WO2019022545A1 - Solvent-free thermosetting organic/inorganic hybrid insulating material - Google Patents

Abstract

The present invention relates to a solvent-free thermosetting organic/inorganic hybrid insulating material comprising: 10 wt% or more of an oligosiloxane having a thermosetting organic group; 10 wt% or more of an organic monomer or an organic oligomer having a carbonated chain structure, and having a thermosetting organic group on the side chains and ends thereof; 20 wt% or less of nanoparticles having a spherical particle form and having a thermosetting organic layer substituted on the surface thereof; 1-15 wt% of a curing accelerator having an organic group capable of covalently bonding by heat treatment; a thermosetting initiator for initiating a thermosetting reaction together with the thermosetting organic group by heat treatment, and a thermosetting agent for proceeding with the thermosetting reaction; 0.01-5 wt% of a thermosetting catalyst to be added so as to accelerate the thermosetting reaction; 0.1-3 wt% of an amphiphilic dispersion stabilizer being polar and nonpolar at both ends thereof; 0.1-15 wt% of a surface energy controller for controlling surface energy; 0.1-10 wt% of a liquid flow control agent composed of liquid; 1-15 wt% of an adhesion enhancer having a carbonated chain structure or a siloxane structure; and 0.1-5 wt% of an antifoaming agent, wherein viscosity is controlled through amounts of the oligosiloxane, the organic monomer or the organic oligomer, and the nanoparticles, and an organic network is formed by heat treatment among the thermosetting organic groups included in respective components. Therefore, the present invention can obtain: an effect of enabling the viscosity of a thermosetting organic/inorganic hybrid insulating material to be controlled in a solvent-free condition by mixing a thermosetting organic material and an organic/inorganic hybrid oligosiloxane material, which have various molecular weights and viscosities; and improved physical properties by adding characteristics and the like, such as water resistance, hardness, low shrinkage and fast curing, of each of the mixed organic material and oligosiloxane material to an organic/inorganic hybrid material.

Description

Non-solvent type thermosetting organic / inorganic hybrid insulating material

The present invention relates to a solventless thermosetting organic / inorganic hybrid material, and more particularly, to a hybrid inorganic / organic hybrid material having various molecular weights and viscosities and a hybrid organic oligosiloxane material, And more particularly, to a thermosetting and non-dispersible hybrid inorganic insulating material.

In general, inorganic materials have excellent properties such as corrosion resistance, chemical resistance, abrasion resistance, heat resistance, hardness, moisture and gas barrier, and are actively used in such fields as structural materials, protective coating materials, abrasive materials, . Minerals with such physical properties are also required to be applied to electric, electronic, and energy materials, and active research for application is underway. However, in addition to the high cost and dry process required for the production of inorganic minerals, the produced inorganic materials are difficult to produce as a thick film due to the brittleness of the material itself, and there are many limitations in applying a simple wet process.

In order to overcome these limitations, researches on the preparation of colloidal inorganic nano-sols capable of wet processing without deteriorating the existing properties of inorganic materials and dispersion studies for application of inorganic materials to wet materials have been conducted. In the case of the conventional inorganic nano-sol, it is generally used as a structural material, and it is possible to improve the mechanical, thermal and chemical properties of the inorganic material by forming a hybrid organic composition by mixing with a polymer resin, which is an organic binder, there was.

Such conventional organic / inorganic hybrid compositions are disclosed in Korean Patent Registration No. 10-1454447 as a method for manufacturing a composite material for improving durability and insulation, and Korean Patent Application No. 10-2016-0014971, which discloses high transparency, And a method of producing a hybrid coating material having the above-mentioned properties. However, when preparing a hybrid composition including a solvent, a step of removing the solvent must be separately included in the process of applying the hybrid composition. In addition, since the solvent may be harmful to the environment or human body, a hybrid composition not containing a solvent It is ideal to obtain. Accordingly, there is known a technique for obtaining a solvent-free composition such as the prior art 'Korean Patent Office Registration No. 10-1198316 Silica Sol for Solvent Formulation and its Manufacturing Method'. However, even in the case of a conventional solventless composition, And then removing the solvent. Therefore, there is a problem that it is difficult to protect the environment or the human body because the process of removing the solvent is reduced or the harmful solvent is not used.

In addition, when the organic hybrid composition is prepared without using a solvent as described above, since the solvent is not used, the viscosity is not easily controlled and the viscosity is high at about 3000 to 10000 cp. It is difficult to perform smoothly.

Accordingly, it is an object of the present invention to provide a solvent-free thermosetting and non-aqueous organic hybrid material capable of controlling the viscosity of a hybrid insulation material under a solventless condition by mixing a thermosetting organic material having various molecular weights and viscosities with an organic hybrid oligosiloxane material .

The above object is achieved by a thermoplastic resin composition comprising 10% by weight or more of an oligosiloxane having a thermosetting organic group; At least 10% by weight of an organic monomer or organic oligomer having a carbon chain structure and having a side chain and a thermosetting organic group at a terminal thereof; Up to 20% by weight of nanoparticles in the form of spherical particles substituted with thermosetting organic groups on their surfaces; 1 to 15% by weight of a curing accelerator having an organic group capable of being covalently bonded by heat treatment; A thermosetting initiator for initiating a thermosetting reaction together with the thermosetting organic group through heat treatment and a thermosetting agent for promoting a thermosetting reaction; 0.01 to 5% by weight of a thermosetting catalyst added to accelerate the thermosetting reaction; 0.1 to 3% by weight of a dispersion stabilizer having polarity and non-polarity polarity at both ends thereof; 0.1 to 15% by weight of a surface energy modifier for surface energy control; 0.1 to 10% by weight of a liquid flowability-regulating agent in a liquid phase; 1 to 15% by weight of an adhesion promoter composed of a carbon chain structure or a siloxane structure; And 0.1 to 5% by weight of an antifoaming agent, wherein viscosity is controlled through the content of the oligosiloxane, the organic monomer or the organic oligomer, and the nanoparticles, and the organic network between the thermosetting organic units Wherein the thermosetting organic / inorganic hybrid material is a non-solvent type thermosetting organic / inorganic hybrid material.

