WO2018139533A1 - 組成物、膜、近赤外線カットフィルタ、固体撮像素子、画像表示装置および赤外線センサ - Google Patents
組成物、膜、近赤外線カットフィルタ、固体撮像素子、画像表示装置および赤外線センサ Download PDFInfo
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- WO2018139533A1 WO2018139533A1 PCT/JP2018/002278 JP2018002278W WO2018139533A1 WO 2018139533 A1 WO2018139533 A1 WO 2018139533A1 JP 2018002278 W JP2018002278 W JP 2018002278W WO 2018139533 A1 WO2018139533 A1 WO 2018139533A1
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- SHDTVGWZVWSJNL-FMIFUCRQSA-N CC[n]1c(ccc(C(c2c(C)cccc2)=O)c2)c2c2cc(C(/C(/CCSc(cc3)ccc3Cl)=N/OC(C)=O)=O)ccc12 Chemical compound CC[n]1c(ccc(C(c2c(C)cccc2)=O)c2)c2c2cc(C(/C(/CCSc(cc3)ccc3Cl)=N/OC(C)=O)=O)ccc12 SHDTVGWZVWSJNL-FMIFUCRQSA-N 0.000 description 1
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Definitions
- the present invention relates to a composition, a film, a near infrared cut filter, a solid-state image sensor, an image display device, and an infrared sensor.
- Video cameras, digital still cameras, mobile phones with camera functions, etc. use CCD (Charge Coupled Device) and CMOS (Complementary Metal Oxide Semiconductor), which are solid-state imaging devices for color images. These solid-state imaging devices use silicon photodiodes having sensitivity to infrared rays in the light receiving portion. For this reason, visual sensitivity correction may be performed using a near-infrared cut filter.
- CCD Charge Coupled Device
- CMOS Complementary Metal Oxide Semiconductor
- the near-infrared cut filter is manufactured using a composition containing a near-infrared absorbing compound.
- a near-infrared absorbing compound a compound having a wide ⁇ -conjugated plane is used.
- Patent Document 1 describes that a near-infrared cut fill is produced using a pyrrolopyrrole compound.
- Near-infrared absorbing compounds having a ⁇ -conjugated plane tend to agglomerate in the composition due to interaction between ⁇ -conjugated planes, etc., and the viscosity of the composition tends to increase over time. For this reason, in recent years, further improvement in the temporal stability of a composition containing a near-infrared absorbing compound is desired.
- the present invention provides the following. ⁇ 1> a near-infrared absorbing compound having a ⁇ -conjugated plane including a monocyclic or condensed aromatic ring; A compound A having a radically polymerizable ethylenically unsaturated group and a weight average molecular weight of 3000 or more, The compound A comprises a repeating unit having a graft chain.
- the radically polymerizable ethylenically unsaturated group of the compound A is at least one selected from vinyl group, vinyloxy group, allyl group, methallyl group, (meth) acryloyl group, styrene group, cinnamoyl group and maleimide group.
- the graft chain includes at least one structure selected from a polyester structure, a polyether structure, a poly (meth) acrylic structure, a polyurethane structure, a polyurea structure, and a polyamide structure, according to ⁇ 1> or ⁇ 2>.
- Composition is at least one selected from vinyl group, vinyloxy group, allyl group, methallyl group, (meth) acryloyl group, styrene group, cinnamoyl group and maleimide group.
- the repeating unit having a graft chain has a weight average molecular weight of 1000 or more.
- the compound A includes a repeating unit having a radical polymerizable ethylenically unsaturated group and a repeating unit having a graft chain.
- Compound A includes a repeating unit represented by the following formula (A-1-1) and a repeating unit represented by the following formula (A-1-2): ⁇ 1> to ⁇ 6> A composition according to any one of;
- X 1 represents a main chain of a repeating unit
- L 1 represents a single bond or a divalent linking group
- Y 1 represents a group having a radical polymerizable ethylenically unsaturated group.
- X 2 represents a main chain of a repeating unit, L 2 represents a single bond or a divalent linking group, and W 1 represents a graft chain.
- amount of the radically polymerizable ethylenically unsaturated group of Compound A is 0.2 to 5.0 mmol / g.
- acid value of compound A is 20 to 150 mgKOH / g.
- the near-infrared absorbing compound is at least one selected from a pyrrolopyrrole compound, a cyanine compound, a squarylium compound, a phthalocyanine compound, a naphthalocyanine compound, and a diimonium compound, and any one of ⁇ 1> to ⁇ 10>
- ⁇ 12> The composition according to any one of ⁇ 1> to ⁇ 11>, further comprising a colorant that transmits infrared rays and blocks visible light.
- ⁇ 13> A film obtained from the composition according to any one of ⁇ 1> to ⁇ 12>.
- ⁇ 14> A near-infrared cut filter having the film according to ⁇ 13>.
- ⁇ 15> A solid-state imaging device having the film according to ⁇ 13>.
- ⁇ 16> An image display device having the film according to ⁇ 13>.
- ⁇ 17> An infrared sensor having the film according to ⁇ 13>.
- a composition capable of producing a film having good temporal stability and excellent adhesion to a support or the like.
- membrane, a near-infrared cut filter, a solid-state image sensor, an image display apparatus, and an infrared sensor can be provided.
- ⁇ is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
- the notation in which neither substitution nor substitution is described includes a group (atomic group) having a substituent together with a group (atomic group) having no 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.
- 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.
- 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-8220GPC (manufactured by Tosoh Corporation), and as columns, TOSOH TSKgel Super HZM-H and TOSOH TSKgel Super HZ4000 It can be determined by using a column connected with TOSOH TSKgel Super HZ2000 and using tetrahydrofuran as a developing solvent.
- Me in the chemical formula represents a methyl group
- Et represents an ethyl group
- Bu represents a butyl group
- Ph represents a phenyl group.
- near-infrared light refers to light (electromagnetic wave) having a wavelength of 700 to 2500 nm.
- the total solid content refers to the total mass of components obtained by removing the solvent from all components of the composition.
- 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. .
- composition of the present invention comprises a near-infrared absorbing compound having a ⁇ -conjugated plane containing a monocyclic or condensed aromatic ring, a compound A having a radical polymerizable ethylenically unsaturated group and a weight average molecular weight of 3000 or more, Compound A is characterized in that it contains a repeating unit having a graft chain.
- the composition of the present invention can produce a film having good temporal stability and excellent adhesion to a support or the like. It is estimated that the reason why such an effect is obtained is as follows.
- the radically polymerizable ethylenically unsaturated group of compound A interacts with the ⁇ -conjugated plane of the near infrared absorbing compound so that compound A comes close to the near infrared absorbing compound, and the near infrared absorbing compound is wrapped in compound A.
- this compound A has the repeating unit which has a graft chain, it is estimated that the near infrared absorption compound association can be suppressed by the steric hindrance by the graft chain.
- the dispersibility of a near-infrared absorption compound can be improved and it can be set as the composition excellent in temporal stability.
- the compound A has a radically polymerizable ethylenically unsaturated group, since the radically polymerizable ethylenically unsaturated group is excellent in reactivity, it is presumed that the curability of the film can be improved.
- the compound A is polymerized in the vicinity of the near-infrared absorbing compound, it is presumed that the increase in molecular weight due to the polymerization is increased, and the curability of the film can be further increased. For this reason, it is estimated that the adhesiveness with respect to the support body etc. of a film
- each component of the composition of the present invention will be described.
- the composition of the present invention contains a near-infrared absorbing compound that is a compound having a ⁇ -conjugated plane including a monocyclic or condensed aromatic ring.
- the near-infrared absorbing compound is preferably a compound having absorption in the near-infrared region (preferably in the wavelength range of 700 to 1300 nm, more preferably in the wavelength range of 700 to 1000 nm).
- the near-infrared absorbing compound in the present invention has a ⁇ -conjugate plane containing a monocyclic or condensed aromatic ring, the interaction between the aromatic rings in the ⁇ -conjugated plane of the near-infrared absorbing compound causes the near-infrared absorbing compound in the film.
- a J-aggregate of an infrared absorbing compound can be easily formed, and a film excellent in near-infrared spectrum can be formed.
- the near-infrared absorbing compound may be a pigment (also referred to as a near-infrared absorbing pigment) or a dye (also referred to as a near-infrared absorbing dye).
- the number of atoms other than hydrogen constituting the ⁇ -conjugated plane of the near-infrared absorbing compound is preferably 14 or more, more preferably 20 or more, still more preferably 25 or more, 30
- the above is particularly preferable.
- the upper limit is preferably 80 or less, and more preferably 50 or less.
- the ⁇ -conjugated plane of the near-infrared absorbing compound preferably contains two or more monocyclic or condensed aromatic rings, more preferably contains three or more of the aforementioned aromatic rings, and includes the aforementioned aromatic rings. More preferably, it contains 4 or more, and particularly preferably contains 5 or more of the aforementioned aromatic rings.
- the upper limit is preferably 100 or less, more preferably 50 or less, and still more preferably 30 or less.
- aromatic ring examples include benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, quaterylene ring, acenaphthene ring, phenanthrene ring, anthracene ring, naphthacene ring, Chrysene ring, triphenylene ring, fluorene ring, pyridine ring, quinoline ring, isoquinoline ring, imidazole ring, benzimidazole ring, pyrazole ring, thiazole ring, benzothiazole ring, triazole ring, benzotriazole ring, oxazole ring, benzoxazole ring, imidazoline Ring, pyrazine ring, quinoxaline ring, pyrimidine ring, qui
- the near-infrared absorbing compound is preferably a compound having a maximum absorption wavelength in the wavelength range of 700 to 1000 nm.
- “having a maximum absorption wavelength in the wavelength range of 700 to 1000 nm” means a wavelength exhibiting the maximum absorbance in the wavelength range of 700 to 1000 nm in the absorption spectrum of the near-infrared absorbing compound solution. It means having.
- the measurement solvent used for measuring the absorption spectrum in the solution of the near-infrared absorbing compound include chloroform, methanol, dimethyl sulfoxide, ethyl acetate, and tetrahydrofuran. In the case of a compound dissolved in chloroform, chloroform is used as a measurement solvent. For compounds that do not dissolve in chloroform, use methanol. Also, dimethyl sulfoxide is used when it does not dissolve in either chloroform or methanol.
- Near-infrared absorbing compound is a compound having a maximum absorption wavelength in the wavelength range of 700 to 1000 nm, and a ratio of absorbance Amax at the maximum absorption wavelength to absorbance A550 at a wavelength of 550 nm is Amax / A550 of 50 to 500 It is preferable that Amax / A550 in the near-infrared absorbing compound is preferably 70 to 450, more preferably 100 to 400. According to this aspect, it is easy to produce a film excellent in visible transparency and near-infrared shielding properties.
- the absorbance A550 at a wavelength of 550 nm and the absorbance Amax at the maximum absorption wavelength are values obtained from an absorption spectrum of the near-infrared absorbing compound in a solution.
- the near-infrared absorbing compound it is also preferable to use at least two compounds having different maximum absorption wavelengths. According to this aspect, the waveform of the absorption spectrum of the film is wider than when one kind of near-infrared absorbing compound is used, and near-infrared rays in a wide wavelength range can be shielded.
- the first near-infrared absorbing compound having a maximum absorption wavelength in the wavelength range of 700 to 1000 nm and a wavelength shorter than the maximum absorption wavelength of the first near-infrared absorbing compound At least a second near-infrared absorbing compound having a maximum absorption wavelength in a wavelength range of 700 to 1000 nm, the maximum absorption wavelength of the first near-infrared absorption compound, and the second near-infrared absorption compound
- the difference from the maximum absorption wavelength is preferably 1 to 150 nm.
- the near-infrared absorbing compound is a pyrrolopyrrole compound, cyanine compound, squarylium compound, phthalocyanine compound, naphthalocyanine compound, quaterylene compound, merocyanine compound, croconium compound, oxonol compound, diimonium compound, dithiol compound, triarylmethane compound, At least one selected from a pyromethene compound, an azomethine compound, an anthraquinone compound and a dibenzofuranone compound is preferable, and at least one selected from a pyrrolopyrrole compound, a cyanine compound, a squarylium compound, a phthalocyanine compound, a naphthalocyanine compound and a diimonium compound is more preferable, At least one selected from a pyrrolopyrrole compound, a cyanine compound, and a squarylium compound But more preferably, pyrrolo-
- Examples of the diimonium compound include compounds described in JP-T-2008-528706, and the contents thereof are incorporated herein.
- Examples of the phthalocyanine compound include compounds described in paragraph No. 0093 of JP2012-77153A, oxytitanium phthalocyanine described in JP2006-343631, paragraph Nos. 0013 to 0029 of JP2013-195480A. And the contents of which are incorporated herein.
- Examples of the naphthalocyanine compound include compounds described in paragraph No. 0093 of JP2012-77153A, the contents of which are incorporated herein.
- the compounds described in paragraph Nos. 0010 to 0081 of JP-A No. 2010-1111750 may be used. Incorporated.
- the cyanine compound for example, “functional pigment, Nobu Okawara / Ken Matsuoka / Kojiro Kitao / Kensuke Hirashima, Kodansha Scientific”, the contents of which are incorporated herein. .
- the near-infrared absorbing compound compounds described in JP-A-2016-146619 can also be used, and the contents thereof are incorporated in the present specification.
- the pyrrolopyrrole compound is preferably a compound represented by the formula (PP).
- R 1a and R 1b each independently represent an alkyl group, an aryl group or a heteroaryl group
- R 2 and R 3 each independently represent a hydrogen atom or a substituent
- R 2 and R 3 are They may combine with each other to form a ring
- each R 4 independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, —BR 4A R 4B , or a metal atom
- R 4 represents R At least one selected from 1a , R 1b and R 3 may be covalently or coordinately bonded
- R 4A and R 4B each independently represent a substituent.
- R 1a and R 1b are each independently preferably an aryl group or a heteroaryl group, more preferably an aryl group. Further, the alkyl group, aryl group and heteroaryl group represented by R 1a and R 1b may have a substituent or may be unsubstituted. Examples of the substituent include an alkoxy group, a hydroxyl group, a halogen atom, a cyano group, a nitro group, —OCOR 11 , —SOR 12 , —SO 2 R 13 and the like. R 11 to R 13 each independently represents a hydrocarbon group or a heterocyclic group. Examples of the substituent include those described in paragraphs 0020 to 0022 of JP-A-2009-263614.
- an alkoxy group, a hydroxyl group, a cyano group, a nitro group, —OCOR 11 , —SOR 12 , and —SO 2 R 13 are preferable.
- an aryl group having an alkoxy group having a branched alkyl group as a substituent, an aryl group having a hydroxyl group as a substituent, or a group represented by —OCOR 11 is substituted.
- An aryl group as a group is preferable.
- the branched alkyl group preferably has 3 to 30 carbon atoms, and more preferably 3 to 20 carbon atoms.
- At least one of R 2 and R 3 is preferably an electron withdrawing group, R 2 represents an electron withdrawing group (preferably a cyano group), and R 3 more preferably represents a heteroaryl group.
- the heteroaryl group is preferably a 5-membered ring or a 6-membered ring.
- the heteroaryl group is preferably a single ring or a condensed ring, more preferably a single ring or a condensed ring having 2 to 8 condensations, and more preferably a single ring or a condensed ring having 2 to 4 condensations.
- the number of heteroatoms constituting the heteroaryl group is preferably 1 to 3, more preferably 1 to 2.
- hetero atom examples include a nitrogen atom, an oxygen atom, and a sulfur atom.
- the heteroaryl group preferably has one or more nitrogen atoms.
- Two R 2 in the formula (PP) may be the same or different.
- two R ⁇ 3 > in Formula (PP) may be the same, and may differ.
- R 4 is a hydrogen atom, an alkyl group, an aryl group, preferably a group represented by heteroaryl group or -BR 4A R 4B, a hydrogen atom, an alkyl group, represented by an aryl group or -BR 4A R 4B More preferably a group represented by —BR 4A R 4B .
- the substituent represented by R 4A and R 4B is preferably a halogen atom, an alkyl group, an alkoxy group, an aryl group, or a heteroaryl group, more preferably an alkyl group, an aryl group, or a heteroaryl group, and an aryl group. Particularly preferred. These groups may further have a substituent.
- Two R 4 s in formula (PP) may be the same or different.
- Specific examples of the compound represented by the formula (PP) include the following compounds.
- Me represents a methyl group
- Ph represents a phenyl group.
- 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 No. 2011-68731, and international publication WO2015 / 166873. Examples include compounds described in paragraph numbers 0010 to 0033 of the publication, and the contents thereof are incorporated in the present specification.
- a 1 and A 2 each independently represents an aryl group, a heteroaryl group or a group represented by formula (A-1);
- Z 1 represents a nonmetallic atomic group that forms a nitrogen-containing heterocyclic ring
- R 2 represents an alkyl group, an alkenyl group, or an aralkyl group
- d represents 0 or 1
- a wavy line represents a connecting hand.
- squarylium compound examples include the following compounds.
- examples of the squarylium compound include compounds described in paragraph numbers 0044 to 0049 of JP2011-208101A, the contents of which are incorporated herein.
- the cyanine compound is preferably a compound represented by the formula (C).
- Z 1 and Z 2 are each independently a nonmetallic atomic group that forms a 5-membered or 6-membered nitrogen-containing heterocyclic ring that may be condensed
- R 101 and R 102 each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group
- L 1 represents a methine chain having an odd number of methine groups
- a and b are each independently 0 or 1
- X 1 represents an anion
- c represents the number necessary for balancing the charge
- the site represented by Cy in the formula is an anion moiety.
