Polysiloxane material and polysiloxane composition containing the same

Abstract

To provide polysiloxane materials with excellent bending performance. [Solution] A polysiloxane having a specific structure, which is a polysiloxane (Pab) comprising a repeating unit represented by formula (ia) and a repeating unit represented by formula (ib), or a mixture of a polysiloxane (Pa) comprising a repeating unit represented by formula (ia) and a polysiloxane (Pb) comprising a repeating unit represented by formula (ib).

Description

Technical Field

[0001] The present invention relates to polysiloxane materials. The present invention relates to a polysiloxane composition comprising the same.

Background Art

[0002] With the development of mobile devices such as smartphones, tablet PCs, and small displays, thinning, slimming, and weight reduction are required. As a material to replace glass, plastic resins have been studied, and resin cured films are incorporated in display devices such as mobile devices.

[0003] Polysiloxane is known as a material for forming a cured film. In order to achieve a desired taper angle of the formed pattern, a photosensitive polysiloxane composition containing a polysiloxane containing a specific repeating unit has been proposed (for example, Patent Document 1). For forming a protective film having chemical resistance, a photosensitive polysiloxane composition containing a polysiloxane containing a specific repeating unit has been proposed (for example, Patent Document 2).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] The inventors of this invention have noticed that displays in which parts are bent or flexible for aesthetic and functional reasons have recently attracted attention, and this trend is particularly pronounced in mobile devices. Therefore, they focused on the fact that cured films implemented in OLED displays and the like that built into such devices require bending performance.

[0006] Therefore, the inventors of this invention believe that there is still one or more issues with polysiloxane materials that require improvement. These include, for example, the following: The cured film has insufficient bending performance; low sensitivity; low resolution of the formed pattern; low heat resistance of the cured film; inability to suppress scum on the cured film; low flatness of the cured film; narrow process window; low manufacturing yield. [Means for solving the problem]

[0007] The (I) polysiloxane material according to the present invention is A polysiloxane (Pab) comprising repeating units represented by formula (ia) and repeating units represented by formula (ib), or This is a mixture of a polysiloxane (Pa) containing repeating units represented by formula (ia) and a polysiloxane (Pb) containing repeating units represented by formula (ib). [ka] [ka] (Here, L 1 C 4-12 It is a linear alkylene, L 1 If H is 1 or greater in the middle, C 1-10 Linear alkyl, C 3-10 Branched-chain alkyl groups, alicyclic C 3-15 Alkyl, C 6-15 It may be replaced by an aryl, -COOH, or -OH. L 1One or more non - adjacent methylene (-CH2-) in it may be replaced by -Ph-, -O-, -S-, -CO-, -CO - O-, -O - CO-, -O - CO - O-, -CR 1 =CR 2 -, or -C≡C-, and R 1 and R 2 are each independently H or C 1-6 linear alkyl).

[0008] The polysiloxane composition according to the present invention comprises the above - mentioned (I) polysiloxane material and (II) solvent.

[0009] The method for manufacturing a film according to the present invention comprises applying the above - mentioned polysiloxane composition to a substrate, optionally exposing it, and developing it.

[0010] The method for manufacturing a cured film according to the present invention comprises manufacturing the film described above, and heating it and.

[0011] The cured film according to the present invention is manufactured by the method described above.

[0012] The display device according to the present invention comprises the above - mentioned cured film. [Advantages of the Invention]

[0013] According to the present invention, it is possible to expect one or more of the following effects: The bending performance of the cured film is sufficient; the sensitivity is sufficient; the resolution of the pattern formed is sufficient; the heat resistance of the cured film is sufficient; scum on the cured film can be suppressed; the flatness of the cured film is sufficient; the process window is sufficient; the manufacturing yield is improved. [Embodiments for Carrying Out the Invention]

[0014] [Definitions] In this specification, unless otherwise specified, the definitions and examples set forth in this paragraph shall prevail. The singular form includes the plural form, and "one" or "that" means "at least one." An element of a certain concept can be expressed by multiple types, and when a quantity (e.g., mass %) is given, that quantity represents the sum of those multiple types. "and / or" includes all combinations of elements, as well as their use individually. When a numerical range is indicated using "~" or "-", it includes both endpoints and has the same unit. For example, 5~25 mol% means between 5 mol% and 25 mol%. "C x-y "C x ~C y " and "C x The notation, such as "," refers to the number of carbon atoms in the molecule or substituent. For example, C 1-6 Alkyl refers to an alkyl chain having between 1 and 6 carbon atoms (such as methyl, ethyl, propyl, butyl, pentyl, and hexyl). When a polymer has multiple types of repeating units, these repeating units copolymerize. These copolymerizations may be alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture of these. When polymers and resins are shown in structural formulas, the n, m, etc., in parentheses indicate the number of repeating units. The unit of temperature used is Celsius. For example, 20 degrees means 20 degrees Celsius. An additive refers to the compound itself that has the function (for example, in the case of a base generator, it is the compound itself that generates a base). The compound may also be added to the composition in the form of being dissolved or dispersed in a solvent. In one embodiment of the present invention, it is preferable that such a solvent is included in the composition according to the present invention as (II) a solvent or other component. The term "aryl" refers to a group containing one or more aromatic rings, and includes, but is not limited to, phenyl, anthracenyl, naphthyl, phenantrenyl, fluorenyl, and pyrenyl. Aralkyl refers to alkyl groups substituted with aryl, and includes, but is not limited to, benzyl and phenylethyl.

[0015] The embodiments of the present invention will be described in detail below.

[0016] (I) Polysiloxane materials The present invention relates to a polysiloxane (Pab) comprising repeating units represented by formula (ia) and repeating units represented by formula (ib), or This invention relates to (I) polysiloxane material (hereinafter sometimes referred to as component (I); the same applies to other components), which is a mixture of polysiloxane (Pa) containing repeating units represented by formula (ia) and polysiloxane (Pb) containing repeating units represented by formula (ib). In this invention, polysiloxane refers to a polymer whose main chain consists of Si-O-Si bonds (siloxane bonds). In this specification, a general polysiloxane is defined as a polymer of formula (RSiO 1.5 ) n This also includes silsesquioxane polymers represented by .

