KR20170034116A - Modified copolymer, producting process and application thereof - Google Patents
Modified copolymer, producting process and application thereof Download PDFInfo
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- KR20170034116A KR20170034116A KR1020150132393A KR20150132393A KR20170034116A KR 20170034116 A KR20170034116 A KR 20170034116A KR 1020150132393 A KR1020150132393 A KR 1020150132393A KR 20150132393 A KR20150132393 A KR 20150132393A KR 20170034116 A KR20170034116 A KR 20170034116A
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- 0 C*N(*)*OC(C(*)=C)=O Chemical compound C*N(*)*OC(C(*)=C)=O 0.000 description 1
- XIEOABHANNZSHP-UHFFFAOYSA-N CC[O](C)N(C)[O](C)=C Chemical compound CC[O](C)N(C)[O](C)=C XIEOABHANNZSHP-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
More particularly, the present invention relates to a modified copolymer that can be applied to a display substrate, a process for producing the same, and a coating composition containing the same.
A flat panel device has been developed in place of a conventional cathode ray tube (CRT). In the 2000s, a flexible display, which is a flexible device in the domestic and international display industries, is attracting attention. The glass substrate, which has been used as a flat panel display substrate conventionally used, is fragile due to the nature of the material, and is used as a portable display or when a large size is used, additional protective material is used.
In order to overcome the disadvantages of the glass substrate and to apply it as a substrate as a flexible material, it is not sufficient merely to have a flexible characteristic, and it is required to satisfy the characteristics required in a conventional display device. With respect to the basic characteristics required for a display device, optical transparency, yellowness, and light-uniformity are required for a transmissive display. Another feature required is suitability for the display process. In order to replace the existing organic substrate process, it is necessary to have sufficient resistance to chemical solvents according to the high-temperature process and the cleaning process.
Flexible substrates that can replace glass are generally based on polymer materials that are thin, lightweight, strong to impact, and capable of imparting bending properties, such as plastic materials. As a plastic substrate material suitable for flexible displays, polycarbonate (PC), polyethersulfone (PES), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimide (PI) Polyimide, Polyarylate, Cycloolefin, and Glass Fiber Reinforced Plastic (FPR) have been studied as composite materials. However, to date, polyimide (PI) is the only ash that meets suitability and properties with display process conditions.
Polyimides are colored in brown or yellow due to their high aromatic ring density and show low transmittance in the visible light region, and such properties are a fatal drawback for optical materials. In order to solve this problem, the density of electrons present in the main chain is reduced by introducing a functional group having a relatively high electronegativity or introducing an olefinic cyclo-olefin structure which is not benzene to form a colorless polyimide CPI) films have been developed. However, it still has a low light transmittance and a high yellowness for use as a transparent material. There is a need to develop new techniques to compensate for the disadvantages of such transparent polyimides.
SUMMARY OF THE INVENTION The present invention has been made in order to overcome the problems of the prior art described above, and an object of the present invention is to provide a hybrid organic / inorganic hybrid material capable of improving heat resistance and optical characteristics while maintaining flexibility and light weight, And a method for producing an organic copolymer as a precursor for producing the hybrid copolymer, an organic hybrid copolymer and an organic copolymer as a precursor.
Another object of the present invention is to provide a coating liquid composition containing an organic / inorganic hybrid copolymer having excellent optical properties and heat resistance, which can improve the optical properties and physical properties of a transparent plastic substrate.
Other objects and advantages of the present invention will become more apparent from the following detailed description of the invention and the accompanying drawings.
The present invention having the above-mentioned objects is achieved by providing an organic / inorganic hybrid copolymer capable of improving, for example, heat resistance and optical properties of a material to be applied to a transparent plastic substrate, a precursor obtained by the process for producing the organic / inorganic hybrid copolymer And a coating liquid composition comprising the organic / inorganic hybrid copolymer.
According to one aspect of the present invention, there is provided a modified organic copolymer represented by the following general formula (I) as a precursor for producing an organic hybrid copolymer.
(In the general formula (Ⅰ) R is a hydrogen atom, each independently C 1 -C 20 alkyl, C 1 -C 20 alkoxy group, C 2 -C 20 alkenyl, C 6 -C 18 aryl, C 3 -C 20-alkyl acrylate group, C 4 -C 20 alkyl methacrylate groups, C 1 -C 20 aminoalkyl group, a mercapto group, a sulfonic acid group, C 1 -C 20 alkyl group selected from the group consisting of vinyl, and vinyl; R 1 And R 2 are each independently a hydrogen atom or a C 1 -C 10 alkyl group, R 3 and R 4 are each independently a C 1 -C 10 alkylene group, m and n are each a number in the range of 0.2-0.8, m + n = 1)
For example, the weight average molecular weight (Mw) of the modified organic copolymer may range from 1,000 to 40,000.
According to another aspect of the present invention, there is provided a process for producing the modified organic copolymer of the general formula (I), which comprises reacting an alkoxysilane compound represented by the following general formula (III) with an alkoxysilane compound represented by the following general formula (IV) And reacting the unsaturated ethylenic compound with a radical.
(R, R 1 , R 2 , R 3 and R 4 in the general formulas (III) and (IV) are the same as defined in the general formula (I)
According to still another aspect of the present invention, there is provided an organic / inorganic hybrid copolymer represented by the following general formula (V).
(In the general formula (Ⅴ) R is a hydrogen atom, each independently C 1 -C 20 alkyl, C 1 -C 20 alkoxy group, C 2 -C 20 alkenyl, C 6 -C 18 aryl, C 3 -C 20-alkyl acrylate group, C 4 -C 20 alkyl methacrylate groups, C 1 -C 20 aminoalkyl group, a mercapto group, a sulfonic acid group, C 1 -C 20 alkyl group selected from the group consisting of vinyl, and vinyl; R 1 And R 2 are each independently a hydrogen atom or a C 1 -C 10 alkyl group, R 3 and R 4 are each independently a C 1 -C 10 alkylene group, R 5 and R 6 are each independently a hydrogen atom, C 1 C 2 -C 20 alkyl group, C 1 -C 20 alkoxy group, C 2 -C 20 alkenyl group, C 6 -C 18 aryl group, C 3 -C 20 alkyl acrylate group, C 4 -C 20 alkyl methacrylate group, C 3 -C 20 alkyl vinyl group and vinyl group, R 7 is a C 1 -C 10 alkyl group or a C 6 -C 18 aryl group, R 8 is a hydrogen atom, a C 1 -C 10 alkyl group, a C 2 -C 20 alkoxyalkyl group, C 2 -C 20 alkenyl, C 6 -C 18 aryl, C 7 -C 19 al A number of m and n are each 0.2 to 0.8 range, provided that m + n = 1 Im;; aryl group, C 7 -C 19 alkoxyaryl groups, C 3 -C 20 alkyl, vinyl, and a vinyl group selected from o and p Is a number ranging from 0.02 to 0.98, with the proviso that o + p = 1 and q is an integer from 1 to 5)
In one exemplary embodiment, the weight average molecular weight (Mw) of the organic or inorganic hybrid copolymer represented by the general formula (V) may range from 5,000 to 100,000.
According to another aspect of the present invention, there is provided a method for producing an organic / inorganic hybrid copolymer represented by the general formula (V).
In one exemplary embodiment, the method for producing the organic / inorganic hybrid copolymer represented by the general formula (V) comprises: hydrating the silicon alkoxy group of the organic copolymer represented by the following general formula (I) Into the form of an organic copolymer of the following general formula (II); And grafting the silazane-based copolymer represented by the following general formula (VI) to the hydrated organic copolymer of the following general formula (II).
(Wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , m, n, o, p and q is the same as defined in formula (V)
At this time, the organic copolymer represented by the general formula (I) can be synthesized by radical-reacting an alkoxysilane compound represented by the following general formula (III) with an ethylenic compound represented by the following general formula (IV) .
(R, R 1 , R 2 , R 3 and R 4 in the general formulas (III) and (IV) are the same as defined in the general formula (I)
The silazane-based copolymer represented by the general formula (VI) is obtained by reacting a halogenated silane compound represented by the following general formula (VII) with an amine compound represented by the following general formula (VIII) Aminoalkyltrialkoxysilane compounds represented by the following formula (I).
