KR20160146250A - Ceramic sol nanohybrid materials using polydimethylsiloxane-polyamideimide copolymers and manufacturing method thereof - Google Patents

Ceramic sol nanohybrid materials using polydimethylsiloxane-polyamideimide copolymers and manufacturing method thereof Download PDF

Info

Publication number
KR20160146250A
KR20160146250A KR1020150083260A KR20150083260A KR20160146250A KR 20160146250 A KR20160146250 A KR 20160146250A KR 1020150083260 A KR1020150083260 A KR 1020150083260A KR 20150083260 A KR20150083260 A KR 20150083260A KR 20160146250 A KR20160146250 A KR 20160146250A
Authority
KR
South Korea
Prior art keywords
polyamideimide
polydimethylsiloxane
group
pdms
copolymer
Prior art date
Application number
KR1020150083260A
Other languages
Korean (ko)
Other versions
KR101704593B1 (en
Inventor
박진희
강동필
이대호
전제홍
한세원
Original Assignee
한국전기연구원
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 한국전기연구원 filed Critical 한국전기연구원
Priority to KR1020150083260A priority Critical patent/KR101704593B1/en
Publication of KR20160146250A publication Critical patent/KR20160146250A/en
Application granted granted Critical
Publication of KR101704593B1 publication Critical patent/KR101704593B1/en

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/14—Polyamide-imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

The present invention relates to a ceramic sol nanohybrid material using a polydimethylsiloxane-polyamideimide copolymer and a manufacturing method thereof and, more specifically, to a ceramic sol nanohybrid material using a polydimethylsiloxane-polyamideimide copolymer and a manufacturing method thereof, wherein the ceramic sol nanohybrid material has excellent lubricity, flexibility, water repellency, durability, heat resistance and abrasion resistance by using polydimethylsiloxane (PDMS) capable of reacting with polyamideimide including a highly reactive isocyanate group at a terminus and is formed by mixing: a ceramic sol; and a polydimethylsiloxane-polyamideimide copolymer formed by binding PDMS to the isocyanate group of the polyamideimide, wherein a hydroxyl or ether group is capped in a part of a chain of the isocyanate group inside the polyamideimide.

Description

TECHNICAL FIELD The present invention relates to a ceramic sol nanohybrid material using a polydimethylsiloxane-polyamideimide copolymer and a method for producing the same.

The present invention relates to a ceramic sol nano hybrid material using a polydimethylsiloxane-polyamideimide-based copolymer and a method for producing the same. More particularly, the present invention relates to a process for producing a polydimethylsiloxane-polyamideimide- Polyamideimide-based copolymer having excellent lubricity, flexibility, water repellency, durability, heat resistance and abrasion resistance by using a siloxane, and a method for producing the same.

Generally, coatings having low surface energy are attracting much attention because they can protect the surface of the coated substrate from the external environment, since nonstick, anti-fouling and water repellent coatings are possible. When the insulated coil is fabricated with a material having such a low surface energy, the workability of the motor manufacturing is improved due to the high lubrication characteristic (lysability).

Particularly, there are many coating varnishes such as polyamideimide (PAI) having good heat resistance and insulation properties. The prior art related to such polyamideimides has been filed in many publications. For example, in the polyamideimide varnish (Application No. 10-2003-0099624), which has excellent heat resistance and bending resistance, the polyamideimide varnish prepared by using an acid anhydride and a diisocyanate Wherein the molar ratio of 4,4'-oxydianiline to diisocyanate is 1: 0.9 to 1: 1 based on the acid anhydride. : 1.1, to provide a polyamideimide varnish.

However, since the polyamide imide has a structure in which an amide group having a polarity and an imide group are repeatedly used, the polyamide imide should be mixed with a material having a low surface energy in order to increase lubrication.

In the case of physical mixing or copolymerization of highly flexible silicon and organic resin having a low surface energy and low surface energy (~ 20 mN / m) due to a low intermolecular force between methyl groups, a small amount of silicon Also has the advantage that a very low surface tension can be obtained by movement of silicon molecules.

Furthermore, the surface tension has a lower surface energy as the polymer is more flexible. Polydimethylsiloxane (PDMS) has a spiral chain form and is composed of relatively long Si-O (0.164 nm) and Si-C And high flexibility due to Si-O bond rotation with low barrier.

In addition, when the polydimethylsiloxane (PDMS) is coated on the surface, it has low surface tension, high thermal / oxidative stability, UV resistance, reduced friction, high water repellency low surface shear viscosity, good lubrication, soft feel, good electrical properties, high permeability to many gases, And low toxicity, and the like.

However, polydimethylsiloxane (PDMS) lacks toughness and has low adhesion to other materials, making it difficult to use PDMS alone. Accordingly, when blending or copolymerizing an organic resin and silicone, it is possible to reduce the above-mentioned characteristics, for example, to reduce moisture adsorption and reduce the degree of oxidation to air, A resin having a toughness while having a corona property can be produced.

Unlike polydimethylsiloxane (PDMS), which is a hydrophobic polymer, resins such as PI, PA, and PAI contain polar groups such as amide and imide. Physical blending of two polymers having opposite physical properties results in phase separation on a macroscopic scale.

However, when chemical substances with different surface energies are made into a single copolymer through covalent bonds, this phase separation can be effectively reduced. In addition, the durability can be effectively increased since the silicon molecules do not readily separate from the surface.

In addition, the types of copolymers include AB diblock, ABA triblock copolymers, (AB) n multiblock copolymers, star like block copolymers and grafted copolymers.

When copolymers are made in this way, phase separation occurs on a microscopic scale and various morphologies can be obtained depending on the size and composition of the segments constituting the copolymer.

In 1966, pyromellitic dianhydride (PMDA) was reacted with an amine terminated siloxane dimer to synthesize a siloxane-imide copolymer. Various amideimide-siloxane, imide-siloxane and amide- Copolymers have been synthesized in a variety of ways.

On the other hand, a method of synthesizing dicarboxyl-terminated imide and dicarboxyl-terminated polysiloxane with block-amide-siloxane- (block-amide-imide) copolymers using a diisocyanate coupling agent has been disclosed. Recently, And polydimethylsiloxane-based technologies.

