KR101379899B1 - Composition of transparent thermal resistance and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a transparent heat resistant material composition and a method for manufacturing the same, wherein the transparent heat resistant material composition according to the present invention comprises a polyamide acid and a covalent polymer, and the pores with respect to 100 parts by weight of the polyamide acid, 5 to 20 parts by weight of an induction polymer, wherein the covalent polymer is characterized in that at least one of polymethyl methacrylate (polymethyl methacrylate), polyvinyl alcohol (polyvinyl alcohol) or polyvinylpyrrolidone (polyvinylpyrrolidone) .
According to the present invention, the polyamide acid formed by mixing and reacting an acid anhydride, a diamine compound, and an organic solvent is mixed at an optimum ratio, thereby minimizing a decrease in the transmittance of visible light, while reducing heat resistance characteristics such as thermal conductivity. It has the advantage of significantly improving.

Description

Transparent heat resistant material composition and manufacturing method thereof {COMPOSITION OF TRANSPARENT THERMAL RESISTANCE AND MANUFACTURING METHOD THEREOF}

The present invention relates to a transparent heat-resisting material composition and a method for manufacturing the same, and more particularly, by mixing polyamide acid formed by reacting an acid anhydride, a diamine compound and an organic solvent in an optimal ratio, The present invention relates to a transparent heat resistant material composition and a method of manufacturing the same, which have a high transmittance and significantly improve heat resistance characteristics such as thermal conductivity.

The development of renewable energy or alternative energy technologies is emerging as an alternative technology due to greenhouse gas reduction and fossil energy depletion, and interest in creating added value through efficient management of energy is increasing rapidly.

Therefore, in summer, the heat rays flowing into the room are blocked to increase the efficiency of the room, while the visible light is kept the same as the existing glass to maintain a comfortable interior, and in winter, the function to manage the heat efficiently by minimizing the heat loss in the room. The demand for materials continues, and the demand for transparent thermal barrier materials is expected to soar.

The concept of heat-absorbing materials was proposed in the 1960s, but full-scale research began around 1998, the first products were launched in 2000, and by 2005 the first generation of products was formed.

These attempts to control the heating wire have been developed in various ways such as tilted glass, tilt film, sputter coated glass and sputter coated film, and some of them have already been commercialized, but performance or reliability are still widely available. There is a limit to. In particular, in the prior art, sputter-coated glass is an expensive process, has a weak disadvantage in oxidation and discoloration, the tilt film has a disadvantage of poor durability.

In Europe, which has been preparing alternatives to energy problems early in the 1990s and 2000s, sputter-coated glass, which is known to have the best thermal barrier properties, has a double layer, and an insulated window filled with an inert gas such as argon in the middle ( Low emission glass, low-E glass) was developed and used.

In addition, metal-coated low-emission glass has institutional devices such as Austria, Switzerland and the UK since Germany, and demand has increased, and the use ratio of Japan, China, etc. is gradually increasing in Asia. However, Korea still has the lowest application rate internationally due to lack of awareness of energy management technology.

However, the thin film metal coating technology can realize the performance characteristics such as high transmittance and heat ray shielding characteristics.However, there is a problem that the membrane is separated or discolored due to corrosion in high humidity areas. There is a problem that interferes with.

In addition, Southwall's V-KOOL product, which uses a technology of depositing a metal thin film on a film, has excellent characteristics such as infrared blocking rate of 96%, but the manufacturing process is very complicated, and thus the product price is very high. There is a disadvantage of being expensive.

In addition, in a product to which high heat-transfer performance is given, there is a problem that a multilayer low-emission glass which is continuously stressed due to a large difference in thermal expansion characteristics due to heat radiation absorption introduced from the outside causes an explosion phenomenon.

In addition, the conventional heat shield glass also has a problem that the inside of the light is also darkened by blocking the visible light wavelength.

In other words, in the case of the conventional thermal barrier glass and film development technology, it is impossible to satisfy all of the heat resistance characteristics, transparency, economy and durability, so it is possible to solve these problems and commercialize them by applying a new concept rather than the conventional method. Technology development is required.

