阅读说明：本技术 组合物、膜及膜的制造方法 (Composition, film, and method for producing film ) 是由 森全弘 中村翔一 于 2020-03-24 设计创作，主要内容包括：本发明提供一种组合物、膜及膜的制造方法,该组合物包含二氧化硅粒子、硅酮系表面活性剂及溶剂,组合物中含有0.01～0.30质量％的硅酮系表面活性剂,或者在组合物的总固体成分中含有0.05～5.00质量％的硅酮系表面活性剂。(The present invention provides a composition, a film and a method for producing a film, wherein the composition comprises silica particles, a silicone surfactant and a solvent, and the composition contains 0.01 to 0.30 mass% of the silicone surfactant, or contains 0.05 to 5.00 mass% of the silicone surfactant in the total solid content of the composition.)

1. A composition comprising silica particles, a silicone-based surfactant and a solvent,

the composition contains 0.01 to 0.30 mass% of the silicone surfactant,

when the composition is coated on a silicon wafer and heated at 200 ℃ for 5 minutes to form a film having a thickness of 0.3 μm, the refractive index of the film at a wavelength of 633nm is 1.4 or less.

2. A composition comprising silica particles, a silicone-based surfactant and a solvent,

the composition contains the silicone surfactant in an amount of 0.05 to 5.00 mass% based on the total solid content,

when the composition is coated on a silicon wafer and heated at 200 ℃ for 5 minutes to form a film having a thickness of 0.3 μm, the refractive index of the film at a wavelength of 633nm is 1.4 or less.

3. A composition comprising silica particles, a silicone-based surfactant and a solvent,

the composition contains 0.01 to 0.30 mass% of the silicone surfactant,

the silica particles include at least 1 selected from the group consisting of silica particles in which a plurality of spherical silicas are connected in a beaded shape, silica particles in which a plurality of spherical silicas are connected in a planar shape, and silica particles having a hollow structure.

4. A composition comprising silica particles, a silicone-based surfactant and a solvent,

the composition contains the silicone surfactant in an amount of 0.05 to 5.00 mass% based on the total solid content,

the silica particles include at least 1 selected from the group consisting of silica particles in which a plurality of spherical silicas are connected in a beaded shape, silica particles in which a plurality of spherical silicas are connected in a planar shape, and silica particles having a hollow structure.

5. The composition according to any one of claims 1 to 4,

the silicone surfactant is contained in an amount of 0.3 to 5.5 parts by mass per 100 parts by mass of the silica particles.

6. The composition according to any one of claims 1 to 5,

the silica particles include at least 1 kind selected from silica particles in which a plurality of spherical silicas are connected in a beaded shape and silica particles in which a plurality of spherical silicas are connected in a planar shape.

7. The composition according to any one of claims 1 to 6,

the composition contains the silica particles in an amount of 50 mass% or more based on the total solid content of the composition.

8. The composition according to any one of claims 1 to 7,

the silicone-based surfactant is a modified silicone compound.

9. The composition according to any one of claims 1 to 8,

the silicone surfactant has a dynamic viscosity of 20mm at 25 ℃²/s～3000mm²/s。

10. The composition according to any one of claims 1 to 9,

when 0.1g of the silicone surfactant is dissolved in 100g of propylene glycol monomethyl ether acetate to prepare a solution, the surface tension of the solution at 25 ℃ is 19.5mN/m to 26.7 mN/m.

11. The composition according to any one of claims 1 to 10,

the surface tension of the composition at 25 ℃ is 27.0mN/m or less.

12. The composition according to any one of claims 1 to 11,

when the composition is applied to a glass substrate and heated at 200 ℃ for 5 minutes to form a film having a thickness of 0.5 [ mu ] m, the contact angle of the film with respect to water at 25 ℃ is 20 DEG or more.

13. A film obtained using the composition of any one of claims 1 to 12.

14. A method for producing a film, comprising a step of applying the composition according to any one of claims 1 to 12 to a support by spin coating.

Technical Field

The present invention relates to a composition containing silica particles, a film using the composition containing silica particles, and a method for producing the same.

Background

An optical functional layer such as a low refractive index film is applied to the surface of the transparent substrate, for example, to prevent reflection of incident light. The product has wide application field, and is applied to products in various fields such as optical equipment, building materials, observation instruments, window glass and the like. As the material, various materials are used regardless of organic/inorganic materials, and development targets are available. Among them, in recent years, development of materials for application to optical devices has been advanced. Specifically, materials having physical properties and processability suitable for products such as display panels, optical lenses, and image sensors have been searched for.

The optical functional layer used in precision optical devices such as image sensors is required to have fine and precise processing formability. Therefore, vapor phase methods such as vacuum deposition and sputtering, which are suitable for microfabrication, have been conventionally used. As the material thereof, for example, MgF is contained₂Single layer films of cryolite, etc. have been practically used. Also, SiO was attempted₂、TiO₂、ZrO₂And the like.

On the other hand, in a vapor phase method such as a vacuum deposition method or a sputtering method, since an apparatus or the like is expensive, a production cost may be increased. Accordingly, the production of an optical functional layer such as a low refractive index film using a composition containing silica particles has been recently studied (see patent documents 1 to 3).

Prior art documents

Patent document

Patent document 1: japanese patent laid-open publication No. 2015-166449

Patent document 2: international publication No. 2015/190374

Patent document 3: international publication No. 2019/017280

Disclosure of Invention

Technical problem to be solved by the invention

As a result of further studies on a composition containing silica particles, the present inventors have found that when a composition containing silica particles is applied by a spin coating method, coating unevenness of a waveform may occur on the surface. Thus, there is still room for improvement in the operation of the composition containing silica particles.

After a film is formed using the composition containing silica particles, another film-forming composition such as an overcoat layer-forming composition may be applied to the film. Therefore, regarding a film formed using a composition containing silica particles, it is also desired that when another film-forming composition is applied to the film, the film has excellent coatability with respect to the other film-forming composition.

Accordingly, an object of the present invention is to provide a composition capable of forming a film having good coatability of other film-forming compositions and suppressed occurrence of uneven coating of waves, a film, and a method for producing a film.

Means for solving the technical problem

According to the studies of the present inventors, it has been found that the above object can be achieved by using the composition described later, and the present invention has been completed. Accordingly, the present invention provides the following.

<1> a composition comprising silica particles, a silicone-based surfactant and a solvent,

the composition contains 0.01 to 0.30 mass% of the silicone surfactant,

when the composition is coated on a silicon wafer and heated at 200 ℃ for 5 minutes to form a film having a thickness of 0.3 μm, the refractive index of the film at a wavelength of 633nm is 1.4 or less.

<2> a composition comprising silica particles, a silicone-based surfactant and a solvent,

the composition contains the silicone surfactant in an amount of 0.05 to 5.00 mass% based on the total solid content,

when the composition is coated on a silicon wafer and heated at 200 ℃ for 5 minutes to form a film having a thickness of 0.3 μm, the refractive index of the film at a wavelength of 633nm is 1.4 or less.

<3> a composition comprising silica particles, a silicone-based surfactant and a solvent,

the composition contains 0.01 to 0.30 mass% of the silicone surfactant,

the silica particles include at least 1 selected from the group consisting of silica particles in which a plurality of spherical silicas are connected in a beaded shape, silica particles in which a plurality of spherical silicas are connected in a planar shape, and silica particles having a hollow structure.

<4> a composition comprising silica particles, a silicone-based surfactant and a solvent,

the composition contains the silicone surfactant in an amount of 0.05 to 5.00 mass% based on the total solid content,

the silica particles include at least 1 selected from the group consisting of silica particles in which a plurality of spherical silicas are connected in a beaded shape, silica particles in which a plurality of spherical silicas are connected in a planar shape, and silica particles having a hollow structure.

<5> the composition as stated in any one of <1> to <4>, wherein,

the silicone surfactant is contained in an amount of 0.3 to 5.5 parts by mass per 100 parts by mass of the silica particles.

<6> the composition as stated in any one of <1> to <5>, wherein,

the silica particles include at least 1 type selected from silica particles in which a plurality of spherical silicas are connected in a beaded shape and silica particles in which a plurality of spherical silicas are connected in a planar shape.

<7> the composition as stated in any one of <1> to <6>, wherein,

the composition contains the silica particles in an amount of 50 mass% or more based on the total solid content.

<8> the composition as stated in any one of <1> to <7>, wherein,

the silicone surfactant is a modified silicone compound.

<9> the composition as stated in any one of <1> to <8>, wherein,

the silicone surfactant has a dynamic viscosity of 20 to 3000mm at 25 DEG C²/s。

<10> the composition as stated in any one of <1> to <9>, wherein,

when 0.1g of the silicone surfactant is dissolved in 100g of propylene glycol monomethyl ether acetate to prepare a solution, the surface tension of the solution at 25 ℃ is 19.5 to 26.7 mN/m.

<11> the composition as stated in any one of <1> to <10>, wherein,

the surface tension of the composition at 25 ℃ is 27.0mN/m or less.

<12> the composition as stated in any one of <1> to <11>, wherein,

when the composition is applied to a glass substrate and heated at 200 ℃ for 5 minutes to form a film having a thickness of 0.5 μm, the contact angle of the film with respect to water at 25 ℃ is 20 ° or more.

<13> a film obtained using the composition of any one of <1> to <12 >.

<14> a method for producing a film, comprising a step of applying the composition of any one of <1> to <12> to a support by spin coating.

Effects of the invention

According to the present invention, it is possible to provide a composition capable of forming a film in which the coating property of another film-forming composition is good and the occurrence of uneven coating of waves is suppressed, a film, and a method for producing a film.

Drawings

Fig. 1 is an enlarged view of a silica particle schematically showing a shape in which a plurality of spherical silicas are connected in a bead-like manner.

Detailed Description

The present invention will be described in detail below.

In the present specification, "to" is used to include numerical values before and after the "to" as a lower limit value and an upper limit value.

In the labeling of a group (atomic group) in the present specification, a label which is not described as substituted or unsubstituted further includes a group (atomic group) having no substituent and a group (atomic group) having a substituent. For example, "alkyl" means that an alkyl group having a substituent (substituted alkyl) is included as well as an alkyl group having no substituent (unsubstituted alkyl).

In the present specification, unless otherwise specified, "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams. Examples of the light used for exposure include actinic rays or radiation such as a bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams.

In the present specification, "(meth) acrylate" represents either or both of acrylate and methacrylate, "(meth) acrylic acid" represents either or both of acrylic acid and methacrylic acid, and "(meth) acryloyl group" represents either or both of acryloyl group and methacryloyl group.

In the present specification, the weight average molecular weight and the number average molecular weight are values measured in terms of standard polystyrene by Gel Permeation Chromatography (GPC). The measurement apparatus and the measurement conditions are set as basic conditions in accordance with the following condition 1, and as allowable conditions in accordance with the solubility of the sample and the like, as condition 2. Among them, an appropriate carrier (eluent) and a column (column) suitable for the carrier may be further selected and used depending on the kind of the polymer. For other things, refer to JISK7252-1 to 4: 2008.

(Condition 1)

Pipe column: connected to TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000 and TOSOH TSKgel Super HZ2000 column

Carrier: tetrahydrofuran (THF)

Measuring the temperature: 40 deg.C

Carrier flow rate: 1.0ml/min

Sample concentration: 0.1% by mass

A detector: RI (refractive index) detector

Injection amount: 0.1ml

(Condition 2)

Pipe column: pipe column connected with two TOSOH TSKgel Super AWM-H

Carrier: 10mM LiBr/N-methylpyrrolidinone

Measuring the temperature: 40 deg.C

Carrier flow rate: 1.0ml/min

Sample concentration: 0.1% by mass

A detector: RI (refractive index) detector

Injection amount: 0.1ml

< composition >

The composition of the invention of claim 1 is a composition, which comprises silica particles, silicone surfactant and solvent, characterized in that,

the composition contains 0.01 to 0.30 mass% of the silicone surfactant,

when the composition is coated on a silicon wafer and heated at 200 ℃ for 5 minutes to form a film having a thickness of 0.3 μm, the refractive index of the film at a wavelength of 633nm is 1.4 or less.

Further, the composition of the invention according to claim 2 is a composition comprising silica particles, a silicone surfactant and a solvent, characterized in that,

The composition contains the silicone surfactant in an amount of 0.05 to 5.00 mass% based on the total solid content,

when the composition is coated on a silicon wafer and heated at 200 ℃ for 5 minutes to form a film having a thickness of 0.3 μm, the refractive index of the film at a wavelength of 633nm is 1.4 or less.

Further, the composition of the invention according to claim 3 is a composition comprising silica particles, a silicone surfactant and a solvent, characterized in that,

the composition contains 0.01 to 0.30 mass% of the silicone surfactant,

the silica particles include at least 1 selected from the group consisting of silica particles in which a plurality of spherical silicas are connected in a beaded shape, silica particles in which a plurality of spherical silicas are connected in a planar shape, and silica particles having a hollow structure.

The composition of the invention according to the 4 th aspect is a composition comprising silica particles, a silicone surfactant and a solvent, wherein the silica particles are dispersed in the silicone surfactant,

the composition contains the silicone surfactant in an amount of 0.05 to 5.00 mass% based on the total solid content,

the silica particles include at least 1 selected from the group consisting of silica particles in which a plurality of spherical silicas are connected in a beaded shape, silica particles in which a plurality of spherical silicas are connected in a planar shape, and silica particles having a hollow structure.

