KR20140100281A - Polyimide silicone resin - Google Patents

Abstract

The present invention relates to a polyimide silicone resin and, more ideally, to a polyimide silicone resin to manufacture films with excellent adhesion and permeability against materials, heat-resistance, mechanical strength and solvent resistance by polymerizing particular tetracarboxylic acid and aromatic diamine and heat processing the polymerized product at low temperatures in a short period of time.

Description

POLYIMIDE SILICONE RESIN [0002]

The present invention relates to a polyimide silicone resin having heat resistance and excellent transmittance in the visible light range.

Polyimide resins are widely used as resin varnishes for electronic parts and the like because of their excellent heat resistance and electrical insulation properties.

Such a polyimide resin is dissolved in an organic solvent having a high boiling point and is applied to a substrate in the form of polyamic acid, which is a precursor of polyimide, and then heat-treated at a temperature of 300 ° C or higher for a long time to dehydrate and imidize the polyimide resin.

However, since the dehydration and imidization reaction of the polyamic acid is heated for a long time at a high temperature, it causes deterioration. In addition, if the heating is insufficient, the polyamic acid remains in the structure of the produced polyimide resin, which causes deterioration of moisture resistance and corrosion resistance.

Thus, a method of applying a polyimide resin solution dissolved in an organic solvent to a base material and then heating the mixture to volatilize the solvent to produce a polyimide resin film has been proposed (JP-A-2-36232). However, the polyimide resin film produced by the above method has a disadvantage of low solvent resistance.

Further, a thermosetting polyimide resin composition (Japanese Patent Laid-Open No. Hei 10-195278) is disclosed which is heat-treated at a low temperature for a short time to produce a polyimide resin film excellent in adhesiveness, solvent resistance and the like. However, the above-mentioned thermosetting resin has a disadvantage that it does not exhibit sufficient heat resistance or its transparency is low, and its use field is limited.

An object of the present invention is to provide a polyimide silicone resin excellent in heat resistance and excellent in transmittance in a visible light region.

In order to accomplish the above object, the present invention provides an aromatic diamine compound represented by the following general formula (1), (2), or a mixture thereof; There is provided a polyimide silicone resin obtained by polymerizing a tetracarboxylic dianhydride represented by the following general formula (3), (4) or a mixture thereof.

(In the formulas (1) to (4), R ₁ and R ₂ are each independently an aliphatic hydrocarbon group or a phenyl group having 1 to 6 carbon atoms, or R ₁ and R ₂ are adjacent carbon atoms to form a ring).

Preferably, R ₁ and R ₂ in the general formulas (1) to (4) are each independently a methyl group, an ethyl group or a phenyl group, or R ₁ and R ₂ may be adjacent carbon atoms to form a ring.

More preferably, the formula (1) may be at least one selected from the following formulas (5) to (8).

More preferably, the formula (2) may be at least one selected from the following formulas (9) to (16).

More preferably, the formula (3) may be at least one selected from the following formulas (17) to (20).

More preferably, the formula (4) may be at least one selected from the following formulas (21) to (24).

The present invention also provides a polyimide silicone film obtained by curing the polyimide silicone resin.

The polyimide silicone resin according to the present invention has an advantage that a polyimide silicone film excellent in heat resistance and transmittance can be produced.

Therefore, it is useful in color filters and light emitting diodes in semiconductor devices, protective films for laser diodes, liquid crystal alignment films, liquid crystal display devices, flexible substrates for optical devices, other electronics fields and optical fields.

The present invention relates to a polyimide silicone resin containing a silicon group in a molecule and having excellent heat resistance and excellent transmittance in the visible light region.

Hereinafter, the present invention will be described in detail.

The polyimide silicone resin of the present invention comprises an aromatic diamine represented by the following general formula (1), (2), or a mixture thereof; A tetracarboxylic dianhydride represented by the following general formula (3), (4), or a mixture thereof is polymerized.

[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

(In the formulas (1) to (4), R ₁ and R ₂ are each independently an aliphatic hydrocarbon group or a phenyl group having 1 to 6 carbon atoms, or R ₁ and R ₂ are adjacent carbon atoms to form a ring).

Preferably, R ₁ and R ₂ in the general formulas (1) to (4) are each independently a methyl group, an ethyl group or a phenyl group, or R ₁ and R ₂ may be adjacent carbon atoms to form a ring.

More preferably, the formula (1) may be at least one selected from the following formulas (5) to (8).

