WO2017159190A1 - 組成物、膜、硬化膜、光学センサおよび膜の製造方法 - Google Patents

組成物、膜、硬化膜、光学センサおよび膜の製造方法 Download PDF

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WO2017159190A1
WO2017159190A1 PCT/JP2017/005531 JP2017005531W WO2017159190A1 WO 2017159190 A1 WO2017159190 A1 WO 2017159190A1 JP 2017005531 W JP2017005531 W JP 2017005531W WO 2017159190 A1 WO2017159190 A1 WO 2017159190A1
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group
composition
resin
mass
particles
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PCT/JP2017/005531
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English (en)
French (fr)
Japanese (ja)
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哲志 宮田
貴規 田口
祐継 室
秀知 高橋
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富士フイルム株式会社
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Priority to JP2018505362A priority Critical patent/JP6688875B2/ja
Publication of WO2017159190A1 publication Critical patent/WO2017159190A1/ja

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    • 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
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds

Definitions

  • the present invention relates to a composition, a film, a cured film, an optical sensor, and a film manufacturing method.
  • Patent Document 1 It is known to produce a film using a composition containing a resin and particles (see Patent Documents 1 and 2).
  • Patent Document 1 describes that a film is produced using a composition containing particles that are white pigments such as titanium oxide.
  • the film using the composition containing resin and particles can be used as an optical sensor using a semiconductor as a white film.
  • the film is a thin film that has a degree of shielding that can conceal the optical sensor, and at the same time, the optical sensor is driven to allow sufficient light to pass through to detect changes in the amount of received light.
  • a membrane is required.
  • the film in the region where L * exceeds 85 in the CIE 1976 L * a * b * color system close to pure white has a low light transmittance and is sufficient to drive the optical sensor to detect the change in the amount of light received. Difficult to transmit an amount of light.
  • the film Even in the case of a thin film, from the viewpoint of concealing the optical sensor, the film needs to have a whiteness of L * in the L * a * b * color system of CIE 1976 of 35 or more. Therefore, in order to achieve both shielding degree and transmittance, it is required that the film has a region where L * is in the range of 35 to 85.
  • Patent Document 1 describes a white light-shielding pattern.
  • Patent Document 1 has no suggestion regarding suppression of density unevenness after one month.
  • Patent Document 2 does not describe a white film. Naturally, white density unevenness of the film does not occur, and there is no suggestion regarding suppression of density unevenness after one month.
  • Patent Documents 1 and 2 have no suggestion of combining a resin having a refractive index of 1.5 or less with respect to light having a wavelength of 589 nm and particles having a high refractive index.
  • L * in the L * a * b * color system of CIE 1976 when a film having a thickness of 3.0 ⁇ m is formed is 35 to 85, and after a lapse of one month. It is providing the composition which can manufacture the film
  • the particles include at least particles having a refractive index of 2.1 or more with respect to light having a wavelength of 589 nm;
  • a composition comprising at least a resin having a refractive index of 1.5 or less with respect to light having a wavelength of 589 nm.
  • a composition comprising particles and a resin, Among the above particles, the refractive index for light with a wavelength of 589 nm of the highest refractive index particle contained in the composition, and the refractive index for light with a wavelength of 589 nm of the resin with the lowest refractive index contained in the composition among the above resins. And the difference is 1.22 or more.
  • composition according to [1] or [2], wherein the composition is a curable composition.
  • Any of [1] to [3], wherein L * in the L * a * b * color system of CIE 1976 when a film having a thickness of 3.0 ⁇ m is formed using the composition is 35 to 85 A composition according to one.
  • the composition according to any one of [1] to [4], wherein the particles include inorganic particles.
  • the composition according to [5], wherein the inorganic particles include a white pigment.
  • the inorganic particles include titanium oxide.
  • the composition further comprises a radical polymerizable compound and a photopolymerization initiator.
  • composition according to [13] wherein the content of the radical polymerizable compound having a refractive index of 1.5 or less with respect to light having a wavelength of 589 nm in the total mass of the radical polymerizable compound is 80% by mass or more.
  • L * in the L * a * b * color system of CIE 1976 is 35 to 85, and density unevenness after one month is suppressed. It is possible to provide a composition capable of producing a coated film. Moreover, according to this invention, the manufacturing method of a film
  • 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.
  • substitution and unsubstituted includes the group (atomic group) which has a substituent with the group (atomic group) which does not have a substituent.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • “(meth) acrylate” represents acrylate and methacrylate
  • “(meth) acryl” represents acryl and methacryl
  • “(meth) acryloyl” represents acryloyl and methacryloyl.
  • exposure includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams.
  • the light used for exposure generally includes active rays or radiation such as an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
  • active rays or radiation such as an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
  • a weight average molecular weight and a number average molecular weight are defined as a polystyrene conversion value measured by gel permeation chromatography (GPC).
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation), and TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6) as a column.
  • 0.0 mm (inner diameter) ⁇ 15.0 cm) can be obtained by
  • the first aspect of the composition of the present invention comprises particles and a resin,
  • the particles include at least particles having a refractive index of 2.1 or more with respect to light having a wavelength of 589 nm;
  • the resin contains at least a resin having a refractive index of 1.5 or less with respect to light having a wavelength of 589 nm.
  • a second aspect of the composition of the present invention is a composition comprising particles and a resin, The refractive index of light with a wavelength of 589 nm of the highest refractive index particles (hereinafter also referred to as the highest refractive index particles) contained in the composition and the lowest refractive index resin (hereinafter referred to as the lowest refractive index) contained in the composition.
  • the difference in refractive index with respect to light having a wavelength of 589 nm is also 1.22 or more.
  • L * in the L * a * b * color system of CIE 1976 is 35 to 85, and density unevenness after one month has elapsed.
  • a composition capable of producing a suppressed film can be provided.
  • the inventors of the present invention manufactured a composition containing particles and a resin by using a resin having a refractive index of about 1.6 as a binder for the film or a dispersant for the particles.
  • the interaction between the low refractive index resins is achieved.
  • density unevenness after one month has been suppressed.
  • the interaction between the resins is reduced, and the interaction between the resin and the particles is advantageous.
  • uneven distribution of resin and particles in the composition is eliminated.
  • density unevenness after one month has been suppressed.
  • a film formed from the composition by increasing the difference between the refractive index of the particles and the refractive index of the resin is advantageous.
  • the composition of the present invention is preferably a curable composition.
  • the “curable composition” refers to a composition containing a curable compound described later.
  • the curable composition may be a photocurable composition or a thermosetting composition. Details of the characteristics of the composition of the present invention will be described.
  • L * in the L * a * b * color system of CIE 1976 is preferably 35 to 85.
  • the upper limit of L * in the L * a * b * color system of CIE1976 is more preferably less than 80, and further preferably 75 or less. Preferably, it is particularly preferably 70 or less.
  • the lower limit of L * in the L * a * b * color system of CIE 1976 is more preferably 40 or more, and particularly preferably 50 or more. preferable.
  • the value of L * in the L * a * b * color system of CIE 1976 is a value measured by the method described in Examples described later.
  • a * and b * in the L * a * b * color system of CIE 1976 are preferably ⁇ 30 to 30, 20 to 20 is more preferable, and ⁇ 10 to 10 is particularly preferable.
  • the composition of the present invention preferably has a solids sedimentation rate of 10% by mass or less when centrifuged at room temperature (25 ° C.) under conditions of 3500 rpm (rotations per minute) for 47 minutes.
  • the mass% or less is more preferable.
  • a method for lowering the solid content sedimentation rate of the composition a method for increasing the viscosity of the composition, a method for lowering the solid content concentration of the composition, or increasing the dispersibility of the solid content (preferably particles) in the composition. Examples thereof include a method, a method of reducing the particle density, and a method of reducing the particle diameter of the particles.
  • the “solid content” in the present specification means the following “solid content before centrifugation” unless otherwise specified.
  • the composition is dried using an oven at 160 ° C. for 1 hour, and the amount of volatilization is determined by measuring the loss on drying before and after drying. The difference between the mass of the composition before drying and the amount of volatilization is calculated. Calculate to calculate the “solid content before centrifugation”.
  • the “solid content after centrifugation” is calculated in the same manner as described above for the supernatant after the composition has been centrifuged for 47 minutes at room temperature and 3500 rpm. The difference between the “solid content after centrifugation” and the “solid content before centrifugation” is divided by the “solid content before centrifugation” to calculate the solids sedimentation rate as a percentage.
  • the solid content concentration of the composition is preferably 20 to 75% by mass.
  • the upper limit is more preferably 60% by mass or less.
  • the lower limit is more preferably 30% by mass or more.
  • composition of the composition will be described in detail.
  • the composition of the present invention comprises particles.
  • the composition of the present invention has a difference between the refractive index of the particles having the highest refractive index contained in the composition with respect to light having a wavelength of 589 nm and the refractive index of the resin having the lowest refractive index contained in the composition with respect to light having a wavelength of 589 nm. Is preferably 1.22 or more, and more preferably 1.27 or more. Within this range, it is preferable because L * in the L * a * b * color system of CIE 1976 when a film having a thickness of 3.0 ⁇ m is formed is easily increased.
  • the composition of the present invention preferably contains particles having a refractive index of 2.1 or more with respect to light having a wavelength of 589 nm.
  • the composition preferably contains at least one kind of particles having a refractive index of 2.1 or more with respect to light having a wavelength of 589 nm, and has a refractive index of 2.1 with respect to light having a wavelength of 589 nm. It is more preferable that only the above particles are included.
  • the content of particles having a refractive index of 2.1 or more with respect to light having a wavelength of 589 nm is 80% by mass or more with respect to the total mass of the particles. It is preferably 90% by mass or more, more preferably 95% by mass or more.
  • the refractive index of light having a wavelength of 589 nm of particles having a refractive index of 2.1 or more with respect to light having a wavelength of 589 nm is preferably 2.1 to 2.75, more preferably 2.5 to 2.75. preferable. If the refractive index for light with a wavelength of 589 nm is 2.1 or more, L * in the L * a * b * color system of CIE 1976 when a film having a thickness of 3.0 ⁇ m is formed can be increased. ,preferable.
  • the refractive index of the particles is measured by the following method. First, dispersion is performed using a dispersant having a known refractive index and PGMEA.
  • the prepared dispersion and a resin having a known refractive index are mixed so that the concentration in the solid content of the particles is 10% by mass, 20% by mass, 30% by mass, and 40% by mass, respectively, and four types of coating are performed.
  • Make a liquid After depositing these coating solutions on a Si wafer at 300 nm, the refractive index of the resulting film is measured using ellipsometry (Lambda Ace RE-3300 (trade name), Dainippon Screen Mfg. Co., Ltd.). Thereafter, the particle concentration and refractive index are plotted and extrapolated to derive the particle refractive index.
  • grains can also be similarly measured by the method as described in the said Example.
  • a method for taking out the particles from the film for example, 2 to 6 mol / L is applied to the film or the cured film (a composition is applied to form a film).
  • a basic solution is added to 10 to 30% by mass of the mass of the film or cured film, heated and refluxed for 12 hours, and then filtered and washed to obtain a particle component.
  • Particles having a refractive index of 2.1 or more with respect to light having a wavelength of 589 nm preferably have an average primary particle diameter of 50 to 300 nm, more preferably 60 to 200 nm from the viewpoint of density unevenness after aging for one month. 70 to 200 nm is particularly preferable from the viewpoint of L *.
  • the particles having an average primary particle size of 50 to 300 nm are preferably circular particles in a transmission electron microscope photograph of the particles.
  • the particles having an average primary particle diameter of 50 to 300 nm are not strictly circular particles but may be particles having a major axis and a minor axis, which will be described later.
  • Particles having a refractive index of 2.1 or more with respect to light having a wavelength of 589 nm are preferable as the proportion of particles having a particle diameter of 50 to 300 nm increases.
  • the particles having a refractive index of 2.1 or more with respect to light having a wavelength of 589 nm preferably contain particles having a particle size of 50 to 300 nm in a proportion of 30% by mass or more, and particles having a particle size of 50 to 300 nm. Is more preferably contained in a proportion of 50% by mass or more.
  • the L * in the L * a * b * color system of CIE 1976 when a film having a thickness of 3.0 ⁇ m is formed can be easily controlled to 35 to 85.
  • the primary particle diameter of the particles can be determined by observing the powder particles with a transmission electron microscope (TEM) and observing the portion where the particles are not aggregated.
  • the particle size distribution of the particles is determined by measuring the particle size distribution with an image processing apparatus using a photograph of a powdered particle, which is a primary particle, using a transmission electron microscope. Ask.
  • the average primary particle diameter of the particles is defined as the average primary particle diameter based on the arithmetic average diameter based on the number calculated from the particle size distribution.
  • an electron microscope (H-7000) manufactured by Hitachi, Ltd. is used as a transmission electron microscope, and Luzex AP manufactured by Nireco Corporation is used as an image processing apparatus.
  • the particles having a refractive index of 2.1 or more with respect to light having a wavelength of 589 nm may be particles having an average major axis length of 50 to 150 nm.
  • Particles having an average major axis length of 50 to 150 nm preferably have an average major axis length of 60 to 140 nm, and more preferably 80 to 130 nm.
  • the particles having an average major axis length of 50 to 150 nm are preferably particles having a major axis and a minor axis.
  • the “major axis of particle” refers to the longest diameter of a particle in a transmission electron microscope photograph of the particle.
  • the “short axis of the particle” means the shortest diameter of the particle in a transmission electron microscope photograph of the particle.
  • Particles having a major axis and a minor axis are sometimes referred to as rod-like particles or elliptical particles.
  • the particles having an average major axis length of 50 to 150 nm in the present invention preferably have an average minor axis length of 5 to 50 nm, more preferably 10 to 30 nm, and particularly preferably 10 to 20 nm.
  • Particles having an average major axis length of 50 to 150 nm preferably have an average major axis length of 2 to 10 times the average minor axis length, more preferably 3 to 6 times, and 4 to 5 times. Is particularly preferred.
  • the particles having an average major axis length of 50 to 150 nm preferably contain particles having a major axis length of 50 to 150 nm in a proportion of 30 to 60% by mass, and the major axis length of 50 to 150 nm.
  • the particles are contained in a proportion of 35 to 50% by mass.
  • L * in the L * a * b * color system of CIE 1976 is controlled to 35 to 85 when a film having a thickness of 3.0 ⁇ m is formed. It is easy to provide the composition which is easy to do and is excellent in liquid aging stability.
  • the particles having an average major axis length of 50 to 150 nm preferably contain particles having a major axis length of 60 to 140 nm in a proportion of 30 to 60% by mass, and particles having a major axis length of 80 to 130 nm are 30 to 50% by mass. It is more preferable to contain it in the ratio of%.
  • the major axis length and minor axis length of the particles can be determined by observing the powder particles with a transmission electron microscope (TEM) and observing the portion where the particles are not aggregated.
  • the particle size distribution of the particles is determined by taking a transmission electron microscope photograph of the powder particles, which are primary particles, using a transmission electron microscope, and then using the photograph to determine the major axis length of the particles.
  • the particle size distribution of the minor axis length is measured and obtained.
  • the average major axis length and the average minor axis length of the particles are the average major axis length and the average minor axis length based on the number-based arithmetic average diameter calculated from the particle size distribution.
  • an electron microscope (H-7000) manufactured by Hitachi, Ltd. is used as a transmission electron microscope
  • Luzex AP manufactured by Nireco Corporation is used as an image processing apparatus.
  • the density of particles having a refractive index of 2.1 or more with respect to light having a wavelength of 589 nm is preferably 1.0 to 6.0 g / cm 3 .
  • Lower limit, 2.5 g / cm 3 or more, more preferably, 3.0 g / cm 3 or more is more preferable.
  • the upper limit is more preferably 4.5 g / cm 3 or less.
  • the density of the particles having a refractive index of 2.1 or more with respect to light having a wavelength of 589 nm is smaller than the upper limit of the preferable range, the particles are less likely to settle in the composition. It can be effectively improved.
  • the proportion of particles having a density of 2.5 g / cm 3 or more (preferably 3.0 g / cm 3 or more) in the total amount of particles is preferably 5% by mass or more, and more preferably 10% by mass or more.
  • the upper limit may be 100% by mass or 99% by mass or less.
  • the type of particles having a refractive index of 2.1 or more with respect to light having a wavelength of 589 nm there is no particular limitation on the type of particles having a refractive index of 2.1 or more with respect to light having a wavelength of 589 nm.
  • the particles having a refractive index of 2.1 or more with respect to light having a wavelength of 589 nm include conventionally known various inorganic particles and organic particles.
  • the particles having a refractive index of 2.1 or more with respect to light having a wavelength of 589 nm preferably include at least inorganic particles. Many inorganic particles have a higher density than organic particles, and particles having a higher density are more likely to settle in the composition.