KR 10-2005-0070290 A

The present invention was made to solve the problems caused by phase separation in the case of physical mixing of the above polydimethylsiloxane and polyamideimide, and it relates to a process for producing a polyamideimide by incorporating polydimethylsiloxane into polyamideimide, Polyamideimide-based copolymer capable of improving thermal / mechanical properties such as moldability, durability and the like as well as improving lubricity, and a process for producing the same. .

In order to achieve the above object, the present invention provides a ceramic sol nanohybrid material, which comprises a polyamideimide in which a hydroxyl group or an ether group is capped in a part of an isocyanic chain, a polydimethylsiloxane (PDMS) in the isocyanic group, A polydimethylsiloxane-polyamideimide-based copolymer formed by bonding together; And a ceramic sol; and a ceramic sol nano hybrid material using the polydimethylsiloxane-polyamideimide-based copolymer.

A first step of polymerizing a diisocyanate compound and an acid anhydride compound to synthesize a polyamideimide having an isocyanic group on a part of the chain; A second step of adding at least one of glycol ethers and alcohols to the polyamideimide so that a hydroxyl group or an ether group is capped in a part of the polyamideimide chain having an isocyanate group; A third step of synthesizing a polydimethylsiloxane-polyamideimide-based copolymer by reacting polydimethylsiloxane (PDMS) with a polyamideimide to which at least one of the glycol ethers and alcohols is added; And a fourth step of mixing a ceramic sol with the polydimethylsiloxane-polyamideimide-based copolymer to prepare a ceramic sol nanohybrid material, wherein the polydimethylsiloxane-polyamideimide-based copolymer Can be achieved through a method of manufacturing a ceramic sol nanohybrid material.

Preferably, the polydimethylsiloxane (PDMS) in the third step has at least one of reactive groups containing hydroxyl groups, an acid group, an amine group, an anhydride group, an epoxy group and a thiol group at both terminals, And is reacted with an isocyanic group of a polyamideimide chain.

The molecular weight of polydimethylsiloxane (PDMS) having at least one of reactive groups including hydroxyl group, an acid group, an amine group, an anhydride group, an epoxy group and a thiol group at both ends is 500 to 20,000 Da .

The molecular weight of the polyamide-imide having an isocyanate group in a part of the terminal of the chain is 5,000 to 500,000 Da.

Wherein the diisocyanate compound is selected from the group consisting of 4,4'-methylenebis (phenyl isocyanate), 2,2-bis (4-isocyanatophenyl) hexafluoropropane (2 4-isocyanatophenyl) hexafluoropropane, 4,4'-diisocyanato-3,3'-dimethylbiphenyl, 4,4'- Diisocyanato-3,3'-dimethyldiphenylmethane, 1,5-diisocyanatonaphthalene, 1-diisocyanate, , 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, and derivatives thereof. The present invention is not limited to these examples.

In order to accomplish the above object, the present invention provides a ceramic sol nanohybrid material comprising a polydimethylsiloxane-polyamide polymer in which a polyamideimide having isocyanate groups at both ends of a chain and a polydimethylsiloxane (PDMS) Polyamideimide-based copolymers; And a ceramic sol; and a ceramic sol nano hybrid material using the polydimethylsiloxane-polyamideimide-based copolymer.

A first step of polymerizing a diisocyanate compound and an acid anhydride compound to synthesize a polyamideimide having isocyanate groups at both ends of the chain; A polyimide siloxane-polyamideimide system (PDMS) in which the polyamideimide and the polydimethylsiloxane (PDMS) are successively bonded in sequence by reacting polydimethylsiloxane (PDMS) with polyamideimide having isocyanate groups at both ends of the chain A second step of synthesizing a copolymer; And a third step of mixing a ceramic sol with the polydimethylsiloxane-polyamideimide-based copolymer to prepare a ceramic sol nanohybrid material, wherein the polydimethylsiloxane-polyamideimide-based copolymer Can be achieved through a method of manufacturing a ceramic sol nanohybrid material.

Preferably, the polydimethylsiloxane (PDMS) in the second step has at least one of reactive groups containing hydroxyl groups, an acid group, an amine group, an anhydride group, an epoxy group and a thiol group at both terminals, And is reacted with an isocyanic group of the polyamideimide chain.

The molecular weight of polydimethylsiloxane (PDMS) having at least one of reactive groups including hydroxyl group, an acid group, an amine group, an anhydride group, an epoxy group and a thiol group at both ends is 500 to 20,000 Da .

A ceramic sol nanohybrid material using the polydimethylsiloxane-polyamideimide-based copolymer according to the present invention by the means for solving the above-mentioned problems and a method for producing the same are characterized in that a polyamideimide having a polar amide group and an imide group repeating structure By adding polydimethylsiloxane, lubricity and flexibility can be improved.

Further, addition of a ceramic sol to the polydimethylsiloxane-polyamideimide-based copolymer has the effect of reinforcing a weak mechanical strength which is a disadvantage of polydimethylsiloxane.

1 shows the synthesis of a polydimethylsiloxane-polyamideimide-based copolymer (AB diblock copolymer) according to a preferred embodiment of the present invention.
FIG. 2 is a comparative state diagram of a polydimethylsiloxane-polyamideimide-based copolymer synthesized by a physical mixing method and a chemical method according to a preferred embodiment of the present invention. FIG.
3 is a contact angle graph of a polydimethylsiloxane-polyamideimide-based copolymer synthesized by a physical method and a chemical method according to a preferred embodiment of the present invention.
4 is a water droplet state diagram on the surface of a polydimethylsiloxane-polyamideimide copolymer synthesized by a chemical method according to a preferred embodiment of the present invention.
FIG. 5 is a graph showing the contact angle difference of a polydimethylsiloxane-polyamideimide-based copolymer synthesized by a physical method and a chemical method according to a preferred embodiment of the present invention.
6 is a solution state diagram in which boron nitride is hybridized with a polydimethylsiloxane-polyamideimide-based diblock copolymer according to a preferred embodiment of the present invention.
7 is a state diagram of a varnish in which a silica sol is hybridized with a polydimethylsiloxane-polyamideimide type diblock copolymer according to a preferred embodiment of the present invention.
8 is a state diagram of a varnish in which a silica sol is hybridized with a polydimethylsiloxane-polyamideimide-based diblock copolymer according to a preferred embodiment of the present invention.
9 is a water droplet state diagram after coating a varnish hybridized with a silica sol on a polydimethylsiloxane-polyamideimide type diblock copolymer according to a preferred embodiment of the present invention.
10 is a polydimethylsiloxane-polyamideimide-based multi-block copolymer having a repeating structure of a polyamideimide and a polydimethylsiloxane according to a preferred embodiment of the present invention.
11 is a water droplet state diagram on a surface coating of a polydimethylsiloxane-polyamideimide-based multi-block copolymer according to a preferred embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