The present invention has been made to solve the above problems, and an object of the present invention is to reduce the transmittance of visible light by mixing polyamide acid and a covalent polymer formed by mixing an acid anhydride, a diamine compound and an organic solvent in an optimum ratio. It is aimed at remarkably improving heat resistance characteristics, such as thermal conductivity, while minimizing this.

In addition, by optimizing the size and dispersion of the pore-forming material and the pores, it is not only to minimize the decrease in visible light transmittance, but also to minimize the decrease in durability.

In addition, compared to the prior art, by optimizing the reaction process, minimizing the process step, it is an object to manufacture a heat resistance material quickly and economically.

The transparent heat resistant material composition according to the present invention for achieving the above object comprises a polyamide acid and a covalent copolymer, with respect to 100 parts by weight of the polyamide acid, 5 to 20 parts by weight of the covalent polymer It is characterized in that it comprises, the group covalent polymer is characterized in that at least one of polymethyl methacrylate (polymethyl methacrylate), polyvinyl alcohol (polyvinyl alcohol) or polyvinylpyrrolidone (polyvinylpyrrolidone).

In addition, the particle size of the pore copolymer is characterized in that 0.1 ㎛ to 3㎛, the molecular weight of the pore copolymer is characterized in that 10,000 to 30,000.

The polyamide acid is formed by mixing an acid anhydride, a diamine compound and an organic solvent. The diamine compound is mixed in an amount of 0.8 to 1.2 equivalents based on 1.0 equivalent of the acid anhydride. Anhydrides are pyromelliticdianhydrides, 4,4 '-(hexafluoroisopropylidene) diphthalic dianhydrides (4,4' (Hexafluoroisopropylidene) diphthalicanhydride), 3,3,4,4- Benzophenonetetracarboxylic dianide, difetylether-3,3 ', 4,4'-tetracarboxylic dianhydride or 4,4'-oxydiphthalic dianhydride.

In addition, the diamine compound is in 4,4'-Oxidianilline, 4,4'- diaminodiphenyl ether or 2,6-bis (3-aminophenoxy) phenonitrile At least one, characterized in that the organic solvent, N-methyl-2-pyrrolidone (N-methyl-2-pyrrolidone), dimethylacetamide, acetonitrile, t-butanol, acetone, dimethylformamide, iso At least one of propyl alcohol or ethyl acetate.

Method for producing a transparent heat resistance material composition according to the present invention for achieving the above object, the mixing step of preparing a mixture by mixing an acid anhydride, a diamine compound and an organic solvent; Reacting the mixture by stirring to prepare a polyamide acid solution; And adding an air-covalent polymer to the polyamide acid solution to prepare a transparent heat resistance material composition.

In the reaction step, the reaction temperature is characterized in that 10 ℃ to 50 ℃, in the reaction step, the reaction time is characterized in that 8 hours to 15 hours, in the addition step, the polyamide acid solution 100 It is characterized by including 5 to 20 parts by weight of the group covalent polymer with respect to parts by weight.

In addition, in the addition step, the group covalent polymer is characterized in that at least one of polymethyl methacrylate (polymethyl methacrylate), polyvinyl alcohol (polyvinyl alcohol) or polyvinylpyrrolidone (polyvinylpyrrolidone).

In the mixing step, with respect to 1.0 equivalent of the acid anhydride, the diamine compound is characterized in that it is mixed in 0.8 to 1.2 equivalents, in the mixing step, the acid anhydride, pyromelliticdian hydride, 4 , 4 '-(hexafluoroisopropylidene) diphthalic hydride (4,4' (Hexafluoroisopropylidene) diphthalicanhydride), 3,3,4,4-benzophenonetetracarboxylic dianideide, difetylether-3 , 3 ', 4,4'-tetracarboxylic dianhydride or at least one of 4,4'-oxydiphthalic dianhydride, the diamine compound is 4,4'-oxydianiline (4,4' -Oxydianilline), 4,4'-diaminodiphenylether or 2,6-bis (3-aminophenoxy) phenozonitrile, and the organic solvent is N-methyl-2-pyrrolidone (N -methyl-2-pyrrolidone), dimethylacetamide, acetonitrile, t-butanol, acetone, dimethylforma De, characterized in that at least one of isopropyl alcohol or ethyl acetate.

