JP6688875B2 - Composition, film, cured film, optical sensor and method for manufacturing film - Google Patents

Description

  The present invention relates to a composition, a film, a cured film, an optical sensor and a method for manufacturing a film.

  It is known to manufacture a film using a composition containing a resin and particles (see Patent Documents 1 and 2). In particular, Patent Document 1 describes manufacturing a film using a composition containing particles which are white pigments such as titanium oxide.

WO2014 / 126013A JP 2012-212114 A

  A film using a composition containing a resin and particles can be used as an optical film using a semiconductor as a white film. In a film for optical sensors using semiconductors, the film is a thin film, but it has a degree of shielding that can conceal the optical sensor, and at the same time, it shields enough light to drive the optical sensor and detect changes in the amount of light received. A membrane is required. Light transmittance is low in the film in the region where L * exceeds 85 in the CIE1976 L * a * b * color system, which is close to pure white, and is sufficient to drive the optical sensor and detect changes in the amount of received light. It is difficult to transmit a certain amount of light. Even in the case of using a thin film, from the viewpoint of concealing the optical sensor, the film needs to have L * of 35 or more in the LIE a * b * color system of CIE1976 as whiteness. Therefore, in order to achieve both the shielding degree and the transmittance, the film is required to have L * in the region of 35 to 85.

On the other hand, when the present inventors used a resin having a refractive index of about 1.6 as a binder for the film or a dispersant for the particles, and examined a white film obtained from a composition containing the particles and the resin, It was later found that density unevenness was recognized. Specifically, when a white film was formed using the composition after one month at room temperature, a new problem was found in which a portion having a whiter density and a portion having a whiter density than normal were clearly observed. Hereinafter, in the case where a white film is formed using the composition that has been stored for one month at room temperature, the white density unevenness of the film is referred to as the 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, the white density unevenness of the film does not occur, and there is no suggestion for suppressing the density unevenness after a lapse of one month.
Further, Patent Documents 1 and 2 do not suggest 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.

  The problem to be solved by the present invention is that the LIE in the L * a * b * color system of CIE1976 when a film having a thickness of 3.0 μm is formed is 35 to 85, and after one month elapses. An object of the present invention is to provide a composition capable of producing a film in which uneven density is suppressed.

  Under the circumstances, as a result of intensive studies by the present inventors, they have found that the above problems can be solved by the following constitutions, and have completed the present invention. The present invention and preferred configurations of the present invention are as follows.

[1] contains particles and a resin,
The particles include at least particles having a refractive index of 2.1 or more for light having a wavelength of 589 nm,
A composition comprising at least a resin having a refractive index of 1.5 or less for light having a wavelength of 589 nm.
[2] A composition comprising particles and a resin,
Among the above particles, the refractive index of the particle having the highest refractive index contained in the composition with respect to the 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 the light having the wavelength of 589 nm, A composition having a difference of 1.22 or more with.
[3] The composition according to [1] or [2], which is a curable composition.
[4] Any of [1] to [3], in which L * in the L * a * b * color system of CIE1976 is 35 to 85 when a film having a thickness of 3.0 μm is formed using the composition The 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 contain a white pigment.
[7] The composition according to [5] or [6], wherein the inorganic particles contain titanium oxide.
[8] The composition according to any one of [1] to [7], in which the content of particles having a refractive index of 2.1 or more for light having a wavelength of 589 nm is 80% by mass or more based on the total mass of the particles. .
[9] The composition according to any one of [1] to [8], in which the content of a 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 based on 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 chains 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], which further comprises a radically polymerizable compound and a photopolymerization initiator.
[14] The composition according to [13], wherein the content of the radically polymerizable compound having a refractive index of 1.5 or less with respect to light having a wavelength of 589 nm is 80% by mass or more based on the total mass of the radically polymerizable compound.
[15] The composition according to any one of [1] to [14], which 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,
Developing the exposed composition to form a pattern.

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 CIE1976 is 35 to 85, and density unevenness after one month is suppressed. It is possible to provide a composition capable of producing a formed film.
Further, according to the present invention, a film, a cured film, an optical sensor, and a method for manufacturing a film can be provided.

It is a figure which shows the standard of evaluation of a pattern shape.

Hereinafter, the content of the present invention will be described in detail.
The description of the constituents described below may be made based on the representative embodiment of the present invention, but the present invention is not limited to such an embodiment.
In the present specification, the numerical range represented by "to" means a range including the numerical values before and after "to" as the lower limit value and the upper limit value.
In the description of the group (atomic group) in the present specification, the notation that does not indicate substitution or non-substitution includes a group (atomic group) having no substituent and a group (atomic group) having 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 the present specification, the term “exposure” includes not only exposure using light but also drawing using a particle beam such as an electron beam or an ion beam, unless otherwise specified. In addition, the light used for the exposure generally includes a bright line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron rays, or radiation.
In the present specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene conversion values measured by gel permeation chromatography (GPC). In the present 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 determined by using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as an eluent.

[Composition]
A 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 for light having a wavelength of 589 nm,
The resin includes at least a resin having a refractive index of 1.5 or less for 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 the particles with the highest refractive index (hereinafter also referred to as the particles with the highest refractive index) contained in the composition with respect to the light having a wavelength of 589 nm, and the resin with the lowest refractive index contained in the composition (hereinafter referred to as the lowest refractive index). (Also called a resin) has a difference of 1.22 or more with respect to the refractive index with respect to light having a wavelength of 589 nm.
With such a configuration, L * in the L * a * b * color system of CIE1976 when a film having a thickness of 3.0 μm is formed is 35 to 85, and density unevenness after one month elapses. It is possible to provide a composition capable of producing a suppressed film.
The present inventors produced a composition containing particles and a resin by using a resin having a refractive index of about 1.6 as a binder for a film or a dispersant for particles. However, when a white film was formed using the composition that had been stored at room temperature for one month, it was apparent that a portion having a whiter density and a portion having a whiter density than usual were observed.
It is considered that if the particles are just aggregated, the white density becomes thin on average except the portion where the white density is high. It is considered that the presence of the white portion having a lower concentration than the surroundings indicates that the solid content other than the particles is unevenly distributed.
On the other hand, a compound having a low refractive index tends to have a low electron density, for example, it tends to have few substituents such as carboxylic acid groups and π-conjugated systems which cause intermolecular interaction. In the first aspect of the composition of the present invention, by using a resin having a refractive index of 1.5 or less for light having a wavelength of 589 nm (a resin having a low refractive index), the interaction between the resins having a low refractive index is The interaction between the resin and the particles having a refractive index of 2.1 or more for light having a wavelength of 589 nm (particles having a high refractive index) is reduced, and uneven distribution of the resin and particles in the composition is eliminated. . As a result, it is estimated that the uneven density after one month was 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. The uneven distribution of resin and particles in the composition is eliminated. As a result, it is estimated that the uneven density after one month was 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 the L * in the LIE of the CIE1976 L * a * b * color system in the case of forming a film having a thickness of 3.0 μm was 35 to 85.
Hereinafter, preferred embodiments of the composition of the present invention will be described. In the following, unless otherwise specified, a composition includes both the first aspect of the composition of the present invention and the second aspect of the composition of the present invention.

<Characteristics>
The composition of the present invention is preferably a curable composition. The "curable composition" refers to a composition containing a curable compound described below. The curable composition may be a photocurable composition or a thermosetting composition.
Details of characteristics of the composition of the present invention will be described.

<< L * >>
The composition of the present invention preferably has an L * in the L * a * b * color system of CIE1976 of 35 to 85 when a film having a thickness of 3.0 μm is formed using the composition. When a film having a thickness of 3.0 μm is formed using the composition, the upper limit of L * in the LIE a * b * color system of CIE1976 is more preferably less than 80, and further preferably 75 or less. It is preferably 70 or less, and particularly preferably 70 or less. When a film having a thickness of 3.0 μm is formed by using the composition, the lower limit of L * in the LIE a * b * color system of CIE1976 is more preferably 40 or more, and particularly preferably 50 or more. preferable. The L * value in the LIE a * b * color system of CIE1976 is a value measured by the method described in Examples below.

<< a * and b * >>
The composition of the present invention preferably has a * and b * in the L * a * b * color system of CIE1976 of −30 to 30 when a film having a thickness of 3.0 μm is formed using the composition, − 20-20 are more preferable, and -10-10 are especially preferable.

<< solid sedimentation rate >>
The composition of the present invention preferably has a solid content sedimentation rate of 10% by mass or less when centrifuged at 47 ° C for 47 minutes at room temperature (25 ° C) at 3500 rpm (rotations per minute). It is more preferably not more than mass%. As a method of decreasing the solid content sedimentation rate of the composition, a method of increasing the viscosity of the composition, a method of decreasing the solid content concentration of the composition, or an increase of the dispersibility of the solid content (preferably particles) in the composition Examples include a method, a method of reducing the density of particles, and a method of reducing the particle size of particles. Unless otherwise specified, the “solid content” in the present specification means the following “solid content before centrifugation”. The composition is dried in an oven under the conditions of 160 ° C. for 1 hour to evaporate the volatile content, and the loss on drying before and after the drying is measured to determine the volatilization amount. The difference between the mass of the composition before drying and the volatilization amount is calculated. By calculation, "solid content before centrifugation" is calculated.
The “solid content after centrifugation” is calculated in the same manner as above for the supernatant after the composition is centrifuged at room temperature and 3500 rpm for 47 minutes. 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 solid content sedimentation rate as a percentage.

<< 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. When the solid content concentration of the composition is in the above range, the viscosity of the composition can be increased, particle sedimentation and the like can be effectively suppressed, and uneven density after one month can be more effectively improved.

<Composition of composition>
Hereinafter, the composition of the composition will be described in detail.

<<<particles>
The composition of the present invention comprises particles.
The composition of the present invention is the difference between the refractive index of the particles having the highest refractive index contained in the composition for the light having a wavelength of 589 nm and the refractive index of the resin having the lowest refractive index contained in the composition for the 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 easy to increase the L * in the LIE a * b * color system of CIE1976 when a film having a thickness of 3.0 μm is formed, which is preferable.

(Particles having a refractive index of 2.1 or more for light having a wavelength of 589 nm)
The composition of the present invention preferably contains particles having a refractive index of at least 2.1 with respect to light having a wavelength of 589 nm.
When the composition contains two or more kinds of particles, it is preferable that the composition 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 to include only the above particles.
The composition of the present invention has a 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) of 80% by mass or more based on 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 the particles having a refractive index of 2.1 or more for the light of the wavelength of 589 nm to the light of the wavelength of 589 nm is preferably 2.1 to 2.75, and more preferably 2.5 to 2.75. preferable. If the particle has a refractive index of 2.1 or more for light having a wavelength of 589 nm, it is possible to increase L * in the L * a * b * color system of CIE1976 when a film having a thickness of 3.0 μm is formed. ,preferable.
The refractive index of particles is measured by the following method.
First, dispersion is performed using a dispersant having a known refractive index and PGMEA. After that, the prepared dispersion liquid and a resin having a known refractive index are mixed so that the concentration in the solid content of the particles becomes 10% by mass, 20% by mass, 30% by mass, and 40% by mass, and four types of coating are applied. Make a liquid. After coating these coating solutions on a Si wafer at 300 nm, the refractive index of the obtained film is measured using ellipsometry (Lambda Ace RE-3300 (trade name), Dainippon Screen Mfg. Co., Ltd.). Then, the particle concentration and the refractive index are plotted and extrapolated to derive the particle refractive index.
Further, after taking out the particles from the composition, the film or the cured film by the following method, the refractive index of the particles can be similarly measured by the method described in the above Examples.
When measuring the refractive index of particles taken out from a film or a cured film, as a method of taking out particles from the film, for example, 2 to 6 mol / L of a film or a cured film (a composition is applied to form a film) is used. A basic solution is added in an amount of 10 to 30% by mass of the mass of the film or cured film, heated under reflux for 12 hours, and then filtered and washed to obtain a particle component.

The 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, and more preferably 60 to 200 nm from the viewpoint of uneven density after one month. , 70 to 200 nm is particularly preferable from the viewpoint of L *. The particles having an average primary particle diameter 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 may be particles having a major axis and a minor axis described later, instead of being strict circular particles.
Particles having a refractive index of 2.1 or more for light having a wavelength of 589 nm are more preferable as the proportion of particles having a particle diameter of 50 to 300 nm is higher. Specifically, the particles having a refractive index of 2.1 or more for light having a wavelength of 589 nm preferably contain particles having a particle diameter of 50 to 300 nm in a proportion of 30% by mass or more, and particles having a particle diameter of 50 to 300 nm. Is more preferably contained in a proportion of 50% by mass or more. When the content of particles having a particle size of 50 to 300 nm is 30% by mass or more, it is easy to control L * in the LIE a * b * color system of CIE1976 to 35 to 85 when a film having a thickness of 3.0 μm is formed. And, it is easy to provide a composition having excellent stability over time in liquid.
In the present invention, the primary particle size of the particles can be determined by observing the powder particles with a transmission electron microscope (TEM) and observing a portion where the particles are not aggregated. In the present invention, the particle size distribution of the particles, powder particles that are primary particles, after taking a transmission electron microscope photograph using a transmission electron microscope, to measure the particle size distribution with an image processing device using the photograph Ask for. In the present invention, the average primary particle size of the particles is defined as the number-based arithmetic average size 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 a Luzex AP manufactured by Nireco Corporation is used as an image processing apparatus.
The particles having a refractive index of 2.1 or more for light having a wavelength of 589 nm may be particles having an average major axis length of 50 to 150 nm. The particles having an average major axis length of 50 to 150 nm preferably have an average major axis length of 60 to 140 nm, 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 “long axis of particles” refers to the longest diameter of particles in a transmission electron microscope photograph of the particles. In the present specification, the “minor axis of the particle” refers to 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-shaped 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. The average major axis length of the particles having an average major axis length of 50 to 150 nm is preferably 2 to 10 times, more preferably 3 to 6 times, and more preferably 4 to 5 times the average minor axis length. Is particularly preferable.
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 a major axis length of 50 to 150 nm. It is more preferable to contain the particles of 35 to 50% by mass. When the particle having the major axis length of 50 to 150 nm is 30% by mass or more, the L * in the L * a * b * color system of CIE1976 is controlled to 35 to 85 when a film having a thickness of 3.0 μm is formed. In addition, it is easy to provide a composition having excellent stability over time in liquid. 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 the minor axis length of the particles can be determined by observing the powder particles with a transmission electron microscope (TEM) and observing a portion where the particles are not aggregated. In the present invention, the particle size distribution of the particles, the powder particles that are primary particles, after taking a transmission electron microscope photograph using a transmission electron microscope, the major axis length of the particles in the image processing device using the photograph Also, 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 are the average major axis length and the average minor axis length, respectively, with the number-based arithmetic mean 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 a 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 for 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 particles having a refractive index of 2.1 or more for light having a wavelength of 589 nm is smaller than the upper limit value of the preferable range, the particles are less likely to settle in the composition, and uneven density and pattern shape after one month are more likely to occur. 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.

There is no particular limitation on the type of particles having a refractive index of 2.1 or more for light having a wavelength of 589 nm.
Examples of particles having a refractive index of 2.1 or more for light having a wavelength of 589 nm include various conventionally known inorganic particles and organic particles. The particles having a refractive index of 2.1 or more for 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 cause sedimentation 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 for light having a wavelength of 589 nm are used in combination with a resin having a refractive index of 1.5 or less for 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 concentration unevenness after one month has been suppressed. According to the 2nd aspect of the composition of this invention, the refractive index with respect to the light of wavelength 589nm of the particle | grains with the highest refractive index contained in a composition, and the wavelength 589nm of the resin with the lowest refractive index contained in a composition. Since the difference between the refractive index with respect to light is 1.22 or more, even when inorganic particles are used as the particles, it is possible to suppress the sedimentation of the inorganic particles and suppress the uneven density after one month. Can be manufactured.
The inorganic particles are preferably particles containing a metal. More preferably, the metal-containing particles contain a simple metal or a metal oxide.

  Examples of particles having a refractive index of 2.1 or more for light having a wavelength of 589 nm include pigments, ceramic materials, magnetic material and other particles, and pigments are preferable.