- X 1 represents
- Examples of the cyanine compound include compounds described in paragraph Nos. 0044 to 0045 of JP-A-2009-108267, compounds described in paragraph Nos. 0026 to 0030 of JP-A No. 2002-194040, and JP-A-2015-172004. And the compounds described in JP-A No. 2015-172102, the compounds described in JP-A-2008-88426, and the like, the contents of which are incorporated herein.
- a commercially available product can be used as the near-infrared absorbing compound.
- SDO-C33 manufactured by Arimoto Chemical Industry Co., Ltd.
- e-ex color IR-14 e-ex color IR-10A
- e-ex color TX-EX-801B e-ex color TX-EX-805K (inc.
- the content of the near-infrared absorbing compound is preferably 10 to 90% by mass with respect to the total solid content of the composition.
- the lower limit is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, and particularly preferably 45% by mass or more.
- the upper limit of the content of the near-infrared absorbing compound is preferably 80% by mass or less, more preferably 70% by mass or less, and further preferably 65% by mass or less.
- the content of the near-infrared absorbing compound is preferably 100 to 500 parts by mass with respect to 100 parts by mass of Compound A described later. In the present invention, only one type of near-infrared absorbing compound may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.
- the composition of the present invention may further contain a near-infrared absorber other than the above-mentioned near-infrared absorbing compound (also referred to as other near-infrared absorber).
- Other near infrared absorbers include inorganic pigments (inorganic particles).
- the shape of the inorganic pigment is not particularly limited, and may be a sheet shape, a wire shape, or a tube shape regardless of spherical or non-spherical.
- metal oxide particles or metal particles are preferable.
- 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). SnO 2 ) particles, niobium-doped titanium dioxide (Nb-doped TiO 2 ) particles, and the like.
- the metal particles include silver (Ag) particles, gold (Au) particles, copper (Cu) particles, and nickel (Ni) particles.
- a tungsten oxide compound can also be used as the inorganic pigment.
- 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 content of the other near infrared absorber is preferably 0.01 to 50% by mass with respect to the total solid content of the composition.
- the lower limit is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more.
- the upper limit is preferably 30% by mass or less, and more preferably 15% by mass or less.
- the content of the other near-infrared absorbing compound in the total mass of the above-mentioned near-infrared absorbing compound and other near-infrared absorbing agent is preferably 1 to 99% by mass.
- the upper limit is preferably 80% by mass or less, more preferably 50% by mass or less, and further preferably 30% by mass or less.
- the composition of this invention does not contain other near-infrared absorbers substantially.
- “Contains substantially no other near-infrared absorber” means that the content of the other near-infrared absorber in the total mass of the above-mentioned near-infrared-absorbing compound and other near-infrared absorber is 0.5% by mass or less. It is preferable that it is 0.1 mass% or less, and it is still more preferable not to contain other near-infrared absorbers.
- composition of the present invention comprises a compound A containing a repeating unit having a graft chain and having a radically polymerizable ethylenically unsaturated group and having a weight average molecular weight (Mw) of 3000 or more.
- compound A can also be used as a dispersant.
- the weight average molecular weight of Compound A is 3000 or more, preferably 3000 to 50,000, more preferably 7000 to 40,000, and still more preferably 10,000 to 30,000.
- the weight average molecular weight of Compound A is 3000 or more, the dispersibility of the light shielding material and the like is good.
- a vinyl group, vinyloxy group, allyl group, methallyl group, (meth) acryloyl group, styrene group, cinnamoyl group and maleimide group are preferable, and a (meth) acryloyl group is preferred.
- (Meth) acryloyl group, styrene group and maleimide group are more preferred, (meth) acryloyl group is still more preferred, and acryloyl group is particularly preferred.
- the (meth) acryloyl group is particularly excellent in reactivity and is a group having a small steric hindrance, the (meth) acryloyl group does not easily interact with the ⁇ -conjugated plane of the near-infrared absorbing compound, and the effects of the present invention can be obtained more remarkably.
- the upper limit is more preferably 4.0 mmol / g or less, and still more preferably 3.0 mmol / g or less.
- the lower limit is more preferably 0.3 mmol / g or more.
- the content can be measured by high performance liquid chromatography (HPLC) and calculated from the following formula.
- HPLC high performance liquid chromatography
- NMR method nuclear magnetic resonance
- the radically polymerizable ethylenically unsaturated group is preferably present in the side chain of the repeating unit. That is, the compound A preferably contains a repeating unit represented by the following formula (A-1-1).
- A-1-1 X 1 represents a main chain of a repeating unit
- L 1 represents a single bond or a divalent linking group
- Y 1 represents a group having a radical polymerizable ethylenically unsaturated group. Represents.
- the main chain of the repeating unit represented by X 1 is not particularly limited.
- Any linking group formed from known polymerizable monomers is not particularly limited.
- Poly (meth) acrylic linking groups and polyalkyleneimine linking groups are preferred, and (meth) acrylic linking groups are more preferred from the viewpoints of availability of raw materials and production suitability.
- the divalent linking group represented by L 1 is an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms) or an alkyleneoxy group (preferably an alkylene having 1 to 12 carbon atoms).
- Oxy group an oxyalkylenecarbonyl group (preferably an oxyalkylenecarbonyl group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), —NH—, —SO—, —SO 2 —. , —CO—, —O—, —COO—, OCO—, —S—, and a group formed by combining two or more thereof.
- the alkylene group, the alkylene group in the alkyleneoxy group, and the alkylene group in the oxyalkylenecarbonyl group may be linear, branched, or cyclic, and are preferably linear or branched. Further, the alkylene group, the alkylene group in the alkyleneoxy group, and the alkylene group in the oxyalkylenecarbonyl group may have a substituent or may be unsubstituted. Examples of the substituent include a hydroxyl group and an alkoxy group, and a hydroxyl group is preferred from the viewpoint of production suitability.
- Y 1 is a group having a radical polymerizable ethylenically unsaturated group, such as vinyl group, vinyloxy group, allyl group, methallyl group, (meth) acryloyl group, styrene group, cinnamoyl. And a group containing at least one selected from a group and a maleimide group, a (meth) acryloyl group, a styrene group and a maleimide group are preferred, a (meth) acryloyl group is more preferred, and an acryloyl group is still more preferred.
- a radical polymerizable ethylenically unsaturated group such as vinyl group, vinyloxy group, allyl group, methallyl group, (meth) acryloyl group, styrene group, cinnamoyl.
- repeating unit represented by the formula (A-1-1) examples include a repeating unit represented by the following formula (A-1-1a) and a repeating unit represented by the following formula (A-1-1b). Examples include units.
- R a1 to R a3 each independently represents a hydrogen atom or an alkyl group
- Q a1 represents —CO—, —COO—, —OCO—, —CONH— or phenylene
- L 1 represents a single bond or a divalent linking group
- Y 1 represents a group having a radical polymerizable ethylenically unsaturated group.
- the alkyl group represented by R a1 to R a3 preferably has 1 to 10 carbon atoms, more preferably 1 to 3 carbon atoms, and still more preferably 1.
- Q a1 is preferably —COO— or —CONH—, and more preferably —COO—.
- R a10 and R a11 each independently represents a hydrogen atom or an alkyl group
- m1 represents an integer of 1 to 5
- L 1 represents a single bond or a divalent linkage.
- Y 1 represents a group having a radical polymerizable ethylenically unsaturated group.
- the alkyl group represented by R a10 and R a11 preferably has 1 to 10 carbon atoms, and more preferably 1 to 3 carbon atoms.
- the graft chain in the compound A means a polymer chain branched and extended from the main chain of the repeating unit.
- the length of the graft chain is not particularly limited, but when the graft chain is long, the steric repulsion effect is enhanced, and the dispersibility of the near-infrared absorbing compound can be enhanced.
- the graft chain preferably has 40 to 10,000 atoms excluding hydrogen atoms, more preferably 50 to 2000 atoms excluding hydrogen atoms, and 60 to 2000 atoms excluding hydrogen atoms. More preferably, it is 500.
- the graft chain preferably includes at least one structure selected from a polyester structure, a polyether structure, a poly (meth) acrylic structure, a polyurethane structure, a polyurea structure, and a polyamide structure, and includes a polyester structure, a polyether structure, and a poly (meta) ) It is more preferable to include at least one structure selected from acrylic structures, and it is even more preferable to include a polyester structure.
- the polyester structure include structures represented by the following formula (G-1), formula (G-4), or formula (G-5).
- examples of the polyether structure include structures represented by the following formula (G-2).
- examples of the poly (meth) acrylic structure include a structure represented by the following formula (G-3).
- R G1 and R G2 each independently represent an alkylene group.
- the alkylene group represented by R G1 and R G2 is not particularly limited, but is preferably a linear or branched alkylene group having 1 to 20 carbon atoms, and a linear or branched alkylene group having 2 to 16 carbon atoms. Group is more preferable, and a linear or branched alkylene group having 3 to 12 carbon atoms is still more preferable.
- R G3 represents a hydrogen atom or a methyl group.
- Q G1 represents —O— or —NH—
- L G1 represents a single bond or a divalent linking group.
- Examples of the divalent linking group include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an alkyleneoxy group (preferably an alkyleneoxy group having 1 to 12 carbon atoms), and an oxyalkylenecarbonyl group (preferably 1 carbon atom).
- an alkylene group preferably an alkylene group having 1 to 12 carbon atoms
- an alkyleneoxy group preferably an alkyleneoxy group having 1 to 12 carbon atoms
- an oxyalkylenecarbonyl group preferably 1 carbon atom.
- arylene groups preferably arylene groups having 6 to 20 carbon atoms
- R G4 represents a hydrogen atom or a substituent.
- substituents examples include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, and a heteroarylthioether group.
- the graft chain when the graft chain includes a polyester structure, it may include only one type of polyester structure, or may include two or more types of polyester structures having different R G1 .
- the graft chain includes a polyether structure it may include only one kind of polyether structure, or may include two or more kinds of polyether structures having different R G2 .
- the graft chain contains a poly (meth) acrylic structure it may contain only one kind of poly (meth) acrylic structure, and at least one selected from R G3 , Q G1 , L G1 and R G4 is Two or more different poly (meth) acrylic structures may be included.
- the terminal structure of the graft chain is not particularly limited. It may be a hydrogen atom or a substituent.
- substituent include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, and a heteroarylthioether group.
- a group having a steric repulsion effect is preferable, and an alkyl group or alkoxy group having 5 to 24 carbon atoms is preferable.
- the alkyl group and alkoxy group may be linear, branched or cyclic, and is preferably linear or branched.
- the graft chain has a structure represented by the following formula (G-1a), formula (G-2a), formula (G-3a), formula (G-4a) or formula (G-5a). Preferably there is.
- R G1 and R G2 each independently represent an alkylene group
- R G3 represents a hydrogen atom or a methyl group
- Q G1 represents —O— or —NH—
- L G1 represents A single bond or a divalent linking group is represented
- R G4 represents a hydrogen atom or a substituent
- W 100 represents a hydrogen atom or a substituent.
- n1 to n5 each independently represents an integer of 2 or more.
- Q G1 , L G1 , Formula (G1) ⁇ (G-5 ) has the same meaning as R G1 ⁇ R G4, Q G1 , L G1 described in, the preferred range is also the same is there.
- W 100 is preferably a substituent.
- the substituent include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, and a heteroarylthioether group.
- a group having a steric repulsion effect is preferable, and an alkyl group or alkoxy group having 5 to 24 carbon atoms is preferable.
- the alkyl group and alkoxy group may be linear, branched or cyclic, and is preferably linear or branched.
- n1 to n5 are each independently preferably an integer of 2 to 100, more preferably an integer of 2 to 80, and still more preferably an integer of 8 to 60.
- R G1 in each repeating unit when n1 is 2 or more may be the same or different. Further, in a case where a repeating unit R G1 is two or more different, the sequence of the repeating units is not particularly limited, random, alternating, and may be either a block. The same applies to the formulas (G-2a) to (G-5a).
- repeating unit having a graft chain examples include a repeating unit represented by the following formula (A-1-2).
- X 2 represents a main chain of a repeating unit
- L 2 represents a single bond or a divalent linking group
- W 1 represents a graft chain.
- main chain of the repeating unit represented by X 2 in formula (A-1-2) include the structures described for X 1 in formula (A-1-1), and preferred ranges are also the same.
- divalent linking group represented by L 2 in the formula (A-1-2) include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms) and an arylene group (preferably an arylene group having 6 to 20 carbon atoms).
- graft chain represented by W 1 in formula (A-1-2) examples include the graft chains described above.
- repeating unit represented by the formula (A-1-2) include a repeating unit represented by the following formula (A-1-2a) and a repeating unit represented by the following formula (A-1-2b). Examples include units.
- R b1 to R b3 each independently represents a hydrogen atom or an alkyl group
- Q b1 represents —CO—, —COO—, —OCO—, —CONH— or phenylene.
- L 2 represents a single bond or a divalent linking group
- W 1 represents a graft chain.
- the number of carbon atoms of the alkyl group represented by R b1 to R b3 is preferably 1 to 10, more preferably 1 to 3, and still more preferably 1.
- Q b1 is preferably —COO— or —CONH—, and more preferably —COO—.
- R b10 and R b11 each independently represent a hydrogen atom or an alkyl group
- m2 represents an integer of 1 to 5
- L 2 represents a single bond or a divalent linkage.
- W 1 represents a graft chain.
- the alkyl group represented by R b10 and R b11 preferably has 1 to 10 carbon atoms, and more preferably 1 to 3 carbon atoms.
- the weight average molecular weight (Mw) of the repeating unit having a graft chain is preferably 1000 or more, more preferably 1000 to 10,000, and still more preferably 1000 to 7500.
- the weight average molecular weight of the repeating unit having a graft chain is a value calculated from the weight average molecular weight of the raw material monomer used for the polymerization of the repeating unit.
- the repeating unit having a graft chain can be formed by polymerizing a macromonomer.
- the macromonomer means a polymer compound in which a polymerizable group is introduced at a polymer terminal.
- the weight average molecular weight of the macromonomer corresponds to the repeating unit having a graft chain.
- Compound A preferably includes a repeating unit having a radical polymerizable ethylenically unsaturated group and a repeating unit having a graft chain.
- the repeating unit having a radical polymerizable ethylenically unsaturated group is preferably contained in an amount of 10 to 80 mol%, more preferably 20 to 70 mol% in all repeating units of compound A.
- the repeating unit having a graft chain is preferably contained in an amount of 1.0 to 60 mol%, more preferably 1.5 to 50 mol%, based on all repeating units of Compound A.
- Compound A preferably further contains a repeating unit having an acid group.
- the dispersibility of the near-infrared absorbing compound can be further improved.
- developability can also be improved.
- the acid group include a carboxyl group, a sulfo group, and a phosphoric acid group.
- repeating unit having an acid group examples include a repeating unit represented by the following formula (A-1-3).
- X 3 represents the main chain of the repeating unit
- L 3 represents a single bond or a divalent linking group
- a 1 represents an acid group.
- Examples of the main chain of the repeating unit represented by X 3 in formula (A-1-3) include the structures described for X 1 in formula (A-1-1), and the preferred ranges are also the same.
- Examples of the divalent linking group represented by L 3 in the formula (A-1-3) include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms) and an alkenylene group (preferably an alkenylene group having 2 to 12 carbon atoms).
- An alkyleneoxy group (preferably an alkyleneoxy group having 1 to 12 carbon atoms), an oxyalkylenecarbonyl group (preferably an oxyalkylenecarbonyl group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms) ), —NH—, —SO—, —SO 2 —, —CO—, —O—, —COO—, OCO—, —S—, and a combination of two or more thereof.
- the alkylene group, the alkylene group in the alkyleneoxy group, and the alkylene group in the oxyalkylenecarbonyl group may be linear, branched, or cyclic, and are preferably linear or branched.
- alkylene group, the alkylene group in the alkyleneoxy group, and the alkylene group in the oxyalkylenecarbonyl group may have a substituent or may be unsubstituted.
- substituent include a hydroxyl group.
- acid group represented by A 1 in formula (A-1-3) include a carboxyl group, a sulfo group, and a phosphate group.
- repeating unit represented by the formula (A-1-3) include a repeating unit represented by the following formula (A-1-3a) and a repeating unit represented by the following formula (A-1-3b). Examples include units.
- R c1 to R c3 each independently represents a hydrogen atom or an alkyl group
- Q b1 represents —CO—, —COO—, —OCO—, —CONH— or phenylene.
- L 3 represents a single bond or a divalent linking group
- a 1 represents an acid group.
- the number of carbon atoms of the alkyl group represented by R c1 to R c3 is preferably 1 to 10, more preferably 1 to 3, and still more preferably 1.
- Q b1 is preferably —COO— or —CONH—, and more preferably —COO—.
- R c10 and R c11 each independently represent a hydrogen atom or an alkyl group
- m3 represents an integer of 1 to 5
- L 3 represents a single bond or a divalent linkage.
- the alkyl group represented by R c10 and R c11 preferably has 1 to 10 carbon atoms, and more preferably 1 to 3 carbon atoms.
- the repeating unit represented by the formula (A-1-3a) is more preferably a repeating unit represented by the following formula (A-1-3a-1).
