WO2017159190A1 - Composition, film, cured film, optical sensor, and film production method - Google Patents

Composition, film, cured film, optical sensor, and film production method Download PDF

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Publication number
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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Prior art keywords
group
composition
resin
mass
particles
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PCT/JP2017/005531
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French (fr)
Japanese (ja)
Inventor
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/en
Publication of WO2017159190A1 publication Critical patent/WO2017159190A1/en

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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.

Abstract

Provided are: a composition enabling production of a film that has an L* value of 35-85 in the CIE 1976 L*a*b* color space when the film has a thickness of 3.0 µm, and that can suppress density unevenness one month after being produced; a film; a cured film; an optical sensor; and a film production method. This composition comprises particles and resins, and the particles at least includes particles that have a refractive index of 2.1 or more with respect to light having a wavelength of 589 nm, while the resins at least includes a resin that has a refractive index of at most 1.5 with respect to light having a wavelength of 589 nm.

Description

組成物、膜、硬化膜、光学センサおよび膜の製造方法Composition, film, cured film, optical sensor, and film production method
　本発明は、組成物、膜、硬化膜、光学センサおよび膜の製造方法に関する。 The present invention relates to a composition, a film, a cured film, an optical sensor, and a film manufacturing method.
　樹脂および粒子を含む組成物を用いて膜を製造することが知られている（特許文献１および２参照）。特に特許文献１には、酸化チタンなどの白色顔料である粒子を含む組成物を用いて膜を製造することが記載されている。 It is known to produce a film using a composition containing a resin and particles (see Patent Documents 1 and 2). In particular, Patent Document 1 describes that a film is produced using a composition containing particles that are white pigments such as titanium oxide.
ＷＯ２０１４／１２６０１３ＡWO2014 / 126013A 特開２０１２－２１２１１４号公報JP 2012-212114 A
　樹脂および粒子を含む組成物を用いた膜は、白色の膜として、半導体を用いた光学センサ用途に用いることができる。半導体を用いた光学センサ用途の膜では、膜は薄膜でありながら光学センサを隠蔽可能な遮蔽度を持ち、同時に光学センサを駆動させて受光量の変化を検出するために十分な光を通す遮蔽膜が求められる。純白色に近いＣＩＥ１９７６のＬ＊ａ＊ｂ＊表色系におけるＬ＊が８５を超える領域の膜では光の透過率が低く、光学センサを駆動させて受光量の変化を検出するために十分な量の光を透過しにくい。薄膜とした場合も光学センサを隠蔽させる観点から、膜は白色度としてＣＩＥ１９７６のＬ＊ａ＊ｂ＊表色系におけるＬ＊が３５以上であることが必要である。そのため、遮蔽度と透過率を両立するためにはＬ＊が３５～８５の領域である膜であることが求められている。 The film using the composition containing resin and particles can be used as an optical sensor using a semiconductor as a white film. For optical sensor films using semiconductors, 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. 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.
　一方、本発明者らが、屈折率１．６程度の樹脂を膜のバインダーまたは粒子の分散剤として用い、粒子および樹脂を含む組成物から得られた白色の膜の検討を行ったところ、経時後に濃度ムラが認められることが分かった。具体的には、常温で一ヶ月経時後の組成物を用いて白色の膜を形成すると、明らかに通常よりも白色の濃度の濃い部分と薄い部分が見られるという新規な課題を見出した。以下、常温で一ヶ月経時後の組成物を用いて白色の膜を形成した場合における、膜の白色の濃度ムラを、一ヶ月経時後の濃度ムラという。
　ここで、特許文献１には白色の遮光パターンが記載されている。しかしながら、特許文献１には一ヶ月経時後の濃度ムラの抑制に関する示唆は無い。
　一方、特許文献２には白色の膜は記載されていない。当然に、膜の白色の濃度ムラは生じず、一ヶ月経時後の濃度ムラの抑制に関する示唆は無い。
　また、特許文献１および２には、波長５８９ｎｍの光に対する屈折率が１．５以下の樹脂と屈折率の高い粒子を組み合わせることについて示唆が無い。 On the other hand, when the present inventors examined a white film obtained from a composition containing particles and a resin using a resin having a refractive index of about 1.6 as a binder of the film or a dispersant for the particles, Later, it was found that uneven density was observed. Specifically, a novel problem has been found that when a white film is formed using a composition after aging for one month at room temperature, a darker white portion and a lighter white portion than usual are clearly seen. Hereinafter, the white density unevenness of the film in the case where the white film is formed using the composition after one month at room temperature is referred to as density unevenness after one month.
Here, Patent Document 1 describes a white light-shielding pattern. However, Patent Document 1 has no suggestion regarding suppression of density unevenness after one month.
On the other hand, 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.
　本発明の解決しようとする課題は、厚さ３．０μｍの膜を形成した場合のＣＩＥ１９７６のＬ＊ａ＊ｂ＊表色系におけるＬ＊が３５～８５であり、かつ、一ヶ月経時後の濃度ムラが抑制された膜を製造できる組成物を提供することにある。 The problem to be solved by the present invention is that L * in the L * a * b * color system of CIE 1976 when a film having a thickness of 3.0 μm is formed is 35 to 85, and after a lapse of one month. It is providing the composition which can manufacture the film | membrane with which the density nonuniformity was suppressed.
　かかる状況のもと、本発明者らが鋭意検討を行った結果、以下の構成とすることにより上記課題を解決できることを見出し、本発明を完成させるに至った。本発明および本発明の好ましい構成は以下のとおりである。 Under such circumstances, as a result of intensive studies by the present inventors, it was found that the above problem can be solved by adopting the following configuration, and the present invention has been completed. The present invention and preferred configurations of the present invention are as follows.
［１］　粒子と樹脂とを含み、
　粒子が波長５８９ｎｍの光に対する屈折率が２．１以上である粒子を少なくとも含み、
　樹脂が波長５８９ｎｍの光に対する屈折率が１．５以下である樹脂を少なくとも含む、組成物。
［２］　粒子と樹脂とを含む組成物であって、
　上記粒子のうち、組成物に含まれる最も屈折率の高い粒子の波長５８９ｎｍの光に対する屈折率と、上記樹脂のうち、組成物に含まれる最も屈折率の低い樹脂の波長５８９ｎｍの光に対する屈折率との差が１．２２以上である、組成物。
［３］　組成物が硬化性組成物である、［１］または［２］に記載の組成物。
［４］　組成物を用いて厚さ３．０μｍの膜を形成した場合のＣＩＥ１９７６のＬ＊ａ＊ｂ＊表色系におけるＬ＊が３５～８５である［１］～［３］のいずれか一つに記載の組成物。［５］　粒子は、無機粒子を含む［１］～［４］のいずれか一つに記載の組成物。
［６］　無機粒子は、白色顔料を含む［５］に記載の組成物。
［７］　無機粒子は、酸化チタンを含む［５］または［６］に記載の組成物。
［８］　粒子の全質量に対する、波長５８９ｎｍの光に対する屈折率が２．１以上の粒子の含有量が８０質量％以上である［１］～［７］のいずれか一つに記載の組成物。
［９］　樹脂の全質量に対する、波長５８９ｎｍの光に対する屈折率が１．５以下の樹脂の含有量が５質量％以上である［１］～［８］のいずれか一つに記載の組成物。
［１０］　樹脂がアルカリ可溶性樹脂である［１］～［９］のいずれか一つに記載の組成物。
［１１］　樹脂がポリシロキサン系樹脂である［１］～［１０］のいずれか一つに記載の組成物。
［１２］　ポリシロキサン系樹脂の側鎖のうち５０モル％以上が炭素数１～４のアルキル基および炭素数１～４のアルコキシ基のうち少なくとも一方である［１１］に記載の組成物。
［１３］　組成物が、さらにラジカル重合性化合物および光重合開始剤を有する［１］～［１２］のいずれか一つに記載の組成物。
［１４］　ラジカル重合性化合物の全質量中における、波長５８９ｎｍの光に対する屈折率が１．５以下のラジカル重合性化合物の含有量が８０質量％以上である［１３］に記載の組成物。
［１５］　組成物が、さらに着色防止剤を有する［１］～［１４］のいずれか一つに記載の組成物。
［１６］　［１］～［１５］のいずれか一つに記載の組成物から形成された、膜。
［１７］　［１６］に記載の膜を硬化した、硬化膜。
［１８］　［１７］に記載の硬化膜を有する、光学センサ。
［１９］　［１］～［１５］のいずれか一つに記載の組成物を、パターンを有するマスクを介して露光する工程と、
　露光された組成物を現像してパターン形成する工程とを含む、膜の製造方法。 [1] including particles and 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;
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.
[2] 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.
[3] The composition according to [1] or [2], wherein the composition is a curable composition.
[4] 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 μm is formed using the composition is 35 to 85 A composition according to one. [5] The composition according to any one of [1] to [4], wherein the particles include inorganic particles.
[6] The composition according to [5], wherein the inorganic particles include a white pigment.
[7] The composition according to [5] or [6], wherein the inorganic particles include titanium oxide.
[8] The composition according to any one of [1] to [7], wherein 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. .
[9] The composition according to any one of [1] to [8], wherein 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 5% by mass or more with respect to the total mass of the resin. .
[10] The composition according to any one of [1] to [9], wherein the resin is an alkali-soluble resin.
[11] The composition according to any one of [1] to [10], wherein the resin is a polysiloxane resin.
[12] The composition according to [11], wherein 50 mol% or more of the side chain of the polysiloxane resin is at least one of an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms.
[13] The composition according to any one of [1] to [12], wherein the composition further comprises a radical polymerizable compound and a photopolymerization initiator.
[14] The 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.
[15] The composition according to any one of [1] to [14], wherein the composition further comprises a coloring inhibitor.
[16] A film formed from the composition according to any one of [1] to [15].
[17] A cured film obtained by curing the film according to [16].
[18] An optical sensor having the cured film according to [17].
[19] A step of exposing the composition according to any one of [1] to [15] through a mask having a pattern;
And a step of developing the exposed composition to form a pattern.
　本発明によれば、厚さ３．０μｍの膜を形成した場合のＣＩＥ１９７６のＬ＊ａ＊ｂ＊表色系におけるＬ＊が３５～８５であり、かつ、一ヶ月経時後の濃度ムラが抑制された膜を製造できる組成物を提供できる。
　また、本発明によれば、膜、硬化膜、光学センサおよび膜の製造方法を提供できる。 According to the present invention, when a film having a thickness of 3.0 μm is formed, 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 | membrane, a cured film, an optical sensor, and a film | membrane can be provided.
パターン形状の評価の基準を示す図である。It is a figure which shows the reference | standard of evaluation of a pattern shape.
　以下において、本発明の内容について詳細に説明する。
　以下に記載する構成要件の説明は、本発明の代表的な実施態様に基づいてなされることがあるが、本発明はそのような実施態様に限定されない。
　本明細書において、「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値及び上限値として含む範囲を意味する。
　本明細書における基（原子団）の表記において、置換及び無置換を記していない表記は、置換基を有さない基（原子団）と共に置換基を有する基（原子団）をも包含する。例えば、「アルキル基」とは、置換基を有さないアルキル基（無置換アルキル基）のみならず、置換基を有するアルキル基（置換アルキル基）をも包含する。
　本明細書において、「（メタ）アクリレート」は、アクリレート及びメタアクリレートを表し、「（メタ）アクリル」は、アクリル及びメタクリルを表し、「（メタ）アクリロイル」は、アクリロイル及びメタクリロイルを表す。
　本明細書において「露光」とは、特に断らない限り、光を用いた露光のみならず、電子線、イオンビーム等の粒子線を用いた描画も露光に含める。また、露光に用いられる光としては、一般的に、水銀灯の輝線スペクトル、エキシマレーザーに代表される遠紫外線、極紫外線（ＥＵＶ光）、Ｘ線、電子線等の活性光線または放射線が挙げられる。
　本明細書において、重量平均分子量および数平均分子量は、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）により測定したポリスチレン換算値として定義される。本明細書において、重量平均分子量（Ｍｗ）及び数平均分子量（Ｍｎ）は、例えば、ＨＬＣ－８２２０（東ソー（株）製）を用い、カラムとしてＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＡＷＭ－Ｈ（東ソー（株）製、６．０ｍｍ（内径）×１５．０ｃｍ）を、溶離液として１０ｍｍｏｌ／Ｌ　リチウムブロミドＮＭＰ（Ｎ－メチルピロリジノン）溶液を用いることによって求めることができる。 Hereinafter, the contents of the present invention will be described in detail.
The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In the description of the group (atomic group) in this specification, the description which does not describe substitution and unsubstituted includes the group (atomic group) which has a substituent with the group (atomic group) which does not have a substituent. For example, 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).
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, and “(meth) acryloyl” represents acryloyl and methacryloyl.
In this specification, unless otherwise specified, “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.
In this specification, a weight average molecular weight and a number average molecular weight are defined as a polystyrene conversion value measured by gel permeation chromatography (GPC). In this specification, 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 using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as an eluent.
［組成物］
　本発明の組成物の第１の態様は、粒子と樹脂とを含み、
　粒子が波長５８９ｎｍの光に対する屈折率が２．１以上である粒子を少なくとも含み、
　樹脂が波長５８９ｎｍの光に対する屈折率が１．５以下である樹脂を少なくとも含む。
　本発明の組成物の第２の態様は、粒子と樹脂とを含む組成物であって、
　組成物に含まれる最も屈折率の高い粒子（以下、最高屈折率の粒子とも言う）の波長５８９ｎｍの光に対する屈折率と、組成物に含まれる最も屈折率の低い樹脂（以下、最低屈折率の樹脂とも言う）の波長５８９ｎｍの光に対する屈折率との差が１．２２以上である。
　これらのような構成により、厚さ３．０μｍの膜を形成した場合のＣＩＥ１９７６のＬ＊ａ＊ｂ＊表色系におけるＬ＊が３５～８５であり、かつ、一ヶ月経時後の濃度ムラが抑制された膜を製造できる組成物を提供できる。
　本発明者らが、屈折率１．６程度の樹脂を膜のバインダーまたは粒子の分散剤として用い、粒子および樹脂を含む組成物を製造した。しかしながら、常温で一ヶ月経時後の組成物を用いて白色の膜を形成すると、明らかに通常よりも白色の濃度の濃い部分と薄い部分が見られた。
　粒子が凝集しただけであれば白色の濃度の濃い部分以外は白色の濃度は平均的に薄くなると考えられる。周囲よりも白色の濃度の薄い部分の存在は、粒子以外の固形分が偏在していることを示していると考えられる。
　一方、低屈折率の化合物は、例えばカルボン酸基やπ共役系のような分子間相互作用を引き起こす置換基が少ない傾向にあるなど、電子密度が低い傾向にある。本発明の組成物の第１の態様では、少なくとも波長５８９ｎｍの光に対する屈折率が１．５以下である樹脂（低屈折率の樹脂）を用いることで、低屈折率の樹脂同士の相互作用が低減し、少なくとも波長５８９ｎｍの光に対する屈折率が２．１以上である粒子（高屈折率の粒子）と樹脂との相互作用が有利になり、組成物中での樹脂および粒子の偏在が解消する。その結果、一ヶ月経時後の濃度ムラが抑制できたと推定される。また、本発明の組成物の第２の態様では、粒子の屈折率と樹脂の屈折率との差を大きくすることで、樹脂同士の相互作用が低減し、樹脂と粒子の相互作用が有利になり、組成物中での樹脂および粒子の偏在が解消する。その結果、一ヶ月経時後の濃度ムラが抑制できたと推定される。
　さらに、本発明の組成物の第１の態様でも本発明の組成物の第２の態様でも、粒子の屈折率と樹脂の屈折率との差を大きくすることで、組成物から形成される膜の反射率を高め、厚さ３．０μｍの膜を形成した場合のＣＩＥ１９７６のＬ＊ａ＊ｂ＊表色系におけるＬ＊が３５～８５を達成することができたと推定される。
　以下、本発明の組成物の好ましい態様について説明する。以下において、特に断りが無く組成物という場合は、本発明の組成物の第１の態様と、本発明の組成物の第２の態様の両方を含む。 [Composition]
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.
With such a configuration, when a film having a thickness of 3.0 μm is formed, 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. However, when a white film was formed by using the composition after aging for one month at room temperature, a darker white portion and a lighter portion than usual were clearly seen.
If the particles are only agglomerated, it is considered that the white density becomes thin on average except for the portion where the white density is high. It is considered that the presence of a portion having a white concentration lower than that of the surroundings indicates that solids other than particles are unevenly distributed.
On the other hand, a compound having a low refractive index tends to have a low electron density, for example, there is a tendency that the number of substituents causing intermolecular interaction such as a carboxylic acid group or a π-conjugated system is small. In the first aspect of the composition of the present invention, by using a resin (low refractive index resin) having a refractive index of 1.5 or less with respect to light having a wavelength of 589 nm, the interaction between the low refractive index resins is achieved. This reduces the interaction between the resin having a refractive index of 2.1 or higher with respect to light having a wavelength of 589 nm (high refractive index particle) and the resin, and eliminates uneven distribution of the resin and particles in the composition. . As a result, it is presumed that density unevenness after one month has been suppressed. Further, in the second aspect of the composition of the present invention, by increasing the difference between the refractive index of the particles and the refractive index of the resin, the interaction between the resins is reduced, and the interaction between the resin and the particles is advantageous. Thus, uneven distribution of resin and particles in the composition is eliminated. As a result, it is presumed that density unevenness after one month has been suppressed.
Further, in both the first aspect of the composition of the present invention and the second aspect of the composition of the present invention, a film formed from the composition by increasing the difference between the refractive index of the particles and the refractive index of the resin. It is estimated that L * in the L * a * b * color system of CIE 1976 when the film having a thickness of 3.0 μm was formed and having a thickness of 3.0 μm was able to achieve 35 to 85.
Hereinafter, preferred embodiments of the composition of the present invention will be described. In the following description, the composition without any notice includes both the first aspect of the composition of the present invention and the second aspect of the composition of the present invention.
＜特性＞
　本発明の組成物は、硬化性組成物であることが好ましい。「硬化性組成物」とは、後述する硬化性化合物を含む組成物をいう。硬化性組成物は、光硬化性組成物であってもよく、熱硬化性組成物であってもよい。
　本発明の組成物の特性の詳細を説明する。 <Characteristic>
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＊＞＞
　本発明の組成物は、組成物を用いて厚さ３．０μｍの膜を形成した場合にＣＩＥ１９７６のＬ＊ａ＊ｂ＊表色系におけるＬ＊が３５～８５であることが好ましい。組成物を用いて厚さ３．０μｍの膜を形成した場合にＣＩＥ１９７６のＬ＊ａ＊ｂ＊表色系におけるＬ＊の上限は８０未満であることがより好ましく、７５以下であることがさらに好ましく、７０以下であることが特に好ましい。組成物を用いて厚さ３．０μｍの膜を形成した場合にＣＩＥ１９７６のＬ＊ａ＊ｂ＊表色系におけるＬ＊の下限は４０以上であることがより好ましく、５０以上であることが特に好ましい。なお、ＣＩＥ１９７６のＬ＊ａ＊ｂ＊表色系におけるＬ＊の値は、後述する実施例に記載の方法で測定した値である。 << L * >>
In the composition of the present invention, when a film having a thickness of 3.0 μm is formed using the composition, L * in the L * a * b * color system of CIE 1976 is preferably 35 to 85. When a film having a thickness of 3.0 μm is formed using the composition, 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. When a film having a thickness of 3.0 μm is formed using the composition, 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. In addition, 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＊およびｂ＊＞＞
　本発明の組成物は、組成物を用いて厚さ３．０μｍの膜を形成した場合にＣＩＥ１９７６のＬ＊ａ＊ｂ＊表色系におけるａ＊およびｂ＊は－３０～３０が好ましく、－２０～２０がより好ましく、－１０～１０が特に好ましい。 << a * and b * >>
In the composition of the present invention, when a film having a thickness of 3.0 μm is formed using the composition, 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.
＜＜固形分沈降率＞＞
　本発明の組成物は、室温（２５℃）にて、３５００ｒｐｍ（ｒｏｔａｔｉｏｎｓ　ｐｅｒ　ｍｉｎｕｔｅ）の条件で４７分間遠心分離した時の組成物の固形分沈降率が１０質量％以下であることが好ましく、５質量％以下がより好ましい。組成物の固形分沈降率を低くする方法としては、組成物の粘度を高める方法や、組成物の固形分濃度を下げる方法や、組成物中における固形分（好ましくは粒子）の分散性を高める方法や、粒子の密度を低くする方法や、粒子の粒子径を小さくする方法などが挙げられる。本明細書中における「固形分」は、特に断りが無い限り、以下の「遠心処理の前の固形分」を意味する。組成物を、オーブンを用いて１６０℃１時間の条件で揮発分を乾燥させ、乾燥前後の乾燥減量を測定することで揮発量を求め、組成物の乾燥前の質量と揮発量との差を計算して、「遠心処理の前の固形分」を算出する。
　組成物を、室温、３５００ｒｐｍの条件で４７分間遠心処理を行った後の上澄み液について、上記と同様の方法で「遠心処理の後の固形分」を算出する。「遠心処理の後の固形分」と「遠心処理の前の固形分」との差を、「遠心処理の前の固形分」で割り、百分率として固形分沈降率を算出する。 << Solid content sedimentation ratio >>
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. As 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.
＜＜固形分濃度＞＞
　組成物の固形分濃度は、２０～７５質量％が好ましい。上限は、６０質量％以下がより好ましい。下限は、３０質量％以上がより好ましい。組成物の固形分濃度が上記の範囲とすることで、組成物の粘度を高めて、粒子の沈降などを効果的に抑制でき、一ヶ月経時後の濃度ムラをより効果的に改良できる。 << Solid content concentration >>
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. By setting the solid content concentration of the composition within the above range, it is possible to increase the viscosity of the composition and effectively suppress the sedimentation of particles and the like, and to effectively improve the density unevenness after one month.
＜組成物の組成＞
　以下、組成物の組成について詳細に説明する。 <Composition of composition>
Hereinafter, the composition of the composition will be described in detail.
＜＜粒子＞＞
　本発明の組成物は、粒子を含む。
　本発明の組成物は、組成物に含まれる最も屈折率の高い粒子の波長５８９ｎｍの光に対する屈折率と、組成物に含まれる最も屈折率の低い樹脂の波長５８９ｎｍの光に対する屈折率との差が１．２２以上であることが好ましく、１．２７以上であることがより好ましい。この範囲であると、厚さ３．０μｍの膜を形成した場合のＣＩＥ１９７６のＬ＊ａ＊ｂ＊表色系におけるＬ＊を高くしやすく、好ましい。 << Particles >>
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 μm is formed is easily increased.
（波長５８９ｎｍの光に対する屈折率が２．１以上である粒子）
　本発明の組成物は、粒子が少なくとも波長５８９ｎｍの光に対する屈折率が２．１以上である粒子を含むことが好ましい。
　組成物が粒子を２種類以上含む場合、組成物は、波長５８９ｎｍの光に対する屈折率が２．１以上である粒子を少なくとも１種類含むことが好ましく、波長５８９ｎｍの光に対する屈折率が２．１以上である粒子のみを含むことがより好ましい。
　本発明の組成物は、粒子の全質量に対する、波長５８９ｎｍの光に対する屈折率が２．１以上の粒子の含有量（屈折率２．１以上の粒子の含有量）が８０質量％以上であることが好ましく、９０質量％以上であることがより好ましく、９５質量％以上であることが特に好ましい。 (Particles having a refractive index of 2.1 or more with respect to light having a wavelength of 589 nm)
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.
When the composition contains two or more kinds of particles, 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.
In the composition of the present invention, the content of particles having a refractive index of 2.1 or more with respect to light having a wavelength of 589 nm (content of particles having a refractive index of 2.1 or more) 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.
　波長５８９ｎｍの光に対する屈折率が２．１以上である粒子の波長５８９ｎｍの光に対する屈折率は、２．１～２．７５であることが好ましく、２．５～２．７５であることがより好ましい。粒子の波長５８９ｎｍの光に対する屈折率が２．１以上であれば、厚さ３．０μｍの膜を形成した場合のＣＩＥ１９７６のＬ＊ａ＊ｂ＊表色系におけるＬ＊を大きくすることができ、好ましい。
　粒子の屈折率は以下の方法で測定される。
　まず、屈折率が既知である分散剤とＰＧＭＥＡを用いて分散を行う。その後、作製した分散液と屈折率が既知の樹脂を、粒子の固形分中の濃度がそれぞれ１０質量％、２０質量％、３０質量％、４０質量％になるように混合し、４種類の塗布液を作製する。これらの塗布液をＳｉウェハ上に３００ｎｍで製膜した後、得られる膜の屈折率をエリプソメトリー（ラムダエースＲＥ－３３００（商品名）、大日本スクリーン製造（株））を用いて測定する。その後、粒子濃度と屈折率をプロットし、外挿し、粒子の屈折率を導出する。
　また、組成物、膜または硬化膜から粒子を以下の方法で取り出した後で、同様に上記の実施例に記載の方法で粒子の屈折率を測定することもできる。
　膜または硬化膜から取り出した粒子について屈折率を測定する場合、粒子を膜から取り出す方法として、例えば、膜または硬化膜（組成物であれば塗布し、膜にする）に２～６ｍｏｌ／Ｌの塩基性溶液を膜または硬化膜の質量の１０～３０質量％加え、１２時間加熱還流後、ろ過および洗浄することで粒子成分を得る。 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 μm 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. 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.
Moreover, after taking out particle | grains from a composition, a film | membrane, or a cured film with the following method, the refractive index of particle | grains can also be similarly measured by the method as described in the said Example.
When measuring the refractive index of particles taken out from a film or a cured film, as 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.
　波長５８９ｎｍの光に対する屈折率が２．１以上である粒子は、平均一次粒子径が５０～３００ｎｍであることが好ましく、６０～２００ｎｍであることが一ヶ月経時後の濃度ムラの観点からより好ましく、７０～２００ｎｍであることがＬ＊の観点から特に好ましい。平均一次粒子径５０～３００ｎｍの粒子は、粒子を撮影した透過型電子顕微鏡の写真において、円状粒子であることが好ましい。平均一次粒子径５０～３００ｎｍの粒子は、厳密な円状粒子ではなく、後述の長軸と短軸を有する粒子であってもよい。
　波長５８９ｎｍの光に対する屈折率が２．１以上である粒子は、粒子径５０～３００ｎｍの粒子の割合が高いほど好ましい。具体的には、波長５８９ｎｍの光に対する屈折率が２．１以上である粒子は、粒子径５０～３００ｎｍの粒子を３０質量％以上の割合で含有することが好ましく、粒子径５０～３００ｎｍの粒子を５０質量％以上の割合で含有することがより好ましい。粒子径５０～３００ｎｍの粒子が３０質量％以上であると、厚さ３．０μｍの膜を形成した場合のＣＩＥ１９７６のＬ＊ａ＊ｂ＊表色系におけるＬ＊を３５～８５に制御しやすく、かつ、液経時安定性が優れる組成物を提供しやすい。
　本発明において、粒子の一次粒子径は、粉体粒子を透過型電子顕微鏡（ＴＥＭ）で観察し、粒子が凝集していない部分を観測することで求めることができる。本発明において、粒子の粒度分布は、一次粒子である粉体粒子を、透過型電子顕微鏡を用いて透過型電子顕微鏡写真を撮影した後、その写真を用いて画像処理装置で粒度分布を測定して求める。本発明において、粒子の平均一次粒子径は、粒度分布から算出された個数基準の算術平均径をもって平均一次粒子径とした。本明細書では、透過型電子顕微鏡として（株）日立製作所製電子顕微鏡（Ｈ－７０００）を用い、画像処理装置として（株）ニレコ製ルーゼックスＡＰを用いる。
　波長５８９ｎｍの光に対する屈折率が２．１以上である粒子は、平均長軸長が５０～１５０ｎｍの粒子であってもよい。平均長軸長が５０～１５０ｎｍの粒子は、平均長軸長が６０～１４０ｎｍであることが好ましく、８０～１３０ｎｍであることがより好ましい。
　平均長軸長が５０～１５０ｎｍの粒子は、長軸と短軸を有する粒子であることが好ましい。本明細書中、「粒子の長軸」とは、粒子を撮影した透過型電子顕微鏡の写真において、粒子の最も長い径のことを言う。本明細書中、「粒子の短軸」とは、粒子を撮影した透過型電子顕微鏡の写真において、粒子の最も短い径のことを言う。長軸と短軸を有する粒子は、棒状粒子または楕円状粒子と言われることもある。
　本発明における平均長軸長が５０～１５０ｎｍの粒子は、平均短軸長が５～５０ｎｍであることが好ましく、１０～３０ｎｍであることがより好ましく、１０～２０ｎｍであることが特に好ましい。平均長軸長が５０～１５０ｎｍの粒子は、平均長軸長が平均短軸長の２～１０倍であることが好ましく、３～６倍であることがより好ましく、４～５倍であることが特に好ましい。
　本発明の組成物では、平均長軸長が５０～１５０ｎｍの粒子は、長軸長が５０～１５０ｎｍの粒子を３０～６０質量％の割合で含有することが好ましく、長軸長が５０～１５０ｎｍの粒子を３５～５０質量％の割合で含有することがより好ましい。長軸長が５０～１５０ｎｍの粒子が３０質量％以上であると、厚さ３．０μｍの膜を形成した場合のＣＩＥ１９７６のＬ＊ａ＊ｂ＊表色系におけるＬ＊を３５～８５に制御しやすく、かつ、液経時安定性が優れる組成物を提供しやすい。平均長軸長が５０～１５０ｎｍの粒子は、長軸長が６０～１４０ｎｍの粒子を３０～６０質量％の割合で含有することが好ましく、長軸長が８０～１３０ｎｍの粒子を３０～５０質量％の割合で含有することがより好ましい。
　本発明において、粒子の長軸長および短軸長は、粉体粒子を透過型電子顕微鏡（ＴＥＭ）で観察し、粒子が凝集していない部分を観測することで求めることができる。本発明において、粒子の粒度分布は、一次粒子である粉体粒子を、透過型電子顕微鏡を用いて透過型電子顕微鏡写真を撮影した後、その写真を用いて画像処理装置で粒子の長軸長および短軸長の粒度分布を測定して求める。本発明において、粒子の平均長軸長および平均短軸長は、粒度分布から算出された個数基準の算術平均径をもって平均長軸長および平均短軸長とした。本明細書では、透過型電子顕微鏡として（株）日立製作所製電子顕微鏡（Ｈ－７０００）を用い、画像処理装置として（株）ニレコ製ルーゼックスＡＰを用いる。 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. Specifically, 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. When the particle diameter is 50 to 300 nm, the L * in the L * a * b * color system of CIE 1976 when a film having a thickness of 3.0 μm is formed can be easily controlled to 35 to 85. In addition, it is easy to provide a composition having excellent liquid aging stability.
In the present invention, 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. In the present invention, 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. In the present invention, 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. In this specification, 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. In the present specification, the “major axis of particle” refers to the longest diameter of a particle in a transmission electron microscope photograph of the particle. In the present specification, 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.
In the composition of the present invention, 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. More preferably, the particles are contained in a proportion of 35 to 50% by mass. When the particle having a major axis length of 50 to 150 nm is 30% by mass or more, 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 μm 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%.
In the present invention, 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. In the present invention, 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. In the present invention, 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. In this specification, 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.
　波長５８９ｎｍの光に対する屈折率が２．１以上である粒子の密度は、１．０～６．０ｇ／ｃｍ3が好ましい。下限は、２．５ｇ／ｃｍ3以上がより好ましく、３．０ｇ／ｃｍ3以上がさらに好ましい。上限は、４．５ｇ／ｃｍ3以下がより好ましい。波長５８９ｎｍの光に対する屈折率が２．１以上である粒子の密度が好ましい範囲の上限値より小さいほど、組成物中に粒子の沈降が生じにくく、一ヶ月経時後の濃度ムラ、パターン形状をより効果的に改善することができる。また、粒子全量中における、密度が２．５ｇ／ｃｍ3以上（好ましくは、３．０ｇ／ｃｍ3以上）の粒子の割合は、５質量％以上が好ましく、１０質量％以上がより好ましい。上限は、１００質量％とすることもでき、９９質量％以下とすることもできる。 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. As 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.
　波長５８９ｎｍの光に対する屈折率が２．１以上である粒子の種類としては特に制限はない。
　波長５８９ｎｍの光に対する屈折率が２．１以上である粒子としては、従来公知の種々の無機粒子および有機粒子を挙げることができる。波長５８９ｎｍの光に対する屈折率が２．１以上である粒子は、無機粒子を少なくとも含むことが好ましい。無機粒子は、有機粒子に比べて密度が大きいものが多く、密度が大きい粒子ほど組成物中において沈降が生じやすい。本発明の組成物の第１の態様によれば、波長５８９ｎｍの光に対する屈折率が２．１以上である粒子を波長５８９ｎｍの光に対する屈折率が１．５以下である樹脂と併用するため、粒子として無機粒子を用いる場合であっても、無機粒子の沈降を抑制して、一ヶ月経時後の濃度ムラが抑制された膜を製造できる。本発明の組成物の第２の態様によれば、組成物に含まれる最も屈折率の高い粒子の波長５８９ｎｍの光に対する屈折率と、組成物に含まれる最も屈折率の低い樹脂の波長５８９ｎｍの光に対する屈折率との差が１．２２以上であるため、粒子として無機粒子を用いる場合であっても、無機粒子の沈降を抑制して、一ヶ月経時後の濃度ムラが抑制された膜を製造できる。
　無機粒子は、金属を含む粒子であることが好ましい。金属を含む粒子は、金属単体または金属酸化物を含むことがより好ましい。 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.
Examples of 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. According to the first aspect of the composition of the present invention, 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. According to the second aspect of the composition of the present invention, 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.
　波長５８９ｎｍの光に対する屈折率が２．１以上である粒子としては、顔料、セラミック材料、磁性体材料やその他の粒子などを挙げることができ、顔料が好ましい。 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.
　本発明の組成物では、無機粒子は、白色顔料であることが好ましい。無機粒子として白色顔料を用いることで、組成物を用いて厚さ３．０μｍの膜を形成した場合において、ＣＩＥ１９７６のＬ＊ａ＊ｂ＊表色系におけるＬ＊を好ましい範囲に制御しやすい。本発明において、白色顔料は純白色のみならず、白に近い明るい灰色（例えば灰白色、薄灰色など）の顔料などを含むこととする。
　白色顔料は、密度が大きい傾向にあり、組成物中において沈降が生じやすい。本発明の組成物の第１の態様によれば、波長５８９ｎｍの光に対する屈折率が２．１以上である粒子を波長５８９ｎｍの光に対する屈折率が１．５以下である樹脂と併用するため、粒子として白色顔料を用いる場合であっても、無機粒子の沈降を抑制して、一ヶ月経時後の濃度ムラが抑制された膜を製造できる。本発明の組成物の第２の態様によれば、組成物に含まれる最も屈折率の高い粒子の波長５８９ｎｍの光に対する屈折率と、組成物に含まれる最も屈折率の低い樹脂の波長５８９ｎｍの光に対する屈折率との差が１．２２以上であるため、粒子として白色顔料を用いる場合であっても、無機粒子の沈降を抑制して、一ヶ月経時後の濃度ムラが抑制された膜を製造できる。
　白色顔料は、例えば、酸化チタン、チタン酸ストロンチウム、チタン酸バリウム、酸化亜鉛、酸化マグネシウム、酸化ジルコニウム、酸化アルミニウム、硫酸バリウム、シリカ、タルク、マイカ、水酸化アルミニウム、ケイ酸カルシウム、ケイ酸アルミニウム、中空樹脂粒子、硫化亜鉛などが挙げられる。白色顔料は、チタン原子を有する粒子が好ましく、酸化チタンがより好ましい。すなわち、本発明の組成物では、無機粒子は、酸化チタンを含むことが好ましい。 In the composition of the present invention, the inorganic particles are preferably a white pigment. By using a white pigment as the inorganic particles, when a film having a thickness of 3.0 μm is formed using the composition, L * in the L * a * b * color system of CIE 1976 can be easily controlled within a preferable range. In the present invention, 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. According to the first aspect of the composition of the present invention, 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. According to the second aspect of the composition of the present invention, 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 with respect to the refractive index with respect to light is 1.22 or more, even when a white pigment is used as the particles, a film that suppresses the sedimentation of inorganic particles and suppresses uneven density after one month has elapsed. Can be manufactured.
Examples of 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.
　酸化チタンは、二酸化チタン（ＴｉＯ2）の純度が７０％以上であることが好ましく、８０％以上であることがより好ましく、８５％以上であることが更に好ましい。酸化チタンは、ＴｉnＯ2n-1（ｎは２～４の数を表す。）で表される低次酸化チタン、酸窒化チタン等の含有量は３０質量％以下であることが好ましく、２０質量％以下であることがより好ましく、１５質量％以下であることが更に好ましい。 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%.
　酸化チタンは、ルチル型酸化チタンでもアナターゼ型酸化チタンでもよく、着色性、液経時安定性の観点から、ルチル型酸化チタンが好ましい。特にルチル型酸化チタンを用いた組成物を硬化して得られる硬化膜は、硬化膜を加熱しても、色差の変化が少なく、良好な着色性を有している。また、酸化チタンのルチル化率は、９５％以上が好ましく、９９％以上がより好ましい。
　ルチル型酸化チタンとしては、公知のものを使用することができる。ルチル型酸化チタンの製造方法には、硫酸法と塩素法の２種類あり、本発明では、いずれの製造方法により製造されたものも好適に使用することができる。ここで、硫酸法は、イルメナイト鉱石やチタンスラグを原料とし、これを濃硫酸に溶解して鉄分を硫酸鉄として分離し、溶液を加水分解することにより水酸化物の沈殿物を得、これを高温で焼成してルチル型酸化チタンを取り出す製造方法をいう。一方、塩素法は、合成ルチルや天然ルチルを原料とし、これを約１０００℃の高温で塩素ガスとカーボンに反応させて四塩化チタンを合成し、これを酸化してルチル型酸化チタンを取り出す製造方法をいう。ルチル型酸化チタンは、塩素法で得られるルチル型酸化チタンが好ましい。 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. In particular, 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. There are two types of production methods for rutile titanium oxide, a sulfuric acid method and a chlorine method. In the present invention, those produced by any production method can be suitably used. Here, 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. On the other hand, 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. Say the method. The rutile type titanium oxide is preferably a rutile type titanium oxide obtained by a chlorine method.
　波長５８９ｎｍの光に対する屈折率が２．１以上である酸化チタン粒子は、光を散乱して白色に見せることができ、組成物を用いて厚さ３．０μｍの膜を形成した場合にＣＩＥ１９７６のＬ＊ａ＊ｂ＊表色系におけるＬ＊を３５～８５に制御しやすい。酸化チタン粒子の平均一次粒子径の好ましい範囲は、波長５８９ｎｍの光に対する屈折率が２．１以上である粒子の平均一次粒子径の好ましい範囲と同様である。 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 μm 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.