In addition, in the reaction step, the viscosity of the polyamide acid solution is characterized in that the 80CPS to 250CPS.

According to the transparent heat-resisting material composition of the present invention and a method for manufacturing the same, the polyamide acid formed by mixing an acid anhydride, a diamine compound, and an organic solvent is mixed with an air-copolymer in an optimal ratio, thereby minimizing a decrease in transmittance of visible light. At the same time, there is an advantage of remarkably improving heat resistance characteristics such as thermal conductivity.

In addition, by optimizing the size and dispersion of the pore-forming material and the pore, not only can the reduction of visible light transmittance be minimized, but also the durability can be minimized.

In addition, compared to the prior art, by optimizing the reaction process, the process step is minimized, there is an advantage that can be produced quickly and economically heat resistant material.

1 is a flow chart sequentially showing a manufacturing method of a transparent heat resistance material composition of the present invention
Figure 2 is a schematic diagram illustrating the formation process of the transparent heat resistance material composition according to the manufacturing method of the transparent heat resistance material composition of the present invention
Figure 3 is a reaction scheme showing a reaction step (S20) in the method for producing a transparent heat resistant material composition of the present invention
Figure 4 is a reaction scheme showing a reaction step (S20) in the method for producing a transparent heat resistant material composition of the present invention
FIG. 5 is a SEM photograph of a transparent heat resistance material formed through the reaction step S20 of FIG. 4.
6 is a SEM photograph of a transparent heat resistance material formed through the reaction step (S20) of FIG.
Figure 7 is a SEM photograph of the transparent heat resistance material produced by the present invention
8 is a graph showing the thermal conductivity of the conventional polyimide material (PI) and the transparent thermal resistance material (PI foam) of the present invention
9 is a graph showing the Young's modulus of the conventional polyimide material (PI) and the transparent thermal resistance material (PI foam) of the present invention

Hereinafter, with reference to the accompanying drawings, a preferred embodiment of the present invention with respect to the transparent heat resistance material composition and its manufacturing method according to the present invention will be described in detail. The present invention may be better understood by the following examples, which are for the purpose of illustrating the present invention and are not intended to limit the scope of protection defined by the appended claims.

First, look at with respect to the transparent heat resistance material composition according to the present invention. The composition of the present invention comprises a polyamide acid and a covalent polymer. This is to minimize the physical property deterioration while significantly reducing the thermal conductivity by forming pores effectively inside.

The polyamic acid is most effective in the present invention formed by mixing and reacting an acid anhydride, a diamine compound and an organic solvent.

Here, for 1.0 equivalent of the acid anhydride, the diamine compound is preferably mixed in an amount of 0.8 to 1.2 equivalents, more preferably 0.9 to 1.1 equivalents. When less than 0.8 equivalent or more than 1.2 equivalent, there is a problem that not only the physical properties of the polyamic acid are lowered but also the transparency is inferior.

In addition, the acid anhydride may be pyromelliticdianhydride, 4,4 '-(hexafluoroisopropylidene) diphthalic dianhydride (4,4'-(Hexafluoroisopropylidene) diphthalicanhydride), 3,3, At least one of 4,4-benzophenonetetracarboxylic dianide, difetylether-3,3 ', 4,4'-tetracarboxylic dianhydride or 4,4'-oxydiphthalic dianhydride Preferably, more preferably, pyromelliticdianhydride is most effective. This is a heat resistance material, to realize the optimum physical properties and transparency.

