JP2001066781A - Polyamide having side chain of acetal or cyclic derivative thereof and heat-resistant photoresist composition prepared from the same - Google Patents

Abstract

(57) Abstract: The present invention provides a polyamide containing a side chain of an acetal or a cyclic derivative thereof, and a heat-resistant photoresist composition. The exposed part is dissolved by a developer,
The unexposed part remains, and a polyamide containing a side chain of an acetal or a cyclic derivative thereof having a function capable of being converted to a heat-resistant polymer by a heating step as a subsequent step,
And a heat-resistant photoresist composition containing the polyamide and a small amount of a photoacid generator, which can be used for a passivation layer, a buffer coat, or an interlayer insulating film of a composite multilayer printed circuit board.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyamide having a side chain of acetal or a cyclic derivative thereof, and a heat-resistant photoresist composition prepared therefrom. The part that has not received light remains, and a polyamide having a side chain of an acetal or a cyclic derivative thereof having a function capable of being converted to a heat-resistant polymer by a heating step as a subsequent step, and a small amount of this polyamide and Of photoacid generator, passivation layer, buffer film (buffer)
The present invention relates to a heat-resistant photoresist which can be used for an interlayer coat or an interlayer insulating film of a multilayer printed circuit board.

[0002]

2. Description of the Related Art A heat-resistant material is used for forming a protective film, a buffer film of a semiconductor or an interlayer insulating film of a composite multilayer printed circuit board. Also, in order to electrically or multilayerly interconnect the upper and lower layers, a photoresist coating, a prebake UV exposure,
Complicated lithographic printing processes such as development, etching, and film removal are performed.

[0003] However, if the thin film material of the heat-resistant insulator has a photosensitive group, even if the above-described photoresist process is not used, a hole necessary for electrical connection when performing the film-forming process of the heat-resistant insulating layer. Can be formed, and the process is greatly simplified. In addition, productivity can be increased by reducing the amount of resist and chemicals used, shortening the process, and the like. Further, it is possible to prevent the reproducibility and the resolving power of the pattern reproduced from the lithographic printing process from being lowered by performing the etching process on the heat-resistant insulator. Therefore, the process can be greatly simplified by using a heat-resistant photoresist in which the function of the photoresist and the function of the heat-resistant insulator are combined.

Further, the photoresist is removed by removing the film after a pattern forming process such as exposure, development, etching and the like is completed. However, in the case of a heat-resistant photoresist, the photoresist is permanently present in the semiconductor element. In addition to the properties as photosensitive functional materials such as photosensitivity, resolution, transparency, developability, etc., the properties required as semiconductor and electronic process materials such as insulation, heat resistance, mechanical properties, low dielectric properties, etc. are required at the same time. .
The heat-resistant photoresist can be applied in all fields where a low-dielectric material in the form of a thin film is used, and is mainly applied to a protective film, a buffer film, a multilayer printed circuit board or the like of a semiconductor device.

Conventional heat-resistant photoresists are disclosed in German Patent No. 2,437,348 or J. Macromolecule Science A
As reported in 21, 1641 (1984) and the like, negative photosensitive polyimides mainly using a photocrosslinkable polyimide precursor into which an ester or an ionic group is introduced as a side chain have been developed. However, negative-type heat-resistant photoresists may cause erroneous shapes due to particles or cracks that may be present on the photomask, and use an organic solvent as a developer. At this time, the resolution may be reduced due to swelling.

On the other hand, in US Pat. No. 4,927,736, as a positive photosensitive heat-resistant photoresist, a photosensitive agent such as naphthoquinonediazide or the like is combined or mixed with an aromatic polyimide containing a hydroxy group. Reporting stuff. The aromatic polyimide containing a hydroxy group blocks light required for the reaction due to its low light transmittance. Therefore, the quantum yield becomes low, so that a large amount of a photosensitizer must be used. However, in the process of heating the unexposed portion to convert it to a heat-resistant polymer, the used photosensitizer has a large amount of polar pyrolysis in the film, and the polar group (for example, -OH group) remains in the main chain of the polymer. Since it remains, the high dielectric constant causes a decrease in heat resistance.

