KR101986122B1 - Siloxane polyhydric alcohol and thermosetting resin omposite containing the same - Google Patents

Abstract

[화학식 2]

[화학식 3]

The present invention relates to a thermosetting resin composition comprising a crosslinking agent and any one of the novel siloxane polyhydric alcohol compounds represented by the following general formulas (1) to (3).
[Chemical Formula 1]

(2)

(3)

Description

[0001] Siloxane polyhydric alcohols and thermosetting resin compositions containing the same [0002]

The present invention relates to a siloxane polyhydric alcohol and a thermosetting resin composition containing the same. More specifically, the present invention relates to a thermosetting resin composition containing a novel siloxane polyhydric alcohol and an insulating film produced thereby.

The present invention also relates to novel siloxane polyhydric alcohols.

Since the discovery of conductive polymers in the 1980s, attempts have been made to introduce organic materials into the electronics and semiconductor industries. In the early '80s, the concept of organic thin film transistors was introduced and new materials and devices developed. Organic thin film transistor materials, which are comparable in performance to amorphous silicon thin film transistors, have been developed and are being studied for commercialization. The reason why the organic thin film transistor is better than the amorphous silicon thin film transistor is that the solution process is possible. In the case of inorganic transistors, the solution process is impossible, and the equipment required for high temperature and vacuum deposition is used in the production process, resulting in higher cost, more energy, and more natural destruction. On the other hand, since organic transistors can be processed in solution, there is no need for high-temperature and vacuum deposition equipment in the production process. Therefore, they can reduce production cost and have environment-friendly aspects because they use less energy. And the biggest advantage is that transistors can be fabricated on flexible substrates. It is possible to use spin coating technology, roll-to-roll process, ink-jet printing process, etc., which are currently in use, so that no additional production cost is incurred, and even a flexible substrate such as plastic, cloth, Since it is usable, it is possible to select a wide range of substrates. Since the silicon oxide layer grown on a single crystal silicon wafer substrate was used as an insulator in the early stage of the organic thin film transistor device, researches on the organic semiconductor material have been concentrated and much research has been carried out to date. At present, excellent organic semiconductor materials have been developed. However, research on organic insulators is relatively inefficient compared with organic semiconducting materials. In addition, a metal having a low work function is generally used for an electrode of an electronic device. If the oxygen and moisture can not be effectively shielded, the device may be deteriorated and the performance and life may be deteriorated. In particular, when a flexible substrate is used, it is strongly desired to shield moisture and oxygen from penetrating into the polymer substrate.

Korean Patent No. 10-0405312 entitled " Organosilicate Polymer and Low Dielectric Insulating Film Containing the Organosilicate Polymer " discloses an organosilicate polymer prepared by hydrolysis and condensation reaction of a linear organosilane oligomer with another silane compound and a low dielectric insulating film using the organosilicate polymer Lt; / RTI > However, it does not provide a sufficiently low dielectric constant and has a disadvantage in that the mechanical properties of the film are insufficient.

In addition, an anti-fouling coating is used on the surface of the ship to prevent adhesion of various marine life (oyster, mussel, barn, etc.), vegetation such as seaweed, or bacteria. When marine organisms attach to the surface of a ship, there is a difficulty in increasing the resistance of the sailing vessel and increasing the fuel cost and periodically removing marine life. For this purpose, various antifouling paints have been developed and used, such as the use of additives that can give toxicity to the attached organisms, and the removal of adhered organisms by the wear of the paint. Currently, additives containing tin in these antifouling paints are known to have negative effects on marine ecosystems, and their use is regulated. Therefore, it is required to develop new antifouling paints which do not affect the marine ecosystem.

Korean Patent No. 10-0405312 (October 31, 2003)

It is an object of the present invention to provide a novel siloxane polyhydric alcohol and a thermosetting resin composition containing the same.

Another object of the present invention is to provide an insulating film made of the thermosetting resin composition. And more specifically, to provide an insulating film excellent in electric insulation.

One aspect of the present invention to accomplish the above object is to provide a thermosetting resin composition comprising a crosslinking agent and at least one siloxane polyhydric alcohol compound selected from the following formulas (1) to (3).

[Chemical Formula 1]

(2)

(3)

Each of R ₁ to R ₆ is independently a linear or branched C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy or (CH ₂ ) _X -OH, provided that one of (CH ₂ ) _X -OH Or more,

R ₇ To R ₈ are each independently a linear or branched C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy or (CH ₂ ) _X -OH, provided that at least one of (CH ₂ ) _X -OH ,

R ₁₀ To R ₁₇ are each independently straight or branched C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy or (CH ₂ ) _X -OH with the proviso that at least one of (CH ₂ ) _X -OH ,

The C ₁ -C ₂₀ alkyl and C ₁ -C ₂₀ alkoxy may each be independently substituted with a linear or branched C ₁ -C ₂₀ alkyl or (CH ₂ ) _X -OH,

Wherein A is a chemical bond or a C ₁ -C ₂₀ alkylene group,

M is an integer of 2 to 10, and x is an integer of 1 to 10.

In the present invention, R ₁ to R ₁₇ are methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, sec-butyl. iso-butyl, tert-butyl, iso-octyl, methoxy, ethoxy, oxygen or (CH ₂ ) _X -OH.

The present invention also relates to a thermosetting resin composition comprising one or more siloxane polyhydric alcohol compounds selected from the following formulas.

Further, the present invention relates to a thermosetting resin composition wherein the crosslinking agent is one or a mixture of two or more selected from compounds containing a melamine derivative, a polyvalent isocyanate and an anhydride group.

The present invention also relates to a thermosetting resin composition, wherein the melamine derivative is one or more selected from the following formulas.

또는

에서 선택되는 하나이고, 상기 n은 1내지 2000의 정수이다.R ₁₁ is hydrogen, C ₁ -C ₂₀ alkyl, and R ₁ is

or

And n is an integer of 1 to 2,000.

