KR20200140509A - Highly heat-resistant nanohybrid siloxane insulating material and method for producing the same - Google Patents

Abstract

The present invention relates to a highly heat-resistant nanohybrid siloxane insulation material and a preparation method therefor and, more specifically, to: a highly heat-resistant nanohybrid siloxane insulation material having high heat resistance and also having basic insulation characteristics through the mixing of surface-treated silica nanoparticles and an oligosiloxane comprising a siloxane structure; and a preparation method therefor. The technical subjects of the present invention are: a highly heat-resistant nanohybrid siloxane insulation material comprising surface-treated silica nanoparticles and an oligosiloxane, which comprises a siloxane structure having at least one from among an alkyl group, an aryl group and an organic group; and a preparation method therefor.

Description

Highly heat-resistant nanohybrid siloxane insulating material and method for producing the same}

The present invention relates to a high heat-resistant nanohybrid siloxane insulating material and a method for manufacturing the same, and more particularly, to a high heat-resistant physical property based on insulating properties through mixing of an oligosiloxane containing a siloxane structure and surface-treated nanosilica particles. It relates to a high heat-resistant nanohybrid siloxane insulating material and a method of manufacturing the same to have together.

As the importance of fire safety has increased in recent years, the use of heat-resistant materials that are resistant to fire in various electrical and electronic components such as flexible displays, wearable devices, and Internet of Things (IoT) devices that require heat resistance, and in construction and transportation is becoming mandatory. to be.

Conventional heat-resistant materials include fluorine-based organic polymer-based heat-resistant coating materials and inorganic polysilazane-based heat-resistant coating materials.

In the case of heat-resistant coating materials based on fluorine-based organic polymers, PTFE is the starting line in terms of molecular structure, and there are various types by introducing CH bonds in addition to CF bonds to facilitate processing characteristics, so it is most often used in applications such as construction and transportation. However, there is a problem in terms of gas harmfulness that generates toxic gases in case of fire, so its use is expected to decrease in the future.

In the case of the inorganic polysilazane-based heat-resistant coating material, fire stability and gas harmfulness are very excellent, but it is expensive, and it is difficult to form a storage and thick film, so that it cannot be used for general use.

Therefore, it is the time when a research on technology development for a high heat-resistant nanohybrid siloxane insulating material that allows it to have high heat-resistant properties while being based on insulation characteristics is desperately required.

Korean Patent Publication No. 10-2018-0026259, published on March 12, 2018.

The present invention was invented to solve the above-described problems, and high heat resistance to have high heat resistance properties while being based on insulation characteristics through mixing of oligosiloxane containing a siloxane structure and surface-treated nanosilica particles. An object thereof is to provide a nanohybrid siloxane insulating material and a method for manufacturing the same.

The present invention for achieving the above object, the steps of preparing an oligosiloxane comprising a siloxane structure having at least one of an alkyl group, an aryl group and an organic group; And preparing a high heat-resistant insulating resin by mixing the surface-treated nanosilica particles with the oligosiloxane. A method of manufacturing a high heat-resistant nanohybrid siloxane insulating material comprising a technical gist.

Preferably, in the step of preparing the oligosiloxane, an organosilane precursor having one or more units of RSiO _3/2 , RR'SiO _2/2 and SiO _4/2 is raised through hydrolysis and condensation reaction in the presence of an acid. It is characterized in that the siloxane is prepared.

Preferably, in the step of preparing the oligosiloxane or the step of preparing the high heat-resistant insulating resin, at least one of an organic monomer or an organic oligomer, a heat condensation reaction accelerator, an adhesion promoter, a radical thermosetting initiator, a surface leveling agent, and an organic solvent It is characterized by mixing an additive containing.

The present invention for achieving the above object, an oligosiloxane comprising a siloxane structure having at least one of an alkyl group, an aryl group and an organic group; And surface-treated silica nanoparticles; a high heat-resistant nanohybrid siloxane insulating material, characterized in that it is formed, as a technical gist.

Preferably, the oligosiloxane is characterized in that it is formed by hydrolysis and condensation reaction of an organosilane precursor having one or more units of RSiO _3/2 , RR'SiO _2/2 and SiO _4/2 in the presence of an acid. .

The high heat-resistant nanohybrid siloxane insulating material according to the present invention and a method for manufacturing the same according to the present invention by means of solving the above problems have the following effects.

First, by mixing oligosiloxane and surface-treated nanosilica particles, there is an effect of obtaining a high heat-resistant nanohybrid siloxane insulating material having high heat-resistance properties while having an insulating property as a basis.

Second, since the high heat-resistant nanohybrid siloxane insulating material can be electrostatically coated due to its low moisture content, it has an effect that can be applied to various fields requiring substrates or substrates such as metals, glass, electrodes, and films.

Third, it is possible to introduce an additive such as an adhesion promoter, so that adhesion to the substrate or substrate and physical properties of the coated film can be supplemented.

Fourth, since the residual inorganic content of the high heat-resistant nanohybrid siloxane insulating material is higher than 65% or more than the conventional organic siloxane-based hybrid materials having a residual inorganic content of 50% or less, there is an effect of achieving a flame retardant grade 1.

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

That is, the present invention relates to a high heat-resistant nanohybrid siloxane insulating material technology using nano-silica particles as a filler in order to further secure low shrinkage, adhesion, crack resistance and heat resistance during curing, using oligosiloxane having high heat resistance as a binder. will be.

