Composition

Abstract

The present invention relates to a composition comprising a polysiloxane.

Description

Technical Field

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

[0002] US2010 2010 / 0016488A1 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 the hydrolyzed monomers to conditions favorable for 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. The document also discloses the use of the composition produced by the method for optical and electrical coatings.

[0003] Patent Literature

[0004] 1. US2010 / 0016488 A1 Summary of the invention

[0005] However, the present inventors have newly discovered that there are still one or more major 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 like a glass substrate for electronic devices, preferably has a minimum haze characteristic; obtaining a layer or a cured composition, which exhibits an improved dielectric constant like a glass substrate for electronic devices, preferably has a minimum haze characteristic; obtaining a polysiloxane-containing composition, preferably a protective layer-forming composition, so that a sufficient amount of thiol can be well dispersed in the composition; obtaining a layer or a cured composition, wherein a sufficient amount of thiol can be well dispersed in the layer or the cured composition; obtaining a polysiloxane-containing composition, preferably a protective layer-forming composition, so that a mild or low-temperature process can be used to form a layer or a cured composition, and the polysiloxane-containing composition can be smoothly coated on any substrate, that is, on PET, CPI, COP or a polarizer.

[0006] The present inventors aim to address one or more of the above-mentioned problems.

[0007] Then, a composition as claimed, preferably a composition for forming a protective layer, was found, which comprises at least the following components, consists essentially of the following components, or consists of the following components:

[0008] i) polysiloxane; and

[0009] ii) A sulfur-containing compound represented by the following chemical formula (I), preferably, which is a dielectric constant promoter preferably used in the polysiloxane-containing composition.

[0010] XS-Y(I)

[0011] in

[0012] X is a hydrogen atom or an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom;

[0013] Y is an unsubstituted or substituted alkyl group having 1 to 12 carbon atoms, an unsubstituted or substituted cyclic alkyl group having 3 to 22 carbon atoms, an unsubstituted or substituted aryl group having 3 to 22 carbon atoms, or an unsubstituted or substituted alkylaryl group having 4 to 22 carbon atoms, which may be substituted with one or more groups R a wherein one or more non-adjacent CH 2 The groups can be independently R a C=CR a 、C≡C、Si(R a ) 2 , Ge(R a ) 2 Sn(R a ) 2 ,C=O,C=S,C=Se,C=NR a ,P(=O)(R a ), SO, CSR a 、SO 2 NR a , OS or CONR a wherein one or more non-adjacent CH groups in the aryl group and / or the alkylaryl group can be replaced independently of each other by SiR a ,GeR a 、SnR a 、CSR a 、SO 2 NR a , O, S, SO or CONR a One or more H atoms can be replaced by D, F, Cl, Br, I, CN or NO 2 replace;

[0014] R ais, on each occurrence, identically or differently, H, D or alkyl having 1 to 10 carbon atoms, cyclic alkyl having 3 to 10 carbon atoms, aryl having 3 to 10 carbon atoms, arylalkyl having 4 to 10 carbon atoms or heteroaryl having 3 to 10 carbon atoms, whereby an H atom may be replaced by D, F, Cl, Br, I; where two or more adjacent substituents R a They may also form mono- or polycyclic aliphatic, aromatic or heteroaromatic ring systems with one another.

[0015] In another aspect, the present invention relates to a method for producing a composition according to any one of the preceding claims, comprising at least the following steps:

[0016] (I x ) mixed with polysiloxane; and

[0017] A sulfur-containing compound represented by the following chemical formula (I):

[0018] XS-Y(I)

[0019] In another aspect, the present invention relates to a composition obtained or obtainable by the method of the present invention.

[0020] 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:

[0021] (I Y ) providing the composition of the invention, preferably onto a substrate, a support layer or a layer of an electronic device;

[0022] (II Y ) heating the provided composition to form a layer, preferably removing the solvent in the composition.

[0023] In another aspect, the invention relates to a layer obtained by curing a composition according to the invention or obtained by a process according to the invention.

[0024] In another aspect, the present invention is directed to a layer comprising at least, consisting essentially of, or consisting of:

[0025] i) polymers made from polysiloxanes; and

[0026] ii) a sulfur-containing compound represented by the following chemical formula (I),

[0027] XS-Y(I)

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

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

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

[0031] Further advantages of the present invention will become apparent from the following detailed description. 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 stated, the singular includes the plural, and "one" or "it" means "at least one". In this specification, unless otherwise specifically stated, an element in a concept may be expressed in multiple species, and when describing an amount (e.g., mass % or mole %), it refers to the sum of multiple species. "And / or" includes all combinations of elements and also includes the use of the elements alone.

[0035] In the present specification, when "to / ~" or "-" is used to express a numerical range, both ends are included and the units are the same. For example, 5 to 25 mol% means 5 mol% or more and 25 mol% or less.

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

[0037] In this specification, an alkyl group refers to a group obtained by removing any hydrogen atom from a straight-chain or branched saturated hydrocarbon, including straight-chain alkyl groups and branched alkyl groups; a cycloalkyl group refers to a group obtained by removing a hydrogen atom from a saturated hydrocarbon having a cyclic structure, and the cyclic structure may contain a straight-chain or branched alkyl group as a side chain.

[0038] In this specification, an aryl group refers to a group obtained by removing any one hydrogen atom from an aromatic hydrocarbon. An alkylene group refers to a group obtained by removing any two hydrogen atoms from a straight-chain or branched saturated hydrocarbon. An arylene group refers to a hydrocarbon group obtained by removing any two hydrogen atoms from an aromatic hydrocarbon.

[0039] In this specification, when a polymer has a plurality 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.

[0040] In this specification, Celsius is used as a temperature unit. For example, 20°C or 20 degrees means 20 degrees Celsius. DETAILED DESCRIPTION OF THE INVENTION

[0042] According to the present invention, in one embodiment, the composition is preferably a composition for forming a protective layer, which contains at least the following components, consists essentially of the following components, or consists of the following components:

[0043] i) polysiloxane; and

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

[0045] XS-Y(I)

[0046] in

[0047] X is a hydrogen atom or an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom;

[0048] Y is an unsubstituted or substituted alkyl group having 1 to 12 carbon atoms, an unsubstituted or substituted cyclic alkyl group having 3 to 22 carbon atoms, an unsubstituted or substituted aryl group having 3 to 22 carbon atoms, or an unsubstituted or substituted alkylaryl group having 4 to 22 carbon atoms, which may be substituted with one or more groups R a wherein one or more non-adjacent CH 2 The groups can be independently R a C=CR a 、C≡C、Si(R a ) 2 , Ge(R a ) 2 Sn(R a ) 2 ,C=O,C=S,C=Se,C=NR a ,P(=O)(R a ), SO, CSR a 、SO2 NR a , OS or CONR a wherein one or more non-adjacent CH groups in the aryl group and / or the alkylaryl group can be replaced independently of each other by SiR a ,GeR a SnR a 、CSR a 、SO 2 NR a , O, S, SO or CONR a One or more H atoms can be replaced by D, F, Cl, Br, I, CN or NO 2 replace;

[0049] R a is, on each occurrence, identically or differently, H, D or alkyl having 1 to 10 carbon atoms, cyclic alkyl having 3 to 10 carbon atoms, aryl having 3 to 10 carbon atoms, arylalkyl having 4 to 10 carbon atoms or heteroaryl having 3 to 10 carbon atoms, whereby an H atom may be replaced by D, F, Cl, Br, I; where two or more adjacent substituents R a They may also form mono- or polycyclic aliphatic, aromatic or heteroaromatic ring systems with one another.