The ceramic sol nanohybrid material using the polydimethylsiloxane-polyamideimide-based copolymer according to a preferred embodiment of the present invention has a hydroxyl group or an ether group capped in a part of the chain having an isocyan (-NCO) group polyamide-imide-based copolymer formed by bonding polydimethylsiloxane (PDMS) to an isocyan (-NCO) group to a polyimide imide having a capping structure and a ceramic sol.

The polydimethylsiloxane-polyamideimide-based copolymer in this case refers to a polydimethylsiloxane-polyamideimide-based diblock copolymer, and a ceramic sol nanohybrid material using the polydimethylsiloxane-polyamideimide-based diblock copolymer The method for fabricating the semiconductor device may include a first step, a second step, a third step and a fourth step.

First, the first step is to synthesize a polyamideimide having an isocyan (-NCO) group in a part of the end of the polymer chain by polymerizing a diisocyanate compound and an acid anhydride compound.

That is, the first step is a step of reacting a diisocyanate compound and an acid anhydride compound at a certain stoichiometric ratio to prepare a polyamideimide of 5,000 to 500,000 Da (molecular weight) having an isocyan (-NCO) group at the terminal.

If the polyamide-imide in the first stage is less than 5,000 Da, it can not maintain a constant strength. If it is higher than 500,000 Da, the viscosity is too high, and when the behavior is low, it is difficult to easily react with reactive polydimethylsiloxane (PDMS) (PDMS) ratio is lowered to lower the lubricity, it is preferable that the polyamideimide has a size of 5,000 to 500,000 Da.

Here, the diisocyanate compound may be 4,4'-methylenebis (phenyl isocyanate), 2,2-bis (4-isocyanatophenyl) hexafluoropropane (2,2'- (4-isocyanatophenyl) hexafluoropropane, 4,4'-diisocyanato-3,3'-dimethylbiphenyl, 4,4'- Diisocyanato-3,3'-dimethyldiphenylmethane, 1,5-diisocyanatonaphthalene, 1,3-diisocyanato- At least one selected from the group consisting of 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate and derivatives thereof can be selected.

The acid anhydride compound may be selected from TMA (trimellitic anhydride) and derivatives thereof.

Next, the second step is to add at least one of glycol ethers and alcohols to the polyamideimide so that hydroxyl group or ether group is capped in a part of the polyamideimide chain having an isocyan (-NCO) group .

Specifically, in the second step, only a portion of the isocyan (-NCO) groups remaining at the ends of the polyamideimide after the first step is capped with glycol ethers or alcohols. have.

Examples of the glycol ethers include 2-methoxyethanol, 1-methoxy-2-propanol, 2-ethoxyethanol, Butanol, 2-propoxyethanol, 2-isopropoxyethanol, 2-butoxyethanol, 2-phenoxyethanol, 2-benzyloxyethanol 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol, 2- (2-methoxyethoxy) (2-butoxyethoxy) ethanol, 1-ethoxy-2-propanol, and derivatives thereof.

As the alcohols, any one or more of ethanol, isopropyl alcohol, benzyl alcohol and derivatives thereof may be selected and used.

Next, the third step is to synthesize a polydimethylsiloxane-polyamideimide-based copolymer by reacting polydimethylsiloxane (PDMS) having a reactive group with a polyamideimide to which at least one of glycol ethers and alcohols is added to be.

That is, in the third step, in order to impart lubricity and flexibility to the polyamideimide after the second step, a poly (dimethylsiloxane-polyamideimide) -based copolymer is obtained through chemical reaction with polydimethylsiloxane (PDMS) . ≪ / RTI >

1 is a synthesis scheme of a polydimethylsiloxane-polyamideimide-based copolymer (A-B diblock copolymer) according to a preferred embodiment of the present invention. Referring to FIG. 1, PAI containing an isocyan (-NCO) group at a terminal is reacted with polydimethylsiloxane (PDMS) containing an amine group to show a reaction for synthesizing a polydimethylsiloxane-polyamideimide copolymer Able to know.

That is, by capping the PAI end with PGME (1-Methoxy-2-propanol) and bonding the remaining isocyan (-NCO) group to diamine-polydimethylsiloxane via urea reaction, A dimethylsiloxane-polyamideimide-based copolymer is synthesized.

In this case, hydroxyl groups, acid groups, and amine groups, which are reactive groups capable of reacting with isocyan (-NCO) groups, are bonded to both ends of polydimethylsiloxane (PDMS) in the range of 500 to 20,000 mol / (-NCO) group at the terminal of the polyamide-imide chain at the second stage and a reactive group at the terminal of the polyamide-imide chain at the second step by having at least one of reactive groups including an epoxy group, an anhydride group, an epoxy group, and a thiol group It is preferable to carry out the reaction.

Additionally, when the length (molecular weight) of polydimethylsiloxane (PDMS) is less than 500 Da, the lubricity is low and longer than 20,000 Da, the lubricity is good but the mechanical strength may deteriorate. Therefore, the length of polydimethylsiloxane (PDMS) Da. ≪ / RTI >

2 is a comparative state diagram in which a polydimethylsiloxane-polyamideimide-based copolymer is synthesized by a physical mixing method and a chemical method according to a preferred embodiment of the present invention.

Referring to FIG. 2, FIG. 2- (a) shows a polydimethylsiloxane-polyamideimide copolymer solution physically mixed according to polydimethylsiloxane (PDMS) content and a film obtained by coating this solution on a slide glass 2- (b) shows a polydimethylsiloxane-polyamideimide copolymer solution chemically mixed according to polydimethylsiloxane (PDMS) content and a film obtained by coating this solution on a slide glass.