First of all, in order to establish high heat resistance or non-flammability in the high heat-resistant nanohybrid siloxane insulating material, the degree of molecular condensation is achieved by appropriately using organosilane precursors such as T, D and Q having one of various alkyl groups, aryl groups and organic groups. And not only can control the molecular structure, but also synthesize various highly heat-resistant oligosiloxanes using two or three organosilane precursors among alkyl groups, aryl groups, and organic groups, and various high heat-resistant nano Allows the manufacture of hybrid siloxane insulating materials.

Along with this, by adding one or more surface-treated nano silica particles among colloidal nanosilica and fumed nanosilica particles dispersed in a solvent to prevent shrinkage during curing of high heat-resistant nanohybrid siloxane insulating material, low shrinkage, heat resistance and crack resistance To improve.

In particular, the high heat-resistant nanohybrid siloxane insulating material in the present invention means that the residual inorganic content is high, where the residual inorganic content can be measured as the mass of the inorganic matter remaining when the high heat-resistant nanohybrid siloxane insulating material is burned at 750°C. have.

Existing organic siloxane-based hybrid materials mainly use silane precursors with a relatively high proportion of organic substances such as epoxy and methacrylic, so the final residual inorganic content is mostly 50% or less.

On the other hand, in the present invention, since the oligosiloxane is mainly synthesized with an alkyl silane precursor having as little organic group as possible, the residual inorganic content is 65% or more. Subsequently, since nanosilica particles composed of mostly inorganic substances are added to the synthesized oligosiloxane, the residual inorganic content of the final high heat-resistant nanohybrid siloxane insulating material may be 65% or more, and further 70% or more.

However, since the alkyl oligosiloxane without a curable group cannot optimally satisfy physical properties such as the hardness of the coated film, at least one of vinyl silane, methacrylic silane, and hydrogen silane is added to the oligosiloxane in a small amount. -The film properties can be improved by curing the final coated film in the form of vinyl siloxane and methyl-ethyl-methacrylic siloxane. At this time, even if the addition of the curable silane loses 2 to 3% of the residual inorganic content, the addition of the curable silane is important because the physical properties of the coating film are improved.

The high heat-resistant nanohybrid siloxane insulating material completed in this way has the advantage of being applied to various fields because it can be electrostatically painted due to its low moisture content, and it has the advantage of being able to introduce additives such as adhesion enhancers to supplement the physical properties of the coated film and adhesion. .

The high heat-resistant nanohybrid siloxane insulating material described above is a step of preparing an oligosiloxane comprising a siloxane structure having at least one of an alkyl group, an aryl group, and an organic group (S10) and mixing the surface-treated nanosilica particles with the oligosiloxane. It may be manufactured including the step of manufacturing a high heat-resistant insulating resin (S20), and each configuration constituting a high heat-resistant nanohybrid siloxane insulating material, which is a high heat-resistant insulating resin, will be described in detail below.

However, the high heat-resistant insulating resin mentioned in the present invention is defined by the same terms as the high heat-resistant nanohybrid siloxane insulating material.

The oligosiloxane of the present invention is a configuration including a siloxane structure having at least one of an alkyl group, an aryl group, and an organic group.

First of all, oligosiloxane has a siloxane-based siloxane structure with excellent thermal stability that can withstand high temperatures as its main structure, and has at least one of an alkyl group, an aryl group, and an organic group at the side chains and terminals. It says to include.

Here, as the alkyl group, any of methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, hexyl group, dimethyl group, and trimethyl group It may be one or more, and the aryl group may be any one or more of a phenyl group, a diphenyl group, and a triphenyl group, and the organic group may be any one or more of a vinyl group, a methacrylic group, and a hydrogen group.

That is, the oligosiloxane containing any one or more of an alkyl group, an aryl group, and an organic group can be synthesized using T, D, and Q types of organosilanes as precursors. At this time, T type has three Si-O bonds and can be described in RSiO _3/2 units, and D type has two Si-O bonds and can be described in RR'SiO _2/2 units, and Q Species can be described as SiO _4/2 units as having four Si-O bonds, where R can be an organic radical bonded to silicon through carbon.

However, as an organosilane precursor, it may include a siloxane structure consisting of various molecular structures such as T, D, and Q types, as well as TD, DQ and TDQ types, and may have a linear or branched or resin type molecular structure. However, it is not necessarily limited thereto.

In addition, as described above, in the case of conventional organic siloxane-based hybrid materials, since a silane precursor having a relatively high proportion of organic matter was used, the residual inorganic content of the material finally produced was as low as 50% or less. However, in the present invention, since the oligosiloxane is synthesized with a precursor such as an alkyl silane having as little organic group as possible, the residual inorganic content of the high heat-resistant nanohybrid siloxane insulating material may be 60% or more.

In summary, oligosiloxane is an organosilane precursor having one or more units of RSiO _3/2 , RR'SiO _2/2 and SiO _4/2 in the presence of an acid by hydrolysis and condensation reaction through thermal condensation method or thermal curing method. It can be manufactured, the content can be described as follows.

First, the thermal condensation method is not formed by curing through crosslinking between organic substances, but is formed in a form in which only inorganic powder of siloxane is dried or cured, and an organic silane precursor having an alkyl group or an aryl group is hydrolyzed and condensed using an acid aqueous solution. This is a method for preparing an alkyl or aryl oligosiloxane by reaction.

