Composition

Abstract

The present invention relates to a composition comprising a polysiloxane.

Description

Field of the Invention

[0001] The present invention relates to a composition containing at least polysiloxane, preferably to a composition for forming a protective layer, a method for producing the composition, a method for producing a layer, a layer, an electronic device, a method of using the compound, and a method of using the composition as a protective layer. Background Art

[0002] US2010 2010 / 0016488 A1 discloses a method for producing an organosiloxane polymer, comprising hydrolyzing trialkoxysilane and tetraalkoxysilane monomers in a hydrolysis step; and polymerizing the hydrolyzed monomers in a polymerization step by subjecting them to conditions conducive to polymerization to form an organosiloxane polymer; wherein the hydrolysis step is carried out in a reaction medium containing an organic compound having a hydroxyl group. It also discloses the use of the composition produced by the method for optical and electrical coatings.

[0003] Patent Literature

[0004] 1. US 2010 / 0016488 A1 SUMMARY OF THE INVENTION

[0006] However, the present inventors have recently discovered that there are still one or more considerable problems that need to be improved, as listed below: obtaining a polysiloxane-containing composition, preferably a protective layer-forming composition, which exhibits an improved dielectric constant similar to that of a glass substrate of an electronic device, preferably with minimal turbidity characteristics; obtaining a layer or cured composition, which exhibits an improved dielectric constant similar to that of a glass substrate of an electronic device, preferably with minimal turbidity characteristics; obtaining a polysiloxane-containing composition, preferably a protective layer-forming composition, which enables a sufficient amount of thiol to be well dispersed in the composition; obtaining a layer or cured composition, wherein a sufficient amount of thiol is well dispersed in the layer or cured composition; obtaining a polysiloxane-containing composition, preferably a protective layer-forming composition, which enables a mild or relatively low temperature process to form a smooth coating of a layer or cured composition, a polysiloxane-containing composition on any substrate, i.e., PET, CPI, COP or polarizer.

[0007] The present inventors aim to address one or more of the above problems.

[0008] Subsequently, it was discovered that the claimed novel composition, preferably a composition forming a protective layer, comprises at least, consists essentially of, or consists of:

[0009] i) polysiloxane; and

[0010] ii) a compound represented by the following chemical formula (I), which is preferably a dielectric constant promoter, preferably for use in a polysiloxane-containing composition,

[0011]

[0012] Where Z X1 Selected from the group consisting of a direct bond, CH2, C=O, O, (C=O)2, (C=O)O, (C=O)3, (C=O)2O, (C=O)2CH2 and C=O(CH2)2, preferably selected from a direct bond, C=O, O, (C=O)2, (C=O)3;

[0013] n is 0 or 1;

[0014] R x1 H, D or OR x3 ;

[0015] R x2 H, D or OR x3 ;

[0016] R x3 is H, D, an unsubstituted or substituted straight-chain alkyl group having 1 to 5 carbon atoms, an unsubstituted or substituted branched-chain alkyl group having 3 to 5 carbon atoms, or a + , Li + , K + , Rb + , Cs + , Fr + , Cu + 、Ag + 、Au + 、Ti + , Pd + 、Ni + , Mn + Cr + 、V + The monovalent metal cation is preferably Na + , Li + , K + , Cu + 、Ag + 、Au + , which is more preferably Na + , Li + , K + .

[0017] In another aspect, the present invention relates to a method for producing a composition as claimed in any one of the preceding claims, comprising at least the following steps:

[0018] (I x ) mixed with polysiloxane; and

[0019] A compound represented by chemical formula (I).

[0020] In another aspect, the invention relates to a composition obtainable or obtainable by the method of the invention.

[0021] In another aspect, the invention relates to a method of manufacturing a layer, comprising at least, consisting essentially of or consisting of the following steps:

[0022] (I Y ) providing the composition of the present invention, preferably providing the composition of the present invention on a substrate, a support layer or an electronic device layer;

[0023] (II Y ) heating the provided composition to form a layer, preferably to remove the solvent in the composition.

[0024] In another aspect, the invention relates to a layer obtained from a composition according to the invention by curing or obtained by a process according to the invention.

[0025] In another aspect, the invention relates to a layer comprising at least, consisting essentially of, or consisting of:

[0026] i) polymers made from polysiloxanes; and

[0027] ii) A compound represented by the chemical formula (I).

[0028] In another aspect, the invention relates to an electronic device comprising at least a layer according to the invention.

[0029] In another aspect, the present invention further relates to a method of using the compound of formula (I) as a dielectric constant enhancer in a polysiloxane-containing composition.

[0030] In another aspect, the present invention further relates to a method of using the composition of the present invention as a composition for forming a protective layer for an electronic device.

[0031] Other advantages of the present invention will become apparent from the following detailed description.

[0032] Definition of terms

[0033] In this specification, unless otherwise specified, symbols, units, abbreviations and terms have the following meanings.

[0034] In this specification, unless otherwise specifically mentioned, the singular includes the plural and "a" or "the" means "at least one". In this specification, unless otherwise specifically mentioned, the elements of a concept may be represented by a plurality of species, and when describing an amount (e.g., mass % or mole %), it means the sum of the plurality of species. "And / or" includes a combination of all elements and also includes the individual use of the elements.

[0035] In the present specification, when "to" or "-" is used to indicate a numerical range, it includes both endpoints and its unit is shared. For example, 5 to 25 mol% means 5 mol% or more and 25 mol% or less.

[0036] In this specification, hydrocarbon means a hydrocarbon including carbon and hydrogen, and optionally including oxygen or nitrogen. Hydrocarbyl means a monovalent or divalent or higher valent hydrocarbon. In this specification, aliphatic hydrocarbon means a straight chain, branched or cyclic aliphatic hydrocarbon, and aliphatic hydrocarbon group means a monovalent or divalent or higher valent aliphatic hydrocarbon. Aromatic hydrocarbon means a hydrocarbon containing an aromatic ring, which may optionally not only contain an aliphatic hydrocarbon group as a substituent, but also be condensed with an alicyclic ring. Aromatic hydrocarbon group means a monovalent or divalent or higher valent aromatic hydrocarbon. In addition, aromatic ring means a hydrocarbon containing a conjugated unsaturated ring structure, and alicyclic ring means a hydrocarbon having a ring structure but not containing a conjugated unsaturated ring structure.

[0037] In the present specification, an alkyl group means a group obtained by removing any one hydrogen from a linear or branched saturated hydrocarbon and includes a linear alkyl group and a branched alkyl group, and a cycloalkyl group means a group obtained by removing one hydrogen from a saturated hydrocarbon including a cyclic structure, and optionally includes a linear or branched alkyl group as a side chain in the cyclic structure.

[0038] In the present specification, an aryl group means a group obtained by removing any one hydrogen from an aromatic hydrocarbon. An alkylene group means a group obtained by removing any two hydrogens from a straight or branched saturated hydrocarbon. An arylene group means a hydrocarbon group obtained by removing any two hydrogens from an aromatic hydrocarbon.

[0039] In the present specification, when a polymer has a plurality of types of repeating units, these repeating units are copolymerized, and these copolymerizations are any of alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture of any of these copolymerizations.

[0040] In this specification, Celsius is used as a temperature unit. For example, 20°C, 20 degrees means 20 degrees Celsius.