　酸化チタンの比表面積は、ＢＥＴ（Ｂｒｕｎａｕｅｒ，　Ｅｍｍｅｔｔ，　Ｔｅｌｌｅｒ）法にて測定した値が１０～４００ｍ2／ｇであることが好ましく、１０～２００ｍ2／ｇであることがより好ましく、１０～１５０ｍ2／ｇであることが更に好ましく、１０～４０ｍ2／ｇであることが特に好ましく、１０～２０ｍ2／ｇであることが最も好ましい。
　酸化チタンのｐＨ（ｐｏｗｅｒ　ｏｆ　ｈｙｄｒｏｇｅｎ）は、６～８が好ましい。
　酸化チタンの吸油量（ｇ／１００ｇ）は、１０～６０（ｇ／１００ｇ）であることが好ましく、１０～４０（ｇ／１００ｇ）であることがより好ましい。
　酸化チタンは、Ｆｅ2Ｏ3、Ａｌ2Ｏ3、ＳｉＯ2、Ｎｂ2Ｏ5、Ｎａ2Ｏの合計量が、０．１質量％以下であることが好ましく、０．０５質量％以下であることがより好ましく、０．０２質量％以下であることがさらに好ましく、実質含まないことが特に好ましい。
　酸化チタンの形状には特に制限はない。例えば、等方性形状（例えば、球状、多面体状等）、異方性形状（例えば、針状、棒状、板状等）、不定形状等などの形状が挙げられる。
　酸化チタンの硬度（モース硬度）は、５～８であることが好ましく、７～７．５であることがより好ましい。
　酸化チタンの真比重（密度）は、１．０～６．０ｇ／ｃｍ3であることが好ましく、３．９～４．５ｇ／ｃｍ3であることがより好ましい。
　酸化チタンの嵩比重は０．１ｇ／ｃｍ3～１．０ｇ／ｃｍ3であることが好ましく、０．２ｇ／ｃｍ3～０．４ｇ／ｃｍ3であることがより好ましい。 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).
In the titanium oxide, 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.
There is no restriction | limiting in particular in the shape of a titanium oxide. For example, shapes such as isotropic shapes (for example, spherical shape, polyhedral shape), anisotropic shapes (for example, needle shape, rod shape, plate shape, etc.), indeterminate shapes and the like can be mentioned.
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 .
　酸化チタンなどの無機粒子は、有機化合物などの表面処理剤により表面処理されたものであってもよい。表面処理に用いる表面処理剤の例には、ポリオール、酸化アルミニウム、水酸化アルミニウム、シリカ（酸化ケイ素）、含水シリカ、アルカノールアミン、ステアリン酸、オルガノシロキサン、酸化ジルコニウム、ハイドロゲンジメチコン、シランカップリング剤、チタネートカップリング剤などが挙げられる。中でもシランカップリング剤が好ましい。また、酸化チタンなどの無機粒子は、Ａｌ（アルミニウム）、Ｓｉ（ケイ素）及び有機物の表面処理剤で処理されたものであることが好ましい。表面処理は、１種類単独の表面処理剤でも、２種類以上の表面処理剤を組み合わせて実施してもよい。また、酸化チタンなどの無機粒子の表面が、酸化アルミニウム、シリカ、酸化ジルコニウムなどの酸化物により覆われていることもまた好ましい。これにより、より耐光性および分散性が向上する。 The inorganic particles such as titanium oxide may be surface-treated with a surface treatment agent such as an organic compound. Examples of 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. Moreover, it is preferable that 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.
　酸化チタンなどの無機粒子は、塩基性金属酸化物又は塩基性金属水酸化物により被覆されていることも好ましい。塩基性金属酸化物又は塩基性金属水酸化物として、マグネシウム、ジルコニウム、セリウム、ストロンチウム、アンチモン、バリウム又はカルシウム等を含有する金属化合物が挙げられる。 It is also preferable that inorganic particles such as titanium oxide are coated with a basic metal oxide or a basic metal hydroxide. Examples of the basic metal oxide or the basic metal hydroxide include metal compounds containing magnesium, zirconium, cerium, strontium, antimony, barium, calcium, or the like.
　塩基性金属酸化物又は塩基性金属水酸化物により被覆された無機粒子は、例えば以下のようにして得ることができる。
　水又は水を主成分とする液中に無機粒子を分散させ、スラリーを得る。必要に応じてサンドミル又はボールミル等により、無機粒子を粉砕する。次いで、スラリーのｐＨを中性又はアルカリ性、場合によっては酸性にする。その後、被覆材料の原料となる水溶性塩をスラリーに添加し、無機粒子の表面を被覆する。その後、スラリーを中和し、無機粒子を回収する。回収した無機粒子は、乾燥又は乾式粉砕してもよい。 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.
　酸化チタンなどの無機粒子は、酸性部位を有し、酸性部位と反応可能な化合物により表面処理されていることが好ましい。無機顔料の酸性部位と反応可能な化合物としては、トリメチロールプロパン、トリメチロールエタン、ジトリメチロールプロパン、トリメチロールプロパンエトキシレートもしくはペンタエリスリトール等の多価アルコール、モノエタノールアミン、モノプロパノールアミン、ジエタノールアミン、ジプロパノールアミン、トリエタノールアミンもしくはトリプロパノールアミン等のアルカノールアミン、クロロシラン又はアルコキシシラン等が挙げられる。
　無機粒子と、無機粒子の酸性部位と反応可能な化合物とを反応させる方法として、（１）流体エネルギー粉砕機もしくは衝撃粉砕機等の乾式粉砕機に上記化合物と無機粒子とを投入し、無機顔料を粉砕する方法、（２）ヘンシェルミキサーもしくはスーパーミキサー等の高速攪拌機を用いて、上記化合物と、乾式粉砕した無機粒子とを攪拌し、混合する方法、（３）無機粒子の水性スラリー中に上記化合物を添加し、撹拌する方法等が挙げられる。 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. Examples of 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.
As a method of reacting inorganic particles with a compound capable of reacting with an acidic site of the inorganic particles, (1) the compound and the inorganic particles are charged into a dry pulverizer such as a fluid energy pulverizer or an impact pulverizer, and an inorganic pigment (2) A method of stirring and mixing the above compound and dry-pulverized inorganic particles using a high-speed stirrer such as a Henschel mixer or a supermixer, and (3) The above-mentioned in an aqueous slurry of inorganic particles Examples thereof include a method of adding a compound and stirring.
　無機粒子は、市販されているものを好ましく用いることができる。酸化チタンの市販品としては、例えば、石原産業（株）製の商品名タイペークＲ－５５０、Ｒ－５８０、Ｒ－６３０、Ｒ－６７０、Ｒ－６８０、Ｒ－７８０、Ｒ－７８０－２、Ｒ－８２０、Ｒ－８３０、Ｒ－８５０、Ｒ－８５５、Ｒ－９３０、Ｒ－９８０、ＣＲ－５０、ＣＲ－５０－２、ＣＲ－５７、ＣＲ－５８、ＣＲ－５８－２、ＣＲ－６０、ＣＲ－６０－２、ＣＲ－６３、ＣＲ－６７、ＣＲ－Ｓｕｐｅｒ７０、ＣＲ－８０、ＣＲ－８５、ＣＲ－９０、ＣＲ－９０－２、ＣＲ－９３、ＣＲ－９５、ＣＲ－９５３、ＣＲ－９７、ＰＦ－７３６、ＰＦ－７３７、ＰＦ－７４２、ＰＦ－６９０、ＰＦ－６９１、ＰＦ－７１１、ＰＦ－７３９、ＰＦ－７４０、ＰＣ－３、Ｓ－３０５、ＣＲ－ＥＬ、ＰＴ－３０１、ＰＴ－４０１Ｍ、ＰＴ－４０１Ｌ、ＰＴ－５０１Ａ、ＰＴ－５０１Ｒ、ＵＴ７７１、ＴＴＯ－５１Ｃ、ＴＴＯ－８０Ａ、ＴＴＯ－Ｓ－２、Ａ－２２０、ＭＰＴ－１３６、ＭＰＴ－１４０、ＭＰＴ－１４１；
　堺化学工業（株）製の商品名Ｒ－３Ｌ、Ｒ－５Ｎ、Ｒ－７Ｅ、Ｒ－１１Ｐ、Ｒ－２１、Ｒ－２５、Ｒ－３２、Ｒ－４２、Ｒ－４４、Ｒ－４５Ｍ、Ｒ－６２Ｎ、Ｒ－３１０、Ｒ－６５０、ＳＲ－１、Ｄ－９１８、ＧＴＲ－１００、ＦＴＲ－７００、ＴＣＲ－５２、Ａ－１１０、Ａ－１９０、ＳＡ－１、ＳＡ－１Ｌ、ＳＴＲ－１００Ａ－ＬＰ、ＳＴＲ－１００Ｃ－ＬＰ、ＴＣＡ－１２３Ｅ；
　テイカ（株）製の商品名ＪＲ、ＪＲＮＣ、ＪＲ－３０１、ＪＲ－４０３、ＪＲ－４０５、ＪＲ－６００Ａ、ＪＲ－６００Ｅ、ＪＲ－６０３、ＪＲ－６０５、ＪＲ－７０１、ＪＲ－８００、ＪＲ－８０５、ＪＲ－８０６、ＪＲ－１０００、ＭＴ－０１、ＭＴ－０５、ＭＴ－１０ＥＸ、ＭＴ－１００Ｓ、ＭＴ－１００ＴＶ、ＭＴ－１００Ｚ、ＭＴ－１００ＡＱ、ＭＴ－１００ＷＰ、ＭＴ－１００ＳＡ、ＭＴ－１００ＨＤ、ＭＴ－１５０ＥＸ、ＭＴ－１５０Ｗ、ＭＴ－３００ＨＤ、ＭＴ－５００Ｂ、ＭＴ－５００ＳＡ、ＭＴ－５００ＨＤ、ＭＴ－６００Ｂ、ＭＴ－６００ＳＡ、ＭＴ－７００Ｂ、ＭＴ－７００ＢＳ、ＭＴ－７００ＨＤ、ＭＴ－７００Ｚ；
　チタン工業（株）製の商品名ＫＲ－３１０、ＫＲ－３８０、ＫＲ－３８０Ｎ、ＳＴ－４８５ＳＡ１５；
　富士チタン工業（株）製の商品名ＴＲ－６００、ＴＲ－７００、ＴＲ－７５０、ＴＲ－８４０、ＴＲ－９００；
　白石カルシウム（株）製の商品名Ｂｒｉｌｌｉａｎｔ１５００等が挙げられる。また、特開２０１５－６７７９４号公報の段落００２５～００２７に記載の酸化チタンを用いることもできる。
　チタン酸ストロンチウムの市販品としては、ＳＷ－１００（チタン工業（株）製）などが挙げられる。硫酸バリウムの市販品としては、ＢＦ－１Ｌ（堺化学工業（株）製）などが挙げられる。酸化亜鉛の市販品としては、Ｚｉｎｃｏｘ　Ｓｕｐｅｒ　Ｆ－１（ハクスイテック（株）製）などが挙げられる。酸化ジルコニウムの市販品としては、Ｚ－ＮＸ（太陽鉱工（株）製）などが挙げられる。
　酸化チタンの市販品を、分級処理してから本発明の組成物に用いてもよい。例えば、ＣＲ－９０－２の分級処理品やＭＰＴ－１４１の分級処理品を好ましく用いることができる。 As the 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. R-820, R-830, R-850, R-855, R-930, R-980, CR-50, CR-50-2, CR-57, CR-58, CR-58-2, CR- 60, CR-60-2, CR-63, CR-67, CR-Super70, CR-80, CR-85, CR-90, CR-90-2, CR-93, CR-95, CR-953, CR-97, PF-736, PF-737, PF-742, PF-690, PF-691, PF-711, PF-739, PF-740, PC-3, S-305, CR-EL, PT- 301, PT-401M, PT-401L, T-501A, PT-501R, UT771, TTO-51C, TTO-80A, TTO-S-2, A-220, MPT-136, MPT-140, MPT-141;
Trade names R-3L, R-5N, R-7E, R-11P, R-21, R-25, R-32, R-42, R-44, R-45M, manufactured by Sakai Chemical Industry Co., Ltd. R-62N, R-310, R-650, SR-1, D-918, GTR-100, FTR-700, TCR-52, A-110, A-190, SA-1, SA-1L, STR- 100A-LP, STR-100C-LP, TCA-123E;
Trade names JR, JRNC, JR-301, JR-403, JR-405, JR-600A, JR-600E, JR-603, JR-605, JR-701, JR-800, JR- 805, JR-806, JR-1000, MT-01, MT-05, MT-10EX, MT-100S, MT-100TV, MT-100Z, MT-100AQ, MT-100WP, MT-100SA, MT-100HD, MT-150EX, MT-150W, MT-300HD, MT-500B, MT-500SA, MT-500HD, MT-600B, MT-600SA, MT-700B, MT-700BS, MT-700HD, MT-700Z;
Trade names KR-310, KR-380, KR-380N, ST-485SA15 manufactured by Titanium Industry Co., Ltd .;
Trade names TR-600, TR-700, TR-750, TR-840, TR-900 manufactured by Fuji Titanium Industry Co., Ltd .;
Examples include trade name Brilliant 1500 manufactured by Shiraishi Calcium Co., Ltd. Further, 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.
　無機粒子の市販品の物性と不純物について以下に示す。 The properties and impurities of commercially available inorganic particles are shown below.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　本発明において、無機粒子は、単一の無機物からなるものだけでなく、他の素材と複合させた粒子を用いてもよい。例えば、内部に空孔や他の素材を有する粒子、コア粒子に無機粒子を多数付着させた粒子、ポリマー粒子からなるコア粒子と無機ナノ微粒子からなるシェル層とからなるコアおよびシェル複合粒子を用いることが好ましい。上記ポリマー粒子からなるコア粒子と無機ナノ微粒子からなるシェル層とからなるコアおよびシェル複合粒子としては、例えば、特開２０１５－４７５２０号公報の段落００１２～００４２の記載を参酌することができ、この内容は本明細書に組み込まれる。 In the present invention, the inorganic particles are not limited to those composed of a single inorganic substance, but may be particles combined with other materials. For example, particles having pores or other materials inside, particles having a large number of inorganic particles attached to the core particles, cores composed of polymer particles and shell layers composed of inorganic nanoparticles are used, and shell composite particles. It is preferable. Examples of the 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.
　波長５８９ｎｍの光に対する屈折率が２．１以上である粒子の含有量は、組成物の全固形分に対して１質量％以上であることが好ましく、３質量％以上であることがより好ましく、５質量％以上であることが特に好ましい。上限としては特に制限はなく、組成物の全固形分に対して７０質量％以下であることがより好ましく、６０質量％以下であることがさらに好ましく、５０質量％以下であることが最も好ましい。
　また、波長５８９ｎｍの光に対する屈折率が２．１以上である粒子中における、無機粒子の割合は、５０質量％以上が好ましく、８０質量％以上がより好ましい。上限は、１００質量％とすることもでき、９９質量％以下とすることもできる。白色度、透過率、リソグラフィー特性の観点から９９質量％以下が好ましく、９５質量％以下が更に好ましい。
　また、波長５８９ｎｍの光に対する屈折率が２．１以上である粒子中における、白色顔料の割合は５０質量％以上が好ましく、８０質量％以上がより好ましい。上限は、１００質量％とすることもでき、９９質量％以下とすることもできる。白色度、透過率、リソグラフィー特性の観点から９９質量％以下が好ましく、９５質量％以下が更に好ましい。
　また、波長５８９ｎｍの光に対する屈折率が２．１以上である粒子中における、酸化チタンの割合は、５０質量％以上が好ましく、８０質量％以上がより好ましい。上限は、１００質量％とすることもでき、９９質量％以下とすることもできる。白色度、透過率、リソグラフィー特性の観点から９９質量％以下が好ましく、９５質量％以下が更に好ましい。
　また、波長５８９ｎｍの光に対する屈折率が２．１以上である粒子中における、密度が１．０～６．０ｇ／ｃｍ3の粒子の割合は、５０質量％以上が好ましく、８０質量％以上がより好ましい。上限は、１００質量％とすることもでき、９９質量％以下とすることもできる。白色度、透過率、リソグラフィー特性の観点から９９質量％以下が好ましく、９５質量％以下が更に好ましい。 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. There is no restriction | 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 | permeability, and a lithography characteristic, and 95 mass% or less is still more preferable.
Further, 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. 99 mass% or less is preferable from a viewpoint of whiteness, the transmittance | permeability, and a lithography characteristic, and 95 mass% or less is still more preferable.
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 | permeability, and a lithography characteristic, and 95 mass% or less is still more preferable.
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 | permeability, and a lithography characteristic, and 95 mass% or less is still more preferable.
＜＜その他の着色剤＞＞
　組成物は波長５８９ｎｍの光に対する屈折率が２．１以上である粒子以外の、その他の着色剤を含有してもよい。その他の着色剤を含有することで、組成物を用いて厚さ３．０μｍの膜を形成した場合にＣＩＥ１９７６のＬ＊ａ＊ｂ＊表色系におけるａ＊およびｂ＊を好ましい範囲に制御しやすい。その他の着色剤としては、有彩色着色剤や黒色着色剤などが挙げられる。 << Other colorants >>
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. By containing other colorants, 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 μm is formed using the composition. Cheap. Examples of other colorants include chromatic colorants and black colorants.
（有彩色着色剤）
　本発明の組成物は、有彩色着色剤を含有することができる。本発明において、「有彩色着色剤」とは、白色着色剤（白色顔料を含む）および黒色着色剤以外の着色剤を意味する。有彩色着色剤は、波長４００ｎｍ以上６５０ｎｍ未満の範囲に吸収極大を有する着色剤であることが好ましい。 (Chromatic colorant)
The composition of the present invention can contain a chromatic colorant. In the present invention, 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.
　有彩色着色剤は、有彩色顔料であってもよく、染料であってもよい。 The chromatic colorant may be a chromatic pigment or a dye.
　有彩色顔料は、有機顔料であることが好ましい。有機顔料としては特に限定されず、公知の有彩色顔料を用いることができる。有機顔料として、例えば、以下のものを挙げることができる。但し本発明は、これらに限定されない。
　カラーインデックス（Ｃ．Ｉ．）Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　１，２，３，４，５，６，１０，１１，１２，１３，１４，１５，１６，１７，１８，２０，２４，３１，３２，３４，３５，３５：１，３６，３６：１，３７，３７：１，４０，４２，４３，５３，５５，６０，６１，６２，６３，６５，７３，７４，７７，８１，８３，８６，９３，９４，９５，９７，９８，１００，１０１，１０４，１０６，１０８，１０９，１１０，１１３，１１４，１１５，１１６，１１７，１１８，１１９，１２０，１２３，１２５，１２６，１２７，１２８，１２９，１３７，１３８，１３９，１４７，１４８，１５０，１５１，１５２，１５３，１５４，１５５，１５６，１６１，１６２，１６４，１６６，１６７，１６８，１６９，１７０，１７１，１７２，１７３，１７４，１７５，１７６，１７７，１７９，１８０，１８１，１８２，１８５，１８７，１８８，１９３，１９４，１９９，２１３，２１４等（以上、黄色顔料）、
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｏｒａｎｇｅ　２，５，１３，１６，１７：１，３１，３４，３６，３８，４３，４６，４８，４９，５１，５２，５５，５９，６０，６１，６２，６４，７１，７３等（以上、オレンジ色顔料）、
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ　１，２，３，４，５，６，７，９，１０，１４，１７，２２，２３，３１，３８，４１，４８：１，４８：２，４８：３，４８：４，４９，４９：１，４９：２，５２：１，５２：２，５３：１，５７：１，６０：１，６３：１，６６，６７，８１：１，８１：２，８１：３，８３，８８，９０，１０５，１１２，１１９，１２２，１２３，１４４，１４６，１４９，１５０，１５５，１６６，１６８，１６９，１７０，１７１，１７２，１７５，１７６，１７７，１７８，１７９，１８４，１８５，１８７，１８８，１９０，２００，２０２，２０６，２０７，２０８，２０９，２１０，２１６，２２０，２２４，２２６，２４２，２４６，２５４，２５５，２６４，２７０，２７２，２７９等（以上、赤色顔料）、
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｇｒｅｅｎ　７，１０，３６，３７，５８，５９等（以上、緑色顔料）、
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｖｉｏｌｅｔ　１，１９，２３，２７，３２，３７，４２等（以上、紫色顔料）、
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌｕｅ　１，２，１５，１５：１，１５：２，１５：３，１５：４，１５：６，１６，２２，６０，６４，６６，７９，８０等（以上、青色顔料）
　有機顔料は、単独または２つ以上を組合せて用いることができる。 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, 166, 167, 168, 169, 170 171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214 like (or more, and yellow pigment),
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. (Orange pigment)
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279, etc. (above, red Pigment)
C. I. Pigment Green 7, 10, 36, 37, 58, 59, etc. (above, green pigment),
C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, etc. (above, purple pigment),
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80, etc. (above, blue pigment)
An organic pigment can be used individually or in combination of 2 or more.
　染料としては特に制限はなく、公知の染料が使用できる。化学構造としては、ピラゾールアゾ系、アニリノアゾ系、トリフェニルメタン系、アントラキノン系、アントラピリドン系、ベンジリデン系、オキソノール系、ピラゾロトリアゾールアゾ系、ピリドンアゾ系、シアニン系、フェノチアジン系、ピロロピラゾールアゾメチン系、キサンテン系、フタロシアニン系、ベンゾピラン系、インジゴ系、ピロメテン系等の染料が使用できる。また、これらの染料の多量体を用いてもよい。また、特開２０１５－０２８１４４号公報、特開２０１５－３４９６６号公報に記載の染料を用いることもできる。
　また、染料は、酸性染料およびその誘導体が好適に使用できる。その他、直接染料、塩基性染料、媒染染料、酸性媒染染料、アゾイック染料、分散染料、油溶染料、食品染料、および、これらの誘導体等も有用に使用することができる。以下に酸性染料の具体例を挙げるが、これらに限定されない。例えば、以下の染料、及び、これらの染料の誘導体が挙げられる。 There is no restriction | limiting in particular as dye, A well-known dye can be used. 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. Further, the dyes described in JP-A-2015-028144 and JP-A-2015-34966 can also be used.
As the dye, acid dyes and derivatives thereof can be preferably used. In addition, 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　１，７，９，１５，１８，２３，２５，２７，２９，４０～４５，６２，７０，７４，８０，８３，８６，８７，９０，９２，１０３，１１２，１１３，１２０，１２９，１３８，１４７，１５８，１７１，１８２，１９２，２４３，３２４：１、
　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　１，４，８，１４，１７，１８，２６，２７，２９，３１，３４，３５，３７，４２，４４，５０，５１，５２，５７，６６，７３，８０，８７，８８，９１，９２，９４，９７，１０３，１１１，１１４，１２９，１３３，１３４，１３８，１４３，１４５，１５０，１５１，１５８，１７６，１８３，１９８，２１１，２１５，２１６，２１７，２４９，２５２，２５７，２６０，２６６，２７４、
　Ａｃｉｄ　Ｖｉｏｌｅｔ　６Ｂ，７，９，１７，１９、
　Ａｃｉｄ　Ｙｅｌｌｏｗ　１，３，７，９，１１，１７，２３，２５，２９，３４，３６，４２，５４，７２，７３，７６，７９，９８，９９，１１１，１１２，１１４，１１６，１８４，２４３、
　Ｆｏｏｄ　Ｙｅｌｌｏｗ　３。 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, 266, 274,
Acid Violet 6B, 7, 9, 17, 19,
Acid Yellow 1,3,7,9,11,17,23,25,29,34,36,42,54,72,73,76,79,98,99,111,112,114,116,184 243,
Food Yellow 3.
　また、上記以外の、アゾ系、キサンテン系、フタロシアニン系の酸性染料も好ましく、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ　Ｂｌｕｅ　４４、３８；Ｃ．Ｉ．Ｓｏｌｖｅｎｔ　ｏｒａｎｇｅ　４５；Ｒｈｏｄａｍｉｎｅ　Ｂ、Ｒｈｏｄａｍｉｎｅ　１１０等の酸性染料及びこれらの染料の誘導体も好ましく用いられる。 Other than the above, azo, xanthene and phthalocyanine acid dyes are also preferred. I. Solvent Blue 44, 38; C.I. I. Acidic dyes such as Solvent orange 45; Rhodamine B, Rhodamine 110, and derivatives of these dyes are also preferably used.
　本発明の組成物が、有彩色着色剤を含有する場合、有彩色着色剤の含有量は、本発明の組成物の全固形分中０．１～７０質量％とすることが好ましい。下限は、０．５質量％以上がより好ましく、１．０質量％以上が特に好ましい。上限は、６０質量％以下がより好ましく、５０質量％以下が特に好ましい。本発明の組成物が、有彩色着色剤を２種類以上含む場合、その合計量が上記範囲内であることが好ましい。 When the composition of the present invention contains a chromatic colorant, 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. When 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.
（黒色着色剤）
　本発明の組成物は、黒色着色剤を含有することができる。黒色着色剤としては、無機系黒色着色剤であってもよく、有機系黒色着色剤であってもよい。 (Black colorant)
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.
　有機系黒色着色剤としては、例えば、ビスベンゾフラノン化合物、アゾメチン化合物、ペリレン化合物、アゾ系化合物などが挙げられ、ビスベンゾフラノン化合物、ペリレン化合物が好ましい。ビスベンゾフラノン化合物としては、特表２０１０－５３４７２６号公報、特表２０１２－５１５２３３号公報、特表２０１２－５１５２３４号公報などに記載のものが挙げられ、例えば、ＢＡＳＦ社製の「Ｉｒｇａｐｈｏｒ　Ｂｌａｃｋ」として入手可能である。ペリレン化合物としては、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌａｃｋ　３１、３２などが挙げられる。アゾメチン化合物としては、特開平１－１７０６０１号公報、特開平２－３４６６４号公報などに記載のものが挙げられ、例えば、大日精化社製の「クロモファインブラックＡ１１０３」として入手できる。 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.
　無機系黒色着色剤としては、特に限定されず、公知のものを用いることができる。例えば、カーボンブラック、チタンブラック、グラファイト等が挙げられ、カーボンブラック、チタンブラックが好ましく、チタンブラックがより好ましい。チタンブラックとは、チタン原子を含有する黒色粒子であり、低次酸化チタンや酸窒化チタンが好ましい。チタンブラックは、分散性向上、凝集性抑制などの目的で必要に応じ、表面を修飾することが可能である。例えば、酸化珪素、酸化チタン、酸化ゲルマニウム、酸化アルミニウム、酸化マグネシウム、又は、酸化ジルコニウムでチタンブラックの表面を被覆することが可能である。また、特開２００７－３０２８３６号公報に表されるような撥水性物質での処理も可能である。黒色顔料として、具体的には、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌａｃｋ　１，７，チタン黒顔料等が挙げられる。 The inorganic black colorant is not particularly limited, and known ones can be used. For example, 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. For example, 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.
　チタンブラックは、個々の粒子の一次粒子径及び平均一次粒子径のいずれもが小さいものが好ましい。具体的には、平均一次粒子径で１０ｎｍ～４５ｎｍの範囲のものが好ましい。 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.
　チタンブラックの比表面積は特に制限されず、ＢＥＴ（Ｂｒｕｎａｕｅｒ，　Ｅｍｍｅｔｔ，　Ｔｅｌｌｅｒ）法にて測定した値が５ｍ2／ｇ以上１５０ｍ2／ｇ以下であることが好ましく、２０ｍ2／ｇ以上１２０ｍ2／ｇ以下であることがより好ましい。チタンブラックの市販品の例としては、チタンブラック１０Ｓ、１２Ｓ、１３Ｒ、１３Ｍ、１３Ｍ－Ｃ、１３Ｒ、１３Ｒ－Ｎ、１３Ｍ－Ｔ（商品名：三菱マテリアル（株）製）、ティラック（Ｔｉｌａｃｋ）Ｄ（商品名：赤穂化成（株）製）などが挙げられる。 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.
　チタンブラックは、分散物として用いることもできる。例えば、チタンブラック粒子とシリカ粒子とを含み、分散物中のＳｉ原子とＴｉ原子との含有比を０．２０～０．５０の範囲に制御した分散物などが挙げられる。上記分散物については、特開２０１２－１６９５５６号公報の段落００２０～０１０５の記載を参酌でき、この内容は本明細書に組み込まれる。 Titanium black can also be used as a dispersion. For example, a dispersion containing titanium black particles and silica particles, in which the content ratio of Si atoms to Ti atoms in the dispersion is controlled to be in the range of 0.20 to 0.50, and the like. Regarding the 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.
＜＜樹脂＞＞
　本発明の組成物は、樹脂を含む。樹脂は、例えば、顔料などの粒子を組成物中で分散させる用途、バインダーの用途で配合される。なお、主に粒子を組成物中で分散させるために用いられる樹脂を分散剤ともいう。ただし、樹脂のこのような用途は一例であって、このような用途以外の目的で使用することもできる。 << Resin >>
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. Note that a resin mainly used for dispersing particles in a composition is also referred to as a dispersant. However, such use of the resin is an example, and the resin can be used for purposes other than such use.
（波長５８９ｎｍの光に対する屈折率が１．５以下である樹脂）
　本発明の組成物は、波長５８９ｎｍの光に対する屈折率が１．５以下である樹脂を含むことが好ましい。
　組成物が樹脂を２種類以上含む場合、組成物は、波長５８９ｎｍの光に対する屈折率が１．５以下である樹脂を少なくとも１種類含むことが好ましく、波長５８９ｎｍの光に対する屈折率が１．５以下である樹脂のみを含むことがより好ましい。
　本発明の組成物は、樹脂の全質量に対する、波長５８９ｎｍの光に対する屈折率が１．５以下の樹脂の含有量が５質量％以上であることが好ましく、３０質量％以上であることがより好ましく、５０質量％以上であることがさらに好ましく、９０質量％以上であることが特に好ましい。 (Resin having a refractive index of 1.5 or less for light having a wavelength of 589 nm)
It is preferable that the composition of this invention contains resin whose refractive index with respect to the light of wavelength 589nm is 1.5 or less.
When the composition contains two or more kinds of resins, 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.
In the composition of the present invention, 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.
　組成物が樹脂を２種類以上含む場合、組成物に含まれるすべての樹脂の波長５８９ｎｍの光に対する質量平均の屈折率（樹脂の質量平均の屈折率）が１．５以下であることが好ましく、１．４９以下であることがより好ましく、１．４７以下であることが特に好ましく、１．４５以下であることがより特に好ましい。「組成物に含まれるすべての樹脂の波長５８９ｎｍの光に対する質量平均の屈折率」とは、ｉ番目の樹脂の波長５８９ｎｍの光に対する屈折率ｎｉと、ｉ番目の樹脂の組成物に含まれるすべての樹脂（ただし、全樹脂中に１質量％以上含まれる樹脂のみを計算に入れる）に対する質量比率Ｘｉとの積を、組成物に含まれるすべての樹脂について足し合わせたものをいう。具体的には、ｎを２以上の整数、ｉを１以上の整数とした場合に、以下の計算式で計算される値のことをいう。
Figure JPOXMLDOC01-appb-M000003
　組成物に含まれるすべての樹脂の波長５８９ｎｍの光に対する質量平均の屈折率の好ましい範囲は、樹脂の波長５８９ｎｍの光に対する屈折率の好ましい範囲と同様である。 When the composition contains two or more types of resins, it is preferable that 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 (however, only the resin contained in the total resin included in the amount of 1% by mass or more) 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.
Figure JPOXMLDOC01-appb-M000003
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.
　樹脂の屈折率は、以下の方法で未硬化の状態で測定することができる。
　具体的な測定方法は、Ｓｉウェハ上に測定対象となる樹脂のみからなる膜を３００ｎｍで製膜した後、得られた膜の屈折率をエリプソメトリー（ラムダエースＲＥ－３３００（商品名）、大日本スクリーン製造（株））を用いて測定する。 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.
　樹脂の重量平均分子量（Ｍｗ）は、１０００～２０００００が好ましく、より好ましくは２０００～１０００００である。これらの範囲であると、樹脂と組成物中の全ての成分との相溶性とＬ＊の観点から好ましい。 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 *.
　波長５８９ｎｍの光に対する屈折率が１．５以下である樹脂の含有量は、組成物の全固形分に対して５～９０質量％であることが好ましく、より好ましくは１０～６０質量％であり、特に好ましくは１０～５０質量％である。これらの範囲であるとパターン形状、耐熱性、Ｌ＊の観点から好ましい。波長５８９ｎｍの光に対する屈折率が１．５以下である樹脂を、１種類のみ含んでいてもよいし、２種類以上含んでいてもよい。２種類以上含む場合は、その合計量が上記範囲となることが好ましい。 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.
　波長５８９ｎｍの光に対する屈折率が１．５以下である樹脂としては、フッ素系樹脂や、ポリシロキサン系樹脂などを挙げることができる。本発明では、樹脂が、ポリシロキサン系樹脂（ポリシロキサンが主骨格であることが好ましい）であることが好ましく、波長５８９ｎｍの光に対する屈折率が１．５以下であるポリシロキサン系樹脂であることがより好ましく、波長５８９ｎｍの光に対する屈折率が１．５以下であるアルカリ可溶性樹脂でもあるポリシロキサン系樹脂であることが特に好ましい。
　アルカリ可溶性樹脂でもあるポリシロキサン系樹脂の、アルカリ可溶性樹脂としての好ましい性質については、その他のバインダーとして用いるアルカリ可溶性樹脂の好ましい性質と同様である。
　波長５８９ｎｍの光に対する屈折率が１．５以下である樹脂は、アルカリ可溶性を付与するため、後述のアルカリ可溶性樹脂が有するアルカリ可溶を促進する基を含む繰り返し単位を有することも好ましい。好ましいアルカリ可溶を促進する基は後述のものと同じである。 Examples of the resin having a refractive index of 1.5 or less with respect to light having a wavelength of 589 nm include a fluorine resin and a polysiloxane resin. In the present invention, 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.
－フッ素系樹脂－
　フッ素系樹脂としては、樹脂にフッ素原子が含まれていれば特に限定されない。例えば、（ａ）一般式（Ｆ１）で示されるモノマーに由来する繰り返し単位を有する高分子化合物をフッ素系樹脂として用いることも好ましい。 -Fluorine resin-
The fluorine-based resin is not particularly limited as long as the resin contains a fluorine atom. For example, it is also preferable to use (a) a polymer compound having a repeating unit derived from the monomer represented by the general formula (F1) as the fluororesin.
Figure JPOXMLDOC01-appb-C000004
　一般式（Ｆ１）中、Ｒｆは、フルオロアルキル基またはパーフルオロアルキル基含有の置換基であり、ｎは１または２を表し、Ｒ1は水素原子またはメチル基を表す。
　Ｒｆはフッ素原子の数が９以上のフルオロアルキル基またはパーフルオロアルキル基含有の置換基であることが好ましい。フッ素原子の数が９以上のフルオロアルキル基またはパーフルオロアルキル基含有の置換基としては、具体的には次のようなフルオロアルキル（メタ）アクリレートが挙げられる。
　ＣＨ2＝ＣＲＣＯ2（ＣＨ2）mＣnＦ2n+1
　ｍは１または２を示し、ｎは４～１２の整数を示す。また、Ｒは炭素数１～４のアルキル基を示す。
　ＣＨ2＝ＣＲＣＯ2（ＣＨ2）m（ＣＦ2）nＨ
　ｍは１または２を示し、ｎは４～１２の整数を示す。またＲは炭素数１～４のアルキル基を示す。
　特に、フルオロアルキル基またはパーフルオロアルキル基含有の置換基あたりのフッ素原子の数が９～３０のものが好ましく、より好ましくは、１３～２５である。
Figure JPOXMLDOC01-appb-C000004
In general formula (F1), 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, and 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.
In particular, 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.
　また、フッ素原子含有不飽和単量体に由来する繰り返し単位を有する高分子化合物をフッ素系樹脂として用いることも好ましい。フッ素原子含有不飽和単量体としては、ポリフルオロアルキル基またはポリフルオロエーテル基を有するラジカル重合性単量体が挙げられ、パーフルオロアルキル基としては、パーフルオロメチル基、パーフルオロエチル基、パーフルオロプロピル基、パーフルオロブチル基、パーフルオロヘキシル基、パーフルオロオクチル基、パーフルオロデシル基、パーフルオロドデシル基、パーフルオロテトラデシル基が好適である。 It is also preferable to use a polymer compound having a repeating unit derived from a fluorine atom-containing unsaturated monomer as the fluorine resin. Examples of the fluorine atom-containing unsaturated monomer include a radical polymerizable monomer having a polyfluoroalkyl group or a polyfluoroether group, and 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.
