CN104252102A

CN104252102A - Negative Photosensitive Resin Composition, Immobilizing Membrane, Electronic Device And Polymer

Info

Publication number: CN104252102A
Application number: CN201410295423.0A
Authority: CN
Inventors: 大西治; 池田阳雄
Original assignee: Sumitomo Bakelite Co Ltd
Current assignee: Sumitomo Bakelite Co Ltd
Priority date: 2013-06-28
Filing date: 2014-06-26
Publication date: 2014-12-31
Anticipated expiration: 2034-06-26
Also published as: JP2015028608A; JP6369132B2; CN104252102B; KR20150002502A; KR102256145B1; TW201510658A

Abstract

The present invention provides a negative photosensitive resin composition comprising a polymer formed by the copolymer represented by the following formula (1), a photo-acid generator and a first cross-linking agent for cross-linking the above polymer by an acid catalyst generated by the above photo-acid generator. In the formula (1), l, p and m represent the Moore containing rate in the polymer, and satisfy the relationships: l+m+p<=1, 0<=l<1, 0<p<1 and 0<m<1; n and q are respectively 0, 1 or 2, R1-R4 and R8-R11 are respectively organic groups having 1-30 hydrogen or carbon atoms, more than one or two selected from the R8, R9, R10 and R11 are organic groups having alcoholic hydroxyl groups, A is a structure unit represented by the following formulas (2a, 2b, 2c or 2d). In the formulas (2a, 2b), R5, R6 and R7 are respectively organic groups having 1-18 carbon atoms.

Description

Negative light-sensitive resin combination, cured film, electronic installation and polymkeric substance

Technical field

The present invention relates to negative light-sensitive resin combination, cured film, electronic installation and polymkeric substance.

Background technology

In the manufacture process of the display surface etc. of SIC (semiconductor integrated circuit), flat-panel monitor (FPD), in order to form fine element or carry out microfabrication, make use of photoetching technique.

In photoetching technique, in order to form Resist patterns, employ photosensitive polymer combination.

Such as, in patent documentation 1 (Japanese Unexamined Patent Publication 2-146045 publication), the photosensitive polymer combination comprising polymkeric substance and emulsion is disclosed.Disclosing above-mentioned polymkeric substance and have the unit that is made up of ring-shaped fat hydrocarbon skeleton and the unit from maleic anhydride, is the polymkeric substance hydrolysis of the anhydride rings of the unit from maleic anhydride obtained.

Prior art document

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 2-146045 publication

Summary of the invention

But, because the efficiency of the cross-linking reaction comprising the photosensitive polymer combination of above-mentioned polymkeric substance is poor, so need to add a large amount of light acid producing agent, crosslinking chemical.

If add a large amount of light acid producing agent, crosslinking chemical in photosensitive polymer combination, then the various properties deteriorate of the negative-type photosensitive dielectric film obtained.

The present inventor etc. find by using the negative light-sensitive resin combination comprising the multipolymer that following formula (1) represents, the negative-type photosensitive dielectric film of the balancing good of the various characteristics required by negative-type photosensitive dielectric film can be formed, thus complete the present invention.

Namely, according to the present invention, a kind of negative light-sensitive resin combination is provided, comprise polymkeric substance that the multipolymer that represented by following formula (1) forms, light acid producing agent and with the acid produced by above-mentioned smooth acid producing agent for catalyzer is by the first crosslinking chemical of above-mentioned crosslinked polymer.

(in formula (1), l, p and m represent mole containing ratio in polymkeric substance, and meet the condition of l+p+m≤1,0≤l < 1,0 < p < 1 and 0 < m < 1

N and q is 0,1 or 2 independently of one another,

R ₁~ R ₄and R ₈~ R ₁₁be the organic group of hydrogen or carbon number 1 ~ 30 independently of one another,

Be selected from R ₈, R ₉, R ₁₀and R ₁₁in more than 1 or 2 for having the organic group of alcoholic extract hydroxyl group,

The structural unit of A for being represented by following formula (2a), (2b), (2c) or (2d))

(in formula (2a) and formula (2b), R ₅, R ₆and R ₇be the organic group of carbon number 1 ~ 18 independently of one another)

In addition, according to the present invention, provide and above-mentioned negative light-sensitive resin combination is solidified and the cured film that obtains.

In addition, according to the present invention, provide the electronic installation possessing above-mentioned cured film.

Further, according to the present invention, the polymkeric substance that the multipolymer represented by following formula (1) is formed is provided.

N and q is 0,1 or 2 independently of one another,

According to the present invention, the negative light-sensitive resin combination of the negative-type photosensitive dielectric film of the balancing good of the various characteristics that can be formed required by negative-type photosensitive dielectric film can be provided.

Accompanying drawing explanation

Fig. 1 is the sectional view of an example of the electronic installation representing present embodiment.

Fig. 2 is the sectional view of an example of the electronic installation representing present embodiment.

Symbol description

10 substrates

12 counter substrate

14 liquid crystal layers

20,50,52,54 dielectric films

22,24,26 openings

30 transistors

31 gate electrodes

32 source electrodes

33 drain electrodes

34 gate insulating films

35 semiconductor layers

40,42 distributions

70 distributions again

72 the superiors' distributions

74 salient points

80 wiring layers again

90,92 alignment films

100 electronic installations

Embodiment

Below, accompanying drawing is used to be described embodiment.Should with explanation, in whole accompanying drawings, mark same symbol to same inscape, suitably the description thereof will be omitted.In addition, " ~ ", when not having specified otherwise, represents above to following.

< negative light-sensitive resin combination >

The negative light-sensitive resin combination P of present embodiment comprise the first polymkeric substance that the multipolymer that represented by following formula (1) forms, light acid producing agent and with the acid produced by above-mentioned smooth acid producing agent for catalyzer is by the first crosslinking chemical of the first crosslinked polymer.

(in formula (1), l, p and m represent mole containing ratio in polymkeric substance, and meet the condition of l+p+m≤1,0≤l < 1,0 < p < 1 and 0 < m < 1, n and q is 0,1 or 2, R independently of one another ₁~ R ₄and R ₈~ R ₁₁be the organic group of hydrogen or carbon number 1 ~ 30 independently of one another, be selected from R ₈, R ₉, R ₁₀and R ₁₁in more than 1 or 2 for having the organic group of alcoholic extract hydroxyl group, A is the structural unit represented by following formula (2a), (2b), (2c) or (2d))

According to such negative light-sensitive resin combination P, by using above-mentioned first polymkeric substance, the negative-type photosensitive dielectric film of the balancing good of the such as various characteristics required by negative-type photosensitive dielectric film such as developability, resolution, residual film, insulativity, the transparency, thermotolerance, solvent resistance can be provided.

Because the first polymkeric substance has alcoholic extract hydroxyl group on side chain, so excellent with the reactivity of the first crosslinking chemical.Thereby, it is possible to reduce the addition of the light acid producing agent of high price, therefore economy is excellent.In addition, owing to can reduce the addition of the crosslinking chemical making developability deterioration, so film when significantly can reduce development reduces, its result, can reduce the uneven thickness of negative-type photosensitive dielectric film or can improve the flatness of film.Further, due to the higher negative-type photosensitive dielectric film of degree of crosslinking can be obtained, so residual film, thermotolerance, the transparency, solvent resistance etc. can be improved.In addition, resolution, insulativity can be maintained existing level.

Negative light-sensitive resin combination P can comprise other the material such as adjuvant further.Below, each composition is described.

< first polymkeric substance >

First polymkeric substance of present embodiment is the multipolymer that following formula (1) represents.

In formula (1), l, p and m represent mole containing ratio (mol%) in polymkeric substance, and meeting the condition of l+p+m≤1,0≤l < 1,0 < p < 1 and 0 < m < 1, n and q is 0,1 or 2 independently of one another.In addition, l, p and m preferably 0≤l≤0.25,0.25≤p≤0.50,0.50≤m≤0.75.

N and q is 0,1 or 2 independently of one another.

R ₁~ R ₄and R ₈~ R ₁₁be the organic group of hydrogen or carbon number 1 ~ 30 independently of one another.R ₁~ R ₄and R ₈~ R ₁₁can be mutually the same, in addition also can be different from each other.

Be selected from R ₈, R ₉, R ₁₀and R ₁₁in more than 1 or 2 for having the organic group of alcoholic extract hydroxyl group.At this, in present embodiment, alcoholic extract hydroxyl group refers to the hydroxyl with the carbon atom bonding of the alkyl of chain or ring-type.

The structural unit of A for being represented by following formula (2a), (2b), (2c) or (2d).In the multipolymer represented by above-mentioned formula (1), comprise the one kind or two or more structural unit A be selected from following formula (2a), (2b), (2c) and (2d).In present embodiment, preferably comprise the one kind or two or more structural unit A be selected from following formula (2a) and (2c), more preferably comprise the one kind or two or more structural unit A be selected from following formula (2a), (2b) and (2c).Should illustrate, the first polymkeric substance can comprise other structural unit beyond the structural unit shown in above-mentioned formula (1).

In formula (2a) and formula (2b), R ₅, R ₆and R ₇be the organic group of carbon number 1 ~ 18 independently of one another.

Form R ₁~ R ₄and R ₈~ R ₁₁the organic group of carbon number 1 ~ 30 can containing more than 1 that is selected from O, N, S, P and Si in its structure.Wherein, R is formed ₁-R ₄organic group all not there is alcoholic extract hydroxyl group.

In present embodiment, as formation R ₁~ R ₄and R ₈~ R ₁₁organic group, such as can enumerate alkyl, alkenyl, alkynyl, alkylidene radical, aryl, aralkyl, alkaryl, naphthenic base and heterocyclic radical.

As alkyl, such as, can enumerate methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl, the tert-butyl group, amyl group, neopentyl, hexyl, heptyl, octyl group, nonyl and decyl.As alkenyl, such as, can enumerate allyl, pentenyl and vinyl.As alkynyl, ethinyl can be enumerated.As alkylidene radical, such as, can enumerate methene base and ethidine.As aryl, such as, can enumerate phenyl, naphthyl and anthryl.As aralkyl, such as, can enumerate benzyl and phenethyl.As alkaryl, such as, can enumerate tolyl, xylyl.As naphthenic base, such as, can enumerate adamantyl, cyclopentyl, cyclohexyl and ring octyl group.As heterocyclic radical, such as, can enumerate epoxy radicals and oxetanyl.

Should illustrate, by comprising alkyl as R ₁~ R ₄and R ₈~ R ₁₁, the masking of the film be made up of the negative light-sensitive resin combination P comprising the first polymkeric substance can be improved.In addition, by comprising aryl as R ₁~ R ₄and R ₈~ R ₁₁, for the film be made up of the negative light-sensitive resin combination P comprising the first polymkeric substance, film when using alkaline-based developer to develop in photo-mask process can be suppressed to reduce.