Wherein R 5 , R 6 , R 7 , R 8 and q are the same as defined in the general formula (VI) in the formulas (VII), (VIII) and (IX) Is a halogen atom)
According to still another aspect of the present invention, there is provided an organic / inorganic hybrid hybrid copolymer comprising an organic or inorganic hybrid copolymer represented by the above general formula (V); And an organic solvent.
At this time, in one exemplary embodiment, the organic or inorganic hybrid copolymer represented by the general formula (V) is contained in the coating composition in an amount of 0.01 to 50 parts by weight, preferably 0.5 to 30 parts by weight, May be contained in an amount of 50 to 99.0 parts by weight, preferably 70 to 99.5 parts by weight.
For example, the organic solvent contained in the coating composition is a C 2 -C 10 aliphatic ethers, C 2 -C 10 aliphatic ketones, C 3 -C 10 aliphatic esters, C 4 -C 10 aliphatic ethers, C 4 -C 10 aliphatic ketones, C 4 -C 10 aliphatic esters, C 1 -C 10 aliphatic alcohols, C 2 -C 10 glycol, unsubstituted or substituted C 5 -C 10 aromatic alcohols, C 1 -C 5 alkyl Substituted C 3 -C 10 aliphatic amide, C 3 -C 10 alkane, unsubstituted or C 1 -C 10 alkyl substituted C 5 -C 20 aryl, and combinations thereof.
Alternatively, the coating composition may further comprise at least one additive selected from the group consisting of a curing agent, a releasing agent, a surfactant, an antioxidant, metal particles, oxide particles, nitride particles, dyes and pigments.
According to another aspect of the present invention, And a cured product of the organic or inorganic hybrid copolymer represented by the general formula (V) formed on one side of the plastic substrate.
In one exemplary embodiment, the plastic substrate is selected from the group consisting of polyimide, polyethylene, polyetherimide, polyethylene naphthalate, polyethersulfone, polyethylene terephthalate, polyethylene terephthalate glycol, polycarbonate, polymethylmethacrylate, A group consisting of polyacrylonitrile, polyacrylonitrile, polyacrylonitrile, polyacrylonitrile, polyacrylonitrile, polyacrylonitrile, polyacrylonitrile, polyacrylonitrile, acrylonitrile, And the like.
According to another aspect of the present invention, there is provided a method of manufacturing a plastic substrate, comprising the steps of: applying the above-described coating composition onto a plastic substrate; And curing the above-mentioned organic-base hybrid copolymer contained in the coating composition applied on the plastic substrate.
In an exemplary embodiment of the present invention, the curing step may include applying heat or light (e.g., ultraviolet light) to the coating composition.
The organic / inorganic hybrid copolymer synthesized according to the present invention has an appropriate combination of an organic component and an inorganic component, thereby maximizing the advantages of each component. For example, a coating film obtained by curing an organic / inorganic hybrid copolymer modified according to the present invention has high heat resistance and excellent light transmittance. Therefore, by laminating the coating film on a plastic substrate such as polyimide which can be applied to a flexible display, the physical properties of the substrate for a flexible display can be improved.
In addition, when it is inserted into the intermediate layer of the material, it has excellent adhesion to black matrices, pressure sensitive adhesives (PSA), optical clear adhesives (OCA), and hard coating layers that can be formed on the coating film.
In particular, the modified organic / inorganic hybrid copolymer according to the present invention can be mass-produced easily by a continuous process such as a roll-to-roll process, which is economical in terms of cost. Accordingly, the modified organic / inorganic hybrid copolymer synthesized according to the present invention can solve various problems caused by the plastic substrate for flexible display. For example, a film obtained by curing a coating composition containing the modified organic-inorganic hybrid copolymer of the present invention can be applied to a plastic substrate that can perform the functions of a window film and an electrode film together.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a graph showing the results of thermogravimetric analysis (TGA) analysis performed on a coating composition containing an organic or inorganic hybrid copolymer synthesized according to an exemplary embodiment of the present invention. FIG.
Figure 2 is a photograph showing the results of the adhesion test on a polyimide film coated with a coating composition comprising an organic-inorganic hybrid copolymer synthesized according to an exemplary embodiment of the present invention.
The inventors of the present invention completed the present invention by, for example, studying materials that can be applied in a high temperature substrate manufacturing process while improving physical properties of a substrate for a flexible display. The present invention relates to an organic copolymer as a precursor for producing a novel organic or inorganic hybrid copolymer, an organic or inorganic hybrid copolymer obtained by side-chain bonding of the organic copolymer and another copolymer, that is, a grafting process, The present invention relates to a coating composition comprising an organic / inorganic hybrid copolymer and an application thereof. Hereinafter, the present invention will be described with reference to the accompanying drawings where necessary.
[Modified Organic Copolymer and Method for Producing the Same]
According to one aspect of the present invention, the present invention relates to a modified organic copolymer as a precursor for producing an organic hybrid copolymer. The modified organic copolymer according to the present invention can be represented by the following general formula (I).
(In the general formula (Ⅰ) R is a hydrogen atom, each independently C 1 -C 20 alkyl, C 1 -C 20 alkoxy group, C 2 -C 20 alkenyl, C 6 -C 18 aryl, C 3 -C 20-alkyl acrylate group, C 4 -C 20 alkyl methacrylate groups, C 1 -C 20 aminoalkyl group, a mercapto group, a sulfonic acid group, C 1 -C 20 alkyl group selected from the group consisting of vinyl, and vinyl; R 1 And R 2 are each independently a hydrogen atom or a C 1 -C 10 alkyl group, R 3 and R 4 are each independently a C 1 -C 10 alkylene group, m and n are each a number in the range of 0.2-0.8, m + n = 1)
In an exemplary embodiment, the alkyl group constituting R in formula (I) above may preferably be a C 1 -C 10 alkyl group, more preferably a C 1 -C 5 alkyl group, and the alkoxy group is preferably C 1 -C 10 alkoxy group, and more preferably may be a C 1 -C 5 alkoxy group. The C 2 -C 20 alkenyl group is preferably a C 2 -C 10 alkenyl group, more preferably a C 2 -C 5 alkenyl group. Non-limiting examples of C 6 -C 18 aryl group include C 6 -C 12 aryl group, for example, a C 6 -C 12 aryl group substituted as phenyl group or tolyl group and a C 1 -C 5 alkyl group. The C 3 -C 20 alkyl acrylate group is preferably a C 3 -C 12 acrylate group, and the C 4 -C 20 alkyl methacrylate group is preferably a C 4 -C 10 alkyl methacrylate group such as methyl Methacrylate group and ethyl methacrylate group. The C 1 -C 20 aminoalkyl group is preferably a C 1 -C 10 aminoalkyl group, more preferably a C 1 -C 5 aminoalkyl group such as an aminomethyl group, an aminoethyl group, an aminopropyl group, or an aminobutyl group. The C 1 -C 20 alkyl vinyl group is preferably a C 1 -C 10 alkyl vinyl group, more preferably a C 1 -C 5 alkyl vinyl group such as a methyl vinyl group, an ethyl vinyl group and a propyl vinyl group. In one exemplary embodiment, the R constituting the general formula (I) is a C 1 -C 5 alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, a phenyl group or a vinyl group.
On the other hand, in the general formula (I), R 1 and R 2 are preferably a hydrogen atom or a C 1 -C 5 alkyl group, particularly preferably a hydrogen atom or a methyl group. In the general formula (I), R 3 and R 4 are preferably a C 1 -C 8 alkylene group, more preferably a C 1 -C 5 alkylene group.
The organic copolymer of the general formula (I) modified according to the present invention has a silicon atom which can be crosslinked through an ether bond, basically has a CC organic backbone skeleton, and has an ethylenic double bond having a hydroxy group For example, an acrylate group or a methacrylate group in the structure. The organic copolymer of formula (I) may constitute a branch of the organic / inorganic hybrid copolymer according to another aspect of the present invention described later.
