WO2018061583A1 - Composition, cured film, color filter, solid-state imaging element, infrared sensor, near-infrared sensor, and proximity sensor - Google Patents
Composition, cured film, color filter, solid-state imaging element, infrared sensor, near-infrared sensor, and proximity sensor Download PDFInfo
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- WO2018061583A1 WO2018061583A1 PCT/JP2017/031044 JP2017031044W WO2018061583A1 WO 2018061583 A1 WO2018061583 A1 WO 2018061583A1 JP 2017031044 W JP2017031044 W JP 2017031044W WO 2018061583 A1 WO2018061583 A1 WO 2018061583A1
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- composition
- titanium nitride
- cured film
- compound
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- KHJHBFLMOSTPIC-UHFFFAOYSA-N prop-2-enylidenechromium Chemical compound C(=C)C=[Cr] KHJHBFLMOSTPIC-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000001047 purple dye Substances 0.000 description 1
- 239000001057 purple pigment Substances 0.000 description 1
- GZTPJDLYPMPRDF-UHFFFAOYSA-N pyrrolo[3,2-c]pyrazole Chemical compound N1=NC2=CC=NC2=C1 GZTPJDLYPMPRDF-UHFFFAOYSA-N 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000019515 salmon Nutrition 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000005156 substituted alkylene group Chemical group 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 125000005369 trialkoxysilyl group Chemical group 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 150000004961 triphenylmethanes Chemical class 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- RSJKGSCJYJTIGS-BJUDXGSMSA-N undecane Chemical group CCCCCCCCCC[11CH3] RSJKGSCJYJTIGS-BJUDXGSMSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- PSUYMGPLEJLSPA-UHFFFAOYSA-N vanadium zirconium Chemical compound [V].[V].[Zr] PSUYMGPLEJLSPA-UHFFFAOYSA-N 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/28—Nitrogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
- H01L27/144—Devices controlled by radiation
- H01L27/146—Imager structures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0232—Optical elements or arrangements associated with the device
Definitions
- the present invention relates to a composition, a cured film, a color filter, a solid-state imaging device, an infrared sensor, a near infrared sensor, and a proximity sensor.
- compositions containing titanium nitride have been used for various applications, for example, for the production of cured films provided in liquid crystal display devices and solid-state imaging devices.
- a color filter used in a liquid crystal display device or the like is provided with a cured film called a black matrix for the purpose of shielding light between colored pixels and improving contrast.
- a solid film is provided with a cured film for the purpose of preventing noise and improving image quality.
- portable terminals of electronic devices such as mobile phones and PDAs (Personal Digital Assistants) are equipped with small and thin solid-state imaging devices.
- Such a solid-state imaging device generally includes a solid-state imaging device such as a CCD (Charge Coupled Device) image sensor and a CMOS (Complementary Metal-Oxide Semiconductor) image sensor, and a lens for forming a subject image on the solid-state imaging device. It is equipped with.
- a solid-state imaging device such as a CCD (Charge Coupled Device) image sensor and a CMOS (Complementary Metal-Oxide Semiconductor) image sensor
- CMOS Complementary Metal-Oxide Semiconductor
- a black resin composition containing at least a light shielding material, a resin and a solvent, and containing at least titanium nitride particles as a light shielding material Is a black resin composition in which the diffraction angle 2 ⁇ of the peak derived from the (200) plane of titanium nitride particles when X is a X-ray source is 42.5 ° or more and 42.8 ° or less.
- the inventors of the present invention have studied a film prepared using the black resin composition described in Patent Document 1, and have found that there is a problem that the electrical characteristics have not reached the level required recently.
- an electrical property intends the electrical property measured by the method described in the Example.
- a composition containing titanium nitride-containing particles and a resin, and when the complex dielectric constant ⁇ of the titanium nitride-containing particles at a wavelength of 400 to 1200 nm is expressed by the following formula (1), ⁇ ′ A composition having a minimum value of less than 0.
- Formula (1) ⁇ ⁇ ′ + ⁇ ′′ j
- ⁇ ′ represents a real part of the complex dielectric constant ⁇
- ⁇ ′′ represents an imaginary part of the complex dielectric constant ⁇
- j represents an imaginary unit.
- the titanium nitride-containing particles contain titanium atoms and nitrogen atoms, and the ratio X of the nitrogen atom content to the titanium atom content in the titanium nitride-containing particles exceeds 0,
- Titanium nitride-containing particles further contain oxygen atoms, and the content ratio Y of oxygen atoms and the ratio X, which are the contents of titanium atoms in the titanium nitride-containing particles, are as follows: The composition according to [3] or [4], which satisfies (4).
- the titanium nitride-containing particles further contain chlorine atoms, and the content of chlorine atoms in the titanium nitride-containing particles is 800 to 3000 ppm by mass.
- a composition capable of producing a cured film having excellent electrical characteristics can be provided.
- a cured film, a color filter, a solid-state image sensor, an infrared sensor, a near-infrared sensor, and a proximity sensor can be provided.
- a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
- group (atomic group) in this specification the description which does not describe substitution and non-substitution includes what does not contain a substituent and what contains a substituent.
- the “alkyl group” includes not only an alkyl group not containing a substituent (unsubstituted alkyl group) but also an alkyl group containing a substituent (substituted alkyl group).
- active light or “radiation” means, for example, the emission line spectrum of a mercury lamp, deep ultraviolet light represented by excimer laser, extreme ultraviolet light (EUV), X-ray, and Means an electron beam. In the present specification, light means actinic rays and radiation.
- exposure in the present specification is not limited to exposure to deep ultraviolet rays, X-rays, EUV light and the like represented by mercury lamps and excimer lasers, but also particle beams such as electron beams and ion beams. Also includes drawing by.
- “(meth) acrylate” represents an acrylate and a methacrylate.
- “(meth) acryl” represents acryl and methacryl.
- “(meth) acryloyl” represents acryloyl and methacryloyl.
- (meth) acrylamide” represents acrylamide and methacrylamide.
- “monomer” and “monomer” are synonymous.
- a monomer is distinguished from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 2,000 or less.
- the polymerizable compound means a compound containing a polymerizable group, and may be a monomer or a polymer.
- the polymerizable group refers to a group that participates in a polymerization reaction.
- the minimum value is less than 0.
- ⁇ ′ represents a real part of the complex dielectric constant ⁇
- ⁇ ′′ represents an imaginary part of the complex dielectric constant ⁇
- j represents an imaginary unit.
- the minimum value of the real part ⁇ ′ of the complex dielectric constant is intended to be the minimum value of the real part ⁇ ′ of the complex dielectric constant corresponding to each wavelength of 400 to 1200 nm.
- the value of the real part ⁇ ′ of the complex dielectric constant is not particularly limited as long as the minimum value at 400 to 1200 nm is less than 0. However, the complex has a complex effect at 400 to 1200 nm in that the composition has more excellent effects of the present invention.
- the minimum value of the real part ⁇ ′ of the dielectric constant is preferably ⁇ 0.5 or less.
- the lower limit of the minimum value is not particularly limited, but is often about ⁇ 20.
- the real part ⁇ ′ of the complex dielectric constant is intended to be a value measured by the following method.
- a film having a thickness of 0.3 ⁇ m is formed using a composition on a silicon wafer.
- the complex dielectric constant of the formed film is measured by the method described in Examples using spectroscopic ellipsometry.
- membrane when forming a film
- a film produced using the black resin composition described in Patent Document 1 was subjected to an electrical property evaluation test described later for 3 months in an environment of a temperature of 25 ° C. and a humidity of 65% RH (relative humidity). After storage, the RC (resistor capacitor) value was likely to rise.
- the inventors of the present invention speculated that the increase in the RC value was caused by alteration of the titanium nitride particles contained in the black resin composition during storage for 3 months. As a result of continuing intensive studies, the present inventors have found that a composition containing titanium nitride-containing particles having a minimum value of ⁇ ′ of less than 0 can suppress the above-mentioned alteration.
- the present inventors have suppressed the aggregation of titanium nitride-containing particles by containing the resin in the composition, and the titanium nitride-containing particles are aggregated in the cured film obtained by curing the composition. It has been found that a local increase in RC value can be suppressed. Obtaining the above findings led to the present invention. Below, the form is demonstrated for every component contained in the composition which concerns on embodiment of this invention.
- the composition contains titanium nitride-containing particles.
- the titanium nitride-containing particles are not particularly limited as long as they contain titanium nitride and satisfy the above complex dielectric constant relationship.
- the content of titanium nitride-containing particles in the composition is not particularly limited, but is 29 to 70% by mass with respect to the total solid content of the composition in that a cured film having better light-shielding properties can be obtained. It is preferably 45 to 60% by mass.
- grains may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of particle
- the content of the titanium nitride-containing particles in the composition and the content of the dispersant described later are not particularly limited, but the titanium nitride in the composition is more excellent in terms of stability over time.
- the content ratio of the content of the dispersant to the content of the contained particles (hereinafter also referred to as “D / P”) is preferably 0.1 to 0.5.
- the density of the titanium nitride-containing particles is not particularly limited, but is preferably 2.5 to 6.0 g / cm 3 in that the composition has better electrical characteristics and better stability over time. 0.0 g / cm 3 or more is more preferable, and less than 5.0 g / cm 3 is preferable. Among these, when the density of the titanium nitride-containing particles is 3.0 g / cm 3 or more, the composition has more excellent temporal stability, and when the density is less than 5.0 g / cm 3 , The obtained cured film has a more excellent appearance after the moisture resistance test.
- the density of the titanium nitride-containing particles is intended to be a density measured by the following method.
- the titanium nitride-containing particles are dried using a vacuum dryer, and then the density is measured using a dry density meter (for example, Accupic II 1340 (Shimadzu Corporation)) under the conditions described in the examples.
- a dry density meter for example, Accupic II 1340 (Shimadzu Corporation)
- the following method can be used as a method of isolate
- the following method can be used as a method of isolate
- the following method can be used as a method of isolate
- the following method can be used as a method of isolate
- the following method can be used as a method of isolate
- the average primary particle size of the titanium nitride-containing particles is not particularly limited, but is generally preferably 1 to 200 nm and more preferably 10 to 50 nm.
- the average primary particle size intends the average primary particle size of particles measured by the following method.
- the average primary particle size can be measured using a transmission electron microscope (TEM).
- TEM transmission electron microscope
- a transmission electron microscope HT7700 manufactured by Hitachi High-Technologies Corporation can be used.
- An image is obtained by observing the sample at a magnification of 20,000 using a transmission electron microscope.
- the area of the titanium nitride-containing particles in the obtained image is calculated by image processing.
- the diameter when the obtained area is converted into a circle is calculated, and the circle-converted diameter evaluated for 400 particles is obtained by arithmetic averaging.
- the titanium nitride-containing particles may contain a layer of a compound containing silicon (hereinafter referred to as “silicon-containing compound”) on the surface thereof. That is, titanium nitride may be coated with a silicon-containing compound to form titanium nitride-containing particles.
- the method for coating titanium nitride is not particularly limited, and a known method can be used.
- JP-A-53-33228 page 2 lower right to page 4 upper right
- titanium Tianium
- the method described in paragraphs 0015 to 0043 of JP-A-2008-69193 titanium nitride is used instead of fine-particle titanium dioxide
- JP-A-2016-74870 Examples include the methods described in paragraphs 0020 and 0124 to 0138 of the publication (in which titanium nitride is used in place of metal oxide fine particles), and the above contents are incorporated herein.
- the titanium nitride-containing particles contain titanium nitride.
- the titanium nitride-containing particles contain titanium atoms (Ti) and nitrogen atoms (N).
- Ti titanium atoms
- N nitrogen atoms
- Examples of the titanium nitride-containing particles include low-order titanium oxide represented by TiN, TiO 2 , and Ti n O 2n-1 (1 ⁇ n ⁇ 20); TiN x O y (0 ⁇ x ⁇ 2.0, 0. And particles containing titanium oxynitride represented by 01 ⁇ y ⁇ 2.0); titanium nitride represented by TiN; and the like.
- the ratio X of the nitrogen atom content to the titanium atom content in the titanium nitride-containing particles is not particularly limited, but the lower limit value exceeds 0.
- the upper limit is preferably 2 or less, more preferably less than 1, and still more preferably less than 0.95.
- X ratio X
- the composition has better stability over time.
- X exceeds 0.40
- the composition has further excellent temporal stability, and when X is less than 0.95, the composition has further excellent patternability.
- X is more preferably 0.64 or less, further preferably 0.62 or less, and particularly preferably 0.57 or less in that the composition has the more excellent effects of the present invention.
- X is preferably 0.44 or more, more preferably 0.45 or more, in that the composition has the more excellent effects of the present invention.
- the content of titanium atoms in the titanium nitride-containing particles is determined by separating the titanium nitride-containing particles in the composition and using ICP (Inductively Coupled Plasma) emission spectroscopy for the separated titanium nitride-containing particles.
- the content of oxygen atoms and nitrogen atoms in the titanium nitride-containing particles can be measured using an inert gas melting-thermal conductivity method.
- the method for separating the titanium nitride-containing particles in the composition is as described above. In the present specification, X may be expressed as “N / Ti”.
- the ratio Y of the oxygen atom content to the titanium atom content in the titanium nitride-containing particles is not particularly limited, but is preferably 0 to 2, more preferably 0 to 1. .
- the ratio Y (hereinafter also simply referred to as “Y”) is 0.001 to 0.2, the composition has better stability over time.
- Y may be expressed as “O / Ti”.
- the sum ((N + O) / Ti) of the ratio X of the nitrogen atom content to the titanium atom content and the ratio Y of the oxygen atom content to the titanium atom content Y is preferable.
- X + Y satisfies the following formula (4).
- X + Y is within the above range, a film formed using the composition has more excellent light shielding properties.
- limit especially as a lower limit of X + Y Generally more than 0.2 is preferable.
- X + Y is more preferably 0.85 or less, and even more preferably 0.70 or less, in that the composition has more excellent effects of the present invention.
- X + Y is more preferably more than 0.40.
- the titanium nitride-containing particles preferably contain chlorine atoms.
- the content of chlorine atoms contained in the titanium nitride-containing particles is not particularly limited, but is generally preferably 300 to 5000 ppm by mass, more preferably 800 to 3000 ppm by mass with respect to the total mass of the titanium nitride-containing particles. Preferably, 1200 to 3000 ppm by mass is more preferable, and 1500 to 2700 ppm by mass is particularly preferable.
- the content of chlorine atoms in the titanium nitride-containing particles is 800 to 3000 ppm by mass, the cured film obtained from the composition has more excellent electrical characteristics.
- grains intends content of the chlorine atom measured with the following method. Titanium nitride-containing particles are burned with an auxiliary agent at 1000 ° C., and the generated chlorine gas is collected in an absorbing solution and analyzed using an ion chromatography apparatus. The method for separating titanium nitride-containing particles from the composition is as described above.
- the peak diffraction angle 2 ⁇ derived from the (200) plane of titanium nitride when CuK ⁇ rays are used as an X-ray source is generally preferably 42.5 ° to 43.5 °, and more excellent. From the viewpoint of easily obtaining a composition capable of obtaining a cured film having a light-shielding property, it is more preferably 42.5 ° to 42.8 °, and further preferably 42.5 to 42.7 °. .
- the diffraction angle 2 ⁇ of the peak derived from the (200) plane of the titanium nitride-containing particles is preferably 42.5 ° or more and 43.5 ° or less, more preferably 42.5 ° or more and 42.8 or less, and 42 More preferably, it is 5 ° or more and 42.7 ° or less.
- the titanium nitride-containing particles contain titanium oxide TiO 2
- TiO 2 is white and causes a reduction in the light-shielding property of a cured film obtained by curing the composition, it is preferably reduced to a level that is not observed as a peak.
- the crystallite size constituting the titanium nitride-containing particles can be determined from the half-value width of the peak obtained by measuring the X-ray diffraction spectrum.
- the crystallite size can be calculated using Scherrer's equation.
- the crystallite size constituting the titanium nitride-containing particles is preferably 50 nm or less, preferably 20 nm or more, and more preferably 20 to 50 nm.
- the cured film formed using the composition tends to have higher ultraviolet (particularly i-line (365 nm)) transmittance, and a composition having higher photosensitivity can be obtained. .
- the specific surface area of the titanium nitride-containing particles is not particularly limited, but can be determined by the BET (Brunauer, Emmett, Teller) method.
- the specific surface area of the titanium nitride-containing particles is preferably 5 ⁇ 100m 2 / g, more preferably 10 ⁇ 60m 2 / g.
- the titanium nitride-containing particles may be combined with other metal fine particles.
- “composite” refers to particles in which titanium nitride and metal fine particles are complexed or in a highly dispersed state.
- “composite” means that the particles are composed of both components of titanium nitride and other metals, and “highly dispersed” means that titanium nitride and other metals This means that the metals are present individually and the other metal particles are not aggregated but are uniformly and uniformly dispersed.
- the material of the metal fine particles is not particularly limited, and for example, copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantalum, calcium, titanium , Bismuth, antimony and lead, and alloys thereof.
- silver is preferred.
- the content of the metal fine particles in the titanium nitride-containing particles is preferably 5% by mass to 50% by mass with respect to the total mass of the titanium nitride-containing particles, and is preferably 10% by mass to 30% by mass. It is more preferable.
- the method for producing titanium nitride-containing particles is not particularly limited, and a known method can be used.
- Examples of the method for producing titanium nitride-containing particles include a gas phase reaction method.
- Examples of the gas phase reaction method include an electric furnace method, a thermal plasma method, and the like.
- the thermal plasma method is preferable in that impurities are less mixed, the particle diameter is easily uniformed, and productivity is high.
- a method for generating thermal plasma is not particularly limited, and includes direct current arc discharge, multilayer arc discharge, radio frequency (RF) plasma, hybrid plasma, and the like, and there is little mixing of impurities from the electrodes. High frequency plasma is preferred.
- a specific method for producing titanium nitride-containing particles by the thermal plasma method is not particularly limited.
- a method for producing titanium nitride titanium tetrachloride and ammonia gas are reacted in a plasma flame (Japanese Patent Application Laid-Open No. Hei. 2-22110), a method in which titanium powder is evaporated by high-frequency thermal plasma, nitrogen is introduced as a carrier gas, and is nitrided and synthesized in the cooling process (Japanese Patent Laid-Open No. 61-11140). Examples include a method of blowing ammonia gas (Japanese Patent Laid-Open No. 63-85007).
- the method for producing titanium nitride-containing particles is not limited to the above, and the production method is not limited as long as titanium nitride-containing particles having desired physical properties are obtained.
- the raw material is liquid, the raw material gas is introduced at a desired flow rate into the plasma flame, and thus the raw material is appropriately heated or cooled. May be.
- the method for producing titanium nitride-containing particles preferably further includes a step of heating and volatilizing and removing impurities (heating step) by heating the particles containing titanium nitride produced by the above production method. .
- the content of impurities, particularly volatile impurities, in the titanium nitride-containing particles tends to decrease.
- the minimum value of the real part ⁇ ′ of the complex dielectric constant at 400 to 1200 nm tends to be less than zero.
- the minimum value of the real part of the complex dielectric constant at 400 to 1200 nm tends to be 0 or more (for example, titanium nitride-containing particles TiN described later) -C))
- the heating temperature in the heating step is not particularly limited and is generally preferably 150 to 500 ° C.
- the heating time is not particularly limited, and generally 1 hour to 3 days is preferable.
- the atmosphere during heating is not particularly limited, but a nitrogen atmosphere or the like in which oxygen is less than 200 ppm is preferable. Further, the pressure may be reduced during heating.
- the composition contains a resin. Although it does not restrict
- the content of the resin in the composition is not particularly limited, but is generally preferably 0.5 to 30% by mass with respect to the total solid content of the composition.
- the composition preferably contains a dispersant (corresponding to a resin).
- a dispersing agent intends the compound different from the alkali-soluble resin mentioned later.
- the content of the dispersant in the composition is not particularly limited, but is generally preferably 8 to 20% by mass with respect to the total solid content of the composition.
- a dispersing agent may be used individually by 1 type, or may use 2 or more types together. When two or more dispersants are used in combination, the total content is preferably within the above range.
- the dispersant for example, a known dispersant can be appropriately selected and used. Of these, polymer compounds are preferable.
- the dispersant include polymer dispersants [for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic type Copolymer, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, and pigment derivatives.
- the polymer compounds can be further classified into linear polymers, terminal-modified polymers, graft polymers, and block polymers based on their structures.
- the polymer compound is adsorbed on the surface of titanium nitride-containing particles (hereinafter sometimes referred to as “pigment”) and acts to prevent re-aggregation of the dispersion. Therefore, a terminal-modified polymer, a graft polymer, and a block polymer containing an anchor site to the pigment surface are preferable.
- the polymer compound preferably contains a structural unit containing a graft chain.
- structural unit is synonymous with “repeating unit”. Since the polymer compound containing a structural unit containing such a graft chain has an affinity for a solvent by the graft chain, the dispersibility of titanium nitride-containing particles and the like, and the dispersion stability after aging ( It has excellent stability over time. Further, due to the presence of the graft chain, the polymer compound containing the structural unit containing the graft chain has an affinity with a polymerizable compound or other resin that can be used in combination. As a result, it becomes difficult to produce a residue by alkali development.
- the graft chain When the graft chain becomes longer, the steric repulsion effect becomes higher and the dispersibility of the titanium nitride-containing particles and the like is improved. On the other hand, if the graft chain is too long, the adsorptive power to the titanium nitride-containing particles and the like is lowered, and the dispersibility of the titanium nitride-containing particles and the like tends to be lowered.
- the graft chain preferably has 40 to 10,000 atoms excluding hydrogen atoms, more preferably 50 to 2000 atoms excluding hydrogen atoms, and the number of atoms excluding hydrogen atoms. More preferred is 60-500.
- the graft chain means from the base of the main chain of the copolymer (the atom bonded to the main chain in a group branched from the main chain) to the end of the group branched from the main chain.
- the graft chain preferably contains a polymer structure.
- a polymer structure include a poly (meth) acrylate structure (for example, a poly (meth) acrylic structure), a polyester structure, a polyurethane structure, a polyurea structure, and a polyamide.
- examples thereof include a structure and a polyether structure.
- the graft chain is from the group consisting of a polyester structure, a polyether structure and a poly (meth) acrylate structure. It is preferably a graft chain containing at least one selected, and more preferably a graft chain containing at least one of a polyester structure and a polyether structure.
- the macromonomer containing such a graft chain (a monomer having a polymer structure and bound to the main chain of the copolymer to constitute the graft chain) is not particularly limited, but includes a reactive double bond group.
- the macromonomer to contain can be used conveniently.
- AA-6 (trade name, manufactured by Toagosei Co., Ltd.), AA-10 (trade name, manufactured by Toagosei Co., Ltd.), AB-6 (trade name, manufactured by Toagosei Co., Ltd.), AS-6 ( A trade name, manufactured by Toagosei Co., Ltd.), AN-6 (trade name, manufactured by Toagosei Co., Ltd.), and Bremer PME-4000 (trade name, manufactured by NOF Corporation) are used.
- the dispersant preferably contains at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and cyclic or chain polyester. More preferably, the dispersant contains at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and chain polyester. More preferably, the dispersant contains at least one structure selected from the group consisting of a polymethyl acrylate structure, a polymethyl methacrylate structure, a polycaprolactone structure, and a polyvalerolactone structure.
- the dispersing agent may contain the above structure alone in one dispersing agent, or may contain a plurality of these structures in one dispersing agent.
- the polycaprolactone structure means a structure containing a ring-opened structure of ⁇ -caprolactone as a repeating unit.
- the polyvalerolactone structure means a structure containing a ring-opened structure of ⁇ -valerolactone as a repeating unit.
- Specific examples of the dispersant containing a polycaprolactone structure include those in which j and k are 5 in the following formula (1) and the following formula (2).
- Specific examples of the dispersant containing a polyvalerolactone structure include those in which j and k in the following formula (1) and the following formula (2) are 4.
- dispersant containing a polymethyl acrylate structure examples include those in which X 5 in the following formula (4) is a hydrogen atom and R 4 is a methyl group. Further, specific examples of the dispersant containing a polymethyl methacrylate structure include those in which X 5 in the following formula (4) is a methyl group and R 4 is a methyl group.
- the polymer compound preferably contains a structural unit represented by any one of the following formulas (1) to (4) as a structural unit containing a graft chain. It is more preferable to contain a structural unit represented by any one of (1A), the following formula (2A), the following formula (3A), the following formula (3B), and the following (4).
- W 1 , W 2 , W 3 , and W 4 each independently represent an oxygen atom or NH.
- W 1 , W 2 , W 3 , and W 4 are preferably oxygen atoms.
- X 1 , X 2 , X 3 , X 4 , and X 5 each independently represent a hydrogen atom or a monovalent organic group.
- X 1 , X 2 , X 3 , X 4 , and X 5 are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms (the number of carbon atoms) from the viewpoint of synthesis constraints.
- Y 1 , Y 2 , Y 3 , and Y 4 each independently represent a divalent linking group, and the linking group is not particularly limited in structure.
- Specific examples of the divalent linking group represented by Y 1 , Y 2 , Y 3 , and Y 4 include the following linking groups (Y-1) to (Y-21). .
- a and B mean binding sites with the left end group and the right end group in formulas (1) to (4), respectively. Of the structures shown below, (Y-2) or (Y-13) is more preferable because of the ease of synthesis.
- Z 1 , Z 2 , Z 3 , and Z 4 each independently represent a monovalent organic group.
- the structure of the organic group is not particularly limited. Specifically, an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, an amino group, and the like Is mentioned.
- the organic group represented by Z 1 , Z 2 , Z 3 , and Z 4 those containing a steric repulsion effect are particularly preferable from the viewpoint of improving dispersibility, and each independently has 5 carbon atoms.
- alkyl groups or alkoxy groups each independently a branched alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms, or an alkoxy group having 5 to 24 carbon atoms. Is more preferable.
- the alkyl group contained in the alkoxy group may be linear, branched, or cyclic.
- n, m, p, and q are each independently an integer of 1 to 500.
- j and k each independently represent an integer of 2 to 8.
- J and k in the formulas (1) and (2) are preferably integers of 4 to 6, and more preferably 5, from the viewpoint of the temporal stability and developability of the composition.
- R 3 represents a branched or straight chain alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, a plurality of R 3 may be the same or different from each other.
- R 4 represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited in terms of structure.
- R 4 is preferably a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and more preferably a hydrogen atom or an alkyl group.
- the alkyl group is preferably a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms.
- a linear alkyl group having 1 to 20 carbon atoms is more preferable, and a linear alkyl group having 1 to 6 carbon atoms is still more preferable.
- a plurality of X 5 and R 4 present in the graft copolymer may be the same or different from each other.
- the polymer compound can contain structural units containing graft chains that differ in two or more structures. That is, the polymer compound molecule may contain structural units represented by formulas (1) to (4) having different structures, and n, m in formulas (1) to (4). , P, and q each represent an integer of 2 or more, in formula (1) and formula (2), j and k may contain structures different from each other in the side chain. In the formula (4), a plurality of R 3 , R 4 and X 5 present in the molecule may be the same or different from each other.
- the structural unit represented by the formula (1) is more preferably a structural unit represented by the following formula (1A) from the viewpoint of temporal stability and developability of the composition.
- a structural unit represented by Formula (2) it is more preferable that it is a structural unit represented by following formula (2A) from a viewpoint of temporal stability of a composition and developability.
- X 1, Y 1, Z 1 and n are as defined X 1, Y 1, Z 1 and n in Formula (1), and preferred ranges are also the same.
- X 2, Y 2, Z 2 and m are as defined X 2, Y 2, Z 2 and m in the formula (2), and preferred ranges are also the same.
- the structural unit represented by the formula (3) is more preferably a structural unit represented by the following formula (3A) or formula (3B) from the viewpoint of the temporal stability and developability of the composition. .
- X 3, Y 3, Z 3 and p are as defined X 3, Y 3, Z 3 and p in formula (3), and preferred ranges are also the same.
- the polymer compound contains a structural unit represented by the formula (1A) as a structural unit containing a graft chain.
- the structural unit containing a graft chain (for example, the structural unit represented by the above formulas (1) to (4)) is 2 to 90% in terms of mass with respect to the total mass of the polymer compound. Preferably, it is contained in the range of 5 to 30%.
- the structural unit containing a graft chain is contained within this range, the dispersibility of the titanium nitride-containing particles is high, and the developability when forming a cured film is good.
- a high molecular compound contains the hydrophobic structural unit different from the structural unit containing a graft chain (namely, it does not correspond to the structural unit containing a graft chain).
- a hydrophobic structural unit is a structural unit which does not have an acid group (for example, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group, etc.).
- the hydrophobic structural unit is preferably a structural unit derived from (corresponding to) a compound (monomer) having a ClogP value of 1.2 or more, more preferably derived from a compound having a ClogP value of 1.2 to 8. A structural unit. Thereby, the effect of this invention can be expressed more reliably.
- ClogP values are available from Daylight Chemical Information System, Inc. It is a value calculated by the program “CLOGP” available from This program provides the value of “computation logP” calculated by Hansch, Leo's fragment approach (see below). The fragment approach is based on the chemical structure of a compound, which divides the chemical structure into substructures (fragments) and estimates the logP value of the compound by summing the logP contributions assigned to that fragment. Details thereof are described in the following documents. In the present invention, the ClogP value calculated by the program CLOGP v4.82 is used. A. J. et al. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C.I. Hansch, P.A. G. Sammunens, J. et al. B.
- log P means the common logarithm of the partition coefficient P (Partition Coefficient), and quantitatively determines how an organic compound is distributed in the equilibrium of a two-phase system of oil (generally 1-octanol) and water. It is a physical property value expressed as a numerical value, and is represented by the following formula.
- logP log (Coil / Cwater)
- Coil represents the molar concentration of the compound in the oil phase
- Cwater represents the molar concentration of the compound in the aqueous phase.
- the polymer compound preferably contains one or more structural units selected from structural units derived from monomers represented by the following formulas (i) to (iii) as hydrophobic structural units.
- R 1 , R 2 , and R 3 each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number of 1 Represents an alkyl group of ⁇ 6 (for example, methyl group, ethyl group, propyl group, etc.).
- R 1 , R 2 , and R 3 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group.
- R 2 and R 3 are more preferably a hydrogen atom.
- X represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
- L is a single bond or a divalent linking group.
- a divalent aliphatic group for example, alkylene group, substituted alkylene group, alkenylene group, substituted alkenylene group, alkynylene group, substituted alkynylene group
- divalent aromatic group for example, arylene group
- Substituted arylene group divalent heterocyclic group, oxygen atom (—O—), sulfur atom (—S—), imino group (—NH—), substituted imino group (—NR 31 —, where R 31 Are aliphatic groups, aromatic groups or heterocyclic groups), carbonyl groups (—CO—), and combinations thereof.
- the divalent aliphatic group may have a cyclic structure or a branched structure.
- the aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms.
- the aliphatic group may be an unsaturated aliphatic group or a saturated aliphatic group, but is preferably a saturated aliphatic group.
- the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group and a heterocyclic group.
- the carbon number of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10.
- the aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group.
- the divalent heterocyclic group preferably contains a 5-membered ring or a 6-membered ring as the heterocyclic ring.
- Another heterocyclic ring, an aliphatic ring or an aromatic ring may be condensed with the heterocyclic ring.
- the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxyl groups, oxo groups ( ⁇ O), thioxo groups ( ⁇ S), imino groups ( ⁇ NH), substituted imino groups ( ⁇ N—R 32 , where R 32 is aliphatic. Group, aromatic group or heterocyclic group), aliphatic group, aromatic group, or heterocyclic group.
- L is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure.
- the oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure.
- L may also contain a polyoxyalkylene structure containing two or more oxyalkylene structures.
- the polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure.
- the polyoxyethylene structure is represented by — (OCH 2 CH 2 ) n—, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.
- Z is an aliphatic group (eg, alkyl group, substituted alkyl group, unsaturated alkyl group, substituted unsaturated alkyl group), aromatic group (eg, aryl group, substituted aryl group, arylene group, substituted arylene group). , A heterocyclic group, or a combination thereof. These groups include an oxygen atom (—O—), a sulfur atom (—S—), an imino group (—NH—), a substituted imino group (—NR 31 —, wherein R 31 is an aliphatic group, an aromatic group Group or heterocyclic group) or a carbonyl group (—CO—) may be contained.
- the aliphatic group may have a cyclic structure or a branched structure.
- the aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms.
- the aliphatic group further includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group. Examples of the ring assembly hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group, and 4 -A cyclohexylphenyl group and the like are included.
- bridged cyclic hydrocarbon ring examples include 2 such as pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.).
- Tricyclic hydrocarbon rings such as cyclic hydrocarbon rings, homobredan, adamantane, tricyclo [5.2.1.0 2,6 ] decane, and tricyclo [4.3.1.1 2,5 ] undecane rings , And tetracyclo [4.4.0.1 2,5 .
- the bridged cyclic hydrocarbon ring includes a condensed cyclic hydrocarbon ring, such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and A condensed ring in which a plurality of 5- to 8-membered cycloalkane rings are condensed, such as a perhydrophenalene ring, is also included.
- a condensed cyclic hydrocarbon ring such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and A condensed ring in which a plurality of 5- to 8-membered cycloalkane rings are condensed, such as a perhydrophenalene ring, is also included.
- the aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. Further, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group. However, the aliphatic group does not have an acid group as a substituent.
- the carbon number of the aromatic group is preferably 6-20, more preferably 6-15, and still more preferably 6-10.
- the aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group. However, the aromatic group does not have an acid group as a substituent.
- a heterocyclic group contains a 5-membered ring or a 6-membered ring as a heterocyclic ring.
- Another heterocyclic ring, an aliphatic ring or an aromatic ring may be condensed with the heterocyclic ring.
- the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxyl groups, oxo groups ( ⁇ O), thioxo groups ( ⁇ S), imino groups ( ⁇ NH), substituted imino groups ( ⁇ N—R 32 , where R 32 is aliphatic. Group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group.
- the heterocyclic group does not have an acid group as a substituent.
- R 4 , R 5 , and R 6 are each independently a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), or an alkyl group having 1 to 6 carbon atoms.
- a halogen atom eg, a fluorine atom, a chlorine atom, a bromine atom, etc.
- an alkyl group having 1 to 6 carbon atoms for example, a methyl group, an ethyl group, a propyl group, etc.
- Z or LZ.
- L and Z are as defined above.
- R 4 , R 5 and R 6 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
- R 1 , R 2 , and R 3 are a hydrogen atom or a methyl group, and L is a single bond, an alkylene group, or a divalent oxyalkylene structure.
- a compound in which X is an oxygen atom or imino group and Z is an aliphatic group, a heterocyclic group or an aromatic group is preferable.
- R 1 is a hydrogen atom or a methyl group
- L is an alkylene group
- Z is an aliphatic group, a heterocyclic group or an aromatic group. Certain compounds are preferred.
- R 4 , R 5 , and R 6 are a hydrogen atom or a methyl group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group. Compounds are preferred.
- Examples of typical compounds represented by formulas (i) to (iii) include radically polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, styrenes, and the like.
- Examples of typical compounds represented by formulas (i) to (iii) compounds described in paragraphs 0089 to 0093 of JP2013-249417A can be referred to, and the contents thereof are described in the present specification. Incorporated into.
- the hydrophobic structural unit is preferably contained in a range of 10 to 90%, more preferably in a range of 20 to 80% with respect to the total mass of the polymer compound in terms of mass. When the content is in the above range, sufficient pattern formation can be obtained.
- the polymer compound can introduce a functional group capable of forming interaction with titanium nitride-containing particles.
- the polymer compound preferably further contains a structural unit containing a functional group capable of forming an interaction with titanium nitride-containing particles.
- the functional group capable of forming an interaction with the titanium nitride-containing particles include an acid group, a basic group, a coordinating group, and a reactive functional group.
- the polymer compound contains an acid group, a basic group, a coordination group, or a reactive functional group, the structural unit containing an acid group, the structural unit containing a basic group, and a coordination group, respectively.
- a structural unit containing a coordinate group or a structural unit having reactivity it is preferable to contain a structural unit containing a coordinate group or a structural unit having reactivity.
- the polymer compound further contains an alkali-soluble group such as a carboxylic acid group as the acid group, developability for pattern formation by alkali development can be imparted to the polymer compound. That is, by introducing an alkali-soluble group into the polymer compound, the polymer compound as a dispersant that contributes to the dispersion of titanium nitride-containing particles or the like in the composition contains alkali-solubility.
- a composition containing such a polymer compound has excellent light-shielding properties in the exposed area, and the alkali developability in the unexposed area is improved.
- a high molecular compound contains the structural unit containing an acid group
- a high molecular compound becomes easy to become compatible with a solvent, and there exists a tendency for applicability
- the acid group in the structural unit containing an acid group easily interacts with the titanium nitride-containing particles and the like, and the polymer compound stably disperses the titanium nitride-containing particles and the like, and the titanium nitride-containing particles and the like It is presumed that the viscosity of the polymer compound in which the polymer is dispersed is low, and the polymer compound itself is easily dispersed stably.
- the structural unit containing an alkali-soluble group as an acid group may be the same structural unit as the structural unit containing the graft chain or a different structural unit.
- the structural unit containing a soluble group is a structural unit different from the hydrophobic structural unit described above (that is, does not correspond to the hydrophobic structural unit described above).
- the acid group that is a functional group capable of forming an interaction with titanium nitride-containing particles include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a phenolic hydroxyl group, and preferably a carboxylic acid Group, sulfonic acid group, and phosphoric acid group, and more preferable is a carboxylic acid group from the viewpoint of good adsorptive power to titanium nitride-containing particles and high dispersibility. It is. That is, the polymer compound preferably further contains a structural unit containing at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.
- the polymer compound may have one or more structural units containing an acid group.
- the polymer compound may or may not contain a structural unit containing an acid group. However, when it is contained, the content of the structural unit containing an acid group is calculated by mass conversion to the total mass of the polymer compound. On the other hand, it is preferably 5 to 80%, and more preferably 10 to 60% from the viewpoint of suppressing damage of image strength due to alkali development.
- Examples of the basic group that is a functional group capable of forming an interaction with titanium nitride-containing particles include a primary amino group, a secondary amino group, a tertiary amino group, and a heterocyclic ring containing an N atom. And an amide group and the like, and a preferable one is a tertiary amino group in terms of good adsorbing power to titanium nitride-containing particles and high dispersibility.
- the polymer compound can contain one or more of these basic groups.
- the polymer compound may or may not contain a structural unit containing a basic group, but when it is contained, the content of the structural unit containing a basic group is the total amount of the polymer compound in terms of mass. Preferably it is 0.01% or more and 50% or less with respect to mass, More preferably, it is 0.01% or more and 30% or less from a viewpoint of developability inhibition suppression.
- Examples of the coordinating group that is a functional group capable of forming an interaction with titanium nitride-containing particles and the functional group having reactivity include, for example, an acetylacetoxy group, a trialkoxysilyl group, an isocyanate group, an acid anhydride, And acid chloride etc. are mentioned.
- Preferable one is an acetylacetoxy group in that the adsorbing power to titanium nitride-containing particles is good and the dispersibility of titanium nitride-containing particles is high.
- the polymer compound may have one or more of these groups.
- the polymer compound may or may not contain a structural unit containing a coordinating group or a structural unit containing a reactive functional group, but if it contains, the content of these structural units Is preferably 10% or more and 80% or less, and more preferably 20% or more and 60% or less, in terms of mass, in terms of suppression of developability inhibition.
- the polymer compound contains a functional group capable of forming an interaction with titanium nitride-containing particles in addition to the graft chain, the functional group capable of forming an interaction with the above various titanium nitride-containing particles.
- the polymer compound is derived from the monomers represented by the following formulas (iv) to (vi) It is preferable to contain one or more structural units selected from these structural units.
- R 11 , R 12 , and R 13 each independently represent a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number of 1 Represents an alkyl group of ⁇ 6 (for example, methyl group, ethyl group, propyl group, etc.).
- R 11 , R 12 and R 13 are preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably each independently Are a hydrogen atom or a methyl group.
- R 12 and R 13 are each particularly preferably a hydrogen atom.
- X 1 in the formula (iv) represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
- Y in the formula (v) represents a methine group or a nitrogen atom.