At this time, since only oligosiloxane without a curable group may not optimally satisfy physical properties such as hardness of the coating film, at least one curable silane among vinyl silane, methacrylic silane and hydrogen silane is added to the oligosiloxane in a small amount to make methyl-ethyl -The film properties can be improved by curing the final coating film in the form of vinyl siloxane and methyl-ethyl-methacrylic siloxane. For reference, even if the addition of the curable silane causes a loss of 2 to 3% of the residual inorganic content, the addition of the curable silane improves the physical properties of the coating film, so the addition of the curable silane has an important meaning.

In the case of curable silane, it may be added in an amount of 1 to 3 parts by weight based on 100 parts by weight of oligosiloxane. If the curable silane is less than 1 part by weight, the curing density may be too low, resulting in a decrease in the strength or hardness of the material, and the soft properties of the film. If it exceeds 3 parts by weight, residual radicals are present after curing and may cause yellowing. Therefore, it is preferable to use the curable silane by appropriately controlling it within the range of 1 to 3 parts by weight.

Second, the thermosetting method is a method of producing a thermosetting oligosiloxane by hydrolysis and condensation reaction in an acid atmosphere using an organosilane precursor having an organic group capable of thermosetting.

For example, the oligosiloxane containing an organic group may be thermally cured as follows. That is, in the process of synthesizing a high heat-resistant nanohybrid siloxane insulating material containing oligosiloxane, a Si-O (siloxane) network is formed through a condensation reaction, and the thermosetting organic groups are 4 coordination of silicon (Si) on the siloxane network. While occupying one of the coordinations, it contains an organic group at the side chain or end of the main structure of the siloxane network. Here, an organic network structure of not only a siloxane network but also an organic network structure can be formed through thermal curing while mixing together an organic mononer or an organic oligomer containing the same organic group. Therefore, an organic network of an inorganic siloxane structure and an organic group capable of thermosetting can be formed at the same time. I can. However, the organic mononer or organic oligomer will be described later.

It is preferable that the oligosiloxane that can be prepared in such various ways has a molecular weight in the range of 300 to 3,000. This is to control the molecular weight of the oligosiloxane and to variously control the siloxane content, which is the inorganic component of the high heat-resistant nanohybrid siloxane insulating material, by mixing two or more oligosiloxanes having different molecular weights.

When the molecular weight is less than 300, it is difficult to form an oligosiloxane, and when the molecular weight exceeds 3,000, the viscosity becomes too high and it is difficult to achieve uniform mixing with other components.Therefore, it is preferable that the oligosiloxane has a molecular weight in the range of 300 to 3,000. Do.

The oligosiloxane prepared through the above-described process is contained in 20 to 40 parts by weight in the high heat-resistant nanohybrid siloxane insulating material and can serve as a binder.If the oligosiloxane is less than 20 parts by weight, the oligosiloxane corresponding to the base component is different. It is preferable that the oligosiloxane is added in the range of 20 to 40 parts by weight, since it is not possible to smoothly mix with the ingredients, and if it exceeds 40 parts by weight, the remaining oligosiloxane without reaction with the surface-treated nanosilica particles may remain. .

The surface-treated nanosilica particles of the present invention are mixed with oligosiloxane to improve adhesion, crack resistance, and heat resistance.

First, the nanosilica of the nanosilica particles may be any one or more of an organic solvent type or water-based colloidal nanosilica, and a fumed nanosilica, wherein the organic solvent in the organic solvent type colloidal nanosilica is alcohol, glycol, cellulite. It can be any one of the Solve, Ketone, and Non-polar series. For reference, the size of the nanosilica particles is preferably in the range of several nanometers to tens of nanometers, and the size is not limited.

Particularly, nanosilica particles mixed with oligosiloxane are preferably surface-treated with a silane precursor, and then the remaining moisture is removed as much as possible.In the case of preparing oligosiloxane through thermal condensation, the nanosilica particles are surface-treated with an alkyl or aryl silane precursor. It can be treated, and when the oligosiloxane is prepared through a thermal curing method, the nanosilica particles can be surface-treated with alkyl and vinyl silane precursors.

For example, in the case of colloidal nanosilica particles surface-treated with an alkyl or aryl silane precursor, a commercial aqueous colloidal silica solution (Ludox HSA, Grace) having a particle size of 12 nm may be used. Alternatively, after surface treatment by adding 5 to 100 parts by weight of an aryl silane precursor, water is removed through reduced pressure distillation to replace the aqueous solvent with a non-polar or quasi-polar solvent, and then another solvent is added to adjust the total solid content to 40%. do.

As another example, in the case of fumed nano-silica particles, 20 to 40 parts by weight of commercial fumed nano-silica particles (SP-30, Amstack) having a particle size of 30 nm are dispersed with respect to 100 parts by weight of a non-polar or quasi-polar solvent, and then colloidal nano As in the case of silica particles, 2 to 50 parts by weight of an alkyl or aryl silane precursor is added to 100 parts by weight of the nano-silica particles for surface treatment, and the total solid content is adjusted to 40%.

The surface-treated nanosilica particles may be included in an amount of 0.1 to 20 parts by weight in the high heat-resistant nanohybrid siloxane insulating material, more preferably 10 parts by weight. As described above, by controlling the content of nano silica particles within 0.1 to 20 parts by weight, there is an effect of reducing shrinkage after curing, improving adhesion, and improving crack resistance. In addition, since nanosilica has heat resistance peculiar to particles, it is effective in enhancing the heat resistance of high heat-resistant nanohybrid siloxane insulating material.

