TW201542694A - High refractive index film forming composition having alkali soluble development and method for forming pattern - Google Patents

Abstract

To provide: a film forming composition which is suitable for the production of a film having high refractive index, high transparency, high heat resistance, high light resistance and high hardness; and a pattern forming method. A film forming composition which contains: a silicon compound (A) that is a hydrolysis-condensation product of a hydrolyzable silane containing a hydrolyzable silane (a1) represented by formula (a1) and a hydrolyzable silane (a2) represented by formula (a2) and has a weight average molecular weight of 700-4,000; inorganic particles (B) having an average particle diameter of 1-100 nm and a refractive index of 1.50-2.70; and a solvent (C). The silicon compound (A) is a polymer that is obtained by hydrolyzing and condensing a hydrolyzable silane which contains the hydrolyzable silane (a1) and the hydrolyzable silane (a2) respectively in an amount of 90-50% by mole and in an amount of 10-50% by mole. Si(R1)4 Formula (a1) L-Si(R2)3 Formula (a2) (In the formulae, each of R1 and R2 represents an alkoxy group having 1-20 carbon atoms, an acyloxy group having 2-20 carbon atoms or a halogen group; and L represents a linear, branched or cyclic alkyl group having 3-6 carbon atoms.).

Description

Alkali-dissolved and developable high-refractive-index film forming composition and pattern forming method

The present invention relates to a film-forming composition containing a polyoxyalkylene oxide and inorganic fine particles and a pattern forming method.

Light-emitting diodes (LEDs) can be used as backlight sources, signals, illumination, lasers, biosensors, etc. for various displays, and are widely used in people's livelihood.

In order to achieve a longer life and lower power consumption, the LED has become a mainstream device for improving light extraction efficiency. In the trend of these, development of component structures and materials for improving light extraction efficiency has been developed.

In order to improve the light extraction efficiency, there is a method of controlling the refractive index of the optical material to form a review report of the high refractive index of the encapsulating material.

For example, a composition for forming a high refractive material containing at least one selected from the group consisting of zirconia, titania, zinc oxide, cerium oxide, indium oxide, cerium oxide, tin oxide, cerium oxide, and the like. Gold a fine particle of an oxide; an alkoxy-containing alkane polymer (b1) having a weight average molecular weight of 1,000 to 100,000; a hydroxyl group-containing polyoxyalkylene (b2) having a weight average molecular weight of 500 to 100,000; Free β-diketones, ketoesters, dicarboxylic acids and their derivatives, hydroxycarboxylic acids and their derivatives, keto alcohols, dihydroxy compounds, oxyaldehyde compounds, and amine compounds and their derivatives At least one type of chelating agent (refer to Patent Document 1), and a resin composition for optical-related device encapsulation comprising an organic polysiloxane having an alkyl group, an aryl group, a hydroxyl group, or the like, a condensed catalyst, and inorganic fine particles (Patent Literature) 2) and a trialkoxy decane (A) having a phenyl group having an alkyl group having 1 to 20 carbon atoms or a hydrocarbon group having 1 to 8 carbon atoms and having a reactive cyclic ether group A resin composition for a B-stage optical element having a trapezoidal or random structure of a sesquiterpene oxide derivative obtained by co-hydrolysis or co-condensation, and a main component of the inorganic fine particles (Refer to Patent Document 3).

The high-refractive-index material of the present invention requires high transparency, high heat resistance, high light resistance, and high hardness, but materials satisfying all of the required properties have not been available so far.

When inorganic particles are added, the film hardness may decrease. The film of polyoxyalkylene has a high hardness and, conversely, does not exhibit a high refractive index. The method of combining inorganic particles with polysiloxanes to form a high refractive index material is well known in the art.

High refractive index film for LED requires alkali developability and is produced In the case of a pattern of 10 μm or less, the developability is required to be dissolved in the alkali. Therefore, the high refractive index composition itself is provided with photosensitivity, and a pattern can be obtained. However, since it contains a photosensitive agent or the like, it is difficult to satisfy long-term light resistance and reliability as a member of the LED element.

The high refractive index composition containing a polysiloxane and an inorganic particle is not known by the patterning of the photosensitive material applied, and the process of manufacturing an LED is considered, and patterning of 10 micrometers or less is formed. The review is still unknown.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2006-316264

[Patent Document 2] Japanese Patent Laid-Open No. 2006-328315

[Patent Document 3] Japan Special Open 2008-202008

[Summary of the Invention]

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a film forming composition and a film which are suitable for a film for a display device which can achieve high refractive index, high transparency, high heat resistance, high light resistance, and high hardness. A method of forming a pattern of the composition and a method of preventing film roughness when the resist film is peeled off.

A first aspect of the present invention is a film-forming composition (1) comprising: a hydrolyzable decane (a1) represented by the formula (a1) and a hydrolyzable decane (a2) represented by the formula (a2): (wherein R ¹ and R ² each represent an alkoxy group having 1 to 20 carbon atoms, a decyloxy group having 2 to 20 carbon atoms, or a halogen group; and L represents a linear chain or a branch having 3 to 6 carbon atoms; Or a hydrolyzed condensate of a hydrolyzable decane of a cyclic alkyl group), and a ruthenium compound (A) having a weight average molecular weight of 700 to 4,000, an inorganic particle having an average particle diameter of from 1 to 100 nm and a refractive index of from 1.50 to 2.70 (B) ), and solvent (C).

The second aspect is the film-forming composition (1) of the first aspect, wherein the ratio of the hydrazine compound (A) to the hydrolyzable decane (a1) to the hydrolyzable decane (a2) is 90 mol% of the hydrolyzable decane (a1). To 50 mol%, the hydrolyzable decane (a2) contains 10 mol% to 50 mol% of hydrolyzable decane to carry out hydrolysis-condensation of the polymer.

The third aspect is the film formation composition (1) of the first aspect, wherein the ruthenium compound (A) is a hydrolysis condensation of a hydrolyzable decane in a non-alcohol solvent. The winner.

The fourth aspect is the film formation composition (1) of the third aspect, wherein the non-alcohol solvent is a ketone or an ether.

The fifth aspect is the film formation composition (1) of the third aspect, wherein the non-alcohol solvent is acetone or tetrahydrofuran.

The sixth aspect is the film-forming composition (1) of the third aspect, wherein the solvent (C) comprises a reaction of the hydrolysis of the hydrolyzable decane and the reaction of the non-alcohol solvent used in the subsequent condensation and the hydrolysis of the hydrolyzable decane. Solvent replacement solvent.

The seventh aspect is the film formation composition (1) of the first aspect, wherein the inorganic particles (B) are zirconium dioxide.

The eighth aspect is the film-forming composition (2) of the third aspect, further comprising a curing catalyst (D) selected from the group consisting of an ammonium salt, a phosphine, a phosphonium salt, a phosphonium salt, or a chelate compound.

The ninth aspect is the film-forming composition (3) of the third aspect, which further contains a diketone compound (E) selected from the group consisting of 1,2-dione and/or 1,3-diketone.

The tenth aspect is the film-forming composition (3) of the ninth aspect, wherein the diketone compound (E) contains the following formula (3) and/or the following formula (4): A compound wherein (wherein W represents a carbon atom or an oxygen atom) is a skeleton.

The eleventh aspect is the film-forming composition (3) of the ninth aspect, wherein the diketone compound (E) is butanedione, methyl pyruvate, ethyl pyruvate, or acetaminoacetone.

The twelfth aspect is the film formation composition (4) of the eighth aspect, which further contains water (F) and acid (G).

A method for producing a film-forming composition (1) according to the first aspect, which comprises the step of: hydrolyzing decane containing a hydrolyzable decane (a1) and a hydrolyzable decane (a2) in a solvent (c1) The step of performing hydrolysis to obtain a varnish of the ruthenium compound (A) having a weight average molecular weight of 700 to 4,000, and measuring inorganic particles having an average particle diameter of from 1 to 100 nm and a refractive index of from 1.50 to 2.70 by dynamic light scattering method (B) Dispersing in the dispersion medium (c2) to obtain a sol (sol), mixing the varnish of the cerium compound (A) with the sol of the inorganic particles (B) to obtain a cerium compound (A), inorganic particles (B) and a solvent (C) The film forms a step of forming a composition.

A method for producing a film-forming composition (2) according to the eighth aspect, which comprises the step of: hydrolyzing decane containing a hydrolyzable decane (a1) and a hydrolyzable decane (a2) in a non-alcohol solvent (c1) The step of performing hydrolysis to obtain a varnish of the ruthenium compound (A) having a weight average molecular weight of 700 to 4,000, and measuring inorganic particles having an average particle diameter of from 1 to 100 nm and a refractive index of from 1.50 to 2.70 by dynamic light scattering method ( B) a step of dispersing in a dispersing medium (c2) to obtain a sol, The varnish of the cerium compound (A) and the sol of the inorganic particles (B) and the curing catalyst (D) are mixed to obtain a cerium compound (A), inorganic particles (B), a curing catalyst (D), and a solvent (C). The step of forming a composition of the film.

The fifteenth aspect is the method for producing the film-forming composition (3) according to the ninth aspect, which comprises the step of: hydrolyzing decane containing a hydrolyzable decane (a1) and a hydrolyzable decane (a2) in a non-alcohol solvent (c1) The step of performing hydrolysis to obtain a varnish of the ruthenium compound (A) having a weight average molecular weight of 700 to 4,000, and measuring inorganic particles having an average particle diameter of from 1 to 100 nm and a refractive index of from 1.50 to 2.70 by dynamic light scattering method ( B) a step of dispersing the dispersing medium (c2) to obtain a sol, mixing the varnish of the cerium compound (A), the sol of the inorganic particles (B), and the diketone compound (E) to obtain a cerium compound (A) and inorganic particles (B) a step of forming a composition of a film of a diketone compound (E) and a solvent (C).

The method for producing a film-forming composition (4) according to the twelfth aspect, which comprises the step of: hydrolyzing decane containing a hydrolyzable decane (a1) and a hydrolyzable decane (a2) in a non-alcohol solvent (c1) The step of performing hydrolysis to obtain a varnish of the ruthenium compound (A) having a weight average molecular weight of 700 to 4,000, and measuring inorganic particles having an average particle diameter of from 1 to 100 nm and a refractive index of from 1.50 to 2.70 by dynamic light scattering method ( B) a step of dispersing in a dispersing medium (c2) to obtain a sol, The varnish of the cerium compound (A), the sol of the inorganic particles (B), the curing catalyst (D), water (F) and the acid (G) are mixed to obtain a cerium compound (A), an inorganic particle (B), and a hardening contact. A step of forming a composition of a film of the medium (D), water (F), acid (G), and solvent (C).

The seventeenth aspect is a pattern forming method in which a photosensitive resist is applied onto a film obtained from a film forming composition according to any one of the first aspect to the twelfth aspect, and after drying, the photosensitive film is formed. The resist film is irradiated with light, and after development, the resist film is peeled off.

The ninth aspect is a film obtained by coating a film-forming composition of any one of the first to twelfth aspects onto a substrate, and having a refractive index of 1.50 to 1.90 at a wavelength of 633 nm.

The 19th aspect is the film of the 18th aspect, wherein a contact angle of water of the film surface is 60° to 80°.

The twentieth aspect is the film of the 18th aspect, which is used as a light extraction film or a protective film.

The twenty-first aspect is an apparatus having an electronic device including the film of the eighteenth aspect.

The 22nd aspect is the apparatus of the 21st aspect, wherein the electronic device is an LED.

A member such as a light extraction film for LED and a protective film requires a high refractive index and alkali developability, and it is necessary to produce a pattern of 10 μm or less. When the pattern of 10 μm or less is produced, the compound (A) and the inorganic particles (B) are produced. The film produced by the composition of the solvent (C) is required to have alkali developability. Alkali development is distinguished by dissolution development and peel development. The dissolution and development means that the film is dissolved while the alkali solution is dissolved, and the development of the pattern is formed. The peeling and development means that the alkali solution makes the film less soluble, causing the film to swell and crack, and at the same time forming a pattern. Here, when a pattern of 10 μm or less is to be formed, it is necessary to be soluble and developable, but in the case of peel development, the pattern formation is difficult. In the case of peel development, the size of cracks cannot be suppressed to 10 μm or less, and a pattern of 10 μm or less in uniformity cannot be obtained.

The film-forming composition of the present invention contains a weight average molecular weight A film-forming composition of the inorganic compound (B) having an average particle diameter of from 1 to 100 nm and a refractive index of from 1.50 to 2.70 and a solvent (C) in an amount of from 700 to 4,000.

矽 compound (A) is a weight average molecular weight of 700 to In addition, a hydrolysis condensate obtained by copolymerizing a hydrolyzable decane (a1) and a highly specific type of hydrolyzable decane (a2) at a specific ratio, thereby hydrolyzing a condensate and an inorganic particle (B) The film produced by the composition exhibits dissolution developability with respect to the alkali solution, and a film having a high refractive index of a pattern of 10 μm or less can be obtained.

Moreover, by limiting the type of hydrolyzable decane (a2), it is possible to suppress The sublimation of the cyclic low molecular compound during the heating process prevents the decrease in the refractive index and the decrease in the film density during heating or the reliability test.

Average particle size of inorganic particles (B) by dynamic light scattering From 1 to 100 nm, good filterability and high transmittance of the film-forming composition can be achieved.

Further, the ruthenium compound (A) is a polysiloxane, and the inorganic particles (B) are a composition composed of an inorganic compound when the zirconia having a high refractive index is exhibited, and thus the light resistance is good.

The hydroxyl groups present on the surface of the ruthenium compound (A) and the inorganic particles (B) start to condense when heat of external stimuli is applied, and a film having a strong and high hardness can be formed.

The composition comprising the polysiloxane of the present invention and inorganic particles having an average particle diameter of 1 to 100 nm or less has solubility developability in an alkali solution. Therefore, a photosensitive resist can be used to form a pattern of 10 μm or less. The process is not simplified by dry etching, and therefore, the steps are simplified, and the production cost can be reduced.

Further, when a composition of a completely hydrolyzed polyoxyalkylene and a partially hydrolyzed polyoxyalkylene was used, the following characteristics were obtained.

The partially hydrolyzed polyoxyalkylene refers to a polymer obtained by using an alcohol having a functional group such as a hydroxyl group in a solvent for hydrolysis or polycondensation. In the stage of hydrolysis and polycondensation of the partially hydrolyzed polyoxyalkylene, the alcohol formed from the solvent alcohol or the alkoxide of the monomer is reacted with the hydrolyzed stanol group to oxidize the decane alkane. The form of the object remains. Further, since the stanol group in the polymer in the solution state is chemically balanced with the decane alkoxide, when the solvent is selected as the solvent in the hydrolysis and condensation, it becomes a polysiloxane having a large residual ratio of the decane alkoxide.

Further, the fully hydrolyzed polyoxyalkylene refers to a polymer obtained by using a solvent containing no hydroxyl group as a solvent for hydrolysis and condensation. The fully hydrolyzed polyoxyalkylene-based solvent and the non-alcoholic solvent of the solvent in the polycondensation do not have The hydroxyl group at the end of the stanol of the polymer is blocked, and therefore, the obtained polymer becomes a polyoxane having a large residual ratio of stanol. That is, since the fully hydrolyzed polyoxyalkylene oxide contains almost no organic component decane alkoxide, it is a polymer which hardly contains carbon which is unfavorable in the light resistance test.

Partially hydrolyzed polyoxyalkylene remains in the oxidation of many decane alkane Therefore, when reacting with the sterol of the fine particles, it is necessary to pass the hydrolysis once, and it is necessary to additionally add an additive or the like. The additive is, for example, a sterol alcohol production promoter or a decane alkoxide decomposition accelerator. However, these additives contain an organic group or a metal to deteriorate light resistance, and thus are not suitable for the composition of the present invention.

Compared with partially hydrolyzed polyoxyalkylene, fully hydrolyzed Since the polyoxyalkylene has a large amount of decyl alcohol remaining at the terminal, it is possible to obtain a highly reliable film after thermal curing, and the solubility in the alkali solution is too high, and it is difficult to form a pattern of 10 μm or less by the photosensitive resist of the object of the present invention. However, by adding the curing catalyst (D), the film is spin-coated, and the alkali solution resistance is improved or controlled at the stage of temporary drying, and a pattern of 10 μm or less can be efficiently formed under conditions suitable for practical steps.

Further, the polysiloxane of the present invention has an average particle diameter of 1 to A composition composed of inorganic particles of 100 nm or less and a hydrogen-bonding film roughness preventing material (for example, a diketone compound) can be patterned using a photosensitive resist, and when a photosensitive resist is further applied, or a resist film When peeling off, film roughness does not occur.

Moreover, by containing water (F) and acid (G), the reactivity is made. The hydroxy group of the group does not change in the quality of the varnish at a storage temperature of 23 ° C or 5 ° C, and can be formed to a good length of 10 μm or less. The film of the pattern.

Moreover, the film obtained by the present invention can satisfy high refractive index and high Transparent, high heat resistance, high light resistance, high hardness conditions, and can be patterned, it can be suitable as liquid crystal display, plasma display, cathode ray tube, organic light-emitting display, electronic paper, LED, solid-state imaging element Use in electronic devices such as solar cells and organic thin film transistors. In particular, it is suitable for use as a member for LEDs requiring high light resistance.

Fig. 1 is a pattern view showing a composition of Example (1-1) containing a polymer TT73.

Fig. 2 is a pattern view showing the use of the composition of Example (1-2) containing the polymer TI73.

Fig. 3 is a pattern view showing the use of the composition of Example (1-3) containing the polymer TH73.

Fig. 4 is a pattern view showing the use of the composition of the example (1-8) containing the polymer TI73M1.

Fig. 5 is a pattern view showing a composition of Comparative Example (1-1) containing a polymer pTEOS.

Fig. 6 is a pattern view showing the use of the composition of Comparative Example (1-5) containing the polymer TI73M4.

Fig. 7 is a pattern view showing a composition of Example (2-10) containing varnish V (2-1).

Fig. 8 is a pattern view showing a composition of Example (2-11) containing varnish V (2-2).

Fig. 9 is a pattern view showing a composition of Example (2-12) containing varnish V (2-3).

Fig. 10 is a pattern view showing a composition of Reference Example (2-14) containing varnish RV (2-1).

Fig. 11 is a pattern view showing a composition of Reference Example (2-15) containing varnish RV (2-2).

Fig. 12 is a pattern view showing a composition of Reference Example (2-16) containing varnish RV (2-3).

Fig. 13 is a view showing a film formation surface after the resist film is peeled off in the case of using the varnish V (3-1) in the embodiment (3-10).

Fig. 14 is a view showing a film formation surface after peeling of the resist film when the varnish RV (3-1) is used in Reference Example (3-14).

Fig. 15 is a pattern view showing a composition of Example (4-1) containing varnish V (4-1).

Fig. 16 is a pattern view showing a composition of Example (4-2) containing varnish V (4-2).

Fig. 17 is a pattern view showing a composition of Example (4-3) containing varnish V (4-3).

Fig. 18 is a pattern view showing the composition of Example (4-10) containing varnish V (4-10).

Fig. 19 is a pattern view showing a composition of Example (4-14) containing varnish V (4-14).

Fig. 20 is a pattern view showing the use of the composition of the embodiment (4-15) containing the varnish V (4-15).

Fig. 21 is a pattern view showing a composition of Examples (4-16) containing varnish V (4-16).

Fig. 22 is a pattern view showing a composition of Example (4-17) containing varnish V (4-17).

Fig. 23 is a view showing a film formation surface of the reference example (4-1) and using the varnish RV (4-1).

Fig. 24 is a view showing a film formation surface after the patterning of the varnish RV (4-2) using Reference Example (4-2).

Fig. 25 is a view showing a film formation surface after the patterning of the varnish RV (4-3) using Reference Example (4-3).

[Formation of the Invention]

The present invention contains a hydrolyzed condensate of a hydrolyzable decane having a hydrolyzable decane (a1) and a hydrolyzable decane (a2), and a ruthenium compound (A) having a weight average molecular weight of 700 to 4,000, having an average particle diameter of from 1 to 100 nm. The inorganic particle (B) having a refractive index of 1.50 to 2.70 and the film of the solvent (C) form a composition. R ¹ and R ² in the formula (1) and the formula (2) each represent an alkoxy group having 1 to 20 carbon atoms, an anthracene group having 2 to 20 carbon atoms, or a halogen group, and L represents a carbon number of 3 a linear, branched or cyclic alkyl group of ~6.

The solid content concentration of the above film-forming composition is as long as it is The film thickness of the film for forming a film which can be obtained is sufficient, and may be in a concentration range of 0.1 to 50% by mass, 1 to 30% by mass, or 5 to 20% by mass. The solid content is the ratio remaining after the solvent is removed from the film-forming composition.

The content of the ruthenium compound (A) and the inorganic particles (B) in the solid content may be 50 to 100% by mass, 70 to 100% by mass, or 70 to 99% by mass.

When the inorganic particles (B) are 100 parts by mass in terms of solid content, the ruthenium compound (A) may be added in an amount of 0.1 to 200 parts by mass, preferably 0.1 to 100 parts by mass, and the storage stability is maintained in order to maintain the film quality. More preferably, it is 0.1 to 50 parts by mass.

The hydrazine compound (A) used in the present invention is a hydrolysis condensate obtained by hydrolyzing and copolymerizing a hydrolyzable decane (a1) represented by the formula (a1) and a hydrolyzable decane (a2) represented by the formula (a2). This hydrolysis condensate may contain a hydrolyzate.

The hydrazine compound (A) has a ratio of the hydrolyzable decane (a1) to the hydrolyzable decane (a2) of 90% by mole to 50% by mole, and 80% by mole to 60% by mole of the hydrolyzable decane (a1). Or 70 mol%, the hydrolyzable decane (a2) contains 10 mol% to 50 mol%, 20 mol% to 40 mol%, or 30 mol% of a hydrolyzable decane hydrolyzed and condensed.

The hydrolyzable decane (a1) contains 95 mol% or more of the alkali solution of the ruthenium compound (A), and the developability is peel development, and the dissolution developability which does not exhibit the important object of the present invention is exhibited. Further, the hydrolyzable decane (a2) containing 55 mol% or more of the ruthenium compound produced has an increased hydrophobicity, repels the alkali solution, and loses developability.

The hydrolyzate is hydrolyzed by a hydrolyzate of a decane monomer to produce a decane Alcohol based. The hydrolysis condensate is a hydrolyzed condensate in which the stanol groups in the hydrolyzate are dehydrated and condensed to each other to form a polyoxyalkylene, and the terminal of the condensate usually has a stanol group. The hydrazine compound (A) is a hydrolysis condensate (polyoxane), but may also have a hydrolyzate of its precursor.

R ¹ and R ² in the formula (a1) and the formula (a2) represent an alkoxy group, a decyloxy group or a halogen group.

Alkoxy groups such as carbon atoms 1 to 20 have a straight chain, a branch Or alkoxy groups of a cyclic alkyl moiety, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, T-butoxy, n-pentyloxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-di Methyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n- Hexyloxy, 1-methyl-n-pentyloxy, 2-methyl-n-pentyloxy, 3-methyl-n-pentyloxy, 4-methyl-n-pentyloxy, 1, 1-dimethyl-n-butoxy, 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy, 2,2-dimethyl-n- Butoxy, 2,3-dimethyl-n-butoxy, 3,3-dimethyl-n-butoxy, 1-ethyl-n-butoxy, 2-ethyl-n- Butoxy, 1,1,2-trimethyl-n-propoxy, 1,2,2,-trimethyl-n-propoxy, 1-ethyl-1-methyl-n-propyl An oxy group, and 1-ethyl-2-methyl-n-propoxy group and the like.

The decyloxy group has, for example, a decyloxy group having 2 to 20 carbon atoms, for example Methylcarbonyloxy, ethylcarbonyloxy, n-propylcarbonyloxy, isopropylcarbonyloxy, n-butylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, T-Butylcarbonyloxy, n-pentylcarbonyloxy, 1-methyl-n- Butylcarbonyloxy, 2-methyl-n-butylcarbonyloxy, 3-methyl-n-butylcarbonyloxy, 1,1-dimethyl-n-propylcarbonyloxy, 1, 2-Dimethyl-n-propylcarbonyloxy, 2,2-dimethyl-n-propylcarbonyloxy, 1-ethyl-n-propylcarbonyloxy, n-hexylcarbonyloxy, 1-methyl-n-pentylcarbonyloxy, 2-methyl-n-pentylcarbonyloxy, 3-methyl-n-pentylcarbonyloxy, 4-methyl-n-pentylcarbonyloxy 1,1,1-dimethyl-n-butylcarbonyloxy, 1,2-dimethyl-n-butylcarbonyloxy, 1,3-dimethyl-n-butylcarbonyloxy, 2,2-Dimethyl-n-butylcarbonyloxy, 2,3-dimethyl-n-butylcarbonyloxy, 3,3-dimethyl-n-butylcarbonyloxy, 1- Ethyl-n-butylcarbonyloxy, 2-ethyl-n-butylcarbonyloxy, 1,1,2-trimethyl-n-propylcarbonyloxy, 1,2,2-trimethyl Base-n-propylcarbonyloxy, 1-ethyl-1-methyl-n-propylcarbonyloxy, 1-ethyl-2-methyl-n-propylcarbonyloxy, phenylcarbonyloxy And the like, and toluenesulfonylcarbonyloxy group, etc., but are not limited thereto.

Further, examples of the halogen group as the hydrolyzable group include fluorine and chlorine. Bromine, iodine, etc.

The hydrolyzable decane (a1) is, for example, tetramethoxy decane, Tetraethoxy decane, tetraethoxy decane, tetra-n-propoxy decane, tetraisopropoxy decane, tetra-n-butoxy decane, tetraethoxy decane, tetrachloro decane, etc., but as long as It is a tetrafunctional (having four hydrolyzable groups) oxosiloxane monomers, and is not limited thereto. Among these, tetramethoxynonane and tetraethoxydecane are preferably used. A commercially available product can be used for the hydrolyzable decane.

L in the hydrolyzable decane (a2) represents a carbon number of 3 to 6 A linear, branched or cyclic alkyl group. For example, there are n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, 1-methyl-n-butyl Base, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2, 2-Dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl- N-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n -butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n- Butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1- Methyl-n-propyl, and 1-ethyl-2-methyl-n-propyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like, but are not limited thereto.