According to the present invention, a composition containing silica particles and a solvent, wherein the composition contains a silicone surfactant at the above-mentioned predetermined ratio, can suppress the occurrence of uneven coating of waves on the surface when the composition is applied by spin coating, and can form a film having a good surface pattern. Further, since the content of the silicone surfactant is in the above range, even when another film-forming composition is applied to a film formed using the composition of the present invention, a film which is less likely to cause coating unevenness and which has excellent coatability with respect to the other film-forming composition can be formed. Further, by using the composition of the present invention, a film having a low refractive index can be formed. In general, a fluorine-based surfactant is considered to have a higher effect of reducing surface tension than a silicone-based surfactant. It is considered that the use of a surfactant having a high effect of reducing the surface tension improves the coating properties, but as shown in examples described later, the use of a fluorine-based surfactant does not sufficiently suppress the occurrence of uneven coating of a waveform. When the composition containing the silica particles and the solvent contains the silicone surfactant at the above-mentioned predetermined ratio, a film having good coatability of other film-forming compositions and suppressed occurrence of uneven coating of waves can be formed, which is a surprising effect that cannot be predicted by a person having ordinary knowledge in the art.

When another film is formed by applying another film-forming composition to the obtained film in contact with the film after the film is formed using the composition of the present invention, migration of components contained in the other film-forming composition to the film obtained using the composition of the present invention can be suppressed, and generation of foreign matter and the like can be suppressed. Although the detailed reason for obtaining such an effect is not clear, it is presumed that the film formed using the composition of the present invention has good affinity for the silicone surfactant, and therefore, interaction between the silica particles and components contained in another film-forming composition can be suppressed, and it is presumed that migration of components contained in another film-forming composition to the film obtained using the composition of the present invention can be suppressed.

As a method for quantitatively evaluating the coating uniformity of the composition on the support, spot measurement such as a film thickness measuring machine can be used. With respect to the coatability (streaks and the like) to the support having the level difference, evaluation can be performed using a line scanning camera that detects light regularly reflected from the support and using a change in intensity of reflected light due to interference. In the evaluation using the line scan camera, the speed of the stage, the magnification of the lens, and the irradiation light for illumination used for the continuous processing can be arbitrarily selected.

The viscosity of the composition of the present invention at 25 ℃ is preferably 3.6 mPas or less, more preferably 3.4 mPas or less, and still more preferably 3.2 mPas or less. The lower limit is preferably 1.0mPa · s or more, more preferably 1.4mPa · s or more, and further preferably 1.8mPa · s or more. If the viscosity of the composition is within the above range, a film in which the coating property of the composition is improved and the occurrence of uneven coating of waves is suppressed can be easily obtained.

The solid content concentration of the composition of the present invention is preferably 5% by mass or more, more preferably 7% by mass or more, and further preferably 8% by mass or more. The upper limit is preferably 15% by mass or less, more preferably 12% by mass or less, and still more preferably 10% by mass or less. If the solid content concentration of the composition of the present invention is within the above range, a film in which the occurrence of uneven coating of waves is suppressed can be easily obtained.

The absolute value of the zeta potential in the present invention is preferably 25mV or more, more preferably 29mV or more, even more preferably 33mV or more, and even more preferably 37mV or more, from the viewpoint of stabilizing the dispersion of the silica particles in the composition and easily suppressing the generation of aggregated foreign matter. The upper limit of the absolute value of the zeta potential is preferably 90mV or less, more preferably 80mV or less, and still more preferably 70mV or less. Further, the zeta potential of the present invention is preferably from-70 to-25 mV because it is easy to stabilize the dispersion of the silica particles in the composition. The lower limit is preferably-60 mV or more, more preferably-50 mV or more, and still more preferably-45 mV or more. The upper limit is preferably-28 mV or less, more preferably-31 mV or less, and still more preferably-34 mV or less. The zeta potential is a potential on a surface (sliding surface) inside the electric double layer that moves together with the particles, among potentials generated by the electric double layer formed by the surface charges of the particles and the electric double layer near the surface, when the potential of the electrically neutral solvent portion sufficiently separated from the particles in the fine particle dispersion is zero. In the present specification, the zeta potential of the composition is a value measured by electrophoresis. Specifically, the electrophoretic mobility of the microparticles was measured using a zeta potential measuring apparatus (Zetasizer Nano, manufactured by Malvern panalitica) and the zeta potential was obtained from the Huckel equation. As the measurement conditions, a general immersion cell was used, and a voltage of 40V or 60V was applied and a voltage for electrophoresis was properly selected, and the measurement was repeatedly performed 20 times in an automatic mode by the attenuator and the analysis model, and the average value thereof was set as the zeta potential of the sample. The sample is used without pretreatment such as dilution.

The surface tension of the composition of the present invention at 25 ℃ is preferably 27.0mN/m or less, more preferably 26.0mN/m or less, still more preferably 25.5mN/m or less, and still more preferably 25.0mN/m or less. The lower limit is preferably 20.0mN/m or more, more preferably 21.0mN/m or more, and further preferably 22.0mN/m or more.

When the composition of the present invention is applied to a glass substrate and heated at 200 ℃ for 5 minutes to form a film having a thickness of 0.5 μm, the contact angle of the film with respect to water at 25 ℃ is preferably 20 ° or more, more preferably 25 ° or more, and further preferably 30 ° or more, from the viewpoint of stability of the composition. From the viewpoint of coatability of the composition, the upper limit is preferably 70 ° or less, more preferably 65 ° or less, and further preferably 60 ° or less. The contact angle is a value measured using a contact angle meter (Kyowa Interface Science Co., Ltd., manufactured by Ltd., DM-701).

When the composition of the present invention is applied to a silicon wafer and heated at 200 ℃ for 5 minutes to form a film having a thickness of 0.3 μm, the refractive index of the film in light having a wavelength of 633nm is preferably 1.4 or less, more preferably 1.35 or less, still more preferably 1.3 or less, and still more preferably 1.27 or less. The lower limit is not particularly limited, and may be 1.15 or more. The above refractive index is a value measured using an ellipsometer (j.a. woollam co., manufactured by inc., VUV-vase [ product name ]). The measurement temperature was 25 ℃.

Hereinafter, each component of the composition of the present invention will be described.

Silica particles

The composition of the present invention contains silica particles. Examples of the silica particles include silica particles in which a plurality of spherical silicas are connected in a beaded shape, silica particles in which a plurality of spherical silicas are connected in a planar shape, silica particles having a hollow structure, and solid silica particles. Examples of commercially available products of the medium silica particles include PL-2L-IPA (manufactured by FUSO CHEMICAL CO., LTD.).

The silica particles used in the composition of the present invention are preferably silica particles in which a plurality of spherical silicas are connected in a beaded form, silica particles in which a plurality of spherical silicas are connected in a planar form, and silica particles having a hollow structure, and are preferably silica particles in which a plurality of spherical silicas are connected in a beaded form, and silica particles in which a plurality of spherical silicas are connected in a planar form, from the viewpoint of easier formation of a film having a small refractive index. Hereinafter, silica particles in which a plurality of spherical silicas are connected in a beaded shape and silica particles in which a plurality of spherical silicas are connected in a planar shape are also collectively referred to as beaded silicas. The silica particles in which a plurality of spherical silicas are connected in a beaded shape may have a shape in which a plurality of spherical silicas are connected in a planar manner.

In the present specification, the term "spherical" in the term "spherical silica" means that the silica is substantially spherical, and may be modified within a range in which the effects of the present invention are exhibited. It is meant to include, for example, a shape having a concave and convex surface, or a flat shape having a long axis in a specific direction. The phrase "the plurality of spherical silicas are connected in a beaded state" means that the plurality of spherical silicas are connected to each other in a linear and/or branched state. As shown in fig. 1, for example, a structure in which a plurality of spherical silica particles 1 are connected to each other via a joint 2 having an outer diameter smaller than that of the spherical silica particles can be given. In the present invention, the structure "a plurality of spherical silicas are connected in a bead-like manner" includes not only a structure in which the spherical silicas are connected in a ring shape, but also a structure in which the spherical silicas are connected in a chain shape having a terminal. The phrase "the plurality of spherical silica are connected in a planar manner" means that the plurality of spherical silica are connected to each other in substantially the same plane. The phrase "substantially the same plane" means not only the same plane but also a plane which may be vertically deviated from the same plane. For example, the particle size of the spherical silica may be deviated up and down within a range of 50% or less.

Average particle diameter D of beaded silica measured by dynamic light scattering method₁And an average particle diameter D obtained by the following formula (1)₂Ratio D of₁/D₂Preferably 3 or more. D₁/D₂The upper limit of (b) is not particularly limited, but is preferably 1000 or less, more preferably 800 or less, and further preferably 500 or less. By mixing D₁/D₂In such a range, favorable optical characteristics can be exhibited.In addition, D in the beaded silica₁/D₂The value of (b) is also an index of the degree of connection of the spherical silica.

D₂＝2720/S······(1)

In the formula, D₂Is the average particle diameter of the beaded silica in nm, and S is the specific surface area of the beaded silica measured by nitrogen adsorption in m²/g。

The above-mentioned average particle diameter D of the beaded silica₂The average particle diameter of the primary particles can be considered to be similar to that of spherical silica. Average particle diameter D₂Preferably 1nm or more, more preferably 3nm or more, still more preferably 5nm or more, and particularly preferably 7nm or more. The upper limit is preferably 100nm or less, more preferably 80nm or less, still more preferably 70nm or less, yet more preferably 60nm or less, and particularly preferably 50nm or less.

Average particle diameter D₂The equivalent circular diameter (D0) of the projected image of the spherical portion measured by a Transmission Electron Microscope (TEM) can be used instead. Unless otherwise specified, the average particle diameter based on the equivalent circle diameter is evaluated by the number average of 50 or more particles.

The above-mentioned average particle diameter D of the beaded silica₁The number average particle diameter of the secondary particles in which a plurality of spherical silicas are aggregated can be regarded as the particle diameter. Thus, in general, D₁＞D₂The relationship of (1) holds. Average particle diameter D₁Preferably 25nm or more, more preferably 30nm or more, and particularly preferably 35nm or more. The upper limit is preferably 1000nm or less, more preferably 700nm or less, still more preferably 500nm or less, and particularly preferably 300nm or less.

The above-mentioned average particle diameter D of the beaded silica₁The measurement of (2) is carried out by using a dynamic light scattering type particle size distribution measuring apparatus (nanometer Wave-EX150 manufactured by NIKK1SOCO., LTD.) [ product name ]]) To proceed with. The sequence is as follows. The dispersion of beaded silica was dispensed into a 20ml sample bottle, diluted with toluene and adjusted to a solid content concentration of 0.2 mass%. Dissolving the diluted sampleThe solution was irradiated with ultrasonic waves at 40kHz for 1 minute and then immediately used for the test. Data acquisition was carried out 10 times at 25 ℃ using a 2ml quartz cell for measurement, and the "number average" obtained was taken as the average particle diameter. As for other detailed conditions and the like, reference is made to JISZ8828 as necessary: 2013 "particle size analysis-dynamic light scattering method". 5 samples were made at 1 level and the average value was used.

The beaded silica is preferably formed by connecting a plurality of spherical silicas having an average particle diameter of 1 to 80nm via a connecting material. The upper limit of the average particle diameter of the spherical silica is preferably 70nm or less, more preferably 60nm or less, and still more preferably 50nm or less. The lower limit of the average particle diameter of the spherical silica is preferably 3nm or more, more preferably 5nm or more, and still more preferably 7nm or more. In the present invention, the average particle diameter of the spherical silica is determined from the equivalent circle diameter of a projection image of a spherical portion measured by a Transmission Electron Microscope (TEM).

Examples of the connecting material for connecting the spherical silicas include silica containing a metal oxide. Examples of the metal oxide include oxides of metals selected from Ca, Mg, Sr, Ba, Zn, Sn, Pb, Ni, Co, Fe, Al, In, Y, and Ti. Examples of the silica containing a metal oxide include those containing a metal oxide and Silica (SiO)₂) The reactants, mixtures, etc. The connecting material can be incorporated in the present specification by referring to the description of international publication No. 2000/015552.

The number of the spherical silica linked in the beaded silica is preferably 3 or more, and more preferably 5 or more. The upper limit is preferably 1000 or less, more preferably 800 or less, and further preferably 500 or less. The number of spherical silica bonds can be measured by TEM.

As the beaded silica, silica having a surface of spherical silica surface-treated with hexamethyldisilazane or the like can be used.

The silica particles may be in the form of a particle solution (sol)) The status of (2) is used. Examples of the medium for dispersing the silica particles include alcohols (e.g., methanol, ethanol, and isopropanol), ethylene glycol, glycol ethers (e.g., propylene glycol monomethyl ether), and glycol ether acetates (e.g., propylene glycol monomethyl ether acetate). Further, a solvent a1, a solvent a2, and the like, which will be described later, can also be used. In a particle solution (sol), SiO₂The concentration is preferably 5 to 40 mass%.

As the solution of beaded silica particles, for example, a silica sol described in japanese patent No. 4328935 can be used. Commercially available solutions (sols) of beaded silica particles can be used. Examples thereof include "SNOWTEXS OUP", "SNOWTEXS UP", "IPA-ST-UP", "SNOWTEXS PS-M", "SNOWTEXS PS-MO", "SNOWTEXS PS-S", "SNOWTEXS PS-SO", JGC Catalysts and Chemicals Ltd. "Fine silica gel (Fine carbohydrate) F-120", FUSO CHEMICAL CO., LTD. "Quartron PL", and the like.

Further, commercially available silica particles can be used as the particle solution of hollow silica particles. For example, "Thruria 4110" manufactured by JGC Catalysts and Chemicals Ltd.

The content of the silica particles in the composition of the present invention is preferably 4% by mass or more, more preferably 6% by mass or more, and further preferably 7% by mass or more. The upper limit is preferably 15% by mass or less, more preferably 13% by mass or less, and further preferably 11% by mass or less.

The content of the silica particles in the total solid content of the composition of the present invention is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass or more. The upper limit may be 99.95% by mass or less, may be 99.9% by mass or less, may be 99% by mass or less, and may be 95% by mass or less. If the content of the silica particles is within the above range, a film having a high antireflection effect at a low refractive index and suppressed defects can be easily obtained. In addition, when the pattern is not formed or when the pattern is formed by an etching method, the content of the silica particles in the total solid content of the composition of the present invention is preferably high, and for example, is preferably 95% by mass or more, more preferably 97% by mass or more, and still more preferably 99% by mass or more.