In addition, if the surface-treated nanosilica particles are mixed with less than 0.1 parts by weight, the content of nanosilica made of inorganic matter is too low, so when the high heat-resistant nanohybrid siloxane insulating material is burned at 750℃, the remaining inorganic content will not be more than 65%. Since there is a fear that the surface-treated nanosilica particles are mixed in an amount of 0.1 parts by weight or more. On the other hand, if the surface-treated nanosilica particles exceed 20 parts by weight, it may affect the physical properties of the coating film sensitively, so that the surface-treated nano-silica particles are in the range of 0.1 to 20 parts by weight in order to create a synergy effect with the oligosiloxane. Mixing is desirable.

As described above, since the oligosiloxane having a residual inorganic content of 60% or more is mixed with nanosilica particles composed of mostly inorganic materials, the residual inorganic content of the final high heat-resistant nanohybrid siloxane insulating material can be achieved by 65% or more (or 70% or more). . This will be of great significance because it is a residual inorganic content that cannot be achieved with a general siloxane material.

That is, according to domestic standards, the evaluation criteria for flame retardant grade 1 (non-flammable grade) materials should have a residual inorganic content of 65% or more when burning at 750°C. As such, the flame retardant grade 1 is the standard for classifying high heat-resistant materials. Therefore, since the surface-treated nanosilica particles are mixed with the oligosiloxane, the residual inorganic content is 65% or more, so that the first grade of flame retardancy can be achieved.

The organic monomer or organic oligomer of the present invention has a carbonized chain structure and includes a thermosetting organic group at the side chain and the terminal.

That is, an organic monomer or an organic oligomer has a carbonized chain structure as a main structure and contains or has a thermosetting organic group at the side chain and at the end, and the carbonized chain structure may be an aliphatic urethane group, an aromatic urethane group, and a polyester group. The curable organic group may be, for example, at least one of an acrylic group, a methacrylic group, and a vinyl group.

Here, in the case of an organic monomer or an organic oligomer containing a thermosetting organic group, it is preferably used when the oligosiloxane contains a thermosetting organic group. This is because the efficiency of the thermal curing process may be degraded, such as a long time for complete thermal curing is required when the high heat-resistant nanohybrid siloxane insulating material is applied and then thermally cured, each containing different organic groups. For reference, the number of organic groups possessed by an organic monomer or an organic oligomer is at least one, and may have a polyfunctional organic group.

In addition, the molecular weight of the organic monomer or the organic oligomer may be in the range of 100 to 3,000, and crack resistance and heat resistance of the high heat-resistant nanohybrid siloxane insulating material can be controlled by controlling the molecular weight within the range of 100 to 3,000.

These organic monomers or organic oligomers may be included in an amount of 0.1 to 10 parts by weight in the high heat-resistant nanohybrid siloxane insulating material.If it is less than 0.1 parts by weight, it is difficult to control crack resistance and heat resistance, and if it exceeds 10 parts by weight, the heat resistance is very Since it was confirmed that a phenomenon of deterioration is caused, it is preferable to control crack resistance and heat resistance by using species having different molecular weights together. In the case of an organic monomer or an organic oligomer, it is most preferably added in an amount of 5 parts by weight.

The thermal condensation reaction accelerator of the present invention is a component for accelerating thermal condensation of oligosiloxane.

The thermal condensation reaction accelerator may be used as a catalyst with any one or more of acids, bases, amines, and metal salts to accelerate the thermal condensation of oligosiloxanes, preferably aluminum acetylacetonate (Al(acac) ₃ ), zirconium acetyl It may be acetonate (Zr(acac) ₄ ), and is not limited thereto, and various heat condensation accelerators may be used for thermal condensation of oligosiloxane.

In the case of the heat condensation reaction accelerator, it may be added in the step (S10) of preparing an oligosiloxane or may be added in the step (S20) of preparing a high heat-resistant insulating resin, and the order of addition is not limited.

If the heat condensation accelerator is added in less than 1 part by weight, the heat condensation reaction accelerating property is not improved, so it takes a lot of time to complete the heat condensation of the oligosiloxane, and if it is added in excess of 5 parts by weight, it changes color over time. Since yellowing, which is a kind of phenomenon, may occur, the heat condensation reaction accelerator is preferably included in the range of 1 to 5 parts by weight. Most preferably, 3 parts by weight is good.

The adhesion promoter of the present invention is configured to control the adhesion, heat resistance and chemical resistance of the high heat-resistant nanohybrid siloxane insulating material including oligosiloxane, as well as the shrinkage after curing.

In other words, the high heat-resistant nanohybrid siloxane insulating material improves adhesion to various substrates or substrates such as metal, glass, electrode, film, etc. through an adhesion promoter.These adhesion promoters are vinyl groups, acrylic groups, and meta that can be covalently bonded by heat. It is composed of an organic monomer or organic oligomer or polymer containing any one or more functional groups of acrylic group, hydroxy group, carboxyl acid group, phosphate group, amine group, olefin group and urethane group to promote adhesion, increase chemical resistance, and promote curing It works.

In the case of adhesion promoter, it may be included in 1 to 20 parts by weight in the high heat-resistant nanohybrid siloxane insulating material.If it is less than 1 part by weight, it cannot improve adhesion on various substrates such as glass, metal, plastic, and wood, and 20 parts by weight. If it is exceeded, it is preferable to use it by appropriately adjusting it within the range of 1 to 20 parts by weight, since sticky phenomenon may occur and deteriorate physical properties. Among them, 5 parts by weight are most preferable.

The radical thermosetting initiator of the present invention is a compound that generates radicals in the presence of a monomer through heat, and is a composition in which a part with weak chemical bonds is boiled by heat to form a radical, and a thermosetting reaction is initiated with an organic group capable of thermosetting. .

