Composition

Abstract

The present invention relates to a composition comprising a photosensitive composition containing at least an alkali-soluble polymer.

Description

Technical Field

[0001] The present invention relates to a photosensitive composition containing at least an alkali-soluble polymer, a method for preparing the photosensitive composition, use of the photosensitive composition, a method for producing a composite material, the composite material, and a display device.

Background Art

[0002] U.S. Patent Application Publication No. 2010 / 0016488 discloses a method for producing an organosiloxane polymer, which includes hydrolyzing tri- and tetraalkoxysilane monomers in a hydrolysis step and subjecting the hydrolyzed monomers to conditions that promote polymerization to polymerize the hydrolyzed monomers in a polymerization step to form an organosiloxane polymer, wherein the hydrolysis step is carried out in a reaction medium containing an organic compound having a hydroxy group. Also disclosed is the use of a composition produced by a process for optical and electrical coatings.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, the inventors have newly found that one or more of the following problems to be considered for improvement still exist: Preferably, to obtain a photosensitive composition that can achieve an improved scattering effect and increase the haze value while maintaining a constant transmittance; to provide a photosensitive composition that can achieve improved brightness from the side angle of the cured film, improved dispersion of scattering particles in the optical layer and / or in the photosensitive composition, and that achieves the aforementioned improved scattering effect and / or improved brightness from the side angle with a small amount of scattering particles.

[0005] The present inventors aimed to solve one or more of the above-mentioned problems. [Means for solving the problem]

[0006] Therefore, as stated in the claims, (I) an alkali-soluble polymer, preferably a polysiloxane, an acrylic polymer, or a combination of a polysiloxane and an acrylic polymer, (II) Polymerization initiator, (III) Scattering particles and Novel photosensitive compositions have been discovered that contain at least, essentially consist of, or consist of.

[0007] In another embodiment, the present invention relates to the following steps: (X) At least, (I) an alkali-soluble polymer, preferably a polysiloxane, an acrylic polymer, or a combination of a polysiloxane and an acrylic polymer, (II) Polymerization initiator, (III) Scattering particles and The process of mixing The present invention relates to a method for preparing a composition comprising, essentially comprising, or consisting of at least the following.

[0008] In another aspect, the present invention relates to the use of the compositions of the present invention for preparing an optical layer containing a metal oxide, preferably for preparing a composite material, and more preferably for preparing a layered composite material.

[0009] In another embodiment, the present invention comprises the following steps: (Xi) A step of applying the composition of the present invention to a layer or substrate to form a coated layer, (Xii) A process of baking the coated layer to obtain a composite material. The present invention relates to a method for manufacturing composite materials, including [specific material].

[0010] Preferably, this method includes the following steps after step (Xi) and before step (Xii): (Xiii) A step of applying a pre-bake (heat treatment) to the coated layer in order to dry the coated layer and reduce the amount of solvent remaining in the coated layer. (Xiv) A step of irradiating the coated layer with light, preferably light having a peak maximum wavelength in the range of 360 to 430 nm (a step of applying light irradiation), preferably a step of using a patterning mask when light irradiation is performed. (Xv) A step of applying a post-exposure bake process, and / or (Xvi) A process of applying a development process to form a patterned hardened layer. This includes one or more of the following.

[0011] In another embodiment, the present invention relates to a composite material, preferably a layered composite material, wherein the aforementioned layered composite material is an optical layer obtained or obtainable by the method of the present invention.

[0012] In another embodiment, the present invention relates to a composite material, preferably a layered composite material, and preferably the aforementioned layered composite material is i) A polymer (A) that is derived from or can be derived from at least (I) an alkali-soluble polymer, preferably the aforementioned alkali-soluble polymer being a polysiloxane, an acrylic polymer, or a combination of a polysiloxane and an acrylic polymer, (III) Scattering particles and An optical layer that includes at least, essentially consists of, or comprises the following.

[0013] In another embodiment, the present invention further relates to a display device comprising a composite material of the present invention and at least one functional medium configured to modulate or emit light.

[0014] Further advantages of the present invention will become apparent from the following detailed description. [Effects of the Invention]

[0015] The present invention provides one or more of the following technical effects: Preferably, to obtain a photosensitive composition that can achieve an improved scattering effect and increase the haze value while maintaining a constant transmittance; to provide a photosensitive composition that can achieve improved brightness from the side angle of the cured film, improved dispersion of scattering particles in the optical layer and / or in the photosensitive composition, and that achieves the aforementioned improved scattering effect and / or improved brightness from the side angle with a small amount of scattering particles. [Modes for carrying out the invention]

[0016] Definition of Terms In this specification, symbols, units, abbreviations, and terms have the following meanings unless otherwise specified.

[0017] In this specification, unless otherwise specifically mentioned, the singular form includes the plural form, and “one” or “it” means “at least one.” In this specification, unless otherwise specifically mentioned, elements of a concept may be represented by multiple types, and if a quantity (e.g., mass % or mole %) is given, it means the sum of multiple types. “And / or” includes all combinations of elements, and further includes single use of an element.

[0018] In this specification, when a numerical range is indicated using "~" or "-", it includes the fact that both endpoints and their units are common. For example, 5~25 mol% means 5 mol% or more and 25 mol% or less.

[0019] In this specification, hydrocarbons mean hydrocarbons containing carbon and hydrogen, and optionally containing oxygen or nitrogen. Hydrocarbyl groups mean monovalent or divalent or more hydrocarbons. In this specification, aliphatic hydrocarbons mean linear, branched or cyclic aliphatic hydrocarbons, and aliphatic hydrocarbon groups mean monovalent or divalent or more aliphatic hydrocarbons. Aromatic hydrocarbons mean hydrocarbons containing aromatic rings that can optionally contain aliphatic hydrocarbon groups as substituents and can also be condensed with alicyclic rings. Aromatic hydrocarbon groups mean monovalent or divalent or more aromatic hydrocarbons. Furthermore, aromatic rings mean hydrocarbons containing a conjugated unsaturated ring structure, and alicyclic rings mean hydrocarbons that have a ring structure but do not contain a conjugated unsaturated ring structure.

[0020] In this specification, alkyl means a group obtained by removing any one hydrogen from a linear or branched saturated hydrocarbon, and includes linear alkyls and branched alkyls, and cycloalkyl means a group obtained by removing one hydrogen from a saturated hydrocarbon containing a cyclic structure, and optionally includes a linear or branched alkyl in the cyclic structure as a side chain.

[0021] In this specification, aryl means a group obtained by removing any one hydrogen from an aromatic hydrocarbon. Alkylene means a group obtained by removing any two hydrogens from a straight-chain or branched saturated hydrocarbon. Arylene means a hydrocarbon group obtained by removing any two hydrogens from an aromatic hydrocarbon.

[0022] In this specification, if a polymer has multiple types of repeating units, these repeating units copolymerize. These copolymerizations are either alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture of these.

[0023] In this specification, Celsius is used as the unit of temperature. For example, 20°C and 20 degrees mean 20 degrees Celsius.

[0024] Detailed description of the invention According to the present invention, in one embodiment, the photosensitive composition is (I) an alkali-soluble polymer, preferably a polysiloxane, an acrylic polymer, or a combination of a polysiloxane and an acrylic polymer, (II) Polymerization initiator, (III) Scattering particles and It includes at least, essentially consists of, or consists of.

[0025] Preferably, the aforementioned photosensitive composition is a negative-type photosensitive composition, and preferably, the aforementioned photosensitive composition is used to manufacture a protective layer for an electronic device. Preferably, the aforementioned photosensitive composition is a filling composition used to manufacture an electronic device, and more preferably, a filling composition for an LED or μLED.

