JPH07295221A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To reduce the velocity of dissolution of an unexposed part, to increase the velocity of dissolution of an exposed part and to attain high resolution by incorporating a high molecular compd. having a carboxyl group and a specified carboxylic ester group in each side chain and a compd. which generates an acid or base under irradiation with light. CONSTITUTION:This photosensitive resin compsn. contains a high molecular compd. having a group contg. a carboxyl group and a group contg. a carboxylic ester group represented by the formula in each side chain and a compd. which generates an acid or base under irradiation with light. In the formula, R<1> is H, methyl or phenyl, R<2> is t-butyl or t-amyl, (i) is 0 or 1, (j) is 0-2, and when (j) is 0 or 1, each of plural (i)'s is 0 or 1. Since the carboxyl group which increases the velocity of dissolution in an alkali developer as well as the carboxylic ester group which is decomposed by the generated acid or base has been introduced into each side chain of the high molecular compd. as a dissolvable component, the velocity of dissolution of an exposed part is increased.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a photosensitive resin composition. More specifically, the present invention relates to a photosensitive resin composition effective against radiation such as deep ultraviolet rays, which is represented by an excimer laser used for forming a fine pattern of a semiconductor device such as a VLSI.

[0002]

2. Description of the Related Art With the demand for high integration of semiconductor devices, development of fine processing technology is in progress. Several techniques have been studied to realize this technique.
Among them, an excimer laser is used as an exposure radiation source to shorten the wavelength of the light source used in optical lithography technology,
Exposure techniques such as the use of electron beams and X-rays as an exposure radiation source, which can ignore problems such as optical interference, are drawing attention.

Conventionally, as a photosensitive resin composition (resist) for photolithography, a photosensitive resin composition comprising a novolak resin and naphthoquinone azide has been known,
This photosensitive resin composition has excellent properties such as high resolution, dry etching resistance, and high sensitivity.

However, in the case of a photosensitive resin composition comprising the novolak resin and naphthoquinone azide,
Since the irradiation energy only causes a sequential reaction, the irradiation energy efficiency is low, and as a result, it is not possible to expect a significant improvement in sensitivity. Further, as the wavelength of the exposure radiation source becomes shorter, problems such as incompatibility between the photosensitive resin composition and the photosensitive wavelength may occur, or the transmittance of the photosensitive resin composition itself to the short wavelength may be low. ing.

In order to solve these problems, a photosensitive resin composition based on the idea of a chemical amplification type mechanism has been studied. In the case of a photosensitive resin composition based on this idea, it is a method of promoting a chemical reaction by heat other than light using an acid generated by irradiation of light as a catalyst. In this method, it is sufficient that a catalytic amount of acid can be generated by irradiation with light, so that a photosensitive resin composition having extremely high sensitivity can be obtained.

For example, JP-A-59-45439 discloses a polymer in which a water-soluble functional group of a resin highly transparent to far-ultraviolet rays is replaced with an acid-labile group, and an ultraviolet ray-containing polymer. It is disclosed that a mixture of a compound capable of generating an acid upon irradiation with is used as a photosensitive resin composition, and irradiation with ultraviolet rays is followed by heating to form a pattern.

Further, in Japanese Patent Application Laid-Open No. 5-279425, a radiation-sensitive resin obtained by polymerizing a phenylacetic acid ester having an olefinically unsaturated group, and a substance which generates an acid upon exposure to actinic radiation are also disclosed. It is described to use a radiation-sensitive composition containing as a positive resist.

In the patterning, in order to form a high resolution pattern, it is necessary to increase the difference in dissolution rate between the exposed portion and the unexposed portion of the photosensitive resin composition in the developing solution. In order to achieve this, a method of changing the solubility of the photosensitive resin in a developing solution has been proposed.

For example, JP-A-4-158363 discloses that by protecting 5 to 50% of a phenol group, which is a functional group for making it soluble in an alkaline developer, with a group which is decomposed by an acid or a base. By using a photosensitive resin composition composed of a polymer compound having reduced solubility, the difference in dissolution rate between the exposed portion and the unexposed portion in an alkali developing solution is increased to enable high-resolution pattern formation. .

[0010]

However, Japanese Laid-Open Patent Publication No. 4-1 is used.
In the case of the composition disclosed in Japanese Patent No. 58363, the dissolution rate of the unexposed area can be reduced and the difference in dissolution rate between the exposed area and the unexposed area can be increased, but the dissolution rate of the exposed area can be increased. It is difficult to increase. Therefore, there is a limit in shortening the development time of the exposed part and substantially increasing the difference in dissolution rate between the exposed part and the unexposed part, and as a result, there is a problem that there is a limit in improving the resolution. .

The present invention has been made in order to solve the problems of the prior art as described above, and suppresses the dissolution rate of the unexposed portion of the photosensitive resin composition to be low and improves the dissolution rate of the exposed portion. In addition, the difference in dissolution rate between the exposed portion and the unexposed portion with respect to the alkali developing solution is increased, and it is made for the purpose of providing a high-resolution photosensitive resin composition having high sensitivity to exposure radiation. Is.

[0012]

The present inventors have completed the present invention as a result of intensive studies to achieve the above object.

That is, the present invention comprises a group containing a carboxyl group and a compound represented by the general formula (I):

[0014]

[Chemical formula 24]

(Wherein R ¹ is a hydrogen atom, a methyl group or a phenyl group, R ² is a t-butyl group or a t-amyl group,
i is 0 or 1, j is 0, 1 or 2, but j is 0
Alternatively, in the case of 1, a plurality of i's each independently represent a group containing a carboxylic acid ester group represented by 0 or 1), a general formula (II):

[0016]

[Chemical 25]

(In the formula, R ³ is t-butyl group, t-amyl group, isopropyl group, allyl group, 1-methylvinyl group,
1,1-dimethylallyl group, 2,5-dioxanyl group or tetrahydrofuranyl group, k is a group containing a carboxylic acid ester group represented by 0, 1 or 2), the general formula (III):

[0018]

[Chemical formula 26]

(Wherein R ⁴ is a hydrogen atom, a methyl group or a phenyl group, and R ³ is the same as above) and a group containing a carboxylic acid ester group and the general formula (IV):

[0020]

[Chemical 27]

(Wherein R ³ is the same as the above), a polymer compound having at least one kind of a group containing a carboxylic acid ester group in its side chain (hereinafter, also referred to as polymer compound (A)) And a compound capable of generating an acid or a base upon irradiation with light (hereinafter, also referred to as an acid-generating compound (a)) (Invention 1) Polymer compound (A), Photosensitive resin composition (Invention 2) containing a polyvalent carboxylic acid ester compound (hereinafter, also referred to as polyvalent carboxylic acid ester compound (b)) and an acid generating compound (a) Polymer compound (Invention 2) A), a carbonic acid ester compound of a polyhydric phenol (hereinafter, a polyhydric phenol carbonic acid ester compound (c)
(Also referred to as ") and a compound (a) that generates an acid or the like (Photosensitive resin composition (Invention 3)) Polymer compound (A), alkali-soluble polymer compound (hereinafter, alkali-soluble polymer compound ( (Also referred to as B)) and a compound such as an acid-generating compound (a) (Invention 4). Polyvalent carboxylic acid ester compound (b) in Invention 2.
Is the general formula (V):

[0022]

[Chemical 28]

(In the formula, R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen atom, a general formula (VI):

[0024]

[Chemical 29]

(In the formula, R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and an alkyl group having 2 to 6 carbon atoms. An alkynyl group, an oxyalkyl group having 1 to 6 carbon atoms or a halogen atom, 1 is a group containing a carboxylic acid ester group represented by 0) to 5 or a general formula (VII):

[0026]

[Chemical 30]

(Wherein R ¹⁰ is the same as above, R ¹¹ is an alkylene group having 3 to 6 carbon atoms, a divalent hydrocarbon group having a double bond, or a general formula (VIII): — (CH ₂ ) _{m -O- (CH 2) n - (} VIII) ( wherein, m, n are each independently 1 or 2) groups represented by, 1 have the same meanings as defined above), provided that, R ^5, R ⁶ and R ⁷ At least one of them has the general formula (VI) or (VII)
A group containing a carboxylic acid ester group represented by the following formula 2) in the molecule
The photosensitive resin composition (Invention 2-1) or the alkali-soluble polymer compound (B) in Invention 4, which is a compound capable of decomposing with one or more contained acids or bases, has a carboxyl group-containing group. Photosensitive resin composition characterized by being a polymer compound having a side chain (Invention 4-1) The group containing a carboxyl group in the polymer compound (A) in Inventions 1 to 4 is represented by the general formula (IX). :

[0028]

[Chemical 31]

(In the formula, R ¹² is a hydrogen atom or a methyl group,
i is 0 or 1, j is 0, 1 or 2), a group represented by the general formula (X):

[0030]

[Chemical 32]

(Wherein k is 0 or 1) and the general formula (XI):

[0032]

[Chemical 33]

(Wherein R ¹³ and R ¹⁴ are each independently represented by a hydrogen atom, a methyl group, a phenyl group, a benzyl group or CH ₂ COOH, and Z is O, N (C ₆ H ₅ ), or NH). Group and general formula (XII):

[0034]

[Chemical 34]

A photosensitive resin composition (Invention 1-1, Invention 2-2, Invention 3-1) characterized in that it is at least one of the groups represented by the formula (i is the same as above). , Invention 4-2).

[0036]

In the invention 1, in place of the phenolic polymer compound used as the soluble component in the photosensitive resin composition described in JP-A-4-158363, the dissolution rate in an alkaline developing solution is significantly increased. By changing the polymer compound (A) in which a carboxyl group that can be increased to a large size is introduced into a side chain together with a group containing a carboxylic acid ester group that is decomposed by an acid or a base, the exposed portion of the photosensitive resin composition film is exposed. The dissolution rate of
The difference in dissolution rate between the exposed area and the unexposed area is larger than in the conventional case.

