CN106462064A

CN106462064A - Positive photosensitive resin composition

Info

Publication number: CN106462064A
Application number: CN201580031678.9A
Authority: CN
Inventors: 古江健太郎; 大野由起
Original assignee: Showa Denko KK
Current assignee: Lishennoco Co ltd; Resonac Holdings Corp
Priority date: 2014-07-18
Filing date: 2015-07-16
Publication date: 2017-02-22
Anticipated expiration: 2035-07-16
Also published as: CN106462064B; KR20160135334A; JPWO2016010124A1; KR101870647B1; WO2016010124A1; JP6524085B2

Abstract

Provided is a positive photosensitive resin composition, a film of which after heating and firing generates less outgas. A positive photosensitive resin composition which contains a polyalkenyl phenol resin having a structure represented by formula (1), an alkali-soluble resin (excluding a polyalkenyl phenol resin having a structure represented by formula (1)), and a quinonediazide compound. (In formula (1), each of R1, R2 and R3 independently represents a hydrogen atom, an alkyl group having 1-5 carbon atoms, an alkenyl group represented by formula (2), an alkoxy group having 1-2 carbon atoms or a hydroxyl group, and at least one of the R1, R2 and R3 moieties represents an alkenyl group represented by formula (2); and each Q independently represents an alkylene group represented by formula -CR4R5-, a cycloalkylene group having 5-10 carbon atoms, a divalent organic group having an aromatic ring, a divalent organic group having an alicyclic fused ring or a divalent group obtained by combining the preceding groups.)

Description

Positive type photosensitive organic compound

Technical field

The present invention relates to a kind of to release the positive type photosensitive organic compound that gas is characterized less.More specifically, relate to And a kind of photosensitive polymer combination forming dielectric film, described composition is for dielectric films such as organic electroluminescent devices In the case of, few at the releasing gas carrying out to the insulating film pattern being formed producing after heat is burnt till, can suppress as organic The generation that the blackspot of the degradation phenomena of electroluminescent cell or image shrink.

Background technology

Photosensitive polymer combination is widely used in passing through radioactive ray in the substrate etc. of semiconductor or liquid crystal panel makes Photoetching process forms fine structure.As photosensitive polymer combination, the resin combination of novolac resin system is in semiconductor system Make with etc. in be widely used (referring for example to patent document the 1st, 2.), but existing novolac resin system photoresist group The gas that compound is released from film after heating is burnt till is many, and the pollution to light-emitting component etc. becomes problem.

Photosensitive polymer combination is applied not only to semiconductor manufacturing, and the inscape also serving as light-emitting component is made With.For example, identification is high because of self-luminous for organic electroluminescent device, and is complete solid-state components, therefore, has resistance to impact The feature such as excellent, so, receive much concern as the light-emitting component in display device, wherein comprise the works such as dielectric film.? The dielectric film of organic electroluminescent device or fine structure thing form in purposes, require photosensitive resin film：(1) cross sectional shape For along conical by its shape；(2) gas that the resin film after heating is burnt till is released is few.

In order to improve the releasing gas of the resin film after heating is burnt till, can illustrate novolac resin and benzo The photonasty tree that piperazine compound, carbodiimide compound, triazine thiol compound or bismaleimide compound are combined into Lipid resin combination (such as patent document 3).But, in this technology, the low novolac resin of heat resistance is principal component, The viewpoint aspect reducing releasing gas is insufficient.

In addition, as the high resin of heat resistance, it is proposed that containing polyimides, polyphenyl simultaneouslyAzoles or their precursor and Novolac resin, crosslinking agent, the photosensitive polymer combination (patent document 4～6) of naphthalene quinone di-azido compound.But, this In a little technology, due to the reduction of the heat resistance due to novolac resin, therefore, the minimizing of gas insufficient is released.

Prior art literature

Patent document

Patent document 1:Japanese Laid-Open Patent Publication 62-260147 publication

Patent document 2:Japanese Unexamined Patent Publication 5-94013 publication

Patent document 3:Japanese Unexamined Patent Publication 2009-222923 publication

Patent document 4:Japanese Unexamined Patent Publication 2005-250160 publication

Patent document 5:Japanese Unexamined Patent Publication 2008-268788 publication

Patent document 6:Japanese Unexamined Patent Publication 2009-198957 publication

Content of the invention

Invent problem to be solved

In view of above-mentioned present situation, it is an object of the invention to, the gas providing a kind of film after heating is burnt till to release is few Positive type photosensitive organic compound.

For solving the means of problem

The present inventor etc. conduct in-depth research, it is found that：Normal Photosensitive resin group containing polyene-based phenol resin The heat resistance of compound is good, so containing polyene-based phenol resin, alkali soluble resin, quinone di-azido compound composition permissible Form pattern by photoetching process, and it is few to release gas after can realizing burning till this pattern.

The present invention is a kind of positive type photosensitive organic compound, the polyene-based phenol resin containing the structure with formula (1), alkali Soluble resin (wherein, not including the polyene-based phenol resin with the structure of formula (1)) and quinone di-azido compound,

(in formula (1), R¹、R²And R³Separately represent that hydrogen atom, the alkyl of carbon number 1～5, formula (2) represent Thiazolinyl, the alkoxyl of carbon number 1～2 or hydroxyl, and R¹、R²And R³In at least 1 thiazolinyl representing for formula (2).Q is respectively Expression-CR independently⁴R⁵The alkylidene of-expression, the cycloalkylidene of carbon number 5～10, the divalent organic base with aromatic rings Roll into a ball, there is the divalent organic group of ester ring type condensed ring or by the divalent group of these moiety combinations, R⁴And R⁵Independently Ground represents hydrogen atom, the alkyl of carbon number 1～5, the thiazolinyl of carbon number 2～6, the cycloalkyl of carbon number 5～10 or carbon The aryl of atomicity 6～12.

In formula (2), R⁶、R⁷、R⁸、R⁹And R¹⁰Separately represent hydrogen atom, the alkyl of carbon number 1～5, carbon atom The cycloalkyl of several 5～10 or the aryl of carbon number 6～12.* in formula (2) represents the key with the carbon atom constituting aromatic rings Conjunction portion.).

The present invention comprises following aspect.

[1] a kind of positive type photosensitive organic compound, polyene-based phenol resin, alkali containing the structure with formula (1) are solvable Property resin (wherein, not including the polyene-based phenol resin with the structure of formula (1)) and quinone di-azido compound,

[2] according to the positive type photosensitive organic compound described in [1], it is characterised in that the structure of formula (1) is formula (3) Structure,

(in formula (3), R¹、R²And R³Represent and the R in formula (1)¹、R²And R³The identical meaning.).

[3] according to the positive type photosensitive organic compound described in [2], it is characterised in that have the polyenoid of the structure of formula (3) Base phenol resin contains the structure of formula (4),

(in formula (4), R¹、R²And R³Represent and the R in formula (1)¹、R²And R³The identical meaning.P is the integer of 0～50.).

[4] according to the positive type photosensitive organic compound according to any one of [1]～[3], it is characterised in that formula (2) table The thiazolinyl showing is pi-allyl.

[5] according to the positive type photosensitive organic compound according to any one of [1]～[4], it is characterised in that alkali-soluble Resin is polyimide precursor.