In an exemplary embodiment, the weight average molecular weight (Mw) of the organic copolymer of formula (I) may be from 1,000 to 40,000, such as from 3,000 to 25,000, more preferably from 4,000 to 20,000. When the weight average molecular weight of the organic copolymer represented by the general formula (I) is less than the above-mentioned range, the coating film formed using the organic / inorganic hybrid copolymer produced from the organic copolymer is insufficient in strength, . On the other hand, when the weight average molecular weight of the organic copolymer represented by the general formula (I) exceeds the above-mentioned range, there is a fear that the optical characteristics are lowered. However, the weight average molecular weight of the modified organic copolymer represented by the general formula (I) synthesized according to the present invention is not necessarily limited to the above-mentioned range. In one exemplary embodiment, the weight average molecular weight of the modified organic copolymer represented by formula (I) can be determined using gel-permeation chromatography (GPC) using polystyrene standards.
In the general formula (I), m and n are each from 0.2 to 0.8, preferably from 0.4 to 0.6, such as from 0.45 to 0.55, with the proviso that m + n = 1. For example, when the mole fractions represented by m and n satisfy the above-described range, the physical properties of the coating film produced by the final organic / inorganic hybrid copolymer can be improved.
Next, a method for producing the modified organic copolymer represented by the above general formula (I) according to the present invention will be described. In one exemplary embodiment, the modified organic copolymer of formula (I) is obtained by polymerizing an alkoxysilane compound represented by the following formula (III) and an unsaturated ethylenic compound represented by the following formula (IV) Reaction, for example, radical polymerization.
(R, R 1 , R 2 , R 3 and R 4 in the general formulas (III) and (IV) are the same as defined in the general formula (I)
Examples of the alkoxysilane compound represented by the general formula (III) are those wherein R is a C 1 -C 5 alkyl group, a phenyl group or a vinyl group, R 1 is a hydrogen atom or a methyl group, R 3 is a C 1 -C 5 alkylene And the like. For example, as the alkoxysilane compound represented by the general formula (III), acryloxyalkyltrialkoxysilane such as acryloxypropyltrimethoxysilane, acryloxypropyltriethoxysilane and acryloxytripropoxysilane, methacryloxypropyltriethoxysilane such as methacryloxypropyltriethoxysilane, And methacryloxyalkyltrialkoxysilanes such as methacryloxypropyltriethoxysilane, methacryloxypropyltriethoxysilane, and methacryloxypropyltripropoxysilane, but the present invention is not limited thereto.
Examples of the unsaturated ethylenic compound represented by the general formula (IV) include those wherein R is a C 1 -C 5 alkyl group, a phenyl group or a vinyl group, R 2 is a hydrogen atom or a methyl group, R 4 is a C 1 -C 5 alkylene And the like. For example, the unsaturated ethylenic compound represented by the general formula (IV) is a compound obtained by copolymerizing 2-hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- Include compounds having an acrylate group or a methacrylate group, but the present invention is not limited thereto. In this connection, the term "(meth) acrylate" as used herein means to include both "acrylate" and "methacrylate".
The polymerization process through reaction between the alkoxysilane compound represented by the general formula (III) and the unsaturated ethylenic compound represented by the general formula (IV) can occur through the radical polymerization reaction. Suitable radical initiators may be included for radical polymerization reactions. As the radical initiator which can be used in the polymerization composition for producing the modified organic copolymer represented by the general formula (I), the same component as the appropriate curing agent component which can be used in the coating solution described later can be used.
The polymerization reaction between the alkoxysilane compound represented by the general formula (III) and the unsaturated ethylenic compound represented by the general formula (IV) can take place in the polymerization solvent. As the polymerization solvent, any polymerization solvent capable of mediating the polymerization reaction between the alkoxysilane compound represented by the general formula (III) and the unsaturated ethylenic compound represented by the general formula (IV) can be used. In general, the polymerization step proceeds under a soluble solvent capable of forming a homogeneous solution. For example, the polymerization solvent may be a C 2 -C 10 aliphatic ether, a C 2 -C 10 aliphatic ketone, a C 3 -C 10 aliphatic ester, a C 4 -C 10 cycloaliphatic ether, a C 4 -C 10 alicyclic ketone, a C 4 -C 10 aliphatic esters, C 1 -C 10 aliphatic alcohols, unsubstituted or substituted C 5 -C 10 aromatic alcohols, C 1 -C 5 alkyl substituted C 3 -C 10 aliphatic amide, C 3 -C 10 Alkane, unsubstituted or C 1 -C 5 alkyl substituted C 6 -C 10 aryl, and combinations thereof. Examples of the polymerization solvent include propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), n-butyl acetate, ethyl lactate, tetrahydrofuran But are not limited to, tetrahydrofuran (THF), cyclohexanone, gamma -butyrolactone, N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide And may be selected from the group consisting of dimethyl sulfoxide, dioxane, methyl ethyl ketone, toluene, xylene, benzene, benzyl alcohol, amyl alcohol and combinations thereof But the polymerization solvent usable in the present invention is not limited thereto.
The polymerization reaction between the alkoxysilane compound represented by the general formula (III) and the unsaturated ethylenic compound represented by the general formula (IV) can be initiated, for example, by dissolving in the above-mentioned polymerization solvent. In one exemplary embodiment, in order to adjust the rate of the reaction by radicals, the reaction is initially carried out at 0 to 30 캜, preferably 10 to 25 캜, for about 1 to 3 hours, preferably about 1 to 2 hours . During stirring, a nitrogen stream can be flowed to minimize the formation of atmospheric oxygen radicals.
The content of the solid content of the alkoxysilane compound represented by the general formula (III) and the unsaturated ethylenic compound represented by the general formula (IV) and the radical initiator dissolved in the polymerization solvent in the polymerization reaction is such that the respective components So long as it can be uniformly dissolved. In one exemplary embodiment, the amount of polymerization solvent used in the polymerization reaction can be adjusted to a range such that the total-concentration of each reactant in the polymerization solvent is about 5 to 60 wt%, preferably about 20 to 50 wt% . For example, the alkoxysilane compound represented by the general formula (III) and the unsaturated ethylenic compound represented by the general formula (IV) in an amount of 25 to 45 parts by weight, preferably 25 to 45 parts by weight, 80 parts by weight, preferably 55 to 75 parts by weight. The amount of the radical initiator added to the reaction solution is not particularly limited, but may be added in a ratio of about 0.1 to 5 parts by weight. Unless otherwise stated herein, "parts by weight" is understood to mean the relative weight ratios between the other ingredients being compounded.
On the other hand, after the completion of the polymerization reaction between the alkoxysilane compound represented by the general formula (III) and the unsaturated ethylenic compound represented by the general formula (IV), unreacted raw materials, catalysts and the like existing in the system are removed May be performed. For example, a method of removing the volatile components by raising the temperature of the reaction vessel to 130 to 230 ° C, a method of separating the polymer by adding an appropriate solvent, and a method of dissolving the polymer in a good solvent and re- Can be used. In one exemplary embodiment, a purification solvent may be used to separate the product obtained in the polymerization reaction from the solution used in the polymerization process. Purified solvents are used to precipitate the product obtained by the polymerization reaction and to separate the precipitated product from the solution. In one exemplary embodiment, the purification solvent may be a C 3 -C 10 alkane, such as hexane, a C 1 -C 5 alcohol such as methanol, ethanol, and / or water (such as distilled water) But is not limited to.
[Silazane-based copolymer and method for producing the same]
The silazane-based copolymer constituting the main chain of the organic / inorganic hybrid copolymer according to the present invention can be represented by the following general formula (VI).