In addition, in the inventions 2 and 3, in addition to the polymer compound (A), a polyvalent carboxylic acid ester compound (b) which is a substance which is easily dissolved in an alkali developing solution by an acid or a base generated by exposure ) And the polyhydric phenol carbonate compound (c) are used in combination, the dissolution rate of the exposed portion of the photosensitive resin composition coating film is further increased.

Further, in the invention 4, since the alkali-soluble polymer compound (B) is used in addition to the polymer compound (A), the polymer compound (A) which has become soluble in the alkali developing solution by exposure is used. The dissolution rate in the alkaline developer is further increased.

Further, in the invention 2-1, as the polycarboxylic acid ester compound (b) in the invention 2, among the polycarboxylic acid ester compounds (b), particularly easily decomposed by an acid or a base generated by exposure, Since a compound that is easily converted into a compound that is easily dissolved by an alkaline developing solution is used, the dissolution rate in the exposed area is further increased.

Further, in Invention 4-1, as the alkali-soluble polymer compound (B) in Invention 4, a polymer compound which is easily dissolved in an alkali developing solution, such as a polymer compound having a carboxyl group in its side chain, is used. To use
The dissolution rate of the exposed area is further increased.

Invention 1-1, invention 2-2, invention 3-
In 1 and Invention 4-2, the polymer compound (A) having a group represented by the general formula (IX), (X), (XI) or (XII) as the carboxyl group in the polymer compound (A) is used. The difference in dissolution rate between the exposed and unexposed areas is further increased.

The reaction of the group having a carboxylic acid ester group, which is decomposed by an acid or a base contained in the polymer compound (A), by the catalytic action of an acid is performed by p-methacryloyloxyphenylacetic acid t-butyl ester. The following is an example of a polymer in which a group having a carboxylic acid ester group is introduced by polymerization.

[0043]

[Chemical 35]

[0044]

EXAMPLE A carboxyl group-containing group used in Invention 1 and a compound represented by the general formula (I):

[0045]

[Chemical 36]

(Wherein R ¹ is a hydrogen atom, a methyl group or a phenyl group, R ² is a t-butyl group or a t-amyl group,
i is 0 or 1, j is 0, 1 or 2, but j is 0
Alternatively, in the case of 1, a plurality of i's each independently represent a group containing a carboxylic acid ester group represented by 0 or 1), a general formula (II):

[0047]

[Chemical 37]

(In the formula, R ³ is a t-butyl group, a t-amyl group, an isopropyl group, an allyl group, a 1-methylvinyl group,
1,1-dimethylallyl group, 2,5-dioxanyl group or tetrahydrofuranyl group, k is a group containing a carboxylic acid ester group represented by 0, 1 or 2), the general formula (III):

[0049]

[Chemical 38]

(Wherein R ⁴ is a hydrogen atom, a methyl group or a phenyl group, and R ³ is the same as the above), and a group containing a carboxylic acid ester group and the general formula (IV):

[0051]

[Chemical Formula 39]

The polymer compound (polymer compound (A)) having in its side chain at least one of the groups containing a carboxylic acid ester group represented by the formula (wherein R ³ is the same as above) is It is a component used as a main material of the photosensitive resin composition of the invention 1, and forms a photosensitive film when applied to the substrate to be patterned, and when exposed, it is generally present in the exposed portion. A group having a carboxylic acid ester group represented by any of the formulas (I) to (IV) uses an acid or a base generated from a compound (acid-generating compound (a)) which generates an acid or a base upon irradiation with light as a catalyst. It is a component that decomposes and is converted into a polymer that dissolves in an alkali developing solution, and forms a positive pattern by development.

The group containing a carboxyl group contained in the polymer compound (A) is a group having a carboxylate group in the polymer compound (A), which is decomposed by exposure to form a carboxyl group, These two kinds of carboxyl groups react with an alkali developing solution to become a group containing a carboxylate group, and the dissolution rate of the polymer compound (A) in the exposed portion depends on the dissolution rate of a group containing no carboxyl group. Is a group used for increasing the difference in the dissolution rate between the unexposed portion and the polymer compound (A).

The carboxyl group-containing group is not particularly limited as long as it is a carboxyl group itself or a group containing a carboxyl group, but in the case of a group containing a carboxyl group, the molecular weight per carboxyl group is 500. It is preferably not more than about 100 to 300, from the viewpoint of increasing the dissolution rate in the alkaline developing solution after exposure.

Among the groups containing a carboxyl group,
A compound of the general formula (IX):

[0056]

[Chemical 40]

(In the formula, R ¹² is a hydrogen atom or a methyl group,
i is a group represented by 0 or 1 and j is 0, 1 or 2), and is preferably a compound represented by the general formula (X): from the viewpoint of excellent solubility in a developing solution.

[0058]

[Chemical 41]

(Wherein, k is 0 or 1), and a preferable one from the viewpoint of low absorption of exposure light and high transparency is represented by the general formula (XI):

[0060]

[Chemical 42]

(Wherein R ¹³ and R ¹⁴ are each independently represented by a hydrogen atom, a methyl group, a phenyl group, a benzyl group or CH ₂ COOH, and Z is O, N (C ₆ H ₅ ), or NH). From the viewpoint of excellent solubility in a group and a developing solution, a compound represented by the general formula (XII):

[0062]

[Chemical 43]

(Wherein i is as defined above) and the like.

Specific examples of the group containing a carboxyl group include, for example, —COOH, —CH ₂ COOH, —
_{CH (CH 3) COOH, -C} (CH 3) 2 COOH, -
_{(CH 2) 2 COOH, -} (CH 2) 3 COOH, -CH
_{(CH 3) CH 2 COOH,} - (CH 2) 4 COOH, -
_{(CH 2) 5 COOH, -} (CH 2) 6 COOH, -CH
_{(COOH) 2, -CH (CH} 2 COOH) 2, -C (C
_{H 3) (COOH) 2,} -C (CH 3) (CH 2 COOH)
_Two

[0065]

[Chemical 44]

And the like. The polymer compound (A) may include only one type of these groups, or may include two or more types thereof.

Among the groups containing a carboxyl group, especially

[0068]

[Chemical formula 45]

And the like are preferable from the viewpoint of high light transmittance at the exposure wavelength, and

[0070]

[Chemical formula 46]

Is preferable from the viewpoint of excellent dry etching resistance.

The group containing a carboxylic acid ester group represented by any one of formulas (I) to (IV) contained in the polymer compound (A) is an acid or a base generated from the compound (a) generating an acid upon exposure. When it is developed with an alkali developer, it facilitates dissolution of the polymer compound (A) in the exposed portion, while the polymer compound (A) in the unexposed portion is decomposed by It is a group that is used to allow the substance to remain substantially insoluble.

--COOR in the general formulas (I) to (IV)
² , -COOR ³ is a group corresponding to the carboxylic acid ester group in the invention 1, R ² and R ³ are t-butyl group or t-amyl group and t-butyl group, t-amyl group,
Isopropyl group, allyl group, 1-methylvinyl group, 1,
Since it is a 1-dimethylallyl group, a 2,5-dioxanyl group or a tetrahydrofuranyl group, it is decomposed by an acid or a base generated from the acid-generating compound (a), preferably by heating at room temperature to 150 ° C., It contributes to increase the dissolution rate of the polymer compound (A) in the exposed portion during development with an alkaline developer. On the other hand, the group before decomposition or the group remaining without decomposition acts so that the polymer compound (A) does not dissolve in the alkaline developer. As a result, the exposed portion of the polymer compound (A) is easily dissolved in the alkali developing solution, and the unexposed portion remains difficult to be dissolved, which acts as a positive resist.

The carboxylic acid ester group represented by -COOR ² or -COOR ³ is a t-butyl group, a t-amyl group, an isopropyl group, an allyl group, a 1-methylvinyl group,
1,1-dimethylallyl group, 2,5-dioxanyl group,
In the case of a tetrahydrofuranyl group, decomposition after exposure is likely to occur (for example, decomposition occurs under mild conditions at room temperature), and the carboxylic acid ester group can be selectively decomposed without side reactions. Is preferred.

The carboxylic acid ester group represented by -COOR ² or -COOR ³ is a polymer compound (A).
May be directly bonded to the main chain of, for example, as shown in the general formula (IV), or may be bonded via a bonding group as shown in the general formulas (I) to (III). From the viewpoint of high solubility in an alkali developing solution and high transmittance for exposure wavelength, it is preferable to bond directly to the main chain as shown in the general formula (IV), while uniform coating property is obtained. From the standpoint of excellent dry etching resistance, it is preferable to bond via a bonding group as shown in the general formulas (I) to (III).

Specific examples of preferable binding groups include, for example,

[0077]

[Chemical 47]

And the like.

Especially in the main chain of the polymer compound (A) in which the group containing a carboxyl group and the group containing a carboxylic acid ester group represented by the general formulas (I) to (IV) are bonded. Although not limited, from the viewpoint of good polymerizability and easy copolymerization, a compound of the general formula (XIII):

[0080]

[Chemical 48]

(Wherein R ¹⁵ is a hydrogen atom, a methyl group or a halogen atom such as Cl, X is a group containing a carboxyl group or a carboxylic acid ester group represented by any of the general formulas (I) to (IV)) It is preferably a main chain composed of (group).