As another example, in order to improve photosensitivity and resolution, a chemically amplified acid-sensitive group is substituted with an aromatic polyimide containing a hydroxy group (Polymers for Advanced Technology).
logy, Vol. 4, 277, 287, 1992) or amic acid tert-
Butyl ester precursor (European Patent Publication 0502400A)
1) to block -OH or -COOH to lower the solubility in a basic aqueous solution as a developer, and the acid generated after the photoreaction of the photoacid generator decomposes the acid-sensitive group, OH or -COOH is regenerated and solubilized in the developer. However, in this case, a chemically amplified photosensitive effect that increases the quantum efficiency can be obtained. In the former case, however, the acid-sensitive group is generated by decomposition of the acid-sensitive group from the final heat treatment process. However, there is a defect that remains in the film. In European Patent Publication No. 0502400A1, the amount of the photoacid generator mixed and used is extremely large,
It causes the dielectric constant to increase and the heat resistance to deteriorate.

On the other hand, US Pat. Nos. 5,449,584 and 5,033
According to 7,720, it has been reported that a polyamide polymer containing a hydroxy group capable of being thermally converted into a polybenzoxazole is mixed or organically bonded with a photosensitive group. Since the photosensitive group used at this time does not use a chemically amplified sensitizer as a derivative of the naphthoquinonediazide compound, a large amount of the sensitizer must be used. Also, in the process of converting the unexposed part of the precursor into a heat-resistant polymer, a large amount of polar pyrolysis products of the used photosensitizer are present in the film, which increases the dielectric constant and causes deterioration of mechanical properties. .

On the other hand, J. Photopolymer Science and Tech
nology, Vol. 9, No. 4, pp. 611 (1996) contains detailed contents of photosensitive compositions in which an acetal group is introduced as an acid-sensitive group into a hydroxypolystyrene polymer. The contents described in this document are limited to application to photoresists, and have extremely poor heat resistance and mechanical strength, making it difficult to use as a photosensitive heat-resistant insulator.

[0010]

As a part of such research, the present inventors have investigated the increase in dielectric constant due to -OH generated after heat treatment, which was a disadvantage of existing photosensitive heat-resistant photoresists. We have intensively studied ways to fundamentally improve problems such as reduced heat resistance and enhance photosensitivity. As a result, a new positive type that combines both chemically amplified photosensitization technology that guarantees a high quantum yield and technology that minimizes the use of photosensitizers and removes unreacted polar groups, which is the cause of increasing the dielectric constant. The present invention was completed by completing the heat resistant and low dielectric technology.

Accordingly, the present invention provides a method for heating a patterned non-exposed portion to induce a hydroxy group generated by thermal decomposition of an acetal or a side chain of a cyclic derivative thereof into a heat-resistant reaction to thermally react the hydroxy group. A novel acetal or its cyclic compound, which is highly molecularly designed to prevent an increase in the dielectric constant due to the remaining hydroxy group by converting to a benzoxazol group that is most stable in order to maintain high heat resistance. It is an object to provide a polyamide having a side chain of a derivative.

Another object of the present invention is to provide a novel heat-resistant photoresist composition having a low dielectric constant by incorporating a minimum amount of a photoacid generator into the polyamide. In particular, the post-exposure heating step (PEB) is performed by utilizing the low activation energy required to separate the acetal or its cyclic derivative contained in the novel heat-resistant photoresist composition of the present invention from the polyamide. It has the advantage of minimizing the influence of the post exposure delay effect (PED).

[0013]

The present invention provides a polyamide having a side chain of an acetal represented by the formula (1) or a cyclic derivative thereof.

[0014]

Embedded image

[0015]

Embedded image R ₁ and R ₂ are the same or different and are each a hydrogen atom or C ₁
Straight -C _10, branched chain, or cyclic hydrocarbon esters, specifically,

[0016]

Embedded image

(Where R ′ is a C ₁ -C ₆ lower alkyl group, specifically an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a cyclohexyl group) shown; z is an integer of 1 to 5); except when R ₁ and R ₂ are hydrogen atoms at the same time; m + n is in the range of 5 to 500; the combination of the above Ar ₁ and Ar ₂ The polyamide having the above formula (1) as a repeating unit is a homopolymer or a copolymer.