As shown in FIG. 2- (a), when phase-separated physical mixing is carried out, the size of a separated domain or phase is large and the refractive indices are different. It can be seen that the PAI is divided into a portion having a low PAI and a lot of portions, resulting in a wave pattern.

In this way, when capping all isocyanin (-NCO) groups, reactive groups of polydimethylsiloxane (PDMS) do not react with PAI, but only physically mixed to divide polydimethylsiloxane (PDMS) and PAI into two layers, Can be confirmed to be opaque.

When such a solution is coated on a slide glass and its surface is examined, the surface is uneven and a large domain is often formed, and it can be confirmed that the non-uniformity increases as the amount of polydimethylsiloxane (PDMS) increases.

As shown in FIG. 2- (b), in the case of a copolymer through covalent bonding, it can be confirmed that the domain is very small and transparent.

Specifically, it can be confirmed that even when polydimethylsiloxane (PDMS) is incorporated into PAI containing an isocyan (-NCO) group capable of reacting with polydimethylsiloxane (PDMS) up to a solid content ratio of 30%.

And the chemical bonding of polydimethylsiloxane (PDMS) and PAI does not make much difference compared to that without polydimethylsiloxane (PDMS) until the surface is very uniform and polydimethylsiloxane (PDMS) is 2.5%. That is, the surface is uniform in the case of chemically bonded PAI and polydimethylsiloxane (PDMS).

3 is a contact angle graph of a polydimethylsiloxane-polyamideimide-based copolymer synthesized by a physical method and a chemical method according to a preferred embodiment of the present invention. Referring to FIG. 3, contact angles of PDMS / PAI coated on a slide glass can be measured to confirm whether polydimethylsiloxane (PDMS) is effectively present on the surface.

In the case of physically mixed PDMS-PAI (fully capped), there is little difference in the contact angle value from 91 to 92 ° even though the polydimethylsiloxane (PDMS) content increases to 10%. In contrast, in the case of chemically mixed PDMS-PAI (partially capped) copolymers, the contact angle increases sequentially from 94 ° to 101 ° as the polydimethylsiloxane (PDMS) content increases.

In addition, polydimethylsiloxane (PDMS) is known to have a water contact angle of 101 °, which is highly mixed with PAI, so that the polydimethylsiloxane (PDMS) It can be seen that it maintains the intrinsic value of dimethylsiloxane (PDMS).

In order to confirm the uniformity of the surface, the deviation of the contact angle was obtained and the deviation was averaged. As a result, it was found that it was 1.17 ° in the case of physically mixed, but 0.751 ° in the case of chemically bonded copolymer.

As a result, it can be seen that the homogeneity of the surface of the copolymer having a relatively small domain size is higher than that of the case where the copolymer is physically mixed.

4 is a water droplet state diagram on the surface of a polydimethylsiloxane-polyamideimide copolymer synthesized by a chemical method according to a preferred embodiment of the present invention. Referring to FIG. 4, the polydimethylsiloxane-polyamideimide-based copolymer showed a water droplet state when the content (%) of polydimethylsiloxane (PDMS) was 1.0, 2.5 and 5.0%, and polydimethylsiloxane ), The contact angle increased from 94 ° to 101 ° as the content increased to 1.0, 2.5 and 5.0%.

FIG. 5 is a graph of the contact angle difference of a polydimethylsiloxane-polyamideimide-based copolymer synthesized by a physical method and a chemical method according to a preferred embodiment of the present invention. Referring to FIG. 5, it can be seen that the film of PDMS / fully capped PAI physically bonded to the chemically bonded PDMS / partially capped PAI exhibited a contact angle difference before and after the toluene washing process. However, in the case of 0% PDMS-PAI containing no polydimethylsiloxane (PDMS), the contact angle increases or does not change after toluene treatment.

Specifically, when a film is made with physically mixed PDMS-PAI (fully capped), the surface polydimethylsiloxane (PDMS) is dissolved when it is washed with an organic solvent such as toluene. That is, the contact angle is relatively largely reduced as compared with the case where polydimethylsiloxane (PDMS) easily melts and chemically bonds.

Finally, the fourth step is a step of preparing a ceramic sol nanohybrid material by mixing a ceramic sol with a polydimethylsiloxane-polyamideimide-based copolymer.

In the fourth step, a polydimethylsiloxane-polyamideimide-based diblock copolymer containing 1% and 5% of polydimethylsiloxane (PDMS) synthesized was hybridized with a ceramic sol to form a ceramic sol nano hybrid material .

Specifically, the fourth step is a step in which a boron nitride (BN) having high thermal conductivity and also used as a lubricant is added to the polydimethylsiloxane-polyamideimide type diblock copolymer, or a silica sol capable of increasing wear resistance heat resistance Micro / nano hybrid material. In this case, the micro / nanohybrid material means that there is no increase in viscosity and can be coated on the surface in the form of a film.

The ceramic sol may be formed by adding a solvent containing water to an oxide, nitride, or carbide nanoparticle such as silica, alumina, boron nitride, or silicon carbide, stirring the solution, modifying the surface with silane, and adding an organic solvent. have.

6 is a solution state diagram in which boron nitride is hybridized with a polydimethylsiloxane-polyamideimide-based diblock copolymer according to a preferred embodiment of the present invention.

6- (a) is a 20% hybrid solution of polydimethylsiloxane-polyamideimide-based diblock copolymer containing 5% polydimethylsiloxane (PDMS) treated with DN silane at 20% b) shows a polydimethylsiloxane-polyamideimide type diblock copolymer containing 5% polydimethylsiloxane (PDMS) in which 20% of boron nitride treated with PN silane is hybridized, and Fig. 6- (c) % Of polydimethylsiloxane (PDMS) and 20% of boron nitride treated with both PN and DN silane.

That is, a solution in which boron nitride and a polydimethylsiloxane-polyamideimide diblock copolymer are hybridized is shown. After the surface coating, the contact angle is maintained at 91 ° or more and 98.5 ° at the maximum, so that the hybrid with boron nitride affects lubrication .

