CN102162996B

CN102162996B - Manufacture method for negative type photosensitive resin composition and cured relief pattern

Info

Publication number: CN102162996B
Application number: CN 201110039006
Authority: CN
Inventors: 藤田充
Original assignee: Asahi Chemical Co Ltd
Current assignee: Asahi Kasei Corp
Priority date: 2010-02-16
Filing date: 2011-02-15
Publication date: 2013-07-17
Anticipated expiration: 2031-02-15
Also published as: CN102162996A; TWI413860B; JP5657414B2; TW201140242A; JP2011191749A

Abstract

The invention provides a manufacture method for a negative type photosensitive resin composition and a cured relief pattern, the negative type photosensitive resin composition can form a cured film with excellent adhesion with a substrate after low-temperature curing. The negative type photosensitive resin composition comprises: 100 mass parts of (A) particularly-structured polyimide precursor; 1-20 mass parts of (B) photopolymerization initiator; and 0.01-10 mass parts of (C) more than one monocarboxylic acid compound containing 2-30 carbons and selected from a functional group formed by hydroxyl group, ether group, and ester group.

Description

The manufacture method of negative light-sensitive resin combination, cured relief pattern

Technical field

The present invention relates to photosensitive polymer combination, use manufacture method and the semiconductor device of its cured relief pattern, described photosensitive polymer combination be used to form electronic unit for example insulating material and the passivating film in the semiconductor device, buffering is filmed and the embossing pattern of interlayer dielectric etc.

Background technology

In the past, uses such as the passivating film of the insulating material of electronic unit and semiconductor device, surface protection film, interlayer dielectric had the polyimide resin of excellent thermotolerance, electrical characteristics and mechanical property concurrently.In this polyimide resin, coating, exposure, the development that the material that provides with the form of photosensitive polyimide precursor can be by this precursor and the hot-imide that solidifies are handled and are easily formed stable on heating embossing pattern overlay film.Compare with non-light sensitive polyimide in the past, such photosensitive polyimide precursor has the feature that can significantly shorten operation.

On the other hand, in recent years, from the viewpoint of short and smallization of the raising of integrated level and function and chip size, the method that semiconductor device is installed in the printed circuit board is also changing.Change the more BGA of high-density installation (Ball Grid Array of use into from the past the installation method that utilizes metal needle and lead-Xi eutectic solder gradually, ball grid array), CSP polyimide overlay films such as (Chip Size Package, chip size packages bodies) directly contacts the structure of solder projection.When forming such projection cube structure, this overlay film need have high thermotolerance and chemical proofing.Disclose by in the composition that comprises polyimide precursor or polybenzoxazole precursor, adding the stable on heating method (with reference to patent documentation 1) that thermal cross-linking agent improves polyimide overlay film or polybenzoxazole overlay film.

And then because the propelling of the miniaturization of semiconductor device, wiring of semiconductor device resistance has become and can't ignore.Therefore, just change from the lower copper of the cloth alignment resistance of the gold that uses so far or aluminium or the wiring of aldary.

The prior art document

Patent documentation

Patent documentation 1: TOHKEMY 2003-287889 communique

Summary of the invention

The problem that invention will solve

Yet, the inventor recognizes, if using in the above-mentioned patent documentation 1 disclosed a kind of photosensitive polymer combination to carry out pattern at the substrate that is formed by copper or aldary forms, when then solidifying under with the low temperature of pattern about 250 ℃, exist the cementability of solidfied material and substrate not reach the problem of usage level, and having carried out deep research, the result has finished the present invention.

The objective of the invention is to, be provided at and form after the low-temperature setting with the negative light-sensitive resin combination of the cured film excellent in adhesion of substrate, use this photosensitive polymer combination to form manufacture method and the semiconductor device of the cured relief pattern of polyimide pattern.

For the scheme of dealing with problems

Discoveries such as the inventor have the compound of ad hoc structure by use, even when using copper or aldary as substrate, also can obtain after low-temperature setting, can to form the negative light-sensitive resin combination with the cured film excellent in adhesion of substrate, thereby finish the present invention.That is, the present invention is as described below.

[1] a kind of negative light-sensitive resin combination, it contains following substances:

100 mass parts (A) have the polyimide precursor of the structure shown in the following general formula (1),

[Chemical formula 1]

In the formula, X ₁Be 4 valency organic groups, Y ₁Be the divalent organic group, n is 2～150 integer, R ₁And R ₂Be 1 valency organic group shown in hydrogen atom or the following general formula (2) or the saturated aliphatic groups of carbon number 1～4 independently of one another, wherein, R ₁And R ₂The two is not hydrogen atom simultaneously,

[Chemical formula 2]

(in the formula, R ₃, R ₄And R ₅Be the organic group of hydrogen atom or carbon number 1～3 independently of one another, and m is 2～10 integer) };

1～20 mass parts (B) Photoepolymerizationinitiater initiater; And

0.01～10 mass parts (C) have the monocarboxylic acid compound of the carbon number 2～30 that is selected from the functional group in the group of being made up of hydroxyl, ether and ester group more than 1.

[2] according to above-mentioned [1] described negative light-sensitive resin combination, above-mentioned (C) monocarboxylic acid compound is at least a kind of monocarboxylic acid compound that is selected from the group of being made up of the compound shown in the following general formula (3),

[chemical formula 3]

In the formula, R ₆Be the organic group of hydrogen atom or carbon number 1～3, R ₇Alkyl or R for hydrogen atom, carbon number 1～3 ₈, at this, R ₈Be the group shown in the following general formula, R ₉Be the alkyl of hydrogen atom, carbon number 1～3 or the alkyl-carbonyl of carbon number 1～3,

[chemical formula 4]

(in the formula, Z ₁Be the alkoxy of hydroxyl or carbon number 1～3, j is 0～5 integer, and Z ₁Existing under a plurality of situations, can be the same or different each other) }.

[3] according to above-mentioned [1] or [2] described negative light-sensitive resin combination, wherein, above-mentioned (C) monocarboxylic acid compound is at least a kind of monocarboxylic acid compound that is selected from the group of being made up of the compound shown in the following general formula (4),

[chemical formula 5]

In the formula, R ₁₀Be the organic group of hydrogen atom or carbon number 1～3, R ₁₁Alkyl or R for hydrogen atom, carbon number 1～3 ₁₂, at this, R ₁₂Be the group shown in the following general formula,

[chemical formula 6]

(in the formula, Z ₂Be the alkoxy of hydroxyl or carbon number 1～3, k is 0～5 integer, and Z ₂Existing under a plurality of situations, can be the same or different each other) }.

[4] according to each the described negative light-sensitive resin combination in above-mentioned [1]～[3], it further contains 0.05～10 mass parts (D) organic titanic compound.

[5] according to above-mentioned [4] described negative light-sensitive resin combination, wherein, above-mentioned (D) organic titanic compound is at least a kind of compound that is selected from the group of being made up of titanium chelate, four alkoxy titanium compounds and cyclopentadiene titanium compound.

[6] a kind of manufacture method of cured relief pattern, it comprises following operation:

(1) forms the operation of photo-sensitive resin at this substrate by each the described negative light-sensitive resin combination in above-mentioned [1]～[5] being coated on the substrate;

(2) operation that this photo-sensitive resin is exposed;

(3) photo-sensitive resin after this exposure is developed and form the operation of embossing pattern;

(4) by this embossing pattern is carried out the operation that heat treated forms cured relief pattern.

[7] a kind of semiconductor device, it has the cured relief pattern that utilizes above-mentioned [6] described manufacture method to obtain and forms.

The effect of invention

The present invention is by cooperating the compound with ad hoc structure in negative light-sensitive resin combination, even can obtain also being formed on by low-temperature setting the negative light-sensitive resin combination of the cured film excellent in adhesion of solidifying back and substrate, and then, the manufacture method and the semiconductor device that use this photosensitive polymer combination to form the cured relief pattern of polyimide pattern can be provided.

Embodiment

Below the present invention is specifically described.In addition, in this instructions scope, the structure of representing with prosign in general formula exists in molecule under a plurality of situations, can be the same or different each other.

Negative light-sensitive resin combination

The invention provides the negative light-sensitive resin combination that contains following substances:

100 mass parts (A) have the polyimide precursor (below be also referred to as (A) polyimide precursor) of the structure shown in the following general formula (1),

[chemical formula 7]

[chemical formula 8]

(in the formula, R ₃, R ₄And R ₅Be the organic group of hydrogen atom or carbon number 1～3 independently of one another, and m is 2～10 integer) }; 1～20 mass parts (B) Photoepolymerizationinitiater initiater; And 0.01～10 mass parts (C) has the monocarboxylic acid compound (below be also referred to as (C) monocarboxylic acid compound) of the carbon number 2～30 that is selected from the functional group in the group of being made up of hydroxyl, ether and ester group more than 1.That is, negative light-sensitive resin combination of the present invention is neccessary composition with 100 mass parts (A) polyimide precursor, 1～20 mass parts (B) Photoepolymerizationinitiater initiater and 0.01～10 mass parts (C) monocarboxylic acid compound.