The above hydrolyzable decane (a2) is, for example, n-propyltrimethoxy Baseline, n-propyltriethoxydecane, isopropyltriethoxydecane, cyclopropyltriethoxydecane, n-butyltriethoxydecane, sec-butyltriethoxydecane , t-butyl triethoxy decane, isobutyl triethoxy decane, cyclobutyl triethoxy decane, n-pentyl triethoxy decane, t-pentyl triethoxy decane, three Ethoxy(pentane-2-yl)decane, triethoxy(pentan-3-yl)decane, cyclopentyltrimethoxydecane, n-hexyltrimethoxydecane, n-hexyltriethoxy Decane, triethoxy(hexane-2-yl)decane, triethoxy(hexane-3-yl)decane, triethoxy(4-methylpentan-2-yl)decane, triethyl An oxy (2-methylpentan-2-yl) decane, a triethoxy (3-methylpentan-3-yl) decane, a cyclohexyl trimethoxy decane, etc., but is not limited thereto.

Among these, n-propyltrimethoxyfluorene is preferably used. Alkane, n-propyltriethoxydecane, isobutyltriethoxydecane, n-hexyltrimethoxydecane. A commercially available product can be used for the hydrolyzable decane.

Hydrolyzing decane (a1) containing formula (a1) The hydrolyzable decane of the hydrolyzable decane (a2) of (a2) is subjected to hydrolysis condensation, The hydrazine compound (A) containing the copolymer of the hydrolysis condensate may be a condensate having a weight average molecular weight of 700 to 4,000 or 1,000 to 2,000. These molecular weights are molecular weights obtained by polystyrene conversion by GPC analysis. When the weight average molecular weight is less than 700, the polymer has an excessively low molecular weight, and a uniform film cannot be obtained. Further, when the weight average molecular weight exceeds 4,000, the polymer is over-polymerized, and the alkali solution is subjected to peel development.

The organic acid as the hydrolysis catalyst may, for example, be acetic acid or C. Acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, capric acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid, butyric acid, benzene Formic acid, arachidonic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzene Sulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, and the like.

The inorganic acid as the hydrolysis catalyst may, for example, be hydrochloric acid or nitrate. Acid, sulfuric acid, hydrofluoric acid, phosphoric acid, and the like.

The organic base as a hydrolysis catalyst may, for example, be pyridine or pyridyl Ol, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethyl monoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclo Octane, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, 1,8-diazabicyclo[5,4,0]-7-undecene, and the like.

Inorganic bases such as ammonia, sodium hydroxide, potassium hydroxide, hydrogen hydroxide Huayu, calcium hydroxide and the like. Among these catalysts, a metal chelate compound, an organic acid, and an inorganic acid are preferable, and these may be used alone or in combination of two or more kinds.

The hydrolysis catalyst is a volatile inorganic acid, for example, applicable hydrochloric acid. The hydrolysis of an alkoxyalkyl group, a decyloxyalkyl group or a halogenated decyl group is 0.1 to 100 moles, 0.1 to 10 moles, 1 to 5 moles, or 2 to 1 mole of the above hydrolyzable group. 3.5 moles of water.

The reaction temperature at the time of hydrolysis and condensation is usually carried out in the range of from 20 ° C (room temperature) to the reflux temperature under normal pressure of the solvent used for the hydrolysis. Further, it can be carried out under pressure, and for example, it can be heated to a liquid temperature of about 200 °C.

A method of obtaining a hydrazine compound (A) containing a hydrolysis condensate (polysiloxane), for example, a method of heating a mixture of hydrolyzable decane, a solvent, pure water, and an acid catalyst. Specifically, the hydrolyzable decane is dissolved in a solvent in advance, and hydrochloric acid and pure water are added as a hydrochloric acid aqueous solution, and then the mixture is dropped into a hydrolyzable decane solution to be heated. In this case, the amount of hydrochloric acid is 1 mol to the total hydrolyzable group (per alkoxy group) of the hydrolyzable decane, and is generally 0.0001 to 0.5 mol. The heating in this method can be carried out at a liquid temperature of 50 to 180 ° C, preferably to avoid evaporation or volatilization of the liquid, for example, for several tens of minutes to several tens of hours under reflux in a closed vessel.

The solvent (c1) used for the hydrolysis and condensation is, for example, n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, 2,2,4-trimethylpentane, Fat of n-octane, isooctane, cyclohexane, methylcyclohexane, etc. Aromatic hydrocarbon solvent; benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, cumene, diethylbenzene, isobutylbenzene, three An aromatic hydrocarbon solvent such as ethylbenzene, diisopropylbenzene or trimethylbenzene; acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, and diethyl Ketone, methyl isobutyl ketone, methyl-n-amyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, diisobutyl ketone, cyclohexanone, methylcyclohexane a ketone solvent such as a ketone; an ether system such as ethyl ether, isopropyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, tetrahydrofuran or 2-methyltetrahydrofuran, p-xylene , o-xylene, styrene, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol Monoisopropyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, propylene glycol monobutyl Ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, dipropylene glycol Methyl ether, diethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, Diethylene glycol, 1-octanol, ethylene glycol, hexanediol, trimethylene glycol, 1-methoxy-2-butanol, cyclohexanol, diacetone alcohol, decyl alcohol, tetrahydroindenyl Alcohol, benzyl alcohol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, γ-butyl lactone, acetone, methyl ethyl ketone, methyl isopropyl Ketone, diethyl ketone, methyl isobutyl ketone, methyl-n-butyl ketone, cyclohexanone, ethyl acetate, isopropyl ketone acetate, n-propyl acetate, isobutyl acetate, acetic acid -butyl, methanol, ethanol, isopropanol, tert-butanol, allyl alcohol, n-propanol, 2-methyl-2-butanol, isobutanol, n-butanol, 2-methyl 1-butanol, 1-pentanol, 2-methyl-1-pentanol, 2-ethylhexanol, isopropyl ether, 1,4-dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, 1,3-Dimethyl-2-imidazolidinone, dimethyl hydrazine, N-cyclohexyl-2-pyrrolidone, and the like. These solvents may be used alone or in combination of two or more.

By hydrolyzing the hydrolyzable decane in the solvent (c1), The hydrolyzate is subjected to a condensation reaction to obtain a hydrolysis condensate (polyoxane), and the condensate can be obtained in the form of a polyoxyalkylene varnish which can be dissolved in a hydrolysis solvent.

The solvent (C) used for the dilution or substitution of the varnish of the hydrazine compound (A) containing the above hydrolysis condensate (polyoxane) may be the same as the solvent (c1) used for the hydrolysis and condensation polymerization of the hydrolyzable decane. For additional solvents. The solvent in the varnish of the hydrazine compound (A) containing a hydrolysis condensate (polyoxyalkylene oxide) may be the above solvent (C).

When used as a varnish of the ruthenium compound (A), the concentration of the ruthenium compound (A) in the varnish can be used in the range of 0.1 to 60% by mass.

The component (C) of the present invention is a solvent. The solvent is preferably the same solvent as the solvent of the component (A), but is not particularly limited as long as the storage stability of the coating liquid for film formation of the present invention is not significantly impaired. The above general organic solvents can be used.

The solvent (C) is more preferably butanol or diacetone from the viewpoint of compatibility of the hydrazine compound (A) containing the hydrolysis condensate (polysiloxane) with the inorganic particles (B) having an average particle diameter of 1 to 100 nm. , methyl ethyl ketone, methyl isobutyl ketone, hexane diol, methyl cellulose, ethyl cellulose, butyl cellulose, ethyl carbitol, butyl carbitol, diethylene glycol methyl Ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monobutyl ether, cyclohexanone, methyl acetate, ethyl acetate, ethyl lactate, and the like.

In the present invention, the hydrazine compound (A) can be used to hydrolyze hydrazine. The alkane is hydrolyzed and condensed in a non-alcoholic solvent.

The hydrazine compound (A) containing the hydrolysis condensate (polysiloxane) of the present invention is obtained by using a non-alcohol containing no hydroxyl group as a solvent for hydrolysis and polycondensation, and is referred to as a fully hydrolyzed type in the present specification. A siloxane, a polyoxyalkylene having a high hydrolysis rate. The polymer obtained by using a hydroxyl group-containing alcohol for the solvent in the case of hydrolysis or polycondensation is referred to as a partially hydrolyzed polysiloxane. The fully hydrolyzed and partially hydrolyzed systems differ greatly in the amount of stanol (Si-OH) present at the end of the polymer, and the fully hydrolyzed polyoxyalkylene-based Si-OH is partially hydrolyzed. More alkane is present. The amount of Si-OH present is determined by using a varnish substituted with a non-alcohol solvent, and the amount of solid components is the same, and it can be quantified by ¹ H-NMR. The quantitative system can be obtained by integrating the peaks of the Si-OH of the polyoxyalkylene to calculate the number of protons in the peak area and comparing the number of protons in which the internal standard or the peak of the solvent is integrated to calculate the peak area.

Set the number of protons calculated from the peak of the internal standard or solvent At 1.00, the calculated number of protons of Si-OH of the fully hydrolyzed polyoxyalkylene is 0.1 or more, preferably 0.2 or more. Further, the partially hydrolyzed polyoxyalkylene is defined such that when the number of protons calculated from the internal standard or the peak of the solvent is 1.00, the number of protons calculated from Si-OH of polyoxyalkylene is less than 0.1.

a non-alcohol solvent (c1) used for hydrolysis and condensation, for example N-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, An aliphatic hydrocarbon solvent such as 2,2,4-trimethylpentane, n-octane, isooctane, cyclohexane or methylcyclohexane; benzene, toluene, xylene, ethylbenzene, three Aromatic groups such as methylbenzene, methylethylbenzene, n-propylbenzene, cumene, diethylbenzene, isobutylbenzene, triethylbenzene, diisopropylbenzene, trimethylbenzene, etc. Hydrocarbon solvent; acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl isobutyl ketone, methyl-n-amyl ketone a ketone solvent such as ethyl-n-butyl ketone, methyl-n-hexyl ketone, diisobutyl ketone, cyclohexanone or methylcyclohexanone; ethyl ether, isopropyl ether, n- An ether solvent such as butyl ether, n-hexyl ether, 2-ethylhexyl ether, tetrahydrofuran or 2-methyltetrahydrofuran. These solvents may be used alone or in combination of two or more. Among them, a ketone solvent such as acetone or an ether solvent such as tetrahydrofuran is preferably used, and acetone is particularly preferably used.

Hydrolyzing hydrazine in a non-alcohol solvent (c1), By subjecting the hydrolyzate to a condensation reaction, a hydrolysis condensate (polyoxane) can be obtained, and the condensate can be obtained in the form of a polyoxyalkylene varnish which can be dissolved in a hydrolysis solvent.

a hydrazine compound containing the obtained hydrolysis condensate (polyoxane) The solvent of the substance (A) can be substituted. Specifically, when the solvent used in the condensation after the hydrolysis and the hydrolysis (the solvent in the synthesis) is selected from acetone, the polysiloxane is obtained in acetone, and the same amount of the solvent for the substitution as the solvent in the synthesis is added, and replaced with another solvent. In the case of a solvent, acetone may be azeotropically distilled off by an evaporator or the like. At this time, a reactant (for example, methanol or ethanol) produced by hydrolysis of hydrolyzable decane can be simultaneously distilled off. Further, when a volatile acid catalyst is used, it can be simultaneously removed.

This substitution solvent will become a hydrolyzed condensate (polyoxyl) The solvent component (C) when the oxime compound (A) forms a varnish.

When the solvent is substituted, the solvent is azeotropically distilled, so The boiling point is preferably lower than the solvent for substitution. For example, a solvent used for the condensation after hydrolysis and hydrolysis may be, for example, acetone or tetrahydrofuran, and the solvent for substitution may, for example, be propylene glycol monomethyl ether acetate or the like.

The solvent (C) used for the dilution or substitution of the varnish of the hydrazine compound (A) containing the above hydrolysis-condensation product (polyoxane) may be the same as or may be the non-alcohol solvent used for the hydrolysis and condensation polymerization of the hydrolyzable decane. Additional solvent. The solvent in the varnish of the hydrazine compound (A) containing a hydrolysis condensate (polyoxyalkylene oxide) may be the above solvent (C).

When used as a varnish of the ruthenium compound (A), the concentration of the ruthenium compound (A) in the varnish can be used in the range of 0.1 to 60% by mass.

Specific examples of the solvent (C) at this time include, for example, toluene, p-xylene, o-xylene, styrene, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, Propylene glycol, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol single ethyl Ethyl acetate, diethylene glycol dimethyl ether, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, diethylene glycol single Methyl ether, dipropylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol, 1-octanol , ethylene glycol, hexanediol, trimethylene glycol, 1-methoxy-2-butanol, cyclohexanol, diacetone alcohol, decyl alcohol, tetrahydrofurfuryl alcohol, benzyl alcohol, 1,3 - Ding Er Alcohol, 1,4-butanediol, 2,3-butanediol, γ-butyl lactone, acetone, methyl ethyl ketone, methyl isopropyl ketone, diethyl ketone, methyl isobutyl Ketone, methyl-n-butyl ketone, cyclohexanone, ethyl acetate, isopropyl ketone acetate, n-propyl acetate, isobutyl acetate, n-butyl acetate, methanol, ethanol, isopropanol, Tert-butanol, allyl alcohol, n-propanol, 2-methyl-2-butanol, isobutanol, n-butanol, 2-methyl-1-butanol, 1-pentanol, 2 -methyl-1-pentanol, 2-ethylhexanol, isopropyl ether, 1,4-dioxane, N,N-dimethylformamide, N,N-dimethylacetamide And N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl hydrazine, N-cyclohexyl-2-pyrrolidone, and the like.

The component (C) of the present invention is a solvent. The solvent is preferably The solvent of the component (A) is the same non-alcoholic solvent, but is not particularly limited as long as the storage stability of the coating liquid for film formation of the present invention is not significantly impaired. The above general organic solvents can be used.

From a hydrazine compound containing a hydrolysis condensate (polyoxane) (A) From the viewpoint of compatibility with the inorganic particles (B) having an average particle diameter of from 1 to 100 nm, the solvent (C) is more preferably butanol, diacetone alcohol, methyl ethyl ketone, methyl isobutyl ketone, Hexanediol, methyl cellulose, ethyl cellulose, butyl cellulose, ethyl carbitol, butyl carbitol, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl Ether, propylene glycol monomethyl ether acetate, propylene glycol monobutyl ether, cyclohexanone, methyl acetate, ethyl acetate, ethyl lactate, and the like.

Containing the hydrolyzable decane (a1) of the present invention and hydrolyzable decane The hydrazine compound (A) which is a hydrolysis condensate of the hydrolyzable decane of (a2) is a hydrolyzable decane (a2) which has a linear chain, a branch or a ring having 3 to 6 carbon atoms. a hydrolyzable decane having an alkyl group and having three hydrolyzable groups, having a hydrolyzable decane (a1) of from 90 mol% to 50 mol%, and a hydrolyzable decane (a2) of from 10 mol% to 50 mol% The ratio of the condensate is such that the weight average molecular weight is from 700 to 4,000. In this way, the film obtained from the composition containing the ruthenium compound (A), the inorganic particles (B), and the solvent (C) has solubility developability with respect to the alkali solution, so that the patterning of 10 μm or less can be formed by using the photosensitive resist. It can simultaneously satisfy high refractive index, high light resistance, and prevent internal mixing of photosensitive resist.

By specifying the weight average molecular weight of the ruthenium compound (A), The copolymerization ratio of the hydrolyzable decane (a1) and the hydrolyzable decane (a2) in the hydrolysis condensate is defined by a fully automatic contact angle meter manufactured by Kyowa Interface Science Co., Ltd., trade name Drop Master series DM700, and pure water is used. The needle having a size of 22 G was used to prepare droplets, and the contact angle of water in which the liquid adhered to the surface of the film was calculated by the droplet method (θ/2 method) was 60° to 80°, and when it was an alkali solution, it was dissolved and developed.

Water contact angle is directly related to the dissolution and developability of alkali solution The important film properties are such that when the water contact angle of the film is less than 60°, the film is peeled and developed. When it exceeds 80°, the alkali solution is repelled and the developability is not exhibited. When the water contact angle is less than 60°, the stanol is large and the hydrophilicity is relatively high, so that the alkali solution becomes easy to permeate into the film. When the alkali solution is impregnated, the decyl alcohol of the ruthenium compound in the film is directly contacted with the alkali, and polycondensation is started before dissolution to carry out polymerization. By performing high molecular weight measurement, it does not become dissolved and developed to be peeled and developed. Moreover, when the water contact angle exceeds 80°, the hydrophobicity of the surface of the film rises, and the alkali solution is repelled, and development cannot be performed, and it becomes invisible. Formed.

By controlling the weight average molecular weight, the copolymerization ratio, and the grain The mixing ratio of the sub- (B) and the temporary heating temperature conditions allow the contact angle of the water of the film to be 60 to 80° to exhibit the optimum dissolution developability to the alkali solution.

The inorganic particle (B) component used in the present invention has 1 to The inorganic particles (B) having an average particle diameter of 100 nm may have a refractive index of 1.50 to 2.70, 1.50 to 1.70, 1.60 to 2.00, 1.90 to 2.20, or 2.20 to 2.70.

The type of the inorganic particles (B) constituting the composition of the present invention together with the above polyoxyalkylene oxide is, for example, a metal oxide such as zirconium dioxide. As the inorganic particles, zirconium dioxide may be used alone or in combination of two or more.

Specific examples of the metal oxide include, in addition to zirconium dioxide, a composite oxide of SiO ₂ or HfO _{2 in} the zirconium dioxide. The composite oxide refers to a compound in which two or more inorganic oxides are mixed at the production stage of the particles.

Further, these compounds may be used singly or in combination of two or more kinds thereof, or may be used in combination with the above oxides.

The inorganic particles (B) used in the present invention may be inorganic particles having an average particle diameter of 1 to 100 nm, 5 to 50 nm, or 1 to 10 nm by dynamic light scattering. Particles having different average particle diameters may be used in combination with the above particle diameter.

Further, when the inorganic particles (B) are used, the particles may be used as they are or a colloidal state in which the particles are dispersed in water or an organic solvent in advance may be used. (The colloidal particles are dispersed in the dispersion medium, that is, the sol). The concentration of the inorganic particles in the sol can be used in the range of 0.1 to 60% by mass.

Dispersion of aqueous sols by dispersing inorganic particles in aqueous media As the medium, an organic solvent sol which is substituted with water to form an organic solvent can be used. This dispersion medium (c2) is combined with a solvent (C) used for dilution or substitution of a varnish of a hydrazine compound (A) containing a hydrolysis condensate (polyoxyalkylene oxide), and is used as a solvent (C) used in the present invention.

Therefore, the dispersion medium (c2) can be used with the above solvent (C) The same. Further, particles obtained by treating the inorganic particles (B) with cerium oxide, an organic cerium compound, an organometallic compound or the like can also be used. The treatment by cerium oxide means that the cerium oxide particles are grown on the surface of the particles by a known method in the dispersion containing the inorganic particles (B). The treatment of the organic ruthenium compound or the organometallic compound means that the compound containing the inorganic particles (B) is added to the compound, and the reaction product of the compound or the compound is adsorbed or bonded to the reaction product. The surface of inorganic particles.

The above organic hydrazine compound, for example, a decane coupling agent or hydrazine Specific examples of the alkane and decane coupling agent are vinyltrichloromethane, vinyltrimethoxydecane, vinyltriethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxynonane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethylbis(triethoxy)decane, 3-glycidoxypropyltriethoxydecane, p - Styryltrimethoxydecane, 3-methylpropenyloxypropylmethyldimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-methylpropenyloxyl Propylmethyldiethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, 3-propene oxime Oxypropyltrimethoxydecane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane, N-2-(aminoethyl)-3-aminopropyl Methyltrimethoxydecane, N-2-(aminoethyl)-3-aminopropylmethyltriethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyl Triethoxy decane, 3-triethoxycarbamido-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxydecane, 3-chloropropyltrimethoxydecane, 3-mercaptopropylmethyldimethoxydecane, 3-mercaptopropyltrimethoxydecane, bis(triethoxycarbamidopropyl)tetrasulfide, 3 - Isocyanate propyl triethoxy decane, and the like.

Further, specific examples of decane include methyltrichlorodecane and dimethyldiene. Chlorodecane, trimethylchlorodecane, phenyltrichlorodecane, methyltrimethoxydecane, dimethyldimethoxydecane, phenyltrimethoxydecane, methyltriethoxydecane, dimethyldi Ethoxy decane, phenyl triethoxy decane, n-propyl trimethoxy decane, n-propyl triethoxy decane, hexyl trimethoxy decane, hexyl triethoxy decane, decyl trimethoxy Decane, trifluoropropyltrimethoxydecane, hexamethyldioxane, and the like.

The above organometallic compound may, for example, be a titanate coupling Specific examples of the agent or the aluminum-based coupling agent and the titanate-based coupling agent include, for example, trade names PLENACT KRTTS, KR46B, KR38B, KR138S, KR238S, KR338X, KR44, KR9SA, KR ET5, KR ET (Ajinomoto Fine-Techno Co Specific examples of the aluminum-based coupling agent include PLENACTAL-M (Ajinomoto Fine-Techno Co., Inc., manufactured by Ajinomoto Fine-Techno Co., Inc.).

The amount of these organic cerium compounds and organometallic compounds It is preferably 2 to 100 parts by mass based on 100 parts by mass of the inorganic particles (B).

Metal oxide colloidal particles used for inorganic particles (B) The product can be produced by a conventional method such as an ion exchange method, a degumming method, a hydrolysis method, or a reaction method.

The ion exchange method is, for example, ion exchange of a salt of the above metal A method of treating and removing particles after ion treatment.

The debonding method is, for example, a case where the salt of the above metal is carried out with an acid or a base. And a method of removing unnecessary electrolytes or adding a dispersion from a method of hydrolyzing an alkoxide of the above metal or a precipitate or gel obtained by hydrolyzing a basic salt of the above metal under heating The method of ion required, etc. Examples of the reaction method include a method of reacting a powder of the above metal with an acid.

Modification of the film of the present invention to form the composition (1) There is no particular limitation on the law. The component (A), the component (B), and the component (C) may be uniformly mixed. The order in which the components (A) to (C) are mixed is not particularly limited as long as a uniform varnish can be obtained.

For example, there is a method for producing a film-forming composition (1), which comprises hydrolyzing a hydrolyzable decane containing a hydrolyzable decane (a1) and a hydrolyzable decane (a2) in a solvent (c1) to obtain a weight average. a step of varnishing a compound (A) having a molecular weight of from 700 to 4,000, and dispersing the inorganic particles (B) having an average particle diameter of from 1 to 100 nm and a refractive index of from 1.50 to 2.70 by a dynamic light scattering method in a dispersion medium (c2) a step of obtaining a sol, mixing a varnish of the cerium compound (A) and a sol of the inorganic particles (B) to obtain a film-forming composition containing the cerium compound (A), the inorganic particles (B), and the solvent (C) .

The method of preparing the film-forming composition (2) of the present invention is not particularly limited. The component (A), the component (B), the component (C), and the component (D) may be uniformly mixed. The order in which the components (A) to (D) are mixed is not particularly limited as long as a uniform varnish can be obtained.

For example, a method for producing a film-forming composition (2), which comprises hydrolyzing a hydrolyzable decane containing a hydrolyzable decane (a1) and a hydrolyzable decane (a2) in a non-alcohol solvent (c1) to obtain a weight. a step of varnishing the compound (A) having an average molecular weight of 700 to 4,000. The inorganic particles (B) having an average particle diameter of 1 to 100 nm and a refractive index of 1.50 to 2.70 are dispersed in a dispersion medium by a dynamic light scattering method. C2) a step of obtaining a sol, mixing a varnish of the cerium compound (A), a sol of the inorganic particles (B), and a curing catalyst (D) to obtain a cerium-containing compound (A), an inorganic particle (B), and a curing catalyst (D) And a step of forming a composition of the film of the solvent (C).

The method of preparing the film-forming composition (3) of the present invention is not particularly limited. The component (A), the component (B), the component (C), and the component (E) may be uniformly mixed. Mixed component (A), component The order of (B), the component (C), and the component (E) is not particularly limited as long as a uniform varnish can be obtained.

For example, there is a method for producing a film-forming composition (3), which comprises hydrolyzing a hydrolyzable decane containing a hydrolyzable decane (a1) and a hydrolyzable decane (a2) in a non-alcohol solvent (c1) to obtain a step of varnishing the compound (A) having a weight average molecular weight of 700 to 4,000. The inorganic particles (B) having an average particle diameter of 1 to 100 nm and a refractive index of 1.50 to 2.70 are dispersed in a dispersion medium by a dynamic light scattering method. (c2) a step of obtaining a sol, mixing a varnish of the cerium compound (A), a sol of the inorganic particles (B), and a diketone compound (E) to obtain a cerium compound (A), an inorganic particle (B), and a diketone compound ( The step of forming a composition from the film of E) and solvent (C).

The method of preparing the film-forming composition (3) of the present invention is not particularly limited. The components (A), (B), (C), and (D), (F), and (G) may be uniformly mixed. The order of mixing the component (A), the component (B), the component (C), the component (D) component, the component (F), and the component (G) is not particularly limited as long as a uniform varnish can be obtained.

For example, there is a method for producing a film-forming composition (4), which comprises hydrolyzing a hydrolyzable decane containing a hydrolyzable decane (a1) and a hydrolyzable decane (a2) in a non-alcohol solvent (c1). Weight average molecule a step of varnishing the compound (A) in an amount of from 700 to 4,000, The step of dispersing the inorganic particles (B) having an average particle diameter of 1 to 100 nm and a refractive index of 1.50 to 2.70 in a dispersion medium (c2) to obtain a sol by dynamic light scattering method, The varnish of the cerium compound (A), the sol of the inorganic particles (B), the curing catalyst (D), water (F) and the acid (G) are mixed to obtain a cerium compound (A), an inorganic particle (B), and a hardening contact. A step of forming a composition of a film of the medium (D), water (F), acid (G), and solvent (C).

