Novel surface treatment agent, silica sol, and photosensitive resin composition

Abstract

[Problem] To provide: a surface treatment agent which has optimum solubility in an alkali developer solution that is used for an electronic device; silica particles which have alkali-soluble sites that are introduced into the surfaces by the surface treatment agent, and an organosol; and a photosensitive resin composition which contains the silica particles. [Solution] A thermosetting photosensitive resin composition which contains component (A), component (B), solvent (C), and component (D) described below. Component (A): silica particles which are surface-modified with an alkali-developable alkoxysilane compound represented by formula (1) and have a particle diameter of 1 nm to 1 µm; Component (B): an alkali-soluble resin; Component (C): a solvent; Component (D): a photosensitizing agent (In the formula, R1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; one of R2, R3, and R4 represents a monovalent group that has an alkoxysilyl group, and the other two each independently represent a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, a branched alkyl group having 3 to 16 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a phenyl group, a benzyl group, a phenethyl group, a phenylsulfonyl group, a meth(acryloyloxy)ethyl group, or a meth(acryloyloxy)propyl group; the alkyl group and the branched alkyl group may be substituted with a halogen atom, or the alkyl group and the branched alkyl group may be substituted with a urea group; the urea group may be substituted with one or more groups selected from among a monovalent group having an ester moiety, an alkyl group having a urea moiety that is substituted with a monovalent group having an ester moiety, a phenyl group having a urea moiety that is substituted with a monovalent group having an ester moiety, a phenyl group, and an alkyl group; a phenyl group, a benzyl group, a phenethyl group, and a phenylsulfonyl group in the above definition may be substituted with a group selected from among an alkyl group, an alkoxy group, a halogen atom, a nitro group, and a cyano group; and L represents an alkylene group having 1 to 4 carbon atoms, or a phenylene group.)

Description

Novel surface treatment agent, silica sol, and photosensitive resin composition

[0001] The present invention relates to a photosensitive resin composition containing silica particles and a cured film obtained therefrom. More specifically, it relates to a surface treatment agent having optimal alkali developability, silica particles and organosols into which alkali-soluble moieties have been introduced using this surface treatment agent, a photosensitive resin composition containing these silica particles and its cured film, and various materials using the cured film.

[0002] Photosensitive resin compositions eliminate the need for resist-based processes, and are therefore used in permanent films such as interphase insulating films and buffer coatings used in semiconductor devices where process simplification is necessary, as well as in electronic devices such as microlenses used in optical elements and solid-state image sensors where miniaturization and high integration are required. Furthermore, as the performance of electronic devices is rapidly improving and there is a growing trend towards lighter, thinner, more transparent, and more flexible devices, it has been proposed to enhance their functionality by incorporating inorganic fillers into the resin (Patent Document 1). For example, among inorganic fillers, spherical silica (hereinafter referred to as silica particles) is known to be used in solder resists and heat-resistant films because of its low coefficient of thermal expansion and excellent packing properties. However, increasing the amount of silica particles improves the elastic modulus derived from the silica particles, while decreasing the tensile strength due to the increase in the interface between the silica particles and the resin. Therefore, surface treatment with a silane coupling agent having reactive functional groups such as amino groups or (meth)acryloyl groups is performed on the surface of the silica particles to suppress the deterioration of the coating film properties (Patent Document 2). For this reason, using a photosensitive hybrid resin composition with appropriately surface-treated silica particles is an important technology from both a process and performance perspective when fabricating high-performance electronic devices. However, silica particles are generally difficult to dissolve in aqueous calcium carbonate, aqueous potassium hydroxide, or aqueous hydroxytetramethylammonium solutions used in photosensitive resin compositions. For this reason, they are generally used in combination with resin compositions that have high alkali developability (Patent Document 3). However, because silica particles have poor developability, it is difficult to add them in large quantities to resin compositions. For this reason, it is necessary to treat the surface of the silica particles with a silane coupling agent (surface treatment agent) that has good alkali developability and contains structures such as carboxylic acid or succinic acid as substituents. However, carboxylic acid is known to dissolve too much in alkaline developers (Non-Patent Document 1), so there has been a need for the development of a surface treatment agent with optimal solubility in alkaline developers, silica particles and organosols in which alkali-soluble parts are introduced to the surface by the surface treatment agent, and a photosensitive resin composition containing the silica particles.

[0003] International Publication No. 2017 / 057741, Japanese Patent Publication No. 2018-165795, Japanese Patent Publication No. 2013-145280

[0004] Recent Advances in Polyimide and Aromatic Polymers, 2010, pp. 27-29.

[0005] The present invention has been made in view of the above circumstances, and the problem it seeks to solve is to provide a surface treatment agent having optimal solubility in an alkaline developer used in electronic devices, silica particles and organosols on which alkali-soluble parts are introduced to the surface by the surface treatment agent, and a photosensitive resin composition containing the silica particles.

[0006] As a result of diligent research to achieve the above objective, the present inventors discovered that by using silica particles surface-modified with a specific compound, the problem of silica particles remaining in the developed portion when developing a patterned film obtained from a photosensitive resin composition can be solved, and thus the present invention was completed.

[0007] In other words, the present invention relates to the following:

[0008] A first aspect of the present invention relates to an alkali-developable alkoxysilane compound represented by the following formula (1). (In the formula, R １ R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ２ , R ３ , R ４Of these, one represents a monovalent group having an alkoxysilyl group, and the remaining two each independently represent a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, a branched alkyl group having 3 to 16 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a phenyl group, a benzyl group, a phenethyl group, a phenylsulfonyl group, a methacryloyloxyethyl group or a methacryloyloxypropyl group. The alkyl group and the branched alkyl group may be substituted with a halogen atom, and the alkyl group and the branched alkyl group may be substituted with a urea group. The urea group may be a monovalent group having an ester moiety, an alkyl group having a urea moiety substituted with a monovalent group having an ester moiety, a phenyl group having a urea moiety substituted with a monovalent group having an ester moiety, or may be substituted with one or more groups selected from a phenyl group and an alkyl group. The phenyl group, benzyl group, phenethyl group and phenylsulfonyl group in the above definition may be substituted with a group selected from an alkyl group, an alkoxy group, a halogen atom, a nitro group and a cyano group. L represents an alkylene group having 1 to 4 carbon atoms or a phenylene group.)

[0009] In the first aspect of the present invention, it is preferable that the compound represented by the formula (1) is a compound represented by the following formula (1-1), (1-2), (1-3) or (1-4). [In the formulas (1-1), (1-2), (1-3) and (1-4), R １ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ５ and R[[ID=IO]] ６ [[ID=1I]]each independently represent an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an alkynyl group having 2 to 4 carbon atoms, R １１ represents a hydrogen atom or a methyl group, R １２ represents a hydrogen atom, a methyl group, an ethyl group or a phenyl group, L represents an alkylene group having 1 to 4 carbon atoms or a phenylene group, and q represents an integer of 1 to 3.]

[0010] The second aspect of the present invention relates to inorganic fine particles mainly composed of silicon surface-treated with the alkali-developable alkoxysilane compound of the first aspect of the present invention.

[0011] A third aspect of the present invention relates to a thermosetting photosensitive resin composition containing component (A), component (B), solvent (C), and component (D). Component (A): Silica particles with an average primary particle diameter of 1 nm to 1 μm, surface-treated with an alkali-developable alkoxysilane compound according to the first aspect of the present invention; Component (B): Binder resin; Solvent (C); Component (D): Photosensitive agent.

[0012] In a third aspect of the present invention, it is preferable that at least one of the following (Z1) to (Z5) is satisfied: (Z1): Further contains a crosslinking agent which is component (E). (Z2): The binder resin which is component (B) has a self-crosslinking group or a group which reacts with at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group and an amino group. (Z3): Component (D) is a photoradical generator and further contains a compound which is component (F) having two or more ethylenically double bonds. (Z4): Component (D) is a photoacid generator and further contains a compound which is component (G) having two or more functional groups which form covalent bonds with the acid generated from component (D). (Z5): Component (D) is a photoacid generator and further contains a compound which is component (H) having two or more functional groups which decompose covalent bonds with the acid generated from component (D).

[0013] In a third embodiment of the present invention, it is preferable that component (D) is a quinone diazide compound.

[0014] In a third embodiment of the present invention, it is preferable that component (D) is a quinone diazide compound that satisfies either (Z1) or (Z2) above.

[0015] In a third embodiment of the present invention, the amount of the compound represented by formula (1) used for surface modification of the silica particles of component (A) is such that the surface area of ​​the silica particles is 1 nm ２ The number of items per unit is preferably in the range of 0.5 to 6.

[0016] In a third embodiment of the present invention, it is preferable that the weight-average molecular weight of the binder resin of component (B) is 1,000 to 50,000 in terms of polystyrene.

[0017] In a third embodiment of the present invention, it is preferable to contain 0.1 to 1000 parts by mass of component (A) per 100 parts by mass of component (B).

[0018] In a third aspect of the present invention, it is preferable that component (E) is present in an amount of 1 to 60 parts by mass relative to a total of 100 parts by mass of components (A) and (B).

[0019] A fourth aspect of the present invention relates to a cured film obtained using the photosensitive resin composition of the third aspect of the present invention.

[0020] The surface treatment agent of the present invention, silica particles and organosols on which alkali-soluble parts are introduced to the surface by the surface treatment agent, and a photosensitive resin composition containing the silica particles exhibit the effect of having optimal solubility in alkaline developers used in electronic devices. Therefore, the photosensitive resin composition of the present invention makes it possible to prevent silica particles from remaining in the developed portion when developing a patterned film obtained from the photosensitive resin composition.

[0021] Figure 1 is an optical microscope image of the residual film area and the developed pattern of Example 4, magnified 50 times (left: unexposed area, right: exposed area). Figure 2 is an optical microscope image of the developed area of ​​Comparative Example 3, magnified 50 times.

[0022] The photosensitive resin composition of the present invention is a photosensitive resin composition containing the following components (A), (B), (C) solvent, and (D): (A) component: silica particles with an average primary particle diameter of 1 nm to 1 μm whose surface is modified with the compound represented by the above formula (1); (B) component: binder resin; (C) solvent; (D) component: photosensitive agent.

[0023] The photosensitive resin composition of the present invention preferably further satisfies at least one of the following (Z1) to (Z5): (Z1): Further contains a crosslinking agent which is component (E). (Z2): The binder resin which is component (B) has a self-crosslinking group or a group which reacts with at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group and an amino group. (Z3): Component (D) is a photoradical generator and further contains a compound which is component (F) having two or more ethylenically double bonds. (Z4): Component (D) is a photoacid generator and further contains a compound which is component (G) having two or more functional groups which form covalent bonds with the acid generated from component (D). (Z5): Component (D) is a photoacid generator and further contains a compound which is component (H) having two or more functional groups which decompose covalent bonds with the acid generated from component (D).

[0024] The photosensitive resin composition of the present invention is preferably a positive-type photosensitive resin composition in which component (D) is a quinone diazide compound.

[0025] The details of each component are described below. <Component (A)> Component (A) is silica particles whose surface is modified with the compound represented by the following formula (1) (hereinafter also referred to as compound (1)). (In the formula, R １ R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ２ , R ３ , R ４One of these represents a monovalent group having an alkoxysilyl group, and the remaining two independently represent a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, a branched alkyl group having 3 to 16 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a phenyl group, a benzyl group, a phenethyl group, a phenylsulfonyl group, a meth(acryloyloxy)ethyl group, or a meth(acryloyloxy)propyl group. The alkyl group and branched alkyl group may be substituted with a halogen atom, and the alkyl group and branched alkyl group may also be substituted with a urea group. The urea group may be substituted with one or more groups selected from a monovalent group having an ester moiety, an alkyl group having a urea moiety substituted with a monovalent group having an ester moiety, a phenyl group having a urea moiety substituted with a monovalent group having an ester moiety, a phenyl group, and an alkyl group. The phenyl group, benzyl group, phenethyl group, and phenylsulfonyl group in the above definition may be substituted with a group selected from an alkyl group, an alkoxy group, a halogen atom, a nitro group, and a cyano group, and L represents an alkylene group or phenylene group having 1 to 4 carbon atoms.

[0026] Examples of the alkyl groups mentioned above include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, and 2-methyl-n-pentyl group. Tyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl- 2-methyl-n-propyl group, n-heptyl group, 1-methyl-n-hexyl group, 2-methyl-n-hexyl group, 3-methyl-n-hexyl group, 1,1-dimethyl-n-pentyl group, 1,2-dimethyl-n-pentyl group, 1,3-dimethyl-n-pentyl group, 2,2-dimethyl-n-pentyl group, 2,3-dimethyl-n-pentyl group, 3,3-dimethyl-n-pentyl group, 1-ethyl-n-pentyl group, 2-ethyl-n-pentyl group, 3-ethyl-n-pentyl group, 1-methyl-1-ethyl- n-butyl group, 1-methyl-2-ethyl-n-butyl group, 1-ethyl-2-methyl-n-butyl group, 2-methyl-2-ethyl-n-butyl group, 2-ethyl-3-methyl-n-butyl group, n-octyl group, 1-methyl-n-heptyl group, 2-methyl-n-heptyl group, 3-methyl-n-heptyl group, 1,1-dimethyl-n-hexyl group, 1,2-dimethyl-n-hexyl group, 1,3-dimethyl-n-hexyl group, 2,2-dimethyl-n-hexyl group, 2,3-dimethyl-n-hexyl group, 3,Examples include 3-dimethyl-n-hexyl group, 1-ethyl-n-hexyl group, 2-ethyl-n-hexyl group, 3-ethyl-n-hexyl group, 1-methyl-1-ethyl-n-pentyl group, 1-methyl-2-ethyl-n-pentyl group, 1-methyl-3-ethyl-n-pentyl group, 2-methyl-2-ethyl-n-pentyl group, 2-methyl-3-ethyl-n-pentyl group, 3-methyl-3-ethyl-n-pentyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, and n-hexadecyl group, each selected within the range of the number of carbon atoms.

[0027] As a monovalent group having an ester moiety, R １ -O-C(=O)-L- groups are preferred. Here, R １ And L is R in equation (1) １ And it represents the same definition as L, but the two R １ The two Ls may be the same or they may be different.

[0028] In this invention, the urea moiety refers to the structure shown below.

[0029] Examples of monovalent organic groups having an alkoxysilyl group include the group represented by the following formula (s). In formula (s), Q represents an alkylene group having 2 to 20 carbon atoms, and R ５ and R ６ Each of these independently represents an alkyl group with 1 to 4 carbon atoms, an alkenyl group with 2 to 4 carbon atoms, or an alkynyl group with 2 to 4 carbon atoms, and q represents an integer from 1 to 3. The dashed line represents a bond with a nitrogen atom.

[0030] R ５ and R ６Examples of these groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or sec-butyl groups. From the viewpoint of raw material availability and reactivity, methyl or ethyl groups are preferred. For Q, for example, trimethylene groups are preferred from the viewpoint of raw material availability. Q is preferably 2 or 3, with 3 being particularly preferred. N is preferably 1, 2, or 3, with 1 or 2 being particularly preferred.

[0031] One embodiment of the compound represented by formula (1) is R ２ is a group represented by formula (s), Q is a trimethylene group, and R ３ The compound is represented by the following formula (1-1), where is a (meth)acryloyloxyethyl group.

[0032]

[0033] The compound of formula (1-1) is obtained by reacting an amine represented by formula (1-1-A) with an isocyanate represented by formula (1-1-B).

[0034] The amine compound represented by formula (1-1-A) may be a commercially available product, or it can be produced by reacting an alkoxysilane compound having an amino group with a haloalkylcarboxylic acid ester compound in the presence of a base.

[0035] Examples of alkoxysilane compounds having an amino group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, and 3-aminopropylmethyldiethoxysilane.

[0036] The compound represented by formula (1-1-B) may also be a commercially available compound. Examples of such compounds include 2-isocyanatoethyl methacrylate (Kalenz MOI [registered trademark], manufactured by Showa Denko K.K.) and 2-isocyanatoethyl acrylate (Kalenz AOI [registered trademark], manufactured by Showa Denko K.K.).

[0037] One embodiment of the compound represented by formula (1) is R２ is a hydrogen atom, R ３ R １２ And R ４ The compound is represented by the following formula (1-2), where is a group represented by formula (s) and Q is a trimethylene group.

[0038]

[0039] The compound of formula (1-2) is obtained by reacting the amine compound represented by formula (1-2-A) with the isocyanate represented by formula (1-2-B).

[0040] The amine compounds represented by formula (1-2-A) include, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-methyl3-aminopropyltrimethoxysilane, N-methyl3-aminopropyltriethoxysilane, N-ethyl3-aminopropyltriethoxysilane, N-ethyl3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-(phenylamino)propyltriethoxysilane, and 3-A Examples of compounds include minopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N-methyl3-aminopropylmethyldimethoxysilane, N-methyl3-aminopropylmethyldiethoxysilane, N-ethyl3-aminopropylmethyldimethoxysilane, N-ethyl3-aminopropylmethyldiethoxysilane, N-phenyl-3-aminopropylmethyldiethoxysilane, 3-(phenylamino)propylmethyldimethoxysilane, and 3-(phenylamino)propylmethyldiethoxysilane.

[0041] As the isocyanate compound represented by formula (1-2-B), a commercially available one can be used.

[0042] Furthermore, the compound of formula (1-2) can also be obtained by reacting an amine compound represented by formula (1-2-C) with an isocyanate compound represented by formula (1-2-D).

[0043] Examples of amine compounds represented by formula (1-2-C) include methyl β-aminoacetate and ethyl β-aminoacetate.

[0044] Examples of isocyanate compounds represented by formula (1-2-D) include 3-trimethoxysilylpropyl isocyanate and 3-triethoxysilylpropyl isocyanate.