The ratio of the group containing a carboxyl group to the group containing a carboxylic acid ester group represented by any one of the general formulas (I) to (IV) in the polymer compound (A) is, as described above, exposed to light. The unexposed portion is not substantially dissolved in the alkali developing solution, and the exposed portion has a high dissolution rate in the alkaline developing solution, which allows development with good resolution in a short time. The molar ratio is preferably in the range of 5/95 to 90/10. When the carboxyl group / carboxylic acid ester group is smaller than 5/95, it becomes difficult to sufficiently obtain the difference between the dissolution rate of the exposed portion in the alkali developing solution and the dissolution rate of the unexposed portion in the alkaline developing solution. On the other hand, when it is more than 90/10, the dissolution rate of the unexposed portion in the alkali developing becomes too high, and it becomes difficult to sufficiently obtain the difference from the dissolution rate of the exposed portion in the alkaline developing solution. The minimum ratio of carboxyl group / carboxylic ester group is 20 /
In the case of 80 or more, more preferably 30/70 or more, the difference in dissolution rate between the exposed portion and the unexposed portion in the alkali developing solution becomes large, and the resolution can be further improved at a large developing rate. Yes, and the maximum ratio is 80/2
In the case of 0 or less, more preferably 70/30 or less, the resolution can be further improved at a high developing speed as described above.

The polymer compound (A) has a weight average molecular weight (Mw) of 2000 to 500.
If it is less than 2000, it is difficult to obtain a uniform coating property and the dry etching resistance tends to be lowered. If it exceeds 50,000, the solubility of the exposed portion at the time of development is lowered. It is easy to do so, and this may lead to the generation of development residues. Further, it is more preferably 5,000 to 40,000 from the viewpoint of coating property (film forming property) and developability. The weight average molecular weight (Mw) / number average molecular weight (M
n) is 1.0 to 4.0, further 1.0 to
It is preferably 3.0.

Next, an example of the method for producing the polymer compound (A) will be described.

The polymer compound (A) includes, for example, a monomer having a group containing a carboxyl group (hereinafter, also referred to as a carboxyl group-containing monomer), and a compound represented by the general formula (I) or (I
What can be obtained by copolymerizing with a monomer having one of the groups containing a carboxylic acid ester group represented by I), (III) or (IV) (hereinafter, also referred to as a carboxylic acid ester group-containing monomer) You can

The carboxy group-containing monomer may be a general monomer such as (meth) acrylic acid, maleic acid, itaconic acid, and the like. Also, a compound having a polymerizable unsaturated group and a carboxyl group may be used. It may be a monomer obtained by reacting with a compound containing.

Examples of the compound having a polymerizable unsaturated group include acrylic acid chloride, methacrylic acid chloride, maleic acid dichloride, itaconic acid dichloride, chloromethylated styrene and derivatives thereof.

Examples of the compound containing a carboxyl group include p-hydroxyphenylacetic acid and p-hydroxyphenylacetic acid.
-Hydroxyphenylpropionic acid, p-hydroxyphenylisobutyric acid, DL-2-phenylglycine, N-phenylglycine, DL-phenylalanine, DL-mandelic acid, benzylic acid, DL-2-phenylbutyric acid, DL-
Examples thereof include malic acid and p-mercaptophenylacetic acid.

As a method for reacting the compound containing a polymerizable unsaturated group with the compound containing a carboxyl group, for example, in a 7 to 10% (wt%, hereinafter the same) NaOH aqueous solution, By reacting both at a low temperature of ~ 5 ° C for 3 to 5 hours and then neutralizing, and isolating and purifying the precipitate, or both in tetrahydrofuran in the presence of pyridine for about 2 to 4 hours. After the reaction, the solvent is distilled off, the residue is put into water, and the precipitate is isolated and purified.

Specific examples of the carboxyl group-containing monomer thus produced include, for example,

[0091]

[Chemical 49]

[0092]

[Chemical 50]

[0093]

[Chemical 51]

[0094]

[Chemical 52]

[0095]

[Chemical 53]

And the like.

On the other hand, the carboxylic acid ester group-containing monomer is generally a compound containing a polymerizable unsaturated group and a carboxyl group, and a compound represented by the general formula (I), (II) or (II
I), a method of reacting with an alcohol forming a carboxylic acid ester group in a group containing any of the groups containing a carboxylic acid ester group represented by (IV), or containing a polymerizable unsaturated group It is synthesized by a method of reacting a compound with a compound containing a carboxylic acid ester group and containing a polymerizable unsaturated group, and a compound containing a reactive group.

Examples of the compound containing a polymerizable unsaturated group and a carboxyl group include the carboxyl group-containing monomer.

Examples of the alcohol forming the carboxylic acid ester group include t-butyl alcohol, t-amyl alcohol, isopropyl alcohol,
Examples thereof include t-hexyl alcohol, allyl alcohol, and tetrahydrofuranyl alcohol.

As a method for reacting the compound containing a polymerizable unsaturated group and a carboxyl group with the alcohol forming the carboxylic acid ester group, for example, the polymerizable unsaturated group and the carboxyl group are combined with each other. The compound contained is dissolved in thionyl chloride, and dimethylformamide is used as an activator. After reacting for 12 hours, thionyl chloride is distilled off to obtain an acid chloride. The acid chloride is dissolved in, for example, tetrahydrofuran, and this is reacted with the alcohol forming the carboxylic acid ester group for 12 hours at room temperature using pyridine, the solvent is distilled off, and the residue is recrystallized from ethanol. And the like.

Examples of the compound containing a polymerizable unsaturated group include acid chlorides mentioned as the raw material of the carboxyl group-containing monomer and chloride derivatives such as p-vinylbenzyl chloride.

Examples of the compound containing a carboxylic acid ester group and a group capable of reacting with a compound containing a polymerizable unsaturated group include, for example, malonic acid di-t.
-Butyl, t-butyl tricarballylate, etc. may be mentioned. These can be reacted with chloride derivatives such as, for example, p-vinylbenzyl chloride.

As a method of reacting the compound having a polymerizable unsaturated group with the compound having a group having a carboxylic acid ester group, metal sodium is used in a solvent such as isopropyl alcohol, After reacting both at room temperature for 1 day, the solvent was distilled off,
The residue can be obtained by a method such as recrystallization with ether.

Specific examples of the carboxylic acid ester group-containing monomer thus produced include, for example,

[0105]

[Chemical 54]

[0106]

[Chemical 55]

[0107]

[Chemical 56]

The polymer compound (A) is used in a solvent such as dioxane, tetrahydrofuran or dimethylformamide in such a manner that the above-produced carboxyl group-containing monomer and carboxylic acid ester group-containing monomer are brought to a predetermined molar ratio. And a polymerization initiator selected from azobisisobutyronitrile, benzoyl peroxide, etc. is dissolved in dioxane, tetrahydrofuran, dimethylformamide, etc. and polymerized at 40-100 ° C., preferably 50-80 ° C. Manufactured by.

Specific examples of the above-mentioned polymer compound (A) include those shown below.

[0110]

[Chemical 57]

[0111]

[Chemical 58]

[0112]

[Chemical 59]

[0113]

[Chemical 60]

[0114]

[Chemical formula 61]

[0115]

[Chemical formula 62]

[0116]

[Chemical formula 63]

[0117]

[Chemical 64]

[0118]

[Chemical 65]

[0119]

[Chemical formula 66]

[0120]

[Chemical formula 67]

Among the above-mentioned polymer compounds (A), compounds A-1, A-5, A-21, A-22, A-23, A
-24 is preferably used in terms of solubility in a developing solution, resistance to dry etching, high transmittance with respect to exposure wavelength, and the like.

The photosensitive resin composition of Invention 1 is prepared from the above-described polymer compound (A) and acid-generating compound (a).

The acid-generating compound (a) is a compound used in a photosensitive resin composition based on the so-called chemical amplification type mechanism, and is decomposed by irradiation with light,
A compound that generates an acid or base. The acid or base generated from this compound acts as a catalyst when decomposing the carboxylic acid ester group in the polymer compound (A), so a small amount of light should be irradiated to generate a catalytic amount of the acid or base. The photosensitive resin composition coating film can be exposed to light and developed.

The acid-generating compound (a) as described above can be used without particular limitation as long as it is a compound which decomposes upon irradiation with light to generate an acid or a base as described above.