[0026] (I) Alkali-soluble polymers - Polysiloxane According to the present invention, in a preferred embodiment, the aforementioned alkali-soluble polymer is a polysiloxane, a (meth)acrylic polymer, or a combination of a polysiloxane and a (meth)acrylic polymer. Any publicly available polysiloxane and / or (meth)acrylic polymer can be used. Preferably, the aforementioned polysiloxane contains a repeating unit of chemical formula (I Ia ). [Chemical Formula] (In the formula, R Ia is hydrogen, C 1-30 (preferably C 1-10 ) linear, C 3-30 (preferably C 3-10 ) branched or cyclic, saturated or unsaturated aliphatic hydrocarbon group or aromatic hydrocarbon group, and these aliphatic hydrocarbon groups and aromatic hydrocarbon groups are each unsubstituted or substituted with fluorine, hydroxy, or alkoxy, in the aliphatic hydrocarbon group and aromatic hydrocarbon group, methylene is not replaced, or one or more methylenes are replaced by oxy, imino or carbonyl, provided that R Ia is not hydroxy or alkoxy).

[0027] Here, the above methylene includes terminal methyl. Further, the above "substituted with fluorine, hydroxy, or alkoxy" means that a hydrogen atom directly bonded to a carbon atom of the aliphatic hydrocarbon group and aromatic hydrocarbon group is replaced by fluorine, hydroxy, or alkoxy. In this specification, the same applies to other similar descriptions.

[0028] In a more preferred embodiment of the present invention, in the repeating unit represented by formula (I a ), R IaThis includes, for example, (i) alkyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and decyl; (ii) aryl groups, such as phenyl, tolyl, and benzyl; (iii) fluoroalkyl groups, such as trifluoromethyl, 2,2,2-trifluoroethyl, and 3,3,3-trifluoropropyl; (iv) fluoroaryl groups; (v) cycloalkyl groups, such as cyclohexyl; (vi) nitrogen-containing groups having an amino or imide structure, such as isocyanates and aminos; and (vii) oxygen-containing groups having an epoxy structure such as glycidyl, or an acryloyl or methacryloyl structure. Preferably, it is methyl, ethyl, propyl, butyl, pentyl, hexyl, and phenyl. Because its raw materials are easily obtained, and its film hardness after curing is high and its chemical resistance is high, R Ia Compounds in which the compound is methyl are preferred. Furthermore, R increases the solubility of the polysiloxane in the solvent and makes the cured film less prone to cracking. Ia Compounds in which the parent molecule is phenyl are preferred.

[0029] In a preferred embodiment of the present invention, the polysiloxane used in the present invention is of formula (I b ): [ka] (In the formula, R Ib (A group obtained by removing multiple hydrogen atoms from a nitrogen and / or oxygen-containing alicyclic hydrocarbon compound having amino, imino, and / or carbonyl groups.) It may further include repeating units represented by .

[0030] In formula (Ib), preferably, R IbThis group is obtained by removing several hydrogens, preferably two or three, from a nitrogen-containing aliphatic hydrocarbon ring, preferably having an imino and / or carbonyl group, and more preferably from a five-membered or six-membered ring containing nitrogen as a member. For example, it is obtained by removing two or three hydrogens from piperidine, pyrrolidine, or isocyanurate. Ib This involves bonding the Si atoms contained within multiple repeating units to each other.

[0031] In a preferred embodiment of the present invention, the polysiloxane used in the present invention is of formula (I c ): [ka] It may further include repeating units represented by .

[0032] Equation (I b ) and (I c If the mixing ratio of repeating units, represented by ), is high, the compatibility with the solvent and additives decreases, the film stress increases, and as a result, cracks may be more likely to occur. Therefore, it is preferably 40 mol% or less, more preferably 20 mol% or less, based on the total number of repeating units of the polysiloxane.

[0033] According to the present invention, in some embodiments, the polysiloxane used in the present invention is of formula (I d ): [ka] (In the formula, R Id These are, independently, hydrogen and C 1-30 (preferably C 1-10 ) Linear chain, C 3-30 (preferably C 3-10 ) Represents a branched or cyclic, saturated or unsaturated aliphatic hydrocarbon group or aromatic hydrocarbon group, Aliphatic hydrocarbon groups and aromatic hydrocarbon groups are either unsubstituted or substituted with fluorine, hydroxyl, or alkoxy, respectively. In aliphatic hydrocarbon groups and aromatic hydrocarbon groups, methylene is either not substituted or is substituted by oxy, imide, or carbonyl. It may further include repeating units represented by .

[0034] Equation (I d In the repeating unit represented by ), R Id It includes, for example, (i) alkyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and decyl; (ii) aryl groups, such as phenyl, tolyl, and benzyl; (iii) fluoroalkyl groups, such as trifluoromethyl, 2,2,2-trifluoroethyl, and 3,3,3-trifluoropropyl; (iv) fluoroaryl groups; (v) cycloalkyl groups, such as cyclohexyl; (vi) nitrogen-containing groups having an amino or imide structure, such as isocyanates and aminos; and (vii) oxygen-containing groups having an epoxy structure such as glycidyl, or an acryloyl or methacryloyl structure. Preferably, it is methyl, ethyl, propyl, butyl, pentyl, hexyl, and phenyl. Because its raw materials are easily obtained, and its film hardness after curing is high and its chemical resistance is high, R Id Compounds in which the compound is methyl are preferred. Furthermore, R increases the solubility of the polysiloxane in the solvent and makes the cured film less prone to cracking. Id Compounds in which the parent molecule is phenyl are preferred.

[0035] The above formula (I d By having repeating units of ), it is possible to produce a polysiloxane with a partially linear structure according to the present invention.

[0036] However, it is preferable to have fewer linear structures because this reduces heat resistance. In particular, formula (I d The repeating units of formula (I) are preferably 30 mol% or less, more preferably 5 mol% or less, based on the total number of repeating units of the polysiloxane. d Another aspect of the present invention is that it does not have repeating units (0 mol%).

[0037] The polysiloxane used in the present invention may contain two or more types of repeating units. For example, it may be formula (Ia) (wherein R Ia A repeating unit represented by (which is methyl or phenyl), and formula (I c It may include three types of repeating units having a repeating unit represented by ).

[0038] In addition, the polysiloxane used in the composition according to the present invention preferably has a silanol. Here, a silanol refers to a polysiloxane in which the OH group is directly bonded to the Si skeleton, and the hydroxyl group is of the above formula (I a )~(I d It is directly bonded to the silicon atom in polysiloxanes that contain repeating units such as ). In other words, silanols are directly bonded to the silicon atom in polysiloxanes that contain repeating units such as ) above. a )~(I d It is formed by bonding -O0.5H and -O0.5- in the ) part. The silanol content in polysiloxane varies depending on the conditions for synthesizing the polysiloxane, such as the monomer mixing ratio and the type of reaction catalyst.

[0039] The silanol content can be evaluated by quantitative infrared absorption spectroscopy. The absorption band attributed to silanol (SiOH) is 900 ± 100 cm⁻¹ in the infrared absorption spectrum. -1 It appears as an absorption band with a peak in the specified range. The intensity of this absorption band increases with higher silanol content.

[0040] In this invention, the intensity of the absorption band attributed to Si-O is used as a reference for quantitatively evaluating the silanol content. 1100±100cm -1Absorption bands having peaks within this range are adopted as peaks attributed to Si-O. The silanol content can be relatively evaluated by the ratio S2 / S1, which is the ratio of the integral intensity S2 of the absorption band attributed to SiOH to the integral intensity S1 of the absorption band attributed to Si-O. In the present invention, the ratio S2 / S1 is preferably 0.003 to 0.15, more preferably 0.01 to 0.10.

[0041] The integrated intensity of the absorption band is determined by taking into account noise in the infrared absorption spectrum. In a typical infrared absorption spectrum of polysiloxanes, this is 900 ± 100 cm⁻¹. -1 Absorption bands attributed to Si-OH with peaks in the range of 1100±100cm -1 Absorption bands attributed to Si-O with peaks in the specified range are observed. The integrated intensity of these absorption bands can be measured as an area considering a baseline that takes noise into account. Note that the foot of the absorption band attributed to Si-OH and the foot of the absorption band attributed to Si-O may overlap; in this case, the wavenumber corresponding to the minimum point between the two absorption bands in the spectrum is set as their boundary. The same applies when the foot of another absorption band overlaps with the foot of an absorption band attributed to Si-OH or Si-O.