[0045] In the reaction between the above amine compound and the isocyanate compound, the amount of isocyanate compound used is NH group or NH ２ For every equivalent of the base, 0.98 to 1.2 equivalents should be reacted. More preferably, 1.0 to 1.05 equivalents.

[0046] One embodiment of the compound represented by formula (1) is R ２ is a hydrogen atom, R ３ is an alkyl group substituted with a urea group, and the urea group is substituted with a monovalent group having an ester moiety, R ４ The compound is represented by the following formulas (1-3), where is a group represented by formula (s) and Q is a trimethylene group.

[0047]

[0048] The compound of formula (1-3) is obtained by reacting the amine compound represented by formula (1-3-A) with the isocyanate compound represented by formula (1-2-B).

[0049] Examples of amine compounds represented by formula (1-3-A) include 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propyltriethoxysilane, 3-(2-aminoethylamino)propylmethyldimethoxysilane, 3-(2-aminoethylamino)propylmethyldiethoxylan, 3-(2-aminoethylamino)propylethyldimethoxylane, 3-(2-aminoethylamino)propylethyldiethoxylan, 3-(2-aminoethylamino)propyldimethylmethoxysilane, 3-(2-aminoethylamino)propyldimethylethoxylan, 3-(2-aminoethylamino)propyldiethylmethoxylane, and 3-(2-aminoethylamino)propyldiethylethoxylan.

[0050] As the isocyanate compound represented by formula (1-2-B), a commercially available one can be used.

[0051] One embodiment of the compound represented by formula (1) is R ２ is a hydrogen atom, R ３ R is an alkyl group substituted with a urea group, and the urea group is substituted with a monovalent group having an ester moiety, and is also substituted with an alkyl group having a urea moiety substituted with a monovalent group having an ester moiety, ４ The compound is represented by the following formulas (1-4), where is a group represented by formula (s) and Q is a trimethylene group.

[0052]

[0053] The compound of formula (1-4) is obtained by reacting an amine compound represented by formula (1-4-A) with an isocyanate compound represented by formula (1-2-B).

[0054] Examples of amine compounds represented by formula (1-4-A) include 3-{2-(2-aminoethyl)aminoethylamino}propyltrimethoxysilane, 3-{2-(2-aminoethyl)aminoethylamino}propyltriethoxysilane, 3-{2-(2-aminoethyl)aminoethylamino}propylmethyldimethoxysilane, 3-{2-(2-aminoethyl)aminoethylamino}propylmethyldiethoxylan, 3-{2-(2-aminoethyl)aminoethylamino}propylethyldimethoxylane, 3-{2-(2-aminoethyl)aminoethylamino}propylethyldiethoxylan, 3-{2-(2-aminoethyl)aminoethylamino}propyldimethylmethoxysilane, 3-{2-(2-aminoethyl)aminoethylamino}propyldimethylethoxylan, 3-{2-(2-aminoethyl)aminoethylamino}propyldiethylmethoxylane, and 3-{2-(2-aminoethyl)aminoethylamino}propyldiethylethoxylan.

[0055] In the reaction between the above amine compound and the isocyanate compound, the amount of isocyanate compound used is NH group or NH ２ For every equivalent of the base, 0.98 to 1.2 equivalents should be reacted. More preferably, 1.0 to 1.05 equivalents.

[0056] The reaction solvent is not particularly limited as long as it is inert to the reaction. Examples include hydrocarbons such as hexane, cyclohexane, benzene, and toluene; halogenated hydrocarbons such as carbon tetrachloride, chloroform, and 1,2-dichloroethane; ethers such as diethyl ether, diisopropyl ether, 1,4-dioxane, and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; nitriles such as acetonitrile and propionitrile; carboxylic acid esters such as ethyl acetate and ethyl propionate; nitrogen-containing aprotic polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and 1,3-dimethyl-2-imidazolidinone; sulfur-containing aprotic polar solvents such as dimethyl sulfoxide and sulfolane; and pyridines such as pyridine and picoline. These solvents may be used individually or in mixtures of two or more. Preferably, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone are used.

[0057] The amount of reaction solvent used (reaction concentration) is not particularly limited. The reaction may be carried out without a solvent, and if a solvent is used, 0.1 to 100 times the mass of the isocyanate compound may be used. From the viewpoint of exothermic reaction and manufacturing stability, the amount of reaction solvent used is preferably 0.5 to 70 times the mass of the isocyanate compound, and more preferably 10 to 50 times the mass from the viewpoint of the concentration at the time of use. The reaction temperature is not particularly limited, but for example, it is -90 to 150°C, preferably -30 to 100°C, and more preferably 0 to 80°C. The reaction time is usually 0.05 to 200 hours, preferably 0.5 to 100 hours.

[0058] To shorten the reaction time, a catalyst may be added. For example, organotin compounds such as dibutyltin dilaurate, dioctyltinbis(isooctylthioglycolate), dibutyltinbis(isooctylthioglycolate), and dibutyltin diacetate; triethylamine, trimethylamine, tripropylamine, tributylamine, diisopropylethylamine, N,N-dimethylcyclohexylamine, pyridine, tetramethylbutanediamine, N-methylmorpholine, and 1,4-diazabicyclo-2. Examples of catalysts include amines such as 2.2-octane, 1,8-diazabicyclo[5.4.0]undecene, and 1,5-diazabicyclo[4.3.0]nonene-5; organic sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid, and fluorosulfuric acid; inorganic acids such as sulfuric acid, phosphoric acid, and perchloric acid; titanium compounds such as tetrabutyl titanate, tetraethyl titanate, and tetraisopropyl titanate; bismuth compounds such as bismastris(2-ethylhexanoate); and quaternary ammonium salts. These catalysts may be used individually or in combination of two or more. These catalysts are preferably liquids or soluble in the reaction solvent.

[0059] The amount of catalyst used is 0.005 to 100% by mass, preferably 0.05 to 10% by mass, and more preferably 0.1 to 5% by mass, relative to the total amount (mass) of compounds having an isocyanate group (isocyanate compounds). When organotin compounds, titanium compounds, or bismuth-based compounds are used as the catalyst, the amount used is preferably 0.005 to 0.1% by mass, relative to the total amount (mass) of compounds having an isocyanate group. The reaction can be carried out under atmospheric pressure or under pressure, and may be in batch or continuous form.

[0060] <Silica sol dispersed in organic solvent> In the present invention, it is preferable to add the silica particles to the composition in the form of a dispersion (silica dispersion) in which the silica particles are dispersed in an organic solvent.

[0061] Examples of the aforementioned organic solvents include alcohols, ketones, hydrocarbons, amides, ethers, esters, cyclic esters, or amines.

[0062] Examples of the aforementioned alcohols include alcohols having 2 to 5 carbon atoms, specifically ethanol, isopropyl alcohol, and n-butanol.

[0063] Examples of the aforementioned ketones include ketones having 1 to 5 carbon atoms, specifically methyl ethyl ketone and methyl isobutyl ketone.

[0064] Examples of the aforementioned hydrocarbons include toluene, xylene, n-pentane, n-hexane, and cyclohexane.

[0065] Examples of the aforementioned amides include dimethylacetamide, N,N-dimethylformamide, dimethylacrylamide, acryloylmorpholine, diethylacrylamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-butyl-2-pyrrolidone, and solvents represented by the following formula (t). [In the formula, R ２1 and R ２２ Each of these is an alkyl group having 1 to 6 carbon atoms, and R ２３ R is an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms with an alkoxy group having 1 to 6 carbon atoms at its terminus, or an alkenyl group having 2 to 6 carbon atoms. ２1 ~R ２３ The total number of carbon atoms is 4 or more.

[0066] Examples of the aforementioned ethers include ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monopropyl ether.

[0067] Examples of the aforementioned esters include ethyl acetate, n-butyl acetate, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, methyl 2-hydroxyisobutyrate, propylene glycol acetate monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl 3-methoxypropionate, and butyl 3-methoxypropionate.

[0068] Examples of the aforementioned cyclic esters include γ-butyrolactone and γ-valerolactone.

[0069] Examples of the aforementioned amines include triethylamine, tributylamine, N,N-dimethylaniline, diisopropylamine, diisopropylethylamine, tripentylamine, pyridine, and picoline.

[0070] Among the above solvents, ketone solvents, amide solvents, ether solvents, ester solvents, and cyclic ester solvents are preferred in that they have excellent resin solubility and the transparency of the resulting resin thin film is also excellent, and amide solvents, ether solvents, ester solvents, and cyclic ester solvents represented by the above formula (t) are even more preferred.

[0071] The organic solvent-dispersed silica sol, which is a dispersion of silica particles in an organic solvent according to the present invention, can be produced, for example, by replacing the alcohol solvent in an alcohol-dispersed silica sol having 1 to 4 carbon atoms, which is a dispersion of silica particles having 1 to 4 carbon atoms, with the above organic solvent. Methods for replacing the solvent in an alcohol-dispersed silica sol having 1 to 4 carbon atoms with the above organic solvent include supplying the solvent to be replaced while removing the alcohol solvent having 1 to 4 carbon atoms under reduced pressure, and replacement by supplying the solvent using an ultrafiltration membrane.

[0072] The silica particle content in an organic solvent-dispersed silica sol can be expressed as the (surface-modified) silica concentration. The silica concentration can be calculated by weighing the calcination residue obtained after calcining the silica dispersion at 1000°C in an atmospheric environment. The silica concentration in the silica dispersion can be, for example, 1% to 60% by mass, or 10% to 60% by mass, or 10% to 40% by mass.

[0073] Furthermore, it is preferable that the water content of the silica dispersion is 5% by mass or less. This water content ensures good stability of the dispersion and facilitates the creation of hybrid materials with organic resin materials.

[0074] <Organosilicon Compounds> Furthermore, at least a portion of the surface of the silica particles contained in the silica sol is coated or modified with compound (1), which is a surface treatment agent, or its hydrolysate. This introduces alkali-soluble sites to the surface of the silica particles, improving alkali developability. The inorganic particles have a structure in which, for example, organosilicon compounds are bonded to the hydroxyl groups on the particle surface.

[0075] The amount of surface treatment (surface modification) by compound (1), which is a surface treatment agent, that is, the amount of compound (1) that coats or is bonded to the surface of the silica particles, is the surface area of ​​the silica particles at 1 nm. ２ For example, the amount can be in the range of 0.5 to 6 particles. That is, the amount of compound (1) added is the surface area of ​​the silica particles at 1 nm. ２ For example, compound (1) can be added in a range of approximately 0.5 to 6.0 particles to modify the surface. For example, silica particles with a surface area of ​​1 nm ２ The amount of compound (1) added per unit can be 0.5 to 10.0 units, or 1.0 to 8.0 units, or 1.0 to 6.0 units. Excess compound (1) that does not contribute to surface modification may be present in the system, but the preferred amount of compound (1) added is such that the silica particles have a surface area of ​​1 nm. ２ The amount of compound (1) added is such that the surface is modified by 1.0 to 6.0 particles per silica particle. ２By setting the number of particles in the range of 1.0 to 6.0 per particle, the silica particles can be given dispersibility in photosensitive resin compositions and solubility in alkaline developers used in electronic devices.

[0076] There are no particular limitations on the method for producing surface-modified silica particles, that is, the method for coating (surface treating) the surface of silica particles with compound (1). For example, by adding compound (1) and, if necessary, a highly soluble solvent such as ketones to an organic solvent dispersion of silica particles and mixing, hydrolysis and condensation of compound (1) can occur, thereby surface-modifying the silica particles.

[0077] The hydrolysis of compound (1) may be carried out completely or partially, but water is required, and it is preferable to add about 1 mole or more of water for every mole of hydrolyzable groups or [Si-O-Si] bonds or [Si-N-Si] bonds of compound (1). Alternatively, water contained in an organic solvent can be used. The amount of water used is not particularly specified, but from a manufacturing standpoint, it is desirable that the water content in the sol be 5% or less.

[0078] A catalyst can be used during hydrolysis and condensation. As a hydrolysis catalyst, chelate compounds, organic acids, inorganic acids, organic bases, or inorganic bases can be used alone or in combination. More specifically, for example, aqueous hydrochloric acid, acetic acid, or aqueous ammonia can be used.

[0079] The above surface modification step for silica particles is preferably carried out at the stage of an alcohol sol with 1 to 4 carbon atoms, from the viewpoint of improving the solubility of compound (1) and the surface modification rate.

[0080] The silica particles described above can be either solid silica particles or hollow silica particles.

[0081] Hollow silica particles are particles that have an outer shell layer mainly composed of silica, with a hollow interior surrounded by the outer shell layer, containing air within the cavity. Hollow silica particles are obtained by forming an outer shell mainly composed of silica on the surface of a core-like portion called a template in a dispersion medium, and then removing the core-like portion. Hollow silica particles have excellent low refractive index and heat insulating properties. On the other hand, solid silica particles are particles that do not have a hollow interior like hollow silica particles. The particle size is not particularly limited, but from the viewpoint of composition stability, the average primary particle diameter measured by nitrogen adsorption or transmission electron microscopy is preferably 3 nm to 5 μm, more preferably 5 nm to 1 μm, even more preferably 5 nm to 500 nm, and even more preferably 10 nm to 100 nm. The average secondary particle diameter measured by dynamic light scattering (DLS) is preferably 3 nm to 10 μm, more preferably 5 nm to 2 μm, even more preferably 5 nm to 500 nm, and even more preferably 10 nm to 200 nm. Furthermore, the shape of the hollow silica particles and solid silica particles is not particularly limited and may be spherical, ellipsoidal, or approximately spherical, such as a polyhedron that can approximate a sphere. The above-mentioned solid silica particles are readily available as commercial products, and the solvent used is not limited as long as it can be replaced with an organic solvent. In addition, the pH of the obtained sol is not particularly limited, but from the viewpoint of usability, a pH of 2 to 12, preferably 2 to 11, is desirable.Specific examples include Snowtex-XS, Snowtex-S, Snowtex-30, Snowtex-50T, Snowtex-30L, MP-1040, MP-2040, MP-4540M, Snowtex-UP, Snowtex-PS-S, Snowtex-PS-M, Snowtex-OXS, Snowtex-OS, Snowtex-O, Snowtex-O40, Snowtex-OL, Snowtex-OYL, Snowtex-OUP, Notex-PS-OS, Snowtex-PS-MO, Snowtex-NXS, Snowtex-NS, Snowtex-N, Snowtex-N-40, Snowtex-CXS, Snowtex-C, Snowtex-CM, Snowtex-AK, Snowtex-AK-L, Snowtex-AK-YL, Snowtex-K2, LSS-35, LSS-45, LSS-75, MT-ST, MA-ST-M, MA-ST-L, MA-ST-ZL, IP A-ST, IPA-ST-L, IPA-ST-UP, EG-ST-XL-30, NPC-ST-30, PGM-ST, PGM-ST-ZL, PMA-ST, DMAC-ST, DMAC-ST-ZL, NMP-ST, MEK-ST-4 0, MEK-ST-L, MEK-ST-ZL, MEK-ST-UP, MIBK-ST, MIBK-ST-L, CHO-ST-M, EAC-ST, EAC-ST-ZL, TOL-ST, MEK-AC-2130Y, MEK-AC-214 Examples include, but are not limited to, 0Z, MEK-AC-5140Z, MEK-AC-5340Z, PGM-AC-2140Y, PGM-AC-3140Y, PGM-AC-4130Y, MIBK-AC-2140Z, MIBK-SD-L, MEK-EC-2130Y (all manufactured by Nissan Chemical Corporation, product names), PL-1, PL-3, PL-7, PL-1OH, PL-1-IPA, PL-1-TOL, PL-2L-PGME, PL-2L-MEK (all manufactured by Fuso Chemical Co., Ltd., product names).Furthermore, the hollow silica particles mentioned above are readily available as commercial products. Specific examples include HKT-A20-40, HKT-A20-70 (both manufactured by Ningbo Dilato, product names), SG-HS60SPGA, SG-HS70PA (both manufactured by Sukgyung AT, product names), and the Through-Ria series (manufactured by JGC Catalysts & Chemicals, product names), represented by Through-Ria 1110, Through-Ria 4110, Through-Ria 2320, Through-Ria 4320, Through-Ria 5320, and Through-Ria 22UB-01AI.

[0082] <Component (B)> Component (B) of the present invention is a binder resin. The binder resin is preferably a solvent-soluble resin that dissolves in a solvent. The solvent referred to here is not particularly limited, but includes inorganic and organic solvents that are liquid at room temperature. The pH of the solvent can be 1 to 14, and from the viewpoint of manufacturing and handling, the pH is preferably 3 to 13, and more preferably 4 to 13. Furthermore, from the viewpoint of the alkali developability of the resin, it is also desirable that it has alkali-soluble groups. Examples of alkali-soluble groups include phenolic hydroxyl groups, carboxyl groups, acid anhydride groups, imide groups, sulfonyl groups, phosphoric acid, boronic acid, and groups represented by the following formula (b1). (In formula (b1), R represents an alkyl group, an alkoxy group, or a phenyl group.)

[0083] Examples of the group represented by the above formula (b1) include the following structures.

[0084] Among the alkali-soluble groups mentioned above, it is preferable that the alkali-soluble resin has at least one organic group selected from the group consisting of phenolic hydroxyl groups and carboxyl groups, and has a number-average molecular weight (Mn) of 2,000 to 50,000.

[0085] The solvent-soluble resin of component (B) above may be any alkali-soluble resin having such a structure, and is not particularly limited in terms of the backbone of the main chain and the type of side chains of the polymer constituting the resin.