- L 1 represents a single bond or a divalent linking group.
- the definition of the divalent linking group is the same as the definition of the divalent linking group represented by L in the above-described formula (i).
- L 1 is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure.
- the oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure.
- L 1 may contain a polyoxyalkylene structure containing two or more oxyalkylene structures.
- the polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure.
- the polyoxyethylene structure is represented by — (OCH 2 CH 2 ) n—, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.
- Z 1 represents a functional group capable of forming an interaction with titanium nitride-containing particles in addition to the graft chain, and is a carboxylic acid group or a tertiary amino group. It is preferable that it is a carboxylic acid group.
- R 14 , R 15 , and R 16 are each independently a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, etc.), - Z 1, or an L 1 -Z 1.
- L 1 and Z 1 are the same meaning as L 1 and Z 1 in the above, it is the preferable examples.
- R 14 , R 15 and R 16 are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
- R 11 , R 12 and R 13 are each independently a hydrogen atom or a methyl group, and L 1 is an alkylene group or a divalent oxyalkylene structure.
- a compound in which X 1 is an oxygen atom or imino group and Z 1 is a carboxylic acid group is preferable.
- R 11 is a hydrogen atom or a methyl group
- L 1 is an alkylene group
- Z 1 is a carboxylic acid group
- Y is a methine group. Is preferred.
- R 14 , R 15 , and R 16 are each independently a hydrogen atom or a methyl group, L 1 is a single bond or an alkylene group, and Z A compound in which 1 is a carboxylic acid group is preferred.
- monomers represented by the formulas (iv) to (vi).
- monomers include methacrylic acid, crotonic acid, isocrotonic acid, a reaction containing a compound having an addition polymerizable double bond and a hydroxyl group in the molecule (for example, 2-hydroxyethyl methacrylate) and succinic anhydride.
- reaction product a reaction product of a compound containing an addition polymerizable double bond and a hydroxyl group in the molecule with phthalic anhydride, a compound containing an addition polymerizable double bond and a hydroxyl group in the molecule and tetrahydroxyphthalic anhydride Reaction product, a reaction product of a compound containing an addition polymerizable double bond and hydroxyl group in the molecule and trimellitic anhydride, a compound containing an addition polymerizable double bond and hydroxyl group in the molecule and pyromellitic anhydride Reaction products with acrylic acid, acrylic acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid, vinylphenol, and 4 Hydroxyphenyl methacrylamide.
- the content of the structural unit containing a functional group capable of forming an interaction with titanium nitride-containing particles, etc. is from the viewpoint of interaction with titanium nitride-containing particles, etc., stability over time, and permeability to developer.
- the amount is preferably 0.05% by mass to 90% by mass, more preferably 1.0% by mass to 80% by mass, and still more preferably 10% by mass to 70% by mass with respect to the total mass of the polymer compound.
- the polymer compound is a structural unit containing a graft chain, a hydrophobic structural unit, and titanium as long as the effects of the present invention are not impaired for the purpose of improving various properties such as image strength.
- other structural units having various functions for example, functional groups having affinity with the solvent used in the dispersion
- Examples of such other structural units include structural units derived from radically polymerizable compounds selected from acrylonitriles, methacrylonitriles, and the like.
- the polymer compound may use one or more of these other structural units, and the content thereof is preferably 0% or more and 80% or less in terms of mass with respect to the total mass of the polymer compound. Especially preferably, it is 10% or more and 60% or less. When the content is in the above range, sufficient pattern formability is maintained.
- the acid value of the polymer compound is preferably in the range of 0 mgKOH / g to 250 mgKOH / g, more preferably in the range of 10 mgKOH / g to 200 mgKOH / g, and even more preferably 20 mgKOH. / G or more and 120 mgKOH / g or less.
- the acid value of the polymer compound is 160 mgKOH / g or less, pattern peeling during development when forming a cured film is more effectively suppressed.
- the acid value of a high molecular compound is 10 mgKOH / g or more, alkali developability will become more favorable.
- the acid value of the polymer compound is 20 mgKOH / g or more, precipitation of titanium nitride-containing particles and the like can be further suppressed, the number of coarse particles can be reduced, and the temporal stability of the composition is further improved. it can.
- the acid value of the polymer compound can be calculated, for example, from the average content of acid groups in the polymer compound. Moreover, the resin which has a desired acid value can be obtained by changing content of the structural unit containing the acid group which is a structural component of a high molecular compound.
- the weight average molecular weight of the polymer compound is 4 in terms of polystyrene conversion by GPC (Gel Permeation Chromatography) method from the viewpoint of pattern peeling inhibition during development and developability when forming a cured film. It is preferably 000 or more and 300,000 or less, more preferably 5,000 or more and 200,000 or less, further preferably 6,000 or more and 100,000 or less, and 10,000 or more and 50,000 or less.
- the GPC method is based on a method using HLC-8020GPC (manufactured by Tosoh), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh, 4.6 mm ID ⁇ 15 cm) as a column and THF (tetrahydrofuran) as an eluent.
- the polymer compound can be synthesized based on a known method.
- polymer compound examples include “DA-7301” manufactured by Enomoto Kasei Co., Ltd., “Disperbyk-101 (polyamidoamine phosphate)” manufactured by BYK Chemie, 107 (carboxylic acid ester), and 110 (copolymer containing acid group).
- Acrybase FFS-6752, Acrybase FFS-187, Acrycure-RD-F8, and Cyclomer P can be used.
- Commercially available amphoteric resins include, for example, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001, DISPERB manufactured by BYK Chemie. 2010, DISPERBYK-2012, DISPERBYK-2025, BYK-9976, Ajisper PB821, Azisper PB822, Azisper PB881, etc. manufactured by Ajinomoto Fine Techno Co., Ltd. These polymer compounds may be used alone or in combination of two or more.
- polymer compound As specific examples of the polymer compound, the polymer compounds described in paragraphs 0127 to 0129 of JP2013-249417A can be referred to, and the contents thereof are incorporated in the present specification.
- graft copolymers described in JP-A 2010-106268, paragraphs 0037 to 0115 (corresponding to columns 0075 to 0133 in US2011 / 0124824) can be used. Is incorporated herein by reference. In addition to the above, it contains a side chain structure in which acidic groups in paragraphs 0028 to 0084 of JP 2011-153283 A (corresponding to paragraphs 0075 to 0133 of US2011 / 0279759) are bonded via a linking group.
- Polymer compounds containing the constituents to be used can be used, the contents of which can be incorporated and incorporated herein.
- the said composition contains alkali-soluble resin (it corresponds to resin).
- the alkali-soluble resin means a resin containing a group that promotes alkali solubility (alkali-soluble group), and a resin different from the dispersant already described.
- the content of the alkali-soluble resin in the composition is not particularly limited, but is generally preferably 0.5 to 30% by mass with respect to the total solid content of the composition, and the composition has a more excellent effect of the present invention. In this respect, 1 to 20% by mass is preferable.
- Alkali-soluble resin may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of alkali-soluble resin together, it is preferable that total content is in the said range.
- alkali-soluble resin examples include resins containing at least one alkali-soluble group in the molecule, such as polyhydroxystyrene resin, polysiloxane resin, (meth) acrylic resin, (meth) acrylamide resin, and (meth) acrylic. / (Meth) acrylamide copolymer resin, epoxy resin, and polyimide resin.
- the alkali-soluble resin include a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound.
- unsaturated carboxylic acid Monocarboxylic acids, such as (meth) acrylic acid, crotonic acid, and vinyl acetic acid; Dicarboxylic acids, such as itaconic acid, maleic acid, and fumaric acid, or its acid anhydride
- polycarboxylic acid monoesters such as monophthalic acid (2- (meth) acryloyloxyethyl).
- Examples of the copolymerizable ethylenically unsaturated compound include methyl (meth) acrylate.
- the compounds described in paragraph 0027 of JP 2010-97210 A and paragraphs 0036 to 0037 of JP 2015-68893 A can also be used, and the above contents are incorporated herein.
- a copolymerizable ethylenically unsaturated compound that contains an ethylenically unsaturated group in the side chain may be used in combination.
- a (meth) acrylic acid group is preferable.
- An acrylic resin having an ethylenically unsaturated group in the side chain is obtained by, for example, adding an ethylenically unsaturated compound containing a glycidyl group or an alicyclic epoxy group to a carboxylic acid group of an acrylic resin containing a carboxylic acid group. Can be obtained.
- alkali-soluble resin examples include JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-54-92723, JP-A-59-.
- alkali-soluble resin for example, compounds described in paragraphs 0225 to 0245 of JP-A-2016-75845 can be used, and the above contents are incorporated in the present specification.
- a polyimide precursor can also be used as the alkali-soluble resin.
- the polyimide precursor intends a resin obtained by subjecting a compound containing an acid anhydride group and a diamine compound to an addition polymerization reaction at 40 to 100 ° C.
- resin containing the repeating unit represented by Formula (1) is mentioned, for example.
- the structure of the polyimide precursor include an amic acid structure represented by the following formula (2), the following formula (3) in which the amic acid structure is partially imide ring-closed, and / or the following formula in which all imide rings are closed: The thing containing the imide structure shown by (4) is mentioned.
- a polyimide precursor having an amic acid structure may be referred to as a polyamic acid.
- R 1 represents a tetravalent organic group having 2 to 22 carbon atoms
- R 2 represents a divalent organic group having 1 to 22 carbon atoms
- n is 1 or 2 Represents.
- polyimide precursor examples include, for example, compounds described in paragraphs 0011 to 0031 of JP-A-2008-106250, compounds described in paragraphs 0022 to 0039 of JP-A-2016-122101, and JP-A Examples include the compounds described in paragraphs 0061 to 0092 of JP-A-2016-68401, and the above contents are incorporated herein.
- the alkali-soluble resin preferably contains at least one selected from the group consisting of a polyimide resin and a polyimide precursor in that the pattern shape of the patterned cured film obtained using the composition is more excellent.
- the polyimide resin containing an alkali-soluble group is not particularly limited, and a known polyimide resin containing an alkali-soluble group can be used. Examples of the polyimide resin include resins described in paragraph 0050 of JP-A-2014-137523, resins described in paragraph 0058 of JP-A-2015-187676, and JP-A-2014-106326. Examples include the resins described in paragraphs 0012 to 0013, and the above contents are incorporated herein.
- the said composition may contain arbitrary components other than the above.
- the optional component include a polymerizable compound, a polymerization initiator, a solvent, a silane coupling agent, an ultraviolet absorber, a surfactant, an adhesion improver, a colorant, and a pigment derivative.
- coloring agents other than titanium nitride containing particle
- the composition preferably contains a polymerizable compound.
- the polymerizable compound means a compound containing a polymerizable group and a component different from the dispersant and the alkali-soluble resin.
- the content of the polymerizable compound in the composition is not particularly limited, but is preferably 1 to 30% by mass and more preferably 5 to 20% by mass with respect to the total solid content of the composition.
- a polymeric compound may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of polymeric compounds together, it is preferable that total content is in the said range.
- the polymerizable compound is preferably a compound containing at least one group containing an ethylenically unsaturated bond, more preferably a compound containing 2 or more, further preferably containing 3 or more, and containing 5 or more. Is particularly preferred.
- the upper limit is 15 or less, for example.
- Examples of the group containing an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
- the polymerizable compound for example, the compounds described in paragraph 0050 of JP2008-260927A and paragraph 0040 of JP2015-68893A can be used. Incorporated into.
- the polymerizable compound may be in any of chemical forms such as a monomer, a prepolymer, an oligomer, a mixture thereof, and a multimer thereof.
- 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 is also preferably a compound having one or more groups containing an ethylenically unsaturated bond and having a boiling point of 100 ° C. or higher under normal pressure.
- compounds described in JP-A-2013-29760, paragraph 0227, and JP-A-2008-292970, paragraphs 0254 to 0257 can be referred to, the contents of which are incorporated herein.
- Polymerizable compounds are dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product; manufactured by Nippon Kayaku), di Pentaerythritol penta (meth) acrylate (KAYARAD D-310 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (KAYARAD DPHA as a commercial product; manufactured by Nippon Kayaku Co., Ltd., A-DPH- 12E; manufactured by Shin-Nakamura Chemical Co., Ltd.) and a structure in which these (meth) acryloyl groups are mediated by an ethylene glycol residue or a propylene glycol residue (for example, SR454, SR499, commercially available from Sartomer).
- oligomer types can also be used.
- NK ester A-TMMT penentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.
- KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd.
- Preferred embodiments of the polymerizable compound are shown below.
- the polymerizable compound may have an acid group such as a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.
- an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound.
- a polymerizable compound having a group is more preferable, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include Aronix TO-2349, M-305, M-510, and M-520 manufactured by Toagosei Co., Ltd.
- the preferred acid value of the polymerizable compound containing an acid group is 0.1 to 40 mgKOH / g, more preferably 5 to 30 mgKOH / g.
- the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the development dissolution properties are good, and when it is 40 mgKOH / g or less, it is advantageous in production and / or handling. Furthermore, the photopolymerization performance is good and the curability is excellent.
- the polymerizable compound is also preferably a compound containing a caprolactone structure.
- the compound containing a caprolactone structure is not particularly limited as long as it contains a caprolactone structure in the molecule.
- compounds containing a caprolactone structure represented by the following formula (Z-1) are preferred.
- R 1 represents a hydrogen atom or a methyl group
- m represents a number of 1 or 2
- “*” represents a bond.
- R 1 represents a hydrogen atom or a methyl group, and “*” represents a bond.
- a compound represented by the following formula (Z-4) or (Z-5) can also be used.
- each E independently represents — ((CH 2 ) y CH 2 O) — or ((CH 2 ) y CH (CH 3 ) O) —.
- Y represents an integer of 0 to 10
- X independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxylic acid group.
- the total number of (meth) acryloyl groups is 3 or 4
- each m independently represents an integer of 0 to 10
- the total of each m is an integer of 0 to 40.
- the total number of (meth) acryloyl groups is 5 or 6
- each n independently represents an integer of 0 to 10 and the total of each n is an integer of 0 to 60.
- m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
- the total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and further preferably an integer of 4 to 8.
- n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
- the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and still more preferably an integer of 6 to 12.
- formula (Z-4) or formula (Z-5) — ((CH 2 ) y CH 2 O) — or ((CH 2 ) y CH (CH 3 ) O) — A form in which the terminal is bonded to X is preferred.
- the compounds represented by formula (Z-4) or formula (Z-5) may be used alone or in combination of two or more.
- all six Xs are acryloyl groups
- all six Xs are acryloyl groups
- An embodiment which is a mixture with a compound having at least one hydrogen atom is preferred. With such a configuration, the developability can be further improved.
- the total content of the compound represented by the formula (Z-4) or the formula (Z-5) in the polymerizable compound is preferably 20% by mass or more, and more preferably 50% by mass or more.
- a pentaerythritol derivative and / or a dipentaerythritol derivative are more preferable.
- the polymerizable compound may contain a cardo skeleton.
- a polymerizable compound containing a 9,9-bisarylfluorene skeleton is preferable.
- Examples of the polymerizable compound containing a cardo skeleton include, but are not limited to, oncoat EX series (manufactured by Nagase Sangyo Co., Ltd.) and Ogsol (manufactured by Osaka Gas Chemical Co., Ltd.).
- the composition preferably contains a polymerization initiator.
- the polymerization initiator is not particularly limited, and a known polymerization initiator can be used.
- a polymerization initiator a photoinitiator, a thermal polymerization initiator, etc. are mentioned, for example, A photoinitiator is preferable.
- the polymerization initiator is preferably a so-called radical polymerization initiator.
- the content of the polymerization initiator is preferably 1 to 20% by mass, more preferably 3 to 10% by mass, based on the total solid content of the composition.
- a polymerization initiator may be used individually by 1 type, or may use 2 or more types together. When two or more polymerization initiators are used in combination, the total content is preferably within the above range.
- thermal polymerization initiator examples include 2,2′-azobisisobutyronitrile (AIBN), 3-carboxypropionitrile, azobismaleonitrile, and dimethyl- (2,2 ′)-azobis (2 -Methylpropionate) [V-601] and the like, and organic peroxides such as benzoyl peroxide, lauroyl peroxide, and potassium persulfate.
- AIBN 2,2′-azobisisobutyronitrile
- 3-carboxypropionitrile 3-carboxypropionitrile
- azobismaleonitrile examples
- organic peroxides such as benzoyl peroxide, lauroyl peroxide, and potassium persulfate.
- organic peroxides such as benzoyl peroxide, lauroyl peroxide, and potassium persulfate.
- the composition preferably contains a photopolymerization initiator.
- a photoinitiator if a polymerization of a polymeric compound can be started, it will not restrict
- the photopolymerization initiator for example, those having photosensitivity from the ultraviolet region to the visible light region are preferable. Further, it may be an activator that generates an active radical by generating some action with a photoexcited sensitizer, and may be an initiator that initiates cationic polymerization according to the type of the polymerizable compound.
- the photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).
- the content of the photopolymerization initiator is preferably 1 to 20% by mass and more preferably 3 to 10% by mass with respect to the total solid content of the composition.
- a photoinitiator may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of photoinitiators together, it is preferable that the total amount is in the said range.
- Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those containing a triazine skeleton, those containing an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, Examples include oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, aminoacetophenone compounds, and hydroxyacetophenones.
- paragraphs 0265 to 0268 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
- the photopolymerization initiator for example, an aminoacetophenone-based initiator described in JP-A-10-291969 and an acylphosphine-based initiator described in Japanese Patent No. 4225898 can also be used.
- an aminoacetophenone-based initiator described in JP-A-10-291969 and an acylphosphine-based initiator described in Japanese Patent No. 4225898 can also be used.
- the hydroxyacetophenone compound IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names: all manufactured by BASF) can be used.
- the aminoacetophenone compound commercially available products IRGACURE-907, IRGACURE-369, or IRGACURE-379EG (trade names: all manufactured by BASF) can be used.
- aminoacetophenone compound a compound described in JP-A-2009-191179 in which an absorption wavelength is matched with a long wave light source such as 365 nm or 405 nm can also be used.
- acylphosphine compound commercially available IRGACURE-819 or IRGACURE-TPO (trade name: all manufactured by BASF) can be used.
- More preferred examples of the photopolymerization initiator include oxime ester polymerization initiators (oxime compounds).
- oxime compounds are preferred because they have high sensitivity and high polymerization efficiency, can cure the composition layer regardless of the content concentration of titanium nitride-containing particles in the composition, and are easy to design with a high content of titanium nitride-containing particles.
- a compound described in JP-A No. 2001-233842 a compound described in JP-A No. 2000-80068, or a compound described in JP-A No. 2006-342166 can be used.
- Examples of the oxime compound include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, and 2-ethoxycarbonyl And oxyimino-1-phenylpropan-1-one.
- J.H. C. S. Perkin II (1979) pp. 1653-1660) J.M. C. S.
- IRGACURE-OXE01 manufactured by BASF
- IRGACURE-OXE02 manufactured by BASF
- IRGACURE-OXE03 manufactured by BASF
- IRGACURE-OXE04 manufactured by BASF
- TR-PBG-304 manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.
- Adeka Arcles NCI-831 and Adeka Arcles NCI-930 manufactured by ADEKA
- N-1919 carboxyl ether skeleton containing photoinitiator
- An agent manufactured by ADEKA
- oxime compounds other than those described above compounds described in JP-A-2009-519904 in which an oxime is linked to the carbazole N-position; compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety; Compounds described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced at the dye moiety; Ketooxime compounds described in International Patent Publication No. 2009-131189; Triazine skeleton and oxime skeleton are the same molecule A compound described in US Pat. No.
- the oxime compound is preferably a compound represented by the following formula (OX-1).
- the N—O bond of the oxime compound may be an (E) oxime compound, a (Z) oxime compound, a mixture of (E) isomer and (Z) isomer. Good.
- R and B each independently represent a monovalent substituent
- A represents a divalent organic group
- Ar represents an aryl group.
- the monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
- the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group.
- these groups may have one or more substituents.
- the substituent mentioned above may be further substituted by another substituent.
- the substituent examples include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.
- the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.
- the divalent organic group represented by A is preferably an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, or an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.
- An oxime compound containing a fluorine atom can also be used as a photopolymerization initiator.
- Specific examples of the oxime compound containing a fluorine atom include compounds described in JP2010-262028; compounds 24 and 36 to 40 described in JP2014-500852; compounds described in JP2013-164471A (C-3); and the like. This content is incorporated herein.
- photopolymerization initiator compounds represented by the following general formulas (1) to (4) can also be used.
- R 1 and R 2 are each independently an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or Represents an arylalkyl group having 7 to 30 carbon atoms, and when R 1 and R 2 are phenyl groups, the phenyl groups may be bonded to each other to form a fluorene group, and R 3 and R 4 are each independently Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms, and X represents a direct bond or carbonyl Indicates a group.
- R 1, R 2, R 3 and R 4 have the same meanings as R 1, R 2, R 3 and R 4 in Formula (1)
- R 5 is -R 6, -OR 6 , —SR 6 , —COR 6 , —CONR 6 R 6 , —NR 6 COR 6 , —OCOR 6 , —COOR 6 , —SCOR 6 , —OCSR 6 , —COSR 6 , —CSOR 6 , —CN
- halogen R 6 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms
- X represents a direct bond or a carbonyl group, and a represents an integer of 0 to 4.
- R 1 represents an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aryl group having 7 to 30 carbon atoms.
- R 3 and R 4 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a carbon number of 4 Represents a heterocyclic group of ⁇ 20, and X represents a direct bond or a carbonyl group.
- R 1, R 3 and R 4 have the same meanings as R 1, R 3 and R 4 in the formula (3)
- R 5 is, -R 6, -OR 6, -SR 6, Represents —COR 6 , —CONR 6 R 6 , —NR 6 COR 6 , —OCOR 6 , —COOR 6 , —SCOR 6 , —OCSR 6 , —COSR 6 , —CSOR 6 , —CN, a halogen atom or a hydroxyl group
- R 6 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms
- X is a direct bond or Represents a carbonyl group, and a represents an integer of 0 to 4.
- R 1 and R 2 are preferably each independently a methyl group, ethyl group, n-propyl group, i-propyl group, cyclohexyl group or phenyl group.
- R 3 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a xylyl group.
- R 4 is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group.
- R 5 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a naphthyl group.
- X is preferably a direct bond.
- R 1 is preferably each independently a methyl group, ethyl group, n-propyl group, i-propyl group, cyclohexyl group or phenyl group.
- R 3 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a xylyl group.
- R 4 is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group.
- R 5 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a naphthyl group.
- X is preferably a direct bond.
- Specific examples of the compounds represented by formula (1) and formula (2) include, for example, compounds described in paragraphs 0076 to 0079 of JP-A No. 2014-137466. This content is incorporated herein.
- oxime compounds preferably used in the above composition are shown below.
- oxime compound a compound described in Table 1 of International Publication No. 2015-036910 can also be used, and the above contents are incorporated herein.
- the oxime compound preferably has a maximum absorption wavelength in the wavelength region of 350 nm to 500 nm, more preferably has a maximum absorption wavelength in the wavelength region of 360 nm to 480 nm, and more preferably has a 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, more preferably 5,000 to 200,000 from the viewpoint of sensitivity. More preferably, it is 000.
- a known method can be used. It is preferable to measure. You may use a photoinitiator in combination of 2 or more type as needed.
- the composition preferably contains a solvent.
- the content of the solvent is not particularly limited, but is preferably adjusted so that the total solid content of the composition is 15 to 40% by mass.
- a solvent may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of solvent together, it is preferable to adjust so that the total solid content of a composition may become in the said range.
- a well-known solvent can be used.
- the solvent include water or an organic solvent.
- the organic solvent include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone.
- Cyclohexanone, cyclopentanone, diacetone alcohol ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol mono Chill ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, ⁇ -butyrolactone, ethyl acetate, Examples include but are not limited to butyl acetate, methyl lactate, N-methyl-2-pyrrolidone, and ethyl lactate.
- the composition preferably contains a surfactant.
- the surfactant contributes to improving the coating property of the composition.
- the content of the surfactant is preferably 0.001 to 2.0% by mass with respect to the total solid content of the composition.
- Surfactant may be used individually by 1 type, or may use 2 or more types together. When two or more surfactants are used in combination, the total amount is preferably within the above range.
- surfactant examples include fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants.
- the liquid properties (particularly fluidity) of the composition are further improved. That is, in the case of forming a film using a composition containing a fluorosurfactant, wettability to the surface to be coated is improved by lowering the interfacial tension between the surface to be coated and the coating liquid. The coating property to the coated surface is improved. For this reason, even when a thin film of about several ⁇ m is formed with a small amount of liquid, it is effective in that a film having a uniform thickness with small thickness unevenness can be more suitably formed.
- the fluorine content in the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and still more preferably 7 to 25% by mass.
- a fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity in the thickness of the coating film and / or liquid-saving properties, and has good solubility in the composition.
- fluorosurfactant examples include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780 (above DIC Corporation), Florad FC430, FC431, FC171 (Sumitomo 3M Limited), Surflon S-382, SC-101, SC- 103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, K-H-40 (above, manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (made by OMNOVA) etc. are mentioned.
- a block polymer can also be used as the fluorosurfactant, and specific examples include compounds described in JP-A No. 2011-89090.
- the composition may contain a colorant.
- a colorant intends a compound different from titanium nitride-containing particles.
- colorant various known pigments (color pigments) and dyes (color dyes) can be used.
- a pigment an inorganic pigment and an organic pigment are mentioned, for example.
- a coloring agent may be used individually by 1 type, or may use 2 or more types together.
- the inorganic pigment is not particularly limited, and a known inorganic pigment can be used.
- examples of inorganic pigments include carbon black, silica, zinc white, lead white, lithopone, titanium oxide, chromium oxide, iron oxide, precipitated barium sulfate and barite powder, red lead, iron oxide red, yellow lead, zinc yellow ( 1 type of zinc yellow, 2 types of zinc yellow), ultramarine blue, prussian blue (potassium ferrocyanide) zircon gray, praseodymium yellow, chrome titanium yellow, chrome green, peacock, Victoria green, bituminous (unrelated to Prussian blue) , Vanadium zirconium blue, chrome tin pink, ceramic red, and salmon pink.
- a black inorganic pigment and as the inorganic pigment, carbon black, titanium black, and at least a content capable of forming a cured film having a high optical density is obtained.
- a metal pigment or the like (hereinafter also referred to as “black pigment”) is preferable.
- the metal pigment include a metal oxide containing one or more metal elements selected from the group consisting of Nb, V, Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag. Product or metal nitrogen product.
- the inorganic pigment preferably contains at least one selected from the group consisting of metal pigments containing silver, metal pigments containing tin, and metal pigments containing silver and tin. Or it is more preferable to contain at least one selected from pigments containing oxynitrides.
- an inorganic pigment may be used individually by 1 type, or may use 2 or more types together.
- colorant examples include those described in paragraphs 0027 to 0200 of JP-A-2014-42375, paragraph 0031 of JP-A-2008-260927, and paragraphs 0015 to 0025 of JP-A-2015-68893. The above content is incorporated herein.
- a pigment having infrared absorptivity can also be used.
- a tungsten compound, a metal boride, and the like are preferable, and among them, a tungsten compound is more preferable in terms of excellent light-shielding properties at wavelengths in the infrared region.
- a tungsten compound is preferable from the viewpoint of excellent light absorption wavelength region of an oxime polymerization initiator related to curing efficiency by exposure and transparency of visible light region.
- Two or more of these pigments may be used in combination, or may be used in combination with a dye described later.
- chromatic colors such as red, green, yellow, orange, purple and blue are added to black or infrared light-shielding pigments.
- the form which mixes the pigment or the dye mentioned later is mentioned. It is preferable to mix a red pigment or dye, or a purple pigment or dye with a black or infrared pigment, and it is more preferable to mix a red pigment with a black pigment or infrared pigment.
- Organic pigment examples include, for example, Color Index (CI) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 16 7,168,169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,19
- a pigment may be used individually by 1 type, or may use 2 or more types together.
- Examples of the dye include, for example, JP-A No. 64-90403, JP-A No. 64-91102, JP-A No. 1-94301, JP-A No. 6-11614, No. 2592207, and US Pat. No. 4,808,501.
- the disclosed dyes can be used.
- a compound etc. can be used.
- a dye multimer may be used as the dye. Examples of the dye multimer include compounds described in JP2011-213925A and JP2013-041097A. Moreover, you may use the polymerizable dye which has polymerizability in a molecule
- the colorant may further contain an infrared absorber.
- the infrared absorber means a compound having absorption in the wavelength region in the infrared region (preferably, a wavelength of 650 to 1300 nm).
- a compound having a maximum absorption wavelength in a wavelength region of 675 to 900 nm is preferable.
- Examples of colorants having such spectral characteristics include pyrrolopyrrole compounds, copper compounds, cyanine compounds, phthalocyanine compounds, iminium compounds, thiol complex compounds, transition metal oxide compounds, squarylium compounds, naphthalocyanine compounds, quaterylenes.
- Examples include compounds, dithiol metal complex compounds, and croconium compounds.
- the phthalocyanine compound naphthalocyanine compound, iminium compound, cyanine compound, squarylium compound, and croconium compound, the compounds disclosed in paragraphs 0010 to 0081 of JP 2010-1111750 A may be used. Incorporated.
- the cyanine compound for example, “functional pigment, Shin Okawara / Ken Matsuoka / Keijiro Kitao / Kensuke Hirashima, written by Kodansha Scientific”, the contents of which are incorporated herein.
- the compound having a maximum absorption wavelength in the wavelength region of 675 to 900 nm is preferably at least one selected from the group consisting of a cyanine compound, a pyrrolopyrrole compound, a squarylium compound, a phthalocyanine compound, and a naphthalocyanine compound.
- the infrared absorber is preferably a compound that dissolves 1% by mass or more in 25 ° C. water, and more preferably a compound that dissolves 10% by mass or more in 25 ° C. water. By using such a compound, the solvent resistance is improved.
- the pyrrolopyrrole compound can be referred to paragraphs 0049 to 0062 of JP 2010-222557 A, the contents of which are incorporated herein.
- the cyanine compounds and squarylium compounds are disclosed in paragraphs 0022 to 0063 of International Publication No. 2014/088063, paragraphs 0053 to 0118 of International Publication No. 2014/030628, paragraphs 0028 to 0074 of JP 2014-59550 A, and International Publication No. 2012/0074.
- paragraphs 0029 to 0085 of JP-A-2015-40895 paragraphs 0022 to 0036 of JP-A-2014-126642, paragraphs 0011 to 0017 of JP-A-2014-148567, and JP-A-2015-157893.
- Paragraphs 0010 to 0025, paragraphs 0013 to 0026 of JP 2014-095007 A, paragraphs 0013 to 0047 of JP 2014-80487 A, paragraphs 0007 to 0028 of JP 2013-227403 A, and the like can be referred to. The contents are incorporated herein.
- the above composition can be prepared by mixing the above-described various components by a known mixing method (for example, a mixing method using a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, or a wet disperser).
- a mixing method for example, a mixing method using a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, or a wet disperser.
- the respective components may be blended together, or the respective components may be blended sequentially after being dissolved or dispersed in a solvent.
- the order of input and the working conditions when blending are not particularly limited.
- the manufacturing method of a composition contains the following processes by the point from which the more excellent effect of this invention is acquired.
- (2) Titanium nitride-containing particle dispersion and other components Mixing step to obtain a composition
- the resin contains a polyimide precursor and / or a polyimide resin (corresponding to an alkali-soluble resin), the titanium nitride-containing particles, the polyimide precursor, and / or Or it is more preferable that it is the process of mixing a polyimide resin and obtaining a titanium nitride containing particle dispersion.
- the composition is preferably filtered with a filter for the purpose of removing foreign substances or reducing defects.
- a filter can be used without particular limitation as long as it has been conventionally used for filtration.
- a filter made of a fluororesin such as PTFE (polytetrafluoroethylene), a polyamide resin such as nylon, and a polyolefin resin (including high density and ultra high molecular weight) such as polyethylene and polypropylene (PP) can be used.
- a filter made of a fluororesin such as PTFE (polytetrafluoroethylene), a polyamide resin such as nylon, and a polyolefin resin (including high density and ultra high molecular weight) such as polyethylene and polypropylene (PP)
- PP polypropylene
- nylon are preferable.
- the filter has a pore diameter of about 0.1 to 7.0 ⁇ m, preferably about 0.2 to 2.5 ⁇ m, more preferably about 0.2 to 1.5 ⁇ m, and still more preferably 0.3 to 0.0 ⁇ m. 7 ⁇ m. By setting this range, it is possible to reliably remove fine foreign matters such as impurities and aggregates contained in the pigment while suppressing filtration clogging of the pigment.
- different filters may be combined. At that time, the filtering by the first filter may be performed only once or may be performed twice or more. When filtering two or more times by combining different filters, it is preferable that the second and subsequent pore diameters are the same or larger than the pore diameter of the first filtering.
- the pore diameter here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Japan Microlith Co., Ltd.) or KITZ Micro Filter Co. .
- a filter formed of the same material as the first filter described above can be used.
- the pore size of the second filter is suitably about 0.2 to 10.0 ⁇ m, preferably about 0.2 to 7.0 ⁇ m, and more preferably about 0.3 to 6.0 ⁇ m.
- the composition does not contain impurities such as metals, metal salts containing halogens, acids, and alkalis.
- the content of impurities contained in these materials is preferably 1 ppm or less, more preferably 1 ppb or less, still more preferably 100 ppt or less, particularly preferably 10 ppt or less, and substantially free (below the detection limit of the measuring device). Is most preferable.
- the impurities can be measured by an inductively coupled plasma mass spectrometer (manufactured by Yokogawa Analytical Systems, Agilent 7500cs type).
- the thickness of the cured film is not particularly limited, but is preferably 0.2 to 25 ⁇ m.
- the above thickness is an average thickness, and is a value obtained by measuring the thicknesses of five or more arbitrary points of the cured film and arithmetically averaging them.
- substrate, forming a coating film, performing a hardening process with respect to a coating film, and manufacturing a cured film is mentioned.
- the method of the curing treatment is not particularly limited, and examples thereof include a photocuring treatment or a thermosetting treatment, and a photocuring treatment (particularly a curing treatment by irradiation with actinic rays or radiation) is preferable from the viewpoint of easy pattern formation. .
- the cured film which concerns on embodiment of this invention is a cured film obtained by hardening
- limit especially as a manufacturing method of a cured film It is preferable to contain the following processes. -Composition layer formation process-Exposure process-Development process Hereinafter, each process is demonstrated.
- the composition layer forming step is a step of forming a composition layer using the composition.
- a process of forming a composition layer using a composition the process of apply
- substrate is not restrict
- a silicon substrate is mentioned, for example, When using as a color filter (including the color filter for solid-state image sensors), a glass substrate etc. are mentioned.
- Various coating methods such as spin coating, slit coating, ink jet method, spray coating, spin coating, cast coating, roll coating, and screen printing can be applied as a method for coating the composition on the substrate. it can.
- the composition coated on the substrate is usually dried at 70 to 150 ° C. for about 1 to 4 minutes to form a composition layer.
- the composition layer formed in the composition layer formation step is exposed by irradiating actinic rays or radiation through a photomask having a patterned opening, and only the composition layer irradiated with light is exposed. Is cured.
- the exposure is preferably performed by irradiation of radiation, and as radiation that can be used for exposure, ultraviolet rays such as g-line, h-line, and i-line are particularly preferably used, and a high-pressure mercury lamp is preferred as a light source.
- the irradiation intensity is preferably 5 ⁇ 1500mJ / cm 2, more preferably 10 ⁇ 1000mJ / cm 2.
- development processing (development step) is performed to elute the light non-irradiated portion in the exposure step into the developer. Thereby, only the photocured part remains.
- An alkaline developer may be used as the developer. In that case, it is preferable to use an organic alkali developer.
- the development temperature is usually preferably 20 to 40 ° C., and the development time is preferably 20 to 180 seconds.
- an alkaline solution for example, as an inorganic developer, an alkaline compound such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, and sodium metaoxalate, Examples thereof include an aqueous alkali solution dissolved so that the concentration is 0.001 to 10% by mass, preferably 0.005 to 0.5% by mass.
- Organic alkaline developers include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, choline , Pyrrole, piperidine, and alkaline compounds such as 1,8-diazabicyclo- [5,4,0] -7-undecene, in a concentration of 0.001 to 10% by mass, preferably 0.005 to 0.5% by mass. %, An aqueous alkali solution dissolved so as to be%.
- a water-soluble organic solvent such as methanol and ethanol, and / or a surfactant, for example, can be added to the alkaline aqueous solution.
- a developer composed of such an alkaline aqueous solution is used, the cured film is generally washed (rinsed) with pure water after development.
- the manufacturing method of a cured film may contain another process.
- the other steps include a substrate surface treatment step, a preheating step (pre-baking step), and a post-heating step (post-baking step).
- the heating temperature in the preheating step and the postheating step is preferably 80 to 300 ° C.
- the upper limit is more preferably 220 ° C. or lower.
- the lower limit is preferably 90 ° C. or higher.
- the heating time in the preheating step and the postheating step is preferably 30 to 300 seconds.
- the cured film preferably has an optical density (OD: Optical Density) of more than 3.5 in a wavelength region of 400 to 1200 nm in a wavelength region of 400 to 1200 nm in terms of having more excellent light shielding properties. More than .7 is more preferable, more than 4.0 is more preferable, and more than 4.2 is particularly preferable.
- the upper limit is not particularly limited, but is generally preferably 10 or less.
- the cured film can be preferably used as a light shielding film.
- an optical density intends the optical density measured by the method described in the Example.
- the optical density per film thickness of 1.0 ⁇ m in the wavelength region of 400 to 1200 nm is greater than 3.5.
- the optical density per 1.0 ⁇ m of film thickness in the entire wavelength range of 400 to 1200 nm is Intended to be greater than 3.5.
- the said cured film has a surface uneven structure. By doing so, the reflectance of a light shielding layer can be reduced. Even if the surface of the light shielding layer itself has a concavo-convex structure, another layer may be provided on the light shielding layer to provide the concavo-convex structure.
- the shape of the surface concavo-convex structure is not particularly limited, but the surface roughness is preferably in the range of 0.55 ⁇ m to 1.5 ⁇ m.
- the reflectance of the light shielding layer is preferably 5% or less, more preferably 3% or less, and particularly preferably 2% or less.
- Solid-state imaging device and solid-state imaging device A solid-state imaging device and a solid-state imaging device according to an embodiment of the present invention contain the cured film.
- the form in which the solid-state imaging device contains a cured film is not particularly limited. For example, a plurality of photodiodes, polysilicon, and the like that form a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) on a substrate And comprising the cured film of the present invention on the side of the support where the light receiving element is formed (for example, the portion other than the light receiving portion and / or the color adjustment pixel) or on the opposite side of the forming surface. The thing which was done is mentioned.
- the solid-state imaging device contains the solid-state imaging element.
- the solid-state imaging device 100 includes a rectangular solid-state imaging element 101 and a transparent cover glass 103 that is held above the solid-state imaging element 101 and seals the solid-state imaging element 101. Yes. Further, a lens layer 111 is provided on the cover glass 103 with a spacer 104 interposed therebetween.
- the lens layer 111 includes a support body 113 and a lens material 112. The lens layer 111 may have a configuration in which the support 113 and the lens material 112 are integrally formed.
- the peripheral region of the lens layer 111 is shielded from light by providing a cured film 114.
- the cured film according to the embodiment of the present invention can also be used as the cured film 114.
- the solid-state imaging device 101 photoelectrically converts an optical image formed on the imaging unit 102 serving as a light receiving surface thereof, and outputs it as an image signal.
- the solid-state imaging device 101 includes a laminated substrate 105 in which two substrates are laminated.
- the laminated substrate 105 includes a rectangular chip substrate 106 and a circuit substrate 107 having the same size, and the circuit substrate 107 is laminated on the back surface of the chip substrate 106.
- the material of the substrate used as the chip substrate 106 is not particularly limited, and a known material can be used.
- An imaging unit 102 is provided at the center of the surface of the chip substrate 106. Further, when stray light is incident on the peripheral area of the imaging unit 102, dark current (noise) is generated from a circuit in the peripheral area. Therefore, the peripheral area is shielded by a cured film 115.
- the cured film according to the embodiment of the present invention can also be used as the cured film 115.