(A) polyimide precursor

(A) polyimide precursor that uses among the present invention is described.(A) polyimide precursor is the resinous principle in the negative light-sensitive resin combination of the present invention, for having the polyamide of the structure shown in the above-mentioned general formula (1).(A) polyimide precursor is converted into polyimide by heating (for example more than 200 ℃) cyclisation processing.

In the above-mentioned general formula (1), from having the viewpoint of thermotolerance and sensitometric characteristic concurrently, with X ₁4 valency organic groups of expression are preferably the organic group of carbon number 6～40, more preferably-and COOR ₁The base and-COOR ₂Base is positioned at aromatic group or the ester ring type aliphatic group at ortho position mutually with-CONH-base.As with X ₁4 valency organic groups of expression can further preferably list the structure shown in the following formula (5), but be not limited to these.

[chemical formula 9]

In addition, X ₁Structure can be combination more than a kind or 2 kinds.From having the viewpoint of thermotolerance and sensitometric characteristic concurrently, has the X of the structure shown in the above-mentioned formula (5) ₁Group is preferred.

In the above-mentioned general formula (1), from having the viewpoint of thermotolerance and sensitometric characteristic concurrently, with Y ₁The divalent organic group of expression is preferably the aromatic group of carbon number 6～40, for example can list the structure shown in the structure shown in the following formula (6) and the following formula (7), but be not limited to these.

[Chemical formula 1 0]

[Chemical formula 1 1]

{ in the formula, A represents methyl (CH ₃), ethyl (C ₂H ₅), propyl group (C ₃H ₇) or butyl (C ₄H ₉).}

In addition, Y ₁Structure can be combination more than a kind or 2 kinds.From having the viewpoint of thermotolerance and sensitometric characteristic concurrently, has the Y of the structure shown in above-mentioned formula (6) and (7) ₁Group is preferred.

About R ₁And R ₂, the R in the above-mentioned general formula (2) ₃Be preferably hydrogen atom or methyl, from the viewpoint of sensitometric characteristic, R ₄And R ₅Be preferably hydrogen atom.In addition, from the viewpoint of sensitometric characteristic, m is more than 2 and below 10, is preferably more than 2 and below 4.

(A) preparation method of polyimide precursor

In (A) polyimide precursor, the structure example shown in the above-mentioned general formula (1) is as can followingly obtaining: at first, make to comprise aforementioned 4 valency organic group X ₁Tetracarboxylic dianhydride and the alcohols with unsaturated double-bond of optical polymerism and the representative examples of saturated aliphatic alcohols reaction of carbon number 1～4 arbitrarily, make the tetrabasic carboxylic acid (below be also referred to as acid-ester body) of partial esterification, then, make it and comprise aforementioned divalent organic group Y ₁Two amines carry out amide polycondensation.

The preparation of acid-ester body

Among the present invention, as can be aptly for the preparation of (A) polyimide precursor, comprise 4 valency organic group X ₁The tetracarboxylic dianhydride, for example can list pyromellitic acid acid anhydride, biphenyl ether-3,3 ', 4,4 '-tetracarboxylic dianhydride, benzophenone-3,3 ', 4,4 '-tetracarboxylic dianhydride, biphenyl-3,3 ', 4,4 '-tetracarboxylic dianhydride, diphenylsulphone-3,3 ', 4,4 '-tetracarboxylic dianhydride, diphenyl-methane-3,3 ', 4,4 '-tetracarboxylic dianhydride, 2, two (3, the 4-phthalic anhydride) propane, 2 of 2-, two (3, the 4-phthalic anhydrides)-1,1,1 of 2-, 3,3,3-HFC-236fa etc., but be not limited to these.In addition, these can use separately certainly, and these also can use mixing more than 2 kinds.

Among the present invention, as can be aptly for the preparation of (A) polyimide precursor, the alcohols with unsaturated double-bond of optical polymerism for example can list 2-acryloxy ethanol, 1-acryloxy-3-propyl alcohol, 2-acrylamido ethanol, the methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxyl-3-methoxy-propyl acrylate, 2-hydroxyl-3-butoxy propyl group acrylate, 2-hydroxyl-3-phenoxy propyl acrylate, 2-hydroxyl-3-butoxy propyl group acrylate, 2-hydroxyl-3-tert-butoxy propyl group acrylate, 2-hydroxyl-3-cyclohexyloxy propyl group acrylate, 2-methacryloxy ethanol, 1-methacryloxy-3-propyl alcohol, 2-methacryl amido ethanol, 2-hydroxyl-3-methoxy-propyl methacrylate, 2-hydroxyl-3-butoxy propyl methyl acid esters, 2-hydroxyl-3-phenoxy propyl methacrylate, 2-hydroxyl-3-butoxy propyl methyl acid esters, 2-hydroxyl-3-tert-butoxy propyl methyl acid esters, 2-hydroxyl-3-cyclohexyloxy propyl methyl acid esters etc.

Also can in above-mentioned alcohols, mix a part as the representative examples of saturated aliphatic alcohol of carbon number 1～4, for example methyl alcohol, ethanol, n-propanol, isopropyl alcohol, normal butyl alcohol, the tert-butyl alcohol waits to use.

In the presence of base catalysts such as pyridine, in the suitable reaction dissolvent, under 20～50 ℃ of the temperature, be suitable for tetracarboxylic dianhydride of the present invention and carry out 4～10 hours stirring and dissolving, mix with above-mentioned alcohols above-mentioned, thereby can carry out the esterification of acid anhydrides, obtain desired acid-ester body.

As above-mentioned reaction dissolvent, be preferably dissolving acid-ester body fully and as the material of the polyimide precursor of the amide polycondensation product of acid-ester body and two amine components, for example can list N-N-methyl-2-2-pyrrolidone N-, N, N-dimethyl acetamide, N, dinethylformamide, dimethyl sulfoxide (DMSO), tetramethylurea, gamma-butyrolacton etc.

For reaction dissolvent, in addition, as ketone, ester class, lactone, ethers, halogenated hydrocarbon, hydro carbons, for example can list acetone, MEK, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, formic acid diethylester, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, methylene chloride, 1,2-ethylene dichloride, 1,4-dichloroetane, chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene,toluene,xylene etc.As required, these may be used alone, can also be 2 or more kinds in combination.

The preparation of polyimide precursor

Under ice-cold, drop in above-mentioned acid-ester body (being typically the solution in the above-mentioned reaction dissolvent) and mix suitable dehydrating condensation agent, for example dicyclohexyl carbodiimide, 1-ethoxy carbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonylic dioxo-two-1,2,3-benzotriazole, N, N '-two succinimidyl carbonates etc. make acid-ester body form poly-acid anhydrides, and that can use in the present invention aptly then comprises divalent organic group Y ₁Two amines be dissolved or dispersed in another solvent and gained solution drip dropped into wherein, make it carry out amide polycondensation, thereby can obtain the polyimide precursor of target.

Comprise divalent organic group Y as what can use in the present invention aptly ₁Two amines, for example can list p-phenylenediamine (PPD), m-phenylene diamine, 4,4-diamino-diphenyl ether, 3,4 '-diamino-diphenyl ether, 3,3 '-diamino-diphenyl ether, 4,4 '-diamino-diphenyl thioether, 3,4 '-diamino-diphenyl thioether, 3,3 '-diamino-diphenyl thioether, 4,4 '-diamino diphenyl sulfone, 3,4 '-diamino diphenyl sulfone, 3,3 '-diamino diphenyl sulfone, 4,4 '-benzidine, 3,4 '-benzidine, 3,3 '-benzidine, 4,4 '-diaminobenzophenone, 3,4 '-diaminobenzophenone, 3,3 '-diaminobenzophenone, 4,4 '-diaminodiphenylmethane, 3,4 '-diaminodiphenylmethane, 3,3 '-diaminodiphenylmethane, 1, two (4-amino-benzene oxygen) benzene of 4-, 1, two (4-amino-benzene oxygen) benzene of 3-, 1, two (3-amino-benzene oxygen) benzene of 3-, two [4-(4-amino-benzene oxygen) phenyl] sulfone, two [4-(3-amino-benzene oxygen) phenyl] sulfone, 4, two (4-amino-benzene oxygen) biphenyl of 4-, 4, two (3-amino-benzene oxygen) biphenyl of 4-, two [4-(4-amino-benzene oxygen) phenyl] ether, two [4-(3-amino-benzene oxygen) phenyl] ether, 1, two (4-aminophenyl) benzene of 4-, 1, two (4-aminophenyl) benzene of 3-, 9, two (4-aminophenyl) anthracenes of 10-, 2, two (4-aminophenyl) propane of 2-, 2, two (4-aminophenyl) HFC-236fa of 2-, 2,2-pair [4-(4-amino-benzene oxygen) phenyl) propane, 2,2-pair [4-(4-amino-benzene oxygen) phenyl) HFC-236fa, 1, two (the 3-aminopropyl dimetylsilyl) benzene of 4-, the o-tolidine sulfone, 9, two (4-aminophenyl) fluorenes of 9-, and a part of hydrogen atom on their phenyl ring is by methyl, ethyl, methylol, hydroxyethyl, the material that halogen etc. replace, for example 3,3 '-dimethyl-4,4 '-benzidine, 2,2 '-dimethyl-4,4 '-benzidine, 3,3 '-dimethyl-4,4 '-diaminodiphenylmethane, 2,2 '-dimethyl-4,4 '-diaminodiphenylmethane, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 3,3 '-two chloro-4,4 '-benzidine, and their potpourri etc., but be not limited to these.