[0042] The mass-average molecular weight of the polysiloxane used in this invention is not particularly limited. However, higher molecular weights tend to result in improved coating properties. On the other hand, lower molecular weights are easier to synthesize because the synthesis conditions are less restricted, while the synthesis of polysiloxanes with significantly high molecular weights is difficult. For these reasons, the mass-average molecular weight of the polysiloxane is usually 500 to 25,000, preferably 1,000 to 20,000, from the viewpoint of solubility in organic solvents. Here, the mass-average molecular weight refers to the mass-average molecular weight in terms of polystyrene, which can be measured by gel permeation chromatography based on polystyrene.

[0043] The method for synthesizing the polysiloxane used in the present invention is not particularly limited. For example, it can be synthesized according to the method disclosed in Japanese Patent No. 6639724.

[0044] As described above, publicly available polysiloxanes fall under the above definition and can preferably be used as described, for example, in International Publication No. 2021 / 099236 and European Patent No. 3717966.

[0045] It is believed that the use / addition of polysiloxane can improve photostability, chemical stability, color change due to degradation of the cured film, and / or thermal stability of the cured film.

[0046] - (meth)acrylic polymer When an acrylic polymer is used as an alkali-soluble polymer in the present invention, it can be selected from commonly used (meth)acrylic polymers, preferably from acrylic polymers such as polyacrylic acid, polymethacrylic acid, polyalkyl acrylate, and polyalkyl methacrylate.

[0047] It is believed that using (meth)acrylic polymers can enable thicker layers, lower process temperatures, and / or improved etching properties.

[0048] The acrylic polymer used in the present invention preferably comprises repeating units containing acryloyl groups. The acrylic polymer may further preferably comprise repeating units containing carboxyl groups and / or repeating units containing alkoxysilyl groups.

[0049] The repeating unit containing a carboxyl group is not particularly limited as long as it contains a carboxyl group in its side chain, but repeating units derived from unsaturated carboxylic acids, unsaturated carboxylic acid anhydrides, or mixtures thereof are preferred.

[0050] A repeating unit containing an alkoxysilyl group may be a repeating unit containing an alkoxysilyl group in its side chain, preferably of the following formula (B): X B -(CH2) a -Si(OR B ) b (CH3) 3-b (B) (In the formula, X B R is a vinyl group, a styryl group, or a (meth)acryloyloxy group, B (where a is a methyl group or an ethyl group, a is an integer from 0 to 3, and b is an integer from 1 to 3) It is a repeating unit derived from monomers represented by .

[0051] Furthermore, the polymer described above preferably contains repeating units containing hydroxyl groups derived from hydroxyl group-containing unsaturated monomers.

[0052] The mass-average molecular weight of the acrylic polymer used in the present invention is not particularly limited, but is preferably 1,000 to 40,000, and more preferably 2,000 to 30,000. The mass-average molecular weight is the mass-average molecular weight on a polystyrene basis determined by gel permeation chromatography.

[0053] The content of acrylic polymer (II) is preferably 18.0 to 35.0% by mass, and more preferably 20.0 to 32.0% by mass, based on the total mass of the composition.

[0054] The content of acrylic polymer (II) is preferably 65.0 to 92.0% by mass, and more preferably 70.0 to 90.0% by mass, based on the total mass of polysiloxane (I) and acrylic polymer (II).

[0055] In preferred embodiments of the present invention, the aforementioned alkali-soluble polymer is a polysiloxane or a combination of a polysiloxane and an acrylic polymer, and the total amount of polysiloxane is in the range of 1 to 40% by mass, preferably 5 to 35% by mass, and more preferably 10 to 30% by mass, based on the total mass of the solvent-free composition.

[0056] In preferred embodiments of the present invention, the aforementioned acrylic polymer is selected from one or more components of the group consisting of polyacrylic acid, polymethacrylic acid, polyalkyl acrylate, and polyalkyl methacrylate. Preferably, the total amount of acrylic polymer in the composition is in the range of 65 to 99% by mass, more preferably 70 to 90% by mass, based on the total mass of the solvent-free composition.

[0057] (II) Polymerization initiator The composition according to the present invention contains a polymerization initiator. Polymerization initiators include polymerization initiators that generate acids, bases, or radicals by radiation, and polymerization initiators that generate acids, bases, or radicals by heat. In the present invention, the reaction is started immediately after irradiation with radiation, and the reheating process, which is carried out after irradiation with radiation and before the development process, can be eliminated. Therefore, from the viewpoint of shortening the process and reducing costs, the former is preferred, and photoradical generators are more preferred.

[0058] Photoradical generators can improve resolution by enhancing the molded pattern or increasing the contrast of the development. The photoradical generators used in this invention are photoradical generators that release radicals when irradiated with radiation. Examples of radiation include visible light, ultraviolet light, infrared light, X-rays, electron beams, alpha rays, and gamma rays.

[0059] The content of the photoradical generator is preferably 0.001 to 30% by mass, more preferably 0.01 to 10% by mass, based on the total mass of components (I) and (II). However, the optimal amount depends on the type and amount of active substances generated by the decomposition of the photoradical generator, the required photosensitivity, and the required dissolution contrast between the exposed and unexposed areas. If the content is less than 0.001% by mass, the dissolution contrast between the exposed and unexposed areas may be too low, and the additive effect may not be observed. On the other hand, if the content of the photoradical generator exceeds 30% by mass, cracks may occur in the coated film, and discoloration may become significant due to the decomposition of the photoradical generator, which may reduce the colorless transparency of the coated film.

[0060] If the content is high, thermal decomposition can cause deterioration of the electrical insulation of the cured product and release of gases, which can be problematic in subsequent processes. Furthermore, the coated film may have reduced resistance to photoresist strippers containing monoethanolamine or similar substances as the main component.

[0061] Examples of photoradical generators include azo, peroxide, acylphosphine oxide, alkylphenone, oxime ester, and titanocene initiators. Among these, alkylphenone, acylphosphine oxide, and oxime ester initiators are preferred, including 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)-benzyl]phenyl}-2-methylpropan-1-one, and 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan- Examples include 1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)-phenyl]-1-butanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzoyl oxime)], and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone-1-(O-acetyloxime).

[0062] (III) Scattering particles According to the present invention, preferably, the average particle size of the scattered particles is 200 nm to 10 μm, preferably 230 nm to 5 μm, and more preferably 250 nm to 2 μm. When the scattered particles are inorganic particles, preferably, the average particle size is in the range of 200 nm to 1 μm, preferably 230 nm to 800 nm, more preferably 250 nm to 700 nm, and even more preferably 300 nm to 600 nm. When the scattered particles are organic particles, preferably, the average particle size is in the range of 300 nm to 10 μm, more preferably 500 nm to 5 μm, even more preferably 700 nm to 3 μm, and even more preferably 800 nm to 2 μm.

[0063] In a preferred embodiment of the present invention, the scattering particles have a refractive index higher than that of the mixture of polysiloxane and acrylic polymer, and preferably, the scattering particles are configured to have a refractive index higher than that of the matrix polymer derived from the polysiloxane and acrylic polymer by polymerization. Preferably, the aforementioned refractive index of the scattering particles is 1.6 or higher, preferably 1.7 or higher, and 2.4 or lower, preferably 2.2 or lower. Most preferably 1.8 to 2.0. When two or more different scattering particles are used in the composition, the average refractive index of the scattering particles is 1.6 or higher, preferably 1.7 or higher, and 2.4 or lower, preferably 2.2 or lower. Most preferably 1.8 to 2.0.

[0064] The high refractive index of the scattering particles, as described above, is thought to enhance the scattering effect. In other words, when the aforementioned scattering particles have the average particle size described above and the refractive index value shown above, the aforementioned scattering effect becomes optimal in the resulting optical layer.

[0065] In another preferred embodiment, the scattering particles are organic particles, and the difference X between the refractive index of the scattering particles and the refractive index of the mixture of polysiloxane and acrylic polymer is in the range of -0.2 to +0.2. Preferably, the difference X' between the refractive index of the scattering particles and the refractive index of the matrix polymer derived from the polysiloxane and acrylic polymer by polymerization is in the range of -0.2 to +0.2.

