Carbon atoms [0133] As R73 and R74 may represent an optionally substituted heterocyclic group containing 2~20 may include pyridine, pyrazine, piperidine, piperazine, pyrimidine, pyridazine, triazine , hexahydro-triazine, furan, tetrahydrofuran, chroman, xanthene, thiophene, tetrahydrothiophene.

[0134] 作为R73和R74表示的上述各种基团可以具有的上述的取代基,可以列举出卤原子、 羟基、硝基。 [0134] As R73 and R74 represents the above groups may have the substituents include a halogen atom, a hydroxyl group, a nitro group.

[0135] 上述通式(II)〜(1-3)表示的单元的构成比(摩尔比)为(II) : (1-2) : (1-3)= 0.1〜0.65:0.3〜0.8:0.001〜2,可以采取无规共聚、嵌段共聚、接枝共聚等任何一种排列。 [0135] the above formula (II) ~ structural units (1-3) represented by the ratio (molar ratio) of (II): (1-2): (1-3) = 0.1~0.65: 0.3~0.8: 0.001~2 can take random copolymerization, block copolymerization, graft copolymerization any arrangement.

[0136] 具有上述通式(II)、(1-2)和(1-3)表示的单元的树脂(β)中,优选以下的树脂。 [0136] having the above general formula (II), the resin (beta]) of the unit (1-2) and (1-3), preferably below the resin.

[0137] R1优选为碳原子数为1〜8的烷基和碳原子数为7〜30的芳烷基,更优选为碳原子数为1〜4的烧基。 [0137] R1 is preferably an alkyl group having a carbon number of 1~8 carbon atoms and is 7~30 aralkyl, more preferably a carbon number of 1 ~ 4 group burning.

[0138] Y1是二价的结合基,在上述通式⑴表示的结构的情况下,X2优选为碳原子数为1〜 15的亚烷基,更优选为具有亚环烷基的碳原子数为7〜15的亚烷基。 [0138] Y1 is a divalent binding group, in the case of the structure represented by the above general formula ⑴, an X2 carbon atoms preferably an alkylene group having 1 ~ 15 carbon atoms, more preferably a cycloalkylene group having an alkylene group of 7~15. 上述亚烷基中的氢原子也可以被卤原子、羟基或硝基原子取代,另外,亚烷基中的链状亚烷基部分中的亚甲基有时也被-〇-、-S-、-CO-、-COO-、-0C0-或-NH-基置换。 A hydrogen atom in the above alkylene group may be a halogen atom, a nitro atom or a hydroxyl group substituted with, in addition, an alkylene chain alkyl moiety a methylene group in the alkylene sometimes -〇 -, - S-, -CO -, - COO -, - 0C0- or -NH- substitution.

[0139] Z1和Z2优选为直接键合。 [0139] Z1 and Z2 are preferably a direct bond.

[0140] 上述树脂(β)的酸值优选为10〜200mg/K0H、更优选为30〜150mg/K0H。 [0140] acid value of the resin (beta]) is preferably 10~200mg / K0H, more preferably 30~150mg / K0H. 酸值如果低于10mg/K0H,则有时无法充分获得碱显影性,如果大于200mg/K0H,则有可能树脂(β)的制造困难。 If the acid value is less than 10mg / K0H, it may not be sufficiently obtain alkali-developable, if more than 200mg / K0H, it is possible to make it difficult for the resin (beta]) a.

[0141] 这里,酸值是指根据JIS K0050和JISK 0211得到的值。 [0141] Here, the acid value is a value according to JIS K0050 and obtained JISK 0211.

[0142] 本发明的热反应性组合物中,上述树脂(β)的含量在本发明的热反应性组合物的固体成分中优选为30〜99质量%、特别优选为60〜95质量%。 [0142] heat-reactive composition of the present invention, the content of the resin (beta]) in the solid content of the heat-reactive composition according to the present invention is preferably 30~99% by mass, and particularly preferably 60~95% by mass. 上述树脂(β)的含量如果小于30质量%,则固化物的力学强度不足,有时产生裂纹,如果大于99质量%,则依赖曝光的固化变得不充分,有时发粘。 The content of the resin (beta]) If less than 30%, the mechanical strength was insufficient curing, a crack may occur, if it exceeds 99% by mass, the dependency of the exposure curing becomes insufficient and sticky.

[0143] 〈热聚合引发剂(γ)> [0143] <Thermal polymerization initiator (γ)>

[0144] 作为上述热聚合引发剂(γ),可以使用以往已知的化合物,例如可以列举出2,2' -偶氮二异丁腈、2,2' -偶氮二(甲基异丁酸酯)、2,2' -偶氮二-2,4-二甲基戊腈、1,1' -偶氮二(1-乙酰氧基-1-苯基乙烧)等偶氮系聚合引发剂;苯甲酰基过氧化物、二叔丁基苯甲酰基过氧化物、叔丁基过氧化新戊酸酯、二(4-叔丁基环己基)过氧化二碳酸酯等过氧化物系聚合引发剂、过硫酸铵、过硫酸钠、过硫酸钾等过硫酸盐等。 [0144] Examples of the thermal polymerization initiator (gamma]), conventionally known compounds may be used, for example, may include 2,2 '- azobisisobutyronitrile, 2,2' - azobis (methyl isobutyrate ester), 2,2 '- azobis-2,4-dimethylvaleronitrile, 1,1' - azobis (1-acetoxy-1-phenyl acetic fever) and other azo-based polymerization initiator; benzoyl peroxide, di-t-butyl-benzoyl peroxide, t-butylperoxy pivalate, di (4-t-butylcyclohexyl) peroxide and other peroxy dicarbonate polymerization initiator, ammonium persulfate, sodium persulfate, potassium persulfate and the like. 它们可以将一种或二种以上混合使用。 They may be one or a mixture of two or more kinds.

[0145] 上述热聚合引发剂(γ)中,从耐热性的观点出发,优选偶氮系聚合引发剂,更优选偶氮二系化合物。 [0145] The thermal polymerization initiator (gamma]), the viewpoint of heat resistance, preferably an azo-based polymerization initiators, and more preferably azobis-based compound. 作为偶氮二系化合物,从工业上容易获得的观点出发,可以优选列举出下述通式㈧表示的化合物。 As the azobis compound, from the viewpoint of readily available industrial starting, it may preferably include a compound represented by the following formula (viii).

[0146] [化18Α] [0146] [Chemical 18Α]

[0147] [0147]

Figure CN107531857AD00241

[0148] (式中,Rm为有时具有取代基的分支或直链的碳原子数为1〜10的烷基,Riq2为有时具有取代基的分支或直链的碳原子数为1〜10的烷基或下述通式⑶表示的基团,前述烷基中的亚甲基也可以被-O-、-CO-O-、-O-CO-、-CO-NH-、-NH-CO-或碳-碳双键置换,与相同的碳原子结合的RlQl和RlQ2也可以相互连接而形成环。XlQl为氛基、-⑶NRiraRltM、-C00R1Q5、-C = N-Riq6或有时具有取代基的分支或直链的碳原子数为1〜10的烷基,和R1Q6分别独立地为氢原子或碳原子数为1〜4的烷基。) [0148] (in the formula, Rm is a substituted group may have a number of branched or straight chain alkyl group of 1~10 carbon atoms, Riq2 branched carbon atoms may have a substituent or a straight chain of 1~10 alkyl group or a group represented by the following general formula ⑶, a methylene group in the alkyl group may be -O -, - CO-O -, - O-CO -, - CO-NH -, - NH-CO - or a carbon - carbon double substitution bonded to the same carbon atom RlQl RlQ2 and may be connected to each other to form a ring .XlQl atmosphere group, -⑶NRiraRltM, -C00R1Q5, -C = N-Riq6 may have a substituent or carbon atoms, branched or straight chain alkyl group of 1~10, and R1Q6 are each independently a hydrogen atom or an alkyl group of 1 ~ 4 carbon atoms.)

[0149] [化18B] [0149] [Chemical 18B]

[0150] [0150]

Figure CN107531857AD00251

[0151] (式中,Rm、Rm和Rm分别独立地为氢原子或有时具有取代基的碳原子数为1〜4 的烷基,Rm、Rm也可以相互连接而形成环,*表示键合部分。) [0151] (in the formula, Rm, Rm and Rm are each independently a hydrogen atom or a carbon atoms and may have a substituent ~ 4 alkyl group, Rm, Rm may be connected to each other to form a ring, * represents a bonding section.)

[0152] 作为1?101、1?1()2、父1()1、1?1()3、1?1()4、1?1()5、1?1()6、1?111、1?112和1?113表不的烧基,可以列举出作为上述R11等表示的烷基所列举的基团中满足上述规定的碳原子数的基团。 [0152] As the 1? 101, 1? 1 () 2, 1 parent () 1, 1? 1 () 3,1? 1 () 4,1? 1 () 5,1? 1 () 6,1 ? 111,1? 1 112 and? 113 of the table does not burn group may include a group number of carbon atoms as the group represented by R11 include alkyl recited satisfying the predetermined.

[0153] 作为R1Q1和R1Q2相互连接而形成的环,可以列举出环烷基环,优选为碳原子数为3〜 8的环烷基环。 [0153] As R1Q1 and R1Q2 are interconnected to form a ring, may include a cycloalkyl ring, preferably a cycloalkyl group having ring carbon atoms of 3 ~ 8.

[0154] 作为Rm、Rm相互连接而形成的环,可以列举出咪唑环。 [0154] As Rm, Rm connected to each other to form a ring include an imidazole ring.

[0155] 作为1?1()1、1?1()2、乂1()1、1?111、1?112和1?113表示的烷基具有取代基时的取代基,可以列举出碳原子数为1〜4的烷氧基、羧基或羟基。 [0155] 1 as? 1 (), 1? 1 () 2, qe 1 () 1,1? 111,1? 1 112 and? 113 represents an alkyl group having a substituent of the substituent include carbon atoms, an alkoxy group, a carboxyl group or a hydroxyl group of 1 ~ 4.

[0156] 本发明的热反应性组合物中,上述热聚合引发剂(γ)的含量在本发明的热反应性组合物的固体成分中优选为0.1〜30质量%、特别优选为0.5〜10质量%。 Content of agent (gamma]) of the [0156] heat-reactive composition of the present invention, the heat polymerization initiator in the solid content of the heat-reactive composition of the present invention is preferably 0.1~30% by mass, and particularly preferably 0.5~10 quality%. 上述热聚合引发剂(Y)的含量如果小于〇. 1质量%,则有可能无法获得充分的耐热性,如果大于30质量%, 则有时在热反应性组合物中析出热聚合引发剂(γ)。 Of the thermal polymerization initiator (Y) content is less than 1% by mass square, it may be impossible to obtain sufficient heat resistance, if it exceeds 30 mass%, the precipitation of a thermal polymerization initiator thermally reactive composition ( γ).