  • particles having a refractive index of 2.1 or more with respect to light having a wavelength of 589 nm are used in combination with a resin having a refractive index of 1.5 or less with respect to light having a wavelength of 589 nm. Even when inorganic particles are used as the particles, it is possible to produce a film in which the sedimentation of the inorganic particles is suppressed and the density unevenness after one month has elapsed.
  • the refractive index with respect to light having a wavelength of 589 nm of the particles having the highest refractive index contained in the composition and the wavelength of 589 nm of the resin having the lowest refractive index contained in the composition Since the difference from the refractive index with respect to light is 1.22 or more, even when inorganic particles are used as the particles, a film that suppresses sedimentation of inorganic particles and suppresses uneven density after one month has elapsed. Can be manufactured.
  • the inorganic particles are preferably particles containing a metal. More preferably, the particles containing metal contain a simple metal or a metal oxide.
  • Examples of the particles having a refractive index of 2.1 or more with respect to light having a wavelength of 589 nm include pigments, ceramic materials, magnetic materials, and other particles, and pigments are preferred.
  • the inorganic particles are preferably a white pigment.
  • a white pigment as the inorganic particles, when a film having a thickness of 3.0 ⁇ m is formed using the composition, L * in the L * a * b * color system of CIE 1976 can be easily controlled within a preferable range.
  • the white pigment includes not only pure white but also a light gray (for example, grayish white, light gray) pigment close to white. White pigments tend to have a high density, and sedimentation tends to occur in the composition.
  • particles having a refractive index of 2.1 or more with respect to light having a wavelength of 589 nm are used in combination with a resin having a refractive index of 1.5 or less with respect to light having a wavelength of 589 nm. Even when a white pigment is used as the particles, it is possible to produce a film in which sedimentation of inorganic particles is suppressed and density unevenness after one month has elapsed.
  • the refractive index with respect to light having a wavelength of 589 nm of the particles having the highest refractive index contained in the composition and the wavelength of 589 nm of the resin having the lowest refractive index contained in the composition are used in combination with a resin having a refractive index of 1.5 or less with respect to light having a wavelength of 589 nm.
  • white pigments include titanium oxide, strontium titanate, barium titanate, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, Examples include hollow resin particles and zinc sulfide.
  • the white pigment is preferably particles having a titanium atom, and more preferably titanium oxide. That is, in the composition of the present invention, the inorganic particles preferably include titanium oxide.
  • the titanium oxide preferably has a purity of titanium dioxide (TiO 2 ) of 70% or more, more preferably 80% or more, and still more preferably 85% or more.
  • the titanium oxide preferably has a content of low-order titanium oxide, titanium oxynitride or the like represented by Ti n O 2n-1 (where n represents a number of 2 to 4) of 30% by mass or less, The content is more preferably no more than mass%, and even more preferably no more than 15 mass%.
  • the titanium oxide may be rutile type titanium oxide or anatase type titanium oxide, and rutile type titanium oxide is preferred from the viewpoints of colorability and liquid aging stability.
  • a cured film obtained by curing a composition using rutile-type titanium oxide has little change in color difference even when the cured film is heated, and has good colorability.
  • the rutile ratio of titanium oxide is preferably 95% or more, and more preferably 99% or more.
  • a well-known thing can be used as a rutile type titanium oxide.
  • the sulfuric acid method uses ilmenite ore or titanium slag as a raw material, dissolves this in concentrated sulfuric acid, separates iron as iron sulfate, and hydrolyzes the solution to obtain a hydroxide precipitate. It refers to a production method in which rutile titanium oxide is taken out by baking at a high temperature.
  • the chlorine method uses synthetic rutile and natural rutile as raw materials, reacts with chlorine gas and carbon at a high temperature of about 1000 ° C to synthesize titanium tetrachloride, and oxidizes this to produce rutile titanium oxide.
  • the rutile type titanium oxide is preferably a rutile type titanium oxide obtained by a chlorine method.
  • Titanium oxide particles having a refractive index of 2.1 or more with respect to light having a wavelength of 589 nm can scatter light and appear white, and when a film having a thickness of 3.0 ⁇ m is formed using the composition, CIE 1976 L * in the L * a * b * color system can be easily controlled to 35 to 85.
  • the preferable range of the average primary particle size of the titanium oxide particles is the same as the preferable range of the average primary particle size of particles having a refractive index of 2.1 or more with respect to light having a wavelength of 589 nm.
  • the specific surface area of titanium oxide is preferably 10 to 400 m 2 / g, more preferably 10 to 200 m 2 / g, as measured by the BET (Brunauer, Emmett, Teller) method. 2 / g is more preferable, 10 to 40 m 2 / g is particularly preferable, and 10 to 20 m 2 / g is most preferable.
  • the pH (power of hydrogen) of titanium oxide is preferably 6-8.
  • the oil absorption (g / 100 g) of titanium oxide is preferably 10 to 60 (g / 100 g), and more preferably 10 to 40 (g / 100 g).
  • the total amount of Fe 2 O 3 , Al 2 O 3 , SiO 2 , Nb 2 O 5 , and Na 2 O is preferably 0.1% by mass or less, and 0.05% by mass or less. It is more preferable that it is 0.02 mass% or less, and it is particularly preferable that it is not substantially contained.
  • the hardness (Mohs' hardness) of titanium oxide is preferably 5 to 8, and more preferably 7 to 7.5.
  • the true specific gravity (density) of titanium oxide is preferably 1.0 to 6.0 g / cm 3 , and more preferably 3.9 to 4.5 g / cm 3 .
  • the bulk specific gravity of titanium oxide is preferably 0.1 g / cm 3 to 1.0 g / cm 3 , and more preferably 0.2 g / cm 3 to 0.4 g / cm 3 .
  • the inorganic particles such as titanium oxide may be surface-treated with a surface treatment agent such as an organic compound.
  • a surface treatment agent such as an organic compound.
  • the surface treatment agent used for the surface treatment include polyol, aluminum oxide, aluminum hydroxide, silica (silicon oxide), hydrous silica, alkanolamine, stearic acid, organosiloxane, zirconium oxide, hydrogen dimethicone, silane coupling agent, Examples include titanate coupling agents. Of these, silane coupling agents are preferred.
  • inorganic particles, such as a titanium oxide are processed with the surface treating agent of Al (aluminum), Si (silicon), and organic substance.
  • the surface treatment may be carried out by using a single type of surface treatment agent or by combining two or more types of surface treatment agents. It is also preferable that the surface of inorganic particles such as titanium oxide is covered with an oxide such as aluminum oxide, silica, or zirconium oxide. Thereby, light resistance and dispersibility improve more.
  • inorganic particles such as titanium oxide are coated with a basic metal oxide or a basic metal hydroxide.
  • the basic metal oxide or the basic metal hydroxide include metal compounds containing magnesium, zirconium, cerium, strontium, antimony, barium, calcium, or the like.
  • the inorganic particles coated with the basic metal oxide or basic metal hydroxide can be obtained, for example, as follows. Inorganic particles are dispersed in water or a liquid containing water as a main component to obtain a slurry. If necessary, the inorganic particles are pulverized by a sand mill or a ball mill. The pH of the slurry is then made neutral or alkaline, optionally acidic. Thereafter, a water-soluble salt as a raw material for the coating material is added to the slurry to coat the surface of the inorganic particles. Thereafter, the slurry is neutralized and the inorganic particles are recovered. The recovered inorganic particles may be dried or dry pulverized.
  • Inorganic particles such as titanium oxide preferably have a surface treatment with a compound having an acidic site and capable of reacting with the acidic site.
  • the compound capable of reacting with the acidic site of the inorganic pigment include polymethyl alcohol such as trimethylolpropane, trimethylolethane, ditrimethylolpropane, trimethylolpropane ethoxylate or pentaerythritol, monoethanolamine, monopropanolamine, diethanolamine, diethanolamine, Examples include alkanolamines such as propanolamine, triethanolamine, and tripropanolamine, chlorosilane, and alkoxysilane.
  • inorganic particles commercially available particles can be preferably used.
  • Commercially available products of titanium oxide include, for example, trade names of Taipei R-550, R-580, R-630, R-670, R-680, R-780, R-780-2 manufactured by Ishihara Sangyo Co., Ltd.
  • titanium oxide described in paragraphs 0025 to 0027 of JP-A-2015-67794 can be used.
  • Examples of commercially available strontium titanate include SW-100 (manufactured by Titanium Industry Co., Ltd.).
  • Examples of commercially available barium sulfate include BF-1L (manufactured by Sakai Chemical Industry Co., Ltd.).
  • Examples of commercially available products of zinc oxide include Zincox Super F-1 (manufactured by Hakutech Co., Ltd.).
  • Examples of commercially available zirconium oxide include Z-NX (manufactured by Taiyo Mining Co., Ltd.).
  • a commercial product of titanium oxide may be used for the composition of the present invention after classification treatment. For example, a classified product of CR-90-2 or a classified product of MPT-141 can be preferably used.
  • the inorganic particles are not limited to those composed of a single inorganic substance, but may be particles combined with other materials.
  • core and shell composite particles composed of the core particles composed of the polymer particles and the shell layer composed of the inorganic nanoparticles can be referred to the descriptions in paragraphs 0012 to 0042 of JP-A-2015-47520. The contents are incorporated herein.
  • the content of particles having a refractive index of 2.1 or more with respect to light having a wavelength of 589 nm is preferably 1% by mass or more, more preferably 3% by mass or more, based on the total solid content of the composition. It is particularly preferably 5% by mass or more.
  • limiting in particular as an upper limit It is more preferable that it is 70 mass% or less with respect to the total solid of a composition, It is more preferable that it is 60 mass% or less, It is most preferable that it is 50 mass% or less.
  • the proportion of inorganic particles in the particles having a refractive index of 2.1 or more with respect to light having a wavelength of 589 nm is preferably 50% by mass or more, and more preferably 80% by mass or more.
  • the upper limit may be 100% by mass or 99% by mass or less. 99 mass% or less is preferable from a viewpoint of whiteness, the transmittance
  • the ratio of the white pigment in the particles having a refractive index of 2.1 or more with respect to light having a wavelength of 589 nm is preferably 50% by mass or more, and more preferably 80% by mass or more.
  • the upper limit may be 100% by mass or 99% by mass or less.
  • the proportion of titanium oxide in the particles having a refractive index of 2.1 or more with respect to light having a wavelength of 589 nm is preferably 50% by mass or more, and more preferably 80% by mass or more.
  • the upper limit may be 100% by mass or 99% by mass or less.
  • 99 mass% or less is preferable from a viewpoint of whiteness, the transmittance
  • the proportion of particles having a density of 1.0 to 6.0 g / cm 3 in particles having a refractive index of 2.1 or more with respect to light having a wavelength of 589 nm is preferably 50% by mass or more, and more preferably 80% by mass or more. More preferred.
  • the upper limit may be 100% by mass or 99% by mass or less. 99 mass% or less is preferable from a viewpoint of whiteness, the transmittance
  • the composition may contain other colorants other than particles having a refractive index of 2.1 or more with respect to light having a wavelength of 589 nm.
  • a * and b * in the L * a * b * color system of CIE 1976 are controlled within a preferable range when a film having a thickness of 3.0 ⁇ m is formed using the composition.
  • Cheap examples of other colorants include chromatic colorants and black colorants.
  • the composition of the present invention can contain a chromatic colorant.
  • the “chromatic colorant” means a colorant other than a white colorant (including a white pigment) and a black colorant.
  • the chromatic colorant is preferably a colorant having an absorption maximum in a wavelength range of 400 nm or more and less than 650 nm.
  • the chromatic colorant may be a chromatic pigment or a dye.
  • the chromatic pigment is preferably an organic pigment. It does not specifically limit as an organic pigment, A well-known chromatic color pigment can be used. Examples of organic pigments include the following. However, the present invention is not limited to these. Color Index (CI) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164
  • C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 22
  • dye there is no restriction
  • Chemical structures include pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, Xanthene, phthalocyanine, benzopyran, indigo, and pyromethene dyes can be used. Moreover, you may use the multimer of these dyes.
  • the dyes described in JP-A-2015-028144 and JP-A-2015-34966 can also be used.
  • acid dyes and derivatives thereof can be preferably used.
  • direct dyes, basic dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dyes, and derivatives thereof can also be used effectively.
  • Specific examples of the acid dye are shown below, but are not limited thereto. Examples thereof include the following dyes and derivatives of these dyes.
  • Acid Alizarin violet N Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40 to 45, 62, 70, 74, 80, 83, 86, 87, 90, 92, 103, 112, 113, 120, 129, 138, 147, 158, 171, 182, 192, 243, 324: 1, Acid Chrome violet K, Acid Fuchsin; acid green 1,3,5,9,16,25,27,50, Acid Orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95, Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252 257, 260, 26
  • azo, xanthene and phthalocyanine acid dyes are also preferred.
  • Acidic dyes such as Solvent orange 45; Rhodamine B, Rhodamine 110, and derivatives of these dyes are also preferably used.
  • the content of the chromatic colorant is preferably 0.1 to 70% by mass in the total solid content of the composition of the present invention.
  • the lower limit is more preferably 0.5% by mass or more, and particularly preferably 1.0% by mass or more.
  • the upper limit is more preferably 60% by mass or less, and particularly preferably 50% by mass or less.
  • the composition of this invention contains 2 or more types of chromatic colorants, it is preferable that the total amount is in the said range.
  • the composition of the present invention can contain a black colorant.
  • the black colorant may be an inorganic black colorant or an organic black colorant.
  • Examples of the organic black colorant include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds, and bisbenzofuranone compounds and perylene compounds are preferable.
  • Examples of the bisbenzofuranone compounds include those described in JP-T 2010-534726, JP-2012-515233, JP-2012-515234, and the like, for example, “Irgaphor Black” manufactured by BASF It is available.
  • Examples of perylene compounds include C.I. I. Pigment Black 31, 32 and the like.
  • Examples of the azomethine compound include those described in JP-A-1-170601, JP-A-2-34664, etc., and can be obtained, for example, as “Chromofine Black A1103” manufactured by Dainichi Seika Co., Ltd.
  • the inorganic black colorant is not particularly limited, and known ones can be used.
  • carbon black, titanium black, graphite, etc. are mentioned, carbon black and titanium black are preferable, and titanium black is more preferable.
  • Titanium black is black particles containing titanium atoms, and low-order titanium oxide and titanium oxynitride are preferable.
  • the surface of titanium black can be modified as necessary for the purpose of improving dispersibility and suppressing aggregation.
  • the surface of titanium black can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide. Further, treatment with a water-repellent substance as disclosed in JP 2007-302836 A is also possible.
  • Specific examples of black pigments include C.I. I. Pigment Black 1, 7, titanium black pigment, and the like.
  • Titanium black preferably has a small primary particle size and average primary particle size for each particle. Specifically, an average primary particle diameter in the range of 10 nm to 45 nm is preferable.
  • the specific surface area of titanium black is not particularly limited, BET (Brunauer, Emmett, Teller ) is preferably measured value is less than 5 m 2 / g or more 150 meters 2 / g by method, 20 m 2 / g or more 120 m 2 / More preferably, it is g or less.
  • Examples of commercially available titanium black include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, 13M-T (trade name: manufactured by Mitsubishi Materials Corporation), Tilack D (trade name: manufactured by Ako Kasei Co., Ltd.) and the like.
  • Titanium black can also be used as a dispersion.
  • the description in paragraphs 0020 to 0105 of JP2012-169556A can be referred to, and the contents thereof are incorporated in the present specification.
  • the composition of the present invention contains a resin.
  • the resin is blended, for example, for the purpose of dispersing particles such as pigments in the composition and the use of a binder.
  • a resin mainly used for dispersing particles in a composition is also referred to as a dispersant.
  • a dispersant such use of the resin is an example, and the resin can be used for purposes other than such use.
  • the composition of this invention contains resin whose refractive index with respect to the light of wavelength 589nm is 1.5 or less.
  • the composition preferably contains at least one kind of resin having a refractive index of 1.5 or less with respect to light having a wavelength of 589 nm, and has a refractive index of 1.5 with respect to light having a wavelength of 589 nm. It is more preferable to include only the following resin.
  • the content of the resin having a refractive index of 1.5 or less with respect to light having a wavelength of 589 nm with respect to the total mass of the resin is preferably 5% by mass or more, and more preferably 30% by mass or more. Preferably, it is more preferably 50% by mass or more, and particularly preferably 90% by mass or more.
  • the mass average refractive index (the mass average refractive index of the resin) of all the resins contained in the composition with respect to light having a wavelength of 589 nm is 1.5 or less, It is more preferably 1.49 or less, particularly preferably 1.47 or less, and particularly preferably 1.45 or less.
  • Mass-average refractive index of light of all resins contained in the composition with respect to light having a wavelength of 589 nm means that the refractive index ni of light of the i-th resin with respect to light of wavelength 589 nm and all of the composition of the i-th resin
  • the product of the mass ratio Xi to the resin is added to all the resins included in the composition. Specifically, it is a value calculated by the following formula when n is an integer of 2 or more and i is an integer of 1 or more.
