JPWO2009145227A1 - Photosensitive resin composition - Google Patents

Abstract

INDUSTRIAL APPLICABILITY According to the present invention, a novel photosensitive resin composition having positive lithographic performance, which has excellent storage stability, high sensitivity and excellent sensitivity over time, and a method for producing a cured relief pattern using the composition And a semiconductor device having the cured relief pattern. The photosensitive resin composition according to the present invention is (A) the following general formula (1): {wherein X1, X2, Y1, Y2, 1, and m are as defined in the claims. } 100 parts by mass of a hydroxypolyamide having a structure represented by: (B) The following general formula (2): {wherein k, X, R1, R2, n, p, q are defined in the claims. is there. } 0.01-30 mass parts of alkoxyalkyl group containing compounds represented, and (C) 1-100 mass parts of diazoquinone compounds are characterized by the above-mentioned.

Description

  The present invention relates to a photosensitive resin composition used as a surface protective film and an interlayer insulating film of a semiconductor device, a method for producing a cured relief pattern having heat resistance using the photosensitive resin composition, and the cured relief pattern. The present invention relates to a semiconductor device.

  Conventionally, a polyimide resin having excellent heat resistance, electrical characteristics, mechanical characteristics, and the like has been used for a surface protective film and an interlayer insulating film of a semiconductor device. This polyimide resin is generally provided in the form of a photosensitive polyimide precursor composition, and is applied to a substrate, patterned with actinic rays, developed, heat imidized, and the like to form a surface protective film on a semiconductor device. In addition, an interlayer insulating film or the like can be easily formed, and the process can be significantly shortened as compared with the conventional non-photosensitive polyimide precursor composition.

  However, the photosensitive polyimide precursor composition needs to use a large amount of an organic solvent such as N-methyl-2-pyrrolidone as a developing solution in the development process. Solvent measures have been demanded. In response to this, recently, various proposals have been made on heat-resistant photosensitive resin materials that can be developed with an alkaline aqueous solution, as with photoresists.

  Among them, a PBO precursor composition obtained by mixing an alkaline aqueous solution-soluble hydroxypolyamide, such as polybenzoxazole (hereinafter also referred to as “PBO”) precursor, with a photoactive component such as a diazoquinone compound is used as a positive photosensitive resin composition. A method to be used has been attracting attention in recent years (for example, see Patent Document 1 below).

  The development mechanism of this positive photosensitive resin is that the unexposed portion of the diazoquinone compound is insoluble in the alkaline aqueous solution, but the exposure causes the diazoquinone compound to undergo a chemical change to become an indenecarboxylic acid compound, which becomes an alkaline aqueous solution. It utilizes the fact that it becomes soluble. By utilizing the difference in the dissolution rate with respect to the developer between the exposed portion and the unexposed portion, it becomes possible to produce a relief pattern of only the unexposed portion.

  The PBO precursor composition described above can form a positive relief pattern by exposure and development with an alkaline aqueous solution. Further, when heated (hereinafter also referred to as “cure”), an oxazole ring is generated, and the cured PBO film has the same thermosetting film characteristics as a polyimide film. Has attracted attention as an alternative material.

  When manufacturing a semiconductor using such a photosensitive resin composition, the photosensitivity of the photosensitive resin composition is particularly important. In the exposure process at the time of manufacturing a semiconductor device, a reduction projection exposure machine called an i-line stepper (hereinafter simply referred to as “stepper”) using the i-line of a mercury lamp is mainly used. Since this stepper is a very expensive machine, if the photosensitive resin composition has a low sensitivity, the exposure time required to form a relief pattern becomes longer, and the number of required steppers increases and the exposure process becomes more expensive. This leads to cost reduction.

  As a technique for improving the photosensitivity of a positive photosensitive resin composition, a technique of adding a compound having a thermally crosslinkable group to the composition is known. When a compound having a thermally crosslinkable group is added to the photosensitive resin composition, it causes an addition reaction with the aromatic ring of the polymer during curing, suppresses shrinkage due to polymer decomposition and thermal relaxation, and cures during curing. It has the function of suppressing membrane shrinkage. When shrinkage during curing is suppressed, a thicker final film thickness can be obtained even with an initial coating film thickness of the same composition. In other words, a thin initial coating film thickness is sufficient to obtain the same final film thickness. The thinner the initial coating film thickness, the easier the light energy in the exposure process reaches the bottom of the film, and high sensitivity can be realized as a positive photosensitive resin composition in which the exposed part opens.

  As a technique for adding a conventionally known thermally crosslinkable group to a composition, for example, a compound having a methylolic thermally crosslinkable urea-based organic group added to an alkali-soluble resin (for example, claim of Patent Document 1) 2) or a compound having an epoxy group added to an alkali-soluble resin (for example, Patent Document 2 below), or a compound having a benzoxazine group added to an alkali-soluble resin (for example, Patent Document 2 below) Has been proposed.

JP 2002-328472 A JP 2004-093816 A JP 2000-305268 A JP 2006-178437 A JP 2005-037925 A JP 2007-016214 A Japanese Patent Laid-Open No. 06-27654

  The thermal crosslinking agent reacts with the polymer with high efficiency and exhibits a high crosslinking effect, but due to its high reactivity, heating in the step of forming the photosensitive resin layer by applying the composition onto the substrate (hereinafter referred to as “pre-baking”) May also cause cross-linking of unexposed areas and loss of resolution, a risk that a thermal cross-linking agent may react with an acid generated by exposure in an exposed area, thereby impairing sensitivity, or loss of storage stability of the composition. May cause problems. Moreover, what added the methylol-type heat-crosslinking compound which has a phenolic hydroxyl group to alkali-soluble resin (for example, refer patent document 1, claim 1, patent document 3, patent document 4) was developed, and these are well-known. Since the compound contains a phenolic hydroxyl group, the alkali solubility of the composition is increased, and when the addition amount is increased to an amount sufficient to suppress shrinkage during curing, the difference in dissolution rate between the exposed area and the unexposed area ( Contrast) is lost, and conversely the sensitivity is lowered. A compound in which a compound containing a methylol group not containing a phenolic hydroxyl group is added to an alkali-soluble resin is known (see, for example, Patent Document 5), but a compound having a methylol group reacts gently in the composition (dark). Reaction), the storage stability (viscosity stability) of the photosensitive resin composition is poor. Moreover, the composition which adds the heat-crosslinkable compound which has an alkoxy methyl group more stable than a methylol group to alkali-soluble resin is disclosed (refer patent document 2, patent document 6), and the compound which does not contain a phenolic hydroxyl group is also used. Although the description which can be seen is seen, the Example by the alkoxymethyl group containing compound which does not actually have a phenolic hydroxyl group is not shown.

  In view of the problems of the prior art, the problem to be solved by the present invention is a novel photosensitivity having positive lithographic performance that has excellent storage stability, high sensitivity, and excellent temporal stability of sensitivity after exposure. It is providing the resin composition, the manufacturing method of the hardening relief pattern using this composition, and the semiconductor device which has this hardening relief pattern.

  As a result of intensive studies to solve the above problems, the present inventor has combined a polybenzoxazole resin precursor with a heat-crosslinkable low molecular weight compound having a specific structure, so that storage stability (viscosity stability) is achieved. It was found that a photosensitive resin composition having high-sensitivity positive-type lithography characteristics can be obtained without impairing the above. Furthermore, in combination with a thermally crosslinkable low molecular weight compound having a specific structure, a photosensitive resin composition having a small sensitivity change with time after exposure of high-sensitivity lithography characteristics and excellent sensitivity stability over time may be obtained. The headline and the present invention were completed.

｛式中、Ｘ^１は、炭素原子を有する４価の有機基であり、Ｘ^２、Ｙ^１及びＹ^２は、それぞれ独立に、２個以上の炭素原子を有する２価の有機基であり、ｌは、２〜１０００の整数であり、ｍは、０〜５００の整数であり、ｌ／（ｌ＋ｍ）＞０．５であり、そしてＸ^１及びＹ^１を含むｌ個のジヒドロキシジアミド単位並びにＸ^２及びＹ^２を含むｍ個のジアミド単位の配列順序は問わない。｝で表される構造を含むヒドロキシポリアミド１００質量部、（Ｂ）下記一般式（２）：

｛式中、ｋは、１〜４の整数であり、（ｉ）ｋ＝１のとき、Ｘは、Ｃ_ｎＨ_２ｎＯＲ^１又はＲ^２であり、Ｒ^１は、メチル基、エチル基、ｎ−プロピル基、及びイソプロピル基からなる群から選ばれる１価の有機基であり、Ｒ^２は、水素原子、炭素数１〜４のアルキル基、炭素数２〜１０のエステル基、炭素数２〜１０のウレタン基、及び炭素数１〜１０のアルコキシ基からなる群より選ばれる１価の有機基であり、ｎは、１〜３の整数であり、ｐは、１〜５の整数であり、ｑは、０〜４の整数であり、そして（ｐ＋ｑ）＝５であり、（ｉｉ）ｋ＝２〜４のとき、Ｘは、単結合又は２〜４価の有機基であり、Ｒ^１は、メチル基、エチル基、ｎ−プロピル基、及びイソプロピル基からなる群から選ばれる１価の有機基であり、Ｒ^２は、水素原子、炭素数１〜４のアルキル基、炭素数２〜１０のエステル基、及び炭素数２〜１０のウレタン基からなる群より選ばれる１価の有機基であり、ｎは、１〜３の整数であり、ｐは、１〜５の整数であり、ｑは０〜４の整数であり、そして（ｐ＋ｑ）＝５である。但し、Ｃ_ｎＨ_２ｎＯＲ^１及びＲ^２が複数存在する場合、ｎ、ｐ、ｑ、Ｒ^１、及びＲ^２は、互いに同一でも異なっていてもよい。｝で表されるアルコキシアルキル基含有化合物０．０１〜３０質量部、及び（Ｃ）ジアゾキノン化合物１〜１００質量部を含むことを特徴とする感光性樹脂組成物。That is, the present invention is as follows.
[1] (A) The following general formula (1):

{Wherein X ¹ is a tetravalent organic group having a carbon atom, and X ² , Y ¹ and Y ² are each independently a divalent organic group having 2 or more carbon atoms, l is an integer from 2 to 1000, m is an integer from 0 to 500, l / (l + m)> 0.5, and ¹ dihydroxydiamide unit containing X ¹ and Y ¹ and X The arrangement order of the m diamide units including ² and Y ² is not limited. } 100 parts by mass of a hydroxypolyamide having a structure represented by the following general formula (2):

{Wherein k is an integer of 1 to 4, (i) when k = 1, X is C _n H _2n OR ¹ or R ² , R ¹ is a methyl group, an ethyl group, n -A monovalent organic group selected from the group consisting of a propyl group and an isopropyl group, and R ² is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an ester group having 2 to 10 carbon atoms, or 2 to 2 carbon atoms. 10 is a monovalent organic group selected from the group consisting of a urethane group and an alkoxy group having 1 to 10 carbon atoms, n is an integer of 1 to 3, p is an integer of 1 to 5, q is an integer of 0 to 4 and (p + q) = 5, (ii) when k = 2 to 4, X is a single bond or a divalent to tetravalent organic group, and R ¹ is , A monovalent organic group selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, and R ² represents a hydrogen atom A monovalent organic group selected from the group consisting of a group, an alkyl group having 1 to 4 carbon atoms, an ester group having 2 to 10 carbon atoms, and a urethane group having 2 to 10 carbon atoms, and n is 1 to 3 Is an integer, p is an integer from 1 to 5, q is an integer from 0 to 4, and (p + q) = 5. However, when there are a plurality of C _n H _2n OR ¹ and R ² , n, p, q, R ¹ , and R ² may be the same as or different from each other. } The photosensitive resin composition characterized by including 0.01-30 mass parts of alkoxyalkyl group containing compounds represented, and (C) 1-100 mass parts of diazoquinone compounds.

｛式中、ｋは、１又は２であり、（ｉ）ｋ＝１のとき、Ｘは、Ｃ_ｎＨ_２ｎＯＲ^１又はＲ^２であり、Ｒ^１は、メチル基、エチル基、ｎ−プロピル基、及びイソプロピル基からなる群から選ばれる１価の有機基であり、Ｒ^２は、水素原子、炭素数１〜４のアルキル基、炭素数２〜１０のエステル基、炭素数２〜１０のウレタン基、及び炭素数１〜１０のアルコキシ基からなる群より選ばれる１価の有機基であり、ｎは、１〜３の整数であり、（ｉｉ）ｋ＝２のとき、Ｘは、単結合又は下記一般式（４）：

で表される基から選ばれる２〜４価の有機基であり、Ｒ^１は、メチル基、エチル基、ｎ−プロピル基、及びイソプロピル基からなる群から選ばれる１価の有機基であり、Ｒ^２は、水素原子、炭素数１〜４のアルキル基、炭素数２〜１０のエステル基、及び炭素数２〜１０のウレタン基からなる群より選ばれる１価の有機基であり、ｎは、１〜３の整数であり、ｐは、１〜５の整数であり、ｑは、０〜４の整数であり、そして（ｐ＋ｑ）＝５である。但し、Ｃ_ｎＨ_２ｎＯＲ^１及びＲ^２が複数存在する場合、ｎ、ｐ、ｑ、Ｒ^１、及びＲ^２は、互いに同一でも異なっていてもよい。｝
で表される、前記［１］に記載の感光性樹脂組成物。[2] The (B) alkoxyalkyl group-containing compound has the following general formula (3):

{Wherein k is 1 or 2, (i) when k = 1, X is C _n H _2n OR ¹ or R ² , R ¹ is a methyl group, an ethyl group, n-propyl A monovalent organic group selected from the group consisting of a group and an isopropyl group, and R ² is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an ester group having 2 to 10 carbon atoms, or an alkyl group having 2 to 10 carbon atoms. A monovalent organic group selected from the group consisting of a urethane group and an alkoxy group having 1 to 10 carbon atoms, n is an integer of 1 to 3, and (ii) when k = 2, X is a single group. Bond or the following general formula (4):

R ¹ is a monovalent organic group selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, R ² is a monovalent organic group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an ester group having 2 to 10 carbon atoms, and a urethane group having 2 to 10 carbon atoms, and n is , 1-3, p is an integer of 1-5, q is an integer of 0-4, and (p + q) = 5. However, when there are a plurality of C _n H _2n OR ¹ and R ² , n, p, q, R ¹ , and R ² may be the same as or different from each other. }
The photosensitive resin composition as described in said [1] represented by these.

