KR100316735B1 - Polyamides having carbonate group and heat-resistant photoresist composition therefrom - Google Patents

Abstract

The present invention relates to a polyamide polymer comprising a carbonate side chain and a photosensitive heat resistant insulator composition, and more particularly, a portion exposed to light is dissolved by a developer, and a portion not receiving light is left afterwards. A polyamide polymer comprising a novel carbonate side chain having a function capable of converting into a heat resistant polymer by a phosphorus heating process, a passivation layer and a buffer film by containing the polyamide polymer and a small amount of photoacid generator. The present invention relates to a photosensitive heat resistant insulating composition that can be used as a buffer coat or an interlayer insulating film of a composite multilayer printed circuit board.

Description

Polyamides having carbonate group and heat-resistant photoresist composition therefrom

The present invention relates to a polyamide polymer comprising a carbonate side chain and a photosensitive heat resistant insulator composition, and more particularly, a portion exposed to light is dissolved by a developer, and a portion not receiving light is left afterwards. A polyamide polymer comprising a novel carbonate side chain having a function capable of converting into a heat resistant polymer by a phosphorus heating process, a passivation layer and a buffer film by containing the polyamide polymer and a small amount of photoacid generator. A photosensitive heat resistant insulating composition that can be used as a buffer coat or an interlayer insulating film of a multilayer printed circuit board.

Heat-resistant insulators have been used for the purpose of forming an interlayer insulating film of a passivation layer, a buffer coat, or a composite multilayer printed circuit board of a semiconductor. In addition, a complex lithography process such as photoresist coating, prebake, UV irradiation, development, etching, and film removal is performed again on the thin film of the heat resistant insulator for the electrical connection of the upper and lower layers or the multilayer wiring.

However, if the thin film material of the heat resistant insulator has a photosensitive device, it is possible to manufacture the holes necessary for the electrical connection in the heat resistant insulation film forming process without the photoresist process as described above, and the process can be greatly simplified, and the resist used And productivity can be increased by reducing the amount of chemicals used, process shortening, and the like. In addition, it is possible to prevent the reproducibility and resolution degradation caused by the pattern reproduced in the litho process by performing the etching process of the heat resistant insulator. Therefore, the process can be greatly simplified by using the photosensitive heat resistant insulator which combines the function of the photoresist and the heat resistant insulator.

In the case of the photoresist, the photoresist is removed by removing the film after the pattern formation process such as exposure and etching, but in the case of the photosensitive heat insulator, the photoresist is permanently present in the semiconductor device. In addition to properties as materials, properties required as semiconductor and electronic process materials such as insulation, heat resistance, mechanical, low dielectric properties, and the like are required. The photosensitive heat insulator is applicable to all fields in which a thin dielectric material is used, and is mainly used in a passivation layer, a buffer coat, or a multilayer printed circuit board of a semiconductor device.

Until now, the photosensitive heat insulator has a negative photosensitive polyimide resin using a photocrosslinked polyimide precursor having an ester group or an ionic group introduced into a side chain, as described in German Patent No. 2,437,348 or J. Macromolecluar Science A21 , 1641 (1984). Mainly developed. However, in the negative type heat resistant insulator, an incorrect shape pattern due to particles or cracks that may exist on the photomask may appear, and since the organic solvent is used as the developer, a reduction in resolution due to swelling during development may occur.

On the other hand, in connection with the positive photosensitive heat-resistant low dielectric, US Patent No. 4,927,736 shows that a photosensitive agent such as naphtoquinone diazide (hereinafter referred to as NQ) is organically bonded or blended to an aromatic polyimide containing a hydroxyl group. have. Since the aromatic polyimide containing a hydroxy group has a large light absorption and eventually has a low quantum yield, a large amount of photosensitive agent should be used to improve the quantum yield. However, in the process of heating the non-exposed part and converting it into a heat-resistant polymer, not only a large amount of polar pyrolysates of the used photosensitive agent exist in the film, but also a polar group (for example, -OH group) remains in the polymer main chain to maintain the dielectric constant. It raises and lowers heat resistance.