The present invention will be described in more detail. As shown in the above formula (1), the polyamide containing a side chain of the novel acetal or a cyclic derivative thereof according to the present invention has --OH
Alternatively, it has a polyamide structure containing a side chain of acetal or a cyclic derivative thereof which is an acid-sensitive group. Due to this molecular structural specificity, the polyamide of the present invention can be used as a positive-type photosensitive heat-resistant low dielectric by mixing with a photoacid generator. That is, after applying a heat-resistant photoresist composition obtained by mixing a polyamide and a photoacid generator in a thin film on a substrate, and exposing it to visible light or ultraviolet light through a photomask engraved with a pattern, exposure is performed. In the part, acetal or a cyclic derivative thereof, which is an acid-sensitive group, is converted into a hydroxy group (—OH) by a thermal decomposition reaction, and is dissolved by a basic aqueous solution such as tetramethylammonium hydroxide. On the other hand, the non-exposed portion not receiving light has low solubility in the basic aqueous solution, so that a positive pattern of polyamide can be formed. By heating the non-exposed portion thus patterned, the acetal or the cyclic derivative thereof, which is an acid-sensitive group in the polyamide, undergoes a thermal decomposition reaction and undergoes a hydroxy group (—O
H) is generated, and when heated at a higher temperature, -OH bonds to an amide group, which is an adjacent reactive group, and can be converted to a benzoxazole group, which is a low dielectric substance group having extremely excellent heat resistance. . Polyoxazole has extremely excellent heat resistance and exhibits heat resistance of 500 ° C or higher, and is not only a very stable substance with almost no organic solvent that dissolves it, but also has a dielectric constant and a water absorption rate higher than that of general polyimide. Low. Acetal or a cyclic derivative thereof introduced into the side chain as an acid-sensitive group is decomposed to be a volatile chemical substance having a low molecular weight (eg, ethyl vinyl ether, 3,4
-Dihydro-2H-pyran) and no decomposed substances remain inside the film. Therefore, photosensitive polyimide (PSP) using conventional naphthoquinonediazide
It shows a much lower dielectric constant than I) or using a polyimide having a tert-butoxy group as a side chain. That is, in addition to removing -OH, which is a cause of lowering the low dielectric property, heat resistance property and electric property, in the polymer, this was applied to a heat-resistance reaction. In addition, since a photoacid generator and an acid-sensitive group are used as a concept of the chemical amplification type, a large amount of acid is generated when decomposed by light or an acid to accelerate the decomposition of the acid-sensitive group. Therefore, since the quantum efficiency is high, not only the amount of the photoacid generator to be used can be minimized, but also the increase in the dielectric constant and the deterioration of various physical properties due to the photoacid generator can be minimized.

General polyimides and polybenzoxazoles have a large light absorption in the visible light and ultraviolet regions and the color of the film is from yellow to brown, so that a considerable amount of ultraviolet light is absorbed and the quantum yield tends to decrease. There is. On the other hand, the polyamide according to the present invention provides a colorless and transparent polymer as a polyamide immediately after coating,
Higher photosensitivity can be exhibited.

Further, the concentration of the acid-sensitive group (—OR ₁ or —OR ₂ ) contained in the polyamide according to the present invention [n /
(M + n)] is in the range of 1 to 90%, preferably 3 to 70%. If the concentration of the acid-sensitive group is too high, the developing speed is reduced, and a long exposure or a large amount of a photoacid generator is required. However, if the concentration of the acid-sensitive group is too low, the photosensitivity and the resolving power may be reduced. The degree of polymerization (m + n) indicating the molecular weight of the polyamide according to the present invention is 5 to 5
00 range. Further, the polyamide having the repeating unit of the above formula (1) includes all homopolymers and copolymers composed of a combination of Ar ₁ and Ar ₂ .

[0021]

DETAILED DESCRIPTION OF THE INVENTION As described above, the polyamide of the present invention is produced from an aromatic diamine having a dihydroxy group and an aromatic dicarboxylic acid or a derivative thereof. It is as follows. Reaction formula 1

[0022]

Embedded image

In the above reaction formula, Ar ₁ , Ar ₂ , R ₁ , R ₂ ,
m and n are the same as defined above, respectively. As a polymerization method of the polyamide according to the above reaction formula 1, polymerization by an acid chloride, a polymerization method using a silyl chloride, an ester substitution reaction, a direct polymerization method, or the like is possible. The molecular weight of the produced polyamide shows an intrinsic viscosity of 0.1 to 2.5 dL / g. Polymerization reaction temperature is 50 ℃
Hereinafter, it is desirable to maintain a low temperature of 30 ° C. or less. If the polymerization reaction temperature is too high, the reaction becomes excessive, and unnecessary polybenzoxazole is easily generated in the solvent, and a polymer having a low molecular weight is formed.

