JP4858079B2 - Positive photosensitive resin composition - Google Patents

Description

  The present invention relates to a positive photosensitive resin composition.

Conventionally, polybenzoxazole resins and polyimide resins having excellent heat resistance and excellent electrical characteristics, mechanical characteristics, and the like have been used for surface protective films and interlayer insulating films of semiconductor elements.
However, circuit pattern formation on a semiconductor integrated circuit or printed circuit board is complicated and diverse, such as film formation of a resist material on the surface of a base material, exposure to a predetermined location, removal of unnecessary portions by etching, etc., and cleaning of the substrate surface. Since the pattern formation is performed through these processes, it is desired to develop a heat-resistant photosensitive material that can be used by leaving a necessary portion of the resist as an insulating material even after pattern formation by exposure and development.

  As a material having such characteristics, Patent Document 1 proposes a positive photosensitive resin composition containing a polybenzoxazole precursor and a compound that generates an acid upon irradiation. Patent Document 2 proposes a positive photosensitive resin composition containing a polybenzoxazole precursor and a photosensitive diazonaphthoquinone compound. The development of the resist is usually performed using 2.38% tetramethylammonium hydroxide as an etching solution. However, in the positive photosensitive resin composition described in the above document, the polybenzoxazole precursor contained in the positive photosensitive resin composition is composed of one kind of diamine and dicarboxylic acid, so that it is highly soluble in an etching solution and difficult to process. There was a case.

JP-A-2005-321466 JP-A-11-119426

  The present invention has been made in view of such circumstances, and provides a positive photosensitive resin composition having appropriate solubility in an etching solution and excellent workability.

式（１）のジアミン以外の、式（２）で表される第２ジアミンと、
Ｈ_２Ｎ−Ｘ−ＮＨ_２ （２）
（式（２）中、Ｘは、有機基である）
以下から選択される少なくとも１種のカルボン酸とを、

（式中、Ａは、−ＣＨ _２ −、−Ｃ（ＣＨ _３ ） _２ −、−Ｏ−、−Ｓ−、−ＳＯ _２ −、−ＣＯ−、−ＮＨＣＯ−、−Ｃ（ＣＦ _３ ） _２ −、又は単結合であり、Ｒ _１１ は水素原子、アルキル基、アルキルエステル基およびハロゲン原子から選ばれた１つを表し、それぞれ同じでも異なっていてもよく、ｒ＝０〜２の整数である）
第１ジアミン（１）の第２ジアミン（２）に対するモル比が１以上９以下の量で重合させて得られるポリベンゾオキサゾール前駆体を含有するポジ型感光性樹脂組成物が提供される。 According to the present invention, the first diamine represented by the formula (1),

A second diamine represented by formula (2) other than the diamine of formula (1);
_{H 2 N-X-NH 2} (2)
(In formula (2), X is an organic group)
At least one carboxylic acid selected from :

(In the formula, A represents —CH ₂ —, —C (CH ₃ ) ₂ — , —O—, —S— , —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —. Or a single bond, and R ₁₁ represents one selected from a hydrogen atom, an alkyl group, an alkyl ester group and a halogen atom, which may be the same or different, and is an integer of r = 0 to 2.)
Provided is a positive photosensitive resin composition containing a polybenzoxazole precursor obtained by polymerizing the first diamine (1) to the second diamine (2) in a molar ratio of 1 or more and 9 or less.

  The polybenzoxazole precursor contained in this positive photosensitive resin composition is obtained by polymerizing the molar ratio of the first diamine (1) to the second diamine (2) in an amount of 1 or more and 9 or less. . Appropriate solubility in 38% tetramethylammonium hydroxide. For this reason, the positive photosensitive resin composition excellent in workability is obtained.

The positive photosensitive resin composition according to the present invention may further include a crosslinking agent and a compound that generates an acid by light or heat.
An oxetane compound can be used as the crosslinking agent, and a mixture of an aluminum complex and a silane coupling agent can be used as the compound that generates an acid by light or heat.
With the above configuration, cyclization of the polybenzoxazole precursor to polybenzoxazole is promoted, and a cured film having excellent physical properties such as heat resistance, moisture resistance, and solvent resistance can be obtained.