As the hardening catalyst of the component (D), an ammonium salt, a phosphine, a phosphonium salt, a phosphonium salt or a metal chelate compound can be used.

The ammonium salt has, for example, the formula (5): (wherein, p represents 2 to 11, q represents an integer of 2 to 3, R ¹¹ represents an alkyl group, an aryl group, or a combination thereof, and Y ^- represents an anion); and has a formula (6): (wherein R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ represent an alkyl group, an aryl group, or a combination thereof, N represents a nitrogen atom, Y ^- represents an anion, and R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ a fourth-order ammonium salt of a structure each of which is bonded to a nitrogen atom by a CN bond; having the formula (7): (In the formula, R ¹⁶ and R ¹⁷ represent an alkyl group, an aryl group, or a combination thereof, and Y ^- represents an anion), and a fourth-order ammonium salt having the structure: (8): (In the formula, R ¹⁸ represents an alkyl group, an aryl group, or a combination thereof, and Y ^- represents an anion), and a fourth-order ammonium salt having the structure: (9): (In the formula, R ¹⁹ and R ²⁰ represent an alkyl group, an aryl group, or a combination thereof, and Y ^- represents an anion) a fourth-order ammonium salt having the formula (10): (In the formula, p represents a second-order ammonium salt of 2 to 11, q represents an integer of 2 to 3, H represents a hydrogen atom, and Y ^- represents an anion).

The onium salt is, for example, a formula (11): [Chem. 9] R ²¹ R ²² R ²³ R ²⁴ P ⁺ Y ^- Formula (11) (wherein R ²¹ , R ²² , R ²³ , and R ²⁴ represent an alkyl group, an aromatic group a group, or a combination thereof, wherein P represents a phosphorus atom, Y ^- represents an anion, and R ²¹ , R ²² , R ²³ , and R ²⁴ are each a terminal salt represented by a bond of a phosphorus bond with a phosphorus atom) .

Further, the onium salt is, for example, represented by the formula (12): [Chem. 10] R ²⁵ R ²⁶ R ²⁷ S ⁺ Y ^- (12) (wherein R ²⁵ , R ²⁶ and R ²⁷ represent an alkyl group, an aryl group, or of their combination, S represents a sulfur atom, Y ^- represents an anion, and R ^25, R ^26, and R ²⁷ each represents a sulfonium salt of level 3 by CS bonds with a sulfur atom are bonded).

The compound of the above formula (5) is a fourth-order ammonium salt derived from an amine, p represents 2 to 11, and q represents an integer of 2 to 3. R ^{11 of} the fourth-order ammonium salt each represents an alkyl group having 1 to 18 carbon atoms, preferably 2 to 10, an aryl group or a combination thereof, and for example, a linear chain such as an ethyl group, a propyl group or a butyl group. An alkyl group, or a benzyl group, a cyclohexyl group, a cyclohexylmethyl group, a dicyclopentadienyl group or the like. Further, the anion (Y ^- ) may, for example, be a halide ion such as a chloride ion (Cl ^- ), a bromide ion (Br ^- ), an iodide ion (I ^- ), or a carboxylate (-COO ^- ) or a sulfate (- An acid group such as SO ₃ ^- ) or an alcoholate (-O ^- ).

The compound of the above formula (6) is a fourth-order ammonium salt represented by R ¹² R ¹³ R ¹⁴ R ¹⁵ N ⁺ Y ^- . R ¹² , R ¹³ , R ¹⁴ and R ^{15 of} the fourth-order ammonium salt are each an alkyl group having 1 to 18 carbon atoms, an aryl group or a combination thereof, or bonded to a ruthenium atom by a Si-C bond. Decane compound. The anion (Y ^- ) is, for example, a halide ion such as a chloride ion (Cl ^- ), a bromide ion (Br ^- ), an iodide ion (I ^- ), or a carboxylate (-COO ^- ) or a sulfate (-SO ₃ ^- ). An acid group such as an alkoxide (-O ^- ). The fourth-grade ammonium salt can be obtained from commercially available products, such as ammonium tetramethylammonium acetate, tetrabutylammonium acetate, triethylbenzylammonium chloride, triethylbenzylammonium bromide, and trioctyl chloride. Alkyl ammonium, tributylbenzylammonium chloride, trimethylbenzylammonium chloride, and the like. These can be added as ammonium compounds.

The compound of the above formula (7) is a fourth-order ammonium salt derived from a 1-substituted imidazole, and R ¹⁶ and R ^{17 have} a carbon number of 1 to 18, and the sum of the number of carbon atoms of R ¹⁶ and R ¹⁷ has 7 or more. It is better. For example, R ¹⁶ represents a methyl group, an ethyl group, a propyl group, a phenyl group, a benzyl group, a decane compound bonded to a ruthenium atom by a Si-C bond, or a combination thereof. R ¹⁷ represents, for example, a benzyl group, an octyl group or an octadecyl group. The anion (Y ^- ) is, for example, a halide ion such as a chloride ion (Cl ^- ), a bromide ion (Br ^- ), an iodide ion (I ^- ), or a carboxylate (-COO ^- ) or a sulfate (-SO ₃ ^- ). An acid group such as an alkoxide (-O ^- ). This compound can be obtained as a commercial product, but an imidazole compound such as 1-methylimidazole or 1-benzylimidazole can be reacted with a halogenated alkyl group or a halogenated aryl group such as a benzyl bromide or a methyl bromide. To manufacture. Further, the compound of the formula (7) can also be used as a hydrogenated 4,5-dihydroimidazole compound at the 4-position and the 5-position. These may be added as a cyclic ammonium compound.

The compound of the above formula (8) is a fourth-order ammonium salt derived from pyridine, and each of R ¹⁸ is an alkyl group having 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms, an aryl group, or the like. Combinations include, for example, butyl, octyl, benzyl, lauryl. The anion (Y ^- ) is, for example, a halide ion such as a chloride ion (Cl ^- ), a bromide ion (Br ^- ), an iodide ion (I ^- ), or a carboxylate (-COO ^- ) or a sulfate (-SO ₃ ^- ). An acid group such as an alkoxide (-O ^- ). This compound can be obtained from a commercial product, but for example, a pyridine can be reacted with a halogenated alkyl group such as lauryl chloride, benzyl chloride, benzyl bromide, methyl bromide or octyl bromide or a halogenated aryl group. Manufacturing. The compound is, for example, N-laurylpyridinium chloride or N-benzylpyridinium bromide.

The compound of the above formula (9) is a fourth-order ammonium salt derived from a substituted pyridine represented by a pyridyl group or the like, and each of R ¹⁹ is an alkyl group having 1 to 18, preferably 4 to 18, an aryl group, Or a combination thereof, for example, a methyl group, an octyl group, a lauryl group, a benzyl group or the like. Each of R ²⁰ is an alkyl group having 1 to 18 carbon atoms, an aryl group, or a combination thereof, and for example, when the fourth-order ammonium is derived from a pyridyl group, R ¹⁹ is a methyl group. The anion (Y ^- ) is, for example, a halide ion such as a chloride ion (Cl ^- ), a bromide ion (Br ^- ), an iodide ion (I ^- ), or a carboxylate (-COO ^- ) or a sulfate (-SO ₃ ^- ). An acid group such as an alkoxide (-O ^- ). This compound can be obtained as a commercial product, but a substituted alkyl group such as methylpyridine or the like, a halogenated alkyl group such as methyl bromide, octyl bromide, lauryl chloride, benzyl chloride or benzyl bromide, or The halogenated aryl group is reacted to produce. The compound is, for example, N-benzylpyridinium chloride, N-benzylpyridinium bromide, N-laurylpyridinium chloride or the like.

The compound of the above formula (10) is a third-order ammonium salt derived from an amine, p represents 2 to 11, and q represents an integer of 2 to 3. Further, the anion (Y ^- ) is, for example, a halide ion such as a chloride ion (Cl ^- ), a bromide ion (Br ^- ), an iodide ion (I ^- ), or a carboxylate (-COO ^- ) or a sulfate (-SO ₃ ^- ), an acid group such as an alkoxide (-O ^- ). It can be produced by reacting an amine with a weak acid such as a carboxylic acid or a phenol. The carboxylic acid is, for example, formic acid or acetic acid. When formic acid is used, the anion (Y ^- ) is (HCOO ^- ); when acetic acid is used, the anion (Y ^- ) is (CH ₃ COO ^- ). Further, when phenol is used, the anion (Y ^- ) is (C ₆ H ₅ O ^- ).

The compound of the above formula (11) is a fourth-order phosphonium salt having a structure of R ²¹ R ²² R ²³ R ²⁴ P ⁺ Y ^- . R ²¹ , R ²² , R ²³ , and R ²⁴ are each an alkyl group having 1 to 18 carbon atoms, an aryl group, or a combination thereof, or a decane compound bonded to a ruthenium atom by Si-C bonding, Preferably, among the four substituents of R ²¹ to R ²⁴ , three are a phenyl group or a substituted phenyl group, for example, a phenyl group or a tolyl group, and the remaining one is each an alkyl group having 1 to 18 carbon atoms. An aryl group or a decane compound bonded to a ruthenium atom by Si-C bonding. Further, the anion (Y ^- ) is, for example, a halide ion such as a chloride ion (Cl ^- ), a bromide ion (Br ^- ), an iodide ion (I ^- ), or a carboxylate (-COO ^- ) or a sulfate (-SO ₃ ^- ), an acid group such as an alkoxide (-O ^- ). The compound is commercially available, and examples thereof include a tetraalkylphosphonium halide such as a tetra-n-butylphosphonium halide or a tetra-n-propylphosphonium halide, and a trialkylbenzylphosphonium halide such as a triethylbenzylphosphonium halide. a triphenylmonoalkylphosphonium halide, a triphenylbenzylphosphonium halide, a tetraphenylphosphonium halide, a tetraphenylphosphonium monoarylphosphonium halide, or the like, or a triphenylmethylphosphonium halide A trimethylphenyl monoalkyl halide (the halogen atom is a chlorine atom or a bromine atom). Particularly preferred are a triphenylmonoarylphosphonium halide such as a triphenylmethylphosphonium halide or a triphenylethylphosphonium halide, a triphenylmonoarylphosphonium halide such as a triphenylbenzylphosphonium halide, or a trimethylhalogen halide. A trimethylphenylmonoarylphosphonium halide such as a monophenylphosphonium group or a trimethylphenylmonoalkylphosphonium halide (a halogen atom is a chlorine atom or a bromine atom).

Further, the phosphines are, for example, methylphosphine, ethylphosphine, propylphosphine or the like. a second phosphine such as a first phosphine such as propylphosphine, isobutylphosphine or phenylphosphine, dimethylphosphine, diethylphosphine, diisopropylphosphine, diisopentylphosphine or diphenylphosphine; A third phosphine such as trimethylphosphine, triethylphosphine, triphenylphosphine, methyldiphenylphosphine or dimethylphenylphosphine.

The compound of the above formula (12) is a third-order phosphonium salt having a structure of R ²⁵ R ²⁶ R ²⁷ S ⁺ Y ^- . R ²⁵ , R ²⁶ and R ²⁷ are each an alkyl group having 1 to 18 carbon atoms, an aryl group, or a combination thereof, or a decane compound bonded to a ruthenium atom by Si-C bonding, preferably 3 of the 4 substituents of R ²⁵ to R ²⁷ are a phenyl group or a substituted phenyl group, for example, a phenyl group or a tolyl group, and the remaining one is an alkyl group which may be substituted with 1 to 18 carbon atoms, An aryl group, or a combination thereof. Further, the anion (Y ^- ) is, for example, a halide ion such as a chloride ion (Cl ^- ), a bromide ion (Br ^- ), an iodide ion (I ^- ), or a carboxylate (-COO ^- ) or a sulfate (-SO ₃ ^- ), an acid group such as an alkoxide (-O ^- ). The compound is commercially available, and examples thereof include a halogenated trialkylsulfonium halide such as a tri-n-butylphosphonium halide or a tri-n-propylphosphonium halide; and a trialkylbenzylphosphonium halide such as a diethylbenzylphosphonium halide; a halogenated diphenylmonoalkylphosphonium halide such as diphenylmethylguanidinium halide or diphenylethylphosphonium halide; a triphenylphosphonium halide (a halogen atom is a chlorine atom or a bromine atom), and a tri-n-butylphosphonium carboxylic acid. a trialkyl hydrazine carboxylic acid ester such as an ester, a tri-n-propyl hydrazine carboxylate or a trialkyl hydrazine carboxylic acid ester such as diethyl benzyl hydrazine carboxylate or a diphenylmethyl hydrazine carboxylic acid. a diphenylmonoalkylphosphonium carboxylate such as an ester or a diphenylethylphosphonium carboxylate; a triphenylsulfonium carboxylate; a triphenylsulfonium trifluoromethanesulfonate; Particularly preferred are triphenylsulfonium halides and triphenylsulfonium carboxylates. These can be added as a compound.

Metal chelating compounds such as triethoxy ‧ mono Acetone) Titanium, tri-n-propoxy ‧ mono(ethinyl acetonide) titanium, triisopropoxy ‧ mono (acetoxyacetone) titanium, tri-n-butoxy ‧ single (acetamidacetone) Titanium, tris-s-butoxy ‧ mono(ethinyl acetonide) titanium, tri-t-butoxy ‧ mono (acetoxyacetone) titanium, diethoxy ‧ bis (ethyl decyl acetonate) titanium , bis-n-propoxy bis(ethinyl acetonate) titanium, diisopropoxy bis bis(acetic acetoxy) titanium, di-n-butoxy bis bis(ethinyl acetonate) titanium, Di-sec-butoxy bis(ethinylacetone) titanium, di-t-butoxy bis bis(acetic acetone) titanium, monoethoxy ‧ cis (acetyl acetonide) titanium, single - N-propoxy ‧ cis (acetonitrile) titanium, monoisopropoxy ‧ cis (acetoxime) titanium, mono-n-butoxy ‧ cis (acetonitrile) titanium, single-sec - Butoxy oxynphthyl (ethinyl acetonide) titanium, mono-t-butoxy ‧ cis (acetoxyacetone) titanium, ruthenium (acetonitrile) titanium, triethoxy ‧ single (ethyl ethyl Indoleacetic acid) titanium, tri-n-propoxy ‧ mono (ethyl acetonitrile) titanium, three different Propoxy ‧ mono (ethyl acetonitrile ) titanium, tri-n-butoxy ‧ mono (ethyl acetonitrile ) titanium, tri-sec-butoxy ‧ mono (ethyl acetonitrile ) titanium, Tri-t-butoxy ‧ mono (ethyl acetonitrile ) titanium, diethoxy bis (ethyl acetonitrile ) titanium, di-n-propoxy bis (ethyl acetonitrile ) titanium , diisopropoxy ‧ bis(ethyl acetoacetate) titanium, di-n-butoxy bis (ethyl acetonitrile) titanium, di-sec-butoxy bis (ethyl acetamidine acetate Titanium, di-t-butoxy bis (ethyl acetoacetate) titanium, monoethoxy ‧ gin (ethyl acetoacetate) titanium, mono-n-propoxy ‧ gin (ethyl acetamidine) Acetic acid) titanium, monoisopropoxy ‧ cis (ethyl acetoacetate) titanium, mono-n-butoxy ‧ cis (ethyl acetoacetate) titanium, mono-sec-butoxy ‧ gin (ethyl Ethylene acetate) titanium, mono-t-butoxy ‧ cis (ethyl acetoacetate) titanium, strontium (ethyl acetoacetate) titanium, mono (acetyl acetonide) ginseng (ethyl acetoacetate) titanium , bis(ethylmercaptoacetone) bis(ethylacetamidineacetic acid) titanium, ginseng (ethionylacetone) mono(ethylacetamidineacetic acid) titanium, titanium chelating compounds, etc.; triethoxy ‧ single (B Mercaptoacetone) zirconium, tri-n-propyl Zirconium mono(acetonitrile)zirconium, triisopropoxy ‧ mono(ethinyl acetonide) zirconium, tri-n-butoxy ‧ mono (acetyl ketone) zirconium, tri-sec-butoxy ‧Single (acetonitrile)zirconium, tris-t-butoxy ‧ mono(ethinyl acetonide) zirconium, diethoxy bis (acetyl acetonide) zirconium, di-n-propoxy ‧ double (Ethyl mercaptoacetate) zirconium, diisopropoxy ‧ bis(ethyl decyl acetonide) zirconium, di-n-butoxy bis bis(ethyl decyl acetonate ) zirconium, di-sec-butoxy ‧ double Ethyl acetonide) zirconium, zirconium di-t-butoxy bis(ethyl decyl acetonate), zirconium monoethoxy phenanthrene (ethinyl acetonide), mono-n-propoxy quinone Zirconium, monoisopropoxy ‧ ginseng (acetonitrile) zirconium, mono-n-butoxy Zirconium (acetyl acetoacetate) zirconium, mono-sec-butoxy ‧ cis (ethinyl acetonide) zirconium, mono-t-butoxy ‧ ginsyl (ethenyl acetonide) zirconium, cerium (ethenyl) Acetone, zirconium, triethoxy, mono(ethylacetamidineacetic acid) zirconium, tri-n-propoxy ‧ mono(ethylacetamidineacetic acid) zirconium, triisopropoxy ‧ mono (ethyl acetoacetic acid Zirconium, tri-n-butoxy ‧ mono (ethyl acetamidine acetic acid) zirconium, tri-sec-butoxy ‧ mono (ethyl acetoacetate) zirconium, tri-t-butoxy ‧ single (B) Ethylene acetoacetate) zirconium, diethoxy bis (ethyl acetonitrile) zirconium, di-n-propoxy bis (ethyl acetonitrile) zirconium, diisopropoxy ‧ bis (ethyl Ethylene acetate) zirconium, di-n-butoxy bis(ethylacetamidineacetic acid) zirconium, di-sec-butoxy bis (ethyl acetonitrile) zirconium, di-t-butoxy ‧ Zirconium bis(ethylacetamidineacetate), zirconium monoethoxy phenate (ethyl acetoacetate), zirconium mono-n-propoxy ‧ cis (ethyl acetoacetate), monoisopropoxy ‧ (Ethylacetamidineacetic acid) zirconium, mono-n-butoxy ‧ cis (ethyl acetoacetate) zirconium, mono-sec-butoxy ‧ ginsyl (ethyl acetoacetate) zirconium, mono-t-butyl Oxygen ginseng (ethyl acetoacetate) zirconium, hafnium (B Ethylene acetate) zirconium, mono(ethylideneacetone) ginseng (ethyl acetoacetate) zirconium, bis(ethyl decyl acetonate) bis(ethyl acetonitrile) zirconium, ginseng (ethyl acetonide) single (B) a zirconium chelate compound such as zirconium acetate; zirconium or the like; an aluminum chelate compound such as aluminum (e, acetonitrile) aluminum or ginseng (ethyl acetoacetate);

The addition amount of the hardening catalyst (D) component is relative to the bismuth compound 100 parts by mass of the component (A) is 0.01 to 10 parts by mass, 0.01 to 5 parts by mass, or 0.01 to 3 parts by mass. The hardening catalyst (D) exhibits the alkali developability of the ruthenium compound (A) of the fully hydrolyzed polyoxyalkylene, and is added for the purpose of control, and when the amount is less than 0.01 parts by mass, the film may be in the base. When the developer is completely dissolved in the developer, if it is more than 10 parts by mass, the hardening proceeds excessively, and the pattern may not be formed.

The component (E) of the present invention is used as a hydrogen bond film roughening prevention A functional diketone compound. The diketone compound which functions as a hydrogen bond film roughening prevention material is a compound which forms a hydrogen bond when it exists in the hydroxy group of the hydrazine compound (A) and inorganic particle (B), and a varnish, or drying. When a hydrogen bond is formed, film roughening at the time of recoating of the photosensitive resist and peeling of the resist film can be suppressed.

The diketone compound (E) is, for example, a 1,2-diketone and/or a 1,3-di ketone. The diketone compound (E) has a partial structure represented by the formula (3) and/or the formula (4). In the formula (3), W represents a carbon atom or an oxygen atom.

Diketone compound as a function of hydrogen bond film roughness preventing material (E) From the viewpoint of workability, a compound having a basic skeleton represented by the above compound (3) is preferably a liquid at 23 ° C under atmospheric pressure.

Specific examples of the above component (E), for example, ethyl acetonitrile Ketone, 3-ethyl-2,4-pentanedione, 3-ethyl-2,4-pentanedione, bis(trimethylethenyl)methane, 2,6-dimethyl-3,5 -heptanedione, 6-methyl-2,4-heptanedione, methyl pyruvate, ethyl pyruvate, butanedione, 3,4-hexanedione, 2,3-pentanedione, 2, 3-heptanedione, 5-methyl-2,3-hexanedione, and the like. In the case where the component (E) is in the formula (3), it has a partial structure O=C-C=O bond, and in the case of the formula (4), it may have a partial structure O=C-C-C=O bond, and is not particularly limited. Some of these structures are capable of suppressing film roughness when the photosensitive resin is removed by the hydroxyl group and the hydrogen bond present in the ruthenium compound (A) and the inorganic particles (B).

The diketone compound (E) is preferably, for example, diacetyl or acetone. Methyl ester, ethyl pyruvate, acetonitrile.

The amount of the diketone compound (E) added is relative to the deuteration 100 parts by mass of the component (A) is from 1 to 10,000 parts by mass, from 100 to 5,000 parts by mass, or from 500 to 2,000 parts by mass, preferably from 100 to 5,000 parts by mass, more preferably from 500 to 2,000 parts by mass.

The water (F) component is preferably ion-exchanged water. Use general In the case of tap water, sodium ions, potassium ions, chloride ions, and the like contained in the tap water are brought into the varnish to deteriorate the storage stability of the polyoxyalkylene, which may impair the uniform varnish quality. The proportion of the water (F) component in the total solvent containing water (F) and solvent (C) must be 6 mass% to 18 mass%.

The proportion of the total solvent of the component (F) is less than 6% by mass In some cases, the storage stability may be impaired, and when it exceeds 18% by mass, the coatability may be deteriorated. The water (F) component is preferably added in an amount of from 8 to 16% by mass, more preferably from 10 to 14% by mass, based on the total solvent.

The acid (G) component contains 1 to 2 carboxyl groups in the molecule, and the final film can be formed into an acid having a pH of 3 to 5 of the composition (varnish).

The amount of the acid (G) to be added is adjusted to a pH of 3 to 5 by the film-forming composition (varnish), and may be added to the film-forming composition (varnish).

Specific examples of the component (G) include, for example, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, capric acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid. , azelaic acid, gallic acid, butyric acid, mellitic acid, arachidonic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, flax Oleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, C Diacid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, and the like. By setting the pH of the final film-forming composition (varnish) to 3 to 5, the stability of the stanol present at the end of the fully hydrolyzed polyoxyalkylene can be improved. The final varnish has a pH of from 3 to 5, preferably near pH 4. It is known that the stability of the stanol is optimized by setting the pH of the film-forming composition (varnish) to 4. From the viewpoint of setting the pH of the final film-forming composition (varnish) to 4, the component (G) is particularly preferably formic acid, acetic acid, propionic acid, oxalic acid or maleic acid.

Adding the above component (F) and component (G) to the varnish Among them, the storage stability of the film-forming composition (varnish) of 5 ° C to 23 ° C can be greatly improved, and a good film can be provided for a long period of time.

a solid component of the film-forming composition containing a ruthenium compound (A), inorganic particles (B), a curing catalyst (D), a diketone compound (E), and an acid (G), but may contain components other than the above.

In the present invention, in addition to not impairing the effects of the present invention, In addition to the component (A), the component (B), the component (C), the component (D), the component (E), the component (F), and the component (G), other components such as a flat agent or a surfactant may be contained. Ingredients.

Surfactants such as polyoxyethylene lauryl ether, polyoxyethylene Polyoxyethylene alkyl allyl groups such as polyoxyethylene alkyl ethers such as stearyl ether, polyoxyethylene hexadecyl ether, and polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, polyoxyethylene nonyl phenol ether, and the like Ethers, polyoxyethylene ‧ polyoxypropylene block copolymers, Sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, etc. Sorbitol fatty acid esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan oil Nonionic surfactant such as polyoxyethylene sorbitan fatty acid ester such as acid ester or polyoxyethylene sorbitan tristearate, trade name Eftop (registered trademark) EF301, EF303, EF352 ((share) TOHKEM PRODUCTS), trade names Megafac F171, F173, F-553, F-554, R-08, R-30, R-30-N (made by Dainippon Ink Chemical Industry Co., Ltd.), Fluorad FC430, FC431 (Sumitomo a 3M (stock) system, a trade name of Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (made by Asahi Glass Co., Ltd.), a fluorine-based surfactant, and an organic siloxane polymer KP341 ( Shin-Etsu Chemical Industry Co., Ltd., BYK-302, BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-370, BYK-375, BYK- 378 (BYK-Chemie Japan). These surfactants may be used singly or in combination of two or more. When the surfactant is used, the ratio thereof is 0.0001 to 5 parts by mass, 0.001 to 1 part by mass, or 0.01 to 0.5 part by mass based on 100 parts by mass of the hydrazine compound (A).

Mix the above other ingredients, solvents, flat agents or interfaces In the method of the active agent, the inorganic particles (B) and the solvent (C) are added to the hydrazine compound (A), and the components (A) to (C) are not particularly limited.

<Formation of film>

The film-forming composition of the present invention can be applied to a substrate to be thermally cured to obtain a desired film. The coating method can be carried out by a known or well-known method. For example, a spin coating method, a dipping method, a shower coating method, an inkjet method, a spray method, a bar coating method, a gravure coating method, a slit coating method, a roll coating method, a transfer printing method, and a brush coating method can be employed. Methods such as a method, a knife coating method, and an air knife coating method. The substrate used at this time may, for example, be ruthenium, indium tin oxide (ITO), indium zinc oxide (IZO), polyethylene terephthalate (PET), triethylenesulfonyl cellulose (TAC), poly Ethylene (PE), ionic polymer (IO), polyimine (PI), polydecylamine (PA), polyvinyl chloride (PVC), polycycloolefin (PCO), polyvinylidene chloride (PVDC), Polyvinyl alcohol (PVA), polypropylene (PP), polycarbonate (PC), polystyrene (PS), polyacrylonitrile (PAN), ethylene vinyl acetate copolymer (EVA), ethylene vinyl alcohol copolymer ( EVOH), ethylene methacrylic acid copolymer (EMMA), polymethacrylic acid (PMMA), nylon, plastic, glass, sapphire, quartz, diamond, ceramic, aluminum gallium arsenide (AlGaAs), gallium arsenide phosphorus (GaAsP) , InGaN, InGaN, GaN, AlGaN, GaP, Zinc Selenide, AlGaInP, Zinc Oxide ) a substrate formed by the like.