[0157] 〈具有不饱和键的单体(ω)> [0157] <monomers ([omega]) having an unsaturated bond>

[0158] 本发明的热反应性组合物中,还可以进一步添加具有不饱和键的单体(ω)。 [0158] heat-reactive composition of the present invention may be further added with the monomer ([omega]) an unsaturated bond. 作为上述具有不饱和键的单体,可以列举出丙烯酸-2-羟基乙酯、丙烯酸-2-羟基丙酯、丙烯酸异丁酯、丙烯酸正辛酯、丙烯酸异辛酯、丙烯酸异壬酯、丙烯酸硬脂酯、丙烯酸甲氧基乙酯、丙烯酸二甲基氨基乙酯、丙烯酸锌、1,6_己二醇二丙烯酸酯、三羟甲基丙烷三丙烯酸酯、甲基丙烯酸-2-羟基乙酯、甲基丙烯酸-2-羟基丙酯、甲基丙烯酸丁酯、甲基丙烯酸叔丁酯、甲基丙烯酸环己酯、三羟甲基丙烷三甲基丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇六丙烯酸酯、季戊四醇四丙烯酸酯、季戊四醇三丙烯酸酯、双酸A二缩水甘油醚(甲基)丙烯酸酯、双酚F二缩水甘油醚(甲基)丙烯酸酯、双酚Z二缩水甘油醚(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯等。 Examples of the monomer having an unsaturated bond, include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobutyl acrylate, n-octyl acrylate, isooctyl acrylate, isononyl acrylate, acrylic acid stearyl acrylate, methoxyethyl acrylate, dimethylaminoethyl acrylate, zinc acrylate, 1,6_ hexanediol diacrylate, trimethylol propane triacrylate, 2-hydroxy ethyl methacrylate, acrylate, 2-hydroxypropyl methacrylate, propyl methacrylate, butyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, trimethylolpropane trimethacrylate, dipentaerythritol pentaacrylate, di dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, bis acid A diglycidyl ether (meth) acrylate, bisphenol F diglycidyl ether (meth) acrylate, bisphenol Z diglycidyl ether (meth) acrylate, tripropylene glycol di (meth) acrylate. 上述的化合物中,具有多个不饱和键的单体可以提高红外线遮蔽性能和耐热性,因而是优选的。 The above-described compounds, a monomer having a plurality of unsaturated bonds can be improved infrared shielding performance and heat resistance, which is preferable.

[0159] 〈溶剂(σ) > [0159] <Solvent (σ)>

[0160] 在本发明的热反应性组合物中,还可以进一步添加溶剂(〇)。 [0160] In the heat-reactive composition of the present invention, a solvent may be further added (square). 作为该溶剂,通常是能够根据需要溶解或分散上述各成分(花青化合物(α)等)的溶剂,可以列举出例如甲乙酮、 甲基戊基酮、二乙酮、丙酮、甲基异丙基酮、甲基异丁基酮、环己酮、2-庚酮等酮类;乙醚、二噁烷、四氢呋喃、1,2-二甲氧基乙烷、1,2 —二乙氧基乙烷、二丙二醇二甲醚等醚系溶剂;乙酸甲酯、乙酸乙酯、乙酸正丙酯、乙酸异丙酯、乙酸正丁酯、乙酸环己酯、乳酸乙酯、琥珀酸二甲酯、2,2,4_三甲基-1,3-戊二醇单异丁酸酯(texanol)等酯系溶剂;乙二醇单甲醚、乙二醇单乙醚等溶纤剂系溶剂;甲醇、乙醇、异丙醇或正丙醇、异丁醇或正丁醇、戊醇、二丙酮醇等醇系溶剂;乙二醇单甲基乙酸酯、乙二醇单乙基乙酸酯、丙二醇-1-单甲醚-2-乙酸酯(PGMEA)、二丙二醇单甲基醚乙酸酯、3-甲氧基丁基乙酸酯、乙氧基乙基丙酸酯、1-叔丁基-2-丙醇、3-甲氧基 Examples of the solvent is generally necessary, a solvent capable of dissolving or dispersing the above components (cyanine compound ([alpha]), etc.) may include, for example, methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone and other ketones; diethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2 - diethoxyethane , ether solvents dipropylene glycol dimethyl ether and the like; methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, 2 , 2,4_-trimethyl-1,3-pentanediol monoisobutyrate (Texanol) and other ester solvents; cellosolve solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and the like; methanol, ethanol, isopropanol or n-propanol, iso-butanol or n-butanol, amyl alcohol-based solvent, alcohol, and diacetone alcohol; ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol 1-monomethyl ether 2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethoxyethyl propionate, 1-tert-butyl -2-propanol, 3-methoxy 丁基乙酸酯、环己醇乙酸酯等醚酯系溶剂;苯、甲苯、二甲苯等BTX系溶剂; 己烷、庚烷、辛烷、环己烷等脂肪族烃系溶剂;松节油、D—柠檬烯、蒎烯等萜烯系烃油;矿油精、SWAZ0L#310 (Cosmo松山石油株式会社)、S0LVESS0#100 (Exxon化学株式会社)等链烷烃系溶剂;四氯化碳、氯仿、三氯乙烯、二氯甲烷、1,2_二氯乙烷等卤代脂肪族烃系溶剂;氯苯等卤代芳香族烃系溶剂;卡必醇系溶剂、苯胺、三乙胺、吡啶、乙酸、乙腈、二硫化碳、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮、二甲亚砜、水等,这些溶剂可以使用1种, 也可以制成2种以上的混合溶剂而使用。 Butyl acetate, cyclohexanol acetate and ether ester-based solvents; the BTX solvent such as benzene, toluene, xylene and the like; hexane, heptane, octane, cyclohexane and other aliphatic hydrocarbon solvents; turpentine, D- limonene, pinene terpene hydrocarbon oil; mineral spirits, SWAZ0L # 310 (Cosmo Matsuyama oil Co., Ltd.), S0LVESS0 # 100 (Exxon chemical Co.) and other paraffinic solvent; carbon tetrachloride, chloroform, trichlorethylene, dichloromethane, dichloroethane, etc. 1,2_ halogenated aliphatic hydrocarbon solvents; chlorobenzene, halogenated aromatic hydrocarbon solvents; carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N- dimethylformamide, N, N- dimethylacetamide, N- methylpyrrolidone, dimethyl sulfoxide, water, etc. these solvents may be used alone, may be made a mixed solvent of two or more species thereof. 其中,酮类、醚酯系溶剂等、特别是丙二醇-1-单甲醚-2-乙酸酯、环己酮等使得在热反应性组合物中树脂(β)与热聚合引发剂(γ)的相容性良好,因而优选。 Wherein, ketone, ester solvents such as an ether, particularly propylene glycol 1-monomethyl ether 2-acetate, cyclohexanone and the like so that a heat reactive resin composition (beta]) and the thermal polymerization initiator (gamma] ) good compatibility, it is preferable.

[0161] 在本发明的热反应性组合物中,上述溶剂(〇)的使用量优选为使得溶剂(〇)以外的组合物的浓度为5〜30质量%。 [0161] In the heat-reactive composition of the present invention, the concentration of the composition the solvent (square) is preferably used in an amount such that the solvent (square) than is 5~30 mass%. 溶剂(〇)以外的组合物的浓度小于5质量%时,难以增加膜厚,或有时无法充分吸收所期望的波长光,而超过30质量%时,有时因组合物的析出而引起组合物的保存性下降,或粘度增加而使处理性下降。 When the concentration of the composition other than the solvent (square) is less than 5 mass%, it is difficult to increase the film thickness, or may not sufficiently absorb the desired wavelength of light, and more than 30 mass%, the composition due to precipitation caused compositions decreased storage stability, viscosity increase or decrease in the process.

[0162] 在本发明的热反应性组合物中,还可以进一步含有无机化合物。 [0162] In the heat-reactive composition of the present invention may further contain an inorganic compound. 作为该无机化合物,可以列举出例如氧化镍、氧化铁、氧化铱、氧化钛、氧化锌、氧化镁、氧化钙、氧化钾、氧化硅、氧化铝等金属氧化物;层状粘土矿物、米洛丽蓝、碳酸钙、碳酸镁、钴系、锰系、玻璃粉末、 云母、滑石、高岭土、亚铁氰化物、各种金属硫酸盐、硫化物、硒化物、硅酸铝、硅酸钙、氢氧化铝、铂、金、银、铜等,其中,优选氧化钛、二氧化硅、层状粘土矿物、银等。 Examples of the inorganic compound, can include, for example, nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silica, alumina and other metal oxides; layered clay mineral, Milo Li blue, calcium carbonate, magnesium carbonate, cobalt compounds, manganese compounds, glass powder, mica, talc, kaolin, ferrocyanides, various metal sulfates, sulfides, selenides, aluminum silicate, calcium silicate, hydrogen aluminum, platinum, gold, silver, copper, etc., wherein, preferably titanium oxide, silica, layered clay minerals, and silver. 本发明的热反应性组合物中,上述无机化合物的含量相对于上述树脂Φ) 100质量份优选为0.1〜50质量份,更优选为0.5〜20质量份,这些无机化合物可以使用1种或2种以上。 Heat-reactive composition of the present invention, the content of the inorganic compound with respect to the resin Φ) 100 parts by mass is preferably 0.1~50 parts by mass, more preferably 0.5~20 mass parts, these inorganic compounds may be used singly or 2 or more kinds.

[0163] 上述无机化合物可以用作例如填充剂、防反射剂、导电剂、稳定剂、阻燃剂、机械强度提尚剂、特殊波长吸收剂、抗油墨剂等。 [0163] The inorganic compound may be used, for example, fillers, antireflection agents, electrically conductive agents, stabilizers, flame retardants, mechanical strength is still mention agent, a specific wavelength absorbing agent of Ink.

[0164] 在本发明的热反应性组合物中,当使用颜料和/或无机化合物时,可以添加分散剂。 [0164] In the heat-reactive composition of the present invention, when a pigment and / or an inorganic compound, a dispersing agent may be added. 作为该分散剂,只要是能够使颜料和/或无机化合物分散或稳定化的分散剂,则没有特另IJ限制,可以使用市售的分散剂、例如BYK-Chemi e公司制的BYK系列等,其中,由具有碱性官能团的聚酯、聚醚、聚氨酯构成的高分子分散剂、具有氮原子作为碱性官能团且具有氮原子的官能团为胺和/或其季铵盐而且胺值为1〜100mgK0H/g的分散剂可以优选使用。 Examples of the dispersing agent, so long as it can pigment and / or an inorganic compound dispersing agent or stabilized dispersion, the other is not particularly restricted IJ, a commercially available dispersing agent, e.g. BYK series manufactured by BYK-Chemi e and the like, wherein the polyester has a basic functional group, a polyether, a polyurethane composed of a polymer dispersant having a basic nitrogen atom as a functional group and a functional group having a nitrogen atom of an amine and / or quaternary ammonium salt and an amine value of 1 ~ 100mgK0H / g of dispersant can be preferably used.

[0165] 此外,在本发明的热反应性组合物中,根据需要可以加入对苯甲醚、氢醌、焦儿茶酚、叔丁基儿茶酚、吩噻嗪等热聚合抑制剂;增塑剂;粘接促进剂;填充剂;消泡剂;流平剂; 表面调整剂;抗氧化剂;紫外线吸收剂;分散助剂;抗凝聚剂;催化剂;固化促进剂;交联剂; 增稠剂等常用的添加物。 [0165] Further, in the heat-reactive composition of the present invention, if necessary, a thermal polymerization inhibitor may be added to the anisole, hydroquinone, pyrocatechol, t-butylcatechol, and phenothiazine; by plasticizers; adhesion promoters; fillers; defoamer; leveling agent; surface modifiers; antioxidants; ultraviolet absorbers; dispersing aid; antiaggregant; catalyst; cure accelerator; crosslinking agent; thickening like conventional additives.