As another example, in order to improve photosensitivity and resolution, an aromatic polyimide containing a hydroxy group as a chemically amplified acid-sensitive group [ Polymers for Advanced Technology , vol. 4 , 277, 287, 1992] or amic acid tert-butyl ester precursor [European Patent Publication No. 0502400A1] to block -OH or -COOH to lower the solubility in the basic aqueous solution, a photoacid generator. Acid sensitization is decomposed by the protons generated after photoreaction, and -OH or -COOH is regenerated and solubilized in the developer. However, in this case, the photosensitization effect of the chemical amplification type which increases the quantum efficiency can be obtained, but in the former case, -OH generated by decomposing the acid sensitizer in the final heat treatment process remains in the film. In the case of Publication No. 0502400A1, the amount of photoacid generators used in a mixture is too high, which causes a high dielectric constant and a low heat resistance.

On the other hand, U.S. Patent Nos. 5,449,584 and 5,037,720 may have mixed or organically bonded a polyamide including a hydroxyl group capable of thermally converting to polybenzoxazole. At this time, the photosensitive device is a naphthoquinone diazide (NQ) derivative, so it does not use a chemically amplified photosensitive agent. Therefore, a large amount of photosensitive agent should be used. Due to the large amount of polar pyrolysates present in the film, the dielectric constant is increased and mechanical properties are degraded.

Accordingly, the present inventors have tried to improve the photosensitivity and fundamentally improve problems such as increase in dielectric constant and heat resistance due to -OH generated after heat treatment, which is a disadvantage of the conventional photosensitive heat insulating material. As a result, the present invention has been completed by completing a new positive photosensitive heat-resistant low-dielectric technology that combines a technique for imparting a chemically amplified photosensitive property that ensures high quantum yield, and minimizes the use of a photosensitive agent that causes the dielectric constant and removes unreacted polar groups. It was completed.

Accordingly, the present invention induces a hydroxyl group generated by carbonate side chain pyrolysis upon heating a patterned non-exposed portion and converts it into a thermally more stable benzoxazole group, thereby inducing a dielectric constant due to the remaining hydroxyl group. It is an object to provide a polyamide polymer comprising a novel carbonate side chain having as its side chain a highly molecular designed carbonate group to prevent an increase of and to maintain high heat resistance.

It is another object of the present invention to provide a novel photosensitive heat resistant insulator composition which contains a minimum amount of photoacid generator in the polyamide polymer as described above so as to have a low dielectric constant.

The present invention is characterized by a polyamide polymer comprising a carbonate side chain having a repeating unit of the following formula (1).

In Formula 1 above:

Ar ₁ is a tetravalent aromatic group , ,

And Wherein X ₁ is —CH ₂ —, —O—, —S—, —SO ₂ —. -CO-, -NHCO-, -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , or Represents;

Ar ₂ is a divalent aromatic group , , , , , , , , , , , , And Is selected from X ₁ wherein X ₁ is as defined above;

R ₁ and R ₂ Wherein R 'and R' represent a C ₁ to C ₄ lower hydrocarbon-based alkyl group, a phenyl group, or a phenyl group substituted with a substituent selected from nitro and halogen atoms;

The polyamide polymer having the general formula 1 as a repeating unit by the combination of Ar ₁ and Ar ₂ may be a homopolymer or a copolymer.

Referring to the present invention in more detail as follows.