In addition, the photo-sensitive resin that forms in order to improve by negative light-sensitive resin combination of the present invention being coated on the substrate and at substrate and the adaptation of various substrates, also can when preparation (A) polyimide precursor, make 1, two (3-aminopropyl) tetramethyl disiloxanes, 1 of 3-, diamido type siloxane copolymerization such as two (3-aminopropyl) the tetraphenyl disiloxane of 3-.

After the amide polycondensation reaction finishes, suction accessory substance with the dehydrating condensation agent that coexists in this reactant liquor leaches as required, then water, aliphatic lower alcohol or their poor solvents such as mixed liquor are put in the resulting polymers composition, component of polymer is separated out, further by repeat to dissolve again, precipitation is separated out operation and is waited purified polymer again, and carry out vacuum drying, isolate the polyimide precursor of target.In order to improve purification degrees, the post of filling is removed ionic impurity by making negative ion and/or Zeo-karb swelling with suitable organic solvent also can to make the solution of this polymkeric substance.

When measuring based on the polystyrene conversion weight-average molecular weight of gel permeation chromatography, (A) molecular weight of polyimide precursor is preferably 8000～150000, and more preferably 9000～50000.Weight-average molecular weight is 8000 when above, and mechanical properties is good, is 150000 when following, the favorable dispersibility in developer solution, and the resolution of embossing pattern is good.As the expansion solvent of gel permeation chromatography, recommend tetrahydrofuran and N-N-methyl-2-2-pyrrolidone N-.In addition, molecular weight is obtained by the typical curve of the standard of use monodisperse polystyrene making.As the standard monodisperse polystyrene, recommending from organic solvent clear and that electrician company makes is to select the standard sample STANDARD SM-105.

(B) Photoepolymerizationinitiater initiater

(B) Photoepolymerizationinitiater initiater that uses among the present invention is described.As (B) Photoepolymerizationinitiater initiater, can at random select to solidify as UV the compound of the Photoepolymerizationinitiater initiater of usefulness in the past.As the compound that can be used as (B) Photoepolymerizationinitiater initiater aptly, for example can preferably list benzophenone derivates such as benzophenone, o-benzoyl yl benzoic acid methyl esters, 4-benzoyl-4 '-methyldiphenyl ketone, dibenzyl ketone, Fluorenone; 2, acetophenone derivs such as 2 '-diethoxy acetophenone, 2-hydroxy-2-methyl propiophenone, 1-hydroxy cyclohexyl phenylketone; Thioxanthone derivates such as thioxanthones, 2-methyl thioxanthones, 2-isopropyl thioxanthone, diethyl thioxanthone; Benzil, benzil dimethyl ketal, benzil-benzil derivants such as 'beta '-methoxy ethyl acetals; Benzoin derivatives such as benzoin, benzoin methylether; 1-phenyl-1,2-diacetyl-2-(O-methoxy carbonyl) oxime, 1-phenyl-1,2-propanedione-2-(O-methoxy carbonyl) oxime, 1-phenyl-1,2-propanedione-2-(adjacent ethoxy carbonyl) oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl base) oxime, 1,3-diphenylprop triketone-2-(adjacent ethoxy carbonyl) oxime, 1-phenyl-oximes such as 3-ethoxy-c triketone-2-(o-benzoyl base) oxime; N-aryl glycine classes such as N-phenylglycine; Peroxides such as benzoyl peroxide; Aromatic series bisglyoxaline class etc., but be not limited to these.In addition, when using these, can be the potpourri more than a kind or 2 kinds.In above-mentioned Photoepolymerizationinitiater initiater, especially from the viewpoint of light sensitivity, oximes is preferred.

With respect to 100 mass parts (A) polyimide precursor, (B) use level of Photoepolymerizationinitiater initiater is 1～20 mass parts, from the viewpoint of light sensitivity characteristic, is preferably 2～15 mass parts.Be above (B) Photoepolymerizationinitiater initiater of 1 mass parts by cooperating with respect to 100 mass parts (A) polyimide precursor, make the light sensitivity excellence by cooperating below 20 mass parts, to make thick film solidify the property excellence.

(C) monocarboxylic acid compound

(C) monocarboxylic acid compound that uses among the present invention is described.(C) the monocarboxylic acid compound is to have only 1 carboxyl in the molecule and have carboxylic acid compound functional group, carbon number 2～30 that is selected from more than 1 in the group of being made up of hydroxyl, ether and ester group.By using (C) monocarboxylic acid compound, even carry out low-temperature setting, the good cementability of the substrate after also can obtaining to solidify (especially copper or aldary) and the polyimide resin that is formed by (A) polyimide precursor.

Also can obtain the chemism of good cementability and uncertain even carry out low-temperature setting, can be presumed as follows: for example copper in the molecule on only 1 carboxyl and the substrate interacts, and, be selected from functional group in the group of being formed by hydroxyl, ether and ester group and be situated between that the carbonyl of the polyimide of cyclisation interacts by hydrogen bond etc. and the carbonyl of (A) polyimide precursor or by heating, thereby the distance that can make substrate and resin keeps certain, improves cementability thus.

The viewpoint of the solidfied material after the curing that improves negative light-sensitive resin combination and the cementability of substrate (especially copper or aldary), (C) carbon number of monocarboxylic acid compound is more than 2 and below 30.This carbon number is preferably 2～20 scope, more preferably 2～15 scope.

Object lesson as (C) monocarboxylic acid compound; can list glycolic acid; methoxyacetic acid; ethoxyacetic acid; isopropoxy acetic acid; lactic acid; the 2-methoxypropionic acid; the 2-hydroxy-iso-butyric acid; benzal lactic acid; 4-hydroxy phenyl lactic acid; the 4-hydroxymandelic acid; 3,4-dihydroxy mandelic acid; 4-hydroxyl-3-methoxyl mandelic acid; 2-hydroxyl-3-phenylpropionic acid; 2-methoxyl-2-(1-naphthyl) propionic acid; mandelic acid; atrolactinic acid; O-acetyl group mandelic acid; α-methoxybenzene guanidine-acetic acid; the 3-hydroxybutyric acid; the 4-hydroxypentanoic acid; 4-methoxyl butyric acid and 3-methoxypropionic acid etc.Wherein, from obtaining the viewpoint of above-mentioned cementability more well, it is preferred that the α position of carboxyl has 1 monocarboxylic acid compound that is selected from the carbon number 2～30 of the functional group in the group of being made up of hydroxyl, ether and ester group at least.

And then from improving the viewpoint of cementability, (C) the monocarboxylic acid compound more preferably is selected from least a kind of monocarboxylic acid compound in the group of being made up of the compound shown in the following general formula (3).

[Chemical formula 1 2]

In the formula, R ₆Be the organic group of hydrogen atom or carbon number 1～3, R ₇Alkyl or R for hydrogen atom, carbon number 1～3 ₈, at this, R ₈Be the group shown in the following general formula, R ₉Be the alkyl of hydrogen atom, carbon number 1～3 or the alkyl-carbonyl of carbon number 1～3.

[Chemical formula 1 3]

(in the formula, Z ₁Be the alkoxy of hydroxyl or carbon number 1～3, j is 0～5 integer, and Z ₁Existing under a plurality of situations, can be the same or different each other.)}

As the compound shown in the above-mentioned general formula (3); particularly; can list glycolic acid, methoxyacetic acid, ethoxyacetic acid, isopropoxy acetic acid, lactic acid, 2-methoxypropionic acid, 2-hydroxy-iso-butyric acid, 4-hydroxymandelic acid, 3,4-dihydroxy mandelic acid, 4-hydroxyl-3-methoxyl mandelic acid, mandelic acid, atrolactinic acid, O-acetyl group mandelic acid and α-methoxybenzene guanidine-acetic acid etc.

Wherein, from the good especially viewpoint of cementability, more preferably be selected from least a kind of monocarboxylic acid compound in the group of being formed by the compound shown in the following general formula (4).

[Chemical formula 1 4]

In the formula, R ₁₀Be the organic group of hydrogen atom or carbon number 1～3, R ₁₁Alkyl or R for hydrogen atom, carbon number 1～3 ₁₂, at this, R ₁₂Be the group shown in the following general formula.