In addition, in abovementioned alkyl, alkenyl, alkynyl, alkylidene radical, aryl, aralkyl, alkaryl, naphthenic base and heterocyclic radical, the hydrogen atom of more than 1 can be replaced by halogen atom.As halogen atom, fluorine, chlorine, bromine and iodine can be enumerated.The wherein haloalkyl that replaced by halogen atom of the hydrogen atom of more than 1 of preferred alkyl.By making R ₁~ R ₄and R ₈~ R ₁₁in at least one be haloalkyl, thus use first polymkeric substance form negative light-sensitive resin combination P time, the specific inductive capacity of this negative light-sensitive resin combination P can be reduced.

R is selected from as formation ₈, R ₉, R ₁₀and R ₁₁in the organic group with alcoholic extract hydroxyl group of more than 1 or 2, such as, be the group with the alcoholic extract hydroxyl group of more than 1 and the alkyl of above-mentioned alcoholic extract hydroxyl group institute bonding.

As above-mentioned alcoholic extract hydroxyl group, it is the tertiary alcohol hydroxyl of primary hydroxyl group or secondary hydroxyl group or chain.Wherein from the viewpoint of cross-linking reaction excellence, the primary hydroxyl group of preferred chain or secondary hydroxyl group, the particularly preferably primary hydroxyl group of chain.

At this, " primary hydroxyl group " refers to the hydroxyl with the primary carbon atom bonding forming chain or cyclic hydrocarbon group." secondary hydroxyl group " refers to the hydroxyl with the secondary carbon bonding forming chain or cyclic hydrocarbon group." tertiary alcohol hydroxyl " refers to the hydroxyl with the tertiary carbon atom bonding forming chain alkyl.

As the alkyl of chain, such as, the alkyl of straight-chain or branched can be enumerated.

In addition, as the alkyl of ring-type, such as, aliphatics ring type group can be enumerated.

In addition, alkyl can be saturated or undersaturated, is usually preferably saturated.In addition, the part forming the hydrogen atom of alkyl can be substituted.The alternatively substituting group of a part for hydrogen atom, can enumerate fluorine atom, oxygen atom (=O), cyano group etc.

When alkyl is straight-chain, preferred carbon number is 1 ~ 10, and more preferably carbon number is 1 ~ 5.

When alkyl is aliphatics ring type group, the group etc. removing more than 2 hydrogen atoms from cyclopentane, cyclohexane, norbornane, isoborneol alkane, diamantane, tristane, tetracyclododecane can be enumerated.

Wherein preferably carbon number is the alkyl of the straight-chain of 1 ~ 10, and more preferably carbon number is the alkyl of the straight-chain of 1 ~ 5.

Form and be selected from R ₈, R ₉, R ₁₀and R ₁₁in the organic group with alcoholic extract hydroxyl group of more than 1 or 2 can containing comprise heteroatomic divalent link group.As such organic group, such as, the group being bonded with alcoholic extract hydroxyl group at the end comprising heteroatomic divalent link group can be enumerated.

As comprise heteroatomic divalent link group, such as, can enumerate-O-,-C (=O)-O-,-C (=O)-,-O-C (=O)-O-,-C (=O)-NH-,-NH-,-S-,-S (=O) ₂-,-S (=O) ₂-O-etc.

Should illustrating, comprising the first polymkeric substance and the light transmission of film that forms, preferred R from the viewpoint of improving ₁, R ₂, R ₃and R ₄in any one be hydrogen, particularly preferably R ₁, R ₂, R ₃and R ₄be all hydrogen.

In addition, preferred R ₈, R ₉, R ₁₀and R ₁₁in any one be hydrogen, be particularly preferably selected from R ₈, R ₉, R ₁₀and R ₁₁in 3 be hydrogen.

Form R ₅, R ₆and R ₇the organic group of carbon number 1 ~ 18 can comprise in O, N, S, P, Si in its structure wantonly more than 1.In addition, R is formed ₅, R ₆and R ₇organic group can become not containing the organic group of acidic functionality.Thereby, it is possible to make the control of the acid number in the first polymkeric substance become easy.

In present embodiment, as formation R ₅, R ₆and R ₇organic group, such as can enumerate alkyl, alkenyl, alkynyl, alkylidene radical, aryl, aralkyl, alkaryl, naphthenic base and heterocyclic radical.As alkyl, such as, can enumerate methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl, the tert-butyl group, amyl group, neopentyl, hexyl, heptyl, octyl group, nonyl and decyl.As alkenyl, such as, can enumerate allyl, pentenyl and vinyl.As alkynyl, ethinyl can be enumerated.As alkylidene radical, such as, can enumerate methene base and ethidine.As aryl, such as, can enumerate phenyl, naphthyl and anthryl.As aralkyl, such as, can enumerate benzyl and phenethyl.As alkaryl, such as, can enumerate tolyl, xylyl.As naphthenic base, such as, can enumerate adamantyl, cyclopentyl, cyclohexyl and ring octyl group.As heterocyclic radical, such as, can enumerate epoxy radicals and oxetanyl.

In addition, the hydrogen atom of more than 1 of abovementioned alkyl, alkenyl, alkynyl, alkylidene radical, aryl, aralkyl, alkaryl, naphthenic base and heterocyclic radical can be replaced by halogen atom.As halogen atom, fluorine, chlorine, bromine and iodine can be enumerated.The wherein haloalkyl that replaced by halogen atom of the hydrogen atom of more than 1 of preferred alkyl.

The alternating copolymer that the repetitive that multipolymer shown in above-mentioned formula (1) is preferably the norbornene-type monomers such as represented from following formula (3) or (4) is alternately arranged with the repetitive from the maleic anhydride shown in following formula (5).Should illustrate, the multipolymer shown in above-mentioned formula (1) can be random copolymers, segmented copolymer.

Repetitive from the maleic anhydride shown in following formula (5) is the structural unit represented by the A in above-mentioned formula (1).Should illustrate, the first polymkeric substance also can comprise the monomer that represented by following formula (3), (4) and (5) as low molecular weight compositions.

In formula (3) and (4), n and q is 0,1 or 2 independently of one another.R ₁~ R ₄and R ₈~ R ₁₁be the organic group of hydrogen or carbon number 1 ~ 30 independently of one another.R ₁~ R ₄and R ₈~ R ₁₁can be mutually the same, in addition also can be different from each other.

Be selected from R ₈, R ₉, R ₁₀and R ₁₁in more than 1 or 2 be have to be selected from alcoholic extract hydroxyl group and hydrolyzable and to form the organic group of at least one in the group of alcoholic extract hydroxyl group.Generate the group of alcoholic extract hydroxyl group as hydrolyzable, can enumerate the group of the protecting group protections such as alcoholic extract hydroxyl group alkyl, acetyl group.

For the first polymkeric substance in present embodiment, such as Mw (weight-average molecular weight)/Mn (number-average molecular weight) is 1.5 ~ 2.5.Should illustrate, Mw/Mn is the dispersion degree of the width representing molecular weight distribution.

The present inventor finds by controlling in certain scope by the molecular weight distribution of the first polymkeric substance, for the film formed by this first polymkeric substance, can suppress the distortion of pattern when solidifying.Therefore, by making the Mw/Mn of the first polymkeric substance be above-mentioned scope, the pattern form of the film formed by the negative light-sensitive resin combination P comprising the first polymkeric substance can be made good.

In addition, the Mw (weight-average molecular weight) of the first polymkeric substance is such as 3000 ~ 30000.

Should illustrate, the polystyrene conversion value that weight-average molecular weight (Mw), number-average molecular weight (Mn) and molecular weight distribution (Mw/Mn) use the typical curve of the polystyrene standard (PS) such as obtained by utilizing GPC to measure to obtain.Condition determination is such as follows.

Dong Cao Inc. gel permeation chromatography device HLC-8320GPC

Chromatographic column: Dong Cao Inc. TSK-GEL Supermultipore HZ-M

Detecting device: phase chromatography-use RI detecting device

Measure temperature: 40 DEG C

Solvent: THF

Sample solution concentration: 2.0mg/ milliliter

First polymkeric substance of present embodiment such as manufactures as follows.

(polymerization process (treatment S 1))

First the norbornene-type monomers that the norbornene-type monomers that formula (4) represents, the maleic anhydride becoming monomer and the formula (3) that uses as required represent is prepared.

In the norbornene-type monomers that formula (3) represents, as long as n is 0,1 or 2, preferably 0 or 1.Thereby, it is possible to improve the flexibility of the film formed by the resin combination of the polymkeric substance comprising present embodiment.

Similarly, in the norbornene-type monomers that formula (4) represents, as long as q is 0,1 or 2, preferably 0 or 1.Thereby, it is possible to improve the flexibility of the film formed by the resin combination of the polymkeric substance comprising present embodiment.

As the norbornene-type monomers that formula (3) represents, specifically, dicyclo [2.2.1]-hept-2-ene" (trivial name: norborene) can be enumerated, in addition, as the norbornene-type monomers with alkyl, 5-methyl-2-norborene can be enumerated, 5-ethyl-2-norborene, 5-butyl-2-norborene, 5 hexyl-2-norborene, 5-decyl-2-norborene etc., as the norbornene-type monomers with alkenyl, 5-allyl-2-norborene can be enumerated, 5-(2-propenyl)-2-norborene, 5-(1-methyl-4 pentenyl)-2-norborene etc., as the norbornene-type monomers with alkynyl, 5-ethinyl-2-norborene etc. can be enumerated, as the norbornene-type monomers with aralkyl, 5-benzyl-2-norborene can be enumerated, 5-phenethyl-2-norborene etc.

As norbornene-type monomers, more than any one in them can be used.Wherein, from the view point of the light transmission of polymkeric substance, preferably use dicyclo [2.2.1]-hept-2-ene" (trivial name: norborene).

As the norbornene-type monomers that formula (4) represents, specifically, the part can enumerating the hydrogen of the norbornene-type monomers above-mentioned formula (3) represented is replaced to have and is selected from alcoholic extract hydroxyl group and hydrolyzable and generates the organic group of at least one in the group of alcoholic extract hydroxyl group and the monomer that obtains.

Next, the norbornene-type monomers that norbornene-type monomers formula (3) represented, formula (4) represent and maleic anhydride addition polymerization.At this, by free radical polymerization, form the multipolymer (copolymer 1) of norbornene-type monomers that formula (3) represents, norbornene-type monomers that formula (4) represents and maleic anhydride.

From the viewpoint of the efficiency that can improve cross-linking reaction further, the molal quantity of the norbornene-type monomers that formula (3) represents is preferably 0mol% ~ 25mol%, the molal quantity of the norbornene-type monomers that formula (4) represents is preferably 25mol% ~ 50mol%, and the molal quantity of maleic anhydride is preferably 50mol% ~ 75mol%.

The norbornene-type monomers, maleic anhydride and the polymerization initiator that are represented by the norbornene-type monomers that formula (3) represented, formula (4) are dissolved in solvent, thereafter, the heating stipulated time, thus norbornene-type monomers, maleic anhydride that norbornene-type monomers formula (3) represented, formula (4) represent carry out solution polymerization.Heating-up temperature is such as 50 ~ 80 DEG C, and the heat time is 10 ~ 20 hours.

As solvent, wantonly more than a kind in such as tetrahydrofuran, toluene, MEK etc. can be used.

As polymerization initiator, wantonly more than a kind in azo-compound and organic peroxide can be used.

