TWI717167B - Photosensitive resin composition and method for producing hardened relief pattern - Google Patents

Abstract

The present invention provides a photosensitive resin composition capable of obtaining a resin layer with high adhesiveness without generating voids at the interface between a Cu layer and a cured photosensitive resin layer after a high temperature storage test. And a method for forming a hardened relief pattern using the photosensitive resin composition. The present invention is a photosensitive resin composition and a cured embossed pattern using the photosensitive resin composition. The photosensitive resin composition can be stored at high temperature by combining a photosensitive resin with a specific plasticizer ( high temperature storage) After the test, there will be no voids at the interface between the Cu layer and the resin layer, and a photosensitive resin with high adhesion.

Description

Photosensitive resin composition and method for producing hardened relief pattern

The present invention relates to a photosensitive resin composition for forming embossed patterns such as insulating materials for electronic parts, passivation films, buffer coatings, interlayer insulating films, etc. in semiconductor devices, and hardened embossed patterns using the same The method of formation.

唑樹脂、酚樹脂等。該等樹脂之中，以感光性樹脂組合物之形式提供者藉由該組合物之塗佈、曝光、顯影、及利用固化而進行之熱醯亞胺化處理，可容易地形成耐熱性之浮凸圖案皮膜。此種感光性樹脂組合物與先前之非感光型材料相比具有能夠大幅縮減步驟之特徵。 Previously, insulating materials for electronic parts, passivation films, surface protection films, and interlayer insulating films for semiconductor devices used polyimide resins and polybenzos that have excellent heat resistance, electrical properties, and mechanical properties.

Azole resin, phenol resin, etc. Among these resins, those provided in the form of a photosensitive resin composition can easily form a heat-resistant float through the coating, exposure, development, and thermal imidization of the composition through curing. Convex pattern film. Compared with the previous non-photosensitive materials, this photosensitive resin composition has the feature of greatly reducing steps.

In addition, semiconductor devices (hereinafter also referred to as "devices") are mounted on a printed circuit board by various methods depending on the purpose. The previous devices are generally manufactured by wire bonding using thin wires to connect the external terminals (pads) of the device to the lead frame. However, with the rapid development of components and the operating frequency has reached GHz today, the difference in the wiring length of each terminal during installation will even affect the operation of the component. Therefore, in the installation of high-end components, the length of the wiring must be accurately controlled. If wire bonding is used, it is difficult to meet this requirement.

唑、酚樹脂等材料之情形時，待形成該樹脂層之圖案後，經過金屬配線層形成步驟。金屬配線層通常係對樹脂層表面進行電漿蝕刻而使表面粗化後，藉由濺鍍以1μm以下之厚度形成成為鍍覆之籽晶層之金屬層後，以該金屬層為電極，藉由電解鍍覆而形成。此時，一般使用Ti作為成為籽晶層之金屬，使用Cu作為藉由電解鍍覆而形成之再配線層之金屬。 Therefore, flip-chip mounting is proposed, that is, a rewiring layer is formed on the surface of a semiconductor chip, and bumps (electrodes) are formed on it, and then the chip is turned over (flip-chip) and directly mounted on a printed substrate (such as Refer to Patent Document 1). The flip-chip mounting is used for high-end components for processing high-speed signals because it can precisely control the wiring distance, or it is used for mobile phones because of its small mounting size, and its demand is rapidly expanding. Use polyimide and polybenzo

In the case of materials such as azole, phenol resin, etc., after the pattern of the resin layer is formed, the metal wiring layer forming step is carried out. The metal wiring layer is usually plasma etched on the surface of the resin layer to roughen the surface, and then a metal layer that becomes the seed layer of plating is formed by sputtering to a thickness of 1 μm or less, and then the metal layer is used as an electrode. It is formed by electrolytic plating. At this time, Ti is generally used as the metal for the seed layer, and Cu is used as the metal for the rewiring layer formed by electrolytic plating.

For this kind of metal rewiring layer, the adhesion between the metal layer and the resin layer of the rewiring is required to be higher after the reliability test. The reliability test performed here includes, for example, a high-temperature storage test in the air at a high temperature of 125°C or higher for more than 100 hours; while assembling wiring and applying voltage, it is confirmed that the temperature is around 125°C in the air. The high temperature action test of the action under the state of storing for more than 100 hours; the low temperature state of about -65~-40℃ and the high temperature state of about 125~150℃ in the air are repeated temperature cycle test; at the temperature of 85 High-temperature and high-humidity storage test in a water vapor environment above ℃ and 85% humidity; high-temperature and high-humidity bias test in which the same test is performed while assembling wiring and applying voltage; passing 260℃ several times in air or nitrogen The reflow soldering test of the reflow oven.

However, in the case of the high-temperature storage test in the above-mentioned reliability test, there was a problem that voids were generated at the interface between the Cu layer of the rewiring and the resin layer after the test. If a void is generated at the interface between the Cu layer and the resin layer, the adhesion between the two will decrease.

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2001-338947

The present invention is based on the research of the previous actual situation, and its purpose is to provide a high-temperature storage (high temperature storage) test after the Cu layer and the resin layer contact interface without voids and high adhesion The photosensitive resin composition of the resin layer, the method of forming a hardened relief pattern using the photosensitive resin composition, and a semiconductor device having the hardened relief pattern.

The inventors found that by combining a specific photosensitive resin with a specific plasticizer, a photosensitive resin composition capable of forming a cured film can be obtained. The cured film can be stored at high temperature. storage) After the test, no voids are generated at the interface between the Cu layer and the resin layer, and the resin layer with higher adhesion is completed, thus completing the present invention. That is, the present invention is as follows.

唑、酚醛清漆、聚羥基苯乙烯及酚樹脂所組成之群中之至少一種樹脂：100質量份，(B)塑化劑：以上述(A)樹脂100質量份為基準計0.1~50質量份，以及(C)感光劑：以上述(A)樹脂100質量份為基準計1~50質量份。 [1] A photosensitive resin composition comprising: (A) selected from the group consisting of polyamide acid, polyamide ester, polyamide acid salt, polyhydroxyamide, polyaminoamide, polyamide, Polyimide, polyimide, polybenzo

At least one resin from the group consisting of azole, novolac, polyhydroxystyrene and phenol resin: 100 parts by mass, (B) plasticizer: 0.1-50 parts by mass based on 100 parts by mass of the above (A) resin , And (C) Sensitizer: 1-50 parts by mass based on 100 parts by mass of the (A) resin.

唑前驅物、包含下述通式(6)之聚醯亞胺、以及酚醛清漆、聚羥基苯乙烯及包含下述通式(7)之酚樹脂所組成之群中之至少一種。 [2] The photosensitive resin composition according to [1], wherein the resin (A) is selected from polyimide precursors containing the following general formula (1) and polyimide precursors containing the following general formula (4) Amide, containing the following general formula (5) poly

An azole precursor, a polyimide containing the following general formula (6), and at least one of the group consisting of novolac, polyhydroxystyrene, and a phenol resin containing the following general formula (7).

The following general formula (1) is

{In the formula, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n ₁ is an integer from 2 to 150, and R ₁ and R ₂ are independently hydrogen atoms and saturated with carbon numbers of 1 to 30 Aliphatic group, aromatic group, or the following general formula (2):

(Wherein, R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or an organic group with 1 to 3 carbons, and m ₁ is an integer from 2 to 10) represented by a monovalent organic group, or 1 ~4 saturated aliphatic group, or the following general formula (3):

(In the formula, R ₆ , R ₇ and R ₈ are each independently a hydrogen atom or an organic group with 1 to 3 carbons, and m ₂ is an integer of 2 to 10), which is represented by a monovalent ammonium ion). The polyimide precursor of polyamide acid, polyamide acid ester or polyamide acid salt, the following general formula (4) has

{In the formula, X ₂ is a trivalent organic group with 6 to 15 carbons, Y ₂ is a divalent organic group with 6 to 35 carbons, and can be the same structure or multiple structures, and R ₉ is at least An organic group with a free radical polymerizable unsaturated bond group with carbon number 3-20, and n ₂ is an integer from 1 to 1000} The polyamide of the structure represented by the following general formula (5) has

{Where, Y ₃ is a 4-valent organic group with carbon atoms, Y ₄ , X ₃ and X ₄ are each independently a divalent organic group with 2 or more carbon atoms, n ₃ is an integer of 1 to 1000 , N ₄ is an integer from 0 to 500, n ₃ /(n ₃ +n ₄ )>0.5, and contains n ₃ dihydroxydiamide units of X ₃ and Y ₃ and n ₄ of X ₄ and Y ₄ The sequence of the diamide units is arbitrary}

唑前驅物之聚羥基醯胺，並且下述通式(6)為具有

The structure of the representation

Azole precursor polyhydroxyamide, and the following general formula (6) has

{In the formula, X ₅ is an organic group with 4 to 14 valences, Y ₅ is an organic group with 2 to 12 valences, R ₁₀ and R ₁₁ each independently represent having at least one selected from a phenolic hydroxyl group, a sulfonic acid group or a thiol The organic group of the base, n ₅ is an integer from 3 to 200, and m ₃ and m ₄ represent an integer from 0 to 10}

The structure represented by polyimide, and the following general formula (7) is

{In the formula, a is an integer from 1 to 3, b is an integer from 0 to 3, 1≦(a+b)≦4, R ₁₂ represents a monovalent organic group selected from 1 to 20 carbon atoms, halogen atoms, A monovalent substituent in the group consisting of a nitro group and a cyano group. When b is 2 or 3, a plurality of R ₁ may be the same or different from each other, and X represents a carbon that may have an unsaturated bond A divalent aliphatic group with 2 to 10, a divalent alicyclic group with 3 to 20 carbons, the following general formula (8): [化 8] -C _p H _2p O- (8)

(In the formula, p is an integer from 1 to 10) The divalent organic group in the group consisting of a divalent alkoxy group and a divalent organic group with an aromatic ring with carbon number 6 to 12基} The phenol resin represented.

[3] The photosensitive resin composition according to [1] or [2], wherein X in the above general formula (7) is selected from the following general formula (9):

{In the formula, R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are each independently a hydrogen atom, a monovalent aliphatic group with 1 to 10 carbon atoms, or a carbon in which part or all of the hydrogen atoms are replaced with fluorine atoms A monovalent aliphatic group of 1 to 10, n ₆ is an integer of 0 to 4, and when n ₆ is an integer of 1 to 4, R ₁₇ is a halogen atom, a hydroxyl group, or 1 of carbon numbers 1 to 12 For a valence organic group, at least one R ₆ is a hydroxyl group, and when n ₆ is an integer of 2 to 4, the plural R ₁₇ may be the same or different from each other. The divalent group represented by the following general formula (10):

{In the formula, R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ each independently represent a hydrogen atom, a monovalent aliphatic group with 1 to 10 carbon atoms, or a carbon in which part or all of the hydrogen atoms are substituted with fluorine atoms A monovalent aliphatic group of 1 to 10, W is a single bond, selected from aliphatic groups with 1 to 10 carbons that can be substituted by fluorine atoms, and alicyclic groups with 3 to 20 carbons that can be substituted by fluorine atoms Base, the following general formula (8): [化11] -C _p H _2p O- (8)

(In the formula, p is an integer from 1 to 10) a divalent alkoxy group represented by the following formula (11):

The divalent base in the group consisting of the indicated divalent radical} The divalent organic group in the group consisting of the indicated divalent radical.

[4] The photosensitive resin composition according to [1], wherein the (B) plasticizer is selected from the following general formula (7):

{In the formula, X is a structure containing saturated or unsaturated hydrocarbons or aromatic hydrocarbons with a carbon number of 1 or more and 15 or less, n is an integer from 1 to 4, when n is 2 or more, R can be the same It can also be different and is represented by saturated hydrocarbons or unsaturated hydrocarbons or aromatic hydrocarbons with carbon numbers of 2 or more and 15 or less, represented by the following general formula (8):

{In the formula, m is an integer from 1 to 4, and when m is 2 or more, R may be the same or different, respectively, representing a saturated or unsaturated hydrocarbon or aromatic hydrocarbon with a carbon number of 2 or more and 15 or less} , And the following general formula (9):

{In the formula, Y is a structure containing saturated or unsaturated hydrocarbons or aromatic hydrocarbons with a carbon number of 1 or more and 10 or less, and R may be the same or different, and represents a saturated hydrocarbon with a carbon number of 2 or more and 15 or less or At least one of the group consisting of unsaturated hydrocarbons or aromatic hydrocarbons.

[5] A method of manufacturing a hardened relief pattern, comprising: step (1) of coating a substrate with the photosensitive resin composition described in any one of [1] to [4]. A photosensitive resin layer is formed on the substrate; step (2) is to expose the photosensitive resin layer; step (3) is to develop the photosensitive resin layer after the exposure to form a relief pattern; and (4) It forms a hardened relief pattern by heating the relief pattern.

[6] The method according to [5], wherein the substrate is formed of copper or copper alloy.

In addition, the inventors of the present invention found that by blending nano particles in the photosensitive resin composition, a photosensitive resin capable of forming a cured film at the interface contacting the Cu layer after the high temperature storage test can be obtained. combination. The present invention can also be applied to the following aspects.

唑、以及酚醛清漆、聚羥基苯乙烯及酚樹脂所組成之群中之至少一種樹脂：100質量份，(B-1)奈米粒子：以上述(A)樹脂100質量份為基準計0.01~10質量份，以及(C)感光劑：以上述(A)樹脂100質量份為基準計1~50質量份。 [1] A photosensitive resin composition comprising (A) selected from the group consisting of polyamide acid, polyamide acid ester, polyamide acid salt, polyhydroxyamide, polyaminoamide, polyamide, polyamide Amide imine, polyimide, polybenzo

At least one resin from the group consisting of azole, novolak, polyhydroxystyrene, and phenol resin: 100 parts by mass, (B-1) Nanoparticles: 0.01~ based on 100 parts by mass of the above (A) resin 10 parts by mass, and (C) photosensitizer: 1 to 50 parts by mass based on 100 parts by mass of the (A) resin.

唑前驅物、包含下述通式(6)之聚醯亞胺、以及酚醛清漆、聚羥基苯乙烯及包含下述通式(7)之酚樹脂所組成之群中之至少一種。 [2] The photosensitive resin composition according to [1], wherein the resin (A) is selected from polyimide precursors containing the following general formula (1) and polyimide precursors containing the following general formula (4) Amide, containing the following general formula (5) poly

An azole precursor, a polyimide containing the following general formula (6), and at least one of the group consisting of novolac, polyhydroxystyrene, and a phenol resin containing the following general formula (7).

The following general formula (1) is

{In the formula, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n ₁ is an integer of 2 to 150, and R ₁ and R ₂ are independently hydrogen atoms and saturated with carbon numbers of 1 to 30 Aliphatic group, aromatic group, or the following general formula (2):

(Wherein, R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or an organic group with 1 to 3 carbons, and m ₁ is an integer from 2 to 10) represented by a monovalent organic group, or 1 ~4 saturated aliphatic group, or the following general formula (3):

(In the formula, R ₆ , R ₇ and R ₈ are each independently a hydrogen atom or an organic group with 1 to 3 carbons, and m ₂ is an integer of 2 to 10), which is represented by a monovalent ammonium ion). The polyimide precursor of polyamide acid, polyamide acid ester or polyamide acid salt, the following general formula (4) has [化19]

{In the formula, X ₂ is a trivalent organic group with 6 to 15 carbons, Y ₂ is a divalent organic group with 6 to 35 carbons, and can be the same structure or multiple structures, and R ₉ is at least An organic group with a radical polymerizable unsaturated bond group with carbon number 3-20, and n ₂ is an integer from 1 to 1000}

The structure of polyamide, the following general formula (5) has

{Where, Y ₃ is a 4-valent organic group with carbon atoms, Y ₄ , X ₃ and X ₄ are each independently a divalent organic group with 2 or more carbon atoms, n ₃ is an integer of 1 to 1000 , N ₄ is an integer from 0 to 500, n ₃ /(n ₃ +n ₄ )>0.5, and contains n ₃ dihydroxydiamide units of X ₃ and Y ₃ and n ₄ of X ₄ and Y ₄ The sequence of the diamide units is arbitrary}

唑前驅物之聚羥基醯胺，下述通式(6)為具有[化21]

The structure of the representation

The polyhydroxyamide of the azole precursor, the following general formula (6) has [化21]

{In the formula, X ₅ is an organic group with 4 to 14 valences, Y ₅ is an organic group with 2 to 12 valences, R ₁₀ and R ₁₁ each independently represent having at least one selected from a phenolic hydroxyl group, a sulfonic acid group or a thiol The organic group of the base, n ₅ is an integer from 3 to 200, and m ₃ and m ₄ represent an integer from 0 to 10}

The structure represented by polyimide, and the following general formula (7) is

{In the formula, a is an integer from 1 to 3, b is an integer from 0 to 3, 1≦(a+b)≦4, R ₁₂ represents a monovalent organic group selected from 1 to 20 carbon atoms, halogen atoms, A monovalent substituent in the group consisting of a nitro group and a cyano group. When b is 2 or 3, a plurality of R ₁ may be the same or different from each other, and X represents a carbon that may have an unsaturated bond A divalent aliphatic group with 2 to 10, a divalent alicyclic group with 3 to 20 carbons, the following general formula (8): [化23] -C _p H _2p O- (8)

(In the formula, p is an integer from 1 to 10) The divalent organic group in the group consisting of a divalent alkoxy group and a divalent organic group with an aromatic ring with carbon number 6 to 12基} The phenol resin represented.

[3] The photosensitive resin composition according to [1] or [2], wherein the photosensitive resin composition comprises a phenol resin having a repeating unit represented by the general formula (7), in the general formula (7) Where X is selected from the following general formula (9):

{In the formula, R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are each independently a hydrogen atom, a monovalent aliphatic group with 1 to 10 carbon atoms, or a carbon in which part or all of the hydrogen atoms are replaced with fluorine atoms A monovalent aliphatic group of 1 to 10, n ₆ is an integer of 0 to 4, and when n ₆ is an integer of 1 to 4, R ₁₇ is a halogen atom, a hydroxyl group, or 1 of carbon numbers 1 to 12 For a valence organic group, at least one R ₁₇ is a hydroxyl group, and when n ₆ is an integer from 2 to 4, the plural R ₁₇ may be the same or different from each other. A divalent group represented by the following general formula (10): [化25]

{In the formula, R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ each independently represent a hydrogen atom, a monovalent aliphatic group with 1 to 10 carbon atoms, or a carbon in which part or all of the hydrogen atoms are substituted with fluorine atoms A monovalent aliphatic group of 1 to 10, W is a single bond, selected from aliphatic groups with 1 to 10 carbons that can be substituted by fluorine atoms, and alicyclic groups with 3 to 20 carbons that can be substituted with fluorine Base, the following general formula (8): [化26] -C _p H _2p O- (8)

(In the formula, p is an integer from 1 to 10) a divalent alkoxy group represented by the following formula (11):

The divalent base in the group consisting of the indicated divalent radical} The divalent organic group in the group consisting of the indicated divalent radical.

[4] A method of manufacturing a hardened relief pattern, comprising: step (1), which is achieved by coating the photosensitive resin composition as described in any one of [1] to [3] on a substrate. A photosensitive resin layer is formed on the substrate; step (2) is to expose the photosensitive resin layer; Step (3) is to develop the photosensitive resin layer after exposure to form a relief pattern; and Step (4) is to heat the relief pattern to form a hardened relief pattern.

[5] The method described in [4], wherein the substrate is formed of copper or copper alloy.

[6] A semiconductor device comprising a hardened relief pattern obtained by the manufacturing method described in [4] or [5].

In addition, the inventors have discovered that by combining a photosensitive resin with a specific thermal crosslinking agent, a cured film can be obtained in which the generation of voids at the interface contacting the Cu layer after the high temperature storage test is suppressed. Negative photosensitive resin composition. The present invention can also be applied to the following aspects.

[1] A negative photosensitive resin composition comprising (A) at least one resin selected from the group consisting of polyamide acid, polyamide acid ester, and polyamide acid salt: 100 parts by mass, ( B-2) Thermal crosslinking agent: 0.01-50 parts by mass based on 100 parts by mass of the above (A) resin, and (C) sensitizer: 1-50 parts by mass based on 100 parts by mass of the above (A) resin Copies.

[2] The photosensitive resin composition according to [1], wherein the resin (A) is selected from polyimide precursors containing the following general formula (1) and polyimide precursors containing the following general formula (4) At least one of the group consisting of amides.

The following general formula (1) is [化28]

{In the formula, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n ₁ is an integer from 2 to 150, and R ₁ and R ₂ are independently hydrogen atoms and saturated with carbon numbers of 1 to 30 Aliphatic group, aromatic group, or the following general formula (2):

(Wherein, R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or an organic group with 1 to 3 carbons, and m ₁ is an integer from 2 to 10) represented by a monovalent organic group, or 1 ~4 saturated aliphatic group, or the following general formula (3):

(In the formula, R ₆ , R ₇ and R ₈ are each independently a hydrogen atom or an organic group with 1 to 3 carbons, and m ₂ is an integer of 2 to 10), which is represented by a monovalent ammonium ion). The polyimide precursor of polyamide acid, polyamide acid ester or polyamide acid salt, the following general formula (4) has

{In the formula, X ₂ is a trivalent organic group with 6 to 15 carbons, Y ₂ is a divalent organic group with 6 to 35 carbons, and can be the same structure or multiple structures, and R ₉ is at least An organic group with a radical polymerizable unsaturated bond group with carbon number 3-20, and n ₂ is an integer from 1 to 1000}

Polyamide of the structure shown.

環之化合物、(B-2-8)含

唑啉環之化合物、(B-2-9)含碳二醯亞胺基之化合物、(B-2-10)烯丙基化合物、(B-2-11)三

硫醇化合物、及(B-2-12)金屬螯合化合物所組成之群中之至少一種。 [3] The photosensitive resin composition according to [1], wherein the (B-2) thermal crosslinking agent is selected from (B-2-1) containing at least one of a methylol group or an alkoxyalkyl group (B-2-2) Compounds containing oxirane ring, (B-2-3) Compounds containing isocyanate group, (B-2-4) Compounds containing bismaleimide group Compound, (B-2-5) Compound containing aldehyde group, (B-2-6) Compound containing oxetane ring, (B-2-7) Compound containing benzo

Ring compound, (B-2-8) containing

Oxazoline compound, (B-2-9) carbodiimide-containing compound, (B-2-10) allyl compound, (B-2-11) three

At least one of the group consisting of thiol compound and (B-2-12) metal chelate compound.

[4] The photosensitive resin composition according to [1] or [3], wherein the (B-2) thermal crosslinking agent is (B-2-1) A compound containing at least one of a hydroxymethyl group or an alkoxyalkyl group.

[5] The photosensitive resin composition according to [1] or [3], wherein the (B-2) thermal crosslinking agent has the following general formula (TS1):

{In the formula, Rs1 is a hydrogen atom, a univalent group selected from the group consisting of methyl, ethyl, n-propyl and isopropyl, and Rs2 is an alkyl group with 1-10 carbon atoms selected from a hydroxyl group , Alkoxy group with 1-10 carbon atoms, ester group with 1-10 carbon atoms, and urethane group, mm1 is an integer of 1 to 5, mm2 is 0-4 Of integers. Here, 1≦(mm1+mm2)≦5, nn1 is an integer of 1~4, V ₁ is CH ₂ ORs1 when nn1=1, single bond or 2~4 valence organic when nn1=2~4 base. When there are plural CH ₂ ORs1 and R ₁₀ , these may be the same or different from each other}

The structure represented.

[6] A method of manufacturing a hardened relief pattern, comprising: step (1), which is achieved by coating the photosensitive resin composition as described in any one of [1] to [5] on a substrate. A photosensitive resin layer is formed on the substrate; step (2) is to expose the photosensitive resin layer; step (3) is to develop the photosensitive resin layer after the exposure to form a relief pattern; and Step (4) is to form a hardened relief pattern by heating the relief pattern.

[7] The method according to [6], wherein the substrate is formed of copper or copper alloy.

In addition, the inventors found that by combining a specific photosensitive resin with a specific fluorine-containing hydrophobic compound, a photosensitive resin composition capable of forming a cured film can be obtained. The cured film can be obtained at high temperatures. After the high temperature storage test, no voids are generated at the interface between the Cu layer and the resin layer and the resin layer with higher adhesion is not generated. The present invention can also be applied to the following aspects.

唑、酚醛清漆、聚羥基苯乙烯及酚樹脂所組成之群中之至少一種樹脂：100質量份，(B-3)含氟疏水性化合物：以上述(A)樹脂100質量份為基準計0.01~50質量份，以及(C)感光劑：以上述(A)樹脂100質量份為基準計1~50質量份。 [1] A photosensitive resin composition comprising (A) selected from the group consisting of polyamide acid, polyamide acid ester, polyamide acid salt, polyhydroxyamide, polyaminoamide, polyamide, polyamide Amide imine, polyimide, polybenzo

At least one resin from the group consisting of azole, novolac, polyhydroxystyrene, and phenol resin: 100 parts by mass, (B-3) fluorine-containing hydrophobic compound: 0.01 based on 100 parts by mass of the above (A) resin ~50 parts by mass, and (C) photosensitizer: 1-50 parts by mass based on 100 parts by mass of the (A) resin.

唑前驅物、包含下述通式(6)之聚醯亞胺、以及酚醛清漆、聚羥基苯乙烯及包含下述通式(7)之酚樹脂所組成之群中之至少一種。 [2] The photosensitive resin composition according to [1], wherein the resin (A) is selected from polyimide precursors containing the following general formula (1) and polyimide precursors containing the following general formula (4) Amide, containing the following general formula (5) poly

An azole precursor, a polyimide containing the following general formula (6), and at least one of the group consisting of novolac, polyhydroxystyrene, and a phenol resin containing the following general formula (7).

The following general formula (1) is [化33]

{In the formula, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n ₁ is an integer from 2 to 150, and R ₁ and R ₂ are independently hydrogen atoms and saturated with carbon numbers of 1 to 30 Aliphatic group, aromatic group, or the following general formula (2):

(Wherein, R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or an organic group with 1 to 3 carbons, and m ₁ is an integer from 2 to 10) represented by a monovalent organic group, or 1 ~4 saturated aliphatic group, or the following general formula (3):

(In the formula, R ₆ , R ₇ and R ₈ are each independently a hydrogen atom or an organic group with 1 to 3 carbons, and m ₂ is an integer of 2 to 10), which is represented by a monovalent ammonium ion). The polyimide precursor of polyamide acid, polyamide acid ester or polyamide acid salt, the following general formula (4) has

{In the formula, X ₂ is a trivalent organic group with 6 to 15 carbons, Y ₂ is a divalent organic group with 6 to 35 carbons, and can be the same structure or multiple structures, and R ₉ is at least An organic group with a radical polymerizable unsaturated bond group with carbon number 3-20, and n ₂ is an integer from 1 to 1000}

The structure of polyamide, the following general formula (5) has

{Where, Y ₃ is a 4-valent organic group with carbon atoms, Y ₄ , X ₃ and X ₄ are each independently a divalent organic group with 2 or more carbon atoms, n ₃ is an integer of 1 to 1000 , N ₄ is an integer from 0 to 500, n ₃ /(n ₃ +n ₄ )>0.5, and contains n ₃ dihydroxydiamide units of X ₃ and Y ₃ and n ₄ of X ₄ and Y ₄ The sequence of the diamide units is arbitrary}

唑前驅物之聚羥基醯胺， 下述通式(6)為具有

The structure of the representation

The polyhydroxyamide of the azole precursor, the following general formula (6) has

{In the formula, X ₅ is an organic group with 4 to 14 valences, Y ₅ is an organic group with 2 to 12 valences, R ₁₀ and R ₁₁ each independently represent having at least one selected from a phenolic hydroxyl group, a sulfonic acid group or a thiol The organic group of the base, n ₅ is an integer from 3 to 200, and m ₃ and m ₄ represent an integer from 0 to 10}

The structure represented by polyimide, and the following general formula (7) is

{In the formula, a is an integer from 1 to 3, b is an integer from 0 to 3, 1≦(a+b)≦4, R ₁₂ represents a monovalent organic group selected from 1 to 20 carbon atoms, halogen atoms, A monovalent substituent in the group consisting of a nitro group and a cyano group. When b is 2 or 3, a plurality of R ₁ may be the same or different from each other, and X represents a carbon that may have an unsaturated bond A bivalent aliphatic group with 2 to 10, a divalent alicyclic group with 3 to 20 carbons, the following general formula (8): [化40] -C _p H _2p O- (8)

(In the formula, p is an integer from 1 to 10) The divalent organic group in the group consisting of a divalent alkoxy group and a divalent organic group with an aromatic ring with carbon number 6 to 12基} The phenol resin represented.

[3] The photosensitive resin composition according to [1] or [2], wherein X in the above general formula (7) is selected from the following general formula (9):

{In the formula, R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are each independently a hydrogen atom, a monovalent aliphatic group with 1 to 10 carbon atoms, or a carbon in which part or all of the hydrogen atoms are replaced with fluorine atoms A monovalent aliphatic group of 1 to 10, n ₆ is an integer of 0 to 4, and when n ₆ is an integer of 1 to 4, R ₁₇ is a halogen atom, a hydroxyl group, or 1 of carbon numbers 1 to 12 For a valence organic group, at least one R ₆ is a hydroxyl group, and when n ₆ is an integer of 2 to 4, the plural R ₁₇ may be the same or different from each other. The divalent group represented by the following general formula (10):

{In the formula, R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ each independently represent a hydrogen atom, a monovalent aliphatic group with 1 to 10 carbon atoms, or a carbon in which part or all of the hydrogen atoms are substituted with fluorine atoms A monovalent aliphatic group of 1 to 10, W is a single bond, selected from aliphatic groups with 1 to 10 carbons that can be substituted by fluorine atoms, and alicyclic groups with 3 to 20 carbons that can be substituted by fluorine atoms Base, the following general formula (8): [化43] -C _p H _2p O- (8)

(In the formula, p is an integer from 1 to 10) a divalent alkoxy group represented by the following formula (11):

The divalent base in the group consisting of the indicated divalent radical} The divalent organic group in the group consisting of the indicated divalent radical.

[4] The photosensitive resin composition according to any one of [1] to [3], wherein the above (B-3) contains The weight ratio of fluorine atoms in the molecule of the fluorine hydrophobic compound is 30% by mass or more and 80% by mass or less.

[5] The photosensitive resin composition according to any one of [1] to [4], wherein the (B-3) fluorine-containing hydrophobic compound has at least one unsaturated double bond in the molecule.

[6] The photosensitive resin composition according to any one of [1] to [5], wherein the (B-3) fluorine-containing hydrophobic compound is an acrylate or methacrylate compound having a perfluoro group.

[7] A method of manufacturing a hardened relief pattern, comprising the step (1), which is applied to the substrate by coating the photosensitive resin composition as described in any one of [1] to [6] on the substrate A photosensitive resin layer is formed on the top; step (2), which is to expose the photosensitive resin layer; step (3), which is to develop the photosensitive resin layer after the exposure to form a relief pattern; and step ( 4), which forms a hardened relief pattern by heating the above-mentioned relief pattern.

[8] The method according to [7], wherein the substrate is formed of copper or copper alloy.

According to the present invention, it is possible to provide a photosensitive resin composition capable of obtaining a photosensitive resin having high adhesiveness without generating voids at the interface between the Cu layer and the resin layer after a high temperature storage test. A method for forming a hardened relief pattern of a photosensitive resin composition, and a semiconductor device having the hardened relief pattern.

Hereinafter, a mode for implementing the present invention (hereinafter referred to as "this embodiment") will be described in detail. Furthermore, this embodiment is an illustration for explaining the present invention, and is not intended to limit the present invention. Bright. The present invention can be implemented with appropriate changes within the scope of its gist.

Furthermore, in this specification, when there are plural structures in the molecule represented by the same symbol in the general formula, they may be the same or different from each other.

<Photosensitive resin composition>

唑、以及酚醛清漆、聚羥基苯乙烯及酚樹脂所組成之群中之至少一種樹脂：100質量份、(B)塑化劑：以(A)樹脂100質量份為基準計0.1~50質量份、(C)感光劑：以(A)樹脂100質量份為基準計1~50質量份。 This embodiment uses the following components as essential components, that is, (A) is selected from polyamide acid, polyamide acid ester, polyamide acid salt, polyhydroxyamide, polyaminoamide, polyamide, Polyimide, polyimide, polybenzo

At least one resin from the group consisting of azole, novolak, polyhydroxystyrene, and phenol resin: 100 parts by mass, (B) plasticizer: 0.1-50 parts by mass based on 100 parts by mass of (A) resin , (C) Sensitizer: 1-50 parts by mass based on 100 parts by mass of (A) resin.

<Photosensitive resin composition>

唑、以及酚酸清漆、聚羥基苯乙烯及酚樹脂所組成之群中之至少一種樹脂：100質量份、(B-1)奈米粒子：以(A)樹脂100質量份為基準計0.01~10質量份、(C)感光劑：以(A)樹脂100質量份為基準計1~50質量份。 In another embodiment, the following components are used as essential components. That is, (A) is selected from the group consisting of polyamide acid, polyamide acid ester, polyamide acid salt, polyhydroxyamide, polyaminoamide, and polyamide. Amide, polyimide, polyimide, polybenzo

At least one resin from the group consisting of azole, phenolic acid varnish, polyhydroxystyrene and phenol resin: 100 parts by mass, (B-1) Nanoparticles: 0.01~ based on 100 parts by mass of (A) resin 10 parts by mass, (C) photosensitizer: 1-50 parts by mass based on 100 parts by mass of (A) resin.

<Photosensitive resin composition>

Moreover, another embodiment is a negative photosensitive resin composition, which has the following components as essential components, namely, (A) selected from the group consisting of polyamide acid, polyamide acid ester, and polyamide acid salt At least one of the resins: 100 parts by mass, (B-2) thermal crosslinking agent: 0.01-10 parts by mass based on 100 parts by mass of (A) resin, (C) photosensitive agent: 100 parts by mass of (A) resin 1-50 parts by mass based on parts.

<Photosensitive resin composition>

唑、以及酚醛清漆、聚羥基苯乙烯及酚樹脂所組成之群中之至少一種樹脂：100質量份、(B-3)含氟疏水性化合物：以上述(A)樹脂100質量份為基準計0.01~50質量份、(C)感光劑：以(A)樹脂100質量份為基準計1~50質量份。 In another embodiment, the following components are used as essential components. That is, (A) is selected from the group consisting of polyamide acid, polyamide acid ester, polyamide acid salt, polyhydroxyamide, polyaminoamide, and polyamide. Amide, polyimide, polyimide, polybenzo

Azole, and at least one resin from the group consisting of novolac, polyhydroxystyrene, and phenol resin: 100 parts by mass, (B-3) fluorine-containing hydrophobic compound: based on 100 parts by mass of the above (A) resin 0.01-50 parts by mass, (C) sensitizer: 1-50 parts by mass based on 100 parts by mass of (A) resin.

(A) Resin

唑、以及酚醛清漆、聚羥基苯乙烯及酚樹脂所組成之群中之至少一種樹脂作為主成分。此處，所謂主成分意指含有占樹脂整體60質量%以上之該等樹脂，較佳為含有80質量%以上。又，視需要亦可含有其他樹脂。 The (A) resin used in the present invention will be described. The (A) resin of the present invention is selected from polyamide acid, polyamide acid ester, polyamide acid salt, polyhydroxyamide, polyaminoamide, polyamide, polyamide imide, Polyimide, polybenzo

As the main component, azole, and at least one resin from the group consisting of novolac, polyhydroxystyrene, and phenol resin. Here, the term “main component” means containing 60% by mass or more of these resins in the entire resin, and preferably containing 80% by mass or more. Moreover, other resins may be contained as needed.

The weight average molecular weight of these resins is preferably 200 or more, more preferably 5,000 or more in terms of polystyrene conversion based on gel permeation chromatography from the viewpoint of heat resistance and mechanical properties after heat treatment. It is preferably 1,000 or more, more preferably 1,000 or more. The upper limit is preferably 500,000 or less, and when a photosensitive resin composition is used, it is more preferably 20,000 or less from the viewpoint of solubility in the developer.

In the present invention, in order to form a relief pattern, the (A) resin is preferably a photosensitive resin. The photosensitive resin is used together with the following (C) photosensitizer to become a photosensitive resin composition, and is a resin that causes dissolution or undissolution in the subsequent development step.

唑、以及包含酚醛清漆、聚羥基苯乙烯之酚樹脂之中，就熱處理後之樹脂之耐熱性、機械特性優異之方面而言，可較佳地使用聚醯亞胺前驅物(聚醯胺酸、聚醯胺酸酯、聚醯胺酸鹽)、聚醯胺、聚羥基醯胺、聚醯亞胺及酚樹脂。 As photosensitive resins, polyamides, polyamides, polyamides, polyhydroxyamides, polyaminoamides, polyamides, polyimides, polyimides, Polybenzo

Among the azoles, and phenol resins containing novolac and polyhydroxystyrene, in terms of the heat resistance and mechanical properties of the heat-treated resin, a polyimide precursor (polyamide acid , Polyamide ester, polyamide acid salt), polyamide, polyhydroxyamide, polyimide and phenol resin.

In addition, these photosensitive resins can be selected according to the desired use together with the following (C) photosensitive agent to prepare any negative or positive photosensitive resin composition.

[(A) Polyamide acid, polyamide acid ester, polyamide acid salt]

In the photosensitive resin composition of the present invention, an example of the resin (A) that is the best in terms of heat resistance and photosensitive characteristics is the above general formula (1):

{In the formula, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n ₁ is an integer from 2 to 150, and R ₁ and R ₂ are independently hydrogen atoms and saturated fats with 1 to 30 carbon atoms. Family group, or the above general formula (2):

(Wherein, R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or an organic group with 1 to 3 carbons, and m ₁ is an integer from 2 to 10) represented by a monovalent organic group, or 1 A monovalent organic group represented by a saturated aliphatic group of ~4, or the following general formula (3):

(In the formula, R ₆ , R ₇ and R ₈ are each independently a hydrogen atom or an organic group with 1 to 3 carbons, and m ₂ is an integer of 2 to 10), which is represented by a monovalent ammonium ion). Polyamide acid, polyamide acid ester or polyamide acid salt of polyimide precursor.

The polyimide precursor is converted into polyimide by performing cyclization treatment with heating (for example, 200°C or higher). The polyimide precursor is suitable for a negative photosensitive resin composition.

In the above general formula (1), the tetravalent organic group represented by X ₁ is preferably an organic group having 6 to 40 carbon atoms, more preferably a -COOR ₁ group, in terms of having both heat resistance and photosensitive properties. And the aromatic group or the alicyclic aliphatic group in which the -COOR ₂ group and the -CONH- group are located in the ortho position to each other. The tetravalent organic group represented by X ₁ is preferably an organic group having 6 to 40 carbon atoms containing an aromatic ring, and more preferably the following formula (30): [化48]

{In the formula, R25 is a monovalent group selected from hydrogen atoms, fluorine atoms, C1-C10 hydrocarbon groups, C1-C10 fluorine-containing hydrocarbon groups, l is an integer selected from 0-2, and m is selected from 0-3 Integer, n is an integer selected from 0~4}

The structure shown is not limited to these. In addition, the structure of X ₁ may be one type or a combination of two or more types. The X ₁ group having the structure represented by the above formula is particularly preferable in terms of having both heat resistance and photosensitive characteristics.

In the above general formula (1), the divalent organic group represented by Y ₁ is preferably an aromatic group having 6 to 40 carbon atoms in terms of having both heat resistance and photosensitive properties. For example, the following formulas (31):

{Where R25 is a monovalent group selected from hydrogen atom, fluorine atom, C1~C10 hydrocarbon group, C1~C10 fluorine-containing hydrocarbon group, n is an integer selected from 0~4}

The structure shown is not limited to these. In addition, the structure of Y ₁ may be one type or a combination of two or more types. The Y ₁ group having the structure represented by the above formula (31) is particularly preferable in terms of having both heat resistance and photosensitive characteristics.

R ₃ in the above general formula (2) is preferably a hydrogen atom or a methyl group, and R ₄ and R ₅ are preferably a hydrogen atom from the viewpoint of photosensitive properties. In addition, m ₁ is an integer of 2 or more and 10 or less, preferably an integer of 2 or more and 4 or less from the viewpoint of photosensitivity.