  ADVANTAGE OF THE INVENTION According to this invention, the positive photosensitive resin composition which has moderate solubility with respect to an etching solution, and has the outstanding workability is provided.

式（１）のジアミン以外の、式（２）で表される第２ジアミンと、
Ｈ_２Ｎ−Ｘ−ＮＨ_２ （２）
（式（２）中、Ｘは、有機基である）
カルボン酸とを、第１ジアミン（１）の第２ジアミン（２）に対するモル比が１以上９以下の量で重合させて得られる。 Hereinafter, preferred embodiments of the positive photosensitive resin composition according to the present invention will be described in detail.
In an embodiment of the present invention, the polybenzoxazole precursor is a 3,3′-diamino-4,4′-dihydroxydiphenyl sulfone (hereinafter referred to as HAB-S) of the first diamine represented by the formula (1). )When,

A second diamine represented by formula (2) other than the diamine of formula (1);
_{H 2 N-X-NH 2} (2)
(In formula (2), X is an organic group)
It is obtained by polymerizing carboxylic acid in an amount of 1 to 9 in molar ratio of the first diamine (1) to the second diamine (2).

ここで、Ａは、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−ＣＯ−、−ＮＨＣＯ−、−Ｃ（ＣＦ_３）_２−、または単結合であり、Ｘ_１は、水素原子、水酸基および−ＯＲ_１３から選択される１種であり、Ｒ_１３は炭素数１〜１５のアルキル基であり、Ｘ_１が水酸基の場合、この水酸基はアミノ基に対してオルソ位にあり、Ｒ_８、Ｒ_１０、Ｒ_１１およびＲ_１２は、それぞれ同じであっても異なっていてもよく、アルキル基、アルキルエステル基およびハロゲン原子から選択され、ｒ、ｓ、ｔおよびｕは、０〜２の整数であり、Ｒ_９は、水素原子、アルキル基、アルキルエステル基、ハロゲン原子およびアルキルカルボニルエーテルから選択される一種である。 In one embodiment, the second diamine is preferably a diamine in which the organic group X of formula (2) above is:

Here, A is —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —, Or a single bond, X ₁ is _one selected from a hydrogen atom, a hydroxyl group and —OR ₁₃ , R ₁₃ is an alkyl group having 1 to 15 carbon atoms, and when X ₁ is a hydroxyl group, this hydroxyl group Are ortho to the amino group and R ₈ , R ₁₀ , R ₁₁ and R ₁₂ may be the same or different and are each selected from an alkyl group, an alkyl ester group and a halogen atom, and r , S, t and u are each an integer of 0 to 2, and R ₉ is one selected from a hydrogen atom, an alkyl group, an alkyl ester group, a halogen atom and an alkylcarbonyl ether.

ここで、Ｘ_１は、水素原子、水酸基および−ＯＲ_１３から選択される１種であり、Ｒ_１３は炭素数１〜１５のアルキル基であり、Ｘ_１が水酸基の場合、この水酸基はアミノ基に対してオルソ位であり、Ｒ_８は、アルキル基、アルキルエステル基およびハロゲン原子から選択され、ｒは、０〜２の整数である
最も好ましくは、第２ジアミンは、上記式（２）の有機基Ｘが以下であるジアミンである：

これらのジアミンは、単独でかまたは２種以上組み合わせて用いてもよい。 More preferably, the second diamine is a diamine in which the organic group X of formula (2) is:

Here, X ₁ is _one selected from a hydrogen atom, a hydroxyl group and —OR ₁₃ , R ₁₃ is an alkyl group having 1 to 15 carbon atoms, and when X ₁ is a hydroxyl group, this hydroxyl group is an amino group R ₈ is selected from an alkyl group, an alkyl ester group and a halogen atom, and r is an integer from 0 to 2. Most preferably, the second diamine is of the above formula (2) A diamine in which the organic group X is:

These diamines may be used alone or in combination of two or more.