In addition, the diamine compound is in 4,4'-Oxidianilline, 4,4'- diaminodiphenyl ether or 2,6-bis (3-aminophenoxy) phenonitrile At least one is preferred, and more preferably 4,4'-oxydianilline is most effective. This is a heat resistance material, to realize the optimum physical properties and transparency.

The organic solvent is at least one of N-methyl-2-pyrrolidone, dimethylacetamide, acetonitrile, t-butanol, acetone, dimethylformamide, isopropyl alcohol or ethyl acetate It is preferable that N-methyl-2-pyrrolidone is more preferable. This is to optimize the synthesis process of polyamide acid.

In addition, the group covalent polymer is preferably at least one of polymethyl methacrylate, polyvinyl alcohol or polyvinylpyrrolidone. This effectively forms pores in the heat resistant material, thereby improving heat resistance characteristics such as thermal conductivity.

The pore-copolymer is effectively reacted in the polyamide acid, evenly distributed pores in the optimum size, while significantly improving the heat resistance characteristics, there is an advantage of minimizing physical property degradation.

In addition, the content of the pore copolymer is preferably 5 to 20 parts by weight, more preferably 8 to 14 parts by weight, most preferably 100 parts by weight of the polyamide acid. It is effective to include 10 parts by weight. If it is less than 5 parts by weight, the effect of improving the heat resistance characteristics is insignificant, and if it exceeds 20 parts by weight, not only the physical properties of the heat resistance material are significantly lowered, but also the transparency is significantly lowered.

The particle size of the pore-copolymer is preferably 0.1 μm to 3 μm, more preferably 0.5 μm to 1 μm. If the thickness is less than 0.1 mu m, the manufacturing process is difficult and economic efficiency is low, and the effect of improving the heat resistance characteristics is low. If the thickness is more than 3 mu m, the transparency is remarkably poor, which makes it difficult to use the transparent heat resistance material. .

In addition, the molecular weight of the group-copolymer is preferably 10,000 to 30,000, more preferably 15,000 to 25,000, most preferably 20,000. If less than 10,000 or more than 30,000, there is a problem that can not effectively form pores in the polyamide acid.

Next, the method for producing a transparent heat resistant material composition of the present invention, as shown in Figure 1, characterized in that it comprises a mixing step (S10), the reaction step (S20) and the addition step (S30). Details that are not described below are as mentioned in the transparent heat resistant material composition of the present invention.

Mixing step (S10) is a step of preparing a mixture by mixing an acid anhydride, a diamine compound and an organic solvent. This is a preparation step for synthesizing polyamide acid.

Here, with respect to 1.0 equivalent of the acid anhydride, the diamine compound is preferably mixed in 0.8 to 1.2 equivalents.

In the mixing step (S10), the acid anhydride, the diamine compound and the organic solvent may be mixed in any order.

In addition, the acid anhydride, pyromelliticdian hydride, 4,4'- (hexafluoroisopropylidene) diphthalic dianhydride (4,4'- (Hexafluoroisopropylidene) diphthalicanhydride), 3,3 At least one of 4,4-benzophenone tetracarboxylic dianide, difetyl ether-3,3 ', 4,4'-tetracarboxylic dianhydride or 4,4'-oxydiphthalic dianhydride. The diamine compound may be at least one of 4,4'-oxydianiline (4,4'-Oxydianilline), 4,4'-diaminodiphenyl ether or 2,6-bis (3-aminophenoxy) phenozonitrile. The organic solvent is N-methyl-2-pyrrolidone, dimethylacetamide, acetonitrile, t-butanol, acetone, dimethylformamide, isopropyl alcohol or ethyl acetate. It is preferable that it is at least one of.

Next, the reaction step (S20) is to react the mixture by stirring, to prepare a polyamide acid solution. This is a process for synthesizing polyamide acid through a reaction.

Here, the reaction temperature is preferably maintained by applying heat or cooling outside the chamber to the mixture in the chamber, and stirring may be performed in any manner, but it is effective to stir at a constant speed using a stirrer.