　このようなフッ素原子含有不飽和単量体としては、ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ2（ＣＦ2）4ＣＦ3、ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ2ＣＨ2（ＣＦ2）6ＣＦ3、ＣＨ2＝ＣＨＣＯＯ（ＣＦ2）6ＣＦ3、ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＨ2（ＣＦ2）7ＣＦ3、ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＨ2（ＣＦ2）5ＣＦ（ＣＦ3）2、ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ（ＯＣＯＣＨ3）ＣＨ2（ＣＦ2）6ＣＦ（ＣＦ3）2、ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＨ（ＯＨ）ＣＨ2（ＣＦ2）6ＣＦ（ＣＦ3）2、ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＨ2（ＣＦ2）8ＣＦ3、ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ2ＣＨ2ＮＨＣＯ（ＣＦ2）8ＣＦ3、ＣＨ2＝ＣＨＯＣＯＮＨＣＯ（ＣＦ2）7ＣＦ（ＣＦ2Ｃｌ）ＣＦ3、ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＨ2Ｎ（Ｃ3Ｈ7）ＳＯ2（ＣＦ2）7ＣＦ3、ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＨ2ＣＨ2ＣＨ2（ＣＦ2）7ＣＦ3、ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ2ＣＨ2Ｎ（Ｃ2Ｈ5）ＳＯ2（ＣＦ2）7ＣＦ3、ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＨ2ＮＨＣＯ（ＣＦ2）7ＣＦ3、ＣＨ2＝ＣＨＣＯＯ（ＣＨ2）3（ＣＦ2）6ＣＦ（ＣＦ3）2、ＣＨ2＝ＣＨＣＯＯＣＨ2（ＣＦ2）10Ｈ、ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ2（ＣＦ2）10ＣＦ2Ｃｌ、ＣＨ2＝ＣＨＣＯＮＨＣＨ2ＣＨ2ＯＣＯＣＦ（ＣＦ3）ＯＣ3Ｆ7、ＣＨ2＝ＣＨＣＯＮＨＣＨ2ＣＨ2ＯＣＯＣＦ（ＣＦ3）（ＯＣ3Ｆ6）2ＯＣ3Ｆ7が好適である。
　フッ素原子含有不飽和単量体は、１種類を単独で使用することができ、または２種類以上を併用することもできる。フッ素原子含有不飽和単量体としては、市販品を使用することもできる。例えば、共栄社化学社製、商品名ライトエステルＦＭ－１０８、ライトエステルＭ－３Ｆ、ライトエステルＭ－４Ｆ；日本メクトロン社製、商品名ＣＨＥＭＩＮＯＸ　ＦＡＡＣ、ＣＨＥＭＩＮＯＸ　ＦＡＭＡＣ、ＣＨＥＭＩＮＯＸ　ＦＡＡＣ－Ｍ、ＣＨＥＭＩＮＯＸ　ＦＡＭＡＣ－Ｍ、ＣＨＥＭＩＮＯＸ　ＰＦＡＥ、ＣＨＥＭＩＮＯＸ　ＰＦＯＥ等がある。 As such a fluorine atom-containing unsaturated monomer, CH 2 ═C (CH 3 ) COOCH 2 (CF 2 ) 4 CF 3 , CH 2 ═C (CH 3 ) COOCH 2 CH 2 (CF 2 ) 6 CF 3 , CH 2 = CHCOO (CF 2 ) 6 CF 3 , CH 2 = CHCOOCH 2 CH 2 (CF 2 ) 7 CF 3 , CH 2 = CHCOOCH 2 CH 2 (CF 2 ) 5 CF (CF 3 ) 2 , CH 2 ═C (CH 3 ) COOCH (OCOCH 3 ) CH 2 (CF 2 ) 6 CF (CF 3 ) 2 , CH 2 ═CHCOOCH 2 CH (OH) CH 2 (CF 2 ) 6 CF (CF 3 ) 2 , CH 2 = CHCOOCH 2 CH 2 (CF 2 ) 8 CF 3, CH 2 = C (CH 3) COOCH 2 CH 2 NHCO (CF 2) 8 CF 3, CH 2 = CHOCONHCO (CF 2) 7 CF (CF 2 Cl) CF 3 , CH 2 = CHCOOCH 2 CH 2 N (C 3 H 7) SO 2 (CF 2) 7 CF 3, CH 2 = CHCOOCH 2 CH 2 CH 2 CH 2 (CF 2) 7 CF 3, CH 2 = C (CH 3) COOCH 2 CH 2 N (C 2 H 5 ) SO 2 (CF 2 ) 7 CF 3 , CH 2 ═CHCOOCH 2 CH 2 NHCO (CF 2 ) 7 CF 3 , CH 2 ═CHCOO (CH 2 ) 3 (CF 2 ) 6 CF (CF 3 ) 2 , CH 2 ═CHCOOCH 2 (CF 2 ) 10 H, CH 2 ═C (CH 3 ) COOCH 2 (CF 2 ) 10 CF 2 Cl, CH 2 ═CHCONHCH 2 CH 2 OCOCF (CF 3 ) OC 3 F 7 CH 2 = CHCONHCH 2 CH 2 OCOCF (CF 3 ) (OC 3 F 6 ) 2 OC 3 F 7 is 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. For example, 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.
　また、（ａ）一般式（Ｆ１）で示されるモノマーに由来する繰り返し単位およびフッ素原子含有不飽和単量体に由来する繰り返し単位のうち少なくとも一方と、アルカリ可溶を促進する基を有する繰り返し単位を有する高分子化合物もフッ素系樹脂として用いることができる。アルカリ可溶を促進する基の好ましい範囲は、後述のアルカリ可溶性樹脂が有するアルカリ可溶を促進する基の好ましい範囲と同様である。 (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.
　フッ素系樹脂の例として、特開平２－８０４号公報の第６ページ右下カラムから第９ページ右上カラムに記載のフッ素系界面活性剤も参酌でき、この内容は本明細書に組み込まれる。 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.
　フッ素系樹脂の好ましい具体例を以下に記載する。 Preferred specific examples of the fluorine-based resin are described below.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
－ポリシロキサン系樹脂－
　ポリシロキサン系樹脂としては特に制限はない。例えば、ポリシロキサン系樹脂としては、下記一般式（１）で示される化合物を単独で加水分解物縮合して得られるポリシロキサン系樹脂や、下記一般式（１）で示される化合物と他のシラン化合物と共加水分解物縮合して得られるポリシロキサン系樹脂を用いることができる。ポリシロキサン系樹脂として、特開２０１４－６６９８８号公報の＜００１４＞～＜００３５＞に記載を参酌でき、この内容は本明細書に組み込まれる。
　ポリシロキサン系樹脂は、下記一般式（１）で示される化合物に加えて、さらに下記一般式（２）で示される化合物を含むアルコキシシラン化合物を共加水分解物縮合して得られるポリシロキサン系樹脂を用いることが、耐溶剤性を高める観点から好ましい。
　ポリシロキサン系樹脂は、下記一般式（１）で示される化合物に加えて、さらに下記一般式（３）で示される化合物を含むアルコキシシラン化合物を共加水分解物縮合して得られるポリシロキサン系樹脂を用いることが、ポリシロキサン系樹脂の酸価を高くし、パターン形状を改善する観点から好ましい。また、下記一般式（３）で示される化合物を含むアルコキシシラン化合物を共加水分解物縮合して得られるポリシロキサン系樹脂は、アルカリ可溶性樹脂として用いることもできる。 -Polysiloxane resin-
There is no restriction | limiting in particular as polysiloxane type resin. For example, as 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. As the polysiloxane resin, descriptions in <0014> to <0035> of JP-A-2014-66988 can be referred to, and the contents thereof are incorporated herein.
In addition to the compound represented by the following general formula (1), 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.
In addition to the compound represented by the following general formula (1), 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. In addition, 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.
一般式（１）
　Ｒ1 2Ｓｉ（ＯＲ2）2 General formula (1)
R 1 2 Si (OR 2 ) 2
　一般式（１）におけるＲ1はそれぞれ独立してアルキル基またはフェニル基を表し、Ｒ2はそれぞれ独立して水素原子又はアルキル基を表す。
　一般式（１）におけるＲ1およびＲ2は炭素数１～６のアルキル基であることが好ましく、炭素数１～４のアルキル基であることがより好ましく、炭素数１～３のアルキル基であることが特に好ましく、炭素数１または２のアルキル基であることがより特に好ましく、メチル基であることが最も好ましい。具体的には、メチル基、エチル基、ｎ－プロピル基、ｉｓｏ－プロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ペンチル基、ヘキシル基、シクロヘキシル基等が挙げられ、中でも、メチル基又はエチル基が特に好ましい。なお、同一分子内にＲ1が複数存在する場合、それらは同一でも異なっていてもよい。一般式（１）におけるＲ2においても同様である。一般式（１）におけるＲ1およびＲ2におけるアルキル基は、直鎖状、分岐状及び環状のいずれでもよく、直鎖状であることが好ましい。 In the general formula (1), each R 1 independently represents an alkyl group or a phenyl group, and 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. Specific examples include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, and a cyclohexyl group. A methyl group or an ethyl group is particularly preferable. In addition, when two or more R < 1 > exists in the same molecule, they may be the same or different. The same applies to R 2 in the general formula (1). The alkyl group in R 1 and R 2 in the general formula (1) may be linear, branched or cyclic, and is preferably linear.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　一般式（２）におけるＲ3はメチル基又は水素原子を表し、Ｒ4は炭素数１～４のアルキレン基を表し、Ｒ5はそれぞれ独立して水素原子又は炭素数１～４のアルキル基を表し、Ｒ6はそれぞれ独立して炭素数１～６のアルキル基を表し、ｎは１～３の整数を表す。
　一般式（２）におけるＲ4は炭素数１～３のアルキレン基であることが好ましく、炭素数３のアルキレン基であることがより好ましい。
　一般式（２）におけるＲ6およびＲ5の好ましい範囲は、それぞれ一般式（１）におけるＲ1およびＲ2の好ましい範囲と同様である。
　一般式（２）におけるｎは２または３であることが好ましく、３であることがより好ましい。 In the general formula (2), R 3 represents a methyl group or a hydrogen atom, R 4 represents an alkylene group having 1 to 4 carbon atoms, and 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, and 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.
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
　一般式（３）におけるｌは０～２の整数を表し、ｍは０～３の整数を表し、Ｒ7は炭素数１～４のアルキレン基を表し、Ｒ8はそれぞれ独立して水素原子又は炭素数１～４のアルキル基を表し、Ｒ9はそれぞれ独立して炭素数１～６のアルキル基を表す。
　一般式（３）におけるｌは１であることがより好ましい。
　一般式（３）におけるｍは２または３であることが好ましく、３であることがより好ましい。
　一般式（３）におけるＲ7は炭素数１～３のアルキレン基であることが好ましく、炭素数３のアルキレン基であることがより好ましい。
　一般式（３）におけるＲ9およびＲ8の好ましい範囲は、それぞれ一般式（１）におけるＲ1およびＲ2の好ましい範囲と同様である。 In general formula (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, and R 8 each independently represents a hydrogen atom or R 1 represents an alkyl group having 1 to 4 carbon atoms, and each R 9 independently represents an alkyl group having 1 to 6 carbon atoms.
In general formula (3), 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.
　一般式（１）で示される化合物としては、例えば、ジメトキシジメチルシラン、ジエトキシジメチルシラン、ジメトキシジフェニルシラン、ジエトキシジフェニルシラン、ジヒドロキシジフェニルシラン、ジメトキシ（メチル）（フェニル）シラン、ジエトキシ（メチル）（フェニル）シラン、ジメトキシ（メチル）（フェネチル）シラン、ジシクロペンチルジメトキシシラン又はシクロヘキシルジメトキシ（メチル）シラン、メチルトリメトキシシラン、エチルトリメトキシシラン、フェニルトリメトキシシラン、メチルトリエトキシシラン、エチルトリエトキシシラン、フェニルトリエトキシシラン、が挙げられる。
　一般式（１）で示される化合物は、ジメトキシジメチルシラン、ジメトキシジフェニルシラン、フェニルトリメトキシシランが好ましく、ジメトキシジメチルシランがより好ましい。 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 phenyltrimethoxysilane, and more preferably dimethoxydimethylsilane.
　共加水分解物縮合に供するアルコキシシラン化合物に占める、一般式（１）で示される化合物の割合は、２５～７５モル％であることが好ましく、３５～７５モル％であることがより好ましく、５０～７０モル％であることが特に好ましい。また、共加水分解物縮合に供するアルコキシシラン化合物に占める、ジメトキシジフェニルシラン、ジエトキシジフェニルシラン及びジヒドロキシジフェニルシランの割合は、０～５０モル％であることが好ましく、０～４５モル％であることがより好ましく、０～３０モル％であることがさらに好ましく、０～１０モル％であることが特に好ましい。 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%. Further, 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%.
　一般式（２）で示される化合物としては、例えば、３－メタクリロキシプロピルトリメトキシシラン、３－メタクリロキシプロピルトリエトキシシラン、３－アクリロキシプロピルトリメトキシシラン、３－メタクリロキシプロピルメチルジメトキシシラン、３－メタクリロキシプロピルメチルジエトキシシラン、３－アクリロキシプロピルメチルジメトキシシラン、３－アクリロキシプロピルトリエトキシシラン又は３－アクリロキシプロピルメチルジエトキシシランが挙げられる。
　一般式（２）で示される化合物は、３－メタクリロキシプロピルトリメトキシシランが好ましい。
　共加水分解物縮合に供するアルコキシシラン化合物に占める、一般式（２）で示される化合物の割合は、１０～４５モル％であることが好ましく、１０～３０モル％であることがより好ましく、１５～２０モル％であることが特に好ましい。共加水分解物縮合に供するアルコキシシラン化合物として一般式（２）で示される化合物を用いることで、耐溶剤性を高めることができる。 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%. By using the compound represented by the general formula (2) as the alkoxysilane compound to be subjected to cohydrolyzate condensation, the solvent resistance can be enhanced.
　一般式（３）で示される化合物としては、例えば、３－トリメトキシシリルプロピル無水コハク酸、３－トリエトキシシリルプロピル無水コハク酸、３－トリメトキシシリルエチル無水コハク酸又は３－トリメトキシシリルブチル無水コハク酸、３－ジエトキシメチルシリルプロピル無水コハク酸、３－ジメトキシメチルシリルエチル無水コハク酸又は３－ジメトキシメチルシリルブチル無水コハク酸が挙げられる。
　一般式（３）で示される化合物は、３－トリメトキシシリルプロピル無水コハク酸が好ましい。
　共加水分解物縮合に供するアルコキシシラン化合物に占める、一般式（３）で示される化合物の割合は、ポリシロキサン系樹脂の酸価を高めてパターン形状を改善する観点から１～３０モル％であることが好ましく、１～２５モル％であることがより好ましく、１～２０モル％であることがさらに一ヶ月経時後の濃度ムラも抑制する観点から特に好ましい。 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.
　共加水分解物縮合に供するアルコキシシラン化合物は、一般式（５）で示される化合物をさらに含むことが好ましい。 The alkoxysilane compound to be subjected to cohydrolyzate condensation preferably further contains a compound represented by the general formula (5).
一般式（５）
　Ｒ12Ｓｉ（ＯＲ13）3 General formula (5)
R 12 Si (OR 13 ) 3
　一般式（５）におけるＲ12はエポキシ基を有する１価の有機基を表し、Ｒ13はそれぞれ独立して、アルキル基を表す。
　一般式（５）におけるＲ12で表されるエポキシ基を有する１価の有機基は、エポキシ基を１～５個有することが好ましく、１または２個有することがより好ましく、１個有することが特に好ましい。一般式（５）におけるＲ12で表されるエポキシ基を有する１価の有機基は、連結基を介して末端にエポキシ基が結合した基であることが好ましく、アルキレン基（好ましくは炭素数１～１０、より好ましくは炭素数１～６、特に好ましくは炭素数１～３）および酸素原子のうち少なくとも一方を介して末端にエポキシ基が結合した基であることがより好ましい。
　一般式（５）におけるＲ13の好ましい範囲は、一般式（１）におけるＲ2の好ましい範囲と同様である。 R 12 in the general formula (5) represents a monovalent organic group having an epoxy group, and 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).
　一般式（５）で示される化合物としては、例えば、３－グリシジロキシプロピルトリメトキシシラン、３－グリシジロキシプロピルトリエトキシシラン、３－（３，４－エポキシシクロヘキシル）プロピルトリメトキシシラン、３－（３，４－エポキシシクロヘキシル）プロピルトリエトキシシランが挙げられる。
　一般式（５）で示される化合物は、３－グリシジロキシプロピルトリメトキシシラン、３－（３，４－エポキシシクロヘキシル）プロピルトリメトキシシランが好ましい。
　共加水分解物縮合に供するアルコキシシラン化合物に占める、一般式（５）で示される化合物の割合は、１０モル％以下であることが好ましく、８モル％以下であることがより好ましく、５モル％以下であることが特に好ましい。 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
　共加水分解物縮合に供するアルコキシシラン化合物は、一般式（１）～（３）及び（５）で示される化合物以外のその他のアルコキシシラン化合物を含んでいてもよい。一般式（１）～（３）及び（５）で示される化合物以外のその他のアルコキシシラン化合物としては、例えば、フェネチルトリメトキシシラン、ナフチルトリメトキシシラン、フェネチルトリエトキシシラン、ナフチルトリエトキシシラン、テトラメトキシシラン又はテトラエトキシシランが挙げられる。
　共加水分解物縮合に供するアルコキシシラン化合物に占める、その他のアルコキシシラン化合物の割合は、一ヶ月経時後の濃度ムラを抑制し、耐溶剤性を改善する観点から、３モル％以下であることが好ましく、２モル％以下であることがより好ましく、１モル％以下であることが特に好ましい。 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.
　本発明では、ポリシロキサン系樹脂の側鎖のうち２０モル％以上（好ましくは４０モル％以上、より好ましくは５０モル％以上、特に好ましくは６０モル％以上）が、炭素数１～４のアルキル基および炭素数１～４のアルコキシ基のうち少なくとも一方であることが、波長５８９ｎｍの光に対する屈折率が１．５以下に制御しやすい観点から好ましく、炭素数１～３のアルキル基および炭素数１～３のアルコキシ基のうち少なくとも一方であることがより好ましく、炭素数１または２のアルキル基および炭素数１または２のアルコキシ基のうち少なくとも一方であることがさらに好ましく、炭素数１または２のアルキル基であることが特に好ましい。
　ポリシロキサン系樹脂の側鎖のうちフェニル基を含む側鎖が２０モル％以下であることがポリシロキサン系樹脂の屈折率を低くする観点から好ましく、１０モル％以下であることがより好ましく、５モル％以下であることが特に好ましい。 In the present invention, 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. Is preferably at least one of a group and an alkoxy group having 1 to 4 carbon atoms from the viewpoint that the refractive index with respect to light having a wavelength of 589 nm is easily controlled to 1.5 or less. More preferably, it is at least one of 1 to 3 alkoxy groups, more preferably at least one of an alkyl group having 1 or 2 carbon atoms and an alkoxy group having 1 or 2 carbon atoms, and 1 or 2 carbon atoms. Particularly preferred is an alkyl group.
Of the side chains of the polysiloxane resin, 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%.
　ポリシロキサン系樹脂は、アルコキシシラン化合物を共加水分解物縮合、すなわち、加水分解及び部分縮合させることにより得られる。共加水分解物縮合には、一般的な方法を用いることができる。例えば、混合物に有機溶剤、水及び必要に応じて触媒を添加し、５０～１５０℃で０．５～１００時間程度加熱撹拌する方法を用いることができる。なお、加熱撹拌中、必要に応じて、蒸留によって加水分解副生物（メタノール等のアルコール）や縮合副生物（水）の留去を行っても構わない。 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.
　ポリシロキサン系樹脂の好ましい例として、下記表に記載のアルコキシシラン化合物であるモノマーを共加水分解物縮合させることにより得られるポリシロキサン系樹脂を挙げることができる。 Preferred examples of the polysiloxane resin include polysiloxane resins obtained by cohydrolyzate condensation of monomers that are alkoxysilane compounds described in the following table.
　　
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-I000010
Figure JPOXMLDOC01-appb-I000011

Figure JPOXMLDOC01-appb-T000012
 　　
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-I000010
Figure JPOXMLDOC01-appb-I000011

Figure JPOXMLDOC01-appb-T000012
（その他のバインダー）
　本発明の組成物は、波長５８９ｎｍの光に対する屈折率が１．５以下である樹脂のほかに、その他のバインダーを含んでいてもよい。その他のバインダーを含有することで、膜特性が向上する。その他のバインダーは、公知のものを任意に使用できる。好ましくは水現像あるいは弱アルカリ水現像を可能とするために、水あるいは弱アルカリ水に可溶性又は膨潤性の樹脂が選択される。例えば、アルカリ可溶性の樹脂を用いるとアルカリ現像が可能になる。このような樹脂としては、側鎖にカルボキシ基を有するラジカル重合体、例えば特開昭５９－４４６１５号公報、特公昭５４－３４３２７号公報、特公昭５８－１２５７７号公報、特公昭５４－２５９５７号公報、特開昭５４－９２７２３号公報、特開昭５９－５３８３６号公報、特開昭５９－７１０４８号公報に記載されているポリマー、すなわち、カルボキシ基を有するモノマーを単独あるいは共重合させた樹脂、酸無水物を有するモノマーを単独あるいは共重合させ酸無水物ユニットを加水分解若しくはハーフエステル化若しくはハーフアミド化させた樹脂、エポキシ樹脂を不飽和モノカルボン酸及び酸無水物で変性させたエポキシアクリレート等が挙げられる。カルボキシ基を有するモノマーとしては、アクリル酸、メタクリル酸、イタコン酸、クロトン酸、マレイン酸、フマル酸、４－カルボキシスチレン等があげられ、酸無水物を有するモノマーとしては、無水マレイン酸等が挙げられる。また、側鎖にカルボキシ基を有する酸性セルロース誘導体がある。また、水酸基を有する重合体に環状酸無水物を付加させた重合体も挙げられる。その他のバインダーは、アルカリ現像液に可溶な樹脂（アルカリ可溶性樹脂ともいう）であることも好ましい。また、その他バインダーとして、エポキシ樹脂やメラミン樹脂などの熱硬化性化合物である樹脂を用いることもできる。 (Other binders)
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. By containing other binders, the film characteristics are improved. Other binders can be arbitrarily used. Preferably, 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. Examples of such resins 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. JP, 54-92723, JP 59-53836, JP 59-71048, ie, a resin obtained by homopolymerizing or copolymerizing a monomer having a carboxy group Resin in which an acid anhydride unit is hydrolyzed, half-esterified or half-amidated, or an epoxy acrylate in which an epoxy resin is modified with an unsaturated monocarboxylic acid and an acid anhydride. Etc. 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. Moreover, there exists an acidic cellulose derivative which has a carboxy group in a side chain. Moreover, the polymer which added the cyclic acid anhydride to the polymer which has a hydroxyl group is also mentioned. The other binder is also preferably a resin soluble in an alkali developer (also referred to as an alkali-soluble resin). In addition, as the binder, a resin that is a thermosetting compound such as an epoxy resin or a melamine resin can be used.
　アルカリ可溶性樹脂は、アルカリ可溶を促進する基を有するポリマーから適宜選択することができる。 The alkali-soluble resin can be appropriately selected from polymers having groups that promote alkali-solubility.
　アルカリ可溶性樹脂の数平均分子量（Ｍｎ）は、１０００～２０，０００であることが好ましい。
　アルカリ可溶性樹脂の酸価は、３０～５００ｍｇＫＯＨ／ｇが好ましい。下限は、５０ｍｇＫＯＨ／ｇ以上がより好ましく、７０ｍｇＫＯＨ／ｇ以上が更に好ましい。上限は、４００ｍｇＫＯＨ／ｇ以下がより好ましく、２００ｍｇＫＯＨ／ｇ以下がさらに好ましく、１５０ｍｇＫＯＨ／ｇ以下が特に好ましく、１２０ｍｇＫＯＨ／ｇ以下が最も好ましい。 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.
　アルカリ可溶性樹脂は、耐熱性の観点からは、ポリヒドロキシスチレン系樹脂、ポリシロキサン系樹脂、アクリル系樹脂、アクリルアミド系樹脂、アクリル／アクリルアミド共重合体樹脂が好ましく、現像性制御の観点からは、アクリル系樹脂、アクリルアミド系樹脂、アクリル／アクリルアミド共重合体樹脂がより好ましい。アルカリ可溶を促進する基（以下、酸基ともいう）としては、例えば、カルボキシ基、リン酸基、スルホ基、フェノール性ヒドロキシ基などが挙げられ、カルボキシ基が好ましい。酸基は、１種類のみであってもよいし、２種類以上であってもよい。 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. Of these resins, acryl-based resins, acrylamide-based resins, and acrylic / acrylamide copolymer resins are more preferable. Examples of the group that promotes alkali solubility (hereinafter also referred to as an acid group) include a carboxy group, a phosphate group, a sulfo group, and a phenolic hydroxy group, and a carboxy group is preferred. There may be only one type of acid group, or two or more types of acid groups.
　アルカリ可溶性樹脂は、例えば、公知のラジカル重合法で合成できる。ラジカル重合法でアルカリ可溶性樹脂を製造する際の温度、圧力、ラジカル開始剤の種類およびその量、溶剤の種類等々の重合条件は、当業者において容易に設定可能であり、実験的に条件を定めることもできる。 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.
　アルカリ可溶性樹脂は、側鎖にカルボキシ基を有するポリマーが好ましく、メタクリル酸共重合体、アクリル酸共重合体、イタコン酸共重合体、クロトン酸共重合体、マレイン酸共重合体、部分エステル化マレイン酸共重合体、ノボラック型樹脂などのアルカリ可溶性フェノール樹脂等、並びに側鎖にカルボキシ基を有する酸性セルロース誘導体、ヒドロキシ基を有するポリマーに酸無水物を付加させたものが挙げられる。特に、（メタ）アクリル酸と、これと共重合可能な他のモノマーとの共重合体が、アルカリ可溶性樹脂として好適である。（メタ）アクリル酸と共重合可能な他のモノマーとしては、特開２０１５－３４９６１号公報の段落００１７～００１９に記載のモノマーが挙げられる。例えば、アルキル（メタ）アクリレート、アリール（メタ）アクリレート、ビニル化合物、Ｎ位置換マレイミドモノマーなどが挙げられる。
　アルキル（メタ）アクリレートおよびアリール（メタ）アクリレートとしては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、フェニル（メタ）アクリレート、ベンジル（メタ）アクリレート、トリル（メタ）アクリレート、ナフチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、グリシジルメタクリレート、テトラヒドロフルフリルメタクリレート等、ビニル化合物としては、スチレン、α－メチルスチレン、ビニルトルエン、アクリロニトリル、ビニルアセテート、Ｎ－ビニルピロリドン、ポリスチレンマクロモノマー、ポリメチルメタクリレートマクロモノマー等、特開平１０－３００９２２号公報に記載のＮ位置換マレイミドモノマーとして、Ｎ－フェニルマレイミド、Ｎ－シクロヘキシルマレイミド等を挙げることができる。なお、これらの（メタ）アクリル酸と共重合可能な他のモノマーは１種類のみであってもよいし、２種類以上であってもよい。 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. 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. In particular, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin. Examples of other monomers copolymerizable with (meth) acrylic acid include monomers described in paragraphs 0017 to 0019 of JP-A-2015-34961. For example, alkyl (meth) acrylate, aryl (meth) acrylate, vinyl compound, N-substituted maleimide monomer and the like can be mentioned.
As 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, α-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.
　アルカリ可溶性樹脂は、ベンジル（メタ）アクリレート／（メタ）アクリル酸共重合体、ベンジル（メタ）アクリレート／（メタ）アクリル酸／２－ヒドロキシエチル（メタ）アクリレート共重合体、ベンジル（メタ）アクリレート／（メタ）アクリル酸／他のモノマーからなる多元共重合体が好ましく用いることができる。また、２－ヒドロキシエチル（メタ）アクリレートを共重合したもの、特開平７－１４０６５４号公報に記載の、２－ヒドロキシプロピル（メタ）アクリレート／ポリスチレンマクロモノマー／ベンジルメタクリレート／メタクリル酸共重合体、２－ヒドロキシ－３－フェノキシプロピルアクリレート／ポリメチルメタクリレートマクロモノマー／ベンジルメタクリレート／メタクリル酸共重合体、２－ヒドロキシエチルメタクリレート／ポリスチレンマクロモノマー／メチルメタクリレート／メタクリル酸共重合体、２－ヒドロキシエチルメタクリレート／ポリスチレンマクロモノマー／ベンジルメタクリレート／メタクリル酸共重合体なども好ましく用いることができる。また、市販品としては、例えばＦＦ－４２６（藤倉化成（株）製）などを用いることもできる。 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. Further, a copolymer of 2-hydroxyethyl (meth) acrylate, a 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer described in JP-A-7-140654, 2 -Hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene A macromonomer / benzyl methacrylate / methacrylic acid copolymer can also be preferably used. Moreover, as a commercial item, FF-426 (made by Fujikura Kasei Co., Ltd.) etc. can also be used, for example.
　また、アルカリ可溶性樹脂は、重合性基を有するアルカリ可溶性樹脂を使用してもよい。この態様によれば、得られる膜の耐溶剤性が向上する傾向にある。重合性基としては、（メタ）アリル基、（メタ）アクリロイル基等が挙げられる。重合性基を有するアルカリ可溶性樹脂は、重合性基を側鎖に有するアルカリ可溶性樹脂等が有用である。重合性基を有するアルカリ可溶性樹脂としては、ダイヤナ－ルＮＲシリーズ（三菱レイヨン（株）製）、Ｐｈｏｔｏｍｅｒ６１７３（ＣＯＯＨ含有　ｐｏｌｙｕｒｅｔｈａｎｅ　ａｃｒｙｌｉｃ　ｏｌｉｇｏｍｅｒ．Ｄｉａｍｏｎｄ　Ｓｈａｍｒｏｃｋ　Ｃｏ．，Ｌｔｄ．製）、ビスコートＲ－２６４、ＫＳレジスト１０６（いずれも大阪有機化学工業（株）製）、サイクロマーＰシリーズ（例えば、ＡＣＡ２３０ＡＡ）、プラクセル　ＣＦ２００シリーズ（いずれも（株）ダイセル製）、Ｅｂｅｃｒｙｌ３８００（ダイセルユーシービー（株）製）、アクリキュアーＲＤ－Ｆ８（日本触媒（株）製）などが挙げられる。 Further, as the alkali-soluble resin, an alkali-soluble resin having a polymerizable group may be used. According to this aspect, the solvent resistance of the obtained film tends to be improved. Examples of the polymerizable group include a (meth) allyl group and a (meth) acryloyl group. As the alkali-soluble resin having a polymerizable group, an alkali-soluble resin having a polymerizable group in the side chain is useful. Examples of 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.), 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.).
　アルカリ可溶性樹脂は、下記式（ＥＤ１）で示される化合物および下記式（ＥＤ２）で表される化合物（以下、これらの化合物を「エーテルダイマー」と称することもある。）のうち少なくとも一方を含むモノマー成分を重合してなるポリマーを含むことも好ましい。エーテルダイマーを含むモノマー成分を重合してなるポリマーの詳細については、特開２０１５－３４９６１号公報の段落００２２～００３１を参酌でき、この内容は本明細書に組み込まれる。 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.
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
　式（ＥＤ１）中、Ｒ1およびＲ2は、それぞれ独立して、水素原子または置換基を有していてもよい炭素数１～２５の炭化水素基を表す。
Figure JPOXMLDOC01-appb-C000014
　式（ＥＤ２）中、Ｒは、水素原子または炭素数１～３０の有機基を表す。式（ＥＤ２）の具体例としては、特開２０１０－１６８５３９号公報の記載を参酌できる。 In formula (ED1), 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.
Figure JPOXMLDOC01-appb-C000014
In the formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of the formula (ED2), the description in JP 2010-168539 A can be referred to.
　エーテルダイマーの具体例としては、例えば、特開２０１３－２９７６０号公報の段落０３１７を参酌することができ、この内容は本明細書に組み込まれる。エーテルダイマーは、１種類のみであってもよいし、２種類以上であってもよい。 As a specific example of the 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.
　アルカリ可溶性樹脂は、下記式（Ｘ）で示される化合物に由来する構造単位を含んでいてもよい。
Figure JPOXMLDOC01-appb-C000015
　式（Ｘ）において、Ｒ1は、水素原子またはメチル基を表し、Ｒ2は炭素数２～１０のアルキレン基を表し、Ｒ3は、水素原子またはベンゼン環を含んでもよい炭素数１～２０のアルキル基を表す。ｎは１～１５の整数を表す。 The alkali-soluble resin may contain a structural unit derived from a compound represented by the following formula (X).
Figure JPOXMLDOC01-appb-C000015
In formula (X), R 1 represents a hydrogen atom or a methyl group, R 2 represents an alkylene group having 2 to 10 carbon atoms, and R 3 represents a hydrogen atom or a benzene ring that may contain a benzene ring. Represents an alkyl group. n represents an integer of 1 to 15.
　上記式（Ｘ）において、Ｒ2のアルキレン基の炭素数は、２～３が好ましい。また、Ｒ3のアルキル基の炭素数は１～２０であり、より好ましくは１～１０であり、Ｒ3のアルキル基はベンゼン環を含んでもよい。Ｒ3で表されるベンゼン環を含むアルキル基としては、ベンジル基、２－フェニル（イソ）プロピル基等を挙げることができる。 In the above formula (X), 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.
　アルカリ可溶性樹脂の具体例としては、例えば、下記の樹脂が挙げられる。また、特開２０１５－３４９６１号公報の段落００３７に記載の樹脂も挙げられる。これらの樹脂の中でも、下記の重合性基を有するアルカリ可溶性樹脂であることが、耐溶剤性の観点から好ましい。
Figure JPOXMLDOC01-appb-C000016
 Specific examples of the alkali-soluble resin 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.
Figure JPOXMLDOC01-appb-C000016
　アルカリ可溶性樹脂は、特開２０１２－２０８４９４号公報の段落０５５８～０５７１（対応する米国特許出願公開第２０１２／０２３５０９９号明細書の＜０６８５＞～＜０７００＞）の記載を参酌でき、これらの内容は本明細書に組み込まれる。さらに、特開２０１２－３２７６７号公報に記載の段落番号００２９～００６３に記載の共重合体（Ｂ）および実施例で用いられているアルカリ可溶性樹脂、特開２０１２－２０８４７４号公報の段落番号００８８～００９８に記載のバインダー樹脂および実施例で用いられているバインダー樹脂、特開２０１２－１３７５３１号公報の段落番号００２２～００３２に記載のバインダー樹脂および実施例で用いられているバインダー樹脂、特開２０１３－０２４９３４号公報の段落番号０１３２～０１４３に記載のバインダー樹脂および実施例で用いられているバインダー樹脂、特開２０１１－２４２７５２号公報の段落番号００９２～００９８および実施例で用いられているバインダー樹脂、特開２０１２－０３２７７０号公報の段落番号００３０～００７２に記載のバインダー樹脂を用いることもできる。これらの内容は本明細書に組み込まれる。 Regarding the alkali-soluble resin, description in paragraphs 0558 to 0571 of JP 2012-208494 A (corresponding to <0685> to <0700> in the corresponding US Patent Application Publication No. 2012/0235099) can be referred to, Incorporated herein. Further, the copolymer (B) described in paragraph Nos. 0029 to 0063 described in JP 2012-32767 A and the alkali-soluble resin used in Examples, paragraph Nos. 0088 to 2020 of JP 2012-208474 A The binder resin described in 0098 and the binder resin used in Examples, the binder resin described in Paragraph Nos. 0022 to 0032 of JP 2012-137531 B, and the binder resin used in Examples, The binder resin described in paragraph Nos. 0132 to 0143 of No. 024934 and the binder resin used in Examples, the binder resin used in paragraph Nos. 0092 to 0098 and Examples of JP 2011-242752 A, Paragraph No. of Kokai 2012-032770 It is also possible to use a binder resin according to 030-0072. These contents are incorporated herein.
　その他のバインダーの含有量は、組成物の全固形分に対して、０～６０質量％が好ましい。上限は、６０質量％以下が好ましく、５０質量％以下がより好ましい。組成物は、その他のバインダーを、１種類のみを含んでいてもよいし、２種類以上含んでいてもよい。２種類以上含む場合は、その合計量が上記範囲となることが好ましい。 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.
（分散剤）
　本発明の組成物は、樹脂として分散剤を含有することができる。分散剤は、酸性樹脂、塩基性樹脂および両性樹脂から選ばれる１種類以上を含むことが好ましく、酸性樹脂および両性樹脂から選ばれる少なくとも１種類がより好ましい。この態様によれば、粒子の分散性が良好である。 (Dispersant)
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.
　本発明において、「酸性樹脂」とは、酸基を有する樹脂であって、酸価が５ｍｇＫＯＨ／ｇ以上、アミン価が５ｍｇＫＯＨ／ｇ未満の樹脂を意味する。酸性樹脂は、塩基性基を有さないことが好ましい。酸性樹脂が有する酸基としては、例えば、カルボキシ基、リン酸基、スルホン酸基、フェノール性ヒドロキシル基などが挙げられ、カルボキシ基が好ましい。酸性樹脂の酸価は、５～２００ｍｇＫＯＨ／ｇが好ましい。下限は、１０ｍｇＫＯＨ／ｇ以上がより好ましく、２０ｍｇＫＯＨ／ｇ以上がさらに好ましい。上限は、１００ｍｇＫＯＨ／ｇ以下がより好ましく、６０ｍｇＫＯＨ／ｇ以下がさらに好ましい。また、酸性樹脂のアミン価は、２ｍｇＫＯＨ／ｇ以下が好ましく、１ｍｇＫＯＨ／ｇ以下がより好ましい。 In the present invention, 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. As an acid group which acidic resin has, a carboxy group, a phosphoric acid group, a sulfonic acid group, a phenolic hydroxyl group etc. are mentioned, for example, A carboxy group is preferable. 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. Further, the amine value of the acidic resin is preferably 2 mgKOH / g or less, and more preferably 1 mgKOH / g or less.
　本発明において、「塩基性樹脂」とは、塩基性基を有する樹脂であって、アミン価が５ｍｇＫＯＨ／ｇ以上、酸価が５ｍｇＫＯＨ／ｇ未満の樹脂を意味する。塩基性樹脂は、酸基を有さないことが好ましい。塩基性樹脂が有する塩基性基としては、アミノ基が好ましい。塩基性樹脂のアミン価は、５～２００ｍｇＫＯＨ／ｇが好ましく、５～１５０ｍｇＫＯＨ／ｇがより好ましく、５～１００ｍｇＫＯＨ／ｇがさらに好ましい。 In the present invention, “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. As a basic group which basic resin has, 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.
　本発明において、「両性樹脂」とは、酸基と塩基性基を有する樹脂であって、酸価が５ｍｇＫＯＨ／ｇ以上で、アミン価が５ｍｇＫＯＨ／ｇ以上である樹脂を意味する。酸基としては、前述したものが挙げられ、カルボキシ基が好ましい。塩基性基としては、アミノ基が好ましい。
　両性樹脂は、酸価が５ｍｇＫＯＨ／ｇ以上で、アミン価が５ｍｇＫＯＨ／ｇ以上であることが好ましい。酸価は、５～２００ｍｇＫＯＨ／ｇが好ましい。下限は、１０ｍｇＫＯＨ／ｇ以上がより好ましく、２０ｍｇＫＯＨ／ｇ以上がさらに好ましい。上限は、１５０ｍｇＫＯＨ／ｇ以下がより好ましく、１００ｍｇＫＯＨ／ｇ以下がさらに好ましい。アミン価は、５～２００ｍｇＫＯＨ／ｇが好ましい。下限は、１０ｍｇＫＯＨ／ｇ以上がより好ましく、２０ｍｇＫＯＨ／ｇ以上がさらに好ましい。上限は、１５０ｍｇＫＯＨ／ｇ以下がより好ましく、１００ｍｇＫＯＨ／ｇ以下がさらに好ましい。両性樹脂の酸価とアミン価の比率は、酸価：アミン価＝１：４～４：１が好ましく、１：３～３：１がより好ましい。 In the present invention, 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. Examples of the acid group include those described above, and a carboxy group is preferable. As 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 ratio between the acid value and the amine value of the amphoteric resin is preferably acid value: amine value = 1: 4 to 4: 1, more preferably 1: 3 to 3: 1.
　分散剤としては、高分子分散剤〔例えば、アミン基を有する樹脂（ポリアミドアミンとその塩など）、オリゴイミン系樹脂、ポリカルボン酸とその塩、高分子量不飽和酸エステル、変性ポリウレタン、変性ポリエステル、変性ポリ（メタ）アクリレート、（メタ）アクリル系共重合体、ナフタレンスルホン酸ホルマリン重縮合物〕等を挙げることができる。高分子分散剤は、その構造から更に直鎖状高分子、末端変性型高分子、グラフト型高分子、ブロック型高分子に分類することができる。 Examples of the dispersant 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.