｛式中、Ｒ^１は、メチル基、エチル基、ｎ−プロピル基、及びイソプロピル基からなる群から選ばれる１価の有機基であり、ｎは、１〜３の整数であり、ｐは、１〜５の整数であり、ｋは、１又は２であり、（ｉ）ｋ＝１のとき、Ｘは、水素原子又はＣ_ｎＨ_２ｎＯＲ^１であり、（ｉｉ）ｋ＝２のとき、Ｘは、単結合又は下記一般式（６）：

で表される基から選ばれる２〜４価の有機基である。但し、（Ｃ_ｎＨ_２ｎＯＲ^１）が複数存在する場合、ｎ及びＲ^１は互いに同一でも異なっていてもよい。｝で表される、前記［１］又は［２］に記載の感光性樹脂組成物。[3] The (B) alkoxyalkyl group-containing compound has the following general formula (5):

{In the formula, R ¹ is a monovalent organic group selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, n is an integer of 1 to 3, and p is An integer of 1 to 5, k is 1 or 2, (i) when k = 1, X is a hydrogen atom or C _n H _2n OR ¹ , and (ii) when k = 2, X is a single bond or the following general formula (6):

Or a divalent to tetravalent organic group selected from the group represented by However, when there are a plurality of (C _n H _2n OR ¹ ), n and R ¹ may be the same as or different from each other. } The photosensitive resin composition as described in said [1] or [2] represented by.

  [4] (B) The alkoxyalkyl group-containing compound is bis (methoxymethyl) benzene, tris (methoxymethyl) benzene, tetrakis (methoxymethyl) benzene, pentakis (methoxymethyl) benzene, hexakis (methoxymethyl) benzene, tris ( Any one of the above [1] to [3] selected from the group consisting of methoxymethyl) trimethoxybenzene, methoxymethylbiphenyl, bis (methoxymethyl) biphenyl, bis (methoxymethyl) diphenyl ether, and bis (methoxymethyl) diphenylmethane The photosensitive resin composition as described in 2.

｛式中、Ｚ_１は、下記一般式（８）：

（式中、Ｒ^３〜Ｒ^５は、それぞれ独立に、炭素数１〜９の有機基であり、Ｒ^６は、メチル基、エチル基、ｎ−プロピル基、及びイソプロピル基からなる群から選ばれる１価の有機基であり、そしてＲ^７〜Ｒ^１０は、それぞれ独立に、炭素数１〜１２の有機基である。）で表される基から選ばれる置換基であり、ｋは、１〜４の整数であり、（ｉ）ｋ＝１のとき、Ｚ^２は、Ｃ_ｎＨ_２ｎＯＲ^１又はＲ^２であり、Ｒは、それぞれ独立に、メチル基又はエチル基であり、Ｒ^１は、メチル基、エチル基、ｎ−プロピル基、及びイソプロピル基からなる群から選ばれる１価の有機基であり、Ｒ^２は、水素原子、及び炭素数１〜４のアルキル基からなる群より選ばれる１価の有機基であり、ｎは、１〜３の整数であり、（ｉｉ）ｋ＝２〜４のとき、Ｚ^２は、単結合又は２〜４価の有機基であり、Ｚ^１が複数存在する場合、Ｚ^１は同一であっても異なっていてもよい。｝で表される、前記［１］に記載の感光性樹脂組成物。[5] The (B) alkoxyalkyl group-containing compound has the following general formula (7):

{In the formula, Z ₁ represents the following general formula (8):

(In the formula, R ^{3 to} R ⁵ are each independently an organic group having 1 to 9 carbon atoms, and R ⁶ is selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Is a monovalent organic group, and R ^{7 to} R ¹⁰ are each independently a substituent selected from a group represented by a C 1-12 organic group. 4 and (i) when k = 1, Z ² is C _n H _2n OR ¹ or R ² , R is independently a methyl group or an ethyl group, and R ¹ is A monovalent organic group selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, and R ² is selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms. A monovalent organic group, n is an integer of 1 to 3, and (ii) when k = 2 to 4 , Z ² is a single bond or a divalent to tetravalent organic group, and when a plurality of Z ¹ are present, Z ¹ may be the same or different. } The photosensitive resin composition as described in [1] above.

｛式中、Ｒは、それぞれ独立に、メチル基又はエチル基であり、Ｚ^１は、それぞれ独立に、下記一般式（１０）：

（式中、Ｒ^３〜Ｒ^５は、それぞれ独立に、炭素数１〜９の有機基であり、Ｒ^６は、メチル基、エチル基、ｎ−プロピル基、及びイソプロピル基からなる群から選ばれる１価の有機基であり、そしてＲ^７〜Ｒ^１０は、それぞれ独立に、炭素数１〜１２の有機基である。）で表される基から選ばれる置換基であり、Ｚ^３は、単結合又は下記一般式（１１）：

で表される基から選ばれる置換基である。｝で表される、前記［５］に記載の感光性樹脂組成物。[6] The (B) alkoxyalkyl group-containing compound has the following general formula (9):

{In the formula, each R is independently a methyl group or an ethyl group, and each Z ¹ independently represents the following general formula (10):

(In the formula, R ^{3 to} R ⁵ are each independently an organic group having 1 to 9 carbon atoms, and R ⁶ is selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. a monovalent organic group, and ^R 7 ^{to R 10} are each independently a substituent selected from the group represented by is an organic group having 1 to 12 carbon atoms.), ^{Z 3} is a single Bond or the following general formula (11):

Is a substituent selected from the group represented by: } The photosensitive resin composition as described in said [5] represented by.

｛式中、Ｒ^３及びＲ^５は、それぞれ独立に、炭素数１〜９の有機基であり、そしてＲ^７は、炭素数１〜１２の有機基である。｝で表される基から選ばれる置換基である、前記［６］に記載の感光性樹脂組成物。[7] In the general formula (9), Z ³ is a single bond, and each Z ¹ independently represents the following general formula (12):

{In the formula, R ³ and R ⁵ are each independently an organic group having 1 to 9 carbon atoms, and R ⁷ is an organic group having 1 to 12 carbon atoms. } The photosensitive resin composition as described in [6] above, which is a substituent selected from the group represented by:

で表される基から選ばれる置換基である、前記［６］に記載の感光性樹脂組成物。[8] In the general formula (9), Z ³ is a single bond, and each Z ¹ independently represents the following general formula (13):

The photosensitive resin composition as described in [6] above, which is a substituent selected from the group represented by:

  [9] A step of forming a photosensitive resin layer comprising the photosensitive resin composition according to any one of [1] to [8] on a substrate, exposure with actinic rays through a mask, light rays, electrons A method for producing a cured relief pattern comprising a step of directly irradiating a line or ion beam, a step of developing, and a step of heating the obtained relief pattern.

  [10] A semiconductor device comprising a cured relief pattern layer obtained by the method according to [9].

  According to the present invention, a novel photosensitive resin composition having excellent storage stability and high-sensitivity positive lithography performance, a method for producing a cured relief pattern using the composition, and the cured relief pattern are provided. A semiconductor device is provided.

｛式中、Ｘ^１は、炭素原子を有する４価の有機基であり、Ｘ^２、Ｙ^１及びＹ^２は、それぞれ独立に、２個以上の炭素原子を有する２価の有機基であり、ｌは、２〜１０００の整数であり、ｍは、０〜５００の整数であり、ｌ／（ｌ＋ｍ）＞０．５であり、Ｘ^１及びＹ^１を含むｌ個のジヒドロキシジアミド単位並びにＸ^２及びＹ^２を含むｍ個のジアミド単位の配列順序は問わない。｝。<Photosensitive resin composition>
Each component which comprises the photosensitive resin composition of this invention is demonstrated concretely below.
(A) Hydroxypolyamide Hydroxypolyamide, which is the base polymer of the photosensitive resin composition of the present invention, includes a structure represented by the following general formula (1).

{Wherein X ¹ is a tetravalent organic group having a carbon atom, and X ² , Y ¹ and Y ² are each independently a divalent organic group having 2 or more carbon atoms, l is an integer from 2 to 1000, m is an integer from 0 to 500, l / (l + m)> 0.5, ¹ dihydroxydiamide unit containing X ¹ and Y ¹ and X ² And the order of arrangement of m diamide units including Y ² is not limited. }.

In general formula (1), X ¹ is preferably a tetravalent organic group having 2 to 30 carbon atoms, and X ² , Y ¹ , and Y ² are each independently two A divalent organic group having 30 or less carbon atoms is preferred.
The dihydroxydiamide unit of the hydroxy polyamide has a structure in which a dicarboxylic acid having a Y ¹ (COOH) ₂ structure and a bisaminophenol having a X ¹ (NH ₂ ) ₂ (OH) ₂ structure are polycondensed. Here, the two amino groups and the hydroxy group of the bisaminophenol are each in the ortho position, and the dihydroxydiamide unit is closed by heating the hydroxypolyamide at about 280 to 400 ° C. Thus, the benzoxazole unit, which is a heat resistant resin, is changed. l is in the range of 2 to 1000, preferably 2 to 200, more preferably 3 to 50, and still more preferably 3 to 20.

If necessary, the hydroxypolyamide may be condensed with m diamide units of the general formula (1). The diamide unit has a structure in which a diamine having a structure of X ² (NH ₂ ) ₂ and a dicarboxylic having a structure of Y ² (COOH) ₂ are polycondensed. m is in the range of 0 to 500, and preferably in the range of 0 to 10. The higher the ratio of hydroxypolyamide units in the hydroxypolyamide, the higher the solubility in an alkaline aqueous solution used as a developing solution, and the shorter the time required for development, the l / (l + m) value is 0.5 or more. Yes, preferably 0.7 or more, more preferably 0.8 or more.

Examples of the bisaminophenol having the structure of X ¹ (NH ₂ ) ₂ (OH) ₂ include 3,3′-dihydroxybenzidine, 3,3′-diamino-4,4′-dihydroxybiphenyl, and 4,4 ′. -Diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, bis- (3-amino- 4-hydroxyphenyl) methane, 2,2-bis- (3-amino-4-hydroxyphenyl) propane, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis -(4-amino-3-hydroxyphenyl) hexafluoropropane, bis- (4-amino-3-hydroxyphenyl) methane, 2,2-bis -(4-amino-3-hydroxyphenyl) propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino- 3,3′-dihydroxydiphenyl ether, 3,3′-diamino-4,4′-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1 , 3-diamino-4,6-dihydroxybenzene and the like. These bisaminophenols may be used alone or in combination.

から選ばれる芳香族基である。Of these bisaminophenols, particularly preferred are those where X ¹ is:

Is an aromatic group selected from

Preferred examples of the diamine having the X ² (NH ₂ ) ₂ structure include aromatic diamines and silicon diamines.
Among these, examples of the aromatic diamine include m-phenylenediamine, p-phenylenediamine, 2,4-tolylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, and 4,4′-diamino. Diphenyl ether, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,4′- Diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl ketone, 4,4′-diaminodiphenyl ketone, 3,4′-diaminodiphenyl ketone, 2,2′-bis (4-aminophenyl) ) Propane, 2,2'-bis (4-aminophenyl) hexa Fluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4-methyl-2,4-bis (4-aminophenyl) -1-pentene, 4-methyl-2,4-bis (4-aminophenyl) -2-pentene, 1,4-bis (α, α-dimethyl-4-aminobenzyl) benzene, Imino-di-p-phenylenediamine, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 4-methyl-2,4-bis (4-aminophenyl) pentane, 5 (or 6) -amino-1- (4-aminophenyl) -1,3,3-trimethylindane, bis (p-aminophenyl) phosphine oxide, 4,4′-diaminoazobenzene, 4,4′-diamino Phenylurea, 4,4′-bis (4-aminophenoxy) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl ] Hexafluoropropane, 2,2-bis [4- (3-aminophenoxy) phenyl] benzophenone, 4,4'-bis (4-aminophenoxy) diphenylsulfone, 4,4'-bis [4- (α, α-dimethyl-4-aminobenzyl) phenoxy] benzophenone, 4,4′-bis [4- (α, α-dimethyl-4-aminobenzyl) phenoxy] diphenylsulfone, 4,4′-diaminobiphenyl, 4,4 '-Diaminobenzophenone, phenylindanediamine, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-di Aminobiphenyl, o-toluidine sulfone, 2,2-bis (4-aminophenoxyphenyl) propane, bis (4-aminophenoxyphenyl) sulfone, bis (4-aminophenoxyphenyl) sulfide, 1,4- (4-amino) Phenoxyphenyl) benzene, 1,3- (4-aminophenoxyphenyl) benzene, 9,9-bis (4-aminophenyl) fluorene, 4,4′-di- (3-aminophenoxy) diphenylsulfone, and 4, 4′-diaminobenzanilide, and at least one selected from the group consisting of a hydrogen atom of an aromatic nucleus of these aromatic diamines consisting of a chlorine atom, a fluorine atom, a bromine atom, a methyl group, a methoxy group, a cyano group, and a phenyl group And a compound substituted by a group or an atom.

  Further, silicon diamine can be selected in order to enhance the adhesion to the substrate. Examples of this include bis (4-aminophenyl) dimethylsilane, bis (4-aminophenyl) tetramethylsiloxane, and bis (4 -Aminophenyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetramethyldisiloxane, 1,4-bis (γ-aminopropyldimethylsilyl) benzene, bis (4-aminobutyl) tetramethyldisiloxane, bis ( γ-aminopropyl) tetraphenyldisiloxane and the like.

｛式中、Ａは、−ＣＨ_２−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−ＣＯ−、−ＮＨＣＯ−、−Ｃ（ＣＦ_３）_２−、及び単結合からなる群から選択される２価の基を示し、Ｒは、それぞれ独立に、水素原子、アルキル基、アルケニル基、及びハロゲン原子からなる群から選択される基を示し、そしてｋは０〜４の整数を示す。｝。Examples of the dicarboxylic acid having a Y ¹ (COOH) ₂ or Y ² (COOH) ₂ structure include those in which Y ¹ and Y ² are an aliphatic group or an aromatic group having a linear, branched, or cyclic structure. It is done. Among these, when Y ¹ and Y ² are aromatic groups, for example, the following may be mentioned as preferred:

{In the formula, A is selected from the group consisting of —CH ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —, and a single bond. R represents a group selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, and a halogen atom, and k represents an integer of 0 to 4. }.