In the composition of the present invention, the inorganic particles are preferably white pigments. By using the white pigment as the inorganic particles, it is easy to control the L * in the L * a * b * color system of CIE1976 within a preferable range when a film having a thickness of 3.0 μm is formed using the composition. In the present invention, white pigments include not only pure white but also light gray pigments close to white (for example, gray white, light gray, etc.).
White pigments tend to have a high density and tend to cause sedimentation 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 for light having a wavelength of 589 nm are used in combination with a resin having a refractive index of 1.5 or less for 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 the sedimentation of the inorganic particles is suppressed and the density unevenness after one month has been suppressed. According to the 2nd aspect of the composition of this invention, the refractive index with respect to the light of wavelength 589nm of the particle | grains with the highest refractive index contained in a composition, and the wavelength 589nm of the resin with the lowest refractive index contained in a composition. Since the difference between the refractive index with respect to light is 1.22 or more, even when a white pigment is used as the particles, it is possible to obtain a film in which the sedimentation of the inorganic particles is suppressed and the uneven density after one month is suppressed. Can be manufactured.
White pigments include, for example, 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 thereof 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 contain titanium oxide.

As for titanium oxide, the purity of titanium dioxide (TiO ₂ ) is preferably 70% or more, more preferably 80% or more, and further preferably 85% or more. Titanium oxide is preferably (the n represents. The number of 2~4) Ti _n O _2n-1 content of such low-order titanium oxide, titanium oxynitride represented by not more than 30 wt%, 20 It is more preferably not more than 15% by mass, further preferably not more than 15% by mass.

The titanium oxide may be rutile type titanium oxide or anatase type titanium oxide, and rutile type titanium oxide is preferable from the viewpoints of colorability and liquid stability over time. 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 conversion rate of titanium oxide is preferably 95% or more, more preferably 99% or more.
As the rutile type titanium oxide, known ones can be used. There are two types of methods for producing rutile-type titanium oxide, a sulfuric acid method and a chlorine method. In the present invention, those produced by either manufacturing method can be preferably used. Here, the sulfuric acid method uses ilmenite ore or titanium slag as a raw material, dissolves this in concentrated sulfuric acid to separate iron as iron sulfate, and obtains a hydroxide precipitate by hydrolyzing the solution, It refers to a manufacturing method in which rutile-type titanium oxide is taken out by firing at high temperature. On the other hand, in the chlorine method, synthetic rutile or natural rutile is used as a raw material, which is reacted with chlorine gas and carbon at a high temperature of about 1000 ° C. to synthesize titanium tetrachloride, which is then oxidized to take out rutile titanium oxide. Say the method. The rutile type titanium oxide is preferably 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 to appear white, and when a composition is used to form a film having a thickness of 3.0 μm, CIE1976 It is easy to control L * in the L * a * b * color system to 35 to 85. The preferable range of the average primary particle diameter of titanium oxide particles is the same as the preferable range of the average primary particle diameter of particles having a refractive index of 2.1 or more for light having a wavelength of 589 nm.

The specific surface area of titanium oxide, BET (Brunauer, Emmett, Teller ) is preferably a value measured by method is 10 to 400 m ² / g, more preferably 10~200m ² / g, 10~150m more preferably from ² / g, particularly preferably from 10 to 40 m ² / g, and most preferably 10 to 20 m ² / g.
The pH (power of hydrogen) of titanium oxide is preferably 6 to 8.
The oil absorption of titanium oxide (g / 100g) is preferably 10 to 60 (g / 100g), and more preferably 10 to 40 (g / 100g).
In 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 the content be 0.02% by mass or less, and it is particularly preferable that the content be substantially zero.
The shape of titanium oxide is not particularly limited. Examples thereof include isotropic shapes (for example, spherical shape, polyhedral shape, etc.), anisotropic shapes (for example, needle shape, rod shape, plate shape, etc.), and irregular shapes.
The hardness (Mohs hardness) of titanium oxide is preferably 5 to 8, and more preferably 7 to 7.5.
True specific gravity of titanium oxide (density) is preferably 1.0~6.0g / cm ^3, more preferably 3.9~4.5g / cm ^3.
Preferably the bulk density of the titanium oxide is ^{0.1g / cm 3 ~1.0g / cm 3} , more preferably ^{0.2g / cm 3 ~0.4g / cm 3} .

  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 and the like. Of these, silane coupling agents are preferred. Further, the inorganic particles such as titanium oxide are preferably treated with a surface treatment agent of Al (aluminum), Si (silicon) and an organic substance. The surface treatment may be carried out by using one type of surface treatment agent alone 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, the light resistance and the dispersibility are further improved.

  It is also preferable that the 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 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 the 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, a ball mill or the like. The pH of the slurry is then made neutral or alkaline, optionally acidic. After that, a water-soluble salt as a raw material of the coating material is added to the slurry to coat the surface of the inorganic particles. Then, the slurry is neutralized and the inorganic particles are collected. The recovered inorganic particles may be dried or dry pulverized.

It is preferable that the inorganic particles such as titanium oxide have an acidic site and are surface-treated with a compound capable of reacting with the acidic site. As the compound capable of reacting with the acidic site of the inorganic pigment, trimethylolpropane, trimethylolethane, ditrimethylolpropane, trimethylolpropane ethoxylate or polyhydric alcohol such as pentaerythritol, monoethanolamine, monopropanolamine, diethanolamine, diethanol Examples thereof include alkanolamines such as propanolamine, triethanolamine and tripropanolamine, chlorosilanes and alkoxysilanes.
As a method of reacting the inorganic particles with a compound capable of reacting with an acidic site of the inorganic particles, (1) the above compound and the inorganic particles are charged into a dry crusher such as a fluid energy crusher or an impact crusher to form an inorganic pigment. Method, (2) using a high-speed stirrer such as a Henschel mixer or a super mixer, and stirring and mixing the above compound and the dry-milled inorganic particles, (3) the above in an aqueous slurry of inorganic particles Examples include a method of adding a compound and stirring.

Commercially available inorganic particles can be preferably used. Examples of commercially available titanium oxide include, for example, Ishihara Sangyo Co., Ltd., trade names TAIPAQUE 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, T-501A, PT-501R, UT771, TTO-51C, TTO-80A, TTO-S-2, A-220, MPT-136, MPT-140, MPT-141;
Product name 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 name JR, JRNC, JR-301, JR-403, JR-405, JR-600A, JR-600E, JR-603, JR-605, JR-701, JR-800, JR- manufactured by TAYCA Corporation. 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 name TR-600, TR-700, TR-750, TR-840, TR-900 manufactured by Fuji Titanium Industry Co., Ltd .;
Examples include Brilliant 1500 manufactured by Shiraishi Calcium Co., Ltd. Further, the titanium oxide described in paragraphs 0025 to 0027 of JP-A-2005-67794 can also 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 (produced by Sakai Chemical Industry Co., Ltd.). Examples of commercially available zinc oxide include Zincox Super F-1 (manufactured by Hakusui Tech 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 being classified. For example, a classified product of CR-90-2 or a classified product of MPT-141 can be preferably used.

  The physical properties and impurities of commercially available inorganic particles are shown below.

  In the present invention, the inorganic particles are not limited to those made of a single inorganic material, and particles mixed with other materials may be used. For example, particles having pores or other materials inside, particles in which a large number of inorganic particles are attached to core particles, core and shell composite particles composed of core particles made of polymer particles and a shell layer made of inorganic nanoparticles are used. It is preferable. As 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, for example, the descriptions in paragraphs 0012 to 0042 of JP-A-2015-47520 can be referred to. The content is 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, and 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. The upper limit is not particularly limited, and is preferably 70% by mass or less, more preferably 60% by mass or less, and most preferably 50% by mass or less, based on the total solid content of the composition.
In addition, the proportion of the inorganic particles in the particles having a refractive index of 2.1 or more for 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. From the viewpoint of whiteness, transmittance and lithographic properties, it is preferably 99% by mass or less, and more preferably 95% by mass or less.
In addition, the proportion of the white pigment in the particles having a refractive index of 2.1 or more for 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. From the viewpoint of whiteness, transmittance and lithographic properties, it is preferably 99% by mass or less, and more preferably 95% by mass or less.
Further, the proportion of titanium oxide in the particles having a refractive index of 2.1 or more for 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. From the viewpoint of whiteness, transmittance and lithographic properties, it is preferably 99% by mass or less, and more preferably 95% by mass or less.
In addition, 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 for light having a wavelength of 589 nm is preferably 50% by mass or more, and 80% by mass or more. More preferable. The upper limit may be 100% by mass or 99% by mass or less. From the viewpoint of whiteness, transmittance and lithographic properties, it is preferably 99% by mass or less, and more preferably 95% by mass or less.

<< Other colorants >>
The composition may contain a colorant other than the particles having a refractive index of 2.1 or more for light having a wavelength of 589 nm. By containing other coloring agent, 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 CIE1976 are controlled within a preferable range. Cheap. Examples of other colorants include chromatic colorants and black colorants.

(Chromatic colorant)
The composition of the present invention may 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.

  The chromatic colorant may be a chromatic color pigment or a dye.

The chromatic color pigment is preferably an organic pigment. The organic pigment is not particularly limited, and a known chromatic 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, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. (Above, 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 (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 (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)
The organic pigments can be used alone or in combination of two or more.

The dye is not particularly limited, and known dyes can be used. The chemical structure, pyrazole azo, anilino azo, triphenylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, Dyes of xanthene type, phthalocyanine type, benzopyran type, indigo type, pyrromethene type and the like can be used. Also, multimers of these dyes may be used. Further, the dyes described in JP-A-2015-028144 and JP-A-2015-34966 can also be used.
As the dye, an acid dye and its derivative can be preferably used. In addition, direct dyes, basic dyes, mordant dyes, acidic 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 will be given below, but the acid dye is not limited thereto. For example, the following dyes and derivatives of these dyes can be mentioned.

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.

  Other than the above, azo, xanthene and phthalocyanine acid dyes are also preferable, and C.I. I. Solvent Blue 44, 38; C.I. I. Acid dyes such as Solvent orange 45; Rhodamine B and Rhodamine 110, and derivatives of these dyes are also preferably used.

  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 based on 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 the present invention contains two or more chromatic colorants, the total amount thereof is preferably within the above range.

(Black colorant)
The composition of the present invention may contain a black colorant. The black colorant may be an inorganic black colorant or an organic black colorant.

  Examples of organic black colorants include bisbenzofuranone compounds, azomethine compounds, perylene compounds, azo compounds, and the like, and bisbenzofuranone compounds and perylene compounds are preferable. Examples of the bisbenzofuranone compound include those described in JP 2010-534726 A, JP 2012-515233 A, JP 2012-515234 A, and the like, for example, as "Irgaphor Black" manufactured by BASF. It is available. Examples of the perylene compound include C.I. I. Pigment Black 31, 32 and the like. Examples of the azomethine compound include those described in JP-A-1-170601 and JP-A-2-34664, and for example, it is available as "Chromofine Black A1103" manufactured by Dainichi Seika.

  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 or titanium oxynitride is preferable. The surface of titanium black can be modified as needed for the purpose of improving dispersibility, suppressing cohesion, and the like. For example, it is possible to coat the surface of titanium black with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide. Further, a treatment with a water-repellent substance as disclosed in JP 2007-302836 A is also possible. Specific examples of the black pigment include C.I. I. Pigment Black 1,7, titanium black pigment and the like.

  Titanium black is preferably one in which both the primary particle size and the average primary particle size of individual particles are small. Specifically, the average primary particle diameter is preferably in the range of 10 nm to 45 nm.

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 / It is more preferably g or less. Examples of commercial products of 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. For example, a dispersion containing titanium black particles and silica particles, in which the content ratio of Si atoms and Ti atoms in the dispersion is controlled to be in the range of 0.20 to 0.50, may be mentioned. Regarding the dispersion, the description in paragraphs 0020 to 0105 of JP 2012-169556 A can be referred to, and the contents thereof are incorporated in the present specification.

<< resin >>
The composition of the present invention comprises a resin. The resin is mixed, for example, for the purpose of dispersing particles such as pigments in the composition and for the purpose of binder. The resin mainly used for dispersing the particles in the composition is also referred to as a dispersant. However, such an application of the resin is an example, and the resin can be used for purposes other than such an application.

(Resin having a refractive index of 1.5 or less for light having a wavelength of 589 nm)
The composition of the present invention preferably contains a resin having a refractive index of 1.5 or less for light having a wavelength of 589 nm.
When the composition contains two or more kinds of resins, it is preferable that the composition 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 resins.
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 is preferably 5% by mass or more, and more preferably 30% by mass or more, based on the total mass of the resin. The content is preferably 50% by mass or more, more preferably 90% by mass or more.

When the composition contains two or more kinds of resins, it is preferable that all resins included in the composition have a mass average refractive index (light mass average refractive index of the resins) of 1.5 or less with respect to light having a wavelength of 589 nm. It is more preferably 1.49 or less, particularly preferably 1.47 or less, and particularly preferably 1.45 or less. "The mass average refractive index of all the resins contained in the composition with respect to the light having a wavelength of 589 nm" means the refractive index ni of the i-th resin with respect to the light with a wavelength of 589 nm, and all contained in the composition of the i-th resin. Of the resin (however, only the resin contained in 1% by mass or more in the total resin is included in the calculation) and the mass ratio Xi for all the resins contained in the composition are added. Specifically, when n is an integer of 2 or more and i is an integer of 1 or more, it means a value calculated by the following calculation formula.

The preferable range of the mass average refractive index of all the resins contained in the composition with respect to the light having the wavelength of 589 nm is the same as the preferable range of the refractive index of the resin with respect to the light having the wavelength of 589 nm.

The refractive index of the resin can be measured in the uncured state by the following method.
A specific measuring method is as follows. After forming a film made of only a resin to be measured on a Si wafer at 300 nm, the refractive index of the obtained film is measured by ellipsometry (Lambda Ace RE-3300 (trade name), large It is measured using Nippon Screen Mfg. Co., Ltd.

  The weight average molecular weight (Mw) of the resin is preferably 1000 to 200000, more preferably 2000 to 100000. Within these ranges, it is preferable from the viewpoint of compatibility between the resin and all the components in the composition and L *.

  The content of the resin having a refractive index of 1.5 or less for light having a wavelength of 589 nm is preferably 5 to 90% by mass, more preferably 10 to 60% by mass, based on the total solid content of the composition. And particularly preferably 10 to 50% by mass. It is preferable that the content is within these ranges from the viewpoint of pattern shape, heat resistance and L *. Only one type of resin having a refractive index of 1.5 or less for light having a wavelength of 589 nm may be contained, or two or more types may be contained. When two or more kinds are included, the total amount is preferably within the above range.

Examples of the resin having a refractive index of 1.5 or less with respect to light having a wavelength of 589 nm include fluororesins and polysiloxane resins. In the present invention, the resin is preferably a polysiloxane resin (preferably polysiloxane is the main skeleton), and is a polysiloxane resin having a refractive index of 1.5 or less for light having a wavelength of 589 nm. Is more preferable, and a polysiloxane-based resin that is also an alkali-soluble resin having a refractive index of 1.5 or less for light having a wavelength of 589 nm 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.
The resin having a refractive index of 1.5 or less with respect to light having a wavelength of 589 nm imparts alkali solubility, and thus preferably has a repeating unit containing a group that promotes alkali solubility of the alkali-soluble resin described below. The preferred groups that promote alkali solubility are the same as those described below.

-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 polymer compound (a) having a repeating unit derived from the monomer represented by the general formula (F1) as the fluororesin.

In formula (F1), Rf is a fluoroalkyl group- or perfluoroalkyl group-containing substituent, n is 1 or 2, and R ¹ is a hydrogen atom or a methyl group.
Rf is preferably a fluoroalkyl group having 9 or more fluorine atoms or a substituent containing a perfluoroalkyl group. 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 shows 1 or 2, n shows the integer of 4-12. R represents an alkyl group having 1 to 4 carbon atoms.
_{CH 2 = CRCO 2 (CH 2} ) m (CF 2) n H
m shows 1 or 2, n shows the integer of 4-12. 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 from 9 to 30, and more preferably from 13 to 25.

  It is also preferable to use a polymer compound having a repeating unit derived from a fluorine atom-containing unsaturated monomer as the fluorine-based resin. Examples of the fluorine atom-containing unsaturated monomer include radically polymerizable monomers having a polyfluoroalkyl group or a polyfluoroether group, and examples of the perfluoroalkyl group include a perfluoromethyl 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 preferable.

