WO2018034082A1 - 組成物、硬化膜、赤外線透過フィルタ、固体撮像素子および赤外線センサ - Google Patents
組成物、硬化膜、赤外線透過フィルタ、固体撮像素子および赤外線センサ Download PDFInfo
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- WO2018034082A1 WO2018034082A1 PCT/JP2017/025239 JP2017025239W WO2018034082A1 WO 2018034082 A1 WO2018034082 A1 WO 2018034082A1 JP 2017025239 W JP2017025239 W JP 2017025239W WO 2018034082 A1 WO2018034082 A1 WO 2018034082A1
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
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- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
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- 125000005369 trialkoxysilyl group Chemical group 0.000 description 1
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
- H01L27/144—Devices controlled by radiation
- H01L27/146—Imager structures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
- H01L27/144—Devices controlled by radiation
- H01L27/146—Imager structures
- H01L27/14601—Structural or functional details thereof
- H01L27/14625—Optical elements or arrangements associated with the device
Definitions
- the present invention relates to a composition that can be used for forming an infrared transmission filter and the like.
- the present invention also relates to a cured film, an infrared transmission filter, a solid-state imaging device, and an infrared sensor using the composition.
- Solid-state image sensors are used as optical sensors for various purposes.
- infrared rays have a wavelength longer than that of visible rays and thus are not easily scattered, and can be used for distance measurement, three-dimensional measurement, and the like.
- Infrared rays are invisible to humans, animals, etc., so even if you illuminate the subject with an infrared light source at night, the subject will not be noticed. It can also be used for shooting.
- an optical sensor infrared sensor
- an optical sensor that senses infrared rays can be used in various applications, and the development of a film that can be used for an infrared sensor is desired.
- Patent Document 1 describes a color filter composition containing a near-infrared transmitting black color material.
- the near-infrared transmitting black color material is preferably a pigment.
- a composition using a dye-type near-infrared transmitting black color material can improve resolution as compared with a composition using a pigment-type near-infrared transmitting black color material.
- the dye-type near-infrared transmitting black color material has an advantage that it is possible to dispense with troubles such as dispersion.
- a cured film using a composition containing a dye-type near-infrared transmitting black color material tends to have lower solvent resistance than a cured film using a composition containing a pigment-type near-infrared transmitting black color material. There was a trend.
- the present inventors have used a dye compound having a crosslinkable group and / or a dye multimer having a structure derived from a dye compound having a crosslinkable group as the near-infrared transmitting black color material.
- the inventors have found that a cured film excellent in pattern formability and solvent resistance can be formed, and have completed the present invention.
- the present invention provides the following.
- a composition comprising a near-infrared transmitting black color material, a curable compound, and a solvent
- the near-infrared transmitting black color material contains at least one selected from a dye compound having a crosslinkable group and a dye multimer having a structure derived from the dye compound,
- composition according to ⁇ 1> wherein the crosslinkable group included in the dye compound is at least one selected from a group having an ethylenically unsaturated bond, an epoxy group, and an alkoxysilyl group.
- the dye compound having a crosslinkable group is at least one selected from a xanthene compound, a perylene compound, an azo compound, and a bisbenzofuranone compound.
- the dye multimer is formed by bonding two or more structures derived from a dye compound to a divalent or higher linking group.
- ⁇ 5> The composition according to any one of ⁇ 1> to ⁇ 3>, wherein the dye multimer has a repeating unit having a structure derived from a dye compound.
- ⁇ 6> The composition according to any one of ⁇ 1> to ⁇ 5>, further comprising a chromatic colorant.
- ⁇ 7> A cured film obtained by curing the composition according to any one of ⁇ 1> to ⁇ 6>.
- ⁇ 8> An infrared transmission filter having the cured film according to ⁇ 7>.
- ⁇ 9> A solid-state imaging device having the cured film according to ⁇ 7>.
- ⁇ 10> An infrared sensor having the cured film according to ⁇ 7>.
- a composition capable of forming a cured film excellent in pattern formability and solvent resistance can be provided.
- the cured film, infrared rays transmission filter, solid-state image sensor, and infrared sensor which used the above-mentioned composition can be provided.
- the total solid content refers to the total mass of components excluding the solvent from the entire composition.
- the notation which does not describe substitution and unsubstituted includes the group which has a substituent with the group which does not have a substituent.
- the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
- exposure includes not only exposure using light, but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified.
- Examples of the light used for exposure include an emission line spectrum of a mercury lamp, actinic rays or radiation such as far ultraviolet rays, extreme ultraviolet rays (EUV light) typified by excimer laser, X-rays, and electron beams.
- EUV light extreme ultraviolet rays
- (meth) acrylate” represents both and / or acrylate and methacrylate
- (meth) acryl” represents both and / or acrylic and “(meth) acrylic”.
- Acryloyl represents both and / or acryloyl and methacryloyl.
- the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .
- a weight average molecular weight and a number average molecular weight are defined as a polystyrene conversion value in gel permeation chromatography (GPC) measurement.
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation), and TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6) as a column.
- 0.0 mm ID (inner diameter) ⁇ 15.0 cm) and a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as an eluent.
- a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
- the composition of the present invention is a composition comprising a near-infrared transmitting black color material, a curable compound, and a solvent
- the near-infrared transmitting black color material contains at least one selected from a dye compound having a crosslinkable group and a dye multimer having a structure derived from a dye compound having a crosslinkable group, A / B, which is a ratio of the minimum absorbance A in the wavelength range of 400 to 700 nm and the maximum absorbance B in the wavelength range of 1100 to 1300 nm, is 4.5 or more.
- the composition of the present invention uses a dye compound having a crosslinkable group and / or a dye multimer having a structure derived from a dye compound having a crosslinkable group as a near-infrared transmitting black color material, thereby providing solvent resistance.
- a cured film excellent in the thickness can be formed.
- this composition has an A / B which is a ratio of the minimum absorbance A in the wavelength range of 400 to 700 nm and the maximum absorbance B in the wavelength range of 1100 to 1300 nm of 4.5 or more.
- a cured film that shields visible light and transmits infrared light in a specific wavelength region can be formed. For this reason, by using the composition of the present invention, an infrared transmission filter having excellent solvent resistance can be formed.
- a color filter or a protective film may be laminated on the infrared transmission filter. If the solvent resistance of the infrared transmission filter is inferior, when these films are laminated on the infrared transmission filter, the near infrared transmission black color material will elute from the infrared transmission filter and the spectral characteristics of the infrared transmission filter will fluctuate. There is.
- a cured film having excellent solvent resistance can be formed. Therefore, when a color filter or a protective film is formed on the cured film formed using the composition of the present invention.
- the composition of the present invention uses a dye compound having a crosslinkable group and / or a dye multimer having a structure derived from a dye compound as a near-infrared transmitting black color material, and therefore has good pattern formability. A finer pattern can be formed.
- the near-infrared transmitting black color material has low transparency such as i-line (365 nm), so that the rectangularity of the pattern may decrease or the pattern may peel off as the pattern size becomes high resolution.
- a dye compound having a crosslinkable group preferably a group having an ethylenically unsaturated bond
- it can be cured to the lower part of the film even with a small amount of exposure, and high resolution Even if it is a pattern, the pattern excellent in rectangularity, adhesiveness, etc. can be formed.
- the above absorbance condition may be achieved by any means.
- the type and content of the near-infrared transmitting black color material, and further containing a chromatic colorant and / or an infrared absorber adjusting the type and content of the above-mentioned absorbance This condition can be suitably achieved.
- the infrared absorber has a role of limiting light to be transmitted (infrared rays) to a longer wavelength side.
- the A / B value described above is preferably 7 or more, more preferably 7.5 or more, still more preferably 10 or more, still more preferably 15 or more, and particularly preferably 30 or more. preferable.
- the absorbance A ⁇ at a certain wavelength ⁇ is defined by the following equation (1).
- a ⁇ ⁇ log (T ⁇ / 100) (1)
- a ⁇ is the absorbance at the wavelength ⁇
- T ⁇ is the transmittance (%) at the wavelength ⁇ .
- the absorbance value may be a value measured in the state of a solution, or may be a value in a film formed using the composition.
- the composition is applied on the glass substrate by a method such as spin coating so that the thickness of the film after drying becomes a predetermined thickness, and 100 ° C. using a hot plate. It is preferable to measure using a film prepared by drying for 120 seconds.
- the thickness of the film can be measured for the substrate having the film using a stylus type surface shape measuring instrument (DEKTAK150 manufactured by ULVAC).
- the absorbance can be measured using a conventionally known spectrophotometer.
- the absorbance measurement conditions are not particularly limited, but the absorbance in the wavelength range of 1100 to 1300 nm is adjusted under the condition that the minimum absorbance A in the wavelength range of 400 to 700 nm is adjusted to 0.1 to 3.0. It is preferable to measure the maximum value B. By measuring the absorbance under such conditions, the measurement error can be further reduced.
- a method of adjusting the optical path length of the sample cell can be mentioned.
- the method etc. which adjust a film thickness are mentioned.
- the composition of the present invention is applied onto a glass substrate by a method such as spin coating so that the thickness of the dried film becomes a predetermined thickness, and dried at 100 ° C. for 120 seconds using a hot plate.
- the thickness of the film is measured using a stylus type surface shape measuring instrument (DEKTAK150 manufactured by ULVAC) for the dried substrate having the film.
- the dried substrate having this film is measured for transmittance in a wavelength range of 300 to 1300 nm using an ultraviolet-visible near-infrared spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).
- composition of the present invention transmits infrared rays, it can also be said to be an infrared transparent composition.
- each component which can comprise the composition of this invention is demonstrated.
- the composition of the present invention contains a near-infrared transmitting black color material.
- the near-infrared transmitting black color material in the present invention contains at least one selected from a dye compound having a crosslinkable group and a dye multimer having a structure derived from a dye compound having a crosslinkable group.
- the near-infrared transmitting black color material is preferably a material that absorbs light in the wavelength range from purple to red.
- the near-infrared transmitting black color material is preferably a color material that blocks light in the wavelength range of 400 to 700 nm.
- A1 / B1 which is a ratio of the minimum absorbance A1 in the wavelength range of 400 to 700 nm and the minimum absorbance B1 in the wavelength range of 900 to 1300 nm is 4.5 or more.
- the near-infrared transmitting black color material is preferably a color material that transmits at least part of light in the wavelength range of 800 to 1300 nm.
- the dye compound having a crosslinkable group (also referred to as a crosslinkable dye) is preferably at least one compound selected from a xanthene compound, a perylene compound, an azo compound, and a bisbenzofuranone compound, and more preferably a xanthene compound.
- the crosslinkable dye is preferably a compound that dissolves 1 g or more with respect to 100 g of propylene glycol monomethyl ether acetate at 23 ° C., and more preferably a compound that dissolves 3 g or more.
- the type of the crosslinkable group possessed by the crosslinkable dye is not particularly limited. Examples thereof include groups capable of causing a crosslinking reaction by the action of heat, light, radicals and the like.
- Specific examples of the crosslinkable group include a group having an ethylenically unsaturated bond, an epoxy group, an alkoxysilyl group, and a methylol group.
- Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
- the alkoxysilyl group include a monoalkoxysilyl group, a dialkoxysilyl group, and a trialkoxysilyl group.
- the number of carbon atoms of the alkoxy group in the alkoxysilyl group is preferably 1 to 5, more preferably 1 to 3, and still more preferably 1 or 2.
- the crosslinkable group an epoxy group and an alkoxysilyl group are preferable, and an epoxy group is more preferable. According to this aspect, there is no difference in the crosslinking rate between the upper part (surface side) and the lower part (support side) of the film, and the entire film can be crosslinked almost uniformly. Moreover, pattern formation property is favorable and the pattern shape obtained is favorable. Furthermore, pattern peeling can be effectively suppressed.
- the crosslinkable dye preferably has 1 to 4 crosslinkable groups in one molecule, more preferably 1 to 3 and even more preferably 1 to 2. According to this aspect, the effect that the tolerance with respect to a solvent improves can be anticipated.
- the crosslinkable dye is preferably a monomer type compound.
- the crosslinkable dye is preferably a compound having one pigment skeleton in one molecule.
- the molecular weight of the crosslinkable dye is preferably 300 to 3000, more preferably 500 to 1500.
- the molecular weight value of the crosslinkable dye is a value calculated from the structural formula.
- crosslinkable dye examples include the following compounds.
- a commercial item can also be used for a crosslinkable dye.
- K01 (Wako Pure Chemical Industries, Ltd., xanthene compound), R56 (Wako Pure Chemical Industries, Ltd., xanthene compound) etc. are mentioned.
- Me is a methyl group.
- the dye multimer used as the near-infrared transmitting black color material is a dye multimer having a structure derived from a dye compound having a crosslinkable group (hereinafter also referred to as dye multimer A).
- the dye multimer A is preferably dissolved in an amount of 1 g or more with respect to 100 g of propylene glycol monomethyl ether acetate at 23 ° C., more preferably 3 g or more.
- the dye multimer A preferably has 2 or more, and more preferably 3 or more of the above-described crosslinkable dye-derived structure in one molecule.
- the upper limit is not particularly limited, but may be 100 or less.
- the dye multimer A is preferably a compound having a structure in which two or more structures derived from a dye compound (crosslinkable dye) are bonded to a divalent or higher linking group.
- the divalent or higher linking group include an alkylene group, an arylene group, —O—, —S—, —SO—, —CO—, —COO—, —OCO—, —SO 2 —, —NR— (R represents A hydrogen atom or an alkyl group having 1 to 20 carbon atoms), or a group consisting of a combination thereof.
- the pigment multimer A is preferably a compound (polymer) having a repeating unit derived from a dye compound (crosslinkable dye).
- the dye multimer A is preferably a polymer containing a repeating unit represented by the formula (A).
- the ratio of the repeating unit represented by the formula (A) is preferably 10 to 100% by mass of all repeating units constituting the dye multimer A.
- the lower limit is more preferably 20% by mass or more, further preferably 30% by mass or more, and further preferably 50% by mass or more.
- the upper limit is more preferably 95% by mass or less.
- X 1 represents the main chain of the repeating unit
- L 1 represents a single bond or a divalent linking group.
- DyeI represents a dye structure.
- X 1 represents the main chain of the repeating unit.
- the main chain of the repeating unit varies depending on the type of crosslinkable group possessed by the crosslinkable dye.
- examples of X 1 include structures represented by the following (XX-1) to (XX-24): (XX -1) or (XX-24) is preferable.
- * represents a connecting hand with L 1 .
- Me represents a methyl group.
- R in (XX-18) and (XX-19) represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group.
- L 1 represents a single bond or a divalent linking group.
- the divalent linking group include an alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, a heterocyclic linking group, —CH ⁇ CH—, —O—, —S—, —C ( ⁇ O )-, -COO-, -NR-, -CONR-, -OCO-, -SO-, -SO 2 -and a linking group formed by linking two or more thereof.
- each R independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group.
- the alkylene group preferably has 1 to 30 carbon atoms.
- the upper limit is more preferably 25 or less, and still more preferably 20 or less.
- the lower limit is more preferably 2 or more, and further preferably 3 or more.
- the alkylene group may be linear, branched or cyclic.
- the carbon number of the arylene group is more preferably 6-20, and further preferably 6-12.
- the heterocyclic linking group is preferably a 5-membered ring or a 6-membered ring.
- the hetero atom that the heterocyclic linking group has is preferably an oxygen atom, a nitrogen atom, or a sulfur atom.
- the number of heteroatoms contained in the heterocyclic linking group is preferably 1 to 3.
- the dye structure represented by DyeI is a dye structure derived from a crosslinkable dye. Examples include xanthene dye structures, perylene dye structures, azo dye structures, and bisbenzofuranone dye structures.
- the repeating unit represented by the formula (A) is preferably a repeating unit represented by the following formulas (A-1) to (A-3).