[0041] DETAILED DESCRIPTION OF THE INVENTION

[0042] According to the present invention, in one aspect, the composition that is preferably the composition for forming the protective layer comprises at least, consists essentially of, or consists of:

[0043] i) polysiloxane; and

[0044] ii) a compound represented by the following chemical formula (I), which is preferably a dielectric constant promoter, preferably for use in a polysiloxane-containing composition,

[0045]

[0046] in

[0047] Z X1 Selected from the group consisting of a direct bond, CH2, C=O, O, (C=O)2, (C=O)O, (C=O)3, (C=O)2O, (C=O)2CH2 and C=O(CH2)2, preferably selected from a direct bond, C=O, O, (C=O)2, (C=O)3;

[0048] n is 0 or 1;

[0049] R x1 H, D or OR x3 ;

[0050] R x2 H, D or OR x3 ;

[0051] R x3 is H, D, an unsubstituted or substituted straight-chain alkyl group having 1 to 5 carbon atoms, an unsubstituted or substituted branched-chain alkyl group having 3 to 5 carbon atoms, or a + , Li + , K + , Rb + , Cs + , Fr + , Cu + 、Ag + 、Au + 、Ti + , Pd + 、Ni + , Mn + Cr + 、V + The monovalent metal cation is preferably Na + , Li + , K + , Cu + 、Ag + 、Au + , which is more preferably Na + , Li + , K + .

[0052] - Composition

[0053] In a preferred embodiment of the present invention, the dielectric constant (ε r) is 3.5 or more and 7 or less, it is preferably 3.9 or more to 6.5, more preferably 4.0 or more, it is preferably 6.5 or less, more preferably 6 or less. Preferably, from the viewpoint of achieving a high dielectric constant of the composition and the resulting layer, the dielectric constant (ε) of the solid content of the composition is r ) is measured by the following method.

[0054] According to the present invention, the dielectric constant (ε r ) is measured by the following method.

[0055] 1) Sample preparation and dielectric constant measurement

[0056] coating the composition on a conductive wafer selected from Al, Si or Mo;

[0057] Using Ag or Al, electrodes were placed on the applied composition by sputtering or vapor deposition to form samples:

[0058] The dielectric constant of the sample was measured by attaching a needle probe to the surface of the conductive wafer and the top electrode on the coated composition, respectively.

[0059] 2) Measurement conditions: The dielectric constant was measured by an LCR meter (E4980A, Agilent (Korea) / 6440B, Toyotechnical (Japan)), where a specific range of frequencies (50-1 MHz) was applied at room temperature and the capacitance indicated in the LCR meter was read. The dielectric constant value was calculated by the following equation: C = KA / d (C = capacitance, K = dielectric constant, A = effective area of ​​the electrode, d = distance between the electrodes).

[0060] ii) Compounds of formula (I)

[0061] According to the present invention, any publicly available compound represented by the chemical formula (I) can be used.

[0062] It is believed that such compounds form a two-dimensional structure in and / or on the film surface and provide a higher dielectric constant, and / or such compounds are regularly aligned through effective strong hydrogen bonding conjugation.

[0063] Preferably, the molecular weight (Mw) of the compound is 250 or less, preferably in the range of 30-250, more preferably in the range of 100-200.

[0064] It is believed that such a molecular weight allows improved dispersibility of the compound of formula (I) in polysiloxane and good compatibility with polysiloxane and allows lower haze values ​​for the composition and the layer obtained therefrom.

[0065] In a preferred embodiment of the present invention, the total amount of the compound of formula (I) is in the range of 0.01 to 40 wt %, preferably in the range of 0.1 to 20 wt %, more preferably in the range of 0.5 to 5.0 wt %, based on the total amount of polysilazane in the composition.

[0066] It is believed that the above total amount of the compound, based on the total amount of polysiloxane in the composition, allows to achieve further improvement in the dispersibility of the compound of formula (I) in the composition and the resulting layer, as well as lower haze values ​​of the layer obtained from the composition, and optimally high values ​​of the dielectric constant of the composition and the resulting layer, similar to that of a glass substrate.

[0067] According to the present invention, Z of formula (I) X1 Preferably selected from direct bond, C=O, O, (C=O)2, (C=O)3;

[0068] n is 0 or 1;

[0069] R x1 H or OR x3 ;

[0070] R x2 H or OR x3 ;

[0071] R x3 is H, an unsubstituted or substituted straight-chain alkyl group having 1 to 3 carbon atoms, or a + , Li + , K + , Cu + 、Ag + 、Au + The monovalent metal cation of the group consisting of Na + , Li + , K + ;

[0072] Preferably, the compound is an oxocabonic acid selected from the following: deltic acid, squaric acid, croconic acid, rhodizonic acid or heptagonic acid, the oxocabonic acid is preferably squaric acid or croconic acid; an oxocabonic acid derivative, the oxocabonic acid derivative is preferably 3,4-dihydroxy-3-cyclobutene-1,2-dione (squaric acid diethyl ester); 3,4-dibutoxy-3-cyclobutene-1,2-dione (squaric acid dibutyl ester), disodium croconic acid, rhodizonic acid dipotassium; maleic anhydride or any combination thereof.

[0073] i) Polysiloxane

[0074] According to the present invention, any publicly available polysiloxane may be used. Preferably, the polysiloxane comprises the chemical formula (I a ) repeating unit.

[0075]

[0076] in

[0077] R Ia For hydrogen, C 1-30 (Preferably C 1-10 ) Straight chain, C 3-30 (Preferably C 3-10 ) a branched or cyclic, saturated or unsaturated aliphatic hydrocarbon group or an aromatic hydrocarbon group, each of which is unsubstituted or substituted with fluorine, hydroxyl or alkoxy, and

[0078] In the aliphatic hydrocarbon group and the aromatic hydrocarbon group, the methylene group is unsubstituted, or one or more methylene groups are substituted by an oxy group, an imino group or a carbonyl group, with the restriction that R Ia It is neither hydroxy nor alkoxy.

[0079] Here, the above-mentioned methylene group also includes a terminal methyl group.

[0080] In addition, the above-described "substituted with fluorine, hydroxyl or alkoxy" means that hydrogen atoms directly bonded to carbon atoms in aliphatic hydrocarbon groups and aromatic hydrocarbon groups are replaced with fluorine, hydroxyl or alkoxy. In the present specification, the above-mentioned contents apply to other similar descriptions.

[0081] In a more preferred embodiment of the present invention, in the a ) in the repeating unit represented by Ia For example, (i) alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl and decyl groups are included, (ii) aryl groups such as phenyl, tolyl and benzyl groups, (iii) fluoroalkyl groups such as trifluoromethyl, 2,2,2-trifluoroethyl and 3,3,3-trifluoropropyl groups, (iv) fluoroaryl groups, (v) cycloalkyl groups such as cyclohexyl groups, (vi) nitrogen-containing groups having amino or imide structures such as isocyanate and amino groups, and (vii) oxygen-containing groups having epoxy structures such as glycidyl or acryl or methacryloyl structures. Preferably, they are methyl, ethyl, propyl, butyl, pentyl, hexyl and phenyl groups. Where R Ia The compound in which R is methyl is preferred because its raw material is easily available, its film hardness after curing is high and it has high chemical resistance. Ia A compound which is a phenyl group is preferable because it increases the solubility of the polysiloxane in the solvent and the cured film becomes less likely to be broken.