The present invention also relates to a thermosetting resin composition wherein the polyisocyanate is one or more selected from the following formulas.

X is an integer of 1 to 20, and n is an integer of 1 to 2000.

The present invention also relates to a thermosetting resin composition wherein the compound containing the anhydride group has the following formula.

In the general formula Rx are each independently a straight-chain or branched-chain C ₁ -C ₂₀ alkyl, k is a calcium atom, m is an integer of 0 to 2,000, n is an integer from 1 to 2000, z is an integer from 1 to 2000 to be.

The present invention also relates to an insulating film made of the above-mentioned thermosetting resin composition.

Another aspect of the present invention relates to a novel siloxane polyhydric alcohol represented by the following general formulas (1) to (4).

[Chemical Formula 1]

(2)

(3)

Each of R ₁ to R ₆ is independently a linear or branched C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy or (CH ₂ ) _X -OH, provided that one of (CH ₂ ) _X -OH Or more,

R ₇ To R ₈ are each independently a linear or branched C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy or (CH ₂ ) _X -OH, provided that at least one of (CH ₂ ) _X -OH ,

R ₁₀ To R ₁₇ are each independently straight or branched C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy or (CH ₂ ) _X -OH with the proviso that at least one of (CH ₂ ) _X -OH ,

The C ₁ -C ₂₀ alkyl and C ₁ -C ₂₀ alkoxy may each be independently substituted with a linear or branched C ₁ -C ₂₀ alkyl or (CH ₂ ) _X -OH,

Wherein A is a chemical bond or a C ₁ -C ₂₀ alkylene group,

M is an integer of 2 to 10, and x is an integer of 1 to 10.

In the present invention, R ₁ to R ₁₇ are methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, sec-butyl. iso-propyl, iso-butyl, tert-butyl, iso-octyl, methoxy, ethoxy, oxygen or (CH ₂ ) _X -OH.

The present invention also relates to siloxane polyhydric alcohols containing the following formula:

The present invention relates to an insulating film prepared by preparing a thermosetting resin composition containing the novel siloxane polyhydric alcohol compound. The process temperature is low due to the condensation reaction between the hydroxyl group of the novel siloxane polyhydric alcohol compound and the crosslinking agent at the time of producing the insulating material with the thermosetting resin composition and the lower leakage current value And a spin coating process and a printing coating process are possible because a solution process is possible. Therefore, there is an advantage that an insulating film can be easily manufactured. Also, various electronic devices can be used as an additive because it is easy to control the surface energy of moisture shielding film and antifouling paint.

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

The present invention relates to a thermosetting resin composition comprising a novel siloxane polyhydric alcohol compound, wherein the siloxane polyhydric alcohol compound is any one selected from the siloxane polyhydric alcohol compounds represented by the following general formulas (1) to (3).

[Chemical Formula 1]

(2)

(3)

Each of R ₁ to R ₆ is independently a linear or branched C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy or (CH ₂ ) _X -OH, provided that one of (CH ₂ ) _X -OH Or more,

R ₇ To R ₈ are each independently a linear or branched C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy or (CH ₂ ) _X -OH, provided that at least one of (CH ₂ ) _X -OH ,

R ₁₀ To R ₁₇ are each independently straight or branched C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy or (CH ₂ ) _X -OH with the proviso that at least one of (CH ₂ ) _X -OH ,

The C ₁ -C ₂₀ alkyl and C ₁ -C ₂₀ Alkoxy can each independently be replaced by a straight or branched C ₁ -C ₂₀ alkyl or (CH ₂ ) _X -OH,

Wherein A is a chemical bond or a C ₁ -C ₂₀ alkylene group,

M is an integer of 2 to 10, and x is an integer of 1 to 10.

More specifically, R ₁ to R ₆ are each independently a linear or branched C ₁ -C ₁₀ alkyl, C ₁ -C ₁₀ alkoxy or (CH ₂ ) _X -OH, provided that at least one of (CH ₂ ) _X - OH,

R ₇ To R ₈ are each independently straight or branched C ₁ -C ₁₀ alkyl, C ₁ -C ₁₀ alkoxy or (CH ₂ ) _X -OH, provided that at least one of (CH ₂ ) _X -OH ,

R ₁₀ To R ₁₇ are each independently include a straight-chain or a C ₁ -C ₁₀ alkyl, C ₁ -C10 alkoxy, or (CH _{2) X} -OH branched, with the proviso be (CH ₂₎ at least one _X -OH,

The C ₁ -C ₁₀ alkyl, C ₁ -C10 alkoxy may be further substituted with, each independently, a linear or branched C ₁ -C ₂₀ alkyl or (CH _{2) X} -OH,

Wherein A is a chemical bond or a C ₁ -C ₁₀ alkylene group,

And m and x may be an integer of 1 to 5.

More specifically, R ₁ to R ₁₇ are methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, sec-butyl. iso-butyl, tert-butyl, iso-octyl, methoxy, ethoxy, oxygen or (CH ₂ ) _x -OH.

The siloxane polyhydric alcohol compound includes the following chemical formulas.

The crosslinking agent may be one or a mixture of two or more compounds selected from melamine derivatives, polyvalent isocyanates and anhydride groups. Preferably, the melamine derivative is used as a thermoplastic resin composition having excellent heat resistance and insulation properties. And it is good because it can cause a crosslinking reaction at a low temperature of 60 to 100 ° C.

Examples of the melamine derivative include, but are not limited to, one or more selected from compounds represented by the following formulas.

또는

에서 선택되는 하나이고, 상기 n은 1내지 2000의 정수이다.)(Wherein R ₁₁ is hydrogen, C ₁ -C ₂₀ alkyl, and R ₁ is

or

And n is an integer of 1 to 2000.)

를 포함하는 것으로, 하기 화학식에서 선택되는 하나 또는 둘 이상일 수 있으나, 이에 제한되지는 않는다.The polyisocyanate

And may be one or two or more selected from the following formulas, but is not limited thereto.