When a polyimide precursor is used as the (A) resin, as a method of imparting photosensitivity to the photosensitive resin composition, ester bond type and ion bond type can be cited. The former is a method of introducing a compound having a photopolymerizable group, that is, an olefinic double bond, into the side chain of a polyimide precursor through an ester bond, and the latter is a method of combining the carboxyl group of the polyimide precursor with an amino group A method in which the amine group of the (meth)acrylic compound is bonded via an ionic bond to provide a photopolymerizable group.

The above-mentioned ester-bonded polyimide precursor is obtained by the following method: firstly, a tetracarboxylic dianhydride containing the above-mentioned 4-valent organic group X ₁ and an alcohol having a photopolymerizable unsaturated double bond And any saturated aliphatic alcohols with carbon number of 1 to 4 are reacted to prepare partially esterified tetracarboxylic acid (hereinafter also referred to as acid/ester body), and then it is combined with the above-mentioned divalent organic group Y Diamines of ₁ undergo condensation polymerization of amides.

(Preparation of acid/ester body)

In the present invention, as a tetracarboxylic dianhydride containing a tetravalent organic group X ₁ suitable for preparing ester-bonded polyimide precursors, four of the structures represented by the general formula (30) can be cited Carboxylic dianhydride is representative such as pyromellitic dianhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'- Tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, diphenylsulfonium-3,3',4,4'-tetracarboxylic dianhydride, diphenyl Methane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, 2,2-bis(3,4-phthalic anhydride) -1,1,1,3,3,3-hexafluoropropane, etc., preferably exemplified: pyromellitic dianhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, Benzophenone-3,3',4,4'-tetracarboxylic dianhydride and biphenyl-3,3',4,4'-tetracarboxylic dianhydride, but are not limited to these. In addition, these can of course be used alone, but two or more types can also be mixed and used.

In the present invention, as an alcohol having a photopolymerizable unsaturated double bond suitable for preparing an ester-bonded polyimide precursor, for example, 2-propenyloxyethanol and 1-propenyloxy -3-Propanol, 2-acrylamidoethanol, hydroxymethyl vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-acrylate Butoxypropyl, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-tertiary butoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate Hydroxy-3-cyclohexyloxypropyl ester, 2-methacryloxyethanol, 1-methacryloxy-3-propanol, 2-methacrylaminoethanol, hydroxymethyl vinyl Ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-methacrylate Phenoxypropyl, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-tert-butoxypropyl methacrylate, 2-hydroxy-3-cyclohexyl methacrylate Propyl propyl and so on.

It is also possible to mix a part of the above-mentioned alcohols as a saturated aliphatic alcohol with 1 to 4 carbon atoms, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, and the like.

The above-mentioned tetracarboxylic dianhydride and the above-mentioned alcohols suitable for the present invention are dissolved in the solvent described below in the presence of a basic catalyst such as pyridine and stirred at a temperature of 20-50°C for 4-10 hours. By mixing, the esterification reaction of acid anhydride is carried out, and the desired acid/ester body can be obtained.

(Preparation of polyimide precursor)

For the above acid/ester body (typically a solution in the following solvent), put a suitable dehydrating condensing agent under ice cooling, such as bicyclic carbodiimide, dicyclohexylcarbodiimide, 1 -Ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-dibutyl Diamidocarbonate, etc. are mixed to form the acid/ester body into a polyanhydride, and then dropped into it to dissolve or disperse the diamine containing the divalent organic group Y ₁ suitable for use in the present invention In the solvent obtained, the amide condensation polymerization is carried out to obtain the target polyimide precursor. Alternatively, after chlorinating the acid part in the above acid/ester body by using sulfite chloride or the like, it is reacted with a diamine compound in the presence of a base such as pyridine to obtain the target polyimide precursor.

Examples of diamines containing a divalent organic group Y ₁ that are suitably used in the present invention include diamines having the structure represented by the general formula (31), such as p-phenylenediamine and m-phenylenediamine , 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl Amino, 3,3'-diaminodiphenyl, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4, 4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4- Aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl] benzene, bis[4-(3-amine Phenyloxy) phenyl) sulfide, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4 -Aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis (4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-amino) Phenyl) hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl)propane, 2,2-bis[4-(4-aminophenoxy)phenyl)hexa Fluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, o-tolidine, 9,9-bis(4-aminophenyl)sulfone, and these benzene rings Part of the above hydrogen atoms is substituted by methyl, ethyl, hydroxymethyl, hydroxyethyl, halogen, etc., such as 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2 '-Dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4, 4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl , 2,2'-Dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4' -Diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc.; preferably examples include: p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 2, 2'-Dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diamine However, it is not limited to methyl biphenyl, 4,4'-diamino octafluorobiphenyl, etc., and mixtures thereof.

In addition, in order to improve the adhesion between the resin layer formed on the substrate by coating the photosensitive resin composition of the present invention on the substrate and various substrates, when preparing the polyimide precursor, it may be combined with 1,3- Diaminosiloxanes such as bis(3-aminopropyl)tetramethyldisiloxane and 1,3-bis(3-aminopropyl)tetraphenyldisiloxane are copolymerized.

After the amide condensation polymerization reaction is completed, if necessary, the water absorption by-product of the dehydration condensing agent coexisting in the reaction solution is filtered and separated, and water, aliphatic lower alcohol, or a mixture thereof, etc. are added to the obtained polymer component The poor solvent causes the polymer to be analyzed, and the re-dissolution and re-precipitation operations are repeated to refine the polymer and vacuum-dried to isolate the target polyimide precursor. In order to improve the purification system, the polymer solution can also be passed through a column filled with anion and/or cation exchange resin swelled with a suitable organic solvent to remove ionic impurities.

On the other hand, the ionic bond type polyimide precursor is typically obtained by reacting tetracarboxylic dianhydride and diamine. In this case, at least one of R ₁ and R ₂ in the general formula (1) is a hydroxyl group.

The tetracarboxylic dianhydride is preferably an anhydride of tetracarboxylic acid containing the structure of the above formula (30), and the diamine is preferably a diamine containing the structure of the above formula (31). By adding the following (meth)acrylic compound having an amino group to the obtained polyamide precursor, a photopolymerizable group is provided by the ionic bonding of the carboxyl group and the amino group.

As the (meth)acrylic compound having an amino group, for example, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, and diethylaminoethyl methacrylate are preferred. Ethyl, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, diethylaminopropyl acrylate, diethylaminopropyl methacrylate, dimethylaminobutyl acrylate, methacrylic acid Dimethylaminobutyl, diethylaminobutyl acrylate, diethylaminobutyl methacrylate, dialkylaminoalkyl acrylate or dialkylaminoalkyl methacrylate, among which, From the viewpoint of photosensitivity, it is preferred that the alkyl group on the amino group has 1 to 10 carbon atoms and the alkyl chain has 1 to 10 carbon atoms. Dialkylaminoalkyl acrylate or dimethacrylate Alkylamino alkyl ester.

Regarding the blending amount of the (meth)acrylic compound having an amine group, it is 1-20 parts by mass relative to 100 parts by mass of the (A) resin, and from the viewpoint of photosensitivity characteristics, it is preferably 2-15 Mass parts. With respect to 100 parts by mass of the resin (A), 1 part by mass or more of the (meth)acrylic compound having an amino group as the photosensitizer (C) is formulated to provide excellent light sensitivity, and a thick film is achieved by formulating 20 parts by mass or less Excellent curability.

Regarding the molecular weight of the ester bond type and the ion bond type polyimide precursor, when measured in the form of polystyrene conversion weight average molecular weight based on gel permeation chromatography, it is preferably 8,000 to 150,000 , More preferably 9,000~50,000. When the weight average molecular weight is above 8,000, the mechanical properties are good, when the weight average molecular weight is below 150,000, the dispersibility in the developer is good, and the resolution of the relief pattern is good. As the developing solvent for gel permeation chromatography, tetrahydrofuran and N-methyl-2-pyrrolidone are recommended. Also, the weight average molecular weight It is calculated based on a calibration curve made using standard monodisperse polystyrene. As standard monodisperse polystyrene, it is recommended to choose from STANDARD SM-105, an organic solvent standard sample manufactured by Showa Denko Corporation.

[(A) Polyamide]

Another example of the preferable (A) resin in the photosensitive resin composition of the present invention has the following general formula (4):

{In the formula, X ₂ is a trivalent organic group with 6 to 15 carbons, Y ₂ is a divalent organic group with 6 to 35 carbons, and can be the same structure or multiple structures, and R ₉ is at least An organic group with a radical polymerizable unsaturated bond group with carbon number 3-20, and n ₂ is an integer from 1 to 1000}

Polyamide of the structure shown. This polyamide is suitable for use in negative photosensitive resin compositions.

In the above general formula (4), as the base represented by R ₉ , in terms of having both photosensitive properties and chemical resistance, the following general formula (32) is preferred [化51]

{In the formula, R ₃₂ is an organic group with at least one radically polymerizable unsaturated bond group with carbon number 2 to 19}

The base expressed.

In the above general formula (4), the trivalent organic group represented by X ₂ is preferably a trivalent organic group with 6 to 15 carbon atoms, for example, preferably selected from the following formula (33):

The aromatic group in the represented group is more preferably an aromatic group obtained by removing a carboxyl group and an amino group from the structure of an amino-substituted isophthalic acid.

In the above general formula (4), the divalent organic group represented by Y ₂ is preferably an organic group with 6 to 35 carbon atoms, and more preferably has 1 to 4 substituted aromatic rings or aliphatic A cyclic organic group of a group ring, or an aliphatic group or siloxane group without a cyclic structure. Examples of the divalent organic group represented by Y ₂ include the following general formula (I) and the following general formulas (34) and (35): [化53]

[化54]

{In the formula, R ₃₃ and R ₃₄ are each independently selected from the group consisting of alkyl, methyl (-CH ₃ ), ethyl (-C ₂ H ₅ ), propyl (-C ₃ H ₇ ) or butyl (-C ₄ H ₉ ) is a group in the group consisting of, and the propyl and butyl include various isomers}

[化55]

{In the formula, m ₇ is an integer from 0 to 8, m ₈ and m ₉ are independently an integer from 0 to 3, m ₁₀ and m ₁₁ are independently an integer from 0 to 10, and R ₃₅ and R ₃₆ are methyl (-CH ₃ ), ethyl (-C ₂ H ₅ ), propyl (-C ₃ H ₇ ), butyl (-C ₄ H ₉ ) or their isomers}.

Regarding the aliphatic group or siloxyalkyl group having no cyclic structure, as the preferred one, the following general formula (36) can be cited:

{In the formula, m ₁₂ is an integer from 2 to 12, m ₁₃ is an integer from 1 to 3, m ₁₄ is an integer from 1 to 20, and R ₃₇ , R ₃₈ , R ₃₉ and R ₄₀ are independently carbon numbers 1~ 3 is an alkyl group or a substituted phenyl group}.

The polyamide resin of the present invention can be synthesized, for example, by the following method.

(Synthesis of end-blocking body of phthalic acid compound)

In the first step, a compound having a trivalent aromatic group X ₂ is selected from the group consisting of phthalic acid substituted with amino groups, phthalic acid substituted with amino groups, and terephthalic acid substituted with amino groups. One mol of at least one compound (hereinafter referred to as "phthalic acid compound") in the composition group reacts with one mol of the compound that reacts with an amine group to synthesize the amine group of the phthalic acid compound A compound modified and blocked with the following radically polymerizable unsaturated bond-containing group (hereinafter referred to as "phthalic acid compound blocked body"). These can be used alone or in combination.

If the phthalic acid compound is terminated by the radical polymerizable unsaturated bond-containing group, it is possible to impart negative photosensitivity (photocuring property) to the polyamide resin.

The group containing a radically polymerizable unsaturated bond is preferably an organic group having a radically polymerizable unsaturated bond group with a carbon number of 3 to 20, and particularly preferably contains a methacryloyl group or an acryloyl group The base.

The above-mentioned phthalic acid compound blocked body can be formed by making the amino group of the phthalic acid compound, and the chlorinated, isocyanate or epoxy compound having at least one radically polymerizable unsaturated bond group with carbon number of 3-20 Obtained by reaction.

Examples of suitable oxychlorides include (meth)acrylic acid chloride, 2-[(meth)acrylic acidoxy]acetoxychloride, 3-[(meth)acrylicoxylic acid chloride, chlorine 2-[(meth)propenoxy] ethyl formate, 3-[(meth)propenoxypropyl] chloroformate, etc. Suitable isocyanates include: 2-(meth)acryloxyethyl isocyanate, 1,1-bis[(meth)acryloxymethyl]ethyl isocyanate, isocyanate 2-[2-(Meth)propenyloxyethoxy] ethyl ester and the like. As a suitable epoxy compound, glycidyl (meth)acrylate etc. are mentioned. These can be used alone or in combination, but it is particularly preferred to use methacrylic acid chloride and/or 2-(methacryloxy)ethyl isocyanate.

Furthermore, as these phthalic acid compound end-blockers, it is preferable that the phthalic acid compound is 5-aminoisophthalic acid to obtain a polyamide having excellent photosensitivity and film properties after heat curing. .

The above-mentioned blocking reaction can be achieved by stirring and dissolving the phthalic acid compound and the blocking agent in the solvent described below due to the presence of a basic catalyst such as pyridine or a tin-based catalyst such as di-n-butyltin dilaurate. Mix and proceed.

Chlorine, etc., will generate hydrogen chloride as a by-product in the process of the capping reaction according to the type of capping agent. In this case, in order to prevent pollution to the subsequent steps, it is better to perform appropriate purification, that is, to temporarily re-precipitate in water and wash and dry it, or to pass it through a column filled with ion exchange resin to remove and reduce ions. Ingredients etc.

(Synthesis of polyamide)

The above-mentioned phthalic acid compound capped body and a diamine compound having a bivalent organic group Y ₂ are mixed in the following solvent in the presence of a basic catalyst such as pyridine or triethylamine to carry out Amine condensation polymerization can obtain the polyamide of the present invention.

As a method of polycondensation polymerization of amides, a method of using a dehydrating condensing agent to make a phthalic acid compound end-capped body into a symmetric polyanhydride and then mixing with a diamine compound, or a known method to make a phthalic acid compound end-capped body A method of mixing with a diamine compound after chlorination, a method of reacting a dicarboxylic acid component with an active esterification agent in the presence of a dehydrating condensing agent to realize a method of mixing with a diamine compound after active esterification, etc.

As the dehydrating condensing agent, for example, preferable ones include: dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1'- Carbonyldioxy-di-1,2,3-benzotriazole, N,N'-dibutanedioxyimino carbonate, etc.

Examples of the chlorinating agent include sulfite chloride.

烯-2,3-二羧醯亞胺、2-羥基亞胺基-2-氰基乙酸乙酯、2-羥基亞胺基-2-氰基乙醯胺等。 As the active esterification agent, N-hydroxysuccinimide or 1-hydroxybenzotriazole, N-hydroxy-5-drop

En-2,3-dicarboxyimide, ethyl 2-hydroxyimino-2-cyanoacetate, 2-hydroxyimino-2-cyanoacetamide, etc.

The diamine compound having the organic group Y ₂ is preferably selected from aromatic diamine compounds, aromatic diaminophenol compounds, alicyclic diamine compounds, linear aliphatic diamine compounds, and silicone diamines At least one diamine compound in the group consisting of compounds may be used in combination of plural kinds if necessary.

Examples of aromatic diamine compounds include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diamine Aminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'- Diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl, 3,4'- Diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diamine Benzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis (4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4- Aminophenoxy) phenyl] ash, bis[4-(3-aminophenoxy)phenyl] ash, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4 '-Bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether , 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2- Bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, o-tolidine, 9,9-bis(4-aminophenyl) sulfide, and one of the hydrogen atoms on the benzene ring are selected from methyl, ethyl, hydroxymethyl, hydroxyethyl and halogen atoms One or more group-substituted diamine compounds in the group.

Examples of diamine compounds in which the hydrogen atom on the benzene ring is substituted include: 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4 ,4'-Diaminobiphenyl, 3,3'-Dimethyl-4,4'-Diaminodiphenylmethane, 2,2'-Dimethyl-4,4'-Diaminodiphenyl Phenylmethane, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, etc.

As the aromatic diaminophenol compound, 3,3'-dihydroxybenzidine, 3,3'-diamino-4,4'-dihydroxybiphenyl, 3,3'-dihydroxy-4 ,4'-Diaminodiphenyl sulfide, 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-(3-hydroxy-4-aminophenyl)hexafluoropropane, bis-(3-hydroxy-4 -Aminophenyl)methane, 2,2-bis-(3-hydroxy-4-aminophenyl)propane, 3,3'-dihydroxy-4,4'-diaminobenzophenone, 3 ,3'-Dihydroxy-4,4'-diaminodiphenyl ether, 4,4'-dihydroxy-3,3'-diaminodiphenyl ether, 2,5-dihydroxy-1,4- Diaminobenzene, 4,6-diaminoresorcinol, 1,1-bis(3-amino-4-hydroxyphenyl)cyclohexane, 4,4-(α-methylbenzylidene) )-Bis(2-aminophenol) and the like.

烷二胺、1-環庚烯-3,7-二胺、4,4'-亞甲基雙(環己基胺)、4,4'-亞甲基雙(2-甲基環己基胺)、1,4-雙(3-胺基丙基)哌

、3,9-雙(3-胺基丙基)-2,4,8,10-四氧雜螺-[5,5]-十一烷等。 As the alicyclic diamine compound, 1,3-diaminocyclopentane, 1,3-diaminocyclohexane, 1,3-diamino-1-methylcyclohexane, 3 ,5-Diamino-1,1-dimethylcyclohexane, 1,5-diamino-1,3-dimethylcyclohexane, 1,3-diamino-1-methyl- 4-isopropylcyclohexane, 1,2-diamino-4-methylcyclohexane, 1,4-diaminocyclohexane, 1,4-diamino-2,5-diethyl Cyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 2-(3-aminocyclopentyl)-2-propane Base amine, menthane diamine, isophorone diamine, drop

Alkanediamine, 1-cycloheptene-3,7-diamine, 4,4'-methylenebis(cyclohexylamine), 4,4'-methylenebis(2-methylcyclohexylamine) , 1,4-bis(3-aminopropyl)piper

, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro-[5,5]-undecane, etc.

Examples of linear aliphatic diamine compounds include: 1,2-diaminoethane, 1,4-diaminobutane, 1,6-diaminohexane, and 1,8-diaminooctane Alkane, 1,10-diaminodecane, 1,12-diaminododecane and other hydrocarbon diamines, or 2-(2-aminoethoxy)ethylamine, 2,2'-( Ethylenedioxy)diethyl Alkoxy-type diamines such as amines and bis[2-(2-aminoethoxy)ethyl]ether.

As the silicone diamine compound, dimethyl (poly)silicone diamine can be cited, for example, PAM-E, KF-8010, X-22-161A, etc., manufactured by Shin-Etsu Chemical Industries.

After the completion of the amide condensation polymerization reaction, the precipitate derived from the dehydrating condensing agent and the like deposited in the reaction liquid are filtered and separated as necessary. Then, a poor solvent for polyamide, such as water, aliphatic lower alcohol, or a mixture thereof, is added to the reaction liquid to precipitate polyamide. Furthermore, the precipitated polyamide is re-dissolved in the solvent, and the reprecipitation operation is repeated to perform purification and vacuum drying to isolate the target polyamide. Furthermore, in order to further improve the precision, the polyamide solution can be passed through a column filled with ion exchange resin to remove ionic impurities.

The polystyrene conversion weight average molecular weight of polyamide based on gel permeation chromatography (hereinafter referred to as "GPC") is preferably 7,000 to 70,000, and more preferably 10,000 to 50,000. If the polystyrene conversion weight average molecular weight is 7,000 or more, the basic physical properties of the cured embossed pattern will be ensured. In addition, if the weight average molecular weight in terms of polystyrene is 70,000 or less, the development solubility when forming the embossed pattern is ensured.

As the eluent for GPC, tetrahydrofuran or N-methyl-2-pyrrolidone is recommended. In addition, the weight average molecular weight value is obtained based on a calibration curve prepared using standard monodisperse polystyrene. As standard monodisperse polystyrene, it is recommended to choose from STANDARD SM-105, an organic solvent standard sample manufactured by Showa Denko.

[(A) Polyhydroxyamide]

Another example of the preferable (A) resin in the photosensitive resin composition of the present invention has the following general formula (5): [化57]

唑前驅物(以下有時將上述通式(5)所表示之聚羥基醯胺簡稱為「聚

唑前驅物」))。 {In the formula, Y ₃ is a tetravalent organic group having carbon atoms, preferably a tetravalent organic group having 2 or more carbon atoms, and Y ₄ , X ₃ and X ₄ are each independently having 2 or more 2 price of the organic carbon atoms, n ₃ is an integer of 1 to 1000., n ₄ is an integer of 0 to _{500., n 3 / (n 3 +} n 4)> 0.5, and comprises X ₃ and Y ₃ of n ₃ The arrangement sequence of n ₄ dihydroxyamide units containing X ₄ and Y ₄ is arbitrary) of the structure represented by polyhydroxyamide (polyhydroxyamide).

Azole precursor (hereinafter sometimes the polyhydroxyamide represented by the above general formula (5) is referred to as "poly

Azole precursors”)).

唑前驅物為具有上述通式(5)中之n₃個二羥基二醯胺單元(以下有時簡稱為二羥基二醯胺單元)之聚合物，亦可具有上述通式(5)中之n₄個二醯胺單元(以下有時簡稱為二醯胺單元)。 Gather

The azole precursor is a polymer having n ₃ dihydroxy diamide units (hereinafter sometimes referred to as dihydroxy diamide units) in the above general formula (5), and may also have the above general formula (5) n ₄ diamide units (hereinafter sometimes referred to as diamide units).

The number of carbon atoms of X ₃ is preferably 2 or more and 40 or less for the purpose of obtaining photosensitive characteristics, and the number of carbon atoms of X ₄ is preferably 2 or more and 40 or less for the purpose of obtaining photosensitive characteristics. Y ₃ The number of carbon atoms is preferably 2 or more and 40 or less based on the purpose of obtaining photosensitive characteristics, and the number of carbon atoms of Y ₄ is preferably 2 or more and 40 or less based on the purpose of obtaining photosensitive characteristics.

唑 結構。通式(5)中之n₃基於獲得感光特性之目的而為1以上，且基於獲得感光特性之目的而為1000以下。n₃較佳為2~1000之範圍，更佳為3~50之範圍，最佳為3~20之範圍。 The dihydroxy diamide unit can be formed by making a diamino dihydroxy compound (preferably diamino phenol) with a structure of Y ₃ (NH ₂ ) ₂ (OH) ₂ and a compound with X ₃ (COOH) ₂ The structure of the dicarboxylic acid is synthesized and formed. Hereinafter, a case where the above-mentioned diaminodihydroxy compound is a diaminophenol is taken as an example to illustrate a typical aspect. The two groups of amine groups and hydroxyl groups of the diaminophenol are located in the ortho position with each other, and the dihydroxydiamide unit is ring-closed under heating at about 250~400℃ to convert into heat-resistant poly

Azole structure. N ₃ in the general formula (5) is 1 or more for the purpose of obtaining photosensitive characteristics, and is 1000 or less for the purpose of obtaining photosensitive characteristics. n _{3 is} preferably in the range of 2 to 1000, more preferably in the range of 3 to 50, and most preferably in the range of 3 to 20.

唑前驅物上縮合n₄個上述二醯胺單元。該二醯胺單元可藉由使具有Y₄(NH₂)₂之結構之二胺與具有X₄(COOH)₂之結構之二羧酸進行合成而形成。通式(5)中之n₄為0~500之範圍，藉由n₄為500以下而獲得良好之感光特性。n₄更佳為0~10之範圍。若二醯胺單元相對於二羥基二醯胺單元之比率過高，則於用作顯影液之鹼性水溶液中之溶解性降低，因此通式(5)中之n₃/(n₃+n₄)之值超過0.5，更佳為0.7以上，最佳為0.8以上。 As needed

Condensate n ₄ diamide units on the azole precursor. The diamide unit can be formed by synthesizing a diamine having a structure of Y ₄ (NH ₂ ) ₂ and a dicarboxylic acid having a structure of X ₄ (COOH) ₂ . In the general formula (5), n ₄ is in the range of 0 to 500, and good photosensitive characteristics can be obtained by n ₄ being 500 or less. n _{4 is more} preferably in the range of 0-10. If the ratio of the diamide unit to the dihydroxy diamide unit is too high, the solubility in the alkaline aqueous solution used as the developer is reduced, so n ₃ /(n ₃ +n in the general formula (5) The value of ₄ ) exceeds 0.5, more preferably 0.7 or more, and most preferably 0.8 or more.

Regarding the diamino phenol as a diamino dihydroxy compound having a structure of Y ₃ (NH ₂ ) ₂ (OH) ₂ , for example, 3,3'-dihydroxybenzidine and 3,3'-diamine can be cited 4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl Chrysene, 4,4'-diamino-3,3'-dihydroxydiphenyl chrysene, 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)hexa Fluoropropane, 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-di Hydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene, etc. These bisaminophenols can be used individually or in combination of 2 or more types. As the Y ₃ group in the bisaminophenol, in terms of photosensitive properties, the following formula (37) is preferred: [化58]

{In the formula, Rs1 and Rs2 each independently represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, a trifluoromethyl group}.

In addition, examples of the diamine having a structure of Y ₄ (NH ₂ ) ₂ include aromatic diamines and silicodiamines. Among them, as aromatic diamines, for example, m-phenylenediamine, p-phenylenediamine, 2,4-toluenediamine, 3,3'-diaminodiphenyl ether, 3,4'-diamino Diphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ash, 4,4'-diaminodiphenyl ash, 3,4'-diamino Diphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-di Amino diphenyl sulfide, 3,3'-diaminodiphenyl ketone, 4,4'-diaminodiphenyl ketone, 3,4'-diaminodiphenyl ketone, 2,2' -Bis(4-aminophenyl)propane, 2,2'-bis(4-aminophenyl)hexafluoropropane, 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-pentane Ene, 4-methyl-2,4-bis(4-aminophenyl)-2-pentene, 1,4-bis(α,α-dimethyl-4-aminobenzyl)benzene, ylidene Amino 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-trimethylindan, bis(p-aminophenyl)phosphine oxide, 4,4'-diaminoazo Benzene, 4,4'-diaminodiphenylurea, 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]bis Benzophenone, 4,4'-bis(4-aminophenoxy)diphenyl sulfide, 4,4'-bis[4-(α,α-dimethyl-4-aminobenzyl)benzene Oxy]benzophenone, 4,4'-bis[4-(α,α-dimethyl-4-aminobenzyl)phenoxy]diphenylsulfonate, 4,4'-diamino Biphenyl, 4,4'-diaminobenzophenone, phenylindandiamine, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-di Methyl-4,4'-diaminobiphenyl, o-toluidine, 2,2-bis(4-aminophenoxyphenyl)propane, bis(4-aminophenoxyphenyl)sulfonate , Bis(4-aminophenoxyphenyl) sulfide, 1,4-(4-aminophenoxyphenyl)benzene, 1,3-(4-aminophenoxyphenyl)benzene, 9,9-bis(4-aminophenyl) pyridium, 4,4'-bis-(3-aminophenoxy) diphenyl pyrene, 4,4'-diaminobenzylaniline, etc., And the hydrogen atoms of the aromatic nuclei of the aromatic diamines are substituted with at least one group or atom selected from the group consisting of chlorine, fluorine, bromine, methyl, methoxy, cyano and phenyl Compound.

In addition, as the above-mentioned diamine, silicon diamine may be selected in order to improve adhesion to the substrate. Examples of silicon diamines include: bis(4-aminophenyl)dimethylsilane, bis(4-aminophenyl)tetramethylsiloxane, bis(4-aminophenyl)tetra Methyl disiloxane, bis(γ-aminopropyl)tetramethyldisiloxane, 1,4-bis(γ-aminopropyldimethylsilyl)benzene, bis(4-aminopropyl) Butyl) tetramethyl disiloxane, bis(γ-aminopropyl) tetraphenyl disiloxane, etc.

In addition, as a preferred dicarboxylic acid having a structure of X ₃ (COOH) ₂ or X ₄ (COOH) ₂ , X ₃ and X ₄ are respectively an aliphatic group having a linear, branched or cyclic structure or Aromatic base. Among them, it is preferably an organic group having 2 or more and 40 or less carbon atoms that may contain an aromatic ring or an aliphatic ring, and X ₃ and X ₄ can be preferably derived from the following formula (38): [化59] ]

{In the formula, R ₄₁ represents a group selected consisting of _{-CH 2 -, - O -,} - S -, - SO 2 -, - CO -, - (CF 3) 2 NHCO- and -C - in the group consisting of 2 Base of price}

It is preferable to choose among the aromatic groups indicated, which is equivalent to the photosensitive characteristic.

唑前驅物亦可為末端基經特定之有機基封端者。於使用經封端基封端之聚

唑前驅物之情形時，有望使本發明之感光性樹脂組合物之加熱硬化後之塗膜之機械物性(尤其伸長率)及硬化浮凸圖案形狀變得良好。作為此種封端基之較佳例，可列舉下述式(39)：[化60]

Gather

The azole precursor can also be one whose terminal group is terminated by a specific organic group. When using the poly capped

In the case of the azole precursor, it is expected to improve the mechanical properties (especially elongation) and the cured relief pattern shape of the coating film of the photosensitive resin composition of the present invention after heat curing. As a preferred example of such an end capping group, the following formula (39) can be cited: [化60]

Represented by.

唑前驅物之基於凝膠滲透層析法之聚苯乙烯換算重量平均分子量較佳為3,000~70,000，更佳為6,000~50,000。該重量平均分子量就硬化浮凸圖案之物性之觀點而言，較佳為3,000以上。又，就解像性之觀點而言，較佳為70,000以下。作為凝膠滲透層析法之展開溶劑，推薦使用四氫呋喃、N-甲基-2-吡咯啶酮。又，分子量係根據使用標準單分散聚苯乙烯所製作之校準曲線而求出。作為標準單分散聚苯乙烯，推薦自昭和電工公司製造之有機溶劑系標準試樣STANDARD SM-105中選擇。 Gather

The polystyrene conversion weight average molecular weight of the azole precursor based on gel permeation chromatography is preferably 3,000 to 70,000, more preferably 6,000 to 50,000. The weight average molecular weight is preferably 3,000 or more from the viewpoint of the physical properties of the hardened relief pattern. Also, from the viewpoint of resolution, it is preferably 70,000 or less. As the developing solvent for gel permeation chromatography, tetrahydrofuran and N-methyl-2-pyrrolidone are recommended. In addition, the molecular weight was calculated based on a calibration curve prepared using standard monodisperse polystyrene. As standard monodisperse polystyrene, it is recommended to choose from STANDARD SM-105, an organic solvent standard sample manufactured by Showa Denko Corporation.

[(A) Polyimide]

Another example of the preferable (A) resin in the photosensitive resin composition of the present invention has the above-mentioned general formula (6): [化61]

{In the formula, X ₅ represents an organic group with 4 to 14 valences, Y ₅ represents an organic group with 2 to 12 valences, and R ₁₀ and R ₁₁ represent at least one selected from a phenolic hydroxyl group, a sulfonic acid group or a thiol group The organic group of the base, which may be the same or different, n ₅ is an integer from 3 to 200, and m ₃ and m ₄ are an integer from 0 to 10}

Polyimide of the structure shown. Here, the resin represented by the general formula (6) does not need to be chemically changed by the heat treatment step when it exhibits sufficient film characteristics, and therefore is suitable for processing at a lower temperature, which is particularly preferred in this respect.

X ₅ in the structural unit represented by the above general formula (6) is preferably an organic group having 4 to 40 carbon valences to 14 valences, and in terms of having both heat resistance and photosensitive properties, it is more preferably An organic group with 5-40 carbon atoms containing aromatic or aliphatic ring.

The polyimide represented by the above general formula (6) can be used to combine tetracarboxylic acid, corresponding tetracarboxylic dianhydride, tetracarboxylic acid diester dichloride, etc. with diamine, corresponding diisocyanate compound, trimethylsilane The alkylated diamine is obtained by reaction. Generally speaking, polyimide can be obtained by chemical treatment of polyimide, which is one of the precursors of polyimide obtained by the reaction of tetracarboxylic dianhydride and diamine, by heating or by acid or alkali. It is obtained by dehydration and closed loop.

Suitable tetracarboxylic dianhydrides include: pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyl Tetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane two anhydride, 2,2-bis(2,3-dicarboxyphenyl) ) Propane two anhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane two anhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane two anhydride, bis( 3,4-Dicarboxyphenyl)methane two anhydride, bis(2,3-dicarboxyphenyl)methane two anhydrate, bis(3,4-dicarboxyphenyl) methane two anhydrate, bis(3, 4-Dicarboxyphenyl) ether two anhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl) dianhydride, 9,9 -Bis{4-(3,4-dicarboxyphenoxy)phenyl} dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic acid Aromatic tetracarboxylic dianhydride such as acid dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, or Aliphatic tetracarboxylic dianhydrides such as butanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 3,3',4,4'-diphenyl tetracarboxylic acid The dianhydride and the following general formula (40):

{In the formula, R ₄₂ represents a group selected from oxygen atom, C(CF ₃ ) ₂ , C(CH ₃ ) ₂ or SO ₂ , and R ₄₃ and R ₄₄ may be the same or different, and represent selected from hydrogen A compound represented by an atom, a hydroxyl group or a thiol group}.

Among them, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-Biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic acid dianhydride Carboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane two anhydrous, 2,2-bis(2,3-dicarboxyphenyl)propane two anhydrate, 1,1-bis (3,4-Dicarboxyphenyl)ethane two anhydrous, 1,1-bis(2,3-dicarboxyphenyl)ethane two anhydrate, bis(3,4-dicarboxyphenyl)methane two Anhydrate, bis(2,3-dicarboxyphenyl) methane two anhydrate, bis(3,4-dicarboxyphenyl) bismuth anhydride, bis(3,4-dicarboxyphenyl) ether two anhydrate , 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane two anhydrous, 3,3',4,4'-diphenyl tetracarboxylic dianhydride, 9,9-bis(3 ,4-Dicarboxyphenyl) dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl) dianhydride and the following general formula (41)

{In the formula, R ₄₅ represents a group selected from oxygen atom, C(CF ₃ ) ₂ , C(CH ₃ ) ₂ or SO ₂ , and R ₄₆ and R ₄₇ may be the same or different, and represent hydrogen An acid dianhydride of the structure represented by the atom, hydroxyl, or thiol group}. These can be used alone or in combination of two or more kinds.

Y _{5 of the} above general formula (6) represents a structural component of a diamine. As the diamine, it represents a 2-12 valent organic group containing an aromatic ring or an aliphatic ring, and preferably has a carbon number of 5-40 Organic base.

Specific examples of diamines include: 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4 '-Diaminodiphenylmethane, 3,4'-Diaminodiphenyl sulfide, 4,4'-Diaminodiphenyl sulfide, 3,4'-Diaminodiphenyl sulfide, 4 ,4'-Diaminodiphenyl sulfide, 1,4-bis(4-aminophenoxy)benzene, phenylacetylene, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2 , 6-Naphthalenediamine, bis(4-aminophenoxyphenyl) bis(4-aminophenoxyphenyl) bis(3-aminophenoxyphenyl) bis(3-aminophenoxyphenyl), bis(4-aminophenoxy)biphenyl, bis{ 4-(4-aminophenoxy)phenyl)ether, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diamino Benzene, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl -4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl -4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 9,9-bis(4-aminophenyl)pyridium Or these aromatic rings substituted by alkyl or halogen atoms, or aliphatic cyclohexyl diamine, methylene bicyclohexyl amine, and the following general formula (42): [化64]

{In the formula, R ₄₈ represents a group selected from oxygen atom, C(CF ₃ ) ₂ , C(CH ₃ ) ₂ or SO ₂ , and R ₄₉ to R ₅₂ may be the same or different, and represent selected from hydrogen Atom, hydroxyl, or thiol group in the structure represented by the diamine, etc.

Among them, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'- Diaminodiphenylmethane, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4 '-Diaminodiphenyl sulfide, m-phenylenediamine, P-phenylenediamine, 1,4-bis(4-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)茀, and the following general formula (43): [化65]

{In the formula, R ₅₃ represents a group selected from oxygen atom, C(CF ₃ ) ₂ , C(CH ₃ ) ₂ or SO ₂ , and R ₅₄ to R ₅₇ may be the same or different, and represent selected from hydrogen Atom, hydroxyl or thiol group}

The diamine of the structure shown.

Among these, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'- Diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, And the following general formula (44):

{In the formula, R ₅₈ represents a group selected from oxygen atom, C(CF ₃ ) ₂ , C(CH ₃ ) ₂ or SO ₂ , and R ₅₉ and R ₆₀ may be the same or different, and represent selected from hydrogen Atom, hydroxyl or thiol group}

The diamine of the structure shown. These can be used alone or in combination of two or more kinds.

R ₁₀ and R _{11 in the} general formula (6) represent a phenolic hydroxyl group, a sulfonic acid group, or a thiol group. In the present invention, as R ₁₀ and R ₁₁ , a phenolic hydroxyl group, a sulfonic acid group and/or a thiol group may be mixed.

By controlling the amount of alkali-soluble groups of R ₁₀ and R ₁₁ , the dissolution rate in the alkaline aqueous solution is changed. Therefore, a photosensitive resin composition having a moderate dissolution rate can be obtained by this adjustment.

Furthermore, in order to improve the adhesion to the substrate, it is also possible to copolymerize with aliphatic groups having a siloxane structure as X ₅ and Y ₅ within a range that does not reduce heat resistance. Specifically, bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane are listed as diamine components with 1~10mol%. Alkane, etc. for copolymerization.

The above-mentioned polyimide can be obtained by using the following methods to obtain a polyimide precursor, and then a method of completely imidizing the polyimide precursor by using a known imidization reaction method, or stopping in the middle A method of introducing a part of the imine structure (in this case, polyimide) by the amination reaction, or by blending a fully imidized polymer with the polyimide precursor Introduce a part of the imine structure to synthesize. The above method to obtain the polyimine precursor is as follows: for example, tetracarboxylic dianhydride and diamine compound (part of it is substituted with a terminal blocking agent as a monoamine) at low temperature Reaction; tetracarboxylic dianhydride (part of it is substituted as an acid anhydride or monochloride compound or monoactive ester compound terminal blocking agent) and diamine compound at low temperature; from tetracarboxylic dianhydride and alcohol to obtain two The ester is then reacted with a diamine (part of it is substituted by a terminal blocking agent as a monoamine) in the presence of a condensing agent; the diester is obtained from tetracarboxylic dianhydride and alcohol, and then the remaining dicarboxylic acid is processed Chlorination of diamine (part of it is substituted by end-capping agent as monoamine) reaction.

It is preferable that the said polyimide has a polyimide so that an imidization rate may be 15% or more with respect to the whole resin which comprises a photosensitive resin composition. More preferably, it is 20% or more. Here, the imidization rate refers to the ratio of imidization present in the entire resin constituting the photosensitive resin composition. If the imidization rate is less than 15%, the shrinkage during thermal curing will increase, making it unsuitable for thick film production.

The imidization rate can be easily calculated by the following method. First, the infrared absorption spectrum of the polymer is measured, and it is confirmed that there are absorption peaks (around 1780 cm-1, around 1377 cm-1) derived from the imine structure of polyimide. Then, the polymer was heat-treated at 350°C for 1 hour, the infrared absorption spectrum after the heat-treatment was measured, and the peak intensity around 1377 cm-1 was compared with the intensity before the heat-treatment to calculate the glutamate in the polymer before the heat-treatment. The imidization rate.

Regarding the molecular weight of the aforementioned polyimide, in the case of measuring the weight average molecular weight in terms of polystyrene based on gel permeation chromatography, it is preferably 3,000 to 200,000, more preferably 5,000 to 50,000. When the weight average molecular weight is above 3,000, the mechanical properties are good. When the weight average molecular weight is below 50,000, the dispersibility in the developer is good, and the relief pattern has good resolution.

As the developing solvent for gel permeation chromatography, tetrahydrofuran and N-methyl-2-pyrrolidone are recommended. In addition, the molecular weight was calculated based on a calibration curve prepared using standard monodisperse polystyrene. As standard monodisperse polystyrene, it is recommended to choose from STANDARD SM-105, an organic solvent standard sample manufactured by Showa Denko Corporation.