- a plurality of electrode pads 108 are provided on the surface edge of the chip substrate 106.
- the electrode pad 108 is electrically connected to the imaging unit 102 via a signal line (not shown) provided on the surface of the chip substrate 106 (which may be a bonding wire).
- External connection terminals 109 are provided on the back surface of the circuit board 107 at positions substantially below the electrode pads 108, respectively. Each external connection terminal 109 is connected to an electrode pad 108 via a through electrode 110 that vertically penetrates the multilayer substrate 105. Each external connection terminal 109 is connected to a control circuit that controls driving of the solid-state image sensor 101, an image processing circuit that performs image processing on an image signal output from the solid-state image sensor 101, and the like via a wiring (not shown). Has been.
- the imaging unit 102 is configured by each unit provided on a substrate 204 such as a light receiving element 201, a color filter 202, and a microlens 203.
- the color filter 202 includes a blue pixel 205b, a red pixel 205r, a green pixel 205g, and a black matrix 205bm.
- the cured film according to the embodiment of the present invention can also be used as the black matrix 205bm.
- a p-well layer 206 is formed on the surface layer of the substrate 204.
- light receiving elements 201 which are n-type layers and generate and store signal charges by photoelectric conversion, are arranged in a square lattice pattern.
- a vertical transfer path 208 made of an n-type layer is formed via a readout gate portion 207 on the surface layer of the p-well layer 206.
- a vertical transfer path 208 belonging to an adjacent pixel is formed on the other side of the light receiving element 201 via an element isolation region 209 made of a p-type layer.
- the read gate unit 207 is a channel region for reading signal charges accumulated in the light receiving element 201 to the vertical transfer path 208.
- a gate insulating film 210 made of an ONO (Oxide-Nitride-Oxide) film is formed on the surface of the substrate 204.
- a vertical transfer electrode 211 made of polysilicon or amorphous silicon is formed on the gate insulating film 210 so as to cover the vertical transfer path 208, the read gate portion 207, and the element isolation region 209.
- the vertical transfer electrode 211 functions as a drive electrode that drives the vertical transfer path 208 to perform charge transfer, and a read electrode that drives the read gate unit 207 to read signal charges.
- the signal charges are sequentially transferred from the vertical transfer path 208 to a horizontal transfer path (not shown) and an output unit (floating diffusion amplifier), and then output as a voltage signal.
- a cured film 212 is formed on the vertical transfer electrode 211 so as to cover the surface thereof.
- the cured film 212 has an opening at a position directly above the light receiving element 201 and shields light from other areas.
- the cured film according to the embodiment of the present invention can also be used as the cured film 212.
- an insulating film 213 made of BPSG (borophosphosilicate glass), an insulating film (passivation film) 214 made of P-SiN, and a transparent intermediate layer made of a planarizing film 215 made of transparent resin or the like are provided. ing.
- the color filter 202 is formed on the intermediate layer.
- a black matrix contains the cured film which concerns on embodiment of this invention.
- the black matrix may be contained in a color filter, a solid-state image sensor, and a liquid crystal display device.
- As the black matrix those already described above; a black edge provided at the periphery of a display device such as a liquid crystal display device; a lattice shape between red, blue, and green pixels, and / or a stripe shape A black portion of the TFT; a dot-like and / or a linear black pattern for shielding a thin film transistor (TFT);
- TFT thin film transistor
- the black matrix improves the display contrast, and in the case of an active matrix liquid crystal display device using a thin film transistor (TFT), in order to prevent deterioration in image quality due to light current leakage, a high light shielding property (with an optical density OD). 3 or more).
- TFT thin film transistor
- the production method of the black matrix is not particularly limited, but can be produced by the same method as the production method of the cured film.
- the composition can be applied to a substrate to form a composition layer, and exposed and developed to produce a patterned cured film (black matrix).
- the thickness of the cured film used as the black matrix is preferably 0.1 to 4.0 ⁇ m.
- the material of the substrate is not particularly limited, but preferably has a transmittance of 80% or more with respect to visible light (wavelength: 400 to 800 nm).
- Specific examples of such materials include glass such as soda lime glass, alkali-free glass, quartz glass, and borosilicate glass; plastics such as polyester-based resins and polyolefin-based resins; In view of chemical resistance and heat resistance, alkali-free glass or quartz glass is preferable.
- the color filter according to the embodiment of the present invention contains a cured film.
- the form in which the color filter contains a cured film is not particularly limited, and examples thereof include a color filter including a substrate and the black matrix. That is, a color filter including red, green, and blue colored pixels formed in the openings of the black matrix formed on the substrate can be exemplified.
- a color filter containing a black matrix can be produced, for example, by the following method.
- a coating film (resin composition layer) of a resin composition containing a colorant corresponding to each colored pixel of a color filter is formed in an opening of a patterned black matrix formed on a substrate.
- the resin composition for each color is not particularly limited, and a known resin composition can be used.
- the titanium nitride-containing particles are colored corresponding to each pixel. What was replaced with the agent may be used.
- it exposes with respect to the resin composition layer through the photomask which has a pattern corresponding to the opening part of a black matrix.
- the colored pixels can be formed in the openings of the black matrix by baking.
- a color filter having red, green, and blue pixels can be manufactured by performing a series of operations using a resin composition for each color that contains red, green, and blue pigments.
- the liquid crystal display device contains a cured film.
- the form in which the liquid crystal display device contains a cured film is not particularly limited, but examples include a form containing a color filter containing the black matrix (cured film) already described.
- liquid crystal display device for example, a mode provided with a pair of substrates arranged opposite to each other and a liquid crystal compound sealed between the substrates can be mentioned.
- the substrate is as already described as the substrate for the black matrix.
- liquid crystal display device for example, from the user side, a polarizing plate / substrate / color filter / transparent electrode layer / alignment film / liquid crystal layer / alignment film / transparent electrode layer / TFT (Thin Film Transistor)
- TFT Thin Film Transistor
- the liquid crystal display device is not limited to the above.
- Display device (Junsho Ibuki) The liquid crystal display device described in the book “Industry Books Co., Ltd.” issued in 1989).
- the infrared sensor which concerns on embodiment of this invention contains the said cured film.
- the infrared sensor which concerns on the said embodiment is demonstrated using FIG.
- reference numeral 310 is a solid-state image sensor.
- the imaging region provided on the solid-state imaging device 310 is configured by combining the infrared absorption filter 311 and the color filter 312 according to the embodiment of the present invention.
- the infrared absorption filter 311 transmits light in the visible light region (for example, light having a wavelength of 400 to 700 nm), light in the infrared region (for example, light having a wavelength of 800 to 1300 nm, preferably light having a wavelength of 900 to 1200 nm, Preferably, it is a film that shields light having a wavelength of 900 to 1000 nm, and a cured film containing an infrared absorber (as already described in the form of the infrared absorber) as a colorant can be used.
- the color filter 312 is a color filter in which pixels that transmit and absorb light of a specific wavelength in the visible light region are formed.
- red (R), green (G), and blue (B) pixels are formed.
- a color filter or the like is used, and its form is as described above.
- a resin film 314 for example, a transparent resin film or the like
- the infrared transmission filter 313 is a filter that has visible light shielding properties and transmits infrared light having a specific wavelength, and is a colorant that absorbs light in the visible light region (for example, a perylene compound and / or bisbenzoic acid).
- a cured film according to an embodiment of the present invention containing a furanone compound or the like and an infrared absorber (for example, a pyrrolopyrrole compound, a phthalocyanine compound, a naphthalocyanine compound, or a polymethine compound) can be used.
- the infrared transmission filter 313 preferably blocks light having a wavelength of 400 to 830 nm and transmits light having a wavelength of 900 to 1300 nm.
- a micro lens 315 is disposed on the incident light h ⁇ side of the color filter 312 and the infrared transmission filter 313.
- a planarization film 316 is formed so as to cover the microlens 315. In the embodiment shown in FIG.
- the resin film 314 is disposed, but an infrared transmission filter 313 may be formed instead of the resin film 314. That is, the infrared transmission filter 313 may be formed on the solid-state image sensor 310.
- the film thickness of the color filter 312 and the film thickness of the infrared transmission filter 313 are the same, but the film thickness of both may be different.
- the color filter 312 is provided closer to the incident light h ⁇ than the infrared absorption filter 311, but the infrared absorption filter 311 and the color filter 312 are switched in order to absorb infrared rays.
- the filter 311 may be provided closer to the incident light h ⁇ than the color filter 312.
- the infrared absorption filter 311 and the color filter 312 are stacked adjacent to each other.
- the two filters are not necessarily adjacent to each other, and other layers are provided between them.
- the cured film according to the embodiment of the present invention can be used as a light-shielding film such as an edge or a side surface of the surface of the infrared absorption filter 311 and can be used for an inner wall of an infrared sensor device to improve sensitivity.
- this infrared sensor since image information can be captured simultaneously, motion sensing or the like that recognizes a target whose motion is to be detected is possible. Furthermore, since distance information can be acquired, an image including 3D information can be taken.
- the solid-state imaging device includes a lens optical system, a solid-state imaging device, an infrared light emitting diode, and the like.
- paragraphs 0032 to 0036 of JP 2011-233983 A can be referred to, and the contents thereof are incorporated in this specification.
- the near-infrared sensor according to an embodiment of the present invention is obtained by replacing the infrared absorption filter of the infrared sensor already described with a near-infrared absorption filter.
- the near-infrared absorbing filter contains a near-infrared absorbing material having a maximum absorption wavelength at a wavelength of 700 nm or more and less than 900 nm, and can be formed using a near-infrared absorbing composition.
- the maximum absorption wavelength is preferably substantially the same as the emission wavelength of an infrared LED (infrared light emitting diode) described later, and the difference between them is preferably within 20 nm, more preferably within 10 nm.
- a pyrrolopyrrole compound is preferable, and a compound represented by the general formula (1) in JP-A No. 2015-200878 is more preferable.
- the proximity sensor according to an embodiment of the present invention is not particularly limited as long as it contains the cured film, and examples thereof include proximity sensors described in JP-A-2008-83675 and JP-A-2015-225423. .
- the cured film is composed of portable devices such as personal computers, tablets, mobile phones, smartphones and digital cameras; OA (Office Automation) devices such as printer multifunction devices and scanners; surveillance cameras, bar code readers, and automatic cash deposits.
- Machine automated teller machine
- high-speed camera and industrial equipment such as personal authentication using face image authentication
- in-vehicle camera equipment medical camera equipment such as endoscope, capsule endoscope and catheter
- Optics used in space equipment such as sensors, biosensors, military reconnaissance cameras, 3D map cameras, weather and ocean observation cameras, land resource exploration cameras, and exploration cameras for space astronomy and deep space targets
- Filter and Light blocking member and the light-shielding layer of the module further is suitable for anti-reflection member and the antireflection layer.
- the cured film can also be used for applications such as micro LED (Light Emitting Diode) and micro OLED (Organic Light Emitting Diode).
- the cured film is suitable for members that provide a light shielding function or an antireflection function, in addition to optical filters and optical films used in micro LEDs and micro OLEDs.
- Examples of the micro LED and the micro OLED include those described in JP-T-2015-500562 and JP-T-2014-533890.
- the cured film is suitable as an optical and optical film used in quantum dot displays. Moreover, it is suitable as a member which provides a light shielding function and an antireflection function.
- quantum dot displays include US Patent Application Publication No. 2013/0335677, US Patent Application Publication No. 2014/0036536, US Patent Application Publication No. 2014/0036203, and US Patent Application Publication No. 2014/0035960. What has been described.
- Titanium nitride-containing particles TiN-1 were produced by the following method. It was produced using the apparatus described in JP 2005-343784 A, paragraph 0042 and FIG. Specifically, titanium nitride using an apparatus (hereinafter referred to as “nanoparticle manufacturing apparatus”) in which the discharge vessel 1 in FIG. 1 of the above publication is a stainless steel vacuum chamber (Fukushin Industries Co., Ltd.) is used. Containing particles were produced. First, the air in the vacuum chamber was exhausted by an exhaust pump. Thereafter, helium (He) gas (purity 99.99%) was supplied to the vacuum chamber until the pressure reached 600 Torr (79.99 kPa).
- He helium
- the discharge electrode of the nanoparticle production apparatus tungsten formed into a hollow rod having a length of 500 mm, a diameter of 12 mm, and a hollow diameter of 6 mm was used.
- the arrangement of the discharge electrodes was the same as that shown in FIG. 1 of JP-A-2005-343784. Specifically, 12 discharge electrodes were arranged in two stages of 6 each. The distance between the upper stage and the lower stage was about 160 mm.
- the discharge electrode having a hollow structure is connected to a raw material supply device so that the raw material gas can be supplied from the hollow portion of the discharge electrode into the vacuum chamber.
- the discharge starts with the tip of each discharge electrode in contact with each discharge electrode while applying an alternating current (voltage 20 to 40 V, current 70 to 100 A) having a phase difference to each discharge electrode.
- an alternating current voltage 20 to 40 V, current 70 to 100 A
- the tip of each discharge electrode is moved outward so as to be separated, and the arc discharge is continued by setting the distance between the tips of the adjacent discharge electrodes to be 5 mm to 10 mm. .
- the supply tank of the raw material supply apparatus was heated and the raw material gas was introduced into the vacuum chamber.
- NH 3 gas liquefied ammonium ECOAN, Showa Denko KK
- H 2 gas hydrogen gas, Showa Denko Gas Products
- Ar gas argon gas, Taiyo Nippon Sanso
- TiCl 4 gas TiCl 4 gas
- the obtained particles were placed in an airtight container into which nitrogen (N 2 ) gas whose O 2 content and water content were controlled to 100 ppm or less, respectively, and allowed to stand for 24 hours.
- nitrogen (N 2 ) gas whose O 2 content and water content were controlled to 100 ppm or less, respectively, and allowed to stand for 24 hours.
- the content of chlorine atoms in the titanium nitride-containing particles TiN-1 is determined by burning the titanium nitride-containing particles together with an auxiliary agent at 1000 ° C., collecting the generated chlorine gas in an absorption liquid, and performing ion chromatography. Analyzed using the instrument. Further, regarding the content (mass%) of nitrogen atoms (N) and oxygen atoms (O) in the titanium nitride-containing particles TiN-1, the oxygen / nitrogen analyzer “EMGA-620W / C” manufactured by HORIBA, Ltd. (Trade name) and calculated by the inert gas melting-thermal conductivity method. The above results are shown in Table 1 as the contents (mass%) of Ti, N, O, and Cl.
- Titanium nitride-containing particles were made in the same manner as the titanium nitride-containing particles TiN-1 except that the amount of gas introduced was adjusted so that the volume ratio of the flow rates of the respective raw material gases was as shown in Table 1.
- TiN-2 to TiN-13 were produced. About each produced titanium nitride containing particle
- titanium nitride-containing particles TiN-C [Production of titanium nitride-containing particles TiN-C] Except for adjusting the amount of gas to be introduced so that the volume ratio of the flow rate of each raw material gas is as shown in Table 1 and not having undergone the above heating step, the titanium nitride-containing particles TiN- In the same manner as in Example 1, titanium nitride-containing particles TiN—C were produced. Regarding the produced titanium nitride-containing particles TiN—C, the contents of Ti, N, O, and Cl were measured by the same method as described above. The results are shown in Table 1.
- Measurement gas Helium cell size: 100cc Flow purge: 10 minutes
- Target pressure 17.5 PSI (pound-force per square inch, 1.0 PSI corresponds to 6894.76 Pa)
- Number of measurements The density was evaluated by the arithmetic average value of the values obtained by the last three measurements (13th to 15th of these measurements).
- Example 1 Preparation of Composition 1
- a dispersant D the structure of the dispersant D will be described later
- an organic solvent PGMEA (propylene glycol 1-monomethyl ether 2-acetate) described in Table 2)
- Cyclopentanone / butyl acetate 30/20/22 (mass ratio)
- the obtained dispersion was subjected to a dispersion treatment under the following conditions using NPM-Pilot manufactured by Shinmaru Enterprises Co., Ltd. to obtain a titanium nitride-containing particle dispersion 1.
- the ratio of the dispersant to the titanium nitride-containing particles (D / P) is as described in Table 2.
- PGMEA propylene glycol 1-monomethyl ether 2- Acetate
- cyclopentanone / butyl acetate 30/20/22 (mass ratio)
- compositions of Other Examples and Comparative Examples Except having adjusted so that the kind and content of each component may become as having described in Table 2, it carried out similarly to Example 1, and obtained the composition of each Example and each comparative example. In addition, the numerical value of content of each component in Table 2 intends mass%.
- Resin A Acryl Cure RD-F8 (trade name, manufactured by Nippon Shokubai Co., Ltd.) was used. The structure of resin A is shown below.
- composition layer [Complex dielectric constant of titanium nitride-containing particles] Each composition was spin-coated on an 8-inch silicon wafer to form a composition layer. The thickness of the composition layer was adjusted by controlling the rotation speed of the spin coat so that the thickness of the resulting cured film was 0.3 ⁇ m. Each composition used was appropriately diluted with PGMEA (propylene glycol 1-monomethyl ether 2-acetate) in consideration of the thickness of the resulting cured film. The silicon wafer was placed on a hot plate at 100 ° C. with the surface opposite to the side on which the composition layer was formed facing, and the composition layer was heated for 2 minutes.
- PGMEA propylene glycol 1-monomethyl ether 2-acetate
- the silicon wafer after the paddle development is fixed to the horizontal rotary table by a vacuum chuck method, and the silicon wafer is rotated at a rotation speed of 50 rpm by a rotating device, and pure water is showered from the jet nozzle from above the rotation center. And then rinsed. As a result, a silicon wafer having a 2 cm ⁇ 2 cm patterned cured film formed on the substrate was obtained.
- the obtained silicon wafer was heated at 220 ° C. for 1 hour using a clean oven (High Temp Clean Oven CLH-300S, manufactured by Koyo Thermo System).
- the obtained cured film was analyzed by spectroscopic ellipsometry (M-2000XI-210: spectroscopic ellipsometry manufactured by JA Woollam Co.) with a phase difference ⁇ between p-polarized light (parallel) and s-polarized light (vertical) at a wavelength of 400 to 1200 nm.
- a spectrum of amplitude ratio ⁇ was obtained. Fitting analysis is performed on the obtained ( ⁇ , ⁇ ) spectrum using Bruggeman's effective medium approximation (EMA) model to determine the dielectric constant of the true titanium nitride-containing particles contained in the film.
- EMA effective medium approximation
- the content of the titanium nitride-containing particles used in the EMA model was determined using the prescribed value, but the titanium nitride-containing particles in the cured film were separated by the method already described, and the titanium nitride in the cured film was separated. The content of the product-containing particles may be measured.) From the obtained complex permittivity, the real part of the following complex permittivity was evaluated and is shown in Table 2. A: The minimum value of the real part of the complex dielectric constant was ⁇ 0.5 or less. B: The minimum value of the real part of the complex dielectric constant was more than ⁇ 0.5 and less than 0. C: The minimum value of the real part of the complex dielectric constant was 0 or more.
- a silicon wafer was prepared on which a test electrode pattern (copper) having a line and space with a height of 2.0 ⁇ m and a line width of 25 ⁇ m was formed. Each composition was spin-coated on the electrode pattern so that the film thickness of the cured film obtained was 0.3 ⁇ m to obtain a composition layer. Then, the surface opposite to the side on which the composition layer of the silicon wafer was formed was placed on a hot plate at 100 ° C., and the composition layer was heated (prebaked) for 120 seconds.
- the silicon wafer after the paddle development is fixed to the horizontal rotating table by a vacuum chuck method, and the silicon wafer is rotated at a rotation speed of 50 rpm by a rotating device, and pure water is sprayed from above the rotation center from a jet nozzle. And rinsed. Thereafter, the silicon wafer was heat-treated in an oven at 220 ° C. for 1 hour to obtain a silicon wafer with a TEG (Test Element Group) pattern.
- TEG Transmission Element Group
- the prepared TEG-patterned silicon wafer was stored for 3 months in an environment of a temperature of 25 ° C. and a humidity of 65% RH (relative humidity), and then the RC value (after storage) was measured.
- the ratio of RC value (after storage) to RC value (before storage) was determined and evaluated according to the following criteria and shown in Table 2. Practically, C or higher is preferable.
- A: RC value (after storage) / RC value (before storage) was 1.00 or more and less than 1.08.
- B: RC value (after storage) / RC value (before storage) was 1.08 or more and less than 1.16.
- C RC value (after storage) / RC value (before storage) was 1.16 or more and less than 1.20.
- D RC value (after storage) / RC value (before storage) was 1.20 or more.
- (Viscosity change rate) ((Viscosity after storage of composition) ⁇ (Viscosity before storage of composition) / (Viscosity before storage of composition)) ⁇ 100 (%)
- D The absolute value of the rate of change in viscosity was more than 10%.
- a cured film (a silicon wafer provided with a cured film) was produced by the same method as that produced in the above evaluation of [Electrical characteristics]. Using a scanning electron microscope (manufactured by Hitachi High-Technologies Corporation, trade name “SU8010”), a portion corresponding to a portion (unexposed portion) masked at the time of exposure of the composition layer of the silicon wafer was 20,000. Observation was performed at a magnification of 2, and the number of particulate residues confirmed in the obtained observation image was counted, and patterning property (development residue) was evaluated according to the following criteria. The results are shown in Tables 2 and 3. A: No development residue was observed in the unexposed area. B: 1 to 49 particulate development residues were observed in the unexposed areas. C: 50 to 100 particulate development residues were observed in the unexposed areas. D: 101 or more particulate development residues were observed in the unexposed area.
- a cured film (a silicon wafer provided with a cured film) was produced by the same method as that produced in the above evaluation of [Electrical characteristics].
- the silicon wafer was exposed for 1000 hours in an environment of 90 ° C. and humidity of 85% RH.
- the exposed silicon wafer was observed using a laser microscope (manufactured by Olympus, trade name “LEXT OLS4500”). The results are shown in Tables 2 and 3.
- the appearance change of the cured film after the moisture resistance test was observed and evaluated according to the following criteria.
- A No difference was observed in the appearance of the cured film before and after the moisture resistance test, or surface roughness with an unevenness difference of 10 nm or less was observed in the cured film after the moisture resistance test.
- B Surface roughness with an unevenness difference of more than 10 nm and 50 nm or less was observed in the cured film after the moisture resistance test.
- C Surface roughness was observed in the cured film after the moisture resistance test, with a difference in roughness of more than 50 nm and 100 nm or less.
- D Surface roughness with an unevenness difference of more than 100 nm was observed on the cured film after the moisture resistance test.
- the OD (optical density, optical density) of the obtained cured film was measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation). Based on the minimum value (minimum OD) of OD at a wavelength of 400 to 1200 nm, the light shielding property was evaluated according to the following criteria. The results are shown in Tables 2 and 3.
- AA The minimum OD of the cured film was over 4.2.
- A The minimum OD of the cured film was more than 4.0 and 4.2 or less.
- B The minimum OD of the cured film was more than 3.7 and 4.0 or less.
- C The minimum OD of the cured film was more than 3.5 and 3.7 or less.
- D The minimum OD of the cured film was 3.5 or less.
- the compositions of Examples 1 to 27 had the effects of the present invention.
- the composition of Comparative Example 1 did not have the effect of the present invention.
- the composition of Example 2 in which the density of the titanium nitride-containing particles is 3.0 g / cm 3 or more and less than 5.0 g / cm 3 is compared with the composition of Example 10 (above the upper limit). Thus, it had better temporal stability.
- the cured film obtained by the composition of Example 1 has a more excellent appearance after the moisture resistance test as compared with the cured film obtained by the composition of Example 11 (less than the lower limit value). It was.
- the titanium nitride-containing particles contain titanium atoms and nitrogen atoms, and the content atom number ratio X of the nitrogen atom content to the titanium atom content in the titanium nitride-containing particles exceeds 0.
- the composition of Example 2 which was less than 1, had better temporal stability and better patterning properties than the composition of Example 10 (above the upper limit). Further, the composition of Example 2 in which the above X exceeds 0.40 and is less than 0.95 has more excellent patternability than the composition of Example 12 (exceeding the upper limit value). It was. In addition, the composition of Example 2 had better temporal stability compared to the composition of Example 9 (less than the lower limit value).
- the titanium nitride-containing particle further contains oxygen atoms, and the content atom number ratio Y of the oxygen atom content to make the titanium atom content in the titanium nitride-containing particle, and the above X is X + Y ⁇
- the cured film obtained by the composition of Example 2 satisfying the relationship of 0.93 has a better light-shielding property than the cured film obtained by the composition of Example 1 (over the upper limit value). It was.
- the cured film obtained by the composition of Example 2 in which the titanium nitride-containing particles further contain chlorine atoms, and the content of chlorine atoms in the titanium nitride-containing particles is 800 to 3000 mass ppm.
- the composition of Example 17 has better patterning properties than the composition of Example 16, and the cured film obtained by curing has better light-shielding properties and electrical characteristics.
- the dispersant E contains fewer acidic groups in the molecule than the dispersant C, and the titanium nitride-containing particles are less likely to aggregate.
- the composition of Example 17 had better patterning properties than the compositions of Example 18 and Example 19. This is presumably because the dispersant E contains a graft chain.
- Example 22B-1 Except that “TO1382” manufactured by Toagosei Co., Ltd. was used instead of the polymerizable compound M1, the following resin B-1 (7.1 parts by mass) was used instead of the resin A, and the dispersant D was not used.
- a composition 22B-1 was produced in the same manner as in Example 4.
- the composition 22B-1 was evaluated in the same manner as described above, and the same evaluation results as in Example 4 were obtained. However, at this time, unlike the solvent description in Table 2, N-methyl-2-pyrrolidone is contained.
- Example 22B-2 Except that “TO1382” manufactured by Toagosei Co., Ltd. was used instead of the polymerizable compound M1, the following resin B-2 (7.1 parts by mass) was used instead of the resin A, and the dispersant D was not used.
- a composition 22B-2 was produced in the same manner as in Example 4. The composition 22B-2 was evaluated in the same manner as described above, and the same evaluation results as in Example 4 were obtained. However, at this time, unlike the solvent description in Table 2, N-methyl-2-pyrrolidone is contained.
- Example 22B-3 Except that “TO1382” manufactured by Toagosei Co., Ltd. was used instead of the polymerizable compound M1, the following resin B-3 (7.1 parts by mass) was used instead of the resin A, and the dispersant D was not used.
- a composition 22B-3 was produced in the same manner as in Example 4.
- the composition 22B-3 was evaluated in the same manner as described above, and the same evaluation results as in Example 4 were obtained. However, at this time, unlike the solvent description in Table 2, N-methyl-2-pyrrolidone is contained.
- Example 22B-4 “TO1382” manufactured by Toagosei Co., Ltd. was used in place of the polymerizable compound M1, and the following resin B-1 (content: 2.3 parts by mass) and resin B-2 (content 3. 5 parts by mass), and the composition 22B-4 was prepared in the same manner as in Example 4 except that the dispersant D was not used.
- the composition 22B-4 was evaluated in the same manner as described above, and the same evaluation results as in Example 4 were obtained. However, at this time, unlike the solvent description in Table 2, N-methyl-2-pyrrolidone is contained.
- Example 22B-5 “TO1382” manufactured by Toagosei Co., Ltd. was used instead of the polymerizable compound M1, and the following resin B-1 (content: 2.3 parts by mass) and resin B-3 (content 3. 5 parts by mass), and the composition 22B-5 was prepared in the same manner as in Example 4 except that the dispersant D was not used.
- the composition 22B-5 was evaluated in the same manner as described above, and the same evaluation results as in Example 4 were obtained. However, at this time, unlike the solvent description in Table 2, N-methyl-2-pyrrolidone is contained.
- Example 23 A composition was prepared in the same manner as in Example 4 except that instead of the polymerizable compound M1, a mixed monomer of the monomer having the following structure and the polymerizable compound M1 (mixing ratio: 50% by mass / 50% by mass) was used. About the produced composition, when evaluation similar to the above was performed, the evaluation result equivalent to Example 4 was obtained. The following monomers were synthesized with reference to JP 2009-169049 A.
- composition 1 was spin-coated on an alkali-free glass substrate so that the dry film thickness was 1.5 ⁇ m to obtain a composition layer. Thereafter, the composition layer was heated together with the silicon wafer on a hot plate (heating condition: 100 ° C., 2 minutes). The composition layer after heating was exposed at an exposure amount of 1000 mJ / cm 2 with an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.) through a 20 ⁇ m line-and-space mask.
- FPA-3000i5 + manufactured by Canon Inc.
- the silicon wafer was placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics), and a composition layer was formed using CD-2000 (manufactured by FUJIFILM Electronics Materials).
- CD-2000 manufactured by FUJIFILM Electronics Materials
- a red (R) resin having a 100 ⁇ m linear pattern in the same manner as the black matrix produced above using the following red (R) resin composition R-1 at the opening of the cured film. A colored pattern was formed.
- green (G) resin composition G-1 is used to give a green (G) coloring pattern
- blue (B) resin composition B-1 is used to give a blue (B) coloring pattern.
- Color patterns were sequentially formed to produce a color filter containing a black matrix.
- the produced color filter was processed with an ITO (Indium Tin Oxide) transparent electrode, an alignment film, and the like to provide a liquid crystal display device. The image quality of the obtained display device was good.
- ITO Indium Tin Oxide
- Example 1-B Production of solid-state imaging device
- a composition 1 is used on the periphery of a color filter of a silicon wafer having a color filter (1 cm square) having a pixel size of 2.0 ⁇ m and a film thickness of 1.5 ⁇ m, a microlens, a metal wiring, and a photodiode, and a width of 100 ⁇ m.
- a cured film having a thickness of 1.5 ⁇ m was formed by photolithography.
- a solid-state image sensor was created using the obtained silicon wafer. The obtained solid-state imaging device had high resolution and excellent color separation.
- Example 1-C Production of infrared sensor
- a composition IR was prepared in the same manner as the composition 1 except that the following pigment mixture was used in place of the titanium nitride-containing particles.
- Pyrrolopyrrole pigment the following structure (synthesized by the method described in JP-A-2009-263614) (infrared absorber having maximum absorption in the wavelength range of 800 to 900 nm)
- PR254 Pigment Red 254 -PB15: 6: Pigment Blue 15: 6 ⁇
- PY139 Pigment Yellow 139 -PV23: Pigment Violet 23
- the above pigments were mixed at the following mass ratio.
- Pyrrolopyrrole pigment / PR254 / PB15: 6 / PY139 / PV23 22.7 / 11.3 / 22.7 / 10.3 / 6.9
- Composition IR was formed by spin coating composition IR so that the dry film thickness was 1.5 ⁇ m on the silicon wafer.
- the silicon wafer was placed on a hot plate at 100 ° C., and the composition layer IR was heated (prebaked) for 120 seconds.
- the composition layer IR was exposed at an optimum exposure amount through a photomask on which a square pixel pattern of 1.4 ⁇ m square was formed. .
- the optimum exposure amount was increased by 50 mJ / cm 2 from 50 to 750 mJ / cm 2 to obtain an exposure amount for resolving the square pixel pattern.
- the silicon wafer on which the composition layer IR has been exposed is placed on a horizontal rotary table of a spin shower developing machine, and CD-2060 (tetramethylammonium hydroxide aqueous solution, manufactured by Fuji Film Electronics Materials) is used. And paddle development at 23 ° C. for 60 seconds. As a result, a colored pattern (corresponding to a cured film) was formed on the silicon wafer.
- the silicon wafer on which the colored pattern was formed was rinsed with pure water and then spray-dried. Further, the silicon wafer was placed on a hot plate at 200 ° C., and the colored pattern was heated (post-baked) for 300 seconds.
- a silicon wafer containing a high-resolution colored pattern as a color filter for an infrared sensor was obtained.
- a cured film having a width of 100 ⁇ m and a film thickness of 1.5 ⁇ m was formed by photolithography using the composition 1 on the periphery of the color filter.
- the obtained color filter was incorporated into a solid-state imaging device according to a known method (corresponding to an infrared sensor).
- the obtained solid-state imaging device was irradiated with a near-infrared LED (light emitting diode) light source having an emission wavelength of 940 nm under a low illuminance environment (0.001 Lux), and an image was captured to compare and evaluate the image performance. In a state where there was little noise derived from visible light, infrared light having an emission wavelength of 940 nm was transmitted, and spectral recognition was good.
- a composition was prepared in the same manner as in Example 2 except that the polymerization initiator I-1 was used instead of IRGACURE OXE-02 (manufactured by BASF). About the produced composition, when the same evaluation as the above was performed, the result similar to Example 2 was obtained.
- a composition was prepared in the same manner as in Example 2 except that PI-04 represented by the following formula was used instead of IRGACURE OXE-02 (manufactured by BASF). About the produced composition, when the same evaluation as the above was performed, the result similar to Example 2 was obtained.
- PI-04 a compound represented by OE74 of WO2015 / 036910, an oxime compound corresponding to a photopolymerization initiator
- Example 2 A composition was prepared in the same manner as in Example 2 except that the surfactant was not used, and the same evaluation as described above was performed. As a result, the same result as in Example 2 was obtained.
- a composition was prepared in the same manner as in Example 2 except that the polymerization inhibitor was not used, and the same evaluation as described above was performed. As a result, the same results as in Example 2 were obtained except that the temporal stability was C. was gotten.
- Example 2 TiN-2 and carbon black (trade name “Color Black S170”, manufactured by Degussa, average primary particle size of 17 nm, BET specific surface area) having a mass ratio of 8: 2 with respect to the whole composition instead of TiN-2
- a composition was prepared in the same manner as in Example 2 except that 200 m 2 / g, carbon black produced by a gas black method) was used. About the produced composition, when evaluation similar to the above was performed, it turned out that it has the performance equivalent to Example 2.
- Example 2 instead of TiN-2, TiN-2 having a mass ratio of 8: 2 to the entire composition and Pigment Yellow 150 (Hangzhou Star-up Pigment Co., Ltd., trade name 6150 Pigment Yellow 5GN) were used.
- a composition was prepared in the same manner as in Example 2 except that it was used. About the produced composition, when evaluation similar to the above was performed, it turned out that it has the performance equivalent to Example 2. FIG. Furthermore, it was found that a dark black light-shielding film was obtained. From this result, it was found that the desired effect can be obtained even when used in combination with other organic pigments or chromatic dyes.
- Solid-state imaging device 101 Solid-state image sensor 102 ... Imaging part 103 ... Cover glass 104 ... Spacer 105 ... Laminated substrate 106 ... Chip substrate 107 ... Circuit board 108 ... Electrode pad 109 ... External connection terminal 110 ... Penetration electrode 111 ... Lens layer 112 ... Lens material 113 ... Supports 114, 115 ... Curing film 201 ... Light receiving element 202 ... Color filter 201 ... Light receiving element 202 ... Color filter 203 ... Micro lens 204 ... Substrate 205b ... Blue pixel 205r ... Red pixel 205g ... Green pixel 205bm ... Black matrix 206...
- P well layer 207 Readout gate portion 208... Vertical transfer path 209. Insulating film 211... Vertical transfer electrode 212... Cured film 213, 214... Insulating film 215. Absorption filter 312 ... Color filter 313 ... Infrared transmission filter 314 ... Resin film 315 ... Micro lens 316 ... Flattening film
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Abstract
Description
具体的には、液晶表示装置等に用いられるカラーフィルタには着色画素間の光を遮蔽し、コントラストを向上させる等の目的で、ブラックマトリクスと呼ばれる硬化膜が備えられている。
また、固体撮像素子においてもノイズ発生防止、画質の向上等を目的として硬化膜が設けられている。現在、携帯電話及びPDA(Personal Digital Assistant)等の電子機器の携帯端末には、小型で薄型な固体撮像装置が搭載されている。このような固体撮像装置は、一般に、CCD(Charge Coupled Device)イメージセンサ及びCMOS(Complementary Metal-Oxide Semiconductor)イメージセンサ等の固体撮像素子と、固体撮像素子上に被写体像を形成するためのレンズと、を備えている。 Conventionally, a composition containing titanium nitride is known as a black composition. Compositions containing titanium nitride have been used for various applications, for example, for the production of cured films provided in liquid crystal display devices and solid-state imaging devices.
Specifically, a color filter used in a liquid crystal display device or the like is provided with a cured film called a black matrix for the purpose of shielding light between colored pixels and improving contrast.
In addition, a solid film is provided with a cured film for the purpose of preventing noise and improving image quality. Currently, portable terminals of electronic devices such as mobile phones and PDAs (Personal Digital Assistants) are equipped with small and thin solid-state imaging devices. Such a solid-state imaging device generally includes a solid-state imaging device such as a CCD (Charge Coupled Device) image sensor and a CMOS (Complementary Metal-Oxide Semiconductor) image sensor, and a lens for forming a subject image on the solid-state imaging device. It is equipped with.
また、本発明は、硬化膜、カラーフィルタ、固体撮像素子、赤外線センサ、近赤外線センサ、及び、近接センサを提供することも課題とする。
なお、本明細書において電気特性とは、実施例に記載された方法により測定される電気特性を意図する。 Therefore, an object of the present invention is to provide a composition capable of producing a cured film having excellent electrical characteristics (hereinafter also referred to as “having the effect of the present invention”).
Another object of the present invention is to provide a cured film, a color filter, a solid-state imaging device, an infrared sensor, a near infrared sensor, and a proximity sensor.
In addition, in this specification, an electrical property intends the electrical property measured by the method described in the Example.
式(1) ε=ε’+ε”j
なお、上記式(1)中、ε’は複素誘電率εの実数部、ε”は複素誘電率εの虚数部、jは虚数単位を表す。
[2] チタン窒化物含有粒子の密度が3.0g/cm3以上、5.0g/cm3未満である、[1]に記載の組成物。
[3] チタン窒化物含有粒子が、チタン原子、及び、窒素原子を含有し、チタン窒化物含有粒子中におけるチタン原子の含有量に対する、窒素原子の含有量の比Xが、0を超え、1未満である、[1]又は[2]に記載の組成物。
[4] 比Xが、0.40を超え、0.95未満である、[3]に記載の組成物。
[5] チタン窒化物含有粒子が、更に酸素原子を含有し、チタン窒化物含有粒子中におけるチタン原子の含有量にする、酸素原子の含有量の比Yと、比Xとが、以下の式(4)を満たす、[3]又は[4]に記載の組成物。
式(4)X+Y<0.93
[6] チタン窒化物含有粒子が、更に塩素原子を含有し、チタン窒化物含有粒子中における塩素原子の含有量が、800~3000質量ppmである、[1]~[5]のいずれかに記載の組成物。
[7] 樹脂が、アルカリ可溶性樹脂を含有する、[1]~[6]のいずれかに記載の組成物。
[8] アルカリ可溶性樹脂が、ポリイミド樹脂、及び、ポリイミド前駆体からなる群から選択される少なくとも1種である、[7]に記載の組成物。
[9] 樹脂が、分散剤を含有する、[1]~[8]のいずれかに記載の組成物。
[10] 更に、重合性化合物を含有する、[1]~[9]のいずれかに記載の組成物。
[11] 更に、重合開始剤を含有する、[1]~[10]のいずれかに記載の組成物。
[12] 重合開始剤が、光重合開始剤を含有する、[11]に記載の組成物。
[13] 光重合開始剤がオキシム化合物である、[12]に記載の組成物。
[14] [1]~[13]のいずれかに記載の組成物を硬化して得られる、硬化膜。
[15] [14]に記載の硬化膜を含有するカラーフィルタ。
[16] [14]に記載の硬化膜を含有する、固体撮像素子。
[17] [14]に記載の硬化膜を含有する、赤外線センサ。
[18] [14]に記載の硬化膜を含有する、近赤外線センサ。
[19] [14]に記載の硬化膜を含有する、近接センサ。 [1] A composition containing titanium nitride-containing particles and a resin, and when the complex dielectric constant ε of the titanium nitride-containing particles at a wavelength of 400 to 1200 nm is expressed by the following formula (1), ε ′ A composition having a minimum value of less than 0.
Formula (1) ε = ε ′ + ε ″ j
In the above formula (1), ε ′ represents a real part of the complex dielectric constant ε, ε ″ represents an imaginary part of the complex dielectric constant ε, and j represents an imaginary unit.