In the reaction step (S20), the reaction temperature is preferably 10 ℃ to 50 ℃, more preferably 20 ℃ to 30 ℃ effective. If the temperature is less than 10 ° C., the synthesis reaction does not occur sufficiently. If the temperature exceeds 50 ° C., there is a problem that the transparency and physical properties of the heat resistant material are significantly reduced due to overreaction.

In addition, in the reaction step (S20), the reaction time is preferably 8 hours to 15 hours, more preferably 10 hours to 12 hours is effective. If it is less than 8 hours, sufficient synthetic reaction does not occur, and if it exceeds 15 hours, there is a problem that not only the transparency is lowered due to overreaction but also the economy is inferior.

In addition, in the reaction step (S20), the viscosity of the polyamide acid solution is preferably 80CPS to 250CPS, more preferably 120CPS to 200CPS, most preferably 140CPS to 170CPS. If it is less than 80CPS or exceeds 250CPS, the synthetic reaction is not made effectively, and the reaction with the covalent polymer in the future addition step (S30) does not sufficiently occur, there is a problem that pores are not formed evenly.

Finally, the adding step (S30) is a step of preparing a transparent heat resistance material composition by adding a covalent polymer to the polyamide acid solution. This is a process for forming pores.

After adding the covalent polymer to the polyamide acid solution produced in the reaction step (S20), and then stirred, the polyamide acid solution and the covalent polymer react with each other to form a heat resistant material having pores.

Here, although stirring may be carried out in any manner, it is effective to stir at a constant speed using a stirrer.

In addition, the temperature in the addition step (S30) is preferably 30 ℃ to 80 ℃, more preferably, it is effective that 50 ℃ to 60 ℃. Outside the temperature range, there is a problem that the pore-forming reaction hardly occurs.

In addition, in the addition step (S30), it is preferable to include 5 to 20 parts by weight of the group covalent polymer, based on 100 parts by weight of the polyamide acid solution, the group covalent polymer is polymethyl methacrylate (polymethyl methacrylate) At least one of polyvinyl alcohol or polyvinylpyrrolidone is effective.

After the addition step (S30), it is preferable to cure for 1 hour to 3 hours at 10 ℃ to 25 ℃.

Hereinafter, look at the experimental results carried out to demonstrate the superiority of the transparent heat resistance material composition and the manufacturing method of the present invention.

First, Figure 2 is a schematic diagram illustrating the formation process of the transparent heat resistance material composition according to the method of manufacturing a transparent heat resistance material composition of the present invention, it shows a process in which pores are formed. Here, the transparent heat resistant material of the present invention was laminated on the matrix.

In addition, Figure 3 and Figure 4 is a reaction formula showing the reaction step (S20) in the method for producing a transparent heat resistant material composition of the present invention, to explain the chemical mechanism of the reaction occurs.

5 to 7 is a SEM photograph of a transparent heat resistant material prepared through the method of manufacturing a transparent heat resistant material composition of the present invention, it can be seen that the pores are uniformly formed in the size required by the present invention. .

8 is a result of measuring the thermal conductivity of the conventional polyimide material and the transparent thermal resistance material of the present invention, it can be seen that the thermal conductivity is reduced by about 10% or more, the thermal resistance characteristic is significantly improved.

In addition, Figure 9 is a result of measuring the Young's modulus (E-modulus) of the conventional polyimide material and the transparent thermal resistance material of the present invention, the Young's modulus is reduced by about 20%, the physical property degradation is minimized, transparent thermal resistance It can be seen that the properties required by the material can be satisfied.