(Wherein x is an integer of 1 to 20 and n is an integer of 1 to 2000)

The compound containing the anhydride group may include, but is not limited to, the following chemical formulas.

(In the general formula Rx are each independently a straight-chain or branched-chain C ₁ -C ₂₀ alkyl, k is a calcium atom, m is an integer of 0 to 2,000, n is an integer from 1 to 2000, z is from 1 to 2000 It is an integer.)

The present invention provides a thermoplastic resin composition comprising the novel siloxane-based polyhydric alcohol compound and one or two or more selected from among compounds containing a melamine derivative, polyvalent isocyanate and anhydride group as a crosslinking agent.

The thermoplastic resin composition according to the present invention can produce an insulating film by a condensation reaction between a siloxane polyhydric alcohol compound and a crosslinking agent. For example, the reaction between a siloxane polyhydric alcohol and a melamine derivative includes the following reaction formula.

[Reaction Scheme]

In the above reaction formula, Ar represents a melamine (aromatic), and in the case of an alkyl chain of a siloxane polyhydric alcohol, n is a linear or branched chain of C ₁ to C ₂₀ , and R represents a siloxane-based linear or branched It corresponds to polymer substance. When heated in the presence of an acid catalyst such as p-toluenesulfonic acid, a condensation reaction occurs in which acid (H ⁺ ) ions are generated and the alcohol is removed, resulting in three-dimensional crosslinking. In addition, the insulating film produced by the three-dimensional crosslinking reaction may have an effect of exhibiting a low current value.

It is preferable that the insulating film according to the present invention contains 1 equivalent of the siloxane polyhydric alcohol: crosslinking agent, 0.5 to 2 equivalents, preferably 1 equivalent: 0.8 to 1.2 equivalents, wherein the siloxane polyhydric alcohol and the crosslinking agent are combined, 29 wt%, 0.1 to 1 wt% of an acid catalyst, and 70 to 90 wt% of a solvent.

Examples of the acid catalyst include sulfuric acid, p-toluenesulfonic acid, dinonylnaphthalene disulfonic acid, dodecylbenzene sulfonic acid, oxalic acid, maleic acid, a mixture of one or more selected from the group consisting of hexamic acid, phosphoric acid, alkyl phosphate ester, phthalic acid and acrylic acid may be used. Preferably, p - Use of toluene sulfonic acid is good because it also shows high curing at low temperatures. It is preferable that the acid catalyst contains 0.1 to 1 wt%, and when the acid catalyst is included in the above range, the time of the crosslinking reaction can be shortened, and the crosslinking reaction becomes more active so that it is easy to form a thin film.

Examples of the solvent include propylene glycol monomethyl ether acetate (PGMEA), toluene, xylene, dibutylether (DBE), and cocosol Or a mixture of two or more of them may be used, and the solvent is preferably contained in an amount of 70 to 90 wt% because the fluidity can be ensured when the insulating film is coated by coating the thermoplastic resin composition, which facilitates the work.

As an electronic device including an insulating film, an organic thin film transistor can be exemplified. Typically, an organic thin film transistor has a bottom gate-top contact (BG-TC) structure, a bottom gate-bottom contact (b) or a top gate-bottom contact (TG-BC) structure (c), and the performance of the organic thin film transistor depends on the performance of the junctions of the respective parts .

In the case of the BG-TC (a) structure, since the junction between the source / drain electrode and the semiconductor layer is the best, the BG-BC (b) exhibits high performance. Layer is located at the bottom of the structure, the bonding between the electrode and the semiconductor is poor and does not show good performance. In addition, TG-BC (c) is a structure in which the gate electrode is located at the upper end and the source and drain electrodes are located at the lower end of the semiconductor layer, which is considered as a circuit structure for printing on a large area, Do. Therefore, in the present invention, an organic thin film transistor is manufactured using the BG-TC (a) structure.

In the present invention, ITO (Indium Tin Oxide), which is a transparent electrode having a high work function, is used as a gate electrode, and a source electrode Au was used for the drain electrode, and pentacene was used for the semiconductor layer. The reason why the pentacene was used is that the work function (5.3 eV) of Au and HOMO (Highly Occupied Molecular Obtellite, 5.1 eV) of pentacene is most similar among various metals.

Finally, the structure of the device according to the present invention will be described. First, a thermosetting resin composition is cured to a thickness of 400 nm to 600 nm by a method such as spin coating or inkjet printing on a glass substrate on which ITO is applied, After deposition of pentacene on the substrate using vacuum deposition method, source and drain electrodes were also deposited by evaporation.

Another embodiment of the present invention relates to a siloxane-based polyhydric alcohol represented by the following general formulas (1) to (4).

[Chemical Formula 1]

(2)

(3)

Each of R ₁ to R ₆ is independently a linear or branched C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy or (CH ₂ ) _X -OH, provided that one of (CH ₂ ) _X -OH Or more,

R ₇ To R ₈ are each independently a linear or branched C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy or (CH ₂ ) _X -OH, provided that at least one of (CH ₂ ) _X -OH ,

R ₁₀ To R ₁₇ are each independently straight or branched C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy or (CH ₂ ) _X -OH with the proviso that at least one of (CH ₂ ) _X -OH ,

The C ₁ -C ₂₀ alkyl and C ₁ -C ₂₀ alkoxy may each be independently substituted with a linear or branched C ₁ -C ₂₀ alkyl or (CH ₂ ) _X -OH,

Wherein A is a chemical bond or a C ₁ -C ₂₀ alkylene group,

And m and x may be an integer of 1 to 10.