[2] The composition according to [1], wherein the density of the titanium nitride-containing particles is 3.0 g / cm 3 or more and less than 5.0 g / cm 3.
[3] The titanium nitride-containing particles contain titanium atoms and nitrogen atoms, and the ratio X of the nitrogen atom content to the titanium atom content in the titanium nitride-containing particles exceeds 0, The composition according to [1] or [2], which is less than
[4] The composition according to [3], wherein the ratio X is greater than 0.40 and less than 0.95.
[5] Titanium nitride-containing particles further contain oxygen atoms, and the content ratio Y of oxygen atoms and the ratio X, which are the contents of titanium atoms in the titanium nitride-containing particles, are as follows: The composition according to [3] or [4], which satisfies (4).
Formula (4) X + Y <0.93
[6] The titanium nitride-containing particles further contain chlorine atoms, and the content of chlorine atoms in the titanium nitride-containing particles is 800 to 3000 ppm by mass. The composition as described.
[7] The composition according to any one of [1] to [6], wherein the resin contains an alkali-soluble resin.
[8] The composition according to [7], wherein the alkali-soluble resin is at least one selected from the group consisting of a polyimide resin and a polyimide precursor.
[9] The composition according to any one of [1] to [8], wherein the resin contains a dispersant.
[10] The composition according to any one of [1] to [9], further comprising a polymerizable compound.
[11] The composition according to any one of [1] to [10], further comprising a polymerization initiator.
[12] The composition according to [11], wherein the polymerization initiator contains a photopolymerization initiator.
[13] The composition according to [12], wherein the photopolymerization initiator is an oxime compound.
[14] A cured film obtained by curing the composition according to any one of [1] to [13].
[15] A color filter containing the cured film according to [14].
[16] A solid-state imaging device containing the cured film according to [14].
[17] An infrared sensor containing the cured film according to [14].
[18] A near-infrared sensor comprising the cured film according to [14].
[19] A proximity sensor comprising the cured film according to [14].
以下に記載する構成要件の説明は、本発明の代表的な実施形態に基づいてなされることがあるが、本発明はそのような実施形態に限定されるものではない。
なお、本明細書において、「~」を用いて表される数値範囲は、「~」の前後に記載される数値を下限値及び上限値として含む範囲を意味する。
また、本明細書における基(原子団)の表記において、置換及び無置換を記していない表記は、置換基を含有しないものと共に置換基を含有するものをも包含するものである。例えば、「アルキル基」とは、置換基を含有しないアルキル基(無置換アルキル基)のみならず、置換基を含有するアルキル基(置換アルキル基)をも包含する。
また、本明細書中における「活性光線」又は「放射線」とは、例えば、水銀灯の輝線スペクトル、及びエキシマレーザーに代表される遠紫外線、極紫外線(EUV:Extreme ultraviolet lithography光)、X線、並びに電子線等を意味する。また本明細書において光とは、活性光線及び放射線を意味する。本明細書中における「露光」とは、特に断らない限り、水銀灯、及びエキシマレーザーに代表される遠紫外線、X線、並びにEUV光等による露光のみならず、電子線及びイオンビーム等の粒子線による描画も包含する。
また、本明細書において、「(メタ)アクリレート」はアクリレート及びメタアクリレートを表す。また、本明細書において、「(メタ)アクリル」はアクリル及びメタアクリルを表す。また、本明細書において、「(メタ)アクリロイル」は、アクリロイル及びメタクリロイルを表す。また、本明細書において、「(メタ)アクリルアミド」は、アクリルアミド及びメタアクリルアミドを表す。また、本明細書中において、「単量体」と「モノマー」とは同義である。単量体は、オリゴマー及びポリマーと区別され、重量平均分子量が2,000以下の化合物をいう。本明細書中において、重合性化合物とは、重合性基を含有する化合物のことをいい、単量体であっても、ポリマーであってもよい。重合性基とは、重合反応に関与する基をいう。 Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
Moreover, in the description of group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not contain a substituent and what contains a substituent. For example, the “alkyl group” includes not only an alkyl group not containing a substituent (unsubstituted alkyl group) but also an alkyl group containing a substituent (substituted alkyl group).
In addition, in the present specification, “active light” or “radiation” means, for example, the emission line spectrum of a mercury lamp, deep ultraviolet light represented by excimer laser, extreme ultraviolet light (EUV), X-ray, and Means an electron beam. In the present specification, light means actinic rays and radiation. Unless otherwise specified, “exposure” in the present specification is not limited to exposure to deep ultraviolet rays, X-rays, EUV light and the like represented by mercury lamps and excimer lasers, but also particle beams such as electron beams and ion beams. Also includes drawing by.
Moreover, in this specification, "(meth) acrylate" represents an acrylate and a methacrylate. In the present specification, “(meth) acryl” represents acryl and methacryl. In the present specification, “(meth) acryloyl” represents acryloyl and methacryloyl. In the present specification, “(meth) acrylamide” represents acrylamide and methacrylamide. In this specification, “monomer” and “monomer” are synonymous. A monomer is distinguished from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 2,000 or less. In the present specification, the polymerizable compound means a compound containing a polymerizable group, and may be a monomer or a polymer. The polymerizable group refers to a group that participates in a polymerization reaction.
上記組成物は、チタン窒化物含有粒子と、樹脂と、を含有し、チタン窒化物含有粒子の複素誘電率εをε=ε’+ε”jで表すとき、波長400~1200nmにおける、ε’の最小値が0未満であることを特徴とする。なお、ε’は複素誘電率εの実数部、ε”は複素誘電率εの虚数部、jは虚数単位を表す。
本明細書において、複素誘電率の実数部ε’の最小値とは、400~1200nmの各波長に対応する複素誘電率の実数部ε’のうちの最小となる値を意図する。 [Composition]
The composition contains titanium nitride-containing particles and a resin, and when the complex dielectric constant ε of the titanium nitride-containing particles is represented by ε = ε ′ + ε ″ j, the ε ′ at a wavelength of 400 to 1200 nm. The minimum value is less than 0. Note that ε ′ represents a real part of the complex dielectric constant ε, ε ″ represents an imaginary part of the complex dielectric constant ε, and j represents an imaginary unit.
In this specification, the minimum value of the real part ε ′ of the complex dielectric constant is intended to be the minimum value of the real part ε ′ of the complex dielectric constant corresponding to each wavelength of 400 to 1200 nm.
その後、形成した膜について、分光エリプソメトリーを用いて、実施例に記載した方法により複素誘電率を測定する。
なお、膜を形成する際、組成物が重合性化合物を含む組成物である場合、シリコンウェハ上に形成した塗膜に対して硬化処理を施して、測定対象となる膜を形成する。 In this specification, the real part ε ′ of the complex dielectric constant is intended to be a value measured by the following method. First, a film having a thickness of 0.3 μm is formed using a composition on a silicon wafer.
Thereafter, the complex dielectric constant of the formed film is measured by the method described in Examples using spectroscopic ellipsometry.
In addition, when forming a film | membrane, when a composition is a composition containing a polymeric compound, a hardening process is performed with respect to the coating film formed on the silicon wafer, and the film | membrane used as a measuring object is formed.
本発明者らは、上記RC値の上昇は、3ヶ月保存する間に、上記黒色樹脂組成物が含有するチタン窒化物粒子が変質することに起因すると推測した。鋭意検討を続けた結果、本発明者らは、ε’の最小値が0未満となるチタン窒化物含有粒子を含有する組成物が、上記変質を抑制できることを見出した。また、本発明者らは、組成物が樹脂を含有することにより、チタン窒化物含有粒子の凝集が抑制され、上記組成物を硬化させた硬化膜中において、チタン窒化物含有粒子が凝集して生ずる局所的なRC値の上昇を抑制することができることを見出した。以上の知見を得たことにより、本発明に至った。以下では、本発明の実施形態に係る組成物に含有される各成分ごとに、その形態を説明する。 A film produced using the black resin composition described in Patent Document 1 was subjected to an electrical property evaluation test described later for 3 months in an environment of a temperature of 25 ° C. and a humidity of 65% RH (relative humidity). After storage, the RC (resistor capacitor) value was likely to rise.
The inventors of the present invention speculated that the increase in the RC value was caused by alteration of the titanium nitride particles contained in the black resin composition during storage for 3 months. As a result of continuing intensive studies, the present inventors have found that a composition containing titanium nitride-containing particles having a minimum value of ε ′ of less than 0 can suppress the above-mentioned alteration. Further, the present inventors have suppressed the aggregation of titanium nitride-containing particles by containing the resin in the composition, and the titanium nitride-containing particles are aggregated in the cured film obtained by curing the composition. It has been found that a local increase in RC value can be suppressed. Obtaining the above findings led to the present invention. Below, the form is demonstrated for every component contained in the composition which concerns on embodiment of this invention.
上記組成物は、チタン窒化物含有粒子を含有する。チタン窒化物含有粒子としては、チタン窒化物を含有し、上記複素誘電率の関係を満たせば特に制限されない。 [Titanium nitride-containing particles]
The composition contains titanium nitride-containing particles. The titanium nitride-containing particles are not particularly limited as long as they contain titanium nitride and satisfy the above complex dielectric constant relationship.
なお、チタン窒化物含有粒子は、1種を単独で用いても、2種以上を併用してもよい。2種以上の粒子を併用する場合には、合計含有量が上記範囲内であることが好ましい。 The content of titanium nitride-containing particles in the composition is not particularly limited, but is 29 to 70% by mass with respect to the total solid content of the composition in that a cured film having better light-shielding properties can be obtained. It is preferably 45 to 60% by mass.
In addition, titanium nitride containing particle | grains may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of particle | grains together, it is preferable that total content is in the said range.
なかでも、チタン窒化物含有粒子の密度が、3.0g/cm3以上であると、組成物はより優れた経時安定性を有し、5.0g/cm3未満であると、組成物により得られた硬化膜はより優れた耐湿試験後の外観を有する。
なお、本明細書において、チタン窒化物含有粒子の密度は、以下の方法により測定した密度を意図する。すなわち、チタン窒化物含有粒子は、真空乾燥機を用いて乾燥させ、その後、乾式密度計(例えば、アキュピックII1340(島津製作所))を用いて、実施例に記載した条件で、密度を測定する。
なお、組成物からチタン窒化物含有粒子を分離する方法としては、以下の方法を用いることができる。まず、組成物にクロロホルムを含有する有機溶剤を添加し、チタン窒化物含有粒子以外の成分を溶解させて、溶解液を得る。上記溶解液を遠心分離して、沈殿物を得る。次に、上記沈殿物を加熱して、濃縮し、チタン窒化物含有粒子を得る。 The density of the titanium nitride-containing particles is not particularly limited, but is preferably 2.5 to 6.0 g / cm 3 in that the composition has better electrical characteristics and better stability over time. 0.0 g / cm 3 or more is more preferable, and less than 5.0 g / cm 3 is preferable.
Among these, when the density of the titanium nitride-containing particles is 3.0 g / cm 3 or more, the composition has more excellent temporal stability, and when the density is less than 5.0 g / cm 3 , The obtained cured film has a more excellent appearance after the moisture resistance test.
In the present specification, the density of the titanium nitride-containing particles is intended to be a density measured by the following method. That is, the titanium nitride-containing particles are dried using a vacuum dryer, and then the density is measured using a dry density meter (for example, Accupic II 1340 (Shimadzu Corporation)) under the conditions described in the examples.
In addition, as a method of isolate | separating a titanium nitride containing particle | grain from a composition, the following method can be used. First, an organic solvent containing chloroform is added to the composition, and components other than titanium nitride-containing particles are dissolved to obtain a solution. The lysate is centrifuged to obtain a precipitate. Next, the precipitate is heated and concentrated to obtain titanium nitride-containing particles.
試料:組成物(例えば、実施例に記載の組成物)をPGMEA(propyleneglycol monomethyl ether acetate)で希釈(例えば、実施例に記載の組成物であれば100倍)したのち、カーボン箔上に滴下し、乾燥させたもの。
上記試料を、透過型電子顕微鏡を用いて倍率2万倍で観察して像を得る。得られた像のなかのチタン窒化物含有粒子の面積を画像処理により算出する。次に、得られた面積を円に換算した場合の直径を算出し、粒子400個について評価した円換算の直径を算術平均して求める。 The average primary particle size of the titanium nitride-containing particles is not particularly limited, but is generally preferably 1 to 200 nm and more preferably 10 to 50 nm. In addition, in this specification, the average primary particle size intends the average primary particle size of particles measured by the following method. The average primary particle size can be measured using a transmission electron microscope (TEM). As the transmission electron microscope, for example, a transmission microscope HT7700 manufactured by Hitachi High-Technologies Corporation can be used.
Sample: The composition (for example, the composition described in the example) was diluted with PGMEA (propyleneglycol ether etherate) (for example, 100 times in the case of the composition described in the example) and then dropped on the carbon foil. , Dried.
An image is obtained by observing the sample at a magnification of 20,000 using a transmission electron microscope. The area of the titanium nitride-containing particles in the obtained image is calculated by image processing. Next, the diameter when the obtained area is converted into a circle is calculated, and the circle-converted diameter evaluated for 400 particles is obtained by arithmetic averaging.
チタン窒化物を被覆する方法としては、特に制限されず、公知の方法を用いることができ、例えば、特開昭53-33228号公報の2頁右下~4頁右上に記載された方法(チタン酸化物に代えて、チタン窒化物を用いる)、特開2008-69193の段落0015~0043段落に記載された方法(微粒子二酸化チタンに代えて、チタン窒化物を用いる)、特開2016-74870号公報の0020段落、及び、0124~0138段落に記載された方法(金属酸化物微粒子に代えて、チタン窒化物を用いる)が挙げられ、上記の内容は本明細書に組み込まれる。 The titanium nitride-containing particles may contain a layer of a compound containing silicon (hereinafter referred to as “silicon-containing compound”) on the surface thereof. That is, titanium nitride may be coated with a silicon-containing compound to form titanium nitride-containing particles.
The method for coating titanium nitride is not particularly limited, and a known method can be used. For example, the method described in JP-A-53-33228, page 2 lower right to page 4 upper right (titanium (Titanium nitride is used instead of oxide), the method described in paragraphs 0015 to 0043 of JP-A-2008-69193 (titanium nitride is used instead of fine-particle titanium dioxide), JP-A-2016-74870 Examples include the methods described in paragraphs 0020 and 0124 to 0138 of the publication (in which titanium nitride is used in place of metal oxide fine particles), and the above contents are incorporated herein.
チタン窒化物含有粒子としては、例えば、TiN、TiO2、TinO2n-1(1≦n≦20)で表せる低次酸化チタン;TiNxOy(0<x<2.0,0.01<y<2.0)で表せる酸窒化チタン;TiNで表される窒化チタン;等を含有する粒子が挙げられる。
なお、チタン窒化物含有粒子中におけるチタン原子の含有量に対する、窒素原子の含有量の比X(窒素原子の含有原子数比X)としては特に制限されないが、下限値としては、0を超え、0.4を超えることが好ましい。上限値としては、2以下が好ましく、1未満がより好ましく、0.95未満が更に好ましい。
比X(以下、単に「X」ともいう。)が、0を超え、1未満であると、組成物は、より優れた経時安定性を有する。また、Xが、0.40を超えると、組成物は更に優れた経時安定性を有し、Xが0.95未満であると、組成物は、更に優れたパターニング性を有する。
また、組成物がより優れた本発明の効果を有する点で、Xは0.64以下がより好ましく、0.62以下が更に好ましく、0.57以下が特に好ましい。
また、組成物がより優れた本発明の効果を有する点で、Xは0.44以上が好ましく、0.45以上がより好ましい。
なお、チタン窒化物含有粒子中におけるチタン原子の含有量は、組成物中のチタン窒化物含有粒子を分離し、分離したチタン窒化物含有粒子について、ICP(Inductively Coupled Plasma)発光分光分析法を用いて測定でき、チタン窒化物含有粒子中における酸素原子、及び、窒素原子の含有量は、不活性ガス融解-熱伝導度法を用いて測定できる。なお、組成物中のチタン窒化物含有粒子を分離する方法としては既に説明したとおりである。
なお、本明細書において、Xを「N/Ti」と表すことがある。 The titanium nitride-containing particles contain titanium nitride. The titanium nitride-containing particles contain titanium atoms (Ti) and nitrogen atoms (N).
Examples of the titanium nitride-containing particles include low-order titanium oxide represented by TiN, TiO 2 , and Ti n O 2n-1 (1 ≦ n ≦ 20); TiN x O y (0 <x <2.0, 0. And particles containing titanium oxynitride represented by 01 <y <2.0); titanium nitride represented by TiN; and the like.
In addition, the ratio X of the nitrogen atom content to the titanium atom content in the titanium nitride-containing particles is not particularly limited, but the lower limit value exceeds 0. It is preferable to exceed 0.4. The upper limit is preferably 2 or less, more preferably less than 1, and still more preferably less than 0.95.
When the ratio X (hereinafter also simply referred to as “X”) is greater than 0 and less than 1, the composition has better stability over time. Moreover, when X exceeds 0.40, the composition has further excellent temporal stability, and when X is less than 0.95, the composition has further excellent patternability.
Further, X is more preferably 0.64 or less, further preferably 0.62 or less, and particularly preferably 0.57 or less in that the composition has the more excellent effects of the present invention.
Further, X is preferably 0.44 or more, more preferably 0.45 or more, in that the composition has the more excellent effects of the present invention.
The content of titanium atoms in the titanium nitride-containing particles is determined by separating the titanium nitride-containing particles in the composition and using ICP (Inductively Coupled Plasma) emission spectroscopy for the separated titanium nitride-containing particles. The content of oxygen atoms and nitrogen atoms in the titanium nitride-containing particles can be measured using an inert gas melting-thermal conductivity method. The method for separating the titanium nitride-containing particles in the composition is as described above.
In the present specification, X may be expressed as “N / Ti”.
比Y(以下、単に「Y」ともいう。)が0.001~0.2であると、組成物はより優れた経時安定性を有する。
なお、本明細書において、Yを「O/Ti」と表すことがある。 The ratio Y of the oxygen atom content to the titanium atom content in the titanium nitride-containing particles (the oxygen atom content atom ratio Y) is not particularly limited, but is preferably 0 to 2, more preferably 0 to 1. .
When the ratio Y (hereinafter also simply referred to as “Y”) is 0.001 to 0.2, the composition has better stability over time.
In this specification, Y may be expressed as “O / Ti”.
式(4)X+Y<0.93
X+Yが上記範囲内であると、組成物を用いて形成された膜は、より優れた遮光性を有する。なお、X+Yの下限値としては特に制限されないが、一般に0.2超が好ましい。
なかでも、組成物がより優れた本発明の効果を有する点で、X+Yとしては、0.85以下がより好ましく、0.70以下が更に好ましい。また、X+Yとしては、0.40超がより好ましい。 Especially in the titanium nitride-containing particles, the sum ((N + O) / Ti) of the ratio X of the nitrogen atom content to the titanium atom content and the ratio Y of the oxygen atom content to the titanium atom content Y Although not limited, generally 1.5 or less is preferable. Especially, it is preferable that X + Y satisfies the following formula (4).
Formula (4) X + Y <0.93
When X + Y is within the above range, a film formed using the composition has more excellent light shielding properties. In addition, although it does not restrict | limit especially as a lower limit of X + Y, Generally more than 0.2 is preferable.
Of these, X + Y is more preferably 0.85 or less, and even more preferably 0.70 or less, in that the composition has more excellent effects of the present invention. X + Y is more preferably more than 0.40.
なお、チタン窒化物含有粒子中における塩素原子の含有量は、以下の方法により測定した塩素原子の含有量を意図する。
チタン窒化物含有粒子を助剤とともに1000℃で燃焼し、発生させた塩素ガスを吸収液に捕集し、イオンクロマトグラフィー装置を用いて分析する。なお、組成物中からチタン窒化物含有粒子を分離する方法としては、既に説明したとおりである。 The titanium nitride-containing particles preferably contain chlorine atoms. The content of chlorine atoms contained in the titanium nitride-containing particles is not particularly limited, but is generally preferably 300 to 5000 ppm by mass, more preferably 800 to 3000 ppm by mass with respect to the total mass of the titanium nitride-containing particles. Preferably, 1200 to 3000 ppm by mass is more preferable, and 1500 to 2700 ppm by mass is particularly preferable. When the content of chlorine atoms in the titanium nitride-containing particles is 800 to 3000 ppm by mass, the cured film obtained from the composition has more excellent electrical characteristics.
In addition, content of the chlorine atom in titanium nitride containing particle | grains intends content of the chlorine atom measured with the following method.
Titanium nitride-containing particles are burned with an auxiliary agent at 1000 ° C., and the generated chlorine gas is collected in an absorbing solution and analyzed using an ion chromatography apparatus. The method for separating titanium nitride-containing particles from the composition is as described above.
チタン窒化物含有粒子が、酸化チタンTiO2を含有する場合、最も強度の強いピークとしてアナターゼ型TiO2(101)に由来するピークが2θ=25.3°近傍に、ルチル型TiO2(110)に由来するピークが2θ=27.4°近傍に見られる。しかし、TiO2は白色であり、組成物を硬化して得られる硬化膜の遮光性を低下させる要因となるため、ピークとして観察されない程度に低減されていることが好ましい。 The diffraction angle 2θ of the peak derived from the (200) plane of the titanium nitride-containing particles is preferably 42.5 ° or more and 43.5 ° or less, more preferably 42.5 ° or more and 42.8 or less, and 42 More preferably, it is 5 ° or more and 42.7 ° or less.
When the titanium nitride-containing particles contain titanium oxide TiO 2 , the peak derived from anatase TiO 2 (101) as the strongest peak is in the vicinity of 2θ = 25.3 °, and the rutile TiO 2 (110). The peak derived from is seen in the vicinity of 2θ = 27.4 °. However, since TiO 2 is white and causes a reduction in the light-shielding property of a cured film obtained by curing the composition, it is preferably reduced to a level that is not observed as a peak.
本明細書において、複合化とは、チタン窒化物と金属微粒子が複合化しているか、高度に分散した状態にある粒子のことをいう。ここで、「複合化している」とは、チタン窒化物と他の金属の両成分によって粒子が構成されていることを意味し、「高度に分散した状態」とは、チタン窒化物と他の金属がそれぞれ個別で存在し、他の金属の粒子が凝集せず均一、一様に分散していることを意味する。
金属微粒子の材料としては特に限定されず、例えば、銅、銀、金、白金、パラジウム、ニッケル、錫、コバルト、ロジウム、イリジウム、ルテニウム、オスミウム、マンガン、モリブデン、タングステン、ニオブ、タンタル、カルシウム、チタン、ビスマス、アンチモン及び鉛、並びにこれらの合金、から選ばれる少なくとも一種が挙げられる。なかでも、銅、銀、金、白金、パラジウム、ニッケル、錫、コバルト、ロジウム及びイリジウム、並びにこれらの合金から選ばれる少なくとも1種であることが好ましく、銅、銀、金、白金及び錫、並びにこれらの合金から選ばれる少なくとも一種であることがより好ましい。耐湿性により優れる観点から、銀であることが好ましい。
チタン窒化物含有粒子における上記金属微粒子の含有量としては、チタン窒化物含有粒子の全質量に対して5質量%以上50質量%以下であることが好ましく、10質量%以上30質量%以下であることがより好ましい。 The titanium nitride-containing particles may be combined with other metal fine particles.
In this specification, “composite” refers to particles in which titanium nitride and metal fine particles are complexed or in a highly dispersed state. Here, “composite” means that the particles are composed of both components of titanium nitride and other metals, and “highly dispersed” means that titanium nitride and other metals This means that the metals are present individually and the other metal particles are not aggregated but are uniformly and uniformly dispersed.
The material of the metal fine particles is not particularly limited, and for example, copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantalum, calcium, titanium , Bismuth, antimony and lead, and alloys thereof. Especially, it is preferable that it is at least 1 sort (s) chosen from copper, silver, gold | metal | money, platinum, palladium, nickel, tin, cobalt, rhodium and iridium, and these alloys, copper, silver, gold | metal | money, platinum and tin, and More preferably, it is at least one selected from these alloys. From the viewpoint of better moisture resistance, silver is preferred.
The content of the metal fine particles in the titanium nitride-containing particles is preferably 5% by mass to 50% by mass with respect to the total mass of the titanium nitride-containing particles, and is preferably 10% by mass to 30% by mass. It is more preferable.
チタン窒化物含有粒子の製造方法としては特に制限されず、公知の方法を用いることができる。チタン窒化物含有粒子の製造方法としては、例えば、気相反応法が挙げられる。気相反応法としては、電気炉法、及び、熱プラズマ法等が挙げられるが、不純物の混入が少なく、粒子径が揃いやすく、また、生産性が高い点で、熱プラズマ法が好ましい。
熱プラズマ法において、熱プラズマを発生させる方法としては、特に制限されず、直流アーク放電、多層アーク放電、高周波(RF)プラズマ、及び、ハイブリッドプラズマ等が挙げられ、電極からの不純物の混入が少ない高周波プラズマが好ましい。
熱プラズマ法によるチタン窒化物含有粒子の具体的な製造方法としては、特に制限されないが、例えば、チタン窒化物の製造方法として、プラズマ炎中で四塩化チタンとアンモニアガスを反応させる方法(特開平2-22110号公報)、チタン粉末を高周波熱プラズマにより蒸発させ窒素をキャリアーガスとして導入し冷却過程にて窒化させ合成する方法(特開昭61-11140号公報)、及び、プラズマの周縁部にアンモニアガスを吹き込む方法(特開昭63-85007号)等が挙げられる。
ただし、チタン窒化物含有粒子の製造方法としては、上記に制限されるものではなく、所望とする物性を有するチタン窒化物含有粒子が得られれば、製造方法は制限されない。
また、熱プラズマ法により、チタン窒化物含有粒子を製造する際、その原料が液体である場合には、プラズマ炎中に所望の流量で原料のガスを導入するため、適宜原料を加熱又は冷却してもよい。 (Method for producing titanium nitride-containing particles)
The method for producing titanium nitride-containing particles is not particularly limited, and a known method can be used. Examples of the method for producing titanium nitride-containing particles include a gas phase reaction method. Examples of the gas phase reaction method include an electric furnace method, a thermal plasma method, and the like. The thermal plasma method is preferable in that impurities are less mixed, the particle diameter is easily uniformed, and productivity is high.
In the thermal plasma method, a method for generating thermal plasma is not particularly limited, and includes direct current arc discharge, multilayer arc discharge, radio frequency (RF) plasma, hybrid plasma, and the like, and there is little mixing of impurities from the electrodes. High frequency plasma is preferred.
A specific method for producing titanium nitride-containing particles by the thermal plasma method is not particularly limited. For example, as a method for producing titanium nitride, titanium tetrachloride and ammonia gas are reacted in a plasma flame (Japanese Patent Application Laid-Open No. Hei. 2-22110), a method in which titanium powder is evaporated by high-frequency thermal plasma, nitrogen is introduced as a carrier gas, and is nitrided and synthesized in the cooling process (Japanese Patent Laid-Open No. 61-11140). Examples include a method of blowing ammonia gas (Japanese Patent Laid-Open No. 63-85007).
However, the method for producing titanium nitride-containing particles is not limited to the above, and the production method is not limited as long as titanium nitride-containing particles having desired physical properties are obtained.
In addition, when producing titanium nitride-containing particles by the thermal plasma method, if the raw material is liquid, the raw material gas is introduced at a desired flow rate into the plasma flame, and thus the raw material is appropriately heated or cooled. May be.
チタン窒化物含有粒子の製造方法は、上記の製造方法で作製したチタンの窒化物を含有する粒子を、加熱して、不純物を揮発させ、除去する工程(加熱工程)を更に含有することが好ましい。
上記加熱工程を経て作製されたチタン窒化物含有粒子は、チタン窒化物含有粒子中における不純物、特に、揮発性の不純物の含有量が低下しやすい。
加熱工程を経て作製されたチタン窒化物含有粒子は、400~1200nmにおける複素誘電率の実数部ε’の最小値が0未満になりやすい。
一方、上記加熱工程を経ずに作製されたチタン窒化物含有粒子は、400~1200nmにおける複素誘電率の実数部の最小値が0以上になりやすい(例えば、後述する、チタン窒化物含有粒子TiN-Cに該当する)。
上記加熱工程における加熱温度としては特に制限されず、一般に150~500℃が好ましい。加熱時間としては特に制限されず、一般に1時間~3日が好ましい。加熱中の雰囲気としては特に制限されないが、酸素が200ppm未満の窒素雰囲気等が好ましい。また、加熱中に減圧してもよい。 (Heating process)
The method for producing titanium nitride-containing particles preferably further includes a step of heating and volatilizing and removing impurities (heating step) by heating the particles containing titanium nitride produced by the above production method. .
In the titanium nitride-containing particles produced through the heating step, the content of impurities, particularly volatile impurities, in the titanium nitride-containing particles tends to decrease.
In the titanium nitride-containing particles produced through the heating step, the minimum value of the real part ε ′ of the complex dielectric constant at 400 to 1200 nm tends to be less than zero.
On the other hand, in the titanium nitride-containing particles produced without the above heating step, the minimum value of the real part of the complex dielectric constant at 400 to 1200 nm tends to be 0 or more (for example, titanium nitride-containing particles TiN described later) -C))
The heating temperature in the heating step is not particularly limited and is generally preferably 150 to 500 ° C. The heating time is not particularly limited, and generally 1 hour to 3 days is preferable. The atmosphere during heating is not particularly limited, but a nitrogen atmosphere or the like in which oxygen is less than 200 ppm is preferable. Further, the pressure may be reduced during heating.
上記組成物は樹脂を含有する。樹脂としては特に制限されないが、分散剤、及び、アルカリ可溶性樹脂等が挙げられる。
組成物中における樹脂の含有量としては特に制限されないが、一般に組成物の全固形分に対して0.5~30質量%が好ましい。 〔resin〕
The composition contains a resin. Although it does not restrict | limit especially as resin, A dispersing agent, alkali-soluble resin, etc. are mentioned.
The content of the resin in the composition is not particularly limited, but is generally preferably 0.5 to 30% by mass with respect to the total solid content of the composition.
上記組成物は分散剤(樹脂に該当する)を含有することが好ましい。なお、本明細書において、分散剤とは、後述するアルカリ可溶性樹脂とは異なる化合物を意図する。
組成物中における分散剤の含有量としては特に制限されないが、一般に組成物の全固形分に対して8~20質量%が好ましい。
分散剤は、1種を単独で用いても、2種以上を併用してもよい。2種以上の分散剤を併用する場合には、合計含有量が上記範囲内であることが好ましい。 <Dispersant>
The composition preferably contains a dispersant (corresponding to a resin). In addition, in this specification, a dispersing agent intends the compound different from the alkali-soluble resin mentioned later.
The content of the dispersant in the composition is not particularly limited, but is generally preferably 8 to 20% by mass with respect to the total solid content of the composition.
A dispersing agent may be used individually by 1 type, or may use 2 or more types together. When two or more dispersants are used in combination, the total content is preferably within the above range.
分散剤としては、高分子分散剤〔例えば、ポリアミドアミンとその塩、ポリカルボン酸とその塩、高分子量不飽和酸エステル、変性ポリウレタン、変性ポリエステル、変性ポリ(メタ)アクリレート、(メタ)アクリル系共重合体、ナフタレンスルホン酸ホルマリン縮合物〕、ポリオキシエチレンアルキルリン酸エステル、ポリオキシエチレンアルキルアミン、及び、顔料誘導体等を挙げることができる。
高分子化合物は、その構造から更に直鎖状高分子、末端変性型高分子、グラフト型高分子、及びブロック型高分子に分類することができる。 As the dispersant, for example, a known dispersant can be appropriately selected and used. Of these, polymer compounds are preferable.
Examples of the dispersant include polymer dispersants [for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic type Copolymer, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, and pigment derivatives.
The polymer compounds can be further classified into linear polymers, terminal-modified polymers, graft polymers, and block polymers based on their structures.
高分子化合物は、チタン窒化物含有粒子(以下、「顔料」ということがある。)の表面に吸着し、被分散体の再凝集を防止するように作用する。そのため、顔料表面へのアンカー部位を含有する、末端変性型高分子、グラフト型高分子、及び、ブロック型高分子が好ましい。 (Polymer compound)
The polymer compound is adsorbed on the surface of titanium nitride-containing particles (hereinafter sometimes referred to as “pigment”) and acts to prevent re-aggregation of the dispersion. Therefore, a terminal-modified polymer, a graft polymer, and a block polymer containing an anchor site to the pigment surface are preferable.
このようなグラフト鎖を含有する構造単位を含有する高分子化合物は、グラフト鎖によって溶剤との親和性を有するために、チタン窒化物含有粒子等の分散性、及び、経時後の分散安定性(経時安定性)に優れるものである。また、グラフト鎖の存在により、グラフト鎖を含有する構造単位を含有する高分子化合物は重合性化合物又はその他の併用可能な樹脂等との親和性を有する。結果として、アルカリ現像で残渣を生じにくくなる。
グラフト鎖が長くなると立体反発効果が高くなりチタン窒化物含有粒子等の分散性は向上する。一方、グラフト鎖が長すぎるとチタン窒化物含有粒子等への吸着力が低下して、チタン窒化物含有粒子等の分散性は低下する傾向となる。このため、グラフト鎖は、水素原子を除いた原子数が40~10000であるものが好ましく、水素原子を除いた原子数が50~2000であるものがより好ましく、水素原子を除いた原子数が60~500であるものが更に好ましい。
ここで、グラフト鎖とは、共重合体の主鎖の根元(主鎖から枝分かれしている基において主鎖に結合する原子)から、主鎖から枝分かれしている基の末端までを示す。 The polymer compound preferably contains a structural unit containing a graft chain. In the present specification, “structural unit” is synonymous with “repeating unit”.
Since the polymer compound containing a structural unit containing such a graft chain has an affinity for a solvent by the graft chain, the dispersibility of titanium nitride-containing particles and the like, and the dispersion stability after aging ( It has excellent stability over time. Further, due to the presence of the graft chain, the polymer compound containing the structural unit containing the graft chain has an affinity with a polymerizable compound or other resin that can be used in combination. As a result, it becomes difficult to produce a residue by alkali development.
When the graft chain becomes longer, the steric repulsion effect becomes higher and the dispersibility of the titanium nitride-containing particles and the like is improved. On the other hand, if the graft chain is too long, the adsorptive power to the titanium nitride-containing particles and the like is lowered, and the dispersibility of the titanium nitride-containing particles and the like tends to be lowered. For this reason, the graft chain preferably has 40 to 10,000 atoms excluding hydrogen atoms, more preferably 50 to 2000 atoms excluding hydrogen atoms, and the number of atoms excluding hydrogen atoms. More preferred is 60-500.
Here, the graft chain means from the base of the main chain of the copolymer (the atom bonded to the main chain in a group branched from the main chain) to the end of the group branched from the main chain.
グラフト鎖と溶剤との相互作用性を向上させ、それによりチタン窒化物含有粒子等の分散性を高めるために、グラフト鎖は、ポリエステル構造、ポリエーテル構造及びポリ(メタ)アクリレート構造からなる群から選ばれた少なくとも1種を含有するグラフト鎖であることが好ましく、ポリエステル構造及びポリエーテル構造の少なくともいずれかを含有するグラフト鎖であることがより好ましい。 The graft chain preferably contains a polymer structure. Examples of such a polymer structure include a poly (meth) acrylate structure (for example, a poly (meth) acrylic structure), a polyester structure, a polyurethane structure, a polyurea structure, and a polyamide. Examples thereof include a structure and a polyether structure.
In order to improve the interaction between the graft chain and the solvent and thereby increase the dispersibility of the titanium nitride-containing particles, the graft chain is from the group consisting of a polyester structure, a polyether structure and a poly (meth) acrylate structure. It is preferably a graft chain containing at least one selected, and more preferably a graft chain containing at least one of a polyester structure and a polyether structure.
ここで、ポリカプロラクトン構造とは、ε-カプロラクトンを開環した構造を繰り返し単位として含有するものをいう。ポリバレロラクトン構造とは、δ-バレロラクトンを開環した構造を繰り返し単位として含有するものをいう。
ポリカプロラクトン構造を含有する分散剤の具体例としては、下記式(1)及び下記式(2)におけるj及びkが5であるものが挙げられる。また、ポリバレロラクトン構造を含有する分散剤の具体例としては、下記式(1)及び下記式(2)におけるj及びkが4であるものが挙げられる。
ポリアクリル酸メチル構造を含有する分散剤の具体例としては、下記式(4)におけるX5が水素原子であり、R4がメチル基であるものが挙げられる。また、ポリメタクリル酸メチル構造を含有する分散剤の具体例としては、下記式(4)におけるX5がメチル基であり、R4がメチル基であるものが挙げられる。 The dispersant preferably contains at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and cyclic or chain polyester. More preferably, the dispersant contains at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and chain polyester. More preferably, the dispersant contains at least one structure selected from the group consisting of a polymethyl acrylate structure, a polymethyl methacrylate structure, a polycaprolactone structure, and a polyvalerolactone structure. The dispersing agent may contain the above structure alone in one dispersing agent, or may contain a plurality of these structures in one dispersing agent.
Here, the polycaprolactone structure means a structure containing a ring-opened structure of ε-caprolactone as a repeating unit. The polyvalerolactone structure means a structure containing a ring-opened structure of δ-valerolactone as a repeating unit.
Specific examples of the dispersant containing a polycaprolactone structure include those in which j and k are 5 in the following formula (1) and the following formula (2). Specific examples of the dispersant containing a polyvalerolactone structure include those in which j and k in the following formula (1) and the following formula (2) are 4.
Specific examples of the dispersant containing a polymethyl acrylate structure include those in which X 5 in the following formula (4) is a hydrogen atom and R 4 is a methyl group. Further, specific examples of the dispersant containing a polymethyl methacrylate structure include those in which X 5 in the following formula (4) is a methyl group and R 4 is a methyl group.
高分子化合物は、グラフト鎖を含有する構造単位として、下記式(1)~式(4)のいずれかで表される構造単位を含有することが好ましく、下記式(1A)、下記式(2A)、下記式(3A)、下記式(3B)、及び下記(4)のいずれかで表される構造単位を含有することがより好ましい。 Structural unit containing a graft chain The polymer compound preferably contains a structural unit represented by any one of the following formulas (1) to (4) as a structural unit containing a graft chain. It is more preferable to contain a structural unit represented by any one of (1A), the following formula (2A), the following formula (3A), the following formula (3B), and the following (4).
式(1)~式(4)において、X1、X2、X3、X4、及びX5は、それぞれ独立に、水素原子又は1価の有機基を表す。X1、X2、X3、X4、及びX5としては、合成上の制約の観点からは、それぞれ独立に、水素原子又は炭素数(炭素原子数)1~12のアルキル基であることが好ましく、それぞれ独立に、水素原子又はメチル基であることがより好ましく、メチル基が更に好ましい。 In the formulas (1) to (4), W 1 , W 2 , W 3 , and W 4 each independently represent an oxygen atom or NH. W 1 , W 2 , W 3 , and W 4 are preferably oxygen atoms.
In the formulas (1) to (4), X 1 , X 2 , X 3 , X 4 , and X 5 each independently represent a hydrogen atom or a monovalent organic group. X 1 , X 2 , X 3 , X 4 , and X 5 are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms (the number of carbon atoms) from the viewpoint of synthesis constraints. Are preferably each independently a hydrogen atom or a methyl group, more preferably a methyl group.
また、式(1)及び式(2)において、j及びkは、それぞれ独立に、2~8の整数を表す。式(1)及び式(2)におけるj及びkは、組成物の経時安定性及び現像性の観点から、4~6の整数が好ましく、5がより好ましい。 In the formulas (1) to (4), n, m, p, and q are each independently an integer of 1 to 500.
In the formulas (1) and (2), j and k each independently represent an integer of 2 to 8. J and k in the formulas (1) and (2) are preferably integers of 4 to 6, and more preferably 5, from the viewpoint of the temporal stability and developability of the composition.