Specific examples of compounds which generate an acid among such compounds include, for example, triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroarsineate, triphenylsulfonium hexafluoro. Phosphate, triphenylsulfonium trifluoromethanesulfonate, 4-thiophenoxydiphenylsulfonium tetrafluoroborate, 4-thiophenoxydiphenylsulfonium hexafluoroantimonate, 4-thiophenoxydiphenylsulfonium hexafluoroarsineate, 4-thiophenoxydiphenylsulfonium Hexafluorophosphate, 4-thiophenoxydiphenylsulfonium trifluorometa Suruhoneito, 4-t-butylphenyl diphenyl sulfonium tetrafluoroborate,
4-t-butylphenyldiphenylsulfonium hexafluoroantimonate, 4-t-butylphenyldiphenylsulfonium hexafluoroarsineate, 4-
t-butylphenyldiphenylsulfonium hexafluorophosphate, 4-t-butylphenyldiphenylsulfonium trifluoromethanesulfonate, tris (4-methylphenyl) sulfonium tetrafluoroborate, tris (4-methylphenyl) sulfonium hexafluoroantimonate, Tris (4-methylphenyl) sulfonium hexafluoroarsineate, tris (4-methylphenyl) sulfonium hexafluorophosphate, tris (4-methylphenyl) sulfonium trifluoromethanesulfonate, tris (4-methoxyphenyl) sulfonium tetrafluoroborate Rate, tris (4-methoxyphenyl) sulfonium hexafluoroantimonate, tris (4-methoxyphenyl) sulfonium Xafluoroarsinate, tris (4-methoxyphenyl) sulfonium hexafluorophosphate, tris (4-methoxyphenyl) sulfonium trifluoromethanesulfonate, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoroantimonate, diphenyliodonium Hexafluoroarsineate, diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, 3,3 '
-Dinitridiphenyliodonium tetrafluoroborate, 3,3'-dinitrodiphenyliodonium hexafluoroantimonate, 3,3'-dinitrodiphenyliodonium hexafluoroarsineate, 3,
3'-dinitrodiphenyliodonium hexafluorophosphate, 3,3'-dinitrodiphenyliodonium trifluoromethanesulfonate, 4,4'-dimethyldiphenyliodonium tetrafluoroborate,
4.4'-Dimethyldiphenyliodonium hexafluoroantimonate, 4,4-dimethylphenyliodonium hexafluoroarsineate, 4,4'-dimethyldiphenyliodonium hexafluorophosphate, 4,4'-dimethylphenyliodonium Trifluoromethanesulfonate, 4,4'-di-t-butylphenyl iodonium tetrafluoroborate, 4,4 '
-Di-t-butyldiphenyliodonium hexafluoroantimonate, 4,4'-di-t-butyldiphenyliodonium hexafluoroarsineate, 4,4 '
-Di-t-butyldiphenyliodonium hexafluorophosphate, onium salts such as 4,4'-di-t-butyldiphenyliodonium trifluoromethanesulfonate; 2,4,6-tris (trichloromethyl) triazine, 2 -Allyl-4,6-bis (trichloromethyl) triazine, α, α, α-tribromomethyl-phenyl sulfone, α, α, α, α ′, α ′, α′-hexachloroxylylene, 2,2- Bis (3,5-dibromo-
4-hydroxyphenyl) -1,1,1,3,3,3-
Hexafluoropropane, 1,1,1-tris (3,5
A halogen-containing compound such as -dibromo-4-hydroxyphenyl) ethane; 2-nitrobenzyl tosylate,
2,6-dinitrobenzyl tosylate, 2,4-dinitrobenzyl tosylate, methylsulfonic acid 2-nitrobenzyl ester, acetic acid 2-nitrobenzyl ester, p
-Nitrobenzyl-9,10-dimethoxyanthracene-2-sulfonate, 1,2,3-tris (methanesulfonyloxy) benzene, 1,2,3-tris (trifluoromethanesulfonyloxy) benzene, 1,2,3
-Tris (ethanesulfonyloxy) benzene, 1,
2,3-tris (propanesulfonyloxy) benzene, 1,2,3-tris (phenylsulfonyloxy)
Sulfonic acid esters such as benzene and 1,2,3-tris (methylphenylsulfonyloxy) benzene; bis (t-butylphenylsulfonyl) diazomethane, bis (4-methylphenylsulfonyl) diazomethane, bis (t-butylphenylsulfonyl) Methane, bis (4-
Methylphenylsulfonyl) methane, 2,2-bis (t
-Butylphenylsulfonyl) propane, 2,2-bis (4-methylphenylsulfonyl) propane, 1-t-
Butylphenyl-1-ethoxycarbonyldiazomethane, 1-t-butylphenyl-1-propyloxycarbonyldiazomethane, 1-p-methylphenyl-1-ethoxycarbonyldiazomethane, 1-p-methylphenyl-1-propyloxycarbonyldiazomethane, 1,
Sulfone compounds such as 2-bis (p-methylphenyldiazomethylcarbonyloxy) ethylene and 1,3-bis (p-methylphenyldiazomethylcarbonyloxy) propylene; hydroxyimides such as hydroxysuccinimide and hydroxyphthalimide Examples thereof include sulfonic acid ester and derivatives thereof. These may be used alone or in combination of two or more.

Among the above-mentioned acid-generating compounds, diphenyliodonium triflate, triphenylsulfonium triflate, triphenylsulfonium hexafluoroantimonate and triphenylsulfonium tetrafluoroborate have a high acid generation rate by light irradiation. Therefore, it is preferably used.

Further, specific examples of the compound generating a base include, for example, triphenylmethanol and tris-p-
Examples thereof include methoxyphenylmethanol, trischlorophenylmethanol and derivatives thereof, o-nitrobenzyl carbanate and the like. These may be used alone or in combination of two or more.

Among the compounds which generate a base, triphenylmethanol and tris-p-methoxyphenylmethanol are preferably used from the viewpoint of high efficiency of generation of a base upon irradiation with light.

The photosensitive resin composition of Invention 1 is prepared from the above-described polymer compound (A) and acid-generating compound (a).

The compounding ratio of the polymer compound (A) and the acid-generating compound (a) is 70 for the polymer compound (A).
The range of ˜99% and the acid generating compound is preferably 1 to 30%. When the blending ratio of the polymer compound (A) is more than 99%, the amount of acid or base acting as a catalyst for accelerating the decomposition reaction of the carboxylic acid ester group is reduced, and thus patterning tends to be difficult. On the other hand, 70%
If the amount is less than the above range, the photosensitive resin composition tends to have insufficient compatibility, and it is difficult to obtain a uniform composition, and a defective pattern to be formed easily occurs.

The minimum compounding ratio of the polymer compound (A) is 70.
% Or more, and more preferably 75% or more is more preferable from the viewpoint that dry etching resistance can be maintained and a uniform film can be formed, and the maximum mixing ratio is 99% or less, further 98% or less. Is preferable from the viewpoint that the amount of acid or base generated by light irradiation is suitably secured and good patterning property can be obtained.

In the photosensitive resin composition of Invention 1, a solvent is usually further used for adjusting the viscosity of the composition, coating property and the like.

The solvent used is not particularly limited as long as it can rapidly dissolve both components and does not react with them, but a solvent having a boiling point of 100 to 220 ° C. is preferable. When the boiling point is lower than 100 ° C, unevenness is likely to occur when applied, and when the boiling point is higher than 220 ° C, drying is not easy. Specific examples of the above-mentioned solvent include, for example, methyl cellosolve, ethyl cellosolve, methyl methoxypropionate, ethyl ethoxy propionate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl acetate, ethyl pyruvate, 2 -Heptanone, dimethyl glyme, diethyl glyme, cyclopentanone, cyclohexanone, γ-butyrolactone, isoamyl acetate, chlorobenzene and the like.

The amount of the solvent used is 50 to 50% in the composition.
95% is preferable from the viewpoint that a uniform film can be formed.

In the photosensitive resin composition of the invention 1, as an optional component, an adhesion improver for further improving the adhesion between the substrate and the photosensitive resin composition, for example, aminosilazane,
Aminoalkoxysilazine, alkylalkoxysilazane and the like are blended in an amount of 0.001 to 0.05%, and other compounds suitable for the purpose can be added if necessary.

The method for producing the photosensitive resin composition of the present invention is not particularly limited as long as both components are uniformly dissolved and mixed. For example, the polymer compound (A) and the acid generating compound (a) are dissolved in a solvent. A method such as letting is used.

The thus-produced photosensitive resin composition generally has a solid content concentration of about 50 to 5% and a viscosity such that it easily flows.

The photosensitive resin composition of the present invention is applied onto a substrate such as a silicon wafer, prebaked, and exposed to UV.
After irradiating radiation such as light, deep UV light, soft X-ray, and electron beam, heating at about 50 to 150 ° C. for 40 seconds to 60
A pattern can be formed by performing the process for 0 seconds.

As a developing solution for the photosensitive resin composition, an alkaline aqueous solution or an organic solvent can be used.
A positive type pattern can be formed by using an alkaline aqueous solution, and a negative type pattern can be formed by using an organic solvent. Examples of the alkaline aqueous solution include ammonia, triethylamine, dimethylaminomethanol,
An aqueous solution of tetramethylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, choline or the like can be used. Further, as the organic solvent, dichloromethane, chloroform, trichloroethylene,
Ethyl acetate, isoamyl acetate, methanol, isopropanol or a mixed solvent thereof can be used.

Invention 2 will be described below.

The photosensitive resin composition of Invention 2 further contains a polyvalent carboxylic acid ester compound (b) in addition to the above-mentioned polymer compound (A) and acid-generating compound (a).

The polycarboxylic acid ester compound (b) is
Like the polymer compound (A), the exposed portion is decomposed by the acid or base generated from the acid-generating compound (a) and converted into a carboxyl group to be easily soluble in an alkali developing solution and dissolved, The non-existing portion is a compound which is not substantially dissolved in the alkaline developer, and since such a compound is used together with the polymer compound (A), the dissolution rate of the exposed portion is higher than that of the polymer compound (A) only. Can be even larger. The reason is that in the case of the polymer compound (A), a group containing a large number of carboxylic acid ester groups is contained in the molecule, and when exposed to light, only a part of the carboxylic acid ester group in the molecule is exposed. In some cases, it does not decompose and is difficult to dissolve in an alkaline developer, and it may be difficult to develop, but in the case of the polyvalent carboxylic acid ester compound (b), it is more likely than the polymer compound (A). And small molecular weight (molecular weight 250-100
Therefore, under the condition that the carboxylic acid ester group is decomposed, most of the carboxylic acid ester group is decomposed and converted into a carboxyl group, which easily dissolves in an alkali developing solution, and has a molecular weight of It is considered that the small size of the polymer makes it less likely to cause entanglement of molecular chains, and that it is easily dissolved.

The number of groups containing a carboxylic acid ester group contained in the polyvalent carboxylic acid ester compound (b) is preferably 2 to 6 from the viewpoint of greatly changing the solubility in a developing solution. It is more preferable that the number is 4 or less.

The molecular weight per one carboxylic acid ester group is 100 to 400, preferably 100 to 200, from the viewpoint of greatly changing the solubility.