Examples of such a fluorine atom-containing unsaturated monomer include CH ₂ ═C (CH ₃ ) COOCH ₂ (CF ₂ ) ₄ CF ₃ and 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 are preferable.
The fluorine atom-containing unsaturated monomer may be used alone or in combination of two or more. A commercial item can also be used as a fluorine atom-containing unsaturated monomer. For example, Kyoeisha Chemical Co., Ltd. product name, Light ester FM-108, Light ester M-3F, Light ester M-4F; Nippon Mektron Co., Ltd. product name, CHEMINOX FAAC, CHEMINOX FAMAC, CHEMINOX FAAC-M, CHEMINOX FAMAC-M, There are CHEMINOX PFOE, CHEMINOX PFOE, and the like.

  Further, (a) at least one of a repeating unit derived from the monomer represented by the general formula (F1) and a repeating unit derived from a fluorine atom-containing unsaturated monomer, and a repeating unit having a group that promotes alkali solubility. A polymer compound having a 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 alkali-soluble resin described below.

  As examples of the fluorine-based resin, the fluorine-based surfactants described in JP-A-2-804, page 6, lower right column to page 9, upper right column, can be referred to, and the contents thereof are incorporated herein.

  Preferred specific examples of the fluorine-based resin are described below.

-Polysiloxane resin-
The polysiloxane resin is not particularly limited. For example, as the polysiloxane resin, a polysiloxane resin obtained by condensing a compound represented by the following general formula (1) alone with a hydrolyzate or a compound represented by the following general formula (1) and another silane A polysiloxane resin obtained by condensing a compound with a cohydrolyzate can be used. As the polysiloxane-based resin, the descriptions in <0014> to <0035> of JP-A-2014-66988 can be referred to, and the contents thereof are incorporated in the present specification.
The polysiloxane resin is obtained by condensing an alkoxysilane compound containing a compound represented by the following general formula (2) with a compound represented by the following general formula (1) as a cohydrolyzate. Is preferable from the viewpoint of improving solvent resistance.
The polysiloxane-based resin is a polysiloxane-based resin obtained by cocondensation of an alkoxysilane compound containing a compound represented by the following general formula (3) with a compound represented by the following general formula (1). Is preferable from the viewpoint of increasing the acid value of the polysiloxane resin and improving the pattern shape. Further, the polysiloxane resin obtained by condensing an alkoxysilane compound containing a compound represented by the following general formula (3) with a cohydrolyzate can also be used as an alkali-soluble resin.

General formula (1)
R ¹ ₂ Si (OR ² ) ₂

In the general formula (1), R ^1's each independently represent an alkyl group or a phenyl group, and R ^2's each independently represent 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. It is particularly preferable that it is, an alkyl group having 1 or 2 carbon atoms is more preferable, and a methyl group is most preferable. Specific examples thereof 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. , Methyl group or ethyl group is particularly preferred. When there are a plurality of R ^{1 s} 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 for R ¹ and R ² in the general formula (1) may be linear, branched or cyclic, and is preferably linear.

R ³ in the general formula (2) represents a methyl group or a hydrogen atom, R ⁴ represents an alkylene group having 1 to ⁴ carbon atoms, and R ⁵ independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ⁶ independently represents 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.

In the 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 independently represents a hydrogen atom or It represents an alkyl group having 1 to 4 carbon atoms, and R ^9's each independently represent an alkyl group having 1 to 6 carbon atoms.
More preferably, l in the general formula (3) is 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 preferred ranges of R ⁹ and R ⁸ in the general formula (3) are the same as the preferred 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 phenyltrimethoxysilane, more preferably dimethoxydimethylsilane.

  The proportion of the compound represented by the general formula (1) in the alkoxysilane compound used for cohydrolyzate condensation is preferably 25 to 75 mol%, more preferably 35 to 75 mol%, and 50 It is particularly preferably about 70 mol%. The proportion of dimethoxydiphenylsilane, diethoxydiphenylsilane and dihydroxydiphenylsilane in the alkoxysilane compound used for cohydrolyzate condensation is preferably 0 to 50 mol%, and 0 to 45 mol%. Is more preferable, 0 to 30 mol% is more preferable, and 0 to 10 mol% is particularly preferable.

Examples of the compound represented by the general formula (2) include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, Mention may be made of 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 used for cohydrolyzate condensation is preferably 10 to 45 mol%, more preferably 10 to 30 mol%, and 15 It is particularly preferably about 20 mol%. By using the compound represented by the general formula (2) as the alkoxysilane compound used for the cohydrolyzate condensation, the solvent resistance can be enhanced.

Examples of the compound represented by the general formula (3) include 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylpropyl succinic anhydride, 3-trimethoxysilylethyl succinic anhydride or 3-trimethoxysilylbutyl. Examples thereof include succinic anhydride, 3-diethoxymethylsilylpropyl succinic anhydride, 3-dimethoxymethylsilylethyl succinic anhydride or 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 used for the cohydrolyzate condensation is 1 to 30 mol% from the viewpoint of increasing the acid value of the polysiloxane resin and improving the pattern shape. It is preferably 1 to 25 mol%, more preferably 1 to 20 mol%, and particularly preferably 1 to 20 mol% from the viewpoint of suppressing uneven density after one month.

  The alkoxysilane compound used for the cohydrolyzate condensation preferably further contains a compound represented by the general formula (5).

General formula (5)
R ¹² Si (OR ¹³ ) ₃

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, and more preferably 1 epoxy group. 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 terminal via a linking group, and an alkylene group (preferably having a carbon number of 1). -10, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms), and an epoxy group bonded to the terminal via at least one of oxygen atoms is more preferable.
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 and 3 -(3,4-epoxycyclohexyl) propyltriethoxysilane may be mentioned.
The compound represented by the general formula (5) is preferably 3-glycidyloxypropyltrimethoxysilane and 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane.
The proportion of the compound represented by the general formula (5) in the alkoxysilane compound used for cohydrolyzate condensation is preferably 10 mol% or less, more preferably 8 mol% or less, and 5 mol%. The following is particularly preferable.

The alkoxysilane compound used for the cohydrolyzate condensation may contain other alkoxysilane compounds other than the compounds represented by the general formulas (1) to (3) and (5). Examples of other alkoxysilane compounds other than the compounds represented by the general formulas (1) to (3) and (5) include phenethyltrimethoxysilane, naphthyltrimethoxysilane, phenethyltriethoxysilane, naphthyltriethoxysilane, and tetra. Methoxysilane or tetraethoxysilane may be mentioned.
The proportion of the other alkoxysilane compound in the alkoxysilane compound used for the cohydrolyzate condensation is 3 mol% or less from the viewpoint of suppressing the concentration unevenness after one month and improving the solvent resistance. It is preferably 2 mol% or less, more preferably 1 mol% or less.

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 chains of the polysiloxane resin is an alkyl group having 1 to 4 carbon atoms. At least one of the group and the alkoxy group having 1 to 4 carbon atoms is preferable from the viewpoint of easily controlling the refractive index to light having a wavelength of 589 nm to be 1.5 or less, and the alkyl group having 1 to 3 carbon atoms and the carbon number. It is more preferably at least one of an alkoxy group having 1 to 3 carbon atoms, 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. The alkyl group of is particularly preferable.
From the viewpoint of lowering the refractive index of the polysiloxane resin, it is preferable that the side chain containing a phenyl group in the side chain of the polysiloxane resin is 20 mol% or less, more preferably 10 mol% or less. It is particularly preferably not more than mol%.

  The polysiloxane resin can be obtained by co-hydrolyzing an alkoxysilane compound, that is, by hydrolyzing and partially condensing the alkoxysilane compound. A general method can be used for co-hydrolyzate condensation. For example, a method may be used in which an organic solvent, water and a catalyst are added to the mixture, and the mixture is heated and stirred at 50 to 150 ° C. for about 0.5 to 100 hours. During heating and stirring, the hydrolysis by-product (alcohol such as methanol) and the condensation by-product (water) may be distilled off by distillation, if necessary.

  As a preferable example of the polysiloxane-based resin, a polysiloxane-based resin obtained by condensing a monomer which is an alkoxysilane compound shown in the following table with a cohydrolyzate can be mentioned.

(Other binders)
The composition of the present invention may contain other binders in addition to the resin having a refractive index of 1.5 or less for light having a wavelength of 589 nm. By containing other binder, the film characteristics are improved. Any other known binder may be used. Preferably, a resin soluble or swellable in water or weak alkaline water is selected so as to enable water development or weak alkaline water development. For example, if an alkali-soluble resin is used, alkali development becomes possible. Examples of such a resin include a radical polymer having a carboxy group in the side chain, for example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, and JP-B-54-25957. Polymers described in JP-A-54-92723, JP-A-59-53836 and JP-A-59-71048, that is, resins obtained by homopolymerizing or copolymerizing a monomer having a carboxy group. , A resin obtained by hydrolyzing, half-esterifying or half-amidating an acid anhydride unit by homopolymerizing or copolymerizing a monomer having an acid anhydride, and an epoxy acrylate obtained by modifying an epoxy resin 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, and examples of the monomer having an acid anhydride include maleic anhydride. To be Further, there is an acidic cellulose derivative having a carboxy group in the side chain. Moreover, the polymer which added the cyclic acid anhydride to the polymer which has a hydroxyl group is also mentioned. It is also preferable that the other binder is a resin soluble in an alkali developing solution (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 also be used.

  The alkali-soluble resin can be appropriately selected from polymers having a group that promotes 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, further 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, and an acrylic resin from the viewpoint of developing property control. Resins, acrylamide resins and acrylic / acrylamide copolymer resins are more preferred. Examples of the group that promotes alkali solubility (hereinafter, also referred to as an acid group) include a carboxy group, a phosphoric acid group, a sulfo group, a phenolic hydroxy group, and the like, and a carboxy group is preferable. The number of acid groups may be only one, or may be two or more.

  The alkali-soluble resin can be synthesized, for example, by 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 a radical polymerization method can be easily set by those skilled in the art, and the conditions are experimentally determined. You can also

The alkali-soluble resin is preferably a polymer having a carboxy group in the side chain, and is a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid. Examples thereof include acid copolymers, alkali-soluble phenol resins such as novolac type resins, acidic cellulose derivatives having a carboxy group in the side chain, and polymers obtained by adding an acid anhydride to a polymer having a hydroxy group. Particularly, 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 the monomers described in paragraphs 0017 to 0019 of JP-A-2005-34961. Examples thereof include alkyl (meth) acrylates, aryl (meth) acrylates, vinyl compounds, and N-substituted maleimide monomers.
Examples of alkyl (meth) acrylate and aryl (meth) acrylate include 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. As the vinyl compound, 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. The other monomer copolymerizable with these (meth) acrylic acid may be only one kind or two or more kinds.

  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 / A multi-component copolymer composed of (meth) acrylic acid / other monomer 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. -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 Macromonomers / benzyl methacrylate / methacrylic acid copolymers 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.

  Moreover, 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 (meth) allyl group and (meth) acryloyl group. As the alkali-soluble resin having a polymerizable group, an alkali-soluble resin having a polymerizable group in its side chain is useful. Examples of the alkali-soluble resin having a polymerizable group include DIALAL NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polymerethan acrylic oligomer. Manufactured by Diamond Shamrock Co., Ltd.), VISCOAT R-264, KS resist. 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (for example, ACA230AA), Praxel CF200 series (all manufactured by Daicel Corporation), Ebecryl3800 (manufactured by Daicel UCB Co., Ltd.), Acrycure RD-F8 (manufactured by Nippon Shokubai Co., Ltd.) and the like can be mentioned.

  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 the polymer obtained by polymerizing a monomer component containing an ether dimer, paragraphs 0022 to 0031 of JP-A-2005-34961 can be referred to, and the contents thereof are incorporated in the present specification.

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.

In 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.

  As specific examples 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. The number of ether dimers may be only one, or may be two or more.

The alkali-soluble resin may include a structural unit derived from the compound represented by the following formula (X).

In the 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 has a hydrogen atom or 1 to 20 carbon atoms which may include a benzene ring. Represents an alkyl group. n represents an integer of 1 to 15.

In the above formula (X), the alkylene group of R ₂ preferably has 2 to 3 carbon atoms. The alkyl group of R ₃ has 1 to 20 carbon atoms, 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.

Specific examples of the alkali-soluble resin include the following resins. Further, the resins described in paragraph 0037 of JP-A-2015-34961 may be mentioned. Among these resins, the alkali-soluble resin having the following polymerizable group is preferable from the viewpoint of solvent resistance.

  Regarding the alkali-soluble resin, the description in paragraphs 0558 to 0571 of JP2012-208494A (<0685> to <0700> of the corresponding US Patent Application Publication No. 2012/0235099) can be referred to, and the contents thereof can be referred to. Incorporated herein. Further, the copolymer (B) described in paragraphs 0029 to 0063 of JP2012-32767A and the alkali-soluble resin used in the Examples, paragraphs 0088 to 1988 of JP2012-208474A. The binder resin described in JP-A No. 009898 and the binder resin used in the examples, the binder resin described in Paragraph Nos. 0022 to 0032 of JP2012-137531A, and the binder resin used in the Examples, JP2013-2013A. No. 024934, paragraph Nos. 0132 to 0143, the binder resin used in Examples and the binder resin used in Examples, No. 2011-242752, Paragraph Nos. 0092 to 0098 and Examples, Paragraph No. of Japanese Unexamined Patent Publication No. 2012-032770 It is also possible to use a binder resin according to 030-0072. These contents are incorporated herein.

  The content of the other binder is preferably 0 to 60 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 include only one type of other binder, or may include two or more types of other binders. When two or more kinds are included, the total amount is preferably within the above range.

(Dispersant)
The composition of the present invention may contain a dispersant as a resin. The dispersant preferably contains at least one 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.

  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 has no basic group. Examples of the acid group of the acidic resin include a carboxy group, a phosphoric acid group, a sulfonic acid group, a phenolic hydroxyl group, and the like, and 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, further preferably 20 mgKOH / g or more. The upper limit is more preferably 100 mgKOH / g or less, further preferably 60 mgKOH / g or less. The amine value of the acidic resin is preferably 2 mgKOH / g or less, more preferably 1 mgKOH / g or less.

  In the present invention, the "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 has no acid group. The basic group of the basic resin is preferably an amino group. The amine value of the basic resin is preferably 5 to 200 mgKOH / g, more preferably 5 to 150 mgKOH / g, and further preferably 5 to 100 mgKOH / g.

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 mentioned above, and a carboxy group is preferable. An amino group is preferred as the basic group.
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, further preferably 20 mgKOH / g or more. The upper limit is more preferably 150 mgKOH / g or less, further 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, further preferably 20 mgKOH / g or more. The upper limit is more preferably 150 mgKOH / g or less, further preferably 100 mgKOH / g or less. The ratio of the acid value and the amine value of the amphoteric resin is preferably acid value: amine value = 1: 4 to 4: 1 and more preferably 1: 3 to 3: 1.

  As the dispersant, a polymer dispersant (for example, a resin having an amine group (polyamide amine and its salt, etc.), oligoimine resin, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, 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 according to its structure.

  The dispersant preferably has a site having an adsorption ability for the pigment (hereinafter, referred to as "adsorption site"). As the adsorption site, 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 Examples thereof include a monovalent substituent 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. Examples of the acid-based adsorption site include acid groups. Above all, it is preferable that the acid-based 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 phosphoric acid ester group, a polyphosphoric acid ester group, and a phosphoric acid group. For details of the adsorption site, reference can be made to paragraphs 0073 to 0080 of JP-A-2005-34961, the contents of which are incorporated herein.

  In the present invention, the resin (dispersant) is preferably a resin represented by the following formula (111).

In the above formula (111), R ¹ represents a (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 kind of 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.

Since the substituent A ¹ of the resin represented by the formula (111) can interact with the 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 can strongly interact with the pigment (for example, inorganic particles such as titanium oxide) and improve the dispersibility of the pigment in the composition. Further, the m number of polymer chains P ¹ of the resin represented by the formula (111) can function as a steric repulsion group, and by having m number, a good steric repulsion force can be exerted, and a pigment (for example, oxidation) can be obtained. Inorganic particles such as titanium) can be uniformly dispersed.

In formula (111), R ¹ represents a (m + n) -valent linking group. The (m + n) -valent linking group includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and Included are groups consisting of 0 to 20 sulfur atoms. Specific examples of the (m + n) -valent linking group include the following structural units or groups formed by combining two or more of the following structural units (which may form a ring structure). . For the details of the (m + n) -valent linking group, paragraphs 0076 to 0084 of JP2007-277514A can be referred to, and the contents thereof are incorporated in the present specification.

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, and the contents thereof are incorporated in the present specification.