[0086] However, if component (B) is a solvent-soluble resin, its weight-average molecular weight (Mw) is in the range of 1,000 to 50,000. If the weight-average molecular weight (Mw) is excessively high, exceeding 50,000, development residue is more likely to occur, and sensitivity will decrease significantly. On the other hand, if the weight-average molecular weight (Mw) is too low, less than 1,000, a considerable amount of film loss occurs in the exposed areas during development, which may result in insufficient curing.

[0087] Examples of the binder resin for component (B) include polysiloxane, phenol novolac resin, acrylic resin, polyhydroxystyrene resin, or polyimide precursor or polyimide, polyether, polyester, etc.

[0088] Furthermore, in the present invention, a binder resin consisting of a copolymer obtained by polymerizing multiple types of monomers (hereinafter referred to as a specific copolymer) can also be used as component (B). In this case, the binder resin of component (B) may be a blend of multiple types of copolymers.

[0089] When the binder resin is an acrylic resin, the copolymer is a copolymer formed using as essential constituent units a monomer that exhibits alkali solubility, i.e., a monomer having at least one selected from the group consisting of a carboxyl group and a phenolic hydroxyl group, and at least one monomer selected from the group of monomers copolymerizable with these monomers, and having a weight-average molecular weight (Mw) of 1,000 to 50,000. If the weight-average molecular weight (Mw) is greater than 50,000, there is a risk of residue formation.

[0090] The above-mentioned "monomer having at least one selected from the group consisting of a carboxyl group and a phenolic hydroxyl group" includes monomers having a carboxyl group and monomers having a phenolic hydroxyl group. These monomers are not limited to having one carboxyl group or phenolic hydroxyl group, but may have multiple groups.

[0091] The following are specific examples of the above monomers, but are not limited to these. Examples of monomers having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloyloxy)ethyl) phthalate, mono-(2-(methacryloyloxy)ethyl) phthalate, N-(carboxyphenyl)maleimide, N-(carboxyphenyl)methacrylamide, and N-(carboxyphenyl)acrylamide.

[0092] Examples of monomers having a phenolic hydroxyl group include hydroxystyrene, N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, N-(hydroxyphenyl)maleimide, and 4-hydroxyphenyl methacrylate.

[0093] In the production of an acrylic resin, which is a type of binder resin of component (B), the ratio of unsaturated carboxylic acid derivatives and / or monomers having a phenolic hydroxyl group and a polymerizable unsaturated group is preferably 10 to 90 mol%, more preferably 5 to 60 mol%, and most preferably 5 to 30 mol%, of all monomers used in the production of the acrylic resin of component (B). If the amount of unsaturated carboxylic acid derivative is less than 10% by mass, there is a risk that the alkali solubility of the polymer will be insufficient.

[0094] In the present invention, the acrylic resin, which is one of the components of (B), is preferably a copolymer of a monomer having a hydroxyalkyl group and a polymerizable unsaturated group, in order to further stabilize the pattern shape after curing.

[0095] Examples of monomers having a hydroxyalkyl group and a polymerizable unsaturated group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2,3-dihydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl methacrylate, glycerin monomethacrylate, and 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone.

[0096] In the production of the acrylic resin of component (B), the ratio of monomers having a hydroxyalkyl group and a polymerizable unsaturated group is preferably 10 to 60% by mass, more preferably 5 to 50% by mass, and most preferably 20 to 40% by mass. If the monomer having a hydroxyalkyl group and a polymerizable unsaturated group is less than 10% by mass, the stabilizing effect on the pattern shape of the copolymer may not be obtained. If it is 60% by weight or more, the alkali-soluble groups of component (B) may be insufficient, and properties such as developability may deteriorate.

[0097] In the present invention, the acrylic resin, which is one of the components of (B), is preferably obtained by further copolymerizing with an N-substituted maleimide compound, in order to increase the Tg of the copolymer.

[0098] Examples of N-substituted maleimide compounds include N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide. From the viewpoint of transparency, compounds without aromatic rings are preferred, and from the viewpoint of developability, transparency, and heat resistance, compounds having an alicyclic skeleton are more preferred, with N-cyclohexylmaleimide being the most preferred among them.

[0099] (B) In the production of an acrylic resin, which is one of the components, the ratio of N-substituted maleimide is preferably 10 to 60% by weight, more preferably 5 to 50% by weight, and most preferably 20 to 40% by weight. If the N-substituted maleimide is less than 10% by weight, the Tg of the copolymer will be low, and there is a risk that the heat resistance will be poor. On the other hand, if the N-substituted maleimide is 60% by weight or more, there is a risk that the transparency will decrease.

[0100] When the photosensitive resin composition of the present invention satisfies requirement (Z2), that is, the binder resin (B) used in the present invention is preferably a copolymer that further has a self-crosslinking group or a group that reacts with at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, and an amino group (hereinafter also referred to as a crosslinking group).

[0101] Examples of the self-crosslinking groups mentioned above include N-alkoxymethyl groups, N-hydroxymethyl groups, alkoxysilyl groups, epoxy groups, oxetane groups, acrylic groups (a type of vinyl group), and blocked isocyanate groups.

[0102] Examples of the above-mentioned crosslinkable groups include N-alkoxymethyl groups, N-hydroxymethyl groups, alkoxysilyl groups, epoxy groups, vinyl groups, and blocked isocyanate groups.

[0103] When such self-crosslinking groups or crosslinking groups are included in the resin of component (B), the content is preferably 0.1 to 0.9 groups per repeating unit in the resin of component (B), and more preferably 0.1 to 0.8 groups from the viewpoint of developability and solvent resistance.

[0104] (B) If the acrylic resin, which is one of the components, further has repeating units having crosslinkable groups such as N-alkoxymethyl groups, N-hydroxymethyl groups, alkoxysilyl groups, epoxy groups, vinyl groups, and blocked isocyanate groups, and self-crosslinkable groups such as N-alkoxymethyl groups, N-hydroxymethyl groups, alkoxysilyl groups, epoxy groups, oxetane groups, vinyl groups, and blocked isocyanate groups, then for example, an unsaturated compound having radical polymerizability and having crosslinkable groups such as epoxy groups, vinyl groups, and blocked isocyanate groups, and self-crosslinkable groups such as N-alkoxymethyl groups, N-hydroxymethyl groups, hydroxymethylamide groups, oxetane groups, and alkoxysilyl groups may be copolymerized.

[0105] Examples of unsaturated compounds that exhibit radical polymerizability and have an N-alkoxymethyl group include N-butoxymethylacrylamide, N-isobutoxymethylacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, and N-methylolacrylamide.

[0106] Examples of unsaturated compounds that have radical polymerizability and further contain a hydroxymethylamide group include N-hydroxymethylacrylamide and N-hydroxymethylmethacrylamide.

[0107] Examples of unsaturated compounds that have radical polymerizability and further contain an oxetane group include (meth)acrylic acid esters containing an oxetane group. Among such monomers are 3-(methacryloyloxymethyl)oxetane, 3-(acryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyl-oxetane, 3-(acryloyloxymethyl)-3-ethyl-oxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(acryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-phenyl-oxetane, 3-(acryloyloxymethyl)-2-phenyl-oxetane, 2-(methacryloyloxymethyl)oxetane, 2-(acryloyloxymethyl)oxetane, 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane, and 2-(acryloyloxymethyl)-4-trifluoromethyloxetane are preferred, and 3-(methacryloyloxymethyl)-3-ethyl-oxetane, 3-(acryloyloxymethyl)-3-ethyl-oxetane, etc. are preferably used.

[0108] Examples of unsaturated compounds that have radical polymerizability and further contain an alkoxysilyl group include 3-acryloyloxytrimethoxysilane, 3-acryloyloxytriethoxysilane, 3-methacryloyloxytrimethoxysilane, and 3-methacryloyloxytriethoxysilane.

[0109] Examples of unsaturated compounds that have radical polymerizability and further contain epoxy groups include glycidyl acrylate, glycidyl methacrylate, α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α-ethyl acrylate, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether, and p-vinylbenzylglycidyl ether. Of these, glycidyl methacrylate, 6,7-epoxyheptyl methacrylate, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether, p-vinylbenzylglycidyl ether, and 3,4-epoxycyclohexyl methacrylate are preferred. These can be used alone or in combination.

[0110] Examples of unsaturated compounds that have radical polymerizability and also contain vinyl groups include 2-(2-vinyloxyethoxy)ethyl acrylate and 2-(2-vinyloxyethoxy)ethyl methacrylate.

[0111] Examples of unsaturated compounds that have radical polymerizability and further contain a blocked isocyanate group include 2-(0-(1'-methylpropyleneneamino)carboxyamino)ethyl methacrylate and 2-(3,5-dimethylpyrazolyl)carbonylamino)ethyl methacrylate.

[0112] When the photosensitive resin composition of the present invention satisfies (Z1), it preferably contains 10 to 70% by mass, particularly preferably 20 to 60% by mass, of structural units derived from an unsaturated compound having acid, base, and / or radical polymerizability and having at least one group selected from crosslinkable groups such as N-alkoxymethyl groups, N-hydroxymethyl groups, alkoxysilyl groups, epoxy groups, vinyl groups, and blocked isocyanate groups, and self-crosslinkable groups such as N-alkoxymethyl groups, N-hydroxymethyl groups, alkoxysilyl groups, epoxy groups, oxetane groups, vinyl groups, and blocked isocyanate groups, based on the total amount of all repeating units in the binder resin (B). If the amount of these structural units is less than 10% by mass, the heat resistance and surface hardness of the resulting cured film tend to decrease, while if the amount of these structural units exceeds 70% by weight, the storage stability of the photosensitive resin composition tends to decrease.

[0113] Furthermore, in the present invention, the acrylic resin, which is one of the components of (B), may be a copolymer formed using monomers other than those described above (hereinafter referred to as "other monomers") as constituent units. Specifically, the other monomers are not particularly limited as long as they are copolymerizable with at least one selected from the group consisting of monomers having a carboxyl group and monomers having a phenolic hydroxyl group, as long as the properties of component (B) are not impaired. Specific examples of such monomers include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide, acrylamide compounds, acrylonitrile, styrene compounds, and vinyl compounds. Specific examples of such other monomers are listed below, but the invention is not limited to these.

[0114] Examples of the acrylic acid ester compounds include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthyl acrylate, anthyl methyl acrylate, phenyl acrylate, glycidyl acrylate, phenoxyethyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, and methoxytriethylene glycol acrylate. Examples include acrylates, 2-ethoxyethyl acrylate, 2-aminoethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-tricyclodecyl acrylate, diethylene glycol monoacrylate, caprolactone 2-(acryloyloxy)ethyl ester, poly(ethylene glycol) ethyl ether acrylate, and the like.

[0115] Examples of the methacrylate ester compounds include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthlyl methacrylate, anthlyl methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, phenoxyethyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2- Examples include ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate, diethylene glycol monomethacrylate, caprolactone 2-(methacryloyloxy)ethyl ester, and poly(ethylene glycol) ethyl ether methacrylate.

[0116] Examples of the acrylamide compounds include N-methylacrylamide, N-methylmethacrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N-butoxymethylacrylamide, and N-butoxymethylmethacrylamide.

[0117] Examples of the vinyl compounds include methyl vinyl ether, benzyl vinyl ether, cyclohexyl vinyl ether, vinylnaphthalene, vinylanthracene, vinylcarbazole, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo[4.1.0]heptane, 1,2-epoxy-5-hexene, and 1,7-octadiene monoepoxide.

[0118] Examples of the styrene compounds mentioned above include styrene, α-methylstyrene, chlorostyrene, bromostyrene, and hydroxystyrene.

[0119] In the production of an acrylic resin, which is one of the components (B), the ratio of the above-mentioned other monomers is preferably 80% by weight or less, more preferably 50% by weight or less, and even more preferably 20% by weight or less. If it is higher than 80% by weight, the essential components will decrease relatively, making it difficult to fully obtain the effects of the present invention.

[0120] The method for obtaining an acrylic resin, which is one of the components (B) used in the present invention, is not particularly limited, but for example, it can be obtained by polymerizing a monomer having at least one selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, and a group that generates a carboxylic acid or phenolic hydroxyl group by the action of heat or acid, a monomer having a hydroxyalkyl group, a monomer having at least one group selected from crosslinkable groups such as N-alkoxymethyl group, N-hydroxymethyl group, alkoxysilyl group, epoxy group, vinyl group, and blocked isocyanate group and self-crosslinkable groups such as N-alkoxymethyl group, N-hydroxymethyl group, alkoxysilyl group, oxetane group, epoxy group, vinyl group, and blocked isocyanate group, a monomer that can be copolymerized if desired, and a polymerization initiator if desired, in a solvent at a temperature of 50 to 110°C. The solvent used in this case is not particularly limited as long as it dissolves the monomer constituting the acrylic resin and the acrylic resin. Specific examples include the solvents described in (C) below.

[0121] The acrylic resin obtained in this way is usually in the form of a solution dissolved in a solvent.

[0122] Furthermore, the acrylic resin solution obtained as described above can be reprecipitated by adding it to a mixture of diethyl ether or water under stirring, and the resulting precipitate can be filtered and washed. After that, the solution can be dried at room temperature or by heating under normal or reduced pressure to obtain a resin powder. This operation removes polymerization initiators and unreacted monomers coexisting with the acrylic resin, resulting in a purified acrylic resin powder. If sufficient purification cannot be achieved in a single operation, the obtained powder can be redissolved in a solvent and the above operation can be repeated. In the present invention, the acrylic resin powder may be used as is, or it may be redissolved in a solvent, for example, (C) described later, and used as a solution.

[0123] Furthermore, as the binder resin of component (B), polyimides such as polyamic acid, polyamic acid esters, polyimide precursors such as partially imidized polyamic acid, phenolic hydroxyl group-containing polyimides, and carboxylic acid group-containing polyimides can be used, and any type is not particularly limited as long as they are alkali-soluble.

[0124] The polyamic acid, which is a polyimide precursor, can generally be obtained by polycondensation of (a) a tetracarboxylic dianhydride compound and (b) a diamine compound.

[0125] The above (a) tetracarboxylic dianhydride compounds are not particularly limited, and specific examples include aromatic tetracarboxylic acids such as pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylethertetracarboxylic dianhydride, and 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, as well as 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,2-dimethyl-1,2,3,4-dimethyl-1,2,3,4-dimethyl-1,2,3,4-dimethyl-1,2 Examples include alicyclic tetracarboxylic dianhydrides such as clobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3,4-cyclohexanetetracarboxylic dianhydride, and 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid dianhydride, as well as aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride. These may be used individually or in combination of two or more compounds.

[0126] Furthermore, the above (b) diamine compounds are not particularly limited, and for example, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,6-diamino-1,3-benzenedicarboxylic acid, 2,5-diamino-1,4-benzenedicarboxylic acid, bis(4-amino-3-carboxyphenyl) ether, bis(4-amino-3,5-dicarboxyphenyl) ether, bis(4-amino-3-carboxyphenyl) sulfone, bis(4-amino-3,5-dicarboxyphenyl) sulfone, Diamine compounds having a carboxyl group such as 4,4'-diamino-3,3'-dicarboxybiphenyl, 4,4'-diamino-3,3'-dicarboxy-5,5'-dimethylbiphenyl, 4,4'-diamino-3,3'-dicarboxy-5,5'-dimethoxybiphenyl, 1,4-bis(4-amino-3-carboxyphenoxy)benzene, 1,3-bis(4-amino-3-carboxyphenoxy)benzene, bis[4-(4-amino-3-carboxyphenoxy)phenyl]sulfone, bis[4-(4-amino-3-carboxyphenoxy)phenyl]propane, 2,2-bis[4-(4-amino-3-carboxyphenoxy)phenyl]hexafluoropropane, 2,4-diaminophenol, 3,5-diaminophenol, 2,5-diaminophenol, 4,6-diaminoresorcinol, 2,5-diaminohydroquinone, bis(3-amino-4 -Hydroxyphenyl) ether, bis(4-amino-3-hydroxyphenyl) ether, bis(4-amino-3,5-dihydroxyphenyl) ether, bis(3-amino-4-hydroxyphenyl)methane, bis(4-amino-3-hydroxyphenyl)methane, bis(4-amino-3,5-dihydroxyphenyl)methane, bis(3-amino-4-hydroxyphenyl) sulfone, bis(4-amino-3-hydroxyphenyl) sulfone, bis(4-amino-3,5-dihydroxyphenyl) sulfone, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-amino-3-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-amino-3,5-dihydroxyphenyl)hexafluoropropane, 4,4'-diamino-3,3'-dihydroxybiphenyl, 4,4'-diamino-3,Diamine compounds having phenolic hydroxyl groups, such as 3'-dihydroxy-5,5'-dimethylbiphenyl, 4,4'-diamino-3,3'-dihydroxy-5,5'-dimethoxybiphenyl, 1,4-bis(3-amino-4-hydroxyphenoxy)benzene, 1,3-bis(3-amino-4-hydroxyphenoxy)benzene, 1,4-bis(4-amino-3-hydroxyphenoxy)benzene, 1,3-bis(4-amino-3-hydroxyphenoxy)benzene, bis[4-(3-amino-4-hydroxyphenoxy)phenyl]sulfone, bis[4-(3-amino-4-hydroxyphenoxy)phenyl]propane, and 2,2-bis[4-(3-amino-4-hydroxyphenoxy)phenyl]hexafluoropropane. Examples include diamine compounds having a thiophenol group, such as 1,3-diamino-4-mercaptobenzene, 1,3-diamino-5-mercaptobenzene, 1,4-diamino-2-mercaptobenzene, bis(4-amino-3-mercaptophenyl) ether, 2,2-bis(3-amino-4-mercaptophenyl)hexafluoropropane, and diamine compounds having a sulfonic acid group, such as 1,3-diaminobenzene-4-sulfonic acid, 1,3-diaminobenzene-5-sulfonic acid, 1,4-diaminobenzene-2-sulfonic acid, bis(4-aminobenzene-3-sulfonic acid) ether, 4,4'-diaminobiphenyl-3,3'-disulfonic acid, and 4,4'-diamino-3,3'-dimethylbiphenyl-6,6'-disulfonic acid. Also, p-phenylenediamine, m-phenylenediamine, 4,4'-methylene-bis(2,6-ethylaniline), 4,4'-methylene-bis(2-isopropyl-6-methylaniline), 4,4'-methylene-bis(2,6-diisopropylaniline), 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, o-tolidine, m-tolidine, 3,3',5,5'-tetramethylbenzidine, bis[4-(3-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, 4,Examples of diamine compounds include 4'-diaminodiphenyl ether, 3,4-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 2,2-bis(4-anilino)hexafluoropropane, 2,2-bis(3-anilino)hexafluoropropane, 2,2-bis(3-amino-4-toluyl)hexafluoropropane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, and 2,2'-bis(trifluoromethyl)benzidine. These may be used individually or in combination of two or more compounds.