Wherein each R independently represents a hydrogen atom, a C 1 -C 20 alkyl group, a C 1 -C 20 alkoxy group, a C 2 -C 20 alkenyl group, a C 6 -C 18 aryl group, a C 3 -C 20 aryl group, A C 1 -C 20 alkyl acrylate group, a C 4 -C 20 alkyl methacrylate group, a C 1 -C 20 aminoalkyl group, a mercapto group, a sulfonic acid group, a C 1 -C 20 alkyl vinyl group, and a vinyl group; R 5 and R 6 are each independently a hydrogen atom, a C 1 -C 20 alkyl group, a C 1 -C 20 alkoxy group, a C 2 -C 20 alkenyl group, a C 6 -C 18 aryl group, a C 3 -C 20 alkyl acrylate group, C 4 -C 20 alkyl methacrylate groups, C 3 -C 20 alkyl, vinyl, and a vinyl group selected from; R 7 is C 1 -C 10 alkyl or C 6 -C 18 aryl group; R 8 is a hydrogen atom , A C 1 -C 10 alkyl group, a C 2 -C 20 alkoxyalkyl group, a C 2 -C 20 alkenyl group, a C 6 -C 18 aryl group, a C 7 -C 19 alkylaryl group, a C 7 -C 19 alkoxyaryl group, C 3 -C 20 alkyl, selected from a vinyl group and a vinyl group; o and p are each a number of 0.02 to 0.98 range, o + p = 1 Im; q is an integer of 1 to 5)
The modified polysilazane polymer represented by the general formula (VI) forms the main chain of the organic or inorganic hybrid copolymer described later, and the modified organic copolymer represented by the general formula (I) described above is side-bonded. The modified polysilazane-based polymer represented by the general formula (VI) has a high heat resistance and flexibility having a main chain skeleton composed of -Si-N-silazane bonds and a combination of chemical resistance due to multiple crosslinking of the alkoxysilyl group introduced into the side chain Hybrid composite material.
The substituent constituting R in formula (VI) includes, for example, a C 1 -C 10 alkyl group, preferably a C 1 -C 5 alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group, The present invention is not limited thereto.
The C 1 -C 20 alkyl group constituting R 5 and R 6 in the modified polysilazane-based polymer represented by the general formula (VI) is preferably a C 1 -C 10 alkyl group, more preferably a methyl group, C 1, such as a propyl group, a butyl group is -C 5 alkyl group. The C 1 -C 20 alkoxy group constituting R 5 and R 6 of the general formula (VI) is preferably a C 1 -C 10 alkoxy group, more preferably a methoxy group, an ethoxy group, a propoxy group, And may be the same C 1 -C 5 alkoxy group. The C 6 -C 18 aryl group constituting R 5 and R 6 of the general formula (VI) is preferably a C 6 -C 12 aryl group, for example, a C 6 -C 12 aryl group such as a phenyl group or a A C 7 -C 12 aryl group substituted with a C 1 -C 5 alkyl group. The C 3 -C 20 alkyl acrylate group constituting R 5 and R 6 of the general formula (VI) is preferably a C 3 -C 10 alkyl acrylate group such as methyl acrylate group and ethyl acrylate group. The C 4 -C 20 alkyl methacrylate group constituting R 5 and R 6 in the general formula (VI) is preferably a C 4 -C 10 alkyl methacrylate group such as a methyl methacrylate group and an ethyl methacrylate group to be. The constituting the R 5 and R 6 in the formula (Ⅵ) C 3 -C 20 alkyl vinyl group, preferably a C 3 -C10 alkyl vinyl group, more preferably methyl vinyl group, an ethyl vinyl group, propyl vinyl And a C 3 -C 6 alkyl vinyl group such as a vinyl group.
The C 1 -C 10 alkyl group constituting R 7 in the general formula (VI) is preferably a C 1 -C 5 alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, and the C 6 -C 18 aryl group is preferably a phenyl group C 6 -C 12 aryl group, or a tolyl group such as C 1 -C a C 7 -C 12 aryl group substituted with an alkyl group, such as 5. The C 1 -C 10 alkyl group constituting R 8 in the general formula (VI) is preferably a C 1 -C 5 alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, and the C 2 -C 20 alkoxyalkyl group is preferably a A C 2 -C 6 alkoxyalkyl group such as a methoxymethyl group, an ethoxymethyl group, and a methoxyethyl group. The C 6 -C 18 aryl group and the C 7 -C 19 alkylaryl group constituting R 8 of the general formula (VI) are preferably a C 6 -C 12 aryl group such as a phenyl group or a C 1 -C 5 alkyl group such as a tolyl group a C 7 -C 12 alkylaryl group is optionally substituted with.
On the other hand, the C 7 -C 19 alkoxyaryl group constituting R 8 of the general formula (VI) is preferably a C 7 -C 13 alkoxyaryl group, and examples thereof include a methoxyphenyl group, an ethoxyphenyl group, a propoxyphenyl group, Naphthyl group, and naphthyl group. C 3 -C 20 alkyl vinyl constituting R 8 of general formula (Ⅵ) is preferably a C 3, such as C 3 -C 10 alkyl groups and vinyl, more preferably methyl vinyl group, a vinyl group or ethyl group and propyl vinyl -C 6 alkyl vinyl group.
According to one exemplary embodiment, the above-mentioned formula (Ⅵ) R in the polysilazane jangye copolymer represented by 5, R 6 and R 7 are each independently a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, a tolyl group Or a vinyl group, R 8 is a hydrogen atom or a methyl group, and R is a methyl group, an ethyl group, a propyl group or a butyl group.
In the polysilazane-based copolymer represented by the general formula (VI), o and p are molar fractions of the constituent monomers. o is a number from 0.01 to 0.99, preferably from 0.30 to 0.99, for example from 0.60 to 0.90, p is a number from 0.01 to 0.99, preferably from 0.10 to 0.70, for example from 0.10 to 0.70 -0.40, with the proviso that o + p = 1. For example, if o is less than 0.01, there may be a problem of poor chemical resistance. If p is more than 0.99, flexibility and solubility may be deteriorated. q is an integer of 1 to 5, and may be an integer of 1 to 3, for example.
The weight average molecular weight (Mw) of the modified polysilazane polymer represented by the general formula (VI) may be 500 to 20,000, for example, 2,000 to 20,000, preferably 30,000 to 18,000, more preferably 5,000 to 15,000 . The weight average molecular weight of the polysilazane-based copolymer can be measured by gel permeation chromatography using a polystyrene standard. The weight average molecular weight of the polymer is not particularly limited, and it is sufficient that the cured product of the polymer can form a coating film.
Next, a method for producing the modified polysilazane-based copolymer represented by the general formula (VI) will be described. In one exemplary embodiment, the modified polysilazane copolymer of the general formula (VI) is obtained by reacting a halogenated silane compound represented by the following general formula (VII) with an amine compound represented by the following general formula (VIII) Can be synthesized by reacting an aminoalkyltrialkoxysilane compound represented by the following general formula (IX) together.
Wherein R 5 , R 6 , R 7 , R 8 and q are the same as defined in the general formula (VI) in the formulas (VII), (VIII) and (IX) Is a halogen atom)
The halogen atom constituting X in the general formula (VII) may be, for example, at least one halogen atom selected from F, Cl, Br and I. Non-limiting examples of the halogenated silane compound represented by the general formula (VII) include difluorodimethylsilane, difluorodiethylsilane, difluorodipropylsilane, dichlorodimethylsilane, dichlorodiethylsilane, dichlorodipropylsilane, The present invention is not limited thereto. Non-limiting examples of the amine compound represented by the general formula (VIII) include primary alkyl amines such as methylamine, ethylamine and propylamine, and primary arylamines such as aniline and toluidine , But the present invention is not limited thereto. Nonlimiting examples of the aminoalkyltrialkoxysilane compound represented by the general formula (IX) include (3-aminopropyl) trimethoxysilane, (3-aminopropyl) triethoxysilane, Tripropoxysilane, and the like, but the present invention is not limited thereto.
According to an exemplary embodiment of the present invention, in order to produce the polysilazane-based copolymer represented by the general formula (VI), a halogenated silane compound represented by the general formula (VII), an amine compound represented by the general formula (VIII) And the aminoalkyltrialkoxysilane compound represented by the general formula (IX) is preferably adjusted to 1: 1 or close to this in view of increasing the molecular weight of the resulting polymer without leaving any residual monomers. The molar amount of the aminoalkyltrialkoxysilane compound represented by the general formula (IX) may be adjusted to the halogenated (meth) acrylate represented by the general formula (VII) in order to lower the shrinkage rate upon high temperature curing after the modified polysilazane- When the total mol number of the amine compound represented by the silane compound + formula (VIII) is 1, it is preferably adjusted to 0.1 to 0.4.