[0066] X: Refractive index of scattering particles - Refractive index of mixture = -0.2 to +0.2, preferably -0.1 to +0.1

[0067] X': Refractive index of scattering particles - Refractive index of matrix polymer derived from polysiloxane and acrylic polymer by polymerization = -0.2 to +0.2, preferably -0.1 to +0.1

[0068] When a mixture of organic particles is used as scattering particles, the definition of X is: average refractive index of the scattering particles minus the refractive index of the mixture = -0.2 to +0.2, preferably -0.1 to +0.1. The definition of X' is: average refractive index of the scattering particles minus the refractive index of the matrix polymer derived from polysiloxane and acrylic polymers by polymerization = -0.2 to +0.2, preferably -0.1 to +0.1.

[0069] If the scattering particles are organic particles, and the difference X between the refractive index of the scattering particles and the refractive index of the mixture of polysiloxane and acrylic polymer is within the range defined above, then the incident light can sufficiently pass through the aforementioned scattering particles.

[0070] When organic scattering is used in an optical layer (composite material), the outermost surface of the resulting optical layer (composite material) has surface roughness caused by organic scattering. On a surface with this roughness, it is thought that the direction of light changes when it exits the optical layer (composite material). This effectively produces a scattering effect, preferably without causing light loss within the optical layer.

[0071] Preferably, any known inorganic / organic scattering particles that satisfy the above conditions can be used as such scattering particles.

[0072] For example, the scattering particles used in the examples can be preferably used.

[0073] - Solvent In preferred embodiments of the present invention, the composition further comprises a solvent from the viewpoint of improving handling, improving coating, and improving the coating of the composition when stringing it or producing layers. Preferably, the aforementioned solvent is an organic solvent, and more preferably, the aforementioned solvent is an ethylene glycol monoalkyl ether (preferably, it is ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and / or ethylene glycol monobutyl ether); diethylene glycol dialkyl ether (preferably, it is diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and / or diethylene glycol dibutyl ether); propylene glycol monoalkyl ether (preferably, it is propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether and / or propylene glycol monopropyl ether); ethylene glycol alkyl ether acetate (preferably, it is methyl cellosolve acetate and / or ethyl cellosolve acetate). ;Propylene glycol alkyl ether acetate (preferably propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate and / or propylene glycol monopropyl ether acetate); Ketones (preferably methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and / or cyclohexanone); Alcohols (preferably ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, triethylene glycol and / or glycerin); Esters (preferably ethyl 3-ethoxypropionate, methyl 3-methoxypropionate and / or ethyl lactate), and cyclic esters (preferably gamma-butyro-lactone); Chlorinated hydrocarbons (preferably chloroform, dichloromethane, chlorobenzene);The solvent is an organic solvent selected from one or more components of the group consisting of trimethylbenzenes (preferably 1,3,5-trimethylbenzene, 1,2,4-trimethylbenzene, and 1,2,3-trimethylbenzene), doceylbenzene, cyclohexylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 3-isopropylbiphenyl, 3-methylbiphenyl, 4-methylbiphenyl, and dichlorobenzene. Preferably, the aforementioned solvent is ethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, propylene glycol, ethylene glycol, propylene glycol monoalkyl ether, ethylene glycol alkyl ether acetate, or propylene glycol alkyl ether acetate. More preferably, the aforementioned solvent is selected from propylene glycol alkyl ether acetate, ethylene glycol monoalkyl ether, propylene glycol, and propylene glycol monoalkyl ether.

[0074] The solvent selected above is considered to have good compatibility with the composition, boiling point, viscosity and / or vapor pressure, and is suitable for production at lower temperatures, resulting in better handling of the composition and / or easier production.

[0075] In preferred embodiments of the present invention, the total amount of solvent is 0 to 300% by weight based on the total amount of polysiloxane. If the composition contains a solvent, it is preferably 0.1 to 150% by weight, more preferably 50 to 90% by weight.

[0076] - Compounds containing two or more (meth)acryloyloxy groups According to the present invention, in preferred embodiments, the composition further comprises a compound containing two or more (meth)acryloyloxy groups (hereinafter sometimes referred to as a (meth)acryloyloxy group-containing compound), and preferably the content of the compound is in the range of 10.0 to 25.0% by mass based on the total mass of the composition excluding the solvent.

[0077] (Meth)acryloyloxy groups are a general term for acryloyloxy groups and methacryloyloxy groups. These compounds can form crosslinked structures by reacting with polysiloxane(I), acrylic polymer(II), and the like. To form a crosslinked structure, a compound containing two or more reactive (meth)acryloyloxy groups is required. To form a higher-order crosslinked structure, it preferably contains three or more (meth)acryloyloxy groups.

[0078] Such compounds containing two or more (meth)acryloyloxy groups are preferably esters obtained by reacting a polyol compound having (α) two or more hydroxyl groups with (β) two or more (meth)acrylic acids. The polyol compound (α) includes compounds having saturated or unsaturated aliphatic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons, primary, secondary or tertiary amines, ethers, etc. as a basic skeleton and having two or more hydroxyl groups as substituents. As long as the effects of the present invention are not impaired, the polyol compound may contain other substituents, such as carboxyl groups, carbonyl groups, amino groups, ether bonds, thiol groups, thioether bonds, etc.

[0079] Preferred polyol compounds include alkyl polyols, aryl polyols, polyalkanolamines, cyanuric acid, and dipentaerythritol. When polyol compound (α) has three or more hydroxyl groups, not all hydroxyl groups need to react with (meth)acrylic acid, and can be partially esterified. This means that the ester may have unreacted hydroxyl groups.

[0080] Examples of such esters include tris(2-acrylooxyethyl) isocyanurate, bis(2-acrylooxyethyl) isocyanurate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipropylene glycol diacrylate, trippropylene glycol diacrylate, trimethylolpropane triacrylate, polytetramethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, ditrimethylolpropane tetraacrylate, tricyclodecanedimethanol diacrylate, 1,9-nonanediol diacrylate, 1,6-hexanediol diacrylate, and 1,10-decanediol diacrylate.

[0081] The composition according to the present invention comprises a combination of two or more (meth)acryloyloxy group-containing compounds, preferably a combination of three or more (meth)acryloyloxy group-containing compounds. In a preferred embodiment of the present invention, the composition according to the present invention comprises a combination of three (meth)acryloyloxy group-containing compounds.

[0082] While we do not wish to be constrained by theory, it is thought that combinations of (meth)acryloyloxy group-containing compounds with different glass transition temperatures can suppress rapid thermal reflow in the post-bake process, which may lead to the formation of specific taper angles.

[0083] Preferably, at least one of the two or more (meth)acryloyloxy group-containing compounds is a compound containing three or more (meth)acryloyloxy groups. More preferably, at least one is a compound containing three or more (preferably three) (meth)acryloyloxy groups, and at least one is a compound containing two (meth)acryloyloxy groups. Even more preferably, to make the pattern surface smoother, component (III) is a combination of one compound containing three (meth)acryloyloxy groups and two compounds containing two (meth)acryloyloxy groups.

[0084] In the composition according to the present invention, the content of the compound containing three or more (meth)acryloyloxy groups is preferably 20.0 to 50.0% by mass, more preferably 30.0 to 40.0% by mass, based on the total mass of component (III).

[0085] In another embodiment of the present invention, in order to improve alkali solubility during development and the heat resistance of the cured film, component (III) preferably comprises a compound having an isocyanurate structure. In particular, such compounds include tris(2-acryloyloxyethyl)isocyanurate. Bis(2-acryloyloxyethyl) isocyanurate, Tris(3-acryloyloxypropyl) isocyanurate, Bis(3-acryloyloxypropyl) isocyanurate, Tris(4-acryloyloxybutyl)isocyanurate, Bis(4-acryloyloxybutyl)isocyanurate, preferably tris(2-acryloyloxyethyl)isocyanurate These are some examples.

[0086] In the composition according to the present invention, the content of the compound having an isocyanurate structure is preferably 10.0 to 50.0% by mass, more preferably 10.0 to 40.0% by mass, based on the total mass of component (III).

[0087] From the viewpoint of reactivity, the molecular weight of a compound containing two or more (meth)acryloyloxy groups is preferably 200 to 2,000, more preferably 200 to 1,500.