[0017] Since the polysiloxane material undergoes further polymerization after film formation to become the main backbone of the cured film, it is believed that the effects of the present invention will be exhibited whether the repeating units represented by formula (ia) and formula (ib) are both contained in a single polymer or in separate polymers in a mixture. Although not bound by theory, it is thought that in the formed cured film, the repeating unit represented by formula (ia) provides a moderate hardness due to its rigid framework, such as SiO2, while the repeating unit represented by formula (ib) provides a moderate flexibility due to its soft structure, which contains organic chains.

[0018] Equation (ia) is as follows: [ka]

[0019] The number of repeating units represented by formula (ia) is preferably 1 to 20%, and more preferably 1 to 10%, based on the total number of repeating units included in component (I).

[0020] Equation (ib) is as follows: [ka] Here, L 1 C 4-12 It is a linear alkylene, L 1 If H is 1 or greater in the middle, C 1-10 Linear alkyl, C 3-10 Branched-chain alkyl groups, alicyclic C 3-15 Alkyl, C 6-15 It may be replaced by aryl, -COOH, or -OH, but is preferably not replaced. L 1 One or more non-adjacent methylene (-CH2-) groups within the group are -Ph- (meaning phenylene), -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CR 1 =CR 2 - or -C≡C- may be used as substitutes, but preferably not. L 1 Preferably, C 4-12 Linear alkylene (where L 1 The H and methylene groups in the middle are not substituted, and more preferably, are straight-chain butylene, hexylene, and octylene. R 1 and R 2 These are, independently, H or C 1-6 It is a linear alkyl group, preferably H or methyl.

[0021] An example of formula (ib) is as follows: [ka]

[0022] The number of repeating units represented by formula (ib) is preferably 1 to 30%, and more preferably 1 to 15%, based on the total number of repeating units included in component (I).

[0023] Preferably, component (I) further comprises a repeating unit represented by formula (ib'). More preferably, each polysiloxane (Pb) further comprises a repeating unit represented by formula (ib'). While not constrained by theory, further inclusion of repeating units in equation (ib') can prevent scum formation, reduce heat flow, increase resolution, and improve sensitivity while maintaining flexibility. [ka] Here, L 2 C 1-3 It is a linear alkylene, L 2 If H is 1 or greater in the middle, C 1-10 Linear alkyl, C 3-10 Branched-chain alkyl groups, alicyclic C 3-15 Alkyl, C 6-15 It may be replaced by aryl, -COOH, or -OH, but is preferably not replaced. L 2 The one or more non-adjacent methylene (-CH2-) groups within the group are -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, and -CR. 3 =CR 4 - or -C≡C- may be used as substitutes, but it is preferable that they are not used. R 3 and R 4 These are, independently, H or C 1-6 It is a linear alkyl group, preferably H or methyl. L 2 The material is preferably methylene, ethylene, or n-propylene, and more preferably methylene or ethylene.

[0024] An example of formula (ib') is shown below. [ka]

[0025] The number of repeating units represented by formula (ib') is preferably 1 to 20%, more preferably 1 to 15%, and even more preferably 1 to 9%, based on the total number of repeats included in component (I).

[0026] Preferably, component (I) further comprises a repeating unit represented by formula (ic). More preferably, each of the polysiloxane (Pab), polysiloxane (Pa), and polysiloxane (Pb) further comprises a repeating unit represented by formula (ic). [ka] Here, X is H, C 1-10 Linear alkyl, C 3-10 Branched-chain alkyl groups, alicyclic C 3-15 Alkyl, C 6-15 It is aryl, -COOH, or -OH, preferably C 1-10 Linear alkyl or C 6-15 It is Ariel. One or more non-adjacent methylene (-CH2-) groups in X are -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CR 5 =CR 6 - or -C≡C- may be used as substitutes, but it is preferable that they are not used. R 5 and R 6 These are, independently, H or C 1-6 It is a linear alkyl group, preferably H or methyl. Examples of X include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and decyl; aryl groups such as phenyl, tolyl, and benzyl; and cycloalkyl groups such as cyclohexyl. Preferably, X is methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl, or tolyl. Compounds in which X is methyl are preferred because, although not bound by theory, the cured film has high hardness and high chemical resistance. Phenyl is also preferred because, although not bound by theory, it increases the solubility of the polysiloxane in the solvent, making the cured film less prone to cracking.

[0027] The number of repeating units represented by formula (ic) is preferably 70-99%, more preferably 80-95%, and even more preferably 85-90%, based on the total number of repeating units included in component (I).

[0028] Component (I) is preferably a mixture of a polysiloxane (Pa) comprising a repeating unit represented by formula (ia) and a polysiloxane (Pb) comprising a repeating unit represented by formula (ib).

[0029] The number of repeating units represented by formula (ia) in the polysiloxane (Pa) is preferably 1% or more, more preferably 3-20%, and even more preferably 5-15%, based on the total number of repeating units contained in the polysiloxane (Pa). The polysiloxane (Pa) preferably further comprises repeating units represented by formula (ic). The number of repeating units represented by formula (ic) in the polysiloxane (Pa) is preferably 80-97%, and more preferably 85-95%, based on the total number of repeating units contained in the polysiloxane (Pa). The polysiloxane (Pa) content is preferably 10% by mass or more, more preferably 30-90% by mass, even more preferably 40-80% by mass, and even more preferably 50-70% by mass, based on the total mass of the polysiloxane material (I).

[0030] The number of repeating units represented by formula (ib) in polysiloxane (Pb) is preferably 1% or more, more preferably 5-30%, and even more preferably 7-20%, based on the total number of repeating units contained in the polysiloxane (Pb). The polysiloxane (Pb) preferably further comprises repeating units represented by formula (ib'). The number of repeating units represented by formula (ib') in the polysiloxane (Pb) is preferably 1 to 20%, more preferably 5 to 15%, and even more preferably 7 to 10%, based on the total number of repeating units contained in the polysiloxane (Pb). The number of repeating units represented by formula (ic) in polysiloxane (Pb) is preferably 80-98%, and more preferably 85-95%, based on the total number of repeating units contained in polysiloxane (Pb). The polysiloxane (Pb) content is preferably 10% by mass or more, more preferably 10 to 70% by mass, even more preferably 20 to 60% by mass, and even more preferably 30 to 50% by mass, based on the total mass of the polysiloxane material.