Specific examples of the polyvalent carboxylic acid ester compound (b) include, for example, the general formula (V):

[0146]

[Chemical 68]

(In the formula, R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom such as —CH ₃ , —C ₂ H ₅ or —C ₃ H).
_7, -C _4, such as H ₉ alkyl group having 1 to 4 carbon atoms, Cl, B
halogen atom such as r, general formula (VI):

[0148]

[Chemical 69]

(In the formula, R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkyl group having 2 to 6 carbon atoms. An alkynyl group, an oxyalkyl group having 1 to 6 carbon atoms or a halogen atom, 1 is a group containing a carboxylic acid ester group represented by 0) to 5 or a general formula (VII):

[0150]

[Chemical 70]

(Wherein R ¹⁰ is the same as described above, R ¹¹ is an alkylene group having 3 to 6 carbon atoms, a divalent hydrocarbon group having a double bond, or a general formula (VIII): — (CH ₂ ) _{m -O- (CH 2) n - (} VIII) ( wherein, m, n are each independently 1 or 2) groups represented by, 1 have the same meanings as defined above), provided that, R ^5, R ⁶ and R ⁷ At least one of which is represented by general formula (VI) or (VII)
A group containing a carboxylic acid ester group represented by the following formula 2) in the molecule
Examples thereof include compounds that are decomposed by an acid or a base containing one or more of them.

In the general formula (V), among R ^{5 to} R ⁷ , there are 2 to 3 groups containing a carboxylic acid ester group represented by the general formula (VI) or the general formula (VII). Is preferable from the viewpoint of greatly changing the solubility in a developing solution.

Specific examples of the alkyl group having 1 to 6 carbon atoms represented by R ⁸ , R ⁹ or R ¹⁰ in the general formula (VI) are as follows:
_{CH 3, -C 2 H 5,} -C 3 H 7, -C 4 H 9, -C 5 H 11 -C
Specific examples of the alkenyl group having 2 to 6 carbon atoms such as ₆ H ₁₃ and a cyclohexyl group include —CH═CH ₂ and —CH═C.
_{H-CH 3, -C (CH} 3) = , etc. CH _2, carbon atoms 1-6
As specific examples of oxyalkyl groups, -OCH _3, -
CH ₂ OCH _{3 and the} like, and specific examples of the halogen atom include Cl, Br and the like.

Specific examples of the alkylene group having 3 to 6 carbon atoms represented by R ¹¹ in the general formula (VII) include-(C
_{H 2) 3 -, - (} CH 2) 4 -, - (CH 2) 2 -O-CH 2
- etc. Specific examples of the divalent hydrocarbon group having a double _{bond, -CH = CH- (CH 2)} 2 -, - CH = CH-
A group represented by the general formula (VIII) such as O—CH ₂ — is
_{CH 2 -O- (CH 2) 2} , -CH 2 -O-CH 2 -, -
_{(CH 2) 2 -O- (CH} 2) -, - (CH 2) 2 -O-
(CH ₂ ) ₂ − and the like.

Specific examples of the group containing a carboxylic acid ester group represented by the general formula (VI) include, for example, isopropyl acetate group, t-butyl acetate group, t-amyl acetate group, vinyl acetate group and isopropenyl acetate group. Group, isopropyl propionate group, t-butyl propionate group, t-amyl propionate group, vinyl propionate group, isopropenyl propionate group, isopropyl butanoate group, t-butyl butanoate group, t-amyl butanoate group , Butanoic acid vinyl group, butanoic acid isopropenyl group and the like.
Of these, a t-butyl acetate group, a t-amyl acetate group, an isopropenyl acetate group, a t-butyl propionate group, a t-amyl propionate group, and an isopropenyl propionate group are preferable from the viewpoint of decomposability.

Specific examples of the group containing a carboxylic acid ester group represented by the above general formula (VII) include, for example, tetrahydropyranyl acetate group, tetrahydrofuranyl acetate group, 2,5-dioxanyl acetate group and propione group. Acid tetrahydropyranyl group, propionic acid 2,5-dioxanyl group, butanoic acid tetrahydropyranyl group, butanoic acid 2,5-dioxanyl group and the like. Among these, a tetrahydropyranyl acetate group and a tetrahydrofuranyl acetate group are preferable from the viewpoint of decomposability.

Specific examples of the compound containing two or more groups containing a carboxylic acid ester group represented by the general formula (V) in the molecule and other polyvalent carboxylic acid ester compounds include, for example, di-t. -Butyl terephthalate, di-t-amyl terephthalate,

[0158]

[Chemical 71]

And the like. Of these, b-2 and b-3 are preferable from the viewpoint of degradability.

The compound containing two or more groups containing a carboxylic acid ester group represented by the general formula (V) in the molecule is a polyvalent carboxylic acid derivative and general formulas (VI) and (VI
It is synthesized by a method of reacting the carboxylic acid ester group-containing alcohol represented by I) with an alcohol forming the carboxylic acid ester group.

Examples of the derivative of the polyvalent carboxylic acid include acid chloride and acid bromide of the polyvalent carboxylic acid, and examples of the alcohol forming the carboxylic acid ester group include t-butyl alcohol and t-amino alcohol. Can be given.

Specific examples of the polycarboxylic acid chloride include terephthalic acid chloride, isophthalic acid chloride,
Examples thereof include biphenyl dicarboxylic acid dichloride, diphenyl ether dicarboxylic acid dichloride, diphenyl sulfone dicarboxylic acid dichloride, phenylenediacetic acid chloride, cyclohexyl dicarboxylic acid chloride, adamantane dicarboxylic acid chloride and trimesic acid trichloride.

In the second aspect of the invention, as the carboxyl group in the polymer compound (A), one of the general formulas (IX), (X) and (X
It is preferable to use the polymer compound (A) having a group represented by I) or (XII) because the difference in dissolution rate between the exposed area and the unexposed area is further increased.

The compounding ratio of the polymer compound (A), the acid generating compound (a) and the polyvalent carboxylic acid ester compound (b) in the photosensitive resin composition of the invention 2 is such that the polymer compound (A) and the polymer compound (A) are mixed with each other. To the compound containing the latter (b) 0.05 to 30% so that the total amount of the compounding ratio with the carboxylic acid ester compound (b) is 99 to 70%, the compound (a) such as an acid is further added. It is preferable to add -30% to 100%.

When the total amount of the polymer compound (A) and the polycarboxylic acid ester compound (b) is more than 99%, an acid or base serving as a catalyst for promoting the decomposition reaction of the carboxylic acid ester group. As a result, the patterning becomes difficult to be performed because the amount of occurrence of is reduced. On the other hand, when the total amount is less than 70%, a photosensitive resin composition having insufficient compatibility tends to be formed, and it is difficult to obtain a uniform composition, and the formed pattern is likely to be defective.

Further, when the blending ratio of the polyvalent carboxylic acid ester compound (b) is 0.05% or less, the combined effect of the polyvalent carboxylic acid ester compound (b) is unlikely to occur, resulting in a better pattern. If it exceeds 30%, it is difficult to form a film, and when it exceeds 30%, a residue is generated during development and the compatibility of the three components becomes difficult, which is not preferable.
However, it is preferable that the polymer compound (A) is blended in an amount of 70 to 99% from the viewpoint of not lowering the dry etching resistance.

The minimum total amount of the compounding ratios of the polymer compound (A) and the polycarboxylic acid ester compound (b) is 70.
% Or more, more preferably 75% or more is more preferable from the viewpoint of compatibility of the composition, and the maximum amount is preferably 99% or less, and further preferably 98% or less is suitable for the amount of acid or base generated by light irradiation. It is preferable because it can be ensured and good patterning property can be obtained.

The minimum mixing ratio of the polycarboxylic acid ester compound (b) is 1% or more, and further 2% or more is the solubility in the developing solution (the difference in the dissolution rate between the unexposed area and the exposed area is different). It is preferable that the maximum blending ratio is 30% or less, further preferably 25% or less from the viewpoint of solubility in a developing solution. However, it is preferable that the minimum compounding ratio of the polymer compound (A) is 70% or more, further 75% or more, because it is possible to form a uniform film, and the maximum compounding ratio is 99% or less. Is preferably 98% or less from the viewpoint of suitably securing the amount of acid or base generated by light irradiation and obtaining good patterning property.

The description of the blending amount and the preferable blending amount of the acid-generating compound (a) is the same as in the case of the invention 1, and thus the duplicated description will be omitted.

The method for producing the photosensitive resin composition of Invention 2 is not particularly limited as long as the above-mentioned three components are uniformly mixed. For example, polymer compound (A), polycarboxylic acid ester compound (b), acid and the like. It is produced by a method such as dissolving the generating compound (a) in a solvent.

The photosensitive resin composition thus prepared generally has a solid content concentration of about 5 to 50% and a viscosity such that it easily flows.

The solvent used in the photosensitive resin composition and its amount, the optional components such as the adhesion improver, the usage mode of the photosensitive resin composition, and the developing solution are the same as those described in Invention 1. Same content.

Invention 3 will be described below.

The photosensitive resin composition of Invention 3 achieves the same purpose as the polyvalent carboxylic acid ester compound (b) in place of the polyvalent carboxylic acid ester compound (b) in the photosensitive resin composition of Invention 2. Therefore, the polyhydric phenol carbonate compound (c) is used.

Specific examples of the polyhydric phenol carbonic acid ester compound (c) include, for example, a dihydric to hexavalent polyhydric phenol and a carbonic acid esterifying agent such as di-t-butyl carbonate or di-t-amyl carbonate. A compound produced by reacting

Specific examples of the polyphenols include hydroquinone, catechol, phloroglucinol, bisphenol A, bisphenol S, bisphenol F,
Trisphenol, diphenyl ether diphenol,
Examples thereof include diphenyl sulfone diphenol, hexahydroxydiphenyl propane, tetrahydroxybenzophenone and the like. Of these, bisphenol A,
Trisphenol is preferable from the viewpoint of compatibility.

