KR101292546B1 - Polyimide type hardner and photosensitive resin composition including the hardner - Google Patents

Abstract

The present invention relates to a polyimide curing agent and a photosensitive resin composition comprising the same, and to a polyimide curing agent represented by the following formula (1) and a photosensitive resin composition comprising the same:

[Formula 1]

(Wherein,

는

The

와 같은 방향족 또는

Aromatic or as

One or two or more selected from alicyclic groups such as;

-Y- is a divalent organic group

One or two selected from among;

Z is an aromatic end group containing 1 to 3 isocyanate groups;

n is an integer from 1 to 20.)

According to the present invention, a polyimide-type curing agent reacting with the hydroxyl group of the polyimide resin and the photosensitive resin composition having excellent heat resistance, hygroscopicity, film properties and mechanical properties by supplementing the weak mechanical properties of the photosensitive polyimide for semiconductors Can be provided.

Polyimide, Curing Agent, High Heat Resistance, Hygroscopicity, Photosensitive Resin Composition

Description

Polyimide-type hardening | curing agent and the photosensitive resin composition containing the same {POLYIMIDE TYPE HARDNER AND PHOTOSENSITIVE RESIN COMPOSITION INCLUDING THE HARDNER}

The present invention relates to a polyimide curing agent and a photosensitive resin composition comprising the same, and more particularly, to a curing agent and a composition included in the photosensitive resin composition applied to a buffer coating layer for a semiconductor, The present invention relates to a photosensitive resin composition in which a network with the resin composition is formed to improve heat resistance and hygroscopicity.

In general, a method of forming a microscopic image of a photosensitive polyimide is a negative type in which a portion to which light is insolubilized in a developer is left as an insulating film in a semiconductor device. However, negative photoresists have problems such as low storage stability, shrinkage in curing reaction, and swelling during development. The use of positive type photosensitive polyimide, in which a lighted section is dissolved and removed in a developer, has been suggested as a way of improving the disadvantage of the negative type. The positive type has the advantage that it is possible to develop in a non-polluting organic alkali aqueous solution, so that it does not need to install a waste solution treatment device. In addition, when applied as an ultra-thin polyimide positive resist, it is expected to play an important role as a resist material because it can solve the problem of light absorption into the resist material and has advantages such as high resolution and shorter light irradiation time.

In general, a polyimide resin refers to a high heat resistant resin prepared by condensation polymerization of aromatic tetracarboxylic acid or a derivative thereof and aromatic diamine or aromatic diisocyanate followed by imidization. The polyimide resin may have various molecular structures depending on the type of monomer used, thereby exhibiting various physical properties.

In addition, polyimide resins are insoluble and insoluble ultra-high heat resistant resins, which have the following characteristics, which possess excellent thermal oxidation resistance and useable temperature are very high, long-term use temperature is about 260 ℃, and short-term use temperature is about 480 ℃. It has excellent heat resistance, excellent electrochemical and mechanical properties, excellent radiation and low temperature properties, inherent flame retardancy, and excellent chemical resistance.

However, in the case of the photosensitive polyimide for semiconductors applied to the buffer coating of the conventional semiconductor, there is a limit in increasing the molecular weight for high resolution and high sensitivity, which results in weak mechanical properties. In addition, it is inevitable to add a monomer containing a hydroxyl group that can be combined with the photosensitizer and to reduce the solubility to implement the photo properties. However, if the hydroxyl group remains after heat curing, it will adversely affect the hygroscopicity.

In the case of organic solvent soluble polyimides as positive photosensitive polyimide compositions, the solvent soluble polyimides of patents JP1914604 and US6627377 have high sensitivity, heat resistance, dimensional stability, storage stability, and are easy to be manufactured industrially, but the hydroxyl groups remain after the curing process. When applied to the field of electronic materials, such as semiconductor, there is a disadvantage that is vulnerable to hygroscopic resistance. In addition, the low molecular weight is advantageous for implementing the photo characteristics, and thus there is a disadvantage that the mechanical properties are more vulnerable.