　分散剤は、顔料に対する吸着能を有する部位を有することが好ましい（以下、「吸着部位」と総称する）。吸着部位としては、酸基、ウレア基、ウレタン基、配位性酸素原子を有する基、塩基性窒素原子を有する基、複素環基、アルキルオキシカルボニル基、アルキルアミノカルボニル基、カルボキシ基、スルホンアミド基、アルコキシシリル基、エポキシ基、イソシアネート基及び水酸基よりなる群から選択される基を少なくとも１種類有する１価の置換基等が挙げられる。吸着部位は、酸系吸着部位であることが好ましい。酸系吸着部位としては酸基等が挙げられる。なかでも、酸系吸着部位がリン原子含有基およびカルボキシ基の少なくとも一方であることが好ましい。リン原子含有基としては、リン酸エステル基、ポリリン酸エステル基、リン酸基等が挙げられる。吸着部位の詳細については、特開２０１５－３４９６１号公報の段落００７３～００８０を参酌でき、この内容は本明細書に組み込まれる。 It is preferable that 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. are mentioned as an acid type adsorption site. Especially, it is preferable that an acid type adsorption site is at least one of a phosphorus atom containing group and a carboxy group. Examples of the phosphorus atom-containing group include a phosphate group, a polyphosphate group, and a phosphate group. For details of the adsorption site, paragraphs 0073 to 0080 of JP-A-2015-34961 can be referred to, the contents of which are incorporated herein.
　本発明において、樹脂（分散剤）は、下記式（１１１）で表される樹脂が好ましい。 In the present invention, the resin (dispersant) is preferably a resin represented by the following formula (111).
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　上記式（１１１）中、Ｒ1は、（ｍ＋ｎ）価の連結基を表し、Ｒ2は単結合又は２価の連結基を表す。Ａ1は、酸基、ウレア基、ウレタン基、配位性酸素原子を有する基、塩基性窒素原子を有する基、複素環基、アルキルオキシカルボニル基、アルキルアミノカルボニル基、カルボキシ基、スルホンアミド基、アルコキシシリル基、エポキシ基、イソシアネート基及び水酸基よりなる群から選択される基を少なくとも１種類有する１価の置換基を表す。ｎ個のＡ1及びＲ2は、それぞれ、同一であっても、異なっていてもよい。ｍは８以下の正の数を表し、ｎは１～９を表し、ｍ＋ｎは３～１０を満たす。Ｐ1は１価のポリマー鎖を表す。ｍ個のＰ1は、同一であっても、異なっていてもよい。 In the above formula (111), R 1 represents an (m + n) -valent linking group, and 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 Represents a monovalent substituent having at least one group selected from the group consisting of an alkoxysilyl group, an epoxy group, an isocyanate group and a hydroxyl 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.
　式（１１１）で表される樹脂が有する、置換基Ａ1は、顔料（例えば、酸化チタンなどの無機粒子）と相互作用することができるので、式（１１１）で表される樹脂は、ｎ個（１～９個）の置換基Ａ1を有することにより、顔料（例えば、酸化チタンなどの無機粒子）と強固に相互作用して、組成物中における顔料の分散性を向上できる。また、式（１１１）で表される樹脂がｍ個有するポリマー鎖Ｐ1は立体反発基として機能することができ、ｍ個有することにより良好な立体反発力を発揮して、顔料（例えば、酸化チタンなどの無機粒子）を均一に分散することができる。 Since the substituent A 1 of 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). In addition, 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.
　式（１１１）において、Ｒ1は、（ｍ＋ｎ）価の連結基を表す。（ｍ＋ｎ）価の連結基としては、１から１００個までの炭素原子、０個から１０個までの窒素原子、０個から５０個までの酸素原子、１個から２００個までの水素原子、および０個から２０個までの硫黄原子から成り立つ基が含まれる。（ｍ＋ｎ）価の連結基は、具体的な例として、下記の構造単位または以下の構造単位が２以上組み合わさって構成される基（環構造を形成していてもよい）を挙げることができる。（ｍ＋ｎ）価の連結基の詳細については、特開２００７－２７７５１４号公報の段落００７６～００８４を参酌でき、この内容は本明細書に組み込まれる。 In Formula (111), 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. . For details of the (m + n) -valent linking group, paragraphs 0076 to 0084 of JP-A-2007-277514 can be referred to, the contents of which are incorporated herein.
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
　式（１１１）において、Ｐ1は、１価のポリマー鎖を表す。１価のポリマー鎖は、ビニル化合物由来の繰り返し単位を有する１価のポリマー鎖が好ましい。ポリマー鎖の詳細については、特開２００７－２７７５１４号公報の段落００８７～００９８を参酌でき、この内容は本明細書に組み込まれる。 In formula (111), 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. For details of the polymer chain, paragraphs 0087 to 0098 of JP-A-2007-277514 can be referred to, the contents of which are incorporated herein.
　式（１１１）において、Ｒ2は単結合又は２価の連結基を表す。２価の連結基としては、１から１００個までの炭素原子、０個から１０個までの窒素原子、０個から５０個までの酸素原子、１個から２００個までの水素原子、および０個から２０個までの硫黄原子から成り立つ基が含まれ、無置換でも置換基を更に有していてもよい。２価の連結基は、具体的な例として、下記の構造単位または以下の構造単位が２以上組み合わさって構成される基を挙げることができる。２価の連結基の詳細については、特開２００７－２７７５１４号公報の段落００７１～００７５を参酌でき、この内容は本明細書に組み込まれる。 In the formula (111), 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.
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
　式（１１１）においてＡ1が表す１価の置換基の詳細については、特開２００７－２７７５１４号公報の段落００４１～００７０を参酌でき、この内容は本明細書に組み込まれる。 For details of the monovalent substituent represented by A 1 in formula (111), paragraphs 0041 to 0070 of JP-A-2007-277514 can be referred to, the contents of which are incorporated herein.
　上記式（１１１）で表される高分子化合物としては、特開２００７－２７７５１４号公報の段落００３９（対応する米国特許出願公開第２０１０／０２３３５９５号明細書の＜００５３＞）以降の記載、および、特開２０１５－３４９６１号公報の段落００８１～０１１７の記載を参酌でき、これらの内容は本明細書に組み込まれる。 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.
　本発明において、樹脂（分散剤）は、下記式（１１）～式（１４）のいずれかで表される繰り返し単位を含むグラフト共重合体を用いることもできる。 In the present invention, as the resin (dispersant), a graft copolymer including a repeating unit represented by any one of the following formulas (11) to (14) can also be used.
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
　式（１１）～式（１４）において、Ｗ1、Ｗ2、Ｗ3、及びＷ4はそれぞれ独立に酸素原子、または、ＮＨを表し、Ｘ1、Ｘ2、Ｘ3、Ｘ4、及びＸ5はそれぞれ独立に水素原子又は１価の基を表し、Ｙ1、Ｙ2、Ｙ3、及びＹ4はそれぞれ独立に２価の連結基を表し、Ｚ1、Ｚ2、Ｚ3、及びＺ4はそれぞれ独立に１価の基を表し、Ｒ3はアルキレン基を表し、Ｒ4は水素原子又は１価の基を表し、ｎ、ｍ、ｐ、及びｑはそれぞれ独立に１～５００の整数を表し、ｊ及びｋはそれぞれ独立に２～８の整数を表し、式（１３）において、ｐが２～５００のとき、複数存在するＲ3は互いに同じであっても異なっていてもよく、式（１４）において、ｑが２～５００のとき、複数存在するＸ5及びＲ4は互いに同じであっても異なっていてもよい。 In the formulas (11) to (14), W 1 , W 2 , W 3 , and W 4 each independently represent an oxygen atom or NH, and 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, and 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, and 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; In the formula (14), when q is 2 to 500, a plurality of X 5 and R 4 may be the same or different from each other.
　Ｗ1、Ｗ2、Ｗ3、及びＷ4は酸素原子であることが好ましい。Ｘ1、Ｘ2、Ｘ3、Ｘ4、及びＸ5は、水素原子又は炭素数１～１２のアルキル基であることが好ましく、それぞれ独立に、水素原子又はメチル基であることがより好ましく、メチル基が特に好ましい。Ｙ1、Ｙ2、Ｙ3、及びＹ4は、それぞれ独立に、２価の連結基を表し、連結基は特に構造上制約されない。Ｚ1、Ｚ2、Ｚ3、及びＺ4が表す１価の基は、特に限定されず、具体的には、アルキル基、水酸基、アルコキシ基、アリールオキシ基、ヘテロアリールオキシ基、アルキルチオエーテル基、アリールチオエーテル基、ヘテロアリールチオエーテル基、及びアミノ基などが挙げられる。これらの中でも、Ｚ1、Ｚ2、Ｚ3、及びＺ4で表される有機基としては、特に分散性向上の観点から、立体反発効果を有するものが好ましく、各々独立に炭素数５～２４のアルキル基又はアルコキシ基が好ましく、その中でも、特に各々独立に炭素数５～２４の分岐状アルキル基、炭素数５～２４の環状アルキル基、又は、炭素数５～２４のアルコキシ基が好ましい。なお、アルコキシ基中に含まれるアルキル基は、直鎖状、分岐鎖状、環状のいずれでもよい。 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. Among these, as 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. Of these, 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.
　式（１１）～式（１４）において、ｎ、ｍ、ｐ、及びｑは、それぞれ独立に、１～５００の整数である。また、式（１１）及び式（１２）において、ｊ及びｋは、それぞれ独立に、２～８の整数を表す。式（１１）及び式（１２）におけるｊ及びｋは、分散安定性、現像性の観点から、４～６の整数が好ましく、５が最も好ましい。 In the formulas (11) to (14), n, m, p, and q are each independently an integer of 1 to 500. In the formulas (11) and (12), 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.
　式（１３）中、Ｒ3はアルキレン基を表し、炭素数１～１０のアルキレン基が好ましく、炭素数２又は３のアルキレン基がより好ましい。ｐが２～５００のとき、複数存在するＲ3は互いに同じであっても異なっていてもよい。 In the formula (13), 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. When p is 2 to 500, a plurality of R 3 may be the same or different from each other.
　式（１４）中、Ｒ4は水素原子又は１価の基を表す。１価の基としては特に構造上限定はされない。Ｒ4として好ましくは、水素原子、アルキル基、アリール基、及びヘテロアリール基が挙げられ、更に好ましくは、水素原子、又はアルキル基である。Ｒ4がアルキル基である場合、炭素数１～２０の直鎖状アルキル基、炭素数３～２０の分岐状アルキル基、又は炭素数５～２０の環状アルキル基が好ましく、炭素数１～２０の直鎖状アルキル基がより好ましく、炭素数１～６の直鎖状アルキル基が特に好ましい。式（１４）において、ｑが２～５００のとき、グラフト共重合体中に複数存在するＸ5及びＲ4は互いに同じであっても異なっていてもよい。 In formula (14), 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. When 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. Are more preferable, and linear alkyl groups having 1 to 6 carbon atoms are particularly preferable. In the formula (14), when q is 2 ~ 500, X 5, and R 4 a plurality present in the graft copolymer may be different from one another the same.
　上記グラフト共重合体については、特開２０１２－２５５１２８号公報の段落番号００２５～００９４の記載を参酌でき、本明細書には上記内容が組み込まれる。上記グラフト共重合体の具体例としては、例えば、以下の樹脂が挙げられる。また、特開２０１２－２５５１２８号公報の段落番号００７２～００９４に記載の樹脂が挙げられ、この内容は本明細書に組み込まれる。
Figure JPOXMLDOC01-appb-C000021
 With respect to the graft copolymer, 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.
Figure JPOXMLDOC01-appb-C000021
　本発明において、樹脂（分散剤）は、主鎖及び側鎖の少なくとも一方に塩基性窒素原子を含むオリゴイミン系分散剤も好ましい。オリゴイミン系分散剤としては、ｐＫａ（ｐｏｗｅｒ　ｏｆ　Ｋａ；Ｋａは酸解離定数）１４以下の官能基を有する部分構造Ｘを有する繰り返し単位と、原子数４０～１０，０００のオリゴマー鎖又はポリマー鎖Ｙを含む側鎖とを有し、かつ主鎖及び側鎖の少なくとも一方に塩基性窒素原子を有する樹脂が好ましい。この樹脂は、窒素原子と、構造Ｘが有するｐＫａ１４以下の官能基との双方で、顔料（例えば、酸化チタンなどの無機粒子）と相互作用し、さらに樹脂が原子数４０～１０，０００のオリゴマー鎖又はポリマー鎖Ｙを有するために、例えば、オリゴマー鎖又はポリマー鎖Ｙが立体反発基として機能することにより、良好な分散性を発揮して、酸化チタンなどの無機粒子を均一に分散することができる。また、オリゴマー鎖又はポリマー鎖Ｙと溶剤とが相互作用を行うことにより、酸化チタンなどの無機粒子の沈降を長期間抑制することができる。さらに、オリゴマー鎖又はポリマー鎖Ｙが立体反発基として機能することで顔料（例えば、酸化チタンなどの無機粒子）の凝集が防止されるため、顔料（好ましくは、酸化チタンなどの無機粒子）の含有量を高くしても、優れた分散性が得られる。 In the present invention, 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. Examples of 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. In order to have the chain or polymer chain Y, for example, 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. Moreover, 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. Furthermore, since 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.
　ここで、「塩基性窒素原子」とは、塩基性を呈する窒素原子であれば特に制限はなく、樹脂がｐＫｂ（ｐｏｗｅｒ　ｏｆ　Ｋｂ；Ｋｂは塩基解離定数）１４以下の窒素原子を有する構造を含有することが好ましく、ｐＫｂ１０以下の窒素原子を有する構造を含有することがより好ましい。本発明において「ｐＫｂ（塩基強度）」とは、水温２５℃でのｐＫｂをいい、塩基の強さを定量的に表すための指標のひとつであり、塩基性度定数と同義である。塩基強度ｐＫｂと、酸強度ｐＫａとは、ｐＫｂ＝１４－ｐＫａの関係にある。 Here, 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. In the present invention, “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 base strength pKb and the acid strength pKa are in a relationship of pKb = 14−pKa.
　部分構造Ｘが有するｐＫａ１４以下の官能基は、特に限定はなく、物性がこの条件を満たすものであれば、その構造などは特に限定されない。特にｐＫａが１２以下の官能基が好ましく、ｐＫａが１１以下の官能基が最も好ましい。具体的には、例えば、カルボキシ基（ｐＫａ　３～５程度）、スルホ基（ｐＫａ　－３～－２程度）、－ＣＯＣＨ2ＣＯ－基（ｐＫａ　８～１０程度）、－ＣＯＣＨ2ＣＮ基（ｐＫａ　８～１１程度）、－ＣＯＮＨＣＯ－基、フェノール性水酸基、－ＲFＣＨ2ＯＨ基又は－（ＲF）2ＣＨＯＨ基（ＲFはペルフルオロアルキル基を表す。ｐＫａ　９～１１程度）、スルホンアミド基（ｐＫａ　９～１１程度）等が挙げられる。ｐＫａ１４以下の官能基を有する部分構造Ｘは、窒素原子を含有する繰り返し単位における塩基性窒素原子に直接結合することが好ましく、塩基性窒素原子を含有する繰り返し単位の塩基性窒素原子と部分構造Ｘとは、共有結合のみならず、イオン結合して塩を形成する態様で連結していてもよい。 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. In particular, 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. Specifically, for example, 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.
　オリゴイミン系分散剤は、ｐＫａ１４以下の官能基を有する部分構造Ｘが結合する塩基性窒素原子を含有する繰り返し単位と、側鎖に原子数４０～１０，０００のオリゴマー鎖又はポリマー鎖Ｙとを有する樹脂であることが好ましい。
　また、オリゴイミン系分散剤は、（ｉ）ポリ（低級アルキレンイミン）系繰り返し単位、ポリアリルアミン系繰り返し単位、ポリジアリルアミン系繰り返し単位、メタキシレンジアミン－エピクロルヒドリン重縮合物系繰り返し単位、及びポリビニルアミン系繰り返し単位から選択される少なくとも１種類の、塩基性窒素原子を含有する繰り返し単位であって、塩基性窒素原子に結合し、かつ、ｐＫａ１４以下の官能基を有する部分構造Ｘを有する繰り返し単位と、側鎖に（ｉｉ）原子数４０～１０，０００のオリゴマー鎖又はポリマー鎖Ｙとを有する樹脂が好ましい。なお、本発明において、ポリ（低級アルキレンイミン）における「低級」とは炭素数が１～５であることを示し、「低級アルキレンイミン」とは炭素数１～５のアルキレンイミンを表す。 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 repeating unit containing at least one basic nitrogen atom selected from the units, the repeating unit having a partial structure X bonded to the basic nitrogen atom and having a functional group of pKa14 or less; A resin having (ii) an oligomer chain having 40 to 10,000 atoms or a polymer chain Y in the chain is preferred. In the present invention, “lower” in poly (lower alkyleneimine) means 1 to 5 carbon atoms, and “lower alkyleneimine” means alkyleneimine having 1 to 5 carbon atoms.
　原子数４０～１０，０００のオリゴマー鎖又はポリマー鎖Ｙとしては、樹脂の主鎖部と連結できるポリエステル、ポリアミド、ポリイミド、ポリ（メタ）アクリル酸エステル等の公知のポリマー鎖が挙げられる。オリゴマー鎖又はポリマー鎖Ｙの樹脂との結合部位は、オリゴマー鎖又はポリマー鎖Ｙの末端であることが好ましい。 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.
　オリゴマー鎖又はポリマー鎖Ｙは、ポリ（低級アルキレンイミン）系繰り返し単位、ポリアリルアミン系繰り返し単位、ポリジアリルアミン系繰り返し単位、メタキシレンジアミン－エピクロルヒドリン重縮合物系繰り返し単位、及びポリビニルアミン系繰り返し単位から選択される少なくとも１種類の窒素原子を含有する繰り返し単位の窒素原子と結合していることが好ましい。ポリ（低級アルキレンイミン）系繰り返し単位、ポリアリルアミン系繰り返し単位、ポリジアリルアミン系繰り返し単位、メタキシレンジアミン－エピクロルヒドリン重縮合物系繰り返し単位、及びポリビニルアミン系繰り返し単位から選択される少なくとも１種類の窒素原子を含有する繰り返し単位などの主鎖部とＹとの結合様式は、共有結合、イオン結合、又は、共有結合及びイオン結合の混合である。Ｙと主鎖部の結合様式の比率は、共有結合：イオン結合＝１００：０～０：１００であり、９５：５～５：９５が好ましい。Ｙは、窒素原子を含有する繰り返し単位の窒素原子とアミド結合、又はカルボン酸塩としてイオン結合していることが好ましい。 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. The ratio of the bonding mode between Y and the main chain is covalent bond: ionic bond = 100: 0 to 0: 100, preferably 95: 5 to 5:95. Y is preferably ion-bonded to a nitrogen atom of a repeating unit containing a nitrogen atom as an amide bond or carboxylate.
　オリゴマー鎖又はポリマー鎖Ｙの原子数としては、分散性、分散安定性および現像性の観点から、５０～５，０００が好ましく、６０～３，０００がより好ましい。また、Ｙの数平均分子量はＧＰＣ法でのポリスチレン換算値により測定することができる。Ｙの数平均分子量は、１，０００～５０，０００が好ましく、１，０００～３０，０００がより好ましい。 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.
　オリゴイミン系分散剤は、例えば、式（Ｉ－１）で表される繰り返し単位と、式（Ｉ－２）で表される繰り返し単位および式（Ｉ－２ａ）で表される繰り返し単位の少なくとも一方とを含む樹脂などが挙げられる。 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.
Figure JPOXMLDOC01-appb-C000022
　Ｒ1及びＲ2は、各々独立に、水素原子、ハロゲン原子又はアルキル基（炭素数１～６が好ましい）を表す。
　ａは、各々独立に、１～５の整数を表す。＊は繰り返し単位間の連結部を表す。
　Ｒ8及びＲ9はＲ1と同義の基である。
　Ｌは単結合、アルキレン基（炭素数１～６が好ましい）、アルケニレン基（炭素数２～６が好ましい）、アリーレン基（炭素数６～２４が好ましい）、ヘテロアリーレン基（炭素数１～６が好ましい）、イミノ基（炭素数０～６が好ましい）、エーテル基、チオエーテル基、カルボニル基、またはこれらの組合せに係る連結基である。なかでも、単結合もしくは－ＣＲ5Ｒ6－ＮＲ7－（イミノ基がＸもしくはＹの方になる）であることが好ましい。ここで、Ｒ5、Ｒ6は各々独立に、水素原子、ハロゲン原子、アルキル基（炭素数１～６が好ましい）を表す。Ｒ7は水素原子または炭素数１～６のアルキル基である。
　ＬaはＣＲ8ＣＲ9とＮとともに環構造形成する構造部位であり、ＣＲ8ＣＲ9の炭素原子と合わせて炭素数３～７の非芳香族複素環を形成する構造部位であることが好ましい。より好ましくは、ＣＲ8ＣＲ9の炭素原子及びＮ（窒素原子）を合わせて５～７員の非芳香族複素環を形成する構造部位であり、さらに好ましくは５員の非芳香族複素環を形成する構造部位であり、ピロリジンを形成する構造部位であることが特に好ましい。この構造部位はさらにアルキル基等の置換基を有していてもよい。ＸはｐＫａ１４以下の官能基を有する基を表す。Ｙは原子数４０～１０，０００のオリゴマー鎖又はポリマー鎖を表す。
Figure JPOXMLDOC01-appb-C000022
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). Are preferred), an imino group (preferably having a carbon number of 0 to 6), an ether group, a thioether group, a carbonyl group, or a combination group thereof. Among these, a single bond or —CR 5 R 6 —NR 7 — (imino group is X or Y) is preferable. Here, 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.
　上記分散剤（オリゴイミン系分散剤）は、さらに式（Ｉ－３）、式（Ｉ－４）、および、式（Ｉ－５）で表される繰り返し単位から選ばれる１種類以上を共重合成分として含有していてもよい。上記分散剤が、このような繰り返し単位を含むことで、粒子の分散性を更に向上させることができる。
Figure JPOXMLDOC01-appb-C000023
 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.
Figure JPOXMLDOC01-appb-C000023
　Ｒ1、Ｒ2、Ｒ8、Ｒ9、Ｌ、Ｌａ、ａ及び＊は式（Ｉ－１）、（Ｉ－２）、（Ｉ－２ａ）における規定と同義である。Ｙａはアニオン基を有する原子数４０～１０，０００のオリゴマー鎖又はポリマー鎖を表す。 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.
　オリゴイミン系分散剤については、特開２０１５－３４９６１号公報の段落番号０１１８～０１９０の記載を参酌でき、本明細書には上記内容が組み込まれる。オリゴイミン系分散剤の具体例としては、例えば、下記の樹脂や、特開２０１５－３４９６１号公報の段落番号０１６９～０１９０に記載の樹脂を用いることができる。
Figure JPOXMLDOC01-appb-C000024
 Regarding the 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. As specific examples of 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.
Figure JPOXMLDOC01-appb-C000024
　本発明では、ポリシロキサン系樹脂である分散剤を用いることが、組成物に含まれるすべての樹脂の波長５８９ｎｍの光に対する質量平均の屈折率を１．５以下にする観点から好ましい。ポリシロキサン系樹脂である分散剤が有する吸着部位としては特に制限はなく、例えば酸基を吸着部位として有することが好ましい。
　ポリシロキサン系樹脂である分散剤は、酸基を有する繰り返し単位と、シロキサン結合を有する繰り返し単位とを少なくとも含むことが好ましい。酸基を有する繰り返し単位としては、（メタ）アクリル酸由来の繰り返し単位などを挙げることができる。
　ポリシロキサン系樹脂である分散剤として、波長５８９ｎｍの光に対する屈折率が１．５以下である樹脂を用いてもよい。ポリシロキサン系樹脂である分散剤の好ましい態様は、波長５８９ｎｍの光に対する屈折率が１．５以下である樹脂の好ましい態様と同様である。 In the present invention, it is preferable to use a dispersant, which is a polysiloxane resin, from the viewpoint of setting the mass average refractive index of all resins contained in the composition to light having a wavelength of 589 nm to 1.5 or less. There is no restriction | limiting in particular as an adsorption site which the dispersing agent which is a polysiloxane resin has, for example, it is preferable to have an acid group as an adsorption site.
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.
As 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.
　分散剤は、市販品としても入手可能であり、そのような具体例としては、ＢＹＫ　Ｃｈｅｍｉｅ（株）製「Ｄｉｓｐｅｒｂｙｋ－１０１（ポリアミドアミン燐酸塩）、１０７（カルボン酸エステル）、１１０、１８０（酸基を含む共重合物）、１３０（ポリアミド）、１６１、１６２、１６３、１６４、１６５、１６６、１７０（高分子共重合物）」、ＢＹＫ　Ｃｈｅｍｉｅ（株）製「ＢＹＫ－Ｐ１０４、Ｐ１０５（高分子量不飽和ポリカルボン酸）」、ＥＦＫＡ（株）製「ＥＦＫＡ４０４７、４０５０、４０１０、４１６５（ポリウレタン系）、ＥＦＫＡ４３３０、４３４０（ブロック共重合体）、４４００、４４０２（変性ポリアクリレート）、５０１０（ポリエステルアミド）、５７６５（高分子量ポリカルボン酸塩）、６２２０（脂肪酸ポリエステル）、６７４５（フタロシアニン誘導体）、６７５０（アゾ顔料誘導体）」、味の素ファインテクノ（株）製「アジスパーＰＢ８２１、ＰＢ８２２」、共栄社化学（株）製「フローレンＴＧ－７１０（ウレタンオリゴマー）」、共栄社化学（株）製「ポリフローＮｏ．５０Ｅ、Ｎｏ．３００（アクリル系共重合体）」、楠本化成（株）製「ディスパロンＫＳ－８６０、８７３ＳＮ、８７４、＃２１５０（脂肪族多価カルボン酸）、＃７００４（ポリエーテルエステル）、ＤＡ－７０３－５０、ＤＡ－７０５、ＤＡ－７２５」、花王（株）製「デモールＲＮ、Ｎ（ナフタレンスルホン酸ホルマリン重縮合物）、ＭＳ、Ｃ、ＳＮ－Ｂ（芳香族スルホン酸ホルマリン重縮合物）」、花王（株）製「ホモゲノールＬ－１８（高分子ポリカルボン酸）」、花王（株）製「エマルゲン９２０、９３０、９３５、９８５（ポリオキシエチレンノニルフェニルエーテル）」、「アセタミン８６（ステアリルアミンアセテート）」、Ｌｕｂｒｉｚｏｌ（株）製「ソルスパース５０００（Ｓｏｌｓｐｅｒｓｅ　５０００）（フタロシアニン誘導体）、２２０００（アゾ顔料誘導体）、１３２４０（ポリエステルアミン）、３０００、１７０００、２７０００（末端部に機能部を有する高分子）、２４０００、２６０００、２８０００、３２０００、３６０００、３８５００（グラフト型高分子）、４１０００、４６０００」、日光ケミカルズ（株）製「ニッコールＴ１０６（ポリオキシエチレンソルビタンモノオレート）、ＭＹＳ－ＩＥＸ（ポリオキシエチレンモノステアレート）」等が挙げられる。
　また、酸系吸着部位としてリン原子含有基（例えば、リン酸基等）を有する分散剤の市販品として、Ｌｕｂｒｉｚｏｌ（株）製「ソルスパース２６０００（Ｓｏｌｓｐｅｒｓｅ　２６０００）、３６０００、４１０００」が挙げられる。これらを好適に用いることができる。
　ポリシロキサン系樹脂である分散剤としては、例えば、アクリルポリマーとジメチルポリシロキサンを含むグラフト共重合体であるＫＰ－５７８、ポリシロキサン樹脂系分散剤であるＸ－２２－３７０１Ｅ（いずれも信越化学工業（株）製）などが挙げられる。
　分散剤は、１種類単独で、あるいは２種類以上を組み合わせて用いることができる。
　分散剤は、上述したその他のバインダーで説明した樹脂を用いることもできる。また、分散剤は、波長５８９ｎｍの光に対する屈折率が１．５以下である樹脂を用いてもよい。 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. Group-containing copolymer), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) ", BYK Chemie Co., Ltd." BYK-P104, P105 (high molecular weight) Unsaturated polycarboxylic acid) ”,“ EFKA 4047, 4050, 4010, 4165 (polyurethane type), EFKA 4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide) manufactured by EFKA Corporation , 5765 (high molecular weight polycarboxylate), 6220 (fat Polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) ", Ajinomoto Fine Techno Co., Ltd." Azisper PB821, PB822 ", Kyoeisha Chemical Co., Ltd." Floren TG-710 (urethane oligomer) ", Kyoeisha Chemical Co., Ltd. "Polyflow No. 50E, No. 300 (acrylic copolymer)" manufactured by Co., Ltd., "Disparon KS-860, 873SN, 874, # 2150 (aliphatic polyvalent carboxylic acid)" manufactured by Enomoto Kasei Co., Ltd., # 7004 (polyetherester), DA-703-50, DA-705, DA-725 "," Demol RN, N (naphthalenesulfonic acid formalin polycondensate), Kao Corporation, MS, C, SN-B ( Aromatic sulfonic acid formalin polycondensate) ”,“ Homogenol L-18 (polymer polycal) manufactured by Kao Corporation “Boonic acid” ”,“ Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) ”manufactured by Kao Corporation,“ Acetamine 86 (stearylamine acetate) ”,“ Solsperse 5000 ”manufactured by Lubrizol Co., Ltd. ) (Phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 26000, 28000, 32000, 36000, 38500 (graft type) Polymer), 41000, 46000 ”,“ Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) ”manufactured by Nikko Chemicals Co., Ltd. It is.
Moreover, as a commercial item of 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" is mentioned. These can be used suitably.
Examples of 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.).
One type of dispersant can be used alone, or two or more types can be used in combination.
As the dispersant, the resins described in the above-described other binders can also be used. Further, as the dispersant, a resin having a refractive index of 1.5 or less with respect to light having a wavelength of 589 nm may be used.
　本発明の組成物は、分散助剤として、酸基と架橋性基を有する分散助剤を含有していてもよい。好ましい酸基としてはスルホン酸基、リン酸基、ホスホン酸基およびカルボン酸基が挙げられ、リン酸基がより好ましい。架橋性基としては、エチレン性不飽和結合を有する基、エポキシ基およびメルカプト基等が挙げられ、エチレン性不飽和結合を有する基がより好ましい。エチレン性不飽和結合を有する基としては、重合性化合物の説明で挙げる付加重合可能なエチレン基も含まれる。
　分散助剤の市販品としては、ライトエステルＰ－１Ｍ、ライトエステルＰ－２Ｍ、ライトエステルＨＯ－ＭＳ、ライトエステルＨＯ－ＨＨ（以上、共栄社化学（株）製）ホスマーＭ、ホスマーＰＥ、ホスマーＭＨ、ホスマーＣＬ、ホスマーＰＰ（以上、ユニケミカル（株）製）、ＴＢＡＳ－Ｑ、ＴＢＡＳ－Ｒ（以上、ＭＲＣユニテック（株）製）などが挙げられる。 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. Examples of 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. Examples of the group having an ethylenically unsaturated bond include addition-polymerizable ethylene groups mentioned in the description of the polymerizable compound.
Commercially available 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.
　分散剤の含有量は、組成物の全固形分に対して、１～８０質量％であることがＬ＊、パターン形状および密着性の観点から好ましい。上限は、７０質量％以下が好ましく、６０質量％以下がより好ましく、２５質量％以下が特に好ましく、２２質量％以下が最も好ましい。下限は、１．５質量％以上が好ましく、２質量％以上がより好ましく、１８質量％以上が特に好ましい。
　また、分散剤の含有量は、顔料１００質量部に対して、１～１００質量部が好ましい。上限は、８０質量部以下が好ましく、６０質量部以下がさらに好ましい。下限は、２．５質量部以上が好ましく、５質量部以上がさらに好ましい。
　また、分散剤の含有量は、無機顔料１００質量部に対して、１～１００質量部が好ましい。上限は、８０質量部以下が好ましく、６０質量部以下がさらに好ましい。下限は、２．５質量部以上が好ましく、５質量部以上がさらに好ましい。
　また、分散剤の含有量は、酸化チタン１００質量部に対して、１～１００質量部が好ましい。上限は、８０質量部以下が好ましく、６０質量部以下がさらに好ましい。下限は、２．５質量部以上が好ましく、５質量部以上がさらに好ましい。 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.
＜＜溶剤＞＞
　本発明の組成物は溶剤を含有することが好ましい。溶剤は種々の有機溶剤を用いて構成することができる。有機溶剤としては、アセトン、メチルエチルケトン、シクロヘキサン、酢酸エチル、エチレンジクロライド、テトラヒドロフラン、トルエン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールジメチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、アセチルアセトン、シクロヘキサノン、ジアセトンアルコール、エチレングリコールモノメチルエーテルアセテート、エチレングリコールエチルエーテルアセテート、エチレングリコールモノイソプロピルエーテル、エチレングリコールモノブチルエーテルアセテート、３－メトキシプロパノール、メトキシメトキシエタノール、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、３－メトキシプロピルアセテート、Ｎ，Ｎ－ジメチルホルムアミド、ジメチルスルホキシド、γ－ブチロラクトン、乳酸メチル、乳酸エチルなどが挙げられる。これらの有機溶剤は、単独あるいは混合して使用することができる。 << Solvent >>
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 glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, methyl lactate, ethyl lactate Etc. These organic solvents can be used alone or in combination.
　本発明において、溶剤は、金属含有量が少ない溶剤を用いることが好ましい。溶剤の金属含有量は、例えば、１０質量ｐｐｂ以下であることが好ましい。必要に応じて質量ｐｐｔレベルのものを用いてもよく、そのような高純度溶剤は、例えば、東洋合成社が提供している（化学工業日報、２０１５年１１月１３日）。
　溶剤から金属等の不純物を除去する方法としては、例えば、蒸留（分子蒸留や薄膜蒸留等）やフィルタを用いた濾過を挙げることができる。濾過に用いるフィルタのフィルタ孔径としては、ポアサイズ１０ｎｍ以下が好ましく、５ｎｍ以下がより好ましく、３ｎｍ以下が更に好ましい。フィルタとしては、ポリテトラフロロエチレン製、ポリエチレン製、または、ナイロン製のフィルタが好ましい。
　溶剤には、異性体（同じ原子数で異なる構造の化合物）が含まれていてもよい。また、異性体は、１種類のみが含まれていてもよいし、複数種類含まれていてもよい。 In the present invention, it is preferable to use a solvent having a low metal content 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. As 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.
　溶剤の含有量は、組成物の固形分濃度が２５～７０質量％となる量が好ましく、組成物の固形分濃度が３０～６０質量％となる量がより好ましい。 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.
＜＜硬化性化合物＞＞
　本発明の組成物は、硬化性化合物を含有することが好ましい。
　硬化性化合物は、ラジカル、酸、熱により架橋（重合および縮合を含む）可能な化合物である。本発明で用いる硬化性化合物は、例えば、エチレン性不飽和結合を有する基を有する化合物、エポキシ基を有する化合物、メチロール基を有する化合物などが挙げられ、エチレン性不飽和結合を有する基を有する化合物が好ましい。エチレン性不飽和結合を有する基としては、ビニル基、（メタ）アリル基、（メタ）アクリロイル基などが挙げられる。
　本発明において、硬化性化合物は、ラジカル重合性化合物が好ましい。ラジカル重合性化合物としては、エチレン性不飽和結合を有する基を有する化合物などが挙げられる。本発明の組成物は硬化性化合物として、後述のエポキシ基を有する化合物を有していてもよい。以下において、特に断りが無く重合性化合物という場合は、ラジカル重合性化合物のことを言う。 << Curable compound >>
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.
In the present invention, the curable compound is preferably a radical polymerizable compound. Examples of 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 | hardenable compound. Below, when there is no notice in particular and it is called a polymerizable compound, it means a radically polymerizable compound.
　硬化性化合物の含有量は、組成物の全固形分に対して、１～７０質量％が好ましい。下限は、３質量％以上が好ましく、５質量％以上がより好ましく、９質量％以上が特に好ましい。上限は、６０質量％以下が好ましく、５０質量％以下がより好ましく、１２質量％以下が特に好ましい。これらの範囲であるとパターン形状、耐熱性、Ｌ＊の観点から好ましい。組成物に用いられる硬化性化合物は、１種類のみでもよく、２種類以上でもよい。２種類以上の場合は、合計量が上記範囲となることが好ましい。 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.
　硬化性化合物として、重合性化合物を用いる場合、重合性化合物の含有量は、組成物の全固形分に対し、１～７０質量％が好ましい。下限は、３質量％以上が好ましく、５質量％以上がより好ましい。上限は、６０質量％以下が好ましく、５０質量％以下がより好ましい。組成物に用いられる重合性化合物は、１種類のみでもよく、２種類以上でもよい。２種類以上の場合は、合計量が上記範囲となることが好ましい。
　また、重合性化合物の含有量は、硬化性化合物の全質量に対して、１０～１００質量％が好ましく、３０～１００質量％がより好ましい。 When a polymerizable compound is used as the curable compound, 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.
（重合性化合物）
　本発明の組成物は、ラジカル重合性化合物の全質量中における、波長５８９ｎｍの光に対する屈折率が１．５５以下（好ましくは１．５２以下、より好ましくは１．５以下）のラジカル重合性化合物の含有量が８０質量％以上であることが好ましく、８５質量％以上であることがより好ましく、９０質量％以上であることが特に好ましい。 (Polymerizable 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.
　重合性化合物としては、少なくとも１個のエチレン性不飽和結合を有する基を有する化合物が好ましく、末端エチレン性不飽和結合を有する基を少なくとも１個（好ましくは２個以上）有する化合物がより好ましい。また、重合性化合物は、エチレン性不飽和結合を有する基を１～８個有する化合物が好ましく、エチレン性不飽和結合を有する基を２～６個有する化合物がより好ましく、エチレン性不飽和結合を有する基を３～４個有する化合物がさらに好ましい。重合性化合物は、エチレン性不飽和結合を有する基を上記範囲で有し、かつ、分子内にＳｉ原子を有する重合性化合物であることが特に好ましい。
　エチレン性不飽和結合を有する基は、（メタ）アクリロイル基、（メタ）アクリロイルオキシ基が好ましい。また、重合性化合物は、ラジカル重合性化合物であることが好ましい。 As the polymerizable compound, 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.
　重合性化合物は、モノマー、ポリマーのいずれの形態であってもよく、モノマーが好ましい。モノマータイプの重合性化合物は、分子量が１００～３０００であることが好ましい。上限は、２０００以下が好ましく、１５００以下が更に好ましい。下限は、１５０以上が好ましく、２５０以上が更に好ましい。 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.
　重合性化合物は、１～８官能の（メタ）アクリレート化合物であることが好ましく、２～６官能の（メタ）アクリレート化合物であることがより好ましく、３～４官能の（メタ）アクリレート化合物であることがさらに好ましい。この態様によれば、得られる膜の耐溶剤性や、基材と密着性を向上できる。また、重合性化合物は、６官能以上の（メタ）アクリレート化合物であることも好ましい。 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.