- R c1 to R c3 each independently represents a hydrogen atom or an alkyl group
- Q c1 represents —CO—, —COO—, —OCO—, —CONH— Or a phenylene group
- L 10 represents a single bond or an alkylene group
- L 11 represents a single bond, —O—, —S—, —NH—, —CO—, —OCO— or —COO—
- R c4 represents an alkylene group or an arylene group
- p is an integer of 0-5. However, when p is 0, L 11 is —COO—, or L 10 and L 11 are a single bond and Q c1 is —COO—.
- the number of carbon atoms of the alkyl group represented by R c1 to R c3 is preferably 1 to 10, more preferably 1 to 3, and still more preferably 1.
- Q b1 is preferably —COO— or —CONH—, and more preferably —COO—.
- the alkylene group represented by L 10 preferably has 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms.
- the alkylene group may be linear, branched, or cyclic, and is preferably linear or branched, more preferably linear.
- L 10 is preferably a single bond.
- L 11 is preferably a single bond or —OCO—, and more preferably a single bond.
- R c4 is preferably an alkylene group.
- the number of carbon atoms of the alkylene machine is preferably 1 to 12, more preferably 1 to 8, still more preferably 2 to 8, and particularly preferably 2 to 6.
- the alkylene group represented by R c4 may be linear, branched or cyclic, preferably linear or branched, and more preferably linear.
- p represents an integer of 0 to 5, preferably an integer of 0 to 3, and more preferably an integer of 0 to 2.
- the repeating unit having an acid group is preferably contained in an amount of 80 mol% or less, more preferably 10 to 80 mol%, based on all repeating units of Compound A. .
- the acid value of Compound A is preferably 20 to 150 mgKOH / g.
- the upper limit is more preferably 100 mgKOH / g or less.
- the lower limit is preferably 30 mgKOH / g or more, and more preferably 35 mgKOH / g or more.
- Compound A may further contain other repeating units.
- the compound A contains a repeating unit represented by the above formula (A-1-2b) as a repeating unit having a graft chain, the following formula (A-1-4b) and / or the formula The repeating unit represented by (A-1-5b) can be contained.
- R d10 and R d11 each independently represent a hydrogen atom or an alkyl group, and m4 represents an integer of 1 to 5.
- the alkyl group represented by R d10 and R d11 preferably has 1 to 10 carbon atoms, and more preferably 1 to 3 carbon atoms.
- R e10 and R e11 each independently represent a hydrogen atom or an alkyl group
- m5 represents an integer of 1 to 5
- D e1 represents an anion group
- L e1 represents It represents a single bond or a divalent linking group
- W e1 represents a graft chain.
- the alkyl group represented by R e10 and R e11 preferably has 1 to 10 carbon atoms, and more preferably 1 to 3 carbon atoms.
- Examples of the anion group represented by D e1 include —SO 3 ⁇ , —COO ⁇ , —PO 4 ⁇ , —PO 4 H —, and the like.
- Examples of the divalent linking group represented by L e1 and the graft chain represented by W e1 include those described above for L 2 and W 1 in formula (A-1-2).
- compound A includes the following.
- the content of Compound A is preferably 5 to 50% by mass with respect to the total solid content of the composition.
- the lower limit is preferably 7% by mass or more, and more preferably 10% by mass or more.
- the upper limit is preferably 40% by mass or less, and more preferably 30% by mass or less.
- the composition of the present invention can contain a polymerizable compound other than the compound A described above.
- a compound that can be polymerized by the action of a radical is preferable. That is, the polymerizable compound is preferably a radical polymerizable compound.
- the polymerizable compound is preferably a compound having one or more ethylenically unsaturated groups, more preferably a compound having two or more ethylenically unsaturated groups, and still more preferably a compound having three or more ethylenically unsaturated groups.
- the upper limit of the number of ethylenically unsaturated groups is preferably 15 or less, and more preferably 6 or less.
- Examples of the ethylenically unsaturated group include a vinyl group, a styrene group, an allyl group, a methallyl group, 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 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 or more and less than 3000.
- 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. 0.0 to 1.3 is more preferable.
- polymerizable compound paragraphs 0033 to 0034 of JP2013-253224A can be referred to, and the contents thereof are incorporated in the present specification.
- the polymerizable compound include ethyleneoxy-modified pentaerythritol tetraacrylate (commercially available NK ester ATM-35E; manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol triacrylate (commercially available KAYARAD D-330).
- Diglycerin EO (ethylene oxide) modified (meth) acrylate commercially available product is M-460; manufactured by Toagosei Co., Ltd.
- pentaerythritol tetraacrylate manufactured by Shin-Nakamura Chemical Co., Ltd., A-TMMT
- 1,6- Hexanediol diacrylate manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA
- 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 carboxyl group, a sulfo group, or a phosphoric acid group.
- Examples of commercially available polymerizable compounds having an acid group include Aronix M-305, M-510, and M-520 (manufactured by Toagosei Co., Ltd.).
- the acid value of the polymerizable compound having an acid group is preferably from 0.1 to 40 mgKOH / g.
- the lower limit is preferably 5 mgKOH / g or more.
- the upper limit is preferably 30 mgKOH / g or less.
- the polymerizable compound is a compound having a caprolactone structure.
- the polymerizable compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule.
- polymerizable compound having a caprolactone structure As the polymerizable compound having a caprolactone structure, the description in paragraph numbers 0042 to 0045 of JP2013-253224A can be referred to, and the contents thereof are incorporated herein.
- Compounds having a caprolactone structure include, for example, DPCA-20, DPCA-30, DPCA-60, DPCA-120, etc. commercially available from Nippon Kayaku Co., Ltd. as KAYARAD DPCA series.
- SR-494 which is a tetrafunctional acrylate having four
- TPA-330 which is a trifunctional acrylate having three isobutyleneoxy chains.
- Examples of the polymerizable compound include urethane acrylates described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, Also suitable are urethane compounds having an ethylene oxide skeleton as described in Japanese Patent Publication Nos. 58-49860, 56-17654, 62-39417, and 62-39418. Further, 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 are used. Can do.
- urethane oligomer UAS-10 UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), 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 other than Compound A is preferably 0.1 to 40% 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 30% by mass or less, and still more preferably 20% by mass or less.
- the composition of the present invention can also be substantially free of polymerizable compounds other than Compound A. That the composition of the present invention does not substantially contain a polymerizable compound other than Compound A means that the content of the polymerizable compound other than Compound A is 0.05% by mass or less based on the total solid content of the composition.
- the total content of the above-described compound A and polymerizable compounds other than compound A is preferably 5 to 50% by mass with respect to the total solid content of the composition.
- the lower limit is more preferably 7% by mass or more, and still more preferably 10% 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 of polymeric compounds together, it is preferable that a total amount becomes the said range.
- the composition of the present invention can contain a photopolymerization initiator.
- a photoinitiator It can select suitably from well-known photoinitiators.
- a compound having photosensitivity to light in the ultraviolet region to the visible region is preferable.
- the photopolymerization initiator is preferably a radical photopolymerization initiator.
- Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazoles, oxime compounds, organic peroxides, Examples include thio compounds, ketone compounds, aromatic onium salts, ⁇ -hydroxy ketone compounds, ⁇ -amino ketone compounds, and the like.
- halogenated hydrocarbon derivatives for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.
- acylphosphine compounds for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.
- acylphosphine compounds for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.
- Photopolymerization initiators are trihalomethyltriazine compounds, benzyldimethylketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazoles from the viewpoint of exposure sensitivity.
- Dimer, onium compound, benzothiazole compound, benzophenone compound, acetophenone compound, cyclopentadiene-benzene-iron complex, halomethyloxadiazole compound and 3-aryl-substituted coumarin compound are preferred, oxime compound, ⁇ -hydroxyketone compound, ⁇ - A compound selected from an aminoketone compound and an acylphosphine compound is more preferable, and an oxime compound is still more preferable.
- the photopolymerization initiator descriptions in paragraphs 0065 to 0111 of JP-A-2014-130173 can be referred to, and the contents thereof are incorporated in the present specification.
- Examples of commercially available ⁇ -hydroxyketone compounds include IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (above, manufactured by BASF).
- Examples of commercially available ⁇ -aminoketone compounds include IRGACURE-907, IRGACURE-369, IRGACURE-379, IRGACURE-379EG (manufactured by BASF).
- Examples of commercially available acylphosphine compounds include IRGACURE-819 and DAROCUR-TPO (above, manufactured by BASF).
- Examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, compounds described in JP-A No. 2006-342166, and JP-A No. 2016-21012. Etc. can be used.
- Examples of the oxime compound that can be suitably used in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyimibutan-2-one, 2- Acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2- ON, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.
- J.H. C. S. Perkin II (1979, pp.1653-1660) J.A. C. S.
- TR-PBG-304 manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.
- Adeka Arcles NCI-831 manufactured by ADEKA Corporation
- Adeka Arcles NCI-930 manufactured by ADEKA Corporation
- Adekaoptomer N -1919 manufactured by ADEKA Corporation, photopolymerization initiator 2 described in JP2012-14052A
- 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 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 compound having a nitro group can be used as a photopolymerization initiator.
- the oxime compound having a nitro group is also preferably a dimer.
- Specific examples of the oxime compound having a nitro group include compounds described in paragraphs 0031 to 0047 of JP2013-114249A, paragraphs 0008 to 0012 and 0070 to 0079 of JP2014-137466A, Examples include compounds described in paragraph Nos. 0007 to 0025 of Japanese Patent No. 4223071, Adeka Arcles NCI-831 (manufactured by ADEKA Corporation).
- oxime compounds that are preferably used in the present invention are shown below, but the present invention is not limited thereto.
- the oxime compound is preferably a compound having a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, and more preferably a compound having a maximum absorption wavelength 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. 000 is particularly preferred.
- the molar extinction coefficient of the compound can be measured using a known method. For example, it is preferable to measure with a 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, the developability is good.
- 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 of photopolymerization initiators are included, the total amount is preferably within the above range.
- the composition of the present invention can further contain a resin other than the compound A described above.
- the resin other than Compound A include a resin having no graft chain and a resin having no radically polymerizable unsaturated bond group.
- the resin is blended, for example, for the purpose of dispersing particles such as pigments in the composition or the use of a binder.
- a resin that is mainly used for dispersing particles such as pigment is also referred to as a dispersant.
- such use of the resin is an example, and the resin can be used for purposes other than such use.
- the weight average molecular weight (Mw) of the resin is preferably 2,000 to 2,000,000.
- the upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less.
- the lower limit is preferably 3,000 or more, and more preferably 5,000 or more.
- the cyclic olefin 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.
- Examples of the epoxy resin 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.
- Epoxy resins glycidylamine epoxy resins, epoxy resins obtained by glycidylation of halogenated phenols, condensates of silicon compounds having an epoxy group with other silicon compounds, polymerizable unsaturated compounds having an epoxy group and others Examples thereof include copolymers with other polymerizable unsaturated compounds.
- 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) , Epoxy group-containing polymer) and the like can also be used.
- the resin as described in the Example of international publication WO2016 / 088645 can also be used for resin.
- the resin used in the present invention may have an acid group.
- the acid group include a carboxyl group, a phosphate group, a sulfo group, a phenolic hydroxyl group, and the like, and a carboxyl group is preferable. These acid groups may be used alone or in combination of two or more. Resins having acid groups can also be used as alkali-soluble resins.
- a polymer having a carboxyl group in the side chain is preferable.
- 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 carboxyl group in the side chain, and resins obtained by adding an acid anhydride to a polymer having a hydroxyl 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.
- the resin having an acid group may further have a polymerizable group.
- the polymerizable group include an allyl group, a methallyl group, and a (meth) acryloyl group.
- Commercially available products include Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (carboxyl group-containing polyurethane acrylate oligomer, Diamond Shamrock Co., Ltd.), Biscote R-264, KS resist 106 (all of which are Osaka organic Chemical Industry Co., Ltd.), Cyclomer P series (for example, ACA230AA), Plaxel CF200 series (all manufactured by Daicel Corp.), Ebecryl 3800 (manufactured by Daicel UCB Corp.), Acryl RD-F8 (Co., Ltd.) Nippon Catalysts).
- Resins having an acid group include benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, benzyl (meth) Multi-component copolymers composed of acrylate / (meth) acrylic acid / other monomers can be preferably used.
- the resin having an acid group is a monomer containing 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”).
- ED1 a compound represented by the following formula
- ED2 a compound represented by the following formula
- a polymer containing a repeating unit derived from a component is also preferred.
- 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.
- ether dimer for example, 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 resin having an acid group may contain a repeating 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 has 1 to 20 carbon atoms which may contain a hydrogen atom or a benzene ring.
- n represents an integer of 1 to 15.
- the acid value of the resin having an acid group is preferably 30 to 200 mgKOH / g.
- the lower limit is preferably 50 mgKOH / g or more, and more preferably 70 mgKOH / g or more.
- the upper limit is preferably 150 mgKOH / g or less, and more preferably 120 mgKOH / g or less.
- Examples of the resin having an acid group include resins having the following structure.
- Me represents a methyl group.
- the composition of the present invention can also contain a resin as a dispersant.
- the dispersant include an acidic dispersant (acidic resin) and a basic dispersant (basic resin).
- the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is larger than the amount of basic groups.
- the acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups occupies 70 mol% or more when the total amount of acid groups and basic groups is 100 mol%. A resin consisting only of groups is more preferred.
- the acid group possessed by the acidic dispersant (acidic resin) is preferably a carboxyl group.
- the acid value of the acidic dispersant is preferably 40 to 105 mgKOH / g, more preferably 50 to 105 mgKOH / g, and still more preferably 60 to 105 mgKOH / g.
- the basic dispersant (basic resin) represents a resin in which the amount of basic groups is larger than the amount of acid groups.
- the basic dispersant (basic resin) is preferably a resin in which the amount of basic groups exceeds 50 mol% when the total amount of acid groups and basic groups is 100 mol%.
- the basic group possessed by the basic dispersant is preferably an amino group.
- the resin used as the dispersant preferably contains a repeating unit having an acid group.
- a residue generated on the base of the pixel can be further reduced when a pattern is formed by a photolithography method.
- the resin used as the dispersant is also preferably a graft copolymer. Since the graft copolymer has an affinity for the solvent by the graft chain, it is excellent in pigment dispersibility and dispersion stability after aging. Details of the graft copolymer can be referred to the descriptions in paragraphs 0025 to 0094 of JP2012-255128A, the contents of which are incorporated herein. Specific examples of the graft copolymer include the following resins. The following resins are also resins having acid groups (alkali-soluble resins). Examples of the graft copolymer include resins described in JP-A-2012-255128, paragraphs 0072 to 0094, the contents of which are incorporated herein.
- an oligoimine dispersant containing a nitrogen atom in at least one of the main chain and the side chain is also preferable to use as the resin (dispersant).
- the oligoimine-based dispersant has a structural unit having a partial structure X having a functional group of pKa14 or less, a side chain containing a side chain Y having 40 to 10,000 atoms, and a main chain and a side chain.
- a resin having at least one basic nitrogen atom is preferred.
- the basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom.
- oligoimine-based dispersant the description of paragraph numbers 0102 to 0166 in JP 2012-255128 A can be referred to, and the contents thereof are incorporated herein.
- resins described in paragraph numbers 0168 to 0174 of JP 2012-255128 A can be used.
- Dispersants are also available as commercial products, and specific examples thereof include Disperbyk-111 (BYK Chemie), Solsperse 76500 (Nihon Lubrizol Co., Ltd.), and the like.
- pigment dispersants described in paragraph numbers 0041 to 0130 of JP-A-2014-130338 can also be used, the contents of which are incorporated herein.
- the resin etc. which have the acid group mentioned above can also be used as a dispersing agent.
- the content of the resin is preferably more than 0% by mass and 30% by mass or less with respect to the total solid content of the composition of the present invention.
- the composition of the present invention can also contain a colorant that transmits infrared rays and blocks visible light (hereinafter also referred to as a colorant that blocks visible light).
- the color material that blocks visible light is preferably a color material that absorbs light in the wavelength range from purple to red.
- the color material that blocks visible light is preferably a color material that blocks light in the wavelength region of 400 to 640 nm.
- the color material that blocks visible light is preferably a color material that transmits light having a wavelength of 900 to 1300 nm.
- the colorant that blocks visible light preferably satisfies at least one of the following requirements (A) and (B).
- Black is formed by a combination of two or more chromatic colorants including two or more chromatic colorants.
- the chromatic colorant means a colorant other than the white colorant and the black colorant.
- the organic black colorant as a colorant that blocks visible light means a material that absorbs visible light but transmits at least part of infrared rays.
- the organic black colorant as a colorant that blocks visible light does not include a black colorant that absorbs both visible light and infrared rays, such as carbon black and titanium black.
- the organic black colorant is preferably a colorant having a maximum absorption wavelength in a wavelength range of 400 nm to 700 nm.
- the colorant that blocks visible light has, for example, an A / B that is a ratio of the minimum absorbance A in the wavelength range of 400 to 640 nm and the minimum absorbance B in the wavelength range of 900 to 1300 nm. It is preferable that it is 4.5 or more.
- the above characteristics may be satisfied by one kind of material, or may be satisfied by a combination of a plurality of materials.
- it is preferable that a plurality of chromatic colorants are combined to satisfy the spectral characteristics.
- the organic black colorant may satisfy the above spectral characteristics.
- the above-described spectral characteristics may be satisfied by a combination of an organic black colorant and a chromatic colorant.