[Chemical formula 1 5]

(in the formula, Z ₂Be the alkoxy of hydroxyl or carbon number 1～3, k is 0～5 integer, and Z ₂Existing under a plurality of situations, can be the same or different each other.)}

As the compound shown in the above-mentioned general formula (4), particularly, can list glycolic acid, lactic acid, 2-hydroxy-iso-butyric acid, 4-hydroxymandelic acid, 3,4-dihydroxy mandelic acid, 4-hydroxyl-3-methoxyl mandelic acid, mandelic acid etc.

From the viewpoint of sensitometric characteristic, the R in the general formula (3) ₆And the R in the general formula (4) ₁₀Be respectively the organic group of hydrogen atom or carbon number 1～3.In addition, from the viewpoint of sensitometric characteristic, the R in the general formula (3) ₇Alkyl or above-mentioned R for hydrogen atom, carbon number 1～3 ₈, based on above-mentioned R ₇Identical reason, the R in the general formula (4) ₁₁Alkyl or above-mentioned R for hydrogen atom, carbon number 1～3 ₁₂The viewpoint of the solidfied material after the curing that improves negative light-sensitive resin combination and the cementability of substrate (especially copper or aldary), the R in the general formula (3) ₉Be the alkyl of hydrogen atom, carbon number 1～3 or the alkyl-carbonyl of carbon number 1～3.

With respect to 100 mass parts (A) polyimide precursor, (C) use level of monocarboxylic acid compound is 0.01～10 mass parts, is preferably 0.05～2 mass parts.Above-mentioned use level is that 0.01 mass parts is when above, show good cementability, on the other hand, be that 10 mass parts are when following, substrate at copper or aldary uses negative light-sensitive resin combination of the present invention to form under the situation of photo-sensitive resin, suppresses the effect excellence of the variable color on copper or the aldary.

(D) organic titanic compound

In negative light-sensitive resin combination of the present invention, can contain (D) organic titanic compound.By containing (D) organic titanic compound, even when being cured with 250 ℃ of such low-temperature settings, also can form the photo-sensitive resin of chemical proofing excellence.In addition, especially contain by making in the negative light-sensitive resin combination (C) monocarboxylic acid compound and (D) organic titanic compound the two, can make the photo-sensitive resin after the curing on the basis of substrate bonding, also bring into play the excellent such effect of chemical proofing.

As the organic titanic compound that can be used as (D) organic titanic compound, can list organic chemicals and be situated between and to be bonded to the material of titanium atom by covalent bond or ionic link.

(D) the concrete example of organic titanic compound is shown in following I)～VII):

I) titanium chelate: wherein, viewpoint from the storage stability that obtains negative light-sensitive resin combination and good pattern, titanium chelate with 2 above alkoxys is preferred, concrete example has two (triethanolamine) diisopropanol titaniums, two normal butyl alcohols two (2, the 4-pentadione) titanium, two (2, the 4-pentadione) titaniums of diisopropanol, two (dipivaloylmethane base) titaniums of diisopropanol, two (oacetic acid) titaniums of diisopropanol etc.

II) four alkoxy titanium compounds: four normal butyl alcohol titaniums, titanium tetraethoxide, four (2-Ethylhexyl Alcohol) titanium, four titanium isobutoxides, titanium tetraisopropylate, tetramethyl alcohol titanium, tetramethoxy titanium propanolate, tetramethyl phenoxide titanium, four n-nonyl alcohol titaniums, four n-propanol titaniums, four stearoyl-oxy titaniums (titanium tetrastearyloxide), four [two { 2,2-(allyloxy methyl) butanols }] titanium etc. are for example arranged.

III) cyclopentadiene titanium compound: three methyl alcohol pentamethyl cyclopentadienyltitaniums, two (η are for example arranged ⁵-2,4-cyclopentadiene-1-yl) two (2,6-difluorophenyl) titanium, two (η ⁵-2,4-cyclopentadiene-1-yl) two (2,6-, two fluoro-3-(1H-pyrroles-1-yl) phenyl) titanium etc.

IV) monoalkoxy titanium compound: for example have three (dioctyl phosphoric acid) isopropyl alcohol to close titanium, three (dodecyl benzenesulfonyl) isopropyl alcohol and close titanium etc.

V) titanium oxide compound: two (pentadione) titanium dioxide, two (dipivaloylmethane base) titanium dioxide, phthalocyanine titanium dioxide etc. are for example arranged.

VI) tetrem acyl acetone titanium compound: four titanium acetylacetones etc. are for example arranged.

VII) titanate coupling agent: isopropyl three (dodecyl benzenesulfonyl) titanate esters etc. is for example arranged.

Wherein, from the viewpoint of the better chemical proofing of performance, (D) organic titanic compound is preferably and is selected from by above-mentioned I) titanium chelate, II) four alkoxy titanium compounds and III) at least a kind of compound in the group formed of cyclopentadiene titanium compound.

With respect to 100 mass parts (A) polyimide precursor, the use level when cooperating (D) organic titanic compound is preferably 0.05～10 mass parts, more preferably 0.1～2 mass parts.This use level is 0.05 mass parts when above, shows good thermotolerance and chemical proofing, on the other hand, is 10 mass parts when following, the storage stability excellence.

(E) other compositions

Negative light-sensitive resin combination of the present invention can further contain the composition except above-mentioned (A)～(D) composition.For negative light-sensitive resin combination of the present invention, be typically, above-mentioned each composition and any composition of as required and further using are dissolved in the negative light-sensitive resin combination that solvent forms the varnish shape, use with this form, therefore as (E) other compositions, can enumerate solvent.As solvent, from the deliquescent viewpoint to (A) polyimide precursor, preferably use the organic solvent of polarity.Particularly; can list N; dinethylformamide, N-N-methyl-2-2-pyrrolidone N-, N-ethyl-2-pyrrolidone, N; N-dimethyl acetamide, dimethyl sulfoxide (DMSO), diethylene glycol dimethyl ether, cyclopentanone, gamma-butyrolacton, α-acetyl group-gamma-butyrolacton, tetramethylurea, 1; 3-dimethyl-2-imidazolone, N-cyclohexyl-2-Pyrrolidone etc., these can use separately or be used in combination more than 2 kinds.

According to desired coating film thickness and the viscosity of negative light-sensitive resin combination, with respect to 100 mass parts (A) polyimide precursor, above-mentioned solvent for example uses with the scope of 30～1500 mass parts, preferably uses with the scope of 100～1000 mass parts.

And then from improving the storage stability viewpoint of negative light-sensitive resin combination, the solvent that comprises alcohols is preferred.For the alcohols that can use aptly, be typically the alcohol that has alcohol hydroxyl group in the molecule and do not have olefinic double bond, as concrete example, can list methyl alcohol, ethanol, n-propanol, isopropyl alcohol, normal butyl alcohol, isobutyl alcohol, alkyl alcohols such as the tert-butyl alcohol, lactic acid esters such as ethyl lactate, propylene glycol-1-methyl ether, propylene glycol-2-methyl ether, propylene glycol-1-ether, propylene glycol-2-ether, propylene glycol-1-positive propyl ether, propylene glycol-propylene-glycol monoalky lether classes such as 2-positive propyl ether, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, single methanol classes such as ethylene glycol positive propyl ether, 2-hydroxy-iso-butyric acid ester class, glycolss such as ethylene glycol and propylene glycol.In these, lactic acid ester, propylene-glycol monoalky lether class, 2-hydroxy-iso-butyric acid ester class and ethanol are preferred, and especially, ethyl lactate, propylene glycol-1-methyl ether, propylene glycol-1-ether and propylene glycol-1-positive propyl ether are preferred.

Solvent contains when not having olefinic double bond pure, does not have the content that the alcohol of olefinic double bond accounts in whole solvents and is preferably 5～50 quality %, more preferably 10～30 quality %.The above-mentioned content that does not have the alcohol of olefinic double bond is 5 quality % when above, and the storage stability of negative light-sensitive resin combination is good, is 50 quality % when following, (A) favorable solubility of polyimide precursor.

Negative light-sensitive resin combination of the present invention can further contain the resinous principle except above-mentioned (A) polyimide precursor.As the resinous principle that can contain, can list polyimide, Ju oxazole, Ju oxazole precursor, phenolics, polyamide, epoxy resin, silicone resin, acrylic resin etc.With respect to 100 mass parts (A) polyimide precursor, the use level of these resinous principles is preferably the scope of 0.01～20 mass parts.