As azo-compound, such as can enumerate azobis isobutyronitrile (AIBN), dimethyl 2,2 '-azo two (2 Methylpropionic acid ester), 1, two (cyclohexane carbonitrile) (ABCN) of 1 '-azo, can use more than any one in them.

In addition, as organic peroxide, such as can enumerate hydrogen peroxide, di-tert-butyl peroxide (DTBP), benzoyl peroxide (Benzoyl peroxide, BPO) and methyl ethyl ketone peroxide (MEKP), more than any one in them can be used.

The amount (molal quantity) of polymerization initiator is preferably 1% ~ 10% of the total molal quantity of norbornene-type monomers that formula (3) represents, norbornene-type monomers that formula (4) represents and maleic anhydride.By the amount of polymerization initiator being suitably set in above-mentioned scope, and suitably set temperature of reaction, reaction time, thus the weight-average molecular weight of the polymkeric substance obtained (Mw) can be adjusted to 3000 ~ 30000.

By this polymerization process (treatment S 1), can by the copolymer 1 polymerization of repetitive that there is the repetitive represented with following formula (6), the repetitive represented with following formula (7) and represent with following formula (8).

Wherein, in copolymer 1, the R of the structure of formula (7) ₁preferably identical in each repetitive, but also can be different in each repetitive.R ₂~ R ₄and R ₈~ R ₁₁too.

(in formula (7), n, R ₁~ R ₄identical with above-mentioned formula (1).That is, n is any one in 0,1,2.R ₁~ R ₄for the organic group of respective independently hydrogen or carbon number 1 ~ 30.In formula (7), R ₁~ R ₄can be identical or different) (in formula (8), q, R ₈~ R ₁₁identical with above-mentioned formula (1).That is, q is any one in 0,1,2.In addition, R ₈~ R ₁₁for the organic group of respective independently hydrogen or carbon number 1 ~ 30.Be selected from R ₈, R ₉, R ₁₀and R ₁₁in more than 1 or 2 for having the organic group of alcoholic extract hydroxyl group.In formula (8), R ₈~ R ₁₁can be identical or different)

Copolymer 1 can be the multipolymer of the random configuration of repetitive that the repetitive that represents of repetitive, the formula (7) formula (6) represented and formula (8) represent, in addition, also can be the multipolymer of alternately configuration.In addition, also can be the multipolymer that the norbornene-type monomers that represents of norbornene-type monomers, formula (4) that formula (3) represents and maleic anhydride carry out block copolymerization.Wherein, from the viewpoint of the deliquescent homogeneity of negative light-sensitive resin combination P guaranteeing to employ the polymkeric substance that present embodiment manufactures, the structure that the repetitive that preferably repetitive that represents of formula (6) and formula (8) represent alternately configures.That is, copolymer 1 preferably has the multipolymer of the repetitive represented with following formula (9).

(in formula (9), q, R ₈~ R ₁₁identical with above-mentioned formula (1).That is, q is any one in 0,1,2.R ₈~ R ₁₁for the organic group of hydrogen or carbon number 1 ~ 30.In addition, R is selected from ₈, R ₉, R ₁₀and R ₁₁in more than 1 or 2 for having the organic group of alcoholic extract hydroxyl group.R ₈~ R ₁₁can be identical or different.In addition, a is the integer of 10 ~ 200)

At this, the R of preferred formula (9) structure ₈identical in each repetitive, but also can be different in each repetitive.R ₉~ R ₁₁too.

(open loop operation (treatment S 2))

Then, in the repetitive of the ring texture from maleic anhydride of the copolymer 1 of gained, the repetitive making a part is the state of closed loop, simultaneously by remaining repetitive open loop.Thus, the amount of the carboxyl in copolymer 1 can be adjusted.That is, the acid number of the first made polymkeric substance can be controlled.

In present embodiment, at copolymer 1 from the repetitive of maleic anhydride, the repetitive not open loop of such as more than 50%, and the ring texture of remaining repetitive above-mentioned (anhydride rings) open loop.That is, the open loop rate of copolymer 1 is such as less than 50%.Wherein, in total number of the repetitive of the ring texture from maleic anhydride of copolymer 1, the preferably repetitive not open loop of 60% ~ 90%.

At this, the open loop rate from the repetitive of maleic anhydride can be measured as follows.

Measure the IR absorption intensity (A1) of (C=O) in the acid anhydride structure of the copolymer 1 before open loop, be calculated as follows open loop rate by the IR absorption intensity (A2) of (C=O) in the acid anhydride structure after open loop.

Open loop rate (%)=((A1-A2)/A1) × 100

Should illustrate, use acetonitrile as internal standard compound matter.

Specifically, will

(A) as the metal alkoxide of alkali

(B) alcohol and the alkali metal hydroxide as alkali

In either party add in the reactant liquor of above-mentioned copolymer 1 polymerization in above-mentioned polymerization process, simultaneously add the organic solvents such as MEK (MEK) further, stir 1 ~ 5 hour at 40 ~ 50 DEG C, obtain reactant liquor L1.In reactant liquor L1, a part of anhydride rings open loop of the repetitive from maleic anhydride of copolymer 1, a part of end simultaneously formed by open loop is esterified.Should illustrate, remaining end is not esterified, becomes slaine structure.

In present embodiment, the molal quantity of metal alkoxide or alkali metal hydroxide is preferably less than 50% of the molal quantity of the maleic anhydride used in polymerization process.Wherein, the molal quantity of metal alkoxide or alkali metal hydroxide is preferably 10% ~ 40% of the molal quantity of the maleic anhydride used in polymerization process, and more preferably less than 30%.Thereby, it is possible to reduce the amount of metal alkoxide or alkali metal hydroxide, the alkali metal concn in the polymkeric substance finally obtained can be reduced.

By reducing the alkali metal concn in polymkeric substance, the migration of metallic ion can be suppressed when forming the equipment using this polymkeric substance.

As above-mentioned metal alkoxide, preferred M (OR ₅) shown in metal alkoxide (M is the metal of 1 valency, R ₅organic group for carbon number 1 ~ 18).As metal M, can alkaline metal be enumerated, wherein, from the view point of operability, preferred sodium.As R ₅, such as, can enumerate and the R in above-mentioned formula (2a) ₅same group.

Should illustrate, as metal alkoxide, two or more different metal alkoxide can be used.But, from the view point of manufacture stability, preferably use a kind of metal alkoxide.

On the other hand, as mentioned above, also can (B) alcohol and as the existence of the alkali metal hydroxide of alkali under by the structure open loop from maleic anhydride of copolymer 1.

As alkali metal hydroxide, from the view point of operability, preferred NaOH.

As alcohol, preferably 1 valency alcohol (R ₅oH).As the R of organic group ₅above-mentioned group can be used.Should illustrate, R ₅be preferably carbon number less than 10.

The repetitive from maleic anhydride of open loop is the structure shown in following formula (10) in this open loop operation (treatment S 2), is the structure of the salt part with carboxyl.The multipolymer of the structure with this formula (10) is called multipolymer 2.

(in formula (10), R ₅with above-mentioned R ₅equally, be group from above-mentioned alcohol or metal alkoxide.)

Should illustrate, in multipolymer 2, although pettiness, sometimes also form the structure shown in following formula (11).

In addition, in multipolymer 2, although pettiness, sometimes also form the structure shown in following formula (12).

Then, in reactant liquor L1, add the aqueous solution of hydrochloric acid or formic acid etc., acid treatment is carried out, by metallic ion (Na to multipolymer 2 ⁺) and proton (H ⁺) displacement.Thus, in the multipolymer 3 obtained by carrying out acid treatment to multipolymer 2, the repetitive from maleic anhydride of the open loop shown in formula (10) is the structure as following formula (13), and an end is carboxyl.

(in formula (13), R ₅with above-mentioned R ₅equally)

Should illustrate, in multipolymer 2, when having the structure shown in formula (12), this structure becomes the structure as following formula (14).

The multipolymer 3 obtained by carrying out acid treatment to multipolymer 2 has the repetitive shown in the repetitive shown in the repetitive shown in above-mentioned formula (8), formula (6), formula (13), and according to circumstances has the repetitive shown in formula (7), the structure of formula (11) and the structure of formula (14).Further, in total number of the structural unit from maleic anhydride, more than 50% is the repetitive shown in formula (6).Repetitive shown in repetitive shown in formula (6) and formula (13) is (during the structure of the structure of contained (11), formula (14), total for the structure of the repetitive shown in formula (13), formula (11) and the structure of formula (14)) ratio (mol ratio (formula (6): formula (13) (during the structure of the structure of contained (11), formula (14), being formula (13)+formula (11)+formula (14)))) be such as 1:1 ~ 3:1.

Wherein, preferably there is the structure that following formula (15) and (16) alternately configure with the structure from maleic anhydride monomer as repetitive, structure from norbornene-type monomers.Should illustrate, also partly can comprise following formula (17) and (18) as repetitive.

In formula (15) and formula (16), q, R ₈~ R ₁₁identical with above-mentioned formula (1).That is, q is any one in 0,1,2.R ₈~ R ₁₁be the organic group of hydrogen or carbon number 1 ~ 30 independently of one another.Be selected from R ₈, R ₉, R ₁₀and R ₁₁in more than 1 or 2 be have to be selected from alcoholic extract hydroxyl group and hydrolyzable and to generate the organic group of at least one in the group of alcoholic extract hydroxyl group.R ₈~ R ₁₁can be identical or different.In addition, in the structure of formula (16), comprise Z and represent-O-H and-O-R ₅in either party, W represents that the structure of the opposing party and Z and W of trace are-O-R ₅structure.R ₅with above-mentioned R ₅equally.

In addition, Z and W sometimes also comprising trace in the repetitive that formula (16) represents is the structure of-O-H.

In addition, when formula (15) becomes repetitive, preferred R ₈identical in each repetitive, also can be different in each repetitive.R ₉~ R ₁₁too.

Similarly, when formula (16) becomes repetitive, preferred R ₈identical in each repetitive, also can be different in each repetitive.R ₉~ R ₁₁, W, Z too.

In formula (17) and formula (18), n, R ₁~ R ₄identical with above-mentioned formula (1).That is, n is any one in 0,1,2.R ₁~ R ₄be the organic group of hydrogen or carbon number 1 ~ 30 independently of one another.R ₁~ R ₄can be identical or different.In addition, in the structure of formula (18), comprise Z and represent-O-H and-O-R ₅either party, W represents that the structure of the opposing party and Z and W of trace are-O-R ₅structure.R ₅with above-mentioned R ₅equally.

In addition, in the repetitive that formula (18) represents, Z and W sometimes also comprising trace is the structure of-O-H.

In addition, when formula (17) becomes repetitive, R ₁preferably identical in each repetitive, also can be different in each repetitive.R ₂~ R ₄too.

Similarly, when formula (18) becomes repetitive, R ₁preferably identical in each repetitive, also can be different in each repetitive.R ₂~ R ₄, W, Z too.