More specifically, R ₁ to R ₆ are each independently a linear or branched C ₁ -C ₁₀ alkyl, C ₁ -C ₁₀ alkoxy or (CH ₂ ) _X -OH, provided that at least one of (CH ₂ ) _X -OH , ≪ / RTI >

R ₇ To R ₈ are each independently include a straight-chain or a C ₁ -C ₁₀ alkyl, C ₁ -C10 alkoxy, or (CH _{2) X} -OH branched, with the proviso be (CH ₂₎ at least one _X -OH,

R ₁₀ To R ₁₇ are each independently include a straight-chain or a C ₁ -C ₁₀ alkyl, C ₁ -C10 alkoxy, or (CH _{2) X} -OH branched, with the proviso be (CH ₂₎ at least one _X -OH,

Said C ₁ -C ₁₀ alkyl, C ₁ -C ₁₀ Alkoxy can each independently be replaced by a straight or branched C ₁ -C ₂₀ alkyl or (CH ₂ ) _X -OH,

Wherein A is a chemical bond or a C ₁ -C ₁₀ alkylene group,

And m and x may be an integer of 1 to 5.

More specifically, R ₁ to R ₁₇ are methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, sec-butyl. iso-butyl, tert-butyl, iso-octyl, methoxy, ethoxy, oxygen or (CH ₂ ) _x -OH.

The siloxane-based polyhydric alcohols may include the following chemical formulas.

The present invention relates to an electronic device comprising a thermosetting resin composition containing the novel siloxane polyhydric alcohol compound and an insulating film prepared using the thermosetting resin composition, , The process temperature is low due to the condensation reaction between the hydroxy group of the novel siloxane-based polyhydric alcohol compound and the cross-linking agent, and there is an effect that the leakage current value is lower than that of a commonly used PVP insulating material. Since spin coating and printing coating are possible, there is an advantage that the formation of the insulating layer can be facilitated. Also, various electronic devices can be used as an additive because it is easy to control the surface energy of moisture shielding film and antifouling paint.

FIG. 1 shows a bottom gate-top contact (BG-TC) structure, a bottom gate-bottom contact (BG-BC) structure and a top gate-bottom contact ). ≪ / RTI >
2 is a ¹ H-NMR spectrum of the compound Octakis (3-hydroxypropyldimethylsiloxy) octaprismosilsesquioxane prepared in Example 10.
3 is a ¹ H-NMR spectrum of hexamethoxymethylmelamine used as a crosslinking agent.
4 is a schematic diagram of a BG-TC structure of an organic / inorganic hybrid insulation film (POSS-OH) produced according to the present invention.
FIG. 5 is an IV curve of the insulating film of the MIM structure manufactured in Examples 11 to 13 and the insulating film prepared in Comparative Example 1. FIG.
6 is a graph of capacitance per unit area of the insulating film of the MIM structure manufactured in Examples 11 to 13 and the insulating film prepared in Comparative Example 1. FIG.
7 is a conversion curve of the organic thin film transistor including the insulating film manufactured in Examples 11 to 13 and the organic thin film transistor including the insulating film manufactured in Comparative Example 1. FIG.
8 is an output curve of the organic thin film transistor including the insulating film manufactured in Examples 11 to 13 and the organic thin film transistor including the insulating film manufactured in Comparative Example 1. FIG.

Hereinafter, the present invention will be described in detail with reference to examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

Example 1 Synthesis of 3,3 '- (1,1,2,2-tetramethyldisilane-1, 2-diyl) dipropan-1-ol (3,3' - (1,1,2,2-tetramethyldisilane -1,2-diyl) dipropan-1-ol

1,1,2,2-tetramethyldisilane (1.00 g, 16.9 mmol) was added to a round-bottomed flask reactor, the reactor was evacuated for 2 hours, and high-purity N ₂ gas was charged into the reactor. 25 ml of anhydrous toluene and 4.6 mmol (11.8 ml) of allyl alcohol were added thereto. The mixture was stirred for 20 minutes, and then Pt (dvs) (0.05 ml) was added thereto at room temperature. After the stirring was completed, the solution was diluted with chloroform for HPLC, 10 g of activated carbon was added to the round flask, and the mixture was further stirred for 24 hours. Thereafter, to remove the activated carbon, the filter paper was used to filter the filter paper, and then anhydrous magnesium sulfate was added to remove water. To remove the anhydrous magnesium sulfate, the filter paper was filtered with a sieve filter, Filtered. After removing the solvent, the residue was dried in a vacuum oven at 60 ° C. for 24 hours to remove the residual solvent.

^{1 H-NMR (300 MHz,} CDCl 3) δ 0.08 (s, 12H), 1.02 (t, 4H), 1.50 (m, 4H), 3.50 (t, 4H) 3.65 (bs, 2H)

[ Example  2] 1,2-bis (3- Hydroxypropyltetramethyldisiloxanyl ) Ethane (1,2-Bis (3-hydroxypropyltetramethyldisiloxanyl) ethane)

1,2-bis (tetramethyldisiloxanyl) ethane (2.00 g, 6.79 mmol) was added to the round flask reactor, and then the inside of the reactor was evacuated for 2 hours and then purged with high purity N ₂ gas. 25 ml of anhydrous toluene and allyl alcohol (27.1 mmol, 1.85 ml) were added and stirred for 20 minutes. Then, Pt (dvs) (0.05 ml) was added at room temperature and stirred for 20 hours. After the stirring was completed, the solution was diluted with chloroform for HPLC, 10 g of activated carbon was added to the round flask, and the mixture was further stirred for 24 hours. Then, to remove the activated carbon, the filter paper was used to filter the filter paper, and then anhydrous magnesium sulfate was added to remove water. To remove the anhydrous magnesium sulfate, the filter paper was filtered with a filter paper, Respectively. After removing the solvent, the residue was dried in a vacuum oven at 60 ° C. for 24 hours to remove the residual solvent.