式(4)中、R4は水素原子又は1価の有機基を表し、この1価の有機基としては特に構造上限定はされない。R4として好ましくは、水素原子、アルキル基、アリール基、又は、ヘテロアリール基が挙げられ、より好ましくは、水素原子、又はアルキル基である。R4がアルキル基である場合、アルキル基としては、炭素数1~20の直鎖状アルキル基、炭素数3~20の分岐鎖状アルキル基、又は炭素数5~20の環状アルキル基が好ましく、炭素数1~20の直鎖状アルキル基がより好ましく、炭素数1~6の直鎖状アルキル基が更に好ましい。式(4)において、qが2~500のとき、グラフト共重合体中に複数存在するX5及びR4は互いに同じであっても異なっていてもよい。 In the formula (3), R 3 represents a branched or straight chain alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, a plurality of R 3 may be the same or different from each other.
In the formula (4), R 4 represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited in terms of structure. R 4 is preferably a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and more preferably a hydrogen atom or an alkyl group. When R 4 is an alkyl group, the alkyl group is preferably a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms. A linear alkyl group having 1 to 20 carbon atoms is more preferable, and a linear alkyl group having 1 to 6 carbon atoms is still more preferable. In the formula (4), when q is 2 to 500, a plurality of X 5 and R 4 present in the graft copolymer may be the same or different from each other.
また、式(2)で表される構造単位としては、組成物の経時安定性及び現像性の観点から、下記式(2A)で表される構造単位であることがより好ましい。 The structural unit represented by the formula (1) is more preferably a structural unit represented by the following formula (1A) from the viewpoint of temporal stability and developability of the composition.
Moreover, as a structural unit represented by Formula (2), it is more preferable that it is a structural unit represented by following formula (2A) from a viewpoint of temporal stability of a composition and developability.
また、高分子化合物は、グラフト鎖を含有する構造単位とは異なる(すなわち、グラフト鎖を含有する構造単位には相当しない)疎水性構造単位を含有することが好ましい。ただし、本明細書において、疎水性構造単位は、酸基(例えば、カルボン酸基、スルホン酸基、リン酸基、フェノール性水酸基等)を有さない構造単位である。 -Hydrophobic structural unit Moreover, it is preferable that a high molecular compound contains the hydrophobic structural unit different from the structural unit containing a graft chain (namely, it does not correspond to the structural unit containing a graft chain). However, in this specification, a hydrophobic structural unit is a structural unit which does not have an acid group (for example, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group, etc.).
A. J. Leo, Comprehensive Medicinal Chemistry, Vol.4, C. Hansch, P. G. Sammnens, J. B. Taylor and C. A. Ramsden, Eds., p.295, Pergamon Press, 1990 C. Hansch & A. J. Leo. SUbstituent Constants For Correlation Analysis in Chemistry and Biology. John Wiley & Sons. A.J. Leo. Calculating logPoct from structure. Chem. Rev., 93, 1281-1306, 1993. ClogP values are available from Daylight Chemical Information System, Inc. It is a value calculated by the program “CLOGP” available from This program provides the value of “computation logP” calculated by Hansch, Leo's fragment approach (see below). The fragment approach is based on the chemical structure of a compound, which divides the chemical structure into substructures (fragments) and estimates the logP value of the compound by summing the logP contributions assigned to that fragment. Details thereof are described in the following documents. In the present invention, the ClogP value calculated by the program CLOGP v4.82 is used.
A. J. et al. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C.I. Hansch, P.A. G. Sammunens, J. et al. B. Taylor and C.M. A. Ramsden, Eds. , P. 295, Pergamon Press, 1990 C.I. Hansch & A. J. et al. Leo. Substituent Constants For Correlation Analysis in Chemistry and Biology. John Wiley & Sons. A. J. et al. Leo. Calculating logPoch from structure. Chem. Rev. , 93, 1281-1306, 1993.
logP=log(Coil/Cwater)
式中、Coilは油相中の化合物のモル濃度を、Cwaterは水相中の化合物のモル濃度を表す。
logPの値が0をはさんでプラスに大きくなると油溶性が増し、マイナスで絶対値が大きくなると水溶性が増すことを意味し、有機化合物の水溶性と負の相関があり、有機化合物の親疎水性を見積るパラメータとして広く利用されている。 log P means the common logarithm of the partition coefficient P (Partition Coefficient), and quantitatively determines how an organic compound is distributed in the equilibrium of a two-phase system of oil (generally 1-octanol) and water. It is a physical property value expressed as a numerical value, and is represented by the following formula.
logP = log (Coil / Cwater)
In the formula, Coil represents the molar concentration of the compound in the oil phase, and Cwater represents the molar concentration of the compound in the aqueous phase.
When the logP value increases to a positive value across 0, the oil solubility increases. When the logP value increases to a negative value, the water solubility increases. There is a negative correlation with the water solubility of the organic compound. It is widely used as a parameter for estimating aqueous properties.
R1、R2、及びR3は、好ましくは水素原子、又は炭素数が1~3のアルキル基であり、より好ましくは水素原子又はメチル基である。R2及びR3は、水素原子であることが更に好ましい。
Xは、酸素原子(-O-)又はイミノ基(-NH-)を表し、酸素原子であることが好ましい。 In the above formulas (i) to (iii), R 1 , R 2 , and R 3 each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number of 1 Represents an alkyl group of ˜6 (for example, methyl group, ethyl group, propyl group, etc.).
R 1 , R 2 , and R 3 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group. R 2 and R 3 are more preferably a hydrogen atom.
X represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
脂肪族基は不飽和脂肪族基よりも飽和脂肪族基の方が好ましい。また、脂肪族基は、置換基を有していてもよい。置換基の例は、ハロゲン原子、芳香族基及び複素環基が挙げられる。ただし、脂肪族基は、置換基として酸基を有さない。 The aliphatic group may have a cyclic structure or a branched structure. The aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms. The aliphatic group further includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group. Examples of the ring assembly hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group, and 4 -A cyclohexylphenyl group and the like are included. Examples of the bridged cyclic hydrocarbon ring include 2 such as pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.). Tricyclic hydrocarbon rings such as cyclic hydrocarbon rings, homobredan, adamantane, tricyclo [5.2.1.0 2,6 ] decane, and tricyclo [4.3.1.1 2,5 ] undecane rings , And tetracyclo [4.4.0.1 2,5 . 1 7, 10 ] dodecane, and tetracyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene ring. The bridged cyclic hydrocarbon ring includes a condensed cyclic hydrocarbon ring, such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and A condensed ring in which a plurality of 5- to 8-membered cycloalkane rings are condensed, such as a perhydrophenalene ring, is also included.
The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. Further, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group. However, the aliphatic group does not have an acid group as a substituent.
また、上記式(ii)で表される単量体として、R1が水素原子又はメチル基であって、Lがアルキレン基であって、Zが脂肪族基、複素環基又は芳香族基である化合物が好ましい。また、上記式(iii)で表される単量体として、R4、R5、及びR6が水素原子又はメチル基であって、Zが脂肪族基、複素環基又は芳香族基である化合物が好ましい。 As the monomer represented by the above formula (i), R 1 , R 2 , and R 3 are a hydrogen atom or a methyl group, and L is a single bond, an alkylene group, or a divalent oxyalkylene structure. A compound in which X is an oxygen atom or imino group and Z is an aliphatic group, a heterocyclic group or an aromatic group is preferable.
Further, as the monomer represented by the above formula (ii), R 1 is a hydrogen atom or a methyl group, L is an alkylene group, Z is an aliphatic group, a heterocyclic group or an aromatic group. Certain compounds are preferred. Further, as the monomer represented by the above formula (iii), R 4 , R 5 , and R 6 are a hydrogen atom or a methyl group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group. Compounds are preferred.
なお、式(i)~(iii)で表される代表的な化合物の例としては、特開2013-249417号公報の段落0089~0093に記載の化合物を参照でき、これらの内容は本明細書に組み込まれる。 Examples of typical compounds represented by formulas (i) to (iii) include radically polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, styrenes, and the like.
As examples of typical compounds represented by formulas (i) to (iii), compounds described in paragraphs 0089 to 0093 of JP2013-249417A can be referred to, and the contents thereof are described in the present specification. Incorporated into.
高分子化合物は、チタン窒化物含有粒子等と相互作用を形成しうる官能基を導入することができる。ここで、高分子化合物は、チタン窒化物含有粒子等と相互作用を形成しうる官能基を含有する構造単位を更に含有することが好ましい。
このチタン窒化物含有粒子等と相互作用を形成しうる官能基としては、例えば、酸基、塩基性基、配位性基、及び、反応性を有する官能基等が挙げられる。
高分子化合物が、酸基、塩基性基、配位性基、又は、反応性を有する官能基を含有する場合、それぞれ、酸基を含有する構造単位、塩基性基を含有する構造単位、配位性基を含有する構造単位、又は、反応性を有する構造単位を含有することが好ましい。
特に、高分子化合物が、更に、酸基として、カルボン酸基等のアルカリ可溶性基を含有することで、高分子化合物に、アルカリ現像によるパターン形成のための現像性を付与することができる。
すなわち、高分子化合物にアルカリ可溶性基を導入することで、上記組成物は、チタン窒化物含有粒子等の分散に寄与する分散剤としての高分子化合物がアルカリ可溶性を含有することになる。このような高分子化合物を含有する組成物は、露光部の遮光性に優れたものとなり、且つ、未露光部のアルカリ現像性が向上される。
また、高分子化合物が酸基を含有する構造単位を含有することにより、高分子化合物が溶剤となじみやすくなり、塗布性も向上する傾向となる。
これは、酸基を含有する構造単位における酸基がチタン窒化物含有粒子等と相互作用しやすく、高分子化合物がチタン窒化物含有粒子等を安定的に分散すると共に、チタン窒化物含有粒子等を分散する高分子化合物の粘度が低くなっており、高分子化合物自体も安定的に分散されやすいためであると推測される。 -Functional group capable of forming interaction with titanium nitride-containing particles, etc. The polymer compound can introduce a functional group capable of forming interaction with titanium nitride-containing particles. Here, the polymer compound preferably further contains a structural unit containing a functional group capable of forming an interaction with titanium nitride-containing particles.
Examples of the functional group capable of forming an interaction with the titanium nitride-containing particles include an acid group, a basic group, a coordinating group, and a reactive functional group.
When the polymer compound contains an acid group, a basic group, a coordination group, or a reactive functional group, the structural unit containing an acid group, the structural unit containing a basic group, and a coordination group, respectively. It is preferable to contain a structural unit containing a coordinate group or a structural unit having reactivity.
In particular, when the polymer compound further contains an alkali-soluble group such as a carboxylic acid group as the acid group, developability for pattern formation by alkali development can be imparted to the polymer compound.
That is, by introducing an alkali-soluble group into the polymer compound, the polymer compound as a dispersant that contributes to the dispersion of titanium nitride-containing particles or the like in the composition contains alkali-solubility. A composition containing such a polymer compound has excellent light-shielding properties in the exposed area, and the alkali developability in the unexposed area is improved.
Moreover, when a high molecular compound contains the structural unit containing an acid group, a high molecular compound becomes easy to become compatible with a solvent, and there exists a tendency for applicability | paintability to improve.
This is because the acid group in the structural unit containing an acid group easily interacts with the titanium nitride-containing particles and the like, and the polymer compound stably disperses the titanium nitride-containing particles and the like, and the titanium nitride-containing particles and the like It is presumed that the viscosity of the polymer compound in which the polymer is dispersed is low, and the polymer compound itself is easily dispersed stably.
すなわち、高分子化合物は、カルボン酸基、スルホン酸基、及び、リン酸基のうち少なくとも1種を含有する構造単位を更に含有することが好ましい。 Examples of the acid group that is a functional group capable of forming an interaction with titanium nitride-containing particles include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a phenolic hydroxyl group, and preferably a carboxylic acid Group, sulfonic acid group, and phosphoric acid group, and more preferable is a carboxylic acid group from the viewpoint of good adsorptive power to titanium nitride-containing particles and high dispersibility. It is.
That is, the polymer compound preferably further contains a structural unit containing at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.
高分子化合物は、酸基を含有する構造単位を含有してもしなくてもよいが、含有する場合、酸基を含有する構造単位の含有量は、質量換算で、高分子化合物の総質量に対して、好ましくは5~80%であり、より好ましくは、アルカリ現像による画像強度のダメージ抑制という観点から、10~60%である。 The polymer compound may have one or more structural units containing an acid group.
The polymer compound may or may not contain a structural unit containing an acid group. However, when it is contained, the content of the structural unit containing an acid group is calculated by mass conversion to the total mass of the polymer compound. On the other hand, it is preferably 5 to 80%, and more preferably 10 to 60% from the viewpoint of suppressing damage of image strength due to alkali development.
高分子化合物は、塩基性基を含有する構造単位を含有してもしなくてもよいが、含有する場合、塩基性基を含有する構造単位の含有量は、質量換算で、高分子化合物の総質量に対して、好ましくは0.01%以上50%以下であり、より好ましくは、現像性阻害抑制という観点から、0.01%以上30%以下である。 Examples of the basic group that is a functional group capable of forming an interaction with titanium nitride-containing particles include a primary amino group, a secondary amino group, a tertiary amino group, and a heterocyclic ring containing an N atom. And an amide group and the like, and a preferable one is a tertiary amino group in terms of good adsorbing power to titanium nitride-containing particles and high dispersibility. The polymer compound can contain one or more of these basic groups.
The polymer compound may or may not contain a structural unit containing a basic group, but when it is contained, the content of the structural unit containing a basic group is the total amount of the polymer compound in terms of mass. Preferably it is 0.01% or more and 50% or less with respect to mass, More preferably, it is 0.01% or more and 30% or less from a viewpoint of developability inhibition suppression.
高分子化合物は、配位性基を含有する構造単位、又は、反応性を有する官能基を含有する構造単位を含有してもしなくてもよいが、含有する場合、これらの構造単位の含有量は、質量換算で、高分子化合物の総質量に対して、好ましくは10%以上80%以下であり、より好ましくは、現像性阻害抑制という観点から、20%以上60%以下である。 Examples of the coordinating group that is a functional group capable of forming an interaction with titanium nitride-containing particles and the functional group having reactivity include, for example, an acetylacetoxy group, a trialkoxysilyl group, an isocyanate group, an acid anhydride, And acid chloride etc. are mentioned. Preferable one is an acetylacetoxy group in that the adsorbing power to titanium nitride-containing particles is good and the dispersibility of titanium nitride-containing particles is high. The polymer compound may have one or more of these groups.
The polymer compound may or may not contain a structural unit containing a coordinating group or a structural unit containing a reactive functional group, but if it contains, the content of these structural units Is preferably 10% or more and 80% or less, and more preferably 20% or more and 60% or less, in terms of mass, in terms of suppression of developability inhibition.
式(iv)~式(vi)中、R11、R12、及びR13は、好ましくは、それぞれ独立に水素原子、又は炭素数が1~3のアルキル基であり、より好ましくは、それぞれ独立に水素原子又はメチル基である。一般式(iv)中、R12及びR13は、それぞれ水素原子であることが特に好ましい。 In formulas (iv) to (vi), R 11 , R 12 , and R 13 each independently represent a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number of 1 Represents an alkyl group of ˜6 (for example, methyl group, ethyl group, propyl group, etc.).
In the formulas (iv) to (vi), R 11 , R 12 and R 13 are preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably each independently Are a hydrogen atom or a methyl group. In general formula (iv), R 12 and R 13 are each particularly preferably a hydrogen atom.
また、式(v)中のYは、メチン基又は窒素原子を表す。 X 1 in the formula (iv) represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
Y in the formula (v) represents a methine group or a nitrogen atom.
また、式(v)で表される単量体として、R11が水素原子又はメチル基であって、L1がアルキレン基であって、Z1がカルボン酸基であって、Yがメチン基である化合物が好ましい。
更に、式(vi)で表される単量体として、R14、R15、及びR16がそれぞれ独立に水素原子又はメチル基であって、L1が単結合又はアルキレン基であって、Z1がカルボン酸基である化合物が好ましい。 As the monomer represented by the formula (iv), R 11 , R 12 and R 13 are each independently a hydrogen atom or a methyl group, and L 1 is an alkylene group or a divalent oxyalkylene structure. A compound in which X 1 is an oxygen atom or imino group and Z 1 is a carboxylic acid group is preferable.
As the monomer represented by the formula (v), R 11 is a hydrogen atom or a methyl group, L 1 is an alkylene group, Z 1 is a carboxylic acid group, and Y is a methine group. Is preferred.
Furthermore, as a monomer represented by the formula (vi), R 14 , R 15 , and R 16 are each independently a hydrogen atom or a methyl group, L 1 is a single bond or an alkylene group, and Z A compound in which 1 is a carboxylic acid group is preferred.
単量体の例としては、メタクリル酸、クロトン酸、イソクロトン酸、分子内に付加重合性二重結合及び水酸基を含有する化合物(例えば、メタクリル酸2-ヒドロキシエチル)とコハク酸無水物との反応物、分子内に付加重合性二重結合及び水酸基を含有する化合物とフタル酸無水物との反応物、分子内に付加重合性二重結合及び水酸基を含有する化合物とテトラヒドロキシフタル酸無水物との反応物、分子内に付加重合性二重結合及び水酸基を含有する化合物と無水トリメリット酸との反応物、分子内に付加重合性二重結合及び水酸基を含有する化合物とピロメリット酸無水物との反応物、アクリル酸、アクリル酸ダイマー、アクリル酸オリゴマー、マレイン酸、イタコン酸、フマル酸、4-ビニル安息香酸、ビニルフェノール、及び、4-ヒドロキシフェニルメタクリルアミド等が挙げられる。 The following are typical examples of monomers (compounds) represented by the formulas (iv) to (vi).
Examples of monomers include methacrylic acid, crotonic acid, isocrotonic acid, a reaction containing a compound having an addition polymerizable double bond and a hydroxyl group in the molecule (for example, 2-hydroxyethyl methacrylate) and succinic anhydride. Product, a reaction product of a compound containing an addition polymerizable double bond and a hydroxyl group in the molecule with phthalic anhydride, a compound containing an addition polymerizable double bond and a hydroxyl group in the molecule and tetrahydroxyphthalic anhydride Reaction product, a reaction product of a compound containing an addition polymerizable double bond and hydroxyl group in the molecule and trimellitic anhydride, a compound containing an addition polymerizable double bond and hydroxyl group in the molecule and pyromellitic anhydride Reaction products with acrylic acid, acrylic acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid, vinylphenol, and 4 Hydroxyphenyl methacrylamide.
更に、高分子化合物は、画像強度等の諸性能を向上する目的で、本発明の効果を損なわない限りにおいて、グラフト鎖を含有する構造単位、疎水性構造単位、及び、チタン窒化物含有粒子等と相互作用を形成しうる官能基を含有する構造単位とは異なる、種々の機能を有する他の構造単位(例えば、分散物に用いられる溶剤との親和性を有する官能基等を含有する構造単位)を更に有していてもよい。
このような、他の構造単位としては、例えば、アクリロニトリル類、及び、メタクリロニトリル類等から選ばれるラジカル重合性化合物に由来の構造単位が挙げられる。
高分子化合物は、これらの他の構造単位を1種或いは2種以上用いることができ、その含有量は、質量換算で、高分子化合物の総質量に対して、好ましくは0%以上80%以下であり、特に好ましくは、10%以上60%以下である。含有量が上記範囲において、十分なパターン形成性が維持される。 Other structural units Furthermore, the polymer compound is a structural unit containing a graft chain, a hydrophobic structural unit, and titanium as long as the effects of the present invention are not impaired for the purpose of improving various properties such as image strength. Different from structural units containing functional groups that can interact with nitride-containing particles, etc., other structural units having various functions (for example, functional groups having affinity with the solvent used in the dispersion) May further have a structural unit containing
Examples of such other structural units include structural units derived from radically polymerizable compounds selected from acrylonitriles, methacrylonitriles, and the like.
The polymer compound may use one or more of these other structural units, and the content thereof is preferably 0% or more and 80% or less in terms of mass with respect to the total mass of the polymer compound. Especially preferably, it is 10% or more and 60% or less. When the content is in the above range, sufficient pattern formability is maintained.
高分子化合物の酸価は、0mgKOH/g以上250mgKOH/g以下の範囲であることが好ましく、より好ましくは10mgKOH/g以上200mgKOH/g以下の範囲であり、更に好ましくは20mgKOH/g以上120mgKOH/g以下の範囲である。
高分子化合物の酸価が160mgKOH/g以下であれば、硬化膜を形成する際の現像時におけるパターン剥離がより効果的に抑えられる。また、高分子化合物の酸価が10mgKOH/g以上であればアルカリ現像性がより良好となる。また、高分子化合物の酸価が20mgKOH/g以上であれば、チタン窒化物含有粒子等の沈降をより抑制でき、粗大粒子数をより少なくすることができ、組成物の経時安定性をより向上できる。 -Physical properties of polymer compound The acid value of the polymer compound is preferably in the range of 0 mgKOH / g to 250 mgKOH / g, more preferably in the range of 10 mgKOH / g to 200 mgKOH / g, and even more preferably 20 mgKOH. / G or more and 120 mgKOH / g or less.
When the acid value of the polymer compound is 160 mgKOH / g or less, pattern peeling during development when forming a cured film is more effectively suppressed. Moreover, if the acid value of a high molecular compound is 10 mgKOH / g or more, alkali developability will become more favorable. Moreover, if the acid value of the polymer compound is 20 mgKOH / g or more, precipitation of titanium nitride-containing particles and the like can be further suppressed, the number of coarse particles can be reduced, and the temporal stability of the composition is further improved. it can.
GPC法は、HLC-8020GPC(東ソー製)を用い、カラムとしてTSKgel SuperHZM-H、TSKgel SuperHZ4000、TSKgel SuperHZ2000(東ソー製、4.6mmID×15cm)を、溶離液としてTHF(テトラヒドロフラン)を用いる方法に基づく。
高分子化合物は、公知の方法に基づいて合成できる。 The weight average molecular weight of the polymer compound is 4 in terms of polystyrene conversion by GPC (Gel Permeation Chromatography) method from the viewpoint of pattern peeling inhibition during development and developability when forming a cured film. It is preferably 000 or more and 300,000 or less, more preferably 5,000 or more and 200,000 or less, further preferably 6,000 or more and 100,000 or less, and 10,000 or more and 50,000 or less. It is particularly preferred that
The GPC method is based on a method using HLC-8020GPC (manufactured by Tosoh), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh, 4.6 mm ID × 15 cm) as a column and THF (tetrahydrofuran) as an eluent. .
The polymer compound can be synthesized based on a known method.
また、両性樹脂の市販品としては、例えば、ビックケミー社製のDISPERBYK-130、DISPERBYK-140、DISPERBYK-142、DISPERBYK-145、DISPERBYK-180、DISPERBYK-187、DISPERBYK-191、DISPERBYK-2001、DISPERBYK-2010、DISPERBYK-2012、DISPERBYK-2025、BYK-9076、味の素ファインテクノ社製のアジスパーPB821、アジスパーPB822、及び、アジスパーPB881等が挙げられる。
これらの高分子化合物は、1種を単独で用いても、2種以上を併用してもよい。 Specific examples of the polymer compound include “DA-7301” manufactured by Enomoto Kasei Co., Ltd., “Disperbyk-101 (polyamidoamine phosphate)” manufactured by BYK Chemie, 107 (carboxylic acid ester), and 110 (copolymer containing acid group). ), 111 (phosphate dispersant), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170, 190 (polymer copolymer) ”,“ BYK-P104, P105 (non-high molecular weight) Saturated polycarboxylic acid) ”,“ EFKA 4047, 4050 to 4010 to 4165 (polyurethane) ”, EFKA 4330 to 4340 (block copolymer), 4400 to 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (polyester), manufactured by EFKA High molecular weight polycarboxylate), 6220 (fatty acid polyester) ), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative), “Ajisper PB821, PB822, PB880, PB881” manufactured by Ajinomoto Fine Techno Co., Ltd., “Floren TG-710 (urethane oligomer)” manufactured by Kyoeisha Chemical Co., Ltd., “Polyflow” No. 50E, No. 300 (acrylic copolymer) ”,“ Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyether ester), DA, manufactured by Enomoto Kasei Co., Ltd. -703-50, DA-705, DA-725 "," Demol RN, N (Naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) "manufactured by Kao Corporation "Homogenol L-18 (polymeric polycarboxylic acid)", "Emulgen 920" 930, 935, 985 (polyoxyethylene nonylphenyl ether) ”,“ acetamine 86 (stearylamine acetate) ”,“ Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), manufactured by Nippon Lubrizol, 3000, 12000, 17000, 20000, 27000 (polymers containing a functional part at the end), 24000, 28000, 32000, 38500 (graft copolymer) ”,“ Nikkor T106 (polyoxyethylene sorbitan mono) manufactured by Nikko Chemicals Oleart), MYS-IEX (polyoxyethylene monostearate), Kawano Fine Chemical's Hinoact T-8000E, Shin-Etsu Chemical Co., Ltd., organosiloxane polymer KP341, Yusho “W001: Cationic surfactant”, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distea Nonionic surfactants such as rate and sorbitan fatty acid esters, anionic surfactants such as “W004, W005, W017”, “EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer manufactured by Morishita Sangyo 400, EFKA Polymer 401, EFKA Polymer 450 ", Sannopco" Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Dispa Polymer dispersants such as “SEAIDE 9100”, manufactured by ADEKA “Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P -123 ", Sanyo Kasei" Ionet (trade name) S-20 ", and the like. Also, Acrybase FFS-6752, Acrybase FFS-187, Acrycure-RD-F8, and Cyclomer P can be used.
Commercially available amphoteric resins include, for example, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001, DISPERB manufactured by BYK Chemie. 2010, DISPERBYK-2012, DISPERBYK-2025, BYK-9976, Ajisper PB821, Azisper PB822, Azisper PB881, etc. manufactured by Ajinomoto Fine Techno Co., Ltd.
These polymer compounds may be used alone or in combination of two or more.
また、上記以外にも、特開2011-153283号公報の段落0028~0084(対応するUS2011/0279759の段落0075~0133欄)の酸性基が連結基を介して結合してなる側鎖構造を含有する構成成分を含有する高分子化合物が使用でき、これらの内容は援用でき、本明細書に組み込まれる。 As the dispersant, in addition to the above-described polymer compound, graft copolymers described in JP-A 2010-106268, paragraphs 0037 to 0115 (corresponding to columns 0075 to 0133 in US2011 / 0124824) can be used. Is incorporated herein by reference.
In addition to the above, it contains a side chain structure in which acidic groups in paragraphs 0028 to 0084 of JP 2011-153283 A (corresponding to paragraphs 0075 to 0133 of US2011 / 0279759) are bonded via a linking group. Polymer compounds containing the constituents to be used can be used, the contents of which can be incorporated and incorporated herein.
上記組成物は、アルカリ可溶性樹脂(樹脂に該当する)を含有することが好ましい。本明細書において、アルカリ可溶性樹脂とは、アルカリ可溶性を促進する基(アルカリ可溶性基)を含有する樹脂を意図し、既に説明した分散剤とは異なる樹脂を意図する。
組成物中におけるアルカリ可溶性樹脂の含有量としては特に制限されないが、一般に組成物の全固形分に対して、0.5~30質量%が好ましく、組成物がより優れた本発明の効果を有する点で、1~20質量%が好ましい。
アルカリ可溶性樹脂は1種を単独で用いても、2種以上を併用してもよい。2種以上のアルカリ可溶性樹脂を併用する場合には、合計含有量が上記範囲内であることが好ましい。 <Alkali-soluble resin>
It is preferable that the said composition contains alkali-soluble resin (it corresponds to resin). In the present specification, the alkali-soluble resin means a resin containing a group that promotes alkali solubility (alkali-soluble group), and a resin different from the dispersant already described.
The content of the alkali-soluble resin in the composition is not particularly limited, but is generally preferably 0.5 to 30% by mass with respect to the total solid content of the composition, and the composition has a more excellent effect of the present invention. In this respect, 1 to 20% by mass is preferable.
Alkali-soluble resin may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of alkali-soluble resin together, it is preferable that total content is in the said range.
不飽和カルボン酸としては特に制限されないが、(メタ)アクリル酸、クロトン酸、及び、ビニル酢酸等のモノカルボン酸類;イタコン酸、マレイン酸、及び、フマル酸等のジカルボン酸、又は、その酸無水物;フタル酸モノ(2-(メタ)アクリロイロキシエチル)等の多価カルボン酸モノエステル類;等が挙げられる。 Specific examples of the alkali-soluble resin include a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound.
Although it does not restrict | limit especially as unsaturated carboxylic acid, Monocarboxylic acids, such as (meth) acrylic acid, crotonic acid, and vinyl acetic acid; Dicarboxylic acids, such as itaconic acid, maleic acid, and fumaric acid, or its acid anhydride And polycarboxylic acid monoesters such as monophthalic acid (2- (meth) acryloyloxyethyl).
ポリイミド前駆体としては、例えば、式(1)で表される繰り返し単位を含有する樹脂が挙げられる。ポリイミド前駆体の構造としては、例えば、下記式(2)で示されるアミック酸構造と、アミック酸構造が一部イミド閉環してなる下記式(3)、及び/又は、全てイミド閉環した下記式(4)で示されるイミド構造を含有するものが挙げられる。
なお、本明細書において、アミック酸構造を有するポリイミド前駆体をポリアミック酸ということがある。 A polyimide precursor can also be used as the alkali-soluble resin. The polyimide precursor intends a resin obtained by subjecting a compound containing an acid anhydride group and a diamine compound to an addition polymerization reaction at 40 to 100 ° C.
As a polyimide precursor, resin containing the repeating unit represented by Formula (1) is mentioned, for example. Examples of the structure of the polyimide precursor include an amic acid structure represented by the following formula (2), the following formula (3) in which the amic acid structure is partially imide ring-closed, and / or the following formula in which all imide rings are closed: The thing containing the imide structure shown by (4) is mentioned.
In this specification, a polyimide precursor having an amic acid structure may be referred to as a polyamic acid.
アルカリ可溶性基を含有するポリイミド樹脂としては、特に制限されず、公知のアルカリ可溶性基を含有するポリイミド樹脂を用いることができる。上記ポリイミド樹脂としては、例えば、特開2014-137523号公報の0050段落に記載された樹脂、特開2015-187676号公報の0058段落に記載された樹脂、及び、特開2014-106326号公報の0012~0013段落に記載された樹脂等が挙げられ、上記の内容は本明細書に組み込まれる。 The alkali-soluble resin preferably contains at least one selected from the group consisting of a polyimide resin and a polyimide precursor in that the pattern shape of the patterned cured film obtained using the composition is more excellent. .
The polyimide resin containing an alkali-soluble group is not particularly limited, and a known polyimide resin containing an alkali-soluble group can be used. Examples of the polyimide resin include resins described in paragraph 0050 of JP-A-2014-137523, resins described in paragraph 0058 of JP-A-2015-187676, and JP-A-2014-106326. Examples include the resins described in paragraphs 0012 to 0013, and the above contents are incorporated herein.
上記組成物は、上記以外の任意成分を含有していてもよい。任意成分としては、例えば、重合性化合物、重合開始剤、溶剤、シランカップリング剤、紫外線吸収剤、界面活性剤、密着改良剤、及び、着色剤、顔料誘導体等が挙げられる。なお、着色剤とは、チタン窒化物含有粒子以外の着色剤を意図する。以下では、各成分について詳述する。 [Optional ingredients]
The said composition may contain arbitrary components other than the above. Examples of the optional component include a polymerizable compound, a polymerization initiator, a solvent, a silane coupling agent, an ultraviolet absorber, a surfactant, an adhesion improver, a colorant, and a pigment derivative. In addition, with a coloring agent, coloring agents other than titanium nitride containing particle | grains are intended. Below, each component is explained in full detail.
上記組成物は、重合性化合物を含有することが好ましい。本明細書において重合性化合物とは、重合性基を含有する化合物を意図し、分散剤、及び、アルカリ可溶性樹脂とは異なる成分を意図する。 <Polymerizable compound>
The composition preferably contains a polymerizable compound. In the present specification, the polymerizable compound means a compound containing a polymerizable group and a component different from the dispersant and the alkali-soluble resin.
重合性化合物は1種を単独で用いても、2種以上を併用してもよい。2種以上の重合性化合物を併用する場合には、合計含有量が上記範囲内であることが好ましい。 The content of the polymerizable compound in the composition is not particularly limited, but is preferably 1 to 30% by mass and more preferably 5 to 20% by mass with respect to the total solid content of the composition.
A polymeric compound may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of polymeric compounds together, it is preferable that total content is in the said range.
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。 The polymerizable compound may be in any of chemical forms such as a monomer, a prepolymer, an oligomer, a mixture thereof, and a multimer thereof.
The polymerizable compound is preferably a 3 to 15 functional (meth) acrylate compound, more preferably a 3 to 6 functional (meth) acrylate compound.
以下に好ましい重合性化合物の態様を示す。 Polymerizable compounds are dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product; manufactured by Nippon Kayaku), di Pentaerythritol penta (meth) acrylate (KAYARAD D-310 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (KAYARAD DPHA as a commercial product; manufactured by Nippon Kayaku Co., Ltd., A-DPH- 12E; manufactured by Shin-Nakamura Chemical Co., Ltd.) and a structure in which these (meth) acryloyl groups are mediated by an ethylene glycol residue or a propylene glycol residue (for example, SR454, SR499, commercially available from Sartomer). These oligomer types can also be used. Further, NK ester A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) and the like can also be used.
Preferred embodiments of the polymerizable compound are shown below.
カプロラクトン構造を含有する化合物としては、分子内にカプロラクトン構造を含有する限り特に限定されるものではないが、例えば、トリメチロールエタン、ジトリメチロールエタン、トリメチロールプロパン、ジトリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、トリペンタエリスリトール、グリセリン、ジグリセロール、トリメチロールメラミン等の多価アルコールと、(メタ)アクリル酸及びε-カプロラクトンとをエステル化することにより得られる、ε-カプロラクトン変性多官能(メタ)アクリレートを挙げることができる。なかでも下記式(Z-1)で表されるカプロラクトン構造を含有する化合物が好ましい。 The polymerizable compound is also preferably a compound containing a caprolactone structure.
The compound containing a caprolactone structure is not particularly limited as long as it contains a caprolactone structure in the molecule. For example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipenta Ε-caprolactone-modified polyfunctional (meth) acrylate obtained by esterifying polyhydric alcohol such as erythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine, (meth) acrylic acid and ε-caprolactone Can be mentioned. Of these, compounds containing a caprolactone structure represented by the following formula (Z-1) are preferred.
式(Z-4)中、(メタ)アクリロイル基の合計は3個又は4個であり、mは各々独立に0~10の整数を表し、各mの合計は0~40の整数である。
式(Z-5)中、(メタ)アクリロイル基の合計は5個又は6個であり、nは各々独立に0~10の整数を表し、各nの合計は0~60の整数である。 In formulas (Z-4) and (Z-5), each E independently represents — ((CH 2 ) y CH 2 O) — or ((CH 2 ) y CH (CH 3 ) O) —. Y represents an integer of 0 to 10, and X independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxylic acid group.
In the formula (Z-4), the total number of (meth) acryloyl groups is 3 or 4, each m independently represents an integer of 0 to 10, and the total of each m is an integer of 0 to 40.
In formula (Z-5), the total number of (meth) acryloyl groups is 5 or 6, each n independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60.
また、各mの合計は、2~40の整数が好ましく、2~16の整数がより好ましく、4~8の整数が更に好ましい。
式(Z-5)中、nは、0~6の整数が好ましく、0~4の整数がより好ましい。
また、各nの合計は、3~60の整数が好ましく、3~24の整数がより好ましく、6~12の整数が更に好ましい。
また、式(Z-4)又は式(Z-5)中の-((CH2)yCH2O)-又は((CH2)yCH(CH3)O)-は、酸素原子側の末端がXに結合する形態が好ましい。 In the formula (Z-4), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
The total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and further preferably an integer of 4 to 8.
In the formula (Z-5), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
The total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and still more preferably an integer of 6 to 12.
In formula (Z-4) or formula (Z-5), — ((CH 2 ) y CH 2 O) — or ((CH 2 ) y CH (CH 3 ) O) — A form in which the terminal is bonded to X is preferred.
式(Z-4)又は式(Z-5)で表される化合物のなかでも、ペンタエリスリトール誘導体及び/又はジペンタエリスリトール誘導体がより好ましい。 Further, the total content of the compound represented by the formula (Z-4) or the formula (Z-5) in the polymerizable compound is preferably 20% by mass or more, and more preferably 50% by mass or more.
Of the compounds represented by the formula (Z-4) or the formula (Z-5), a pentaerythritol derivative and / or a dipentaerythritol derivative are more preferable.
カルド骨格を含有する重合性化合物としては、9,9-ビスアリールフルオレン骨格を含有する重合性化合物が好ましい。
カルド骨格を含有する重合性化合物としては、限定されないが、例えば、オンコートEXシリーズ(長瀬産業社製)及びオグソール(大阪ガスケミカル社製)等が挙げられる。 The polymerizable compound may contain a cardo skeleton.
As the polymerizable compound containing a cardo skeleton, a polymerizable compound containing a 9,9-bisarylfluorene skeleton is preferable.
Examples of the polymerizable compound containing a cardo skeleton include, but are not limited to, oncoat EX series (manufactured by Nagase Sangyo Co., Ltd.) and Ogsol (manufactured by Osaka Gas Chemical Co., Ltd.).
上記組成物は、重合開始剤を含有することが好ましい。重合開始剤としては、特に制限されず、公知の重合開始剤を用いることができる。重合開始剤としては、例えば、光重合開始剤、及び、熱重合開始剤等が挙げられ、光重合開始剤が好ましい。なお、重合開始剤としては、いわゆるラジカル重合開始剤が好ましい。
重合開始剤の含有量としては、組成物の全固形分に対して1~20質量%が好ましく、3~10質量%がより好ましい。
重合開始剤は1種を単独で用いても、2種以上を併用してもよい。2種以上の重合開始剤を併用する場合には、合計含有量が上記範囲内であることが好ましい。 <Polymerization initiator>
The composition preferably contains a polymerization initiator. The polymerization initiator is not particularly limited, and a known polymerization initiator can be used. As a polymerization initiator, a photoinitiator, a thermal polymerization initiator, etc. are mentioned, for example, A photoinitiator is preferable. The polymerization initiator is preferably a so-called radical polymerization initiator.
The content of the polymerization initiator is preferably 1 to 20% by mass, more preferably 3 to 10% by mass, based on the total solid content of the composition.
A polymerization initiator may be used individually by 1 type, or may use 2 or more types together. When two or more polymerization initiators are used in combination, the total content is preferably within the above range.
重合開始剤の具体例としては、例えば、加藤清視著「紫外線硬化システム」(株式会社総合技術センター発行:平成元年)の第65~148頁に記載されている重合開始剤などを挙げることができる。 Examples of the thermal polymerization initiator include 2,2′-azobisisobutyronitrile (AIBN), 3-carboxypropionitrile, azobismaleonitrile, and dimethyl- (2,2 ′)-azobis (2 -Methylpropionate) [V-601] and the like, and organic peroxides such as benzoyl peroxide, lauroyl peroxide, and potassium persulfate.
Specific examples of the polymerization initiator include, for example, polymerization initiators described on pages 65 to 148 of “Ultraviolet curing system” written by Kiyoto Kato (published by General Technology Center Co., Ltd .: 1989). Can do.
上記組成物は光重合開始剤を含有することが好ましい。
光重合開始剤としては、重合性化合物の重合を開始することができれば特に制限されず、公知の光重合開始剤を用いることができる。光重合開始剤としては、例えば、紫外線領域から可視光領域に対して感光性を有するものが好ましい。また、光励起された増感剤と何らかの作用を生じ、活性ラジカルを生成する活性剤であってもよく、重合性化合物の種類に応じてカチオン重合を開始させるような開始剤であってもよい。
また、光重合開始剤は、約300nm~800nm(330nm~500nmがより好ましい。)の範囲内に少なくとも約50のモル吸光係数を有する化合物を、少なくとも1種含有していることが好ましい。 (Photopolymerization initiator)
The composition preferably contains a photopolymerization initiator.
As a photoinitiator, if a polymerization of a polymeric compound can be started, it will not restrict | limit, A well-known photoinitiator can be used. As the photopolymerization initiator, for example, those having photosensitivity from the ultraviolet region to the visible light region are preferable. Further, it may be an activator that generates an active radical by generating some action with a photoexcited sensitizer, and may be an initiator that initiates cationic polymerization according to the type of the polymerizable compound.
The photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).
光重合開始剤は、1種を単独で用いても、2種以上を併用してもよい。光重合開始剤を2種以上併用する場合には、その合計量が上記範囲内であることが好ましい。 The content of the photopolymerization initiator is preferably 1 to 20% by mass and more preferably 3 to 10% by mass with respect to the total solid content of the composition.
A photoinitiator may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of photoinitiators together, it is preferable that the total amount is in the said range.
光重合開始剤の具体例としては、例えば、特開2013-29760号公報の段落0265~0268を参酌することができ、この内容は本明細書に組み込まれる。 Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those containing a triazine skeleton, those containing an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, Examples include oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, aminoacetophenone compounds, and hydroxyacetophenones.
As specific examples of the photopolymerization initiator, for example, paragraphs 0265 to 0268 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
ヒドロキシアセトフェノン化合物としては、IRGACURE-184、DAROCUR-1173、IRGACURE-500、IRGACURE-2959、及びIRGACURE-127(商品名:いずれもBASF社製)を用いることができる。
アミノアセトフェノン化合物としては、市販品であるIRGACURE-907、IRGACURE-369、又はIRGACURE-379EG(商品名:いずれもBASF社製)を用いることができる。アミノアセトフェノン化合物としては、365nm又は405nm等の長波光源に吸収波長がマッチングされた特開2009-191179公報に記載の化合物も用いることができる。
アシルホスフィン化合物としては、市販品であるIRGACURE-819、又はIRGACURE-TPO(商品名:いずれもBASF社製)を用いることができる。 More specifically, as the photopolymerization initiator, for example, an aminoacetophenone-based initiator described in JP-A-10-291969 and an acylphosphine-based initiator described in Japanese Patent No. 4225898 can also be used. .
As the hydroxyacetophenone compound, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names: all manufactured by BASF) can be used.
As the aminoacetophenone compound, commercially available products IRGACURE-907, IRGACURE-369, or IRGACURE-379EG (trade names: all manufactured by BASF) can be used. As the aminoacetophenone compound, a compound described in JP-A-2009-191179 in which an absorption wavelength is matched with a long wave light source such as 365 nm or 405 nm can also be used.
As the acylphosphine compound, commercially available IRGACURE-819 or IRGACURE-TPO (trade name: all manufactured by BASF) can be used.
光重合開始剤として、より好ましくはオキシムエステル系重合開始剤(オキシム化合物)が挙げられる。特にオキシム化合物は高感度で重合効率が高く、組成物中におけるチタン窒化物含有粒子の含有量濃度によらず組成物層を硬化でき、チタン窒化物含有粒子の含有量を高く設計しやすいため好ましい。
オキシム化合物の具体例としては、特開2001-233842号公報記載の化合物、特開2000-80068号公報記載の化合物、又は特開2006-342166号公報記載の化合物を用いることができる。
オキシム化合物としては、例えば、3-ベンゾイロキシイミノブタン-2-オン、3-アセトキシイミノブタン-2-オン、3-プロピオニルオキシイミノブタン-2-オン、2-アセトキシイミノペンタン-3-オン、2-アセトキシイミノ-1-フェニルプロパン-1-オン、2-ベンゾイロキシイミノ-1-フェニルプロパン-1-オン、3-(4-トルエンスルホニルオキシ)イミノブタン-2-オン、及び2-エトキシカルボニルオキシイミノ-1-フェニルプロパン-1-オン等が挙げられる。
また、J.C.S.Perkin II(1979年)pp.1653-1660)、J.C.S.Perkin II(1979年)pp.156-162、Journal of Photopolymer Science and Technology(1995年)pp.202-232、特開2000-66385号公報記載の化合物、特開2000-80068号公報、特表2004-534797号公報、及び特開2006-342166号公報の各公報に記載の化合物等も挙げられる。
市販品ではIRGACURE-OXE01(BASF社製)、IRGACURE-OXE02(BASF社製)、IRGACURE-OXE03(BASF社製)、又はIRGACURE-OXE04(BASF社製)も好適に用いられる。また、TR-PBG-304(常州強力電子新材料有限公司製)、アデカアークルズNCI-831及びアデカアークルズNCI-930(ADEKA社製)、又はN-1919(カルバゾール・オキシムエステル骨格含有光開始剤(ADEKA社製)も用いることができる。 (Oxime compounds)
More preferred examples of the photopolymerization initiator include oxime ester polymerization initiators (oxime compounds). In particular, oxime compounds are preferred because they have high sensitivity and high polymerization efficiency, can cure the composition layer regardless of the content concentration of titanium nitride-containing particles in the composition, and are easy to design with a high content of titanium nitride-containing particles. .
As specific examples of the oxime compound, a compound described in JP-A No. 2001-233842, a compound described in JP-A No. 2000-80068, or a compound described in JP-A No. 2006-342166 can be used.
Examples of the oxime compound include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, and 2-ethoxycarbonyl And oxyimino-1-phenylpropan-1-one.
In addition, J.H. C. S. Perkin II (1979) pp. 1653-1660), J.M. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995), pp. 156-162. Examples thereof include compounds described in 202-232, JP-A No. 2000-66385, JP-A No. 2000-80068, JP-T 2004-534797, and JP-A No. 2006-342166. .
IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF), IRGACURE-OXE03 (manufactured by BASF), or IRGACURE-OXE04 (manufactured by BASF) are also suitably used as commercial products. Also, TR-PBG-304 (manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), Adeka Arcles NCI-831 and Adeka Arcles NCI-930 (manufactured by ADEKA), or N-1919 (carbazole oxime ester skeleton containing photoinitiator An agent (manufactured by ADEKA) can also be used.
好ましくは、例えば、特開2013-29760号公報の段落0274~0275を参酌することができ、この内容は本明細書に組み込まれる。
具体的には、オキシム化合物としては、下記式(OX-1)で表される化合物が好ましい。なお、オキシム化合物のN-O結合が(E)体のオキシム化合物であっても、(Z)体のオキシム化合物であっても、(E)体と(Z)体との混合物であってもよい。 Further, as oxime compounds other than those described above, compounds described in JP-A-2009-519904 in which an oxime is linked to the carbazole N-position; compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety; Compounds described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced at the dye moiety; Ketooxime compounds described in International Patent Publication No. 2009-131189; Triazine skeleton and oxime skeleton are the same molecule A compound described in US Pat. No. 7,556,910 contained therein; a compound described in JP-A-2009-221114 having a maximum absorption at 405 nm and good sensitivity to a g-line light source; and the like may be used.
Preferably, for example, paragraphs 0274 to 0275 of JP 2013-29760 A can be referred to, the contents of which are incorporated herein.
Specifically, the oxime compound is preferably a compound represented by the following formula (OX-1). The N—O bond of the oxime compound may be an (E) oxime compound, a (Z) oxime compound, a mixture of (E) isomer and (Z) isomer. Good.
式(OX-1)中、Rで表される一価の置換基としては、一価の非金属原子団であることが好ましい。
一価の非金属原子団としては、アルキル基、アリール基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、複素環基、アルキルチオカルボニル基、及び、アリールチオカルボニル基等が挙げられる。また、これらの基は、1以上の置換基を有していてもよい。また、前述した置換基は、更に他の置換基で置換されていてもよい。
置換基としてはハロゲン原子、アリールオキシ基、アルコキシカルボニル基又はアリールオキシカルボニル基、アシルオキシ基、アシル基、アルキル基、及び、アリール基等が挙げられる。
式(OX-1)中、Bで表される一価の置換基としては、アリール基、複素環基、アリールカルボニル基、又は、複素環カルボニル基が好ましい。これらの基は1以上の置換基を有していてもよい。置換基としては、前述した置換基が例示できる。
式(OX-1)中、Aで表される二価の有機基としては、炭素数1~12のアルキレン基、シクロアルキレン基、又は、アルキニレン基が好ましい。これらの基は1以上の置換基を有していてもよい。置換基としては、前述した置換基が例示できる。 In formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.
In the formula (OX-1), the monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
Examples of the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. Moreover, these groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.
In the formula (OX-1), the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.
In the formula (OX-1), the divalent organic group represented by A is preferably an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, or an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.
また、上記式(3)及び(4)において、R1は、それぞれ独立に、メチル基、エチル基、n-プロピル基、i-プロピル基、シクロヘキシル基又はフェニル基が好ましい。R3はメチル基、エチル基、フェニル基、トリル基又はキシリル基が好ましい。R4は炭素数1~6のアルキル基又はフェニル基が好ましい。R5はメチル基、エチル基、フェニル基、トリル基又はナフチル基が好ましい。Xは直接結合が好ましい。
式(1)及び式(2)で表される化合物の具体例としては、例えば、特開2014-137466号公報の段落0076~0079に記載された化合物が挙げられる。この内容は本明細書に組み込まれることとする。 In the above formulas (1) and (2), R 1 and R 2 are preferably each independently a methyl group, ethyl group, n-propyl group, i-propyl group, cyclohexyl group or phenyl group. R 3 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a xylyl group. R 4 is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. R 5 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a naphthyl group. X is preferably a direct bond.
In the above formulas (3) and (4), R 1 is preferably each independently a methyl group, ethyl group, n-propyl group, i-propyl group, cyclohexyl group or phenyl group. R 3 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a xylyl group. R 4 is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. R 5 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a naphthyl group. X is preferably a direct bond.
Specific examples of the compounds represented by formula (1) and formula (2) include, for example, compounds described in paragraphs 0076 to 0079 of JP-A No. 2014-137466. This content is incorporated herein.
オキシム化合物の365nm又は405nmにおけるモル吸光係数は、感度の観点から、1,000~300,000であることが好ましく、2,000~300,000であることがより好ましく、5,000~200,000であることが更に好ましい。
化合物のモル吸光係数は、公知の方法を用いることができるが、例えば、紫外可視分光光度計(Varian社製Cary-5 spctrophotometer)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。
光重合開始剤は、必要に応じて2種以上を組み合わせて使用してもよい。 The oxime compound preferably has a maximum absorption wavelength in the wavelength region of 350 nm to 500 nm, more preferably has a maximum absorption wavelength in the wavelength region of 360 nm to 480 nm, and more preferably has a 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, more preferably 5,000 to 200,000 from the viewpoint of sensitivity. More preferably, it is 000.
For the molar extinction coefficient of the compound, a known method can be used. It is preferable to measure.
You may use a photoinitiator in combination of 2 or more type as needed.
上記組成物は、溶剤を含有することが好ましい。組成物が溶剤を含有する場合、溶剤の含有量としては特に制限されないが、組成物の全固形分が15~40質量%となるよう調整されることが好ましい。
溶剤は、1種を単独で用いても、2種以上を併用してもよい。2種以上の溶剤を併用する場合には、組成物の全固形分が上記範囲内となるよう調整されることが好ましい。 <Solvent>
The composition preferably contains a solvent. When the composition contains a solvent, the content of the solvent is not particularly limited, but is preferably adjusted so that the total solid content of the composition is 15 to 40% by mass.
A solvent may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of solvent together, it is preferable to adjust so that the total solid content of a composition may become in the said range.
有機溶剤としては、例えば、アセトン、メチルエチルケトン、シクロヘキサン、酢酸エチル、エチレンジクロライド、テトラヒドロフラン、トルエン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールジメチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、アセチルアセトン、シクロヘキサノン、シクロペンタノン、ジアセトンアルコール、エチレングリコールモノメチルエーテルアセテート、エチレングリコールエチルエーテルアセテート、エチレングリコールモノイソプロピルエーテル、エチレングリコールモノブチルエーテルアセテート、3-メトキシプロパノール、メトキシメトキシエタノール、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、3-メトキシプロピルアセテート、N,N-ジメチルホルムアミド、ジメチルスルホキシド、γ-ブチロラクトン、酢酸エチル、酢酸ブチル、乳酸メチル、N-メチル-2-ピロリドン、及び、乳酸エチル等が挙げられるが、これらに限定されない。 It does not restrict | limit especially as a kind of solvent, A well-known solvent can be used. Examples of the solvent include water or an organic solvent.
Examples of the organic solvent include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone. , Cyclohexanone, cyclopentanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol mono Chill ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, ethyl acetate, Examples include but are not limited to butyl acetate, methyl lactate, N-methyl-2-pyrrolidone, and ethyl lactate.
組成物は、界面活性剤を含有することが好ましい。界面活性剤は、組成物の塗布性向上に寄与する。
上記組成物が、界面活性剤を含有する場合、界面活性剤の含有量としては、組成物の全固形分に対して、0.001~2.0質量%が好ましい。
界面活性剤は、1種を単独で用いても、2種以上を併用してもよい。界面活性剤を2種以上併用する場合は、合計量が上記範囲内であることが好ましい。 <Surfactant>
The composition preferably contains a surfactant. The surfactant contributes to improving the coating property of the composition.
When the composition contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass with respect to the total solid content of the composition.
Surfactant may be used individually by 1 type, or may use 2 or more types together. When two or more surfactants are used in combination, the total amount is preferably within the above range.
フッ素系界面活性剤としてブロックポリマーを用いることもでき、具体例としては、例えば特開第2011-89090号公報に記載されたが化合物が挙げられる。 Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780 (above DIC Corporation), Florad FC430, FC431, FC171 (Sumitomo 3M Limited), Surflon S-382, SC-101, SC- 103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, K-H-40 (above, manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (made by OMNOVA) etc. are mentioned.
A block polymer can also be used as the fluorosurfactant, and specific examples include compounds described in JP-A No. 2011-89090.
組成物は、着色剤を含有してもよい。本明細書において、着色剤とはチタン窒化物含有粒子とは異なる化合物を意図する。 <Colorant>
The composition may contain a colorant. In this specification, a colorant intends a compound different from titanium nitride-containing particles.
着色剤を含有する場合、その含有量は、硬化して得られる遮光膜の光学特性に応じて決定することができる。また、着色剤は1種を単独で用いても、2種以上を併用してもよい。 As the colorant, various known pigments (color pigments) and dyes (color dyes) can be used. In addition, as a pigment, an inorganic pigment and an organic pigment are mentioned, for example.
When it contains a colorant, its content can be determined according to the optical properties of the light-shielding film obtained by curing. Moreover, a coloring agent may be used individually by 1 type, or may use 2 or more types together.
上記無機顔料としては、特に制限されず、公知の無機顔料を用いることができる。
無機顔料としては、例えば、カーボンブラック、シリカ、亜鉛華、鉛白、リトポン、酸化チタン、酸化クロム、酸化鉄、沈降性硫酸バリウム及びバライト粉、鉛丹、酸化鉄赤、黄鉛、亜鉛黄(亜鉛黄1種、亜鉛黄2種)、ウルトラマリン青、プロシア青(フェロシアン化鉄カリ)ジルコングレー、プラセオジムイエロー、クロムチタンイエロー、クロムグリーン、ピーコック、ビクトリアグリーン、紺青(プルシアンブルーとは無関係)、バナジウムジルコニウム青、クロム錫ピンク、陶試紅、並びに、サーモンピンク等が挙げられる。また、黒色の無機顔料であることが好ましく、無機顔料としては、含有量が少なくとも、高い光学濃度を有する硬化膜を形成することができる組成物が得られる点で、カーボンブラック、チタンブラック、及び金属顔料等(以下、「黒色顔料」ともいう。)が好ましい。金属顔料としては、例えば、Nb、V、Co、Cr、Cu、Mn、Ru、Fe、Ni、Sn、Ti、及びAgからなる群より選ばれる1種又は2種以上の金属元素を含む金属酸化物又は金属窒素物が挙げられる。
無機顔料としては、銀を含有する金属顔料、錫を含有する金属顔料、並びに、銀及び錫を含有する金属顔料からなる群から選択される少なくとも1種を含有することが好ましく、後述する窒化物又は酸窒化物を含有する顔料から選択される少なくとも1種を含有することがより好ましい。
なお、無機顔料は1種を単独で用いても、2種以上を併用してもよい。 (Inorganic pigment)
The inorganic pigment is not particularly limited, and a known inorganic pigment can be used.
Examples of inorganic pigments include carbon black, silica, zinc white, lead white, lithopone, titanium oxide, chromium oxide, iron oxide, precipitated barium sulfate and barite powder, red lead, iron oxide red, yellow lead, zinc yellow ( 1 type of zinc yellow, 2 types of zinc yellow), ultramarine blue, prussian blue (potassium ferrocyanide) zircon gray, praseodymium yellow, chrome titanium yellow, chrome green, peacock, Victoria green, bituminous (unrelated to Prussian blue) , Vanadium zirconium blue, chrome tin pink, ceramic red, and salmon pink. Further, it is preferably a black inorganic pigment, and as the inorganic pigment, carbon black, titanium black, and at least a content capable of forming a cured film having a high optical density is obtained. A metal pigment or the like (hereinafter also referred to as “black pigment”) is preferable. Examples of the metal pigment include a metal oxide containing one or more metal elements selected from the group consisting of Nb, V, Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag. Product or metal nitrogen product.
The inorganic pigment preferably contains at least one selected from the group consisting of metal pigments containing silver, metal pigments containing tin, and metal pigments containing silver and tin. Or it is more preferable to contain at least one selected from pigments containing oxynitrides.
In addition, an inorganic pigment may be used individually by 1 type, or may use 2 or more types together.
赤外線吸収性を有する顔料としては、タングステン化合物、及び金属ホウ化物等が好ましく、なかでも、赤外領域の波長における遮光性に優れる点から、タングステン化合物がより好ましい。特に露光による硬化効率に関わるオキシム系重合開始剤の光吸収波長領域と、可視光領域の透光性に優れる観点からタングステン化合物が好ましい。 As the colorant, a pigment having infrared absorptivity can also be used.
As the pigment having infrared absorptivity, a tungsten compound, a metal boride, and the like are preferable, and among them, a tungsten compound is more preferable in terms of excellent light-shielding properties at wavelengths in the infrared region. In particular, a tungsten compound is preferable from the viewpoint of excellent light absorption wavelength region of an oxime polymerization initiator related to curing efficiency by exposure and transparency of visible light region.
更に、後述する近赤外線吸収剤、赤外線吸収剤を加えてもよい。 Two or more of these pigments may be used in combination, or may be used in combination with a dye described later. In order to adjust the color tone and to improve the light-shielding property in a desired wavelength region, for example, chromatic colors such as red, green, yellow, orange, purple and blue are added to black or infrared light-shielding pigments. The form which mixes the pigment or the dye mentioned later is mentioned. It is preferable to mix a red pigment or dye, or a purple pigment or dye with a black or infrared pigment, and it is more preferable to mix a red pigment with a black pigment or infrared pigment.
Furthermore, you may add the near-infrared absorber and infrared absorber which are mentioned later.
有機顔料としては、例えば、カラーインデックス(C.I.)ピグメントイエロー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、
C.I.ピグメントオレンジ 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、
C.I.ピグメントレッド 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;
C.I.ピグメントグリーン 7,10,36,37,58,59等;
C.I.ピグメントバイオレット 1,19,23,27,32,37,42等;
C.I.ピグメントブルー 1,2,15,15:1,15:2,15:3,15:4,15:6,16,22,60,64,66,79,80等;
が挙げられる。なお、顔料は1種を単独で用いても、2種以上を併用してもよい。 Organic pigment Examples of the organic pigment include, for example, Color Index (CI) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 16 7,168,169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214, etc.
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. ,
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, etc .;
C. I. Pigment green 7, 10, 36, 37, 58, 59, etc .;
C. I. Pigment violet 1, 19, 23, 27, 32, 37, 42, etc .;
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80, etc .;
Is mentioned. In addition, a pigment may be used individually by 1 type, or may use 2 or more types together.
染料としては、例えば特開昭64-90403号公報、特開昭64-91102号公報、特開平1-94301号公報、特開平6-11614号公報、特登2592207号、米国特許4808501号明細書、米国特許5667920号明細書、米国特許505950号明細書、特開平5-333207号公報、特開平6-35183号公報、特開平6-51115号公報、及び、特開平6-194828号公報等に開示されている色素を使用できる。化学構造として区分すると、ピラゾールアゾ化合物、ピロメテン化合物、アニリノアゾ化合物、トリフェニルメタン化合物、アントラキノン化合物、ベンジリデン化合物、オキソノール化合物、ピラゾロトリアゾールアゾ化合物、ピリドンアゾ化合物、シアニン化合物、フェノチアジン化合物、及び、ピロロピラゾールアゾメチン化合物等を使用できる。また、染料としては色素多量体を用いてもよい。色素多量体としては、特開2011-213925号公報、特開2013-041097号公報に記載されている化合物が挙げられる。また、分子内に重合性を有する重合性染料を用いてもよく、市販品としては、例えば、和光純薬株式会社製RDWシリーズが挙げられる。 (dye)
Examples of the dye include, for example, JP-A No. 64-90403, JP-A No. 64-91102, JP-A No. 1-94301, JP-A No. 6-11614, No. 2592207, and US Pat. No. 4,808,501. U.S. Pat. No. 5,667,920, U.S. Pat. No. 505950, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, and JP-A-6-194828. The disclosed dyes can be used. Pyrazole azo compounds, pyromethene compounds, anilinoazo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, and pyrrolopyrazole azomethines A compound etc. can be used. A dye multimer may be used as the dye. Examples of the dye multimer include compounds described in JP2011-213925A and JP2013-041097A. Moreover, you may use the polymerizable dye which has polymerizability in a molecule | numerator, As a commercial item, the RDW series by Wako Pure Chemical Industries, Ltd. is mentioned, for example.
上記着色剤は、更に赤外線吸収剤を含有してもよい。
赤外線吸収剤は、赤外領域(好ましくは、波長650~1300nm)の波長領域に吸収を有する化合物を意味する。赤外線吸収剤としては、波長675~900nmの波長領域に極大吸収波長を有する化合物が好ましい。
このような分光特性を有する着色剤としては、例えば、ピロロピロール化合物、銅化合物、シアニン化合物、フタロシアニン化合物、イミニウム化合物、チオール錯体系化合物、遷移金属酸化物系化合物、スクアリリウム化合物、ナフタロシアニン化合物、クアテリレン化合物、ジチオール金属錯体系化合物、及び、クロコニウム化合物等が挙げられる。
フタロシアニン化合物、ナフタロシアニン化合物、イミニウム化合物、シアニン化合物、スクアリリウム化合物及びクロコニウム化合物は、特開2010-111750号公報の段落0010~0081に開示の化合物を使用してもよく、この内容は本明細書に組み込まれる。シアニン化合物は、例えば、「機能性色素、大河原信/松岡賢/北尾悌次郎/平嶋恒亮・著、講談社サイエンティフィック」を参酌することができ、この内容は本明細書に組み込まれる。 (Infrared absorber)
The colorant may further contain an infrared absorber.
The infrared absorber means a compound having absorption in the wavelength region in the infrared region (preferably, a wavelength of 650 to 1300 nm). As the infrared absorber, a compound having a maximum absorption wavelength in a wavelength region of 675 to 900 nm is preferable.
Examples of colorants having such spectral characteristics include pyrrolopyrrole compounds, copper compounds, cyanine compounds, phthalocyanine compounds, iminium compounds, thiol complex compounds, transition metal oxide compounds, squarylium compounds, naphthalocyanine compounds, quaterylenes. Examples include compounds, dithiol metal complex compounds, and croconium compounds.
As the phthalocyanine compound, naphthalocyanine compound, iminium compound, cyanine compound, squarylium compound, and croconium compound, the compounds disclosed in paragraphs 0010 to 0081 of JP 2010-1111750 A may be used. Incorporated. As the cyanine compound, for example, “functional pigment, Shin Okawara / Ken Matsuoka / Keijiro Kitao / Kensuke Hirashima, written by Kodansha Scientific”, the contents of which are incorporated herein.
また、赤外線吸収剤は、25℃の水に1質量%以上溶解する化合物であることが好ましく、25℃の水に10質量%以上溶解する化合物がより好ましい。このような化合物を用いることで、耐溶剤性が良化する。
ピロロピロール化合物は、特開2010-222557号公報の段落0049~0062を参酌でき、この内容は本明細書に組み込まれることとする。シアニン化合物及びスクアリリウム化合物は、国際公開2014/088063号公報の段落0022~0063、国際公開2014/030628号公報の段落0053~0118、特開2014-59550号公報の段落0028~0074、国際公開2012/169447号公報の段落0013~0091、特開2015-176046号公報の段落0019~0033、特開2014-63144号公報の段落0053~0099、特開2014-52431号公報の段落0085~0150、特開2014-44301号公報の段落0076~0124、特開2012-8532号公報の段落0045~0078、特開2015-172102号公報の段落0027~0067、特開2015-172004号公報の段落0029~0067、特開2015-40895号公報の段落0029~0085、特開2014-126642号公報の段落0022~0036、特開2014-148567号公報の段落0011~0017、特開2015-157893号公報の段落0010~0025、特開2014-095007号公報の段落0013~0026、特開2014-80487号公報の段落0013~0047、及び特開2013-227403号公報の段落0007~0028等を参酌でき、この内容は本明細書に組み込まれることとする。 The compound having a maximum absorption wavelength in the wavelength region of 675 to 900 nm is preferably at least one selected from the group consisting of a cyanine compound, a pyrrolopyrrole compound, a squarylium compound, a phthalocyanine compound, and a naphthalocyanine compound.
Further, the infrared absorber is preferably a compound that dissolves 1% by mass or more in 25 ° C. water, and more preferably a compound that dissolves 10% by mass or more in 25 ° C. water. By using such a compound, the solvent resistance is improved.
The pyrrolopyrrole compound can be referred to paragraphs 0049 to 0062 of JP 2010-222557 A, the contents of which are incorporated herein. The cyanine compounds and squarylium compounds are disclosed in paragraphs 0022 to 0063 of International Publication No. 2014/088063, paragraphs 0053 to 0118 of International Publication No. 2014/030628, paragraphs 0028 to 0074 of JP 2014-59550 A, and International Publication No. 2012/0074. 169447, paragraphs 0013 to 0091, JP2015-176046, paragraphs 0019 to 0033, JP2014-63144, paragraphs 0053 to 00099, JP201452431, paragraphs 0085 to 0150, JP Paragraphs 0076 to 0124 of Japanese Patent Application Laid-Open No. 2014-44301, Paragraphs 0045 to 0078 of Japanese Patent Application Laid-Open No. 2012-8532, Paragraphs 0027 to 0067 of Japanese Patent Application Laid-Open No. 2015-172102, and Paragraph 002 of Japanese Patent Application Laid-Open No. 2015-172004. To 0067, paragraphs 0029 to 0085 of JP-A-2015-40895, paragraphs 0022 to 0036 of JP-A-2014-126642, paragraphs 0011 to 0017 of JP-A-2014-148567, and JP-A-2015-157893. Paragraphs 0010 to 0025, paragraphs 0013 to 0026 of JP 2014-095007 A, paragraphs 0013 to 0047 of JP 2014-80487 A, paragraphs 0007 to 0028 of JP 2013-227403 A, and the like can be referred to. The contents are incorporated herein.
上記組成物は、上述した各種成分を公知の混合方法(例えば、攪拌機、ホモジナイザー、高圧乳化装置、湿式粉砕機、又は、湿式分散機を用いた混合方法)により混合して調製することができる。
組成物の調製に際しては、各成分を一括配合してもよいし、各成分をそれぞれ、溶剤に溶解又は分散した後に逐次配合してもよい。また、配合する際の投入順序及び作業条件は特に制限されない。 [Production Method of Composition]
The above composition can be prepared by mixing the above-described various components by a known mixing method (for example, a mixing method using a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, or a wet disperser).
In preparing the composition, the respective components may be blended together, or the respective components may be blended sequentially after being dissolved or dispersed in a solvent. Moreover, the order of input and the working conditions when blending are not particularly limited.
(1)樹脂と、チタン窒化物含有粒子と、を混合して、チタン窒化物含有粒子分散液を得る、チタン窒化物含有粒子分散工程
(2)チタン窒化物含有粒子分散液と、その他の成分とを混合して、組成物を得る、混合工程 Especially, it is preferable that the manufacturing method of a composition contains the following processes by the point from which the more excellent effect of this invention is acquired.
(1) Titanium nitride-containing particle dispersion step of mixing a resin and titanium nitride-containing particles to obtain a titanium nitride-containing particle dispersion (2) Titanium nitride-containing particle dispersion and other components Mixing step to obtain a composition
フィルタの孔径は、0.1~7.0μm程度が適しており、好ましくは0.2~2.5μm程度、より好ましくは0.2~1.5μm程度、更に好ましくは0.3~0.7μmである。この範囲とすることにより、顔料のろ過詰まりを抑えつつ、顔料に含まれる不純物及び凝集物など、微細な異物を確実に除去することが可能となる。
フィルタを使用する際、異なるフィルタを組み合わせてもよい。その際、第1のフィルタでのフィルタリングは、1回のみでもよいし、2回以上行ってもよい。異なるフィルタを組み合わせて2回以上フィルタリングを行う場合は1回目のフィルタリングの孔径より2回目以降の孔径が同じ、又は、大きい方が好ましい。また、上述した範囲内で異なる孔径の第1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、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、上述した第1のフィルタと同様の材料等で形成されたものを使用することができる。第2のフィルタの孔径は、0.2~10.0μm程度が適しており、好ましくは0.2~7.0μm程度、更に好ましくは0.3~6.0μm程度である。
組成物は、金属、ハロゲンを含む金属塩、酸、アルカリ等の不純物を含まないことが好ましい。これら材料に含まれる不純物の含有量としては、1ppm以下が好ましく、1ppb以下がより好ましく、100ppt以下が更に好ましく、10ppt以下が特に好ましく、実質的に含まないこと(測定装置の検出限界以下であること)が最も好ましい。
なお、上記不純物は、誘導結合プラズマ質量分析装置(横河アナリティカルシステムズ製、Agilent 7500cs型)により測定することができる。 The composition is preferably filtered with a filter for the purpose of removing foreign substances or reducing defects. Any filter can be used without particular limitation as long as it has been conventionally used for filtration. For example, a filter made of a fluororesin such as PTFE (polytetrafluoroethylene), a polyamide resin such as nylon, and a polyolefin resin (including high density and ultra high molecular weight) such as polyethylene and polypropylene (PP) can be used. . Among these materials, polypropylene (including high density polypropylene) and nylon are preferable.
The filter has a pore diameter of about 0.1 to 7.0 μm, preferably about 0.2 to 2.5 μm, more preferably about 0.2 to 1.5 μm, and still more preferably 0.3 to 0.0 μm. 7 μm. By setting this range, it is possible to reliably remove fine foreign matters such as impurities and aggregates contained in the pigment while suppressing filtration clogging of the pigment.
When using filters, different filters may be combined. At that time, the filtering by the first filter may be performed only once or may be performed twice or more. When filtering two or more times by combining different filters, it is preferable that the second and subsequent pore diameters are the same or larger than the pore diameter of the first filtering. Moreover, you may combine the 1st filter of a different hole diameter within the range mentioned above. The pore diameter here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Japan Microlith Co., Ltd.) or KITZ Micro Filter Co. .
As the second filter, a filter formed of the same material as the first filter described above can be used. The pore size of the second filter is suitably about 0.2 to 10.0 μm, preferably about 0.2 to 7.0 μm, and more preferably about 0.3 to 6.0 μm.
It is preferable that the composition does not contain impurities such as metals, metal salts containing halogens, acids, and alkalis. The content of impurities contained in these materials is preferably 1 ppm or less, more preferably 1 ppb or less, still more preferably 100 ppt or less, particularly preferably 10 ppt or less, and substantially free (below the detection limit of the measuring device). Is most preferable.
The impurities can be measured by an inductively coupled plasma mass spectrometer (manufactured by Yokogawa Analytical Systems, Agilent 7500cs type).
組成物を用いることにより、硬化膜を形成することができる。
硬化膜の厚みは特に制限されないが、0.2~25μmが好ましい。
上記厚みは平均厚みであり、硬化膜の任意の5点以上の厚みを測定し、それらを算術平均した値である。 [Curing film and manufacturing method thereof]
By using the composition, a cured film can be formed.
The thickness of the cured film is not particularly limited, but is preferably 0.2 to 25 μm.
The above thickness is an average thickness, and is a value obtained by measuring the thicknesses of five or more arbitrary points of the cured film and arithmetically averaging them.
硬化処理の方法は特に制限されず、光硬化処理又は熱硬化処理が挙げられ、パターン形成が容易である点から、光硬化処理(特に、活性光線又は放射線を照射することによる硬化処理)が好ましい。 Although the manufacturing method in particular of a cured film is not restrict | limited, The method of apply | coating the composition mentioned above on a board | substrate, forming a coating film, performing a hardening process with respect to a coating film, and manufacturing a cured film is mentioned.
The method of the curing treatment is not particularly limited, and examples thereof include a photocuring treatment or a thermosetting treatment, and a photocuring treatment (particularly a curing treatment by irradiation with actinic rays or radiation) is preferable from the viewpoint of easy pattern formation. .
硬化膜の製造方法としては特に制限されないが、以下の工程を含有することが好ましい。
・組成物層形成工程
・露光工程
・現像工程
以下、各工程について説明する。 The cured film which concerns on embodiment of this invention is a cured film obtained by hardening | curing the composition layer formed using the said composition.
Although it does not restrict | limit especially as a manufacturing method of a cured film, It is preferable to contain the following processes.
-Composition layer formation process-Exposure process-Development process Hereinafter, each process is demonstrated.
組成物層形成工程は、上記組成物を用いて、組成物層を形成する工程である。組成物を用いて、組成物層を形成する工程としては、例えば、基板上に、組成物を塗布して、組成物層を形成する工程が挙げられる。
基板の種類は特に制限されないが、固体撮像素子として用いる場合は、例えば、ケイ素基板が挙げられ、カラーフィルタ(固体撮像素子用カラーフィルタを含む)として用いる場合には、ガラス基板等が挙げられる。
基板上への組成物の塗布方法としては、スピンコート、スリット塗布、インクジェット法、スプレー塗布、回転塗布、流延塗布、ロール塗布、及び、スクリーン印刷法等の各種の塗布方法を適用することができる。
基板上に塗布された組成物は、通常、70~150℃で1~4分程度の条件下で乾燥され、組成物層が形成される。 <Composition layer formation step>
The composition layer forming step is a step of forming a composition layer using the composition. As a process of forming a composition layer using a composition, the process of apply | coating a composition on a board | substrate and forming a composition layer is mentioned, for example.
Although the kind of board | substrate is not restrict | limited in particular, When using as a solid-state image sensor, a silicon substrate is mentioned, for example, When using as a color filter (including the color filter for solid-state image sensors), a glass substrate etc. are mentioned.
Various coating methods such as spin coating, slit coating, ink jet method, spray coating, spin coating, cast coating, roll coating, and screen printing can be applied as a method for coating the composition on the substrate. it can.
The composition coated on the substrate is usually dried at 70 to 150 ° C. for about 1 to 4 minutes to form a composition layer.
露光工程では、組成物層形成工程において形成された組成物層に、パターン状の開口部を備えるフォトマスクを介して、活性光線又は放射線を照射して露光し、光照射された組成物層だけを硬化させる。
露光は放射線の照射により行うことが好ましく、露光に際して用いることができる放射線としては、特に、g線、h線、及び、i線等の紫外線が好ましく用いられ、光源としては高圧水銀灯が好まれる。照射強度は5~1500mJ/cm2が好ましく、10~1000mJ/cm2がより好ましい。 <Exposure process>
In the exposure step, the composition layer formed in the composition layer formation step is exposed by irradiating actinic rays or radiation through a photomask having a patterned opening, and only the composition layer irradiated with light is exposed. Is cured.
The exposure is preferably performed by irradiation of radiation, and as radiation that can be used for exposure, ultraviolet rays such as g-line, h-line, and i-line are particularly preferably used, and a high-pressure mercury lamp is preferred as a light source. The irradiation intensity is preferably 5 ~ 1500mJ / cm 2, more preferably 10 ~ 1000mJ / cm 2.
露光工程に次いで、現像処理(現像工程)を行い、露光工程における光未照射部分を現像液に溶出させる。これにより、光硬化した部分だけが残る。
現像液としては、アルカリ現像液を用いてもよい。その場合は、有機アルカリ現像液を用いことが好ましい。現像温度としては通常20~40℃が好ましく、現像時間は20~180秒が好ましい。
アルカリ水溶液(アルカリ現像液)としては、例えば、無機系現像液としては、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸水素ナトリウム、硅酸ナトリウム、及び、メタ硅酸ナトリウム等のアルカリ性化合物を、濃度が0.001~10質量%、好ましくは0.005~0.5質量%となるように溶解したアルカリ水溶液が挙げられる。
また、有機アルカリ現像液としては、アンモニア水、エチルアミン、ジエチルアミン、ジメチルエタノールアミン、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド、ベンジルトリメチルアンモニウムヒドロキシド、コリン、ピロール、ピペリジン、及び、1,8-ジアザビシクロ-[5,4,0]-7-ウンデセン等のアルカリ性化合物を、濃度が0.001~10質量%、好ましくは0.005~0.5質量%となるように溶解したアルカリ水溶液が挙げられる。
アルカリ水溶液には、例えば、メタノール、エタノール等の水溶性有機溶剤、及び/又は、界面活性剤等を適量添加することもできる。なお、このようなアルカリ水溶液からなる現像液を使用した場合には、一般に現像後に硬化膜を純水で洗浄(リンス)する。 <Development process>
Subsequent to the exposure step, development processing (development step) is performed to elute the light non-irradiated portion in the exposure step into the developer. Thereby, only the photocured part remains.
An alkaline developer may be used as the developer. In that case, it is preferable to use an organic alkali developer. The development temperature is usually preferably 20 to 40 ° C., and the development time is preferably 20 to 180 seconds.
As an aqueous alkaline solution (alkali developer), for example, as an inorganic developer, an alkaline compound such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, and sodium metaoxalate, Examples thereof include an aqueous alkali solution dissolved so that the concentration is 0.001 to 10% by mass, preferably 0.005 to 0.5% by mass.
Organic alkaline developers include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, choline , Pyrrole, piperidine, and alkaline compounds such as 1,8-diazabicyclo- [5,4,0] -7-undecene, in a concentration of 0.001 to 10% by mass, preferably 0.005 to 0.5% by mass. %, An aqueous alkali solution dissolved so as to be%.
An appropriate amount of a water-soluble organic solvent such as methanol and ethanol, and / or a surfactant, for example, can be added to the alkaline aqueous solution. When a developer composed of such an alkaline aqueous solution is used, the cured film is generally washed (rinsed) with pure water after development.
その他の工程としては、特に制限はなく、目的に応じて適宜選択することができる。
その他の工程としては、例えば、基材の表面処理工程、前加熱工程(プリベーク工程)、後加熱工程(ポストベーク工程)等が挙げられる。
上記前加熱工程、及び後加熱工程における加熱温度は、80~300℃が好ましい。上限は、220℃以下がより好ましい。下限は90℃以上が好ましい。
前加熱工程及び後加熱工程における加熱時間は、30~300秒が好ましい。 In addition, the manufacturing method of a cured film may contain another process.
There is no restriction | limiting in particular as another process, According to the objective, it can select suitably.
Examples of the other steps include a substrate surface treatment step, a preheating step (pre-baking step), and a post-heating step (post-baking step).
The heating temperature in the preheating step and the postheating step is preferably 80 to 300 ° C. The upper limit is more preferably 220 ° C. or lower. The lower limit is preferably 90 ° C. or higher.
The heating time in the preheating step and the postheating step is preferably 30 to 300 seconds.
・OD(Optical Density)
上記硬化膜は、より優れた遮光性を有する点で、400~1200nmの波長領域における膜厚1.0μmあたりの光学濃度(OD:Optical Density)が、3.5超であることが好ましく、3.7超がより好ましく、4.0超が更に好ましく、4.2超が特に好ましい。なお、上限値は特に制限されないが、一般に10以下が好ましい。上記硬化膜は、遮光膜として好ましく用いることができる。
なお、本明細書において、光学濃度とは、実施例に記載された方法により測定した光学濃度を意図する。また、本明細書において、400~1200nmの波長領域における膜厚1.0μmあたりの光学濃度が、3.5超とは、波長400~1200nmの全域において、膜厚1.0μmあたりの光学濃度が3.5超であることを意図する。
また、上記硬化膜は、表面凹凸構造を有することが好ましい。そうすることで、遮光層の反射率を低減することができる。遮光層そのものの表面に凹凸構造を有するものであっても、遮光層上に別の層を設けて凹凸構造を付与しても良い。表面凹凸構造の形状は特に限定されないが、表面粗さが0.55μm以上1.5μm以下の範囲であることが好ましい。
遮光層の反射率は、5%以下であることが好ましく、3%以下であることがより好ましく、2%以下であることが特に好ましい。 [Curing film]
・ OD (Optical Density)
The cured film preferably has an optical density (OD: Optical Density) of more than 3.5 in a wavelength region of 400 to 1200 nm in a wavelength region of 400 to 1200 nm in terms of having more excellent light shielding properties. More than .7 is more preferable, more than 4.0 is more preferable, and more than 4.2 is particularly preferable. The upper limit is not particularly limited, but is generally preferably 10 or less. The cured film can be preferably used as a light shielding film.