In addition, in negative light-sensitive resin combination of the present invention, can at random cooperate sensitizer in order to improve light sensitivity.As this sensitizer; for example can list michaelis ketone; 4; 4 '-two (diethylamino) benzophenone; 2; two (the 4 '-diethylamino benzal) cyclopentane of 5-; 2; two (the 4 '-diethylamino benzal) cyclohexanone of 6-; 2; two (4 '-diethylamino benzal)-4-methyl cyclohexanones of 6-; 4; 4 '-two (dimethylamino) chalcone; 4; 4 '-two (diethylamino) chalcone; to dimethylamino cinnamylidene indone; to dimethylamino benzal indone; 2-(to the dimethylaminophenyl biphenylene)-benzothiazole; 2-(to the dimethylaminophenyl ethenylidene) benzothiazole; the different aphthothiazoles of 2-(to the dimethylaminophenyl ethenylidene); 1; two (the 4 '-dimethylamino benzal) acetone of 3-; 1; two (the 4 '-diethylamino benzal) acetone of 3-; 3; 3 '-carbonyl-two (7-diethyl amino coumarin); 3-acetyl group-7-dimethylamino cumarin; 3-ethoxy carbonyl-7-dimethylamino cumarin; 3-benzyloxycarbonyl-7-dimethylamino cumarin; 3-methoxycarbonyl-7-diethyl amino coumarin; 3-ethoxy carbonyl-7-diethyl amino coumarin; N-phenyl-N '-ehtylethanolamine; the N-phenyldiethanol-amine; N-p-methylphenyl diethanolamine; the N-phenylethanol amine; 4-morpholine benzophenone; the dimethylaminobenzoic acid isopentyl ester; the diethylamino isoamyl benzoate; 2-mercaptobenzimidazole; 1-phenyl-5-mercapto-tetrazole; 2-mercaptobenzothiazole; 2-is (to dimethylamino styryl) benzoxazole; 2-(to the dimethylamino styryl) benzothiazole; 2-(to the dimethylamino styryl) naphtho-(1,2-d) thiazole; 2-(to the dimethylamino benzoyl) styrene etc.These can use or use for example 2～5 kinds combination separately.

Negative light-sensitive resin combination contains when being useful on the sensitizer that improves light sensitivity, and with respect to 100 mass parts (A) polyimide precursor, its use level is preferably 0.1～25 mass parts.

In addition, in order to improve the resolution of embossing pattern, can at random cooperate the monomer with unsaturated link of optical polymerism.As such monomer, (methyl) acrylic compounds of utilizing Photoepolymerizationinitiater initiater to carry out Raolical polymerizable is preferred, can list following substances but be not particularly limited to this: with the diethylene glycol dimethylacrylate, the TEG dimethylacrylate is representative, the mono acrylic ester of ethylene glycol or polyglycol or diacrylate and methacrylate, the mono acrylic ester of propylene glycol or polypropylene glycol or diacrylate and methacrylate, the mono acrylic ester of glycerine, diacrylate or triacrylate and methacrylate, cyclohexane diacrylate and cyclohexane dimethylacrylate, 1, the diacrylate of 4-butylene glycol and dimethylacrylate, 1, the diacrylate of 6-hexanediol and dimethylacrylate, the diacrylate of neopentyl glycol and dimethylacrylate, the mono acrylic ester of bisphenol-A or diacrylate and methacrylate, benzene trimethyl acrylic ester (benzene trimethacrylate), isobornyl acrylate and isobornyl methacrylate, acrylamide and derivant thereof, Methacrylamide and derivant thereof, the triacrylate of trimethylolpropane and methacrylate, the diacrylate of glycerine or triacrylate and methacrylate, the diacrylate of pentaerythrite, triacrylate or tetraacrylate and methacrylate, and compounds such as the oxirane of these compounds or propylene oxide adduct.

Negative light-sensitive resin combination contain the above-mentioned optical polymerism that is useful on the resolution that improves embossing pattern have the monomer of unsaturated link the time, with respect to 100 mass parts (A) polyimide precursor, the use level of the monomer with unsaturated link of above-mentioned optical polymerism is preferably 1～50 mass parts.

In addition, to use film that negative light-sensitive resin combination of the present invention forms and the cementability of base material in order improving, can at random to cooperate bonding auxiliary agent.As bonding auxiliary agent, can list gamma-amino propyl group dimethoxy silane, N-(beta-aminoethyl)-gamma-amino propyl group methyl dimethoxysilane, γ-glycidoxy propyl group methyl dimethoxysilane, γ-sulfydryl propyl group methyl dimethoxysilane, 3-methacryloxypropyl dimethoxy-methyl silane, the 3-methacryloxypropyl trimethoxy silane, dimethoxy-methyl-3-piperidyl propyl silane, diethoxy-3-glycidoxy propyl group methyl-monosilane, N-(3-diethoxymethyl silicyl propyl group) succinimide, N-[3-(triethoxysilyl) propyl group] phthalamic acid, benzophenone-3,3 '-two (the N-[3-triethoxysilyl] propyl amides)-4,4 '-dicarboxylic acid, benzene-1,4-pair (the N-[3-triethoxysilyl] propyl amides)-2, the 5-dicarboxylic acid, 3-(triethoxysilyl) propyl group succinic anhydride, silane coupling agents such as N-phenyl amino propyl trimethoxy silicane, and three (oacetic acid base) aluminium, aluminium tris(acetylacetonate), aluminium such as diisopropyl acid oacetic acid base aluminium are bonding auxiliary agent etc.

In these bonding auxiliary agents, from the viewpoint of bonding force, more preferably use silane coupling agent.With respect to 100 mass parts (A) polyimide precursor, when containing bonding auxiliary agent in the negative light-sensitive resin combination, the use level of bonding auxiliary agent is preferably the scope of 0.5～25 mass parts.

In addition, especially for the viscosity that improves under the state of the solution that comprises solvent the negative light-sensitive resin combination when preserving and the stability of light sensitivity, can at random cooperate hot polymerization inhibitor.As hot polymerization inhibitor, can use quinhydrones, N-nitroso-diphenylamine, p-tert-butyl catechol, phenothiazine, N-phenyl naphthyl amines, ethylenediamine tetraacetic acid, 1,2-CDTA, glycoletherdiaminotetraacetic acid, 2,6-di-t-butyl-p-methyl phenol, 5-nitroso--oxine, 1-Nitroso-2-naphthol, 2-nitroso--1-naphthols, 2-nitroso--5-(N-ethyl-N-sulfo group propyl group amino) phenol, N-nitroso--N-Phenylhydroxylamine ammonium salt, N-nitroso--N (1-naphthyl) azanol ammonium salt etc.

The use level of the hot polymerization inhibitor during as cooperation in negative light-sensitive resin combination with respect to 100 mass parts (A) polyimide precursor, is preferably the scope of 0.005～12 mass parts.

In addition, can at random cooperate crosslinking chemical.Crosslinking chemical can be in the time will using the formed embossing pattern of negative light-sensitive resin combination of the present invention to be heating and curing, can make the crosslinked crosslinking chemical of (A) polyimide precursor or can make crosslinking chemical self form the crosslinking chemical of cross-linked network.Crosslinking chemical can further be strengthened thermotolerance and the chemical proofing of the cured film that is formed by negative light-sensitive resin combination.As crosslinking chemical, can use amino resins and derivant thereof aptly, wherein, can use urea resin, glycol urea resin (glycol urea resin), hydroxy ethylene urea resin, melamine resin, benzoguanamine resin and their derivant aptly.Be preferably alkoxy methyl urea compounds and alkoxy methyl melamine compound especially, as an example, can list MX-290 (NIPPON CARBIDEINDUSTRIES CO., INC. manufacturing), UFR-65 (Mitsui Cytec Co., Ltd. make) and MW-390 (NIPPON CARBIDE INDUSTRIES CO., INC. makes).

From taking into account with thermotolerance and chemical proofing each performance in addition, with respect to 100 mass parts (A) polyimide precursor, the use level when negative light-sensitive resin combination contains crosslinking chemical is preferably 0.5～20 mass parts, more preferably 2～10 mass parts.This use level is 0.5 mass parts when above, shows good thermotolerance and chemical proofing, on the other hand, is 20 mass parts when following, the storage stability excellence.

In addition, when for example using the substrate that is formed by copper or aldary, in order to suppress the substrate variable color, can at random cooperate azole compounds.As azole compounds, can list the 1H-triazole, 5-methyl isophthalic acid H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, the 4-tert-butyl group-5-phenyl-1H-triazole, 5-hydroxy phenyl-1H-triazole, Phenyltriazole, to the ethoxyl phenenyl triazole, 5-phenyl-1-(2-dimethyl aminoethyl) triazole, 5-benzyl-1H-triazole, the hydroxy phenyl triazole, 1, the 5-triazol-dimethyl, 4,5-diethyl-1H-triazole, the 1H-benzotriazole, 2-(5-methyl-2-hydroxy phenyl) benzotriazole, 2-[2-hydroxyl-3, two (the α of 5-, α-Er Jiajibianji) phenyl]-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxy phenyl) benzotriazole, 2-(the 3-tert-butyl group-5-methyl-2-hydroxy phenyl)-benzotriazole, 2-(3,5-, two tertiary pentyls-2-hydroxy phenyl) benzotriazole, 2-(2 '-hydroxyl-5 '-uncle's octyl phenyl) benzotriazole, the hydroxy phenyl benzotriazole, tolyl-triazole, 5-methyl isophthalic acid H-benzotriazole, 4-methyl isophthalic acid H-benzotriazole, 4-carboxyl-1H-benzotriazole, 5-carboxyl-1H-benzotriazole, the 1H-tetrazolium, 5-methyl isophthalic acid H-tetrazolium, 5-phenyl-1H-tetrazolium, 5-amino-1H-tetrazolium, 1-methyl isophthalic acid H-tetrazolium etc.Can especially preferably list tolyl-triazole, 5-methyl isophthalic acid H-benzotriazole and 4-methyl isophthalic acid H-benzotriazole.In addition, these azole compounds can use a kind of potpourri that also can use more than 2 kinds.