Polyamide polymer containing a carbonate side chain according to the present invention is a dicarboxylic acid and a dicarboxylic acid of an aromatic diamine containing an alkyl oxycarbonyloxy group (-OCOOR) -OH or an acid sensitive group as shown in the formula (1) And polyamide structures synthesized from the derivatives thereof. Due to this molecular structural specificity, the polyamide polymer of the present invention can be mixed with a photoacid generator and used as a positive photosensitive heat resistant low dielectric material. That is, when a photosensitive heat insulating composition obtained by mixing a polyamide polymer and a photoacid generator is applied on a substrate as a thin film and then exposed through a photomask engraved with visible or ultraviolet light, the exposed portion is alkyloxycarbonyl, which is an acid sensitive group. The oxy (-OCOOR) side chain is thermally decomposed to be converted into a hydroxyl group (-OH) and dissolved in a basic aqueous solution such as tetramethylammonium hydroxide (hereinafter referred to as TMAH). On the other hand, since the non-exposed portion that does not receive light has low solubility in the basic aqueous solution, it is possible to form a positive pattern of the polyamide polymer. As the patterned non-exposed part is heated, an alkyloxycarbonyloxy group (-OCOOR), an acid sensitive group in the polyamide polymer, is pyrolyzed to produce a hydroxyl group (-OH), and when heated to a higher temperature, -OH May be converted to a benzoxazole group which is a low dielectric group having excellent heat resistance by combining with a carbonyl group which is a neighboring reactor. This polybenzoxazole has excellent heat resistance and shows heat resistance of 500 ° C. or higher, and is not only a very stable material with almost no organic solvent capable of dissolving it. The dielectric constant and water absorption rate are also lower than those of general polyimide. In addition, -OCOOR, used as an acid-sensitizer, decomposes and vaporizes into volatile low molecular weight chemicals (e.g. isobutene, styrene or its derivatives) and CO ₂ so that no degradant remains inside the coating, naphthoquinonedia It exhibits a much lower dielectric constant than using photosensitive polyimide (PSPI) with zide (NQ) or polyimide with side chains of tert-butoxy groups (hereinafter referred to as t-boc). That is, -OH, which is a cause of low dielectric properties, heat resistance and electrical properties, is not only removed from the polymer, but also applied to the heat-resistant reaction. In addition, since a photo-acid generator and acid sensitizer with a chemical amplification concept are used, a large amount of acid is generated when decomposed by light or acid to promote the decomposition of the acid sensitizer. Therefore, the high quantum efficiency can minimize the amount of photoacid generator used, it is possible to minimize the increase in dielectric constant and deterioration of physical properties by the photoacid generator.

In general, polyimide and polybenzoxazole have a high light absorption in the visible and ultraviolet regions, so that the color of the film is yellow to brown, so that a large amount of ultraviolet light is absorbed and thus the quantum yield tends to be lowered. On the contrary, since the polyamide polymer according to the present invention is a polyamide immediately after coating, a colorless transparent polymer can be obtained, which can exhibit higher photosensitivity.

In addition, the concentration [n / (m + n) of the acid sensitive group (-OCOOR) contained in the polyamide polymer according to the present invention is in the range of 1% to 90%, preferably 3% to 70%. . If the concentration of the acid-sensitizer (-OCOOR) is too high, the development speed is lowered, and a long exposure time or a large amount of photoacid generator is required. In addition, when the concentration of the acid-sensitizer (-OCOOR) is too small, problems such as lack of resolution and thickness reduction may occur. And the polymerization degree (m + n) which shows the molecular weight of the polyamide polymer which concerns on this invention has the range of 5-500.

In addition, the polyamide polymer having a repeating unit of Formula 1 includes both a homopolymer and a copolymer composed of a combination of Ar ₁ and Ar ₂ .

The polyamide polymer of the present invention as described above is prepared from an aromatic diamine having an dihydroxy group, an aromatic dicarboxylic acid or a derivative thereof, and the process thereof is briefly shown in the following Scheme 1.

In Scheme 1: Ar ₁ , Ar ₂ , R ₁ and R ₂ are each as defined above; X represents -OH, a halogen atom, an alkoxy group or a phenoxy group.

The polymerization method of the polyamide polymer according to Scheme 1 may be polymerized by polymerization with acid chloride, polymerization with silyl chloride, ester substitution reaction, direct polymerization and the like. The molecular weight of a polyamide polymer shows intrinsic viscosity to 0.1-2.5 dL / g. The polymerization temperature is preferably 50 ° C. or lower, preferably 30 ° C. or lower. If the polymerization temperature is too high, excessive reaction occurs to form polybenzoxazole which is insoluble in a solvent, and a polymer having low molecular weight is formed.