[0127] When the polyamic acid used in the present invention is produced from (a) a tetracarboxylic dianhydride compound and (b) a diamine compound, it is desirable that the mixing ratio of the two compounds, i.e., the total number of moles of the diamine compound (b) / the total number of moles of the tetracarboxylic dianhydride compound (a), be 0.7 to 1.2. Similar to ordinary polycondensation reactions, the closer this molar ratio is to 1, the higher the degree of polymerization of the resulting polyamic acid and the higher its molecular weight.

[0128] Furthermore, (b) when a diamine compound is polymerized in excess, the terminal amino groups of the remaining polyamic acid can be protected by reacting them with a carboxylic acid anhydride. Examples of such carboxylic acid anhydrides include phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalic anhydride, hydrogenated phthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic acid anhydride, itaconic anhydride, and tetrahydrophthalic anhydride.

[0129] In the production of polyamic acid, the reaction temperature for the reaction between (b) the diamine compound and (a) the tetracarboxylic dianhydride compound can be selected from any temperature between -20 and 150°C, preferably between -5 and 100°C. To obtain high molecular weight polyamic acid, the reaction temperature can be appropriately selected from 5°C to 40°C and the reaction time from 1 to 48 hours. To obtain a low molecular weight polyamic acid with high storage stability and partial imidization, it is more preferable to select a reaction temperature between 40°C and 90°C and a reaction time of 10 hours or more. Furthermore, when protecting the terminal amino group with an acid anhydride, the reaction temperature can be selected from any temperature between -20 and 150°C, preferably between -5 and 100°C.

[0130] (b) The reaction between the diamine compound and (a) the tetracarboxylic dianhydride compound can be carried out in a solvent. Suitable solvents include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylisobutylamide, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-butyl-2-pyrrolidone, N-vinylpyrrolidone, N-methylcaprolactam, and dimethyl Sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, m-cresol, γ-butyrolactone, γ-valerolactone, ethyl butyrolactone, butyl acetate, ethyl lactate, methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-hydroxyisobutyrate, Examples include ethyl 2-hydroxyisobutyrate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, carbitol acetate, ethyl cellosolve acetate, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, etc. These may be used individually or in combination. Furthermore, even solvents that do not dissolve polyamic acid may be mixed with the above solvents, as long as the polyamic acid produced by the polymerization reaction does not precipitate.

[0131] The solution containing the polyamic acid obtained in this way can be used directly in the preparation of a negative-type photosensitive resin composition. Alternatively, the polyamic acid can be precipitated and isolated in a poor solvent such as water, methanol, or ethanol, and then recovered for use.

[0132] Furthermore, any polyimide can be used as component (B). The polyimide used in the present invention is obtained by chemically or thermally imidizing a polyimide precursor such as the polyamic acid by 50% or more.

[0133] The polyimide used in the photosensitive resin composition of the present invention preferably has a group selected from a carboxyl group and a phenolic hydroxyl group in order to provide alkali solubility. Methods for introducing a carboxyl group or a phenolic hydroxyl group into the polyimide include using a monomer having a carboxyl group or a phenolic hydroxyl group, sealing the amine end with an acid anhydride having a carboxyl group or a phenolic hydroxyl group, or imidizing a polyimide precursor such as a polyamic acid to 99% or less.

[0134] Such polyimides can be obtained by synthesizing polyimide precursors such as the polyamic acids mentioned above, followed by imidation by heating in a specific solvent, chemical imidation, or thermal imidation. For imidation by heating in a specific solvent, it is desirable to use amides such as N,N'-dimethylacetamide, cyclic amides such as N-methylpyrrolidone, esters such as methyl 2-hydroxyisobutyrate, ethyl lactate, and propylene glycol monomethyl ether acetate, cyclic esters such as γ-butyrolactone, or alcohols such as propylene glycol monomethyl ether as the specific solvent, with a heating temperature of 50°C to 200°C and a heating time of 1 to 72 hours. Furthermore, from the viewpoint of subsequent use, it is desirable to use cyclic amides such as N-methylpyrrolidone, esters such as methyl 2-hydroxyisobutyrate, ethyl lactate, and propylene glycol monomethyl ether acetate, cyclic esters such as γ-butyrolactone, or alcohols such as propylene glycol monomethyl ether as the specific solvent, with a heating temperature of 50°C to 110°C and a heating time of 3 to 24 hours. Generally, chemical imidation involves adding excess acetic anhydride and pyridine to a polyimide precursor solution and reacting it at room temperature to 100°C. Alternatively, thermal imidation generally involves heating the polyimide precursor solution at 180°C to 250°C while simultaneously dehydrating it.

[0135] Furthermore, a phenol novolac resin can be used as the binder resin for component (B).

[0136] Furthermore, polyester polycarboxylic acid can be used as the binder resin for component (B). Polyester polycarboxylic acid can be obtained from an acidic dianhydride and a diol by the method described in WO2009 / 051186. Examples of acidic dianhydrides include the above-mentioned (a) tetracarboxylic dianhydride. Examples of diols include aromatic diols such as bisphenol A, bisphenol F, 4,4'-dihydroxybiphenyl, benzene-1,3-dimethanol, and benzene-1,4-dimethanol; alicyclic diols such as hydrogenated bisphenol A, hydrogenated bisphenol F, 1,4-cyclohexanediol, 1,3-cyclohexanedimethanol, and 1,4-cyclohexanedimethanol; and aliphatic diols such as ethylene glycol, propylene glycol, 1,4-butanediol, and 1,6-hexanediol.

[0137] Furthermore, polysiloxane can be used as the binder resin for component (B). Polysiloxane can be synthesized by hydrolysis of a silane compound followed by dehydration condensation. This hydrolysis and condensation are carried out under the hydrolysis conditions of the silane coupling agent described above. The silane compounds used can be produced by combining tetrafunctional silanes (silane compounds having four hydrolysis groups), trifunctional silanes (silane compounds having three hydrolysis groups and one organic group), difunctional silanes (silane compounds having two hydrolysis groups and two organic groups), and monofunctional silanes (silane compounds having one hydrolysis group and three organic groups). Among these, for example, a polysiloxane-based resin produced by combining a tetrafunctional silane and a trifunctional silane can be cited. Examples of tetrafunctional silanes include tetraethoxysilane and tetramethoxysilane. Tetraethoxysilane can be used particularly favorably. Examples of trifunctional silanes include alkyl silanes such as methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, and decyltrimethoxysilane; aryl silanes such as phenyltrimethoxysilane, phenyltriethoxysilane, phenylmethyltrimethoxysilane, and phenylmethyltriethoxysilane; vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane; epoxy silanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane; and styryl silanes such as p-styryltrimethoxysilane. Methacryl silanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane; acrylic silanes such as 3-acryloxypropyltrimethoxysilane;Amine silanes such as N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N,N-dimethylaminopropyltrimethoxysilane, and hydrochloride salts of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; isocyanurate silanes such as tris-(trimethoxysilylpropyl)isocyanurate and diallyl(trimethoxysilylpropyl)isocyanurate; ureido silanes such as 3-ureidopropyltrialkoxysilane; mercapto silanes such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; Examples include functional cyclic compound silanes such as 3-(3-(triethoxysilyl)propyl)dihydrofuran-2,5-dione, 3-(3-(trimethoxysilyl)propyl)dihydrofuran-2,5-dione, triethoxy[3-(1H-imidazole-1-yl)propyl]silane, product name X-121214A (manufactured by Shin-Etsu Chemical Co., Ltd.); and isocyanate silanes such as 3-isocyanatetopropyltriethoxysilane. One type of trifunctional silane may be used, or two or more types may be used. Examples of polysiloxane resins used as the binder resin (component B) include polysiloxane resins copolymerized with tetraethoxysilane, methyltrimethoxysilane, and phenyltrimethoxysilane; polysiloxane resins copolymerized with diallyl(trimethoxysilylpropyl) isocyanurate, tetraethoxysilane, methyltrimethoxysilane, and N,N-dimethylaminopropyltrimethoxysilane; and polysiloxane resins copolymerized with tetraethoxysilane, 3-(3-(trimethoxysilyl)propyl)dihydrofuran-2,5-dione, and 3-methacryloyloxypropyltrimethoxysilane. The weight-average molecular weight (Mw) of these linear to spherical polysiloxane resins can be set in the range of 1,000 to 100,000, or 1,000 to 5,000.

[0138] Furthermore, in the present invention, the solvent-soluble resin of component (B) may be a mixture of multiple types of solvent-soluble resins.

[0139] The ratio of component (A) to component (B) is 0.1 to 1000 parts by mass of component (A) per 100 parts by mass of component (B).

[0140] <(C) Solvent> The (C) solvent used in the present invention dissolves component (A), component (B), and components (D), (E), (F), and (G) as described later, as well as component (H) and other additives as desired. The type and structure of the solvent are not particularly limited as long as it has such dissolving ability.

[0141] Examples of such (C) solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, and 3-methyl Examples include 2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0142] These solvents can be used individually or in combination of two or more. Among these (C) solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetate, ethyl lactate, and butyl lactate are preferred from the viewpoint of good film-forming properties and high safety. These solvents are generally used as solvents for photoresist materials.

[0143] <Component (D)> Examples of photosensitive agents that constitute component (D) include (D-1) 1,2-quinone diazide compounds, (D-2) photoradical generators, and (D-3) photoacid generators.

[0144] (D-1) As the 1,2-quinone diazide compound, a compound having either a hydroxyl group or an amino group, or both a hydroxyl group and an amino group, can be used, in which preferably 10 to 100 mol%, and particularly preferably 20 to 95 mol%, of these hydroxyl groups or amino groups (or the total amount thereof if both a hydroxyl group and an amino group are present) is esterified or amidated with 1,2-quinone diazidosulfonic acid. Examples of the above 1,2-quinone diazidosulfonic acid include 1,2-naphthoquinone-2-diazide-5-sulfonic acid, 1,2-naphthoquinone-2-diazide-4-sulfonic acid, 1,2-benzoquinone-2-diazide-4-sulfonic acid, etc., and in the reaction with the above-mentioned compound having either a hydroxyl group or an amino group or both, the chloride of the 1,2-quinone diazidosulfonic acid can be used.

[0145] Examples of compounds having the aforementioned hydroxyl group include phenol, o-cresol, m-cresol, p-cresol, hydroquinone, resorcinol, catechol, methyl gallate, ethyl gallate, 1,3,3-tris(4-hydroxyphenyl)butane, 4,4-isopropridenediphenol, 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 4,4'-dihydroxyphenylsulfone, 4,4-hexafluoroisopropyridenediphenol, 4,4',4''-trishydroxyphenylethane, 1,1,1-trishydroxyphenylethane, and 4,4'-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethyl Examples of phenolic compounds such as bisphenol, 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2',3,4,4'-pentahydroxybenzophenone, and 2,5-bis(2-hydroxy-5-methylbenzyl)methyl; and aliphatic alcohols such as ethanol, 2-propanol, 4-butanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 2-methoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-butoxypropanol, ethyl lactate, and butyl lactate.

[0146] Furthermore, examples of compounds having an amino group include anilines such as aniline, o-toluidine, m-toluidine, p-toluidine, 4-aminodiphenylmethane, 4-aminodiphenyl, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminophenylmethane, and 4,4'-diaminodiphenyl ether, as well as aminocyclohexane.

[0147] Furthermore, examples of compounds having both hydroxyl and amino groups include aminophenols such as o-aminophenol, m-aminophenol, p-aminophenol, 4-aminoresorcinol, 2,3-diaminophenol, 2,4-diaminophenol, 4,4'-diamino-4''-hydroxytriphenylmethane, 4-amino-4',4''-dihydroxytriphenylmethane, bis(4-amino-3-carboxy-5-hydroxyphenyl) ether, bis(4-amino-3-carboxy-5-hydroxyphenyl)methane, 2,2-bis(4-amino-3-carboxy-5-hydroxyphenyl)propane, and 2,2-bis(4-amino-3-carboxy-5-hydroxyphenyl)hexafluoropropane, as well as alkanolamines such as 2-aminoethanol, 3-aminopropanol, and 4-aminocyclohexanol.

[0148] These 1,2-quinone diazide compounds can be used individually or in combination of two or more.

[0149] When the photosensitive resin composition of the present invention is a positive-type photosensitive resin composition, the amount of the compound having a quinone diazide group of component (D-1) is preferably 5 to 100 parts by mass, more preferably 8 to 50 parts by mass, and even more preferably 10 to 40 parts by mass, relative to 100 parts by mass of the total of components (A) and (B). If the amount is less than 5 parts by mass, the difference in dissolution rate between the exposed and unexposed parts of the positive-type photosensitive resin composition in the developer becomes small, which may make patterning by development difficult. If the amount exceeds 100 parts by mass, the 1,2-quinone diazide compound may not decompose sufficiently with short exposure times, which may reduce sensitivity, or component (D-1) may absorb light, which may reduce the transparency of the cured film.

[0150] (D-2) There are no particular restrictions on the photoradical generator as long as it generates radicals upon exposure. Specific examples include aromatic ketones such as benzophenone, Michler ketone, 4,4'-bisdiethylaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-ethylanthraquinone, phenanthrene, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether, benzoins such as methylbenzoin and ethyl benzoin, and 2-(o-chlorophenyl)-4,5-phenyl Imidazoles such as nilimidazole dimer, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4,5-triarylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(m-methylphenyl)imidazole dimer, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl- Halomethyloxadiazole compounds such as 5-(p-cyanostyryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole, 2,4-bis(trichloromethyl)-6-p-methoxystyryl-S-triazine, 2,4-bis(trichloromethyl)-6-(1-p-dimethylaminophenyl-1,3-butadienyl)-S-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-S-triazine, 2-(naphtho-1-yl)-4,6 Halomethyl-S-triazine compounds such as -bis-trichloromethyl-S-triazine, 2-(4-ethoxynaphtho-1-yl)-4,6-bis-trichloromethyl-S-triazine, 2-(4-butoxynaphtho-1-yl)-4,6-bis-trichloromethyl-S-triazine, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone, 1,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,1-Hydroxycyclohexyl-phenyl ketone, benzyl, benzoylbenzoate, methyl benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl sulfide, benzyl methyl ketal, dimethylaminobenzoate, p-dimethylaminobenzoate isoamyl, 2-n-butoxyethyl-4-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 1-(4-phenylthiophenyl)-1,2-octanedione-2-(O-benzoyloxime), ethanone, 1-[9-ethyl -6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyloxime), 4-benzoyl-methyldiphenyl sulfide, 1-hydroxycyclohexyl-phenyl ketone, 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, α-dimethoxy-α-phenylacetophenone, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, diphenyl(2,4,Examples include 6-trimethylbenzoyl)phosphine oxide and 2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone. The above photoradical generators are readily available as commercial products. Specific examples include IRGACURE 173, IRGACURE 500, IRGACURE 2959, IRGACURE 754, IRGACURE 907, IRGACURE 369, IRGACURE 1300, IRGACURE 819, IRGACURE 819DW, IRGACURE 1880, IRGACURE 1870, DAROCURE TPO, DAROCURE 4265, IRGACURE 784, IRGACURE OXE01, IRGACURE OXE02, and IRGACURE... Examples include 250 (manufactured by BASF), KAYACURE DETX-S, KAYACURE CTX, KAYACURE BMS, KAYACURE 2-EAQ (manufactured by Nippon Kayaku Co., Ltd.), TAZ-101, TAZ-102, TAZ-103, TAZ-104, TAZ-106, TAZ-107, TAZ-108, TAZ-110, TAZ-113, TAZ-114, TAZ-118, TAZ-122, TAZ-123, TAZ-140, TAZ-204 (manufactured by Midori Chemical Co., Ltd.). These photoradical generators can be used individually or in combination of two or more types.

[0151] When the photosensitive resin composition of the present invention contains component (D-2), the amount is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, and particularly preferably 1 to 15 parts by mass, per 100 parts by mass of component (A). If this ratio is too small, the exposed areas may not harden sufficiently, making pattern formation impossible or resulting in an unreliable film. If this ratio is too large, the transmittance of the coating film may decrease, or development problems may occur in the unexposed areas.

[0152] (D-3) The photoacid generator is not particularly limited as long as it is a compound that decomposes upon ultraviolet irradiation to produce acid. Examples of acids produced when the photoacid generator decomposes include hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, camphosulfonic acid, trifluoromethanesulfonic acid, p-phenolsulfonic acid, 2-naphthalenesulfonic acid, mesitylenesulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzenesulfonic acid, 1H,1H,2H,2H-perfluorooctanesulfonic acid, perfluoro(2-ethoxyethane)sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1-sulfonic acid, dodecylbenzenesulfonic acid, and other sulfonic acids or their hydrates or salts.