[0031] The polysiloxanes (Pab), (Pa), and (Pb) may also contain repeating units other than those described above, but the number of these other repeating units is preferably 20% or less, and more preferably 10% or less, based on the total number of repeating units contained in the polysiloxanes (Pab), (Pa), and (Pb). Not containing any of the above-mentioned repeating units is also a preferred embodiment of the present invention.

[0032] In the present invention, the ratio of repeating units can be calculated using known structural analysis methods for compounds, for example, 1 It can be calculated based on the peak ratio of the HNMR spectrum.

[0033] The polysiloxane used in the present invention preferably has a silanol at its terminus. Here, silanol refers to a group consisting of Si of the polysiloxane and an OH group bonded to that Si. That is, -O in the above formula. 0.5 - vs. -O 0.5 Silanols are formed by the bonding of hydrogen atoms. The silanol content in polysiloxanes varies depending on the synthesis conditions of the polysiloxane, such as the monomer mixing ratio and the type of reaction catalyst. This 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 when the silanol content is high.

[0034] The mass-average molecular weight (Mw) of the polysiloxane used in the present invention is preferably 500 to 30,000, more preferably 500 to 25,000, and even more preferably 1,000 to 20,000, from the viewpoint of solubility in organic solvents, coatability on substrates, and solubility in alkaline developers. Here, the mass-average molecular weight is the polystyrene-equivalent mass-average molecular weight, which can be measured by gel permeation chromatography using polystyrene as the reference.

[0035] (I) Component can be obtained by hydrolysis and condensation of a suitable silicon compound in the presence of an acidic or basic catalyst as needed.

[0036] Component (I) can be used in photosensitive compositions, in which case it is necessary for there to be a difference in solubility between the exposed and unexposed areas. In the case of positive-type compositions, the coating film in the exposed area should have a certain level of solubility in the developer, and in the case of negative-type compositions, the coating film in the unexposed area should have a certain level of solubility in the developer. For example, if the dissolution rate (hereinafter sometimes referred to as alkali dissolution rate or ADR; details below) of the pre-baked coating film in a 2.38% tetramethylammonium hydroxide (hereinafter sometimes referred to as TMAH) aqueous solution is 50 Å / sec or higher, it is considered that pattern formation by exposure-development is possible. However, the required solubility differs depending on the thickness of the formed cured film and the development conditions, so polysiloxane should be appropriately selected according to the development conditions. Although it varies depending on the type and amount of photoactivator included in the composition, for example, if the film thickness is 0.1 to 100 μm (1,000 to 1,000,000 Å), in the case of a positive-type composition, the dissolution rate in a 2.38% TMAH aqueous solution is preferably 50 to 5,000 Å / second, and more preferably 200 to 3,000 Å / second. In the case of a negative-type composition, the dissolution rate in a 2.38% TMAH aqueous solution is preferably 50 to 20,000 Å / second, and more preferably 1,000 to 10,000 Å / second.

[0037] <Polysiloxane composition> The polysiloxane composition according to the present invention (hereinafter also simply referred to as "the composition") comprises (I) the polysiloxane material and (II) the solvent described above. (I) The content of component is preferably 10 to 50% by mass, and more preferably 20 to 40% by mass, based on the total mass of the composition excluding the solvent.

[0038] (II) Solvent The composition according to the present invention comprises a solvent. The solvent is selected from those that uniformly dissolve or disperse each component contained in the composition. Specifically, for example, ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; and propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether. Examples of solvents include ethers, propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate, aromatic hydrocarbons such as benzene, toluene, and xylene, ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin, esters such as ethyl lactate, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate, and cyclic esters such as γ-butyrolactone. Preferably, PGMEA, PGME, or γ-butyrolactone are used. These solvents can be used individually or in combination of two or more.

[0039] (II) The solvent mixing ratio varies depending on the coating method and the required film thickness after coating. For example, in the case of spray coating, it may be 90% by mass or more based on the total mass of the composition, but in slit coating of large glass substrates used in the manufacture of displays, it is usually 50% by mass or more, preferably 60% by mass or more, usually 90% by mass or less, and preferably 85% by mass or less.

[0040] (III) Photoactivators The composition according to the present invention may be a non-photosensitive composition or a photosensitive composition. When the composition according to the present invention is a photosensitive composition, the composition according to the present invention further comprises (III) a photoactivator. Photosensitive compositions are classified into positive-type photosensitive compositions or negative-type photosensitive compositions. In the present invention, a positive-type photosensitive composition is a composition that, when applied to form a coating film and exposed to light, increases the solubility of the exposed area in an alkaline developer, and the exposed area is removed by development to form a positive image. A negative-type photosensitive composition is a composition that, when applied to form a coating film and exposed to light, becomes insoluble in an alkaline developer, and the unexposed area is removed by development to form a negative image. In the present invention, a compound that changes the solubility of the exposed or unexposed area of ​​a polysiloxane composition coating film is called a photoactivator. In negative-type photosensitive compositions, the solubility of the exposed or unexposed area may be changed by heat treatment after exposure. In this invention, for convenience, compounds having such functions are also collectively referred to as photoactivators.

[0041] When the composition according to the present invention is a positive-type photosensitive composition, a compound that increases the solubility of the exposed portion of the coating film upon light irradiation is used as a photoactivator. Such compounds are well known in the field of resist materials and are sometimes called, for example, dissolution inhibitors. In the case of a positive-type photosensitive composition, it is preferable that it contains a diazonaphthoquinone derivative as a photoactivator. A composition containing a diazonaphthoquinone derivative can form a positive image that is removed by development because the exposed areas become soluble in the alkaline developer. This is because, upon exposure, the solubility of the exposed areas in the alkaline developer increases due to the indenecarboxylic acid generated, while the solubility of the unexposed areas decreases due to interaction with the silanol groups remaining in the polysiloxane.

[0042] Preferred diazonaphthoquinone derivatives are compounds in which naphthoquinone diazidosulfonic acid is esterified to a compound having a phenolic hydroxyl group. While the structure is not particularly limited, it is preferably an ester compound with a compound having one or more phenolic hydroxyls. As the naphthoquinone diazidosulfonic acid, 4-naphthoquinone diazidosulfonic acid or 5-naphthoquinone diazidosulfonic acid can be used. 4-naphthoquinone diazidosulfonic acid ester compounds have absorption in the i-line (wavelength 365 nm) region and are therefore suitable for i-line exposure. Furthermore, 5-naphthoquinone diazidosulfonic acid ester compounds have absorption over a wide wavelength range and are therefore suitable for exposure over a wide wavelength range. It is preferable to select an appropriate diazonaphthoquinone derivative depending on the exposure wavelength. 4-naphthoquinone diazidosulfonic acid ester compounds and 5-naphthoquinone diazidosulfonic acid ester compounds can also be used in combination.

