KR100322234B1 - Polyamides having acetal and/or its cyclic derivative, and heat-resistant photoresist composition therefrom - Google Patents

Abstract

The present invention relates to a polyamide polymer and a photosensitive heat insulating composition comprising acetal or a cyclized derivative thereof as a side chain, and more particularly, a portion exposed to light is dissolved by a developer, and a portion not receiving light remains. And a new polyamide polymer comprising acetal or a cyclized derivative thereof as a side chain, which has a function capable of converting into a heat-resistant polymer by a post-heating step, and the polyamide polymer and a small amount of photoacid generator as described above. The present invention relates to a photosensitive heat resistant insulating composition that can be used as a passivation layer, a buffer coat, or an interlayer insulating film of a composite multilayer printed circuit board.

Description

Polyamides having acetal and / or its cyclic derivative, and heat-resistant photoresist composition therefrom}

The present invention relates to a polyamide polymer and a photosensitive heat insulating composition comprising acetal or a cyclized derivative thereof as a side chain, and more particularly, a portion exposed to light is dissolved by a developer, and a portion not receiving light remains. And a new polyamide polymer comprising acetal or a cyclized derivative thereof as a side chain, which has a function capable of converting into a heat-resistant polymer by a post-heating step, and the polyamide polymer and a small amount of photoacid generator as described above. The present invention relates to a photosensitive heat resistant insulating composition that can be used as a passivation layer, a buffer coat, or an interlayer insulating film of a composite multilayer printed circuit board.

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

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 after removal of the pattern forming process such as exposure, development, etching, etc., but in the case of the photosensitive heat insulator, since the photoresist is permanently present in the semiconductor device, photosensitization, resolution, transparency, developability, etc. Along with the properties as functional materials, properties required as semiconductor and electronic processing 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 acid sensitivity in the final heat treatment process remains in the film. In the case of heading 0502400A1, the amount of photoacid generators to be mixed and used is too high, which causes a high dielectric constant and lowers 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.

Meanwhile, J. Photopolymer Science and Thechnology Vol. 9, No, 4, pp. 611, (1996), describe details of photosensitive compositions in which acetal groups are introduced as acid sensitive groups in hydroxypolystyrene polymers. The content described in this document is limited to the application to photoresist, and its heat resistance and mechanical strength are very poor, making it difficult to use as a photosensitive heat resistant insulation.

Accordingly, the present inventors have tried to improve the photosensitivity and fundamentally improve the problems such as increased dielectric constant due to -OH generated after heat treatment, which is a disadvantage of the conventional photosensitive heat insulating material, and decrease in heat resistance. 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 pyrolyzing the side chain of acetal or a cyclized derivative thereof by heating the patterned non-exposed portion and converting the hydroxyl group into a thermally more stable benzoxazole group, thereby converting the remaining hydroxyl group to It is an object to provide a novel polyamide polymer that is highly molecular designed to prevent an increase in dielectric constant 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 above polyamide polymer so as to have a low dielectric constant. In particular, minimization of post-exposure heating process (PEB) and post-exposure delay by utilizing the low activation energy of the polyamide polymer including acetal or cyclized derivatives thereof as a side chain contained in the novel photosensitive heat-insulator composition of the present invention. This has the advantage of minimizing the effect of the effect (PED).

The present invention is characterized by a polyamide polymer comprising as a side chain acetal or a cyclized derivative thereof having the following formula (1) as a repeating unit.

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 the same as or different from each other, and are hydrogen atoms, or C _{1 to} C ₁₀ linear, pulverized or cyclic hydrocarbon ether groups. or Where R 'is a lower alkyl group having _{1 to 6} carbon atoms, specifically, represents an ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, cyclohexyl group, and z is 1 An integer of -5); With the exception that R ₁ and R ₂ are hydrogen atoms at the same time;

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.

The novel polyamide polymer according to the present invention has a polyamide structure in which acetal or a cyclized derivative thereof is included as a side chain as -OH or an acid sensitive group as shown in Chemical Formula 1. 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 coated on a substrate with a thin film and then exposed through a photomask engraved with visible light or ultraviolet light, the exposed portion is acetal or a ring thereof. The pyrolytic derivative is pyrolyzed to be converted to 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, the acid-sensitive group acetal or its cyclized derivative in the polyamide polymer is pyrolyzed to form a hydroxyl group (-OH), and when heated to a higher temperature, -OH is an amide group which is a neighboring reactor. In combination, it can be converted into a benzoxazole group which is a low dielectric group having excellent heat resistance. 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, acetals or cyclized derivatives thereof introduced into the side chain as acid sensitive groups are decomposed and vaporized into volatile low molecular weight chemicals (e.g., ethyl vinyl ether, 3,4-dihydro-2 H -pyran) to form an internal coating. There is no decomposer left in it, which shows a much lower dielectric constant than using a photosensitive polyimide (PSPI) using a conventional naphthoquinone diazide (NQ) or a polyimide having a tert-butoxy group as a side chain. 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.