  • the preferable range of the refractive index of the mass average for light with a wavelength of 589 nm of all the resins contained in the composition is the same as the preferable range of the refractive index for light with a wavelength of 589 nm of the resin.
  • the refractive index of the resin can be measured in an uncured state by the following method.
  • a specific measuring method is that after a film made of only a resin to be measured is formed on a Si wafer at 300 nm, the refractive index of the obtained film is determined by ellipsometry (Lambda Ace RE-3300 (trade name), large Measured using Nippon Screen Manufacturing Co., Ltd.
  • the weight average molecular weight (Mw) of the resin is preferably from 1,000 to 200,000, more preferably from 2,000 to 100,000. These ranges are preferable from the viewpoints of compatibility between the resin and all components in the composition and L *.
  • the content of the resin having a refractive index of 1.5 or less with respect to light having a wavelength of 589 nm is preferably 5 to 90% by mass, more preferably 10 to 60% by mass with respect to the total solid content of the composition. Particularly preferred is 10 to 50% by mass. These ranges are preferable from the viewpoints of pattern shape, heat resistance, and L *.
  • One type of resin having a refractive index of 1.5 or less with respect to light having a wavelength of 589 nm may be included, or two or more types may be included. When two or more types are included, the total amount is preferably within the above range.
  • the resin having a refractive index of 1.5 or less with respect to light having a wavelength of 589 nm examples include a fluorine resin and a polysiloxane resin.
  • the resin is preferably a polysiloxane resin (polysiloxane is preferably a main skeleton), and a polysiloxane resin having a refractive index of 1.5 or less with respect to light having a wavelength of 589 nm. Is more preferable, and a polysiloxane resin that is also an alkali-soluble resin having a refractive index with respect to light having a wavelength of 589 nm of 1.5 or less is particularly preferable.
  • the preferable properties of the polysiloxane resin, which is also an alkali-soluble resin, as the alkali-soluble resin are the same as the preferable properties of the alkali-soluble resin used as the other binder.
  • a resin having a refractive index of 1.5 or less with respect to light having a wavelength of 589 nm preferably has a repeating unit containing a group that promotes alkali solubility of an alkali-soluble resin described later in order to impart alkali solubility. Preferred groups that promote alkali solubility are the same as those described below.
  • the fluorine-based resin is not particularly limited as long as the resin contains a fluorine atom.
  • Rf is a substituent containing a fluoroalkyl group or a perfluoroalkyl group, n represents 1 or 2, and R 1 represents a hydrogen atom or a methyl group.
  • Rf is preferably a fluoroalkyl group having 9 or more fluorine atoms or a perfluoroalkyl group-containing substituent.
  • Specific examples of the fluoroalkyl group or perfluoroalkyl group-containing substituent having 9 or more fluorine atoms include the following fluoroalkyl (meth) acrylates.
  • CH 2 CRCO 2 (CH 2 ) m C n F 2n + 1 m represents 1 or 2
  • n represents an integer of 4 to 12.
  • R represents an alkyl group having 1 to 4 carbon atoms.
  • CH 2 CRCO 2 (CH 2 ) m (CF 2 ) n H m represents 1 or 2, and n represents an integer of 4 to 12.
  • R represents an alkyl group having 1 to 4 carbon atoms.
  • the number of fluorine atoms per substituent containing a fluoroalkyl group or perfluoroalkyl group is preferably 9 to 30, and more preferably 13 to 25.
  • a polymer compound having a repeating unit derived from a fluorine atom-containing unsaturated monomer as the fluorine resin.
  • the fluorine atom-containing unsaturated monomer include a radical polymerizable monomer having a polyfluoroalkyl group or a polyfluoroether group
  • examples of the perfluoroalkyl group include a perfluoromethyl group, a perfluoroethyl group, a perfluoroethyl group, and a perfluoroethyl group.
  • a fluoropropyl group, a perfluorobutyl group, a perfluorohexyl group, a perfluorooctyl group, a perfluorodecyl group, a perfluorododecyl group, and a perfluorotetradecyl group are preferred.
  • a fluorine atom containing unsaturated monomer can be used individually by 1 type, or can also use 2 or more types together.
  • a commercial item can also be used as a fluorine atom containing unsaturated monomer.
  • trade name light ester FM-108, light ester M-3F, light ester M-4F trade name CHEMINOX FAAC, CHEMINOX FAMAC, CHEMINOX FAAC-M, CHEMINOX FAMAC-M, manufactured by Kyoeisha Chemical Co., Ltd. CHEMINOX PFAE, CHEMINOX PFOE, etc.
  • (A) a repeating unit having at least one of a repeating unit derived from the monomer represented by formula (F1) and a repeating unit derived from a fluorine atom-containing unsaturated monomer, and a group that promotes alkali solubility.
  • a high molecular compound having can also be used as the fluororesin.
  • the preferred range of the group that promotes alkali solubility is the same as the preferred range of the group that promotes alkali solubility of the later-described alkali-soluble resin.
  • fluorine-based resin As an example of the fluorine-based resin, the fluorine-based surfactants described in the lower right column on page 6 to the upper right column on page 9 of JP-A-2-804 can be referred to, and the contents thereof are incorporated herein.
  • polysiloxane resin- There is no restriction
  • a polysiloxane resin a polysiloxane resin obtained by hydrolyzing and condensing a compound represented by the following general formula (1) alone, or a compound represented by the following general formula (1) and another silane A polysiloxane resin obtained by condensation with a compound and a cohydrolyzate can be used.
  • the polysiloxane resin descriptions in ⁇ 0014> to ⁇ 0035> of JP-A-2014-66988 can be referred to, and the contents thereof are incorporated herein.
  • the polysiloxane resin is a polysiloxane resin obtained by cohydrolyzate condensation of an alkoxysilane compound containing a compound represented by the following general formula (2) It is preferable to use from the viewpoint of improving the solvent resistance.
  • the polysiloxane-based resin is a polysiloxane resin obtained by cohydrolyzate condensation of an alkoxysilane compound containing a compound represented by the following general formula (3) Is preferably used from the viewpoint of increasing the acid value of the polysiloxane resin and improving the pattern shape.
  • a polysiloxane resin obtained by cohydrolyzate condensation of an alkoxysilane compound containing a compound represented by the following general formula (3) can also be used as an alkali-soluble resin.
  • each R 1 independently represents an alkyl group or a phenyl group
  • each R 2 independently represents a hydrogen atom or an alkyl group.
  • R 1 and R 2 in the general formula (1) are preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and an alkyl group having 1 to 3 carbon atoms. Particularly preferred is an alkyl group having 1 or 2 carbon atoms, and most preferred is a methyl group.
  • R 1 and R 2 in the general formula (1) may be linear, branched or cyclic, and is preferably linear.
  • R 3 represents a methyl group or a hydrogen atom
  • R 4 represents an alkylene group having 1 to 4 carbon atoms
  • R 5 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R 6 represents each independently an alkyl group having 1 to 6 carbon atoms
  • n represents an integer of 1 to 3.
  • R 4 in the general formula (2) is preferably an alkylene group having 1 to 3 carbon atoms, and more preferably an alkylene group having 3 carbon atoms.
  • the preferred ranges of R 6 and R 5 in the general formula (2) are the same as the preferred ranges of R 1 and R 2 in the general formula (1), respectively.
  • N in the general formula (2) is preferably 2 or 3, and more preferably 3.
  • l represents an integer of 0 to 2
  • m represents an integer of 0 to 3
  • R 7 represents an alkylene group having 1 to 4 carbon atoms
  • R 8 each independently represents a hydrogen atom or
  • R 1 represents an alkyl group having 1 to 4 carbon atoms
  • each R 9 independently represents an alkyl group having 1 to 6 carbon atoms.
  • l is more preferably 1.
  • M in the general formula (3) is preferably 2 or 3, and more preferably 3.
  • R 7 in the general formula (3) is preferably an alkylene group having 1 to 3 carbon atoms, and more preferably an alkylene group having 3 carbon atoms.
  • the preferable ranges of R 9 and R 8 in the general formula (3) are the same as the preferable ranges of R 1 and R 2 in the general formula (1), respectively.
  • Examples of the compound represented by the general formula (1) include dimethoxydimethylsilane, diethoxydimethylsilane, dimethoxydiphenylsilane, diethoxydiphenylsilane, dihydroxydiphenylsilane, dimethoxy (methyl) (phenyl) silane, diethoxy (methyl) ( Phenyl) silane, dimethoxy (methyl) (phenethyl) silane, dicyclopentyldimethoxysilane or cyclohexyldimethoxy (methyl) silane, methyltrimethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, Phenyltriethoxysilane.
  • the compound represented by the general formula (1) is preferably dimethoxydimethylsilane, dimethoxydiphenylsilane, or phenyl
  • the proportion of the compound represented by the general formula (1) in the alkoxysilane compound to be subjected to cohydrolyzate condensation is preferably 25 to 75 mol%, more preferably 35 to 75 mol%, It is particularly preferable that the amount be ⁇ 70 mol%.
  • the proportion of dimethoxydiphenylsilane, diethoxydiphenylsilane and dihydroxydiphenylsilane in the alkoxysilane compound to be subjected to cohydrolyzate condensation is preferably 0 to 50 mol%, and preferably 0 to 45 mol%. Is more preferably 0 to 30 mol%, particularly preferably 0 to 10 mol%.
  • Examples of the compound represented by the general formula (2) include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, Examples include 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-acryloxypropyltriethoxysilane, or 3-acryloxypropylmethyldiethoxysilane.
  • the compound represented by the general formula (2) is preferably 3-methacryloxypropyltrimethoxysilane.
  • the proportion of the compound represented by the general formula (2) in the alkoxysilane compound to be subjected to cohydrolyzate condensation is preferably 10 to 45 mol%, more preferably 10 to 30 mol%, Particularly preferred is ⁇ 20 mol%.
  • Examples of the compound represented by the general formula (3) include 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylpropyl succinic anhydride, 3-trimethoxysilylethyl succinic anhydride, and 3-trimethoxysilylbutyl.
  • Examples thereof include succinic anhydride, 3-diethoxymethylsilylpropyl succinic anhydride, 3-dimethoxymethylsilylethyl succinic anhydride, and 3-dimethoxymethylsilylbutyl succinic anhydride.
  • the compound represented by the general formula (3) is preferably 3-trimethoxysilylpropyl succinic anhydride.
  • the proportion of the compound represented by the general formula (3) in the alkoxysilane compound to be subjected to cohydrolyzate condensation is 1 to 30 mol% from the viewpoint of improving the pattern shape by increasing the acid value of the polysiloxane resin. It is preferably 1 to 25% by mole, more preferably 1 to 20% by mole from the viewpoint of further suppressing density unevenness after one month.
  • the alkoxysilane compound to be subjected to cohydrolyzate condensation preferably further contains a compound represented by the general formula (5).
  • R 12 in the general formula (5) represents a monovalent organic group having an epoxy group
  • R 13 each independently represents an alkyl group.
  • the monovalent organic group having an epoxy group represented by R 12 in the general formula (5) preferably has 1 to 5 epoxy groups, more preferably 1 or 2 epoxy groups. Particularly preferred.
  • the monovalent organic group having an epoxy group represented by R 12 in the general formula (5) is preferably a group having an epoxy group bonded to the end via a linking group, and an alkylene group (preferably having 1 carbon atom). More preferably, it is a group having an epoxy group bonded to the terminal via at least one of ⁇ 10, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms and oxygen atoms.
  • the preferable range of R 13 in the general formula (5) is the same as the preferable range of R 2 in the general formula (1).
  • Examples of the compound represented by the general formula (5) include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, 3 -(3,4-epoxycyclohexyl) propyltriethoxysilane.
  • the compound represented by the general formula (5) is preferably 3-glycidyloxypropyltrimethoxysilane or 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane.
  • the proportion of the compound represented by the general formula (5) in the alkoxysilane compound subjected to cohydrolyzate condensation is preferably 10 mol% or less, more preferably 8 mol% or less, and more preferably 5 mol%. It is particularly preferred that
  • the alkoxysilane compound to be subjected to cohydrolyzate condensation may contain other alkoxysilane compounds other than the compounds represented by the general formulas (1) to (3) and (5).
  • Other alkoxysilane compounds other than the compounds represented by the general formulas (1) to (3) and (5) include, for example, phenethyltrimethoxysilane, naphthyltrimethoxysilane, phenethyltriethoxysilane, naphthyltriethoxysilane, tetra Examples include methoxysilane or tetraethoxysilane.
  • the proportion of the other alkoxysilane compound in the alkoxysilane compound to be subjected to cohydrolyzate condensation is 3 mol% or less from the viewpoint of suppressing concentration unevenness after one month and improving solvent resistance. Preferably, it is 2 mol% or less, more preferably 1 mol% or less.
  • 20 mol% or more (preferably 40 mol% or more, more preferably 50 mol% or more, particularly preferably 60 mol% or more) of the side chain of the polysiloxane resin is an alkyl having 1 to 4 carbon atoms.
  • the side chain containing a phenyl group is preferably 20 mol% or less from the viewpoint of lowering the refractive index of the polysiloxane resin, more preferably 10 mol% or less. It is particularly preferable that the amount is not more than mol%.
  • the polysiloxane resin can be obtained by co-hydrolyzate condensation, that is, hydrolysis and partial condensation of an alkoxysilane compound.
  • a general method can be used for cohydrolyzate condensation. For example, a method of adding an organic solvent, water and, if necessary, a catalyst to the mixture and heating and stirring at 50 to 150 ° C. for about 0.5 to 100 hours can be used. During heating and stirring, if necessary, hydrolysis by-products (alcohols such as methanol) and condensation by-products (water) may be distilled off by distillation.
  • polysiloxane resins obtained by cohydrolyzate condensation of monomers that are alkoxysilane compounds described in the following table.
  • the composition of the present invention may contain other binder in addition to the resin having a refractive index of 1.5 or less with respect to light having a wavelength of 589 nm.
  • other binders can be arbitrarily used.
  • a resin that is soluble or swellable in water or weak alkaline water is selected to enable water development or weak alkaline water development. For example, when an alkali-soluble resin is used, alkali development becomes possible.
  • resins examples include radical polymers having a carboxy group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-54-25957.
  • Etc radical polymers having a carboxy group in the side chain
  • Examples of the monomer having a carboxy group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid and 4-carboxystyrene.
  • Examples of the monomer having an acid anhydride include maleic anhydride. It is done.
  • an acidic cellulose derivative which has a carboxy group in a side chain is also mentioned.
  • the other binder is also preferably a resin soluble in an alkali developer (also referred to as an alkali-soluble resin).
  • a resin that is a thermosetting compound such as an epoxy resin or a melamine resin can be used as the binder.
  • the alkali-soluble resin can be appropriately selected from polymers having groups that promote alkali-solubility.
  • the number average molecular weight (Mn) of the alkali-soluble resin is preferably 1000 to 20,000.
  • the acid value of the alkali-soluble resin is preferably 30 to 500 mgKOH / g.
  • the lower limit is more preferably 50 mgKOH / g or more, and still more preferably 70 mgKOH / g or more.
  • the upper limit is more preferably 400 mgKOH / g or less, further preferably 200 mgKOH / g or less, particularly preferably 150 mgKOH / g or less, and most preferably 120 mgKOH / g or less.
  • the alkali-soluble resin is preferably a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin, or an acrylic / acrylamide copolymer resin from the viewpoint of heat resistance.
  • acryl-based resins, acrylamide-based resins, and acrylic / acrylamide copolymer resins are more preferable.
  • the group that promotes alkali solubility include a carboxy group, a phosphate group, a sulfo group, and a phenolic hydroxy group, and a carboxy group is preferred. There may be only one type of acid group, or two or more types of acid groups.
  • the alkali-soluble resin can be synthesized by, for example, a known radical polymerization method.
  • Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and the conditions are determined experimentally. You can also.
  • the alkali-soluble resin is preferably a polymer having a carboxy group in the side chain, such as a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, and a partially esterified malein.
  • a polymer having a carboxy group in the side chain such as a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, and a partially esterified malein.
  • examples include an acid copolymer, an alkali-soluble phenol resin such as a novolak resin, an acidic cellulose derivative having a carboxy group in the side chain, and a polymer having a hydroxy group added with an acid anhydride.
  • Examples of other monomers copolymerizable with (meth) acrylic acid include monomers described in paragraphs 0017 to 0019 of JP-A-2015-34961.
  • alkyl (meth) acrylate, aryl (meth) acrylate, vinyl compound, N-substituted maleimide monomer and the like can be mentioned.
  • alkyl (meth) acrylate and aryl (meth) acrylate methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, Hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, etc.
  • Vinyl compounds include styrene, ⁇ -methylstyrene, vinyltoluene, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, polystyrene Macromonomer, polymethylmethacrylate macromonomer, as N-position-substituted maleimide monomer described in JP-A-10-300922, may be mentioned N- phenylmaleimide, an N- cyclohexyl maleimide and the like. In addition, only 1 type may be sufficient as the other monomer copolymerizable with these (meth) acrylic acid, and 2 or more types may be sufficient as it.