- R 1A represents a hydrogen atom or an alkyl group
- L 1A represents a single bond or a divalent linking group
- Diel represents a dye structure
- L 2A represents a single bond or a divalent linking group
- Diel represents a dye structure
- R 3A represents an alkyl group or an aryl group
- L 3A represents a single bond or a divalent linking group
- a represents 0 or 1
- Diel represents a dye structure.
- the divalent linking group represented by L 1A to L 3A in formulas (A-1) to (A-3) has the same meaning as the divalent linking group represented by L 1 in formula (A), and the preferred range is also the same. It is.
- the dye structure represented by Diel in formulas (A-1) to (A-3) is synonymous with the dye structure represented by Diel in formula (A), and the preferred range is also the same.
- the number of carbon atoms of the alkyl group represented by R 1A in formula (A-1) is preferably 1 to 5, more preferably 1 to 3, and still more preferably 1.
- R 1A is preferably a hydrogen atom or a methyl group.
- the number of carbon atoms of the alkyl group in formula (A-3) is preferably 1 to 10, more preferably 1 to 8, and further preferably 1 to 6.
- the alkyl group may be linear, branched or cyclic, and is preferably linear.
- the number of carbon atoms of the aryl group in formula (A-3) is preferably 6 to 20, more preferably 6 to 14, and still more preferably 6 to 10.
- the dye multimer A may contain other repeating units in addition to the repeating unit represented by the formula (A).
- Other repeating units may contain a functional group such as a crosslinkable group or an acid group.
- Other repeating units may not contain a functional group.
- the crosslinkable group include a group having an ethylenically unsaturated bond, an epoxy group, an alkoxysilyl group, and a methylol group.
- the acid group include a carboxyl group, a sulfo group, and a phosphoric acid group.
- the ratio of the repeating unit having a crosslinkable group may be more than 0% by mass and not more than 50% by mass of all the repeating units constituting the dye multimer A.
- the lower limit is more preferably 1% by mass or more, and further preferably 3% by mass or more.
- the upper limit is more preferably 35% by mass or less, and further preferably 30% by mass or less.
- the ratio of the repeating unit having an acid group is preferably more than 0 mass% and not more than 50 mass% of all repeating units constituting the dye multimer A.
- the lower limit is more preferably 1% by mass or more, and further preferably 3% by mass or more.
- the upper limit is more preferably 35% by mass or less, and further preferably 30% by mass or less.
- the content of the near-infrared transmitting black color material is preferably 1 to 60% by mass of the total solid content of the composition.
- the lower limit is more preferably 5% by mass or more, and further preferably 10% by mass or more.
- the upper limit is more preferably 50% by mass or less, and further preferably 40% by mass or less.
- the content of the crosslinkable dye is preferably 1 to 60% by mass of the total solid content of the composition.
- the lower limit is more preferably 5% by mass or more, and further preferably 10% by mass or more.
- the upper limit is more preferably 50% by mass or less, and further preferably 40% by mass or less.
- the content of the crosslinkable dye in the total mass of the near-infrared transmitting black color material is preferably 10 to 100% by mass, more preferably 25 to 100% by mass, and further preferably 50 to 100% by mass. Only 1 type may be used for a crosslinkable dye and it may use 2 or more types together. When using 2 or more types of crosslinkable dye together, it is preferable that a total amount is the said range.
- the content of the dye multimer A is preferably 1 to 60% by mass of the total solid content of the composition.
- the lower limit is more preferably 5% by mass or more, and further preferably 10% by mass or more.
- the upper limit is more preferably 50% by mass or less, and further preferably 40% by mass or less.
- the content of the dye multimer A in the total mass of the near-infrared transmitting black color material is preferably 10 to 100% by mass, more preferably 25 to 100% by mass, and further preferably 50 to 100% by mass.
- the dye multimer A may be used alone or in combination of two or more. When two or more dye multimers A are used in combination, the total amount is preferably within the above range.
- the content of the crosslinkable dye is preferably 10 to 90 parts by weight, more preferably 25 to 75 parts by weight, more preferably 40 to 60 parts by weight based on 100 parts by weight of the dye multimer A. More preferably, it is part by mass.
- the composition of the present invention is a near-infrared transmitting black color material (hereinafter also referred to as other near-infrared transmitting black color material) other than the above-mentioned crosslinkable dye and the above-described dye multimer A as the near-infrared transmitting black color material. You may contain.
- Other near-infrared transmitting black color materials are pigment-type near-infrared transmitting black color materials and dye-type near-infrared transmitting black color materials, and include dye compounds that do not have a crosslinkable group.
- Examples of other near-infrared transmitting black color materials include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds, with bisbenzofuranone compounds and perylene compounds being preferred.
- Examples of the bisbenzofuranone compounds include those described in JP-T 2010-534726, JP-2012-515233, JP-2012-515234, and the like, for example, “Irgaphor Black” manufactured by BASF It is available.
- Examples of perylene compounds include C.I. I. Pigment Black 31, 32 and the like.
- Examples of the azomethine compound include those described in JP-A-1-170601, JP-A-2-34664, etc., and can be obtained, for example, as “Chromofine Black A1103” manufactured by Dainichi Seika Co., Ltd.
- the azo compound is not particularly limited, and preferred examples include a compound represented by the following formula (A-1).
- the bisbenzofuranone compound is preferably a compound represented by the following general formula or a mixture thereof.
- R 1 and R 2 each independently represent a hydrogen atom or a substituent
- R 3 and R 4 each independently represent a substituent
- a and b each independently represent an integer of 0 to 4 To express.
- a is 2 or more
- the plurality of R 3 may be the same or different, and the plurality of R 3 may be bonded to form a ring.
- b 2 or more
- the plurality of R 4 may be the same or different, and the plurality of R 4 may be bonded to form a ring.
- the content of the other near-infrared transmitting black color material is preferably 1 to 60% by mass of the total solid content of the composition, It is more preferably 1 to 30% by mass. Further, the content of the other near-infrared transmitting black color material in the total amount of the near-infrared transmitting black color material is preferably 5 to 50% by mass, and more preferably 5 to 30% by mass. Moreover, the composition of this invention can also contain substantially no other near-infrared transmission black color material.
- the other near-infrared transmitting black color material is not substantially contained means that the content of the other near-infrared transmitting black color material in the near-infrared transmitting black color material is preferably 3% by mass or less. % Or less is more preferable, and it is still more preferable not to contain.
- the composition of the present invention can contain an infrared absorber.
- the infrared absorber has a role of limiting transmitted light (near infrared rays) to the longer wavelength side.
- the infrared absorber a compound having a maximum absorption wavelength in the wavelength region of the infrared region (preferably exceeding the wavelength of 700 nm and not more than 1300 nm) can be preferably used.
- the infrared absorber may be a pigment or a dye.
- Examples of infrared absorbers include pyrrolopyrrole compounds, copper compounds, cyanine compounds, phthalocyanine compounds, diiminium compounds, transition metal oxides, squarylium compounds, naphthalocyanine compounds, quaterylene compounds, dithiol metal complex compounds, croconium compounds, and the like.
- Examples of the pyrrolopyrrole compound include compounds described in paragraph Nos. 0016 to 0058 of JP-A-2009-263614, compounds described in paragraph Nos. 0037 to 0052 of JP-A-2011-68731, and the like. The contents are incorporated herein.
- Examples of the squarylium compound include compounds described in JP-A-2011-208101, paragraphs 0044 to 0049, the contents of which are incorporated herein.
- Examples of the cyanine compound include compounds described in paragraph Nos. 0044 to 0045 of JP-A-2009-108267, and compounds described in paragraph Nos. 0026 to 0030 of JP-A No. 2002-194040. Incorporated herein.
- Examples of the diiminium compound include compounds described in JP-T-2008-528706, and the contents thereof are incorporated in the present specification.
- Examples of the phthalocyanine compound include compounds described in paragraph No.
- cyanine compound for example, “functional pigment, Nobu Okawara / Ken Matsuoka / Keijiro Kitao / Kensuke Hirashima, Kodansha Scientific”, the contents of which are incorporated herein. It is.
- infrared absorbers compounds described in paragraph Nos. 0004 to 0016 of JP-A-07-164729, compounds described in paragraph Nos. 0027 to 0062 of JP-A No. 2002-146254, Near-infrared absorbing particles comprising crystallites of oxides containing Cu and / or P described in paragraph Nos. 0034 to 0067 of Japanese Patent No. 164583 and having a number average aggregate particle diameter of 5 to 200 nm may be used. These contents are incorporated herein. Further, FD-25 (manufactured by Yamada Chemical Co., Ltd.), IRA842 (naphthalocyanine compound, manufactured by Exiton) and the like can be used.
- Inorganic fine particles can also be used as the infrared absorber.
- the inorganic fine particles are preferably metal oxide fine particles or metal fine particles from the viewpoint of better infrared shielding properties.
- the metal oxide particles include indium tin oxide (ITO) particles, antimony tin oxide (ATO) particles, zinc oxide (ZnO) particles, Al-doped zinc oxide (Al-doped ZnO) particles, and fluorine-doped tin dioxide (F-doped).
- ITO indium tin oxide
- ATO antimony tin oxide
- ZnO zinc oxide
- Al-doped zinc oxide Al-doped zinc oxide
- F-doped fluorine-doped tin dioxide
- SnO 2 niobium-doped titanium dioxide (Nb-doped TiO 2 ) particles, and the like.
- the metal fine particles include silver (Ag) particles, gold (Au) particles, copper (Cu) particles, and nickel (Ni) particles.
- a tungsten oxide compound can be used as the inorganic fine particles.
- the tungsten oxide compound is preferably cesium tungsten oxide.
- paragraph No. 0080 of JP-A-2016-006476 can be referred to, the contents of which are incorporated herein.
- the shape of the inorganic fine particles is not particularly limited, and may be a sheet shape, a wire shape, or a tube shape regardless of spherical or non-spherical.
- the content of the infrared absorber is preferably 1 to 60% by mass, and more preferably 10 to 40% by mass, based on the total solid content of the composition. preferable.
- the content of the infrared absorber is preferably 10 to 200 parts by weight, more preferably 20 to 150 parts by weight, and still more preferably 30 to 80 parts by weight with respect to 100 parts by weight of the near-infrared transmitting black color material.
- An infrared absorber may be used individually by 1 type, and may be used together 2 or more types. When using 2 or more types of infrared absorbers together, it is preferable that the sum total is the said range.
- the composition of the present invention preferably contains a chromatic colorant.
- the chromatic colorant means a colorant other than the white colorant and the black colorant.
- the chromatic colorant is preferably a colorant having a maximum absorption wavelength in the range of 400 to 650 nm.
- the chromatic colorant may be a pigment or a dye.
- a dye is preferred.
- the chromatic colorant is preferably a compound having a crosslinkable group.
- the pigment is preferably an organic pigment, and examples thereof include the following. However, the present invention is not limited to these. Color Index (CI) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170 171,172,173,174,175,176,177
- C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 22
- the dye is not particularly limited, and a known dye can be used.
- the chemical structure includes pyrazole azo, anilino azo, triaryl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, Xanthene, phthalocyanine, benzopyran, indigo, and pyromethene dyes can be used.
- a dye multimer may be used as the chromatic colorant.
- the dye multimer is preferably a dye used by being dissolved in a solvent, but may form particles. When the dye multimer is a particle, the dye multimer is dispersed in a solvent or the like.
- the particulate dye multimer can be obtained, for example, by emulsion polymerization. Specific examples thereof include compounds and production methods described in JP-A-2015-214682.
- compounds described in JP 2011-213925 A, JP 2013-041097 A, JP 2015-028144 A, JP 2015-030742 A, and the like can also be used. .
- Examples of the chromatic colorant having a crosslinkable group include the following compounds. This compound is a red dye.
- composition of the present invention preferably contains at least one colorant selected from a red colorant, a blue colorant and a purple colorant as the chromatic colorant, and contains the red colorant and / or the blue colorant. It is more preferable to contain. According to this aspect, the light shielding property in the visible region can be improved more effectively.
- the content of the chromatic colorant is preferably 0.1 to 60% by mass in the total solid content of the composition of the present invention.
- the lower limit is more preferably 0.5% by mass or more, and further preferably 1.0% by mass or more.
- the upper limit is more preferably 50% by mass or less, and still more preferably 40% by mass or less.
- the content of the chromatic colorant is preferably 1 to 100 parts by mass and more preferably 30 to 100 parts by mass with respect to 100 parts by mass of the near-infrared transmitting black color material.
- the content of the chromatic colorant is preferably 1 to 100 parts by mass, more preferably 30 to 100 parts by mass with respect to 100 parts by mass in total of the crosslinkable dye and the dye multimer A described above.
- a chromatic colorant may be used individually by 1 type, and may be used together 2 or more types. When two or more chromatic colorants are used in combination, the total amount is preferably within the above range.
- the composition of the present invention contains a curable compound.
- the curable compound include a polymerizable compound and a resin.
- the resin may be a non-crosslinkable resin (a resin having no crosslinkable group) or a crosslinkable resin (a resin having a crosslinkable group).
- the crosslinkable group include a group having an ethylenically unsaturated bond, an epoxy group, and an alkoxysilyl group.
- resin contains the alkali-soluble resin mentioned later.
- the curable compound is a component other than the near-infrared transmitting black color material.
- the content of the curable compound is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, and 15% by mass with respect to the total solid content of the composition. % Or more is particularly preferable.
- the upper limit is preferably 90% by mass or less, more preferably 80% by mass or less, and further preferably 75% by mass or less.
- the polymerizable compound may be in the form of either a monomer or a polymer, but is preferably a monomer.
- the monomer type polymerizable compound preferably has a molecular weight of 100 to 3,000.
- the upper limit is preferably 2000 or less, and more preferably 1500 or less.
- the lower limit is preferably 150 or more, and more preferably 250 or more.
- a polymeric compound is a compound which does not have molecular weight distribution substantially.
- “having substantially no molecular weight distribution” means that the dispersity of the compound (weight average molecular weight (Mw) / number average molecular weight (Mn)) is preferably 1.0 to 1.5.
- the polymerizable compound is preferably a compound that can be polymerized by the action of radicals. That is, the polymerizable compound is preferably a radical polymerizable compound.
- the polymerizable compound is preferably a compound having one or more groups having an ethylenically unsaturated bond, more preferably a compound having two or more groups having an ethylenically unsaturated bond, and 3 groups having an ethylenically unsaturated bond. More preferred are compounds having one or more.
- the upper limit of the number of groups having an ethylenically unsaturated bond is, for example, preferably 15 or less, and more preferably 6 or less.
- Examples of the group having an ethylenically unsaturated bond include a vinyl group, a styryl group, a (meth) allyl group, and a (meth) acryloyl group, and a (meth) acryloyl group is preferable.
- the polymerizable compound is preferably a 3 to 15 functional (meth) acrylate compound, more preferably a 3 to 6 functional (meth) acrylate compound.
- the description in paragraph numbers 0033 to 0034 of JP2013-253224A can be referred to, and the contents thereof are incorporated in the present specification.
- the compound include ethyleneoxy-modified pentaerythritol tetraacrylate (commercially available product is NK ester ATM-35E; manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol triacrylate (commercially available product is KAYARAD D-330; Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available products are KAYARAD D-320; Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) acrylate (commercially available products are KAYARAD D- 310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available products are KAYARAD D- 310; manufactured
- Pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-TMMT) and 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA) are also preferable. These oligomer types can also be used. Examples thereof include RP-1040 (manufactured by Nippon Kayaku Co., Ltd.).
- the polymerizable compound may have an acid group such as a carboxy group, a sulfo group, or a phosphoric acid group.
- the polymerizable compound having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an unreacted hydroxy group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to form an acid group.
- a compound in which the aliphatic polyhydroxy compound is at least one of pentaerythritol and dipentaerythritol is more preferable.
- the acid value of the polymerizable compound having an acid group is preferably from 0.1 to 40 mgKOH / g.
- the lower limit is more preferably 5 mgKOH / g or more.