Furthermore, in the present invention, a phenol resin can also be preferably used.

[(A) Phenolic resin]

The so-called phenol resin in this embodiment means a tree having repeating units containing phenolic hydroxyl groups fat. (A) The phenol resin does not undergo structural changes such as the cyclization (imidization) of the polyimide precursor during thermal curing, and therefore has the advantage of being able to be cured at low temperatures (for example, below 250°C).

In this embodiment, the weight average molecular weight of (A) phenol resin is preferably 700 to 100,000, more preferably 1,500 to 80,000, and still more preferably 2,000 to 50,000. The weight average molecular weight is preferably 700 or more from the viewpoint of the applicability of the cured film for reflow treatment, and on the other hand, from the viewpoint of the alkali solubility of the photosensitive resin composition, it is preferably 100,000 or less.

The determination of the weight average molecular weight herein can be performed by gel permeation chromatography (GPC) and calculated based on a calibration curve made using standard polystyrene.

(A) The phenol resin is preferably selected from novolac and polyhydroxystyrene in terms of solubility in alkaline aqueous solution, sensitivity and resolution when forming a resist pattern, and residual stress of the cured film , Has the following general formula (7):

{In the formula, a is an integer from 1 to 3, b is an integer from 0 to 3, 1≦(a+b)≦4, R ₂₆ represents a monovalent organic group selected from 1 to 20 carbon atoms, halogen atoms, A monovalent substituent in the group consisting of a nitro group and a cyano group. When b is 2 or 3, a plurality of R ₁₂ may be the same or different from each other, and X represents a carbon that may have an unsaturated bond A divalent aliphatic group with 2 to 10, a divalent alicyclic group with 3 to 20 carbons, the following general formula (8): [化68] -C _p H _2p O- (8)

(In the formula, p is an integer from 1 to 10) The divalent organic group in the group consisting of a divalent alkoxy group and a divalent organic group with an aromatic ring with carbon number 6 to 12 base}

At least one kind of phenol resin among the phenol resin of the repeating unit and the phenol resin modified by the compound having the unsaturated hydrocarbon group with carbon number of 4-100.

(Novolak)

Here, the novolak refers to the entire polymer obtained by condensation of phenols and formaldehyde in the presence of a catalyst. Generally speaking, novolac can be obtained by condensing 1 mol of phenols and less than 1 mol of formaldehyde with respect to the phenols. As the above-mentioned phenols, for example, phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butyl phenol Base phenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol , 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, catechol, resorcinol, pyrogallol, α-naphthol, β-naphthol, etc. Specific examples of novolak resins include phenol/formaldehyde condensation novolak resins, cresol/formaldehyde condensation novolak resins, phenol-naphthol/formaldehyde condensation novolak resins, and the like.

The weight average molecular weight of the novolak is preferably 700 to 100,000, more preferably 1,500 to 80,000, and still more preferably 2,000 to 50,000. The weight average molecular weight is preferably 700 or more from the viewpoint of the applicability of the cured film for reflow treatment, and on the other hand, from the viewpoint of the alkali solubility of the photosensitive resin composition, it is preferably 100,000 or less.

(Polyhydroxystyrene)

In this context, the term "polyhydroxystyrene" means the entire polymer containing hydroxystyrene as a polymerization unit. As a preferable example of polyhydroxystyrene, poly(p-vinylphenol) can be mentioned. Polyp-vinylphenol means the entire polymer containing p-vinylphenol as a polymerized unit. Therefore, as long as it does not violate the purpose of the present invention, polymer units other than hydroxystyrene (for example, p-vinylphenol) can be used to form polyhydroxystyrene (for example, polyp-vinylphenol). In polyhydroxystyrene, the ratio of the number of moles of hydroxystyrene units based on the number of moles of all polymerized units is preferably 10 mole% to 99 mole%, more preferably 20 to 97 mole%, More preferably, it is 30 to 95 mol%. When the above ratio is 10 mol% or more, it is advantageous from the viewpoint of the alkali solubility of the photosensitive resin composition, and when it is 99 mol% or less, the composition containing the following copolymerization components is cured It is advantageous from the viewpoint of reflow soldering applicability of the resulting cured film. The polymerization unit other than hydroxystyrene (for example, p-vinylphenol) may be any polymerization unit that can be copolymerized with hydroxystyrene (for example, p-vinylphenol). The copolymerization component that forms polymerized units other than hydroxystyrene (for example, p-vinylphenol) is not limited, and examples include methyl acrylate, methyl methacrylate, hydroxyethyl acrylate, butyl methacrylate, and acrylic acid. Octyl ester, 2-ethoxyethyl methacrylate, tertiary butyl acrylate, 1,5-pentanediol diacrylate, N,N-diethylaminoethyl acrylate, ethylene glycol diacrylate , 1,3-propanediol diacrylate, decanediol diacrylate, decanediol dimethacrylate, 1,4-cyclohexanediol diacrylate, 2,2-dimethylolpropane diacrylate , Glycerol diacrylate, tripropylene glycol diacrylate, glycerol triacrylate, 2,2-bis(p-hydroxyphenyl)propane dimethacrylate, triethylene glycol diacrylate, polyoxyethyl-2- 2-Di(p-hydroxyphenyl)propane dimethacrylate, triethylene glycol dimethacrylate, polyoxypropyl trimethylolpropane triacrylate, ethylene glycol dimethacrylate, butanedi Alcohol dimethacrylate, 1,3-propanediol dimethacrylate, butanediol dimethacrylate, 1,3-propanediol dimethacrylate, 1,2,4-butanetriol trimethyl Acrylate, 2,2,4-tri Methyl-1,3-pentanediol dimethacrylate, pentaerythritol trimethacrylate, 1,2-dimethacrylate 1-phenylethylene glycol, pentaerythritol tetramethacrylate, trimethylol Acrylic acid esters such as propane trimethacrylate, 1,5-pentanediol dimethacrylate, and 1,4-benzenediol dimethacrylate; styrene and, for example, 2-methylstyrene and Substituted styrenes such as vinyl toluene; vinyl ester monomers such as vinyl acrylate and vinyl methacrylate; and o-vinyl phenol, m-vinyl phenol, etc.

In addition, as the novolak and polyhydroxystyrene described above, each may be used alone or in combination of two or more.

The weight average molecular weight of polyhydroxystyrene is preferably 700 to 100,000, more preferably 1,500 to 80,000, and still more preferably 2,000 to 50,000. The weight average molecular weight is preferably 700 or more from the viewpoint of the applicability of the cured film for reflow treatment, and on the other hand, from the viewpoint of the alkali solubility of the photosensitive resin composition, it is preferably 100,000 or less.

(Phenolic resin represented by general formula (7))

In this embodiment, (A) the phenol resin also preferably contains the following general formula (7):

{In the formula, a is an integer from 1 to 3, b is an integer from 0 to 3, 1≦(a+b)≦4, R ₁₂ represents a monovalent organic group selected from 1 to 20 carbon atoms, halogen atoms, A monovalent substituent in the group consisting of a nitro group and a cyano group. When b is 2 or 3, a plurality of R ₁₂ may be the same or different from each other, and X represents a carbon that may have an unsaturated bond A divalent aliphatic group with 2 to 10, a divalent alicyclic group with 3 to 20 carbons, the following general formula (8): [化70] -C _p H _2p O- (8)

唑樹脂相比能夠於低溫下硬化，且能夠形成具有良好之伸長率之硬化膜，於該方面而言特別有利。酚樹脂分子中所存在之上述重複單元可為1種或2種以上之組合。 (In the formula, p is an integer from 1 to 10) The divalent organic group in the group consisting of a divalent alkoxy group and a divalent organic group with an aromatic ring with carbon number 6 to 12 The phenolic resin of the repeating unit represented by the group. The phenol resin with the above repeating unit and the previously used polyimide resin and polybenzo

The azole resin can be cured at a low temperature and can form a cured film with good elongation, which is particularly advantageous in this respect. The aforementioned repeating units present in the phenol resin molecule may be one type or a combination of two or more types.

In the above general formula (7), R ₁₂ is selected from monovalent organic groups with 1 to 20 carbon atoms, halogen atoms, nitro groups and cyano groups from the viewpoint of the reactivity when synthesizing the resin of general formula (7) A monovalent substituent in the group formed. From the viewpoint of alkali solubility, R ₁₂ is preferably selected from a halogen atom, a nitro group, a cyano group, an aliphatic group having 1 to 10 carbons which may have an unsaturated bond, and an aromatic group having 6 to 20 carbons. , And the following general formula (45):

{In the formula, R ₆₁ , R ₆₂ and R ₆₃ each independently represent a hydrogen atom, an aliphatic group with 1 to 10 carbons that may have an unsaturated bond, an alicyclic group with 3 to 20 carbons, or a carbon 6 to 20 aromatic group, and R ₆₄ represents a divalent aliphatic group with 1 to 10 carbons, a divalent alicyclic group with 3 to 20 carbons, or 6 to 20 carbons that may have unsaturated bonds A monovalent substituent in the group consisting of four groups represented by divalent aromatic group}.

In this embodiment, in the above general formula (7), a is an integer of 1 to 3, but from the viewpoint of alkali solubility and elongation, it is preferably 2. In addition, when a is 2, the substitution positions of the hydroxyl groups can be any positions of ortho, meta, and para positions. In addition, when a is 3, the substitution positions of the hydroxyl groups can be any positions such as 1,2,3-position, 1,2,4-position and 1,3,5-position.

In this embodiment, in the above general formula (7), when a is 1, in order to improve the alkali solubility, a phenol resin having a repeating unit represented by the general formula (7) (hereinafter also referred to as (a1) ) Resin) and further mix a phenol resin selected from novolac and polyhydroxystyrene (hereinafter also referred to as (a2) resin).

The mixing ratio of (a1) resin and (a2) resin is preferably in the range of (a1)/(a2)=10/90 to 90/10 in terms of mass ratio. The mixing ratio is preferably (a1)/(a2)=10/90~90/10 from the viewpoint of solubility in alkaline aqueous solution and elongation of cured film, and more preferably (a1)/ (a2)=20/80~80/20, more preferably (a1)/(a2)=30/70~70/30.

Regarding the novolak and polyhydroxystyrene as the above (a2) resin, the same resins as those shown in the above (novolak) and (polyhydroxystyrene) can be used.

In this embodiment, in the above general formula (7), b is an integer of 0 to 3. However, from the viewpoint of alkali solubility and elongation, it is preferably 0 or 1. In addition, when b is 2 or 3, a plurality of R ₁₂ may be the same or different from each other.

Furthermore, in this embodiment, in the above-mentioned general formula (7), a and b satisfy the relationship of 1≦(a+b)≦4.

In this embodiment, in the above general formula (7), X is selected from divalent fats with 2-10 carbons that may have unsaturated bonds in terms of the shape of the cured relief pattern and the elongation of the cured film. A group consisting of a divalent alicyclic group with 3 to 20 carbons, an alkoxy group represented by the above general formula (8), and a divalent organic group with an aromatic ring with 6 to 12 carbons The divalent organic group in the group. Among the divalent organic groups, from the viewpoint of the toughness of the cured film, X is preferably selected from the following general formula (9):

{In the formula, R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are each independently a hydrogen atom, a monovalent aliphatic group with 1 to 10 carbon atoms, or a carbon in which part or all of the hydrogen atoms are replaced with fluorine atoms A monovalent aliphatic group of 1 to 10, n ₆ is an integer of 0 to 4, and when n ₆ is an integer of 1 to 4, R ₁₇ is a halogen atom, a hydroxyl group, or 1 of carbon numbers 1 to 12 For a valence organic group, at least one R ₁₇ is a hydroxyl group, and when n ₆ is an integer from 2 to 4, the plural R ₁₇ may be the same or different from each other. A divalent group represented by the following general formula (10): [化73]

{In the formula, R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ each independently represent a hydrogen atom, a monovalent aliphatic group with 1 to 10 carbon atoms, or a carbon in which part or all of the hydrogen atoms are substituted with fluorine atoms A monovalent aliphatic group of 1 to 10, W is a single bond, selected from aliphatic groups with 1 to 10 carbons that can be substituted by fluorine atoms, and alicyclic groups with 3 to 20 carbons that can be substituted by fluorine atoms Base, the following general formula (8): [化74] -C _p H _2p O- (8)

(In the formula, p is an integer from 1 to 10) a divalent alkoxy group represented by the following formula (11):

The divalent organic group in the group consisting of the indicated divalent radical} The divalent organic group in the group consisting of the indicated divalent radical. The carbon number of the divalent organic group X having an aromatic ring with carbon number of 6-12 is preferably 8 to 75, and more preferably 8 to 40. Furthermore, the structure of the divalent organic group X having an aromatic ring with carbon number of 6 to 12 is generally different from that in the general formula (7) where an OH group and any R ₁₂ group are bonded to the aromatic ring The structure.

Furthermore, the divalent organic group represented by the above general formula (10) is more preferably the following formula (12) in terms of the pattern formability of the resin composition and the elongation of the cured film after curing:

The expressed divalent organic group is more preferably the following formula (13):

The indicated divalent organic group.

Among the structures represented by the general formula (7), X is preferably the structure represented by the above formula (12) or (13), and the ratio of the parts represented by the structure represented by the formula (12) or (13) is From the viewpoint of elongation, it is preferably 20% by mass or more, and more preferably 30% by mass or more. From the viewpoint of the alkali solubility of the composition, the above ratio is preferably 80% by mass or less, and more preferably 70% by mass or less.

Furthermore, among the phenol resins having the structure represented by the above general formula (7), from the viewpoint of the alkali solubility of the composition and the elongation of the cured film, it is particularly preferable to have the following generalities in the same resin skeleton The structure represented by the formula (14) and the structure represented by the following general formula (15) are both structures.

[化78]

{In the formula, R ₂₁ is a monovalent group with 1 to 10 carbons selected from the group consisting of hydrocarbon groups and alkoxy groups, n ₇ is 2 or 3, n ₈ is an integer of 0 to 2, m ₅ is An integer from 1 to 500, 2≦(n ₇ +n ₈ )≦4, when n ₈ is 2, the plural R ₂₁ may be the same or different from each other}

{In the formula, R ₂₂ and R ₂₃ are each independently a monovalent group selected from the group consisting of a hydrocarbon group and an alkoxy group with 1 to 10 carbon atoms, n ₉ is an integer of 1 to 3, and n ₁₀ is 0 to Integer of 2, n ₁₁ is an integer of 0~3, m ₆ is an integer of 1~500, 2≦(n ₉ +n ₁₀ )≦4, when n ₁₀ is 2, plural R ₂₂ can be the same Or it may be different. When n ₁₁ is 2 or 3, a plurality of R ₂₃ may be the same or different from each other}

M the formula (14) _{m. 5} and of the general formula (15) represents the total number ₆ of the main chain of the phenol resin in the respective repeating units. That is, in (A) the phenol resin, for example, the repeating unit in parentheses in the structure represented by the general formula (14) and the repeating unit in parentheses in the structure represented by the general formula (15) may be random or embedded Arrangement in the form of paragraphs or combinations of these. m ₅ and m ₆ are each independently an integer of 1 to 500, the lower limit is preferably 2, more preferably 3, and the upper limit is preferably 450, more preferably 400, and more preferably 350. From the viewpoint of the toughness of the cured film, m ₅ and m ₆ are preferably 2 or more independently, and preferably 450 or less from the viewpoint of solubility in an alkaline aqueous solution. The total of m ₅ and m ₆ is preferably 2 or more, more preferably 4 or more, and still more preferably 6 or more from the viewpoint of the toughness of the cured film, from the viewpoint of solubility in alkaline aqueous solution In particular, it is preferably 200 or less, more preferably 175 or less, and still more preferably 150 or less.

In the (A) phenol resin having the structure represented by the general formula (14) and the structure represented by the general formula (15) in the same resin skeleton, the structure represented by the general formula (14) is The higher the ear ratio, the better the physical properties of the film after curing, and the better the heat resistance. On the other hand, the higher the molar ratio of the structure represented by the general formula (15), the better the alkali solubility, and the better after curing. The better the shape of the pattern. Therefore, the ratio m ₅ /m ₆ of the structure represented by the general formula (14) to the structure represented by the general formula (15) is preferably 20/80 or more from the viewpoint of the physical properties of the film after curing. It is more preferably 40/60 or more, and particularly preferably 50/50 or more. From the viewpoints of alkali solubility and hardened relief pattern shape, it is preferably 90/10 or less, more preferably 80/20 or less, and still more preferably Below 70/30.

烷般分解生成醛化合物之化合物)、具有酮基之化合物、分子內具有2個羥甲基之化合物、分子內具有2個烷氧基甲基之化合物、及分子內具有2個鹵烷基之化合物所組成之群中之1種以上之化合物)，更典型而言可藉由使包含該等之單體成分進行聚合反應而合成。例如可使如下所述之苯酚及/或苯酚衍生物(以下亦統稱為「酚化合物」)與醛化合物、酮化合物、羥甲基化合物、烷氧基甲基化合物、二烯化合物或鹵烷基化合物等共聚成分進行聚合而獲得(A)酚樹脂。於該情形時，上述通式(7)中，芳香環上鍵結有OH基及任意 之R₁₂基之結構所表示之部分源自上述酚化合物，X所表示之部分源自上述共聚成分。就反應控制、以及所獲得之(A)酚樹脂及感光性樹脂組合物之穩定性之觀點而言，酚化合物與上述共聚成分之添加莫耳比(酚化合物)：(共聚成分)較佳為5：1~1.01：1，更佳為2.5：1~1.1：1。 The phenol resin having the repeating unit represented by the general formula (7) typically contains a phenol compound and a copolymer component (specifically, selected from compounds having an aldehyde group (also including three

Compounds that decompose like alkanes to produce aldehydes), compounds with ketone groups, compounds with 2 hydroxymethyl groups in the molecule, compounds with 2 alkoxymethyl groups in the molecule, and compounds with 2 haloalkyl groups in the molecule One or more compounds in the group consisting of compounds), more typically, can be synthesized by polymerizing monomer components containing them. For example, the following phenol and/or phenol derivatives (hereinafter also collectively referred to as "phenol compounds") can be combined with aldehyde compounds, ketone compounds, methylol compounds, alkoxymethyl compounds, diene compounds or haloalkyl Copolymer components such as compounds are polymerized to obtain (A) phenol resin. In this case, in the above general formula (7), the part represented by the structure in which the OH group and any R ₁₂ group are bonded to the aromatic ring is derived from the above phenol compound, and the part represented by X is derived from the above copolymer component. From the viewpoint of reaction control and the stability of the obtained (A) phenol resin and photosensitive resin composition, the molar ratio of the phenol compound and the above-mentioned copolymerization component (phenol compound): (copolymerization component) is preferably 5:1~1.01:1, more preferably 2.5:1~1.1:1.

The weight average molecular weight of the phenol resin having the repeating unit represented by the general formula (7) is preferably 700 to 100,000, more preferably 1,500 to 80,000, and still more preferably 2,000 to 50,000. The weight average molecular weight is preferably 700 or more from the viewpoint of the applicability of the cured film for reflow treatment, and on the other hand, from the viewpoint of the alkali solubility of the photosensitive resin composition, it is preferably 100,000 or less.

烯-2,3-二羧基醯亞胺、N-(羥基苯基)-5-甲基-5-降

烯-2,3-二羧基醯亞胺、三氟甲基苯酚、羥基苯甲酸、羥基苯甲酸甲酯、羥基苯甲酸乙酯、羥基苯甲酸苄酯、羥基苯甲醯胺、羥基苯甲醛、羥基苯乙酮、羥基二苯甲酮、羥基苯甲腈、間苯二酚、二甲苯酚、兒茶酚、甲基兒茶酚、乙基兒茶酚、己基兒茶酚、苄基兒茶酚、硝基苄基兒茶酚、甲基間苯二酚、乙基間苯二酚、己基間苯二酚、苄基間苯二酚、硝基苄基間苯二酚、氫醌、咖啡酸、二羥基苯甲酸、二羥基苯甲酸甲酯、二羥基苯甲酸乙酯、二羥基苯甲酸丁酯、二羥基苯甲酸丙酯、二羥基苯甲酸苄酯、二羥基苯甲醯胺、二羥基苯甲醛、二羥基苯乙酮、二羥基二苯甲酮、二羥基苯甲腈、N-(二羥基苯基)-5-降

烯-2,3-二羧基醯亞胺、N-(二羥基苯基)-5-甲基-5-降

烯-2,3-二羧基醯亞胺、硝基兒茶酚、氟兒茶酚、氯兒茶酚、溴兒茶酚、三氟甲基兒茶酚、硝基間苯二酚、氟間苯二酚、氯間苯二酚、溴間苯二酚、三氟甲基間苯二酚、連苯三酚、間苯三酚、1,2,4-三羥基苯、三羥基苯甲酸、三羥基苯甲酸甲酯、三羥基苯甲酸乙酯、三羥基苯甲酸丁酯、三羥基苯甲酸丙酯、三羥基苯甲酸苄酯、三羥基苯甲醯胺、三羥基苯甲醛、三羥基苯乙酮、三羥基二苯甲酮、三羥基苯甲腈等。 Examples of phenol compounds that can be used to obtain a phenol resin having a repeating unit represented by the general formula (7) include: cresol, ethylphenol, propylphenol, butylphenol, amylphenol, cyclohexylphenol, and hydroxyl Biphenyl, benzylphenol, nitrobenzylphenol, cyanobenzylphenol, adamantanephenol, nitrophenol, fluorophenol, chlorophenol, bromophenol, trifluoromethylphenol, N-(hydroxyphenyl)- 5-drop

Ene-2,3-dicarboxyimide, N-(hydroxyphenyl)-5-methyl-5-nor

Ene-2,3-dicarboxyimidine, trifluoromethylphenol, hydroxybenzoic acid, methyl hydroxybenzoate, ethyl hydroxybenzoate, benzyl hydroxybenzoate, hydroxybenzamide, hydroxybenzaldehyde, Hydroxyacetophenone, hydroxybenzophenone, hydroxybenzonitrile, resorcinol, xylenol, catechol, methylcatechol, ethylcatechol, hexylcatechol, benzylcatechol Phenol, nitrobenzyl catechol, methyl resorcinol, ethyl resorcinol, hexyl resorcinol, benzyl resorcinol, nitrobenzyl resorcinol, hydroquinone, coffee Acid, dihydroxybenzoic acid, methyl dihydroxybenzoate, ethyl dihydroxybenzoate, butyl dihydroxybenzoate, propyl dihydroxybenzoate, benzyl dihydroxybenzoate, dihydroxybenzamide, two Hydroxybenzaldehyde, dihydroxyacetophenone, dihydroxybenzophenone, dihydroxybenzonitrile, N-(dihydroxyphenyl)-5-drop

Ene-2,3-dicarboxyimide, N-(dihydroxyphenyl)-5-methyl-5-nor

En-2,3-dicarboxyl imine, nitrocatechol, fluorocatechol, chlorocatechol, bromocatechol, trifluoromethylcatechol, nitroresorcinol, fluorocatechol Hydroquinone, chlororesorcinol, bromoresorcinol, trifluoromethylresorcinol, pyrogallol, phloroglucinol, 1,2,4-trihydroxybenzene, trihydroxybenzoic acid, Methyl trihydroxybenzoate, ethyl trihydroxybenzoate, butyl trihydroxybenzoate, propyl trihydroxybenzoate, benzyl trihydroxybenzoate, trihydroxybenzamide, trihydroxybenzaldehyde, trihydroxybenzene Ethyl ketone, trihydroxybenzophenone, trihydroxybenzonitrile, etc.

烷、乙二醛、環己醛、二苯基乙醛、乙基丁醛、苯甲醛、乙醛醛、5-降

烯-2-羧基醛、丙二醛、丁二醛、戊二醛、柳醛、萘甲醛、對苯二甲醛等。 Examples of the above-mentioned aldehyde compound include: acetaldehyde, propionaldehyde, trimethylacetaldehyde, butyraldehyde, valeraldehyde, hexanal, tri

Alkane, glyoxal, cyclohexanal, diphenylacetaldehyde, ethyl butyraldehyde, benzaldehyde, acetaldehyde aldehyde, 5-drop

En-2-carboxaldehyde, malondialdehyde, succinaldehyde, glutaraldehyde, salicaldehyde, naphthaldehyde, terephthalaldehyde, etc.

酮、金剛酮、2,2-雙(4-氧雜環己基)丙烷等。 Examples of the ketone compound include acetone, methyl ethyl ketone, diethyl ketone, dipropyl ketone, dicyclohexyl ketone, dibenzyl ketone, cyclopentanone, cyclohexanone, dicyclohexanone, and cyclohexanone. Hexanedione, 3-butyn-2-one, 2-drop

Ketone, Adamantone, 2,2-bis(4-oxocyclohexyl)propane, etc.

烯-2,2-二甲醇、5-降

烯-2,3-二甲醇、季戊四醇、2-苯基-1,3-丙二醇、三羥甲基乙烷、三羥甲基丙烷、3,6-雙(羥基甲基)均四甲苯、2- 硝基對苯二甲醇、1,10-二羥基癸烷、1,12-二羥基十二烷、1,4-雙(羥基甲基)環己烷、1,4-雙(羥基甲基)環己烯、1,6-雙(羥基甲基)金剛烷、1,4-苯二甲醇、1,3-苯二甲醇、2,6-雙(羥基甲基)-1,4-二甲氧基苯、2,3-雙(羥基甲基)萘、2,6-雙(羥基甲基)萘、1,8-雙(羥基甲基)蒽、2,2'-雙(羥基甲基)二苯醚、4,4'-雙(羥基甲基)二苯醚、4,4'-雙(羥基甲基)二苯硫醚、4,4'-雙(羥基甲基)二苯甲酮、4-羥基甲基苯甲酸-4'-羥基甲基苯酯、4-羥基甲基苯甲酸-4'-羥基甲基苯胺、4,4'-雙(羥基甲基)苯基脲、4,4'-雙(羥基甲基)苯基胺基甲酸酯、1,8-雙(羥基甲基)蒽、4,4'-雙(羥基甲基)聯苯、2,2'-二甲基-4,4'-雙(羥基甲基)聯苯、2,2-雙(4-羥基甲基苯基)丙烷、乙二醇、二乙二醇、三乙二醇、四乙二醇、丙二醇、二丙二醇、三丙二醇、四丙二醇等。 Examples of the above-mentioned hydroxymethyl compound include: 2,6-bis(hydroxymethyl)p-cresol, 2,6-bis(hydroxymethyl)-4-ethylphenol, 2,6-bis(hydroxymethyl) Yl)-4-propylphenol, 2,6-bis(hydroxymethyl)-4-n-butylphenol, 2,6-bis(hydroxymethyl)-4-tert-butylphenol, 2,6- Bis(hydroxymethyl)-4-methoxyphenol, 2,6-bis(hydroxymethyl)-4-ethoxyphenol, 2,6-bis(hydroxymethyl)-4-propoxyphenol, 2,6-bis(hydroxymethyl)-4-n-butoxyphenol, 2,6-bis(hydroxymethyl)-4-tertiary butoxyphenol, 1,3-bis(hydroxymethyl)urea , Ribitol, arabitol, allitol, 2,2-bis(hydroxymethyl)butanoic acid, 2-benzyloxy-1,3-propanediol, 2,2-dimethyl-1,3-propanediol , 2,2-Diethyl-1,3-propanediol, glycerol monoacetate, 2-methyl-2-nitro-1,3-propanediol, 5-nor

Ene-2,2-dimethanol, 5-nor

Ene-2,3-dimethanol, pentaerythritol, 2-phenyl-1,3-propanediol, trimethylolethane, trimethylolpropane, 3,6-bis(hydroxymethyl) mesitylene, 2 -Nitro-terephthalic methanol, 1,10-dihydroxydecane, 1,12-dihydroxydodecane, 1,4-bis(hydroxymethyl)cyclohexane, 1,4-bis(hydroxymethyl) )Cyclohexene, 1,6-bis(hydroxymethyl)adamantane, 1,4-benzenedimethanol, 1,3-benzenedimethanol, 2,6-bis(hydroxymethyl)-1,4-di Methoxybenzene, 2,3-bis(hydroxymethyl)naphthalene, 2,6-bis(hydroxymethyl)naphthalene, 1,8-bis(hydroxymethyl)anthracene, 2,2'-bis(hydroxymethyl) Base) diphenyl ether, 4,4'-bis(hydroxymethyl)diphenyl ether, 4,4'-bis(hydroxymethyl)diphenyl sulfide, 4,4'-bis(hydroxymethyl)diphenyl Methyl ketone, 4-hydroxymethylbenzoic acid-4'-hydroxymethylphenyl ester, 4-hydroxymethylbenzoic acid-4'-hydroxymethylaniline, 4,4'-bis(hydroxymethyl)phenylurea , 4,4'-bis(hydroxymethyl)phenyl carbamate, 1,8-bis(hydroxymethyl)anthracene, 4,4'-bis(hydroxymethyl)biphenyl, 2,2'-Dimethyl-4,4'-bis(hydroxymethyl)biphenyl, 2,2-bis(4-hydroxymethylphenyl)propane, ethylene glycol, diethylene glycol, triethylene glycol, four Ethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, etc.

烯、2,3-雙(甲氧基甲基)-5-降

烯、1,4-雙(甲氧基甲基)環己烷、1,4-雙(甲氧基甲基)環己烯、1,6-雙(甲氧基甲基)金剛烷、1,4-雙(甲氧基甲基)苯、1,3-雙(甲氧基甲基)苯、2,6-雙(甲氧基甲基)-1,4-二甲氧基苯、2,3-雙(甲氧基甲基)萘、2,6-雙(甲氧基甲基)萘、1,8-雙(甲氧基甲基)蒽、2,2'-雙(甲氧基甲基)二苯醚、4,4'-雙(甲氧基甲基)二苯醚、4,4'-雙(甲氧基甲基)二苯硫醚、4,4'-雙(甲氧基甲基)二苯甲酮、4-甲氧基甲基苯甲酸-4'-甲氧基甲基苯基、4-甲氧 基甲基苯甲酸-4'-甲氧基甲基苯胺、4,4'-雙(甲氧基甲基)苯基脲、4,4'-雙(甲氧基甲基)苯基胺基甲酸酯、1,8-雙(甲氧基甲基)蒽、4,4'-雙(甲氧基甲基)聯苯、2,2'-二甲基-4,4'-雙(甲氧基甲基)聯苯、2,2-雙(4-甲氧基甲基苯基)丙烷、乙二醇二甲醚、二乙二醇二甲醚、三乙二醇二甲醚、四乙二醇二甲醚、丙二醇二甲醚、二丙二醇二甲醚、三丙二醇二甲醚、四丙二醇二甲醚等。 Examples of the above-mentioned alkoxymethyl compound include 2,6-bis(methoxymethyl)p-cresol, 2,6-bis(methoxymethyl)-4-ethylphenol, 2, 6-bis(methoxymethyl)-4-propylphenol, 2,6-bis(methoxymethyl)-4-n-butylphenol, 2,6-bis(methoxymethyl)- 4-tert-butylphenol, 2,6-bis(methoxymethyl)-4-methoxyphenol, 2,6-bis(methoxymethyl)-4-ethoxyphenol, 2, 6-bis(methoxymethyl)-4-propoxyphenol, 2,6-bis(methoxymethyl)-4-n-butoxyphenol, 2,6-bis(methoxymethyl) )-4-tert-butoxyphenol, 1,3-bis(methoxymethyl)urea, 2,2-bis(methoxymethyl)butyric acid, 2,2-bis(methoxymethyl) Base)-5-drop

Ene, 2,3-bis(methoxymethyl)-5-nor

Ene, 1,4-bis(methoxymethyl)cyclohexane, 1,4-bis(methoxymethyl)cyclohexene, 1,6-bis(methoxymethyl)adamantane, 1 ,4-bis(methoxymethyl)benzene, 1,3-bis(methoxymethyl)benzene, 2,6-bis(methoxymethyl)-1,4-dimethoxybenzene, 2,3-bis(methoxymethyl)naphthalene, 2,6-bis(methoxymethyl)naphthalene, 1,8-bis(methoxymethyl)anthracene, 2,2'-bis(methyl) Oxymethyl)diphenyl ether, 4,4'-bis(methoxymethyl)diphenyl ether, 4,4'-bis(methoxymethyl)diphenyl sulfide, 4,4'-bis (Methoxymethyl) benzophenone, 4-methoxymethylbenzoic acid-4'-methoxymethylphenyl, 4-methoxymethylbenzoic acid-4'-methoxymethyl Aniline, 4,4'-bis(methoxymethyl)phenylurea, 4,4'-bis(methoxymethyl)phenyl carbamate, 1,8-bis(methoxy Methyl)anthracene, 4,4'-bis(methoxymethyl)biphenyl, 2,2'-dimethyl-4,4'-bis(methoxymethyl)biphenyl, 2,2- Bis(4-methoxymethylphenyl) propane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol dimethyl ether, Dipropylene glycol dimethyl ether, tripropylene glycol dimethyl ether, tetrapropylene glycol dimethyl ether, etc.

二烯、四氫茚、5-亞乙基-2-降

烯、5-乙烯基-2-降

烯、三聚氰酸三烯丙酯、異三聚氰酸二烯丙酯、異三聚氰酸三烯丙酯、異三聚氰酸二烯丙基丙酯等。 Examples of the diene compound include butadiene, pentadiene, hexadiene, heptadiene, octadiene, 3-methyl-1,3-butadiene, 1,3-butanediol -Dimethacrylate, 2,4-hexadiene-1-ol, methylcyclohexadiene, cyclopentadiene, cyclohexadiene, cycloheptadiene, cyclooctadiene, dicyclopentadiene Ene, 1-hydroxydicyclopentadiene, 1-methylcyclopentadiene, methyldicyclopentadiene, diallyl ether, diallyl sulfide, diallyl adipate, 2, 5-drop

Diene, tetrahydroindene, 5-ethylene-2-nor

Ene, 5-vinyl-2-nor

Ethylene, triallyl cyanurate, diallyl isocyanurate, triallyl isocyanurate, diallyl isocyanurate, etc.

As the above-mentioned haloalkyl compound, for example, dichloroxylene, bischloromethyldimethoxybenzene, bischloromethyl mesitylene, bischloromethylbiphenyl, bischloromethyl-biphenylcarboxy Acid, bischloromethyl-biphenyldicarboxylic acid, bischloromethyl-methylbiphenyl, bischloromethyl-dimethylbiphenyl, bischloromethylanthracene, ethylene glycol bis(chloroethyl) Ether, diethylene glycol bis(chloroethyl) ether, triethylene glycol bis(chloroethyl) ether, tetraethylene glycol bis(chloroethyl) ether, etc.

、1,4-二氮雜雙環[2.2.2]辛烷、1,8-二氮雜雙環[5.4.0]-7-十一烯、1,5-二氮雜雙環[4.3.0]-5-壬烯、氨、六亞甲基四胺等。 The above-mentioned phenol compound and the copolymer component are condensed by dehydration, dehydrohalogenation, or dealcoholization, or polymerization is performed while the unsaturated bond is broken, thereby obtaining (A) phenol resin, and a catalyst can also be used during polymerization . Examples of acid catalysts include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, phosphorous acid, methanesulfonic acid, p-toluenesulfonic acid, dimethylsulfuric acid, diethylsulfuric acid, acetic acid, oxalic acid, and 1-hydroxyethylene. -1,1'-Diphosphonic acid, zinc acetate, boron trifluoride, boron trifluoride-phenol complex, boron trifluoride-ether complex, etc. On the other hand, as alkaline catalysts, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, triethylamine, pyridine, 4-N,N- Dimethylaminopyridine, piperidine, piper

, 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0] -5-nonene, ammonia, hexamethylenetetramine, etc.

Regarding the amount of the catalyst used to obtain the phenol resin having the repeating structure represented by the general formula (7), relative to the total moles of the copolymer component (ie, components other than the phenol compound), it is preferably an aldehyde compound or a ketone compound The total molar number of hydroxymethyl compound, alkoxymethyl compound, diene compound and haloalkyl compound is 100 mol%, preferably in the range of 0.01 mol% to 100 mol%.

(A) In the synthesis reaction of the phenol resin, the reaction temperature is generally preferably 40°C to 250°C, more preferably 100°C to 200°C, and the reaction time is preferably about 1 hour to 10 hours.

If necessary, a solvent capable of sufficiently dissolving the resin can be used.

Furthermore, the phenol resin having the repeating structure represented by the general formula (7) may be a phenol compound that does not become the raw material of the structure of the general formula (7) polymerized within a range that does not impair the effect of the present invention. The range that does not impair the effect of the present invention is, for example, 30% or less of the total moles of the phenol compound used as the raw material of the (A) phenol resin.

(Phenolic resin modified by a compound having an unsaturated hydrocarbon group with 4 to 100 carbons)

The phenol resin modified by a compound having an unsaturated hydrocarbon group with 4 to 100 carbons is phenol or its derivatives and a compound with an unsaturated hydrocarbon group with 4 to 100 carbons (hereinafter sometimes referred to as "unsaturated hydrocarbon group-containing compound ") The reaction product (hereinafter also referred to as "unsaturated hydrocarbyl-modified phenol derivative") and the condensation polymerization product of aldehydes, or the reaction product of a phenol resin and an unsaturated hydrocarbyl-containing compound.

The phenol derivative can be used as the phenol tree having the repeating unit represented by the general formula (7). The phenol derivatives described in the fat raw materials are the same.

Regarding the unsaturated hydrocarbon group of the unsaturated hydrocarbon group-containing compound, from the viewpoint of the residual stress of the cured film and the suitability of the reflow process, it is preferable to include two or more unsaturated groups. In addition, from the viewpoint of compatibility when the resin composition is made and the residual stress of the cured film, the unsaturated hydrocarbon group preferably has a carbon number of 4 to 100, more preferably a carbon number of 8 to 80, and even more preferably a carbon number 10~60.

Examples of compounds containing unsaturated hydrocarbon groups include: unsaturated hydrocarbons with 4 to 100 carbon atoms, polybutadiene with carboxyl groups, epoxidized polybutadiene, linolenic alcohol, oleyl alcohol, unsaturated fatty acids, and unsaturated fats Acid ester. Suitable unsaturated fatty acids include crotonic acid, myristic acid, palmitoleic acid, oleic acid, elaidic acid, isoleic acid, codoleic acid, erucic acid, arachidonic acid, linoleic acid , Α-linolenic acid, eleostearic acid, stearidonic acid, arachidonic acid, eicosapentaenoic acid, herring acid and docosahexaenoic acid. Among them, particularly from the viewpoints of the elongation of the cured film and the flexibility of the cured film, vegetable oil as an unsaturated fatty acid ester is particularly preferred.

Vegetable oils usually contain esters of glycerin and unsaturated fatty acids. There are non-drying oils with an iodine value of 100 or less, semi-drying oils with an iodine value of more than 100 and less than 130, or drying oils with an iodine value of 130 or more. As the non-drying oil, for example, olive oil, morning glory seed oil, fleeceflower oil, camellia oil, camellia oil, castor oil, and peanut oil can be cited. Examples of semi-drying oils include corn oil, cottonseed oil, and sesame oil. Examples of drying oils include tung oil, linseed oil, soybean oil, walnut oil, safflower oil, sunflower oil, stalk oil, and mustard oil. In addition, processed vegetable oils processed from these vegetable oils can also be used.

Among the above-mentioned vegetable oils, it is preferable to use non-drying oils from the viewpoint of preventing gelation caused by the excessive progress of the reaction during the reaction of phenol or its derivatives or phenol resin with vegetable oils and improving the yield. On the other hand, regarding the adhesion, mechanical properties and thermal shock resistance of the resist pattern From a high point of view, it is preferable to use a drying oil. Among the dry oils, in terms of more effectively and reliably exerting the effects of the present invention, tung oil, linseed oil, soybean oil, walnut oil, and safflower oil are preferable, and tung oil and linseed oil are more preferable. These vegetable oils can be used individually by 1 type or in combination of 2 or more types.

The reaction of phenol or its derivatives with the unsaturated hydrocarbon group-containing compound is preferably carried out at 50-130°C. Regarding the reaction ratio of phenol or its derivatives and unsaturated hydrocarbon group-containing compounds, from the viewpoint of reducing the residual stress of the cured film, the unsaturated hydrocarbon group-containing compound is preferably 1 relative to 100 parts by mass of phenol or its derivatives. ~100 parts by mass, more preferably 5-50 parts by mass. If the unsaturated hydrocarbon group-containing compound is less than 1 part by mass, the flexibility of the cured film tends to decrease, and if it exceeds 100 parts by mass, the heat resistance of the cured film tends to decrease. In the above reaction, p-toluenesulfonic acid, trifluoromethanesulfonic acid, etc. can also be used as a catalyst as necessary.