¹ H-NMR (300 MHz, CDCl ₃ )? 0.21 (s, 24H), 1.02 (t, 4H), 1.06 (s, 4H). 1.50 (m, 4H), 3.50 (t, 4H), 3.65 (bs, 2H)

Example 3 Synthesis of 3,3 '- (4- (dimethoxy (methyl) silyl) -3,5-dimethoxy-2,6-dioxa-3,5-dicylheptane- 3,5-dimethoxy-2,6-dioxa-3,5-disilaheptane-3,5-diyl) dipropan- 1-ol < / RTI >

1,1,3,3-tetramethoxy-2- (dimethoxysilyl) -1,3-disilabutane (2.00 g, 6.65 mmol) was added to a round-bottomed flask reactor, And filled with high purity N ₂ gas. 25 ml of anhydrous toluene and 26.6 mmol (1.81 ml) of allyl alcohol were added, and the mixture was stirred for 20 minutes. Then, Pt (dvs) (0.05 ml) was further added at room temperature and further stirred for 20 hours. After the stirring was completed, the solution was diluted with chloroform for HPLC, and then 10 g of activated carbon was added to the round flask reactor and stirred for 24 hours. Thereafter, to remove the activated carbon, the filter paper was used to filter the filter paper, and then anhydrous magnesium sulfate was added to remove water. To remove the anhydrous magnesium sulfate, the filter paper was filtered with a sieve filter, Filtered. After removing the solvent, the residue was dried in a vacuum oven at 60 ° C. for 24 hours to remove the residual solvent.

^{1 H-NMR (300 MHz,} CDCl 3) δ 0.14 (s, 3H), 1.02 (t, 5H), 1.50 (m, 4H), 3.50 (t, 4H) 3.59 (s, 18H), 3.65 (bs, 2H)

[ Example  4] 3,3 '- (3,5- Dimethoxy -2,6- Dioxa -3,5- Dissile Hentan -3,5- Dill ) Di-propane (3,3 '- (3,5-dimethoxy-2,6-dioxa-3,5-disilaheptane-3,5-diyl) dipropan-1-ol

Bis (dimethoxysilyl) methane (2.00 g, 10.2 mmol) was placed in a round-bottomed flask reactor and vacuumed for 2 hours, after which high-purity N ₂ gas was charged into the reactor. 25 ml of anhydrous toluene and allyl alcohol (40.7 mmol, 2.78 ml) were added. After stirring for 20 minutes, Pt (dvs) (0.05 ml) was added at room temperature and then stirred for 20 hours. After the stirring was completed, the solution was diluted with chloroform for HPLC, 10 g of activated carbon was added to the round flask, and the mixture was further stirred for 24 hours. Thereafter, to remove the activated carbon, the filter paper was used to filter the filter paper, and then anhydrous magnesium sulfate was added to remove water. To remove the anhydrous magnesium sulfate, the filter paper was filtered with a sieve filter, Filtered. After removing the solvent, the residue was dried in a vacuum oven at 60 DEG C for 24 hours to remove residual solvent, and a clear liquid compound was obtained after the completion of the operation

^{1 H-NMR (300 MHz,} CDCl 3) δ 1.02 (t, 4H), 1.40 (s, 2H), 1.50 (m, 4H), 3.50 (t, 4H) 3.55 (s, 12H), 3.65 (bs, 2H)

Example 5 Synthesis of 3,3 '- (4,6-dimethyl-3,7-dioxa-4,6-disilanonan-4,6-diyl) 4,6- dimethyl -3,7- dioxa -4,6- disilanonane -4,6- diyl ) dipropane -One- be )

2,4-Diethoxy-2,4-disilapentane (2.00 g, 10.4 mmol) was added to the round-flask reactor, and after the reactor was evacuated for 2 hours, the inside of the reactor was filled with high-purity N ₂ gas. 25 ml of anhydrous toluene and allyl alcohol (41.9 mmol, 2.83 ml) were added and stirred for 20 minutes. Then, Pt (dvs) (0.05 ml) was added at room temperature and stirred for 20 hours. After the stirring was completed, the solution was diluted with chloroform for HPLC, 10 g of activated carbon was added to the round flask, and the mixture was further stirred for 24 hours. Thereafter, to remove the activated carbon, the filter paper was used to filter the filter paper, and then anhydrous magnesium sulfate was added to remove water. To remove the anhydrous magnesium sulfate, the filter paper was filtered with a sieve filter, Filtered. After removing the solvent, the residue was dried in a vacuum oven at 60 ° C. for 24 hours to remove the residual solvent.

¹ H-NMR (300 MHz, CDCl ₃ )? 0.21 (s, 6H), 1.02 (t, 4H), 1.21 , 4H) 3.55 (s, 12H), 3.65 (bs, 2H), 3.83 (q, 4H)

[ Sylinka  6] 3-Hydroxypropylmethylcyclosiloxane (3- hydroxypropylmethylcyclosiloxanes)  Produce

Methylhydrothacyclosiloxane (2.00 g, 6.65 mmol) was added to the flask reactor and allowed to vacuum for 2 hours, then purged with high purity N ₂ gas. 25 ml of anhydrous toluene and allyl alcohol (66.5 mmol, 4.54 ml) were added and stirred for 20 minutes. Then, Pt (dvs) (0.05 ml) was added at room temperature and stirred for 20 hours. After the stirring was completed, the solution was diluted with chloroform for HPLC, 10 g of activated carbon was added to the round flask, and the mixture was further stirred for 24 hours. Thereafter, to remove the activated carbon, the filter paper was used to filter the filter paper, and then anhydrous magnesium sulfate was added to remove water. To remove the anhydrous magnesium sulfate, the filter paper was filtered with a sieve filter, Filtered. After removing the solvent, the residue was dried in a vacuum oven at 60 ° C. for 24 hours to remove the residual solvent.