The present invention is to solve the above problems, to efficiently compensate for the weak mechanical properties of the photosensitive polyimide for semiconductor, to provide a photosensitive resin composition excellent in high heat resistance, moisture absorption, film properties and mechanical properties, and The purpose is to provide a polyimide type curing agent that reacts with the hydroxyl group of the polyimide resin.

The present invention is to achieve the above object, and provides a polyimide-type curing agent represented by the following formula (1):

[Formula 1]

(Wherein,

는

The

와 같은 방향족 또는

Aromatic or as

One or two or more selected from alicyclic groups such as;

-Y- is a divalent organic group

One or two selected from among;

Z is an aromatic end group containing 1 to 3 isocyanate groups;

n is an integer from 1 to 20.)

In addition, the present invention provides a photosensitive resin composition comprising a polyimide, a photosensitive acid generator and a polyimide type curing agent represented by the following general formula (1):

[Formula 1]

(Wherein,

는

The

와 같은 방향족 또는

Aromatic or as

One or two or more selected from alicyclic groups such as;

-Y- is a divalent organic group

One or two selected from among;

Z is an aromatic end group containing 1 to 3 isocyanate groups;

n is an integer from 1 to 20.)

In addition, the substituent Z is

It is characterized in that one of the selected.

Moreover, the ratio of the isocyanate group (-NCO) of a polyimide-type hardening | curing agent is 10-100 mol% with respect to the hydroxyl group (-OH) in the said polyimide.

In addition, the polyimide in the photosensitive resin composition is characterized in that 10 to 80wt%.

In addition, the photosensitive acid generator in the photosensitive resin composition is characterized in that 5 ~ 40wt%.

According to the present invention, by including the polyimide type curing agent reacting with the hydroxyl group of the polyimide resin and the curing agent, the weak mechanical properties of the photosensitive polyimide for semiconductor are supplemented, and thus the photosensitivity excellent in high heat resistance, hygroscopic resistance, film properties and mechanical properties. A resin composition can be provided.

The present invention relates to a polyimide curing agent represented by the following formula (1).

[Formula 1]

(Wherein,

는

The

와 같은 방향족 또는

Aromatic or as

One or two or more selected from alicyclic groups such as;

-Y- is a divalent organic group

One or two selected from among;

Z is an aromatic end group containing 1 to 3 isocyanate groups;

n is an integer from 1 to 20.)

Hereinafter, the present invention will be described in detail.

The present invention aims to improve the hygroscopicity resistance and the heat resistance by adding a polyimide low molecular weight curing agent having a hydroxyl group of the solvent-soluble polyimide resin and an NCO terminal which is curable, to the composition.

To this end, the polyimide curing agent according to the present invention is a compound represented by the formula (1), has a rigid main chain, n has a low molecular weight in the range of 1 to 20 to improve solubility in a solvent such as NMP, GBL And a terminal containing an NCO (isocyanate) group.

In addition, it is preferable that the molar ratio of the isocyanate group in a polyimide-type hardening | curing agent with respect to the hydroxyl group in polyimide is 10 to 100%. If the molar ratio is less than 10%, the degree of curing in the resin is low, there are many live hydroxyl groups are not preferable because the effect on the hygroscopicity is insufficient, and if it exceeds 100% it is not preferable because the physical properties of the film worsens.

The curing agent may cap the ends with phenol for storage stability, and isocyanate groups are activated near 200 ° C. during the curing process to form a network with hydroxyl groups in the polyimide.

The present invention also relates to a photosensitive resin composition comprising a polyimide containing a group having developability in an alkaline solution, a polyimide type curing agent represented by the formula (1), and a photosensitive acid generator.

The polyimide which can be used in the present invention is not particularly limited as long as it contains a group having developability in an alkaline solution, for example, a COOH and OH group having the following structure.

The photosensitive acid generator that can be used in the present invention is a compound having a reactivity when it is illuminated with PAC (Photo Active Compound). In the present invention, the PAC is not particularly limited, and any one widely used in the art may be used. Specific examples of the PAC may include a compound of diazonaphthoquinone (DNQ) represented by the following formula (2).