（式中、Ａは、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−ＣＯ−、−ＮＨＣＯ−、−Ｃ（ＣＦ_３）_２−、又は単結合であり、Ｒ_１１は水素原子、アルキル基、アルキルエステル基およびハロゲン原子から選ばれた１つを表し、それぞれ同じでも異なっていてもよく、ｒ＝０〜２の整数である）。
特に好ましいカルボン酸としては、以下が挙げられる。 In an embodiment of the present invention, the carboxylic acid used in the synthesis of the polybenzoxazole precursor includes the following:

(In the formula, A represents —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —. Or a single bond, and R ₁₁ represents one selected from a hydrogen atom, an alkyl group, an alkyl ester group and a halogen atom, which may be the same or different, and is an integer of r = 0 to 2.) .
Particularly preferred carboxylic acids include the following.

(In the formula, R ₁₂ represents one selected from a hydrogen atom, an alkyl group, an alkyl ester group and a halogen atom, which may be the same or different, and is an integer of r = 0 to 2).
These carboxylic acids may be used alone or in combination of two or more.

  The polybenzoxazole precursor of the present invention comprises 3,3′-diamino-4,4′-dihydroxydiphenylsulfone, a diamine having the structure of the above formula (2), a carboxylic acid, an acid chloride method, and polyphosphorus It can be obtained by a method such as condensation in the presence of an acid and a dehydrating condensing agent such as dicyclohexylcarbodiimide.

  Moreover, in this invention, it is desirable to seal the terminal of a polybenzoxazole precursor from a viewpoint of preservability. For sealing, a derivative having an aliphatic group or a cyclic compound group having at least one alkenyl group or alkynyl group can be introduced as an acid derivative or an amine derivative at the terminal of the polybenzoxazole precursor.

  Specifically, for example, after a first and second diamine and a carboxylic acid are reacted to obtain a polybenzoxazole precursor, the terminal amino group contained in the polybenzoxazole precursor is converted to an alkenyl group or It is preferable to seal as an amide using an acid anhydride or acid derivative containing an aliphatic group having at least one alkynyl group or a cyclic compound group.

  Examples of the end-capping functional group include those represented by the following formula.

  Among these, a functional group represented by the following formula is particularly preferable. These may be used alone or in combination of two or more. Further, the present invention is not limited to this method, and the terminal acid contained in the polyamide resin is sealed as an amide using an amine derivative containing an aliphatic group or a cyclic compound group having at least one alkenyl group or alkynyl group. You can also.

  The polybenzoxazole precursor of the present invention preferably has a weight average molecular weight (Mw) of 5,000 or more and 30,000 or less. The number average molecular weight (Mn) is preferably 5,000 or more and 20,000 or less. The molecular weight can be measured by gel permeation chromatography (GPC) and calculated in terms of polystyrene. When the molecular weight is within the above range, moderate solubility in a solvent and good resolution can be obtained.

  In the synthesis of the polybenzoxazole precursor of the present invention, the molar ratio of the diamine (1) used to the diamine (2) is 1 or more and 9 or less, preferably 1.5 or more and 4.5 or less. When the molar ratio is within the above range, the resulting polybenzoxazole precursor has moderate solubility in 2.38% tetramethylammonium hydroxide (TMAH). When the structure of diamine (1) is larger than the said range, the solubility to TMAH will become high and processing will become difficult. Moreover, when diamine (1) is smaller than the said range, the solubility with respect to TMAH will become low, and processing will become difficult.

The positive photosensitive resin composition of the present invention may contain a compound that generates an acid by light together with the polybenzoxazole precursor.
Examples of the compound that generates an acid by light used in the present invention include a diazoquinone compound. This diazoquinone compound is a compound having a 1,2-benzoquinonediazide or 1,2-naphthoquinonediazide structure, and is a substance known from US Pat. Nos. 2,727,975, 2,797,213, and 3,669,658.
For example, the compound represented by the following formula is mentioned.