  • Alkali-soluble resins include benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, benzyl (meth) acrylate / Multi-component copolymers composed of (meth) acrylic acid / other monomers can be preferably used.
  • FF-426 made by Fujikura Kasei Co., Ltd.
  • an alkali-soluble resin having a polymerizable group may be used as the alkali-soluble resin.
  • the solvent resistance of the obtained film tends to be improved.
  • the polymerizable group include a (meth) allyl group and a (meth) acryloyl group.
  • the alkali-soluble resin having a polymerizable group an alkali-soluble resin having a polymerizable group in the side chain is useful.
  • the alkali-soluble resin having a polymerizable group include a dial NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polyurethane acrylic oligomer.
  • Diamond Shamrock Co., Ltd. shows a variety of materials that are used for the following reasons: Diamond Shamrock Co., Ltd., Viscoat R-264, KS resist. 106 (both manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (for example, ACA230AA), Plaxel CF200 series (both manufactured by Daicel Corporation), Ebecryl 3800 (manufactured by Daicel UCB Co., Ltd.), Acryl And RD-F8 (manufactured by Nippon Shokubai Co., Ltd.).
  • Cyclomer P series for example, ACA230AA
  • Plaxel CF200 series both manufactured by Daicel Corporation
  • Ebecryl 3800 manufactured by Daicel UCB Co., Ltd.
  • Acryl And RD-F8 manufactured by Nippon Shokubai Co., Ltd.
  • the alkali-soluble resin is a monomer containing at least one of a compound represented by the following formula (ED1) and a compound represented by the following formula (ED2) (hereinafter, these compounds may be referred to as “ether dimers”). It is also preferable to include a polymer obtained by polymerizing the components. For details of a polymer obtained by polymerizing a monomer component containing an ether dimer, paragraphs 0022 to 0031 of JP-A-2015-34961 can be referred to, the contents of which are incorporated herein.
  • R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
  • R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms.
  • the description in JP 2010-168539 A can be referred to.
  • ether dimer for example, paragraph 0317 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification. Only one type of ether dimer may be used, or two or more types may be used.
  • the alkali-soluble resin may contain a structural unit derived from a compound represented by the following formula (X).
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents an alkylene group having 2 to 10 carbon atoms
  • R 3 represents a hydrogen atom or a benzene ring that may contain a benzene ring.
  • n represents an integer of 1 to 15.
  • the alkylene group of R 2 preferably has 2 to 3 carbon atoms. Further, the alkyl group of R 3 has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and the alkyl group of R 3 may contain a benzene ring. Examples of the alkyl group containing a benzene ring represented by R 3 include a benzyl group and a 2-phenyl (iso) propyl group.
  • alkali-soluble resin examples include the following resins. Moreover, the resin described in JP-A-2015-34961, paragraph 0037 is also included. Among these resins, an alkali-soluble resin having the following polymerizable group is preferable from the viewpoint of solvent resistance.
  • the content of other binders is preferably 0 to 60% by mass with respect to the total solid content of the composition.
  • the upper limit is preferably 60% by mass or less, and more preferably 50% by mass or less.
  • the composition may contain only one type of other binder, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
  • the composition of the present invention can contain a dispersant as a resin.
  • the dispersant preferably contains one or more selected from acidic resins, basic resins and amphoteric resins, and more preferably at least one selected from acidic resins and amphoteric resins. According to this aspect, the dispersibility of the particles is good.
  • the “acidic resin” means a resin having an acid group and having an acid value of 5 mgKOH / g or more and an amine value of less than 5 mgKOH / g.
  • the acidic resin preferably does not have a basic group.
  • the acid value of the acidic resin is preferably 5 to 200 mgKOH / g.
  • the lower limit is more preferably 10 mgKOH / g or more, and further preferably 20 mgKOH / g or more.
  • the upper limit is more preferably 100 mgKOH / g or less, and still more preferably 60 mgKOH / g or less.
  • the amine value of the acidic resin is preferably 2 mgKOH / g or less, and more preferably 1 mgKOH / g or less.
  • “basic resin” means a resin having a basic group and having an amine value of 5 mgKOH / g or more and an acid value of less than 5 mgKOH / g.
  • the basic resin preferably does not have an acid group.
  • an amino group is preferable.
  • the amine value of the basic resin is preferably 5 to 200 mgKOH / g, more preferably 5 to 150 mgKOH / g, and still more preferably 5 to 100 mgKOH / g.
  • the “amphoteric resin” means a resin having an acid group and a basic group and having an acid value of 5 mgKOH / g or more and an amine value of 5 mgKOH / g or more.
  • the acid group include those described above, and a carboxy group is preferable.
  • the basic group an amino group is preferable.
  • the amphoteric resin preferably has an acid value of 5 mgKOH / g or more and an amine value of 5 mgKOH / g or more.
  • the acid value is preferably 5 to 200 mgKOH / g.
  • the lower limit is more preferably 10 mgKOH / g or more, and further preferably 20 mgKOH / g or more.
  • the upper limit is more preferably 150 mgKOH / g or less, and even more preferably 100 mgKOH / g or less.
  • the amine value is preferably 5 to 200 mgKOH / g.
  • the lower limit is more preferably 10 mgKOH / g or more, and further preferably 20 mgKOH / g or more.
  • the upper limit is more preferably 150 mgKOH / g or less, and even more preferably 100 mgKOH / g or less.
  • the dispersant examples include polymer dispersants [for example, resins having amine groups (polyamideamine and salts thereof), oligoimine resins, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, Modified poly (meth) acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid formalin polycondensate] and the like.
  • the polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer from the structure thereof.
  • the dispersant has a site having an adsorption ability for the pigment (hereinafter, collectively referred to as “adsorption site”).
  • Adsorption sites include acid groups, urea groups, urethane groups, groups having coordinating oxygen atoms, groups having basic nitrogen atoms, heterocyclic groups, alkyloxycarbonyl groups, alkylaminocarbonyl groups, carboxy groups, sulfonamides And monovalent substituents having at least one group selected from the group consisting of a group, an alkoxysilyl group, an epoxy group, an isocyanate group and a hydroxyl group.
  • the adsorption site is preferably an acid-based adsorption site. An acid group etc.
  • an acid type adsorption site is at least one of a phosphorus atom containing group and a carboxy group.
  • the phosphorus atom-containing group include a phosphate group, a polyphosphate group, and a phosphate group.
  • the resin (dispersant) is preferably a resin represented by the following formula (111).
  • R 1 represents an (m + n) -valent linking group
  • R 2 represents a single bond or a divalent linking group
  • a 1 is an acid group, a urea group, a urethane group, a group having a coordinating oxygen atom, a group having a basic nitrogen atom, a heterocyclic group, an alkyloxycarbonyl group, an alkylaminocarbonyl group, a carboxy group, a sulfonamide group
  • the n A 1 and R 2 may be the same or different.
  • m represents a positive number of 8 or less
  • n represents 1 to 9, and m + n satisfies 3 to 10.
  • P 1 represents a monovalent polymer chain.
  • the m P 1 may be the same or different.
  • the resin represented by the formula (111) can interact with a pigment (for example, inorganic particles such as titanium oxide), the resin represented by the formula (111) is n By having one (1 to 9) substituents A 1 , it is possible to improve the dispersibility of the pigment in the composition by strongly interacting with the pigment (for example, inorganic particles such as titanium oxide).
  • m polymer chains P 1 of the resin represented by the formula (111) can function as a steric repulsion group. Inorganic particles such as titanium) can be uniformly dispersed.
  • R 1 represents an (m + n) -valent linking group.
  • (M + n) -valent linking groups include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and Groups consisting of 0 to 20 sulfur atoms are included.
  • Specific examples of the (m + n) -valent linking group include a group (which may form a ring structure) constituted by combining two or more of the following structural units or the following structural units. .
  • paragraphs 0076 to 0084 of JP-A-2007-277514 can be referred to, the contents of which are incorporated herein.
  • P 1 represents a monovalent polymer chain.
  • the monovalent polymer chain is preferably a monovalent polymer chain having a repeating unit derived from a vinyl compound.
  • paragraphs 0087 to 0098 of JP-A-2007-277514 can be referred to, the contents of which are incorporated herein.
  • R 2 represents a single bond or a divalent linking group.
  • Divalent linking groups include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 To 20 sulfur atoms are included, which may be unsubstituted or further substituted.
  • Specific examples of the divalent linking group include a group constituted by combining two or more of the following structural units or the following structural units. For details of the divalent linking group, paragraphs 0071 to 0075 of JP-A-2007-277514 can be referred to, the contents of which are incorporated herein.
  • Examples of the polymer compound represented by the above formula (111) include a description after paragraph 0039 (corresponding to ⁇ 0053> of US Patent Application Publication No. 2010/0233595) of JP-A-2007-277514, and The description in paragraphs 0081 to 0117 of JP-A-2015-34961 can be referred to, and the contents thereof are incorporated in this specification.
  • a graft copolymer including a repeating unit represented by any one of the following formulas (11) to (14) can also be used.
  • W 1 , W 2 , W 3 , and W 4 each independently represent an oxygen atom or NH
  • X 1 , X 2 , X 3 , X 4 , and X 5 each independently represents a hydrogen atom or a monovalent group
  • Y 1 , Y 2 , Y 3 , and Y 4 each independently represent a divalent linking group
  • Z 1 , Z 2 , Z 3 , and Z 4 independently represents a monovalent group
  • R 3 represents an alkylene group
  • R 4 represents a hydrogen atom or a monovalent group
  • n, m, p, and q are each independently an integer of 1 to 500 J and k each independently represents an integer of 2 to 8, and in formula (13), when p is 2 to 500, a plurality of R 3 may be the same or different from each other;
  • q is 2 to 500
  • a plurality of X 5 and R 4 may be the same or different from each other.
  • W 1 , W 2 , W 3 , and W 4 are preferably oxygen atoms.
  • X 1 , X 2 , X 3 , X 4 , and X 5 are preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, more preferably each independently a hydrogen atom or a methyl group, A methyl group is particularly preferred.
  • 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.
  • the monovalent group represented by Z 1 , Z 2 , Z 3 , and Z 4 is not particularly limited, and specifically includes an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, and an alkylthioether group. , Arylthioether group, heteroarylthioether group, amino group and the like.
  • the organic group represented by Z 1 , Z 2 , Z 3 , and Z 4 those having a steric repulsion effect are particularly preferable from the viewpoint of improving dispersibility, and each independently has 5 to 24 carbon atoms.
  • 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 particularly 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 (11) and (12) are preferably integers of 4 to 6 and most preferably 5 from the viewpoints of dispersion stability and developability.
  • R 3 represents an alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms.
  • 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 group.
  • the monovalent 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, more preferably a hydrogen atom or an alkyl group.
  • R 4 is an alkyl group, 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 is preferable, and 1 to 20 carbon atoms is preferable.
  • linear alkyl groups having 1 to 6 carbon atoms are particularly preferable.
  • q is 2 ⁇ 500
  • X 5 a plurality present in the graft copolymer may be different from one another the same.
  • the description in paragraphs 0025 to 0094 of JP2012-255128A can be referred to, and the above contents are incorporated in this specification.
  • Specific examples of the graft copolymer include the following resins. Further, there are resins described in JP-A-2012-255128, paragraphs 0072 to 0094, the contents of which are incorporated herein.
  • the resin (dispersant) is also preferably an oligoimine dispersant containing a basic nitrogen atom in at least one of the main chain and the side chain.
  • the oligoimine dispersant include a repeating unit having a partial structure X having a functional group of 14 or less pKa (power of Ka; Ka is an acid dissociation constant), and an oligomer chain or a polymer chain Y having 40 to 10,000 atoms.
  • a resin having a containing side chain and having a basic nitrogen atom in at least one of the main chain and the side chain is preferred.
  • This resin interacts with a pigment (for example, inorganic particles such as titanium oxide) at both a nitrogen atom and a functional group of pKa 14 or less that the structure X has, and the resin is an oligomer having 40 to 10,000 atoms.
  • a pigment for example, inorganic particles such as titanium oxide
  • the oligomer chain or polymer chain Y functions as a steric repulsion group, thereby exhibiting good dispersibility and uniformly dispersing inorganic particles such as titanium oxide. it can.
  • sedimentation of inorganic particles such as titanium oxide can be suppressed for a long period of time by the interaction between the oligomer chain or polymer chain Y and the solvent.
  • the oligomer chain or polymer chain Y functions as a steric repulsion group, aggregation of pigments (for example, inorganic particles such as titanium oxide) is prevented, so that the inclusion of pigments (preferably inorganic particles such as titanium oxide) is included. Even if the amount is increased, excellent dispersibility can be obtained.
  • pigments for example, inorganic particles such as titanium oxide
  • the “basic nitrogen atom” is not particularly limited as long as it is a basic nitrogen atom, and the resin contains a structure having a nitrogen atom having a pKb (power of Kb; Kb is a base dissociation constant) of 14 or less. It is preferable to include a structure having a nitrogen atom of pKb10 or less.
  • pKb (base strength) refers to pKb at a water temperature of 25 ° C., which is one of the indexes for quantitatively representing the strength of the base, and is synonymous with the basicity constant.
  • the functional group of pKa14 or less possessed by the partial structure X is not particularly limited, and the structure thereof is not particularly limited as long as the physical properties satisfy this condition.
  • a functional group having a pKa of 12 or less is preferable, and a functional group having a pKa of 11 or less is most preferable.
  • a carboxy group (about pKa 3 to 5), a sulfo group (about pKa -3 to -2), a —COCH 2 CO— group (about pKa 8 to 10), a —COCH 2 CN group (pKa) About 8 to 11), —CONHCO— group, phenolic hydroxyl group, —R F CH 2 OH group or — (R F ) 2 CHOH group (R F represents a perfluoroalkyl group; pKa about 9 to 11), sulfonamide Group (about pKa 9 to 11) and the like.
  • the partial structure X having a functional group of pKa14 or less is preferably directly bonded to the basic nitrogen atom in the repeating unit containing a nitrogen atom, and the basic nitrogen atom and the partial structure X of the repeating unit containing a basic nitrogen atom. And may be linked in a form that forms not only a covalent bond but also an ionic bond to form a salt.
  • the oligoimine-based dispersant has a repeating unit containing a basic nitrogen atom to which a partial structure X having a functional group of pKa14 or less is bonded, and an oligomer chain or polymer chain Y having 40 to 10,000 atoms in the side chain.
  • a resin is preferred.
  • the oligoimine-based dispersant includes (i) a poly (lower alkyleneimine) -based repeating unit, a polyallylamine-based repeating unit, a polydiallylamine-based repeating unit, a metaxylenediamine-epichlorohydrin polycondensate-based repeating unit, and a polyvinylamine-based repeating unit.
  • a resin having (ii) an oligomer chain having 40 to 10,000 atoms or a polymer chain Y in the chain is preferred.
  • “lower” in poly (lower alkyleneimine) means 1 to 5 carbon atoms
  • “lower alkyleneimine” means alkyleneimine having 1 to 5 carbon atoms.
  • Examples of the oligomer chain or polymer chain Y having 40 to 10,000 atoms include known polymer chains such as polyester, polyamide, polyimide, and poly (meth) acrylate that can be connected to the main chain portion of the resin.
  • the bonding site of the oligomer chain or polymer chain Y with the resin is preferably the terminal of the oligomer chain or polymer chain Y.
  • the oligomer chain or polymer chain Y is selected from poly (lower alkylene imine) -based repeating units, polyallylamine-based repeating units, polydiallylamine-based repeating units, metaxylenediamine-epichlorohydrin polycondensate-based repeating units, and polyvinylamine-based repeating units. It is preferably bonded to a nitrogen atom of a repeating unit containing at least one kind of nitrogen atom.
  • At least one nitrogen atom selected from poly (lower alkyleneimine) -based repeating units, polyallylamine-based repeating units, polydiallylamine-based repeating units, metaxylenediamine-epichlorohydrin polycondensate-based repeating units, and polyvinylamine-based repeating units
  • the bonding mode between the main chain portion such as a repeating unit containing bismuth and Y is a covalent bond, an ionic bond, or a mixture of a covalent bond and an ionic bond.
  • Y is preferably ion-bonded to a nitrogen atom of a repeating unit containing a nitrogen atom as an amide bond or carboxylate.
  • the number of atoms of the oligomer chain or polymer chain Y is preferably 50 to 5,000, more preferably 60 to 3,000, from the viewpoint of dispersibility, dispersion stability, and developability. Moreover, the number average molecular weight of Y can be measured by the polystyrene conversion value by GPC method. The number average molecular weight of Y is preferably 1,000 to 50,000, and more preferably 1,000 to 30,000.
  • the oligoimine dispersant includes, for example, at least one of a repeating unit represented by the formula (I-1), a repeating unit represented by the formula (I-2), and a repeating unit represented by the formula (I-2a). And the like.