[Formula 2]

또는 H이다.Where D is

Or H.

Hereinafter, the present invention will be described in detail with reference to Examples. The following examples are intended to illustrate the invention, but the scope of the invention is not limited to the scope of the following examples.

[Example]

Polyimide Hardener Synthesis

Into a 250 ml round flask, 6 g of 4,4-oxydianiline and 6.5 g of 4-aminophenol were added 55 g of NMP (N-methyl-2-pyrrolidone) as a diamine and slowly stirred to completely dissolve. 26.7 g of 4,4'-hexafluoro isopropylidenediphthalic anhydride and 20 g of NMP were sequentially added and stirred at room temperature for 6 hours. Then, 15.2 g of toluene was added thereto, followed by a dean-stark distillation. It was installed to remove the water and refluxed at 165 ℃ for 3 hours. After removing the produced water, the toluene in the solution was removed by heating at 165 ℃ for 1 hour and then cooled to a temperature of 80 ℃.

Add 10.4 g of 2,4-Diisocyanatotoluene and let it react for another 2 hours. The isocyanate ends thus prepared are preferably used capped with phenol for storage stability. After 5.6g of phenol was added, the mixture was further reacted at 80 ° C for 3 hours, and then cooled to room temperature. The solution was slowly poured into a methanol: water = 7: 3 mixture to solidify, dried in a vacuum oven at 40 ° C. for one day, and then 40 g of a curing agent was obtained. The number average molecular weight determined by GPC standard polystyrene conversion was 1,350 g / mol.

Representing the curing agent synthesized as described above is as follows.

Polyimide Synthesis (Polymer I)

The synthesis of the polyimide is polymerized in a similar manner to the synthesis of the polyimide type curing agent. 38.4 g of 2,2'-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 2.8 g of aniline, and 100 g of NMP were added to a 250 ml round flask, and slowly stirred to completely dissolve 3,3 ', 37.2g of 4,4'-diphenylethertetracarboxylic anhydride and 52g of NMP were sequentially added and stirred at room temperature for 6 hours. Then, 30g of toluene was added and water was removed by dean-stark distillation. After the installation was allowed to reflux at 165 ℃ for 3 hours. The solution was cooled to room temperature, poured slowly into a methanol: water = 1: 4 mixture to solidify, and dried in a vacuum drying oven at 40 ° C. for one day to obtain 65 g of soluble polyimide. The number average molecular weight of the polymer I determined by GPC standard polystyrene conversion was 20,000 g / mol.

Example 1

10 g of the polyimide (polymer I) synthesized above, 5 g of the polyimide-type curing agent (NCO / OH molar ratio 0.3) synthesized above were mixed with 21.3 g of GBL (r-Butyrolactone) as a solvent to prepare a mixture solution. Subsequently, 2.5 g of diazonaphthoquinone ester compound (TPPA 320, 60% esterification rate) represented by the following Chemical Formula 3 was added to the mixture solution and stirred at room temperature for 1 hour, followed by a filter having a pore size of 1 μm. Filtration was carried out to prepare a photosensitive resin composition.

(3)

또는 H이다. Where D is

Or H.

[Example 2]

A mixture solution was prepared by mixing 10 g of the polyimide (polymer I) synthesized above and 9 g of the polyimide-type curing agent (NCO / OH molar ratio ≒ 0.5) synthesized above. Subsequently, 2.5 g of diazonaphthoquinone ester compound (TPPA 320) represented by Chemical Formula 3 was added to the mixture solution, stirred at room temperature for 1 hour, and then filtered through a filter having a pore size of 1 μm. Was prepared.

Comparative Example 1

No curing agent was added in the same composition as in Example 1.

That is, 15.3 g of GBL was mixed with 10 g of polyimide (polymer I) to prepare a mixture solution. Subsequently, 2.5 g of diazonaphthoquinone ester compound (TPPA 320) represented by Chemical Formula 3 was added to the mixture solution, stirred at room temperature for 1 hour, and then filtered through a filter having a pore size of 1 μm. Was prepared.