The polymerization reaction between the monomers represented by the general formulas (VII), (VIII) and (IX) is typically carried out in an inert atmosphere such as N 2 , Ar and He at -20 to 0 Deg.] C, preferably -10 to 0 [deg.] C for about 1 to about 3 hours, preferably about 1 to about 2 hours. The post-polymerization is then carried out for about 3 to about 20 hours, preferably about 4 to about 10 hours, while maintaining the reaction temperature under an inert atmosphere at 5 to 40 캜, preferably 10 to 30 캜, more preferably around room temperature To increase the molecular weight of the polymer and to stabilize the properties of the polymer solution.
The polymerization solvent used for synthesizing the organic copolymer represented by the general formula (I) described above can also be used for synthesizing the polysilazane copolymer represented by the general formula (VI). For example, the polymerization reaction for synthesizing the polysilazane based copolymer may be carried out in the presence of a catalyst such as propylene glycol monomethyl ether acetate (PGME), N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc) Or a nonpolar aromatic organic solvent such as benzene, toluene or xylene or a nonpolar aliphatic organic solvent such as pentane, hexane or heptane or an alkyl ether such as diisopropyl ether, dibutyl ether, methylal (dimethoxymethane) or diethyl ether . Typically, the amount of organic solvent used in the polymerization reaction is such that the total concentration of reactants in the organic solvent is from about 5 to about 40 wt%, preferably from about 5 to about 30 wt%.
On the other hand, in the reaction, a basic compound (hereinafter referred to as " basic compound ") for capturing hydrogen halide such as hydrogen chloride, hydrogen bromide or the like which is generated by condensation of a halogen atom in the general formula (VII) with hydrogen atoms of the amino group of the general formula And the like. A basic compound which can be used for this purpose is not particularly proposed if it is capable of forming a salt by bonding with a hydrogen halide. For example, the basic compound is preferably a tertiary aliphatic amine compound such as trimethylamine, triethylamine or an aromatic amine compound such as pyridine.
The order of introduction of the reactants in the reaction is not particularly limited. In an exemplary embodiment, an amine compound represented by the general formula (VIII) and an aminoalkyltrialkoxysilane compound represented by the general formula (IX) are first introduced into a reaction solvent to dissolve the compound, and then the compound represented by the general formula It is preferable to add the halogenated silane compound in such a manner that the halogenated silane compound is gradually added thereto in terms of reaction control.
[Organic-inorganic hybrid copolymer and production method thereof]
According to the present invention, there is provided a modified polysilazane-based copolymer represented by the above-mentioned general formula (VI) as a main chain, wherein the modified organic copolymer represented by the general formula (I) is a side chain- The hybrid copolymer may be represented by the following general formula (V).
(In the general formula (Ⅴ) R is a hydrogen atom, each independently C 1 -C 20 alkyl, C 1 -C 20 alkoxy group, C 2 -C 20 alkenyl, C 6 -C 18 aryl, C 3 -C 20-alkyl acrylate group, C 4 -C 20 alkyl methacrylate groups, C 1 -C 20 aminoalkyl group, a mercapto group, a sulfonic acid group, C 1 -C 20 alkyl group selected from the group consisting of vinyl, and vinyl; R 1 And R 2 are each independently a hydrogen atom or a C 1 -C 10 alkyl group, R 3 and R 4 are each independently a C 1 -C 10 alkylene group, R 5 and R 6 are each independently a hydrogen atom, C 1 C 2 -C 20 alkyl group, C 1 -C 20 alkoxy group, C 2 -C 20 alkenyl group, C 6 -C 18 aryl group, C 3 -C 20 alkyl acrylate group, C 4 -C 20 alkyl methacrylate group, C 3 -C 20 alkyl vinyl group and vinyl group, R 7 is a C 1 -C 10 alkyl group or a C 6 -C 18 aryl group, R 8 is a hydrogen atom, a C 1 -C 10 alkyl group, a C 2 -C 20 alkoxyalkyl group, C 2 -C 20 alkenyl, C 6 -C 18 aryl, C 7 -C 19 al A number of m and n are each 0.2 to 0.8 range, provided that m + n = 1 Im;; aryl group, C 7 -C 19 alkoxyaryl groups, C 3 -C 20 alkyl, vinyl, and a vinyl group selected from o and p Is a number ranging from 0.02 to 0.98, with the proviso that o + p = 1 and q is an integer from 1 to 5)
Preferable examples of the respective substituents constituting the general formula (V) are the same as those described for the organic copolymer represented by the general formula (I) and / or the polysilazane copolymer represented by the general formula (VI) , And a detailed description thereof will be omitted. In one exemplary embodiment, the weight average molecular weight (Mw) of the organic or inorganic hybrid copolymer represented by the general formula (V) may range from 5,000 to 100,000, for example, from 7,000 to 50,000. If the weight average molecular weight of the organic or inorganic hybrid copolymer represented by the general formula (V) is less than the above-mentioned range, the strength of the coating film may be insufficient or the physical properties such as heat resistance may be deteriorated. There is a possibility that the characteristics are deteriorated. The weight average molecular weight of the organic / inorganic hybrid copolymer can be measured using gel-permeation chromatography (GPC) using polystyrene standards.
Next, a method for producing the organic / inorganic hybrid copolymer represented by the general formula (V) according to an exemplary embodiment of the present invention will be described. In one exemplary embodiment, in order to graft the polysilazane copolymer of the general formula (VI) previously prepared to the modified organic copolymer represented by the general formula (I) (Si-OR) should be hydrated in the form of silanol (Si-OH).
According to one exemplary embodiment, in one method for hydrating the silicon alkoxy group of the general formula (I) into the silanol form, the organic copolymer represented by the general formula (I) and the poly (poly) represented by the general formula (VI) The silazane-based copolymer is diluted with a solvent. Water and acid are added to the modified organic copolymer diluted in the solvent and heat is applied. In an exemplary embodiment, the amount of water added is less than 50 parts by mole of the alkoxysilane equivalent number contained in the modified organic copolymer. If added in excess of 50 moles, a rapid condensation reaction may occur between silanols produced. The hydration reaction is conducted at 0 to 30 캜, preferably 10 to 25 캜, for about 1 to about 3 hours, preferably about 1 to about 2 hours, in the initial stage of the reaction so as to appropriately control the reaction rate. By this process, the hydration reaction proceeds in at least one silicon alkoxy group of the silicon alkoxy group (Si-OR) formed in the organic copolymer of the general formula (I) to form an alcohol, .
(Wherein R, R 1 , R 2 , R 3 , R 4 , m and n are the same as defined in formula (I) or formula (V)
Next, the compound represented by the general formula (II) obtained by hydration is reacted with strong stirring at 50 to 90 ° C, preferably 60 to 80 ° C, more preferably 70 to 75 ° C for 1 to 5 hours , Preferably for 2 to 3 hours. Then, the polysilazane compound represented by the general formula (VI) which is diluted is slowly added over 1 to 5 hours, preferably 1 to 2 hours. After the addition, the composition is further stirred for about 2 to 4 hours and the solution is cooled at a temperature of 20 to 30 캜, preferably 25 캜 for about 15 minutes to complete the polymerization reaction. Based hybrid copolymer can be obtained.
[Coating Composition and Application]
Another aspect of the present invention relates to a coating composition comprising the organic or inorganic hybrid copolymer represented by the above general formula (V), a plastic substrate coated with such a coating composition, and a process for producing the same.
For example, the coating composition comprises the organic or inorganic hybrid copolymer represented by the above-mentioned general formula (V) and an organic solvent. In one exemplary embodiment, the organic or inorganic hybrid copolymer represented by the general formula (V) may be contained in the coating composition in an amount of 0.1 to 50 parts by weight, and the organic solvent may be included in the coating composition in an amount of 50 to 99.9 parts by weight. Considering the workability and safety of the mixed solution when the coating composition is coated on, for example, a plastic substrate, the content of the organic or inorganic hybrid copolymer represented by the general formula (V) is preferably 0.5 to 30 parts by weight, More preferably 1 to 10 parts by weight, and the content of the organic solvent is preferably 70 to 99.5 parts by weight, more preferably 90 to 99 parts by weight. For example, when the content of the organic solvent is low, the concentration of the coating composition is increased and the coating surface may become uneven when applied to a plastic substrate. If the amount of the solvent is too large, the viscosity becomes small and it is difficult to form a uniform coated surface.