Further, the concentration [n / (m + n)] of the acid sensitivity group (-OR ₁ or -OR ₂ ) contained in the polyamide polymer according to the present invention is 1% to 90%, preferably 3% to 70%. Have a range. If the concentration of acid-sensitizer is too high, the developing 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 retardant 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 Reaction Scheme 1: Ar ₁ , Ar ₂ , R ₁ and R ₂ are as defined above, respectively.

As a polymerization method of the polyamide polymer according to Scheme 1, polymerization by acid chloride, polymerization using silyl chloride, ester substitution reaction, direct polymerization and the like can be carried out. The molecular weight of the produced polyamide polymer shows an intrinsic viscosity up 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, an excessive reaction occurs to form a polybenzoxazole which is insoluble in a solvent, and a polymer having a low molecular weight is formed.

In order to control the development speed and fine control of the photosensitivity, an acid sensitive group is introduced into the polyamide polymer prepared by the above polymerization method. As acid sensitive introduction compounds or The C ₁ to C ₁₀ linear, pulverized or cyclic unsaturated hydrocarbon ether compound represented by is used. Specific examples of the acid sensitive group introducing compound include ethyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, tert-butyl vinyl ether, cyclohexyl vinyl ether, 2,3-dihydrofuran, 3, 4-dihydro-2H-pyran and the like. These acid sensitive compounds can also be used 1 type or in mixture of 2 or more types.

As a method of binding the acid sensitive group to the polymer, a method of reacting the acid sensitive group with an acid catalyst condition using an excess of the acid sensitive group compound is preferable. At this time, a strong acid substance such as p-toluenesulfonic acid, phosphoric acid, hydrochloric acid or the like is preferably used as the acid 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 unsubstituted or substituted with an alkyl group, or a camphoryl group, and specifically, a methyl group, an ethyl group, a trifluoromethyl group, a phenyl group, 4-methylphenyl group, camphoryl group, etc .;

R ₆ , R ₇ , and R ₉ each represent a hydrogen atom, a halogen atom, an alkyl group of C _{1 to} C ₁₀ , and specifically, a hydrogen atom, a chlorine atom, a bromine atom, a fluorine atom, a methyl group, an ethyl group, a propyl group, and 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 pattern was formed when the exposure time was measured by changing the exposure time from 10 to 200 seconds. When a powerful exposure apparatus is 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 obtained white precursor powder was again dissolved in tetrahydrofuran (THF), and then 27.6 g of 4 times equivalent of 3,4-dihydro-2H-pyran was dissolved again with 4 g of p-toluenesulfonic acid as an acidic catalyst, and again for 30 minutes. The viscous solution obtained by stirring 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 with a molecular weight of 0.76 dL / g. The substitution rate of the acid sensitive group was confirmed by the ¹ H-NMR spectroscopic spectrum. The integral area of aromatic hydrogen (peak positions: 8.50, 8.10, 7.91, 7.65, 7.28, 7.12, 7.00 ppm) and the aliphatic hydrogen atom of cyclized acetal (5.57) , 3.83, 3.52, 1.77, 1.47 ppm), and the concentration of the substituted acid sensitivity was [n / (n + m)] was 28 mol%.

The polyamide polymer (obtained viscosity of 0.76 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 for 5 minutes at 110 ° C. to obtain an insulator thin film having a thickness of 10 μm. It was exposed for 30 seconds through a photomask using an ultraviolet exposure equipment equipped with a 365 nm filter. Thereafter, the mixture was heated at 90 ° C. for 1 minute, and then developed in a developer of 2.38 wt% of tetramethylammonium hydroxide (TMAH), followed by washing 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

To prepare a polyamide polymer in the same manner as in Example 1, the amount of 3,4-dihydro-2H-pyran to be added is changed to 1 times, 2 times, 12 times, 20 times The concentration of the tetrahydropyran-2-yl group, which is an acid sensitive group, was adjusted. ^As a result of analyzing the ¹ H-NMR spectroscopic spectrum, the acid-sensitive substitution rate [n / (n + m)] of the synthesized polyamide polymer was 6 mol%, 13 mol%, 82 mol%, and 97 mol%, respectively. And dissolving and coating in the same manner as in Example 1 using 2% by weight 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 10 second, 15 second, 110 second, and 200 second, respectively. The results are shown in Table 2 below.