The oligosiloxane preferably has a molecular weight of 300 to 3,000 and the molecular weight of the organic monomer or the organic oligomer is preferably 100 to 10,000. The nanoparticles may be organic nanoparticles, inorganic oxide nanoparticles, And the organic nanoparticles are selected from the group consisting of polystyrene, polyurethane, polymethylmethacrylate, and mixtures thereof, and the inorganic nanoparticles are selected from the group consisting of , Silica, zirconia, alumina, titania, and mixtures thereof.

 It is preferable that the thermosetting initiator is a radical thermosetting initiator or a cationic thermosetting initiator and that the type of the thermosetting initiator is selected depending on the kind of the thermosetting organic group. The thermosetting agent may be selected from the group consisting of the oligosiloxane having the thermosetting organic group, And a functional group selected from the group consisting of an acid anhydride system, a phenolic system, an isocyanate system, a mercaptan system, an amine system, and a mixture thereof.

The curing accelerator includes a thermosetting organic group at one end and a side chain, and at least one of a hydroxyl group, a carboxyl group, a phosphate group, an amine group, an epoxy group, an oxetane group, an olefin group, a urethane group, A functional group selected from the group consisting of an acrylic group, a methacryl group, an aryl group, a vinyl group urethane group, a mercapto group, a carboxyl group, an amine group, an olefin group and a mixture thereof.

Preferably, the hybrid insulation material further comprises a surface leveling agent, and the surface leveling agent is selected from the group consisting of silicone resin, silane, acrylic resin, methacrylic resin, fluorine resin, and mixtures thereof.

According to the constitution of the present invention described above, it is possible to control the viscosity of a thermosetting organic / inorganic hybrid material in a non-solvent condition by mixing a thermosetting organic material having various molecular weights and viscosities and an organic hybrid oligosiloxane material, The improved physical properties of the organic and oligosiloxane materials added to the organic hybrid materials can be obtained, such as water resistance, hardness, low shrinkage and fast curing properties.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a solventless thermosetting organic / inorganic hybrid material according to an embodiment of the present invention will be described in detail.

The solventless thermosetting organic / inorganic hybrid material of the present invention includes an oligosiloxane, an organic monomer or an organic oligomer and nanoparticles, and the viscosity of the insulating material is controlled by the oligosiloxane, organic monomer or organic oligomer and nanoparticles. Therefore, the solventless thermosetting inorganic hybrid An insulating material can be obtained. In other words, when high viscosity is desired according to the application field of organic / inorganic hybrid insulating material, an insulating material is produced by controlling the viscosity to a high level. When an insulating material having low viscosity is required, conventionally, In the present invention, it is possible to obtain an insulation material capable of controlling the viscosity of the solventless type through controlling the mixing ratio of oligosiloxane, organic monomer or organic oligomer and nanoparticles.

The oligosiloxane, organic monomer or organic oligomer mixed for controlling the viscosity of the insulating material, the first of the nanoparticles, since the oligosiloxane is basically a material having a high molecular weight, if the content of oligosiloxane is increased, the viscosity of the insulating material is increased do. The organic monomer or organic oligomer is suitable for obtaining an insulating material having a low viscosity when the molecular weight is smaller than the oligosiloxane, and the viscosity of the insulating material can be increased when the molecular weight of the organic oligomer is higher than that of the siloxane. Also, as the content of nanoparticles increases, the viscosity increases. Therefore, when an insulating material having a high viscosity is required as in the case of oligosiloxane, the content of the nanoparticles increases within the control range of the physical properties. However, in the case of an insulating material requiring light transmittance, it is necessary to control the size and content of nanoparticles according to required light transmittance.

Oligosiloxane has siloxane as the main structure and functional organic groups at the side chain and terminal. Wherein the functional organic group comprises a thermoset organic group and may further comprise a functional organic group other than a thermosetting organic group. The thermosetting organic group means a radical thermosetting organic group capable of acting in radical thermal polymerization or a cationic thermosetting organic group capable of acting in cationic thermal polymerization. The thermosetting organic group is preferably selected from the group consisting of a cycloaliphatic epoxy group, a glycidyl epoxy group, an ether group, a cyclic acetal group, a cyclic sulfide group, a lactone group, a lactam group, an oxetane group and a mixture thereof. Here, the number of functional organic groups is at least one, and it may have a polyfunctional organic group.

The oligosiloxane containing a thermosetting organic group and further containing a functional organic group preferably has a molecular weight of 300 to 3000. It is preferable to use an oligosiloxane having a molecular weight controlled and a mixture of oligosiloxanes having different molecular weights, The viscosity can be controlled in various ways. Oligosiloxane is difficult to form with a molecular weight of less than 300, and when the molecular weight exceeds 3000, the viscosity is so high that it can not be uniformly mixed with other components during mixing to form an insulating material, Therefore, the molecular weight of the oligosiloxane is preferably 300 to 3,000.