Comparative Example 2

A mixture solution was prepared by mixing 10 g of the polyimide (polymer I) synthesized above and 1.3 g of hexamethylene diisocyanate (TCI, NCO / OH molar ratio ≒ 0.5) as an aliphatic curing agent. Subsequently, 2.5 g of diazonaphthoquinone ester compound (TPPA 320) represented by Chemical Formula 3 was added to the mixture solution, stirred at room temperature for 1 hour, and then filtered through a filter having a pore size of 1 μm. Was prepared.

 [Experimental Example]

In order to compare the physical properties of the photosensitive resin compositions prepared in Examples 1 and 2 and Comparative Examples 1 and 2, the following experiment was carried out and the results are shown in Table 1.

Assessment Methods

(1) Film Preparation and Mechanical Properties:

The coated photosensitive composition was spin-coated on a glass plate, and heat-treated sequentially at 180 ° C. for 60 minutes at 300 ° C. and at 60 ° C. for 60 minutes in a furnace under a nitrogen stream.

After forming a polyimide film having a μm, the edges are cut and then peeled off with water. The peeled film is dried at 100 ° C. for 30 minutes to remove water, and then the film is cut into 100 × 10 mm size based on ASTM-D882. Elongation at break was measured using UTM analysis.

(2) Heat resistance (T _{d, 5%} ):

The prepared film was measured using a thermogravimetric analysis (TGA-Q500). When the temperature was raised from 10 ° C./min up to 600 ° C. in a nitrogen atmosphere, the temperature of the part having a mass loss of 5% relative to the initial mass was confirmed.

(3) Hygroscopicity:

The film is prepared using the method for producing a film. The prepared film was heated for 5 minutes from room temperature to 150 ° C. using a moisture trap device (WDS-400), and then the amount of moisture generated while isothermalizing at 150 ° C. for 10 minutes was measured. After the measurement is completed, the film is maintained at 121 ° C and 2 atmospheres for 24 hours using a pressure cooking treatment (PCT) equipment, and after 2 hours of vacuum drying at room temperature, the amount of water generated under the same conditions using a water trap equipment. Is measured again to calculate the absorbed amount of the film.

T _{d, 5%}
(℃) Modulus
(GPa) Tensile st.
(MPa) Hygroscopicity
Example 1 450 3.5 150 0.5 Example 2 480 3.8 160 0.3 Comparative Example 1 400 Not measurable Not measurable 1.5 Comparative Example 2 400 3.0 45 0.4

In the case of the photosensitive resin composition including the polyimide-type curing agent of the present invention, Comparative Example 2 including the non-curing agent of the present invention even if the curing agent is included, of course, rather than Comparative Example 1 containing no curing agent in terms of heat resistance, mechanical properties, and hygroscopicity. Better results were shown. This shows that the curing agent of the present invention has a polyimide backbone, which improves mechanical properties as well as heat resistance compared to other curing agents having a weak alkyl group as a main chain.

Claims (7)

delete delete A photosensitive resin composition comprising a polyimide, a photosensitive acid generator, and a polyimide type curing agent having a molar ratio of 10 to 100% of an isocyanate group molar ratio in the polyimide type curing agent with respect to the hydroxyl group in the polyimide: [Formula 1]

(Wherein,

The

Aromatic selected from the group consisting of

Alicyclic selected from the group consisting of; -Y- is a divalent organic group

, ≪ / RTI > Z is an aromatic terminal group containing 1 to 3 isocyanate groups

Is one of n is an integer from 1 to 20.) delete The method of claim 3, The photosensitive resin composition comprising 10 to 80 wt% of the polyimide and 5 to 40 wt% of the photosensitive acid generator in the photosensitive resin composition. delete The method of claim 3, The photosensitive acid generator (PAC) is a photosensitive resin composition, characterized in that at least one type of diazonaphthoquinone (DNQ) compounds represented by the following formula (2): [Formula 2]

Where D is

Or H.