In the formula, Q is selected from a hydrogen atom, formula (2), and formula (3). Here, at least one of Q of each compound is represented by formula (2) or formula (3).

  Among these, an ester of a phenol compound and 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid is particularly preferable. Specific examples thereof include the following formula. These may be used alone or in combination of two or more.

In the formula, Q is selected from a hydrogen atom, formula (4), and formula (5). Here, at least one of Q of each compound is represented by formula (4) or formula (5).
The preferable addition amount of the diazoquinone compound used in the present invention is 1 part by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the polybenzoxazole precursor. If the amount is less than 1 part by weight, a good pattern cannot be obtained, and if it exceeds 50 parts by weight, the sensitivity is greatly reduced.

The positive photosensitive resin composition of the present invention may contain a crosslinking agent and a compound that generates an acid by light or heat. Examples of the crosslinking agent include oxetane compounds. The oxetane compound used in the present invention is a compound having an oxetanyl group in the molecule, and capable of cationic ring-opening polymerization reaction or addition reaction with carboxylic acid, thiol and phenol.
Examples of the oxetane compound include compounds represented by the following formula (C-1):

  Specific examples of the oxetane compound of the formula C-1 include, for example, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, bis [1-ethyl (3-oxetanyl)] methyl ether, 4,4′-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl, 4,4′-bis (3-ethyl-3-oxetanylmethoxy) biphenyl, ethylene glycol bis (3-ethyl-3-oxetanyl) Methyl) ether, diethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, bis (3-ethyl-3-oxetanylmethyl) diphenoate, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-Ethyl-3-oxetanylmethyl Ether and the like, but not limited thereto. These may be used alone or in combination.

  When the addition amount of the oxetanyl compound is less than 1 part by weight relative to 100 parts by weight of the polybenzoxazole precursor, sufficient reflow resistance and chemical resistance cannot be obtained. It is preferable to use 1 part by weight or more.

  As a compound that generates an acid by light or heat, a mixture of an aluminum complex and a silane coupling agent can be used.

  The aluminum complex is preferably an aluminum chelate complex. For example, aluminum ethyl acetoacetate diisopropylate, aluminum tris (ethyl acetoacetate), aluminum tris (acetylacetonate), alkyl acetoacetate aluminum diisopropylate, aluminum bisethyl Examples include acetoacetate monoacetylacetonate. Of these, aluminum tris (acetylacetonate) and aluminum ethylacetoacetate diisopropylate are preferable. These may be used alone or in combination.

  It is preferable that the addition amount of an aluminum complex compound is 0.1-20 weight part with respect to 100 weight part of polybenzoxazole precursors, More preferably, it is 0.5-10 weight part. When the lower limit is exceeded, it becomes possible to obtain a cured film having excellent physical properties such as heat resistance, moisture resistance, and solvent resistance. When the upper limit is not reached, problems such as precipitation during frozen storage are reduced. .

A silane coupling agent means what a silanol group produces | generates by heating. The silane coupling agent has a Si—O—C bond, and more preferably is an alkoxysilane compound. Among alkoxysilane compounds, a silane coupling agent represented by R′—Si— (O—R) ₃ (R is an alkyl group and R ′ is an organic group) is preferable because it has many reactive sites. Used for. Such a silane coupling agent is hydrolyzed when heated to produce silanol groups. It is preferable that the silanol group is not generated at the pre-bake temperature at the time of pattern processing, but is generated at the time of temperature increase in the curing process. Note that the pre-beg temperature generally used is 80 ° C. to 130 ° C.

  Specific examples of the silane coupling agent include, for example, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiisopropoxysilane, diphenyldiacetoxysilane, diphenyldiphenoxysilane, triphenylmethoxysilane, triphenylethoxysilane, diphenylvinylethoxysilane. , Vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ- (methacryloxypropyl) trimethoxysilane, β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxy Propyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-amino Propylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, triethoxy (4- (trifluoromethyl) phenyl) silane, pentafluorophenyl An alkoxysilane compound such as trimethoxysilane or an active silicon compound having the following structure can also be used. Of these, γ- (methacryloxypropyl) trimethoxysilane and an active silicon compound having the following structure are preferable. These may be used alone or in combination.