[0082] In a preferred embodiment of the present invention, the polysiloxane used in the present invention may further comprise b ) represents a repeating unit:

[0083]

[0084] in

[0085] R Ib It is a group obtained by removing a plurality of hydrogen atoms from a nitrogen-containing and / or oxygen-containing cycloaliphatic hydrocarbon compound having an amino group, an imino group and / or a carbonyl group.

[0086] In formula (Ib), R Ib Preferred is a group obtained by removing a plurality of hydrogen atoms, preferably two or three hydrogen atoms, from a nitrogen-containing aliphatic hydrocarbon ring preferably having an imino group and / or a carbonyl group, more preferably a 5-membered or 6-membered ring containing nitrogen as a member. For example, a group obtained by removing two or three hydrogen atoms from piperidine, pyrrolidine or isocyanurate. Ib The Si included in the plurality of repeating units are connected to each other.

[0087] In a preferred embodiment of the present invention, the polysiloxane used in the present invention may further comprise c ) represents a repeating unit:

[0088]

[0089] When the formula (I b ) and (I c ) When the mixing ratio of the repeating unit represented by is high, the compatibility with the solvent and the additive is reduced, and the film stress is increased, so that cracks are sometimes easily generated. Therefore, based on the total number of repeating units of the polysiloxane, it is preferably 40 mol% or less, more preferably 20 mol% or less.

[0090] According to the present invention, in some embodiments, the polysiloxane used in the present invention may further comprise a d ) represents a repeating unit:

[0091]

[0092] in

[0093] R Id Each independently represents hydrogen, C 1-30 (Preferably C 1-10 ) Straight chain, C 3-30 (Preferably C 3-10 ) a branched or cyclic, saturated or unsaturated aliphatic or aromatic hydrocarbon group;

[0094] The aliphatic hydrocarbon group and the aromatic hydrocarbon group are each unsubstituted or substituted with fluorine, hydroxyl or alkoxy, and

[0095] In the aliphatic hydrocarbon group and the aromatic hydrocarbon group, the methylene group is unsubstituted or substituted with an oxy group, an imide group or a carbonyl group.

[0096] In the formula (I d ) in the repeating unit represented by Id For example, (i) alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl and decyl groups are included, (ii) aryl groups such as phenyl, tolyl and benzyl groups, (iii) fluoroalkyl groups such as trifluoromethyl, 2,2,2-trifluoroethyl and 3,3,3-trifluoropropyl groups, (iv) fluoroaryl groups, (v) cycloalkyl groups such as cyclohexyl groups, (vi) nitrogen-containing groups having amino or imide structures such as isocyanate and amino groups, and (vii) oxygen-containing groups having epoxy structures such as glycidyl or acryl or methacryloyl structures. Preferably, they are methyl, ethyl, propyl, butyl, pentyl, hexyl and phenyl groups. Where R Id The compound in which R is methyl is preferred because its raw material is easily available, its film hardness after curing is high and it has high chemical resistance. Id A compound which is a phenyl group is preferable because it increases the solubility of the polysiloxane in the solvent and the cured film becomes less likely to be broken.

[0097] By having the above formula (I d ) can make the polysiloxane according to the present invention partially have a linear structure.

[0098] However, since heat resistance is reduced, it is preferred that the linear structure portion is less. In particular, based on the total number of repeating units of the polysiloxane, the formula (I d ) is preferably 30 mol% or less, more preferably 5 mol% or less. d ) repeating units (0 mol %) are also an aspect of the present invention.

[0099] The polysiloxane further comprises the chemical formula (I e ) repeating unit.

[0100]

[0101] in

[0102] R Ieis a straight-chain alkyl group having 1 to 5 carbon atoms or a branched-chain alkyl group having 3 to 7 carbon atoms, wherein one or more non-adjacent CH2 groups of the straight-chain alkyl group or the branched-chain alkyl group may be replaced by C=CH2, C=O or OH, or the terminal CH3 group of the straight-chain alkyl group having 1 to 5 carbon atoms or the branched-chain alkyl group having 3 to 7 carbon atoms may be replaced by C=CH3, R Ie It is preferably a straight-chain alkyl group having 1 to 4 carbon atoms, a branched-chain alkyl group having 3 to 5 carbon atoms, it is more preferably a branched-chain alkyl group having 3 to 5 carbon atoms, it is further preferably a branched-chain alkyl group having 3 carbon atoms,

[0103] More preferably, at least one CH2 group in the straight-chain alkyl group having 1 to 5 carbon atoms or the branched-chain alkyl group having 3 to 7 carbon atoms is replaced by C=CH2, or the terminal CH3 group of the straight-chain alkyl group having 1 to 5 carbon atoms or the branched-chain alkyl group having 3 to 7 carbon atoms may be replaced by C=CH3, R Ie Furthermore, C═CH3 or C═CH2-CH3 is preferred.

[0104] Most preferably, the chemical formula (I e )for

[0105]

[0106] ma is an integer of 1 to 6, preferably an integer of 2 to 5, and more preferably 3, respectively.

[0107] It is believed that such acrylic functional substituted siloxane polymers can produce higher dielectric constants. In other words, the siloxane polymers containing formula (I e ) can produce a higher dielectric constant. As the siloxane polymer containing the repeating unit of formula (Ie), it is preferred to use publicly available siloxane polymers. For example, siloxane polymers from Torey fine chemical, siloxane polymers from Merck,

[0108] The polysiloxane used in the present invention may contain two or more types of the above-mentioned repeating units. For example, it may contain three types of repeating units having a structure in which R Ia The repeating unit represented by the formula (Ia) is a methyl group or a phenyl group, and the repeating unit represented by the formula (I c ) represents a repeating unit.

[0109] In addition, the polysiloxane used in the composition according to the present invention preferably has silanol. Herein, silanol refers to a silanol in which the OH group is directly bonded to the Si backbone of the polysiloxane and the hydroxyl group is directly bonded to a silanol containing a polysiloxane such as the above formula (I a ) to (I d) of the repeating unit of the polysiloxane. That is, the silanol is obtained by making the above formula (I a ) to (I d ) is bonded to -O0.5-. The content of silanol in polysiloxane varies depending on the conditions for synthesizing polysiloxane, such as the mixing ratio of monomers, the type of reaction catalyst, and the like.

[0110] The silanol content can be evaluated by quantitative infrared absorption spectroscopy. The absorption band attributed to silanol (SiOH) appears as a peak at 900 ± 100 cm in the infrared absorption spectrum. -1 When the content of silanol is high, the intensity of this absorption band increases.

[0111] It is believed that the highly silanol-residual siloxane polymers are effective in dispersing the compound of formula (I) well in the composition / resulting film.

[0112] In the present invention, in order to quantitatively evaluate the silanol content, the intensity of the absorption band attributed to Si-0 is used as a reference. The peak is at 1100 ± 100 cm -1 The absorption band in the range of is used as the peak attributed to Si-O. The silanol content can be relatively evaluated by the S2 / S1 ratio, which is the ratio of the integrated intensity S2 of the absorption band attributed to SiOH to the integrated intensity SI of the absorption band attributed to Si-O. In the present invention, the S2 / S1 ratio is preferably 0.003 to 0.15, more preferably 0.01 to 0.10.