It is also preferable to use a derivative of 5-aminoisophthalic acid for a part or all of the dicarboxylic acid having the Y ¹ (COOH) ₂ or Y ² (COOH) ₂ structure.
Specific compounds to be reacted with 5-aminoisophthalic acid to obtain the derivative include 5-norbornene-2,3-dicarboxylic acid anhydride, exo-3,6-epoxy-1,2,3, 6-tetrahydrophthalic anhydride, 3-ethynyl-1,2-phthalic anhydride, 4-ethynyl-1,2-phthalic anhydride, cis-4-cyclohexene-1,2-dicarboxylic anhydride, 1 -Cyclohexene-1,2-dicarboxylic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, allyl succinic anhydride , Isocyanate ethyl methacrylate, 3-isopropenyl-α, α-dimethylbenzyl isocyanate 3-cyclohexene-1-carboxylic acid chloride, 2-furancarboxylic acid chloride, crotonic acid chloride, cinnamic acid chloride, methacrylic acid chloride, acrylic acid chloride, propiolic acid chloride, tetrolic acid chloride, thiophene-2-acetyl chloride, p-styrene sulfonyl chloride, glycidyl methacrylate, allyl glycidyl ether, chloroformate methyl ester, chloroformate ethyl ester, chloroformate n-propyl ester, chloroformate isopropyl ester, chloroformate isobutyl ester, chloroformate 2- Ethoxy ester, chloroformate-sec-butyl ester, chloroformate benzyl ester, chloroformate 2-ethylhexyl ester, chloroformate allyl ester, chloroformate phenyl ester, chloride Formic acid 2,2,2-trichloroethyl ester, chloroformic acid-2-butoxyethyl ester, chloroformic acid-p-nitrobenzyl ester, chloroformic acid-p-methoxybenzyl ester, isobornyl benzyl chloroformate , Chloroformic acid-p-biphenylisopropylbenzyl ester, 2-t-butyloxycarbonyl-oxyimino-2-phenylacetonitrile, St-butyloxycarbonyl-4,6-dimethyl-thiopyrimidine, di-t-butyl- Dicarbonate, N-ethoxycarbonylphthalimide, ethyldithiocarbonyl chloride, formic acid chloride, benzoyl chloride, p-toluenesulfonic acid chloride, methanesulfonic acid chloride, acetyl chloride, trityl chloride, trimethylchlorosilane, hexamethyldisi Zan, N, O-bis (trimethylsilyl) acetamide, bis (trimethylsilyl) trifluoroacetamide, (N, N-dimethylamino) trimethylsilane, (dimethylamino) trimethylsilane, trimethylsilyldiphenylurea, bis (trimethylsilyl) urea, isocyanic acid Examples include phenyl, n-butyl isocyanate, n-octadecyl isocyanate, o-tolyl isocyanate, 1,2-phthalic anhydride, cis-1,2-cyclohexanedicarboxylic anhydride, and glutaric anhydride.

｛式中、Ｂは、−ＣＨ_２−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−ＣＯ−、−ＮＨＣＯ−、及び−Ｃ（ＣＦ_３）_２−からなる群から選択される２価の基を意味する。｝。Furthermore, as a dicarboxylic acid having a Y ¹ (COOH) ₂ or Y ² (COOH) ₂ structure, a compound obtained by ring-opening a tetracarboxylic dianhydride with a monoalcohol, a monoamine or the like can also be used. Examples of the monoalcohol include methanol, ethanol, propanol, isopropanol, butanol, t-butanol, benzyl alcohol and the like, and examples of the monoamine include butylamine and aniline. Examples of the tetracarboxylic dianhydride include the following:

_{Wherein, B is, -CH 2 -, - O - , - S -, - SO 2 -, - CO -, - NHCO-, and -C _{(CF 3) 2} - ₂ is selected from the group consisting of Means a valent group. }.

｛式中、Ｘ^３は、Ｘ^１（ＯＨ）_２（ＮＨ−）_２を表し、そしてＸ^１は、上記一般式（１）に定義したものと同じである。｝。Further, by reacting trimellitic acid chloride to the bisaminophenol generates tetracarboxylic dianhydride, by ring-opening in the same way ^Y 1 _{(COOH) 2} or ^Y _{2 (COOH)} 2 It can also be used as a dicarboxylic acid having a structure. The tetracarboxylic dianhydrides obtained here include the following:

{Wherein X ³ represents X ¹ (OH) ₂ (NH—) ₂ , and X ¹ is the same as defined in the general formula (1). }.

  Alternatively, the tetracarboxylic dianhydride and the bisaminophenol can be reacted, and the resulting carboxylic acid residue can be esterified or amidated with a monoalcohol or monoamine.

When Y ¹ and Y ² are aliphatic groups, substituents such as an alkyl chain, a cyclobutyl ring, a cyclopentyl ring, a cyclohexyl ring, and a bicyclo ring are exemplified. Examples of the dicarboxylic acid having a Y ¹ (COOH) ₂ or Y ² (COOH) ₂ structure having an aliphatic group include malonic acid, methyl malonic acid, dimethyl malonic acid, succinic acid, glutaric acid, adipic acid, and itaconic acid. , Maleic acid, diglycolic acid, 1,2-cyclobutanedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-adamantanedicarboxylic acid, octahydro-1H-4,7-methanoindenedicarboxylic acid and the like can be mentioned, but as dicarboxylic acid having an aliphatic group , Octahydro-1H-4,7-methanoindene dicarboxylic acid In the case of using, since you can achieve both high transparency, a high solubility in solvents, preferred.

As a method for polycondensation of a dicarboxylic acid having a Y ¹ (COOH) ₂ structure and a bisaminophenol having a X ¹ (NH ₂ ) ₂ (OH) ₂ structure to produce a dihydroxydiamide unit, a dicarboxylic acid is used. And thionyl chloride to form diacid chloride and then react with bisaminophenol, and dicarboxylic acid and bisaminophenol are polycondensed with dicyclohexylcarbodiimide. In the method using dicyclohexylcarbodiimide, hydroxybenztriazole can be allowed to act simultaneously. In the above-mentioned (A) hydroxypolyamide, it is also preferable to use the end group sealed with an organic group (hereinafter referred to as “sealing group”).

In the polycondensation of hydroxypolyamide, when the dicarboxylic acid component is used in an excessive number of moles compared to the sum of the bisaminophenol component and the diamine component, a compound having an amino group or a hydroxyl group is used as the sealing group. Is preferred. Examples of the compound include aniline, ethynylaniline, norborneneamine, butylamine, propargylamine, ethanol, propargyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, hydroxyethyl acrylate and the like.
Conversely, when the sum of the bisaminophenol component and the diamine component is used in an excessive number of moles compared to the dicarboxylic acid component, the sealing group has an acid anhydride, carboxylic acid, acid chloride, isocyanate group, etc. It is preferable to use a compound. Examples of such compounds include benzoyl chloride, norbornene dicarboxylic anhydride, norbornene carboxylic acid, ethynyl phthalic anhydride, glutaric anhydride, maleic anhydride, phthalic anhydride, cyclohexane dicarboxylic anhydride, methyl cyclohexane dicarboxylic anhydride Products, cyclohexene dicarboxylic acid anhydride, methacryloyloxyethyl methacrylate, phenyl isocyanate, mesyl chloride, tosylic chloride and the like.

  (A) The weight average molecular weight in terms of polystyrene by gel permeation chromatography (hereinafter also referred to as “GPC”) of hydroxypolyamide is preferably 3,000 to 50,000, and preferably 6,000 to 30,000. It is more preferable. The weight average molecular weight is preferably 3,000 or more from the viewpoint of the physical properties of the cured relief pattern. Moreover, from a viewpoint of resolution, 50,000 or less is preferable. As developing solvents for GPC, tetrahydrofuran (hereinafter also referred to as “THF”) and N-methyl-2-pyrrolidone (hereinafter also referred to as “NMP”) are recommended. The molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from organic solvent standard sample STANDARD SM-105 manufactured by Showa Denko.

｛式中、ｋは、１〜４の整数であり、（ｉ）ｋ＝１のとき、Ｘは、Ｃ_ｎＨ_２ｎＯＲ^１又はＲ^２であり、Ｒ^１は、メチル基、エチル基、ｎ−プロピル基、及びイソプロピル基からなる群から選ばれる１価の有機基であり、Ｒ^２は、水素原子、炭素数１〜４のアルキル基、炭素数１〜１０のアルコキシ基、炭素数２〜１０のエステル基、及び炭素数２〜１０のウレタン基からなる群より選ばれる１価の有機基であり、ｎは、１〜３の整数であり、ｐは、１〜５の整数であり、ｑは、０〜４の整数であり、そして（ｐ＋ｑ）＝５であり、（ｉｉ）ｋ＝２〜４のとき、Ｘは、単結合又は２〜４価の有機基であり、Ｒ^１は、メチル基、エチル基、ｎ−プロピル基、及びイソプロピル基からなる群から選ばれる１価の有機基であり、Ｒ^２は、水素原子、炭素数１〜４のアルキル基、炭素数２〜１０のエステル基、及び炭素数２〜１０のウレタン基からなる群より選ばれる１価の有機基であり、ｎは、１〜３の整数であり、Ｒ^１は、メチル基、エチル基、ｎ−プロピル基、及びイソプロピル基からなる群から選ばれる１価の有機基であり、Ｒ^２は、水素原子、炭素数１〜４のアルキル基、炭素数２〜１０のエステル基、及び炭素数２〜１０のウレタン基からなる群より選ばれる１価の有機基であり、そしてｎは、１〜３の整数である。但し、Ｃ_ｎＨ_２ｎＯＲ^１及びＲ^２が複数存在する場合、ｎ、ｐ、ｑ、Ｒ^１、及びＲ^２は、互いに同一でも異なっていてもよい。｝。(B) Alkoxyalkyl group-containing compound The photosensitive resin composition includes (B) at least one alkoxyalkyl group-containing compound selected from the group consisting of compounds represented by the following general formula (2):

{Wherein k is an integer of 1 to 4, (i) when k = 1, X is C _n H _2n OR ¹ or R ² , R ¹ is a methyl group, an ethyl group, n -A monovalent organic group selected from the group consisting of a propyl group and an isopropyl group, wherein R ² is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or 2 to 2 carbon atoms. A monovalent organic group selected from the group consisting of 10 ester groups and urethane groups having 2 to 10 carbon atoms, n is an integer of 1 to 3, and p is an integer of 1 to 5, q is an integer of 0 to 4 and (p + q) = 5, (ii) when k = 2 to 4, X is a single bond or a divalent to tetravalent organic group, and R ¹ is , A monovalent organic group selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, and R ² represents a hydrogen atom A monovalent organic group selected from the group consisting of a group, an alkyl group having 1 to 4 carbon atoms, an ester group having 2 to 10 carbon atoms, and a urethane group having 2 to 10 carbon atoms, and n is 1 to 3 R ¹ is a monovalent organic group selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, and R ² is a hydrogen atom, an alkyl having 1 to 4 carbon atoms. A monovalent organic group selected from the group consisting of a group, an ester group having 2 to 10 carbon atoms, and a urethane group having 2 to 10 carbon atoms, and n is an integer of 1 to 3. However, when there are a plurality of C _n H _2n OR ¹ and R ² , n, p, q, R ¹ , and R ² may be the same as or different from each other. }.

  The present inventor has achieved high-sensitivity lithography performance without impairing storage stability by adding the (B) alkoxyalkyl group-containing compound to the photosensitive resin composition containing (A) hydroxypolyamide. It was also found that the sensitivity change after exposure was small and the sensitivity stability was excellent. That is, by adding the compound (B) to the photosensitive resin composition, it is crosslinked to the aromatic ring of the hydroxypolyamide during curing to suppress shrinkage due to thermal decomposition or thermal relaxation of the hydroxypolyamide, and shrinkage of the film thickness due to curing. Can be suppressed. Therefore, the photosensitive resin composition to which the compound (B) is added can reduce the coating film thickness, thereby enabling the light energy in the exposure process to reach the bottom of the film efficiently, resulting in high sensitivity. By having an alkoxyalkyl group as a crosslinkable group, the storage stability of the varnish is excellent, and by not having a phenolic hydroxyl group, the difference in dissolution rate (contrast) between the exposed and unexposed areas is not lowered, resulting in high sensitivity. It becomes. Although details of the reason why the change in sensitivity after exposure is small is not clear, and it is not desired to be bound by a specific theory, the (B) alkoxyalkyl group-containing compound of the present invention is a diazoquinone compound in the exposed portion. However, even if indenecarboxylic acid is generated due to a chemical change and is in an acidic condition, it is considered that a chemical reaction that lowers the sensitivity is not caused.

  The (B) alkoxyalkyl group-containing compound of the present invention is synthesized by a known method. For example, after adding a halogenated alkyl group to a compound having an aromatic ring, the compound is reacted with an alcohol to obtain an alkoxyalkyl group-containing compound. Method, a method obtained by reacting an alcohol with an aromatic alkyl alcohol compound obtained by reducing an aromatic compound having an alkyl group or a carboxyl group, or a reaction after adding a halogenated alkyl group to a phenol compound. And a method of acylating the alkoxyalkyl group-containing phenol obtained above.