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

More preferably, the formula (2) may be at least one selected from the following formulas (9) to (16).

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

More preferably, the formula (3) may be at least one selected from the following formulas (17) to (20).

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

[Chemical Formula 20]

More preferably, the formula (4) may be at least one selected from the following formulas (21) to (24).

[Chemical Formula 21]

[Chemical Formula 22]

(23)

≪ EMI ID =

In the present invention, in addition to the aromatic diamines of the above formulas (1) and (2), diamines generally used in the art can be mixed in the range satisfying the object. For example, aliphatic diamines such as tetramethylenediamine, 1,4-diaminocyclohexane and 4,4'-diaminodicyclohexylmethane, phenylene diamine, 4,4'-diaminodiphenyl ether, 2,2 -Bis (4-aminophenyl) propane, etc. These aromatic diamines may be used alone or in combination of two or more.

In this case, the diamine mixed with the aromatic diamine of the formulas (1) and (2) is preferably contained in an amount of 100 parts by weight or less based on 100 parts by weight of the compound of the formula (1) in consideration of heat resistance and light transmittance.

In addition, the tetracarboxylic dianhydride of the general formula (3) and the general formula (4) may be mixed with the tetracarboxylic dianhydride generally used in the art within the range satisfying the object of the present invention.

For example, aromatic tetracarboxylic acid dianhydrides represented by the following formula (25) may be used, either alone or in combination.

(25)

(Wherein X is CH ₂ , O, S, C (CH ₃ ) ₂ , C (CF ₃ ) ₂ or SO ₂ ).

The tetracarboxylic dianhydride mixed with the tetracarboxylic dianhydrides of the formulas (3) and (4) is preferably contained in an amount of 100 parts by weight or less based on 100 parts by weight of the above formulas (3) and (4) in consideration of heat resistance and light transmittance .

The process for producing a polyimide silicone resin according to the present invention is a one-step polymerization method in which an aromatic diamine and a tetracarboxylic dianhydride are used in almost equimolar amounts in the presence of a solvent and is polymerized only at a high temperature, And a two-stage polymerization method in which imidization is carried out at a high temperature.

The ratio of the aromatic diamine to the tetracarboxylic dianhydride can be appropriately adjusted depending on the molecular weight of the polyimide silicone resin and the like. The aromatic diamine preferably has a molar ratio of 0.95 to 1.05, preferably 0.98 to 1.02.

In order to adjust the molecular weight of the polyimide silicone resin, monofunctional raw materials such as phthalic anhydride and aniline may be added. In this case, it is preferably 2 mol% or less based on the polyimide silicone resin.

In the case of the one-stage polymerization method, the reaction temperature is 150 to 300 ° C, and the reaction time is 1 to 15 hours. In the case of a two-stage polymerization method, the polyamic acid synthesis is carried out at a temperature of 0 to 120 ° C for 1 to 100 hours, and the imidization is carried out at a temperature of 0 to 300 ° C for 1 to 15 hours.

It is preferable that the solvent usable in the synthesis has compatibility with the aromatic diamine as the raw material, the tetracarboxylic dianhydride and the product polyimide silicone resin. Specifically, phenols such as phenol, 4-methoxypheno-4-methoxyphenol, 2,6-dimethylphenol and m-cresol; Ethers such as tetrahydrofuran and anisole; Ketones such as cyclohexanone, 2-butanone, methyl isobutyl ketone, 2-heptanone, 2-octanone and acetophenone; Esters such as butyl acetate, methyl benzoate and? -Butyrolactone; Cellosolves such as butyl cellosolve acetate and propylene glycol monomethyl ether acetate; Amides such as N, N-dimethylformamide, N, N-dimethylacetoamide and N-methyl-2-pyrrolidone can be used.

In addition, when aromatic hydrocarbons such as toluene and xylene are used in combination, it is easy to remove water generated by imidization by azeotropy. These solvents may be used alone or in combination of two or more.

In the case of using a plurality of aromatic diamines and tetracarboxylic dianhydrides in plural types, the present invention is characterized in that the raw materials are mixed beforehand and then subjected to polycondensation together, or a method in which two or more aromatic diamines or tetracarboxylic acid dianhydrides And then adding them sequentially while reacting them individually.

Further, in the imidization process, a method of adding a dehydrating agent and an imidation catalyst, and heating and imidizing them if necessary can be used. As the dehydrating agent, for example, acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used. Such a dehydrating agent is preferably used in an amount of 1 to 10 moles per mole of the aromatic diamine.