烷等甲醛前驅物。該等醛類可單獨使用1種或將2種以上組合使用。 The unsaturated hydrocarbon group-modified phenol derivative produced by the above reaction is polycondensed with aldehydes, thereby producing a phenol resin modified with an unsaturated hydrocarbon group-containing compound. Aldehydes such as formaldehyde, acetaldehyde, furfural, benzaldehyde, hydroxybenzaldehyde, methoxybenzaldehyde, hydroxyphenylacetaldehyde, methoxyphenylacetaldehyde, crotonaldehyde, chloroacetaldehyde, chlorophenylacetaldehyde , Acetone, glyceraldehyde, glyoxylic acid, methyl glyoxylate, phenyl glyoxylate, hydroxyphenyl glyoxylate, formylacetic acid, methylformylacetate, 2-formylpropionic acid, 2 -Methyl methacrylate, pyruvic acid, acetylpropionic acid, 4-acetylbutyric acid, acetone dicarboxylic acid and 3,3'-4,4'-benzophenone tetracarboxylic acid are selected. In addition, paraformaldehyde, three

Formaldehyde precursors such as alkanes. These aldehydes can be used individually by 1 type or in combination of 2 or more types.

The reaction between the above-mentioned aldehydes and the above-mentioned unsaturated hydrocarbon group-modified phenol derivative is a condensation polymerization reaction, and the previously known synthesis conditions of phenol resin can be used. The reaction is preferably carried out in the presence of a catalyst such as an acid or a base. From the viewpoint of the degree of polymerization (molecular weight) of the resin, it is more preferable to use an acid catalyst. As Examples of acid catalysts include hydrochloric acid, sulfuric acid, formic acid, acetic acid, p-toluenesulfonic acid, and oxalic acid. These acid catalysts can be used individually by 1 type or in combination of 2 or more types.

The above reaction is usually preferably carried out at a reaction temperature of 100 to 120°C. In addition, the reaction time varies depending on the type or amount of the catalyst used, but is usually 1 to 50 hours. After the reaction is completed, the reaction product is dehydrated under reduced pressure at a temperature below 200° C. to obtain a phenol resin modified with an unsaturated hydrocarbon group-containing compound. In addition, solvents such as toluene, xylene, methanol, etc. can be used for the reaction.

A phenol resin modified with an unsaturated hydrocarbon group-containing compound can also be obtained by polycondensation of a compound other than phenol such as meta-xylene and aldehydes with the above-mentioned unsaturated hydrocarbon group-modified phenol derivative. In this case, the added molar ratio of the compound other than phenol to the compound obtained by reacting the phenol derivative with the unsaturated hydrocarbon group-containing compound is preferably less than 0.5.

The phenol resin modified with the unsaturated hydrocarbon group-containing compound can also be obtained by reacting the phenol resin with the unsaturated hydrocarbon group-containing compound. The phenol resin used in this case is a polycondensation product of a phenol compound (ie, phenol and/or phenol derivatives) and aldehydes. In this case, as the phenol derivatives and aldehydes, the same ones as the above-mentioned phenol derivatives and aldehydes can be used, and the phenol resin can be synthesized under the previously known conditions as described above.

Specific examples of phenol resins obtained from phenol compounds and aldehydes suitable for forming phenol resins modified with unsaturated hydrocarbon group-containing compounds include: phenol/formaldehyde novolac resins, cresol/formaldehyde novolac resins , Hydroquinone/formaldehyde novolac resin, resorcinol/formaldehyde novolac resin and phenol-naphthol/formaldehyde novolac resin.

The unsaturated hydrocarbon group-containing compound that reacts with the phenol resin can be the same as the unsaturated hydrocarbon group-containing compound that participates in the production of the unsaturated hydrocarbon group-modified phenol derivative that reacts with aldehydes.

The reaction of the phenol resin and the unsaturated hydrocarbon group-containing compound is usually preferably carried out at 50 to 130°C. In addition, the reaction ratio of the phenol resin and the unsaturated hydrocarbon group-containing compound increases the cured film From the viewpoint of flexibility of the (resist pattern), relative to 100 parts by mass of the phenol resin, the unsaturated hydrocarbon group-containing compound is preferably 1 to 100 parts by mass, more preferably 2 to 70 parts by mass, and still more preferably 5-50 parts by mass. If the unsaturated hydrocarbon group-containing compound is less than 1 part by mass, the flexibility of the cured film tends to decrease, and if it exceeds 100 parts by mass, the possibility of gelation during the reaction tends to increase, and the cured film The heat resistance tends to decrease. When the phenol resin reacts with an unsaturated hydrocarbon group-containing compound, if necessary, p-toluenesulfonic acid, trifluoromethanesulfonic acid, etc. can also be used as a catalyst. In addition, solvents such as toluene, xylene, methanol, tetrahydrofuran and the like can be used during the reaction, which will be described in detail below.

It is also possible to use a phenol resin that is acid-modified by reacting the remaining phenolic hydroxyl group in the phenol resin modified with an unsaturated hydrocarbon group-containing compound produced by the above method with a polybasic acid anhydride. By acid modification with polybasic acid anhydride to introduce carboxyl groups, the solubility in alkaline aqueous solution (used as a developer) is further improved.

The polybasic acid anhydride is not particularly limited as long as it has an acid anhydride group formed by dehydration and condensation of the carboxyl group of a polybasic acid containing a plurality of carboxy groups. Examples of polybasic acid anhydrides include phthalic anhydride, succinic anhydride, octenyl succinic anhydride, pentadecenyl succinic anhydride, maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, and hexahydro Phthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, phthalic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, methylene Dibasic acid anhydrides such as methyltetrahydrophthalic anhydride, tetrabromophthalic anhydride and trimellitic anhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, diphenyl ether tetracarboxylic acid Aromatic tetrabasic acid dianhydrides such as anhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pyromellitic dianhydride and benzophenone tetracarboxylic dianhydride. These can be used individually by 1 type or in combination of 2 or more types. Among them, the polybasic acid anhydride is preferably a dibasic acid anhydride, and more preferably one or more selected from the group consisting of tetrahydrophthalic anhydride, succinic anhydride, and hexahydrophthalic anhydride. In this case, it is possible to The advantage of forming a better-shaped resist pattern.

The reaction of phenolic hydroxyl group and polybasic acid anhydride can be carried out at 50~130℃. In this reaction, with respect to 1 mole of the phenolic hydroxyl group, it is preferable to react a polybasic acid anhydride of 0.10 to 0.80 moles, more preferably to react 0.15 to 0.60 moles, and more preferably to react 0.20 to 0.40 moles. The ear reacts. If the polybasic acid anhydride is less than 0.10 mol, the developability tends to decrease, and if it exceeds 0.80 mol, the alkali resistance of the unexposed area tends to decrease.

Furthermore, from the viewpoint of making the reaction proceed quickly, the above-mentioned reaction may optionally contain a catalyst. Examples of catalysts include tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, imidazole compounds such as 2-ethyl-4-methylimidazole, and phosphorus compounds such as triphenylphosphine. .

Furthermore, the acid value of the phenol resin modified by the polybasic acid anhydride is preferably 30-200 mgKOH/g, more preferably 40-170 mgKOH/g, and still more preferably 50-150 mgKOH/g. If the acid value is less than 30mgKOH/g, there is a tendency for alkaline development to take longer than when the acid value is in the above range. If it exceeds 200mgKOH/g, it will be longer than when the acid value is in the above range. The tendency of the unexposed area to decrease the resistance to developing solution.

Regarding the molecular weight of the phenol resin modified by the unsaturated hydrocarbon group-containing compound, considering the solubility in the alkaline aqueous solution, or the balance between the photosensitive characteristics and the physical properties of the cured film, the weight average molecular weight is preferably 1,000 to 100,000, and more Preferably, it is 2000 to 100,000.

As the (A) phenol resin of this embodiment, it is also preferably selected from the phenol resin having the repeating unit represented by the above general formula (7) and the above modified compound having an unsaturated hydrocarbon group having 4 to 100 carbons A mixture of at least one phenol resin (hereinafter also referred to as (a3) resin) among phenol resins and a phenol resin selected from novolac and polyhydroxystyrene (hereinafter also referred to as (a4) resin). The mixing ratio of (a3) resin and (a4) resin is in the range of (a3)/(a4)=5/95~95/5 in terms of mass ratio. The mixing ratio is based on the solubility in alkaline aqueous solution, the sensitivity and resolution when forming resist patterns, and the cured film From the viewpoint of the residual stress and the suitability of the reflow process, it is preferably (a3)/(a4)=5/95~95/5, more preferably (a3)/(a4)=10/90~90/ 10, more preferably (a3)/(a4)=15/85~85/15. Regarding the novolak and polyhydroxystyrene as the above (a4) resin, the same resins as those shown in the above (novolak) and (polyhydroxystyrene) can be used.

(B) Plasticizer

The (B) plasticizer in this embodiment will be described in detail below. (B) The plasticizer is used to heat and harden the embossed pattern formed by using the photosensitive resin composition of this embodiment to improve the fluidity of (A) resin and the accumulation of polymer of (A) resin Compound. By improving the stackability, the generation of voids during the high-temperature storage test can be suppressed, and the decrease in adhesion at the interface between the Cu layer and the resin layer can be suppressed. (B) The plasticizer is not particularly limited as long as it meets the above conditions.

Regarding compounds that function as (B) plasticizers, the following general formula (7) can be used particularly preferably:

{In the formula, X is a structure containing saturated or unsaturated hydrocarbons or aromatic hydrocarbons with a carbon number of 1 or more and 15 or less, n is an integer from 1 to 4, when n is 2 or more, R can be the same It can also be different, it is represented by saturated hydrocarbons or unsaturated hydrocarbons or aromatic hydrocarbons with carbon number of 2 or more and 15 or less Compound.

Among them, as the plasticizer of the present invention, it is preferably selected from the following general formula (8):

{In the formula, m is an integer from 1 to 4, and when m is 2 or more, R may be the same or different, respectively, representing a saturated or unsaturated hydrocarbon or aromatic hydrocarbon with a carbon number of 2 or more and 15 or less} , Or the following general formula (9):

{In the formula, Y is a structure containing saturated or unsaturated hydrocarbons or aromatic hydrocarbons with a carbon number of 1 or more and 10 or less, and R may be the same or different, and represents a saturated hydrocarbon with a carbon number of 2 or more and 15 or less Or at least one of the group consisting of unsaturated hydrocarbons or aromatic hydrocarbons.

As the plasticizer represented by the above general formula (7), benzoate, phthalate, isophthalate, terephthalate, trimellitate, homo Pyromellitic acid ester and aliphatic acid tetrahydrofurfuryl ester, etc. Examples of specific compounds of benzoate include methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, pentyl benzoate, heptyl benzoate, n-octyl benzoate, Nonyl benzoate, isononyl benzoate, isodecyl benzoate, 2-ethylhexyl benzoate, isodecyl benzoate, butyl benzyl benzoate, cyclopropyl benzoate, cyclobutyl benzoate , Cyclopentyl benzoate, cyclohexyl benzoate, cycloheptyl benzoate, allyl benzoate, butyl benzyl benzoate, phenyl benzoate. Among them, 2-ethylhexyl benzoate, cyclohexyl benzoate, and phenyl benzoate are particularly suitably used.

Examples of specific compounds of phthalates include: dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, phthalate Dipentyl dicarboxylate, diheptyl phthalate, di-n-octyl phthalate, dinonyl phthalate, diisononyl phthalate, diisodecyl phthalate, o- Bis(2-ethylhexyl) phthalate, diisodecyl phthalate, butyl benzyl phthalate, dicyclopropyl phthalate, dicyclobutyl phthalate, ortho Dicyclopentyl phthalate, dicyclohexyl phthalate, dicycloheptyl phthalate, diallyl phthalate, dibutyl benzyl phthalate, dicyclohexyl phthalate Phenyl ester. Among them, bis(2-ethylhexyl) phthalate, dicyclohexyl phthalate, and diphenyl phthalate are particularly suitably used.

Examples of specific compounds of isophthalate include: dimethyl isophthalate, diethyl isophthalate, dipropyl isophthalate, dibutyl isophthalate, and isobenzene Dipentyl dicarboxylate, diheptyl isophthalate, di-n-octyl isophthalate, dinonyl isophthalate, diisononyl isophthalate, diisodecyl isophthalate, Phthalic acid bis(2-ethyl Hexyl) ester, diisodecyl isophthalate, butyl benzyl isophthalate, dicyclopropyl isophthalate, dicyclobutyl isophthalate, dicyclopentyl isophthalate, Dicyclohexyl phthalate, dicycloheptyl isophthalate, diallyl isophthalate, dibutyl benzyl isophthalate, diphenyl isophthalate. Among them, bis(2-ethylhexyl) isophthalate, dicyclohexyl isophthalate, and diphenyl isophthalate are particularly suitably used.

Examples of specific compounds of terephthalate include: dimethyl terephthalate, diethyl terephthalate, dipropyl terephthalate, dibutyl terephthalate, and terephthalate Dipentyl dicarboxylate, diheptyl terephthalate, di-n-octyl terephthalate, dinonyl terephthalate, diisononyl terephthalate, diisodecyl terephthalate, p- Bis(2-ethylhexyl) phthalate, diisodecyl terephthalate, butyl benzyl terephthalate, dicyclopropyl terephthalate, dicyclobutyl terephthalate, p- Dicyclopentyl phthalate, dicyclohexyl terephthalate, dicycloheptyl terephthalate, diallyl terephthalate, dibutyl benzyl terephthalate, dicyclohexyl terephthalate Phenyl ester. Among them, bis(2-ethylhexyl) terephthalate, dicyclohexyl terephthalate, and diphenyl terephthalate are particularly suitably used.

Examples of specific compounds of trimellitate include: trimethyl trimellitate, triethyl trimellitate, tripropyl trimellitate, tributyl trimellitate, trimellitate Triamyl formate, Triheptyl trimellitate, Tri-n-octyl trimellitate, Trinonyl trimellitate, Triisononyl trimellitate, Triisodecyl trimellitate, Trimellitic acid Tris (2-ethylhexyl) tricarboxylate, triisodecyl trimellitate, tributyl benzyl trimellitate, tricyclopropyl trimellitate, tricyclobutyl trimellitate, partial Tricyclopentyl trimellitate, Tricyclohexyl trimellitate, Tricycloheptyl trimellitate, Triallyl trimellitate, Tributylbenzyl trimellitate, Trimellitic acid Phenyl ester. Among them, tris(2-ethylhexyl) trimellitate, tricyclohexyl trimellitate, and triphenyl trimellitate are particularly suitably used.

Examples of specific compounds of pyromellitic acid esters include tetramethyl pyromellitic acid, tetraethyl pyromellitic acid, tetrapropyl pyromellitic acid, tetrabutyl pyromellitic acid, and pyromellitic acid. Tetrapentyl tetracarboxylate, tetraheptyl pyromellitic acid, tetra-n-octyl pyromellitic acid, tetranonyl pyromellitic acid, tetraisononyl pyromellitic acid, tetraisodecyl pyromellitic acid, all Pyromellitic acid tetra(2-ethylhexyl) ester, pyromellitic acid tetraisodecyl ester, pyromellitic acid tetrabutyl benzyl ester, pyromellitic acid tetracyclopropyl ester, pyromellitic acid tetracyclobutyl ester, Pyromellitic acid tetracyclopentyl, pyromellitic tetracyclohexyl, pyromellitic tetracycloheptyl, pyromellitic tetraallyl, pyromellitic tetra-butyl benzyl, pyromellitic acid Tetraphenyl ester. Among them, pyromellitic tetrakis (2-ethylhexyl), pyromellitic tetracyclohexyl, and pyromellitic tetraphenyl tetracarboxylate are particularly suitably used.

As the plasticizer represented by the above general formula (8), malonate, succinate, glutarate, adipate, pimelate, suberate, azelate, Sebacate etc. Examples of specific compounds of malonate include: dimethyl malonate, diethyl malonate, dipropyl malonate, dibutyl malonate, dipentyl malonate, propylene Diheptyl diacid, di-n-octyl malonate, dinonyl malonate, diisononyl malonate, diisodecyl malonate, bis(2-ethylhexyl) malonate, Diisodecyl malonate, butyl benzyl malonate, dicyclopropyl malonate, dicyclobutyl malonate, dicyclopentyl malonate, dicyclohexyl malonate, malonate Dicycloheptyl malonate, diallyl malonate, dibutyl benzyl malonate, diphenyl malonate. Among them, bis(2-ethylhexyl) malonate, dicyclohexyl malonate, and diphenyl malonate are particularly suitably used.

Examples of specific compounds of succinate include: dimethyl succinate, diethyl succinate, dipropyl succinate, dibutyl succinate, dipentyl succinate, diheptyl succinate, succinate Di-n-octyl succinate, dinonyl succinate, diisononyl succinate, diisodecyl succinate, bis(2-ethylhexyl) succinate, diisodecyl succinate, butyl benzyl succinate Ester, dicyclopropyl succinate, dicyclobutyl succinate, dicyclopentyl succinate, dicyclohexyl succinate, dicyclohexyl succinate Heptyl ester, diallyl succinate, dibutyl benzyl succinate, diphenyl succinate. Among them, bis(2-ethylhexyl) succinate, dicyclohexyl succinate, and diphenyl succinate are particularly suitably used.

Examples of specific compounds of glutaric acid esters include: dimethyl glutarate, diethyl glutarate, dipropyl glutarate, dibutyl glutarate, dipentyl glutarate, and glutarate. Diheptyl diacid, di-n-octyl glutarate, dinonyl glutarate, diisononyl glutarate, diisodecyl glutarate, bis(2-ethylhexyl) glutarate, Diisodecyl glutarate, butyl benzyl glutarate, dicyclopropyl glutarate, dicyclobutyl glutarate, dicyclopentyl glutarate, dicyclohexyl glutarate, glutaric acid Dicycloheptyl glutarate, diallyl glutarate, dibutyl benzyl glutarate, diphenyl glutarate. Among them, bis(2-ethylhexyl) glutarate, dicyclohexyl glutarate, and diphenyl glutarate are particularly suitably used.

Examples of specific compounds of adipate include: dimethyl adipate, diethyl adipate, dipropyl adipate, dibutyl adipate, dipentyl adipate, and adipate. Diheptyl diacid, di-n-octyl adipate, dinonyl adipate, diisononyl adipate, diisodecyl adipate, bis(2-ethylhexyl) adipate, Diisodecyl adipate, butyl benzyl adipate, dicyclopropyl adipate, dicyclobutyl adipate, dicyclopentyl adipate, dicyclohexyl adipate, adipate Dicycloheptyl adipate, diallyl adipate, dibutyl benzyl adipate, diphenyl adipate. Among them, bis(2-ethylhexyl) adipate, dicyclohexyl adipate, and diphenyl adipate are particularly suitably used.

Examples of specific compounds of pimelate include: dimethyl pimelate, diethyl pimelate, dipropyl pimelate, dibutyl pimelate, dipentyl pimelate, and Diheptyl diacid, di-n-octyl pimelate, dinonyl pimelate, diisononyl pimelate, diisodecyl pimelate, bis(2-ethylhexyl) pimelate, Diisodecyl pimelate, butyl benzyl pimelate, dicyclopropyl pimelate, dicyclobutyl pimelate, dicyclopentyl pimelate, dicyclohexyl pimelate, pimelate Dicycloheptyl pimelate, diallyl pimelate, dibutyl benzyl pimelate, diphenyl pimelate. Among them, bis(2-ethylhexyl) pimelate, dicyclohexyl pimelate, and diphenyl pimelate are particularly suitably used.

Examples of specific compounds of suberic acid esters include: dimethyl suberate, diethyl suberate, dipropyl suberate, dibutyl suberate, dipentyl suberate, octane Diheptyl diacid, di-n-octyl suberate, dinonyl suberate, diisononyl suberate, diisodecyl suberate, bis(2-ethylhexyl) suberate, Diisodecyl suberate, butyl benzyl suberate, dicyclopropyl suberate, dicyclobutyl suberate, dicyclopentyl suberate, dicyclohexyl suberate, suberyl Dicycloheptyl suberate, diallyl suberate, dibutyl benzyl suberate, diphenyl suberate. Among them, bis(2-ethylhexyl) suberate, dicyclohexyl suberate, and diphenyl suberate are particularly suitably used.

Specific examples of compounds of azelaic acid esters include: dimethyl azelate, diethyl azelate, dipropyl azelate, dibutyl azelate, dipentyl azelate, azela Diheptyl azelate, di-n-octyl azelate, dinonyl azelate, diisononyl azelate, diisodecyl azelate, bis(2-ethylhexyl) azelate, Diisodecyl azelate, butyl benzyl azelate, dicyclopropyl azelate, dicyclobutyl azelate, dicyclopentyl azelate, dicyclohexyl azelate, azelaic acid Dicycloheptyl azelate, diallyl azelate, dibutyl benzyl azelate, diphenyl azelate. Among them, bis(2-ethylhexyl) azelate, dicyclohexyl azelate, and diphenyl azelate are particularly suitably used.

Examples of specific compounds of sebacate include: dimethyl sebacate, diethyl sebacate, dipropyl sebacate, dibutyl sebacate, dipentyl sebacate, and sebacate. Diheptyl diacid, di-n-octyl sebacate, dinonyl sebacate, diisononyl sebacate, diisodecyl sebacate, bis(2-ethylhexyl) sebacate, Diisodecyl sebacate, butyl benzyl sebacate, dicyclopropyl sebacate, dicyclobutyl sebacate, dicyclopentyl sebacate, dicyclohexyl sebacate, sebacate Dicycloheptyl sebacate, diallyl sebacate, dibutyl benzyl sebacate, diphenyl sebacate. Among them, bis(2-ethylhexyl) sebacate, dicyclohexyl sebacate, and diphenyl sebacate are particularly suitably used.

Examples of specific compounds of the aliphatic acid tetrahydrofurfuryl include: tetrahydrofurfuryl formate, tetrahydrofurfuryl acetate, tetrahydrofurfuryl propionate, tetrahydrofurfuryl butyrate, and tetrahydrofurfuryl isobutyrate. , E Tetrahydrofurfuryl acid, tetrahydrofurfuryl isovalerate, tetrahydrofurfuryl caproate, etc. Among them, tetrahydrofurfuryl propionate, tetrahydrofurfuryl butyrate, and tetrahydrofurfuryl isobutyrate are particularly suitably used.

Regarding the content of the plasticizer (B), relative to 100 parts by mass of the resin (A), it is preferably 0.1 to 50 parts by mass, more preferably 1 to 40 parts by mass, and still more preferably 1 to 30 parts by mass. If the content is more than this range, the glass transition temperature is lowered, so it is not preferable. If the content is less than this range, sufficient plasticization cannot be obtained, and voids are likely to occur between the copper surface.

The function of the plasticizer (B) in this embodiment is to increase the fluidity of (A) resin and improve (A) when the embossed pattern formed by using the photosensitive resin composition of this embodiment is heated and hardened. ) The accumulation of the resin polymer. Thereby, a strong cured film can be obtained, the generation of voids during the high temperature storage test can be suppressed, and the adhesion drop at the interface between the Cu layer and the resin layer can be suppressed.

The photosensitive resin composition of this embodiment may contain any one of (B-1) nano particles, (B-2) thermal crosslinking agent, and (B-3) fluorine-containing hydrophobic compound instead of the above (B) Plasticizer or combined with it.

By combining photosensitive resin with specific (B-1) nanoparticle, (B-2) thermal crosslinking agent, or (B-3) fluorine-containing hydrophobic compound, a photosensitive resin combination can be provided And the method for forming a hardened relief pattern using the photosensitive resin composition, the photosensitive resin composition can be obtained after high temperature storage test, and it does not appear at the interface between the Cu layer and the resin layer. A photosensitive resin with high adhesiveness due to voids.

(B-1) Nanoparticles

(B-1) Nanoparticles are solid at room temperature and are particles with an average primary particle diameter of 1 μm or less, preferably 300 nm or less from the viewpoint of light transmittance. The primary particle size can be determined by SEM observation or laser diffraction. In addition, from the viewpoint of Cu migration resistance during HTS, plate-shaped, scaly, needle-shaped, or fibrous particles with an aspect ratio of 5 or more are preferable, and the compatibility with (A) resin From a viewpoint, it is preferable to perform surface treatment with a silane coupling agent or the like. Furthermore, from the viewpoint of water resistance, the nanoparticles preferably contain oxides, composite oxides, doped oxides, oxyacids, oxyacid salts, nitrides, carbides, or sulfides.

As the (B-1) nanoparticle that can be used in the present invention, for example, SiO ₂ , Al ₂ O ₃ , TiO ₂ , ZrO ₂ , HfO ₂ , V ₂ O ₅ , WO ₃ , In ₂ O ₃ , SnO ₂ , Sb ₂ O ₃ , Nb ₂ O ₅ , MoO ₃ , Fe ₂ O ₃ , CuO, ZnO, CaO, MgO, Aerosil, Silica, Mica, Montmorillonite, Talc, Clay, Water Aluminum Mineral, kaolin, (poly) zirconium phosphate, barium titanate, calcium carbonate, (poly) zirconium tungstate, PZT (Lead Zirconium Titanate, lead zirconium titanate), glass, aluminum borate, aluminum nitride, titanium nitride, nitrogen Silicon, boron nitride, or a mixture of these, etc.

By adding nano particles, the thermal expansion coefficient of the photosensitive resin can be reduced. By reducing the thermal expansion coefficient, the thermal expansion of the resin during the high-temperature storage test is suppressed, and the occurrence of copper migration is suppressed. At this time, as the nanoparticle, a shape with a high aspect ratio can reduce the thermal expansion coefficient by adding a smaller amount, so it is preferable. In addition, a shape with a high aspect ratio tends to decrease the number of voids on the copper surface and improve developability or chemical resistance, which is better.

From the viewpoint of the number of voids on the copper surface, developability, or chemical resistance, the aspect ratio of the nanoparticle is preferably greater than 1, and the aspect ratio is preferably 2 or greater, more preferably 3 or greater, and more preferably 4 or greater. Furthermore, the aspect ratio is more preferably 5 or more, more preferably 8 or more, more preferably 10 or more, still more preferably 12 or more, still more preferably 15 or more, and particularly preferably 20 or more.

The aspect ratio is the value of the length of the long axis/the length of the short axis of the nanoparticle. When the nanoparticle is a standard sphere, the aspect ratio becomes 1. When the nanoparticle is not a standard sphere or a standard ellipsoid, the diameter of the smallest sphere that can completely enclose the nanoparticle in the inner size of the sphere is used as the long axis of the nanoparticle to be completely contained in the nanoparticle. The diameter of the largest sphere among the spheres of the inner size of the rice particle is taken as the minor axis of the nanoparticle.

Regarding the blending amount of (B-1) nanoparticle, it is 0.1-50 mass parts with respect to 100 mass parts of (A) resin, Preferably it is 0.05-10 mass parts. From the viewpoint of migration resistance, it is more preferably 0.1 parts by mass or more, and from the viewpoint of solubility, it is more preferably less than 50 parts by mass.

(B-2) Thermal crosslinking agent

The (B-2) thermal crosslinking agent used in the present invention will be described. (B-2) The thermal crosslinking agent is capable of crosslinking with the resin (A) or the crosslinking agent itself when the embossed pattern formed using the photosensitive resin composition of this embodiment is cured by heating Network-like structure compound. (B) The thermal crosslinking agent is not particularly limited as long as it satisfies the above conditions, but it is preferably any one of the following (B-2-1) to (B-2-12).

(B-2-1) Compounds containing hydroxymethyl and/or alkoxymethyl

The so-called hydroxymethyl and/or alkoxymethyl-containing compounds contain the following general formula (TS2) in the molecule:

{In the formula, Rs3 is a monovalent organic group or a hydrogen atom} represented by an organic compound.

Specifically, it has the following general formula (TS1):

{In the formula, Rs1 is a hydrogen atom, a univalent group selected from the group consisting of methyl, ethyl, n-propyl and isopropyl, and Rs2 is an alkyl group with 1-10 carbon atoms selected from a hydroxyl group , Alkoxy group with 1-10 carbon atoms, ester group with 1-10 carbon atoms, and urethane group, mm1 is an integer of 1 to 5, mm2 is 0-4 Of integers. Here, 1≦(mm1+mm2)≦5, nn1 is an integer of 1~4, V ₁ is CH ₂ ORs1 when nn1=1, single bond or 2~4 valence organic when nn1=2~4 base. When there are plural CH ₂ ORs1 and R ₁₀ , these may be the same or different from each other}, and the general formulas (TS3) and (TS4):

{In the formula, Rs3 and Rs4 are each independently a hydrogen atom and a monovalent organic group selected from the group consisting of hydrocarbon groups with 1 to 10 carbon atoms}

[化86]

{Where, Rs5 is independently a hydrogen atom and a monovalent organic group selected from the group consisting of hydrocarbon groups with 1 to 10 carbon atoms} N-methylol compound and N-alkoxy The base methyl compound etc. are not limited to these.

As preferred specific examples, include: Cymel (registered trademark) 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR 65, 300, Micoat 102, 105 (the above are manufactured by Mitsui Cytec), NIKALAC (registered trademark) MX-270, -280, -290, NIKALAC MS-11, NIKALAC MW-30, -100, -300,- 390, -750 (manufactured by SANWA CHEMICAL), DML-OCHP, DML-MBPC, DML-BPC, DML-PEP, DML-34X, DML-PSBP, DML-PTBP, DML-PCHP, DML-POP, DML -PFP, DML-MBOC, BisCMP-F, DML-BisOC-Z, DML-BisOCHP-Z, DML-BisOC-P, DMOM-PTBT, TMOM-BP, TMOM-BPA, TML-BPAFMF, TM-BIP-A , HMOM-TP-HAP (manufactured by Benzhou Chemical Industry Company above), benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether , Bis(hydroxymethyl)benzophenone, hydroxymethylphenyl hydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl) Base) benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)di Benzophenone, methoxymethyl benzoic acid methoxy Methyl phenyl ester, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, methylolated form of novolac, etc.

Among them, it is more preferable to have the structure represented by the above general formula (12), and specifically, include: DML-OCHP, DML-MBPC, DML-BPC, DML-PEP, DML-34X, DML-PSBP, DML -PTBP, DML-PCHP, DML-POP, DML-PFP, DML-MBOC, BisCMP-F, DML-BisOC-Z, DML-BisOCHP-Z, DML-BisOC-P, DMOM-PTBT, TMOM-BP, TMOM -BPA, TML-BPAFMF, TM-BIP-A, HMOM-TP-HAP (manufactured by Benzhou Chemical Industry Co., Ltd. above), benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxy Benzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenyl hydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxy) Methyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)di Phenyl ether, bis(methoxymethyl)benzophenone, methoxymethyl phenyl methoxymethyl benzoate, bis(methoxymethyl)biphenyl, dimethylbis(methoxy) (Methyl) biphenyl and hydroxymethylated form of novolac.

Among these, TMOM-BP, TMOM-BPA, TML-BPAFMF, TM-BIP-A, and HMOM-TP-HAP are particularly preferred.

(B-2-2) Ethylene oxide compound

The ethylene oxide (epoxy) compound is not particularly limited as long as it is a compound containing an epoxy group in the molecule. Specifically, it includes: phenol novolak type epoxy resin, cresol novolak type epoxy Resin, bisphenol epoxy resin, triphenol epoxy resin, tetraphenol epoxy resin, phenol-xylylene epoxy resin, naphthol-xylylene epoxy resin, phenol-naphthol Type epoxy resin, phenol-dicyclopentadiene type epoxy resin, alicyclic epoxy resin, chain aliphatic epoxy resin, diethylene glycol diglycidyl ether, sorbitol polyglycidyl ether, propylene glycol two Shrink Glycidyl ether, trimethylolpropane polyglycidyl ether, 1,1,2,2-tetra(p-hydroxyphenyl)ethane tetraglycidyl ether, glycerol triglycidyl ether, o-second butylphenyl glycidyl ether Glyceryl ether, 1,6-bis(2,3-glycidyloxy)naphthalene, diglycerol polyglycidyl ether, polyethylene glycol glycidyl ether, YDB-340, YDB-412, YDF-2001, YDF- 2004 (trade name, manufactured by Nippon Steel Chemical Co., Ltd.), GAN, GOT, NC-3000-H, EPPN-501H, EPPN-502H, EOCN-1020, NC-6000, NC-7000L, EPPN-201L, XD -1000, EOCN-4600 (trade name, manufactured by Nippon Kayaku Co., Ltd.), Epikote (registered trademark) 1001, Epikote 1007, Epikote 1009, Epikote 5050, Epikote 5051, Epikote 1031S, Epikote 180S65, Epikote 157H70, YX-315 -75 (trade name, manufactured by Japan Epoxy Resins Co., Ltd.), EHPE3150, PLACCEL G402, PUE101, PUE105 (trade name, manufactured by Diacel Chemical Industries Co., Ltd.), EPICLON (registered trademark) 830, 850, 1050, N-680 , N-690, N-695, N-770, HP-7200, HP-820, EXA-850CRP, 860, EXA-4701, EXA-4850-1000 (trade name, manufactured by DIC), DENACOL (registered trademark) EX-201, EX-212L, EX-214L, EX-216L, EX-251, EX-203, EX-313, EX-314, EX-321, EX-411, EX-511, EX-512, EX- 612, EX-614, EX-614B, EX-711, EX-731, EX-810, EX-850L, EX-911, EM-150 (trade name, manufactured by Nagase chemteX), Epolight (registered trademark) 70P, 40E, 100E, 100MF, 200E, 400E, 200P, 400P, 1500NP, 80MF, 4000, 3002 (trade name, manufactured by Kyoeisha Chemical), jER (registered trademark) 828, 834, 1001, 1002, 1003, 1004, 1005 , 1007, 1010, 1100L, 630, ESCN-220L, 220F, 220H, 220HH, 180H65, 1032H60, YX400 0H, 152, 157S70, 1031 (manufactured by Mitsubishi Chemical), Adeka Resin (registered trademark) EP-4000s, EP- 4003s (manufactured by Adeka) and so on.

Among them, from the viewpoint of reliability after the HTS test, triglycidyl isocyanurate, EPICLON 830, 850, 1050, N-680, N-690, N-695, N -770, HP-7200, HP-820, EXA-4850-1000, DENACOL EX-201, EX-313, EX-314, EX-321, EX-411, EX-511, EX-512, EX-612, Epoxy compounds of EX-614, EX-614B, EX-731, EX-810, EX-911, and EM-150.

(B-2-3) Compounds containing isocyanate groups

The isocyanate group-containing compound is not particularly limited as long as it is a compound containing an isocyanate group in the molecule. From the viewpoint of reliability after the HTS test, 4,4'-diphenylmethane diisocyanate, Toluene diisocyanate, 1,3-xylylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, Takenate (registered trademark) 500, 600, Cosmonate (registered trademark) NBDI, ND (trade name, manufactured by Mitsui Chemicals) Duranate (registered trademark) 17B-60PX, TPA-B80E, MF-B60X, MF-K60X, E402-B80T (trade name, Asahi Kasei Chemicals) Company manufacturing) etc.

(B-2-4) Bismaleimide compound

As the bismaleimide compound, as long as it is a compound containing a maleimide group in the molecule, it is not particularly limited. From the viewpoint of reliability after the HTS test, it is preferably 4, 4'-Diphenylmethane bismaleimide, phenylmethane maleimide, meta-phenyl bismaleimide, bisphenol A diphenyl ether bismaleimide Diimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3- Phenylene bismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, 4,4'-diphenyl ether biscis Butylene diimide, 4,4'-diphenyl bismaleimide, 1,3-bis(3-maleimide phenoxy)benzene, 1,3- Bis (4-maleimide phenoxy) benzene, BMI-1000, BMI-1100, BMI-2000, BMI-2300, BMI-3000, BMI-4000, BMI-5100, BMI-7000, BMI -TMH, BMI-6000, BMI-8000 (trade name, manufactured by Daiwa Chemical Industry Co., Ltd.), etc.

(B-2-5) Compounds containing aldehyde groups

烷、丙二醛、丁二醛等。 The aldehyde group-containing compound is not particularly limited as long as it is a compound containing an aldehyde group in the molecule. From the viewpoint of reliability after the HTS test, formaldehyde, benzaldehyde, acetaldehyde, propionaldehyde, and benzene are preferred. Acetaldehyde, α-phenylpropanal, β-phenylpropanal, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde , Furfural, glyoxal, glutaraldehyde, terephthalaldehyde, isophthalaldehyde, hexamethylenetetramine, three

Alkane, malondialdehyde, succinaldehyde, etc.

(B-2-6) Compounds containing oxetane ring

The so-called oxetane ring-containing compound contains the following formula:

The compound represented by the divalent radical.

The compound containing an oxetane ring is not particularly limited as long as it contains an oxetanyl group in the molecule, and examples include: 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-oxetanylmethyl) ) Ether, diethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, bis(3-ethyl-3-oxetanylmethyl)diphenolate, trimethylolpropane (3-Ethyl-3-oxetanylmethyl)ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl)ether, 3-ethyl-3{[(3-ethyloxane Butane-yl)methoxy)methyl)oxetane, 3-ethyl-3-hydroxymethyloxetane (OXT-101), 2-ethyl, manufactured by Toagosei Co., Ltd. Hexyl oxetane (OXT-212), xylylene dioxetane (OXT-121), 3-ethyl-3-{[(3-ethyloxetane-3- Yl)methoxy]methyl)oxetane (OXT-221), OX-SQ-H, OXT-191, PNOX-1009, RSOX, one of the following:

Etanacol EHO, OXBP, OXMA, OXIPA, HBOX, OXTP, etc. of Ube Industries Co., Ltd.

Among them, from the viewpoint of solubility in the developer and elongation of the cured film obtained, OXBP, OXIPA, OXT-121, and OXT-221 are preferred.

環之化合物 (B-2-7) Containing benzo

Ring compound

環之化合物，只要為分子內含有苯并

環之化合物，則並無特別限制，就HTS試驗後之可靠性之觀點而言，較佳為日本專利特開2006-335671號公報所揭示之化合物、以及雙酚F型苯并

BF-BXZ、雙酚A型苯并

BA-BXZ、雙酚S型苯并

BS-BXZ(商品名，小西化學工業製造)等。 As containing benzo

Ring compound, as long as the molecule contains benzo

The compound of the ring is not particularly limited. From the viewpoint of reliability after the HTS test, the compound disclosed in Japanese Patent Laid-Open No. 2006-335671 and the bisphenol F-type benzo

BF-BXZ, bisphenol A benzo

BA-BXZ, bisphenol S type benzo

BS-BXZ (trade name, manufactured by Konishi Chemical Industry), etc.

唑啉環之化合物 (B-2-8) contains

Oxazoline compound

唑啉環之化合物，只要為分子內含有

唑啉環之化合物，則並無特別限制，可列舉：2-

唑啉、2-胺基-2-

唑啉、2,2'-雙(2-

唑啉)、1,3-雙(4,5-二氫-2-

唑基)苯、1,4-雙(4,5-二氫-2-

唑基)苯、1,3,5-三(4,5-二氫-2-

唑基)苯、2,2'-(2,6-吡啶二基)雙(4-異丙基-2-

唑啉)、2,2'-(2,6-吡啶二基)雙(4-苯基-2-

唑啉)、2-苯基(2-

唑啉)、4,4-二甲基-2-

唑啉、2,2'-亞異丙基雙(4-苯基-2-

唑啉)、2-乙基-2-

唑啉、2,2'-亞異丙基雙(4-第三丁基-2-

唑啉)、2-異丙基-2-

唑啉、4-甲氧基甲基-2-甲基-5-苯基-2-

唑啉、2-甲基-2-

唑啉、2,4,4-三甲基-2-

唑啉、日本觸媒公司製造之Epocros系列K-1010E、K-2010E、K-1020E、K-2020E、K-1030E、K-2030E、WS-500、WS-700、RPS-1005、RAS-1005等。 As containing

The oxazoline ring compound, as long as the molecule contains

The compounds of the oxazoline ring are not particularly limited. Examples include: 2-

Oxazoline, 2-amino-2-

Oxazoline, 2,2'-bis(2-

Oxazoline), 1,3-bis(4,5-dihydro-2-

Azolyl)benzene, 1,4-bis(4,5-dihydro-2-

Azolyl)benzene, 1,3,5-tris(4,5-dihydro-2-

Azolyl)benzene, 2,2'-(2,6-pyridinediyl)bis(4-isopropyl-2-

Oxazoline), 2,2'-(2,6-pyridinediyl)bis(4-phenyl-2-

Oxazoline), 2-phenyl (2-

Oxazoline), 4,4-dimethyl-2-

Oxazoline, 2,2'-isopropylidene bis(4-phenyl-2-

Oxazoline), 2-ethyl-2-

Oxazoline, 2,2'-isopropylidene bis(4-tertiary butyl-2-

Oxazoline), 2-isopropyl-2-

Oxazoline, 4-methoxymethyl-2-methyl-5-phenyl-2-

Oxazoline, 2-methyl-2-

Oxazoline, 2,4,4-trimethyl-2-

Oxazoline, Epocros series manufactured by Nippon Shokubai Co., Ltd. K-1010E, K-2010E, K-1020E, K-2020E, K-1030E, K-2030E, WS-500, WS-700, RPS-1005, RAS-1005 Wait.