　重合性化合物は、少なくとも１個の付加重合可能なエチレン基を有する、常圧下で１００℃以上の沸点を持つエチレン性不飽和結合を有する基を持つ化合物も好ましい。その例としては、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート、フェノキシエチル（メタ）アクリレート等の単官能のアクリレートやメタアクリレート；ポリエチレングリコールジ（メタ）アクリレート、トリメチロールエタントリ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ヘキサンジオール（メタ）アクリレート、トリメチロールプロパントリ（アクリロイルオキシプロピル）エーテル、トリ（アクリロイルオキシエチル）イソシアヌレート及びこれらの混合物を挙げることができ、ペンタエリスリトールテトラ（メタ）アクリレートであることが好ましい。 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. Examples include 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 ( (Meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) iso Cyanurate and can mixtures thereof, is preferably pentaerythritol tetra (meth) acrylate.
　重合性化合物は、下記式（ＭＯ－１）～（ＭＯ－５）で表される、重合性化合物も好適に用いることができる。なお、式中、Ｔがオキシアルキレン基の場合には、炭素原子側の末端がＲに結合する。 As the polymerizable compound, polymerizable compounds represented by the following formulas (MO-1) to (MO-5) can also be suitably used. In the formula, when T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R.
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
　上記の式において、ｎは０～１４の整数であり、ｍは１～８の整数である。同一分子内に複数存在するＲ、Ｔ、は、各々同一であっても、異なっていてもよい。
　上記式（ＭＯ－１）～（ＭＯ－５）で表される重合性化合物の各々において、複数のＲの内の少なくとも１つは、－ＯＣ（＝Ｏ）ＣＨ＝ＣＨ2、又は、－ＯＣ（＝Ｏ）Ｃ（ＣＨ3）＝ＣＨ2で表される基を表す。
　上記式（ＭＯ－１）～（ＭＯ－５）で表される、重合性化合物の具体例としては、特開２００７－２６９７７９号公報の段落０２４８～０２５１に記載されている化合物が挙げられる。
　また、特開平１０－６２９８６号公報に記載の、多官能アルコールにエチレンオキサイドやプロピレンオキサイドを付加させた後に（メタ）アクリレート化した化合物も、重合性化合物として用いることができる。 In the above formula, 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.
In each of the polymerizable compounds represented by the above formulas (MO-1) to (MO-5), 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.
Further, 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.
　重合性化合物は、ペンタエリスリトールテトラアクリレート（市販品としては、ＮＫエステル　Ａ－ＴＭＭＴ；新中村化学工業（株）製）、ジペンタエリスリトールトリアクリレート（市販品としては　ＫＡＹＡＲＡＤ　Ｄ－３３０；日本化薬（株）製）、ジペンタエリスリトールテトラアクリレート（市販品としては　ＫＡＹＡＲＡＤ　Ｄ－３２０；日本化薬（株）製）ジペンタエリスリトールペンタ（メタ）アクリレート（市販品としては
　ＫＡＹＡＲＡＤ　Ｄ－３１０；日本化薬（株）製）、ジペンタエリスリトールヘキサ（メタ）アクリレート（市販品としては　ＫＡＹＡＲＡＤ　ＤＰＨＡ；日本化薬（株）製）が好ましく、ペンタエリスリトールテトラアクリレートがパターン形状の観点からより好ましい。 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.
　重合性化合物は、カルボキシ基、スルホ基、リン酸基等の酸基を有していてもよい。酸基を有する重合性化合物は、多官能アルコールの一部のヒドロキシ基を（メタ）アクリレート化し、残ったヒドロキシ基に酸無水物を付加反応させてカルボキシ基とするなどの方法で得られる。酸基を有する重合性化合物としては、脂肪族ポリヒドロキシ化合物と不飽和カルボン酸とのエステルなどが挙げられる。酸基を有する重合性化合物は、脂肪族ポリヒドロキシ化合物の未反応のヒドロキシ基に、非芳香族カルボン酸無水物を反応させて酸基を持たせた化合物が好ましく、特に好ましくは、このエステルにおいて、脂肪族ポリヒドロキシ化合物がペンタエリスリトールおよびジペンタエリスリトールのうち少なくとも一方であるものである。市販品としては、例えば、東亞合成（株）製の多塩基酸変性アクリルオリゴマーとして、アロニックスシリーズのＭ－３０５、Ｍ－５１０、Ｍ－５２０などが挙げられる。酸基を有する重合性化合物の酸価は、０．１～４０ｍｇＫＯＨ／ｇが好ましい。下限は５ｍｇＫＯＨ／ｇ以上が好ましい。上限は、３０ｍｇＫＯＨ／ｇ以下が好ましい。 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.
　また、重合性化合物は、カプロラクトン構造を有する重合性化合物も好ましい態様である。カプロラクトン構造を有する重合性化合物としては、分子内にカプロラクトン構造を有する限り特に限定されず、例えば、トリメチロールエタン、ジトリメチロールエタン、トリメチロールプロパン、ジトリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、トリペンタエリスリトール、グリセリン、ジグリセロール、トリメチロールメラミン等の多価アルコールと、（メタ）アクリル酸及びε－カプロラクトンをエステル化することにより得られる、ε－カプロラクトン変性多官能（メタ）アクリレートを挙げることができる。カプロラクトン構造を有する重合性化合物は、下記式（Ｚ－１）で表される化合物が好ましい。 Also, 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. For example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tripenta Mention may be made of ε-caprolactone-modified polyfunctional (meth) acrylates obtained by esterifying polyhydric alcohols such as erythritol, glycerin, diglycerol, trimethylolmelamine, (meth) acrylic acid and ε-caprolactone. . The polymerizable compound having a caprolactone structure is preferably a compound represented by the following formula (Z-1).
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
　式（Ｚ－１）中、６個のＲは全てが式（Ｚ－２）で表される基であるか、又は６個のＲのうち１～５個が式（Ｚ－２）で表される基であり、残余が式（Ｚ－３）で表される基である。 In the formula (Z-1), all six Rs are groups represented by the formula (Z-2), or 1 to 5 of the six Rs are represented by the formula (Z-2). And the remainder is a group represented by the formula (Z-3).
Figure JPOXMLDOC01-appb-C000027
　式（Ｚ－２）中、Ｒ1は水素原子又はメチル基を示し、ｍは１又は２の数を示し、「＊」は結合手であることを示す。
Figure JPOXMLDOC01-appb-C000027
In formula (Z-2), R 1 represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and “*” represents a bond.
Figure JPOXMLDOC01-appb-C000028
　式（Ｚ－３）中、Ｒ1は水素原子又はメチル基を示し、「＊」は結合手であることを示す。
Figure JPOXMLDOC01-appb-C000028
In formula (Z-3), R 1 represents a hydrogen atom or a methyl group, and “*” represents a bond.
　カプロラクトン構造を有する重合性化合物は、例えば、日本化薬（株）からＫＡＹＡＲＡＤ　ＤＰＣＡシリーズとして市販されており、ＤＰＣＡ－２０（上記式（Ｚ－１）～（Ｚ－３）においてｍ＝１、式（Ｚ－２）で表される基の数＝２、Ｒ1が全て水素原子である化合物）、ＤＰＣＡ－３０（同式、ｍ＝１、式（Ｚ－２）で表される基の数＝３、Ｒ1が全て水素原子である化合物）、ＤＰＣＡ－６０（同式、ｍ＝１、式（Ｚ－２）で表される基の数＝６、Ｒ1が全て水素原子である化合物）、ＤＰＣＡ－１２０（同式においてｍ＝２、式（Ｚ－２）で表される基の数＝６、Ｒ1が全て水素原子である化合物）等が挙げられる。 Polymerizable compounds having a caprolactone structure are commercially available from, for example, Nippon Kayaku Co., Ltd. as KAYARAD DPCA series, and DPCA-20 (m = 1 in the above formulas (Z-1) to (Z-3), Number of groups represented by (Z-2) = 2, a compound in which R 1 is all hydrogen atoms), DPCA-30 (formula, m = 1, number of groups represented by formula (Z-2)) = 3, a compound in which R 1 is all hydrogen atoms), DPCA-60 (same formula, m = 1, number of groups represented by formula (Z-2) = 6, a compound in which R 1 is all hydrogen atoms) ), DPCA-120 (a compound in which m = 2 in the formula, the number of groups represented by formula (Z-2) = 6, and all R 1 are hydrogen atoms).
　重合性化合物は、式（Ｚ－４）又は（Ｚ－５）で表される化合物を用いることもできる。 As the polymerizable compound, a compound represented by the formula (Z-4) or (Z-5) can also be used.
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
　式（Ｚ－４）及び（Ｚ－５）中、Ｅは、各々独立に、－（（ＣＨ2）yＣＨ2Ｏ）－、又は－（（ＣＨ2）yＣＨ（ＣＨ3）Ｏ）－を表し、ｙは、各々独立に０～１０の整数を表し、Ｘは、各々独立に、（メタ）アクリロイル基、水素原子、又はカルボキシ基を表す。
　式（Ｚ－４）中、（メタ）アクリロイル基の合計は３個又は４個であり、ｍは各々独立に０～１０の整数を表し、各ｍの合計は０～４０の整数である。
　式（Ｚ－５）中、（メタ）アクリロイル基の合計は５個又は６個であり、ｎは各々独立に０～１０の整数を表し、各ｎの合計は０～６０の整数である。 In formulas (Z-4) and (Z-5), each E independently represents — ((CH 2 ) y CH 2 O) — or — ((CH 2 ) y CH (CH 3 ) O) —. Each represents independently an integer of 0 to 10, and each X independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxy group.
In the formula (Z-4), the total number of (meth) acryloyl groups is 3 or 4, each m independently represents an integer of 0 to 10, and the total of each m is an integer of 0 to 40.
In formula (Z-5), the total number of (meth) acryloyl groups is 5 or 6, each n independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60.
　式（Ｚ－４）中、ｍは、０～６の整数が好ましく、０～４の整数がより好ましい。
　また、各ｍの合計は、２～４０の整数が好ましく、２～１６の整数がより好ましく、４～８の整数が特に好ましい。
　式（Ｚ－５）中、ｎは、０～６の整数が好ましく、０～４の整数がより好ましい。
　また、各ｎの合計は、３～６０の整数が好ましく、３～２４の整数がより好ましく、６～１２の整数が特に好ましい。
　また、式（Ｚ－４）又は式（Ｚ－５）中の－（（ＣＨ2）yＣＨ2Ｏ）－又は－（（ＣＨ2）yＣＨ（ＣＨ3）Ｏ）－は、酸素原子側の末端がＸに結合する形態が好ましい。 In the formula (Z-4), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
The total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8.
In the formula (Z-5), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
The total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.
In formula (Z-4) or formula (Z-5), — ((CH 2 ) y CH 2 O) — or — ((CH 2 ) y CH (CH 3 ) O) — represents the oxygen atom side. A form in which the terminal of X is bonded to X is preferred.
　式（Ｚ－４）又は式（Ｚ－５）で表される化合物は１種類単独で用いてもよいし、２種類以上併用してもよい。特に、式（Ｚ－５）において、６個のＸ全てがアクリロイル基である形態が好ましい。 The compounds represented by formula (Z-4) or formula (Z-5) may be used alone or in combination of two or more. In particular, in the formula (Z-5), a form in which all six Xs are acryloyl groups is preferable.
　また、式（Ｚ－４）又は式（Ｚ－５）で表される化合物の重合性化合物中における全含有量としては、２０質量％以上が好ましく、５０質量％以上がより好ましい。 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.
　式（Ｚ－４）又は式（Ｚ－５）で表される化合物は、従来公知の工程である、ペンタエリスリト－ル又はジペンタエリスリトールにエチレンオキシド又はプロピレンオキシドを開環付加反応により開環骨格を結合する工程と、開環骨格の末端ヒドロキシ基に、例えば（メタ）アクリロイルクロライドを反応させて（メタ）アクリロイル基を導入する工程と、から合成することができる。各工程は良く知られた工程であり、当業者は容易に式（Ｚ－４）又は式（Ｚ－５）で表される化合物を合成することができる。 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).
　式（Ｚ－４）又は式（Ｚ－５）で表される化合物の中でも、ペンタエリスリトール誘導体およびジペンタエリスリトール誘導体のうち少なくとも一方がより好ましい。
　具体的には、下記式（ａ）～（ｆ）で表される化合物（以下、「例示化合物（ａ）～（ｆ）」とも称する。）が挙げられ、中でも、例示化合物（ａ）、（ｂ）、（ｅ）、（ｆ）が好ましい。 Among the compounds 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)”). Among them, exemplary compounds (a), (f) b), (e) and (f) are preferred.
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
　式（Ｚ－４）、（Ｚ－５）で表される重合性化合物の市販品としては、例えばサートマー（株）製のエチレンオキシ基を４個有する４官能アクリレートであるＳＲ－４９４、日本化薬（株）製のペンチレンオキシ基を６個有する６官能アクリレートであるＤＰＣＡ－６０、イソブチレンオキシ基を３個有する３官能アクリレートであるＴＰＡ－３３０などが挙げられる。 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.
　重合性化合物は、特公昭４８－４１７０８号公報、特開昭５１－３７１９３号公報、特公平２－３２２９３号公報、特公平２－１６７６５号公報に記載されているようなウレタンアクリレート類や、特公昭５８－４９８６０号公報、特公昭５６－１７６５４号公報、特公昭６２－３９４１７号公報、特公昭６２－３９４１８号公報記載のエチレンオキサイド系骨格を有するウレタン化合物類も好適である。また、特開昭６３－２７７６５３号公報、特開昭６３－２６０９０９号公報、特開平１－１０５２３８号公報に記載される、分子内にアミノ構造やスルフィド構造を有する付加重合性化合物類をも好ましい。
　重合性化合物の市販品としては、ウレタンオリゴマーＵＡＳ－１０、ＵＡＢ－１４０（山陽国策パルプ（株）製）、Ｕ－４ＨＡ、Ｕ－６ＬＰＡ、ＵＡ－３２Ｐ、Ｕ－１０ＨＡ、Ｕ－１０ＰＡ、ＵＡ－１２２Ｐ、ＵＡ－１１００Ｈ、ＵＡ－７２００（新中村化学工業（株）製）、ＤＰＨＡ－４０Ｈ（日本化薬（株）製）、ＵＡ－３０６Ｈ、ＵＡ－３０６Ｔ、ＵＡ－３０６Ｉ、ＡＨ－６００、Ｔ－６００、ＡＩ－６００（共栄社化学（株）製）、ＵＡ－９０５０、ＵＡ－９０４８（ＢＡＳＦ（株）製）などが挙げられる。 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. Also preferred are 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. .
Commercially available 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.
　また、重合性化合物は、分子内にＳｉ原子を有する重合性化合物も好ましい態様である。特に本発明では、波長５８９ｎｍの光に対する屈折率が１．５以下のラジカル重合性化合物として分子内にＳｉ原子を有する重合性化合物を用いることが、好ましい。波長５８９ｎｍの光に対する屈折率が１．５以下のラジカル重合性化合物を含む組成物を用いて膜を形成し、硬化して硬化膜とすることで、後述の硬化膜の粒子以外の成分の波長５８９ｎｍの光に対する屈折率を１．５以下にしやすい。
　分子内にＳｉ原子を有する重合性化合物の市販品としては、シロキサン結合含有の多官能アクリレートであるＥＢＥＣＲＹＬ１３６０（ダイセルオルネクス（株）製）、Ｓｉ原子含有多官能ビニル化合物であるＶＩＮＹＬＴＲＩＩＳＯＰＲＯＰＥＮＯＸＹＳＩＬＡＮＥ（アズマックス株式会社製）などが挙げられる。 In addition, the polymerizable compound is also preferably a polymerizable compound having a Si atom in the molecule. In particular, in the present invention, it is preferable to use 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. By forming a film using a composition containing a radical polymerizable compound having a refractive index of 1.5 or less with respect to light having a wavelength of 589 nm, and curing it to obtain a cured film, wavelengths of components other than particles of the cured film described later It is easy to make the refractive index for light of 589 nm 1.5 or less.
Commercially available 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).
　これらの重合性化合物について、その構造、単独使用か併用か、添加量等の使用方法の詳細は、組成物の最終的な性能設計にあわせて任意に設定できる。例えば、感度の観点では、１分子あたりのエチレン性不飽和結合を有する基の含有量が多い構造が好ましく、多くの場合は２官能以上が好ましい。また、硬化膜の強度を高める観点では、３官能以上の化合物が好ましく、さらに、官能数および重合性基（例えばアクリル酸エステル、メタクリル酸エステル、スチレン系化合物、ビニルエーテル系化合物）のうち少なくとも一方が異なる化合物を併用することで、感度と強度の両方を調節する方法も有効である。さらに、３官能以上の化合物であって、エチレンオキサイド鎖長の異なる重合性化合物を併用することも好ましい。この態様によれば、組成物の現像性を調節することができ、優れたパターン形成が得られる。また、組成物に含まれる他の成分（例えば、光重合開始剤、樹脂等）との相溶性および分散性のうち少なくとも一方に対しても、重合性化合物の選択および使用方法のうち少なくとも一方は好ましい要因であり、例えば、低純度化合物の使用や２種類以上の併用により、相溶性などを向上することができる。 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. For example, from the viewpoint of sensitivity, 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. Further, from the viewpoint of increasing the strength of the cured film, 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. In addition, 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.
（エポキシ基を有する化合物）
　本発明の組成物は、硬化性化合物としてエポキシ基を有する化合物を用いることもできる。この態様によれば、得られる膜の耐溶剤性を向上できる。エポキシ基を有する化合物としては、単官能または多官能グリシジルエーテル化合物や、多官能脂肪族グリシジルエーテル化合物などが挙げられる。また、グリシジル（メタ）アクリレートやアリルグリシジルエーテル等のエポキシ基をグリシジル基の一部として有する化合物や、脂環式エポキシ基を有する化合物を用いることもできる。 (Compound having an epoxy group)
In the composition of the present invention, a compound having an epoxy group can also be used as the curable compound. According to this aspect, the solvent resistance of the obtained film can be improved. Examples of the compound having an epoxy group include monofunctional or polyfunctional glycidyl ether compounds and polyfunctional aliphatic glycidyl ether compounds. Moreover, 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.
　エポキシ基を有する化合物は、１分子にエポキシ基を１つ以上有する化合物が挙げられる。エポキシ基は、１分子に１～１００個有することが好ましい。上限は、例えば、１０個以下とすることもでき、５個以下とすることもできる。下限は、２個以上が好ましい。 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. For example, the upper limit may be 10 or less, and may be 5 or less. The lower limit is preferably 2 or more.
　エポキシ基を有する化合物は、エポキシ当量（＝エポキシ基を有する化合物の分子量／エポキシ基の数）が５００ｇ／当量以下であることが好ましく、１００～４００ｇ／当量であることがより好ましく、１００～３００ｇ／当量であることがさらに好ましい。 The compound having an epoxy group preferably has an epoxy equivalent (= molecular weight of the compound having an epoxy group / number of epoxy groups) of 500 g / equivalent or less, more preferably 100 to 400 g / equivalent, and 100 to 300 g. / Equivalent is more preferable.
　エポキシ基を有する化合物は、低分子化合物（例えば、分子量１０００未満）でもよいし、高分子化合物（ｍａｃｒｏｍｏｌｅｃｕｌｅ）（例えば、分子量１０００以上、ポリマーの場合は、重量平均分子量が１０００以上）のいずれでもよい。エポキシ基を有する化合物の重量平均分子量は、２００～１０００００が好ましく、５００～５００００がより好ましい。重量平均分子量の上限は、１００００以下が好ましく、５０００以下がより好ましく、３０００以下が更に好ましい。
　エポキシ基を有する化合物は、脂肪族エポキシ樹脂であることが、耐溶剤性の観点から好ましい。 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.
　エポキシ基を有する化合物は、特開２０１３－０１１８６９号公報の段落番号００３４～００３６、特開２０１４－０４３５５６号公報の段落番号０１４７～０１５６、特開２０１４－０８９４０８号公報の段落番号００８５～００９２に記載された化合物を用いることもできる。これらの内容は、本明細書に組み込まれる。市販品としては、例えば、ビスフェノールＡ型エポキシ樹脂としては、ｊＥＲ８２５、ｊＥＲ８２７、ｊＥＲ８２８、ｊＥＲ８３４、ｊＥＲ１００１、ｊＥＲ１００２、ｊＥＲ１００３、ｊＥＲ１０５５、ｊＥＲ１００７、ｊＥＲ１００９、ｊＥＲ１０１０（以上、三菱化学（株）製）、ＥＰＩＣＬＯＮ８６０、ＥＰＩＣＬＯＮ１０５０、ＥＰＩＣＬＯＮ１０５１、ＥＰＩＣＬＯＮ１０５５（以上、ＤＩＣ（株）製）等であり、ビスフェノールＦ型エポキシ樹脂としては、ｊＥＲ８０６、ｊＥＲ８０７、ｊＥＲ４００４、ｊＥＲ４００５、ｊＥＲ４００７、ｊＥＲ４０１０（以上、三菱化学（株）製）、ＥＰＩＣＬＯＮ８３０、ＥＰＩＣＬＯＮ８３５（以上、ＤＩＣ（株）製）、ＬＣＥ－２１、ＲＥ－６０２Ｓ（以上、日本化薬（株）製）等であり、フェノールノボラック型エポキシ樹脂としては、ｊＥＲ１５２、ｊＥＲ１５４、ｊＥＲ１５７Ｓ７０、ｊＥＲ１５７Ｓ６５（以上、三菱化学（株）製）、ＥＰＩＣＬＯＮ　Ｎ－７４０、ＥＰＩＣＬＯＮ　Ｎ－７７０、ＥＰＩＣＬＯＮ　Ｎ－７７５（以上、ＤＩＣ（株）製）等であり、クレゾールノボラック型エポキシ樹脂としては、ＥＰＩＣＬＯＮ　Ｎ－６６０、ＥＰＩＣＬＯＮ　Ｎ－６６５、ＥＰＩＣＬＯＮ　Ｎ－６７０、ＥＰＩＣＬＯＮ　Ｎ－６７３、ＥＰＩＣＬＯＮ　Ｎ－６８０、ＥＰＩＣＬＯＮ　Ｎ－６９０、ＥＰＩＣＬＯＮ　Ｎ－６９５（以上、ＤＩＣ（株）製）、ＥＯＣＮ－１０２０（以上、日本化薬（株）製）等であり、脂肪族エポキシ樹脂としては、ＡＤＥＫＡ　ＲＥＳＩＮ　ＥＰ－４０８０Ｓ、同ＥＰ－４０８５Ｓ、同ＥＰ－４０８８Ｓ（以上、（株）ＡＤＥＫＡ製）、セロキサイド２０２１Ｐ、セロキサイド２０８１、セロキサイド２０８３、セロキサイド２０８５、ＥＨＰＥ３１５０、ＥＰＯＬＥＡＤ　ＰＢ　３６００、同ＰＢ　４７００（以上、（株）ダイセル製）、デナコール　ＥＸ－２１２Ｌ、ＥＸ－２１４Ｌ、ＥＸ－２１６Ｌ、ＥＸ－３２１Ｌ、ＥＸ－８５０Ｌ（以上、ナガセケムテックス（株）製）等である。その他にも、ＡＤＥＫＡ　ＲＥＳＩＮ　ＥＰ－４０００Ｓ、同ＥＰ－４００３Ｓ、同ＥＰ－４０１０Ｓ、同ＥＰ－４０１１Ｓ（以上、（株）ＡＤＥＫＡ製）、ＮＣ－２０００、ＮＣ－３０００、ＮＣ－７３００、ＸＤ－１０００、ＥＰＰＮ－５０１、ＥＰＰＮ－５０２（以上、（株）ＡＤＥＫＡ製）、ｊＥＲ１０３１Ｓ（三菱化学（株）製）等が挙げられる。 Compounds having an epoxy group are described in paragraph numbers 0034 to 0036 of JP2013-011869A, paragraph numbers 0147 to 0156 of JP2014043556A, and paragraphs 0085 to 0092 of JP2014089408A. The prepared compounds can also be used. These contents are incorporated herein. As commercial products, for example, as 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., and bisphenol F-type epoxy resins include jER806, jER807, jER4004, jER4005, jER4007, jER4010 (above, Mitsubishi Chemical Corporation), EPICLON830, EPICLON835. (Above, DIC Corporation), LCE-21, RE-602S (above, Nippon Kayaku Co., Ltd.), etc. Yes, as phenol novolac type epoxy resin, jER152, jER154, jER157S70, jER157S65 (Mitsubishi Chemical Co., Ltd.), EPICLON N-740, EPICLON N-770, EPICLON N-775 (above, DIC Corporation) 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. In addition, 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.
　エポキシ基を有する化合物は、特開２００９－２６５５１８号公報の段落００４５等に記載の化合物を用いることもでき、この内容は本明細書に組み込まれる。 As the compound having an epoxy group, a compound described in paragraph 0045 of JP-A-2009-265518 can also be used, the contents of which are incorporated herein.
＜＜重合開始剤＞＞
　本発明の組成物は、重合開始剤を含むことが好ましい。
　重合開始剤の含有量は、組成物の全固形分に対し０．１～５０質量％が耐溶剤性、着色性の観点から好ましく、より好ましくは０．５～３０質量％であり、さらに好ましくは１～１０質量％である。組成物は、重合開始剤を、１種類のみを含んでいてもよいし、２種類以上含んでいてもよい。２種類以上含む場合は、その合計量が上記範囲となることが好ましい。
　重合開始剤としては、光重合開始剤または熱重合開始剤が好ましく、光重合開始剤が好ましい。熱重合開始剤としては特に制限は無く、公知の化合物を用いることができる。 << Polymerization initiator >>
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. There is no restriction | limiting in particular as a thermal-polymerization initiator, A well-known compound can be used.
（光重合開始剤）
　本発明の組成物は、光重合開始剤を含有することができる。特に、組成物が、重合性化合物を含む場合、光重合開始剤を含有することが好ましい。光重合開始剤としては、特に制限はなく、公知の光重合開始剤の中から適宜選択することができる。例えば、紫外線領域から可視領域の光線に対して感光性を有するものが好ましい。光重合開始剤は、光ラジカル重合開始剤が好ましい。また、光重合開始剤は、約３００ｎｍ～８００ｎｍ（３３０ｎｍ～５００ｎｍがより好ましい。）の範囲内に少なくとも約５０のモル吸光係数を有する化合物を、少なくとも１種類含有していることが好ましい。 (Photopolymerization initiator)
The composition of the present invention can contain a photopolymerization initiator. In particular, when the composition contains a polymerizable compound, it preferably contains a photopolymerization initiator. There is no restriction | limiting in particular as a photoinitiator, It can select suitably from well-known photoinitiators. For example, those having photosensitivity to light in the ultraviolet region to the visible region are preferable. 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).
　光重合開始剤としては、例えば、ハロゲン化炭化水素誘導体（例えば、トリアジン骨格を有するもの、オキサジアゾール骨格を有するものなど）、アシルホスフィンオキサイド等のアシルホスフィン化合物、ヘキサアリールビイミダゾール、オキシム誘導体等のオキシム化合物、有機過酸化物、チオ化合物、ケトン化合物、芳香族オニウム塩、ケトオキシムエーテル、アミノアセトフェノン化合物、ヒドロキシアセトフェノンなどが挙げられる。トリアジン骨格を有するハロゲン化炭化水素化合物としては、例えば、若林ら著、Ｂｕｌｌ．Ｃｈｅｍ．Ｓｏｃ．Ｊａｐａｎ，４２、２９２４（１９６９）記載の化合物、英国特許１３８８４９２号明細書記載の化合物、特開昭５３－１３３４２８号公報記載の化合物、独国特許３３３７０２４号明細書記載の化合物、Ｆ．Ｃ．Ｓｃｈａｅｆｅｒら著、Ｊ．Ｏｒｇ．Ｃｈｅｍ．；２９、１５２７（１９６４）記載の化合物、特開昭６２－５８２４１号公報記載の化合物、特開平５－２８１７２８号公報記載の化合物、特開平５－３４９２０号公報記載の化合物、米国特許第４２１２９７６号明細書に記載されている化合物などが挙げられる。 Examples of the photopolymerization initiator 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. Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent No. 1388492, a compound described in JP-A-53-133428, a compound described in German Patent No. 3337024, F.I. C. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, US Pat. No. 4,221,976 Examples include compounds described in the specification.
　また、露光感度の観点から、トリハロメチルトリアジン化合物、ベンジルジメチルケタール化合物、α－ヒドロキシケトン化合物、α－アミノケトン化合物、アシルホスフィン化合物、フォスフィンオキサイド化合物、メタロセン化合物、オキシム化合物、トリアリルイミダゾールダイマー、オニウム化合物、ベンゾチアゾール化合物、ベンゾフェノン化合物、アセトフェノン化合物及びその誘導体、シクロペンタジエン－ベンゼン－鉄錯体及びその塩、ハロメチルオキサジアゾール化合物、３－アリール置換クマリン化合物からなる群より選択される化合物が好ましい。トリハロメチルトリアジン化合物である光重合開始剤としては、トリクロロメチルトリアジン化合物であるであるトリアジンＰＰ（ＢＡＳＦ製）を用いることができる。 From the viewpoint of exposure sensitivity, trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-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. As a photopolymerization initiator that is a trihalomethyltriazine compound, triazine PP (manufactured by BASF) that is a trichloromethyltriazine compound can be used.
　光重合開始剤としては、ヒドロキシアセトフェノン化合物、アミノアセトフェノン化合物、及び、アシルホスフィン化合物も好適に用いることができる。より具体的には、例えば、特開平１０－２９１９６９号公報に記載のアミノアセトフェノン系開始剤、特許第４２２５８９８号公報に記載のアシルホスフィン系開始剤も用いることができる。ヒドロキシアセトフェノン系開始剤としては、ＩＲＧＡＣＵＲＥ　１８４、ＤＡＲＯＣＵＲ　１１７３、ＩＲＧＡＣＵＲＥ　５００、ＩＲＧＡＣＵＲＥ　２９５９、ＩＲＧＡＣＵＲＥ　１２７（商品名：いずれもＢＡＳＦ（株）製）を用いることができる。アミノアセトフェノン系開始剤としては、市販品であるＩＲＧＡＣＵＲＥ　９０７、ＩＲＧＡＣＵＲＥ　３６９、及び、ＩＲＧＡＣＵＲＥ　３７９、ＩＲＧＡＣＵＲＥ　３７９ＥＧ（商品名：いずれもＢＡＳＦ（株）製）を用いることができる。アミノアセトフェノン系開始剤は、３６５ｎｍ又は４０５ｎｍ等の長波光源に吸収波長がマッチングされた特開２００９－１９１１７９号公報に記載の化合物も用いることができる。
　アシルホスフィン系開始剤としては、市販品であるＩＲＧＡＣＵＲＥ　８１９やＩＲＧＡＣＵＲＥ　ＴＰＯ（商品名：いずれもＢＡＳＦ（株）製）を用いることができる。
　着色性の観点からアミノアセトフェノン系開始剤またはアシルホスフィン系開始剤が好ましく、着色性および密着性の観点からアシルホスフィン系開始剤がより好ましい。 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. As the hydroxyacetophenone-based initiator, IRGACURE 184, DAROCUR 1173, IRGACURE 500, IRGACURE 2959, IRGACURE 127 (trade names: all manufactured by BASF Corporation) can be used. As the aminoacetophenone-based initiator, commercially available products IRGACURE 907, IRGACURE 369, IRGACURE 379, IRGACURE 379EG (trade names: all manufactured by BASF Corporation) can be used. As the 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.
As the 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.
　光重合開始剤は、オキシム化合物を好ましく用いることもできる。オキシム化合物としては、オキシムエステル化合物がより好ましい。オキシム化合物の具体例としては、特開２００１－２３３８４２号公報記載の化合物、特開２０００－８００６８号公報記載の化合物、特開２００６－３４２１６６号公報記載の化合物、特開２０１６－２１０１２号公報に記載の化合物を用いることができる。 An oxime compound can also be preferably used as the photopolymerization initiator. As the oxime compound, 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.
　本発明において、好適に用いることのできるオキシム化合物としては、例えば、３－ベンゾイルオキシイミノブタン－２－オン、３－アセトキシイミノブタン－２－オン、３－プロピオニルオキシイミノブタン－２－オン、２－アセトキシイミノペンタン－３－オン、２－アセトキシイミノ－１－フェニルプロパン－１－オン、２－ベンゾイルオキシイミノ－１－フェニルプロパン－１－オン、３－（４－トルエンスルホニルオキシ）イミノブタン－２－オン、及び２－エトキシカルボニルオキシイミノ－１－フェニルプロパン－１－オンなどが挙げられる。また、Ｊ．Ｃ．Ｓ．Ｐｅｒｋｉｎ　ＩＩ（１９７９年）ｐｐ．１６５３－１６６０、Ｊ．Ｃ．Ｓ．Ｐｅｒｋｉｎ　ＩＩ（１９７９年）ｐｐ．１５６－１６２、Ｊｏｕｒｎａｌ　ｏｆ　Ｐｈｏｔｏｐｏｌｙｍｅｒ　Ｓｃｉｅｎｃｅ　ａｎｄ　Ｔｅｃｈｎｏｌｏｇｙ（１９９５年）ｐｐ．２０２－２３２、特開２０００－６６３８５号公報記載の化合物、特開２０００－８００６８号公報、特表２００４－５３４７９７号公報、特開２００６－３４２１６６号公報の各公報に記載の化合物等も挙げられる。市販品ではＩＲＧＡＣＵＲＥ　ＯＸＥ０１（ＢＡＳＦ（株）製）、ＩＲＧＡＣＵＲＥ　ＯＸＥ０２（ＢＡＳＦ（株）製）も好適に用いられる。また、ＴＲ－ＰＢＧ－３０４（常州強力電子新材料有限公司社製）、アデカアークルズＮＣＩ－９３０、アデカオプトマーＮ－１９１９（以上、（株）ＡＤＥＫＡ製）も用いることができる。 Examples of oxime compounds that can be preferably used in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, -Acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2 -One, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. In addition, J.H. C. S. Perkin II (1979) pp. 1653-1660, J.A. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. Examples thereof include compounds described in 202-232, JP-A 2000-66385, compounds described in JP-A 2000-80068, JP-T 2004-534797, JP-A 2006-342166, and the like. IRGACURE OXE01 (manufactured by BASF Corp.) and IRGACURE OXE02 (manufactured by BASF Corp.) are also suitably used as commercial products. Also, TR-PBG-304 (manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), Adeka Arcles NCI-930, Adeka Optomer N-1919 (above, manufactured by ADEKA Corporation) can be used.
　また上記以外のオキシム化合物として、カルバゾールＮ位にオキシムが連結した特表２００９－５１９９０４号公報に記載の化合物、ベンゾフェノン部位にヘテロ置換基が導入された米国特許第７６２６９５７号公報に記載の化合物、色素部位にニトロ基が導入された特開２０１０－１５０２５号公報及び米国特許公開２００９－２９２０３９号記載の化合物、国際公開特許２００９－１３１１８９号公報に記載のケトオキシム化合物、トリアジン骨格とオキシム骨格を同一分子内に含有する米国特許７５５６９１０号公報に記載の化合物、４０５ｎｍに吸収極大を有しｇ線光源に対して良好な感度を有する特開２００９－２２１１１４号公報記載の化合物、特開２０１４－１３７４６６号公報の段落番号００７６～００７９に記載された化合物などを用いてもよい。
　好ましくは、例えば、特開２０１３－２９７６０号公報の段落０２７４～０２７５を参酌することができ、この内容は本明細書に組み込まれる。
　具体的には、オキシム化合物としては、下記式（ＯＸ－１）で表される化合物が好ましい。オキシム化合物は、オキシムのＮ－Ｏ結合が（Ｅ）体のオキシム化合物であっても、オキシムのＮ－Ｏ結合が（Ｚ）体のオキシム化合物であってもよく、（Ｅ）体と（Ｚ）体との混合物であってもよい。 Further, as 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. 7,556,910, 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.
Preferably, for example, paragraphs 0274 to 0275 of JP 2013-29760 A can be referred to, the contents of which are incorporated herein.
Specifically, the oxime compound is preferably a compound represented by the following formula (OX-1). The 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.
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
　式（ＯＸ－１）中、ＲおよびＢは各々独立に一価の置換基を表し、Ａは二価の有機基を表し、Ａｒはアリール基を表す。
　式（ＯＸ－１）中、Ｒで表される一価の置換基としては、一価の非金属原子団であることが好ましい。
　一価の非金属原子団としては、アルキル基、アリール基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、複素環基、アルキルチオカルボニル基、アリールチオカルボニル基等が挙げられる。また、これらの基は、１以上の置換基を有していてもよい。また、前述した置換基は、さらに他の置換基で置換されていてもよい。
　置換基としてはハロゲン原子、アリールオキシ基、アルコキシカルボニル基またはアリールオキシカルボニル基、アシルオキシ基、アシル基、アルキル基、アリール基等が挙げられる。
　式（ＯＸ－１）中、Ｂで表される一価の置換基としては、アリール基、複素環基、アリールカルボニル基、又は、複素環カルボニル基が好ましい。これらの基は１以上の置換基を有していてもよい。置換基としては、前述した置換基が例示できる。
　式（ＯＸ－１）中、Ａで表される二価の有機基としては、炭素数１～１２のアルキレン基、シクロアルキレン基、アルキニレン基が好ましい。これらの基は１以上の置換基を有していてもよい。置換基としては、前述した置換基が例示できる。 In formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.
In the formula (OX-1), the monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
Examples of the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. Moreover, these groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.
In the formula (OX-1), the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.
In the formula (OX-1), the divalent organic group represented by A is preferably an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, or an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.
　本発明は、光重合開始剤として、フルオレン環を有するオキシム化合物を用いることもできる。フルオレン環を有するオキシム化合物の具体例としては、特開２０１４－１３７４６６号公報記載の化合物が挙げられる。この内容は本明細書に組み込まれる。 In the present invention, 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.
　本発明は、光重合開始剤として、フッ素原子を有するオキシム化合物を用いることもできる。フッ素原子を有するオキシム化合物の具体例としては、特開２０１０－２６２０２８号公報記載の化合物、特表２０１４－５００８５２号公報記載の化合物２４、３６～４０、特開２０１３－１６４４７１号公報記載の化合物（Ｃ－３）などが挙げられる。この内容は本明細書に組み込まれる。 In the present invention, 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.
　本発明は、光重合開始剤として、ニトロ基を有するオキシム化合物を用いることができる。ニトロ基を有するオキシム化合物は、二量体とすることも好ましい。ニトロ基を有するオキシム化合物の具体例としては、特開２０１３－１１４２４９号公報の段落００３１～００４７、特開２０１４－１３７４６６号公報の段落０００８～００１２、００７０～００７９に記載されている化合物、特許第４２２３０７１号公報の段落０００７～００２５に記載されている化合物、アデカアークルズＮＣＩ－８３１（（株）ＡＤＥＫＡ製）が挙げられる。 In the present invention, 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).