[0088] The content of component (III) is adjusted according to the type of polymer or (meth)acryloyloxy group-containing compound used, but from the viewpoint of compatibility with the polymer, it is preferably 10.0 to 25.0% by mass, more preferably 10.0 to 20.0% by mass, based on the total mass of polysiloxane (I) and acrylic polymer (II).

[0089] - Additives In some embodiments of the present invention, the composition may optionally further contain one or more additives. However, in some cases, the amount of the aforementioned additives may be zero. Such additives can be selected from, for example, one or more components of the group consisting of surfactants, adhesion promoters, silane coupling agents, thermoacid generators, thermobase generators, crosslinkable monomers, and polymerization initiators. Publicly available additives, as described in European Patent Application Publication No. 3717966 or International Publication No. 2021 / 099236, can preferably be used. Since the aforementioned additives are not essential to the present invention, the amount of additives in the composition or layer is preferably 5% by weight or less, more preferably 1% by weight or less, based on the total amount of polysiloxane. The composition and / or the layer obtained from the composition may not contain any of the aforementioned additives.

[0090] In another embodiment, the present invention further comprises the following steps: (X) at least (I) an alkali-soluble polymer, preferably a polysiloxane, an acrylic polymer, or a combination of a polysiloxane and an acrylic polymer, (II) Polymerization initiator, (III) Scattering particles and The present invention relates to a method for preparing a composition of the present invention, which includes at least a step of mixing, essentially consists of, or comprises a step of mixing.

[0091] Preferably, the aforementioned mixing step (X) is carried out in the presence of a solvent, more preferably in the presence of an organic solvent. Preferably, a compound containing two or more (meth)acryloyloxy groups is also mixed in mixing step (X) to form a composition.

[0092] In another aspect, the present invention further relates to compositions obtained or that can be obtained by methods for producing the above compositions.

[0093] In another aspect, the present invention also relates to the use of the compositions of the present invention for preparing optical layers containing metal oxides, preferably for preparing composites, and more preferably for preparing layered composites.

[0094] In another embodiment, the present invention further comprises the following steps: (Xi) A step of applying the composition of the present invention to a layer or substrate to form a coated layer, (Xii) The process of baking the coated layer to obtain a composite material (post-bake process) The present invention relates to a method for producing a composite material comprising, essentially, or consisting of at least the following:

[0095] Preferably, this method further includes the following steps after step (Xi) and before step (Xii): (Xiii) A step of applying a pre-bake (heat treatment) to the coated layer in order to dry the coated layer and reduce the amount of solvent remaining in the coated layer. (Xiv) A step of irradiating the coated layer with light, preferably light having a peak maximum wavelength in the range of 360 to 430 nm (a step of applying light irradiation), preferably a step of using a patterning mask when light irradiation is performed. (Xv) A step of applying a post-exposure bake process, and / or (Xvi) A process of applying a development process to form a patterned hardened layer. Includes one or more of the following.

[0096] (1) Application process First, the above composition is applied to the substrate. In this invention, "on top of the substrate" includes cases where the composition is applied directly to the substrate and cases where the composition is applied to the substrate via one or more intermediate layers. The formation of the coating film of the composition in this invention can be carried out by any conventionally known method for applying a photosensitive composition. This can be freely selected from dip coating, roll coating, bar coating, brush coating, spray coating, doctor coating, flow coating, spin coating, slit coating, etc. Suitable substrates such as silicon substrates, glass substrates, and resin films can be used as the substrate to which the composition is applied. Various semiconductor devices, etc., can be formed on these substrates as needed. If the substrate is a film, gravure coating can also be used. If desired, a drying process can be added after the film has been applied. Furthermore, if necessary, the application process can be repeated once, twice, or more times to achieve the desired thickness of the formed coating film.

[0097] (2) Pre-bake process After applying the composition to form a coating film, it is preferable to dry the coating film and perform a pre-bake (heat treatment) of the coating film to reduce the amount of residual solvent in the coating film. The pre-bake process can generally be carried out at a temperature of 50 to 150°C, preferably 90 to 120°C, for 10 to 300 seconds, preferably 30 to 120 seconds, on a hot plate, or for 1 to 30 minutes in a clean oven.

[0098] (3) Exposure process (light irradiation) After forming the coating film, the surface of the coating film is then irradiated with light. Any light source conventionally used in pattern formation methods can be used for light irradiation. Examples of such light sources include high-pressure mercury lamps, low-pressure mercury lamps, lamps containing metal halides and xenon, laser diodes, and LEDs. Ultraviolet light, such as g-rays, h-rays, and i-rays, is typically used for irradiation. Except for ultrafine processing of semiconductors, it is common to use 360-430 nm light (high-pressure mercury lamp) for pattern formation of several micrometers to tens of micrometers. In particular, 430 nm light is often used in the case of liquid crystal display devices. In such cases, as described above, it is advantageous to combine the additive with the composition according to the present invention. The energy of the irradiated light is generally 5-2,000 mJ / cm², depending on the light source and the thickness of the coating film. 2 Preferably 10 to 1,000 mJ / cm² 2 The energy of the irradiated light is 5 mJ / cm². 2 If the light energy is lower, sufficient resolution may not be obtained in some cases. On the other hand, if the irradiation light energy is 2,000 mJ / cm² 2 If the exposure is too high, overexposure may occur, resulting in halation.

[0099] A general-purpose photomask can be used to irradiate the substrate with patterned light. Such a photomask can be freely selected from well-known options. The irradiation environment is not particularly limited and can generally be set to ambient air or a nitrogen atmosphere. Furthermore, when forming a film over the entire surface of the substrate, light irradiation can be performed over the entire surface of the substrate. In this invention, the patterned film also includes cases where a film is formed over the entire surface of the substrate.

[0100] (4) Post-exposure baking process After exposure, post-exposure baking can be performed as needed to promote the reaction between polymers in the film by a polymerization initiator. Unlike the heating process (6) described later, this heating treatment is not performed to completely cure the coating film, but rather to leave only the desired pattern on the substrate after development, allowing other areas to be removed by development. Therefore, it is not essential in the present invention.

[0101] When post-exposure baking is performed, a hot plate, oven, furnace, etc., can be used. Since it is undesirable for acids, bases, or radicals generated in the exposed area by light irradiation to diffuse into the unexposed area, the heating temperature should not be excessively high. From this viewpoint, the range of the post-exposure heating temperature is preferably 40 to 150°C, more preferably 60 to 120°C. To control the curing rate of the composition, heating can be performed in stages as needed. Furthermore, the atmosphere during heating is not particularly limited and can be selected from inert gases such as nitrogen, under vacuum, under reduced pressure, or in oxygen gas, etc., for the purpose of controlling the curing rate of the composition. Furthermore, the heating time is preferably above a certain level to maintain a higher degree of uniformity in the temperature history of the wafer surface, and is preferably not excessively long in order to suppress the diffusion of generated acids, bases, or radicals. From this viewpoint, the heating time is preferably 20 to 500 seconds, more preferably 40 to 300 seconds.

[0102] (5) Development process After exposure, a post-exposure bake is optionally performed, and then the coating film is developed. Any developer conventionally used for developing photosensitive compositions can be used as the developer. Preferred examples of developers include alkaline developers, which are aqueous solutions of alkaline compounds such as tetraalkylammonium hydroxide, choline, alkali metal hydroxides, alkali metal metasilicate (hydrate), alkali metal phosphate (hydrate), ammonia, alkylamines, alkanolamines, and heterocyclic amines. Particularly preferred alkaline developers are aqueous solutions of tetramethylammonium hydroxide (TMAH), potassium hydroxide, or sodium hydroxide. This alkaline developer may further contain, if necessary, water-soluble organic solvents such as methanol and ethanol, or surfactants. The development method can be freely selected from conventionally known methods. Specifically, this may include methods such as dipping, paddle, shower, slit, cap coat, and spray in the developer. After development with a developer capable of obtaining a pattern, rinsing with water is preferable.