[6] according to the positive type photosensitive organic compound according to any one of [1]～[5], it is characterised in that described polyamides Imines precursor is represented by formula (5),

(in formula (5), R¹¹Represent the divalent organic group of carbon number more than 2, R¹²Represent the trivalent of carbon number more than 2 Or the organic group of tetravalence, R¹³Represent the organic group of hydrogen atom or carbon number 1～20, R¹⁴Represent hydrogen atom or carbon atom The organic group of several 1～50, m represents the integer that 1 or 2, n represent 5～200.).

[7] according to the positive type photosensitive organic compound described in [6], it is characterised in that the R of formula (5)¹⁴Containing unsaturated group Group.

[8] according to the positive type photosensitive organic compound described in [7], it is characterised in that described unsaturated group is Malaysia Imide.

[9] according to the positive type photosensitive organic compound described in [8], it is characterised in that described polyimide precursor passes through Following methods manufactures, and described method comprises following operation：

Operation (i)：Make the acid compound that diamine compound that formula (6) represents and formula (7) represent with 1:0.8～0.95 rub You obtain, than carrying out reacting, the polyamic acid that end has amino；

H₂N-R¹¹-NH₂(6)

(wherein, x, y represent the integer that 0 or 1, z represent 0～4.)

And

Operation (ii)：By making amino and the bismaleimide amine compounds of the end of the polyamic acid obtaining in operation (i) Thing reaction obtains the polyimide precursor that end has dimaleoyl imino.

[10] according to the positive type photosensitive organic compound according to any one of [1]～[9], it is characterised in that contain many Thiazolinyl phenol resin 20～50 mass parts, alkali soluble resin 100 mass parts and quinone di-azido compound 20～70 mass parts.

[11] according to the positive type photosensitive organic compound according to any one of [6]～[10], it is characterised in that formula (5) The solid constituent acid number of the polyimide precursor representing is 110～210mgKOH/g.

[12] a kind of radioactive ray photolithographic structures thing, it obtains by the following method, and described method comprises following operation：

(1) painting process：Positive type photosensitive organic compound according to any one of [1]～[11] for the coating on base material；

(2) drying process：Solvent in positive type photosensitive organic compound after coating is removed；

(3) exposure process：Irradiate radioactive ray across photomask；

(4) developing procedure：Developed by alkali and form pattern；And

(5) heating treatment step：Heat at a temperature of 150～350 DEG C.

[13] according to the radioactive ray photolithographic structures thing described in [12], it is characterised in that temperature when thermal weight loss is 5 mass % It is more than 350 DEG C.

Invention effect

According to the present invention it is possible to the positive-type photolithography photonasty tree that the gas of the film releasing that offer is after heat is burnt till is few Oil/fat composition.Especially by organic electroluminescent device use, can manufacture there is no concern that because gas release and cause The element of performance degradation.

Detailed description of the invention

Hereinafter, the present invention is described in detail.

(polyene-based phenol resin)

Polyene-based phenol resin can be by making phenol resol resins, cresol novolac resin, triphenyl methane type The known phenol such as phenol resin, phenol aralkyl resin, xenyl aralkyl-phenol resin, phenol-dicyclopentadiene copolymer resin The hydroxyl generation thiazolinyl etherificate of resin, and then make thiazolinyl ether generation Claisen rearangement obtain.

Polyene-based phenol resin used in the photosensitive polymer combination of the present invention has the structure of formula (1).By containing There is this resin, the developing property of the photosensitive polymer combination obtaining can be improved, and also contribute to release subtracting of gas Few.Particularly can be work perfectly well as phenol resol resins, cresol novolac resin, the replacement of many vinyl phenols resin Product and use.

(in formula (1), R¹、R²And R³Separately represent that hydrogen atom, the alkyl of carbon number 1～5, formula (2) represent Thiazolinyl, the alkoxyl of carbon number 1～2 or hydroxyl, and R¹、R²And R³In at least 1 thiazolinyl representing for formula (2).Q is respectively It independently is formula-CR⁴R⁵The alkylidene of-expression, the cycloalkylidene of carbon number 5～10, the divalent organic base with aromatic rings Roll into a ball, there is the divalent organic group of ester ring type condensed ring or by the divalent group of these moiety combinations, R⁴And R⁵Independently Ground represents hydrogen atom, the alkyl of carbon number 1～5, the thiazolinyl of carbon number 2～6, the cycloalkyl of carbon number 5～10 or carbon The aryl of atomicity 6～12.

In formula (2), R⁶、R⁷、R⁸、R⁹And R¹⁰Separately represent hydrogen atom, the alkyl of carbon number 1～5, carbon atom The cycloalkyl of several 3～10 or the aryl of carbon number 6～12.* in formula (2) represents the key with the carbon atom constituting aromatic rings Conjunction portion.)

R in formula (1)¹、R²And R³Represent the thiazolinyl shown in hydrogen atom, the alkyl of carbon number 1～5, formula (2), carbon atom The alkoxyl of several 1～2 or hydroxyl, and R¹、R²And R³In at least 1 thiazolinyl representing for formula (2).

R in formula (1)¹、R²And R³In, as the concrete example of the alkyl of carbon number 1～5, can enumerate：Methyl, second Base, n-propyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, n-pentyl etc..Alkoxyl concrete as carbon number 1～2 Example, can enumerate methoxyl group, ethyoxyl.

In the thiazolinyl that formula (2) represents, R⁶、R⁷、R⁸、R⁹And R¹⁰Separately represent hydrogen atom, the alkane of carbon number 1～5 The aryl of base, the cycloalkyl of carbon number 5～10 or carbon number 6～12.As the concrete example of the alkyl of carbon number 1～5, Can enumerate：Methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, n-pentyl etc..As carbon number 5 The cycloalkyl of～10, can enumerate：Cyclopenta, cyclohexyl, methylcyclohexyl, suberyl etc..Virtue as carbon number 6～12 The concrete example of base, can enumerate：Phenyl, aminomethyl phenyl, ethylphenyl, xenyl, naphthyl etc..As R⁶、R⁷、R⁸、R⁹And R¹⁰, It is preferably separately the alkyl of hydrogen atom or carbon number 1～5.The thiazolinyl representing as preferred formula (2), from reactivity From the aspect of, pi-allyl, methacrylic, more preferably pi-allyl can be enumerated.And, R¹、R²And R³In, most preferably one For pi-allyl or methacrylic, other 2 is hydrogen atom.

Q is separately formula-CR⁴R⁵-represent alkylidene, carbon number 5～10 cycloalkylidene, there is aromatic rings Divalent organic group, there is the divalent organic group of ester ring type condensed ring or by the divalent group of these moiety combinations. R⁴And R⁵Separately represent hydrogen atom, the alkyl of carbon number 1～5, the thiazolinyl of carbon number 2～6, carbon number 5～10 Cycloalkyl or the aryl of carbon number 6～12.R⁴And R⁵In, as the concrete example of the alkyl of carbon number 1～5, Ke Yiju Go out：Methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, n-pentyl etc..Alkene as carbon number 2～6 The concrete example of base, can enumerate：Vinyl, pi-allyl, cyclobutenyl, pentenyl, hexenyl etc..As carbon number 5～10 Cycloalkyl, can enumerate：Cyclopenta, cyclohexyl, methylcyclohexyl, suberyl etc..Tool as the aryl of carbon number 6～12 Style, can enumerate：Phenyl, aminomethyl phenyl, ethylphenyl, xenyl, naphthyl etc..R⁴And R⁵It is separately preferably hydrogen former Son or the alkyl of carbon number 1～3, most preferably hydrogen atom.