In order to control the development speed and finely adjust the photosensitivity, an acid-sensitive group is introduced into the polyamide produced by the above polymerization method. As a compound introducing an acid-sensitive group,

[0025]

Embedded image

The C _{1 to} C ₁₀ linear, branched or cyclic unsaturated hydrocarbon ester compound represented by the formula (1) is used.
Specific examples of the above-mentioned acid-sensitive group-introduced compound include:
Ethyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether,
tert-butyl vinyl ether, cyclohexyl ether, 2,3-dihydropyran, 3,4-dihydro-2H
-Pyran and the like. One or more acid-sensitive group compounds can be used in combination.

As a method for bonding the acid-sensitive group to the polymer, a method in which the compound having the acid-sensitive group is reacted in the presence of an acid catalyst is preferable. According to the invention, examples of acid catalysts include strongly acidic substances such as p-toluenesulfonic acid, phosphoric acid, hydrochloric acid and the like. The introduction reaction of the acid-sensitive group is desirably performed at room temperature or lower if possible. If the reaction temperature is high, there is a possibility that the thermal decomposition reaction of the acid-sensitive group and the formation of polybenzoxazole may occur.

On the other hand, the present invention includes a heat-resistant photoresist composition obtained by including the polyamide represented by the above formula (1) and a photoacid generator. As the photoacid generator contained in the heat-resistant photoresist composition according to the present invention, various photoacid generators known in the literature as substances generating an acid upon exposure can be used. Desirably, a substance that absorbs light in a light absorption region of 300 nm or more longer than the light absorption region of the polyamide used at the same time to generate an acid is used. The above-mentioned photoacid generators are exemplified, but not limited thereto.

[0029]

Embedded image

In the above compound, R ₃ , R ₄ , R ₈ , R ₁₀ , R
₁₁ and R ₁₂ are each an alkoxy group hydrogen atom or a C ₁ -C _10, specifically, a hydrogen atom, a methoxy group, an ethoxy group, a propoxy group, a butoxy group; R ₅ is C ₁ -C ₁₀ alkyl groups, C ₁ -C ₁₀ haloalkyl groups,
A phenyl group substituted or unsubstituted with an alkyl group, or a camforyl group, specifically, a methyl group,
An ethyl group, a trifluoromethyl group, a phenyl group, a 4-methylphenyl group, a camforyl group, and the like; R ₆ , R ₇ ,
R ₉ represents a hydrogen atom, a halogen atom, or a C ₁ -C ₁₀ alkyl group, specifically, hydrogen, chlorine, bromine, fluorine, a methyl group, an ethyl group, a propyl group or a butyl group.

The above-mentioned photoacid generator is used in an amount of 0.
3-20% by weight. If too much photoacid generator is used,
In addition to reducing the dielectric properties, mechanical strength, and heat resistance in the film, the film also has poor light transmittance, making it difficult to form a complete hole. However, if the amount is too small, sufficient acid does not exist and the role as an acid generator cannot be sufficiently exhibited, resulting in poor photosensitivity.

The heat-resistant photoresist composition according to the present invention is manufactured and used in a solution state. Examples of the solvent include dimethyl sulfoxide, hexamethylphosphamide, dimethylacetamide, dimethylformamide, N
-Methyl-2-pyrrolidone, γ-butyrolactone, diglyme, butoxyethanol, propylene glycol methyl ether acetate, and the like, but are not limited to these solvents. However, ester-based or ether-based solvents are preferred over amide-based solvents. Further, two or more solvents may be used as the solvent in order to control the uniformity and thickness of the thin film and to improve the adhesive strength. The heat-resistant photoresist composition has a concentration of
It is manufactured so as to be in the range of 0.1 to 70% by weight, and is used by adjusting the thickness of the coating.

The formation of the thin film using the heat-resistant photoresist composition can be performed by any of spin coating, bar coating and doctor blade methods widely used in the electronics industry. The drying temperature for forming a thin film is suitably from 40 to 150 ° C. If the drying temperature is low, the drying time is prolonged. If the drying temperature is too high, the acid-sensitive group is thermally decomposed, and the color is deeply discolored due to the formation of benzoxazole, so that the transmittance decreases. Exposure may be performed using an exposure device that exhibits visible light or ultraviolet light having a wavelength of 200 to 500 nm, but it is desirable to use an exposure device equipped with a filter that exhibits a monochromatic wavelength, from the viewpoint of resolution and workability. It is. The present invention is not limited to a specific equipment or exposure apparatus.