- the chromatic colorant is preferably a colorant selected from a red colorant, a green colorant, a blue colorant, a yellow colorant, a purple colorant and an orange colorant.
- the chromatic colorant may be a pigment or a dye.
- a pigment is preferable.
- the pigment preferably has an average particle size (r) of 20 nm ⁇ r ⁇ 300 nm, more preferably 25 nm ⁇ r ⁇ 250 nm, and still more preferably 30 nm ⁇ r ⁇ 200 nm.
- the “average particle size” means an average particle size of secondary particles in which primary particles of the pigment are aggregated.
- the particle size distribution of secondary particles of the pigment that can be used (hereinafter also simply referred to as “particle size distribution”) is such that the secondary particles contained in the range of the average particle size ⁇ 100 nm are 70% by mass or more of the total. It is preferable that it is 80% by mass or more.
- the particle size distribution of the secondary particles can be measured using the scattering intensity distribution.
- the pigment is preferably an organic pigment.
- the following are mentioned as an organic pigment.
- 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. Moreover, you may use the multimer of these dyes. Further, the dyes described in JP-A-2015-028144 and JP-A-2015-34966 can also be used.
- the colorant that blocks visible light preferably includes two or more selected from a red colorant, a blue colorant, a yellow colorant, a purple colorant, and a green colorant. That is, the colorant that blocks visible light may form black with a combination of two or more colorants selected from a red colorant, a blue colorant, a yellow colorant, a purple colorant, and a green colorant. preferable. Examples of preferable combinations include the following. (1) An embodiment containing a red colorant and a blue colorant. (2) An embodiment containing a red colorant, a blue colorant, and a yellow colorant. (3) An embodiment containing a red colorant, a blue colorant, a yellow colorant and a purple colorant.
- An embodiment containing a red colorant, a blue colorant, a yellow colorant, a purple colorant, and a green colorant (5) An embodiment containing a red colorant, a blue colorant, a yellow colorant, and a green colorant. (6) An embodiment containing a red colorant, a blue colorant, and a green colorant. (7) An embodiment containing a yellow colorant and a purple colorant.
- C.I. I. Pigment Yellow 139, 150, 185 are preferred.
- I. Pigment Yellow 139,150 is more preferable, and C.I. I. Pigment Yellow 139 is more preferable.
- blue colorants include C.I. I. Pigment Blue 15: 6 is preferable.
- purple colorants include C.I. I. Pigment Violet 23 is preferable.
- As the red colorant Pigment Red 122, 177, 224, 254 is preferable, Pigment Red 122, 177254 is more preferable, and Pigment Red 254 is more preferable.
- the green colorant include C.I. I. Pigment Green 7, 36, 58, 59 are preferable.
- organic black colorant examples include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds, and bisbenzofuranone compounds and perylene compounds are preferable.
- examples of the bisbenzofuranone compounds include compounds 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.
- perylene compounds examples 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 bisbenzofuranone compound is preferably a compound represented by the following 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
- the plurality of R 3 may be the same or different
- the plurality of R 3 may be bonded to form a ring
- b is 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 substituents represented by R 1 to R 4 are a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heteroaryl group, —OR 301 , —COR 302 , —COOR 303 , —OCOR 304 , —NR 305 R 306 , —NHCOR 307 , —CONR 308 R 309 , —NHCONR 310 R 311 , —NHCOOR 312 , —SR 313 , —SO 2 R 314 , —SO 2 OR 315 , —NHSO 2 R 316 or —SO 2 NR 317 R 318 , each of R 301 to R 318 independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group
- an organic black colorant when used as a colorant that blocks visible light, it is preferably used in combination with a chromatic colorant.
- a chromatic colorant By using an organic black colorant and a chromatic colorant in combination, excellent spectral characteristics are easily obtained.
- the chromatic colorant used in combination with the organic black colorant include a red colorant, a blue colorant, and a purple colorant, and a red colorant and a blue colorant are preferable. These may be used alone or in combination of two or more.
- the mixing ratio of the chromatic colorant and the organic black colorant is preferably 10 to 200 parts by weight, more preferably 15 to 150 parts by weight for the chromatic colorant with respect to 100 parts by weight of the organic black colorant. preferable.
- the content of the pigment in the color material that blocks visible light is preferably 95% by mass or more, more preferably 97% by mass or more, based on the total amount of the color material that blocks visible light. 99% by mass or more is more preferable.
- the content of the colorant that blocks visible light is preferably 10 to 60% by mass with respect to the total solid content of the composition.
- the upper limit is preferably 50% by mass or less, and more preferably 45% by mass or less.
- the lower limit is preferably 20% by mass or more, and more preferably 25% by mass or more.
- the composition of the present invention may further contain a pigment derivative.
- the pigment derivative include compounds having a structure in which a part of the pigment is substituted with an acid group, a basic group, a group having a salt structure, or a phthalimidomethyl group.
- a compound represented by the formula (B1) is preferable.
- P represents a dye structure
- L represents a single bond or a linking group
- X represents an acid group, a basic group, a group having a salt structure, or a phthalimidomethyl group
- m is an integer of 1 or more.
- N represents an integer of 1 or more.
- P represents a dye structure, and pyrrolopyrrole dye structure, diketopyrrolopyrrole dye structure, quinacridone dye structure, anthraquinone dye structure, dianthraquinone dye structure, benzoisoindole dye structure, thiazine indigo dye structure Azo dye structure, quinophthalone dye structure, phthalocyanine dye structure, naphthalocyanine dye structure, dioxazine dye structure, perylene dye structure, perinone dye structure, benzimidazolone dye structure, benzothiazole dye structure, benzimidazole dye structure and benzoxazole dye structure At least one selected from the group consisting of pyrrolopyrrole dye structure, diketopyrrolopyrrole dye structure, quinacridone dye structure and benzoimidazolone dye structure is more preferable. Pyrrole dye structure is particularly preferred.
- L represents a single bond or a linking group.
- the linking group is preferably a group consisting of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms. , May be unsubstituted or may further have a substituent.
- X represents an acid group, a basic group, a group having a salt structure, or a phthalimidomethyl group, and an acid group or a basic group is preferable.
- the acid group include a carboxyl group and a sulfo group.
- An amino group is mentioned as a basic group.
- Examples of the pigment derivative include compounds having the following structure.
- the compounds described in JP-A-10-195326, paragraphs 0086 to 0098 of International Publication WO2011 / 024896, paragraphs 0063 to 0094 of International Publication WO2012 / 102399, etc. can be used. Incorporated in the description.
- the content of the pigment derivative is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the pigment.
- the lower limit is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more.
- the upper limit is preferably 40 parts by mass or less, and more preferably 30 parts by mass or less. If content of a pigment derivative is the said range, the dispersibility of a pigment can be improved and aggregation of a pigment can be suppressed efficiently. Only one pigment derivative may be used, or two or more pigment derivatives may be used. When using 2 or more types, it is preferable that a total amount becomes the said 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 the solubility of each component and the coating property of the composition are satisfied.
- the organic solvent include esters, ethers, ketones, aromatic hydrocarbons and the like. Regarding these details, paragraph number 0223 of International Publication No. WO2015 / 1666779 can be referred to, the contents of which are incorporated herein. Further, ester solvents substituted with a cyclic alkyl group and ketone solvents substituted with a cyclic alkyl group can also be preferably used.
- the organic solvent examples include dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, Examples include cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate.
- the organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.
- aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as solvents may be better reduced for environmental reasons (for example, 50 mass ppm (parts per to the total amount of organic solvent)). (million) or less, or 10 mass ppm or less, or 1 mass ppm or less).
- 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 diameter of the filter used for filtration is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and even more preferably 3 ⁇ m or less.
- the filter material is preferably polytetrafluoroethylene, polyethylene or nylon.
- the solvent may contain isomers (compounds having the same number of atoms but different structures). Moreover, only 1 type may be included and the isomer may be included multiple types.
- 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 can contain a polymerization inhibitor.
- Polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-tert-butylphenol), Examples include 2,2′-methylenebis (4-methyl-6-tert-butylphenol) and N-nitrosophenylhydroxyamine salts (ammonium salt, primary cerium salt, etc.). Of these, p-methoxyphenol is preferred.
- the content of the polymerization inhibitor is preferably 0.001 to 5% by mass with respect to the total solid content of the composition.
- the composition of the present invention can contain a silane coupling agent.
- the 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 generate 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. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group.
- Examples of functional groups other than hydrolyzable groups include vinyl groups, styrene groups, (meth) acryloyl groups, mercapto groups, epoxy groups, oxetanyl groups, amino groups, ureido groups, sulfide groups, isocyanate groups, and phenyl groups. (Meth) acryloyl group and epoxy group are preferable.
- Examples of the silane coupling agent include compounds described in paragraph Nos. 0018 to 0036 of JP-A-2009-288703, and compounds described in paragraph numbers 0056 to 0066 of JP-A-2009-242604. Incorporated in the description.
- the content of the silane coupling agent is preferably 0.01 to 15.0 mass%, more preferably 0.05 to 10.0 mass%, based on the total solid content of the composition. Only one type of silane coupling agent may be used, or two or more types may be used. In the case of two or more types, the total amount is preferably within the above range.
- the composition of the present invention may contain a surfactant.
- a surfactant 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.
- the surfactant is preferably a fluorosurfactant.
- a fluorosurfactant in the composition of the present invention, liquid properties (particularly fluidity) can be further improved, and liquid-saving properties can be further improved.
- a film with small thickness unevenness can be formed.
- the fluorine content in the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly 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. Examples of commercially available fluorosurfactants include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780 (and above, DIC).
- 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.
- 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. % Which shows the ratio of a repeating unit in said compound is the mass%.
- 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% by mass to 5.0% by mass and more preferably 0.005% by mass to 3.0% by mass with respect to the total solid content of the composition of the present invention. Only one type of surfactant may be used, or two or more types may be used. In the case of two or more types, the total amount is preferably within the above range.
- the composition of the present invention can contain an ultraviolet absorber.
- an ultraviolet absorber a conjugated diene compound, an aminobutadiene compound, a methyldibenzoyl compound, a coumarin compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyltriazine compound, or the like can be used.
- paragraph numbers 0052 to 0072 of JP2012-208374A and paragraph numbers 0317 to 0334 of JP2013-68814A the contents of which are incorporated herein.
- UV-503 manufactured by Daito Chemical Co., Ltd.
- MYUA series Chemical Industry Daily, February 1, 2016
- the ultraviolet absorber is preferably a compound represented by the formula (UV-1) to the formula (UV-3), more preferably a compound represented by the formula (UV-1) or the formula (UV-3), The compound represented by (UV-1) is more preferable.
- R 101 and R 102 each independently represent a substituent
- m1 and m2 each independently represent 0 to 4.
- R 201 and R 202 each independently represent a hydrogen atom or an alkyl group
- R 203 and R 204 each independently represent a substituent.
- R 301 to R 303 each independently represents a hydrogen atom or an alkyl group
- R 304 and R 305 each independently represent a substituent.
- the content of the ultraviolet absorber is preferably from 0.01 to 10% by mass, more preferably from 0.01 to 5% by mass, based on the total solid content of the composition.
- the present invention only one type of ultraviolet absorber may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.
- the composition of the present invention can contain an antioxidant.
- the antioxidant include a phenol compound, a phosphite compound, and a thioether compound.
- the phenol compound any phenol compound known as a phenol-based antioxidant can be used.
- Preferable phenolic compounds include hindered phenolic compounds.
- a compound having a substituent at a site (ortho position) adjacent to the phenolic hydroxyl group is preferred.
- the aforementioned substituent is preferably a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms.
- the antioxidant is also preferably a compound having a phenol group and a phosphite group in the same molecule.
- phosphorus antioxidant can also be used suitably for antioxidant.
- phosphorus-based antioxidant tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphine-6 -Yl] oxy] ethyl] amine, tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-2-yl ) Oxy] ethyl] amine, ethylbisphosphite (2,4-di-tert-butyl-6-methylphenyl), and the like.
- antioxidants include, for example, ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-50F, ADK STAB AO-60, ADK STAB AO-60G and ADK STAB AO-80.
- Adeka Stub AO-330 (above, ADEKA Co., Ltd.) and the like.
- the content of the antioxidant is preferably 0.01 to 20% by mass, more preferably 0.3 to 15% by mass, based on the total solid content of the composition. preferable. Only one type of antioxidant may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.
- the composition of the present invention may contain a sensitizer, a curing accelerator, a filler, a thermosetting accelerator, a plasticizer, and other auxiliary agents (for example, conductive particles, a filler, an antifoaming agent, a difficult agent, if necessary).
- auxiliary agents for example, conductive particles, a filler, an antifoaming agent, a difficult agent, if necessary.
- Properties such as film properties can be adjusted by appropriately containing these components.
- the viscosity (23 ° C.) of the composition of the present invention is preferably 1 to 100 mPa ⁇ s, for example, when a film is formed by coating.
- the lower limit is more preferably 2 mPa ⁇ s or more, and further preferably 3 mPa ⁇ s or more.
- the upper limit is more preferably 50 mPa ⁇ s or less, further preferably 30 mPa ⁇ s or less, and particularly preferably 15 mPa ⁇ s or less.
- the container for the composition of the present invention is not particularly limited, and a known container can be used.
- a storage container for the purpose of suppressing contamination of impurities in raw materials and compositions, a multilayer bottle in which the inner wall of the container is composed of six types and six layers of resin, and a bottle having six types of resins in a seven layer structure are used. It is also preferable to use it.
- Examples of such a container include a container described in JP-A-2015-123351.
- composition of the present invention is not particularly limited.
- it can be preferably used to form a near infrared cut filter.
- transmit only the near infrared rays more than a specific wavelength can also be formed by containing the coloring material which shields visible light further.
- the composition of the present invention can be prepared by mixing the aforementioned components.
- the composition may be prepared by dissolving or dispersing all the components in the solvent at the same time. If necessary, two or more solutions or dispersions appropriately blending each component may be prepared in advance. They may be prepared and mixed to prepare a composition at the time of use (at the time of application).
- the composition of the present invention when it 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 the 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 a 1st filter may be performed only with respect to a dispersion liquid, and after mixing other components, it may filter with a 2nd filter.
- the film of the present invention is obtained from the above-described composition of the present invention.
- the film of the present invention can be preferably used as a near-infrared cut filter or an infrared transmission filter. It can also be used as a heat ray shielding filter.
- the film of the present invention may have a pattern, or may be a film without a pattern (flat film).
- the film of the present invention may be used by being laminated on a support, or the film of the present invention may be peeled off from a support.
- examples of the infrared transmission filter include a filter that blocks visible light and transmits light having a wavelength of 900 nm or more.
- a near-infrared absorbing compound and a colorant that blocks visible light preferably a colorant containing two or more chromatic colorants, or an organic material
- the near-infrared absorption compound When using the film
- the film thickness of the film of the present invention can be appropriately adjusted according to the purpose.
- the film thickness is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and even more preferably 5 ⁇ m or less.
- the lower limit of the film thickness is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, and further preferably 0.3 ⁇ m or more.
- the film of the present invention can also be used in combination with a color filter containing a chromatic colorant.
- the film and the color filter in the present invention can be laminated to be used as a laminate.
- the film of the present invention and the color filter may or may not be adjacent to each other in the thickness direction.
- the film of the present invention may be formed on a support different from the support on which the color filter is formed.
- Another member for example, a microlens, a flattening layer, or the like constituting the solid-state imaging device may be interposed between the film and the color filter.
- a color filter can be manufactured using the coloring composition containing a chromatic colorant. Examples of the chromatic colorant include the chromatic colorant described in the composition of the present invention.
- the near-infrared cut filter means a filter that transmits light having a wavelength in the visible region (visible light) and shields at least a part of light having a wavelength in the near-infrared region (near-infrared light). .
- the near-infrared cut filter may transmit all light having a wavelength in the visible region, transmits light in a specific wavelength region out of light in the visible region, and blocks light in a specific wavelength region. You may do.
- the color filter means a filter that transmits light in a specific wavelength region and blocks light in a specific wavelength region out of light in the visible region.
- the infrared transmission filter means a filter that blocks light having a wavelength in the visible region and transmits at least part of light having a wavelength in the near infrared region (near infrared).
- the film of the present invention When the film of the present invention is used as a near infrared cut filter, the film of the present invention preferably has a maximum absorption wavelength in the wavelength range of 700 to 1000 nm.
- the average transmittance at a wavelength of 400 to 550 nm is preferably 70% or more, more preferably 80% or more, further preferably 85% or more, and particularly preferably 90% or more.
- the transmittance in the entire range of wavelengths from 400 to 550 nm is preferably 70% or more, more preferably 80% or more, and further preferably 90% or more.
- the preferred range of the near-infrared shielding property of the near-infrared cut filter varies depending on the application, but the transmittance at at least one point in the wavelength range of 700 to 1000 nm is preferably 20% or less, more preferably 15% or less. 10% or less is more preferable.
- the film of the present invention When the film of the present invention is used as an infrared transmission filter, the film of the present invention has a maximum light transmittance of 20% or less in the wavelength range of 400 to 830 nm in the thickness direction of the film.
- the minimum value of light transmittance in the wavelength range of 1000 to 1300 nm is preferably 80% or more.
- a film having such spectral characteristics can be preferably used as an infrared transmission filter that blocks light in the wavelength range of 400 to 750 nm and transmits light having a wavelength of 900 nm or more.