The concrete example of the cycloalkylidene of the carbon number 5～10 representing as Q, can enumerate：Cyclopentylene, sub-hexamethylene Base, methylcyclohexylidene, cycloheptylidene etc..As the concrete example of the divalent organic group with aromatic rings, can enumerate：Sub-benzene Base, xylene, naphthylene, biphenylene, fluorenylidene, anthrylene, xylylene, 4,4-methylene diphenylene, formula (8) The base etc. representing.

As the concrete example of the divalent organic group with ester ring type condensed ring, sub-dicyclopentadienyl etc. can be enumerated.

In polyene-based phenol resin used in the photosensitive polymer combination of the present invention, from alkali-developable, release gas From the aspect of, as particularly preferred polyene-based phenol resin, the polyene-based phenol tree with the structure that formula (3) represents can be enumerated Fat.

(in formula (3), R¹、R²And R³Represent and the R in formula (1)¹、R²And R³The identical meaning.)

Preferred R¹、R²And R³With the preferred R in formula (1)¹、R²And R³Equally.

Phenolic hydroxyl group ionizes in the presence of alkali compounds, can be dissolved in water, therefore, from alkali-developable Viewpoint is set out, and phenolic hydroxyl group needs for more than a certain amount of.Therefore, the structure that formula (1) or formula (3) represent is in polyene-based phenol resin It is preferably 50～100 mass %, more preferably 70～100 mass %.The polyene-based phenol resin of the structure containing formula (3) is further The polyene-based phenol resin that particularly preferably formula (4) represents.

(in formula (4), R¹、R²And R³Represent and the R in formula (1)¹、R²And R³The identical meaning.In addition, p be 0～50 whole Number.)

In addition, the number-average molecular weight of the polyene-based phenol resin used in the present invention is preferably 800～5000, more preferably 1000～3000.If number-average molecular weight is less than 800, then the quantitative change releasing gas is many, and when it is more than 5000, alkali-developable drops Low.

It should be noted that number-average molecular weight and weight average molecular weight in the application are the polyphenyl being obtained by GPC mensuration The value of ethene conversion.

(manufacture method of polyene-based phenol resin)

The polyene-based phenol resin of the structure with formula (1) used in the present invention is by becoming the phenol resin of raw material Hydroxyl carry out thiazolinyl etherificate after occur Claisen rearangement react and make thiazolinyl reset ortho position or the contraposition of original hydroxyl Obtained from resin.

Raw material phenol resin as the polyene-based phenol resin of the structure with formula (1), it is possible to use there is the structure of formula (9) Known phenol resin.

(in formula (9), X¹、X²And X³Separately represent hydrogen atom, the alkyl of carbon number 1～5, carbon number 1～2 Alkoxyl or hydroxyl, and the taking of the carbon atom bonding that the carbon atom of the phenyl ring being bonded with relative to hydroxyl is ortho position or contraposition At least 1 of Dai Jizhong is hydrogen atom.Q represents the meaning identical with the Q in formula (1).)

X in formula (9)¹、X²And X³In, as the concrete example of the alkyl of carbon number 1～5, can enumerate：Methyl, second Base, n-propyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, n-pentyl etc..Alkoxyl concrete as carbon number 1～2 Example, can enumerate methoxyl group, ethyoxyl.In addition, Q, R⁴And R⁵Respectively with Q, the R in formula (1)⁴And R⁵Identical.

As the concrete example of the phenol resin that formula (9) represents, can enumerate：Phenol resol resins, cresol novolak Resin, triphenyl methane type phenol resin, phenol aralkyl resin, xenyl aralkyl-phenol resin, phenol-dicyclopentadiene copolymerization Resins etc., from the viewpoint of alkali-developable, it may be preferred to use Q is-CR⁴R⁵The alkylidene of-expression and R⁴And R⁵Former for hydrogen The phenol resol resins of son, cresol novolac resin.

(the thiazolinyl etherification reaction of phenol resin)

The thiazolinyl etherification reaction of phenol resin can illustrate the following two kinds method：(i) make allyl chloride, methallyl chloride, The known method that the halogenated alkenes based compounds such as allyl bromide, bromoallylene and phenol resin react；(ii) the carboxylic acid alkene of allyl acetate etc is made The method that based compound and phenol resin react.

The thiazolinyl etherification reaction using halogenated alkenes based compound can use in such as Japanese Unexamined Patent Publication 2-91113 publication The method recorded.In addition, the method making carboxylic acid alkenyl compound and phenol resin react can use such as Japanese Unexamined Patent Publication 2011- Method described in No. 26253 publications.From the aspect of requiring long-term insulating properties, the photosensitive polymer combination of the present invention is excellent Choosing will not be mixed into and be possible to bring the upper of the dysgenic halogen compound from halogenated alkenes based compound to long-term insulating properties State the method for (ii).

Halogenated alkenes based compound or alkenyl carboxylate are preferably 0.3～1.0 equivalent relative to the addition amount of phenolic hydroxyl group, more It is preferably 0.5～1.0 equivalent.If being less than 0.3 equivalent, then there is the reaction with BMI after Claisen rearangement Property reduce situation.

(the Claisen rearangement reaction of polyene-based ether resin)

Target polyene-based phenol resin can be by making to utilize the method described in above-mentioned " the thiazolinyl etherification reaction of phenol resin " Manufactured polyene-based ether resin generation Claisen rearangement reaction obtains.Claisen rearangement reaction can be by being heated to 100 Temperature, the reaction of～250 DEG C obtain for 1～20 hour.Claisen rearangement reaction can use high boiling solvent, it is also possible to no Use solvent.In addition, in order to promote rearrangement reaction, the inorganic salts such as sodium thiosulfate, sodium carbonate can be added.Specifically, remember It is loaded in Japanese Unexamined Patent Publication 2-91113 publication.

Reaction by phenol resol resins → alkene ether resin → (Claisen rearangement reaction) → polyene-based phenol resin The example of formula is shown in following reaction equation 1.

(content of polyene-based phenol resin)

It as the content of the polyene-based phenol resin in photosensitive polymer combination, with alkali soluble resin 100 mass parts is Benchmark, preferably 20～50 mass parts, more preferably 30～40 mass parts.More than 20 mass parts, then 300～400 DEG C Heat resistance when burning till becomes good, if which is below 50 mass parts, then patternability during alkali development becomes good.

(alkali soluble resin)

The photosensitive polymer combination of the present invention contains alkali soluble resin and (wherein, does not includes having the structure of formula (1) Polyene-based phenol resin.).Alkali soluble resin makes favorable solubility in aqueous slkali for the composition.

As alkali soluble resin, preferably there is hydroxyl or carboxyl, can enumerate：Phenol resol resins, cresol novolac Varnish gum, many vinyl phenols resin, containing carboxylic acid acrylic acid series polymeric compounds, containing phenylol acrylic acid series polymeric compounds, contain carboxylic The silicone resin of acid, the silicone resin containing phenylol, polyphenyl are simultaneouslyAzoles precursor, polyimide precursor, the polyamides containing phenylol are sub- Amine etc..

Here, as the characteristic of alkali soluble resin, make the resin coating film of 2 μm preferably on a glass, impregnated in It during 2.38% tetramethylammonium hydroxide aqueous solution, was completely dissolved within 60 seconds.