The exposure time can be changed according to the experimental conditions.
According to the present invention, the exposure time can be changed from 10 to 200 seconds using an ultraviolet exposure apparatus equipped with a used 365 nm filter, and the exposure time can be reduced by a powerful exposure apparatus. The exposure energy is quantified by an energy meter, and the resolving power is confirmed by depth and width by a profile meter. The cross section of the thin film is confirmed by an electron microscope.

[0035]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. Example 1 Under a nitrogen atmosphere, pyridine (2
0 ml), 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (30 g, 0.082 mol) and isophthalic acid dichloride (16.62 g, 0.082 mol) and stirred. After dissolution, the reaction was allowed to proceed for 12 hours while maintaining the temperature at 0 ° C. A methanol solution (1 liter) obtained by cooling the obtained viscous liquid to 0 ° C
And dried in a vacuum oven at 50 ° C. After dissolving the obtained white precursor powder again in tetrahydrofuran (THF), 4 equivalents of 3,4-dihydro-2H-pyran (27.6 g) were dissolved together with p-toluenesulfonic acid (4 g) as an acidic catalyst. While stirring again for 30 minutes. The obtained viscous liquid was precipitated in a methanol solution cooled to 0 ° C., filtered, washed and dried several times with methanol and water to obtain a powder of a polyamide to which an acid-sensitive group was bound. The intrinsic viscosity of the obtained polymer was 0.76 dl / g.

According to the contents shown in the following Table 1, the polyamide obtained above (intrinsic viscosity: 0.76 dl / g) and p-nitrobenzyl-9,10-dimethoxyanthracene-2-sulfonic acid as a photoacid generator were used. The salt (NBAS) was dissolved in gamma-butyrolactone (150 ml) and filtered through a 0.25 μm filter. The solution was spin-coated on a silicon wafer and dried at 110 ° C. for 5 minutes to obtain a 10 μm-thick insulator thin film. Exposure was performed for 30 seconds through a photomask using an ultraviolet exposure apparatus equipped with a 365 nm filter. Thereafter, the mixture was heated at 90 ° C. for 1 minute, developed with 2.38% by weight of tetramethylammonium hydroxide (TMAH) as a developing solution, and washed with water. The wafer on which this pattern was formed was heated in an oven at 350 ° C. to obtain a cured pattern. Regarding the resolving power, the depth and width were confirmed with a profile instrument, and the cross section of the thin film was observed with an electron microscope. The results are shown in Table 1 below.

[0037]

[Table 1]

Example 2 A polyamide was produced in the same manner as in Example 1,
The amount of 3,4-dihydro-2H-pyran to be added is changed to 1 equivalent, 2 equivalents, 12 equivalents, and 20 equivalents, respectively, to adjust the concentration of the acid-sensitive group, tetrahydropyran-2-yl. did. Further, using the synthesized polyamide and 2% by weight of p-nitrobenzyl-9,10-dimethoxyanthracene-2-sulfonate (NBAS) as a photoacid generator, dissolving and coating in the same manner as in Example 1. ,
Dry, develop and cure, exposure time is 10
Seconds, 15 seconds, 110 seconds and 200 seconds. The results are shown in Table 2 below.
Shown in

[0039]

[Table 2]

Example 3 A polymerization reaction temperature was raised to 50 ° C. in the same manner as in Example 1 to obtain a polyamide having an intrinsic viscosity of 0.25 dl / g. Also,
Synthesized polyamide and 2% by weight of p as photoacid generator
-Nitrobenzyl-9,10-dimethoxyanthracene-
Using 2-sulfonate (NBAS), dissolution, coating, drying, exposure, development, and curing were performed in the same manner as in Example 1. The results are shown in Table 3 below.

[0041]

[Table 3]

Example 4 A polyamide precursor was produced in the same manner as in Example 1. The obtained white powder is again mixed with tetrahydrofuran (TH
After dissolving in F), the mixture was stirred again for 60 minutes while dissolving 8 equivalents of ethyl vinyl ether together with p-toluenesulfonic acid (4 g) as an acid catalyst. The obtained viscous liquid was precipitated in a methanol solution cooled to 0 ° C., filtered, washed and dried several times with methanol and water to obtain a polyamide powder having an acid-sensitive group bonded thereto.