- the upper limit is more preferably 30 mgKOH / g or less. If the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the development and dissolution characteristics are good, and if it is 40 mgKOH / g or less, it is advantageous in production and handling. Furthermore, it is excellent in curability.
- the polymerizable compound is also preferably a compound having a caprolactone structure.
- the compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule. Mention may be made of ⁇ -caprolactone-modified polyfunctional (meth) acrylates obtained by esterifying (meth) acrylic acid and ⁇ -caprolactone with polyhydric alcohols such as glycerin, diglycerol and trimethylolmelamine.
- the compound having a caprolactone structure can be referred to the description of paragraph numbers 0153 to 0170 in International Publication No. WO2015 / 166679, the contents of which are incorporated herein.
- Examples of commercially available products include SR-494, which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, and DPCA-60, which is a hexafunctional acrylate having six pentyleneoxy chains, manufactured by Nippon Kayaku Co., Ltd. And TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.
- the polymerizable compound is also preferably isocyanuric acid ethylene oxide-modified (meth) acrylate.
- examples of commercially available products include Aronix M-315 and M-313 (manufactured by Toagosei Co., Ltd.), NK ester A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.), SR368 (manufactured by Sartomer), and the like.
- the polymerizable compound used in combination with the titanyl phthalocyanine pigment preferably has a higher SP value (Solubility Parameter) from the viewpoint of heat resistance.
- examples of the polymerizable compound having a high SP value include Aronix M-315 and M-313 (manufactured by Toagosei Co., Ltd.).
- Examples of the polymerizable compound include urethane acrylates described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, Urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable.
- addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 A composition excellent in the photosensitive speed can be obtained.
- urethane oligomer UAS-10 UAB-140 (manufactured by Sanyo Kokusaku Pulp), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA -306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like.
- the content of the polymerizable compound in the composition is preferably 0.1 to 50% by mass with respect to the total solid content of the composition.
- the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more.
- the upper limit is more preferably 45% by mass or less, and still more preferably 40% by mass or less.
- One type of polymerizable compound may be used alone, or two or more types may be used in combination. When using 2 or more types together, it is preferable that a total amount becomes the said range.
- the composition of the present invention can contain a resin as a curable compound.
- the resin include alkali-soluble resins.
- the weight average molecular weight (Mw) of the resin is preferably 2,000 to 2,000,000.
- the upper limit is more preferably 1,000,000 or less, and further preferably 500,000 or less.
- the lower limit is more preferably 3,000 or more, and even more preferably 5,000 or more.
- the content of the resin is preferably 10 to 80% by mass, more preferably 20 to 60% by mass, based on the total solid content of the composition.
- the composition may contain only one type of resin, or may contain two or more types. When two or more types of resins are included, the total amount is preferably within the above range.
- composition of this invention contains alkali-soluble resin as resin. By containing an alkali-soluble resin, developability and pattern formability are improved.
- the molecular weight of the alkali-soluble resin is not particularly limited, but the weight average molecular weight (Mw) is preferably 5,000 to 100,000.
- the number average molecular weight (Mn) is preferably 1,000 to 20,000.
- the alkali-soluble resin can be appropriately selected from resins having a group that promotes alkali dissolution. Examples of the group that promotes alkali dissolution (hereinafter also referred to as an acid group) include a carboxy group, a phosphate group, a sulfo group, and a phenolic hydroxy group, and a carboxy group is preferable. These acid groups may be used alone or in combination of two or more.
- the alkali-soluble resin is preferably a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin, or an acrylic / acrylamide copolymer resin from the viewpoint of heat resistance. From the viewpoint of development control, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferred.
- the alkali-soluble resin is preferably a polymer having a carboxy group in the side chain.
- Specific examples include methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, and alkali-soluble resins such as novolac resins.
- alkali-soluble resins such as novolac resins.
- examples thereof include phenol resins, acidic cellulose derivatives having a carboxy group in the side chain, and resins obtained by adding an acid anhydride to a polymer having a hydroxy group.
- a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin.
- Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds.
- alkyl (meth) acrylate and aryl (meth) acrylate methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate
- Examples of vinyl compounds such as hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, ⁇ -methylstyrene, vinylto
- N-substituted maleimide monomers described in JP-A-10-300922 such as N-phenylmaleimide and N-cyclohexylmaleimide can also be used.
- only 1 type may be sufficient as the other monomer copolymerizable with these (meth) acrylic acids, and 2 or more types may be sufficient as it.
- an alkali-soluble resin having a polymerizable group may be used.
- the polymerizable group include a (meth) allyl group and a (meth) acryloyl group.
- the alkali-soluble resin having a polymerizable group an alkali-soluble resin containing a polymerizable group in a side chain is useful.
- the alkali-soluble resin containing a polymerizable group include Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polyurethane acrylic oligomer. Diamond Shamrock Co., Ltd.), Biscote R-264, KS resist 106.
- Alkali-soluble resins include benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, benzyl (meth) acrylate / Multi-component copolymers composed of (meth) acrylic acid / other monomers can be preferably used.
- the alkali-soluble resin includes a monomer component including a compound represented by the following formula (ED1) and / or a compound represented by the following formula (ED2) (hereinafter, these compounds may be referred to as “ether dimers”). It is also preferable to include a polymer obtained by polymerization.
- R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
- R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms.
- the description in JP 2010-168539 A can be referred to.
- the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R 1 and R 2 is not particularly limited, and examples thereof include methyl, ethyl, n- Linear or branched alkyl groups such as propyl, isopropyl, n-butyl, isobutyl, tert-butyl, tert-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; cyclohexyl, tert-butylcyclohexyl, Alicyclic groups such as dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl and 2-methyl-2-adamantyl; alkyl groups substituted with alkoxy groups such as 1-methoxyethyl and 1-ethoxyethyl; benzyl An alkyl group substituted with an aryl group such as;
- ether dimer paragraph number 0317 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification. Only one type of ether dimer may be used, or two or more types may be used.
- the alkali-soluble resin may contain a structural unit derived from a compound represented by the following formula (X).
- R 1 represents a hydrogen atom or a methyl group
- R 2 represents an alkylene group having 2 to 10 carbon atoms
- R 3 represents an alkyl group having 1 to 20 carbon atoms which may contain a hydrogen atom or a benzene ring. Represents a group.
- n represents an integer of 1 to 15.
- the alkylene group of R 2 preferably has 2 to 3 carbon atoms.
- the alkyl group of R 3 has 1 to 20 carbon atoms, but more preferably 1 to 10 carbon atoms, and the alkyl group of R 3 may contain a benzene ring.
- Examples of the alkyl group containing a benzene ring represented by R 3 include a benzyl group and a 2-phenyl (iso) propyl group.
- alkali-soluble resin examples include the following.
- the numerical values attached to the main chain are molar ratios.
- the acid value of the alkali-soluble resin is preferably 30 to 500 mgKOH / g.
- the lower limit is more preferably 50 mgKOH / g or more, and still more preferably 70 mgKOH / g or more.
- the upper limit is more preferably 400 mgKOH / g or less, still more preferably 200 mgKOH / g or less, still more preferably 150 mgKOH / g or less, and particularly preferably 120 mgKOH / g or less.
- the content of the alkali-soluble resin is preferably 0.1 to 20% by mass with respect to the total solid content of the composition.
- the lower limit is more preferably 0.5% by mass or more, further preferably 1% by mass or more, still more preferably 2% by mass or more, and particularly preferably 3% by mass or more.
- As for an upper limit 12 mass% or less is more preferable, and 10 mass% or less is still more preferable.
- the composition of this invention may contain only 1 type of alkali-soluble resin, and may contain 2 or more types. When two or more types are included, the total amount is preferably within the above range.
- the composition of this invention can contain other than alkali-soluble resin mentioned above (it is also called other resin).
- other resins include (meth) acrylic resin, (meth) acrylamide resin, ene / thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, and polyarylene ether.
- examples include phosphine oxide resin, polyimide resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, siloxane resin, and epoxy resin.
- a norbornene resin can be preferably used from the viewpoint of improving heat resistance.
- Examples of commercially available norbornene resins include the ARTON series (for example, ARTON F4520) manufactured by JSR Corporation.
- the epoxy resin examples include an epoxy resin that is a glycidyl etherified product of a phenol compound, an epoxy resin that is a glycidyl etherified product of various novolak resins, an alicyclic epoxy resin, an aliphatic epoxy resin, a heterocyclic epoxy resin, and a glycidyl ester type.
- commercially available products include Marproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (manufactured by NOF Corporation) and the like.
- the epoxy equivalent of the epoxy resin is preferably 310 to 3300 g / eq, more preferably 310 to 1700 g / eq, and further preferably 310 to 1000 g / eq. You may use an epoxy resin 1 type or in mixture of 2 or more types.
- a commercially available epoxy resin can also be used.
- the following epoxy resins are mentioned, for example.
- Bisphenol F-type epoxy resins are JER806, JER807, JER4004, JER4005, JER4007, JER4010 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON830, EPICLON835 (above, manufactured by DIC Corporation), LCE-21, RE-602S ( As mentioned above, Nippon Kayaku Co., Ltd.) etc. are mentioned.
- As phenol novolac type epoxy resins JER152, JER154, JER157S70, JER157S65 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON N-740, EPICLON N-770, EPICLON N-775 (above, manufactured by DIC Corporation), etc. Can be mentioned.
- EPICLON N-660 As cresol novolac type epoxy resin, EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (above, manufactured by DIC Corporation) And EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.).
- ADEKA RESIN EP-4080S, EP-4085S, EP-4088S (above, manufactured by ADEKA), Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEAD PB 3600, PB 4700 (above, manufactured by Daicel Corporation), Denacol EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (above, manufactured by Nagase ChemteX Corporation), and the like.
- ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (manufactured by ADEKA Corporation), JER1031S (manufactured by Mitsubishi Chemical Corporation), and the like.
- the content of the epoxy resin is preferably 1 to 30% by mass with respect to the total solid content of the composition.
- the lower limit is more preferably 2% by mass or more, and further preferably 3% by mass or more.
- the upper limit is more preferably 25% by mass or less, and still more preferably 20% by mass or less.
- the composition of the present invention may contain only one type of epoxy resin, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
- the composition of the present invention may contain a polyfunctional thiol compound having two or more mercapto groups in the molecule for the purpose of promoting the reaction of the polymerizable compound.
- the polyfunctional thiol compound is preferably a secondary alkanethiol, and particularly preferably a compound having a structure represented by the following general formula (T1).
- T1 In the formula (T1), n represents an integer of 2 to 4, and L represents a divalent to tetravalent linking group.
- the content of the polyfunctional thiol compound is preferably 0.3 to 8.9% by mass, and more preferably 0.8 to 6.4% by mass with respect to the total solid content of the composition.
- the polyfunctional thiol compound may be added for the purpose of improving stability, odor, resolution, developability, adhesion and the like.
- the composition of the present invention preferably contains a photopolymerization initiator when a polymerizable compound is used as the curable compound.
- the photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of a polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, a compound having photosensitivity to light in the ultraviolet region to the visible region is preferable.
- the photopolymerization initiator is preferably a photoradical polymerization initiator.
- the photopolymerization initiator examples include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton and compounds having an oxadiazole skeleton), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazoles, oxime derivatives, and the like. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, and the like.
- the halogenated hydrocarbon compound having a triazine skeleton examples include those described in Wakabayashi et al., Bull. Chem. Soc.
- Photopolymerization initiators are trihalomethyltriazine compounds, benzyldimethylketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryls from the viewpoint of exposure sensitivity.
- Compounds selected from the group consisting of imidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxadiazole compounds and 3-aryl substituted coumarin compounds are preferred.
- the composition of the present invention when used for a solid-state imaging device, it is necessary to form a fine pattern with a sharp shape. It is. From such a viewpoint, it is particularly preferable to use an oxime compound as the photopolymerization initiator.
- an oxime compound as the photopolymerization initiator.
- paragraph numbers 0265 to 0268 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
- ⁇ -hydroxyketone compounds As the photopolymerization initiator, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, and acylphosphine compounds can also be suitably used.
- ⁇ -aminoketone compounds described in JP-A-10-291969 and acylphosphine compounds described in Japanese Patent No. 4225898 can also be used.
- ⁇ -hydroxyketone compound IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (above, manufactured by BASF) can be used.
- ⁇ -aminoketone compound IRGACURE-907, IRGACURE-369, IRGACURE-379, and IRGACURE-379EG (manufactured by BASF) can be used.
- ⁇ -aminoketone compound compounds described in JP2009-191179A can be used.
- acylphosphine compound commercially available products such as IRGACURE-819 and DAROCUR-TPO (above, manufactured by BASF) can be used.
- the photopolymerization initiator is preferably an oxime compound.
- Specific examples of the oxime compound include compounds described in JP-A-2001-233842, JP-A-2000-80068, JP-A-2006-342166, and JP-A-2016-21012.
- TR-PBG-304 (Changzhou Power Electronics New Materials Co., Ltd.), Adeka Arkles NCI-831 (Adeka Co., Ltd.), Adeka Arkles NCI-930 (Adeka Co., Ltd.), Adeka Optomer N-1919 (Photopolymerization initiator 2 manufactured by ADEKA Corporation and described in JP2012-14052A) can also be used.
- oxime compounds other than the above compounds described in JP-A-2009-519904 in which an oxime is linked to the N-position of the carbazole ring, compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety, Compounds described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced at the dye site, ketoxime compounds described in International Publication No. WO2009 / 131189, and triazine skeleton and oxime skeleton are the same A compound described in US Pat. No. 7,556,910 contained in the molecule, a compound described in JP 2009-221114 A having an absorption maximum at 405 nm and good sensitivity to a g-ray light source may be used. .
- the oxime compound is preferably a compound represented by the following formula (OX-1).
- the oxime N—O bond may be an (E) oxime compound, a (Z) oxime compound, or a mixture of (E) and (Z) isomers. .
- R and B each independently represent a monovalent substituent
- A represents a divalent organic group
- Ar represents an aryl group.
- the description of paragraph numbers 0276 to 0304 in JP 2013-029760 A can be referred to, and the contents thereof are incorporated in this specification.
- An oxime compound having a fluorine atom can also be used as a photopolymerization initiator.
- Specific examples of the oxime compound having a fluorine atom include compounds described in JP 2010-262028 A, compounds 24 and 36 to 40 described in JP-A-2014-500852, and JP-A 2013-164471. Compound (C-3). This content is incorporated herein.
- An oxime initiator having a nitro group can also be used as a photopolymerization initiator.
- the oxime compound having a nitro group is also preferably a dimer.
- Specific examples of oxime compounds having a nitro group include compounds described in paragraph numbers 0031 to 0047 of JP2013-114249A, paragraphs 0008 to 0012 and 0070 to 0079 of JP2014-137466A, And compounds described in paragraph Nos. 0007 to 0025 of Japanese Patent No. 4223071, ADEKA ARKLES NCI-831 (manufactured by ADEKA Corporation)).
- An oxime compound having a fluorene ring can also be used as a photopolymerization initiator.
- Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A-2014-137466. This content is incorporated herein.
- An oxime compound having a benzofuran skeleton can also be used as a photopolymerization initiator.
- Specific examples include compounds OE-01 to OE-75 described in International Publication No. WO2015 / 036910.
- the oxime compound is preferably a compound having an absorption maximum in a wavelength region of 350 nm to 500 nm, and more preferably a compound having an absorption maximum in a wavelength region of 360 nm to 480 nm.
- the oxime compound is preferably a compound having high absorbance at 365 nm and 405 nm.
- the molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably 1,000 to 300,000, more preferably 2,000 to 300,000 from the viewpoint of sensitivity, and 5,000 to 200,000. More preferably, it is 000.
- the molar extinction coefficient of the compound can be measured using a known method. For example, it is preferable to measure with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g / L.
- the photopolymerization initiator preferably contains an oxime compound and an ⁇ -aminoketone compound. By using both in combination, the developability is improved and a pattern having excellent rectangularity can be easily formed.