｛式中、Ｌは互いに同じであっても異なっていてもよく、メトキシメチル基、エトキシメチル基、プロポキシメチル基、メトキシエチル基、エトキシエチル基、メトキシプロピル基又はメトキシイソプロピル基を示す。｝。Preferred examples of the alkoxyalkyl group-containing compound represented by the general formula (2) are those having one alkoxyalkyl group, such as methoxymethylbenzene, ethoxymethylbenzene, methoxyethylbenzene, ethoxymethylbenzene, 2-methoxymethyl. As having two such as toluene, 3-methoxymethyltoluene, 4-methoxymethyltoluene, 2-methoxymethylbiphenyl, 3-methoxymethylbiphenyl, 4-methoxymethylbiphenyl, 1,2-bis (methoxymethyl) benzene, 1,3-bis (methoxymethyl) benzene, 1,4-bis (methoxymethyl) benzene, 1,2-bis (ethoxymethyl) benzene, 1,3-bis (ethoxymethyl) benzene, 1,4-bis ( Ethoxymethyl) benzene, 2,4'-bi (Methoxymethyl) biphenyl, 3,4'-bis (methoxymethyl) biphenyl, 4,4'-bis (methoxymethyl) biphenyl, 2,4'-bis (methoxymethyl) diphenyl ether, 3,4'-bis ( Methoxymethyl) diphenyl ether, 4,4′-bis (methoxymethyl) diphenyl ether, 2,4′-bis (methoxymethyl) diphenylmethane, 3,4′-bis (methoxymethyl) diphenylmethane, 4,4′-bis (methoxymethyl) ) Diphenylmethane, 2,4′-bis (methoxymethyl) diphenylsulfone, 3,4′-bis (methoxymethyl) diphenylsulfone, 4,4′-bis (methoxymethyl) diphenylsulfone, 2,4′-bis (methoxy) Methyl) diphenylpropane, 3,4'-bis (methoxymethyl) diphenyl Lopan, 4,4′-bis (methoxymethyl) diphenylpropane, 2,4′-bis (methoxymethyl) diphenylhexafluoropropane, 3,4′-bis (methoxymethyl) diphenylhexafluoropropane, 4,4′- Examples of those having three or more include bis (methoxymethyl) diphenylhexafluoropropane and the like:

{In the formula, L may be the same as or different from each other, and represents a methoxymethyl group, ethoxymethyl group, propoxymethyl group, methoxyethyl group, ethoxyethyl group, methoxypropyl group or methoxyisopropyl group. }.

｛式中、Ｒ^１は、メチル基、エチル基、ｎ−プロピル基、及びイソプロピル基からなる群から選ばれる１価の有機基であり、Ｒ^２は、水素原子、炭素数１〜４のアルキル基、炭素数２〜１０のエステル基、及び炭素数２〜１０のウレタン基からなる群より選ばれる１価の有機基であり、ｎは、１〜３の整数であり、ｐは、１〜５の整数であり、ｑは、０〜４の整数であり、（ｐ＋ｑ）＝５であり、ｋは、１又は２であり、（ｉ）ｋ＝１のとき、Ｘは、Ｃ_ｎＨ_２ｎＯＲ^１又はＲ^２であり、（ｉｉ）ｋ＝２のとき、Ｘは、単結合又は下記一般式（４）：

で表される基から選ばれる２〜４価の有機基を示す。但し、Ｃ_ｎＨ_２ｎＯＲ^１及びＲ^２が複数存在する場合、ｎ、ｐ、ｑ、Ｒ^１、及びＲ^２は、互いに同一でも異なっていてもよい。｝。Furthermore, from the viewpoint of dissolution time (development time) during alkali development, the (B) alkoxyalkyl group-containing compound of the present invention is at least one selected from the group consisting of compounds represented by the following general formula (3). Alkoxyalkyl group-containing compounds are preferred:

{Wherein R ¹ is a monovalent organic group selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, and R ² is a hydrogen atom, an alkyl having 1 to 4 carbon atoms. A monovalent organic group selected from the group consisting of a group, an ester group having 2 to 10 carbon atoms, and a urethane group having 2 to 10 carbon atoms, n is an integer of 1 to 3, and p is 1 to 1 5 is an integer of 5; q is an integer of 0 to 4; (p + q) = 5; k is 1 or 2; (i) when k = 1, X is C _n H _2n is oR ¹ or ^{R 2,} (ii) when k = 2, X is a single bond or the following general formula (4):

A divalent to tetravalent organic group selected from the group represented by: However, when there are a plurality of C _n H _2n OR ¹ and R ² , n, p, q, R ¹ , and R ² may be the same as or different from each other. }.

｛式中、Ｌは、互いに同じであっても異なっていてもよく、メトキシメチル基、エトキシメチル基、プロポキシメチル基、メトキシエチル基、エトキシエチル基、メトキシプロピル基又はメトキシイソプロピル基を示す。｝
が挙げられる。Specific examples include methoxymethylbenzene, ethoxymethylbenzene, methoxyethylbenzene, ethoxymethylbenzene, 2-methoxymethyltoluene, 3-methoxymethyltoluene, 4-methoxymethyltoluene, 2-methoxymethylbiphenyl, 3-methoxymethylbiphenyl, 4-methoxymethylbiphenyl, 1,2-bis (methoxymethyl) benzene, 1,3-bis (methoxymethyl) benzene, 1,4-bis (methoxymethyl) benzene, 1,2-bis (ethoxymethyl) benzene, 1,3-bis (ethoxymethyl) benzene, 1,4-bis (ethoxymethyl) benzene, 2,4′-bis (methoxymethyl) biphenyl, 3,4′-bis (methoxymethyl) biphenyl, 4,4 ′ -Bis (methoxymethyl) biphenyl, 2,4'-bis (Methoxymethyl) diphenyl ether, 3,4'-bis (methoxymethyl) diphenyl ether, 4,4'-bis (methoxymethyl) diphenyl ether, 2,4'-bis (methoxymethyl) diphenylmethane, 3,4'-bis (methoxy) Methyl) diphenylmethane, 4,4′-bis (methoxymethyl) diphenylmethane, 2,4′-bis (methoxymethyl) diphenylsulfone, 3,4′-bis (methoxymethyl) diphenylsulfone, 4,4′-bis (methoxy) Methyl) diphenylsulfone, 2,4′-bis (methoxymethyl) diphenylpropane, 3,4′-bis (methoxymethyl) diphenylpropane, 4,4′-bis (methoxymethyl) diphenylpropane, 2,4′-bis (Methoxymethyl) diphenylhexafluoropropane, 3, '- bis (methoxymethyl) diphenyl hexafluoropropane, 4,4'-bis (methoxymethyl) diphenyl hexafluoropropane, etc., and the following compounds:

{In the formula, L may be the same or different from each other, and represents a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a methoxyethyl group, an ethoxyethyl group, a methoxypropyl group or a methoxyisopropyl group. }
Is mentioned.

｛式中、Ｒ^１は、メチル基、エチル基、ｎ−プロピル基、及びイソプロピル基からなる群から選ばれる１価の有機基であり、ｎは、１〜３の整数であり、ｐは、１〜５の整数であり、ｋは、１又は２であり、（ｉ）ｋ＝１のとき、Ｘは、水素原子又はＣ_ｎＨ_２ｎＯＲ^１であり、（ｉｉ）ｋ＝２のとき、Ｘは、単結合又は下記一般式（６）：

で表される群から選ばれる２〜４価の有機基を示す。但し、（Ｃ_ｎＨ_２ｎＯＲ^１）が複数存在する場合、ｎ及びＲ^１は互いに同一でも異なっていてもよい。｝。Furthermore, from the viewpoint of heat resistance of the crosslinked structure by curing, the (B) alkoxyalkyl group-containing compound of the present invention is at least one alkoxyalkyl group selected from the group consisting of compounds represented by the following general formula (5). Preferred compounds are:

{In the formula, R ¹ is a monovalent organic group selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, n is an integer of 1 to 3, and p is An integer of 1 to 5, k is 1 or 2, (i) when k = 1, X is a hydrogen atom or C _n H _2n OR ¹ , and (ii) when k = 2, X is a single bond or the following general formula (6):

A divalent to tetravalent organic group selected from the group represented by: However, when there are a plurality of (C _n H _2n OR ¹ ), n and R ¹ may be the same as or different from each other. }.

｛式中、Ｌは、互いに同じであっても異なっていてもよく、メトキシメチル基、エトキシメチル基、プロポキシメチル基、メトキシエチル基、エトキシエチル基、メトキシプロピル基又はメトキシイソプロピル基を示す。｝が挙げられる。Specific examples include methoxymethylbenzene, ethoxymethylbenzene, methoxyethylbenzene, ethoxymethylbenzene, 2-methoxymethyltoluene, 3-methoxymethyltoluene, 4-methoxymethyltoluene, 2-methoxymethylbiphenyl, 3-methoxymethylbiphenyl, 4-methoxymethylbiphenyl, 1,2-bis (methoxymethyl) benzene, 1,3-bis (methoxymethyl) benzene, 1,4-bis (methoxymethyl) benzene, 1,2-bis (ethoxymethyl) benzene, 1,3-bis (ethoxymethyl) benzene, 1,4-bis (ethoxymethyl) benzene, 2,4′-bis (methoxymethyl) biphenyl, 3,4′-bis (methoxymethyl) biphenyl, 4,4 ′ -Bis (methoxymethyl) biphenyl, 2,4'-bis (Methoxymethyl) diphenyl ether, 3,4'-bis (methoxymethyl) diphenyl ether, 4,4'-bis (methoxymethyl) diphenyl ether, 2,4'-bis (methoxymethyl) diphenylmethane, 3,4'-bis (methoxy) Methyl) diphenylmethane, 4,4′-bis (methoxymethyl) diphenylmethane, 2,4′-bis (methoxymethyl) diphenylsulfone, 3,4′-bis (methoxymethyl) diphenylsulfone, 4,4′-bis (methoxy) Methyl) diphenylsulfone, 2,4′-bis (methoxymethyl) diphenylpropane, 3,4′-bis (methoxymethyl) diphenylpropane, 4,4′-bis (methoxymethyl) diphenylpropane, 2,4′-bis (Methoxymethyl) diphenylhexafluoropropane, 3, '- bis (methoxymethyl) diphenyl hexafluoropropane, 4,4'-bis (methoxymethyl) diphenyl hexafluoropropane, etc., and the following compounds:

{In the formula, L may be the same or different from each other, and represents a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a methoxyethyl group, an ethoxyethyl group, a methoxypropyl group or a methoxyisopropyl group. }.

  Furthermore, from the viewpoint of the effect of suppressing the shrinkage of the film thickness due to curing, the (B) alkoxyalkyl group-containing compound of the present invention includes methoxymethylbiphenyl, bis (methoxymethyl) benzene, bis (methoxymethyl) biphenyl, bis (methoxymethyl). ) At least one compound selected from the group consisting of diphenyl ether and bis (methoxymethyl) diphenylmethane is particularly preferred.

  Further, from the viewpoint of the chemical resistance of the cured film, tris (methoxymethyl) benzene, tetrakis (methoxymethyl) benzene, pentakis (methoxymethyl) benzene, hexakis (methoxymethyl) benzene, tris (methoxymethyl) trimethoxybenzene, and Particularly preferred is at least one compound selected from the group consisting of tetrakis (methoxymethyl) dimethoxybenzene.

｛式中、Ｚ_１は、下記一般式（８）：

（式中、Ｒ^３〜Ｒ^５は、それぞれ独立に、炭素数１〜９の有機基であり、Ｒ^６は、メチル基、エチル基、ｎ−プロピル基、及びイソプロピル基からなる群から選ばれる１価の有機基であり、そしてＲ^７〜Ｒ^１０は、それぞれ独立に、炭素数１〜１２の有機基である。）で表される基から選ばれる置換基であり、ｋは、１〜４の整数であり、（ｉ）ｋ＝１のとき、Ｚ^２は、Ｃ_ｎＨ_２ｎＯＲ^１又はＲ^２であり、Ｒは、それぞれ独立に、メチル基又はエチル基であり、Ｒ^１は、メチル基、エチル基、ｎ−プロピル基、及びイソプロピル基からなる群から選ばれる１価の有機基であり、Ｒ^２は、水素原子、及び炭素数１〜４のアルキル基からなる群より選ばれる１価の有機基であり、ｎは、１〜３の整数であり、（ｉｉ）ｋ＝２〜４のとき、Ｚ^２は、単結合又は２〜４価の有機基であり、Ｚ^１が複数存在する場合、Ｚ^１は同一であっても異なっていてもよい。｝で表される化合物からなる群より選ばれる少なくとも一種のアルコキシアルキル基含有化合物であることが好ましい。アルコキシアルキル基含有化合物は、相当する下記一般式（１４）：

｛式中、ｋは、１〜４の整数であり、（ｉ）ｋ＝１のとき、Ｚ^２は、Ｃ_ｎＨ_２ｎＯＲ^１又はＲ^２であり、Ｒ^１は、メチル基、エチル基、ｎ−プロピル基、及びイソプロピル基からなる群から選ばれる１価の有機基であり、Ｒ^２は、水素原子、及び炭素数１〜４の炭化水素基からなる群より選ばれる１価の有機基であり、ｎは、１〜３の整数であり、（ｉｉ）ｋ＝２〜４のとき、Ｚ^２は単結合又は２〜４価の有機基を示す。｝で表されるアルコキシアルキル基含有フェノールと、イソシアネート化合物、カルボン酸クロリド、スルホン酸無水物、及びスルホニルクロリド、シリルクロリド等を、適当な溶剤中で反応させることにより、得ることができる。The photosensitive resin composition of the present invention is (B) the following general formula (7):
The following general formula (7):

{In the formula, Z ₁ represents the following general formula (8):

(In the formula, R ^{3 to} R ⁵ are each independently an organic group having 1 to 9 carbon atoms, and R ⁶ is selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Is a monovalent organic group, and R ^{7 to} R ¹⁰ are each independently a substituent selected from a group represented by a C 1-12 organic group. 4 and (i) when k = 1, Z ² is C _n H _2n OR ¹ or R ² , R is independently a methyl group or an ethyl group, and R ¹ is A monovalent organic group selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, and R ² is selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms. A monovalent organic group, n is an integer of 1 to 3, and (ii) when k = 2 to 4 , Z ² is a single bond or a divalent to tetravalent organic group, and when a plurality of Z ¹ are present, Z ¹ may be the same or different. Are at least one alkoxyalkyl group-containing compound selected from the group consisting of compounds represented by: The alkoxyalkyl group-containing compound has the following general formula (14):

{Wherein k is an integer of 1 to 4, and (i) when k = 1, Z ² is C _n H _2n OR ¹ or R ² , R ¹ is a methyl group, an ethyl group, a monovalent organic group selected from the group consisting of an n-propyl group and an isopropyl group, and R ² is a monovalent organic group selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 4 carbon atoms. and a, n is an integer of 1 to 3, when ^{(ii) k = 2~4, Z} 2 is a single bond or a divalent to tetravalent organic group. } Is reacted with an isocyanate compound, carboxylic acid chloride, sulfonic acid anhydride, sulfonyl chloride, silyl chloride, and the like in an appropriate solvent.