  • R 1 and R 2 each independently represents a hydrogen atom, a halogen atom or an alkyl group (preferably having 1 to 6 carbon atoms).
  • a independently represents an integer of 1 to 5; * Represents a connecting part between repeating units.
  • R 8 and R 9 are the same groups as R 1 .
  • L is a single bond, an alkylene group (preferably having 1 to 6 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), an arylene group (preferably having 6 to 24 carbon atoms), a heteroarylene group (having 1 to 6 carbon atoms).
  • an imino group preferably having a carbon number of 0 to 6
  • an ether group preferably having a carbon number of 0 to 6
  • a thioether group preferably having a carbonyl group, or a combination group thereof.
  • a single bond or —CR 5 R 6 —NR 7 — is preferable.
  • R 5 and R 6 each independently represents a hydrogen atom, a halogen atom, or an alkyl group (preferably having 1 to 6 carbon atoms).
  • R 7 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • L a is a structural site ring structure formed together with CR 8 CR 9 and N, it is preferable together with the carbon atom of CR 8 CR 9 is a structural site that form a non-aromatic heterocyclic ring having 3 to 7 carbon atoms . More preferably, it is a structural part that forms a 5- to 7-membered non-aromatic heterocyclic ring by combining the carbon atom of CR 8 CR 9 and N (nitrogen atom), and more preferably a 5-membered non-aromatic heterocyclic ring. It is a structural part to be formed, and a structural part to form pyrrolidine is particularly preferable. This structural part may further have a substituent such as an alkyl group.
  • X represents a group having a functional group of pKa14 or less.
  • Y represents an oligomer chain or a polymer chain having 40 to 10,000 atoms.
  • the dispersing agent (oligoimine-based dispersing agent) further comprises at least one copolymer component selected from repeating units represented by formula (I-3), formula (I-4), and formula (I-5). It may contain as. When the dispersant contains such a repeating unit, the dispersibility of the particles can be further improved.
  • R 1 , R 2 , R 8 , R 9 , L, L a , a and * are as defined in the formulas (I-1), (I-2) and (I-2a).
  • Ya represents an oligomer chain or a polymer chain having an anion group and having 40 to 10,000 atoms.
  • oligoimine-based dispersant the description of paragraph numbers 0118 to 0190 in JP-A-2015-34961 can be referred to, and the above contents are incorporated in this specification.
  • the oligoimine dispersant for example, the following resins and the resins described in paragraph numbers 0169 to 0190 of JP-A-2015-34961 can be used.
  • a dispersant which is a polysiloxane resin
  • a dispersant which is a polysiloxane resin
  • the dispersant which is a polysiloxane resin preferably includes at least a repeating unit having an acid group and a repeating unit having a siloxane bond. Examples of the repeating unit having an acid group include a repeating unit derived from (meth) acrylic acid.
  • the dispersant which is a polysiloxane resin a resin having a refractive index of 1.5 or less with respect to light having a wavelength of 589 nm may be used.
  • a preferred embodiment of the dispersant which is a polysiloxane resin is the same as the preferred embodiment of the resin having a refractive index of 1.5 or less with respect to light having a wavelength of 589 nm.
  • the dispersant is also available as a commercial product. Specific examples of such a dispersant include “Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylic acid ester), 110, 180 (acid) manufactured by BYK Chemie Co., Ltd.
  • the dispersing agent which has a phosphorus atom containing group (for example, phosphoric acid group etc.) as an acid system adsorption site
  • Lubrizol Solsperse 26000 (Solsperse 26000), 36000, 41000"
  • the dispersant that is a polysiloxane resin include, for example, KP-578, which is a graft copolymer containing an acrylic polymer and dimethylpolysiloxane, and X-22-3701E, which is a polysiloxane resin dispersant (both are Shin-Etsu Chemical Co., Ltd.). Etc.).
  • dispersant can be used alone, or two or more types can be used in combination.
  • the resins described in the above-described other binders can also be used.
  • a resin having a refractive index of 1.5 or less with respect to light having a wavelength of 589 nm may be used.
  • the composition of the present invention may contain a dispersion aid having an acid group and a crosslinkable group as a dispersion aid.
  • Preferred acid groups include sulfonic acid groups, phosphoric acid groups, phosphonic acid groups and carboxylic acid groups, with phosphoric acid groups being more preferred.
  • the crosslinkable group include a group having an ethylenically unsaturated bond, an epoxy group and a mercapto group, and a group having an ethylenically unsaturated bond is more preferable.
  • the group having an ethylenically unsaturated bond include addition-polymerizable ethylene groups mentioned in the description of the polymerizable compound.
  • dispersion aids include light ester P-1M, light ester P-2M, light ester HO-MS, light ester HO-HH (manufactured by Kyoeisha Chemical Co., Ltd.) Phosmer M, Phosmer PE, Phosmer MH , Hosmer CL, Hosmer PP (above, Unichemical Co., Ltd.), TBAS-Q, TBAS-R (above, MRC Unitech Co., Ltd.) and the like.
  • the content of the dispersant is preferably 1 to 80% by mass with respect to the total solid content of the composition from the viewpoints of L *, pattern shape and adhesion.
  • the upper limit is preferably 70% by mass or less, more preferably 60% by mass or less, particularly preferably 25% by mass or less, and most preferably 22% by mass or less.
  • the lower limit is preferably 1.5% by mass or more, more preferably 2% by mass or more, and particularly preferably 18% by mass or more.
  • the content of the dispersant is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the pigment.
  • the upper limit is preferably 80 parts by mass or less, and more preferably 60 parts by mass or less.
  • the lower limit is preferably 2.5 parts by mass or more, and more preferably 5 parts by mass or more.
  • the content of the dispersant is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the inorganic pigment.
  • the upper limit is preferably 80 parts by mass or less, and more preferably 60 parts by mass or less.
  • the lower limit is preferably 2.5 parts by mass or more, and more preferably 5 parts by mass or more.
  • the content of the dispersant is preferably 1 to 100 parts by mass with respect to 100 parts by mass of titanium oxide.
  • the upper limit is preferably 80 parts by mass or less, and more preferably 60 parts by mass or less.
  • the lower limit is preferably 2.5 parts by mass or more, and more preferably 5 parts by mass or more.
  • the composition of the present invention preferably contains a solvent.
  • the solvent can be composed of various organic solvents.
  • Organic solvents 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 , 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 monomethyl ether, diethylene Recall monoethyl ether, diethylene glyco
  • a solvent having a low metal content is used as the solvent.
  • the metal content of the solvent is preferably 10 mass ppb or less, for example. If necessary, those having a mass ppt level may be used, and such a high-purity solvent is provided, for example, by Toyo Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015).
  • Examples of the method for removing impurities such as metals from the solvent include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter.
  • the filter pore diameter of the filter used for filtration is preferably 10 nm or less, more preferably 5 nm or less, and still more preferably 3 nm or less.
  • the filter a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable.
  • the solvent may contain isomers (compounds having the same number of atoms and different structures). Further, only one type of isomer may be included, or a plurality of types may be included.
  • the content of the solvent is preferably such that the solid concentration of the composition is 25 to 70% by mass, and more preferably the amount of solid content of the composition is 30 to 60% by mass.
  • the composition of the present invention preferably contains a curable compound.
  • the curable compound is a compound that can be crosslinked (including polymerization and condensation) by radicals, acids, and heat.
  • examples of the curable compound used in the present invention include a compound having a group having an ethylenically unsaturated bond, a compound having an epoxy group, a compound having a methylol group, etc., and a compound having a group having an ethylenically unsaturated bond Is preferred.
  • Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
  • the curable compound is preferably a radical polymerizable compound.
  • the radical polymerizable compound include compounds having a group having an ethylenically unsaturated bond.
  • the composition of this invention may have the compound which has the below-mentioned epoxy group as a sclerosing
  • the content of the curable compound is preferably 1 to 70% by mass with respect to the total solid content of the composition.
  • the lower limit is preferably 3% by mass or more, more preferably 5% by mass or more, and particularly preferably 9% by mass or more.
  • the upper limit is preferably 60% by mass or less, more preferably 50% by mass or less, and particularly preferably 12% by mass or less. These ranges are preferable from the viewpoints of pattern shape, heat resistance, and L *.
  • the curable compound used in the composition may be only one type or two or more types. In the case of two or more types, the total amount is preferably within the above range.
  • the content of the polymerizable compound is preferably 1 to 70% by mass with respect to the total solid content of the composition.
  • the lower limit is preferably 3% by mass or more, and more preferably 5% by mass or more.
  • the upper limit is preferably 60% by mass or less, and more preferably 50% by mass or less.
  • the polymerizable compound used in the composition may be only one type or two or more types. In the case of two or more types, the total amount is preferably within the above range.
  • the content of the polymerizable compound is preferably 10 to 100% by mass, more preferably 30 to 100% by mass, based on the total mass of the curable compound.
  • the composition of the present invention comprises a radical polymerizable compound having a refractive index of 1.55 or less (preferably 1.52 or less, more preferably 1.5 or less) with respect to light having a wavelength of 589 nm in the total mass of the radical polymerizable compound.
  • the content of is preferably 80% by mass or more, more preferably 85% by mass or more, and particularly preferably 90% by mass or more.
  • a compound having at least one group having an ethylenically unsaturated bond is preferable, and a compound having at least one (preferably two or more) groups having a terminal ethylenically unsaturated bond is more preferable.
  • the polymerizable compound is preferably a compound having 1 to 8 groups having an ethylenically unsaturated bond, more preferably a compound having 2 to 6 groups having an ethylenically unsaturated bond, and an ethylenically unsaturated bond.
  • a compound having 3 to 4 groups is more preferable.
  • the polymerizable compound is particularly preferably a polymerizable compound having a group having an ethylenically unsaturated bond in the above range and having a Si atom in the molecule.
  • the group having an ethylenically unsaturated bond is preferably a (meth) acryloyl group or a (meth) acryloyloxy group.
  • the polymerizable compound is preferably a radical polymerizable compound.
  • the polymerizable compound may be in the form of either a monomer or a polymer, and is preferably a monomer.
  • the monomer type polymerizable compound preferably has a molecular weight of 100 to 3,000.
  • the upper limit is preferably 2000 or less, and more preferably 1500 or less.
  • the lower limit is preferably 150 or more, and more preferably 250 or more.
  • the polymerizable compound is preferably a 1 to 8 functional (meth) acrylate compound, more preferably a 2 to 6 functional (meth) acrylate compound, and more preferably a 3 to 4 functional (meth) acrylate compound. More preferably. According to this aspect, the solvent resistance of the film obtained and the adhesion to the substrate can be improved.
  • the polymerizable compound is also preferably a hexafunctional or higher (meth) acrylate compound.
  • the polymerizable compound is also preferably a compound having an ethylenically unsaturated bond having at least one addition-polymerizable ethylene group and having a boiling point of 100 ° C. or higher under normal pressure.
  • monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri ( (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol ( (
  • polymerizable compounds represented by the following formulas (MO-1) to (MO-5) can also be suitably used.
  • T is an oxyalkylene group
  • the terminal on the carbon atom side is bonded to R.
  • n is an integer from 0 to 14, and m is an integer from 1 to 8.
  • a plurality of R and T present in the same molecule may be the same or different.
  • at least one of the plurality of R is —OC ( ⁇ O) CH ⁇ CH 2 or —OC A group represented by ( ⁇ O) C (CH 3 ) ⁇ CH 2 is represented.
  • Specific examples of the polymerizable compounds represented by the above formulas (MO-1) to (MO-5) include the compounds described in paragraphs 0248 to 0251 of JP-A-2007-2699779.
  • a compound described in JP-A No. 10-62986 and (meth) acrylated after addition of ethylene oxide or propylene oxide to a polyfunctional alcohol can also be used as the polymerizable compound.
  • Polymerizable compounds include pentaerythritol tetraacrylate (commercially available NK ester A-TMMT; manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol triacrylate (commercially available KAYARAD D-330; Nippon Kayaku ( ), Dipentaerythritol tetraacrylate (as a commercial product, KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.) dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; Nippon Kayaku ( Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercial product, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) is preferred, and pentaerythritol tetraacrylate is more preferred from the viewpoint of pattern shape.
  • the polymerizable compound may have an acid group such as a carboxy group, a sulfo group, or a phosphoric acid group.
  • the polymerizable compound having an acid group can be obtained by a method in which a part of the hydroxy group of the polyfunctional alcohol is (meth) acrylated, and an acid anhydride is added to the remaining hydroxy group to form a carboxy group.
  • Examples of the polymerizable compound having an acid group include esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids.
  • the polymerizable compound having an acid group is preferably a compound in which an unreacted hydroxy group of an aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to give an acid group, and particularly preferably in this ester.
  • the aliphatic polyhydroxy compound is at least one of pentaerythritol and dipentaerythritol.
  • Commercially available products include, for example, Aronix series M-305, M-510, and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
  • the acid value of the polymerizable compound having an acid group is preferably from 0.1 to 40 mgKOH / g.
  • the lower limit is preferably 5 mgKOH / g or more.
  • the upper limit is preferably 30 mgKOH / g or less.
  • the polymerizable compound is preferably a polymerizable compound having a caprolactone structure.
  • the polymerizable compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule.
  • trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tripenta Mention may be made of ⁇ -caprolactone-modified polyfunctional (meth) acrylates obtained by esterifying polyhydric alcohols such as erythritol, glycerin, diglycerol, trimethylolmelamine, (meth) acrylic acid and ⁇ -caprolactone.
  • the polymerizable compound having a caprolactone structure is preferably a compound represented by the following formula (Z-1).
  • 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
  • “*” represents a bond
  • a compound represented by the 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) —.
  • Each represents independently an integer of 0 to 10
  • each X independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxy 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 particularly 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 particularly preferably an integer of 6 to 12.
  • — ((CH 2 ) y CH 2 O) — or — ((CH 2 ) y CH (CH 3 ) O) — represents the oxygen atom side.
  • a form in which the terminal of X 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.
  • a form in which all six Xs are acryloyl groups is preferable.
  • 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.
  • the compound represented by the formula (Z-4) or the formula (Z-5) is a ring-opening skeleton obtained by ring-opening addition reaction of ethylene oxide or propylene oxide with pentaerythritol or dipentaerythritol, which is a conventionally known process. And a step of reacting, for example, (meth) acryloyl chloride with the terminal hydroxy group of the ring-opening skeleton to introduce a (meth) acryloyl group. Each step is a well-known step, and a person skilled in the art can easily synthesize a compound represented by formula (Z-4) or formula (Z-5).
  • At least one of a pentaerythritol derivative and a dipentaerythritol derivative is more preferable.
  • Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”).
  • exemplary compounds (a), (f) b), (e) and (f) are preferred.
  • Examples of commercially available polymerizable compounds represented by the formulas (Z-4) and (Z-5) include SR-494, a tetrafunctional acrylate having four ethyleneoxy groups manufactured by Sartomer Co., Ltd. Examples thereof include DPCA-60, which is a hexafunctional acrylate having 6 pentyleneoxy groups, and TPA-330, which is a trifunctional acrylate having 3 isobutyleneoxy groups.
  • Polymerizable compounds include urethane acrylates such as those described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765.
  • Urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable.
  • addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238. .
  • polymerizable compounds include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), U-4HA, U-6LPA, UA-32P, U-10HA, U-10PA, UA- 122P, UA-1100H, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T -600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), UA-9050, UA-9048 (manufactured by BASF Corp.) and the like.
  • the polymerizable compound is also preferably a polymerizable compound having a Si atom in the molecule.
  • a polymerizable compound having a Si atom in the molecule as a radical polymerizable compound having a refractive index with respect to light having a wavelength of 589 nm of 1.5 or less.
  • polymerizable compounds having Si atoms in the molecule include EBECRYL 1360 (manufactured by Daicel Ornex Co., Ltd.), a polyfunctional acrylate containing a siloxane bond, and VINYLTRIISOPROPENOXYSILANE (Azmax Corporation), a polyfunctional vinyl compound containing Si atoms. Manufactured).
  • the details of the use method such as the structure, single use or combined use, and addition amount of these polymerizable compounds can be arbitrarily set in accordance with the final performance design of the composition.
  • a structure having a large content of groups having an ethylenically unsaturated bond per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable.
  • a compound having three or more functional groups is preferable, and at least one of the functional number and the polymerizable group (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound) is included.
  • a method of adjusting both sensitivity and intensity by using different compounds in combination is also effective. Further, it is also preferable to use a trifunctional or higher functional compound having different ethylene oxide chain lengths. According to this aspect, the developability of the composition can be adjusted, and excellent pattern formation can be obtained.
  • at least one of the selection and use method of the polymerizable compound is compatible with at least one of compatibility and dispersibility with other components (eg, photopolymerization initiator, resin, etc.) included in the composition. This is a preferable factor. For example, compatibility and the like can be improved by using a low-purity compound or using two or more kinds in combination.
  • a compound having an epoxy group in the composition of the present invention, can also be used as the curable compound. According to this aspect, the solvent resistance of the obtained film can be improved.