Hydrolysate of alkoxysilane

The composition of the present invention preferably contains at least 1 component (referred to as alkoxysilane hydrolysate) selected from the group consisting of alkoxysilane and hydrolysate of alkoxysilane. The composition of the present invention further contains an alkoxysilane hydrolysate, whereby silica particles are firmly bonded to each other during film formation, and the effect of increasing the porosity in the film can be exhibited during film formation. Further, the use of the alkoxysilane hydrolysate can improve the wettability of the film surface. The alkoxysilane hydrolysate is preferably a product produced by condensation based on hydrolysis of an alkoxysilane compound, and more preferably a product produced by condensation based on hydrolysis of an alkoxysilane compound and a fluoroalkyl group-containing alkoxysilane compound. Examples of the alkoxysilane hydrolysate include alkoxysilane hydrolysates described in paragraphs 0022 to 0027 of international publication No. 2015/190374, the contents of which are incorporated herein. When the composition of the present invention contains an alkoxysilane hydrolysate, the total content of the silica particles and the alkoxysilane hydrolysate is preferably 0.1 mass% or more, more preferably 1 mass% or more, and particularly preferably 2 mass% or more, based on the total solid content in the composition. The upper limit is preferably 99.99% by mass or less, more preferably 99.95% by mass or less, and particularly preferably 99.9% by mass or less.

Silicone surfactant

The composition of the present invention contains a silicone surfactant. In the present specification, the silicone surfactant is a compound having a repeating unit including a siloxane bond in the main chain and including a hydrophobic portion and a hydrophilic portion in 1 molecule.

The silicone surfactant used in the present invention is preferably a compound containing no fluorine atom. According to this aspect, the uniformity of the surface tension is easily improved and the effects of the present invention are easily more remarkably obtained.

When 0.1g of a silicone surfactant is dissolved in 100g of propylene glycol monomethyl ether acetate to prepare a solution, the solution preferably has a surface tension of 19.5 to 26.7mN/m at 25 ℃.

The silicone surfactant preferably has a dynamic viscosity of 20 to 3000mm at 25 DEG C²And s. The lower limit of the dynamic viscosity is preferably 22mm²More preferably 25 mm/s or more²At least s, more preferably 30mm²More than s. The upper limit of the dynamic viscosity is preferably 2500mm²Less than s, more preferably 2000mm²(ii) less than s, more preferably 1500mm²The ratio of the water to the water is less than s. When the dynamic viscosity of the silicone surfactant is within the above range, more excellent coatability can be easily obtained, and the occurrence of coating unevenness of a wave shape can be more effectively suppressed.

The silicone surfactant preferably has a weight average molecular weight of 500 to 50000. The lower limit of the weight average molecular weight is preferably 600 or more, more preferably 700 or more, and further preferably 800 or more. The upper limit of the weight average molecular weight is preferably 40000 or less, more preferably 30000 or less, and still more preferably 20000 or less.

The silicone surfactant is preferably a modified silicone compound. Examples of the modified silicone compound include compounds having a structure in which an organic group is introduced into a side chain and/or a terminal of polysiloxane. Examples of the organic group include an amino group, an epoxy group, an alicyclic epoxy group, a carbinol group, a mercapto group, a carboxyl group, a group containing a functional group selected from a fatty acid ester group and a fatty acid amide group, and a group containing a polyether chain, and the group containing a carbinol group and the group containing a polyether chain are preferable because the effect of the present invention can be more remarkably obtained.

Examples of the group containing a carbinol group include a group represented by the following formula (G-1).

-L^G1-CH₂OH……(G-1)

In the formula (G-1), L^G1Represents a single bond or a linking group. As L^G1Is shown connected toExamples of the linking group include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms, more preferably an arylene group having 6 to 12 carbon atoms), -NH-, -SO-, -SO ₂-, -CO-, -O-, -COO-, -OCO-, -S-, and a combination of 2 or more of these.

The group containing a carbinol group is preferably a group represented by formula (G-2).

-L^G2-O-L^G3-CH₂OH……(G-2)

In the formula (G-2), L^G2And L^G3Each independently represents a single bond or an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms), preferably an alkylene group.

Examples of the group containing a polyether chain include a group represented by the following formula (G-11) and a group represented by the following formula (G-12).

-L^G11-(R^G1O)_n1R^G2……(G-11)

-L^G11-(OR^G1)_n1OR^G2……(G-12)

In the formulae (G-11) and (G-12), L^G11Represents a single bond or a linking group. As L^G11The linking group includes an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms, more preferably an arylene group having 6 to 12 carbon atoms), -NH-, -SO-, -SO₂-, -CO-, -O-, -COO-, -OCO-, -S-, and a combination of 2 or more of these.

In the formulae (G-11) and (G-12), n1 represents a number of 2 or more, preferably 2 to 200.

In the formulae (G-11) and (G-12), R^G1Represents an alkylene group. The number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, and particularly preferably 2 or 3. R ^G1The alkylene group represented may be either a straight chain or a branched chain. n 1R^G1The alkylene groups may be the same or different.

Formula (G-11) and formula (G)In-12), R^G2Represents a hydrogen atom, an alkyl group or an aryl group. R^G2The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 5, and still more preferably 1 to 3. The alkyl group may be either linear or branched. R^G2The number of carbon atoms of the aryl group is preferably 6 to 20, more preferably 6 to 10.

The group containing a polyether chain is preferably a group represented by the following formula (G-13) or a group represented by the following formula (G-14).

-L^G12-(C₂H₄O)_n2(C₃H₆O)_n3R^G3……(G-13)

-L^G12-(OC₂H₄)_n2(OC₃H₆)_n3OR^G3……(G-14)

In the formulae (G-13) and (G-14), L^G12Represents a single bond or a linking group. As L^G12The linking group includes an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms, more preferably an arylene group having 6 to 12 carbon atoms), -NH-, -SO-, -SO₂-, -CO-, -O-, -COO-, -OCO-, -S-, and a combination of 2 or more of these.

In the formulae (G-13) and (G-14), n2 and n3 each independently represent a number of 1 or more, preferably 1 to 100.

In the formulae (G-13) and (G-14), R^G3Represents a hydrogen atom, an alkyl group or an aryl group. R ^G3The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 5, and still more preferably 1 to 3. The alkyl group may be either linear or branched. R^G3The number of carbon atoms of the aryl group is preferably 6 to 20, more preferably 6 to 10.

The modified silicone compound is preferably a compound represented by the following formulae (Si-1) to (Si-5).

[ chemical formula 1]

In the formula (Si-1), R¹～R⁷Each independently represents an alkyl group or an aryl group,

X¹represents a group containing a functional group selected from an amino group, an epoxy group, an alicyclic epoxy group, a carbinol group, a mercapto group, a carboxyl group, a fatty acid ester group and a fatty acid amide group, or a polyether chain-containing group,

m1 represents a number of 2 to 200.

R¹～R⁷The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 5, still more preferably 1 to 3, and particularly preferably 1. R¹～R⁷The alkyl group represented may be either linear or branched, and is preferably linear. R¹～R⁷The number of carbon atoms of the aryl group is preferably 6 to 20, more preferably 6 to 12, and particularly preferably 6. R¹～R⁷Preferably methyl or phenyl, more preferably methyl.

X¹Preferred are groups containing a carbinol group or groups containing a polyether chain, and more preferred are groups containing a carbinol group. Preferred ranges for the group comprising a carbinol group and the group comprising a polyether chain are as defined above.

In the formula (Si-2), R¹¹～R¹⁶Each independently represents an alkyl group or an aryl group,

X¹¹and X¹²Each independently represents a group containing a functional group selected from an amino group, an epoxy group, an alicyclic epoxy group, a carbinol group, a mercapto group, a carboxyl group, a fatty acid ester group and a fatty acid amide group, or a polyether chain-containing group,

m11 represents a number of 2 to 200.

R of formula (Si-2)¹¹～R¹⁶With R of formula (Si-1)¹～R⁷The same meanings are given above, and preferred ranges are also the same. X of formula (Si-2)¹¹And X¹²With X of formula (Si-1)¹The same meanings are given above, and preferred ranges are also the same.

In the formula (Si-3), R²¹～R²⁹Each independently represents an alkyl group or an aryl group,

X²¹represents a group containing a functional group selected from an amino group, an epoxy group, an alicyclic epoxy group, a carbinol group, a mercapto group, a carboxyl group, a fatty acid ester group and a fatty acid amide group, or a polyether chain-containing group,

m21 and m22 each independently represent a number of 1 to 199, and when m22 is 2 or more, m 22X²¹May be the same or different.

R of formula (Si-3)²¹～R²⁹With R of formula (Si-1)¹～R⁷The same meanings are given above, and preferred ranges are also the same. X of formula (Si-3)²¹With X of formula (Si-1)¹The same meanings are given above, and preferred ranges are also the same.

In the formula (Si-4), R³¹～R³⁸Each independently represents an alkyl group or an aryl group,

X³¹and X³²Each independently represents a group containing a functional group selected from an amino group, an epoxy group, an alicyclic epoxy group, a carbinol group, a mercapto group, a carboxyl group, a fatty acid ester group and a fatty acid amide group, or a polyether chain-containing group,

m31 and m32 each independently represent a number of 1 to 199, and when m32 is 2 or more, m 32X³¹May be the same or different.

R of formula (Si-4)³¹～R³⁸With R of formula (Si-1)¹～R⁷The same meanings are given above, and preferred ranges are also the same. X of formula (Si-4)³¹And X³²With X of formula (Si-1)¹The same meanings are given above, and preferred ranges are also the same.

In the formula (Si-5), R⁴¹～R⁴⁷Each independently represents an alkyl group or an aryl group,

X⁴¹～X⁴³each independently represents a group containing a functional group selected from an amino group, an epoxy group, an alicyclic epoxy group, a carbinol group, a mercapto group, a carboxyl group, a fatty acid ester group and a fatty acid amide group, or a polyether chain-containing group,

m41 and m42 each independently represent a number of 1 to 199, and when m42 is 2 or more, m 42X⁴²May be the same or different.

Formula (S)R of i-5)⁴¹～R⁴⁷With R of formula (Si-1)¹～R⁷The same meanings are given above, and preferred ranges are also the same. X of formula (Si-4)⁴¹～X⁴³With X of formula (Si-1)¹The same meanings are given above, and preferred ranges are also the same.

Specific examples of the silicone surfactant include the compounds described in the examples described below. Further, commercially available Silicone surfactants 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 (manufactured by Dow Corning Toray Co., Ltd.), Silwet L-77, L-7280, L-7001, L-7002, L-7200, L-7210, L-7220, L-7230, L7500, L-7600, L-7602, L-7604, L-7605, L-7622, L-7657, L-8500, L-8610 (manufactured by film Materials for use, Gm76341, GmBYK 6002, manufactured by Chemical K600330, and/or more), Toray Silicone surfactants (manufactured by Toray Silicone surfactants) and so forth.

The content of the silicone surfactant in the composition of the present invention is preferably 0.01 to 0.3% by mass. The lower limit is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and still more preferably 0.15% by mass or more, from the viewpoint of easily suppressing the occurrence of uneven coating of the waveform more effectively. The upper limit is preferably 0.28% by mass or less, more preferably 0.25% by mass or less, and still more preferably 0.2% by mass or less, for the reason of facilitating further improvement of the coatability of the other film-forming composition. The content of the silicone surfactant in the total solid content of the composition of the present invention is preferably 0.05 to 5.00 mass%. The lower limit is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, and still more preferably 1.2 mass% or more, from the viewpoint of easily suppressing the occurrence of uneven application of the waveform more effectively. The upper limit is preferably 4% by mass or less, and more preferably 3% by mass or less, for the reason of facilitating further improvement of the coatability of the other film-forming composition. The silicone surfactant is preferably contained in an amount of 0.3 to 5.5 parts by mass per 100 parts by mass of the silica particles. The lower limit is preferably 0.5 parts by mass or more, and more preferably 1.0 part by mass or more, from the viewpoint of easily suppressing the occurrence of uneven coating of the waveform more effectively. The upper limit is preferably 5.0 parts by mass or less, and more preferably 4.0 parts by mass or less, for the reason of facilitating further improvement of the coatability of the other film-forming composition. The composition of the present invention may contain only 1 kind of silicone surfactant, or may contain 2 or more kinds. When the composition of the present invention contains 2 or more silicone surfactants, the total amount of these is preferably within the above range.

Other surfactants

The composition of the present invention may contain a surfactant other than silicone surfactants (hereinafter, also referred to as other surfactants). As the other surfactant, any of a nonionic surfactant, a cationic surfactant, and an anionic surfactant can be used. Examples of the nonionic surfactant include a fluorine-based surfactant.

When the surfactant is a polymer compound, the weight average molecular weight of the surfactant is preferably 1500 or more, more preferably 2500 or more, further preferably 5000 or more, and particularly preferably 10000 or more. The upper limit is preferably 50000 or less, more preferably 25000 or less, and particularly preferably 17500 or less.

The fluorine-based surfactant is preferably a polymer (high molecular weight) surfactant having a polyethylene main chain. Among them, a polymer (high molecular weight) surfactant having a poly (meth) acrylate structure is preferable. Among these, in the present invention, a copolymer containing a (meth) acrylate constituent unit having the above-mentioned polyoxyalkylene structure and a fluoroalkyl acrylate constituent unit is preferable.

Further, as the fluorine-based surfactant, a compound having a fluoroalkyl group or a fluoroalkylene group (preferably having 1 to 24 carbon atoms, more preferably 2 to 12 carbon atoms) can be suitably used at any position. The polymer compound having the fluoroalkyl group or the fluoroalkylene group can be preferably used for the side chain. The fluorine-based surfactant preferably further has the above-mentioned polyoxyalkylene structure, and more preferably has a polyoxyalkylene structure in a side chain. Examples of the compound having a fluoroalkyl group or a fluoroalkylene group include compounds described in paragraphs 0034 to 0040 of International publication No. 2015/190374, the contents of which are incorporated herein.