The heating machine is not particularly limited, for example, using a hot plate, grilling The tank and the furnace are heated under an appropriate atmosphere, that is, an inert gas such as the atmosphere or nitrogen, or a vacuum. Thereby, a quilt having a uniform film forming surface can be obtained membrane.

Heating temperature is the purpose of evaporating the solvent, no special limit For example, it can be carried out at 40 to 200 ° C. In these cases, in order to exhibit higher uniform film forming properties or to carry out a reaction on a substrate, there may be a temperature change of two or more stages.

Heating temperature and heating time select the appropriate electronic equipment The conditions of the process steps may be set, and the physical properties of the polyoxane film may be selected to suit the desired characteristics of the electronic device.

含有 containing the hydrolysis condensate (polyoxane) of the present invention The film-forming composition of the compound (A), the inorganic particles (B), the solvent (C), the component (D), the component (E), the component (F), and the component (G) is preferably such a component. The film-forming composition (varnish) formed by the hybridization becomes a uniform dispersion.

Here, mixing refers to the mixing of different properties in a broad sense. The mass is mixed in a solution state in which the different solutes may or may not have chemical or physical interaction with each other as long as the dispersibility is maintained.

Mixing as long as the final film forming composition is available When the stability of (varnish) is used, the preparation method is not particularly limited.

For example, the method (1): containing a hydrolysis condensate (polyoxyl) The alkane compound (A) is mixed in a solution state (varnish) in a dispersion (sol) of the inorganic particles (B), and the method (2): a hydrazine compound containing a hydrolysis condensate (polyoxane) (A) Various methods such as dispersing inorganic particles (B) in a solution (in a varnish), but from the viewpoint of workability, it is preferred to use a hydrazine compound (A) containing a hydrolysis condensate (polyoxane). A method in which the state of the solution (varnish) is mixed with the dispersion (sol) of the inorganic particles (B).

The stability of the final varnish of the mixture is not The precipitation due to the decrease in dispersibility, the large change in the primary particle diameter or the secondary particle diameter, the deterioration in coatability, the coloration (whitening, yellowing), and the deterioration of the film quality may be sufficient.

The content of the inorganic particles in the composition does not impair the obtained The range of the dispersibility of the final varnish can be controlled, and can be controlled in accordance with the refractive index, transmittance, and heat resistance of the intended film.

Containing a hydrolysis condensate (polyoxyalkylene) containing the present invention The film-forming composition (coating liquid) of the compound (A), the inorganic particles (B), and the solvent (C) is not precipitated due to a decrease in dispersibility, primary particle size or secondary particle size. The storage conditions of the large-diameter change, the deterioration of the coating property, the coloring (whitening, yellowing), and the deterioration of the film quality are not particularly limited. For example, it can be stored at 23 ° C (stored at room temperature), 5 ° C (storage storage), and -20 ° C (refrigerated storage). In the varnish state, in order to prevent the hydroxyl groups from reacting with each other, it is stored at -20 ° C (freezing storage). It is better.

The present invention coats the above film forming composition on a substrate The upper surface is heated to have a refractive index of 1.50 to 1.90, 1.50 to 1.70, or 1.70 to 1.90 at a wavelength of 633 nm and a pencil hardness of H~9H, H~5H, or H as determined by JIS specification K5600. A film with a hardness of ~3H.

<Method of patterning the film>

Although the film-forming composition of the present invention has no photosensitivity, it has solubility developability in an alkali solution. Therefore, a pattern of 10 μm or less can be formed by using a photosensitive resist. The reason why the film forming composition is not provided with photosensitivity is because the photosensitizer added as a photosensitive material causes deterioration of light resistance.

The method of patterning is completed by the following steps 1 to 9.

Step 1: Coating the film forming composition on the substrate

Step 2: Temporarily drying the film on the substrate

Step 3: Coating a photosensitive resist on the film forming composition

Step 4: Dry the photosensitive resist

Step 5: Light irradiation from the photosensitive resist through the mask

Step 6: Perform alkali development

Step 7: Wash with pure water (rinse)

Step 8: Stripping Resist

Step 9: Formally heat the patterned film forming composition

Step 2 is a step of temporarily drying the film-forming composition, and is not particularly limited as long as it is heated until it is dissolved in the main solvent of the photosensitive resist of the step 3, and is 40 to 200 ° C or 80 ° C. The heating may be carried out at 150 ° C or 90 ° C to 120 ° C, and the heating time may be 30 seconds to 300 seconds, or 60 seconds to 120 seconds, or 180 seconds to 240 seconds.

Step 3 is a step of coating a photosensitive resist, and is commercially available. A general positive photosensitive resist or a negative photosensitive resist can be used. For example, THMR-iP1800 (manufactured by Tokyo Ohka Kogyo Co., Ltd.), AZ3100, AZ1500 (manufactured by AZ ELECTRONIC MATERIALS Co., Ltd.), or the like can be used.

Step 5 is a step of irradiating light through the mask, using The general exposure machine can be. For example, an aligner PLA-600FA (manufactured by Canon), an i-line stepper NSR-2205i12D (manufactured by Nikon), or the like can be used.

Step 6 is a step of alkali development, and the alkali developer is generally used. The aqueous solution of tetramethylammonium hydroxide (TMAH) can be used. The concentration of TMAH may be 0.1% by mass to 2.38% by mass, 0.5% by mass to 1.0% by mass, or 1.0% by mass to 2.0% by mass, and the developing time is 10 seconds to 180 seconds, 20 seconds to 60 seconds, or 90 seconds to 120 seconds. Further, the alkali developing solution may be an inorganic base such as sodium carbonate, sodium hydroxide or potassium hydroxide aqueous solution.

Step 8 is a step of stripping the resist, a general resist solvent Just fine. For example, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl pyruvate, and the like.

Step 9 is a step of subjecting the film forming composition to formal heating. The heating may be carried out at 80 ° C to 300 ° C, or 100 ° C to 150 ° C, or 180 ° C to 230 ° C, or 250 ° C to 300 ° C.

Through the method of patterning as above, even the film formation group The product is a non-photosensitive material and can be patterned due to alkali developability.

The film composed of the composition of the present invention thus obtained may be It satisfies high refractive index, high transparency, high heat resistance, high light resistance, and high hardness, so it can be applied to liquid crystal displays, plasma displays, cathode ray tubes, organic light-emitting displays, electronic paper, LEDs, solid-state imaging devices, and solar energy. An electronic device such as a battery or an organic thin film transistor. In particular, it can be suitably used as a member for LEDs which requires high light resistance.

More specifically, it can be applied as a backlight for various displays. Light source, signal, lighting, laser, biosensor, etc.

[Examples]

Hereinafter, the present invention will be specifically described by way of Examples and Comparative Examples, but the present invention is not limited to the examples described below. Further, each measuring device used in the examples is as follows.

[GPC]

Device: HTC-8200 GPC made by Tosoh Corporation

Column: Shodex KF-804L+KF-805L

Column temperature: 40 ° C

Solvent: tetrahydrofuran (hereinafter THF)

Detector: UV (254nm)

Checking line: standard polystyrene

[ ¹ H-NMR]

Device: Japan Electronics Co., Ltd. ECP300

Solvent: heavy acetone

[Refractive index of the film / elliptical thickness gauge]

Device: J.A. Woollam Japan Multi-incidence Angle Spectroscopic Elliptical Thickness Gauge VASE

Measured at a wavelength of 450 nm.

[UV visible spectrophotometer]

Device: (share) Shimadzu SU-3600 made by Shimadzu Corporation

[refractive index of particles]

Device: J.A. Woollam Japan multi-incident angle spectroscopic elliptical thickness gauge VASE.

Measured at a wavelength of 450 nm.

The inorganic particles (B) were made to have a film thickness of 100 nm, diluted with propylene glycol monomethyl ether, and spin-coated on a ruthenium substrate, and measured at 100 ° C for 1 minute, heated by a hot plate, and heated at 200 ° C for 5 minutes. The refractive index of the film after the plate is heated.

[The average particle size]

Device: N5 made by Beckman Coulter

The inorganic particle (B) dispersion was diluted with the same solvent as the dispersion medium, and the particle diameter (Unimodal mode, strength average particle diameter) of the dynamic light scattering method was measured.

[Rot coating method]

Device: Tokyo Electron system, clean track, device name ACT8

[exposure]

Device: (share) Nikon system, i line stepper, device name NSR-2205i12D

[water contact angle]

Using the Concord Interface Science (stock) system, the fully automatic contact angle meter Drop Master series, the device name DM700, the pure water was made into a droplet of 22G needle, and the liquid method was attached to the film by the droplet method (θ/2 method). The water contact angle of the droplets on the surface.

[Optical microscope]

Device: manufactured by Nikon Corporation, device name ECLIPSE E600 POL

The optical microscope was observed at a magnification of 50 times.

[electron microscope]

Device: (share) Hitachi High-Tech Company, device name S-4800

[Synthesis Example (1-1)]

29.17 g of tetraethoxynonane, 116.66 g of propylene glycol monomethyl Ether (PGME for short) was placed in a 300 ml flask, and the mixture was stirred with a magnetic stirrer while dropping 0.019 g of 0.01 mol/L hydrochloric acid into the mixed solution. After the addition, the flask was transferred to an oil bath adjusted to 100 ° C, and the reaction was allowed to proceed for 240 minutes under heating under reflux. Then, the reaction solution was cooled to room temperature, and 116.66 g of PGME was added to the reaction solution, and ethanol, water, and hydrochloric acid of the reaction by-product were distilled off under reduced pressure, and concentrated to obtain a PGME solution of the hydrolyzed condensate (polymer). Next, PGME was added, and the solid residue at 140 ° C was adjusted to 14 mass %. The obtained polymer was a varnish of polyoxyalkylene (pTEOS) composed only of a hydrolyzable decane (a1) component. The weight average molecular weight of the obtained pTEOS by GPC was Mw 1800 in terms of polystyrene.

[Synthesis Example (1-2)]

29.17 g of tetraethoxy decane, 10.70 g of methyltriethoxy decane, and 159.46 g of PGME were placed in a 300 ml flask, and the solution was stirred with a magnetic stirrer while being 0.01 mol/L. 13.33 g of hydrochloric acid was dropped into the mixed solution. After the addition, the flask was transferred to an oil bath adjusted to 100 ° C, and the reaction was allowed to proceed for 240 minutes under heating under reflux. Then, in the same manner as in the synthesis example (1-1), the solid residue at 140 ° C was adjusted to be 14% by mass. The obtained polymer is obtained by dissolving 70 mol% of hydrolyzable decane (a1) and hydrolyzed decane (a2) with a decane monomer having a methyl group having 1 carbon atom and 3 hydrolyzable groups, and 30 mol. The ratio of the % of the ear is a varnish of a hydrolyzed copolymerized polyoxyalkylene (TM73 for short). The weight average molecular weight of the obtained TM73 by GPC is converted into polystyrene. Mw1155.

[Synthesis Example (1-3)]

29.17 g of tetraethoxy decane, 11.54 g of ethyl triethoxy decane, and 162.82 g of PGME were placed in a 300 ml flask, and the solution was stirred with a magnetic stirrer while being 0.01 mol/L. 13.33 g of hydrochloric acid was dropped into the mixed solution. After the addition, the flask was transferred to an oil bath adjusted to 100 ° C, and the reaction was allowed to proceed for 240 minutes under heating under reflux. Then, in the same manner as in the synthesis example (1-1), the solid residue at 140 ° C was adjusted to be 14% by mass. The obtained polymer was 70 mol% of hydrolyzable decane (a1) and hydrolyzed decane (a2) was substituted with a decane monomer having an ethyl group having 3 carbon atoms and 3 hydrolyzable groups, and was 30 mol. A ratio of % to a varnish of a hydrolyzed copolymerized polyoxyalkylene (referred to as TE73). The weight average molecular weight of the obtained TE73 by GPC was Mw1310 in terms of polystyrene.

[Synthesis Example (1-4)]

29.17 g of tetraethoxydecane, 9.86 g of propyltrimethoxydecane, and 156.09 g of PGME were placed in a 300 ml flask, and the solution was stirred with a magnetic stirrer while 0.01 mol/L hydrochloric acid was added. 13.33 g was dropped into the mixed solution. After the addition, the flask was transferred to an oil bath adjusted to 100 ° C, and the reaction was allowed to proceed for 240 minutes under heating under reflux. Then, in the same manner as in the synthesis example (1-1), the solid residue at 140 ° C was adjusted to be 14% by mass. The resulting polymer is 70 mol% hydrolyzed decane (a1) and C as a hydrolyzable decane (a2) having a carbon number of 3 A varnish of a polyoxyalkylene (abbreviated as TT73) hydrolyzed at a ratio of 30 mol% to a decane monomer having three hydrolyzable groups. The weight average molecular weight by GPC of the obtained TT73 was Mw1041 in terms of polystyrene.

[Synthesis Example (1-5)]

29.17 g of tetraethoxydecane, 13.22 g of isobutyltriethoxydecane, and 169.56 g of PGME were placed in a 300 ml flask, and the solution was stirred with a magnetic stirrer while being 0.01 mol/L. 13.33 g of hydrochloric acid was dropped into the mixed solution. After the addition, the flask was transferred to an oil bath adjusted to 100 ° C, and the reaction was allowed to proceed for 240 minutes under heating under reflux. Then, in the same manner as in the synthesis example (1-1), the solid residue at 140 ° C was adjusted to be 14% by mass. The obtained polymer was 70 mol% of hydrolyzable decane (a1) and decane monomer having hydrolyzable decane (a2) having an isobutyl group having 4 carbon atoms and 3 hydrolyzable groups, at 30 mol. A ratio of % is a varnish of a hydrolyzed copolymerized polyoxyalkylene (TI73 for short). The weight average molecular weight of the obtained TI73 by GPC was Mw 1087 in terms of polystyrene.

[Synthesis Example (1-6)]

29.17 g of tetraethoxynonane, 12.38 g of n-hexyltrimethoxydecane, and 166.19 g of PGME were placed in a 300 ml flask, and the solution was stirred with a magnetic stirrer while being 0.01 mol/L. hydrochloric acid 13.33 g was dropped into the mixed solution. After the addition, the flask was transferred to an oil bath adjusted to 100 ° C, and the reaction was allowed to proceed for 240 minutes under heating under reflux. Then, in the same manner as in the synthesis example (1-1), the solid residue at 140 ° C was adjusted to be 14% by mass. The obtained polymer was 70 mol% of hydrolyzable decane (a1) and decane monomer having a hydrolyzable decane (a2) having n-hexyl group having 6 carbon atoms and 3 hydrolyzable groups, at 30 mol. A ratio of % to a varnish of a hydrolyzed copolymerized polyoxyalkylene (referred to as TH73). The weight average molecular weight of the obtained TH73 by GPC was Mw 1060 in terms of polystyrene.

[Synthesis Example (1-7)]

29.17 g of tetraethoxy decane, 3.43 g of isobutyl triethoxy decane, and 130.38 g of PGME were placed in a 300 ml flask, and the solution was stirred with a magnetic stirrer while being 0.01 mol/L. 10.93 g of hydrochloric acid was dropped into the mixed solution. After the addition, the flask was transferred to an oil bath adjusted to 100 ° C, and the reaction was allowed to proceed for 240 minutes under heating under reflux. Then, in the same manner as in the synthesis example (1-1), the solid residue at 140 ° C was adjusted to be 14% by mass. The obtained polymer is obtained by combining 90 mol% of hydrolyzable decane (a1) with a hydrocarbyl decane (a2) having a tetraalkyl group having 4 carbon atoms and 3 hydrolyzable groups of decane monomer. The proportion of the ear % is a varnish of a hydrolyzed copolymerized polyoxyalkylene (TI91 for short). The weight average molecular weight of the obtained TI91 by GPC was Mw1237 in terms of polystyrene.

[Synthesis Example (1-8)]

29.17 g of tetraethoxy decane, 7.71 g of isobutyl triethoxy decane, and 147.52 g of PGME were placed in a 300 ml flask, and the solution was mixed with a magnetic stirrer while being 0.01 mol/L hydrochloric acid. 11.98 g was dropped into the mixed solution. After the addition, the flask was transferred to an oil bath adjusted to 100 ° C, and the reaction was allowed to proceed for 240 minutes under heating under reflux. Then, in the same manner as in the synthesis example (1-1), the solid residue at 140 ° C was adjusted to be 14% by mass. The obtained polymer is obtained by dissolving 80 mol% of hydrolyzable decane (a1) with a hydrocarbyl decane (a2) having a tetrahydric butyl group having 4 carbon atoms and 3 hydrolyzable decane monomers, 20 mol. The proportion of the ear % is a varnish of a hydrolyzed copolymerized polyoxyalkylene (TI82 for short). The weight average molecular weight of the obtained TI82 by GPC was Mw1235 in terms of polystyrene.

[Synthesis Example (1-9)]

20.83 g of tetraethoxy decane, 14.69 g of isobutyl triethoxy decane, and 140.10 g of PGME were placed in a 300 ml flask, and the solution was mixed with a magnetic stirrer while being 0.01 mol/L. 10.81 g of hydrochloric acid was dropped into the mixed solution. After the addition, the flask was transferred to an oil bath adjusted to 100 ° C, and the reaction was allowed to proceed for 240 minutes under heating under reflux. Then, in the same manner as in the synthesis example (1-1), the solid residue at 140 ° C was adjusted to be 14% by mass. The obtained polymer is obtained by dissolving 60 mol% of hydrolyzable decane (a1) with a hydrocarbyl decane (a2) having a tetraalkyl group having 4 carbon atoms and 3 hydrolyzable groups of decane monomers, 40 mol. The percentage of the ear A varnish of a hydrolyzed copolymerized polyoxyalkylene (TI64 for short). The weight average molecular weight of the obtained TI64 by GPC was Mw1051 in terms of polystyrene.

[Synthesis Example (1-10)]

20.83 g of tetraethoxy decane, 22.04 g of isobutyl triethoxy decane, and 171.48 g of PGME were placed in a 300 ml flask, and the solution was mixed with a magnetic stirrer while being 0.01 mol/L. 12.61 g of hydrochloric acid was dropped into the mixed solution. After the addition, the flask was transferred to an oil bath adjusted to 100 ° C, and the reaction was allowed to proceed for 240 minutes under heating under reflux. Then, in the same manner as in the synthesis example (1-1), the solid residue at 140 ° C was adjusted to be 14% by mass. The obtained polymer is obtained by combining 50 mol% of hydrolyzable decane (a1) with a hydrocarbyl decane (a2) having a tetraalkyl group having 4 carbon atoms and 3 hydrolyzable groups of decane monomer. The proportion of the ear % is a varnish of a hydrolyzed copolymerized polyoxyalkylene (TI55 for short). The weight average molecular weight of the obtained TI55 by GPC was Mw 1025 in terms of polystyrene.

[Synthesis Example (1-11)]

16.67 g of tetraethoxydecane, 26.45 g of isobutyltriethoxydecane, and 172.45 g of PGME were placed in a 300 ml flask, and the solution was mixed with a magnetic stirrer while being 0.01 mol/L. 12.25 g of hydrochloric acid was dropped into the mixed solution. After the addition, the flask was transferred to an oil bath adjusted to 100 ° C, and the reaction was allowed to proceed for 240 minutes under heating under reflux. Then, with the synthesis example (1-1) In the same operation, the solid residue adjusted to 140 ° C is converted into 14% by mass. The obtained polymer is obtained by dissolving 40 mol% of hydrolyzable decane (a1) and decane monomer having a hydrolyzable decane (a2) having an isobutyl group having 4 carbon atoms and 3 hydrolyzable groups, 60 mol. The ratio of the % of the ear is a varnish of a hydrolyzed copolymerized polyoxyalkylene (TI46 for short). The weight average molecular weight of the obtained TI46 by GPC was Mw 1015 in terms of polystyrene.

[Synthesis Example (1-12)]

The TI73 obtained in the synthesis example (1-5) was heated and stirred in an oil bath of 100 ° C for 9 hours to confirm that it was Mw 2097 in terms of polystyrene, and a varnish of polyoxyalkylene (TI73M1 for short) was obtained.

[Synthesis Example (1-13)]

The TI73 obtained in the synthesis example (1-5) was heated and stirred in an oil bath of 100 ° C for 20 hours, and it was confirmed that Mw 3014 was converted into polystyrene to obtain a varnish of polysiloxane (TI73M2 for short).

[Synthesis Example (1-14)]

The TI73 obtained in the synthesis example (1-5) was heated and stirred in an oil bath of 100 ° C for 32 hours, and it was confirmed that Mw 4235 was converted into polystyrene (TI73M3) varnish in terms of polystyrene.

[Synthesis Example (1-15)]

The TI73 obtained in the synthesis example (1-5) was heated and stirred in an oil bath of 100 ° C for 62 hours, and it was confirmed that Mw 6357 was obtained in terms of polystyrene to obtain a varnish of polyoxyalkylene (TI73M4 for short).

[Synthesis Example (1-16)]

10.42 g of tetraethoxydecane, 4.72 g of isobutyltriethoxydecane, and 136.25 g of PGME were placed in a 300 ml flask, and the solution was mixed with a magnetic stirrer while being 0.01 mol/L. 4.76 g of hydrochloric acid was dropped into the mixed solution. After the addition, the flask was transferred to an oil bath adjusted to 100 ° C, and the reaction was allowed to proceed for 240 minutes under heating under reflux. Then, in the same manner as in the synthesis example (1-1), the solid residue at 140 ° C was adjusted to be 14% by mass. The obtained polymer is obtained by combining 70 mol% of hydrolyzable decane (a1) with a decane monomer having a hydrolyzable decane (a2) having an isobutyl group having 4 carbon atoms and 3 hydrolyzable groups, to 30 mol. The proportion of the ear % is a varnish of a hydrolyzed copolymerized polyoxyalkylene (TI73L1 for short). The weight average molecular weight of the obtained TI73L1 by GPC was Mw760 in terms of polystyrene.

[Synthesis Example (1-17)]

5.21 g of tetraethoxy decane, 2.36 g of isobutyl triethoxy decane, and 143.82 g of PGME were placed in a 300 ml flask, and the solution was mixed with a magnetic stirrer while being 0.01 mol/L. 2.38 g of hydrochloric acid was dropped into the mixed solution. After the addition, the flask was transferred to an oil bath adjusted to 100 ° C, and the reaction was allowed to proceed for 240 minutes under heating under reflux. Then, with the synthesis example (1-1) In the same operation, the solid residue adjusted to 140 ° C is converted into 14% by mass. The obtained polymer is obtained by combining 70 mol% of hydrolyzable decane (a1) with a decane monomer having a hydrolyzable decane (a2) having an isobutyl group having 4 carbon atoms and 3 hydrolyzable groups, to 30 mol. A proportion of the ear % is a varnish of a hydrolyzed copolymerized polyoxyalkylene (TI73L2 for short). The weight average molecular weight of the obtained TI73L2 by GPC was Mw652 in terms of polystyrene.

[Synthesis Example (1-18)]

20.83 g of tetraethoxydecane, 9.62 g of n-octyltrimethoxydecane, and 121.80 g of PGME were placed in a 300 ml flask, and the solution was mixed with a magnetic stirrer while being 0.01 mol/L. 9.52 g of hydrochloric acid was dropped into the mixed solution. After the addition, the flask was transferred to an oil bath adjusted to 100 ° C, and the reaction was allowed to proceed for 240 minutes under heating under reflux. Then, in the same manner as in the synthesis example (1-1), the solid residue at 140 ° C was adjusted to be 14% by mass. The obtained polymer is obtained by using 70 mol% of a hydrolyzable decane (a1) and a substituted hydrolyzable decane (a2) as a decane monomer having an n-octyl group having 8 carbon atoms and 3 hydrolyzable groups. A varnish of a hydrolyzed copolymerized polyoxyalkylene (TO73 for short) at a ratio of 30 mol%. The weight average molecular weight of the obtained TO73 by GPC was Mw998 in terms of polystyrene.

[Synthesis Example (2-1)]

20.83 g of tetraethoxynonane, 7.04 g of n-propyltrimethoxy 矽 、, 111.49 g of acetone was placed in a 300 ml flask, and the solution was mixed with a magnetic stirrer while dropping 9.52 g of 0.01 mol/L hydrochloric acid into the mixed solution. After the addition, the flask was transferred to an oil bath adjusted to 85 ° C, and the reaction was allowed to proceed for 240 minutes under heating under reflux. Then, the reaction solution was cooled to room temperature, and 111.49 g of propylene glycol monomethyl ether acetate (PGMEA) was added to the reaction solution, and ethanol, methanol, water, hydrochloric acid, and acetone of the reaction by-products were distilled off under reduced pressure. The PGMEA solution of the hydrolysis condensate (polymer) was concentrated. Further, PGMEA was added, and the solid residue at 140 ° C was adjusted to be 14% by mass. The obtained polymer was a varnish of a hydrazine compound (A) containing a hydrolysis condensate (polyoxane), and a varnish of a fully hydrolyzed polyoxyalkylene (P1). The weight average molecular weight of the obtained P1 by GPC was Mw1541 in terms of polystyrene.

PGMEA varnish of P1 was added with PGMEA, and the solid residue at 140 ° C was converted into 6% by mass, and 1H-NMR was measured. As a result of ¹ H-NMR, it was confirmed that the peak of 5.1 ppm of the proton of the PGMEA attributed to the solvent was 1.00, and the peak near 6.0 ppm of the decyl alcohol (Si-OH) attributed to the polyoxyalkylene was 0.32, and many remained. Si-OH. The weight average molecular weight and the ratio of the number of protons by ¹ H-NMR are shown in Table 1.