[0153] (D-3) Examples of photoacid generators include diazomethane compounds, onium salt compounds, sulfonimide compounds, disulfone compounds, sulfonic acid derivative compounds, nitrobenzyl compounds, benzointosylate compounds, iron arene complexes, halogen-containing triazine compounds, acetophenone derivative compounds, and cyano group-containing oximesulfonate compounds. Any conventionally known or conventionally used photoacid generators can be applied in the present invention without any particular limitations. In the present invention, the photoacid generator of component (D) may be used alone or in combination of two or more. Specific examples include compounds represented by the following formulas [PAG-1] to [PAG-41].

[0154]

[0155]

[0156]

[0157]

[0158]

[0159]

[0160]

[0161] When component (D-3) is included in the photosensitive resin composition of this embodiment, its content is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 8 parts by mass, relative to 100 parts by mass of the total of components (A) and (B). By including 0.01 parts by mass or more of component (D-3), sufficient thermosetting properties and solvent resistance can be provided. However, if the amount is greater than 20 parts by mass, there is a risk that unexposed areas will develop poorly or that the storage stability of the composition will decrease.

[0162] <Component (E)> Component (E) is a crosslinking agent and is introduced into the photosensitive resin composition of the present invention when the composition satisfies requirement (Z1). More specifically, it is a compound having a structure that can form a crosslinking structure by thermal reaction with the heat-reactive site of component (B) (for example, a carboxyl group and / or a phenolic hydroxyl group). Specific examples are given below, but the invention is not limited to these. The thermal crosslinking agent is preferably selected from, for example, (E1) a crosslinkable compound having two or more substituents selected from alkoxymethyl groups and hydroxymethyl groups, or (E2) a crosslinkable compound represented by formula (3). These crosslinking agents can be used individually or in combination of two or more.

[0163] A crosslinkable compound having two or more substituents selected from alkoxymethyl and hydroxymethyl groups of component (E1) undergoes a crosslinking reaction via dehydration condensation when exposed to high temperatures during thermosetting. Examples of such compounds include alkoxymethylated glycoluryl, alkoxymethylated benzoguanamine, and alkoxymethylated melamine, as well as phenoplast compounds.

[0164] Specific examples of alkoxymethylated glycoluryls include 1,3,4,6-tetrakis(methoxymethyl) glycoluryl, 1,3,4,6-tetrakis(butoxymethyl) glycoluryl, 1,3,4,6-tetrakis(hydroxymethyl) glycoluryl, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, 1,1,3,3-tetrakis(methoxymethyl)urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolinone, and 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolinone. Examples of commercially available products include glycoluryl compounds manufactured by Mitsui Cytec Co., Ltd. (product names: Cymel® 1170, Powderlink® 1174), methylated urea resins (product name: UFR® 65), butylated urea resins (product names: UFR® 300, U-VAN10S60, U-VAN10R, U-VAN11HV), and urea / formaldehyde resins manufactured by DIC Corporation (high condensation type, product names: Beccamine® J-300S, P-955, N).

[0165] Specific examples of alkoxymethylated benzoguanamine include tetramethoxymethylbenzoguanamine. Commercially available products include those manufactured by Mitsui Cytec Co., Ltd. (product name: Cymel® 1123) and Sanwa Chemical Co., Ltd. (product names: Nikalac® BX-4000, BX-37, BL-60, BX-55H).

[0166] Specific examples of alkoxymethylated melamines include hexamethoxymethylmelamine. Commercially available products include methoxymethyl type melamine compounds (product names: Cymel® 300, 301, 303, 350) and butoxymethyl type melamine compounds (product names: Mycoat® 506, 508) manufactured by Mitsui Cytec Co., Ltd., methoxymethyl type melamine compounds (product names: Nikalac® MW-30, MW-22, MW-11, MW-100LM, MS-001, MX-002, MX-730, MX-750, MX-035) and butoxymethyl type melamine compounds (product names: Nikalac® MX-45, MX-410, MX-302) manufactured by Sanwa Chemical Co., Ltd.

[0167] Furthermore, component (E) may be a compound obtained by condensing melamine compounds, urea compounds, glycoluryl compounds, and benzoguanamine compounds in which the hydrogen atoms of such amino groups are substituted with methylol groups or alkoxymethyl groups. For example, high molecular weight compounds produced from melamine compounds and benzoguanamine compounds described in U.S. Patent No. 6,323,310 can be mentioned. A commercially available example of the melamine compound is trade name: Cymel® 303 (manufactured by Mitsui Cytec Co., Ltd.), and a commercially available example of the benzoguanamine compound is trade name: Cymel® 1123 (manufactured by Mitsui Cytec Co., Ltd.).

[0168] Specific examples of phenoplast compounds include 2,6-bis(hydroxymethyl)phenol, 2,6-bis(hydroxymethyl)cresol, 2,6-bis(hydroxymethyl)-4-methoxyphenol, 3,3',5,5'-tetrakis(hydroxymethyl)biphenyl-4,4'-diol, 3,3'-methylenebis(2-hydroxy-5-methylbenzenemethanol), 4,4'-(1-methylethylidene)bis[2-methyl-6-hydroxymethylphenol], 4,4'-methylenebis[2-methyl-6-hydroxymethylphenol], 4,4'-(1-methylethylidene)bis[2,6-bis(hydroxymethyl)phenol], and 4,4'-methylenebis[2,6-bis(hydroxymethyl) Examples include methyl(methyl)phenol, 2,6-bis(methoxymethyl)phenol, 2,6-bis(methoxymethyl)cresol, 2,6-bis(methoxymethyl)-4-methoxyphenol, 3,3',5,5'-tetrakis(methoxymethyl)biphenyl-4,4'-diol, 3,3'-methylenebis(2-methoxy-5-methylbenzenemethanol), 4,4'-(1-methylethylidene)bis[2-methyl-6-methoxymethylphenol], 4,4'-methylenebis[2-methyl-6-methoxymethylphenol], 4,4'-(1-methylethylidene)bis[2,6-bis(methoxymethyl)phenol], and 4,4'-methylenebis[2,6-bis(methoxymethyl)phenol]. These are also available as commercially produced products, and specific examples include 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A, BISA-F, BI25X-DF, and BI25X-TPA (all manufactured by Asahi Organic Chemicals Co., Ltd.).

[0169] Furthermore, as component (E1), polymers produced using acrylamide compounds or methacrylamide compounds substituted with hydroxymethyl or alkoxymethyl groups, such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, and N-butoxymethylmethacrylamide, can also be used.

[0170] Examples of such polymers include poly(N-butoxymethylacrylamide), copolymers of N-butoxymethylacrylamide and styrene, copolymers of N-hydroxymethylmethacrylamide and methyl methacrylate, copolymers of N-ethoxymethylmethacrylamide and benzyl methacrylate, and copolymers of N-butoxymethylacrylamide, benzyl methacrylate and 2-hydroxypropyl methacrylate. The weight-average molecular weight (Mw) of such polymers is 1,000 to 50,000, preferably 1,500 to 20,000, and more preferably 2,000 to 10,000.

[0171] Furthermore, the photosensitive resin composition of the present invention may contain a crosslinkable compound represented by formula (3) as component (E2). (In the formula, k is an integer from 2 to 10, m is an integer from 0 to 4, and R ３１ (This represents a k-valent organic group.)

[0172] The (E2) component is not particularly limited as long as it is a compound having a cycloalkene oxide structure represented by formula (3). Specific examples include formulas E3-1 and E3-2 below, and the commercially available products shown below.

[0173] Commercially available products include Epolid GT-401, GT-403, GT-301, GT-302, Celoxide 2021, Celoxide 3000 (all product names from Daicel Chemical Industries, Ltd.), the alicyclic epoxy resin Denacol EX-252 (product name from Nagase Chemtex Co., Ltd.), CY175, CY177, CY179 (all product names from CIBA-GEIGY A.G.), Araldite CY-182, CY-192, CY-184 (all from CIBA-GEIGY A.G. Examples include A. G brand name), Epiclon 200, Epiclon 400 (both brand names from DIC Corporation), Epicote 871, Epicote 872 (both brand names from Yuka Shell Epoxy Co., Ltd.), ED-5661, ED-5662 (both brand names from Celanese Coating Co., Ltd.), etc. Furthermore, these crosslinkable compounds can be used individually or in combination of two or more types.

[0174] Of these, compounds represented by formulas E3-1 and E3-2, Epolid GT-401, GT-403, GT-301, GT-302, Celoxide 2021, and Celoxide 3000, which have a cyclohexene oxide structure, are preferred from the viewpoint of heat resistance, solvent resistance, process resistance such as resistance to long-term firing, and transparency.

[0175] Furthermore, as component E, compounds other than those indicated as components (E1) and (E2) that can form a cross-linking structure through thermal reaction with the thermally reactive sites of component (B) (for example, carboxyl groups and / or phenolic hydroxyl groups) can also be used. Specifically, epoxy compounds such as ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, and N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, VESTANAT B1358 / 100, VESTAGON BF Examples include isocyanate compounds such as 1540 (isocyanurate-type modified polyisocyanate, manufactured by Degussa Japan Co., Ltd.), Takenate® B-882N, and Takenate B-7075 (both isocyanurate-type modified polyisocyanate, manufactured by Mitsui Chemicals, Inc.).

[0176] Furthermore, as component E, a polymer can be used that has two or more structures capable of forming a cross-linking structure through a thermal reaction with the heat-reactive sites of component (B) (for example, carboxyl groups and / or phenolic hydroxyl groups). Specifically, examples include polymers produced using compounds having epoxy groups such as glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, and 3,4-epoxycyclohexylmethyl methacrylate; polymers produced using compounds having alkoxysilyl groups such as 3-methacryloxypropyltrimethoxysilane; compounds having isocyanate groups such as 2-isocyanatoethyl methacrylate (Karenz MOI [registered trademark], manufactured by Showa Denko K.K.), 2-isocyanatoethyl acrylate (Karenz AOI [registered trademark], manufactured by Showa Denko K.K.), or compounds having blocked isocyanate groups such as 2-(0-[1'-methylpropyleneneamino]carboxyamino)ethyl methacrylate (Karenz MOI-BM [registered trademark], manufactured by Showa Denko K.K.), 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate (Karenz MOI-BP [registered trademark], manufactured by Showa Denko K.K.). These compounds may be used individually or in combination to produce polymers, or they may be used in combination with other compounds to produce polymers.

[0177] If component (B) has a group that reacts with at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, and an amino group, then a compound having two or more groups represented by a hydroxyl group, a carboxyl group, an amide group, or an amino group can be used as component (E).

[0178] These crosslinkable compounds can be used individually or in combination of two or more.

[0179] When component (E) is selected as the crosslinking agent in the photosensitive resin composition of the present invention, its content is 1 to 50 parts by mass, preferably 1 to 40 parts by mass, and more preferably 1 to 30 parts by mass, per 100 parts by mass of the total of components (A) and (B). If the content of the crosslinking compound is low, the density of the crosslinks formed by the crosslinking compound may not be sufficient, and the effect of improving heat resistance, solvent resistance, and resistance to long-term firing after pattern formation may not be obtained. On the other hand, if it exceeds 50 parts by mass, uncrosslinked crosslinking compounds may be present, which may reduce heat resistance, solvent resistance, and resistance to long-term firing after pattern formation, and may also worsen the storage stability of the photosensitive resin composition.

[0180] <Component (F)> Component (F) is a compound having two or more ethylenically polymerizable groups (corresponding to the ethylenically double bonds described herein). A compound having two or more ethylenically polymerizable groups, as used herein, means a compound having two or more polymerizable groups in one molecule, and where these polymerizable groups are located at the molecular ends. These polymerizable groups mean at least one polymerizable group selected from the group consisting of acrylate groups, methacrylate groups, vinyl groups, and allyl groups. When the photosensitive resin composition of the present invention is a negative-type photosensitive resin composition, the compound having two or more ethylenically polymerizable groups, which is component (F), is preferably a compound with a molecular weight (or weight-average molecular weight (Mw) if the compound is a polymer) of 1,000 or less, from the viewpoint of having good compatibility with each component in a solution of the composition and not affecting developability.

[0181] Specific examples of such compounds include dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 1,3,5-triacryloylhexahydro-S-triazine, 1,3,5-trimethacryloylhex Sahydro-S-triazine, tris(hydroxyethyl acryloyl) isocyanurate, tris(hydroxyethyl methacryloyl) isocyanurate, triacryloyl formal, trimethacryloyl formal, 1,6-hexanediol acrylate, 1,6-hexanediol methacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, ethanediol diacrylate, ethanediol dimethacrylate, 2-hydroxypropanediol diacrylate, 2-hydroxypropanediol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, isopropylene glycol diacrylate, isopropylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, N,N'-bis(acryloyl)cysteine, N,Examples include N'-bis(methacryloyl)cysteine, thiodiglycol diacrylate, thiodiglycol dimethacrylate, bisphenol A diacrylate, bisphenol A dimethacrylate, bisphenol F diacrylate, bisphenol F dimethacrylate, bisphenol S diacrylate, bisphenol S dimethacrylate, bisphenoxyethanol full orange acrylate, bisphenoxyethanol full orange methacrylate, diallyl ether bisphenol A, o-diallylbisphenol A, diallyl maleate, triallyl trimellitate, etc.

[0182] The above-mentioned polyfunctional acrylate compounds are readily available as commercial products. Specific examples include, for example, KYARAD T-1420, DPHA, DPHA-2C, D-310, D-330, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, R-526, NPGDA, PEG400DA, MANDA, R-167, HX-220, HX620, R-551, R-712, R-604, and R- 684, GPO-303, TMPTA, THE-330, TPA-320, TPA-330, PET-30, RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), Aronix M -210, M-240, M-6200, M-309, M-400, M-402, M-405, M-450, M-7100, M-8030, M-8060, M-131 0, M-1600, M-1960, M-8100, M-8530, M-8560, M-9050 (manufactured by Toagosei Co., Ltd.), Viscoat 295, 300, 360, G PT, 3PA, 400, 260, 312, 335HP (manufactured by Osaka Organic Chemical Industry Co., Ltd.), A-9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-T Examples include MM-3L, A-TMM-3LM-N, A-TMPT, AD-TMP, ATM-35E, A-TMMT, A-9550, A-DPH, TMPT, 9PG, 701, 1206PE, NPG, NOD-N, HD-N, DOD-N, DCP, BPE-1300N, BPE-900, BPE-200, BPE-100, BPE-80N, 23G, 14G, 9G, 4G, 3G, 2G, and 1G (all manufactured by Shin Nakamura Chemical Industry Co., Ltd.). These compounds having two or more ethylenically polymerizable groups can be used individually or in combination of two or more.

[0183] When component (F) is included in the photosensitive resin composition of the present invention, the amount is preferably 5 to 100 parts by mass, more preferably 10 to 80 parts by mass, and particularly preferably 20 to 70 parts by mass, per 100 parts by mass of the total of components (A) and (B). If this ratio is too low, the exposed areas may not harden sufficiently, making pattern formation impossible or resulting in an unreliable film even if it is possible. Conversely, if this ratio is too high, tack may occur in the coating film after pre-baking, or the unexposed areas may not dissolve properly during development.

[0184] <Component (G)> Component (G) used in the photosensitive resin composition of the present invention is a compound having two or more functional groups that form covalent bonds with an acid generated from component (D). Examples of functional groups that form covalent bonds with such an acid include epoxy groups and methylol groups.

[0185] Examples of compounds having two or more epoxy groups include tris(2,3-epoxypropyl) isocyanurate, 1,4-butanediol diglycidyl ether, 1,2-epoxy-4-(epoxyethyl)cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, 2,6-diglycidylphenyl glycidyl ether, 1,1,3-tris[p-(2,3-epoxypropoxy)phenyl]propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4'-methylenebis(N,N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, bisphenol-A-diglycidyl ether, and pentaerythritol polyglycidyl ether.

[0186] Furthermore, as compounds having two or more epoxy groups, commercially available compounds may be used because they are readily available. The following are some specific examples (product names), but are not limited to these: epoxy resins having amino groups such as YH-434 and YH434L (manufactured by Toto Chemical Co., Ltd.); epoxy resins having a cyclohexene oxide structure such as Epolid GT-401, GT-403, GT-301, GT-302, Celoxide 2021, and Celoxide 3000 (manufactured by Daicel Chemical Industries, Ltd.); bisphenol A type epoxy resins such as Epicote 1001, 1002, 1003, 1004, 1007, 1009, 1010, and 828 (all manufactured by Yuka Shell Epoxy Co., Ltd. (now Japan Epoxy Resin Co., Ltd.)); and bisphenol A epoxy resins such as Epicote 807 (manufactured by Yuka Shell Epoxy Co., Ltd. (now Japan Epoxy Resin Co., Ltd.)). F-type epoxy resins; Epicote 152, Epicote 154 (both manufactured by Yuka Shell Epoxy Co., Ltd. (now Japan Epoxy Resin Co., Ltd.)), EPPN 201, EPPN 202 (both manufactured by Nippon Kayaku Co., Ltd.), etc. Phenol novolac type epoxy resins; EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 ( The above are cresol novolac type epoxy resins such as Nippon Kayaku Co., Ltd., Epicote 180S75 (manufactured by Yuka Shell Epoxy Co., Ltd. (now Japan Epoxy Resin Co., Ltd.)); Denacol EX-252 (manufactured by Nagase ChemteX Corporation), CY175, CY177, CY179, Araldite CY-182, CY-192, CY-184 (all manufactured by CIBA-GEIGY Alicyclic epoxy resins such as A.G., Epiclon 200, Epiclon 400 (both manufactured by Dainippon Ink and Chemicals, Inc.), Epicote 871, Epicote 872 (both manufactured by Yuka Shell Epoxy Co., Ltd. (now Japan Epoxy Resin Co., Ltd.)), ED-5661, ED-5662 (both manufactured by Celanese Coating Co., Ltd.); aliphatic polyglycidyl ethers such as Denacol EX-611, EX-612, EX-614, EX-622, EX-411, EX-512, EX-522, EX-421, EX-313, EX-314, EX-321 (manufactured by Nagase ChemteX Corporation).