In this open loop operation (treatment S 2), copolymer 1 from the repetitive of maleic anhydride, by the repetitive not open loop of more than 50%, by ring texture (anhydride rings) open loop of remaining repetitive, obtain multipolymer 2.In multipolymer 2, as mentioned above, the end bond wire (such as, Na) formed in the open loop of maleic acid anhydro ring, but pass through the repetitive not open loop of more than 50%, thus amount of metal contained in the polymkeric substance as product can be reduced.Thereby, it is possible to the alkali-metal amount in the polymkeric substance finally obtained in reduction present embodiment, characteristic required in the negative light-sensitive resin combination P using this polymkeric substance can be played.

(matting (treatment S 3))

Then, the potpourri of the solution with water and organic solvent (such as, MEK) that comprise the multipolymer 3 obtained by above operation is cleaned, removes kish composition.Multipolymer 3, residual monomer and oligomer are transferred to organic layer.Thereafter, water layer (the first cleaning) is removed.

Thereafter, in organic layer, again add the potpourri of water and organic solvent (such as, MEK), carry out cleaning (the second cleaning).

(low molecular weight compositions removal step (treatment S 4))

Then, after being concentrated by the above-mentioned organic layer comprising multipolymer 3 and the low molecular weight compositions such as residual monomer and oligomer, it is made again to be dissolved in the organic solvents such as THF.Then, in this solution, add hexane and methyl alcohol, make the polymer coagulates precipitation comprising multipolymer 3.At this, as low molecular weight compositions, comprise residual monomer, oligomer and polymerization initiator etc.Then, filter, and make the coagulum of gained dry.Thereby, it is possible to the polymkeric substance that the multipolymer 3 obtaining eliminating low molecular weight compositions is major component (principal product).

Should illustrate, when implementing aftermentioned heating process, in this low molecular weight compositions removing step (treatment S 4), such as, by comprising the mixed liquor cleaning of the above-mentioned organic layer methyl alcohol of multipolymer 3, residual monomer and oligomer, water, hexane, remove organic layer.

(heating process (treatment S 5))

In present embodiment, by adjusting the open loop rate from the repetitive of maleic anhydride by above-mentioned open loop operation (treatment S 2), thus have adjusted the first polymkeric substance to alkaline-based developer (such as, TMAH (tetramethylammonium hydroxide aqueous solution)) dissolution velocity, needs further strictly adjust dissolution velocity time preferably implement this heating process (treatment S 5).In this heating process (treatment S 5), adjust the first polymkeric substance further to the dissolution velocity of alkaline developer by heating multipolymer 3.

Heating process (treatment S 5) is carried out as follows.

Eliminate in the liquid of organic layer in low molecular weight compositions removing step (S4) and add alcohol, after making methyl alcohol evaporate, 120 ~ 140 DEG C of heating 0.5 ~ 10 hour.Alcohol can be used as above-mentioned alcohol (R as used herein ₅oH) illustrative alcohol.

In this heating process (treatment S 5), by a part of carboxyl of multipolymer 3, namely at the carboxyl esterification that the end of the open loop structure of the structure from maleic anhydride is formed.In addition, in this heating process (treatment S 5), the dehydration of the open loop structure of the structure from maleic anhydride of multipolymer 3 and closed loop again.

Therefore, the multipolymer 4 obtained through this operation possesses the repetitive shown in above-mentioned formula (8), the repetitive shown in formula (6), the repetitive shown in the repetitive shown in formula (13) and following formula (19).

In formula (19), comprise R ₆and R ₇with the R in above-mentioned formula (2b) ₆and R ₇equally, be the structure of organic group of independently carbon number 1 ~ 18.

Structure shown in this formula (19) comprises R ₇for above-mentioned R ₅, R ₆the organic group of carbon number 1 ~ 18 be the situation of the group from the alcohol used in this heating process (treatment S 5).Now, R ₆can be above-mentioned R ₅in any one in illustrative organic group.

In addition, in the structure that formula (19) represents, the structure shown in above-mentioned formula (11) can be comprised.Now, the R of formula (19) ₆and R ₇be and the R shown in formula (11) ₅identical group.

In addition, can comprise the structure of 2 carboxyl esterifications in formula (14) in the structure shown in formula (19).Now, R ₆and R ₇being all the groups from the alcohol used in this heating process (treatment S 5), can be above-mentioned R ₅in any one in illustrative organic group.

Thereby, it is possible to the product (polymkeric substance) that to obtain with multipolymer 4 be principal product.

This multipolymer 4 is also same with multipolymer 3, the structure that the structure preferably from norbornene-type monomers alternately configures with the structure from maleic anhydride monomer.And multipolymer 4 preferably has the following structure shown in formula (20) further on the basis of above-mentioned formula (15), (16).

In formula (20), q, R ₈~ R ₁₁identical with above-mentioned formula (1).That is, q is any one in 0,1,2.R ₈~ R ₁₁respective is independently the organic group of hydrogen or carbon number 1 ~ 30.In addition, R is selected from ₈, R ₉, R ₁₀and R ₁₁in more than 1 or 2 be have to be selected from alcoholic extract hydroxyl group and hydrolyzable and to generate the organic group of at least one in the group of alcoholic extract hydroxyl group.R ₈~ R ₁₁can be identical or different.X represents-O-R ₆with-O-R ₇in either party, Y represents the opposing party.R ₆, R ₇same with above-mentioned formula (19).

Through above operation, obtain the first polymkeric substance of the present embodiment shown in above-mentioned formula (1).

By all solids composition of negative light-sensitive resin combination P (namely, composition except desolventizing) when being set to 100 quality %, the ratio of the first polymkeric substance in negative light-sensitive resin combination P is preferably 40 quality % ~ 90 quality %, is more preferably 60 quality % ~ 80 quality %.

< light acid producing agent >

Negative light-sensitive resin combination P contains irradiation by ultraviolet isoreactivity light and acidic smooth acid producing agent.As light acid producing agent, can enumerate salt compound, such as, can enumerate sulfonium salt, iodine salt etc.

As sulfonium salt, such as, triarylsulfonium salt, triakylsulfonium salts, dialkylphenacylsulfonium salts, dialkyl group-4-hydroxyphenyl sulfonium salt etc. can be enumerated.Wherein preferred triarylsulfonium salt.

As iodine salt, preferred Diaryl iodonium salt.

Light acid producing agent can be used alone a kind, also can combine two or more and use.

As the commercially available product of light acid producing agent, such as, CPI-100P, CPI-101A, CPI-200K, CPI-210S (San-Apro Inc.) etc. can be enumerated.

When becoming to be divided into 100 quality % by all solids of negative light-sensitive resin combination P, the ratio of the light acid producing agent in negative light-sensitive resin combination P is preferably 0.1 ~ 5 quality %.

< first crosslinking chemical >

As the first crosslinking chemical, as long as just can be not particularly limited by the crosslinking chemical of the first crosslinked polymer by the effect of acid, such as, melamine series crosslinking chemical, urea system crosslinking chemical, glycoluril system crosslinking chemical etc. can be enumerated.

As melamine series crosslinking chemical, such as, HMMM, six ethoxyl methyl melamines, six propoxy methyl melamines, six butoxybutyl melamines etc. can be enumerated, wherein preferred HMMM.

As the commercially available product of HMMM, such as, Mw-390 (Sanwa-Chemical Inc.) etc. can be enumerated.

As urea system crosslinking chemical, such as, the carbamide resin that methylates, bi-methoxy MU, two ethoxyl methyl urea, two propoxy methyl urea, two butoxymethyl ureas etc. can be enumerated, wherein preferable methyl carbamide resin.

As the commercially available product of the carbamide resin that methylates, such as, MX-280, MX-290 (Sanwa-Chemical Inc.) etc. can be enumerated.

As glycoluril system crosslinking chemical, such as, N can be enumerated, N, N, N-tetra-(methoxy) glycoluril, N, N, N, N-tetra-(ethoxyl methyl) glycoluril, N, N, N, N-tetra-(propoxy methyl) glycoluril, N, N, N, N-tetra-(i-propoxymethyl) glycoluril, N, the aikoxymethytated glycolurils such as N, N, N-tetra-(butoxymethyl) glycoluril.

As the commercially available product of glycoluril system crosslinking chemical, such as, can enumerate PL-1170,1171,1172 and 1174 (Mitsui Cytec Co., Ltd. systems), MX-270 (Sanwa-Chemical Inc.) etc.

In first crosslinking chemical, preferred glycoluril system crosslinking chemical, more preferably aikoxymethytated glycolurils, particularly preferably N, N, N, N-tetra-(methoxy) glycoluril.

Because the reactivity of the glycoluril in the alcoholic extract hydroxyl group in the first polymkeric substance and glycoluril system crosslinking chemical is more excellent, so when using glycoluril system crosslinking chemical as the first crosslinking chemical, then the thermotolerance of the negative-type photosensitive dielectric film obtained and residual film can be improved further.

When all solids of negative light-sensitive resin combination P is become to be divided into 100 quality %, the ratio of the first crosslinking chemical in negative light-sensitive resin combination P is preferably 5 ~ 40 quality %, from the viewpoint of resolution, be more preferably 5 ~ 30 quality %, more preferably 10 ~ 25 quality %.

< second crosslinking chemical >

Negative light-sensitive resin combination P also can comprise can make the first crosslinked polymer and heat cured second crosslinking chemical different from the first crosslinking chemical by applying heat.This second crosslinking chemical preferably has the compound of cyclic ether group as reactive group, wherein, preferably has the compound of glycidyl or oxetanyl.By using the second such crosslinking chemical, the reagent resistance of the film be made up of negative light-sensitive resin combination P can be improved.

As the compound with glycidyl, can epoxy resin be enumerated, any one epoxy resin following can be used.

Such as, bisphenol A epoxide resin can be enumerated (such as, LX-1, DAISO CHEMICAL Co., Ltd.), 2, 2 '-((((1-(4-(2-(4-(oxirane-2-base-methoxyl) phenyl) propane-2-base) phenyl) ethane-1, 1-bis-base) two (4, 1-phenylene)) two (oxygen base)) two (methylene)) and two (oxirane) (such as, Techmore, VG3101L, PRINTEC Co., Ltd.), trihydroxymethylpropanyltri diglycidyl ether (such as, TMPTGE, CVC SPECIALTY CHEMICALS company) and 1, 1, 3, 3, 5, 5-vegolysen, trisiloxanes (such as 5-two (3-(oxirane-2-ylmethoxy) propyl group), DMS-E09, GELEST company).These structures are below shown.In addition, ARALDITE MT0163 and ARALDITE CY179 (CIBA GEIGY company), EHPE-3150 and Epolite GT300 (DAICEL chemical industry Co., Ltd.) etc. can be enumerated.Can use with more than upper any one.Should illustrate, be not limited to illustration here.

At this, the mean value of n is the integer of 0 ~ 3.

In addition, as epoxy resin, from the viewpoint of the transparency, the specific inductive capacity of negative light-sensitive resin combination P, preferably use multifunctional alicyclic epoxy resin.

As multifunctional alicyclic epoxy resin, such as, the epoxy resin shown in following chemical formula can be used.This epoxy resin is such as poly-[(2-Oxyranyle)-1,2-cyclohexanediol] 2-ethyl-2-(hydroxymethyl)-1,3-PD ether (3:1).This multifunctional alicyclic epoxy resin is preferably made to be 20 quality % ~ 100 quality % of whole second crosslinking chemical (except the first crosslinking chemical).Wherein, this multifunctional alicyclic epoxy resin is more preferably made to be more than the 50 quality % of whole second crosslinking chemical.

