KR20150001278A - Polyimide resin and resin composition thereof - Google Patents

Abstract

The present invention relates to a polyimide resin and a resin composition of the same and, more specifically, to a polyimide resin having a polyimide resin composition containing a diamine compound of chemical formula 1 and a tetracarboxylic acid dianhydride of chemical formula 2 polymerized to make the polymer have a linear structure and maintain thermal expansion coefficient at 50-300°C of 10 ppm/°C or less to have excellent thermal dimension stability. (In the formula, X is a cyclic hydrocarbon group including or not including hetero atoms, or substituted or unsubstituted aromatic hydrocarbon group.) (In the chemical formula 2, R is a cyclic hydrocarbon group.)

Description

POLYIMIDE RESIN AND RESIN COMPOSITION THEREOF [

The present invention relates to a polyimide resin having excellent transmittance and heat resistance in a visible light region and having a small thermal expansion coefficient and a composition thereof.

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.

Further, polyimide films obtained by forming polyimide resins into films have shrinkage and swelling due to the characteristics of the film when temperature is changed at a high temperature. This change appears as hysteresis, and since the width of the change is not always constant, it is troublesome to change the temperature several times in order to check the width of the change, and when the glass is bonded and subjected to the high temperature heat treatment, The film may warp. And the use thereof is limited particularly in the field where thermal dimensional stability is required.

Accordingly, although various methods for controlling the thermal expansion coefficient have been proposed (Korean Patent No. 1,142,723 and No. 1,227,317), it is still required to secure thermal dimensional stability.

An object of the present invention is to provide a polyimide resin having a reduced thermal expansion coefficient and improved thermal dimensional stability.

Another object of the present invention is to provide a polyimide resin composition containing a specific compound in which a polymer of a diamine compound and a tetracarboxylic dianhydride has a linear structure.

In order to achieve the above object, the present invention provides a polyimide resin having a linear structure of polymerization of a diamine compound and a tetracarboxylic dianhydride and a thermal expansion coefficient of 10 ppm / ° C or less at 50 to 300 ° C.

Preferably, the thermal expansion coefficient (50 to 300 ° C) may be 5 ppm / ° C or less.

Further, the present invention is a film obtained by curing the polyimide resin, wherein the film has a transmittance of 85% or more (at a film thickness of 10 m) in a region of 400 to 700 nm and a temperature at which the weight of the film is reduced by 5% And a thermal decomposition initiation temperature of 300 DEG C or higher.

The present invention also provides a polyimide resin composition containing a diamine compound of the following formula (1) and a tetracarboxylic acid dianhydride of the formula (2).

[Chemical Formula 1]

(Wherein X is an alicyclic hydrocarbon group containing or not containing a hetero atom, or a substituted or unsubstituted aromatic hydrocarbon group)

(2)

(Wherein R is an alicyclic hydrocarbon group)

,

,

,

,

,

,

,

,

또는

일 수 있다.Preferably, X is

,

,

,

,

,

,

,

,

or

Lt; / RTI >

,

또는

일 수 있다.
Preferably, R is selected from the group consisting of

,

or

Lt; / RTI >

The polyimide resin of the present invention has an advantage of excellent thermal dimensional stability because of its small thermal expansion coefficient.

In addition, the polyimide resin according to the present invention has an advantage that a polyimide 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 resin having excellent transmittance and heat resistance and a low thermal expansion coefficient in a visible light region, and a composition thereof.

Hereinafter, the present invention will be described in detail.

In the polyimide resin of the present invention, the polymerization of the diamine compound and the tetracarboxylic dianhydride is linear.

In the present invention, the linear structure means that the amine group of the diamine compound to be polymerized with the tetracarboxylic dianhydride has a trans structure, so that the prepared polymer has a linear structure. If the amine group of the diamine compound has a cis structure, the resulting polymer has an angle formed by amine groups at both ends and has a bent structure as shown in the schematic diagram of the following structure, which is not a linear structure.

This is because the respective central structures of the diamine compound and the tetracarboxylic dianhydride used in the present invention have a cyclic structure (R in the formula (1) and R in the formula (2)) to prevent the polymer from being bent.

As described above, when the amine group of the diamine compound is a trans structure and each central structure of the diamine and the dianhydride is composed of a cyclic structure, the induction and bent structure of the bent structure as shown in the above- The polyimide resin can maintain a low coefficient of thermal expansion.