In addition, in this specification, an optical density intends the optical density measured by the method described in the Example. Further, in this specification, the optical density per film thickness of 1.0 μm in the wavelength region of 400 to 1200 nm is greater than 3.5. The optical density per 1.0 μm of film thickness in the entire wavelength range of 400 to 1200 nm is Intended to be greater than 3.5.
Moreover, it is preferable that the said cured film has a surface uneven structure. By doing so, the reflectance of a light shielding layer can be reduced. Even if the surface of the light shielding layer itself has a concavo-convex structure, another layer may be provided on the light shielding layer to provide the concavo-convex structure. The shape of the surface concavo-convex structure is not particularly limited, but the surface roughness is preferably in the range of 0.55 μm to 1.5 μm.
The reflectance of the light shielding layer is preferably 5% or less, more preferably 3% or less, and particularly preferably 2% or less.
本発明の実施形態に係る固体撮像装置、及び、固体撮像素子は、上記硬化膜を含有する。固体撮像素子が硬化膜を含有する形態としては特に制限されず、例えば、基板上に、固体撮像素子(CCDイメージセンサ、CMOSイメージセンサ等)の受光エリアを構成する複数のフォトダイオード及びポリシリコン等からなる受光素子を有し、支持体の受光素子形成面側(例えば、受光部以外の部分及び/又は色調整用画素等)又は該形成面の反対側に本発明の硬化膜を備えて構成したものが挙げられる。
固体撮像装置は、上記固体撮像素子を含有する。 [Solid-state imaging device and solid-state imaging device]
A solid-state imaging device and a solid-state imaging device according to an embodiment of the present invention contain the cured film. The form in which the solid-state imaging device contains a cured film is not particularly limited. For example, a plurality of photodiodes, polysilicon, and the like that form a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) on a substrate And comprising the cured film of the present invention on the side of the support where the light receiving element is formed (for example, the portion other than the light receiving portion and / or the color adjustment pixel) or on the opposite side of the forming surface. The thing which was done is mentioned.
The solid-state imaging device contains the solid-state imaging element.
図1に示すように、固体撮像装置100は、矩形状の固体撮像素子101と、固体撮像素子101の上方に保持され、この固体撮像素子101を封止する透明なカバーガラス103とを備えている。更に、このカバーガラス103上には、スペーサー104を介してレンズ層111が重ねて設けられている。レンズ層111は、支持体113とレンズ材112とで構成されている。レンズ層111は、支持体113とレンズ材112とが一体成形された構成でもよい。レンズ層111の周縁領域に迷光が入射すると光の拡散によりレンズ材112での集光の効果が弱くなり、撮像部102に届く光が低減する。また、迷光によるノイズの発生も生じる。そのため、このレンズ層111の周縁領域は、硬化膜114が設けられて遮光されている。本発明の実施形態に係る硬化膜は上記硬化膜114としても用いることができる。 Configuration examples of the solid-state imaging device and the solid-state imaging device will be described with reference to FIGS. In FIG. 1 and FIG. 2, in order to clarify each part, the ratio of the thickness and / or width is disregarded and partly exaggerated.
As shown in FIG. 1, the solid-
硬化膜212上には、BPSG(borophospho silicate glass)からなる絶縁膜213、P-SiNからなる絶縁膜(パシベーション膜)214、透明樹脂等からなる平坦化膜215からなる透明な中間層が設けられている。カラーフィルタ202は、中間層上に形成されている。 A cured
On the cured
ブラックマトリクスは、本発明の実施形態に係る硬化膜を含有する。ブラックマトリクスは、カラーフィルタ、固体撮像素子、及び、液晶表示装置に含有されることがある。
ブラックマトリクスとしては、上記で既に説明したもの;液晶表示装置等の表示装置の周縁部に設けられた黒色の縁;赤、青、及び、緑の画素間の格子状、及び/又は、ストライプ状の黒色の部分;TFT(thin film transistor)遮光のためのドット状、及び/又は、線状の黒色パターン;等が挙げられる。このブラックマトリクスの定義については、例えば、菅野泰平著、「液晶ディスプレイ製造装置用語辞典」、第2版、日刊工業新聞社、1996年、p.64に記載がある。
ブラックマトリクスは表示コントラストを向上させるため、また薄膜トランジスタ(TFT)を用いたアクティブマトリクス駆動方式の液晶表示装置の場合には光の電流リークによる画質低下を防止するため、高い遮光性(光学濃度ODで3以上)を有することが好ましい。 [Black matrix]
A black matrix contains the cured film which concerns on embodiment of this invention. The black matrix may be contained in a color filter, a solid-state image sensor, and a liquid crystal display device.
As the black matrix, those already described above; a black edge provided at the periphery of a display device such as a liquid crystal display device; a lattice shape between red, blue, and green pixels, and / or a stripe shape A black portion of the TFT; a dot-like and / or a linear black pattern for shielding a thin film transistor (TFT); For the definition of this black matrix, see Taihei Kanno, “Liquid Crystal Display Manufacturing Dictionary”, 2nd edition, Nikkan Kogyo Shimbun, 1996, p. 64.
The black matrix improves the display contrast, and in the case of an active matrix liquid crystal display device using a thin film transistor (TFT), in order to prevent deterioration in image quality due to light current leakage, a high light shielding property (with an optical density OD). 3 or more).
本発明の実施形態に係るカラーフィルタは、硬化膜を含有する。
カラーフィルタが硬化膜を含有する形態としては、特に制限されないが、基板と、上記ブラックマトリクスと、を備えるカラーフィルタが挙げられる。すなわち、基板上に形成された上記ブラックマトリクスの開口部に形成された赤色、緑色、及び、青色の着色画素と、を備えるカラーフィルタが例示できる。 [Color filter]
The color filter according to the embodiment of the present invention contains a cured film.
The form in which the color filter contains a cured film is not particularly limited, and examples thereof include a color filter including a substrate and the black matrix. That is, a color filter including red, green, and blue colored pixels formed in the openings of the black matrix formed on the substrate can be exemplified.
まず、基板上に形成されたパターン状のブラックマトリクスの開口部に、カラーフィルタの各着色画素に対応する着色剤を含有した樹脂組成物の塗膜(樹脂組成物層)を形成する。なお、各色用樹脂組成物としては特に制限されず、公知の樹脂組成物を用いることができるが、本発明の実施形態に係る組成物において、チタン窒化物含有粒子を、各画素に対応した着色剤に置き換えたものを用いてもよい。
次に、樹脂組成物層に対して、ブラックマトリクスの開口部に対応したパターンを有するフォトマスクを介して露光する。次いで、現像処理により未露光部を除去した後、ベークすることでブラックマトリクスの開口部に着色画素を形成することができる。一連の操作を、例えば、赤色、緑色、及び、青色顔料を含有した各色用樹脂組成物を用いて行うことにより、赤色、緑色、及び、青色画素を有するカラーフィルタを製造することができる。 A color filter containing a black matrix (cured film) can be produced, for example, by the following method.
First, a coating film (resin composition layer) of a resin composition containing a colorant corresponding to each colored pixel of a color filter is formed in an opening of a patterned black matrix formed on a substrate. The resin composition for each color is not particularly limited, and a known resin composition can be used. In the composition according to the embodiment of the present invention, the titanium nitride-containing particles are colored corresponding to each pixel. What was replaced with the agent may be used.
Next, it exposes with respect to the resin composition layer through the photomask which has a pattern corresponding to the opening part of a black matrix. Next, after removing the unexposed portions by development processing, the colored pixels can be formed in the openings of the black matrix by baking. For example, a color filter having red, green, and blue pixels can be manufactured by performing a series of operations using a resin composition for each color that contains red, green, and blue pigments.
本発明の実施形態に係る液晶表示装置は、硬化膜を含有する。液晶表示装置が硬化膜を含有する形態としては特に制限されないが、すでに説明したブラックマトリクス(硬化膜)を含有するカラーフィルタを含有する形態が挙げられる。 [Liquid Crystal Display]
The liquid crystal display device according to the embodiment of the present invention contains a cured film. The form in which the liquid crystal display device contains a cured film is not particularly limited, but examples include a form containing a color filter containing the black matrix (cured film) already described.
本発明の実施形態に係る赤外線センサは、上記硬化膜を含有する。
上記実施形態に係る赤外線センサについて、図3を用いて説明する。図3に示す赤外線センサ300において、図番310は、固体撮像素子である。
固体撮像素子310上に設けられている撮像領域は、赤外線吸収フィルタ311と本発明の実施形態に係るカラーフィルタ312とを組み合せて構成されている。
赤外線吸収フィルタ311は、可視光領域の光(例えば、波長400~700nmの光)を透過し、赤外領域の光(例えば、波長800~1300nmの光、好ましくは波長900~1200nmの光、更に好ましくは波長900~1000nmの光)を遮蔽する膜であり、着色剤として赤外線吸収剤(赤外線吸収剤の形態としては既に説明したとおりである。)を含有する硬化膜を用いることができる。
カラーフィルタ312は、可視光領域における特定波長の光を透過及び吸収する画素が形成されたカラーフィルタであって、例えば、赤色(R)、緑色(G)、青色(B)の画素が形成されたカラーフィルタ等が用いられ、その形態は既に説明したとおりである。 赤外線透過フィルタ313と固体撮像素子310との間には、赤外線透過フィルタ313を透過した波長の光を透過させることができる樹脂膜314(例えば、透明樹脂膜など)が配置されている。
赤外線透過フィルタ313は、可視光線遮蔽性を有し、かつ、特定波長の赤外線を透過させるフィルタであって、可視光領域の光を吸収する着色剤(例えば、ペリレン化合物、及び/又は、ビスベンゾフラノン化合物等)と、赤外線吸収剤(例えば、ピロロピロール化合物、フタロシアニン化合物、ナフタロシアニン化合物、及び、ポリメチン化合物等)と、を含有する、本発明の実施形態に係る硬化膜を用いることができる。赤外線透過フィルタ313は、例えば、波長400~830nmの光を遮光し、波長900~1300nmの光を透過させることが好ましい。
カラーフィルタ312及び赤外線透過フィルタ313の入射光hν側には、マイクロレンズ315が配置されている。マイクロレンズ315を覆うように平坦化膜316が形成されている。
図3に示す実施形態では、樹脂膜314が配置されているが、樹脂膜314に代えて赤外線透過フィルタ313を形成してもよい。すなわち、固体撮像素子310上に、赤外線透過フィルタ313を形成してもよい。
また、図3に示す実施形態では、カラーフィルタ312の膜厚と、赤外線透過フィルタ313の膜厚が同一であるが、両者の膜厚は異なっていてもよい。
また、図3に示す実施形態では、カラーフィルタ312が、赤外線吸収フィルタ311よりも入射光hν側に設けられているが、赤外線吸収フィルタ311と、カラーフィルタ312との順序を入れ替えて、赤外線吸収フィルタ311を、カラーフィルタ312よりも入射光hν側に設けてもよい。
また、図3に示す実施形態では、赤外線吸収フィルタ311とカラーフィルタ312は隣接して積層しているが、両フィルタは必ずしも隣接している必要はなく、間に他の層が設けられていても良い。本発明の実施形態に係る硬化膜は、赤外線吸収フィルタ311の表面の端部や側面などの遮光膜として用いることができるほか、赤外線センサの装置内壁に用いることで、感度を向上させることができる。
この赤外線センサによれば、画像情報を同時に取り込むことができるため、動きを検知する対象を認識したモーションセンシングなどが可能である。更には、距離情報を取得できるため、3D情報を含んだ画像の撮影等も可能である。 [Infrared sensor]
The infrared sensor which concerns on embodiment of this invention contains the said cured film.
The infrared sensor which concerns on the said embodiment is demonstrated using FIG. In the
The imaging region provided on the solid-
The
The
The
A
In the embodiment shown in FIG. 3, the
In the embodiment shown in FIG. 3, the film thickness of the
In the embodiment shown in FIG. 3, the
In the embodiment shown in FIG. 3, the
According to this infrared sensor, since image information can be captured simultaneously, motion sensing or the like that recognizes a target whose motion is to be detected is possible. Furthermore, since distance information can be acquired, an image including 3D information can be taken.
上記固体撮像装置は、レンズ光学系と、固体撮像素子と、赤外発光ダイオード等を含有する。なお、固体撮像装置の各構成については、特開2011-233983号公報の段落0032~0036を参酌することができ、この内容は本明細書に組み込まれる。 Next, a solid-state imaging device to which the infrared sensor is applied will be described.
The solid-state imaging device includes a lens optical system, a solid-state imaging device, an infrared light emitting diode, and the like. As for each configuration of the solid-state imaging device, paragraphs 0032 to 0036 of JP 2011-233983 A can be referred to, and the contents thereof are incorporated in this specification.
本発明の実施形態に係る近赤外線センサについて説明する。
本発明の実施形態に係る近赤外線センサは、既に説明した赤外線センサの赤外線吸収フィルタを近赤外線吸収フィルタに置き換えたものである。
近赤外線吸収フィルタは、波長700nm以上900nm未満に極大吸収波長を有する近赤外線吸収物質を含有し、近赤外線吸収組成物を用いて形成することができる。極大吸収波長は、後述する赤外LED(赤外発光ダイオード)の発光波長とほぼ同じであることが好ましく、それらの差が20nm以内であることが好ましく、10nm以内であることがより好ましい。上記近赤外線吸収物質としては、ピロロピロール化合物が好ましく、特開2015-200878号公報の一般式(1)で表される化合物がより好ましい。 [Near infrared sensor]
A near-infrared sensor according to an embodiment of the present invention will be described.
The near-infrared sensor according to the embodiment of the present invention is obtained by replacing the infrared absorption filter of the infrared sensor already described with a near-infrared absorption filter.
The near-infrared absorbing filter contains a near-infrared absorbing material having a maximum absorption wavelength at a wavelength of 700 nm or more and less than 900 nm, and can be formed using a near-infrared absorbing composition. The maximum absorption wavelength is preferably substantially the same as the emission wavelength of an infrared LED (infrared light emitting diode) described later, and the difference between them is preferably within 20 nm, more preferably within 10 nm. As the near-infrared absorbing substance, a pyrrolopyrrole compound is preferable, and a compound represented by the general formula (1) in JP-A No. 2015-200878 is more preferable.
本発明の実施形態に係る近接センサについて説明する。
本発明の実施形態に係る近接センサとしては、上記硬化膜を含有していれば特に制限されず、例えば特開2008-83675号公報、及び、特開2015-225423に記載の近接センサが挙げられる。 [Proximity sensor]
A proximity sensor according to an embodiment of the present invention will be described.
The proximity sensor according to the embodiment of the present invention is not particularly limited as long as it contains the cured film, and examples thereof include proximity sensors described in JP-A-2008-83675 and JP-A-2015-225423. .
マイクロLED及びマイクロOLEDの例としては、特表2015-500562号及び特表2014-533890に記載されたものが挙げられる。 The cured film can also be used for applications such as micro LED (Light Emitting Diode) and micro OLED (Organic Light Emitting Diode). The cured film is suitable for members that provide a light shielding function or an antireflection function, in addition to optical filters and optical films used in micro LEDs and micro OLEDs.
Examples of the micro LED and the micro OLED include those described in JP-T-2015-500562 and JP-T-2014-533890.
量子ドットディスプレイの例としては、米国特許出願公開第2013/0335677号、米国特許出願公開第2014/0036536号、米国特許出願公開第2014/0036203号、及び、米国特許出願公開第2014/0035960号に記載されたものが挙げられる。 The cured film is suitable as an optical and optical film used in quantum dot displays. Moreover, it is suitable as a member which provides a light shielding function and an antireflection function.
Examples of quantum dot displays include US Patent Application Publication No. 2013/0335677, US Patent Application Publication No. 2014/0036536, US Patent Application Publication No. 2014/0036203, and US Patent Application Publication No. 2014/0035960. What has been described.
以下の方法により、チタン窒化物含有粒子TiN-1を作製した。
特開2005-343784号公報の段落0042、及び、図1に記載された装置を用いて作製した。具体的には、上記公報の図1における、放電容器1をステンレス製の真空チャンバ(福伸工業株式会社製)とした装置(以下、「ナノ粒子製造装置」という。)を用いてチタン窒化物含有粒子を作製した。まず、排気ポンプにより真空チャンバ内の空気を排気した。その後、真空チャンバに、ヘリウム(He)ガス(純度99.99%)を600Torr(79.99kPa)の圧力となるまで供給した。 [Production of titanium nitride-containing particles TiN-1]
Titanium nitride-containing particles TiN-1 were produced by the following method.
It was produced using the apparatus described in JP 2005-343784 A, paragraph 0042 and FIG. Specifically, titanium nitride using an apparatus (hereinafter referred to as “nanoparticle manufacturing apparatus”) in which the discharge vessel 1 in FIG. 1 of the above publication is a stainless steel vacuum chamber (Fukushin Industries Co., Ltd.) is used. Containing particles were produced. First, the air in the vacuum chamber was exhausted by an exhaust pump. Thereafter, helium (He) gas (purity 99.99%) was supplied to the vacuum chamber until the pressure reached 600 Torr (79.99 kPa).
中空構造の放電電極は、原料供給装置と接続されており、放電電極の中空部分から原料ガスを真空チャンバ内へと供給できるようにした。 As the discharge electrode of the nanoparticle production apparatus, tungsten formed into a hollow rod having a length of 500 mm, a diameter of 12 mm, and a hollow diameter of 6 mm was used. The arrangement of the discharge electrodes was the same as that shown in FIG. 1 of JP-A-2005-343784. Specifically, 12 discharge electrodes were arranged in two stages of 6 each. The distance between the upper stage and the lower stage was about 160 mm.
The discharge electrode having a hollow structure is connected to a raw material supply device so that the raw material gas can be supplied from the hollow portion of the discharge electrode into the vacuum chamber.
静置後の粒子を、減圧オーブンVAC-101P(エスペック製)を用いて200℃で2時間加熱して、チタン窒化物含有粒子TiN-1を得た。なお、加熱中の減圧オーブンの内圧は1.0×103Paとした。 (Heating process)
The particles after standing were heated at 200 ° C. for 2 hours using a vacuum oven VAC-101P (manufactured by ESPEC) to obtain titanium nitride-containing particles TiN-1. The internal pressure of the vacuum oven during heating was 1.0 × 10 3 Pa.
得られたチタン窒化物含有粒子TiN-1について、ICP(Inductively Coupled Plasma)発光分光分析法によって、チタン(Ti)原子(酸分解、又は、アルカリ融解による分解後に測定)の含有量(質量%)を測定した。なお、ICP発光分光分析法には、セイコーインスツルメンツ社製のICP発光分光分析装置「SPS3000」(商品名)を用いた。
また、チタン窒化物含有粒子TiN-1中の塩素原子の含有量は、チタン窒化物含有粒子を助剤とともに1000℃で燃焼し、発生させた塩素ガスを吸収液に捕集し、イオンクロマトグラフィー装置を用いて分析した。
また、チタン窒化物含有粒子TiN-1中における窒素原子(N)、及び、酸素原子(O)の含有量(質量%)については、堀場製作所製の酸素・窒素分析装置「EMGA-620W/C」(商品名)を用いて測定し、不活性ガス融解-熱伝導度法により算出した。
上記の結果は、Ti、N、O、及び、Clの含有量(質量%)として、表1に示した。 (Measurement of Ti, N, O, and Cl contents in titanium nitride-containing particles TiN-1)
Content (mass%) of titanium (Ti) atoms (measured after acid decomposition or decomposition by alkali melting) of the obtained titanium nitride-containing particles TiN-1 by ICP (Inductively Coupled Plasma) emission spectrometry Was measured. For the ICP emission spectroscopic analysis, an ICP emission spectroscopic analyzer “SPS3000” (trade name) manufactured by Seiko Instruments Inc. was used.
The content of chlorine atoms in the titanium nitride-containing particles TiN-1 is determined by burning the titanium nitride-containing particles together with an auxiliary agent at 1000 ° C., collecting the generated chlorine gas in an absorption liquid, and performing ion chromatography. Analyzed using the instrument.
Further, regarding the content (mass%) of nitrogen atoms (N) and oxygen atoms (O) in the titanium nitride-containing particles TiN-1, the oxygen / nitrogen analyzer “EMGA-620W / C” manufactured by HORIBA, Ltd. (Trade name) and calculated by the inert gas melting-thermal conductivity method.
The above results are shown in Table 1 as the contents (mass%) of Ti, N, O, and Cl.
各原料ガスの流量の体積比率が表1に記載したとおりになるよう、導入するガスの量を調整した以外はチタン窒化物含有粒子TiN-1の作製方法と同様にして、チタン窒化物含有粒子TiN-2~TiN-13を作製した。
作製した各チタン窒化物含有粒子については、上記と同様の方法により、Ti、N、O、及び、Clの含有量を測定した。結果を表1にまとめて示した。
なお、表1中における各原料ガスの流量の体積比(体積%)は、標準状態換算である。 [Production of titanium nitride-containing particles TiN-2 to TiN-13]
Titanium nitride-containing particles were made in the same manner as the titanium nitride-containing particles TiN-1 except that the amount of gas introduced was adjusted so that the volume ratio of the flow rates of the respective raw material gases was as shown in Table 1. TiN-2 to TiN-13 were produced.
About each produced titanium nitride containing particle | grain, content of Ti, N, O, and Cl was measured by the method similar to the above. The results are summarized in Table 1.
In addition, the volume ratio (volume%) of the flow volume of each raw material gas in Table 1 is standard state conversion.
各原料ガスの流量の体積比率が表1に記載したとおりになるよう、導入するガスの量を調整し、かつ、上記加熱工程を経なかったことを除いては、チタン窒化物含有粒子TiN-1と同様にして、チタン窒化物含有粒子TiN-Cを作製した。
作製したチタン窒化物含有粒子TiN-Cについては、上記と同様の方法により、Ti、N、O、及び、Clの含有量を測定した。結果を表1に示した。 [Production of titanium nitride-containing particles TiN-C]
Except for adjusting the amount of gas to be introduced so that the volume ratio of the flow rate of each raw material gas is as shown in Table 1 and not having undergone the above heating step, the titanium nitride-containing particles TiN- In the same manner as in Example 1, titanium nitride-containing particles TiN—C were produced.
Regarding the produced titanium nitride-containing particles TiN—C, the contents of Ti, N, O, and Cl were measured by the same method as described above. The results are shown in Table 1.
各チタン窒化物含有粒子を20g秤量し、真空乾燥機ADP200(ヤマト科学製)を用いて圧力5kPa、温度100℃にて2時間乾燥した後、乾式密度計アキュピックII1340(島津製作所)を用いて、各チタン窒化物含有粒子の密度を評価した。なお、密度の測定条件は以下のとおりである。結果は、表2及び表3に示した。
測定ガス : ヘリウムセル
サイズ : 100cc
フローパージ : 10分
目標圧力 : 17.5PSI(pound-force per square inch、1.0PSIは6894.76Paに対応する。)
測定回数 : 15回
(このうち、最後の3回(第13回~第15回)の測定で得られた値の算術平均値により、密度を評価した。
<0239>
20 g of each titanium nitride-containing particle was weighed and dried for 2 hours at a pressure of 5 kPa and a temperature of 100 ° C. using a vacuum drier ADP200 (manufactured by Yamato Kagaku). The density of each titanium nitride-containing particle was evaluated. The density measurement conditions are as follows. The results are shown in Tables 2 and 3.
Measurement gas: Helium cell size: 100cc
Flow purge: 10 minutes Target pressure: 17.5 PSI (pound-force per square inch, 1.0 PSI corresponds to 6894.76 Pa)
Number of measurements: The density was evaluated by the arithmetic average value of the values obtained by the last three measurements (13th to 15th of these measurements).
<0239>
<チタン窒化物含有粒子分散液1の調製>
まず、チタン窒化物含有粒子TiN-1、分散剤D(分散剤Dの構造については、後述する。)及び、有機溶剤(表2に記載した、PGMEA(プロピレングリコール1-モノメチルエーテル2-アセタート)/シクロペンタノン/酢酸ブチル=30/20/22(質量比))を、攪拌機(IKA社製EUROSTAR)によって15分間混合し、分散物を得た。次に、得られた分散物に対して、(株)シンマルエンタープライゼス製のNPM-Pilotを使用して下記条件にて分散処理を行い、チタン窒化物含有粒子分散液1を得た。なお、チタン窒化物含有粒子に対する分散剤の比率(D/P)は、表2に記載したとおりである。
(分散条件)
・ビーズ径:φ0.05mm、(ニッカトー製ジルコニアビーズ、YTZ)
・ビーズ充填率:65体積%
・ミル周速:10m/sec
・セパレータ周速:13m/sec
・分散処理する混合液量:15kg
・循環流量(ポンプ供給量):90kg/hour
・処理液温度:19~21℃
・冷却水:水
・処理時間:22時間 [Example 1: Preparation of Composition 1]
<Preparation of titanium nitride-containing particle dispersion 1>
First, titanium nitride-containing particles TiN-1, a dispersant D (the structure of the dispersant D will be described later) and an organic solvent (PGMEA (propylene glycol 1-monomethyl ether 2-acetate) described in Table 2) / Cyclopentanone / butyl acetate = 30/20/22 (mass ratio)) was mixed with a stirrer (EUROSTAR manufactured by IKA) for 15 minutes to obtain a dispersion. Next, the obtained dispersion was subjected to a dispersion treatment under the following conditions using NPM-Pilot manufactured by Shinmaru Enterprises Co., Ltd. to obtain a titanium nitride-containing particle dispersion 1. The ratio of the dispersant to the titanium nitride-containing particles (D / P) is as described in Table 2.
(Distribution condition)
・ Bead diameter: 0.05mm, (Nikkato zirconia beads, YTZ)
・ Bead filling rate: 65% by volume
・ Mill peripheral speed: 10m / sec
・ Separator peripheral speed: 13m / sec
・ Amount of liquid mixture to be dispersed: 15kg
・ Circulating flow rate (pump supply amount): 90 kg / hour
・ Processing liquid temperature: 19-21 ℃
・ Cooling water: Water ・ Processing time: 22 hours
次に、上記チタン窒化物含有粒子分散液1、アルカリ可溶性樹脂、重合性化合物、界面活性剤、重合禁止剤、及び、有機溶剤(表2に記載した、PGMEA(プロピレングリコール1-モノメチルエーテル2-アセタート)/シクロペンタノン/酢酸ブチル=30/20/22(質量比))を混合し、攪拌して、組成物1を得た。
なお、表2中の含有量欄は、各成分の質量部を表す。 <Preparation of Composition 1>
Next, the titanium nitride-containing particle dispersion 1, alkali-soluble resin, polymerizable compound, surfactant, polymerization inhibitor, and organic solvent (PGMEA (propylene glycol 1-monomethyl ether 2- Acetate) / cyclopentanone / butyl acetate = 30/20/22 (mass ratio)) were mixed and stirred to obtain composition 1.
In addition, the content column in Table 2 represents parts by mass of each component.
各成分の種類、及び、含有量が表2に記載したとおりとなるよう調整した以外は、実施例1と同様にして、各実施例、及び、各比較例の組成物を得た。
なお、表2における、各成分の含有量の数値は質量%を意図する。 [Compositions of Other Examples and Comparative Examples]
Except having adjusted so that the kind and content of each component may become as having described in Table 2, it carried out similarly to Example 1, and obtained the composition of each Example and each comparative example.
In addition, the numerical value of content of each component in Table 2 intends mass%.
・樹脂A:アクリキュアRD-F8(商品名、日本触媒社製)を用いた。以下に樹脂Aの構造を示す。
Resin A: Acryl Cure RD-F8 (trade name, manufactured by Nippon Shokubai Co., Ltd.) was used. The structure of resin A is shown below.
・M1:日本化薬社製、商品名「KAYARAD DPHA」、下記式参照
・M2:日本化薬社製、商品名「KAYARAD RP-1040」、下記式参照
・ M1: Nippon Kayaku Co., Ltd., trade name “KAYARAD DPHA”, see formula below ・ M2: Nippon Kayaku Co., Ltd., trade name “KAYARAD RP-1040”, see formula below
・OXE-01:IRGACURE OXE01(商品名、BASFジャパン社製、光重合開始剤に該当するオキシム化合物。)
・OXE-02:IRGACURE OXE02(商品名、BASFジャパン社製、光重合開始剤に該当するオキシム化合物。)
・I-1:下記式(I-1)の重合開始剤(光重合開始剤に該当するオキシム化合物。)
・I-2:下記式(I-2)の重合開始剤(商品名「B-CIM」、保土ヶ谷化学工業社製、光重合開始剤に該当する。)
・I-3:下記式(I-3)の重合開始剤(光重合開始剤に該当する)
・I-4:下記式(I-4)の重合開始剤(光重合開始剤に該当するオキシム化合物。)
・I-5:下記式(I-5)の重合開始剤(光重合開始剤に該当するオキシム化合物。)
・NCI-831:アデカアークルズ NCI-831(商品名、アデカ社製、光重合開始剤に該当するオキシム化合物。)
・N-1919:アデカオプトマーN-1919(商品名、アデカ社製、光重合開始剤に該当するオキシム化合物。)
OXE-01: IRGACURE OXE01 (trade name, manufactured by BASF Japan, an oxime compound corresponding to a photopolymerization initiator)
OXE-02: IRGACURE OXE02 (trade name, manufactured by BASF Japan, an oxime compound corresponding to a photopolymerization initiator)
I-1: polymerization initiator represented by the following formula (I-1) (an oxime compound corresponding to a photopolymerization initiator)
I-2: polymerization initiator represented by the following formula (I-2) (trade name “B-CIM”, manufactured by Hodogaya Chemical Co., Ltd., corresponding to a photopolymerization initiator)
I-3: a polymerization initiator of the following formula (I-3) (corresponding to a photopolymerization initiator)
I-4: a polymerization initiator of the following formula (I-4) (an oxime compound corresponding to a photopolymerization initiator)
I-5: polymerization initiator of the following formula (I-5) (an oxime compound corresponding to a photopolymerization initiator)
NCI-831: Adeka Arcles NCI-831 (trade name, manufactured by Adeka, an oxime compound corresponding to a photopolymerization initiator)
N-1919: Adekaoptomer N-1919 (trade name, manufactured by Adeka, an oxime compound corresponding to a photopolymerization initiator)
・PGMEA:プロピレングリコール1-モノメチルエーテル2-アセタート
・シクロペンタノン
・酢酸ブチル (Organic solvent)
・ PGMEA: Propylene glycol 1-monomethyl ether 2-acetate ・ Cyclopentanone ・ Butyl acetate
下記式により表される界面活性剤(重量平均分子量(Mw)=15311)
ただし、下記式において、式中(A)及び(B)で表される構造単位はそれぞれ62モル%、38モル%である。式(B)で表される構造単位中、aは、b、cは、それぞれ、a+c=14、b=17の関係を満たす。 (Surfactant)
Surfactant represented by the following formula (weight average molecular weight (Mw) = 15311)
However, in the following formula, the structural units represented by the formulas (A) and (B) are 62 mol% and 38 mol%, respectively. In the structural unit represented by the formula (B), a, b, and c satisfy the relationships of a + c = 14 and b = 17, respectively.
p-メトキシフェノール <Polymerization inhibitor>
p-methoxyphenol
各組成物を以下の方法により評価した。各評価結果は、表2及び表3に示した。 [Evaluation]
Each composition was evaluated by the following methods. The evaluation results are shown in Tables 2 and 3.
8インチのシリコンウェハ上に、各組成物スピンコートして、組成物層を形成した。組成物層の厚みは、得られる硬化膜の膜厚が0.3μmとなるように、スピンコートの回転数を制御して調整した。なお、使用した各組成物は、得られる硬化膜の膜厚を考慮して、適宜PGMEA(プロピレングリコール1-モノメチルエーテル2-アセタート)により希釈した。
100℃のホットプレートに、シリコンウェハの、組成物層を形成した側とは反対側の面を向けて載置し、組成物層を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)を使用して、2cm×2cmの領域が露光されるレチクルを通して、365nmの波長の光、および、500mJ/cm2の露光量で組成物層を露光した。その後、露光された組成物層が形成されたシリコンウェハを、スピン・シャワー現像機(DW-30型、(株)ケミトロニクス製)の水平回転テーブル上に載置し、CD-2000(富士フイルムエレクトロニクスマテリアルズ社製、有機アルカリ現像液)を用いて23℃で60秒間パドル現像した。次いで、パドル現像後のシリコンウェハを、真空チャック方式で上記水平回転テーブルに固定し、回転装置によって上記シリコンウェハを回転数50rpmで回転させつつ、その回転中心の上方より純水を噴出ノズルからシャワー状に供給してリンス処理した。これにより、基板上に2cm×2cmのパターン状の硬化膜が形成されたシリコンウェハを得た。得られたシリコンウェハをクリーンオーブン(ハイテンプクリーンオーブンCLH-300S、光洋サーモシステム製)を用いて220℃で1時間加熱した。
得られた硬化膜について、分光エリプソメトリー(M-2000XI-210:J.A.Woollam社製分光エリプソメトリー)により波長400~1200nmにおけるp偏光(平行)とs偏光(垂直)の位相差Δと振幅比Ψのスペクトルを得た。得られた(Δ,Ψ)スペクトルに対し、Bruggemanの有効媒質近似 (EMA;Effective medium approximation)モデルを用いてFitting解析を行い、膜中に含有される真のチタン窒化物含有粒子の誘電率を求めた(EMAモデルで用いたチタン窒化物含有粒子の含有量は、処方値を用いたが、すでに説明した方法により、硬化膜中のチタン窒化物含有粒子を分離し、硬化膜中のチタン窒化物含有粒子の含有量を実測してもよい。)。得られた複素誘電率から、以下の基準の複素誘電率の実数部の評価を行い、表2に示した。
A:複素誘電率の実数部の最小値が-0.5以下だった。
B:複素誘電率の実数部の最小値が-0.5超、0未満だった。
C:複素誘電率の実数部の最小値が0以上だった。 [Complex dielectric constant of titanium nitride-containing particles]
Each composition was spin-coated on an 8-inch silicon wafer to form a composition layer. The thickness of the composition layer was adjusted by controlling the rotation speed of the spin coat so that the thickness of the resulting cured film was 0.3 μm. Each composition used was appropriately diluted with PGMEA (propylene glycol 1-monomethyl ether 2-acetate) in consideration of the thickness of the resulting cured film.
The silicon wafer was placed on a hot plate at 100 ° C. with the surface opposite to the side on which the composition layer was formed facing, and the composition layer was heated for 2 minutes. Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Co., Ltd.), through a reticle on which an area of 2 cm × 2 cm is exposed, at a wavelength of 365 nm and an exposure dose of 500 mJ / cm 2 The composition layer was exposed. Thereafter, the silicon wafer on which the exposed composition layer was formed was placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics Co., Ltd.), and CD-2000 (Fuji Film). Paddle development was performed at 23 ° C. for 60 seconds using an organic alkali developer (manufactured by Electronics Materials). Next, the silicon wafer after the paddle development is fixed to the horizontal rotary table by a vacuum chuck method, and the silicon wafer is rotated at a rotation speed of 50 rpm by a rotating device, and pure water is showered from the jet nozzle from above the rotation center. And then rinsed. As a result, a silicon wafer having a 2 cm × 2 cm patterned cured film formed on the substrate was obtained. The obtained silicon wafer was heated at 220 ° C. for 1 hour using a clean oven (High Temp Clean Oven CLH-300S, manufactured by Koyo Thermo System).
The obtained cured film was analyzed by spectroscopic ellipsometry (M-2000XI-210: spectroscopic ellipsometry manufactured by JA Woollam Co.) with a phase difference Δ between p-polarized light (parallel) and s-polarized light (vertical) at a wavelength of 400 to 1200 nm. A spectrum of amplitude ratio Ψ was obtained. Fitting analysis is performed on the obtained (Δ, Ψ) spectrum using Bruggeman's effective medium approximation (EMA) model to determine the dielectric constant of the true titanium nitride-containing particles contained in the film. The content of the titanium nitride-containing particles used in the EMA model was determined using the prescribed value, but the titanium nitride-containing particles in the cured film were separated by the method already described, and the titanium nitride in the cured film was separated. The content of the product-containing particles may be measured.) From the obtained complex permittivity, the real part of the following complex permittivity was evaluated and is shown in Table 2.
A: The minimum value of the real part of the complex dielectric constant was −0.5 or less.
B: The minimum value of the real part of the complex dielectric constant was more than −0.5 and less than 0.
C: The minimum value of the real part of the complex dielectric constant was 0 or more.
表面に高さ2.0μm、線幅25μmのラインアンドスペースを有するテスト電極パターン(銅)が形成されたシリコンウェハを用意した。その電極パターン上に、得られる硬化膜の膜厚が0.3μmになるように、各組成物をスピンコートして、組成物層を得た。その後、100℃のホットプレートに、シリコンウェハの組成物層を形成した側とは反対側の面を向けて載置し、組成物層を120秒間加熱(プリベーク)した。
次いで、i線ステッパー露光装置FPA-3000i5+(Canon(株)製)を使用して、テスト電極パターン部分に硬化膜が形成されるパターンマスクを通して、365nmの波長の光、および、500mJ/cm2の露光量で組成物層を露光した。
その後、露光された組成物層を備えたシリコンウェハ基板を、スピン・シャワー現像機(DW-30型、(株)ケミトロニクス製)の水平回転テーブル上に載置し、CD-2000(富士フイルムエレクトロニクスマテリアルズ社製、有機アルカリ現像液)を用いて23℃で60秒間パドル現像した。
次いで、パドル現像後のシリコンウェハを、真空チャック方式で上記水平回転テーブルに固定し、回転装置によってシリコンウェハを回転数50rpmで回転させつつ、その回転中心の上方より純水を噴出ノズルからシャワー状に供給してリンス処理した。その後220℃のオーブンでシリコンウェハを1時間熱処理することにより、TEG(Test Element Group)パターン付きシリコンウェハを得た。
硬化膜の電気特性は以下の方法により評価した。
マニュアルプローバー(計測器としてネットワークアナライザE5061B-3L5)を用いて、上記TEGパターンの抵抗値×静電容量=RC(resistor capacitor)値(保存前)を測定した。更に、作製したTEGパターン付きシリコンウェハを温度25℃、湿度65%RH(relative humidity)の環境下で3ヶ月保存した後、RC値(保存後)を測定した。RC値(保存前)に対する、RC値(保存後)の比(RC値(保存後)/RC値(保存前))を求め、以下の基準により評価し、表2に示した。実用上、C以上が好ましい。
A:RC値(保存後)/RC値(保存前)が1.00以上1.08未満だった。
B:RC値(保存後)/RC値(保存前)が1.08以上1.16未満だった。
C:RC値(保存後)/RC値(保存前)が1.16以上1.20未満だった。
D:RC値(保存後)/RC値(保存前)が1.20以上だった。 [Electrical properties of cured film]
A silicon wafer was prepared on which a test electrode pattern (copper) having a line and space with a height of 2.0 μm and a line width of 25 μm was formed. Each composition was spin-coated on the electrode pattern so that the film thickness of the cured film obtained was 0.3 μm to obtain a composition layer. Then, the surface opposite to the side on which the composition layer of the silicon wafer was formed was placed on a hot plate at 100 ° C., and the composition layer was heated (prebaked) for 120 seconds.
Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), light having a wavelength of 365 nm and 500 mJ / cm 2 through a pattern mask in which a cured film is formed on the test electrode pattern portion The composition layer was exposed with an exposure amount.