In formula, R ³⁶for the alkyl of carbon number 1 ~ 10, s is the integer of 1 ~ 30, and t is the integer of 1 ~ 6.

In addition, as the compound with oxetanyl, such as, following any one can be used.

Such as can enumerate Isosorbide-5-Nitrae-bis-{ [(3-ethyl-3-oxetanyl) methoxyl] methyl } benzene, two [1-ethyl (3-oxetanyl)] methyl ether, 4,4 '-bis-[(3-ethyl-3-oxetanyl) methoxy] 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, two (3-ethyl-3-oxetanylmethyl) hexichol phenates (PVC ス (3-エチ Le-3-オキセタニ Le メチ Le) ジ Off ェノエート), trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythrite four (3-ethyl-3-oxetanylmethyl) ether, poly-[[3-[(3-ethyl-3-oxetanyl) methoxyl] propyl group] silsesquioxane] derivant, oxetanyl silicate, phenol novolak type oxetanes, two [(3-Ethyloxetane-3-base) methoxyl] benzene of 1,3-etc., but be not limited to this.They can be used alone, and also can combine multiple use.

When all solids composition (that is, the composition except desolventizing) of negative light-sensitive resin combination P is set to 100 quality %, the ratio of the second crosslinking chemical in negative light-sensitive resin combination P is preferably 5 quality % ~ 40 quality %.

Other adjuvant of < >

In addition, the adjuvants such as antioxidant, filler, surfactant, sensitizer can be added as required in negative light-sensitive resin combination P.

As antioxidant, more than a kind that is selected from phenol system antioxidant, phosphorous antioxidant and thioether system antioxidant can be used.Antioxidant can suppress the oxidation of the film in oxidation when solidifying and technique thereafter.

As phenol system antioxidant, pentaerythrite base-four (3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester) can be enumerated, two { 2-(3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy)-1,1-dimethyl ethyl } 2,4,8,10-tetra-oxaspiros (5, the 5) undecane of 3,9-, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester, 1,6-hexanediol-bis-(3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester), 1,3,5-trimethyl-2,4,6-tri-(3,5-di-t-butyl-4-acrinyl) benzene, 2,6-di-tert-butyl-4-methy phenol, 2,6-di-t-butyl-4-ethyl-phenol, 2,6-diphenyl-4-octade-cyloxyphenol, (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid stearyl ester, (3,5-di-t-butyl-4-acrinyl) phosphonic acids distearyl ester, thio-diethylene glycol two ((3,5-di-t-butyl-4-hydroxyphenyl) propionic ester), 4,4 '-thiobis (the 6-tert-butyl group-metacresol), 2-octylsulfo-4,6-bis-(3,5-di-t-butyl-4-hydroxyphenoxy)-s-triazine, 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert butyl-6-butylphenol), 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol), two (two (4-hydroxyl-3-tert-butyl-phenyl) butyric acid of 3,3-) glycol ethers, 4,4 '-butylidene two (the 6-tert-butyl group-metacresol), 2,2 '-ethylenebis (4,6-DI-tert-butylphenol compounds), 2,2 '-ethylenebis (4-sec-butyl-6-tert-butyl phenol), 1,1,3-tri-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, two (the 2-tert-butyl group-4-methyl-6-(the 2-hydroxyl-3-tert-butyl group-5-methyl-benzyl) phenyl) terephthalate, 1.3.5-three (2,6-dimethyl-3-hydroxyl-4-t-butylbenzyl) isocyanuric acid ester, 1,3,5-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl)-2,4,6-trimethylbenzenes, 1,3,5-tri-((3,5-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl) isocyanuric acid ester, four (methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester) methane, the 2-tert-butyl group-4-methyl-6-(the 2-acryloxy-3-tert-butyl group-5-methyl-benzyl) phenol, two (1,1-dimethyl-2-hydroxyethyl)-2,4-8,10-tetra-oxaspiros [5, the 5] undecane-bis-(β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester) of 3,9-, triethylene glycol two (β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester), 1,1 '-bis-(4-hydroxyphenyl) cyclohexane, 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert-butylphenol), 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol), 2,2 '-di-2-ethylhexylphosphine oxide (6-(1-methylcyclohexyl)-4-methylphenol), 4,4 '-butylidene-bis(3-methyl-6-t-butyl phenol), two (2-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl propionyloxy) 1,1-dimethyl ethyl)-2,4,8,10-tetra-oxaspiro (5, the 5) undecanes of 3,9-, 4,4 '-thiobis (3 methy 6 tert butyl phenol), 4,4 '-bis-(3,5-di-tert-butyl-4-hydroxyl benzyl) thioether, 4,4 '-thiobis (the 6-tert-butyl group-2-methylphenol), 2,5-di-tert-butyl hydroquinone, 2,5-bis-tertiary pentyl p-dihydroxy-benzene, the 2-tert-butyl group-6-(the 3-tert-butyl group-2-hydroxy-5-methyl base benzyl)-4-aminomethyl phenyl acrylate, 2,4-dimethyl-6-(1-methylcyclohexyl) phenol, styrenated phenol, two ((octylsulfo) methyl)-5-methylphenols of 2,4-etc.Wherein, preferred hindered phenol system antioxidant.

As phosphorous antioxidant, two-(2 can be enumerated, 6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites, three (2, 4-di-tert-butyl-phenyl phosphite ester), four (2, 4-di-t-butyl-5-aminomethyl phenyl)-4, 4 '-biphenylen, 3, 5-di-tert-butyl-4-hydroxyl benzyl phosphonate ester-diethyl ester, two-(2, 6-dicumylphenyl) pentaerythritol diphosphites, 2, 2-di-2-ethylhexylphosphine oxide (4, 6-di-tert-butyl-phenyl) octyl group phosphite ester, three (list of mixing and two-nonylphenylphosphite), two (2, 4-di-tert-butyl-phenyl) pentaerythrite-diphosphites, two (2, 6-di-t-butyl-4-dion e-phenyl) pentaerythritol diphosphites, two (2, 6-di-t-butyl-4-octadecane oxygen base carbonylethyl-phenyl) pentaerythritol diphosphites etc.Wherein, preferred phosphite ester and phosphate.

As thioether system antioxidant, can 3 be enumerated, 3 '-dilauryl thiodipropionate, two (2-methyl-4-(3-dodecyl) sulfo-propionyloxy)-5-tert-butyl-phenyl) thioether, 3,3 '-distearylthiodi-propionate, pentaerythrite-four (3-lauryl thiopropionate) etc.

Antioxidant can be 0.1 ~ 5 % by weight of whole negative light-sensitive resin combination P.

In addition, above-mentioned negative light-sensitive resin combination P can comprise Polyphenols.

As Polyphenols, such as, phenol novolacs, o-cresol novolak, paracresol novolaks, p-t-butyl phenol novolaks, hydroxyl naphthol novolak varnish, bisphenol A novolac, bisphenol F phenolic varnish, terpene modified novolaks, dicyclopentadiene-modified novolaks, P-xylene modified novolac, polybutadiene-modified phenol etc. can be illustrated, wantonly more than a kind can be used.

Also following phenoloid can be used in addition.

Orthoresol can be enumerated, metacresol, paracresol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, bisphenol-A, B, C, E, F and G, 4,4 ', 4 "-methine trisphenol, two [(2-hydroxy-5-methyl base phenyl) the methyl]-4-methylphenol of 2,6-, 4,4 '-[1-[4-[1-(4-hydroxyphenyl)-1-Methylethyl] phenyl] ethylidene] bis-phenol, 4,4 '-[1-[4-[2-(4-hydroxyphenyl)-2-propyl group] phenyl] ethylidene] bis-phenol, 4,4 ', 4 "-ethylidine trisphenol, 4-[two (4-hydroxyphenyl) methyl]-2-thanatol, 4,4 '-[(2-hydroxyphenyl) methylene] two [2,3-xylenol], 4,4 '-[(3-hydroxyphenyl) methylene] two [2,6-xylenol], 4,4 '-[(4-hydroxyphenyl) methylene] two [2,6-xylenol], 2,2 '-[(2-hydroxyphenyl) methylene] two [MX], 2,2 '-[(4-hydroxyphenyl) methylene] two [MX], 4,4 '-[(3,4-dihydroxy phenyl) methylene] two [2,3,6-TMP], 4-[two (3-cyclohexyl-4-hydroxyl-6-aminomethyl phenyl) methyl]-1,2-Benzenediol, two [(3,5-dimethyl-4-hydroxyphenyl) methyl]-1,2, the 3-benzene triols of 4,6-, 4,4 '-[(2-hydroxyphenyl) methylene] two [3-methylphenol], 4,4 ', 4 "-(3-methyl isophthalic acid-propyl-3-base) trisphenol, 4,4 ', 4 ", 4 " '-(Isosorbide-5-Nitrae-phenylene two methine) four phenol, 2,4,6-tri-[(3,5-dimethyl-4-hydroxyphenyl) methyl]-1,3-Benzenediol, 2,4,6-tri-[(3,5-dimethyl-2-hydroxyphenyl) methyl]-1,3-Benzenediol, 4,4 '-[1-[4-[1-[4-hydroxyl-3, two [(hydroxy-3-methyl phenyl) methyl] phenyl of 5-]-1-Methylethyl] phenyl] ethylidene] two [two (hydroxy-3-methyl phenyl) methyl of 2,6-] phenol etc.

In these compounds, preferably 4,4 '; 4 "-methine trisphenol, 2, two [(2-hydroxy-5-methyl base phenyl) the methyl]-4-methylphenol, 4 of 6-, 4 '-[1-[4-[1-(4-hydroxy phenyl)-1-Methylethyl] phenyl] ethylidene] bis-phenol, 4,4 '-[1-[4-[2-(4-hydroxyphenyl)-2-propyl group] phenyl] ethylidene] bis-phenol, 4,4 ', 4 "-ethylidine trisphenol etc.Wantonly more than a kind in them can be used.

Wantonly more than a kind in particularly preferably following compound.

In negative light-sensitive resin combination P, when solid constituent is in addition to the solvents set to 100 quality %, the content of Polyphenols is such as preferably 0 quality % ~ 30 quality %, wherein, is preferably more than 3 quality %.

< solvent >

Negative light-sensitive resin combination P can comprise solvent.As solvent, such as, propylene glycol monomethyl ether (PGME), propylene glycol methyl ether acetate (PGMEA), ethyl lactate, methyl isobutyl carbinol (MIBC), gamma-butyrolacton (GBL), 1-METHYLPYRROLIDONE (NMP), methyl-n-amyl ketone (MAK), diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethylmethyl ether or their potpourri can be adopted.Should illustrate, be not limited at this illustrative solvent.

The preparation method > of < negative light-sensitive resin combination P

The preparation method of negative light-sensitive resin combination P is not particularly limited, and can utilize generally well-known method manufacture.Such as, following method can be enumerated.By coordinating the first polymkeric substance, light acid producing agent, the first crosslinking chemical, the second crosslinking chemical as required, other adjuvant, solvent make them mix equably above-mentioned, obtain negative light-sensitive resin combination P.