[0050] - Composition

[0051] In a preferred embodiment of the present invention, the dielectric constant (ε r ) is 3.5 to 7, more preferably 4 to 6.5, and even more preferably 4.5 to 6. 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 preferably r ) was determined by the following method.

[0052] According to the present invention, the dielectric constant (ε r ) is measured using the following method.

[0053] 1) Sample preparation and dielectric constant measurement

[0054] coating the composition on a conductive wafer selected from Al, Si or Mo;

[0055] Electrodes were placed on the composition coated with Ag or Al by sputtering or vapor deposition to form samples:

[0056] 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.

[0057] 2) Measurement conditions: The dielectric constant was measured by applying a specific frequency range (50-1 MHz) at room temperature using an LCR meter (E4980A, Agilent (Korea) / 6440B, ToyoTechnical (Japan)) and reading the capacitance displayed on the LCR meter. The value of the dielectric constant was calculated by the following formula, C=KA / d (C=capacitance, K=dielectric constant, A=electrode effective area, d=distance between electrodes).

[0058] ii) Sulfur compounds

[0059] According to the present invention, any known compound of formula (I) or formula (I) can be used. z ). It is preferred to use any known sulfur-containing compound represented by chemical formula (I). Preferably, the molecular weight (Mw) of the sulfur-containing compound is 600 or less, preferably 500 or less, more preferably 400 or less, further preferably in the range of 80 to 400, and most preferably in the range of 100 to 210. When the sulfur-containing compound represented by chemical formula (I) is used, the molecular weight (Mw) of the sulfur-containing compound is preferably 400 or less, more preferably in the range of 80 to 400, and further preferably in the range of 100 to 210.

[0060] It is believed that the above molecular weight can improve the dispersibility of the sulfur-containing compound in polysiloxane and have better compatibility with polysiloxane, thereby reducing the haze value of the composition and the layer obtained from the composition.

[0061] In a preferred embodiment of the present invention, the total amount of the sulfur-containing compound is 0.01 to 40 wt %, preferably 0.1 to 20 wt %, more preferably 0.5 to 5.0 wt %, based on the total amount of polysilazane in the composition.

[0062] It is believed that by using the total amount of the above sulfur-containing compound based on the total amount of polysilazane in the composition, the dispersibility of the sulfur-containing compound in the composition can be further improved, the haze value of the obtained layer can be lower, and the dielectric constant value of the composition can be optimized, and the dielectric constant of the obtained layer can be closer to that of the glass substrate.

[0063] According to the present invention, preferably, the sulfur-containing compound of formula (I) is represented by the following chemical formula (IIa) or (IIb),

[0064] X a SY a -Z a (IIa)

[0065] X a is a hydrogen atom or an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom;

[0066] Ya is an unsubstituted or substituted straight chain alkylene group having 1 to 12 carbon atoms or an unsubstituted or substituted branched chain alkylene group having 3 to 12 carbon atoms, which may be substituted with one or more groups R a wherein one or more non-adjacent CH 2 The groups can be independently R a C=CR a 、C≡C、Si(R a ) 2 , Ge(R a ) 2 Sn(R a ) 2 ,C=O,C=S,C=Se,C=NR a ,P(=O)(R a ), SO, CSH, SO 2 NR a , OS or CONR a One or more H atoms can be replaced by D, F, Cl, Br, I, CN or NO 2 replace;

[0067] R a is, on each occurrence, identically or differently, H, D or alkyl having 1 to 10 carbon atoms, cyclic alkyl having 3 to 10 carbon atoms, aryl having 3 to 10 carbon atoms, arylalkyl having 4 to 10 carbon atoms or heteroaryl having 3 to 10 carbon atoms, whereby an H atom may be replaced by D, F, Cl, Br, I; where two or more adjacent substituents R a They may also form monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring systems with each other;

[0068] Z a *-CR a1 R a2 R a3 , where R a1 , R a2 and R a3 are each independently a hydrogen atom or a halogen atom selected from Cl, Br, F or I, and R a1 , R a2 and R a3 At least one of them is a halogen atom, preferably R a1 , R a2 and R a3 At least two of them are halogen atoms, more preferably R a1 , R a2 and R a3 are all halogen atoms, preferably the halogen atoms are Cl or F, more preferably the halogen atoms are F,

[0069] X b SY b (IIb)

[0070] X b is a hydrogen atom or an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom;

[0071] Y b is an unsubstituted or substituted cyclic alkyl group having 3 to 22 carbon atoms, an unsubstituted or substituted aryl group having 3 to 22 carbon atoms, or an unsubstituted or substituted alkylaryl group having 4 to 22 carbon atoms, which may be substituted with one or more groups R a wherein one or more non-adjacent CH 2 The groups can be independently R a C=CR a 、C≡C、Si(R a ) 2 , Ge(R a ) 2 Sn(R a ) 2 ,C=O,C=S,C=Se,C=NR a ,P(=O)(R a ), SO, CSR a 、SO 2 NR a , OS or CONR a wherein one or more non-adjacent CH groups in the aryl group and / or the alkylaryl group can be replaced independently of each other by SiR a ,GeR a SnR a 、CSR a 、SO 2 NR a , O, S, SO or CONR a and one or more of the H atoms can be replaced by D, F, Cl, Br, I, CN or NO 2 replace;

[0072] R a is, on each occurrence, identically or differently, H, D or alkyl having 1 to 10 carbon atoms, cyclic alkyl having 3 to 10 carbon atoms, aryl having 3 to 10 carbon atoms, arylalkyl having 4 to 10 carbon atoms or heteroaryl having 3 to 10 carbon atoms, whereby an H atom may be replaced by D, F, Cl, Br, I; where two or more adjacent substituents R aThey may also form mono- or polycyclic aliphatic, aromatic or heteroaromatic ring systems with one another.

[0073] For example, 1,2-mercaptobenzimidazole, 2-mercaptoimidazole, benzene-1,2-dithiol, cyclohexanethiol, 2,2,2-trifluoroethanethiol, 1-phenethyl-1H-benzo[d]imidazole-2-thiol, PEMP (pentaerythritol tetrakis(3-mercaptopropionate)), and TMMP (trimethylolpropane tris(3-mercaptopropionate)) can be preferably used.

[0074] In another aspect of the present invention, the present invention also relates to a composition, preferably a protective layer-forming composition, which contains at least the following components, consists essentially of the following components, or consists of the following components:

[0075] i) polysiloxane; and

[0076] ii) by the following chemical formula (I z ), preferably, it is a dielectric constant promoter preferably used in the polysiloxane-containing composition.