　本発明において好ましく使用されるオキシム化合物の具体例を以下に示すが、本発明はこれらに限定されない。 Specific examples of oxime compounds that are preferably used in the present invention are shown below, but the present invention is not limited thereto.
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000034
　オキシム化合物は、３５０ｎｍ～５００ｎｍの波長領域に極大吸収波長を有する化合物が好ましく、３６０ｎｍ～４８０ｎｍの波長領域に吸収波長を有する化合物がより好ましく、３６５ｎｍ及び４０５ｎｍの吸光度が高い化合物が特に好ましい。 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.
　オキシム化合物の３６５ｎｍ又は４０５ｎｍにおけるモル吸光係数は、感度の観点から、１，０００～３００，０００であることが好ましく、２，０００～３００，０００であることがより好ましく、５，０００～２００，０００であることが特に好ましい。化合物のモル吸光係数の測定は、公知の方法を用いることができ、具体的には、紫外可視分光光度計（Ｖａｒｉａｎ（株）製、Ｃａｒｙ－５　ｓｐｅｃｔｒｏｐｈｏｔｏｍｅｔｅｒ）にて、酢酸エチルを用い、０．０１ｇ／Ｌの濃度で測定することが好ましい。 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. For the measurement of the molar extinction coefficient of the compound, 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.
　本発明において、光重合開始剤は、２種類以上併用することも好ましい。例えば、メタノール中での３６５ｎｍの吸光係数が１．０×１０3ｍＬ／ｇｃｍ以上の光重合開始剤と、メタノール中での３６５ｎｍの吸光係数が１．０×１０2ｍＬ／ｇｃｍ以下であり、２５４ｎｍの吸光係数が１．０×１０3ｍＬ／ｇｃｍ以上の光重合開始剤とを併用することも好ましい。具体例として、アミノアセトフェノン化合物と、オキシム化合物との併用が挙げられる。この態様によれば、低温条件下であっても、硬化性に優れた膜を製造することができる。例えば、パターン形成工程において、現像工程前および現像工程後の２段階で組成物を露光することにより、最初の露光で組成物を適度に硬化させることができ、次の露光で組成物全体をほぼ硬化させることができる。このため、低温条件でも、組成物の硬化性を向上させることができる。 In this invention, it is also preferable to use 2 or more types of photoinitiators together. For example, 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, It is also preferred to use a photopolymerization initiator having an extinction coefficient of 254 nm of 1.0 × 10 3 mL / gcm or more in combination. As a specific example, combined use of an aminoacetophenone compound and an oxime compound can be mentioned. According to this aspect, a film having excellent curability can be produced even under low temperature conditions. For example, 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.
＜＜着色防止剤＞＞
　本発明の組成物は、着色防止剤を含有することが好ましい。
　本明細書に記載の着色防止剤は酸化防止剤としても使用でき、酸化防止剤は着色防止剤としても使用できる。
　着色防止剤としては、フェノール化合物、亜リン酸エステル化合物、チオエーテル化合物などが挙げられ、分子量５００以上のフェノール化合物、分子量５００以上の亜リン酸エステル化合物又は分子量５００以上のチオエーテル化合物がより好ましい。また、着色防止剤は、フェノール化合物が好ましく、分子量５００以上のフェノール化合物がより好ましい。 << anti-coloring agent >>
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.
Examples of 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. Further, the coloring inhibitor is preferably a phenol compound, and more preferably a phenol compound having a molecular weight of 500 or more.
　フェノール化合物としては、フェノール系着色防止剤として知られる任意のフェノール化合物を使用することができる。好ましいフェノール化合物としては、ヒンダードフェノール化合物が挙げられる。特に、フェノール性水酸基に隣接する部位（オルト位）に置換基を有する化合物が好ましい。前述の置換基としては炭素数１～２２の置換又は無置換のアルキル基が好ましく、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔ－ブチル基、ペンチル基、イソペンチル基、ｔ－ペンチル基、ヘキシル基、オクチル基、イソオクチル基、２－エチルへキシル基がより好ましい。また、同一分子内にフェノール基と亜リン酸エステル基を有する化合物も好ましい。 As the phenolic compound, any phenolic compound known as a phenolic anti-coloring agent can be used. Preferable phenolic compounds include hindered phenolic compounds. In particular, a compound having a substituent at a site (ortho position) adjacent to the phenolic hydroxyl group is preferable. As the above-mentioned substituent, 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.
　フェノール系水酸基含有化合物類としては、特に多置換フェノール系化合物が好適に用いられる。
　多置換フェノール系化合物には、安定なフェノキシラジカル生成に起因する、捕捉するパーオキシラジカルへの反応性から、その置換位置および構造の違う３種類：下記式（Ａ）ヒンダードタイプ、式（Ｂ）セミヒンダードタイプおよび式（Ｃ）レスヒンダードタイプがある。
Figure JPOXMLDOC01-appb-C000035
　着色防止機能を発現する構造部分である上記式（Ａ）～（Ｃ）において、Ｒは置換基であり、水素原子、ハロゲン原子、置換基を有してもよいアミノ基、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいアルコキシ基、置換基を有してもよいアリールオキシ基、置換基を有してもよいアルキルアミノ基、置換基を有してもよいアリールアミノ基、置換基を有してもよいアルキルスルホニル基、置換基を有してもよいアリールスルホニル基などが挙げられ、なかでも置換基を有してもよいアミノ基、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいアルコキシ基、置換基を有してもよいアリールオキシ基、置換基を有してもよいアルキルアミノ基、置換基を有してもよいアリールアミノ基が好ましい。 As the phenolic hydroxyl group-containing compounds, polysubstituted phenolic compounds are particularly preferably used.
There are three types of 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.
Figure JPOXMLDOC01-appb-C000035
In the above formulas (A) to (C), which are structural parts that exhibit a coloration preventing function, R is a substituent, having a hydrogen atom, a halogen atom, an amino group that may have a substituent, or a substituent. An alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylamino which may have a substituent Group, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, and the like. 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.
　さらに好ましい形態は、上記式（Ａ）～（Ｃ）で表される着色防止機能を発現する構造が同一分子内に複数存在する複合系着色防止剤であり、具体的には上記式（Ａ）～（Ｃ）で表される着色防止機能を発現する構造が同一分子内に２～４個存在する化合物が好ましい。これらの中では、式（Ｂ）セミヒンダードタイプが着色性の観点からより好ましい。
　フェノール系水酸基含有化合物としては、例えばパラメトキシフェノール、ジ－ｔ－ブチル－パラクレゾール、ピロガロール、ｔ－ブチルカテコール、４，４－チオビス（３－メチル－６－ｔ－ブチルフェノール）、２，２’－メチレンビス（４－メチル－６－ｔ－ブチルフェノール）、フェノール樹脂類、及びクレゾール樹脂類からなる群より選択される化合物などが挙げられる。
　市販品として入手できる代表例には、（Ａ）としてはＳｕｍｉｌｉｚｅｒ　ＢＨＴ（住友化学製）、Ｉｒｇａｎｏｘ　１０１０、１２２２（ＢＡＳＦ製）、アデカスタブＡＯ－２０、ＡＯ－５０、ＡＯ－６０（ＡＤＥＫＡ製）などがあり、（Ｂ）としてはＳｕｍｉｌｉｚｅｒ　ＢＢＭ－Ｓ（住友化学製）、Ｉｒｇａｎｏｘ　２４５（ＢＡＳＦ製）、アデカスタブＡＯ－８０（ＡＤＥＫＡ製）などがあり、（Ｃ）としてはアデカスタブＡＯ－３０、ＡＯ－４０（ＡＤＥＫＡ製）などがある。 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. Specifically, 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. In these, a formula (B) semi hindered type is more preferable from a viewpoint of coloring property.
Examples of 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 ′. And 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).
　亜リン酸エステル化合物としてはトリス［２－［［２，４，８，１０－テトラキス（１，１－ジメチルエチル）ジベンゾ［ｄ，ｆ］［１，３，２］ジオキサホスフェピン－６－イル］オキシ］エチル］アミン、トリス［２－［（４，６，９，１１－テトラ－ｔｅｒｔ－ブチルジベンゾ［ｄ，ｆ］［１，３，２］ジオキサホスフェピン－２－イル）オキシ］エチル］アミン、および亜りん酸エチルビス（２，４－ジｔｅｒｔ－ブチル－６－メチルフェニル）からなる群から選ばれる少なくとも１種類の化合物が挙げられる。 As a 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).
　チオエーテル化合物としては、例えば、チオジプロピオン酸ジラウリル、チオジプロピオン酸ジミリスチル、チオジプロピオン酸ジステアリル等のジアルキルチオジプロピオネート類、および、ペンタエリスリトールテトラ（β－アルキルチオプロピオン酸）エステル類；ペンタエリスリチルテトラキス（３－ラウリルチオプロピオネート）、ジラウリル－３，３’－チオジプロピオネート、ジミリスチル－３，３’－チオジプロピオネート、ジステアリル－３，３’－チオジプロピオネート等；テトラキス［メチレン－３－（ラウリルチオ）プロピオネート］メタン、ビス（メチル－４－［３－ｎ－アルキル（Ｃ１２／Ｃ１４）チオプロピオニルオキシ］５－ｔ－ブチルフェニル）スルファイド、ジトリデシル－３，３’－チオジプロピオネート、ジラウリル－３，３’－チオジプロピオネート、ジミリスチル－３，３´－チオジプロピオネート、ジステアリル－３，３’－チオジプロピオネート、ラウリル／ステアリルチオジプロピオネート、４，４’－チオビス（６－ｔ－ブチル－ｍ－クレゾール）、２，２’－チオビス（６－ｔ－ブチル－ｐ－クレゾール）、ジステアリル－ジサルファイドが好ましい。
　チオエーテル化合物として市販品として入手できる代表例には、アデカスタブ　ＡＯ－４１２Ｓ（ＣＡＳ：２９５９８－７６－３、（株）ＡＤＥＫＡ製）、アデカスタブ　ＡＯ－５０３（ＣＡＳ：１０５９５－７２－９、（株）ＡＤＥＫＡ製）、ＫＥＭＩＮＯＸ　ＰＬＳ（ＣＡＳ：２９５９８－７６－３、ケミプロ化成（株）製）を挙げることができる。
　着色防止剤は、市販品として容易に入手可能であり、市販品として入手できる代表例とした上述したもののほかに、アデカスタブ　ＡＯ－５０Ｆ、アデカスタブ　ＡＯ－６０Ｇ、アデカスタブ　ＡＯ－３３０、アデカスタブ　ＰＥＰ－３６Ａ（（株）ＡＤＥＫＡ製）などが挙げられる。 Examples of the thioether compound include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate, and pentaerythritol tetra (β-alkylthiopropionic acid) esters; Erythrityltetrakis (3-laurylthiopropionate), dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, etc. Tetrakis [methylene-3- (laurylthio) propionate] methane, bis (methyl-4- [3-n-alkyl (C12 / C14) thiopropionyloxy] 5-tert-butylphenyl) sulfide, ditridecyl-3,3 ′ -Thiodipropionate Dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, lauryl / stearylthiodipropionate, 4,4'- Preference is given to thiobis (6-tert-butyl-m-cresol), 2,2′-thiobis (6-tert-butyl-p-cresol), distearyl-disulfide.
Representative examples of commercially available 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. In addition to the above-described representative examples that can be obtained as commercial products, ADK STAB AO-50F, ADK STAB AO-60G, ADK STAB AO-330, ADK STAB PEP-36A ( (Made by ADEKA Corporation).
　着色防止剤の含有量は、組成物の全固形分に対して、０．０１～２０質量％であることが着色性および耐溶剤性の観点から好ましく、０．１～１５質量％がより好ましく、０．３～５質量％が特に好ましい。着色防止剤は、１種類のみでもよく、２種類以上でもよい。２種類以上の場合は、合計量が上記範囲となることが好ましい。 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.
＜＜紫外線吸収剤＞＞
　本発明の組成物は、紫外線吸収剤を含有してもよい。紫外線吸収剤は、共役ジエン系化合物が好ましく、下記式（Ｉ）で表される化合物がより好ましい。
Figure JPOXMLDOC01-appb-C000036
 << UV absorber >>
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).
Figure JPOXMLDOC01-appb-C000036
　式（Ｉ）において、Ｒ1及びＲ2は、各々独立に、水素原子、炭素原子数１～２０のアルキル基、又は炭素原子数６～２０のアリール基を表し、Ｒ1とＲ2とは互いに同一でも異なっていてもよいが、同時に水素原子を表すことはない。
　Ｒ1及びＲ2は、Ｒ1及びＲ2が結合する窒素原子と共に、環状アミノ基を形成してもよい。環状アミノ基としては、例えば、ピペリジノ基、モルホリノ基、ピロリジノ基、ヘキサヒドロアゼピノ基、ピペラジノ基等が挙げられる。
　Ｒ1及びＲ2は、各々独立に、炭素原子数１～２０のアルキル基が好ましく、炭素原子数１～１０のアルキル基がより好ましく、炭素原子数１～５のアルキル基がさらに好ましい。
　Ｒ3及びＲ4は、電子求引基を表す。ここで電子求引基は、ハメットの置換基定数σp値
（以下、単に「σp値」という。）が、０．２０以上１．０以下の電子求引基である。好ましくは、σp値が０．３０以上０．８以下の電子求引基である。Ｒ3及びＲ4は互いに結合して環を形成してもよい。Ｒ3及びＲ4は、アシル基、カルバモイル基、アルキルオキシカルボニル基、アリールオキシカルボニル基、シアノ基、ニトロ基、アルキルスルホニル基、アリールスルホニル基、スルホニルオキシ基、スルファモイル基が好ましく、アシル基、カルバモイル基、アルキルオキシカルボニル基、アリールオキシカルボニル基、シアノ基、アルキルスルホニル基、アリールスルホニル基、スルホニルオキシ基、スルファモイル基がより好ましい。
　上記のＲ1、Ｒ2、Ｒ3、及びＲ4の少なくとも１つは、連結基を介して、ビニル基と結合したモノマーより導かれるポリマーの形になっていてもよい。他のモノマーとの共重合体であっても良い。 In the 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. Here, the electron withdrawing group is an electron withdrawing group having a Hammett's substituent constant σ p value (hereinafter simply referred to as “σ p value”) of 0.20 or more and 1.0 or less. Preferably, it is an electron withdrawing group having a σ p value of 0.30 or more and 0.8 or less. 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.
　式（Ｉ）で示される紫外線吸収剤の置換基の説明は、ＷＯ２００９／１２３１０９Ａの段落００２４～００３３（対応する米国特許出願公開第２０１１／００３９１９５号明細書の＜００４０＞～＜００５９＞）の記載を参酌でき、これらの内容は本明細書に組み込まれる。式（Ｉ）で表される化合物の好ましい具体例は、ＷＯ２００９／１２３１０９Ａの段落００３４～００３７（対応する米国特許出願公開第２０１１／００３９１９５号明細書の＜００６０＞）の例示化合物（１）～（１４）の記載を参酌でき、これらの内容は本明細書に組み込まれる。
　式（Ｉ）で示される紫外線吸収剤の具体例としては、下記化合物（後述の実施例で用いる紫外線吸収剤Ｉ－１）が挙げられる。
Figure JPOXMLDOC01-appb-C000037
 The description of the substituents of the ultraviolet absorber represented by the formula (I) is described in paragraphs 0024 to 0033 of WO2009 / 123109A (corresponding to <0040> to <0059> of US Patent Application Publication No. 2011/0039195). Which are incorporated herein by reference. Preferred specific examples of the compound represented by the formula (I) are exemplified compounds (1) to (1) of paragraphs 0034 to 0037 of WO2009 / 123109A (corresponding to <0060> of US Patent Application Publication No. 2011/0039195). 14) can be referred to, and the contents thereof are incorporated in the present specification.
Specific examples of the ultraviolet absorber represented by the formula (I) include the following compounds (ultraviolet absorber I-1 used in Examples described later).
Figure JPOXMLDOC01-appb-C000037
　紫外線吸収剤の含有量は、組成物の全固形分に対して、０．１～１０質量％であることがパターン形状および耐溶剤性の観点から好ましく、０．１～７質量％であることがより好ましく、０．１～５質量％であることがさらに好ましく、０．１～３質量％であることが特に好ましい。また、本発明においては、紫外線吸収剤は、１種類のみでもよく、２種類以上でもよい。２種類以上の場合は、合計量が上記範囲となることが好ましい。 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.
＜＜密着剤＞＞
　本発明の組成物は、さらに密着剤を含有することが好ましい。密着剤としては特に制限は無く、公知の密着剤が使用できる。密着剤としては、例えば、シランカップリング剤を挙げることができる。この態様によれば、膜の基材との密着性を良化できる。
　本発明において、「シランカップリング剤」は、加水分解性基とそれ以外の官能基とを有するシラン化合物を意味する。また、「加水分解性基」とは、珪素原子に直結し、加水分解反応および縮合反応のうち少なくとも一方によってシロキサン結合を生じ得る置換基をいう。加水分解性基としては、例えば、ハロゲン原子、アルコキシ基、アシルオキシ基などが挙げられ、アルコキシ基が好ましい。すなわち、シランカップリング剤は、アルコキシシリル基を有する化合物が好ましい。また、加水分解性基以外の官能基は、樹脂との間で相互作用もしくは結合形成して親和性を示す基を有が好ましい。例えば、（メタ）アクリロイル基、フェニル基、メルカプト基、エポキシ基、オキセタニル基が挙げられ、（メタ）アクリロイル基およびエポキシ基が好ましい。即ち、シランカップリング剤は、アルコキシシリル基と、（メタ）アクリロイル基およびエポキシ基のうち少なくとも一方と、を有する化合物が好ましい。
　アルコキシシリル基におけるアルコキシ基の炭素数は、１～５が好ましく、１～３がより好ましく、１または２が特に好ましい。アルコキシシリル基は、同一分子内に２個以上有することが好ましく、２～３個有することがさらに好ましい。 << Adhesive >>
The composition of the present invention preferably further contains an adhesive. There is no restriction | limiting in particular as an adhesive agent, A well-known adhesive agent can be used. Examples of the adhesive include a silane coupling agent. According to this aspect, the adhesion between the film and the substrate can be improved.
In the present invention, the “silane coupling agent” means a silane compound having a hydrolyzable group and other functional groups. In addition, 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. As a hydrolysable group, a halogen atom, an alkoxy group, an acyloxy group etc. are mentioned, for example, An alkoxy group is preferable. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Further, 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. That is, 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.
　シランカップリング剤の具体例としては、例えば、３－メタクリロキシプロピルトリメトキシシラン、３－メタクリロキシプロピルトリエトキシシラン、３－アクリロキシプロピルトリメトキシシラン、３－アクリロキシプロピルトリエトキシシラン、３－メルカプトプロピルトリメトキシシラン、３－アミノプロピルトリエトキシシラン、フェニルトリメトキシシラン、メチルトリメトキシシラン、ジメチルジメトキシシラン、メチルトリエトキシシラン、ジメチルジエトキシシラン、フェニルトリエトキシシラン、ｎ－プロピルトリメトキシシラン、ｎ－プロピルトリエトキシシラン、ヘキシルトリメトキシシラン、ヘキシルトリエトキシシラン、オクチルトリエトキシシラン、デシルトリメトキシシラン、１，６－ビス（トリメトキシシリル）ヘキサン、トリフルオロプロピルトリメトキシシラン、ヘキサメチルジシラザン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、３－グリシドキシプロピルメチルジメトキシシラン、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルメチルジエトキシシラン、３－グリシドキシプロピルトリエトキシシラン、パラスチリルトリメトキシシラン、３－メタクリロキシプロピルメチルジメトキシシラン、３－メタクリロキシプロピルメチルジエトキシシラン、Ｎ－２－（アミノメチルエチル）－３－アミノプロピルメチルジメトキシシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルメチルジメトキシシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリメトキシシラン、３－トリエトキシシリル－Ｎ－（１，３－ジメチル－ブチリデン）プロピルアミン、Ｎ－フェニル－３－アミノプロピルトリメトキシシラン、Ｎ－（ビニルベンジル）－２－アミノエチル－３－アミノプロピルトリメトキシシランの塩酸塩、トリス－（トリメトキシシリルプロピル）イソシアヌレート、３－ウレイドプロピルトリエトキシシラン、３－メルカプトプロピルメチルジメトキシシラン、ビス（トリエトキシシリルプロピル）テトラスルフィド、３－イソシアネートプロピルトリエトキシシランなどが挙げられる。また、上記以外にアルコキシオリゴマーを用いることができる。また、下記化合物を用いることもできる。
Figure JPOXMLDOC01-appb-C000038
 Specific examples of the silane coupling agent 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 (trimethoxy Yl) hexane, trifluoropropyltrimethoxysilane, hexamethyldisilazane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, parastyryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacrylic Roxypropylmethyldiethoxysilane, N-2- (aminomethylethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- ( Minoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, tris- (trimethoxysilylpropyl) isocyanurate, 3-ureidopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane Bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, and the like. In addition to the above, alkoxy oligomers can be used. Also, the following compounds can be used.
Figure JPOXMLDOC01-appb-C000038
　市販品としては、信越シリコーン（株）製のＫＢＭ－１３、ＫＢＭ－２２、ＫＢＭ－１０３、ＫＢＥ－１３、ＫＢＥ－２２、ＫＢＥ－１０３、ＫＢＭ－３０３３、ＫＢＥ－３０３３、ＫＢＭ－３０６３、ＫＢＭ－３０６６、ＫＢＭ－３０８６、ＫＢＥ－３０６３、ＫＢＥ－３０８３、ＫＢＭ－３１０３、ＫＢＭ－３０６６、ＫＢＭ－７１０３、ＳＺ－３１、ＫＰＮ－３５０４、ＫＢＭ－１００３、ＫＢＥ－１００３、ＫＢＭ－３０３、ＫＢＭ－４０２、ＫＢＭ－４０３、ＫＢＥ－４０２、ＫＢＥ－４０３、ＫＢＭ－１４０３、ＫＢＭ－５０２、ＫＢＭ－５０３、ＫＢＥ－５０２、ＫＢＥ－５０３、ＫＢＭ－５１０３、ＫＢＭ－６０２、ＫＢＭ－６０３、ＫＢＭ－９０３、ＫＢＥ－９０３、ＫＢＥ－９１０３、ＫＢＭ－５７３、ＫＢＭ－５７５、ＫＢＭ－９６５９、ＫＢＥ－５８５、ＫＢＭ－８０２、ＫＢＭ－８０３、ＫＢＥ－８４６、ＫＢＥ－９００７、Ｘ－４０－１０５３、Ｘ－４１－１０５９Ａ、Ｘ－４１－１０５６、Ｘ－４１－１８０５、Ｘ－４１－１８１８、Ｘ－４１－１８１０、Ｘ－４０－２６５１、Ｘ－４０－２６５５Ａ、ＫＲ－５１３、ＫＣ－８９Ｓ、ＫＲ－５００、ＫＲ－５１６、ＫＲ－５１７、Ｘ－４０－９２９６、Ｘ－４０－９２２５、Ｘ－４０－９２４６、Ｘ－４０－９２５０、ＫＲ－４０１Ｎ、Ｘ－４０－９２２７、Ｘ－４０－９２４７、ＫＲ－５１０、ＫＲ－９２１８、ＫＲ－２１３、Ｘ－４０－２３０８、Ｘ－４０－９２３８などが挙げられる。また、シランカップリング剤は、特開２００９－２８８７０３号公報の段落番号００１８～００３６に記載の化合物、特開２００９－２４２６０４号公報の段落００５６～００６６に記載の化合物が挙げられ、この内容は本明細書に組み込まれる。
　また、アルコキシシリル基を有する化合物は、アルコキシシリル基を側鎖に有するポリマーを用いることもできる。
　シランカップリング剤として、特開２００９－２８８７０３号公報の＜００１１＞～＜００３７＞に記載の特定シラン化合物も参酌して使用でき、この内容は本明細書に組み込まれる。 Commercially available products include KBM-13, KBM-22, KBM-103, KBE-13, KBE-22, KBE-103, KBM-3033, KBE-3033, KBM-3063, KBM- manufactured by Shin-Etsu Silicone Co., Ltd. 3066, KBM-3086, KBE-3063, KBE-3083, KBM-3103, KBM-3066, KBM-7103, SZ-31, KPN-3504, KBM-1003, KBE-1003, KBM-303, KBM-402, KBM-403, KBE-402, KBE-403, KBM-1403, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBM-903, KBE- 903, KBE-9103, KBM-573, KBM-575 KBM-9659, KBE-585, KBM-802, KBM-803, KBE-846, KBE-9007, X-40-1053, X-41-1059A, X-41-1056, X-41-1805, X- 41-1818, X-41-1810, X-40-2651, X-40-2655A, KR-513, KC-89S, KR-500, KR-516, KR-517, X-40-9296, X- 40-9225, X-40-9246, X-40-9250, KR-401N, X-40-9227, X-40-9247, KR-510, KR-9218, KR-213, X-40-2308, X-40-9238 and the like. Examples of the silane coupling agent 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.
　シランカップリング剤の中では、分子内にケイ素原子と窒素原子と重合性基とを含むシラン化合物が好ましい。
　密着剤の含有量は、組成物の全固形分に対して、０．０１～１０質量％が好ましく、０．１～７質量％がより好ましく、１～５質量％が特に好ましい。これらの範囲であると密着性と一ヶ月経時後の濃度ムラの観点から好ましい。また、本発明においては、組成物が含有する密着剤は、１種類のみでもよく、２種類以上でもよい。２種類以上の場合は、合計量が上記範囲となることが好ましい。 Among the silane coupling agents, 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. Moreover, in this invention, 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.
＜＜連鎖移動剤＞＞
　本発明の組成物は、連鎖移動剤を含有することが好ましい。この態様によれば、パターン形成時の露光において、露光により膜表面（パターン表面）の硬化を促進できる。このため、露光時の膜の厚さの減少などを抑制でき、より矩形性および密着性に優れたパターンを形成しやすい。 << Chain transfer agent >>
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 | decrease of the thickness of the film | membrane at the time of exposure, etc. can be suppressed, and it is easy to form the pattern which was more excellent in rectangularity and adhesiveness.
　連鎖移動剤としては、Ｎ，Ｎ－ジアルキルアミノ安息香酸アルキルエステルや、チオール化合物などが挙げられ、チオール化合物が好ましい。チオール化合物は、分子内に２個以上（好ましくは２～８個、より好ましくは３～６個）のメルカプト基を有する化合物が好ましい。チオール化合物の具体例としては、２－メルカプトベンゾチアゾール、２－メルカプトベンゾオキサゾール、２－メルカプトベンゾイミダゾール、Ｎ－フェニルメルカプトベンゾイミダゾール、１，３，５－トリス（３－メルカプトブチルオキシエチル）－１，３，５－トリアジン－２，４，６（１Ｈ，３Ｈ，５Ｈ）－トリオンなどの複素環を有するチオール化合物、ペンタエリスリトールテトラキス（３－メルカプトブチレート）、１，４－ビス（３－メルカプトブチリルオキシ）ブタンなどの脂肪族系のチオール化合物などが挙げられる。
　また、連鎖移動剤の市販品としては、ＰＥＭＰ（ＳＣ有機化学株式会社製、チオール化合物）、サンセラー　Ｍ（三新化学工業（株）製、チオール化合物）、カレンズＭＴ　ＢＤ１（昭和電工（株）製、チオール化合物）などが挙げられる。
　また、下記化合物を用いることも好ましい。
Figure JPOXMLDOC01-appb-C000039
 Examples of the chain transfer agent 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. Specific examples of the thiol compound 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.
In addition, commercially available 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.
Figure JPOXMLDOC01-appb-C000039
　連鎖移動剤の含有量は、組成物の全固形分に対して０．２～５．０質量％が好ましく、０．４～３．０質量％がより好ましい。
　連鎖移動剤の含有量は、重合性化合物の１００質量部に対し、１～４０質量部が好ましく、２～２０質量部がより好ましい。
　連鎖移動剤は、１種類のみでもよく、２種類以上でもよい。２種類以上の場合は、合計量が上記範囲となることが好ましい。 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.
＜＜増感剤＞＞
　本発明の組成物は、光重合開始剤のラジカル発生効率の向上、感光波長の長波長化の目的で、増感剤を含有していてもよい。増感剤としては、光重合開始剤に対し、電子移動機構又はエネルギー移動機構で増感させるものが好ましい。増感剤は、３００ｎｍ～４５０ｎｍの波長領域に吸収波長を有するものが挙げられる。具体的には、特開２０１０－１０６２６８号公報の段落０２３１～０２５３（対応する米国特許出願公開第２０１１／０１２４８２４号明細書の＜０２５６＞～＜０２７３＞）の説明を参酌でき、これらの内容は本明細書に組み込まれる。 << Sensitizer >>
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. As the sensitizer, a photosensitizer that is sensitized by an electron transfer mechanism or an energy transfer mechanism is preferable. Examples of the sensitizer include those having an absorption wavelength in a wavelength region of 300 nm to 450 nm. Specifically, 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.
　増感剤の含有量は、組成物の全固形分に対して、０．１～２０質量％が好ましく、０．５～１５質量％がより好ましい。増感剤は、１種類のみでもよく、２種類以上でもよい。２種類以上の場合は、合計量が上記範囲となることが好ましい。 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.
＜＜共増感剤＞＞
　本発明の組成物は、更に共増感剤を含有することも好ましい。共増感剤は、光重合開始剤や増感剤の活性放射線に対する感度を一層向上させる、あるいは、酸素の重合性化合物の重合阻害を抑制する等の作用を有する。共増感剤としては、具体的には、特開２０１０－１０６２６８号公報の段落０２５４～０２５７（対応する米国特許出願公開第２０１１／０１２４８２４号明細書の＜０２７７＞～＜０２７９＞）の説明を参酌でき、これらの内容は本明細書に組み込まれる。 << Co-sensitizer >>
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.
　共増感剤の含有量は、重合成長速度と、硬化速度の向上の観点から、組成物の全固形分に対して、０．１～３０質量％が好ましく、１～２５質量％がより好ましく、１．５～２０質量％が更に好ましい。共増感剤は１種類のみでもよく、２種類以上でもよい。２種類以上の場合は、合計量が上記範囲となることが好ましい。 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. There may be only one kind of co-sensitizer or two or more kinds. In the case of two or more types, the total amount is preferably within the above range.
＜＜重合禁止剤＞＞
　本発明の組成物は、組成物の製造中あるいは保存中において重合性化合物などの不要な重合を阻止するために、重合禁止剤を添加することが好ましい。
　重合禁止剤としては、
　フェノール系水酸基含有化合物（好ましくは、ハイドロキノン、パラメトキシフェノール、ジ－ｔ－ブチル－パラクレゾール、ピロガロール、ｔ－ブチルカテコール、ベンゾキノン、４，４－チオビス（３－メチル－６－ｔ－ブチルフェノール）、２，２’－メチレンビス（４－メチル－６－ｔ－ブチルフェノール）、２，６－ジ－ｔ－ブチル－４－メチルフェノール（ＢＨＴ）、フェノール樹脂類、及びクレゾール樹脂類からなる群より選択される化合物）；
　Ｎ－オキシド化合物類（好ましくは、５，５－ジメチル－１－ピロリンＮ－オキシド、４－メチルモルホリンＮ－オキシド、ピリジンＮ－オキシド、４－ニトロピリジンＮ－オキシド、３－ヒドロキシピリジンＮ－オキシド、ピコリン酸Ｎ－オキシド、ニコチン酸Ｎ－オキシド、及びイソニコチン酸Ｎ－オキシドからなる群より選択される化合物）；
　ピペリジン１－オキシルフリーラジカル化合物類（好ましくは、ピペリジン１－オキシルフリーラジカル、２，２，６，６－テトラメチルピペリジン１－オキシルフリーラジカル、４－オキソ－２，２，６，６－テトラメチルピペリジン１－オキシルフリーラジカル、４－ヒドロキシ－２，２，６，６－テトラメチルピペリジン１－オキシルフリーラジカル、４－アセトアミド－２，２，６，６－テトラメチルピペリジン１－オキシルフリーラジカル、４－マレイミド－２，２，６，６－テトラメチルピペリジン１－オキシルフリーラジカル、及び４－ホスホノキシ－２，２，６，６－テトラメチルピペリジン１－オキシルフリーラジカルからなる群より選択される化合物）；
　ピロリジン１－オキシルフリーラジカル化合物類（好ましくは、３－カルボキシプロキシルフリーラジカル（３－カルボキシ－２，２，５，５－テトラメチルピロリジン１－オキシルフリーラジカル））；
　Ｎ－ニトロソフェニルヒドロキシアミン類（好ましくは、Ｎ－ニトロソフェニルヒドロキシアミン第一セリウム塩及びＮ－ニトロソフェニルヒドロキシアミンアルミニウム塩からなる化合物群から選択される化合物）；
　ジアゾニウム化合物類（好ましくは、４－ジアゾフェニルジメチルアミンの硫酸水素塩、４－ジアゾジフェニルアミンのテトラフルオロホウ酸塩、及び３－メトキシ－４－ジアゾジフェニルアミンのヘキサフルオロリン酸塩からなる群より選択される化合物）；
　カチオン染料類；
　スルフィド基含有化合物類；
　ニトロ基含有化合物類；
　ＦｅＣｌ3、ＣｕＣｌ2等の遷移金属化合物類が挙げられる。また、これらの化合物類においては、フェノール骨格やリン含有骨格などの重合禁止機能を発現する構造が同一分子内に複数存在する複合系化合物であってもよい。例えば特開平１０－４６０３５号公報に記載の化合物なども好適に用いられる。 << Polymerization inhibitor >>
In the composition of the present invention, 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.
As 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 , A compound selected from the group consisting of picolinic acid N-oxide, nicotinic acid N-oxide, and isonicotinic acid N-oxide);
Piperidine 1-oxyl free radical compounds (preferably piperidine 1-oxyl free radical, 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-oxo-2,2,6,6-tetramethyl Piperidine 1-oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-acetamido-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4 -A compound selected from the group consisting of maleimide-2,2,6,6-tetramethylpiperidine 1-oxyl free radical and 4-phosphonoxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical) ;
Pyrrolidine 1-oxyl free radical compounds (preferably, 3-carboxyproxyl free radical (3-carboxy-2,2,5,5-tetramethylpyrrolidine 1-oxyl free radical));
N-nitrosophenylhydroxyamines (preferably compounds selected from the group consisting of N-nitrosophenylhydroxyamine primary cerium salts and N-nitrosophenylhydroxyamine aluminum salts);
Diazonium compounds (preferably selected from the group consisting of 4-diazophenyldimethylamine hydrogen sulfate, 4-diazodiphenylamine tetrafluoroborate, and 3-methoxy-4-diazodiphenylamine hexafluorophosphate Compound);
Cationic dyes;
Sulfide group-containing compounds;
Nitro group-containing compounds;
Examples thereof include transition metal compounds such as FeCl 3 and CuCl 2 . In addition, 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. For example, the compounds described in JP-A-10-46035 are also preferably used.
　重合禁止剤の具体例としては、特開２０１５－３４９６１号公報の段落０２１１～０２２３に記載の化合物が挙げられ、この内容は本明細書に組み込まれる。 Specific examples of the polymerization inhibitor include compounds described in JP-A-2015-34961, paragraphs 0211 to 0223, the contents of which are incorporated herein.
　重合禁止剤の含有量は、光重合開始剤１００質量部に対して、０．０１質量部～１０質量部が好ましく、０．０１～８質量部がより好ましく、０．０１～５質量部が最も好ましい。上記範囲とすることで、非画像部における硬化反応抑制及び画像部における硬化反応促進が充分おこなわれ、パターン形状及び感度が良好となる。重合禁止剤は、１種類のみでもよく、２種類以上でもよい。２種類以上の場合は、合計量が上記範囲となることが好ましい。 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.
＜＜界面活性剤＞＞
　本発明の組成物は、塗布適性をより向上させる観点から、各種類の界面活性剤を含有させてもよい。界面活性剤としては、フッ素系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤、シリコーン系界面活性剤などの各種類の界面活性剤を使用できる。 << Surfactant >>
The composition of the present invention may contain various types of surfactants from the viewpoint of further improving coating suitability. As the surfactant, various types of surfactants such as a fluorosurfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant can be used.
　上記組成物にフッ素系界面活性剤を含有させることで、塗布液として調製したときの液特性（特に、流動性）がより向上し、塗布厚の均一性や省液性をより改善することができる。即ち、フッ素系界面活性剤を含有する組成物を適用した塗布液を用いて膜形成する場合においては、被塗布面と塗布液との界面張力が低下して、被塗布面への濡れ性が改善され、被塗布面への塗布適性が向上する。このため、厚みムラの小さい均一厚の膜形成をより好適に行うことができる。 By including a fluorosurfactant in the above composition, 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.
　フッ素系界面活性剤中のフッ素含有率は、３～４０質量％が好適であり、より好ましくは５～３０質量％であり、特に好ましくは７～２５質量％である。フッ素含有率がこの範囲内であるフッ素系界面活性剤は、塗布膜の厚さの均一性や省液性の点で効果的であり、組成物中における溶解性も良好である。 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.
　フッ素系界面活性剤として具体的には、特開２０１４－４１３１８号公報の段落００６０～００６４（対応する国際公開２０１４／１７６６９号パンフレットの段落００６０～００６４）等に記載の界面活性剤、特開２０１１－１３２５０３号公報の段落０１１７～０１３２に記載の界面活性剤が挙げられ、これらの内容は本明細書に組み込まれる。フッ素系界面活性剤の市販品としては、例えば、メガファックＦ１７１、同Ｆ１７２、同Ｆ１７３、同Ｆ１７６、同Ｆ１７７、同Ｆ１４１、同Ｆ１４２、同Ｆ１４３、同Ｆ１４４、同Ｒ３０、同Ｆ４３７、同Ｆ４７５、同Ｆ４７９、同Ｆ４８２、同Ｆ５５４、同Ｆ７８０（以上、ＤＩＣ（株）製）、フロラードＦＣ４３０、同ＦＣ４３１、同ＦＣ１７１（以上、住友スリーエム（株）製）、サーフロンＳ－３８２、同ＳＣ－１０１、同ＳＣ－１０３、同ＳＣ－１０４、同ＳＣ－１０５、同ＳＣ－１０６８、同ＳＣ－３８１、同ＳＣ－３８３、同Ｓ－３９３、同ＫＨ－４０（以上、旭硝子（株）製）、ＰｏｌｙＦｏｘ　ＰＦ６３６、ＰＦ６５６、ＰＦ６３２０、ＰＦ６５２０、ＰＦ７００２（ＯＭＮＯＶＡ社製）等が挙げられる。 Specific examples of the fluorosurfactant 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. Commercially available 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.