Organic solvent which may be added in the coating composition is a C 2 -C 10 aliphatic ethers, C 2 -C 10 aliphatic ketones, C 3 -C 10 aliphatic esters, C 4 -C 10 aliphatic ethers, C 4 -C 10 cycloaliphatic ketones, C 4 -C 10 aliphatic esters, C 1 -C 10 aliphatic alcohols, unsubstituted or substituted C 5 -C 10 aromatic alcohols, C 2 -C 10 glycols, C 1 -C 5 alkyl substituted C 3 - C 10 aliphatic amide, C 3 -C 10 alkane, unsubstituted or C 3 -C 10 alkyl substituted C 5 -C 20 aryl, and combinations thereof.
Specific examples of the organic solvent include, but are not limited to, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol diacetate , PGDA), propylene glycol normal propyl ether (PnP), propylene glycol normal butyl ether (PnB), butyl cellosolve (BC), methyl cellosolve methyl cellosolve, MC), ethylene glycol (EG), propylene glycol (PG), cyclohexanone, gamma-butyrolactone (GBL), ethyl lactate N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethyl acetamide (DMAc), tetrahydrofuran (THF), ethyl-3-ethoxypropionate, toluene, xylene, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, n-propanol, isopropanol , Butanol, butoxyethanol, pentanol, octanol, hexane, heptane, ether, ketone, and combinations thereof, but the present invention is not limited thereto.
In an alternative embodiment, the coating composition of the present invention may contain, in addition to the organic solvent hybrid copolymer and the organic solvent represented by the general formula (V), a curing agent, a releasing agent, a surfactant, an antioxidant, metal particles, oxide particles and nitride particles And at least one additive selected from the group consisting of
A non-limiting example of a curing agent that may be included in the coating composition is a thermosetting agent, and it is desirable to use a latent heat curing agent that does not cause curing at low temperatures and causes curing at high temperatures. As the latent heat curing agent, a mixture of one or more selected from amine type, imidazole type, dihydrazide type, and peroxide (organic peroxide) may be used.
Specific examples of the amine type thermosetting agent include ajicure MY-24 (hereinafter, referred to as AJIMOTO), Ajyurea MY-H, Ajyurea MY-HK, Ajyure PN-23J, Ajyure PN- PN-40J, Fuji Cure FXR-1020 (hereinafter referred to as Fuji Kasei Co., Ltd.), Fuji Cure FXR-1030 and the like. Specific examples of the imidazole type thermosetting agent include 2-methylimidazole, 2-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole (manufactured by Shikoku Kasei Co., Ltd.) Specific examples of the dihydrazide type thermosetting agent include ADJUREARD VDH, ADJURYARD UDH, MDH (manufactured by Ajinomoto) ADH, SDH, DDH, IDH (manufactured by Otsuka Chemical), NDH (manufactured by Japan Hydrazine Industry Co., Ltd.) .
Specific examples of the peroxide type thermosetting agent include 2,2-bis (t-butylperoxy) butane, 1,1-bis (t-butylperoxycyclohexane), n-butyl 4,4- (4,4-di-t-butylperoxycyclohexyl) propane, t-butyl hydroperoxide, diisopropylbenzene hydroperoxide, t-butylcumyl peroxide, ,? '- bis (t-butylperoxy) diisobenzene, dicuxyl peroxide, isobutyl peroxide, succinic peroxide, 3,5,5-trimethylhexanoyl peroxide, Butyl peroxyacetate, t-butylperoxy 2-ethylhexyl monocarbonate, t-butylperoxyisobutyrate, t-butylperoxybenzoate, t-butylperoxy 3.5 2,5-dimethyl-2,5-bis (m-toluylperoxy) hexane, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, t- Amyl peroxy-2-ethyl And the like Sano benzoate.
The curing agent is preferably included in an amount of 0.1 to 5 parts by weight, for example, 0.5 to 3 parts by weight, based on the weight of the modified organic / inorganic hybrid copolymer. When the curing agent is included in the content within the above range, And coating stability can be satisfied. If the content of the curing agent is less than 0.1 parts by weight, sufficient curing may not proceed. If the content of the curing agent is more than 5 parts by weight, the storage stability may be lowered and cracking of the coating film may occur due to overcuring.
The coating composition according to the present invention may further comprise a surfactant for improving the applicability. Surfactants that can be used include, but are not limited to, polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, polyether-modified hydroxy-functional polydimethylsiloxane, polyether-ester-modified hydroxy-functional polydimethylsiloxane, Polyester-modified polydimethylsiloxane, polyoxyethylene alkyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkylallyl ethers, polyoxyethylene polyoxypropylene block copolymer, sorbitan fatty acid ester Based surfactant such as polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and the like. The content thereof is preferably 0.01 to 0.1 parts by weight, for example, 0.05 to 0.01 parts by weight, based on the weight of the modified organic / inorganic hybrid copolymer.
The coating compositions according to the present invention may further comprise conventional antioxidants, metal particles, metal oxide particles and / or metal nitride particles for the purpose of increasing hardness. As the releasing agent, those conventionally used in vinyl-based polymers, polysiloxane polymers, polyacrylic acid, and the like can be used. These antioxidants, metal particles, metal oxide particles, metal nitride particles and / or releasing agents may be added in an amount of 0.01 to 3 parts by weight, for example 0.05 to 1 part by weight, based on the weight of the modified organic / inorganic hybrid copolymer, .
Dyestuffs or pigments may be used to compensate for the yellowness in the optical properties of the coating compositions according to the present invention. Dyestuffs or pigments can be used to compensate for yellowness. The specific kind of the dye is not particularly limited, and for example, a conventional organic dye used for dyeing plastic materials can be used. Examples of the dyes include nitroso dyes, nitro dyes, azo dyes, triphenylmethane dyes, phthalic anhydride dyes, indigo dyes, an indigo dye or anthroquinone dye may be used. An anthraquinone dye may be preferably used as a blue dye.
As the pigment, a blue pigment and a purple pigment can be used. As the structure, various inorganic pigments can be used in addition to organic pigments such as azo pigments, phthalocyanine pigments, quinacridone pigments, benzimidazolone pigments, isoindolinone pigments, dioxazine pigments, indanthrene pigments, and perylene pigments.
If necessary, the coating composition of the present invention may further contain additives such as an antistatic agent, a crosslinking agent, a fluorescent whitening agent, a light diffusing agent, a pH adjusting agent, a defoamer, a defoaming agent, and a leveling agent to enhance the surface and mechanical properties of the coating film, , Lubricants, anti-curling agents, surface modifiers, thickeners, ultraviolet absorbers, deterioration inhibitors, preservatives, and the like. These other additives may be contained in the coating composition in an amount of 0.001 to 2 parts by weight, for example, 0.05 to 0.1 part by weight, based on the weight of the modified organic or inorganic hybrid copolymer, respectively.
A coated plastic substrate according to another aspect of the present invention includes a plastic substrate; And a coating film formed on the plastic substrate. The coating film includes a cured product of the modified organic hybrid copolymer. The coating film preferably comprises a cured product of the modified organic hybrid copolymer. The film composed of the cured product of the modified organic / inorganic hybrid copolymer can function together with the window film and the electrode film. Illustratively, since the coated plastic substrate of the present invention, which is produced by coating and curing an organic hybrid resin on such a conventional plastic substrate, can realize heat resistance and high transmittance characteristics, an LCD capable of being applied to, for example, a flexible display , A display device such as an organic electroluminescent device (OLED), or other electric / electronic devices.