[0077] (X z SY z ) n -A z (I z )

[0078] X z is a hydrogen atom or an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom;

[0079] Y z For R z -C=O;

[0080] R z is an unsubstituted or substituted straight chain alkylene group having 1 to 5 carbon atoms or an unsubstituted or substituted branched chain alkylene group having 3 to 5 carbon atoms, wherein one or more non-adjacent CH 2 The groups can be independently R a C=CR a 、C≡C、Si(R a ) 2 , Ge(R a ) 2 Sn(R a ) 2 ,C=O,C=S,C=Se,C=NR a ,P(=O)(R a ), SO, CSH, SO 2 NR a , OS or CONR aand one or more of the H atoms can be replaced by D, F, Cl, Br, I, CN or NO 2 replace;

[0081] A z is a polyol group selected from pentaerythritol, trimethylolpropane, glycerol, ethylene glycol or propylene, wherein the oxygen atom of each hydroxyl group in the polyol group directly reacts with Y in the form of -COO- z C=O carbon atoms connected, or A z is a nitrogen-containing heterocyclic compound selected from a 3-membered ring containing 1 to 3 nitrogen atoms, a 4-membered ring containing 1 to 4 nitrogen atoms, a 5-membered ring containing 1 to 4 nitrogen atoms, a 6-membered ring containing 1 to 4 nitrogen atoms or a 7-membered ring containing 1 to 4 nitrogen atoms as ring atoms, preferably isocyanurate;

[0082] n is an integer from 1 to 4 and is z The number of functional groups or A z The molecular charges are the same.

[0083] As the chemical formula (I z ) as the sulfur-containing compound, preferably used are pentaerythritol tetrakis(3-mercaptobutyrate), tris(3-mercaptobutoxyethyl)isocyanurate, trimethylolpropane tris(3-mercaptobutyrate), and pentaerythritol tetrakis(3-mercaptopropionate).

[0084] i) Polysiloxane

[0085] According to the present invention, any publicly available polysiloxane may be used. Preferably, the polysiloxane comprises the chemical formula (I a ),

[0086]

[0087] in

[0088] R Ia For hydrogen, C 1-30 (Preferred C 1-10 ) Straight chain, C 3-30 (Preferred 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

[0089] The methylene groups in the aliphatic hydrocarbon group and the aromatic hydrocarbon group are not replaced, or one or more methylene groups are replaced by oxy, imino or carbonyl groups, provided that R Ia Neither hydroxy nor alkoxy.

[0090] Here, the above-mentioned methylene group also includes a terminal methyl group.

[0091] In addition, the above-mentioned "substituted with fluorine, hydroxyl or alkoxyl group" means that the hydrogen atom directly bonded to the carbon atom in the aliphatic hydrocarbon group and the aromatic hydrocarbon group is replaced with fluorine, hydroxyl or alkoxyl group. In this specification, other similar expressions are the same.

[0092] In a more preferred embodiment of the present invention, in the a ) in the repeating unit represented by Ia Including, for example, (i) alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl and decyl, (ii) aryl groups such as phenyl, tolyl and benzyl, (iii) fluoroalkyl groups such as trifluoromethyl, 2,2,2-trifluoroethyl and 3,3,3-trifluoropropyl, (iv) fluoroaryl groups, (v) cycloalkyl groups such as cyclohexyl, (vi) nitrogen-containing groups having an amino or imide structure such as isocyanate and amino, (vii) oxygen-containing groups having an epoxy structure such as glycidyl, or an acryloyl structure or a methacryloyl structure. Preferred are methyl, ethyl, propyl, butyl, pentyl, hexyl and phenyl. Preferred R Ia The compound with methyl group is easy to obtain, and the hardness of the cured coating film is high and the chemical resistance is high. Ia The phenyl compound can improve the solubility of polysiloxane in the solvent, and the cured coating film is not easy to crack.

[0093] In a preferred embodiment of the present invention, the polysiloxane used in the present invention may also contain a chemical formula (I b ),

[0094]

[0095] in

[0096] R Ib It is a group obtained by removing a plurality of hydrogen atoms from a nitrogen-containing and / or oxygen-containing alicyclic hydrocarbon compound having an amino group, an imino group and / or a carbonyl group.

[0097] Formula (I b ), R Ib It is preferably a group obtained by removing multiple hydrogen atoms, preferably two or three hydrogen atoms, from a nitrogen-containing aliphatic hydrocarbon ring having an imino group and / or a carbonyl group, and more preferably a 5-membered or 6-membered ring containing nitrogen as a member. For example, it is a group obtained by removing two or three hydrogen atoms from piperidine, pyrrolidine or isocyanurate. Ib Si is linked to each other and included in a plurality of repeating units.

[0098] In a preferred embodiment of the present invention, the polysiloxane used in the present invention may also contain a c ) represents a repeating unit:

[0099]

[0100] When the formula (I b ) and formula (I c ) When the mixing ratio of the repeating units represented by is high, the compatibility with solvents and additives is reduced, and the film stress is increased, and cracks are sometimes easily generated. Therefore, based on the total number of repeating units of polysiloxane, it is preferably 40 mol% or less, and more preferably 20 mol% or less.

[0101] According to the present invention, in some embodiments, the polysiloxane used in the present invention may also include a d ) represents a repeating unit:

[0102]

[0103] in

[0104] R Id Each independently represents hydrogen, C 1-30 (Preferred C 1-10 ) Straight chain, C 3-30 (Preferred C 3-10 ) branched or cyclic, saturated or unsaturated aliphatic or aromatic hydrocarbon groups;

[0105] The aliphatic hydrocarbon group and the aromatic hydrocarbon group are each unsubstituted or substituted with fluorine, hydroxyl or alkoxy, and

[0106] The methylene group in the aliphatic hydrocarbon group and the aromatic hydrocarbon group is not replaced, or is replaced by an oxy group, an imido group, or a carbonyl group.

[0107] In the formula (I d ) in the repeating unit represented by Id Examples include: (i) alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl and decyl; (ii) aryl groups such as phenyl, tolyl and benzyl; (iii) fluoroalkyl groups such as trifluoromethyl, 2,2,2-trifluoroethyl and 3,3,3-trifluoropropyl; (iv) fluoroaryl groups; (v) cycloalkyl groups such as cyclohexyl; (vi) nitrogen-containing groups having an amino or imide structure such as an isocyanate group and an amino group; (vii) oxygen-containing groups having an epoxy structure such as a glycidyl group, or an acryloyl structure or a methacryloyl structure. Preferred are methyl, ethyl, propyl, butyl, pentyl, hexyl and phenyl. Preferred R Id The compound with methyl group is easy to obtain, and the hardness of the cured coating film is high and the chemical resistance is high. Id The phenyl compound can improve the solubility of polysiloxane in the solvent, and the cured coating film is not easy to crack.

[0108] By having the above formula (I d ) can make the polysiloxane part of the present invention a linear structure.

[0109] However, since heat resistance is reduced, it is preferred that the linear structure portion is less. Specifically, based on the total number of repeating units of polysiloxane, formula (I d ) is preferably 30 mol % or less, more preferably 5 mol % or less. d ) repeating unit (0 mol %) is also one aspect of the present invention.

[0110] The polysiloxane used in the present invention may contain two or more repeating units, for example, it may contain the following three repeating units: a ) represented by a repeating unit, wherein R Ia is methyl or phenyl; and c ) represents a repeating unit.

[0111] In addition, the polysiloxane used in the composition of the present invention preferably has silanol. Here, silanol refers to a silanol in which the OH group is directly bonded to the Si skeleton of the polysiloxane, that is, the hydroxyl group is directly bonded to the Si skeleton of the above formula (I a ) to (I d ) and the like. That is, the silanol is composed of the above formula (I a ) to (I d ) 0.5 H and -O 0.5 The content of silanol in polysiloxane varies with the synthesis conditions of polysiloxane, such as the mixing ratio of monomers, the type of reaction catalyst, etc.