　フッ素系界面活性剤は、ブロックポリマーを用いることもできる。例えば特開２０１１－８９０９０号公報に記載された化合物が挙げられる。フッ素系界面活性剤は、フッ素原子を有する（メタ）アクリレート化合物に由来する繰り返し単位と、アルキレンオキシ基（好ましくはエチレンオキシ基、プロピレンオキシ基）を２以上（好ましくは５以上）有する（メタ）アクリレート化合物に由来する繰り返し単位と、を含む含フッ素高分子化合物も好ましく用いることができる。下記化合物も本発明で用いられるフッ素系界面活性剤として例示される。
Figure JPOXMLDOC01-appb-C000040
　上記の化合物の重量平均分子量は、好ましくは３，０００～５０，０００であり、例えば、１４，０００である。 As the fluorosurfactant, 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.
Figure JPOXMLDOC01-appb-C000040
The weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example, 14,000.
　また、フッ素系界面活性剤は、エチレン性不飽和結合を有する基を側鎖に有する含フッ素重合体を用いることもできる。具体例としては、特開２０１０－１６４９６５号公報００５０～００９０段落および０２８９～０２９５段落に記載された化合物、例えばＤＩＣ（株）製のメガファックＲＳ－１０１、ＲＳ－１０２、ＲＳ－７１８Ｋ、ＲＳ－７２－Ｋ等が挙げられる。フッ素系界面活性剤は、特開２０１５－１１７３２７号公報の段落００１５～０１５８に記載の化合物を用いることもできる。 Further, as the fluorosurfactant, 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. As the fluorine-based surfactant, compounds described in paragraphs 0015 to 0158 of JP-A No. 2015-117327 can also be used.
　ノニオン系界面活性剤としては、グリセロール、トリメチロールプロパン、トリメチロールエタン並びにそれらのエトキシレート及びプロポキシレート（例えば、グリセロールプロポキシレート、グリセリンエトキシレート等）、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリエチレングリコールジラウレート、ポリエチレングリコールジステアレート、ソルビタン脂肪酸エステル、プルロニックＬ１０、Ｌ３１、Ｌ６１、Ｌ６２、１０Ｒ５、１７Ｒ２、２５Ｒ２（ＢＡＳＦ社製）、テトロニック３０４、７０１、７０４、９０１、９０４、１５０Ｒ１（ＢＡＳＦ社製）、ソルスパース２００００（日本ルーブリゾール（株）製）、ＮＣＷ－１０１、ＮＣＷ－１００１、ＮＣＷ－１００２（和光純薬工業（株）製）、パイオニンＤ－６１１２、Ｄ－６１１２－Ｗ、Ｄ－６３１５（竹本油脂（株）製）、オルフィンＥ１０１０、サーフィノール１０４、４００、４４０（日信化学工業（株）製）などが挙げられる。 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 Chemical Industries, Ltd.), Pionin D-6112, D-6112-W, D- 6315 (manufactured by Takemoto Yushi Co., Ltd.), Olphine E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry Co., Ltd.) and the like.
　カチオン系界面活性剤としては、オルガノシロキサンポリマーＫＰ３４１（信越化学工業（株）製）、（メタ）アクリル酸系（共）重合体ポリフローＮｏ．７５、Ｎｏ．９０、Ｎｏ．９５（共栄社化学（株）製）、Ｗ００１（裕商（株）製）等が挙げられる。 Examples of cationic surfactants 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.
　アニオン系界面活性剤としては、Ｗ００４、Ｗ００５、Ｗ０１７（裕商（株）製）、サンデットＢＬ（三洋化成（株）製）等が挙げられる。 Examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.), Sandet BL (manufactured by Sanyo Chemical Co., Ltd.), and the like.
　シリコーン系界面活性剤としては、例えば、トーレシリコーンＤＣ３ＰＡ、トーレシリコーンＳＨ７ＰＡ、トーレシリコーンＤＣ１１ＰＡ、トーレシリコーンＳＨ２１ＰＡ、トーレシリコーンＳＨ２８ＰＡ、トーレシリコーンＳＨ２９ＰＡ、トーレシリコーンＳＨ３０ＰＡ、トーレシリコーンＳＨ８４００（以上、東レ・ダウコーニング（株）製）、ＴＳＦ－４４４０、ＴＳＦ－４３００、ＴＳＦ－４４４５、ＴＳＦ－４４６０、ＴＳＦ－４４５２（以上、モメンティブ・パフォーマンス・マテリアルズ社製）、ＫＰ３４１、ＫＦ６００１、ＫＦ６００２（以上、信越シリコーン株式会社製）、ＢＹＫ３０７、ＢＹＫ３２３、ＢＹＫ３３０（以上、ビックケミー社製）等が挙げられる。 Examples of 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.
　界面活性剤は、１種類のみを用いてもよいし、２種類以上を組み合わせてもよい。
　界面活性剤の含有量は、組成物の全固形分に対して、０．００１～２．０質量％が好ましく、０．００５～１．０質量％がより好ましい。 Only one type of surfactant may be used, or two or more types may be combined.
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.
＜＜その他の添加剤＞＞
　更に、組成物に対しては、膜または硬化膜の物性を改良するために可塑剤や感脂化剤等の公知の添加剤を加えてもよい。可塑剤としては、例えば、ジオクチルフタレート、ジドデシルフタレート、トリエチレングリコールジカプリレート、ジメチルグリコールフタレート、トリクレジルホスフェート、ジオクチルアジペート、ジブチルセバケート、トリアセチルグリセリン等が挙げられる。可塑剤の含有量は、重合性化合物と樹脂との合計質量に対し１０質量％以下が好ましい。 << Other additives >>
Furthermore, 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. Examples of 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.
＜組成物の調製方法＞
　上述の組成物は、前述の成分を混合して調製できる。
　組成物の調製に際しては、各成分を一括配合してもよいし、各成分を溶剤に溶解および分散のうち少なくとも一方をした後に逐次配合してもよい。また、配合する際の投入順序や作業条件は特に制約を受けない。
　また、顔料を分散させるプロセスとしては、顔料の分散に用いる機械力として、圧縮、圧搾、衝撃、剪断、キャビテーションなどを使用するプロセスが挙げられる。これらプロセスの具体例としては、ビーズミル、サンドミル、ロールミル、高速インペラー、サンドグラインダー、フロージェットミキサー、高圧湿式微粒化、超音波分散などが挙げられる。また「分散技術大全、株式会社情報機構発行、２００５年７月１５日」や「サスペンション（固／液分散系）を中心とした分散技術と工業的応用の実際　総合資料集、経営開発センター出版部発行、１９７８年１０月１０日」に記載のプロセス及び分散機を好適に使用出来る。 <Method for preparing composition>
The aforementioned composition can be prepared by mixing the aforementioned components.
In preparing the composition, 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. In addition, there are no particular restrictions on the charging order and working conditions when blending.
Examples of 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. Specific examples of these processes include a bead mill, a sand mill, a roll mill, a high speed impeller, a sand grinder, a flow jet mixer, high pressure wet atomization, and ultrasonic dispersion. Also, “Dispersion Technology Taizen, Issued by Information Technology Corporation, July 15, 2005” and “Dispersion Technology and Industrial Application Centered on Suspension (Solid / Liquid Dispersion System)” The process and the dispersing machine described in “Issuance, October 10, 1978” can be preferably used.
　組成物の調製にあたり、異物の除去や欠陥の低減などの目的で、フィルタでろ過することが好ましい。フィルタとしては、従来からろ過用途等に用いられるものであれば特に限定されることなく用いることができる。例えば、ポリテトラフルオロエチレン（ＰＴＦＥ）等のフッ素系樹脂、ナイロン（例えばナイロン－６、ナイロン－６，６）等のポリアミド系樹脂、ポリエチレン、ポリプロピレン（ＰＰ）等のポリオレフィン樹脂（高密度、超高分子量を含む）等を用いたフィルタが挙げられる。これら素材の中でもポリプロピレン（高密度ポリプロピレンを含む）およびナイロンが好ましい。
　フィルタの孔径は、０．０１～７．０μｍ程度が適しており、好ましくは０．０１～３．０μｍ程度、さらに好ましくは０．０５～０．５μｍ程度である。この範囲とすることにより、後工程において均一及び平滑な組成物の調製を阻害する、微細な異物を確実に除去することが可能となる。また、ファイバ状のフィルタを用いることも好ましく、フィルタとしては例えばポリプロピレンファイバ、ナイロンファイバ、グラスファイバ等が挙げられ、具体的にはロキテクノ（株）製のＳＢＰタイプシリーズ（ＳＢＰ００８など）、ＴＰＲタイプシリーズ（ＴＰＲ００２、ＴＰＲ００５など）、ＳＨＰＸタイプシリーズ（ＳＨＰＸ００３など）のフィルタカートリッジを用いることができる。 In preparing the composition, it is preferable to filter with a filter for the purpose of removing foreign substances or reducing defects. As a filter, if it is conventionally used for the filtration use etc., it can use without being specifically limited. For example, 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. Among these materials, polypropylene (including high density polypropylene) and nylon are preferable.
The pore size of the filter is suitably about 0.01 to 7.0 μm, preferably about 0.01 to 3.0 μm, more preferably about 0.05 to 0.5 μm. 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. Examples of 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.
　フィルタを使用する際、異なるフィルタを組み合わせてもよい。その際、第１のフィルタでのフィルタリングは、１回のみでもよいし、２回以上行ってもよい。
　また、上述した範囲内で異なる孔径の第１のフィルタを組み合わせてもよい。ここでの孔径は、フィルタメーカーの公称値を参照することができる。市販のフィルタとしては、例えば、日本ポール株式会社（ＤＦＡ４２０１ＮＸＥＹなど）、アドバンテック東洋株式会社、日本インテグリス株式会社（旧日本マイクロリス株式会社）又は株式会社キッツマイクロフィルタ等が提供する各種類のフィルタの中から選択することができる。
　第２のフィルタは、上述した第１のフィルタと同様の材料等で形成されたものを使用することができる。
　例えば、第１のフィルタでのフィルタリングは、分散液のみで行い、他の成分を混合した後で、第２のフィルタリングを行ってもよい。 When using filters, different filters may be combined. At that time, the filtering by the first filter may be performed only once or may be performed twice or more.
Moreover, you may combine the 1st filter of a different hole diameter within the range mentioned above. The pore diameter here can refer to the nominal value of the filter manufacturer. As commercially available 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.
As the second filter, a filter formed of the same material as the first filter described above can be used.
For example, the filtering by the first filter may be performed only with the dispersion, and the second filtering may be performed after mixing other components.
［膜］
　本発明の膜は、本発明の組成物を用いて形成された膜である。 [film]
The film of the present invention is a film formed using the composition of the present invention.
＜Ｌ＊＞
　本発明の膜は、ＣＩＥ１９７６のＬ＊ａ＊ｂ＊表色系におけるＬ＊が３５～８５であることが好ましい。膜は、ＣＩＥ１９７６のＬ＊ａ＊ｂ＊表色系におけるＬ＊の上限は８０未満であることがより好ましく、７５以下であることが特に好ましく、７０以下であることがより特に好ましい。膜は、ＣＩＥ１９７６のＬ＊ａ＊ｂ＊表色系におけるＬ＊の下限は４０以上であることがより好ましく、５０以上であることが特に好ましい。 <L *>
In the film 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＊およびｂ＊＞
　本発明の膜は、ＣＩＥ１９７６のＬ＊ａ＊ｂ＊表色系におけるａ＊およびｂ＊は－３０～３０が好ましく、－２０～２０がより好ましく、－１０～１０が特に好ましい。 <A * and b *>
In the film of the present invention, 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.
＜厚さ＞
　本発明の膜は、厚さが１０μｍ以下であることが好ましく、３μｍ以下であることがより好ましく、１μｍ以下であることが特に好ましい。厚さの下限値は、０．５μｍ以上であることが好ましい。 <Thickness>
The film of the present invention preferably has a thickness of 10 μm or less, more preferably 3 μm or less, and particularly preferably 1 μm or less. The lower limit value of the thickness is preferably 0.5 μm or more.
＜平均透過率＞
　本発明の膜は、厚さ３μｍの波長４００～７００ｎｍの範囲における平均透過率が１％以上であることが好ましく、１０％以上であることがより好ましく、３０％以上であることが特に好ましい。波長４００～７００ｎｍの範囲における平均透過率の上限値は、５０％以下であることが好ましい。 <Average transmittance>
In the film of the present invention, the average transmittance in a wavelength range of 400 to 700 nm with a thickness of 3 μm 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.
＜用途＞
　本発明の膜は、固体撮像素子などの各種類のセンサや、画像表示装置（例えば、液晶表示装置や有機エレクトロルミネッセンス（有機ＥＬ）表示装置など）に組み込んで用いることができる。また、光学部材の外観調整用途の材料として用いることもできる。
　本発明の膜は、例えば、各種類のセンサや、画像表示装置などに組み込んで、光を適度に遮光ないし透過する部材や、光を散乱する部材として用いることもできる。また、発光ダイオード（ＬＥＤ）反射用途、有機ＥＬ光散乱層用途、導電材料、絶縁材料、太陽電池用材料などに用いることもできる。 <Application>
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.
［硬化膜］
　本発明の硬化膜は、本発明の膜を硬化した、硬化膜である。硬化膜は、本発明の膜から溶剤を除去されたことが好ましい。また、硬化膜は、本発明の膜の重合性化合物を重合して硬化されたことが好ましい。
　本発明の硬化膜は、硬化膜の状態でＣＩＥ１９７６のＬ＊ａ＊ｂ＊表色系におけるＬ＊が３５～８５であることが好ましい。本発明の硬化膜は、硬化膜の状態でＣＩＥ１９７６のＬ＊ａ＊ｂ＊表色系におけるＬ＊の上限は８０未満であることがより好ましく、７５以下であることが特に好ましく、７０以下であることがより特に好ましい。本発明の硬化膜は、硬化膜の状態でＣＩＥ１９７６のＬ＊ａ＊ｂ＊表色系におけるＬ＊の下限は４０以上であることがより好ましく、５０以上であることが特に好ましい。
　本発明の硬化膜は、粒子と樹脂を含み、粒子が少なくとも波長５８９ｎｍの光に対する屈折率が２．１以上である粒子を含み、樹脂が少なくとも波長５８９ｎｍの光に対する屈折率が１．５以下である樹脂を含むことが好ましい。本発明の硬化膜における波長５８９ｎｍの光に対する屈折率の粒子の好ましい屈折率の範囲は、本発明の組成物における波長５８９ｎｍの光に対する屈折率の粒子の好ましい屈折率の範囲と同様である。また、本発明の硬化膜における波長５８９ｎｍの光に対する屈折率の樹脂の好ましい屈折率の範囲は、本発明の組成物における波長５８９ｎｍの光に対する屈折率の樹脂の好ましい屈折率の範囲と同様である。
　本発明の硬化膜は、粒子と樹脂を含み、粒子の波長５８９ｎｍの光に対する屈折率と、樹脂の波長５８９ｎｍの光に対する屈折率との差が１．２２以上であることが好ましく、１．２７以上であることがより好ましい。この範囲であると、硬化膜のＣＩＥ１９７６のＬ＊ａ＊ｂ＊表色系におけるＬ＊を高くしやすい。
　本発明の硬化膜の組成を、粒子と粒子以外の成分とに分類した場合、硬化膜の粒子以外の成分は、波長５８９ｎｍの光に対する屈折率（粒子以外の成分の屈折率の平均値と同義）が１．５以下であることが好ましく、１．００～１．４５であることがより好ましく、１．１０～１．４０であることがさらに好ましい。 [Curing film]
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.
In the cured 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. In the cured film of the present invention, 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. In the cured film of the present invention, 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.
When 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.
［光学センサ］
　本発明の光学センサは、本発明の硬化膜を有する光学センサである。光学センサとしては、固体撮像素子などを挙げることができる。 [Optical sensor]
The optical sensor of the present invention is an optical sensor having the cured film of the present invention. Examples of the optical sensor include a solid-state image sensor.
［膜の製造方法］
　本発明の膜の製造方法は、本発明の組成物を、パターンを有するマスクを介して露光する工程と、
　露光された組成物を現像してパターン形成する工程とを含む。 [Membrane production method]
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.
　本発明の組成物を、パターンを有するマスクを介して露光する工程の前に、本発明の組成物を基材などに適用して膜を形成する工程、膜を乾燥する工程を経ることが好ましい。膜厚、積層構造などについては、目的に応じて適宜選択することができる。 Before the step of exposing the composition of the present invention through a mask having a pattern, 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. . About a film thickness, laminated structure, etc., it can select suitably according to the objective.
　膜を形成する工程において、組成物の適用方法としては、公知の方法を用いることができる。例えば、滴下法（ドロップキャスト）；スリットコート法；スプレー法；ロールコート法；回転塗布法（スピンコーティング）；流延塗布法；スリットアンドスピン法；プリウェット法（たとえば、特開２００９－１４５３９５号公報に記載されている方法）；インクジェット（例えばオンデマンド方式、ピエゾ方式、サーマル方式）、ノズルジェット等の吐出系印刷、フレキソ印刷、スクリーン印刷、グラビア印刷、反転オフセット印刷、メタルマスク印刷法などの各種類の印刷法；金型等を用いた転写法；ナノインプリント法などが挙げられる。インクジェットを用いた適用方法としては、組成物を吐出可能であれば特に限定されず、例えば「広がる・使えるインクジェット－特許に見る無限の可能性－、２００５年２月発行、住ベテクノリサーチ」に示された特許公報に記載の方法（特に１１５ページ～１３３ページ）や、特開２００３－２６２７１６号公報、特開２００３－１８５８３１号公報、特開２００３－２６１８２７号公報、特開２０１２－１２６８３０号公報、特開２００６－１６９３２５号公報などにおいて、吐出する組成物を本発明の組成物に置き換える方法が挙げられる。スピンコート法での塗布は、塗布適性の観点から、３００～６０００ｒｐｍの範囲でスピン塗布することが好ましく、４００～３０００ｒｐｍの範囲でスピン塗布することが更に好ましい。また、スピンコート時における基材温度は、１０～１００℃が好ましく、２０～７０℃がより好ましい。上記の範囲であれば、塗布均一性に優れた膜を製造しやすい。 In the step of forming a film, a known method can be used as a method for applying the composition. For example, a dropping method (drop casting); a slit coating method; 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. For example, “Expanding and usable ink jet: Infinite possibilities seen in patents, published in February 2005, Sumibe Techno Research” 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. From the viewpoint of coating suitability, 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 | membrane excellent in the coating uniformity.
　滴下法（ドロップキャスト）の場合、所定の膜厚で、均一な膜が得られるように、基材上にフォトレジストを隔壁とする組成物の滴下領域を形成することが好ましい。組成物の滴下量および固形分濃度、滴下領域の面積を制御することで、所望の膜厚が得られる。乾燥後の膜の厚みとしては、特に制限はなく、目的に応じて適宜選択することができる。 In the case of the dropping method (drop casting), it is preferable to form 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. There is no restriction | limiting in particular as thickness of the film | membrane after drying, According to the objective, it can select suitably.
　基材としては、特に限定は無く、用途に応じて適宜選択できる。例えば、液晶表示装置等に用いられる無アルカリガラス、ソーダガラス、パイレックス（登録商標）ガラス、石英ガラス、及びこれらに透明導電膜を付着させた基材、固体撮像素子等に用いられる光電変換素子基材、シリコン基材等、相補性金属酸化膜半導体（ＣＭＯＳ）等が挙げられる。また、これらの基材上には、必要により、上部の層との密着改良、物質の拡散防止あるいは表面の平坦化のために下塗り層を設けてもよい。 The substrate is not particularly limited and can be appropriately selected depending on the application. For example, 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. In addition, 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.
　膜を乾燥する工程において、乾燥条件としては、各成分、溶剤の種類、使用割合等によっても異なる。例えば、６０～１５０℃の温度で、３０秒間～１５分間が好ましい。 In the process of drying the film, the drying conditions vary depending on each component, the type of solvent, the use ratio, and the like. For example, the temperature is preferably 60 to 150 ° C. and preferably 30 seconds to 15 minutes.
　本発明の組成物を、パターンを有するマスクを介して露光する工程と、露光された組成物を現像してパターン形成する工程としては、例えば、本発明の組成物を基材上に適用して膜状の組成物層を形成する工程と、組成物層をパターン形状に露光する工程と、未露光部を現像除去してパターンを形成する工程とを含む方法などが挙げられる。パターンを形成する工程としては、フォトリソグラフィ法でパターン形成してもよいし、ドライエッチング法でパターンを形成してもよい。 As the step of exposing the composition of the present invention through a mask having a pattern and the step of developing the exposed composition to form a pattern, for example, 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. As a pattern forming step, a pattern may be formed by a photolithography method, or a pattern may be formed by a dry etching method.
　露光工程では、基材上に形成された膜をパターン形状に露光することが好ましい。例えば、基材上の膜に対し、ステッパー等の露光装置を用いて、所定のマスクパターンを有するマスクを介して露光することで、パターン露光することができる。これにより、露光部分を硬化することができる。
　露光に際して用いることができる放射線（光）としては、ｇ線、ｉ線等の紫外線が好ましく（特に好ましくはｉ線）用いられる。照射量（露光量）は、例えば、０．０３～２．５Ｊ／ｃｍ2が好ましく、０．０５～１．０Ｊ／ｃｍ2がより好ましい。
　露光時における酸素濃度については適宜選択することができ、大気下で行う他に、例えば酸素濃度が１９体積％以下の低酸素雰囲気下（例えば、１５体積％以下、さらには５体積％以下、特には実質的に無酸素）で露光してもよく、酸素濃度が２１体積％を超える高酸素雰囲気下（例えば、２２体積％以上、さらには３０体積％以上、特には５０体積％以上）で露光してもよい。また、露光照度は適宜設定することが可能であり、通常１０００Ｗ／ｍ2～１０００００Ｗ／ｍ2（例えば、５０００Ｗ／ｍ2以上、さらには１５０００Ｗ／ｍ2以上、特には３５０００Ｗ／ｍ2以上）の範囲から選択することができる。酸素濃度と露光照度は適宜条件を組み合わせてよく、例えば、酸素濃度１０体積％で照度１００００Ｗ／ｍ2、酸素濃度３５体積％で照度２００００Ｗ／ｍ2などとすることができる。 In the exposure step, it is preferable to expose the film formed on the substrate into a pattern shape. For example, 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.
As radiation (light) that can be used for exposure, ultraviolet rays such as g-line and i-line are preferable (particularly preferably i-line). Irradiation dose (exposure dose), for example, preferably 0.03 ~ 2.5J / cm 2, more preferably 0.05 ~ 1.0J / cm 2.
The oxygen concentration at the time of exposure can be appropriately selected. In addition to being performed in the air, for example, in 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) and exposed in 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). May be. 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.
　次に、未露光部を現像除去してパターンを形成することが好ましい。未露光部の現像除去は、現像液を用いて行うことができる。これにより、露光工程における未露光部の組成物層が現像液に溶出し、光硬化した部分だけが残る。現像液としては、下地の回路などにダメージを起さない、アルカリ現像液が望ましい。現像液として、本明細書に記載の溶剤を用いて現像してもよい。現像液の温度は、例えば、２０～３０℃が好ましい。現像時間は、２０～１８０秒間が好ましく、２０～９０秒間がより好ましい。 Next, it is preferable to develop and remove the unexposed portion to form a pattern. The development removal of the unexposed portion can be performed using a developer. Thereby, the composition layer of the unexposed part in an exposure process elutes in a developing solution, and only the photocured part remains. 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.
　アルカリ現像液に用いるアルカリ剤としては、例えば、アンモニア水、エチルアミン、ジエチルアミン、ジメチルエタノールアミン、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド、ベンジルトリメチルアンモニウムヒドロキシド、コリン、ピロール、ピペリジン、１，８－ジアザビシクロ［５，４，０］－７－ウンデセン、ジメチルビス（２－ヒドロキシエチル）アンモニウムヒドロキシドなどの有機アルカリ性化合物が挙げられる。これらのアルカリ剤を濃度が０．００１～１０質量％、好ましくは０．０１～１質量％となるように純水で希釈したアルカリ性水溶液が現像液として好ましく使用される。
　また、現像液には無機アルカリを用いてもよい。無機アルカリとしては、例えば、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸水素ナトリウム、硅酸ナトリウム、メタ硅酸ナトリウムなどが好ましい。
　また、現像液には、界面活性剤を用いてもよい。界面活性剤の例としては、上述した組成物で説明した界面活性剤が挙げられ、ノニオン系界面活性剤が好ましい。
　なお、このようなアルカリ性水溶液からなる現像液を使用した場合には、一般に現像後純水で洗浄（リンス）することが好ましい。 Examples of the alkaline agent used in the alkaline developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxy. And organic alkaline compounds such as 1,8-diazabicyclo [5,4,0] -7-undecene, dimethylbis (2-hydroxyethyl) ammonium hydroxide. An alkaline aqueous solution obtained by diluting these alkaline agents with pure water so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass, is preferably used as the developer.
Moreover, you may use an inorganic alkali for a developing solution. As the inorganic alkali, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, sodium metasuccinate and the like are preferable.
Further, 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.
In addition, when using the developing solution which consists of such alkaline aqueous solution, generally it is preferable to wash | clean (rinse) with a pure water after image development.
　その他の工程を含んでいても良い。その他の工程としては、特に制限はなく、目的に応じて適宜選択することができる。例えば、基材の表面処理工程、前加熱工程（プリベーク工程）、後加熱工程（ポストベーク工程）などが挙げられる。現像後に、更に、加熱および露光のうち少なくとも一方を行ってもよい。この態様によれば、膜の硬化をさらに進行して、より強固に硬化した膜を製造できる。 ) Other processes may be included. There is no restriction | limiting in particular as another process, According to the objective, it can select suitably. For example, the surface treatment process of a base material, a pre-heating process (pre-baking process), a post-heating process (post-baking process), etc. are mentioned. After development, at least one of heating and exposure may be further performed. According to this aspect, the film can be further cured to produce a film that is more firmly cured.
　前加熱工程および後加熱工程における加熱温度は、８０～２００℃が好ましい。上限は１５０℃以下がより好ましい。下限は９０℃以上がより好ましい。また、前加熱工程および後加熱工程における加熱時間は、３０～２４０秒間が好ましい。上限は１８０秒間以下がより好ましい。下限は６０秒間以上がより好ましい。 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.
　加熱処理の方法としては、形成された上記膜の全面を加熱する方法が挙げられる。加熱処理により、パターンの膜強度が高められる。加熱温度は、１００～２６０℃が好ましい。下限は１２０℃以上がより好ましく、１６０℃以上が特に好ましい。上限は２４０℃以下がより好ましく、２２０℃以下が特に好ましい。加熱温度が上記範囲であれば、強度に優れた膜が得られやすい。加熱時間は、１～１８０分間が好ましい。下限は３分間以上がより好ましい。上限は１２０分間以下がより好ましい。加熱装置としては、特に制限はなく、公知の装置の中から、目的に応じて適宜選択することができ、例えば、ドライオーブン、ホットプレート、赤外線ヒータなどが挙げられる。 As 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. When the heating temperature is in the above range, a film having excellent strength is easily obtained. 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. There is no restriction | 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.
　以下、本発明を実施例により具体的に説明するが、本発明はこれらの実施例に限定されない。なお、特に断りのない限り、「部」及び「％」は質量基準である。
　粘度は、Ｅ型粘度計（東機産業製ＲＥ８５Ｌ）、コーンローターとして１°３４’×Ｒ２４を用いて、回転数５ｒｐｍの条件で測定した。なお、前述の条件で測定できない場合は、適宜、回転数を変更して測定した。 EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples. Unless otherwise specified, “part” and “%” are based on mass.
The viscosity was measured using an E-type viscometer (RE85L manufactured by Toki Sangyo Co., Ltd.) and 1 ° 34 ′ × R24 as a cone rotor under the condition of 5 rpm. In addition, when it was not possible to measure under the above-mentioned conditions, the measurement was performed by appropriately changing the rotation speed.
＜重量平均分子量の測定＞
　樹脂の重量平均分子量は、以下の方法で測定した。
カラムの種類：ＴＯＳＯＨ　ＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺＭ－Ｈと、ＴＯＳＯＨ　ＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺ４０００と、ＴＯＳＯＨ　ＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺ２０００とを連結したカラム
展開溶媒：テトラヒドロフラン
カラム温度：４０℃
流量（サンプル注入量）：１．０μＬ（サンプル濃度：０．１質量％）
装置名：東ソー（株）製　ＨＬＣ－８２２０ＧＰＣ
検出器：ＲＩ（屈折率）検出器
検量線ベース樹脂：ポリスチレン <Measurement of weight average molecular weight>
The weight average molecular weight of the resin was measured by the following method.
Column type: TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, and TOSOH TSKgel Super HZ2000 linked column developing solvent: Tetrahydrofuran Column temperature: 40 ° C
Flow rate (sample injection amount): 1.0 μL (sample concentration: 0.1% by mass)
Device name: HLC-8220GPC manufactured by Tosoh Corporation
Detector: RI (refractive index) detector Calibration curve Base resin: Polystyrene
＜酸価の測定方法＞
　酸価は、固形分１ｇあたりの酸性成分を中和するのに要する水酸化カリウムの質量を表したものである。測定サンプルをテトラヒドロフラン／水＝９／１（質量比）混合溶媒に溶解し、電位差滴定装置（商品名：ＡＴ－５１０、京都電子工業製）を用いて、得られた溶液を、２５℃にて、０．１ｍｏｌ／Ｌ水酸化ナトリウム水溶液で中和滴定した。滴定ｐＨ曲線の変曲点を滴定終点として、次式により酸価を算出した。
　Ａ＝５６．１１×Ｖｓ×０．５×ｆ／ｗ
　Ａ：酸価（ｍｇＫＯＨ／ｇ）
　Ｖｓ：滴定に要した０．１ｍｏｌ／Ｌ水酸化ナトリウム水溶液の使用量（ｍＬ）
　ｆ：０．１ｍｏｌ／Ｌ水酸化ナトリウム水溶液の力価
　ｗ：測定サンプル質量（ｇ）（固形分換算） <Method for measuring acid value>
The acid value represents the mass of potassium hydroxide required to neutralize acidic components per gram of solid content. The measurement sample was dissolved in a tetrahydrofuran / water = 9/1 (mass ratio) mixed solvent, and the obtained solution was obtained at 25 ° C. using a potentiometric titrator (trade name: AT-510, manufactured by Kyoto Electronics Industry Co., Ltd.). And neutralization titration with 0.1 mol / L sodium hydroxide aqueous solution. 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
A: Acid value (mgKOH / g)
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)
＜アミン価の測定＞
　アミン価は、固形分１ｇあたりの塩基性成分と当量の水酸化カリウム（ＫＯＨ）の質量で表したものである。測定サンプルを酢酸に溶解し、電位差滴定装置（商品名：ＡＴ－５１０、京都電子工業製）を用いて、得られた溶液を、２５℃にて、０．１ｍｏｌ／Ｌ過塩素酸／酢酸溶液で中和滴定した。滴定ｐＨ曲線の変曲点を滴定終点として次式によりアミン価を算出した。
　Ｂ＝５６．１１×Ｖｓ×０．１×ｆ／ｗ
　Ｂ：アミン価（ｍｇＫＯＨ／ｇ）
　Ｖｓ：滴定に要した０．１ｍｏｌ／Ｌ過塩素酸／酢酸溶液の使用量（ｍＬ）
　ｆ：０．１ｍｏｌ／Ｌ過塩素酸／酢酸溶液の力価
　ｗ：測定サンプルの質量（ｇ）（固形分換算） <Measurement of amine value>
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.
B = 56.11 × Vs × 0.1 × f / w
B: 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 w: mass (g) of measurement sample (in solid content)
＜粒子の平均一次粒子径の測定＞
　粉体粒子の一次粒子径を、透過型電子顕微鏡（ＴＥＭ）で観察し、粒子が凝集していない部分を観測することで求めた。また、粒子の粒度分布について、一次粒子である粉体粒子を、透過型電子顕微鏡を用いて透過型電子顕微鏡写真を撮影した後、その写真を用いて画像処理装置で粒度分布を測定した。粒子の平均一次粒子径は、粒度分布から算出された個数基準の算術平均径をもって平均一次粒子径とした。透過型電子顕微鏡として（株）日立製作所製電子顕微鏡（Ｈ－７０００）を用い、画像処理装置として（株）ニレコ製ルーゼックスＡＰを用いた。 <Measurement of average primary particle diameter of particles>
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 | grains, after taking the transmission electron micrograph of the powder particle which is a primary particle using the transmission electron microscope, the particle size distribution was measured with the image processing apparatus using the photograph. 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.
［実施例１～４４、比較例１～３］
＜分散液の製造＞
　下記組成の混合液に対し、循環型分散装置（ビーズミル）として、寿工業（株）製ウルトラアペックスミルを用いて、以下のようにして分散処理を行い、分散液を製造した。
＜＜混合液の組成＞＞
　下記表に記載の粒子：３０質量部
　下記表に記載の分散剤：下記表に記載の量
　溶剤：プロピレングリコール－１－モノメチルエーテル－２－アセテート（ＰＧＭＥＡ）：下記表に記載の量 [Examples 1 to 44, Comparative Examples 1 to 3]
<Manufacture of dispersion>
Dispersion treatment was carried out as follows using a Ultra Apex mill manufactured by Kotobuki Kogyo Co., Ltd. as a circulation type dispersion device (bead mill) for a mixed solution having the following composition.
<< Composition of liquid mixture >>
Particles listed in the table below: 30 parts by mass Dispersant listed in the table below: Amount listed in the table below Solvent: Propylene glycol-1-monomethyl ether-2-acetate (PGMEA): Amount listed in the table below
　また、循環型分散装置は以下の条件で運転した。
・ビーズ径：直径０．２ｍｍ
・ビーズ充填率：６５体積％
・周速：６ｍ／秒
・ポンプ供給量：１０．８ｋｇ／時
・冷却水：水道水
・ビーズミル環状通路内容積：０．１５Ｌ
・分散処理する混合液量：０．６５ｋｇ 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
　分散開始後、３０分間隔で、粒子の平均粒子径の測定を行った。粒子の平均粒子径は分散時間とともに減少したが、次第にその変化量が少なくなった。粒度分布におけるｄ５０（積算値５０％）の変化量がなくなった時点で分散を終了した。
　得られた分散液２～１９の組成を下記表に示す。 After the start of dispersion, 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.
Figure JPOXMLDOC01-appb-T000041
Figure JPOXMLDOC01-appb-T000041
（粒子）
　Ｂ－２～Ｂ－１３として、以下の表に示す粒子を用いた。
Figure JPOXMLDOC01-appb-T000042
 (particle)
As B-2 to B-13, particles shown in the following table were used.
Figure JPOXMLDOC01-appb-T000042
　粒子の屈折率は以下の方法で測定される。
　まず、屈折率が既知である分散剤とＰＧＭＥＡを用いて分散を行う。その後、作製した分散液と屈折率が既知の樹脂を、粒子の固形分中の濃度がそれぞれ１０質量％、２０質量％、３０質量％、４０質量％になるように混合し、４種類の塗布液を作製する。これらの塗布液をＳｉウェハ上に３００ｎｍで製膜した後、得られる膜の屈折率をエリプソメトリー（ラムダエースＲＥ－３３００（商品名）、大日本スクリーン製造（株））を用いて測定する。その後、粒子濃度と屈折率をプロットし、外挿し、粒子の屈折率を導出する。 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.
（分散剤）
Ｆ－１：Ｓｏｌｓｐｅｒｓｅ　３６０００、Ｌｕｂｒｉｚｏｌ（株）製、屈折率１．５２。
Ｆ－２：Ｓｏｌｓｐｅｒｓｅ　４６０００、Ｌｕｂｒｉｚｏｌ（株）製、屈折率１．５２。
Ｆ－３：下記構造の樹脂（Ｍｗ＝２００００、屈折率１．５１）。各繰り返し単位に併記した数値は、各繰り返し単位の含有量〔質量比〕を表す。側鎖の繰り返し部位に併記される数値は、繰り返し部位の繰り返し数を示す。
Ｆ－４：下記構造の樹脂（Ｍｗ＝２２９００、屈折率１．５１）。各繰り返し単位に併記した数値は、各繰り返し単位の含有量〔質量比〕を表す。側鎖の繰り返し部位に併記される数値は、繰り返し部位の繰り返し数を示す。
Ｆ－５：ポリシロキサン樹脂系分散剤であるＸ－２２－３７０１Ｅ（酸性吸着基を持つポリアルキルシロキサン）、信越シリコーン製、屈折率１．４３。
Figure JPOXMLDOC01-appb-C000043
 (Dispersant)
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-3: Resin having the following structure (Mw = 20000, refractive index 1.51). The numerical value written together with each repeating unit represents content [mass ratio] of each repeating unit. The numerical value written together with the repeating part of the side chain indicates the number of repeating parts.
F-4: Resin having the following structure (Mw = 22900, refractive index 1.51). The numerical value written together with each repeating unit represents content [mass ratio] of each repeating unit. The numerical value written together with the repeating part of the side chain indicates the number of repeating parts.
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.
Figure JPOXMLDOC01-appb-C000043
＜組成物の調製＞
　下記表に記載の原料を混合して、組成物を調製した。
<Preparation of composition>
The raw materials described in the following table were mixed to prepare a composition.
Figure JPOXMLDOC01-appb-T000045
Figure JPOXMLDOC01-appb-T000045
Figure JPOXMLDOC01-appb-T000046
Figure JPOXMLDOC01-appb-T000046
Figure JPOXMLDOC01-appb-T000047
Figure JPOXMLDOC01-appb-T000047
＜＜原料＞＞
　上記表に記載の原料は以下である。
（分散液）
　分散液２～１９：上記にて製造した分散液２～１９。 << Raw material >>
The raw materials described in the above table are as follows.
(Dispersion)
Dispersions 2-19: Dispersions 2-19 produced above.
（樹脂）
Ａ－１：前述のフッ素系樹脂１であるフッ素系樹脂（酸価１１４．１ｍｇＫＯＨ／ｇ、ＭＷ＝１００００、下記構造）。
Figure JPOXMLDOC01-appb-C000048
 (resin)
A-1: Fluorine resin (acid value 114.1 mgKOH / g, MW = 10000, the following structure) which is the above-mentioned fluorine resin 1.
Figure JPOXMLDOC01-appb-C000048
Ａ－２：前述の具体例５３であるポリシロキサン系樹脂（Ｍｗ＝１００００）。ＷＯ２０１４／１２６０１３Ａの＜０１１７＞の合成例１１および＜０１０７＞の合成例１を参考にして、以下の手順にしたがって合成した。この公報の内容は本明細書に組み込まれる。
　５００ｍＬのナスフラスコに下記材料を仕込んで、室温で撹拌しながら２ｇのリン酸を５４ｇの水で溶かした水溶液を３０分間かけて滴下した。その後４０℃で３０分間撹拌した後、７０℃で３０分間撹拌した。最後に１１０℃で３時間加熱し、反応を終了した。溶媒はエバポレータで取り除いた。
－材料－
ジメトキシジメチルシラン　７５質量部（６２．６モル％）
３－アクリロキシプロピルトリメトキシシラン　４２質量部（１７．９モル％）
３－トリメトキシシリルプロピル無水コハク酸　３９質量部（１５モル％）
３－グリシジロキシプロピルトリメトキシシラン　１２質量部（４．５モル％）
ＰＧＭＥＡ　１０９質量部 A-2: Polysiloxane resin (Mw = 10000) which is the specific example 53 described above. 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 solvent was removed with an evaporator.