In addition, as a method of binding the acid sensitized alkyloxycarbonyloxy group (-OCOOR) to the polymer, an acid anhydride or chloride containing an alkyloxycarbonyloxy group is excessively reacted in a basic solution. At this time, a basic substance such as pyridine, potassium tert-butoxide, triethylamine, dimethylaminopyridine, 1,4-diazabicyclo [2,2,2] octane and the like is used as the reaction catalyst. The acid sensitivity introduction reaction is preferably carried out at room temperature or lower if possible. If the reaction temperature is high, thermal decomposition reaction of the acid sensitivity and formation of polybenzoxazole may occur.

On the other hand, the present invention includes a photosensitive heat resistant insulating composition obtained by containing a polyamide polymer having a formula (1) as a repeating unit and a photoacid generator.

Photoacid generators included in the photosensitive heat-resistant insulator composition according to the present invention can be used a variety of photoacid generators known through the literature as a material for generating an acid by exposure. Preferably, a material that absorbs light in an absorption region (300 nm or more) longer than the absorption region of the polyamide polymer used together generates an acid. Specific examples of such a photoacid generator are as follows, and the photoacid generator in the present invention is not limited to the materials exemplified below.

, ,

, ,

, ,

, ,

From above:

_{R 3, R 4, R 8} , R 10, R 11, and R ₁₂ each represents a hydrogen atom or an alkoxy group of C ₁ ~C _10, specifically, a hydrogen atom, a methoxy group, an ethoxy group, a propoxy group, a butoxy Indicating when, etc .;

R ₅ represents a C ₁ -C ₁₀ alkyl group, a C ₁ -C ₁₀ haloalkyl group, a phenyl group or a camphoryl group unsubstituted or substituted, and specifically, a methyl group, an ethyl group, a trifluoromethyl group, a phenyl group, 4 -Methylphenyl group, camphoryl group and the like;

R _6, R _7, R ₉ is a hydrogen atom, a halogen atom, an alkyl group of C ₁ ~C _10, specifically, a hydrogen-party, a chlorine atom, a bromine atom, a fluorine atom, a methyl group, an ethyl group, a propyl group, a butyl group And the like.

The photoacid generator as described above is contained in the range of 0.3 to 20% by weight based on the polyamide polymer. If the amount of photoacid generator is used too much, not only the dielectric properties, mechanical strength and heat resistance of the film may be lowered, but also the light transmittance may be difficult to form a complete hole. If the amount of the photoacid generator is too small, sufficient acid may not be present. It can't fully play its role as zero, resulting in poor resolution.

The photosensitive heat insulator composition according to the present invention can be prepared and used in a solution state, and as a solvent, dimethylsulfooxide, hexamethylphosphoamide, dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone, Solvents such as gamma-butyrolactone, diglyme, butoxyethanol and propylene glycol methyl ether acetate (PGMEA) may be used but are not limited to specific solvents. However, it is preferable to use ester or ether solvent rather than amide solvent. In addition, these solvents may be used by mixing two or more solvents in order to improve the uniformity, thickness control and adhesion of the thin film. The photosensitive heat insulating composition is prepared in a concentration of 0.1 to 70% by weight, and can be used by adjusting it according to a desired coating thickness.

In addition, the formation of a thin film using the photosensitive heat insulating insulator composition can be applied to any method such as spin coating, bar coating, and duct blades, which are widely used in the electronics industry. The drying temperature is 40 ~ 150 ℃ for thin film formation. If the drying temperature is too low, the drying time is long. If the drying temperature is too high, the color is dark due to pyrolysis of acid sensitivity and the formation of benzoxazole group. Because of the conversion, the decrease in transmittance occurs.