｛式中、Ｒは、それぞれ独立に、メチル基又はエチル基であり、Ｚ^３は、単結合又は下記一般式（１６）：

に示す基から選ばれる置換基を示す。｝に示すアルコキシアルキル基含有フェノール化合物が挙げられる。As one of the alkoxyalkyl group-containing phenol compounds represented by the general formula (8), the following general formula (15):

{In the formula, each R is independently a methyl group or an ethyl group, and Z ³ is a single bond or the following general formula (16):

And a substituent selected from the groups shown below. } The alkoxyalkyl group containing phenolic compound shown to} is mentioned.

｛式中、Ｒは、互いに同じであっても異なっていてもよく、メチル基又はエチル基を示す。｝に示すアルコキシアルキル基含有フェノールを用いることが好ましく、さらにその中でも、耐熱性の観点から、下記一般式（１８）：

｛式中、Ｒは、互いに同じであっても異なっていてもよく、メチル基又はエチル基を示す。｝に示すアルコキシアルキル基含有フェノール化合物を用いることが最も好ましい。Among these, from the viewpoint of the sensitivity of the resin composition, the following general formula (17):

{In the formula, R may be the same or different from each other, and represents a methyl group or an ethyl group. } It is preferable to use an alkoxyalkyl group-containing phenol represented by the following general formula (18) from the viewpoint of heat resistance:

{In the formula, R may be the same or different from each other, and represents a methyl group or an ethyl group. } It is most preferable to use an alkoxyalkyl group-containing phenol compound represented by

｛式中、Ｒ^３〜Ｒ^５は、それぞれ独立に、炭素数１〜９の有機基であり、Ｒ^６は、メチル基、エチル基、ｎ−プロピル基、及びイソプロピル基からなる群から選ばれる１価の有機基であり、そしてＲ^７〜Ｒ^１０は、それぞれ独立に、炭素数１〜１２の有機基である。｝に示す化合物が挙げられる。As a compound to be reacted with an alkoxyalkyl group-containing phenol, the following general formula (19):

{Wherein R ^{3 to} R ⁵ are each independently an organic group having 1 to 9 carbon atoms, and R ⁶ is selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. It is a monovalent organic group, and R < ⁷ > -R < ¹⁰ > is a C1-C12 organic group each independently. } The compound shown to} is mentioned.

  Examples of the compound represented by the general formula (19) include acetyl chloride, cyclopropanecarbonyl chloride, oxalic acid monoethyl chloride, tert-butylacetyl chloride, 3-cyclohexene-1-carboxylic acid chloride, and 2-furancarboxylic acid chloride. , Crotonic acid chloride, cinnamic acid chloride, methacrylic acid chloride, acrylic acid chloride, propiolic acid chloride, tetrolic acid chloride, thiophene-2-acetyl chloride, 2-ethoxybenzoyl chloride, 2-methoxybenzoyl chloride, 4-methoxybenzoyl chloride , Trimellitic acid chloride, 3,5,5-trimethylhexanoyl chloride, 2,4,6-trimethylbenzoyl chloride, 4-nitrophenyl chloroformate, 9-fluorenylmethylchlorophore , Di-tert-butyl dicarbonate, dibenzyl dicarbonate, 4-ethylbenzenesulfonyl chloride, p-toluenesulfonyl chloride, benzenesulfonyl chloride, p-xylene-2-sulfonyl chloride, 2-mesitylenesulfonyl chloride, 4-propylbenzene Sulfonyl chloride, 4-methoxybenzenesulfonyl chloride, 4-tert-butylbenzenesulfonyl chloride, 4-biphenylsulfonyl chloride, 2,4,6-triisopropylbenzenesulfonyl chloride, methanesulfonyl chloride, phenyl isocyanate, isocyanate ethyl methacrylate, 3 -Isopropenyl-α, α-dimethylbenzyl isocyanate, isocyanate-2-trifluoromethylphenyl, n-butyl isocyanate, n isocyanate Octadecyl, o-tolyl isocyanate, chlorodimethylsilane, trimethylchlorosilane, chlorotriethylsilane, chlorodiisopropylsilane, diethylisopropylsilyl chloride, tert-butyldimethylchlorosilane, dimethylethylchlorosilane, dimethylisopropylchlorosilane, triisopropylsilyl chloride, chlorodimethylpropyl Silane, allylchlorodimethylsilane, n-butyldimethylchlorosilane, chlorodimethylvinylsilane, dimethyl-n-octylchlorosilane, chloro (decyl) dimethylsilane, chloro (dodecyl) dimethylsilane, (3-cyanopropyl) dimethylchlorosilane, (chloromethyl) ) Dimethylchlorosilane, (bromomethyl) chlorodimethylsilane, etc. Chill chlorosilane, p- toluenesulfonyl chloride, chloride of methacrylic acid, chloride crotonate. Among these, methacrylic acid chloride is most preferable from the viewpoint of solubility in an organic solvent.

  Solvents used for synthesizing the compound represented by the general formula (7) include acetone, tetrahydrofuran (THF), γ-butyrolactone (GBL), N-methyl-2-pyrrolidone (NMP), N, N-dimethyl. Examples include acetamide (DMAc) and dimethyl sulfoxide (DMSO).

  Further, in order to accelerate the reaction when synthesizing the present compound, it is preferable to coexist a basic compound such as pyridine, picoline, collidine, lutidine, triethylamine, 4-dimethylaminopidine. The basic catalysts may be used alone or in combination of two or more. The amount of the basic catalyst used can be adjusted according to the type of the basic catalyst, and can be selected from a range of 0.01 to 10 equivalents (molar equivalent) with respect to 1 mol of the alkoxyalkyl group-containing phenol compound as a raw material. Usually, it is 0.1-5 equivalent, More preferably, it is about 1-3 equivalent.

  It is preferable to control reaction temperature between 10 degreeC-50 degreeC, and 10 degreeC-30 degreeC is preferable in highly reactive compounds, such as carboxylic acid chloride and a sulfonyl chloride. The reaction time varies depending on the amount and type of the compound to be reacted and the catalyst, and is preferably 1 hour to 48 hours. For highly reactive compounds such as carboxylic acid chloride and sulfonyl chloride, about 1 hour to 5 hours is preferred.

  As a method for removing the basic compound contained in the alkoxyalkyl group-containing compound synthesized in this way, after reprecipitating in a poor solvent such as water, it is redissolved in a solvent such as THF, and a cation One method is treatment with an exchange resin. When synthesizing this compound, when a halide such as carboxylic acid chloride is used, it is possible to precipitate the salt out of the reaction system by selecting a solvent for the catalyst and collect the salt by filtration. It is preferable to treat the filtrate not only with a cation exchange resin but also with an anion exchange resin. The treated solution is concentrated by evaporation, dissolved in a good solvent such as ethyl acetate, recrystallized in a poor solvent such as hexane, and vacuum dried to isolate the target product.

｛式中、Ｒは、それぞれ独立に、メチル基又はエチル基であり、Ｚ^１は、それぞれ独立に、下記一般式（１０）：

（式中、Ｒ^３〜Ｒ^５は、それぞれ独立に、炭素数１〜９の有機基であり、Ｒ^６は、メチル基、エチル基、ｎ−プロピル基、及びイソプロピル基からなる群から選ばれる１価の有機基であり、そしてＲ^７〜Ｒ^１０は、それぞれ独立に、炭素数１〜１２の有機基である。）で表される基から選ばれる置換基であり、Ｚ^３は、単結合又は下記一般式（１１）：

で表される基から選ばれる置換基である。｝で表されるアルコキシアルキル基含有化合物である。中でも、一般式（９）において、Ｚ^３は、単結合であり、Ｚ^１は、それぞれ独立に、下記一般式（１２）：

｛式中、Ｒ^３及びＲ^５は、それぞれ独立に、炭素数１〜９の有機基であり、そしてＲ^７は、炭素数１〜１２の有機基である。｝で表されるアルコキシアルキル基含有化合物が好ましい。更に、一般式（９）において、Ｚ^３は、単結合であり、Ｚ^１は、それぞれ独立に、下記一般式（１３）：

で表される基から選ばれる置換基であるアルコキシアルキル基含有化合物が、耐熱性の観点から好ましい。The alkoxyalkyl group-containing compound obtained by the above method has the following general formula (9):

{In the formula, each R is independently a methyl group or an ethyl group, and each Z ¹ independently represents the following general formula (10):

(In the formula, R ^{3 to} R ⁵ are each independently an organic group having 1 to 9 carbon atoms, and R ⁶ is selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. a monovalent organic group, and ^R 7 ^{to R 10} are each independently a substituent selected from the group represented by is an organic group having 1 to 12 carbon atoms.), ^{Z 3} is a single Bond or the following general formula (11):

Is a substituent selected from the group represented by: } It is an alkoxyalkyl group containing compound represented by this. Among them, in the general formula (9), Z ³ is a single bond, and each Z ¹ independently represents the following general formula (12):

{In the formula, R ³ and R ⁵ are each independently an organic group having 1 to 9 carbon atoms, and R ⁷ is an organic group having 1 to 12 carbon atoms. } An alkoxyalkyl group-containing compound represented by Further, in the general formula (9), ^{Z 3} is a single bond, ^{Z 1} is each independently represented by the following general formula (13):

An alkoxyalkyl group-containing compound that is a substituent selected from the group represented by formula (II) is preferred from the viewpoint of heat resistance.

(B) The alkoxyalkyl group-containing compound may be used alone or in combination of two or more.
(B) The compounding quantity of an alkoxyalkyl group containing compound is 0.01-30 mass parts with respect to 100 mass parts of (A) hydroxy polyamide, and 1-20 mass parts is preferable. (B) When the compounding amount of the alkoxyalkyl group-containing compound is 1 part by mass or more, the remaining film ratio after curing ((film thickness of relief pattern after curing) / (film thickness of relief pattern after development) × 100) And the sensitivity is good when it is 30 parts by mass or less.

｛式中、Ｑは、水素原子又は以下：

に示すナフトキノンジアジドスルホン酸エステル基であり、すべてのＱが同時に水素原子であることはない。｝のものが挙げられる。(C) Diazoquinone Compound The diazoquinone compound used in the photosensitive resin composition is a compound having a 1,2-benzoquinone diazide structure or a 1,2-naphthoquinone diazide structure, and is disclosed in US Pat. 797, 213, 3,669, 658 and the like. Examples of preferred ones include, for example:

{Wherein Q is a hydrogen atom or the following:

The naphthoquinonediazide sulfonic acid ester group shown in the following, and not all Q are hydrogen atoms at the same time. }.

。Among these, particularly preferred are:

.

  (C) The compounding quantity of a diazoquinone compound is 1-100 mass parts with respect to 100 mass parts of (A) hydroxy polyamide, and 10-30 mass parts is preferable. (C) When the blending amount of the diazoquinone compound is 1 part by mass or more, the patterning property of the resin is good. On the other hand, when it is 100 parts by mass or less, the tensile elongation of the cured film is good and the development residue (scum) in the exposed part Less is.

  A thermal radical generator may be added to the photosensitive resin composition. The radical generator used here is preferably one that generates radicals under heat treatment conditions, and examples of preferable ones include organic peroxides such as dicumyl peroxide and organic non-peroxides such as dimethyldiphenylbutane.

  When the thermal radical generator is added, the addition amount is preferably 0 to 20 parts by mass and more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of (A) hydroxypolyamide. If the addition amount is within 20 parts by mass, the storage stability is good.

In the photosensitive resin composition, if necessary, a phenol compound, a dye, a surfactant, an adhesion aid for increasing the adhesion to the substrate, a stability, which are conventionally used as additives of the photosensitive resin composition, It is also possible to add an agent or the like.
More specifically, the additive may be a ballast agent, paracumylphenol, bisaminophenol, resorcinol, or the like. In addition, a ballast agent means the phenol compound currently used as a raw material for the above-mentioned diazoquinone compound which is a phenol compound in which a part of the phenolic hydrogen atom is converted to naphthoquinonediazide sulfonic acid ester. Examples of the dye include methyl violet, crystal violet, and malachite green.

The addition amount in the case of adding a phenol compound is preferably 0 to 50 parts by mass and more preferably 1 to 30 parts by mass with respect to 100 parts by mass of (A) hydroxypolyamide. If the addition amount is within 50 parts by mass, the tensile elongation of the film after thermosetting is good.
In addition, as the surfactant, for example, nonionic surfactants made of polyglycols such as polypropylene glycol or polyoxyethylene lauryl ether or derivatives thereof, such as Fluorard (registered trademark, trade name, manufactured by Sumitomo 3M), Fluorosurfactants such as Megafuck (registered trademark, trade name, manufactured by Dainippon Ink and Chemicals) or Lumiflon (registered trademark, trade name, manufactured by Asahi Glass), such as KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) And organosiloxane surfactants such as DBE (trade name, manufactured by Chisso Corporation) and Granol (trade name, manufactured by Kyoeisha Chemical Co., Ltd.).

  0-10 mass parts is preferable with respect to 100 mass parts of (A) hydroxy polyamide, and, when adding surfactant, 0.01-1 mass part is more preferable. If the addition amount is within 10 parts by mass, the tensile elongation of the film after thermosetting is good. By adding the surfactant, it is possible to make it more difficult for the coating film to be repelled at the wafer edge during coating.

  Examples of the adhesion assistant include alkyl imidazoline, butyric acid, alkyl acid, polyhydroxystyrene, polyvinyl methyl ether, t-butyl novolac, epoxy silane, epoxy polymer, and various silane coupling agents.

  Specific preferred examples of the silane coupling agent include, for example, N-phenyl-3-aminopropyltrialkoxysilane, 3-mercaptopropyltrialkoxysilane, 2- (trialkoxysilylethyl) pyridine, and 3-methacryloxypropyl. Trialkoxysilane, 3-methacryloxypropyl dialkoxyalkylsilane, 3-glycidoxypropyltrialkoxysilane, 3-glycidoxypropyl dialkoxyalkylsilane, 3-aminopropyltrialkoxysilane or 3-aminopropyl dialkoxyalkyl Silane and acid anhydride or dianhydride reactant, 3-aminopropyltrialkoxysilane or 3-aminopropyl dialkoxyalkylsilane amino group converted to urethane group or urea group Etc. can be mentioned. In this case, methyl group, ethyl group, butyl group, etc. as the alkyl group, maleic anhydride, phthalic anhydride, etc. as the acid anhydride, pyromellitic dianhydride as the acid dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, etc., t-butoxycarbonylamino group as a urethane group, phenylamino as a urea group Examples thereof include a carbonylamino group.