[0113] The integrated intensity of the absorption band is measured by taking into account the noise in the infrared absorption spectrum. In a typical infrared absorption spectrum of polysiloxane, a band of 900±100 cm-1 attributable to Si-OH is confirmed. -1 The absorption band of the peak in the range of 1100±100cm -1 The absorption bands of the peaks in the range of . The integrated intensity of these absorption bands can be measured in the form of area taking into account the baseline (wherein noise and the like are taken into account). Incidentally, it is possible that the bottom of the absorption band attributed to Si-OH overlaps with the bottom of the absorption band attributed to Si-O; however, in this case, the wave number corresponding to the minimum point between the two absorption bands in the spectrum is set as its boundary. The above situation applies to the case where the bottom of another absorption band overlaps with the bottom of the absorption band attributed to Si-OH or Si-O.

[0114] The mass average molecular weight of the polysiloxane used in the present invention is not subject to specific restrictions. However, the higher the molecular weight, the more the coating properties tend to be improved. On the other hand, the lower the molecular weight, the fewer the restricted synthesis conditions, making it easy to synthesize, and it is difficult to synthesize polysiloxanes with extremely high molecular weight. For these reasons, from the viewpoint of solubility in organic solvents, the mass average molecular weight of polysiloxane is generally 500 to 25,000, and preferably 1,000 to 20,000. Herein, the mass average molecular weight means the mass average molecular weight with respect to polystyrene, which can be measured based on polystyrene by gel permeation chromatography.

[0115] As stated above, preferably publicly available polysiloxanes falling within the above definition may be used, for example as described in WO 2021 / 099236 A1, EP 3717966 B1.

[0116] Solvents

[0117] In a preferred embodiment of the present invention, the composition may further contain a solvent from the viewpoint of improving the handling, coating, coating of the composition when stringing or when making a layer. Or from the viewpoint of providing a solvent-free composition, the composition contains 5% by weight or less of a solvent based on the total amount of polysiloxane in the composition, and preferably, the composition does not contain any solvent.

[0118] Preferably, the solvent is selected from one or more members of the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol diacetate, diethylene glycol monohexyl ether and methyl 3-methoxypropionate, methyl isobutyl ketone, methyl ethyl ketone, and the amine solvent is preferably selected from one or more members of the group consisting of N-methylpyrrolidone (NMP), 3-methoxy-N,N-dimethylpropionamide, N,N-dimethylacetamide (DMA), N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), hexamethylphosphoric triamide (HMPA), acetonitrile, and more preferably N-methylpyrrolidone (NMP) or 3-methoxy-N,N-dimethylpropionamide.

[0119] It is believed that the above selected solvents have good compatibility with the composition, boiling point, viscosity and / or vapor pressure, thereby achieving better handling of the composition suitable for low temperature fabrication of the layer, and / or achieving easy fabrication.

[0120] It is believed that an amine-type solvent, preferably an aprotic polar solvent, preferably one or more members selected from the group consisting of: N-methylpyrrolidone (NMP), 3-methoxy-N,N-dimethylpropionamide, N,N-dimethylacetamide (DMA), N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), hexamethylphosphoric triamide (HMPA), acetonitrile, more preferably N-methylpyrrolidone (NMP) or 3-methoxy-N,N-dimethylpropionamide; can improve the dispersibility of the compound of formula (I) in the polymer composition and / or in the resulting layer.

[0121] Therefore, in a preferred embodiment of the present invention, the solvent contains at least one amine solvent selected from one or more members of the group consisting of: N-methylpyrrolidone (NMP), 3-methoxy-N,N-dimethylpropionamide, N,N-dimethylacetamide (DMA), N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), hexamethylphosphoric triamide (HMPA), acetonitrile, and the amine solvent is preferably N-methylpyrrolidone (NMP) or 3-methoxy-N,N-dimethylpropionamide.

[0122] Preferably, the solvent may further contain another solvent selected from one or more members of the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol diacetate, diethylene glycol monohexyl ether, methyl 3-methoxypropionate, methyl isobutyl ketone, methyl ethyl ketone and γ-butyrolactone.

[0123] In a preferred embodiment of the present invention, the total amount of the solvent is 0 to 300 wt % based on the total amount of the polysiloxane. When the composition contains a solvent, it is preferably 0.1 to 150 wt %, more preferably 10 to 90 wt %.

[0124] additive

[0125] In some embodiments of the present invention, the composition may optionally further include one or more additives. Such additives may be selected from one or more members of the group consisting of: for example, surfactants, adhesion promoters, silane coupling agents, thermal acid generators, thermal base generators, crosslinkable monomers and polymerization initiators. Preferably, publicly available additives can be used, as described in EP3717966A1 or WO2021 / 099236A1. Since the additive is not required for the present invention, the amount of the additive 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 additives.

[0126] In another aspect, the present invention further relates to a method of making a composition of the present invention, comprising at least, consisting essentially of, or consisting of the following steps:

[0127] (I x ) mixed with polysiloxane; and

[0128] A compound represented by the following chemical formula (I), which is preferably a dielectric constant promoter, is preferably used in a polysiloxane-containing composition,

[0129]

[0130] in

[0131] Z X1 Selected from the group consisting of a direct bond, CH2, C=O, O, (C=O)2, (C=O)O, (C=O)3, (C=O)2O, (C=O)2CH2 and C=O(CH2)2, preferably selected from a direct bond, C=O, O, (C=O)2, (C=O)3;

[0132] n is 0 or 1;

[0133] R x1 H, D or OR x3 ;

[0134] R x2 H, D or OR x3 ;

[0135] R x3 is H, D, an unsubstituted or substituted straight-chain alkyl group having 1 to 5 carbon atoms, an unsubstituted or substituted branched-chain alkyl group having 3 to 5 carbon atoms, or a + , Li + , K + , Rb + , Cs + , Fr + , Cu + 、Ag + 、Au + 、Ti + , Pd + 、Ni + , Mn + Cr + 、V + The monovalent metal cation is preferably Na + , Li + , K + , Cu + 、Ag + 、Au + , which is more preferably Na+ , Li + , K + .

[0136] The detailed description of the compounds and polysiloxanes, including preferred amounts, is indicated above in the sections ii) Compounds of formula (I) and i) Polysiloxanes.

[0137] In another aspect, the present invention further relates to a composition obtainable or obtainable by the method for manufacturing a composition as described above.

[0138] In another aspect, the present invention further relates to a method of manufacturing a layer, comprising at least, consisting essentially of or consisting of the following steps:

[0139] (I Y ) providing the composition of the present invention, preferably providing the composition of the present invention on a substrate, a support layer or an electronic device layer;

[0140] (II Y ) heating the provided composition to form a layer, preferably to remove the solvent in the composition, the heating is preferably carried out at a temperature in the range of 60 to 140° C., more preferably in the range of 80 to 130° C.

[0141] (III Y ) Optionally, the provided composition is irradiated with ultraviolet (UV) light to cure.

[0142] According to the present invention, the UV light is light having a peak light wavelength in the range of 250-450 nm.

[0143] In another aspect, the present invention further relates to a layer obtained by curing the composition of the present invention or by the above-mentioned method for producing a layer. Preferably, the layer is a protective layer for an electrical device. Preferably, the curing is thermal curing and / or UV light curing.