- the oxime compound and the ⁇ -aminoketone compound are used in combination, the ⁇ -aminoketone compound is preferably 50 to 600 parts by mass, more preferably 150 to 400 parts by mass with respect to 100 parts by mass of the oxime compound.
- the content of the photopolymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and still more preferably 1 to 20% by mass with respect to the total solid content of the composition. If the content of the photopolymerization initiator is within the above range, better sensitivity and pattern formability can be obtained.
- the composition of the present invention may contain only one type of photopolymerization initiator, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
- the composition of the present invention can contain a solvent.
- the solvent include organic solvents.
- the solvent is basically not particularly limited as long as it satisfies the solubility of each component and the applicability of the composition, but is preferably selected in consideration of the applicability and safety of the composition.
- organic solvent examples include esters, ethers, ketones, and aromatic hydrocarbons. Specific examples include methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, Examples include butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol monomethyl ether acetate. Details of the organic solvent can be referred to the description of paragraph number 0223 of International Publication No.
- aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as a solvent may be better reduced for environmental reasons, for example, 50 ppm by weight (parts per to the total amount of organic solvent). (million) or less, preferably 10 ppm by mass or less, more preferably 1 ppm by mass or less.
- Organic solvents may be used alone or in combination of two or more.
- a mixed solution composed of two or more selected from ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate is preferable.
- a solvent having a low metal content it is preferable to use a solvent having a low metal content, and the metal content of the solvent is preferably, for example, 10 mass ppb (parts per billion) or less. If necessary, a solvent having a mass ppt (parts per trillation) level may be used, and such a high-purity solvent is provided, for example, by Toyo Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015).
- Examples of the method for removing impurities such as metals from the solvent include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter.
- the filter pore size of the filter used for filtration is preferably 10 nm or less, more preferably 5 nm or less, and still more preferably 3 nm or less.
- the filter material is preferably polytetrachloroethylene, polyethylene or nylon.
- the solvent may contain isomers (compounds having the same number of atoms and different structures). Only one kind of isomer may be contained, or a plurality of isomers may be contained.
- the organic solvent preferably has a peroxide content of 0.8 mmol / L or less, and more preferably contains substantially no peroxide.
- the content of the solvent is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and still more preferably 25 to 75% by mass with respect to the total amount of the composition.
- the composition of the present invention may contain a polymerization inhibitor.
- Polymerization inhibitors include hydroquinone, paramethoxyphenol, di-tert-butyl-paracresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2, 2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like. Of these, paramethoxyphenol is preferred.
- the content of the polymerization inhibitor is preferably 0.01 to 5% by mass with respect to the total solid content of the composition.
- the composition of the present invention can further contain a silane coupling agent.
- the silane coupling agent in this invention is a component different from the near-infrared transmission black color material mentioned above.
- a silane coupling agent means a silane compound having a hydrolyzable group and other functional groups.
- the hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can form a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction.
- a hydrolysable group a halogen atom, an alkoxy group, an acyloxy group etc. are mentioned, for example, An alkoxy group is preferable.
- the silane coupling agent is preferably a compound having an alkoxysilyl group.
- the functional group other than the hydrolyzable group is preferably a group that exhibits affinity by forming an interaction or bond with the resin. Examples thereof include a vinyl group, a styryl group, a (meth) acryloyl group, a mercapto group, an epoxy group, an oxetanyl group, an amino group, a ureido group, a sulfide group, and an isocyanate group, and a (meth) acryloyl group and an epoxy group are preferable.
- silane coupling agent examples include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxy.
- silane coupling agent compounds described in paragraph Nos. 0018 to 0036 of JP-A-2009-288703, compounds described in paragraph Nos. 0056 to 0066 of JP-A-2009-242604, and international publication WO2015 / 166679 Examples include the compounds described in paragraphs 0229-0236, the contents of which are incorporated herein.
- the content of the silane coupling agent is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and still more preferably 1 to 10% by mass with respect to the total solid content of the composition.
- the composition of this invention may contain various surfactant from a viewpoint of improving applicability
- various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.
- paragraph numbers 0238 to 0245 of International Publication No. WO2015 / 166679 can be referred to, the contents of which are incorporated herein.
- liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, and uniformity of coating thickness and liquid-saving properties are further improved. be able to.
- a fluorosurfactant in the composition of the present invention, liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, and uniformity of coating thickness and liquid-saving properties are further improved. be able to.
- the interfacial tension between the surface to be coated and the coating liquid is reduced, the wettability to the surface to be coated is improved, and The coating property to the coated surface is improved. For this reason, it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.
- the fluorine content in the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and even more preferably 7 to 25% by mass.
- a fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in the composition.
- fluorosurfactant examples include surfactants described in JP-A-2014-41318, paragraph numbers 0060 to 0064 (corresponding to paragraph numbers 0060 to 0064 of international publication 2014/17669), and the like. Examples include surfactants described in paragraphs 0117 to 0132 of JP2011-132503A, the contents of which are incorporated herein.
- fluorosurfactants include, for example, Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (above, OMNOVA company make) etc. are mentioned.
- the fluorine-based surfactant has a molecular structure having a functional group containing a fluorine atom, and an acrylic compound in which the fluorine atom is volatilized by cleavage of the functional group containing the fluorine atom when heated is suitably used.
- a fluorosurfactant include Megafac DS series manufactured by DIC Corporation (Chemical Industry Daily, February 22, 2016) (Nikkei Sangyo Shimbun, February 23, 2016). -21, which can be used.
- a block polymer can be used. Examples thereof include compounds described in JP2011-89090A.
- the fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy group or propyleneoxy group) (meth).
- a fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used.
- the following compounds are also exemplified as the fluorosurfactant used in the present invention.
- the weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example, 14,000. In the above compounds,% indicating the ratio of repeating units is mol%.
- a fluoropolymer having an ethylenically unsaturated group in the side chain can also be used.
- Specific examples thereof include compounds described in paragraph Nos. 0050 to 0090 and paragraph Nos. 0289 to 0295 of JP2010-164965A, for example, Megafac RS-101, RS-102, RS-718K manufactured by DIC Corporation. RS-72-K and the like.
- the fluorine-based surfactant compounds described in paragraph numbers 0015 to 0158 of JP-A No. 2015-117327 can also be used.
- Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF ), Tetronic 304, 701, 704, 901, 904, 150R1 (BAS) Solsperse 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure
- the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the composition. Only one type of surfactant may be used, or two or more types may be combined. When using 2 or more types, it is preferable that the total amount becomes the said range.
- the composition of the present invention comprises a thermal polymerization initiator, a thermal polymerization component, an ultraviolet absorber, an antioxidant, a plasticizer, a developing agent such as a low molecular weight organic carboxylic acid, other fillers, an antioxidant, and an aggregation inhibitor.
- Various additives such as can be contained.
- an ultraviolet absorber such as an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, or a triazine compound can be used, and specific examples include compounds described in JP2013-68814A. It is done.
- benzotriazole compound MYUA series (Chemical Industry Daily, February 1, 2016) manufactured by Miyoshi Oil and Fat may be used.
- the antioxidant for example, a phenol compound, a phosphorus compound (for example, a compound described in paragraph No. 0042 of JP2011-90147A), a thioether compound, or the like can be used.
- Examples of commercially available products include ADEKA Corporation's ADK STAB series (AO-20, AO-30, AO-40, AO-50, AO-50F, AO-60, AO-60G, AO-80, AO- 330).
- the metal element may be contained in the composition depending on the raw material used, but the content of the Group 2 element (calcium, magnesium, etc.) in the composition is 50 mass ppm or less from the viewpoint of suppressing the occurrence of defects. It is preferably 0.01 to 10 ppm by mass.
- the total amount of inorganic metal salt in the composition is preferably 100 mass ppm or less, more preferably 0.5 to 50 mass ppm.
- the composition of the present invention can be prepared by mixing the aforementioned components.
- the respective components may be blended together, or may be blended sequentially after each component is dissolved or dispersed in a solvent.
- the composition may be prepared by dissolving or dispersing all the components in a solvent at the same time. If necessary, two or more solutions or dispersions containing each component appropriately prepared in advance may be used. You may mix these at the time of application
- the composition of the present invention contains particles such as pigments, it preferably includes a process of dispersing the particles.
- the mechanical force used for dispersing the particles includes compression, squeezing, impact, shearing, cavitation and the like.
- Specific examples of these processes include a bead mill, a sand mill, a roll mill, a ball mill, a paint shaker, a microfluidizer, a high speed impeller, a sand grinder, a flow jet mixer, a high pressure wet atomization, and an ultrasonic dispersion.
- the particles may be refined in a salt milling process.
- materials, equipment, processing conditions, etc. used in the salt milling process for example, descriptions in JP-A Nos. 2015-194521 and 2012-046629 can be referred to.
- any filter can be used without particular limitation as long as it is a filter that has been conventionally used for filtration.
- fluororesin such as polytetrafluoroethylene (PTFE), polyamide resin such as nylon (eg nylon-6, nylon-6,6), polyolefin resin such as polyethylene and polypropylene (PP) (high density, ultra high molecular weight)
- PP polypropylene
- polypropylene including high density polypropylene
- nylon are preferable.
- the pore size of the filter is suitably about 0.01 to 7.0 ⁇ m, preferably about 0.01 to 3.0 ⁇ m, and more preferably about 0.05 to 0.5 ⁇ m. If the pore diameter of the filter is in the above range, fine foreign matters can be reliably removed. It is also preferable to use a fiber-shaped filter medium.
- the fiber-shaped filter medium include polypropylene fiber, nylon fiber, and glass fiber.
- filter cartridges of SBP type series (such as SBP008), TPR type series (such as TPR002 and TPR005), and SHPX type series (such as SHPX003) manufactured by Loki Techno Co., Ltd. may be mentioned.
- filters for example, a first filter and a second filter
- filtration with each filter may be performed only once or may be performed twice or more.
- the pore diameter here can refer to the nominal value of the filter manufacturer.
- a commercially available filter for example, select from various filters provided by Nippon Pole Co., Ltd. (DFA4201NXEY, etc.), Advantech Toyo Co., Ltd., Japan Integris Co., Ltd. (former Nihon Microlith Co., Ltd.) can do.
- the second filter a filter formed of the same material as the first filter can be used. Filtration with the first filter may be performed only on the dispersion, and after mixing other components, filtration may be performed with the second filter.
- the total solid content (solid content concentration) of the composition varies depending on the application method, but is preferably 1 to 50% by mass, for example.
- the lower limit is more preferably 10% by mass or more.
- the upper limit is more preferably 30% by mass or less.
- the composition of the present invention has a maximum light transmittance in the wavelength range of 400 to 700 nm when a film having a thickness of 1 ⁇ m, 2 ⁇ m, 3 ⁇ m, 4 ⁇ m or 5 ⁇ m after drying is formed.
- the value is preferably 20% or less, and the light transmission in the thickness direction of the film preferably satisfies the spectral characteristics such that the minimum value in the wavelength range of 1100 to 1300 nm is 70% or more.
- the maximum value in the wavelength range of 400 to 700 nm is more preferably 15% or less, still more preferably 10% or less.
- the minimum value in the wavelength range of 1100 to 1300 nm is more preferably 75% or more, and still more preferably 80% or more.
- the composition of the present invention more preferably satisfies any of the following spectral characteristics (1) to (3).
- the maximum value of the light transmittance in the thickness direction of the film in the wavelength range of 400 to 750 nm is 20%. Or less (preferably 15% or less, more preferably 10% or less), and the minimum value of light transmittance in the thickness direction of the film in the wavelength range of 900 to 1300 nm is 70% or more (preferably 75% or more, more An embodiment that is preferably 80% or more.
- the maximum value of the light transmittance in the thickness direction of the film in the wavelength range of 400 to 830 nm is 20 % Or less (preferably 15% or less, more preferably 10% or less)
- the minimum value of light transmittance in the thickness direction of the film in the wavelength range of 1000 to 1300 nm is 70% or more (preferably 75% or more, More preferably, 80% or more).
- the maximum value of the light transmittance in the thickness direction of the film in the wavelength range of 400 to 950 nm is 20 % Or less (preferably 15% or less, more preferably 10% or less)
- the minimum value of light transmittance in the thickness direction of the film in the wavelength range of 1100 to 1300 nm is 70% or more (preferably 75% or more, More preferably, 80% or more).
- the pattern forming method includes a step of forming a composition layer on a support using the composition of the present invention, and a step of forming a pattern on the composition layer by a photolithography method or a dry etching method. It is preferable.
- Pattern formation by the photolithography method includes a step of forming a composition layer on a support using the composition of the present invention, a step of exposing the composition layer in a pattern, and developing and removing an unexposed portion. Forming a pattern.
- Pattern formation by the dry etching method includes forming a composition layer on a support using the composition of the present invention and curing to form a cured product layer, and forming a photoresist layer on the cured product layer. It is preferable to include a step of patterning the photoresist layer by exposure and development to obtain a resist pattern, and a step of forming a pattern by dry etching the cured product layer using the resist pattern as an etching mask.
- each step will be described.
- Step of Forming Composition Layer In the step of forming the composition layer, the composition layer is formed on the support using the composition of the present invention.
- a known method can be used as a method for applying the composition to the support.
- a dropping method drop casting
- a slit coating method for example, a spray method; a roll coating method; a spin coating method (spin coating); a casting coating method; a slit and spin method; a pre-wet method (for example, JP 2009-145395 A).
- Methods described in the publication inkjet (for example, on-demand method, piezo method, thermal method), ejection printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing method, etc.
- the application method in the ink jet is not particularly limited.
- the composition layer formed on the support may be dried (prebaked).
- pre-baking may not be performed.
- the prebaking temperature is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, and further preferably 110 ° C. or lower.
- the lower limit may be 50 ° C. or higher, and may be 80 ° C. or higher.
- the pre-bake time is preferably 10 to 3000 seconds, more preferably 40 to 2500 seconds, and still more preferably 80 to 2200 seconds. Drying can be performed with a hot plate, oven, or the like.
- Exposure process When forming a pattern by photolithography, ⁇ Exposure process >> Next, the composition layer is exposed in a pattern (exposure process).
- pattern exposure can be performed by exposing the composition layer through a mask having a predetermined mask pattern using an exposure apparatus such as a stepper. Thereby, an exposed part can be hardened.
- radiation (light) that can be used for exposure ultraviolet rays such as g-line and i-line are preferable (particularly preferably i-line).
- Irradiation dose (exposure dose) for example, preferably 0.03 ⁇ 2.5J / cm 2, more preferably 0.05 ⁇ 1.0J / cm 2, more preferably 0.08 ⁇ 0.5J / cm 2 .
- the oxygen concentration at the time of exposure can be appropriately selected.
- Exposure intensity is can be set appropriately, usually 1000W / m 2 ⁇ 100000W / m 2 ( preferably 5000 W / m 2 or more, more preferably 15000W / m 2 or more, more preferably 35000W / m 2 or more) You can choose from a range.
- Oxygen concentration and exposure illuminance may appropriately combined conditions, for example, illuminance 10000 W / m 2 at an oxygen concentration of 10 vol%, oxygen concentration of 35 vol% can be such illuminance 20000W / m 2.
- the development removal of the unexposed portion can be performed using a developer.
- the developer is preferably an alkaline developer that does not damage the underlying solid-state imaging device or circuit.
- the temperature of the developer is preferably 20 to 30 ° C., for example.
- the development time is preferably 20 to 180 seconds. Further, in order to improve the residue removability, the process of shaking off the developer every 60 seconds and further supplying a new developer may be repeated several times.
- alkaline agent used in the developer examples include ammonia water, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, Organic alkalinity such as tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene Compounds, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, sodium metasilicate Inorganic alkaline compounds such as arm and the like.
- an alkaline aqueous solution obtained by diluting these alkaline agents with pure water is preferably used.
- concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass.
- a surfactant may be used for the developer. Examples of the surfactant include the surfactant described in the above-described composition, and a nonionic surfactant is preferable.