(polyimide precursor)

In the case of requiring higher heat resistance, polyimide precursor is preferably used as alkali soluble resin.The present invention Photosensitive polymer combination preferably comprise the polyimide precursor that formula (5) represents.

(in formula (5), R¹¹Represent the divalent organic group of carbon number more than 2, R¹²Represent the trivalent of carbon number more than 2 Or the organic group of tetravalence, R¹³Represent the organic group of hydrogen atom or carbon number 1～20, R¹⁴Represent hydrogen atom or carbon atom The organic group of several 1～50, m represents the integer that 1 or 2, n represent 5～200.)

In formula (5), R¹¹And R¹²Preferably having aromatic ring, preferred above-mentioned aromatic ring is phenyl ring and naphthalene nucleus.As R¹¹ Example, can enumerate：

Deng.As R¹²Example, can enumerate：

Deng.In addition, as R¹³The example of organic group of carbon number 1～20, can enumerate：Methyl, ethyl, propyl group, Butyl, amyl group, hexyl, trimethyl silyl, phenyl, hydroxy phenyl, carboxyl phenyl, methyl carboxyl phenyl etc..Show to alkali From the aspect of the dissolubility of shadow liquid, preferably hydrogen atom, hydroxy phenyl or carboxyl phenyl.As R¹⁴The having of carbon number 1～50 The example of machine group, is carboxylic acid compound, carboxylic acid anhydrides or maleimide and the reacted residue of amino, shows alkali to adjust The dissolubility of shadow liquid and suitably select.Now, preferably the solid constituent acid number of the compound of formula (5) is set to 110～ 210mgKOH/g.If the solid constituent acid number of the compound of formula (5) is more than 110mgKOH/g, then coordinate polyene-based phenol tree When fat and quinone di-azido compound, becoming good to the dissolubility of alkaline developer, if which is below 210mgKOH/g, then alkali shows The pattern form of movie queen becomes good.In addition, R¹⁴Preferably comprise unsaturated group.As unsaturated group, do not limit, can lift Go out：Dimaleoyl imino, vinyl, pi-allyl, acryloyl group, methylacryloyl etc., wherein, preferably dimaleoyl imino. Here, the hydrogen atom that dimaleoyl imino is the nitrogen atom bonding with maleimide occurs to depart from and become the form of associative key Monovalent organic group.R¹⁴During containing dimaleoyl imino, carrying out cross-linking reaction with polyene-based phenol resin, therefore, heat resistance is entered One step improves, so preferably.The preferred number-average molecular weight of the compound of formula (5) is 5000～20000.

The polyimide precursor that formula (5) represents can be by making diamine compound or derivatives thereof and tricarboxylic acids, tetrabasic carboxylic acid It is dissolved in such as METHYLPYRROLIDONE, gamma-butyrolacton, N, N-dimethyl sulfoxide (DMSO), N, N-Deng acid compound or derivatives thereof Dimethylacetylamide, N,N-dimethylformamide, propylene carbonate, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, butyl In cellosolve, ethyl cellosolve equal solvent, and react in the range of-30 DEG C～300 DEG C and obtain.

Now, preferably make diamines or derivatives thereof and acid compound such as tricarboxylic acids, tetrabasic carboxylic acid or derivatives thereof with 1:0.8～ The mol ratio of 0.95 is reacted, so that end becomes amino.Also can make further the amino of end and carboxylic acid compound, Carboxylic acid anhydrides or maleimide etc. react.

Preferred diamines formula (6) for manufacturing the compound of formula (5) represents.

H₂N-R¹¹-NH₂(6)

In formula (6), R¹¹R with formula (5)¹¹Identical.

As the concrete example of the diamine compound using, can enumerate：1,4-phenylenediamine, 1,3-phenylenediamine, 4, 4 '-diamino-diphenyl ether, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino diphenyl sulfone, 4,4 '-diamino-diphenyl Thioethers etc., these materials can be used alone or mix two or more and use.

Preferred acid compound formula (7) for manufacturing the compound of formula (5) represents.

(wherein, x, y represent the integer that 0 or 1, z represent 0～4.And then for x+y+z ＞ 0, xy=1 when, z=0, xy=0 and During x+y=1, z=1 or 2, during x=0 and y=0, is z=3 or 4.)

It should be noted that in formula (7), R¹²R with formula (5)¹²Identical.

As the concrete example of the acid compound using, can enumerate：Pyromellitic Acid, 3,3 ', 4,4 '-biphenyltetracarboxylic acid, 2,3,3 ', 4 '-biphenyltetracarboxylic acid, 3,3 ', 4,4 '-benzophenone tetracarboxylic, 4,4 '-epoxide two phthalic acid, 3,3 ', 4, 4 '-diphenyl sulfone tetracarboxylic acid, 2,2 '-bis-(3,4-dicarboxyphenyi) HFC-236fas, 2,3,6,7-naphthalenetetracarbacidic acidic, 1,2,5,6-naphthalene Tetracarboxylic acid, 1,4,5,8 naphthalenetetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic, 1,2,3,4-ethylene-dimalonic acid, 1,2,4,5-ring penta Alkane tetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 3,3 ', 4,4 '-dicyclohexyl tetracarboxylic acid, 2,3,5-tricarboxylic cyclopentyl acetic acid Deng or their acid anhydrides, these materials can be used alone or mix two or more and use.

The maleimide compound reacting as the amino with end, can enumerate：N-phenylmaleimide, to hydroxyl Phenyl maleimide, a hydroxyphenyl-maleimides, to carboxyl phenyl maleimide, N-dodecyl maleimide In simple function maleimide compound, double (4-maleimidophenyl) methane, 4-methyl isophthalic acid, 3-dimaleimide base Dimaleoyl imino compound, three (the 4-Malaysia acyls such as benzene, double (3-ethyl-5-methyl-4-maleimidophenyl) methane Imido grpup phenyl) four Malaysias such as three maleimide based compounds, double (3,4-dimaleimide base phenyl) methane such as methane The polymaleimide based compound such as imide compound and poly-(4-dimaleoyl imino styrene), these materials can be single Solely use or mix two or more and use.

(quinone di-azido compound)

The positive type photosensitive organic compound of the present invention contains quinone di-azido compound as radiation-sensitive compound. As quinone di-azido compound, can enumerate：Obtained from the sulfonic acid of quinone two nitrine is bonded with polyol with the form of ester Compound；The sulfonic acid of quinone two nitrine be bonded with multiamino compound in the way of sulfonamide obtained from compound；Quinone two nitrine Sulfonic acid be bonded with polyhydroxy multiamino compound in the way of ester and/or sulfonamide obtained from compound etc..From exposure portion From the viewpoint of the contrast in unexposed portion, the preferably functional group of these polyols or multiamino compound is overall 50 moles of more than % are by quinone two azide substitution.By using this quinone di-azido compound, can obtain as Conventional UV Carry out the photoresist of photosensitive eurymeric under the i ray (365nm) of the mercury lamp of line, h ray (405nm), g ray (436nm) Composition.