[0166] 本发明的热反应性组合物中,上述的花青化合物(α)、树脂(β)和热聚合引发剂(γ)以外的任意成分(其中,具有不饱和键的单体(ω)和溶剂(σ)除外)的含量可以根据其使用目的来适当选择,没有特别限制,但优选的是,相对于上述树脂(β) 100质量份,将总量设定为50质量份以下。 [0166] heat-reactive composition of the present invention, the above-described cyanine compound ([alpha]), resin (beta]) and the thermal polymerization initiator of any component other than the agent (gamma]) (where a monomer having an unsaturated bond ([omega] content) and a solvent ([sigma]) excluded) can be appropriately selected depending on its purpose, is not particularly limited, but is preferably, with respect to 100 parts by mass of the resin (beta]), the total amount was 50 parts by mass or less.

[0167] 本发明的热反应性组合物中,通过与上述树脂〇3) —起使用其它的有机聚合物,也能改善由本发明的热反应性组合物形成的固化物的特性。 [0167] heat-reactive composition of the present invention, by the above-described resin 〇3) - from other organic polymers, can also improve the properties of the cured product formed by thermal reaction of the composition of the present invention. 作为上述有机聚合物,可以列举出例如聚苯乙烯、聚甲基丙烯酸甲酯、甲基丙烯酸甲酯一丙烯酸乙酯共聚物、聚(甲基)丙烯酸、苯乙烯一(甲基)丙烯酸共聚物、(甲基)丙烯酸一甲基丙烯酸甲酯共聚物、乙烯一氯乙烯共聚物、乙烯一乙烯基共聚物、聚氯乙烯树脂、ABS树脂、尼龙6、尼龙66、尼龙12、聚氨酯树月旨、聚碳酸酯聚乙烯醇缩丁醛、纤维素酯、聚丙烯酰胺、饱和聚酯、酚醛树脂、苯氧基树脂、聚酰胺酰亚胺树脂、聚酰胺酸树脂、环氧树脂等,其中优选聚苯乙烯、(甲基)丙烯酸一甲基丙烯酸甲酯共聚物、环氧树脂。 Examples of the organic polymer, may include for example, polystyrene, polymethyl methacrylate, a methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylate, a styrene (meth) acrylic acid copolymers , (meth) acrylic acid-methyl methacrylate copolymer, a vinyl chloride copolymer, ethylene-vinyl copolymers, polyvinyl chloride resins, ABS resins, nylon 6, nylon 66, nylon 12, urethane resins purpose month , polycarbonate, polyvinyl butyral, cellulose esters, polyacrylamide, saturated polyesters, phenol resins, phenoxy resins, polyamide-imide resins, polyamic acid resins, epoxy resins, preferably wherein polystyrene, (meth) acrylic acid-methyl methacrylate copolymer, an epoxy resin.

[0168] 在使用其它有机聚合物时,其使用量相对于上述树脂(β) 100质量份,优选为10〜 500质量份。 [0168] When other organic polymer, its amount with respect to 100 parts by mass of the resin (beta]), preferably 10~ 500 parts by mass.

[0169] 本发明的热反应性组合物中可以进一步并用链转移剂、增感剂、表面活性剂、硅烷偶联剂、三聚氰胺化合物等。 [0169] heat-reactive composition of the present invention may furthermore contain chain transfer agents, sensitizers, surface active agents, silane coupling agents, melamine compounds and the like.

[0170] 作为上述链转移剂或增感剂,一般使用含硫原子的化合物。 [0170] Examples of the chain transfer agent or sensitizer, sulfur atom-containing compound is generally used. 可以列举出例如巯基乙酸、硫代苹果酸、硫代水杨酸、2-巯基丙酸、3-巯基丙酸、3-巯基丁酸、N- (2-巯基丙酰基) 甘氨酸、2-巯基烟酸、3- [Ν- (2-巯基乙基)氨基甲酰基]丙酸、3- [Ν- (2-巯基乙基)氨基]丙酸、N- (3-巯基丙酰基)丙氨酸、2-巯基乙磺酸、3-巯基丙磺酸、4-巯基丁磺酸、十二烷基(4-甲硫基)苯基醚、2-巯基乙醇、3-巯基-1,2-丙二醇、1 -巯基-2-丙醇、3-巯基-2-丁醇、巯基苯酚、2-巯基乙胺、2-巯基咪唑、2-巯基苯并咪唑、2-巯基-3-羟基吡啶、2-巯基苯并噻唑、巯基乙酸、三羟甲基丙烷三(3-巯基丙酸酯)、季戊四醇四(3-巯基丙酸酯)等巯基化合物、将该巯基化合物氧化而得到的二硫化物、碘乙酸、碘丙酸、2-碘乙醇、2-碘乙磺酸、3-碘丙磺酸等碘代烷基化合物、三羟甲基丙烷三(3 —巯基异丁酸酯)、丁二醇双(3 —巯基异丁酸酯)、己二硫醇、癸二硫醇、1,4 May include, for example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercapto butyric acid, N- (2- mercaptopropionyl) glycine, 2-mercaptoethanol acid, 3- [Ν- (2- mercaptoethyl) carbamoyl] propionic acid, 3- [Ν- (2- mercaptoethyl) amino] propionic acid, N- (3- mercapto-propionyl) alanyl acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2 - propanediol - mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole, 2-mercapto-3-hydroxypyridine , thiazol-2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate) and the like mercapto compounds, and the mercapto compound is oxidized disulfide group is obtained thereof, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodo-ethanesulfonic acid, propanesulfonic acid, 3-iodo-iodo-alkyl compounds and the like, trimethylol propane tris (3 - mercapto isobutyrate), butanediol bis (3 - mercapto isobutyrate), hexane dithiol, decanedithiol, 1,4 一二甲基巯基苯、丁二醇二硫代丙酸酯、丁二醇二巯基乙酸酯、乙二醇二巯基乙酸酯、三羟甲基丙烷三巯基乙酸酯、丁二醇二硫代丙酸酯、三羟甲基丙烷三硫代丙酸酯、三羟甲基丙烷三巯基乙酸酯、季戊四醇四硫代丙酸酯、季戊四醇四巯基乙酸酯、三羟基乙基三硫代丙酸酯、下述化合物CU三巯基丙酸三(2—羟乙基)异氰脲酸酯等脂肪族多官能硫醇化合物、昭和电工公司制的KARENZ MT BDl、PE1、NR1等。 Twelve methyl mercaptobenzothiazole, thiopropionate butanediol dimethacrylate, butylene glycol dimercapto acetate, glycol dimercapto acetate, trimethylol propane tris thioglycolate, butanediol di thiopropionate, trimethylol propane tris thiopropionate, trimethylol propane tris thioglycolate, pentaerythritol tetrakis thiopropionate, pentaerythritol tetrakis mercaptoacetate, tris-hydroxyethyl trisulfide Generation propionate, the following compound CU trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate and other aliphatic polyfunctional thiol compounds, manufactured by Showa Denko KARENZ MT BDl, PE1, NR1 like.

[0171] [化19] [0171] [Chemical Formula 19]

[0172] 化合物No. Cl [0172] Compound No. Cl

[0173] [0173]

Figure CN107531857AD00271

[0174] 作为上述表面活性剂,可以使用全氟烷基磷酸酯、全氟烷基羧酸盐等含氟表面活性剂、高级脂肪酸碱金属盐、烷基磺酸盐、烷基硫酸盐等阴离子系表面活性剂;高级胺卤酸盐、季铵盐等阳离子系表面活性剂;聚乙二醇烷基醚、聚乙二醇脂肪酸酯、山梨糖醇酐脂肪酸酯、脂肪酸单甘油酯等非离子表面活性剂;两性表面活性剂;娃酮系表面活性剂等表面活性剂,它们也可以组合起来使用。 [0174] Examples of the surfactant may be used perfluoroalkyl phosphate, perfluoroalkyl carboxylate salts and the like fluorine-containing surfactants, metal salts of higher fatty acid, alkyl sulfonates, alkyl sulfates, etc. anionic surfactant; higher amine halogen acid salts and quaternary ammonium salts cationic surfactants; polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan aliphatic acid esters, fatty acid monoglycerides and other nonionic surfactants; amphoteric surfactants; baby ketone surfactant surfactant, they can also be used in combination.

[0175] 作为上述硅烷偶联剂,可以使用例如信越化学公司制的硅烷偶联剂,其中,KBE — 9007、KBM—502、KBE — 403等具有异氰酸酯基、甲基丙烯酰基、环氧基的硅烷偶联剂可以优选使用。 [0175] As the silane coupling agent may be used by Shin-Etsu Chemical Co., Ltd., for example, a silane coupling agent, wherein, KBE - 9007, KBM-502, KBE - 403 and the like having an isocyanate group, a methacryloyl group, an epoxy group The silane coupling agent can be preferably used.

[0176] 作为上述三聚氰胺化合物,可以列举出(聚)羟甲基三聚氰胺、(聚)羟甲基甘脲、 (聚)羟甲基苯并胍胺、(聚)羟甲基脲等氮化合物中的活性羟甲基(CH2OH基)的全部或一部分(至少2个)被烷基醚化后的化合物。 [0176] Examples of the melamine compound include (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, (poly) methylol urea and other nitrogen compound all or part of active methylol groups (CH2OH groups) in the (at least two) are the alkyl-etherified compound. 其中,作为构成烷基醚的烷基,可以列举出甲基、乙基或丁基,相互可以相同,也可以不同。 Wherein the alkyl group constituting the alkyl ether include methyl, ethyl or butyl, each may be the same or different. 另外,未烷基醚化的羟甲基可以在一个分子内进行自缩合,也可以二个分子间进行缩合,结果形成低聚物成分。 Further, non-alkyl-etherified methylol groups in one molecule may be self-condensation, the condensation can be performed between the two molecules, resulting in an oligomer component. 具体地,可以使用六甲氧基甲基三聚氰胺、六丁氧基甲基三聚氰胺、四甲氧基甲基甘脲、四丁氧基甲基甘脲等。 Specifically, using hexamethoxymethylmelamine, six butoxymethyl melamine, tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril like. 其中,优选六甲氧基甲基三聚氰胺、六丁氧基甲基三聚氰胺等烷基醚化后的三聚氰胺。 The alkyl-etherified melamine wherein, preferably hexamethoxymethylmelamine, six butoxymethyl melamine.

[0177] 本发明的热反应性组合物在无溶剂的固体状态的情况下,可以在溶剂中溶解或分散后,用旋涂器、辊涂器、棒涂器、模涂器、帘式涂布器、狭缝涂布器、浸渍涂布器、各种印刷、 浸渍等公知的手段应用于钠玻璃、石英玻璃、半导体基板、金属、纸、塑料等支撑基体上。 [0177] After the heat-reactive composition of the present invention in the case of a solvent-free solid state may be dissolved or dispersed in a solvent, with a spin coater, roll coater, bar coater, a die coater, a curtain coating cloth, a slit coater, dip coater, various printing, dipping known means used in soda glass, quartz glass, semiconductor substrates, metals, paper, plastic and other support base. 此夕卜,也可以暂时施加到薄膜等支撑基体上后再转印到其它支撑基体上,其应用方法没有限制。 This evening Bu, may be temporarily applied to the support base film or the like and then transferred onto another support base, the application method is not limited.

[0178] 使本发明的热反应性组合物固化时的加热条件是70〜250°C下1〜100分钟。 [0178] of the present invention, heating the reaction conditions during heat-curable composition is 70~250 ° C 1~100 minutes. 可以在预烘烤后,进行加压,再进行后烘烤,也可以在不同的数个阶段的温度下进行烘烤。 After the pre-baking can, pressurized, baking, baking may be carried out at a temperature of several different stages after then.