  It is preferable that the addition amount of an active silicon compound is 0.1-50 weight part with respect to 100 weight part of polybenzoxazole precursors, More preferably, it is 1-30 weight part. If it exceeds the lower limit, it can react with the aluminum complex compound to generate sufficient acid, and if it is lower than the upper limit, good storage stability can be obtained.

  The silane coupling agent is inactive to other resin compositions of the present invention at room temperature, but a silanol group is generated by heating to a certain temperature and reacts with the aluminum complex in the resin composition. Have It is considered that Bronsted acid is generated after the reaction, which promotes cyclization of the polybenzoxazole precursor and initiates a crosslinking reaction of polybenzoxazole. The silane coupling agent of the present invention and an aluminum complex react to generate Bronsted acid, and at the same time, an aluminum silicate compound is also generated.

  By coexisting a silane coupling agent and an aluminum complex in the resin composition, no acid is generated at room temperature, but when heated, the acid is generated and the effect of promoting the cyclization of the polybenzoxazole precursor is exhibited. Then, a system for initiating the crosslinking reaction is constructed.

  The positive type photosensitive resin composition of the present invention forms a pattern through coating, patterning (including pre-baking), alkali development, cyclization step, and the like as described in a later paragraph. Here, when an acid is present from the beginning of the positive photosensitive resin composition, the acid required for alkali development is deactivated, and the cyclization promoting effect of the cyclization step is not sufficiently exhibited. There is a point. Therefore, it is desirable that the cyclization accelerator is generated as an acid for the first time in the cyclization step.

  In the present invention, these components are dissolved in a solvent and used in the form of a varnish. Solvents include N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl 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, methyl-3-methoxypropio And the like, and may be used alone or in combination.

  In the method of using the positive photosensitive resin composition of the present invention, first, the composition is applied to a suitable support such as a silicon wafer, a ceramic substrate, an aluminum substrate and the like. In the case of a semiconductor device, the coating amount is applied so that the final film thickness after curing is 0.1 to 30 μm. If the film thickness is below the lower limit value, it will be difficult to fully function as a protective surface film of the semiconductor element. If the film thickness exceeds the upper limit value, it will be difficult to obtain a fine processing pattern. Takes a long time to reduce throughput. Examples of the coating method include spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, and the like. Next, after prebaking at 60 to 130 ° C. to dry the coating film, actinic radiation is applied to the desired pattern shape. As the actinic radiation, X-rays, electron beams, ultraviolet rays, visible rays and the like can be used, but those having a wavelength of 200 to 500 nm are preferable.

  Next, a relief pattern is obtained by dissolving and removing the irradiated portion with a developer. Developers include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine, and di-n. Secondary amines such as propylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, quaternary ammonium such as tetramethylammonium hydroxide and tetraethylammonium hydroxide An aqueous solution of an alkali such as a salt and an aqueous solution to which an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant is added can be preferably used. As a developing method, methods such as spraying, paddle, dipping, and ultrasonic waves are possible.

  Next, the relief pattern formed by development is rinsed. Distilled water is used as the rinse liquid. Next, heat treatment is performed to form an oxazole ring and the like, and a final pattern having high heat resistance is obtained.

  The development mechanism of this positive photosensitive resin composition is hardly soluble in an alkaline aqueous solution in the unexposed area due to the effect of inhibiting dissolution of the diazoquinone compound in a resin such as polybenzoxazole resin or polyimide resin. On the other hand, in the exposed area, the diazoquinone compound undergoes a chemical change and becomes soluble in an alkaline aqueous solution. By utilizing the difference in solubility between the exposed portion and the unexposed portion to dissolve and remove the exposed portion, it is possible to create a coating film pattern of only the unexposed portion.