唑啉)、1,3-雙(4,5-二氫-2-

唑基)苯、1,4-雙(4,5-二氫-2-

唑基)苯、1,3,5-三(4,5-二氫-2-

唑基)苯、2-苯基(2-

唑啉)、Epocros WS-500等。 From the viewpoint of reliability after the HTS test, for example, 2,2'-double (2-

Oxazoline), 1,3-bis(4,5-dihydro-2-

Azolyl)benzene, 1,4-bis(4,5-dihydro-2-

Azolyl)benzene, 1,3,5-tris(4,5-dihydro-2-

Azolyl)benzene, 2-phenyl(2-

Oxazoline), Epocros WS-500 and so on.

唑啉環之化合物更佳為下述通式(TS5)：[化89]

Also, including

The compound of the oxazoline ring is more preferably the following general formula (TS5): [化89]

{In the formula, Rs6 is an organic group with 1 to 10 carbon atoms, and nn2 is an integer from 0 to 4}

唑基)苯及1,3,5-三(4,5-二氫-2-

唑基)苯。 The compound represented is 1,3-bis(4,5-dihydro-2-

Azolyl)benzene and 1,3,5-tris(4,5-dihydro-2-

Azolyl)benzene.

(B-2-9) Compound containing carbodiimide group

The carbodiimide group-containing compound is not particularly limited as long as it is a compound containing a carbodiimide group in the molecule. From the viewpoint of reliability after the HTS test, bis(2, 6-Diisopropylphenyl) carbodiimide, Carbodilite SV-02, V-01, V-02, V-03, V-04, V-05, V-07, V-09, E- 01, E-02, LA-1 (trade name, manufactured by Nisshinbo Chemical), etc.

(B-2-10) Allyl compound

The allyl compound is not particularly limited as long as it contains an allyl group in the molecule. Examples thereof include trimethylolpropane trimethacrylate, triallyl 1,3,5-benzenetricarboxylic acid, and partial Triallyl trimellitate, tetraallyl pyromellitic acid, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, ditrimethylol Hydroxymethylpropane tetraacrylate, NK Ester 1G, 2G, 3G, 4G, 9G, 14G, NPG, BPE-100, BPE-200, BPE-500, BPE-1400, A-200, A-400, A- 600, TMPT, A-TMM-3 (trade name, manufactured by Shinnakamura Chemical Industry Co., Ltd.), BANI-M, BANI-X (trade name, manufactured by Maruzen Petrochemical Co., Ltd.) Wait.

Among them, from the viewpoint of reliability after the HTS test, vinyl acetate, trimethylolpropane trimethacrylate, triallyl 1,3,5-benzenetricarboxylic acid, Triallyl trimellitate, tetraallyl pyromellitate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, two Trimethylolpropane tetraacrylate, BANIM and BANI-X.

硫醇化合物 (B-2-11)Three

Thiol compound

硫醇化合物，只要分子內含有三聚硫氰酸基，則並無特別限制，就HTS試驗後之可靠性之觀點而言，較佳為2,4,6-三硫醇-1,3,5-三

、2-二甲基胺基-4,6-二硫醇-1,3,5-三

、2-二丁基胺基-4,6-二硫醇-1,3,5-三

、2-苯基胺基-4,6-二硫醇-1,3,5-三

等。 As three

The thiol compound is not particularly limited as long as it contains a trimer thiocyanate group in the molecule. From the viewpoint of reliability after the HTS test, 2,4,6-trithiol-1,3, 5-Three

, 2-Dimethylamino-4,6-dithiol-1,3,5-tri

, 2-Dibutylamino-4,6-dithiol-1,3,5-tri

, 2-Phenylamino-4,6-dithiol-1,3,5-tri

Wait.

(B-2-12) Metal chelating compound

Examples of metal chelating compounds include aluminum chelating compounds, titanium chelating compounds, zirconium chelating compounds, chromium chelating compounds, magnesium chelating compounds, nickel chelating compounds, etc. From the viewpoint of reliability after the HTS test Preferably, they are aluminum (III) acetone, titanium (IV) acetone, chromium (III) acetone, magnesium (II) acetonate, nickel (II) acetone, Zirconium(IV) Acetate, Aluminum(III) Trifluoroacetone, Titanium(IV) Trifluoroacetone, Chromium(III) Trifluoroacetone, Magnesium(II) Trifluoroacetone ) Salt, nickel trifluoroacetone(II) salt, zirconium(IV) trifluoroacetone, diisopropoxy bis(acetylpyruvate) titanium, tetraacetyl pyruvate titanium, di-2- Ethylhexyloxybis(2-ethyl-3-hydroxyhexanol)titanium, diisopropoxybis(ethylacetate)titanium and the like.

Among these compounds, from the standpoint of reliability after the HTS test, preferred are aluminum (III) acetylacetonate, titanium (IV) acetylacetonate, zirconium (IV) acetylacetonate, and acetylacetone. Nickel(II) acetone, aluminum(III) trifluoroacetate, titanium(IV) trifluoroacetone, nickel trifluoroacetone (II) salt, trifluoroacetone zirconium (IV) salt, diisopropoxy bis (acetyl pyruvic acid) titanium, tetraacetyl pyruvate titanium, di-2-ethylhexyloxy bis (2- Ethyl-3-hydroxyhexanol)titanium and diisopropoxybis(ethylacetate)titanium are preferably aluminum acetone (III) from the viewpoint of adhesion to silicon wafer ) Salt, titanium (IV) acetylacetonate, zirconium (IV) acetylacetonate, aluminum (III) trifluoroacetone, titanium (IV) trifluoroacetone, zirconium trifluoroacetone ( IV) Salt, and diisopropoxy bis(acetylpyruvate) titanium.

環之化合物、(B-2-8)含

唑啉環之化合物、(B-2-10)烯丙基化合物，更佳為(B-2-1)含羥甲基及/或烷氧基甲基之化合物、(B-2-3)含異氰酸酯基之化合物、(B-2-4)含雙順丁烯二醯亞胺基之化合物、(B-2-6)含氧雜環丁烷環之化合物、(B-2-7)含苯并

環之化合物、(B-2-10)烯丙基化合物，最佳為(B-2-1)含羥甲基及/或烷氧基甲基之化合物。 Among the crosslinking agents described in (B-2-1)~(B-2-12), from the viewpoint of reliability after HTS test, it is preferable that (B-2-1) contains hydroxymethyl Group and/or alkoxymethyl compound, (B-2-2) oxirane compound, (B-2-3) isocyanate group-containing compound, (B-2-4) dimaleate-containing compound Diamido compound, (B-2-5) aldehyde group-containing compound, (B-2-6) oxetane ring-containing compound, (B-2-7) benzo-containing compound

Ring compound, (B-2-8) containing

Oxazoline ring compound, (B-2-10) allyl compound, more preferably (B-2-1) hydroxymethyl and/or alkoxymethyl-containing compound, (B-2-3) Compounds containing isocyanate groups, (B-2-4) compounds containing bismaleimide groups, (B-2-6) compounds containing oxetane ring, (B-2-7) Contains benzo

The ring compound, (B-2-10) allyl compound, the most preferred is (B-2-1) the compound containing hydroxymethyl and/or alkoxymethyl.

These crosslinking agents (B-2) can be used individually by 1 type or in combination of 2 or more types.

Among the above (B-2) crosslinking agents, the present invention preferably uses (B-2-1) a hydroxymethyl and/or alkoxymethyl-containing compound, and more preferably uses the following general formula ( 12): [化90]

{In the formula, Rs1 is a hydrogen atom, a univalent group selected from the group consisting of methyl, ethyl, n-propyl and isopropyl, and Rs2 is an alkyl group with 1-10 carbon atoms selected from a hydroxyl group , Alkoxy group with 1-10 carbon atoms, ester group with 1-10 carbon atoms, and urethane group, mm1 is an integer of 1 to 5, mm2 is 0-4 Of integers. Here, 1≦(mm1+mm2)≦5, nn1 is an integer of 1~4, V ₁ is CH ₂ ORs1 when nn1=1, single bond or 2~4 valence organic when nn1=2~4 base. When there are a plurality of CH ₂ ORs1 and R ₁₀ , these may be the same or different from each other. The hydroxymethyl compound and the alkoxymethyl compound represented by}.

By adding a crosslinking agent, the glass transition temperature of the resin under the same curing temperature can be increased. The glass transition temperature of the resin is increased to suppress the migration of copper into the resin.

Regarding the blending amount of the crosslinking agent (B-2), relative to 100 parts by mass of the resin (A), preferably 0.1-50 parts by mass, more preferably 1-30 parts by mass, and still more preferably 5-20 parts by mass .

(B-3) Fluorine-containing hydrophobic compound

The (B-3) fluorine-containing hydrophobic compound in this embodiment will be described in detail below. (B) The fluorine-containing hydrophobic compound is not particularly limited as long as it contains a fluorine atom in the molecule and has hydrophobicity.

Compounds that can be preferably used as the (B-3) fluorine-containing hydrophobic compound of this embodiment are acid fluoride, fluorinated acrylate, fluorinated methacrylate, fluorinated alcohol, and fluorinated alkane. , Fluorinated ester and fluorinated ether, etc.

<Alkyl Fluoride>

Regarding specific compound examples of the fluorine-containing hydrophobic compound (B-3), perfluoropentanyl fluoride, perfluorohexyl fluoride, perfluoroheptanyl fluoride, and perfluorooctyl fluoride can be preferably used. , Perfluorosuccinate fluoride, hexafluoroglutaric fluoride, octafluorohexamethylene fluoride, perfluoromethoxypropane fluoride, perfluorobutoxy ethoxy acetyl fluoride, perfluoropolyether dipropylene fluoride (n=1), perfluoropolyether dipropylene fluoride (n=2), perfluorohexanoic acid, perfluoroheptanoic acid, perfluorooctanoic acid, perfluorononanoic acid, perfluorodecanoic acid, perfluoroundecanoic acid, perfluoro Dodecanoic acid, perfluorotetradecanoic acid, perfluorohexadecanoic acid, perfluoro-3,5,5-trimethylhexanoic acid, perfluoro-3,7-dimethyloctanoic acid, perfluorosuccinic acid, perfluoro Glutaric acid, perfluoroadipic acid, perfluorosuccinic acid, perfluoroazelaic acid, perfluorosebacic acid, perfluorododecanedioic acid, perfluoro-3,6-dioxaheptanoic acid, all Fluoro-3,6,9-trioxadecanoic acid, perfluoro-3,6-dioxadecanoic acid, perfluoro-3,6,9-trioxatridecanoic acid, perfluoro-3,6- Dioxaoctane-1,8-dioic acid, perfluoro-3,6,9-trioxaundecane-1,11-dioic acid, etc.

<Fluorinated Acrylate>

Regarding specific compound examples of the fluorinated acrylate as the fluorine-containing hydrophobic compound (B-3), 1H,1H-perfluoro-n-butyl acrylate, 1H,1H-perfluoro-n-octyl acrylate, Acrylic acid 1H,1H-perfluoro-n-decyl ester, 1H,1H,6H,6H-perfluoro-1,6-hexanediol diacrylate, 1H,1H,8H,8H-perfluorotetraethylene glycol diacrylate , 1H,1H,6H,6H-perfluorotriethylene glycol diacrylate, 1H,1H,4H,4H-perfluorodiethylene glycol diacrylate, 1H,1H,10H,10H-pentaethylene glycol two Acrylate, 1H, 1H, 18H, 18H-nonaethylene glycol diacrylate, perfluoro-1,6-hexanediol diacrylate, perfluorotetraethylene glycol diacrylate, perfluorotriethylene glycol diacrylate Acrylate, perfluorodiethylene glycol diacrylate, pentaethylene glycol diacrylate, nonaethylene glycol diacrylate, etc. Among them, 1H,1H,6H,6H-perfluoro-1,6-hexanediol diacrylate and 1H,1H,8H,8H-perfluorotetraethylene glycol diacrylate can be used particularly preferably as It is obtained by the product name C6DIACRY and the product name DA-F4EO manufactured by Exfluor.

<Fluorinated Methacrylate>

Regarding specific compound examples of the fluorinated methacrylate as the fluorine-containing hydrophobic compound (B-3), 1H,1H-perfluoro-n-butyl methacrylate and 1H,1H-methacrylate are preferably used. Perfluoro-n-octyl ester, 1H, 1H-perfluoro-n-decyl methacrylate, 1H, 1H, 6H, 6H-perfluoro-1,6-hexanediol dimethacrylate, 1H, 1H, 8H, 8H -Perfluorotetraethylene glycol dimethacrylate, 1H,1H,6H,6H-perfluorotriethylene glycol dimethacrylate, 1H,1H,4H,4H-perfluorodiethylene glycol dimethyl Acrylate, 1H,1H,10H,10H-pentaethylene glycol dimethacrylate, 1H,1H,18H,18H-nonaethylene glycol dimethacrylate, perfluoro-1,6-hexanediol two Methacrylate, perfluorotetraethylene glycol dimethacrylate, perfluorotriethylene glycol dimethacrylate, perfluorodiethylene glycol dimethacrylate, pentaethylene glycol dimethacrylate , Nonaethylene glycol dimethacrylate, etc.

<Fluorinated Alcohol>

Regarding specific compound examples of fluorinated alcohols as (B-3) fluorine-containing hydrophobic compounds, 1H,1H-perfluoro-1-hexanol and 1H,1H-perfluoro-1-heptanol can be preferably used , 1H,1H-perfluoro-1-octanol, 1H,1H-perfluoro-1-nonanol, 1H,1H-perfluoro-1-decanol, 1H,1H-perfluoro-1-undecyl alcohol, 1H,1H-perfluoro-1-dodecanol, 1H,1H-perfluoro-1-tetradecanol, 1H,1H-perfluoro-1-hexadecanol, perfluoro-3,5,5-trimethyl Hexane-1-ol, perfluoro-3,7-dimethyloctane-1-ol, 1H,1H,4H,4H-perfluoro-1,4-butanediol, 1H,1H,5H, 5H-perfluoro-1,5-pentanediol, 1H,1H,5H,5H-perfluoro-1,5-pentanediol, 1H,1H,6H,6H-perfluoro-1,6-hexanediol , 1H,1H,8H,8H-perfluoro-1,8-octanediol, 1H,1H,9H,9H-perfluoro-1,9-nonanediol, 1H,1H,10H,10H-perfluoro- 1,10-decanediol, 1H,1H,12H,12H-perfluoro-1,12-dodecanediol, perfluoro-tert-butanol, fluorinated diethylene glycol monomethyl ether, trifluoride Ethylene glycol monomethyl ether, fluorinated diethylene glycol monobutyl ether, fluorinated triethylene glycol monobutyl ether, fluorinated triethylene glycol, fluorinated tetraethylene glycol, etc.

<Fluorinated Alkanes>

Regarding specific compound examples of fluorinated alkanes as (B-3) fluorine-containing hydrophobic compounds, perfluoroheptane, perfluorooctane, perfluorononane, perfluorotridecane, and perfluoro Pentadecane, 1H-perfluoropentane, 1H-perfluorohexane, 1H-perfluoroheptane, 1H-perfluorooctane, 1H-perfluorononane, 1H-perfluorodecane, 1H-perfluoro Undecane, 1H-perfluorotridecane, 1H-perfluoropentadecane, 1H-perfluoro-2,4,4-trimethylpentane, 1H-perfluoro-2,6-dimethylheptane Alkanes, 1H,4H-perfluorobutane, 1H,6H-perfluorohexane, 1H,7H-perfluoroheptane, 1H,8H-perfluorooctane, 1H,10H-perfluorodecane, etc.

<Fluorinated Ester>

Regarding specific compound examples of fluorinated esters as (B-3) fluorine-containing hydrophobic compounds, methyl perfluorovalerate, methyl perfluorohexanoate, methyl perfluoroheptanoate, methyl perfluorooctanoate can be preferably used. Ester, methyl perfluorononanoate, methyl perfluorodecanoate, methyl perfluoroundecanoate, methyl perfluorododecanoate, methyl perfluoromyristate, methyl perfluorohexadecanoate, perfluoromethyl Dimethyl succinate, dimethyl perfluoroglutarate, dimethyl perfluoroadipate, dimethyl perfluorosuccinate, dimethyl perfluoroazelaate, dimethyl perfluorosebacate , Perfluoro-1,12-dimethyl sebacate, perfluoro-3,6-dioxaheptanoate methyl, perfluoro-3,6,9-trioxadecanoic acid methyl ester, perfluoro- Methyl 3,6-dioxadecanoate, methyl perfluoro-3,6,9-trioxatridecanoate, perfluoro-3,6-dioxaoctane-1,8-dioic acid Methyl ester, perfluoro-3,6,9-trioxaundecane-1,11-dioic acid dimethyl ester, etc.

<Fluorinated Ether>

Regarding specific compound examples of fluorinated ethers as (B-3) fluorine-containing hydrophobic compounds, perfluoro(diethylene glycol dimethyl ether) and perfluoro(triethylene glycol dimethyl ether) can be preferably used , Perfluoro (triethylene glycol dimethyl ether), etc.

(B-3) The weight ratio of the fluorine atoms in the molecule of the fluorine-containing hydrophobic compound is preferably 30% by mass or more and 80% by mass or less. If the weight ratio of fluorine is less than this range, sufficient Hydrophobicity. Moreover, if fluorine is more than this range, the compatibility with a solvent will fall, and it will become difficult to obtain the coating film with uniform surface flatness, and it is unsatisfactory. The range of the fluorine weight content ratio is more preferably 35% by mass or more and within 75% by mass.

The (B-3) fluorine-containing hydrophobic compound in this embodiment preferably has at least one unsaturated double bond in the molecule. If it has an unsaturated double bond, in the exposure step, a crosslinking reaction occurs between the molecules of (B-3) the fluorine-containing hydrophobic compound and between the molecules of the resin (A). Thereby, (B-3) the fluorine-containing hydrophobic compound is not easily volatilized during the heat treatment, and can exhibit sufficient hydrophobic effect. Preferable examples of unsaturated double bonds are acrylate and methacrylate.

Regarding the content of (B-3) the fluorine-containing hydrophobic compound, relative to 100 parts by mass of the resin (A), it is preferably 0.01-50 parts by mass, more preferably 0.02-30 parts by mass, and still more preferably 0.05-20 parts by mass Copies. If the content is more than this range, the compatibility with the solvent is reduced, and it is difficult to obtain a coating film with uniform surface flatness. Therefore, it is not good. If the content is less than this range, sufficient hydrophobic effect cannot be obtained. Easy to produce gaps between.

(C) Sensitizer

唑前驅物、可溶性聚醯亞胺、酚醛清漆、聚羥基苯乙烯及酚樹脂之至少一種作為(A)樹脂之正型等而不同。 The (C) photosensitizer used in the present invention will be described. (C) Sensitizer The photosensitive resin composition according to the present invention is, for example, a negative type that mainly uses polyimide precursors and/or polyamides as the (A) resin, or is, for example, mainly uses polyimide

At least one of the azole precursor, soluble polyimide, novolac, polyhydroxystyrene, and phenol resin is different as the positive type of (A) resin.

About the compounding quantity of (C) photosensitive agent in the photosensitive resin composition, it is 1-50 mass parts with respect to 100 mass parts of (A) photosensitive resin. The above-mentioned blending amount is 1 part by mass or more from the viewpoint of photosensitivity and patterning properties, and is 50 parts by mass or less from the viewpoint of the curability of the photosensitive resin composition or the physical properties of the photosensitive resin layer after curing.

[(C) Negative sensitizer: polymerization initiator, photoacid generator]

、2-甲基9-氧硫

、2-異丙基9-氧硫

、二乙基9-氧硫

等9-氧硫

衍生物，苯偶醯、苯偶醯二甲基縮酮、苯偶醯-β-甲氧基乙基縮醛等苯偶醯衍生物， First, the case where the expectation is negative will be explained. In this case, a photopolymerization initiator and/or a photoacid generator are used as the (C) sensitizer. As the photopolymerization initiator, a photoradical polymerization initiator is preferred, preferably, diphenyl Benzophenone derivatives such as methyl ketone, methyl phthalate benzoate, 4-benzyl-4'-methyl benzophenone, dibenzyl ketone, quinone, 2,2'-di Acetophenone derivatives such as ethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenylketone, 9-oxysulfur

, 2-Methyl 9-oxysulfur

, 2-isopropyl 9-oxysulfur

, Diethyl 9-oxysulfur

9-oxysulfur

Derivatives, benzyl derivatives, benzyl dimethyl ketal, benzyl-β-methoxyethyl acetal, etc.,

Benzoin, benzoin methyl ether and other benzoin derivatives, 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2- (O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o Benzoyl)oxime, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxypropanetrione-2-(o-benzyl)oxime Oxime such as oxime, N-arylglycine such as N-phenylglycine, peroxides such as benzyl perchloride, aromatic biimidazole, titanocene, α-( Photoacid generators, such as n-octylsulfonyloxyimino)-4-methoxybenzyl cyanide, etc., are not limited to these. Among the above-mentioned photopolymerization initiators, particularly in terms of photosensitivity, oximes are more preferred.

In the case of using a photoacid generator as the (C) photosensitizer in a negative photosensitive resin composition, it becomes acidic under the irradiation of active light such as ultraviolet rays, and has the following effects due to this effect The linking agent and the resin as the component (A) are crosslinked, or the crosslinking agent is polymerized with each other. As an example of the photoacid generator, diarylsulfonium salt, triarylsulfonium salt, dialkylbenzylmethylsulfonate, diaryliodonium salt, aryldiazonium salt, and aromatic tetracarboxylic acid can be used. Acid esters, aromatic sulfonates, nitrobenzyl esters, oxime sulfonates, aromatic N-oxyimide sulfonates, aromatic sulfonamides, halogenated alkyl-containing hydrocarbon compounds, halogen-containing Alkyl heterocyclic compound, naphthoquinone diazide -4-sulfonate etc. Such compounds can be used in combination of two or more types or in combination with other sensitizers as necessary. Among the aforementioned photoacid generators, particularly in terms of photosensitivity, aromatic oxime sulfonate and aromatic N-oxyamidosulfonate are more preferred.

Regarding the blending amount of the photosensitive agents in the case of a negative type, it is 1-50 parts by mass relative to 100 parts by mass of the (A) resin, and preferably 2-15 parts by mass from the viewpoint of photosensitivity characteristics. The (C) photosensitizer is prepared in an amount of 1 part by mass or more with respect to 100 parts by mass of the (A) resin, and the light sensitivity is excellent, and the thick film hardenability is excellent in the preparation of 50 parts by mass or less.

Furthermore, as described above, when the (A) resin represented by the general formula (1) is an ionic bond type, in order to impart a photopolymerizable group to the side chain of the (A) resin via the ionic bond, an amino group is used (Meth) acrylic compound. In this case, the (meth)acrylic compound having an amino group is used as the (C) sensitizer. As described above, for example, dimethylaminoethyl acrylate and dimethylaminoethyl methacrylate are preferred. , Diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, diethylaminopropyl acrylate, diethyl methacrylate Aminopropyl, dimethylaminobutyl acrylate, dimethylaminobutyl methacrylate, diethylaminobutyl acrylate, diethylaminobutyl methacrylate and other dialkylaminoalkyl acrylates Or dialkylaminoalkyl methacrylate, among them, from the viewpoint of photosensitive properties, it is preferable that the carbon number of the alkyl group on the amino group is 1-10, and the carbon number of the alkyl chain is 1-10 Dialkylaminoalkyl acrylate or dialkylaminoalkyl methacrylate.

Regarding the compounding amount of the (meth)acrylic compound having an amine group, it is 1-20 parts by mass relative to 100 parts by mass of the (A) resin, and from the viewpoint of photosensitivity characteristics, it is preferably 2-15 parts by mass Copies. By blending 1 part by mass or more of (meth)acrylic compound having an amino group with respect to 100 parts by mass of (A) resin as (C) photosensitizer, the light sensitivity is excellent. By blending 20 parts by mass or less, thick film Excellent curability.

Next, the case where the expectation is positive is explained. In this case, a photoacid generator is used as the (C) sensitizer. Specifically, a diazoquinone compound, an onium salt, a halogen-containing compound, etc. can be used. From the viewpoint of solvent solubility and storage stability, It is preferably a compound having a quinone diazide structure.

[(C) Positive sensitizer: compound with quinonediazide group]

As (C) a compound having a quinonediazide group (hereinafter also referred to as "(C)quinonediazide compound"), a compound having a 1,2-benzoquinonediazide structure, and a compound having 1,2- -The compound of the naphthoquinone diazide structure is a known substance in the specification of US Patent No. 2,772,972, US Patent No. 2,797,213, and US Patent No. 3,669,658. The (C) quinonediazide compound is preferably selected from 1,2-naphthoquinonediazide-4-sulfonate of a polyhydroxy compound with a specific structure described in detail below, and the polyhydroxy compound 1, At least one compound in the group consisting of 2-naphthoquinonediazide-5-sulfonate (hereinafter also referred to as "NQD compound").

烷、丙酮或四氫呋喃等溶劑中，於三乙胺等鹼性觸媒之存在下反應而進行酯化，將所獲得之產物水洗並加以乾燥。 The NQD compound is obtained by the following method: according to the conventional method, the naphthoquinone diazide sulfonic acid compound is sulfonated with chlorosulfonic acid or sulfite chloride to make the obtained naphthoquinone diazide sulfonyl chloride Condensation reaction with polyhydroxy compound. For example, it can be obtained by combining a polyhydroxy compound with a specific amount of 1,2-naphthoquinonediazide-5-sulfonyl chloride or 1,2-naphthoquinonediazide-4-sulfonyl chloride in two

In a solvent such as alkane, acetone or tetrahydrofuran, it is reacted in the presence of a basic catalyst such as triethylamine for esterification, and the obtained product is washed with water and dried.

In this embodiment, from the viewpoint of sensitivity and resolution when forming a resist pattern, (C) the compound having a quinonediazide group is preferably represented by the following general formulas (70) to (74) Hydroxy compound 1,2-naphthoquinone diazide-4-sulfonate and/or 1,2-naphthoquinone diazide-5-sulfonate.

The general formula (70) is derived from [化91]

{In the formula, X ₁₁ and X ₁₂ each independently represent a hydrogen atom or a monovalent organic group with a carbon number of 1 to 60 (preferably carbon number 1 to 30), and X ₁₃ and X ₁₄ each independently represent a hydrogen atom or a carbon number A monovalent organic group of 1 to 60 (preferably carbon number 1 to 30), r1, r2, r3, and r4 are each independently an integer of 0 to 5, and at least one of r3 and r4 is an integer of 1 to 5. (r1+r3)≦5, and (r2+r4)≦5}.

The general formula (71) is given by

{In the formula, Z represents a tetravalent organic group with 1 to 20 carbons, X ₁₅ , X ₁₆ , X ₁₇ and X ₁₈ each independently represent a monovalent organic group with 1 to 30 carbons, and r6 is 0 or 1. Integers, r5, r7, r8, and r9 are independently integers from 0 to 3, r10, r11, r12, and r13 are independently integers from 0 to 2, and r10, r11, r12, and r13 are not all represented by 0} .

And the general formula (72) is given by

{In the formula, r14 represents an integer from 1 to 5, r15 represents an integer from 3 to 8, (r14×r15) each independently represents a monovalent organic group with 1 to 20 carbon atoms, and (r15) T ¹ And (r15) T ² each independently represents a hydrogen atom or a monovalent organic group with 1 to 20 carbon atoms}.

And the general formula (73) is given by

{In the formula, A represents an aliphatic divalent organic group containing tertiary or quaternary carbon, and M represents a divalent organic group, preferably selected from the following chemical formulas: [化95]

Among the three bases indicated, the base of 2 valence} is expressed.

Furthermore, the general formula (74) is given by

{In the formula, r17, r18, r19, and r20 are each independently an integer from 0 to 2, at least one of r17, r18, r19, and r20 is 1 or 2, and X ₂₀ to X ₂₉ each independently represent a hydrogen atom, a halogen atom, A monovalent group selected from the group consisting of alkyl, alkenyl, alkoxy, allyl and acyl groups, and Y ₁₀ , Y ₁₁ and Y ₁₂ each independently represent a single bond, selected from -O-, -S-, -SO-, -SO ₂ -, -CO-, -CO ₂ -, cyclopentylene, cyclohexylene, phenylene, and a divalent organic group with 1 to 20 carbons The base of the price of 2 in the group}.

In another embodiment, in the above general formula (74), Y ₁₀ to Y _{12 are} preferably independently derived from the following general formula: [化97]

{In the formula, X ₃₀ and X ₃₁ each independently represent a hydrogen atom, at least one monovalent group selected from the group consisting of an alkyl group, an alkenyl group, an aryl group, and a substituted aryl group, X ₃₂ , X ₃₃ , X ₃₄ and X ₃₅ each independently represent a hydrogen atom or an alkyl group, r21 is an integer of 1 to 5, and X ₃₆ , X ₃₇ , X ₃₈ and X ₃₉ each independently represent a hydrogen atom or an alkyl group}

Choose from the three divalent organic groups indicated.

As the compound represented by the above general formula (70), the following formulae (75) to (79) can be cited The hydroxy compound.

Here, the general formula (75) is

{Wherein, R16 are each independently integers of 0 to 2 of, and X ₄₀ each independently represent a hydrogen atom or a C 1 to 20. The monovalent The organic group, when in X ₄₀ there is a case a plurality, the plurality of X ₄₀ each It may be the same or different, and X _{40 is} preferably the following general formula:

(In the formula, r18 is an integer from 0 to 2, X ₄₁ represents a hydrogen atom, a monovalent organic group selected from the group consisting of alkyl and cycloalkyl, and when r18 is 2, two Xs ₄₁ can be the same or different from each other)

The monovalent organic group represented by }, the general formula (76) is given by

{In the formula, X ₄₂ represents a hydrogen atom, a monovalent organic selected from the group consisting of an alkyl group with 1 to 20 carbons, an alkoxy group with 1 to 20 carbons, and a cycloalkyl group with 1 to 20 carbons基} indicated.

Also, the general formula (77) is

{In the formula, r19 is independently an integer from 0 to 2, and X ₄₃ independently represents a hydrogen atom or the following general formula:

(In the formula, r20 is an integer from 0 to 2, and X _{45 is} selected from the group consisting of a hydrogen atom, an alkyl group and a cycloalkyl group, and when r20 is 2, two X ₄₅ may be the same or different. ) Represents a monovalent organic group, and X _{44 is} selected from the group consisting of a hydrogen atom, an alkyl group with 1 to 20 carbons, and a cycloalkyl group with 1 to 20 carbons}, formulas (78) and ( 79) is the following structure.

The compound represented by the general formula (70) is preferably the following formula (80) in terms of its high sensitivity when it is made into an NQD compound and low precipitation in the photosensitive resin composition ~(82) The hydroxy compound represented by.

The structure of formula (80)~(82) is shown below.

[化108]

The compound represented by the above general formula (76) is preferably the following formula (83) in terms of its high sensitivity when it is made into an NQD compound and low precipitation in the photosensitive resin composition :

The hydroxy compound represented.

As the compound represented by the above general formula (77), the following formula (84) is preferable in terms of high sensitivity when it is made into an NQD compound and low precipitation in the photosensitive resin composition ~(86) The hydroxy compound represented by.

The structure of formula (84)~(86) is shown below.

[化112]

In the above general formula (71), Z is not particularly limited as long as it is a tetravalent organic group with 1 to 20 carbon atoms. From the viewpoint of sensitivity, it preferably has the following formula:

The 4 valence base of the structure shown.

Among the compounds represented by the above general formula (71), the following formula (87) is preferable in terms of the high sensitivity when the NQD compound is formed and the low precipitation in the photosensitive resin composition )~(90) represents the hydroxyl compound.

The structure of formulas (87)~(90) is shown below.

[化117]

As the compound represented by the above general formula (72), the following formula (91) is preferred in terms of high sensitivity when it is made into an NQD compound and low precipitation in the photosensitive resin composition : [化119]

{Where, r40 is each independently an integer of 0-9} represents a hydroxyl compound.

As the compound represented by the above general formula (73), the following formula (92) is preferred in terms of high sensitivity when it is made into an NQD compound and low precipitation in the photosensitive resin composition And the hydroxy compound represented by (93).

The structures of formulas (92) and (93) are shown below.

[化121]

As the compound represented by the general formula (74), in terms of high sensitivity and low precipitation in the photosensitive resin composition, the following formula (94) is particularly preferred:

The NQD product of the polyhydroxy compound shown.

When (C) the compound having a quinonediazide group has a 1,2-naphthoquinonediazide sulfonyl group, the group may be 1,2-naphthoquinonediazide-5-sulfonyl group or 1 , Any of 2-naphthoquinonediazide-4-sulfonyl. 1,2-Naphthoquinonediazide-4-sulfonyl can absorb the i-ray region of mercury lamps, so it is suitable for exposure by i-ray. On the other hand, 1,2-naphthoquinonediazide-5-sulfonyl can even absorb the g-ray region of mercury lamps, so it is suitable for exposure by g-ray.

In this embodiment, it is preferable to select one of the 1,2-naphthoquinonediazide-4-sulfonate compound and 1,2-naphthoquinonediazide-5-sulfonate compound according to the wavelength of exposure Or both. In addition, 1,2-naphthoquinonediazide having 1,2-naphthoquinonediazide-4-sulfonyl and 1,2-naphthoquinonediazide-5-sulfonyl in the same molecule can also be used Nitrogen sulfonate compounds, and 1,2-naphthoquinone diazide-4-sulfonic acid esterification The compound is mixed with 1,2-naphthoquinone diazide-5-sulfonate compound for use.

(C) Among the compounds having a quinonediazide group, from the viewpoint of development contrast, the average esterification rate of the naphthoquinonediazidesulfonyl ester of the hydroxyl compound is preferably 10% to 100%, and more preferably It is 20%~100%.

From the viewpoint of the physical properties of the cured film such as sensitivity and elongation, preferred examples of NQD compounds include those represented by the following general formula groups.

It can be enumerated {where Q is a hydrogen atom, or the following group of formulas:

The naphthoquinone diazide sulfonate group represented by any one of them, but not all Q are represented by hydrogen atoms at the same time.

In this case, as an NQD compound, it can be used in a naphthoquinonediazidesulfonyl ester compound having 4-naphthoquinonediazidesulfonyl group and 5-naphthoquinonediazidesulfonyl group in the same molecule. The 4-naphthoquinone diazide sulfonyl ester compound and the 5-naphthoquinone diazide sulfonyl ester compound can be mixed and used.

Among the naphthoquinone diazide sulfonate groups described in the above paragraph [0243], the following general formula (95) is particularly preferred:

Represented by.

Examples of the onium salt include: phosphonium salt, sulfonium salt, phosphonium salt, ammonium salt, and diazonium salt, etc., preferably selected from the group consisting of diarylsulfonium salt, triarylsulfonium salt and trialkylsulfonium salt Onium salt in the group.

。 Examples of the halogen-containing compounds include halogenated alkyl-containing hydrocarbon compounds, etc., preferably trichloromethyl tri

.

Regarding the blending amount of the photoacid generators in the case of the positive type, it is 1-50 parts by mass, preferably 5-30 parts by mass relative to 100 parts by mass of the (A) resin. If the blending amount of the photoacid generator as the photosensitizer is 1 part by mass or more, the patternability of the photosensitive resin composition is good, and if it is 50 parts by mass or less, the photosensitive resin composition will be cured The tensile elongation of the film is good, and the development residue (scum) of the exposed part is less.

The above-mentioned NQD compounds may be used alone, or two or more of them may be mixed and used.

In this embodiment, the compounding amount of (C) the compound having a quinonediazide group in the photosensitive resin composition is 0.1 to 70 parts by mass relative to 100 parts by mass of the (A) resin, and preferably 1 part by mass to 40 parts by mass, more preferably 3 parts by mass to 30 parts by mass, and still more preferably 5 parts by mass to 30 parts by mass. If the compounding amount is 0.1 parts by mass or more, good sensitivity is obtained, and if it is 70 parts by mass or less, the mechanical properties of the cured film are good.

唑前驅物、可溶性聚醯亞胺及酚樹脂等之正型等而不同。 The photosensitive resin composition of the present invention may further contain components other than the above-mentioned (A) to (C) components. The preferred one is based on (A) resin, such as the use of polyimide precursors and polyamides, etc., or the use of polyimide

The azole precursor, soluble polyimide, phenol resin, etc. are different.

唑樹脂組合物、可溶性聚醯亞胺樹脂組合物及酚樹脂組合物中可包含用以使該等樹脂溶解之溶劑。 The above-mentioned polyimide precursor resin composition and polyimide resin composition as the negative resin composition in this embodiment, or the polyimide resin composition as the positive photosensitive resin composition

The azole resin composition, the soluble polyimide resin composition, and the phenol resin composition may include a solvent for dissolving these resins.

<Solvent>

啉、二氯甲烷、1,2-二氯乙烷、1,4-二氯丁烷、氯苯、鄰二氯苯、苯甲醚、己烷、庚烷、苯、甲苯、二甲苯、均三甲苯等。其中，就樹脂之溶解性、樹脂組合物之穩定性、及對基板之接著性之觀點而言，較佳為N-甲基-2-吡咯啶酮、二甲基亞碸、四甲基脲、乙酸丁酯、乳酸乙酯、γ-丁內酯、丙二醇單甲醚乙酸酯、丙二醇單甲醚、二乙二醇二甲醚、苄醇、苯乙二醇及四氫呋喃甲醇。 Examples of solvents include amides, sulfides, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, alcohols, etc., for example, N-methyl-2 can be used -Pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfide, tetramethylurea, acetone, methyl ethyl ketone, methyl isobutyl Ketone, cyclopentanone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethyl lactate, methyl lactate, butyl lactate, γ-butyrolactone, propylene glycol monomethyl ether Acetate, propylene glycol monomethyl ether, benzyl alcohol, phenyl glycol, tetrahydrofuran methanol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran,

Morpholine, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane, benzene, toluene, xylene, homogeneous Trimethylbenzene and so on. Among them, from the viewpoints of the solubility of the resin, the stability of the resin composition, and the adhesion to the substrate, N-methyl-2-pyrrolidone, dimethylsulfene, and tetramethylurea are preferred , Butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol dimethyl ether, benzyl alcohol, phenyl glycol and tetrahydrofuran methanol.

Among such solvents, those that can completely dissolve the resulting polymer are particularly preferred. Examples include: N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethyl Methamide, dimethyl sulfide, tetramethylurea, γ-butyrolactone, etc.

Examples of solvents suitable for the above phenol resin include: bis(2-methoxyethyl) ether, methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, di Ethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, cyclohexanone, cyclopentanone, toluene, xylene, γ-butyrolactone, N-methyl-2-pyrrolidone, etc., but not limited to these Wait.

In the photosensitive resin composition of the present invention, the amount of solvent used is preferably 100 to 1000 parts by mass, more preferably 120 to 700 parts by mass, and still more preferably 125 to 100 parts by mass of (A) resin. The range of 500 parts by mass.

The photosensitive resin composition of the present invention may further contain components other than the above-mentioned (A) to (C) components.