7 is a state diagram of a varnish in which a silica sol is hybridized with a polydimethylsiloxane-polyamideimide-based diblock copolymer according to a preferred embodiment of the present invention. 7- (a) is a polydimethylsiloxane-polyamideimide-based diblock copolymer containing 1% polydimethylsiloxane (PDMS), which is a varnish obtained by 10% hybridization of silica sol and FIG. 7- (b) (PDMS) -based polydimethylsiloxane-polyamideimide diblock copolymer containing polydimethylsiloxane (PDMS) and 15% of silica sol. FIG. 7- (c) A polydimethylsiloxane-polyamideimide type diblock copolymer is a varnish obtained by 20% hybridization of silica sol.

8 is a state diagram of a varnish in which a silica sol is hybridized with a polydimethylsiloxane-polyamideimide-based diblock copolymer according to a preferred embodiment of the present invention. 8- (a) is a polydimethylsiloxane-polyamideimide-based diblock copolymer containing 1% polydimethylsiloxane (PDMS) in which 20% of silica sol is hybridized and FIG. 8- (b) A polydimethylsiloxane-polyamideimide-based diblock copolymer containing polydimethylsiloxane (PDMS) is a 20% -hybridized silica sol.

Referring to FIGS. 7 and 8, when a silica sol is hybridized with a polydimethylsiloxane-polyamideimide-based diblock copolymer, a transparent varnish in which nano-sized silica sol is not visible can be identified.

FIG. 9 is a water droplet state diagram of a polydimethylsiloxane-polyamideimide-based diblock copolymer surface-coated with a varnish obtained by hybridizing silica sol according to a preferred embodiment of the present invention. Referring to FIG. 9, a varnish was prepared by surface-coating a polydimethylsiloxane-polyamideimide diblock copolymer containing 1% polydimethylsiloxane (PDMS) with 10%, 15% and 20% And the droplet is measured.

In other words, when the silica sol was hybridized with 10%, 15%, and 20% of the hybrid sol, the hybrid varnish was coated on the surface and the contact angle was measured. As a result, the contact angle was 98 ° or more .

In addition, as a result of pencil hardness test, it is possible to produce a hybrid varnish which satisfies both lubricity and hardness because polydimethylsiloxane (PDMS) having low hardness is treated and the hardness dropped can be maintained well by the hybridization with silica .

Meanwhile, a ceramic sol nanohybrid material using another polydimethylsiloxane-polyamideimide-based copolymer (AB) n multiblock copolymer according to a preferred embodiment of the present invention has isocyan (-NCO) groups at both ends of the chain, Polyamide-imide-based copolymer in which a polyamide-imide having at least one functional group and a polydimethylsiloxane (PDMS) are successively bonded in sequence, and a ceramic sol. In this case, the polydimethylsiloxane-poly The amide imide-based copolymer means a polydimethylsiloxane-polyamideimide-based multi-block copolymer.

10 is a polydimethylsiloxane-polyamideimide-based multi-block copolymer having a repeating structure of polyamideimide and polydimethylsiloxane (PDMS) according to a preferred embodiment of the present invention. Referring to FIG. 10, a polydimethylsiloxane-polyamideimide-based multi-block copolymer is shown in which the structures of polyamideimide and polydimethylsiloxane (PDMS) can be repeatedly formed.

11 is a water droplet state diagram on a surface coating of a polydimethylsiloxane-polyamideimide-based multi-block copolymer according to a preferred embodiment of the present invention. Referring to FIG. 11, it can be seen that the polydimethylsiloxane-polyamideimide-based multi-block copolymer containing 5% polydimethylsiloxane (PDMS) has a water droplet state on the coated surface.

The method for producing the ceramic sol nanohybrid material using the polydimethylsiloxane-polyamideimide-based multi-block copolymer can be largely composed of the first step, the second step, and the third step.

First, the first step is a step of synthesizing a polyamideimide having isocyan (-NCO) groups at both terminals of a polymer chain by polymerizing a diisocyanate compound and an acid anhydride compound.

Briefly, the first step is to synthesize a PAI segment having isocyan (-NCO) groups at the ends of 2,000 to 10,000 Da in size to synthesize a multi-block copolymer.

For reference, when the PAI segment is less than 2,000 Da, the mixing property is poor. When the PAI segment is more than 10,000 Da, the amount of the polydimethylsiloxane (PDMS) that can be included in one polymer is limited. Therefore, the PAI segment has a size of 2,000 to 10,000 Da .

Here, the diisocyanate compound may be 4,4'-methylenebis (phenyl isocyanate), 2,2-bis (4-isocyanatophenyl) hexafluoropropane (2,2'- (4-isocyanatophenyl) hexafluoropropane, 4,4'-diisocyanato-3,3'-dimethylbiphenyl, 4,4'- Diisocyanato-3,3'-dimethyldiphenylmethane, 1,5-diisocyanatonaphthalene, 1,3-diisocyanato- At least one of phenylene diisocyanate, 1,4-phenylene diisocyanate and derivatives thereof can be selected and used.

The acid anhydride compound can be selected from TMA (trimellitic anhydride) and derivatives thereof.

Next, in the second step, polyimide siloxane (PDMS) is reacted with a polyamideimide having isocyan (-NCO) groups at both ends of the chain so that the polyamideimide and the polydimethylsiloxane (PDMS) are successively bonded To synthesize a polydimethylsiloxane-polyamideimide-based copolymer.

Wherein the polydimethylsiloxane (PDMS) has at least one of reactive groups including hydroxyl groups, acid groups, amine groups, anhydride groups, epoxy groups and thiol groups at both ends, and the reactive groups of the polyamideimide chain ends of the first stage When the length (molecular weight) of the polydimethylsiloxane (PDMS) is less than 500 Da, the lubricity is low. When the polydimethylsiloxane (PDMS) is longer than 20,000 Da, the lubricity is good but the mechanical strength is deteriorated. The length of the siloxane (PDMS) is preferably in the range of 500 to 20,000 Da.

That is, in the second step, a reactive group such as a hydroxyl group, an acid group, an anhydride group, an amine group, an epoxy group and a thiol group at both terminals of polydimethylsiloxane (PDMS) is reacted with an isocyanic (-NCO) - polyamideimide-based multi-block copolymer can be synthesized.