  • the compound having an epoxy group include monofunctional or polyfunctional glycidyl ether compounds and polyfunctional aliphatic glycidyl ether compounds.
  • the compound which has epoxy groups such as glycidyl (meth) acrylate and allyl glycidyl ether, as a part of glycidyl group, and the compound which has an alicyclic epoxy group can also be used.
  • Examples of the compound having an epoxy group include compounds having one or more epoxy groups per molecule. It is preferable to have 1 to 100 epoxy groups per molecule.
  • the upper limit may be 10 or less, and may be 5 or less.
  • the lower limit is preferably 2 or more.
  • the compound having an epoxy group may be either a low molecular weight compound (for example, a molecular weight of less than 1000) or a high molecular weight compound (for example, a molecular weight of 1000 or more, and in the case of a polymer, the weight average molecular weight is 1000 or more).
  • the weight average molecular weight of the compound having an epoxy group is preferably 200 to 100,000, more preferably 500 to 50,000.
  • the upper limit of the weight average molecular weight is preferably 10,000 or less, more preferably 5000 or less, and still more preferably 3000 or less.
  • the compound having an epoxy group is preferably an aliphatic epoxy resin from the viewpoint of solvent resistance.
  • bisphenol A type epoxy resin jER825, jER827, jER828, jER834, jER1001, jER1002, jER1003, jER1055, jER1007, jER1009, jER1010 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON860, EPICLON1050 , EPICLON1051, EPICLON1055 (manufactured by DIC Corporation), etc.
  • bisphenol F-type epoxy resins include jER806, jER807, jER4004, jER4005, jER4007, jER4010 (above, Mitsubishi Chemical Corporation), EPICLON830, EPICLON835.
  • Cresol novolac type epoxy resins include EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (or more DIC Co., Ltd.), EOCN-1020 (Nippon Kayaku Co., Ltd.), etc., and aliphatic epoxy resins are ADEKA RESIN EP-4080S, EP-4085.
  • EP-4088S (above, manufactured by ADEKA Corporation), Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEEAD PB 3600, PB 4700 (above, Daicel Corporation), Denacol EX-212L EX-214L, EX-216L, EX-321L, EX-850L (manufactured by Nagase ChemteX Corporation) and the like.
  • ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation), jER1031S (manufactured by Mitsubishi Chemical Corporation), and the like.
  • the composition of the present invention preferably contains a polymerization initiator.
  • the content of the polymerization initiator is preferably 0.1 to 50% by mass with respect to the total solid content of the composition from the viewpoint of solvent resistance and colorability, more preferably 0.5 to 30% by mass, and still more preferably. Is 1 to 10% by mass.
  • the composition may contain only one type of polymerization initiator, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
  • As the polymerization initiator a photopolymerization initiator or a thermal polymerization initiator is preferable, and a photopolymerization initiator is preferable.
  • limiting in particular as a thermal-polymerization initiator A well-known compound can be used.
  • the composition of the present invention can contain a photopolymerization initiator.
  • a photopolymerization initiator preferably contains a photopolymerization initiator.
  • the photopolymerization initiator is preferably a photoradical polymerization initiator.
  • 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 photopolymerization initiator examples include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazoles, oxime derivatives, etc. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, and the like.
  • halogenated hydrocarbon compound having a triazine skeleton examples include those described in Wakabayashi et al., Bull. Chem. Soc.
  • trihalomethyltriazine compounds benzyldimethylketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triallylimidazole dimers, oniums
  • compounds selected from the group consisting of compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds are preferred.
  • a photopolymerization initiator that is a trihalomethyltriazine compound
  • triazine PP manufactured by BASF
  • BASF trichloromethyltriazine compound
  • hydroxyacetophenone compounds As the photopolymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, an aminoacetophenone initiator described in JP-A-10-291969 and an acylphosphine initiator described in Japanese Patent No. 4225898 can also be used.
  • hydroxyacetophenone-based initiator IRGACURE 184, DAROCUR 1173, IRGACURE 500, IRGACURE 2959, IRGACURE 127 (trade names: all manufactured by BASF Corporation) can be used.
  • aminoacetophenone-based initiator commercially available products IRGACURE 907, IRGACURE 369, IRGACURE 379, IRGACURE 379EG (trade names: all manufactured by BASF Corporation) can be used.
  • aminoacetophenone-based initiator 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-based initiator commercially available products such as IRGACURE 819 and IRGACURE TPO (trade names: both manufactured by BASF Corporation) can be used.
  • An aminoacetophenone initiator or an acylphosphine initiator is preferable from the viewpoint of colorability, and an acylphosphine initiator is more preferable from the viewpoint of colorability and adhesion.
  • An oxime compound can also be preferably used as the photopolymerization initiator.
  • an oxime ester compound is more preferable.
  • Specific examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, compounds described in JP-A No. 2006-342166, and JP-A No. 2016-21012. These compounds can be used.
  • J.H. C. S. Perkin II (1979) pp. 1653-1660
  • oxime compounds other than the above compounds described in JP-A-2009-519904 in which oxime is linked to carbazole N position, compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety, and dyes A compound described in JP 2010-15025 A and US Patent Publication No. 2009-292039 in which a nitro group is introduced at the site, a ketoxime compound described in International Publication No. 2009-131189, a triazine skeleton and an oxime skeleton in the same molecule The compound described in US Pat. No.
  • the compound described in JP2009-221114A having an absorption maximum at 405 nm and good sensitivity to a g-ray light source and JP2014-137466A Conversions described in paragraph numbers 0076-0079 Or the like may be used things.
  • paragraphs 0274 to 0275 of JP 2013-29760 A can be referred to, the contents of which are incorporated herein.
  • the oxime compound is preferably a compound represented by the following formula (OX-1).
  • the oxime compound may be an oxime compound in which the N—O bond of the oxime is an (E) isomer, or an oxime compound in which the N—O bond of the oxime is a (Z) isomer. ) It may be a mixture with the body.
  • 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 having a fluorene ring can also be used as a photopolymerization initiator.
  • Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A No. 2014-137466. This content is incorporated herein.
  • an oxime compound having a fluorine atom can also be used as a photopolymerization initiator.
  • Specific examples of the oxime compound having a fluorine atom include compounds described in JP 2010-262028 A, compounds 24 and 36 to 40 described in JP-A-2014-500852, and compounds described in JP-A 2013-164471 ( C-3). This content is incorporated herein.
  • an oxime compound having a nitro group can be used as a photopolymerization initiator.
  • the oxime compound having a nitro group is also preferably a dimer.
  • Specific examples of the oxime compound having a nitro group include compounds described in paragraphs 0031 to 0047 of JP 2013-114249 A, paragraphs 0008 to 0012 and 0070 to 0079 of JP 2014-137466 A, patent No. Examples include compounds described in paragraphs 0007 to 0025 of No. 4223071, ADEKA ARKLES NCI-831 (manufactured by ADEKA Corporation).
  • oxime compounds that are preferably used in the present invention are shown below, but the present invention is not limited thereto.
  • the oxime compound is preferably a compound having a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, more preferably a compound having an absorption wavelength in a wavelength region of 360 nm to 480 nm, and particularly preferably a compound having high absorbance at 365 nm and 405 nm.
  • the molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, more preferably 5,000 to 200,000 from the viewpoint of sensitivity. 000 is particularly preferred.
  • a known method can be used. Specifically, using a UV-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian, Inc.), ethyl acetate is used. It is preferable to measure at a concentration of 01 g / L.
  • a photopolymerization initiator having an extinction coefficient of 365 nm in methanol of 1.0 ⁇ 10 3 mL / gcm or more and an extinction coefficient of 365 nm in methanol of 1.0 ⁇ 10 2 mL / gcm or less
  • a photopolymerization initiator having an extinction coefficient of 254 nm of 1.0 ⁇ 10 3 mL / gcm or more in combination.
  • an aminoacetophenone compound and an oxime compound can be mentioned.
  • a film having excellent curability can be produced even under low temperature conditions.
  • the composition in the pattern formation process, by exposing the composition in two stages before the development process and after the development process, the composition can be appropriately cured in the first exposure, and the entire composition is almost completely exposed in the next exposure. It can be cured. For this reason, the curability of the composition can be improved even under low temperature conditions.
  • the composition of the present invention preferably contains a coloring inhibitor.
  • the anti-coloring agents described herein can also be used as antioxidants, and the antioxidants can also be used as anti-coloring agents.
  • the coloring inhibitor include phenol compounds, phosphite compounds, thioether compounds, and the like, and phenol compounds having a molecular weight of 500 or more, phosphite compounds having a molecular weight of 500 or more, or thioether compounds having a molecular weight of 500 or more are more preferable.
  • the coloring inhibitor is preferably a phenol compound, and more preferably a phenol compound having a molecular weight of 500 or more.
  • phenolic compound any phenolic compound known as a phenolic anti-coloring agent can be used.
  • Preferable phenolic compounds include hindered phenolic compounds.
  • a compound having a substituent at a site (ortho position) adjacent to the phenolic hydroxyl group is preferable.
  • a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, an isopentyl group.
  • T-pentyl group, hexyl group, octyl group, isooctyl group and 2-ethylhexyl group are more preferable.
  • a compound having a phenol group and a phosphite group in the same molecule is also preferred.
  • polysubstituted phenolic compounds are particularly preferably used.
  • polysubstituted phenolic compounds with different substitution positions and structures due to the reactivity to the captured peroxy radicals due to stable phenoxy radical formation: the following formula (A) hindered type, formula (B There are semi-hindered type and formula (C) less hindered type.
  • R is a substituent, having a hydrogen atom, a halogen atom, an amino group that may have a substituent, or a substituent.
  • An amino group that may have a substituent an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkoxy group that may have a substituent, an aryloxy group that may have a substituent, Alkylamino group which may have a substituent, Substituent Aryl amino group which may have preferred.
  • a more preferable form is a composite anti-coloring agent in which a plurality of structures expressing the anti-coloring function represented by the above formulas (A) to (C) are present in the same molecule.
  • the above formula (A) A compound in which 2 to 4 structures expressing the anti-coloring function represented by (C) are present in the same molecule is preferable.
  • a formula (B) semi hindered type is more preferable from a viewpoint of coloring property.
  • the phenolic hydroxyl group-containing compound include paramethoxyphenol, di-t-butyl-paracresol, pyrogallol, t-butylcatechol, 4,4-thiobis (3-methyl-6-t-butylphenol), 2,2 ′.
  • a compound selected from the group consisting of -methylenebis (4-methyl-6-t-butylphenol), phenol resins, and cresol resins Typical examples of commercially available products include (A) Sumilizer BHT (manufactured by Sumitomo Chemical), Irganox 1010, 1222 (manufactured by BASF), Adeka Stub AO-20, AO-50, AO-60 (manufactured by ADEKA) (B) includes Sumilizer BBM-S (manufactured by Sumitomo Chemical), Irganox 245 (manufactured by BASF), Adeka Stub AO-80 (manufactured by ADEKA), etc. ADEKA).
  • phosphite compound tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphin-6 -Yl] oxy] ethyl] amine, tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-2-yl And at least one compound selected from the group consisting of) oxy] ethyl] amine and ethylbisphosphite (2,4-ditert-butyl-6-methylphenyl).
  • thioether compound examples include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate, and pentaerythritol tetra ( ⁇ -alkylthiopropionic acid) esters; Erythrityltetrakis (3-laurylthiopropionate), dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, etc.
  • dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate, and pentaerythritol tetra ( ⁇ -alkylthiopropionic
  • thioether compounds include ADK STAB AO-412S (CAS: 29598-76-3, manufactured by ADEKA Corporation), ADK STAB AO-503 (CAS: 10595-72-9, ADEKA Corporation). And KEMINOX PLS (CAS: 29598-76-3, manufactured by Chemipro Kasei Co., Ltd.). Anti-coloring agents are readily available as commercial products.
  • ADK STAB AO-50F, ADK STAB AO-60G, ADK STAB AO-330, ADK STAB PEP-36A (Made by ADEKA Corporation).
  • the content of the anti-coloring agent is preferably 0.01 to 20% by mass with respect to the total solid content of the composition from the viewpoint of colorability and solvent resistance, and more preferably 0.1 to 15% by mass. 0.3 to 5% by mass is particularly preferable. Only one type of anti-coloring agent or two or more types may be used. In the case of two or more types, the total amount is preferably within the above range.
  • the composition of the present invention may contain an ultraviolet absorber.
  • the ultraviolet absorber is preferably a conjugated diene compound, and more preferably a compound represented by the following formula (I).
  • R 1 and R 2 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R 1 and R 2 are Although they may be the same or different from each other, they do not represent a hydrogen atom at the same time.
  • R 1 and R 2 may form a cyclic amino group together with the nitrogen atom to which R 1 and R 2 are bonded. Examples of the cyclic amino group include piperidino group, morpholino group, pyrrolidino group, hexahydroazepino group, piperazino group and the like.
  • R 1 and R 2 are each independently preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and still more preferably an alkyl group having 1 to 5 carbon atoms.
  • R 3 and R 4 represent an electron withdrawing group.
  • the electron withdrawing group is an electron withdrawing group having a Hammett's substituent constant ⁇ p value (hereinafter simply referred to as “ ⁇ p value”) of 0.20 or more and 1.0 or less.
  • ⁇ p value Hammett's substituent constant
  • R 3 and R 4 may combine with each other to form a ring.
  • R 3 and R 4 are preferably acyl, carbamoyl, alkyloxycarbonyl, aryloxycarbonyl, cyano, nitro, alkylsulfonyl, arylsulfonyl, sulfonyloxy, sulfamoyl, acyl, carbamoyl Group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, and sulfamoyl group are more preferable.
  • At least one of the above R 1 , R 2 , R 3 , and R 4 may be in the form of a polymer derived from a monomer bonded to a vinyl group via a linking group. It may be a copolymer with another monomer.
  • the content of the ultraviolet absorber is preferably 0.1 to 10% by mass with respect to the total solid content of the composition from the viewpoint of pattern shape and solvent resistance, and preferably 0.1 to 7% by mass. Is more preferable, 0.1 to 5% by mass is further preferable, and 0.1 to 3% by mass is particularly preferable. Moreover, in this invention, only one type may be sufficient as an ultraviolet absorber, and two or more types may be sufficient as it. In the case of two or more types, the total amount is preferably within the above range.
  • the composition of the present invention preferably further contains an adhesive.
  • an adhesive agent A well-known adhesive agent can be used.
  • the adhesive include a silane coupling agent.
  • the adhesion between the film and the substrate can be improved.
  • the “silane coupling agent” means a silane compound having a hydrolyzable group and other functional groups.
  • the “hydrolyzable group” refers to a substituent that is directly bonded to a silicon atom and can form a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction.
  • the silane coupling agent is preferably a compound having an alkoxysilyl group.
  • the functional group other than the hydrolyzable group preferably has a group that exhibits affinity by interacting or forming a bond with the resin. Examples include (meth) acryloyl group, phenyl group, mercapto group, epoxy group, and oxetanyl group, and (meth) acryloyl group and epoxy group are preferable.
  • the silane coupling agent is preferably a compound having an alkoxysilyl group and at least one of a (meth) acryloyl group and an epoxy group.
  • the number of carbon atoms of the alkoxy group in the alkoxysilyl group is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1 or 2.
  • the number of alkoxysilyl groups is preferably 2 or more, more preferably 2 to 3 in the same molecule.
  • silane coupling agent examples include, for example, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3- Mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, phenyltrimethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis (trimethoxys
  • silane coupling agent examples include compounds described in paragraph Nos. 0018 to 0036 of JP-A-2009-288703, and compounds described in paragraphs 0056 to 0066 of JP-A-2009-242604. Incorporated in the description. Moreover, the compound which has an alkoxy silyl group in a side chain can also be used for the compound which has an alkoxy silyl group. As the silane coupling agent, the specific silane compounds described in ⁇ 0011> to ⁇ 0037> of JP-A-2009-288703 can also be used, the contents of which are incorporated herein.
  • a silane compound containing a silicon atom, a nitrogen atom and a polymerizable group in the molecule is preferable.
  • the content of the adhesion agent is preferably 0.01 to 10% by mass, more preferably 0.1 to 7% by mass, and particularly preferably 1 to 5% by mass with respect to the total solid content of the composition. These ranges are preferable from the viewpoints of adhesion and density unevenness after one month.
  • the adhesive agent which a composition contains may be only 1 type, and 2 or more types may be sufficient as it. In the case of two or more types, the total amount is preferably within the above range.
  • the composition of the present invention preferably contains a chain transfer agent. According to this aspect, in exposure at the time of pattern formation, curing of the film surface (pattern surface) can be promoted by exposure. For this reason, the reduction
  • chain transfer agent examples include N, N-dialkylaminobenzoic acid alkyl esters and thiol compounds, and thiol compounds are preferred.
  • the thiol compound is preferably a compound having 2 or more (preferably 2 to 8, more preferably 3 to 6) mercapto groups in the molecule.