- a developer composed of such an alkaline aqueous solution it is preferably washed (rinsed) with pure water after development.
- a curing step of curing by heat treatment (post-baking) or post-exposure may be performed.
- Post bake is a heat treatment after development for complete curing.
- the heating temperature in the post baking is preferably 100 to 240 ° C., for example, and more preferably 200 to 240 ° C.
- the heating temperature is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, and more preferably 100 ° C. or lower. Is more preferable, and 90 ° C. or less is particularly preferable.
- the lower limit can be, for example, 50 ° C. or higher.
- Post-baking can be performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), or a high-frequency heater so that the film after development is in the above condition. it can.
- the post-exposure can be performed with g-line, h-line, i-line, excimer laser such as KrF or ArF, electron beam, X-ray, etc., but it can be performed with an existing high-pressure mercury lamp at a low temperature of about 20 to 50 ° C. preferable.
- the irradiation time is preferably 10 seconds to 180 seconds, more preferably 30 seconds to 60 seconds.
- post-exposure and post-heating are used in combination, post-exposure is preferably performed first.
- the pattern formation by the dry etching method is performed by curing the composition layer formed on the support to form a cured product layer, and then using the patterned photoresist layer as a mask to etch the obtained cured product layer. Can be used.
- a pre-bake treatment a mode in which heat treatment after exposure and heat treatment after development (post-bake treatment) are desirable.
- the description in paragraphs 0010 to 0067 of JP2013-064993A can be referred to, and the contents thereof are incorporated in this specification.
- the infrared transmission filter may be constituted by only pixels having specific spectral characteristics of the present invention, and pixels having specific spectral characteristics of the present invention, and red, green, blue, magenta, yellow, cyan, black, colorless.
- An infrared transmission filter may be configured by combining with other pixels.
- the pattern of pixels having specific spectral characteristics of the present invention may be formed first. After forming the pattern of other pixels described above, the pattern of pixels having specific spectral characteristics of the present invention may be formed.
- the film of the present invention is formed by curing the above-described composition of the present invention.
- the cured film of the present invention can be preferably used as an infrared transmission filter.
- the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 700 nm is 20% or less (preferably 15% or less, more preferably 10% or less).
- the minimum value of the light transmittance in the thickness direction in the wavelength range of 1100 to 1300 nm is preferably 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 700 nm can be shielded, and a film that can transmit infrared rays with less visible light-derived noise can be obtained.
- the cured film of the present invention preferably has one of the following spectral characteristics (1) to (3).
- the spectral characteristic of the cured film represents a value obtained by measuring the transmittance in a wavelength range of 300 to 1300 nm using an ultraviolet-visible near-infrared spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation).
- the maximum value of the light transmittance in the thickness direction of the film in the wavelength range of 400 to 750 nm is 20% or less (preferably 15% or less, more preferably 10% or less).
- a mode in which the minimum value of light transmittance in the wavelength range of 900 to 1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light having a wavelength in the range of 400 to 750 nm can be shielded, and a film capable of transmitting infrared light having a wavelength of 900 nm or more can be obtained with less noise derived from visible light.
- the maximum value of light transmittance in the thickness direction of the film in the wavelength range of 400 to 830 nm is 20% or less (preferably 15% or less, more preferably 10% or less).
- An embodiment in which the minimum value of light transmittance in the wavelength range of 1000 to 1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light having a wavelength in the range of 400 to 830 nm can be shielded, and a film capable of transmitting infrared light having a wavelength of 1000 nm or more can be obtained with little noise derived from visible light.
- the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 950 nm is 20% or less (preferably 15% or less, more preferably 10% or less).
- a mode in which the minimum value of light transmittance in the wavelength range of 1100 to 1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 950 nm can be shielded, and a film that can transmit infrared rays having a wavelength of 1100 nm or more can be obtained with little noise derived from visible light.
- the cured film having the spectral characteristic (1) can be formed using the composition of the present invention containing a near-infrared transmitting black color material. Furthermore, by containing a chromatic colorant, it is easy to adjust the spectrum of (1) above to a preferred range.
- the cured film having the spectral characteristic (2) can be formed by using the composition of the present invention further containing an infrared absorber in addition to the near-infrared transmitting black color material.
- the infrared absorber is preferably a compound having a maximum absorption wavelength in a wavelength range of 800 nm or more and less than 900 nm. Further, by further containing a chromatic colorant, the spectrum of (2) can be easily adjusted to a preferred range.
- the cured film having the spectral characteristic (3) can be formed by using the composition of the present invention further containing an infrared absorber in addition to the near-infrared transmitting black color material.
- the infrared absorber is preferably a compound having a maximum absorption wavelength in a wavelength range of 900 nm or more and less than 1000 nm.
- the spectrum of the above (3) can be easily adjusted to a preferred range by further including a chromatic colorant and / or a compound having a maximum absorption wavelength in a wavelength range of 800 nm to less than 900 nm.
- the thickness of the cured film of the present invention is not particularly limited, but is preferably 0.1 to 20 ⁇ m, more preferably 0.5 to 10 ⁇ m.
- the infrared transmission filter of the present invention has the cured film of the present invention.
- the infrared transmission filter of the present invention is preferably used by being laminated on a support.
- the support include a substrate made of a material such as silicon, alkali-free glass, soda glass, Pyrex (registered trademark) glass, or quartz glass.
- a charge coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, or the like may be formed on the support.
- the support may be formed with a black matrix that isolates each pixel. If necessary, the support may be provided with an undercoat layer for improving adhesion to the upper layer, preventing diffusion of substances, or flattening the substrate surface.
- the infrared transmission filter of the present invention can be used in combination with a color filter containing a chromatic colorant.
- a color filter can be manufactured using the coloring composition containing a chromatic colorant.
- the chromatic colorant include the chromatic colorant described in the above composition.
- the coloring composition can further contain a resin, a polymerizable compound, a photopolymerization initiator, a surfactant, a solvent, a polymerization inhibitor, an ultraviolet absorber, and the like. About these details, the material demonstrated by the above-mentioned composition is mentioned, They can be used.
- the infrared transmission filter of the present invention has a pixel of the film or laminate of the present invention and a pixel selected from red, green, blue, magenta, yellow, cyan, black and colorless.
- the solid-state imaging device of the present invention has the cured film of the present invention.
- the configuration of the solid-state imaging device of the present invention is not particularly limited as long as it has the cured film body of the present invention and functions as a solid-state imaging device, and examples thereof include the following configurations.
- the support has a transfer electrode made of a plurality of photodiodes and polysilicon constituting a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.). It has a light-shielding film made of tungsten or the like that is opened only in the light-receiving part, and has a device protective film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire light-shielding film and the photodiode light-receiving part Furthermore, it is the structure which has the cured film of this invention.
- the structure having a light collecting means for example, a microlens, etc., the same shall apply hereinafter
- a light collecting means for example, a microlens, etc., the same shall apply hereinafter
- the structure etc. which have a condensing means may be sufficient.
- the infrared sensor of the present invention has the cured film of the present invention.
- the configuration of the infrared sensor of the present invention is not particularly limited as long as it has the cured film of the present invention and functions as an infrared sensor.
- reference numeral 110 denotes a solid-state image sensor.
- the imaging area provided on the solid-state imaging device 110 includes an infrared cut filter 111 and a color filter 112.
- the infrared cut filter 111 transmits light in the visible light region (for example, light having a wavelength of 400 to 700 nm) and transmits at least part of light in the infrared region (for example, light having a wavelength of 800 to 1300 nm, preferably 900 to 1200 nm).
- the color filter 112 is a color filter in which pixels that transmit and absorb light of a specific wavelength in the visible light region are formed. For example, red (R), green (G), and blue (B) pixels are formed. A color filter or the like is used.
- a region 114 where the infrared cut filter 111 is not formed is provided between the infrared transmission filter 113 and the solid-state image sensor 110. In the region 114, a resin layer (for example, a transparent resin layer) that can transmit light having a wavelength that has passed through the infrared transmission filter 113 is disposed.
- the infrared transmission filter 113 is a filter that has visible light shielding properties and transmits infrared rays having a specific wavelength, and is formed of the cured film of the present invention.
- a micro lens 115 is disposed on the incident light h ⁇ side of the color filter 112 and the infrared transmission filter 113.
- a planarization layer 116 is formed so as to cover the microlens 115.
- the resin layer is disposed in the region 114, but the infrared transmission filter 113 may be formed in the region 114. That is, the infrared transmission filter 113 may be formed on the solid-state image sensor 110.
- FIG. 1 the resin layer is disposed in the region 114, but the infrared transmission filter 113 may be formed in the region 114. That is, the infrared transmission filter 113 may be formed on the solid-state image sensor 110. In the embodiment shown in FIG.
- the film thickness of the color filter 112 and the film thickness of the infrared transmission filter 113 are the same, but the film thicknesses of both may be different.
- the color filter 112 is provided on the incident light h ⁇ side with respect to the infrared cut filter 111, but the order of the infrared cut filter 111 and the color filter 112 is changed to change the infrared cut filter 111. May be provided closer to the incident light h ⁇ than the color filter 112.
- the infrared cut filter 111 and the color filter 112 are stacked adjacent to each other. However, the filters do not necessarily have to be adjacent to each other, and other layers may be provided therebetween. . According to this infrared sensor, since image information can be captured in real time, motion sensing or the like that recognizes a target whose motion is to be detected is possible. Furthermore, since distance information can be acquired, an image including 3D information can be taken.
- composition 1 ⁇ Preparation of composition> (Composition 1; Example 1) 9.0 parts by mass of resin A1, 2.0 parts by mass of coloring material D1, 1.5 parts by mass of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) as a polymerizable compound, and 1 photopolymerization initiator .5 parts by mass and 86.0 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) as a solvent were mixed and stirred, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.5 ⁇ m. Thus, composition 1 was obtained.
- PGMEA propylene glycol monomethyl ether acetate
- composition 2 (Composition 2; Example 2) A composition 2 was obtained in the same manner as the composition 1 except that the color material D2 was used instead of the color material D1.
- composition 3 (Composition 3; Example 3) A composition 3 was obtained in the same manner as the composition 1 except that the color material D3 was used instead of the color material D1.
- composition 4 Composition 4; Example 4
- 9.0 parts by mass of resin A2, 2.0 parts by mass of coloring material D4, 1.5 parts by mass of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) as a polymerizable compound, and 1 photopolymerization initiator .5 parts by mass and 86.0 parts by mass of PGMEA as a solvent were mixed and stirred, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.5 ⁇ m to obtain composition 4. It was.
- composition 5 (Composition 5; Example 5) 9.0 parts by mass of resin A2, 0.5 parts by mass of color material D5, 1.5 parts by mass of color material D3, and 1.
- KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) as a polymerizable compound 5 parts by mass, 1.5 parts by mass of a photopolymerization initiator and 86.0 parts by mass of PGMEA as a solvent were mixed and stirred, and then a nylon filter having a pore diameter of 0.5 ⁇ m (manufactured by Nippon Pole Co., Ltd.) ) To obtain a composition 5.
- composition 6 (Composition 6; Example 6) 8.0 parts by mass of resin A1, 1.0 part by mass of resin A3, 2.0 parts by mass of coloring material D1, and 1.5 KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) as a polymerizable compound
- a nylon filter having a pore size of 0.5 ⁇ m was mixed with 1.5 parts by weight of a photopolymerization initiator, 70.0 parts by weight of PGMEA, and 16.0 parts by weight of methylene chloride and stirred. It filtered with (Nippon Pole Co., Ltd. product), and the composition 6 was obtained.
- composition 7 (Composition 7; Example 7) 8.0 parts by mass of resin A1, 1.0 part by mass of resin A4, 2.0 parts by mass of color material D3, 0.2 part by mass of color material D7, and KAYARAD DPHA as a polymerizable compound (Japan) 1.5 parts by mass of Kayaku Co., Ltd.), 1.5 parts by mass of photopolymerization initiator, and 86.0 parts by mass of PGMEA were mixed and stirred, and then made of nylon having a pore size of 0.5 ⁇ m.
- the composition 7 was obtained by filtering with a filter (manufactured by Nippon Pole Co., Ltd.).
- composition 8 Comparative Example 1
- a composition 8 was obtained in the same manner as the composition 1 except that the color material D6 was used instead of the color material D1.
- composition 9 Comparative Example 2
- a composition 9 was obtained in the same manner as the composition 8 except that the content of the coloring material D6 was changed to 0.5 part by mass.
- composition 10 Comparative Example 3
- black pigment Irgaphor Black S0100CF manufactured by BASF
- 93.8 g of a dispersant BYK21116; manufactured by Big Chemie
- PGMEA propylene glycol monoethyl ether acetate
- the mixture was stirred for 1 hour with a homomixer (manufactured by Tokushu Kika) to obtain Preliminary Dispersion 1.
- the preliminary dispersion 1 was supplied to an ultra apex mill (manufactured by Kotobuki Kogyo) equipped with a centrifugal separator filled with 70% of zirconia beads (manufactured by Toray) having a diameter of 0.10 mm, and rotated at a rotational speed of 8 m / s for 2 hours. Dispersion was performed to obtain a black pigment dispersion 1 having a solid content concentration of 25 mass% and a pigment / resin (mass ratio) of 80/20. 0.38 g of Adeka Arcles (registered trademark) NCI-831 as a photopolymerization initiator was added to 29.52 g of PGMEA and stirred until the solid content was dissolved.
- Adeka Arcles registered trademark
- Color materials D1 to D7 Compounds having the following structures.
- D1, D3, and D4 are near-infrared transmitting black color materials made of a dye compound having a crosslinkable group.
- D5 is a red colorant comprising a dye compound having a crosslinkable group.
- D6 is a near-infrared transmitting black color material made of a dye compound having no crosslinkable group.
- the color materials D1 to D7 are compounds that are dissolved in 3 g or more in 100 g of propylene glycol monomethyl ether acetate at 23 ° C.
- Resin A3 ARTON F4520 (manufactured by JSR Corporation), norbornene resin)
- Resin A4 Marproof G-0150M (manufactured by NOF Corporation, glycidyl methacrylate skeleton random polymer)
- Photopolymerization initiator Compound with the following structure
- Each composition was spin-coated on a glass substrate so that the film thickness after post-baking was 1.1 ⁇ m, and dried by heating at 100 ° C. for 120 seconds using a hot plate. After drying, the film was further heated (post-baked) at 220 ° C. for 300 seconds using a hot plate to form a cured film.
- a UV-visible near-infrared spectrophotometer U-4100, manufactured by Hitachi High-Technologies Corporation
- the glass substrate on which the cured film was formed was measured for transmittance in the wavelength range of 300 to 1300 nm and absorbance in the wavelength range of 400 to 700 nm.
- the minimum value A and the maximum absorbance B in the wavelength range of 1100 to 1300 nm were measured.
- the values of spectral characteristics A / B of each composition are shown in the following table.
- Each composition was spin-coated on a silicon wafer so that the film thickness after post-baking was 1.1 ⁇ m, and dried by heating at 100 ° C. for 120 seconds using a hot plate. Then, using an i-line stepper exposure apparatus FPA-3000i5 + (Canon (Ltd.)), 50 mJ / cm 2 from 50 using a photomask 1.1 ⁇ m square square pixel pattern is formed to 750 mJ / cm 2 The optimum exposure amount for resolving the square pixel pattern was determined by increasing each time, and exposure was performed at this optimum exposure amount.
- FPA-3000i5 + Canon (Ltd.)
- the silicon wafer on which the exposed coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics), and CD-2060 (tetramethylammonium salt).
- Paddle development was performed at 23 ° C. for 60 seconds using a hydroxide aqueous solution (Fuji Film Electronics Materials Co., Ltd.) to form a pattern on the silicon wafer.
- the silicon wafer on which the pattern was formed was rinsed with pure water and then spin-dried.
- heat treatment post-baking was performed for 300 seconds using a 220 ° C. hot plate to obtain a silicon wafer having a pattern (infrared transmitting filter).