- the film of the present invention can be used for various devices such as a solid-state imaging device such as a CCD (Charge Coupled Device) and a CMOS (Complementary Metal Oxide Semiconductor), an infrared sensor, and an image display device.
- a solid-state imaging device such as a CCD (Charge Coupled Device) and a CMOS (Complementary Metal Oxide Semiconductor), an infrared sensor, and an image display device.
- membrane of this invention can be manufactured through the process of apply
- the composition is preferably coated 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. These substrates may be formed with an organic film or an inorganic film. As a material of the organic film, for example, the resin described in the column of the composition described above can be given. Further, as the support, a substrate made of a resin can be used.
- the support may be formed with a charge coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, or the like.
- CMOS complementary metal oxide semiconductor
- the support may be formed with a black matrix that isolates each pixel.
- 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, if necessary.
- an inorganic film formed on the glass substrate or dealkalized on the glass substrate it is preferable to use an inorganic film formed on the glass substrate or dealkalized on the glass substrate.
- a known method can be used as a method for applying the composition.
- 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.
- Various printing methods transfer methods using a mold or the like; nanoimprint methods and the like.
- the composition layer formed by applying the composition 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 even more 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 seconds to 3000 seconds, more preferably 40 to 2500 seconds, and further preferably 80 to 220 seconds. Drying can be performed with a hot plate, oven, or the like.
- the film production method of the present invention may further include a step of forming a pattern.
- a pattern forming method using a photolithography method is preferable.
- the pattern forming method by the photolithography method includes a step of exposing the composition layer formed by applying the composition of the present invention (exposure step), and developing and removing the composition layer in the unexposed area. And a step of forming a pattern (development step). If necessary, a step of baking the developed pattern (post-bake step) may be provided.
- exposure step exposing the composition layer formed by applying the composition of the present invention
- development step a step of forming a pattern
- post-bake step a step of baking the developed pattern
- the composition layer is exposed in a pattern.
- the composition layer can be subjected to pattern exposure 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 is preferably ultraviolet rays such as g-line and i-line, and i-line is more preferable.
- Irradiation dose (exposure dose) for example, preferably 0.03 ⁇ 2.5J / cm 2, more preferably 0.05 ⁇ 1.0J / cm 2, most preferably 0.08 ⁇ 0.5J / cm 2 .
- the oxygen concentration at the time of exposure can be appropriately selected.
- the exposure illuminance can be set as appropriate, and can usually be selected from the range of 1000 W / m 2 to 100,000 W / m 2 (for example, 5000 W / m 2 , 15000 W / m 2 , 35000 W / m 2 ). .
- 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.
- a pattern is formed by developing and removing the unexposed composition layer in the exposed composition layer.
- the development removal of the composition layer in the unexposed area 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.
- the 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.
- the developer may contain a surfactant. Examples of the surfactant include the surfactant described in the above-described composition, and a nonionic surfactant is preferable.
- the developer may be once manufactured as a concentrated solution and diluted to a necessary concentration at the time of use from the viewpoint of convenience of transportation and storage.
- the dilution factor is not particularly limited, but can be set, for example, in the range of 1.5 to 100 times.
- clean (rinse) with a pure water after image development.
- Post-baking is a heat treatment after development for complete film curing.
- the post-baking temperature is preferably 100 to 240 ° C., for example. From the viewpoint of film curing, 200 to 230 ° C is more preferable.
- the post-bake temperature is preferably 150 ° C. or lower, more preferably 120 ° C. or lower. Preferably, 100 ° C. or lower is more preferable, and 90 ° C. or lower is particularly preferable.
- the lower limit can be, for example, 50 ° C. or higher.
- Post-bake is 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 as to satisfy the above conditions for the developed film. Can do. Further, when a pattern is formed by a low temperature process, post baking is not necessary.
- the near-infrared cut filter of the present invention has the above-described film of the present invention.
- the near-infrared cut filter of the present invention may further have a copper-containing layer, a dielectric multilayer film, an ultraviolet absorption layer and the like in addition to the film of the present invention.
- the near-infrared cut filter of the present invention further has a copper-containing layer and / or a dielectric multilayer film, whereby a near-infrared cut filter having a wide viewing angle and excellent near-infrared shielding properties can be easily obtained.
- the near-infrared cut filter of this invention can be set as the near-infrared cut filter excellent in ultraviolet-shielding property by having an ultraviolet absorption layer further.
- the ultraviolet absorbing layer for example, the absorbing layer described in paragraph Nos.
- the glass base material (copper containing glass base material) comprised with the glass containing copper and the layer (copper complex containing layer) containing a copper complex can also be used.
- the copper-containing glass substrate include a phosphate glass containing copper and a fluorophosphate glass containing copper.
- Examples of commercially available copper-containing glass include NF-50 (manufactured by AGC Techno Glass Co., Ltd.), BG-60, BG-61 (manufactured by Schott Corp.), CD5000 (manufactured by HOYA Co., Ltd.), and the like.
- the near-infrared cut filter of the present invention can be used for various devices such as a solid-state imaging device such as a CCD (Charge Coupled Device) and a CMOS (Complementary Metal Oxide Semiconductor), an infrared sensor, and an image display device.
- a solid-state imaging device such as a CCD (Charge Coupled Device) and a CMOS (Complementary Metal Oxide Semiconductor)
- an infrared sensor and an image display device.
- the near-infrared cut filter of the present invention comprises a film pixel (pattern) obtained using the composition of the present invention, and a pixel (pattern) selected from red, green, blue, magenta, yellow, cyan, black and colorless.
- a film pixel obtained using the composition of the present invention
- a pixel selected from red, green, blue, magenta, yellow, cyan, black and colorless.
- An embodiment having a is also a preferred embodiment.
- the solid-state imaging device of the present invention includes the above-described film of the present invention.
- the configuration of the solid-state imaging device is not particularly limited as long as it is a configuration having the film of the present invention and functions as a solid-state imaging device. For example, the following configurations can be mentioned.
- the device protective film has a condensing means (for example, a microlens, etc., the same shall apply hereinafter) under the film in the present invention (on the side close to the support), or on the film in the present invention.
- the structure etc. which have a means may be sufficient.
- the color filter may have a structure in which a film forming each pixel is embedded in a space partitioned by a partition, for example, in a lattice shape.
- the partition wall preferably has a lower refractive index than each pixel. Examples of the image pickup apparatus having such a structure include apparatuses described in JP 2012-227478 A and JP 2014-179577 A.
- the image display device of the present invention includes the film of the present invention.
- Examples of the image display device include a liquid crystal display device and an organic electroluminescence (organic EL) display device.
- organic EL organic electroluminescence
- image display devices refer to, for example, “Electronic Display Device (Akio Sasaki, published by Industrial Research Institute, 1990)”, “Display Device (written by Junaki Ibuki, published in 1989 by Sangyo Tosho). ) "Etc.
- the liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”.
- the liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.
- the image display device may have a white organic EL element.
- the white organic EL element preferably has a tandem structure.
- JP 2003-45676 A supervised by Akiyoshi Mikami, “Frontier of Organic EL Technology Development-High Brightness, High Precision, Long Life, Know-how Collection”, Technical Information Association, 326-328 pages, 2008, etc.
- the spectrum of white light emitted from the organic EL element preferably has a strong maximum emission peak in the blue region (430 nm to 485 nm), the green region (530 nm to 580 nm) and the yellow region (580 nm to 620 nm). In addition to these emission peaks, those having a maximum emission peak in the red region (650 nm to 700 nm) are more preferable.
- the infrared sensor of the present invention includes the above-described film of the present invention.
- the configuration of the infrared sensor is not particularly limited as long as it functions as an infrared sensor.
- an embodiment of an infrared sensor of the present invention will be described with reference to the drawings.
- reference numeral 110 denotes a solid-state image sensor.
- the imaging region provided on the solid-state imaging device 110 includes a near infrared cut filter 111 and an infrared transmission filter 114.
- a color filter 112 is laminated on the near infrared cut filter 111.
- a micro lens 115 is disposed on the incident light h ⁇ side of the color filter 112 and the infrared transmission filter 114.
- a planarization layer 116 is formed so as to cover the microlens 115.
- the near-infrared cut filter 111 can be formed using the composition of the present invention.
- the spectral characteristic of the near-infrared cut filter 111 is selected according to the emission wavelength of the infrared light-emitting diode (infrared LED) to be used.
- the color filter 112 is a color filter in which pixels that transmit and absorb light of a specific wavelength in the visible region are formed, and is not particularly limited, and a conventionally known color filter for pixel formation can be used.
- a color filter in which red (R), green (G), and blue (B) pixels are formed is used.
- R red
- G green
- B blue
- paragraph numbers 0214 to 0263 in Japanese Patent Application Laid-Open No. 2014-043556 can be referred to, and the contents thereof are incorporated in the present specification.
- the characteristics of the infrared transmission filter 114 are selected according to the emission wavelength of the infrared LED used.
- the infrared transmission filter 114 preferably has a maximum light transmittance of 30% or less in the wavelength range of 400 to 650 nm in the thickness direction of the film. % Or less, more preferably 10% or less, and particularly preferably 0.1% or less. This transmittance preferably satisfies the above conditions throughout the wavelength range of 400 to 650 nm.
- the minimum value of the light transmittance in the thickness direction of the film in the wavelength range of 800 nm or more is preferably 70% or more, more preferably 80% or more. More preferably, it is 90% or more.
- the above transmittance preferably satisfies the above condition in a part of the wavelength range of 800 nm or more, and preferably satisfies the above condition at a wavelength corresponding to the emission wavelength of the infrared LED.
- the film thickness of the infrared transmission filter 114 is preferably 100 ⁇ m or less, more preferably 15 ⁇ m or less, further preferably 5 ⁇ m or less, and particularly preferably 1 ⁇ m or less.
- the lower limit is preferably 0.1 ⁇ m.
- a method for measuring the spectral characteristics, film thickness, etc. of the infrared transmission filter 114 is shown below.
- the film thickness was measured using a stylus type surface shape measuring instrument (DEKTAK150 manufactured by ULVAC) for the dried substrate having the film.
- the spectral characteristic of the film is a value obtained by measuring the transmittance in the wavelength range of 300 to 1300 nm using an ultraviolet-visible near-infrared spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).
- the infrared transmission filter 114 has a maximum light transmittance in the thickness direction of the film in the wavelength range of 450 to 650 nm of 20% or less.
- the transmittance of light having a wavelength of 835 nm is preferably 20% or less
- the minimum value of the transmittance of light in the thickness direction of the film in the wavelength range of 1000 to 1300 nm is preferably 70% or more.
- a near-infrared cut filter (another near-infrared cut filter) different from the near-infrared cut filter 111 may be further disposed on the planarizing layer 116.
- Other near infrared cut filters include those having a layer containing copper and / or a dielectric multilayer film. About these details, what was mentioned above is mentioned. Further, as another near infrared cut filter, a dual band pass filter may be used.
- the acid value of compound A and resin represents the mass of potassium hydroxide required to neutralize the acidic component per gram of solid content.
- the acid value was calculated by the following formula using the inflection point of the titration pH curve as the titration end point.
- A 56.11 ⁇ Vs ⁇ 0.5 ⁇ f / w
- f Potency of 0.1 mol / L sodium hydroxide aqueous solution
- the C ⁇ C value of Compound A represents the molar amount of C ⁇ C groups per gram of the solid content of Compound A, and the C ⁇ C group site (for example, P-1 described above) from Compound A by alkali treatment.
- the low molecular component (a) of methacrylic acid in (2) and acrylic acid (in P-2) was taken out, and the content thereof was measured by high performance liquid chromatography (HPLC) and calculated from the following formula.
- the reaction solution was neutralized with 10.2 mL of a 4 mol / L methanesulfonic acid aqueous solution, and then a mixed solution containing 5 mL of ion-exchanged water and 2 mL of methanol was transferred to a 100 mL volumetric flask, and measured up by measuring with HPLC.
- HPLC 100 mL volumetric flask
- ⁇ C C value calculation formula>
- ⁇ HPLC measurement conditions> Measuring instrument: Agilent-1200 Column: Phenomenex Synergy 4u Polar-RP 80A, 250 mm x 4.60 mm (inner diameter) + guard column Column temperature: 40 ° C Analysis time: 15 minutes Flow rate: 1.0 mL / min (maximum liquid feed pressure: 182 bar) Injection volume: 5 ⁇ l Detection wavelength: 210 nm El
- the dispersions of Examples 1 to 9 had a low viscosity increase rate and excellent stability over time.
- the curable composition was prepared by mixing the raw materials described in the following table.
- the numerical values described below are parts by mass.
- the numerical value of the mass part described in the column of the near-infrared absorbing compound, the chromatic colorant, the dispersant, the resin, the polymerizable compound, the ultraviolet absorber, the surfactant, the polymerization inhibitor, and the coloring inhibitor is the value of the solid content. It is.
- the dispersion prepared as follows was used.
- the chromatic colorant of the type described in the column of the dispersion B, the dispersant and the solvent are mixed in the parts by mass described in the column of the dispersion B in the following table, respectively, and further 230 masses of zirconia beads having a diameter of 0.3 mm. Part was added, a dispersion treatment was performed for 5 hours using a paint shaker, and beads were separated by filtration to prepare dispersion B.
- CT-4000 (manufactured by FUJIFILM Electronics Materials Co., Ltd.) is applied on a silicon wafer by spin coating so that the film thickness becomes 0.1 ⁇ m, and heated at 220 ° C. for 1 hour using a hot plate. A stratum was formed.
- a curable composition is applied onto the silicon wafer with the underlayer by a spin coating method, and then heated at 100 ° C. for 2 minutes using a hot plate to obtain a composition layer having a thickness described in the following table. It was.
- an i-line stepper FPA-3000i5 + (manufactured by Canon Inc.) was used, and a square pixel having a side of 1.1 ⁇ m was arranged in a 4 mm ⁇ 3 mm region on the substrate through a mask pattern. Exposure was performed with light having a wavelength of 365 nm and an exposure amount of 500 mJ / cm 2 . The composition layer after the exposure was subjected to paddle development for 60 seconds at 23 ° C. using a 0.3 mass% aqueous solution of tetramethylammonium hydroxide. Then, it rinsed using water in the spin shower, and also washed with pure water.
- the examples had excellent adhesion.
- (Pigment derivative) B1 to B3 Compounds having the following structures.
- Me represents a methyl group
- Ph represents a phenyl group.
- Dispersant P-1 to P-8, P-16: P-1 to P-8 and P-16 mentioned as specific examples of the compound A described above.
- E1 Polymerizable compound
- E2 Aronix M-305 (Toagosei Co., Ltd.)
- E2 NK ester A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)
- E3 KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)
- E4 Aronix M-510 (Toagosei Co., Ltd.)
- Example 2 The curable compositions of Examples 101 to 109 were applied on a silicon wafer by spin coating so that the film thickness after film formation was 1.0 ⁇ m. Subsequently, it heated at 100 degreeC for 2 minute (s) using the hotplate. Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), exposure was performed through a mask having a Bayer pattern of 2 ⁇ m square at an exposure amount of 1000 mJ / cm 2 . Subsequently, paddle development was performed at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH).
- TMAH tetramethylammonium hydroxide
- TMAH tetramethylammonium hydroxide
- the Red composition was patterned on the Bayer pattern of the near-infrared cut filter by heating at 200 ° C. for 5 minutes using a hot plate.
- the Green composition and the Blue composition were sequentially patterned to form red, green, and blue coloring patterns.
- the infrared transmission filter forming composition was applied onto the patterned film by spin coating so that the film thickness after film formation was 2.0 ⁇ m. Subsequently, it heated at 100 degreeC for 2 minute (s) using the hotplate.
- i-line stepper exposure apparatus FPA-3000i5 + manufactured by Canon Inc.
- exposure was performed through a mask having a Bayer pattern of 2 ⁇ m square at an exposure amount of 1000 mJ / cm 2 .
- paddle development was performed at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH).
- TMAH tetramethylammonium hydroxide
- the infrared transmission filter was patterned in the portion where the Bayer pattern of the near infrared cut filter was removed by heating at 200 ° C. for 5 minutes using a hot plate.
- the obtained solid-state imaging device was irradiated with light from an infrared light emitting diode (infrared LED) light source in a low illuminance environment (0.001 Lux), and an image was captured to evaluate the image performance.
- the subject was clearly recognized on the image. Moreover, the incident angle dependency was good.
- the Red composition, Green composition, Blue composition, and infrared transmission filter forming composition used in Test Example 2 are as follows.
- Red composition The following components were mixed and stirred, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 ⁇ m to prepare a Red composition.
- Red pigment dispersion 51.7 parts by weight
- Resin 104 ... 0.6 parts by weight
- Polymerizable compound 104 ... 0.6 parts by weight
- Photopolymerization initiator 101 ... 0.4 parts by weight
- Ultraviolet absorber UV-503, manufactured by Daito Chemical Co., Ltd.
- PGMEA Ultraviolet absorber
- Green composition The following components were mixed and stirred, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 ⁇ m to prepare a Green composition.
- Green pigment dispersion 73.7 parts by weight
- Resin 104 0.3 parts by weight
- Polymerizable compound 101 1.2 parts by weight
- Photopolymerization initiator 101 0.6 parts by weight
- Blue composition The following components were mixed and stirred, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 ⁇ m to prepare a Blue composition.
- the raw materials used in the Red composition, the Green composition, the Blue composition, and the infrared transmission filter forming composition are as follows.