The addition amount in the case of adding an adhesion assistant is preferably 0 to 30 parts by mass and more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of (A) hydroxypolyamide. If the addition amount is within 30 parts by mass, the tensile elongation of the film after thermosetting is good.
The above-described photosensitive resin composition can be dissolved in a solvent to form a varnish and used as a photosensitive resin composition solution.

  Examples of such a solvent include N-methyl-2-pyrrolidone, γ-butyrolactone (hereinafter also referred to as “GBL”), isophorone, N, N-dimethylacetamide (hereinafter also referred to as “DMAc”), dimethylimidazo. Linone, tetramethylurea, dimethyl sulfoxide, diethylene glycol dimethyl ether (hereinafter also referred to as “DMDG”), diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl Ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol 3-monomethyl ether, methyl pyruvate, ethyl pyruvate, may be used alone or as a mixture of methyl 3-methoxy propionate or the like. Among these solvents, non-amide solvents are preferable because they have little influence on photoresists, and specifically, γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate. And so on.

  The addition amount of the solvent is preferably 50 to 1000 parts by mass with respect to 100 parts by mass of the hydroxy polyamide. The addition amount of the solvent is preferably set to a viscosity suitable for the coating apparatus and the coating thickness within the above range, because the production of the cured relief pattern can be facilitated.

<Curing relief pattern and method for manufacturing semiconductor device>
Hereinafter, a method for producing a cured relief pattern by applying the photosensitive resin composition of the present invention to a substrate will be specifically described.
(1) A step of forming a photosensitive resin layer made of a photosensitive resin composition on a substrate (first step).
The photosensitive resin composition solution is applied to a substrate such as a silicon wafer, a ceramic substrate, or an aluminum substrate by spin coating using a spin coater or a coater such as a die coater or a roll coater. Or it is also possible to apply | coat to a predetermined place using an inkjet nozzle or a dispenser. This is dried at 50 to 140 ° C. using an oven or a hot plate to remove the solvent (“pre-bake”).

(2) A step of exposing with active light through a mask or directly irradiating with a light beam, an electron beam or an ion beam (second step).
Subsequently, the photosensitive resin layer is exposed to actinic rays through a mask, that is, exposed to actinic radiation using a contact aligner or a stepper. Alternatively, exposure is performed by directly irradiating a light beam, an electron beam or an ion beam. As the actinic ray, g-line, h-line, i-line, or KrF laser can also be used.

(3) Step of developing (third step)
As a third step, the exposed portion or irradiated portion is eluted or removed with a developer. Subsequently, a desired relief pattern is obtained preferably by rinsing with a rinsing liquid. As a developing method, methods such as spray, paddle, dip, and ultrasonic can be used. Distilled water, deionized water, etc. can be used for the rinse liquid.
The developer used for developing the photosensitive resin layer made of the photosensitive resin composition dissolves and removes the alkali-soluble polymer, and needs to be an alkaline aqueous solution in which an alkali compound is dissolved. The alkali compound dissolved in the alkaline aqueous solution may be either an inorganic alkali compound or an organic alkali compound.

  Examples of the inorganic alkali compound include lithium hydroxide, sodium hydroxide, potassium hydroxide, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, lithium silicate, sodium silicate, potassium silicate. , Lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, sodium borate, potassium borate, and ammonia.

Examples of the organic alkali compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, methylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, n-propylamine, diethylamine. -N-propylamine, isopropylamine, diisopropylamine, methyldiethylamine, dimethylethanolamine, ethanolamine, triethanolamine.
Furthermore, if necessary, an appropriate amount of a water-soluble organic solvent such as methanol, ethanol, propanol, or ethylene glycol, a surfactant, a storage stabilizer, a resin dissolution inhibitor, or the like can be added to the alkaline aqueous solution.

(4) Step of heating the obtained relief pattern (fourth step)
Finally, the obtained relief pattern is heat-treated to form a heat-resistant cured relief pattern made of a resin having a polybenzoxazole structure. As the heating device, an oven furnace, a hot plate, a vertical furnace, a belt conveyor furnace, a pressure oven, or the like can be used. As a heating method, heating by hot air, infrared rays, electromagnetic induction, or the like is recommended. The temperature is preferably 200 to 450 ° C, more preferably 250 to 400 ° C.
The heating time is preferably 15 minutes to 8 hours, and more preferably 1 hour to 4 hours.
The atmosphere is preferably in an inert gas such as nitrogen or argon. A semiconductor device combines a cured relief pattern with a known semiconductor device manufacturing method as a surface protective film, an interlayer insulating film, a rewiring insulating film, a protective film for a flip chip device, or a protective film for a device having a bump structure. Can be manufactured.
The photosensitive resin composition of the present invention is also useful for applications such as interlayer insulation of multilayer circuits, cover coating of flexible copper-clad plates, solder resist films, or liquid crystal alignment films.

The present invention will be described based on reference examples and examples. Evaluation of the photosensitive resin composition in an Example followed the following method.
<Evaluation of photosensitive resin composition>
(1) Evaluation of patterning characteristics The photosensitive resin composition was spin-coated on a 5-inch silicon wafer with a spin coater (Dspin SW-636, manufactured by Dainippon Screen Mfg. Co., Ltd.), and heated at 125 ° C. and 180 ° C. Pre-baking was performed for 2 seconds to form a coating film having a film thickness of 9.0 μm. This coating film is heat-treated (cured) at 320 ° C. for 1 hour in a nitrogen atmosphere using a temperature rising program type curing furnace (VF-2000 type, manufactured by Koyo Lindberg Co., Ltd.) to form a cured film on the silicon wafer. I got it. The film thickness was measured with an optical film thickness measuring device (Lambda Ace VM-1200, manufactured by Dainippon Screen Mfg. Co., Ltd.) with a refractive index of 1.65. The cure shrinkage rate (%) was calculated from the film thickness before and after the cure.

  Next, the photosensitive resin composition was spin-coated on a 5-inch wafer by the method described above to form a coating film. This coating film was exposed through a reticle with a test pattern by using a Nikon stepper (NSR2005i8A) having an exposure wavelength of i-line (365 nm) while changing the exposure stepwise. Using an alkali developer (AZ300MIF developer, 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution) manufactured by AZ Electric Materials, the development time was such that the development residual film ratio in the unexposed area was 85%. Then, paddle development was performed at 23 ° C. and rinsed with pure water to form a positive relief pattern. Thereafter, curing was performed at 320 ° C. for 1 hour. At this time, the applied film thickness of the coating film was set by calculating backward from the cure shrinkage so that the final film thickness of the relief pattern obtained by performing the curing at 320 ° C. for 1 hour was 7.0 μm.

In addition, the sensitivity of the photosensitive resin composition, the resolution, the temporal stability of the sensitivity after exposure, and the storage stability were evaluated as follows.
[Sensitivity (mJ / cm ² )]
The minimum exposure amount that can completely dissolve and remove the exposed portion of the coating film during the development time.
[Resolution (μm)]
Minimum resolution pattern size at the above exposure.
[Stability of sensitivity after exposure]
The photosensitive resin composition was spin-coated on a 5-inch wafer by the method described above to form a coating film, and this coating film was exposed by the method described above, and then left in a clean room for 24 hours. Then, it developed by the method mentioned above and formed the relief pattern. In this case, change with time of sensitivity after exposure and good than ^{± 50 (mJ / cm 2)} , and defective or more ^{± 50 (mJ / cm 2)} .
[Storage stability evaluation]
The above-mentioned photosensitive resin composition was measured for viscosity at 23 ° C. using an E-type viscometer (RE-80E, manufactured by Toki Sangyo Co., Ltd.), allowed to stand at room temperature for 2 weeks, and then measured for viscosity again. The change rate (thickening rate) was calculated. A viscosity change of less than ± 5% was considered good, and a viscosity change of ± 5% or more was judged poor.

<Synthesis of hydroxy polyamide>
[Reference Example 1]
In a 2 L separable flask, 197.8 g (0.54 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 75.9 g (0.96 mol) of pyridine and 692 g of DMAc were added at room temperature. (25 ° C.) The mixture was stirred and dissolved. A solution obtained by dissolving 19.7 g (0.12 mol) of 5-norbornene-2,3-dicarboxylic anhydride in 88 g of DMDG was added dropwise thereto from a dropping funnel. The time required for the dropwise addition was 40 minutes, and the maximum reaction solution temperature was 28 ° C.
After completion of dropping, the mixture was heated to 50 ° C. with a hot water bath and stirred for 18 hours, and then the IR spectrum of the reaction solution was measured to confirm that characteristic absorption of imide groups at 1385 cm ⁻¹ and 1772 cm ⁻¹ appeared.

  Next, this was cooled to 8 ° C. with a water bath, and a solution prepared by dissolving 142.3 g (0.48 mol) of 4,4′-diphenyl ether dicarboxylic acid dichloride in 398 g of DMDG was added dropwise from the dropping funnel. The time required for the dropping was 80 minutes, and the maximum reaction solution temperature was 12 ° C. Three hours after the completion of the dropwise addition, the reaction solution was dropped into 12 liters of water under high-speed stirring to disperse and precipitate the polymer, which was recovered, washed with water as appropriate, dehydrated and then vacuum-dried. 1) was obtained. The weight average molecular weight of the thus synthesized hydroxy polyamide by GPC was 14,000 in terms of polystyrene. The analysis conditions for GPC are described below.

Column: Showa Denko Co., Ltd. Trade name: Shodex 805/804/803 in series Separation: Tetrahydrofuran 40 ° C
Flow rate: 1.0 ml / min Detector: Showa Denko brand name Shodex RI SE-61

[Reference Example 2]
In Reference Example 1, instead of 142.3 g (0.48 mol) of 4,4′-diphenyl ether dicarboxylic acid dichloride, 125.35 g (0.48 mol) of octahydro-1H-4,7-methanoindene dicarboxylic acid dichloride was replaced with 2 , 2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane instead of 197.8 g (0.54 mol), 2,2-bis (3-amino-4-hydroxyphenyl) -propane 139.45 g A polybenzoxazole resin precursor was obtained in the same manner as in Reference Example 1 except that (0.54 mol) was used (P-2). The polystyrene equivalent weight average molecular weight of this resin was 22000 (Mw).

[Reference Example 3]
In a 1 L separable flask, 109.9 g (0.3 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 330 g of tetrahydrofuran (THF), 47.5 g (0.6 mol) of pyridine. Into this, 98.5 g (0.6 mol) of 5-norbornene-2,3-dicarboxylic anhydride was added in powder form at room temperature. After stirring for 3 days at room temperature, the reaction was confirmed by HPLC. As a result, no starting material was detected and the product was detected as a single peak with a purity of 99%. This reaction solution was dropped as it was into 1 L of ion-exchanged water with stirring, and the precipitate was filtered off, and then 500 mL of THF was added to dissolve it with stirring. The remaining pyridine was removed. Next, this solution was dropped into 3 L of ion exchange water under high-speed stirring to precipitate a product, which was filtered off and then vacuum-dried.

The product is imidized, it not characteristic absorption of amide groups in the vicinity of 1540 cm ^-1 and 1650 cm ^-1 appear characteristic absorption of an imide group 1394Cm ^-1 and 1774 cm ^-1 in the IR spectrum is present and, NMR The spectrum was confirmed by the absence of amide and carboxylic acid proton peaks.
Next, 65.9 g (0.1 mol) of the product, 53.7 g (0.2 mol) of 1,2-naphthoquinonediazide-4-sulfonyl chloride and 560 g of acetone were added and dissolved by stirring at 20 ° C. A solution prepared by diluting 21.2 g (0.21 mol) of triethylamine with 106.2 g of acetone was added dropwise thereto at a constant rate over 30 minutes. At this time, the temperature of the reaction solution was controlled in the range of 20 to 30 ° C. using an ice water bath or the like.

  After completion of the dropwise addition, the mixture was allowed to stir at 20 ° C. for another 30 minutes, and then 5.6 g of a 36 wt% hydrochloric acid aqueous solution was added at once. The reaction solution was then cooled in an ice water bath, and the precipitated solid was filtered off with suction. . The filtrate obtained at this time was dropped into 5 L of a 0.5% by weight aqueous hydrochloric acid solution over 1 hour with stirring to precipitate the desired product, which was collected by suction filtration. The obtained cake-like recovered material was dispersed again in 5 L of ion-exchanged water, stirred, washed, collected by filtration, and this water washing operation was repeated three times. Finally, the cake-like material obtained was vacuum-dried at 40 ° C. for 24 hours to obtain a diazoquinone compound (Q-1).

[Reference Example 4]
In a 1 L separable flask, 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol (trade name Tris-P-PA-MF, Honshu Chemical Industry Co., Ltd.) (30.6 g, 0.1 mol), 1,2-naphthoquinonediazide-4-sulfonyl chloride (67.1 g, 0.25 mol), and acetone (560 g) were added and dissolved by stirring at 20 ° C. A solution prepared by diluting 26.2 g (0.26 mol) of triethylamine with 131.1 g of acetone was added dropwise thereto at a constant rate over 30 minutes. At this time, the temperature of the reaction solution was controlled in the range of 20 to 30 ° C. using an ice water bath or the like.
After completion of the dropwise addition, the mixture was allowed to stir at 20 ° C. for another 30 minutes, and then 5.6 g of a 36 wt% hydrochloric acid aqueous solution was added at once. The reaction solution was then cooled in an ice water bath, and the precipitated solid was filtered off with suction. . The filtrate obtained at this time was dropped into 5 L of a 0.5% by weight aqueous hydrochloric acid solution over 1 hour with stirring to precipitate the desired product, which was collected by suction filtration. The obtained cake-like recovered material was dispersed again in 5 L of ion-exchanged water, stirred, washed, collected by filtration, and this water washing operation was repeated three times. Finally, the cake-like product obtained was vacuum-dried at 40 ° C. for 24 hours to obtain a diazoquinone compound (Q-2).