  • thiol compound examples include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, N-phenylmercaptobenzimidazole, 1,3,5-tris (3-mercaptobutyloxyethyl) -1 , 3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and other thiol compounds having a heterocyclic ring, pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercapto) And aliphatic thiol compounds such as butyryloxy) butane.
  • chain transfer agents include PEMP (manufactured by SC Organic Chemical Co., Ltd., thiol compound), Sunseller M (manufactured by Sanshin Chemical Industry Co., Ltd., thiol compound), Karenz MT BD1 (manufactured by Showa Denko KK). And thiol compounds). Moreover, it is also preferable to use the following compound.
  • the content of the chain transfer agent is preferably 0.2 to 5.0% by mass, more preferably 0.4 to 3.0% by mass, based on the total solid content of the composition.
  • the content of the chain transfer agent is preferably 1 to 40 parts by mass and more preferably 2 to 20 parts by mass with respect to 100 parts by mass of the polymerizable compound. Only one type of chain transfer agent may be used, or two or more types may be used. In the case of two or more types, the total amount is preferably within the above range.
  • the composition of the present invention may contain a sensitizer for the purpose of improving the radical generation efficiency of the photopolymerization initiator and increasing the photosensitive wavelength.
  • a photosensitizer that is sensitized by an electron transfer mechanism or an energy transfer mechanism is preferable.
  • the sensitizer include those having an absorption wavelength in a wavelength region of 300 nm to 450 nm.
  • the description of paragraphs 0231 to 0253 of JP 2010-106268 A (corresponding ⁇ 0256> to ⁇ 0273> of US Patent Application Publication No. 2011/0124824) can be referred to. Incorporated herein.
  • the content of the sensitizer is preferably 0.1 to 20% by mass and more preferably 0.5 to 15% by mass with respect to the total solid content of the composition. Only one type of sensitizer may be used, or two or more types may be used. In the case of two or more types, the total amount is preferably within the above range.
  • the composition of the present invention preferably further contains a co-sensitizer.
  • the co-sensitizer has functions such as further improving the sensitivity of the photopolymerization initiator and the sensitizer to actinic radiation, or suppressing inhibition of polymerization of the oxygen-polymerizable compound.
  • Specific examples of the co-sensitizer include those described in JP-A 2010-106268, paragraphs 0254 to 0257 (corresponding to ⁇ 0277> to ⁇ 0279> in US Patent Application Publication No. 2011/0124824). Which are incorporated herein by reference.
  • the content of the co-sensitizer is preferably 0.1 to 30% by mass, more preferably 1 to 25% by mass, based on the total solid content of the composition, from the viewpoint of improving the polymerization growth rate and the curing rate. 1.5 to 20% by mass is more preferable.
  • a polymerization inhibitor is preferably added in order to prevent unnecessary polymerization of a polymerizable compound or the like during production or storage of the composition.
  • a polymerization inhibitor Phenolic hydroxyl group-containing compounds (preferably hydroquinone, paramethoxyphenol, di-t-butyl-paracresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4-thiobis (3-methyl-6-t-butylphenol), Selected from the group consisting of 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,6-di-t-butyl-4-methylphenol (BHT), phenolic resins, and cresol resins Compound); N-oxide compounds (preferably 5,5-dimethyl-1-pyrroline N-oxide, 4-methylmorpholine N-oxide, pyridine N-oxide, 4-nitropyridine N-oxide, 3-hydroxypyridine N-oxide
  • these compounds may be composite compounds in which a plurality of structures that exhibit a polymerization inhibiting function such as a phenol skeleton and a phosphorus-containing skeleton are present in the same molecule.
  • a polymerization inhibiting function such as a phenol skeleton and a phosphorus-containing skeleton
  • the compounds described in JP-A-10-46035 are also preferably used.
  • polymerization inhibitor examples include compounds described in JP-A-2015-34961, paragraphs 0211 to 0223, the contents of which are incorporated herein.
  • the content of the polymerization inhibitor is preferably 0.01 to 10 parts by weight, more preferably 0.01 to 8 parts by weight, and 0.01 to 5 parts by weight with respect to 100 parts by weight of the photopolymerization initiator. Most preferred. By setting it as the said range, hardening reaction suppression in a non-image part and hardening reaction promotion in an image part are fully performed, and a pattern shape and a sensitivity become favorable. Only one type of polymerization inhibitor may be used, or two or more types may be used. In the case of two or more types, the total amount is preferably within the above range.
  • the composition of the present invention may contain various types of surfactants from the viewpoint of further improving coating suitability.
  • various types of surfactants such as a fluorosurfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant can be used.
  • the liquid properties (particularly fluidity) when prepared as a coating liquid can be further improved, and the uniformity of coating thickness and liquid saving can be further improved. it can. That is, in the case of forming a film using a coating liquid to which a composition containing a fluorosurfactant is applied, the interfacial tension between the coated surface and the coating liquid decreases, and the wettability to the coated surface is reduced. This improves the applicability to the coated surface. For this reason, it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.
  • the fluorine content in the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass.
  • a fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in the composition.
  • fluorosurfactant examples include surfactants described in paragraphs 0060 to 0064 of JP 2014-41318 A (paragraphs 0060 to 0064 of the corresponding international publication 2014/17669 pamphlet) and the like, JP 2011 Examples include surfactants described in paragraphs 0117 to 0132 of JP-A-1252503, the contents of which are incorporated herein.
  • fluorosurfactants include, for example, Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (made by OMNOVA) etc. are mentioned.
  • a block polymer can be used. Examples thereof include compounds described in JP2011-89090A.
  • the fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy group or propyleneoxy group) (meth).
  • a fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used.
  • the following compounds are also exemplified as the fluorosurfactant used in the present invention.
  • the weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example, 14,000.
  • a fluoropolymer having a group having an ethylenically unsaturated bond in the side chain can also be used.
  • Specific examples thereof include compounds described in JP-A 2010-164965, paragraphs 0050 to 0090 and 0289 to 0295, for example, Megafac RS-101, RS-102, RS-718K, RS-manufactured by DIC Corporation. 72-K and the like.
  • the fluorine-based surfactant compounds described in paragraphs 0015 to 0158 of JP-A No. 2015-117327 can also be used.
  • Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF ), Tetronic 304, 701, 704, 901, 904, 150R1 (BASF) Solsperse 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure
  • cationic surfactants examples include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.
  • anionic surfactant examples include W004, W005, W017 (manufactured by Yusho Co., Ltd.), Sandet BL (manufactured by Sanyo Chemical Co., Ltd.), and the like.
  • silicone-based surfactants include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torresilicone SH21PA, Torree Silicone SH28PA, Torree Silicone SH29PA, Torree Silicone SH30PA, Torree Silicone SH8400 (above, Toray Dow Corning Co., Ltd.) )), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4442 (above, manufactured by Momentive Performance Materials), KP341, KF6001, KF6002 (above, manufactured by Shin-Etsu Silicone Co., Ltd.) , BYK307, BYK323, BYK330 (above, manufactured by BYK Chemie) and the like.
  • the content of the surfactant is preferably 0.001 to 2.0 mass%, more preferably 0.005 to 1.0 mass%, based on the total solid content of the composition.
  • a known additive such as a plasticizer or a sensitizer may be added to the composition in order to improve the physical properties of the film or cured film.
  • the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin and the like.
  • the content of the plasticizer is preferably 10% by mass or less with respect to the total mass of the polymerizable compound and the resin.
  • the aforementioned composition can be prepared by mixing the aforementioned components.
  • the respective components may be blended in a lump, or the components may be blended sequentially after at least one of dissolving and dispersing each component in a solvent.
  • the process for dispersing the pigment include a process using compression, squeezing, impact, shearing, cavitation and the like as the mechanical force used for dispersing the pigment.
  • a filter for the purpose of removing foreign substances or reducing defects.
  • a filter if it is conventionally used for the filtration use etc., it can use without being specifically limited.
  • fluorine resins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (eg nylon-6, nylon-6,6), polyolefin resins such as polyethylene and polypropylene (PP) (high density, ultra high (Including molecular weight) and the like.
  • PTFE polytetrafluoroethylene
  • nylon eg nylon-6, nylon-6,6)
  • polyolefin resins such as polyethylene and polypropylene (PP) (high density, ultra high (Including molecular weight) and the like.
  • PP polypropylene
  • nylon high density polypropylene
  • the pore size of the filter is suitably about 0.01 to 7.0 ⁇ m, preferably about 0.01 to 3.0 ⁇ m, more preferably about 0.05 to 0.5 ⁇ m. By setting it as this range, it becomes possible to remove reliably the fine foreign material which inhibits preparation of a uniform and smooth composition in a post process. It is also preferable to use a fiber-like filter.
  • the filter include polypropylene fiber, nylon fiber, glass fiber, and the like. Specifically, SBP type series (SBP008 etc.) and TPR type series manufactured by Loki Techno Co., Ltd. (Such as TPR002 and TPR005) and SHPX type series (such as SHPX003) filter cartridges can be used.
  • the filtering by the first filter may be performed only once or may be performed twice or more.
  • the pore diameter here can refer to the nominal value of the filter manufacturer.
  • filters for example, among various types of filters provided by Nippon Pole Co., Ltd. (DFA4201NXEY, etc.), Advantech Toyo Co., Ltd., Japan Integris Co., Ltd. (formerly Nihon Microlith Co., Ltd.) You can choose from.
  • the second filter a filter formed of the same material as the first filter described above can be used.
  • the filtering by the first filter may be performed only with the dispersion, and the second filtering may be performed after mixing other components.
  • the film of the present invention is a film formed using the composition of the present invention.
  • L * in the L * a * b * color system of CIE 1976 is preferably 35 to 85.
  • the upper limit of L * in the CIE 1976 L * a * b * color system is more preferably less than 80, particularly preferably 75 or less, and more preferably 70 or less.
  • the lower limit of L * in the CIE 1976 L * a * b * color system is more preferably 40 or more, and particularly preferably 50 or more.
  • a * and b * in the L * a * b * color system of CIE 1976 are preferably -30 to 30, more preferably -20 to 20, and particularly preferably -10 to 10.
  • the film of the present invention preferably has a thickness of 10 ⁇ m or less, more preferably 3 ⁇ m or less, and particularly preferably 1 ⁇ m or less.
  • the lower limit value of the thickness is preferably 0.5 ⁇ m or more.
  • the average transmittance in a wavelength range of 400 to 700 nm with a thickness of 3 ⁇ m is preferably 1% or more, more preferably 10% or more, and particularly preferably 30% or more.
  • the upper limit of the average transmittance in the wavelength range of 400 to 700 nm is preferably 50% or less.
  • the film of the present invention can be used by being incorporated in various types of sensors such as a solid-state imaging device or an image display device (for example, a liquid crystal display device or an organic electroluminescence (organic EL) display device). It can also be used as a material for adjusting the appearance of optical members.
  • the film of the present invention can be incorporated into various types of sensors, image display devices, and the like, and can be used as a member that appropriately shields or transmits light or a member that scatters light. It can also be used for light emitting diode (LED) reflection applications, organic EL light scattering layer applications, conductive materials, insulating materials, solar cell materials, and the like.
  • LED light emitting diode
  • the cured film of the present invention is a cured film obtained by curing the film of the present invention.
  • the cured film is preferably obtained by removing the solvent from the film of the present invention.
  • the cured film is preferably cured by polymerizing the polymerizable compound of the film of the present invention.
  • L * in the L * a * b * color system of CIE 1976 is preferably 35 to 85 in the cured film state.
  • the upper limit of L * in the L * a * b * color system of CIE 1976 is more preferably less than 80, particularly preferably 75 or less, and 70 or less. More particularly preferred.
  • the lower limit of L * in the L * a * b * color system of CIE 1976 is more preferably 40 or more and particularly preferably 50 or more in the cured film state.
  • the cured film of the present invention includes particles and a resin, the particles include particles having a refractive index of 2.1 or more for light having a wavelength of 589 nm, and the resin has a refractive index of 1.5 or less for light having a wavelength of 589 nm. It is preferable to contain a certain resin.
  • the preferable refractive index range of the particles having a refractive index with respect to light having a wavelength of 589 nm in the cured film of the present invention is the same as the preferable refractive index range of the particles having refractive index with respect to light having a wavelength of 589 nm in the composition of the present invention.
  • the preferred refractive index range of the resin having a refractive index with respect to light having a wavelength of 589 nm in the cured film of the present invention is the same as the preferred refractive index range of the resin having a refractive index with respect to light having a wavelength of 589 nm in the composition of the present invention. .
  • the cured film of the present invention contains particles and a resin, and the difference between the refractive index of the particles with respect to light having a wavelength of 589 nm and the refractive index of the resin with respect to light having a wavelength of 589 nm is preferably 1.22 or more. More preferably. Within this range, it is easy to increase L * in the L * a * b * color system of CIE 1976 of the cured film.
  • the composition of the cured film of the present invention is classified into particles and components other than the particles, the components other than the particles of the cured film are the same as the refractive index of light having a wavelength of 589 nm (the average value of the refractive indices of the components other than the particles).
  • Is preferably 1.5 or less, more preferably 1.00 to 1.45, and even more preferably 1.10 to 1.40.
  • optical sensor of the present invention is an optical sensor having the cured film of the present invention.
  • optical sensor include a solid-state image sensor.
  • the method for producing a film of the present invention comprises a step of exposing the composition of the present invention through a mask having a pattern; And developing the exposed composition to form a pattern.
  • a step of forming a film by applying the composition of the present invention to a substrate and the like it is preferable to pass a step of forming a film by applying the composition of the present invention to a substrate and the like, and a step of drying the film. .
  • a film thickness, laminated structure, etc. it can select suitably according to the objective.
  • a known method can be used as a method for applying the composition.
  • a dropping method drop casting
  • a slit coating method for example, a spray method; a roll coating method; a spin coating method (spin coating); a casting coating method; a slit and spin method; a pre-wet method (for example, JP 2009-145395 A).
  • Methods described in the publication inkjet (for example, on-demand method, piezo method, thermal method), ejection printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing method, etc.
  • Examples of each type of printing method include: a transfer method using a mold or the like; and a nanoimprint method.
  • the application method using the ink jet is not particularly limited as long as the composition can be ejected.
  • the methods described in the patent publications indicated (particularly, pages 115 to 133), JP-A 2003-262716, JP-A 2003-185831, JP-A 2003-261827, JP-A 2012-126830 JP-A 2006-169325 discloses a method of replacing the composition to be discharged with the composition of the present invention.
  • spin coating is preferably performed by spin coating in the range of 300 to 6000 rpm, and more preferably spin coating in the range of 400 to 3000 rpm.
  • the substrate temperature during spin coating is preferably 10 to 100 ° C, more preferably 20 to 70 ° C. If it is said range, it will be easy to manufacture the film
  • a dropping region of the composition having a photoresist as a partition on the substrate so that a uniform film can be obtained with a predetermined film thickness.
  • a desired film thickness is obtained by controlling the dropping amount and solid content concentration of the composition and the area of the dropping region.
  • the substrate is not particularly limited and can be appropriately selected depending on the application.
  • alkali-free glass soda glass, Pyrex (registered trademark) glass, quartz glass used for liquid crystal display devices, etc., and substrates obtained by attaching a transparent conductive film to these, photoelectric conversion element groups used for solid-state imaging devices, etc.
  • Examples thereof include complementary metal oxide semiconductors (CMOS) such as materials and silicon substrates.
  • CMOS complementary metal oxide semiconductors
  • an undercoat layer may be provided on these base materials, if necessary, in order to improve adhesion to the upper layer, prevent diffusion of substances, or flatten the surface.
  • the drying conditions vary depending on each component, the type of solvent, the use ratio, and the like.
  • the temperature is preferably 60 to 150 ° C. and preferably 30 seconds to 15 minutes.
  • the composition of the present invention is applied on a substrate.
  • examples include a method including a step of forming a film-shaped composition layer, a step of exposing the composition layer to a pattern shape, and a step of developing and removing an unexposed portion to form a pattern.
  • a pattern forming step a pattern may be formed by a photolithography method, or a pattern may be formed by a dry etching method.
  • the exposure step it is preferable to expose the film formed on the substrate into a pattern shape.
  • the pattern exposure can be performed by exposing the film on the base material through a mask having a predetermined mask pattern using an exposure apparatus such as a stepper. Thereby, an exposed part can be hardened.
  • radiation light
  • ultraviolet rays such as g-line and i-line are preferable (particularly preferably i-line).
  • Irradiation dose exposure dose
  • the oxygen concentration at the time of exposure can be appropriately selected.
  • a low oxygen atmosphere having an oxygen concentration of 19% by volume or less for example, 15% by volume or less, further 5% by volume or less, particularly May be exposed in a substantially oxygen-free manner
  • a high oxygen atmosphere with an oxygen concentration exceeding 21% by volume for example, 22% by volume or more, further 30% by volume or more, particularly 50% by volume or more.