[0112] The content of silanol can be evaluated by quantitative infrared absorption spectroscopy. The absorption band attributed to silanol (SiOH) appears at 900±100cm in the infrared absorption spectrum. -1 The absorption band has a peak in the range of 1:1 to 2:1. When the content of silanol is high, the intensity of the absorption band increases.

[0113] In the present invention, in order to quantitatively evaluate the silanol content, the intensity of the absorption band assigned to Si-0 is used as a reference. -1 The absorption band having a peak in the range of 0.504 to 0.707 is a peak attributable to Si-O. The silanol content can be relatively evaluated by the ratio S2 / S1 of the integrated intensity S2 of the absorption band attributable to SiOH to the integrated intensity S1 of the absorption band attributable to Si-O. In the present invention, S2 / S1 is preferably 0.003 to 0.15, more preferably 0.01 to 0.10.

[0114] The integrated intensity of the absorption band is determined by taking into account the noise in the infrared absorption spectrum. In the typical infrared absorption spectrum of polysiloxane, a peak at 900 ± 100 cm -1 The absorption bands and peaks at 1100 ± 100 cm-1 are attributed to Si-OH. -1 The absorption bands attributed to Si-O within the range. The integrated intensity of these absorption bands can be measured as the area of ​​the baseline taking into account noise, etc. By the way, there is a possibility that the bottom of the absorption band attributed to Si-OH and the bottom of the absorption band attributed to Si-O overlap; however, in this case, the wave number corresponding to the minimum point between the two absorption bands in the spectrum is set as their boundary. The same is true for the case where the foot of the other absorption band overlaps with the bottom of the absorption band attributed to Si-OH or Si-O.

[0115] The mass average molecular weight of the polysiloxane used in the present invention is not particularly limited. However, the higher the molecular weight, the easier it is to improve the coating property. On the other hand, the lower the molecular weight, the fewer the synthetic conditions are restricted, so the synthesis is easy, while the synthesis of polysiloxanes with very high molecular weight is difficult. Therefore, from the viewpoint of solubility in organic solvents, the mass average molecular weight of polysiloxane is generally 500 to 25,000, preferably 1,000 to 20,000. Here, the mass average molecular weight refers to the mass average molecular weight based on polystyrene, which can be measured by gel permeation chromatography based on polystyrene.

[0116] As mentioned above, publicly available polysiloxanes meeting the above definition can preferably be used as described, for example, in WO 2021 / 099236 A1, EP 3717966 B1.

[0117] -Solvent

[0118] In a preferred embodiment of the present invention, the composition may further contain a solvent from the viewpoint of improving the coating of the composition during handling, coating, stringing or layer preparation. Alternatively, from the viewpoint of providing a solvent-free composition, the composition contains a solvent in an amount of 5% by weight or less based on the total amount of polysiloxane in the composition, and preferably does not contain any solvent.

[0119] Preferably, the solvent is selected from one or more of the group consisting of propylene glycol methyl ether acetate, propylene glycol methyl ether, γ-butyrolactone, propylene glycol diacetate, diethylene glycol monohexyl ether, methyl 3-methoxypropionate, methyl isobutyl ketone, and methyl ethyl ketone, more preferably γ-butyrolactone, propylene glycol methyl ether acetate, or a mixture of γ-butyrolactone and propylene glycol methyl ether acetate.

[0120] It is believed that the above selected solvents have good compatibility with the composition, boiling point, viscosity and / or vapor pressure, can better handle the composition, are suitable for lower temperature manufacturing of the layer and / or achieve easy manufacturing.

[0121] 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 50 to 90 wt %.

[0122] -additive

[0123] In some embodiments of the present invention, optionally, the composition may further include one or more additives. Such additives may be selected from one or more of the group consisting of surfactants, adhesion promoters, silane coupling agents, thermal acid generators, thermal alkali generators, crosslinkable monomers and polymerization initiators. It is preferred to use publicly available additives, as described in EP3717966A1 or WO 2021 / 099236 A1. Since the additive is not mandatory 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 by the composition may not contain any of the additives.

[0124] In another aspect, the present invention also relates to a method for preparing the composition of the present invention, which comprises at least the following steps, consists essentially of the following steps, or consists of the following steps:

[0125] (I x ) mixed with polysiloxane; and

[0126] The following chemical formula (I) or chemical formula (I z ), preferably a sulfur-containing compound represented by the following chemical formula (I), optionally together with a solvent and / or other additives.

[0127] XS-Y(I)

[0128] Details of the sulfur-containing compounds and polysiloxanes, including preferred amounts, have been indicated above in the sections ii) sulfur-containing compounds and i) polysiloxanes.

[0129] In another aspect, the present invention also relates to a composition obtained or obtainable by the above method for producing a composition.

[0130] In another aspect, the present invention also relates to a method for manufacturing a layer, which comprises at least the following steps, essentially comprises the following steps, or consists of the following steps:

[0131] (I Y) providing the composition of the invention, preferably onto a substrate, a support layer or a layer of an electronic device;

[0132] (II Y ) heating the provided composition to form a layer, preferably removing the solvent in the composition, preferably the heating is carried out at a temperature in the range of 60 to 140°C, more preferably in the range of 80 to 130°C.

[0133] (III Y ) Optionally, the provided composition is irradiated with ultraviolet (UV) light for curing.

[0134] According to the present invention, the ultraviolet light is light with a peak wavelength in the range of 250 to 450 nm.

[0135] In another aspect, the present invention also relates to a layer obtained by curing the composition of the present invention or by the above-mentioned method for making a layer. Preferably, the layer is a protective layer of an electronic device. Preferably, the curing is thermal curing and / or UV curing.

[0136] In another aspect, the present invention also relates to a layer comprising at least, essentially consisting of, or consisting of the following components:

[0137] i) polymers made from polysiloxanes; and

[0138] ii) the following chemical formula (I) or chemical formula (I z ), preferably a sulfur-containing compound represented by the following chemical formula (I),

[0139] XS-Y(I)

[0140] Details of the sulfur-containing compounds and polysiloxanes, including preferred amounts, have been indicated above in the sections ii) sulfur-containing compounds and i) polysiloxanes.

[0141] In a preferred embodiment of the invention, the dielectric constant (ε r ) is 3.5 to 10, more preferably 3.6 to 8, even more preferably 4 to 7, further preferably 4.5 to 6.

[0142] It is believed that when the layer is used as a protective layer of a device, that is, an electronic device, such as an OLED or LCD, the dielectric constant (ε r ) can achieve improved touch sensitivity of the same layer as the glass substrate.

[0143] The dielectric constant of this layer was measured as described above in the "Composition" section.

[0144] 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%.

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

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

[0147] Parallel transmittance (T P ) is determined by measuring the light intensity in the sphere relative to the sample; the total transmittance (T T ), including diffracted light transmittance (T D ) and T P , is obtained by measuring the light passing through the sample, using the formula T T =T P +T D The degree of light scattering in the sample, i.e., haze (H), is defined as H = T D / T T . The transmittance and haze were measured.

[0148] In another form, the present invention also relates to an electronic device comprising at least one layer of the present 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 replaces the cover glass substrate to achieve a cover glass-free electronic device with good touch sensitivity, preferably with a lower haze value.

[0149] In another aspect, the present invention also relates to a method of using the sulfur-containing compound of formula (I) as a dielectric constant enhancer in a polysiloxane-containing composition.