- Red pigment dispersion C.I. I. Pigment Red 254, 9.6 parts by mass, C.I. I. Pigment Yellow 139 (4.3 parts by mass), a dispersant (Disperbyk-161, manufactured by BYK Chemie) (6.8 parts by mass) and PGMEA (79.3 parts by mass) were mixed in a bead mill (zirconia bead 0.3 mm diameter).
- the pigment dispersion was prepared by mixing and dispersing for 3 hours. Thereafter, the dispersion treatment was further performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm 3 using a high-pressure disperser NANO-3000-10 with a decompression mechanism (manufactured by Nippon BEE Co., Ltd.). This dispersion treatment was repeated 10 times to obtain a Red pigment dispersion.
- Green pigment dispersion C.I. I. 6.4 parts by mass of Pigment Green 36, C.I. I. Pigment Yellow 150, 5.3 parts by mass of a dispersing agent (Disperbyk-161, manufactured by BYK Chemie), and a mixed solution consisting of 83.1 parts by mass of PGMEA were used as a bead mill (zirconia beads 0.3 mm diameter).
- a dispersing agent Dispersing agent (Disperbyk-161, manufactured by BYK Chemie)
- a mixed solution consisting of 83.1 parts by mass of PGMEA were used as a bead mill (zirconia beads 0.3 mm diameter).
- the dispersion treatment was further performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm 3 using a high-pressure disperser NANO-3000-10 with a decompression mechanism (manufactured by Nippon BEE Co., Ltd.). This dispersion treatment was repeated 10 times to obtain a Green pigment dis
- Blue pigment dispersion C.I. I. Pigment Blue 15: 6 is 9.7 parts by mass, C.I. I. Pigment Violet 23, 2.4 parts by mass, Dispersant (Disperbyk-161, manufactured by BYK Chemie) 5.5 parts by mass, and PGMEA 82.4 parts by mass were mixed in a bead mill (zirconia beads 0.3 mm diameter). Was mixed and dispersed for 3 hours to prepare a pigment dispersion. Thereafter, the dispersion treatment was further performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm 3 using a high-pressure disperser NANO-3000-10 with a decompression mechanism (manufactured by Nippon BEE Co., Ltd.). This dispersion treatment was repeated 10 times to obtain a Blue pigment dispersion.
- Pigment dispersion 1-1 A mixed solution having the following composition was mixed and dispersed for 3 hours using a zirconia bead having a diameter of 0.3 mm in a bead mill (high pressure disperser NANO-3000-10 with a pressure reducing mechanism (manufactured by Nippon BEE Co., Ltd.)). Thus, a pigment dispersion 1-1 was prepared. -Mixed pigment consisting of red pigment (CI Pigment Red 254) and yellow pigment (CI Pigment Yellow 139) ... 11.8 parts by mass-Resin (Disperbyk-111, manufactured by BYKChemie) ... 9.1 parts by mass / PGMEA 79.1 parts by mass
- Pigment dispersion 1-2 A mixed solution having the following composition was mixed and dispersed for 3 hours using a zirconia bead having a diameter of 0.3 mm in a bead mill (high pressure disperser NANO-3000-10 with a pressure reducing mechanism (manufactured by Nippon BEE Co., Ltd.)). Thus, a pigment dispersion 1-2 was prepared. -Mixed pigment consisting of blue pigment (CI Pigment Blue 15: 6) and purple pigment (CI Pigment Violet 23) ...
- Polymerizable compound 101 KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)
- Polymerizable compound 104 Compound having the following structure
- Polymerizable compound 105 Compound having the following structure (a mixture in which the molar ratio of the left compound to the right compound is 7: 3)
- Photopolymerization initiator 101 IRGACURE-OXE01 (manufactured by BASF)
- Photopolymerization initiator 102 Compound having the following structure
- Silane coupling agent A compound having the following structure.
- Et represents an ethyl group.
- 110 Solid-state imaging device
- 111 Near-infrared cut filter
- 112 Color filter
- 114 Infrared transmission filter
- 115 Micro lens
- 116 Flattening layer
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Abstract
Description
<1> 単環または縮合環の芳香族環を含むπ共役平面を有する近赤外線吸収化合物と、
ラジカル重合性のエチレン性不飽和基を有する重量平均分子量3000以上の化合物Aと、を含み、
化合物Aは、グラフト鎖を有する繰り返し単位を含む、組成物。
<2> 化合物Aが有するラジカル重合性のエチレン性不飽和基は、ビニル基、ビニロキシ基、アリル基、メタリル基、(メタ)アクリロイル基、スチレン基、シンナモイル基およびマレイミド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> グラフト鎖は、ポリエステル構造、ポリエーテル構造、ポリ(メタ)アクリル構造、ポリウレタン構造、ポリウレア構造およびポリアミド構造から選ばれる少なくとも1種の構造を含む、<1>または<2>に記載の組成物。
<4> グラフト鎖は、ポリエステル構造を含む、<3>に記載の組成物。
<5> グラフト鎖を有する繰り返し単位の重量平均分子量が1000以上である、<1>~<4>のいずれか1つに記載の組成物。
<6> 化合物Aは、ラジカル重合性のエチレン性不飽和基を有する繰り返し単位と、グラフト鎖を有する繰り返し単位とを含む、<1>~<5>のいずれか1つに記載の組成物。
<7> 化合物Aは、下記式(A-1-1)で表される繰り返し単位と、下記式(A-1-2)で表される繰り返し単位とを含む、<1>~<6>のいずれか1つに記載の組成物;
式(A-1-2)において、X2は繰り返し単位の主鎖を表し、L2は単結合または2価の連結基を表し、W1はグラフト鎖を表す。
<8> 化合物Aは、更に、酸基を有する繰り返し単位を含む、<1>~<7>のいずれか1つに記載の組成物。
<9> 化合物Aのラジカル重合性のエチレン性不飽和基量が0.2~5.0mmol/gである、<1>~<8>のいずれか1つに記載の組成物。
<10> 化合物Aの酸価が20~150mgKOH/gである、<1>~<9>のいずれか1つに記載の組成物。
<11> 近赤外線吸収化合物は、ピロロピロール化合物、シアニン化合物、スクアリリウム化合物、フタロシアニン化合物、ナフタロシアニン化合物およびジイモニウム化合物から選ばれる少なくとも1種である、<1>~<10>のいずれか1つに記載の組成物。
<12> 更に、赤外線を透過させて可視光を遮光する色材を含む、<1>~<11>のいずれか1つに記載の組成物。
<13> <1>~<12>のいずれか1つに記載の組成物から得られる膜。
<14> <13>に記載の膜を有する近赤外線カットフィルタ。
<15> <13>に記載の膜を有する固体撮像素子。
<16> <13>に記載の膜を有する画像表示装置。
<17> <13>に記載の膜を有する赤外線センサ。
本明細書において、「~」とはその前後に記載される数値を下限値および上限値として含む意味で使用される。
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(原子団)と共に置換基を有する基(原子団)をも包含する。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)をも包含する。
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露光に含める。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、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(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-8220GPC(東ソー(株)製)を用い、カラムとして、TOSOH TSKgel Super HZM-HとTOSOH TSKgel Super HZ4000とTOSOH TSKgel Super HZ2000とを連結したカラムを用い、展開溶媒としてテトラヒドロフラン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、化学式中のMeはメチル基を表し、Etはエチル基を表し、Buはブチル基を表し、Phはフェニル基を表す。
本明細書において、近赤外線とは、波長700~2500nmの光(電磁波)をいう。
本明細書において、全固形分とは、組成物の全成分から溶剤を除いた成分の総質量をいう。
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。
本発明の組成物は、単環または縮合環の芳香族環を含むπ共役平面を有する近赤外線吸収化合物と、ラジカル重合性のエチレン性不飽和基を有する重量平均分子量3000以上の化合物Aと、を含み、化合物Aはグラフト鎖を有する繰り返し単位を含むことを特徴とする。
本発明の組成物は、単環または縮合環の芳香族環を含むπ共役平面を有する化合物である近赤外線吸収化合物を含有する。本発明において、近赤外線吸収化合物は、近赤外領域(好ましくは、波長700~1300nmの範囲、さらに好ましくは波長700~1000nmの範囲)に吸収を有する化合物であることが好ましい。
式(C)
R101およびR102は、それぞれ独立に、アルキル基、アルケニル基、アルキニル基、アラルキル基またはアリール基を表し、
L1は、奇数個のメチン基を有するメチン鎖を表し、
aおよびbは、それぞれ独立に、0または1であり、
aが0の場合は、炭素原子と窒素原子とが二重結合で結合し、bが0の場合は、炭素原子と窒素原子とが単結合で結合し、
式中のCyで表される部位がカチオン部である場合、X1はアニオンを表し、cは電荷のバランスを取るために必要な数を表し、式中のCyで表される部位がアニオン部である場合、X1はカチオンを表し、cは電荷のバランスを取るために必要な数を表し、式中のCyで表される部位の電荷が分子内で中和されている場合、cは0である。
本発明の組成物において、近赤外線吸収化合物の含有量は、後述する化合物Aの100質量部に対して、100~500質量部であることが好ましい。
本発明において、近赤外線吸収化合物は1種のみを用いてもよく、2種以上を用いてもよい。2種以上を用いる場合は、合計量が上記範囲となることが好ましい。
本発明の組成物において、上述した近赤外線吸収化合物以外の近赤外線吸収剤(他の近赤外線吸収剤ともいう)を更に含んでもよい。他の近赤外線吸収剤としては、無機顔料(無機粒子)が挙げられる。無機顔料の形状は特に制限されず、球状、非球状を問わず、シート状、ワイヤー状、チューブ状であってもよい。無機顔料としては、金属酸化物粒子または金属粒子が好ましい。金属酸化物粒子としては、例えば、酸化インジウムスズ(ITO)粒子、酸化アンチモンスズ(ATO)粒子、酸化亜鉛(ZnO)粒子、Alドープ酸化亜鉛(AlドープZnO)粒子、フッ素ドープ二酸化スズ(FドープSnO2)粒子、ニオブドープ二酸化チタン(NbドープTiO2)粒子などが挙げられる。金属粒子としては、例えば、銀(Ag)粒子、金(Au)粒子、銅(Cu)粒子、ニッケル(Ni)粒子など挙げられる。また、無機顔料としては酸化タングステン系化合物を用いることもできる。酸化タングステン系化合物は、セシウム酸化タングステンであることが好ましい。酸化タングステン系化合物の詳細については、特開2016-006476号公報の段落番号0080を参酌でき、この内容は本明細書に組み込まれる。
また、上述した近赤外線吸収化合物と他の近赤外線吸収剤との合計質量中における他の近赤外線吸収化合剤の含有量は、1~99質量%が好ましい。上限は、80質量%以下が好ましく、50質量%以下がより好ましく、30質量%以下がさらに好ましい。
また、本発明の組成物は他の近赤外線吸収剤を実質的に含有しないことも好ましい。他の近赤外線吸収剤を実質的に含有しないとは、上述した近赤外線吸収化合物と他の近赤外線吸収剤との合計質量中における他の近赤外線吸収剤の含有量が0.5質量%以下であることが好ましく、0.1質量%以下であることがより好ましく、他の近赤外線吸収剤を含有しないことが更に好ましい。
本発明の組成物は、グラフト鎖を有する繰り返し単位を含み、かつ、ラジカル重合性のエチレン性不飽和基を有する重量平均分子量(Mw)3000以上の化合物Aを含む。本発明において、化合物Aは、分散剤として用いることもできる。
化合物AのC=C価[mmol/g]=(低分子成分(a)の含有量[ppm]/低分子成分(a)の分子量[g/mol])/(化合物Aの秤量値[g]×(化合物Aの固形分濃度[質量%]/100)×10
上記式において、RG3は、水素原子またはメチル基を表す。
上記式において、QG1は、-O-または-NH-を表し、LG1は、単結合または2価の連結基を表す。2価の連結基としては、アルキレン基(好ましくは炭素数1~12のアルキレン基)、アルキレンオキシ基(好ましくは炭素数1~12のアルキレンオキシ基)、オキシアルキレンカルボニル基(好ましくは炭素数1~12のオキシアルキレンカルボニル基)、アリーレン基(好ましくは炭素数6~20のアリーレン基)、-NH-、-SO-、-SO2-、-CO-、-O-、-COO-、OCO-、-S-およびこれらの2以上を組み合わせてなる基が挙げられる。
RG4は、水素原子または置換基を表す。置換基としては、アルキル基、アリール基、ヘテロアリール基、アルコキシ基、アリールオキシ基、ヘテロアリールオキシ基、アルキルチオエーテル基、アリールチオエーテル基、ヘテロアリールチオエーテル基等が挙げられる。
式(A-1-2)におけるX2が表す繰り返し単位の主鎖としては、式(A-1-1)のX1で説明した構造が挙げられ、好ましい範囲も同様である。式(A-1-2)におけるL2が表す2価の連結基としては、アルキレン基(好ましくは炭素数1~12のアルキレン基)、アリーレン基(好ましくは炭素数6~20のアリーレン基)、-NH-、-SO-、-SO2-、-CO-、-O-、-COO-、OCO-、-S-およびこれらの2以上を組み合わせてなる基が挙げられる。式(A-1-2)におけるW1が表すグラフト鎖としては、上述したグラフト鎖が挙げられる。
式(A-1-3)におけるX3が表す繰り返し単位の主鎖としては、式(A-1-1)のX1で説明した構造が挙げられ、好ましい範囲も同様である。
式(A-1-3)におけるL3が表す2価の連結基としては、アルキレン基(好ましくは炭素数1~12のアルキレン基)、アルケニレン基(好ましくは炭素数2~12のアルケニレン基)、アルキレンオキシ基(好ましくは炭素数1~12のアルキレンオキシ基)、オキシアルキレンカルボニル基(好ましくは炭素数1~12のオキシアルキレンカルボニル基)、アリーレン基(好ましくは炭素数6~20のアリーレン基)、-NH-、-SO-、-SO2-、-CO-、-O-、-COO-、OCO-、-S-およびこれらの2以上を組み合わせてなる基が挙げられる。アルキレン基、アルキレンオキシ基におけるアルキレン基、オキシアルキレンカルボニル基におけるアルキレン基は、直鎖状、分岐状、及び、環状のいずれでもよく、直鎖状または分岐状が好ましい。また、アルキレン基、アルキレンオキシ基におけるアルキレン基、オキシアルキレンカルボニル基におけるアルキレン基は、置換基を有していてもよく、無置換であってもよい。置換基としては、ヒドロキシル基などが挙げられる。
式(A-1-3)におけるA1が表す酸基としては、カルボキシル基、スルホ基、リン酸基が挙げられる。
本発明の組成物は、上述した化合物A以外の重合性化合物を含有することができる。重合性化合物としては、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。エチレン性不飽和基としては、ビニル基、スチレン基、アリル基、メタリル基、(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、上述した化合物Aと、化合物A以外の重合性化合物との合計含有量は、組成物の全固形分に対して、5~50質量%が好ましい。下限は、例えば7質量%以上がより好ましく、10質量%以上が更に好ましい。上限は、例えば、45質量%以下がより好ましく、40質量%以下が更に好ましい。