In the invention 3, the carboxyl group in the polymer compound (A) is represented by the general formulas (IX), (X), (X
It is preferable to use the polymer compound (A) having a group represented by I) or (XII) because the difference in dissolution rate between the exposed area and the unexposed area is further increased.

The compounding ratio of the polymer compound (A), the acid-generating compound (a) and the polyhydric phenol carbonate compound (c) in the photosensitive resin composition of Invention 3 is such that the polymer compound (A) and the polymer compound (A) are mixed. To the compound containing 0.05 to 30% of the latter (c) so that the total amount of the compounding ratio with the polyhydric phenol carbonate compound (c) is 99 to 70%, the compound (a) such as an acid is further added. ~ 30% blended 100%
It is preferable that

When the total amount of the polymer compound (A) and the polyhydric phenol carbonate compound (c) is more than 99%, an acid or base serving as a catalyst for promoting the decomposition reaction of the carboxylic acid ester group. As a result, the patterning becomes difficult to be performed because the amount of occurrence of is reduced. On the other hand, when the total amount is less than 70%, a photosensitive resin composition having insufficient compatibility tends to be formed, and it is difficult to obtain a uniform composition, and the formed pattern is likely to be defective.

When the blending ratio of the polyhydric phenol carbonate compound (c) is 0.05% or less, the combined effect of the polyhydric phenol carbonate compound (c) is unlikely to occur and a more excellent pattern is formed. If it exceeds 30%, it is difficult to form a film, and when it exceeds 30%, a residue is generated during development and the compatibility of the three components becomes difficult, which is not preferable.
However, it is preferable that the polymer compound (A) is blended in an amount of 70 to 99% from the viewpoint of not lowering the dry etching resistance.

Compatibility of the composition is that the minimum total amount of the compounding ratio of the polymer compound (A) and the polyhydric phenol carbonate compound (c) is 70% or more, further 75% or more. More preferably, the maximum amount is 99% or less, further preferably 98% or less from the viewpoint that the amount of acid or base generated by light irradiation can be suitably secured and good patterning property can be obtained.

Polyhydric phenol carbonate compound (c)
The minimum blending ratio is 1% or more, further 2% or more, and the maximum blending ratio is 30% or less, further 25%.
The following is preferable from the viewpoint of solubility in a developing solution. However, the minimum compounding ratio of the polymer compound (A) is 70
% Or more, more preferably 75% or more is preferable from the viewpoint that a uniform film can be formed, and the maximum compounding ratio is 99% or less, and further 98% or less is the acid by light irradiation or It is preferable in that the amount of generated base can be suitably secured and good patterning property can be obtained.

The description of the compounding amount and the preferable compounding amount of the acid-generating compound (a) is the same as in the case of the invention 1, so that the duplicated description will be omitted.

The method for preparing the photosensitive resin composition of Invention 3 is not particularly limited, and may be prepared by the same method as Invention 2.

The photosensitive resin composition thus prepared generally has a solid content concentration of about 5 to 50% and a viscosity such that it easily flows.

The solvent used in the photosensitive resin composition and the amount thereof, the optional components such as the adhesion improver, the usage of the photosensitive resin composition, and the developing solution are the same as those described in Invention 1. Same content.

The invention 4 will be described below.

The photosensitive resin composition of the invention 4 further contains an alkali-soluble polymer compound (B) in addition to the polymer compound (A) and the acid-generating compound (a).

In Invention 4, since the alkali-soluble polymer compound (B) is used in addition to the polymer compound (A), the alkali development of the polymer compound (A) made soluble in the alkali developing solution by exposure is carried out. The dissolution rate in the liquid is further increased.

As the alkali-soluble polymer compound, a polymer compound which is easily dissolved in an alkali developing solution, such as a polymer compound having a carboxyl group-containing group in its side chain, is used. growing.

Description of the group containing a carboxyl group (contents of the group containing a carboxyl group, specific examples,
Preferred examples, specific examples of carboxyl group-containing monomers, production methods, etc.) are the same as in the case of the invention 1, and thus duplicated description will be omitted.

The characteristic of the alkali-soluble polymer compound is that the weight average molecular weight is 5,000 to 10,000.
It is preferably 0, more preferably 5,000 to 50,000, from the viewpoint of solubility in a developing solution and coating property.

The polymer compound having a carboxyl group-containing group in the side chain can be obtained by polymerizing the carboxyl group-containing monomer under the same polymerization conditions as those for obtaining the polymer compound (A).

Specific examples of the obtained polymer compound (B) include those shown below.

[0195]

[Chemical 72]

[0196]

[Chemical formula 73]

[0197]

[Chemical 74]

[0198]

[Chemical 75]

[0199]

[Chemical 76]

[0200]

[Chemical 77]

[0201]

[Chemical 78]

[0202]

[Chemical 79]

[0203]

[Chemical 80]

Among them, it is preferable to use the polymer compound (B) having a structure relatively similar to that of the used polymer compound (A) because the compatibility between the polymer compounds is good and the photosensitive resin composition It is preferable in that the obtained film is uniformly dissolved.

In addition to the above, examples of the alkali-soluble polymer compound include phenol / formaldehyde resins such as phenol novolac resin, cresol novolac resin and naphthol novolac resin, polyvinylphenol resin or vinylphenol and acrylic or styrene monomer. The copolymer, acrylic resin, styrene resin and the like are used, and among these, polyvinylphenol resin, acrylic resin, styrene resin and the like are preferable from the viewpoint of compatibility of the composition.

In the invention 4, the carboxyl group in the polymer compound (A) is represented by the general formulas (IX), (X) and (X
It is preferable to use the polymer compound (A) having a group represented by I) or (XII) because the difference in dissolution rate between the exposed area and the unexposed area is further increased.

The compounding ratio of the polymer compound (A), the acid-generating compound (a) and the alkali-soluble polymer compound (B) in the photosensitive resin composition of the invention 4 is from 98 to 80 for the polymer compound (A). 70%, acid generating compound (a) is 1
~ 29% and 1% of alkali-soluble polymer (B)
It is preferably ˜29%.

The minimum compounding amount of the polymer compound (A) is 70%.
From the viewpoint of compatibility of the composition, 75% or more is preferable, and the maximum compounding amount is 98% or less, and further 97%.
% Or less is preferable from the viewpoint that the amount of acid or base generated by light irradiation is suitably secured and good patterning property can be obtained.

The minimum compounding amount of the acid-generating compound (a) is 1%.
As described above, more preferably 2% or more from the viewpoint that the amount of acid or base generated by light irradiation is suitably secured and good patterning property is obtained, and the maximum compounding amount is 29% or less, further 25% or less. It is preferable from the viewpoint of compatibility of the composition.

It is preferable that the minimum amount of the alkali-soluble polymer compound (B) is 1% or more, further preferably 2% or more from the viewpoint of solubility in the developing solution, and the maximum amount is 29%.
Hereafter, it is preferably 25% or less from the viewpoint of controlling the solubility in a developing solution.

The method for producing the photosensitive resin composition of Invention 4 is not particularly limited as long as the above-mentioned three components are uniformly dissolved and mixed, and examples thereof include polymer compound (A), alkali-soluble polymer compound (B) and acid. It is produced by a method such as dissolving the isogenic compound (a) in a solvent.

The solvent used in the photosensitive resin composition and the amount thereof, the optional components such as the adhesion improver, the usage mode of the photosensitive resin composition and the developing solution are the same as those described in Invention 1. Same content.

Hereinafter, the photosensitive resin composition of the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

[Production Examples 1 to 19] (Monomer of alkali-soluble polymer compound (B) (monomer containing carboxyl group) and polymer compound (B))
Synthesis 1) In a solution prepared by dissolving the raw material compound Y described in Tables 1 and 2 in the amounts described in Tables 1 and 2 in 1 liter of an aqueous NaOH solution having the concentration described in Tables 1 and 2, Table 1,
The starting compound X described in 2 was added dropwise while keeping the temperature of the solution at 0 to 5 ° C. After that, the reaction was carried out at the same temperature for the time shown in Tables 1 and 2. After completion of the reaction, the mixture was neutralized with hydrochloric acid, and the precipitate was filtered and washed with water. The obtained reaction product was recrystallized from toluene, and the synthetic monomer (M-1 to 1) described in Tables 1 and 2 was used.
M-19) was obtained.

The yields of the obtained monomers are shown in Tables 1 and 2.

Next, 10 g of the monomers shown in Tables 3 and 4
And azobisisobutyronitrile 0.1 as a polymerization initiator
5 g and 40 g of dioxane were charged into a reaction vessel in which nitrogen gas was replaced, dissolved, and then polymerized at 60 ° C. for 12 hours.

After completion of the polymerization, the reaction solution was dropped into toluene to precipitate a polymer, which was filtered and then dried in a vacuum drier to obtain the polymer compounds (B-1 to B-1) shown in Tables 3 and 4.
9) was obtained.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained polymer compound were measured by the following methods. The results are shown in Tables 3 and 4.

(Weight average molecular weight and number average molecular weight) The weight average molecular weight and the number average molecular weight were determined by GPC measurement using HLC8020 manufactured by Tosoh Corporation. Solvent: Tetrahydrofuran, Flow rate: 0.8m
1 / min Column oven temperature: 40 ° C. Detection: RI and UV (254 nm) Each abbreviation in Tables 1 to 4 means the following components. _{X-1: CH 2 = C} (CH 3) COCl methacrylic chloride _{X-2: CH 2 = C} (Cl) COCl α- chloro acrylic acid chloride _X-3: CH 2 = CHCOCl acrylic acid chloride X-4: HOOCHC = CHCOCl fumaric acid monochloride Y-1: p-HO- C 6 H 4 -CH 2 COOH p- hydroxyphenyl acetic Y-2: p-HO- C 6 H 4 -CH 2 CH 2 COOH 3-
(P- hydroxyphenyl) propionic acid Y-3: p-HO- C 6 H 4 -C (CH 3) 2 COOH p
- hydroxyphenyl isobutyric acid Y-4: p-HO- C 6 H 4 -C (CH 3) 2 CH 2 COO
H 3- (p-hydroxyphenyl) -2,2-dimethylpropionic acid

[0220]

[Chemical 81]

Y-6: NH ₂ —CH (COOH) CH ₂ C
₆ H ₅ DL-phenylalanine _{Y-7: C 6 H 5} -NH-CH 2 COOH N- phenylglycine M-1 to M-19 and B-1 to B-19 are as defined above.