Examples of the fluorine-based surfactant include Megafacef171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F479, F482, F554, F559, F780, F781F (see above, manufactured by DIC CORPORATION), Fluorad FC430, FC431, FC171 (see above, manufactured by Sumitomo 3M Limited), Surflon S-382, S-141, S-145, SC-101, SC-103, Surflon SC-104, SC-105, SC1068, SC-381, SC-383, S-393, S-40 (see above, ASAHI GLASS CO., manufactured by LTD., LTD.), EftEF 301, EF303, EF351, 352 (see above, manufactured by Jemco, Ltd., PF6320, PF6520, and SolutionVA, manufactured by OMPF 2, Inc.

Further, a block polymer can be used as the fluorine-based surfactant. For example, compounds described in Japanese patent application laid-open No. 2011-089090 can be mentioned. The fluorine-containing surfactant can also preferably use a fluorine-containing polymer compound containing: a repeating unit derived from a (meth) acrylate compound having a fluorine atom; and a repeating unit derived from a (meth) acrylate compound having 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups). The following compounds are also exemplified as the fluorine-based surfactant used in the present invention.

[ chemical formula 2]

The weight average molecular weight of the compound is preferably 3000 to 50000, for example 14000. In the above compounds,% representing the proportion of the repeating unit is mol%.

The nonionic surfactant, anionic surfactant and cationic surfactant other than the fluorine-based surfactant include the surfactants described in paragraphs 0042 to 0045 of International publication No. 2015/190374, the contents of which are incorporated herein.

As the other surfactant, a surfactant having a polyoxyalkylene structure can be used. The polyoxyalkylene structure is a structure in which an alkylene group is present adjacent to a 2-valent oxygen atom, and specific examples thereof include an Ethylene Oxide (EO) structure and a Propylene Oxide (PO) structure. The polyoxyalkylene structure may constitute a graft chain of the propylene polymer.

The content of the other surfactant is preferably 5.0 parts by mass or less, more preferably 3.0 parts by mass or less, and still more preferably 1.0 part by mass or less, based on 100 parts by mass of the total of the silicone surfactant and the other surfactant. The content of the other surfactant in the composition of the present invention is preferably 0.1% by mass or less, more preferably 0.05% by mass or less, and still more preferably 0.02% by mass or less. The content of the other surfactant in the total solid content of the composition of the present invention is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, and still more preferably 0.2% by mass or less. Also, the composition of the present invention preferably contains substantially no other surfactant. The case where the composition of the present invention contains substantially no other surfactant means that the content of the surfactant in the total solid content of the composition of the present invention is 0.01% by mass or less, preferably 0.005% by mass or less, and more preferably contains no other surfactant.

Solvents

The composition of the present invention contains a solvent. Examples of the solvent include an organic solvent and water, and preferably include at least an organic solvent. Examples of the organic solvent include aliphatic hydrocarbon solvents, halogenated hydrocarbon solvents, alcohol solvents, ether solvents, ester solvents, ketone solvents, nitrile solvents, amide solvents, sulfoxide solvents, and aromatic solvents.

Examples of the aliphatic hydrocarbon solvent include hexane, cyclohexane, methylcyclohexane, pentane, cyclopentane, heptane, octane, and the like.

Examples of the halogenated hydrocarbon solvent include methyl chloride, chloroform, dichloromethane, dichloroethane, carbon tetrachloride, trichloroethylene, tetrachloroethylene, epichlorohydrin, monochlorobenzene, o-dichlorobenzene, chloropropene, methyl monochloroacetate, ethyl monochloroacetate, monochloroacetic trichloroacetic acid, methyl bromide, and tris (tetra) vinyl chloride.

Examples of the alcohol solvent include methanol, ethanol, 1-propanol, 2-butanol, ethylene glycol, propylene glycol, glycerol, 1, 6-hexanediol, cyclohexanediol, sorbitol, xylitol, 2-methyl-2, 4-pentanediol, 3-methoxy-1-butanol, 1, 3-butanediol, and 1, 4-butanediol.

Examples of the ether solvent include dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, cyclohexyl methyl ether, anisole, tetrahydrofuran, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol methyl-n-propyl ether, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, Tripropylene glycol monobutyl ether, tetraethylene glycol dimethyl ether, polyethylene glycol monomethyl ether, polyethylene glycol dimethyl ether, and the like.

Examples of the ester-based solvent include propylene carbonate, dipropylene ester, 1, 4-butanediol diacetate, 1, 3-butanediol diacetate, 1, 6-hexanediol diacetate, cyclohexanol acetate, dipropylene glycol methyl ether acetate, methyl acetate, ethyl acetate, isopropyl acetate, n-propyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and glycerol triacetate.

Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and 2-heptanone.

The nitrile solvent includes acetonitrile and the like.

Examples of the amide solvent include N, N-dimethylformamide, 1-methyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, 2-pyrrolidone, epsilon-caprolactam, formamide, N-methylformamide, acetamide, N-methylacetamide, N-dimethylacetamide, N-methylpropanamide, hexamethylphosphoric triamide, 3-methoxy-N, N-dimethylpropionamide, and 3-butoxy-N, N-dimethylpropionamide.

Examples of the sulfoxide solvent include dimethyl sulfoxide and the like.

Examples of the aromatic solvent include benzene and toluene.

The content of the solvent in the composition of the present invention is preferably 70 to 99% by mass. The upper limit is preferably 93% by mass or less, more preferably 92% by mass or less, and still more preferably 90% by mass or less. The lower limit is preferably 75% by mass or more, more preferably 80% by mass or more, and still more preferably 85% by mass or more.

In the present invention, it is preferable to use a solvent containing solvent a1 having a boiling point of 190 ℃ or higher and 280 ℃ or lower. In the present specification, the boiling point of the solvent is a value at 1 atmosphere (0.1 MPa).

The boiling point of the solvent a1 is preferably 200 ℃ or higher, more preferably 210 ℃ or higher, and still more preferably 220 ℃ or higher. The boiling point of the solvent a1 is preferably 270 ℃ or lower, and more preferably 265 ℃ or lower.

The viscosity of the solvent a1 is preferably 10mPa · s or less, more preferably 7mPa · s or less, and still more preferably 4mPa · s or less. From the viewpoint of coatability, the lower limit of the viscosity of the solvent a1 is preferably 1.0mPa · s or more, more preferably 1.4mPa · s or more, and still more preferably 1.8mPa · s or more.

The molecular weight of the solvent a1 is preferably 100 or more, more preferably 130 or more, further preferably 140 or more, and particularly preferably 150 or more. From the viewpoint of coatability, the upper limit is preferably 300 or less, more preferably 290 or less, still more preferably 280 or less, and particularly preferably 270 or less.

The solubility parameter of the solvent A1 is preferably 8.5-13.3 (cal/cm)³)^0.5. The upper limit is preferably 12.5 (cal/cm)³)^0.5Hereinafter, more preferably 11.5 (cal/cm)³)^0.5More preferably 10.5 (cal/cm) or less³)^0.5The following. The lower limit is preferably 8.7 (cal/cm)³)^0.5Above, more preferably 8.9 (cal/cm)³)^0.5Above, more preferably 9.1 (cal/cm)³)^0.5The above. As long as the solubility parameter of the solvent a1 is within the above range, high affinity with the silica particles a can be obtained, and excellent coatability is easily obtained. In addition, 1 (cal/cm)³)^0.5Is 2.0455MPa^0.5. And, the solubility parameter of the solvent is a value calculated from HSPiP.

In the present specification, hansen solubility parameter is used as the solubility parameter of the solvent. Specifically, the value calculated using hansen solubility parameter software "HSPiP 5.0.09".

The solvent a1 is preferably an aprotic solvent. By using an aprotic solvent as the solvent a1, aggregation of the silica particles a during film formation can be more effectively suppressed.

The solvent a1 is preferably an ether solvent and an ester solvent, and more preferably an ester solvent. The ester solvent used as the solvent a1 is preferably a compound containing no hydroxyl group or terminal alkoxy group. By using an ester-based solvent having no such functional group, the effects of the present invention can be more easily and significantly obtained.

The solvent a1 is preferably at least 1 selected from alkylene glycol diacetate and cyclic carbonate, from the viewpoint that high affinity with the silica particles a can be obtained and excellent coatability can be easily obtained. Examples of the alkylene glycol diacetate include propylene glycol diacetate, 1, 4-butanediol diacetate, 1, 3-butanediol diacetate, and 1, 6-hexanediol diacetate. Examples of the cyclic carbonate include propylene carbonate and ethylene carbonate.

Specific examples of the solvent A1 include propylene carbonate (boiling point: 240 ℃ C.), ethylene carbonate (boiling point: 260 ℃ C.), propylene glycol diacetate (boiling point: 190 ℃ C.), dipropylene glycol methyl-n-propyl ether (boiling point: 203 ℃ C.), dipropylene glycol methyl ether acetate (boiling point: 213 ℃ C.), 1, 4-butanediol diacetate (boiling point: 232 ℃ C.), 1, 3-butanediol diacetate (boiling point: 232 ℃ C.), 1, 6-hexanediol diacetate (boiling point: 260 ℃ C.), diethylene glycol monoethyl ether acetate (boiling point: 217 ℃ C.), diethylene glycol monobutyl ether acetate (boiling point: 247 ℃ C.), glycerol triacetate (boiling point: 260 ℃ C.), dipropylene glycol monomethyl ether (boiling point: 190 ℃ C.), diethylene glycol monoethyl ether (boiling point: 202 ℃ C.), dipropylene glycol monopropyl ether (boiling point: 212 ℃ C.), dipropylene glycol monobutyl ether (boiling point: 229 ℃ C.), tripropylene glycol monomethyl ether (boiling point: 242 ℃ C.), and propylene glycol monomethyl ether (boiling point: 242 ℃ C.) Tripropylene glycol monobutyl ether (boiling point 274 ℃ C.), and the like.

The solvent used in the composition of the present invention is preferably a solvent containing 3 mass% or more of the above-mentioned solvent a1, more preferably 4 mass% or more, and still more preferably 5 mass% or more. According to this aspect, the above-described effects of the present invention can be easily obtained remarkably. The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 12% by mass or less. According to this embodiment, a film having a good surface state can be easily obtained. The solvent A1 may be used alone or in combination of 2 or more. When the composition of the present invention contains 2 or more kinds of the solvent a1, the total amount of these is preferably within the above range.

The solvent used in the composition of the present invention preferably further contains solvent a2 having a boiling point of 110 ℃ or higher and less than 190 ℃. According to this embodiment, the drying property of the composition can be appropriately improved, thereby effectively suppressing the occurrence of uneven coating of the waveform and easily forming a film having a good surface state.

The boiling point of the solvent a2 is preferably 115 ℃ or higher, more preferably 120 ℃ or higher, and still more preferably 130 ℃ or higher. The boiling point of the solvent a2 is preferably 170 ℃ or lower, and more preferably 150 ℃ or lower. As long as the boiling point of the solvent a2 is within the above range, the above effect is more easily obtained significantly.

From the viewpoint of more easily obtaining the above-described effect remarkably, the molecular weight of the solvent a2 is preferably 100 or more, more preferably 130 or more, further preferably 140 or more, and particularly preferably 150 or more. From the viewpoint of coatability, the upper limit is preferably 300 or less, more preferably 290 or less, still more preferably 280 or less, and particularly preferably 270 or less.

The solubility parameter of the solvent A2 is preferably 9.0-11.4 (cal/cm)³)^0.5. The upper limit is preferably 11.0 (cal/cm)³)^0.5More preferably 10.6 (cal/cm) or less³)^0.5More preferably 10.2 (cal/cm) or less³)^0.5The following. The lower limit is preferably 9.2 (cal/cm)³)^0.5Above, more preferably 9.4 (cal/cm)³)^0.5Above, more preferably 9.6 (cal/cm)³)^0.5The above. As long as the solubility parameter of the solvent a2 is within the above range, high affinity with the silica particles a can be obtained, and excellent coatability is easily obtained. The absolute value of the difference between the solubility parameter of the solvent A1 and the solubility parameter of the solvent A2 is preferably 0.01 to 1.1 (cal/cm)³)^0.5. The upper limit is preferably 0.9 (cal/cm)³)^0.5Hereinafter, more preferably 0.7 (cal/cm)³)^0.5More preferably 0.5 (cal/cm) or less³)^0.5The following. The lower limit is preferably 0.03 (cal/cm)³)^0.5Above, more preferably 0.05 (cal/cm)³)^0.5Above, more preferably 0.08 (cal/cm) ³)^0.5The above.

The solvent a2 preferably contains at least 1 selected from the group consisting of ether solvents and ester solvents, more preferably at least ester solvents, and still more preferably ether solvents and ester solvents. Specific examples of the solvent a2 include cyclohexanol acetate (boiling point 173 ℃), dipropylene glycol dimethyl ether (boiling point 175 ℃), butyl acetate (boiling point 126 ℃), ethylene glycol monomethyl ether acetate (boiling point 145 ℃), propylene glycol monomethyl ether acetate (boiling point 146 ℃), 3-methoxybutyl acetate (boiling point 171 ℃), propylene glycol monomethyl ether (boiling point 120 ℃), 3-methoxybutanol (boiling point 161 ℃), propylene glycol monopropyl ether (boiling point 150 ℃), propylene glycol monobutyl ether (boiling point 170 ℃), ethylene glycol monobutyl ether acetate (boiling point 188 ℃), and the like, and from the viewpoint of obtaining high affinity with the silica particles a and easily obtaining excellent coatability, it is preferable to include at least propylene glycol monomethyl ether acetate.