Thereafter, the silicon wafer substrate provided with the exposed composition layer is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics Co., Ltd.), and CD-2000 (FUJIFILM Corporation). Paddle development was performed at 23 ° C. for 60 seconds using an organic alkali developer (manufactured by Electronics Materials).
Next, the silicon wafer after the paddle development is fixed to the horizontal rotating table by a vacuum chuck method, and the silicon wafer is rotated at a rotation speed of 50 rpm by a rotating device, and pure water is sprayed from above the rotation center from a jet nozzle. And rinsed. Thereafter, the silicon wafer was heat-treated in an oven at 220 ° C. for 1 hour to obtain a silicon wafer with a TEG (Test Element Group) pattern.
The electrical properties of the cured film were evaluated by the following methods.
Using a manual prober (network analyzer E5061B-3L5 as a measuring instrument), the resistance value of the TEG pattern × capacitance = RC (resistor capacitor) value (before storage) was measured. Furthermore, the prepared TEG-patterned silicon wafer was stored for 3 months in an environment of a temperature of 25 ° C. and a humidity of 65% RH (relative humidity), and then the RC value (after storage) was measured. The ratio of RC value (after storage) to RC value (before storage) (RC value (after storage) / RC value (before storage)) was determined and evaluated according to the following criteria and shown in Table 2. Practically, C or higher is preferable.
A: RC value (after storage) / RC value (before storage) was 1.00 or more and less than 1.08.
B: RC value (after storage) / RC value (before storage) was 1.08 or more and less than 1.16.
C: RC value (after storage) / RC value (before storage) was 1.16 or more and less than 1.20.
D: RC value (after storage) / RC value (before storage) was 1.20 or more.
各組成物中の水分含有量について、カールフィッシャー法を測定原理とするMKV-710(商品名、京都電子工業社製)により測定した。結果を表2に示した。 [Moisture content in composition (water content)]
The water content in each composition was measured by MKV-710 (trade name, manufactured by Kyoto Electronics Industry Co., Ltd.) using the Karl Fischer method as a measurement principle. The results are shown in Table 2.
各組成物について、カプセルフィルターDFA(日本ポール社製、ナイロン孔径0.45μm、2inch)を用いて、ろ過性を評価した。なお、組成物16kgを0.05MPaに加圧して送液し、ろ過して、以下の基準により評価を行った。結果を表2に示した。
A:16kgすべてろ過できた。
B:10kg以上、16kg未満ろ過したところで、フィルタに詰まりが発生した。
C:5kg以上、10kg未満ろ過したところで、フィルタに詰まりが発生した。
D:5kg未満ろ過したところで、フィルタにろ過詰まりが発生した。 [Filterability of composition]
About each composition, filterability was evaluated using the capsule filter DFA (Nippon Pole company make, nylon hole diameter 0.45 micrometer, 2 inch). Note that 16 kg of the composition was pressurized to 0.05 MPa, fed, filtered, and evaluated according to the following criteria. The results are shown in Table 2.
A: All 16 kg could be filtered.
B: The filter was clogged when 10 kg or more and less than 16 kg were filtered.
C: When filtering 5 kg or more and less than 10 kg, the filter was clogged.
D: Filtration clogged in the filter when less than 5 kg was filtered.
各組成物を23℃において10日間保存した後、7℃において90日間保存した。
組成物の粘度の経時安定性は、保存前後の各組成物の粘度を比較することにより評価した。
すなわち、保存前後の各組成物の粘度をE型粘度計(東機産業社製、商品名「R85形粘度計」)を用いて回転数10rpm、23℃の条件にて測定し、以下の式から粘度の変化率(%)を算出した。結果については、以下の基準により評価した。結果を表2及び表3に示した。
(式)(粘度の変化率)=((組成物の保存後の粘度)-(組成物の保存前の粘度)/(組成物の保存前の粘度))×100(%)
A:粘度の変化率の絶対値が3.0%以内だった。
B:粘度の変化率の絶対値が3.0%超、5.0%以内だった。
C:粘度の変化率の絶対値が5.0%超、10%以内だった。
D:粘度の変化率の絶対値が10%超だった。 [Stability of viscosity of composition over time]
Each composition was stored at 23 ° C. for 10 days and then stored at 7 ° C. for 90 days.
The temporal stability of the viscosity of the composition was evaluated by comparing the viscosity of each composition before and after storage.
That is, the viscosity of each composition before and after storage was measured using an E-type viscometer (trade name “R85 type viscometer” manufactured by Toki Sangyo Co., Ltd.) under the conditions of 10 rpm and 23 ° C. From this, the rate of change in viscosity (%) was calculated. The results were evaluated according to the following criteria. The results are shown in Tables 2 and 3.
(Formula) (Viscosity change rate) = ((Viscosity after storage of composition) − (Viscosity before storage of composition) / (Viscosity before storage of composition)) × 100 (%)
A: The absolute value of the rate of change in viscosity was within 3.0%.
B: The absolute value of the rate of change in viscosity was more than 3.0% and within 5.0%.
C: The absolute value of the rate of change in viscosity was more than 5.0% and within 10%.
D: The absolute value of the rate of change in viscosity was more than 10%.
上記の〔電気特性〕の評価で作製したのと同様の方法により硬化膜(硬化膜を備えたシリコンウェハ)を作製した。上記のシリコンウェハの、組成物層の露光時にマスクされていた部分(未露光部)に対応する部分を走査型電子顕微鏡(日立ハイテクノロジーズ社製、商品名「SU8010」)を用いて、2万倍の倍率にて観察し、得られた観察像に確認される粒子状の残渣の個数をカウントし、パターニング性(現像残渣)の評価を以下の基準により行った。結果は表2、及び、表3に示した。
A:未露光部に現像残渣が観察されなかった。
B:未露光部に粒子状の現像残渣が1~49個観察された。
C:未露光部に粒子状の現像残渣が50~100個観察された。
D:未露光部に粒子状の現像残渣が101個以上観察された。 [Patternability (development residue)]
A cured film (a silicon wafer provided with a cured film) was produced by the same method as that produced in the above evaluation of [Electrical characteristics]. Using a scanning electron microscope (manufactured by Hitachi High-Technologies Corporation, trade name “SU8010”), a portion corresponding to a portion (unexposed portion) masked at the time of exposure of the composition layer of the silicon wafer was 20,000. Observation was performed at a magnification of 2, and the number of particulate residues confirmed in the obtained observation image was counted, and patterning property (development residue) was evaluated according to the following criteria. The results are shown in Tables 2 and 3.
A: No development residue was observed in the unexposed area.
B: 1 to 49 particulate development residues were observed in the unexposed areas.
C: 50 to 100 particulate development residues were observed in the unexposed areas.
D: 101 or more particulate development residues were observed in the unexposed area.
上記の〔電気特性〕の評価で作製したのと同様の方法により硬化膜(硬化膜を備えたシリコンウェハ)を作製した。上記のシリコンウェハを、90℃、湿度85%RHの環境下に1000時間曝露した。暴露後のシリコンウェハを、レーザー顕微鏡(オリンパス社製、商品名「LEXT OLS4500」)を用いて観察した。結果は表2、及び、表3に示した。
耐湿試験後の硬化膜の外観変化を観察し、以下の基準により評価した。
A:硬化膜の外観に耐湿試験前後で差異が観察されない、又は、耐湿試験後の硬化膜には凹凸差10nm以下の表面荒れが観察された。
B:耐湿試験後の硬化膜には凹凸差10nm超、50nm以下の表面荒れが観察された。
C:耐湿試験後の硬化膜には凹凸差50nm超、100nm以下の表面荒れが観察された。
D:耐湿試験後の硬化膜には凹凸差100nm超の表面荒れが観察された。 [Appearance of cured film after moisture resistance test]
A cured film (a silicon wafer provided with a cured film) was produced by the same method as that produced in the above evaluation of [Electrical characteristics]. The silicon wafer was exposed for 1000 hours in an environment of 90 ° C. and humidity of 85% RH. The exposed silicon wafer was observed using a laser microscope (manufactured by Olympus, trade name “LEXT OLS4500”). The results are shown in Tables 2 and 3.
The appearance change of the cured film after the moisture resistance test was observed and evaluated according to the following criteria.
A: No difference was observed in the appearance of the cured film before and after the moisture resistance test, or surface roughness with an unevenness difference of 10 nm or less was observed in the cured film after the moisture resistance test.
B: Surface roughness with an unevenness difference of more than 10 nm and 50 nm or less was observed in the cured film after the moisture resistance test.
C: Surface roughness was observed in the cured film after the moisture resistance test, with a difference in roughness of more than 50 nm and 100 nm or less.
D: Surface roughness with an unevenness difference of more than 100 nm was observed on the cured film after the moisture resistance test.
厚さ0.7mm,10cm角のガラス板(EagleXG,Corning)上に、乾燥膜厚が1.0μmとなるよう回転数を調整し、各組成物をスピンコートして組成物層を形成した。100℃のホットプレートに、上記ガラス板の、組成物層を形成した側とは反対側の面を向けて載置し、組成物層を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)を使用して、365nmの波長の光、および、500mJ/cm2の露光量で、組成物層を露光し、硬化膜を得た。得られた硬化膜のOD(optical density、光学濃度)を分光光度計U-4100(日立ハイテクノロジーズ社製)を用いて測定した。
波長400~1200nmにおけるODの最小値(最小OD)に基づいて、以下の基準により遮光性を評価した。結果は表2、及び、表3に示した。
AA:硬化膜の最小ODが4.2超だった。
A :硬化膜の最小ODが、4.0超、4.2以下だった。
B :硬化膜の最小ODが、3.7超、4.0以下だった。
C :硬化膜の最小ODが、3.5超、3.7以下だった。
D :硬化膜の最小ODが、3.5以下だった。 [Shading of cured film]
On a glass plate (Eagle XG, Corning) having a thickness of 0.7 mm and 10 cm square, the number of revolutions was adjusted so that the dry film thickness was 1.0 μm, and each composition was spin-coated to form a composition layer. The surface of the glass plate opposite to the side on which the composition layer was formed was placed on a hot plate at 100 ° C., and the composition layer was heated for 2 minutes. Then, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), the composition layer is exposed with light having a wavelength of 365 nm and an exposure amount of 500 mJ / cm 2 to obtain a cured film. It was. The OD (optical density, optical density) of the obtained cured film was measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation).
Based on the minimum value (minimum OD) of OD at a wavelength of 400 to 1200 nm, the light shielding property was evaluated according to the following criteria. The results are shown in Tables 2 and 3.
AA: The minimum OD of the cured film was over 4.2.
A: The minimum OD of the cured film was more than 4.0 and 4.2 or less.
B: The minimum OD of the cured film was more than 3.7 and 4.0 or less.
C: The minimum OD of the cured film was more than 3.5 and 3.7 or less.
D: The minimum OD of the cured film was 3.5 or less.
また、チタン窒化物含有粒子の密度が3.0g/cm3以上、5.0g/cm3未満である、実施例2の組成物は、実施例10(上限値超)の組成物と比較して、より優れた経時安定性を有していた。また、実施例1の組成物により得られた硬化膜は、実施例11(下限値未満)の組成物により得られた硬化膜と比較して、より優れた耐湿試験後の外観を有していた。
また、チタン窒化物含有粒子が、チタン原子、及び、窒素原子を含有し、チタン窒化物含有粒子中におけるチタン原子の含有量に対する、窒素原子の含有量の含有原子数比Xが、0を超え、1未満である、実施例2の組成物は、実施例10(上限値超)の組成物と比較して、より優れた経時安定性、及び、より優れたパターニング性を有していた。
また、上記Xが0.40を超え、0.95未満である、実施例2の組成物は、実施例12(上限値超)の組成物と比較して、より優れたパターニング性を有していた。また、実施例2の組成物は、実施例9(下限値未満)の組成物と比較して、より優れた経時安定性を有していた。
また、チタン窒化物含有粒子が、更に酸素原子を含有し、チタン窒化物含有粒子中におけるチタン原子の含有量にする、酸素原子の含有量の含有原子数比Yと、上記Xとが、X+Y<0.93の関係を満たす実施例2の組成物により得られる硬化膜は、実施例1(上限値超)の組成物により得られる硬化膜と比較して、より優れた遮光性を有していた。
チタン窒化物含有粒子が、更に塩素原子を含有し、チタン窒化物含有粒子中における塩素原子の含有量が、800~3000質量ppmである、実施例2の組成物により得られる硬化膜は、実施例8~12の組成物により得られる硬化膜と比較して、より優れた電気特性を有していた。
また、実施例17の組成物は、実施例16の組成物と比較してより優れたパターニング性を有しており、また硬化して得られる硬化膜がより優れた遮光性と電気特性を有していた。これは、分散剤Eが分散剤Cと比較して、分子内により少ない酸性基を含有しており、チタン窒化物含有粒子が凝集しにくいためと推測される。
また、実施例17の組成物は、実施例18及び実施例19の組成物と比較して、より優れたパターニング性を有していた。これは分散剤Eがグラフト鎖を含有しているためと推測される。 From the results shown in Table 2, the compositions of Examples 1 to 27 had the effects of the present invention. On the other hand, the composition of Comparative Example 1 did not have the effect of the present invention.
The composition of Example 2 in which the density of the titanium nitride-containing particles is 3.0 g / cm 3 or more and less than 5.0 g / cm 3 is compared with the composition of Example 10 (above the upper limit). Thus, it had better temporal stability. Moreover, the cured film obtained by the composition of Example 1 has a more excellent appearance after the moisture resistance test as compared with the cured film obtained by the composition of Example 11 (less than the lower limit value). It was.
Further, the titanium nitride-containing particles contain titanium atoms and nitrogen atoms, and the content atom number ratio X of the nitrogen atom content to the titanium atom content in the titanium nitride-containing particles exceeds 0. The composition of Example 2, which was less than 1, had better temporal stability and better patterning properties than the composition of Example 10 (above the upper limit).
Further, the composition of Example 2 in which the above X exceeds 0.40 and is less than 0.95 has more excellent patternability than the composition of Example 12 (exceeding the upper limit value). It was. In addition, the composition of Example 2 had better temporal stability compared to the composition of Example 9 (less than the lower limit value).
Further, the titanium nitride-containing particle further contains oxygen atoms, and the content atom number ratio Y of the oxygen atom content to make the titanium atom content in the titanium nitride-containing particle, and the above X is X + Y <The cured film obtained by the composition of Example 2 satisfying the relationship of 0.93 has a better light-shielding property than the cured film obtained by the composition of Example 1 (over the upper limit value). It was.
The cured film obtained by the composition of Example 2 in which the titanium nitride-containing particles further contain chlorine atoms, and the content of chlorine atoms in the titanium nitride-containing particles is 800 to 3000 mass ppm. Compared to the cured films obtained with the compositions of Examples 8-12, they had better electrical properties.
In addition, the composition of Example 17 has better patterning properties than the composition of Example 16, and the cured film obtained by curing has better light-shielding properties and electrical characteristics. Was. This is presumably because the dispersant E contains fewer acidic groups in the molecule than the dispersant C, and the titanium nitride-containing particles are less likely to aggregate.
Further, the composition of Example 17 had better patterning properties than the compositions of Example 18 and Example 19. This is presumably because the dispersant E contains a graft chain.
・PGMEA:プロピレングリコール1-モノメチルエーテル2-アセタート In Table 2, each abbreviation represents the following components.
・ PGMEA: Propylene glycol 1-monomethyl ether 2-acetate
重合性化合物M1に代えて東亞合成社製「TO1382」を用い、樹脂Aに代えて下記の樹脂B-1(7.1質量部)を用い、さらに、分散剤Dを用いなかったこと以外は実施例4と同様にして組成物22B-1を作製した。組成物22B-1について、上記と同様の評価を行ったところ、実施例4と同等の評価結果を得た。ただしこの時、表2の溶媒記載と異なり、N-メチル-2-ピロリドンが含有されている。 [Example 22B-1]
Except that “TO1382” manufactured by Toagosei Co., Ltd. was used instead of the polymerizable compound M1, the following resin B-1 (7.1 parts by mass) was used instead of the resin A, and the dispersant D was not used. A composition 22B-1 was produced in the same manner as in Example 4. The composition 22B-1 was evaluated in the same manner as described above, and the same evaluation results as in Example 4 were obtained. However, at this time, unlike the solvent description in Table 2, N-methyl-2-pyrrolidone is contained.
重合性化合物M1に代えて東亞合成社製「TO1382」を用い、樹脂Aに代えて下記の樹脂B-2(7.1質量部)を用い、さらに、分散剤Dを用いなかったこと以外は実施例4と同様にして組成物22B-2を作製した。組成物22B-2について、上記と同様の評価を行ったところ、実施例4と同等の評価結果を得た。ただしこの時、表2の溶媒記載と異なり、N-メチル-2-ピロリドンが含有されている。 [Example 22B-2]
Except that “TO1382” manufactured by Toagosei Co., Ltd. was used instead of the polymerizable compound M1, the following resin B-2 (7.1 parts by mass) was used instead of the resin A, and the dispersant D was not used. A composition 22B-2 was produced in the same manner as in Example 4. The composition 22B-2 was evaluated in the same manner as described above, and the same evaluation results as in Example 4 were obtained. However, at this time, unlike the solvent description in Table 2, N-methyl-2-pyrrolidone is contained.
重合性化合物M1に代えて東亞合成社製「TO1382」を用い、樹脂Aに代えて下記の樹脂B-3(7.1質量部)を用い、さらに、分散剤Dを用いなかったこと以外は実施例4と同様にして組成物22B-3を作製した。組成物22B-3について、上記と同様の評価を行ったところ、実施例4と同等の評価結果を得た。ただしこの時、表2の溶媒記載と異なり、N-メチル-2-ピロリドンが含有されている。 [Example 22B-3]
Except that “TO1382” manufactured by Toagosei Co., Ltd. was used instead of the polymerizable compound M1, the following resin B-3 (7.1 parts by mass) was used instead of the resin A, and the dispersant D was not used. A composition 22B-3 was produced in the same manner as in Example 4. The composition 22B-3 was evaluated in the same manner as described above, and the same evaluation results as in Example 4 were obtained. However, at this time, unlike the solvent description in Table 2, N-methyl-2-pyrrolidone is contained.
重合性化合物M1に代えて東亞合成社製「TO1382」を用い、樹脂Aに代えて下記の樹脂B-1(含有量:2.3質量部)、及び、樹脂B-2(含有量3.5質量部)を用い、さらに、分散剤Dを用いなかったこと以外は実施例4と同様にして組成物22B-4を作製した。組成物22B-4について、上記と同様の評価を行ったところ、実施例4と同等の評価結果を得た。ただしこの時、表2の溶媒記載と異なり、N-メチル-2-ピロリドンが含有されている。 [Example 22B-4]
“TO1382” manufactured by Toagosei Co., Ltd. was used in place of the polymerizable compound M1, and the following resin B-1 (content: 2.3 parts by mass) and resin B-2 (content 3. 5 parts by mass), and the composition 22B-4 was prepared in the same manner as in Example 4 except that the dispersant D was not used. The composition 22B-4 was evaluated in the same manner as described above, and the same evaluation results as in Example 4 were obtained. However, at this time, unlike the solvent description in Table 2, N-methyl-2-pyrrolidone is contained.
重合性化合物M1に代えて東亞合成社製「TO1382」を用い、樹脂Aに代えて下記の樹脂B-1(含有量:2.3質量部)、及び、樹脂B-3(含有量3.5質量部)を用い、さらに、分散剤Dを用いなかったこと以外は実施例4と同様にして組成物22B-5を作製した。組成物22B-5について、上記と同様の評価を行ったところ、実施例4と同等の評価結果を得た。ただしこの時、表2の溶媒記載と異なり、N-メチル-2-ピロリドンが含有されている。 [Example 22B-5]
“TO1382” manufactured by Toagosei Co., Ltd. was used instead of the polymerizable compound M1, and the following resin B-1 (content: 2.3 parts by mass) and resin B-3 (content 3. 5 parts by mass), and the composition 22B-5 was prepared in the same manner as in Example 4 except that the dispersant D was not used. The composition 22B-5 was evaluated in the same manner as described above, and the same evaluation results as in Example 4 were obtained. However, at this time, unlike the solvent description in Table 2, N-methyl-2-pyrrolidone is contained.
4、4’-ジアミノジフェニルエーテル95.1g、及び、ビス(3-アミノプロピル)テトラメチルジシロキサン6.2gを、γ-ブチロラクトン525g、及び、N-メチル-2-ピロリドン220gと混合し、混合液を得た。上記混合液に、3、3’、4、4’-ビフェニルテトラカルボン酸二無水物144.1gを添加し、70℃で3時間反応させた。次いで、反応後の溶液に、無水フタル酸3.0gを添加し、更に70℃で2時間反応させて、25質量%の樹脂B-1溶液(樹脂B-1はポリアミック酸に該当する。)を得た。 [Synthesis of Resin B-1]
4,5′-Diaminodiphenyl ether 95.1 g and bis (3-aminopropyl) tetramethyldisiloxane 6.2 g were mixed with γ-butyrolactone 525 g and N-methyl-2-pyrrolidone 220 g. Got. To the above mixed solution, 144.1 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was added and reacted at 70 ° C. for 3 hours. Next, 3.0 g of phthalic anhydride is added to the solution after the reaction, and the mixture is further reacted at 70 ° C. for 2 hours to obtain a 25% by mass resin B-1 solution (resin B-1 corresponds to polyamic acid). Got.
4、4’-ジアミノベンズアニリド161.3gを、3-メチル-2-ピロリドン527gと混合し混合液を得た。上記混合液に3、3’、4、4’-ビフェニルテトラカルボン酸二無水物439.1gを添加し、70℃で3時間反応させた。次いで、反応後の溶液に、無水フタル酸 2.2gを添加し、更に70℃で2時間反応させて、20質量%の樹脂B-2溶液(樹脂B-2はポリアミック酸に該当する)を得た。 [Synthesis of Resin B-2]
161.3 g of 4,4′-diaminobenzanilide was mixed with 527 g of 3-methyl-2-pyrrolidone to obtain a mixed solution. 439.1 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was added to the above mixed solution and reacted at 70 ° C. for 3 hours. Next, 2.2 g of phthalic anhydride is added to the solution after the reaction, and further reacted at 70 ° C. for 2 hours to obtain 20% by mass of a resin B-2 solution (resin B-2 corresponds to polyamic acid). Obtained.
3’-ジアミノジフェニルスルホン176.7g、及び、ビス(3-アミノプロピル)テトラメチルジシロキサン18.6gをγ-ブチロラクトン2667g、Nメチル-2-ピロリドン527gと混合し、混合液を得た。上記混合液に3、3’、4、4’-ビフェニルテトラカルボン酸二無水物439.1gを添加し、70℃で3時間反応させた。次いで、反応後の溶液に、無水フタル酸2.2gを添加し、更に70℃で2時間反応させて、20質量%の樹脂B-3溶液(樹脂B-3はポリアミック酸に該当する。)を得た。 [Synthesis of Resin B-3]
176.7 g of 3′-diaminodiphenylsulfone and 18.6 g of bis (3-aminopropyl) tetramethyldisiloxane were mixed with 2667 g of γ-butyrolactone and 527 g of N-methyl-2-pyrrolidone to obtain a mixed solution. 439.1 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was added to the above mixed solution and reacted at 70 ° C. for 3 hours. Next, 2.2 g of phthalic anhydride is added to the solution after the reaction, and the mixture is further reacted at 70 ° C. for 2 hours to give a 20% by mass resin B-3 solution (resin B-3 corresponds to polyamic acid). Got.
重合性化合物M1に代えて下記構造のモノマーと重合性化合物M1との混合モノマー(混合比:50質量%/50質量%)を用いた以外は実施例4と同様にして組成物を作製した。作製した組成物について、上記と同様の評価を行ったところ、実施例4と同等の評価結果を得た。なお、下記モノマーは、特開2009-169049号公報を参照して合成した。
A composition was prepared in the same manner as in Example 4 except that instead of the polymerizable compound M1, a mixed monomer of the monomer having the following structure and the polymerizable compound M1 (mixing ratio: 50% by mass / 50% by mass) was used. About the produced composition, when evaluation similar to the above was performed, the evaluation result equivalent to Example 4 was obtained. The following monomers were synthesized with reference to JP 2009-169049 A.
組成物1を、乾燥膜厚が1.5μmになるように、無アルカリガラス基板上にスピンコートして、組成物層を得た。その後、組成物層をシリコンウェハごとホットプレート上で加熱した(加熱条件:100℃、2分間)。加熱後の組成物層に対して、20μmのラインアンドスペース状のマスクを介してi線ステッパー露光装置FPA-3000i5+(Canon(株)製)で1000mJ/cm2の露光量で露光した。その後、シリコンウェハをスピン・シャワー現像機(DW-30型、ケミトロニクス製)の水平回転テーブル上に載置しCD-2000(富士フイルムエレクトロニクスマテリアルズ社製)を用いて、組成物層を23℃で60秒間パドル現像したこのようにして得られたパターン状の硬化膜(ブラックマトリクス)を200℃、5分間の条件で乾燥した。
次に、上記硬化膜の開口部に、下記赤色(R)用樹脂組成物R-1を用いて、上記で作製したブラックマトリクスと同様の方法で100μmのライン状パターンを有する赤色(R)の着色パターンを形成した。更に、同様にして下記緑色(G)用樹脂組成物G-1を用いて緑色(G)の着色パターンを、及び、青色(B)用樹脂組成物B-1を用いて青色(B)の着色パターンを順次形成してブラックマトリクスを含有するカラーフィルタを作製した。作製したカラーフィルタにITO(Indium Tin Oxide)透明電極、配向膜等の加工を施し、液晶表示装置を設けた。得られた表示装置の画質は良好であった。 [Example 1-A: Production of color filter]
Composition 1 was spin-coated on an alkali-free glass substrate so that the dry film thickness was 1.5 μm to obtain a composition layer. Thereafter, the composition layer was heated together with the silicon wafer on a hot plate (heating condition: 100 ° C., 2 minutes). The composition layer after heating was exposed at an exposure amount of 1000 mJ / cm 2 with an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.) through a 20 μm line-and-space mask. Thereafter, the silicon wafer was placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics), and a composition layer was formed using CD-2000 (manufactured by FUJIFILM Electronics Materials). The pattern-like cured film (black matrix) thus obtained, which was paddle developed at 60 ° C. for 60 seconds, was dried at 200 ° C. for 5 minutes.
Next, a red (R) resin having a 100 μm linear pattern in the same manner as the black matrix produced above using the following red (R) resin composition R-1 at the opening of the cured film. A colored pattern was formed. Further, similarly, the following green (G) resin composition G-1 is used to give a green (G) coloring pattern, and blue (B) resin composition B-1 is used to give a blue (B) coloring pattern. Color patterns were sequentially formed to produce a color filter containing a black matrix. The produced color filter was processed with an ITO (Indium Tin Oxide) transparent electrode, an alignment film, and the like to provide a liquid crystal display device. The image quality of the obtained display device was good.
チタン窒化物含有粒子に代えて、以下の顔料を用いたことを除いては組成物1と同様にして、赤色(R)用樹脂組成物R-1、緑色(G)用樹脂組成物G-1、及び、青色(B)用樹脂組成物B-1を作製した。
・赤色(R)用顔料: C.I.ピグメントレッド254
・緑色(G)用顔料: C.I.ピグメントグリーン36とC.I.ピグメントイエロー219との30/70〔質量比〕混合物
・青色(B)用顔料: C.I.ピグメントブルー15:6とC.I.ピグメントバイオレット23との30/70〔質量比〕混合物 <Preparation of Resin Composition for Red (R), Resin Composition for Green (G), and Resin Composition for Blue (B)>
The red (R) resin composition R-1 and the green (G) resin composition G- were the same as the composition 1 except that the following pigments were used in place of the titanium nitride-containing particles. 1 and a blue (B) resin composition B-1.
-Red (R) pigment: C.I. I. Pigment Red 254
-Green (G) pigment: C.I. I. Pigment Green 36 and C.I. I. Pigment Yellow 219 30/70 [mass ratio] mixture and blue (B) pigment: C.I. I. Pigment blue 15: 6 and C.I. I. 30/70 [mass ratio] mixture with pigment violet 23
画素サイズが2.0μm、膜厚1.5μmのカラーフィルタ(1cm四方)、マイクロレンズ、金属配線、及び、フォトダイオードを備えたシリコンウェハのカラーフィルタ周縁部に、組成物1を用いて幅100μm、膜厚1.5μmの硬化膜をフォトリソグラフィ法で形成した。得られたシリコンウェハを用いて固体撮像素子を作成した。得られた固体撮像素子は、高解像度で色分離性に優れていた。 [Example 1-B: Production of solid-state imaging device]
A composition 1 is used on the periphery of a color filter of a silicon wafer having a color filter (1 cm square) having a pixel size of 2.0 μm and a film thickness of 1.5 μm, a microlens, a metal wiring, and a photodiode, and a width of 100 μm. A cured film having a thickness of 1.5 μm was formed by photolithography. A solid-state image sensor was created using the obtained silicon wafer. The obtained solid-state imaging device had high resolution and excellent color separation.
チタン窒化物含有粒子に代えて以下に示す顔料の混合物を用いたこと以外は組成物1と同様にして組成物IRを作製した。 [Example 1-C: Production of infrared sensor]
A composition IR was prepared in the same manner as the composition 1 except that the following pigment mixture was used in place of the titanium nitride-containing particles.
・ピロロピロール顔料:下記構造(特開2009-263614号公報に記載の方法で合成した)(波長800~900nmの範囲に極大吸収を有する赤外線吸収剤)
・PR254 :Pigment Red 254
・PB15:6 :Pigment Blue 15:6
・PY139 :Pigment Yellow 139
・PV23 :Pigment Violet 23
上記の顔料を、以下の質量比で混合した。ピロロピロール顔料/PR254/PB15:6/PY139/PV23=22.7/11.3/22.7/10.3/6.9 (Mixture of pigments)
Pyrrolopyrrole pigment: the following structure (synthesized by the method described in JP-A-2009-263614) (infrared absorber having maximum absorption in the wavelength range of 800 to 900 nm)
PR254: Pigment Red 254
-PB15: 6: Pigment Blue 15: 6
・ PY139: Pigment Yellow 139
-PV23: Pigment Violet 23
The above pigments were mixed at the following mass ratio. Pyrrolopyrrole pigment / PR254 / PB15: 6 / PY139 / PV23 = 22.7 / 11.3 / 22.7 / 10.3 / 6.9
次いで、i線ステッパー露光装置FPA-3000i5+(Canon(株)製)を使用して、1.4μm角の正方形ピクセルパターンが形成されるフォトマスクを通して、最適露光量にて組成物層IRを露光した。最適露光量は、50~750mJ/cm2まで50mJ/cm2ずつ上昇させて、上記正方形ピクセルパターンを解像する露光量とした。
その後、組成物層IRが露光されたシリコンウェハを、スピン・シャワー現像機の水平回転テーブル上に載置し、CD-2060(テトラメチルアンモニウムヒドロキシド水溶液、富士フイルムエレクトロニクスマテリアルズ社製)を用いて23℃で60秒間パドル現像した。これによりシリコンウェハ上に着色パターン(硬化膜に該当する。)を形成した。
着色パターンが形成されたシリコンウェハを、純水でリンスし、その後スプレー乾燥した。更に、上記シリコンウェハを200℃のホットプレート上に載置して、着色パターンを300秒間加熱(ポストベーク)した。上記により、赤外線センサ用のカラーフィルタとしての、高解像度な着色パターンを含有するシリコンウェハを得た。カラーフィルタ周縁部に、組成物1を用いて幅100μm、膜厚1.5μmの硬化膜をフォトリソグラフィ法で形成した。得られたカラーフィルタを、公知の方法に従い固体撮像素子に組み込んだ(赤外線センサに該当する)。得られた固体撮像素子にて低照度の環境下(0.001Lux)で発光波長940nmの近赤外LED(light emitting diode)光源を照射し、画像の取り込みを行い、画像性能を比較評価した。可視光線由来のノイズが少ない状態で、発光波長940nmの赤外線を透過し、分光認識が良好であった。 Composition IR was formed by spin coating composition IR so that the dry film thickness was 1.5 μm on the silicon wafer. The silicon wafer was placed on a hot plate at 100 ° C., and the composition layer IR was heated (prebaked) for 120 seconds.
Next, using the i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), the composition layer IR was exposed at an optimum exposure amount through a photomask on which a square pixel pattern of 1.4 μm square was formed. . The optimum exposure amount was increased by 50 mJ / cm 2 from 50 to 750 mJ / cm 2 to obtain an exposure amount for resolving the square pixel pattern.
Thereafter, the silicon wafer on which the composition layer IR has been exposed is placed on a horizontal rotary table of a spin shower developing machine, and CD-2060 (tetramethylammonium hydroxide aqueous solution, manufactured by Fuji Film Electronics Materials) is used. And paddle development at 23 ° C. for 60 seconds. As a result, a colored pattern (corresponding to a cured film) was formed on the silicon wafer.
The silicon wafer on which the colored pattern was formed was rinsed with pure water and then spray-dried. Further, the silicon wafer was placed on a hot plate at 200 ° C., and the colored pattern was heated (post-baked) for 300 seconds. As described above, a silicon wafer containing a high-resolution colored pattern as a color filter for an infrared sensor was obtained. A cured film having a width of 100 μm and a film thickness of 1.5 μm was formed by photolithography using the composition 1 on the periphery of the color filter. The obtained color filter was incorporated into a solid-state imaging device according to a known method (corresponding to an infrared sensor). The obtained solid-state imaging device was irradiated with a near-infrared LED (light emitting diode) light source having an emission wavelength of 940 nm under a low illuminance environment (0.001 Lux), and an image was captured to compare and evaluate the image performance. In a state where there was little noise derived from visible light, infrared light having an emission wavelength of 940 nm was transmitted, and spectral recognition was good.
・PI-04(WO2015/036910 のOE74で表される化合物、光重合開始剤に該当するオキシム化合物。) A composition was prepared in the same manner as in Example 2 except that PI-04 represented by the following formula was used instead of IRGACURE OXE-02 (manufactured by BASF). About the produced composition, when the same evaluation as the above was performed, the result similar to Example 2 was obtained.
PI-04 (a compound represented by OE74 of WO2015 / 036910, an oxime compound corresponding to a photopolymerization initiator)
101・・・固体撮像素子
102・・・撮像部
103・・・カバーガラス
104・・・スペーサー
105・・・積層基板
106・・・チップ基板
107・・・回路基板
108・・・電極パッド
109・・・外部接続端子
110・・・貫通電極
111・・・レンズ層
112・・・レンズ材
113・・・支持体
114、115・・・硬化膜
201・・・受光素子
202・・・カラーフィルタ
201・・・受光素子
202・・・カラーフィルタ
203・・・マイクロレンズ
204・・・基板
205b・・・青色画素
205r・・・赤色画素
205g・・・緑色画素
205bm・・・ブラックマトリクス
206・・・pウェル層
207・・・読み出しゲート部
208・・・垂直転送路
209・・・素子分離領域
210・・・ゲート絶縁膜
211・・・垂直転送電極
212・・・硬化膜
213、214・・・絶縁膜
215・・・平坦化膜
300・・・赤外線センサ
310・・・固体撮像素子
311・・・赤外線吸収フィルタ
312・・・カラーフィルタ
313・・・赤外線透過フィルタ
314・・・樹脂膜
315・・・マイクロレンズ
316・・・平坦化膜 DESCRIPTION OF
Claims (19)
- チタン窒化物含有粒子と、樹脂と、を含有する組成物であって、
波長400~1200nmにおける、前記チタン窒化物含有粒子の複素誘電率εを下記式(1)で表すとき、ε’の最小値が0未満である、組成物。
式(1) ε=ε’+ε”j
なお、上記式(1)中、ε’は複素誘電率εの実数部、ε”は複素誘電率εの虚数部、jは虚数単位を表す。 A composition containing titanium nitride-containing particles and a resin,
A composition in which the minimum value of ε ′ is less than 0 when the complex dielectric constant ε of the titanium nitride-containing particles at a wavelength of 400 to 1200 nm is represented by the following formula (1).
Formula (1) ε = ε ′ + ε ″ j
In the above formula (1), ε ′ represents a real part of the complex dielectric constant ε, ε ″ represents an imaginary part of the complex dielectric constant ε, and j represents an imaginary unit. - 前記チタン窒化物含有粒子の密度が3.0g/cm3以上、5.0g/cm3未満である、請求項1に記載の組成物。 The composition of Claim 1 whose density of the said titanium nitride containing particle | grain is 3.0 g / cm < 3 > or more and less than 5.0 g / cm < 3 >.
- 前記チタン窒化物含有粒子が、チタン原子、及び、窒素原子を含有し、前記チタン窒化物含有粒子中における前記チタン原子の含有量に対する、前記窒素原子の含有量の比Xが、0を超え、1未満である、請求項1又は2に記載の組成物。 The titanium nitride-containing particles contain titanium atoms and nitrogen atoms, and the ratio X of the nitrogen atom content to the titanium atom content in the titanium nitride-containing particles exceeds 0, The composition according to claim 1 or 2, wherein the composition is less than 1.
- 前記比Xが、0.40を超え、0.95未満である、請求項3に記載の組成物。 The composition according to claim 3, wherein the ratio X is more than 0.40 and less than 0.95.
- 前記チタン窒化物含有粒子が、更に酸素原子を含有し、
前記チタン窒化物含有粒子中における前記チタン原子の含有量にする、前記酸素原子の含有量の比Yと、前記比Xとが、以下の式(4)を満たす、請求項3又は4に記載の組成物。
式(4)X+Y<0.93 The titanium nitride-containing particles further contain oxygen atoms,
The ratio Y of the content of the oxygen atoms, which is the content of the titanium atoms in the titanium nitride-containing particles, and the ratio X satisfy the following formula (4). Composition.
Formula (4) X + Y <0.93 - 前記チタン窒化物含有粒子が、更に塩素原子を含有し、前記チタン窒化物含有粒子中における前記塩素原子の含有量が、800~3000質量ppmである、請求項1~5のいずれか一項に記載の組成物。 The titanium nitride-containing particle further contains a chlorine atom, and the content of the chlorine atom in the titanium nitride-containing particle is 800 to 3000 mass ppm. The composition as described.
- 前記樹脂が、アルカリ可溶性樹脂を含有する、請求項1~6のいずれか一項に記載の組成物。 The composition according to any one of claims 1 to 6, wherein the resin contains an alkali-soluble resin.
- 前記アルカリ可溶性樹脂が、ポリイミド樹脂、及び、ポリイミド前駆体からなる群から選択される少なくとも1種である、請求項7に記載の組成物。 The composition according to claim 7, wherein the alkali-soluble resin is at least one selected from the group consisting of a polyimide resin and a polyimide precursor.
- 前記樹脂が、分散剤を含有する、請求項1~8のいずれか一項に記載の組成物。 The composition according to any one of claims 1 to 8, wherein the resin contains a dispersant.
- 更に、重合性化合物を含有する、請求項1~9のいずれか一項に記載の組成物。 The composition according to any one of claims 1 to 9, further comprising a polymerizable compound.
- 更に、重合開始剤を含有する、請求項1~10のいずれか一項に記載の組成物。 The composition according to any one of claims 1 to 10, further comprising a polymerization initiator.
- 前記重合開始剤が、光重合開始剤を含有する、請求項11に記載の組成物。 The composition according to claim 11, wherein the polymerization initiator contains a photopolymerization initiator.
- 前記光重合開始剤がオキシム化合物である、請求項12に記載の組成物。 The composition according to claim 12, wherein the photopolymerization initiator is an oxime compound.
- 請求項1~13のいずれか一項に記載の組成物を硬化して得られる、硬化膜。 A cured film obtained by curing the composition according to any one of claims 1 to 13.
- 請求項14に記載の硬化膜を含有するカラーフィルタ。 A color filter containing the cured film according to claim 14.
- 請求項14に記載の硬化膜を含有する、固体撮像素子。 A solid-state imaging device containing the cured film according to claim 14.
- 請求項14に記載の硬化膜を含有する、赤外線センサ。 An infrared sensor containing the cured film according to claim 14.
- 請求項14に記載の硬化膜を含有する、近赤外線センサ。 A near-infrared sensor containing the cured film according to claim 14.
- 請求項14に記載の硬化膜を含有する、近接センサ。 A proximity sensor comprising the cured film according to claim 14.
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