The oligosiloxane is preferably contained in an amount of 10% by weight or more based on 100% by weight of the total composition. This is because the oligosiloxane together with the organic monomer or organic oligomer in the insulating material corresponds to the base component. Therefore, it is preferable that 10 wt% or more of the total composition is contained in order to smoothly mix with other components, and 50 wt% have. The oligosiloxane may additionally contain other organic substituents as well as thermosetting organic groups, wherein the organic substituent may be an alkyl group, a perfluoroalkyl group, a hydroxyl group, a carboxylate group, or the like.

The organic monomer or organic oligomer has a main structure of a carbonized chain structure and a thermosetting organic group at its side chain and terminal. When the molecular weight is small, the viscosity of the insulating material can be reduced. When the molecular weight is large, Can be increased. In particular, the main structure of the carbon chain of the organic oligomer is selected from the group consisting of a cycloaliphatic epoxy group, a glycidyl epoxy group, an ether group, a cyclic acetal group, a cyclic sulfide group, a lactone group, a lactam group, . The thermoset organic group contained in the organic monomer or organic oligomer means a radical thermosetting organic group or a cationic thermosetting organic group like the oligosiloxane. Here, when the oligosiloxane contains a radical thermosetting organic group, it is preferable to use a material including a radical thermosetting organic group in the organic group, and vice versa. This is because, when thermally curing after applying the insulating material, if different organic groups are included, the efficiency of the thermal curing process such as a long heat treatment time for complete thermal curing may be lowered. The kind of radical thermosetting organic group and the kind of cationic thermosetting organic group are applicable to the same as oligosiloxane. Also, the number of functional organic groups possessed by the organic monomer and the organic oligomer is at least one or more, and may be a polyfunctional organic group.

The molecular weight of the organic monomer or organic oligomer is preferably 100 to 10,000, and when the molecular weight is closer to 100, the viscosity of the insulating material can be reduced. When the organic oligomer having a molecular weight close to 10,000 is used, It is possible to adjust the amount appropriately according to the viscosity of the insulating material required. Such an organic monomer or organic oligomer may be contained in an amount of 10% by weight or more, preferably 50% by weight or more, based on 100% by weight of the entire composition, and the range may be adjusted according to required properties. When the content of the organic monomer or organic oligomer is less than 10% by weight, the viscosity of the insulating material can not be controlled properly. Viscosity can also be controlled by using some kinds of organic materials having different molecular weights and molecular weights.

Nanoparticles having a spherical particle shape mean organic nanoparticles, inorganic oxide nanoparticles, silicon nanoparticles, and particles composed of a mixture thereof, and thermosetting organic groups are substituted on the surface of the particles.

Among them, the organic nanoparticles similarly have a carbonized-chain structure as a main structure, and a functional organic group at a side chain and a terminal. Examples of the organic nanoparticles include, but are not limited to, polystyrene, polyurethane, polymethylmethacrylate, and mixtures thereof. The organic nanoparticles may have a particle size of 1 to 500 nm. If the thickness of the organic nanoparticles is less than 1 nm, it is impossible to produce the organic nanoparticles. When the thickness exceeds 500 nm, So that it is not beautiful in appearance.

The optimum content of the organic nanoparticles is preferably in the range of 0 to 20 wt% based on the total mass weight ratio of the composition. That is, the organic nanoparticles may not be added if necessary, desirable. A more preferable addition amount is 10% by weight or less. Since the organic nanoparticles are polymers, the viscosity of the insulating material increases as the content of the organic nanoparticles increases. Therefore, the viscosity can be controlled by controlling the content. It also reduces the shrinkage after curing and improves the flatness of the surface. These organic nanoparticles can be expected to contribute to enhancement of mechanical properties and dimensional stability of the coating film and the structure through size control and mixing of different size particles.

The inorganic oxide nanoparticles are selected from the group consisting of silica, zirconia, alumina, titania, and mixtures thereof. The particle size is preferably 1 to 500 nm, similarly to the organic nanoparticles. The inorganic oxide nanoparticles are preferably contained in an amount of 0 to 20 wt%, more preferably 10 wt% or less, based on 100 wt% of the entire composition. The inorganic oxide nanoparticles not only control the viscosity through the content control but also reduce the shrinkage after curing as in the case of the organic particles, thereby improving the flatness of the surface and improving the mechanical properties. It can be expected to contribute not only to the content but also to the mechanical properties of the coating film and the structure and to the dimensional stability through control of the size and mixing of different size particles. However, when the dispersibility is lowered, uniform dispersion is required because the light transmittance is lowered and the flatness and the related mechanical properties may be lowered due to problems such as aggregation.

Silicon nanoparticles are spherical particles that have a siloxane structure as the main structure. The optimum content of the silicon nanoparticles is in the range of 0 to 20 wt%, more preferably 10 wt% or less, of 100 wt% of the whole. By controlling the content of silicon nanoparticles, it is possible not only to control the pores but also to reduce the shrinkage after curing and improve the flatness.