[0103] (6) Post-bake process After development, the obtained pattern film is cured by heating. The same heating device used for the post-exposure baking described above can be used for the heating process. The heating temperature in the heating process is not particularly limited, as long as it is a temperature that can cure the coating film and can be freely determined. However, if silanol groups of polysiloxane remain, the chemical resistance of the cured film may be insufficient, or the dielectric constant of the cured film may become higher. From this viewpoint, a relatively high temperature is generally selected as the heating temperature. In order to maintain a high ratio of film remaining after curing, the curing temperature is more preferably 350°C or lower, and particularly preferably 250°C or lower. On the other hand, in order to promote the curing reaction and obtain a sufficiently cured film, the curing temperature is preferably 70°C or higher, more preferably 80°C or higher, and particularly preferably 90°C or higher. The heating time is not particularly limited, and is generally 10 minutes to 24 hours, preferably 30 minutes to 3 hours. In addition, this heating time is the time from when the temperature of the pattern film reaches the desired heating temperature. Typically, it takes several minutes to several hours for the pattern film to reach the desired temperature from the temperature before heating.

[0104] In another aspect, the present invention further relates to a composite material, preferably a layered composite material, obtained or obtainable by the method for producing the composite material of the present invention as described above, wherein the layered composite material is preferably an optical layer. Preferably, the layer is a protective layer for an electrical device. Preferably, the curing is thermal curing and / or UV light curing.

[0105] In another embodiment, the present invention further relates to a composite material, preferably a layered composite material, wherein the aforementioned layered composite material is an optical layer, and the composite material is i) A polymer (A) that is derived from or can be derived from at least (I) an alkali-soluble polymer, preferably the aforementioned alkali-soluble polymer being a polysiloxane, an acrylic polymer, or a combination of a polysiloxane and an acrylic polymer, (III) Scattering particles and It includes at least, essentially consists of, or consists of.

[0106] Preferably, the polymer (A) described above is derived from or can be derived from at least (I) an alkali-soluble polymer and (II) a polymerization initiator, and more preferably from or can be derived from a compound comprising at least (I) an alkali-soluble polymer, (II) a polymerization initiator and two or more (meth)acryloyloxy groups.

[0107] In a preferred embodiment of the present invention, the composite material contains one or more organic particles as scattering particles, the outermost surface of the composite material has an uneven structure, preferably the surface of the composite material has a finely roughened structure, more preferably the entire surface of the composite material has a finely roughened structure, and even more preferably the uneven structure and the finely roughened structure are caused by one or more organic particles of the aforementioned organic material.

[0108] In a preferred embodiment of the present invention, the composite material has an average layer thickness in the range of 1 μm to 200 μm, preferably 1.5 to 100 μm, and more preferably 2 to 100 μm.

[0109] In another aspect, the present invention further relates to a display device comprising a composite material of the present invention and at least one functional medium configured to modulate or emit light.

[0110] Preferably, the aforementioned display device is selected from the group consisting of OLED, LCD, LED, and μLED. Therefore, the aforementioned functional medium is an OLED layer, an LCD layer, an LED array, and / or a μLED array.

[0111] Preferred Embodiment 1. A photosensitive composition comprising at least, (I) an alkali-soluble polymer, preferably a polysiloxane, an acrylic polymer, or a combination of a polysiloxane and an acrylic polymer, (II) Polymerization initiator, (III) Scattering particles and A photosensitive composition containing [a specific substance].

[0112] Preferably, the aforementioned photosensitive composition is a negative-type photosensitive composition, and preferably, the aforementioned photosensitive composition is used to manufacture a protective layer for an electronic device. Preferably, the aforementioned photosensitive composition is a filling composition used to manufacture an electronic device, and more preferably, a filling composition for an LED or μLED.

[0113] 2. The composition of Embodiment 1, wherein the aforementioned scattering particles are selected from inorganic particles, organic particles, and mixtures of inorganic and organic particles.

[0114] 3. The composition of Embodiment 1 or 2, wherein the average particle size of the scattered particles is 200 nm to 10 μm, preferably 230 nm to 5 μm, and more preferably 250 nm to 2 μm. When the scattered particles are inorganic particles, preferably the average particle size is in the range of 200 nm to 1 μm, preferably 230 to 800 nm, more preferably 250 to 700 nm, and even more preferably 300 to 600 nm. When the scattered particles are organic particles, preferably the average particle size is in the range of 300 nm to 10 μm, more preferably 500 nm to 5 μm, even more preferably 700 nm to 3 μm, and even more preferably 800 nm to 2 μm.

[0115] 4. A composition according to any one of the above embodiments, wherein the aforementioned scattering particles have a refractive index higher than that of the mixture of polysiloxane and acrylic polymer, and preferably the scattering particles are configured to have a refractive index higher than that of the matrix polymer derived from the polysiloxane and acrylic polymer by polymerization. Preferably, the aforementioned refractive index of the scattering particles is 1.6 or higher, preferably 1.7 or higher, and 2.4 or lower, preferably 2.2 or lower. Most preferably 1.8 to 2.0. When two or more different scattering particles are used in the composition, the average refractive index of the scattering particles is 1.6 or higher, preferably 1.7 or higher, and 2.4 or lower, preferably 2.2 or lower. Most preferably 1.8 to 2.0.

[0116] 5. A composition of any one of Embodiments 1 to 3, wherein the scattering particles are organic particles, and the difference X between the refractive index of the scattering particles and the refractive index of the mixture of polysiloxane and acrylic polymer is in the range of -0.2 to +0.2. Preferably, the difference X' between the refractive index of the scattering particles and the refractive index of the matrix polymer derived from the polysiloxane and acrylic polymer by polymerization is in the range of -0.2 to +0.2.

[0117] X: Refractive index of scattering particles - Refractive index of mixture = -0.2 to +0.2, preferably -0.1 to +0.1

[0118] X': Refractive index of scattering particles - Refractive index of matrix polymer derived from polysiloxane and acrylic polymer by polymerization = -0.2 to +0.2, preferably -0.1 to +0.1

[0119] When a mixture of organic particles is used as scattering particles, the definition of X is: average refractive index of the scattering particles - refractive index of the mixture = -0.2 to +0.2, preferably -0.1 to +0.1. The definition of X' is: average refractive index of the scattering particles - refractive index of the matrix polymer derived from polysiloxane and acrylic polymers by polymerization = -0.2 to +0.2, preferably -0.1 to +0.1.

[0120] 6. The aforementioned alkali-soluble polymer is a polysiloxane, or a combination of a polysiloxane and an acrylic polymer, preferably the polysiloxane having chemical formula (I a A composition comprising any one of the above embodiments, wherein the repeating unit of ) is present. [ka] (In the formula, R Ia is hydrogen, C 1-30 (preferably C 1-10 ) Linear chain, C 3-30 (preferably C 3-10 ) A branched or cyclic, saturated or unsaturated aliphatic hydrocarbon group or aromatic hydrocarbon group, wherein the aliphatic hydrocarbon group and aromatic hydrocarbon group are either unsubstituted or substituted with fluorine, hydroxyl, or alkoxy. In aliphatic hydrocarbon groups and aromatic hydrocarbon groups, methylene is not substituted, or one or more methylene groups are substituted by oxy, imino, or carbonyl groups, except R Ia (It is neither hydroxyl nor alkoxy.)

[0121] 7. The aforementioned alkali-soluble polymer is polysiloxane, or a combination of polysiloxane and acrylic polymer, and polysiloxane has chemical formula (I b A composition comprising any one of the above embodiments, wherein the repeating unit of ) is present. [ka] (In the formula, R Ib This group is obtained by removing multiple hydrogen atoms from a nitrogen and / or oxygen-containing alicyclic hydrocarbon compound having amino, imino, and / or carbonyl groups. Preferably, R IbThis group is obtained by removing several hydrogens, preferably two or three, from a nitrogen-containing aliphatic hydrocarbon ring, preferably having an imino and / or carbonyl group, and more preferably from a five-membered or six-membered ring containing nitrogen as a member. For example, it is obtained by removing two or three hydrogens from piperidine, pyrrolidine, or isocyanurate. Ib This involves bonding the Si atoms contained within multiple repeating units to each other.