An exposure apparatus may be an exposure apparatus that displays visible light or ultraviolet rays having a wavelength of 200 to 500 nm using ultraviolet rays. However, it is preferable to use an exposure apparatus equipped with a filter capable of displaying monochromatic wavelengths in terms of resolution and fairness. . The present invention does not limit specific equipment or exposure equipment.

The exposure time can be changed according to the experimental conditions, and when using the ultraviolet exposure apparatus equipped with the 365 nm filter used in the present invention, the exposure time was changed from 15 to 110 seconds, and the more powerful exposure apparatus was used. The exposure time can be shorter. The exposure energy is quantified using an energy meter, the resolution is checked by depth and width using a profilometer, and the cross section of the thin film is confirmed by an electron microscope.

The present invention as described above will be described in more detail based on the following examples, but the present invention is not limited thereto.

Example 1

In a 500 mL flask under nitrogen atmosphere, 20 mL of pyridine, 30 g (0.082 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 16.62 g (0.082 mol) of isophthalic acid dichloride were added. The solution was dissolved in dimethylacetamide while stirring and reacted for 12 hours while maintaining 0 ° C. The viscous liquid obtained was precipitated in 1 L of methanol cooled to 0 ° C. and dried in a vacuum oven at 50 ° C. The white precursor powder thus obtained was again dissolved in tetrahydrofuran (THF), and 71.5 g of 4-fold equivalent di-tert-butyldicarbonate was dissolved together with 0.5 g of pyridine as a basic catalyst, followed by stirring again for 12 hours. The solution was precipitated in a methanol solution cooled to 0 ° C., filtered, washed several times with methanol and water, and dried to obtain a polyamide polymer powder having an acid sensitivity. The intrinsic viscosity of the obtained polymer was obtained with a molecular weight of 0.70 dL / g, and the acid sensitivity was 34%. The concentration of acid sensitizer (-OCOOR ₁ ) was confirmed by IR spectral spectrum. The acid sensitizer concentration was carbonate peak (approximately 1769) based on the aromatic CH modification peak (approximately 889 cm ^-1 ) on the IR spectral spectrum. cm ^-1 ), which is also the value of n / (n + m) in the polymer represented by the formula (1).

The polyamide polymer (obtained viscosity of 0.70 dL / g) obtained above and p-nitrobenzyl-9,10-dimethoxyanthracene-2-sulfonate (NBAS) as a photoacid generator were gamma to a content as shown in Table 1 below. -Dissolved in 150 mL butyrolactone and filtered through a 0.25 μm filter. The solution was spin coated onto a silicon wafer and accelerated to dry at 110 ° C. for 5 minutes to obtain an insulator thin film having a thickness of 12 μm. It was exposed for 45 seconds through a photomask using an ultraviolet exposure apparatus equipped with a 365 nm filter. After heating at 110 ° C. for 5 minutes, it was developed in a developer solution of 2.38 wt% of tetramethylammonium hydroxide (TMAH) and washed with water. The wafer on which this pattern was formed was heated in 350 degreeC oven, and the hardened pattern was obtained. The resolution was checked for depth and width using a profilometer, and the cross section of the thin film was observed with an electron microscope. The results are shown in Table 1 below.

Example 2

In Example 1, a polyamide polymer having an intrinsic viscosity of 0.25 dL / g was obtained by raising the temperature of the polymerization reaction to 50 ° C. And dissolving and coating in the same manner as in Example 1 using 3 wt% of p-nitrobenzyl-9,10-dimethoxyanthracene-2-sulfonate (NBAS) as a synthesized polyamide polymer and a photoacid generator. Dried, exposed, developed and cured. The results are shown in Table 2 below.

Example 3

To prepare a polyamide polymer in the same manner as in Example 1, the acid-sensitized group by changing the amount of di-tert- butyl dicarbonate added to 0.5 times equivalent, 2 times equivalent, 10 times equivalent, 20 times equivalent Phosphorus t-boc concentrations were adjusted to 15%, 25%, 42% and 52%, respectively. And dissolving and coating in the same manner as in Example 1 using 3 wt% of p-nitrobenzyl-9,10-dimethoxyanthracene-2-sulfonate (NBAS) as a synthesized polyamide polymer and a photoacid generator. It dried, developed, and hardened, and exposure time was 15 second, 25 second, 70 second, and 110 second, respectively. The results are shown in Table 3 below.