[0043] Compounds having phenolic hydroxyl groups are not particularly limited, but examples include bisphenol A, BisP-AF, BisOTBP-A, Bis26B-A, BisP-PR, BisP-LV, BisP-OP, BisP-NO, BisP-DE, BisP-AP, BisOTBP-AP, TrisP-HAP, BisP-DP, TrisP-PA, BisOTBP-Z, BisP-FL, TekP-4HBP, TekP-4HBPA, and TrisP-TC (Honshu Chemical Industry Co., Ltd.).

[0044] The optimal amount of diazonaphthoquinone derivative to add varies depending on the esterification rate of naphthoquinone diazidosulfonic acid, the physical properties of the polysiloxane used, the required sensitivity, and the dissolution contrast between the exposed and unexposed areas. However, it is preferably 20 parts by mass or less per 100 parts by mass of polysiloxane, for example, 1 to 20 parts by mass, and more preferably 3 to 15 parts by mass. When the amount of diazonaphthoquinone derivative added is 1 part by mass or more, the dissolution contrast between the exposed and unexposed areas increases, resulting in sufficient photosensitive properties. Furthermore, to obtain an even better dissolution contrast, 3 parts by mass or more is preferable. On the other hand, the less diazonaphthoquinone derivative added, the more the colorless transparency of the cured film improves and the transmittance increases, which is preferable.

[0045] When the composition according to the present invention is a negative-type photosensitive composition, a compound that reduces the solubility of the exposed portion of the coating film upon light irradiation is used as a photoactivator. Such compounds are generally called photosensitive agents and are selected according to the type of resist resin used, but examples include compounds selected from the group consisting of photoacid generators, photobase generators, photothermal acid generators, and photothermal base generators. The negative-type photosensitive composition according to the present invention preferably contains one or more of these.

[0046] The optimal amount of photoactivator used in a negative-type photosensitive composition varies depending on the type and amount of active substances generated by decomposition, the required sensitivity, and the dissolution contrast between exposed and unexposed areas. However, it is preferably 20 parts by mass or less, for example, 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass, per 100 parts by mass of total polysiloxane. If the amount added is less than 0.1 parts by mass, the amount of acid or base generated is too small, and polymerization during post-bake is not accelerated, making pattern sagging more likely. On the other hand, if the amount added is more than 20 parts by mass, cracks may occur in the formed cured film, or discoloration due to decomposition may become significant, which can reduce the colorless transparency of the cured film. Furthermore, if the amount added is too high, thermal decomposition can cause deterioration of the electrical insulation properties of the cured product and gas release, which can lead to problems in subsequent processes. In addition, the resistance of the cured film to photoresist stripping solutions, such as those mainly composed of monoethanolamine, may decrease.

[0047] In the present invention, a photoacid generator or photobase generator refers to a compound that generates an acid or base by undergoing bond cleavage upon exposure. The generated acid or base is thought to contribute to the polymerization of polysiloxane. Here, examples of light include visible light, ultraviolet light, infrared light, X-rays, electron beams, alpha rays, or gamma rays.

[0048] The photoacid generator can be arbitrarily selected from those commonly used, but examples include diazomethane compounds, triazine compounds, sulfonic acid esters, diphenyliodonium salts, triphenylsulfonium salts, sulfonium salts, ammonium salts, phosphonium salts, and sulfonimide compounds.

[0049] In addition to those mentioned above, specific photoacid generators that can be used include: 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium methanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium-p-toluenesulfonate, 4-phenylthiophenyldiphenyltetrafluoroborate, 4-phenylthiophenyldiphenylhexafluorophosphonate, triphenylsulfonium methanesulfonate, triphenylsulfonium trifluoroacetate, and triphenylsulfonium-p-toluenesulfonate. Examples include 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-phenylthiophenyldiphenylhexafluoroarsenate, 4-phenylthiophenyldiphenyl-p-toluenesulfonate, N-(trifluoromethylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, 5-norbornene-2,3-diccarboxyimidyl triflate, 5-norbornene-2,3-diccarboxyimidyl-p-toluenesulfonate, 4-phenylthiophenyldiphenyltrifluoromethanesulfonate, 4-phenylthiophenyldiphenyltrifluoroacetate, N-(trifluoromethylsulfonyloxy)diphenylmaleimide, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-diccarboxyimide, N-(trifluoromethylsulfonyloxy)naphthylimide, and N-(nonafluorobutylsulfonyloxy)naphthylimide. Furthermore, 5-propylsulfonyloxyimino-5H-thiophene-2-ylidene-(2-methylphenyl)acetonitrile, 5-octylsulfonyloxyimino-5H-thiophene-2-ylidene-(2-methylphenyl)acetonitrile, 5-camphorsulfonyloxyimino-5H-thiophene-2-ylidene-(2-methylphenyl)acetonitrile, and 5-methylphenylsulfonyloxyimino-5H-thiophene-2-ylidene-(2-methylphenyl)acetonitrile have absorption in the h-ray wavelength region, so their use should be avoided if absorption in the h-ray region is undesirable.

[0050] Examples of photobase generators include polysubstituted amide compounds, lactams, imide compounds having an amide group, or those containing the same structure. In addition, ionic photobase generators containing an amide anion, methide anion, borate anion, phosphate anion, sulfonate anion, or carboxylate anion can also be used.

[0051] In the present invention, photothermal acid generators and photothermal base generators refer to compounds whose chemical structure changes upon exposure to light but do not generate an acid or base, and then undergo bond cleavage due to heat to generate an acid or base. Of these, photothermal base generators are preferred.

[0052] (IV) Other additives In addition to the above-mentioned (I) to (III), the composition according to the present invention may optionally be combined with (IV) and other additives. Examples of components (IV) include surfactants, acids, bases, thermal acid generators, thermal base generators, developer dissolution accelerators, scum removers, adhesion enhancers, polymerization initiators, defoamers, or sensitizers, and one or more of these can be selected. (IV) The content of component is preferably 0 to 0.5% by mass, and more preferably 0.01 to 0.1% by mass, based on the total mass of the composition excluding the solvent.