Example 3:

In Example 1, the temperature of the polymerization reaction was increased to 50 ° C. to obtain a polyamide polymer having an intrinsic viscosity of 0.25 dL / g of acid sensitive group substitution ratio [n / (n + m)] of 29 mol%. And dissolving and coating in the same manner as in Example 1 using 2% by weight 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 3 below.

Example 4:

The white powder obtained by preparing the polyamide precursor by the same preparation method as in Example 1 was dissolved in tetrahydrofuran (THF), and then 8 times equivalent of ethyl vinyl ether was added with 4 g of p-toluenesulfonic acid as an acid catalyst. The viscous solution obtained by stirring for 60 minutes while dissolving 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 substitution rate of the acid sensitive group was confirmed by ¹ H-NMR spectroscopic spectrum. The integral area of aromatic hydrogen (peak positions: 8.50, 8.10, 7.91, 7.65, 7.28, 7.12, 7.00 ppm) and the aliphatic hydrogen atom of acetal (5.52, 3.60, 1.43, 1.04 ppm) of the integrated area was compared, the concentration of the substituted acid sensitivity group [n / (n + m)] was 35 mol%.

Then, using the synthesized polyamide polymer and p-nitrobenzyl-9,10-dimethoxyanthracene-2-sulfonate (NBAS) as a photoacid generator, dissolution, coating, drying, development And curing, and the exposure time was 25 seconds. The results are shown in Table 4 below.

Example 5:

The white powder obtained by preparing a polyamide precursor in the same manner as in Example 1 was dissolved in tetrahydrofuran (THF) again, and then the acid sensitive group introduced compound as shown in Table 5 was added to the reactor and reacted. During the reaction, a viscous solution obtained by stirring for 60 minutes while dissolving with 4 g of p-toluenesulfonic acid as an acidic catalyst was precipitated in a methanol solution cooled to 0 ° C, filtered, washed several times with methanol and water, dried, and replaced. [n / (n + m)] A polyamide polymer powder having an acid sensitivity of 30 to 37 mol% is obtained.

And dissolving and coating in the same manner as in Example 1 using 2% by weight 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 25 second. The results are shown in Table 5 below.

Example 6

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 obtained pale yellow precursor powder was again dissolved in tetrahydrofuran (THF), and then stirred again for 30 minutes while dissolving 4 times the equivalent of 3,4-dihydro-2H-pyran with 4 g of p-toluenesulfonic acid as an acid catalyst. The resulting viscous solution was precipitated in a methanol solution cooled to 0 ° C., filtered, washed several times with methanol and water, dried, and bound to 25 mol% of acid-sensitive group with a substitution rate of [n / (n + m)]. An amide polymer powder was obtained. The intrinsic viscosity of the obtained polymer was obtained with a molecular weight of 0.62 dL / g.

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. It dried, developed, and hardened and the exposure time was 70 second. The results are shown in Table 6 below.

Example 7

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 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 obtained white precursor powder was again dissolved in tetrahydrofuran (THF), followed by stirring again for 30 minutes while dissolving 4 times the equivalent of 3,4-dihydro-2H-pyran with 4 g of p-toluenesulfonic acid as an acid catalyst. The resulting viscous solution was precipitated in a methanol solution cooled to 0 ° C., filtered, washed several times with methanol and water, dried and then replaced with a polyamide having an acid sensitivity of 29 mol% substituted with [n / (n + m)]. Polymer powder was obtained. The intrinsic viscosity of the obtained polymer was obtained with a molecular weight of 0.54 dL / g.

And dissolving and coating in the same manner as in Example 1 using 2% by weight 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 7 below.

Example 8

5 mL of triethylamine, 10 g (0.0273 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane in a 300 mL flask under nitrogen atmosphere, 2.77 g (0.0136 mol) of isophthalic acid dichloride ) And 4.0 g (0.0136 mol) of oxydibenzoic acid chloride were mixed, dissolved in dimethylformamide with 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 copolymer precursor powder thus obtained was again dissolved in tetrahydrofuran (THF), followed by stirring again for 30 minutes while dissolving 4 times the equivalent of 3,4-dihydro-2H-pyran with 5 g of p-toluenesulfonic acid as an acid catalyst. The resulting viscous solution was precipitated in a methanol solution cooled to 0 ° C., filtered, washed with methanol and water several times, dried and then replaced with a polyamide containing 31 mol% of an acid-sensitive group [n / (n + m)]. Copolymer powder was obtained. The intrinsic viscosity of the obtained polymer was obtained with a molecular weight of 0.46 dL / g.