The plastic substrate may be at least one of polyimide, polyethylene, polyetherimide, polyethylene naphthalate, polyethersulfone, polyethylene terephthalate, polyethylene terephthalate glycol, polycarbonate, polymethylmethacrylate, polymethylmethacrylimide, polyoxymethylenepoly A plastic made of a mixture of two or more of these materials, such as polypropylene, polypropylene sulfide, polyphenylene sulfone, polystyrene, polysulfone, polytetrafluoroethylene, polyurethane, polyvinyl chloride, polyvinylidene fluoride, Substrate. In an exemplary embodiment, these plastic substrates may be formed to a thickness of 20 to 500 mu m, preferably 20 to 200 mu m. When the thickness of the plastic substrate is less than 20 탆, the treatment may be difficult. When the thickness exceeds 500 탆, the plastic substrate may not be suitable as a thin flexible display material.
On the other hand, the coating film composed of the cured product of the modified organic-inorganic hybrid copolymer according to the present invention is laminated on top of the plastic film to a thickness of about 50 nm to 10 탆, preferably about 80 to 500 nm .
Optionally, a barrier barrier layer may further be formed on top of the coating film according to the present invention. This barrier barrier layer is formed in order to improve the gas and / or water barrier property of the plastic substrate, and can be formed with an inorganic material having a low moisture permeability and a low permeation rate of 100 nm or less, for example, 1 to 100 nm. The barrier layer may be formed using a metal oxide such as silicon oxide, aluminum oxide, tantalum oxide, or titanium oxide. The metal oxide may be formed by chemical vapor deposition (CVD) such as plasma enhanced chemical vapor deposition (PECVD) And may be laminated on top of the coating film through chemical and / or physical methods such as sputtering.
The modified organic or inorganic copolymer is thermally cured to form a coating film on a plastic substrate. This cured product forms a three-dimensional transparent cured coating film while condensing residual vinyl groups (C = C), alkoxy groups (Si-OR), silanol groups (Si-OH) and alcohol groups (C-OH). The chemical structure of the cured product includes both silsesquioxane, siloxane, and silicon carbide (Si-C) and silazane (Si-N) structures. The film shrinkage caused by the densification of the film can be controlled as much as possible and cracks can be effectively prevented.
The method for applying the coating composition containing the modified organic / inorganic hybrid copolymer on a plastic substrate is not particularly limited, and examples thereof include spin coating, roll coating, flow coating, dip coating, spray coating, doctor coat, May be used.
In the case of thermal curing, the coating film may be pre-baked at 80 to 180 ° C for 5 to 60 minutes and cured at 150 to 300 ° C, preferably 200 to 350 ° C for 5 to 15 minutes.
Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the technical ideas described in the following examples.
[Preparation of modified organic / inorganic hybrid copolymer]
Example 1: Synthesis of Modified Organic Copolymer
0.4 mol of methacryloxypropyl- (trimethoxy) silane, 0.1 mol of 2-hydroxyethyl methacrylate and 1.4 mol of propylene glycol monomethyl ether were placed in a reaction vessel and stirred at 20 占 폚 for 10 minutes. To this mixture, 0.002 mol of azobisisobutyronitrile (AIBN) was added to initiate the polymerization reaction. After sealing the reaction vessel, nitrogen gas was purged at a rate of 25 cc / min and stirred for 30 minutes. The temperature in the reaction vessel was raised to 30 DEG C over a period of about 10 minutes and further stirred for 30 minutes to thoroughly mix the reactants. Thereafter, the temperature in the reaction vessel was raised to 75 캜 over about 30 minutes and further stirred for 2 hours to obtain a modified organic copolymer.
The reaction product containing the copolymer was cooled to 10 DEG C over about 30 minutes, and propylene glycol monomethyl ether was further added. The weight average molecular weight of the synthesized organic copolymer was 8,000 to 20,000. The prepared solution was placed in a polypropylene container, the periphery was sealed, purged with nitrogen, and stored in a refrigerator.
Example 2: Preparation of modified polysilazane based polymer
0.8 mol of aniline and 0.2 mol of (3-aminopropyl) triethoxysilane were placed in a reaction vessel containing 0.5 L of toluene in a nitrogen atmosphere, and after stirring and dissolving, 2 mol of triethylamine was added and dissolved again. The mixture was stirred at -5 ° C for about 30 minutes. Then, a solution prepared by dissolving 1 mole of dichlorodimethylsilane in 0.5 L of toluene was slowly added to the reaction vessel over about 1 hour. When the addition was completed, the temperature in the reaction vessel was raised to 30? Over a period of about 2 hours and further stirred for 5 hours. After that, the reaction solution was filtered, purged with nitrogen, and stored for about 24 hours to obtain a stabilized solution.
The stabilized solution was further vacuum filtered using a filter paper to remove excess solid salt to obtain a transparent toluene solution. To the solution was added 1 L of anhydrous propylene glycol monomethyl ether acetate and the toluene was removed by vacuum distillation. The weight average molecular weight of the synthesized polysilazane copolymer was 7,000 to 10,000. An anhydrous propylene glycol monomethyl ether acetate solution of the modified polysilazane polymer thus obtained was placed in a 500 ml polypropylene container, filled with nitrogen gas, and the periphery was sealed and freezed.
Example 3: Grafting of a modified polysilazane polymer to a copolymer with a modified organic copolymer
The modified polysilazane polymer prepared in Example 2 was mixed with propylene glycol monomethyl ether so that the solids content of the modified organic copolymer prepared in Example 1 and Example 2 was 15% After the addition of acetate was further added, the mixture was stirred at 30 DEG C for 30 minutes. When the mixed solution of 0.55 mol of water and 0.01 mol of formic acid was added slowly to the diluted organic copolymer with strong stirring for 1 hour, the suspension gradually changed to a clear state as the hydration reaction proceeded.
When the addition was completed, the temperature in the reaction vessel was raised to 75? Over about 30 minutes and further stirred for 1 hour. The diluted polysilazane polymer was slowly added over 2 hours with vigorous stirring. The composition that had been added was stirred for another 3 hours and the temperature of the solution was cooled to 20 DEG C over 15 minutes to terminate the reaction. The weight average molecular weight of the resultant organic / inorganic hybrid copolymer was 10,000 to 50,000.
[Preparation of coating composition and application of plastic substrate]
Example 4: Preparation of a modified organic-inorganic copolymer coating composition
The modified organic-inorganic copolymer prepared in Example 3 was diluted with propylene glycol monomethyl ether acetate to a solids content of 1%. Polydimethylsiloxane-based leveling agent was added in an amount of 0.01 part by mass as the total amount of the composition, followed by stirring at 30 ° C for 4 hours and then cooling to 20 ° C over 30 minutes.
Example 5: Coating and coating with a plastic substrate
The coating composition obtained in Example 4 was coated on a colorless and transparent polyimide (CPI) film having a thickness of about 80 占 퐉 for a market using a bar coater, and then pre-baked at about 80 占 폚 for about 2 minutes ). Followed by a final heat treatment at about 220 DEG C for 8 minutes to produce a coated polyimide film.
Comparative Example 1
A colorless transparent polyimide (CPI) film having a thickness of about 80 占 퐉 for a commercial use not coated with any coating film was prebaked at about 150 占 폚 for about 2 minutes, and then subjected to a final heat treatment at about 220 占 폚 for about 8 minutes.
Experimental Example 1: Evaluation of optical characteristics of a coated substrate
<Measurement of light transmittance>
Coated polyimide film coated with the coating composition containing the novel organic or inorganic hybrid copolymer prepared in Example 5 and the uncoated commercial polyimide film of Comparative Example 1 were measured in accordance with ASTM E-1164 and DIN 5033, (Manufactured by Konica Minolta, model name: CM5), and the light transmittance was measured in the visible light region.
<Measurement of yellow color>
Coated polyimide film coated with the coating composition containing the novel organic or inorganic hybrid copolymer prepared in Example 5 and the uncoated commercial polyimide film of Comparative Example 1 were measured with a spectroscopic colorimeter (manufacturer: Konica Minolta, model name: CM5 ) Was used to measure the yellowness in the visible light region with a D65 light source according to ASTM E313.
<Measurement of HAZE>
The polyimide film coated with the novel organic or inorganic hybrid copolymer prepared in Example 5 and the uncoated commercial polyimide film obtained in Comparative Example 1 were subjected to ASTM D1003 using a spectroscopic colorimeter (manufacturer: Konica Minolta, product name: CM5) HAZE was measured in the same manner. Table 1 summarizes the measurement results of the optical characteristics obtained in this Experimental Example.