As polyol, can enumerate：Bis-Z、BisP-EZ、TekP-4HBPA、TrisP-HAP、TrisP-PA、 TrisP-SA、TrisOCR-PA、BisOCHP-Z、BisP-MZ、BisP-PZ、BisP-IPZ、BisOCP-IPZ、BisP-CP、 BisRS-2P、BisRS-3P、BisP-OCHP、メチレントリス-FR-CR、BisRS-26X、DML-MBPC、DML-MBOC、 DML-OCHP、DML-PCHP、DML-PC、DML-PTBP、DML-34X、DML-EP、DML-POP、ジメチロール-BisOC- P、DML-PFP、DML-PSBP、DML-MTrisPC、TriML-P、TriML-35XL、TML-BP、TML-HQ、TML-pp-BPF、 TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (being trade name above, Honshu Chemical Ind's system), BIR-OC、BIP-PC、BIR-PC、BIR-PTBP、BIR-PCHP、BIP-BIOC-F、4PC、BIR-BIPC-F、TEP-BIP-A、 46DMOC, 46DMOEP, TM-BIP-A (being trade name above, rising sun organic material Industrial Co., Ltd system), 2,6-dimethoxy first Base-4-TBP, 2,6-dimethoxy-methyl-paracresol, 2,6-diacetoxy methyl-paracresol, naphthols, tetrahydroxy Benzophenone, gallic acid methyl esters, bisphenol-A, bis-phenol E, methylene bis-phenol, BisP-AP (above be trade name, Honshu chemistry work Industry Co., Ltd. system) etc., but it is not limited to these.

As the example of quinone di-azido compound, can enumerate：The 1,2-naphthoquinones two nitrine-4-sulphur of above-mentioned polyol Acid esters or 1,2-naphthoquinones two nitrine-5-sulphonic acid ester.

Quinone di-azido compound, when with exposures such as ultraviolet lights, generates carboxyl through the reaction shown in following reaction equation 2. By generating carboxyl, the part being exposed (epithelium) becomes to be dissolvable in water aqueous slkali, manifests alkali-developable.

The content of the quinone di-azido compound in photosensitive polymer combination is different because of the quinone di-azido compound of use, On the basis of alkali soluble resin 100 mass parts, preferably 20～70 mass parts, more preferably 30～60 mass parts.It is 20 matter When more than amount part, alkali-developable is good.In addition, below if 70 mass parts, then the thermal weight loss of more than 300 DEG C is not variable greatly.

The photosensitive polymer combination of the present invention can be dissolved in solvent and use with solution state.For example, by polyene-based phenol Resin, alkali soluble resin are dissolved in solvent, mix quinone di-azido compound, as required in this solution in certain proportion Thermal curing agents, surfactant or the colouring agent such as dyestuff, pigment, thus can prepare the photosensitive resin composition of solution state Thing.

As solvent, can enumerate for example：Glycol monoethyl ether, glycol dimethyl ether, Ethylene Glycol Methyl ethylether, ethylene glycol Ethylene glycol alkyl ether acetic acid esters, the diethylene glycols such as glycol ethers, methylcellosolve acetate, ethyl cellosolve acetate such as single ether Monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, diethyl two The propylene glycol alkyl ether acetic acid esters such as the diethylene glycol classes such as alcohol monobutyl ether, propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetic acid esters, Toluene, dimethylbenzene etc. are aromatic hydrocarbon, methyl ethyl ketone, methyl amyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, ring The ketones such as hexanone, 2 hydroxy propanoic acid ethyl ester, 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, ethyoxyl Ethyl acetate, hydroxyl ethyl acetate, 2-hydroxy-2-methyl methyl butyrate, 3-methoxy methyl propionate, 3-methoxypropionic acid second Ester, 3-ethoxypropanoate, 3-ethoxyl ethyl propionate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, γ- The amide-types such as the esters such as butyrolactone, METHYLPYRROLIDONE, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide.These Solvent can be used alone, it is also possible to combines two or more.

The positive type photosensitive organic compound of the present invention is as any composition, it is possible to use hot radical producing agent is as heat Curing agent.As preferred hot radical producing agent, organic peroxide can be enumerated specifically, diamyl peroxide can be enumerated Compound, 2,5-dimethyl-2,5-two (t-butylperoxy) hexane, t-butyl amyl peroxide, di-tert-butyl peroxide, 10 hours half life temperatures such as 1,1,3,3-tetramethyl butyl hydroperoxide, isopropyl benzene hydroperoxide are 100～170 DEG C organic Peroxide etc..

As for the preferred content of the thermal curing agents in positive type photosensitive organic compound, with polyene-based phenol resin, alkali can On the basis of total amount 100 mass parts of soluble resin, preferably 0.1～5 mass parts, more preferably 0.5～3 mass parts.

The positive type photosensitive organic compound of the present invention is further used as any composition, for example in order to improve coating or In order to improve the developability of film, surfactant can be contained.

As this surfactant, can enumerate for example：Polyoxyethylene lauryl ether, polyoxyethylene stearyl base ether, polyoxy The polyoxyethylene alkyl ether classes such as ethene oleyl ether；The polyoxyethylene such as NONIN HS 240, ethylene nonyl phenyl ether Aryl ethers；The nonionic systems such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate, polyoxyethylene distearate Surfactant；メガファックF-251、メガファックF-281、メガファックF-430、メガファックF- 444th, メガ Off ァッ Network R-40 (more than, trade name, Dainippon Ink Chemicals's system), サ Off ロ Application S-242, サ Off ロ Application S- 243rd, サ Off ロ Application S-420, サ Off ロ Application S-611 (being trade name above, ACG セイミケミカ Le Co., Ltd. system) etc. Fluorine system surfactant；Organic siloxane polymer KP323, KP326, KP341 (it is trade name above, SHIN-ETSU HANTOTAI's chemical industry strain Formula commercial firm system) etc..These materials also can use two or more.As for the amount of this surfactant, with polyene-based phenol resin, On the basis of total amount 100 mass parts of alkali soluble resin, coordinate below 2 mass parts, below preferably 1 mass parts.

And then, the positive type photosensitive organic compound of the present invention, can be containing the coloring such as dyestuff, pigment as any composition Material.The coloured materials such as this dyestuff or pigment can be inorganic pigment or organic pigment.As this coloured material Concrete example, can enumerate：Black pigment or the C.I. such as carbon black, CNT, acetylene black, graphite, iron oxide black, nigrosine, titanium are black Pigment yellow the 20th, the 24th, the 86th, the 93rd, the 109th, the 110th, the 117th, the 125th, the 137th, the 138th, the 147th, the 148th, the 153rd, the 154th, the 166th, C.I. pigment orange 36, 43rd, the 51st, the 55th, the 59th, the 61st, C.I. Pigment Red 9, the 97th, the 122nd, the 123rd, the 149th, the 168th, the 177th, the 180th, the 192nd, the 215th, the 216th, the 217th, the 220th, 223rd, the 224th, the 226th, the 227th, the 228th, the 240th, C.I. pigment violet 1 the 9th, the 23rd, the 29th, the 30th, the 37th, the 40th, the 50th, C.I. pigment blue 15,15:1、15: 4th, the 22nd, the 60th, the 64th, C.I. pigment Green 7, C.I. pigment brown the 23rd, the 25th, coloring pigments such as 26.

(preparation method)

The positive type photosensitive organic compound of the present invention is by by above-mentioned polyene-based phenol resin, alkali soluble resin, quinone Two azido compounds and other composition as required are dissolved or dispersed in above-mentioned solvent mixing and prepare, and make according to it By purpose, suitable solid component concentration can be used, for example, can be set to solid component concentration 10～60 mass %.In addition, The composition liquid prepared as described above generally filters before use.As the method filtering, such as aperture can be enumerated The millipore filter etc. of 0.05～1.0 μm.