- Pattern resolution pattern formability
- the obtained pattern shape was evaluated according to the following criteria. 3: A clear square shape can be recognized. 2: A square shape can be recognized. 1: The shape is broken.
- the obtained infrared transmission filter was incorporated into a solid-state imaging device according to a known method.
- the obtained solid-state imaging device was irradiated with a near-infrared LED (light-emitting diode) light source having an emission wavelength of 940 nm in a low-illuminance environment (0.001 Lux), and an image was captured to compare and evaluate image performance.
- Spectral recognition was evaluated according to the following criteria. 3: Good The subject can be clearly recognized on the image. 2: Slightly good The subject can be recognized on the image. 1: Inadequate The subject cannot be recognized on the image.
- the examples were excellent in pattern resolution and solvent resistance. Moreover, the infrared transmission filter formed using the composition of an Example had favorable spectral recognition. On the other hand, the comparative example was inferior in at least one of solvent resistance or pattern resolution.
- Example 1 the same effect can be obtained by using a crosslinkable dye having a pigment skeleton of a perylene compound, an azo compound or a bisbenzofuranone compound instead of the color material D1.
- Infrared sensor 110: Solid-state imaging device
- 111 Infrared cut filter
- 112 Color filter
- 113 Infrared transmission filter
- 114 Region (resin layer)
- 115 Microlens
- 116 Flattening layer
- h ⁇ Incident light
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Abstract
Description
<1> 近赤外線透過黒色色材と、硬化性化合物と、溶剤とを含む組成物であって、
近赤外線透過黒色色材は、架橋性基を有する染料化合物、および、染料化合物由来の構造を有する色素多量体から選ばれる少なくとも1種を含有し、
組成物の波長400~700nmの範囲における吸光度の最小値Aと、波長1100~1300nmの範囲における吸光度の最大値Bとの比であるA/Bが4.5以上である、組成物。
<2> 染料化合物が有する架橋性基は、エチレン性不飽和結合を有する基、エポキシ基およびアルコキシシリル基から選ばれる少なくとも1種である、<1>に記載の組成物。
<3> 架橋性基を有する染料化合物は、キサンテン化合物、ペリレン化合物、アゾ化合物およびビスベンゾフラノン化合物から選ばれる少なくとも1種である、<1>または<2>に記載の組成物。
<4> 色素多量体は、2価以上の連結基に染料化合物由来の構造が2以上結合してなる、<1>~<3>のいずれか1つに記載の組成物。
<5> 色素多量体は、染料化合物由来の構造を有する繰り返し単位を有する、<1>~<3>のいずれか1つに記載の組成物。
<6> 更に、有彩色着色剤を含む、<1>~<5>のいずれか1つに記載の組成物。
<7> <1>~<6>のいずれか1つに記載の組成物を硬化してなる硬化膜。
<8> <7>に記載の硬化膜を有する赤外線透過フィルタ。
<9> <7>に記載の硬化膜を有する固体撮像素子。
<10> <7>に記載の硬化膜を有する赤外線センサ。
本明細書における基(原子団)の表記において、置換および無置換を記していない表記は、置換基を有さない基と共に置換基を有する基を包含する。例えば、「アルキル基」とは、置換基を有さないアルキル基(無置換アルキル基)のみならず、置換基を有するアルキル基(置換アルキル基)を包含する。
本明細書において「露光」とは、特に断らない限り、光を用いた露光のみならず、電子線、イオンビーム等の粒子線を用いた描画も含む。また、露光に用いられる光としては、水銀灯の輝線スペクトル、エキシマレーザに代表される遠紫外線、極紫外線(EUV光)、X線、電子線等の活性光線または放射線が挙げられる。
本明細書において、「(メタ)アクリレート」は、アクリレートおよびメタクリレートの双方、または、いずれかを表し、「(メタ)アクリル」は、アクリルおよびメタクリルの双方、または、いずれかを表し、「(メタ)アクリロイル」は、アクリロイルおよびメタクリロイルの双方、または、いずれかを表す。
本明細書において「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の作用が達成されれば、本用語に含まれる。
本明細書において、重量平均分子量および数平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)測定でのポリスチレン換算値として定義される。本明細書において、重量平均分子量(Mw)及び数平均分子量(Mn)は、例えば、HLC-8220(東ソー(株)製)を用い、カラムとしてTSKgel Super AWM―H(東ソー(株)製、6.0mmID(内径)×15.0cm)を用い、溶離液として10mmol/L リチウムブロミドNMP(N-メチルピロリジノン)溶液を用いることによって求めることができる。
本明細書において、「~」を用いて表される数値範囲は、「~」の前後に記載される数値を下限値及び上限値として含む範囲を意味する。
本発明の組成物は、近赤外線透過黒色色材と、硬化性化合物と、溶剤とを含む組成物であって、
近赤外線透過黒色色材は、架橋性基を有する染料化合物、および、架橋性基を有する染料化合物由来の構造を有する色素多量体から選ばれる少なくとも1種を含有し、
組成物の波長400~700nmの範囲における吸光度の最小値Aと、波長1100~1300nmの範囲における吸光度の最大値Bとの比であるA/Bが4.5以上であることを特徴とする。
また、赤外線センサ等のデバイスの製造プロセスにおいて、赤外線透過フィルタ上にカラーフィルタや保護膜などを積層することがある。赤外線透過フィルタの耐溶剤性が劣ると、赤外線透過フィルタ上にこれらの膜を積層した際に、赤外線透過フィルタから近赤外線透過黒色色材などが溶出して赤外線透過フィルタの分光特性が変動することがある。これに対し、本発明の組成物によれば、耐溶剤性に優れた硬化膜を形成できるので、本発明の組成物を用いて形成した硬化膜上にカラーフィルタや保護膜などを形成した場合であっても、硬化膜から近赤外線透過黒色色材が溶出することなどを抑制できる。
また、本発明の組成物は、近赤外線透過黒色色材として、架橋性基を有する染料化合物、および/または、染料化合物由来の構造を有する色素多量体を用いるので、パターン形成性が良好であり、より微細なパターンを形成することができる。
また、近赤外線透過黒色色材は、i線(365nm)などの透過性が低いため、パターンサイズが高解像になるに従いパターンの矩形性が低下したり、パターンはがれが生じる場合があるが、近赤外線透過黒色色材として、架橋性基(好ましくはエチレン性不飽和結合を有する基)を有する染料化合物を用いることで、少ない露光量でも膜の下部まで硬化させることができ、高解像のパターンであっても、矩形性および密着性などに優れたパターンを形成することができる。
Aλ=-log(Tλ/100) ・・・(1)
Aλは、波長λにおける吸光度であり、Tλは、波長λにおける透過率(%)である。
吸光度の値は、溶液の状態で測定した値であってもよく、組成物を用いて製膜した膜での値であってもよい。膜の状態で吸光度を測定する場合は、ガラス基板上にスピンコート等の方法により、乾燥後の膜の厚さが所定の厚さとなるように組成物を塗布し、ホットプレートを用いて100℃、120秒間乾燥して調製した膜を用いて測定することが好ましい。膜の厚さは、膜を有する基板について、触針式表面形状測定器(ULVAC社製 DEKTAK150)を用いて測定することができる。
本発明の組成物を、ガラス基板上にスピンコート等の方法により、乾燥後の膜の厚さが所定の厚さとなるように塗布し、ホットプレートを用いて100℃、120秒間乾燥する。膜の厚さは、膜を有する乾燥後の基板を、触針式表面形状測定器(ULVAC社製 DEKTAK150)を用いて測定する。この膜を有する乾燥後の基板を、紫外可視近赤外分光光度計(日立ハイテクノロジーズ社製 U-4100)を用いて、波長300~1300nmの範囲において透過率を測定する。
本発明の組成物は近赤外線透過黒色色材を含有する。本発明における近赤外線透過黒色色材は、架橋性基を有する染料化合物、および、架橋性基を有する染料化合物由来の構造を有する色素多量体から選ばれる少なくとも1種を含有する。
近赤外線透過黒色色材は、紫色から赤色の波長域の光を吸収する材料であることが好ましい。近赤外線透過黒色色材は、波長400~700nmの範囲の光を遮光する色材であることが好ましい。近赤外線透過黒色色材は、波長400~700nmの範囲における吸光度の最小値A1と、波長900~1300nmの範囲における吸光度の最小値B1との比であるA1/B1が4.5以上であることが好ましい。近赤外線透過黒色色材は、波長800~1300nmの範囲の光の少なくとも一部を透過させる色材であることが好ましい。
架橋性基を有する染料化合物(架橋性染料ともいう)は、キサンテン化合物、ペリレン化合物、アゾ化合物およびビスベンゾフラノン化合物から選ばれる少なくとも1種の化合物であることが好ましく、キサンテン化合物がより好ましい。
近赤外線透過黒色色材として用いる色素多量体は、架橋性基を有する染料化合物由来の構造を有する色素多量体(以下、色素多量体Aともいう)である。
式(A)中、X1は繰り返し単位の主鎖を表し、L1は単結合または2価の連結基を表す。DyeIは色素構造を表す。
式(A-1)におけるR1Aが表すアルキル基の炭素数は、1~5が好ましく、1~3がより好ましく、1が更に好ましい。R1Aは、水素原子またはメチル基が好ましい。
式(A-3)におけるアルキル基の炭素数は、1~10が好ましく、1~8がより好ましく、1~6がさらに好ましい。また、アルキル基は、直鎖、分岐、環状のいずれであってもよく、直鎖が好ましい。式(A-3)におけるアリール基の炭素数は、6~20が好ましく、6~14がより好ましく、6~10がさらに好ましい。
本発明の組成物は、近赤外線透過黒色色材として、上述した架橋性染料および上述した色素多量体A以外の近赤外線透過黒色色材(以下、他の近赤外線透過黒色色材ともいう)を含有してもよい。他の近赤外線透過黒色色材は、顔料タイプの近赤外線透過黒色色材や、染料タイプの近赤外線透過黒色色材であって、架橋性基を有さない染料化合物が挙げられる。他の近赤外線透過黒色色材としては、ビスベンゾフラノン化合物、アゾメチン化合物、ペリレン化合物、アゾ系化合物などが挙げられ、ビスベンゾフラノン化合物、ペリレン化合物が好ましい。
ビスベンゾフラノン化合物としては、特表2010-534726号公報、特表2012-515233号公報、特表2012-515234号公報などに記載のものが挙げられ、例えば、BASF社製の「Irgaphor Black」として入手可能である。
ペリレン化合物としては、C.I.Pigment Black 31、32などが挙げられる。
アゾメチン化合物としては、特開平1-170601号公報、特開平2-34664号公報などに記載のものが挙げられ、例えば、大日精化社製の「クロモファインブラックA1103」として入手できる。
アゾ系化合物は、特に限定されないが、下記式(A-1)で表される化合物等を好適に挙げることができる。
式中、R1およびR2はそれぞれ独立して水素原子又は置換基を表し、R3およびR4はそれぞれ独立して置換基を表し、aおよびbはそれぞれ独立して0~4の整数を表す。aが2以上の場合、複数のR3は、同一であってもよく、異なってもよく、複数のR3は結合して環を形成していてもよい。bが2以上の場合、複数のR4は、同一であってもよく、異なってもよく、複数のR4は結合して環を形成していてもよい。
また、本発明の組成物は、他の近赤外線透過黒色色材を実質的に含有しないこともできる。他の近赤外線透過黒色色材を実質的に含有しない場合とは、近赤外線透過黒色色材中における他の近赤外線透過黒色色材の含有量が3質量%以下であることが好ましく、1質量%以下であることがより好ましく、含有しないことが更に好ましい。
本発明の組成物は、赤外線吸収剤を含有することができる。赤外線透過フィルタにおいて、赤外線吸収剤は、透過する光(近赤外線)をより長波長側に限定する役割を有している。
本発明の組成物は、有彩色着色剤を含有することが好ましい。なお、本明細書において、有彩色着色剤とは、白色着色剤および黒色着色剤以外の着色剤を意味する。有彩色着色剤は、極大吸収波長が400~650nmの範囲に有する着色剤が好ましい。
カラーインデックス(C.I.)Pigment Yellow 1,2,3,4,5,6,10,11,12,13,14,15,16,17,18,20,24,31,32,34,35,35:1,36,36:1,37,37:1,40,42,43,53,55,60,61,62,63,65,73,74,77,81,83,86,93,94,95,97,98,100,101,104,106,108,109,110,113,114,115,116,117,118,119,120,123,125,126,127,128,129,137,138,139,147,148,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214等(以上、黄色顔料)、
C.I.Pigment Orange 2,5,13,16,17:1,31,34,36,38,43,46,48,49,51,52,55,59,60,61,62,64,71,73等(以上、オレンジ色顔料)、
C.I.Pigment Red 1,2,3,4,5,6,7,9,10,14,17,22,23,31,38,41,48:1,48:2,48:3,48:4,49,49:1,49:2,52:1,52:2,53:1,57:1,60:1,63:1,66,67,81:1,81:2,81:3,83,88,90,105,112,119,122,123,144,146,149,150,155,166,168,169,170,171,172,175,176,177,178,179,184,185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,254,255,264,270,272,279等(以上、赤色顔料)、
C.I.Pigment Green 7,10,36,37,58,59等(以上、緑色顔料)、
C.I.Pigment Violet 1,19,23,27,32,37,42等(以上、紫色顔料)、
C.I.Pigment Blue 1,2,15,15:1,15:2,15:3,15:4,15:6,16,22,60,64,66,79,80等(以上、青色顔料)。
これら有機顔料は、単独若しくは種々組み合わせて用いることができる。
有彩色着色剤の含有量は、近赤外線透過黒色色材の100質量部に対し、1~100質量部が好ましく、30~100質量部がより好ましい。また、有彩色着色剤の含有量は、上述した架橋性染料と上述した色素多量体Aとの合計100質量部に対し、1~100質量部が好ましく、30~100質量部がより好ましい。
有彩色着色剤は1種単独で用いてもよく、2種以上併用してもよい。有彩色着色剤を2種以上併用する場合、その合計量が上記範囲内であることが好ましい。