[Reference Example 5]
235 g (1.4 mol) of 1,3,5-trimethoxybenzene, 156 g (5.19 mol) of acetaldehyde, and 532 g of glacial acetic acid were added to a 5 L separable flask equipped with a stir bar, a drying tube, and a thermometer. The slurry was stirred at 25 ° C. for 2 hours. When 2000 g of a mixed solution of 30% aqueous solution of hydrogen bromide and acetic acid equivalent to 7.41 mol was added dropwise thereto, heat was generated up to 56 ° C. The color of the solution changed from white to yellow and purple as dripping. After completion of the dropwise addition, the solution was completely dissolved when stirred at 70 ° C. for 50 minutes, and the reaction solution changed to brown when stirred for 3 hours. Thereafter, the mixture was cooled to 20 ° C., and the reaction solution was added to 7860 g of water. To this, 9000 g of chloroform was added, and the reaction product was extracted. To this, 4080 g of 5% sodium bicarbonate water and 600 g of sodium bicarbonate were added for washing. Thereafter, 4080 g of 20% saline is added, and 600 g of magnesium sulfate is further added to dehydrate, and the chloroform layer is filtered and washed, and then the solvent is distilled off by vacuum drying at 8 mmHg while heating the solvent to 50 ° C. to obtain 456 g of brown liquid. Of 1,3,5-trimethoxy-2,4,6-tribromomethylbenzene.

  Next, 108.28 g (0.2435 mol) of 1,3,5-tris (bromomethyl) -2,4,6-trimethoxymethylbenzene was added to a 1 L four-necked flask equipped with a stirrer, a nitrogen introducing tube and a thermometer. Was dissolved in 435 g of toluene. To this was added 235.05 g (1.217 mol) of a 28% sodium methoxide solution dropwise at around 23 ° C. over 8 minutes. After stirring at 35 ° C. for 27 hours, 46.97 g (1.0 mol) of 28% sodium methoxide solution was further added and stirred for 25 hours. This reaction liquid was poured into 2176 g of cold water at 5 ° C., 1741 g of toluene was further added, and the mixture was separated into an organic solvent layer and an aqueous layer. The aqueous layer was discarded by adding 1306 g of 20% brine and this was repeated three times. After adding 200 g of magnesium sulfate to the toluene layer and adding 300 ml of toluene, the magnesium sulfate was filtered and washed, and the toluene solvent was distilled off by vacuum drying at 10 mmHg while heating the solvent to 50 ° C. A crude product of the desired product was obtained, and this was subjected to column chromatogram purification with 3 kg of silica gel using a developing solvent in which hexane and ethanol were mixed at a ratio of 4: 1. The main chromatogram was recovered and vacuum dried at 50 ° C. for 40 hours. By performing, 56 g of 1,3,5-tris (methoxymethyl) -2,4,6-trimethoxybenzene was obtained. When the reaction was confirmed by HPLC, no starting material was detected, and the product was detected as a single peak with a purity of 99%.

[Reference Example 6]
In a 2.0 L four-necked flask equipped with a thermometer, a drying tube and a stirrer, 101.7 g (0.226 mol) of 1,2,4,5-tetrakis (bromomethyl) benzene (Aldrich) and Methanol 1.5 L was charged and stirred at room temperature. When 80.9 g (1.49 mol) of sodium methoxide was added thereto, the temperature increased by about 20 ° C. It was immersed in an oil bath at 65 ° C. and stirred at 65 ° C. for 4 hours. After the stirring was completed, 500 ml of methanol was distilled off using a rotary evaporator, and a concentration operation was performed. This concentrated reaction liquid was put into 2 L of ice water. After adding 2 L of toluene to this, it moved to the separatory funnel, extraction operation was performed, and the target object was extracted to the toluene layer. 50 g of magnesium sulfate was added thereto to perform a dehydration operation, and after magnesium sulfate was filtered off, toluene was distilled off using a rotary evaporator to obtain a crude product of interest. This was subjected to column chromatography purification using 600 g of silica gel using toluene and ethyl acetate as developing solvents. The main part was recovered and the solvent was distilled off again using a rotary evaporator to obtain 20 g of a purified product of 1,2,4,5-tetrakis (trimethoxymethyl) benzene. When the target product was confirmed by HPLC, no starting material was detected, and the product was detected as a single peak with a purity of 99%.

[Reference Example 7]
In a separable flask having a volume of 500 ml, 3,3 ′, 5,5′-tetrakis (methoxymethyl) -4,4′-dihydroxybiphenyl (trade name TMOM-BP, manufactured by Honshu Chemical Industry Co., Ltd. 36.2 g (0.1 mol), GBL 110 g, and pyridine 19.0 g (0.24 mol) were added, and 28.1 g (0.2 mol) of benzoic acid chloride was added dropwise. At this time, the temperature of the reaction solution was controlled in the range of 10 to 30 ° C. using an ice-water bath, and the reaction was stirred for 2 hours, and then the reaction was confirmed by HPLC. A single peak was detected with a purity of 99%. This reaction solution is dropped as it is into 1 L of ion-exchanged water with stirring, and the precipitate is separated by filtration. Then, 500 ml of GBL is added and dissolved by stirring, and this homogeneous solution is filled with a cation exchange resin and an anion exchange resin. The remaining chlorine ions and pyridine were removed through a glass column. Next, this solution was dropped into 3 L of ion-exchanged water under high-speed stirring to precipitate the product, which was filtered and dried under vacuum to obtain an alkoxyalkyl group-containing compound (C-1, structural formula It is shown below).

[Reference Example 8]
In Reference Example 7, all containing alkoxyalkyl groups in the same manner as in Reference Example 7 except that 21.0 g (0.2 mol) of methacrylic acid chloride was used instead of 28.1 g (0.2 mol) of benzoic acid chloride. A compound was obtained (C-2, structural formula is shown below). When the reaction was confirmed by HPLC, no starting material was detected, and the product was detected as a single peak with a purity of 99%.

[Reference Example 9]
In Reference Example 7, the same procedure as in Reference Example 7 was conducted except that 38.2 g (0.2 mol) of p-toluenesulfonic acid chloride was used instead of 28.1 g (0.2 mol) of benzoic acid chloride. An alkyl group-containing compound was obtained (C-3, the structural formula is shown below). When the reaction was confirmed by HPLC, no starting material was detected, and the product was detected as a single peak with a purity of 97.7%.

[Reference Example 10]
In Reference Example 7, instead of 3,3 ′, 5,5′-tetrakis (methoxymethyl) -4,4′-dihydroxybiphenyl 36.2 g (0.1 mol), 3,3 ′, 5,5′- Except for using 30.6 g (0.1 mol) of tetrakis (hydroxymethyl) -4,4′-dihydroxybiphenyl (trade name TML-BP, manufactured by Honshu Chemical Industry Co., Ltd., the structural formula is shown below) In the same manner as in Reference Example 7, a methylol group-containing compound was obtained (C-4, the structural formula is shown below). When the reaction was confirmed by HPLC, no starting material was detected, and the product was detected as a single peak with a purity of 99%.

[Example 1]
As an alkoxyalkyl group-containing compound, 20 parts by mass of the diazoquinone compound (Q-1) obtained in Reference Example 3 with respect to 100 parts by mass of the hydroxypolyamide (P-1) obtained in Reference Example 1 above. After dissolving 2 parts by mass of 4,4′-bis (methoxymethyl) biphenyl in 170 parts by mass of γ-butyrolactone, it was filtered through a 0.2 μm filter to prepare a photosensitive resin composition A. Using the obtained photosensitive resin composition, a relief pattern was created on a silicon wafer by the method described above, and the cure shrinkage, the sensitivity of the composition, and the resolution were evaluated. Furthermore, the temporal stability of sensitivity after exposure was evaluated by the method described above. Further, the viscosity of the composition was measured by the method described above, and the storage stability was evaluated.

[Example 2]
As an alkoxyalkyl group-containing compound, 20 parts by mass of the diazoquinone compound (Q-1) obtained in Reference Example 3 with respect to 100 parts by mass of the hydroxypolyamide (P-1) obtained in Reference Example 1 above. 8 parts by mass of 4,4′-bis (methoxymethyl) biphenyl was dissolved in 170 parts by mass of γ-butyrolactone, and then filtered through a 0.2 μm filter to prepare a photosensitive resin composition B. Using the obtained photosensitive resin composition, a relief pattern was created on a silicon wafer by the method described above, and the cure shrinkage, the sensitivity of the composition, and the resolution were evaluated. Furthermore, the temporal stability of sensitivity after exposure was evaluated by the method described above. Further, the viscosity of the composition was measured by the method described above, and the storage stability was evaluated.

Example 3
As an alkoxyalkyl group-containing compound, 20 parts by mass of the diazoquinone compound (Q-1) obtained in Reference Example 3 with respect to 100 parts by mass of the hydroxypolyamide (P-1) obtained in Reference Example 1 above. After dissolving 20 parts by mass of 4,4′-bis (methoxymethyl) biphenyl in 170 parts by mass of γ-butyrolactone, it was filtered through a 0.2 μm filter to prepare a photosensitive resin composition C. Using the obtained photosensitive resin composition, a relief pattern was created on a silicon wafer by the method described above, and the cure shrinkage, the sensitivity of the composition, and the resolution were evaluated. Furthermore, the temporal stability of sensitivity after exposure was evaluated by the method described above. Further, the viscosity of the composition was measured by the method described above, and the storage stability was evaluated.

Example 4
Photosensitive resin composition D was prepared in the same manner as in Example 2 except that 1,4-bis (methoxymethyl) benzene was used as the alkoxyalkyl group-containing compound. Using the obtained photosensitive resin composition, a relief pattern was created on a silicon wafer by the method described above, and the cure shrinkage, the sensitivity of the composition, and the resolution were evaluated. Furthermore, the temporal stability of sensitivity after exposure was evaluated by the method described above. Further, the viscosity of the composition was measured by the method described above, and the storage stability was evaluated.

Example 5
Photosensitive resin composition E was prepared in the same manner as in Example 2 except that 4,4′-bis (methoxymethyl) diphenyl ether was used as the alkoxyalkyl group-containing compound. Using the obtained photosensitive resin composition, a relief pattern was created on a silicon wafer by the method described above, and the cure shrinkage, the sensitivity of the composition, and the resolution were evaluated. Furthermore, the temporal stability of sensitivity after exposure was evaluated by the method described above. Further, the viscosity of the composition was measured by the method described above, and the storage stability was evaluated.

Example 6
Photosensitive resin composition F was prepared in the same manner as in Example 2, except that the alkoxyalkyl group-containing compound was 4,4′-bis (methoxymethyl) diphenylmethane. Using the obtained photosensitive resin composition, a relief pattern was created on a silicon wafer by the method described above, and the cure shrinkage, the sensitivity of the composition, and the resolution were evaluated. Furthermore, the temporal stability of sensitivity after exposure was evaluated by the method described above. Further, the viscosity of the composition was measured by the method described above, and the storage stability was evaluated.

Example 7
Photosensitive resin composition G was prepared in the same manner as in Example 2 except that 4-methoxymethylbiphenyl was used as the alkoxyalkyl group-containing compound. Using the obtained photosensitive resin composition, a relief pattern was created on a silicon wafer by the method described above, and the cure shrinkage, the sensitivity of the composition, and the resolution were evaluated. Furthermore, the temporal stability of sensitivity after exposure was evaluated by the method described above. Further, the viscosity of the composition was measured by the method described above, and the storage stability was evaluated.

Example 8
Photosensitive resin composition H was prepared in the same manner as in Example 2 except that the alkoxyalkyl group-containing compound (C-1) obtained in Reference Example 7 was used as the alkoxyalkyl group-containing compound. Using the obtained photosensitive resin composition, a relief pattern was created on a silicon wafer by the method described above, and the cure shrinkage, the sensitivity of the composition, and the resolution were evaluated. Furthermore, the temporal stability of sensitivity after exposure was evaluated by the method described above. Further, the viscosity of the composition was measured by the method described above, and the storage stability was evaluated.

Example 9
The diazoquinone obtained in Reference Example 4 was used instead of 20 parts by mass of the diazoquinone compound (Q-1), using the hydroxypolyamide (P-2) obtained in Reference Example 2 instead of the hydroxypolyamide (P-1). A photosensitive resin composition I was prepared in the same manner as in Example 2 except that 14 parts by mass of the compound (Q-2) was used. Using the obtained photosensitive resin composition, a relief pattern was created on a silicon wafer by the method described above, and the cure shrinkage, the sensitivity of the composition, and the resolution were evaluated. Furthermore, the temporal stability of sensitivity after exposure was evaluated by the method described above. Further, the viscosity of the composition was measured by the method described above, and the storage stability was evaluated.

Example 10
The diazoquinone obtained in Reference Example 4 was used instead of 20 parts by mass of the diazoquinone compound (Q-1), using the hydroxypolyamide (P-2) obtained in Reference Example 2 instead of the hydroxypolyamide (P-1). A photosensitive resin composition J was prepared in the same manner as in Example 4 except that 14 parts by mass of the compound (Q-2) was used. Using the obtained photosensitive resin composition, a relief pattern was created on a silicon wafer by the method described above, and the cure shrinkage, the sensitivity of the composition, and the resolution were evaluated. Furthermore, the temporal stability of sensitivity after exposure was evaluated by the method described above. Further, the viscosity of the composition was measured by the method described above, and the storage stability was evaluated.

Example 11
The hydroxypolyamide (P-2) obtained in Reference Example 2 was used in place of the hydroxypolyamide (P-1), and the alkoxyalkyl group-containing compound was converted to 1,3,5-tris (methoxymethyl) -2,4,6. A photosensitive resin composition K was prepared in the same manner as in Example 2 except that -trimethoxybenzene was used. Using the obtained photosensitive resin composition, a relief pattern was created on a silicon wafer by the method described above, and the cure shrinkage, the sensitivity of the composition, and the resolution were evaluated. Furthermore, the temporal stability of sensitivity after exposure was evaluated by the method described above. Further, the viscosity of the composition was measured by the method described above, and the storage stability was evaluated.

Example 12
Photosensitive resin composition L was prepared in the same manner as in Example 11, except that the alkoxyalkyl group-containing compound was 1,2,4,5-tetrakis (methoxymethyl) benzene. Using the obtained photosensitive resin composition, a relief pattern was created on a silicon wafer by the method described above, and the cure shrinkage, the sensitivity of the composition, and the resolution were evaluated. Furthermore, the temporal stability of sensitivity after exposure was evaluated by the method described above. Further, the viscosity of the composition was measured by the method described above, and the storage stability was evaluated.