[0150] In another aspect, the present invention also relates to a method of using the composition of the present invention as a composition for forming a protective layer of an electronic device, preferably using the composition instead of an upper glass substrate of the electronic device.

[0151] Preferred Implementation

[0152] 1. A composition, preferably a protective layer-forming composition, comprising at least, essentially consisting of, or consisting of the following components:

[0153] i) polysiloxane; and

[0154] ii) the following chemical formula (I) or chemical formula (I z ), preferably a sulfur-containing compound represented by the following chemical formula (I), preferably, it is a dielectric constant promoter preferably used in the polysiloxane-containing composition,

[0155] XS-Y(I)

[0156] in

[0157] X is a hydrogen atom or an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom;

[0158] Y is an unsubstituted or substituted alkyl group having 1 to 12 carbon atoms, an unsubstituted or substituted cyclic alkyl group having 3 to 22 carbon atoms, an unsubstituted or substituted aryl group having 3 to 22 carbon atoms, or an unsubstituted or substituted alkylaryl group having 4 to 22 carbon atoms, which may be substituted with one or more groups R a wherein one or more non-adjacent CH 2 The groups can be independently R a C=CR a 、C≡C、Si(R a ) 2 , Ge(R a ) 2 Sn(R a ) 2 ,C=O,C=S,C=Se,C=NR a ,P(=O)(R a ), SO, CSR a 、SO 2 NR a , OS or CONR a wherein one or more non-adjacent CH groups in the aryl group and / or the alkylaryl group can be replaced independently of each other by SiR a ,GeR a SnR a 、CSR a 、SO 2 NR a , O, S, SO or CONR a One or more H atoms can be replaced by D, F, Cl, Br, I, CN or NO2 replace;

[0159] R a is, on each occurrence, identically or differently, H, D or alkyl having 1 to 10 carbon atoms, cyclic alkyl having 3 to 10 carbon atoms, aryl having 3 to 10 carbon atoms, arylalkyl having 4 to 10 carbon atoms or heteroaryl having 3 to 10 carbon atoms, whereby an H atom may be replaced by D, F, Cl, Br, I; where two or more adjacent substituents R a They may also form mono- or polycyclic aliphatic, aromatic or heteroaromatic ring systems with one another.

[0160] 2. A composition according to embodiment 1, wherein the molecular weight (Mw) of the sulfur-containing compound is 600 or less, preferably 500 or less, more preferably 400 or less, further preferably 80 to 400, and most preferably 100 to 210.

[0161] 3. The composition according to embodiment 1 or 2, wherein the total amount of the sulfur-containing compound is 0.01 to 40 wt %, preferably 0.1 to 20 wt %, more preferably 0.5 to 5.0 wt %, based on the total amount of polysilazane in the composition.

[0162] 4. A composition according to any of the preceding embodiments, wherein the dielectric constant (ε r ) is in the range of 3.5 to 7, more preferably in the range of 4 to 6.5, even more preferably in the range of 4.5 to 6. Preferably, the dielectric constant (ε r ) is measured by the following method.

[0163] 1) Sample preparation and dielectric constant measurement

[0164] coating the composition on a conductive wafer selected from Al, Si or Mo;

[0165] Electrodes were placed on the composition coated with Ag or Al by sputtering or vapor deposition to form samples:

[0166] 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.

[0167] 2) Measurement conditions: The dielectric constant was measured by applying a specific frequency range (50-1 MHz) at room temperature using an LCR meter (E4980A, Agilent (Korea) / 6440B, ToyoTechnical (Japan)) and reading the capacitance displayed on the LCR meter. The value of the dielectric constant was calculated by the following formula, C=KA / d (C=capacitance, K=dielectric constant, A=electrode effective area, d=distance between electrodes).

[0168] 5. A composition according to any of the preceding embodiments, wherein the sulfur-containing compound (I) is represented by the following chemical formula (IIa) or (IIb):

[0169] X a SY a -Z a (IIa)

[0170] X a is a hydrogen atom or an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom;

[0171] Y a is an unsubstituted or substituted straight chain alkylene group having 1 to 12 carbon atoms or an unsubstituted or substituted branched chain alkylene group having 3 to 12 carbon atoms, which may be substituted with one or more groups R a wherein one or more non-adjacent CH 2 The groups can be independently R a C=CR a 、C≡C、Si(R a ) 2 , Ge(R a ) 2 Sn(R a ) 2 ,C=O,C=S,C=Se,C=NR a ,P(=O)(R a ), SO, CSH, SO 2 NR a , OS or CONR a One or more H atoms can be replaced by D, F, Cl, Br, I, CN or NO 2 replace;

[0172] R ais, on each occurrence, identically or differently, H, D or alkyl having 1 to 10 carbon atoms, cyclic alkyl having 3 to 10 carbon atoms, aryl having 3 to 10 carbon atoms, arylalkyl having 4 to 10 carbon atoms or heteroaryl having 3 to 10 carbon atoms, whereby an H atom may be replaced by D, F, Cl, Br, I; where two or more adjacent substituents R a They may also form monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring systems with each other;

[0173] Z a *-CR a1 R a2 R a3 , where R a1 , R a2 and R a3 are each independently a hydrogen atom or a halogen atom selected from Cl, Br, F or I, and R a1 , R a2 and R a3 At least one of them is a halogen atom, preferably R a1 , R a2 and R a3 At least two of them are halogen atoms, more preferably R a1 , R a2 and R a3 are all halogen atoms, preferably the halogen atoms are Cl or F, more preferably the halogen atoms are F,

[0174] X b SY b (IIb)

[0175] X b is a hydrogen atom or an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom;

[0176] Y b is an unsubstituted or substituted cyclic alkyl group having 3 to 22 carbon atoms, an unsubstituted or substituted aryl group having 3 to 22 carbon atoms, or an unsubstituted or substituted alkylaryl group having 4 to 22 carbon atoms, which may be substituted with one or more groups R a wherein one or more non-adjacent CH 2 The groups can be independently R a C=CR a 、C≡C、Si(R a ) 2 , Ge(R a ) 2 Sn(R a ) 2 ,C=O,C=S,C=Se,C=NRa ,P(=O)(R a ), SO, CSR a 、SO 2 NR a , OS or CONR a wherein one or more non-adjacent CH groups in the aryl group and / or the alkylaryl group can be replaced independently of each other by SiR a ,GeR a SnR a 、CSR a 、SO 2 NR a , O, S, SO or CONR a and one or more of the H atoms can be replaced by D, F, Cl, Br, I, CN or NO 2 replace;

[0177] R a is, on each occurrence, identically or differently, H, D or alkyl having 1 to 10 carbon atoms, cyclic alkyl having 3 to 10 carbon atoms, aryl having 3 to 10 carbon atoms, arylalkyl having 4 to 10 carbon atoms or heteroaryl having 3 to 10 carbon atoms, whereby an H atom may be replaced by D, F, Cl, Br, I; where two or more adjacent substituents R a They may also form mono- or polycyclic aliphatic, aromatic or heteroaromatic ring systems with one another.

[0178] 6. A composition according to any of the preceding embodiments, wherein the polysiloxane comprises formula (I a ),

[0179]

[0180] in

[0181] R Ia For hydrogen, C 1-30 (Preferred C 1-10 ) Straight chain, C 3-30 (Preferred 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

[0182] The methylene groups in the aliphatic hydrocarbon group and the aromatic hydrocarbon group are not replaced, or one or more methylene groups are replaced by oxy, imino or carbonyl groups, provided that R Ia Neither hydroxy nor alkoxy.