The same procedure as in Example 1 was carried out using the synthesized polyamide and 2% by weight of p-nitrobenzyl-9,10-dimethoxyanthracene-2-sulfonate (NBAS) as a photoacid generator. Dissolution, coating, drying, development and curing were performed, and the exposure time was 25 seconds. The results are shown in Table 4 below.

[0044]

[Table 4]

Example 5 A polyamide precursor was produced in the same manner as in Example 1. The obtained white powder is again mixed with tetrahydrofuran (TH
After dissolving in F), an acid-sensitive introduced compound shown in the following Table 5 was charged into the reactor and reacted. During the reaction, the mixture was stirred again for 60 minutes while being dissolved together with p-toluenesulfonic acid (4 g) as an acidic catalyst. The obtained viscous liquid is
The precipitate was precipitated in a methanol solution cooled to ° C., filtered, washed several times with methanol and water, and dried to obtain a polyamide powder having acid-sensitive groups bonded thereto.

Further, a method similar to that of Example 1 was carried out using the synthesized polyamide and 2% by weight of p-nitrobenzyl-9,10-dimethoxyanthracene-2-sulfonate (NBAS) as a photoacid generator. Dissolution, coating, drying, development and curing were performed, and the exposure time was 25 seconds. The results are shown in Table 5 below.

[0047]

[Table 5]

EXAMPLE 6 Under a nitrogen atmosphere, pyridine (6
ml), 3,3′-diamino-4,4′-dihydroxybiphenyl (10 g, 0.046 mol) and isophthalic dichloride (9.4 g,
0.46 mol) was added thereto, stirred and dissolved in dimethylformamide, and the reaction was allowed to proceed for 12 hours while maintaining the temperature at 0 ° C. The obtained viscous liquid was precipitated in a methanol solution (1 liter) cooled to 0 ° C and dried in a vacuum oven at 50 ° C. After dissolving the obtained pale yellow precursor powder again in tetrahydrofuran (THF), while dissolving 4 equivalents of 3,4-dihydro-2H-pyran with p-toluenesulfonic acid (4 g) as an acid catalyst. And stirred again for 12 hours. The obtained viscous liquid was precipitated in a methanol solution cooled to 0 ° C., filtered, washed and dried several times with methanol and water to obtain a polyamide powder having acid-sensitive groups bonded thereto. The intrinsic viscosity of the obtained polymer was 0.62 dl / g.

The same procedure as in Example 1 was carried out using the synthesized polyamide and 3% by weight of p-nitrobenzyl-9,10-dimethoxyanthracene-2-sulfonate (NBAS) as a photoacid generator. Dissolution, coating, drying, development and curing were performed, and the exposure time was 75 seconds. The results are shown in Table 6 below.

[0050]

[Table 6]

Example 7 Under a nitrogen atmosphere, triethylamine (5 ml) and 2,2'-bis (3-amino-4-hydroxybiphenyl) hexafluoropropane (10 g, 0.0273 m) were placed in a 300 ml flask.
ol) and oxy-di-benzoic acid chloride (8.0 g, 0.0273mo)
l) was added and stirred, dissolved in dimethylformamide, and allowed to proceed for 12 hours while maintaining the temperature at 0 ° C. The obtained viscous liquid was cooled to 0 ° C. in a methanol solution (1
Liters) and dried in a vacuum oven at 50 ° C. After dissolving the obtained white precursor powder again in tetrahydrofuran (THF), four equivalents of 3,4-dihydro-2H were obtained.
-Pyran is converted to p-toluenesulfonic acid (4
Stir again for 30 minutes while dissolving with g). The obtained viscous liquid was precipitated in a methanol solution cooled to 0 ° C., filtered, washed and dried several times with methanol and water to obtain a polyamide powder having acid-sensitive groups bonded thereto. The intrinsic viscosity of the obtained polymer was 0.54 dl / g.