[0053] <Method for manufacturing films and cured films> The method for producing a film according to the present invention comprises applying the above-mentioned composition to a substrate, and optionally exposing it to light and developing it. The method for producing a cured film according to the present invention further includes heating.

[0054] First, the aforementioned composition is applied to a substrate. The formation of the coating film of the composition in the present invention can be carried out by any conventionally known method for applying the composition. Specifically, it can be arbitrarily selected from dip coating, roll coating, bar coating, brush coating, spray coating, doctor blade coating, flow coating, spin coating, and slit coating. Suitable substrates for coating the composition include silicon substrates, glass substrates, and resin films. These substrates may have various semiconductor elements formed on them as needed. If the substrate is a film, gravure coating can also be used. A drying step can be added separately after coating if desired. Furthermore, the coating process can be repeated one or more times as needed to achieve the desired film thickness.

[0055] After forming a coating film of the composition according to the present invention, it is preferable to pre-bake (heat treat) the coating film in order to dry the coating film and reduce the amount of residual solvent. The pre-bake process can generally be carried out at a temperature of 70 to 150°C, preferably 90 to 120°C, for 10 to 180 seconds, preferably 30 to 90 seconds, using a hot plate, or for 1 to 30 minutes using a clean oven.

[0056] In the case of non-photosensitive compositions, the coating film is then heated to cure it. The heating temperature in this heating step is not particularly limited as long as it is a temperature at which the coating film can be cured, and can be set arbitrarily. However, if silanol groups remain, the chemical resistance of the cured film may be insufficient, or the dielectric constant of the cured film may be high. From this viewpoint, a relatively high heating temperature is generally selected. To promote the curing reaction and obtain a sufficiently cured film, the curing temperature is preferably 200°C or higher. The heating time is not particularly limited, and is generally 10 minutes to 24 hours, preferably 20 minutes to 3 hours. 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.

[0057] In the case of photosensitive compositions, the surface of the coating 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, metal halide lamps, xenon lamps, laser diodes, LEDs, etc. Ultraviolet light such as g-line, h-line, and i-line is usually used as the irradiation light. Except for ultrafine processing such as semiconductors, it is common to use 360-430 nm light (high-pressure mercury lamp) for patterning of several micrometers to tens of micrometers. In particular, 430 nm light is often used in the case of liquid crystal display devices. The energy of the irradiation light depends on the light source and the thickness of the coating, but is generally 5-2,000 mJ / cm². 2 Preferably 10 to 1,000 mJ / cm² 2 Let's assume the irradiation light energy is 5 mJ / cm². 2 If the level is lower than this, sufficient resolution may not be obtained, while conversely, 2,000 mJ / cm² may not be sufficient. 2 If the exposure level is higher than this, it can result in overexposure and cause halation.

[0058] A general-purpose photomask can be used to irradiate light in a patterned manner. Such a photomask can be arbitrarily selected from well-known ones. The irradiation environment is not particularly limited, but generally, ambient atmosphere (air) or a nitrogen atmosphere is acceptable. Furthermore, when forming a cured film over the entire surface of the substrate, the entire surface of the substrate should be irradiated with light. In this invention, the term "patterned film" also includes the case in which a cured film is formed over the entire surface of the substrate.

[0059] After exposure, the acid or base generated at the exposed area promotes the interpolymer reaction within the coating film. Therefore, especially in the case of negative type film, post-exposure baking can be performed as needed. Unlike the heating process described later, this heating treatment is not performed to completely harden the coating film, but rather to ensure that only the desired pattern remains on the substrate after development, with the rest being removable by development. When heating is performed after exposure, a hot plate, oven, or furnace can be used. The heating temperature should not be excessively high, as it is undesirable for the acid or base generated in the exposed area due to light irradiation to diffuse into the unexposed area. From this viewpoint, the range of the heating temperature after exposure is preferably 40°C to 150°C, and more preferably 60°C to 120°C. Stepwise heating can also be applied as needed to control the curing rate of the composition. The atmosphere during heating is not particularly limited, but can be selected from inert gas such as nitrogen, under vacuum, under reduced pressure, or in oxygen gas, for the purpose of controlling the curing rate of the composition. Furthermore, the heating time should preferably be above a certain level in order to maintain a higher level of uniformity in the temperature history within the wafer surface, and should not be excessively long in order to suppress the diffusion of the generated acid. From this viewpoint, the heating time is preferably 20 seconds to 500 seconds, and more preferably 40 seconds to 300 seconds. When using a positive-type photosensitive composition, it is preferable to omit the post-exposure heating step, as this does not promote crosslinking between polymers.

[0060] After exposure, the coating film is developed. Any developer conventionally used for developing photosensitive compositions can be used as the developer. Preferred developers include alkaline developers, which are aqueous solutions of alkaline compounds such as tetraalkylammonium hydroxide, choline, alkali metal hydroxides, alkali metal metasilicates (hydrates), alkali metal phosphates (hydrates), aqueous ammonia, alkylamines, alkanolamines, and heterocyclic amines. Particularly preferred alkaline developers are aqueous solutions of tetramethylammonium hydroxide. These alkaline developers may further contain water-soluble organic solvents such as methanol and ethanol, or surfactants, as needed. The development method can also be arbitrarily selected from conventionally known methods. Specifically, methods include immersion in the developer (dip), paddle, shower, slit, cap coat, and spray. A pattern can be obtained by this development. After development with the developer, it is preferable to wash with water.

[0061] Subsequently, a flood exposure process is typically performed. If a photoacid generator or photobase generator is used, the acid or base is generated during this flood exposure process. If a photothermal acid generator or photothermal base generator is used, the chemical structure of the photothermal acid generator or photothermal base generator changes during this flood exposure process. Furthermore, if unreacted diazonaphthoquinone derivatives remain in the coating film, they are photodegraded, further improving the phototransparency of the cured film. Therefore, if transparency is desired, it is preferable to perform the flood exposure process. Even when a thermoacid generator or thermobase generator is added in the case of a positive type, it is preferable to perform flood exposure for the above purposes. As a method for flood exposure, an ultraviolet-visible exposure machine such as an aligner (e.g., Canon Inc. PLA-501F) is used, with a radiation level of 100 to 2,000 mJ / cm². 2 One method involves exposing the entire surface to a certain degree (equivalent to the exposure amount at a wavelength of 365 nm).