Organic nanoparticles, inorganic oxide nanoparticles, and silicon nanoparticles are added when the viscosity control and shrinkage-preventing function are not sufficient by the composition of oligosiloxane, organic monomer or organic oligomer. The shrinkage problem that occurs during the heat treatment increases the density of the structure while strengthening the siloxane network, which can prevent shrinkage considerably. However, in order to improve the dimensional stability of a coating film or a structure, organic nanoparticles, inorganic oxide nanoparticles, or silicon nanoparticles are added to and mixed with the main component, and the deformation caused by heat treatment and curing is supported by organic or inorganic nanoparticles Can be prevented. Therefore, the surface change of the coating film can be minimized, and the coating film and the dimensional stability of the formed structure can be contributed. However, when the particle size is too large or when too much content is applied, the mechanical properties such as shrinkage prevention can be increased but the optical transmittance may be lowered. Therefore, size control of organic nanoparticles to be mixed with the content control is indispensable. In addition, the mixing of these nanoparticles can increase the viscosity of the mixed constituent solution and can act as an incremental agent when an increase in viscosity is required in the process. However, as mentioned above, the dispersion of the matrix material of the heterogeneous nanoparticles causes problems such as flocculation and settling primarily due to the difference in surface energy, and due to such a problem, the drop of the optical thickness of the coating film and the cause of the surface defect of the coating film Uniform distribution of organic and inorganic nanoparticles having viscosity control and anti-shrinkage function is indispensable. A dispersant is necessarily required for such uniform dispersion.

The thermosetting organic / inorganic hybrid insulating material should further include not only oligosiloxane, organic monomer or organic oligomer, nanoparticles but also a curing accelerator, a thermosetting initiator, a thermosetting agent, a thermosetting catalyst, a dispersion stabilizer, a surface energy regulator, a liquid flow regulator, .

The curing accelerator is used for enhancing adhesion of thermosetting organic monomer, oligomer and polymer, enhancing durability, enhancing chemical resistance, and acting as a crosslinking promoter. It is also used as a crosslinking agent capable of covalent bond by heat, such as hydroxyl group, carboxyl group, phosphate group, , An epoxy group, an olefin group, a urethane group, and a mixture thereof. Or an organosilane containing a functional group selected from the group consisting of a hydroxyl group, a hydrogen group, a urethane group, a mercapto group, a carboxyl group, an amine group, an olefin group and a mixture thereof may act as a curing accelerator.

The content of the curing accelerator is 1 to 15% by weight, more preferably 5% by weight or more, of 100% by weight of the whole. A hybrid material coating film after thermosetting for improving chemical bonding to oligosiloxane, organic monomer, oligomer or polymer having a thermosetting organic group and improving adhesion to various substrates and materials such as metal, glass, electrode, film and the like through a curing accelerator And the mechanical properties including the adhesive force of the hybrid material can be improved. Further, not only is there a merit that mechanical properties such as shrinkage and cracking after the curing of thermosetting resin can be lowered, but also water resistance and chemical resistance can be enhanced at the same time.

The thermoset initiator can be divided into a cationic thermal initiator and a radical thermal decomposition agent. The cationic thermal initiator is an ionic compound composed of an organic cation and an initiator having an inorganic anion as a double ion. Refers to a compound that generates organic cations and inorganic anions in the presence of monomers through exposure to thermal energy, and the bonds of weak chemical bonds are broken by heat to form cations and anions. The ions formed can serve to initiate and grow the cationic thermosetting reaction. Typical cationic thermal initiators are preferably selected from the group consisting of organic metal salts, iodonium salts, metallocene compounds, aromatic diazonium salts, triarylsulfuric acid salts, latent sulfuric acid, and mixtures thereof.

The content of the cationic thermal initiator is preferably 0.1 to 10% by weight based on 100% by weight of the oligosiloxane, organic monomer, organic oligomer or organic polymer having a thermosetting organic group. When the amount of the cationic initiator is less than 0.1 wt%, it takes a long time for the heat curing to take place by heat treatment. When the amount exceeds 10 wt%, the heat curing is performed within a very short period of time, There is a problem that curing occurs.

A radical thermal initiator is a compound that generates radicals in the presence of monomers through heat. Radicals are formed by breaking bonds at weak chemical bonds by heat. The radicals formed may serve to initiate the thermosetting reaction together with the thermosetting organic groups. As the radical thermal initiator, a peroxide initiator is typically used, and the peroxide initiator is selected from the group consisting of benzoyl peroxide, acetyl peroxide, dilauryl peroxide, potassium persulfate, and mixtures thereof. In addition to the peroxide initiator, the azo compound system can also be used as a thermosetting initiator capable of forming radicals by heat.

The content of the radical thermal initiator is preferably 1 to 5% by weight based on 100% by weight of the oligosiloxane, organic monomer, organic oligomer or organic polymer having a thermosetting organic group. When the radical scavenging agent is less than 1% by weight, it takes a long time for thermal curing to take place by heat treatment. If it exceeds 5% by weight, the thermosetting is performed within a very short period of time, There is a problem that curing occurs.

The oligosiloxane containing a radical thermosetting organic group is thermoset through the following action. Si-O-Si (siloxane) network is formed through a sufficient condensation reaction in the process of synthesizing an insulating material including an oligosiloxane, and a thermosetting radical thermosetting organic group is formed on the siloxane network in a four- The main structure of the siloxane network contains a radical thermosetting organic group in the side chain and the like. Since the organic radicals and organic oligomers containing the same radical thermosetting organic groups are mixed together, the organic network structure of the siloxane inorganic structure and the radical thermosetting organic group can be obtained through heat treatment as well as the siloxane network formed in the solution reaction. Can be formed at the same time.