In formula (111), R ² represents a single bond or a divalent linking group. The divalent linking group includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 To a group consisting of up to 20 sulfur atoms are included and may be unsubstituted or may further have a substituent. Specific examples of the divalent linking group include the following structural units or groups formed by combining two or more of the following structural units. Regarding the details of the divalent linking group, paragraphs 0071 to 0075 of JP2007-277514A can be referred to, and the contents thereof are incorporated in the present specification.

For details of the monovalent substituent represented by A ¹ in the formula (111), paragraphs 0041 to 0070 of JP-A-2007-277514 can be referred to, and the contents thereof are incorporated in the present specification.

  As the polymer compound represented by the above formula (111), the description after paragraph 0039 of JP 2007-277514 A (<0053> of corresponding US Patent Application Publication No. 2010/0233595), and, Reference can be made to paragraphs 0081 to 0117 of JP-A-2005-34961, the contents of which are incorporated in the present specification.

  In the present invention, as the resin (dispersant), a graft copolymer containing a repeating unit represented by any one of the following formulas (11) to (14) can be used.

In 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 each 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. And j and k each independently represent an integer of 2 to 8, and in the formula (13), when p is 2 to 500, a plurality of R ^3's 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.

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, and 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, an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group. , An aryl thioether group, a heteroaryl thioether group, and an amino group. Among these, as the organic groups represented by Z ¹ , Z ² , Z ³ , and Z ⁴ , those having a steric repulsion effect are preferable from the viewpoint of improving dispersibility, and each independently has 5 to 24 carbon atoms. Is preferable, and among them, 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.

  In formulas (11) to (14), n, m, p, and q are each independently an integer of 1 to 500. Moreover, in Formula (11) and Formula (12), j and k represent the integer of 2-8 each independently. From the viewpoint of dispersion stability and developability, j and k in formulas (11) and (12) are preferably integers of 4 to 6, and most preferably 5.

In 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 s} that are present may be the same or different.

In formula (14), R ⁴ represents a hydrogen atom or a monovalent group. The monovalent group is not particularly limited in structure. R ⁴ is preferably a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and more preferably a hydrogen atom or an alkyl group. When R ⁴ is an alkyl group, it is preferably a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms, and 1 to 20 carbon atoms. Is more preferable, and a linear alkyl group having 1 to 6 carbon atoms is particularly preferable. In the formula (14), when q is 2 to 500, a plurality of X ⁵ and R ⁴ present in the graft copolymer may be the same or different from each other.

Regarding the graft copolymer, the description in paragraphs 0025 to 0094 of JP 2012-255128 A can be referred to, and the above contents are incorporated in the present specification. Specific examples of the graft copolymer include the following resins. Further, the resins described in paragraph numbers 0072 to 0094 of JP 2012-255128 A are mentioned, and the contents thereof are incorporated in the present specification.

  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. As the oligoimine dispersant, 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 polymer chain Y having 40 to 10,000 atoms are used. A resin having a side chain that includes and a basic nitrogen atom in at least one of the main chain and the side chain is preferable. This resin interacts with a pigment (for example, inorganic particles such as titanium oxide) with both a nitrogen atom and a functional group having a pKa of 14 or less in the structure X, and further, the resin is an oligomer having 40 to 10,000 atoms. Since the oligomer chain or the polymer chain Y has a chain or a polymer chain Y, for example, the oligomer chain or the polymer chain Y functions as a steric repulsion group, thereby exhibiting good dispersibility and uniformly dispersing inorganic particles such as titanium oxide. it can. Further, the interaction between the oligomer chain or the polymer chain Y and the solvent makes it possible to suppress sedimentation of inorganic particles such as titanium oxide for a long period of time. Further, since the aggregation of the pigment (for example, inorganic particles such as titanium oxide) is prevented by the oligomer chain or the polymer chain Y functioning as a steric repulsion group, the inclusion of the pigment (preferably inorganic particles such as titanium oxide) is included. Even if the amount is increased, excellent dispersibility can be obtained.

  Here, the "basic nitrogen atom" is not particularly limited as long as it is a nitrogen atom exhibiting basicity, and the resin contains a structure having a nitrogen atom of pKb (power of Kb; Kb is a base dissociation constant) 14 or less. Is preferable, and it is more preferable to contain a structure having a nitrogen atom of pKb10 or less. In the present invention, “pKb (base strength)” means pKb at a water temperature of 25 ° C., which is one of the indexes for quantitatively expressing the strength of the base, and is synonymous with the basicity constant. The base strength pKb and the acid strength pKa have a relationship of pKb = 14-pKa.

The functional group having a pKa of 14 or less contained in the partial structure X is not particularly limited, and the structure and the like are not particularly limited as long as the physical properties satisfy this condition. Particularly, 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, carboxy (about pKa 3 to 5), a sulfo group (about pKa -3~-2), - COCH 2 CO- group (about pKa 8~10), - COCH ₂ CN group (pKa about 8~11), - CONHCO- group, a phenolic hydroxyl group, -R _F CH ₂ OH group, or - (R _{F) 2} CHOH group (R _F about .PKa 9 to 11 represents a perfluoroalkyl group), sulfonamide A group (pKa about 9 to 11) and the like can be mentioned. The partial structure X having a functional group of pKa 14 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 are preferable. May be linked not only by a covalent bond but also by 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 bound, and an oligomer chain or polymer chain Y having 40 to 10,000 atoms in a side chain. It is preferably a resin.
The oligoimine-based dispersant includes (i) 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. At least one repeating unit containing a basic nitrogen atom selected from the units, which has 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 preferable. In the present invention, “lower” in poly (lower alkyleneimine) means that the carbon number is 1 to 5, and “lower alkyleneimine” means the 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) acrylic acid ester that can be linked to the main chain portion of the resin. The binding site of the oligomer chain or polymer chain Y with the resin is preferably the end of the oligomer chain or polymer chain Y.

  The oligomer chain or polymer chain Y is 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. Preferably, it is bonded to the nitrogen atom of the repeating unit containing at least one type of nitrogen atom. At least one nitrogen atom selected from poly (lower alkyleneimine) repeating units, polyallylamine repeating units, polydiallylamine repeating units, metaxylenediamine-epichlorohydrin polycondensate repeating units, and polyvinylamine repeating units The bonding mode between the main chain portion such as a repeating unit containing Y and Y is covalent bond, ionic bond, or a mixture of covalent bond and ionic bond. The ratio of the bonding mode between Y and the main chain part is covalent bond: ionic bond = 100: 0 to 0: 100, preferably 95: 5 to 5:95. Y is preferably amide-bonded to the nitrogen atom of the repeating unit containing a nitrogen atom or ionically bonded as a 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 the GPC method. The number average molecular weight of Y is preferably 1,000 to 50,000, more preferably 1,000 to 30,000.

  The oligoimine dispersant is, 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). Examples thereof include resins containing and.

R ¹ and R ² each independently represent a hydrogen atom, a halogen atom or an alkyl group (preferably having 1 to 6 carbon atoms).
a represents the integer of 1-5 each independently. * Represents a connecting part between repeating units.
R ⁸ and R ⁹ have the same meaning as R ¹ .
L is a single bond, an alkylene group (preferably having a carbon number of 1 to 6), an alkenylene group (preferably having a carbon number of 2 to 6), an arylene group (preferably having a carbon number of 6 to 24), a heteroarylene group (having 1 to 6 carbon atoms). Is preferred), an imino group (preferably having a carbon number of 0 to 6), an ether group, a thioether group, a carbonyl group, or a linking group related to a combination thereof. Of 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 represent 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 moiety that forms a ring structure with CR ⁸ CR ⁹ and N, and is preferably a structural moiety that forms a non-aromatic heterocycle having 3 to 7 carbon atoms with the carbon atom of CR ⁸ CR ^9. . More preferably, it is a structural moiety that forms a 5- to 7-membered non-aromatic heterocycle by combining the carbon atom of CR ⁸ CR ⁹ and N (nitrogen atom), and even more preferably a 5-membered non-aromatic heterocycle. It is a structural site to be formed, and particularly preferably a structural site to form pyrrolidine. 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 polymer chain having 40 to 10,000 atoms.

The dispersant (oligoimine-based dispersant) further comprises one or more copolymerizable components selected from the repeating units represented by formula (I-3), formula (I-4), and formula (I-5). May be contained as. When the dispersant contains such a repeating unit, the dispersibility of particles can be further improved.

^{R 1, R 2, R 8} , R 9, L, L a, a and * have the formula (I-1), (I -2), the same meaning as defined in (I-2a). Ya represents an oligomer chain or polymer chain having an anion group and having 40 to 10,000 atoms.

Regarding the oligoimine-based dispersant, the description in paragraphs 0118 to 0190 of JP-A-2005-34961 can be referred to, and the above contents are incorporated in the present specification. Specific examples of the oligoimine-based dispersant include the following resins and the resins described in paragraph Nos. 0169 to 0190 of JP-A-2013-34961.

In the present invention, it is preferable to use a dispersant which is a polysiloxane resin from the viewpoint of making all resins included in the composition have a mass average refractive index of 1.5 or less for light having a wavelength of 589 nm. The adsorption site of the dispersant, which is a polysiloxane resin, is not particularly limited, and it is preferable to have, for example, an acid group as the adsorption site.
The dispersant, which is a polysiloxane resin, preferably contains 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.
A resin having a refractive index of 1.5 or less for light having a wavelength of 589 nm may be used as the dispersant which is a polysiloxane resin. A preferred embodiment of the dispersant which is a polysiloxane resin is the same as a preferred embodiment of a resin having a refractive index of 1.5 or less for light having a wavelength of 589 nm.

The dispersant is also available as a commercial product, and specific examples thereof 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 Corporation "EFKA 4047, 4050, 4010, 4165 (polyurethane type), EFKA 4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyester amide)" , 5765 (high molecular weight polycarboxylate), 6220 (fat Polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) ", Ajinomoto Fine-Techno Co., Ltd." Addisper PB821, PB822 ", Kyoeisha Chemical Co., Ltd." Floren TG-710 (urethane oligomer) ", Kyoeisha Chemical "Polyflow No. 50E, No. 300 (acrylic copolymer)" manufactured by Co., Ltd., "Disparlon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid) manufactured by Kusumoto Kasei Co., Ltd., # 7004 (polyether ester), DA-703-50, DA-705, DA-725 ", Kao Corporation's" Demol RN, N (naphthalene sulfonic acid formalin polycondensate), MS, C, SN-B ( Aromatic sulfonic acid formalin polycondensate) ", Kao Corporation" Homogenol L-18 (polymer high molecular weight) " Boric acid) ", Kao Corporation" Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) "," acetamine 86 (stearylamine acetate) ", Lubrizol Co., Ltd." Solsperse 5000 (Solsperse 5000) ". ) (Phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyester amine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 26000, 28000, 32000, 36000, 38500 (graft type) Polymer), 41000, 46000 ", Nikko Chemicals Co., Ltd." Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) "and the like. Be done.
Further, as a commercial product of a dispersant having a phosphorus atom-containing group (for example, a phosphoric acid group or the like) as an acid-based adsorption site, “Solsperse 26000, 36000, 41000” manufactured by Lubrizol Corporation can be mentioned. These can be used suitably.
Examples of the polysiloxane resin dispersant include KP-578, which is a graft copolymer containing an acrylic polymer and dimethylpolysiloxane, and polysiloxane resin dispersant X-22-3701E (both Shin-Etsu Chemical Co., Ltd.). Co., Ltd.) and the like.
The dispersant may be used alone or in combination of two or more.
As the dispersant, the resins described for the other binders described above can also be used. Further, as the dispersant, a resin having a refractive index of 1.5 or less for light having a wavelength of 589 nm may be used.

The composition of the present invention may contain, as a dispersion aid, a dispersion aid having an acid group and a crosslinkable group. 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 also include addition-polymerizable ethylene groups mentioned in the description of the polymerizable compound.
Examples of commercially available products of the dispersion aid include light ester P-1M, light ester P-2M, light ester HO-MS, light ester HO-HH (above, Kyoeisha Chemical Co., Ltd.) Phosmer M, Hosmer PE, Phosmer MH. , Hosmer CL, Hosmer PP (all manufactured by Unichemical Co., Ltd.), TBAS-Q, TBAS-R (all manufactured by MRC Unitech Co., Ltd.), and the like.

The content of the dispersant is preferably 1 to 80% by mass based on the total solid content of the composition, from the viewpoint of L *, pattern shape and adhesiveness. 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, more preferably 60 parts by mass or less. The lower limit is preferably 2.5 parts by mass or more, more preferably 5 parts by mass or more.
Further, 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, more preferably 60 parts by mass or less. The lower limit is preferably 2.5 parts by mass or more, more preferably 5 parts by mass or more.
Further, 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, more preferably 60 parts by mass or less. The lower limit is preferably 2.5 parts by mass or more, more preferably 5 parts by mass or more.

<< solvent >>
The composition of the present invention preferably contains a solvent. The solvent may be composed of various organic solvents. As the organic solvent, 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 And so on. These organic solvents can be used alone or in combination.

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, for example, 10 mass ppb or less. 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 methods for removing impurities such as metals from the solvent include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter. The pore size of the filter used for filtration is preferably 10 nm or less, more preferably 5 nm or less, and further 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, the isomer may contain only one kind or plural kinds.

  The content of the solvent is preferably such that the solid content concentration of the composition is 25 to 70% by mass, more preferably 30 to 60% by mass.

<< 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) with a radical, an acid, or heat. The curable compound used in the present invention includes, for example, a compound having a group having an ethylenically unsaturated bond, a compound having an epoxy group, a compound having a methylol group, and the like, 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 radically polymerizable compound. Examples of the radically polymerizable compound include compounds having a group having an ethylenically unsaturated bond. The composition of the present invention may have a compound having an epoxy group described below as a curable compound. Hereinafter, unless otherwise specified, the term "polymerizable compound" means a radically polymerizable compound.

  The content of the curable compound is preferably 1 to 70 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 mass% or less, more preferably 50 mass% or less, particularly preferably 12 mass% or less. It is preferable that the content is within these ranges from the viewpoint of pattern shape, heat resistance and L *. The curable compound used in the composition may be only one kind or two or more kinds. In the case of two or more kinds, the total amount is preferably within the above range.

When a polymerizable compound is used as the curable compound, the content of the polymerizable compound is preferably 1 to 70 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 kind or two or more kinds. In the case of two or more kinds, 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.

(Polymerizable compound)
The composition of the present invention has a refractive index of 1.55 or less (preferably 1.52 or less, more preferably 1.5 or less) for light having a wavelength of 589 nm in the total mass of the radically polymerizable compound. Is preferably 80% by mass or more, more preferably 85% by mass or more, and particularly preferably 90% by mass or more.

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 group (preferably two or more) having a terminal ethylenically unsaturated bond is more preferable. Further, 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, more preferably 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. In addition, the polymerizable compound is preferably a radically polymerizable compound.

  The polymerizable compound may be in the form of a monomer or a polymer, and the monomer is preferable. The molecular weight of the monomer-type polymerizable compound is preferably 100 to 3000. The upper limit is preferably 2000 or less, more preferably 1500 or less. The lower limit is preferably 150 or more, 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 a 3 to 4 functional (meth) acrylate compound. Is more preferable. According to this aspect, the solvent resistance of the obtained film and the adhesion to the substrate can be improved. The polymerizable compound is also preferably a hexafunctional or higher functional (meth) acrylate compound.

  The polymerizable compound is also preferably a compound having at least one addition-polymerizable ethylene group and a group having an ethylenically unsaturated bond having a boiling point of 100 ° C. or higher under normal pressure. Examples thereof 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.

  As the polymerizable compound, polymerizable compounds represented by the following formulas (MO-1) to (MO-5) can also be preferably used. In the formula, when T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R.

In the above formula, n is an integer of 0 to 14 and m is an integer of 1 to 8. Plural R and T existing in the same molecule may be the same or different.
In each of the above formulas (MO-1) ~ (MO -5) polymerizable compound represented by at least one of the plurality of R may, -OC (= O) CH = CH 2, or, -OC (= O) C (CH ₃ ) = Represents a group represented by CH ₂ .
Specific examples of the polymerizable compound represented by the formulas (MO-1) to (MO-5) include the compounds described in paragraphs 0248 to 0251 of JP2007-269779A.
Further, a compound described in JP-A-10-62986, which is obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylated, can be used as the polymerizable compound.