  The positive photosensitive resin composition according to the present invention is used not only for semiconductor applications, but also as interlayer insulation for multilayer circuits, cover coats for flexible copper-clad plates, solder resist films and liquid crystal alignment films, and interlayer insulation films for elements in display devices. Is also useful.

  Examples of semiconductor device applications include a passivation film obtained by forming the above-described positive photosensitive resin composition film on a semiconductor element, and a positive photosensitive resin composition described above on a passivation film formed on a semiconductor element. Examples thereof include a buffer coat film formed by forming a physical film, and an interlayer insulating film formed by forming the above-described positive photosensitive resin composition film on a circuit formed on a semiconductor element.

  Examples of display device applications include TFT interlayer insulating films, TFT element flattening films, color filter flattening films, protrusions for MVA liquid crystal display devices, and cathode barriers for organic EL elements. The usage method is based on forming a positive photosensitive resin composition layer patterned on the substrate on which the display element and the color filter are formed according to the semiconductor application by the above method. High transparency is required for display device applications, especially interlayer insulation films and planarization films, but by introducing a post-exposure process before curing this positive photosensitive resin composition layer, transparency It is also possible to obtain a resin layer that is excellent in practical use, which is more preferable in practical use.

Example 1
(Preparation of polybenzoxazole precursor)
Dicarboxylic acid derivative 6 obtained by reacting 3.36 g (0.013 mol) of diphenyl ether-4,4′-dicarboxylic acid with 3.51 g (0.026 mol) of 1-hydroxy-1,2,3-benzotriazole Dicarboxylic acid obtained by reacting .40 g (0.013 mol), 0.50 g (0.003 mol) of isophthalic acid and 0.81 g (0.006 mol) of 1-hydroxy-1,2,3-benzotriazole 0.81 g (0.003 mol) of the derivative, 3.36 g (0.016 mol) of 3,3′-diamino-4,4′-dihydroxydiphenylsulfone, and 1.24 g (0. 30 mol) of 3,3′-diaminodiphenylsulfone. 002 mol) in a four-necked separable flask equipped with a thermometer, stirrer, raw material inlet, and dry nitrogen gas inlet tube, 44.6 g of N-methyl-2-pyrrolidone was added and dissolved. Thereafter, the mixture was reacted at 75 ° C. for 12 hours using an oil bath. Next, 0.69 g (0.004 mol) of 5-ethynylisophthalic anhydride and 7 g of N-methyl-2-pyrrolidone were added, and the reaction was terminated by further stirring for 3 hours. After the reaction mixture is filtered, the reaction mixture is poured into a solution of water / isophthalic acid = 7/4 (volume ratio), the precipitate is collected by filtration, washed thoroughly with water, dried under vacuum, and the target polybenzo An oxazole precursor was obtained.

(Examples 2 to 10)
A polybenzoxazole precursor was synthesized in the same manner as in Example 1 except that the amount of diamine was changed to the amount shown in Table 1.

(Comparative Examples 1-2)
A polybenzoxazole precursor was synthesized in the same manner as in Example 1 except that the amount of diamine was changed to the amount shown in Table 1.

(Preparation of positive photosensitive resin composition)
10 g of the synthesized polybenzoxazole precursors of Examples 1 to 10 and Comparative Examples 1 and 2, 2.7 g of photosensitive diazoquinone, 4 g of oxetanyl group-containing compound, 0.2 g of silicon compound, 0.3 g of aluminum chelate and 20 g of γ-butyrolactone Then, it was filtered through a 0.2 μm fluororesin filter to obtain a positive photosensitive resin composition.