With respect to 100 mass parts (A) polyimide precursor, when negative light-sensitive resin combination contains above-mentioned azole compounds, the use level of above-mentioned azole compounds is preferably 0.1～20 mass parts, from the viewpoint of light sensitivity characteristic, and 0.5～5 mass parts more preferably.Azole compounds is that 0.1 mass parts is when above with respect to the use level of 100 mass parts (A) polyimide precursor, form under the situation of negative light-sensitive resin combination of the present invention at copper or aldary, the variable color of copper or copper alloy surface is inhibited, on the other hand, be 20 mass parts when following, the light sensitivity excellence.

In addition, in order to suppress the variable color on the copper, can at random cooperate hindered phenol compound.As hindered phenol compound, can list 2,6-di-tert-butyl-4-methy phenol, 2,5-di-t-butyl-quinhydrones, octadecyl-3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester, iso-octyl-3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester, 4,4 '-di-2-ethylhexylphosphine oxide (2,6-DI-tert-butylphenol compounds), 4,4 '-sulphur-two (3 methy 6 tert butyl phenol), 4,4 '-butylidene-two (3 methy 6 tert butyl phenol), triethylene glycol-two [3-(the 3-tert-butyl group-5-methyl-4-hydroxy phenyl) propionic ester], 1,6-hexanediol-two [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester], 2,2-sulphur-di ethylene bis [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester], N, N '-hexa-methylene two (3,5-di-t-butyl-4-hydroxyl-hydrocinnamamide), 2,2 '-methylene-two (4-methyl-6-tert butyl phenol), 2,2 '-methylene-two (4-ethyl-6-tert-butyl phenol), [3-(3 for pentaerythrite-four, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], three-(3,5-di-tert-butyl-4-hydroxyl benzyl)-isocyanuric acid ester, 1,3,5-trimethyl-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, 1,3,5-three (3-hydroxyl-2,6-dimethyl-4-isopropyl benzyl)-1,3,5-triazines-2,4,6-(1H, 3H, 5H)-triketone, 1,3,5-three (the 4-tert-butyl group-3-hydroxyl-2,6-dimethyl benzyl)-1,3,5-triazine-2,4,6-(1H, 3H, 5H)-triketone, 1,3,5-three (4-s-butyl-3-hydroxyl-2,6-dimethyl benzyl)-1,3,5-triazine-2,4,6-(1H, 3H, 5H)-triketone, 1,3,5-three [4-(1-ethyl propyl)-3-hydroxyl-2, the 6-dimethyl benzyl]-1,3,5-triazine-2,4,6-(1H, 3H, 5H)-triketone, 1,3,5-three [4-triethyl methyl-3-hydroxyl-2, the 6-dimethyl benzyl]-1,3,5-triazines-2,4,6-(1H, 3H, 5H)-triketone, 1,3,5-three (3-hydroxyl-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H, 3H, 5H)-triketone, 1,3,5-three (the 4-tert-butyl group-3-hydroxyl-2,5, the 6-trimethyl benzyl)-1,3,5-triazine-2,4,6-(1H, 3H, 5H)-triketone, 1,3,5-three (the 4-tert-butyl group-5-ethyl-3-hydroxyl-2, the 6-dimethyl benzyl)-1,3,5-triazines-2,4,6-(1H, 3H, 5H)-triketone, 1,3,5-three (the 4-tert-butyl group-6-ethyl-3-hydroxy-2-methyl benzyl)-1,3,5-triazines-2,4,6-(1H, 3H, 5H)-triketone, 1,3,5-three (the 4-tert-butyl group-6-ethyl-3-hydroxyl-2,5-dimethyl benzyl)-1,3,5-triazine-2,4,6-(1H, 3H, 5H)-triketone, 1,3,5-three (the 4-tert-butyl group-5,6-diethyl-3-hydroxy-2-methyl benzyl)-1,3,5-triazine-2,4,6-(1H, 3H, 5H)-triketone, 1,3,5-three (the 4-tert-butyl group-3-hydroxy-2-methyl benzyl)-1,3,5-triazine-2,4,6-(1H, 3H, 5H)-triketone, 1,3,5-three (the 4-tert-butyl group-3-hydroxyl-2, the 5-dimethyl benzyl)-1,3,5-triazine-2,4,6-(1H, 3H, 5H)-triketone, 1,3,5-three (the 4-tert-butyl group-5-ethyl-3-hydroxy-2-methyl benzyl)-1,3,5-triazine-2,4,6-(1H, 3H, 5H)-triketone etc., but be not limited to these.In these, 1,3,5-three (the 4-tert-butyl group-3-hydroxyl-2,6-dimethyl benzyl)-1,3,5-triazines-2,4,6-(1H, 3H, 5H)-triketone etc. is particularly preferred.

With respect to 100 mass parts (A) polyimide precursor, the use level of hindered phenol compound is preferably 0.1～20 mass parts, from the viewpoint of light sensitivity characteristic, and 0.5～10 mass parts more preferably.Hindered phenol compound is that 0.1 mass parts is when above with respect to the use level of 100 mass parts (A) polyimide precursor, for example form under the situation of negative light-sensitive resin combination of the present invention at copper or aldary, can prevent variable color and the corrosion of copper or aldary, on the other hand, be 20 mass parts when following, the light sensitivity excellence.

The manufacture method of cured relief pattern

The present invention also provides the manufacture method of the cured relief pattern that comprises following operation: (1) forms the operation of photo-sensitive resin at this substrate by the negative light-sensitive resin combination of the invention described above being coated on the substrate; (2) operation that this photo-sensitive resin is exposed; (3) photo-sensitive resin after this exposure is developed and form the operation of embossing pattern; (4) by this embossing pattern is carried out the operation that heat treated forms cured relief pattern.Below, the typical way of each operation is described.

(1) by negative light-sensitive resin combination being coated on the substrate and at this base Form the operation of photo-sensitive resin on the plate

In this operation, negative light-sensitive resin combination of the present invention is coated on the base material, after this make its drying form photo-sensitive resin as required.As coating process, can use in the past to be used for the photosensitive resin coating method for compositions, for example the method that is coated with spin coater, excellent spreader, Scraper applicator, curtain formula spreader, screen process press etc., with the spray applicators method that is coated with etc. of spraying.

As required, can be dry by filming that negative light-sensitive resin combination forms, as drying means, can use methods such as air-dry, as to utilize baking oven or heating plate heat drying, vacuum drying.In addition, it is desirable to, the drying of filming (A) polyimide precursor in negative light-sensitive resin combination does not take place to carry out under the condition of imidizate.Particularly, when carrying out air-dry or heat drying, can under 20 ℃～140 ℃, 1 minute～1 hour condition, carry out drying.Can form photo-sensitive resin at substrate thus.

(2) operation that photo-sensitive resin is exposed

In this operation; use exposure devices such as contact alignment device, mirror surface projection (mirrorprojection), ledex; utilize ultraviolet light source etc., across the photomask with pattern or mask or the photo-sensitive resin that forms in directly to above-mentioned operation expose.

After this, in order to improve light sensitivity etc., as required, can implement based on the postexposure bake (PEB) of the combination of temperature and time arbitrarily and/or the preceding baking of developing.The scope of baking condition is preferably 10 second～240 seconds of 40～120 ℃ of temperature, time, as long as each characteristic that does not hinder negative light-sensitive resin combination of the present invention then is not defined as this scope.

(3) photo-sensitive resin after the exposure is developed and form embossing pattern Operation

In this operation, unexposed in the photo-sensitive resin after the exposure is developed and remove.As the developing method that the photo-sensitive resin after the exposure (irradiation) is developed, can be from the developing method of existing known photoresist, for example rotary spraying technique, stirring (Paddle) method, follow in the infusion process that ultrasound wave handles etc. and select arbitrary method to use.In addition, after the development, for shape of adjusting embossing pattern etc., can implement as required based on the postdevelopment bake of the combination of temperature and time arbitrarily.