[0179] 加热条件根据各成分的种类和配合比例的不同而不同,例如、在70〜180°C下,烘箱的话加热5〜15分钟,热板的话加热1〜5分钟。 [0179] The heating conditions depending on the kind and blending ratio of each component is different, e.g., at 70~180 ° C, then oven heated 5~15 minutes, then heated hot plate ~ 5 minutes. 然后,为了使涂膜固化,在100〜250 °C、优选在180〜250 °C、更优选在200〜250 °C下,烘箱的话加热处理30〜90分钟、热板的话加热处理5〜30分钟,就能够得到固化膜。 Then, in order to cure the coating, at 100~250 ° C, preferably at 180~250 ° C, more preferably at 200~250 ° C, then a heat treatment oven 30~90 minutes, then the hot plate heating treatment 5~30 minutes, a cured film can be obtained.

[0180] 本发明的热反应性组合物(或其固化物)可以用于热反应性涂料或清漆、热反应性粘接剂、印制电路板或彩色电视机、PC监视器、便携信息终端、数码相机等彩色显示的液晶显示面板中的滤色器、CCD图像传感器的滤色器、等离子体显示面板用的电极材料、粉末涂层、印刷油墨、印刷版、粘接剂、齿科用组合物、立体造型用树脂、凝胶涂层、电子工程学用的光致抗蚀剂、电镀抗蚀剂、蚀刻抗蚀剂、液状和干燥膜这两者、阻焊剂、用于制造各种显示用途用的滤色器或在等离子体显示面板、电致发光显示装置以及LCD的制造工序中用于形成结构的抗蚀剂、用于密封电气或电子部件的组合物、阻焊剂、磁记录材料、微小机械部件、波导、光学开关、镀覆用掩模、蚀刻掩模、彩色试验体系、玻璃纤维电缆涂层、丝网印刷用模版、 用于通过立体平版印刷制造三 [0180] heat-reactive composition of the present invention (or cured) may be used to heat the reaction paint or varnish, the heat-reactive adhesive, printed circuit board or a color television, PC monitors, portable information terminal LCD, digital cameras and other color display panel color filter, the color filter of the CCD image sensor, a plasma display panel with the electrode material, the powder coatings, printing inks, printing plates, adhesives, dental composition, three-dimensional shape with a resin, gel coats, photoresists used in electrical engineering, a plating resist, etch resist, both liquid and dry films, solder resists, used in the manufacture the use of color filters with a display or panel, an electroluminescent display device and a manufacturing process for an LCD forming the resist structure, the composition for sealing electric or electronic component, the solder resist in the plasma display, recording materials, fine machine parts, waveguides, optical switches, plating masks, etch masks, color test systems, glass fiber cable coatings, screen printing stencils, for producing by stereolithography three 物体的材料、全息照相记录用材料、图像记录材料、微细电路、脱色材料、用于图像记录材料的脱色材料、使用微囊的图像记录材料用的脱色材料、印制电路板用光致抗蚀剂材料、UV和可见激光直接图像系用的光致抗蚀剂材料、用于形成印制电路基板的逐次叠层中的电介质层的光致抗蚀剂材料或保护膜等各种用途中,其用途并没有特别限制。 The material of the object, the hologram recording material masked with a photo resist, image recording materials, fine circuits, decolorizing materials, decolorizing materials for image recording materials, decolorizing materials for image recording materials using microcapsules used, the printed circuit board binder material, UV and visible laser direct use of the image-based photoresist material used to form various purposes photoresist materials or protective film sequentially laminated dielectric layers of the printed circuit board in their use is not particularly limited.

[0181] 本发明的热反应性组合物是为了遮断特定的红外线的目的而使用的,特别是作为用于形成波长截止滤光器的热反应性组合物而有用。 [0181] heat-reactive composition of the present invention to a specific object blocking infrared rays is used, in particular is useful for forming thermally reactive composition wavelength cut filter as.

[0182] 下面,对本发明的波长截止滤光器进行说明。 [0182] Next, a wavelength cut filter of the present invention will be described.

[0183] 本发明的波长截止滤光器中,在玻璃基板(A)的一个面上具有由本发明的热反应性组合物得到的涂布层⑶,并且在玻璃基板㈧的另一个面上具有红外线反射膜(C)。 [0183] The wavelength cut filter according to the present invention, in one surface of a glass substrate (A) having a coating layer obtained from the heat-reactive ⑶ composition of the present invention, and having the other surface of the glass substrate (viii) infrared reflecting film (C). 涂布层⑶和红外线反射膜(C)分别层叠于玻璃基板(A)的各面上。 ⑶ coating layer and the infrared reflecting film (C) are stacked on a glass substrate (A) of each side. 如图1所示,可以将具有由本发明的热反应性组合物得到的涂布层⑶的一侧作为光的入射侧,如图2所示,也可以将具有红外线反射膜(C)的一侧作为光的入射侧。 As shown in FIG 1, a side having a coating layer may be obtained from ⑶ heat-reactive composition of the present invention as the light incident side, as shown, may be provided with a infrared reflecting film (C), 2 side as the light incident side. 以下,对各层依次进行说明。 Hereinafter, each layer sequentially described.

[0184] 〈玻璃基板㈧〉 [0184] <glass substrate (viii)>

[0185] 作为本发明的波长截止滤光器中使用的玻璃基板(A),可以从在可见区域透明的玻璃材料中适当选择来使用,可以使用钠钙玻璃、白板玻璃、硼硅酸玻璃、强化玻璃、石英玻璃、磷酸盐系玻璃等,其中,钠钙玻璃便宜而且容易获得,因而优选,白板玻璃、硼硅酸玻璃和强化玻璃由于容易获得,而且硬度高,加工性优良,因而优选。 [0185] As the wavelength cut filter according to the present invention, the glass substrate (A) used, may be selected for use from the transparent in the visible region of the glass material suitably can be used soda lime glass, white glass, borosilicate glass, glass, quartz glass, phosphate glass, wherein the soda-lime glass is inexpensive and easily available, it is preferable, white plate glass, tempered glass, and borosilicate glass because it is easy to obtain, but also a high hardness, excellent formability, which is preferable.

[0186] 进而,如果对玻璃基板实施了硅烷偶联剂等的前处理后涂布由本发明的热反应性组合物构成的涂布液而形成涂布层(B),则涂布液干燥后的含有染料的涂布层⑶对玻璃基板的密着性提高。 After [0186] Further, if the glass substrate was a silane coupling agent treatment before coating the coating liquid by a heat-reactive composition of the present invention configured to form a coating layer (B), the coating was dried ⑶ coating layer containing a dye to improve the adhesion of the glass substrate.

[0187] 作为上述硅烷偶联剂,可列举出γ-环氧丙氧丙基三甲氧基硅烷、γ-环氧丙氧丙基甲基二乙氧基硅烷、β-(3,4-环氧环己基)乙基三甲氧基硅烷等环氧官能性烷氧基硅烷、 Ν-β (氨基乙基)-γ -氨基丙基三甲氧基硅烷、γ -氨基丙基三乙氧基硅烷、N-苯基-γ -氨基丙基二甲氧基娃烧等氣基官能性烧氧基娃烧、y _疏基丙基二甲氧基娃烧等疏基官能性烧氧基娃烧等。 [0187] Examples of the silane coupling agent include [gamma] glycidoxypropyl trimethoxysilane, [gamma] glycidoxypropyl methyl diethoxy silane, β- (3,4- ring oxo-cyclohexyl) ethyltrimethoxysilane and the like epoxy-functional alkoxysilane, Ν-β (aminoethyl) -γ - aminopropyl trimethoxy silane, γ - aminopropyl triethoxysilane, N- phenyl -γ - aminopropyl dimethoxy baby burning and other gas-functional group baby burn burn, y _ mercapto propyl dimethoxy baby burn burn like mercapto functional group, and the like baby burn .

[0188] 另外,在玻璃基板㈧与涂布层⑶之间还可以具有底层。 [0188] Further, (viii) between the glass substrate and the coating layer may have further ⑶ underlayer. 底层是如下获得的:将平均一次粒径为5〜IOOnm的一次粒子凝聚而成的平均二次粒径为20〜250nm的金属氧化物微粒的凝聚体分散于下述所示的溶剂中,得到涂布液,将该涂布液用下述所示的涂布方法进行涂布而得到底层,厚度为30〜lOOOnm。 The bottom layer is obtained as follows: the average primary particle diameter of primary particles agglomerated 5~IOOnm average secondary particle diameter of the metal oxide fine particles 20~250nm aggregates dispersed in a solvent as shown below to give coating liquid the coating liquid was coated with a coating obtained by the method shown below underlayer thickness 30~lOOOnm. 上述金属氧化物微粒的凝聚体相对于涂布液总量优选为0.1〜50质量%。 Fine particles of the metal oxide agglomerates with respect to the total amount of the coating solution is preferably 0.1~50% by mass.

[0189] 玻璃基板(A)的厚度没有特别限定,但优选为0.05〜8mm,从轻量化和强度的观点出发,更优选为〇· 05〜lmm〇 [0189] The thickness of the glass substrate (A) is not particularly limited, but is preferably 0.05~8mm, from the viewpoint of strength and weight reduction, more preferably square-05~lmm〇

[0190] 本发明中,由于基材是玻璃板,所以能够在基材上直接涂布,干燥后进行切断加工,构造和工艺变得简易。 [0190] In the present invention, since the substrate is a glass plate, it can be directly coated on the substrate, a cutting process, the process becomes simple construction and dried. 另外,由于基板是玻璃板,所以与塑料的情况相比,耐热性(260°C 的耐软熔性)较高。 Further, since the substrate is a glass plate, as compared with the case of plastic, heat resistance (reflow resistance of 260 ° C) higher.

[0191] 〈涂布层⑶〉 [0191] <Coating Layer ⑶>

[0192] 本发明的波长截止滤光器中使用的、由本发明的热反应性组合物得到的涂布层⑶如上所述,可以通过将本发明的热反应性组合物涂布于玻璃基板(A)上而形成。 [0192] The wavelength cut filter of the present invention is used, the heat obtained from the reactive composition according to the present invention ⑶ coating layer described above, can be obtained by heat-reactive composition of the present invention is applied to a glass substrate ( A upper) is formed. 得到的涂膜根据需要加热而使其固化。 The resulting coating film cured by heating as necessary.

[0193] 含有染料的涂布层(B)的厚度为1〜200μπι时,能得到均匀的膜,有利于薄膜化,因而是优选的。 [0193] thickness of the coating layer (B) containing the dye is 1~200μπι, a uniform film can be obtained, in favor of the film, which is preferable. 如果低于Ιμπι,则不能充分显现功能,如果超过200μπι,则涂布时有可能残留溶剂。 If less than Ιμπι, the function can not be sufficiently developed, and if it exceeds 200μπι, there is a possibility of residual solvent during coating.

[0194] 〈红外线反射膜(C) > [0194] <infrared reflecting film (C)>

[0195] 本发明的波长截止滤光器中使用的红外线反射膜(C)具有遮断700〜1200nm的波长区域的光的功能,由低折射率层和高折射率层交替层叠而成的电介体多层膜形成。 Dielectric [0195] The cutoff wavelength of the present invention, the infrared reflecting film (C) used in the filter has a function of blocking light in a wavelength region 700~1200nm, a low refractive index layer and a high refractive index layer laminated alternately formed multilayer film.