[0222]

[Table 1]

[0223]

[Table 2]

[0224]

[Table 3]

[0225]

[Table 4]

[Production Examples 20 to 29] (Monomer of alkali-soluble polymer compound (B) (carboxyl group-containing monomer) and polymer compound (B))
Synthesis 2) The starting compound Y shown in Table 5 in an amount shown in Table 5 and 80 g of pyridine were dissolved in 500 cc of tetrahydrofuran. After cooling this solution in an ice bath, the starting material compound X shown in Table 5 in the amount shown in Table 5 was added at a temperature of the solution of 0 to 5
The solution was added dropwise while keeping it at 0 ° C, and then reacted for 4 hours. The solvent was distilled off with a rotary evaporator,
The residue was poured into 2 liters of water to obtain a purified precipitate. This was washed several times with water, dried under reduced pressure, and then recrystallized from ethanol to obtain the synthetic monomers (M-20 to M-29) shown in Table 5.

Next, 10 g of the monomers shown in Table 6, 0.16 g of azobisisobutyronitrile as a polymerization initiator, and 40 g of dioxane were charged into a reaction vessel in which nitrogen gas was replaced and dissolved, and then at 80 ° C. for 6 hours. Polymerized. After completion of the polymerization, the reaction solution was dropped into hexane to precipitate a polymer, which was filtered and then dried in a vacuum drier to obtain a polymer compound (B-20 to B-29) shown in Table 6.

The yield of the obtained monomer is shown in Table 5, and the molecular weight of the obtained polymer compound is shown in Table 6.

The abbreviations in Tables 5 and 6 mean the following components. _{X-5: p-CH 2} = CH-C 6 H 4 -CH 2 Cl P- vinylbenzyl chloride _{Y-8: C 6 H 5} -CH (OH) COOH DL- mandelic acid Y-9: malonic anhydride

[0230]

[Chemical formula 82]

X-1 to X-3, M-20 to M-29 and B-20 to B-29 are the same as above.

[0232]

[Table 5]

[0233]

[Table 6]

[Production Examples 30 to 44] (Synthesis of Monomer of Polymer Compound Having Carboxylic Acid Ester Group in Side Chain (1)) The amount of Monomer M shown in Table 7 shown in Table 7 was dissolved in 100 ml of thionyl chloride. Then, 0.5 ml of dimethylformamide was added and the reaction was carried out for 12 hours. After the reaction, thionyl chloride was distilled off, and the residue was dissolved in 200 ml of tetrahydrofuran. After reacting this with the raw material compound Y shown in Table 7 for 12 hours at room temperature using pyridine, the solvent was distilled off, the residue was put into 2 liters of water, and the precipitate was recrystallized with ethanol to give Table 7. To obtain monomers M-30 to M-44.

The yield of the obtained monomer is shown in Table 7.

Each abbreviation in Table 7 means the following components. _{Y-13: C (CH 3} ) 2 (C 2 H 5) -OH t- amyl alcohol _{Y-14: C (CH 3} ) 3 -OH t- butyl alcohol _{Y-15: CH (CH 3} ) 2 -OH 2-propanol _{Y-16: CH 2 = CHCH} 2 -OH 2- propene -1
- All _{Y-17: CH 2 = C} (CH 3) 3 -OH 1- methylvinyl alcohol

[0237]

[Chemical 83]

Y-20: HO-C (CH ₃ ) ₂ CH = CH
₂ 1,1-Dimethylallyl alcohol MA: Methacrylic acid M-1, M-2, M-5, M-6, M-19 to M-2
2, M-30 to M-44 are the same as above.

[0239]

[Table 7]

[Production Examples 45 to 47] (Synthesis of Polymer Compound Monomer Having Carboxylic Acid Ester Group on Side Part 2) Isopropyl alcohol 50
To 0 cc, 10.5 g of sodium metal and the raw material compound Y shown in Table 8 in the amount shown in Table 8 were added. To this solution was added the starting compound X shown in Table 8 in the amount shown in Table 8 and reacted at room temperature for 24 hours. The solvent was distilled off with a rotary evaporator,
The residue was recrystallized from ether to give synthetic monomers (M-45 to M-47) shown in Table 8.

The yield of the obtained monomer is shown in Table 8.

The abbreviations in Table 8 mean the following components. X-5: same as above Y-21: CH ₂ (COO-t-Bu) ₂ malonic acid-di-butyl ester Y-22: CH (COO-t-Bu) (CH ₂ COO-
t-Bu) ₂ tricarballylic acid-tri-t-butyl ester Y-23: CH (COO-t-Bu) ₃ methanetricarboxylic acid-tri-t-butyl ester M-45 to M-47 are the same as above.

[0243]

[Table 8]

[Production Examples 48 to 71] (Synthesis of Polymer Compound (A) Having Both of Carboxyl Group-Containing Group and Carboxylate Group-Containing Group in Side Chain of Polymer) Polymer compound (A) was obtained by copolymerizing the monomer of the alkali-soluble polymer compound and the monomer of the polymer compound having the carboxylic acid ester group in the side chain.

The amounts of the monomers shown in Tables 9 and 10 and 2 kinds of the monomers shown in Tables 9 and 10 and 0.15 g of azobisisobutyronitrile as a polymerization initiator and 40 g of dioxane were charged into a reaction vessel in which nitrogen gas was replaced and dissolved. Then, at 60 ℃ 12
Polymerized for hours. After completion of the polymerization, the reaction solution was dropped into toluene to precipitate a polymer, which was filtered and then dried in a vacuum drier to obtain the polymer compound (A-1 to A-) described in Tables 9 and 10.
24) was obtained.

The molecular weights of the obtained polymer compounds are shown in Tables 9 and 1.
It shows in 0.

The abbreviations of monomers and A-1 to A-24 in Tables 9 and 10 are the same as above.

[0248]

[Table 9]

[0249]

[Table 10]

[Production Example 72] (Synthesis of polyvalent carboxylic acid ester compound) 12 g of metallic sodium and 75 g of Meldrum's acid were added to 500 cc of isopropyl alcohol. 45 g of p-xylylene dichloride was added to this solution and the reaction was carried out at room temperature for 24 hours. The solvent was distilled off on a rotary evaporator, the residue was dissolved in ether and the ether layer was washed several times with water. The ether layer was dried and recrystallized with ethanol to obtain the target xylylene bismel drum acid compound b-1.

The chemical formulas of b-1 and the following b-2 to b-4 are the same as above.

[Production Example 73] (Synthesis of polyvalent carboxylic acid ester compound 2) p-
Dissolve 50 g of phenylenediacetic acid in 100 ml of thionyl chloride, add 0.5 ml of dimethylformamide, and add 12
A time reaction was performed. After the reaction, thionyl chloride was distilled off under reduced pressure, and the residue was dissolved in 200 cc of tetrahydrofuran. This was added to a solution prepared by mixing 40 g of t-butyl alcohol and 45 g of pyridine in 200 cc of tetrahydrofuran, and reacted at room temperature for 12 hours. After that, the solvent was distilled off with a rotary evaporator, the residue was put into 2 liters of water, and the precipitate was recrystallized with ethanol to obtain the desired phenylenediacetate compound b-
I got 2.

Production Example 74 (Synthesis of Polycarboxylic Acid Ester Compound 3) 45 g of potassium carbonate and 0.1 g of potassium iodide were added to a solution of 50 g of bisphenol A dissolved in 500 cc of acetone. Further, 90 g of t-butyl bromoacetic acid was added and the mixture was refluxed for 24 hours for reaction. After the reaction, the solvent was distilled off with a rotary evaporator, the residue was put into 2 liters of water, and the precipitate was recrystallized with ethanol to obtain the desired phenoxyacetic acid ester compound b-3.

[Production Example 75] (Synthesis of polyvalent carboxylic acid ester compound 4) 2,
50 g of 5-dimethyl-2,5-hexadiol and 60 g of pyridine were dissolved in 500 cc of tetrahydrofuran. While cooling this solution in an ice bath, 110 g of phenylacetic acid chloride was added and reacted at 0 to 5 ° C for 4 hours. After the reaction, the solvent was distilled off with a rotary evaporator, the residue was put into 2 liters of water, and the precipitate was recrystallized with ethanol to obtain the desired diol phenylacetic acid ester compound b-4.

[Examples 1 to 30 and Comparative Examples 1 to 3] (Preparation of resist solution) Polymer compounds shown in Tables 11 to 16, acid-generating compounds, polyvalent carboxylic acid ester compounds,
Dissolving a predetermined amount of a polyhydric phenol carbonate compound and an alkali-soluble polymer compound in a solvent (diethylene glycol dimethyl ether) in an amount described in Tables 11 to 16,
A resist solution was prepared using a 0.25 micron filter. The resolution was measured by the following method using this resist. The results are shown in Tables 11-16. (Measurement of Resolution) The resist was applied on a silicon wafer using a spin coater to obtain a pattern forming film having a film thickness of about 1 micron. After irradiating the film with the amount of light described in Tables 11 to 16, the film was heated on a hot plate at 100 ° C. for 90 seconds. After that, development was performed for 60 seconds with a 2.38% tetramethylammonium hydroxide aqueous solution. The resolution was defined as the mask size at which the line and space pattern could be resolved in good shape.