The polyimide resin of the present invention preferably has a thermal expansion coefficient of 10 ppm / 占 폚 or less, preferably 5 ppm / 占 폚 or less at 50 to 300 占 폚.

The coefficient of thermal expansion is a factor for evaluating dimensional stability with respect to heat, and the polyimide resin of the present invention exhibits a linear structure and has a low coefficient of thermal expansion.

If the coefficient of thermal expansion is less than 10 ppm / ° C, the glass can be prevented from being warped in the process of being coated on the glass. If the coefficient of thermal expansion exceeds 10 ppm / ° C, warpage due to difference in thermal expansion coefficient between the film and the glass occurs at a high temperature There is a possibility that the accuracy of the process is lowered.

The resin according to the present invention is produced by polymerizing a polyimide resin composition containing a diamine of the following formula (1) and a tetracarboxylic acid dianhydride of the formula (2).

[Chemical Formula 1]

(Wherein X is an alicyclic hydrocarbon group containing or not containing a hetero atom, or a substituted or unsubstituted aromatic hydrocarbon group)

,

,

,

,

,

,

,

,

또는

일 수 있다.Preferably, X is

,

,

,

,

,

,

,

,

or

Lt; / RTI >

(2)

(Wherein R is an alicyclic hydrocarbon group)

,

또는

일 수 있다.
Preferably, R is selected from the group consisting of

,

or

Lt; / RTI >

The method for producing a polyimide resin according to the present invention is a one-step polymerization method in which a diamine compound of the formula (1) and a tetracarboxylic dianhydride of the formula (2) are used in almost equimolar amounts in the presence of a solvent, Or a two-stage polymerization method in which amic acid is synthesized at a high temperature and then imidized at a high temperature may be used.

The ratio of the diamine compound of the formula (1) to the tetracarboxylic dianhydride can be appropriately controlled depending on the molecular weight of the polyimide resin and the like. The diamine compound represented by the formula (1) 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 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 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.

The solvent usable in the synthesis is preferably compatible with the diamine compound of formula (1) as the starting material, the tetracarboxylic dianhydride and the polyimide resin as the product. 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.

When at least one of the diamine compound represented by the formula (1) and the tetracarboxylic acid dianhydride is used in plurality, the present invention is characterized in that the raw materials are mixed in advance and then subjected to polycondensation together, or a method in which two or more diamines or tetracarboxylic acids A method in which acid dianhydrides are added one by one while being reacted individually, and the like can be used.

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. It is preferable that such a dehydrating agent is used in an amount of 1 to 10 moles per 1 mole of the diamine compound of the formula (1).

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 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 resin may be a general organic solvent used in the synthesis of polyimide 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 can be used for re-dissolving the purified polyimide resin by a method such as adding a poor solvent to the prepared polyimide resin solution and re-precipitating .

The substrate on which the polyimide 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 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 resin film obtained by curing the polyimide 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 resin film has a transmittance of 80% or more (at a film thickness of 10 m) in a 400 to 700 nm region (visible light) when the film thickness is 10 탆, a temperature at which the weight of the film is reduced by 5% And the pyrolysis initiation temperature is 300 占 폚 or higher.

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.

Example  1-12 and Comparative Example  1-8

0.2 mol of tetracarboxylic dianhydride and 200 g of dimethylacetylamide (DMA) shown in the following Table 1 were charged into a flask equipped with a stirrer, a thermometer, a dropping device and a nitrogen substitution device, and heated to 50 캜 and stirred to dissolve. Thereafter, 0.2 mol of the aromatic diamine shown in Table 1 below was dissolved in 200 g of dimethylacetamide (DMA) at room temperature, followed by dropping funnel for 1 hour, followed by stirring at 50 DEG C for 5 hours. A portion of the reaction mixture was dissolved in a solvent of DMSO-d ₆ and NMR was measured to confirm that no diamine was present in the reactant, and it was confirmed that polyamic acid was formed 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 film.

division Aromatic diamine Tetracarboxylic dianhydride Example 1

(0.2몰)

(0.2 mole)

(0.2 mole) Example 2

(0.2 mole)

(0.2 mole) Example 3

(0.2 mole)

(0.2 mole) Example 4

(0.2 mole)

(0.2 mole) Example 5

(0.2 mole)

(0.2 mole) Example 6

(0.2 mole)

(0.2 mole) Example 7

(0.2 mole)

(0.2 mole) Example 8

(0.2 mole)