The positive type photosensitive organic compound of the so prepared present invention, its long-standing storage-stable is also excellent.

(pattern formation method and curing)

When using the positive type photosensitive organic compound of the present invention in radioactive ray photoetching process purposes, first, by the present invention Positive type photosensitive organic compound coat substrate surface, can by the methods such as heating by solvent by be dried wait and remove Go, form film.The coating process of the positive type photosensitive organic compound of substrate surface is not particularly limited, example can be used Such as various methods such as spray-on process, rolling method, Narrow slit, method of spin coating.

After the positive type photosensitive organic compound of the present invention is coated substrate surface, generally by heating (prebake conditions) Solvent seasoning is made film.Heating condition is also different because of the species of each composition, mixing ratio etc., generally 70～120 Heat the stipulated time at DEG C, if for example on electric hot plate, then heat 1～20 minute, heat 3 in an oven ～60 minutes, it is hereby achieved that film.

Then, via the mask of predetermined pattern, radioactive ray (such as luminous ray, ultraviolet are irradiated to the film through prebake conditions Line, far ultraviolet, X-ray, electron beam, gamma-rays, synchrotron radioactive ray etc.) etc. (exposure process), thereafter, utilize development Liquid develops, and removes unwanted part, forms predetermined pattern shape film (developing procedure).As for the eurymeric sense to the present invention Preferred radioactive ray for photosensitive resin composition, owing to being preferably used naphthalene quinone di-azide sulfonic acid ester as positive light sensitivity chemical combination Thing, so being the ultraviolet～luminous ray of the wavelength with 250～450nm.As developer solution, for example, can use：Hydrogen-oxygen Change the inorganic bases such as sodium, potassium hydroxide, sodium carbonate, sodium metasilicate, sodium metasilicate, ammoniacal liquor；The primary amine classes such as ethylamine, n-propyl amine； The secondary amine classes such as diethylamide, two-n-propyl amine；The tertiary amines such as triethylamine, methyidiethylamine；Dimethylethanolamine, three second The alcamines such as hydramine；The quaternary ammonium salts such as TMAH, tetraethyl ammonium hydroxide, choline；Pyrroles, piperidines, 1,8-diaza The aqueous solution of the bases such as cyclic amine such as bicyclic [5.4.0]-7-endecatylene, 1,5-diazabicyclo [4.3.0]-5-nonane. Alternatively, it is also possible to use water-miscible organic solvent, the surface-actives such as methyl alcohol, the ethanol adding appropriate amount in above-mentioned aqueous alkali The aqueous solution of agent etc. is as developer solution.Developing time is usually 30～180 seconds, in addition, the method for development can be liquid pool method, spray Pouring method, infusion process etc. any one.After development, carry out flowing water and clean 30～90 seconds, remove unwanted part, by compressed air or Compressed nitrogen air-dries, and is consequently formed pattern.Thereafter, this pattern is utilized the heater such as electric hot plate, baking oven, in set point of temperature For example heat 20～200 minutes at 150～350 DEG C, it is hereby achieved that film, it is also possible to periodically improve temperature (heating treatment step).

Employ the radioactive ray photolithographic structures thing of the positive type photosensitive organic compound of the present invention making in aforementioned manners Also can remove volatile ingredient by burning till 350～450 DEG C under conditions of further, make temperature during 5% Mass lost Spend high radioactive ray photolithographic structures thing.If firing temperature is less than 450 DEG C, then radioactive ray photolithographic structures thing is not susceptible to hot bad Change.The atmosphere burnt till can in air or under the inert gas atmosphere such as nitrogen any one.Burn till in addition, firing time also depends on Temperature, preferably 5～60 minutes, more preferably 10～40 minutes.If firing time is less than 5 minutes, then sometimes can't see effect, When it was more than 60 minutes, productivity ratio reduces sometimes.

Embodiment

Hereinafter, based on embodiment and comparative example, specifically illustrate the present invention, but the present invention is not limited to these in fact Execute example.

(1) resins synthesis

The manufacture of [Production Example 1] many allyl phenols Resin A-1

3 shape of the mouth as one speaks flasks of 1000mL load by molten for potassium carbonate (Tso Tat Co., Ltd., Japan's system) 201g (1.45mol) Solution that solution is formed in pure water 150g, phenol resol resins " ショウノ Le " (trade mark) BRG-556 (Showa electrician Co., Ltd.'s system) 150.0g, reactor is carried out nitrogen displacement and is heated to 85 DEG C.Put into allyl acetate under nitrogen flowing (Showa Denko K. K's system) 204g (2.04mol), containing 50% water 5%-Pd/C-STD type (by Metal Palladium in activated carbon with The content of 5 mass % disperses, and the hydrous water in the way of becoming 50 mass % by above-mentioned Metal Palladium and activated carbon dispersion And the catalyst of the allylation reaction stabilizing, エヌイケ system キャット Co., Ltd. system) 0.62g (0.291mmol) and triphenylphosphine (uses the activator of the allylation reaction catalyst of above-mentioned palladium, northern emerging chemical industry strain formula Commercial firm's system) 3.82g (14.6mmol), blanket of nitrogen is warming up to 105 DEG C, after reacting 4 hours, chases after and add allyl acetate 29g (0.291mol), heating 10 hours is continued.Thereafter stop stirring, stand, be thus separated into the two-layer of organic layer and water layer.Add Pure water (200g), dissolving to the salt separating out, then, adds toluene 200g, confirms that the temperature being maintained at more than 80 DEG C does not has After separating out white precipitate, by filtering, (membrane filter of 1 μm (uses ADVANTEC society KST-142-JA by pressurization (0.3MPa)) Pd/C is reclaimed.This filter residue toluene 100g is cleaned, its cleaning fluid is merged with filtrate.By the water layer of this filtrate Separate, organic layer water 200g is cleaned 2 times, confirm its cleaning fluid for neutrality.After separating organic layer, under reduced pressure enter Row concentrates, and obtains the polyallyl ethers resin of the phenol novolak type of brown oil.This material is carried out¹H-NMR measures Results verification：Polyallyl ethers resin containing phenol novolak type is as principal component.The following institute of determination data of feature State.¹H-NMR (400MHz, CDCl₃, 27 DEG C), δ 3.6-4.0 (m ,-Ph-CH ₂-Ph-) δ 4.4-4.8 (2H, m ,-CH ₂CH=CH₂), δ 5.1-5.3 (1H, m ,-CH₂CH=CHH), δ 5.3-5.5 (1H, m ,-CH₂CH=CHH), δ 5.8-6.2 (1H, m ,-CH₂CH= CH₂), δ 6.6-7.3 (m, phenyl ring).

It in addition, measure the hydroxyl value of this material, but is nearly no detectable.

Then, the burning of the 500mL being fixed with mechanical agitator put into by the polyallyl ethers resin by phenol novolak type In Ping.While being stirred with 300rpm, being warming up to 190 degree, carrying out Claisen rearangement reaction 10 in this state little When, obtain many allyl phenols Resin A-1 of phenol novolak type.The hydroxyl equivalent of many allyl phenols Resin A-1 is 165, can To confirm the generation of hydroxyl.In addition, number-average molecular weight is 1000, weight average molecular weight is 2400.This material is carried out¹H-NMR The results verification measuring：Many allyl phenols Resin A-1 containing phenol novolak type is as principal component.The determination data of feature As described below, can confirm that the chemical shift of the hydrogen atom of pi-allyl is moved after Claisen rearangement reaction.¹H-NMR (400MHz, CDCl₃, 27 DEG C), δ 3.2-3.4 (2H, m ,-CH ₂CH=CH₂), δ 3.6-4.0 (m ,-Ph-CH₂-Ph-,-OH), δ 4.6-5.0 (1H, m ,-CH₂CH=CHH), δ 5.0-5.3 (1H, m ,-CH₂CH=CHH), δ 5.8-6.1 (1H, m ,-CH₂CH= CH₂), δ 6.6-7.2 (m, phenyl ring).