[0183] 7. A composition according to any of the preceding embodiments, wherein the polysiloxane comprises formula (Ib ),

[0184]

[0185] in

[0186] R Ib It is a group obtained by removing a plurality of hydrogen atoms from a nitrogen-containing and / or oxygen-containing alicyclic hydrocarbon compound having an amino group, an imino group and / or a carbonyl group.

[0187] Formula (I b ), R Ib It is preferably a group obtained by removing multiple hydrogen atoms, preferably two or three hydrogen atoms, from a nitrogen-containing aliphatic hydrocarbon ring having an imino group and / or a carbonyl group, and more preferably a 5-membered or 6-membered ring containing nitrogen as a member. For example, it is a group obtained by removing two or three hydrogen atoms from piperidine, pyrrolidine or isocyanurate. Ib Si is linked to each other and included in a plurality of repeating units.

[0188] 8. A composition according to any of the preceding embodiments, wherein the polysiloxane comprises formula (I c ),

[0189]

[0190] 9. A composition according to any of the preceding embodiments, wherein the polysiloxane comprises formula (I d ),

[0191]

[0192] in

[0193] R Id Each independently represents hydrogen, C 1-30 (Preferred C 1-10 ) Straight chain, C 3-30 (Preferred C 3-10 ) branched or cyclic, saturated or unsaturated aliphatic or aromatic hydrocarbon groups;

[0194] The aliphatic hydrocarbon group and the aromatic hydrocarbon group are each unsubstituted or substituted with fluorine, hydroxyl or alkoxy, and

[0195] The methylene group in the aliphatic hydrocarbon group and the aromatic hydrocarbon group is not replaced, or is replaced by an oxy group, an imido group, or a carbonyl group.

[0196] 10. The composition according to any of the preceding embodiments, further comprising an additive.

[0197] 11. The composition according to any of the preceding embodiments, further comprising a solvent. Preferably, the solvent is selected from one or more of the group consisting of propylene glycol methyl ether acetate, propylene glycol methyl ether, γ-butyrolactone, propylene glycol diacetate, diethylene glycol monohexyl ether, methyl 3-methoxypropionate, methyl isobutyl ketone, and methyl ethyl ketone, more preferably γ-butyrolactone, propylene glycol methyl ether acetate, or a mixture of γ-butyrolactone and propylene glycol methyl ether acetate.

[0198] 12. A method for producing a composition according to any of the preceding embodiments, comprising at least the following steps:

[0199] (I x ) mixed with polysiloxane; and

[0200] The following chemical formula (I) or chemical formula (I z ), preferably a sulfur-containing compound represented by the following chemical formula (I),

[0201] XS-Y(I)

[0202] in

[0203] X is a hydrogen atom or an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom;

[0204] Y is an unsubstituted or substituted alkyl group having 1 to 12 carbon atoms, an unsubstituted or substituted cyclic alkyl group having 3 to 22 carbon atoms, an unsubstituted or substituted aryl group having 3 to 22 carbon atoms, or an unsubstituted or substituted alkylaryl group having 4 to 22 carbon atoms, which may be substituted with one or more groups R a wherein one or more non-adjacent CH 2 The groups can be independently R a C=CR a 、C≡C、Si(R a ) 2 , Ge(R a ) 2 Sn(R a ) 2 ,C=O,C=S,C=Se,C=NR a ,P(=O)(R a ), SO, CSR a 、SO 2 NR a , OS or CONR a wherein one or more non-adjacent CH groups in the aryl group and / or the alkylaryl group can be replaced independently of each other by SiR a ,GeR a SnRa 、CSR a 、SO 2 NR a , O, S, SO or CONR a One or more H atoms can be replaced by D, F, Cl, Br, I, CN or NO 2 replace;

[0205] R a is, on each occurrence, identically or differently, H, D or alkyl having 1 to 10 carbon atoms, cyclic alkyl having 3 to 10 carbon atoms, aryl having 3 to 10 carbon atoms, arylalkyl having 4 to 10 carbon atoms or heteroaryl having 3 to 10 carbon atoms, whereby an H atom may be replaced by D, F, Cl, Br, I; where two or more adjacent substituents R a They may also form mono- or polycyclic aliphatic, aromatic or heteroaromatic ring systems with one another.

[0206] 13. A composition obtained or obtainable by the method according to embodiment 12.

[0207] 14. A method for manufacturing a layer, comprising at least the following steps;

[0208] (I Y ) Providing the composition described in any one of Embodiments 1 to 11 and 13, preferably onto a substrate, a supporting layer or a layer of an electronic device; preferably, such substrate is selected from a glass substrate, a plastic substrate or a polarizer.

[0209] (II Y ) heating the provided composition to form a layer, preferably removing the solvent in the composition, preferably the heating is carried out at a temperature in the range of 60 to 140°C, more preferably in the range of 80 to 130°C.

[0210] 15. A layer obtained by curing the composition of any one of embodiments 1 to 13, or obtained by the method of embodiment 14. Preferably, the layer is a protective layer of an electrical device. Preferably, the curing is thermal curing.

[0211] 16. A layer comprising at least the following components:

[0212] i) polymers made from polysiloxanes; and

[0213] ii) the following chemical formula (I) or chemical formula (I z ), preferably a sulfur-containing compound represented by the following chemical formula (I),

[0214] XS-Y(I)

[0215] in

[0216] X is a hydrogen atom or an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom;

[0217] Y is an unsubstituted or substituted alkyl group having 1 to 12 carbon atoms, an unsubstituted or substituted cyclic alkyl group having 3 to 22 carbon atoms, an unsubstituted or substituted aryl group having 3 to 22 carbon atoms, or an unsubstituted or substituted alkylaryl group having 4 to 22 carbon atoms, which may be substituted with one or more groups R a wherein one or more non-adjacent CH 2 The groups can be independently R a C=CR a 、C≡C、Si(R a ) 2 , Ge(R a ) 2 Sn(R a ) 2 ,C=O,C=S,C=Se,C=NR a ,P(=O)(R a ), SO, CSR a 、SO 2 NR a , OS or CONR a wherein one or more non-adjacent CH groups in the aryl group and / or the alkylaryl group can be replaced independently of each other by SiR a ,GeR a SnR a 、CSR a 、SO 2 NR a , O, S, SO or CONR a One or more H atoms can be replaced by D, F, Cl, Br, I, CN or NO 2 replace;

[0218] R a is, on each occurrence, identically or differently, H, D or alkyl having 1 to 10 carbon atoms, cyclic alkyl having 3 to 10 carbon atoms, aryl having 3 to 10 carbon atoms, arylalkyl having 4 to 10 carbon atoms or heteroaryl having 3 to 10 carbon atoms, whereby an H atom may be replaced by D, F, Cl, Br, I; where two or more adjacent substituents R a They may also form mono- or polycyclic aliphatic, aromatic or heteroaromatic ring systems with one another.

[0219] 17. The layer according to embodiment 15 or 16, wherein the dielectric constant (εr ) is in the range of 3.5 to 10, more preferably in the range of 3.6 to 8, even more preferably in the range of 4 to 7, further preferably in the range of 4.5 to 6.

[0220] 18. The layer according to any one of embodiments 15 to 17, 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%.