Here, the organic crosslinking of the radical thermosetting organic group is promoted and the whole organic network reaction proceeds, and the organic network progresses sufficiently through the heat treatment. Finally, the chemical structure of the hybrid insulation material can form an organic / inorganic chemical structure through formation of a sufficient organic network structure of the radical thermosetting organic group through the siloxane inorganic network structure and the heat treatment through the solution synthesis of the siloxane material. However, in the case of the insulating material composed only of the oligosiloxane main component, it is necessary to compensate for the shrinkage caused by thermal curing, the more closely adherence to the substrate, and the improvement of the chemical resistance related thereto, and depending on the process, The molecular weight control of the oligosiloxane main component may be added, or a component having various viscosities may be constituted through mixing of the main components having different molecular weights.

In addition, in the organic network reaction through heat treatment, the structure of the organic network through the mixing of the organic monomers and the organic oligomers having different molecular weights and the chemical structure of the organic compounds through the heat treatment of the oligosiloxane and the organic monomer or organic oligomer . In addition to viscosity control by controlling the molecular weight of the main components such as oligosiloxane, organic monomer or organic oligomer, it is possible to control the water resistance, hardness, low shrinkage, chemical resistance, Fast curability and other properties. In addition, functional added materials are required to facilitate dispersion among different dissimilar materials.

The thermosetting agent and the thermosetting catalyst are added so as to promote thermosetting through heat treatment. The thermosetting agent is selected from the group consisting of acid anhydride, phenolic, isocyanate, mercaptan, amine and mixtures thereof. At this time, the content of the thermosetting agent is determined theoretically in consideration of the equivalent of the host material. In the case of the thermosetting catalyst, an amine-based catalyst or phosphorus-based catalyst may be used. The content of the thermosetting catalyst may be 0.01 to 5 wt% of 100 wt%. This can determine the content depending on the required curing temperature, curing time and required process temperature, and can increase the curing density as well as increase the bond strength with use of the curing catalyst.

The dispersion stabilizer is a composition that facilitates dispersion of nanoparticles, inorganic oxide nanoparticles, silicon nanoparticles, oligosiloxane, organic monomers, or organic oligomers. As the dispersion stabilizer, organic polymers having polarities of polarity and non- A silane, a bipolar organic monomer, and a mixture thereof. The dispersant may be used in an amount of 0.1 to 3% by weight, preferably 1% by weight, based on 100% by weight of the total composition.

The surface energy regulator plays a role in control of material flow, defect control such as pinhole, and improvement of wet processability by controlling the surface energy of the hybrid material of the non-use type. The surface energy regulator is preferably selected from the group consisting of silicone resins, silanes, acrylic resins, methacrylic resins, fluororesins, and mixtures thereof. The content of the surface energy regulating agent can be appropriately adjusted from 0.1 to 15% by weight based on 100% by weight of the whole.

The flow control agent is in the form of a liquid phase, which is additionally controllable to control the viscosity. By controlling the viscosity and flowability, it improves wet processability, improves flow control and storage stability, and controls the thickness of the coating film. Examples of the fluidity controlling agent include polycarboxylic acid amides, polyhydroxycarboxylic acid amides, polyhydroxycarboxylic acid esters, modified ureas, urea-modified polyurethanes, polyamides and And mixtures thereof. The fluidity control agent may be used in an amount of 0.1 to 10% by weight, preferably 5% or more, based on 100% by weight of the total composition. When the amount of the flow control agent is less than 0.1 wt%, it is difficult to finely control the viscosity of the insulating material. When the amount of the flow control agent is more than 10 wt%, the liquid flow control agent fails to thermoset.

The antifoaming agent is added to remove air bubbles which can be caused by mixing the components contained in the hybrid insulation material, and can exhibit such effects as wet processability improvement, coating film defect control, and appearance improvement. The defoaming agent may be classified into a silicone type and a non-silicone type. The silicone type is polysilicon. The non-silicone type is selected from the group consisting of acrylic resin, fluorine-acrylic resin, fluorine resin and mixtures thereof. Do. Such antifoaming agents may be added in an amount of 0.1 to 5% by weight, preferably 3% by weight, based on 100% by weight of the total composition. If the antifoaming agent is less than 0.1 wt%, the bubbles can not be removed sufficiently, and if the antifoaming agent is more than 5 wt%, the uniform dispersion between the components may be hindered.

The hybrid insulation material of the present invention may further be mixed together with an adhesion promoter and a surface leveling agent. Among these, the adhesion promoter has a thermosetting organic group at one terminal and side chains while having a carbon chain structure or a siloxane structure as a main structure and has a hydroxyl group, a carboxyl group, a phosphate group, an amine group, an epoxy group, Oxetane groups, olefin groups, urethane groups, and mixtures thereof. Or an organosilane containing functional groups selected from the group consisting of a hydroxyl group, an acrylic group, a methacrylic group, an aryl group, a vinyl group urethane group, a mercapto group, a carboxyl group, an amine group, an olefin group, It may also act as an enhancer. The content of the adhesion-promoting agent is preferably 1 to 15% by weight, more preferably 5% by weight, of 100% by weight of the total composition.

In the case of a material comprising an oligosiloxane, an organic monomer or an organic oligomer or nanoparticles, if the reaction site is not enough to form a chemical bond through a covalent bond with the substrate or a hydrogen bond, the chemical bond with the substrate and the cross- Adhesion promoting agent that can be used in the present invention is required. It is possible to improve the adhesion to various substrates and materials such as metals, glass, electrodes, films and the like through the adhesion promoter and to improve the chemical crosslinking with oligosiloxane, organic monomer or organic oligomer having a thermosetting organic group, The mechanical properties including the adhesive force of the material can be improved.