[Synthesis Example (2-2)]

20.83 g of tetraethoxy decane, 9.44 g of isobutyl triethoxy decane, and 121.11 g of acetone were placed in a 300 ml flask, and the solution was mixed with a magnetic stirrer while being 0.01 mol/L. 9.52 g of hydrochloric acid was dropped into the mixed solution. After the addition, the flask was transferred to an oil bath adjusted to 85 ° C, and the reaction was allowed to proceed for 240 minutes under heating under reflux. Then, the reaction solution was cooled to room temperature, and 121.11 g of PGMEA was added to the reaction solution, and ethanol, water, hydrochloric acid, and acetone of the reaction by-product were distilled off under reduced pressure, and the PGMEA solution of the hydrolyzed condensate (polymer) was obtained by concentration. Further, PGMEA was added, and the solid residue at 140 ° C was adjusted to be 14% by mass. The obtained polymer was a varnish of a hydrazine compound (A) containing a hydrolysis condensate (polyoxane), and was a varnish of a fully hydrolyzed polyoxyalkylene (P2). The weight average molecular weight of P2 and the ratio of the number of protons by ¹ H-NMR are shown in Table 1.

[Synthesis Example (2-3)]

20.83 g of tetraethoxydecane, 8.84 g of n-hexyltrimethoxydecane, and 118.71 g of acetone were placed in a 300 ml flask, and the solution was mixed with a magnetic stirrer while 0.01 mol/L hydrochloric acid was added. 9.52 g was dropped into the mixed solution. After the addition, the flask was transferred to an oil bath adjusted to 85 ° C, and the reaction was allowed to proceed for 240 minutes under heating under reflux. Then, the reaction solution was cooled to room temperature, and 118.71 g of PGMEA was added to the reaction solution, and ethanol, methanol, water, hydrochloric acid, acetone of the reaction by-products were distilled off under reduced pressure, and PGMEA of the hydrolysis condensate (polymer) was obtained by concentration. Solution. Further, PGMEA was added, and the solid residue at 140 ° C was adjusted to be 14% by mass. The obtained polymer was a varnish of a hydrazine compound (A) containing a hydrolysis condensate (polysiloxane), and was a varnish of a fully hydrolyzed polyoxyalkylene (P3). The weight average molecular weight of P3 and the ratio of the number of protons by ¹ H-NMR are shown in Table 1.

[Synthesis Example (2-4)]

20.83 g of tetraethoxy decane, 2.45 g of isobutyl triethoxy decane, and 93.13 g of acetone were placed in a 300 ml flask, and the solution was mixed with a magnetic stirrer while being 0.01 mol/L. 7.80 g of hydrochloric acid was dropped into the mixed solution. After the addition, the flask was transferred to an oil bath adjusted to 85 ° C, and the reaction was allowed to proceed for 240 minutes under heating under reflux. Then, the reaction solution was cooled to room temperature, and 93.13 g of PGMEA was added to the reaction solution, and ethanol, water, hydrochloric acid, and acetone of the reaction by-product were distilled off under reduced pressure, and the PGMEA solution of the hydrolyzed condensate (polymer) was obtained by concentration. Further, PGMEA was added, and the temperature was adjusted to 14% by mass in terms of solid residue at 140 °C. The obtained polymer was a varnish of a hydrazine compound (A) containing a hydrolysis condensate (polysiloxane), and was a varnish of a fully hydrolyzed polyoxyalkylene (P4). The weight average molecular weight of P4 and the ratio of the number of protons by ¹ H-NMR are shown in Table 1.

[Synthesis Example (2-5)]

12.50 g of tetraethoxy decane, 13.22 g of isobutyl triethoxy decane, and 102.89 g of acetone were placed in a 300 ml flask, and the solution was mixed with a magnetic stirrer while being 0.01 mol/L. 7.56 g of hydrochloric acid was dropped into the mixed solution. After the addition, the flask was transferred to an oil bath adjusted to 85 ° C, and the reaction was allowed to proceed for 240 minutes under heating under reflux. Then, the reaction solution was cooled to room temperature, and 102.89 g of PGMEA was added to the reaction solution, and ethanol, water, hydrochloric acid, and acetone of the reaction by-product were distilled off under reduced pressure, and the PGMEA solution of the hydrolyzed condensate (polymer) was obtained by concentration. Further, PGMEA was added, and the solid residue at 140 ° C was adjusted to be 14% by mass. The obtained polymer was a varnish of a hydrazine compound (A) containing a hydrolysis condensate (polysiloxane), and was a varnish of a fully hydrolyzed polyoxyalkylene (P5). The weight average molecular weight of P5 and the ratio of the number of protons by ¹ H-NMR are shown in Table 1.

[Synthesis Example (2-6)]

5.21 g of tetraethoxydecane, 2.36 g of isobutyltriethoxydecane, and 118.59 g of acetone were placed in a 300 ml flask, and the solution was mixed with a magnetic stirrer while being 0.01 mol/L. 2.38 g of hydrochloric acid was dropped into the mixed solution. After the addition, the flask was transferred to an oil bath adjusted to 85 ° C, and the reaction was allowed to proceed for 240 minutes under heating under reflux. Then, the reaction solution was cooled to room temperature, and 118.59 g of PGMEA was added to the reaction solution, and ethanol, water, hydrochloric acid, and acetone of the reaction by-product were distilled off under reduced pressure, and the PGMEA solution of the hydrolyzed condensate (polymer) was obtained by concentration. Further, PGMEA was added, and the temperature was adjusted to 14% by mass in terms of solid residue at 140 °C. The obtained polymer was a varnish of a hydrazine compound (A) containing a hydrolysis condensate (polysiloxane), and was a varnish of a fully hydrolyzed polyoxyalkylene (P6). The weight average molecular weight of P6 and the ratio of the number of protons by ¹ H-NMR are shown in Table 1.

[Synthesis Example (2-7)]

20.83 g of tetraethoxy decane and 83.33 g of acetone were placed in a 300 ml flask, and the solution was mixed with a magnetic stirrer while dropping 7.20 g of 0.01 mol/L hydrochloric acid into the mixed solution. After the addition, the flask was transferred to an oil bath adjusted to 85 ° C, and the reaction was allowed to proceed for 240 minutes under heating under reflux. Then, the reaction solution was cooled to room temperature, and 83.33 g of PGMEA was added to the reaction solution, and ethanol, water, hydrochloric acid, and acetone of the reaction by-product were distilled off under reduced pressure, and the PGMEA solution of the hydrolyzed condensate (polymer) was obtained by concentration. Further, PGMEA was added, and the solid residue at 140 ° C was adjusted to be 14% by mass. The obtained polymer was a varnish of a hydrazine compound (A) containing a hydrolysis condensate (polysiloxane), and was a varnish of a fully hydrolyzed polyoxyalkylene (P7). The weight average molecular weight of P7 and the ratio of the number of protons by ¹ H-NMR are shown in Table 1.

[Synthesis Example (2-8)]

10.42 g of tetraethoxynonane, 16.53 g of isobutyltriethoxydecane, and 107.78 g of acetone were placed in a 300 ml flask, and the solution was mixed with a magnetic stirrer while being 0.01 mol/L. 7.65 g of hydrochloric acid was dropped into the mixed solution. After the addition, the flask was transferred to an oil bath adjusted to 85 ° C, and the reaction was allowed to proceed for 240 minutes under heating under reflux. Then, the reaction solution was cooled to room temperature, and 107.78 g of PGMEA was added to the reaction solution, and ethanol, water, hydrochloric acid, and acetone of the reaction by-product were distilled off under reduced pressure, and the PGMEA solution of the hydrolyzed condensate (polymer) was obtained by concentration. Further, PGMEA was added, and the solid residue at 140 ° C was adjusted to be 14% by mass. The obtained polymer was a varnish of a hydrazine compound (A) containing a hydrolysis condensate (polysiloxane), and was a varnish of a fully hydrolyzed polyoxyalkylene (P8). The weight average molecular weight of P8 and the proton number ratio by ¹ H-NMR are shown in Table 1.

[Synthesis Example (2-9)]

P2 obtained in Synthesis Example 2 was heated and stirred in an oil bath of 100 ° C for 22 hours, and it was confirmed that polystyrene (P9) varnish was obtained by converting polystyrene into Mw3401. The weight average molecular weight of P9 and the ratio of the number of protons by ¹ H-NMR are shown in Table 1.

[Synthesis Example (2-10)]

P2 obtained in Synthesis Example 2 was heated and stirred in an oil bath of 100 ° C for 35 hours, and it was confirmed that polystyrene was converted into Mw 4545 to obtain a varnish of polyoxyalkylene oxide (abbreviated as P10). The weight average molecular weight of P10 and the ratio of the number of protons by ¹ H-NMR are shown in Table 1.

[Synthesis Example (2-11)]

20.83 g of tetraethoxynonane, 7.64 g of methyltriethoxydecane, and 113.90 g of acetone were placed in a 300 ml flask, and the solution was mixed with a magnetic stirrer while 0.01 mol/L of hydrochloric acid was added. 9.52 g was dropped into the mixed solution. After the addition, the flask was transferred to an oil bath adjusted to 85 ° C, and the reaction was allowed to proceed for 240 minutes under heating under reflux. Then, the reaction solution was cooled to room temperature, and 113.90 g of PGMEA was added to the reaction solution, and ethanol, water, hydrochloric acid, and acetone of the reaction by-product were distilled off under reduced pressure, and the PGMEA solution of the hydrolyzed condensate (polymer) was obtained by concentration. Further, PGMEA was added, and the solid residue at 140 ° C was adjusted to be 14% by mass. The obtained polymer was a varnish of a hydrazine compound (A) containing a hydrolysis condensate (polysiloxane), and was a varnish of a fully hydrolyzed polyoxyalkylene (P11). The weight average molecular weight of P11 and the ratio of the number of protons by ¹ H-NMR are shown in Table 1.

[Synthesis Example (2-12)]

20.83 g of tetraethoxynonane, 8.24 g of ethyltriethoxysilane, and 116.30 g of acetone were placed in a 300 ml flask, and the solution was mixed with a magnetic stirrer while 0.01 mol/L hydrochloric acid was added. 9.52 g was dropped into the mixed solution. After the addition, the flask was transferred to an oil bath adjusted to 85 ° C, and the reaction was allowed to proceed for 240 minutes under heating under reflux. Then, the reaction solution was cooled to room temperature, and 116.30 g of PGMEA was added to the reaction solution, and ethanol, water, hydrochloric acid, and acetone of the reaction by-products were distilled off under reduced pressure, and the PGMEA solution of the hydrolyzed condensate (polymer) was obtained by concentration. Further, PGMEA was added, and the solid residue at 140 ° C was adjusted to be 14% by mass. The obtained polymer was a varnish of a hydrazine compound (A) containing a hydrolysis condensate (polysiloxane), and was a varnish of a fully hydrolyzed polyoxyalkylene (P12). The weight average molecular weight of P12 and the ratio of the number of protons by ¹ H-NMR are shown in Table 1.

[Synthesis Example (2-13)]

20.83 g of tetraethoxynonane, 8.24 g of n-octyltrimethoxydecane, and 123.47 g of acetone were placed in a 300 ml flask, and the solution was mixed with a magnetic stirrer while being 0.01 mol/L. 9.52 g of hydrochloric acid was dropped into the mixed solution. After the addition, the flask was transferred to an oil bath adjusted to 85 ° C, and the reaction was allowed to proceed for 240 minutes under heating under reflux. Then, the reaction solution was cooled to room temperature, 123.47 g of PGMEA was added to the reaction solution, and ethanol, methanol, water, hydrochloric acid, acetone of the reaction by-products were distilled off under reduced pressure, and PGMEA of the hydrolysis condensate (polymer) was obtained by concentration. Solution. Further, PGMEA was added, and the solid residue at 140 ° C was adjusted to be 14% by mass. The obtained polymer was a varnish of a hydrazine compound (A) containing a hydrolysis condensate (polysiloxane), and was a varnish of a fully hydrolyzed polyoxyalkylene (P13). The weight average molecular weight of P13 and the ratio of the number of protons by ¹ H-NMR are shown in Table 1.

[Synthesis Example (2-14)]

20.83 g of tetraethoxy decane and 7.04 g of n-propyltrimethoxydecane 111.49 g of ethanol were placed in a 300 ml flask, and the solution was mixed with a magnetic stirrer while 0.01 mol/L hydrochloric acid was added. 9.52 g was dropped into the mixed solution. After the addition, the flask was transferred to an oil bath adjusted to 85 ° C, and the reaction was allowed to proceed for 240 minutes under heating under reflux. Then, the reaction solution was cooled to room temperature, 111.49 g of PGMEA was added to the reaction solution, and ethanol of the solvent, ethanol of the reaction by-product, methanol, water, hydrochloric acid were distilled off under reduced pressure, and the mixture was concentrated to obtain a hydrolyzed condensate (polymer). PGMEA solution. Further, PGMEA was added, and the solid residue at 140 ° C was adjusted to be 14% by mass. The obtained polymer is a varnish of a hydrazine compound containing a hydrolysis condensate (polysiloxane), and is a partially hydrolyzed polyoxy siloxane (referred to as P14). Varnish. The weight average molecular weight of the obtained P14 by GPC was Mw1520 in terms of polystyrene.

The PGMEA varnish of P14 was added with PGMEA, and the solid residue at 140 ° C was converted into 6% by mass, and ¹ H-NMR was measured.

When the peak of 5.1 ppm of the proton of the PGMEA attributed to the solvent was 1.00, the peak near 6.0 ppm of the decyl alcohol (Si-OH) belonging to the polyoxyalkylene was 0.06, and Si was obtained as a result of ¹ H-NMR. -O is very small.

[Synthesis Example (2-15)]

20.83 g of tetraethoxy decane and 9.44 g of isobutyltrimethoxydecane 121.11 g of ethanol were placed in a 300 ml flask, and the solution was mixed with a magnetic stirrer while adding 0.01 mol/L of hydrochloric acid 9.52. g was dropped into the mixed solution. After the addition, the flask was transferred to an oil bath adjusted to 85 ° C, and the reaction was allowed to proceed for 240 minutes under heating under reflux. Then, the reaction solution was cooled to room temperature, 121.11 g of PGMEA was added to the reaction solution, ethanol of the solvent, ethanol of the reaction by-product, water, hydrochloric acid were distilled off under reduced pressure, and the hydrolyzed condensate (polymer) PGMEA solution was obtained by concentration. . Further, PGMEA was added, and the solid residue at 140 ° C was adjusted to be 14% by mass. The obtained polymer was a varnish of a hydrazine compound containing a hydrolysis condensate (polysiloxane), and was a varnish of a partially hydrolyzed polyoxyalkylene (P15). The weight average molecular weight of P15 and the ratio of the number of protons by ¹ H-NMR are shown in Table 1.

[Manufacturing Example 1]

Zirconium dioxide dispersion; propylene glycol monomethyl ether dispersion (abbreviated as B1) containing zirconia particles surface-treated with alkoxy decane (manufactured by Nissan Chemical Industries Co., Ltd.)

The physical property values of the inorganic particle sol obtained in Production Example 1 are shown in Table 2.

<Production of Film Forming Composition (1) and Film> [Example (1-1)]

6.5000 g of B1 obtained in Production Example 1 was weighed in a 50 mL eggplant type flask, followed by addition of 23.8851 g of PGME, and 4.9563 g of TT73 obtained in Synthesis Example (1-4) was added (relative to the solid content of B1, polyfluorene) The solid content of the oxane was 35 mass%), and R-30-N manufactured by Dainippon Ink Chemical Industry Co., Ltd., which is a surfactant, was added to a solution of 0.3965 g diluted to 1% by mass with PGME, and mixed at room temperature until completely uniform. Thus, a varnish (referred to as V(1-1)) having a total mass of the solid component of 7.5% by mass was obtained.

The obtained V(1-1) was evaluated for patterning characteristics. V (1-1) was spin-coated on an 8 inch ruthenium substrate treated with hexamethyldioxane (HMDS) using a clean track ACT8 manufactured by Tokyo Electron Co., Ltd. to a film thickness of 100 nm, and a hot plate was used. Heat at 150 ° C for 1 minute. Next, AZ3100 (manufactured by AZ ELECTRONIC MATERIALS Co., Ltd.) was spin-coated on the obtained film of V (1-1) to have a film thickness of 1.5 μm, and heated at 100 ° C for 1 minute using a hot plate. Then, using an i-line stepper NSR-2205i12D manufactured by Nikon, a light exposure amount of 300 mJ/cm ² was irradiated through a photomask. After the light irradiation, 2.38 mass% of tetramethylammonium hydroxide (TMAH) was used for development for 30 seconds, and the mixture was washed with pure water for 1 minute, and then dried with air. Next, the photosensitive resist was immersed in PGME for 2 minutes, and the resist was peeled off, and the line: Space was observed by an optical microscope to be 5 μm of 1:1. As a result of observation by an optical microscope, an example in the vicinity of Line:Space of 1:1 to 5 μm was evaluated as ○, and an example in which Line:Space was 1:1 to 5 μm or an example of the residual film was evaluated as ×. The results observed with an optical microscope are shown in Fig. 1.

Further, when Line:Space is 1:1 to 5 μm, the length of the Space portion is measured from the top direction of the pattern using an electron microscope. As a result of measuring the length, the width of the Space portion was 5.15 μm. The Space portion was dissolved in the portion of the alkali developer, and the closer to 5 μm, the better the pattern was formed.

The obtained V(1-1) was used to evaluate the heat-resistant refractive index. The film was spin-coated on a ruthenium substrate so that the film thickness of V (1-1) was 100 nm, and the mixture was heated at 150 ° C for 1 minute using a hot plate. After heating, the refractive index at 450 nm was measured. Next, using a hot plate, the film was heated at 300 ° C for 1 hour, and the refractive index at 450 nm was measured, and then the refractive index before and after heating at 300 ° C was compared. The results of the comparison of the refractive indices are shown in Table 3.

The resulting V(1-1) measures the water contact angle. The film was spin-coated on a ruthenium substrate so that the film thickness of V (1-1) was 100 nm, and the mixture was heated at 150 ° C for 1 minute using a hot plate. Then, it was heated at 100 ° C for 1 minute. This heating The two-stage heating of the plate reproduces the heating conditions under which the photosensitive resist is applied and the heat before drying by the dried alkali is developed.

The obtained film was made by using the Drop Master series DM700 of the fully automatic contact angle meter made by Concord Interface Science Co., Ltd., and the pure water was made into a droplet of 22G needle, and the liquid method was attached to the surface of the film by the droplet method (θ/2 method). The water contact angle of the droplets. The results are shown in Table 3.

[Embodiment (1-2)]

The TT73 of Example (1-1) was replaced with TI73 obtained in Synthesis Example (1-5), and the alkali developability, heat resistance, and water contact angle were measured in the same manner as in Example (1-1). The results are shown in Table 3. The results of the optical microscope observation of the pattern are shown in Fig. 2.

Further, when Line:Space is 1:1 to 5 μm, the length of the Space portion is measured from the top direction of the pattern using an electron microscope. As a result of measuring the length, the width of the Space portion was 5.12 μm.

[Example (1-3)]

The TT73 of Example (1-1) was replaced with TH73 obtained in Synthesis Example (1-6), and the alkali developability, heat resistance, and water contact angle were measured in the same manner as in Example (1-1). The results are shown in Table 3. The results of the optical microscope observation of the pattern are shown in Fig. 3.

Further, when Line:Space is 1:1 to 5 μm, the length of the Space portion is measured from the top direction of the pattern using an electron microscope. As a result of measuring the length, the width of the Space portion was 5.12 μm.

[Example (1-4)]

The TT73 of Example (1-1) was replaced with TI91 obtained in Synthesis Example (1-7), and alkali developability, heat resistance, and water contact angle were measured in the same manner as in Example (1-1). The results are shown in Table 3.

[Example (1-5)]

The TT73 of Example (1-1) was replaced with TI82 obtained in Synthesis Example (1-8), and alkali developability, heat resistance, and water contact angle were measured in the same manner as in Example (1-1). The results are shown in Table 3.

[Example (1-6)]

The TT73 of Example (1-1) was replaced with TI64 obtained in Synthesis Example (1-9), and alkali developability, heat resistance, and water contact angle were measured in the same manner as in Example (1-1). The results are shown in Table 3.

[Embodiment (1-7)]

The TT73 of the example (1-1) was replaced with the TI55 obtained in the synthesis example (1-10), and the alkali developability, heat resistance, and water contact angle were measured in the same manner as in the example (1-1). The results are shown in Table 3.

[Embodiment (1-8)]

The TT73 of Example (1-1) was replaced with TI73M1 obtained in Synthesis Example (1-12), and alkali development was measured in the same manner as in Example (1-1). Sex, heat resistance, water contact angle. The results are shown in Table 3. The results of the optical microscope observation of the pattern are shown in Fig. 4.

Further, when Line:Space is 1:1 to 5 μm, the length of the Space portion is measured from the top direction of the pattern using an electron microscope. As a result of measuring the length, the width of the Space portion was 5.15 μm.

[Embodiment (1-9)]

The TT73 of Example (1-1) was replaced with TI73M2 obtained in Synthesis Example (1-13), and alkali developability, heat resistance, and water contact angle were measured in the same manner as in Example (1-1). The results are shown in Table 3.

[Example (1-10)]

The TT73 of Example (1-1) was replaced with TI73L1 obtained in Synthesis Example (1-16), and alkali developability, heat resistance, and water contact angle were measured in the same manner as in Example (1-1). The results are shown in Table 3.

[Embodiment (1-11)]

The TT73 of Example (1-1) was replaced with TI46 obtained in Synthesis Example (1-11), and alkali developability, heat resistance, and water contact angle were measured in the same manner as in Example (1-1). The results are shown in Table 3.

[Comparative Example (1-1)]

The TT73 of Example (1-1) was replaced with the pTEOS obtained in Synthesis Example (1-1), and the alkali development was measured in the same manner as in Example (1-1). Sex, heat resistance, water contact angle. The results are shown in Table 3. The results of the optical microscope observation of the pattern are shown in Fig. 5.

[Comparative Example (1-2)]

The TT73 of Example (1-1) was replaced with TM73 obtained in Synthesis Example (1-2), and alkali developability, heat resistance, and water contact angle were measured in the same manner as in Example (1-1). The results are shown in Table 3.

[Comparative Example (1-3)]

The TT73 of Example (1-1) was replaced with TE73 obtained in Synthesis Example (1-3), and the alkali developability, heat resistance, and water contact angle were measured in the same manner as in Example (1-1). The results are shown in Table 3.

[Comparative Example (1-4)]

The TT73 of Example (1-1) was replaced with TI73M3 obtained in Synthesis Example (1-14), and alkali developability, heat resistance, and water contact angle were measured in the same manner as in Example (1-1). The results are shown in Table 3.

[Comparative Example (1-5)]

The TT73 of Example (1-1) was replaced with TI73M4 obtained in Synthesis Example (1-15), and alkali developability, heat resistance, and water contact angle were measured in the same manner as in Example (1-1). The results are shown in Table 3. The results of the optical microscope observation of the pattern are shown in Fig. 6.

[Comparative Example (1-6)]

The TT73 of Example (1-1) was replaced with TI73L2 obtained in Synthesis Example (1-17), and alkali developability, heat resistance, and water contact angle were measured in the same manner as in Example (1-1). Using TI73L2, the obtained spin coating film was visually confirmed, and the coating unevenness in the form of radiation was clearly observed, and the film forming property was poor.

[Comparative Example (1-7)]

The TT73 of Example (1-1) was replaced with TO73 obtained in Synthesis Example (1-18), and alkali developability, heat resistance, and water contact angle were measured in the same manner as in Example (1-1). The results are shown in Table 3.

With respect to the results of Table 3, Comparative Examples (1-1) to (1-11) and Comparative Examples (1-1) to Comparative Examples (1-7) were compared.

Examples (1-1) to (1-11) and Comparative Examples (1-2) to (1-3) were compared with Comparative Examples (1-4) to Comparative Examples (1-5). In the comparison of the examples (1-7), it was found that the patterning alkali developability of 5 μm of 10 μm or less was good.

Example (1-11) is a weight average molecular weight of 700 to 4000, but the hydrolyzable decane (a1) constituting the hydrazine compound (A) is 40 mol%, and the hydrolyzable decane (a2) is 60 mol%. Total The composition of the polymerization, but some of the water contact angles are outside the preferred range, but can be used depending on the application.

Comparative Examples (1-4) and Comparative Examples (1-5) constitute a bismuth compound The hydrolyzable decane (a1) of the substance (A) is 70 mol%, and the hydrolyzable decane (a2) is a composition in a range in which the polymerization ratio is 30 mol%, but the weight average molecular weight is in the range of 700 to 4,000. outer.

Comparative Example (1-7) has a weight average molecular weight of 700 to In the range of 4000, the polymerization ratio of the hydrolyzable decane (a1) constituting the ruthenium compound (A) is 70 mol%, and the hydrolyzable decane (a2) is 30 mol%, but the hydrolyzable decane is in the range. L in (a2) is an alkyl group having 8 carbon atoms, and is outside the range of a linear, branched or cyclic alkyl group having 3 to 6 carbon atoms.

Example (1-1) to Example (1-11) and Comparative Example (1-1) and Comparative Examples (1-4) to (1-5) and Comparative Example (1-7) were compared with Comparative Example (1-2) and Comparative Example (1-3) to find refraction. The rate of change is good.

Comparative Example (1-2) and Comparative Example (1-3) are hydrolyzable decane L in (a2) is an alkyl group having 1 and 2 carbon atoms, and is outside the range of a linear, branched or cyclic alkyl group having 3 to 6 carbon atoms. When the refractive index is lowered during heat, when L is a compound (A) having 1 and 2 carbon atoms, the low molecular compound which is a ring in the polymer undergoes sublimation upon heat and becomes an air layer. Since the refractive index of air is 1.0, it is known that the refractive index of the film is lowered when the air layer is mixed in the film.