¹ H-NMR (300 MHz, CDCl ₃ )? 0.14 (bs, 15H), 1.02 (bt, 10H), 1.50

Example 7 Synthesis of 3,3 ', 3 ", 3' '' - (2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxa Tetrasiloxane-2,4,6,8-tetrayl) tetrapropan-1-ol (3,3 ', 3' ', 3' '- (2,4,6,8-tetramethyl- , 7,2,4,6,8-tetraoxatetrasiloxane-2,4,6,8-tetrayl) tetrapropan-1-ol

1,3,5,7-Tetramethylcyclotetrasiloxane (2.00 g, 8.32 mmol) was added to the round-flask reactor, and the reactor was evacuated for 2 hours and filled with high-purity N ₂ gas. 30 ml of anhydrous toluene and allyl alcohol (66.5 mmol, 4.53 ml) were added and stirred for 20 minutes. Then, Pt (dvs) (0.05 ml) was added at room temperature and stirred for 20 hours. After stirring, the solution was diluted with chloroform for HPLC, 10 g of activated carbon was added to a round flask, and the mixture was further stirred for 24 hours. Thereafter, to remove the activated carbon, the filter paper was used to filter the filter paper, and then anhydrous magnesium sulfate was added to remove water. To remove the anhydrous magnesium sulfate, the filter paper was filtered with a sieve filter, Filtered. After removing the solvent, the residue was dried in a vacuum oven at 60 ° C for 24 hours to remove the residual solvent, and a yellow transparent liquid compound was obtained after the completion of the operation.

^{1 H-NMR (300 MHz,} CDCl 3) δ 0.14 (s, 12H), 1.02 (t, 8H), 1.50 (m, 8H), 3.50 (t, 8H) 3.65 (bs, 4H)

[ Example  8] 3 ', 3' ', 3' '- (2,4,6,8- Tetraethyl -1,3,5,7,2,4,6,8- Tetraoxatetrasiloxane -2,4,6,8- Tetraallyl ) Tetrapropane (3 ', 3' ', 3' '- (2,4,6,8- tetraethyl -1,3,5,7,2,4,6,8- tetraoxatetrasilocane -2,4,6,8- tetrayl ) tetrapropane -1-ol < / RTI >

To the round flask reactor, 1,3,5,7-tetraethylcyclotetrasiloxane (2.00 g, 6.74 mmol) was added, and the mixture was purged for 2 hours and then charged with high purity N ₂ gas. Then, 25 ml of anhydrous toluene, Alcohol (53.9 mmol, 3.68 ml) was added and stirred for 20 minutes. Pt (dvs) (0.05 ml) was added at room temperature and stirred for 20 hours. After diluting the solution with chloroform for HPLC, 10 g of activated carbon was added to the round flask, and the mixture was further stirred for 24 hours. After that, filter paper was used to remove activated charcoal. Anhydrous magnesium sulfate was added to remove moisture. Then, to remove anhydrous magnesium sulfate, the filter paper was further filtered using a filter paper, and further filtered using a syringe filter. After removing the solvent, the residual solvent was removed in a vacuum to obtain a transparent liquid compound.

^{1 H-NMR (300 MHz,} CDCl 3) δ 0.90 (t, 12H), 1.02 ~ 1,06 (m, 16H), 1.50 (m, 8H), 3.50 (t, 8H) 3.65 (bs, 4H)

[Example 9] 3,3 ', 3 ", 3'", 3 "" - (2,4,6,8,10-pentamethyl-1,3,5,7,9,2 (3,3 ', 3' ', 3' ', 3', 5'-tetramethylpiperazin-4,6,8,10-pentaoxapentasiloxane- - (2,4,6,8,10-pentamethyl-1,3,5,7,9,2,4,6,8,10-pentaoxapentacyclene-2,4,6,8,10-pentyl ) pentapropan-1-ol < / RTI >

1,3,5,7,9-Pentamethylcyclopentasiloxane (2.00 g, 6.65 mmol) was added to the round-flask reactor, and then the reactor was evacuated for 2 hours and filled with high-purity N ₂ gas. Then, 30 ml of anhydrous toluene and allyl alcohol (66.5 mmol, 4.53 ml) were added and stirred for 20 minutes. Then, Pt (dvs) (0.05 ml) was added at room temperature and stirred for 20 hours. After the stirring was completed, the solution was diluted with chloroform for HPLC, 10 g of activated carbon was added to the round flask, and the mixture was further stirred for 24 hours. Thereafter, to remove the activated carbon, the filter paper was used to filter the filter paper, and then anhydrous magnesium sulfate was added to remove water. To remove the anhydrous magnesium sulfate, the filter paper was filtered with a sieve filter, Filtered. After removing the solvent, the residue was dried in a vacuum oven at 60 ° C. for 24 hours to remove the residual solvent.

^{1 H-NMR (300 MHz,} CDCl 3) δ 0.27 (s, 12H), 1.02 (t, 4H), 1.50 (m, 4H), 3.50 (t, 4H) 3.65 (bs, 2H)

[ Example  10] octakiz (3-hydroxypropyldimethylsiloxane) Octaprismosilsuquioxane ( Octakis (3- hydroxypropyldimethylsiloxy ) octaprismosilsesesquioxane (POSS-OH))

Octakis (dimethylsiloxy) octaprismosilsesquioxane (2.00 g, 1.94 mmol) was added to the round flask reactor, and the reactor was evacuated for 2 hours and then purged with high purity N ₂ gas. 25 ml of anhydrous toluene and allyl alcohol (31.4 mmol, 2.14 ml) were added and stirred for 20 minutes. Then, Pt (dvs) (0.05 ml) was added thereto at room temperature and stirred for 20 hours. After the stirring was completed, the solution was diluted with chloroform for HPLC, and then 10 g of activated carbon was added to the round flask, followed by further stirring for 24 hours. Thereafter, to remove the activated carbon, the filter paper was used to filter the filter paper, and then anhydrous magnesium sulfate was added to remove water. To remove the anhydrous magnesium sulfate, the filter paper was filtered with a sieve filter, Filtered. After removing the solvent, the residue was dried in a vacuum oven at 60 ° C for 24 hours to remove the residual solvent, and a solid white compound was obtained after the completion of the operation.