For reference, the size of the PAI synthesized in the first step can be determined according to the size of the polydimethylsiloxane (PDMS) used and the ratio of the organic resin and polydimethylsiloxane (PDMS). For example, in order to adjust the ratio of the diamine-PDMS to 2,600 g / mol and the ratio of the organic resin to the PAI to 1: 1, the amount of MDI in the MDI over- Da-sized PAI can be synthesized.

It is preferred that the isocyan (-NCO) groups at both ends of PAI are repeatedly bonded to amine groups of polydimethylsiloxane (PDMS) to obtain polydimethylsiloxane-polyamideimide-based multi-block copolymers having a size of 6 to 70,000 Da .

This is because the size of the final polydimethylsiloxane-polyamideimide multi-block copolymer may be changed depending on the purpose, but in the present invention, it is synthesized with a goal of 6-70,000 Da because it is used in combination with 10,000 Da of general PAI.

In the case of the synthesized polydimethylsiloxane-polyamideimide multiblock copolymer, the proportion of -NO = CN-PAI-NC = ON- and polydimethylsiloxane (PDMS) is almost 1: 1, Mixed. That is, it can be confirmed that the synthesized polydimethylsiloxane-polyamideimide-based multi-block copolymer is homogeneously mixed well with PAI.

However, in the case of a polymer made by 1: 1 reaction of diamine-PDMS with MDI, the polarity of -N-O = C-N-MDI-N-C = O-N- When the contact angle was measured by mixing the thus-synthesized copolymer with PAI at a ratio of 5:95, the results were similar to those obtained by capping polydimethylsiloxane (PDMS) at only 10 to 20% at the terminal at 101.9 ° And the synthesis of a multi-block copolymer is an effective method.

Finally, the third step is a step of preparing a ceramic sol nanohybrid material by mixing a ceramic sol with a polydimethylsiloxane-polyamideimide-based copolymer.

This third step technique is the same as the fourth step of the manufacturing method of the ceramic sol nanohybrid material using the polydimethylsiloxane-polyamideimide-based copolymer (AB diblock copolymer). .

Hereinafter, embodiments relating to a ceramic sol nano hybrid material using the polydimethylsiloxane-polyamideimide-based copolymer of the present invention and a manufacturing method thereof will be described.

≪ Example 1 >

Polydimethylsiloxane - polyamideimide type copolymer (A-B diblock copolymer )

A solution of 3.67 g of 1-methoxy-2-propanol (PGME) in 48.17 g of 1-methyl-2-pyrrolidinone (NMP) was prepared and dissolved in 200 g of PAI having a solid content of 34% After the addition, the PGME and PAI solutions are heated to 80 ° C and held for 2 hours.

Thereafter, the temperature is lowered to room temperature, and diamine-PDMS (Tegomer A-Si 2322, ~ 2600 g / mol) is added at a solid content ratio of 0.5 to 30% and stirred at 200 rpm for 2 hours or more. When PAI capped with PGME without immediately reacting diamine-PDMS is kept at room temperature for more than one week, the remaining PGME reacts with all isocyan (-NCO) groups of PAI to react with polydimethylsiloxane (PDMS) Can not.

2 * 5 cm 2 The solution is coated on PDMS-PAI synthesized on a slide glass and the temperature is raised stepwise to make a film. Finally, the properties of the film can be evaluated by measuring the contact angle, TGA, and DSC of the film.

≪ Example 2 >

Polydimethylsiloxane - polyamideimide-based copolymer ((AB) n multiblock  copolymer

12.51 g (50 mmol) of 4,4'-methylenebis (phenylisocyanate), 8.38 g (43.6 mmol) of TMA and 82.14 g of NMP are placed in a flask filled with nitrogen and heated to 50 ° C. with stirring at 200 rpm. When both MDI and TMA are dissolved, the temperature is raised to 80 ° C., then maintained for 2 hours, elevated to 110 ° C., and reacted for 1 hour.

Thereafter, the temperature was lowered to room temperature, and 19.56 g (7.52 mmol) of polydimethylsiloxane (PDMS) was added to conduct the polymerization for 3 hours.

As a result, it was confirmed that the PDMS-PAI copolymer was homogeneously mixed with the general PAI.

As described above, the ceramic sol nanohybrid material using the polydimethylsiloxane-polyamideimide-based copolymer according to the present invention and the method for producing the same are characterized in that an amine group having polarity and a polyamideimide having an imide group repeating structure are reacted with isocyanurate (PDMS) having a reactive group capable of reacting with a silane coupling agent and a reactive group capable of reacting with a silane coupling agent .

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention may be embodied otherwise without departing from the spirit and scope of the invention. Therefore, the embodiments disclosed in the present invention are not intended to limit the technical spirit of the present invention, but are for the purpose of explanation, and the scope of technical spirit of the present invention is not limited by these embodiments. The scope of protection of the present invention should be construed according to the following claims, and all technical ideas within the scope of the claims should be construed as being included in the scope of the present invention.

Claims (19)