The polymerizable compound is pentaerythritol tetraacrylate (commercially available, NK ester A-TMMT; manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol triacrylate (commercially available as KAYARAD D-330; Nippon Kayaku ( Ltd.), dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Nippon Kayaku Co., Ltd.) dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; Nippon Kayaku (Nippon Kayaku) Co., Ltd.) and dipentaerythritol hexa (meth) acrylate (commercially available KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) are preferable, and pentaerythritol tetraacrylate is more preferable from the viewpoint of pattern shape.

  The polymerizable compound may have an acid group such as a carboxy group, a sulfo group and a phosphoric acid group. The polymerizable compound having an acid group can be obtained by, for example, converting a part of the hydroxy groups of the polyfunctional alcohol into (meth) acrylate and adding the acid anhydride to the remaining hydroxy group to form a carboxy group. Examples of the polymerizable compound having an acid group include an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid. 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 have an acid group, and particularly preferably in this ester. The aliphatic polyhydroxy compound is at least one of pentaerythritol and dipentaerythritol. Examples of commercially available products include 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 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.

  In addition, the polymerizable compound is also 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, and examples thereof include trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, and tripenta. Examples thereof include ε-caprolactone-modified polyfunctional (meth) acrylate obtained by esterifying (meth) acrylic acid and ε-caprolactone with a polyhydric alcohol such as erythritol, glycerin, diglycerol, and trimethylolmelamine. . The polymerizable compound having a caprolactone structure is preferably a compound represented by the following formula (Z-1).

  In formula (Z-1), 6 Rs are all groups represented by formula (Z-2), or 1 to 5 of 6 Rs are represented by formula (Z-2). And the remainder is a group represented by the formula (Z-3).

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.

In formula (Z-3), R ¹ represents a hydrogen atom or a methyl group, and “*” represents a bond.

The polymerizable compound having a caprolactone structure is commercially available, for example, from Nippon Kayaku Co., Ltd. as KAYARAD DPCA series, and DPCA-20 (m = 1 in the above formulas (Z-1) to (Z-3), the formula: Number of groups represented by (Z-2) = 2, compounds in which all R ¹ are hydrogen atoms, DPCA-30 (same formula, m = 1, number of groups represented by formula (Z-2)) = 3, a compound in which R ¹ is all hydrogen atoms), DPCA-60 (the same formula, m = 1, the number of groups represented by formula (Z-2) = 6, and a compound in which R ¹ is all hydrogen atoms ), DPCA-120 (m = 2 in the formula, the number of groups represented by the formula (Z-2) = 6, and compounds in which all R ¹ are hydrogen atoms) and the like.

  As the polymerizable compound, a compound represented by the formula (Z-4) or (Z-5) can also be used.

Wherein (Z-4) and (Z-5), E are each _{independently, - ((CH 2) y} CH 2 O) -, or _{- ((CH 2) y CH} (CH 3) O) - And y each independently represents an integer of 0 to 10, and X each independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxy group.
In formula (Z-4), the total of (meth) acryloyl groups is 3 or 4, m each independently represents an integer of 0 to 10, and the sum of each m is an integer of 0 to 40.
In formula (Z-5), the total of (meth) acryloyl groups is 5 or 6, n is each independently an integer of 0 to 10, and the sum of each n is an integer of 0 to 60.

In formula (Z-4), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
Moreover, the sum 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 formula (Z-5), n is preferably an integer of 0 to 6, more preferably an integer of 0 to 4.
Moreover, the sum 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.
Further, the formula (Z-4) or formula (Z-5) in the _{- ((CH 2) y CH} 2 O) - or _{- ((CH 2) y CH} (CH 3) O) - , the oxygen atom side A form in which the end of is bound 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. In particular, in the formula (Z-5), a form in which all six X are acryloyl groups is preferable.

  The total content of the compound represented by formula (Z-4) or 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 by a ring-opening addition reaction of pentaerythritol or dipentaerythritol with ethylene oxide or propylene oxide, which is a conventionally known step. Can be synthesized, and a terminal hydroxy group of the ring-opening skeleton is reacted with, for example, (meth) acryloyl chloride to introduce a (meth) acryloyl group. Each step is a well-known step, and a person skilled in the art can easily synthesize the compound represented by the formula (Z-4) or the formula (Z-5).

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)”), and among them, exemplary compounds (a) and ( Preferred are b), (e) and (f).

  Examples of commercially available polymerizable compounds represented by Formulas (Z-4) and (Z-5) include SR-494, which is a 4-functional acrylate having four ethyleneoxy groups manufactured by Sartomer Co., Ltd. Examples include DPCA-60, which is a hexafunctional acrylate having 6 pentyleneoxy groups, and TPA-330, which is a trifunctional acrylate having 3 isobutyleneoxy groups, manufactured by Yakuhin Co., Ltd.

The polymerizable compound is a urethane acrylate as described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, or JP-B-2-16765, or a special compound. 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. Further, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule, which are described in JP-A-63-277653, JP-A-63-260909 and JP-A-1-105238, are also preferable. .
As commercially available products of the polymerizable compound, urethane oligomer 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 Co., Ltd.) and the like.

Further, the polymerizable compound is also preferably a polymerizable compound having a Si atom in the molecule. Particularly 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 of 1.5 or less for light having a wavelength of 589 nm. By forming a film using a composition containing a radically polymerizable compound having a refractive index of 1.5 or less with respect to light having a wavelength of 589 nm and curing the film to form a cured film, the wavelengths of components other than the particles of the cured film described below. It is easy to set the refractive index for light of 589 nm to 1.5 or less.
Examples of commercially available polymerizable compounds having Si atoms in the molecule include EBECRYL1360 (manufactured by Daicel Ornex Co., Ltd.), which is a siloxane bond-containing polyfunctional acrylate, and VINYLTRIISOPROPENOXYSILANE, which is a Si atom-containing polyfunctional vinyl compound. Manufactured) and the like.

  Regarding these polymerizable compounds, the details of the structure, usage alone or in combination, usage such as addition amount, etc. 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 a group having an ethylenically unsaturated bond per molecule is preferable, and in many cases, a bifunctional or more functional group is preferable. Further, from the viewpoint of increasing the strength of the cured film, a trifunctional or higher functional compound is preferable, and further, at least one of the functional number and the polymerizable group (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound). A method of controlling both sensitivity and intensity by using different compounds in combination is also effective. Further, it is also preferable to use together a polymerizable compound having three or more functional groups and 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. Further, at least one of the compatibility and dispersibility with other components contained in the composition (for example, a photopolymerization initiator, a resin, etc.) is at least one of the methods for selecting and using the polymerizable compound. This is a preferable factor, and for example, compatibility can be improved by using a low-purity compound or by using two or more kinds in combination.

(Compound having an epoxy group)
In the composition of the present invention, a compound having an epoxy group can 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 a monofunctional or polyfunctional glycidyl ether compound and a polyfunctional aliphatic glycidyl ether compound. Further, a compound having an epoxy group such as glycidyl (meth) acrylate or allyl glycidyl ether as a part of the glycidyl group, or a compound having an alicyclic epoxy group can also be used.

  Examples of the compound having an epoxy group include compounds having one or more epoxy groups in one molecule. It is preferable to have 1 to 100 epoxy groups in one molecule. The upper limit may be, for example, 10 or less, or 5 or less. The lower limit is preferably 2 or more.

  The compound having an epoxy group has an epoxy equivalent (= molecular weight of the compound having an epoxy group / the number of epoxy groups) of preferably 500 g / equivalent or less, more preferably 100 to 400 g / equivalent, and 100 to 300 g. More preferably, it is equivalent.

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 macromolecular compound (for example, a molecular weight of 1000 or more, and in the case of a polymer, a weight average molecular weight of 1000 or more). . 200-100,000 are preferable and, as for the weight average molecular weight of the compound which has an epoxy group, 500-50000 are more preferable. The upper limit of the weight average molecular weight is preferably 10,000 or less, more preferably 5000 or less, still more preferably 3000 or less.
The compound having an epoxy group is preferably an aliphatic epoxy resin from the viewpoint of solvent resistance.

  The compound having an epoxy group is described in paragraph numbers 0034 to 0036 of JP2013-011869A, paragraphs 0147 to 0156 of JP2014-043556A, and paragraphs 0085 to 0092 of JP2014-0889408A. The compound can also be used. These contents are incorporated herein. As commercially available 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 (above, manufactured by DIC Corporation), etc., and as bisphenol F type epoxy resin, jER806, jER807, jER4004, jER4005, jER4007, jER4010 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON830, EPICLON835. (Above, manufactured by DIC Corporation), LCE-21, RE-602S (above, manufactured by Nippon Kayaku Co., Ltd.), etc. As the phenol novolac type epoxy resin, jER152, jER154, jER157S70, jER157S65 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON N-740, EPICLON N-770, EPICLON N-775 (above, manufactured by DIC Corporation) ) Etc., as the cresol novolac type epoxy resin, EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (above, DIC Co., Ltd.), EOCN-1020 (above, Nippon Kayaku Co., Ltd.), and the like, as the aliphatic epoxy resin, ADEKA RESIN EP-4080S, EP-4085S, EP. -4088S (above, manufactured by ADEKA Co., Ltd.), Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEAD PB 3600, PB 4700 (above, Daicel Corporation), Denacol EX-212L, EX-. 214L, EX-216L, EX-321L, EX-850L (above, Nagase Chemtex Co., Ltd. product) etc. In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (above, manufactured by ADEKA), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, ADEKA Corporation make), jER1031S (Mitsubishi Chemical Corporation make) etc. are mentioned.

  As the compound having an epoxy group, the compound described in paragraph 0045 of JP-A-2009-265518 can be used, and the contents thereof are incorporated in the present specification.

<< 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 based on the total solid content of the composition, from the viewpoint of solvent resistance and colorability, more preferably 0.5 to 30% by mass, and further preferably Is 1 to 10% by mass. The composition may include only one type of polymerization initiator, or may include two or more types. When two or more kinds 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. The thermal polymerization initiator is not particularly limited, and known compounds can be used.

(Photopolymerization initiator)
The composition of the present invention may contain a photopolymerization initiator. In particular, when the composition contains a polymerizable compound, it is preferable to contain a photopolymerization initiator. The photopolymerization initiator is not particularly limited and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity to light rays 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 in the range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).

  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, hexaarylbiimidazole, oxime derivatives, etc. Oxime compound, organic peroxide, thio compound, ketone compound, aromatic onium salt, ketoxime ether, aminoacetophenone compound, hydroxyacetophenone, and the like. As the halogenated hydrocarbon compound having a triazine skeleton, for example, Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), compounds described in British Patent No. 1388492, compounds described in JP-A No. 53-133428, compounds described in German Patent No. 3337024, F.I. C. Schaefer et al., J. Org. Chem. 29, 1527 (1964), the compound described in JP-A-62-58241, the compound described in JP-A-5-281728, the compound described in JP-A-5-34920, and U.S. Pat. No. 4,129,976. Examples thereof include the compounds described in the specification.

  Further, from the viewpoint of exposure sensitivity, trihalomethyltriazine compound, benzyldimethylketal compound, α-hydroxyketone compound, α-aminoketone compound, acylphosphine compound, phosphine oxide compound, metallocene compound, oxime compound, triallylimidazole dimer, onium. A compound selected from the group consisting of a compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound and its derivative, a cyclopentadiene-benzene-iron complex and its salt, a halomethyloxadiazole compound, and a 3-aryl-substituted coumarin compound is preferable. As the photopolymerization initiator which is a trihalomethyltriazine compound, triazine PP (manufactured by BASF) which is a trichloromethyltriazine compound can be used.

As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be preferably used. More specifically, for example, the aminoacetophenone type initiator described in JP-A-10-291969 and the acylphosphine type initiator described in Japanese Patent No. 4225898 can be used. As the hydroxyacetophenone-based initiator, IRGACURE 184, DAROCUR 1173, IRGACURE 500, IRGACURE 2959, IRGACURE 127 (trade name: all manufactured by BASF Corporation) can be used. As the aminoacetophenone initiator, commercially available products such as IRGACURE 907, IRGACURE 369, and IRGACURE 379, IRGACURE 379EG (trade names: all manufactured by BASF Corporation) can be used. As the aminoacetophenone-based initiator, the compound described in JP-A-2009-191179 in which the absorption wavelength is matched with a long-wave light source of 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: all 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. As the oxime compound, an oxime ester compound is more preferable. Specific examples of the oxime compound include compounds described in JP 2001-233842 A, compounds described in JP 2000-80068 A, compounds described in JP 2006-342166 A, and JP 2010-21012 A. Can be used.

  Examples of oxime compounds that can be suitably used in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, and 2 -Acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2 -One, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, and the like. Also, J. C. S. Perkin II (1979) pp. 1653-1660, J. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, the compound described in JP-A-2000-66385, the compound described in JP-A-2000-80068, JP-A-2004-534797, JP-A-2006-342166, and the like. Among commercially available products, IRGACURE OXE01 (manufactured by BASF Ltd.) and IRGACURE OXE02 (manufactured by BASF Ltd.) are also preferably used. Moreover, TR-PBG-304 (manufactured by Changzhou Power Electronics Co., Ltd.), ADEKA ARKUL'S NCI-930, ADEKA OPTOMER N-1919 (above, manufactured by ADEKA Corporation) can also be used.

In addition, as the oxime compound other than the above, the compound described in Japanese Patent Publication No. 2009-519904 in which an oxime is linked to the N-position of carbazole, the compound described in U.S. Pat. No. 7,626,957 in which a hetero substituent is introduced into a benzophenone site, and a dye JP-A-2010-15025 and a compound described in U.S. Patent Publication No. 2009-292039 in which a nitro group is introduced at a site, a ketoxime compound described in International Publication No. 2009-131189, a triazine skeleton and an oxime skeleton in the same molecule. Disclosed in U.S. Pat. No. 7,556,910, a compound described in JP-A-2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-ray light source, and a compound described in JP-A-2014-137466. Paragraph numbers 0076 to 0079 Or the like may be used things.
Preferably, for example, paragraphs 0274 to 0275 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
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 the (E) form or an oxime compound in which the N—O bond of the oxime is the (Z) form, and the (E) form and (Z ) It may be a mixture with the body.

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 non-metal atomic group.
Examples of the monovalent non-metal 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 above-mentioned substituent may be further substituted with 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 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-mentioned substituents.
In 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-mentioned substituents.

  In the present invention, an oxime compound having a fluorene ring can be used as the photopolymerization initiator. Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A-2014-137466. This content is incorporated herein.

  In the present invention, an oxime compound having a fluorine atom can be used as the photopolymerization initiator. Specific examples of the oxime compound having a fluorine atom include compounds described in JP2010-262028A, compounds 24, 36 to 40 described in JP-A-2014-500852, and compounds described in JP2013-164471A. C-3) etc. are mentioned. This content is incorporated herein.

  In the present invention, an oxime compound having a nitro group can be used as the photopolymerization initiator. The oxime compound having a nitro group is also preferably dimerized. Specific examples of the oxime compound having a nitro group include compounds described in paragraphs 0031 to 0047 of JP2013-114249A, paragraphs 0008 to 0012, and 0070 to 0079 of JP2014-137466A. Compounds described in paragraphs 0007 to 0025 of JP 4223071 A, ADEKA ARKUL'S NCI-831 (manufactured by ADEKA Co., Ltd.) can be mentioned.

  Specific examples of the oxime compound 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 the wavelength region of 350 nm to 500 nm, more preferably a compound having an absorption wavelength in the wavelength region of 360 nm to 480 nm, particularly preferably a compound having a high absorbance at 365 nm and 405 nm.

  From the viewpoint of sensitivity, the molar absorption coefficient of the oxime compound at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and 5,000 to 200, 000 is particularly preferable. A known method can be used to measure the molar extinction coefficient of the compound. Specifically, a UV-visible spectrophotometer (manufactured by Varian Co., Ltd., Cary-5 spectrophotometer) is used, and ethyl acetate is used. It is preferable to measure at a concentration of 01 g / L.

In the present invention, it is also preferable to use two or more photopolymerization initiators in combination. For example, a photopolymerization initiator having an absorption coefficient of 365 nm in methanol of 1.0 × 10 ³ mL / gcm or more, and an absorption coefficient of 365 nm in methanol of 1.0 × 10 ² mL / gcm or less, It is also preferable to use together with a photopolymerization initiator having an absorption coefficient at 254 nm of 1.0 × 10 ³ mL / gcm or more. A specific example is the combined use of an aminoacetophenone compound and an oxime compound. According to this aspect, it is possible to produce a film having excellent curability even under low temperature conditions. For example, in the pattern forming step, by exposing the composition in two stages before and after the developing step, the composition can be appropriately cured by the first exposure, and the entire composition can be almost completely exposed by the second exposure. Can be cured. Therefore, the curability of the composition can be improved even under low temperature conditions.