[0187] Furthermore, polymers having epoxy groups can also be used as compounds having two or more epoxy groups. These epoxy-group-containing polymers can be produced, for example, by addition polymerization using an addition-polymerizable monomer having epoxy groups. Examples include addition polymerization polymers such as polyglycidyl acrylate, copolymers of glycidyl methacrylate and ethyl methacrylate, copolymers of glycidyl methacrylate, styrene and 2-hydroxyethyl methacrylate, and condensation polymerization polymers such as epoxy novolac.

[0188] Alternatively, the polymer having the epoxy group can also be produced by reacting a polymer compound having a hydroxyl group with an epoxy group compound such as epichlorohydrin or glycidyl tosylate.

[0189] The weight-average molecular weight (Mw) of such polymers is, for example, between 300 and 20,000.

[0190] Compounds having two or more epoxy groups can be used individually or in combination of two or more.

[0191] In the present invention, compounds having two or more methylol groups include compounds having two or more methylol groups and derivatives in which the methylol groups have been etherified. Examples of such compounds having two or more methylol groups include 1,3,4,6-tetrakis(methoxymethyl)glycoluryl, 1,3,4,6-tetrakis(butoxymethyl)glycoluryl, 1,3,4,6-tetrakis(hydroxymethyl)glycoluryl, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, 1,1,3,3-tetrakis(methoxymethyl)urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolinone, and 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolinone. Examples of commercially available products include glycoluryl compounds manufactured by Mitsui Cytec Co., Ltd. (product names: Cymel® 1170, Powderlink® 1174), methylated urea resin (product name: UFR® 65), butylated urea resin (product names: UFR® 300, U-VAN10S60, U-VAN10R, U-VAN11HV), urea / formaldehyde resins manufactured by DIC Corporation (high condensation type, product names: Beccamine® J-300S, P-955, N), and tetramethoxymethylbenzoguanamine. Examples of commercially available products include those manufactured by Mitsui Cytec Co., Ltd. (product name: Cymel® 1123), Sanwa Chemical Co., Ltd. (product names: Nikalac® BX-4000, BX-37, BL-60, BX-55H), and hexamethoxymethylmelamine. Examples of commercially available products include methoxymethyl type melamine compounds manufactured by Mitsui Cytec Co., Ltd. (product names: Cymel® 300, 301, 303, 350), butoxymethyl type melamine compounds (product names: Mycoat® 506, 508), methoxymethyl type melamine compounds manufactured by Sanwa Chemical (product names: Nikalac® MW-30, MW-22, MW-11, MS-001, MX-002, MX-730, MX-750, MX-035), and butoxymethyl type melamine compounds (product names: Nikalac® MX-45, MX-410, MX-302).

[0192] Furthermore, polymers containing methylol groups can also be used as compounds having two or more methylol groups.

[0193] Examples of polymers having two or more methylol groups include polymers produced using acrylamide compounds or methacrylamide compounds substituted with hydroxymethyl groups or alkoxymethyl groups, such as N-hydroxymethyl(meth)acrylamide, N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, and N-butoxymethyl(meth)acrylamide.

[0194] Specific examples of such polymers include, for example, poly(N-butoxymethylacrylamide), copolymers of N-butoxymethylacrylamide and styrene, copolymers of N-hydroxymethylmethacrylamide and methyl methacrylate, copolymers of N-ethoxymethylmethacrylamide and benzyl methacrylate, and copolymers of N-butoxymethylacrylamide, benzyl methacrylate and 2-hydroxypropyl methacrylate. The weight-average molecular weight (Mw) of such polymers is 1,000 to 200,000, more preferably 3,000 to 150,000, and even more preferably 3,000 to 50,000.

[0195] These compounds having two or more methylol groups can be used individually or in combination of two or more.

[0196] When the photosensitive resin composition of the present invention contains a compound having two or more functional groups that form a covalent bond with the acid of component (G), the content is preferably 5 to 200 parts by mass, and more preferably 50 to 150 parts by mass, based on 100 parts by mass of the total of components (A) and (B). If this ratio is too small, the photocurability of the photosensitive resin composition of the present invention as a negative-type photosensitive resin composition may decrease, while if it is too large, the developability of the unexposed areas may decrease, potentially causing residual film or residue.

[0197] <Component (H)> Component (H) used in the photosensitive resin composition of the present invention is a compound having two or more functional groups that decompose covalent bonds with an acid generated from component (D). Examples of functional groups that form covalent bonds with such an acid include vinyl ether groups. This can be any compound having two or more vinyl ether groups in one molecule that can be thermally crosslinked with the binder resin of component (B) at a conventional pre-bake temperature, and there are no particular limitations on its type or structure.

[0198] The compound of component (H) is separated (decrosslinked) from the binder resin of component (B) by an acid generated by exposure in the presence of a photoacid generator after thermal crosslinking with the binder resin of component (B), and is then removed together with the binder resin of component (B) by development using an alkaline developer. Therefore, as this type of compound, vinyl ether compounds, which are generally used as components of vinyl ether type chemically amplified resists, can be applied. When such a compound is used, there is an advantage that the shape of the formed film can be controlled by adjusting the thermal crosslinking density by changing the amount of the compound blended.

[0199] Specific examples of compounds of component (H) include m-divinyloxybenzene, p-divinyloxybenzene, 1,2,4-trivinyloxybenzene, 1,3,5-trivinyloxybenzene bis(4-(vinyloxymethyl)cyclohexylmethyl)glutarate, tri(ethylene glycol) divinyl ether, divinyl adipate ester, diethylene glycol divinyl ether, tris(4-vinyloxy)butyl trimellilate, bis(4-(vinyloxy)butyl) terephthalate, bis(4-(vinyloxy)butyl isophthalate, and cyclohexanedimethanol divinyl ether.

[0200] The compound of component (H) is preferably 5 to 200 parts by mass, more preferably 5 to 150 parts by mass, based on 100 parts by mass of the total of components (A) and (B). If this ratio is too small, the photocurability of the photosensitive resin composition of the present invention may decrease when it is a positive-type photosensitive resin composition. On the other hand, if it is too large, the developability of the exposed area may decrease, which may cause residual film or residue.

[0201] <Other Additives> Furthermore, the photosensitive resin composition of the present invention may optionally contain rheology modifiers, pigments, dyes, preservative stabilizers, defoamers, adhesion promoters, or dissolution promoters such as polyhydric phenols and polyhydric carboxylic acids, as long as they do not impair the effects of the present invention.

[0202] <Photosensitive Resin Composition> The photosensitive resin composition of the present invention is a photosensitive resin composition containing the following components (A), (B), (C) solvent, and (D), and optionally further containing one or more of the following: a crosslinking agent of component (E), a compound having two or more polymerizable groups of component (F), a compound having two or more functional groups that form covalent bonds with acid of component (G), and other additives. Component (A): Silica particles with an average primary particle diameter of 1 nm to 1 μm whose surface is modified with the compound represented by the above formula (1); Component (B): Binder resin; (C) Solvent; Component (D): Photosensitive agent.

[0203] Among them, preferred examples of the photosensitive resin composition of the present invention are as follows: [1]: A photosensitive resin composition containing 0.1 to 1,000 parts by mass of component (A) per 100 parts by mass of component (B), wherein these components are dissolved in solvent (C). [2]: A photosensitive resin composition containing 0.1 to 1,000 parts by mass of component (A) and 5 to 100 parts by mass of component (D) per 100 parts by mass of component (B), wherein these components are dissolved in solvent (C). [3]: A photosensitive resin composition containing 0.1 to 1,000 parts by mass of component (A) and 5 to 100 parts by mass of component (D) per 100 parts by mass of component (B), wherein these components are dissolved in solvent (C), and further containing 1 to 50 parts by mass of a crosslinking agent which is component (E) per 100 parts by mass of the total of components (A) and (B).

[0204] The proportion of solids in the photosensitive resin composition of the present invention is not particularly limited, as long as each component is uniformly dissolved in the solvent, but for example it is 1 to 80% by mass, or for example 5 to 60% by mass, or 10 to 50% by mass. Here, solids refer to the components of the photosensitive resin composition excluding (C) the solvent.

[0205] The method for preparing the photosensitive resin composition of the present invention is not particularly limited, but examples of such preparation methods include dissolving component (A) (surface-modified silica particles) in solvent (C), mixing in predetermined proportions the solvent-soluble resin component (B), the photosensitive agent component (D), a crosslinking agent component (E) if necessary, a compound component (F) having two or more polymerizable groups, and a compound component (G) having two or more functional groups that form covalent bonds with acid, to obtain a homogeneous solution, or adding and mixing other additives as necessary at an appropriate stage of this preparation method.

[0206] In preparing the photosensitive resin composition of the present invention, the copolymer solution obtained by the polymerization reaction in solvent (C) can be used as is. In this case, when adding components (B), (D), and optionally components (E), (F), (G), etc., to the solution of component (A) in the same manner as described above to make a homogeneous solution, additional solvent (C) may be added for the purpose of adjusting the concentration. At this time, the solvent (C) used in the formation process of the specific copolymer and the solvent (C) used for concentration adjustment during the preparation of the photosensitive resin composition may be the same or different.

[0207] Therefore, it is preferable to use the prepared photosensitive resin composition solution after filtering it using a filter with a pore size of about 0.2 to 1.0 μm.

[0208] <Coating Film and Cured Film> The photosensitive resin composition of the present invention can be applied to a semiconductor substrate (for example, a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, or chromium, a glass substrate, a quartz substrate, an ITO substrate, etc.) by rotary coating, flow coating, roll coating, slit coating, rotary coating followed by slit coating, inkjet coating, spray coating, etc., and then pre-dried on a hot plate or in an oven to form a coating film. Subsequently, a photosensitive resin film can be formed by heat treatment of this coating film.

[0209] The conditions for this heat treatment include, for example, a heating temperature and heating time appropriately selected from the range of 70°C to 160°C and 0.3 to 60 minutes. Preferably, the heating temperature and heating time are 80°C to 140°C and 0.5 to 10 minutes.

[0210] Furthermore, the thickness of the photosensitive resin film formed from the photosensitive resin composition is, for example, 0.1 to 30 μm, or for example, 0.2 to 10 μm, and even more specifically, 0.3 to 8 μm.

[0211] On the coating film obtained as described above, a mask having a predetermined pattern is attached and irradiated with light such as ultraviolet light, and then developed with an alkaline developer. Depending on the material composition, either the exposed or unexposed areas are washed away, and the remaining patterned film is heated at 80°C to 140°C for 0.5 to 10 minutes as needed to obtain a sharp relief pattern on the edges. Alternatively, if necessary, the film can be heated again at 80°C to 140°C for 0.5 to 10 minutes after irradiating with light such as ultraviolet light while attached to a mask having a predetermined pattern.

[0212] Examples of alkaline developers that can be used include aqueous solutions of alkali metal hydroxides such as potassium carbonate, sodium carbonate, potassium hydroxide, and sodium hydroxide; aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, ethyltrimethylammonium hydroxide, tetraethylammonium hydroxide, and choline; and aqueous solutions of amines such as ethanolamine, propylamine, and ethylenediamine. Furthermore, surfactants and other additives may be added to these developers.

[0213] Among the above, a 0.1 to 2.58% by mass aqueous solution of tetraethylammonium hydroxide or a 0.01 to 1% by mass aqueous solution of potassium hydroxide is commonly used as a developer for photoresists, and in the photosensitive resin composition of the present invention, these alkaline developers can be used to develop it well without causing problems such as swelling.

[0214] Furthermore, various development methods such as the liquid-filling method, dipping method, and agitation immersion method can be used. The development time in these cases is usually between 15 and 180 seconds.

[0215] After development, the photosensitive resin film is washed with running water for, for example, 20 to 120 seconds, and then air-dried using compressed air or compressed nitrogen, or by spinning, to remove moisture from the substrate and obtain a patterned film.

[0216] Next, by performing a post-bake on the pattern-forming film for heat curing, specifically by heating it using a hot plate, oven, etc., a film with excellent heat resistance, transparency, planarity, low water absorption, chemical resistance, and a good relief pattern can be obtained.

[0217] Post-baking generally involves heating at a temperature selected from the range of 140°C to 270°C for 5 to 30 minutes on a hot plate, or for 30 to 90 minutes in an oven.

[0218] Thus, by this post-baking process, a cured film with the desired good pattern shape can be obtained.

[0219] As described above, the photosensitive resin composition of the present invention has high storage stability, is sufficiently sensitive, exhibits very little film loss in unexposed areas during development, and can form a coating film with a fine pattern.

[0220] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The molecular weight of the polymer was measured as follows.

[0221] <Measurement of Number-Average Molecular Weight (Mn) and Weight-Average Molecular Weight (Mw)> The molecular weight of the polymer was measured using a GPC system manufactured by JASCO Corporation, with Shodex® KF-804L and 803L columns, under the following conditions: Column oven: 40°C Flow rate: 1 mL / min

[0222] <Measurement of Imidization Rate> The imidization rate is, １ The 1H-NMR (JNM-LA series, manufactured by JEOL Ltd.) was used to measure the proton ratio of aromatic groups in the polymer skeleton, the proton ratio of the NH moieties of polyamic acid or amic acid, and the proton ratio of hydroxyl groups. Dimethyl sulfoxide was used as the deuterated solvent. The number of cumulative measurements was 64, and the imidization rate was measured twice and then calculated as the average value.

[0223] The meanings of the abbreviations used in the following examples are as follows: <Monomers> MAA: Methacrylic acid MMA: Methyl methacrylate HEMA: 2-Hydroxyethyl methacrylate PQMA: 4-Hydroxyphenyl methacrylate CHMI: N-Cyclohexylmaleimide AIBN: Azobisisobutyronitrile TEOS: Tetraethoxysilane MTMS: Methyltrimethoxysilane PTMS: Phenyltrimethoxysilane BAHF: 2,2'-Bis(3-amino-4-hydroxyphenyl)hexafluoropropane DSDA: 3,3'-4,4'-Diphenylsulfonetetracarboxylic dianhydride APS: 3-Aminopropyltriethoxysilane M33TMSPAP: Methyl 3-((3-(trimethoxysilyl)propyl)amino)propanoate, manufactured by Shin-Etsu Chemical Co., Ltd., trade name X-88-475 ADEMS: 3-Aminopropyldiethoxymethylsilane 3(AEA)PTS: 3-(2-aminoethylamino)propyltrimethoxysilane (isocyanate compound) AOI-VM: 2-acryloyloxyethyl isocyanate, manufactured by Resonaq Corporation, trade name AOI-VM EICYA: Isocyanate ethyl acetate VE: Tris[4-(vinyloxybutyl)]trimellitate, manufactured by Allied Signal, trade name: Vectormer VE5015 PL-LI: Tetramethoxymethylglycoluryl, manufactured by Nippon Scitec Industries, Ltd. (formerly Mitsui Scitec Co., Ltd.), trade name: Powderlink 1174

[0224] <Photosensitive Agents> PA-3: Manufactured by Daito Chemistry Co., Ltd. PA-3 (trade name) (A photosensitive agent synthesized by the condensation reaction of 1 mole of 4,4'-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol and 2 moles of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride) PAG: Benzeneacetonitrile, 2-methyl-α-[5-[(propylsulfonyloxy)imino]-2(2H)-thienylidene], manufactured by BASF Japan Ltd., product name: Irgacure PAG103, (a compound represented by the above formula [PAG-4])

[0225] <Solvents> PGME: Propylene glycol monomethyl ether PGEE: Propylene glycol monoethyl ether PGMEA: Propylene glycol monomethyl ether acetate

[0226] <Water-dispersed silica sol, organic solvent-dispersed silica sol> ・Product name Snowtex O-40: Water-dispersed silica sol with an average primary particle size of 22 nm (manufactured by Nissan Chemical Corporation, water-dispersed sol of solid silica particles) ・Product name HKT-A20-40: Water-dispersed silica sol with an average primary particle size of 40 nm (manufactured by Ningbo Dilato, water-dispersed sol of hollow silica particles) ・Product name MT-ST: Methanol-dispersed silica sol with an average primary particle size of 12 nm (manufactured by Nissan Chemical Corporation, methanol-dispersed sol of solid silica particles)

[0227] <Silica (SiO ２ (Measurement of concentration) The silica concentration of aqueous-dispersed silica sol, methanol-dispersed silica sol, and dispersion of surface-modified silica particles was calculated by placing the silica sol or dispersion in a crucible, removing the solvent by heating, firing at 1000°C, and weighing the residue. (Measurement of composition concentration) The concentration (solid content concentration) of the composition was calculated by measuring approximately 1.00 g in an aluminum cup, firing at 200°C for 2 hours, and weighing the residue.

[0228] <Method for measuring the pH of water-dispersed silica sol> The pH of the water-dispersed silica sol was measured using a pH meter (manufactured by Toa DKK Co., Ltd., product name: MM-43X).