The same procedure as in Example 1 was carried out using the synthesized polyamide and 2% by weight of p-nitrobenzyl-9,10-dimethoxyanthracene-2-sulfonate (NBAS) as a photoacid generator. Dissolution, coating, drying, exposure, development and curing were performed. The results are shown in Table 7 below.
Shown in

[0053]

[Table 7]

Example 8 Under a nitrogen atmosphere, a 300 ml flask was charged with triethylamine (5 ml) and 2,2'-bis (3-amino-4-hydroxybiphenyl) hexafluoropropane (10 g, 0.0273 m 2).
ol), isophthalic dichloride (2.77 g, 0.0136 mol) and oxy-di-benzoic acid chloride (4.0 g, 0.0136 mol) were stirred and dissolved in dimethylformamide, and then 0 ° C.
The reaction was allowed to proceed for 12 hours while maintaining the temperature. The obtained viscous liquid was precipitated in a methanol solution (1 liter) cooled to 0 ° C and dried in a vacuum oven at 50 ° C. The obtained white precursor powder is again mixed with tetrahydrofuran (TH
After dissolving in F), the mixture was stirred again for 30 minutes while dissolving 4 equivalents of 3,4-dihydro-2H-pyran with p-toluenesulfonic acid (5 g) as an acid catalyst. Precipitating the resulting viscous liquid in a methanol solution cooled to 0 ° C.
The mixture was filtered, washed several times with methanol and water, and dried to obtain a polyamide powder having acid-sensitive groups bonded thereto. The intrinsic viscosity of the obtained polymer was 0.46 dl / g.

The same procedure as in Example 1 was carried out using the synthesized polyamide and 2% by weight of p-nitrobenzyl-9,10-dimethoxyanthracene-2-sulfonate (NBAS) as a photoacid generator. Dissolution, coating, drying, exposure, development and curing were performed. The results are shown in Table 8 below.
Shown in

[0056]

[Table 8]

Example 9 Under a nitrogen atmosphere, triethylamine (5 ml) and 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (10 g, 0.0273 mol) were placed in a 300 ml flask.
l), isophthalic acid dichloride (2.77 g, 0.0136 mol) and oxy-di-benzoic acid chloride (4.0 g, 0.0136 mol) were added, stirred, and dissolved in dimethylformamide.
The reaction was allowed to proceed for 12 hours while maintaining the temperature. The obtained viscous liquid was precipitated in a methanol solution (1 liter) cooled to 0 ° C and dried in a vacuum oven at 50 ° C. The obtained white precursor powder is again mixed with tetrahydrofuran (TH
After dissolving in F), 2 equivalents of 3,4-dihydro-2H-
The mixture was stirred again for 60 minutes while dissolving pyran and 5 equivalents of ethyl vinyl ether together with p-toluenesulfonic acid (5 g) as an acid catalyst. The obtained viscous liquid was precipitated in a methanol solution cooled to 0 ° C., filtered, washed and dried several times with methanol and water to obtain a polyamide powder having acid-sensitive groups bonded thereto. The intrinsic viscosity of the obtained polymer is
It was 0.47 dl / g.

Further, a method similar to that of Example 1 was carried out using the synthesized polyamide and 2% by weight of p-nitrobenzyl-9,10-dimethoxyanthracene-2-sulfonate (NBAS) as a photoacid generator. Dissolution, coating, drying, exposure, development and curing were performed. The results are shown in Table 9 below.
Shown in

[0059]

[Table 9]

Example 10 The intrinsic viscosity produced by the production method of Example 1 was 0.76 dl /
Coating, drying, exposure, development, and curing were carried out in the same manner as in Example 1 using a polyamide maintaining the range of g and the respective compounds shown in the following Table 10 as photoacid generators. The results are shown in Table 10 below.

[0061]

[Table 10]

[0062]

As described above, the polyamide containing a side chain of the acetal or the cyclic derivative thereof according to the present invention is OH
As a functionalized polymer capable of inducing a heat-resistant reaction of a group, particularly a polyamide containing a side chain of an acetal or a cyclic derivative thereof bonded as an acid-sensitive group is decomposed and has a volatile low molecular weight. Since there is no decomposed substance remaining inside the film after being gasified into a chemical substance, naphthoquinone diazide compound (N
Heat-resistant photoresist composition using Q) or tert-
It shows a much lower dielectric constant than a polyimide precursor having a butoxy group.