^{1 H-NMR (300 MHz,} CDCl 3) δ 0.14 (s, 48H), 0.59 (t, 8H), 1.61 (m, 8H), 2.98 (bs, 8H), 3.56 (t, 8H)

[Example 11] Fabrication of Organic Thin Film Transistor Element

1 equivalent of Octakis (3-hydroxypropyldimethylsiloxane) Octapis (3-hydroxypropyldimethylsiloxy) octaprismmosilsesquioxane (hereinafter referred to as "POSS-OH" hereinafter) prepared in Example 10 was added to the reactor And 1.4 equivalents of a melamine crosslinking agent were added in an amount of 48% by weight, and 0.2% by weight of p-toluenesulfonic acid and 84.8% by weight of propylene glycol monomonyl ester acetate were added as an acid catalyst and the mixture was stirred at 25 DEG C for 24 hours to prepare a mixed solution .

After the ITO patterned glass substrate was cleaned by the UV-O ₃ method, the prepared mixed solution was spin-coated at 1000 rpm for 10 seconds while being filtered using a 0.20 μm syringe filter at room temperature. The glass substrate on which the mixed solution was spin-coated was baked at 80 ° C for 20 minutes. At this time, a crosslinking reaction was carried out by the condensation reaction between the POSS-OH and the melamine crosslinking agent to prepare an insulating film.

At this time, pentacene was deposited to a thickness of 60 nm using an evaporator, and an Au electrode was deposited to have a thickness of 50 nm to form an insulator of MIM structure.

The characteristics and the electrostatic capacity of the MIM insulator thus manufactured are shown in the following Table 1, and the electrical characteristics were evaluated in a glove box under nitrogen, and are shown in FIGS. 5 to 8.

[ Example  12] Organic thin film transistor  Device fabrication

A total of 15% by weight of the compound POSS-OH prepared in Example 10 and 1.2 equivalent of a melamine crosslinking agent were added to the reactor, and 0.2% by weight of p-toluenesulfonic acid, 84.8% by weight of propylene glycol monomonyl ester acetate %, And the mixture was stirred at 25 占 폚 for 24 hours to prepare a mixed solution.

After the ITO patterned glass substrate was cleaned by the UV-O ₃ method, the prepared mixed solution was spin-coated at 1000 rpm for 10 seconds while being filtered using a 0.20 μm syringe filter at room temperature. The glass substrate on which the mixed solution was spin-coated was baked at 80 ° C for 20 minutes. At this time, a crosslinking reaction was carried out by the condensation reaction between the POSS-OH and the melamine crosslinking agent to prepare an insulating film.

At this time, pentacene was deposited to a thickness of 60 nm using an evaporator, and an Au electrode was deposited to a thickness of 50 nm to form a MIM structure insulator.

The characteristics and the electrostatic capacity of the MIM insulator thus manufactured are shown in the following Table 1, and the electrical characteristics were evaluated in a glove box under nitrogen, and are shown in FIGS. 5 to 8.

[Example 13] Fabrication of Organic Thin Film Transistor Element

To the reactor was added 15% by weight in total of 1 equivalent of the compound POSS-OH prepared in Example 10 and 1.6 equivalents of a melamine crosslinking agent, and 0.2% by weight of p-toluenesulfonic acid, 84.8% by weight of propylene glycol monomonyl ester acetate And the mixture was stirred at 25 캜 for 24 hours to prepare a mixed solution.

After the ITO patterned glass substrate was cleaned by the UV-O ₃ method, the prepared mixed solution was spin-coated at 1000 rpm for 10 seconds while being filtered using a 0.20 μm syringe filter at room temperature. The glass substrate on which the mixed solution was spin-coated was baked at 80 ° C for 10 minutes. At this time, a crosslinking reaction was carried out by a condensation reaction between Octakis (3-hydroxypropyldimethylsiloxy) octaprismosilsilsquioxane (POSS-OH) and a melamine crosslinking agent.

At this time, pentacene was deposited to a thickness of 60 nm using an evaporator, and an Au electrode was deposited to a thickness of 50 nm to form a MIM structure insulator.

The characteristics and the electrostatic capacity of the MIM insulator thus manufactured are shown in the following Table 1, and the electrical characteristics were evaluated in a glove box under nitrogen, and are shown in FIGS. 5 to 8.

[Example 14] Fabrication of organic thin film transistor device

The reactor was charged with the compound 3,3 ', 3 ", 3' '' - (2,4,6,8-tetramethyl-1,3,5,7,2,4,6, Tetraoxetetrasiloxane-2,4,6,8-tetrayl) tetrapropan-1-ol (3,3 ', 3 " Tetraoxatetrasiloxane-2,4,6,8-tetrayl) tetrapropan-1-ol): CTS-OH (hereinafter referred to as "CTS- Melamine crosslinking agent in an amount of 0.7 equivalents, a total amount of 20 wt% was added, and 0.2 wt% of p-toluenesulfonic acid and 79.8 wt% of propylene glycol monomonyl ester acetate as an acid catalyst were added and stirred at 25 캜 for 24 hours to prepare a mixed solution.

After the ITO patterned glass substrate was cleaned by the UV-O ₃ method, the prepared mixed solution was spin-coated at 1000 rpm for 10 seconds while being filtered using a 0.20 μm syringe filter at room temperature. Then, the glass substrate on which the mixed solution was spin-coated was baked at 80 ° C for 20 minutes. At this time, the cross-linking reaction was carried out by the condensation reaction between CTS-OH and melamine cross-linking agent.

At this time, pentacene was deposited to a thickness of 60 nm using an evaporator, and an Au electrode was deposited to a thickness of 50 nm to form an insulator of MIM structure.

The characteristics and the electrostatic capacity of the MIM insulator thus manufactured are shown in the following Table 1, and the electrical characteristics were evaluated in a glove box under nitrogen, and are shown in FIGS. 5 to 8.