本発明の組成物は、硬化性化合物を含有する。硬化性化合物としては、重合性化合物、樹脂等が挙げられる。樹脂は、非架橋性の樹脂(架橋性基を有さない樹脂)であってもよく、架橋性の樹脂(架橋性基を有する樹脂)であってもよい。架橋性基としては、エチレン性不飽和結合を有する基、エポキシ基、アルコキシシリル基などが挙げられる。本発明では、硬化性化合物として、重合性化合物(好ましくはラジカル重合性化合物)と樹脂とを併用することが好ましい。また、樹脂は、後述するアルカリ可溶性樹脂を含むことが好ましい。なお、本発明において、硬化性化合物は、近赤外線透過黒色色材以外の成分である。
重合性化合物は、モノマー、ポリマーのいずれの形態であってもよいが、モノマーが好ましい。モノマータイプの重合性化合物は、分子量が100~3000であることが好ましい。上限は、2000以下が好ましく、1500以下が更に好ましい。下限は、150以上が好ましく、250以上が更に好ましい。また、重合性化合物は、分子量分布を実質的に有さない化合物であることも好ましい。ここで、分子量分布を実質的に有さないとは、化合物の分散度(重量平均分子量(Mw)/数平均分子量(Mn))が、1.0~1.5であることが好ましく、1.0~1.3がより好ましい。重合性化合物は、ラジカルの作用により重合可能な化合物が好ましい。すなわち、重合性化合物は、ラジカル重合性化合物であることが好ましい。重合性化合物は、エチレン性不飽和結合を有する基を1個以上有する化合物が好ましく、エチレン性不飽和結合を有する基を2個以上有する化合物がより好ましく、エチレン性不飽和結合を有する基を3個以上有する化合物が更に好ましい。エチレン性不飽和結合を有する基の個数の上限は、たとえば、15個以下が好ましく、6個以下がより好ましい。エチレン性不飽和結合を有する基としては、ビニル基、スチリル基、(メタ)アリル基、(メタ)アクリロイル基などが挙げられ、(メタ)アクリロイル基が好ましい。重合性化合物は、3~15官能の(メタ)アクリレート化合物であることが好ましく、3~6官能の(メタ)アクリレート化合物であることがより好ましい。
また、ジグリセリンEO(エチレンオキシド)変性(メタ)アクリレート(市販品としては M-460;東亞合成(株)製)が好ましい。ペンタエリスリトールテトラアクリレート(新中村化学工業(株)製、A-TMMT)、1,6-ヘキサンジオールジアクリレート(日本化薬(株)製、KAYARAD HDDA)も好ましい。これらのオリゴマータイプも使用できる。例えば、RP-1040(日本化薬(株)製)などが挙げられる。
カプロラクトン構造を有する化合物としては、分子内にカプロラクトン構造を有する限り特に限定されないが、例えば、トリメチロールエタン、ジトリメチロールエタン、トリメチロールプロパン、ジトリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、トリペンタエリスリトール、グリセリン、ジグリセロール、トリメチロールメラミン等の多価アルコールと、(メタ)アクリル酸及びε-カプロラクトンをエステル化することにより得られる、ε-カプロラクトン変性多官能(メタ)アクリレートを挙げることができる。カプロラクトン構造を有する化合物は、国際公開WO2015/166779号公報の段落番号0153~0170の記載を参酌でき、この内容は本明細書に組み込まれる。市販品としては、例えばサートマー社製のエチレンオキシ鎖を4個有する4官能アクリレートであるSR-494、日本化薬(株)製のペンチレンオキシ鎖を6個有する6官能アクリレートであるDPCA-60、イソブチレンオキシ鎖を3個有する3官能アクリレートであるTPA-330などが挙げられる。
市販品としては、ウレタンオリゴマーUAS-10、UAB-140(山陽国策パルプ社製)、UA-7200(新中村化学工業(株)製)、DPHA-40H(日本化薬(株)製)、UA-306H、UA-306T、UA-306I、AH-600、T-600、AI-600(共栄社化学(株)製)などが挙げられる。
本発明の組成物は、硬化性化合物として樹脂を含有することができる。樹脂としては、アルカリ可溶性樹脂などが挙げられる。樹脂の重量平均分子量(Mw)は、2,000~2,000,000が好ましい。上限は、1,000,000以下がより好ましく、500,000以下が更に好ましい。下限は、3,000以上がより好ましく、5,000以上が更に好ましい。樹脂の含有量は、組成物の全固形分の10~80質量%であることが好ましく、20~60質量%であることがより好ましい。組成物は、樹脂を1種類のみ含んでいてもよいし、2種類以上含んでいてもよい。樹脂を2種類以上含む場合は、その合計量が上記範囲となることが好ましい。
本発明の組成物は、樹脂としてアルカリ可溶性樹脂を含有することが好ましい。アルカリ可溶性樹脂を含有することにより、現像性およびパターン形成性が向上する。
アルカリ可溶性樹脂としては、アルカリ溶解を促進する基を有する樹脂の中から適宜選択することができる。アルカリ溶解を促進する基(以下、酸基ともいう)としては、例えば、カルボキシ基、リン酸基、スルホ基、フェノール性ヒドロキシ基などが挙げられ、カルボキシ基が好ましい。これら酸基は、1種のみであってもよいし、2種以上であってもよい。
式(ED2)中、Rは水素原子または炭素数1~30の有機基を表す。式(ED2)の具体例としては、特開2010-168539号公報の記載を参酌できる。
式(X)において、R1は水素原子またはメチル基を表し、R2は炭素数2~10のアルキレン基を表し、R3は水素原子またはベンゼン環を含んでもよい炭素数1~20のアルキル基を表す。nは1~15の整数を表す。
本発明の組成物は、上述したアルカリ可溶性樹脂以外(その他の樹脂ともいう)を含有することができる。その他の樹脂としては、例えば、(メタ)アクリル樹脂、(メタ)アクリルアミド樹脂、エン・チオール樹脂、ポリカーボネート樹脂、ポリエーテル樹脂、ポリアリレート樹脂、ポリスルホン樹脂、ポリエーテルスルホン樹脂、ポリフェニレン樹脂、ポリアリーレンエーテルフォスフィンオキシド樹脂、ポリイミド樹脂、ポリアミドイミド樹脂、ポリオレフィン樹脂、環状オレフィン樹脂、ポリエステル樹脂、スチレン樹脂、シロキサン樹脂、エポキシ樹脂などが挙げられる。環状オレフィン樹脂としては、耐熱性向上の観点からノルボルネン樹脂が好ましく用いることができる。ノルボルネン樹脂の市販品としては、例えば、JSR(株)製のARTONシリーズ(例えば、ARTON F4520)などが挙げられる。
また、組成物がエポキシ樹脂と重合性化合物とを含む場合、重合性化合物と、エポキシ樹脂との質量比は、重合性化合物:エポキシ樹脂=100:1~100:400が好ましく、100:1~100:100がより好ましい。
本発明の組成物は、重合性化合物の反応を促進させることなどを目的として、分子内に2個以上のメルカプト基を有する多官能チオール化合物を含んでいてもよい。多官能チオール化合物は、2級のアルカンチオール類であることが好ましく、特に下記一般式(T1)で表される構造を有する化合物であることが好ましい。
一般式(T1)
(式(T1)中、nは2~4の整数を表し、Lは2~4価の連結基を表す。)
本発明の組成物は、硬化性化合物として重合性化合物を用いる場合、光重合開始剤を含有することが好ましい。光重合開始剤としては、重合性化合物の重合を開始する能力を有する限り、特に制限はなく、公知の光重合開始剤の中から適宜選択することができる。例えば、紫外線領域から可視領域の光に対して感光性を有する化合物が好ましい。光重合開始剤は、光ラジカル重合開始剤が好ましい。
市販品ではIRGACURE-OXE01、IRGACURE-OXE02、IRGACURE-OXE03、IRGACURE-OXE04(以上、BASF社製)も好適に用いられる。TR-PBG-304(常州強力電子新材料有限公司製)、アデカアークルズNCI-831((株)ADEKA製)、アデカアークルズNCI-930((株)ADEKA製)、アデカオプトマーN-1919((株)ADEKA製、特開2012-14052号公報に記載の光重合開始剤2)も用いることができる。
オキシム化合物の365nm又は405nmにおけるモル吸光係数は、感度の観点から、1,000~300,000であることが好ましく、2,000~300,000であることがより好ましく、5,000~200,000であることが更に好ましい。
化合物のモル吸光係数は、公知の方法を用いて測定することができる。例えば、紫外可視分光光度計(Varian社製Cary-5 spectrophotometer)にて、酢酸エチル溶媒を用い、0.01g/Lの濃度で測定することが好ましい。
本発明の組成物は、溶剤を含有することができる。溶剤としては、有機溶剤が挙げられる。溶剤は、各成分の溶解性や組成物の塗布性を満足すれば基本的には特に制限はないが、組成物の塗布性、安全性を考慮して選ばれることが好ましい。
ただし溶剤としての芳香族炭化水素類(ベンゼン、トルエン、キシレン、エチルベンゼン等)は、環境面等の理由により低減したほうがよい場合があり、例えば、有機溶剤全量に対して、50質量ppm(parts per million)以下が好ましく、10質量ppm以下がより好ましく、1質量ppm以下が更に好ましい。
本発明の組成物は、重合禁止剤を含有してもよい。重合禁止剤としては、ハイドロキノン、パラメトキシフェノール、ジ-tert-ブチル-パラクレゾール、ピロガロール、tert-ブチルカテコール、ベンゾキノン、4,4’-チオビス(3-メチル-6-tert-ブチルフェノール)、2,2’-メチレンビス(4-メチル-6-t-ブチルフェノール)、N-ニトロソフェニルヒドロキシアミン第一セリウム塩等が挙げられる。中でも、パラメトキシフェノールが好ましい。
重合禁止剤の含有量は、組成物の全固形分に対して、0.01~5質量%が好ましい。
本発明の組成物は、更に、シランカップリング剤を含有することができる。なお、本発明におけるシランカップリング剤は、上述した近赤外線透過黒色色材とは異なる成分である。
本明細書において、シランカップリング剤は、加水分解性基とそれ以外の官能基とを有するシラン化合物を意味する。加水分解性基とは、ケイ素原子に直結し、加水分解反応及び縮合反応の少なくともいずれかによってシロキサン結合を生じ得る置換基をいう。加水分解性基としては、例えば、ハロゲン原子、アルコキシ基、アシルオキシ基などが挙げられ、アルコキシ基が好ましい。すなわち、シランカップリング剤は、アルコキシシリル基を有する化合物が好ましい。加水分解性基以外の官能基は、樹脂との間で相互作用もしくは結合を形成して親和性を示す基が好ましい。例えば、ビニル基、スチリル基、(メタ)アクリロイル基、メルカプト基、エポキシ基、オキセタニル基、アミノ基、ウレイド基、スルフィド基、イソシアネート基などが挙げられ、(メタ)アクリロイル基およびエポキシ基が好ましい。
本発明の組成物は、塗布性をより向上させる観点から、各種の界面活性剤を含有してもよい。界面活性剤としては、フッ素系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤、シリコーン系界面活性剤などの各種界面活性剤を使用できる。界面活性剤は、国際公開WO2015/166779号公報の段落番号0238~0245を参酌でき、この内容は本明細書に組み込まれる。
上記の化合物の重量平均分子量は、好ましくは3,000~50,000であり、例えば、14,000である。上記の化合物中、繰り返し単位の割合を示す%はモル%である。
本発明の組成物は、熱重合開始剤、熱重合成分、紫外線吸収剤、酸化防止剤、可塑剤、低分子量有機カルボン酸などの現像性向上剤、その他充填剤、酸化防止剤、凝集防止剤などの各種添加物を含有することができる。紫外線吸収剤は、アミノジエン化合物、サリシレート化合物、ベンゾフェノン化合物、ベンゾトリアゾール化合物、アクリロニトリル化合物、トリアジン化合物等の紫外線吸収剤を用いることができ、具体例としては特開2013-68814号に記載の化合物が挙げられる。ベンゾトリアゾール化合物としてはミヨシ油脂製のMYUAシリーズ(化学工業日報、2016年2月1日)を用いてもよい。酸化防止剤としては、例えばフェノール化合物、リン系化合物(例えば特開2011-90147号公報の段落番号0042に記載の化合物)、チオエーテル化合物などを用いることができる。市販品としては、例えば(株)ADEKA製のアデカスタブシリーズ(AO-20、AO-30、AO-40、AO-50、AO-50F、AO-60、AO-60G、AO-80、AO-330など)が挙げられる。
本発明の組成物は、前述の成分を混合して調製できる。
組成物の調製に際しては、各成分を一括配合してもよいし、各成分を溶剤に溶解または分散した後に逐次配合してもよい。配合する際の投入順序や作業条件は特に制約を受けない。例えば、全成分を同時に溶剤に溶解または分散して組成物を調製してもよいし、必要に応じては、各成分を適宜配合した2つ以上の溶液または分散液をあらかじめ調製し、使用時(塗布時)にこれらを混合して組成物として調製してもよい。
フィルタの孔径は、0.01~7.0μm程度が適しており、0.01~3.0μm程度が好ましく、0.05~0.5μm程度がより好ましい。フィルタの孔径が上記範囲であれば、微細な異物を確実に除去できる。ファイバ状のろ材を用いることも好ましい。ファイバ状のろ材としては、例えばポリプロピレンファイバ、ナイロンファイバ、グラスファイバ等が挙げられる。具体的には、ロキテクノ社製のSBPタイプシリーズ(SBP008など)、TPRタイプシリーズ(TPR002、TPR005など)、SHPXタイプシリーズ(SHPX003など)のフィルタカートリッジが挙げられる。
上述した範囲内で異なる孔径のフィルタを組み合わせてもよい。ここでの孔径は、フィルタメーカーの公称値を参照することができる。市販のフィルタとしては、例えば、日本ポール株式会社(DFA4201NXEYなど)、アドバンテック東洋株式会社、日本インテグリス株式会社(旧日本マイクロリス株式会社)又は株式会社キッツマイクロフィルタ等が提供する各種フィルタの中から選択することができる。
第2のフィルタは、第1のフィルタと同様の素材等で形成されたものを使用することができる。
第1のフィルタでのろ過は、分散液のみに対して行い、他の成分を混合した後で、第2のフィルタでろ過を行ってもよい。
(1)乾燥後の膜厚が1μm、2μm、3μm、4μmまたは5μmの膜を製膜した際に、膜の厚み方向における光の透過率の、波長400~750nmの範囲における最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、膜の厚み方向における光の透過率の、波長900~1300nmの範囲における最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)である態様。
(2):乾燥後の膜厚が1μm、2μm、3μm、4μmまたは5μmの膜を製膜した際に、膜の厚み方向における光の透過率の、波長400~830nmの範囲における最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、膜の厚み方向における光の透過率の、波長1000~1300nmの範囲における最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)である態様。
(3):乾燥後の膜厚が1μm、2μm、3μm、4μmまたは5μmの膜を製膜した際に、膜の厚み方向における光の透過率の、波長400~950nmの範囲における最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、膜の厚み方向における光の透過率の、波長1100~1300nmの範囲における最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)である態様。
次に、本発明の組成物を用いたパターン形成方法について説明する。パターン形成方法は、本発明の組成物を用いて支持体上に組成物層を形成する工程と、フォトリソグラフィ法またはドライエッチング法により、組成物層に対してパターンを形成する工程と、を含むことが好ましい。
ドライエッチング法でのパターン形成は、本発明の組成物を用いて支持体上に組成物層を形成し、硬化して硬化物層を形成する工程と、硬化物層上にフォトレジスト層を形成する工程と、露光および現像することによりフォトレジスト層をパターニングしてレジストパターンを得る工程と、レジストパターンをエッチングマスクとして硬化物層をドライエッチングしてパターンを形成する工程とを含むことが好ましい。以下、各工程について説明する。
組成物層を形成する工程では、本発明の組成物を用いて、支持体上に組成物層を形成する。
<<露光工程>>
次に、組成物層を、パターン状に露光する(露光工程)。例えば、組成物層に対し、ステッパー等の露光装置を用いて、所定のマスクパターンを有するマスクを介して露光することで、パターン露光することができる。これにより、露光部分を硬化することができる。
露光に際して用いることができる放射線(光)としては、g線、i線等の紫外線が好ましく(特に好ましくはi線)用いられる。照射量(露光量)は、例えば、0.03~2.5J/cm2が好ましく、0.05~1.0J/cm2がより好ましく、0.08~0.5J/cm2が更に好ましい。
露光時における酸素濃度については適宜選択することができ、大気下で行う他に、例えば酸素濃度が19体積%以下の低酸素雰囲気下(好ましくは15体積%以下、より好ましくは5体積%以下、更に好ましくは実質的に無酸素)で露光してもよく、酸素濃度が21体積%を超える高酸素雰囲気下(好ましくは22体積%以上、より好ましくは30体積%以上、更に好ましくは50体積%以上)で露光してもよい。露光照度は適宜設定することが可能であり、通常1000W/m2~100000W/m2(好ましくは5000W/m2以上、より好ましくは15000W/m2以上、更に好ましくは35000W/m2以上)の範囲から選択することができる。酸素濃度と露光照度は適宜条件を組み合わせてよく、例えば、酸素濃度10体積%で照度10000W/m2、酸素濃度35体積%で照度20000W/m2などとすることができる。