Example (1-1) to Example (1-11) and Comparative Example The water contact angles of (1-1) to Comparative Example (1-7) were compared. Examples (1-1) to (1-10) were made by using the Concord Interface Science (system), fully automatic contact angle meter Drop Master series DM700, and the pure water was made into droplets of 22G needles. The drop method (θ/2 method) calculates the contact angle of water in which the liquid adheres to the droplets on the surface of the film is 60° to 80°. The contact angles of water of Comparative Example (1-2), Comparative Example (1-3), Comparative Example (1-4), and Comparative Example (1-5) were 60° to 80°, in the range, but the refractive index When the heat is not changed, or the 5 μm of the patterned alkali of 10 μm or less is poor in developability, the performance is insufficient when it is used as a target film.

In the present invention, according to the results shown in Table 3 of <Film Forming Composition (1) and Film Preparation>, it is possible to form a high refractive index, high transparency, high heat resistance, high light resistance, and high hardness. In the film forming composition and the pattern forming method of the film for a display device, depending on the use, there is a need for a higher level of patterning property or a film roughness preventing property and a ripening property after the resist film is peeled off. For example, [1] the hydrazine compound (A) is obtained by hydrolyzing and condensing a hydrolyzable decane in a non-alcoholic solvent, [2] using a hardening catalyst (D), [3] using a diketone compound (E), [4] Water (F) and acid (G) are used, and <film formation composition (2) and film production>, <film formation composition (3) and film production>, <film formation composition (4) and The results of the production of the film > can be applied to the above applications, as shown below.

<Film formation composition (2) and production of film> [Embodiment (2-1)]

3.000 g of B1 obtained in Production Example 1 was weighed in a 20 mL eggplant type flask, and then 10.94446 g of propylene glycol monoethyl ether (PGEE) was added, and 2.2875 g of P1 obtained in Synthesis Example (2-1) was added (relatively In the case of the solid component of B1, the solid content of polyoxymethane is 35% by mass), and benzyl triethylammonium chloride (abbreviated as BTEAC) as a curing catalyst (D) is added to form a 1% by mass solution by dilution with PGEE. 0.0915 g, R-30-N, manufactured by Dainippon Ink Chemical Industry Co., Ltd., as a surfactant, was diluted with PGEE to form a 0.1 mass% solution of 0.1830 g, and mixed at room temperature until completely homogeneous to obtain a total solid content. A varnish having a mass of 7.5% by mass (V(2-1) for short).

[Embodiment (2-2)]

A varnish having a total mass of 7.5% by mass of a solid component (V for short) was obtained in the same manner as in Example (2-1) except that P1 of Example (2-1) was replaced by P2 obtained in Synthesis Example (2-2). (2-2)).

[Embodiment (2-3)]

In the same manner as in Example (2-1) except that P1 of Example (2-1) was replaced by P3 obtained in Synthesis Example (2-3), a varnish having a total mass of 7.5% by mass of solid content (V for short) was obtained. (2-3)).

[Example (2-4)]

The P1 obtained in the example (2-1) was replaced with the P4 obtained in the synthesis example (2-4), and the total mass of the solid component was obtained in the same manner as in the example (2-1). A varnish having a quantity of 7.5% by mass (V(2-4) for short).

[Embodiment (2-5)]

In the same manner as in the example (2-1) except that P1 of the example (2-1) was replaced by the P5 obtained in the synthesis example (2-5), a varnish having a total mass of the solid component of 7.5% by mass (abbreviated as V) was obtained. (2-5)).

[Embodiment (2-6)]

In the same manner as in the example (2-1) except that P1 of the example (2-1) was replaced by the P6 obtained in the synthesis example (2-6), a varnish having a total mass of the solid component of 7.5% by mass (abbreviated as V) was obtained. (2-6)).

[Example (2-7)]

In the same manner as in the example (2-1) except that P1 of the example (2-1) was replaced by the P9 obtained in the synthesis example (2-9), a varnish having a total mass of the solid component of 7.5% by mass (abbreviated as V) was obtained. (2-7)).

[Embodiment (2-8)]

3.000 g of B1 obtained in Production Example 1 was weighed in a 20 mL eggplant type flask, and then 9.4379 g of PGEE was added, and 2.2875 g of P2 obtained in Synthesis Example (2-2) was added (when it was solid relative to the solid content of B1) The solid content of the siloxane is 35% by mass), and 1.8300 g of a 1% by mass solution of BTEAC as a curing catalyst (D) is added and diluted with PGEE, and a large Japanese ink chemical industry (share) is added as a surfactant. R-30- N was diluted with PGEE to form 0.1830 g of a 1% by mass solution, and mixed at room temperature until it was completely uniform, and a varnish (referred to as V(2-8)) having a total mass of the solid component of 7.5% by mass was obtained.

[Embodiment (2-9)]

3.000 g of B1 obtained in Production Example 1 was weighed in a 20 mL eggplant type flask, and then 10.94446 g of PGEE was added, and 2.2875 g of P2 obtained in Synthesis Example (2-2) was added (when it was compared with the solid content of B1, it was gathered. The solid content of the siloxane is 35% by mass), and benzyl trimethylammonium chloride (abbreviated as BTMAC) as a curing catalyst (D) is added to dilute PGEE to form a 0.01% by mass solution of 0.019% by weight, and is added as a surfactant. R-30-N manufactured by Nippon Ink Chemical Industry Co., Ltd. was diluted with PGEE to form a solution of 0.1830 g of a 1% by mass solution, and mixed at room temperature until completely uniform, to obtain a varnish having a total mass of 7.5% by mass of solid components ( Referred to as V (2-9)).

[Reference Example (2-1)]

3.000 g of B1 obtained in Production Example 1 was weighed in a 20 mL eggplant type flask, and then 1,1.0239 g of PGEE was added, and 2.2875 g of P1 obtained in Synthesis Example (2-1) was added (when it was compared with the solid content of B1, it was gathered. The solid content of the decane was 35 mass%), and R-30-N manufactured by Dainippon Ink Chemical Industry Co., Ltd., which is a surfactant, was added and diluted with PGEE to form a 0.1 mass% solution of 0.1830 g, and mixed at room temperature until When it was completely uniform, a varnish (abbreviated as RV (2-1)) having a total mass of the solid component to which no hardening catalyst was added was 7.5% by mass.

[Reference Example (2-2)]

A varnish having a total mass of the solid component of 7.5% by mass was obtained in the same manner as in Reference Example (2-1) except that P1 of Reference Example (2-1) was substituted with P2 obtained in Synthesis Example (2-2). RV (2-2)).

[Reference Example (2-3)]

A varnish having a total mass of the solid component of 7.5% by mass was obtained in the same manner as in Reference Example (2-1) except that P1 of Reference Example (2-1) was substituted with P3 obtained in Synthesis Example (2-3). RV (2-3)).

[Reference Example (2-4)]

A varnish having a total mass of the solid component of 7.5% by mass was obtained in the same manner as in Reference Example (2-1) except that P1 of Reference Example (2-1) was substituted with P4 obtained in Synthesis Example (2-4). RV (2-4)).

[Reference Example (2-5)]

A varnish having a total mass of the solid component of 7.5% by mass was obtained in the same manner as in Reference Example (2-1) except that P1 of Reference Example (2-1) was substituted with P5 obtained in Synthesis Example (2-5). RV (2-5)).

[Reference Example (2-6)]

A solid component was obtained in the same manner as in Reference Example (2-1) except that P1 of Reference Example (2-1) was substituted with P7 obtained in Synthesis Example (2-7). A varnish (referred to as RV2-6) with a total mass of 7.5% by mass.

[Reference Example (2-7)]

A varnish having a total mass of the solid component of 7.5% by mass was obtained in the same manner as in Reference Example (2-1) except that P1 of Reference Example (2-1) was substituted with P8 obtained in Synthesis Example (2-8). RV (2-7)).

[Reference Example (2-8)]

A varnish having a total mass of the solid component of 7.5% by mass was obtained in the same manner as in Reference Example (2-1) except that P1 of Reference Example (2-1) was replaced by P10 obtained in Synthesis Example (2-10). RV (2-8)).

[Reference Example (2-9)]

A varnish having a total mass of the solid component of 7.5% by mass was obtained in the same manner as in Reference Example (2-1) except that P1 of Reference Example (2-1) was replaced by P11 obtained in Synthesis Example (2-11). RV (2-9)).

[Reference Example (2-10)]

A varnish having a total mass of the solid component of 7.5% by mass was obtained in the same manner as in Reference Example (2-1) except that P1 of Reference Example (2-1) was substituted with P12 obtained in Synthesis Example (2-12). RV (2-10)).

[Reference Example (2-11)]

Substituting P1 of Reference Example (2-1) for Synthesis Example (2-13) In the same manner as in Reference Example (2-1), a varnish (abbreviated as RV (2-11)) having a total mass of the solid component of 7.5% by mass was obtained.

[Reference Example (2-12)]

A varnish having a total mass of the solid component of 7.5% by mass was obtained in the same manner as in Reference Example (2-1) except that P1 of Reference Example (2-1) was substituted with P14 obtained in Synthesis Example (2-14). RV (2-12)).

[Reference Example (2-13)]

A varnish having a total mass of the solid component of 7.5% by mass was obtained in the same manner as in Reference Example (2-1) except that P1 of Reference Example (2-1) was substituted with P15 obtained in Synthesis Example (2-15). RV (2-13)).

<production of film> [Examples (2-10) to (2-18) and Reference Examples (2-14) to Reference Examples (2-26)] [Characteristic characteristics (tests which have been rigorously evaluated by the alkali developability test of Table 3)]

The obtained V(2-1) to V(2-9) and RV(2-1) to RV(2-13) were evaluated for patterning characteristics. Each varnish was spin-coated on an 8 inch ruthenium substrate treated with hexamethyldioxane (HMDS) to a thickness of 100 nm using a clean track ACT8 manufactured by Tokyo Electron Co., Ltd., and heated at 150 ° C using a hot plate. 1 minute. Next, AZ3100 (manufactured by AZ ELECTRONIC MATERIALS Co., Ltd.) was spin-coated on the obtained film to have a film thickness of 1.5 μm, and heated at 100 ° C for 1 minute using a hot plate. Then, using an i-line stepper NSR-2205i12D manufactured by Nikon, a light exposure amount of 300 mJ/cm ² was irradiated through a photomask. After the light irradiation, 2.38 mass% of tetramethylammonium hydroxide (TMAH) was used for development for 30 seconds, and the mixture was washed with pure water for 1 minute, and then dried with air. Next, the photosensitive resist was immersed in PGME for 2 minutes, and the resist was peeled off, and the line: Space was observed by an optical microscope to be 5 μm of 1:1. As a result of observation by an optical microscope, an example in the vicinity of Line:Space of 1:1 to 5 μm was evaluated as ○, and an example in which Line:Space was 1:1 to 5 μm or an example of the residual film was evaluated as ×.

The results of V(2-1) to V(2-9) and RV(2-1) to RV(2-13) are shown in Table 4. Further, observation results of V(2-1) to V(2-3) and RV(2-1) to RV(2-3) are shown in FIGS. 7 to 12.

Further, Fig. 7 to Fig. 9 measure the length of the Space portion from the top direction of the pattern using an electron microscope where Line:Space is 1:1 to 5 μm. As a result of measuring the length, the width of the Space portion of Fig. 7 was 5.10 μm, the width of the Space portion of Fig. 8 was 5.07 μm, and the width of the Space portion of Fig. 9 was 5.07 μm. Here, the Space portion is dissolved in the portion of the alkali developing solution, and the closer to 5 μm, the better the pattern can be formed.

[heat resistant refractive index]

The obtained V(2-1) to V(2-9) and RV(2-1) to RV(2-13) were evaluated for the heat-resistant refractive index. Each varnish was spin-coated on a ruthenium substrate to have a film thickness of 100 nm, and heated at 150 ° C for 1 minute using a hot plate. plus After the heat, the refractive index at 450 nm was measured. Next, using a hot plate, the film was heated at 300 ° C for 1 hour, and the refractive index at 450 nm was measured, and then the refractive index before and after heating at 300 ° C was compared. The results of the comparison of the refractive indices are shown in Table 4.

[water contact angle]

Each varnish measures the water contact angle. The film was spin-coated on a ruthenium substrate to a thickness of 100 nm, and heated at 150 ° C for 1 minute using a hot plate, followed by heating at 100 ° C for 1 minute. The two-stage heating of the hot plate reproduces the heating conditions under which the photosensitive resist is applied and the heat before drying by the dried alkali is developed.

The obtained film was made by using the Concord Interface Science Co., Ltd., a fully automatic contact angle meter, Drop Master series DM700, and the pure water was made into a droplet of a size of 22 G, and the liquid was attached to the film by the droplet method (θ/2 method). The water contact angle of the droplets on the surface. The results are shown in Table 4.

Note) In the alkali developability test of Table 3, Line:Space is The width of the portion of 1:1 is 5.12 to 5.15 μm, which is also evaluated as ○. However, the test for the patterning characteristic of Table 4 is a test requiring the above level. Therefore, it is evaluated as × when it is less than 5 μm.

From V(2-1) to V(2-9) and RV(2-1) to RV (2-13) When comparing the patterning characteristics of the film as a film, Examples (2-10) to (2-18), Reference Example (2-25), and Reference Examples (2-26) The patterning characteristics are good.

Embodiments (2-10) to (2-18) are the inventions The weight average molecular weight of the compound (A) is in the range of from 700 to 4,000, and the hydrolyzable decane (a1) constituting the hydrazine compound (A) is from 90 mol% to 50 mol%, and the hydrolyzable decane (a2) is 10 mol% to 50 mol% of the copolymerization, and the L of the hydrolyzable decane (a2) is a linear, branched or cyclic alkyl group having 3 to 6 carbon atoms, and has an average particle size of 1 to 100 nm. The contact angle of the water of the film obtained by the composition of the inorganic particles (B) having a refractive index of 1.50 to 2.70, the curing catalyst (C) and the solvent (D) is in the range of 60 to 80.

From the viewpoint of the necessity of hardening the catalyst, the embodiment (2- 10) Comparison to Example (2-14) and Reference Example (2-14) to Reference Example (2-18). Examples (2-10) to (2-14) contained BTEAC as a curing catalyst, and Reference Examples (2-14) to Reference Examples (2-18) contained a composition of BTEAC. By containing a curing catalyst, it is hardened by heat, and the film is provided with a solvent resistance to a resist, an alkali developer, and a resist film peeling liquid, and a pattern of 10 μm or less can be formed. The reference example (2-14) to the reference example (2-18), which does not contain the hardening catalyst, is not imparted with the solvent resistance of the resist, the alkali developer and the resist film peeling liquid, and particularly the alkali resistance is insufficient, so that it is formed. Before the pattern, all the film portions were dissolved in the alkali developing solution, and the pattern could not be obtained.

From the viewpoint of weight average molecular weight, examples (2- 11), Example (2-15), Example (2-16), and Reference Example (2-21) were compared. The weight average molecular weight of the polymer is an example (2- 11) is 1500, embodiment (2-15) is 735, embodiment (2-16) is 3401, and reference example (2-21) is 4545. Here, a polymer having a weight average molecular weight of 700 to 4,000 is used, and the patterning property of the composition or the film is good. When the polymer having a weight average molecular weight of more than 4,000 in Reference Example (2-21) was used, the patterning property of the composition and the film as a film was a residual film because the solubility of the high molecular weight body was lowered.

Hydrolyzable decane (a1) constituting hydrazine compound (A) and water From the viewpoints of the copolymerization ratio of the deuterated decane (a2), the examples (2-11), the examples (2-13), the examples (2-14), and the reference examples (2-20) were compared. The copolymerization ratio of the polymer is (a1) / (a2) = 70 mol% / 30 mol%, and the embodiment (2-13) is (a1) / (a2) = 90. Mohr%/10 mol%, Example (2-14) is (a1)/(a2)=50 mol%/50 mol%, and reference example (2-20) is (a1)/(a2) = 40 mole % / 60 mole %. Here, the polymer copolymerized with the hydrolyzable decane (a1) constituting the hydrazine compound (A) is from 90 mol% to 50 mol%, and the hydrolyzable decane (a2) is from 10 mol% to 50 mol%. The composition and the patterning property of the film are good. When the copolymerization ratio of the reference example (2-20) was (a1)/(a2)=40 mol%/60 mol%, the patterning property of the composition or the film was not obtained. As a result, the hydrophobicity is too high, and the solubility in the alkali developer is lost.

In the hydrolyzable decane (a2) constituting the hydrazine compound (A) From the viewpoints of the number of carbon atoms of L, the examples (2-10) to the examples (2-12) and the reference examples (2-19), the reference examples (2-22) to the reference examples (2-24) Line comparison. The number of carbon atoms of L in the hydrolyzable decane (a2) is 3, the examples (2-11) are 4, the examples (2-12) are 6, and the reference examples (2-19) ) is 0, reference example (2-22) is 1, reference example (2-23) is 2, and reference example (2-24) is 8. Here, L which is a hydrolyzable decane (a2) is a polymer having 3 to 6 carbon atoms, and the composition, the patterning property as a film, and the heat-resistant refractive index are good. Reference Example (2-19) A polyoxyalkylene having a carbon number of 0, a polymer having a carbon number of 1 in Reference Example (2-22), and a carbon number of 2 in Reference Example (2-23) The polymer patterning property was peel development, and a uniform pattern of 5 μm could not be formed. When the polymer having a carbon number of 0 to 2 is copolymerized, the film is condensed, and the solubility developability to the alkali developer cannot be obtained.

The monomer of the reference example (2-24) having a carbon number of 8 is carried out. The copolymerized polymer does not dissolve in the alkali developer and has poor patterning properties. This result can be illustrated by the hydrophilicity of the film surface upon alkali development. The alkali developer is usually an aqueous solution, for example, a thin aqueous solution of TMAH or an aqueous solution of potassium hydroxide. Since these developing solutions are aqueous solutions, when the hydrophobicity of the film is high, they do not permeate into the film and repel. Therefore, the developing property is originally lost. When the film is immersed in the alkali developing solution for a long period of time, it may be dissolved. However, in consideration of the productivity of the process, it is preferable to terminate the alkali developing step at least within 120 seconds, so that the hydrophobicity of the alkali developing solution is repelled, which is a poor film property. .

As a result of this, it was found that it is desirable to take into account the patterning characteristics and resistance. In the case of the thermal refractive index, it is important to copolymerize a specific monomer in a specific ratio, and particularly, among the number of carbon atoms of L in the hydrolyzable decane (a2), there is an optimum value.

Regarding alkali developability, the film surface which has been developed by the above alkali The hydrophobicity is extremely important, and as a result of the examples (2-10) to (2-18) and the reference examples (2-14) to (2-26), the margin of alkali developability (MARGIN) is wide, and It is proved that the parameter of the film which can be formed into a pattern of 10 μm or less in the dissolution developability is a range in which the contact angle of water is from 60° to 80°.

[Light resistance test] [Examples (2-19) to (2-20) and Reference Examples (2-27) to Reference Examples (2-28)]

The obtained V(2-1) to V(2-2) and RV(2-12) to RV(2-13) were evaluated for light resistance.

V(2-1) to V(2-2) and RV(2-12) to RV(2-13) were spin-coated on a ruthenium substrate to have a film thickness of 100 nm, and heated at 150 ° C using a hot plate. 60 minutes. After heating, the film thickness, the refractive index at 450 nm, and the average transmittance were measured. Next, the light resistance test was performed, and the film thickness, refractive index, and average transmittance of the film after the light resistance test were measured. The results are shown in Table 5.

The film thickness and the refractive index of 450 nm measure the film on the ruthenium substrate, and the average transmittance is a film on the quartz substrate. The average transmittance is calculated as an average transmittance of 400 nm to 800 nm.

The light irradiation in the light resistance test was carried out by a general weather corporation Japan Weathering Test Center, and a xenon Arc Lamp having an illuminance of 38.7 W/m ² and an exposure wavelength of 320 nm to 400 nm was used as a light source. The test machine was made of SX75-AP type using a suga test machine. The test environment has a temperature of 42 ± 3 ° C and a relative humidity of 50 ± 5% RH.

The light resistance of the examples (2-19) to (2-20) and the reference examples (2-27) to the reference examples (2-28) were compared. The heat-resistant refractive index and patterning characteristics of Examples (2-19) to (2-20) and Reference Examples (2-27) to Reference (2-28) were good, but Reference Example (2-27) In Reference Example (2-28), the film thickness after the light resistance test was lowered, the refractive index was increased, and the average transmittance was lowered. On the other hand, in Example (2-19) to Example (2-20), the film thickness, the refractive index, and the average transmittance after the light resistance test were not changed.

As a result of the light resistance test, only the polymers of V(2-1) to V(2-2) are completely hydrolyzed, and the polymers of RV(2-12) to RV(2-13) are partially hydrolyzed. Differently, the copolymerization ratio of the monomers is the same, and the weight average molecular weight is also the same degree of the polymer, and therefore, a significant difference occurs due to the difference in the polymerization method of the polymer. That is, it was found that the polymer of the fully hydrolyzed type had a good light resistance test. Fully hydrolyzed polymer, in addition In the thermal step, the thermosetting reaction of the film is completed, and the partially hydrolyzed polymer is in the heating step, the thermosetting reaction is not completely completed, and the alkoxy group remains, which may be caused by the reaction in the light resistance test.

In summary, the above results are used as materials for LEDs. When all of the required heat-resistant refractive index, patterning property, and light resistance are satisfied, it can be achieved by satisfying the following requirements, that is, the weight average molecular weight of the ruthenium compound (A) of the present invention is in the range of 700 to 4,000. The hydrolyzable decane (a1) of the hydrazine compound (A) is from 90 mol% to 50 mol%, and the hydrolyzable decane (a2) is copolymerized from 10 mol% to 50 mol%, and the hydrolyzable decane (a2) L is a linear, branched or cyclic alkyl group having 3 to 6 carbon atoms, and has inorganic particles (B) having an average particle diameter of 1 to 100 nm and a refractive index of 1.50 to 2.70, and a hardening catalyst (D). And the contact angle of the water of the film obtained by the composition of the solvent (C) is in the range of 60 to 80.

<Production of Film Forming Composition (3) and Film> [Example (3-1)]

3.000 g of B1 obtained in Production Example 1 was weighed in a 20 mL eggplant type flask, and then 7.9724 g of propylene glycol monoethyl ether (PGEE) was added, and 2.2875 g of P1 obtained in Synthesis Example (2-1) was added (relatively In the case of the solid component of B1, the solid content of the polyoxyalkylene oxide is 35% by mass), and 3.0515 g of a diketone compound (E) ethyl pyruvate (abbreviated as PE) as a hydrogen bond film roughness preventing material is added, and the interface is added as an interface. R-30-N made by the Japanese ink chemical industry (shares) of the active agent is diluted with PGME 0.1830 g of a 1 mass% solution was mixed at room temperature until it was completely uniform, and a varnish (referred to as V(3-1)) having a total mass of the solid component of 7.5% by mass was obtained.

The obtained V(3-1) was used to evaluate the refractive index. The film was spin-coated on a ruthenium substrate so that the film thickness of V(3-1) was 100 nm, and the mixture was heated at 150 ° C for 1 minute using a hot plate. Next, heating was performed at 300 ° C for 1 hour using a hot plate, and the refractive index at 450 nm was measured and found to be 1.613.

[Embodiment (3-2)]

A varnish having a total mass of 7.5% by mass of a solid component (V for short) was obtained in the same manner as in Example (3-1) except that P1 of Example (3-1) was replaced by P2 obtained in Synthesis Example (2-2). (3-2)).

The obtained V(3-2) was measured in the same manner as in the example (3-1), and the result was 1.610.

[Embodiment (3-3)]

A varnish having a total mass of 7.5% by mass of a solid component (V for short) was obtained in the same manner as in Example (3-1) except that P1 of Example (3-1) was replaced by P3 obtained in Synthesis Example (2-3). (3-3)).

The obtained V(3-3) was measured in the same manner as in the example (3-1), and the result was 1.603.

[Embodiment (3-4)]

Substituting P1 of the embodiment (3-1) for the synthesis example (2-4) In the same manner as in Example (3-1) except for P4, a varnish (abbreviated as V(3-4)) having a total mass of the solid component of 7.5% by mass was obtained.

[Embodiment (3-5)]

A varnish having a total mass of 7.5% by mass of a solid component (V for short) was obtained in the same manner as in Example (3-1) except that P1 of Example (3-1) was replaced by P5 obtained in Synthesis Example (2-5). (3-5)).

[Embodiment (3-6)]

The P1 obtained in the example (3-1) was replaced with the P6 obtained in the synthesis example (2-6), and the same procedure as in the example (3-1) was carried out to obtain a varnish having a total mass of the solid component of 7.5% by mass (abbreviated as V). (3-6)).

[Embodiment (3-7)]

The P1 obtained in the example (3-1) was replaced with the P8 obtained in the synthesis example (2-8), and the same procedure as in the example (3-1) was carried out to obtain a varnish having a total mass of 7.5% by mass of the solid component (abbreviated as V). (3-7)).

[Embodiment (3-8)]

A varnish having a total mass of 7.5% by mass of a solid component (V(3) was obtained in the same manner as in Example (3-1) except that the PE of Example (3-1) was substituted with methyl pyruvate (abbreviated as PM). -8)).

[Embodiment (3-9)]

A varnish having a total mass of a solid component of 7.5% by mass (abbreviated as V (3) was obtained in the same manner as in Example (3-1) except that the PE of Example (3-1) was replaced with ethyl acetoacetone (ACA for short). -9)).

[Reference Example (3-1)]

3.000 g of B1 obtained in Production Example 1 was weighed in a 20 mL eggplant type flask, and then 1,1.0239 g of PGEE was added, and 2.2875 g of P1 obtained in Synthesis Example (2-1) was added (when it was compared with the solid content of B1, it was gathered. The solid content of the decane was 35 mass%), and R-30-N manufactured by Dainippon Ink Chemical Industry Co., Ltd., which is a surfactant, was added and diluted with PGEE to form a 0.1 mass% solution of 0.1830 g, and mixed at room temperature until A varnish (abbreviated as RV (3-1)) having a total mass of the solid content of the diketone compound (E) to which the hydrogen bond film roughness preventing material was not added was obtained.