[Example 15] Fabrication of organic thin film transistor device

The reactor was charged with the compound 3,3 ', 3 ", 3' '' - (2,4,6,8-tetramethyl-1,3,5,7,2,4,6, Tetraoxetetrasiloxane-2,4,6,8-tetrayl) tetrapropan-1-ol (3,3 ', 3 " Tetraoxatetrasiloxane-2,4,6,8-tetrayl) tetrapropan-1-ol): CTS-OH (hereinafter referred to as "CTS- 0.2 wt% of p-toluenesulfonic acid and 79.8 wt% of propylene glycol monomonyl ester acetate as an acid catalyst were added to 0.5 equivalent of a melamine crosslinking agent, and the mixture was stirred at 25 캜 for 24 hours to prepare a mixed solution.

After the ITO patterned glass substrate was cleaned by the UV-O ₃ method, the prepared mixed solution was spin-coated at 1000 rpm for 10 seconds while being filtered using a 0.20 μm syringe filter at room temperature. Then, the glass substrate on which the mixed solution was spin-coated was baked at 80 ° C for 20 minutes. At this time, the cross-linking reaction was carried out by the condensation reaction between CTS-OH and melamine cross-linking agent.

At this time, pentacene was deposited to a thickness of 60 nm using an evaporator, and an Au electrode was deposited to a thickness of 50 nm to form an insulator of MIM structure.

[ Example  16] Organic thin film transistor  Device fabrication

The reactor was charged with the compound 3,3 ', 3 ", 3' '' - (2,4,6,8-tetramethyl-1,3,5,7,2,4,6, Tetraoxetetrasiloxane-2,4,6,8-tetrayl) tetrapropan-1-ol (3,3 ', 3 " Tetraoxatetrasiloxane-2,4,6,8-tetrayl) tetrapropan-1-ol): CTS-OH (hereinafter referred to as "CTS- 0.2 weight% of p-toluenesulfonic acid and 79.8 weight% of propylene glycol monomonyl ester acetate were added as an acid catalyst, and the mixture was stirred at 25 占 폚 for 24 hours to prepare a mixed solution.

After the ITO patterned glass substrate was cleaned by the UV-O ₃ method, the prepared mixed solution was spin-coated at 1000 rpm for 10 seconds while being filtered using a 0.20 μm syringe filter at room temperature. Then, the glass substrate on which the mixed solution was spin-coated was baked at 80 ° C for 20 minutes. At this time, the cross-linking reaction was carried out by the condensation reaction between CTS-OH and melamine cross-linking agent.

At this time, pentacene was deposited to a thickness of 60 nm using an evaporator, and an Au electrode was deposited to a thickness of 50 nm to form an insulator of MIM structure.

The characteristics and the electrostatic capacity of the MIM insulator thus manufactured are shown in the following Table 1, and the electrical characteristics were evaluated in a glove box under nitrogen, and are shown in FIGS. 5 to 8.

[Comparative Example 1]

The thickness of the insulating film made of PGMEA solution containing PVP (12 wt%, Aldrich) and poly (melamine-co-formaldehyde) (Aldrich) as a crosslinking agent was 620 nm, Pentacene was deposited to a thickness of 60 nm using an evaporator, and an Au electrode was deposited to a thickness of 50 nm to prepare a MIM structure insulator.

The characteristics and capacitance of the MIM insulator thus manufactured are shown in the following Table 1, and the electrical characteristics were evaluated in a glove box under nitrogen, and are shown in FIGS. 5 to 7.

[Table 1]

Table 1 shows the electrostatic capacity values and the characteristics of the organic thin film transistor. It can be seen that Examples 11, 13 and 14 show similar or higher mobility than Comparative Example 1, and Comparative Example 1 And the ON / OFF ratio is measured in the same manner. In Examples 13 and 14, the characteristics of the organic thin film transistor are improved because the alcohol groups of the siloxane derivative are all reacted during the thermal curing process.

The organic thin film transistor devices manufactured in Examples 11 and 13 to 14 have similar or better characteristics compared to Comparative Example 1 using PVP.

First, in the case of the I-V curve of FIG. 5 measured in the MIM structure, both the comparative example 1 and the embodiment show a similar value and the example 16 shows a slightly higher leakage current value.

The capacitance per unit area shown in FIG. 6 is similar to or higher than that of the embodiment 12. As the frequency increases, it can be seen that the value of the capacitance is changed less than that of the comparative example 1.

FIG. 7 shows a transition curve of characteristics of the organic thin film transistor, and it was confirmed that the characteristics of the organic thin film transistor appeared.

Claims (11)

A thermosetting resin composition comprising a melamine crosslinking agent represented by the following formula (1) and a siloxane-based polyhydric alcohol compound represented by the following formula (2) or (3)
[Chemical Formula 1]

(2)

(3)

(Wherein R < _{1 &}

or

, ≪ / RTI >
R ₇ and R ₈ are each independently straight or branched C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy or (CH ₂ ) _X -OH, provided that at least two (CH ₂ ) _X -OH Including,
R ₁₀ to R ₁₇ are each independently a linear or branched C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy or (CH ₂ ) _X -OH, provided that at least two (CH ₂ ) _X -OH Including,
The C ₁ -C ₂₀ alkyl and C ₁ -C ₂₀ alkoxy may each be independently substituted with a linear or branched C ₁ -C ₂₀ alkyl or (CH ₂ ) _X -OH,
M is an integer of 2 to 10,
And x is an integer of 1 to 10.) The method according to claim 1,
Wherein R ₇ , R ₈ and R ₁₀ to R ₁₇ are selected from the group _consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, iso-butyl, tert-butyl, iso-octyl, methoxy, ethoxy, oxygen or (CH ₂ ) _X -OH. The method according to claim 1,
Wherein the siloxane polyhydric alcohol compound is selected from the following formulas.

delete delete delete delete An insulating film made of the thermosetting resin composition according to any one of claims 1 to 3. delete delete delete

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