For example, when the photosensitive resin composition of the present invention is used to form a cured film on a substrate containing copper or copper alloy, in order to suppress discoloration on the copper, nitrogen-containing heterocycles such as azole compounds and purine derivatives can be optionally formulated Compound.

Examples of azole compounds include: 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl -1H-triazole, 4-tert-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5- Phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-di Ethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α -Dimethylbenzyl)phenyl)-benzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-tert-butyl- 5-Methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-tert-pentyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5 '-Third octyl phenyl) benzotriazole, hydroxyphenyl benzotriazole, tolutriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole , 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5- Amino-1H-tetrazole, 1-methyl-1H-tetrazole, etc.

Particularly preferred examples are: tolyltriazole, 5-methyl-1H-benzotriazole and 4-methyl-1H-benzotriazole. In addition, these azole compounds can be used singly or as a mixture of two or more.

Specific examples of purine derivatives include: purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyl Base adenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine, 9-( 2-hydroxyethyl) adenine, guanine oxime, N-(2-hydroxyethyl) adenine, 8-amino adenine, 6-amino-8-phenyl-9H-purine, 1-ethyl Adenine, 6-ethylaminopurine, 1-benzyl adenine, N-methylguanine, 7-(2-hydroxy Ethyl)guanine, N-(3-chlorophenyl)guanine, N-(3-ethylphenyl)guanine, 2-azaadenine, 5-azaadenine, 8-azaadenine Adenine, 8-azaguanine, 8-azapurine, 8-azaxanthine, 8-azahypoxanthine, etc. and their derivatives.

Regarding the compounding amount when the photosensitive resin composition contains the above-mentioned azole compound or purine derivative, it is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the (A) resin. From the viewpoint of photosensitivity characteristics, More preferably, it is 0.5 to 5 parts by mass. If the compounding amount of the azole compound relative to 100 parts by mass of the resin (A) is 0.1 parts by mass or more, when the photosensitive resin composition of the present invention is formed on copper or copper alloy, the surface of copper or copper alloy is suppressed Discoloration, on the other hand, when it is 20 parts by mass or less, the photosensitivity is excellent.

-2,4,6-(1H,3H,5H)-三酮、1,3,5-三(4-第三丁基-3-羥基-2,6-二甲基苄基)- 1,3,5-三

-2,4,6-(1H,3H,5H)-三酮、1,3,5-三(4-第二丁基-3-羥基-2,6-二甲基苄基)-1,3,5-三

-2,4,6-(1H,3H,5H)-三酮、1,3,5-三[4-(1-乙基丙基)-3-羥基-2,6-二甲基苄基]-1,3,5-三

-2,4,6-(1H,3H,5H)-三酮、1,3,5-三[4-三乙基甲基-3-羥基-2,6-二甲基苄基]-1,3,5-三

-2,4,6-(1H,3H,5H)-三酮、1,3,5-三(3-羥基-2,6-二甲基-4-苯基苄基)-1,3,5-三

-2,4,6-(1H,3H,5H)-三酮、1,3,5-三(4-第三丁基-3-羥基-2,5,6-三甲基苄基)-1,3,5-三

-2,4,6-(1H,3H,5H)-三酮、1,3,5-三(4-第三丁基-5-乙基-3-羥基-2,6-二甲基苄基)-1,3,5-三

-2,4,6-(1H,3H,5H)-三酮、1,3,5-三(4-第三丁基-6-乙基-3-羥基-2-甲基苄基)-1,3,5-三

-2,4,6-(1H,3H,5H)-三酮、1,3,5-三(4-第三丁基-6-乙基-3-羥基-2,5-二甲基苄基)-1,3,5-三

-2,4,6-(1H,3H,5H)-三酮、1,3,5-三(4-第三丁基-5,6-二乙基-3-羥基-2-甲基苄基)-1,3,5-三

-2,4,6-(1H,3H,5H)-三酮、1,3,5-三(4-第三丁基-3-羥基-2-甲基苄基)-1,3,5-三

-2,4,6-(1H,3H,5H)-三酮、1,3,5-三(4-第三丁基-3-羥基-2,5-二甲基苄基)-1,3,5-三

-2,4,6-(1H,3H,5H)-三酮、1,3,5-三(4-第三丁基-5-乙基-3-羥基-2-甲基苄基)-1,3,5-三

-2,4,6-(1H,3H,5H)-三酮等，但並不限定於此。該等之中，尤佳為1,3,5-三(4-第三丁基-3-羥基-2,6-二甲基苄基)-1,3,5-三

-2,4,6-(1H,3H,5H)-三酮等。 In addition, in order to suppress discoloration on the copper surface, a hindered phenol compound can be optionally blended. Examples of hindered phenol compounds include 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-butyl-hydroquinone, and 3-(3,5-di-tert-butyl- 4-hydroxyphenyl) stearyl propionate, 3-(3,5-di-tert-butyl-4-hydroxyphenyl) isooctyl propionate, 4,4'-methylenebis(2 ,6-Di-tert-butylphenol), 4,4'-thio-bis(3-methyl-6-tert-butylphenol), 4,4'-butylene-bis(3-methyl- 6-tert-butylphenol), triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol- Bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylene bis[3-(3,5-di-tert-butyl) 4-hydroxyphenyl) propionate), N,N'-hexamethylene bis(3,5-di-tert-butyl-4-hydroxy-phenylpropionamide), 2,2'- Methyl-bis(4-methyl-6-tertiary butylphenol), 2,2'-methylene-bis(4-ethyl-6-tertiary butylphenol), tetrakis[3-(3 ,5-Di-tert-butyl-4-hydroxyphenyl)propionic acid) pentaerythritol ester, tris-(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5 -Trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl -4-isopropylbenzyl)-1,3,5-tri

-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tertiarybutyl-3-hydroxy-2,6-dimethylbenzyl)-1, 3,5-Three

-2,4,6-(1H,3H,5H)-triketone, 1,3,5-tris(4-secondbutyl-3-hydroxy-2,6-dimethylbenzyl)-1, 3,5-Three

-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl ]-1,3,5-Three

-2,4,6-(1H,3H,5H)-triketone, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1 ,3,5-three

-2,4,6-(1H,3H,5H)-triketone, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3, 5-Three

-2,4,6-(1H,3H,5H)-triketone, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,5,6-trimethylbenzyl)- 1,3,5-Three

-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tertiarybutyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl Base) -1,3,5-three

-2,4,6-(1H,3H,5H)-triketone, 1,3,5-tris(4-tert-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)- 1,3,5-Three

-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tertiarybutyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl Base) -1,3,5-three

-2,4,6-(1H,3H,5H)-triketone, 1,3,5-tris(4-tertiarybutyl-5,6-diethyl-3-hydroxy-2-methylbenzyl Base) -1,3,5-three

-2,4,6-(1H,3H,5H)-triketone, 1,3,5-tris(4-tert-butyl-3-hydroxy-2-methylbenzyl)-1,3,5 -three

-2,4,6-(1H,3H,5H)-triketone, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,5-dimethylbenzyl)-1, 3,5-Three

-2,4,6-(1H,3H,5H)-triketone, 1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)- 1,3,5-Three

-2,4,6-(1H,3H,5H)-trione, etc., but not limited to this. Among these, 1,3,5-tris(4-tertiarybutyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris

-2,4,6-(1H,3H,5H)-triketone etc.

The compounding amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the (A) resin, and more preferably 0.5 to 10 parts by mass from the viewpoint of photosensitivity characteristics. If the compounding amount of the hindered phenol compound relative to 100 parts by mass of the resin (A) is 0.1 parts by mass or more, for example, when the photosensitive resin composition of the present invention is formed on copper or copper alloy, the production of copper or copper alloy is prevented Discoloration or corrosion, on the other hand, if it is 20 parts by mass or less, the photosensitivity is excellent.

The photosensitive resin composition of this invention may contain a crosslinking agent. The crosslinking agent may be a crosslinking agent that can crosslink (A) the resin when the embossed pattern formed using the photosensitive resin composition of the present invention is heat-cured, or the crosslinking agent itself can form a crosslinked network structure Agent. The crosslinking agent can further strengthen the heat resistance and chemical resistance of the cured film formed from the photosensitive resin composition.

As the crosslinking agent, for example, Cymel (registered trademark) 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, which are compounds containing hydroxymethyl and/or alkoxymethyl groups, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR 65, 300, Micoat 102, 105 (the above are made by Mitsui Cytec); NIKALAC (registered trademark) MX-270, -280, -290, NIKALAC MS-11, NIKALAC MW-30, -100, -300, -390, -750 (manufactured by SANWA CHEMICAL); DML-OCHP, DML-MBPC, DML-BPC, DML-PEP, DML-34X, DML -PSBP, DML-PTBP, DML-PCHP, DML-POP, DML-PFP, DML-MBOC, BisCMP-F, DML-BisOC-Z, DML-BisOCHP-Z, DML-BisOC-P, DMOM-PTBT, TMOM -BP, TMOM-BPA, TML-BPAF-MF (manufactured by Benzhou Chemical Industry Company above); benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxyl) Methyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethyl phenyl hydroxymethyl benzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, Bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methyl) (Oxymethyl) benzophenone, methoxymethyl phenyl methoxymethyl benzoate, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, etc. .

In addition, examples of ethylene oxide compounds include phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol type epoxy resin, triphenol type epoxy resin, and tetraphenol type epoxy resin. Epoxy resin, phenol-xylylene type epoxy resin, naphthol-xylylene type epoxy resin, phenol-naphthol type epoxy resin, phenol-dicyclopentadiene type epoxy resin, alicyclic Formula epoxy resin, aliphatic epoxy resin, diethylene glycol diglycidyl ether, sorbitol polyglycidyl ether, propylene glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, 1,1,2,2 -Tetra(p-hydroxyphenyl)ethane tetraglycidyl ether, glycerol triglycidyl ether, o-second butylphenyl glycidyl ether, 1,6-bis(2,3-glycidoxy)naphthalene, Diglycerol polyglycidyl ether, polyethylene glycol glycidyl ether, YDB-340, YDB-412, YDF-2001, YDF-2004 (the above are trade names, manufactured by Nippon Steel Chemical Co., Ltd.), NC-3000- H, EPPN-501H, EOCN-1020, NC-7000L, EPPN-201L, XD-1000, EOCN-4600 (the above are trade names, manufactured by Nippon Kayaku Co., Ltd.), Epikote (registered trademark) 1001, Epikote 1007, Epikote 1009, Epikote 5050, Epikote 5051, Epikote 1031S, Epikote 180S65, Epikote 157H70, YX-315-75 (the above are trade names, manufactured by Japan Epoxy Resins Co., Ltd.), EHPE3150, PLACCEL G402, PUE101, PUE105 (the above are products) Name, manufactured by Diacel Chemical Industries Co., Ltd.), EPICLON (registered trademark) 830, 850, 1050, N-680, N-690, N-695, N-770, HP-7200, HP-820, EXA-4850- 1000 (the above are trade names, manufactured by DIC), DENACOL (registered trademark) EX-201, EX-251, EX-203, EX-313, EX-314, EX-321, EX-411, EX-511, EX -512, EX-612, EX-614, EX-614B, EX-711, EX-731, EX-810, EX-911, EM-150 (the above are trade names, manufactured by Nagase chemteX), Epolight (registered trademarks) ) 70P, Epolight 100MF (the above are the trade names, manufactured by Kyoeisha Chemical), etc.

In addition, examples include 4,4'-diphenylmethane diisocyanate, toluene diisocyanate, 1,3-xylylene diisocyanate, and dicyclohexylmethane-4,4'- as isocyanate group-containing compounds Diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, Takenate (registered trademark) 500, 600, Cosmonate (registered trademark) NBDI, ND (the above are trade names, manufactured by Mitsui Chemicals), Duranate (registered trademark) ) 17B-60PX, TPA-B80E, MF-B60X, MF-K60X, E402-B80T (the above are trade names, manufactured by Asahi Kasei Chemicals) and the like.

In addition, examples include: 4,4'-diphenylmethane bismaleimide, phenylmethane maleimide, and meta-phenylene bis Maleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane Bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide-(2,2,4 -Trimethyl) hexane, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenyl bismaleimide, 1,3-bis(3 -Maleimide phenoxy)benzene, 1,3-bis(4-maleimide phenoxy)benzene, BMI-1000, BMI-1100, BMI-2000, BMI-2300 , BMI-3000, BMI-4000, BMI-5100, BMI-7000, BMI-TMH, BMI-6000, BMI-8000 (the above are trade names, manufactured by Daiwa Chemical Industry Co., Ltd.), etc., but as long as they are as mentioned above Generally, compounds that undergo thermal crosslinking are not limited to these.

Regarding the compounding amount in the case of using a crosslinking agent, it is preferably 0.5-20 parts by mass, more preferably 2-10 parts by mass relative to 100 parts by mass of the (A) resin. When the compounding amount is 0.5 parts by mass or more, it exhibits good heat resistance and chemical resistance. On the other hand, when it is 20 parts by mass or less, the storage stability is excellent.

The photosensitive resin composition of this invention may contain an organic titanium compound. By containing the organic titanium compound, even when it is cured at a low temperature of about 250°C, a photosensitive resin layer with excellent chemical resistance can be formed. Moreover, especially by making the photosensitive resin composition contain (B) compound Both of the organic titanium compound and the organic titanium compound, and the cured resin layer has the effect of not only excellent substrate adhesion but also excellent chemical resistance.

In particular, by containing both (B-1) nanoparticle and organic titanium compound in the photosensitive resin composition, the cured resin layer has the effect of not only excellent substrate adhesion, but also chemical resistance .

In addition, especially by containing both the (B-2) thermal crosslinking agent and the organic titanium compound in the photosensitive resin composition, the cured resin layer has not only excellent substrate adhesion but also excellent chemical resistance effect.

In particular, by containing both the (B-3) compound and the organic titanium compound in the photosensitive resin composition, the cured resin layer has the effect of not only having excellent substrate adhesion but also excellent chemical resistance.

As the organotitanium compound that can be used, an organic chemical substance is bonded to a titanium atom via a covalent bond or an ionic bond.

Specific examples of organotitanium compounds are shown in the following I)~VII):

I) Titanium chelate compound: Among them, in terms of the storage stability of the negative photosensitive resin composition and obtaining a good pattern, it is more preferably a titanium chelate compound having two or more alkoxy groups. Specific examples are Bottom: bis(triethanolamine) titanium diisopropoxide, bis(2,4-glutaric acid) di-n-butoxide titanium, bis(2,4-glutaric acid) titanium diisopropoxide, bis(tetramethyl) Pimelic acid) titanium diisopropoxide, bis(ethyl acetic acid) titanium diisopropoxide and the like.

II) Tetraalkoxide titanium compounds: for example tetra(n-butoxide) titanium, tetraethoxide, tetra(2-ethylhexanol) titanium, tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, Titanium methoxypropoxide, titanium tetramethylphenoxide, tetra(n-nonyl alcohol) titanium, tetra(n-propanol) titanium, tetrastearyl titanium, tetra[bis{2,2-(allyloxymethyl ) Butanol}] Titanium etc.

III) Titanocene compounds: for example (pentamethylcyclopentadienyl)titanium trimethoxide, bis(η ⁵ -2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl) ) Titanium, bis(η ⁵ -2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium and the like.

IV) Monoalkoxy titanium compounds: for example, tris(dioctyl phosphate) titanium isopropoxide, tris(dodecylbenzene sulfonic acid) titanium isopropoxide, and the like.

V) Titanium oxide compounds: for example, bis(glutaric acid) titanium oxide, bis(tetramethylpimelic acid) titanium oxide, titanyl phthalocyanine, and the like.

VI) Titanium tetraacetylpyruvate compounds: for example, titanium tetraacetylpyruvate and the like.

VII) Titanate coupling agent: for example, tris(dodecylbenzenesulfonyl)isopropyl titanate and the like.

Among them, from the viewpoint of exhibiting better chemical resistance, the organic titanium compound is preferably selected from the group consisting of I) titanium chelate compound, II) tetraalkoxy titanium compound and III) titanocene compound. At least one compound in the group of constituents. Particularly preferred are bis (ethyl acetyl acetate) titanium diisopropoxide, tetra (n-butoxide) titanium, and bis (η ⁵ -2,4-cyclopentadien-1-yl) bis (2,6- Difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium.

Regarding the blending amount in the case of blending the organotitanium compound, it is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass relative to 100 parts by mass of the (A) resin. When the compounding amount is 0.05 parts by mass or more, it exhibits good heat resistance and chemical resistance. On the other hand, when it is 10 parts by mass or less, the storage stability is excellent.

Furthermore, in order to improve the adhesiveness of the film formed using the photosensitive resin composition of this invention, and a base material, you may mix|blend an adhesive auxiliary agent arbitrarily. Examples of the adhesive agent include: γ-aminopropyl dimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyl dimethoxysilane, and γ-glycidoxy Propylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyl dimethoxymethylsilane, 3-methacryloxy Propyl trimethoxysilane, Dimethoxymethyl-3-piperidinyl propyl silane, diethoxy-3-glycidoxy propyl methyl silane, N-(3-diethoxy methyl silyl propyl) butyl Diimide, N-[3-(triethoxysilyl)propyl]phthalic acid, benzophenone-3,3'-bis(N-[3-triethoxysilane Propyl]propylamide)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid , 3-(Triethoxysilyl)propyl succinic anhydride, N-phenylaminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxy Silane coupling agents such as silyl silane, 3-(trialkoxysilyl) propyl succinic anhydride, and aluminum tris(ethylacetate), aluminum tris(acetypyruvate), ethyl aluminum diisoacetate Aluminum-based adhesives such as propyl ester, etc.

Among these bonding aids, it is more preferable to use a silane coupling agent in terms of adhesion. When the photosensitive resin composition contains an adhesive auxiliary agent, the blending amount of the adhesive auxiliary agent is preferably in the range of 0.5 to 25 parts by mass relative to 100 parts by mass of the (A) resin.

As the silane coupling agent, 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name KBM803, manufactured by Chisso Co., Ltd.: trade name Sila-Ace S810), 3-mercaptopropyl trimethoxysilane Ethoxysilane (manufactured by Azmax Co., Ltd.: trade name SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name LS1375, manufactured by Azmax Co., Ltd.: product Name SIM6474.0), mercaptomethyltrimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SIM6473.5C), mercaptomethylmethyldimethoxysilane (manufactured by Azmax Co., Ltd. trade name SIM6473.0) , 3-Mercaptopropyl diethoxy methoxy silane, 3-mercaptopropyl ethoxy dimethoxy silane, 3-mercaptopropyl tripropoxy silane, 3-mercaptopropyl diethoxy propyl Oxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercaptoethyl Trimethoxysilane, 2-mercaptoethyldiethoxymethoxysilane, 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltripropane Oxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercaptoethyldimethoxypropoxysilane, 2-mercaptoethylmethoxysilane Dipropoxysilane, 4-mercaptobutyltrimethoxysilane, 4-mercaptobutyltriethoxysilane, 4-mercaptobutyltripropoxysilane, N-(3-triethoxysilyl Propyl) urea (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name LS3610, manufactured by Azmax Co., Ltd.: trade name SIU9055.0), N-(3-trimethoxysilylpropyl)urea (manufactured by Azmax Co., Ltd.) ：Trade name SIU9058.0), N-(3-diethoxymethoxysilylpropyl)urea, N-(3-ethoxydimethoxysilylpropyl)urea, N-(3 -Tripropoxysilylpropyl)urea, N-(3-diethoxypropoxysilylpropyl)urea, N-(3-ethoxydipropoxysilylpropyl)urea, N-(3-Dimethoxypropoxysilylpropyl)urea, N-(3-methoxydipropoxysilylpropyl)urea, N-(3-trimethoxysilylethyl) ) Urea, N-(3-ethoxydimethoxysilylethyl)urea, N-(3-tripropoxysilylethyl)urea, N-(3-tripropoxysilylethyl) Base) urea, N-(3-ethoxydipropoxysilylethyl)urea, N-(3-dimethoxypropoxysilylethyl)urea, N-(3-methoxy Dipropoxysilylethyl)urea, N-(3-trimethoxysilylbutyl)urea, N-(3-triethoxysilylbutyl)urea, N-(3-tripropoxy Silyl butyl) urea, 3-(m-aminophenoxy) propyl trimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SLA0598.0), m-aminophenyl trimethoxysilane (Azmax Manufactured by Co., Ltd.: trade name SLA0599.0), p-aminophenyl trimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SLA0599.1), aminophenyl trimethoxysilane (manufactured by Azmax Co., Ltd.: Trade name SLA0599.2), 2-(Trimethoxysilylethyl)pyridine (manufactured by Azmax Co., Ltd.: Trade name SIT8396.0), 2-(Triethoxysilylethyl)pyridine, 2-( Dimethoxysilylmethylethyl)pyridine, 2-(diethoxysilylmethylethyl)pyridine, aminoformic acid (3-triethoxysilylpropyl) tertiary butyl ester, ( 3-glycidoxypropyl) triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxy Silane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, tetra-third-butoxysilane, tetra(methoxyethoxysilane), tetra(methoxy-n-propoxy) Silane), tetra(ethoxyethoxysilane), tetra(methoxyethoxyethoxysilane), bis(trimethoxysilyl)ethane, bis(trimethoxysilyl)hexane , Bis(triethoxysilyl)methane, bis(triethoxysilyl)ethane, bis(triethoxysilyl)ethylene, bis(triethoxysilyl)octane, bis(triethoxysilyl) Ethoxysilyl)octadiene, bis[3-(triethoxysilyl)propyl]disulfide, bis[3-(triethoxysilyl)propyl]tetrasulfide, second Tributoxydiethoxysilane, diisobutoxyaluminumoxytriethoxysilane, bis(glutaric acid)titanium-O,O'-bis(oxyethyl)-aminopropyl Triethoxysilane, phenyl silane triol, methyl phenyl silane diol, ethyl phenyl silane diol, n-propyl phenyl silane diol, isopropyl phenyl silane diol, n-butyl benzene Silane diol, isobutyl phenyl silane diol, tertiary butyl phenyl silane diol, diphenyl silane diol, dimethoxy diphenyl silane, diethoxy diphenyl silane, two Methoxy di-p-tolyl silanol, ethyl methyl phenyl silanol, n-propyl methyl phenyl silanol, isopropyl methyl phenyl silanol, n-butyl methyl phenyl silanol, isobutyl methyl benzene Silanol, tertiary butyl methyl phenyl silanol, ethyl n-propyl phenyl silanol, ethyl isopropyl phenyl silanol, n-butyl ethyl phenyl silanol, isobutyl ethyl phenyl Silanol, tertiary butyl ethyl phenyl silanol, methyl diphenyl silanol, ethyl diphenyl silanol, n-propyl diphenyl silanol, isopropyl diphenyl silanol, n-butyl Diphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, triphenylsilanol, etc., but not limited to these. These can be used alone or in combination of plural kinds.

As the silane coupling agent, among the above-mentioned silane coupling agents, from the viewpoint of storage stability, phenyl silane triol, trimethoxyphenyl silane, trimethoxy (p-tolyl) silane, and diphenyl are preferred. Silanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, triphenylsilanol, and a silane coupling agent represented by the following structure.

Regarding the compounding amount when the silane coupling agent is used, it is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the (A) resin.

唑前驅物、可溶性聚醯亞胺及酚樹脂等之正型等而不同。 The photosensitive resin composition of the present invention may further contain components other than the above-mentioned components. The preferred one is based on (A) resin such as the use of polyimide precursors and polyamides and other negative types or the use of poly

The azole precursor, soluble polyimide, phenol resin, etc. are different.

啉基二苯甲酮、二甲基胺基苯甲酸異戊酯、二乙基胺基苯甲酸異戊酯、2-巰基苯并咪唑、1-苯基-5-巰基四唑、2-巰基苯并噻唑、2-(對二甲基胺基苯乙烯基)苯并

唑、2-(對二甲基胺基苯乙烯基)苯并噻唑、2-(對二甲基胺基苯乙烯基)萘并(1,2-d)噻唑、2-(對二甲基胺基苯甲醯基)苯乙烯等。該等可單獨使用或以例如2~5者之組合之形式使用。 When using a polyimide precursor or polyimide as the negative type of (A) resin, a sensitizer can be optionally blended in order to improve the photosensitivity. As the sensitizer, for example, Michelone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylamino)benzylidene )Cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methyl Cyclohexanone, 4,4'-bis(dimethylamino) chalcone, 4,4'-bis(diethylamino) chalcone, p-dimethylamino cinnamicindanone , P-dimethylaminobenzylidene indanone, 2-(p-dimethylaminophenyl biphenylene) benzothiazole, 2-(p-dimethylaminophenyl vinylene) benzothiazole , 2-(p-dimethylaminophenyl vinylene) isonaphththiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-di Ethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3- Ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin Element, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-benzene Ethanolamine, 4-

Linyl benzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercapto Benzothiazole, 2-(p-dimethylaminostyryl)benzo

Azole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminostyryl) Aminobenzyl) styrene and the like. These can be used alone or in the form of a combination of, for example, 2 to 5.

Regarding the compounding amount when the photosensitive resin composition contains a sensitizer for improving photosensitivity, it is preferably 0.1 to 25 parts by mass relative to 100 parts by mass of the (A) resin.

酯及甲基丙烯酸異

酯、丙烯醯胺及其衍生物、甲基丙烯醯胺及其衍生物、三羥甲基丙烷三丙烯酸酯及甲基丙烯酸酯、甘油之二或三丙烯酸酯及甲基丙烯酸酯、季戊四醇之二、三或四丙烯酸酯及甲基丙烯酸酯、以及該等化合物之環氧乙烷或環氧丙烷加成物等化合物。 In addition, in order to improve the resolution of the embossed pattern, a monomer having a photopolymerizable unsaturated bond can be arbitrarily formulated. As such a monomer, a (meth)acrylic compound that undergoes a radical polymerization reaction with a photopolymerization initiator is preferred, and it is not particularly limited to those listed below. Examples include: diethylene glycol dimethyl Mono- or diacrylate and methacrylate of ethylene glycol or polyethylene glycol such as methacrylate, tetraethylene glycol dimethacrylate, mono- or diacrylate and methacrylate of propylene glycol or polypropylene glycol, Glycerin mono-, di- or tri-acrylate and methacrylate, cyclohexane diacrylate and dimethacrylate, 1,4-butanediol diacrylate and dimethacrylate, 1,6- Diacrylate and dimethacrylate of hexanediol, diacrylate and dimethacrylate of neopentyl glycol, mono or diacrylate and methacrylate of bisphenol A, benzene trimethacrylate , Acrylic acid

Esters and methacrylic acid iso

Ester, acrylamide and its derivatives, methacrylamide and its derivatives, trimethylolpropane triacrylate and methacrylate, glycerol bis or triacrylate and methacrylate, pentaerythritol bis , Tri- or tetra-acrylate and methacrylate, and compounds such as ethylene oxide or propylene oxide adducts of these compounds.

When the photosensitive resin composition contains the above-mentioned monomer having a photopolymerizable unsaturated bond to improve the resolution of the relief pattern, regarding the monomer having a photopolymerizable unsaturated bond The blending amount is preferably 1-50 parts by mass relative to 100 parts by mass of (A) resin.

、N-苯基萘基胺、乙二胺四乙酸、1,2-環己二胺四乙酸、二醇醚二胺四乙酸、2,6-二第三丁基對甲基苯酚、5-亞硝基-8-羥基喹啉、1-亞硝基-2-萘酚、2-亞硝基-1-萘酚、2-亞硝基-5-(N-乙基-N-磺丙基胺基)苯酚、N-亞硝基-N-苯基羥基胺銨鹽、N-亞硝基-N(1-萘基)羥基胺銨鹽等。 In addition, in the case of using polyimide precursors or polyamides as the negative type of (A) resin, especially to increase the viscosity and lightness of the photosensitive resin composition when stored in a solution containing a solvent. For the stability of sensitivity, thermal polymerization inhibitors can be arbitrarily formulated. As thermal polymerization inhibitors, hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenanthrene can be used

, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5- Nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropyl) -Amino)phenol, N-nitroso-N-phenylhydroxyamine ammonium salt, N-nitroso-N(1-naphthyl)hydroxyamine ammonium salt, etc.

The blending amount when blending the thermal polymerization inhibitor in the photosensitive resin composition is preferably in the range of 0.005 to 12 parts by mass relative to 100 parts by mass of the (A) resin.

唑前驅物、可溶性聚醯亞胺或酚樹脂等作為(A)樹脂之正型之情形時，視需要可適當添加先前作為感光性樹脂組合物之添加劑而使用之染料、界面活性劑、以及熱酸產生劑、溶解促進劑、用以提高與基材之密接性之接著助劑等。 On the other hand, in the photosensitive resin composition of the present invention, the use of poly

When azole precursors, soluble polyimides, or phenol resins are used as the positive type of (A) resin, if necessary, dyes, surfactants, and heat previously used as additives to the photosensitive resin composition can be appropriately added. Acid generators, dissolution accelerators, adhesive additives to improve adhesion to the substrate, etc.

If the above-mentioned additives are explained more specifically, examples of dyes include methyl violet, crystal violet, malachite green and the like. Moreover, as the surfactant, for example, nonionic surfactants containing polyglycols such as polypropylene glycol or polyoxyethylene lauryl ether or their derivatives, such as Fluorad (trade name, manufactured by Sumitomo 3M), MEGAFAC ( Trade name, Dainippon Ink & Chemical Industry Co., Ltd.) or Lumiflon (trade name, manufactured by Asahi Glass Co., Ltd.) and other fluorine-based surfactants, such as KP341 (trade name, manufactured by Shin-Etsu Chemical Industry Co., Ltd.), DBE (trade name, manufactured by Chisso Co., Ltd.) , Glanol (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) and other organosiloxane surfactants. As the adhesive auxiliary agent, for example, alkyl imidazoline, butane Acid, alkyl acid, polyhydroxystyrene, polyvinyl methyl ether, tertiary butyl novolac, epoxy silane, epoxy polymer, etc., and various silane coupling agents.

About the compounding quantity of the said dye and surfactant, 0.1-30 mass parts is preferable with respect to 100 mass parts of (A) resin.

In addition, from the viewpoint of showing good thermal and mechanical properties of the cured product even when the curing temperature is lowered, a thermal acid generator can be optionally blended.

From the viewpoint of showing good thermal and mechanical properties of the cured product even when the curing temperature is lowered, it is preferable to prepare a thermal acid generator.

Examples of the thermal acid generator include salts of strong acids and bases, such as onium salts having the function of generating acid by heat, or imidate sulfonates.

Examples of onium salts include diaryl iodonium salts such as aryl diazonium salt and diphenyl iodonium salt; di(alkylaryl) iodonium salts such as di(tertiary butylphenyl) iodonium salt; three Trialkylsulfonium salts such as methylsulfonium salt; Dialkylmonoarylsulfonium salts such as dimethylphenylsulfonium salt; Diarylmonoalkylsulfonium salts such as diphenylmethylsulfonium salt; Triarylsulfonium salt Salt etc.

Among these, the di(tertiary butylphenyl) iodonium salt of p-toluenesulfonic acid, the di(tertiary butylphenyl) iodonium salt of trifluoromethanesulfonic acid, and the third trifluoromethanesulfonic acid Methyl sulfonic acid salt, dimethyl phenyl sulfonic acid salt of trifluoromethanesulfonic acid, diphenyl methyl sulfonic acid salt of trifluoromethanesulfonic acid, di(tertiary butyl phenyl) iodine salt of nonafluorobutanesulfonic acid , Camphor sulfonic acid diphenyl iodonium salt, ethanesulfonic acid diphenyl iodonium salt, benzene sulfonic acid dimethyl phenyl sulfonium salt, toluene sulfonic acid diphenyl methyl sulfonium salt, etc.

Moreover, as the salt formed of a strong acid and a base, in addition to the above-mentioned onium salt, a salt formed of the following strong acid and a base, such as a pyridinium salt, can also be used. Examples of strong acids include aryl sulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, perfluoroalkylsulfonic acids such as camphorsulfonic acid, trifluoromethanesulfonic acid, and nonafluorobutanesulfonic acid, and methanesulfonic acid , Ethanesulfonic acid, butanesulfonic acid and other alkyl sulfonic acids. As a base, it can Examples include pyridine, alkylpyridines such as 2,4,6-trimethylpyridine, N-alkylpyridines such as 2-chloro-N-methylpyridine, and halogenated-N-alkylpyridines.

As the imine sulfonate, for example, naphthyl imine sulfonate, phthalimide sulfonate, etc. can be used, and it is not limited as long as it is a compound that generates an acid under the action of heat.

Regarding the blending amount when using a thermal acid generator, relative to 100 parts by mass of (A) resin, preferably 0.1-30 parts by mass, more preferably 0.5-10 parts by mass, and still more preferably 1-5 parts by mass .

烯-2,3-二羧酸酐以莫耳比1：2進行反應而獲得之化合物、使雙-(3-胺基-4-羥基苯基)碸與1,2-環己基二羧酸酐以莫耳比1：2進行反應而獲得之化合物、N-羥基琥珀醯亞胺、N-羥基苯二甲醯亞胺、N-羥基5-降

烯-2,3-二羧醯亞胺等。作為具有羧基之化合物之例，可列舉：3-苯基乳酸、4-羥基苯基乳酸、4-羥基苦杏仁酸、3,4-二羥基苦杏仁酸、4-羥基-3-甲氧基苦杏仁酸、2-甲氧基-2-(1-萘基)丙酸、苦杏仁酸、2-苯乳酸、α-甲氧基苯基乙酸、O-乙醯基苦杏仁酸、伊康酸等。 In the case of a positive photosensitive resin composition, in order to promote the removal of useless resin after exposure, a dissolution accelerator can be used. Preferably, for example, a compound having a hydroxyl group or a carboxyl group. Examples of compounds having a hydroxyl group include: ballasts used for the above-mentioned naphthoquinone diazide compounds, and straight-chains such as p-cumyl phenol, bisphenols, resorcinols, and MtrisPC and MtetraPC. Non-linear phenol compounds such as TrisP-HAP, TrisP-PHBA, TrisP-PA (all manufactured by Honshu Chemical Industry Co., Ltd.), 2~5 phenol substitutions of diphenylmethane, 3,3-di 1~5 phenol substitutions of phenylpropane, make 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane and 5-

A compound obtained by reacting ene-2,3-dicarboxylic acid anhydride at a molar ratio of 1:2, bis-(3-amino-4-hydroxyphenyl) sulfonate and 1,2-cyclohexyl dicarboxylic anhydride The compound obtained by reacting at a molar ratio of 1:2, N-hydroxysuccinimide, N-hydroxyxylylenedimethanimide, N-hydroxy 5-n

En-2,3-dicarboxyimines and others. Examples of compounds having a carboxyl group include 3-phenyllactic acid, 4-hydroxyphenyllactic acid, 4-hydroxymandelic acid, 3,4-dihydroxymandelic acid, 4-hydroxy-3-methoxy Mandelic acid, 2-methoxy-2-(1-naphthyl)propionic acid, mandelic acid, 2-phenyllactic acid, α-methoxyphenylacetic acid, O-acetylmandelic acid, Ikon Acid etc.

Regarding the compounding amount in the case of using the dissolution accelerator, it is preferably 0.1 to 30 parts by mass relative to 100 parts by mass of the (A) resin.

<Method for manufacturing hardened relief pattern and semiconductor device>

In addition, the present invention provides a method for manufacturing a hardened relief pattern, which includes: step (1) of forming a resin layer on the substrate by coating the photosensitive resin composition of the present invention on the substrate; step ( 2), which is to expose the resin layer; step (3), which is to develop the exposed resin layer to form a relief pattern; and step (4), which is to perform the relief pattern by Heat treatment to form a hardened relief pattern. The following describes the typical state of each step.

(1) Step of forming a resin layer on the substrate by coating the photosensitive resin composition on the substrate

In this step, the photosensitive resin composition of the present invention is coated on a substrate, and then dried as necessary to form a resin layer. As the coating method, the method previously used for coating the photosensitive resin composition can be used, for example, using a spin coater, bar coater, knife coater, curtain coater, screen printer, etc. The method of coating, the method of spray coating with a spray coater, etc.

As a method for forming a relief pattern using the photosensitive resin composition of the present invention, not only can a resin layer be formed on the substrate by coating the photosensitive resin composition on the substrate, but also by combining the photosensitive resin After the product is in the form of a film, a layer of the photosensitive resin composition is laminated on the substrate to form a resin layer. In addition, when a film of the photosensitive resin composition of the present invention is formed on a support substrate, when the film is used, the support substrate can be removed after lamination, or the support substrate can be removed before lamination.

If necessary, the coating film containing the photosensitive resin composition can be dried. As the drying method, air drying, heating drying using an oven or hot plate, vacuum drying, etc. can be used. Specifically, in the case of air drying or heat drying, it can be dried at 20°C to 140°C for 1 minute to 1 hour. The resin layer can be formed on the substrate by the above method.

(2) Steps to expose the resin layer

In this step, an exposure device such as a contact exposure machine, a mirror projection exposure machine, a stepper, etc. is used, through a photomask or reticle with a pattern, or directly by an ultraviolet light source. The formed resin layer is exposed.

Thereafter, in order to improve light sensitivity, etc., post-exposure bake (PEB) and/or pre-development bake under any combination of temperature and time may be implemented as needed. The range of baking conditions is preferably temperature: 40 to 120°C, time: 10 seconds to 240 seconds, but it is not limited to this range as long as the characteristics of the photosensitive resin composition of the present invention are not impaired.

(3) The step of developing the exposed resin layer to form a relief pattern

唑前驅物或可溶性聚醯亞胺作為(A)樹脂之情形)時，將曝光部顯影去除。作為顯影方法，可自先前已知之光阻之顯影方法、例如旋轉噴霧法、覆液法、伴有超音波處理之浸漬法等中選擇任意方法而使用。又，於顯影後，為了調整浮凸圖案之形狀等，視需要亦可實施任意之溫度及時間之組合之條件下之顯影後烘烤。 In this step, the exposed part or unexposed part of the photosensitive resin layer after exposure is developed and removed. In the case of using a negative photosensitive resin composition (for example, when polyimide precursor or polyamide is used as the resin (A)), develop and remove the unexposed part, and use a positive photosensitive resin Composition (e.g. using poly

When an azole precursor or soluble polyimide is used as (A) resin), the exposed part is developed and removed. As the development method, any method can be selected and used from previously known development methods of photoresist, such as a rotary spray method, a liquid coating method, and a dipping method accompanied by ultrasonic treatment. In addition, after development, in order to adjust the shape of the relief pattern, etc., post-development baking under any combination of temperature and time can be implemented as needed.

As the developer used during development, a good solvent for the photosensitive resin composition, or a combination of the good solvent and the poor solvent is preferred. For example, in the case of a photosensitive resin composition insoluble in an alkaline aqueous solution, as a good solvent, N-methylpyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethyl Acetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, etc. As a poor solvent, toluene, xylene, methanol, ethanol, isopropanol are preferred , Ethyl lactate, propylene glycol methyl ether acetate and water, etc. For mixing good solvents with poor solvents When used, it is preferable to adjust the ratio of the poor solvent to the good solvent according to the solubility of the polymer in the photosensitive resin composition. In addition, two or more kinds of each solvent, for example, a plurality of kinds of solvents may be used in combination.

On the other hand, in the case of a photosensitive resin composition dissolved in an alkaline aqueous solution, the developer used during development is one that dissolves and removes the soluble polymer in the alkaline aqueous solution, and is typically alkaline in which an alkaline compound is dissolved. Aqueous solution. The alkaline compound dissolved in the developer solution may be any of an inorganic alkaline compound or an organic alkaline compound.

As the inorganic basic compound, for example, 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.

Moreover, as the organic basic compound, for example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, methylamine, dimethylamine, trimethylamine, monoethylamine , Diethylamine, triethylamine, n-propylamine, di-n-propylamine, isopropylamine, diisopropylamine, methyldiethylamine, dimethylethanolamine, ethanolamine, and triethanolamine.

Furthermore, if necessary, an appropriate amount of water-soluble organic solvents such as methanol, ethanol, propanol, or ethylene glycol, surfactants, storage stabilizers, and resin dissolution inhibitors can be added to the above-mentioned alkaline aqueous solution. The embossed pattern can be formed by the above method.