<< coloration preventing agent >>
The composition of the present invention preferably contains a coloring preventing agent.
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 anti-coloring agent include a phenol compound, a phosphite ester compound, and a thioether compound, and a phenol compound having a molecular weight of 500 or more, a phosphite compound having a molecular weight of 500 or more, or a thioether compound having a molecular weight of 500 or more is more preferable. Further, the coloring agent is preferably a phenol compound, and more preferably a phenol compound having a molecular weight of 500 or more.

  As the phenol compound, any phenol compound known as a phenolic color preventive agent can be used. Preferable phenol compounds include hindered phenol compounds. In particular, a compound having a substituent at the 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 ester group in the same molecule is also preferable.

As the phenolic hydroxyl group-containing compounds, polysubstituted phenolic compounds are particularly preferably used.
There are three types of polysubstituted phenolic compounds having different substitution positions and structures due to their reactivity with peroxy radicals to be trapped 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.

In the above formulas (A) to (C), which are structural portions that exhibit a coloring preventing function, R is a substituent, which has a hydrogen atom, a halogen atom, an amino group which may have a substituent, and a substituent. Optionally substituted alkyl group, optionally substituted aryl group, optionally substituted alkoxy group, optionally substituted aryloxy group, optionally substituted alkylamino Group, an arylamino group that may have a substituent, an alkylsulfonyl group that may have a substituent, an arylsulfonyl group that may have a substituent, and the like. Good amino group, 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 group which may have a substituent, a substituent Aryl amino group which may have preferred.

A more preferable form is a composite color preventive agent having a plurality of structures exhibiting a color preventive function represented by the above formulas (A) to (C) in the same molecule, and specifically, the above formula (A). Compounds represented by (C) to (C) having 2 to 4 structures exhibiting a coloring preventing function in the same molecule are preferable. Among these, the formula (B) semi-hindered type is more preferable from the viewpoint of colorability.
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) and 2,2 ′. -Methylenebis (4-methyl-6-t-butylphenol), a compound selected from the group consisting of 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 Stab AO-20, AO-50, AO-60 (manufactured by ADEKA). Yes, (B) includes Sumilizer BBM-S (manufactured by Sumitomo Chemical), Irganox 245 (manufactured by BASF), ADEKA STAB AO-80 (manufactured by ADEKA), etc., and (C) ADEKA STAB AO-30, AO-40 ( Made by ADEKA).

  Examples of the phosphite compound include tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphepine-6. -Yl] oxy] ethyl] amine, tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphepin-2-yl ) Oxy] ethyl] amine and at least one compound selected from the group consisting of ethyl bis (2,4-ditert-butyl-6-methylphenyl) phosphite.

Examples of the thioether compound include dialkyl thiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate and distearyl thiodipropionate, and pentaerythritol tetra (β-alkylthiopropionate) esters; penta Erythrityl tetrakis (3-lauryl thiopropionate), 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-t-butylphenyl) sulfide, ditridecyl-3,3 ′ -Thiodipropionate Dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, lauryl / stearyl thiodipropionate, 4,4'- Thiobis (6-t-butyl-m-cresol), 2,2'-thiobis (6-t-butyl-p-cresol) and distearyl-disulfide are preferred.
Typical examples of commercially available thioether compounds include Adeka Stab AO-412S (CAS: 29598-76-3, manufactured by ADEKA), Adeka Stab AO-503 (CAS: 10595-72-9, manufactured by ADEKA). Manufactured by Kemipro Chemicals Co., Ltd.) and KEMINOX PLS (CAS: 29598-76-3).
The anti-coloring agent is easily available as a commercial product, and in addition to the above-mentioned representatives that are commercially available, ADEKA STAB AO-50F, ADEKA STAB AO-60G, ADEKA STAB AO-330, ADEKA STAB PEP-36A ( (Made by ADEKA Co., Ltd.) and the like.

  The content of the anti-coloring agent is preferably 0.01 to 20 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 mass%. , 0.3 to 5 mass% is particularly preferable. The anti-coloring agent may be only one type or two or more types. In the case of two or more kinds, the total amount is preferably within the above range.

<< UV absorber >>
The composition of the present invention may contain an ultraviolet absorber. The ultraviolet absorber is preferably a conjugated diene compound, more preferably a compound represented by the following formula (I).

In formula (I), R ¹ and R ² each independently represent 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 They may be the same or different from each other, but do not represent hydrogen atoms 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 a piperidino group, a morpholino group, a pyrrolidino group, a hexahydroazepino group, and a piperazino group.
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. Preferred 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 an acyl group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, an alkylsulfonyl group, an arylsulfonyl group, a sulfonyloxy group or a sulfamoyl group, and an acyl group or a carbamoyl group. A group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, a sulfonyloxy group, and a 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 description of the substituents of the ultraviolet absorber represented by the formula (I) is described in WO2009 / 123109A, paragraphs 0024 to 0033 (corresponding US Patent Application Publication No. 2011/0039195, <0040> to <0059>). Can be referred to, and the contents thereof are incorporated herein. Preferable specific examples of the compound represented by the formula (I) are exemplified compounds (1) to (of paragraphs 0034 to 0037 of WO2009 / 123109A (<0060> of the corresponding US Patent Application Publication No. 2011/0039195)). The description of 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).

  The content of the ultraviolet absorber is preferably 0.1 to 10 mass% with respect to the total solid content of the composition from the viewpoint of the pattern shape and solvent resistance, and is 0.1 to 7 mass%. Is more preferable, 0.1 to 5 mass% is still more preferable, and 0.1 to 3 mass% is particularly preferable. Further, in the present invention, the ultraviolet absorber may be only one kind or two or more kinds. In the case of two or more kinds, the total amount is preferably within the above range.

<< Adhesive >>
The composition of the present invention preferably further contains an adhesive agent. The adhesive agent is not particularly limited, and known adhesive agents can be used. Examples of the adhesive agent include a silane coupling agent. According to this aspect, the adhesion of the film to the base material can be improved.
In the present invention, the “silane coupling agent” means a silane compound having a hydrolyzable group and a functional group other than that. Further, the “hydrolyzable group” refers to a substituent which 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. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group and the like, and 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 which exhibits affinity by interacting with or forming a bond with the resin. Examples thereof 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.
1-5 are preferable, as for carbon number of the alkoxy group in an alkoxy silyl group, 1-3 are more preferable, and 1 or 2 is especially preferable. It is preferable to have two or more alkoxysilyl groups in the same molecule, and it is more preferable to have two to three alkoxysilyl groups.

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 Ryl) hexane, trifluoropropyltrimethoxysilane, hexamethyldisilazane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane , 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, parastyryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryl 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, an alkoxy oligomer can be used. Moreover, the following compounds can also be used.

Examples of commercially available products include KBM-13, KBM-22, KBM-103, KBE-13, KBE-22, KBE-103, KBM-3033, KBE-3033, KBM-3063, and 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 can be mentioned. Examples of the silane coupling agent include compounds described in paragraph Nos. 0018 to 0036 of JP 2009-288703 A and compounds described in paragraphs 0056 to 0066 of JP 2009-242604 A. Incorporated in the description.
Further, as the compound having an alkoxysilyl group, a polymer having an alkoxysilyl group in its side chain can be used.
As the silane coupling agent, the specific silane compounds described in <0011> to <0037> of JP 2009-288703 A can also be used in consideration of the contents, and the contents thereof are incorporated in the present specification.

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 adhesive 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, based on the total solid content of the composition. It is preferable that the amount is within the range from the viewpoints of adhesion and unevenness in density after one month. Further, in the present invention, the adhesive agent contained in the composition may be only one kind or two or more kinds. In the case of two or more kinds, the total amount is preferably within the above range.

<< chain transfer agent >>
The composition of the present invention preferably contains a chain transfer agent. According to this aspect, the curing of the film surface (pattern surface) can be promoted by the exposure during the exposure during pattern formation. Therefore, it is possible to suppress a decrease in film thickness during exposure, and it is easy to form a pattern having more excellent rectangularity and adhesiveness.

Examples of the chain transfer agent include N, N-dialkylaminobenzoic acid alkyl esters and thiol compounds, and thiol compounds are preferable. The thiol compound is preferably a compound having two 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 heterocycles, pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercapto) Examples include aliphatic thiol compounds such as butyryloxy) butane.
Commercially available chain transfer agents include PEMP (SC Organic Chemical Co., Ltd., thiol compound), Sancellar M (Sanshin Chemical Industry Co., Ltd., thiol compound), Karens MT BD1 (Showa Denko KK). , Thiol compounds) and the like.
It is also preferable to use the following compounds.

The content of the chain transfer agent is preferably 0.2 to 5.0% by mass, and 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.
The chain transfer agent may be only one type or two or more types. In the case of two or more kinds, the total amount is preferably within the above range.

<< 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, those that sensitize the photopolymerization initiator by an electron transfer mechanism or an energy transfer mechanism are preferable. Examples of the sensitizer include those having an absorption wavelength in the wavelength region of 300 nm to 450 nm. Specifically, the description of paragraphs 0231 to 0253 of JP 2010-106268 A (<0256> to <0273> of the corresponding US Patent Application Publication No. 2011/0124824) can be referred to, and the contents thereof 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, based on the total solid content of the composition. The sensitizer may be only one type or two or more types. In the case of two or more kinds, the total amount is preferably within the above range.

<< Co-sensitizer >>
The composition of the present invention preferably further contains a co-sensitizer. The co-sensitizer has a function of further improving the sensitivity of the photopolymerization initiator or the sensitizer to actinic radiation, or suppressing the inhibition of polymerization of oxygen-polymerizable compounds. Specific examples of the co-sensitizer are described in paragraphs 0254 to 0257 of JP 2010-106268 A (<0277> to <0279> of corresponding US Patent Application Publication No. 2011/0124824). Reference may be made to these contents, which are incorporated herein.

  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 mass% is more preferable. The co-sensitizer may be only one type or two or more types. In the case of two or more kinds, the total amount is preferably within the above range.

<< polymerization inhibitor >>
A polymerization inhibitor is preferably added to the composition of the present invention 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 compound (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-tetramethyl piperidine 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-carboxyproxil free radical (3-carboxy-2,2,5,5-tetramethylpyrrolidine 1-oxyl free radical));
N-nitrosophenylhydroxyamines (preferably compounds selected from the group of compounds consisting of N-nitrosophenylhydroxyamine primary cerium salts and N-nitrosophenylhydroxyamine aluminum salts);
Diazonium compounds (preferably selected from the group consisting of hydrogen sulfate of 4-diazophenyldimethylamine, tetrafluoroborate salt of 4-diazodiphenylamine, and hexafluorophosphate salt of 3-methoxy-4-diazodiphenylamine) 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 having 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 No. 10-46035 are preferably used.

  Specific examples of the polymerization inhibitor include compounds described in paragraphs 0121 to 0223 of JP-A-2005-34961, the contents of which are incorporated herein.

  The content of the polymerization inhibitor is preferably 0.01 parts by mass to 10 parts by mass, more preferably 0.01 to 8 parts by mass, and 0.01 to 5 parts by mass with respect to 100 parts by mass of the photopolymerization initiator. Most preferred. When the content is in the above range, the curing reaction is suppressed in the non-image area and the curing reaction is promoted in the image area, and the pattern shape and sensitivity are improved. The polymerization inhibitor may be only one type or two or more types. In the case of two or more kinds, the total amount is preferably within the above range.

<< Surfactant >>
The composition of the present invention may contain a surfactant of each type from the viewpoint of further improving suitability for coating. As the surfactant, various kinds of surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.

  By containing a fluorine-based surfactant in the above composition, the liquid properties (particularly, the fluidity) when prepared as a coating liquid can be further improved, and the uniformity of the coating thickness and the liquid saving property 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 fluorine-based surfactant is applied, the interfacial tension between the surface to be coated and the coating liquid decreases, and the wettability to the surface to be coated is reduced. It is improved, and the suitability for coating on the surface to be coated is improved. Therefore, it is possible to more favorably form a film having a uniform thickness with a small thickness unevenness.

  The content of fluorine in the fluorine-based surfactant 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, and also has good solubility in the composition.

  Specific examples of the fluorine-based surfactant include the surfactants described in JP-A-2014-41318, paragraphs 0060 to 0064 (corresponding to WO 2014/17669, paragraphs 0060 to 0064), JP-A-2011. The surfactants described in paragraphs 0117 to 0132 of JP-A-132503 can be mentioned, and the contents thereof are incorporated herein. Examples of commercially available fluorine-based surfactants include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437 and F475. Same F479, Same F482, Same F554, Same F780 (above, DIC Corporation), Florard FC430, Same FC431, Same FC171 (above, Sumitomo 3M Ltd.), Surflon S-382, Same SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (above Asahi Glass Co., Ltd.), PolyFox. Examples thereof include PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA).

A block polymer can also be used as the fluorine-based surfactant. For example, the compounds described in JP 2011-89090 A may be mentioned. 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 groups and propyleneoxy groups) (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 fluorine-based surfactant 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.

  Further, as the fluorine-based surfactant, a fluorine-containing polymer having a side chain of a group having an ethylenically unsaturated bond can be used. As specific examples, compounds described in JP-A-2010-164965, paragraphs 0050 to 0090 and paragraphs 0289 to 0295, for example, Megafac RS-101, RS-102, RS-718K, and RS- manufactured by DIC Corporation. 72-K and the like. As the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of JP-A-2005-117327 can also be used.

  Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerolpropoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl 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 Corporation) ), Sols Perth 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.), Olfine E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry Co., Ltd.) and the like.

  Examples of the cationic surfactant include organosiloxane polymer KP341 (produced by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid-based (co) polymer polyflow No. 75, no. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.

  Examples of anionic surfactants include W004, W005, W017 (manufactured by Yusho Co., Ltd.), and Sandet BL (manufactured by Sanyo Kasei Co., Ltd.).

  Examples of the silicone-based surfactant include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (above, Toray Dow Corning Co., Ltd. )), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (above, Momentive Performance Materials Inc.), KP341, KF6001, KF6002 (above, Shinetsu Silicone Co., Ltd.). , BYK307, BYK323, BYK330 (above, manufactured by Big Chemie) and the like.

As the surfactant, only one kind may be used, or two or more kinds may be combined.
The content of the surfactant is preferably 0.001 to 2.0 mass% and more preferably 0.005 to 1.0 mass% with respect to the total solid content of the composition.

<< Other additives >>
Further, known additives such as a plasticizer and an oil 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 based on the total mass of the polymerizable compound and the resin.

<Method for preparing composition>
The above composition can be prepared by mixing the above components.
Upon preparation of the composition, the respective components may be blended together, or the respective components may be dissolved and / or dispersed in a solvent and then sequentially blended. In addition, there is no particular restriction on the order of addition and the working conditions when blending.
Further, as the process for dispersing the pigment, a process using compression, squeezing, impact, shearing, cavitation or the like as a mechanical force used for dispersing the pigment can be mentioned. 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. In addition, "Dispersion Technology Taizen, published by Information Technology Co., Ltd., July 15, 2005" and "Practice of dispersion technology and industrial applications centering on suspension (solid / liquid dispersion system) Comprehensive collection of materials, Management Development Center Publishing Department Issued October 10, 1978 ”and the disperser can be preferably used.

When preparing the composition, it is preferable to filter with a filter for the purpose of removing foreign matters and reducing defects. The filter can be used without particular limitation as long as it has been conventionally used for filtration and the like. For example, fluorine resin such as polytetrafluoroethylene (PTFE), polyamide resin such as nylon (eg nylon-6, nylon-6,6), polyolefin resin such as polyethylene and polypropylene (PP) (high density, ultra high Filters using (including molecular weight) and the like can be mentioned. Among these materials, polypropylene (including high-density polypropylene) and nylon are preferable.
A suitable pore size of the filter is about 0.01 to 7.0 μm, preferably about 0.01 to 3.0 μm, and more preferably about 0.05 to 0.5 μm. Within this range, it becomes possible to surely remove fine foreign substances that hinder the preparation of a uniform and smooth composition in the subsequent step. It is also preferable to use a fiber filter, and examples of the filter include polypropylene fiber, nylon fiber, glass fiber, and the like. Specifically, SBP type series (such as SBP008) and TPR type series manufactured by Roki Techno Co., Ltd. (TPR002, TPR005, etc.) and SHPX type series (SHPX003, etc.) filter cartridges can be used.