The formation method > of < Resist patterns

In addition, for the formation method of Resist patterns employing negative light-sensitive resin combination P, such as, following method can be enumerated.

First, negative light-sensitive resin combination P is coated the supporting masses such as silicon chip.As method negative light-sensitive resin combination P being coated supporting mass, the coating processes such as spin coating, roller coat, flow coat, dip-coating, spraying, scraper for coating can be used.Wherein, preferred spin coating, its revolution is preferably 1000 ~ 3000rpm.

Then, in order to remove the solvent in most negative light-sensitive resin combination P, with suitable temperature and time heating supporting mass, film is formed.Acid extraction is such as 60 ~ 130 DEG C, 1 ~ 5 minute, is preferably 80 ~ 120 DEG C, 1 ~ 3 minute.In addition, the thickness of the film of negative light-sensitive resin combination P is preferably 1.0 ~ 5.0 μm.

Thereafter, expose via the mask for the formation of target pattern, and heat.

It is use the mask for the formation of target pattern that pattern on film is formed, and irradiates active ray etc. and carries out.Then, 80 ~ 140 DEG C of heating 1 ~ 5 minute, preferably 90 ~ 130 DEG C of heating 1 ~ 3 minute, promote solidification.Should illustrate, condition of cure is not limited to above-mentioned condition.

Thereafter, utilize alkaline-based developer to develop, dissolve, remove unexposed portion, heat further, target Resist patterns can be obtained thus.

As developing method, such as, spray development method, spray development method, immersion development method etc. can be enumerated.As development conditions, be generally 23 DEG C, about 1 ~ 10 minute.

As developer solution, such as, the alkaline aqueous solution of the concentration of about 0.1 ~ 10 quality % of Tetramethylammonium hydroxide, NaOH, potassium hydroxide etc. can be enumerated.Cure 30 ~ 120 minutes at 150 ~ 300 DEG C further after development, make it solidify fully, can target pattern be obtained.Should illustrate, condition of cure is not limited to above-mentioned condition.

< characteristic >

According to negative light-sensitive resin combination P described above, the negative-type photosensitive dielectric film of at least 1 characteristic possessed in the following characteristic enumerated can be realized.Should illustrate, as shown in following embodiment, even if when negative light-sensitive resin combination P comprises other adjuvant, these characteristics also can realize.

< characteristic 1: high residual film ratio >

By spin-coating method by after negative light-sensitive resin combination P film forming is on silicon chip, cure 100 seconds with the heating plates of 110 DEG C, thus form the 1st layer, using the thickness of the 1st layer as the 1st thickness (the 1st thickness is 2.0 μm ~ 4.0 μm).Then, use exposure device to take pattern dimension as the line of 10um and the width in space be the optimum exposure of 1:1 to expose.Then cure 120 seconds with heating plate at 120 DEG C further to the 1st layer, with 0.5 quality % tetramethylammonium hydroxide aqueous solution 23 DEG C, under the condition in 20 seconds after development, obtain the 2nd layer, using the thickness of the 2nd layer as the 2nd thickness.Now, meet { (the 2nd thickness)/(the 1st thickness) } × 100 >=80 (%), preferably meet { (the 2nd thickness)/(the 1st thickness) } × 100 >=90 (%).

In addition, after carrying out the heating of 60 minutes with 230 DEG C in an oven by the 2nd layer, the 3rd layer is obtained, using the thickness of the 3rd layer as the 3rd thickness.Now, meet { (the 3rd thickness)/(the 2nd thickness) } × 100 >=70 (%), preferably meet { (the 3rd thickness)/(the 2nd thickness) } × 100 >=75 (%).

According to the negative light-sensitive resin combination P possessing this characteristic 1, due to development treatment, cure the with low uncertainty of thickness caused by process, therefore, it is possible to control the thickness after these process accurately.

But, if negative light-sensitive resin combination P during not only may be used for as photoresist only there is regulation not; the film forming of the film removed, does not remove after also may be used for film forming and stays the film forming of permanent film in the product always.Such permanent film need be controlled to the thickness of design, because negative light-sensitive resin combination P can control thickness as mentioned above accurately, so preferably.

< characteristic 2: low relative dielectric constant >

After using this negative light-sensitive resin combination P to form the film of thickness 3 μm, the relative dielectric constant measured with frequency 10kHz, for less than 4.0, is preferably less than 3.5.The lower limit of relative dielectric constant is not particularly limited, such as, be 2.5.

Relative dielectric constant can be measured as follows.

By negative light-sensitive resin combination P rotary coating (revolution 1000 ~ 3000rpm) on aluminium base, cured for 100 seconds at 110 DEG C with heating plate.Next, exposure device is used to press 500mJ/cm ²exposure.Cured for 120 seconds with heating plate further at 120 DEG C.Thereafter, in an oven with 230 DEG C of heating 60 minutes, the film of thickness 3 μm is formed.

Thereafter, this film forms gold electrode, measure under the condition of room temperature (25 DEG C), 10kHz.

But if during negative light-sensitive resin combination P not only may be used for only there is regulation as photoresist not, the film forming of the interim film removed, does not remove after also may be used for film forming and stays the film forming of permanent film in the product always.When this permanent film is applied to electronic installation, preferred specific inductive capacity is low.Therefore, the negative light-sensitive resin combination P of present embodiment is also suitable for the permanent film being equipped on electronic installation.

< characteristic 3: high-transmission rate >

In addition, negative light-sensitive resin combination P is made to solidify and the cured film of thickness 3 μm that obtains is more than 85% in the transmissivity of the light of the wavelength 400nm in thickness direction.Wherein, above-mentioned transmissivity is preferably more than 90%.There is no particular limitation for the higher limit of transmissivity, such as, be 99%.

Transmissivity can be measured as follows.

By negative light-sensitive resin combination P rotary coating (revolution 1000 ~ 3000rpm) on glass substrate, cured for 100 seconds at 110 DEG C with heating plate.Next, exposure device is used to press 500mJ/cm ²exposure.Cured for 120 seconds with heating plate further at 120 DEG C.Thereafter, in an oven with 230 DEG C of heating 60 minutes, the film of thickness 3 μm is formed.

Ultraviolet-visible spectrophotometer is used to be determined at the transmissivity of the wavelength 400nm of light to this film.

< characteristic 4: high solvent patience >

By negative light-sensitive resin combination P rotary coating (revolution 1000 ~ 3000rpm) on glass substrate, cured for 100 seconds at 110 DEG C with heating plate.Next, exposure device is used to press 500mJ/cm ²exposure.Cured for 120 seconds with heating plate further at 120 DEG C.Thereafter, in an oven with 230 DEG C of heating 60 minutes, the 1st film of thickness 3 μm is obtained.Using the thickness of the 1st film as the 1st thickness, using the 1st film the thickness of room temperature immersion in 1-METHYLPYRROLIDONE after 10 minutes as the 2nd thickness time, meet [{ (the 2nd thickness)-(the 1st thickness) }/(the 1st thickness)] × 100≤5 (%).

According to the negative light-sensitive resin combination P possessing this characteristic 4, even if impregnated in 1-METHYLPYRROLIDONE in the manufacturing process after film forming, thickness also changes hardly.Therefore, it is possible to manufacture the film of the design thickness of regulation accurately.

< purposes >

Next, the purposes of negative light-sensitive resin combination P is described.

If negative light-sensitive resin combination P during not only may be used for only there is regulation as photoresist not; the film forming of the film removed, does not remove after also may be used for film forming and stays the film forming of permanent film (cured film) in the product always.

Such as, as shown in Figure 1, the planarization film of covering transistor can be used as.

In addition, as shown in Figure 2, the interlayer dielectric of the wiring layer again of coating semiconductor device can be also used as.In addition, the colored resist being dispersed with pigment is also gone for.

In addition, negative light-sensitive resin combination P also can as microlens array.Such as, negative light-sensitive resin combination P can be filled in the mould of microlens array, thereafter, carry out photocuring, and carry out heat curing as required and form microlens array.

The microlens array of such manufacture may be used for liquid crystal indicator, plasma display, electric field releasing escope, electroluminescent display etc.

Below, an example of the electronic installation with the film using negative light-sensitive resin combination P to be formed is described.

< electronic installation >

Fig. 1 and Fig. 2 is the sectional view of an example of the electronic installation 100 representing present embodiment respectively.A part for the dielectric film 20 comprised in electronic installation 100 is all shown in any one.

The electronic installation 100 of present embodiment possesses such as the dielectric film 20 of the permanent film formed by negative light-sensitive resin combination P.

As an example of the electronic installation 100 of present embodiment, figure 1 illustrates liquid crystal indicator.But the electronic installation 100 of present embodiment is not limited to liquid crystal indicator, comprise other electronic installation possessing the permanent film formed by negative light-sensitive resin combination P.

As shown in Figure 1, the electronic installation 100 as liquid crystal indicator such as possesses substrate 10, the transistor 30 be arranged on substrate 10, the distribution 40 that is arranged at the dielectric film 20 on substrate 10 in the mode of covering transistor 30 and is arranged on dielectric film 20.

Substrate 10 is such as glass substrate.

Transistor 30 is such as forming the thin film transistor (TFT) of the on-off element of liquid crystal indicator.On the substrate 10, such as multiple transistor 30 is arranged in array-like.The transistor 30 of present embodiment is such as made up of gate electrode 31, source electrode 32, drain electrode 33, gate insulating film 34 and semiconductor layer 35.Gate electrode 31 is such as arranged on substrate 10.Gate insulating film 34 is arranged on substrate 10 in the mode of covering grid electrode 31.Semiconductor layer 35 is arranged on gate insulating film 34.In addition, semiconductor layer 35 is such as silicon layer.Source electrode 32 is that the mode contacted with semiconductor layer 35 with a part is arranged on substrate 10.Drain electrode 33 is to separate with source electrode 32 and the mode that contacts with semiconductor layer 35 of a part is arranged on substrate 10.

Dielectric film 20 forms the planarization film on smooth surface on the substrate 10 as the difference in height for eliminating caused by transistor 30 grade and plays function.In addition, dielectric film 20 is made up of the solidfied material of negative light-sensitive resin combination P.Be provided with the opening 22 of through dielectric film 20 in the mode be connected with drain electrode 33 in dielectric film 20.

On dielectric film 20 be formed with the distribution 40 be connected with drain electrode 33 in opening 22.Distribution 40 plays function as the pixel electrode forming pixel together with liquid crystal.

In addition, dielectric film 20 arranges alignment films 90 in the mode covering distribution 40.

Above the one side being provided with transistor 30 in substrate 10, the mode opposed with substrate 10 is provided with counter substrate 12.One side opposed with substrate 10 in counter substrate 12 is provided with distribution 42.Distribution 42 is arranged at the position opposed with distribution 40.In addition, on this face above-mentioned of counter substrate 12, the mode covering distribution 42 is provided with alignment films 92.

The liquid crystal forming liquid crystal layer 14 is filled with between substrate 10 and this counter substrate 12.

Electronic installation 100 shown in Fig. 1 is such as formed as follows.