Example 13
A photosensitive resin composition M was prepared in the same manner as in Example 11, except that the alkoxyalkyl group-containing compound (C-2) obtained in Reference Example 8 was used as the alkoxyalkyl group-containing compound. Using the obtained photosensitive resin composition, a relief pattern was created on a silicon wafer by the method described above, and the cure shrinkage, the sensitivity of the composition, and the resolution were evaluated. Furthermore, the temporal stability of sensitivity after exposure was evaluated by the method described above. Further, the viscosity of the composition was measured by the method described above, and the storage stability was evaluated.

Example 14
Photosensitive resin composition N was prepared in the same manner as in Example 11, except that the alkoxyalkyl group-containing compound (C-3) obtained in Reference Example 9 was used as the alkoxyalkyl group-containing compound. Using the obtained photosensitive resin composition, a relief pattern was created on a silicon wafer by the method described above, and the cure shrinkage, the sensitivity of the composition, and the resolution were evaluated. Furthermore, the temporal stability of sensitivity after exposure was evaluated by the method described above. Further, the viscosity of the composition was measured by the method described above, and the storage stability was evaluated.

[Comparative Example 1]
Photosensitization was carried out in the same manner as in Example 1 except that 8 parts by mass of a methylol group-containing compound DML-PTBP (Honshu Chemical Industry Co., Ltd.) (the structural formula is shown below) was used instead of the alkoxyalkyl group-containing compound. Resin composition O was prepared. Using the obtained photosensitive resin composition, a relief pattern was created on a silicon wafer by the method described above, and the cure shrinkage, the sensitivity of the composition, and the resolution were evaluated. Furthermore, the temporal stability of sensitivity after exposure was evaluated by the method described above. Further, the viscosity of the composition was measured by the method described above, and the storage stability was evaluated.

[Comparative Example 2]
As the alkoxyalkyl group-containing compound, the photosensitive resin composition P was prepared in the same manner as in Example 1 except that 8 parts by mass of DMOM-PTBP (Honshu Chemical Industry Co., Ltd.) (the structural formula is shown below) was used. Was prepared. Using the obtained photosensitive resin composition, a relief pattern was created on a silicon wafer by the method described above, and the cure shrinkage, the sensitivity of the composition, and the resolution were evaluated. Furthermore, the temporal stability of sensitivity after exposure was evaluated by the method described above. Further, the viscosity of the composition was measured by the method described above, and the storage stability was evaluated.

[Comparative Example 3]
Photosensitive resin composition Q was prepared in the same manner as in Example 1 except that 8 parts by mass of 2,6-dimethylol-p-cresol was used instead of the alkoxyalkyl group-containing compound. Using the obtained photosensitive resin composition, a relief pattern was created on a silicon wafer by the method described above, and the cure shrinkage, the sensitivity of the composition, and the resolution were evaluated. Furthermore, the temporal stability of sensitivity after exposure was evaluated by the method described above. Further, the viscosity of the composition was measured by the method described above, and the storage stability was evaluated.

[Comparative Example 4]
A photosensitive resin composition R was prepared in the same manner as in Example 1 except that 8 parts by mass of 1,4-dibenzyl alcohol was used instead of the alkoxyalkyl group-containing compound. Using the obtained photosensitive resin composition, a relief pattern was created on a silicon wafer by the method described above, and the cure shrinkage, the sensitivity of the composition, and the resolution were evaluated. Furthermore, the temporal stability of sensitivity after exposure was evaluated by the method described above. Further, the viscosity of the composition was measured by the method described above, and the storage stability was evaluated.

[Comparative Example 5]
In the same manner as in Example 1 except that 8 parts by mass of the methylol group-containing compound TML-BP (Honshu Chemical Industry Co., Ltd.) (structural formula was described above) was used instead of the alkoxyalkyl group-containing compound. Resin composition S was prepared. Using the obtained photosensitive resin composition, a relief pattern was created on a silicon wafer by the method described above, and the cure shrinkage, the sensitivity of the composition, and the resolution were evaluated. Furthermore, the temporal stability of sensitivity after exposure was evaluated by the method described above. Further, the viscosity of the composition was measured by the method described above, and the storage stability was evaluated.

[Comparative Example 6]
A photosensitive resin composition T was prepared in the same manner as in Example 1 except that 8 parts by mass of TMOM-BP (manufactured by Honshu Chemical Industry Co., Ltd.) (structural formula was described above) was used as the alkoxyalkyl group-containing compound. Prepared. Using the obtained photosensitive resin composition, a relief pattern was created on a silicon wafer by the method described above, and the cure shrinkage, the sensitivity of the composition, and the resolution were evaluated. Furthermore, the temporal stability of sensitivity after exposure was evaluated by the method described above. Further, the viscosity of the composition was measured by the method described above, and the storage stability was evaluated.

[Comparative Example 7]
A photosensitive resin composition U was prepared in the same manner as in Example 1, except that 8 parts by mass of the methylol group-containing compound (C-4) obtained in Reference Example 10 was used instead of the alkoxyalkyl group-containing compound. did. Using the obtained photosensitive resin composition, a relief pattern was created on a silicon wafer by the method described above, and the cure shrinkage, the sensitivity of the composition, and the resolution were evaluated. Furthermore, the temporal stability of sensitivity after exposure was evaluated by the method described above. Further, the viscosity of the composition was measured by the method described above, and the storage stability was evaluated.

[Comparative Example 8]
A photosensitive resin composition V was prepared in the same manner as in Example 1, except that the alkoxyalkyl group-containing compound was 8 parts by mass of dimethoxymethylurea (trade name MX-290, manufactured by Mitsui Cytec Co., Ltd.). . Using the obtained photosensitive resin composition, a relief pattern was created on a silicon wafer by the method described above, and the cure shrinkage, the sensitivity of the composition, and the resolution were evaluated. Furthermore, the temporal stability of sensitivity after exposure was evaluated by the method described above. Further, the viscosity of the composition was measured by the method described above, and the storage stability was evaluated.

[Comparative Example 9]
Except for using 8 parts by mass of hydrogenated bisphenol A diglycidyl ether (trade name Epolite 4000, manufactured by Kyoeisha Chemical Co., Ltd.), which is an epoxy group-containing compound, instead of the alkoxyalkyl group-containing compound, the same procedure as in Example 1 was performed. A photosensitive resin composition W was prepared. Using the obtained photosensitive resin composition, a relief pattern was created on a silicon wafer by the method described above, and the cure shrinkage, the sensitivity of the composition, and the resolution were evaluated. Furthermore, the temporal stability of sensitivity after exposure was evaluated by the method described above. Further, the viscosity of the composition was measured by the method described above, and the storage stability was evaluated.

[Comparative Example 10]
A photosensitive resin was prepared in the same manner as in Example 1, except that 8 parts by mass of a benzoxazine compound (trade name Ba type benzoxazine, manufactured by Shikoku Kasei Kogyo Co., Ltd.) was used instead of the alkoxyalkyl group-containing compound. Composition X was prepared. Using the obtained photosensitive resin composition, a relief pattern was created on a silicon wafer by the method described above, and the cure shrinkage, the sensitivity of the composition, and the resolution were evaluated. Furthermore, the temporal stability of sensitivity after exposure was evaluated by the method described above. Further, the viscosity of the composition was measured by the method described above, and the storage stability was evaluated.

A list of compositions of the photosensitive resin compositions of Examples 1 to 14 and Comparative Examples 1 to 10 is shown in Table 1 below, and the evaluation results are shown in Table 2 below.
From Table 2, it can be seen that the photosensitive resin composition of the present invention has good storage stability, can form a relief pattern with high sensitivity and high resolution, and is excellent in sensitivity over time after exposure. . On the other hand, the compositions of Comparative Examples 1 to 10 that do not contain an alkoxyalkyl group-containing compound that satisfies the requirements of the present invention have a problem that good sensitivity, resolution cannot be obtained, or the stability of the composition is poor. I understand.

  The photosensitive resin composition of the present invention includes a surface protective film for a semiconductor device, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip chip device, a protective film for a device having a bump structure, an interlayer insulating film for a multilayer circuit, It can be suitably used as a cover coat of a flexible copper-clad plate, a solder resist film, and a liquid crystal alignment film.

Claims (10)

(A) The following general formula (1):

{Wherein X ¹ is a tetravalent organic group having a carbon atom, and X ² , Y ¹ and Y ² are each independently a divalent organic group having 2 or more carbon atoms, l is an integer from 2 to 1000, m is an integer from 0 to 500, l / (l + m)> 0.5, and ¹ dihydroxydiamide unit containing X ¹ and Y ¹ and X The arrangement order of the m diamide units including ² and Y ² is not limited. } 100 parts by mass of a hydroxypolyamide having a structure represented by the following general formula (2):

{Wherein k is an integer of 1 to 4, and (i) when k = 1, X is C _n H _2n OR ¹ or R ² , R ¹ is a methyl group, an ethyl group, n -A monovalent organic group selected from the group consisting of a propyl group and an isopropyl group, and R ² is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an ester group having 2 to 10 carbon atoms, or 2 to 2 carbon atoms. 10 is a monovalent organic group selected from the group consisting of a urethane group and an alkoxy group having 1 to 10 carbon atoms, n is an integer of 1 to 3, p is an integer of 1 to 5, q is an integer of 0 to 4 and (p + q) = 5, (ii) when k = 2 to 4, X is a single bond or a divalent to tetravalent organic group, and R ¹ is , A monovalent organic group selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, R ² represents a hydrogen atom, a carbon number of 1 A monovalent organic group selected from the group consisting of -4 alkyl groups, C2-C10 ester groups, and C2-C10 urethane groups, n is an integer of 1-3, p Is an integer from 1 to 5, q is an integer from 0 to 4, and (p + q) = 5. However, when there are a plurality of C _n H _2n OR ¹ and R ² , n, p, q, R ¹ and R ² may be the same or different from each other. } The photosensitive resin composition characterized by including 0.01-30 mass parts of alkoxyalkyl group containing compounds represented, and (C) 1-100 mass parts of diazoquinone compounds. (B) The alkoxyalkyl group-containing compound has the following general formula (3):

{Wherein k is 1 or 2, and (i) when k = 1, X is C _n H _2n OR ¹ or R ² , R ¹ is a methyl group, an ethyl group, n-propyl A monovalent organic group selected from the group consisting of a group and an isopropyl group, and R ² is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an ester group having 2 to 10 carbon atoms, or an alkyl group having 2 to 10 carbon atoms. A monovalent organic group selected from the group consisting of a urethane group and an alkoxy group having 1 to 10 carbon atoms, n is an integer of 1 to 3, and (ii) when k = 2, X is a single group. Bond or the following general formula (4):

R ¹ is a monovalent organic group selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, R ² is a monovalent organic group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an ester group having 2 to 10 carbon atoms, and a urethane group having 2 to 10 carbon atoms, and n is , 1-3, p is an integer of 1-5, q is an integer of 0-4, and (p + q) = 5. However, when there are a plurality of C _n H _2n OR ¹ and R ² , n, p, q, R ¹ and R ² may be the same or different from each other. }
The photosensitive resin composition of Claim 1 represented by these. (B) The alkoxyalkyl group-containing compound has the following general formula (5):

{Wherein R ¹ is a monovalent organic group selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, n is an integer of 1 to 3, and p is An integer of 1 to 5, k is 1 or 2, (i) when k = 1, X is a hydrogen atom or C _n H _2n OR ¹ , and (ii) when k = 2, X is a single bond or the following general formula (6):

Or a divalent to tetravalent organic group selected from the group represented by However, when there are a plurality of (C _n H _2n OR ¹ ), n and R ¹ may be the same as or different from each other. } The photosensitive resin composition of Claim 1 represented by these.   (B) an alkoxyalkyl group-containing compound is bis (methoxymethyl) benzene, tris (methoxymethyl) benzene, tetrakis (methoxymethyl) benzene, pentakis (methoxymethyl) benzene, hexakis (methoxymethyl) benzene, tris (methoxymethyl) The photosensitive resin composition according to claim 1, which is selected from the group consisting of trimethoxybenzene, methoxymethylbiphenyl, bis (methoxymethyl) biphenyl, bis (methoxymethyl) diphenyl ether, and bis (methoxymethyl) diphenylmethane. (B) The alkoxyalkyl group-containing compound has the following general formula (7):

{In the formula, Z ₁ represents the following general formula (8):

(Wherein R ^{3 to} R ⁵ are each independently an organic group having 1 to 9 carbon atoms, and R ⁶ is selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Is a monovalent organic group, and R ^{7 to} R ¹⁰ are each independently a substituent selected from a group represented by a C 1-12 organic group, and k is 1 to 1 And (i) when k = 1, Z ² is C _n H _2n OR ¹ or R ² , R is independently a methyl group or an ethyl group, and R ¹ is A monovalent organic group selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, and R ² is selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms. a monovalent organic group, n is an integer of 1 to 3, when (ii) k = 2~4, Z 2 is a single bond also A divalent to tetravalent organic group, if Z ¹ there are a plurality, Z ¹ may be different even in the same. } The photosensitive resin composition of Claim 1 represented by these. (B) The alkoxyalkyl group-containing compound has the following general formula (9):

{In the formula, each R independently represents a methyl group or an ethyl group; and each Z ¹ independently represents the following general formula (10):

(Wherein R ^{3 to} R ⁵ are each independently an organic group having 1 to 9 carbon atoms, and R ⁶ is selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Z ³ is a monovalent organic group, and R ^{7 to} R ¹⁰ are each independently a substituent selected from the group represented by C 1-12. Bond or the following general formula (11):

Is a substituent selected from the group represented by: } The photosensitive resin composition of Claim 5 represented by these. In the general formula (9), Z ³ is a single bond, and each Z ¹ independently represents the following general formula (12):

{Wherein R ³ and R ⁵ are each independently an organic group having 1 to 9 carbon atoms, and R ⁷ is an organic group having 1 to 12 carbon atoms. } The photosensitive resin composition of Claim 6 which is a substituent chosen from group represented by these. In the general formula (9), Z ³ is a single bond, and each Z ¹ independently represents the following general formula (13):

The photosensitive resin composition of Claim 6 which is a substituent chosen from group represented by these.   The process of forming the photosensitive resin layer which consists of the photosensitive resin composition of any one of Claims 1-8 on a board | substrate, it exposes with an active ray through a mask, or a light ray, an electron beam, or an ion beam A method for producing a cured relief pattern, comprising a step of directly irradiating, a step of developing, and a step of heating the obtained relief pattern.   A semiconductor device comprising a cured relief pattern layer obtained by the method according to claim 9.