重合性化合物は1種単独であってもよいし、2種以上を併用してもよい。重合性化合物を2種以上併用する場合は、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、光重合開始剤を含有することができる。光重合開始剤としては、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線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であることが好ましい。
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であることが特に好ましい。
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、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、上述した化合物A以外の樹脂をさらに含有することができる。化合物A以外の樹脂としては、グラフト鎖を有さない樹脂、ラジカル重合性の不飽和結合基を有さない樹脂などが挙げられる。本発明において樹脂は、例えば、顔料などの粒子を組成物中で分散させる用途やバインダーの用途で配合される。なお、主に顔料などの粒子を分散させるために用いられる樹脂を分散剤ともいう。ただし、樹脂のこのような用途は一例であって、このような用途以外の目的で樹脂を使用することもできる。
本発明の組成物は、赤外線を透過させて可視光を遮光する色材(以下、可視光を遮光する色材ともいう)を含有することもできる。本発明において、可視光を遮光する色材は、紫色から赤色の波長領域の光を吸収する色材であることが好ましい。また、本発明において、可視光を遮光する色材は、波長400~640nmの波長領域の光を遮光する色材であることが好ましい。また、可視光を遮光する色材は、波長900~1300nmの光を透過する色材であることが好ましい。本発明において、可視光を遮光する色材は、以下の(A)および(B)の少なくとも一方の要件を満たすことが好ましい。
(1):2種類以上の有彩色着色剤を含み、2種以上の有彩色着色剤の組み合わせで黒色を形成している。
(2):有機系黒色着色剤を含む。(2)の態様において、更に有彩色着色剤を含有することも好ましい。
なお、本発明において、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。また、本発明において、可視光を遮光する色材としての有機系黒色着色剤は、可視光を吸収するが、赤外線の少なくとも一部は透過する材料を意味する。したがって、本発明において、可視光を遮光する色材としての有機系黒色着色剤は、可視光線および赤外線の両方を吸収する黒色着色剤、例えば、カーボンブラックやチタンブラックは含まない。有機系黒色着色剤は、波長400nm以上700nm以下の範囲に極大吸収波長を有する着色剤が好ましい。
上記の特性は、1種類の素材で満たしていてもよく、複数の素材の組み合わせで満たしていてもよい。例えば、上記(1)の態様の場合、複数の有彩色着色剤を組み合わせて上記分光特性を満たしていることが好ましい。また、上記(2)の態様の場合、有機系黒色着色剤が上記分光特性を満たしていてもよい。また、有機系黒色着色剤と有彩色着色剤との組み合わせで上記の分光特性を満たしていてもよい。
本発明において、有彩色着色剤は、赤色着色剤、緑色着色剤、青色着色剤、黄色着色剤、紫色着色剤およびオレンジ色着色剤から選ばれる着色剤であることが好ましい。本発明において、有彩色着色剤は、顔料であってもよく、染料であってもよい。好ましくは顔料である。顔料は、平均粒径(r)が、20nm≦r≦300nmであることが好ましく、25nm≦r≦250nmであることがより好ましく、30nm≦r≦200nmであることが更に好ましい。ここでいう「平均粒径」とは、顔料の一次粒子が集合した二次粒子についての平均粒径を意味する。また、使用しうる顔料の二次粒子の粒径分布(以下、単に「粒径分布」ともいう。)は、平均粒径±100nmの範囲に含まれる二次粒子が全体の70質量%以上であることが好ましく、80質量%以上であることがより好ましい。なお、二次粒子の粒径分布は、散乱強度分布を用いて測定することができる。
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合せて用いることができる。
(1)赤色着色剤と青色着色剤とを含有する態様。
(2)赤色着色剤と青色着色剤と黄色着色剤とを含有する態様。
(3)赤色着色剤と青色着色剤と黄色着色剤と紫色着色剤とを含有する態様。
(4)赤色着色剤と青色着色剤と黄色着色剤と紫色着色剤と緑色着色剤とを含有する態様。
(5)赤色着色剤と青色着色剤と黄色着色剤と緑色着色剤とを含有する態様。
(6)赤色着色剤と青色着色剤と緑色着色剤とを含有する態様。
(7)黄色着色剤と紫色着色剤とを含有する態様。
上記(2)の態様において、赤色着色剤と青色着色剤と黄色着色剤の質量比は、赤色着色剤:青色着色剤:黄色着色剤=10~80:20~80:10~40であることが好ましく、10~60:30~80:10~30であることがより好ましく、10~40:40~80:10~20であることが更に好ましい。
上記(3)の態様において、赤色着色剤と青色着色剤と黄色着色剤と紫色着色剤との質量比は、赤色着色剤:青色着色剤:黄色着色剤:紫色着色剤=10~80:20~80:5~40:5~40であることが好ましく、10~60:30~80:5~30:5~30であることがより好ましく、10~40:40~80:5~20:5~20であることが更に好ましい。
上記(4)の態様において、赤色着色剤と青色着色剤と黄色着色剤と紫色着色剤と緑色着色剤の質量比は、赤色着色剤:青色着色剤:黄色着色剤:紫色着色剤:緑色着色剤=10~80:20~80:5~40:5~40:5~40であることが好ましく、10~60:30~80:5~30:5~30:5~30であることがより好ましく、10~40:40~80:5~20:5~20:5~20であることが更に好ましい。
上記(5)の態様において、赤色着色剤と青色着色剤と黄色着色剤と緑色着色剤の質量比は、赤色着色剤:青色着色剤:黄色着色剤:緑色着色剤=10~80:20~80:5~40:5~40であることが好ましく、10~60:30~80:5~30:5~30であることがより好ましく、10~40:40~80:5~20:5~20であることが更に好ましい。
上記(6)の態様において、赤色着色剤と青色着色剤と緑色着色剤の質量比は、赤色着色剤:青色着色剤:緑色着色剤=10~80:20~80:10~40であることが好ましく、10~60:30~80:10~30であることがより好ましく、10~40:40~80:10~20であることが更に好ましい。
上記(7)の態様において、黄色着色剤と紫色着色剤の質量比は、黄色着色剤:紫色着色剤=10~50:40~80であることが好ましく、20~40:50~70であることがより好ましく、30~40:60~70であることが更に好ましい。
本発明において、有機系黒色着色剤としては、例えば、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化合物が挙げられ、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。
また、有彩色着色剤と有機系黒色着色剤との混合割合は、有機系黒色着色剤100質量部に対して、有彩色着色剤が10~200質量部が好ましく、15~150質量部がより好ましい。
本発明の組成物は、更に顔料誘導体を含有することができる。顔料誘導体としては、顔料の一部を、酸基、塩基性基、塩構造を有する基又はフタルイミドメチル基で置換した構造を有する化合物が挙げられる。顔料誘導体としては、式(B1)で表される化合物が好ましい。
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。有機溶剤の例としては、例えば、エステル類、エーテル類、ケトン類、芳香族炭化水素類などが挙げられる。これらの詳細については、国際公開WO2015/166779号公報の段落番号0223を参酌でき、この内容は本明細書に組み込まれる。また、環状アルキル基が置換したエステル系溶剤、環状アルキル基が置換したケトン系溶剤を好ましく用いることもできる。有機溶剤の具体例としては、ジクロロメタン、3-エトキシプロピオン酸メチル、3-エトキシプロピオン酸エチル、エチルセロソルブアセテート、乳酸エチル、ジエチレングリコールジメチルエーテル、酢酸ブチル、3-メトキシプロピオン酸メチル、2-ヘプタノン、シクロヘキサノン、酢酸シクロヘキシル、シクロペンタノン、エチルカルビトールアセテート、ブチルカルビトールアセテート、プロピレングリコールモノメチルエーテル、及びプロピレングリコールモノメチルエーテルアセテートなどが挙げられる。本発明において有機溶剤は、1種単独で用いてもよく、2種以上を組み合わせて用いてもよい。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る(例えば、有機溶剤全量に対して、50質量ppm(parts per million)以下とすることもでき、10質量ppm以下とすることもでき、1質量ppm以下とすることもできる)。
本発明の組成物は、重合禁止剤を含有することができる。重合禁止剤としては、ハイドロキノン、p-メトキシフェノール、ジ-tert-ブチル-p-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塩(アンモニウム塩、第一セリウム塩等)が挙げられる。中でも、p-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、0.001~5質量%が好ましい。
本発明の組成物は、シランカップリング剤を含有することができる。本発明において、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。また、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。また、加水分解性基以外の官能基としては、例えば、ビニル基、スチレン基、(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、フェニル基などが挙げられ、(メタ)アクリロイル基およびエポキシ基が好ましい。シランカップリング剤は、特開2009-288703号公報の段落番号0018~0036に記載の化合物、特開2009-242604号公報の段落番号0056~0066に記載の化合物が挙げられ、これらの内容は本明細書に組み込まれる。
本発明の組成物は、界面活性剤を含有させてもよい。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することができる。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。
本発明の組成物は、紫外線吸収剤を含有することができる。紫外線吸収剤としては、共役ジエン化合物、アミノブタジエン化合物、メチルジベンゾイル化合物、クマリン化合物、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、ヒドロキシフェニルトリアジン化合物などを用いることができる。これらの詳細については、特開2012-208374号公報の段落番号0052~0072、特開2013-68814号公報の段落番号0317~0334の記載を参酌でき、これらの内容は本明細書に組み込まれる。共役ジエン化合物の市販品としては、例えば、UV-503(大東化学(株)製)などが挙げられる。また、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。紫外線吸収剤としては、式(UV-1)~式(UV-3)で表される化合物が好ましく、式(UV-1)または式(UV-3)で表される化合物がより好ましく、式(UV-1)で表される化合物が更に好ましい。
式(UV-2)において、R201及びR202は、各々独立に、水素原子またはアルキル基を表し、R203及びR204は、各々独立に、置換基を表す。
式(UV-3)において、R301~R303は、各々独立に、水素原子またはアルキル基を表し、R304及びR305は、各々独立に、置換基を表す。
本発明の組成物は、酸化防止剤を含有することができる。酸化防止剤としては、フェノール化合物、亜リン酸エステル化合物、チオエーテル化合物などが挙げられる。フェノール化合物としては、フェノール系酸化防止剤として知られる任意のフェノール化合物を使用することができる。好ましいフェノール化合物としては、ヒンダードフェノール化合物が挙げられる。フェノール性水酸基に隣接する部位(オルト位)に置換基を有する化合物が好ましい。前述の置換基としては炭素数1~22の置換又は無置換のアルキル基が好ましい。また、酸化防止剤は、同一分子内にフェノール基と亜リン酸エステル基を有する化合物も好ましい。また、酸化防止剤は、リン系酸化防止剤も好適に使用することができる。リン系酸化防止剤としてはトリス[2-[[2,4,8,10-テトラキス(1,1-ジメチルエチル)ジベンゾ[d,f][1,3,2]ジオキサホスフェピン-6-イル]オキシ]エチル]アミン、トリス[2-[(4,6,9,11-テトラ-tert-ブチルジベンゾ[d,f][1,3,2]ジオキサホスフェピン-2-イル)オキシ]エチル]アミン、亜リン酸エチルビス(2,4-ジ-tert-ブチル-6-メチルフェニル)などが挙げられる。酸化防止剤の市販品としては、例えば、アデカスタブ AO-20、アデカスタブ AO-30、アデカスタブ AO-40、アデカスタブ AO-50、アデカスタブ AO-50F、アデカスタブ AO-60、アデカスタブ AO-60G、アデカスタブ AO-80、アデカスタブ AO-330(以上、(株)ADEKA)などが挙げられる。
本発明の組成物は、必要に応じて、増感剤、硬化促進剤、フィラー、熱硬化促進剤、可塑剤及びその他の助剤類(例えば、導電性粒子、充填剤、消泡剤、難燃剤、レベリング剤、剥離促進剤、香料、表面張力調整剤、連鎖移動剤など)を含有してもよい。これらの成分を適宜含有させることにより、膜物性などの性質を調整することができる。これらの成分は、例えば、特開2012-003225号公報の段落番号0183以降(対応する米国特許出願公開第2013/0034812号明細書の段落番号0237)の記載、特開2008-250074号公報の段落番号0101~0104、0107~0109等の記載を参酌でき、これらの内容は本明細書に組み込まれる。
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、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、好ましくは0.01~3.0μm程度であり、更に好ましくは0.05~0.5μm程度である。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。また、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。
また、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。
また、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。
次に、本発明の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から得られるものである。本発明の膜は、近赤外線カットフィルタや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。また、熱線遮蔽フィルタとして用いることもできる。本発明の膜は、パターンを有していてもよく、パターンを有さない膜(平坦膜)であってもよい。また、本発明の膜は、支持体上に積層して用いてもよく、本発明の膜を支持体から剥離して用いてもよい。なお、本発明の膜を赤外線透過フィルタとして用いる場合、赤外線透過フィルタとしては、例えば、可視光を遮光し、波長900nm以上の波長の光を透過するフィルタが挙げられる。なお、本発明の膜を、赤外線透過フィルタとして用いる場合、近赤外線吸収化合物と、可視光を遮光する色材(好ましくは、2種以上の有彩色着色剤を含有する色材、または、有機系黒色着色剤を少なくとも含有する色材)とを含む組成物を用いたフィルタであるか、近赤外線吸収化合物を含む層の他に、可視光を遮光する色材の層が別途存在するフィルタであることが好ましい。本発明の膜を赤外線透過フィルタとして用いる場合、近赤外線吸収化合物は、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。
次に、本発明の膜の製造方法について説明する。本発明の膜は、本発明の組成物を塗布する工程を経て製造できる。
プリベーク時間は、10秒~3000秒が好ましく、40~2500秒がより好ましく、80~220秒がさらに好ましい。乾燥は、ホットプレート、オーブン等で行うことができる。
次に、本発明の近赤外線カットフィルタについて説明する。本発明の近赤外線カットフィルタは、上述した本発明の膜を有する。
本発明の固体撮像素子は、上述した本発明の膜を含む。固体撮像素子の構成としては、本発明の膜を有する構成であり、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。例えば、以下のような構成が挙げられる。
本発明の画像表示装置は、本発明の膜を含む。画像表示装置としては、液晶表示装置や有機エレクトロルミネッセンス(有機EL)表示装置などが挙げられる。画像表示装置の定義や詳細については、例えば「電子ディスプレイデバイス(佐々木 昭夫著、(株)工業調査会 1990年発行)」、「ディスプレイデバイス(伊吹 順章著、産業図書(株)平成元年発行)」などに記載されている。また、液晶表示装置については、例えば「次世代液晶ディスプレイ技術(内田 龍男編集、(株)工業調査会 1994年発行)」に記載されている。本発明が適用できる液晶表示装置に特に制限はなく、例えば、上記の「次世代液晶ディスプレイ技術」に記載されている色々な方式の液晶表示装置に適用できる。画像表示装置は、白色有機EL素子を有するものであってもよい。白色有機EL素子としては、タンデム構造であることが好ましい。有機EL素子のタンデム構造については、特開2003-45676号公報、三上明義監修、「有機EL技術開発の最前線-高輝度・高精度・長寿命化・ノウハウ集-」、技術情報協会、326-328ページ、2008年などに記載されている。有機EL素子が発光する白色光のスペクトルは、青色領域(430nm-485nm)、緑色領域(530nm-580nm)及び黄色領域(580nm-620nm)に強い極大発光ピークを有するものが好ましい。これらの発光ピークに加え更に赤色領域(650nm-700nm)に極大発光ピークを有するものがより好ましい。
本発明の赤外線センサは、上述した本発明の膜を含む。赤外線センサの構成としては、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。以下、本発明の赤外線センサの一実施形態について、図面を用いて説明する。
赤外線透過フィルタ114の分光特性、膜厚等の測定方法を以下に示す。
膜厚は、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)を用いて測定した。
膜の分光特性は、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した値である。
化合物Aおよび樹脂の重量平均分子量は、以下の条件に従って、ゲルパーミエーションクロマトグラフィ(GPC)によって測定した。
カラムの種類:TOSOH TSKgel Super HZM-Hと、TOSOH TSKgel Super HZ4000と、TOSOH TSKgel Super HZ2000とを連結したカラム
展開溶媒:テトラヒドロフラン
カラム温度:40℃
流量(サンプル注入量):1.0μL(サンプル濃度0.1質量%)
装置名:東ソー(株)製 HLC-8220GPC
検出器:RI(屈折率)検出器
検量線ベース樹脂:ポリスチレン樹脂
化合物Aおよび樹脂の酸価は、固形分1gあたりの酸性成分を中和するのに要する水酸化カリウムの質量を表したものである。化合物Aおよび樹脂の酸価は次のようにして測定した。すなわち、測定サンプルをテトラヒドロフラン/水=9/1(質量比)混合溶媒に溶解し、電位差滴定装置(商品名:AT-510、京都電子工業製)を用いて、得られた溶液を、25℃にて、0.1mol/L水酸化ナトリウム水溶液で中和滴定した。滴定pH曲線の変曲点を滴定終点として、次式により酸価を算出した。
A=56.11×Vs×0.5×f/w
A:酸価(mgKOH/g)
Vs:滴定に要した0.1mol/L水酸化ナトリウム水溶液の使用量(mL)
f:0.1mol/L水酸化ナトリウム水溶液の力価
w:測定サンプル質量(g)(固形分換算)