[0062] The resulting patterned film is heated to cure the coating. The heating conditions are the same as those used when the non-photosensitive composition described above is used.

[0063] The Young's modulus of the resulting cured film can be measured by methods such as nanoindentation. Nanoindentation is a method in which an indenter is pressed into a desired location on the sample to be measured, and the load and displacement are measured simultaneously. From the load-displacement curve obtained at this time, the hardness and Young's modulus (elastic modulus) of the sample can be determined. Specific measuring devices include the ENT series (Elionix). The Young's modulus of the formed cured film is preferably 3.4 GPa or less, and more preferably 3.0 GPa or less.

[0064] The cured film formed in this manner can be suitably used in a wide range of applications, such as an interlayer insulating film for various devices, a transparent protective film, an interlayer insulating film for low-temperature polysilicon, or a buffer coating film for IC chips. The formed cured film is then subjected to further post-processing, such as processing or circuit formation on the substrate, as needed, to form a device, preferably a display device. Any conventionally known method can be applied to these post-processing steps. [Examples]

[0065] The present invention will be described below with reference to various examples. However, the embodiments of the present invention are not limited to these examples.

[0066] The mass-average molecular weight (Mw) is measured by gel permeation chromatography (GPC) with polystyrene as the reference. GPC is performed using the alliance™ e2695 high-speed GPC system (Waters Japan Ltd.) and the Super Multipore HZ-N GPC column (Tosoh Corporation). The measurement is performed using monodisperse polystyrene as the standard sample, with tetrahydrofuran as the developing solvent, at a flow rate of 0.6 ml / min and a column temperature of 40°C, and Mw is calculated as the relative molecular weight to the standard sample.

[0067] [Synthesis of polysiloxane Pa-1] In a 2L flask equipped with a stirrer, thermometer, and condenser, 49.0g of 25% by mass tetramethylammonium hydroxide (TMAH) aqueous solution, 470g of isopropyl alcohol (IPA), and 4.0g of water were charged. Next, a mixed solution of 68.0g of methyltrimethoxysilane, 79.2g of phenyltrimethoxysilane, and 15.2g of tetramethoxysilane was prepared in a dropping funnel. This mixed solution was added dropwise at 40°C and stirred at the same temperature for 2 hours, after which a 10% HCl aqueous solution was added to neutralize it. 400ml of toluene and 600ml of water were added to the neutralized solution to separate it into two phases, and the aqueous phase was removed. The mixture was then washed three times with 300ml of water, and the resulting organic phase was concentrated under reduced pressure to remove the solvent. PGMEA was added to the concentrate to adjust the solid content to 35% by mass. The obtained polysiloxane Pa-1 has a Mw of 1800. The obtained resin solution was coated onto a silicon wafer using a spin coater (MS-A100 (Mikasa Corporation)) to a film thickness of 2 μm after pre-baking. The dissolution rate (ADR) in a 2.38% TMAH aqueous solution after pre-baking was measured to be 1200 Å / sec.

[0068] [Synthesis of polysiloxane Pb-1] In a 300 mL flask equipped with a stirrer, thermometer, and condenser, 26.03 g of 25% by mass TMAH aqueous solution and 40 g of PGME were charged. Then, a mixed solution of 13.6 g of methyltrimethoxysilane, 15.84 g of phenyltrimethoxysilane, and 14.18 g of 1,2-bis(trimethoxysilyl)ethane was prepared in a dropping funnel. This mixed solution was added dropwise at 5°C and stirred at 25°C for 2 hours. Then, 29.63 g of 28% by mass maleic acid-containing PGME solution was added to neutralize it. 100 g of n-propyl acetate (nPA) and 60 g of water were added to the neutralized solution to separate it into two phases, and the aqueous phase was removed. The mixture was then washed three times with 60 g of water, and the resulting organic phase was concentrated under reduced pressure to remove the solvent. PGMEA was added to the concentrate to adjust the solid content to 45% by mass. The obtained polysiloxane Pb-1 had a Mw of 7,790 and an ADR of 4,850 Å / sec.

[0069] [Synthesis of polysiloxane Pb-2] In a 300 mL flask equipped with a stirrer, thermometer, and condenser, 27.23 g of 25% by mass TMAH aqueous solution and 40 g of PGME were charged. Next, a mixed solution of 8.16 g of methyltrimethoxysilane, 23.76 g of phenyltrimethoxysilane, and 14.18 g of 1,2-bis(trimethoxysilyl)ethane was prepared in a dropping funnel. This mixed solution was added dropwise at 5°C and stirred at 25°C for 2 hours. Then, 31.02 g of 28% by mass maleic acid-containing PGME solution was added to neutralize it. 180 g of ethyl acetate and 60 g of water were added to the neutralized solution to separate it into two phases, and the aqueous phase was removed. The mixture was then washed three times with 60 g of water, and the resulting organic phase was concentrated under reduced pressure to remove the solvent. PGMEA was added to the concentrate to adjust the solid content to 40% by mass. The obtained polysiloxane Pb-2 had a Mw of 5,120 and an ADR of 2,640 Å / sec.

[0070] [Synthesis of polysiloxane Pb-3] In a 300 mL flask equipped with a stirrer, thermometer, and condenser, 28.03 g of 25% by mass TMAH aqueous solution and 40 g of PGME were charged. Then, a mixed solution of 13.6 g of methyltrimethoxysilane, 15.84 g of phenyltrimethoxysilane, and 13.06 g of 1,6-bis(trimethoxysilyl)hexane was prepared in a dropping funnel. This mixed solution was added dropwise at 5°C and stirred at 25°C for 2 hours. Then, 31.92 g of 28% by mass maleic acid-containing PGME solution was added to neutralize it. 100 g of nPA and 60 g of water were added to the neutralized solution to separate it into two phases, and the aqueous phase was removed. The mixture was then washed three times with 60 g of water, and the resulting organic phase was concentrated under reduced pressure to remove the solvent. PGMEA was added to the concentrate to adjust the solid content to 35% by mass. The obtained polysiloxane Pb-3 had a Mw of 6,450 and an ADR of 6,860 Å / sec.