The surface leveling agent can control the flow control of insulation material, defect control such as pinhole, and improve wet processability through surface energy control of solventless type hybrid insulation material. The surface leveling agent may be selected from the group consisting of silicone resins, silanes, acrylic resins, methacrylic resins, fluororesins, and mixtures thereof, but is not limited thereto. Also, the content of the surface leveling agent may be 0.1 to 15% by weight, preferably 5% by weight or more, of 100% by weight of the total composition.

Hereinafter, embodiments of the present invention will be described in more detail.

≪ Examples 1 to 5 >

Examples 1 to 5 use a cationic thermosetting type system and use an aqueous nitric acid solution which is a catalyst for hydrolysis and condensation reaction of epoxycyclohexylethyltrimethoxysilane having a cycloaliphatic epoxy group as an organic group capable of cationic thermosetting A thermosetting epoxy cycloaliphatic siloxane was prepared. Here, the molecular weight can be controlled by controlling the reaction parameters including the concentration of the catalyst and the reaction time. The molecular weight of the produced siloxane is approximately 2,000 to 3,000, respectively, and the molecular weight can be controlled up to 3,000 by increasing the catalyst concentration and the reaction time. This molecular weight control can control the viscosity of the solution, which is an important process parameter of the wet material. The molecular weight control can also improve the mechanical and chemical properties of the insulating material after final curing. In Examples 1 to 5, cationic thermosetting cycloaliphatic epoxy siloxane having a molecular weight of 2,000 to 3,000 was prepared and used as a main constituent material of a transparent hybrid insulation material. The content was 25 to 75% by weight of 100% And the viscosity of the solution can be controlled according to the mixing amount.

Next, 10 to 70% by weight of an organic monomer having a molecular weight of about 140, which has a thermosetting epoxy cycloaliphatic organic group and mixed with the mixed siloxane, is mixed with 100% by weight of the total composition, and the polystyrene nanoparticles having an average size of 60 nm are mixed with a siloxane The organic monomer mixture was mixed with a solution of 10 wt% based on 100 wt% of the total composition, and then the materials and the properties of the coating film were compared with each other. The mixing method of the constituent materials was uniformly mixed using a high viscosity vacuum mixing mixer to obtain a transparent solution. Polystyrene nano-organic particles having a size of 60 nm were prepared by mixing styrene monomer, water as a reaction solvent, acetone and AIBA (2-methylpropionamidine) as a cationic initiator, DVB (divinyl benzene) as a crosslinking agent, PVP polyvinylpyrrolidone) for 24 hours at 70 ° C. Polymerization Polystyrene organic nanoparticles were finally made into polystyrene nanoparticles through centrifugation and solvent drying.

Si-60L (Sanshin Chem.) Was mixed in an amount of 1.5% by weight at the time of cationic curing for thermosetting and 1.5% by weight of an amine-based adhesion promoter was added to a mixed solution containing siloxane, organic monomer and nano- A leveling agent, a bipolar ether-type polymer dispersant, a polycarboxylic acid amide-based fluidity control agent and a non-silicone-based defoaming agent were each mixed at 0.5 wt%, and finally a transparent thermosetting organic hybrid material . At this time, mixing of the hybrid insulation material was able to obtain a transparent and uniformly mixed insulating material by using a high viscosity vacuum stirring mixer.

As can be seen from the following Table 1, the obtained hybrid insulation material has a viscosity of 250 to 25,000 cp, which can control the viscosity by controlling the molecular weight, content, or particle size of the mixed material. The prepared thermosetting organic / inorganic hybrid insulation material is coated on a glass and metal substrate having a size of 10 cm × 10 cm by bar coating to have a thickness of about 10 μm. The prepared coating film was thermally treated in an oven at 130 ° C. for 30 minutes to finally produce a thermally cured tubular insulation insulating film. The results of confirming the permeability, adhesive strength, cracking resistance and chemical resistance of the organic solvent of the prepared transparent hybrid insulating material film were confirmed to have excellent physical properties as shown in Table 1. These physical properties may be different depending on the blending ratio of the mixed constituent materials and the kinds of the applied materials. Therefore, the selection of the constituent materials and the determination of the mixing ratio are very important factors for control and enhancement of physical properties.

Experimental results according to Examples 1 to 5 are shown in Table 1. Here, the degree of hardening is determined by checking whether or not sticky after curing, and it is expressed as?: Very excellent,?: Excellent,?: Poor, and X: poor. The viscosity is measured with a Brookfield viscometer, the UV-Vis spectroscopy (Coatings on quartz glass), and the adhesive strength measured with a cross-cut tape test (ASTM D3359-97). In case of cracks, it is measured by visual observation after curing of coating film and OEM observation. In case of chemical resistance, DI water, alcohols, medium polarity cellosolve, and nonpolar ketone were applied. Cracking, swelling, decomposition, etc. of the coating film after seven days from completely immersing the coating film in each solvent were measured by visual observation and OEM observation. The results are shown as ⊚: very excellent, ◯: excellent, △: insufficient, and X: defective.

Siloxane is a thermal curable cyclo-epoxy siloxane and the monomer is a cationic thermal epoxy monomer.