[Reference Example (3-2)]

The P1 obtained in the reference example (3-1) was replaced with the P2 obtained in the synthesis example (2-2), and the same procedure as in the reference example (3-1) was carried out to obtain a varnish having a total mass of the solid component of 7.5% by mass (abbreviated as RV). (3-2)).

[Reference Example (3-3)]

The P1 obtained in the reference example (3-1) was replaced with the P3 obtained in the synthesis example (2-3), and the same procedure as in the reference example (3-1) was carried out to obtain a varnish having a total mass of the solid component of 7.5% by mass (abbreviated as RV). (3-3)).

[Reference Example (3-4)]

The P1 obtained in the reference example (3-1) was replaced with the P4 obtained in the synthesis example (2-4), and the same procedure as in the reference example (3-1) was carried out to obtain a varnish having a total mass of the solid component of 7.5% by mass (abbreviated as RV). (3-4)).

[Reference Example (3-5)]

The P1 obtained in the reference example (3-1) was replaced with the P5 obtained in the synthesis example (2-5), and the same procedure as in the reference example (3-1) was carried out to obtain a varnish having a total mass of the solid component of 7.5% by mass (abbreviated as RV). (3-5)).

[Reference Example (3-6)]

The P1 obtained in the reference example (3-1) was replaced with the P7 obtained in the synthesis example (2-7), and the same procedure as in the reference example (3-1) was carried out to obtain a varnish having a total mass of the solid component of 7.5% by mass (abbreviated as RV). (3-6)).

<production of film> [Examples (3-10) to Examples (3-18) and Reference Examples (3-7) to Reference Examples (3-12)] [Alkaline solubility and film roughness characteristics after peeling of the resist film]

The obtained alkali solubility was evaluated from V(3-1) to V(3-9) and RV(3-1) to RV(3-6). Each varnish was spin-coated on an 8 inch ruthenium substrate treated with hexamethyldioxane (HMDS) to a thickness of 100 nm using a clean track ACT8 manufactured by Tokyo Electron Co., Ltd., and heated at 150 ° C using a hot plate. 1 minute. Next, AZ3100 (manufactured by AZ ELECTRONIC MATERIALS Co., Ltd.) was spin-coated on the obtained film to have a film thickness of 1.5 μm, and heated at 100 ° C for 1 minute using a hot plate. Then, using an i-line stepper NSR-2205i12D manufactured by Nikon, a light exposure amount of 300 mJ/cm ² was irradiated through a photomask. After the light irradiation, 2.38 mass% of tetramethylammonium hydroxide (TMAH) was used for development for 30 seconds, and the mixture was washed with pure water for 1 minute, and then dried with air. In this case, the case where the alkali developing solution was dissolved and developed was evaluated as ○, and the example of peeling development or undissolved was evaluated as ×, as shown in Table 6.

Next, the photosensitive resist was immersed in PGME for 2 minutes, and the resist was peeled off, and the pattern was not observed by an optical microscope (where the photosensitive resist was laminated and peeled off). As a result of observation by an optical microscope, the case where no film roughness did not occur was evaluated as ○, and the case where film roughness occurred was evaluated as ×, V(3-1) to V(3-9) and RV(3-1) to RV(3- The results of 6) are shown in Table 6. Further, the observation results of V(3-1) to RV(3-1) are shown in Figs. 13 to 14.

When V(3-1) to V(3-9) and RV(3-1) to RV(3-6) are used as a film, and the alkali solubility of the film is compared, Example (3-10) is The alkali solubility of the examples (3-18) and the reference examples (3-7) to the reference examples (3-11) was good. On the other hand, in the hydrolyzable decane (a2) of the reference example (3-12), the number of carbon atoms of L was 0, and the alkali developer was peeled off, and the desired solution developability could not be obtained.

When V(3-1) to V(3-9) and RV(3-1) to RV(3-6) are used as a film, the film roughness characteristics after the film of the film is peeled off are compared, and Examples (3-10) to Example (3-18), film roughness after peeling of the resist film did not occur, and Reference Example (3-7) to Reference Example (3- 12) Film roughness occurs. These differences are differences in the presence or absence of the diketone compound (E) of the hydrogen bond film roughness preventive agent.

From the results of Table 6, it was found that both alkali solubility and resist were desired. In the film roughening property after film peeling, it is important to copolymerize a specific monomer at a specific ratio, and in particular, the number of carbon atoms of L in the hydrolyzable decane (a2) has an optimum value.

When combining the above results, it is intended to be used as a material for LEDs. The required alkali solubility and the film roughness characteristic after the release of the resist film can be achieved by satisfying the following requirements, that is, the weight average molecular weight of the ruthenium compound (A) of the present invention is in the range of 700 to 4000. Preferably, the hydrolyzable decane (a1) constituting the hydrazine compound (A) is from 90 mol% to 50 mol%, and the hydrolyzable decane (a2) is from 10 mol% to 50 mol% for copolymerization, and hydrolyzable decane (a2) L is a linear, branched or cyclic alkyl group having 3 to 6 carbon atoms, and has inorganic particles (B) having an average particle diameter of 1 to 100 nm and a refractive index of 1.50 to 2.70, and hydrogen bonding. The constituents of the composition composed of the film roughness preventing agent (E) and the solvent (C).

<Production of Film Forming Composition (4) and Film> [Example (4-1)]

3.000 g of B1 obtained in Production Example 1 was weighed in a 20 mL eggplant type flask, and then 8.3058 g of propylene glycol monoethyl ether (PGEE) was added, and 2.2875 g of P1 obtained in Synthesis Example (2-1) was added (relatively In the case of the solid component of B1, the solid content of polyoxymethane is 35% by mass), and benzyltriethylammonium chloride as a hardening catalyst (D) is added (simple BTEAC) was diluted with PGEE to form 0.019 g of a 1% by mass solution, and acetic acid was added to dilute with PGEE to form a 0.9% by mass solution of 1% by mass, and R-30-N manufactured by Dainippon Ink Chemical Industry Co., Ltd. as a surfactant was added. 0.1830 g of a 1% by mass solution was diluted with PGEE, and 1.8458 g of ion-exchanged water (12% by mass in the total solvent) was added thereto, and mixed at room temperature until completely uniform, and the total mass of the solid component was 7.5% by mass. Varnish (referred to as V (4-1)).

The obtained V(4-1) was used to evaluate the refractive index. The film was spin-coated on a ruthenium substrate so that the film thickness of V(4-1) was 100 nm, and the hot plate was heated at 150 ° C for 1 minute. Next, the film was heated at 300 ° C for 1 hour using a hot plate, and the refractive index at 450 nm was measured and found to be 1.616.

[Embodiment (4-2)]

A varnish having a total mass of 7.5% by mass of a solid component (V for short) was obtained in the same manner as in Example (4-1) except that P1 of Example (4-1) was substituted with P2 obtained in Synthesis Example (2-2). (4-2)).

The obtained V(4-2) was measured in the same manner as in the example (4-1), and the result was 1.612.

[Embodiment (4-3)]

A varnish having a total mass of 7.5% by mass of a solid component (V for short) was obtained in the same manner as in Example (4-1) except that P1 of Example (4-1) was replaced by P3 obtained in Synthesis Example (2-3). (4-3)).

The obtained V(4-3) was measured in the same manner as in the example (4-1). The result is 1.608.

[Example (4-4)]

A varnish having a total mass of 7.5% by mass of a solid component (V for short) was obtained in the same manner as in Example (4-1) except that P1 of Example (4-1) was replaced by P4 obtained in Synthesis Example (2-4). (4-4)).

[Embodiment (4-5)]

The P1 obtained in the example (4-1) was replaced with the P5 obtained in the synthesis example (2-5), and the same procedure as in the example (4-1) was carried out to obtain a varnish having a total mass of the solid component of 7.5% by mass (abbreviated as V). (4-5)).

[Example (4-6)]

A varnish having a total mass of 7.5% by mass of a solid component (V for short) was obtained in the same manner as in Example (4-1) except that P1 of Example (4-1) was replaced with P6 obtained in Synthesis Example (2-6). (4-6)).

[Embodiment (4-7)]

In the same manner as in Example (4-1) except that P1 of Example (4-1) was replaced with P9 obtained in Synthesis Example (2-9), a varnish having a total mass of 7.5% by mass of solid content (V for short) was obtained. (4-7)).

[Embodiment (4-8)]

3.000 g of the scale obtained in Production Example 1 in a 20 mL eggplant type flask B1, Next, 7.9832 g of PGEE was added, and 2.2875 g of P2 obtained in Synthesis Example (2-2) was added (the solid content of polysiloxane was 35 mass% with respect to the solid content of B1), and it was added as a hardening contact. The BTEAC of the medium (D) was diluted with PGEE to form a solution of 0.475 g of a 1% by mass solution, and 0.960 g of a solution of 1% by mass was added by diluting acetic acid with PGEE, and R-made by Dainippon Ink Chemical Industry Co., Ltd. as a surfactant was added. 30-N was diluted with PGEE to form 0.1830 g of a 1% by mass solution, and 1.8512 g of ion-exchanged water (12% by mass in the total solvent) was added, and mixed at room temperature until completely homogeneous, and the total mass of the solid component was obtained. 7.5% by mass of varnish (referred to as V(4-8)).

[Embodiment (4-9)]

A varnish having a total mass of 7.5% by mass of a solid component was obtained in the same manner as in Example (4-1) except that the BTEAC of Example (4-1) was changed to benzyltrimethylammonium chloride (abbreviated as BTMAC). (referred to as V (4-9)).

[Embodiment (4-10)]

3.000 g of B1 obtained in Production Example 1 was weighed in a 20 mL eggplant type flask, and then 8.2252 g of PGEE was added, and 2.2875 g of P2 obtained in Synthesis Example (2-2) was added (when it was compared with the solid content of B1, it was gathered. The solid content of the siloxane is 35% by mass), and 0.1830 g of a solution of 1% by mass of BTEAC as a curing catalyst (D) is added by dilution with PGEE, and 0.9150 g of a solution of 1% by mass is added by diluting acetic acid with PGEE. R-30-N manufactured by Dainippon Ink Chemical Industry Co., Ltd., which is a surfactant, was diluted with PGEE to form a solution of 0.1830 g of a 1% by mass solution, and then added 1.8471 g of ion-exchanged water (the ratio of the total solvent was 12% by mass) The mixture was mixed at room temperature until it was completely uniform, and a varnish (referred to as V(4-10)) having a total mass of the solid component of 7.5% by mass was obtained.

[Embodiment (4-11)]

3.000 g of B1 obtained in Production Example 1 was weighed in a 20 mL eggplant type flask, and then 8.8409 g of PGEE was added, and 2.2875 g of P2 obtained in Synthesis Example (2-2) was added (when it was compared with the solid content of B1, it was gathered. The solid content of the siloxane is 35% by mass), and the amount of the BTEAC as the curing catalyst (D) is 0.1830 g, which is diluted with PGEE to form a 1% by mass solution, and the acetic acid is added to the PGEE to form a 0.9% by mass solution of 1% by mass. R-30-N manufactured by Nippon Ink Chemical Industry Co., Ltd., which is a surfactant, is diluted with PGEE to form a solution of 0.1830 g of a 1% by mass solution, and 1.2314 g of ion-exchanged water is added (the ratio of the total solvent is 8% by mass). The mixture was mixed at room temperature until it was completely homogeneous, and a varnish (referred to as V(4-11)) having a total mass of the solid component of 7.5% by mass was obtained.

[Embodiment (4-12)]

3.0000 g of B1 obtained in Production Example 1 was weighed in a 20 mL eggplant type flask, and then 7.6095 g of PGEE was added, and 2.2875 g of P2 obtained in Synthesis Example (2-2) was added (when it was compared with the solid content of B1, it was gathered. The solid content of the siloxane is 35% by mass), and is added as a hardening catalyst (D). BTEAC was diluted with PGEE to form 0.1830 g of a 1% by mass solution, and acetic acid was added to dilute with PGEE to form a 0.9% by mass solution of 1% by mass, and R-30-N manufactured by Dainippon Ink Chemical Industry Co., Ltd. as a surfactant was added to PGEE. 0.1830 g of a solution of 1% by mass was diluted, and 2.4628 g of ion-exchanged water was added (the ratio of the total solvent was 16% by mass), and the mixture was mixed at room temperature until it was completely uniform, and a varnish having a total mass of 7.5% by mass of the solid component was obtained ( Referred to as V (4-12)).

[Embodiment (4-13)]

3.000 g of B1 obtained in Production Example 1 was weighed in a 20 mL eggplant type flask, and then 6.6121 g of PGEE was added, and 2.2875 g of P2 obtained in Synthesis Example (2-2) was added (when it was compared with the solid content of B1, it was gathered. The solid content of the decane was 35 mass%), and the BTEAC as a curing catalyst (D) was added to dilute PGEE to form a solution of 0.1830 g of a 1 mass% solution, and the acetic acid was added to dilute PGEE to form a solution of 2.7450 g of a 1 mass% solution. R-30-N manufactured by Nippon Ink Chemical Industry Co., Ltd., which is a surfactant, is diluted with PGEE to form a solution of 0.1830 g of a 1% by mass solution, and 1.8742 g of ion-exchanged water is added (the ratio of the total solvent is 12% by mass). The mixture was mixed at room temperature until it was completely uniform, and a varnish (referred to as V(4-13)) having a total mass of the solid component of 7.5% by mass was obtained.

[Embodiment (4-14)]

3.000 g of B1 obtained in Production Example 1 was weighed in a 20 mL eggplant type flask, and then 7.4186 g of PGEE was added, and Synthesis Example (2-2) was added. 2.2875 g of P2 (solid content of polyoxymethane was 35 mass% with respect to the solid content of B1), and BTAAC as a hardening catalyst (D) was added and diluted with PGEE to form a solution of 0.1830 g of a 1 mass% solution. Addition of formic acid to a solution of 1.300 g of a 1% by mass solution diluted with PGEE, and addition of R-30-N manufactured by Dainippon Ink Chemical Industry Co., Ltd. as a surfactant, diluted with PGEE to form a solution of 0.18% by mass of 1 mass%, and then added with ions 1.8607 g of water (12% by mass in the total solvent) was exchanged, and it was mixed at room temperature until it was completely uniform, and a varnish (referred to as V(4-14)) having a total mass of the solid component of 7.5% by mass was obtained.

[Embodiment (4-15)]

3.000 g of B1 obtained in Production Example 1 was weighed in a 20 mL eggplant type flask, and then 4.9990 g of PGEE was added, and 2.2875 g of P2 obtained in Synthesis Example (2-2) was added (when it was compared with the solid content of B1, it was gathered. The solid content of the siloxane is 35% by mass), and the amount of the BTEAC as the curing catalyst (D) is 0.1830 g, which is diluted with PGEE to form a 1% by mass solution, and the propionic acid is added and diluted with PGEE to form a 4.5% by mass solution of 4.5% by weight. As a surfactant, R-30-N manufactured by Dainippon Ink Chemical Industry Co., Ltd. was diluted with PGEE to form a solution of 0.1830 g of a 1% by mass solution, and 1.9013 g of ion-exchanged water was added (the ratio of the total solvent was 12% by mass). The mixture was mixed at room temperature until it was completely homogeneous, and a varnish (referred to as V(4-15)) having a total mass of the solid component of 7.5% by mass was obtained.

[Embodiment (4-16)]

The acetal (abbreviated as V(4-16)) having a total mass of the solid component of 7.5% by mass was obtained in the same manner as in Example (4-10) except that the acetic acid of Example (4-10) was replaced with oxalic acid.

[Embodiment (4-17)]

The acetic acid of Example (4-10) was replaced with maleic acid, and the same procedure as in Example (4-10) was carried out to obtain a varnish (referred to as V(4-17)) having a total mass of the solid component of 7.5% by mass.

[Embodiment (4-18)]

3.000 g of B1 obtained in Production Example 1 was weighed in a 20 mL eggplant type flask, and then 5.2295 g of PGEE and 3.0763 g of ethyl pyruvate (abbreviated as PE. diketone compound) were added, and Synthesis Example (2-2) was added. The obtained 2.2875 g of P2 (solid content of polyoxymethane was 35 mass% with respect to the solid content of B1), and BREAAC as a hardening catalyst (D) was added and diluted with PGEE to form a 0.01 mass% solution of 0.015 g. The addition of acetic acid was diluted with PGEE to form 0.9150 g of a 1% by mass solution, and R-30-N manufactured by Dainippon Ink Chemical Industry Co., Ltd. as a surfactant was added to dilute with PGEE to form a solution of 0.18% by mass of 1 mass%, and then add ions. 1.8458 g of water (12% by mass in the total solvent) was exchanged, and it was mixed at room temperature until it was completely uniform, and a varnish (referred to as V(4-18)) having a total mass of the solid component of 7.5% by mass was obtained.

[Embodiment (4-19)]

3.000 g of B1 obtained in Production Example 1 was weighed in a 20 mL eggplant type flask, and then 5.1466 g of PGEE and 3.0785 g of PE were added, and 2.2875 g of P2 obtained in Synthesis Example (2-2) was added (relative to B1). In the case of a solid component, the solid content of polyoxymethane is 35% by mass), and B830AC as a curing catalyst (D) is added to dilute PGEE to form a solution of 0.1830 g of a 1% by mass solution, and acetic acid is added to dilute with PGEE to form a 1% by mass solution. 0.9150 g, R-30-N manufactured by Dainippon Ink Chemical Industry Co., Ltd., which is a surfactant, is diluted with PGEE to form a 1 mass% solution of 0.1830 g, and then ion-exchanged water is added to 1.8471 g (the ratio in the total solvent is 12% by mass), mixed at room temperature until completely uniform, and a varnish (referred to as V(4-19)) having a total mass of the solid component of 7.5% by mass was obtained.

[Embodiment (4-20)]

3.000 g of B1 obtained in Production Example 1 was weighed in a 20 mL eggplant type flask, and then 2.8637 g of PGEE and 3.1237 g of PE were added, and 2.2875 g of P2 obtained in Synthesis Example (2-2) was added (relative to B1). In the case of a solid component, the solid content of polyoxymethane is 35% by mass), and B830AC as a curing catalyst (D) is added to dilute PGEE to form a solution of 0.1830 g of a 1% by mass solution, and acetic acid is added to dilute with PGEE to form a 1% by mass solution. 2.7450g, R-30-N manufactured by Dainippon Ink Chemical Industry Co., Ltd., which is a surfactant, is diluted with PGEE to form a 1 mass% solution of 0.1830 g, and then ion-exchanged water is added to 2.990 g (the ratio of the total solvent is 16% by mass), mixed at room temperature until completely uniform, and a varnish (referred to as V(4-20)) having a total mass of the solid component of 7.5% by mass was obtained.

[Reference Example (4-1)]

3.000 g of B1 obtained in Production Example 1 was weighed in a 20 mL eggplant type flask, and then 8.3865 g of PGEE was added, and 2.2875 g of P1 obtained in (2-1) was added (Polyoxime relative to the solid content of B1) The solid content of the alkane was 35% by mass), and 0.9150 g of a solution of 1% by mass was added by diluting acetic acid with PGEE, and R-30-N manufactured by Dainippon Ink Chemical Industry Co., Ltd. as a surfactant was added to form a dilution with PGEE. 0.1830 g of a mass % solution, and 1.8444 g of ion-exchanged water (12% by mass in the total solvent) were added, and the mixture was mixed at room temperature until it was completely uniform, and a hardening catalyst (D) without the addition of the example (4-1) was obtained. Example: A varnish having a total mass of the solid component of 7.5% by mass (abbreviated as RV (4-1)).

[Reference Example (4-2)]

The P1 obtained in the reference example (4-1) was replaced with the P2 obtained in the synthesis example (2-2), and the same procedure as in the reference example (4-1) was carried out to obtain a hardening catalyst to which the compound (4-2) was not added. Example: a varnish having a total mass of a solid component of 7.5% by mass (abbreviated as RV (4-2)).

[Reference Example (4-3)]

The P1 obtained in Reference Example (4-1) was replaced with P3 obtained in Synthesis Example (2-3), and the same procedure as in Reference Example (4-1) was carried out to obtain a hardening catalyst to which Example (4-3) was not added. Example: a varnish having a total mass of a solid component of 7.5% by mass (abbreviated as RV (4-3)).

[Reference Example (4-4)]

The P1 of Reference Example (4-1) was replaced with P4 obtained in Synthesis Example (2-4), and the same procedure as Reference Example (4-1) was carried out to obtain a hardening catalyst to which Example (4-4) was not added. Example: a varnish having a total mass of a solid component of 7.5% by mass (abbreviated as RV (4-4)).

[Reference Example (4-5)]

The P1 of Reference Example (4-1) was replaced with P5 obtained in Synthesis Example (2-5), and the same procedure as Reference Example (4-1) was carried out to obtain a hardening catalyst to which Example (4-5) was not added. Example: a varnish having a total mass of a solid component of 7.5% by mass (abbreviated as RV (4-5)).

[Reference Example (4-6)]

3.000 g of B1 obtained in Production Example 1 was weighed in a 20 mL eggplant type flask, and then 10.1516 g of PGEE was added, and 2.2875 g of P1 obtained in Synthesis Example (2-1) was added (when it was solid relative to the solid content of B1) The solid content of the decane was 35 mass%), and benzyl triethylammonium chloride (BTEAC) as a hardening catalyst (D) was added to dilute with PGEE to form a 0.01% by mass solution of 0.01% by mass, and acetic acid was added to dilute with PGEE. 0.9150 g of a 1% by mass solution was formed, and R-30-N manufactured by Dainippon Ink Chemical Industry Co., Ltd. as a surfactant was added to dilute with PGEE to form a 0.1 mass% solution of 0.1830 g, and mixed at room temperature until completely homogeneous. An example in which ion-exchanged water of Example (4-1) was not added was obtained: the total mass of the solid component was 7.5% by mass of varnish (referred to as RV (4-6)).

[Reference Example (4-7)]

The P1 of Reference Example (4-6) was replaced with P2 obtained in Synthesis Example (2-2), and the same procedure as Reference Example (4-6) was carried out to obtain ion-exchanged water to which Example (4-2) was not added. Example: a varnish having a total mass of a solid component of 7.5% by mass (abbreviated as RV (4-7)).

[Reference Example (4-8)]

The P1 of Reference Example (4-6) was replaced with P3 obtained in Synthesis Example (2-3), and the same procedure as Reference Example (4-6) was carried out to obtain ion-exchanged water to which Example (4-3) was not added. Example: a varnish having a total mass of a solid component of 7.5% by mass (abbreviated as RV (4-8)).

[Reference Example (4-9)]

The P1 of Reference Example (4-6) was replaced with P4 obtained in Synthesis Example (2-4), and the same procedure as Reference Example (4-6) was carried out to obtain ion-exchanged water to which Example (4-4) was not added. Example: a varnish having a total mass of a solid component of 7.5% by mass (abbreviated as RV (4-9)).

[Reference Example (4-10)]

The P1 of Reference Example (4-6) was replaced with P5 obtained in Synthesis Example (2-5), and the same procedure as Reference Example (4-6) was carried out to obtain ion-exchanged water to which Example (4-5) was not added. Example: The total mass of solid components is 7.5 mass % varnish (referred to as RV (4-10)).

[Reference Example (4-11)]

3.000 g of B1 obtained in Production Example 1 was weighed in a 20 mL eggplant type flask, and then 9.1124 g of PGEE was added, and 2.2875 g of P1 obtained in Synthesis Example (2-1) was added (when it was compared with the solid content of B1, it was gathered. The solid content of the oxime is 35 mass%), and BREAAC as a curing catalyst (D) is added to a mixture of 0.0915 g of a solution of 1% by mass diluted with PGEE, and a large Japanese ink chemical industry (share) is added as a surfactant. R-30-N was diluted with PGEE to form 0.1830 g of a 1% by mass solution, and 1.8322 g of ion-exchanged water (12% by mass in the total solvent) was added, and mixed at room temperature until completely uniform, and an unadded example was obtained. 4-1) Examples of the acid: a varnish having a total mass of the solid component of 7.5% by mass (abbreviated as RV (4-11)).

[Reference Example (4-12)]

In the same manner as in Reference Example (4-11), except that P1 of Reference Example (4-11) was replaced with P2 obtained in Synthesis Example (2-2), an example in which the acid of Example (4-2) was not added was obtained: A varnish having a total mass of the solid component of 7.5% by mass (abbreviated as RV (4-12)).

[Reference Example (4-13)]

The P1 of Reference Example (4-11) was replaced with P3 obtained in Synthesis Example (2-3), and the same operation as Reference Example (4-11) was carried out to obtain an unadded Example. (4-3) Example of the acid: a varnish having a total mass of the solid component of 7.5% by mass (abbreviated as RV (4-13)).

[Reference Example (4-14)]

In the same manner as in Reference Example (4-11), except that P1 of Reference Example (4-11) was substituted with P4 obtained in Synthesis Example (2-4), an example in which the acid of Example (4-4) was not added was obtained: A varnish having a total mass of the solid component of 7.5% by mass (abbreviated as RV (4-14)).

[Reference Example (4-15)]

The P1 of Reference Example (4-11) was replaced with P5 obtained in Synthesis Example (2-5), and the same procedure as Reference Example (4-11) was carried out to obtain an example in which the acid of Example (4-5) was not added: A varnish having a total mass of the solid component of 7.5% by mass (abbreviated as RV (4-15)).

[Reference Example (4-16)]

In the same manner as in Example (4-1) except that P1 of Example (4-1) was replaced by P7 obtained in Synthesis Example (2-7), a varnish having a total mass of 7.5% by mass of solid content (abbreviated as RV) was obtained. (4-16)).

[Reference Example (4-17)]

A varnish (referred to as RV for a total mass of 7.5% by mass) of a solid component was obtained in the same manner as in Example (4-1) except that P1 of Example (4-1) was substituted with P8 obtained in Synthesis Example (2-8). (4-17)).

[Reference Example (4-18)]

A varnish (referred to as RV for a total mass of 7.5% by mass) of a solid component was obtained in the same manner as in Example (4-1) except that P1 of Example (4-1) was replaced by P10 obtained in Synthesis Example (2-10). (4-18)).

[Reference Example (4-19)]

In the same manner as in Example (4-1), P1 of Example (4-1) was replaced with P11 obtained in Synthesis Example (2-11), and a varnish having a total mass of 7.5% by mass of solid content (abbreviated as RV) was obtained. (4-19)).