[0196] 作为构成上述低折射率层的材料,可以使用折射率为1.2〜1.6的材料,例如可以列举出二氧化硅、氧化铝、氟化镧、氟化镁、六氟化铝钠等。 [0196] As a material constituting the low refractive index layer, a refractive index of the material of 1.2~1.6, and examples include silica, alumina, lanthanum fluoride, magnesium fluoride, sodium aluminum hexafluoride like.

[0197] 作为构成上述高折射率层的材料,可以使用折射率为1.7〜2.5的材料,可以列举出例如氧化钛、氧化错、五氧化钽、五氧化银、氧化镧、氧化纪、氧化锌、硫化锌、氧化铟等,此夕卜,还可以列举出以它们为主成分、并含有少量的氧化钛、氧化锡、氧化铈等的材料等。 [0197] As a material constituting the high refractive index layer, a refractive index of the material may be used 1.7~2.5 may include, for example, titanium oxide, wrong, tantalum pentoxide, silver pentoxide, lanthanum oxide, Ji, zinc oxide , zinc sulfide, indium oxide or the like, this evening Bu, may also include in their main component, and a small amount of material is titanium oxide, tin oxide, cerium oxide containing like.

[0198] 有关层叠上述低折射率层和高折射率层的方法,只要是能形成将上述的层层叠而成的电介体多层膜,就没有特别限制,例如可以列举出在玻璃基板上,使用CVD法、溅射法、 真空蒸镀法等将低折射率层和高折射率层交替层叠而形成电介体多层膜的方法。 [0198] Method For laminating the low refractive index layer and the high refractive index layer, as long as it can form a dielectric multilayer film to the above-described layers are laminated, is not particularly limited, and examples include a glass substrate to form a dielectric multilayer film for low refractive index layer and high refractive index layers are alternately laminated CVD method, a sputtering method, a vacuum deposition method or the like method. 另外,还可以预先形成电介体多层膜,并用粘接剂将其贴合于玻璃基板上。 Further, a dielectric multilayer film may also be formed in advance, and with an adhesive which is bonded to the glass substrate.

[0199] 层叠数为10〜80层,为25〜50层时,从工艺和强度的观点出发是优选的。 [0199] number of laminated layers 10~80, 25~50 layer is, the starting process is preferable from the viewpoint of strength and.

[0200] 上述低折射率层和高折射率层的厚度分别通常为要遮断的光线的波长λ (nm)的1/ 10〜1/2的厚度。 [0200] The thickness of the high refractive index layer and the low refractive index layer are typically the wavelength λ of the light to be blocked (nm) thickness of 1 / 10~1 / 2. 厚度如果低于0. U或大于〇.5λ,则折射率(η)与物理膜厚(d)的积(nd)与用λ/4的倍数表示的光学膜厚大大不同,因而有可能无法进行特定波长的遮断\透射。 The optical thickness of a multiple of the thickness of the product is less than or greater than 0. U 〇.5λ, the refractive index ([eta]) and a physical film thickness (d), (nd) and a λ / 4 indicates significantly different, it may be not be specific wavelength cutoff \ transmission.

[0201] 作为上述红外线反射膜(C),除了前述的电介体多层膜之外,还可以使用含有最大吸收波长为700〜IlOOnm的染料的膜、层叠了高分子的膜、涂布胆留醇型液晶而形成的膜等使用了有机材料的膜。 [0201] Examples of the infrared reflecting film (C), in addition to the dielectric multilayer film outside, may be used contain a maximum absorption wavelength 700~IlOOnm dye film, the polymer film is laminated, coated bile leaving the formed alcohol type liquid crystal film using a film of an organic material.

[0202] 本发明的波长截止滤光器优选透射率满足下述(i)〜(iii)。 [0202] The wavelength cut filter according to the present invention preferably satisfies the following transmittance (i) ~ (iii). 此外,透射率的测定是使用日本分光株式会社制的紫外可见近红外分光光度计V-570来测定。 Further, transmittance was measured using a Nippon Bunko Co., Ltd. ultraviolet visible near-infrared spectrophotometer V-570 was determined.

[0203] (i)在波长430〜580nm的范围内从波长截止滤光器的垂直方向(与玻璃基板的板面垂直的方向、以下同样)测定时的透射率的平均值为75%以上。 [0203] (i) in the vertical direction in the range of 430~580nm wavelength from the wavelength cut-off filter (a direction perpendicular to the plate surface of the glass substrate, the same applies hereinafter) when the average value of the transmittance measured was 75% or more.

[0204] (ii)在波长800〜IOOOnm内从波长截止滤光器的垂直方向测定时的透射率的平均值为5%以下。 [0204] (ii) the average transmittance when measured from the vertical wavelength cutoff filter in the wavelength 800~IOOOnm 5% or less.

[0205] (iii)在波长560〜800nm的范围内从波长截止滤光器的垂直方向测定时的透射率达到80%的波长的值(Ya)与从相对于波长截止滤光器的垂直方向为35°的角度测定时的透射率达到80%的波长的值(Yb)的差的绝对值为30nm以下。 [0205] (iii) transmittance measured from the vertical wavelength cutoff filter in the wavelength range reaches a value of 80% of 560~800nm ​​wavelength (Ya) from the vertical direction with respect to the wavelength cutoff filter the absolute value of the difference between the measured value of transmittance of an angle of 35 ° is 80% of the wavelength (Yb) is 30nm or less.

[0206] 对于波长截止滤光器来说,在上述(i)的波长430〜580nm的范围内的透射率的平均值如果低于75%,则几乎不能透射可见光区域的光。 [0206] For a wavelength cut filter, the average transmittance in a wavelength range of (i) If the 430~580nm of less than 75%, it hardly transmits light in the visible region. 在(i)的波长430〜580nm的范围内的透射率的平均值更优选为80%以上。 The average transmittance in the wavelength range of (i) of 430~580nm more preferably 80% or more. 在上述(ii)的波长800〜IOOOnm内的透射率的平均值如果超过5%,则几乎不能截止红外线区域的光,所以有可能难以以接近人的视见度的方式校正感度。 The average transmittance in the wavelength 800~IOOOnm above (ii), if more than 5%, it hardly off infrared light region, it may be difficult to approach the visibility of the human sense of correction. (ii)的波长800〜IOOOnm内的透射率的平均值更优选为1 %以下。 The average transmittance in (ii) a wavelength 800~IOOOnm more preferably 1% or less.

[0207] 另外,上述(iii)的Ya与Yb的差的绝对值如果超过30nm,则对光的入射角的依赖性变高,波长截止滤光器的特性会随着光的入射角的变化而变化,所以有可能发生色彩在画面的中心和周边发生变化等弊端。 [0207] Further, the absolute value of the difference between Ya and Yb in the above (iii), and if it exceeds 30 nm, the light incident angle dependency increases, wavelength cutoff filter characteristics vary with the angle of incidence of the light the change, it is possible to change the color in the center and periphery of the screen of other defects occur. (iii)的Ya与Yb的差的绝对值更优选为5nm以下,进一步优选为3nm以下。 Absolute difference of (iii) Ya and Yb is more preferably 5nm or less, more preferably 3nm or less.

[0208] 作为本发明的波长截止滤光器的具体的用途,可以列举出安装于汽车和建筑物的窗玻璃等上的热射线截止滤光器;数码相机、数字摄像机、监视照相机、车载用照相机、网络摄像头、手机用照相机等固体摄像装置中的CCD和CMOS等固体摄像元件用视见度校正用;自动曝光计;等离子体显示器等显示装置等。 [0208] As the wavelength cut filter of the present invention the specific use, may include a heat ray cut filter is mounted on the window glass of automobiles and buildings; digital cameras, digital video cameras, monitoring cameras, vehicle camera, web camera, a mobile phone with a solid-state imaging device and a CCD camera or the like CMOS, with the visibility correction; automatic exposure meter; display device like a plasma display.

[0209] 下面,对本发明的固体摄像装置和照相机模块进行说明。 [0209] Next, the solid-state imaging device and a camera module of the present invention will be described.

[0210] 本发明的固体摄像装置除了在摄像元件的前表面具备本发明的波长截止滤光器以外,与以往的固体摄像装置同样地构成。 [0210] The solid-state imaging device of the present invention, the present invention is provided in addition to the front surface of the imaging element other than a wavelength cut filter, and the configuration of the conventional solid state imaging device in the same manner. 本发明的波长截止滤光器1可以如图5和图6所示那样,在固体摄像元件2的光入射侧固定于固体摄像元件以外的部分上,也可以如图3和图4 所示那样,直接固定于固体摄像元件2的前表面。 A wavelength cut filter of the present invention may be 1 and 5 as shown in FIG. 6, on the light incident side portion 2 is fixed to the solid-state imaging device other than the solid-state imaging device, may be shown in FIG. 3 and FIG. 4 , directly fixed to the front surface of the solid-state image pickup element 2.

[0211] 本发明的固体摄像装置上,根据需要还可以配置光学低通滤波器、防反射滤光器、 滤色器等,将它们层叠的顺序没有特别限制。 [0211] solid-state imaging device of the present invention, may also be required configuration of the optical low-pass filter, anti-reflection filter, color filters, the order in which they are stacked is not particularly limited.

[0212] 如图3和图4所示,有关作为本发明的固体摄像装置之一的照相机模块,下面对本发明的波长截止滤光器1在固体摄像元件2的光入射侧层叠于固体摄像元件上的情况进行具体说明。 [0212] FIGS. 3 and 4, as related to one of the camera module of the present invention is a solid-state imaging device, the following cut-off wavelength of the filter of the present invention is a light incident side of the solid-state imaging element 2 laminated to the solid-state imaging device the situation will be specifically described.

[0213] 图3和图4是表示作为本发明的固体摄像装置之一的照相机模块的构成的一个形态的截面图。 [0213] FIG. 3 and FIG. 4 is a sectional view showing a configuration of a form of one of the camera module of the present invention, the solid-state imaging device. 照相机模块具有:在半导体基板上形成为俯视矩形状的固体摄像元件2;和在固体摄像元件2的受光部3的相反侧,从光入射侧开始依次层叠了含有染料的涂布层⑶、玻璃基板(A)、红外线反射膜(C)而成的波长截止滤光器1 (图3) /或依次层叠了红外线反射膜(C)、玻璃基板(A)、含有染料的涂布层(B)而成的波长截止滤光器1 (图4),通过在固体摄像元件2的一面的除去受光部3以外的区域上形成的粘接剂4将固体摄像素子2和波长截止滤光器1接合。 The camera module comprising: in a plan rectangular solid-state imaging element on a semiconductor substrate 2; and a side opposite to the light receiving unit 3 of the solid-state image pickup element 2, starting from the light incident side are sequentially laminated layer ⑶ coating containing a dye, a glass the substrate (a), an infrared reflecting film (C) obtained by wavelength cutoff filter 1 (FIG. 3) / or infrared reflective film are sequentially laminated (C), a glass substrate (a), a dye-containing coating layer (B ) obtained by wavelength cutoff filter 1 (FIG. 4), the solid imaging element by removing one side by an adhesive 2 is formed on the region other than the third optical unit 4 and the solid image pickup element 2, and the sub-wavelength cutoff filter 1 engagement. 作为固体摄像装置的照相机模块通过波长截止滤光器1取入来自外部的光,并通过配置于固体摄像元件2的受光部3中的受光元件来受光。 As a solid-state imaging device of the camera module wavelength cutoff filter 1 takes in light from the outside, and by the light receiving element by arranging the solid-receiving element 3 in the light receiving section 2 by the light.