As the developer solution that uses in developing, be preferred for the good solvent of negative light-sensitive resin combination or the combination of this good solvent and poor solvent.As good solvent; N-N-methyl-2-2-pyrrolidone N-, N-cyclohexyl-2-Pyrrolidone, N; N-dimethyl acetamide, cyclopentanone, cyclohexanone, gamma-butyrolacton, α-acetyl group-gamma-butyrolacton etc. are preferred; as poor solvent, toluene, dimethylbenzene, methyl alcohol, ethanol, isopropyl alcohol, ethyl lactate, methyl proxitol acetate and water etc. are preferred.When good solvent is mixed to use with poor solvent, preferably adjust the ratio of poor solvent and good solvent according to the dissolubility of the polymkeric substance in the negative light-sensitive resin combination.In addition, can be with each solvent more than 2 kinds, for example several combinations are used.

(4) form cured relief pattern by embossing pattern being carried out heat treated Operation

In this operation, heat to make photographic composition to disperse the above-mentioned embossing pattern that obtains by development, make (A) polyimide precursor imidizate simultaneously, thereby be converted into the cured relief pattern that is formed by polyimide.As the method that is heating and curing, but can select to utilize the whole bag of tricks such as method of the temperature lifting type baking oven of the method for heating plate, the method for using baking oven, use design temperature program.Heating can be carried out under for example 200 ℃～400 ℃, 30 minutes～5 hours condition.Atmosphere gas when being heating and curing can use air, also can use inert gases such as nitrogen, argon gas.

Semiconductor device

The semiconductor device that the cured relief pattern that the present invention also provides the manufacture method of the cured relief pattern with the invention described above utilized to obtain forms.The present invention also provides following semiconductor device: have as the base material of semiconductor element and utilize the cured relief pattern of the polyimide that above-mentioned cured relief pattern manufacture method forms at this base material.In addition, the present invention is also applicable to the manufacture method of following semiconductor device: use semiconductor element as base material, and comprise that the manufacture method of above-mentioned cured relief pattern is as the part of operation.Semiconductor device of the present invention can followingly be made: the cured relief pattern that will form with above-mentioned cured relief pattern manufacture method as surface protection film, interlayer dielectric, again wiring with dielectric film, flip-chip device with diaphragm or have projection cube structure semiconductor device diaphragm etc. and form, and make up with the manufacture method of known semiconductor device.

Negative light-sensitive resin combination of the present invention can be applied to as above-mentioned in the semiconductor device, also can be used for the layer insulation of multilayer circuit, the purposes such as seal coat, soldering-resistance layer and liquid crystal orientation film of flexible copper-clad plate.

Embodiment

Below, specify the present invention by embodiment, but the present invention is not limited to this.In embodiment, comparative example and Production Example, measure and estimate the rerum natura of negative light-sensitive resin combination according to following method.

(1) weight-average molecular weight

Measure the weight-average molecular weight (Mw) of each polyimide precursor with gel permeation chromatography (polystyrene standard conversion).The post that uses in the mensuration is clear and the trade (brand) name Shodex 805M/806M columns in series of electrician company manufacturing, the standard monodisperse polystyrene is selected Shodex STANDARD SM-105 clear and that electrician's (strain) makes, launching solvent is the N-N-methyl-2-2-pyrrolidone N-, and detecting device uses trade (brand) name Shodex RI-930 clear and that the electrician makes.

(2) adhesive test

Coat on the copper base negative light-sensitive resin combination rotation and drying, formation is filmed as the thickness 17 μ m's of photo-sensitive resin, then, use heating schedule formula curing oven (VF-2000 type, Japan, Koyo Thermo Systems Co., Ltd. makes) under nitrogen atmosphere, carry out 200 ℃ following 1 hour, then in 250 ℃ of following heat treated of 2 hours (curing), thereby obtain the polyimide coating film of thickness 10 μ m.Determining film thickness uses Tencor P-15 type section difference meter (KLA-Tencor Corporation manufacturing) to carry out.For the film after solidifying, according to the cross-hatching (crosscut method) of JIS K 5600-5-6 standard, based on the adhesion properties between following benchmark evaluation metal material (copper base) and the heat-resistant resin (polyimide coating film).

" the best ": with the grid number of the polyimide coating film of substrate bonding be 100.

" good ": with the grid number of the polyimide coating film of substrate bonding be 80～99.

" slightly good ": with the grid number of the polyimide coating film of substrate bonding be 50～79.

" slightly poor ": with the grid number of the polyimide coating film of substrate bonding be 20～49.

" poor ": with the grid number of the polyimide coating film of substrate bonding less than 20.

(3) chemical proofing test

On the silicon chip (KYODO INTERNATIONAL, INC. make) of 6 inches band nitride films, be rotated coating and dry, form filming as the thickness 17 μ m of photo-sensitive resin.Use the girdle tests pattern mask, utilize ghi ledex (Inc. makes for Prisma-ghi, Ultratech) with 200mJ/cm ²This irradiation energy of filming is exposed.Then, use cyclopentanone, utilize developing machine (D-SPIN636 type, Japan, DAINIPPON SCREEN MFG.CO., LTD. make) carry out spray development to being formed at filming on the wafer, wash with methyl proxitol acetate unexposed development removed, obtain the embossing pattern of polyimide precursor.For the wafer that is formed with embossing pattern, use heating schedule formula curing oven (VF-2000 type, Japan, Koyo Thermo Systems Co., Ltd. make) under nitrogen atmosphere, carry out 200 ℃ following 1 hour, then 250 ℃ of following heat treated of 2 hours, thereby obtain the cured relief pattern of the polyimide of thickness 10 μ m at band nitride film silicon chip.

The gained polyimide pattern was flooded 1 hour down at 100 ℃ in the solution that is formed by 1wt% potassium hydroxide, 39wt%3-methoxyl-3-methyl isophthalic acid-butanols, 60wt% dimethyl sulfoxide (DMSO).The washing and air-dry after, carry out the evaluation of polyimide coating film by the observation under determining film thickness and the optical microscope.For filming behind the dipping, will with dipping before compare the Thickness Variation of filming and be " the best " ± 1% with average evaluation interior and that do not crack, the Thickness Variation of filming is " good " ± 3% with average evaluation interior and that do not crack, with Thickness Variation surpass ± 3% or the average evaluation that cracks be " poor ".

Production Example 1 (as the polymer A of (A) polyimide precursor synthetic)

With 155.1g 4, the two O-phthalic acid dianhydrides (ODPA) of 4 '-oxygen are put into the removable flask of 2 liters of capacity, add 131.2g methacrylic acid 2-hydroxyl ethyl ester (HEMA) and 400ml gamma-butyrolacton, at room temperature stir, add the 81.5g pyridine while stirring, obtain reaction mixture.After the heating that is caused by reaction finishes, naturally cool to room temperature, placed 16 hours.

Then, under ice-cold, added in reaction mixture with 40 minutes while stirring 206.3g dicyclohexyl carbodiimide (DCC) is dissolved in the solution that the 180ml gamma-butyrolacton forms, then make 93.0g 4 with adding in 60 minutes while stirring, 4 '-diamino-diphenyl ether (DADPE) is suspended in the material that the 350ml gamma-butyrolacton forms.Further at room temperature stirred 2 hours, then, adding 30ml ethanol also stirred 1 hour, then, added the 400ml gamma-butyrolacton.Remove the sediment that produces in the reaction mixture by filtration, obtain reactant liquor.

The gained reactant liquor joined in 3 liters the ethanol, generate the sediment that is formed by crude polymer.The crude polymer that generates is leached, is dissolved in 1.5 liters of tetrahydrofurans, obtain crude polymer solution.Gained crude polymer drips of solution is added in 28 liters the water and makes polymer precipitation, the gained sediment is leached, vacuum drying then obtains pulverous polymkeric substance (polymer A).With the molecular weight of gel permeation chromatography (polystyrene standard conversion) mensuration polymer A, weight-average molecular weight (Mw) is 20000 as a result.

Production Example 2 (as the polymer B of (A) polyimide precursor synthetic)

Use 147.1g 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride replaces the 155.1g 4 of Production Example 1, the two O-phthalic acid dianhydrides of 4 '-oxygen, in addition with aforementioned Production Example 1 in the method for record similarly react, obtain polymer B.With the molecular weight of gel permeation chromatography (polystyrene standard conversion) mensuration polymer B, weight-average molecular weight (Mw) is 22000 as a result.

Embodiment 1

Use polymer A, B, prepare negative light-sensitive resin combination with following method, prepared composition is estimated.To be dissolved in the mixed solvent that is formed by 80g N-N-methyl-2-2-pyrrolidone N-(hereinafter referred to as NMP) and 20g ethyl lactate with following substances as 50g polymer A and the 50g polymer B ((A) polyimide precursor) of polyimide precursor: 4g 1-phenyl-1,2-propanedione-2-(O-ethoxy carbonyl)-oxime ((B) Photoepolymerizationinitiater initiater), 0.2g mandelic acid ((C) monocarboxylic acid compound), 0.15g benzotriazole, 1.5g 1,3,5-three (the 4-tert-butyl group-3-hydroxyl-2, the 6-dimethyl benzyl)-1,3,5-triazine-2,4,6-(1H, 3H, 5H)-triketone, 10g N-phenyldiethanol-amine, 4g methoxy urea resin (MX-290), 8g TEG dimethylacrylate, 1.5g N-[3-(triethoxysilyl) propyl group] phthalamic acid, and 0.05g 2-nitroso--1-naphthols.Further a small amount of this mixed solvent of adding is adjusted into about 35 pools with the viscosity of gained solution, forms negative light-sensitive resin combination.