[0144] In another aspect, the present invention further relates to a layer at least comprising, consisting essentially of, or consisting of:

[0145] i) polymers made from polysiloxanes; and

[0146] A compound represented by the following chemical formula (I), which is preferably a dielectric constant promoter, is preferably used in a polysiloxane-containing composition,

[0147]

[0148] in

[0149] Z X1Selected from the group consisting of a direct bond, CH2, C=O, O, (C=O)2, (C=O)O, (C=O)3, (C=O)2O, (C=O)2CH2 and C=O(CH2)2, preferably selected from a direct bond, C=O, O, (C=O)2, (C=O)3;

[0150] n is 0 or 1;

[0151] R x1 H, D or OR x3 ;

[0152] R x2 H, D or OR x3 ;

[0153] R x3 is H, D, an unsubstituted or substituted straight-chain alkyl group having 1 to 5 carbon atoms, an unsubstituted or substituted branched-chain alkyl group having 3 to 5 carbon atoms, or a + , Li + , K + , Rb + , Cs + , Fr + , Cu + 、Ag + 、Au + 、Ti + , Pd + 、Ni + , Mn + Cr + 、V + The monovalent metal cation is preferably Na + , Li + , K + , Cu + 、Ag + 、Au + , which is more preferably Na + , Li + , K + .

[0154] The detailed description of the compounds of formula (I) and polysiloxanes, including preferred amounts, is indicated above in the sections ii) Compounds of formula (I) and i) Polysiloxanes.

[0155] In a preferred embodiment of the invention, the dielectric constant (ε r) is 3.5 or more and 7 or less, it is preferably 3.9 or more to 6.5, more preferably 4.0 or more, it is preferably 6.5 or less, more preferably 6 or less. It is preferably in the range of 3.5 to 7, it is more preferably in the range of 3.6 to 6.5, even more preferably in the range of 4 to 6.

[0156] It is believed that when the layer is used as a protective layer for a device (ie, an electronic device such as an OLED, LCD), the above dielectric constant (ε r ) achieves touch sensitivity improvement of the layer, similar to a glass substrate.

[0157] The dielectric constant of the layer is measured as described above in the composition section.

[0158] In a preferred embodiment of the present invention, the haze value of the layer is less than 100%, preferably in the range of 0.01 to 10%, more preferably in the range of 0.1 to 5%.

[0159] According to the present invention, the turbidity value is measured in air at room temperature using a turbidity measurement system with an integrating sphere (NDH-7000, Nippon Denshoku, Japan, light source white LED 3W, wavelength range 380-780 nm). The sample thickness is between 2 μm and 700 μm. In particular, it is 700 μm.

[0160] Schematic diagram of an integrating sphere used for transmittance and turbidity measurements, total transmittance (T T )T T =T P +T D , turbidity (H) H = T D / T T .

[0161] Parallel transmittance (T P ) is determined by measuring the light intensity at a position relative to the position of the sample in the sphere, and the total transmittance (T T ), including diffracted light transmittance (T D ) and T P , is to use the equation T T =T P +T D It is obtained by measuring the light passing through the sample. The light scattering in the sample, i.e. turbidity (H), is defined as H = T D / T T .Measure transmittance and turbidity.

[0162] In another aspect, the invention further relates to an electronic device comprising at least the layer of the invention, preferably the electronic device comprises a light modulating layer or a light emitting layer, preferably the layer is placed on the outermost surface of the electronic device. More preferably, it is the light extraction side (viewing side) of the electronic device. Preferably, the electronic device does not comprise a cover glass substrate and the layer is used instead of the cover glass substrate to achieve an electronic device without cover glass with good touch sensitivity, preferably with lower haze values.

[0163] In another aspect, the present invention further relates to a method of using the compound of formula (I) as a dielectric constant enhancer in a polysiloxane-containing composition.

[0164] In another aspect, the present invention further relates to a method of using the composition of the present invention as a composition for forming a protective layer for an electronic device, preferably using the composition to replace an upper glass substrate of the electronic device.

[0165] Preferred Implementation

[0166] 1. A composition, preferably a composition for forming a protective layer, comprising at least, essentially consisting of, or consisting of:

[0167] i) polysiloxane; and

[0168] ii) a compound represented by the following chemical formula (I), which is preferably a dielectric constant promoter, preferably for use in a polysiloxane-containing composition,

[0169]

[0170] in

[0171] Z X1 Selected from the group consisting of a direct bond, CH2, C=O, O, (C=O)2, (C=O)O, (C=O)3, (C=O)2O, (C=O)2CH2 and C=O(CH2)2, preferably selected from a direct bond, C=O, O, (C=O)2, (C=O)3;

[0172] n is 0 or 1;

[0173] R x1 H, D or OR x3 ;

[0174] R x2 H, D or OR x3 ;

[0175] R x3 is H, D, an unsubstituted or substituted straight-chain alkyl group having 1 to 5 carbon atoms, an unsubstituted or substituted branched-chain alkyl group having 3 to 5 carbon atoms, or a+ , Li + , K + , Rb + , Cs + , Fr + , Cu + 、Ag + 、Au + 、Ti + , Pd + 、Ni + , Mn + Cr + 、V + The monovalent metal cation is preferably Na + , Li + , K + , Cu + 、Ag + 、Au + , which is more preferably Na + , Li + , K + .

[0176] 2. The composition of embodiment 1, wherein the molecular weight (Mw) of the compound is 250 or less, preferably in the range of 30 to 250, more preferably in the range of 100 to 200.

[0177] 3. A composition according to embodiment 1 or 2, wherein the total amount of the compound of formula (I) is in the range of 0.01 to 40 wt %, preferably in the range of 0.1 to 20 wt %, more preferably in the range of 0.3 to 5.0 wt %, based on the total amount of polysilazane in the composition.

[0178] 4. A composition as in any of the preceding embodiments, wherein the dielectric constant (ε r ) is 3.5 or more and 7 or less, it is preferably 3.9 or more to 6.5, more preferably 4.0 or more, it is preferably 6.5 or less, more preferably 6 or less.

[0179] Preferably, the dielectric constant (ε r ) is measured by:

[0180] 1) Sample preparation and dielectric constant measurement

[0181] coating the composition on a conductive wafer selected from Al, Si or Mo;

[0182] Using Ag or Al, electrodes were placed on the applied composition by sputtering or vapor deposition to form samples:

[0183] The dielectric constant of the sample was measured by attaching a needle probe to the surface of the conductive wafer and the top electrode on the coated composition, respectively.

[0184] 2) Measurement conditions; The dielectric constant was measured by an LCR meter (E4980A, Agilent (Korea) / 6440B, Toyotechnical (Japan)), where a specific range of frequencies (50 to 1 MHz) was applied at room temperature and the capacitance indicated in the LCR meter was read. The dielectric constant value was calculated by the following equation C = KA / d (C = capacitance, K = dielectric constant, A = effective area of ​​the electrode, d = distance between the electrodes)

[0185] 5. A composition according to any one of the preceding embodiments,

[0186] Z X1 is selected from a direct bond, C=O, O, (C=O)2, (C=O)3;

[0187] n is 0 or 1;

[0188] R x1 H or OR x3 ;

[0189] R x2 H or OR x3 ;

[0190] R x3 is H, an unsubstituted or substituted straight-chain alkyl group having 1 to 3 carbon atoms, or a + , Li + , K + , Cu + 、Ag + 、Au + The monovalent metal cation of the group consisting of Na + , Li + , K + ;

[0191] Preferably, the compound is an oxocarbonic acid selected from the following: triangular acid, squaric acid, ketoic acid, rose palmitic acid or heptagonal acid, and the oxocarbonic acid is preferably squaric acid or ketoic acid; an oxocarbonic acid derivative, and the oxocarbonic acid derivative is preferably 3,4-dihydroxy-3-cyclobutene-1,2-dione (squaric acid diethyl ester); 3,4-dibutoxy-3-cyclobutene-1,2-dione (squaric acid dibutyl ester), ketoic acid disodium salt, rose palmitic acid dipotassium; maleic anhydride or any combination thereof.