[0229] <Method for measuring the pH of organic solvent-dispersed silica sol> The pH of methanol-dispersed silica sol was measured using a pH meter (MM-43X) manufactured by Toa DKK Co., Ltd., by mixing the target sample containing the methanol-dispersed silica sol with methanol and pure water in a mass ratio of 1:1:1.

[0230] <Moisture Content> The moisture content in the dispersion of surface-modified silica particles and the silica sol used in its manufacturing process was measured by Karl Fischer titration using a Karl Fischer moisture meter (manufactured by Kyoto Electronics Manufacturing Co., Ltd., product name: MKA-610).

[0231] (Organic solvent content) The organic solvent content in the dispersion of surface-modified silica particles was determined by gas chromatography (Shimadzu Corporation, product name: GC-2014s). Gas chromatography conditions: Column: 3 mm x 1 m glass column Packing material: Polar Pack Q Column temperature: 130 to 230 °C (heating increase of 8 °C / min) Carrier: N ２ 40 mL / min Detector: FID Injection volume: 1 μL Internal standard: Acetonitrile was used. (Viscosity measurement) The viscosity of the dispersion liquid during the surface-treated silica particle manufacturing process was measured at 25°C using an Ostwald viscometer (manufactured by Shibata Scientific Co., Ltd.).

[0232] (Specific surface area (S) of the nitrogen adsorption method (BET method) Ｎ２ ) Measurement of specific surface area (S) of silica particles by nitrogen adsorption method in aqueous silica sol Ｎ２ In this method, water-soluble cations in a water-dispersed silica sol were removed using a cation exchange resin (Dow Chemical Company, product name: Amberlite IR-120B), and the silica sol was dried at 290°C to obtain a measurement sample. This sample was then measured using a nitrogen adsorption specific surface area analyzer, Monosorb (Quantachrome Instruments Japan LLC).

[0233] (Average primary particle diameter by nitrogen adsorption method) The average primary particle diameter by nitrogen adsorption method is the specific surface area S obtained by the nitrogen adsorption method described above. Ｎ２ (m ２ The average primary particle diameter (nm) was calculated by converting it to spherical particles using the following formula ( / g): Average primary particle diameter (nm) by nitrogen adsorption method = 2720 / S Ｎ２ (m ２ / g)

[0234] (Dynamic Light Scattering Particle Size (Average Particle Size (nm) by DLS Method)) The average particle size (Z-average particle size) by the DLS method was measured using a dynamic light scattering particle size analyzer (Malvern Panalogical, product name: Zetasizer Nano). The diluent used when measuring the average particle size by the DLS method was the same solvent as the main component contained in the dispersion medium of the silica particle dispersion.

[0235] (Measurement of average primary particle diameter by TEM (transmission electron microscope)) Particles in silica sol were photographed using a transmission electron microscope (JEM-F200, manufactured by JEOL Ltd.), and approximately 300 arbitrarily selected particles were binarized using an automated image processing and analysis system (LUZEX' AP, manufactured by Nireco Corporation). The diameter obtained by converting the projected area to a circular size was measured as the average primary particle diameter (HEYWOOD diameter).

[0236] (Measurement / Dissolution Method of the Amount of Aluminum Present in the Entire Silica Particle (B)) The precisely weighed silica sol was dried, the silica component was removed by treatment with hydrofluoric acid solution, and the residue was dissolved in an aqueous nitric acid solution. The hydrofluoric acid solution can be used at a concentration of, for example, 48% by mass, as long as it is an amount sufficient to sufficiently dissolve the silica particles. The amount of aluminum in the obtained aqueous solution was measured using an ICP emission spectrometer, and the amount of aluminum present in the entire silica particle was determined as Al ２ O ３ Converted to silica SiO ２ (Al ２ O ３ (ppm) / SiO ２ ) was sought.

[0237] (Measurement of the amount of aluminum (A) bonded to the surface of silica particles / leaching method) Cationic components in silica sol were removed with H-type cation exchange resin, and the solvent was removed by heat treatment. The dried material was pulverized in a mortar and pestle and further treated at 250°C for 2 hours. 0.2 g of the obtained powder was placed in a polypropylene container (PP sample bottle, 50 mL) containing 20 mL of 0.1 mol / liter (N / 10) nitric acid aqueous solution and shaken vigorously by hand. Next, ultrasonic treatment was performed for 10 minutes using an ultrasonic cleaner (AS ONE product name ASU CLEANER ASU-10M) to thoroughly mix the powder and the nitric acid aqueous solution. This was then placed in a 50°C constant temperature bath and held for 17 hours. Subsequently, the internal solution was cooled to room temperature, charged into a centrifugal ultrafiltration filter (product name Amicon Ultra-15, molecular weight cutoff 10,000), and the amount of aluminum in the filtrate obtained by centrifugation was measured using an ICP emission spectrometer. The amount of aluminum bound to the surface of the silica particles was then determined as Al ２ O ３ Converted to silica SiO ２ (Al２ O ３ (ppm) / SiO ２ ) was sought.

[0238] (Measurement of surface charge of silica particles) Silica sol was added and diluted in 10 mL of methanol to a silica concentration of 0.5% by mass to prepare the measurement sample. Using a particle charge meter (Voyt Turbo Co., Ltd., product name PCD-06), a 0.001 mol / liter (N / 1000) DADMAC solution (Voyt Turbo Co., Ltd.) was used as the cation standard titrator to measure the titration value until the flow potential of the measurement sample became zero. The obtained titration value was divided by the mass of silica contained in the measurement sample to convert it to a value per gram of hollow silica particles, and the surface charge (μeq / g-SiO₂) was calculated. ２ ) was used. Note that DADMAC refers to poly(diallyldimethylammonium chloride).

[0239] (IR measurement) A sample (surface treatment agent: a mixture of M33TMOSPAP, MEK, and AOI-VM from Synthesis Example 5 described later) is applied to a silicon substrate, heated at 100°C for 10 minutes to remove the solvent, and then IR measurement by transmission is performed using an infrared absorption spectrometer (instrument name iS50 FT-IR, manufactured by Thermo Fisher Scientific Co., Ltd.) with 32 cumulative measurements (measurement range: 4000-400 cm). －１ The following was performed: From the graph obtained by IR measurement, the IR peak position (cm －１ ) was obtained.

[0240] <Synthesis Example 1> Synthesis of Polysiloxane (P1) 14.58 g of TEOS (70 mol% of the total silane compound), 3.57 g of MTMS (20 mol% of the total silane compound), 1.98 g of PTMS (10 mol% of the total silane compound), and 31 g of acetone were placed in a 200 mL flask. While stirring the mixed solution with a magnetic stirrer, 6.67 g of 0.01 mol / L hydrochloric acid was added dropwise. After addition, the flask was transferred to an oil bath adjusted to 85°C and reacted under heated reflux for 240 minutes. Then, the reaction solution was cooled to room temperature, 40 g of PGMEA was added to the reaction solution, and the reaction by-products methanol, ethanol, water, and hydrochloric acid were removed by vacuum distillation. The solution was then concentrated to obtain a hydrolysis condensate (polymer) PGMEA solution. PGEE was added to this solution, and solvent replacement was performed by solvent distillation to obtain a PGEE polymer solution. The obtained solution was adjusted with PGEE to a solid residue percentage of 15 mass at 200°C. The weight-average molecular weight (Mw) of the obtained polymer was 1,500 in terms of polystyrene.

[0241] <Synthesis Example 2> Synthesis of Polyhydroxyimide (P2) 240 g of PGMEA, to which 30.3 g (0.083 mol) of BAHF was dissolved, was mixed with 29.7 g (0.083 mol) of DSDA, and the mixture was reacted at room temperature for 48 hours to synthesize a polyamic acid solution. This solution was heated at 90°C for 24 hours. The imidization rate of the obtained polyhydroxyimide solution was 90%, and the weight-average molecular weight (Mw) was 12,000. Furthermore, 30 g of this polyhydroxyimide solution was precipitated in methylene chloride to obtain a polymer, which was filtered and then dried in a vacuum oven (60°C, 18 hours). The obtained powder was １ 1H-NMR analysis revealed the presence of a hydroxyl group. The imidization rate was 90%.

[0242] <Synthesis Example 3> Synthesis of MeOH-dispersed hollow silica sol (a1) (1) Preparation of aqueous dispersion sol (a) of aluminum-containing hollow silica particles Put 2015 g of commercially available hollow silica aqueous sol HKT-A20-40 (product name) into a 3 L plastic container, Al ２ O ３Diluted sodium aluminate (169 g), diluted to a concentration of 1.0% by mass, was added dropwise over 1 minute, and then sodium sulfate aqueous solution (Na) was added. ２ SO ４ 6 g of an aqueous solution (converted to 10% by mass) was added dropwise, and the mixture was stirred for 30 minutes at a rotation speed of 600 rpm using a mechanical stirrer equipped with a glass stirring blade. Next, 800 g of this mixture was placed in a glass separable flask and subjected to a heat treatment at 80°C for 5 hours, and then cooled to room temperature. Next, the mixture was passed through a cation exchange resin (product name H-type Amberlite IR-120B) packed into a column at a space velocity (SV) of 5 / hour to obtain an aqueous dispersion sol (a) of aluminum-containing hollow silica particles. The physical properties of the obtained sol were measured, and the result showed that SiO ２ Concentration 16.9% by mass, pH 2.6, average particle size 54 nm by DLS method, specific surface area (C) 149 m² by BET method. ２ / g, the amount of aluminum bound to the particle surface (A) is 1500 ppm, and the amount of aluminum present throughout the silica particles (B) is Al ２ O ３ Converted to silica SiO ２ The concentration is 1900 ppm per 1 g, the A / B ratio is 0.79, the average primary particle size observed by TEM is 43 nm, and the TEM-equivalent specific surface area (D) is 63 m². ２ The particle size was 1.26 / g, with a specific surface area ratio (C / D ratio) of 2.4, a particle refractive index of 1.26, and an outer shell thickness of 6.7 nm. (2) Preparation of MeOH dispersion sol (a1) of aluminum-containing hollow silica particles 118.3 g of aqueous dispersion sol (a) of aluminum-containing hollow silica particles was placed in a 300 mL round-bottom flask, and 15.0 g of methanol was added. Using a rotary evaporator, the pressure was reduced to 580 Torr, and methanol substitution was performed while heated at 120°C to obtain MeOH dispersion sol (a1) of aluminum-containing hollow silica particles. The physical properties of the obtained sol were pH 3.7, average particle size 64 nm by DLS method, and SiO ２ Concentration 24.2% by mass, moisture content 0.3% by mass, viscosity 1.9 mPa·s, SiO2 of hollow silica particles ２ The surface charge, when converted to a per-gram amount, was 59 μeq / g.

[0243] <Synthesis Example 4> Synthesis of solid silica sol (a2) in MeOH dispersion: 14,000 g of Snowtex O-40 (trade name) was subjected to water substitution by ultrafiltration using MeOH. The substitution was terminated when the water content reached 0.5% by mass, and the synthesis of solid silica sol in MeOH dispersion was obtained. The physical properties of the obtained sol were SiO ２ concentration 40.6% by mass, water content 0.5% by mass, viscosity 5.4 mPa·s, average particle diameter 18 nm by the DLS method, and the amount of Na present in the whole silica particles was Na ２ in terms of O, 2210 ppm / SiO ２ per 1 g of silica. The amount of sulfate ions present in the silica sol was SO ２ , and in terms of SO ４ per 1 g of silica in terms of SiO ２ was 0.7 ppm / SiO ４ ２ . Also, the amount of aluminum present in the whole silica particles was Al ２ in terms of O ３ was 2500 ppm / SiO ２ per 1 g of silica in terms of SiO ２ －１ .

[0244] <Synthesis Example 5> Synthesis of alkali-developable surface treatment agent 1: 16 g of MEK in which 2.49 g of M33TMOSPAP was dissolved was placed in a 100 mL eggplant flask, and 1.51 g of AO I-VM was further added and stirred at room temperature for 3 hours to obtain a 20% by mass solution of the target surface treatment agent 1. The IR (cm －１ ) of the prepared surface treatment material was 3370, 2947, 1729, 1635, 1537, 1268, 1193, 1085.

[0245] <Synthesis Example 6> Synthesis of solid silica sol with surface treated with alkali-developable surface treatment agent 1 (AA1): 13 g of the 20% by mass MEK solvent solution of surface treatment agent 1 prepared in Synthesis Example 5 was added to a 500 mL eggplant flask with a condenser containing 50 g of solid silica sol (a2) in MeOH dispersion obtained in Synthesis Example 4, 35.9 g of methanol, and 1.5 g of pure water, and heated at 65 °C for 3 hours to obtain the target sol. The obtained sol had an average particle diameter of 45 nm by the DLS method with methanol as the standard, pH 3.41, SiO ２The concentration was 20% by mass and the moisture content was 1.2% by mass. Furthermore, there was no sedimentation, indicating good dispersibility.

[0246] <Synthesis Example 7> Synthesis of Alkali-developable Surface Treatment Agent 2 1.47 g of EICYA was added to 16 g of MEK containing 2.52 g of APS dissolved in a 100 mL round-bottom flask, and the mixture was stirred at room temperature for 3 hours to obtain a 20% by mass solution of the target surface treatment agent 2. The IR (cm²) of the prepared surface treatment material was also measured. －１ The numbers were 3361, 2976, 1748, 1644, 1574, 1281, 1199, and 1081.

[0247] <Synthesis Example 8> Synthesis of hollow silica treated with alkali-developable surface treatment agent 2 (AA2) 13 g of the surface treatment agent 2 solution in 20% MEK solvent prepared in Synthesis Example 7 was added to a 500 mL round-bottom flask with a condenser containing 150 g of the MeOH-dispersed hollow silica sol (a1) obtained in Synthesis Example 3, 18.5 g of methanol, and 2 g of pure water. The mixture was heated at 65°C for 3 hours while stirring with a magnetic stirrer to obtain the desired sol. The obtained sol had an average particle size of 62 nm, pH 6.60, and SiO2 by DLS method. ２ The concentration was 20% by mass and the moisture content was 1.2% by mass. Furthermore, there was no sedimentation, indicating good dispersibility.

[0248] <Synthesis Example 9> Synthesis of Polyacrylic (P3) Using 6.0 g of MAA, 16.0 g of CHMI, 10.0 g of HEMA, 2.0 g of PQMA, and 6.0 g of MMA, and using 2.5 g of AIBN as a radical polymerization initiator, these were polymerized in 63.6 g of the solvent PGME at a temperature of 60°C to 100°C to obtain a solution of alkali-soluble polymer components (solid content concentration: 40% by mass) with a number average molecular weight (Mn) of 3,600 and a weight average molecular weight (Mw) of 8,600.

[0249] <Synthesis Example 10> Synthesis of PGME-dispersed hollow silica sol (a3) ​​1856g of HKT-A20-40D (manufactured by Ningbo Dilato, trade name) was placed in a 3L plastic container and stirred at a rotational speed of 650 rpm with a mechanical stirrer equipped with a glass stirring blade, Al ２ O ３32.2 g of an aqueous sodium aluminate solution diluted to a concentration of 1.0% by mass was added dropwise over 1 minute, and the mixture was stirred at the same rotational speed for 30 minutes. Then, 643.6 g of pure water was added, and the mixture was stirred for an additional 20 minutes to obtain the mixture. Next, 2502 g of this mixture was placed in a 3 L stainless steel autoclave container and heated at 150°C for 5 hours under stirring at 80 rpm, then cooled to below 50°C to obtain an aqueous sol. Next, 2200 g of the obtained aqueous sol was placed in a 3 L round-bottom flask, and the solvent was replaced using an evaporator while adding 6 L of PGME (60 ppm for methanol content) under conditions of 90°C and 150 Torr. Afterward, the concentration was adjusted to obtain the target PGME sol (PGME-1). The obtained PGME sol had a silica particle concentration of 14.9% by mass, an average secondary particle diameter of 67 nm by DLS method, a moisture content of 0.5% by mass, a pH of 6.9, and a methanol content of 66 ppm. Next, 100 g of H-type cation exchange resin (manufactured by Dow Chemical, trade name Amberlite IR-120B), which had been previously washed with PGME, was added to 1000 g of the obtained PGME sol. After stirring at 23°C for 5 hours, the ion exchange resin was removed to obtain the desired ion-exchanged PGME sol (PGME-2). The obtained ion-exchanged PGME sol (PGME-2) had a silica particle concentration of 14.9% by mass, an average secondary particle diameter of 67 nm by DLS method, a moisture content of 0.5% by mass, a pH of 3.4, and a methanol content of 66 ppm.

[0250] <Synthesis Example 11> Synthesis of Alkali-developable Surface Treatment Agent 3 2.44 g of EICYA was added to 14 g of MEK containing 3.63 g of ADEMS dissolved in a 100 mL round-bottom flask, and the mixture was stirred at room temperature for 3 hours to obtain a 30% by mass solution of the target surface treatment agent 3. The IR (cm²) of the prepared surface treatment material was measured. －１ The numbers were 3358, 2977, 2933, 2877, 1705, 1640, 1571, 1259, 1199, and 1080.

[0251] <Synthesis Example 12> Synthesis of Alkali-developable Surface Treatment Agent 4 3.70 g of 3(AEA)PTS was dissolved in 12 g of MEK in a 100 mL round-bottom flask. 4.29 g of EICYA was added to this solution and stirred at room temperature for 3 hours to obtain a 41% by mass solution of the target surface treatment agent 4. The IR (cm²) of the prepared surface treatment material was measured. －１ The numbers were 3367, 2990, 2941, 2842, 1750, 1650, 1565, 1270, 1199, and 1081.