The radical thermosetting initiator may include any one or more of peroxide-based and azo-based initiators. First, as peroxide systems, benzoyl peroxide, acetyl peroxide, amyl peroxybenzoate, butyl peroxide, dicumyl peroxide, lauryl peroxide, butyl hydroperoxide, butyl peracetate, butyl peroxybenzoate, cumin hide Any one or more of loperoxide, cyclohexanone peroxide, butylperoxy isopropyl carbonate, and potassium persulfate may be selected. Second, as the azo system, any one or more of azo beads cyano valeric acid, azo beads cyclosecate carbonitril, and azo beads isobutyronitrile may be selected.

At this time, the radical thermosetting initiator may be applied in an amount of 1 to 5 parts by weight when the content of the oligosiloxane containing an organic group capable of thermosetting and an organic monomer or organic oligomer is 100 parts by weight. If the radical thermosetting initiator is less than 1 part by weight, it takes a lot of time to heat cure, and if it exceeds 5 parts by weight, heat curing takes place within too fast time, so that only the outside is heat cured without heat curing. Since there is a concern that this may be achieved, there is a need to appropriately adjust the radical thermosetting initiator within the range of 1 to 5 parts by weight.

The surface leveling agent of the present invention is a composition that improves fairness by imparting control effects of wetting properties and defects such as pinholes through control of surface energy of high heat-resistant nanohybrid siloxane insulating material.

As the surface leveling agent, any one or more of acrylic resins, methacrylic resins, fluorine resins, silicone resins, and silanes may be selectively used.

Such a surface leveling agent may be included in an amount of 0.1 to 1 parts by weight, and if it is less than 0.1 parts by weight, it is difficult to control the surface energy, so it is not easy to control flowability, and defects such as pinholes may occur. Since control may become difficult, it is recommended to use it by appropriately adjusting within the range of 0.1 to 1 parts by weight, and 0.5 parts by weight is most preferred.

The organic solvent of the present invention is composed of at least one of alcohol-based, glycol-based, cellosolve-based, ketone-based, and non-polar-based, thereby achieving homogenization between components.

In the case of an organic solvent, it may be contained in an amount of 50 to 70 parts by weight, and if it is less than 50 parts by weight, the miscibility with other components cannot be properly achieved, and if it exceeds 70 parts by weight, it is significant compared to the case where a less amount is added. Since there is no effect, the organic solvent is preferably included in the range of 50 to 70 parts by weight.

Hereinafter, a preferred embodiment of the present invention will be described in more detail as follows.

<Example 1>

Example 1 is a method using an alkyl or aryl oligosiloxane through a thermal condensation method. In other words, hydrolysis and condensation of methyltrimethoxysilane and dimethyldiethoxysilane having a methyl group, ethyltrimethoxysilane having an ethyl group, propyltrimethoxysilane having a propyl group, phenyltrimethoxysilane having a phenyl group, and TEOS For the reaction, an alkyl or aryl oligosiloxane was prepared using an aqueous hydrochloric acid solution (T, TD, TQ species). Here, the molecular weight was controlled by controlling reaction variables including catalyst concentration and reaction time.

In Example 1, the content of the oligosiloxane prepared by varying the types and molar ratios of the alkyl and aryl organosilane precursors was within the range of 20 to 40 parts by weight, and the residual inorganic content could be changed according to the mixed content.

Colloidal nano-silica particles or fumed nano-silica particles surface-treated with an alkyl or aryl organosilane precursor in different amounts of oligosiloxane were prepared and mixed in an amount of 0.1 to 20 parts by weight.

For colloidal silica nanoparticles surface-treated with an alkyl or aryl organosilane precursor, a commercial aqueous colloidal silica solution (Ludox HSA, Grace) having a particle size of about 12 nm was used, that is, 5 to 50 parts by weight per 100 parts by weight of nano silica particles. Negative alkyl or aryl organosilane precursors were added and surface treated. Subsequently, in order to replace the aqueous solvent with a non-polar or quasi-polar solvent, water was removed using a vacuum distillation method, and then another solvent was added to adjust the total solid content to about 40%.

In the case of fumed nano-silica particles, commercial fumed nano-silica particles (SP-30, Amstack) having a particle size of 30 nm are dispersed in a non-polar or semi-polar solvent by 20 to 40%, and then, like colloidal nano-silica particles, nano-silica particles 100 Based on parts by weight, 5 to 50 parts by weight of an alkyl or aryl silane organosilane precursor was added to treat the surface, and the total solid content was adjusted to be about 40%.

In addition, 0.1 to 3 parts by weight of aluminum acetylacetonate (Al(acac) ₃ ), which is a thermal condensation reaction accelerator of oligosiloxane, was added. In addition, 2 parts by weight of a carboxyl acid-based adhesion promoter were mixed, 0.5 parts by weight of a surface leveling agent, 20 parts by weight of butyl cellosolve as an organic solvent, and 40 parts by weight of xylene as a non-polar organic solvent were mixed.

High heat-resistant nanohybrid siloxane insulating materials through this thermal condensation method are shown in Examples 1-1, 1-2, 1-3, 1-4 and 1-5 as follows.

In Example 1-1, 16 parts by weight of methyl-ethyl oligosiloxane, 10 parts by weight of methyl-propyl oligosiloxane, 10 parts by weight of colloidal nanosilica, 0.5 parts by weight of surface leveling agent, 1.5 parts by weight of heat condensation accelerator, adhesion promoter 2 A high heat-resistant nanohybrid siloxane insulating material consisting of parts by weight, 20 parts by weight of butyl cellosolve, and 40 parts by weight of xylene was prepared.