When the solvent used in the composition of the present invention contains solvent a2, the content of solvent a2 is preferably 500 to 5000 parts by mass per 100 parts by mass of solvent a 1. The upper limit is preferably 4500 parts by mass or less, more preferably 4000 parts by mass or less, and further preferably 3500 parts by mass or less. The lower limit is preferably 600 parts by mass or more, more preferably 700 parts by mass or more, and further preferably 750 parts by mass or more. The content of the solvent a2 in the total amount of solvents is preferably 50 mass% or more, more preferably 60 mass% or more, and still more preferably 70 mass% or more. The upper limit is preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass or less. As long as the content of the solvent a2 is within the above range, the effect of the present invention is more easily obtained significantly. The solvent A2 may be used alone or in combination of 2 or more. When the composition of the present invention contains 2 or more kinds of the solvent a2, the total amount of these is preferably within the above range.

The solvent used in the composition of the present invention is preferably a solvent containing 62 mass% or more of the solvent a1 and the solvent a2 in total, more preferably 72 mass% or more, and still more preferably 82 mass% or more. The upper limit may be 100 mass%, 96 mass% or less, or 92 mass% or less.

The solvent used in the composition of the present invention also preferably further contains at least 1 solvent a3 selected from methanol, ethanol, and 2-propanol. According to this embodiment, high affinity with the silica particles a can be obtained, and excellent coatability can be easily obtained. When the solvent used in the composition of the present invention further contains solvent A3, the content of solvent A3 in the total amount of solvent is preferably 0.1 to 10% by mass. The upper limit is preferably 8% by mass or less, more preferably 6% by mass or less, and further preferably 4% by mass or less. The lower limit is preferably 0.3% by mass or more, more preferably 0.5% by mass or more, and further preferably 1% by mass or more. As long as the content of the solvent a3 is within the above range, the above effect is more easily obtained significantly. The solvent A3 may be used alone or in combination of 2 or more. When the composition of the present invention contains 2 or more kinds of the solvent a3, the total amount of these is preferably within the above range.

The solvent used in the composition of the present invention also preferably further contains water. According to this embodiment, high affinity with the silica particles a can be obtained, and excellent coatability can be easily obtained. When the solvent used in the composition of the present invention further contains water, the content of water in the total amount of the solvent is preferably 0.1 to 5% by mass. The upper limit is preferably 4% by mass or less, more preferably 2.5% by mass or less, and further preferably 1.5% by mass or less. The lower limit is preferably 0.3% by mass or more, more preferably 0.5% by mass or more, and further preferably 1.0% by mass or more. As long as the content of water is within the above range, the above effects are more easily obtained significantly.

The solvent used in the composition of the present invention also preferably comprises the above-mentioned solvent a3 and water. High affinity with the silica particles a can be obtained and excellent coatability can be easily obtained. When the solvent used in the composition of the present invention contains the solvent A3 and water, the total content of the solvent A3 and water in the total amount of the solvent is preferably 0.2 to 15% by mass. The upper limit is preferably 12% by mass or less, more preferably 9% by mass or less, and further preferably 6% by mass or less. The lower limit is preferably 0.4% by mass or more, more preferably 0.7% by mass or more, and further preferably 1.5% by mass or more. If the total content of the solvent a3 and water is within the above range, the above-described effects can be more easily and remarkably obtained.

The solvent used in the composition of the invention can further contain solvent a4 having a boiling point greater than 280 ℃. According to this embodiment, the drying property of the composition can be appropriately improved, thereby effectively suppressing the occurrence of uneven coating of the waveform and easily forming a film having a good surface state. The upper limit of the boiling point of the solvent a4 is preferably 400 ℃ or lower, more preferably 380 ℃ or lower, and still more preferably 350 ℃ or lower. The solvent a4 is preferably at least 1 selected from ether solvents and ester solvents. Specific examples of the solvent a4 include polyethylene glycol monomethyl ether. When the solvent used in the composition of the present invention further contains solvent a4, the content of solvent a4 in the total amount of solvent is preferably 0.5 to 15% by mass. The upper limit is preferably 10% by mass or less, more preferably 8% by mass or less, and further preferably 6% by mass or less. The lower limit is preferably 1% by mass or more, more preferably 1.5% by mass or more, and further preferably 2% by mass or more. The solvent used in the composition of the present invention is also preferably substantially free of solvent a 4. The substantial absence of the solvent a4 means that the content of the solvent a4 in the total amount of the solvents is 0.1 mass% or less, preferably 0.05 mass% or less, more preferably 0.01 mass% or less, and even more preferably none.

The solvent used in the composition of the present invention may contain a solvent (other solvent) other than the above-mentioned solvent a1, solvent a2, solvent A3, solvent a4 and water, and preferably, it does not substantially contain other solvent. The term "substantially not containing any other solvent" means that the content of the other solvent in the total amount of the solvents is 0.1% by mass or less, preferably 0.05% by mass or less, more preferably 0.01% by mass or less, and still more preferably not containing any other solvent.

The content of the compound having a molecular weight (weight average molecular weight in the case of a polymer) of more than 300 in the solvent used in the composition of the present invention is preferably 10% by mass or less, more preferably 8% by mass or less, still more preferably 5% by mass or less, still more preferably 3% by mass or less, and particularly preferably 1% by mass or less. According to this embodiment, more excellent coatability and a film having an excellent surface state can be easily obtained.

The content of the compound having a viscosity of more than 10mPa · s at 25 ℃ in the solvent used in the composition of the present invention is preferably 10% by mass or less, more preferably 8% by mass or less, still more preferably 5% by mass or less, still more preferably 3% by mass or less, and particularly preferably 1% by mass or less. According to this embodiment, more excellent coatability and a film having an excellent surface state can be easily obtained.

Dispersing agent

The compositions of the present invention can contain a dispersant. Examples of the dispersant include polymeric dispersants (e.g., polyamidoamine and salts thereof, polycarboxylic acid and salts thereof, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic copolymer, formalin condensate of naphthalenesulfonic acid), polyoxyethylene alkyl phosphate, polyoxyethylene alkylamine, and alkanolamine. The polymer dispersants can be further classified into linear polymers, terminal-modified polymers, graft polymers, and block polymers according to their structures. The polymeric dispersant is adsorbed on the surface of the particles and acts to prevent reagglomeration. Therefore, preferred examples of the structure include a terminal-modified polymer, a graft polymer, and a block polymer having a site to be fixed to the particle surface. The dispersant may be a commercially available product. For example, a product described in paragraph 0050 of international publication No. 2016/190374 can be mentioned, and the contents thereof are incorporated in the present specification.

The content of the dispersant is preferably 1 to 100 parts by mass, more preferably 3 to 100 parts by mass, and still more preferably 5 to 80 parts by mass, per 100 parts by mass of the silica particles. The content of the dispersant is preferably 1 to 30% by mass based on the total solid content of the composition. The number of the dispersants may be only 1, or may be 2 or more. When the composition of the present invention contains 2 or more dispersants, the total amount of these is preferably within the above range.

Polymerizable Compound

The composition of the present invention may contain a polymerizable compound. As the polymerizable compound, a known compound that can be crosslinked by a radical, an acid, or heat can be used. In the present invention, the polymerizable compound is preferably a radical polymerizable compound. The radical polymerizable compound is preferably a compound having an ethylenically unsaturated bond.

The polymerizable compound may be any of chemical forms such as a monomer, a prepolymer, and an oligomer, but is preferably a monomer. The molecular weight of the polymerizable compound is preferably 100 to 3000. The upper limit is more preferably 2000 or less, and still more preferably 1500 or less. The lower limit is more preferably 150 or more, and still more preferably 250 or more.

The polymerizable compound is preferably a compound having 2 or more ethylenically unsaturated bond groups, and more preferably a compound having 3 or more ethylenically unsaturated bond groups. The upper limit of the number of ethylenically unsaturated bond groups is, for example, preferably 15 or less, and more preferably 6 or less. Examples of the ethylenically unsaturated bond group include a vinyl group, a styryl group, (meth) allyl group, and a (meth) acryloyl group is preferable. The polymerizable compound is preferably a 3-15 functional (meth) acrylate compound, and more preferably a 3-6 functional (meth) acrylate compound. Specific examples of the polymerizable compound include compounds described in paragraphs 0059 to 0079 of international publication No. 2016/190374.

As the polymerizable compound, dipentaerythritol triacrylate (as a commercially available product, KAYARAD-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercially available product, KAYARAD-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) acrylate (as a commercially available product, KAYARAD-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercially available product, KAYARAD DPHA; Nippon Kayaku Co., manufactured by Ltd., Estk. A-DPH-12E; Shin-Nakamura Chemical Co., Ltd., manufactured by Ltd.) and a compound having a structure in which a (meth) acryloyl group of these compounds is bonded to a propylene glycol residue (for example, commercially available modified glycerol acrylate, SARTER 454, DME-modified ethylene oxide (SR) (as a commercially available product, EO-454), m-460; TOAGOSEI CO., ltd., manufactured), neopentylglycol tetraacrylate (Shin-Nakamura Chemical CO., ltd., manufactured, NK EsterA-TMMT), 1, 6-hexanediol diacrylate (Nippon Kayaku CO., ltd., manufactured, KAYARAD HDDA), RP-1040(Nippon Kayaku CO., ltd., manufactured), aroni-2349 (toagoseico., ltd., manufactured), NK Oligo UA-7200(Shin-Nakamura Chemical CO., ltd., manufactured), 8UH-1006, 8UH-1012(TAISEI FINE CHEMICAL CO., ltd., manufactured), light acrylate POB-a0(KYOEISHA Chemical CO., ltd., manufactured), and the like. As the polymerizable compound, a compound having the following structure can also be used.

[ chemical formula 3]

Further, as the polymerizable compound, a 3-functional (meth) acrylate compound such as trimethylolpropane tri (meth) acrylate, trimethylolpropane-propylene oxide-modified tri (meth) acrylate, trimethylolpropane-ethylene oxide-modified tri (meth) acrylate, isocyanuric acid-ethylene oxide-modified tri (meth) acrylate, pentaerythritol tri (meth) acrylate, or the like can be used. Commercially available products of 3-functional (meth) acrylate compounds include ARONIX M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, M-305, M-303, M-452, M-450 (manufactured by TOAGOSEI CO., LTD.), NK EsterA9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, TMPT (Shin-Nakamura Chemical Co., manufactured by Ltd.), KARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.).

As the polymerizable compound, a compound having an acid group can be used. By using a polymerizable compound having an acid group, the polymerizable compound in the unexposed portion is easily removed during development, and generation of development residue can be suppressed. Examples of the acid group include a carboxyl group, a sulfo group, a phosphate group and the like, and a carboxyl group is preferable. Commercially available products of polymerizable compounds having an acid group include ARONIX M-510, M-520, and ARONIX TO-2349 (manufactured by TOAGOSEI CO., LTD.). The acid value of the polymerizable compound having an acid group is preferably 0.1 to 40mgKOH/g, more preferably 5 to 30 mgKOH/g. The acid value of the polymerizable compound is preferably 0.1mgKOH/g or more, and the solubility in a developer is good, and preferably 40mgKOH/g or less, from the viewpoint of production and handling.

As the polymerizable compound, a compound having a caprolactone structure can be used. Polymerizable compounds having a caprolactone structure are sold as KAYARAD DPCA series by Nippon Kayaku Co., Ltd., and examples thereof include DPCA-20, DPCA-30, DPCA-60, DPCA-120 and the like.

The polymerizable compound having an alkyleneoxy group can also be used. The polymerizable compound having an alkyleneoxy group is preferably a polymerizable compound having an ethyleneoxy group and/or a propyleneoxy group, more preferably a polymerizable compound having an ethyleneoxy group, and still more preferably a 3-6 functional (meth) acrylate compound having 4-20 ethyleneoxy groups. Commercially available products of the polymerizable compound having an alkyleneoxy group include, for example, SR-494 of a 4-functional (meth) acrylate having 4 ethyleneoxy groups and KAYARAD TPA-330 of a 3-functional (meth) acrylate having 3 isobutylene oxy groups, which are manufactured by Sartomer Company, Inc.

The polymerizable compound having a fluorene skeleton can also be used as the polymerizable compound. Examples of commercially available products of polymerizable compounds having a fluorene skeleton include OGSOL EA-0200 and EA-0300 (a (meth) acrylate monomer having a fluorene skeleton, manufactured by Osaka Gas Chemical Co., Ltd.).

As the polymerizable compound, a compound substantially not containing an environmental control substance such as toluene is also preferably used. Commercially available products of these compounds include KAYARAD DPHA LT and KAYARAD DPEA-12LT (manufactured by Nippon Kayaku Co., Ltd.).

When the composition of the present invention contains a polymerizable compound, the content of the polymerizable compound in the composition of the present invention is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and still more preferably 0.5% by mass or more. The upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less. The content of the polymerizable compound in the total solid content of the composition of the present invention is preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 5% by mass or more. The upper limit is preferably 30% by mass or less, more preferably 25% by mass or less, and still more preferably 20% by mass or less. The composition of the present invention may contain only 1 polymerizable compound, or may contain 2 or more polymerizable compounds. When the composition of the present invention contains 2 or more polymerizable compounds, the total amount of these is preferably within the above range.

The composition of the present invention also preferably contains substantially no polymerizable compound. When the composition of the present invention contains substantially no polymerizable compound, a film having a lower refractive index is easily formed. Further, a film with low haze can be easily formed. The case where the composition of the present invention contains substantially no polymerizable compound means that the content of the polymerizable compound in the total solid content of the composition of the present invention is 0.05% by mass or less, preferably 0.01% by mass or less, and more preferably contains no polymerizable compound.

Photopolymerization initiator

When the composition of the present invention contains a polymerizable compound, it preferably further contains a photopolymerization initiator. When the composition of the present invention contains a polymerizable compound and a photopolymerization initiator, the composition of the present invention can be preferably used as a composition for forming a pattern by photolithography.