  • the exposure illuminance can be appropriately set, and is usually 1000 W / m 2 to 100,000 W / m 2 (for example, 5000 W / m 2 or more, further 15000 W / m 2 or more, particularly 35000 W / m 2 or more). You can choose from a range.
  • Oxygen concentration and exposure illuminance may appropriately combined conditions, for example, illuminance 10000 W / m 2 at an oxygen concentration of 10 vol%, oxygen concentration of 35 vol% can be such illuminance 20000W / m 2.
  • the development removal of the unexposed portion can be performed using a developer.
  • the developer is preferably an alkaline developer that does not cause damage to the underlying circuit. You may develop using the solvent as described in this specification as a developing solution.
  • the temperature of the developer is preferably 20 to 30 ° C., for example.
  • the development time is preferably 20 to 180 seconds, more preferably 20 to 90 seconds.
  • alkaline agent used in the alkaline developer examples include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxy.
  • organic alkaline compounds such as 1,8-diazabicyclo [5,4,0] -7-undecene, dimethylbis (2-hydroxyethyl) ammonium hydroxide.
  • the inorganic alkali for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, sodium metasuccinate and the like are preferable.
  • a surfactant may be used for the developer. Examples of the surfactant include the surfactant described in the above-described composition, and a nonionic surfactant is preferable.
  • clean (rinse) with a pure water after image development.
  • the heating temperature in the preheating step and the postheating step is preferably 80 to 200 ° C.
  • the upper limit is more preferably 150 ° C. or lower.
  • the lower limit is more preferably 90 ° C. or higher.
  • the heating time in the preheating step and the postheating step is preferably 30 to 240 seconds.
  • the upper limit is more preferably 180 seconds or less.
  • the lower limit is more preferably 60 seconds or more.
  • the heat treatment method a method of heating the entire surface of the formed film can be mentioned.
  • the film strength of the pattern is increased by the heat treatment.
  • the heating temperature is preferably 100 to 260 ° C.
  • the lower limit is more preferably 120 ° C. or higher, and particularly preferably 160 ° C. or higher.
  • the upper limit is more preferably 240 ° C. or less, and particularly preferably 220 ° C. or less.
  • the heating time is preferably 1 to 180 minutes.
  • the lower limit is more preferably 3 minutes or more.
  • the upper limit is more preferably 120 minutes or less.
  • limiting in particular as a heating apparatus According to the objective, it can select suitably from well-known apparatuses, For example, a dry oven, a hot plate, an infrared heater etc. are mentioned.
  • the acid value represents the mass of potassium hydroxide required to neutralize acidic components per gram of solid content.
  • the acid value was calculated by the following formula using the inflection point of the titration pH curve as the titration end point.
  • A 56.11 ⁇ Vs ⁇ 0.5 ⁇ f / w
  • Vs Amount of 0.1 mol / L sodium hydroxide aqueous solution required for titration (mL)
  • f Potency of 0.1 mol / L sodium hydroxide aqueous solution
  • w Mass of measurement sample (g) (solid content conversion)
  • the amine value is expressed by the mass of potassium hydroxide (KOH) equivalent to the basic component per gram of the solid content. Dissolve the measurement sample in acetic acid, and use a potentiometric titrator (trade name: AT-510, manufactured by Kyoto Denshi Kogyo Co., Ltd.) to obtain the resulting solution at 25 ° C. in a 0.1 mol / L perchloric acid / acetic acid solution. And neutralization titration. The amine value was calculated by the following formula using the inflection point of the titration pH curve as the titration end point.
  • KOH potassium hydroxide
  • Vs Amine value (mgKOH / g)
  • Vs Amount of 0.1 mol / L perchloric acid / acetic acid solution required for titration (mL)
  • f 0.1 mol / L perchloric acid / acetic acid solution titer
  • mass g of measurement sample (in solid content)
  • the primary particle diameter of the powder particles was observed with a transmission electron microscope (TEM), and was determined by observing a portion where the particles were not aggregated. Moreover, about the particle size distribution of particle
  • the average primary particle size of the particles was defined as the number average arithmetic particle size calculated from the particle size distribution as the average primary particle size.
  • An electron microscope (H-7000) manufactured by Hitachi, Ltd. was used as the transmission electron microscope, and Luzex AP manufactured by Nireco Co., Ltd. was used as the image processing apparatus.
  • the circulation type dispersion apparatus was operated under the following conditions. ⁇ Bead diameter: 0.2mm in diameter ⁇ Bead filling rate: 65% by volume ⁇ Peripheral speed: 6 m / sec ⁇ Pump supply rate: 10.8 kg / hour ⁇ Cooling water: Tap water ⁇ Bead mill annular passage volume: 0.15 L ⁇ Amount of liquid mixture to be dispersed: 0.65 kg
  • the average particle diameter of the particles was measured at 30 minute intervals.
  • the average particle diameter of the particles decreased with the dispersion time, but the amount of change gradually decreased.
  • Dispersion was terminated when there was no change in d50 (integrated value 50%) in the particle size distribution.
  • the compositions of the obtained dispersions 2 to 19 are shown in the following table.
  • the refractive index of the particles is measured by the following method. First, dispersion is performed using a dispersant having a known refractive index and PGMEA. Thereafter, the prepared dispersion and a resin having a known refractive index are mixed so that the concentration in the solid content of the particles is 10% by mass, 20% by mass, 30% by mass, and 40% by mass, respectively, and four types of coating are performed. Make a liquid. After depositing these coating solutions on a Si wafer at 300 nm, the refractive index of the resulting film is measured using ellipsometry (Lambda Ace RE-3300 (trade name), Dainippon Screen Mfg. Co., Ltd.). Thereafter, the particle concentration and refractive index are plotted and extrapolated to derive the particle refractive index.
  • ellipsometry Libda Ace RE-3300 (trade name), Dainippon Screen Mfg. Co., Ltd.
  • F-1 Solsperse 36000, manufactured by Lubrizol Co., Ltd., refractive index 1.52.
  • F-2 Solsperse 46000, manufactured by Lubrizol Co., Ltd., refractive index 1.52.
  • F-5 X-22-3701E (polyalkylsiloxane having an acidic adsorption group) which is a polysiloxane resin dispersant, manufactured by Shin-Etsu Silicone, refractive index 1.43.
  • the synthesis was performed according to the following procedure with reference to Synthesis Example 11 of ⁇ 0117> of WO2014 / 126033A and Synthesis Example 1 of ⁇ 0107>. The contents of this publication are incorporated herein.
  • the following materials were charged in a 500 mL eggplant flask, and an aqueous solution obtained by dissolving 2 g of phosphoric acid in 54 g of water was added dropwise over 30 minutes while stirring at room temperature. Thereafter, the mixture was stirred at 40 ° C. for 30 minutes, and then stirred at 70 ° C. for 30 minutes. Finally, the reaction was terminated by heating at 110 ° C. for 3 hours.
  • the refractive index of each resin was measured in an uncured state by the method described in this specification.
  • D-1 Multifunctional acrylate, NK ester A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd., refractive index 1.51)
  • D-2 Polyfunctional vinyl compound containing Si atoms, VINYLTRIISOPPROPENOXYSILANE (manufactured by Azmax Co., Ltd., refractive index 1.44)
  • E-1 Photopolymerization initiator which is a trihalomethyltriazine compound (trichloromethyltriazine compound), triazine PP (manufactured by BASF)
  • E-2 Oxime ester-based photopolymerization initiator, IRGACURE OXE01 (manufactured by BASF)
  • G-1 Thioether-based anti-coloring agent, ADK STAB AO-412S (manufactured by ADEKA Corporation), the following structure.
  • G-2 Phenol-based anti-coloring agent, ADK STAB AO-80 (manufactured by ADEKA Corporation), the following structure.
  • UV absorber I-1 Compound III of JP 2009-217221 A, the following structure.
  • the glass wafer on which the exposed coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics), and tetramethylammonium hydroxide (TMAH).
  • the paddle development was performed at 23 ° C. for 60 seconds using a 0.3 mass% aqueous solution of No. 1 to form a white pattern on the glass wafer.
  • a glass wafer on which a white pattern is formed is fixed to a horizontal rotary table by a vacuum chuck method, and pure water is supplied in a shower form from an ejection nozzle above the rotation center while rotating the glass wafer at a rotation speed of 50 rpm by a rotating device. Then, a rinse treatment was performed, followed by spray drying.
  • L * is measured in a state where the solvent contained in the film is 1% by mass or less.
  • the measurement conditions are a D65 light source, the observation field of view is 2 °, and the white standard is attached to X-rite 528 (trade name, manufactured by X-rite).
  • the white pattern obtained was measured using a white patch of the calibration reference plate.
  • the L * value in the CIE 1976 L * a * b * color system was evaluated according to the following criteria. If the evaluation is A, B or C, it is determined that there is no practical problem. An evaluation of A or B is preferable, and an evaluation of A is more preferable. The results obtained are listed in the table below.
  • A: L * in the L * a * b * color system of CIE 1976 when a film having a thickness of 3.0 ⁇ m is formed is 50 or more and 75 or less.
  • B: L * in the L * a * b * color system of CIE 1976 when a film having a thickness of 3.0 ⁇ m is formed is 40 or more and less than 50 or more than 75 and 80 or less.
  • L * in the L * a * b * color system of CIE 1976 when a film having a thickness of 3.0 ⁇ m is formed is 20 or more and less than 35 or more than 85 and 90 or less.
  • the a * and b * in the L * a * b * color system of CIE 1976 when a film having a thickness of 3.0 ⁇ m was formed using each composition was a composition of an example other than the following.
  • compositions of Examples 22, 29 and 30 were used, -20 or more and less than -10 or more than 10 and 20 or less.
  • the compositions of Examples 21 to 24 were used. When it was, it was -30 or more and less than -20 or more than 20 and 30 or less.
  • C The difference between the maximum value and the minimum value of L * is 1.5 or more and less than 2.0.
  • D The difference between the maximum value and the minimum value of L * is 2.0 or more and less than 5.0.
  • E The difference between the maximum value and the minimum value of L * is 5.0 or more.
  • a film thickness of 3.0 ⁇ m can be applied in the range of the main rotation speed of 1000 to 2000 rpm.
  • B Under the condition of A, a film thickness of 3.0 ⁇ m cannot be applied, but a film thickness of 3.0 ⁇ m can be applied in the range of 750 to less than 1000 rpm and greater than 2000 and 2500 rpm or less.
  • C Under the conditions of A and B, a film thickness of 3.0 ⁇ m cannot be applied, but a film thickness of 3.0 ⁇ m can be applied in the range of main rotation number 500 to less than 750 rpm and greater than 2500 and 3000 rpm or less.
  • a film thickness of 3.0 ⁇ m cannot be applied, but a film thickness of 3.0 ⁇ m can be applied in the range of more than 3000 rpm and less than 4000 rpm.
  • E A film thickness of 3.0 ⁇ m cannot be obtained within the range of the main rotational speed.
  • the glass wafer on which the exposed coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics), and tetramethylammonium hydroxide (TMAH).
  • a spin shower developing machine DW-30 type, manufactured by Chemitronics
  • TMAH tetramethylammonium hydroxide
  • paddle development was performed at 23 ° C. for 60 seconds to form a white pattern on the glass wafer.
  • a glass wafer on which a white pattern is formed is fixed to a horizontal rotary table by a vacuum chuck method, and pure water is supplied in a shower form from an ejection nozzle above the rotation center while rotating the glass wafer at a rotation speed of 50 rpm by a rotating device.
  • a rinse treatment was performed, followed by spray drying.
  • A, B, C or D is preferable, an evaluation of A, B or C is more preferable, an evaluation of A or B is more preferable, and an evaluation of A is particularly preferable .
  • the results obtained are listed in the table below.
  • TMAH tetramethylammonium hydroxide
  • ⁇ Adhesion> Among the patterns produced in the evaluation of the pattern shape, a pattern group having a pattern size of 20 ⁇ m was observed with an optical microscope (manufactured by Olympus Corporation).
  • the evaluation criteria for adhesion are as follows. It is preferably an evaluation of A, B, C or D, more preferably an evaluation of A, B or C, particularly preferably an evaluation of A or B, and more particularly an evaluation of A. preferable.
  • the results obtained are listed in the table below.
  • B The observed pattern peeling or chipping is greater than 0% and less than 5%.
  • C Peeling or chipping of the observed pattern is 5% or more and less than 10%.
  • D The observed pattern peeling or chipping is 10% or more and less than 30%.
  • E Peeling or chipping of the observed pattern is 30% or more.
  • the spectrophotometer is used to measure the spectral L *, a *, and b * of the pattern prepared by the same method as the solvent resistance evaluation, the observation field is 2 °, the white reference is X-rite 528 ( Measurement was performed using a white patch of a calibration reference plate attached to the product name (manufactured by X-rite). X-rite 528 (trade name, manufactured by X-rite) was used as a spectrophotometer. In the measurement, the glass wafer on which the pattern was formed was placed on a table (black table) covered with a black resist.
  • the OD (Optical Density) of the black resist layer on the black platform is 3.5 (transmittance 0.03%) at 400 nm, 3.2 (transmittance 0.06) at 550 nm, and 2.5 (transmittance 0) at 700 nm. .32%), and the average reflectance in the range of 400 nm to 700 nm was 7%.
  • the OD of the black table was measured by “MCPD-3700” manufactured by Otsuka Electronics Co., Ltd., and the reflectance was measured by “U-4100” manufactured by Hitachi High-Tech Science Co., Ltd.
  • the prepared pattern was heated at 265 ° C. for 15 minutes using a hot plate, the spectrum of the pattern after heating was measured, and the color difference ⁇ E * ab before and after heating in the CIE 1976 L * a * b * color system was calculated.
  • B Color difference ⁇ E * ab is 0.5 or more and less than 1.0.
  • C Color difference ⁇ E * ab is 1.0 or more and less than 2.0.
  • D Color difference ⁇ E * ab is 2.0 or more and less than 3.0.
  • E Color difference ⁇ E * ab is 3.0 or more.
  • An evaluation of A, B, C or D is preferable, an evaluation of A, B or C is more preferable, an evaluation of A or B is more preferable, and an evaluation of A is particularly preferable .
  • the results obtained are listed in the table below.
  • the composition of each example has an L * in the L * a * b * color system of CIE 1976 of 35 to 85 when a film having a thickness of 3.0 ⁇ m is formed, It turned out that the film
  • particles having a refractive index lower than 2.1 for the resin having a wavelength of 589 nm are used, and the difference between the refractive index of the particles for the light having a wavelength of 589 nm and the refractive index of the resin having a wavelength of 589 nm is 1.
  • Comparative Examples 1 and 2 below 22 were found to have an L * of less than 35 or more than 85 in the CIE 1976 L * a * b * color system when a 3.0 ⁇ m thick film was formed.
  • Comparative Example 3 in which a resin having a refractive index with respect to light with a wavelength of 589 nm exceeds 1.5, and the difference between the refractive index with respect to light with a wavelength of 589 nm of the particle and the refractive index with respect to light with a wavelength of 589 nm is less than 1.22. This composition was found to have large density unevenness after one month.
  • ⁇ Average transmittance> With respect to a film having a thickness of 3.0 ⁇ m, which is a pattern formed by evaluating the solvent resistance using the composition of each example, transmittance in the wavelength range of 400 to 700 nm was measured using MCPD-3000 manufactured by Otsuka Electronics Co., Ltd. And measured at a pitch of 5 nm, and the average value was defined as the average transmittance. As a result, it was found that the film of each Example had an average transmittance of 1 to 45% in a wavelength range of 400 to 700 nm when converted to a thickness of 3.0 ⁇ m.
  • the film formed from the composition of the present invention has an L * in the L * a * b * color system of CIE 1976 of 35 to 85 when a film having a thickness of 3.0 ⁇ m is formed, It is a film in which subsequent density unevenness is suppressed.
  • L * in the L * a * b * color system of CIE 1976 of 35 to 85 when a film having a thickness of 3.0 ⁇ m is formed, It is a film in which subsequent density unevenness is suppressed.

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WO2021066084A1 (ja) * 2019-10-03 2021-04-08 ダウ・東レ株式会社 紫外線硬化性オルガノポリシロキサン組成物およびその用途
WO2021199748A1 (ja) 2020-03-30 2021-10-07 富士フイルム株式会社 組成物、膜及び光センサ
TWI773833B (zh) * 2017-09-28 2022-08-11 日商東麗股份有限公司 感光性樹脂組成物、感光性片材暨該等之硬化膜、其製造方法、使用其之中空構造體及電子零件
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WO2021066084A1 (ja) * 2019-10-03 2021-04-08 ダウ・東レ株式会社 紫外線硬化性オルガノポリシロキサン組成物およびその用途
WO2021199748A1 (ja) 2020-03-30 2021-10-07 富士フイルム株式会社 組成物、膜及び光センサ
WO2023054142A1 (ja) 2021-09-29 2023-04-06 富士フイルム株式会社 組成物、樹脂、膜および光センサ

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