First, transistor 30 is formed on the substrate 10.Then, be provided with in the one side of transistor 30 in substrate 10, by print process or spin-coating method coating negative light-sensitive resin combination P, form the dielectric film 20 of covering transistor 30.Thus, the planarization film covering the transistor 30 be arranged on substrate 10 is formed.

Then, exposure imaging is carried out to dielectric film 20, form opening 22 in a part for dielectric film 20.Now, unexposed portion is dissolved in developer solution, and exposed portion remains.This in each example of aftermentioned electronic installation 100 too.

Then, dielectric film 20 is made to be heating and curing.Then, in the opening 22 of dielectric film 20, form the distribution 40 be connected with drain electrode 33.Thereafter, dielectric film 20 configures counter substrate 12, filling liquid crystal between counter substrate 12 and dielectric film 20, form liquid crystal layer 14.

Thus, the electronic installation 100 shown in Fig. 1 is formed.

In addition, as an example of the electronic installation 100 of present embodiment, figure 2 illustrates the semiconductor device utilizing the permanent film formed by negative light-sensitive resin combination P to form again wiring layer 80.

Electronic installation 100 shown in Fig. 2 possesses the semiconductor substrate being provided with the semiconductor elements such as transistor and the multilayer wired layer (not shown) be arranged on semiconductor substrate.The superiors in multilayer wired layer are provided with dielectric film 50 as interlayer dielectric and the superiors' distribution 72 of being arranged on dielectric film 50.The superiors' distribution 72 is such as made up of Al.

In addition, dielectric film 50 is provided with wiring layer 80 again.The mode that wiring layer 80 has to cover the superiors' distribution 72 is again arranged at dielectric film 52 on dielectric film 50, be arranged at the distribution again 70 on dielectric film 52 and be arranged on dielectric film 52 and dielectric film 54 again on distribution 70.

The opening 24 be connected with the superiors distribution 72 is formed at dielectric film 52.Distribution 70 to be formed on dielectric film 52 and in opening 24 again, is connected with the superiors distribution 72.The opening 26 be connected with distribution 70 is again provided with at dielectric film 54.

These dielectric films 52 and dielectric film 54 utilize the permanent film formed by negative light-sensitive resin combination P to form.Dielectric film 52 is by such as exposing the negative light-sensitive resin combination P coated on dielectric film 50, develop, and after forming opening 24, is heating and curing obtains it.In addition, dielectric film 54 is by such as exposing the negative light-sensitive resin combination P coated on dielectric film 52, develop, and after forming opening 26, is heating and curing obtains it.

Salient point 74 is such as formed in opening 26.Electronic installation 100 is such as connected with wiring substrate etc. via salient point 74.

Further, the electronic installation 100 of present embodiment can be utilize the permanent film formed by negative light-sensitive resin combination P to form lenticular optical device.As optical device, such as, liquid crystal indicator, plasma display, electric field releasing escope or electroluminescent display can be enumerated.

Above, embodiments of the present invention are illustrated, but they are illustrations of the present invention, also can adopt various formation other than the above.

In addition, the present invention is not limited to above-mentioned embodiment, and the distortion in the scope that can realize object of the present invention, improvement etc. all comprise in the present invention.

Embodiment

Below, by embodiment and comparative example, the present invention will be described, but the invention is not restricted to these embodiments and comparative example.

[embodiment 1]

Synthesis example 1 > of < first polymkeric substance

To in the reaction vessel of appropriate size possessing stirring machine, measure maleic anhydride (MA, 5.88g, 60mmol), 5-(acetoxy-methyl) norborneol-2-alkene (MeOAcNB, 9.96g, 60mmol) and dimethyl 2, two (2 Methylpropionic acid the ester) (1.38g of 2 '-azo, 6mmol), them are made to be dissolved in MEK (MEK, 2.7g) and toluene (2.7g).In this lysate, logical 10 minutes nitrogen removes oxygen, thereafter, while stirring 70 DEG C of heating 16 hours.Thereafter use MEK (56.6g) diluted reaction mixture, and be injected in a large amount of methyl alcohol, polymkeric substance is separated out.Leach solid, carry out vacuum drying at 40 DEG C, obtain polymkeric substance 13.3g thus.Weight-average molecular weight is 6900, and molecular weight distribution (Mw/Mn) is 1.7.

To in the reaction vessel of appropriate size possessing stirring machine, measure NaOH (6.1g, 0.15mol), butanols (14.0g), toluene (20g), 45 DEG C of mixing 1 hour.Polymkeric substance obtained above (10g) is dissolved in MEK again and makes 25wt% solution, add in above-mentioned suspending liquid and add thermal agitation 3 hours at 45 DEG C further.This mixed liquor is cooled to 40 DEG C, carries out proton addition with formic acid (88 % by weight aqueous solution, 23.8g, 0.46mol) process, thereafter, add MEK and water, water layer is separated, thus remove inorganic residue.Next, reaction mixture is injected in a large amount of hexanes polymkeric substance is separated out.Leach solid, carry out vacuum drying at 40 DEG C, obtain polymkeric substance 10.6g thus.Weight-average molecular weight is 7800, and molecular weight distribution (Mw/Mn) is 2.0.

The preparation > of < negative light-sensitive resin combination

Make 20% propylene glycol monomethyl ether (PGME) solution of the first polymkeric substance of synthesis in 25g synthesis example 1 respectively, 0.1g is as the San-Apro Inc. CPI-210S of light acid producing agent, 1.5g is as the glycoluril system crosslinking chemical (Mx-270 of the first crosslinking chemical, Sanwa-Chemical Inc.), 0.05g is for improving the silane coupling agent (KBM-303 with the adaptation of substrate, Shin-Etsu Silicone Inc.), the F-557 (DIC Inc.) of the actinoid striped occurred on negative-type photosensitive dielectric film when 200ppm is for preventing rotary coating is dissolved in after appropriate PGMEA stirs, with the metre filter of 0.2 μm, prepare resin combination.

[embodiment 2]

First polymkeric substance is changed to following material, in addition, prepares negative light-sensitive resin combination similarly to Example 1 and evaluate.

Synthesis example 2 > of < first polymkeric substance

To in the reaction vessel of appropriate size possessing stirring machine, measure maleic anhydride (MA, 6.13g, 62.5mmol), 5-norborene-2-butylacetic acid ester (BuOAcNB, 13.00g, 62.5mmol) and dimethyl 2, two (2 Methylpropionic acid the ester) (1.44g of 2 '-azo, 6.3mmol), them are made to be dissolved in MEK (MEK, 3.4g) and toluene (3.4g).Oxygen is removed to this lysate logical 10 minutes nitrogen, thereafter, while stirring 70 DEG C of heating 16 hours.Thereafter use MEK (68.3g) diluted reaction mixture, and be injected in a large amount of methyl alcohol, polymkeric substance is separated out.Leach solid, carry out vacuum drying at 40 DEG C, obtain polymkeric substance 15.0g thus.Weight-average molecular weight is 10800, and molecular weight distribution (Mw/Mn) is 1.7.

To in the reaction vessel of appropriate size possessing stirring machine, measure NaOH (5.2g, 0.13mol), butanols (12.1g), toluene (20g), 45 DEG C of mixing 1 hour.Polymkeric substance obtained above (10g) is dissolved in MEK again and makes 25wt% solution, add in above-mentioned suspending liquid and add thermal agitation 3 hours at 45 DEG C further.This mixed liquor is cooled to 40 DEG C, carries out proton addition with formic acid (88 % by weight aqueous solution, 20.5g, 0.39mol) process, thereafter, add MEK and water, water layer is separated, removes inorganic residue thus.Next, reaction mixture is injected in a large amount of hexanes polymkeric substance is separated out.Leach solid, carry out vacuum drying at 40 DEG C, obtain polymkeric substance 10.8g thus.Weight-average molecular weight is 15300, and molecular weight distribution (Mw/Mn) is 2.3.

[embodiment 3]

Synthesis example 3 > of < first polymkeric substance

To in the reaction vessel of appropriate size possessing stirring machine, measure maleic anhydride (MA, 6.13g, 62.5mmol), 5-norborene-2-butylacetic acid ester (BuOAcNB, 11.70g, 56.25mmol), 2-norborene (NB, 0.59g, 6.25mmol) and dimethyl 2, two (2 Methylpropionic acid the ester) (1.44g of 2 '-azo, 6.3mmol), them are made to be dissolved in MEK (MEK, 4.0g) and toluene (3.5g).In this lysate, logical 10 minutes nitrogen removes oxygen, thereafter, while stirring 60 DEG C of heating 12 hours.Thereafter use MEK (70g) diluted reaction mixture, and be injected in a large amount of methyl alcohol, polymkeric substance is separated out.Leach solid, carry out vacuum drying at 40 DEG C, obtain polymkeric substance 15.5g thus.Weight-average molecular weight is 12500, and molecular weight distribution (Mw/Mn) is 1.9.

To in the reaction vessel of appropriate size possessing stirring machine, measure NaOH (5.6g, 0.14mol), butanols (14g), toluene (20g), 45 DEG C of mixing 1 hour.Make polymkeric substance obtained above (10g) again be dissolved in MEK and make 25wt% solution, add in above-mentioned suspending liquid and add thermal agitation 3 hours at 45 DEG C further.This mixed liquor is cooled to 40 DEG C, carries out proton addition with formic acid (88 % by weight aqueous solution, 19.3g, 0.42mol) process, thereafter, add MEK and water, water layer is separated, remove inorganic residue.Next, reaction mixture is injected in a large amount of hexanes polymkeric substance is separated out.Leach solid, carry out vacuum drying at 40 DEG C, obtain polymkeric substance 10.5g thus.Weight-average molecular weight is 15800, and molecular weight distribution (Mw/Mn) is 2.4.

[embodiment 4]

Make 20% propylene glycol monomethyl ether (PGME) solution of the first polymkeric substance of synthesis in 25g synthesis example 2 respectively, 0.1g is as the San-Apro Inc. CPI-210S of light acid producing agent, 1.5g is as the glycoluril system crosslinking chemical (Mx-270 of the first crosslinking chemical, Sanwa-Chemical Inc.), 1.0g is as the epoxy resin (VG-3101L of the second crosslinking chemical, Printec Inc.), 0.05g is for improving the silane coupling agent (KBM-303 with the adaptation of substrate, Shin-Etsu Silicone Inc.), the F-557 (DIC Inc.) of the actinoid striped occurred on negative-type photosensitive dielectric film when 200ppm is for preventing rotary coating is dissolved in after appropriate PGME stirs, with the metre filter of 0.2 μm, prepare resin combination.

[embodiment 5]

Make 20% propylene glycol monomethyl ether (PGME) solution of the first polymkeric substance of synthesis in 25g synthesis example 2 respectively, 0.1g is as the San-Apro Inc. CPI-210S of light acid producing agent, 1.5g is as the glycoluril system crosslinking chemical (Mx-270 of the first crosslinking chemical, Sanwa-Chemical Inc.), 1.0g is as the epoxy resin (Epolite100MF of the second crosslinking chemical, common prosperity corporatization length of schooling), 0.05g is for improving the silane coupling agent (KBM-303 with the adaptation of substrate, Shin-Etsu Silicone Inc.), the F-557 (DIC Inc.) of the actinoid striped occurred on negative-type photosensitive dielectric film when 200ppm is for preventing rotary coating is dissolved in appropriate PGME and after stirring, with the metre filter of 0.2 μm, prepare resin combination.