Referring to Table 1, it can be seen that the coated polyimide film according to Example 5 has better optical properties than the commercially available colorless transparent polyimide (CPI) film of Comparative Example 1.
Experimental Example 2: Measurement of thermal decomposition degree of coating composition
For accurate analysis, a coating composition having a solids content of 12% adjusted to the ratio described in Example 4 was prepared as a coating composition. The new organic / inorganic hybrid copolymer composition thus prepared was subjected to a measurement of a temperature range of 50 to 300 占 폚 using a thermogravimetric analyzer (TA instruments, model number: SDT Q600) according to ISO 11358 The pyrolysis temperature was measured. The measurement results are shown in Fig. Referring to FIG. 1, it can be seen that the composition comprising the novel organic or inorganic hybrid copolymer prepared through Example 4 is stable at high temperature except for mass loss and endothermic reduction at less than 80 ° C due to volatilization of the solvent used .
Experimental Example 3: Adhesive force measurement
The polyimide film coated with the new organic / inorganic hybrid copolymer prepared in Example 5 was scratched in a lattice pattern on the surface using a cross hatch cutter (manufacturer: YU-KIN Corporation, model name: YCC-230/1) The adhesion of the coating film was measured according to ASTM D6677. Adhesion was evaluated by scaling from 1B to 5B according to the KS L 2108 and KS L 2107 methods of thin film adhesion test of organic substrates. The closer to 5B, the greater the adhesive force, and the closer to 1B the smaller the adhesive force. The measurement results are shown in Fig. Referring to FIG. 2, it can be seen that the composition coated with the novel organic / inorganic hybrid copolymer of Example 5 prepared in Example 4 has excellent adhesion to the polyimide film.
Although the present invention has been described based on the exemplary embodiments and examples of the present invention, the present invention is not limited to the technical ideas described in the above-described embodiments and examples. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. It will be apparent, however, that such modifications and variations are all within the scope of the present invention.
Claims (12)
(In the general formula (Ⅰ) R is a hydrogen atom, each independently C 1 -C 20 alkyl, C 1 -C 20 alkoxy group, C 2 -C 20 alkenyl, C 6 -C 18 aryl, C 3 -C 20-alkyl acrylate group, C 4 -C 20 alkyl methacrylate groups, C 1 -C 20 aminoalkyl group, a mercapto group, a sulfonic acid group, C 1 -C 20 alkyl group selected from the group consisting of vinyl, and vinyl; R 1 And R 2 are each independently a hydrogen atom or a C 1 -C 10 alkyl group, R 3 and R 4 are each independently a C 1 -C 10 alkylene group, m and n are each a number in the range of 0.2-0.8, m + n = 1)
Comprising radical-reacting an alkoxysilane compound represented by the following general formula (III) and an unsaturated ethylenic compound represented by the following general formula (IV).
(R, R 1 , R 2 , R 3 and R 4 in the general formulas (III) and (IV) are the same as defined in the general formula (I)
(In the general formula (Ⅴ) R is a hydrogen atom, each independently C 1 -C 20 alkyl, C 1 -C 20 alkoxy group, C 2 -C 20 alkenyl, C 6 -C 18 aryl, C 3 -C 20-alkyl acrylate group, C 4 -C 20 alkyl methacrylate groups, C 1 -C 20 aminoalkyl group, a mercapto group, a sulfonic acid group, C 1 -C 20 alkyl group selected from the group consisting of vinyl, and vinyl; R 1 And R 2 are each independently a hydrogen atom or a C 1 -C 10 alkyl group, R 3 and R 4 are each independently a C 1 -C 10 alkylene group, R 5 and R 6 are each independently a hydrogen atom, C 1 C 2 -C 20 alkyl group, C 1 -C 20 alkoxy group, C 2 -C 20 alkenyl group, C 6 -C 18 aryl group, C 3 -C 20 alkyl acrylate group, C 4 -C 20 alkyl methacrylate group, C 3 -C 20 alkyl vinyl group and vinyl group, R 7 is a C 1 -C 10 alkyl group or a C 6 -C 18 aryl group, R 8 is a hydrogen atom, a C 1 -C 10 alkyl group, a C 2 -C 20 alkoxyalkyl group, C 2 -C 20 alkenyl, C 6 -C 18 aryl, C 7 -C 19 al A number of m and n are each 0.2 to 0.8 range, provided that m + n = 1 Im;; aryl group, C 7 -C 19 alkoxyaryl groups, C 3 -C 20 alkyl, vinyl, and a vinyl group selected from o and p Is a number ranging from 0.02 to 0.98, with the proviso that o + p = 1 and q is an integer from 1 to 5)
Converting the silicon alkoxy group of the organic copolymer represented by the following general formula (I) into a silanol type and converting it into an organic copolymer of the following general formula (II); And
Grafting a silazane-based copolymer of the following formula (VI) to a hydrated organic copolymer of the following formula (II).
(Wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , m, n, o, p and q is the same as defined in formula (V)
(R, R 1 , R 2 , R 3 and R 4 in the general formulas (III) and (IV) are the same as defined in the general formula (I)
Wherein R 5 , R 6 , R 7 , R 8 and q are the same as defined in the general formula (VI) in the formulas (VII), (VIII) and (IX) Is a halogen atom)
A coating composition comprising an organic solvent.
(In the general formula (Ⅴ) R is a hydrogen atom, each independently C 1 -C 20 alkyl, C 1 -C 20 alkoxy group, C 2 -C 20 alkenyl, C 6 -C 18 aryl, C 3 -C 20-alkyl acrylate group, C 4 -C 20 alkyl methacrylate groups, C 1 -C 20 aminoalkyl group, a mercapto group, a sulfonic acid group, C 1 -C 20 alkyl group selected from the group consisting of vinyl, and vinyl; R 1 And R 2 are each independently a hydrogen atom or a C 1 -C 10 alkyl group, R 3 and R 4 are each independently a C 1 -C 10 alkylene group, R 5 and R 6 are each independently a hydrogen atom, C 1 C 2 -C 20 alkyl group, C 1 -C 20 alkoxy group, C 2 -C 20 alkenyl group, C 6 -C 18 aryl group, C 3 -C 20 alkyl acrylate group, C 4 -C 20 alkyl methacrylate group, C 3 -C 20 alkyl vinyl group and vinyl group, R 7 is a C 1 -C 10 alkyl group or a C 6 -C 18 aryl group, R 8 is a hydrogen atom, a C 1 -C 10 alkyl group, a C 2 -C 20 alkoxyalkyl group, C 2 -C 20 alkenyl, C 6 -C 18 aryl, C 7 -C 19 al A number of m and n are each 0.2 to 0.8 range, provided that m + n = 1 Im;; aryl group, C 7 -C 19 alkoxyaryl groups, C 3 -C 20 alkyl, vinyl, and a vinyl group selected from o and p Is a number ranging from 0.02 to 0.98, with the proviso that o + p = 1 and q is an integer from 1 to 5)
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20190060576A (en) * | 2017-11-24 | 2019-06-03 | 한국생산기술연구원 | Fluoro-polysilazane materials incorporating fluorine groups and methods for their preparation |
| CN116284571A (en) * | 2021-12-20 | 2023-06-23 | 凯斯科技股份有限公司 | Surface treatment agent for organic-inorganic composite composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150086314A (en) | 2012-11-16 | 2015-07-27 | 닛산 가가쿠 고교 가부시키 가이샤 | Polyimide resin film and electronic-device substrate comprising polyimide resin film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20150086314A (en) | 2012-11-16 | 2015-07-27 | 닛산 가가쿠 고교 가부시키 가이샤 | Polyimide resin film and electronic-device substrate comprising polyimide resin film |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190060576A (en) * | 2017-11-24 | 2019-06-03 | 한국생산기술연구원 | Fluoro-polysilazane materials incorporating fluorine groups and methods for their preparation |
| CN116284571A (en) * | 2021-12-20 | 2023-06-23 | 凯斯科技股份有限公司 | Surface treatment agent for organic-inorganic composite composition |
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