[0071] [Synthesis of polysiloxane Pb-4] In a 300 mL flask equipped with a stirrer, thermometer, and condenser, 36.04 g of 25% by mass TMAH aqueous solution and 40 g of PGME were charged. Next, a mixed solution of 13.6 g of methyltrimethoxysilane, 15.84 g of phenyltrimethoxysilane, and 17.55 g of 1,8-bis(triethoxysilyl)octane was prepared in a dropping funnel. This mixed solution was added dropwise at 5°C and stirred at 25°C for 2 hours. Then, 41.03 g of 28% by mass maleic acid-containing PGME solution was added to neutralize it. 140 g of nPA and 60 g of water were added to the neutralized solution to separate it into two phases, and the aqueous phase was removed. The mixture was then washed three times with 60 g of water, and the resulting organic phase was concentrated under reduced pressure to remove the solvent. PGMEA was added to the concentrate to adjust the solid content to 20% by mass. The obtained polysiloxane Pb-4 had a Mw of 9,940 and an ADR of 2,440 Å / sec.

[0072] [Synthesis of polysiloxane Pb-5] In a 300 mL flask equipped with a stirrer, thermometer, and condenser, 30.43 g of 25% by mass TMAH aqueous solution and 40 g of PGME were charged. Then, a mixed solution of 13.6 g of methyltrimethoxysilane, 15.84 g of phenyltrimethoxysilane, 7.09 g of 1,2-bis(trimethoxysilyl)ethane, and 6.53 g of 1,6-bis(trimethoxysilyl)hexane was prepared in a dropping funnel. This mixed solution was added dropwise at 5°C and stirred at 25°C for 2 hours. Then, 34.67 g of 28% by mass maleic acid-containing PGME solution was added to neutralize it. 140 g of nPA and 60 g of water were added to the neutralized solution to separate it into two phases, and the aqueous phase was removed. The mixture was then washed three times with 60 g of water, and the resulting organic phase was concentrated under reduced pressure to remove the solvent. PGMEA was added to the concentrate to adjust the solid content to 40% by mass. The obtained polysiloxane Pb-5 had a Mw of 7,840 and an ADR of 3,360 Å / sec.

[0073] [Synthesis of polysiloxane Pb-6] In a 300 mL flask equipped with a stirrer, thermometer, and condenser, 29.63 g of 25% by mass TMAH aqueous solution and 40 g of PGME were charged. Next, a mixed solution of 13.6 g of methyltrimethoxysilane, 15.84 g of phenyltrimethoxysilane, 7.09 g of 1,2-bis(trimethoxysilyl)ethane, and 8.78 g of 1,8-bis(triethoxysilyl)octane was prepared in a dropping funnel. This mixed solution was added dropwise at 5°C and stirred at 25°C for 2 hours. Then, 33.74 g of 28% by mass maleic acid-containing PGME solution was added to neutralize it. 140 g of nPA and 60 g of water were added to the neutralized solution to separate it into two phases, and the aqueous phase was removed. The mixture was then washed three times with 60 g of water, and the resulting organic phase was concentrated under reduced pressure to remove the solvent. PGMEA was added to the concentrate to adjust the solid content to 40% by mass. The obtained polysiloxane Pb-6 had a Mw of 8,250 and an ADR of 2,420 Å / sec.

[0074] Table 1 summarizes the ratio of the number of repeating units in the polysiloxanes synthesized above. In Table 1, (ia), (ib), (ib'), and (ic) represent the repeating units represented by formulas (ia), (ib), (ib'), and (ic), respectively. [Table 1]

[0075] [Example 1] Composition of Example 1 is obtained by dissolving 28.256 parts by mass of polysiloxane in which polysiloxane Pa-1 and polysiloxane Pb-5 are in a mass ratio of 50:50, 1.695 parts by mass of diazonaphthoquinone derivative "TPPA-280A" (Toyo Gosei Kogyo Co., Ltd.), 0.028 parts by mass of surfactant "AKS-10" (Shin-Etsu Chemical Co., Ltd.), and 0.02 parts by mass of maleic acid in a mixed solvent of 36.75 parts by mass of PGMEA, 26.25 parts by mass of PGME, and 7 parts by mass of γ-butyrolactone.

[0076] [Examples 2-5 and Comparative Examples 1-7] The compositions of Examples 2-5 and Comparative Examples 1-7 were prepared in the same manner as in Example 1, except that the type of polysiloxane and its mixing ratio (by mass) were changed as shown in Table 2. [Table 2]

[0077] [Sensitivity evaluation] Each of the compositions from Examples 1-5 and Comparative Examples 1-3 was applied to a 4-inch silicon wafer that had undergone HMDS treatment by spin coating to a final film thickness of 1.5 μm. Each of the resulting coatings was pre-baked at 100°C for 90 seconds to evaporate the solvent. After drying, each coating was exposed to light at 50 mJ / cm² using a g+h+i line stepper (NES2W-ghi06, Nikon Corporation). 2 From 200 mJ / cm 2 The exposure is varied until a pattern is exposed using a contact hole containing a 5 μm hole and a 15 μm space. After exposure, the pattern is paddle developed for 70 seconds using a 2.38% TMAH aqueous solution, then rinsed with pure water for 60 seconds, and each pattern is dried. After drying, each pattern is subjected to 1000 mJ / cm² using a g+h+i line mask aligner (PLA-501F type, Canon Inc.). 2 The samples were flood-exposed and then heated in air at 250°C for 60 minutes to cure. The hole diameters of each pattern after curing were measured using a scanning electron microscope (SEM), and holes with a diameter of 5 ± 0.5 μm were identified. The exposure dose (E) for each identified hole during pattern exposure was confirmed, and the corresponding values ​​of E and the resulting cured pattern sizes are recorded in Table 2. E is 70 mJ / cm 2 Less than A, 70 mJ / cm² 2 More than 150mJ / cm 2 Less than B, 150 mJ / cm³ 2 The above is rated as C, and the results are shown in Table 2.