(0.2 mole) Example 9

(0.2 mole)

(0.2 mole) Example 10

(0.2 mole)

(0.2 mole) Example 11

(0.2 mole)

(0.2 mole) Example 12

(0.2 mole)

(0.2 mole) Comparative Example 1

(0.2 mole)

(0.2 mole) Comparative Example 2

(0.2 mole)

(0.2 mole) Comparative Example 3

(0.2 mole)

(0.2 mole) Comparative Example 4

(0.2 mole)

(0.2 mole) Comparative Example 5

(0.2 mole)

(0.2 mole) Comparative Example 6

(0.2 mole)

(0.2 mole) Comparative Example 7

(0.2 mole)

(0.2 mole) Comparative Example 8

(0.2 mole)

(0.2 mole)

Test Example

The physical properties of the polyimide resin prepared in the 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.

[Evaluation standard]

Transmittance 90% or more: ○

Transmittance: 85% or more and less than 90%: Δ

Transmittance less than 85%: x

2. Heat resistance

The temperature at which the weight of the polyimide film was reduced by 5% and the pyrolysis initiation temperature were measured using a Q50 instrument manufactured by TA instruments, and classified as follows.

[Evaluation standard]

Temperature at which the weight is reduced by 5% and the thermal decomposition starting temperature is 320 ° C or higher:

The temperature at which the weight is reduced by 5% and the pyrolysis initiation temperature from 300 ° C or more to less than 320 ° C:

The temperature at which the weight is reduced by 5% and the pyrolysis initiation temperature is less than 300 ° C:

3. Thermal Expansion Coefficient (CTE)

The thermal expansion coefficient at 50 to 300 ° C was measured three times using TMA (Perkin Elmer, Diamond TMA) according to the TMA-Method, ie, first run, second run and third run, ℃, then lowered again to 50 ℃ and then increased to 300 ℃ again.

The average value of measured thermal expansion coefficient values was obtained and measured.

[Evaluation standard]

Thermal expansion coefficient 5ppm / ℃ or less: ○

A thermal expansion coefficient of more than 5 ppm / DEG C to less than 10 ppm / DEG C:

Thermal expansion coefficient 10ppm / ℃ or higher: x

division Transmittance Heat resistance Coefficient of thermal expansion Example 1 ○ ○ ○ Example 2 ○ ○ ○ Example 3 ○ ○ ○ Example 4 ○ ○ ○ Example 5 △ ○ ○ Example 6 △ ○ ○ Example 7 △ ○ ○ Example 8 ○ ○ ○ Example 9 △ ○ ○ Example 10 △ ○ ○ Example 11 △ ○ ○ Example 12 ○ ○ ○ Comparative Example 1 ○ ○ × Comparative Example 2 ○ ○ × Comparative Example 3 ○ ○ × Comparative Example 4 ○ ○ × Comparative Example 5 ○ ○ × Comparative Example 6 ○ ○ × Comparative Example 7 × ○ × Comparative Example 8 ○ ○ ×

As shown in Table 2, it was confirmed that the polyimide resins of Examples 1 to 12 according to the present invention had heat resistance and transmittance equal to or more than those of Comparative Examples 1 to 8 and excellent thermal expansion coefficient.

Claims (6)

Wherein the polymerization of the diamine compound and the tetracarboxylic dianhydride has a linear structure and the coefficient of thermal expansion is 10 ppm / 占 폚 or less at 50 to 300 占 폚.
The polyimide resin according to claim 1, wherein the thermal expansion coefficient (50 to 300 ° C) is 5 ppm / ° C or less.
A film obtained by curing a polyimide resin according to claim 1 or 2, wherein the film has a transmittance of 85% or more (at a film thickness of 10 μm) in a region of 400 to 700 nm and a temperature at which the weight of the film is reduced by 5% , And a pyrolysis initiation temperature of 300 ° C or higher.
A polyimide resin composition comprising a diamine compound represented by the following formula (1) and a tetracarboxylic dianhydride represented by the following formula (2)
[Chemical Formula 1]

(Wherein X is an alicyclic hydrocarbon group containing or not containing a hetero atom, or a substituted or unsubstituted aromatic hydrocarbon group)
(2)

(Wherein R is an alicyclic hydrocarbon group)
5. The compound according to claim 4, wherein X is X

,

,

,

,

,

,

,

,

or

/ RTI >
5. The method of claim 4,

,

or

/ RTI >