Example 4

In a 300 mL flask under nitrogen atmosphere, add 6 mL of pyridine, 10 g (0.046 mol) of 3,3'-diamino-4,4'-dihydroxybiphenyl, and 9.4 g (0.046 mol) of isophthalic acid dichloride. It was dissolved in dimethylformamide while maintaining the reaction at 0 ° C for 12 hours. The viscous liquid obtained was precipitated in 1 L of methanol cooled to 0 ° C. and dried in a vacuum oven at 50 ° C. The resulting light yellow precursor powder was dissolved in tetrahydrofuran (THF) again, and then stirred again for 12 hours while dissolving 4 times the equivalent of di-tert-butyldicarbonate with 0.4 g of potassium-t-butoxide as a basic catalyst. The viscous solution thus obtained was precipitated in a methanol solution cooled to 0 ° C., filtered, washed with methanol and water several times, and dried to obtain a polyamide polymer powder having an acid sensitivity. The intrinsic viscosity of the obtained polymer was obtained at a molecular weight of 0.52 dL / g, and the acid sensitivity was 40%.

And dissolving and coating in the same manner as in Example 1 using 3 wt% of p-nitrobenzyl-9,10-dimethoxyanthracene-2-sulfonate (NBAS) as a synthesized polyamide polymer and a photoacid generator. It dried, developed, and hardened and the exposure time was 75 second. The results are shown in Table 4 below.

Example 5

5 mL of triethylamine, 10 g (0.0273 mol) of hexafluoropropane and 8.0 g (0.0273 mol) of oxydibenzoic acid chloride in a 300 mL flask under nitrogen atmosphere. The solution was dissolved in dimethylformamide while stirring, and reacted for 12 hours while maintaining 0 ° C. The viscous liquid obtained was precipitated in 1 L of methanol cooled to 0 ° C. and dried in a vacuum oven at 50 ° C. The obtained white precursor powder was dissolved in tetrahydrofuran (THF) again, and then stirred again for 12 hours while dissolving 4 times the equivalent of di-tert-butyldicarbonate with 0.5 g of pyridine as a basic catalyst. Precipitated in a methanol solution cooled to 0 ° C., filtered, washed with methanol and water several times, and dried to obtain a polyamide polymer powder having an acid-sensitive group. The intrinsic viscosity of the obtained polymer was obtained with a molecular weight of 0.47 dL / g, and the acid sensitivity was 35%.

And dissolving and coating in the same manner as in Example 1 using 4 wt% of the synthesized polyamide polymer and p-nitrobenzyl-9,10-dimethoxyanthracene-2-sulfonate (NBAS) as a photoacid generator. Dried, exposed, developed and cured. The results are shown in Table 5 below.

Example 6

5 mL of triethylamine, 10 g (0.0273 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2.27 g of isophthalic acid dichloride and oxydibenzoic acid in a 300 mL flask under nitrogen atmosphere 4.0 g of chloride was mixed and dissolved in dimethylformamide while stirring, and reacted for 12 hours while maintaining 0 ° C. The viscous liquid obtained was precipitated in 1 L of methanol cooled to 0 ° C. and dried in a vacuum oven at 50 ° C. The obtained white copolymer precursor powder was again dissolved in tetrahydrofuran (THF), and then viscous solution obtained by stirring again for 12 hours while dissolving 4 times the equivalent of di-tert-butyldicarbonate with 0.5 g of pyridine as a basic catalyst. The precipitate was precipitated in a methanol solution cooled to 0 ° C., filtered, washed with methanol and water several times, and dried to obtain a polyamide copolymer powder having an acid sensitivity. The intrinsic viscosity of the obtained polymer was obtained with a molecular weight of 0.43 dL / g, and the acid sensitivity was 34%.