[0214] 如图5和图6所示,有关作为本发明的固体摄像装置之一的照相机模块,下面对本发明的波长截止滤光器1在固体摄像元件2的光入射侧固定于固体摄像元件以外的部分上的情况进行具体说明。 [0214] As shown in FIGS. 5 and 6, the camera module as one of the relevant solid state imaging device according to the present invention, the following cut-off wavelength of the filter of the present invention is a light incident side of the solid-state imaging element 2 is fixed to the solid-state imaging device on portions other than the case will be specifically described.

[0215] 图5和图6是表示作为本发明的固体摄像装置之一的照相机模块的构成的一个形态的截面图。 [0215] FIG. 5 and FIG. 6 is a sectional view showing a configuration of a form of one of the camera module solid state imaging device according to the present invention. 照相机模块具有:在半导体基板上形成为俯视矩形状的固体摄像元件2;和在固体摄像元件2的受光部3的相反侧,从光入射侧开始依次层叠了含有染料的涂布层⑶、玻璃基板(A)、红外线反射膜(C)而成的波长截止滤光器1 (图5) /或依次层叠了红外线反射膜(C)、玻璃基板㈧、含有染料的涂布层⑶而成的波长截止滤光器1 (图6),在固体摄像元件2 的一面的除去受光部3以外的区域上形成。 The camera module comprising: in a plan rectangular solid-state imaging element on a semiconductor substrate 2; and a side opposite to the light receiving unit 3 of the solid-state image pickup element 2, starting from the light incident side are sequentially laminated layer ⑶ coating containing a dye, a glass the substrate (a), an infrared reflecting film (C) obtained by wavelength cutoff filter 1 (FIG. 5) / or an infrared reflective film are sequentially laminated (C), (viii) a glass substrate, the coating layer containing a dye formed ⑶ a wavelength cut-off filter (FIG. 6), one surface 2 is formed by removing a region other than the light part 3 the solid imaging element. 作为固体摄像装置的照相机模块通过波长截止滤光器1取入来自外部的光,并通过配置于固体摄像元件2的受光部3中的受光元件来受光。 As a solid-state imaging device of the camera module wavelength cutoff filter 1 takes in light from the outside, and by the light receiving element by arranging the solid-receiving element 3 in the light receiving section 2 by the light.

[0216] 作为粘接剂4,可以使用丙烯酸系树脂、环氧系树脂等UV固化性粘接剂或热固化性树脂,均匀地涂布该粘接剂4之后,根据需要使用众所周知的光刻技术将粘接剂进行布图, 并通过热固化而接合。 After [0216] As the adhesive agent 4 can be used acrylic resin, epoxy resin, UV curable adhesive or a thermosetting resin, uniformly applying the adhesive 4, as necessary, using well known photolithographic techniques for patterning the adhesive, and bonded by thermal curing. 接合时,也可以在真空环境内贴合后进行真空加压。 When engaged, vacuum pressing may be performed after bonding in a vacuum environment.

[0217] 安装基板8是使用了玻璃环氧基板或陶瓷基板等硬质基板,并设置有控制固体摄像元件2的控制电路。 [0217] mounting substrate 8 is the use of a rigid substrate or a glass epoxy substrate, ceramic substrate, and the solid-state imaging device provided with a control of the control circuit 2.

[0218] 在安装基板8上配置固体摄像元件2,然后在安装基板8的固着镜头支架7的位置上预先涂布粘接剂4。 [0218] solid-state image pickup device 2 disposed on the mounting substrate 8, and then mounting the fixing position of the lens holder 7 of the substrate 8 on the adhesive 4 previously applied.

[0219] 镜头盖6是用于保护镜头5的。 [0219] 6 is a lens cover to protect the lens 5. 另外,镜头支架7用于保持镜头5,具有安装于安装基板8上并覆盖固体摄像元件2的箱状的基盘部7a、和保持镜头5的圆筒形状的镜筒部7b。 Further, the lens holder 7 for holding a lens 5, having a barrel portion 7b is mounted on the mounting substrate and covers the solid-state imaging device 8 a box-shaped portion 7a 2 of the base plate, and a cylindrical lens holder 5.

[0220] 然后,按照镜头支架7的下端面与涂布的粘接剂4接触的方式将镜头支架7配置于安装基板8上,再以固体摄像元件2的受光部3与镜头支架7内的镜头5的距离与镜头5的焦点距离一致的方式进行镜头支架7的位置的调节。 Embodiment [0220] Then, according to the lens holder 7 in contact with the lower end surface of the adhesive 4 is applied to the lens holder 7 is disposed on the mounting substrate 8, and then the solid imaging element 3 and the light receiving portion in the lens holder 2 7 5 and the focus lens from the lens 5 is adjusted position of the lens holder 7 in a manner consistent distance.

[0221] 进行了镜头支架7的位置调节后,对粘接剂4照射紫外线,使粘接剂4固化,由此可以制造照相机t吴块。 After [0221] the position of the lens holder 7 has been adjusted, 4 irradiated with ultraviolet rays for the adhesive, curing the adhesive 4, thereby manufacturing a camera block Wu t.

[0222] 也可以将固定了镜头支架7的安装基板8整体在约85°C下加热,通过热固化而使粘接剂4的固化充分进行。 [0222] may be a fixed lens holder 7 is mounted integrally substrate 8 at about 85 ° C is heated by heat curing of the adhesive is sufficiently cured 4.

[0223] 此外,在照相机模块的制造方法中,由于在照射紫外线的工序之后,包含加热安装基板8整体的工序,所以镜头支架7、镜头5和波长截止滤光器1均必须使用耐热性高的材料。 [0223] Further, in the method of manufacturing a camera module, since ultraviolet rays after the step of mounting comprising a step of heating the entire substrate 8, so that the lens holder 7, the lens 5 and the wavelength cutoff filter 1 must use the heat-resistant high material. 具体而言,除了如前述那样的为了粘接剂4的热固化而进行的加热之外,由于将配置于安装基板8的下表面的多处软钎料在约260°C下进行加热熔融处理后与其它基板进行软钎焊,因此优选由具有耐软熔性的材料形成。 Specifically, in addition to the heating as described above thermosetting adhesive 4 is carried out, since the multiple solder disposed on the mounting surface of the lower substrate 8 material is heated in a melting treatment at about 260 ° C after soldering the other substrate, preferably formed of a material having resistance to reflow resistance.

[0224]实施例 [0224] Example

[0225]以下,列举实施例等来更详细地说明本发明,但本发明不受这些实施例等的限定。 [0225] Hereinafter, other embodiments of the present invention include embodiments described in more detail, but the present invention is not limited to these Examples and the like. [0226][制造例1 ]树脂Φ) No. 1的调制 [0226] [Manufacturing Example 1] The resin Φ) No. 1 prepared

[0227] 将丙烯酸40质量份和甲基丙烯酸丁酯50质量份溶解于丙二醇-1-单甲基醚-2-乙酸酯(PGMEA) 200质量份中,向该溶液中加入偶氮二异丁腈4质量份作为自由基聚合引发剂, 在80°C下搅拌3小时。 [0227] 40 parts by mass of acrylic acid and 50 parts by mass of butyl methacrylate were dissolved in propylene glycol 1-monomethyl ether 2-acetate 200 parts by mass (PGMEA), and to the solution was added azobisisobutyronitrile nitrile 4 parts by mass of a radical polymerization initiator, and stirred at 80 ° C 3 hours. 然后,加入用丙烯酸改性过的CELLOXIDE 2021P(Daicel化学公司制的脂环式环氧树脂)10质量份,在120°C下搅拌3小时,得到树脂(β) No. 1。 Then, through the addition of an acrylic-modified CELLOXIDE 2021P (Daicel Chemical Co., Ltd. alicyclic epoxy resin) 10 parts by mass, stirred at 120 ° C 3 hours to obtain a resin (β) No. 1.

[0228] 该树脂(β) No. 1是下述的树脂(β):在上述通式⑴中,X1为氢原子或甲基,Y1为上述通式⑴表示的二价的结合基(X2为下述式(η)表示的基团,Z1和Z2为直接键合),R1为碳原子数为1〜8的烧基,R2〜R3为氢原子,R4为甲基。 [0228] The resin (β) No. 1 is the following resin (β): In the above general formula ⑴, X1 is a hydrogen atom or a methyl group, Y1 is a divalent binding represented by the above general formula ⑴ group (X2 a group represented by the following formula ([eta]) represented by, Z1 and Z2 is a direct bond), R1 is a group burning carbon atoms of 1~8, R2~R3 is a hydrogen atom, R4 is a methyl group.

[0229] [化20] [0229] [Formula 20]

[0230] [0230]

Figure CN107531857AD00321

[0231 ][制造例2]树脂(β) No · 2的调制 Modulation [0231] [Manufacturing Example 2] The resin (β) No · 2 of

[0232] 将甲基丙烯酸20质量份、甲基丙烯酸缩水甘油酯20质量份和甲基丙烯酸苄酯50质量份溶解于环己酮500质量份中,加入偶氮二异丁腈4质量份作为自由基聚合引发剂,在80 °C下搅拌3小时。 [0232] 20 parts by mass of methacrylic acid, glycidyl methacrylate 20 parts by mass of benzyl methacrylate and 50 parts by mass of cyclohexanone were dissolved in 500 parts by mass, azobisisobutyronitrile was added 4 parts by mass of a radical polymerization initiator, and stirred at 80 ° C 3 hours. 然后,加入丙烯酸20质量份,在120°C下搅拌3小时,得到树脂(β) No. 2。 Then, 20 parts by mass of acrylic acid were added, with stirring at 120 ° C 3 hours to obtain a resin (β) No. 2.

[0233] [制造例3]树脂(β) No · 3的调制 Modulation [0233] [Production Example 3] Resin (β) No · 3 of

[0234] 将甲基丙烯酸缩水甘油酯50质量份、甲基丙烯酸苄酯5份和苯乙烯40质量份溶解于丙二醇-1-单甲基醚-2-乙酸酯(PGMEA) 500质量份中,加入1-二(叔丁基过氧化)-3,3,5-三甲基环己烷1质量份作为自由基聚合引发剂,在140°C下搅拌2小时。 [0234] The glycidyl methacrylate 50 parts by mass, benzyl methacrylate 40 parts Styrene 5 parts by mass, and dissolved in propylene glycol 1-monomethyl ether 2 parts methyl acetate (PGMEA) 500 mass , 1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane 1 parts by mass of a radical polymerization initiator, and stirred at 140 ° C 2 hours. 然后,加入丙烯酸20 质量份,在120°C下搅拌3小时,得到树脂(β) No. 3。 Then, 20 parts by mass of acrylic acid were added, with stirring at 120 ° C 3 hours to obtain a resin (β) No. 3.

[0235] [制造例4]树脂(β) No · 4的调制 Modulation [0235] [Manufacturing Example 4] The resin (β) No · 4 of

[0236] 将甲基丙烯酸缩水甘油酯40质量份、甲基丙烯酸苄酯5份、苯乙烯40质量份溶解于丙二醇-1-单甲基醚-2-乙酸酯(PGMEA) 500质量份中,使用偶氮二异丁腈10质量份作为自由基聚合引发剂,在80°C下搅拌3小时。 [0236] The glycidyl methacrylate 40 parts by mass, 5 parts of benzyl methacrylate, 40 parts by mass of styrene were dissolved in propylene glycol 1-monomethyl ether 2-acetate (PGMEA) 500 parts by mass using azobisisobutyronitrile 10 parts by mass of a radical polymerization initiator, and stirred at 80 ° C 3 hours. 然后,加入丙烯酸20质量份,在120°C下搅拌3小时,得到树脂Φ) No.4。 Then, 20 parts by mass of acrylic acid were added, with stirring at 120 ° C 3 hours to obtain a resin Φ) No.4.