The photopolymerization initiator is not particularly limited as long as it has an ability to start polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. When a radical polymerizable compound is used as the polymerizable compound, a photo radical polymerization initiator is preferably used as the photopolymerization initiator. Examples of the photo radical polymerization initiator include trihalomethyltri The compound, benzyl dimethyl ketal compound, α -hydroxyketone compound, α -aminoketone compound, acylphosphine compound, phosphine oxide compound, metallocene compound, oxime compound, triarylimidazole dimer, onium compound, benzothiazole compound, diphenylketone compound, acetophenone compound, cyclopentadiene-benzene-iron complex compound, halomethyl oxadiazole compound, coumarin compound, and the like, preferably oxime compound, α -hydroxyketone compound, α -aminoketone compound, and acylphosphine compound, more preferably oxime compound, α -aminoketone compound, and still more preferably oxime compound. An example of the photopolymerization initiator is Japanese patent laid-open publication No. 2015-166449The contents of the compounds described in the paragraphs 0099-0125 are incorporated herein.

Examples of the oxime compound include a compound described in Japanese patent laid-open No. 2001-233842, a compound described in Japanese patent laid-open No. 2000-080068, a compound described in Japanese patent laid-open No. 2006-342166, a compound described in J.C.S.Perkin II (1979, pp.1653-1660), a compound described in J.C.S.Perkin II (1979, pp.156-162), a compound described in Journal of Photopharmaceuticals Science and Technology (1995, pp.202-232), a compound described in Japanese patent laid-open No. 2000-630685, a compound described in Japanese patent laid-open No. 2000-080068, a compound described in Japanese patent laid-open No. 2004-534797, a compound described in Japanese patent laid-open No. 2006-342166, a compound described in Japanese patent laid-open No. 2017-019766, a compound described in Japanese patent laid-open No. 6065596, A compound described in International publication No. 2015/152153, a compound described in International publication No. 2017/051680, a compound described in Japanese patent laid-open publication No. 2017-198865, a compound described in paragraphs No. 0025 to 0038 of 2017/164127, a compound described in International publication No. 2013/167515, and the like. Specific examples of oxime compounds include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutyl-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. Commercially available products include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (manufactured by BASF Corporation), TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), and ADEKA OPTOMER N-1919 (manufactured by ADEKA CORPORATION, photopolymerization initiator 2 described in Japanese patent application laid-open No. 2012-014052). Further, as the oxime compound, a compound having no coloring property or a compound having high transparency and being less likely to be discolored is also preferably used. Examples of commercially available products include ADEKA ARKLS NCI-730, NCI-831 and NCI-930 (manufactured by ADEKA CORPORATION).

In the present invention, an oxime compound having a fluorene ring can also be used as a photopolymerization initiator. Specific examples of the oxime compounds having fluorene rings include the compounds described in Japanese patent laid-open publication No. 2014-137466. The contents of which are incorporated in this specification.

In the present invention, an oxime compound having a fluorine atom can also be used as a photopolymerization initiator. Specific examples of the oxime compound having a fluorine atom include the compounds described in Japanese patent application laid-open No. 2010-262028, the compounds 24 and 36 to 40 described in Japanese patent application laid-open No. 2014-500852, and the compound (C-3) described in Japanese patent application laid-open No. 2013-164471.

In the present invention, an oxime compound having a nitro group can be used as a photopolymerization initiator. Oxime compounds having a nitro group are also preferred as dimers. Specific examples of the oxime compound having a nitro group include compounds described in paragraphs 0031 to 0047 of Japanese patent application laid-open No. 2013-114249, paragraphs 0008 to 0012 and 0070 to 0079 of Japanese patent application laid-open No. 2014-137466, compounds described in paragraphs 0007 to 0025 of Japanese patent application laid-open No. 4223071, and ADEKA ARKLS NCI-831 (manufactured by ADEKA CORPORATION).

In the present invention, an oxime compound having a benzofuran skeleton can also be used as a photopolymerization initiator. Specific examples thereof include OE-01 to OE-75 as described in International publication No. 2015/036910.

The oxime compound is preferably a compound having a maximum absorption wavelength in a wavelength range of 350 to 500nm, and more preferably a compound having a maximum absorption wavelength in a wavelength range of 360 to 480 nm. From the viewpoint of sensitivity, the molar absorption coefficient of the oxime compound at a wavelength of 365nm or 405nm is preferably high, more preferably 1000 to 300000, still more preferably 2000 to 300000, and particularly preferably 5000 to 200000. The molar absorption coefficient of a compound can be measured by a known method. For example, it is preferable to use a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian corporation) and to perform measurement at a concentration of 0.01g/L using ethyl acetate.

As the photopolymerization initiator, a 2-functional or 3-or more-functional photo radical polymerization initiator can be used. By using such a photo radical polymerization initiator, 2 or more radicals are generated from 1 molecule of the photo radical polymerization initiator, and thus good sensitivity can be obtained. In addition, when a compound having an asymmetric structure is used, the crystallinity is reduced, the solubility in an organic solvent or the like is improved, and the compound is less likely to precipitate with the passage of time, whereby the stability of the composition with the passage of time can be improved. Specific examples of the 2-functional or 3-or more-functional photo radical polymerization initiator include dimers of oxime compounds described in Japanese patent application No. 2010-527339, Japanese patent application No. 2011-524436, International publication No. 2015/004565, Japanese patent application No. 2016-532675, paragraphs 0407 to 0412, and International publication No. 2017/033680, paragraphs 0039 to 0055, the compound (E) and the compound (G) described in JP-A-2013-522445, Cmpd 1-7 described in International publication No. 2016/034963, the oxime ester photoinitiator described in JP-A-2017-523465, the photoinitiator described in JP-A-2017-0020-0033, and the photopolymerization initiator (A) described in JP-A-2017-151342-0017-0026.

When the composition of the present invention contains a photopolymerization initiator, the content of the photopolymerization initiator in the composition of the present invention is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and still more preferably 0.5% by mass or more. The upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less. The content of the photopolymerization initiator in the total solid content of the composition of the present invention is preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 5% by mass or more. The upper limit is preferably 30% by mass or less, more preferably 25% by mass or less, and still more preferably 20% by mass or less. Further, it is preferable that the photopolymerization initiator is contained in an amount of 10 to 1000 parts by mass based on 100 parts by mass of the polymerizable compound. The upper limit is preferably 500 parts by mass or less, more preferably 300 parts by mass or less, and still more preferably 100 parts by mass or less. The lower limit is preferably 20 parts by mass or more, more preferably 40 parts by mass or more, and further preferably 60 parts by mass or more. The composition of the present invention may contain only 1 kind of photopolymerization initiator, or may contain 2 or more kinds. When the composition of the present invention contains 2 or more kinds of photopolymerization initiators, the total amount of these is preferably within the above range.

The composition of the present invention also preferably contains substantially no photopolymerization initiator. The case where the composition of the present invention contains substantially no photopolymerization initiator means that the content of the photopolymerization initiator in the total solid content of the composition of the present invention is 0.005% by mass or less, preferably 0.001% by mass or less, and more preferably does not contain a photopolymerization initiator.

Resin (resin)

The composition of the present invention may further contain a resin. The weight average molecular weight (Mw) of the resin is preferably 3000 to 2000000. The upper limit is preferably 1000000 or less, more preferably 500000 or less. The lower limit is preferably 4000 or more, and more preferably 5000 or more.

Examples of the resin include (meth) acrylic resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene ether phosphine oxide resins, polyimide resins, polyamideimide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, and silicone resins. These resins may be used alone in 1 kind, or 2 or more kinds may be mixed and used. Further, the resins described in paragraphs 0041 to 0060 of Japanese patent application laid-open No. 2017-206689, the resins described in paragraphs 0022 to 0071 of Japanese patent application laid-open No. 2018-010856, the resins described in Japanese patent application laid-open No. 2017-057265, the resins described in Japanese patent application laid-open No. 2017-032685, the resins described in Japanese patent application laid-open No. 2017-075248, the resins described in Japanese patent application laid-open No. 2017-066240, and the resins described in paragraph 0016 of Japanese patent application laid-open No. 2018-145339 can be used.

In the present invention, a resin having an acid group is also preferably used as the resin. According to this aspect, the developability can be further improved when forming a pattern by photolithography. Examples of the acid group include a carboxyl group, a phosphoric group, a sulfo group, a phenolic hydroxyl group, and the like, and a carboxyl group is preferable. Resins having acid groups can be used as alkali-soluble resins, for example.

The resin having an acid group preferably includes a repeating unit having an acid group on a side chain, and more preferably includes 5 to 70 mol% of a repeating unit having an acid group on a side chain among all repeating units of the resin. The upper limit of the content of the repeating unit having an acid group in a side chain is preferably 50 mol% or less, and more preferably 30 mol% or less. The lower limit of the content of the repeating unit having an acid group in a side chain is preferably 10 mol% or more, and more preferably 20 mol% or more.

The acid value of the resin having an acid group is preferably 30 to 500 mgKOH/g. The lower limit is preferably 50mgKOH/g or more, more preferably 70mgKOH/g or more. The upper limit is preferably 400mgKOH/g or less, more preferably 300mgKOH/g or less, and still more preferably 200mgKOH/g or less. The weight average molecular weight (Mw) of the resin having an acid group is preferably 5000 to 100000. The number average molecular weight (Mn) of the resin having an acid group is preferably 1000 to 20000.

When the composition of the present invention contains a resin, the content of the resin in the composition of the present invention is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and still more preferably 0.1% by mass or more. The upper limit is preferably 2% by mass or less, more preferably 1% by mass or less, and still more preferably 0.5% by mass or less. The resin content of the composition of the present invention in the total solid content is preferably 0.2% by mass or more, more preferably 0.7% by mass or more, and still more preferably 1.2% by mass or more. The upper limit is preferably 18% by mass or less, more preferably 12% by mass or less, and still more preferably 5% by mass or less. The composition of the present invention may contain only 1 kind of resin, or may contain 2 or more kinds. When the composition of the present invention contains 2 or more kinds of resins, the total amount of these is preferably within the above range.

Adhesion improving agent

The composition of the present invention may further contain an adhesion improving agent. By containing the adhesion improver, a film having excellent adhesion to the support can be formed. As the adhesion improving agent, for example, the adhesion improving agents described in Japanese patent application laid-open Nos. H05-011439, H05-341532 and H06-043638 can be cited as appropriate. Specific examples thereof include benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 3-morpholinomethyl-1-phenyl-triazole-2-thione, 3-morpholinomethyl-5-phenyl-oxadiazole-2-thione, 5-amino-3-morpholinomethyl-thiadiazole-2-thione, 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, aminobenzotriazole, and silane coupling agent. The adhesion improver is preferably a silane coupling agent.

The silane coupling agent is preferably a compound having an alkoxysilyl group as a hydrolyzable group capable of chemically bonding to an inorganic material. Further, a compound having a group which exhibits affinity by forming an interaction or a bond with the resin is preferable, and examples of such a group include a vinyl group, a styryl group, a (meth) acryloyl group, a mercapto group, an epoxy group, an oxetanyl group, an amino group, a ureido group, a thioether group, an isocyanate group, and the like, and a (meth) acryloyl group and an epoxy group are preferable.

The silane coupling agent is also preferably a silane compound having at least 2 functional groups different in reactivity in 1 molecule, and particularly preferably a compound having an amino group and an alkoxy group as the functional groups. Examples of such silane coupling agents include N- β -aminoethyl- γ -aminopropyl-methyldimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-602, manufactured by Ltd.), N- β -aminoethyl- γ -aminopropyl-trimethoxysilane (Shin-Etsu Chemical Co., manufactured by Ltd., KBM-603), N- β -aminoethyl- γ -aminopropyl-triethoxysilane (Shin-Etsu Chemical Co., manufactured by Ltd., KBE-602), γ -aminopropyl-trimethoxysilane (Shin-Etsu Chemical Co., manufactured by Ltd., KBM-903), γ -aminopropyl-triethoxysilane (Shin-Etsu Chemical Co., manufactured by Ltd., manufactured by Lbm-903, manufactured by KBE-903), 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-503, manufactured by Ltd.), and the like. As the silane coupling agent, the following compounds can also be used. In the following structural formula, Et is ethyl.

[ chemical formula 4]

When the composition of the present invention contains an adhesion improving agent, the content of the adhesion improving agent in the total solid content of the composition of the present invention is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and particularly preferably 0.1% by mass or more. The upper limit is preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less. The composition of the present invention may contain only 1 kind of adhesion improving agent, or may contain 2 or more kinds. When the composition of the present invention contains 2 or more adhesion improving agents, the total of these is preferably within the above range. The composition of the present invention also preferably contains substantially no adhesion improving agent. The case where the composition of the present invention does not substantially contain an adhesion improving agent means that the content of the adhesion improving agent in the total solid content of the composition of the present invention is 0.0005 mass% or less, preferably 0.0001 mass% or less, and more preferably does not contain an adhesion improving agent.

Other ingredients

In the composition of the present invention, the content of the free metal not bound or coordinated to the silica particles or the like is preferably 300ppm or less, more preferably 250ppm or less, further preferably 100ppm or less, and particularly preferably substantially not contained. Examples of the kind of the free metal include K, Sc, Ti, Mn, Cu, Zn, Fe, Cr, Co, Mg, Sn, Zr, Ga, Ge, Ag, Au, Pt, Cs, Ni, Cd, Pb, and Bi. Examples of the method for reducing the free metal in the composition include washing with ion-exchanged water, filtration, ultrafiltration, and purification with an ion-exchange resin.

Uses of the composition

The composition of the present invention can be preferably used as a composition for forming an optically functional layer in an optical device such as a display panel, a solar cell, an optical lens, a camera module, a photosensor, or the like. Examples of the optically functional layer include an antireflection layer, a low refractive index layer, and a waveguide.