And dissolving and coating in the same manner as in Example 1 using 2% by weight 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 8 below.

Example 9

5 mL of triethylamine, 10 g (0.0273 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane in a 300 mL flask under nitrogen atmosphere, 2.77 g (0.0136 mol) of isophthalic acid dichloride ) And 4.0 g (0.0136 mol) of oxydibenzoic acid chloride were mixed, dissolved in dimethylacetamide with 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 dissolved in tetrahydrofuran (THF) again, and then 2 times of 3,4-dihydro-2H-pyran and 5 times of ethyl vinyl ether were catalyzed by 5 g of p-toluenesulfonic acid; The viscous solution obtained by stirring for 60 minutes while dissolving together was precipitated in a methanol solution cooled to 0 ° C., filtered, washed with methanol and water several times, dried, and added to a total substitution rate [n / (n + m)] 32 mol Polyamide copolymer powders having two acid sensitivity groups in% were obtained. The intrinsic viscosity of the obtained polymer was obtained with a molecular weight of 0.47 dL / g.

And dissolving and coating in the same manner as in Example 1 using 2% by weight 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 9 below.

Example 10

Dissolving, coating, drying, and exposure in the same manner as in Example 1, using the polyamide polymer having an intrinsic viscosity of 0.76 dL / g and the photoacid generator as shown in Table 7 below, respectively, as the photoacid generator. , Developed and cured. The results are shown in Table 10 below.

As described above, the polyamide polymer including acetal or a cyclized derivative thereof according to the present invention as a side chain is a functionalized polymer capable of inducing a heat-resistant reaction of an OH group, particularly an acetal or a cyclization thereof bonded to an acid sensitive group. Derivatives are decomposed and vaporized into volatile low-molecular weight chemicals, so that no decomposable substances remain inside the film. Thus, polyimide having a photosensitive heat insulating or tert-butoxy group using naphthoquinone diazide (NQ), which has been commonly used It has a much lower dielectric constant than the precursor.

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 (8)

A polyamide polymer comprising acetal or a cyclized derivative thereof as a side chain, characterized in that the following 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 the same as or different from each other and are hydrogen atoms, or C _{1 to} C ₁₀ linear, pulverized or cyclic hydrocarbon ether groups. or (Wherein R 'is a lower alkyl group of C ₁ to C ₆ , z represents an integer of 1 to 5); With the exception that R ₁ and R ₂ are hydrogen atoms at the same time; 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. The method according to claim 1, wherein R ₁ and R ₂ are the same as or different from each other hydrogen atom, And (Wherein, R 'is an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t- butyl group, a lower alkyl group of C ₁ ~C ₆ containing a cyclohexyl group, z is an integer of from 1 to 4 ), Except that R ₁ and R ₂ are hydrogen atoms at the same time, except that a polyamide copolymer comprising acetal or a cyclized derivative thereof as a side chain. The hydrogen atom, ethoxyethyl group, propoxyethyl group, isopropoxyethyl group, n-butoxyethyl group, tert-butoxyethyl group, cyclohexyloxyethyl group according to claim 1, wherein R ₁ and R ₂ are the same or different. , 2-tetrahydrofuranyl group and 2-tetrahydropyranyl group, except that when R ₁ and R ₂ are hydrogen atoms at the same time, characterized in that a poly containing acetal or a cyclized derivative thereof as a side chain Amide copolymers. The acetal or ring thereof according to claim 1, wherein the concentration [n / (n + m)] of the acid sensitive group (-OR ₁ or -OR ₂ ) contained in the polyamide polymer is 3% to 70%. A polyamide polymer comprising a side derivative as a side chain. The polyamide polymer according to claim 1, wherein the polyamide has a intrinsic viscosity range of 0.1 to 2.5 dL / g and has acetal or a cyclized derivative thereof as a side chain. 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 , R ₂ , m and n are as defined in claim 1, respectively. 7. The photosensitive heat insulating composition according to claim 6, 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. 8. The photosensitive heat insulating composition according to claim 6 or 7, 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 to C ₁₀ alkyl group, a C _{1 to} C ₁₀ haloalkyl group, a phenyl group unsubstituted or substituted with an alkyl group, or a camphoryl group; R _6, R _7, and R ₉ represents an alkyl group of a hydrogen atom, a halogen atom, or a C ₁ ~C _10.