[0237] [制造例5]树脂(β) No · 5的调制 Modulation [0237] [Production Example 5] The resin (β) No · 5 to

[0238] 将甲基丙烯酸缩水甘油酯40质量份、甲基丙烯苄酯5份、苯乙烯40质量份溶解于丙二醇-1-单甲基醚-2-乙酸酯(PGMEA) 500质量份中,加入偶氮二异丁腈5质量份作为自由基聚合引发剂,在80 °C下搅拌3小时。 [0238] The mass of glycidyl methacrylate 40 parts, 5 parts of benzyl methacrylate, 40 parts by mass of styrene were dissolved in propylene glycol 1-monomethyl ether 2-acetate (PGMEA) 500 parts by mass , parts of azobisisobutyronitrile was added 5 mass of a radical polymerization initiator, and stirred at 80 ° C 3 hours. 然后,加入丙烯酸20质量份,在120°C下搅拌3小时。 Then, 20 parts by mass of acrylic acid were added, with stirring at 120 ° C 3 hours. 然后, 加入四氢邻苯二甲酸酐5质量份,在120°C下搅拌3小时后,得到树脂(β) No. 5。 Then, after addition of tetrahydrophthalic anhydride 5 parts by mass, stirred at 120 ° C 3 hours to obtain a resin (β) No. 5.

[0239] [实施例1-1〜1-10和比较例1-1〜1-5]热反应性组合物No. 1〜No. 11和比较组合物No. 1〜No. 5的调制 Modulation [0239] heat-reactive composition No. [1-1~1-5 1-1~1-10 Examples and Comparative Examples] 1~No. 11 and comparative composition No. 1~No. 5 in

[0240] 〈步骤1>染料液No. 1〜No. 10和比较染料液No. 1〜No. 5的调制 Modulation [0240] <Step 1> dye solution No. 1~No. 10 and Comparative dye bath No. 1~No. 5 in

[0241] 在作为㈧成分的[表1]〜[表3]所示的花青化合物(α)中加入溶剂(〇),搅拌溶解后得到染料液No. 1〜No. 10和比较染料液No. 1〜No. 5。 [0241] added to the solvent (square) as component (viii) [Table 1] - [Table 3] shown cyanine compound ([alpha]), stirred solution dissolving a dye No. 1~No. 10 and Comparative dye solution No. 1~No. 5.

[0242] 〈步骤2>热反应性组合物No. 1〜No. 10和比较组合物No. 1〜No. 5的调制 Modulation [0242] <Step 2> The heat-reactive composition No. 1~No. 10 and comparative composition No. 1~No. 5 in

[0243] 按照[表1]〜[表3]的配比,在上述染料液No. 1〜No. 10和比较染料液No . 1〜No. 5 中加入树脂(β)、聚合引发剂(Y)(或(γ 0)和具有不饱和键的单体(ω)以及溶剂(〇)并搅拌,调制热反应性组合物No. 1〜No. 10和比较组合物No. 1〜No. 5。 [0243] according to [Table 1] - [Table 3] ratio. In 1~No. 5 was added to the dye solution No. 1~No. 10 No resin solution and the comparative dye (beta]), a polymerization initiator ( Y) (or (γ 0) and a monomer having an unsaturated bond ([omega]) and a solvent (square) and stirred to prepare a heat-reactive composition No. 1~No. 10 and comparative composition No. 1~No. 5.

[0244] 表1 [0244] TABLE 1

[0245] [0245]

Figure CN107531857AD00341

[0246] AI:化合物No. 76的六氟磷酸盐 [0246] AI: Compound No. 76 hexafluorophosphate

[0247] A-2:化合物No. 100的六氟磷酸盐 [0247] A-2: hexafluorophosphate of compound No. 100

[0248] A-3:化合物No · 100的双(三氟甲磺酰)亚胺酸盐 [0248] A-3: Compound 100 No · bis (trifluoromethanesulfonyl) imide salt

[0249] A-4:化合物No. 102的双(三氟甲磺酰)亚胺酸盐 [0249] A-4: Compound No. 102 bis (trifluoromethanesulfonyl) imide salt

[0250] A-5:化合物No · 103的双(三氟甲磺酰)亚胺酸盐 [0250] A-5: Compound No · bis (trifluoromethanesulfonyl) imide acid 103

[0251] BI:制造例1中得到的树脂(β) No · 1 [0251] BI: in Production Example 1 to obtain a resin (β) No · 1

[0252] B_2:ACA Z251 (Daicel-Allnex公司制的丙烯酸化丙烯酸酯) [0252] B_2: ACA Z251 (Daicel-Allnex Corporation acrylated acrylate)

[0253] B-3:ACA Z250 (Daicel-Allnex公司制的丙烯酸化丙烯酸酯) [0253] B-3: ACA Z250 (Daicel-Allnex Corporation acrylated acrylate)

[0254] B_4:ACA 200M(Daicel-Allnex公司制的丙稀酸化丙稀酸酯) [0254] B_4: ACA 200M (Daicel-Allnex manufactured by acrylic esters of acrylic)

[0255] B-5:SPC-1000 (昭和电工公司制的丙烯酸树脂) [0255] B-5: SPC-1000 (acrylic resin, manufactured by Showa Denko)

[0256] B-6:SPC-3000 (昭和电工公司制的丙烯酸树脂) [0256] B-6: SPC-3000 (acrylic resin, manufactured by Showa Denko)

[0257] B-7:制造例2中得到的树脂(β) No. 2 [0257] B-7: Production Example 2 was resin (β) No. 2

[0258] B-8:制造例3中得到的树脂(β) No. 3 [0258] B-8: Resin (beta]) obtained in Production Example 3 No. 3

[0259] B-9:制造例4中得到的树脂(β) No. 4 [0259] B-9: obtained in Production Example 4 Resin (β) No. 4

[0260] B-IO:制造例5中得到的树脂(β) No. 5 [0260] B-IO: Resin (beta]) obtained in Production Example 5 No. 5

[0261] CI :V-60(和光纯药公司制的油溶性偶氮聚合引发剂) [0261] CI: V-60 (oil-soluble azo Wako Pure Chemical Industries, Ltd. and a polymerization initiator)

[0262] C-2:V_70 (和光纯药公司制的油溶性偶氮聚合引发剂) [0262] C-2: V_70 (oil-soluble azo Wako Pure Chemical Industries, Ltd. and a polymerization initiator)

[0263] C-3:V_65 (和光纯药公司制的油溶性偶氮聚合引发剂) [0263] C-3: V_65 (oil-soluble azo Wako Pure Chemical Industries, Ltd. and a polymerization initiator)

[0264] C-4:V_59 (和光纯药公司制的油溶性偶氮聚合引发剂) [0264] C-4: V_59 (oil-soluble azo Wako Pure Chemical Industries, Ltd. and a polymerization initiator)

[0265] C-5:V_40 (和光纯药公司制的油溶性偶氮聚合引发剂) [0265] C-5: V_40 (oil-soluble azo Wako Pure Chemical Industries, Ltd. and a polymerization initiator)

[0266] C-6:VAm-110 (和光纯药公司制的油溶性偶氮聚合引发剂) [0266] C-6: VAm-110 (oil-soluble azo Wako Pure Chemical Industries, Ltd. and a polymerization initiator)

[0267] C' -1: Irg-907 (BASF公司制的光聚合引发剂) [0267] C '-1: Irg-907 (BASF Corporation photopolymerization initiator)

[0268] C' -2:SP-246 (ADEKA公司制的光聚合引发剂) [0268] C '-2: SP-246 (ADEKA Corporation photopolymerization initiator)

[0269] C' -3:0XE-01 (BASF公司制的光聚合引发剂) [0269] C '-3: 0XE-01 (manufactured by BASF light polymerization initiator)

[0270] C' -4:0XE-02 (BASF公司制的光聚合引发剂) [0270] C '-4: 0XE-02 (BASF Corporation photopolymerization initiator)

[0271] DI :Aronix M450 (东亚合成公司制的丙稀酸系单体) [0271] DI: Aronix M450 (acrylic monomer manufactured by Toagosei)

[0272] D_2:Aronix M315 (东亚合成公司制的丙稀酸系单体) [0272] D_2: Aronix M315 (acrylic monomer manufactured by Toagosei)

[0273] EI:环己酮 [0273] EI: cyclohexanone

[0274] E-2:双丙酮醇 [0274] E-2: diacetone alcohol

[0275] E-3:甲乙酮 [0275] E-3: methyl ethyl ketone

[0276] 表2 [0276] TABLE 2

[0277] [0277]

Figure CN107531857AD00361

[0278] 表3 [0278] TABLE 3

[0279] [0279]

Figure CN107531857AD00371

[0280] [评价例I -1〜I -10和比较评价例I -1〜I -5] [0280] [Evaluation Example I -1~I -10 and Comparative Evaluation Example I -1~I -5]

[0281] 将实施例1 -1〜I -10中得到的热反应性组合物No . 1〜No. 10和比较例1 -1〜1 -5中得到的比较组合物No. 1〜No. 5分别在410rpm X 7秒的条件下涂布于玻璃基板上,用热板使其干燥(90°C、10分钟)。 [0281] The heat obtained in Example reactive composition No. 1~No. 10 and Comparative Examples 1 -5 -1~1 obtained comparative composition No. 1~No 1 -1~I -10 in. 5, respectively, under conditions of 410rpm X 7 seconds coated on a glass substrate, and dried with a hot plate (90 ° C, 10 minutes). 干燥后,用热板在150°C下加热10分钟使涂膜固化。 After drying, a hot plate heated at 150 ° C 10 minutes to cure the coating. 将固化后的涂膜在150°CX 1小时的条件下加热以评价耐热性。 The cured coating film after heating to evaluate heat resistance at 150 ° CX ​​1 hour conditions. 评价是通过算出加热前后的最大吸收波长的透射率变化来进行。 Evaluation is performed by the maximum absorption wavelength change in transmittance before and after heating was calculated. 透射率变化量用以下的式子求出。 Transmittance change amount calculated by the following equation.

[0282] 透射率变化量(%) = (XY) /XX 100 (X是加热前的最大吸收波长的透射率,Y是加热后测定的该波长处的透射率) [0282] an amount of change in transmittance (%) = (XY) / XX 100 (X is the maximum absorption wavelength transmittance before heating, Y is transmittance of the wavelength measured after heating)

[0283] 上述的结果示于表4中。 [0283] These results are shown in Table 4.

[0284] 表4 [0284] TABLE 4

[0285] [0285]

Figure CN107531857AD00381

[0286] (表4中,表示不能均匀地成膜,所以无法进行评价。) [0286] (Table 4 shows the film formation is not uniform, it could not be evaluated.)

[0287] 由上述表4的结果可知,本发明的热反应性组合物的色差的变化较少,耐热性较尚。 [0287] From the results in Table 4, the color change of less heat-reactive composition according to the present invention, the heat resistance still more.