次に、未露光部を現像除去してパターンを形成する。未露光部の現像除去は、現像液を用いて行うことができる。これにより、露光工程における未露光部の組成物層が現像液に溶出し、光硬化した部分だけが支持体上に残る。
現像液としては、下地の固体撮像素子や回路などにダメージを与えないアルカリ現像液が望ましい。
現像液の温度は、例えば、20~30℃が好ましい。現像時間は、20~180秒が好ましい。また、残渣除去性を向上するため、現像液を60秒ごとに振り切り、更に新たに現像液を供給する工程を数回繰り返してもよい。
ドライエッチング法でのパターン形成は、支持体上に形成した組成物層を硬化して硬化物層を形成し、次いで、得られた硬化物層を、パターニングされたフォトレジスト層をマスクとしてエッチングガスを用いて行うことができる。フォトレジスト層の形成においては、更にプリベーク処理を施すことが好ましい。特に、フォトレジストの形成プロセスとしては、露光後の加熱処理、現像後の加熱処理(ポストベーク処理)を実施する形態が望ましい。ドライエッチング法でのパターン形成については、特開2013-064993号公報の段落番号0010~0067の記載を参酌でき、この内容は本明細書に組み込まれる。
次に、本発明における硬化膜について説明する。本発明の膜は、上述した本発明の組成物を硬化して形成されるものである。本発明の硬化膜は、赤外線透過フィルタとして好ましく用いることができる。
本発明の硬化膜は、膜の厚み方向における光の透過率の、波長400~700nmの範囲における最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、膜の厚み方向における光の透過率の、波長1100~1300nmの範囲における最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)であることが好ましい。この態様によれば、波長400~700nmの範囲の光を遮光して、可視光線由来のノイズが少ない状態で赤外線を透過可能な膜とすることができる。
(2):膜の厚み方向における光の透過率の、波長400~830nmの範囲における最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、膜の厚み方向における光の透過率の、波長1000~1300nmの範囲における最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)である態様。この態様によれば、波長400~830nmの範囲の光を遮光して、可視光線由来のノイズが少ない状態で波長1000nm以上の赤外線を透過可能な膜とすることができる。
(3):膜の厚み方向における光の透過率の、波長400~950nmの範囲における最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、膜の厚み方向における光の透過率の、波長1100~1300nmの範囲における最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)である態様。この態様によれば、波長400~950nmの範囲の光を遮光して、可視光線由来のノイズが少ない状態で波長1100nm以上の赤外線を透過可能な膜とすることができる。
上記(2)の分光特性を有する硬化膜は、近赤外線透過黒色色材の他にさらに赤外線吸収剤を含む本発明の組成物を用いて形成できる。赤外線吸収剤は、波長800nm以上900nm未満の範囲に極大吸収波長を有する化合物であることが好ましい。また、更に有彩色着色剤を含有させることで、上記(2)の分光を好ましい範囲に調整しやすい。
上記(3)の分光特性を有する硬化膜は、近赤外線透過黒色色材の他にさらに赤外線吸収剤を含む本発明の組成物を用いて形成できる。赤外線吸収剤は、波長900nm以上1000nm未満の範囲に極大吸収波長を有する化合物であることが好ましい。また、更に有彩色着色剤および/または波長800nm以上900nm未満の範囲に極大吸収波長を有する化合物を含有させることで、上記(3)の分光を好ましい範囲に調整しやすい。
次に、本発明の赤外線透過フィルタについて説明する。本発明の赤外線透過フィルタは、本発明の硬化膜を有する。
本発明の固体撮像素子は、本発明の硬化膜を有する。本発明の固体撮像素子の構成は、本発明の硬化膜体を有し、固体撮像素子として機能する構成であれば特に限定はないが、例えば、以下のような構成が挙げられる。
本発明の赤外線センサは、本発明の硬化膜を有する。本発明の赤外線センサの構成は、本発明の硬化膜を有し、赤外線センサとして機能する構成であれば特に限定はない。
図1に示す赤外線センサ100において、符号110は、固体撮像素子である。
固体撮像素子110上に設けられている撮像領域は、赤外線カットフィルタ111とカラーフィルタ112を有する。
赤外線カットフィルタ111は、可視光線領域の光(例えば、波長400~700nmの光)を透過させ、赤外領域の光(例えば、波長800~1300nmの光の少なくとも一部、好ましくは波長900~1200nmの光の少なくとも一部、更に好ましくは波長900~1000nmの光の少なくとも一部)を遮蔽するフィルタである。
カラーフィルタ112は、可視光線領域における特定波長の光を透過及び吸収する画素が形成されたカラーフィルタであって、例えば、赤色(R)、緑色(G)、青色(B)の画素が形成されたカラーフィルタなどが用いられる。
赤外線透過フィルタ113と固体撮像素子110との間には赤外線カットフィルタ111が形成されていない領域114が設けられている。領域114には、赤外線透過フィルタ113を透過した波長の光が透過可能な樹脂層(例えば、透明樹脂層など)が配置されている。
赤外線透過フィルタ113は、可視光線遮蔽性を有し、かつ、特定波長の赤外線を透過させるフィルタであって、本発明の硬化膜で構成されている。
カラーフィルタ112および赤外線透過フィルタ113の入射光hν側には、マイクロレンズ115が配置されている。マイクロレンズ115を覆うように平坦化層116が形成されている。
図1に示す実施形態では、領域114に樹脂層が配置されているが、領域114に赤外線透過フィルタ113を形成してもよい。すなわち、固体撮像素子110上に、赤外線透過フィルタ113を形成してもよい。
図1に示す実施形態では、カラーフィルタ112の膜厚と、赤外線透過フィルタ113の膜厚が同一であるが、両者の膜厚は異なっていてもよい。
図1に示す実施形態では、カラーフィルタ112が、赤外線カットフィルタ111よりも入射光hν側に設けられているが、赤外線カットフィルタ111と、カラーフィルタ112との順序を入れ替えて、赤外線カットフィルタ111を、カラーフィルタ112よりも入射光hν側に設けてもよい。
図1に示す実施形態では、赤外線カットフィルタ111とカラーフィルタ112は隣接して積層しているが、両フィルタは必ずしも隣接している必要はなく、間に他の層が設けられていても良い。
この赤外線センサによれば、画像情報をリアルタイムに取り込むことができるため、動きを検知する対象を認識したモーションセンシングなどが可能である。更には、距離情報を取得できるため、3D情報を含んだ画像の撮影等も可能である。
(組成物1;実施例1)
樹脂A1を9.0質量部と、色材D1を2.0質量部と、重合性化合物としてKAYARAD DPHA(日本化薬(株)製)を1.5質量部と、光重合開始剤を1.5質量部と、溶剤としてプロピレングリコールモノメチルエーテルアセテート(PGMEA)を86.0質量部とを混合し、撹拌した後、孔径0.5μmのナイロン製フィルタ(日本ポール(株)製)でろ過して、組成物1を得た。
色材D1のかわりに色材D2を用いた以外は組成物1と同様にして、組成物2を得た。
色材D1のかわりに色材D3を用いた以外は組成物1と同様にして、組成物3を得た。
樹脂A2を9.0質量部と、色材D4を2.0質量部と、重合性化合物としてKAYARAD DPHA(日本化薬(株)製)を1.5質量部と、光重合開始剤を1.5質量部と、溶剤としてPGMEAを86.0質量部とを混合し、撹拌した後、孔径0.5μmのナイロン製フィルタ(日本ポール(社)製)でろ過して、組成物4を得た。
樹脂A2を9.0質量部と、色材D5を0.5質量部と、色材D3を1.5質量部と、重合性化合物としてKAYARAD DPHA(日本化薬(株)製)を1.5質量部と、光重合開始剤を1.5質量部と、溶剤としてPGMEAを86.0質量部とを混合し、撹拌した後、孔径0.5μmのナイロン製フィルタ(日本ポール(株)製)でろ過して、組成物5を得た。
樹脂A1を8.0質量部と、樹脂A3を1.0質量部と、色材D1を2.0質量部と、重合性化合物としてKAYARAD DPHA(日本化薬(株)製)を1.5質量部と、光重合開始剤を1.5質量部と、PGMEAを70.0質量部と、塩化メチレンを16.0質量部とを混合し、撹拌した後、孔径0.5μmのナイロン製フィルタ(日本ポール(株)製)でろ過して、組成物6を得た。
樹脂A1を8.0質量部と、樹脂A4を1.0質量部と、色材D3を2.0質量部と、色材D7を0.2質量部と、重合性化合物としてKAYARAD DPHA(日本化薬(株)製)を1.5質量部と、光重合開始剤を1.5質量部と、PGMEAを86.0質量部とを混合し、撹拌した後、孔径0.5μmのナイロン製フィルタ(日本ポール(株)製)でろ過して、組成物7を得た。
色材D1のかわりに色材D6を用いた以外は組成物1と同様にして、組成物8を得た。
色材D6の含有量を0.5質量部に変更した以外は組成物8と同様にして、組成物9を得た。
黒色顔料(BASF社製 Irgaphor Black S0100CF)を600.0gと、アクリル樹脂A(メチルメタクリレート/メタクリル酸/スチレン共重合体(質量比30/40/30、Mw=10,000、酸価=110mgKOH/g))のプロピレングリコールモノメチルエーテルアセテート35質量%溶液を321.4gと、分散剤(BYK21116;ビックケミー社製)を93.8gと、プロピレングリコールモノエチルエーテルアセテート(PGMEA)を1984.8gとをタンクに加え、ホモミキサー(特殊機化製)で1時間撹拌し、予備分散液1を得た。その後、直径0.10mmのジルコニアビーズ(東レ製)を70%充填した遠心分離セパレーターを具備した、ウルトラアペックスミル(寿工業製)に予備分散液1を供給し、回転速度8m/sで2時間分散を行い、固形分濃度25質量%、顔料/樹脂(質量比)=80/20の黒色顔料分散液1を得た。
PGMEA29.52gに、光重合開始剤としてアデカアークルズ(登録商標)NCI-831を0.38g添加し、固形分が溶解するまで撹拌した。さらに、アクリル樹脂AのPGMEA35質量%溶液を16.03g、重合性化合物としてKAYARAD DPHA(日本化薬(株)製)を3.38g、界面活性剤としてシリコーン系界面活性剤BYK333のプロピレングリコールモノメチルエーテルアセテート(PMA)10質量%溶液を0.24g添加し、室温にて1時間撹拌し、感光性レジストを得た。この感光性レジストに黒色顔料分散液1を10.46g添加することで組成物10を調製した。
樹脂A1:下記構造の樹脂(Mw=40,000)。主鎖に付記した数値はモル比である。
樹脂A2:下記構造の樹脂(Mw=14,000)。主鎖に付記した数値はモル比である。
樹脂A3:ARTON F4520(JSR(株)製)、ノルボルネン樹脂)
樹脂A4:マープルーフG-0150M(日油(株)製、メタクリル酸グリシジル骨格ランダムポリマー)
光重合開始剤:下記構造の化合物
各組成物を、ポストベーク後の膜厚が1.1μmとなるようにガラス基板上にスピンコートし、ホットプレートを用いて100℃、120秒間加熱して乾燥した。乾燥後、さらに、ホットプレートを用いて220℃、300秒間加熱(ポストベーク)して硬化膜を形成した。硬化膜を形成したガラス基板を、紫外可視近赤外分光光度計(日立ハイテクノロジーズ社製 U-4100)を用いて、波長300~1300nmの範囲の透過率、波長400~700nmの範囲における吸光度の最小値A、波長1100~1300nmの範囲における吸光度の最大値Bを測定した。各組成物の分光特性A/Bの値を下記表に示す。
各組成物を、ポストベーク後の膜厚が1.1μmとなるようにシリコンウェハ上にスピンコートし、ホットプレートを用いて100℃、120秒間加熱して乾燥した。次いで、i線ステッパー露光装置FPA-3000i5+(Canon(株)製)を使用して、1.1μm四方の正方形ピクセルパターンが形成されるフォトマスクを用いて50から750mJ/cm2まで50mJ/cm2ずつ上昇させて、上記正方形ピクセルパターンを解像する最適露光量を決定し、この最適露光量にて露光を行った。その後、露光された塗布膜が形成されているシリコンウェハをスピン・シャワー現像機(DW-30型、(株)ケミトロニクス製)の水平回転テーブル上に載置し、CD-2060(テトラメチルアンモニウムヒドロキシド水溶液、富士フイルムエレクトロニクスマテリアルズ(株)製)を用いて23℃で60秒間パドル現像を行い、シリコンウェハ上にパターンを形成した。パターンが形成されたシリコンウェハを純水でリンス処理を行い、その後スピン乾燥した。次いで、220℃のホットプレートを用いて300秒間加熱処理(ポストベーク)を行い、パターンを有するシリコンウェハ(赤外線透過フィルタ)を得た。
赤外線透過フィルタをPGMEAに300秒浸漬し、PGMEAに浸漬前後の波長400~700nmの光の透過率(単位%)を測定し、下記式により透過率の変化を求めた。なお、透過率の変化は、PGMEAに浸漬前後の透過率の変化が最も大きい波長における透過率にて評価した。
透過率の変化=|(PGMEAに浸漬した後の透過率(%)-PGMEAに浸漬する前の透過率(%))|
耐溶剤性を以下の基準に従い評価した。
3:浸漬前後の透過率の変化が3%未満
2:浸漬前後の透過率の変化が3%以上5%未満
1:浸漬前後の透過率の変化が5%以上
得られたパターン形状を以下の基準に従い評価した。
3:明瞭な正方形形状を認識できる。
2:正方形形状を認識できる
1:形状が崩れている
得られた赤外線透過フィルタを公知の方法に従い固体撮像素子に組み込んだ。得られた固体撮像素子にて低照度の環境下(0.001Lux)で発光波長940nmの近赤外LED(発光ダイオード)光源を照射し、画像の取り込みを行い、画像性能を比較評価した。
分光認識を以下の基準に従い評価した。
3:良好 画像上で被写体をはっきり認識できる。
2:やや良好 画像上で被写体を認識できる。
1:不十分 画像上で被写体を認識できない。
Claims (10)
- 近赤外線透過黒色色材と、硬化性化合物と、溶剤とを含む組成物であって、
前記近赤外線透過黒色色材は、架橋性基を有する染料化合物、および、前記染料化合物由来の構造を有する色素多量体から選ばれる少なくとも1種を含有し、
前記組成物の波長400~700nmの範囲における吸光度の最小値Aと、波長1100~1300nmの範囲における吸光度の最大値Bとの比であるA/Bが4.5以上である、組成物。 - 前記染料化合物が有する架橋性基は、エチレン性不飽和結合を有する基、エポキシ基およびアルコキシシリル基から選ばれる少なくとも1種である、請求項1に記載の組成物。
- 前記架橋性基を有する染料化合物は、キサンテン化合物、ペリレン化合物、アゾ化合物およびビスベンゾフラノン化合物から選ばれる少なくとも1種である、請求項1または2に記載の組成物。
- 前記色素多量体は、2価以上の連結基に前記染料化合物由来の構造が2以上結合してなる、請求項1~3のいずれか1項に記載の組成物。
- 前記色素多量体は、前記染料化合物由来の構造を有する繰り返し単位を有する、請求項1~3のいずれか1項に記載の組成物。
- 更に、有彩色着色剤を含む、請求項1~5のいずれか1項に記載の組成物。
- 請求項1~6のいずれか1項に記載の組成物を硬化してなる硬化膜。
- 請求項7に記載の硬化膜を有する赤外線透過フィルタ。
- 請求項7に記載の硬化膜を有する固体撮像素子。
- 請求項7に記載の硬化膜を有する赤外線センサ。
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WO2019230684A1 (ja) * | 2018-06-01 | 2019-12-05 | 東レ株式会社 | 着色樹脂組成物とその製造方法、近赤外線透過遮光膜および加飾基板 |
WO2023022199A1 (ja) * | 2021-08-18 | 2023-02-23 | 積水化学工業株式会社 | 近赤外線透過黒色粒子 |
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KR20190008327A (ko) | 2019-01-23 |
KR102129747B1 (ko) | 2020-07-03 |
JP6629976B2 (ja) | 2020-01-15 |
TWI733858B (zh) | 2021-07-21 |
JPWO2018034082A1 (ja) | 2019-06-13 |
TW201809874A (zh) | 2018-03-16 |
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