When using the 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. For the pore size here, the nominal value of the filter manufacturer can be referred to. Examples of commercially available filters include various types of filters provided by Nippon Pole Co., Ltd. (DFA4201NXEY, etc.), Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Japan Microlith Co., Ltd.), or Kitz Micro Filter Co., Ltd. You can choose from.
The second filter can be made of the same material as the first filter described above.
For example, the filtering with the first filter may be performed only with the dispersion liquid, and the second filtering may be performed after mixing the other components.

[film]
The film of the present invention is a film formed using the composition of the present invention.

<L *>
The film of the present invention preferably has an L * of 35 to 85 in the CIE1976 L * a * b * color system. The upper limit of L * in the LIE a * b * color system of CIE1976 is more preferably less than 80, particularly preferably 75 or less, and particularly preferably 70 or less. The lower limit of L * in the LIE a * b * color system of CIE1976 is more preferably 40 or more, and particularly preferably 50 or more.

<A * and b *>
In the film of the present invention, a * and b * in the CIE1976 L * a * b * color system are preferably −30 to 30, more preferably −20 to 20, and particularly preferably −10 to 10.

<Thickness>
The thickness of the film of the present invention is preferably 10 μm or less, more preferably 3 μm or less, and particularly preferably 1 μm or less. The lower limit of the thickness is preferably 0.5 μm or more.

<Average transmittance>
The film of the present invention preferably has an average transmittance of 1% or more in a wavelength range of 400 to 700 nm with a thickness of 3 μm, 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.

<Use>
The film of the present invention can be used by incorporating it into each type of sensor such as a solid-state image sensor 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, for example, various types of sensors or image display devices and 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.

[Cured film]
The cured film of the present invention is a cured film obtained by curing the film of the present invention. The cured film preferably has the solvent removed 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.
The cured film of the present invention preferably has an L * in the LIE of the CIE1976 L * a * b * color system of 35 to 85 in the cured film state. In the cured film of the present invention, the upper limit of L * in the L * a * b * color system of CIE1976 in the cured film is more preferably less than 80, particularly preferably 75 or less, and 70 or less. It is more preferable that there is. In the cured film of the present invention, the lower limit of L * in the CIE1976 L * a * b * color system is more preferably 40 or more, and particularly preferably 50 or more in the state of the cured film.
The cured film of the present invention contains particles and a resin, the particles include particles having a refractive index of at least 2.1 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 include a resin. The preferable range of the refractive index of the particles having a refractive index with respect to the light having a wavelength of 589 nm in the cured film of the present invention is the same as the preferable range of the refractive index of the particles having a refractive index with respect to the light having a wavelength of 589 nm in the composition of the present invention. The preferable range of the refractive index of the resin having the refractive index for the light having a wavelength of 589 nm in the cured film of the present invention is the same as the preferable range of the refractive index of the resin having the refractive index for the light of the wavelength 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 for light having a wavelength of 589 nm and the refractive index of the resin for light having a wavelength of 589 nm is preferably 1.22 or more, and 1.27. The above is more preferable. Within this range, the L * in the L * a * b * color system of CIE1976 of the cured film can be easily increased.
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 have a refractive index with respect to light having a wavelength of 589 nm (synonymous with 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, still more preferably 1.10 to 1.40.

[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.

[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,
Developing the exposed composition to form a pattern.

  Prior to the step of exposing the composition of the present invention through a mask having a pattern, a step of applying the composition of the present invention to a substrate or the like to form a film and a step of drying the film are preferable. . The film thickness, laminated structure and the like can be appropriately selected according to the purpose.

  As a method of applying the composition in the step of forming the film, a known method can be used. For example, a dropping method (drop casting); a slit coating method; a spraying method; a roll coating method; a spin coating method (spin coating); a cast coating method; a slit and spin method; a pre-wet method (for example, JP 2009-145395A). Methods described in the publication); inkjet (for example, on-demand method, piezo method, thermal method), ejection-type printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing method, etc. Examples include various types of printing methods; transfer methods using dies and the like; nanoimprint methods and the like. The application method using an inkjet is not particularly limited as long as the composition can be discharged. The method described in the indicated patent publication (especially pages 115 to 133), JP-A-2003-262716, JP-A-2003-185831, JP-A-2003-261827, JP-A-2012-126830. In JP-A 2006-169325, there is a method of replacing the composition to be discharged with the composition of the present invention. From the viewpoint of coating suitability, the spin coating method is preferably spin coating in the range of 300 to 6000 rpm, and more preferably 400 to 3000 rpm. The substrate temperature during spin coating is preferably 10 to 100 ° C, more preferably 20 to 70 ° C. Within the above range, it is easy to produce a film having excellent coating uniformity.

  In the case of the dropping method (drop casting), it is preferable to form a dropping region of the composition having photoresist as partition walls on the base material so that a uniform film having a predetermined film thickness can be obtained. A desired film thickness can be obtained by controlling the dropping amount and solid content concentration of the composition and the area of the dropping region. The thickness of the dried film is not particularly limited and can be appropriately selected depending on the purpose.

  The base material is not particularly limited and can be appropriately selected depending on the application. For example, non-alkali glass used for liquid crystal display devices, soda glass, Pyrex (registered trademark) glass, quartz glass, and substrates having a transparent conductive film adhered to these, photoelectric conversion element substrates used for solid-state imaging devices, etc. Materials, silicon base materials and the like, complementary metal oxide semiconductors (CMOS) and the like. If necessary, an undercoat layer may be provided on these base materials to improve adhesion with the upper layer, prevent diffusion of substances, or flatten the surface.

  In the step of drying the film, the drying conditions vary depending on each component, the type of solvent, the usage ratio, and the like. For example, at a temperature of 60 to 150 ° C., 30 seconds to 15 minutes is preferable.

  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 include, for example, applying the composition of the present invention onto a substrate. Examples thereof 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. In the step of forming the pattern, the pattern may be formed by a photolithography method or the pattern may be formed by a dry etching method.

In the exposure step, it is preferable to expose the film formed on the base material in a pattern shape. For example, pattern exposure can be performed by exposing the film on the substrate through an exposure device such as a stepper through a mask having a predetermined mask pattern. Thereby, the exposed portion can be cured.
As the radiation (light) that can be used at the time of exposure, ultraviolet rays such as g rays and i rays are preferably used (particularly preferably i rays). Irradiation dose (exposure dose), for example, preferably ^{0.03~2.5J / cm 2, 0.05~1.0J / cm} 2 is more preferable.
The oxygen concentration at the time of exposure can be appropriately selected, and in addition to performing 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 to substantially no oxygen), and may be exposed in a high oxygen atmosphere in which the oxygen concentration exceeds 21% by volume (for example, 22% by volume or more, further 30% by volume or more, and particularly 50% by volume or more). You may. The exposure illuminance can be appropriately set and is usually 1000 W / m ^{2 to} 100000 W / m ² (for example, 5000 W / m ² or more, further 15000 W / m ² or more, and 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.

  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 developing solution. As a result, the composition layer in the unexposed portion in the exposure step is eluted into the developing solution, and only the photocured portion remains. As the developing solution, an alkaline developing solution that does not damage the underlying circuit is desirable. 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.

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 hydroxide. Examples thereof include organic alkaline compounds such as choline, choline, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene, and dimethylbis (2-hydroxyethyl) ammonium hydroxide. An alkaline aqueous solution prepared by diluting these alkaline agents with pure water to a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass is preferably used as a developer.
Further, an inorganic alkali may be used in the developing solution. As the inorganic alkali, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate, sodium metasilicate and the like are preferable.
A surfactant may be used in the developer. Examples of the surfactant include the surfactants described in the above composition, and the nonionic surfactant is preferable.
When a developing solution containing such an alkaline aqueous solution is used, it is generally preferable to wash (rinse) with pure water after the development.

  Other steps may be included. The other steps are not particularly limited and can be appropriately selected depending on the purpose. For example, a substrate surface treatment step, a pre-heating step (pre-baking step), a post-heating step (post-baking step), etc. may be mentioned. At least one of heating and exposure may be further performed after the development. According to this aspect, the hardening of the film is further advanced, and a more strongly hardened film can be manufactured.

  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.

  Examples of the heat treatment method include a method of heating the entire surface of the formed film. The heat treatment increases the film strength of the pattern. The heating temperature is preferably 100 to 260 ° C. The lower limit is more preferably 120 ° C or higher, particularly preferably 160 ° C or higher. The upper limit is more preferably 240 ° C or lower, particularly preferably 220 ° C or lower. When the heating temperature is within the above range, a film having excellent strength can be 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. The heating device is not particularly limited and may be appropriately selected from known devices according to the purpose, and examples thereof include a dry oven, a hot plate, and an infrared heater.

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. In addition, "part" and "%" are based on mass unless otherwise specified.
The viscosity was measured using an E-type viscometer (RE85L manufactured by Toki Sangyo Co., Ltd.) and a cone rotor of 1 ° 34 ′ × R24 under the condition of a rotation speed of 5 rpm. If the measurement cannot be performed under the above-mentioned conditions, the number of rotations was appropriately changed.

<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 connected to a column developing solvent: tetrahydrofuran Column temperature: 40 ° C
Flow rate (sample injection amount): 1.0 μL (sample concentration: 0.1% by mass)
Device name: Tosoh Corp. HLC-8220GPC
Detector: RI (refractive index) detector calibration curve Base resin: polystyrene

<Method of measuring acid value>
The acid value represents the mass of potassium hydroxide required to neutralize the acidic component per 1 g of solid content. A measurement sample is dissolved in a tetrahydrofuran / water = 9/1 (mass ratio) mixed solvent, and the obtained solution is used at 25 ° C. using a potentiometric titrator (trade name: AT-510, manufactured by Kyoto Electronics Manufacturing Co., Ltd.). Neutralization titration with a 0.1 mol / L sodium hydroxide aqueous solution. Using the inflection point of the titration pH curve as the titration end point, the acid value was calculated by the following formula.
A = 56.11 × Vs × 0.5 × f / w
A: Acid value (mgKOH / g)
Vs: Amount of 0.1 mol / L sodium hydroxide aqueous solution used for titration (mL)
f: titer of 0.1 mol / L sodium hydroxide aqueous solution w: measured sample mass (g) (solid content conversion)

<Measurement of amine value>
The amine value is represented by the mass of the basic component and equivalent potassium hydroxide (KOH) per 1 g of the solid content. A measurement sample is dissolved in acetic acid, and a potentiometric titrator (trade name: AT-510, manufactured by Kyoto Electronics Manufacturing Co., Ltd.) is used to obtain a solution of 0.1 mol / L perchloric acid / acetic acid solution at 25 ° C. Neutralization titration with. Using the inflection point of the titration pH curve as the end point of titration, the amine value was calculated by the following formula.
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 used for titration (mL)
f: titer of 0.1 mol / L perchloric acid / acetic acid solution w: mass of measurement sample (g) (solid content conversion)

<Measurement of average primary particle size of particles>
The primary particle size of the powder particles was observed by a transmission electron microscope (TEM), and it was determined by observing a part where the particles were not aggregated. Regarding the particle size distribution of the particles, powder particles that were primary particles were photographed with a transmission electron microscope using a transmission electron microscope, and then the particle size distribution was measured with an image processing device using the photograph. The average primary particle diameter of the particles was defined as the average primary particle diameter based on the number-based arithmetic average diameter calculated from the particle size distribution. An electron microscope (H-7000) manufactured by Hitachi, Ltd. was used as a transmission electron microscope, and Luzex AP manufactured by Nireco Corporation was used as an image processing apparatus.

[Examples 1-44, Comparative Examples 1-3]
<Production of dispersion>
A dispersion liquid was produced by performing a dispersion treatment on the mixed liquid having the following composition using an Ultra Apex Mill manufactured by Kotobuki Industries Co., Ltd. as a circulation type dispersion device (bead mill) as follows.
<< composition of mixed solution >>
Particles described in the table below: 30 parts by mass Dispersant described in the table below: amount described in the table below Solvent: propylene glycol-1-monomethyl ether-2-acetate (PGMEA): amount described in the table below

Further, the circulation type dispersion device was operated under the following conditions.
・ Bead diameter: Diameter 0.2 mm
・ Bead filling rate: 65% by volume
・ Peripheral speed: 6m / sec ・ Pump supply: 10.8kg / h ・ Cooling water: Tap water ・ Bead mill annular passage internal volume: 0.15L
・ Amount of mixed liquid for dispersion treatment: 0.65 kg

After the start of dispersion, the average particle size of the particles was measured at intervals of 30 minutes. The average particle size 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 table below.

(particle)
The particles shown in the following table were used as B-2 to B-13.

The refractive index of particles is measured by the following method.
First, dispersion is performed using a dispersant having a known refractive index and PGMEA. After that, the prepared dispersion liquid and a resin having a known refractive index are mixed so that the concentration in the solid content of the particles becomes 10% by mass, 20% by mass, 30% by mass, and 40% by mass, and four types of coating are applied. Make a liquid. After coating these coating solutions on a Si wafer at 300 nm, the refractive index of the obtained film is measured using ellipsometry (Lambda Ace RE-3300 (trade name), Dainippon Screen Mfg. Co., Ltd.). Then, the particle concentration and the refractive index are plotted and extrapolated to derive the particle refractive index.

(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 = 20,000, refractive index 1.51). The numerical value written together with each repeating unit represents the content [mass ratio] of each repeating unit. The numerical value written together with the side chain repeat site indicates the number of repeats of the repeat site.
F-4: Resin having the following structure (Mw = 22900, refractive index 1.51). The numerical value written together with each repeating unit represents the content [mass ratio] of each repeating unit. The numerical value written together with the side chain repeat site indicates the number of repeats of the repeat site.
F-5: X-22-3701E (polyalkylsiloxane having an acidic adsorption group), which is a polysiloxane resin-based dispersant, made by Shin-Etsu Silicone, refractive index 1.43.

<Preparation of composition>
Compositions were prepared by mixing the raw materials listed in the table below.

<< raw materials >>
The raw materials described in the above table are as follows.
(Dispersion liquid)
Dispersions 2 to 19: Dispersions 2 to 19 produced above.

(resin)
A-1: A fluororesin which is the above-mentioned fluororesin 1 (acid value 114.1 mgKOH / g, MW = 10000, structure below).

A-2: The polysiloxane resin (Mw = 10000) which is the above-mentioned Example 53. Synthesis was carried out according to the following procedure with reference to Synthesis Example 11 of <0117> and Synthesis Example 1 of <0107> of WO2014 / 126013A. The contents of this publication are incorporated herein.
The following materials were placed in a 500 mL eggplant-shaped flask, and an aqueous solution in which 2 g of phosphoric acid was dissolved in 54 g of water was added dropwise over 30 minutes while stirring at room temperature. Then, the mixture was stirred at 40 ° C for 30 minutes and then at 70 ° C for 30 minutes. Finally, it was heated at 110 ° C. for 3 hours to complete the reaction. The solvent was removed by an evaporator.
-Material-
Dimethoxydimethylsilane 75 parts by mass (62.6 mol%)
42 parts by mass of 3-acryloxypropyltrimethoxysilane (17.9 mol%)
3-trimethoxysilylpropyl succinic anhydride 39 parts by mass (15 mol%)
3-glycidyloxypropyltrimethoxysilane 12 parts by mass (4.5 mol%)
PGMEA 109 parts by mass

A-3: Polysiloxane-based resin (Mw = 10000) which is the above-described Concrete Example 54. It was synthesized in the same manner as in A-2 except that the materials were changed as follows.
-Material-
Dimethoxydimethylsilane 84 parts by mass (70 mol%)
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%)
PGMEA 102 parts by mass

A-4: Polysiloxane-based resin (Mw = 10000) which is the above-mentioned specific example 55. It was synthesized in the same manner as in A-2 except that the materials were changed as follows.
-Material-
Dimethoxydimethylsilane 80 parts by mass (66.3 mol%)
3-acryloxypropyltrimethoxysilane 44 parts by mass (19 mol%)
3-trimethoxysilylpropyl succinic anhydride 26 parts by mass (10 mol%)
3-glycidyloxypropyltrimethoxysilane 13 parts by mass (4.7 mol%)
PGMEA 106 parts by mass

A-5: Polysiloxane resin (Mw = 10000) which is the above-mentioned specific example 56. It was synthesized in the same manner as in A-2 except that the materials were changed as follows.
-Material-
71 parts by mass of dimethoxydimethylsilane (59 mol%)
39 parts by mass of 3-acryloxypropyltrimethoxysilane (16.8 mol%)
3-trimethoxysilylpropyl succinic anhydride 52 parts by mass (20 mol%)
3-glycidyloxypropyltrimethoxysilane 12 parts by mass (4.2 mol%)
113 parts by mass of PGMEA

A-6: Polysiloxane resin (Mw = 10000) which is the above-mentioned specific example 57. It was synthesized in the same manner as in A-2 except that the materials were changed as follows.
-Material-
66 parts by mass of dimethoxydimethylsilane (55.3 mol%)
3-acryloxypropyltrimethoxysilane 37 parts by mass (15.8 mol%)
3-trimethoxysilylpropyl succinic anhydride 66 parts by mass (25 mol%)
3-glycidyloxypropyltrimethoxysilane 11 parts by mass (3.9 mol%)
117 parts by mass of PGMEA

A-7: Polysiloxane resin (Mw = 10000, which is Specific Example 58 described above) was synthesized in the same manner as A-2 except that the materials were changed as follows.
-Material-
41 parts by mass of dimethoxydimethylsilane (80.0 mol%)
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: Polysiloxane resin (Mw = 10000) which is the specific example 59 described above. It was synthesized 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%)
3-acryloxypropyltrimethoxysilane 44 parts by mass (20.0 mol%)
3-Trimethoxysilylpropyl succinic anhydride 29 parts by mass (15.0 mol%)
3-glycidyloxypropyltrimethoxysilane 10 parts by mass (5.0 mol%)
Tetraethoxysilane 10 parts by mass (5.0 mol%)
PGMEA 136.72 parts by mass

A-10: Methacrylic resin having the following structure (acid value 79.3 mg KOH / g, Mw = 17,000, manufactured by Fujikura Kasei Co., Ltd.). The numerical value written together with each repeating unit represents the content [mass ratio] of each repeating unit.