Also, the composition of the present invention can be preferably used as a composition for forming partition walls. Examples of the partition wall include a partition wall for defining adjacent pixels when forming pixels in an imaging region of the solid-state imaging device. Examples of the pixels include colored pixels, transparent pixels, and pixels having a near-infrared transmitting filter layer. As an example, a partition wall for forming a grid structure for defining pixels may be used. Examples thereof include the structures described in, for example, japanese patent laid-open nos. 2012-227478, 2010-232537, 2009-111225, 1 of 2017-028241, and 4D of 2016-201524, which are incorporated herein by reference. Further, a partition wall for forming an edge structure around a filter such as a color filter or a near infrared ray transmission filter may be used. An example of this is a structure described in japanese patent application laid-open No. 2014-048596, which is incorporated herein.

The composition of the present invention can also be used for the production of an optical sensor. Examples of the optical sensor include an image sensor such as a solid-state imaging device. One mode of the optical sensor includes a structure in which a film formed using the composition of the present invention is applied to an antireflection film, an intermediate film, an edge of a filter or a near-infrared ray transmission filter, a partition wall such as a grid disposed between pixels, or the like on a microlens. An example of an embodiment of the optical sensor includes a light receiving element (photodiode), a lower planarization film, a filter, an upper planarization film, and a microlens. Examples of the filter include a filter having colored pixels such as red (R), green (G), and blue (B) or pixels having a near-infrared transmitting filter layer.

< method for producing composition >

The composition of the present invention can be produced by mixing the above-mentioned compositions. In the production of the composition, it is preferable to perform filtration with a filter in order to remove foreign matter, reduce defects, and the like. The filter may be used without particular limitation as long as it is a filter conventionally used for filtration or the like. Examples of the filter include filters made of materials such as fluororesins (e.g., polytetrafluoroethylene), polyamide resins (e.g., nylon), and polyolefin resins (including high-density and ultrahigh-molecular-weight polyolefin resins) such as Polyethylene and Polypropylene (PP). Among the raw materials, polypropylene (including high-density polypropylene) and nylon are preferable.

The pore diameter of the filter is preferably 0.1 to 7 μm, more preferably 0.2 to 2.5 μm, still more preferably 0.2 to 1.5 μm, and still more preferably 0.2 to 0.7. mu.m. If the pore diameter of the filter is within the above range, fine foreign matters can be removed more reliably. With regard to the pore size value of the filter, reference can be made to the nominal value of the filter manufacturer. The filters can be any of the filters provided by NIHON PALL LTD. (DFA4201NIEY et al), Advantec Toyo Kaisha, Ltd., Nihon Entegris K.K. (Formerly Nippon micro liquid Co., Ltd.), and KITZMICROSFILTER CORPORATION et al.

When filters are used, different filters may be combined. In this case, the filtration using each filter may be performed only 1 time, or may be performed 2 or more times. Also, filters of different pore sizes may be combined.

< storage Container >

The container for the composition of the present invention is not particularly limited, and a known container can be used. Further, as the storage container, it is also preferable to use a multilayer bottle having 6 kinds of 6-layer resins on the inner wall of the container or a bottle having a 7-layer structure of 6 kinds of resins in order to suppress the mixing of impurities into the raw material or the composition. Examples of such a container include those disclosed in Japanese patent laid-open publication No. 2015-123351.

Further, the inner wall of the storage container is preferably made of glass, stainless steel, or the like. According to this aspect, it is possible to prevent elution of metal from the inner wall of the container to improve the storage stability of the composition or to suppress deterioration of the components of the composition.

< film >

Next, the film of the present invention is a film obtainable using the above-described composition of the present invention.

The film of the present invention has a refractive index of preferably 1.4 or less, more preferably 1.35 or less, still more preferably 1.3 or less, and still more preferably 1.27 or less in light having a wavelength of 633 nm. The refractive index is a value at a measurement temperature of 25 ℃.

The film of the present invention preferably has sufficient hardness. The young's modulus of the film is preferably 2 or more, more preferably 3 or more, and particularly preferably 4 or more. The upper limit value is preferably 10 or less.

The thickness of the film of the present invention can be appropriately selected depending on the application. For example, the thickness of the film is preferably 5 μm or less, more preferably 3 μm or less, and particularly preferably 1.5 μm or less. The lower limit is not particularly limited, but is preferably 50nm or more.

The film of the present invention can be used for an optical functional layer and the like in optical devices such as display panels, solar cells, optical lenses, camera modules, and optical sensors. Examples of the optically functional layer include an antireflection layer, a low refractive index layer, and a waveguide. The film of the present invention can be used as a partition wall for dividing adjacent pixels when forming pixels on an imaging region of a solid-state imaging device, for example.

< method for producing film >

The method for producing a film of the present invention includes a step of applying the composition of the present invention to a support by spin coating. The application by the spin coating method may be performed by a method (static dispensing method) in which the composition is dropped from a nozzle in a state where the rotation of the support is stopped when the composition is applied to the support, and then the support is rapidly rotated, or may be performed by a method (dynamic dispensing method) in which the composition is dropped from a nozzle in a state where the rotation of the support is not stopped and the support is rotated when the composition is applied to the support. In the coating by the spin coating method, it is also preferable to perform the coating by changing the rotation speed stepwise. For example, it is preferable to include a main rotation step of determining the film thickness and a drying rotation step for drying. When the time in the main rotation step is as short as 10 seconds or less, the rotation speed in the subsequent drying rotation step for drying is preferably 400rpm to 1200rpm, more preferably 600rpm to 1000 rpm. From the viewpoint of achieving both the suppression of streaks and the drying, the time of the main rotation step is preferably 1 second or more and 20 seconds or less, more preferably 2 seconds or more and 15 seconds or less, and still more preferably 2.5 seconds or more and 10 seconds or less. When the time of the main rotation step is within the above range, the occurrence of streaks can be more effectively suppressed as the time becomes shorter. In the case of the dynamic dispensing method, it is also preferable to reduce the difference between the rotation speed at the time of dropping the composition and the rotation speed in the main rotation step in order to suppress the uneven application of the waveform. Further, the coating by the spin coating method can be carried out by increasing the rotation speed during the coating process as described in Japanese patent application laid-open Nos. H10-142603, H11-302413 and 2000-157922. Further, the spin coating process described in "most advanced process technology and chemicals" 31.1.2006, CMC Publishing co.

The support to which the composition is applied can be appropriately selected depending on the application. Examples of the substrate include a wafer made of a material such as silicon, alkali-free glass, soda glass, pyrex (registered trademark) glass, or quartz glass. Further, an InGaAs substrate or the like is also preferably used. Since the InGaAs substrate has good sensitivity to light having a wavelength of more than 1000nm, a light sensor having excellent sensitivity to light having a wavelength of more than 1000nm can be easily obtained by forming each near-infrared ray transmission filter layer on the InGaAs substrate. A Charge Coupled Device (CCD), a Complementary Metal Oxide Semiconductor (CMOS), a transparent conductive film, or the like may be formed on the support. Further, a Black matrix (Black matrix) made of a light-shielding material such as tungsten may be formed on the support. The support may be provided with a base layer for improving adhesion to the upper layer, preventing diffusion of a substance, or flattening the surface of the substrate. As the support, a microlens can also be used. By applying the composition of the present invention to the surface of the microlens, a microlens unit can be formed whose surface is covered with a film formed from the composition of the present invention. The microlens unit can be used by being incorporated into an optical sensor such as a solid-state imaging element.

Further, in the case of using a wafer as the support, the diameter of the wafer is not particularly limited, and in the case of using a wafer having a large diameter, the uneven coating of the waveform can be remarkably suppressed, and therefore, in the case of using a wafer having a large diameter, the effect of the present invention can be remarkably obtained. For example, the diameter of the wafer is preferably 8 inches (20.32 cm) or more, and more preferably 12 inches (30.48 cm) or more. Further, the inventors have found that, when a composition containing silica particles is spin-coated on a support as the diameter of a wafer increases, uneven coating of a waveform tends to occur on the surface. By using the composition of the present invention, even if the wafer has a large diameter, the composition has a remarkable effect of suppressing the occurrence of coating unevenness of a waveform.

In the present invention, the composition layer formed on the support may be dried (prebaked). Drying is preferably carried out at a temperature of 50 to 140 ℃ for 10 to 300 seconds by using a hot plate, an oven or the like.

After drying the composition layer, a heat treatment (post-baking) may be further performed. The post-baking temperature is preferably 250 ℃ or lower, more preferably 240 ℃ or lower, and still more preferably 230 ℃ or lower. The lower limit is not particularly limited, but is preferably 50 ℃ or higher, and more preferably 100 ℃ or higher.

In the present invention, the composition layer dried (after post-baking in the case of post-baking) may be subjected to an adhesion treatment. The adhesion treatment may be, for example, an HMDS treatment. In this treatment, HMDS (Hexamethyldisilazane, hexamethylidilazane) was used. It is considered that when HMDS is applied to a composition layer formed using the composition of the present invention, it reacts with Si-OH bonds present on the surface thereof to form Si-O-Si (CH)₃)₃. This makes it possible to make the surface of the composition layer hydrophobic. Thereby, by makingThe surface of the composition layer is hydrophobic, and when a resist pattern described later is formed on the composition layer, adhesion of the resist pattern can be improved and penetration of a developer into the composition layer can be prevented.

The film production method of the present invention may further include a step of forming a pattern. Examples of the patterning step include a patterning method by photolithography and a patterning method by etching.

(Pattern formation by photolithography)

First, a case where a pattern is formed by photolithography using the composition of the present invention will be described. The pattern formation by the photolithography method preferably includes a step of forming a composition layer by applying the composition of the present invention onto a support by a spin coating method, a step of exposing the composition layer to a pattern, and a step of forming a pattern by removing an unexposed portion of the composition layer by development.

In the step of forming the composition layer, the composition of the present invention is applied to a support by spin coating to form the composition layer. Examples of the support include the above-mentioned supports. The composition layer formed on the support may be dried (prebaked). Drying is preferably carried out at a temperature of 50 to 140 ℃ for 10 to 300 seconds by using a hot plate, an oven or the like.

Next, the composition layer is exposed to light in a pattern (exposure step). For example, the composition layer can be exposed in a pattern form by performing exposure through a mask having a predetermined mask pattern by using a stepper, a scanner, or the like. Thereby, the exposed portion can be cured.

Examples of the radiation (light) that can be used for exposure include g-rays and i-rays. Light having a wavelength of 300nm or less (preferably light having a wavelength of 180 to 300 nm) can also be used. Examples of the light having a wavelength of 300nm or less include KrF rays (wavelength: 248nm), ArF rays (wavelength: 193nm), and the like, and KrF rays (wavelength: 248nm) are preferable. Further, a light source having a long wavelength of 300nm or more can be used.

In addition, in the exposure, the exposure may be performed by continuously irradiating light, or may be performed by pulse irradiation Exposure (pulse exposure) is performed by irradiation. The pulse exposure is an exposure method of repeating irradiation and suspension of light in a short period of time (for example, millisecond order or less) to perform exposure. In the pulse exposure, the pulse width is preferably 100 nanoseconds (ns) or less, more preferably 50 nanoseconds or less, and still more preferably 30 nanoseconds or less. The lower limit of the pulse width is not particularly limited, but may be 1 femtosecond (fs) or more, or 10 femtoseconds or more. The frequency is preferably 1kHz or more, more preferably 2kHz or more, and still more preferably 4kHz or more. The upper limit of the frequency is preferably 50kHz or less, more preferably 20kHz or less, and further preferably 10kHz or less. The maximum instantaneous illumination is preferably 50000000W/m²Above, more preferably 100000000W/m²The above is more preferably 200000000W/m²The above. Further, the upper limit of the maximum instantaneous illuminance is preferably 1000000000W/m²Hereinafter, 800000000W/m is more preferable²Hereinafter, 500000000W/m is more preferable²The following. In addition, the pulse width refers to the time during which light is irradiated in the pulse period. And, the frequency means the number of pulse periods per 1 second. The maximum instantaneous illuminance is an average illuminance over the time period during which light is irradiated in the pulse period. The pulse period is a period in which the irradiation and pause of light in the pulse exposure are 1 period.

The dose (exposure) is preferably 0.03 to 2.5J/cm²More preferably 0.05 to 1.0J/cm². The oxygen concentration at the time of exposure can be appropriately selected, and in addition to the atmospheric air, for example, exposure may be performed in a low oxygen environment (for example, 15 vol%, 5 vol%, or substantially no oxygen) in which the oxygen concentration is 19 vol% or less, or exposure may be performed in a high oxygen environment (for example, 22 vol%, 30 vol%, or 50 vol%) in which the oxygen concentration is more than 21 vol%. Further, the exposure illuminance can be appropriately set, and usually can be set from 1000W/m²～100000W/m²(e.g., 5000W/m)²，15000W/m²Or 35000W/m²) Is selected. The oxygen concentration and the exposure illuminance may be appropriately combined, and for example, the illuminance may be set to 10000W/m at an oxygen concentration of 10 vol%²In the presence of oxygenThe illumination intensity is set to 20000W/m under the temperature of 35 volume percent²And the like.

Next, the unexposed portion of the composition layer is removed by development to form a pattern. The unexposed portions of the composition layer can be removed by development using a developer. Thereby, the composition layer of the unexposed portion in the exposure step is eluted in the developer, and only the photo-cured portion remains. The developing solution may be an alkali developing solution or an organic solvent, and is preferably an alkali developing solution. The temperature of the developing solution is preferably 20 to 30 ℃. The developing time is preferably 20 to 180 seconds.