	Example 1	Example 2	Example 3	Example 4	Example 5
Siloxane (MW: 2,000 ~ 3,000)	75	75	50	50	25
The monomer (MW: 140)	10	25	40	45	70
PS nanoparticles	10	-	5	-	-
Thermal initiator (SL-60L)	1.5	1.5	1.5	1.5	1.5
Adhesion promoter	1.5	1.5	1.5	1.5	1.5
Surface leveling agent	0.5	0.5	0.5	0.5	0.5
Dispersion stabilizer	0.5	0.5	0.5	0.5	0.5
Liquid fluidity control agent	0.5	0.5	0.5	0.5	0.5
Defoamer	0.5	0.5	0.5	0.5	0.5
Degree of hardening	◎	◎	◎	◎	◎
Viscosity (cP)	~ 25,000	~ 10,000	~ 3,500	~ 1,500	~ 300
Permeability (%)	91	91	91	91	91
Adhesion (B)	5	5	5	5	5
Crack (O: yes, X: no)	X	X	X	X	X
Chemical resistance	◎	◎	◎	◎	◎

≪ Examples 6 to 10 >

In Examples 6 to 10, a thermosetting glycidyl epoxy siloxane was prepared by using a nitric acid aqueous solution as a catalyst for the hydrolysis and condensation reaction of glycidylpropyl methoxysilane having a glycidyl epoxy group as an organic group capable of thermosetting . Here, the molecular weight can be controlled by controlling the reaction parameters including the concentration of the catalyst and the reaction time. The molecular weight of the prepared siloxane was approximately 2,000 to 3,000, respectively, and the molecular weight could be controlled up to 3,000 by increasing the catalyst concentration and the reaction time. This molecular weight control can control the viscosity of the solution, which is an important process parameter of the wet material. The molecular weight control can also improve the mechanical and chemical properties of the material after final curing. In Examples 6 to 10, a thermosetting glycidyl epoxy siloxane material having a molecular weight of 2,000 to 3,000 was prepared and used as a main constituent material of the transparent hybrid insulation material. The content of the glycidyl epoxy siloxane material was 20 to 80 wt% And the viscosity of the solution could be controlled according to the mixing amount.

Next, 20 to 80% by weight of a molecular weight organic monomer and an organic polymer material having thermosetting glycidyl epoxy organic groups in different contents of siloxane material, based on 100% by weight of the total composition, were mixed. An organic anhydride curing agent was mixed with a thermosetting agent for thermosetting in a mixed solution containing a siloxane, an organic monomer and a polymer. The amine curing catalyst was mixed with a siloxane, an organic monomer, a polymer And 0.05% by weight of the total amount of the mixed liquid including the curing agent. (Shin-Etsu chemical Co.) having an average size of 700 nm was mixed with 10 wt% of 100 wt% of a solution containing a siloxane having an epoxy group, an organic monomer, a polymer, a curing agent and a catalyst, And the physical properties of the material and the coating film were compared with each other.

In addition, for adhesion enhancement, an amine-based adhesion promoter containing an excited group was mixed in an amount of 1.5% by weight based on the mixing amount of the epoxy composition and the spherical silicon nano-particles, and a silicone surface leveling agent, a bipolar cross- ) Amide-based fluidity control agent and a non-silicone based defoaming agent were mixed at 0.5 wt% with respect to the mixing amount of the epoxy composition and spherical silicon particles, respectively, to finally prepare a thermosetting epoxy siloxane-epoxy resin hybrid insulation material. At this time, mixing of the hybrid insulation material was able to obtain a transparent and uniformly mixed insulating material by using a high viscosity vacuum stirring mixer.

As can be seen from Table 2, the viscosity of the obtained hybrid insulation material varied from 10,000 to 25,000 cP in the high viscosity region, which could be controlled by controlling the molecular weight and content of the mixed material. By controlling the content of the constituent material in addition to the viscosity range shown in Table 2, it is possible to control the viscosity more variously. The prepared thermosetting organic / inorganic hybrid insulation material is coated on a glass and metal substrate having a size of 10 cm × 10 cm by bar coating to have a thickness of about 10 μm. The prepared coating film was heat treated in an oven at 180 ° C. for 90 minutes to finally produce a thermally cured hybrid insulating film. The results of confirming the surface resistance, adhesive strength, cracking resistance and chemical resistance of the organic solvent of the prepared transparent hybrid insulating material film were confirmed to have excellent physical properties as shown in Table 2. These physical properties may be different depending on the blending ratio of the mixed constituent materials and the kinds of the applied materials. Therefore, the selection of the constituent materials and the determination of the mixing ratio are very important factors for control and enhancement of physical properties.

Experimental results according to Examples 6 to 11 are shown in Table 2. Here, the degree of hardening is determined by checking whether or not sticky after curing, and it is expressed as?: Very excellent,?: Excellent,?: Poor, and X: poor. The viscosity is measured with a Brookfield viscometer, the UV-Vis spectroscopy (Coatings on quartz glass), and the adhesive strength measured with a cross-cut tape test (ASTM D3359-97). In case of cracks, it is measured by visual observation after curing of coating film and OEM observation. In case of chemical resistance, DI water, alcohols, medium polarity cellosolve, non-polar ketone are applied. Cracking, swelling, decomposition, etc. of the coating film after 7 days from completely immersing the coating film in each solvent were measured by visual observation and OEM observation, and were marked as ⊚: very excellent, ◯: excellent, △: insufficient, and X: poor.

The siloxane of the contents shown in the following Table 2 is a thermosetting glycidyl-epoxy siloxane, and the organic monomer and the polymer are a thermosetting glycidyl epoxy monomer and a thermosetting glycidyl Means a thermal curable glycidyl epoxy resin, and the heat curing agent and curing catalyst means an acid anhydride curing agent and an amine curing catalyst.