(4) The step of forming a hardened relief pattern by heating the relief pattern

In this step, the embossed pattern obtained by the above development is converted into a hardened embossed pattern by heating. As the method of heating and hardening, various methods can be selected, such as those who use hot plates, those who use ovens, and those who use temperature-rising ovens that can set the temperature control program. The heating can be performed under conditions of, for example, 180°C to 400°C for 30 minutes to 5 hours. As the ambient gas during heating and hardening, air can be used, or inert gases such as nitrogen and argon can also be used.

<Semiconductor Device>

The present invention also provides a semiconductor device including the hardened relief pattern obtained by the above-mentioned method of manufacturing the hardened relief pattern of the present invention. The present invention also provides a semiconductor device including a substrate as a semiconductor element, and a cured relief pattern of resin formed on the substrate by the above-mentioned cured relief pattern manufacturing method. In addition, the present invention is also applicable to a method of manufacturing a semiconductor device that uses a semiconductor element as a substrate, and includes the method of manufacturing a hardened relief pattern as part of the steps. The semiconductor device of the present invention can be formed into a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for flip-chip devices, or having a hardened relief pattern formed by the above-mentioned hardened relief pattern manufacturing method. The protective film of the bump structure of the semiconductor device, etc., is combined with the known manufacturing method of the semiconductor device to be manufactured.

The photosensitive resin composition of the present invention is not only suitable for semiconductor devices as described above, but can also be used for interlayer insulation of multilayer circuits, protective coatings for flexible copper-clad plates, solder resist films, and liquid crystal alignment films.

[Example]

Hereinafter, the present invention will be specifically explained with examples, but the present invention is not limited to these. In the examples, comparative examples, and production examples, the physical properties of the photosensitive resin composition were measured and evaluated according to the following methods.

(1) Weight average molecular weight

The weight average molecular weight (Mw) of each resin was measured by gel permeation chromatography (standard polystyrene conversion). The column used for the measurement is the brand name "Shodex 805M/806M series" manufactured by Showa Denko Co., Ltd. The standard monodisperse polystyrene is selected as "Shodex STANDARD SM-105" manufactured by Showa Denko Co., Ltd., and the solvent is developed. It is N-methyl-2-pyrrolidone, the detector uses the brand name manufactured by Showa Denko Co., Ltd. "Shodex RI-930".

(2) Production of hardened embossed patterns on Cu

Using a sputtering device (type L-440S-FHL, manufactured by Canon Anelva), a 6-inch silicon wafer (manufactured by Fujimi Electronic Industry Co., Ltd., thickness 625±25μm) was sputtered sequentially with 200nm thick Ti and thick 400nm Cu. Then, using a Coater Developer (Model D-Spin60A, manufactured by SOKUDO), the photosensitive resin composition prepared by the following method was spin-coated on the wafer, and dried to form A coating film with a thickness of 10μm (a coating film with a thickness of 6-10μm is formed in the second embodiment). Using a photomask with a test pattern, using a parallel light mask alignment exposure machine (Model PLA-501FA, manufactured by Canon), the coating film was irradiated with an energy of 300mJ/cm ² . Then, in the case of the negative type, cyclopentanone is used as the developer, and in the case of the positive type, 2.38% TMAH (tetramethylammonium hydroxide) is used as the developer, and the coating developer (D-Spin60A Type, manufactured by SOKUDO company) spray-develop the coating film, rinse with propylene glycol methyl ether acetate in the case of the negative type, and rinse with pure water in the case of the positive type to obtain the embossment on Cu pattern.

Using a temperature-raising curing furnace (model VF-2000, manufactured by Koyo Lindberg), under a nitrogen atmosphere, the wafer with the embossed pattern formed on the Cu was heated for 2 hours at the temperature described in each embodiment To obtain a hardened embossed pattern containing resin with a thickness of about 6-7μm on Cu.

(3) The high temperature storage test of the hardened relief pattern on Cu and its subsequent evaluation

A temperature-rising program curing furnace (VF-2000, manufactured by Koyo Lindberg) was used to heat the wafer with the hardened relief pattern formed on Cu at 150° C. for 168 hours in air. Then, using a plasma surface treatment device (EXAM type, manufactured by Shinko Seiki Co., Ltd.), all the resin layer on Cu was removed by plasma etching. The plasma etching conditions are as follows.

Output: 133W

Gas type and flow rate: O ₂ : 40ml/min+CF ₄ : 1ml/min

Gas pressure: 50Pa

Mode: hard mode

Etching time: 1800 seconds

Use FE-SEM (field emission-scanning electron microscope, field emission scanning electron microscope) (S-4800, made by Hitachi High-Technologies) to observe the Cu surface with all the resin layer removed, and use image analysis software (A image Jun, manufactured by Asahi Kasei Corporation), calculate the area ratio of voids on the surface of the Cu layer.

<First Example>

As the first example, the following experiment was performed.

<Production Example 1> ((A) Synthesis of Polymer (A)-1 as Polyimide Precursor)

Put 155.1g of 4,4'-oxydiphthalic dianhydride (ODPA) in a separable flask with a volume of 2L, add 131.2g of 2-hydroxyethyl methacrylate (HEMA) and γ-butyrolactone 400 ml was stirred at room temperature, and 81.5 g of pyridine was added while stirring to obtain a reaction mixture. After the exotherm caused by the reaction is over, it is allowed to stand and cool to room temperature for 16 hours.

Then, under cooling in an ice bath, a solution obtained by dissolving 206.3 g of dicyclohexyl carbodiimide (DCC) in 180 ml of γ-butyrolactone was added to the reaction mixture while stirring for 40 minutes, and then stirring was carried out. What was obtained by suspending 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) in 350 ml of γ-butyrolactone was added over 60 minutes. After further stirring for 2 hours at room temperature, 30 ml of ethanol was added and stirred for 1 hour, and then 400 ml of γ-butyrolactone was added. By filtering The precipitate formed in the reaction mixture is removed to obtain a reaction liquid.

The obtained reaction solution was added to 3 L of ethanol to generate a precipitate containing crude polymer. The produced crude polymer was separated by filtration and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 L of water to precipitate the polymer, and the obtained precipitate was separated by filtration and then vacuum dried to obtain a powdery polymer (polymer (A)-1). The molecular weight of the polymer (A)-1 was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 20,000.

In addition, the weight average molecular weight of the resin obtained in each production example was measured by gel permeation chromatography (GPC) under the following conditions to obtain the weight average molecular weight in terms of standard polystyrene.

Pump: JASCO PU-980

Detector: JASCO RI-930

Column oven: JASCO CO-965 40℃

Column: 2 Shodex KD-806M in series

Mobile phase: 0.1mol/L LiBr/NMP (N-methylpyrrolidone, N-methylpyrrolidone)

Flow rate: 1ml/min.

<Production Example 2> ((A) Synthesis of polymer (A)-2 as a precursor of polyimide)

Use 147.1g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) instead of 155.1g of 4,4'-oxydiphthalic dianhydride (ODPA) of Production Example 1, except that Otherwise, the reaction was carried out in the same manner as the method described in Production Example 1 above to obtain polymer (A)-2. The molecular weight of the polymer (A)-2 was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 22,000.

<Production Example 3> ((A) Synthesis of polymer (A)-3 as a precursor of polyimide)

Use 147.8g of 2,2'-bistrifluoromethyl-4,4'-diaminobiphenyl (TFMB) instead of 93.0g of 4,4'-diaminodiphenyl ether (DADPE) of Production Example 1, except Otherwise, the reaction was carried out in the same manner as the method described in Production Example 1 above to obtain polymer (A)-3. The molecular weight of the polymer (A)-3 was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 21,000.

<Production Example 4> ((A) Synthesis of Polyamide (A)-4)

(Synthesis of phthalic acid compound end cap AIPA-MO)

Put 5-aminoisophthalic acid {herein abbreviated as AIPA}543.5g and 1700g of N-methyl-2-pyrrolidone into a separable flask with a volume of 5L, mix and stir, and heat to 50°C in a water bath . Dilute 512.0 g (3.3 mol) of 2-methacryloyloxyethyl isocyanate with 500 g of γ-butyrolactone into the dropping funnel, and directly stir at 50°C for about 2 hours.

After confirming the completion of the reaction (the disappearance of 5-aminoisophthalic acid) by low-molecular-weight gel permeation chromatography {hereinafter referred to as low-molecular-weight GPC}, the reaction solution was poured into 15L of ion-exchanged water, stirred, and Let stand, filter and separate the reaction product after crystallization and precipitation, after proper washing with water, vacuum drying at 40°C for 48 hours, thereby obtaining the amine group of 5-aminoisophthalic acid and isocyanic acid AIPA-MO obtained by the action of isocyanate group of 2-methacryloxyethyl. The low molecular weight GPC purity of the obtained AIPA-MO is about 100%.

(Synthesis of polymer (A)-4)

Put the obtained AIPA-MO 100.89g (0.3mol), pyridine 71.2g (0.9mol), and GBL (butyrolactone, γ-butyrolactone) 400g into a separable flask with a volume of 2L, and mix them with an ice bath Cool to 5°C. In an ice bath, add it dropwise for about 20 minutes Dissolve and dilute 125.0 g (0.606 mol) of dicyclohexylcarbodiimide (DCC) with 125 g of GBL, and then add 4,4'-bis(4-aminophenoxy) dropwise over 20 minutes Biphenyl {hereinafter referred to as BAPB} 103.16g (0.28mol) was dissolved in 168g of NMP, maintained in an ice bath for 3 hours below 5°C, then the ice bath was removed, and stirred at room temperature for 5 hours. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.

A mixed solution of 840 g of water and 560 g of isopropanol was added dropwise to the obtained reaction liquid, and the precipitated polymer was separated and redissolved in 650 g of NMP. The obtained crude polymer solution was dropped into 5 L of water to precipitate the polymer, and the obtained precipitate was separated by filtration and then vacuum dried to obtain a powdery polymer (polymer (A)-4). The molecular weight of the polymer (A)-4 was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 34,700.

唑前驅物之聚合物(A)-5之合成) <Manufacturing Example 5> ((A) is used as poly

(Synthesis of azole precursor polymer (A)-5)

In a separable flask with a volume of 3L, 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane 183.1g, N,N-dimethylacetamide (DMAc) 640.9g, 63.3 g of pyridine was mixed and stirred at room temperature (25°C) to make a uniform solution. The solution obtained by dissolving 118.0 g of 4,4'-diphenyl ether dimethyl chloride in 354 g of diethylene glycol dimethyl ether (DMDG) was added dropwise to it using a dropping funnel. At this point, cool the separable flask in a water bath at 15-20°C. The time required for dripping is 40 minutes, and the temperature of the reaction solution is up to 30°C.

唑前驅物。 After 3 hours after the dripping, add 30.8g (0.2mol) of 1,2-cyclohexyldicarboxylic anhydride to the reaction solution, stir and stand at room temperature for 15 hours to make the polymer chain account for 99% of the total amine The terminal group is capped with a carboxycyclohexylamino group. The reaction rate at this time can be easily calculated by tracing the residual amount of the charged 1,2-cyclohexyldicarboxylic anhydride by high performance liquid chromatography (HPLC). After that, the above reaction solution was added dropwise to 2L of water under high-speed stirring to disperse and precipitate the polymer. The polymer was recovered, washed with water, dehydrated, and vacuum dried to obtain a gel permeation chromatography (GPC) Crude polybenzo with a weight-average molecular weight of 9,000 (in terms of polystyrene) measured by the method

Azole precursors.

唑前驅物再溶解於γ-丁內酯(GBL)後，對其利用陽離子交換樹脂及陰離子交換樹脂進行處理，將藉此獲得之溶液投入至離子交換水中後，過濾分離所析出之聚合物，進行水洗並真空乾燥，藉此獲得經精製之聚苯并

唑前驅物(聚合物(A)-5)。 Make the crude polybenzo

After the azole precursor is re-dissolved in γ-butyrolactone (GBL), it is treated with a cation exchange resin and an anion exchange resin, the resulting solution is poured into ion exchange water, and the precipitated polymer is separated by filtration. Wash with water and dry in vacuum to obtain refined polybenzo

Azole precursor (Polymer (A)-5).

<Production Example 6> ((A) Synthesis of polyimide polymer (A)-6)

Install a cooling tube with a Dean-Stark separator to a glass separable four-neck flask equipped with a Teflon (registered trademark) anchor type stirrer. While nitrogen gas was introduced, the flask was immersed in a silicon oil bath for stirring.

烯-2,3-二羧酸酐(東京化成工業股份有限公司製造)4.6g(28mmol)，一面通入氮氣一面於矽浴溫度50℃下以100rpm加熱攪拌8小時。其後，加熱至矽浴溫度180℃，以100rpm加熱攪拌2小時。去除於反應中所餾出之甲苯、水。醯亞胺化反應結束後恢復至室溫。 Add 2,2-bis(3-amino-4-hydroxyphenyl)propane (manufactured by Clariant Japan) (hereinafter referred to as BAP) 72.28g (280mmol), 5-(2,5-dioxotetrahydro- 3-furyl)-3-methyl-cyclohexene-1,2 dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) (hereinafter referred to as MCTC) 70.29 g (266 mmol), γ-butyrolactone 254.6 g, 60g of toluene, after stirring at 100 rpm for 4 hours at room temperature, add 5-drop

4.6 g (28 mmol) of ene-2,3-dicarboxylic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was heated and stirred at 100 rpm at a silicon bath temperature of 50° C. for 8 hours while passing nitrogen gas. Then, it heated to 180 degreeC of silicon bath temperature, and it heated and stirred at 100 rpm for 2 hours. Remove the toluene and water distilled out in the reaction. After the imidization reaction is over, return to room temperature.

After that, the above reaction solution was added dropwise to 3L of water under high-speed stirring to disperse and precipitate the polymer, which was recovered, washed with appropriate water, dehydrated, and vacuum dried to obtain a gel permeation chromatography (GPC) method. The measured crude polyimide (polymer (A)-6) with a weight average molecular weight of 23,000 (in terms of polystyrene).

<Production Example 7> ((A) Synthesis of Polymer (A)-8 as Phenolic Resin)

A separable flask with a Dean-Stark device with a volume of 1.0L was replaced with nitrogen. Then, 81.3g (0.738mol) of resorcinol and 84.8g (0.35mol of BMMB) were added to the separable flask. ), 3.81 g (0.02 mol) of p-toluenesulfonic acid and 116 g of propylene glycol monomethyl ether (hereinafter also referred to as PGME) were mixed and stirred at 50°C to dissolve the solids.

The mixed solution was heated to 120°C in an oil bath, and it was confirmed that methanol was generated from the reaction solution. The reaction solution was stirred directly at 120°C for 3 hours.

Then, 24.9g (0.150mol) of 2,6-bis(hydroxymethyl)p-cresol and 249g of PGME were mixed and stirred in another container to make them uniformly dissolved, and the obtained solution was used in a dropping funnel for 1 It was added dropwise to the separable flask for 2 hours, and stirred for 2 hours after the dropping.

After the reaction was completed, the same treatment as in Production Example 7 was performed to obtain a copolymer (polymer H) containing resorcinol/BMMB/2,6-bis(hydroxymethyl)p-cresol at a yield of 77%. The weight average molecular weight of this polymer H calculated by the standard polystyrene conversion of the GPC method was 9,900.

<Example 1>

Using polymers (A)-1 and (A)-2, a negative photosensitive resin composition was prepared by the following method, and the photosensitive resin composition was evaluated. The polymer (A)-1 50g and (A)-2 50g (equivalent to (A) resin) as the precursor of polyimide were combined with dicyclohexyl phthalate (manufactured by Tokyo Chemical Industry Co., Ltd., Equivalent to (B)-1) 4g, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime (denoted as "PDO" in Table 1) (equivalent to (C ) Sensitizer) 4g, 8g of tetraethylene glycol dimethacrylate, 1.5g of N-[3-(triethoxysilyl)propyl] phthalic acid and 1.5g are dissolved in N-methyl A mixed solvent of 80 g of -2-pyrrolidone (hereinafter referred to as NMP) and 20 g of ethyl lactate. The viscosity of the obtained solution was adjusted to about 35 poise by further adding a small amount of the above-mentioned mixed solvent, and a negative photosensitive resin composition was prepared.

For this composition, cured at 230°C by the above-mentioned method to produce a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated, and a result of 4.1% was obtained.

<Example 2>

In Example 1 above, the component (B) was changed to diphenyl phthalate (manufactured by Tokyo Chemical Industry Co., Ltd.), except that the negative photosensitive resin composition was prepared in the same manner as in Example 1.物solution.

For the composition, cured at 230°C by the above-mentioned method to produce a hardened relief pattern on the Cu layer. After a high temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated, and a result of 4.9% was obtained.

<Example 3>

In Example 1 above, the component (B) was changed to di-2-ethylhexyl phthalate (manufactured by Tokyo Chemical Industry Co., Ltd.), except that the negative was prepared in the same manner as in Example 1. Type photosensitive resin composition solution.

For this composition, cured at 230°C by the above-mentioned method to produce a hardened relief pattern on the Cu layer. After a high temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated, and a result of 5.2% was obtained.

<Example 4>

In the above Example 1, the component (B) was changed to dicyclohexyl trimellitate (manufactured by Tokyo Chemical Industry Co., Ltd.), except that the negative photosensitive resin was prepared in the same manner as in Example 1. Composition solution.

For this composition, cured at 230°C by the above-mentioned method to produce a hardened relief pattern on the Cu layer, and after a high temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated Rate, and get a result of 4.3%.

<Example 5>

In Example 1, the component (B) was changed to pyromellitic acid dicyclohexyl ester (manufactured by Tokyo Chemical Industry Co., Ltd.), except that the negative photosensitive resin was prepared in the same manner as in Example 1. Composition solution.

For this composition, cured at 230°C by the above method to produce a hardened relief pattern on the Cu layer, and after a high temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated, and a result of 4.2% was obtained.

<Example 6>

In the above Example 1, the component (B) was changed to dicyclohexyl adipate (manufactured by Tokyo Chemical Industry Co., Ltd.), except that the negative photosensitive resin composition was prepared in the same manner as in Example 1.物solution.

For this composition, cured at 230°C by the above method to produce a hardened relief pattern on the Cu layer, and after a high temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated, and a result of 5.9% was obtained.

<Example 7>

In the above Example 1, the component (B) was changed to dicyclohexyl sebacate (manufactured by Tokyo Chemical Industry Co., Ltd.), except that the negative photosensitive resin composition was prepared in the same manner as in Example 1.物solution.

For the composition, cured at 230°C by the above method to produce a hardened relief pattern on the Cu layer, and after a high temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated, and a result of 5.8% was obtained.

<Example 8>

In the above Example 1, the component (B) was changed to tetrahydrofurfuryl butyrate (manufactured by Tokyo Chemical Industry Co., Ltd.), except that the negative photosensitive resin composition was prepared in the same manner as in Example 1. Solution.

For this composition, cured at 230°C by the above method to produce a hardened relief pattern on the Cu layer, and after a high temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated, and a result of 4.8% was obtained.

<Example 9>

In the above-mentioned Example 1, except that the addition amount of the component (B)-1 was changed to 2 g, a negative photosensitive resin composition solution was prepared in the same manner as in Example 1.

For this composition, cured at 230°C by the above-mentioned method to make a hardened relief pattern on the Cu layer. After a high temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated, and a result of 7.6% was obtained.

<Example 10>

In the above-mentioned Example 1, except that the addition amount of the component (B)-1 was changed to 8 g, a negative photosensitive resin composition solution was prepared in the same manner as in Example 1.

For this composition, cured at 230°C by the above method to produce a hardened relief pattern on the Cu layer, and after a high temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated, and a result of 4.8% was obtained.

<Example 11>

In the above-mentioned Example 1, except that the addition amount of the (B)-1 component was changed to 16 g, a negative photosensitive resin composition solution was prepared in the same manner as in Example 1.

For this composition, cured at 230°C by the above-mentioned method to produce a hardened relief pattern on the Cu layer, and after a high temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated Rate, and get a result of 10.5%.

<Example 12>

In the above-mentioned Example 1, except that the curing temperature was changed from 230°C to 350°C, a negative photosensitive resin composition solution was prepared in the same manner as in Example 1.

For this composition, a hardened relief pattern was made on the Cu layer, and after a high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated, and a result of 4.5% was obtained.

<Example 13>

In the above Example 1, as the resin (A), 50 g of polymer (A)-1 and 50 g of polymer (A)-2 were changed to 100 g of polymer (A)-1, and the component (C) was changed from PDO to 1,2-octanedione-1-{4-(phenylthio)-2-(O-benzyloxime)} (Irgacure OXE01 (manufactured by BASF Corporation, trade name)) 2.5 g, other than , In the same manner as in Example 1, a negative photosensitive resin composition solution was prepared.

For this composition, a hardened relief pattern was made on the Cu layer, and after a high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated, and a result of 4.3% was obtained.

<Example 14>

In Example 12, the solvent was changed to 85 g of γ-butyrolactone and 15 g of dimethylsulfene. In the same manner as in Example 12, a negative photosensitive resin composition solution was prepared.

For this composition, a hardened relief pattern was made on the Cu layer, and after a high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated, and a result of 4.5% was obtained.

<Example 15>

In the above Example 1, as the resin (A), 50 g of polymer (A)-1 and 50 g of polymer (A)-2 were changed to 100 g of polymer (A)-3, and the curing temperature was changed from 230°C to Except for this at 350° C., a negative photosensitive resin composition solution was prepared in the same manner as in Example 1.

For the composition, a hardened relief pattern was made on the Cu layer, and after a high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated, and a result of 4.8% was obtained.

<Example 16>

In the above Example 1, as the (A) resin, 50 g of polymer (A)-1 and 50 g of polymer (A)-2 were changed to 100 g of polymer (A)-4. 1 The negative photosensitive resin composition solution was prepared in the same manner.

For this composition, a hardened relief pattern was made on the Cu layer, and after a high temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated, and a result of 4.9% was obtained.

<Example 17>

唑前驅物之聚合物(A)-5 100g(相當於(A)樹脂)與下述式(96)：

Using polymer (A)-5, a positive photosensitive resin composition was prepared by the following method, and the prepared photosensitive resin composition was evaluated. Will be as poly

100g of azole precursor polymer (A)-5 (equivalent to (A) resin) and the following formula (96):

77% of the phenolic hydroxyl group expressed by naphthoquinone diazide-4-sulfonic acid esterified photosensitive diazoquinone Compound (manufactured by Toyo Gosei, corresponding to (C) component) (C1) 15 g was dissolved in 100 g of γ-butyrolactone (as a solvent). Further, by adding a small amount of γ-butyrolactone, the viscosity of the obtained solution was adjusted to about 20 poises to prepare a positive photosensitive resin composition.

For this composition, a hardened relief pattern was made on the Cu layer by curing at 350°C by the above-mentioned method. After a high temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated, and a result of 5.1% was obtained.

<Example 18>

In Example 17 above, as the resin (A), 100 g of polymer (A)-5 was changed to 100 g of polymer (A)-6, except that the positive photosensitive resin was prepared in the same manner as in Example 17. Resin composition solution.

For this composition, cured at 250°C by the above-mentioned method to produce a hardened relief pattern on the Cu layer. After a high temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated, and a result of 6.2% was obtained.

<Example 19>

In the above-mentioned Example 17, as the resin (A), 100 g of polymer (A)-6 was changed to polymer (A)-7 (novolac resin, polystyrene conversion weight average molecular weight (Mw) = 10,600 (Asahi Except for 100 g manufactured by Jicai Co., Ltd., product name EP-4080G), a positive photosensitive resin composition solution was prepared in the same manner as in Example 17.

For the composition, cured at 250°C by the above method to produce a hardened relief pattern on the Cu layer, and after a high temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated, and a result of 5.2% was obtained.

<Example 20>

In the above-mentioned Example 17, as (A) resin, 100 g of polymer (A)-6 was changed to polymer (A)-7 (Novolak resin, polystyrene conversion weight average molecular weight (Mw)=10,600 (manufactured by Asahi Organic Materials, product name EP-4080G) 100g, and the component (B) is changed to tetrahydrofurfuryl butyrate (Manufactured by Tokyo Chemical Industry Co., Ltd.) Except for this, a positive photosensitive resin composition solution was prepared in the same manner as in Example 17.

For this composition, cured at 250°C by the above-mentioned method to produce a hardened relief pattern on the Cu layer. After a high temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated, and a result of 5.6% was obtained.

<Example 21>

In the above Example 17, as the resin (A), 100 g of polymer (A)-6 was changed to 100 g of polymer (A)-8, except that the positive photosensitive resin was prepared in the same manner as in Example 17. Resin composition solution.

For the composition, cured at 250°C by the above method to produce a hardened relief pattern on the Cu layer, and after a high temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated, and a result of 4.6% was obtained.

<Example 22>

In the above example 17, as the resin (A), 100 g of polymer (A)-6 was changed to 100 g of polymer (A)-8, and the component (B) was changed to tetrahydrofurfuryl butyrate (Tokyo Chemical Industry Co., Ltd. Co., Ltd.), except for this, a positive photosensitive resin composition solution was prepared in the same manner as in Example 17.

For this composition, cured at 250°C by the above-mentioned method to make a hardened relief pattern on the Cu layer. After a high temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated, and a result of 4.3% was obtained.

<Comparative Example 1>

In the composition of Example 1, except that the component (B)-1 was not added, a negative photosensitive resin composition was prepared in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. Since it does not contain the (B) plasticizer of the present invention, the evaluation result is 15.2%.

<Comparative Example 2>

In the composition of Example 16, except that the component (B)-1 was not added, a negative photosensitive resin composition was prepared in the same manner as in Example 15, and the same evaluation as in Example 15 was performed. Since it does not contain the (B) plasticizer of the present invention, the evaluation result is 14.3%.

<Comparative Example 3>

In the composition of Example 14, except that the component (B)-1 was not added, a negative photosensitive resin composition was prepared in the same manner as in Example 13, and the same evaluation as in Example 13 was performed. Since the plasticizer (B) of the present invention is not contained, the evaluation result is 15.7%.

<Comparative Example 4>

In the composition of Example 18, except that the component (B)-1 was not added, a positive photosensitive resin composition was prepared in the same manner as in Example 17, and the same evaluation as in Example 17 was performed. Since it does not contain the (B) plasticizer of the present invention, the evaluation result is 16.3%.

<Comparative Example 5>

In the composition of Example 1, the addition amount of the (B)-1 component was changed to 0.05 g, except that the negative photosensitive resin composition was prepared in the same manner as in Example 1, and the same as in Example 1. The same evaluation. The evaluation result was 13.1%.

<Comparative Example 6>

In the composition of Example 1, the addition amount of the (B)-1 component was changed to 60 g, except that the negative photosensitive resin composition was prepared in the same manner as in Example 1, and the same as in Example 1 The evaluation. The evaluation result was 15.2%.

Table 1 summarizes the results of these Examples 1-22 and Comparative Examples 1-6.

<Second embodiment>

As a second example, the following experiment was performed.

<Production Example 1> ((A) Synthesis of polymer A as a precursor of polyimide)

Put 155.1g of 4,4'-oxydiphthalic dianhydride (ODPA) in a separable flask with a volume of 2L, add 131.2g of 2-hydroxyethyl methacrylate (HEMA) and γ-butyrolactone 400 ml was stirred at room temperature, and 81.5 g of pyridine was added while stirring to obtain a reaction mixture. After the exotherm caused by the reaction is over, it is allowed to stand and cool to room temperature for 16 hours.

Then, under cooling in an ice bath, a solution obtained by dissolving 206.3 g of dicyclohexyl carbodiimide (DCC) in 180 ml of γ-butyrolactone was added to the reaction mixture while stirring for 40 minutes, and then stirring was carried out. What was obtained by suspending 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) in 350 ml of γ-butyrolactone was added over 60 minutes. After further stirring for 2 hours at room temperature, 30 ml of ethanol was added and stirred for 1 hour, and then 400 ml of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.

The obtained reaction solution was added to 3 L of ethanol to generate a precipitate containing crude polymer. The produced crude polymer was separated by filtration and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 L of water to precipitate the polymer, and the obtained precipitate was separated by filtration, and then vacuum dried to obtain a powdery polymer (polymer A). The molecular weight of polymer A was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 20,000.

In addition, the weight average molecular weight of the resin obtained in each production example was measured by gel permeation chromatography (GPC) under the following conditions to obtain the weight average molecular weight in terms of standard polystyrene.

Pump: JASCO PU-980

Detector: JASCO RI-930

Column oven: JASCO CO-965 40℃

Column: 2 Shodex KD-806M in series

Mobile phase: 0.1mol/L LiBr/NMP

Flow rate: 1ml/min.

<Production Example 2> ((A) Synthesis of Polymer B as a Polyimide Precursor)

Use 147.1g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) instead of 155.1g of 4,4'-oxydiphthalic dianhydride (ODPA) of Production Example 1, except that Otherwise, the reaction was carried out in the same manner as the method described in Production Example 1 above to obtain polymer B. The molecular weight of polymer B was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 22,000.

<Production Example 3> ((A) Synthesis of Polymer C as a Polyimide Precursor)

Use 147.8g of 2,2'-bistrifluoromethyl-4,4'-diaminobiphenyl (TFMB) instead of 93.0g of 4,4'-diaminodiphenyl ether (DADPE) of Production Example 1, except Otherwise, the reaction was carried out in the same manner as the method described in Production Example 1 above to obtain polymer C. The molecular weight of polymer C was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 21,000.

<Production Example 4> ((A) Synthesis of polymer D as polyamide)

(Synthesis of phthalic acid compound end cap AIPA-MO)

Put 5-aminoisophthalic acid {herein abbreviated as AIPA}543.5g and 1700g of N-methyl-2-pyrrolidone into a separable flask with a volume of 5L, mix and stir, and heat to 50°C in a water bath . Add 512.0g (3.3mol) of 2-methacryloxyethyl isocyanate to 500g of γ-butyrolactone by adding dropwise into it using a dropping funnel, and stir directly at 50°C for 2 hours about.

After confirming the completion of the reaction (the disappearance of 5-aminoisophthalic acid) by low-molecular-weight gel permeation chromatography {hereinafter referred to as low-molecular-weight GPC}, the reaction solution was poured into 15L of ion-exchanged water, stirred, and Let stand, filter and separate the reaction product after crystallization and precipitation, after proper washing with water, vacuum drying at 40°C for 48 hours, thereby obtaining the amine group of 5-aminoisophthalic acid and isocyanic acid AIPA-MO obtained by the action of isocyanate group of 2-methacryloxyethyl. The low molecular weight GPC purity of the obtained AIPA-MO is about 100%.

(Synthesis of polymer D)

Put the obtained AIPA-MO 100.89g (0.3mol), pyridine 71.2g (0.9mol), and GBL 400g into a separable flask with a volume of 2L, mix them, and cool to 5°C with an ice bath. Under ice-bath cooling, the dicyclohexylcarbodiimide (DCC) 125.0g (0.606mol) was dissolved and diluted in GBL 125g, and then the mixture was added dropwise for about 20 minutes. ,4'-bis(4-aminophenoxy)biphenyl {hereafter referred to as BAPB} 103.16g (0.28mol) dissolved in 168g of NMP, kept in an ice bath for 3 hours below 5℃, then removed Ice bath, stirring at room temperature for 5 hours. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.

A mixed solution of 840 g of water and 560 g of isopropanol was added dropwise to the obtained reaction liquid, and the precipitated polymer was separated and redissolved in 650 g of NMP. The obtained crude polymer solution was dropped into 5 L of water to precipitate the polymer, and the obtained precipitate was separated by filtration, and then vacuum dried to obtain a powdery polymer (polymer E). The molecular weight of polymer D was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 34,700.

唑前驅物之聚合物E之合成) <Manufacturing Example 5> ((A) is used as poly

(Synthesis of polymer E of azole precursor)

Put 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane in a 3L separable flask 183.1 g, 640.9 g of N,N-dimethylacetamide (DMAc), and 63.3 g of pyridine were mixed and stirred at room temperature (25°C) to prepare a uniform solution. The solution obtained by dissolving 118.0 g of 4,4'-diphenyl ether dimethyl chloride in 354 g of diethylene glycol dimethyl ether (DMDG) was added dropwise to it using a dropping funnel. At this point, cool the separable flask in a water bath at 15-20°C. The time required for dripping is 40 minutes, and the temperature of the reaction solution is up to 30°C.

唑前驅物。 After 3 hours after the dripping, add 30.8g (0.2mol) of 1,2-cyclohexyldicarboxylic anhydride to the reaction solution, stir and stand at room temperature for 15 hours to make the polymer chain account for 99% of the total amine The terminal group is capped with a carboxycyclohexylamino group. The reaction rate at this time can be easily calculated by tracing the residual amount of the charged 1,2-cyclohexyldicarboxylic anhydride by high performance liquid chromatography (HPLC). After that, the above reaction solution was added dropwise to 2L of water under high-speed stirring to disperse and precipitate the polymer. The polymer was recovered, washed with water, dehydrated, and vacuum dried to obtain a gel permeation chromatography (GPC) Crude polybenzo with a weight-average molecular weight of 9,000 (in terms of polystyrene) measured by the method

Azole precursors.

唑前驅物再溶解於γ-丁內酯(GBL)後，對其利用陽離子交換樹脂及陰離子交換樹脂進行處理，將藉此獲得之溶液投入至離子交換水中後，過濾分離所析出之聚合物，進行水洗並真空乾燥，藉此獲得經精製之聚苯并

唑前驅物(聚合物E)。 Make the crude polybenzo

After the azole precursor is re-dissolved in γ-butyrolactone (GBL), it is treated with a cation exchange resin and an anion exchange resin, the resulting solution is poured into ion exchange water, and the precipitated polymer is separated by filtration. Wash with water and dry in vacuum to obtain refined polybenzo

Azole precursor (Polymer E).

<Production Example 6> ((A) Synthesis of Polymer F as Polyimine)

Install a cooling tube with a Dean-Stark separator to a glass separable four-neck flask equipped with a Teflon (registered trademark) anchor type stirrer. While nitrogen gas was introduced, the flask was immersed in a silicon oil bath for stirring.

烯-2,3-二羧酸酐(東京化成工業股份有限公司製造)4.6g(28mmol)，一面通入氮氣一面於矽浴溫度50℃下以100rpm加熱攪拌8小時。其後，加熱至矽浴溫度180℃，以100rpm加熱攪拌2小時。去除於反應中所餾出之甲苯、水。醯亞胺化反應結束後恢復至室溫。 Add 2,2-bis(3-amino-4-hydroxyphenyl)propane (manufactured by Clariant Japan) (hereinafter referred to as BAP) 72.28g (280mmol), 5-(2,5-dioxotetrahydro- 3-furyl)-3-methyl-cyclohexene-1,2 dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) (hereinafter referred to as MCTC) 70.29 g (266 mmol), γ-butyrolactone 254.6 g, 60g of toluene, after stirring at 100 rpm for 4 hours at room temperature, add 5-drop

4.6 g (28 mmol) of ene-2,3-dicarboxylic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was heated and stirred at 100 rpm at a silicon bath temperature of 50° C. for 8 hours while passing nitrogen gas. Then, it heated to 180 degreeC of silicon bath temperature, and it heated and stirred at 100 rpm for 2 hours. Remove the toluene and water distilled out in the reaction. After the imidization reaction is over, return to room temperature.

After that, the above reaction solution was added dropwise to 3L of water under high-speed stirring to disperse and precipitate the polymer, which was recovered, washed with appropriate water, dehydrated, and vacuum dried to obtain a gel permeation chromatography (GPC) method. The measured weight average molecular weight of 23,000 (polystyrene conversion) crude polyimide (polymer F).

<Production Example 7> ((A) Synthesis of polymer G as phenol resin)

Put 128.3g (0.76mol) of methyl 3,5-dihydroxybenzoate and 4,4'-bis(methoxymethyl) into a separable flask with a Dean-Stark device with a volume of 0.5L Biphenyl (hereinafter also referred to as "BMMB") 121.2g (0.5mol), diethylsulfuric acid 3.9g (0.025mol), and diethylene glycol dimethyl ether 140g were mixed and stirred at 70°C to dissolve the solid .

The mixed solution was heated to 140°C in an oil bath, and it was confirmed that methanol was generated from the reaction solution. The reaction solution was stirred directly at 140°C for 2 hours.

Then, the reaction vessel was cooled in the atmosphere, and 100 g of tetrahydrofuran was additionally added thereto and stirred. The above-mentioned reaction diluent was added dropwise to 4L of water under high-speed stirring to disperse and precipitate the resin, recovered, washed with water, dehydrated and vacuum dried to obtain 3,5-dihydroxybenzene with a yield of 70% Copolymer of methyl formate/BMMB (polymer G). The weight average molecular weight of this polymer G calculated by the standard polystyrene conversion of the GPC method was 21,000.

<Production Example 8> ((A) Synthesis of polymer H as phenol resin)

A separable flask with a Dean-Stark device with a volume of 1.0L was replaced with nitrogen. Then, 81.3g (0.738mol) of resorcinol and 84.8g (0.35mol of BMMB) were added to the separable flask. ), 3.81 g (0.02 mol) of p-toluenesulfonic acid and 116 g of propylene glycol monomethyl ether (hereinafter also referred to as PGME) were mixed and stirred at 50°C to dissolve the solids.

The mixed solution was heated to 120°C in an oil bath, and it was confirmed that methanol was generated from the reaction solution. The reaction solution was stirred directly at 120°C for 3 hours.

Then, 24.9g (0.150mol) of 2,6-bis(hydroxymethyl)p-cresol and 249g of PGME were mixed and stirred in another container to make them uniformly dissolved, and the obtained solution was used in a dropping funnel for 1 It was added dropwise to the separable flask for 2 hours, and stirred for 2 hours after the dropping.

After the reaction was completed, the same treatment as in Production Example 7 was performed to obtain a copolymer (polymer H) containing resorcinol/BMMB/2,6-bis(hydroxymethyl)p-cresol at a yield of 77%. The weight average molecular weight of this polymer H calculated by the standard polystyrene conversion of the GPC method was 9,900.

<Example 1>

Using polymers A and B, a negative photosensitive resin composition was prepared by the following method, and the prepared photosensitive resin composition was evaluated. The polyimide precursor polymers A 50g and B 50g (equivalent to (A) resin) and zirconium phosphate (plate-like particles with a long axis of 100nm and a short axis of 5nm, equivalent to an aspect ratio of 20 (B-1 ) Nanoparticles) 5g, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime (denoted as "PDO" in Table 1) (equivalent to (C) sensitizer ) 4g, 8g of tetraethylene glycol dimethacrylate, 1.5g of N-[3-(triethoxysilyl)propyl]phthalic acid and 1.5g are dissolved in N-methyl-2- A mixed solvent of 80 g of pyrrolidone (hereinafter referred to as NMP) and 20 g of ethyl lactate. The viscosity of the obtained solution was adjusted to about 35 poise by further adding a small amount of the above-mentioned mixed solvent, and a negative photosensitive resin composition was prepared.

For this composition, a hardened float was produced on the Cu layer by curing at 230°C by the above method. The convex pattern was subjected to a high-temperature storage test to evaluate the area ratio of the voids on the surface of the Cu layer, and a result of 5.5% was obtained.

<Example 2>

In Example 1 described above, as the component (B-1), except that the addition amount of zirconium phosphate was changed to 1 g, a negative photosensitive resin composition solution was prepared in the same manner as in Example 1.

For the composition, cured at 230°C by the above-mentioned method to produce a hardened relief pattern on the Cu layer. After a high temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated, and a result of 6.6% was obtained.

<Example 3>

In the above-mentioned Example 1, as the component (B-1), montmorillonite (plate-like particles with a long axis of 100 nm, a short axis of 10 nm, and an aspect ratio of 10) was used instead of zirconium phosphate, except that it was the same as in Example 1 In this way, a negative photosensitive resin composition solution was prepared.

For the composition, cured at 230°C by the above method to produce a hardened relief pattern on the Cu layer, and after a high temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated, and a result of 5.8% was obtained.

<Example 4>

In the above-mentioned Example 1, as the component (B-1), 1 g of Airotech (spherical particles with a particle diameter of 12 nm, aspect ratio 1) was used instead of 5 g of zirconium phosphate, except that it was prepared in the same manner as in Example 1. Negative photosensitive resin composition solution.

For this composition, cured at 230°C by the above method to produce a hardened relief pattern on the Cu layer, and after a high temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated, and a result of 5.4% was obtained.