For this resin, in formula (4), R¹、R²、R³In 1 be pi-allyl, other represent hydrogen atom.

The manufacture of [Production Example 2] polyimide precursor 1

By 4,4 '-diamino-diphenyl ether (Wako Pure Chemical Industries, Ltd.'s system, hereinafter referred to as " ODA ".)10.00g (0.05 mole) is dissolved in 1-METHYLPYRROLIDONE (Wako Pure Chemical Industries, Ltd.'s system, hereinafter referred to as " NMP ".) 70g, add Enter 3,3 ', 4,4 '-biphenyltetracarboxylic acid acid anhydride (Wako Pure Chemical Industries, Ltd.'s system, hereinafter referred to as " BPDA ".)13.22g (0.045 mole), stirs 5 hours at 40 DEG C.Thereafter, double (3-ethyl-5-methyl-4-maleimidophenyl) first is added (ケイアイ is melted into Co., Ltd.'s system, hereinafter referred to as " BMI-70 " to alkane.) 4.42g (0.01 mole), further at 90 DEG C Lower stirring 3 hours.After reaction solution is returned to room temperature, devote in acetone 1500mL, reclaim sediment, obtain faint yellow Solid.Further the solid obtaining is cleaned by water 1500mL, be dried 10 hours with the vacuum drier of 50 DEG C thereafter, gathered The pale yellow powder of imide precursor 1.The solid constituent acid number of polyimide precursor 1 is 175mgKOH/g.

The manufacture of [Production Example 3] polyimide precursor 2

ODA (Wako Pure Chemical Industries, Ltd.'s system) 10.00g (0.05 mole) is dissolved in NMP (with Wako Pure Chemical Industries strain Formula commercial firm system) 70g, add BPDA (Wako Pure Chemical Industries, Ltd.'s system) 13.22g (0.045 mole), at 40 DEG C, stir 5 Hour.Thereafter, add to hydroxy-benzyl alcohol (Wako Pure Chemical Industries, Ltd.'s system, hereinafter referred to as " p-HBzOH ".)5.58g (0.045 mole), stirs 3 hours further at 100 DEG C.After reaction solution is returned to room temperature, devote acetone In 1500mL, reclaim sediment, obtain faint yellow solid.Further the solid obtaining is cleaned by water 1500mL, thereafter, with 50 DEG C vacuum drier be dried 10 hours, obtain the pale yellow powder of polyimide precursor 2.The solid of polyimide precursor 2 becomes Acid number is divided to be 150mgKOH/g.

The manufacture of [Production Example 4] polyimide precursor 3

ODA (Wako Pure Chemical Industries, Ltd.'s system) 10.00g (0.05 mole) is dissolved in NMP (with Wako Pure Chemical Industries strain Formula commercial firm system) 70g, add BPDA (Wako Pure Chemical Industries, Ltd.'s system) 13.22g (0.045 mole), at 40 DEG C, stir 5 Hour.Thereafter, BMI-70 (ケイアイ is melted into Co., Ltd.'s system) 4.42g (0.01 mole) is added, further at 90 DEG C Stir 3 hours, add p-HBzOH (Wako Pure Chemical Industries, Ltd.'s system) 5.58g (0.045 mole), further at 100 DEG C Stir 3 hours.After reaction solution is returned to room temperature, devote in acetone 1500mL, reclaim sediment, obtain pale yellow colored solid Body.Further the solid obtaining is cleaned by water 1500mL, be dried 10 hours with the vacuum drier of 50 DEG C thereafter, obtain polyamides The pale yellow powder of imines precursor 3.The solid constituent acid number of polyimide precursor 3 is 115mgKOH/g.

The manufacture of [Production Example 5] polyimide precursor 4

ODA (Wako Pure Chemical Industries, Ltd.'s system) 10.00g (0.05 mole) is dissolved in NMP (with Wako Pure Chemical Industries strain Formula commercial firm system) 70g, add BPDA (Wako Pure Chemical Industries, Ltd.'s system) 13.22g (0.045 mole), at 40 DEG C, stir 5 Hour.Reaction solution is devoted in acetone 1500mL, reclaim sediment, obtain faint yellow solid.Further by consolidating of obtaining Body water 1500mL cleans, and is dried 10 hours with the vacuum drier of 50 DEG C thereafter, obtains the yellowish toner of polyimide precursor 4 End.The solid constituent acid number of polyimide precursor 4 is 210mgKOH/g.

(2) preparation of positive type photosensitive organic compound and evaluation

Embodiment 1

Using molten as the polyimide precursor 1 of alkali soluble resin for 6 mass parts many allyl phenols Resin A-1 and 20 mass parts Solution, in METHYLPYRROLIDONE 100 mass parts, adds 9 mass parts as TS-200A (Japan's conjunction of quinone di-azido compound Become Industrial Co., Ltd's system, the 1 of α, α, α-three (4-hydroxy phenyl)-1-ethyl-4-cumene, 2-naphthoquinones two nitrine-5-sulphur Acid esters).After visually confirming to dissolve, filter with the millipore filter in 1 μm of aperture, prepare normal Photosensitive resin combination Thing.

Embodiment 2

Polyimide precursor 1 is changed to polyimide precursor 2, in addition, prepares similarly to Example 1.

Embodiment 3

Polyimide precursor 1 is changed to polyimide precursor 3, in addition, prepares similarly to Example 1.

Embodiment 4

Polyimide precursor 1 is changed to polyimide precursor 4, in addition, prepares similarly to Example 1.

Embodiment 5

Polyimide precursor 1 is changed to phenol resol resins " ショウノ Le " (trade mark) BRG-556 (Showa Electrician Co., Ltd. system), in addition, prepare similarly to Example 1.

Embodiment 6

Polyimide precursor 1 is changed to cresol novolac resin " ショウノ Le " (trade mark) CRG-951 " (Showa Electrician Co., Ltd. system), in addition, prepare similarly to Example 1.

Comparative example 1

Polyene-based phenol resin A-1 is changed to cresol novolac resin " ショウノ Le ", and (trade mark) CRG-951 is (clear With electrician Co., Ltd. system), in addition, prepare similarly to Example 1.

Comparative example 2

Polyimide precursor 1 and polyene-based phenol resin A-1 are all changed to phenol resol resins " ショウノ Le " (trade mark) BRG-556 (Showa Denko K. K's system), in addition, prepares similarly to Example 1.

Comparative example 3

Polyimide precursor 1 and polyene-based phenol resin A-1 are all changed to cresol novolac resin " ショウノ Le " (trade mark) CRG-591 (Showa Denko K. K's system), in addition, prepares similarly to Example 1.

Acid number is measured to the polyimide precursor using in each embodiment and each comparative example, to each embodiment and each comparative example The positive type photosensitive organic compound of middle preparation, evaluation pattern generating formation, alkali-developable, releasing gas.Show the result in table 1.