[0252] <Synthesis Example 13> Synthesis of PGME hollow silica sol (AA3) whose surface was treated with alkali-developable surface treatment agent 3. 8.0 g of the surface treatment agent 3 solution in 30% MEK solvent prepared in Synthesis Example 11 was added to a 500 mL round-bottom flask with a condenser containing 100 g of the PGME dispersed hollow silica sol (a3) ​​obtained in Synthesis Example 10. The mixture was heated at 70°C for 3 hours while stirring with a magnetic stirrer to obtain the target sol. The obtained sol had an average particle size of 65 nm, pH 3.9, and SiO2 by DLS method. ２ The concentration was 14.9% by mass and the moisture content was 0.5% by mass. Furthermore, there was no sedimentation, indicating good dispersibility.

[0253] <Synthesis Example 14> Synthesis of PGME hollow silica sol (AA3-2) obtained by surface treatment with alkali-developable surface treatment agent 3 and 3-(methoxydimethylsilyl)propyl acrylate. 30 g of hollow silica PGME sol, surface-treated with alkali-developable surface treatment agent 3 prepared in Synthesis Example 13, was placed in a 100 mL round-bottom flask with a condenser. 0.84 g of 3-(methoxydimethylsilyl)propyl acrylate was added dropwise, and the mixture was heated at 70°C for 3 hours to obtain the desired sol. DLS method yielded an average particle size of 64 nm, pH 3.9, and SiO2. ２ The concentration was 14.9% by mass and the moisture content was 0.5% by mass. Furthermore, there was no sedimentation, indicating good dispersibility.

[0254] <Synthesis Example 15> Synthesis of PGME hollow silica sol (AA3-2-2) whose surface was treated with alkali-developable surface treatment agent 3. 30 g of PGME hollow silica sol (AA3-2) whose surface was treated with 3-(methoxydimethylsilyl)propyl as prepared in Synthesis Example 14 was placed in a 100 mL round-bottom flask with a condenser. 0.01 g of tripentylamine was added and heated at 70°C for 1 hour to obtain the target sol. The average particle size was 65 nm, pH 3.9, and SiO was obtained by DLS method. ２ The concentration was 14.9% by mass and the moisture content was 0.5% by mass. Furthermore, there was no sedimentation, indicating good dispersibility.

[0255] <Synthesis Example 16> Synthesis of PGME hollow silica sol treated with alkali-developable surface treatment agent 3 (AA3-3) 30 g of hollow silica PGME sol, which was surface-treated with alkali-developable surface treatment agent 3 prepared in Synthesis Example 13, was placed in a 100 mL round-bottom flask with a condenser. 0.14 g of dimethylethoxyvinylsilane was added dropwise, and the mixture was heated at 70°C for 3 hours to obtain the desired sol. DLS method yielded an average particle size of 64 nm, pH 3.9, and SiO ２ The concentration was 14.9% by mass and the moisture content was 0.5% by mass. Furthermore, there was no sedimentation, indicating good dispersibility.

[0256] <Synthesis Example 17> Synthesis of PGME hollow silica sol treated with alkali-developable surface treatment agent 3 (AA3-3-2) 30 g of PGME hollow silica sol, surface-treated in the same manner as in Synthesis Example 16, was placed in a 100 mL round-bottom flask with a condenser. 0.01 g of tripentylamine was added and heated at 70°C for 1 hour to obtain the target sol. DLS method yielded an average particle size of 65 nm, pH 7.5, and SiO ２ The concentration was 14.9% by mass and the moisture content was 0.5% by mass. Furthermore, there was no sedimentation, indicating good dispersibility.

[0257] <Synthesis Example 18> Synthesis of hollow silica treated with alkali-developable surface treatment agent 4 (AA4) 8.6 g of the surface treatment agent 4 solution in 40% MEK solvent prepared in Synthesis Example 12 was added to a 500 mL round-bottom flask with a condenser containing 100 g of the PGME-dispersed hollow silica sol (a3) ​​obtained in Synthesis Example 10. The mixture was heated at 70°C for 3 hours while stirring with a magnetic stirrer to obtain the desired sol. The obtained sol had an average particle size of 65 nm, pH 4.6, and SiO2 by DLS method. ２ The concentration was 14.9% by mass and the moisture content was 0.5% by mass. Furthermore, there was no sedimentation, indicating good dispersibility.

[0258] <Synthesis Example 19> Synthesis of hollow silica surface treated with alkali-developable surface treatment agent 4 (AA4-2) 30 g of hollow silica PGME sol, surface treated with alkali-developable surface treatment agent 4 prepared in Synthesis Example 18, was placed in a 100 mL round-bottom flask with a condenser. 2.48 g of ethoxylyl cydimethoxypropyl methacrylate was added dropwise, and the mixture was heated at 70°C for 3 hours to obtain the desired sol. DLS method yielded an average particle size of 64 nm, pH 4.6, and SiO2. ２ The concentration was 14.9% by mass and the moisture content was 0.5% by mass. Furthermore, there was no sedimentation, indicating good dispersibility.

[0259] <Example 1> Synthesis of Alkaline Developable Solid Silica Particles (DAA1) 5 g of solid silica sol obtained in Synthesis Example 6 was placed in a 50 mL round-bottom flask and treated in an evaporator at 60°C / 50 Torr for 1 hour to obtain 1 g of silica particle powder. 5 mg of this powder was added to 10 mL of 1% KOH aqueous solution and immersed for 1 minute. As a result, it was visually confirmed that the silica particles dissolved in the 1% KOH aqueous solution.

[0260] <Example 2> Synthesis of Alkaline Detergent Hollow Silica Particles (DAA2) 5 g of the hollow silica sol obtained in Synthesis Example 8 was placed in a 50 mL round-bottom flask and treated in an evaporator at 60°C / 50 Torr for 1 hour to obtain 1 g of silica particle powder. 5 mg of this powder was added to 10 mL of 1% KOH aqueous solution and immersed for 1 minute. As a result, it was visually confirmed that the silica particles dissolved in the 1% KOH aqueous solution.

[0261] <Example 3> Synthesis of Alkaline Detergent Hollow Silica Particles (DAA3) 10 g of PGME silica sol obtained in Synthesis Example 13 was placed in a 50 mL round-bottom flask and treated with an evaporator at 60°C / 50 Torr for 1 hour to obtain 1.5 g of silica particle powder. 5 mg of this powder was added to 10 mL of 1% KOH aqueous solution and immersed for 10 minutes. As a result, it was visually confirmed that the silica particles dissolved in the 1% KOH aqueous solution.

[0262] <Examples 4-9> Synthesis of Alkaline Developerable Silica Particles (DAA4-9) Similar to Example 3, 10 g each of the PGME silica sols obtained in Examples 14-19 were placed in 50 mL round-bottom flasks and treated in an evaporator at 60°C / 50 Torr for 1 hour to obtain 1.5 g of silica particle powder from each sample. 5 mg of each of these powders was added to 10 mL of 1% KOH aqueous solution and immersed for 1 hour. As a result, it was visually confirmed that the silica particles dissolved in the 1% KOH aqueous solution.

[0263] <Comparative Example 1> Synthesis of Acidic Sol 100 g of MT-ST was added to a 500 mL round-bottom flask, followed by 5.3 g of M33TMOSPAP. The mixture was heated at 65°C for 3 hours while stirring with a magnetic stirrer. As a result, the sol gelled, and the desired sol could not be obtained.

[0264] <Comparative Example 2> Synthesis of Silica Particles 4 g of the MeOH-dispersed solid silica sol (a2) obtained in Synthesis Example 4 was placed in a round-bottom flask and treated with an evaporator at 60°C / 50 Torr for 1 hour to obtain 1.2 g of silica particle powder. 5 mg of this powder was added to 10 mL of a 1% KOH aqueous solution and immersed for 1 minute. As a result, it was visually confirmed that the silica particles were insoluble in the 1% KOH aqueous solution.

[0265] <Example 10> Synthesis of Photosensitive Resin Composition 1 (Ex1) 10 g of the 20% MeOH / MEK mixed solution of AA2 obtained in Synthesis Example 8 and 8 g of PGEE were placed in a 100 mL round-bottom flask, and the mixture was reduced under reduced pressure at 60°C / 100 Torr to prepare a 20% PGEE sol. Then, 2.3 g of this solution was placed in a 30 mL brown sample bottle under yellow room conditions, and then 3 g of the polysiloxane (P1) PGEE solution obtained in Synthesis Example 1, 0.14 g of PA-3, and 0.37 g of PGEE were added. After removing methanol, the mixture was stirred in a mix rotor at 23°C for 4 hours to obtain the target photosensitive resin composition 1 (Ex1).

[0266] <Example 11> Synthesis of Photosensitive Resin Composition 2 (Ex2) Under yellow room conditions, 5 g of a 20% PGMEA solution of polyhydroxyimide (P2) obtained in Synthesis Example 2 and 5 g of a 20% MeOH / MEK mixed solution of AA1 obtained in Synthesis Example 6 were added to a 30 mL brown sample bottle. Methanol was then removed, and 0.6 g of PA-3 and 0.01 g of PGEE were added. The mixture was stirred at room temperature for 3 hours to obtain the target photosensitive resin composition (Ex2).

[0267] <Example 12> Synthesis of Photosensitive Resin Composition 3 (Ex3) Under yellow room conditions, 5 g of a 20% PGMEA solution of polyhydroxyimide (P2) obtained in Synthesis Example 2 and 5 g of a 20% MeOH / MEK mixed solution of AA1 obtained in Synthesis Example 6 were added to a 30 mL brown sample bottle. Methanol was then removed, 0.3 g of VE and 0.05 g of PAG were added, and the mixture was stirred at room temperature for 3 hours to obtain the target photosensitive resin composition (Ex3).

[0268] <Example 13> Synthesis of photosensitive resin composition 4 (Ex4) Under yellow room conditions, 1.5 g of a 40% PGME solution of polyacrylic (P4) obtained in Synthesis Example 9 and 3 g of a 20% MeOH / MEK mixed solution of AA2 obtained in Synthesis Example 8 were added to a 30 mL brown sample bottle. Methanol was then removed, and 0.3 g of PL-LI and 0.03 g of PAG were added. The mixture was stirred at room temperature for 3 hours to obtain the target photosensitive resin composition (Ex4).

[0269] <Example 14> Synthesis of photosensitive resin composition 5 (Ex5) Under yellow room conditions, 1.5 g of a 40% PGME solution of polyacrylic (P4) obtained in Synthesis Example 9 and 3 g of a 20% MeOH / MEK mixed solution of AA1 obtained in Synthesis Example 6 were added to a 30 mL brown sample bottle. Methanol was then removed, and 0.3 g of PL-LI and 0.03 g of PAG were added. The mixture was stirred at room temperature for 3 hours to obtain the target photosensitive resin composition (Ex5).

[0270] <Comparative Example 3> Synthesis of Photosensitive Resin Composition 1 (HEx1) 30 g of MT-ST and 21 g of PGEE were placed in a 200 mL round-bottom flask, and the mixture was reduced under reduced pressure at 60°C / 100 Torr to prepare a 30% PGEE sol. 3.3 g of this solution was placed in a 30 mL brown sample bottle under yellow room conditions, and 5 g of a 20% PGMEA solution of polyhydroxyimide (P2) obtained in Synthesis Example 2 and 0.6 g of PA-3 were added. The mixture was stirred at room temperature for 3 hours to obtain the target photosensitive resin composition (HEx1).

[0271] <Evaluation of Photosensitive Properties> [Coating Film Thickness] The photosensitive resin compositions obtained in Examples 10 to 14 and Comparative Example 3 were dropped onto a 4-inch silicon wafer and coated using a spin coater (Mikasa Corporation, product name MS-B100) at 800 rpm x 5 seconds. The wafers were then baked on a hot plate at 100°C for 2 minutes, and then further baked at 180°C for 30 minutes to form a coating film after pre-baking. The film thickness was measured using a contact-type film thickness gauge (ULVAC Corporation, product name Dektak 3ST).

[0272] [Exposure] After pre-baking, the coating film is exposed to an alkali-free mask and cured using an ultraviolet curing conveyor system (manufactured by Iwasaki Electric, product name iGrandage 4KW) at a rate of 1 J / cm². ２ Exposure.

[0273] [Post-exposure heating] The coating films obtained in Examples 12, 13, and 14 were again exposed to light on a hot plate and then heated and baked.

[0274] [Post-development condition and film thickness] After immersion in alkaline developer, the developer was rinsed with pure water. After development, the film thickness of the unexposed and exposed areas was measured. The presence or absence of residue in the developed area was checked using an optical microscope (50x magnification).

[0275] <Examples and Comparative Examples> Photosensitivity Evaluation Results Table 1 shows the results for Examples 10 to 14 and Comparative Example 3, including the composition used, development type, calcination conditions, film thickness, post-exposure heating and calcination conditions, development conditions, post-development film thickness change, and exposure residue. The post-development film thickness change was determined as follows. Figure 1 shows the pattern images of the residual film and developed areas for Example 4, and Figure 2 shows the developed area image for Comparative Example 3. <Post-development film thickness change> A: Residual film rate of 90% or more B: Residual film rate of 80% or more and less than 90% C: Residual film rate of 60% or more and less than 80% D: Residual film rate of less than 60%

[0276]

[0277] As shown in Table 1 and Figure 1, the cured films prepared from the photosensitive resin compositions of Examples 10 to 14, which used alkali-developable surface-treated silica particles, showed no residue after development. On the other hand, as shown in Table 1 and Figure 2, the cured film prepared from the photosensitive resin composition of Comparative Example 3, which used untreated silica particles, showed a large amount of residue after development.

Claims

1. An alkali-developable alkoxysilane compound represented by the following formula (1). (In the formula, R １ R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ２ , R ３ , R ４ One of these represents a monovalent group having an alkoxysilyl group, and the remaining two independently represent a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, a branched alkyl group having 3 to 16 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a phenyl group, a benzyl group, a phenethyl group, a phenylsulfonyl group, a meth(acryloyloxy)ethyl group, or a meth(acryloyloxy)propyl group, wherein the alkyl group and branched alkyl group may be substituted with a halogen atom, and the alkyl group and branched alkyl group may also be substituted with a urea group. The urea group may be substituted with one or more groups selected from a monovalent group having an ester moiety, an alkyl group having a urea moiety substituted with a monovalent group having an ester moiety, a phenyl group having a urea moiety substituted with a monovalent group having an ester moiety, a phenyl group, and an alkyl group. The phenyl group, benzyl group, phenethyl group, and phenylsulfonyl group in the above definition may be substituted with a group selected from an alkyl group, an alkoxy group, a halogen atom, a nitro group, and a cyano group, and L represents an alkylene group or phenylene group having 1 to 4 carbon atoms.

2. The alkali-developable alkoxysilane compound according to claim 1, wherein the compound represented by the formula (1) is a compound represented by the following formula (1-1), (1-2), (1-3) or (1-4). [In the formulas (1-1), (1-2), (1-3) and (1-4), R １ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ５ and R ６ each independently represent an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an alkynyl group having 2 to 4 carbon atoms, R １１ represents a hydrogen atom or a methyl group, R １２ represents a hydrogen atom, a methyl group, an ethyl group or a phenyl group, L represents an alkylene group having 1 to 4 carbon atoms or a phenylene group, and q represents an integer of 1 to 3.] 3. Silicon-based inorganic fine particles surface-treated with a compound represented by the following formulas (1-1), (1-2), (1-3), or (1-4). [In formulas (1-1), (1-2), (1-3), and (1-4), R １ R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ５ and R ６ Each of these independently represents an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an alkynyl group having 2 to 4 carbon atoms, R １１ represents a hydrogen atom or a methyl group, R １２ represents a hydrogen atom, methyl group, ethyl group, or phenyl group; L represents an alkylene group or phenylene group with 1 to 4 carbon atoms; and q represents an integer from 1 to 3.

4. A thermosetting photosensitive resin composition containing the following components (A), (B), (C) solvent, and (D): (A) component: silica particles with an average primary particle diameter of 1 nm to 1 μm, surface-treated with the alkali-developable alkoxysilane compound described in claim 1; (B) component: binder resin; (C) solvent; (D) component: photosensitive agent.

5. The photosensitive resin composition according to claim 4, satisfying at least one of the following (Z1) to (Z5): (Z1): Further contains a crosslinking agent which is component (E). (Z2): The binder resin which is component (B) has a self-crosslinking group or a group which reacts with at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group and an amino group. (Z3): Component (D) is a photoradical generator, and further contains a compound which is component (F) having two or more ethylenically double bonds. (Z4): Component (D) is a photoacid generator, and further contains a compound which is component (G) having two or more functional groups which form covalent bonds with the acid generated from component (D). (Z5): Component (D) is a photoacid generator, and further contains a compound which is component (H) having two or more functional groups which decompose covalent bonds with the acid generated from component (D).

6. The photosensitive resin composition according to claim 5, wherein component (D) is a quinone diazide compound.

7. The photosensitive resin composition according to claim 6, wherein component (D) is a quinone diazide compound and satisfies either (Z1) or (Z2) above.

8. The amount of the compound represented by formula (1) used for surface modification of the silica particles of component (A) is equal to the surface area of ​​the silica particles per 1 nm. ２ The photosensitive resin composition according to claim 4, wherein the number of particles per unit ranges from 0.5 to 6.

9. The photosensitive resin composition according to claim 4, wherein the weight-average molecular weight of the binder resin of component (B) is 1,000 to 50,000 in terms of polystyrene.

10. The photosensitive resin composition according to claim 4, characterized in that it contains 0.1 to 1000 parts by mass of component (A) per 100 parts by mass of component (B).

11. The photosensitive resin composition according to claim 5, characterized in that component (E) is 1 to 60 parts by mass with respect to a total of 100 parts by mass of component (A) and component (B).

12. A cured film obtained using the photosensitive resin composition according to any one of claims 4 to 11.

Images