Accordingly, the heat-resistant photoresist composition containing the polyamide according to the present invention and a small amount of the photoacid generator is:
It can be used in all fields where low dielectric materials are used, especially semiconductor passivation layer, buffer layer (buffer c)
oat) or as a material for an interlayer insulating film of a composite multilayer printed circuit board.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01L 21/027 H01L 21/30 502R (72) Inventor Choi, Kil-Yeon Korea 305-340, Daejeon, Yusun -K, Doryeong-Dong 431-6, Hyundai Apartment, 101-904 (72) Inventor Wong, Jong Chang 305-333, Dae Jung, Yusun-Ku, Uhaeun-Dong 99, Hanbit Apartment, 129-801 (72) ) Inventor Kim, Tae-Kyun Republic of Korea 138-170, Seoul, Sonpark, Songpadong, 130-17 (72) Inventor Wo, Sansun Republic of Korea 137-070, Seoul, Seochouk, Seochodong, 1334, Shindonga Apartment, 8- 1008 (72) 305-390, Daejong, Yusun-ku, Junmin-dong, Sejong apartmentment, 103-1504 (72) Inventor Oh, Jaemin 305-390, Daejeon, Yusun-ku, Junmin-dong, Expo Appartment, 404-1605 (72) Inventor Lee, Moon Yang, Republic of Korea 305-390, Daejeon, Yusun-ku, Junmin-Don, Sejong Apartment, 111-307

Claims (8)

[Claims] 1. A polyamide having a side chain of an acetal represented by the formula (1) or a cyclic derivative thereof. Embedded image Embedded image R ₁ and R ₂ are the same or different and are each a hydrogen atom or C ₁
Linear, branched -C _10, or cyclic hydrocarbon esters, in particular embedded image Wherein R ′ represents a C ₁ -C ₆ lower alkyl group, specifically, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a cyclohexyl group; Represents an integer of 1 to 5);
Except when ₁ and R ₂ are both hydrogen atoms; m + n is 5
The polyamide having the above formula (1) as a repeating unit is a homopolymer or a copolymer depending on the combination of Ar ₁ and Ar ₂ . 2. The above R ₁ and R ₂ are the same or different from each other and are a hydrogen atom, (Where R ′ is a C ₁ -C ₆ lower alkyl group including an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group and a cyclohexyl group; z
Is an integer from 1 to 4), provided that R ₁
The polyamide having a side chain of acetal or a cyclic derivative thereof according to claim 1, wherein R and R ₂ are not hydrogen atoms at the same time. 3. R ₁ and R ₂ are the same or different from each other;
Hydrogen atom, ethoxyethyl group, propoxyethyl group, isopropoxyethyl group, n-butoxyethyl group, tert-
Butoxyethyl group, cyclohexyloxyethyl group, 2
- selected from among tetrahydrofuranyl group and a 2-tetrahydropyranyl group; provided that, except where R ₁ and R ₂ are hydrogen atoms at the same time, the acetal or cyclic derivative according to claim 1, wherein the Polyamide having side chains. 4. The acetal or cyclic derivative thereof according to claim 1, wherein the concentration of the acid-sensitive group (—OR ₁ or —OR ₂ ) contained in the polyamide is in the range of 3 to 70%. Polyamide having a side chain of 5. An intrinsic viscosity of the polyamide is 0.1 to 2.5 dL.
The polyamide having a side chain of the acetal or a cyclic derivative thereof according to claim 1, wherein the polyamide is in the range of / g. 6. A photosensitive heat-resistant photo-polymer comprising a polyamide represented by the formula (1) according to claim 1 and a photoacid generator in an amount of 0.3 to 20% by weight based on the polyamide. Resist composition. Embedded image In the formula, Ar ₁ , Ar ₂ , R ₁ , R ₂ , m and n are the same as those defined in claim 1. 7. The heat-resistant photoresist according to claim 6, wherein the photoacid generator is a substance that generates an acid by absorbing light in a long wavelength region of 300 nm or more in a polyamide absorption region. Composition. 8. The photoacid generator according to claim 1, wherein
8. The method according to claim 6, wherein the object is selected from objects.
The heat-resistant photoresist composition described above. Embedded imageIn the above, R_Three, R_Four, R₈, R_Ten, R₁₁And R₁₂Is it
Hydrogen atom or C respectively₁~ C _TenR represents an alkoxy group;_Five
Is C₁~ C_TenAn alkyl group of C₁~ C_TenAl halide
Substituted or unsubstituted with a kill or alkyl group
A phenyl group or a camfornyl group;₆, R₇, R
₉Is a hydrogen atom, a halogen atom, or C₁~ C _TenThe alkyl of
Represents a group.