[0221] The haze value is measured at room temperature in air using an integrating sphere haze measurement system (NDH-7000, Nippon Denshoku, Japan, light source: white LED 3W, wavelength range: 380-780 nm).

[0222] · Schematic diagram of integrating sphere for transmittance and haze measurement, total transmittance (T T )T T =T P +T D , haze (H) H = T D / T T .

[0223] Parallel transmittance (T P ) is determined by measuring the light intensity in the sphere relative to the sample; the total transmittance (T T ), including diffracted light transmittance (T D ) and T P , is obtained by measuring the light passing through the sample, using the formula T T =T P +T D The degree of light scattering in the sample, i.e., haze (H), is defined as H = T D / T T . The transmittance and haze were measured.

[0224] 19. An electronic device comprising at least one layer of embodiments 15 to 18, preferably the electronic device comprises a light regulating 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.

[0225] 20. Use of chemical formula (I) or chemical formula (I z ) as a dielectric constant promoter in a polysiloxane-containing composition.

[0226] 21. A method of using the composition of any one of Embodiments 1 to 11 and 13 as a composition for forming a protective layer of an electronic device, preferably using the composition instead of an upper glass substrate of the electronic device.

[0227] Technical Effects of the Invention

[0228] The present invention provides one or more of the following technical effects:

[0229] A polysiloxane-containing composition, preferably a protective layer-forming composition, is obtained, which exhibits an improved dielectric constant like a glass substrate for electronic devices, preferably with the lowest haze characteristics; a layer or a cured composition is obtained, which exhibits an improved dielectric constant like a glass substrate for electronic devices, preferably with the lowest haze characteristics; a polysiloxane-containing composition, preferably a protective layer-forming composition, is obtained so that a sufficient amount of thiol can be well dispersed in the composition; a layer or a cured composition is obtained, wherein a sufficient amount of thiol can be well dispersed in the layer or the cured composition; a polysiloxane-containing composition, preferably a protective layer-forming composition, is obtained so that a mild or lower temperature process can be used to form a layer or a cured composition, and the polysiloxane-containing composition can be smoothly applied to any substrate, i.e., applied to PET, CPI, COP or a polarizer.

[0230] Embodiments of the invention

[0231] The present invention is described in the following Inventive Examples 1 to 10, and the preparation methods thereof are described in detail. However, the present invention is not limited to these Inventive Examples.

[0232] Invention Example 1: Mixture sample preparation

[0233] The polysiloxane polymer of Merck represented by the following chemical formula was mixed with 1% or 5% by weight of the thiol-containing compound 1;2-mercaptobenzimidazole based on the total amount of polysiloxane in the presence of a mixture of propylene glycol monomethyl ether acetate and γ-butyrolactone (the total weight of the siloxane polymer and the thiol-containing compound: the solvent mixture = 3:7). After the above compounds were mixed, they were respectively coated on Al-deposited silicon wafers by spin coating to obtain samples (sample 1-1 contained 1% of 1;2-mercaptobenzimidazole, and sample 1-2 contained 5% of 1;2-mercaptobenzimidazole). Then, the solvent mixture was evaporated in a curing process at 120° C. to obtain samples 1-1 (1%) and 1-2 (5%).

[0234] n=0.5、m=0.4、l=0.1

[0235] Inventive Examples 2 to 9: Mixture sample preparation

[0236] Examples 2 to 9 were carried out, which were the same as Example 1 of the invention except that the following thiol-containing compounds were used instead of 1;2-mercaptobenzimidazole, and 1% thiol compound samples (samples 2-1, 3-1, 4-1, 5-1, 6-1, 7-1, 8-1, 9-1) and 5% thiol compound samples (samples 2-2, 3-2, 4-2, 5-2, 6-2, 7-2, 8-2, 9-2) were obtained respectively.

[0237] - Thiol-containing compounds used in Inventive Examples 1 to 9

[0238] Comparative Example 1: No thiol-containing compound is used

[0239] Inventive Example 1: 1; 2-Mercaptobenzimidazole

[0240] Inventive Example 2: 2-Mercaptoimidazole

[0241] Inventive Example 3: Benzene-1,2-dithiol

[0242] Inventive Example 4: Cyclohexanethiol

[0243] Inventive Example 5: 2,2,2-Trifluoroethanethiol

[0244] Inventive Example 6: Pentaerythritol tetrakis (3-mercaptobutyrate)

[0245] Inventive Example 7: Tris(3-mercaptobutoxyethyl)isocyanurate

[0246] Inventive Example 8: Trimethylolpropane tris(3-mercaptobutyrate)

[0247] Inventive Example 9: Pentaerythritol tetrakis (3-mercaptopropionate)

[0248] Other thiol-containing compounds, such as 1-phenethyl-1H-benzo[d]imidazole-2-thiol, may also be used with preference.

[0249] Comparative Example 1: Reference sample preparation

[0250] A reference sample was prepared in the same manner as described in Inventive Example 1, except that the thiol-containing compound was not added / mixed into the siloxane polymer. A reference sample was then obtained.

[0251] Invention Example 10: Dielectric constant measurement of samples of inventive examples 1 to 6 and comparative example 1

[0252] The haze values ​​of the samples of Inventive Examples 1 to 6 and Comparative Example 1 were measured at room temperature using an integrating sphere haze measurement system (NDH-7000, Nippon Denshoku, Japan, light source white LED 3W, wavelength range 380-780 nm). The sample thickness was between 2 μm and 700 μm, especially 700 μm.

[0253] · Schematic diagram of integrating sphere for transmittance and haze measurement, total transmittance (T T )T T =T P +T D , haze (H) H = T D / T T .

[0254] Parallel transmittance (T P ) is determined by measuring the light intensity in the sphere relative to the sample; the total transmittance (T T ), including diffracted light transmittance (T D ) and T P , is obtained by measuring the light passing through the sample, using the formula T T =T P +T D The degree of light scattering in the sample, i.e., haze (H), is defined as H = T D / T T . The transmittance and haze were measured.

[0255] Table 1 below shows the measurement results.

[0256] Table 1:

[0257]

[0258] As shown in Table 1 above, the thiol-containing compound, preferably the thiol-containing compound used in Samples 1 to 5, significantly improves the dielectric constant of the polysiloxane composition. And it is believed that it can help glass-free electronic devices (such as touch-free glass OLED concepts) to improve touch sensitivity.

Claims

1. A composition, preferably a protective layer-forming composition, comprising at least: i) polysiloxane; and ii) a sulfur-containing compound represented by the following chemical formula (I), XS-Y(I) in X is a hydrogen atom or an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom; Y is an unsubstituted or substituted alkyl group having 1 to 12 carbon atoms, an unsubstituted or substituted cyclic alkyl group having 3 to 22 carbon atoms, an unsubstituted or substituted aryl group having 3 to 22 carbon atoms, or an unsubstituted or substituted alkylaryl group having 4 to 22 carbon atoms, which may be substituted with one or more groups R a wherein one or more non-adjacent CH2 groups in the alkyl group, cyclic alkyl group, aryl group and / or the alkylaryl group can be independently replaced by R a C=CR a 、C≡C、Si(R a )2、Ge(R a )2、Sn(R a )2. C=O, C=S, C=Se, C=NR a ,P(=O)(R a ), SO, CSR a 、SO2、NR a , OS or CONR a wherein one or more non-adjacent CH groups in the aryl group and / or the alkylaryl group can be replaced independently of each other by SiR a ,GeR a 、SnR a 、CSR a 、SO2、NR a , O, S, SO or CONR a Replacement, wherein one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2; R a is, on each occurrence, identically or differently, H, D or alkyl having 1 to 10 carbon atoms, cyclic alkyl having 3 to 10 carbon atoms, aryl having 3 to 10 carbon atoms, arylalkyl having 4 to 10 carbon atoms or heteroaryl having 3 to 10 carbon atoms, whereby an H atom may be replaced by D, F, Cl, Br, I; where two or more adjacent substituents R a They may also form mono- or polycyclic aliphatic, aromatic or heteroaromatic ring systems with one another.