As the imidization catalyst, for example, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used. The imidization catalyst is preferably used in an amount of 0.5 to 10 moles per mole of the dehydrating agent.

Since the polyimide silicone resin according to the present invention has excellent solubility, it can be dissolved in an organic solvent and adjusted to a suitable viscosity so as to be easily coated on various substrates.

The organic solvent capable of dissolving the polyimide silicone resin may be a general organic solvent used for the synthesis of polyimide silicone resin, an aromatic hydrocarbon solvent different from the synthetic solvent, a ketone solvent, or the like. When it is desired to dissolve in a double low boiling aromatic hydrocarbon solvent or a ketone solvent, it is preferable to use the polyimide silicone resin which is refined by a method such as adding a poor solvent to the prepared polyimide silicone resin solution and re- .

The substrate to which the polyimide silicone resin of the present invention can be coated is a metal such as iron, copper, nickel, or aluminum; Inorganic substances such as glass; An epoxy resin, and an acrylic resin.

In addition, the present invention can further improve the thermosetting property by adding a substance that reacts with a phenol group in the produced polyimide silicone resin. Examples of the substance that reacts with the phenol group include a multifunctional organic compound such as a resin or oligomer containing two or more functional groups capable of reacting with a phenol group such as a carboxyl group, an amino group, and an epoxy group.

Further, the present invention is characterized by a polyimide silicone resin film obtained by curing the polyimide silicone resin.

The curing may be carried out under ordinary conditions, specifically at a temperature of 80 to 300 ° C, preferably 100 to 250 ° C. If the curing temperature is less than 80 캜, the curing time is long and practicality is low, and storage stability may be a problem when selecting a device to be used at a low temperature.

In addition, unlike the conventional polyamic acid solution, it does not require heating for a long period of time at a high temperature higher than 300 deg. C after coating, and deterioration due to heat of the substrate can be suppressed.

The polyimide silicone resin film exhibits a transmittance of 80% or more (at a film thickness of 10 mu m) in a region of 400 to 700 nm (visible light) when the film thickness is 10 mu m.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.

Synthetic example  1 to 8: aromatic Diamine

Synthetic example  1: Formula 5

p-Bromoaniline (68.8 g, 0.40 mol) was dissolved in THF (400 ml) and the temperature was lowered to 0 占 폚. Subsequently, the solution was slowly added dropwise to a 2.2M solution of n-butyllithium / hexane (418 ml, 0.92 mol), the temperature was raised to room temperature, and the mixture was stirred for 3 hours. Then, chlorotrimethylsilane (117 ml, 0.92 mol) was slowly added dropwise and stirred at room temperature for 24 hours. The reaction mixture was filtered with a glass filter, and the solvent was distilled off under reduced pressure. The resulting reaction mixture was dissolved in acetone (500 mL) and distilled water (20 mL), stirred for 24 hours, added with MgSO ₄ (100 g), and stirred for 1 hour. Thereafter, after filtering with a glass filter, the solvent was distilled off under reduced pressure to obtain a compound of formula (5).

[Reaction Scheme 1]

(Chemical Formula 5) NMR CDCl ₃ ; 7.20 (4H), 6.40 (4H), 3.35 (4H), 0.40 (6H)

Synthetic example  2: 6

The reaction was carried out in the same manner as in Synthesis Example 1, but was carried out as shown in the following Reaction Scheme 2 to obtain Formula (6).

[Reaction Scheme 2]

(Formula 6) NMR CDCl _3; 7.20 (4H), 6.40 (4H), 3.35 (4H), 0.97 (6H), 0.79 (4H).

Synthetic example  3: Formula 7

The reaction was carried out in the same manner as in Synthesis Example 1, but was carried out according to the following Reaction Scheme 3 to obtain the formula (7).

[Reaction Scheme 3]

(Formula 7) NMR CDCl _3; 6.85-7.6 (9H), 6.40 (4H), 3.35 (4H), 0.4 (3H).

Synthetic example  4: Formula 8

The reaction was carried out in the same manner as in Synthesis Example 1, but performing the following Reaction Scheme 4 to obtain the compound of Formula 8.

[Reaction Scheme 4]

(Formula 8) NMR CDCl _3; 7.20 (4H), 6.40 (4H), 3.35 (4H), 1.61 (4H), 0.78 (4H).