  The refractive index of each resin was measured in the uncured state by the method described herein.

(Polymerizable compound having an ethylenically unsaturated bond)
D-1: Polyfunctional acrylate, NK ester A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd., refractive index 1.51)
D-2: Si atom-containing polyfunctional vinyl compound, VINYLTRIISOPROPENOXYSILANE (manufactured by Asmax Co., Ltd., refractive index 1.44)

(Polymerization initiator)
E-1: Photopolymerization initiator that is a trihalomethyltriazine compound (trichloromethyltriazine compound), triazine PP (manufactured by BASF)
E-2: IRGACURE OXE01 (manufactured by BASF), an oxime ester-based photopolymerization initiator

(solvent)
PGMEA: Propylene glycol-1-monomethyl ether-2-acetate

(Anti-coloring agent)
G-1: Thioether-based coloring preventing agent, ADEKA STAB AO-412S (manufactured by ADEKA), the following structure.
G-2: Phenol-based anti-coloring agent, ADEKA STAB AO-80 (manufactured by ADEKA Corporation), the following structure.

(Compound having an epoxy group)
H-1: EHPE3150 (manufactured by Daicel Corporation)

(UV absorber)
I-1: Compound III of JP 2009-217221 A, the following structure.

(Adhesive)
J-1: Compound C of JP 2009-288703 A, the following structure.

[Evaluation]
<L *>
Each of the compositions obtained above was dried on a glass wafer with 8 inches (1 inch is 2.54 cm) with an undercoat layer (CT-4000L manufactured by FUJIFILM Electronic Materials Co., Ltd .; film thickness 0.1 μm). The film was then applied using a spin coater to a film thickness of 3.0 μm, and heat-treated (prebaked) for 120 seconds using a 110 ° C. hot plate.
Then, using an i-line stepper exposure device FPA-3000i5 + (manufactured by Canon Inc.), light having a wavelength of 365 nm was exposed at 1000 mJ / cm ² through a mask having a pattern of 2 cm × 2 cm.
After that, 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 Co., Ltd.), and tetramethylammonium hydroxide (TMAH) is placed. Was used for paddle development at 23 ° C. for 60 seconds to form a white pattern on the glass wafer.
A glass wafer on which a white pattern has been formed is fixed to a horizontal rotary table using a vacuum chuck method, and while rotating the glass wafer at a rotation speed of 50 rpm by a rotating device, pure water is supplied from above the center of rotation in the form of a shower from a jet nozzle. And rinsed, and then spray-dried. In the present specification, L * is measured when the solvent contained in the film is 1% by mass or less.
Using spectrophotometer X-rite 528 (trade name, manufactured by X-rite), measurement conditions are D65 light source, observation field of view is 2 °, and white reference is attached to X-rite 528 (trade name, manufactured by X-rite) The white pattern obtained was measured using the white patch of the calibration reference plate of. The L * value in the LIE a * b * color system of CIE1976 was evaluated according to the following criteria. If the evaluation is A, B or C, it is judged that there is no practical problem. The evaluation of A or B is preferable, and the evaluation of A is more preferable. The results obtained are shown in the table below.
A: L * in the LIE a * b * color system of CIE1976 is 50 or more and 75 or less when a film having a thickness of 3.0 μm is formed.
B: L * in the L * a * b * color system of CIE1976 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 CIE1976 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 CIE1976 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: LIE in the L * a * b * color system of CIE1976 when a film having a thickness of 3.0 μm is formed is less than 20 or more than 90.
When a film having a thickness of 3.0 μm was formed using each composition, a * and b * in the L * a * b * color system of CIE1976 were compositions of Examples other than the following. In the case of -10 or more and 10 or less, when using the composition of Examples 22, 29, 30 is -20 or more and less than -10 or more than 10 and 20 or less, using the compositions of Examples 21-24 In the case of being, it was -30 or more and less than -20 or more than 20 and 30 or less.

<Density unevenness after 1 month>
Each composition obtained above was aged for 1 month at room temperature (23 ° C.). Using each composition aged for 1 month, a white pattern was prepared in the same manner as the L * measuring method. Then, 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 judged that there is no practical problem. The evaluation of A or B is preferable, and the evaluation of A is more preferable. The results obtained are shown 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.

<Applicability>
Each composition obtained above was left to stand in a constant temperature oven at 50 ° C. for 12 hours. Using a spin coater MS-B100 manufactured by Mikasa, the composition heated to 50 ° C. is applied to a 4-inch wafer under the conditions of 300 rpm for 5 seconds and a main rotation speed of 20 seconds to produce a film having a thickness of 3.0 μm. did. The main number of revolutions at that time was classified as follows, and the suitability for coating was evaluated. The evaluation of A, B, C or D is preferable, the evaluation of A, B or C is more preferable, the evaluation of A or B is further preferable, and the evaluation of A is particularly preferable. . The results obtained are shown 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.
Under the conditions of B: A, the film thickness of 3.0 μm cannot be applied, but the film thickness of 3.0 μm can be applied in the range of the main rotation speed of 750 or more and less than 1000 rpm, or more than 2000 and 2500 rpm or less.
Under the conditions of C: A and B, the film thickness of 3.0 μm cannot be applied, but the film thickness of 3.0 μm can be applied within the range of the main rotation speed of 500 or more and less than 750 rpm and more than 2500 and 3000 rpm or less.
D: Under the conditions of A, B, and C, the film thickness of 3.0 μm cannot be applied, but the film thickness of 3.0 μm can be applied within the range of 3000 rpm or more and 4000 rpm or less.
E: A film thickness of 3.0 μm cannot be obtained within the range of the above main rotation speed.

<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 would be 3.0 μm, and heated for 120 seconds using a 110 ° C. hot plate. Processing (prebaking) was performed.
Then, using an i-line stepper exposure device FPA-3000i5 + (manufactured by Canon Inc.), light having a wavelength of 365 nm was exposed at 1000 mJ / cm ² through a mask having a pattern of 2 cm × 2 cm.
After that, 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 Co., Ltd.), and tetramethylammonium hydroxide (TMAH) is placed. Using a 0.3 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 has been formed is fixed to a horizontal rotary table using a vacuum chuck method, and while rotating the glass wafer at a rotation speed of 50 rpm by a rotating device, pure water is supplied from above the center of rotation in the form of a shower from a jet nozzle. And rinsed, and then spray-dried. After that, heat treatment (post-baking) 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 wavelength of the white pattern at 400 to 700 nm after the white pattern was immersed in N-methyl-2-pyrrolidinone for 5 minutes. Measured. With respect to the spectral fluctuation (ΔT%), the fluctuation at the wavelength where the spectral fluctuation is the largest was set to ΔTmax, and the solvent resistance was evaluated. The smaller the variation is, the better the solvent resistance is, which is more desirable. The evaluation of A, B, C or D is preferable, the evaluation of A, B or C is more preferable, the evaluation of A or B is further preferable, and the evaluation of A is particularly preferable. . The results obtained are shown 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%.

<Pattern shape>
Each composition obtained above was applied onto an 8-inch silicon wafer with an undercoat layer by spin coating so that the film thickness after application would be 3.0 μm, and then applied on a hot plate at 100 ° C. for 2 hours. It heated for a minute and the composition layer was obtained.
Then, using the i-line stepper exposure device FPA-3000i5 + (manufactured by Canon Inc.), the resulting 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 (Act8 manufactured by Tokyo Electron). A 0.3 mass% tetramethylammonium hydroxide (TMAH) aqueous solution was used as a developing solution, and shower development was performed at 23 ° C. for 60 seconds. Then, rinse was performed by a spin shower using pure water to obtain a pattern. The shape of the obtained pattern was observed (magnification: 5000 times) using a scanning electron microscope (SEM) (S-4800H, manufactured by Hitachi High-Technologies Corporation) and evaluated. The evaluation criteria of the pattern shape are as follows. The evaluation of A, B, C or D is preferable, the evaluation of A, B or C is more preferable, the evaluation of A or B is further preferable, and the evaluation of A is particularly preferable. . The results obtained are shown 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.

<Adhesion>
Among the patterns produced by 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 of adhesion are as follows. The evaluation is preferably A, B, C or D, more preferably the evaluation of A, B or C, particularly preferably the evaluation of A or B, and more preferably the evaluation of A. preferable. The results obtained are shown in the table below.
A: No peeling or chipping in the pattern.
B: Peeling or chipping of the observed pattern is more than 0% and less than 5%.
C: Peeling or chipping of the observed pattern is 5% or more and less than 10%.
D: Peeling or chipping of the observed pattern is 10% or more and less than 30%.
E: Peeling or chipping of the observed pattern is 30% or more.

<Colorability>
The pattern L *, a *, b * of the pattern produced by the same method as the evaluation of the solvent resistance is measured by using a spectrophotometer, the measurement conditions are D65 light source, the observation field of view is 2 °, and the white reference is X-rite 528 ( It was measured 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 addition, at the time of measurement, the glass wafer on which the pattern was formed was placed on a table (black table) covered with a black resist for measurement. The OD (Optical Density) of the black resist layer on the black stand is 3.5 at 400 nm (transmission factor 0.03%), 3.2 at 550 nm (transmission factor 0.06), and 2.5 at 700 nm (transmission factor 0). .32%), and the average reflectance in the range of 400 nm to 700 nm was 7%. The OD of the black stand 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 is heated at 265 ° C. for 15 minutes using a hot plate, the spectrum of the pattern after heating is measured, and the color difference ΔE * ab between the pattern before and after heating in the LIE * b * color system of CIE1976. Was calculated. The formula for calculating the color difference ΔE * ab is as follows.
ΔE * ab = [(ΔL *) ² + (Δa *) ² + (Δb *) ² ] ^1/2
A: The color difference ΔE * ab is 0 or more and less than 0.5.
B: The 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: The color difference ΔE * ab is 2.0 or more and less than 3.0.
E: The color difference ΔE * ab is 3.0 or more.
The evaluation of A, B, C or D is preferable, the evaluation of A, B or C is more preferable, the evaluation of A or B is further preferable, and the evaluation of A is particularly preferable. . The results obtained are shown in the table below.

From the above table, the composition of each example shows that the L * a * b * color system L * of CIE1976 is 35 to 85 when a film having a thickness of 3.0 μm is formed, and the composition is aged for one month. It was found that it is possible to manufacture a film in which uneven density afterward is suppressed.
On the other hand, particles of a resin having a refractive index of less than 2.1 with respect to light having a wavelength of 589 nm are used, and the difference between the refractive index of the particles 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 * in the L * a * b * color system of CIE1976 of less than 35 or more than 85 when a film having a thickness of 3.0 μm was formed. . Comparative Example 3 using a resin having a refractive index of more than 1.5 with respect to light having a wavelength of 589 nm, and having a difference between the refractive index of particles having a wavelength of 589 nm and the resin having a refractive index of light having a wavelength of 589 nm of less than 1.22. It was found that the composition (1) had a large concentration unevenness after one month.

<Average transmittance>
Regarding the film having a thickness of 3.0 μm, which is a pattern formed by the evaluation of the solvent resistance using the composition of each example, the transmittance in the wavelength range of 400 to 700 nm was measured by MCPD-3000 manufactured by Otsuka Electronics Co., Ltd. The measurement was performed at a pitch of 5 nm, and the average value was used 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 the wavelength range of 400 to 700 nm when converted to a thickness of 3.0 μm.

<Influence of developer>
The same pattern can be obtained by developing the composition of each Example with the solvent described in the present specification instead of the developer used in the evaluation of <Pattern shape>.

The film formed from the composition of the present invention has an L * in the L * a * b * color system of CIE1976 of 35 to 85 when a film having a thickness of 3.0 μm is formed, and is aged for one month. It is a film in which uneven density afterward is suppressed. When such a film is cured and used as a cured film for each type of optical sensor such as a solid-state image sensor, it is possible to achieve both good optical sensor function and good design, and has industrial applicability. high.

Claims (12)

Including particles and resin,
The particles include at least particles having a refractive index of 2.1 or more for light having a wavelength of 589 nm,
A composition, wherein the resin contains at least a resin having a refractive index of 1.5 or less for light having a wavelength of 589 nm,
The particles having a refractive index of 2.1 or more for light having a wavelength of 589 nm is titanium oxide having an average particle diameter of 60 to 200 nm,
Of the particles having a refractive index of 2.1 or more with respect to the light of the wavelength of 589 nm with respect to the total mass of the particles of 95% by mass or more, and having a refractive index of 2.1 or more with respect to the light of the wavelength of 589 nm. The content is 5 to 50 mass% with respect to the total solid content of the composition,
The resin includes an alkali-soluble resin,
The resin having a refractive index of 1.5 or less for light having a wavelength of 589 nm includes a fluorine-based resin having a repeating unit derived from a monomer represented by the general formula (F1),
Of the resin having a refractive index of 1.5 or less with respect to the light of the wavelength of 589 nm with respect to the total mass of the resin of 30% by mass or more, and having a refractive index of 1.5 or less with respect to the light of the wavelength of 589 nm. content, Ri 10-50% by mass relative to the total solids of the composition,
L3 in the L * a * b * color system of CIE1976 is 35 to 85 when a film having a thickness of 3.0 μm is formed using the composition.
Composition.
In general formula (F1), Rf is a fluoroalkyl group- or perfluoroalkyl group-containing substituent, n is 1 or 2, and R ¹ is hydrogen or a methyl group.   Of the particles, the highest refractive index particle contained in the composition has a refractive index of 589 nm with respect to light, and the resin has the lowest refractive index resin contained in the composition with respect to light having a wavelength of 589 nm. The composition according to claim 1, which has a difference from the refractive index of 1.22 or more.   The composition according to claim 1 or 2, wherein the composition is a curable composition. The resin comprising a polysiloxane-based resin composition according to any one of claims 1-3. The composition according to claim 4 , wherein 50 mol% or more of the side chains 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. Wherein the composition further comprises a radical polymerizable compound and a photopolymerization initiator composition according to any one of claims 1-5. The composition according to claim 6 , wherein the content of the radically polymerizable compound having a refractive index of 1.5 or less with respect to light having a wavelength of 589 nm is 80% by mass or more based on the total mass of the radically polymerizable compound. The composition according to any one of claims 1 to 8 , wherein the composition further comprises a coloring preventing agent. It formed from the composition according to any one of claims 1-8, film. A cured film obtained by curing the film according to claim 9 . An optical sensor comprising the cured film according to claim 10 . The composition according to any one of claims 1-8, comprising the steps of exposing through a mask having a pattern,
Developing the exposed composition to form a pattern, the method for producing a film.