Claims (17)

Polyamide acid and covalent polymer,
To about 100 parts by weight of the polyamide acid, containing 5 to 20 parts by weight of the covalent polymer, the particle size of the covalent polymer is characterized in that the transparent heat resistance material composition characterized in that 0.1㎛ to 3㎛
The method according to claim 1,
The covalent polymer is a transparent heat resistance material composition, characterized in that at least one of polymethyl methacrylate (polymethyl methacrylate), polyvinyl alcohol (polyvinyl alcohol) or polyvinylpyrrolidone (polyvinylpyrrolidone)
delete 3. The method according to claim 1 or 2,
The molecular weight of the covalent polymer is a transparent heat resistance material composition, characterized in that 10,000 to 30,000
3. The method according to claim 1 or 2,
The polyamide acid is formed by mixing an acid anhydride, a diamine compound and an organic solvent to react.
6. The method of claim 5,
With respect to 1.0 equivalent of the acid anhydride, the diamine compound is a transparent heat resistance material composition, characterized in that mixed in 0.8 to 1.2 equivalents
6. The method of claim 5,
The acid anhydride is pyromelliticdian hydride, 4,4 '-(hexafluoroisopropylidene) diphthalic dianhydride (4,4'-(Hexafluoroisopropylidene) diphthalicanhydride), 3,3,4 At least one of 4-benzophenone tetracarboxylic dianide, difetyl ether-3,3 ', 4,4'-tetracarboxylic dianhydride or 4,4'-oxydiphthalic dianhydride. Transparent heat resistant material composition 6. The method of claim 5,
The diamine compound is at least one of 4,4'-oxydianiline (4,4'-Oxydianilline), 4,4'-diaminodiphenyl ether or 2,6-bis (3-aminophenoxy) phenozonitrile Transparent heat resistance material composition, characterized in that
6. The method of claim 5,
The organic solvent is at least one of N-methyl-2-pyrrolidone, dimethylacetamide, acetonitrile, t-butanol, acetone, dimethylformamide, isopropyl alcohol or ethyl acetate Transparent heat resistance material composition, characterized in that
A mixing step of preparing a mixture by mixing an acid anhydride, a diamine compound and an organic solvent;
Reacting the mixture by stirring to prepare a polyamide acid solution; And
And adding an air-covalent polymer to the polyamide acid solution to prepare a transparent heat resistance material composition.
In the reaction step, the reaction time is a method for producing a transparent heat resistant material composition, characterized in that 8 hours to 15 hours. 11. The method of claim 10,
In the reaction step, the reaction temperature is a method for producing a transparent heat resistance material composition, characterized in that 10 ℃ to 50 ℃.
delete The method according to claim 10 or 11,
In the addition step, with respect to 100 parts by weight of the polyamide acid solution, a method for producing a transparent heat resistance material composition comprising 5 to 20 parts by weight of the group covalent polymer
The method according to claim 10 or 11,
In the addition step, the group covalent polymer is at least one of polymethyl methacrylate (polymethyl methacrylate), polyvinyl alcohol (polyvinyl alcohol) or polyvinylpyrrolidone (polyvinylpyrrolidone) of the transparent heat resistance material composition Manufacturing method
The method according to claim 10 or 11,
In the mixing step, with respect to 1.0 equivalent of the acid anhydride, the diamine compound is a method for producing a transparent heat resistance material composition, characterized in that mixed in 0.8 to 1.2 equivalents
The method according to claim 10 or 11,
In the mixing step, the acid anhydride, pyromelliticdian hydride, 4,4'- (hexafluoroisopropylidene) diphthalic dianhydride (4,4'- (Hexafluoroisopropylidene) diphthalicanhydride), In 3,3,4,4-benzophenonetetracarboxylic dianide, dipetylether-3,3 ', 4,4'-tetracarboxylic dianhydride or 4,4'-oxydiphthalic dianhydride At least one, and the said diamine compound is 4,4'- oxy dianiline (4,4'- Oxydianilline), 4,4'- diamino diphenyl ether or 2, 6-bis (3-amino phenoxy) phenzo At least one of nitriles, and the organic solvent is N-methyl-2-pyrrolidone, dimethylacetamide, acetonitrile, t-butanol, acetone, dimethylformamide, isopropyl alcohol Or at least one of ethyl acetate.
The method according to claim 10 or 11,
In the reaction step, the viscosity of the polyamide acid solution is a method for producing a transparent heat resistance material composition, characterized in that 80CPS to 250CPS

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