	Example 6	Example 7	Example 8	Example 9	Example 10	Example 11
Siloxane	80	50	20	-	20	30
Organic monomer	-	10	30	-	10	30
Organic polymer	-	20	30	80	50	20
Heat curing agent	78	79	83	69	75	84
Thermosetting catalyst	0.05	0.05	0.05	0.05	0.05	0.05
Silicon spherical particles	-	10	5	5	10	-
Adhesion promoter	5	5	5	5	5	-
Surface leveling agent	0.5	0.5	0.5	0.5	0.5	0.5
Dispersant	0.5	0.5	0.5	0.5	0.5	0.5
Liquidity control agent	0.5	0.5	0.5	0.5	0.5	0.5
Defoamer	0.5	0.5	0.5	0.5	0.5	0.5
Degree of hardening	◎	◎	◎	◎	◎	◎
Viscosity (cP)	~ 25,000	~ 17,500	~ 12,500	~ 23,000	~ 16,000	~ 10,000
Insulation resistance (Ωcm)	1 x 10 18	1 x 10 18	1 x 10 18	1 x 10 18	1 x 10 18	1 x 10 18
Permeability (%)	91	70	80	80	70	91
Adhesion (B)	5	5	5	5	5	2
Crack (O: yes, X: no)	X	X	X	X	X	X
Chemical resistance	◎	◎	◎	◎	◎	◎

As can be seen from the above examples, the viscosity of the insulating material can be controlled even under solvent-free conditions without using a solvent as in the prior art. In particular, the higher the content of oligosiloxane having a lower molecular weight, the lower the viscosity and the higher molecular weight siloxane content The higher the viscosity, the higher the viscosity. It is also possible to control the viscosity depending on the molecular weight and addition amount of the organic monomer and the organic oligomer, and it is also confirmed that the viscosity increases even when the nanoparticles are included. Thus, a wide range of viscosity can be controlled finely and freely through oligosiloxane, organic monomer or organic oligomer, and nanoparticles. Since the prepared insulating material does not use a solvent, the degree of cure, permeability , Adhesive strength and chemical resistance, and cracks are not formed.

Claims (9)

1. A thermosetting organic / inorganic hybrid insulating material of no solvent type,

   At least 10% by weight of an oligosiloxane having a thermoset organic group;

   At least 10% by weight of an organic monomer or organic oligomer having a carbon chain structure and having a side chain and a thermosetting organic group at a terminal thereof;

   Up to 20% by weight of nanoparticles in the form of spherical particles substituted with thermosetting organic groups on their surfaces;

   1 to 15% by weight of a curing accelerator having an organic group capable of being covalently bonded by heat treatment;

   A thermosetting initiator for initiating a thermosetting reaction together with the thermosetting organic group through heat treatment and a thermosetting agent for promoting a thermosetting reaction;

   0.01 to 5% by weight of a thermosetting catalyst added to accelerate the thermosetting reaction;

   0.1 to 3% by weight of a dispersion stabilizer having polarity and non-polarity polarity at both ends thereof;

   0.1 to 15% by weight of a surface energy modifier for surface energy control;

   0.1 to 10% by weight of a liquid flowability-regulating agent in a liquid phase;

   1 to 15% by weight of an adhesion promoter composed of a carbon chain structure or a siloxane structure;

   0.1 to 5% by weight of an antifoaming agent,

   Wherein the viscosity of the oligosiloxane, the organic monomer or the organic oligomer, and the nanoparticles are controlled, and an organic network is formed between the thermosetting organic groups of the oligosiloxane, thermosetting organic group, Hybrid insulation material.
2. The method according to claim 1,

   Wherein the oligosiloxane has a molecular weight of 300 to 3,000. The thermosetting organic /
3. The method according to claim 1,

   Wherein the organic monomer or the organic oligomer has a molecular weight of 100 to 10,000, and a thermosetting organic / inorganic hybrid material.
4. The method according to claim 1,

   Wherein the nanoparticles are selected from the group consisting of organic nanoparticles, inorganic oxide nanoparticles, silicon nanoparticles, and mixtures thereof, and have a size of 1 to 500 nm.
5. 5. The method of claim 4,

   Wherein the organic nanoparticles are selected from the group consisting of polystyrene, polyurethane, polymethylmethacrylate, and mixtures thereof,

   Wherein the inorganic oxide nanoparticles are selected from the group consisting of silica, zirconia, alumina, titania, and mixtures thereof.
6. The method according to claim 1,

   Wherein the thermosetting initiator is a radical thermosetting initiator or a cationic thermosetting initiator,

   Wherein the type of the thermosetting initiator is selected according to the kind of the thermosetting organic polymer.
7. The method according to claim 1,

   The content of the thermosetting agent is determined theoretically by the equivalents of the oligosiloxane having the thermosetting organic group, the organic monomer and the organic oligomer,

   And a functional group selected from the group consisting of anhydride-based, phenolic-based, isocyanate-based, mercaptan-based, amine-based, and mixtures thereof.
8. The method according to claim 1,

   The curing accelerator includes a thermosetting organic group at one end and a side chain, and at least one of a hydroxyl group, a carboxyl group, a phosphate group, an amine group, an epoxy group, an oxetane group, an olefin group, a urethane group, And a functional group selected from the group consisting of an acrylic group, a methacryl group, an aryl group, a vinyl group urethane group, a mercapto group, a carboxyl group, an amine group, an olefin group and a mixture thereof. Type thermosetting organic / inorganic hybrid insulating material.
9. The method according to claim 1,

   Wherein the hybrid insulation material further comprises a surface leveling agent,

   Wherein the surface leveling agent is selected from the group consisting of a silicone resin, a silane, an acrylic resin, a methacrylic resin, a fluororesin, and a mixture thereof.