[0192] 6. A composition according to any one of the preceding embodiments, wherein the polysiloxane comprises formula (I a )'s repeating unit:

[0193]

[0194] in

[0195] R Ia For hydrogen, C 1-30 (Preferably C 1-10 ) Straight chain, C 3-30 (Preferably C 3-10 ) a branched or cyclic, saturated or unsaturated aliphatic hydrocarbon group or an aromatic hydrocarbon group, each of which is unsubstituted or substituted with fluorine, hydroxyl or alkoxy, and

[0196] In the aliphatic hydrocarbon group and the aromatic hydrocarbon group, the methylene group is unsubstituted, or one or more methylene groups are substituted by an oxy group, an imino group or a carbonyl group, with the restriction that R Ia Neither hydroxy nor alkoxy.

[0197] 7. A composition according to any one of the preceding embodiments, wherein the polysiloxane comprises formula (I b )'s repeating unit:

[0198]

[0199] in

[0200] R Ib It is a group obtained by removing a plurality of hydrogen atoms from a nitrogen-containing and / or oxygen-containing cycloaliphatic hydrocarbon compound having an amino group, an imino group and / or a carbonyl group.

[0201] R Ib Preferred is a group obtained by removing a plurality of hydrogen atoms, preferably two or three hydrogen atoms, from a nitrogen-containing aliphatic hydrocarbon ring preferably having an imino group and / or a carbonyl group, more preferably a 5-membered or 6-membered ring containing nitrogen as a member. For example, a group obtained by removing two or three hydrogen atoms from piperidine, pyrrolidine or isocyanurate. Ib The Si included in the plurality of repeating units are connected to each other.

[0202] 8. A composition according to any one of the preceding embodiments, wherein the polysiloxane comprises formula (I c )'s repeating unit:

[0203]

[0204] 9. A composition according to any one of the preceding embodiments, wherein the polysiloxane comprises formula (I d )'s repeating unit:

[0205]

[0206] in

[0207] R Id Each independently represents hydrogen, C 1-30 (Preferably C 1-10 ) Straight chain, C 3-30 (Preferably C 3-10 ) a branched or cyclic, saturated or unsaturated aliphatic or aromatic hydrocarbon group;

[0208] The aliphatic hydrocarbon group and the aromatic hydrocarbon group are each unsubstituted or substituted with fluorine, hydroxyl or alkoxy, and

[0209] In the aliphatic hydrocarbon group and the aromatic hydrocarbon group, the methylene group is unsubstituted or substituted with an oxy group, an imide group or a carbonyl group.

[0210] 10. A composition according to any one of the preceding embodiments, wherein the polysiloxane comprises formula (I e )'s repeating unit:

[0211]

[0212] in

[0213] R Ie is a straight-chain alkyl group having 1 to 5 carbon atoms or a branched-chain alkyl group having 3 to 7 carbon atoms, wherein one or more non-adjacent CH2 groups of the straight-chain alkyl group or the branched-chain alkyl group may be replaced by C=CH2, C=O or OH, or the terminal CH3 group of the straight-chain alkyl group having 1 to 5 carbon atoms or the branched-chain alkyl group having 3 to 7 carbon atoms may be replaced by C=CH3, R Ie Preferably, it is a straight-chain alkyl group having 1 to 4 carbon atoms, a branched-chain alkyl group having 3 to 5 carbon atoms, more preferably a branched-chain alkyl group having 3 to 5 carbon atoms, and more preferably a branched-chain alkyl group having 3 carbon atoms,

[0214] More preferably, at least one CH2 group in the straight-chain alkyl group having 1 to 5 carbon atoms or the branched-chain alkyl group having 3 to 7 carbon atoms is replaced by C=CH2, or the terminal CH3 group of the straight-chain alkyl group having 1 to 5 carbon atoms or the branched-chain alkyl group having 3 to 7 carbon atoms may be replaced by C=CH3, R Ie Furthermore, C═CH3 or C═CH2-CH3 is preferred.

[0215] Most preferably, the chemical formula (I e )for

[0216]

[0217] ma is an integer of 1 to 6, preferably an integer of 2 to 5, and more preferably 3, respectively.

[0218] 11. The composition according to any of the preceding embodiments, further comprising an additive.

[0219] 12. A composition as in any one of the preceding embodiments, further comprising a solvent. Preferably, the solvent is selected from one or more members of the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol diacetate, diethylene glycol monohexyl ether and 3-methoxypropionic acid methyl ester, methyl isobutyl ketone, methyl ethyl ketone, and the amine solvent is preferably selected from one or more members of the group consisting of N-methylpyrrolidone (NMP), 3-methoxy-N, N-dimethylpropionamide, N, N-dimethylacetamide (DMA), N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetonitrile, and more preferably N-methylpyrrolidone (NMP) or 3-methoxy-N, N-dimethylpropionamide.

[0220] 13. A method of making a composition according to any of the preceding embodiments, comprising at least, consisting essentially of, or consisting of the following steps:

[0221] (I x ) mixed with polysiloxane; and

[0222] A compound represented by the following chemical formula (I), which is preferably a dielectric constant promoter, is preferably used in a composition containing polysiloxane,

[0223]

[0224] in

[0225] Z X1 Selected from the group consisting of a direct bond, CH2, C=O, O, (C=O)2, (C=O)O, (C=O)3, (C=O)2O, (C=O)2CH2 and C=O(CH2)2, preferably selected from a direct bond, C=O, O, (C=O)2, (C=O)3;

[0226] n is 0 or 1;

[0227] R x1 H, D or OR x3 ;

[0228] R x2 H, D or OR x3 ;

[0229] R x3 is H, D, an unsubstituted or substituted straight-chain alkyl group having 1 to 5 carbon atoms, an unsubstituted or substituted branched-chain alkyl group having 3 to 5 carbon atoms, or a + , Li + , K+ , Rb + , Cs + , Fr + , Cu + 、Ag + 、Au + 、Ti + , Pd + 、Ni + , Mn + Cr + 、V + The monovalent metal cation is preferably Na + , Li + , K + , Cu + 、Ag + 、Au + , which is more preferably Na + , Li + , K + .

[0230] 14. A composition obtainable or obtainable by the method according to embodiment 13.

[0231] 15. A method for manufacturing a layer, comprising at least the following steps:

[0232] (I Y ) providing a composition as in any one of embodiments 1 to 12 and 14, preferably providing the composition on a substrate, a support layer or an electronic device layer;

[0233] (II Y ) heating the provided composition to form a layer, preferably to remove the solvent in the composition, the heating is preferably carried out at a temperature in the range of 60 to 140° C., more preferably in the range of 80 to 130° C.

[0234] 16. A layer obtained by curing the composition of any one of embodiments 1 to 12 and 14 or by the method of embodiment 15. Preferably, the layer is a protective layer of an electrical device. Preferably, the curing is thermal curing.