<Example 5>

A negative photosensitive resin composition solution was prepared in the same manner as in Example 1 above. The composition was cured at 350°C by the above method to form a hardened relief pattern on the Cu layer, and after a high temperature storage test, The area ratio of voids to the surface of the Cu layer was evaluated, and a result of 4.5% was obtained.

<Example 6>

In the above Example 1, as the (A) resin, 50 g of polymer A and 50 g of polymer B were changed to 100 g of polymer A, and 4 g of PDO was changed to 1,2-octanedione-1 as component (C). -{4-(phenylthio)-2-(O-benzyloxime)} (Irgacure OXE01 (manufactured by BASF Corporation, trade name)) 2.5g, except for this, in the same manner as in Example 1 A negative photosensitive resin composition solution is prepared.

For the composition, cured at 230°C by the above method to produce a hardened relief pattern on the Cu layer, and after a high temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated, and a result of 5.3% was obtained.

<Example 7>

In the above Example 1, as the (A) resin, 50 g of polymer A and 50 g of polymer B were changed to 100 g of polymer A, and 4 g of PDO was changed to 1,2-octanedione-1 as component (C). -{4-(phenylthio)-2-(O-benzyl oxime)} (Irgacure OXE01 (manufactured by BASF, trade name)) 2.5g, and then the solvent is changed to 85g of γ-butyrolactone and two Except 15 g of methyl sulfene, a negative photosensitive resin composition solution was prepared in the same manner as in Example 1.

For the composition, cured at 230°C by the above method to produce a hardened relief pattern on the Cu layer, and after a high temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated, and a result of 5.3% was obtained.

<Example 8>

In Example 1 above, as the resin (A), a negative photosensitive resin composition was prepared in the same manner as in Example 1, except that 50 g of polymer A and 50 g of polymer B were changed to 100 g of polymer C. Solution.

For this composition, cured at 350°C by the above method to produce a hardened relief pattern on the Cu layer, and after a high temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated, and a result of 4.8% was obtained.

<Example 9>

In Example 1 above, as the resin (A), a negative photosensitive resin composition was prepared in the same manner as in Example 1, except that 50 g of polymer A and 50 g of polymer B were changed to 100 g of polymer D. Solution.

For this composition, cured at 250°C by the above-mentioned method to produce a hardened relief pattern on the Cu layer. After a high temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated, and a result of 5.6% was obtained.

<Example 10>

唑前驅物之聚合物E 100g(相當於(A)樹脂)與下述式(96)： [化128]

Using the polymer E, a positive photosensitive resin composition was prepared by the following method, and the prepared photosensitive resin composition was evaluated. Will be as poly

100g of polymer E of the azole precursor (equivalent to (A) resin) and the following formula (96): [化128]

77% of the phenolic hydroxyl group represented by naphthoquinone diazide-4-sulfonic acid esterified photosensitive diazoquinone compound (manufactured by Toyo Gosei, equivalent to (C) sensitizer) (C1) 15g, zirconium phosphate (Plate particles with a length of 100nm and a thickness of 5nm are equivalent to (B) nanoparticle) 5g and 6g of 3-tertiary butoxycarbonylaminopropyltriethoxysilane are dissolved in γ-butyrolactone (As a solvent) 100g. Further, by adding a small amount of γ-butyrolactone, the viscosity of the obtained solution was adjusted to about 20 poises to prepare a positive photosensitive resin composition.

For this composition, a hardened relief pattern was made on the Cu layer by curing at 350°C by the above method. After a high temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated, and a result of 5.7% was obtained.

<Example 11>

In the above-mentioned Example 10, as the (A) resin, except that 100 g of the polymer E was changed to 100 g of the polymer F, a positive photosensitive resin composition solution was prepared in the same manner as in Example 10.

For this composition, cured at 250°C by the above-mentioned method to produce a hardened relief pattern on the Cu layer, and after a high temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated Rate, and get a result of 5.7%.

<Example 12>

In the above Example 10, as the (A) resin, a positive photosensitive resin composition solution was prepared in the same manner as in Example 10 except that 100 g of the polymer E was changed to 100 g of the polymer G.

For this composition, cured at 220°C by the above method to produce a hardened relief pattern on the Cu layer, and after a high temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated, and a result of 5.4% was obtained.

<Example 13>

In the above-mentioned Example 10, as the (A) resin, a positive photosensitive resin composition solution was prepared in the same manner as in Example 10, except that 100 g of the polymer E was changed to 100 g of the polymer H.

For this composition, cured at 220°C by the above-mentioned method to make a hardened relief pattern on the Cu layer. After a high temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated, and a result of 5.5% was obtained.

<Comparative Example 1>

In the composition of Example 1, except that zirconium phosphate was not added, a negative photosensitive resin composition was prepared in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. Since the compound (B) of the present invention is not contained, the evaluation result is 14.3%.

<Comparative Example 2>

In the composition of Example 8, a negative photosensitive resin composition was prepared in the same manner as in Example 8 except that zirconium phosphate was not added, and the same evaluation as in Example 10 was performed. Since the compound (B) of the present invention is not contained, the evaluation result is 14.9%.

<Comparative Example 3>

In the composition of Example 10, except that zirconium phosphate was not added, a positive photosensitive resin composition was prepared in the same manner as in Example 10, and the same evaluation as in Example 10 was performed. Since the compound (B) of the present invention is not contained, the evaluation result is 14.6%.

These results are summarized in Table 2.

<The third embodiment>

As a third example, the following experiment was performed.

<Production Example 1> ((A) Synthesis of polymer A as a precursor of polyimide)

Put 155.1g of 4,4'-oxydiphthalic dianhydride (ODPA) in a separable flask with a volume of 2L, add 131.2g of 2-hydroxyethyl methacrylate (HEMA) and γ-butyrolactone 400 ml was stirred at room temperature, and 81.5 g of pyridine was added while stirring to obtain a reaction mixture. After the exotherm caused by the reaction is over, it is allowed to stand and cool to room temperature for 16 hours.

Then, under cooling in an ice bath, a solution obtained by dissolving 206.3 g of dicyclohexyl carbodiimide (DCC) in 180 ml of γ-butyrolactone was added to the reaction mixture while stirring for 40 minutes, and then stirring was carried out. What was obtained by suspending 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) in 350 ml of γ-butyrolactone was added over 60 minutes. After further stirring for 2 hours at room temperature, 30 ml of ethanol was added and stirred for 1 hour, and then 400 ml of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.

The obtained reaction solution was added to 3 L of ethanol to generate a precipitate containing crude polymer. The produced crude polymer was separated by filtration and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 L of water to precipitate the polymer, and the obtained precipitate was separated by filtration, and then vacuum dried to obtain a powdery polymer (polymer A). The molecular weight of polymer A was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 20,000.

In addition, the weight average molecular weight of the resin obtained in each production example was measured by gel permeation chromatography (GPC) under the following conditions to obtain the weight average molecular weight in terms of standard polystyrene.

Pump: JASCO PU-980

Detector: JASCO RI-930

Column oven: JASCO CO-965 40℃

Column: 2 Shodex KD-806M in series

Mobile phase: 0.1mol/L LiBr/NMP

Flow rate: 1ml/min.

<Production Example 2> ((A) Synthesis of Polymer B as a Polyimide Precursor)

Use 147.1g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) instead of 155.1g of 4,4'-oxydiphthalic dianhydride (ODPA) of Production Example 1, except that Otherwise, the reaction was carried out in the same manner as the method described in Production Example 1 above to obtain polymer B. The molecular weight of polymer B was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 22,000.

<Production Example 3> ((A) Synthesis of Polymer C as a Polyimide Precursor)

Use 147.8g of 2,2'-bistrifluoromethyl-4,4'-diaminobiphenyl (TFMB) instead of 93.0g of 4,4'-diaminodiphenyl ether (DADPE) of Production Example 1, except Otherwise, the reaction was carried out in the same manner as the method described in Production Example 1 above to obtain polymer C. The molecular weight of polymer C was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 21,000.

<Production Example 4> ((A) Synthesis of polymer D as polyamide)

(Synthesis of phthalic acid compound end cap AIPA-MO)

Put 5-aminoisophthalic acid {herein abbreviated as AIPA}543.5g and 1700g of N-methyl-2-pyrrolidone into a separable flask with a volume of 5L, mix and stir, and heat to 50°C in a water bath . Add 512.0g (3.3mol) of 2-methacryloxyethyl isocyanate to 500g of γ-butyrolactone by adding dropwise into it using a dropping funnel, and stir directly at 50°C for 2 hours about.

After confirming the completion of the reaction (the disappearance of 5-aminoisophthalic acid) by low-molecular-weight gel permeation chromatography {hereinafter referred to as low-molecular-weight GPC}, the reaction solution was poured into 15L of ion-exchanged water, stirred, and Let stand, filter and separate the reaction product after crystallization and precipitation, after proper washing with water, vacuum drying at 40°C for 48 hours, thereby obtaining the amine group of 5-aminoisophthalic acid and isocyanic acid AIPA-MO obtained by the action of isocyanate group of 2-methacryloxyethyl. The low molecular weight GPC purity of the obtained AIPA-MO is about 100%.

(Synthesis of polymer D)

Put the obtained AIPA-MO 100.89g (0.3mol), pyridine 71.2g (0.9mol), and GBL 400g into a separable flask with a volume of 2L, mix them, and cool to 5°C with an ice bath. Under ice-bath cooling, the dicyclohexylcarbodiimide (DCC) 125.0g (0.606mol) was dissolved and diluted in GBL 125g, and then the mixture was added dropwise for about 20 minutes. ,4'-bis(4-aminophenoxy)biphenyl {hereafter referred to as BAPB} 103.16g (0.28mol) dissolved in 168g of NMP, kept in an ice bath for 3 hours below 5℃, then removed Ice bath, stirring at room temperature for 5 hours. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.

A mixed solution of 840 g of water and 560 g of isopropanol was added dropwise to the obtained reaction liquid, and the precipitated polymer was separated and redissolved in 650 g of NMP. The obtained crude polymer solution was dropped into 5 L of water to precipitate the polymer, and the obtained precipitate was separated by filtration, and then vacuum dried to obtain a powdery polymer (polymer E). The molecular weight of polymer D was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 34,700.

<Example 1>

Using polymers A and B, a negative photosensitive resin composition was prepared by the following method, and The prepared photosensitive resin composition was evaluated. Combine polymer A 50g and B 50g (equivalent to (A) resin) as polyimide precursors and TMOM-BP (trade name, Honshu Chemical, equivalent to (B-2) thermal crosslinking agent) 10g, 1 -Phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime (denoted as "PDO" in Table 1) (equivalent to (C) sensitizer) 4g, tetraethylene glycol two 8g of methacrylate, 1.5g of N-[3-(triethoxysilyl)propyl]phthalic acid and 1.5g of methacrylic acid were dissolved together in N-methyl-2-pyrrolidone (hereinafter referred to as NMP ) A mixed solvent of 80 g and 20 g of ethyl lactate. The viscosity of the obtained solution was adjusted to about 35 poise by further adding a small amount of the above-mentioned mixed solvent, and a negative photosensitive resin composition was prepared.

For the composition, cured at 230°C by the above method to produce a hardened relief pattern on the Cu layer, and after a high temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated, and a result of 5.7% was obtained.

<Example 2>

In the above-mentioned Example 1, except that the addition amount of TMOM-BP was changed to 20 g as the component (B-2), a negative photosensitive resin composition solution was prepared in the same manner as in Example 1.

For the composition, cured at 230°C by the above method to produce a hardened relief pattern on the Cu layer, and after a high temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated, and a result of 3.8% was obtained.

<Example 3>

In the above-mentioned Example 1, except that the addition amount of TMOM-BP was changed to 5 g as the component (B-2), the negative photosensitive resin composition solution was prepared in the same manner as in Example 1.

For this composition, cured at 230°C by the above method to produce a hardened relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated, and a result of 9.3% was obtained.

<Example 4>

In the above-mentioned Example 1, as the component (B-2), TM-BIP-A (trade name, Honshu Chemical) was used instead of TMOM-BP, except that the negative photosensitive was prepared in the same manner as in Example 1. Resin composition solution.

For this composition, cured at 230°C by the above-mentioned method to produce a hardened relief pattern on the Cu layer. After a high temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated, and a result of 5.2% was obtained.

<Example 5>

In the above-mentioned Example 1, as the component (B-2), HMOM-TP-HAP (trade name, Honshu Chemical) was used instead of TMOM-BP, except that the negative photosensitive was prepared in the same manner as in Example 1. Resin composition solution.

For the composition, cured at 230°C by the above method to produce a hardened relief pattern on the Cu layer, and after a high temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated, and a result of 5.8% was obtained.

<Example 6>

In the above-mentioned Example 1, as the component (B-2), NIKALAC MW-390 (trade name, SANWA CHEMICAL) was used instead of TMOM-BP, except that the negative photosensitive resin was prepared in the same manner as in Example 1. Composition solution.

For the composition, cured by the above method at 230°C to produce a hardened relief pattern on the Cu layer, and after a high temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated, and a result of 10.3% was obtained.

<Example 7>

In the above Example 1, as the resin (A), 50 g of polymer A and 50 g of polymer B were changed to Except for 100 g of polymer A, a negative photosensitive resin composition solution was prepared in the same manner as in Example 1.

For the composition, cured at 230°C by the above method to produce a hardened relief pattern on the Cu layer, and after a high temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated, and a result of 5.3% was obtained.

<Example 8>

In the above Example 1, as the (A) resin, 50 g of polymer A and 50 g of polymer B were changed to 100 g of polymer A, and 4 g of PDO was changed to 1,2-octanedione-1 as component (C). -{4-(phenylthio)-2-(O-benzyl oxime)} (Irgacure OXE01 (manufactured by BASF Corporation, trade name)) 2.0g, and then change the solvent to 80g of γ-butyrolactone and two Except 20 g of methyl sulfene, a negative photosensitive resin composition solution was prepared in the same manner as in Example 1.

For the composition, cured at 230°C by the above method to produce a hardened relief pattern on the Cu layer, and after a high temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated, and a result of 5.8% was obtained.

<Example 9>

In Example 1 above, as the resin (A), a negative photosensitive resin composition was prepared in the same manner as in Example 1, except that 50 g of polymer A and 50 g of polymer B were changed to 100 g of polymer C. Solution.

For the composition, cured at 350°C by the above method to produce a hardened relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated, and a result of 5.0% was obtained.

<Example 10>

In the above Example 1, as the resin (A), 50 g of polymer A and 50 g of polymer B were changed to Except for the polymer D 100 g, a negative photosensitive resin composition solution was prepared in the same manner as in Example 1.

For this composition, cured at 250°C by the above-mentioned method to produce a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated, and a result of 6.9% was obtained.

<Comparative Example 1>

In the composition of Example 1, except that TMOM-BP was not added, a negative photosensitive resin composition was prepared in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. Since the compound (B) of the present invention is not contained, the evaluation result is 14.3%.

<Comparative Example 2>

In the composition of Example 10, except that TMOM-BP was not added, a negative photosensitive resin composition was prepared in the same manner as in Example 10, and the same evaluation as in Example 11 was performed. Since the compound (B) of the present invention is not included, the evaluation result is 15.5%.

The results of these Examples 1-10 and Comparative Examples 1-2 are collectively shown in Table 3.

<Fourth embodiment>

As a fourth example, the following experiment was performed.

<Production Example 1> ((A) Synthesis of Polymer (A)-1 as Polyimide Precursor)

Put 155.1g of 4,4'-oxydiphthalic dianhydride (ODPA) in a separable flask with a volume of 2L, add 131.2g of 2-hydroxyethyl methacrylate (HEMA) and γ-butyrolactone 400 ml was stirred at room temperature, and 81.5 g of pyridine was added while stirring to obtain a reaction mixture. After the exotherm caused by the reaction is over, it is allowed to stand and cool to room temperature for 16 hours.

Then, under cooling in an ice bath, a solution obtained by dissolving 206.3 g of dicyclohexyl carbodiimide (DCC) in 180 ml of γ-butyrolactone was added to the reaction mixture while stirring for 40 minutes, and then stirring was carried out. What was obtained by suspending 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) in 350 ml of γ-butyrolactone was added over 60 minutes. After further stirring for 2 hours at room temperature, 30 ml of ethanol was added and stirred for 1 hour, and then 400 ml of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.

The obtained reaction solution was added to 3 L of ethanol to generate a precipitate containing crude polymer. The produced crude polymer was separated by filtration and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 L of water to precipitate the polymer, and the obtained precipitate was separated by filtration and then vacuum dried to obtain a powdery polymer (polymer (A)-1). The molecular weight of the polymer (A)-1 was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 20,000.

In addition, the weight average molecular weight of the resin obtained in each production example was measured by gel permeation chromatography (GPC) under the following conditions to obtain the weight average molecular weight in terms of standard polystyrene.

Pump: JASCO PU-980

Detector: JASCO RI-930

Column oven: JASCO CO-965 40℃

Column: 2 Shodex KD-806M in series

Mobile phase: 0.1mol/L LiBr/NMP

Flow rate: 1ml/min.

<Production Example 2> ((A) Synthesis of polymer (A)-2 as a precursor of polyimide)

Use 147.1g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) instead of 155.1g of 4,4'-oxydiphthalic dianhydride (ODPA) of Production Example 1, except that Otherwise, the reaction was carried out in the same manner as the method described in Production Example 1 above to obtain polymer (A)-2. The molecular weight of the polymer (A)-2 was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 22,000.

<Production Example 3> ((A) Synthesis of polymer (A)-3 as a precursor of polyimide)

Use 147.8g of 2,2'-bistrifluoromethyl-4,4'-diaminobiphenyl (TFMB) instead of 93.0g of 4,4'-diaminodiphenyl ether (DADPE) of Production Example 1, except Otherwise, the reaction was carried out in the same manner as the method described in Production Example 1 above to obtain polymer (A)-3. The molecular weight of the polymer (A)-3 was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 21,000.

<Production Example 4> ((A) Synthesis of Polyamide (A)-4)

(Synthesis of phthalic acid compound end cap AIPA-MO)

Put 5-aminoisophthalic acid {herein abbreviated as AIPA}543.5g and 1700g of N-methyl-2-pyrrolidone into a separable flask with a volume of 5L, mix and stir, and heat to 50°C in a water bath . Add 512.0g (3.3mol) of 2-methacryloxyethyl isocyanate to 500g of γ-butyrolactone by adding dropwise into it using a dropping funnel, and stir directly at 50°C for 2 hours about.

After confirming the completion of the reaction (the disappearance of 5-aminoisophthalic acid) by low-molecular-weight gel permeation chromatography {hereinafter referred to as low-molecular-weight GPC}, the reaction solution was poured into 15L of ion-exchanged water, stirred, and Let stand, filter and separate the reaction product after crystallization and precipitation, after proper washing with water, vacuum drying at 40°C for 48 hours, thereby obtaining the amine group of 5-aminoisophthalic acid and isocyanic acid AIPA-MO obtained by the action of isocyanate group of 2-methacryloxyethyl. The low molecular weight GPC purity of the obtained AIPA-MO is about 100%.

(Synthesis of polymer (A)-4)

Put the obtained AIPA-MO 100.89g (0.3mol), pyridine 71.2g (0.9mol), and GBL 400g into a separable flask with a volume of 2L, mix them, and cool to 5°C with an ice bath. Under ice-bath cooling, the dicyclohexylcarbodiimide (DCC) 125.0g (0.606mol) was dissolved and diluted in GBL 125g, and then the mixture was added dropwise for about 20 minutes. ,4'-bis(4-aminophenoxy)biphenyl {hereafter referred to as BAPB} 103.16g (0.28mol) dissolved in 168g of NMP, kept in an ice bath for 3 hours below 5℃, then removed Ice bath, stirring at room temperature for 5 hours. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.

A mixed solution of 840 g of water and 560 g of isopropanol was added dropwise to the obtained reaction liquid, and the precipitated polymer was separated and redissolved in 650 g of NMP. The obtained crude polymer solution was dropped into 5 L of water to precipitate the polymer, and the obtained precipitate was separated by filtration and then vacuum dried to obtain a powdery polymer (polymer (A)-4). The molecular weight of the polymer (A)-4 was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 34,700.

唑前驅物之聚合物(A)-5之合成) <Manufacturing Example 5> ((A) is used as poly

(Synthesis of azole precursor polymer (A)-5)

In a separable flask with a volume of 3L, 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane 183.1g, N,N-dimethylacetamide (DMAc) 640.9g, 63.3 g of pyridine was mixed and stirred at room temperature (25°C) to make a uniform solution. The solution obtained by dissolving 118.0 g of 4,4'-diphenyl ether dimethyl chloride in 354 g of diethylene glycol dimethyl ether (DMDG) was added dropwise to it using a dropping funnel. At this point, cool the separable flask in a water bath at 15-20°C. The time required for dripping is 40 minutes, and the temperature of the reaction solution is up to 30°C.

After 3 hours after the dripping, add 30.8g (0.2mol) of 1,2-cyclohexyldicarboxylic anhydride to the reaction solution, stir and stand at room temperature for 15 hours to make the polymer chain account for 99% of the total amine The terminal group is capped with a carboxycyclohexylamino group. The reaction rate at this time can be easily calculated by tracing the residual amount of the charged 1,2-cyclohexyldicarboxylic anhydride by high performance liquid chromatography (HPLC). After that, the above reaction solution was added dropwise to 2L of water under high-speed stirring to disperse and precipitate the polymer. The polymer was recovered, washed with water, dehydrated, and vacuum dried to obtain a gel permeation chromatography (GPC) A crude precursor with a weight average molecular weight of 9,000 (in terms of polystyrene) measured by the method.

唑前驅物再溶解於γ-丁內酯(GBL)後，對其利用陽離子交換樹脂及陰離子交換樹脂進行處理，將藉此獲得之溶液投入至離子交換水中後，過濾分離所析出之聚合物，進行水洗並真空乾燥，藉此獲得經精製之聚苯并

唑前驅物(聚合物(A)-5)。 Make the crude polybenzo

After the azole precursor is re-dissolved in γ-butyrolactone (GBL), it is treated with a cation exchange resin and an anion exchange resin, the resulting solution is poured into ion exchange water, and the precipitated polymer is separated by filtration. Wash with water and dry in vacuum to obtain refined polybenzo

Azole precursor (Polymer (A)-5).

<Production Example 6> ((A) Synthesis of polyimide polymer (A)-6)

Install a cooling tube with a Dean-Stark separator to a glass separable four-neck flask equipped with a Teflon (registered trademark) anchor type stirrer. While nitrogen gas was introduced, the flask was immersed in a silicon oil bath for stirring.

烯-2,3-二羧酸酐(東京化成工業股份有限公司製造)4.6g(28mmol)，一面通入氮氣一面於矽浴溫度50℃下以100rpm加熱攪拌8小時。其後，加熱至矽浴溫度180℃，以100rpm加熱攪拌2小時。去除於反應中所餾出之甲苯、水。醯亞胺化反應結束後恢復至室溫。 Add 2,2-bis(3-amino-4-hydroxyphenyl)propane (manufactured by Clariant Japan) (hereinafter referred to as BAP) 72.28g (280mmol), 5-(2,5-dioxotetrahydro- 3-furyl)-3-methyl-cyclohexene-1,2 dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) (hereinafter referred to as MCTC) 70.29 g (266 mmol), γ-butyrolactone 254.6 g, 60g of toluene, after stirring at 100 rpm for 4 hours at room temperature, add 5-drop

4.6 g (28 mmol) of ene-2,3-dicarboxylic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was heated and stirred at 100 rpm at a silicon bath temperature of 50° C. for 8 hours while passing nitrogen gas. Then, it heated to 180 degreeC of silicon bath temperature, and it heated and stirred at 100 rpm for 2 hours. Remove the toluene and water distilled out in the reaction. After the imidization reaction is over, return to room temperature.

After that, the above reaction solution was added dropwise to 3L of water under high-speed stirring to disperse and precipitate the polymer, which was recovered, washed with appropriate water, dehydrated, and vacuum dried to obtain a gel permeation chromatography (GPC) method. The measured crude polyimide (polymer (A)-6) with a weight average molecular weight of 23,000 (in terms of polystyrene).

<Production Example 7> ((A) Synthesis of Polymer (A)-8 as Phenolic Resin)

A separable flask with a Dean-Stark device with a volume of 1.0L was replaced with nitrogen. Then, 81.3g (0.738mol) of resorcinol and 84.8g (0.35mol of BMMB) were added to the separable flask. ), 3.81 g (0.02 mol) of p-toluenesulfonic acid and 116 g of propylene glycol monomethyl ether (hereinafter also referred to as PGME) were mixed and stirred at 50°C to dissolve the solids.

The mixed solution was heated to 120°C in an oil bath, and it was confirmed that methanol was generated from the reaction solution. The reaction solution was stirred directly at 120°C for 3 hours.

Then, 24.9g (0.150mol) of 2,6-bis(hydroxymethyl)p-cresol and 249g of PGME were mixed and stirred in another container to make them uniformly dissolved, and the obtained solution was used in a dropping funnel for 1 It was added dropwise to the separable flask for 2 hours, and stirred for 2 hours after the dropping.

After the reaction was completed, the same treatment as in Production Example 7 was performed to obtain a copolymer (polymer H) containing resorcinol/BMMB/2,6-bis(hydroxymethyl)p-cresol at a yield of 77%. The weight average molecular weight of this polymer H calculated by the standard polystyrene conversion of the GPC method was 9,900.

<Example 1>

Using polymers (A)-1 and (A)-2, a negative photosensitive resin composition was prepared by the following method, and the photosensitive resin composition was evaluated. Combine the polymer (A)-1 50g and (A)-2 50g (equivalent to (A) resin) as the precursor of polyimide and 1H, 1H, 8H, 8H-perfluorotetraethylene glycol diacrylate (Expressed by the following formula (B-3-1), manufactured by Exfluor) 8g, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime (in Table 1 "PDO") (equivalent to (C) sensitizer) 4g, tetraethylene glycol dimethacrylate 8g, N-[3-(triethoxysilyl)propyl]phthalic acid 1.5g It was dissolved in a mixed solvent containing 80 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) and 20 g of ethyl lactate. The viscosity of the obtained solution was adjusted to about 35 poise by further adding a small amount of the above-mentioned mixed solvent, and a negative photosensitive resin composition was prepared.

For this composition, cured by the above method at 230°C to produce a hardened relief pattern on the Cu layer, and after a high temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated, and a result of 3.1% was obtained. Furthermore, (B-3)-1 compound (represents a compound of the following formula (B-3-1). Hereinafter, the compound represented by the following formula (B-3-X) (X is 1 to 9) The weight ratio of fluorine atoms in the molecule of (B-3)-X) is 44% by mass.

<Example 2>

In the above Example 1, the component (B-3) was changed to 1H, 1H, 6H, 6H-perfluoro-1,6-hexanediol diacrylate (represented by (the following formula (B-2), Exfluor Company manufactured), except for this, a negative photosensitive resin composition solution was prepared in the same manner as in Example 1.

For the composition, cured at 230°C by the above-mentioned method to produce a hardened relief pattern on the Cu layer. After a high temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated, and a result of 3.3% was obtained. Furthermore, the weight ratio of fluorine atoms in the molecule of (B-3)-2 compound is 41% by mass.

<Example 3>

In the above-mentioned Example 1, the component (B-3) was changed to 1H,1H-perfluoro-n-decyl methacrylate (represented by the following formula (B-3-3), manufactured by Exfluor). Otherwise, borrow In the same manner as in Example 1, a negative photosensitive resin composition solution was prepared.

For the composition, cured at 230°C by the above method to produce a hardened relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated, and a result of 3.4% was obtained. Furthermore, the weight ratio of fluorine atoms in the molecule of (B-3)-3 compound is 64% by mass.

<Example 4>

In the above-mentioned Example 1, the component (B-3) was changed to perfluorodecanoic acid (represented by the following formula (B-3-4), manufactured by Exfluor), except for this, in the same manner as in Example 1 A negative photosensitive resin composition solution is prepared.

For this composition, cured at 230°C by the above method to produce a hardened relief pattern on the Cu layer. After a high temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated, and a result of 6.2% was obtained. Furthermore, the weight ratio of fluorine atoms in the molecule of (B-3)-4 compound is 70% by mass.

<Example 5>

In the above Example 1, the component (B-3) was changed to 1H,1H-perfluoro-1-decanol (represented by the following formula (B-3-5), manufactured by Exfluor). In addition, by In the same manner as in Example 1, a negative photosensitive resin composition solution was prepared.

For the composition, cured at 230°C by the above method to produce a hardened relief pattern on the Cu layer, and after a high temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated, and a result of 6.9% was obtained. Furthermore, the weight of the fluorine atom in the molecule of (B-3)-5 compound The ratio is 72% by mass.

<Example 6>

In the above-mentioned Example 1, the component (B-3) was changed to perfluorotridecane (represented by the following formula (B-3-6), manufactured by Exfluor), except that it was the same as in Example 1 Method Prepare a negative photosensitive resin composition solution.

For the composition, cured at 230°C by the above-mentioned method to produce a hardened relief pattern on the Cu layer. After a high temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated, and a result of 7.7% was obtained. Furthermore, the weight ratio of fluorine atoms in the molecule of (B-3)-6 compound is 77% by mass.

<Example 7>

In the above-mentioned Example 1, the component (B-3) was changed to methyl perfluorodecanoate (represented by the following formula (B-7), manufactured by Exfluor), except for this, in the same manner as in Example 1 A negative photosensitive resin composition solution is prepared.

For the composition, cured at 230°C by the above method to produce a hardened relief pattern on the Cu layer, and after a high temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated, and a result of 6.9% was obtained. Furthermore, the weight ratio of fluorine atoms in the molecule of (B-3)-7 compound is 68% by mass.

<Example 8>

In the above-mentioned Example 1, the component (B-3) was changed to perfluorotetraethylene glycol dimethyl ether (represented by the following formula (B-3-8), manufactured by Exfluor). The negative photosensitive resin composition solution was prepared in the same manner as in Example 1.

For this composition, cured at 230°C by the above-mentioned method to produce a hardened relief pattern on the Cu layer, and after a high temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated Rate, and get a result of 6.8%. Furthermore, the weight ratio of fluorine atoms in the molecule of the (B-3)-8 compound is 68% by mass.

<Example 9>

In the above-mentioned Example 1, except that the addition amount of the (B-3)-1 component was changed to 2 g, a negative photosensitive resin composition solution was prepared in the same manner as in Example 1.

For the composition, cured at 230°C by the above-mentioned method to produce a hardened relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated, and a result of 4.5% was obtained.

<Example 10>

In the above-mentioned Example 1, except that the addition amount of the (B-3)-1 component was changed to 20 g, a negative photosensitive resin composition solution was prepared in the same manner as in Example 1.

For the composition, cured at 230°C by the above method to produce a hardened relief pattern on the Cu layer, and after a high temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated, and a result of 3.8% was obtained.

<Example 11>

In the above-mentioned Example 1, except that the curing temperature was changed from 230°C to 350°C, a negative photosensitive resin composition solution was prepared in the same manner as in Example 1.

For this composition, a hardened relief pattern was made on the Cu layer, and after a high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated, and a result of 4.2% was obtained.

<Example 12>

In the above Example 1, as the resin (A), 50 g of polymer (A)-1 and 50 g of polymer (A)-2 were changed to 100 g of polymer (A)-1, and the component (C) was changed from PDO to 1,2-octanedione-1-{4-(phenylthio)-2-(O-benzyloxime)} (Irgacure OXE01 (manufactured by BASF Corporation, product Name)) 2.5 g, except for this, a negative photosensitive resin composition solution was prepared in the same manner as in Example 1.

For this composition, a hardened relief pattern was made on the Cu layer, and after a high temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated, and a result of 4.6% was obtained.

<Example 13>

In Example 12, the solvent was changed to 85 g of γ-butyrolactone and 15 g of dimethylsulfene. In the same manner as in Example 12, a negative photosensitive resin composition solution was prepared.

For the composition, a hardened relief pattern was made on the Cu layer, and after a high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated, and a result of 4.8% was obtained.

<Example 14>

In the above Example 1, as the resin (A), 50 g of polymer (A)-1 and 50 g of polymer (A)-2 were changed to 100 g of polymer (A)-3, and the curing temperature was changed from 230°C to Except for this at 350° C., a negative photosensitive resin composition solution was prepared in the same manner as in Example 1.

For this composition, a hardened relief pattern was made on the Cu layer, and after a high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated, and a result of 4.7% was obtained.

<Example 15>

In the above Example 1, as the resin (A), 50g of polymer (A)-1 and 50g of polymer (A)-2 were changed to 100g of polymer (A)-4, and the curing temperature was changed from 230°C to Except for this at 250° C., a negative photosensitive resin composition solution was prepared in the same manner as in Example 1.

For this composition, a hardened relief pattern was made on the Cu layer, and after a high temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated, and a result of 4.4% was obtained.

<Example 16>

唑前驅物之聚合物(A)-5 100g(相當於(A)樹脂)與下述式(96)：

Using polymer (A)-5, a positive photosensitive resin composition was prepared by the following method, and the prepared photosensitive resin composition was evaluated. Will be as poly

100g of azole precursor polymer (A)-5 (equivalent to (A) resin) and the following formula (96):

A photosensitive diazoquinone compound (manufactured by Toyo Gosei Co., Ltd., equivalent to component (C)) in which 77% of the phenolic hydroxyl group is esterified with naphthoquinone diazide-4-sulfonic acid (C1) 15g is dissolved in γ- Butyrolactone (as a solvent) 100g. Further, by adding a small amount of γ-butyrolactone, the viscosity of the obtained solution was adjusted to about 20 poises to prepare a positive photosensitive resin composition.

For this composition, cured at 350°C by the above-mentioned method to make a hardened relief pattern on the Cu layer. After a high temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated, and a result of 5.2% was obtained.

<Example 17>

In Example 16 above, as the resin (A), 100 g of polymer (A)-5 was changed to 100 g of polymer (A)-6, except that the positive photosensitive resin was prepared in the same manner as in Example 11. Resin composition solution.

For the composition, cured at 250°C by the above-mentioned method to produce a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated, and a result of 5.5% was obtained.

<Example 18>

In Example 16, as the resin (A), 100 g of polymer (A)-5 was changed to polymer (A)-7 (novolak resin, polystyrene conversion weight average molecular weight (Mw) = 10,600 (Asahi Except for 100 g manufactured by Jicai Co., Ltd., product name EP-4080G), a positive photosensitive resin composition solution was prepared in the same manner as in Example 11.

For this composition, cured at 250°C by the above-mentioned method to make a hardened relief pattern on the Cu layer. After a high temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated, and a result of 4.8% was obtained.

<Example 19>

In the above Example 16, as the resin (A), 100 g of the polymer (A)-5 was changed to 100 g of the polymer (A)-8, except that the positive photosensitive was prepared in the same manner as in Example 11. Resin composition solution.

For this composition, cured at 250°C by the above-mentioned method to produce a hardened relief pattern on the Cu layer, and after a high temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated, and a result of 5.1% was obtained.

<Comparative Example 1>

In the composition of Example 1, except that the component (B)-1 was not added, a negative photosensitive resin composition was prepared in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. Since the (B) fluorine-containing hydrophobic compound of the present invention is not contained, the evaluation result is 15.2%.

<Comparative Example 2>

Tetraethylene glycol dimethacrylate (represented by the following formula (B-9), manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of the component (B)-1 of Example 1. In addition, the following 1 In the same manner, a negative photosensitive resin composition was prepared, and the same evaluation as in Example 1 was performed. Since the (B) fluorine-containing hydrophobic compound of the present invention is not contained, the evaluation result is 15.5%. Furthermore, the weight ratio of the fluorine atoms in the molecule of the (B)-9 compound is 0% by mass.

<Comparative Example 3>

Tetraethylene glycol dimethacrylate ((B)-9, manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of the component (B)-1 of Example 15, except that the same method as Example 15 A negative photosensitive resin composition was prepared, and the same evaluation as in Example 15 was performed. Since the (B) fluorine-containing hydrophobic compound of the present invention is not included, the evaluation result is 14.3%.

<Comparative Example 4>

Tetraethylene glycol dimethacrylate ((B)-9, manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of the component (B)-1 of Example 12, except that the method was the same as in Example 12 A negative photosensitive resin composition was prepared, and the same evaluation as in Example 12 was performed. Since the (B) fluorine-containing hydrophobic compound of the present invention is not contained, the evaluation result is 15.7%.

<Comparative Example 5>

Tetraethylene glycol dimethacrylate ((B)-9, manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of the component (B)-1 of Example 17, except that the same method as Example 17 was used. A positive photosensitive resin composition was prepared, and the same evaluation as in Example 17 was performed. Since the (B) fluorine-containing hydrophobic compound of the present invention is not included, the evaluation result is 16.3%.

Below, the weight ratios of fluorine atoms in the molecules of (B-3)-1 to (B-3)-9 compounds are collectively shown in Table 4.

[化132]

[化136]

The results of Examples 1 to 19 and Comparative Examples 1 to 5 are collectively shown in Table 5.

[Industrial availability]

The photosensitive resin composition of the present invention can be preferably used in the field of photosensitive materials useful for the manufacture of electrical and electronic materials such as semiconductor devices and multilayer wiring boards.

Claims (4)

A negative photosensitive resin composition comprising: (A) at least one resin selected from the group consisting of polyamide acid, polyamide acid ester, and polyamide acid salt: 100 parts by mass, (B- 2) Thermal crosslinking agent: 0.01-50 parts by mass based on 100 parts by mass of the above (A) resin, and (C) photosensitive agent: 1-50 parts by mass based on 100 parts by mass of the above (A) resin, The above-mentioned (B-2) thermal crosslinking agent has the following general formula (TS1) or the following general formula (TS4):

{In the formula, Rs1 is a hydrogen atom, a univalent group selected from the group consisting of methyl, ethyl, n-propyl and isopropyl, and Rs2 is an alkyl group with 1-10 carbon atoms selected from a hydroxyl group , Alkoxy group with 1-10 carbon atoms, ester group with 1-10 carbon atoms, and urethane group, mm1 is an integer of 1 to 5, mm2 is 0-4 Here, 1≦(mm1+mm2)≦5, nn1 is an integer of 1~4, V ₁ is CH ₂ ORs1 when nn1=1, and is a single bond or 2~4 when nn1=2~4 Valence organic group; when there are plural CH ₂ ORs1 and R ₁₀ , these may be the same or different from each other}

{In the formula, Rs5 is independently a hydrogen atom and a monovalent organic group selected from the group consisting of hydrocarbon groups with 1 to 10 carbon atoms}. The photosensitive resin composition according to claim 1, wherein the resin (A) is selected from the group consisting of polyimide precursors comprising the following general formula (1) and polyamides comprising the following general formula (4) At least one of the group, the following general formula (1) is

{In the formula, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n ₁ is an integer from 2 to 150, and R ₁ and R ₂ are independently hydrogen atoms and saturated with carbon numbers of 1 to 30 Aliphatic group, aromatic group, or the following general formula (2):

(Wherein, R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or an organic group with 1 to 3 carbons, and m ₁ is an integer from 2 to 10) represented by a monovalent organic group, or 1 ~4 saturated aliphatic group, or the following general formula (3):

(In the formula, R ₆ , R ₇ and R ₈ are each independently a hydrogen atom or an organic group with 1 to 3 carbons, and m ₂ is an integer of 2 to 10), which is represented by a monovalent ammonium ion). The polyimide precursor of polyamide acid, polyamide acid ester or polyamide acid salt, the following general formula (4) has

{In the formula, X ₂ is a trivalent organic group with 6 to 15 carbons, Y ₂ is a divalent organic group with 6 to 35 carbons, and can be the same structure or multiple structures, and R ₉ is at least An organic group with a carbon number of 3-20, a radically polymerizable unsaturated bond group, and n ₂ is an integer from 1 to 1000}, a polyamide of the structure represented. A method for manufacturing a hardened relief pattern, comprising: step (1), which is achieved by coating the photosensitive resin group as described in claim 1 or 2 on a substrate The photosensitive resin layer is formed on the substrate; step (2) is to expose the photosensitive resin layer; step (3) is to develop the photosensitive resin layer after the exposure to form a floating Convex pattern; and step (4), which forms a hardened relief pattern by heating the above-mentioned relief pattern. The method of claim 3, wherein the substrate is formed of copper or copper alloy.