Synthetic example  5: 10

After dissolving P-bromophenol (172 g, 1 mol) and benzyl bromide (178.5 g, 1.05 mol) in acetonitrile (1 L), K ₂ CO ₃ (176 g, 2 mol) was added and reacted at 50 ° C for 24 hours, After filtering with a glass filter, the solvent was removed by distillation under reduced pressure. The reaction mixture was dissolved in anhydrous THF, the temperature was lowered to -78 ° C, and a 2.2M n-BuLi hexane solution was slowly added dropwise so that n-BuLi became 1.15mol. Dimethyldichlorosilane (64 g, 0.5 mol) was then slowly added dropwise, the temperature was raised to room temperature, stirred for 24 hours, filtered through a glass filter, and then the solvent was distilled off under reduced pressure. The reaction mixture was again dissolved in THF (500 mL) and EtOH (500 mL), and 10% Pd / C was added thereto so that the concentration of Pd became 0.05 mol, 200 g of ammonium formate was added and the mixture was refluxed for 2 hours. Thereafter, the reaction mixture was filtered with a glass filter, and then the solvent was distilled off under reduced pressure to obtain a diol intermediate (Formula 26).

Dissolve the intermediate diol (100g, 0.41mol) and nitrobenzene (141g, 1.0mol) obtained in the fluoro DMF (500mL), CuI (0.1mol ) and K ₂ CO ₃ (138 g, 1 mol) was added, and the mixture was refluxed for 2 hours, filtered with a glass filter, and the solvent was distilled off under reduced pressure to obtain a nitro intermediate (Formula 27).

The obtained nitro intermediate was dissolved again in THF (500 mL) and EtOH (500 mL), and 10% Pd / C was added thereto so that the concentration of Pd became 0.05 mol. Then, 200 g of ammonium formate was added and refluxed for 2 hours. The reaction mixture was filtered with a glass filter, and the solvent was distilled off under reduced pressure to obtain the compound of formula (10).

[Reaction Scheme 5]

(26) NMR / Acetone-d ₆ ; 8.42 (2H), 7.35 (4H), 6.84 (4H), 0.45 (6H).

(Formula 27) NMR / CDCl _3; 8.20 (4H), 7.57 (4H), 7.08 (4H), 7.04 (4H), 0.59 (6H).

(Formula 10) NMR / CDCl _3; 7.41 (4H), 6.90 (4H), 6.87 (4H), 6.67 (4H), 3.59 (4H), 0.50 (6H).

Synthetic example  6:

Was carried out in the same manner as in Synthesis Example 5, but performing the following Reaction Scheme 6 to obtain the compound of Formula 12.

[Reaction Scheme 6]

(28) NMR / Acetone-d ₆ ; 8.43 (2H), 7.34 (4H), 6.83 (4H), 0.98 (6H), 0.80 (4H).

(Formula 29) NMR / CDCl _3; 8.21 (4H), 7.58 (4H), 7.09 (4H), 7.05 (4H), 0.97 (6H), 0.79 (4H).

(Formula 12) NMR / CDCl _3; 7.42 (4H), 6.91 (4H), 6.88 (4H), 6.69 (4H), 3.61 (4H), 0.96 (6H), 0.78 (4H).

Synthetic example  7: 14

The reaction was carried out in the same manner as in Synthesis Example 5, but performing the following Reaction Scheme 7 to obtain the formula (14).

[Reaction Scheme 7]

(30) NMR / Acetone-d ₆ ; 7.53 (3H), 7.35 (4H), 6.87 (2H), 6.84 (4H), 0.55 (3H).

(Formula 31) NMR / CDCl _3; 8.20 (4H), 7.57 (4H), 7.55 (3H), 7.08 (4H), 7.04 (4H), 6.88 (2H), 0.56 (3H).

(Formula 14) NMR / CDCl _3; 7.55 (3H), 7.41 (4H), 6.90 (4H), 6.87 (6H), 6.67 (4H), 3.62 (4H), 0.55 (6H).

Synthetic example  8: 16

The reaction was carried out in the same manner as in Synthesis Example 5, but performing the following Reaction Scheme 8 to obtain the compound of Formula 16.

[Reaction Scheme 8]

(32) NMR / Acetone-d ₆ ; 8.43 (2H), 7.34 (4H), 6.86 (4H), 1.61 (4H), 0.78 (4H).

(Formula 33) NMR / CDCl _3; 8.21 (4H), 7.56 (4H), 7.09 (4H), 7.03 (4H), 1.65 (4H), 0.79 (4H).