[0235] 17. A layer comprising at least:

[0236] i) polymers made from polysiloxanes; and

[0237] ii) a compound represented by the following chemical formula (I), which is preferably a dielectric constant promoter, preferably for use in a polysiloxane-containing composition,

[0238]

[0239] in

[0240] Z X1 Selected from the group consisting of a direct bond, CH2, C=O, O, (C=O)2, (C=O)O, (C=O)3, (C=O)2O, (C=O)2CH2 and C=O(CH2)2, preferably selected from a direct bond, C=O, O, (C=O)2, (C=O)3;

[0241] n is 0 or 1;

[0242] R x1 H, D or OR x3 ;

[0243] R x2 H, D or OR x3 ;

[0244] R x3 is H, D, an unsubstituted or substituted straight-chain alkyl group having 1 to 5 carbon atoms, an unsubstituted or substituted branched-chain alkyl group having 3 to 5 carbon atoms, or a + , Li + , K + , Rb + , Cs + , Fr + , Cu + 、Ag + 、Au + 、Ti + , Pd + 、Ni + , Mn + Cr + 、V + The monovalent metal cation is preferably Na + , Li + , K + , Cu + 、Ag + 、Au + , which is more preferably Na + , Li + , K + .

[0245] 18. A layer according to embodiment 16 or 17, wherein the dielectric constant (ε r ) is 3.5 or more and 7 or less, it is preferably 3.9 or more to 6.5, more preferably 4.0 or more, it is preferably 6.5 or less, more preferably 6 or less. It is preferably in the range of 3.5 to 7, it is more preferably in the range of 3.6 to 6.5, even more preferably in the range of 4 to 6.

[0246] 19. The layer according to any of embodiments 16 to 18, wherein the layer has a haze value of less than 100%, preferably in the range of 0.01 to 10%, more preferably in the range of 0.1 to 5%.

[0247] The turbidity value was measured in air at room temperature using a turbidity measurement system with an integrating sphere (NDH-7000, Nippon Denshoku, Japan, light source white LED 3W, wavelength range 380-780 nm).

[0248] Schematic diagram of an integrating sphere used for transmittance and turbidity measurements, total transmittance (T T )T T =T P +T D , turbidity (H) H = T D / T T .

[0249] Parallel transmittance (T P ) is determined by measuring the light intensity at a position relative to the position of the sample in the sphere, and the total transmittance (T T ), including diffracted light transmittance (T D ) and T P , is to use the equation T T =T P +T D It is obtained by measuring the light passing through the sample. The light scattering in the sample, i.e. turbidity (H), is defined as H = T D / T T .Measure transmittance and turbidity.

[0250] 20. An electronic device comprising at least the layer according to any one of embodiments 16 to 19, preferably comprising a light modulating layer or a light emitting layer, preferably, the layer is placed on the outermost surface of the electronic device. More preferably, it is the light extraction side (observation side) of the electronic device.

[0251] 21. A method of using a compound of formula (I) as a dielectric constant enhancer in a polysiloxane-containing composition.

[0252] 22. A method of using the composition as any one of embodiments 1 to 12 and 14 as a composition for forming a protective layer for an electronic device, preferably using the composition to replace an upper glass substrate of the electronic device.

[0253] Technical Effects of the Invention

[0254] The present invention provides one or more of the following technical effects:

[0255] A polysiloxane-containing composition, preferably a protective layer-forming composition, is obtained, which exhibits an improved dielectric constant similar to that of a glass substrate of an electronic device, preferably with minimal turbidity characteristics; a layer or cured composition is obtained, which exhibits an improved dielectric constant similar to that of a glass substrate of an electronic device, preferably with minimal turbidity characteristics; a polysiloxane-containing composition, preferably a protective layer-forming composition, is obtained, which allows a sufficient amount of thiol to be well dispersed in the composition; a layer or cured composition is obtained, wherein a sufficient amount of thiol is well dispersed in the layer or cured composition; a polysiloxane-containing composition, preferably a protective layer-forming composition, is obtained, which allows a mild or relatively low temperature process to form a smooth coating of a layer or cured composition, a polysiloxane-containing composition on any substrate, i.e., PET, CPI, COP or polarizer.

[0256] Working Example

[0257] The following working examples provide a description of the invention, as well as a detailed description of its manufacture. However, the invention is not limited to these working examples.

[0258] Working Example 1: Mixed Sample Preparation

[0259] In the presence of a mixture of propylene glycol monomethyl ether acetate and NMP (N-methylpyrrolidone), a polysiloxane polymer represented by the following chemical formula from Merck was mixed with 0.5 wt% (sample 1-1), 1 wt% (sample 1-2) and 2 wt% (sample 1-3) of squaric acid as a compound of formula (I) based on the total amount of polysiloxane (total weight of the siloxane polymer and the compound of formula (I): solvent mixture = 3:7). After mixing the above compounds, they were respectively coated on Al-deposited silicon wafers by spin coating to obtain samples. Subsequently, the solvent mixture was evaporated under a curing process at 120° C. to obtain sample 1-1 (0.5 wt% squaric acid), sample 1-2 (1 wt% squaric acid) and sample 1-3 (2 wt% squaric acid).

[0260] a:b:c:d=2:4:3:1

[0261] Working Examples 2 to 4: Mixed Sample Preparation

[0262] Working Examples 2 to 4 were performed in the same manner as described in Working Example 1, except that the compounds listed below were used instead of squaric acid. Then, samples containing 0.5 wt % of the compound (samples 2-1, 3-1, 4-1), samples containing 1 wt % of the compound (samples 2-2, 3-2, 4-2), and samples containing 2 wt % of the compound (samples 2-3, 3-3, 4-3) were obtained in each working example.

[0263] - The compound represented by the chemical formula (I) used in working examples 1 to 4

[0264] Comparative Example 1: No use of thiol-containing compound

[0265] Working Example 1: Squaric Acid

[0266] Working Example 2: 3,4-dihydroxy-3-cyclobutene-1,2-dione

[0267] Working Example 3: Ketone acid

[0268] Working Example 4: Maleic Anhydride

[0269] Comparative Example 1: Reference Sample Preparation

[0270] A reference sample was prepared in the same manner as described in Working Example 1, but without adding the compound of formula (I) / mixing it with the siloxane polymer, and using the following polymer as the siloxane polymer. Reference sample 1 was then obtained.

[0271] n=0.5、m=0.4、l=0.1

[0272] Comparative Example 2: Reference Sample Preparation

[0273] A reference sample was prepared in the same manner as described in working example 1, but without adding the compound of formula (I) / mixing the compound of formula (I) with the siloxane polymer. Reference sample 2 was then obtained.

[0274] Working Example 5: Measurement of Dielectric Constants of Samples from Working Examples 1 to 4 and Comparative Example 1

[0275] The dielectric constant was measured by an LCR meter (E4980A, Agilent (Korea) / 6440B, Toyo technical (Japan)), where a specific range of frequencies (50 to 1 MHz) was applied at room temperature and the capacitance indicated in the LCR meter was read. The dielectric constant value was calculated by the following equation C = KA / d (C = capacitance, K = dielectric constant, A = effective area of ​​the electrode, d = distance between the electrodes)

[0276] Table 1 below shows the results of the measurements.

[0277] Table 1:

[0278]

[0279]

[0280] As shown in Table 1 above, the compound of formula (I), preferably the compound used in samples 1 to 4, significantly increases the dielectric constant of the polysiloxane composition. And it is believed that it can contribute to the touch sensitivity of glass-free electronic devices, such as touch-free glass OLED concepts.