A first step of polymerizing a diisocyanate compound and an acid anhydride compound to synthesize a polyamideimide having an isocyanic group in a part of the chain ends;
A second step of adding at least one of glycol ethers and alcohols to the polyamideimide so that a hydroxyl group or an ether group is capped in a part of the polyamideimide chain having an isocyanate group;
A third step of synthesizing a polydimethylsiloxane-polyamideimide-based copolymer by reacting polydimethylsiloxane (PDMS) with a polyamideimide to which at least one of the glycol ethers and alcohols is added; And
And a fourth step of preparing a ceramic sol nanohybrid hybrid material by mixing a ceramic sol with the polydimethylsiloxane-polyamideimide-based copolymer, and a fourth step of mixing the ceramics sol with the polydimethylsiloxane-polyamideimide- A method for producing a sol nano hybrid material. The method according to claim 1,
The polydimethylsiloxane (PDMS) in the third step may be,
And at least one of reactive groups containing hydroxyl groups, an acid group, an amine group, an anhydride group, an epoxy group and a thiol group at both ends and reacting with an isocyanic group of the polyamideimide chain (Method for producing ceramic sol nanohybrid material using polyamideimide type copolymer). 3. The method of claim 2,
The molecular weight of polydimethylsiloxane (PDMS) having at least one of reactive groups including hydroxyl groups, acid groups, amine groups, anhydride groups, epoxy groups and thiol groups at both ends is 500 to 20,000 Da Wherein the poly (dimethylsiloxane) -based polyamide-imide-based copolymer is a poly (dimethylsiloxane) -based copolymer. The method according to claim 1,
Wherein the polyamideimide having an isocyanate group in a part of the chain ends has a molecular weight of 5,000 to 500,000 Da. The method according to claim 1,
The diisocyanate compound,
4,4'-methylenebis (phenyl isocyanate), 2,2-bis (4-isocyanatophenyl) hexafluoropropane, 2,2-bis (4- isocyanatophenyl) hexafluoropropane, 4,4'-diisocyanato-3,3'-dimethylbiphenyl, 4,4'-diisocyanato-3 , 3'-dimethyldiphenylmethane, 1,5-diisocyanatonaphthalene, 1,3-phenylene diisocyanate, Polyamide-imide-based copolymer which is at least one of poly (1,3-phenylene diisocyanate), 1,4-phenylene diisocyanate and derivatives thereof, A method for manufacturing a nanohybrid material. The method according to claim 1,
The acid anhydride compound,
Polyamideimide-based copolymer, which is characterized in that it is at least one of TMA (trimellitic anhydride) and derivatives thereof. The method according to claim 1,
In the fourth step,
A polydimethylsiloxane-polyamideimide copolymer is formed by adding a solvent containing water to at least one of oxide, nitride, and carbide nanoparticles, stirring the solution, modifying the surface with silane, and adding an organic solvent. A method for producing a ceramic sol nanohybrid material using the same. In a ceramic sol nanohybrid material,
A polydimethylsiloxane-polyamideimide-based copolymer in which polydimethylsiloxane (PDMS) is bonded to a polyamideimide in which a hydroxyl or ether group is capped in a part of an isocyanic chain, and isocyanic groups; And
Wherein the ceramic sol nano hybrid material is a mixture of a poly (dimethyl siloxane-polyamide-imide) copolymer and a ceramic sol. 9. The method of claim 8,
The polydimethylsiloxane (PDMS)
And at least one of reactive groups containing hydroxyl groups, an acid group, an amine group, an anhydride group, an epoxy group and a thiol group at both ends and reacting with an isocyanic group of the polyamideimide chain - Ceramic sol nanohybrid materials using polyamideimide type copolymer. 9. The method of claim 8,
In the ceramic sol,
A polydimethylsiloxane-polyamideimide copolymer is formed by adding a solvent containing water to at least one of oxide, nitride, and carbide nanoparticles, stirring the resultant, modifying the surface with silane, and adding an organic solvent. Ceramic sol nanohybrid material used. A first step of polymerizing a diisocyanate compound and an acid anhydride compound to synthesize a polyamideimide having isocyanate groups at both ends of the chain;
A polyimide siloxane-polyamideimide system (PDMS) in which the polyamideimide and the polydimethylsiloxane (PDMS) are successively bonded in sequence by reacting polydimethylsiloxane (PDMS) with a polyamideimide having isocyanate groups at both ends of the chain A second step of synthesizing a copolymer; And
And a third step of mixing a ceramic sol with the polydimethylsiloxane-polyamideimide-based copolymer to prepare a ceramic sol nano hybrid material. A method for producing a sol nano hybrid material. 12. The method of claim 11,
The polydimethylsiloxane (PDMS) in the second step may be,
And at least one of reactive groups containing hydroxyl groups, an acid group, an amine group, an anhydride group, an epoxy group and a thiol group at both ends and reacting with an isocyanic group of the polyamideimide chain (Method for producing ceramic sol nanohybrid material using polyamideimide type copolymer). 13. The method of claim 12,
The molecular weight of polydimethylsiloxane (PDMS) having at least one of reactive groups including hydroxyl groups, acid groups, amine groups, anhydride groups, epoxy groups and thiol groups at both ends is 500 to 20,000 Da Wherein the poly (dimethylsiloxane) -based polyamide-imide-based copolymer is a poly (dimethylsiloxane) -based copolymer. 12. The method of claim 11,
The diisocyanate compound,
4,4'-methylenebis (phenyl isocyanate), 2,2-bis (4-isocyanatophenyl) hexafluoropropane, 2,2-bis (4- isocyanatophenyl) hexafluoropropane, 4,4'-diisocyanato-3,3'-dimethylbiphenyl, 4,4'-diisocyanato-3 , 3'-dimethyldiphenylmethane, 1,5-diisocyanatonaphthalene, 1,3-phenylene diisocyanate, Polyamideimide-based copolymer characterized by being at least one selected from the group consisting of 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, and derivatives thereof. The polydimethylsiloxane- A method for producing a sol nano hybrid material. 12. The method of claim 11,
The acid anhydride compound,
Polyamideimide-based copolymer, which is characterized in that it is at least one of TMA (trimellitic anhydride) and derivatives thereof. 12. The method of claim 11,
Wherein the ceramic sol of the third step comprises:
A polydimethylsiloxane-polyamideimide copolymer is formed by adding a solvent containing water to at least one of oxide, nitride, and carbide nanoparticles, stirring the resultant, modifying the surface with silane, and adding an organic solvent. A method for producing a ceramic sol nanohybrid material using the same. In a ceramic sol nanohybrid material,
A polydimethylsiloxane-polyamideimide-based copolymer in which a polyamideimide having isocyanate groups at both ends of the chain and polydimethylsiloxane (PDMS) are sequentially and sequentially bonded; And
Wherein the ceramic sol nano hybrid material is a mixture of a poly (dimethyl siloxane-polyamide-imide) copolymer and a ceramic sol. 18. The method of claim 17,
The polydimethylsiloxane (PDMS)
And at least one of reactive groups containing hydroxyl groups, an acid group, an amine group, an anhydride group, an epoxy group and a thiol group at both ends and reacting with an isocyanic group of the polyamideimide chain - Ceramic sol nanohybrid materials using polyamideimide type copolymer. 18. The method of claim 17,
In the ceramic sol,
A polydimethylsiloxane-polyamideimide copolymer is formed by adding a solvent containing water to at least one of oxide, nitride, and carbide nanoparticles, stirring the resultant, modifying the surface with silane, and adding an organic solvent. Ceramic sol nanohybrid material used.
KR1020150083260A 2015-06-12 2015-06-12 Ceramic sol nanohybrid materials using polydimethylsiloxane-polyamideimide copolymers and manufacturing method thereof KR101704593B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1020150083260A KR101704593B1 (en) 2015-06-12 2015-06-12 Ceramic sol nanohybrid materials using polydimethylsiloxane-polyamideimide copolymers and manufacturing method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1020150083260A KR101704593B1 (en) 2015-06-12 2015-06-12 Ceramic sol nanohybrid materials using polydimethylsiloxane-polyamideimide copolymers and manufacturing method thereof