(Formula 16) NMR / CDCl _3; 7.41 (4H), 6.90 (4H), 6.87 (4H), 6.67 (4H), 3.59 (4H), 1.59 (4H), 0.75 (4H).

Synthetic example  9 to 16: Tetracarboxylic acid Water

Synthetic example  9: 17

(73.2 g, 0.40 mol) was dissolved in THF (400 ml), and the temperature was lowered to 0 ° C to slowly add a 2.2 M solution of n-butyllithium / hexane (209 ml, 0.46 mol) After the temperature was raised to room temperature, the mixture was stirred for 3 hours. Then, dichlorodimethylsilane (25.6 g, 0.2 mol) was slowly added dropwise and further stirred at room temperature for 24 hours. The obtained reaction mixture was filtered with a glass filter, and the solvent was distilled off under reduced pressure. The resulting reaction mixture was dissolved in pyridine (300 mL) and distilled water (200 mL), KMnO ₄ (100 g) was added, and the mixture was stirred at 80 ° C for 24 hours. The mixture was filtered through a glass filter and the solvent was distilled off under reduced pressure.

Thereafter, 300 mL of acetic anhydride was added, and the mixture was refluxed for 10 hours. The solvent was distilled off under reduced pressure to obtain the compound of formula (17).

 [Reaction Scheme 9]

(Formula 17) NMR / CDCl _3; 7.98 (2H), 7.94 (2H), 7.77 (2H), 0.56 (6H).

Synthetic example  10: 18

The reaction was carried out in the same manner as in Synthesis Example 9, but performing the following Reaction Scheme 10 to obtain the compound of Formula 18.

[Reaction Scheme 10]

(Formula 18) NMR / CDCl _3; 7.99 (2H), 7.93 (2H), 7.79 (2H), 0.97 (6H), 0.84 (4H).

Synthetic example  11: 19

The reaction was carried out in the same manner as in Synthesis Example 9, but performing the following Reaction Scheme 11 to obtain the compound of Formula 19.

[Reaction Scheme 11]

(Formula 19) NMR / CDCl _3; 8.02 (2H), 7.98 (2H), 7.83 (2H), 7.57 (3H), 6.91 (2H), 0.58 (3H).

Synthetic example  12: 20

The reaction was carried out in the same manner as in Synthesis Example 9, but using the following Reaction Scheme 12 to obtain the compound of Formula 20.

[Reaction Scheme 12]

(Formula 20) NMR / CDCl _3; 7.96 (2H), 7.91 (2H), 7.75 (2H), 1.64 (4H), 0.79 (4H).

Synthetic example  13: Formula 21

(122 g, 0.5 mol) and 3-chlorophthalimide (182 g, 1 mol) obtained in Synthesis Example 5 were dissolved in acetonitrile (500 ml) and KOH (50 g) was added. Thereafter, the mixture was stirred at 80 DEG C for 24 hours, filtered through a glass filter, and then the solvent was distilled off under reduced pressure to obtain the compound (21).

[Chemical Formula 13]

(Formula 21) NMR / CDCl _3; 8.08 (2H), 7.79 (2H), 7.71 (2H), 7.43 (4H), 6.92 (4H), 0.50 (6H).

Synthetic example  14: 22

The reaction was carried out in the same manner as in Synthesis Example 13, but performing the following Reaction Scheme 14 to obtain Formula 22.

[Reaction Scheme 14]

(22) NMR / CDCl _3; 8.08 (2H), 7.79 (2H), 7.71 (2H), 7.43 (4H), 6.92 (4H), 0.97 (6H), 0.79 (4H).

Synthetic example  15: Formula 23

The reaction was carried out in the same manner as in Synthesis Example 13, but using the following Reaction Scheme 15 to obtain the compound of Formula 23.

[Reaction Scheme 15]

(Formula 23) NMR / CDCl _3; 8.10 (2H), 7.81 (2H), 7.74 (2H), 7.55 (3H), 7.08 (4H), 7.04 (4H), 6.88 (2H), 0.56

Synthetic example  16: 24

The reaction was carried out in the same manner as in Synthesis Example 13, but performing the following Reaction Scheme 16 to obtain the compound of Formula 24.

[Reaction Scheme 16]

(Formula 24) NMR / CDCl _3; 8.06 (2H), 7.77 (2H), 7.69 (2H), 7.43 (4H), 6.92 (4H), 1.62 (4H), 0.79 (4H).