[0122] 8. The alkali-soluble polymer described above is a polysiloxane, or a combination of a polysiloxane and an acrylic polymer, and the total amount of polysiloxane is in the range of 1 to 40% by mass, preferably 5 to 35% by mass, and more preferably 10 to 30% by mass, based on the total mass of the solvent-free composition, one of the compositions described above.

[0123] 9. The alkali-soluble polymer is an acrylic polymer, or a combination of polysiloxane and an acrylic polymer, preferably the acrylic polymer is selected from one or more components of the group consisting of polyacrylic acid, polymethacrylic acid, polyalkyl acrylate, and polyalkyl methacrylate, one of the compositions of the embodiments described above. Preferably, the total amount of acrylic polymer in the composition is in the range of 65 to 99% by mass, more preferably 70 to 90% by mass, based on the total mass of the composition excluding the solvent.

[0124] 10. Any one of the compositions of the embodiments described above further comprises a solvent, preferably the solvent being an organic solvent, and more preferably the solvent being an ethylene glycol monoalkyl ether (preferably, it is ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and / or ethylene glycol monobutyl ether); diethylene glycol dialkyl ether (preferably, it is diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and / or diethylene glycol dibutyl ether); propylene glycol monoalkyl ether (preferably, it is propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether and / or propylene glycol monopropyl ether); ethylene glycol alkyl ether acetate (preferably, it is methyl cellosolve acetate and / or ethylene Lucerosolve acetate); propylene glycol alkyl ether acetate (preferably propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate and / or propylene glycol monopropyl ether acetate); ketone (preferably methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and / or cyclohexanone); alcohol (preferably ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, triethylene glycol and / or glycerin); esters (preferably ethyl 3-ethoxypropionate, methyl 3-methoxypropionate and / or ethyl lactate), and cyclic esters (preferably gamma-butyro-lactone); chlorinated hydrocarbons (preferably chloroform, dichloromethane, chlorobenzene);The solvent is an organic solvent selected from one or more components of the group consisting of trimethylbenzenes (preferably 1,3,5-trimethylbenzene, 1,2,4-trimethylbenzene, 1,2,3-trimethylbenzene), doceylbenzene, cyclohexylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 3-isopropylbiphenyl, 3-methylbiphenyl, 4-methylbiphenyl; and dichlorobenzene. Preferably, the aforementioned solvent is ethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, propylene glycol, ethylene glycol, propylene glycol monoalkyl ether, ethylene glycol alkyl ether acetate, or propylene glycol alkyl ether acetate. More preferably, the aforementioned solvent is selected from propylene glycol alkyl ether acetate, ethylene glycol monoalkyl ether, propylene glycol, and propylene glycol monoalkyl ether.

[0125] 11. Any one of the above embodiments, further comprising a compound containing two or more (meth)acryloyloxy groups, preferably the content of the compound being in the range of 10.0 to 25.0% by mass based on the total mass of the solvent-free composition.

[0126] 12. The following steps, (X) At least, (I) an alkali-soluble polymer, preferably a polysiloxane, an acrylic polymer, or a combination of a polysiloxane and an acrylic polymer, (II) Polymerization initiator, (III) Scattering particles and A method for preparing any one of the compositions of the above embodiments, comprising at least the step of mixing the following.

[0127] Preferably, the aforementioned mixing step (X) is carried out in the presence of a solvent, more preferably in the presence of an organic solvent. Preferably, a compound containing two or more (meth)acryloyloxy groups is also mixed in mixing step (X) to form a composition.

[0128] 13. Use of any one of the compositions from Embodiments 1 to 11 for preparing an optical layer containing a metal oxide, preferably for preparing a composite material, more preferably for preparing a layered composite material.

[0129] 14. A method for manufacturing composite materials, (Xi) A step of applying any one of the compositions from Embodiments 1 to 11 to a layer or substrate to form a coated layer, (Xii) A process of baking the coated layer to obtain a composite material. A method for manufacturing composite materials, including [the specified element].

[0130] Preferably, this method further includes the following steps after step (Xi) and before step (Xii): (Xiii) A step of applying a pre-bake (heat treatment) to the coated layer in order to dry the coated layer and reduce the amount of solvent remaining in the coated layer. (Xiv) A step of irradiating the coated layer with light, preferably light having a peak maximum wavelength in the range of 360 to 430 nm (a step of applying light irradiation), preferably a step of using a patterning mask when light irradiation is performed. (Xv) A step of applying a post-exposure bake process, and / or (Xvi) A process of applying a development process to form a patterned hardened layer. Includes one or more of the following.

[0131] 15. A composite material, preferably a layered composite material, that can be obtained or obtained by the method of Embodiment 14, wherein the layered composite material is an optical layer.

[0132] 16. A composite material, preferably a layered composite material, wherein the aforementioned layered composite material is an optical layer. i) A polymer (A) that is derived from or can be derived from at least (I) an alkali-soluble polymer, preferably the aforementioned alkali-soluble polymer being a polysiloxane, an acrylic polymer, or a combination of a polysiloxane and an acrylic polymer, (III) Scattering particles and A composite material containing at least [a certain element].

[0133] Preferably, the polymer (A) described above is derived from or can be derived from at least (I) an alkali-soluble polymer and (II) a polymerization initiator, and more preferably from or can be derived from a compound comprising at least (I) an alkali-soluble polymer, (II) a polymerization initiator and two or more (meth)acryloyloxy groups.

[0134] 17. A composite material of Embodiment 15 or 16, comprising one or more organic particles as scattering particles, wherein the outermost surface of the composite material has an uneven structure, preferably the surface of the composite material has a finely roughened structure, more preferably the entire surface of the composite material has a finely roughened structure, and even more preferably the aforementioned uneven structure and finely roughened structure are caused by one or more of the aforementioned organic particles.

[0135] A composite material according to any one of embodiments 15 to 17, having an average layer thickness in the range of 18.1 μm to 200 μm, preferably 1.5 to 100 μm, and more preferably 2 to 100 μm.

[0136] 19. A display device comprising at least one functional medium configured to modulate or emit light, and one composite material from any one of embodiments 15 to 18. [Examples]

[0137] The following embodiments provide a description of the present invention and a detailed description of their manufacture. However, the present invention is not limited to these embodiments.

[0138] <Synthesis Example 1: Polysiloxane A> In a 2 L flask equipped with a stirrer, thermometer, and condenser, 49.0 g of 25% by mass TMAH aqueous solution, 600 mL of isopropyl alcohol (IPA), and 4.0 g of water were added. Then, using a dropping funnel, a mixed solution of 68.0 g of methyltrimethoxysilane, 79.2 g of phenyltrimethoxysilane, and 15.2 g of tetramethoxysilane was prepared. The mixed solution was added dropwise at 40°C and stirred at the same temperature for 2 hours, and neutralized by adding a 10% by mass aqueous solution of HCl. 400 mL of toluene and 600 mL of water were added to the neutralization solution to separate it into two layers, and the aqueous layer was removed. Furthermore, the obtained product was rinsed three times with 300 mL of water, and the obtained organic layer was concentrated under reduced pressure to remove the solvent. PGMEA was added to the concentrate to adjust the solid content to 35% by mass, thereby obtaining a polysiloxane A solution. The mass-average molecular weight (Mw) of the obtained polysiloxane A was 1,700.

[0139] <Synthesis Example 2: Acrylic Polymer A> In a 2 L flask equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet tube, n-butanol and PGMEA solvent are placed, and the temperature is raised to an appropriate temperature under a nitrogen gas atmosphere, while referring to the 10-hour half-life temperature of the initiator. Separately, a mixed liquid is prepared with acrylic acid, γ-methacrylateoxypropyltrimethoxysilane, 2-hydroxyethyl methacrylate and methyl methacrylate in a 10:20:20:50 ratio, azobisisobutyronitrile, and PGMEA, and this mixed liquid is added dropwise to the above solvent over 4 hours. The resulting product is then reacted for 3 hours to obtain acrylic polymer A. The Mw of the obtained acrylic polymer A is 8,700.