The evaluation method of the assay method of acid number and pattern formation, alkali-developable and releasing gas is as described below.

[acid number]

It is measured according to JIS K0070.

[patternability and alkali-developable]

Glass substrate (size 100mm × 100mm × 1mm) becomes to be about each reality of spin coating in the way of 2 μm by dry film thickness Execute example and the positive type photosensitive organic compound of each comparative example, by solvent seasoning 2 minutes at 110 DEG C.Further with equipped with super The exposure device of high-pressure sodium lamp (trade name マ Le チライト ML-251A/B, ウシオ Electric Co., Ltd system), via quartz The photomask of system is with 600mJ/cm²It is exposed.Use ultraviolet accumulated light meter (trade name UIT-150, light accepting part UVD- S365, ウシオ Electric Co., Ltd system) measure light exposure.The film of exposure is further with 2.38% TMAH water Solution carries out alkali development, and the live width measuring pattern becomes the alkali developing time roughly the same with the live width of photomask, evaluation pattern generating Formative.This alkali developing time is 30～100 seconds and can carry out the situation of pattern formation and be judged to zero, by 100～180 seconds Situation is judged to △, the situation that will deviate from this scope is judged to ×.Photomask as the evaluation object of patternability The live width of pattern is 50 μm.

Using rotary developing device (AD-1200, Long Ze Industry Co., Ltd system) to carry out alkali development, live width measures and makes to use up Learn microscope (VH-Z250, Co., Ltd.'s Keyemce system).In addition, the live width at pattern becomes the substantially phase of the live width with photomask By the presence or absence of the development residue of observation by light microscope exposure portion in same alkali developing time, thus evaluate alkali-developable.To not have The situation having residue is judged to zero, the situation having residue is judged to ×.

[releasing gas]

The positive type photosensitive organic compound of each embodiment of application and comparative example on aluminium sheet, is dried 30 points at 100 DEG C Clock, makes the film of thickness 10～20 μm.After being dried 30 minutes at 130 DEG C in atmosphere further, under a nitrogen at 250 DEG C Lower solidification 60 minutes.Use its film, use differential thermogravimetric amount determinator TG/DTA7000 (Co., Ltd. Hitachi Ha イ simultaneously テ Network サイエ Application ス system), under nitrogen atmosphere from room temperature with 10 DEG C/min of intensifications, measure heating decrement as releasing gas. The temperature of the Mass lost 1% before heating up is designated as Td1, the temperature of Mass lost 5% is designated as Td5, is 370 DEG C by Td5 Above situation is judged to zero, is judged to △ by 350 DEG C less than the situation of 370 DEG C, and the situation that will be less than 350 DEG C judges For ×.

[table 1]

Industrial applicability

The radiation-ray sensitive composition of the present invention goes for positive radiation linear light lithography.Particularly go for The formation of the dielectric films such as organic electroluminescent device.

Claims

1. a positive type photosensitive organic compound, the polyene-based phenol resin containing the structure with formula (1), alkali soluble resin And quinone di-azido compound, wherein, described alkali soluble resin does not includes the polyene-based phenol resin with the structure of formula (1),

In formula (1), R¹、R²And R³Separately represent the alkene represented by hydrogen atom, the alkyl of carbon number 1～5, formula (2) Base, the alkoxyl of carbon number 1～2 or hydroxyl, and R¹、R²And R³In at least 1 thiazolinyl representing for formula (2)；Q is respectively solely On the spot expression-CR⁴R⁵The alkylidene of-expression, the cycloalkylidene of carbon number 5～10, the divalent organic base with aromatic rings Roll into a ball, there is the divalent organic group of ester ring type condensed ring or by the divalent group of these moiety combinations, R⁴And R⁵Independently Ground represents hydrogen atom, the alkyl of carbon number 1～5, the thiazolinyl of carbon number 2～6, the cycloalkyl of carbon number 5～10 or carbon The aryl of atomicity 6～12；

In formula (2), R⁶、R⁷、R⁸、R⁹And R¹⁰Separately represent hydrogen atom, the alkyl of carbon number 1～5, carbon number 5～ The cycloalkyl of 10 or the aryl of carbon number 6～12；* in formula (2) represents the bonding part with the carbon atom constituting aromatic rings.

2. positive type photosensitive organic compound according to claim 1, it is characterised in that

The structure of formula (1) is the structure of formula (3),

In formula (3), R¹、R²And R³Represent and the R in formula (1)¹、R²And R³The identical meaning.

3. positive type photosensitive organic compound according to claim 2, it is characterised in that the structure with formula (3) is many Thiazolinyl phenol resin contains the structure of formula (4),

In formula (4), R¹、R²And R³Represent and the R in formula (1)¹、R²And R³The identical meaning, in addition, the integer that p is 0～50.

4. the positive type photosensitive organic compound according to according to any one of claims 1 to 3, it is characterised in that formula (2) institute table The thiazolinyl showing is pi-allyl.

5. the positive type photosensitive organic compound according to according to any one of Claims 1 to 4, it is characterised in that alkali-soluble Resin is polyimide precursor.

6. the positive type photosensitive organic compound according to according to any one of Claims 1 to 5, it is characterised in that

Described polyimide precursor formula (5) represents,

In formula (5), R¹¹Represent the divalent organic group of carbon number more than 2, R¹²Represent trivalent or the tetravalence of carbon number more than 2 Organic group, R¹³Represent the organic group of hydrogen atom or carbon number 1～20, R¹⁴Represent hydrogen atom or carbon number 1～50 Organic group, m represents the integer that 1 or 2, n represent 5～200.

7. positive type photosensitive organic compound according to claim 6, it is characterised in that the R in formula (5)¹⁴Containing insatiable hunger And group.

8. positive type photosensitive organic compound according to claim 7, it is characterised in that described unsaturated group is Malaysia Imide.

9. positive type photosensitive organic compound according to claim 8, it is characterised in that described polyimide precursor passes through Following methods manufactures, and described method comprises following operation：

Operation (i)：Make the diamine compound represented by formula (6) with the acid compound represented by formula (7) with 1:0.8～0.95 rub You obtain, than carrying out reacting, the polyamic acid that end has amino,

H₂N-R¹¹-NH₂(6)

Wherein, x, y represent the integer that 0 or 1, z represent 0～4；And

Operation (ii)：Anti-with bismaleimide compound by the amino that makes the end of the polyamic acid obtaining in operation (i) End should be obtained there is the polyimide precursor of dimaleoyl imino.

10. the positive type photosensitive organic compound according to according to any one of claim 1～9, containing polyene-based phenol resin 20 ～50 mass parts, alkali soluble resin 100 mass parts and quinone di-azido compound 20～70 mass parts.

11. positive type photosensitive organic compounds according to according to any one of claim 6～10, it is characterised in that formula (5) institute The solid constituent acid number of the polyimide precursor representing is 110～210mgKOH/g.

12. 1 kinds of radioactive ray photolithographic structures things, it obtains by the following method, and described method comprises following operation：

(1) painting process：Positive type photosensitive organic compound according to any one of claim 1～11 for the coating on base material；

(3) exposure process：Irradiate radioactive ray across photomask；

(4) developing procedure：Developed by alkali and form pattern；And

(5) heating treatment step：Heat at a temperature of 150～350 DEG C.

13. radioactive ray photolithographic structures things according to claim 12, it is characterised in that temperature when thermal weight loss is 5 mass % Degree is more than 350 DEG C.