[Reference Example (4-20)]

A varnish (referred to as RV for a total mass of 7.5% by mass) of a solid component was obtained in the same manner as in Example (4-1) except that P1 of Example (4-1) was replaced by P12 obtained in Synthesis Example (2-12). (4-20)).

[Reference Example (4-21)]

A varnish (referred to as RV for a total mass of 7.5% by mass) of a solid component was obtained in the same manner as in Example (4-1) except that P1 of Example (4-1) was replaced by P13 obtained in Synthesis Example (2-13). (4-21)).

[Reference Example (4-22)]

The P1 obtained in the example (4-1) was substituted with the P14 obtained in the synthesis example (2-14), and the same procedure as in the example (4-1) was carried out to obtain the total mass of the solid component. A varnish of 7.5 mass% (referred to as RV (4-22)).

[Reference Example (4-23)]

In the same manner as in Example (4-1) except that P1 of Example (4-1) was replaced with P15 obtained in Synthesis Example (2-15), a varnish having a total mass of 7.5% by mass of solid content (abbreviated as RV) was obtained. (4-23)).

[Reference Example (4-24)]

3.000 g of B1 obtained in Production Example 1 was weighed in a 20 mL eggplant type flask, and then 6.6927 g of PGEE was added, and 2.2875 g of P2 obtained in Synthesis Example (2-2) was added (when it was compared with the solid content of B1, it was gathered. The solid content of the decane was 35% by mass), and 0.0915 g of a solution of 1% by mass of BTEAC as a curing catalyst (D) was added and diluted with PGEE, and 2.7450 g of a solution of 1% by mass was added by diluting with PGEE. R-30-N manufactured by Nippon Ink Chemical Industry Co., Ltd., which is a surfactant, is diluted with PGEE to form a solution of 0.1830 g of a 1% by mass solution, and 1.8729 g of ion-exchanged water is added (the ratio of the total solvent is 12% by mass). The mixture was mixed at room temperature until it was completely homogeneous, and a varnish (abbreviated as RV (4-24)) having a total mass of the solid component of 7.5% by mass was obtained.

[Reference Example (4-25)]

The nitric acid of Reference Example (4-24) was replaced with sulfuric acid, and a varnish (abbreviated as RV (4-25)) having a total mass of 7.5% by mass of a solid component was obtained in the same manner as in Reference Example (4-24).

[Reference Example (4-26)]

3.000 g of B1 obtained in Production Example 1 was weighed in a 20 mL eggplant type flask, and then 9.1043 g of PGEE was added, and 2.2875 g of P2 obtained in Synthesis Example (2-2) was added (when it was compared with the solid content of B1, it was gathered. The solid content of the oxane was 35% by mass), and 0.0915 g of a 1% by mass solution of BTEAC as a curing catalyst (D) was added and diluted with PGEE, and acetic acid was added to dilute PGEE to form a solution of 1% by mass of 0.0092 g, which was added as R-30-N manufactured by Nippon Ink Chemical Industry Co., Ltd., which is a surfactant, is diluted with PGEE to form a solution of 0.1830 g of a 1% by mass solution, and 1.8324 g of ion-exchanged water is added (the ratio of the total solvent is 12% by mass). The mixture was mixed at room temperature until it was completely homogeneous, and a varnish (abbreviated as RV (4-26)) having a total mass of the solid component of 7.5% by mass was obtained.

[Reference Example (4-27)]

3.000 g of B1 obtained in Production Example 1 was weighed in a 20 mL eggplant type flask, and then 9.5363 g of PGEE was added, and 2.2875 g of P2 obtained in Synthesis Example (2-2) was added (when it was compared with the solid content of B1, it was gathered. The solid content of the siloxane is 35% by mass), and 0.0915 g of a solution of 1% by mass of BTEAC as a curing catalyst (D) is added by dilution with PGEE, and 0.9150 g of a solution of 1% by mass is added by diluting acetic acid with PGEE, and added as R-30-N manufactured by Nippon Ink Chemical Industry Co., Ltd., which is a surfactant, is diluted with PGEE to form a solution of 0.1830 g of a 1% by mass solution, and 0.6153 g of ion-exchanged water is added (the ratio of the total solvent is 4% by mass). Room temperature mixing The varnish (abbreviated as RV (4-27)) having a total mass of the solid component of 7.5% by mass was obtained until the mixture was completely uniform.

[Reference Example (4-28)]

3.000 g of B1 obtained in Production Example 1 was weighed in a 20 mL eggplant type flask, and then 7.0753 g of PGEE was added, and 2.2875 g of P2 obtained in Synthesis Example (2-2) was added (when it was compared with the solid content of B1, it was gathered. The solid content of the siloxane is 35% by mass), and 0.0915 g of a solution of 1% by mass of BTEAC as a curing catalyst (D) is added by dilution with PGEE, and 0.9150 g of a solution of 1% by mass is added by diluting acetic acid with PGEE, and added as R-30-N manufactured by Nippon Ink Chemical Industry Co., Ltd., which is a surfactant, is diluted with PGEE to form a solution of 0.1830 g of a 1% by mass solution, and 3.0763 g of ion-exchanged water is added (the ratio of the total solvent is 20% by mass). The mixture was mixed at room temperature until it was completely uniform, and a varnish (abbreviated as RV (4-28)) having a total mass of the solid component of 7.5% by mass was obtained.

V(4-1) to V(4-20) and RV(4) obtained in Examples (4-1) to (4-20) and Reference Examples (4-1) to Reference Examples (4-28) The composition of -1) to RV (4-28) is shown in Tables 7 to 10. Further, each varnish was measured for pH using a digital pH meter, and the results are shown in Table 7.

Table 7 to Table 10 show the weight average molecular weight of the parameter of the present invention, the copolymerization ratio of the hydrolyzable decane (a1) constituting the hydrazine compound (A) and the hydrolyzable decane (a2), and the L in the hydrolyzable decane (a2). The number of carbon atoms, the presence or absence of the addition of the hardening catalyst, the presence or absence of acid addition, and The type, the presence or absence of water addition, and the proportion (% by weight) of water in the total solvent.

In Tables 7 to 10, the acid type is acetic acid with G1 It is indicated that formic acid is represented by G2, propionic acid is represented by G3, oxalic acid is represented by G4, maleic acid is represented by G5, nitric acid is represented by G6, and sulfuric acid is represented by G7.

<Preservation stability test of varnish> [cooking test]

V(4-1) to V(4-20) and RV(4) obtained in Examples (4-1) to (4-20) and Reference Examples (4-1) to Reference Examples (4-28) -1) After the varnish of RV (4-28) was prepared, the aging test was carried out in an oven having a temperature of 40 ° C and a relative humidity of 50%. The ripening test time was 336 hours.

Before the aging test, the varnish was made into a film to confirm whether or not foreign matter was generated on the surface of the film. Each of the varnishes was spin-coated on an 8-inch ruthenium substrate using a clean track ACT8 manufactured by Tokyo Electron Co., Ltd. to a thickness of 100 nm, and fired at 150 ° C for 1 minute using a hot plate.

The film was observed with an optical microscope, and no foreign matter was observed on the surface of the coating film. A uniform film was obtained as an example. ○, a foreign matter was generated, and an example in which the storage stability test was defective was evaluated as ×, as shown in Tables 11 to 12.

<production of film> [graphical characteristics]

The obtained V(4-1) to V(4-20) and RV(4-1) to RV(4-28) were evaluated for patterning characteristics. Each of the varnishes was spin-coated on an 8 inch ruthenium substrate treated with hexamethyldioxane (HMDS) to a thickness of 100 nm using a clean track ACT8 manufactured by Tokyo Electron Co., Ltd., and was heated at 150 ° C using a hot plate. Fired in 1 minute. Then, AZ3100 (manufactured by AZ ELECTRONIC MATERIALS Co., Ltd.) was spin-coated on the obtained film to have a film thickness of 1.5 μm, and baked at 100 ° C for 1 minute using a hot plate. Then, using an i-line stepper NSR-2205i12D made of Nikon, a dose of 300 mJ/cm ² was irradiated with light through a reticle. After the light irradiation, 2.38 mass% of tetramethylammonium hydroxide (TMAH) was used for development for 30 seconds, and the mixture was washed with pure water for 1 minute, and then dried with air. Next, the photosensitive resist was immersed in PGME for 2 minutes, and the resist was peeled off, and the line: Space was observed by an optical microscope to be 5 μm of 1:1. As a result of observation by an optical microscope, an example in which the Line:Space is 1:1 to 5 μm is evaluated as ○, and an example in which Line:Space is 1:1 to 5 μm or an example of the residual film is evaluated as ×, V (4-1) The results up to V(4-20) and RV(4-1) to RV(4-28) are shown in Tables 11 to 12. Also, V(4-1) to V(4-3), V(4-10), V(4-14) to V(4-17), and RV(4-1) to RV(4-3) The observation results are shown in Figs. 15 to 25 .

Further, Fig. 15 to Fig. 22 measure the length of the Space portion from the top direction of the pattern using an electron microscope where Line:Space is 1:1 to 5 μm. As a result of measuring the length, the width of the Space portion of FIG. 15 is 5.04 μm, the width of the Space portion of FIG. 16 is 5.02 μm, the width of the Space portion of FIG. 17 is 5.02 μm, and the width of the Space portion of FIG. 18 is 5.01 μm. The width of the Space portion of 19 is 5.01 μm, the width of the Space portion of Fig. 20 is 5.01 μm, the width of the Space portion of Fig. 21 is 5.01 μm, and the width of the Space portion of Fig. 22 is 5.01 μm. Here, the Space portion is dissolved in the portion of the alkali developing solution, and the closer to 5 μm, the better the pattern can be formed.

[water contact angle]

The obtained water contact angles were measured from V(4-1) to V(4-20) and RV(4-1) to RV(4-28). The film was spin-coated on a ruthenium substrate to a thickness of 100 nm, and fired at 150 ° C for 1 minute using a hot plate, followed by firing at 100 ° C for 1 minute. The two-stage firing in the hot plate reproduces the firing conditions under which the photosensitive resist is applied and the heat before drying by the dried alkali is developed.

The obtained film was made by using the Drop Master series DM700 of the fully automatic contact angle meter made by Concord Interface Science Co., Ltd., and the pure water was made into a droplet of 22G needle, and the liquid method was attached to the surface of the film by the droplet method (θ/2 method). The water contact angle of the droplets. The results are shown in Tables 11 to 12.

In Tables 7 to 12, V(4-1) to V(4-20) and The foreign matter of the varnish before and after the ripening of RV (4-1) and RV (4-28) and the patterning characteristics of the film were compared.

Varnished weight average molecules of V(4-1) to V(4-20) The hydrolyzable decane (a1) constituting the hydrazine compound (A) is from 90 mol% to 50 mol%, and the hydrolyzable decane (a2) is from 10 mol% to 50 mol% in the range of from 700 to 4,000. Copolymerization, and the L of the hydrolyzable decane (a2) is a linear, branched or cyclic alkyl group having 3 to 6 carbon atoms, and has an average particle diameter of 1 to 100 nm and a refractive index of 1.50 to 2.70. a varnish composed of particles (B), a curing catalyst (D), water (F), an acid (G), and a solvent (C), wherein the ratio of water (F) in the total solvent is from 6% by weight to 18% by weight. The pH of the varnish was controlled to 3 to 5, and no foreign matter was generated in the varnish before and after the aging, and no foreign matter was found on the obtained film.

Reference Example (4-1) to Reference Example (4-5) are free from hardening touch In the case of the medium (D), when the patterning property was evaluated, the film was excessively dissolved in the alkali developing solution, and the pattern could not be obtained. From this result, it was found that the hardening catalyst (D) was an essential component.

Reference example (4-6) to reference example (4-10) are not containing water In the example of (F), when the patterning property was evaluated, the film was not dissolved in the alkali developing solution, and the pattern could not be obtained. Water (F) is a component which is required to exhibit the sclerosing property of the hydrazine compound (A) in the varnish, to improve the hardenability at the time of heat, and to stabilize and moderately exhibit the hydrogen ion concentration of the acid (G).

Reference Example (4-11) to Reference Example (4-15) are acid free In the case of (G), there is a problem that foreign matter is generated after the ripening. This is the varnish pH of 6.8, which is more stable with stanol but promotes decane. Alcohol condensation, foreign matter is produced in the varnish. This result shows that the acid (G) is an essential component.

Reference Example (4-16), Reference Example (4-19), and Reference Example (4-20) are examples in which L of the hydrolyzable decane (a2) is an alkyl group having 0 to 2 carbon atoms, but evaluation patterning In the case of the characteristics, the film was peeled and developed for the alkali developing solution, and the pattern could not be obtained. This is because the condensation is excessively carried out, and the alkali developing solution does not exhibit dissolution developability. In addition, the reference example (4-21) is an example in which L of the hydrolyzable decane (a2) is an alkyl group having 8 carbon atoms. However, when the patterning property is evaluated, the film is not dissolved in the alkali developer, and the pattern cannot be obtained. . As a result of the above, it is known that L of the hydrolyzable decane (a2) is a linear, branched or cyclic alkyl group having 3 to 6 carbon atoms. Further, since the L of the hydrolyzable decane (a2) is a linear, branched or cyclic alkyl group having 3 to 6 carbon atoms, the water contact angle of the obtained film is in the range of 60 to 80 . In order to obtain dissolution developability for an alkali developer, it is apparent that the hydrophilicity of the film is very important, and the optimum hydrophobicity is found from the structure of the ruthenium compound.

Reference Example (4-17) is a non-hydrolyzable decane (a1) constituting the hydrazine compound (A) of 90 mol% to 50 mol%, and a hydrolyzable decane (a2) of 10 mol% to 50 mol%. The polymer to be copolymerized is an example of a polymer obtained by copolymerizing a hydrolyzable decane (a1) of 40 mol% and a hydrolyzable decane (a2) of 60 mol%, but when evaluating the patterning property, The film was not dissolved in the alkali developer, and the pattern could not be obtained. From this result, it was found that the copolymerization ratio of the hydrolyzable decane (a1) and the hydrolyzable decane (a2) was important, and the example (4-5) used the hydrolyzable decane (a1). An example of a polymer copolymerized by 50 mol% and hydrolyzable decane (a2) of 50 mol%, no alkali solubility was found, and thus a total of hydrolyzable decane (a1) and hydrolyzable decane (a2) were known. The polymerization ratio has the best value.

Reference Example (4-18) uses a weight average molecular weight of In the case of the polymer of 4545, when the patterning property was evaluated, the film was peeled and developed for the alkali developer, and the pattern could not be obtained. From the results, it was found that when the weight average molecular weight of the ruthenium compound (A) is too high, it is peeled and developed, and the weight average molecular weight has an optimum value.

Reference example (4-22) and reference example (4-23) are both used An example of the hydrazine compound (A) which is hydrolyzed. Both of them showed no foreign matter in the patterning characteristics and before and after ripening, which was a good result. The results of the light resistance test are described later.

Reference examples (4-24) and reference examples (4-25) are acid species The type was changed to a strong acid, and the pH of the varnish was set to 1.2. The varnish of Reference Example (4-24) and Reference Example (4-25) produced a gel insoluble in solvent (C) after aging. From this result, it was found that the pH of the varnish had the optimum value.

Reference example (4-26) reduces the amount of acetic acid added, An example of adding 0.01 phr to make the pH of the varnish 5.6. Reference Example (4-26) After the ripening, foreign matter was generated. From this result, it was found that the pH of the varnish had the optimum value.

Reference example (4-27) and reference example (4-28) are water The addition amount of (F) was set to 4% and 20%. In Reference Example (4-27), foreign matter was generated after the aging, and in Reference Example (4-28), when the varnish was applied to the substrate, streaks were generated, and a uniform film could not be obtained. thus As a result, it was found that the amount of water (F) added had the optimum value.

[Light resistance test] [Examples (4-21) to Examples (4-22) and Reference Examples (4-29) to Reference Examples (4-30)]

The obtained V(4-1) to V(4-2) and RV(4-22) to RV(4-23) were evaluated for light resistance.

V(4-1) to V(4-2) and RV(4-22) to RV(4-23) were spin-coated on a ruthenium substrate to have a film thickness of 100 nm, and were heated at 150 ° C using a hot plate. Fired in 60 minutes. After the firing, the film thickness, the refractive index at 450 nm, and the average transmittance were measured. Next, the light resistance test was performed, and the film thickness, refractive index, and average transmittance of the film after the light resistance test were measured. The results are shown in Table 13.

The film thickness and the refractive index of 450 nm measure the film on the ruthenium substrate, and the average transmittance is a film on the quartz substrate. The average transmittance is an average transmittance of 400 nm to 800 nm.

The light irradiation in the light resistance test was carried out by a general weather corporation Japan Weathering Test Center, and a xenon Arc Lamp having an illuminance of 38.7 W/m ² and an exposure wavelength of 320 nm to 400 nm was used as a light source. The test machine was made of SX75-AP type using a suga test machine. The test environment has a temperature of 42 ± 3 ° C and a relative humidity of 50 ± 5% RH.

The light resistances of Examples (4-21) to (4-22) and Reference Examples (4-29) to Reference Examples (4-30) were compared. In the examples (4-21) to (4-22) and the reference examples (4-29) to (4-30), after the patterning property and the ripening, no foreign matter was generated and it was good, but the reference example was used. (4-29) to Reference Example (4-30), the film thickness after the light resistance test was lowered, the refractive index was increased, and the average transmittance was lowered. The film thickness, refractive index, and average transmittance of the examples (4-21) to (4-22) after the light resistance test were not changed.

As a result of the light resistance test, the polymers of V(4-1) to V(4-2) are completely hydrolyzed, and the polymers of RV(4-22) to RV(4-23) are partially hydrolyzed. However, since the copolymerization ratio of the monomers is the same and the weight average molecular weight is also the same degree of the polymer, there is a significant difference depending on the polymerization method of the polymer. That is, it was found that the fully hydrolyzed polymer was excellent in the light resistance test. The fully hydrolyzed polymer is subjected to a calcination step, the thermal hardening reaction of the film is completed, and the partially hydrolyzed polymer is not completely finished in the calcination step, and the reaction is carried out in the light resistance test due to the residual alkoxy group. Caused by it.

In summary, when the high refractive index, the heat-resistant refractive index, the high-patterning property, the light resistance, and the varnish stability after the ripening are required as the materials for the LED, the hydrolysis of the present invention can be contained. The hydrazine is subjected to hydrolytic condensation in a non-alcohol solvent to obtain a ruthenium compound (A) having a weight average molecular weight of 700 to 4,000, an inorganic particle (B) having an average particle diameter of 1 to 100 nm and a refractive index of 1.50 to 2.70, and a hardening contact. The film forming composition of the medium (D), water (F), acid (G), and solvent (C) is achieved.

[Industrial availability]

The film-forming composition of the present invention has a hydrolyzable decane (a1) of 90 mol% to 50 mol% by using a weight average molecular weight of the ruthenium compound (A) of from 700 to 4,000, and hydrolyzable decane ( A2) is a range of copolymerization of 10 mol% to 50 mol%, L of the hydrolyzable decane (a2) is a range of linear, branched or cyclic alkyl groups having 3 to 6 carbon atoms, water contact angle It is a very characteristic composition in the range of 60° to 80°, and can be used as a coating film for LEDs. The patterning property of 10 μm or less is good, and the heat of refractive index can be obtained without a step such as a dry process. A well-changing permanent film.

The film obtained by the present invention can satisfy the high refractive index, high transparency, high heat resistance, high light resistance, and patterning characteristics of 10 μm or less at a time, and thus can be suitably used as a liquid crystal display, a plasma display, a cathode ray tube, and an organic It is used in electronic devices such as light-emitting displays, electronic papers, LEDs, solid-state imaging devices, solar cells, and organic thin film transistors. In particular, it is suitable for use as a member for LEDs requiring high light resistance.

Claims (22)

A film-forming composition (1) comprising: a hydrolyzable decane (a1) represented by the formula (a1) and a hydrolyzable decane (a2) represented by the formula (a2): [Chem. 1] Si(R ¹ ) ₄ Formula (a1) L-Si(R ² ) ₃ Formula (a2) (wherein R ¹ and R ² each represent an alkoxy group having 1 to 20 carbon atoms, a decyloxy group having 2 to 20 carbon atoms or a halogen a hydrolytic condensate of a hydrolyzable decane having a weight average molecular weight of from 700 to 4,000, having a weight average molecular weight of from 700 to 4,000, having a molecular weight of from 700 to 4,000, having a molecular weight of from 700 to 4,000, and having from 1 to 100 nm Inorganic particles (B) and a solvent (C) having an average particle diameter of 1.50 to 2.70. The film forming composition (1) of claim 1, wherein the ratio of the hydrazine compound (A) to the hydrolyzable decane (a1) to the hydrolyzable decane (a2) is 90 mol% to 50 mol% of the hydrolyzable decane (a1). %, hydrolyzable decane (a2) contains 10 mol% to 50 mol% of hydrolyzable decane for hydrolysis condensation. The film formation composition (1) of claim 1, wherein the hydrazine compound (A) is obtained by hydrolyzing and condensing a hydrolyzable decane in a non-alcohol solvent. The film of claim 3 forms a composition (1) in which the non-alcohol solvent is a ketone Or ether. The film of claim 3 forms a composition (1) in which the non-alcohol solvent is acetone or tetrahydrofuran. The film forming composition (1) of claim 3, wherein the solvent (C) comprises a solvent for the hydrolysis of the hydrolyzable decane and a solvent for the reaction of the non-alcoholic solvent used for the subsequent hydrolysis, and a solvent for removing the hydrolysis of the hydrolyzed decane. Solvent. The film of claim 1 is a composition (1) in which the inorganic particles (B) are zirconium dioxide. The film of claim 3 is a composition (2) further comprising a hardening catalyst (D) selected from the group consisting of an ammonium salt, a phosphine, a phosphonium salt, a phosphonium salt, or a chelate compound. The film of claim 3 is a composition (3) further containing a diketone compound (E) selected from the group consisting of 1,2-dione and/or 1,3-diketone. The film forming composition (3) of claim 9, wherein the diketone compound (E) contains the following formula (3) and/or the following formula (4): A compound wherein (wherein W represents a carbon atom or an oxygen atom) is a skeleton. The film of claim 9 is a composition (3) wherein the diketone compound (E) is butanedione, methyl pyruvate, ethyl pyruvate or ethyl acetonactone. The film of claim 8 forms a composition (4) further comprising water (F) and acid (G). A method for producing a film-forming composition (1) according to claim 1, which comprises the step of hydrolyzing a hydrolyzable decane containing a hydrolyzable decane (a1) and a hydrolyzable decane (a2) in a solvent (c1), A step of obtaining a varnish of the compound (A) having a weight average molecular weight of 700 to 4,000, and dispersing the inorganic particles (B) having an average particle diameter of 1 to 100 nm and a refractive index of 1.50 to 2.70 by dispersion by a dynamic light scattering method The medium (c2) is obtained by a step of obtaining a sol, and mixing the varnish of the cerium compound (A) with the sol of the inorganic particles (B) to obtain a film-forming composition containing the cerium compound (A), the inorganic particles (B), and the solvent (C). step. A process for producing a film-forming composition (2) according to claim 8, which comprises the step of: hydrolyzing a hydrolyzable decane containing a hydrolyzable decane (a1) and a hydrolyzable decane (a2) in a non-alcohol solvent (c1) Hydrolysis to obtain a varnish of the ruthenium compound (A) having a weight average molecular weight of 700 to 4,000, and dispersion of inorganic particles (B) having an average particle diameter of 1 to 100 nm and a refractive index of 1.50 to 2.70 as measured by dynamic light scattering method In the step of obtaining a sol in the dispersion medium (c2), the varnish of the cerium compound (A) and the sol of the inorganic particles (B) and the curing catalyst (D) are mixed to obtain a cerium-containing compound (A), inorganic particles (B), and hardening. Step of forming a composition of the catalyst (D) and the solvent (C) Step. A process for producing a film-forming composition (3) according to claim 9, which comprises the step of: hydrolyzing a hydrolyzable decane containing a hydrolyzable decane (a1) and a hydrolyzable decane (a2) in a non-alcohol solvent (c1) Hydrolysis to obtain a varnish of the ruthenium compound (A) having a weight average molecular weight of 700 to 4,000, and dispersion of inorganic particles (B) having an average particle diameter of 1 to 100 nm and a refractive index of 1.50 to 2.70 as measured by dynamic light scattering method The step of obtaining a sol in the dispersion medium (c2), mixing the varnish of the cerium compound (A), the sol of the inorganic particles (B), and the diketone compound (E) to obtain a cerium compound (A), inorganic particles (B), and The step of forming a composition of the film of the ketone compound (E) and the solvent (C). A process for producing a film-forming composition (4) of claim 12, which comprises the step of: hydrolyzing a hydrolyzable decane containing a hydrolyzable decane (a1) and a hydrolyzable decane (a2) in a non-alcohol solvent (c1) Hydrolysis to obtain a varnish of the ruthenium compound (A) having a weight average molecular weight of 700 to 4,000, and dispersion of inorganic particles (B) having an average particle diameter of 1 to 100 nm and a refractive index of 1.50 to 2.70 as measured by dynamic light scattering method In the step of obtaining a sol in the dispersion medium (c2), the varnish of the cerium compound (A), the sol of the inorganic particles (B), the curing catalyst (D), water (F) and the acid (G) are mixed to obtain a cerium-containing compound ( A), inorganic particles (B), hardening catalyst (D), water (F), acid The step of forming a composition of the film of (G) and solvent (C). A pattern forming method for applying a photosensitive resist to a film obtained by forming a composition of any one of Claim 1 to Claim 12, and drying the photosensitive resist film After light irradiation, followed by development, the resist film was peeled off. A film obtained by coating a film-forming composition of any one of Claims 1 to 12 with a refractive index of 1.50 to 1.90 at a wavelength of 633 nm. The film of claim 18, wherein the contact angle of the water of the film surface is from 60° to 80°. The film of claim 18 is used as a light extraction film or a protective film. A device having an electronic device containing the film of claim 18. The device of claim 21, wherein the electronic device is an LED.