And dissolving and coating in the same manner as in Example 1 using 3 wt% of p-nitrobenzyl-9,10-dimethoxyanthracene-2-sulfonate (NBAS) as a synthesized polyamide polymer and a photoacid generator. Dried, exposed, developed and cured. The results are shown in Table 6 below.

Example 7

Dissolving, coating, drying, and exposure in the same manner as in Example 1, using the polyamide polymer having an intrinsic viscosity of 0.70 dL / g and the compounds shown in Table 7 as photoacid generators prepared by the method of Example 1, respectively. , Developed and cured. The results are shown in Table 7 below.

As described above, the polyamide polymer including the carbonate side chain according to the present invention is a functionalized polymer capable of inducing a heat-resistant reaction of the OH group, in particular, -OCOOR bonded with an acid-sensitized group is decomposed to have a low volatile molecular weight. Much lower dielectric than photosensitive heat-resistant insulators using naphthoquinone diazide (NQ) or polyimide precursors with tert-butoxy groups, which have been gasified with chemicals and CO ₂ , leaving no decomposition products inside the coating. Represents a constant.

Accordingly, the photosensitive heat insulating composition including the polyamide polymer according to the present invention and a small amount of photoacid generator can be used in all fields in which low dielectric materials are used. In particular, a passivation layer and a buffer film of a semiconductor device may be used. It is useful as an interlayer insulating film material for a buffer coat) or a composite multilayer printed circuit board.

Claims (7)

Next, a polyamide polymer comprising a carbonate side chain characterized in that the formula (1) as a repeating unit. Formula 1 In Formula 1 above: Ar ₁ is a tetravalent aromatic group , , , And Wherein X ₁ is —CH ₂ —, —O—, —S—, —SO ₂ —. -CO-, -NHCO-, -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , or Represents; Ar ₂ is a divalent aromatic group , , , , , , , , , , , , And Is selected from X ₁ wherein X ₁ is as defined above; R ₁ and R ₂ are each Wherein R 'and R' represent a C ₁ to C ₄ lower hydrocarbon-based alkyl group, a phenyl group, or a phenyl group substituted with a substituent selected from nitro and halogen atoms; m + n is a degree of polymerization which represents the molecular weight of the polyamide polymer, ranging from 5 to 500; The polyamide polymer having the general formula 1 as a repeating unit by the combination of Ar ₁ and Ar ₂ may be a homopolymer or a copolymer. delete The polyamide polymer comprising a carbonate side chain according to claim 1, wherein the concentration of the acid sensitive group (-OCOOR) contained in the polyamide polymer is 3% to 70%. The polyamide polymer comprising a carbonate side chain according to claim 1, wherein the polyamide has an inherent viscosity range of 0.1 to 2.5 dL / g. A polyamide polymer having the following formula (1) as a repeating unit and 0.3 to 20% by weight of a photoacid generator based on the polyamide described above. Formula 1 In Formula 1: Ar ₁ , Ar ₂ , R ₁ and R ₂ are as defined in claim 1, respectively. 6. The photosensitive heat insulating composition according to claim 5, wherein the photoacid generator is a material that absorbs light having a wavelength longer than that of the polyamide polymer (300 nm or more) to generate an acid. 7. The photosensitive heat insulating composition according to claim 5 or 6, wherein the photoacid generator is selected from the compounds exemplified below. , , , , , , , , From above: R ₃ , R ₄ , R ₈ , R ₁₀ , R ₁₁ , and R ₁₂ each represent a hydrogen atom or a C _{1 to} C ₁₀ alkoxy group; R ₅ represents a C ₁ -C ₁₀ alkyl group, a C ₁ -C ₁₀ haloalkyl group, a phenyl group or camphoryl group unsubstituted or substituted with an alkyl group; R _6, R _7, R ₉ represents an alkyl group of a hydrogen atom, a halogen atom, C ₁ ~C _10.