[0078] [Bending performance evaluation] A 7cm square polyimide (PI) film with a thickness of 15μm was fixed to a 4-inch silicon wafer with Kapton tape, and each composition from Examples 1-5 and Comparative Examples 1-7 was applied by spin coating to achieve a final film thickness of 2μm. Each resulting coating was pre-baked at 120°C for 90 seconds to evaporate the solvent. After drying, each coating was paddle-developed without exposure using a 2.38% TMAH aqueous solution for 70 seconds, then rinsed with pure water for 60 seconds, and finally dried. After drying, each coating was subjected to 1000mJ / cm² using a g+h+i line mask aligner (PLA-501F type, Canon Inc.). 2 The wafers are flood exposed and then heated in air at 230°C for 30 minutes to form a cured film. The cured PI film is peeled off each silicon wafer, and the PI film is folded along a piano wire placed on the back. A crease is made on the front side of the PI film with the thumb, and then the surface of the cured film on each opened PI film is observed with an optical microscope. The thickness of the piano wire is changed in the order of 1.0 mm, 0.5 mm, 0.3 mm, 0.2 mm, and 0.1 mm. Depending on the degree of scratching of each cured film, Level 0: No damage detected. Level 1: Only slight, fine line scratches are visible. Level 2: Slightly visible thick line scratches. Level 3: Numerous scratches are observed, or the hardened film is peeling off. The levels are categorized and evaluated according to the following criteria. A: All piano wires are at level 0. B: The piano wire thickness when the evaluation first reaches level 1, 2, or 3 is 0.2 mm or 0.1 mm. C: The piano wire thickness when the evaluation first reaches level 1, 2, or 3 is 1.0 mm, 0.5 mm, or 0.3 mm. The results obtained are shown in Table 2.

[0079] [Pattern hardness: Young's modulus] 29.9 parts by mass of polysiloxane Pb-1, polysiloxane Pb-3, and polysiloxane Pb-4 were each individually dissolved in a mixture of 0.1 parts by mass of surfactant "AKS-10" (Shin-Etsu Chemical Co., Ltd.) and 70 parts by mass of PGME to prepare compositions Pb-1, Pb-3, and Pb-4. Using these compositions and the composition of Comparative Example 1, cured films were formed in the same manner as the bending performance evaluation described above, and the hardness of each cured film was measured using a nanoindenter (ENT-2100, Elionix Co., Ltd.). The test load was 0.15 mN. The results obtained were 3.5 GPa for the composition of Comparative Example 1, 3.4 GPa for composition Pb-1, 2.1 GPa for composition Pb-3, and 2.0 GPa for composition Pb-4. Although not bound by theory, this result suggests that the repeating unit represented by equation (ia) imparts appropriate hardness to the cured film, and the repeating unit represented by equation (ib) imparts appropriate flexibility to the cured film.

Claims

1. A polysiloxane (Pab) comprising repeating units represented by formula (ia) and repeating units represented by formula (ib), or (I) A polysiloxane material, which is a mixture of a polysiloxane (Pa) containing repeating units represented by formula (ia) and a polysiloxane (Pb) containing repeating units represented by formula (ib); 【Chemistry 1】 【Chemistry 2】 (Here, L 1 C ４－１2 It is a linear alkylene; L １ If H is 1 or greater in the middle, C １－１０ Linear alkyl, C ３－１０ Branched-chain alkyl groups, including alicyclic C ３－１５ Alkyl, C ６－１５ It may be replaced by an aryl, -COOH, or -OH; L １ One or more non-adjacent methylene (-CH ２ -) in may be replaced by -Ph-, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CR 1 =CR 2 - or -C≡C-; R １ and R ２ These are, independently, H or C １－６ (It is a linear alkyl group.)

2. L １ However, C ４－１２ Linear alkylene (where L １ The (I) polysiloxane material according to claim 1, wherein the H and methylene in the material are not substituted.

3. The (I) polysiloxane material according to claim 1 or 2, wherein the polysiloxane (Pab), polysiloxane (Pa), and polysiloxane (Pb) further comprise a repeating unit represented by formula (ic); 【Transformation 3】 (Here, X is H, C １－１０ Linear alkyl, C ３－１０ Branched-chain alkyl groups, including alicyclic C ３－１５ Alkyl, C ６－１５ It is aryl, -COOH, or -OH; One or more non-adjacent methylene (-CH) in X ２ -) is -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CR ５ =CR ６ It may also be replaced by - or -C≡C-; R ５ and R ６ These are, independently, H or C １－６ (It is a linear alkyl group.)

4. X is C １－１０ Linear alkyl or C ６－１５ The polysiloxane material (I) according to claim 3, wherein it is an aryl polysiloxane material.

5. The (I) polysiloxane material according to any one of claims 1 to 4, which is a mixture of a polysiloxane (Pa) comprising a repeating unit represented by formula (ia) and a polysiloxane (Pb) comprising a repeating unit represented by formula (ib).

6. The polysiloxane material (I) according to claim 5, wherein the polysiloxane (Pb) content is 10% by mass or more, based on the total mass of the polysiloxane material (I).

7. The (I) polysiloxane material according to claim 5 or 6, wherein the number of repeating units represented by formula (ib) in the polysiloxane (Pb) is 5% or more based on the total number of repeating units contained in the polysiloxane (Pb).

8. The (I) polysiloxane material according to any one of claims 5 to 7, wherein the polysiloxane (Pb) further comprises repeating units represented by formula (ib'); 【Chemistry 4】 (Here, L ２ C １－３ It is a linear alkylene; L ２ If H is 1 or greater in the middle, C １－１０ Linear alkyl, C ３－１０ Branched-chain alkyl groups, including alicyclic C ３－１５ Alkyl, C ６－１５ It may be replaced by an aryl, -COOH, or -OH; L ２ One or more non-adjacent methylene (-CH) ２ -) is -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CR ３ =CR ４ It may also be replaced by - or -C≡C-; R ３ and R ４ These are, independently, H or C １－６ (It is a linear alkyl group.)

9. L ２ The (I) polysiloxane material according to claim 8, wherein the polysiloxane material is methylene, ethylene, or propylene.

10. A polysiloxane composition comprising (I) a polysiloxane material and (II) a solvent according to any one of claims 1 to 9.

11. (III) The composition according to claim 10, further comprising a photoactivator.

12. The composition according to claim 10 or 11, which is a positive-type photosensitive composition.

13. The composition according to claim 10 or 11, which is a negative-type photosensitive composition.

14. A method for producing a film, comprising applying the composition according to any one of claims 10 to 13 to a substrate, and optionally exposing it to light and developing it.

15. To manufacture the film described in claim 14, and Heat A method for producing a cured film comprising the above.

16. A cured film produced by the method described in claim 15.

17. The cured film according to claim 16, wherein the Young's modulus is 3.4 GPa or less.

18. A display device comprising the cured film according to claim 16 or 17.

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