Publications (2)

Publication Number Publication Date
KR20160146250A true KR20160146250A (en) 2016-12-21
KR101704593B1 KR101704593B1 (en) 2017-02-08

Family

ID=57734876

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1020150083260A KR101704593B1 (en) 2015-06-12 2015-06-12 Ceramic sol nanohybrid materials using polydimethylsiloxane-polyamideimide copolymers and manufacturing method thereof

Country Status (1)

Country Link
KR (1) KR101704593B1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102462940B1 (en) 2017-11-03 2022-11-04 삼성전자주식회사 Polyimide, composition for preparing polyimide, article including polyimide, and display device including the article

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4374221A (en) * 1981-11-17 1983-02-15 Essex Group, Inc. High solids polyamide-imide magnet wire enamel
KR20050070290A (en) 2003-12-30 2005-07-07 주식회사 코오롱 Polyamideimide vanish improved thermal resistance and folding endurance
KR101104390B1 (en) * 2011-02-18 2012-01-16 한국전기연구원 Manufacturing method of organic inorganic nanohybrid/nanocomposite varnish materials and the coated electrical wire
US20130153261A1 (en) * 2010-08-10 2013-06-20 Schwering & Hasse Elektrodraht Gmbh Electrical Insulation Enamels Composed of Modified Polymers and Electrical Conductors Produced Therefrom and Having Improved Sliding Capacity

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4374221A (en) * 1981-11-17 1983-02-15 Essex Group, Inc. High solids polyamide-imide magnet wire enamel
KR20050070290A (en) 2003-12-30 2005-07-07 주식회사 코오롱 Polyamideimide vanish improved thermal resistance and folding endurance
US20130153261A1 (en) * 2010-08-10 2013-06-20 Schwering & Hasse Elektrodraht Gmbh Electrical Insulation Enamels Composed of Modified Polymers and Electrical Conductors Produced Therefrom and Having Improved Sliding Capacity
KR101104390B1 (en) * 2011-02-18 2012-01-16 한국전기연구원 Manufacturing method of organic inorganic nanohybrid/nanocomposite varnish materials and the coated electrical wire

Also Published As

Publication number Publication date
KR101704593B1 (en) 2017-02-08

Similar Documents

Publication Publication Date Title
Wang et al. Fluorinated and thermo-cross-linked polyhedral oligomeric silsesquioxanes: New organic–inorganic hybrid materials for high-performance dielectric application
Huang et al. Organic–inorganic nanocomposites from cubic silsesquioxane epoxides: direct characterization of interphase, and thermomechanical properties
KR100880500B1 (en) Resin composition and coating film forming material
Kizilkaya et al. Synthesis and characterization of novel polyimide/SiO2 nanocomposite materials containing phenylphosphine oxide via sol‐gel technique
JP4774754B2 (en) Solvent-soluble polyimide copolymer and polyimide varnish
US20120190802A1 (en) Polyimide polymer from non-stoichiometric components
KR101690544B1 (en) Siloxane-containing polyimide resin
JP2016538411A (en) Cross-linked composition and method for producing the same
Zhang et al. Preparation and characterization of aqueous polyurethane dispersions with well‐defined soft segments
WO2021150666A1 (en) Curable silicone-acrylate compositions, conductive materials prepared therewith, and related methods
KR20210138701A (en) Polyamic acid composition and manufacturing method thereof, polyamic acid solution, polyimide, polyimide film, laminate and manufacturing method thereof, and flexible device and manufacturing method thereof
Huang et al. Synthesis and characterization of sustainable polyurethane based on epoxy soybean oil and modified by double-decker silsesquioxane
KR101704593B1 (en) Ceramic sol nanohybrid materials using polydimethylsiloxane-polyamideimide copolymers and manufacturing method thereof
Jiang et al. Moisture‐cured polyurethane/polysiloxane copolymers: Effects of the structure of polyester diol and NCO/OH ratio
CN101484532B (en) Heat-resistant resin varnish, heat-resistant resin films, heat-resistant resin composites, and insulated wire
Im et al. Preparation and properties of polyimide/silica hybrid composites based on polymer‐modified colloidal silica
KR101597683B1 (en) Ceramic sol nanohybrid materials using modified polyamideimide capped with hydroxyl group or ether group and manufacturing method of thereof
KR20170032726A (en) Micro/Nano hybrid materials using a Polydimethylsiloxane-Polyamideimide tri-block copolymer and method of manufacturing the same
JP2016017085A (en) Material for electrical insulation, electrically insulated product, electrical insulation coating, and electrically insulated wire
JP4543654B2 (en) Solvent-soluble polyimide copolymer
JP7247604B2 (en) Resin composition for insulating coating material and insulating coating material
JPWO2020158736A1 (en) Compositions and metal insulating coatings
Srividhya et al. Synthesis and characterization of polyimide containing PEG/PDMS amphiphilic conetworks by hydrosilylation: Correlation between structure and properties
Wen et al. Synthesis and properties of epoxy soybean oil-based polyurethanes modified by 3, 13-dimethyhydroxysilyl double-decker phenylsilsesquioxane
Liaw et al. Preparation and properties of poly (imide siloxane) segmented copolymer/silica hybrid nanocomposites

Legal Events

Date Code Title Description
A201 Request for examination
E902 Notification of reason for refusal
E701 Decision to grant or registration of patent right
GRNT Written decision to grant