The abbreviations in Tables 11 to 16 indicate the following contents. a-1: triphenylsulfonium triflate a-2: diphenyliodonium triflate a-3: triphenylsulfonium tetrafluoroborate a-4: triphenylsulfonium hexafluoroantimonate b-6: di-t-butyl terephthalate c- 1: Bisphenol A di-t-butyl carbonate c-2: Trisphenol tris-t-butyl carbonate B-30: Polyvinylphenol B-31: 20 mol% of the hydroxyl group of polyvinylphenol
Protected by t-butoxycarbonyl group KrF: KrF excimer laser polymer compound (A), alkali-soluble polymer compound (B), polyvalent carboxylic acid ester compounds b-1 to b-5
Is the same as above.

[0257]

[Table 11]

[0258]

[Table 12]

[0259]

[Table 13]

[0260]

[Table 14]

[0261]

[Table 15]

[0262]

[Table 16]

[0263]

As described above, the photosensitive resin composition of Invention 1 has high sensitivity to radiation exposure and high resolution, and is extremely useful as a radiation-sensitive resist material.
It can be effectively used for manufacturing a semiconductor device such as a VLSI that requires a fine pattern.

In addition to the effects of Invention 1, the photosensitive resin composition of Invention 2 is further excellent in the difference in dissolution rate between the unexposed area and the exposed area in the developing solution.

In addition to the effects of Invention 1, the photosensitive resin composition of Invention 3 is further excellent in the difference in dissolution rate between the unexposed area and the exposed area in the developing solution.

In addition to the effects of Invention 1, the photosensitive resin composition of Invention 4 has an improved dissolution rate in the exposed area and further excellent pattern removal.

The photosensitive resin composition of Invention 2-1 is the same as Invention 2
In addition to the above effect, the dissolution rate of the exposed area is improved, and the difference between the dissolution rates of the unexposed area and the exposed area is further increased.

The photosensitive resin composition of Invention 4-1 is the same as Invention 4
In addition to the above effect, the dissolution rate of the exposed area is improved, and the difference between the dissolution rates of the unexposed area and the exposed area is further increased.

The photosensitive resin composition of Invention 1-1 is the same as Invention 1
In addition to the above effect, the dry etching resistance is further excellent.

The photosensitive resin composition of Invention 2-2 is the same as Invention 2
In addition to the above effect, the dry etching resistance is further excellent.

The photosensitive resin composition of Invention 3-1 is the same as Invention 3
In addition to the above effect, the dry etching resistance is further excellent.

The photosensitive resin composition of Invention 4-2 is the same as Invention 4
In addition to the above effect, the dry etching resistance is further excellent.

Front Page Continuation (72) Inventor Hideo Horibe 8-1-1 Tsukaguchihonmachi, Amagasaki City Mitsubishi Electric Corporation Material Device Research Center (72) Inventor Shigeru Kubota 8-1-1 Tsukaguchihonmachi, Amagasaki Mitsubishi Electric Corporation Company Materials Device Laboratory

Claims (7)

[Claims] 1. A group containing a carboxyl group and a compound represented by the general formula (I): (In the formula, R ¹ is a hydrogen atom, a methyl group or a phenyl group,
R ² is a t-butyl group or a t-amyl group, i is 0 or 1, j is 0, 1 or 2, provided that when j is 0 or 1, a plurality of i are independently 0 or 1). A group containing a carboxylic acid ester group represented by the general formula (I
I): [Chemical 2] (In the formula, R ³ is a t-butyl group, a t-amyl group, an isopropyl group, an allyl group, a 1-methylvinyl group, a 1,1-dimethylallyl group, a 2,5-dioxanyl group or a tetrahydrofuranyl group, and k is A group containing a carboxylic acid ester group represented by 0, 1 or 2), the general formula (III): (In the formula, R ⁴ is a hydrogen atom, a methyl group or a phenyl group,
R ³ is the same as the above) and a group containing a carboxylic acid ester group and a compound represented by the general formula (IV): (Wherein R ³ is the same as above) containing a polymer compound having at least one kind of a group containing a carboxylic acid ester group in its side chain and a compound capable of generating an acid or a base upon irradiation with light. A photosensitive resin composition comprising: 2. A group containing a carboxyl group and a compound represented by the general formula (I): (In the formula, R ¹ is a hydrogen atom, a methyl group or a phenyl group,
R ² is a t-butyl group or a t-amyl group, i is 0 or 1, j is 0, 1 or 2, provided that when j is 0 or 1, a plurality of i are independently 0 or 1). A group containing a carboxylic acid ester group represented by the general formula (I
I): (In the formula, R ³ is a t-butyl group, a t-amyl group, an isopropyl group, an allyl group, a 1-methylvinyl group, a 1,1-dimethylallyl group, a 2,5-dioxanyl group or a tetrahydrofuranyl group, and k is A group containing a carboxylic acid ester group represented by 0, 1 or 2), represented by the general formula (III): (In the formula, R ⁴ is a hydrogen atom, a methyl group or a phenyl group,
R ³ is the same as above) and a group containing a carboxylic acid ester group and a compound represented by the general formula (IV): (In the formula, R ³ is the same as above), a polymer compound having at least one kind of a group containing a carboxylic acid ester group in a side chain, a polyvalent carboxylic acid ester compound and an acid or A photosensitive resin composition comprising a compound that generates a base. 3. A group containing a carboxyl group and a compound represented by the general formula (I): (In the formula, R ¹ is a hydrogen atom, a methyl group or a phenyl group,
R ² is a t-butyl group or a t-amyl group, i is 0 or 1, j is 0, 1 or 2, provided that when j is 0 or 1, a plurality of i are independently 0 or 1). A group containing a carboxylic acid ester group represented by the general formula (I
I): (In the formula, R ³ is a t-butyl group, a t-amyl group, an isopropyl group, an allyl group, a 1-methylvinyl group, a 1,1-dimethylallyl group, a 2,5-dioxanyl group or a tetrahydrofuranyl group, and k is A group containing a carboxylic acid ester group represented by 0, 1 or 2), represented by the general formula (III): (In the formula, R ⁴ is a hydrogen atom, a methyl group or a phenyl group,
R ³ is the same as above) and a group containing a carboxylic acid ester group and a compound represented by the general formula (IV): (In the formula, R ³ is the same as above), a polymer compound having at least one kind of a group containing a carboxylic acid ester group in its side chain, a carbonic acid ester compound of a polyhydric phenol, and an acid by irradiation with light. Alternatively, a photosensitive resin composition containing a compound that generates a base. 4. A group containing a carboxyl group and a compound represented by the general formula (I): (In the formula, R ¹ is a hydrogen atom, a methyl group or a phenyl group,
R ² is a t-butyl group or a t-amyl group, i is 0 or 1, j is 0, 1 or 2, provided that when j is 0 or 1, a plurality of i are independently 0 or 1). A group containing a carboxylic acid ester group represented by the general formula (I
I): [Chemical 14] (In the formula, R ³ is a t-butyl group, a t-amyl group, an isopropyl group, an allyl group, a 1-methylvinyl group, a 1,1-dimethylallyl group, a 2,5-dioxanyl group or a tetrahydrofuranyl group, and k is A group containing a carboxylic acid ester group represented by 0, 1 or 2), represented by the general formula (III): (In the formula, R ⁴ is a hydrogen atom, a methyl group or a phenyl group,
R ³ is the same as the above) and a group containing a carboxylic acid ester group and a compound represented by the general formula (IV): (Wherein R ³ is the same as above), a polymer compound having at least one kind of a group containing a carboxylic acid ester group in its side chain, an alkali-soluble polymer compound, and an acid or a base upon irradiation with light. A photosensitive resin composition comprising a compound that generates 5. The polyvalent carboxylic acid ester compound has the general formula (V): (In the formula, R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen atom, a compound represented by the general formula (VI): (In the formula, R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or 2 carbon atoms.
~ 6 alkenyl group, C2-6 alkynyl group, C1-6 oxyalkyl group or halogen atom, 1
Is a group containing a carboxylic acid ester group represented by the formula (VII) or represented by the general formula (VII): (In the formula, R ¹⁰ is the same as described above, R ¹¹ is an alkylene group having 3 to 6 carbon atoms, a divalent hydrocarbon group having a double bond, or a general formula (VIII): — (CH ₂ ) _m —O— (CH ₂ ) _n- (VIII) (wherein m and n are each independently 1 or 2), and 1 is as defined above, provided that at least R ⁵ , R ⁶ and R ⁷ One type is general formula (VI) or (VII)
A group containing a carboxylic acid ester group represented by the following formula 2) in the molecule
The photosensitive resin composition according to claim 2, which is a compound that is decomposed by one or more contained acids or bases. 6. The photosensitive resin composition according to claim 4, wherein the alkali-soluble polymer compound is a polymer compound having a side chain with a group containing a carboxyl group. 7. At least one of a group containing a carboxyl group and a group containing a carboxylic acid ester group represented by formula (I), (II), (III) or (IV).
A group containing a carboxyl group in a polymer compound having a seed and a side chain is represented by the general formula (IX): (In the formula, R ¹² is a hydrogen atom or a methyl group, i is 0 or 1, and j is 0, 1 or 2.), a compound represented by the general formula (X): (Wherein, k is 0 or 1), a group represented by the general formula (X
I): (In the formula, R ¹³ and R ¹⁴ are each independently a hydrogen atom,
Methyl group, phenyl group, benzyl group or CH ₂ COO
H and Z are a group represented by O, N (C ₆ H ₅ ) or NH) and the general formula (XII): The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition is at least one kind of groups represented by the formula (i is the same as above).