In Example 1-2, 16 parts by weight of methyl-ethyl oligosiloxane, 10 parts by weight of methyl-propyl oligosiloxane, 0.5 parts by weight of surface leveling agent, 1.5 parts by weight of heat condensation accelerator, 2 parts by weight of adhesion promoter, 20 parts by weight of butyl cellosolve Parts and 40 parts by weight of xylene, but unlike Example 1-1, a high heat-resistant nanohybrid siloxane insulating material containing 10 parts by weight of fumed nano-silica particles was prepared.

In Example 1-3, 16 parts by weight of methyl-ethyl oligosiloxane, 20 parts by weight of methyl-propyl oligosiloxane, 0.5 parts by weight of surface leveling agent, 1.5 parts by weight of heat condensation accelerator, 2 parts by weight of adhesion promoter, 20 parts by weight of butyl cellosolve A high heat-resistant nanohybrid siloxane insulating material consisting of parts and 40 parts by weight of xylene was prepared.

In Example 1-4, 8 parts by weight of methyl-propyl oligosiloxane, 8 parts by weight of methyl-phenyl oligosiloxane, 5 parts by weight of methyl oligosiloxane, 5 parts by weight of propyl-TEOS oligosiloxane, 5 parts by weight of colloidal nano silica, and fumed nano A highly heat-resistant nanohybrid siloxane insulating material consisting of 5 parts by weight of silica, 0.5 parts by weight of a surface leveling agent, 1.5 parts by weight of a heat condensation reaction accelerator, 2 parts by weight of an adhesion promoter, 20 parts by weight of butyl cellosolve and 40 parts by weight of xylene was prepared.

In Example 1-5, 5 parts by weight of methyl-ethyl oligosiloxane, 5 parts by weight of methyl-propyl oligosiloxane, 5 parts by weight of methyl-phenyl oligosiloxane, 5 parts by weight of methyl oligosiloxane, 5 parts by weight of propyl-TEOS oligosiloxane, Colloidal nanosilica 6 parts by weight, fumed nano silica 5 parts by weight, surface leveling agent 0.5 parts by weight, heat condensation reaction accelerator 1.5 parts by weight, adhesion promoter 2 parts by weight, butyl cellosolve 20 parts by weight and xylene 40 parts by weight A heat-resistant nanohybrid siloxane insulating material was prepared.

These Examples 1-1, 1-2, 1-3, 1-4, and 1-5 are summarized and shown in Table 1 below. However, although not described in Table 1, in Examples 1-1, 1-2, 1-3, 1-4 and 1-5, a trace amount of curable silane was added to improve the film properties of the final coating film.

Example 1-1 Example 1-2 Example 1-3 Example 1-4 Example 1-5 Methyl-ethyl
Oligosiloxane
(MW: 300~3,000) 16 16 16 - 5 Methyl-propyl
Oligosiloxane
(MW: 300~3,000) 10 10 20 8 5 Methyl-phenyl
Oligosiloxane
(MW: 300~3,000) - - - 8 5 methyl
Oligosiloxane
(MW: 300~2,500) - - - 5 5 Profile-TEOS
Oligosiloxane
(MW: 500~3,000) - - - 5 5 Colloidal Nanosilica 10 - - 5 6 Fumed nano silica - 10 - 5 5 Surface leveling agent 0.5 0.5 0.5 0.5 0.5 Heat condensation reaction accelerator 1.5 1.5 1.5 1.5 1.5 Adhesion enhancer 2 2 2 2 2 Butyl Cellosolve 20 20 20 20 20 Xylene 40 40 40 40 40 Unit: parts by weight

Experimental results according to Examples 1-1, 1-2, 1-3, 1-4 and 1-5 through the above-described thermal condensation method are shown in Table 2 below.

Example 1-1 Example 1-2 Example 1-3 Example 1-4 Example 1-5 Hardness ◎ ◎ ◎ ◎ ◎ Residual inorganic content (%) 70 or more 70 or more 70 or more 65 or more 67 or more Transmittance(%) 91 91 91 91 91 Adhesion (B) 5 5 5 5 5 crack × × × × × Moisture content (%) 0.1 or less 0.1 or less 0.1 or less 0.1 or less 0.1 or less Pencil hardness H H HB or less H H

Looking at Table 2, the degree of curing is to check whether or not it is sticky after curing, and is expressed as ◎: very good, ○: excellent, △: insufficient, x: poor. The residual inorganic content is a numerical value indicating the content of inorganic content during combustion at 750°C after curing. The transmittance was measured through UV-Vis Spectroscopy (Coatings on quartz glass). Adhesion was measured through ASTM D3359-97 standard (Cross-Cut Tape Test, glass substrate). The presence or absence of cracks was measured through visual observation and OEM observation after curing, and was marked as ○: Yes, ×: No. The moisture content was numerically expressed as how much moisture remained relative to the total weight in the finished high heat-resistant nanohybrid siloxane insulating material. Pencil hardness is a 45 degree angle for each type of pencil (2B, B, HB, F, H, 2H and 3H) on the cured coating film of high heat-resistant nanohybrid siloxane insulating material cured using a pencil hardness tester according to the pencil hardness method. It was shown by visually evaluating the degree of scratching when drawn with

<Example 2>

Example 2 is a hydrolysis and condensation reaction in an acidic atmosphere using vinyl trimethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, and propyltrimethoxysilane having a vinyl group capable of thermal curing through a thermal curing method. It is a method using a thermosetting oligosiloxane prepared by proceeding. Here, the molecular weight was controlled by controlling the reaction variables including the concentration of the acid and the reaction time, and the residual inorganic content was controlled through this, and the molecular weight of the prepared oligosiloxane was approximately 1,000 to 3,000.