Example  1-15 and Comparative Example  1-13

Into a flask equipped with a stirrer, a thermometer, a dropping device and a nitrogen substitution device, 0.2 mol of tetracarboxylic dianhydride of formula (3) or (4) shown below in Table 1 and 200 g of dimethylacetamide (DMA) And dissolved by stirring. Thereafter, 0.2 mol of the aromatic diamine of the formula (1) or (2) according to the following Table 1 was dissolved in 200 g of dimethyl acetylamide (DMA) at room temperature, and then dropped for 1 hour using a dropping funnel, followed by stirring at 50 ° C for 5 hours. A part of the reaction mixture was dissolved in a solvent of DMSO-d ₆ and NMR was measured to confirm that diamine was not present in the reactant, and it was confirmed that polyamic acid was generated by IR.

The obtained polyamic acid solution was coated on a glass substrate and dried in a hot air drier at 100 占 폚 for 10 minutes to produce a film having a thickness of 10 占 퐉. The amic acid remaining on the film was heated to the following temperature profile to imidize it.

Thereafter, the film produced from the glass substrate was peeled off to produce a polyimide silicone film.

division Aromatic diamine Tetracarboxylic dianhydride Example 1

Example 2

Example 3

Example 4

Example 5

+

Example 6

+

Example 7

Example 8

+

Example 9

+

+

Comparative Example 1

Comparative Example 2

Comparative Example 3

Comparative Example 4

Comparative Example 5

+

Comparative Example 6

+

Comparative Example 7

+

Comparative Example 8

+

Comparative Example 9

+

+

Comparative Example 10

+

+

Comparative Example 11

+

+

Comparative Example 12

Comparative Example 13

Test Example

The physical properties of the polyimide silicone resin prepared in the above Examples and Comparative Examples and the films prepared therefrom were measured by the following methods, and the results are shown in Table 2 below.

1. Transmittance

The transmittance at a wavelength of 500 nm was measured using a UV-3100PC instrument manufactured by Shimadzu Corporation.

2. Heat resistance

Tg was measured using a Q1000 instrument manufactured by TA instruments, and classified as follows.

[Evaluation standard]

O: Tg of 300 DEG C or higher

占 Tg less than 300 占

division Transmittance (%) Heat resistance Example 1 95 O Example 2 95 O Example 3 94 O Example 4 95 O Example 5 95 O Example 6 94 O Example 7 96 O Example 8 95 O Example 9 94 O Comparative Example 1 91 × Comparative Example 2 89 × Comparative Example 3 90 × Comparative Example 4 85 O Comparative Example 5 96 × Comparative Example 6 91 × Comparative Example 7 92 × Comparative Example 8 89 × Comparative Example 9 78 O Comparative Example 10 88 × Comparative Example 11 85 × Comparative Example 12 73 O Comparative Example 13 88 ×

As shown in Table 2, it was confirmed that the polyimide silicone resins of Examples 1 to 9 according to the present invention had better heat resistance and transmittance than Comparative Examples 1 to 13.

Claims (7)

An aromatic diamine represented by the following formula (1), (2), or a mixture thereof; A polyimide silicone resin obtained by polymerizing a tetracarboxylic dianhydride represented by the following general formula (3), (4), or a mixture thereof:
[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

(In the formulas (1) to (4), R ₁ and R ₂ are each independently an aliphatic hydrocarbon group or a phenyl group having 1 to 6 carbon atoms, or R ₁ and R ₂ are adjacent carbon atoms to form a ring).
The polyimide silicone resin according to claim 1, wherein R ₁ and R ₂ in formulas (1) to (4) are each independently a methyl group, an ethyl group or a phenyl group, or R ₁ and R ₂ are adjacent carbon atoms to form a ring.
The polyimide silicone resin according to claim 2, wherein the formula (1) is at least one selected from the following formulas (5) to (8)
[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

The polyimide silicone resin according to claim 2, wherein the formula (2) is at least one selected from the following formulas (9) to (16):
[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

The polyimide silicone resin according to claim 2, wherein the formula (3) is at least one selected from the following formulas (17) to (20)
[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

[Chemical Formula 20]

The polyimide silicone resin according to claim 2, wherein the formula (4) is at least one selected from the following formulas (21) to (24):
[Chemical Formula 21]

[Chemical Formula 22]

(23)

≪ EMI ID =

8. A polyimide silicone film according to any one of claims 1 to 6, wherein the film has a transmittance of 80% or more (at a film thickness of 10 mu m) in a region of 400 to 700 nm.