Claims

1. A composition, preferably a composition for forming a protective layer, comprising at least: i) polysiloxane; and ii) a compound represented by the following chemical formula (I), which is preferably a dielectric constant promoter, preferably for use in a polysiloxane-containing composition, in Z X1 Selected from the group consisting of a direct bond, CH2, C=O, O, (C=O)2, (C=O)O, (C=O)3, (C=O)2O, (C=O)2CH2 and C=O(CH2)2, preferably selected from a direct bond, C=O, O, (C=O)2, (C=O)3; n is 0 or 1; R x1 is H, D or OR x3 ; R x2 is H, D or OR x3 ; R x3 is H, D, an unsubstituted or substituted straight-chain alkyl group having 1 to 5 carbon atoms, an unsubstituted or substituted branched-chain alkyl group having 3 to 5 carbon atoms, or a + , Li + , K + , Rb + , Cs + 、Fr + , Cu + 、Ag + 、Au + 、Ti + , Pd + 、Ni + , Mn + Cr + 、V + The monovalent metal cation is preferably Na + , Li + , K + , Cu + 、Ag + 、Au + , which is more preferably Na + , Li + , K + .

2. The composition according to claim 1, wherein the molecular weight (Mw) of the compound is 250 or less.

3. The composition according to claim 1 or 2, wherein the total amount of the compound is in the range of 0.01 to 40% by weight, based on the total amount of polysilazane in the composition.

4. A composition as claimed in any one of the preceding claims, wherein the dielectric constant (ε r ) is 3.5 or more and 7 or less, it is preferably 3.9 or more to 6.5, more preferably 4.0 or more, it is preferably 6.5 or less, more preferably 6 or less.

5. A composition according to any one of the preceding claims, wherein Z X1 is selected from a direct bond, C=O, O, (C=O)2, (C=O)3; n is 0 or 1; R x1 is H or OR x3 ; R x2 is H or OR x3 ; R x3 is H, an unsubstituted or substituted straight-chain alkyl group having 1 to 3 carbon atoms, or a + , Li + , K + , Cu + 、Ag + 、Au + The monovalent metal cation of the group consisting of Na + , Li + , K + ; Preferably, the compound is an oxocarbonic acid selected from the following: triangular acid, squaric acid, ketoic acid, rose palmitic acid or heptagonal acid, and the oxocarbonic acid is preferably squaric acid or ketoic acid; an oxocarbonic acid derivative, and the oxocarbonic acid derivative is preferably 3,4-dihydroxy-3-cyclobutene-1,2-dione (squaric acid diethyl ester); 3,4-dibutoxy-3-cyclobutene-1,2-dione (squaric acid dibutyl ester), ketoic acid disodium salt, rose palmitic acid dipotassium; maleic anhydride or any combination thereof.

6. A composition according to any one of the preceding claims, wherein the polysiloxane comprises formula (I a )'s repeating unit: in R Ia For hydrogen, C 1-30 (Preferably C 1-10 ) Straight chain, C 3-30 (Preferably C 3-10 ) a branched or cyclic, saturated or unsaturated aliphatic hydrocarbon group or an aromatic hydrocarbon group, each of which is unsubstituted or substituted with fluorine, hydroxyl or alkoxy, and In the aliphatic hydrocarbon group and the aromatic hydrocarbon group, the methylene group is unsubstituted, or one or more methylene groups are substituted by an oxy group, an imino group or a carbonyl group, with the restriction that R Ia It is neither a hydroxyl group nor an alkoxy group.

7. A composition according to any one of the preceding claims, wherein the polysiloxane comprises the formula (I b )'s repeating unit: in R Ib is a group obtained by removing a plurality of hydrogen atoms from a nitrogen-containing and / or oxygen-containing cycloaliphatic hydrocarbon compound having an amino group, an imino group and / or a carbonyl group; R Ib Preferably, it is a group obtained by removing a plurality of hydrogen atoms, preferably two or three hydrogen atoms, from a nitrogen-containing aliphatic hydrocarbon ring preferably having an imino group and / or a carbonyl group, more preferably a 5-membered or 6-membered ring containing nitrogen as a member, for example, a group obtained by removing two or three hydrogen atoms from piperidine, pyrrolidine or isocyanurate, R Ib The Si included in the plurality of repeating units are connected to each other.

8. A composition as claimed in any preceding claim further comprising a solvent.

9. A method for producing a composition according to any one of the preceding claims, comprising at least the following steps: (I x ) mixed with polysiloxane; and A compound represented by the following chemical formula (I), which is preferably a dielectric constant promoter, is preferably used in a composition containing polysiloxane, in Z X1 Selected from the group consisting of a direct bond, CH2, C=O, O, (C=O)2, (C=O)O, (C=O)3, (C=O)2O, (C=O)2CH2 and C=O(CH2)2, preferably selected from a direct bond, C=O, O, (C=O)2, (C=O)3; n is 0 or 1; R x1 is H, D or OR x3 ; R x2 is H, D or OR x3 ; R x3 is H, D, an unsubstituted or substituted straight-chain alkyl group having 1 to 5 carbon atoms, an unsubstituted or substituted branched-chain alkyl group having 3 to 5 carbon atoms, or a + , Li + , K + , Rb + , Cs + 、Fr + , Cu + 、Ag + 、Au + 、Ti + , Pd + 、Ni + , Mn + Cr + 、V + The monovalent metal cation is preferably Na + , Li + , K + , Cu + 、Ag + 、Au + , which is more preferably Na + , Li + , K + .

10. A method for manufacturing a layer, comprising at least the following steps: (I Y ) providing a composition according to any one of claims 1 to 8; (II Y ) heating the provided composition to form a layer, preferably to remove the solvent in the composition, the heating is preferably carried out at a temperature in the range of 60 to 140° C., more preferably in the range of 80 to 130° C.

11. A layer obtained from a composition according to any one of claims 1 to 8 by curing or obtained by a process according to claim 10.

12. A layer comprising at least: i) polymers made from polysiloxanes; and ii) a compound represented by the following chemical formula (I), which is preferably a dielectric constant promoter, preferably for use in a polysiloxane-containing composition, in Z X1 Selected from the group consisting of a direct bond, CH2, C=O, O, (C=O)2, (C=O)O, (C=O)3, (C=O)2O, (C=O)2CH2 and C=O(CH2)2, preferably selected from a direct bond, C=O, O, (C=O)2, (C=O)3; n is 0 or 1; R x1 is H, D or OR x3 ; R x2 is H, D or OR x3 ; R x3 is H, D, an unsubstituted or substituted straight-chain alkyl group having 1 to 5 carbon atoms, an unsubstituted or substituted branched-chain alkyl group having 3 to 5 carbon atoms, or a + , Li + , K + , Rb + , Cs + 、Fr + , Cu + 、Ag + 、Au + 、Ti + , Pd + 、Ni + , Mn + Cr + 、V + The monovalent metal cation is preferably Na + , Li + , K + , Cu + 、Ag + 、Au + , which is more preferably Na + , Li + , K + .

13. A layer according to claim 11 or 12, wherein the dielectric constant (ε r ) is 3.5 or higher and 7 or lower, it is preferably 3.9 or higher to 6.5, more preferably 4.0 or higher, it is preferably 6.5 or lower, more preferably 6 or lower, it is preferably in the range of 3.5 to 7, it is more preferably in the range of 3.6 to 6.5, even more preferably in the range of 4 to 6.

14. The layer according to any one of claims 11 to 13, wherein the layer has a haze value of less than 100%.

15. An electronic device comprising at least a layer according to any one of claims 11 to 14.

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