-material-
75 parts by mass of dimethoxydimethylsilane (62.6 mol%)
3-Acryloxypropyltrimethoxysilane 42 parts by mass (17.9 mol%)
3-Trimethoxysilylpropyl succinic anhydride 39 parts by mass (15 mol%)
3-glycidyloxypropyltrimethoxysilane 12 parts by mass (4.5 mol%)
109 parts by weight of PGMEA
Ａ－３：前述の具体例５４であるポリシロキサン系樹脂（Ｍｗ＝１００００）。材料を以下のとおりに変更した以外はＡ－２と同様の方法で合成した。
－材料－
ジメトキシジメチルシラン　８４質量部（７０モル％）
３－アクリロキシプロピルトリメトキシシラン　４７質量部（２０モル％）
３－トリメトキシシリルプロピル無水コハク酸　１３質量部（５モル％）
３－グリシジロキシプロピルトリメトキシシラン　１４質量部（５モル％）
ＰＧＭＥＡ　１０２質量部 A-3: Polysiloxane resin (Mw = 10000) which is the specific example 54 described above. Synthesis was performed in the same manner as in A-2 except that the materials were changed as follows.
-material-
84 parts by mass (70 mol%) of dimethoxydimethylsilane
3-Acryloxypropyltrimethoxysilane 47 parts by mass (20 mol%)
3-Trimethoxysilylpropyl succinic anhydride 13 parts by mass (5 mol%)
3-glycidyloxypropyltrimethoxysilane 14 parts by mass (5 mol%)
102 parts by mass of PGMEA
Ａ－４：前述の具体例５５であるポリシロキサン系樹脂（Ｍｗ＝１００００）。材料を以下のとおりに変更した以外はＡ－２と同様の方法で合成した。
－材料－
ジメトキシジメチルシラン　８０質量部（６６．３モル％）
３－アクリロキシプロピルトリメトキシシラン　４４質量部（１９モル％）
３－トリメトキシシリルプロピル無水コハク酸　２６質量部（１０モル％）
３－グリシジロキシプロピルトリメトキシシラン　１３質量部（４．７モル％）
ＰＧＭＥＡ　１０６質量部 A-4: Polysiloxane resin (Mw = 10000) which is the specific example 55 described above. Synthesis was performed in the same manner as in A-2 except that the materials were changed as follows.
-material-
80 parts by mass (66.3 mol%) of dimethoxydimethylsilane
44 parts by mass (19 mol%) of 3-acryloxypropyltrimethoxysilane
26 parts by mass (10 mol%) of 3-trimethoxysilylpropyl succinic anhydride
3-glycidyloxypropyltrimethoxysilane 13 parts by mass (4.7 mol%)
106 parts by mass of PGMEA
Ａ－５：前述の具体例５６であるポリシロキサン系樹脂（Ｍｗ＝１００００）。材料を以下のとおりに変更した以外はＡ－２と同様の方法で合成した。
－材料－
ジメトキシジメチルシラン　７１質量部（５９モル％）
３－アクリロキシプロピルトリメトキシシラン　３９質量部（１６．８モル％）
３－トリメトキシシリルプロピル無水コハク酸　５２質量部（２０モル％）
３－グリシジロキシプロピルトリメトキシシラン　１２質量部（４．２モル％）
ＰＧＭＥＡ　１１３質量部 A-5: Polysiloxane resin (Mw = 10000) which is the above-described specific example 56. Synthesis was performed in the same manner as in A-2 except that the materials were changed as follows.
-material-
Dimethoxydimethylsilane 71 parts by mass (59 mol%)
39 parts by mass (16.8 mol%) of 3-acryloxypropyltrimethoxysilane
3-trimethoxysilylpropyl succinic anhydride 52 parts by mass (20 mol%)
3-glycidyloxypropyltrimethoxysilane 12 parts by mass (4.2 mol%)
PGMEA 113 parts by mass
Ａ－６：前述の具体例５７であるポリシロキサン系樹脂（Ｍｗ＝１００００）。材料を以下のとおりに変更した以外はＡ－２と同様の方法で合成した。
－材料－
ジメトキシジメチルシラン　６６質量部（５５．３モル％）
３－アクリロキシプロピルトリメトキシシラン　３７質量部（１５．８モル％）
３－トリメトキシシリルプロピル無水コハク酸　６６質量部（２５モル％）
３－グリシジロキシプロピルトリメトキシシラン　１１質量部（３．９モル％）
ＰＧＭＥＡ　１１７質量部 A-6: Polysiloxane resin (Mw = 10000) which is the specific example 57 described above. Synthesis was performed in the same manner as in A-2 except that the materials were changed as follows.
-material-
66 parts by mass (55.3 mol%) of dimethoxydimethylsilane
37 parts by mass (15.8 mol%) of 3-acryloxypropyltrimethoxysilane
3-Trimethoxysilylpropyl succinic anhydride 66 parts by mass (25 mol%)
11 parts by mass (3.9 mol%) of 3-glycidyloxypropyltrimethoxysilane
117 parts by mass of PGMEA
Ａ－７：前述の具体例５８であるポリシロキサン系樹脂（Ｍｗ＝１００００。材料を以下のとおりに変更した以外はＡ－２と同様の方法で合成した。
－材料－
ジメトキシジメチルシラン　４１質量部（８０．０モル％）
３－トリメトキシシリルプロピル無水コハク酸　３６質量部（１５．０モル％）
３－グリシジロキシプロピルトリメトキシシラン　１６質量部（５．０モル％）
ＰＧＭＥＡ　１２９．９３質量部 A-7: Polysiloxane-based resin (Mw = 10000) which is the above-described specific example 58 (synthesized by the same method as A-2 except that the materials were changed as follows).
-material-
41 parts by mass (80.0 mol%) of dimethoxydimethylsilane
3-Trimethoxysilylpropyl succinic anhydride 36 parts by mass (15.0 mol%)
3-glycidyloxypropyltrimethoxysilane 16 parts by mass (5.0 mol%)
PGMEA 129.93 parts by mass
Ａ－８：前述の具体例５９であるポリシロキサン系樹脂（Ｍｗ＝１００００）。材料を以下のとおりに変更した以外はＡ－２と同様の方法で合成した。
－材料－
ジメトキシジメチルシラン　３４質量部（５５．０モル％）
３－アクリロキシプロピルトリメトキシシラン　４４質量部（２０．０モル％）
３－トリメトキシシリルプロピル無水コハク酸　２９質量部（１５．０モル％）
３－グリシジロキシプロピルトリメトキシシラン　１０質量部（５．０モル％）
テトラエトキシシラン　１０質量部（５．０モル％）
ＰＧＭＥＡ　１３６．７２質量部 A-8: Polysiloxane resin (Mw = 10000) which is the specific example 59 described above. Synthesis was performed in the same manner as in A-2 except that the materials were changed as follows.
-material-
34 parts by mass of dimethoxydimethylsilane (55.0 mol%)
44 parts by mass (20.0 mol%) of 3-acryloxypropyltrimethoxysilane
29 parts by mass (15.0 mol%) of 3-trimethoxysilylpropyl succinic anhydride
3-glycidyloxypropyltrimethoxysilane 10 parts by mass (5.0 mol%)
10 parts by mass of tetraethoxysilane (5.0 mol%)
PGMEA 136.72 parts by mass
　Ａ－１０：下記構造のメタクリル系樹脂（酸価７９．３ｍｇＫＯＨ／ｇ、Ｍｗ＝１７０００、藤倉化成（株）製）。各繰り返し単位に併記した数値は、各繰り返し単位の含有量〔質量比〕を表す。
Figure JPOXMLDOC01-appb-C000049
 A-10: Methacrylic resin having the following structure (acid value: 79.3 mg KOH / g, Mw = 17000, manufactured by Fujikura Kasei Co., Ltd.). The numerical value written together with each repeating unit represents content [mass ratio] of each repeating unit.
Figure JPOXMLDOC01-appb-C000049
　各樹脂の屈折率を、本明細書中に記載の方法で、未硬化の状態で測定した。 The refractive index of each resin was measured in an uncured state by the method described in this specification.
（エチレン性不飽和結合を有する重合性化合物）
　Ｄ－１：多官能アクリレート、ＮＫエステル　Ａ－ＴＭＭＴ（新中村化学工業（株）製、屈折率１．５１）
　Ｄ－２：Ｓｉ原子含有の多官能ビニル化合物、ＶＩＮＹＬＴＲＩＩＳＯＰＲＯＰＥＮＯＸＹＳＩＬＡＮＥ（アズマックス株式会社製、屈折率１．４４） (Polymerizable compound having an ethylenically unsaturated bond)
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)
（重合開始剤）
　Ｅ－１：トリハロメチルトリアジン化合物（トリクロロメチルトリアジン化合物）である光重合開始剤、トリアジンＰＰ（ＢＡＳＦ製）
　Ｅ－２：オキシムエステル系の光重合開始剤、ＩＲＧＡＣＵＲＥ　ＯＸＥ０１（ＢＡＳＦ製） (Polymerization initiator)
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)
（溶剤）
　ＰＧＭＥＡ：プロピレングリコール－１－モノメチルエーテル－２－アセテート (solvent)
PGMEA: Propylene glycol-1-monomethyl ether-2-acetate
（着色防止剤）
　Ｇ－１：チオエーテル系の着色防止剤、アデカスタブ　ＡＯ－４１２Ｓ（（株）ＡＤＥＫＡ製）、下記構造。
　Ｇ－２：フェノール系の着色防止剤、アデカスタブ　ＡＯ－８０（（株）ＡＤＥＫＡ製）、下記構造。
Figure JPOXMLDOC01-appb-C000050
 (Anti-coloring agent)
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.
Figure JPOXMLDOC01-appb-C000050
（エポキシ基を有する化合物）
　Ｈ－１：ＥＨＰＥ３１５０（（株）ダイセル製） (Compound having an epoxy group)
H-1: EHPE3150 (manufactured by Daicel Corporation)
（紫外線吸収剤）
　Ｉ－１：特開２００９－２１７２２１号公報の化合物ＩＩＩ、下記構造。
Figure JPOXMLDOC01-appb-C000051
 (UV absorber)
I-1: Compound III of JP 2009-217221 A, the following structure.
Figure JPOXMLDOC01-appb-C000051
（密着剤）
　Ｊ－１：特開２００９－２８８７０３号公報の化合物Ｃ、下記構造。
Figure JPOXMLDOC01-appb-C000052
 (Adhesive)
J-1: Compound C of JP 2009-288703 A, the following structure.
Figure JPOXMLDOC01-appb-C000052
［評価］
＜Ｌ＊＞
　上記で得られた各組成物を、下塗り層（富士フイルムエレクトロニクスマテリアルズ（株）製ＣＴ－４０００Ｌ；膜厚０．１μｍ）付き８インチ（１インチは２．５４ｃｍである）ガラスウェハ上に乾燥後の膜厚が３．０μｍになるようにスピンコータを用いて塗布し、１１０℃のホットプレートを用いて１２０秒間加熱処理（プリベーク）を行った。
　次いで、ｉ線ステッパー露光装置ＦＰＡ－３０００ｉ５＋（Ｃａｎｏｎ（株）製）を使用して、３６５ｎｍの波長光を１０００ｍＪ／ｃｍ2にて、２ｃｍ×２ｃｍのパターンを有するマスクを介して露光した。
　その後、露光された塗布膜が形成されているガラスウェハをスピンシャワー現像機（ＤＷ－３０型、（株）ケミトロニクス製）の水平回転テーブル上に載置し、水酸化テトラメチルアンモニウム（ＴＭＡＨ）の０．３質量％水溶液を用い、２３℃で６０秒間パドル現像を行い、ガラスウェハ上に白色パターンを形成した。
　白色パターンが形成されたガラスウェハを真空チャック方式で水平回転テーブルに固定し、回転装置によってガラスウェハを回転数５０ｒｐｍで回転させつつ、その回転中心の上方より純水を噴出ノズルからシャワー状に供給してリンス処理を行い、その後スプレー乾燥した。本明細書中、Ｌ＊は、膜に含まれる溶剤が１質量％以下になった状態で測定する。
　分光測光器Ｘ－ｒｉｔｅ５２８（商品名、Ｘ－ｒｉｔｅ社製）を用いて、測定条件をＤ６５光源、観測視野を２°、白色基準はＸ－ｒｉｔｅ５２８（商品名、Ｘ－ｒｉｔｅ社製）に付属のキャリブレーション基準板のホワイトパッチを用いて、得られた白色パターンを測定した。ＣＩＥ１９７６のＬ＊ａ＊ｂ＊表色系におけるＬ＊値を、以下の基準で評価した。Ａ、ＢまたはＣの評価であれば実用上問題ないと判断する。ＡまたはＢの評価であることが好ましく、Ａの評価であることがより好ましい。得られた結果を下記表に記載した。
　Ａ：厚さ３．０μｍの膜を形成した場合のＣＩＥ１９７６のＬ＊ａ＊ｂ＊表色系におけるＬ＊が５０以上７５以下である。
　Ｂ：厚さ３．０μｍの膜を形成した場合のＣＩＥ１９７６のＬ＊ａ＊ｂ＊表色系におけるＬ＊が４０以上５０未満または７５を超え８０以下である。
　Ｃ：厚さ３．０μｍの膜を形成した場合のＣＩＥ１９７６のＬ＊ａ＊ｂ＊表色系におけるＬ＊が３５以上４０未満または８０を超え８５以下である。
　Ｄ：厚さ３．０μｍの膜を形成した場合のＣＩＥ１９７６のＬ＊ａ＊ｂ＊表色系におけるＬ＊が２０以上３５未満または８５を超え９０以下である。
　Ｅ：厚さ３．０μｍの膜を形成した場合のＣＩＥ１９７６のＬ＊ａ＊ｂ＊表色系におけるＬ＊が２０未満または９０を超える。
　なお、各組成物を用いて厚さ３．０μｍの膜を形成した場合のＣＩＥ１９７６のＬ＊ａ＊ｂ＊表色系におけるａ＊およびｂ＊は、下記以外の実施例の組成物を用いた場合は－１０以上１０以下であり、実施例２２、２９、３０の組成物を用いた場合は－２０以上－１０未満または１０を超え２０以下であり、実施例２１～２４の組成物を用いた場合は－３０以上－２０未満または２０を超え３０以下であった。 [Evaluation]
<L *>
Each composition obtained above was dried on an 8-inch (1 inch is 2.54 cm) glass wafer with an undercoat layer (CT-4000L manufactured by FUJIFILM Electronics Materials Co., Ltd .; film thickness 0.1 μm). The subsequent coating was applied using a spin coater so that the film thickness was 3.0 μm, and a heat treatment (prebaking) was performed for 120 seconds using a 110 ° C. hot plate.
Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), exposure was performed through a mask having a pattern of 2 cm × 2 cm at a wavelength of 365 nm at 1000 mJ / cm 2 .
Thereafter, 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. In this specification, L * is measured in a state where the solvent contained in the film is 1% by mass or less.
Using a spectrophotometer X-rite 528 (trade name, manufactured by X-rite), 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 μm 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 μm is formed is 40 or more and less than 50 or more than 75 and 80 or less.
C: L * in the L * a * b * color system of CIE 1976 when a film having a thickness of 3.0 μm is formed is 35 or more and less than 40 or more than 80 and 85 or less.
D: L * in the L * a * b * color system of CIE 1976 when a film having a thickness of 3.0 μm is formed is 20 or more and less than 35 or more than 85 and 90 or less.
E: L * in the L * a * b * color system of CIE 1976 when a film having a thickness of 3.0 μm is formed is less than 20 or more than 90.
The a * and b * in the L * a * b * color system of CIE 1976 when a film having a thickness of 3.0 μm was formed using each composition was a composition of an example other than the following. -10 or more and 10 or less, and when the 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.
＜一ヶ月経時後の濃度ムラ＞
　上記で得られた各組成物を用いて、常温（２３℃）の条件で１ヶ月経時させた。１ヶ月経時した各組成物を用いてＬ＊の測定方法と同様に白色パターンを作製した。その後、白色パターンの面内におけるＬ＊の最大値と最小値の差を測定し、以下の基準で評価した。Ａ、ＢまたはＣの評価であれば実用上問題ないと判断する。ＡまたはＢの評価であることが好ましく、Ａの評価であることがより好ましい。得られた結果を下記表に記載した。
　Ａ：Ｌ＊の最大値と最小値の差が１．０未満。
　Ｂ：Ｌ＊の最大値と最小値の差が１．０以上、１．５未満。
　Ｃ：Ｌ＊の最大値と最小値の差が１．５以上、２．０未満。
　Ｄ：Ｌ＊の最大値と最小値の差が２．０以上、５．０未満。
　Ｅ：Ｌ＊の最大値と最小値の差が５．０以上。 <Density unevenness after a month>
Each composition obtained above was aged for one month at room temperature (23 ° C.). A white pattern was prepared in the same manner as the L * measurement method using each composition that had passed for one month. Thereafter, the difference between the maximum value and the minimum value of L * in the plane of the white pattern was measured and 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: The difference between the maximum value and the minimum value of L * is less than 1.0.
B: The difference between the maximum value and the minimum value of L * is 1.0 or more and less than 1.5.
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.
＜塗布適性＞
　上記で得られた各組成物を、恒温オーブン中に５０℃で１２時間静置した。５０℃に昇温された組成物を、ミカサ製スピンコータＭＳ－Ｂ１００を用い、３００ｒｐｍで５秒間、メイン回転数で２０秒間の条件で４インチウェハに塗布し、膜厚３．０μｍの膜を製造した。その際のメイン回転数について、下記のように分類を行い、塗布適性の評価とした。Ａ、Ｂ、ＣまたはＤの評価であることが好ましく、Ａ、ＢまたはＣの評価であることがより好ましく、ＡまたはＢの評価であることがさらに好ましく、Ａの評価であることが特に好ましい。得られた結果を下記表に記載した。
　Ａ：メイン回転数１０００以上２０００ｒｐｍ以下の範囲で膜厚３．０μｍが塗布可能。
　Ｂ：Ａの条件では、膜厚３．０μｍを塗布できないが、メイン回転数７５０以上１０００ｒｐｍ未満、２０００より大きく２５００ｒｐｍ以下の範囲で膜厚３．０μｍが塗布可能。
　Ｃ：ＡおよびＢの条件では、膜厚３．０μｍを塗布できないが、メイン回転数５００以上７５０ｒｐｍ未満、２５００より大きく３０００ｒｐｍ以下の範囲で膜厚３．０μｍが塗布可能。
　Ｄ：Ａ、ＢおよびＣの条件では、膜厚３．０μｍを塗布できないが、メイン回転数３０００より大きく４０００ｒｐｍ以下の範囲で膜厚３．０μｍが塗布可能。
　Ｅ：上記のメイン回転数の範囲内では膜厚３．０μｍを得ることができない。 <Applicability>
Each composition obtained above was allowed to stand at 50 ° C. for 12 hours in a constant temperature oven. The composition heated to 50 ° C. was applied to a 4-inch wafer using a Mikasa spin coater MS-B100 under conditions of 300 rpm for 5 seconds and main rotation for 20 seconds to produce a film having a thickness of 3.0 μm. did. The main rotational speed at that time was classified as follows to evaluate the coating suitability. 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.
A: A film thickness of 3.0 μm 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 μm cannot be applied, but a film thickness of 3.0 μm 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 μm cannot be applied, but a film thickness of 3.0 μm 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.
D: Under the conditions of A, B, and C, a film thickness of 3.0 μm cannot be applied, but a film thickness of 3.0 μm can be applied in the range of more than 3000 rpm and less than 4000 rpm.
E: A film thickness of 3.0 μm cannot be obtained within the range of the main rotational speed.
＜耐溶剤性＞
　上記で得られた各組成物を、下塗り層付き８インチガラスウェハ上に乾燥後の膜厚が３．０μｍになるようにスピンコータを用いて塗布し、１１０℃のホットプレートを用いて１２０秒間加熱処理（プリベーク）を行った。
　次いで、ｉ線ステッパー露光装置ＦＰＡ－３０００ｉ５＋（Ｃａｎｏｎ（株）製）を使用して、３６５ｎｍの波長光を１０００ｍＪ／ｃｍ2にて、２ｃｍ×２ｃｍのパターンを有するマスクを介して露光した。
　その後、露光された塗布膜が形成されているガラスウェハをスピンシャワー現像機（ＤＷ－３０型、（株）ケミトロニクス製）の水平回転テーブル上に載置し、水酸化テトラメチルアンモニウム（ＴＭＡＨ）０．３質量％水溶液を用い、２３℃で６０秒間パドル現像を行い、ガラスウェハ上に白色パターンを形成した。
　白色パターンが形成されたガラスウェハを真空チャック方式で水平回転テーブルに固定し、回転装置によってガラスウェハを回転数５０ｒｐｍで回転させつつ、その回転中心の上方より純水を噴出ノズルからシャワー状に供給してリンス処理を行い、その後スプレー乾燥した。その後２３０℃のホットプレートを用いて５分間加熱処理（ポストベーク）を行った。
　得られた白色パターンと、白色パターンをＮ－メチル－２－ピロリジノン中に５分間浸漬した後の白色パターンの波長４００～７００ｎｍにおける透過率をＭＣＰＤ－３０００（大塚電子（株）製）を使用して測定した。その分光変動（ΔＴ％）について、最も分光変動が大きい波長での変動をΔＴｍａｘとし、耐溶剤性の評価とした。変動が小さいほど耐溶剤性が良好であり、より望ましい。Ａ、Ｂ、ＣまたはＤの評価であることが好ましく、Ａ、ＢまたはＣの評価であることがより好ましく、ＡまたはＢの評価であることがさらに好ましく、Ａの評価であることが特に好ましい。得られた結果を下記表に記載した。
　Ａ：ΔＴｍａｘ＜０．５％。
　Ｂ：０．５％≦ΔＴｍａｘ＜１．０％。
　Ｃ：１．０％≦ΔＴｍａｘ＜３．０％。
　Ｄ：３．０％≦ΔＴｍａｘ＜５．０％。
　Ｅ：ΔＴｍａｘ≧５．０％。 <Solvent resistance>
Each composition obtained above was applied onto an 8-inch glass wafer with an undercoat layer using a spin coater so that the film thickness after drying was 3.0 μm, and heated for 120 seconds using a 110 ° C. hot plate. Processing (pre-baking) was performed.
Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), exposure was performed through a mask having a pattern of 2 cm × 2 cm at a wavelength of 365 nm at 1000 mJ / cm 2 .
Thereafter, 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). Using a 0.3% by mass aqueous solution, 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. Then, a rinse treatment was performed, followed by spray drying. Thereafter, heat treatment (post-bake) was performed for 5 minutes using a 230 ° C. hot plate.
MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.) was used for the transmittance of the obtained white pattern and the white pattern after immersing the white pattern in N-methyl-2-pyrrolidinone for 5 minutes at a wavelength of 400 to 700 nm. Measured. With respect to the spectral fluctuation (ΔT%), the fluctuation at the wavelength having the largest spectral fluctuation was ΔTmax, and the solvent resistance was evaluated. The smaller the fluctuation, the better the solvent resistance, and more desirable. 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.
A: ΔTmax <0.5%.
B: 0.5% ≦ ΔTmax <1.0%.
C: 1.0% ≦ ΔTmax <3.0%.
D: 3.0% ≦ ΔTmax <5.0%.
E: ΔTmax ≧ 5.0%.
＜パターン形状＞
　上記で得られた各組成物を、塗布後の膜厚が３．０μｍになるように、下塗り層付き８インチシリコンウェハ上にスピンコート法で塗布し、その後ホットプレート上で、１００℃で２分間加熱して組成物層を得た。
　次いで、得られた組成物層に対し、ｉ線ステッパー露光装置ＦＰＡ－３０００ｉ５＋（Ｃａｎｏｎ（株）製）を用い、２０μｍ四方のアイランドパターンを、マスクを介して露光（露光量５０～１７００ｍＪ／ｃｍ2）した。
　次いで、露光後の組成物層に対し、現像装置（東京エレクトロン製Ａｃｔ８）を使用して現像を行った。現像液には水酸化テトラメチルアンモニウム（ＴＭＡＨ）０．３質量％水溶液を用い、２３℃で６０秒間シャワー現像を行った。その後、純水を用いたスピンシャワーにてリンスを行い、パターンを得た。得られたパターンの形状を走査型電子顕微鏡（ＳＥＭ）（Ｓ－４８００Ｈ、（株）日立ハイテクノロジーズ製）を用いて観察（倍率：５０００倍）し、評価した。パターン形状の評価基準は以下の通りである。Ａ、Ｂ、ＣまたはＤの評価であることが好ましく、Ａ、ＢまたはＣの評価であることがより好ましく、ＡまたはＢの評価であることがさらに好ましく、Ａの評価であることが特に好ましい。得られた結果を下記表に記載した。
　Ａ：図１の（ａ）のようにパターンの一辺が直線である。
　Ｂ：図１の（ｂ）のようにパターンの角がやや丸まっている。
　Ｃ：図１の（ｃ）のようにパターンの一辺がやや丸まっている。
　Ｄ：図１の（ｄ）のようにパターンが丸まっている。
　Ｅ：図１の（ｅ）のようにパターンが丸い。 <Pattern shape>
Each composition obtained above was applied by spin coating onto an 8-inch silicon wafer with an undercoat layer so that the film thickness after application was 3.0 μm, and then 2 hours at 100 ° C. on a hot plate. The composition layer was obtained by heating for a minute.
Next, using the i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), the obtained composition layer was exposed to a 20 μm square island pattern through a mask (exposure amount: 50 to 1700 mJ / cm 2). )did.
Next, the composition layer after exposure was developed using a developing device (Act 8 manufactured by Tokyo Electron). A 0.3% by weight aqueous solution of tetramethylammonium hydroxide (TMAH) was used as the developer, and shower development was performed at 23 ° C. for 60 seconds. Then, it rinsed with the spin shower using a pure water, and the pattern was obtained. The shape of the pattern obtained was observed (magnification: 5000 times) using a scanning electron microscope (SEM) (S-4800H, manufactured by Hitachi High-Technologies Corporation) and evaluated. The evaluation criteria for the pattern shape are as follows. 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.
A: One side of the pattern is a straight line as shown in FIG.
B: The corners of the pattern are slightly rounded as shown in FIG.
C: One side of the pattern is slightly rounded as shown in FIG.
D: The pattern is rounded as shown in FIG.
E: The pattern is round as shown in FIG.
＜密着性＞
　パターン形状の評価で作製したパターンの中で２０μｍのパターンサイズのパターン群を光学顕微鏡（オリンパス（株）製）にて観察した。密着性の評価基準は以下の通りである。Ａ、Ｂ、ＣまたはＤの評価であることが好ましく、Ａ、ＢまたはＣの評価であることがより好ましく、ＡまたはＢの評価であることが特に好ましく、Ａの評価であることがより特に好ましい。得られた結果を下記表に記載した。
　Ａ：パターンに剥がれまたは欠けなし。
　Ｂ：観測されるパターンの剥がれまたは欠けが０％より大きく５％未満である。
　Ｃ：観測されるパターンの剥がれまたは欠けが５％以上１０％未満である。
　Ｄ：観測されるパターンの剥がれまたは欠けが１０％以上３０％未満である。
　Ｅ：観測されるパターンの剥がれまたは欠けが３０％以上である。 <Adhesion>
Among the patterns produced in the evaluation of the pattern shape, a pattern group having a pattern size of 20 μm 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.
A: No peeling or chipping in the pattern.
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.
＜着色性＞
　耐溶剤性の評価と同様の方法で作製したパターンの分光Ｌ＊、ａ＊、ｂ＊を分光測光器を用いて、測定条件をＤ６５光源、観測視野を２°、白色基準はＸ－ｒｉｔｅ５２８（商品名、Ｘ－ｒｉｔｅ社製）に付属のキャリブレーション基準板のホワイトパッチを用いて測定した。分光測光器として、Ｘ－ｒｉｔｅ５２８（商品名、Ｘ－ｒｉｔｅ社製）を用いた。なお、測定の際には、パターンを形成したガラスウェハを、黒色レジストで被覆した台（黒色台）に置いて測定した。黒色台の黒色レジスト層のＯＤ（Ｏｐｔｉｃａｌ　Ｄｅｎｓｉｔｙ）は、４００ｎｍで３．５（透過率０．０３％）、５５０ｎｍで３．２（透過率０．０６）、７００ｎｍで２．５（透過率０．３２％）であり、４００ｎｍ～７００ｎｍの範囲における平均反射率は７％であった。黒色台のＯＤは大塚電子（株）製「ＭＣＰＤ－３７００」で測定し、反射率は日立ハイテクサイエンス（株）製「Ｕ－４１００」で測定した。 <Colorability>
Using a spectrophotometer, 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.
　作製したパターンを、２６５℃で１５分間、ホットプレートを用いて加熱し、加熱後のパターンの分光を測定し、ＣＩＥ１９７６のＬ＊ａ＊ｂ＊表色系における加熱前後のパターンの色差ΔＥ＊ａｂを算出した。なお、色差ΔＥ＊ａｂの算出式は以下の通りである。
　ΔＥ＊ａｂ＝〔（ΔＬ＊）2＋（Δａ＊）2＋（Δｂ＊）2〕1/2
　Ａ：色差ΔＥ＊ａｂが０以上０．５未満である。
　Ｂ：色差ΔＥ＊ａｂが０．５以上１．０未満である。
　Ｃ：色差ΔＥ＊ａｂが１．０以上２．０未満である。
　Ｄ：色差ΔＥ＊ａｂが２．０以上３．０未満である。
　Ｅ：色差ΔＥ＊ａｂが３．０以上である。
　Ａ、Ｂ、ＣまたはＤの評価であることが好ましく、Ａ、ＢまたはＣの評価であることがより好ましく、ＡまたはＢの評価であることがさらに好ましく、Ａの評価であることが特に好ましい。得られた結果を下記表に記載した。 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 ΔE * ab before and after heating in the CIE 1976 L * a * b * color system Was calculated. The calculation formula of the color difference ΔE * ab is as follows.
ΔE * ab = [(ΔL *) 2 + (Δa *) 2 + (Δb *) 2 ] 1/2
A: Color difference ΔE * ab is 0 or more and less than 0.5.
B: Color difference ΔE * ab is 0.5 or more and less than 1.0.
C: Color difference ΔE * ab is 1.0 or more and less than 2.0.
D: Color difference ΔE * ab is 2.0 or more and less than 3.0.
E: Color difference ΔE * 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.
Figure JPOXMLDOC01-appb-T000053
Figure JPOXMLDOC01-appb-T000053
　上記表より、各実施例の組成物は、厚さ３．０μｍの膜を形成した場合のＣＩＥ１９７６のＬ＊ａ＊ｂ＊表色系におけるＬ＊が３５～８５であり、かつ、一ヶ月経時後の濃度ムラが抑制された膜を製造できることがわかった。
　これに対し、樹脂の波長５８９ｎｍの光に対する屈折率が２．１を下回る粒子を用い、また、粒子の波長５８９ｎｍの光に対する屈折率と樹脂の波長５８９ｎｍの光に対する屈折率との差が１．２２を下回る比較例１および２の組成物は、厚さ３．０μｍの膜を形成した場合のＣＩＥ１９７６のＬ＊ａ＊ｂ＊表色系におけるＬ＊が３５未満または８５を超えることがわかった。波長５８９ｎｍの光に対する屈折率が１．５を超える樹脂を用い、また、粒子の波長５８９ｎｍの光に対する屈折率と樹脂の波長５８９ｎｍの光に対する屈折率との差が１．２２を下回る比較例３の組成物は、一ヶ月経時後の濃度ムラが大きいことがわかった。 From the above table, 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 μm is formed, It turned out that the film | membrane with which the density | concentration unevenness after that was suppressed can be manufactured.
On the other hand, 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. The compositions of 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 μm 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.
＜平均透過率＞
　各実施例の組成物を用いて耐溶剤性の評価で形成したパターンである厚さ３．０μｍの膜について、波長４００～７００ｎｍの範囲における透過率を、大塚電子（株）製ＭＣＰＤ－３０００を用いて５ｎｍピッチで測定し、その平均値を平均透過率とした。
　その結果、各実施例の膜は、厚さ３．０μｍ換算時の波長４００～７００ｎｍの範囲における平均透過率が１～４５％であることがわかった。 <Average transmittance>
With respect to a film having a thickness of 3.0 μm, 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 μm.
＜現像液の影響＞
　各実施例の組成物について、＜パターン形状＞の評価で用いた現像液の代わりに、本明細書に記載の溶剤で現像しても同様のパターンが得られる。 <Effect of developer>
About the composition of each Example, the same pattern is obtained even if it develops with the solvent as described in this specification instead of the developing solution used by evaluation of <pattern shape>.
　本発明の組成物から形成された膜は、厚さ３．０μｍの膜を形成した場合のＣＩＥ１９７６のＬ＊ａ＊ｂ＊表色系におけるＬ＊が３５～８５であり、かつ、一ヶ月経時後の濃度ムラが抑制された膜である。このような膜は、硬化して硬化膜として固体撮像素子などの各種類の光学センサに利用した場合に、良好な光学センサ機能と意匠性の両立が可能であり、産業上の利用可能性が高い。
  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 μm is formed, It is a film in which subsequent density unevenness is suppressed. When such a film is cured and used as a cured film in various types of optical sensors such as a solid-state imaging device, it is possible to achieve both good optical sensor function and designability, and industrial applicability. high.

Claims (19)

  1. 　粒子と樹脂とを含み、
    　前記粒子が波長５８９ｎｍの光に対する屈折率が２．１以上である粒子を少なくとも含み、
    　前記樹脂が波長５８９ｎｍの光に対する屈折率が１．５以下である樹脂を少なくとも含む、組成物。     Including particles and 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 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.
  2. 　粒子と樹脂とを含む組成物であって、
    　前記粒子のうち、前記組成物に含まれる最も屈折率の高い粒子の波長５８９ｎｍの光に対する屈折率と、前記樹脂のうち、前記組成物に含まれる最も屈折率の低い樹脂の波長５８９ｎｍの光に対する屈折率との差が１．２２以上である、組成物。     A composition comprising particles and a resin,
    Of the particles, the refractive index of the highest refractive index particle contained in the composition with respect to light having a wavelength of 589 nm, and of the resin, the resin having the lowest refractive index contained in the composition with respect to light having a wavelength of 589 nm. A composition having a difference from the refractive index of 1.22 or more.
  3. 　前記組成物が硬化性組成物である、請求項１または２に記載の組成物。 The composition according to claim 1 or 2, wherein the composition is a curable composition.
  4. 　前記組成物を用いて厚さ３．０μｍの膜を形成した場合のＣＩＥ１９７６のＬ＊ａ＊ｂ＊表色系におけるＬ＊が３５～８５である、請求項１～３のいずれか一項に記載の組成物。 The L * in the L * a * b * color system of CIE 1976 when a film having a thickness of 3.0 μm is formed using the composition is 35 to 85, according to any one of claims 1 to 3. The composition as described.
  5. 　前記粒子は、無機粒子を含む、請求項１～４のいずれか一項に記載の組成物。 The composition according to any one of claims 1 to 4, wherein the particles include inorganic particles.
  6. 　前記無機粒子は、白色顔料を含む、請求項５に記載の組成物。 The composition according to claim 5, wherein the inorganic particles include a white pigment.
  7. 　前記無機粒子は、酸化チタンを含む、請求項５または６に記載の組成物。 The composition according to claim 5 or 6, wherein the inorganic particles include titanium oxide.
  8. 　前記粒子の全質量に対する、波長５８９ｎｍの光に対する屈折率が２．１以上の粒子の含有量が８０質量％以上である、請求項１～７のいずれか一項に記載の組成物。 The composition according to any one of claims 1 to 7, wherein the content of particles having a refractive index of 2.1 or more with respect to light having a wavelength of 589 nm with respect to the total mass of the particles is 80% by mass or more.
  9. 　前記樹脂の全質量に対する、波長５８９ｎｍの光に対する屈折率が１．５以下の樹脂の含有量が５質量％以上である、請求項１～８のいずれか一項に記載の組成物。 The composition according to any one of claims 1 to 8, wherein the content of the resin having a refractive index of 1.5 or less with respect to light having a wavelength of 589 nm is 5% by mass or more with respect to the total mass of the resin.
  10. 　前記樹脂がアルカリ可溶性樹脂である、請求項１～９のいずれか一項に記載の組成物。 The composition according to any one of claims 1 to 9, wherein the resin is an alkali-soluble resin.
  11. 　前記樹脂がポリシロキサン系樹脂である、請求項１～１０のいずれか一項に記載の組成物。 The composition according to any one of claims 1 to 10, wherein the resin is a polysiloxane resin.
  12. 　前記ポリシロキサン系樹脂の側鎖のうち５０モル％以上が炭素数１～４のアルキル基および炭素数１～４のアルコキシ基のうち少なくとも一方である、請求項１１に記載の組成物。 The composition according to claim 11, wherein 50 mol% or more of the side chain of the polysiloxane resin is at least one of an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms.
  13. 　前記組成物が、さらにラジカル重合性化合物および光重合開始剤を有する、請求項１～１２のいずれか一項に記載の組成物。 The composition according to any one of claims 1 to 12, wherein the composition further comprises a radical polymerizable compound and a photopolymerization initiator.
  14. 　前記ラジカル重合性化合物の全質量中における、波長５８９ｎｍの光に対する屈折率が１．５以下のラジカル重合性化合物の含有量が８０質量％以上である、請求項１３に記載の組成物。 The composition according to claim 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.
  15. 　前記組成物が、さらに着色防止剤を有する、請求項１～１４のいずれか一項に記載の組成物。 The composition according to any one of claims 1 to 14, wherein the composition further comprises a coloring inhibitor.
  16. 　請求項１～１５のいずれか一項に記載の組成物から形成された、膜。 A film formed from the composition according to any one of claims 1 to 15.
  17. 　請求項１６に記載の膜を硬化した、硬化膜。 A cured film obtained by curing the film according to claim 16.
  18. 　請求項１７に記載の硬化膜を有する、光学センサ。 An optical sensor having the cured film according to claim 17.
  19. 　請求項１～１５のいずれか一項に記載の組成物を、パターンを有するマスクを介して露光する工程と、
    　露光された前記組成物を現像してパターン形成する工程と、を含む、膜の製造方法。
          Exposing the composition according to any one of claims 1 to 15 through a mask having a pattern;
    And developing the exposed composition to form a pattern.
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