The alkali developing solution is preferably an alkaline aqueous solution (alkali developing solution) obtained by diluting an alkali agent with pure water. Examples of the alkali agent include organic basic compounds such as amine, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxylamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, and 1, 8-diazabicyclo [5.4.0] -7-undecene, and inorganic basic compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, and sodium metasilicate. The alkaline agent is preferably a compound having a large molecular weight from the viewpoint of environment and safety. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. The developer may further contain a surfactant. The surfactant includes the above-mentioned surfactants, and preferably a nonionic surfactant. The developer may be once produced as a concentrated solution from the viewpoint of convenience in transportation and storage, and diluted to a desired concentration at the time of use. The dilution ratio is not particularly limited, but can be set, for example, in the range of 1.5 to 100 times. Further, it is also preferable to perform cleaning (rinsing) with pure water after development. The rinsing is preferably performed by rotating the support on which the developed composition layer is formed and supplying the rinsing liquid to the developed composition layer. It is also preferable that the rinse liquid is discharged from a nozzle that discharges the rinse liquid from the center of the support to the peripheral edge of the support. In this case, the nozzle may be moved while gradually decreasing the moving speed of the nozzle when moving from the center portion to the peripheral portion of the support body of the nozzle. By performing flushing in this way, in-plane variations during flushing can be suppressed. Further, the same effect can be obtained by gradually decreasing the rotation speed of the support body while moving the nozzle from the central portion to the peripheral portion of the support body.

After the development, it is preferable to perform additional exposure treatment and heating treatment (post-baking) after drying. The additional exposure treatment and the post-baking are post-development curing treatments for complete curing. The heating temperature at the time of the post-baking is preferably 250 ℃ or lower, more preferably 240 ℃ or lower, and further preferably 230 ℃ or lower. The lower limit is not particularly limited, but is preferably 50 ℃ or higher, and more preferably 100 ℃ or higher. When the additional exposure treatment is performed, the light used for the exposure is preferably light having a wavelength of 400nm or less. The additional exposure treatment can be performed by the method described in Korean laid-open patent publication No. 10-2017-0122130.

(Pattern formation by etching method)

Next, a case where a pattern is formed by an etching method using the composition of the present invention will be described. The pattern formation by the etching method preferably includes a step of forming a cured product layer by applying the composition of the present invention onto a support by a spin coating method to form a composition layer and curing the entire composition layer, a step of forming a photoresist layer on the cured product layer, a step of forming a resist pattern by exposing the photoresist layer to light in a pattern and then developing, a step of etching the cured product layer using the resist pattern as a mask, and a step of removing the resist pattern from the cured product layer.

The resist used for forming the resist pattern is not particularly limited, and for example, a book "fine processing of polymer new material One Point 3 and resist: eupolyphaga three sheers, pubic: resists containing alkali-soluble phenolic resins and naphthoquinone diazide are described in Kyoritsu Shuppan Co., Ltd. (first edition 1 print issue at 11/15 of 1987) on pages 16 to 22. Further, it is also possible to use the resists described in examples and the like of japanese patent No. 2568883, japanese patent No. 2761786, japanese patent No. 2711590, japanese patent No. 2987526, japanese patent No. 3133881, japanese patent No. 3501427, japanese patent No. 3373072, japanese patent No. 3361636, and japanese patent No. h 06-054383. As the resist, a so-called chemically amplified resist can be used. Examples of the chemically amplified resist include "1 st printing release maintenance on 5/31/1996, newly developed optical functional polymer material: city country macro, issue department: a Resist described on pages 129 and later of CMC Publishing co., ltd. "(particularly preferably a Resist containing a resin in which a hydroxy group of a polyhydroxystyrene resin is protected by an acid-decomposable group described on page 131 or an ESCAP Resist (Environmentally Stable Chemical Amplification Positive Resist) similarly described on page 131), and the like). The resists described in examples of Japanese patent laid-open Nos. 2008-268875, 2008-249890, 2009-244829, 2011-013581, 2011-232657, 2012-003070, 2012-003071, 3638068, 4006492, 4000407 and 4194249 can also be used.

The method of etching the cured material layer may be dry etching or wet etching. Dry etching is preferred.

In dry etching of the cured layer, it is preferable to use O and a fluorine-based gas₂The mixed gas of (2) is used as an etching gas. Fluorine-based gas and O₂Mixing ratio (fluorine-based gas/O)₂) The flow rate ratio is preferably 4/1-1/5, and more preferably 1/2-1/4. As the fluorine-containing gas, CF is mentioned₄、C₂F₆、C₃F₈、C₂F₄、C₄F₈、C₄F₆、C₅F₈、CHF₃Etc., preferably C₄F₆、C₅F₈、C₄F₈And CHF₃More preferably C₄F₆、C₅F₈More preferably C₄F₆. The fluorine-based gas may be one selected from the group described above, and may include a mixture of 2 or more kinds.

The mixed gas is not only the fluorine-based gas and O from the viewpoint of stability of partial pressure control of the etching plasma and maintenance of verticality of a specific etching shape₂In addition, a rare gas such as helium (He), neon (Ne), argon (Ar), krypton (Kr), or xenon (Xe) may be further mixed. As other gases that can be mixed, 1 or 2 or more gases from the above group can be selected. As the mixing ratio of other gases which can be mixed, O is measured in terms of the flow ratio₂When 1 is used, it is preferably more than 0 and 25 or less, preferably 10 or more and 20 or less, and particularly preferably 16.

The internal pressure of the chamber during dry etching is preferably 0.5 to 6.0Pa, and more preferably 1 to 5 Pa.

The dry etching conditions include those described in International publication No. 2015/190374, paragraphs No. 0102 to No. 0108, and Japanese patent application laid-open No. 2016-014856, which are incorporated herein by reference.

The method for manufacturing a film of the present invention can be applied to manufacture an optical sensor and the like.

Examples

The present invention will be described with reference to examples, but the present invention is not limited to these examples. The amounts and ratios shown in the examples are defined as quality standards unless otherwise specified.

< method for measuring dynamic viscosity >

The dynamic viscosity of the measurement sample was measured using an Ubbelohde viscometer.

< method for measuring surface tension >

The temperature of the measurement sample was adjusted to 25 ℃, and the surface tension of the measurement sample was measured by a plate method using a platinum plate using a surface tensiometer CBVP-Z (Kyowa Interface Science co., ltd.).

< preparation of composition >

The ingredients were mixed to the composition of the following table, and filtered using DFA4201NIEY (0.45 μm nylon filter) manufactured by Nihon Pall ltd. The numerical values of the blending amounts shown in the following tables are parts by mass. And the doping amount of the silica particle solution is SiO in the silica particle solution ₂The value of (c). The value of the amount of the solvent blended is a total value of the amounts of the solvents contained in the silica particle solution. The content of the silicone surfactant in the total solid content of the composition is also shown in the following table.

[ Table 1]

[ Table 2]

[ Table 3]

[ Table 4]

The raw materials listed in the above table are as follows.

(silica particle solution)

P1: a solution of silica particles (beaded silica) in which a plurality of spherical silicas having an average particle diameter of 15nm are beaded by silica (connecting material) containing a metal oxide.

P2: thruria 4110 (manufactured by JGC Catalysts and Chemicals Ltd., average particle diameter of 60 nm)A solution of silica particles (hollow silica particles). SiO 2₂The converted solid content concentration was 20 mass%. The silica particle solution is a solution containing neither silica particles having a shape in which a plurality of spherical silica particles are connected in a beaded form nor silica particles having a shape in which a plurality of spherical silica particles are connected in a planar form

In the silica particle solution P1, the average particle diameter of the spherical silica particles was determined by calculating the number average of the equivalent circle diameters in the projection images of the spherical portions of 50 spherical silica particles measured by a Transmission Electron Microscope (TEM). In the silica particle solutions P1 and P2, whether or not the solutions were silica particle solutions containing silica particles in which a plurality of spherical silica particles were connected in a string-like manner and silica particles in which a plurality of spherical silica particles were connected in a shape below was confirmed by TEM observation.

(Silicone surfactant)

F1: a compound having the following structure (methanol-modified silicone compound having a weight average molecular weight of 3000 and a dynamic viscosity at 25 ℃ of 45mm²/s)

[ chemical formula 5]

F2: silwet L-7220 (manufactured by Momentive Performance Materials inc., a compound having the following structure (polyether-modified silicone compound, n: m: 20: 80 (molar ratio), weight average molecular weight: 17000, and dynamic viscosity at 25 ═ 1100mm²/s)

[ chemical formula 6]

(other surfactants)

rF 1: megaface F-551 (fluorine-based surfactant, manufactured by DIC Corporation)

(polymerizable Compound)

M1: KAYARAD DPHA (Nippon Kayaku Co., Ltd.; manufactured by Ltd.)

M2: a compound of the structure

[ chemical formula 7]

(resin)

B1: a resin having the following structure (numerical values shown in the main chain are molar ratios. Mw: 11000)

[ chemical formula 8]

(photopolymerization initiator)

I1: 1RGACURE-OXE01 (manufactured by BASF CORPORATION)

I2: a compound of the structure

[ chemical formula 9]

(solvent)

S1: 1, 4-butanediol diacetate (boiling point 232 ℃, viscosity 3.1mpa s, molecular weight 174)

S2: propylene glycol monomethyl ether acetate (boiling point 146 ℃, viscosity 1.1 mPa. multidot.s, molecular weight 132)

S3: propylene glycol monomethyl ether (boiling point 120 ℃, molecular weight 90, viscosity 1.8 ═ mPa · s)

S4: ethanol, methanol or a mixture thereof (methanol having a boiling point of 64 ℃, methanol having a viscosity of 0.6mPa · s, ethanol having a boiling point of 78 ℃, ethanol having a viscosity of 1.2mPa · s)

S5: water (boiling point 100 ℃ C., viscosity 0.9 mPa. multidot.s)

< evaluation of surface tension >

The surface tension of the composition obtained above was measured according to the above method.

< evaluation of contact Angle >

The composition obtained above was coated on a glass substrate and heated at 200 ℃ for 5 minutes to form a film having a thickness of 0.5 μm. The contact angle of the obtained film with respect to water at 25 ℃ was measured using a contact angle meter (Kyowa Interface Science Co., Ltd., manufactured by Ltd., DM-701).

< evaluation of refractive index >

The composition obtained above was coated on a silicon wafer having a diameter of 12 inches (═ 30.48cm) by a spin coating method in a clean room of Class 1000 (Class) so that the film thickness after coating became 0.3 μm. The rotation speed of the silicon wafer was set at 1500rpm at the time of coating. Then, the resultant was heated at 200 ℃ for 5 minutes to form a film having a thickness of 0.3. mu.m. The refractive index of the obtained film (wavelength of 633nm, measurement temperature of 25 ℃) was measured using an ellipsometer (j.a. woollam co., manufactured by inc., VUV-vase [ product name ]).

< evaluation of coatability >

The composition obtained above was coated on a silicon wafer having a diameter of 12 inches (═ 30.48cm) by a spin coating method in a clean room of Class 1000 (Class) so that the film thickness after coating became 0.6 μm. The rotation speed of the silicon wafer was set at 1500rpm at the time of coating. Then, the film was heated at 100 ℃ for 2 minutes and at 220 ℃ for 5 minutes to produce a film.

The surface of the wafer end of the obtained film was observed using an optical microscope (magnification of 200 times), and the presence or absence of coating unevenness of a waveform was confirmed. In addition, the unevenness of the waveform generated at an angle of 45 degrees with respect to the normal line of the silicon wafer was regarded as the coating unevenness of the waveform.

3: no uneven coating of the waveform was observed.

2: coating unevenness of a very slight wave shape was observed.

1: coating unevenness was observed for many waveforms.

< coatability of composition for Forming topcoat layer >

The composition obtained above was coated on a silicon wafer having a diameter of 12 inches (═ 30.48cm) by a spin coating method in a clean room of Class 1000 (Class) so that the film thickness after coating became 0.6 μm. The rotation speed of the silicon wafer was set at 1500rpm at the time of coating. Then, the film was heated at 100 ℃ for 2 minutes and at 220 ℃ for 5 minutes to produce a film.

On the obtained film, as a composition for forming an overcoat layer, CT-4000L (manufactured by FUJIFILM Electronic Materials co., Ltd) was applied so that the film thickness after baking became 0.1 μm, and then heated (post-baked) for 5 minutes with a hot plate at 220 ℃. The coating layer was visually observed, and the coatability of the composition for forming a coating layer was evaluated according to the following criteria.

1: an upper coating layer without a recess can be formed.

2: the upper coating layer has depressions. Or no topcoat layer is formed.

[ Table 5]

As shown in the above table, the compositions of the examples can form a film having good coatability and suppressed occurrence of uneven coating of waves. Further, an upper coat layer having no dishing can be formed on the film formed using the composition of example, and the composition for forming an upper coat layer is excellent in coatability.

When the composition of the example is used to prepare the partition walls 40 to 43 shown in FIG. 1 of Japanese patent application laid-open Nos. 2017 and 028241 and prepare the image sensor shown in FIG. 1 of Japanese patent application laid-open Nos. 2017 and 028241, the sensitivity of the image sensor is excellent.

< production of partition wall >

The composition of the example was applied to a silicon wafer having a diameter of 12 inches (═ 30.48cm) by a spin coating method, and heated at 100 ℃ for 2 minutes and further at 230 ℃ for 2 minutes using a hot plate, to form a composition layer having a film thickness of 0.5 μm. A positive photoresist (FFPS-0283, made by FUJIFILM Electronic Materials co., Ltd.) was applied on the composition layer by spin coating and heated at 90 ℃ for 1 minute, to form A photoresist layer with a thickness of 1.0 μm. Next, a KrF scanner exposure machine (FPA6300ES6a, manufactured by Canon Inc.) was used at 16J/cm through a mask₂After exposure with the exposure amount of (2), heat treatment was performed at 100 ℃ for 1 minute. Then, after a development treatment was performed for 1 minute using a developing solution (FHD-5, manufactured by FUJIFILM Electronic materials co., ltd.), a heating treatment was performed for 1 minute at 100 ℃. This pattern was used as a mask, and was patterned by dry etching under the conditions described in Japanese patent laid-open Nos. 2016-014856, paragraphs 0129 to 0130, so that partition walls having a width of 0.1 μm and a height of 0.5 μm were formed in a lattice shape at intervals of 1 μm. The opening size of the partition wall on the silicon wafer (the region of 1 pixel on the silicon wafer partitioned by the partition wall) was 0.9 μm in length by 0.9 μm in width.

Description of the symbols

1-spherical silica, 2-junctions.