[0288] [实施例2-1〜2-10]波长截止滤光器No. 1〜No. 10的制造 [0288] [Example 2-1~2-10] No. wavelength cutoff filter manufacturing 1~No. 10 is

[0289] 在厚度为ΙΟΟμπι的玻璃基板(A)的一个面上,通过真空蒸镀法交替层叠二氧化硅(SiO2)层和氧化钛(TiO2)层,形成了总层数为30层、厚度约为3μπι的红外线反射膜(C)。 [0289] In one surface of the glass substrate having a thickness of ΙΟΟμπι (A) by alternately laminating silicon dioxide (SiO2) layer and a titanium oxide (TiO2) layer, a vacuum deposition method, formation of a layer 30 of a total number of layers, thickness the infrared reflecting film is about 3μπι (C).

[0290] 在得到的施加了红外线反射膜(C)的玻璃基板(A)的与红外线反射膜不同的面上, 用棒涂器#30涂布(膜厚ΙΟμπι)实施例1-1〜1-10中得到的热反应性组合物(涂布液)No. 1〜 No. 10之后,在100 °C下干燥10分钟,制作波长截止滤光器No. 1〜No. 10。 [0290] In the infrared reflecting film is applied to the surface of different infrared reflecting film (C) a glass substrate (A) obtained in, Example 1-1~1 embodiment using a bar coater # 30 coating (film thickness ΙΟμπι) -10 obtained heat-reactive composition (coating liquid) No. after 1~ No. 10, dried for 10 minutes at 100 ° C, that a wavelength cut filter No. 1~No. 10.

[0291] [评价例2-1 〜2-10] [0291] [Evaluation Example 2-1 ~2-10]

[0292] 对于实施例2-1〜2-10中得到的本发明的波长截止滤光器No. 1〜No. 10,求出i)在波长430〜580nm的范围内从波长截止滤光器的垂直方向测定时的透射率的平均值、ii)在波长800〜IOOOnm内从波长截止滤光器的垂直方向测定时的透射率的平均值、和iii)在波长560〜800nm的范围内从波长截止滤光器的垂直方向测定时的透射率达到80%的波长的值(Ya)与从相对于波长截止滤光器的垂直方向为35°的角度测定时的透射率达到80%的波长的值(Yb)的差的绝对值。 [0292] For the embodiment of the present invention the wavelength obtained 2-1~2-10 cut filter No. 1~No. 10, obtains i) in the wavelength range from 430~580nm wavelength cut filter when the average transmittance measured in the vertical direction, ii) the average transmittance, as measured 800~IOOOnm wavelength from the wavelength cut-off filter in the vertical direction, and iii) in the wavelength range from 560~800nm transmittance cutoff filter in the vertical direction measurement wavelength reaches a value of 80% of the wavelength (Ya) and the transmittance when measured from a vertical direction with respect to the wavelength cutoff filter 35 ° angle for 80% of the wavelength absolute difference value (Yb) is. 结果示于表5中。 The results are shown in Table 5. 此外,上述透射率的测定是用日本分光株式会社制的紫外可见近红外分光光度计V-570来测定。 In addition, measurement of the transmittance is measured visible-near infrared spectrophotometer V-570 manufactured by Nippon Bunko Co. ultraviolet.

[0293] 表5 [0293] TABLE 5

[0294] [0294]

Figure CN107531857AD00391

[0295] 由上述表5的结果可知,本发明的波长截止滤光器在波长430〜580nm的范围内透射率较高,在波长800〜IOOOnm内透射率较低,并且入射角依赖性较低。 [0295] From the results in Table 5, the present invention is a wavelength cut filter in the wavelength range of 430~580nm high transmittance, low transmittance in the wavelength 800~IOOOnm, low incident angle dependence and .

[0296] 由以上的结果可知,以在玻璃基板(A)的一个面上形成含有染料的涂布层(B)、并且在玻璃基板(A)的另一个面上具有红外线反射膜(C)为特征的本发明的波长截止滤光器的入射角依赖性较低。 [0296] From the above results, in order to form a coating layer (B) containing a dye on one surface of a glass substrate (A), and having an infrared reflecting film (C) on the other surface of the glass substrate (A), lower cutoff wavelength filter according to the present invention is characterized incident angle dependence. 因此,本发明的波长截止滤光器对于固体摄像装置和照相机模块是有用的。 Thus, the wavelength cut filter of the present invention is useful for solid-state imaging device and a camera module.

Claims (8)

1. 一种热反应性组合物,其含有:花青化合物中的至少一种(α)、至少具有烯键式不饱和键和亲水性基团的树脂⑹、以及热聚合引发剂(γ)。 A heat-reactive composition, comprising: at least one cyanine compound ([alpha]), having at least ethylenically unsaturated bond ⑹ resin and a hydrophilic group, and a thermal polymerization initiator (gamma] ).
2. 根据权利要求1所述的热反应性组合物,其特征在于,至少具有烯键式不饱和键和亲水性基团的树脂〇3)含有下述通式(II)表示的单元、下述通式(1-2)表示的单元和下述通式(1-3)表示的单元, The heat-reactive composition according to claim 1, wherein at least a resin having an ethylenically unsaturated bond and a hydrophilic group 〇3) following general formula (II) represented by the unit, means the following general formula and the following formula (1-2) (1-3) represented by the unit,
Figure CN107531857AC00021
式中,X1表示氢原子或甲基,Y1是二价的结合基,R1表示碳原子数为1〜20的烷基、碳原子数为6〜30的芳基或碳原子数为7〜30的芳烷基,该烷基、芳基和芳烷基也可被卤原子、羟基或硝基取代,该烷基和芳烷基中的亚甲基也可被-〇_、-S-、-CO-、-⑶0-、-OCO-或-NH-、或它们的组合的结合基置换,R2、R3和R4分别独立地为氢原子或甲基。 Wherein, the X1 represents a hydrogen atom or a methyl group, Y1 is a divalent bonding group, Rl represents an alkyl group of 1~20 carbon atoms, 6~30 carbon atoms, or an aryl group of 7~30 carbon atoms, aralkyl group, the alkyl, aryl and aralkyl groups may also be a halogen atom, a hydroxyl group or a nitro group, the alkyl group and aralkyl group may be methylene -〇 _, - S-, -CO -, - ⑶0 -, - OCO- or -NH-, or combinations thereof in conjunction with the substitution, R2, R3 and R4 are each independently a hydrogen atom or a methyl group.
3. 根据权利要求1或2所述的热反应性组合物,其特征在于,热聚合引发剂(γ)是偶氮热聚合引发剂。 3. The heat-reactive composition according to claim 12, wherein the thermal polymerization initiator (gamma]) is an azo thermal polymerization initiator.
4. 根据权利要求1〜3中任一项所述的热反应性组合物,其特征在于,相对于至少具有烯键式不饱和键和亲水性基团的树脂⑹的固体成分100质量份,含有合计为0.01〜10.0质量份的花青化合物中的至少一种(α)。 ~ 3 The heat-reactive composition according to any one of the preceding claims, characterized in that, with respect to 100 mass of the solid component having at least ethylenically unsaturated bond ⑹ resin and the hydrophilic group parts , a total amount of at least one ([alpha]) 0.01~10.0 parts by mass of the cyanine compound.
5. —种波长截止滤光器,其特征在于,在玻璃基板(A)的一个面上具有由权利要求1〜4 中任一项所述的热反应性组合物得到的涂布层(B),并且在玻璃基板(A)的另一个面上具有红外线反射膜⑹。 5 - Wavelength cut-off filter, wherein a coating layer made of claims 1 ~ 4 of the heat-reactive composition according to any one surface of the obtained glass substrate (A), (B ), and having an infrared reflective film on the other surface of the glass substrate ⑹ (a) is.
6. 根据权利要求5所述的波长截止滤光器,其特征在于,所述波长截止滤光器的透射率满足下述⑴〜(iii): (i) 在波长430〜580nm的范围内,从波长截止滤光器的垂直方向测定时的透射率的平均值为75%以上, (ii) 在波长800〜IOOOnm内,从波长截止滤光器的垂直方向测定时的透射率的平均值为5%以下, (iii) 在波长560〜800nm的范围内,从波长截止滤光器的垂直方向测定时的透射率达到80%的波长的值(Ya)与从相对于波长截止滤光器的垂直方向为35°的角度测定时的透射率达到80%的波长的值(Yb)的差的绝对值为30nm以下。 5 according to the wavelength cut-off filter as claimed in claim, wherein said wavelength cutoff filter transmittance satisfies the following ⑴~ (iii): (i) in the wavelength range of 430~580nm, average transmittance when measured from the vertical direction of the wavelength cut filter is at least 75%, (ii) in the wavelength 800~IOOOnm, the average transmittance when measured from the vertical direction of the wavelength cut filter is 5% or less, (iii) in the range of 560~800nm ​​wavelength, the transmittance was measured from the vertical direction of the wavelength cut filter reaches a value of 80% of the wavelength (Ya) with respect to the wavelength cutoff filter the absolute value of the difference between the value of the transmission rate of 35 ° vertical angle detection wavelength of 80% (Yb) is 30nm or less.
7. —种固体摄像装置,其特征在于,其具备权利要求5或6所述的波长截止滤光器。 7. - kinds of solid-state imaging device, wherein the wavelength of 5 or claim 6, which includes a cut filter.
8. —种照相机模块,其特征在于,其具备权利要求5或6所述的波长截止滤光器。 8. - kind of the camera module, wherein a wavelength of 5 or claim 6 which includes a cut filter.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11171945A (en) * 1997-12-05 1999-06-29 Showa Denko Kk Production of composition for decorating sheet and production thereof
CN102947733A (en) * 2010-06-23 2013-02-27 三菱化学株式会社 Colored resin composition, color filter, liquid crystal display device, and organic EL display
JP2013173848A (en) * 2012-02-24 2013-09-05 Adeka Corp Colored alkali developable photosensitive resin composition
JP2014126642A (en) * 2012-12-26 2014-07-07 Adeka Corp Wavelength cut filter
CN103930806A (en) * 2012-04-25 2014-07-16 株式会社艾迪科 Wavelength cut filter
WO2014157427A1 (en) * 2013-03-26 2014-10-02 富士フイルム株式会社 Curable composition, cured film, color filter, protective film, display device and solid-state imaging element
CN104823083A (en) * 2012-11-30 2015-08-05 富士胶片株式会社 Curable resin composition, and image-sensor-chip production method and image sensor chip using same

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11171945A (en) * 1997-12-05 1999-06-29 Showa Denko Kk Production of composition for decorating sheet and production thereof
CN102947733A (en) * 2010-06-23 2013-02-27 三菱化学株式会社 Colored resin composition, color filter, liquid crystal display device, and organic EL display
JP2013173848A (en) * 2012-02-24 2013-09-05 Adeka Corp Colored alkali developable photosensitive resin composition
CN103930806A (en) * 2012-04-25 2014-07-16 株式会社艾迪科 Wavelength cut filter
CN104823083A (en) * 2012-11-30 2015-08-05 富士胶片株式会社 Curable resin composition, and image-sensor-chip production method and image sensor chip using same
JP2014126642A (en) * 2012-12-26 2014-07-07 Adeka Corp Wavelength cut filter
WO2014157427A1 (en) * 2013-03-26 2014-10-02 富士フイルム株式会社 Curable composition, cured film, color filter, protective film, display device and solid-state imaging element

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
孙道兴,等: "《涂料调配与配色技术》", 30 November 2008, 中国纺织出版社 *

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