In Example 2, an oligosiloxane having various types and molar ratios of alkyl and vinyl organosilane precursors was prepared, and the content was in the range of 20 to 40 parts by weight, and the residual inorganic content and coating properties could be changed according to the content.

Subsequently, colloidal nanosilica particles surface-treated with alkyl and vinyl in different contents of oligosiloxane were prepared and mixed in a range of 0.1 to 20 parts by weight. The colloidal nanosilica particles surface-treated with alkyl and vinyl organosilane precursors are prepared by using a commercial aqueous colloidal silica solution (Ludow HSA, Grace) having a particle size of about 12 nm, using 33 to 100 parts by weight of alkyl and Surface treatment was performed by adding a vinyl organosilane precursor. In order to replace the aqueous solvent with a non-polar or quasi-polar solvent, water was removed using a vacuum distillation method and another solvent was added to adjust the solid content to 40%.

In addition, 0.1 to 3 parts by weight of aluminum acetylacetonate (Al(acac) ₃ ), which is a thermal condensation reaction accelerator of oligosiloxane, was added, additionally, 2 parts by weight of a carboxyl acid-based adhesion promoter was mixed, and 0.5 parts by weight of a surface leveling agent , 20 parts by weight of butyl Cellosolve as an organic solvent and 40 parts by weight of xylene as a non-polar organic solvent were mixed.

High heat-resistant nanohybrid siloxane insulating materials through this thermosetting method are shown in Examples 2-1, 2-2, 2-3, 2-4 and 2-5 as follows.

In Example 2-1, 18 parts by weight of methyl-propyl-vinyl oligosiloxane, 18 parts by weight of methyl-ethyl-vinyl oligosiloxane, 0.5 parts by weight of surface leveling agent, 1.5 parts by weight of thermal condensation accelerator, 2 parts by weight of adhesion promoter, butyl A highly heat-resistant nanohybrid siloxane insulating material consisting of 20 parts by weight of Cellosolve and 40 parts by weight of xylene was prepared.

In Example 2-2, 18 parts by weight of methyl-propyl-vinyl oligosiloxane, 18 parts by weight of colloidal nanosilica, 0.5 parts by weight of surface leveling agent, 1.5 parts by weight of heat condensation accelerator, 2 parts by weight of adhesion promoter, butyl cellosolve 20 A high heat-resistant nanohybrid siloxane insulating material consisting of parts by weight and 40 parts by weight of xylene was prepared.

In Example 2-3, 26 parts by weight of methyl-propyl-vinyl oligosiloxane, 10 parts by weight of colloidal nanosilica, 0.5 parts by weight of a surface leveling agent, 1.5 parts by weight of a heat condensation accelerator, 2 parts by weight of adhesion promoter, butyl cellosolve 20 A high heat-resistant nanohybrid siloxane insulating material consisting of parts by weight and 40 parts by weight of xylene was prepared.

In Example 2-4, 13 parts by weight of methyl-vinyl oligosiloxane, 13 parts by weight of ethyl-vinyl oligosiloxane, 5 parts by weight of propyl-vinyl oligosiloxane, 5 parts by weight of colloidal nanosilica, 0.5 parts by weight of surface leveling agent, thermal condensation A highly heat-resistant nanohybrid siloxane insulating material consisting of 1.5 parts by weight of a reaction accelerator, 2 parts by weight of an adhesion promoter, 20 parts by weight of butyl cellosolve, and 40 parts by weight of xylene was prepared.

In Example 2-5, 5 parts by weight of methyl-vinyl oligosiloxane, 5 parts by weight of ethyl-vinyl oligosiloxane, 5 parts by weight of propyl-vinyl oligosiloxane, 11 parts by weight of methyl-propyl-vinyl oligosiloxane, and methyl-ethyl-vinyl oligo High heat-resistant nano consisting of 5 parts by weight of siloxane, 5 parts by weight of colloidal nano silica, 0.5 parts by weight of surface leveling agent, 1.5 parts by weight of heat condensation reaction accelerator, 2 parts by weight of adhesion promoter, 20 parts by weight of butyl cellosolve and 40 parts by weight of xylene A hybrid siloxane insulating material was prepared.

These Examples 2-1, 2-2, 2-3, 2-4, and 2-5 are summarized in Table 3 below.

Example 2-1 Example 2-2 Example 2-3 Example 2-4 Example 2-5 Methyl-vinyl
Oligosiloxane
(MW: 1,000~3,000) - - - 13 5 Ethyl-vinyl
Oligosiloxane
(MW: 1,000~3,000) - - - 13 5 Propyl-vinyl
Oligosiloxane
(MW: 1,000~3,000) - - - 5 5 Methyl-propyl-vinyl
Oligosiloxane
(MW: 1,000~2,500) 18 18 26 - 11 Methyl-ethyl-vinyl
Oligosiloxane
(MW: 1,000~3,000) 18 - - - 5 Colloidal Nanosilica 0 18 10 5 5 Surface leveling agent 0.5 0.5 0.5 0.5 0.5 Heat condensation reaction accelerator 1.5 1.5 1.5 1.5 1.5 Adhesion enhancer 2 2 2 2 2 Butyl Cellosolve 20 20 20 20 20 Xylene 40 40 40 40 40 Unit: parts by weight

Experimental results according to Examples 2-1, 2-2, 2-3, 2-4 and 2-5 through the above-described thermal curing method are shown in Table 4 below.