[0140] <Synthesis Example 3: Acrylic Polymer B> In a 1 L flask equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet tube, 16.4 g of azobisisobutyronitrile and 120 g of butanol were placed, and the temperature was raised to an appropriate temperature under a nitrogen gas atmosphere, while referring to the 10-hour half-life temperature of the initiator. Separately, a mixed liquid was prepared containing 5.16 g of methacrylic acid, 46.5 g of 3-methacrylateoxypropylmethyldimethoxysilane, 6.5 g of 2-hydroxyethyl methacrylate, and 70.08 g of methyl methacrylate, and this mixed liquid was added dropwise to the solvent over 4 hours. The resulting product was then reacted for 3 hours to obtain acrylic polymer B. The Mw of the obtained acrylic polymer B was 7,350.

[0141] Example 1: Preparation of a mixed sample The negative compound mixture is prepared as follows: Dissolve Merck's alkali-soluble siloxane polymer (polysiloxane A) represented by the following chemical formula, alkali-soluble acrylic polymer A from Synthesis Example 2, alkali-soluble acrylic polymer B from Synthesis Example 3, photoinitiator NCI-831E, IRGACURE OXE03, monomer A-9300S, and additives A-DCP, A-DOD-N, and AKS-10 in PGMEA. Adjust the mixture in PGMEA to a solids content of 44% by weight. [ka]

[0142] Next, the obtained negative-type formulation is mixed with the following nanoparticles listed in Table 1 to obtain efficient optical properties.

[0143] - Preparation of substrate: Coat a non-alkaline glass substrate with the mixture. After coating with a spin coater, bake the glass substrate on a hot plate at 100°C for 90 seconds. Then expose the glass substrate to i-line exposure. Next, for development, immerse the coated glass substrate in a 2.38% TMAH aqueous solution for 60 seconds. After rinsing with water, cure the glass in an oven at 160°C for 30 minutes.

[0144] TT stands for "total transmittance" in the wavelength range of 380 to 780 nm.

[0145] According to the present invention, the aforementioned haze value is measured in air at room temperature using a haze measurement system equipped with an integrating sphere (NDH-7000, Nippon Denshoku, Japan, light source White LED 3W, wavelength range 380~780nm). The sample thickness is 2μm to 700μm. In particular, the sample thickness is 700μm.

[0146] Schematic of an integrating sphere for transmittance and haze measurement, total transmittance (T T )T T =T P +T D Hayes (H)H=T D / T T .

[0147] Parallel transmittance (T P The diffracted light transmittance (T) is determined by measuring the light intensity at a position opposite the sample inside the sphere, and the diffracted light transmittance (T) is determined by the diffracted light transmittance (T) D ) and T P Total transmittance (T T ) is, formula T T =T P +T D This is obtained by measuring the light passing through the sample using the following method: The degree of light scattering in the sample, i.e., haze (H), is given by H = T D / T T It is defined as [a specific function / method]. It measures transmittance and haze.

[0148] Particle size is obtained from catalogs published by material suppliers. The RI (refractive index) value is not measured, but the publicly available RI data (catalog value) for the material is used.

[0149] Reflection at 450nm: Measured with CM-5, Konica Minolta, SCI mode.

[0150] [Table 1]

[0151] [Table 2]

[0152] As shown in the table above, nanoparticle mixtures can yield higher haze values ​​and higher transmittance. This is considered promising for future displays such as rollable, foldable, and vendable flexible displays.

Claims

1. A photosensitive composition comprising at least, (I) An alkali-soluble polymer, preferably a polysiloxane, an acrylic polymer, or a combination of a polysiloxane and an acrylic polymer, (II) Polymerization initiator and (III) Scattering particles and A photosensitive composition containing [a specific substance].

2. The composition according to claim 1, wherein the scattering particles are selected from inorganic particles, organic particles, and a mixture of inorganic particles and organic particles.

3. The composition according to claim 1 or 2, wherein the average particle size of the scattering particles is 200 nm or more and 10 μm or less.

4. The composition according to any one of claims 1 to 3, wherein the scattering particles have a refractive index higher than that of the mixture of the polysiloxane and the acrylic polymer.

5. The scattering particles are organic particles, and the difference X between the refractive index of the scattering particles and the refractive index of the mixture of the polysiloxane and the acrylic polymer is in the range of -0.2 to +0.

2. X: The refractive index of the scattering particles minus the refractive index of the mixture = -0.2 to +0.2, preferably -0.1 to +0.

1. The composition according to any one of claims 1 to 3, wherein, when a mixture of organic particles is used as the scattering particles, X is defined as: the average refractive index of the scattering particles minus the refractive index of the mixture = -0.2 to +0.2, preferably -0.1 to +0.

1.

6. The composition according to any one of claims 1 to 5, wherein the alkali-soluble polymer is a polysiloxane or a combination of a polysiloxane and an acrylic polymer.

7. The alkali-soluble polymer is a polysiloxane, or a combination of a polysiloxane and an acrylic polymer, wherein the polysiloxane has the chemical formula (I ｂ The composition according to any one of claims 1 to 6, comprising a repeating unit of ) 【Chemistry 1】 (In the formula, R Ｉｂ This group is obtained by removing multiple hydrogen atoms from a nitrogen and / or oxygen-containing alicyclic hydrocarbon compound having amino, imino, and / or carbonyl groups. Preferably, R Ｉｂ This group is obtained by removing multiple hydrogens, preferably two or three, from a nitrogen-containing aliphatic hydrocarbon ring, preferably having an imino and / or carbonyl group, and more preferably from a five-membered or six-membered ring containing nitrogen as one member. For example, it is obtained by removing two or three hydrogens from piperidine, pyrrolidine, or isocyanurate. Ｉｂ This involves bonding the Si atoms contained within multiple repeating units to each other.

8. The alkali-soluble polymer is a polysiloxane, or a combination of a polysiloxane and an acrylic polymer, and the total amount of the polysiloxane is in the range of 1 to 40% by mass, preferably 5 to 35% by mass, and more preferably 10 to 30% by mass, based on the total mass of the composition excluding the solvent, according to any one of claims 1 to 7.

9. The alkali-soluble polymer is an acrylic polymer, or a combination of polysiloxane and an acrylic polymer, preferably the acrylic polymer is selected from one or more components of the group consisting of polyacrylic acid, polymethacrylic acid, polyalkyl acrylate, and polyalkyl methacrylate, in the composition according to any one of claims 1 to 8, preferably the total amount of the acrylic polymer in the composition is in the range of 65 to 99% by mass, more preferably 70 to 90% by mass, based on the total mass of the composition excluding the solvent.

10. The composition according to any one of claims 1 to 9, further comprising a solvent.

11. The composition according to any one of claims 1 to 10, further comprising a compound containing two or more (meth)acryloyloxy groups, preferably the content of the compound being in the range of 10.0 to 25.0% by mass based on the total mass of the composition without the solvent.

12. The following steps, (X) At least, (I) An alkali-soluble polymer, preferably a polysiloxane, an acrylic polymer, or a combination of a polysiloxane and an acrylic polymer, (II) Polymerization initiator and (III) Scattering particles and The process of mixing A method for preparing the composition according to any one of claims 1 to 11, comprising at least the following:

13. A method for manufacturing composite materials, (Xi) A step of applying the composition according to any one of claims 1 to 11 to a layer or substrate to form a coated layer, (Xii) A process of baking the coated layer to obtain a composite material and A method for manufacturing composite materials, including [the specified element].

14. A composite material, preferably a layered composite material, wherein the layered composite material is an optical layer. i) A polymer (A) derived from or capable of being derived from at least (I) an alkali-soluble polymer, preferably the alkali-soluble polymer being a polysiloxane, an acrylic polymer, or a combination of a polysiloxane and an acrylic polymer, (III) Scattering particles and A composite material containing at least [a certain element].

15. The composite material according to claim 14, wherein the scattering particles include one or more organic particles, the outermost surface of the composite material has an uneven structure, preferably the surface of the composite material has a finely roughened structure, more preferably the entire surface of the composite material has a finely roughened structure, and even more preferably the uneven structure and the finely roughened structure are caused by one or more organic particles.

16. The composite material according to claim 14 or 15, having an average layer thickness in the range of 1 μm to 200 μm.

17. A display device comprising at least one functional medium configured to modulate or emit light, and a composite material according to any one of claims 14 to 16.

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