These positive photosensitive resin compositions were evaluated for the following items.
[Solubility measurement method]
The prepared positive photosensitive resin composition was applied to a 6-inch silicon wafer using a spin coater and then dried on a hot plate at 120 ° C. for 4 minutes to obtain a coating film having a thickness of about 7.5 μm. The film thickness of the coating film is measured. Next, development was carried out with a 2.38% tetramethylammonium hydroxide aqueous solution for 10 to 20 seconds, followed by rinsing with pure water for 30 seconds. After development, the thickness of the coating film was measured, and the amount of film slip (nm / sec) relative to the development time was calculated.
[Light transmittance measurement method]
After applying a solution in which only the polybenzoxazole precursor used in each Example and Comparative Example was dissolved in NMP to a glass substrate using a spinner, it was dried on a hot plate at 120 ° C. for 4 minutes to obtain a film thickness of about A coating film of 5.0 μm was obtained. The absorbance of this coating film at 365 nm was measured with a spectrophotometer.
The amounts of HAB-S and other diamines and carboxylic acids used (moles), and the resulting positive photosensitive resin composition solubility in TMAH (nm / sec) and light transmittance (%) were measured. It is shown in Table 1 below.
The positive photosensitive resin composition according to the present invention exhibited moderate solubility in TMAH and excellent light transmittance.

  It should be noted that the present invention is not limited to the embodiments presented above, and various modifications can be made without departing from the spirit of the present invention.

Claims (10)

A first diamine represented by formula (1);

A second diamine represented by formula (2) other than the diamine of formula (1);
_{H 2 N-X-NH 2} (2)
(In formula (2), X is an organic group)
At least one carboxylic acid selected from :

(In the formula, A represents —CH ₂ —, —C (CH ₃ ) ₂ — , —O—, —S— , —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —. Or a single bond, and R ₁₁ represents one selected from a hydrogen atom, an alkyl group, an alkyl ester group and a halogen atom, which may be the same or different, and is an integer of r = 0 to 2.)
A positive photosensitive resin composition containing a polybenzoxazole precursor obtained by polymerizing the first diamine (1) to the second diamine (2) in a molar ratio of 1 or more and 9 or less. The positive photosensitive resin composition according to claim 1, wherein the organic group X in the formula (2) is at least one selected from the following:

(Here, A is —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —. Or a single bond, X ₁ is _one selected from a hydrogen atom, a hydroxyl group and —OR ₁₃ , R ₁₃ is an alkyl group having 1 to 15 carbon atoms, and when X ₁ is a hydroxyl group, The hydroxyl group is ortho to the amino group and R ₈ , R ₁₀ , R ₁₁ and R ₁₂ may be the same or different, each selected from an alkyl group, an alkyl ester group and a halogen atom; r, s, t and u are each an integer of 0 to 2, and R ₉ is one selected from a hydrogen atom, an alkyl group, an alkyl ester group, a halogen atom and an alkylcarbonyl ether). The positive photosensitive resin composition according to claim 2, wherein the organic group X of the formula (2) is at least one selected from the following:

(Here, X ₁ is _one selected from a hydrogen atom, a hydroxyl group and —OR ₁₃ , R ₁₃ is an alkyl group having 1 to 15 carbon atoms, and when X ₁ is a hydroxyl group, this hydroxyl group is an amino group. Ortho is relative to the group, R ₈ is selected from an alkyl group, an alkyl ester group and a halogen atom, and r is an integer from 0 to 2. The positive photosensitive resin composition according to claim 2, wherein the organic group X of the formula (2) is at least one selected from the following:

  The positive photosensitive resin composition of any one of Claims 1-4 which further contains the compound which generate | occur | produces an acid by light.   The positive photosensitive resin composition according to claim 5, wherein the compound that generates an acid by light is a diazoquinone compound.   The positive photosensitive resin composition according to claim 1, which has a light transmittance of 60% or more.   The positive photosensitive resin composition of any one of Claims 1-7 which further contains a crosslinking agent and the compound which generate | occur | produces an acid by light or a heat | fever.   The positive photosensitive resin composition according to claim 8, wherein the crosslinking agent is an oxetane compound.   The positive photosensitive resin composition according to claim 8, wherein the compound that generates an acid by light or heat is a mixture of an aluminum complex and a silane coupling agent.