2. The composition of claim 1, wherein the molecular weight (Mw) of the sulfur-containing compound is 600 or less.

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

4. A composition according to any one of the preceding claims, wherein the dielectric constant (ε r ) is in the range of 3.5 to 7.

5. A composition according to any one of the preceding claims, wherein the sulfur-containing compound is represented by the following chemical formula (IIa) or (IIb), X a SY a -Z a (IIa) X a is a hydrogen atom or an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom; Y a is an unsubstituted or substituted straight chain alkylene group having 1 to 12 carbon atoms or an unsubstituted or substituted branched chain alkylene group having 3 to 12 carbon atoms, which may be substituted with one or more groups R a wherein one or more non-adjacent CH2 groups in the alkyl group, cyclic alkyl group, aryl group and / or the alkylaryl group can be independently replaced by R a C=CR a 、C≡C、Si(R a )2、Ge(R a )2、Sn(R a )2. C=O, C=S, C=Se, C=NR a ,P(=O)(R a )、SO、CSH、SO2、NR a , OS or CONR a Replacement, wherein one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2; R a is, on each occurrence, identically or differently, H, D or alkyl having 1 to 10 carbon atoms, cyclic alkyl having 3 to 10 carbon atoms, aryl having 3 to 10 carbon atoms, arylalkyl having 4 to 10 carbon atoms or heteroaryl having 3 to 10 carbon atoms, whereby an H atom may be replaced by D, F, Cl, Br, I; where two or more adjacent substituents R a They may also form monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring systems with each other; Z a *-CR a1 R a2 R a3 ,in, R a1 , R a2 and R a3 are each independently a hydrogen atom or a halogen atom selected from Cl, Br, F or I, and R a1 , R a2 and R a3 At least one of them is a halogen atom, preferably R a1 , R a2 and R a3 At least two of them are halogen atoms, more preferably R a1 , R a2 and R a3 are all halogen atoms, preferably the halogen atoms are Cl or F, more preferably the halogen atoms are F, X b SY b (IIb).

6. A composition according to any one of the preceding claims, wherein the polysiloxane comprises formula (I a ), in R Ia For hydrogen, C 1-30 (Preferred C 1-10 ) Straight chain, C 3-30 (Preferred 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 The methylene groups in the aliphatic hydrocarbon group and the aromatic hydrocarbon group are not replaced, or one or more methylene groups are replaced by oxy, imino or carbonyl groups, provided that R Ia Neither hydroxy nor alkoxy.

7. A composition according to any one of the preceding claims, wherein the polysiloxane comprises formula (I b ), in R Ib It is a group obtained by removing a plurality of hydrogen atoms from a nitrogen-containing and / or oxygen-containing alicyclic hydrocarbon compound having an amino group, an imino group and / or a carbonyl group. R Ib Preferably, it is a group obtained by removing multiple hydrogen atoms, preferably two or three hydrogen atoms, from a nitrogen-containing aliphatic hydrocarbon ring 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 Si is linked to each other and included in a plurality of repeating units.

8. A composition according to any one of the preceding claims, 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; as well as A sulfur-containing compound represented by the following chemical formula (I), XS-Y(I) in X is a hydrogen atom or an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom; Y is an unsubstituted or substituted alkyl group having 1 to 12 carbon atoms, an unsubstituted or substituted cyclic alkyl group having 3 to 22 carbon atoms, an unsubstituted or substituted aryl group having 3 to 22 carbon atoms, or an unsubstituted or substituted alkylaryl group having 4 to 22 carbon atoms, which may be substituted with one or more groups R a wherein one or more non-adjacent CH2 groups in the alkyl group, cyclic alkyl group, aryl group and / or the alkylaryl group can be independently replaced by R a C=CR a 、C≡C、Si(R a )2、Ge(R a )2、Sn(R a )2. C=O, C=S, C=Se, C=NR a ,P(=O)(R a ), SO, CSR a 、SO2、NR a , OS or CONR a wherein one or more non-adjacent CH groups in the aryl group and / or the alkylaryl group can be replaced independently of each other by SiR a ,GeR a SnR a 、CSR a 、SO2、NR a , O, S, SO or CONR a Replacement, wherein one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2; R a is, on each occurrence, identically or differently, H, D or alkyl having 1 to 10 carbon atoms, cyclic alkyl having 3 to 10 carbon atoms, aryl having 3 to 10 carbon atoms, arylalkyl having 4 to 10 carbon atoms or heteroaryl having 3 to 10 carbon atoms, whereby an H atom may be replaced by D, F, Cl, Br, I; where two or more adjacent substituents R a They may also form mono- or polycyclic aliphatic, aromatic or heteroaromatic ring systems with one another.

10. A method for manufacturing a layer, comprising at least the following steps: (I Y ) provides a composition as described in any one of claims 1 to 8; (II Y ) heating the provided composition to form a layer, preferably removing the solvent in the composition, preferably the heating is 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 sulfur-containing compound represented by the following chemical formula (I), XS-Y(I) in X is a hydrogen atom or an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom; Y is an unsubstituted or substituted alkyl group having 1 to 12 carbon atoms, an unsubstituted or substituted cyclic alkyl group having 3 to 22 carbon atoms, an unsubstituted or substituted aryl group having 3 to 22 carbon atoms, or an unsubstituted or substituted alkylaryl group having 4 to 22 carbon atoms, which may be substituted with one or more groups R a wherein one or more non-adjacent CH2 groups in the alkyl group, cyclic alkyl group, aryl group and / or the alkylaryl group can be independently replaced by R a C=CR a 、C≡C、Si(R a )2、Ge(R a )2、Sn(R a )2. C=O, C=S, C=Se, C=NR a ,P(=O)(R a ), SO, CSR a 、SO2、NR a , OS or CONR a wherein one or more non-adjacent CH groups in the aryl group and / or the alkylaryl group can be replaced independently of each other by SiR a ,GeR a SnR a 、CSR a 、SO2、NR a , O, S, SO or CONR a Replacement, wherein one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2; R a is, on each occurrence, identically or differently, H, D or alkyl having 1 to 10 carbon atoms, cyclic alkyl having 3 to 10 carbon atoms, aryl having 3 to 10 carbon atoms, arylalkyl having 4 to 10 carbon atoms or heteroaryl having 3 to 10 carbon atoms, whereby an H atom may be replaced by D, F, Cl, Br, I; where two or more adjacent substituents R a They may also form mono- or polycyclic aliphatic, aromatic or heteroaromatic ring systems with one another.

13. A layer according to claim 11 or 12, wherein the dielectric constant (ε r ) is in the range of 3.5 to 10.

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 one layer according to any one of claims 11 to 14.

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