[comparative example 1]

The synthesis > of < polymkeric substance

To possess stirring machine, cooling tube suitable size reaction vessel in, measure maleic anhydride (MA, 122.4g, 1.25mol), 2-norborene (NB, 117.6g, 1.25mol) and dimethyl 2, two (2 Methylpropionic acid the ester) (11.5g of 2 '-azo, 50.0mmol), them are made to be dissolved in MEK (MEK, 150.8g) and toluene (77.7g).In this lysate, lead to the nitrogen of 10 minutes and remove oxygen, thereafter, warming while stirring to 60 DEG C, heats 16 hours.Thereafter, after adding MEK (320g) to this lysate, joined NaOH (12.5g, 0.31mol), butanols (463.1g, 6.25mol), in the suspending liquid of toluene (480g), 45 DEG C of mixing 3 hours.Then, this mixed liquor is cooled to 40 DEG C, carries out proton addition with formic acid (88 % by weight aqueous solution, 49.0g, 0.94mol) process, thereafter, add MEK and water, water layer is separated, thus remove inorganic residue.Then, add methyl alcohol, hexane and be separated organic layer, thus remove unreacted monomer.Further interpolation PGMEA, carries out decompression distillation until the residual quantity of methyl alcohol in system and butanols is less than 1%.Thus, the polymer solution (GPC Mw=13700, Mn=7400) of 20 % by weight of 1107.7g is obtained.

The preparation > of < negative light-sensitive resin combination

20% propylene glycol methyl ether acetate (PGMEA) solution of the polymkeric substance making 25g obtain respectively, 0.1g as San-Apro Inc. CPI-210S, 1.5g of light acid producing agent as the glycoluril system crosslinking chemical (Mx-270 of the first crosslinking chemical, Sanwa-Chemical Inc.), 0.05g is for improving silane coupling agent (KBM-303, Shin-Et with the adaptation of substrate _susili _con _einc.), 200ppm is dissolved in appropriate PGMEA and after stirring for the F-557 (DIC Inc.) of the actinoid striped preventing rotary coating and occur on negative-type photosensitive dielectric film, with the metre filter of 0.2 μm, prepare resin combination.

[comparative example 2]

CPI-210S is changed to 0.5g, Mx-270 is changed to 3.0g, in addition, prepare negative light-sensitive resin combination and evaluate in the same manner as comparative example 1.

With the evaluation > curing rear residual film ratio after < development

For each embodiment, comparative example, the resin combination obtained is used to carry out the rear evaluation with curing rear residual film ratio of developing as follows.

By the resin combination rotary coating of gained on 4 inch silicon wafer processed through HMDS (hexamethyldisilazane), after curing for 100 seconds at 110 DEG C with heating plate, obtain 3 μm of thick film A.With CANON Inc. g+h+i line mask aligner (PLA-501F), use the mask that the line of 10 μm and the width in space are 1:1, with the optimum exposure that pattern dimension be the line of 10 μm and the width in space is 1:1, this film A is exposed.Cured for 120 seconds at 120 DEG C with heating plate further, with 0.5 quality % tetramethylammonium hydroxide aqueous solution 23 DEG C of 20 seconds of development, thus to obtain line and gap length be the wired film B with void pattern of the band of 1:1.Thereafter, by curing process after carrying out with 230 DEG C of heating 60 minutes in an oven, obtain being with figuratum film C.

By the thickness of the film A obtained with said method, film B and film C, by calculating residual film ratio with following formula.

Residual film ratio (%)={ (thickness (μm) of film B)/(thickness (μm) of film A) } × 100 after development

Cure rear residual film ratio (%)=(thickness (μm) of film C)/(thickness (μm) of film A)) × 100

The evaluation > of < developability

To each embodiment, comparative example, observe the pattern of 10 μm of the film B illustrated in " with the evaluation of curing rear residual film ratio after development " with SEM (scanning electron microscope).Low and the situation that is that can not evaluate of situation, the resolution of all being dissolved by film in development is designated as ×, the situation that can't see residue is designated as 〇, evaluates developability thus.

The evaluation > of < specific inductive capacity

To each embodiment, comparative example, evaluate specific inductive capacity as follows.

By the resin combination rotary coating obtained on the aluminium base processed through HMDS (hexamethyldisilazane), cured for 110 seconds at 110 DEG C with heating plate.With CANON Inc. g+h+i line mask aligner (PLA-501F) with 500mJ/cm ²the film obtained is exposed.Cured for 120 seconds at 120 DEG C with heating plate further, thereafter, in an oven with 230 DEG C of heating 60 minutes, on aluminium base, obtain the film of patternless thickness 3 μm thus.

Form gold electrode on the thin film, the electrostatic capacitance obtained by using Hewlett Packard Inc. LCR tester (4282A) under the condition of room temperature (25 DEG C), 10kHz calculates specific inductive capacity.

The evaluation > of < transmissivity

By the composition rotary coating obtained on 1737 glass substrates of the CORNING Inc. of the vertical 100mm processed through HMDS (hexamethyldisilazane), horizontal 100mm size, cured for 100 seconds at 110 DEG C with heating plate.With CANON Inc. g+h+i line mask aligner (PLA-501F) with 500mJ/cm ²the film obtained is exposed.Cured for 120 seconds at 120 DEG C with heating plate further, thereafter, in an oven with 230 DEG C of heating 60 minutes, obtain the film of patternless thickness 3 μm thus on the glass substrate.

The evaluation > of < solvent resistance

The membrane glass substrate obtained by carrying out the operation same with " evaluation of transmissivity " to be immersed in 1-METHYLPYRROLIDONE (Northeast chemistry) after 10 minutes in room temperature (25 DEG C), to carry out pure water rinsing.The average evaluation being less than 5% by the Thickness Variation rate defined by following arithmetic expression is 〇, by the average evaluation more than 5% be ×.

Thickness Variation rate (%)=[{ (thickness after solvent impregnated)-(thickness before solvent impregnated) }/(thickness before solvent impregnated)] × 100

(sensitivity)

By the resin combination rotary coating obtained on 4 inch silicon wafer processed through HMDS (hexamethyldisilazane), after curing for 100 seconds at 110 DEG C with heating plate, obtain about 3.0 μm of thick film A.With CANON Inc. g+h+i line mask aligner (PLA-501F), use the mask that the line of 10 μm and the width in space are 1:1, this film A is exposed.Then after curing for 120 seconds at 120 DEG C with heating plate, forming Resist patterns with 0.5 quality % tetramethylammonium hydroxide aqueous solution 23 DEG C of 20 seconds of development, is the line width of 10 μm by this Resist patterns: exposure (mJ/cm during gap length=1:1 ²) as sensitivity.

Above evaluation result is shown in table 1 in the lump.

Table 1

As can be known from the above results according to the embodiment 1 ~ 5 employing the polymkeric substance with alcoholic extract hydroxyl group, the film that residual film ratio is high, resolution is high can be obtained.Thereby, it is possible to reliably form desired pattern.

Further, in embodiment 1 ~ 5, the film that specific inductive capacity is low, the transparency is high, solvent resistance is also high is become.

On the other hand, if employ the comparative example 1 of the polymkeric substance of not alcoholic hydroxy, then dissolve at development phase film.This is presumably because that the polymkeric substance of not alcoholic hydroxy lacks bridging property.In addition, even if add a large amount of first crosslinking chemical and light acid producing agent, even 50um also cannot differentiate (comparative example 2).

This application is the Japanese publication Patent 2013-137189 CLAIM OF PRIORITY based on application on June 28th, 2013, quotes full content disclosed in it at this.

Claims

1. a negative light-sensitive resin combination, comprise polymkeric substance that the multipolymer that represented by following formula (1) forms, light acid producing agent and with the acid produced by described smooth acid producing agent for catalyzer is by the first crosslinking chemical of described crosslinked polymer,

In formula (1), l, p and m represent mole containing ratio in polymkeric substance, and meet the condition of l+p+m≤1,0≤l < 1,0 < p < 1 and 0 < m < 1

N and q is 0,1 or 2 independently of one another,

The structural unit of A for being represented by following formula (2a), (2b), (2c) or (2d),

2. negative light-sensitive resin combination according to claim 1, wherein, the multipolymer that described formula (1) represents at least comprises the structural unit represented by described formula (2a) and the structural unit represented by described formula (2c).

3. negative light-sensitive resin combination according to claim 1, wherein, described in there is alcoholic extract hydroxyl group organic group be the group of the alkyl with alcoholic extract hydroxyl group and described alcoholic extract hydroxyl group institute bonding.

4. negative light-sensitive resin combination according to claim 3, wherein, the described alkyl of described alcoholic extract hydroxyl group institute bonding is straight-chain,

The carbon number of the described alkyl of straight-chain is 1 ~ 5.

5. negative light-sensitive resin combination according to claim 4, wherein, described alcoholic extract hydroxyl group is primary hydroxyl group.

6. the negative light-sensitive resin combination according to any one of Claims 1 to 5, comprises heat cured second crosslinking chemical different from described first crosslinking chemical further, and this second crosslinking chemical can by applying heat by described crosslinked polymer.

7. negative light-sensitive resin combination according to claim 6, wherein, described second crosslinking chemical is epoxy resin.

8. negative light-sensitive resin combination according to claim 7, wherein, described epoxy resin is multifunctional alicyclic epoxy resin.

9. negative light-sensitive resin combination according to claim 1, wherein, described smooth acid producing agent comprises sulfonium salt.

10. negative light-sensitive resin combination according to claim 1, wherein, described first crosslinking chemical is glycoluril system crosslinking chemical.

11. 1 kinds of cured film, make the negative light-sensitive resin combination according to any one of claim 1 ~ 10 solidify and obtain.

12. 1 kinds of electronic installations, possess cured film according to claim 11.

13. electronic installations according to claim 12, wherein, described cured film is interlayer dielectric or planarization film.

14. 1 kinds of polymkeric substance, the multipolymer represented by following formula (1) is formed,

N and q is 0,1 or 2 independently of one another,

15. polymkeric substance according to claim 14, wherein, the multipolymer that described formula (1) represents at least comprises the structural unit represented by described formula (2a) and the structural unit represented by described formula (2c).

16. polymkeric substance according to claim 15, wherein, described in there is alcoholic extract hydroxyl group organic group be the group of the alkyl with alcoholic extract hydroxyl group and described alcoholic extract hydroxyl group institute bonding.

17. polymkeric substance according to claim 16, wherein, the described alkyl of described alcoholic extract hydroxyl group institute bonding is straight-chain,

The carbon number of the described alkyl of straight-chain is 1 ~ 5.

18. polymkeric substance according to claim 17, wherein, described alcoholic extract hydroxyl group is primary hydroxyl group.

19. polymkeric substance according to any one of claim 14 ~ 18, wherein, this polymkeric substance is the polymkeric substance for negative light-sensitive resin combination.