Example 2-1 Example 2-2 Example 2-3 Example 2-4 Example 2-5 Hardness ◎ ◎ ◎ ◎ ◎ Residual inorganic content (%) 70 or more 75 or more 72 or more 65 or more 65 or more Transmittance(%) 91 91 91 91 91 Adhesion (B) 5 5 0 5 5 crack ○ × × × × Moisture content (%) 0.1 or less 0.1 or less 0.1 or less 0.1 or less 0.1 or less Pencil hardness HB or less 2H 2H H H

Looking at Table 4, it can be seen that the experiment was conducted in the same manner as in Table 2. The degree of curing was confirmed as to whether or not it was sticky after curing, ◎: very good, ○: excellent, △: insufficient, ×: indicated as poor I did. In the case of the residual inorganic content, the content of the inorganic content during combustion at 750°C after curing is expressed as a numerical value. Transmittance is a value measured through UV-Vis Spectroscopy (Coatings on quartz glass). Adhesion is a value measured through ASTM D3359-97 standard (Cross-Cut Tape Test, glass substrate). The presence or absence of cracks was measured through visual observation and OEM observation after curing, and was expressed as ○: Yes, ×: No. The moisture content is a numerical representation of how much moisture remains relative to the total weight in the finished high heat-resistant nanohybrid siloxane insulating material. Pencil hardness is a 45 degree angle for each type of pencil (2B, B, HB, F, H, 2H and 3H) on the cured coating film of high heat-resistant nanohybrid siloxane insulating material cured using a pencil hardness tester according to the pencil hardness method. It is expressed by visually evaluating the degree of scratching when drawn with

As can be seen from Examples 1 and 2, the degree of curing and residual inorganic content due to mixing of the oligosiloxane containing a siloxane structure having at least one of an alkyl group, an aryl group, and an organic group and the surface-treated nanosilica particles , Transmittance, adhesion, moisture content and pencil hardness all have excellent advantages.

However, in Example 1-3 prepared through the thermal condensation method, the nanosilica was not mixed and no crack was generated despite the lack of adhesion, but in Example 2-1 prepared through the thermal curing method, nanosilica was mixed. Although not, the adhesion was excellent, but cracks occurred.

Regarding the residual inorganic content, conventional organic siloxane-based hybrid materials mainly use silane precursors with a relatively high proportion of organic substances such as epoxy and methacrylic, so the final residual inorganic content was mostly 50% or less. In Examples 1 and 2, since the oligosiloxane was synthesized mainly with a precursor such as an alkyl organosilane, it was found that most of the residual inorganic content was 65% or more. This means that the evaluation criteria for flame retardant grade 1 (non-flammable grade) materials according to domestic standards should have a residual inorganic content of 65% or more after burning at 750°C. Most of the highly heat-resistant nanohybrids through Examples 1 and 2 Siloxane insulating materials are meaningful in obtaining a flame retardant grade 1 as the residual inorganic content of 65% or more after combustion at 750°C.

Therefore, it was found that both adhesion and crack-free physical properties were satisfied only when nano-silica was included. Therefore, the mixture of oligosiloxane and surface-treated nano-silica made it possible to have high heat-resistance properties while being based on insulating properties. In addition, it has the effect of satisfying all physical properties.

The above description is merely illustrative of the technical idea of the present invention, and those of ordinary skill in the art to which the present invention pertains will be able to make various modifications and variations without departing from the essential characteristics of the present invention.

Therefore, the embodiments disclosed in the present invention are not intended to limit the technical idea of the present invention, but to explain the technical idea, and the scope of the technical idea of the present invention is not limited by these embodiments.

The scope of protection of the present invention should be interpreted by the claims, and all technical ideas within the scope equivalent thereto should be construed as being included in the scope of the present invention.

Claims (5)

Preparing an oligosiloxane including a siloxane structure having at least one of an alkyl group, an aryl group, and an organic group; And
A method of producing a high heat-resistant nanohybrid siloxane insulating material comprising; mixing the oligosiloxane with surface-treated nanosilica particles to prepare a high heat-resistant insulating resin. The method of claim 1,
In the step of preparing the oligosiloxane,
High heat-resistant nanohybrid, characterized in that oligosiloxane is produced through hydrolysis and condensation reaction of an organosilane precursor having one or more units of RSiO _3/2 , RR'SiO _2/2 and SiO _4/2 in the presence of an acid Method of manufacturing siloxane insulating material. The method of claim 1,
In the step of preparing the oligosiloxane or the step of preparing the high heat-resistant insulating resin,
An organic monomer or an organic oligomer, a thermal condensation reaction accelerator, an adhesion promoter, a radical thermosetting initiator, a surface leveling agent, and an additive comprising at least one of an organic solvent is mixed. An oligosiloxane containing a siloxane structure having at least one of an alkyl group, an aryl group, and an organic group; And
Surface-treated silica nanoparticles; High heat-resistant nanohybrid siloxane insulating material, characterized in that formed, including. The method of claim 4,
The oligosiloxane is,
High heat-resistant nanohybrid siloxane insulating material, characterized in that formed by hydrolysis and condensation reaction of an organosilane precursor having one or more units of RSiO _3/2 , RR'SiO _2/2 and SiO _4/2 in the presence of an acid.