Estimating said composition according to preceding method, even the evaluation of result's cementability when low-temperature setting is 100 still, is " the best ", being evaluated as of chemical proofing " good ".

Embodiment 2,3

The use level as the mandelic acid of (C) monocarboxylic acid compound among the present invention of embodiment 1 is changed to the component content shown in the table 1 prepare negative light-sensitive resin combination, carry out same evaluation with embodiment 1 respectively.All by the method evaluation identical with embodiment 1, its evaluation result is identical with embodiment 1 in either case.

Embodiment 4

The use level as the mandelic acid of (C) monocarboxylic acid compound among the present invention of embodiment 1 is changed to the component content shown in the table 1 prepare negative light-sensitive resin combination, carry out same evaluation with embodiment 1.Estimate cementability, the result is 80, is " good ".The evaluation result of chemical proofing is identical with embodiment 1.

Embodiment 5

The use level as the mandelic acid of (C) monocarboxylic acid compound among the present invention of embodiment 1 is changed to the component content shown in the table 1 prepare negative light-sensitive resin combination, carry out same evaluation with embodiment 1.Evaluation result is identical with embodiment 1.

Embodiment 6

Use the 2-hydroxy-iso-butyric acid to replace the mandelic acid as (C) monocarboxylic acid compound among the present invention of embodiment 1 to prepare negative light-sensitive resin combination by the component content shown in the table 1, carry out same evaluation with embodiment 1.Evaluation result is identical with embodiment 1.

Embodiment 7

Use lactic acid to replace the mandelic acid as (C) monocarboxylic acid compound among the present invention of embodiment 1 to prepare negative light-sensitive resin combination by the component content shown in the table 1, carry out same evaluation with embodiment 1.Estimate cementability, the result is 85, is " good ".The evaluation result of chemical proofing is identical with embodiment 1.

Embodiment 8

Use the methoxybenzene guanidine-acetic acid to replace the mandelic acid as (C) monocarboxylic acid compound among the present invention of embodiment 1 to prepare negative light-sensitive resin combination by the component content shown in the table 1, carry out same evaluation with embodiment 1.Estimate cementability, the result is 60, is " slightly good ".The evaluation result of chemical proofing is identical with embodiment 1.

Embodiment 9

In the composition of embodiment 1, further add as two (oacetic acid base) titanium (the Titanium diisopropoxidebis (ethyl acetoacetate) of the 0.1g diisopropanol of (D) organic titanic compound, D1), in addition prepare negative light-sensitive resin combination similarly to Example 1.Carry out the chemical proofing evaluation, the Thickness Variation of film is not observed crackle yet in ± 1% as a result, is " the best ".The evaluation result of cementability is identical with embodiment 1.

Embodiment 10

In the composition of embodiment 1, further add the 0.1g four normal butyl alcohol titaniums (D2) as (D) organic titanic compound, in addition prepare negative light-sensitive resin combination similarly to Example 1.Carry out the chemical proofing evaluation, the Thickness Variation of film is not observed crackle yet in ± 1% as a result, is " the best ".The evaluation result of cementability is identical with embodiment 1.

Embodiment 11

In the composition of embodiment 1, further add two (η as the 0.1g of (D) organic titanic compound ⁵-2,4-cyclopentadiene-1-yl) two (2,6-, two fluoro-3-(1H-pyrroles-1-yl) phenyl) titanium (D3) in addition prepares negative light-sensitive resin combination similarly to Example 1.Carry out the chemical proofing evaluation, the Thickness Variation of film is not observed crackle yet in ± 1% as a result, is " the best ".The evaluation result of cementability is identical with embodiment 1.

Embodiment 12

Use the replacement of 100g polymer A as 50g polymer A and the 50g polymer B of (A) polyimide precursor among the present invention, in addition prepare negative light-sensitive resin combination similarly to Example 9, carry out same evaluation with embodiment 1.Evaluation result is identical with embodiment 9.

Comparative example 1

From the composition of embodiment 1, remove mandelic acid, in addition prepare negative light-sensitive resin combination similarly to Example 1, carry out same evaluation with embodiment 1.Being evaluated as of chemical proofing by the polyimide coating film that the foundation preceding method is coated with at silicon chip and copper base, drying, exposure, development and heat treated obtain " good ", but owing to do not comprise (C) of the present invention monocarboxylic acid compound, cementability is 40, is " slightly poor ".

Comparative example 2

In the composition of comparative example 1, add as two (oacetic acid base) titaniums (D1) of the 0.1g diisopropanol of (D) organic titanic compound, in addition similarly prepare negative light-sensitive resin combination with comparative example 1, carry out same evaluation with embodiment 1.By the foundation preceding method in the coating of silicon chip and copper base, dry, exposure, develop and being evaluated as of the chemical proofing of the polyimide coating film that heat treated obtains " the best ", but owing to do not comprise (C) of the present invention monocarboxylic acid compound, cementability is 0, is " poor ".

[table 1]

Utilizability on the industry

Negative light-sensitive resin combination of the present invention can use in the photosensitive material field for the manufacture of for example electric and electronic such as semiconductor device, multi-layer wire substrate material aptly.

Claims

1. negative light-sensitive resin combination, it contains following substances:

In the formula, X ₁Be 4 valency organic groups of the carbon number 6 ~ 40 shown in the following general formula (5), Y ₁Be the divalent organic group of the carbon number 6 ~ 40 shown in following general formula (6) or the following general formula (7), n is 2 ~ 150 integer, R ₁And R ₂Be 1 valency organic group shown in hydrogen atom or the following general formula (2) or the saturated aliphatic groups of carbon number 1 ~ 4 independently of one another, wherein, R ₁And R ₂The two is not hydrogen atom simultaneously,

In the formula, R ₃, R ₄And R ₅Be hydrogen atom or methyl independently of one another, and m is 2 ~ 10 integer,

In the general formula (7), A represents methyl-CH ₃, ethyl-C ₂H ₅, propyl group-C ₃H ₇Or butyl-C ₄H ₉

1 ~ 20 mass parts (B) Photoepolymerizationinitiater initiater; And

0.01 ~ 10 mass parts (C) have the monocarboxylic acid compound of the carbon number 2 ~ 30 that is selected from the functional group in the group of being made up of hydroxyl, ether and ester group more than 1.

2. negative light-sensitive resin combination according to claim 1, wherein, described (C) monocarboxylic acid compound is for being selected from least a kind of monocarboxylic acid compound in the group of being made up of the compound shown in the following general formula (3),

In the formula, R ₆Be hydrogen atom or methyl, R ₇Alkyl or R for hydrogen atom, carbon number 1 ~ 3 ₈, at this, R ₈Be the group shown in the following general formula, R ₉Be the alkyl of hydrogen atom, carbon number 1 ~ 3 or the alkyl-carbonyl of carbon number 1 ~ 3,

In the formula, Z ₁Be the alkoxy of hydroxyl or carbon number 1 ~ 3, j is 0 ~ 5 integer, and Z1 can be the same or different each other existing under a plurality of situations.

3. negative light-sensitive resin combination according to claim 1 and 2, wherein, described (C) monocarboxylic acid compound is for being selected from least a kind of monocarboxylic acid compound in the group of being made up of the compound shown in the following general formula (4),

In the formula, R ₁₀Be hydrogen atom or methyl, R ₁₁Alkyl or R for hydrogen atom, carbon number 1 ~ 3 ₁₂, at this, R ₁₂Be the group shown in the following general formula,

In the formula, Z ₂Be the alkoxy of hydroxyl or carbon number 1 ~ 3, k is 0 ~ 5 integer, and Z ₂Existing under a plurality of situations, can be the same or different each other.

4. negative light-sensitive resin combination according to claim 1 and 2, it further contains 0.05 ~ 10 mass parts (D) organic titanic compound.

5. negative light-sensitive resin combination according to claim 4, wherein, described (D) organic titanic compound is at least a kind of compound that is selected from the group of being made up of titanium chelate, four alkoxy titanium compounds and cyclopentadiene titanium compound.

6. the manufacture method of a cured relief pattern, it comprises following operation:

(1) forms the operation of photo-sensitive resin at this substrate by each the described negative light-sensitive resin combination in the claim 1 ~ 5 being coated on the substrate;

(2) operation that this photo-sensitive resin is exposed;

7. semiconductor device, it has the cured relief pattern that utilizes the described manufacture method of claim 6 to obtain and forms.