化合物AのC=C価は、化合物Aの固形分1gあたりのC=C基のモル量を表したものであり、アルカリ処理により化合物AからC=C基部位(例えば、上記のP-1においてはメタクリル酸、P-2においてはアクリル酸)の低分子成分(a)を取り出し、その含有量を高速液体クロマトグラフィー(HPLC)により測定し、下記式から算出した。具体的には、測定サンプル0.1gをテトラヒドロフラン/メタノール=50mL/15mLに溶解させ、4mol/L水酸化ナトリウム水溶液10mLを加え、40℃2時間反応させた。反応液を4mol/Lメタンスルホン酸水溶液10.2mLで中和し、その後、イオン交換水5mL、メタノール2mL加えた混合液を100mLメスフラスコに移液し、メタノールでメスアップすることでHPLC測定サンプルを調製し、以下の条件で測定した。なお、低分子成分(a)の含有量は別途作成した低分子成分(a)の検量線から算出し、C=C価は下記式より算出した。
<C=C価算出式>
C=C価[mmol/g]=(低分子成分(a)含有量[ppm] /低分子成分(a)の分子量[g/mol])/(調液ポリマーの秤量値[g]×(ポリマー液の固形分濃度[%]/100)×10)
<HPLC測定条件>
測定機器: Agilent-1200
カラム: Phenomenex製 Synergi 4u Polar-RP 80A,250mm×4.60mm(内径)+ガードカラム
カラム温度:40℃
分析時間:15分
流速:1.0mL/min(最大送液圧力:182bar)
注入量:5μl
検出波長:210nm
溶離液:テトラヒドロフラン(安定剤不含HPLC用)/バッファー溶液(リン酸0.2vol%およびトリエチルアミン0.2vol%を含有するイオン交換水溶液)=55/45(vol%)
<分散液の調製>
下記の表に記載の原料を混合したのち、直径0.3mmのジルコニアビーズ230質量部を加えて、ペイントシェーカーを用いて5時間分散処理を行い、ビーズをろ過で分離して分散液を製造した。下記の表記記載の数値は質量部である。また、近赤外線吸収化合物、誘導体および分散剤の欄に記載した質量部の数値は固形分の値である。
得られた分散液の製造直後の粘度を測定した。粘度を測定した分散液を45℃の恒温槽で72時間保管し、粘度を測定した。なお、粘度は、分散液の温度を23℃に調整して測定した。以下の計算式から増粘率を算出し、経時安定性を評価した。
増粘率(%)=((45℃の恒温槽で72時間保管の分散液の粘度/製造直後の分散液の粘度)-1)×100
下記の表に記載の原料を混合して、硬化性組成物を調製した。下記の表記記載の数値は質量部である。また、近赤外線吸収化合物、有彩色着色剤、分散剤、樹脂、重合性化合物、紫外線吸収剤、界面活性剤、重合禁止剤、着色防止剤の欄に記載した質量部の数値は固形分の値である。なお、分散液Bを用いた硬化性組成物においては、以下のように調製した分散液を用いた。分散液Bの欄に記載の種類の有彩色着色剤、分散剤および溶剤を、それぞれ下記の表の分散液Bの欄に記載の質量部で混合し、更に直径0.3mmのジルコニアビーズ230質量部を加えて、ペイントシェーカーを用いて5時間分散処理を行い、ビーズをろ過で分離して分散液Bを製造した。
シリコンウエハ上にCT-4000(富士フイルムエレクトロニクスマテリアルズ(株)製)を膜厚が0.1μmとなるようにスピンコート法で塗布し、ホットプレートを用いて220℃で1時間加熱して下地層を形成した。この下地層付きのシリコンウエハ上に硬化性組成物をスピンコート法で塗布し、その後、ホットプレートを用いて100℃で2分間加熱して、下記表に記載の膜厚の組成物層を得た。
この組成物層に対して、i線ステッパーFPA-3000i5+(Canon(株)製)を使用し、一辺1.1μmの正方ピクセルがそれぞれ基板上の4mm×3mmの領域に配列されたマスクパターンを介し、365nmの波長の光を照射し、露光量500mJ/cm2にて露光を行った。
露光後の組成物層に対し、テトラメチルアンモニウムハイドロオキサイドの0.3質量%水溶液を用い、23℃で60秒間パドル現像を行った。その後、スピンシャワーにて水を用いてリンスを行い、更に純水にて水洗いを行った。その後、水滴を高圧のエアーで飛ばし、シリコンウエハを自然乾燥させたのち、ホットプレートを用いて220℃で300秒間ポストベークを行い、パターンを形成した。得られたパターンについて、光学顕微鏡を用いて観察し、全パターン中密着しているパターンをカウントして密着性を評価した。
5:すべてのパターンが密着している。
4:密着しているパターンが、全パターンの90%以上100%未満である。
3:密着しているパターンが、全パターンの80%以上90%未満である。
2:密着しているパターンが、全パターンの70%以上80%未満である。
1:密着しているパターンが、全パターンの70%未満である。
P-1~P-8、P-16:上述した化合物Aの具体例として挙げたP-1~P-8、P-16。
分散剤1:下記構造の樹脂(主鎖に付記した数値はモル比であり、側鎖に付記した数値は繰り返し単位の数である。Mw=20,000)
PR254 : C.I.Pigment Red 254
PB15:6 : C.I.Pigment Blue 15:6
PY139 : C.I.Pigment Yellow 139
D1:下記構造の樹脂。(主鎖に付記した数値はモル比である。Mw=40,000、酸価=100mgKOH/g)
D2:下記構造の樹脂。(主鎖に付記した数値はモル比である。Mw=10,000、酸価=70mgKOH/g)
E1:アロニックス M-305 (東亞合成(株)製)
E2:NKエステル A-TMMT (新中村化学工業(株)製)
E3:KAYARAD DPHA(日本化薬(株)製)
E4:アロニックスM-510 (東亞合成(株)製)
F1:IRGACURE OXE02 (BASF製)
F2:IRGACURE 369 (BASF製)
F3:IRGACURE OXE03 (BASF製)
(紫外線吸収剤)
G1、G2:下記構造の化合物
H1:下記混合物(Mw=14000、フッ素系界面活性剤)。下記の式中、繰り返し単位の割合を示す%は質量%である。
I1:p-メトキシフェノール
(酸化防止剤)
J1:アデカスタブ AO-80((株)ADEKA製)
(溶剤)
PGMEA:プロピレングリコールモノメチルエーテルアセテート
実施例101~109の硬化性組成物を、製膜後の膜厚が1.0μmになるように、シリコンウエハ上にスピンコート法で塗布した。次いで、ホットプレートを用いて、100℃で2分間加熱した。次いで、i線ステッパー露光装置FPA-3000i5+(Canon(株)製)を用い、1000mJ/cm2の露光量にて、2μm四方のBayerパターンを有するマスクを介して露光した。
次いで、水酸化テトラメチルアンモニウム(TMAH)0.3質量%水溶液を用い、23℃で60秒間パドル現像を行った。その後、スピンシャワーにてリンスを行い、さらに純水にて水洗した。次いで、ホットプレートを用いて、200℃で5分間加熱することで2μm四方のBayerパターン(近赤外線カットフィルタ)を形成した。
次に、近赤外線カットフィルタのBayerパターン上に、Red組成物を製膜後の膜厚が1.0μmになるようにスピンコート法で塗布した。次いで、ホットプレートを用い、100℃で2分間加熱した。次いで、i線ステッパー露光装置FPA-3000i5+(Canon(株)製)を用い、1000mJ/cm2の露光量にて、2μm四方のBayerパターンを有するマスクを介して露光した。次いで、水酸化テトラメチルアンモニウム(TMAH)0.3質量%水溶液を用い、23℃で60秒間パドル現像を行った。その後、スピンシャワーにてリンスを行い、さらに純水にて水洗した。次いで、ホットプレートを用い、200℃で5分間加熱することで、近赤外線カットフィルタのBayerパターン上にRed組成物をパターニングした。同様にGreen組成物、Blue組成物を順次パターニングし、赤、緑および青の着色パターンを形成した。
次に、上記パターン形成した膜上に、赤外線透過フィルタ形成用組成物を、製膜後の膜厚が2.0μmになるようにスピンコート法で塗布した。次いで、ホットプレートを用いて100℃で2分間加熱した。次いで、i線ステッパー露光装置FPA-3000i5+(Canon(株)製)を用い、1000mJ/cm2の露光量にて、2μm四方のBayerパターンを有するマスクを介して露光した。次いで、水酸化テトラメチルアンモニウム(TMAH)0.3質量%水溶液を用い、23℃で60秒間パドル現像を行った。その後、スピンシャワーにてリンスを行い、さらに純水にて水洗した。次いで、ホットプレートを用いて、200℃で5分間加熱することで、近赤外線カットフィルタのBayerパターンの抜け部分に、赤外線透過フィルタのパターニングを行った。これ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ついて、低照度の環境下(0.001Lux)で赤外発光ダイオード(赤外LED)光源から光を照射し、画像の取り込みを行い、画像性能を評価した。画像上で被写体をはっきりと認識できた。また、入射角依存性が良好であった。
下記成分を混合し、撹拌した後、孔径0.45μmのナイロン製フィルタ(日本ポール(株)製)でろ過して、Red組成物を調製した。
Red顔料分散液 ・・51.7質量部
樹脂104 ・・・0.6質量部
重合性化合物104 ・・・0.6質量部
光重合開始剤101 ・・・0.4質量部
界面活性剤101 ・・・4.2質量部
紫外線吸収剤(UV-503、大東化学(株)製) ・・・0.3質量部
PGMEA ・・・42.6質量部
下記成分を混合し、撹拌した後、孔径0.45μmのナイロン製フィルタ(日本ポール(株)製)でろ過して、Green組成物を調製した。
Green顔料分散液 ・・・73.7質量部
樹脂104 ・・・0.3質量部
重合性化合物101 ・・・1.2質量部
光重合開始剤101 ・・・0.6質量部
界面活性剤101 ・・・4.2質量部
紫外線吸収剤(UV-503、大東化学(株)製) ・・・0.5質量部
PGMEA ・・・19.5質量部
下記成分を混合し、撹拌した後、孔径0.45μmのナイロン製フィルタ(日本ポール(株)製)でろ過して、Blue組成物を調製した。
Blue顔料分散液 44.9質量部
樹脂104 ・・・2.1質量部
重合性化合物101 ・・・1.5質量部
重合性化合物104 ・・・0.7質量部
光重合開始剤101 ・・・0.8質量部
界面活性剤101 ・・・4.2質量部
紫外線吸収剤(UV-503、大東化学(株)製) ・・・0.3質量部
PGMEA ・・・45.8質量部
下記成分を混合し、撹拌した後、孔径0.45μmのナイロン製フィルタ(日本ポール(株)製)でろ過して、赤外線透過フィルタ形成用組成物を調製した。
顔料分散液1-1 ・・・46.5質量部
顔料分散液1-2 ・・・37.1質量部
重合性化合物105 ・・・1.8質量部
樹脂104 ・・・1.1質量部
光重合開始剤102 ・・・0.9質量部
界面活性剤101 ・・・4.2質量部
重合禁止剤(p-メトキシフェノール) ・・・0.001質量部
シランカップリング剤 ・・・0.6質量部
PGMEA ・・・7.8質量部
C.I.Pigment Red 254を9.6質量部、C.I.Pigment Yellow 139を4.3質量部、分散剤(Disperbyk-161、BYKChemie社製)を6.8質量部、PGMEAを79.3質量部とからなる混合液を、ビーズミル(ジルコニアビーズ0.3mm径)により3時間混合および分散して、顔料分散液を調製した。その後さらに、減圧機構付き高圧分散機NANO-3000-10(日本ビーイーイー(株)製)を用いて、2000kg/cm3の圧力下で流量500g/minとして分散処理を行なった。この分散処理を10回繰り返し、Red顔料分散液を得た。
C.I.Pigment Green 36を6.4質量部、C.I.Pigment Yellow 150を5.3質量部、分散剤(Disperbyk-161、BYKChemie社製)を5.2質量部、PGMEAを83.1質量部からなる混合液を、ビーズミル(ジルコニアビーズ0.3mm径)により3時間混合および分散して、顔料分散液を調製した。その後さらに、減圧機構付き高圧分散機NANO-3000-10(日本ビーイーイー(株)製)を用いて、2000kg/cm3の圧力下で流量500g/minとして分散処理を行なった。この分散処理を10回繰り返し、Green顔料分散液を得た。
C.I.Pigment Blue 15:6を9.7質量部、C.I.Pigment Violet 23を2.4質量部、分散剤(Disperbyk-161、BYKChemie社製)を5.5質量部、PGMEAを82.4質量部からなる混合液を、ビーズミル(ジルコニアビーズ0.3mm径)により3時間混合および分散して、顔料分散液を調製した。その後さらに、減圧機構付き高圧分散機NANO-3000-10(日本ビーイーイー(株)製)を用いて、2000kg/cm3の圧力下で流量500g/minとして分散処理を行なった。この分散処理を10回繰り返し、Blue顔料分散液を得た。
下記組成の混合液を、0.3mm径のジルコニアビーズを使用して、ビーズミル(減圧機構付き高圧分散機NANO-3000-10(日本ビーイーイー(株)製))で、3時間、混合、分散して、顔料分散液1-1を調製した。
・赤色顔料(C.I.Pigment Red 254)及び黄色顔料(C.I.Pigment Yellow 139)からなる混合顔料 ・・・11.8質量部
・樹脂(Disperbyk-111、BYKChemie社製) ・・・9.1質量部
・PGMEA ・・・79.1質量部
下記組成の混合液を、0.3mm径のジルコニアビーズを使用して、ビーズミル(減圧機構付き高圧分散機NANO-3000-10(日本ビーイーイー(株)製))で、3時間、混合、分散して、顔料分散液1-2を調製した。
・青色顔料(C.I.Pigment Blue 15:6)及び紫色顔料(C.I.Pigment Violet 23)からなる混合顔料 ・・・12.6質量部
・樹脂(Disperbyk-111、BYKChemie社製) ・・・2.0質量部
・樹脂A ・・・3.3質量部
・シクロヘキサノン ・・・31.2質量部
・PGMEA ・・・50.9質量部
樹脂A:下記構造の樹脂(Mw=14,000、構造単位における比はモル比である)
Claims (17)
- 単環または縮合環の芳香族環を含むπ共役平面を有する近赤外線吸収化合物と、
ラジカル重合性のエチレン性不飽和基を有する重量平均分子量3000以上の化合物Aと、を含み、
前記化合物Aは、グラフト鎖を有する繰り返し単位を含む、組成物。 - 前記化合物Aが有するラジカル重合性のエチレン性不飽和基は、ビニル基、ビニロキシ基、アリル基、メタリル基、(メタ)アクリロイル基、スチレン基、シンナモイル基およびマレイミド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。
- 前記グラフト鎖は、ポリエステル構造、ポリエーテル構造、ポリ(メタ)アクリル構造、ポリウレタン構造、ポリウレア構造およびポリアミド構造から選ばれる少なくとも1種の構造を含む、請求項1または2に記載の組成物。
- 前記グラフト鎖は、ポリエステル構造を含む、請求項3に記載の組成物。
- 前記グラフト鎖を有する繰り返し単位の重量平均分子量が1000以上である、請求項1~4のいずれか1項に記載の組成物。
- 前記化合物Aは、ラジカル重合性のエチレン性不飽和基を有する繰り返し単位と、グラフト鎖を有する繰り返し単位とを含む、請求項1~5のいずれか1項に記載の組成物。
- 前記化合物Aは、更に、酸基を有する繰り返し単位を含む、請求項1~7のいずれか1項に記載の組成物。
- 前記化合物Aのラジカル重合性のエチレン性不飽和基量が0.2~5.0mmol/gである、請求項1~8のいずれか1項に記載の組成物。
- 前記化合物Aの酸価が20~150mgKOH/gである、請求項1~9のいずれか1項に記載の組成物。
- 前記近赤外線吸収化合物は、ピロロピロール化合物、シアニン化合物、スクアリリウム化合物、フタロシアニン化合物、ナフタロシアニン化合物およびジイモニウム化合物から選ばれる少なくとも1種である、請求項1~10のいずれか1項に記載の組成物。
- 更に、赤外線を透過させて可視光を遮光する色材を含む、請求項1~11のいずれか1項に記載の組成物。
- 請求項1~12のいずれか1項に記載の組成物から得られる膜。
- 請求項13に記載の膜を有する近赤外線カットフィルタ。
- 請求項13に記載の膜を有する固体撮像素子。
- 請求項13に記載の膜を有する画像表示装置。
- 請求項13に記載の膜を有する赤外線センサ。
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| JP2017198816A (ja) * | 2016-04-27 | 2017-11-02 | 東洋インキScホールディングス株式会社 | 固体撮像素子用近赤外線吸収性組成物およびフィルタ |
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| DE602005003244T2 (de) * | 2004-01-23 | 2008-09-25 | Fujifilm Corp. | Lithographiedruckplattenvorläufer und lithographisches Druckverfahren |
| JP5380019B2 (ja) | 2008-03-30 | 2014-01-08 | 富士フイルム株式会社 | 赤外線吸収性化合物および該化合物からなる微粒子 |
| US9382387B2 (en) * | 2012-03-13 | 2016-07-05 | California Institute Of Technology | Rapid self-assembly of block copolymers to photonic crystals |
| JP2014026178A (ja) | 2012-07-27 | 2014-02-06 | Fujifilm Corp | 近赤外線吸収性組成物、これを用いた近赤外線カットフィルタ及びその製造方法、並びに、カメラモジュール及びその製造方法 |
| WO2014142259A1 (ja) | 2013-03-14 | 2014-09-18 | 富士フイルム株式会社 | 固体撮像素子及びその製造方法、赤外光カットフィルタ形成用硬化性組成物、カメラモジュール |
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| JP2004302077A (ja) * | 2003-03-31 | 2004-10-28 | Fuji Photo Film Co Ltd | 重合性組成物、及びそれを用いた平版印刷版原版 |
| JP2006248113A (ja) * | 2005-03-11 | 2006-09-21 | Fuji Photo Film Co Ltd | 平版印刷版原版および平版印刷方法 |
| JP2010211200A (ja) * | 2009-02-16 | 2010-09-24 | Fujifilm Corp | 顔料分散組成物、着色硬化性組成物、カラーフィルタ、液晶表示装置、および固体撮像素子 |
| JP2011122115A (ja) * | 2009-12-14 | 2011-06-23 | Fujifilm Corp | 分散組成物、着色感光性組成物、カラーフィルタ、ブラックマトリックス、ウエハレベルレンズ、固体撮像素子、及び液晶表示装置 |
| WO2016190162A1 (ja) * | 2015-05-22 | 2016-12-01 | 富士フイルム株式会社 | 着色組成物、膜、カラーフィルタ、パターン形成方法、カラーフィルタの製造方法、固体撮像素子および赤外線センサ |
| WO2017135300A1 (ja) * | 2016-02-03 | 2017-08-10 | 富士フイルム株式会社 | 膜、膜の製造方法、光学フィルタ、積層体、固体撮像素子、画像表示装置、および、赤外線センサ |
| JP2017198816A (ja) * | 2016-04-27 | 2017-11-02 | 東洋インキScホールディングス株式会社 | 固体撮像素子用近赤外線吸収性組成物およびフィルタ |
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| JP6782309B2 (ja) | 2020-11-11 |
| TW201840566A (zh) | 2018-11-16 |
| KR20190096419A (ko) | 2019-08-19 |
| KR102219144B1 (ko) | 2021-02-23 |
| JPWO2018139533A1 (ja) | 2019-11-07 |
| CN110235033B (zh) | 2021-10-19 |
| CN110235033A (zh) | 2019-09-13 |
| US20190345321A1 (en) | 2019-11-14 |
| TWI769218B (zh) | 2022-07-01 |
| US10961381B2 (en) | 2021-03-30 |
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